KR960011551B1 - Resin composition for encapsulating semiconductor element - Google Patents

Resin composition for encapsulating semiconductor element Download PDF

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KR960011551B1
KR960011551B1 KR1019930001390A KR930001390A KR960011551B1 KR 960011551 B1 KR960011551 B1 KR 960011551B1 KR 1019930001390 A KR1019930001390 A KR 1019930001390A KR 930001390 A KR930001390 A KR 930001390A KR 960011551 B1 KR960011551 B1 KR 960011551B1
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resin composition
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silica
resin
polysiloxane
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KR940019803A (en
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김성균
우희우
박윤철
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제일모직 주식회사
채오병
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention relates to resin compositions for encaptulating semiconductor having excellent strain and moisture resistant property and high adhesion property. The improvement is achieved by employing the special molten silica, which has the middle shape of angled and spherical molten silica. The special molten silica is prepared by crushing the siloxane group epoxy compounds as a modifying agent and molten spherical silica as inorganic filler.

Description

반도체 소자 봉지용 수지조성물(2)Resin Compositions for Semiconductor Device Encapsulation (2)

본 발명은 반도체 소자 봉지 재료에 관한 것으로, 특히 내습성, 내응력성 및 접착성이 우수한 반도체 소자 봉지용 수지조성물에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor element encapsulation material, and more particularly to a resin composition for semiconductor element encapsulation excellent in moisture resistance, stress resistance and adhesion.

IC, LSI, 초 LIS 등의 반도체 소자는 열, 수분, 충격과 같은 외부환경으로부터의 보호 및 전기절연 등을 목적으로 봉지되고 있으며, 가격 및 양산성 면에서 유리한 수지형 봉지가 주로 사용되고 있다.Semiconductor devices such as IC, LSI, ultra LIS and the like are encapsulated for the purpose of protection from external environment such as heat, moisture, impact, electrical insulation, etc., and resin type bags are advantageously used in terms of cost and mass productivity.

특히 근년에는 실장 합리화를 위해 종래의 삽입형 DIP 형으로 SOJ형 들의 표면실장형으로의 이행 및 패케지의 소형 박형화로 인해 수지형 봉지재에 내습성, 내응력성 및 고접착성의 부여가 요구되고 있다.In particular, in recent years, in order to rationalize mounting, it has been required to impart moisture resistance, stress resistance, and high adhesiveness to resin-type encapsulant due to the transition from the conventional insert type DIP type to the surface mount type and the small size of the package.

수지형 봉지제에 내응력성, 내습성 및 접착성을 부여하기 위한 종래의 기술로는 일본 특허공보 평 3-100015, 평 4-153213, 평 4-164953, 평 4-183711, 평 4-198252호 등이 있다.Conventional techniques for imparting stress resistance, moisture resistance, and adhesion to resin-type encapsulants include Japanese Patent Publication No. Hei 3-100015, Hei 4-153213, Hei 4-164953, Hei 4-183711, Hei 4-198252 Etc.

이중 일본특허공보 평3-100015호는 폴리 실록산계 실리콘오일류를 조성물의 변성제로 적용하여 내습성 및 접착성에서 취약하며, 일본특허공보 평4-153213호는 이미드기를 함유한 페놀수지의 적용으로 접착성의 향상을 기할 수 있었으나, 유리전이온도의 상승 및 극성기에 의한 내습성의 저하를 가져왔으며, 일본특허공보 평4-164953 및 평 4-198252호는 내습성 향상을 목적으로 무기 충전재의 함량 및 형태의 조합으로 이를 개선코자하였지만 적용소자의 한정 및 구상용융 실리카의 적용에 따른 내크랙성 취약의 문제점이 있다.Japanese Patent Application Laid-Open No. 3-100015 is vulnerable to moisture resistance and adhesion by applying polysiloxane silicone oils as a modifier of the composition, and Japanese Patent Application Laid-open No. Hei 4-153213 is applied by applying a phenol resin containing an imide group. Although the adhesion could be improved, the glass transition temperature was increased and the moisture resistance was reduced by the polar group. Japanese Patent Publications No. Hei 4-164953 and Hei 4-198252 contained inorganic fillers for the purpose of improving moisture resistance. Although it is intended to improve this by a combination of shapes, there is a problem of fragility resistance due to the limitation of the device and the application of spherical fused silica.

