JP2005330315A - Liquid epoxy resin composition and semiconductor device - Google Patents
Liquid epoxy resin composition and semiconductor device Download PDFInfo
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- JP2005330315A JP2005330315A JP2004147553A JP2004147553A JP2005330315A JP 2005330315 A JP2005330315 A JP 2005330315A JP 2004147553 A JP2004147553 A JP 2004147553A JP 2004147553 A JP2004147553 A JP 2004147553A JP 2005330315 A JP2005330315 A JP 2005330315A
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Abstract
Description
本発明は、半導体封止用として好適で、シリコンチップの素子表面（特に感光性ポリイミド、窒化膜、酸化膜）との密着性が非常に良好であり、耐湿性の高い硬化物を与え、特にリフロー温度２６０℃以上の高温熱衝撃に対して優れた封止材となり得る液状エポキシ樹脂組成物、及びこの組成物にて封止された半導体装置に関する。 The present invention is suitable for semiconductor sealing, has very good adhesion to the element surface (especially photosensitive polyimide, nitride film, oxide film) of the silicon chip, and gives a cured product with high moisture resistance. The present invention relates to a liquid epoxy resin composition that can be an excellent sealing material against a high temperature thermal shock at a reflow temperature of 260 ° C. or higher, and a semiconductor device sealed with this composition.
電気機器の小型化、軽量化、高機能化に伴い、半導体の実装方法もピン挿入タイプから表面実装が主流になっている。また、半導体素子の高集積化に伴い、ダイサイズの一辺が１０ｍｍを超えるものもあり、ダイサイズの大型化が進んできている。このような大型ダイを用いた半導体装置では、半田リフロー時にダイと封止材にかかる応力が増大し、封止材とダイ及び基板の界面での剥離、基板実装時にパッケージにクラックが入るといった問題がクローズアップされてきている。 Along with the downsizing, weight reduction, and higher functionality of electrical equipment, semiconductor mounting methods have become mainstream from pin insertion type to surface mounting. In addition, along with the high integration of semiconductor elements, there are cases in which one side of the die size exceeds 10 mm, and the die size is increasing. In a semiconductor device using such a large die, the stress applied to the die and the sealing material during solder reflow increases, peeling at the interface between the sealing material and the die and the substrate, and cracks in the package when mounted on the substrate. Has been close up.
更に、近い将来に鉛含有半田が使用できなくなることから、鉛代替半田が多数開発されている。この種の半田は、溶融温度が鉛含有の半田より高くなることから、リフローの温度も２６０〜２７０℃で検討されており、従来の液状エポキシ樹脂組成物の封止材では、より一層の不良が予想される。このようにリフローの温度が高くなると、従来においては何ら問題のなかったフリップチップ型のパッケージもリフロー時にクラック発生、チップ界面、基板界面との剥離が発生するという重大な問題が起こるようになった。 Furthermore, since lead-containing solder cannot be used in the near future, a number of lead substitute solders have been developed. Since this type of solder has a melting temperature higher than that of lead-containing solder, the reflow temperature has been studied at 260 to 270 ° C., and the conventional liquid epoxy resin composition sealing material is even more defective. Is expected. Thus, when the reflow temperature becomes high, the flip chip type package, which has no problem in the past, also has a serious problem in that cracking occurs during reflow and separation from the chip interface and the substrate interface occurs. .
これらの要求を満たす材料として、液状エポキシ樹脂／アルキル置換芳香族ジアミン系の液状封止樹脂が提案されている（特許文献１：特開平７−３４１５８０号公報、特許文献２：特開平７−３４１５８２号公報参照）。この材料は、基板、金属、ソルダーレジスト等との接着性に優れ、更に耐リフロー性、耐温度サイクルクラック性に優れ、高信頼性パッケージを可能としている。 As materials satisfying these requirements, liquid epoxy resins / alkyl-substituted aromatic diamine-based liquid sealing resins have been proposed (Patent Document 1: JP-A-7-341580, Patent Document 2: JP-A-7-341582). No. publication). This material is excellent in adhesion to a substrate, metal, solder resist, etc., and further excellent in reflow resistance and temperature cycle crack resistance, enabling a highly reliable package.
しかし、上記の樹脂系は硬化時間が長く（１５０℃／３時間）、パッケージ生産性という観点からは問題であった。また、ゲル化時間が長いためにフィラーの沈降、それに伴う表面クラックの発生、可使時間が短い等の欠点があった。また、硬化時間を短くするために硬化促進剤の検討が考えられ、その例としてはフェノール類、サリチル酸のようなフェノール酸が挙げられるが、可使時間が短く、作業性が著しく低下する等の欠点があった。 However, the above resin system has a long curing time (150 ° C./3 hours), which is a problem from the viewpoint of package productivity. In addition, since the gelation time is long, there are disadvantages such as sedimentation of the filler, generation of surface cracks associated therewith, and short pot life. Further, in order to shorten the curing time, a study of a curing accelerator can be considered, and examples thereof include phenols and phenolic acids such as salicylic acid, but the pot life is short and workability is remarkably reduced. There were drawbacks.
本発明は、上記事情に鑑みなされたもので、従来に比べて短時間に硬化が可能であり、シリコンチップの表面、特に感光性ポリイミド樹脂や窒化膜との密着性に優れ、かつ強靭性に優れた硬化物を与え、リフローの温度が従来温度２４０℃付近から２６０〜２７０℃に上昇しても不良が発生せず、更にＰＣＴ（１２０℃／２．１ａｔｍ）などの高温多湿の条件下でも劣化せず、−６５℃／１５０℃の温度サイクルにおいて数百サイクルを超えても剥離、クラックが発生しない半導体装置の封止材となり得る液状エポキシ樹脂組成物、及びこの組成物の硬化物で封止された半導体装置を提供することを目的とする。 The present invention has been made in view of the above circumstances, can be cured in a shorter time than conventional, has excellent adhesion to the surface of a silicon chip, in particular, a photosensitive polyimide resin or a nitride film, and toughness. Gives an excellent cured product, no defects occur even when the reflow temperature rises from about 240 ° C. to about 260 to 270 ° C., and even under high temperature and high humidity conditions such as PCT (120 ° C./2.1 atm) Sealed with a liquid epoxy resin composition that can be a sealing material for a semiconductor device that does not deteriorate and does not peel or crack even if it exceeds several hundred cycles in a temperature cycle of -65 ° C / 150 ° C, and a cured product of this composition. An object of the present invention is to provide a stopped semiconductor device.
