JP2013256547A - Liquid sealing resin composition and semiconductor package - Google Patents

Liquid sealing resin composition and semiconductor package Download PDF

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JP2013256547A
JP2013256547A JP2010225784A JP2010225784A JP2013256547A JP 2013256547 A JP2013256547 A JP 2013256547A JP 2010225784 A JP2010225784 A JP 2010225784A JP 2010225784 A JP2010225784 A JP 2010225784A JP 2013256547 A JP2013256547 A JP 2013256547A
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resin composition
liquid
liquid sealing
acrylic
sealing resin
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Masaya Mitsuta
昌也 光田
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Sumitomo Bakelite Co Ltd
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Sumitomo Bakelite Co Ltd
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Priority to JP2010225784A priority Critical patent/JP2013256547A/en
Priority to PCT/JP2011/072447 priority patent/WO2012046636A1/en
Priority to TW100135738A priority patent/TW201224049A/en
Publication of JP2013256547A publication Critical patent/JP2013256547A/en
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H01L21/563—Encapsulation of active face of flip-chip device, e.g. underfilling or underencapsulation of flip-chip, encapsulation preform on chip or mounting substrate
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    • 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
    • C08G59/40—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 curing agents used
    • C08G59/50—Amines
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Abstract

PROBLEM TO BE SOLVED: To provide a liquid resin composition having a low linear heat-expansion, a low elastic modulus at room temperature, and high reliability, and being excellent in a repletion into a narrow gap, in an underfill material of a flip-chip semiconductor device.SOLUTION: There is provided a liquid sealing resin composition containing a liquid epoxy resin (A), an amine curing agent (B), an acrylic resin (C), and an inorganic filler (D). In the liquid resin composition, preferably the content of the acrylic resin (C) is ≥0.5 wt.% and ≤20 wt.%, and the acrylic resin (C) is composed of an acrylic copolymer containing a plurality of different monomer components.

Description

本発明は、液状封止樹脂組成物および半導体パッケージに関するものである。   The present invention relates to a liquid sealing resin composition and a semiconductor package.

フリップチップ方式の半導体装置では、半導体素子と基板とを半田バンプで電気的に接続している。このフリップチップ方式の半導体装置は、接続信頼性を向上するために半導体素子と基板との間にアンダーフィル材と呼ばれる液状樹脂組成物を充填して半田バンプの周辺を補強している。このようなアンダーフィル充填型のフリップチップパッケージにおいては、近年のＬｏｗ−Ｋチップの採用や半田バンプの鉛フリー化に伴い、熱応力によるＬｏｗ−Ｋ層の破壊や半田バンプのクラックを防ぐためにアンダーフィル材にはより一層の低熱膨張化および低弾性率化が求められる。
アンダーフィル材を低弾性率化するには、液状又は固形のゴム成分を導入する方法があるが、液状のゴム成分を添加した場合はＴｇ（ガラス転移温度）の低下を伴い、固形のゴム成分を添加した場合は、充填量の上昇に伴って粘度の増加する問題がある。さらに液状のゴム成分を添加した場合は、線膨張係数が増大傾向にあり、低熱膨張化には、不利であった。
これらの問題に対して、ゴム粒子を添加するという手法も提案されているが（特許文献１、２参照）、増粘の問題から低弾性率化の範囲が限られていた。そこで現在の弾性率よりさらに低弾性率化するための手法が求められている。 In a flip chip type semiconductor device, a semiconductor element and a substrate are electrically connected by solder bumps. In this flip-chip type semiconductor device, in order to improve connection reliability, a liquid resin composition called an underfill material is filled between the semiconductor element and the substrate to reinforce the periphery of the solder bumps. In such an underfill-filled flip chip package, with the recent adoption of a Low-K chip and lead-free solder bumps, the under-filling type flip-chip package is used to prevent destruction of the Low-K layer and cracks in the solder bumps due to thermal stress. The fill material is required to have further lower thermal expansion and lower elastic modulus.
To lower the elastic modulus of the underfill material, there is a method of introducing a liquid or solid rubber component. However, when a liquid rubber component is added, the solid rubber component is accompanied by a decrease in Tg (glass transition temperature). When is added, there is a problem that the viscosity increases as the filling amount increases. Further, when a liquid rubber component is added, the linear expansion coefficient tends to increase, which is disadvantageous for low thermal expansion.
To solve these problems, a method of adding rubber particles has also been proposed (see Patent Documents 1 and 2), but the range of low elastic modulus has been limited due to the problem of thickening. Therefore, a technique for lowering the elastic modulus further than the current elastic modulus is demanded.

特開２００６−１６９３９５号公報JP 2006-169395 A 特開２００７−１８２５６０号公報JP 2007-182560 A

本発明の目的は、フリップチップ方式の半導体装置のアンダーフィル材において、低熱線膨張かつ室温低弾性率で、高い信頼性を有し、狭ギャップへの充填性に優れる液状樹脂組成物を提供することである。 An object of the present invention is to provide a liquid resin composition that has low thermal linear expansion, low room temperature elasticity, high reliability, and excellent fillability in a narrow gap in an underfill material of a flip-chip semiconductor device. That is.

本発明は以下の通りである。
（１）（Ａ）液状エポキシ樹脂、（Ｂ）アミン硬化剤、（Ｃ）アクリル樹脂、および（Ｄ）無機充填剤を含有する液状封止樹脂組成物。
（２）前記液状樹脂組成物のうち、（Ｃ）アクリル樹脂の含有量が、０．４重量％以上２０重量％以下である（１）記載の液状封止樹脂組成物。
（３）前記（Ｃ）アクリル樹脂が、複数の異なるモノマー成分のアクリル共重合体から構成される（１）又は（２）に記載の液状封止樹脂組成物。
（４）前記（Ｃ）アクリル樹脂が、複数の異なるモノマー成分から構成されるブロックポリマー又はグラフトポリマーである（１）〜（３）いずれかに記載の液状封止樹脂組成物。
（５）前記（Ｃ）アクリル樹脂が、トリブロックポリマーである（１）〜（４）いずれか記載の液状封止樹脂組成物。
（６）前記（Ｃ）アクリル樹脂が、複数の異なる成分のアクリルポリマーから構成され、少なくとも１つの成分のガラス転移温度が０℃以下であるブロックポリマーである（１）〜（５）いずれかに記載の液状封止樹脂組成物。
（７）前記（Ｃ）アクリル樹脂が、エポキシ樹脂と親和性の高い成分が、ガラス転移温度が０℃以下である成分を挟み込んだ構造を持つトリブロックポリマーである（１）〜（６）いずれかに記載の液状封止樹脂組成物。
（８）前記（Ｃ）アクリル樹脂が、ポリメタクリル酸メチル（ＰＭＭＡ）及びポリアクリル酸ｎ−ブチル（ＰｎＢＡ）からなるブロックポリマーである（１）〜（７）のいずれかに記載の液状封止樹脂組成物。
（９）ポリメタクリル酸メチル（ＰＭＭＡ）成分の割合が１０〜５０重量％である（８）記載の液状封止樹脂組成物。
（１０）前記（Ｃ）アクリル樹脂の重量平均分子量が５０００以上１５００００以下である（１）〜（８）いずれかに記載の液状封止樹脂組成物。
（１１）（１）〜（１０）のいずれかに記載の液状封止樹脂組成物を用いて、半導体素子と基板を封止して作製された半導体装置。 The present invention is as follows.
(1) A liquid sealing resin composition comprising (A) a liquid epoxy resin, (B) an amine curing agent, (C) an acrylic resin, and (D) an inorganic filler.
(2) The liquid sealing resin composition according to (1), wherein the content of (C) acrylic resin in the liquid resin composition is 0.4% by weight or more and 20% by weight or less.
(3) The liquid sealing resin composition according to (1) or (2), wherein the (C) acrylic resin is composed of acrylic copolymers of a plurality of different monomer components.
(4) The liquid sealing resin composition according to any one of (1) to (3), wherein the (C) acrylic resin is a block polymer or graft polymer composed of a plurality of different monomer components.
(5) The liquid sealing resin composition according to any one of (1) to (4), wherein the (C) acrylic resin is a triblock polymer.
(6) In any one of (1) to (5), the (C) acrylic resin is a block polymer composed of a plurality of different component acrylic polymers, and at least one component has a glass transition temperature of 0 ° C. or lower. The liquid sealing resin composition as described.
(7) The (C) acrylic resin is a triblock polymer having a structure in which a component having a high affinity with an epoxy resin sandwiches a component having a glass transition temperature of 0 ° C. or lower (1) to (6) A liquid sealing resin composition according to claim 1.
(8) The liquid sealing according to any one of (1) to (7), wherein the (C) acrylic resin is a block polymer composed of polymethyl methacrylate (PMMA) and poly (n-butyl acrylate) (PnBA). Resin composition.
(9) The liquid sealing resin composition according to (8), wherein the proportion of the polymethyl methacrylate (PMMA) component is 10 to 50% by weight.
(10) The liquid sealing resin composition according to any one of (1) to (8), wherein the weight average molecular weight of the (C) acrylic resin is from 5,000 to 150,000.
(11) A semiconductor device manufactured by sealing a semiconductor element and a substrate using the liquid sealing resin composition according to any one of (1) to (10).