일본특허공보 평4-182711호는 2관능기의 에폭시수지 및 페놀수지를 주제 및 경화제로 적용하여 내습 및 접착성의 개선을 볼 수 있었으나 작업성 및 내열성이 부족한 문제점이 있다.Japanese Patent Application Laid-Open No. 4-182711 shows the improvement of moisture resistance and adhesion by applying an epoxy resin and a phenol resin of a bifunctional group as a main agent and a curing agent, but there is a problem in that workability and heat resistance are insufficient.

본 발명은 상기한 바와 같이 문제점을 해결하기 위한 것으로, 내응력성, 내습성 및 고접착성을 가진 반도체 소자 봉지용 수지 조성물을 제공하기 위한 것이다.The present invention is to solve the problem as described above, and to provide a resin composition for sealing semiconductor elements having stress resistance, moisture resistance and high adhesion.

본 발명자는 상기 목적을 달성하기 위하여 연구한 결과, 수지 조성물의 변성제로 나프틸기를 가진 실록산계 에폭시 화합물과 무기 충전제로 용융 구상 실라카를 파쇄하여 각상 및 구상 용융 실리카의 중간형을 가진 특수 용융실리카를 사용하게 되면 수지 조성물의 저응력화는 물론, 고접착성 및 고 내습성의 반도체소자 봉지용 수지 조성물을 얻을 수 있음을 밝혀 내게 되었다.The present inventors have studied in order to achieve the above object, and as a result of modifying the resin composition, a fused epoxy silica compound having a naphthyl group and a fused spherical silica with an inorganic filler were used to prepare a special fused silica having an intermediate form of each phase and spherical fused silica. It has been found that when used, a resin composition for sealing a semiconductor element can be obtained, as well as reducing the stress of the resin composition.

이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

본 발명의 수지 조성물의 조성은 다음의 표 1과 같다.The composition of the resin composition of this invention is as Table 1 following.

본 발명에 사용되는 에폭시 수지는 올소 크레졸 노블락형 에폭시 수지로 에폭시 당량이 185-210 이고, 연화점이 55-80℃이며, 이온화 할로겐 불순물 함량이 50ppm 이하인 고순도 에폭시 수지이어야 하며, 사용량은 5.0-15.0중량%가 적당하다.The epoxy resin used in the present invention is an oxo cresol noblock type epoxy resin with an epoxy equivalent of 185-210, a softening point of 55-80 ° C., an ionized halogen impurity content of 50 ppm or less, and an amount of 5.0-15.0 weight. % Is suitable.

노블락형 페놀수지는 수산기 당량이 100-110이고, 연화점이 70-100℃이며, 이온화 할로겐 불순물 함량이 5ppm 이하인 고순도의 것으로 그 사용량은 5.0-10.0중량%가 적합하다. 경화촉진제로는 유기 포스핀계 화합물인 트리페닐 포스핀을 0.1-0.5중량% 사용하며, 반응정도에 따라 이를 가감하여 적용한다.Noble-type phenolic resin is of high purity having a hydroxyl equivalent of 100-110, a softening point of 70-100 ° C., and an ionized halogen impurity content of 5 ppm or less, and its usage is suitably 5.0-10.0% by weight. As a curing accelerator, 0.1-0.5% by weight of triphenyl phosphine, an organic phosphine compound, is applied depending on the degree of reaction.

본 발명의 변성제는 아래의 구조식(1)과 같은 α-나프틸기 도는 β-나프틸기를 가진 폴리 실록산계 에폭시 화합물로서 수지 조성물에 적용시 실록산계 에폭시 화합물에 비해 내습성 및 접착성이 우수하며, 그 사용량은 2.0~10.0중량%가 적합하다.The modifying agent of the present invention is a polysiloxane-based epoxy compound having an α-naphthyl group or β-naphthyl group as shown in Structural Formula (1) below, and when applied to a resin composition, has excellent moisture resistance and adhesion as compared to a siloxane epoxy compound. The usage-amount is suitable for 2.0-10.0 weight%.

