KR890004089B1

KR890004089B1 - Epoxy resin composition for encapsulating semiconductor

Info

Publication number: KR890004089B1
Application number: KR1019860008697A
Authority: KR
Inventors: 이정대; 오동섭; 문창모
Original assignee: 고려화학 주식회사; 정상영
Priority date: 1986-10-16
Filing date: 1986-10-16
Publication date: 1989-10-20
Also published as: KR880005204A

Abstract

The epoxy resin having an improved flowability, anti-humidity and electrical insulation property, is composed of novolac epoxy resin, phenolic accelerator, organic phosphine compd. and bisamide (I;R1=C15-20 straight hydrocarbon; R2=H, Me; n=2-10). Thus, 100 parts cresol novolac epoxy resin (epoxy equiv. 220), 350 parts silica, 2 parts-glycioxypropyl trimethoxy silane, 2 parts carbon black, 2.5 parts triphenyl phosphine, 0.5 parts N,N'-diphenyl thiourea and 3 parts (I)(R1=stearyl; R2=Me; n=2) are mixed to give the epoxy molding compd.

Description

Epoxy Resin Composition for Semiconductor Encapsulation

본 발명은 반도체 봉지용 에폭시수지 조성물에 관한 것으로, 특히 성형시 유동특성이 우수하며, 경화물의 내습성 및 고온에서의 전기절연특성이 향상된 에폭시수지 조성물에 관한 것이다.The present invention relates to an epoxy resin composition for semiconductor encapsulation, and more particularly, to an epoxy resin composition having excellent flow characteristics during molding, and improved moisture resistance of the cured product and electrical insulation at high temperatures.

에폭시수지는 전기절연특성, 기계적특성, 내약품성등이 우수한 신뢰성이 높은 전기절연 재료로서, IC, VLSI, 트란지스터, 다이오드등의 반도체 장치의 봉지재료로 광범위하게 응용되어 왔었다.Epoxy resin is a highly reliable electrical insulation material with excellent electrical insulation properties, mechanical properties, and chemical resistance, and has been widely applied as a sealing material for semiconductor devices such as ICs, VLSIs, transistors, and diodes.

이러한 반도체 봉지용 성형재료는 신뢰성, 성형 가공성등을 고려하여 에폭시수지, 페놀수지계 경화제, 이미다졸계 경화촉매 및 충진재로 구성되는 에폭시수지 조성물로서 이용되어왔다.The molding material for semiconductor encapsulation has been used as an epoxy resin composition composed of an epoxy resin, a phenol resin curing agent, an imidazole curing catalyst, and a filler in consideration of reliability, molding processability, and the like.

그러나, 최근에 들어서 전자부품 분야의 소형 경량화 경향에 따라 반도체 대용량화, 고집적화되고, 봉지형태도 SOP, FPP등으로 반도체 소자 크기에 비해 상대적으로 축소되어지고 그에 따라서, 반도체 봉지용 에폭시수지 조성물도 성형시 유동특성 및 경화물의 내습성, 고온에서의 전기절연특성의 향상이 요구되고 있으나, 종래의 반도체 봉지용 에폭시수지 조성물로는 이 요구를 충분히 만족시킬 수 없었다.However, in recent years, according to the trend of miniaturization and light weight in the field of electronic components, semiconductors have increased in capacity and high density, and the encapsulation forms have been reduced in size relative to the size of semiconductor devices such as SOP and FPP. Although the flow characteristics, the moisture resistance of hardened | cured material, and the improvement of the electrical insulation characteristic at high temperature are calculated | required, this request could not be fully satisfied by the conventional epoxy resin composition for semiconductor sealing.

유동특성의 불량은 성형중에 결속된(Bonding Wire) 및 반도체 소자를 손상시키거나, 반도체 소자와 경화수지층을 밀착성을 감소시키고, 그 결과 에폭시수지 봉지된 반도체 장치의 내습성을 저하시킨다.Poor flow characteristics damage the bonding wire and the semiconductor element during molding, or reduce the adhesion between the semiconductor element and the cured resin layer, and consequently lower the moisture resistance of the epoxy resin encapsulated semiconductor device.