本発明によれば、フリップチップ方式の半導体装置のアンダーフィル材として、低熱線膨張かつ室温低弾性率で、高い信頼性を有し、狭ギャップへの充填性に優れる液状樹脂組成物を提供することができる。 According to the present invention, as an underfill material for a flip-chip semiconductor device, a liquid resin composition having low thermal linear expansion, low room temperature elasticity, high reliability, and excellent fillability in a narrow gap is provided. be able to.

本発明は、（Ａ）液状エポキシ樹脂、（Ｂ）アミン硬化剤、（Ｃ）アクリル樹脂、および（Ｄ）無機充填剤を含有する液状封止樹脂組成物であり、フリップチップ方式の半導体装置のアンダーフィル材に適用した場合において、低熱線膨張かつ室温低弾性率で、高い信頼性を有し、狭ギャップへの充填性に優れる。   The present invention is a liquid sealing resin composition containing (A) a liquid epoxy resin, (B) an amine curing agent, (C) an acrylic resin, and (D) an inorganic filler. When applied to an underfill material, it has low thermal linear expansion, low room temperature elasticity, high reliability, and excellent fillability in narrow gaps.

以下、本発明を詳細に説明する。
本発明に用いる（Ａ）液状エポキシ樹脂としては、一分子中にエポキシ基を２個以上有するものであれば特に分子量や構造は限定されるものではない。
例えば、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂などのノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂などのビスフェノール型エポキシ樹脂、Ｎ，Ｎ−ジグリシジルアニリン、Ｎ，Ｎ−ジグリシジルトルイジン、ジアミノジフェニルメタン型グリシジルアミン、アミノフェノール型グリシジルアミンなどの芳香族グリシジルアミン型エポキシ樹脂、ハイドロキノン型エポキシ樹脂、ビフェニル型エポキシ樹脂、スチルベン型エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、トリフェノールプロパン型エポキシ樹脂、アルキル変性トリフェノールメタン型エポキシ樹脂、トリアジン核含有エポキシ樹脂、ジシクロペンタジエン変性フェノール型エポキシ樹脂、ナフトール型エポキシ樹脂、ナフタレン型エポキシ樹脂、フェニレンおよび／またはビフェニレン骨格を有するフェノールアラルキル型エポキシ樹脂、フェニレンおよび／またはビフェニレン骨格を有するナフトールアラルキル型エポキシ樹脂などのアラルキル型エポキシ樹脂などのエポキシ樹脂、ビニルシクロヘキセンジオキシド、ジシクロペンタジエンオキシド、アリサイクリックジエポキシ−アジペイドなどの脂環式エポキシなどの脂肪族エポキシ樹脂が挙げられる。 Hereinafter, the present invention will be described in detail.
The (A) liquid epoxy resin used in the present invention is not particularly limited in molecular weight or structure as long as it has two or more epoxy groups in one molecule.
For example, novolak type epoxy resins such as phenol novolac type epoxy resin and cresol novolak type epoxy resin, bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, N, N-diglycidylaniline, N, N- Aromatic glycidylamine type epoxy resins such as diglycidyl toluidine, diaminodiphenylmethane type glycidylamine, aminophenol type glycidylamine, hydroquinone type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, triphenolmethane type epoxy resin, triphenolpropane Type epoxy resin, alkyl modified triphenol methane type epoxy resin, triazine core-containing epoxy resin, dicyclopentadiene modified phenol type epoxy Epoxy resins such as cis-resin, naphthol type epoxy resin, naphthalene type epoxy resin, phenol aralkyl type epoxy resin having phenylene and / or biphenylene skeleton, and aralkyl type epoxy resin such as naphthol aralkyl type epoxy resin having phenylene and / or biphenylene skeleton And aliphatic epoxy resins such as alicyclic epoxy such as vinylcyclohexene dioxide, dicyclopentadiene oxide, and alicyclic diepoxy-adipade.

さらに本発明の場合、芳香族環にグリシジル構造またはグリシジルアミン構造が結合した構造を含むエポキシ樹脂が耐熱性、機械特性、耐湿性が高くなる点からより好ましく、脂肪族または脂環式エポキシ樹脂は信頼性、特に接着性が低くなる点から使用する量を制限するほうがさらに好ましい。これらは単独でも２種以上混合して使用しても良い。   Furthermore, in the case of the present invention, an epoxy resin containing a structure in which a glycidyl structure or a glycidylamine structure is bonded to an aromatic ring is more preferable from the viewpoint of high heat resistance, mechanical properties, and moisture resistance. It is more preferable to limit the amount to be used from the viewpoint of lowering reliability, particularly adhesiveness. These may be used alone or in combination of two or more.

本発明の液状樹脂組成物は、室温で液状であるので、（Ａ）エポキシ樹脂として、１種の（Ａ）エポキシ樹脂のみを含む場合は、その１種の（Ａ）エポキシ樹脂は、室温で液状であり、また、２種以上の（Ａ）エポキシ樹脂を含む場合は、それら２種以上の（Ａ）エポキシ樹脂全部の混合物が、室温で液状である。そのため、（Ａ）エポキシ樹脂が、２種以上の（Ａ）エポキシ樹脂の組合せの場合、（Ａ）エポキシ樹脂は、全てが室温で液状のエポキシ樹脂の組合せであってもよく、あるいは、一部が室温で固形のエポキシ樹脂あっても他の室温で液状のエポキシ樹脂と混合することにより、混合物が室温で液状となるのであれば、室温で液状のエポキシ樹脂と室温で固形のエポキシ樹脂との組合せであってもよい。なお、（Ａ）エポキシ樹脂が、２種以上のエポキシ樹脂が組合せの場合、必ずしも、使用する全てのエポキシ樹脂を混合してから、他の成分と混合して、液状樹脂組成物を製造する必要はなく、使用するエポキシ樹脂を別々に混合して、液状樹脂組成物を製造してもよい。本発明で、（Ａ）エポキシ樹脂が、室温で液状であるとは、エポキシ樹脂成分（Ａ）として使用する全てのエポキシ樹脂を混合した場合に、その混合物が室温で液状になるということである。
本発明において、室温で液状であるが、室温とは２５℃を指し、また、液状とは樹脂組成物が流動性を有していることを指す。 Since the liquid resin composition of the present invention is liquid at room temperature, when only one type of (A) epoxy resin is included as the (A) epoxy resin, the one type of (A) epoxy resin is at room temperature. When it is liquid and contains two or more types of (A) epoxy resins, the mixture of all of the two or more types of (A) epoxy resins is liquid at room temperature. Therefore, when the (A) epoxy resin is a combination of two or more types of (A) epoxy resins, the (A) epoxy resin may be a combination of epoxy resins that are all liquid at room temperature, or partly If the mixture becomes liquid at room temperature by mixing with other epoxy resins that are solid at room temperature, the liquid epoxy resin that is liquid at room temperature and the epoxy resin that is solid at room temperature It may be a combination. In addition, when (A) 2 or more types of epoxy resins are a combination, it is necessary to manufacture a liquid resin composition by mixing all the epoxy resins used and then mixing with other components. Rather, the epoxy resin to be used may be mixed separately to produce a liquid resin composition. In the present invention, (A) the epoxy resin is liquid at room temperature means that when all the epoxy resins used as the epoxy resin component (A) are mixed, the mixture becomes liquid at room temperature. .
In this invention, although it is liquid at room temperature, room temperature refers to 25 degreeC, and liquid refers to that the resin composition has fluidity | liquidity.