(A는 폴리실록산계 에폭사이드를 나타냄)(A represents polysiloxane-based epoxide)

본 발명의 충전재는 반구상 용융 실라카로서 용융 구상 실리카를 파쇄하여 각상 및 구상 용융 실리카의 중간형을 가진 특수용융 반구상 실리카로서 평균입자 크기가 11-15㎛이며, 입도분포는 45㎛ 이하가 95% 이상, 45㎛ 이상 75㎛ 이하가 4.0% 이하, 75㎛ 이상 150㎛ 이하가 0.1% 이하로서, 그 사용량은 70.0-85.0중량%가 적합하며, 용융각상 실리카를 충전재 사용량의 10.0-50.0중량% 적용하면 내크릭성 및 접착성을 보다 개선시킬 수 있다.The filler of the present invention is a specially melted hemispherical silica having the intermediate form of spherical and spherical fused silica by crushing the molten spherical silica as hemispherical fused silica, the average particle size is 11-15㎛, the particle size distribution is 45㎛ or less 95% or more, 45 micrometers or more and 75 micrometers or less are 4.0% or less, 75 micrometers or more and 150 micrometers or less are 0.1% or less, The usage-amount is suitable 70.0-85.0 weight%, and 10.0-50.0 weight of fused corner silica is used Application of% can further improve creep resistance and adhesion.

커플링제는 에폭시 또는 아민 관능기의 실란계 커플링제를 0.5-2.0중량% 사용하며, 이론 산출치의 0.5-1.0이 적합하다. 이형제는 천연 왁스계 및 합성왁스계를 각각 또는 이들의 조합으로 사용하며, 사용량은 0.2-1.0중량%가 적합하다. 착색제는 카아본 블랙을 0.2-0.5중량% 사용한다.The coupling agent uses 0.5-2.0% by weight of a silane coupling agent of an epoxy or amine functional group, and 0.5-1.0 of the theoretical calculation is suitable. The release agent uses natural waxes and synthetic waxes, respectively, or a combination thereof, and the amount of the release agent is 0.2-1.0% by weight. Colorants use 0.2-0.5% by weight of carbon black.

유기 난연제로는 브롬화 에폭시 수지를 1.0-5.0중량% 사용하며, 무기난연제로는 유기난연제의 사용량에 따라 1.0-3.0중량% 범위내에서 사용한다.The organic flame retardant is used in the brominated epoxy resin 1.0-5.0% by weight, the inorganic flame retardant is used within the range of 1.0-3.0% by weight depending on the amount of the organic flame retardant.

본 발명의 실시예는 다음과 같다.Embodiments of the present invention are as follows.

[실시예 1-3 및 비교예 1-2][Example 1-3 and Comparative Example 1-2]

표 2의 조성대로 헨셀믹서에서 균일하게 건식혼합한 후, 이를 롤밀(Roll Mill)에서 90℃, 5분의 조건으로 용융 혼합 후, 냉각, 분쇄, 분말화 과정을 거쳐 반도체 소자 봉지용 수지 조성물을 얻었다. 사용된 변성제는 아래의 표 3과 같다.After dry mixing uniformly in Henschel mixer according to the composition shown in Table 2, melt mixing at 90 ° C. for 5 minutes in a roll mill, and then cooling, pulverizing and powdering the resin composition for semiconductor element encapsulation. Got it. The modifiers used are shown in Table 3 below.

그리고 이 재료의 내습성, 내응력성 및 접착성의 정도를 평가하기 위하여 175℃, 70kg·f/cm 에서 110초간 성형하고, 175℃ 5시간 후 경화시킨 그 결과는 아래의 표 4와 같다.And 175 ℃, 70kg · f / cm to evaluate the degree of moisture resistance, stress resistance and adhesion of this material. Molded for 110 seconds at, and cured after 5 hours at 175 ℃ The results are shown in Table 4 below.

1) 흡수율(%) : PCT(2기압, 121℃, 24시간)후의 시편의 흡수율을 측정함.1) Absorption (%): Measure the absorption of the specimen after PCT (2 atm, 121 ℃, 24 hours).

2) 고온굴곡강도 (kg·f/mm ) : ASTM D 790에 의거하여 시편을 제작하고, UTM을 이용하여 측정함.2) High temperature bending strength (kgf / mm ): Specimens were prepared according to ASTM D 790 and measured using UTM.

3) 고온굴곡탄성율 (kg·f/mm ) : ASTM D 790에 의거하여 시편을 제작하고, UTM을 이용하여 측정함.3) High temperature flexural modulus (kgf / mm ): Specimens were prepared according to ASTM D 790 and measured using UTM.

4) 열선팽창계수(1/℃) : TMA를 이용하여 측정함.4) Coefficient of thermal expansion (1 / ℃): Measured using TMA.