本発明者は、上記目的を達成するために鋭意検討を重ねた結果、（Ａ）液状エポキシ樹脂、（Ｂ）芳香族アミン系硬化剤、（Ｃ）硬化触媒としてカルボキシル基を有する化合物をマイクロカプセル化したマイクロカプセル型硬化促進剤、及び好ましくは（Ｄ）無機質充填剤を含有する液状エポキシ樹脂組成物を用いること、この場合、特に、（Ａ）液状エポキシ樹脂のエポキシ当量と（Ｂ）芳香族アミン系硬化剤のアミン当量との当量比〔（Ａ）／（Ｂ）〕を０．７以上１．２以下とすることにより、シリコンチップの表面、特に感光性ポリイミド樹脂や窒化膜との密着性に優れ、ＰＣＴ（１２０℃／２．１ａｔｍ）などの高温多湿の条件下でも劣化せず、熱衝撃に対して優れており、特に大型ダイサイズの半導体装置の封止材として有効となり得ることを見出し、本発明をなすに至ったものである。 As a result of intensive studies to achieve the above object, the present inventor has obtained (A) a liquid epoxy resin, (B) an aromatic amine-based curing agent, and (C) a compound having a carboxyl group as a curing catalyst. A liquid epoxy resin composition containing a microcapsule-type curing accelerator and preferably (D) an inorganic filler, in this case, in particular, (A) epoxy equivalent of liquid epoxy resin and (B) aromatic By setting the equivalent ratio [(A) / (B)] of the amine curing agent to 0.7 or more and 1.2 or less, adhesion to the surface of the silicon chip, particularly to the photosensitive polyimide resin or nitride film It is excellent in heat resistance, does not deteriorate even under high-temperature and high-humidity conditions such as PCT (120 ° C / 2.1 atm), is excellent against thermal shock, and is particularly effective as a sealing material for large die size semiconductor devices. Found that to obtain Ri are those able to complete the present invention.
従って、本発明は、（Ａ）液状エポキシ樹脂、（Ｂ）芳香族アミン系硬化剤、（Ｃ）硬化触媒としてカルボキシル基を有する化合物をマイクロカプセル化したマイクロカプセル型硬化促進剤を必須成分とすることを特徴とする液状エポキシ樹脂組成物、及び上記液状エポキシ樹脂組成物の硬化物で封止した半導体装置を提供する。更に、上記液状エポキシ樹脂組成物の硬化物をアンダーフィル材として封止したフリップチップ型半導体装置を提供する。 Therefore, the present invention comprises (A) a liquid epoxy resin, (B) an aromatic amine curing agent, and (C) a microcapsule type curing accelerator obtained by microencapsulating a compound having a carboxyl group as a curing catalyst. A liquid epoxy resin composition, and a semiconductor device sealed with a cured product of the liquid epoxy resin composition are provided. Furthermore, a flip chip type semiconductor device in which a cured product of the liquid epoxy resin composition is sealed as an underfill material is provided.
本発明の液状エポキシ樹脂組成物は、保存性を維持しつつ硬化時間を短縮することができる。また、シリコンチップの表面、特に感光性ポリイミド樹脂や窒化膜との密着性に優れた硬化物を与え、吸湿後のリフローの温度が従来温度２４０℃付近から２６０〜２７０℃に上昇しても不良が発生せず、更にＰＣＴ（１２０℃／２．１ａｔｍ）などの高温多湿の条件下でも劣化せず、−６５℃／１５０℃の温度サイクルにおいて数百サイクルを超えても剥離、クラックが起こらない半導体装置を提供することができる。 The liquid epoxy resin composition of the present invention can shorten the curing time while maintaining storability. In addition, it gives a cured product with excellent adhesion to the surface of the silicon chip, particularly photosensitive polyimide resin and nitride film, and even if the reflow temperature after moisture absorption rises from around 240 ° C. to 260 to 270 ° C. Does not occur, and does not deteriorate even under high temperature and high humidity conditions such as PCT (120 ° C / 2.1 atm), and peeling and cracking do not occur even if the temperature cycle of -65 ° C / 150 ° C exceeds several hundred cycles. A semiconductor device can be provided.
本発明の液状エポキシ樹脂組成物において、液状エポキシ樹脂（Ａ）は、一分子内に３官能基以下のエポキシ基を含有する常温で液状のエポキシ樹脂であればいかなるものでも使用可能であるが、２５℃における粘度が８００Ｐａ・ｓ以下、特に５００Ｐａ・ｓ以下のものが好ましく、具体的には、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂等のビスフェノール型エポキシ樹脂、ナフタレン型エポキシ樹脂、フェニルグリシジルエーテルなどが挙げられ、これらの中でも室温（２５℃）で液状のエポキシ樹脂を使用することが好ましい。また、本発明の液状エポキシ樹脂は、１種を単独で又は２種以上を併用することができる。 In the liquid epoxy resin composition of the present invention, the liquid epoxy resin (A) may be any epoxy resin that is liquid at room temperature and contains an epoxy group having three or less functional groups in one molecule. Those having a viscosity at 25 ° C. of 800 Pa · s or less, particularly 500 Pa · s or less are preferred. Specifically, bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, naphthalene type epoxy resins, phenylglycidyl An ether etc. are mentioned, Among these, it is preferable to use a liquid epoxy resin at room temperature (25 degreeC). Moreover, the liquid epoxy resin of this invention can be used individually by 1 type or in combination of 2 or more types.
また、本発明のエポキシ樹脂は、下記構造式（１），（２）で示されるエポキシ樹脂を侵入性に影響を及ぼさない範囲で含有していてもよい。 Moreover, the epoxy resin of this invention may contain the epoxy resin shown by following Structural formula (1), (2) in the range which does not affect intrusion property.
ここで、Ｒ1は水素原子、又は炭素数１〜２０、好ましくは炭素数１〜１０、更に好ましくは炭素数１〜３の一価炭化水素基であり、一価炭化水素基としては、メチル基、エチル基、プロピル基等のアルキル基、ビニル基、アリル基等のアルケニル基等が挙げられる。また、ｘは１〜４の整数であり、特に好ましくは１又は２である。 Here, R 1 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms, and the monovalent hydrocarbon group is methyl. Groups, alkyl groups such as ethyl group and propyl group, and alkenyl groups such as vinyl group and allyl group. Moreover, x is an integer of 1-4, Most preferably, it is 1 or 2.
