KR20060002853A - Resin composition for sealing semiconductor and semiconductor device using the same - Google Patents

Resin composition for sealing semiconductor and semiconductor device using the same Download PDF

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KR20060002853A
KR20060002853A KR1020057017829A KR20057017829A KR20060002853A KR 20060002853 A KR20060002853 A KR 20060002853A KR 1020057017829 A KR1020057017829 A KR 1020057017829A KR 20057017829 A KR20057017829 A KR 20057017829A KR 20060002853 A KR20060002853 A KR 20060002853A
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resin composition
semiconductor
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epoxy resin
weight
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KR100697938B1 (en
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구니하루 우메노
시게히사 우에다
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스미토모 베이클라이트 가부시키가이샤
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
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    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32245—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
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    • H01L2224/45001—Core members of the connector
    • H01L2224/45099—Material
    • H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
    • H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
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    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
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    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
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    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
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    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
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    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
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    • H01L2224/732—Location after the connecting process
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    • H01L23/3107—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed
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Abstract

A resin composition for sealing a semiconductor, which comprises a phenol aralkyl type epoxy resin having a biphenylene skeleton (A), a phenol aralkyl resin having a phenylene skeleton or biphenylene skeleton (B), an inorganic filler (C) in an amount of 84 to 90 wt % and a curing accelerator (D), as main components, and further comprises a silane coupling agent (E) in an amount of 0.01 wt % to 1 wt % and an aromatic compound (F) having two or more hydroxyl groups bonded to adjacent carbon atoms in an aromatic ring in an amount of 0.01 wt % or more, the percentages being relative to the total amount of the resin composition. The resin composition exhibits improved flowability, without detriment to its curability.

Description

반도체 봉지용 수지 조성물 및 이것을 사용한 반도체장치{Resin composition for sealing semiconductor and semiconductor device using the same}Resin composition for sealing semiconductor and semiconductor device using the same}

본 발명은 반도체 봉지용 수지 조성물 및 그것을 사용한 반도체장치에 관한 것이다.The present invention relates to a resin composition for semiconductor encapsulation and a semiconductor device using the same.

최근, 반도체장치는 생산성, 비용, 신뢰성 등의 균형이 우수한 것으로부터 에폭시 수지 조성물을 사용하여 봉지(encapsulating)되는 것이 주류로 되어 있다. 반도체장치의 소형화, 박형화에 수반하여, 봉지용 에폭시 수지 조성물에 대해서는, 보다 한층 저점도화, 고강도화가 요구되고 있다. 또한, 환경문제로부터 Br 화합물이나 산화안티몬 등의 난연제를 사용하지 않고 난연화하는 요구가 높아지고 있다. 이러한 배경으로부터, 최근의 에폭시 수지 조성물의 동향은, 보다 저점도의 수지를 적용하여, 보다 많은 무기 충전제를 배합하는 경향이 강해지고 있다.BACKGROUND ART In recent years, semiconductor devices have become mainstream to be encapsulated using an epoxy resin composition because of excellent balance of productivity, cost, and reliability. With miniaturization and thinning of a semiconductor device, further lowering viscosity and high strength are calculated | required about the epoxy resin composition for sealing. In addition, there is an increasing demand for flame retardation without using flame retardants such as Br compounds and antimony oxide due to environmental problems. From such a background, the tendency of the recent epoxy resin composition to apply more low viscosity resin and to mix | blend more inorganic fillers becomes strong.

또한 새로운 움직임으로서, 반도체장치를 실장(mounting)할 때, 종래 보다도 융점이 높은 무연 땜납(unleaded solder)의 사용이 높아지고 있다. 이 땜납의 적용에 의해 실장온도(mounting temperature)를 종래에 비해 약 20℃ 높게 할 필요가 있어, 실장 후의 반도체장치의 신뢰성이 현재상태에 비해 현저히 저하되는 문제가 발생하고 있다. 이와 같은 사실로부터 에폭시 수지 조성물의 레벨 업에 의한 반도 체장치의 신뢰성의 향상 요구가 가속적으로 강해지고 있어, 수지의 저점도화와 무기 충전제의 고충전화에 박차가 가해지고 있다.In addition, as a new move, the use of unleaded solder having a higher melting point than in the past when mounting a semiconductor device is increasing. The application of this solder requires a mounting temperature of about 20 ° C. higher than in the prior art, which causes a problem that the reliability of the semiconductor device after mounting is significantly lower than in the current state. From these facts, the demand for improving the reliability of semiconductor devices due to the level-up of the epoxy resin composition is rapidly increasing, and spurs are being applied to the low viscosity of the resin and the high filling of the inorganic filler.

성형시에 저점도이고 고유동성을 유지하기 위해서는, 용융점도가 낮은 수지를 사용하거나(특허문헌 1), 또한 무기 충전제의 배합량을 높기이 위해 무기 충전제를 실란커플링제(silane coupling agent)로 표면처리하는 방법이 알려져 있다(특허문헌 2).In order to maintain a low viscosity and high fluidity during molding, a resin having a low melt viscosity is used (Patent Document 1), or an inorganic filler is surface-treated with a silane coupling agent in order to increase the compounding amount of the inorganic filler. The method is known (patent document 2).

그런데, 이들 방법만으로는 내크랙성(crack resistance), 유동성(flowability) 및 난연성(fire resistance) 모두를 만족하는 수법은 아직 발견되지 않았다. 내크랙성, 난연성이 우수한 수지를 사용하고, 추가로 무기 충전제의 배합량을 높여 신뢰성을 만족시켜, 유동성과 경화성을 손상시키지 않는 추가의 기술이 요구되고 있었다.However, these methods alone have not yet found a method that satisfies both crack resistance, flowability, and fire resistance. The use of resins excellent in crack resistance and flame retardancy, further increased the compounding amount of the inorganic filler to satisfy the reliability, and further technology that does not impair fluidity and curability has been required.

특허문헌 1 일본국 특허공개 제(평)7-130919호 공보(제2~5페이지)Patent Document 1 Japanese Patent Application Laid-Open No. 7-130919 (pages 2-5)

특허문헌 2 일본국 특허공개 제(평)8-20673호 공보(제2~4페이지)Patent Document 2: Japanese Patent Application Laid-Open No. 8-20673 (Page 2 to 4)

발명의 개시Disclosure of the Invention

본 발명은 상기 사정에 비추어 이루어진 것으로, 그 목적은 반도체 봉지용 수지 조성물 성형시의 경화성을 손상시키지 않고 유동성을 향상시키는 기술을 제공하는 것에 있다.This invention is made | formed in view of the said situation, The objective is to provide the technique of improving fluidity, without impairing the curability at the time of shaping | molding of the resin composition for semiconductor sealing.

본 발명에 의하면, 화학식 1로 표시되는 에폭시 수지(A), 하기 화학식 2로 표시되는 페놀 수지(B), 무기 충전제(C), 경화 촉진제(D), 실란커플링제(E) 및 방향고리(aromatic ring)를 구성하는 2개 이상의 인접하는 탄소원자에 각각 수산기가 결합된 화합물(F)를 포함하는 것을 특징으로 하는 반도체 봉지용 수지 조성물이 제공된다.According to the present invention, an epoxy resin (A) represented by the formula (1), a phenol resin (B) represented by the following formula (2), an inorganic filler (C), a curing accelerator (D), a silane coupling agent (E) and an aromatic ring ( A resin composition for semiconductor encapsulation is provided comprising a compound (F) having a hydroxyl group bonded to at least two adjacent carbon atoms constituting an aromatic ring).