5) 접착력(kg·f) : PULL TEST법으로 리이드 프레임과 수지조성물과의 접착력을 UTM을 이용하여 측정함.5) Adhesive force (kg · f): The adhesive force between the lead frame and the resin composition is measured by UTM using the PULL TEST method.

상기 실시예 및 비교예에 의하여 확인되는 바와 같이, 변성제를 α-나프틸기 또는 β-나프틸기를 가진 폴리실록산계 에폭시 화합물과 충전재로서 특수 용융 반구상 실리카를 적용함으로써 흡수율, 고온굴곡강도, 고온굴곡탄성율, 열선팽창계수 및 접착력이 개선되어 내습성, 저응력성 및 접착성이 우수한 반도체 소자 봉지용 수지 조성물로 유용하게 사용될 수 있다.As confirmed by the above Examples and Comparative Examples, the modifier is a polysiloxane-based epoxy compound having an α-naphthyl group or a β-naphthyl group, and by applying special molten hemispherical silica as a filler, absorption rate, high temperature flexural strength, and high temperature flexural modulus. In addition, the coefficient of thermal expansion and adhesion may be improved, and thus it may be usefully used as a resin composition for encapsulating semiconductor devices having excellent moisture resistance, low stress, and adhesion.

Claims (5)

하기 성분을 함유하는 것을 특징으로 하는 반도체 소자 봉지용 수지 조성물.The following composition contains the resin composition for sealing semiconductor elements. 가) 에폭시 수지A) epoxy resin 나) 노볼락형페놀수지B) novolac type phenolic resin 다) 하기 구조식(I)을 가진 폴리실록산 에폭시 화합물의 변성제C) Modifiers of polysiloxane epoxy compounds having the following structural formula (I) (A는 폴리 실록산계 에폭사이드를 나타냄)(A represents polysiloxane-based epoxide) 라) 용융 구상 실리카를 파쇄하여 각상 및 구상 용융 실리카의 중간형을 가진 용융 반구상 실리카 충전재.D) fused hemispherical silica filler having an intermediate form of angular and spherical fused silica by crushing the fused spherical silica. 마) 이형제E) release agent 바) 착색제F) colorants 사) 경화촉진제G) curing accelerator 아) 유기난연제H) organic flame retardant 자) 무기난연제Inorganic flame retardants 제1항에 있어서, 충전재(라)는 평균입자 크기가 11-15㎛, 입도분포는 45㎛ 이하가 95% 이상, 45㎛ 이상 75㎛ 이하가 4.0% 이하, 75㎛ 이상 150㎛ 이하가 0.1% 이하인 용융 반구상 실리카 충전재인 것을 특징으로 하는 반도체 소자 봉지용 수지 조성물.The filler (D) has an average particle size of 11-15 µm and a particle size distribution of 45 µm or less, 95% or more, 45 µm or more and 75 µm or less, 4.0% or less, 75 µm or more and 150 µm or less. It is a molten hemispherical silica filler which is% or less, The resin composition for semiconductor element sealing characterized by the above-mentioned. 제1항에 있어서, 수지조성물 전체에 대하여 다)의 변성제의 조성비가 2.0-10.0중량%인 것을 특징으로 하는 수지조성물.The resin composition according to claim 1, wherein the composition ratio of the modifier of c) to the whole resin composition is 2.0 to 10.0% by weight. 제1항에 있어서, 수지조성물 전체에 대하여 라)의 충전재의 조성비가 70-85중량%인 것을 특징으로 하는 수지조성물.The resin composition according to claim 1, wherein the composition ratio of the filler of d) is 70-85 wt% with respect to the entire resin composition. 제1항에 있어서, 다)의 변성제는 α-나프틸기 또는 β-나프틸기를 가진 에폭시 수지가 70-80중량%, 아민관능기의 폴리실록산제 실리콘오일이 20-30중량%인 폴리실록산계 에폭시 화합물을 질소분위기 110-160℃에서 2-5시간 반응시킨 것을 특징으로 하는 수지조성물.The polysiloxane-based epoxy compound according to claim 1, wherein the modifier of c) comprises 70-80% by weight of an epoxy resin having an α-naphthyl group or a β-naphthyl group and 20-30% by weight of a polysiloxane silicone oil having an amine function. Resin composition characterized in that the reaction for 2-5 hours at 110-160 ℃ nitrogen atmosphere.
KR1019930001390A 1993-02-02 1993-02-02 Resin composition for encapsulating semiconductor element KR960011551B1 (en)

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