なお、上記式（２）で示されるエポキシ樹脂を配合する場合、その配合量は、全エポキシ樹脂中２５質量％以上、より好ましくは５０質量％以上、更に好ましくは７５質量％以上であることが推奨される。２５質量％未満であると組成物の粘度が上昇したり、硬化物の耐熱性が低下したりするおそれがある。なお、その上限は１００質量％でもよい。 In addition, when mix | blending the epoxy resin shown by said Formula (2), the compounding quantity is 25 mass% or more in all the epoxy resins, More preferably, it is 50 mass% or more, More preferably, it is 75 mass% or more. Recommended. If it is less than 25% by mass, the viscosity of the composition may increase or the heat resistance of the cured product may decrease. The upper limit may be 100% by mass.
上記式（２）で示されるエポキシ樹脂の例としては、ＲＥ６００ＮＭ（日本化薬（株）製）等が挙げられる。 Examples of the epoxy resin represented by the above formula (2) include RE600NM (manufactured by Nippon Kayaku Co., Ltd.).
上記液状エポキシ樹脂中の全塩素含有量は、１，５００ｐｐｍ以下、望ましくは１，０００ｐｐｍ以下であることが好ましい。また、１００℃で５０％エポキシ樹脂濃度における２０時間での抽出水塩素が１０ｐｐｍ以下であることが好ましい。全塩素含有量が１，５００ｐｐｍを超え、又は抽出水塩素が１０ｐｐｍを超えると半導体素子の信頼性、特に耐湿性に悪影響を与えるおそれがある。 The total chlorine content in the liquid epoxy resin is preferably 1,500 ppm or less, more preferably 1,000 ppm or less. Moreover, it is preferable that the extraction water chlorine in 20 hours in the 50% epoxy resin density | concentration at 100 degreeC is 10 ppm or less. If the total chlorine content exceeds 1,500 ppm or the extracted water chlorine exceeds 10 ppm, the reliability of the semiconductor element, particularly the moisture resistance, may be adversely affected.
次に、本発明に使用する芳香族アミン系硬化剤（Ｂ）としては、芳香族ジアミノジフェニルメタン化合物、例えば、３，３’−ジエチル−４，４’−ジアミノフェニルメタン、３，３’，５，５’−テトラメチル−４，４’−ジアミノフェニルメタン、３，３’，５，５’−テトラエチル−４，４’−ジアミノフェニルメタン、２，４−ジアミノトルエン、１，４−ジアミノベンゼン、１，３−ジアミノベンゼン等の芳香族アミンであることが好ましい。これらは単独又は混合して用いても差し支えない。 Next, as the aromatic amine curing agent (B) used in the present invention, an aromatic diaminodiphenylmethane compound such as 3,3′-diethyl-4,4′-diaminophenylmethane, 3,3 ′, 5 is used. , 5'-tetramethyl-4,4'-diaminophenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminophenylmethane, 2,4-diaminotoluene, 1,4-diaminobenzene An aromatic amine such as 1,3-diaminobenzene is preferable. These may be used alone or in combination.
上記芳香族アミン系硬化剤において、常温で固体である場合はそのまま配合すると樹脂粘度が上昇し、作業性が著しく悪くなるため、予めエポキシ樹脂と溶融混合することが好ましく、後述する指定の配合量で、７０〜１５０℃の温度範囲で１〜２時間溶融混合することが望ましい。混合温度が７０℃未満であると芳香族アミン系硬化剤が十分に相溶しにくくなるおそれがあり、１５０℃を超える温度であると、エポキシ樹脂と反応して粘度上昇するおそれがある。また、混合時間が１時間未満であると芳香族アミン系硬化剤が十分に相溶せず、粘度上昇を招くおそれがあり、２時間を超えるとエポキシ樹脂と反応し、粘度上昇するおそれがある。 In the above aromatic amine-based curing agent, if it is solid at room temperature, the resin viscosity increases and workability is significantly deteriorated. Therefore, it is preferably melt-mixed with an epoxy resin in advance, and the specified blending amount described later Therefore, it is desirable to melt and mix in a temperature range of 70 to 150 ° C. for 1 to 2 hours. If the mixing temperature is less than 70 ° C., the aromatic amine curing agent may not be sufficiently compatible, and if the mixing temperature is higher than 150 ° C., it may react with the epoxy resin and increase the viscosity. Also, if the mixing time is less than 1 hour, the aromatic amine curing agent is not sufficiently compatible and may increase the viscosity, and if it exceeds 2 hours, it may react with the epoxy resin and increase the viscosity. .
なお、本発明に用いられる芳香族アミン系硬化剤の総配合量は、液状エポキシ樹脂と芳香族アミン系硬化剤との当量比〔（Ａ）液状エポキシ樹脂のエポキシ当量／（Ｂ）芳香族アミン系硬化剤のアミン当量〕を０．７以上１．２以下、好ましくは０．７以上１．１以下にすることが好ましい。当量比が０．７未満では未反応のアミン基が残存し、ガラス転移温度の低下となり、また密着性が低下するおそれがある。逆に１．２を超えると硬化物が硬く脆くなり、リフロー時にクラックが発生するおそれがある。 The total amount of the aromatic amine curing agent used in the present invention is the equivalent ratio of the liquid epoxy resin to the aromatic amine curing agent [(A) epoxy equivalent of the liquid epoxy resin / (B) aromatic amine. The amine equivalent of the system curing agent] is 0.7 to 1.2, preferably 0.7 to 1.1. If the equivalent ratio is less than 0.7, unreacted amine groups remain, resulting in a decrease in the glass transition temperature and a decrease in adhesion. On the other hand, if it exceeds 1.2, the cured product becomes hard and brittle, and cracks may occur during reflow.