Figure 112005053150148-PCT00001
Figure 112005053150148-PCT00001

(다만, 상기 화학식 1에 있어서, R은 수소 또는 탄소수 4 이하의 알킬기이다. 또한, n은 평균값으로, 1~10의 양수이다.)(However, in the general formula (1), R is hydrogen or an alkyl group having 4 or less carbon atoms. In addition, n is an average value and is a positive number of 1 to 10.

Figure 112005053150148-PCT00002
Figure 112005053150148-PCT00002

(다만, 상기 화학식 2에 있어서, R1은 페닐렌기 또는 비페닐렌기, R2는 탄소수 4 이하의 알킬기이다. 또한, n은 평균값으로, 1~10의 양수이다.)(However, in the above formula (2), R 1 is a phenylene group or a biphenylene group, R 2 is an alkyl group having 4 or less carbon atoms. N is an average value and is a positive number of 1 to 10.

본 발명의 반도체 봉지 수지 조성물은, 상기 화학식 1 및 2로 나타내어지는 수지를 포함하고, 화합물(F)를 필수 성분으로서 포함하기 때문에, 성형시의 경화성 및 유동성을 충분히 확보할 수 있다.Since the semiconductor sealing resin composition of this invention contains resin represented by the said General formula (1) and (2), and contains compound (F) as an essential component, the curability and fluidity at the time of shaping | molding can fully be ensured.

본 발명의 반도체 봉지 수지 조성물은, 상기 에폭시 수지(A), 상기 페놀 수 지(B), 상기 무기 충전제(C) 및 경화 촉진제(D)를 주성분으로 할 수 있다.The semiconductor sealing resin composition of this invention can have the said epoxy resin (A), the said phenol resin (B), the said inorganic filler (C), and a hardening accelerator (D) as a main component.

본 발명의 반도체 봉지용 수지 조성물에 있어서, 상기 화합물(F)를 해당 수지 조성물 전체의 0.01 중량% 이상 포함해도 된다. 이렇게 함으로써, 반도체 봉지용 수지 조성물 성형시의 경화성을 저하시키지 않고 유동성을 향상시킬 수 있다.In the resin composition for semiconductor encapsulation of the present invention, the compound (F) may contain 0.01% by weight or more of the entire resin composition. By doing in this way, fluidity | liquidity can be improved, without reducing curability at the time of shaping | molding of the resin composition for semiconductor sealing.

또한, 본 발명의 반도체 봉지용 수지 조성물에 있어서, 상기 실란커플링제(E)를 해당 수지 조성물 전체의 0.01 중량% 이상 1.0 중량% 이하 포함해도 된다. 이렇게 함으로써, 반도체 봉지용 수지 조성물 성형시의 경화성 및 유동성을 더욱 향상시킬 수 있다.Moreover, in the resin composition for semiconductor sealing of this invention, you may contain the said silane coupling agent (E) 0.01 weight% or more and 1.0 weight% or less of the whole said resin composition. By doing in this way, sclerosis | hardenability and fluidity | liquidity at the time of shaping | molding of the resin composition for semiconductor sealing can be improved further.

본 발명의 반도체 봉지용 수지 조성물에 있어서, 상기 무기 충전제(C)를 해당 수지 조성물 전체의 84 중량% 이상 90 중량% 이하 포함해도 된다. 이렇게 함으로써, 수지 조성물을 확실하게 저점도화하고, 또한 고강도화할 수 있다.In the resin composition for semiconductor sealing of this invention, you may contain the said inorganic filler (C) 84 weight% or more and 90 weight% or less of the said resin composition whole. By doing in this way, a resin composition can be reliably low-viscosity and also high strength.

본 발명의 반도체 봉지용 수지 조성물에 있어서, 상기 화합물(F)는 방향고리를 구성하는 2개의 인접하는 탄소원자에 각각 수산기가 결합된 화합물이어도 된다. 이렇게 함으로써, 성형시의 경화성 및 유동성을 적합하게 확보할 수 있다. In the resin composition for semiconductor encapsulation of the present invention, the compound (F) may be a compound in which a hydroxyl group is bonded to two adjacent carbon atoms constituting the aromatic ring, respectively. By doing in this way, the curability and fluidity at the time of shaping | molding can be ensured suitably.

본 발명의 반도체 봉지용 수지 조성물에 있어서, 상기 방향고리가 나프탈렌고리인 구성으로 할 수 있다. 이렇게 함으로써, 성형시의 경화성및 유동성을 더욱 향상시킬 수 있다.In the resin composition for semiconductor sealing of this invention, it can be set as the structure whose said aromatic ring is a naphthalene ring. By doing in this way, the curability and fluidity at the time of shaping | molding can be improved further.

본 발명의 반도체 봉지용 수지 조성물에 있어서, 상기 화합물(F)는 나프탈렌고리를 구성하는 2개의 인접하는 탄소원자에 각각 수산기가 결합된 화합물이어도 된다. 이렇게 함으로써, 성형시의 경화성 및 유동성의 균형을 보다 한층 향상시킬 수 있다. In the resin composition for semiconductor encapsulation of the present invention, the compound (F) may be a compound in which a hydroxyl group is bonded to two adjacent carbon atoms constituting the naphthalene ring, respectively. By doing in this way, the balance of curability and fluidity at the time of shaping | molding can be improved more.

본 발명에 의하면, 상기 반도체 봉지용 수지 조성물을 사용하여 반도체 소자를 봉지해서 되는 것을 특징으로 하는 반도체장치가 제공된다. 본 발명의 반도체장치는, 상술한 반도체 봉지용 수지 조성물을 사용해서 봉지되기 때문에, 제조안정성을 충분히 확보할 수 있다.According to this invention, the semiconductor device is provided by sealing a semiconductor element using the said resin composition for semiconductor sealing. Since the semiconductor device of this invention is sealed using the resin composition for semiconductor sealing mentioned above, manufacturing stability can fully be ensured.

이상 설명한 바와 같이 본 발명에 의하면, 경화성을 유지하면서 성형시의 유동성이 우수한 에폭시 수지 조성물을 얻을 수 있다.As explained above, according to this invention, the epoxy resin composition excellent in the fluidity | liquidity at the time of shaping | molding can be obtained, maintaining curability.

도면의 간단한 설명Brief description of the drawings

상술한 목적 및 그 밖의 목적, 특징 및 이점은, 이하에 기술하는 적합한 실시형태 및 그것에 부수하는 이하의 도면에 의해 더욱 명확해진다.The above objects and other objects, features, and advantages are further clarified by the following preferred embodiments and the accompanying drawings.

도 1은 본 발명의 실시형태의 반도체장치 구성의 일례를 나타내는 단면도이다.1 is a cross-sectional view showing an example of the configuration of a semiconductor device of an embodiment of the present invention.

발명을 실시하기 위한 최선의 형태Best Mode for Carrying Out the Invention

본 발명의 수지 조성물은,The resin composition of the present invention,

하기 화학식 1로 나타내어지는 에폭시 수지(A)Epoxy resin (A) represented by the following formula (1)

[화학식 1][Formula 1]

Figure 112005053150148-PCT00003
Figure 112005053150148-PCT00003

(다만, 상기 화학식 1에 있어서, R은 수소 또는 탄소수 4 이하의 알킬기이다. 또한, n은 평균값으로, 1~10의 양수이다.)(However, in the general formula (1), R is hydrogen or an alkyl group having 4 or less carbon atoms. In addition, n is an average value and is a positive number of 1 to 10.