前記（Ａ）エポキシ樹脂の含有量は、特に限定されないが、本発明の液状樹脂組成物全体の５重量％以上３０重量％以下が好ましく、特に５重量％以上２０重量％以下が好ましい。含有量が前記範囲内であると、反応性や組成物の耐熱性や機械的強度、封止時の流動特性に優れる。 The content of the (A) epoxy resin is not particularly limited, but is preferably 5% by weight or more and 30% by weight or less, and particularly preferably 5% by weight or more and 20% by weight or less of the entire liquid resin composition of the present invention. When the content is within the above range, the reactivity, the heat resistance and mechanical strength of the composition, and the flow characteristics at the time of sealing are excellent.

本発明に用いる（Ｂ）アミン硬化剤としては、エポキシ樹脂を硬化し得るものであれば特に構造は限定されない。
前記アミン硬化剤としては、例えばジエチレントリアミン、トリエチレンテトラアミン、テトラエチレンペンタミン、ｍ−キシレンジアミン、トリメチルヘキサメチレンジアミン、２−メチルペンタメチレンジアミン脂肪族ポリアミン、イソフォロンジアミン、１，３−ビスアミノメチルシクロヘキサン、ビス（４−アミノシクロヘキシル）メタン、ノルボルネンジアミン、１，２−ジアミノシクロヘキサンなどの脂環式ポリアミン、Ｎ−アミノエチルピペラジン、１，４−ビス（２−アミノ−２−メチルプロピル）ピペラジンなどのピペラジン型のポリアミン、ジアミノジフェニルメタン、ｍ−フェニレンジアミン、ジアミノジフェニルスルホン、ジエチルトルエンジアミン、トリメチレンビス（４−アミノベンゾエート）、ポリテトラメチレンオキシド−ジ−Ｐ−アミノベンゾエートなどの芳香族ポリアミン類などが挙げられる。
これらのアミン硬化剤は、１種単独で用いても、２種以上の組合せでも良い。
また、本発明の効果が達成される範囲であれば、芳香族アミン、脂肪族アミン、固形アミン、フェノール性硬化剤、酸無水物などの硬化剤を併用することもできる。
さらに半導体装置の封止用途では、耐熱性、電気的特性、機械的特性、密着性、耐湿性が高くなる点から芳香族ポリアミン型硬化剤が一層好ましい。さらに本発明の液状樹脂組成物がアンダーフィルとして用いられる場合には、室温（２５℃）で液状を呈するものがより好ましい。 The (B) amine curing agent used in the present invention is not particularly limited in structure as long as it can cure an epoxy resin.
Examples of the amine curing agent include diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine aliphatic polyamine, isophoronediamine, 1,3-bisamino. Cycloaliphatic polyamines such as methylcyclohexane, bis (4-aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, N-aminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine Piperazine type polyamines such as diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylenebis (4-aminobenzoate), polytetramethyl Ren'okishido - and aromatic polyamines such as di -P- amino benzoate.
These amine curing agents may be used alone or in combination of two or more.
Moreover, as long as the effect of this invention is achieved, hardening agents, such as an aromatic amine, an aliphatic amine, a solid amine, a phenolic hardening | curing agent, and an acid anhydride, can also be used together.
Further, for semiconductor device sealing applications, aromatic polyamine type curing agents are more preferred from the viewpoints of high heat resistance, electrical characteristics, mechanical characteristics, adhesion, and moisture resistance. Furthermore, when the liquid resin composition of this invention is used as an underfill, what exhibits a liquid state at room temperature (25 degreeC) is more preferable.

前記（Ｂ）アミン硬化剤の含有量は、特に限定されないが、本発明の液状樹脂組成物全体の５重量％以上３０重量％以下が好ましく、特に５重量％以上２０重量％以下が好ましい。含有量が前記範囲内であると、反応性や組成物の機械的特性や耐熱性などに優れる。
前記（Ａ）エポキシ樹脂のエポキシ当量に対する前記（Ｂ）アミン硬化剤の活性水素当量の比は０．６以上１．４以下が好ましく、特に０．７以上１．３以下が好ましい。前記（Ｂ）アミン硬化剤の活性水素当量が前記範囲内であると、反応性や樹脂組成物の耐熱性が特に向上する。 The content of the (B) amine curing agent is not particularly limited, but is preferably 5% by weight to 30% by weight, particularly preferably 5% by weight to 20% by weight, based on the entire liquid resin composition of the present invention. When the content is within the above range, the reactivity, the mechanical properties of the composition, the heat resistance and the like are excellent.
The ratio of the active hydrogen equivalent of the (B) amine curing agent to the epoxy equivalent of the (A) epoxy resin is preferably from 0.6 to 1.4, particularly preferably from 0.7 to 1.3. When the active hydrogen equivalent of the (B) amine curing agent is within the above range, the reactivity and the heat resistance of the resin composition are particularly improved.

本発明に用いる（Ｃ）アクリル樹脂は、樹脂組成物を低弾性率化させることができ、エポキシ樹脂に溶解できれば、成分は、限定されるものではないが、メタクリル酸エステル又はアクリル酸エステルのモノマーを重合させて得られる重合体であることが好ましい。
メタクリル酸エステルとしては、例えば、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ−ブチル、メタクリル酸ｎ−プロピル、メタクリル酸イソプロピル、メタクリル酸イソブチル、メタクリル酸ターシャルブチル、メタクリル酸グリシジル、メタクリル酸ラウリル、メタクリル酸n−ヘキシル、メタクリル酸ｎ−オクチル、メタクリル酸トリデシル、メタクリル酸イソボルニル、メタクリル酸シクロヘキシル等が挙げられる。
アクリル酸エステルとしては、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−プロピル、アクリル酸イソプロピル、アクリル酸n−ブチル、アクリル酸イソブチル、アクリル酸ｔ−ブチル、アクリル酸２−エチルヘキシル、アクリル酸ｎ−オクチル、アクリル酸ｎ−ヘキシル、アクリル酸ラウリル、アクリル酸トリデシル、アクリル酸ステアリル等が挙げられる。
これらのモノマーの単独重合体又は共重合体などが選択できるが、共重合体が好ましい。 (C) Acrylic resin used in the present invention is not limited as long as it can lower the elastic modulus of the resin composition and can be dissolved in an epoxy resin. A polymer obtained by polymerizing is preferred.
Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate, glycidyl methacrylate, lauryl methacrylate, Examples include n-hexyl methacrylate, n-octyl methacrylate, tridecyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate and the like.
Examples of acrylic esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and n-acrylate. Examples include octyl, n-hexyl acrylate, lauryl acrylate, tridecyl acrylate, stearyl acrylate, and the like.
A homopolymer or copolymer of these monomers can be selected, but a copolymer is preferred.