本発明において用いられるマイクロカプセル型硬化促進剤は、硬化促進剤（硬化触媒）としてカルボキシル基を有する化合物がマイクロカプセル中に閉じ込められたもので、この場合、本発明で使用するマイクロカプセルは、（メタ）アクリル系単量体、例えばアクリル酸エステル、イタコン酸エステル、クロトン酸エステル等の炭素数１〜８のアルキルエステル、このアルキルエステルのアルキル基がアリル基等の置換基を有するもの、スチレン、α−メチルスチレン、アクリロニトリル、メタクリロニトリル、酢酸ビニル等の単官能性単量体及びエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ジビニルベンゼン、ビスフェノールＡジ（メタ）アクリレート、メチレンビス（メタ）アクリルアミド等の多官能単量体から選ばれる１種を単独で又は２種以上の単量体を（共）重合することにより得られたポリマー中に硬化触媒が閉じ込められたものである。なお、上記ポリマーの中では、（メタ）アクリレート系単量体の重合物が好ましい。 The microcapsule type curing accelerator used in the present invention is a compound having a carboxyl group as a curing accelerator (curing catalyst) confined in a microcapsule. In this case, the microcapsule used in the present invention is ( (Meth) acrylic monomers, for example, alkyl esters having 1 to 8 carbon atoms such as acrylic acid ester, itaconic acid ester, crotonic acid ester, the alkyl group of this alkyl ester having a substituent such as allyl group, styrene, Monofunctional monomers such as α-methylstyrene, acrylonitrile, methacrylonitrile, vinyl acetate and ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, divinylbenzene, bisphenol A di (meth) acrylate, methylenebis (Meta) Acry In which curing one selected from polyfunctional monomers amide alone, or two or more monomers (co) in polymer obtained by polymerizing catalyst is confined. In addition, in the said polymer, the polymer of a (meth) acrylate type monomer is preferable.
一方、このマイクロカプセルに入れられる硬化促進剤（硬化触媒）としては、カルボキシル基を有する化合物が用いられる。このカルボキシル基含有化合物としては、安息香酸、４’−エチルビフェニル−４−カルボン酸、４’−プロピルビフェニル−４−カルボン酸、４’−ブチルビフェニル−４−カルボン酸、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ウンデカン二酸、ドデカン二酸、トリデカン二酸、テトラデカン二酸、ペンタデカン二酸、ヘキサデカン二酸、オクタデカン二酸、ノナデカン二酸、エイコサン二酸、メチルマロン酸、エチルマロン酸、ｎ−プロピルマロン酸、ｎ−ブチルマロン酸、メチルコハク酸、エチルコハク酸、１，１，３，５−テトラメチルオクチルコハク酸、マレイン酸、フマル酸、シトラコン酸、γ−メチルシトラコン酸、メサコン酸、γ−メチルメサコン酸、イタコン酸、グルタコン酸、ヘキサヒドロフタル酸、ヘキサヒドロイソフタル酸、ヘキサヒドロテレフタル酸、メチルヘキサヒドロフタル酸、メチルヘキサヒドロイソフタル酸、メチルヘキサヒドロテレフタル酸、シクロヘキセン−１，２−ジカルボン酸、シクロヘキセン−１，６−ジカルボン酸、シクロヘキセン−３，４−ジカルボン酸、シクロヘキセン−４，５−ジカルボン酸、シクロヘキセン−１，３−ジカルボン酸、シクロヘキセン−１，５−ジカルボン酸及びシクロヘキセン−３，５−ジカルボン酸、シクロヘキセン−１，４−ジカルボン酸、シクロヘキセン−３，６−ジカルボン酸、１，３−シクロヘキサジエン−１，２−ジカルボン酸、１，３−シクロヘキサジエン−１，６−ジカルボン酸、１，３−シクロヘキサジエン−２，３−ジカルボン酸、１，３−シクロヘキサジエン−５，６−ジカルボン酸、１，４−シクロヘキサジエン−１，２−ジカルボン酸、１，４−シクロヘキサジエン−１，６−ジカルボン酸、１，３−シクロヘキサジエン−１，３−ジカルボン酸、１，３−シクロヘキサジエン−３，５−ジカルボン酸、１，３−シクロヘキサジエン−１，４−ジカルボン酸、１，３−シクロヘキサジエン−２，５−ジカルボン酸、１，４−シクロヘキサジエン−１，４−ジカルボン酸、１，４−シクロヘキサジエン−３，６−ジカルボン酸、メチルテトラヒドロフタル酸、メチルヘキサヒドロフタル酸、ヘキサヒドロフタル酸、メチルハイミック酸、ピロメリット酸、ベンゾフェノンテトラカルボン酸、３，３’−４，４’−ビフェニルテトラビスベンゾフェノンテトラカルボン酸、ビス（３，４−ジカルボキシフェニル）メタン、２，２−ビス（３，４−ジカルボキシフェニル）プロパンなどが挙げられる。 On the other hand, a compound having a carboxyl group is used as a curing accelerator (curing catalyst) put in the microcapsule. Examples of the carboxyl group-containing compound include benzoic acid, 4′-ethylbiphenyl-4-carboxylic acid, 4′-propylbiphenyl-4-carboxylic acid, 4′-butylbiphenyl-4-carboxylic acid, oxalic acid, malonic acid, Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, nonadecane Diacid, eicosane diacid, methylmalonic acid, ethylmalonic acid, n-propylmalonic acid, n-butylmalonic acid, methylsuccinic acid, ethylsuccinic acid, 1,1,3,5-tetramethyloctylsuccinic acid, maleic acid, Fumaric acid, citraconic acid, γ-methylcitraconic acid, mesaconic acid, γ-methylmesaconic acid , Itaconic acid, glutaconic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, methylhexahydrophthalic acid, methylhexahydroisophthalic acid, methylhexahydroterephthalic acid, cyclohexene-1,2-dicarboxylic acid, cyclohexene -1,6-dicarboxylic acid, cyclohexene-3,4-dicarboxylic acid, cyclohexene-4,5-dicarboxylic acid, cyclohexene-1,3-dicarboxylic acid, cyclohexene-1,5-dicarboxylic acid and cyclohexene-3,5- Dicarboxylic acid, cyclohexene-1,4-dicarboxylic acid, cyclohexene-3,6-dicarboxylic acid, 1,3-cyclohexadiene-1,2-dicarboxylic acid, 1,3-cyclohexadiene-1,6-dicarboxylic acid, 1 , 3-Cyclohexadiene- , 3-dicarboxylic acid, 1,3-cyclohexadiene-5,6-dicarboxylic acid, 1,4-cyclohexadiene-1,2-dicarboxylic acid, 1,4-cyclohexadiene-1,6-dicarboxylic acid, 3-cyclohexadiene-1,3-dicarboxylic acid, 1,3-cyclohexadiene-3,5-dicarboxylic acid, 1,3-cyclohexadiene-1,4-dicarboxylic acid, 1,3-cyclohexadiene-2,5 -Dicarboxylic acid, 1,4-cyclohexadiene-1,4-dicarboxylic acid, 1,4-cyclohexadiene-3,6-dicarboxylic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, hexahydrophthalic acid, methylhigh Mic acid, pyromellitic acid, benzophenone tetracarboxylic acid, 3,3'-4,4'-biphenyltetrabisbenzof Non tetracarboxylic acid, bis (3,4-carboxyphenyl) methane, and 2,2-bis (3,4-carboxyphenyl) propane.