하기 화학식 2로 나타내어지는 페놀 수지(B)Phenolic resin (B) represented by the following formula (2)

[화학식 2][Formula 2]

Figure 112005053150148-PCT00004
Figure 112005053150148-PCT00004

(다만, 상기 화학식 2에 있어서, R1은 페닐렌기 또는 비페닐렌기, R2는 탄소수 4 이하의 알킬기이다. 또한, n은 평균값으로, 1~10의 양수이다.)(However, in the above formula (2), R 1 is a phenylene group or a biphenylene group, R 2 is an alkyl group having 4 or less carbon atoms. N is an average value and is a positive number of 1 to 10.

무기 충전제(C)Inorganic Filler (C)

경화 촉진제(D)Curing Accelerator (D)

실란커플링제(E)Silane Coupling Agent (E)

방향고리를 구성하는 2개 이상의 인접하는 탄소원자에 각각 수산기가 결합된 화합물(F)Compound (F) having hydroxyl groups bonded to two or more adjacent carbon atoms constituting the aromatic ring

를 필수 성분으로 한다.Is an essential ingredient.

에폭시 수지 조성물 전체를 기준으로 하여, (A)~(F) 성분의 함유량은, 예를 들면 이하와 같이 할 수 있다.Based on the whole epoxy resin composition, content of (A)-(F) component can be performed as follows, for example.

(A): 1~40 중량%,(A): 1-40 wt%,

(B): 1~40 중량%,(B): 1-40% by weight,

(C): 40~97 중량%,(C): 40 to 97% by weight,

(D): 0.001~5 중량%,(D): 0.001-5% by weight,

(E): 0.01~1 중량%,(E): 0.01 to 1% by weight,

(F): 0.01~1 중량%.(F): 0.01-1 weight%.

이하, 본 발명의 반도체 봉지용 에폭시 수지 조성물을 구성하는 각 성분에 대해서 설명한다.Hereinafter, each component which comprises the epoxy resin composition for semiconductor sealing of this invention is demonstrated.

상기 화학식 1로 표시되는 에폭시 수지는, 주쇄(main chain)에 소수성(hydrophobic)이고 강직(rigid)한 비페닐렌 골격을 가지고 있어, 이것을 사용한 에폭시 수지 조성물의 경화물은 흡습율이 낮고, 유리전이온도(이하, Tg라고 한다.)를 초과한 고온역에서의 탄성율이 낮아, 반도체 소자, 유기 기판 및 금속 기판과의 밀착성이 우수하다. 또한, 난연성도 우수하고, 가교밀도가 낮은 것에 비해서는 내열성이 높다고 하는 특징을 가지고 있다.The epoxy resin represented by the formula (1) has a hydrophobic and rigid biphenylene skeleton in the main chain, and the cured product of the epoxy resin composition using the same has low moisture absorption and glass transition. The elasticity modulus in the high temperature range exceeding temperature (henceforth Tg) is low, and it is excellent in adhesiveness with a semiconductor element, an organic substrate, and a metal substrate. Moreover, it is excellent in flame retardancy and has the characteristic that heat resistance is high compared with low crosslinking density.

화학식 1로 표시되는 에폭시 수지(A)로서는, 예를 들면 페놀 비페닐아랄킬형 에폭시 수지 등을 들 수 있는데, 화학식 1의 구조라면 특별히 한정되는 것은 아니다.As an epoxy resin (A) represented by General formula (1), a phenol biphenyl aralkyl type epoxy resin etc. are mentioned, for example, If it is a structure of General formula (1), it will not specifically limit.

또한, 화학식 1로 표시되는 에폭시 수지에 의한 효과가 손상되지 않는 범위 에서, 다른 에폭시 수지와 병용할 수 있다. 병용할 수 있는 에폭시 수지로서는, 예를 들면 비페닐형(biphenyl type) 에폭시 수지, 비스페놀형(bisphenol type) 에폭시 수지, 스틸벤형(stilbene type) 에폭시 수지, 페놀 노볼락형(phenol novolac type) 에폭시 수지, 크레졸 노볼락형(cresol novolac type) 에폭시 수지, 트리페놀메탄형(triphenolmethane type) 에폭시 수지, 페놀아랄킬형(phenolaralkyl type) 에폭시 수지, 나프톨형(naphthol type) 에폭시 수지, 알킬 변성(alkyl-modified) 트리페놀메탄형 에폭시 수지, 트리아진 핵 함유 에폭시 수지, 디시클로펜타디엔 변성 페놀형 에폭시 수지 등을 들 수 있다.Moreover, it can use together with another epoxy resin in the range in which the effect by the epoxy resin represented by General formula (1) is not impaired. As an epoxy resin which can be used together, it is a biphenyl type epoxy resin, a bisphenol type epoxy resin, a stilbene type epoxy resin, a phenol novolac type epoxy resin, for example. Cresol novolac type epoxy resin, triphenolmethane type epoxy resin, phenolaralkyl type epoxy resin, naphthol type epoxy resin, alkyl-modified Triphenol methane type epoxy resin, a triazine nucleus containing epoxy resin, a dicyclopentadiene modified phenol type epoxy resin, etc. are mentioned.

반도체 봉지용 에폭시 수지 조성물로서의 내습(moisture-resistance) 신뢰성을 고려하면, 이온성 불순물인 Na 이온이나 Cl 이온이 매우 적은 쪽이 바람직하고, 경화성 면에서 에폭시 당량을, 예를 들면 100 g/eq 이상 500 g/eq 이하로 할 수 있다.In view of moisture-resistance reliability as an epoxy resin composition for semiconductor encapsulation, it is preferable that Na ions and Cl ions which are ionic impurities are very small, and the epoxy equivalent is, for example, 100 g / eq or more in terms of curability. It can be made into 500 g / eq or less.

상기 화학식 2로 표시되는 페놀 수지(B)는 주쇄에 소수성인 페닐렌기 또는 소수성이고 강직한 비페닐렌 골격을 가지고 있어, 이것을 사용한 에폭시 수지 조성물의 경화물은 흡습율이 낮고, Tg를 초과한 고온역에서의 탄성율이 낮아, 반도체 소자, 유기 기판 및 금속 기판과의 밀착성이 우수하다. 또한, 난연성도 우수하고, 가교밀도도 낮은 것에 비해서는 내열성이 높다고 하는 특징을 가지고 있다.The phenol resin (B) represented by the formula (2) has a hydrophobic phenylene group or a hydrophobic, rigid biphenylene skeleton in the main chain, and the cured product of the epoxy resin composition using the same has a low moisture absorption rate and a high temperature exceeding Tg. The elasticity modulus in the area is low, and it is excellent in adhesiveness with a semiconductor element, an organic substrate, and a metal substrate. Moreover, it is excellent in flame retardancy, and has the characteristic that heat resistance is high compared with low crosslinking density.

화학식 2로 표시되는 페놀 수지(B)로서는, 예를 들면 페놀 비페닐아랄킬 수지나 페놀아랄킬 수지 등을 들 수 있는데, 화학식 2의 구조라면 특별히 한정되지는 않는다.As a phenol resin (B) represented by General formula (2), a phenol biphenyl aralkyl resin, a phenol aralkyl resin, etc. are mentioned, for example, If it is a structure of general formula (2), it will not specifically limit.