반도체 장치의 경화수지층과 금속부품과의 계면 및 경화수지층을 통해 침투하는 수분은 경화수지 내부의 이온성 불순물과 반응하여, 금속부품을 부식시키고, 경화수지층의 전기절연특성을 저하시켜 반도체 장치의 정상적인 작동 및 수명등의 신뢰성에 치명적인 악영향을 준다.Moisture penetrating through the interface between the cured resin layer and the metal part of the semiconductor device and the cured resin layer reacts with the ionic impurities inside the cured resin, corrodes the metal part, and lowers the electrical insulating properties of the cured resin layer. It has a fatal adverse effect on the reliability of the device's normal operation and service life.

본 발명은 종래의 이미다졸계 경화촉매를 함유하는 반도체 봉지용 에폭시수지 조성물의 이러한 문제점을 해결하여, 유동특성 및 내습성, 고온에서의 전기절연 특성등이 향상된 반도체 봉지용 에폭시수지 조성물을 제공하기 위하여 개발되었다.The present invention solves these problems of the conventional epoxy resin composition for semiconductor encapsulation containing the imidazole series curing catalyst, to provide an epoxy resin composition for semiconductor encapsulation improved flow characteristics, moisture resistance, electrical insulation properties at high temperatures, etc. Was developed for.

본 발명에서는 노볼락형 에폭시수지와 페놀수지계 경화제를 기본성분으로 하는 에폭시수지 조성물에 유기포스핀계 화합물과 티오우레아 화합물중에서 선정된 화합물과 다음 일반식(Ⅰ)에 비스아미드계 화합물을 배합하여 반도체 봉지용 에폭시수지 조성물을 제조하였다.In the present invention, a semiconductor encapsulated by blending a compound selected from an organic phosphine compound and a thiourea compound and a bisamide compound in the following general formula (I) to an epoxy resin composition containing a novolak-type epoxy resin and a phenol resin-based curing agent An epoxy resin composition was prepared.

상기식에서 R₁은 탄소수 15-20인 직쇄의 탄화수소기, R₂는 수소 또는 메틸기, n은 2-10의 정수를 의미한다. 본 발명에서 사용되는 유기포스핀계 화합물과 티오우레아 화합물중에서 선정된 화합물은 종래의 반도체 봉지용 에폭시수지의 경화촉매로 사용되는 이마다졸계 화합물에 비해 내습성, 고온에서의 전기절연 특성이 향상된 경화물을 형성하며, 일반식(Ⅰ)의 비스아마이드계 화합물은 이형성, 성형시 유동특성 및 내습성 향상에 기여한다.In the above formula, R ₁ is a straight chain hydrocarbon group having 15-20 carbon atoms, R ₂ is hydrogen or methyl group, n is an integer of 2-10. The compound selected from the organic phosphine compound and the thiourea compound used in the present invention is a cured product having improved moisture resistance and electrical insulation at high temperature, compared to the imidazole compound used as a curing catalyst of a conventional epoxy encapsulation epoxy resin. In addition, the bisamide-based compound of the general formula (I) contributes to the release property, the flow characteristics and the moisture resistance improvement during molding.

본 발명에 적용가능한 노블락형 에폭시수지는 페놀 노볼락 에폭시수지 및 크레졸 노블락 에폭시수지중 에폭시 당량이 300이하이며, 연화점이 50-130℃ 범위인것이 적당하다.The noblock type epoxy resin applicable to the present invention has an epoxy equivalent of 300 or less in the phenol novolak epoxy resin and the cresol noblock epoxy resin, and a softening point of 50-130 ° C. is appropriate.

에폭시당량 300이상인 수지는 경화물의 경화밀도가 저하되며, 내열성이 부족하며, 연화점이 130℃이상인 에폭시 수지를 사용하는 경우에는 성형시 유동특성이 불량한 문제가 있으며 연화점 50℃이하인 경우에는 성형재료의 제조작업성 및 내습성이 불량하게 되는 문제가 있었다.When epoxy resin having a epoxy equivalent of 300 or more is lowered in the curing density of the cured product, heat resistance is insufficient, and when an epoxy resin having a softening point of 130 ° C. or higher is used, there is a problem in that the flow characteristics are poor during molding. There was a problem that workability and moisture resistance were poor.