本発明の上記硬化触媒を含有するマイクロカプセル型硬化促進剤の製造方法としては様々な方法が挙げられるが、生産性及び球状度が高いマイクロカプセルを製造するためには、通常、懸濁重合法及び乳化重合法などの従来から公知の方法で製造することができる。 There are various methods for producing the microcapsule-type curing accelerator containing the curing catalyst of the present invention. In order to produce microcapsules with high productivity and high sphericity, the suspension polymerization method is usually used. And can be produced by a conventionally known method such as an emulsion polymerization method.
この場合、一般的に使用されている触媒の分子構造から高濃度マイクロカプセル触媒を得るためには、硬化触媒１０重量部に対して使用する上記単量体の総量は１０〜２００質量部程度が好ましく、より好ましくは１０〜１００質量部、更に好ましくは２０〜５０質量部である。１０質量部未満では潜在性を十分に寄与することが困難となる場合があり、２００質量部を超えると、触媒の比率が低くなり、十分な硬化性を得るためには多量に使用しなければならなくなるため、経済的に不利となる場合がある。 In this case, in order to obtain a high-concentration microcapsule catalyst from the molecular structure of a commonly used catalyst, the total amount of the monomer used with respect to 10 parts by weight of the curing catalyst is about 10 to 200 parts by weight. More preferably, it is 10-100 mass parts, More preferably, it is 20-50 mass parts. If the amount is less than 10 parts by mass, it may be difficult to sufficiently contribute the potential. If the amount exceeds 200 parts by mass, the ratio of the catalyst is lowered, and in order to obtain sufficient curability, a large amount must be used. This may be economically disadvantageous.
このような方法で得られるマイクロカプセルとしては、平均粒径が０．５〜１０μｍ、最大粒径が５０μｍ以下のものを使用することが好ましい。より好ましくは平均粒径が２〜５μｍ、かつ最大粒径が２０μｍ以下のものが望ましい。硬化促進剤の粒径が小さすぎると、比表面積が大きくなり、混合した時の粘度が高くなるおそれがある。また平均粒径が１０μｍを超えると、樹脂への分散が不均一になり、信頼性の低下を引き起こすおそれがある。 As the microcapsules obtained by such a method, those having an average particle diameter of 0.5 to 10 μm and a maximum particle diameter of 50 μm or less are preferably used. More preferably, the average particle diameter is 2 to 5 μm and the maximum particle diameter is 20 μm or less. If the particle size of the curing accelerator is too small, the specific surface area increases and the viscosity when mixed may increase. On the other hand, if the average particle size exceeds 10 μm, the dispersion in the resin becomes non-uniform, which may cause a decrease in reliability.
なお、この平均粒径は、例えばレーザー光回折法による粒度分布測定における重量平均値Ｄ50（又は、メジアン径）等として求めることができる（以下、同様）。 Incidentally, the average particle size, for example, a weight average value D 50 (or median diameter) in particle size distribution measurement by laser diffraction method can be determined as such (hereinafter, the same).
また、上記マイクロカプセルとしては、下記性能を有するものを使用することが好ましい。即ち、硬化触媒を含有するマイクロカプセルを１ｇ秤量し、これをクレゾール３０ｇに混合した後、３０℃で放置し、溶出する触媒をガスクロマトグラフィーで定量した場合、マイクロカプセルから溶出する触媒が３０℃、１５分でマイクロカプセル中に含まれる全触媒量の７０質量％以上であるものを用いる。７０質量％未満では、硬化時間が長くかかるおそれがあり、生産性が低下する場合がある。望ましくは、溶出量が７５質量％以上である。 Moreover, it is preferable to use what has the following performance as said microcapsule. That is, 1 g of microcapsules containing a curing catalyst are weighed, mixed with 30 g of cresol, left at 30 ° C., and when the eluted catalyst is quantified by gas chromatography, the catalyst eluted from the microcapsule is 30 ° C. , Which is 70% by mass or more of the total amount of catalyst contained in the microcapsule in 15 minutes. If it is less than 70% by mass, the curing time may take a long time, and the productivity may decrease. Desirably, the amount of elution is 75 mass% or more.
上記本発明のマイクロカプセル型硬化剤の配合量は、（Ａ）液状エポキシ樹脂と、（Ｂ）芳香族アミン系硬化剤との総量１００質量部に対して０．５〜２０質量部、特に１〜１５質量部であることが好ましい。０．５質量部未満では硬化性が低下するおそれがあり、２０質量部を超える量では硬化性に優れるが、保存性が低下するおそれがある。 The blending amount of the microcapsule type curing agent of the present invention is 0.5 to 20 parts by mass, particularly 1 with respect to 100 parts by mass of the total amount of (A) liquid epoxy resin and (B) aromatic amine curing agent. It is preferably ~ 15 parts by mass. If the amount is less than 0.5 parts by mass, the curability may be lowered. If the amount exceeds 20 parts by mass, the curability is excellent, but the storage stability may be lowered.
また、硬化促進剤として、マイクロカプセル化しない上述の触媒を上記マイクロカプセル触媒と併用添加してもよい。その場合の配合量は、マイクロカプセル触媒とマイクロカプセル化していない触媒の合計が（Ａ）液状エポキシ樹脂と、（Ｂ）芳香族アミン系硬化剤との総量１００質量部に対して０．５〜２０質量部、望ましくは０．５〜１５質量部であることが好ましい。０．５質量部未満では硬化性が低下するおそれがあり、１５質量部を超える量では硬化性に優れるが、保存性が低下するおそれがある。なお、マイクロカプセル化していない触媒の添加量は全触媒添加量の１／１０以下であることが好ましく、１／１０を超える量では硬化性に優れるが保存性が低下するおそれがある。 Further, as the curing accelerator, the above-mentioned catalyst that is not microencapsulated may be added in combination with the microcapsule catalyst. In such a case, the total amount of the microcapsule catalyst and the non-microencapsulated catalyst is 0.5 to 100 parts by mass with respect to 100 parts by mass of the total amount of (A) liquid epoxy resin and (B) aromatic amine curing agent. It is preferable that it is 20 mass parts, desirably 0.5 to 15 mass parts. If the amount is less than 0.5 parts by mass, the curability may be lowered. If the amount exceeds 15 parts by mass, the curability is excellent, but the storage stability may be lowered. In addition, it is preferable that the addition amount of the catalyst which is not microencapsulated is 1/10 or less of the total catalyst addition amount. If the amount exceeds 1/10, the curability is excellent but the storage stability may be lowered.