본 발명에서는, 화학식 2로 표시되는 페놀 수지에 의한 효과가 손상되지 않는 범위에서, 다른 페놀 수지와 병용할 수 있다. 병용할 수 있는 페놀 수지로서는, 예를 들면 페놀 노볼락 수지, 크레졸 노볼락 수지, 트리페놀메탄 수지, 테르펜 변성(terpene-modified) 페놀 수지, 디시클로펜타디엔 변성 페놀 수지, 나프톨아랄킬 수지(페닐렌 골격, 비페닐렌 골격 등을 포함한다) 등을 들 수 있다. 경화성 면에서 수산기 당량은, 예를 들면 90 g/eq 이상 250 g/eq 이하로 하는 것이 바람직하다.In this invention, it can use together with another phenol resin in the range in which the effect by the phenol resin represented by General formula (2) is not impaired. As a phenol resin which can be used together, a phenol novolak resin, a cresol novolak resin, a triphenol methane resin, a terpene-modified phenol resin, a dicyclopentadiene modified phenol resin, a naphthol aralkyl resin (phenyl Lene skeleton, biphenylene skeleton, and the like). In view of curability, the hydroxyl equivalent is preferably, for example, 90 g / eq or more and 250 g / eq or less.

무기 충전제(C)의 재료로서는, 일반적으로 봉지재료에 사용되고 있는 용융 실리카, 구형상 실리카, 결정 실리카, 알루미나, 질화규소, 질화알루미늄 등을 들 수 있다. 무기 충전제의 입경(particle size)으로서는 금형(mold)으로의 충전성을 고려하면, 예를 들면 0.01 ㎛ 이상 150 ㎛ 이하로 할 수 있다.As a material of an inorganic filler (C), fused silica, spherical silica, crystalline silica, alumina, silicon nitride, aluminum nitride, etc. which are generally used for sealing materials are mentioned. The particle size of the inorganic filler can be, for example, 0.01 µm or more and 150 µm or less in consideration of the filling property in a mold.

또한 무기 충전제(C)의 충전량을, 예를 들면 에폭시 수지 조성물 전체의 84 중량% 이상 90 중량% 이하로 할 수 있다. 충전량이 지나치게 작으면 에폭시 수지 조성물 경화물의 수흡수량이 증가하여, 강도가 저하되기 때문에 내땜납성(solder resistance)이 불만족스러워질 우려가 있다. 또한, 충전량이 지나치게 크면, 유동성이 손상되기 때문에 성형성이 저하될 우려가 있다.Moreover, the filling amount of an inorganic filler (C) can be made into 84 weight% or more and 90 weight% or less of the whole epoxy resin composition, for example. When the filling amount is too small, the water absorption amount of the cured epoxy resin composition increases, and the strength is lowered, so that solder resistance may be unsatisfactory. In addition, when the filling amount is too large, there is a fear that the moldability is lowered because the fluidity is impaired.

경화 촉진제(D)의 재료는, 에폭시 수지의 에폭시기와 페놀 수지의 수산기와의 반응을 촉진시키는 것이면 되고, 일반적으로 반도체 소자의 봉지재인 에폭시 수지 조성물에 사용되고 있는 것을 이용할 수 있다. 구체예로서 유기 포스핀, 테트라 치환 포스포늄화합물, 포스포베타인화합물 등의 인원자 함유 화합물, 1,8-디아자비시클로(5,4,0)운데센-7, 벤질디메틸아민, 2-메틸이미다졸 등의 질소원자 함유 화합 물을 들 수 있다.The material of a hardening accelerator (D) should just promote reaction of the epoxy group of an epoxy resin with the hydroxyl group of a phenol resin, and what is generally used for the epoxy resin composition which is a sealing material of a semiconductor element can be used. Specific examples include a person-containing compound such as an organic phosphine, a tetra-substituted phosphonium compound, and a phosphobetaine compound, 1,8-diazabicyclo (5,4,0) undecene-7, benzyldimethylamine, 2-methyl Nitrogen atom containing compounds, such as imidazole, are mentioned.

유기 포스핀으로서는, 예를 들면 에틸포스핀, 페닐포스핀 등의 제1 포스핀;As an organic phosphine, For example, 1st phosphines, such as ethyl phosphine and phenyl phosphine;

디메틸포스핀, 디페닐포스핀 등의 제2 포스핀; 및 트리메틸포스핀, 트리에틸포스핀, 트리부틸포스핀, 트리페닐포스핀 등의 제3 포스핀;Second phosphines such as dimethyl phosphine and diphenyl phosphine; And third phosphines such as trimethyl phosphine, triethyl phosphine, tributyl phosphine and triphenyl phosphine;

등을 들 수 있다.Etc. can be mentioned.

테트라 치환 포스포늄화합물로서, 하기 화학식 3에 나타내는 화합물을 들 수 있다.As a tetra substituted phosphonium compound, the compound shown by following General formula (3) is mentioned.

Figure 112005053150148-PCT00005
Figure 112005053150148-PCT00005

(상기 화학식 3에 있어서, P는 인원자, R1, R2, R3 및 R4는 치환 또는 무치환의 방향족기, 또는 알킬기, A는 히드록실기, 카르복실기, 티올기로부터 선택되는 관능기 중 어느 하나를 방향고리에 적어도 하나 갖는 방향족 유기산의 음이온, AH는 히드록실기, 카르복실기, 티올기 중 어느 하나를 방향고리에 적어도 하나 갖는 방향족 유기산을 나타낸다. a, b는 1 이상 3 이하의 정수, c는 0 이상 3 이하의 정수이고, 또한 a=b이다.)(In Formula 3, P is a person group, R 1 , R 2 , R 3 and R 4 is a substituted or unsubstituted aromatic group, or an alkyl group, A is a functional group selected from a hydroxyl group, a carboxyl group, a thiol group An anion of an aromatic organic acid having at least one in the aromatic ring, AH represents an aromatic organic acid having at least one of a hydroxyl group, a carboxyl group and a thiol group in the aromatic ring, a, b is an integer of 1 or more and 3 or less, c is an integer of 0 or more and 3 or less, and a = b.)

상기 화학식 3에 나타내는 화합물은, 예를 들면 이하와 같이 하여 얻어진다. 먼저, 테트라 치환 포스포늄 브로마이드와 방향족 유기산과 염기를 유기용제에 섞 어 균일하게 혼합하고, 그 용액계 내에 방향족 유기산 음이온을 발생시킨다. 이어서 물을 가한다. 그러면, 상기 화학식 3에 나타내는 화합물을 침전시킬 수 있다.The compound shown by the said General formula (3) is obtained as follows, for example. First, tetra-substituted phosphonium bromide, an aromatic organic acid, and a base are mixed in an organic solvent, uniformly mixed, and an aromatic organic acid anion is generated in the solution system. Then water is added. Then, the compound shown in Formula 3 can be precipitated.

상기 화학식 3에 나타내는 화합물에 있어서, 인원자에 결합하는 R1, R2, R3 및 R4가 페닐기이고, 또한 AH는 히드록실기를 방향고리에 갖는 화합물, 즉 페놀류이며, 또한 A는 상기 페놀류의 음이온인 것이 바람직하다.In the compound represented by the formula (3), R 1 , R 2 , R 3 and R 4 bonded to the phosphorus atom are phenyl groups, and AH is a compound having a hydroxyl group in the aromatic ring, that is, phenols, and A is It is preferable that it is an anion of phenols.

포스포베타인화합물로서, 하기 화학식 4에 나타내는 화합물을 들 수 있다.As a phosphobetaine compound, the compound shown by following General formula (4) is mentioned.