페놀수지계 경화제로는 페놀, 크레졸, 레조시놀, 클로로페놀, 페닐페놀, 비스페놀-A중 하나 또는 둘이상의 혼합물과 포름알데히드 또는 파라포름 알데히드를 산촉매하에서 반응시켜 얻게되는 화합물로 1분자중 2개이상의 페놀성 수산기를 지니는 화합물인데, 특히 본 발명의 목적상 미반응 단량체가 적은것일수록 유리하다.Phenolic resin curing agent is a compound obtained by reacting one or two or more of phenol, cresol, resorcinol, chlorophenol, phenylphenol and bisphenol-A with formaldehyde or paraformaldehyde under an acidic catalyst. Compounds having phenolic hydroxyl groups, in particular for the purposes of the present invention, the less unreacted monomers are advantageous.

첨가량은 에폭시수지 1당량에 대하여 0.5-1.5당량에 범위가 가장 적당하다.The amount of addition is most suitably in the range of 0.5-1.5 equivalents to 1 equivalent of epoxy resin.

유기포스핀계 화합물 중에서 트리페닐포스핀, 트리부틸포스핀, 페틸디페닐 포스핀등과 같은 제3포스핀계 화합물, 부틸페닐포스핀, 디페닐포스핀등과 같은 제2포스핀계화합물, 페닐포스핀, 옥틸포스핀 등과 같은 제1포스핀계 화합물 및 비스(디페닐포스핀) 메탄, 1, 2-비스(디페닐포스핀)에탄등과 같은 비스포스핀계 화합물등이 적합하다.Among the organic phosphine compounds, a third phosphine compound such as triphenylphosphine, tributyl phosphine, petyldiphenyl phosphine, etc., a second phosphine compound such as butyl phenyl phosphine, diphenyl phosphine, phenyl phosphine And first phosphine compounds such as octylphosphine and bisphosphine compounds such as bis (diphenylphosphine) methane and 1,2-bis (diphenylphosphine) ethane.

티오우레아 중에는 에틸렌 티오우레아, N,N'-디페닐 티오우레아 및 디올소토릴티오우레아가 사용가능하다.Among the thioureas, ethylene thiourea, N, N'-diphenyl thiourea and diolsotorylthiourea can be used.

유기포스핀계 화합물과 티오우레아계의 배합비는 무게비로 95 : 5-80 : 20의 범위가 성형가공성, 저장안정성, 내습성, 고온에서의 전기특성등에서 가장 우수한 결과를 나타내며, 이 혼합물의 첨가량은 노볼락형 에폭시수지와 페놀수지계 경화제를 합한양의 0.05-10중량%의 범위가 적당하다.The compounding ratio of the organic phosphine compound and the thiourea compound is 95: 5-80: 20 in weight ratio, which shows the best results in moldability, storage stability, moisture resistance, and electrical properties at high temperature. The range of 0.05-10 weight% of the sum total of the condensation epoxy resin and the phenol resin hardener is suitable.

0.05중량%이하에서는 내습성 및 고온에서의 전기절연 특성의 개선이 불충분하며, 경화성이 불량해지고 10중량%이상에서는 저장안정성 및 가공특성이 불량해진다.Below 0.05% by weight, the improvement of the electrical insulation properties at moisture resistance and high temperature is insufficient, and the curability is poor, and above 10% by weight, the storage stability and the processing property are poor.

일반식(Ⅰ)의 구조를 지니는 비스아마이드 중에서 특히 에틸렌 비스 스테아릴 아마이드, 에틸렌 비스(N·메틸·N·스테아릴) 아마이드, 부틸렌 비스 스테아릴 아마이드, 등이 특히 유효하며, 첨가량은 전체 조성물에 대하여 0.5-5.0중량%범위가 가장 우수한 특성을 나타내었다.Among the bisamides having the structure of general formula (I), ethylene bis stearyl amide, ethylene bis (N-methyl N-stearyl) amide, butylene bis stearyl amide, and the like are particularly effective. 0.5-5.0% by weight with respect to the most excellent properties.

그러나, 0.5중량%이하에서는 이형성, 유동특성, 내습성등이 불량하며, 5.0중량%이상에서는 기계적, 전기적특성 및 내열성이 저하되는 문제가 있다.However, less than 0.5% by weight is poor in releasability, flow characteristics, moisture resistance, etc., there is a problem that mechanical, electrical properties and heat resistance is lowered at 5.0% by weight or more.

그밖에 본 발명의 반도체 봉지용 에폭시수지 조성물에는 실리카, 수산화 알미늄, 산화알미늄, 탄산칼슘, 활성분등의 무기를 충진재 및 실란계화합물 또는 티타니움계 무기물 표면처리제, 카본블랙등의 착색제가 첨가 가능하다.In addition, to the epoxy resin composition for semiconductor encapsulation of the present invention, fillers such as silica, aluminum hydroxide, aluminum oxide, calcium carbonate, and active ingredients can be added with fillers and colorants such as silane-based compounds or titanium-based inorganic surface treatment agents and carbon black.