本発明においては、膨張係数を小さくする目的から、公知の各種無機質充填剤（Ｄ）を添加することができる。無機質充填剤として、具体的には、溶融シリカ、結晶シリカ、アルミナ、ボロンナイトライド、窒化アルミニウム、窒化珪素、マグネシア、マグネシウムシリケートなどが挙げられる。中でも真球状の溶融シリカが低粘度化のため望ましい。 In the present invention, various known inorganic fillers (D) can be added for the purpose of reducing the expansion coefficient. Specific examples of the inorganic filler include fused silica, crystalline silica, alumina, boron nitride, aluminum nitride, silicon nitride, magnesia, magnesium silicate, and the like. Among them, spherical fused silica is desirable for reducing the viscosity.
無機質充填剤は、樹脂と無機質充填剤との結合強度を強くするため、シランカップリング剤、チタネートカップリング剤などのカップリング剤で予め表面処理したものを配合することが好ましい。このようなカップリング剤としては、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン等のエポキシシラン、Ｎ−β（アミノエチル）−γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン等のアミノシラン、γ−メルカプトシラン等のメルカプトシランなどのシランカップリング剤を用いることが好ましい。ここで表面処理に用いるカップリング剤の配合量及び表面処理方法については、特に制限されるものではない。 In order to increase the bond strength between the resin and the inorganic filler, the inorganic filler is preferably blended in advance with a surface treatment with a coupling agent such as a silane coupling agent or a titanate coupling agent. As such a coupling agent, epoxy silane such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N Silane cups such as amino silanes such as -β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and mercaptosilane such as γ-mercaptosilane It is preferable to use a ring agent. Here, the blending amount of the coupling agent used for the surface treatment and the surface treatment method are not particularly limited.
本発明の組成物をポッティング材として使用する場合、無機質充填剤は、平均粒径が２〜２０μｍで、最大粒径が７５μｍ以下、特に５０μｍ以下のものが望ましい。平均粒径が２μｍ未満では粘度が高くなり、多量に充填できない場合があり、一方２０μｍを超えると粗い粒子が多くなり、リード線につまり、ボイドとなるおそれがある。 When the composition of the present invention is used as a potting material, the inorganic filler preferably has an average particle diameter of 2 to 20 μm and a maximum particle diameter of 75 μm or less, particularly 50 μm or less. If the average particle size is less than 2 μm, the viscosity is high and a large amount may not be filled. On the other hand, if the average particle size is more than 20 μm, coarse particles increase, which may lead to a lead wire, that is, a void.
この場合、無機質充填剤の充填量は、（Ａ）液状エポキシ樹脂と（Ｂ）芳香族アミン系硬化剤との総量１００質量部に対して５０〜１，２００質量部、特に１００〜１，２００質量部の範囲が好ましい。１００質量部未満では、膨張係数が大きく冷熱試験においてクラックの発生を誘発させるおそれがある。１，２００質量部を超えると、粘度が高くなり流動性の低下をもたらすおそれがある。 In this case, the filling amount of the inorganic filler is 50 to 1,200 parts by weight, particularly 100 to 1,200, based on 100 parts by weight of the total amount of (A) liquid epoxy resin and (B) aromatic amine curing agent. A range of parts by mass is preferred. If the amount is less than 100 parts by mass, the coefficient of expansion is large and there is a risk of inducing cracks in the cooling test. When it exceeds 1,200 mass parts, there exists a possibility that a viscosity may become high and the fluidity | liquidity may be reduced.
なお、アンダーフィル材として使用する場合には、無機質充填剤は、侵入性の向上と低線膨張化の両立を図るためフリップチップギャップ幅（基板と半導体チップとの隙間）に対して平均粒径が約１／１０以下、最大粒径が１／２以下とすることが好ましい。 When used as an underfill material, the inorganic filler has an average particle diameter with respect to the flip chip gap width (gap between the substrate and the semiconductor chip) in order to achieve both improved penetration and low linear expansion. Is preferably about 1/10 or less and the maximum particle size is preferably ½ or less.
この場合の無機質充填剤の配合量としては、（Ａ）液状エポキシ樹脂と（Ｂ）芳香族アミン系硬化剤との総量１００質量部に対して５０〜４００質量部で配合することが好ましく、より好ましくは１００〜２５０質量部の範囲で配合する。５０質量部未満では、膨張係数が大きく、冷熱試験においてクラックの発生を誘発させるおそれがある。４００質量部を超えると、粘度が高くなり、薄膜侵入性の低下をもたらすおそれがある。 As a compounding quantity of the inorganic filler in this case, it is preferable to mix | blend by 50-400 mass parts with respect to 100 mass parts of total amounts of (A) liquid epoxy resin and (B) aromatic amine type hardening | curing agent, More Preferably it mix | blends in 100-250 mass parts. If it is less than 50 parts by mass, the expansion coefficient is large, and there is a risk of inducing cracks in the cold test. If it exceeds 400 parts by mass, the viscosity will increase and the thin film penetration may be reduced.
本発明のエポキシ樹脂組成物には、応力を低下させる目的でシリコーンゴム、シリコーンオイルや液状のポリブタジエンゴム、メタクリル酸メチル−ブタジエン−スチレンよりなる熱可塑性樹脂などを配合してもよい。好ましくは、アルケニル基含有エポキシ樹脂又はフェノール樹脂のアルケニル基と下記平均組成式（３）で示される１分子中の珪素原子の数が２０〜４００であり、珪素原子に結合した水素原子（ＳｉＨ基）の数が１〜５であるオルガノポリシロキサンのＳｉＨ基との付加反応により得られる共重合体を配合することが好ましい。
ＨaＲ2 bＳｉＯ(4-a-b)/2 （３）
（但し、式中Ｒ2は置換又は非置換の一価の炭化水素基、ａは０．０１〜０．１、ｂは１．８〜２．２、１．８１≦ａ＋ｂ≦２．３である。）
The epoxy resin composition of the present invention may be blended with silicone rubber, silicone oil, liquid polybutadiene rubber, thermoplastic resin made of methyl methacrylate-butadiene-styrene, or the like for the purpose of reducing stress. Preferably, the alkenyl group of the alkenyl group-containing epoxy resin or phenol resin and the number of silicon atoms in one molecule represented by the following average composition formula (3) are 20 to 400, and a hydrogen atom (SiH group bonded to the silicon atom) ) Is preferably blended with a copolymer obtained by addition reaction with SiH groups of organopolysiloxane having 1-5.