Figure 112005053150148-PCT00006
Figure 112005053150148-PCT00006

(상기 화학식 4에 있어서, X는 수소 또는 탄소수 1~3의 알킬기, Y는 수소 또는 히드록실기를 나타낸다. m, n은 1~3의 정수.)(In the formula (4), X represents hydrogen or an alkyl group having 1 to 3 carbon atoms, and Y represents hydrogen or a hydroxyl group. M, n are integers of 1 to 3.)

상기 화학식 4에 나타내는 화합물은, 예를 들면 이하와 같이 하여 얻을 수 있다. 먼저, 요오드화페놀류와 트리방향족 치환 포스핀을 유기용매에 균일하게 혼합하고, 니켈촉매에 의해 요오드늄염으로서 침전시킨다. 이 요오드늄염과 염기를 유기용재에 균일하게 혼합하고, 필요에 따라 물을 가하면, 상기 화학식 4에 나타내는 화합물을 침전시킬 수 있다.The compound shown by the said General formula (4) can be obtained as follows, for example. First, iodide phenols and triaromatic substituted phosphines are uniformly mixed with an organic solvent, and precipitated as an iodonium salt by a nickel catalyst. If this iodonium salt and a base are mixed uniformly with an organic solvent, and water is added as needed, the compound shown by the said General formula (4) can be precipitated.

상기 화학식 4에 나타내는 화합물로서는, 바람직하게는 X가 수소 또는 메틸 기이고, 또한 Y가 수소 또는 히드록실기인 것이 바람직하다. 그러나 이들에 한정되지 않고, 단독으로도 병용해도 된다.As the compound represented by the formula (4), preferably X is hydrogen or a methyl group, and Y is preferably hydrogen or a hydroxyl group. However, it is not limited to these and may be used alone or in combination.

경화 촉진제(D)의 배합량은, 예를 들면 에폭시 수지 조성물 전체의 0.1 중량% 이상 1 중량% 이하로 할 수 있고, 0.1 중량% 이상 0.6 중량% 이하로 하는 것이 바람직하다. 경화 촉진제(D)의 배합량이 지나치게 적으면 목적으로 하는 경화성이 얻어지지 않을 우려가 있다. 또한, 지나치게 많으면 유동성이 손상될 우려가 있다.The compounding quantity of a hardening accelerator (D) can be 0.1 weight% or more and 1 weight% or less of the whole epoxy resin composition, for example, It is preferable to set it as 0.1 weight% or more and 0.6 weight% or less. When the compounding quantity of a hardening accelerator (D) is too small, the target hardenability may not be obtained. Moreover, when too much, there exists a possibility that fluidity may be impaired.

실란커플링제(E)는 에폭시실란, 아미노실란, 우레이도실란, 메르캅토실란 등 특별히 한정되지 않고, 에폭시 수지 조성물과 무기 충전제 사이에서 반응하여, 에폭시 수지 조성물과 무기 충전제의 계면(界面) 강도를 향상시키는 것이면 된다.The silane coupling agent (E) is not particularly limited, such as epoxy silane, amino silane, ureido silane, mercapto silane, and the like. The silane coupling agent (E) reacts between the epoxy resin composition and the inorganic filler, and the interface strength between the epoxy resin composition and the inorganic filler is increased. You just need to improve it.

방향고리를 구성하는 2개 이상의 인접하는 탄소원자에 각각 수산기가 결합된 화합물(F)(이하, 화합물(F)라 칭한다.)는, 실란커플링제(E)와의 상승효과에 의해, 점도 특성과 유동 특성을 현저히 개선시키기 때문에, 실란커플링제(E)는 화합물(F)의 효과를 충분히 얻기 위해서는 필수이다.Compound (F) (hereinafter referred to as compound (F)) in which a hydroxyl group is bonded to two or more adjacent carbon atoms constituting the aromatic ring, respectively, has a viscosity characteristic and a synergistic effect with the silane coupling agent (E). Since the flow characteristic is remarkably improved, the silane coupling agent (E) is essential for fully obtaining the effect of the compound (F).

이들 실란커플링제(E)는 단독으로도 병용해도 된다. 실란커플링제(E)의 배합량은, 예를 들면 에폭시 수지 조성물 전체의 0.01 중량% 이상 1 중량% 이하, 바람직하게는 0.05 중량% 이상 0.8 중량% 이하, 특히 바람직하게는 0.1 중량% 이상 0.6 중량% 이하로 할 수 있다. 배합량이 지나치게 작으면 화합물(F)의 효과가 충분히 얻어지지 않고, 또한 반도체 팩키지(package)에 있어서의 내땜납성이 저하될 우려가 있다. 또한, 지나치게 크면 에폭시 수지 조성물의 수흡수성이 커지고, 역시 반도체 팩키지에 있어서의 내땜납성이 저하될 우려가 있다.These silane coupling agents (E) may be used alone or in combination. The blending amount of the silane coupling agent (E) is, for example, 0.01 wt% or more and 1 wt% or less, preferably 0.05 wt% or more and 0.8 wt% or less, particularly preferably 0.1 wt% or more and 0.6 wt% or less of the entire epoxy resin composition. It can be set as follows. If the compounding amount is too small, the effect of the compound (F) is not sufficiently obtained, and there is a fear that the solder resistance in the semiconductor package is lowered. Moreover, when too big | large, there exists a possibility that the water absorption of an epoxy resin composition may become large, and also solder resistance in a semiconductor package may fall.

방향고리를 구성하는 2개 이상의 인접하는 탄소원자에 각각 수산기가 결합된 화합물(F)는, 수산기 이외의 치환기를 가지고 있어도 된다. 화합물(F)로서, 하기 화학식 5로 나타내어지는 단환식 화합물(monocyclic compound) 또는 하기 화학식 6으로 나타내어지는 다환식 화합물(polycyclic compound)을 사용할 수 있다.The compound (F) in which the hydroxyl group is bonded to two or more adjacent carbon atoms constituting the aromatic ring may have a substituent other than the hydroxyl group. As the compound (F), a monocyclic compound represented by the following formula (5) or a polycyclic compound represented by the following formula (6) can be used.

Figure 112005053150148-PCT00007
Figure 112005053150148-PCT00007

(상기 화학식 5에 있어서 R1, R5는 어느 한쪽이 수산기이고, 한쪽이 수산기일 때 다른 한쪽은 수소, 수산기 또는 수산기 이외의 치환기. R2, R3, R4는 수소, 수산기 또는 수산기 이외의 치환기.)(In formula (5), R 1 and R 5 each represent a hydroxyl group, and when one is a hydroxyl group, the other is a substituent other than hydrogen, a hydroxyl group or a hydroxyl group. R 2 , R 3 , and R 4 are other than hydrogen, a hydroxyl group or a hydroxyl group. Substituents.)

Figure 112005053150148-PCT00008
Figure 112005053150148-PCT00008

(상기 화학식 6에 있어서, R1, R7은 어느 한쪽이 수산기이고, 한쪽이 수산기일 때 다른 한쪽은 수소, 수산기 또는 수산기 이외의 치환기. R2, R3, R4, R5, R6는 수소, 수산기 또는 수산기 이외의 치환기.)(In the formula (6), R 1 , R 7 is a hydroxyl group, when one is a hydroxyl group, the other is a substituent other than hydrogen, hydroxyl groups or hydroxyl groups. R 2 , R 3 , R 4 , R 5 , R 6 Is a substituent other than hydrogen, hydroxyl or hydroxyl.)