共重合体とは、２種類以上のモノマーから重合されたポリマーの総称であり、２種類以上のモノマーがランダムに重合されたランダム共重合体、2種のモノマーが交互に重合された交互共重合体、一つの分子中に２種類以上のポリマーが共存していて、共に主鎖を形成しているタイプであるブロック共重合体、一つのポリマー成分が主鎖、別の異なるポリマー成分が枝のようにぶら下がっているタイプであるグラフト共重合体などが選択できる。
これらの中でより好ましいのは、ブロック共重合体である。
ブロック共重合体とは、単一組成の重合物Aと別の単一組成の重合物Bが同一の分子中にA−Bという形でつながれている構造の共重合体である。ブロック共重合体には、ジブロックタイプA−B、トリブロックタイプA−B−A、トリブロックタイプでも3種類の組成からなるA−B−Cなどのタイプが選択できる。
本発明に使用する（Ｃ）アクリル樹脂は、A−B−Aタイプのトリブロック共重合体が好ましく、AおよびBについては、上記の例に挙げたモノマーから選択したモノマーから構成される重合体ブロックである。 Copolymer is a general term for polymers polymerized from two or more types of monomers. Random copolymers in which two or more types of monomers are randomly polymerized, alternating copolymers in which two types of monomers are alternately polymerized A block copolymer in which two or more kinds of polymers coexist in one molecule and form a main chain together, one polymer component is a main chain, and another different polymer component is a branch A graft copolymer that is a hanging type can be selected.
Among these, a block copolymer is more preferable.
The block copolymer is a copolymer having a structure in which a polymer A having a single composition and a polymer B having another single composition are connected in the form of AB in the same molecule. As the block copolymer, a diblock type AB, a triblock type ABA, and a triblock type can be selected from types such as ABC having three kinds of compositions.
The acrylic resin (C) used in the present invention is preferably an ABA type triblock copolymer, and A and B are polymers composed of monomers selected from the monomers listed in the above examples. It is a block.

Ａ−Ｂ−Ａタイプのトリブロック共重合体の重合体ブロックＡは、トリブロック共重合体をエポキシ樹脂に溶解させるためにエポキシ樹脂との親和性が高く、ハンドリング性を向上させるためにガラス転移温度が室温以上であることが好ましく、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル、メタクリル酸グリシジルなどから選択したモノマーから構成される重合体ブロックであり、好ましくは、メタクリル酸メチル重合体ブロックである。
重合体ブロックＢは、低弾性率効果を発揮するためにガラス転移温度が０℃以下であることが好ましく、アクリル酸エチル、アクリル酸メチル、アクリル酸ブチル、アクリル酸２−エチルヘキシルなどから選択したモノマーから構成される重合体ブロックであり、好ましくは、アクリル酸ｎ−ブチル重合体ブロックである。 The polymer block A of the A-B-A type triblock copolymer has a high affinity with the epoxy resin in order to dissolve the triblock copolymer in the epoxy resin, and a glass transition in order to improve the handling property. The temperature is preferably room temperature or higher, and is a polymer block composed of monomers selected from methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, and the like, preferably, a methyl methacrylate polymer block. is there.
The polymer block B preferably has a glass transition temperature of 0 ° C. or lower in order to exert a low elastic modulus effect, and is a monomer selected from ethyl acrylate, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like The polymer block is preferably an n-butyl acrylate polymer block.

Ａ−Ｂ−Ａタイプのトリブロック共重合体において、重合体ブロックＡと重合体ブロックＢの比率については、どのような割合についても選択できるが、好ましくは、重合体ブロックＢが５０〜９０重量％、より好ましくは、６０〜８０重量％である。重合体ブロックＢは、低弾性率効果を示す成分であり、より多く含まれる方が、低弾性率化でき有利である。しかし重合体ブロックＢのみになるとエポキシ樹脂への親和性が悪くなり、エポキシ樹脂へ溶解できなくなる。そのため、重合体ブロックＡが１０重量％以上含まれる事が好ましく、２０重量％以上含まれることがより好ましい。   In the A-B-A type triblock copolymer, the ratio of the polymer block A and the polymer block B can be selected in any proportion, but preferably the polymer block B is 50 to 90 weights. %, More preferably 60 to 80% by weight. The polymer block B is a component that exhibits a low elastic modulus effect, and it is advantageous that the polymer block B is contained in a larger amount because the elastic modulus can be lowered. However, when only the polymer block B is used, the affinity for the epoxy resin is deteriorated and the resin cannot be dissolved in the epoxy resin. Therefore, the polymer block A is preferably contained in an amount of 10% by weight or more, more preferably 20% by weight or more.

（Ｃ）アクリル樹脂の重量平均分子量は、好ましくは５０００以上１５００００以下、より好ましくは、１００００以上１０００００以下である。   (C) The weight average molecular weight of an acrylic resin becomes like this. Preferably it is 5000-150,000, More preferably, it is 10,000-100,000.

（Ｃ）アクリル樹脂の添加量は、特に制限されるものではないが、上記液状樹脂組成物に対して、好ましくは０．２重量％以上３０重量％以下であり、より好ましくは０．４重量％以上２０重量％以下である。（Ｃ）アクリル樹脂の添加量が上記下限値未満の場合は低弾性率の効果が得られない恐れがある。一方、添加量が上記上限値を超える場合は均一分散させることが困難となり、樹脂組成物全体が脆くなる恐れがある。   (C) The addition amount of the acrylic resin is not particularly limited, but is preferably 0.2% by weight or more and 30% by weight or less, more preferably 0.4% by weight with respect to the liquid resin composition. % To 20% by weight. (C) When the amount of the acrylic resin added is less than the lower limit, the effect of low elastic modulus may not be obtained. On the other hand, when the addition amount exceeds the above upper limit value, it is difficult to uniformly disperse, and the entire resin composition may be brittle.

本発明に用いる（Ｄ）無機充填剤は、破壊靭性などの機械的強度、熱時寸法安定性、耐湿性を向上することから、半導体装置の信頼性を特に向上することができる。
前記（Ｄ）無機充填剤としては、例えばタルク、焼成クレー、未焼成クレー、マイカ、ガラスなどのケイ酸塩、酸化チタン、アルミナ、溶融シリカ（溶融球状シリカ、溶融破砕シリカ）、合成シリカ、結晶シリカなどのシリカ粉末の酸化物、炭酸カルシウム、炭酸マグネシウム、ハイドロタルサイトなどの炭酸塩、水酸化アルミニウム、水酸化マグネシウム、水酸化カルシウムなどの水酸化物、硫酸バリウム、硫酸カルシウム、亜硫酸カルシウムなどの硫酸塩または亜硫酸塩、ホウ酸亜鉛、メタホウ酸バリウム、ホウ酸アルミニウム、ホウ酸カルシウム、ホウ酸ナトリウムなどのホウ酸塩、窒化アルミニウム、窒化ホウ素、窒化ケイ素などの窒化物などを用いることができる。これらの（Ｄ）無機充填剤は、１種単独でも２種以上の組合せでも良い。これらの中でも樹脂組成物の耐熱性、耐湿性、強度などを向上できることから溶融シリカ、結晶シリカ、又は合成シリカ粉末が好ましい。前記（Ｄ）無機充填剤の形状は、特に限定されないが、粘度・流動特性の観点から形状は球状であることが好ましい。 Since the inorganic filler (D) used in the present invention improves mechanical strength such as fracture toughness, thermal dimensional stability, and moisture resistance, the reliability of the semiconductor device can be particularly improved.
Examples of the (D) inorganic filler include silicates such as talc, fired clay, unfired clay, mica, and glass, titanium oxide, alumina, fused silica (fused spherical silica, fused crushed silica), synthetic silica, and crystals. Silica powder oxides such as silica, carbonates such as calcium carbonate, magnesium carbonate, hydrotalcite, hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium sulfate, calcium sulfate, calcium sulfite, etc. Sulfates or sulfites, borates such as zinc borate, barium metaborate, aluminum borate, calcium borate, and sodium borate, and nitrides such as aluminum nitride, boron nitride, and silicon nitride can be used. These (D) inorganic fillers may be used alone or in combination of two or more. Among these, fused silica, crystalline silica, or synthetic silica powder is preferable because the heat resistance, moisture resistance, strength, and the like of the resin composition can be improved. The shape of the (D) inorganic filler is not particularly limited, but the shape is preferably spherical from the viewpoint of viscosity and flow characteristics.