H a R 2 b SiO (4-ab) / 2 (3)
Wherein R 2 is a substituted or unsubstituted monovalent hydrocarbon group, a is 0.01 to 0.1, b is 1.8 to 2.2, and 1.81 ≦ a + b ≦ 2.3. is there.)
なお、Ｒ2の一価炭化水素基としては、炭素数１〜１０、特に炭素数１〜８のものが好ましく、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ヘキシル基、オクチル基、デシル基等のアルキル基、ビニル基、アリル基、プロペニル基、ブテニル基、ヘキセニル基等のアルケニル基、フェニル基、キシリル基、トリル基等のアリール基、ベンジル基、フェニルエチル基、フェニルプロピル基等のアラルキル基などや、これらの炭化水素基の水素原子の一部又は全部を塩素、フッ素、臭素等のハロゲン原子で置換したフロロメチル基、ブロモエチル基、トリフルオロプロピル基等のハロゲン置換一価炭化水素基を挙げることができる。 The monovalent hydrocarbon group for R 2 is preferably a group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, and is preferably a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert- Alkyl groups such as butyl, hexyl, octyl and decyl, alkenyl such as vinyl, allyl, propenyl, butenyl and hexenyl, aryl such as phenyl, xylyl and tolyl, and benzyl Fluoromethyl group, bromoethyl group, trifluoropropyl, etc., wherein aralkyl groups such as phenylethyl group, phenylpropyl group, etc., or some or all of hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as chlorine, fluorine, bromine, etc. And halogen-substituted monovalent hydrocarbon groups such as a group.
上記共重合体としては、中でも下記構造式（４）のものが望ましい。 As the above-mentioned copolymer, the following structural formula (4) is preferable.
上記式中、Ｒ2は上記と同じであり、Ｒ3は−ＣＨ2ＣＨ2ＣＨ2−、−ＯＣＨ2−ＣＨ（ＯＨ）−ＣＨ2−Ｏ−ＣＨ2ＣＨ2ＣＨ2−又は−Ｏ−ＣＨ2ＣＨ2ＣＨ2−であり、Ｒ4は水素原子又は炭素数１〜４のアルキル基である。ｎは４〜１９９、好ましくは１９〜１０９の整数、ｐは１〜１０の整数、ｑは１〜１０の整数である。 In the above formula, R 2 is the same as above, and R 3 is —CH 2 CH 2 CH 2 —, —OCH 2 —CH (OH) —CH 2 —O—CH 2 CH 2 CH 2 — or —O—. CH 2 CH 2 CH 2 —, and R 4 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n is an integer of 4 to 199, preferably 19 to 109, p is an integer of 1 to 10, and q is an integer of 1 to 10.
上記共重合体をジオルガノポリシロキサン単位が（Ａ）液状エポキシ樹脂１００質量部に対して０〜２０質量部、特には２〜１５質量部含まれるように配合することで応力をより一層低下させることができる。 The stress is further reduced by blending the above copolymer so that the diorganopolysiloxane unit is contained in an amount of 0 to 20 parts by mass, particularly 2 to 15 parts by mass with respect to 100 parts by mass of the liquid epoxy resin (A). be able to.
本発明の液状エポキシ樹脂組成物には、更に必要に応じ、接着向上用炭素官能性シラン、カーボンブラックなどの顔料、染料、酸化防止剤、その他の添加剤を本発明の目的を損なわない範囲で配合することができる。但し、本発明においては、表面処理剤として使用する以外に接着向上用炭素官能性シラン等としてアルコキシ系シランカップリング剤を添加しないことが好ましい。特に、アンダーフィル材として用いる場合、少量でもアルコキシ系シランカップリング剤を配合すると、ボイドの原因となるおそれがある。 In the liquid epoxy resin composition of the present invention, if necessary, a carbon functional silane for improving adhesion, a pigment such as carbon black, a dye, an antioxidant, and other additives within a range not impairing the object of the present invention. Can be blended. However, in the present invention, it is preferable not to add an alkoxy-based silane coupling agent as a carbon-functional silane for improving adhesion other than the use as a surface treatment agent. In particular, when used as an underfill material, if an alkoxy-based silane coupling agent is blended even in a small amount, it may cause voids.
本発明の液状エポキシ樹脂組成物は、例えば、液状エポキシ樹脂、芳香族アミン系硬化剤、マイクロカプセル型硬化促進剤、必要に応じて無機質充填剤及びその他の添加剤等を同時に又は別々に、必要により加熱処理を加えながら、撹拌、溶解、混合、分散させることにより得ることができる。これらの混合、撹拌、分散等の装置としては、特に限定されるものではないが、撹拌、加熱装置を備えたライカイ機、３本ロール、ボールミル、プラネタリーミキサー等を用いることができる。またこれら装置を適宜組み合わせて使用してもよい。 The liquid epoxy resin composition of the present invention requires, for example, a liquid epoxy resin, an aromatic amine-based curing agent, a microcapsule-type curing accelerator, an inorganic filler and other additives as necessary, or simultaneously. It can be obtained by stirring, dissolving, mixing and dispersing while applying heat treatment. The apparatus for mixing, stirring, dispersing and the like is not particularly limited, and a lykai machine, a three roll, a ball mill, a planetary mixer and the like equipped with a stirring and heating device can be used. Moreover, you may use combining these apparatuses suitably.
なお、本発明において、封止材として用いる液状エポキシ樹脂組成物の粘度は、２５℃において１，０００Ｐａ・ｓ以下、特に５００Ｐａ・ｓ以下のものが好ましい。また、この組成物の成形方法、成形条件は、常法とすることができるが、好ましくは、先に１００〜１２０℃、０．５時間以上、その後１５０〜１７５℃、０．５時間以上の条件で熱オーブンキュアを行う。１００〜１２０℃での加熱が０．５時間未満では、硬化後にボイドが発生する場合がある。また１５０〜１７５℃での加熱が０．５時間未満では、十分な硬化物特性が得られない場合がある。この場合、キュアの時間は加熱温度に応じて適宜選定される。 In the present invention, the viscosity of the liquid epoxy resin composition used as the sealing material is preferably 1,000 Pa · s or less, particularly 500 Pa · s or less at 25 ° C. The molding method and molding conditions of this composition may be conventional methods, but preferably 100 to 120 ° C. for 0.5 hour or longer, and then 150 to 175 ° C. for 0.5 hour or longer. Heat oven cure under conditions. When heating at 100 to 120 ° C. is less than 0.5 hour, voids may occur after curing. Further, if the heating at 150 to 175 ° C. is less than 0.5 hours, sufficient cured product characteristics may not be obtained. In this case, the curing time is appropriately selected according to the heating temperature.