상기 화학식 5로 나타내어지는 단환식 화합물의 구체예로서, 예를 들면, 카테콜(catechol), 피로갈롤(pyrogallol), 몰식자산(gallic acid), 몰식자산 에스테르 또는 이들의 유도체 등을 들 수 있다. 또한, 상기 화학식 6으로 나타내어지는 다환식 화합물의 구체예로서, 예를 들면, 1,2-디히드록시나프탈렌, 2,3-디히드록시나프탈렌 및 이들의 유도체 등을 들 수 있다.Specific examples of the monocyclic compound represented by Formula 5 include catechol, pyrogallol, gallic acid, molar esters, and derivatives thereof. Moreover, as a specific example of the polycyclic compound represented by the said General formula (6), 1, 2- dihydroxy naphthalene, 2, 3- dihydroxy naphthalene, derivatives thereof, etc. are mentioned, for example.

그 중, 유동성과 경화성 제어의 용이함으로부터 방향고리에 인접하는 수산기는 2개가 보다 바람직하다. 또한, 혼련공정에서의 휘발을 고려한 경우, 모핵은 저휘발성으로 칭량 안정성(weighing stability)이 높은 나프탈렌고리인 화합물인 것이 바람직하다.Among them, two hydroxyl groups adjacent to the aromatic ring are more preferable from the ease of fluidity and curability control. In addition, in consideration of volatilization in the kneading step, the mother nucleus is preferably a compound having a low volatile naphthalene ring with high weighing stability.

이 경우, 화합물(F)를 구체적으로는 예를 들면, 1,2-디히드록시나프탈렌, 2,3-디히드록시나프탈렌 및 그의 유도체 등의 나프탈렌고리를 갖는 화합물로 할 수 있다. 이러한 화합물을 사용함으로써, 에폭시 수지 조성물의 핸들링(handling)시의 제어성을 보다 한층 향상시킬 수 있다. 또한, 에폭시 수지 조성물의 휘발성을 저하시킬 수 있다.In this case, the compound (F) can be made into the compound which has naphthalene ring, such as 1, 2- dihydroxy naphthalene, 2, 3- dihydroxy naphthalene, and its derivative specifically ,. By using such a compound, the controllability at the time of handling of an epoxy resin composition can be improved further. Moreover, volatility of an epoxy resin composition can be reduced.

이들 화합물(F)는 2종류 이상 병용해도 된다.You may use together 2 or more types of these compounds (F).

이러한 화합물(F)의 배합량은 에폭시 수지 조성물 전체의 0.01 중량% 이상 0.5 중량% 이하, 바람직하게는 0.02 중량% 이상 0.3 중량% 이하이다. 지나치게 작으면 실란커플링제(E)와의 상승효과에 의한 기대하는 바와 같은 점도 특성 및 유동 특성이 얻어지지 않는다. 또한, 지나치게 크면 에폭시 수지 조성물의 경화가 저해되고, 또한 경화물의 물성이 떨어져, 반도체 봉지 수지로서의 성능이 저하된다.The compounding quantity of such a compound (F) is 0.01 weight% or more and 0.5 weight% or less of the whole epoxy resin composition, Preferably they are 0.02 weight% or more and 0.3 weight% or less. When too small, the viscosity characteristic and flow characteristic as expected by the synergistic effect with a silane coupling agent (E) cannot be obtained. Moreover, when too large, hardening of an epoxy resin composition will be inhibited, the physical property of hardened | cured material will fall, and the performance as a semiconductor sealing resin will fall.

본 발명의 에폭시 수지 조성물은, 상기 (A)~(F) 성분을 필수 성분으로 하는데, 이것 이외에 필요에 따라 브롬화 에폭시 수지, 삼산화 안티몬 등의 난연제(fire retardant), 이형제(mold release), 카본블랙(carbon black) 등의 착색제, 실리콘오일, 실리콘고무 등의 저응력 첨가제, 무기 이온 교환체 등의 첨가제를 적절히 배합해도 된다.Although the epoxy resin composition of this invention makes the said (A)-(F) component an essential component, In addition, if necessary, a flame retardant, a mold release agent, carbon black, such as a brominated epoxy resin and antimony trioxide, etc. You may mix | blend suitably coloring agents, such as (carbon black), additives, such as low stress additives, such as silicone oil and silicone rubber, and an inorganic ion exchanger.

본 발명의 에폭시 수지 조성물은 (A)~(F) 성분 및 그 밖의 첨가제 등을 믹서 등으로 사용하여 상온에서 균일하게 혼합한 후, 가열롤(heating roller) 또는 니더(kneader), 압출기(extruder) 등으로 용융혼련하고, 냉각 후 분쇄하여 제조할 수 있다. The epoxy resin composition of the present invention is uniformly mixed at room temperature by using (A) to (F) components and other additives as a mixer, etc., and then a heating roller or kneader or an extruder. Melt-kneaded, or the like after cooling, to be pulverized.

또한, 본 발명의 에폭시 수지 조성물을 사용하여 반도체 소자를 봉지하고, 반도체장치를 제조하기 위해서는, 트랜스퍼 몰드(transfer molding), 컴프레션 몰드(compression molding), 인젝션 몰드(injection molding) 등의 성형방법으로 성형 경화하면 된다.In addition, in order to seal a semiconductor element using the epoxy resin composition of this invention and to manufacture a semiconductor device, it shape | molds by shaping | molding methods, such as transfer molding, compression molding, injection molding, and the like. It is enough to cure.

본 발명의 에폭시 수지 조성물은, 각종 반도체장치의 봉지에 적합하게 사용된다. 예를 들면, QFP(quad flat package), TSOP(thin small outline package) 등의 표면실장형(surface mounting type) 반도체장치의 봉지재료로서 사용할 수 있 다. 도 1은 본 발명의 에폭시 수지 조성물을 사용한 반도체장치 구성의 일례를 나타내는 단면도이다. 다이 패드(die pad)(2) 위에, 다이 본드재 경화체(6)을 매개로 하여 반도체 소자(1)이 고정되어 있다. 반도체 소자(1)과 리드 프레임(lead frame)(4) 사이는 금선(gold wire)(3)에 의해 접속되어 있다. 반도체 소자(1)은 봉지 수지(5)에 의해 봉지되어 있다. The epoxy resin composition of this invention is used suitably for sealing various semiconductor devices. For example, it can be used as a sealing material for surface mounting type semiconductor devices such as quad flat package (QFP) and thin small outline package (TSOP). BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows an example of the structure of the semiconductor device using the epoxy resin composition of this invention. The semiconductor element 1 is fixed on the die pad 2 via the die bond material hardened body 6. The semiconductor element 1 and the lead frame 4 are connected by a gold wire 3. The semiconductor element 1 is sealed by the sealing resin 5.

도 1에 나타내어지는 반도체장치는, 봉지 수지(5)로서 상술한 에폭시 수지 조성물을 사용하여 트랜스퍼 몰드, 컴프레션 몰드, 인젝션 몰드 등의 방법으로 경화 성형하고, 반도체 소자(1)을 봉지함으로써 얻을 수 있다.The semiconductor device shown in FIG. 1 can be obtained by hardening and molding the semiconductor element 1 by a method such as a transfer mold, a compression mold, an injection mold, and the like using the epoxy resin composition described above as the sealing resin 5. .