본 발명의 에폭시수지 조성물을 제조하는 방법은 가열가능한 혼합용롤을 이용하는 방법 및 연속식 혼련장치를 이용하는 방법 모두가 적용가능하며 이때 온도는 에폭시수지의 특성 및 조성에 따라 다를 수 있으나, 70-110℃의 범위가 적당하다.The method of preparing the epoxy resin composition of the present invention is applicable to both the method using a heatable mixing roll and the method using a continuous kneading apparatus, wherein the temperature may vary depending on the properties and composition of the epoxy resin, 70-110 ℃ The range of is suitable.

본 발명의 에폭시수지 조성물의 성형방법은 이송성형, 압축성형, 사출성형등의 방법이 적용가능하며 성형조건은 이송성형의 경우 온도 150-180℃, 압력 50-150kg/㎠으로, 60초-180초동안 성형후, 160-200℃에서 5-15시간 후 경과하여, 원하는 성형품을 얻을 수 있다.The molding method of the epoxy resin composition of the present invention is applicable to the method of transfer molding, compression molding, injection molding, etc. The molding conditions in the case of the transfer molding temperature 150-180 ℃, pressure 50-150kg / ㎠, 60 seconds-180 After molding for seconds, after 5-15 hours at 160-200 ° C., the desired molded article can be obtained.

다음의 실시예에서 본 발명의 구체적인 적용방법 및 효과에 대하여 설명한다.In the following examples, specific application methods and effects of the present invention will be described.

그러나, 다음의 실시예가 본 발명의 범위를 한정하는 것은 아니다.However, the following examples do not limit the scope of the present invention.

[실시예 1]Example 1

크레졸 노볼락형 에폭시수지(에폭시당량 220) 100중량부, 페놀노볼락수지(수산기당량 105) 50중량부, 실리카 350중량부, 3-글리시옥시프로필 트리메톡시실란 2중량부 및 카본블랙 2중량부를 균질 혼합하고, 이 혼합물에 트리페닐포스핀 2.5중량부, N,N'-디페닐티오우레아 0.5중량부, 에틸렌 비스-N-메틸-N-스테아릴아마이드 3중량부를 에폭시수지 조성물을 제조하였다.100 parts by weight of cresol novolac-type epoxy resin (epoxy equivalent 220), 50 parts by weight of phenol novolac resin (hydroxyl equivalent 105), 350 parts by weight of silica, 2 parts by weight of 3-glycioxypropyl trimethoxysilane and carbon black 2 By weight homogeneously mixed, 2.5 parts by weight of triphenylphosphine, 0.5 parts by weight of N, N'-diphenylthiourea, and 3 parts by weight of ethylene bis-N-methyl-N-stearylamide were prepared in this mixture. It was.

[실시예 2]Example 2

실시예 1의 조성물중에서 트리페닐포스핀 3중량부, N,N'-디페닐 티오우레아 0.5중량부를 사용한 것이외에는 동일한 조성으로 에폭시수지 조성물을 제조하였다.An epoxy resin composition was prepared in the same composition except that 3 parts by weight of triphenylphosphine and 0.5 part by weight of N, N'-diphenyl thiourea were used in the composition of Example 1.

[실시예 3]Example 3

실시예 1의 조성물중에서 트리페닐포스핀 5중량부를 사용한 것이외에는 동일한 조성으로 에폭시수지 조성물을 제조하였다.An epoxy resin composition was prepared in the same composition except that 5 parts by weight of triphenylphosphine was used in the composition of Example 1.

[비교예 1]Comparative Example 1

실시예 1의 조성물중에서 트리페닐포스핀 2.5중량부 대신에 5중량부를 사용하고, N,N'-디페닐 티오우레아와 에틸렌-비스-N-메틸-N-스테아릴 아마이드를 사용하여 않고 스테아린산아연 2중량부를 사용한것 이외에는 동일한 조성으로 에폭시수지 조성물을 제조하였다.Zinc stearate without using 2.5 parts by weight of triphenylphosphine in the composition of Example 1 instead of N, N'-diphenyl thiourea and ethylene-bis-N-methyl-N-stearyl amide An epoxy resin composition was prepared in the same composition except that 2 parts by weight was used.