前記（Ｄ）無機充填剤の最大粒子径および平均粒子径は特に限定されないが、最大粒子径が２５μｍ以下、かつ平均粒子径が０．１μｍ以上１０μｍ以下であることが好ましい。前記最大粒子径を前記上限値以下とすることにより液状封止樹脂組成物が半導体装置へ流動する際のフィラー詰まりによる部分的な未充填や充填不良を抑制する効果が高くなる。また前記平均粒子径を前記下限値以上にすることにより、液状封止樹脂組成物の粘度が適度に低下し、充填性が向上する。   The maximum particle size and the average particle size of the (D) inorganic filler are not particularly limited, but it is preferable that the maximum particle size is 25 μm or less and the average particle size is 0.1 μm or more and 10 μm or less. By setting the maximum particle size to the upper limit value or less, the effect of suppressing partial unfilling or poor filling due to filler clogging when the liquid sealing resin composition flows to the semiconductor device is enhanced. Moreover, the viscosity of a liquid sealing resin composition falls moderately by making the said average particle diameter more than the said lower limit, and a fillability improves.

前記液状封止樹脂組成物には、前記（Ａ）エポキシ樹脂、（Ｂ）アミン硬化剤などの上述した各成分以外に、必要に応じてカップリング剤、液状低応力剤、希釈剤、顔料、難燃剤、レベリング剤、消泡剤などの添加剤を用いることができる。   In the liquid sealing resin composition, in addition to the above-described components such as the (A) epoxy resin and (B) amine curing agent, a coupling agent, a liquid low stress agent, a diluent, a pigment, Additives such as flame retardants, leveling agents and antifoaming agents can be used.

本発明の液状封止樹脂組成物は、上述した各成分、添加剤などをプラネタリーミキサー、三本ロール、二本熱ロール、ライカイ機などの装置を用いて分散混練したのち、真空下で脱泡処理して製造することができる。   The liquid encapsulating resin composition of the present invention is prepared by dispersing and kneading the above-described components and additives using a planetary mixer, a triple roll, a two-heat roll, a laika machine, etc. It can be produced by foam treatment.

本発明の半導体装置は、本発明の液状封止樹脂組成物を用いて製造される。
具体的にはフリップチップ型半導体装置が挙げられる。このフリップチップ型半導体装置に関しては、半田電極が具備された半導体素子を基板に接続し、該半導体素子と該基板の間隙を封止する。この場合一般的に基板側の半田電極が接合する部位以外の領域は半田が流れないようにソルダーレジストが形成されている。
次に、半導体素子と基板との間隙に本発明の液状樹脂組成物を充填する。充填する方法としては、毛細管現象を利用する方法が一般的である。具体的には、半導体素子の一辺に本発明の液状樹脂組成物を塗布した後、半導体素子と基板との間隙に毛細管現象で流し込む方法、半導体素子の２辺に前記液状樹脂組成物を塗布した後、半導体素子と基板との間隙に毛細管現象で流し込む方法、半導体素子の中央部にスルーホールを開けておき、半導体素子の周囲に本発明の液状樹脂組成物を塗布した後、半導体素子と基板との間隙に毛細管現象で流し込む方法などが挙げられる。また、一度に全量を塗布するのではなく、２度に分けて塗布する方法なども行われる。また、ポッテッィング、印刷などの方法を用いることもできる
次に、充填した本発明の液状樹脂組成物を硬化させる。硬化条件は、特に限定されないが、例えば１００℃〜１７０℃の温度範囲で１〜１２時間加熱を行うことにより硬化できる。さらに、例えば１００℃で１時間加熱した後、引き続き１５０℃で２時間加熱するような、段階的に温度を変化させながら加熱硬化を行っても良い。
このようにして、半導体素子と基板との間が、本発明の液状樹脂組成物の硬化物で封止されている半導体装置を得ることができる。
このような半導体装置には、フリップチップ方式の半導体装置、キャビティーダウン型ＢＧＡ（Ｂａｌｌ Ｇｒｉｄ Ａｒｒａｙ）、ＰＯＰ（Ｐａｃｋａｇｅ ｏｎ Ｐａｃｋａｇｅ）型ＢＧＡ（Ｂａｌｌ Ｇｒｉｄ Ａｒｒａｙ）、ＴＡＢ（Ｔａｐｅ Ａｕｔｏｍａｔｅｄ Ｂｏｎｄｉｎｇ）型ＢＧＡ（Ｂａｌｌ Ｇｒｉｄ Ａｒｒａｙ）、ＣＳＰ（Ｃｈｉｐ Ｓｃａｌｅ Ｐａｃｋａｇｅ）などが挙げられる。 The semiconductor device of the present invention is manufactured using the liquid sealing resin composition of the present invention.
Specifically, a flip chip type semiconductor device can be given. In this flip chip type semiconductor device, a semiconductor element provided with a solder electrode is connected to a substrate, and a gap between the semiconductor element and the substrate is sealed. In this case, a solder resist is generally formed so that the solder does not flow in a region other than the portion where the solder electrode on the substrate side is joined.
Next, the liquid resin composition of the present invention is filled in the gap between the semiconductor element and the substrate. As a filling method, a method utilizing a capillary phenomenon is common. Specifically, the liquid resin composition of the present invention is applied to one side of a semiconductor element and then poured into the gap between the semiconductor element and the substrate by capillary action, and the liquid resin composition is applied to two sides of the semiconductor element. Thereafter, a method of pouring into the gap between the semiconductor element and the substrate by capillary action, a through hole is opened in the central part of the semiconductor element, the liquid resin composition of the present invention is applied around the semiconductor element, and then the semiconductor element and the substrate And a method of pouring into the gap by capillary action. Further, instead of applying the whole amount at once, a method of applying in two steps is also performed. Moreover, methods, such as potting and printing, can also be used. Next, the filled liquid resin composition of this invention is hardened. Although hardening conditions are not specifically limited, For example, it can harden | cure by heating for 1 to 12 hours in the temperature range of 100 to 170 degreeC. Furthermore, for example, after heating at 100 ° C. for 1 hour, heat curing may be performed while changing the temperature stepwise, such as heating at 150 ° C. for 2 hours.
In this manner, a semiconductor device in which the space between the semiconductor element and the substrate is sealed with the cured product of the liquid resin composition of the present invention can be obtained.
Such a semiconductor device includes a flip-chip type semiconductor device, a cavity down type BGA (Ball Grid Array), a POP (Package on Package) type BGA (Ball Grid Array), and a TAB (Tape Automated Bonding) type BGA (Ball). Grid Array) and CSP (Chip Scale Package).

以下、実施例について説明する。配合量は重量部である。
［実施例１］
（Ａ）液状エポキシ樹脂として、ビスフェノールＦ型エポキシ樹脂を１００重量部、（Ｂ）アミン硬化剤として、芳香族１級アミン型硬化剤を３２重量部、（Ｃ）アクリル樹脂として、トリブロックアクリル樹脂Ｃ１１を２重量部、無機充填剤を２７０重量部、シランカップリング剤としてエポキシシランカップリング剤を４重量部、希釈剤を５重量部、着色剤を０．０５重量部、配合し、プラネタリーミキサーと３本ロールを用いて混合し、真空脱泡処理することにより液状封止樹脂組成物を作製した。得られた液状封止樹脂組成物について、以下の評価方法により評価した。 Examples will be described below. A compounding quantity is a weight part.
[Example 1]
(A) 100 parts by weight of bisphenol F type epoxy resin as liquid epoxy resin, (B) 32 parts by weight of aromatic primary amine type curing agent as amine curing agent, (C) triblock acrylic resin as acrylic resin 2 parts by weight of C11, 270 parts by weight of an inorganic filler, 4 parts by weight of an epoxy silane coupling agent as a silane coupling agent, 5 parts by weight of a diluent, 0.05 part by weight of a colorant, and planetary The liquid sealing resin composition was produced by mixing using a mixer and 3 rolls, and carrying out a vacuum defoaming process. About the obtained liquid sealing resin composition, it evaluated with the following evaluation methods.