도 1에 나타낸 반도체장치는, 방향고리를 구성하는 2개 이상의 인접하는 탄소원자에 각각 수산기가 결합된 화합물(F)를 포함하는 봉지 수지 조성물에 의해 봉지되기 때문에, 봉지 수지 조성물의 점도 특성과 유동 특성을 적합한 것으로 할 수 있다. 이 때문에, 성형성이 우수한 반도체장치를 안정적으로 얻을 수 있다.Since the semiconductor device shown in FIG. 1 is sealed by the sealing resin composition containing the compound (F) in which the hydroxyl group was couple | bonded with two or more adjacent carbon atoms which comprise an aromatic ring, the viscosity characteristic and flow of the sealing resin composition A characteristic can be made suitable. For this reason, the semiconductor device excellent in moldability can be obtained stably.

또한, 화학식 1로 표시되는 에폭시 수지 및 화학식 2로 표시되는 페놀 수지를 포함하는 에폭시 수지 조성물에 의해 봉지함으로써, 난연성, 내땜납성이 더욱 우수한 반도체장치를 보다 한층 안정적으로 얻을 수 있다.Moreover, by sealing with the epoxy resin composition containing the epoxy resin represented by General formula (1) and the phenol resin represented by General formula (2), the semiconductor device excellent in flame retardancy and solder resistance can be obtained more stably.

이하, 본 발명을 실시예에서 구체적으로 설명하는데, 본 발명은 이들 실시예에 의해 조금도 한정되는 것은 아니다. 배합비율은 중량부로 한다.Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by these Examples. The blending ratio is made by weight part.

(실시예 1)(Example 1)

페놀 비페닐아랄킬형 에폭시 수지(닛폰 가야쿠(주)제, NC3000P, 에폭시 당량 274, 상기 화학식 1에 있어서의 n은 평균값으로 2.8, 연화점(softening point) 58℃) 7.35 중량부,Phenol biphenyl aralkyl type epoxy resin (Nippon Kayaku Co., Ltd. make, NC3000P, epoxy equivalent 274, n in the said Formula 1 is 2.8 in average value, 58 degreeC of softening point, 7.35 weight part,

페놀 비페닐아랄킬 수지(메이와 가세이(주)제, MEH-7851SS, 수산기 당량 203, 상기 화학식 2에 있어서의 n은 평균값으로 2.5, 연화점 65℃) 5.5 중량부,5.5 weight part of phenol biphenyl aralkyl resin (made by Meiwa Kasei Co., Ltd., MEH-7851SS, hydroxyl equivalent 203, n in the said General formula (2) is 2.5, softening point 65 degreeC in average value),

구형상 용융 실리카(평균입경 30 ㎛) 86.0 중량부,86.0 parts by weight of spherical fused silica (average particle diameter: 30 μm),

γ-글리시딜프로필트리메톡시실란 0.4 중량부,0.4 parts by weight of γ-glycidylpropyltrimethoxysilane,

트리페닐포스핀 0.2 중량부,0.2 parts by weight of triphenylphosphine,

2,3-디히드록시나프탈렌(시약) 0.05 중량부,0.05 part by weight of 2,3-dihydroxynaphthalene (reagent),

카나우바 왁스(carnauba wax) 0.2 중량부 및0.2 parts by weight of carnauba wax and

카본블랙 0.3 중량부 0.3 parts by weight of carbon black

를 믹서에서 상온 혼합하여, 80~100℃의 가열롤로 용융혼련하고, 냉각 후 분쇄하여 에폭시 수지 조성물을 얻었다. 얻어진 에폭시 수지 조성물을 이하의 방법으로 평가하였다. 평가결과를 표 1에 나타낸다.The mixture was mixed at room temperature in a mixer, melt kneaded with a heating roll at 80 to 100 ° C., and cooled and pulverized to obtain an epoxy resin composition. The obtained epoxy resin composition was evaluated by the following method. Table 1 shows the evaluation results.

스파이럴 플로우(spiral flow): EMMI-1-66에 준한 금형을 사용하여, 상기 에폭시 수지 조성물을 저압 트랜스퍼 성형기에서 175℃, 성형압(molding pressure) 6.9 MPa, 보압시간(pressure keeping time) 120초의 조건으로 성형해서 측정하였다. 스파이럴 플로우는, 유동성의 파라미터로, 수치가 큰 쪽이 유동성이 양호하다. 단위는 ㎝.Spiral flow: Using the mold according to EMMI-1-66, the epoxy resin composition was 175 ° C in a low pressure transfer molding machine, molding pressure of 6.9 MPa, pressure keeping time of 120 seconds. Molded and measured. Spiral flow is a parameter of fluidity, and the larger the value, the better the fluidity. The unit is cm.

경화 토크비(curing torque ratio): 큐라스토미터(curastometer)(오리엔텍(주)제, JSR 큐라스토미터 IVPS형)를 사용하여, 금형온도 175℃, 가열개시 90초 후, 300초 후의 토크를 구하여, 경화 토크비: (90초 후의 토크)/(300초 후의 톨쿠)를 계산하였다. 큐라스토미터에 있어서의 토크는 열강성(thermal rigidity)의 파라미터로, 경화 토크비가 큰 쪽이 경화성이 양호하다. 단위는 %.Curing torque ratio: Curingometer (Orientec Co., Ltd., JSR Curator Meter IVPS type) is used, and the torque after 300 seconds after 90 seconds of heating at a mold temperature of 175 캜 is started. The hardening torque ratio: (torque after 90 second) / (torque after 300 second) was calculated. Torque in a curator meter is a parameter of thermal rigidity, and the harder torque ratio is larger, and its hardenability is favorable. Unit is%.

내땜납 리플로 크랙성(solder resistance-reflow cracking): 저압 트랜스퍼 성형기를 사용하여, 바디 사이즈 14×14×1.4 ㎜의 100pQFP(Cu 프레임)에 6×6×0.30 ㎜의 Si 칩을 접착한 프레임을 금형온도 175℃, 주입시간 10 sec, 경화시간 90 sec, 주입압 9.8 MPa로 성형하고, 175℃ 8 hr의 조건으로 후경화 후 85℃ 85% 48 hr의 조건으로 가습처리하고, 피크온도 260℃의 IR 리플로에 연속 3회(255℃ 이상이 10초×3회) 통과시키고, 초음파 탐상기(ultrasonic flaw detector)를 사용하여 내부 크랙, 박리의 유무를 측정하고, 10 팩키지 중의 칩 박리와 내부 크랙의 수로 판정하였다.Solder resistance-reflow cracking: Using a low pressure transfer molding machine, a frame in which a Si chip of 6 × 6 × 0.30 mm is bonded to 100pQFP (Cu frame) having a body size of 14 × 14 × 1.4 mm. After molding at a mold temperature of 175 ° C, an injection time of 10 sec, a curing time of 90 sec, and an injection pressure of 9.8 MPa, after curing at 175 ° C for 8 hr, humidification was performed at a condition of 85 ° C to 85% 48 hr and a peak temperature of 260 ° C. Three consecutive passes of IR reflow (10 seconds x 3 times above 255 ° C) are performed using an ultrasonic flaw detector to measure the presence of internal cracks and delamination. Judging by the number.

난연성: 저압 트랜스퍼 성형기를 사용하여, 금형온도 175℃, 주입시간 15 sec, 경화시간 120 sec, 주입압 9.8 MPa로 두께 3.2 ㎜의 난연 시험편(test piece)을 성형하고, UL94의 규격에 따라 난연시험을 행하였다.Flame retardant: Using a low pressure transfer molding machine, a flame retardant test piece having a thickness of 3.2 mm was formed at a mold temperature of 175 ° C., an injection time of 15 sec, a curing time of 120 sec, and an injection pressure of 9.8 MPa. It was done.