[비교예 2]Comparative Example 2

실시예 1의 조성물중에서 트리페닐포스핀과 N,N'-디페닐 티오우레아를 사용하지 않고 2-헵타메틸 이미다졸 2.5중량부를 사용한 것 이외에는 동일한 조성으로 에폭시수지 조성물을 제조하였다.The epoxy resin composition was prepared in the same composition except that 2.5 parts by weight of 2-heptamethyl imidazole was used without using triphenylphosphine and N, N'-diphenyl thiourea in the composition of Example 1.

[비교예 3]Comparative Example 3

실시예 1의 조성물중에서 트리페닐포스핀, N,N'-디페닐 티오우레아 및 에틸렌-비스-N-메틸-N-스테아릴아마이드 대신에 2-헵타메틸 이미다졸 2.5중량부와 스테아린산 아연 2중량부를 사용한것 이외에는 동일한 조성으로 에폭시수지 조성물을 제조하였다.2.5 parts by weight of 2-heptamethyl imidazole and 2 parts by weight of zinc stearate in place of triphenylphosphine, N, N'-diphenyl thiourea and ethylene-bis-N-methyl-N-stearylamide in the composition of Example 1 An epoxy resin composition was prepared in the same composition except that parts were used.

상기한 실시예 및 비교예로부터 제조된 조성물을 이용하여 유동특성 및 고온에서의 전기특성 평가를 위해 스파이럴 플로어 및 150℃에서의 체적 저항율을 측정하였으며, MOS형 IC소자를 함유하는 반도체 장치를 제조하여 신뢰성을 평가하였다.Using the compositions prepared from the above-described examples and comparative examples, the volume resistivity at 150 ° C. and the spiral floor were measured to evaluate the flow characteristics and the electrical characteristics at high temperatures, and a semiconductor device containing a MOS IC device was fabricated. Reliability was evaluated.

또한 MOS형 IC소자를 함유하는 반도체 장치 제조 공정중에 작업성도 함께 평가하였다.In addition, workability was also evaluated during the manufacturing process of a semiconductor device containing a MOS IC device.

평가결과는 다음과 같다.The evaluation results are as follows.

[표][table]

1)EMMI-1-66 시험방법에 의함.1) According to the test method of EMMI-1-66.

2) 120℃에서의 2kg/㎠의 수증기압, 500시간 처리후 불량품수(시료수 100)2) Water vapor pressure of 2kg / ㎠ at 120 ℃, defective product after 500 hours treatment (sample number 100)

3) 연속작업 2000회 성형시 금형청소 및 이형성 불량등의 원인으로 설비를 일시 중단하는 횟수.3) The number of times the equipment is suspended due to mold cleaning and mold release defects during 2000 consecutive molding operations.

상기한 결과에 의해 본 발명의 에폭시수지 조성물은 유동특성, 내습성, 고온에서의 전기절연특성이 향상되어, 신뢰성이 높은 반도체 장치의 제조가 가능하며 제조시 작업성도 대단히 우수한 것을 알 수 있다.As a result, it can be seen that the epoxy resin composition of the present invention has improved flow characteristics, moisture resistance, and electrical insulation properties at high temperatures, and therefore, it is possible to manufacture highly reliable semiconductor devices and to have excellent workability during manufacturing.

Claims

Epoxy resin composition comprising a novolak type epoxy resin and a phenol resin curing agent, wherein an organic phosphine compound, a thiourea compound, and a bisamide compound of the following general formula (I) are compounded. Resin composition.

In the above formula, R ₁ is a straight chain hydrocarbon group having 15-20 carbon atoms, R ₂ is hydrogen or methyl group, n is an integer of 2-10.

The method of claim 1, wherein the mixing ratio of the organic phosphine compound and the thiourea compound is 95: 5-80: 20 by weight, and the di-mixture contains 0.05-10% by weight based on the total weight of the novolak-type epoxy and phenol resin curing agent. An epoxy resin composition for semiconductor encapsulation.

The epoxy resin composition for semiconductor encapsulation according to claim 1, wherein the addition amount of the bisamide compound of the general formula (I) is 0.5-5% by weight based on the total composition.

The epoxy resin composition for semiconductor encapsulation according to claim 1 or 2, wherein the thiourea-based compound is ethylene thiourea, N, N'-diphenylthiourea and diolsotorylthiourea.