［評価方法］
・粘度：ＴＶ−Ｅ型粘度計にて、２５℃で５ｒｐｍの条件で測定を実施した。単位はＰａ・ｓである。
・ガラス転移温度、線膨張係数：熱機械分析装置（ＴＭＡ）を用いて、四角柱状に硬化（硬化条件：１５０℃、１２０分）した液状封止樹脂組成物を測定し、ガラス転移温度および線膨張係数（−１０℃〜１０℃までの線膨張係数の平均値）を測定した。
・弾性率：粘弾性測定装置（ＤＭＡ）を用いて、板状に硬化（硬化条件：１５０℃、１２０分）した液状封止樹脂組成物を測定し、室温（２５℃）での弾性率を測定した。 [Evaluation method]
Viscosity: Measurement was performed with a TV-E viscometer at 25 ° C. and 5 rpm. The unit is Pa · s.
Glass transition temperature and linear expansion coefficient: Using a thermomechanical analyzer (TMA), a liquid sealing resin composition cured in a square column shape (curing conditions: 150 ° C., 120 minutes) was measured, and the glass transition temperature and the line were measured. The expansion coefficient (average value of linear expansion coefficient up to -10 ° C to 10 ° C) was measured.
Elastic modulus: Using a viscoelasticity measuring device (DMA), the liquid sealing resin composition cured in a plate shape (curing conditions: 150 ° C., 120 minutes) is measured, and the elastic modulus at room temperature (25 ° C.) is measured. It was measured.

上記で得られた液状封止樹脂組成物を半導体装置の基板とチップの間に充填、封止し、液状封止樹脂組成物の充填性試験、耐リフロー試験および温度サイクル試験を実施した。結果を表１に記載した。
試験、評価に使用した半導体装置の構成部材は以下のとおりである。
チップとしては、日立超ＬＳＩ社製ＰＨＡＳＥ−２ＴＥＧウエハー（ウエハー厚さ０．７２ｍｍ）にチップの回路保護膜としてポリイミドを用い、半田バンプとしてＳｎ／Ａｇ／Ｃｕ組成の無鉛半田を形成したものを１５ｍｍ×１５ｍｍに切断し使用した。
基板には、住友ベークライト（株）製ＦＲ５相当の０．８ｍｍｔのガラスエポキシ基板をベースとして用い、その両面に太陽インキ製造（株）製ソルダーレジストＰＳＲ４０００／ＡＵＳ３０８を形成し、片面に上記の半田バンプ配列に相当する金メッキパッドを形成したものを５０ｍｍ×５０ｍｍの大きさに切断し使用した。接続用のフラックスにはＴＳＦ−６５０２（Ｋｅｓｔｅｒ製、ロジン系フラックス）を使用した。
半導体装置の組立は、まず充分平滑な金属またはガラス板にドクターブレードを用いてフラックスを５０μｍ厚程度に均一塗布し、次にフリップチップボンダーを用いてフラックス膜にチップの回路面を軽く接触させたのちに離し、半田バンプにフラックスを転写させ、次にチップを基板上に圧着させた。ＩＲリフロー炉で加熱処理し半田バンプを溶融接合して作製した。溶融接合後に洗浄液を用いて洗浄を実施した。液状封止樹脂組成物の充填、封止方法は、作製したチップを搭載した基板を１１０℃の熱板上で加熱し、チップの一辺に作製した液状封止樹脂組成物を塗布し隙間充填させた後、１５０℃のオーブンで１２０分間液状封止樹脂組成物を加熱硬化し、評価試験用のチップ厚さ０．７２ｍｍの半導体装置を得た。 The liquid sealing resin composition obtained above was filled and sealed between the substrate and the chip of the semiconductor device, and a filling property test, a reflow resistance test, and a temperature cycle test of the liquid sealing resin composition were performed. The results are shown in Table 1.
The components of the semiconductor device used for testing and evaluation are as follows.
As a chip, a chip made of Hitachi Ultra LSI's PHASE-2TEG wafer (wafer thickness 0.72 mm) using polyimide as a circuit protection film of the chip, and lead-free solder of Sn / Ag / Cu composition formed as a solder bump is 15 mm. It cut | disconnected and used for * 15mm.
As a substrate, a 0.8 mmt glass epoxy substrate equivalent to FR5 manufactured by Sumitomo Bakelite Co., Ltd. is used as a base, and a solder resist PSR4000 / AUS308 manufactured by Taiyo Ink Mfg. Co., Ltd. is formed on both sides, and the solder bumps are formed on one side A gold-plated pad corresponding to the array was cut into a size of 50 mm × 50 mm and used. TSF-6502 (manufactured by Kester, rosin flux) was used as a flux for connection.
In assembling the semiconductor device, a flux is uniformly applied to a sufficiently smooth metal or glass plate to a thickness of about 50 μm using a doctor blade, and then the circuit surface of the chip is lightly brought into contact with the flux film using a flip chip bonder. Later, the flux was transferred to the solder bumps, and then the chip was pressed onto the substrate. A heat treatment was performed in an IR reflow furnace, and solder bumps were melted and produced. Cleaning was performed using a cleaning liquid after the melt bonding. The liquid sealing resin composition is filled and sealed by heating the substrate on which the manufactured chip is mounted on a hot plate at 110 ° C., and applying the liquid sealing resin composition prepared on one side of the chip to fill the gap. After that, the liquid sealing resin composition was heated and cured in an oven at 150 ° C. for 120 minutes to obtain a semiconductor device having a chip thickness of 0.72 mm for evaluation test.

・充填性：上記作製した半導体装置について、超音波探傷装置を用いて、液状封止樹脂組成物を充填した部分のボイドの発生を確認し、充填不良ボイドが観察されない場合は良好、観察された場合は不良と判定した。
・耐リフロー性：上記作製した半導体装置をＪＥＤＥＣレベル３の吸湿処理（３０℃、相対湿度６０％で１９２時間処理）を行った後、ＩＲリフロー処理（ピーク温度２６０℃）を３回行い、超音波探傷装置にて半導体装置内部での液状封止樹脂組成物の剥離の有無を確認し、さらに光学顕微鏡を用いてチップ側面部の液状封止樹脂組成物表面にある亀裂の有無を観察した。剥離および亀裂が無い場合は○、剥離又は亀裂が有る場合は×と表示した。
・温度サイクル試験：温度サイクル試験としては、上記のリフロー試験を行った半導体装置に（−５５℃／３０分）と（１２５℃／３０分）の冷熱サイクル処理を施し、２５０サイクル毎に超音波探傷装置にて半導体装置内部の半導体チップと液状樹脂組成物界面の剥離の有無を確認し、さらに光学顕微鏡を用いてチップ側面部の液状樹脂組成物表面を観察し、亀裂の有無を観測した。上記温度サイクル試験は最終的に１０００サイクルまで実施した。亀裂又は剥離のあるものを「×」で、亀裂及び剥離のないものを「○」で表示した。
以上の結果を表１に詳細にまとめた。 ・ Fillability: Using the ultrasonic flaw detector, the generation of voids in the portion filled with the liquid sealing resin composition was confirmed for the semiconductor device produced above. The case was determined to be bad.
-Reflow resistance: After the above semiconductor device was subjected to a JEDEC level 3 moisture absorption treatment (treatment at 30 ° C. and a relative humidity of 60% for 192 hours), IR reflow treatment (peak temperature 260 ° C.) was conducted three times. The presence or absence of peeling of the liquid encapsulating resin composition inside the semiconductor device was confirmed with an acoustic flaw detector, and the presence or absence of cracks on the surface of the liquid encapsulating resin composition on the side surface of the chip was further observed using an optical microscope. When there was no peeling or cracking, it was indicated as “◯”, and when there was peeling or cracking, it was indicated as “x”.
Temperature cycle test: As the temperature cycle test, the semiconductor device subjected to the above reflow test was subjected to a thermal cycle treatment of (−55 ° C./30 minutes) and (125 ° C./30 minutes), and an ultrasonic wave every 250 cycles. The presence or absence of peeling of the interface between the semiconductor chip and the liquid resin composition inside the semiconductor device was confirmed with a flaw detector, and the surface of the liquid resin composition on the side surface of the chip was observed using an optical microscope to observe the presence or absence of cracks. The temperature cycle test was finally performed up to 1000 cycles. Those with cracks or delamination are indicated by “x”, and those without cracks or delamination are indicated by “◯”.
The above results are summarized in Table 1.