(실시예 2~13, 비교예 1~15)(Examples 2-13, Comparative Examples 1-15)

표 1 및 표 2의 배합에 따라, 실시예 1과 동일하게 하여 에폭시 수지 조성물을 제조하고, 실시예 1과 동일하게 해서 평가하였다. 평가결과를 표 1 및 표 2에 나타낸다.According to the formulation of Table 1 and Table 2, an epoxy resin composition was produced in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 and Table 2.

실시예 1 이외에서 사용한 성분에 대해서, 이하에 나타낸다.About the component used other than Example 1, it shows below.

비페닐형 에폭시 수지(재팬 에폭시 레진(주)제, YX4000H, 에폭시 당량 195, 융점 105℃),Biphenyl type epoxy resin (made in Japan epoxy resin Co., Ltd., YX4000H, epoxy equivalent 195, melting | fusing point 105 degreeC),

페놀아랄킬 수지(미쯔이 가가쿠(주)제, XLC-LL, 수산기 당량 174, 상기 화학식 2에 있어서의 n은 평균값으로 3.6, 연화점 79℃),Phenol aralkyl resin (manufactured by Mitsui Chemical Industries, Ltd., XLC-LL, hydroxyl equivalent 174, n in the formula (2) is 3.6, softening point of 79 ° C as an average value),

크레졸 노볼락형 에폭시 수지(닛폰 가야쿠(주)제, EOCN1020-55, 에폭시 당량 198, 연화점 55℃),Cresol novolak type epoxy resin (made by Nippon Kayaku Co., Ltd., EOCN1020-55, epoxy equivalent 198, softening point 55 degrees Celsius),

페놀 노볼락 수지(수산기 당량 104, 연화점 80℃),Phenolic novolac resin (hydroxyl equivalent 104, softening point 80 degrees Celsius),

γ-메르캅토프로필트리메톡시실란,γ-mercaptopropyltrimethoxysilane,

1,8-디아자비시클로(5,4,0)운데센-7(이하, DBU로 약칭한다),1,8-diazabicyclo (5,4,0) undecene-7 (hereinafter abbreviated as DBU),

하기 화학식 7로 나타내어지는 경화 촉진제,A curing accelerator represented by the following formula (7),

Figure 112005053150148-PCT00009
Figure 112005053150148-PCT00009

하기 화학식 8로 나타내어지는 경화 촉진제,A curing accelerator represented by the following formula (8),

Figure 112005053150148-PCT00010
Figure 112005053150148-PCT00010

1,2-디히드록시나프탈렌(시약),1,2-dihydroxynaphthalene (reagent),

카테콜(시약),Catechol (reagent),

피로갈롤(시약),Pyrogallol (reagent),

1,6-디히드록시나프탈렌(시약),1,6-dihydroxynaphthalene (reagent),

레조르시놀(resorcinol)(시약).Resorcinol (reagent).

Figure 112005053150148-PCT00011
Figure 112005053150148-PCT00011

Figure 112005053150148-PCT00012
Figure 112005053150148-PCT00012

Claims (8)

하기 화학식 1로 표시되는 에폭시 수지(A), 하기 화학식 2로 표시되는 페놀 수지(B), 무기 충전제(C), 경화 촉진제(D), 실란커플링제(E) 및 방향고리를 구성하는 2개 이상의 인접하는 탄소원자에 각각 수산기가 결합된 화합물(F)를 포함하는 것을 특징으로 하는 반도체 봉지용 수지 조성물.Epoxy resin (A) represented by the following general formula (1), phenol resin (B) represented by the following general formula (2), an inorganic filler (C), a hardening accelerator (D), a silane coupling agent (E), and two which comprise an aromatic ring A resin composition for semiconductor encapsulation comprising a compound (F) having a hydroxyl group bonded to each of the above adjacent carbon atoms. [화학식 1][Formula 1]
Figure 112005053150148-PCT00013
Figure 112005053150148-PCT00013
 (다만, 상기 화학식 1에 있어서, R은 수소 또는 탄소수 4 이하의 알킬기이다. 또한, n은 평균값으로, 1~10의 양수이다.)(However, in the general formula (1), R is hydrogen or an alkyl group having 4 or less carbon atoms. In addition, n is an average value and is a positive number of 1 to 10. [화학식 2][Formula 2]
Figure 112005053150148-PCT00014
Figure 112005053150148-PCT00014
 (다만, 상기 화학식 2에 있어서, R1은 페닐렌기 또는 비페닐렌기, R2는 탄소수 4 이하의 알킬기이다. 또한, n은 평균값으로, 1~10의 양수이다.)(However, in the above formula (2), R 1 is a phenylene group or a biphenylene group, R 2 is an alkyl group having 4 or less carbon atoms. N is an average value and is a positive number of 1 to 10. 제1항의 반도체 봉지용 수지 조성물에 있어서, 상기 화합물(F)를 해당 수지 조성물 전체의 0.01 중량% 이상 포함하는 것을 특징으로 하는 반도체 봉지용 수지 조성물.The resin composition for semiconductor encapsulation of Claim 1 WHEREIN: The said resin (F) contains 0.01 weight% or more of the whole resin composition, The resin composition for semiconductor encapsulation. 제1항의 반도체 봉지용 수지 조성물에 있어서, 상기 실란커플링제(E)를 해당 수지 조성물 전체의 0.01 중량% 이상 1.0 중량% 이하 포함하는 것을 특징으로 하는 반도체 봉지용 수지 조성물.The resin composition for semiconductor encapsulation of Claim 1 WHEREIN: The resin composition for semiconductor encapsulation containing 0.01 weight% or more and 1.0 weight% or less of the said silane coupling agent (E) as a whole. 제1항의 반도체 봉지용 수지 조성물에 있어서, 상기 화합물(F)는 상기 방향고리를 구성하는 2개의 인접하는 탄소원자에 각각 수산기가 결합된 화합물인 것을 특징으로 하는 반도체 봉지용 수지 조성물.The resin composition for semiconductor encapsulation according to claim 1, wherein the compound (F) is a compound in which a hydroxyl group is bonded to two adjacent carbon atoms constituting the aromatic ring, respectively. 제1항의 반도체 봉지용 수지 조성물에 있어서, 상기 방향고리가 나프탈렌고리인 것을 특징으로 하는 반도체 봉지용 수지 조성물.The resin composition for semiconductor encapsulation according to claim 1, wherein the aromatic ring is a naphthalene ring. 제5항의 반도체 봉지용 수지 조성물에 있어서, 상기 화합물(F)는 상기 나프탈렌고리를 구성하는 2개의 인접하는 탄소원자에 각각 수산기가 결합된 화합물인 것을 특징으로 하는 반도체 봉지용 수지 조성물.The resin composition for semiconductor encapsulation according to claim 5, wherein the compound (F) is a compound in which hydroxyl groups are bonded to two adjacent carbon atoms constituting the naphthalene ring, respectively. 제1항의 반도체 봉지용 수지 조성물에 있어서, 해당 수지 조성물 중에 84 중 량% 이상 90 중량% 이하의 무기 충전제(C)를 포함하는 것을 특징으로 하는 반도체 봉지용 수지 조성물.The resin composition for semiconductor encapsulation of Claim 1 containing 84 weight% or more and 90 weight% or less of inorganic filler (C) in the said resin composition, The resin composition for semiconductor encapsulations characterized by the above-mentioned. 제1항의 반도체 봉지용 수지 조성물을 사용하여 반도체 소자를 봉지해서 되는 것을 특징으로 하는 반도체장치.The semiconductor device is sealed by using the resin composition for semiconductor sealing of Claim 1.
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