［実施例２〜５］
（Ｃ）アクリル樹脂の成分割合又は配合量を変え、（Ｄ）無機充填剤の配合量を変えた以外は、実施例１と同様の方法によって、液状樹脂組成物を作製した。成分割合の異なるアクリル樹脂は、下記トリブロックアクリル樹脂Ｃ１２、Ｃ１３を用いた。得られた液状樹脂組成物を用いて、実施例１と同様に評価した。詳細な配合、液状樹脂組成物および半導体装置の評価結果を表1にまとめた。 [Examples 2 to 5]
(C) The liquid resin composition was produced by the method similar to Example 1 except having changed the component ratio or compounding quantity of the acrylic resin, and having changed the compounding quantity of (D) inorganic filler. As the acrylic resins having different component ratios, the following triblock acrylic resins C12 and C13 were used. Evaluation was conducted in the same manner as in Example 1 using the obtained liquid resin composition. Table 1 summarizes the detailed formulation, the liquid resin composition, and the evaluation results of the semiconductor device.

［比較例１］
（Ｃ）アクリル樹脂を配合しないものであり、実施例１と同様の方法によって液状樹脂組成物を得た。得られた液状樹脂組成物を用いて実施例１と同様に評価した。詳細な配合、液状樹脂組成物および半導体装置の評価結果を表1にまとめた。
［比較例２］
（Ｃ）アクリル樹脂の代わりに、液状ポリブタジエンを配合したこと以外は、実施例２と同様の方法によって液状樹脂組成物を得た。得られた液状樹脂組成物を用いて実施例１と同様に評価した。詳細な配合、液状樹脂組成物および半導体装置の評価結果を表1にまとめた。
［比較例３］
（Ｃ）アクリル樹脂の代わりに、アクリルゴム粒子を配合し、配合量および（Ｄ）無機添加剤の配合量を変えた以外は、実施例と同様の方法によって液状樹脂組成物を得た。得られた液状樹脂組成物を用いて実施例１と同様に評価した。詳細な配合、液状樹脂組成物および半導体装置の評価結果を表1にまとめた。 [Comparative Example 1]
(C) An acrylic resin was not blended, and a liquid resin composition was obtained by the same method as in Example 1. Evaluation was performed in the same manner as in Example 1 using the obtained liquid resin composition. Table 1 summarizes the detailed formulation, the liquid resin composition, and the evaluation results of the semiconductor device.
[Comparative Example 2]
(C) A liquid resin composition was obtained by the same method as in Example 2 except that liquid polybutadiene was blended in place of the acrylic resin. Evaluation was performed in the same manner as in Example 1 using the obtained liquid resin composition. Table 1 summarizes the detailed formulation, the liquid resin composition, and the evaluation results of the semiconductor device.
[Comparative Example 3]
(C) A liquid resin composition was obtained in the same manner as in Example except that acrylic rubber particles were blended instead of the acrylic resin, and the blending amount and (D) the blending amount of the inorganic additive were changed. Evaluation was performed in the same manner as in Example 1 using the obtained liquid resin composition. Table 1 summarizes the detailed formulation, the liquid resin composition, and the evaluation results of the semiconductor device.

実施例では、以下の材料を使用した。
・ビスフェノールＦ型エポキシ樹脂：大日本インキ化学工業（株）製、ＥＸＡ−８３０ＬＶＰ、ビスフェノールＦ型液状エポキシ樹脂、エポキシ当量１６１
・芳香族１級アミン型硬化剤：日本化薬（株）製、カヤハード−ＡＡ、３，３’−ジエチル−４，４’−ジアミノジフェニルメタン、アミン当量６３．５
・アクリル樹脂：トリブロックアクリル樹脂Ｃ１１、クラレ（株）製 ＬＡ２１４０Ｅ、Ａ−Ｂ−Ａ型アクリルトリブロック共重合体、ＰＭＭＡ（ポリメタクリル酸メチル、ガラス転移温度：１００〜１２０℃ ）−ＰｎＢＡ（ポリアクリル酸ｎ−ブチル、ガラス転移温度：−４０〜−５０ ℃ ）−ＰＭＭＡ ）、ＰＭＭＡ割合２０重量％、Ｍｗ＝８００００
・アクリル樹脂：トリブロックアクリル樹脂Ｃ１２、クラレ（株）製 ＬＡ２２５０、
Ａ−Ｂ−Ａ型アクリルトリブロック共重合体、ＰＭＭＡ（ポリメタクリル酸メチル、ガラス転移温度：１００〜１２０℃ ）−ＰｎＢＡ（ポリアクリル酸ｎ−ブチル、ガラス転移温度：−４０〜−５０ ℃ ）−ＰＭＭＡ ）、ＰＭＭＡ割合３０重量％、Ｍｗ＝８００００
・アクリル樹脂：トリブロックアクリル樹脂Ｃ１３、クラレ（株）製 ＬＡ４２８５、
Ａ−Ｂ−Ａ型アクリルトリブロック共重合体、ＰＭＭＡ（ポリメタクリル酸メチル、ガラス転移温度：１００〜１２０℃ ）−ＰｎＢＡ（ポリアクリル酸ｎ−ブチル、ガラス転移温度：−４０〜−５０ ℃ ）−ＰＭＭＡ ）、ＰＭＭＡ割合５０重量％、Ｍｗ＝８００００
・液状ポリブタジエン：ダイセル化学工業(株)製、ＰＢ３６００
・アクリルゴム粒子：三菱レイヨン(株)製 ＫＷ８８１５
・無機充填剤（合成球状シリカ）：アドマテクス（株）製、アドマファインＳＯ−Ｅ３、合成球状シリカ、平均粒径１μｍ
・エポキシシランカップリング剤： 信越化学工業（株）製、ＫＢＭ４０３Ｅ、γ−グリシドキシプロピルトリメトキシシラン
・着色剤：三菱化学（株）製、ＭＡ−６００ カーボンブラック
・希釈剤：東京化成工業（株）製、（試薬）ＢＣＳＡ、エチレングリコールモノ−ノルマル−ブチルエーテルアセテート In the examples, the following materials were used.
-Bisphenol F type epoxy resin: manufactured by Dainippon Ink and Chemicals, EXA-830LVP, bisphenol F type liquid epoxy resin, epoxy equivalent 161
Aromatic primary amine type curing agent: manufactured by Nippon Kayaku Co., Ltd., Kayahard-AA, 3,3′-diethyl-4,4′-diaminodiphenylmethane, amine equivalent 63.5
Acrylic resin: Triblock acrylic resin C11, Kuraray Co., Ltd. LA2140E, ABA type acrylic triblock copolymer, PMMA (polymethyl methacrylate, glass transition temperature: 100 to 120 ° C.)-PnBA (poly N-butyl acrylate, glass transition temperature: −40 to −50 ° C.)-PMMA), PMMA ratio 20% by weight, Mw = 80000
Acrylic resin: Triblock acrylic resin C12, Kuraray Co., Ltd. LA2250,
A-B-A type acrylic triblock copolymer, PMMA (polymethyl methacrylate, glass transition temperature: 100 to 120 ° C.)-PnBA (poly-n-butyl acrylate, glass transition temperature: −40 to −50 ° C.) -PMMA), PMMA ratio 30% by weight, Mw = 80000
Acrylic resin: triblock acrylic resin C13, LA4285 manufactured by Kuraray Co., Ltd.
A-B-A type acrylic triblock copolymer, PMMA (polymethyl methacrylate, glass transition temperature: 100 to 120 ° C.)-PnBA (poly-n-butyl acrylate, glass transition temperature: −40 to −50 ° C.) -PMMA), PMMA ratio 50% by weight, Mw = 80000
・ Liquid polybutadiene: Daicel Chemical Industries, PB3600
Acrylic rubber particles: KW8815 manufactured by Mitsubishi Rayon Co., Ltd.
Inorganic filler (synthetic spherical silica): Admatechs Co., Ltd., Admafine SO-E3, synthetic spherical silica, average particle size 1 μm
・ Epoxysilane coupling agent: Shin-Etsu Chemical Co., Ltd., KBM403E, γ-glycidoxypropyltrimethoxysilane ・ Colorant: Mitsubishi Chemical Co., Ltd., MA-600 carbon black ・ Diluent: Tokyo Chemical Industry ( Co., Ltd., (Reagent) BCSA, Ethylene glycol mono-normal-butyl ether acetate

本発明において、アクリル樹脂を含まない比較例１では、温度サイクル試験中に剥離が発生した。
比較例２のようにアクリル樹脂の代わりに、液状のゴム成分が含まれる場合は、弾性率は低下するものの、ガラス転移温度も低下してしまい、耐リフロー試験にて剥離が発生した。耐リフロー試験にて剥離が発生したため、その後の温度サイクル試験は実施しなかった。
比較例３のようにアクリル樹脂の代わりに、アクリルゴム粒子が含まれる場合は、アクリル樹脂と同程度の弾性率にするためには、添加量が多くする必要があるため、樹脂粘度が非常に高くなってしまい、ボイドなく充填する事ができなかった。そのため、耐リフロー試験および温度サイクル試験は実施しなかった。
これに対して、実施例１〜５については、アクリル樹脂を含有するため、低弾性率かつ低熱線膨張が達成され、温度サイクル試験において剥離および亀裂が発生しなかった。
アクリル樹脂を含む液状樹脂組成物は、低弾性率、低熱線膨張を達成し、半導体装置の信頼性を改善することができた。 In the present invention, in Comparative Example 1 containing no acrylic resin, peeling occurred during the temperature cycle test.
When a liquid rubber component was contained instead of the acrylic resin as in Comparative Example 2, although the elastic modulus was lowered, the glass transition temperature was also lowered, and peeling occurred in the reflow resistance test. Since peeling occurred in the reflow resistance test, the subsequent temperature cycle test was not performed.
When acrylic rubber particles are included instead of acrylic resin as in Comparative Example 3, the resin viscosity is very high because it is necessary to increase the amount of addition in order to obtain the same elastic modulus as that of the acrylic resin. It became expensive and could not be filled without voids. Therefore, the reflow resistance test and the temperature cycle test were not performed.
On the other hand, about Examples 1-5, since acrylic resin was contained, the low elastic modulus and the low heat linear expansion were achieved, and peeling and a crack did not generate | occur | produce in the temperature cycle test.
The liquid resin composition containing an acrylic resin achieved a low elastic modulus and a low thermal linear expansion, and was able to improve the reliability of the semiconductor device.

Figure 2013256547
Figure 2013256547

Claims (11)

（Ａ）液状エポキシ樹脂、（Ｂ）アミン硬化剤、（Ｃ）アクリル樹脂、および（Ｄ）無機充填剤を含有する液状封止樹脂組成物。 A liquid sealing resin composition comprising (A) a liquid epoxy resin, (B) an amine curing agent, (C) an acrylic resin, and (D) an inorganic filler. 前記液状樹脂組成物のうち、（Ｃ）アクリル樹脂の含有量が、０．４重量％以上２０重量％以下である請求項１記載の液状封止樹脂組成物。 The liquid sealing resin composition according to claim 1, wherein the content of the acrylic resin (C) in the liquid resin composition is 0.4 wt% or more and 20 wt% or less. 前記（Ｃ）アクリル樹脂が、複数の異なるモノマー成分のアクリル共重合体から構成される請求項１又は２に記載の液状封止樹脂組成物。 The liquid sealing resin composition according to claim 1, wherein the (C) acrylic resin is composed of an acrylic copolymer of a plurality of different monomer components. 前記（Ｃ）アクリル樹脂が、複数の異なるモノマー成分から構成されるブロックポリマー又はグラフトポリマーである請求項１〜３のいずれか１項に記載の液状封止樹脂組成物。 The liquid sealing resin composition according to any one of claims 1 to 3, wherein the (C) acrylic resin is a block polymer or a graft polymer composed of a plurality of different monomer components. 前記（Ｃ）アクリル樹脂が、トリブロックポリマーである請求項１〜４のいずれか１項に記載の液状封止樹脂組成物。 The liquid sealing resin composition according to any one of claims 1 to 4, wherein the (C) acrylic resin is a triblock polymer. 前記（Ｃ）アクリル樹脂が、複数の異なる成分のアクリルポリマーから構成され、少なくとも１つの成分のガラス転移温度が０℃以下であるブロックポリマーである請求項１〜５のいずれか1項に記載の液状封止樹脂組成物。 The said (C) acrylic resin is comprised from the acrylic polymer of a several different component, The glass transition temperature of at least 1 component is a block polymer which is 0 degrees C or less, The any one of Claims 1-5 Liquid sealing resin composition. 前記（Ｃ）アクリル樹脂が、エポキシ樹脂と親和性の高い成分が、ガラス転移温度が０℃以下である成分を挟み込んだ構造を持つトリブロックポリマーである請求項１〜６のいずれか１項に記載の液状封止樹脂組成物。 The component (C) having high affinity with the epoxy resin is a triblock polymer having a structure in which a component having a glass transition temperature of 0 ° C. or less is sandwiched between the acrylic resin (C). The liquid sealing resin composition as described. 前記（Ｃ）アクリル樹脂が、ポリメタクリル酸メチル（ＰＭＭＡ）及びポリアクリル酸ｎ−ブチル（ＰｎＢＡ）からなるブロックポリマーである請求項１〜７のいずれかの1項に記載の液状封止樹脂組成物。 The liquid sealing resin composition according to any one of claims 1 to 7, wherein the (C) acrylic resin is a block polymer composed of polymethyl methacrylate (PMMA) and poly (n-butyl acrylate) (PnBA). object. ポリメタクリル酸メチル（ＰＭＭＡ）成分の割合が１０〜５０重量％である請求項８に記載の液状封止樹脂組成物。 The liquid sealing resin composition according to claim 8, wherein the proportion of the polymethyl methacrylate (PMMA) component is 10 to 50% by weight. 前記（Ｃ）アクリル樹脂の重量平均分子量が５０００以上１５００００以下である請求項１〜８のいずれか１項に記載の液状封止樹脂組成物。 The liquid sealing resin composition according to any one of claims 1 to 8, wherein the weight average molecular weight of the (C) acrylic resin is from 5,000 to 150,000. 請求項１〜１０のいずれか１項に記載の液状封止樹脂組成物を用いて、半導体素子と基板を封止して作製された半導体装置。 The semiconductor device produced by sealing a semiconductor element and a board | substrate using the liquid sealing resin composition of any one of Claims 1-10.
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