ここで、本発明に用いるフリップチップ型半導体装置としては、例えば図１に示したように、通常、有機基板１の配線パターン面に複数個のバンプ２を介して半導体チップ３が搭載されているものであり、上記有機基板１と半導体チップ３との隙間（バンプ２間の隙間）にアンダーフィル材４が充填され、その側部がフィレット材５で封止されたものとすることができるが、本発明の封止材は、特にこのようなアンダーフィル材として使用する場合に有効である。
Here, as a flip chip type semiconductor device used in the present invention, for example, as shown in FIG. 1, for example, a
以下、実施例及び比較例を挙げて本発明を詳細に説明するが、本発明は下記の実施例に制限されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not restrict | limited to the following Example.
［実施例１〜６、比較例１〜４］
表１で示す成分を３本ロールで均一に混練することにより、１０種の樹脂組成物を得た。これらの樹脂組成物を用いて、以下に示す試験を行った。その結果を表２に示す。
［粘度］
ＢＨ型回転粘度計を用いて４ｒｐｍの回転数で２５℃における粘度を測定した。
［保存性］
２５℃／６０％ＲＨにおいて樹脂組成物を保存し、上記測定条件で２０％粘度上昇するのに要した時間の１／２の時間を保存性とした。
［ゲル化時間］
１５０℃のホットプレートに０．５ｃｃの液状樹脂組成物を滴下し、スパチュラで撹拌して糸引きが切れるところでゲル化時間とした。
［Ｔｇ（ガラス転移温度）、ＣＴＥ１（膨張係数）、ＣＴＥ２（膨張係数）］
樹脂組成物を１２０℃／０．５時間＋１６５℃／３時間で硬化させた５ｍｍ×５ｍｍ×１５ｍｍの硬化物試験片を用いて、ＴＭＡ（熱機械分析装置）により毎分５℃の速さで昇温した時のＴｇを測定した。また、以下の温度範囲の膨張係数を測定した。
ＣＴＥ１の温度範囲は５０〜８０℃、ＣＴＥ２の温度範囲は２００〜２３０℃である。
[Examples 1-6, Comparative Examples 1-4]
Ten types of resin compositions were obtained by uniformly kneading the components shown in Table 1 with three rolls. The test shown below was done using these resin compositions. The results are shown in Table 2.
[viscosity]
The viscosity at 25 ° C. was measured at a rotation speed of 4 rpm using a BH type rotational viscometer.
[Preservation]
The resin composition was stored at 25 ° C./60% RH, and half the time required to increase the viscosity by 20% under the above measurement conditions was defined as storage stability.
[Gelification time]
A 0.5 cc liquid resin composition was dropped onto a 150 ° C. hot plate and stirred with a spatula to determine the gelation time when the stringing was broken.
[Tg (glass transition temperature), CTE1 (expansion coefficient), CTE2 (expansion coefficient)]
Using a cured product test piece of 5 mm × 5 mm × 15 mm in which the resin composition was cured at 120 ° C./0.5 hours + 165 ° C./3 hours, TMA (thermomechanical analyzer) was used at a rate of 5 ° C. per minute. Tg when the temperature was raised was measured. Moreover, the expansion coefficient in the following temperature range was measured.
The temperature range of CTE1 is 50 to 80 ° C, and the temperature range of CTE2 is 200 to 230 ° C.
［接着力テスト］
感光性ポリイミドをコートしたシリコンチップ上に上面の直径２ｍｍ、下面の直径５ｍｍ、高さ３ｍｍの円錐台形状の樹脂組成物試験片を載せ、１２０℃で０．５時間、次いで１６５℃で３時間硬化させた。硬化後、得られた試験片の剪断接着力を測定し、初期値とした。更に、硬化させた試験片をＰＣＴ（１２１℃／２．１ａｔｍ）で３３６時間吸湿させた後、接着力を測定した。いずれの場合も試験片の個数は５個で行い、その平均値を接着力として表記した。
［ＰＣＴ剥離テスト］
ポリイミドコートした１０ｍｍ×１０ｍｍのシリコンチップを３０ｍｍ×３０ｍｍのＦＲ−４基板に約１００μｍのスペーサを用いて設置し、生じた隙間に組成物を侵入させて１２０℃／０．５時間＋１６５℃／３時間の条件で硬化させ、３０℃／６５％ＲＨ／１９２時間後に最高温度２６５℃に設定したＩＲリフローにて５回処理した後の剥離、更にＰＣＴ（１２１℃／２．１ａｔｍ）の環境下に置き、３３６時間後の剥離をＣ−ＳＡＭ（ＳＯＮＩＸ社製）で確認した。
［熱衝撃テスト］
ポリイミドコートした１０ｍｍ×１０ｍｍのシリコンチップを３０ｍｍ×３０ｍｍのＦＲ−４基板に約１００μｍのスペーサを用いて設置し、生じた隙間に組成物を侵入させて１２０℃／０．５時間＋１６５℃／３時間の条件で硬化させ、３０℃／６５％ＲＨ／１９２時間後に最高温度２６５℃に設定したＩＲリフローにて５回処理した後、−６５℃／３０分、１５０℃／３０分を１サイクルとし、２５０サイクル、５００サイクル、７５０サイクル、１，０００サイクル後の剥離、クラックを確認した。
[Adhesion test]
A resin composition test piece in the shape of a truncated cone having a diameter of 2 mm on the upper surface, a diameter of 5 mm on the lower surface, and a height of 3 mm is placed on a silicon chip coated with photosensitive polyimide, and is 0.5 hours at 120 ° C., then 3 hours at 165 ° C. Cured. After curing, the shear strength of the obtained specimen was measured and used as the initial value. Further, the cured test piece was absorbed with PCT (121 ° C./2.1 atm) for 336 hours, and then the adhesive strength was measured. In any case, the number of test pieces was five, and the average value was expressed as adhesive strength.
[PCT peel test]
A polyimide-coated 10 mm × 10 mm silicon chip was placed on a 30 mm × 30 mm FR-4 substrate with a spacer of about 100 μm, and the composition was intruded into the resulting gap, resulting in 120 ° C./0.5 hours + 165 ° C./3. It is cured under the conditions of time, peeled after being treated 5 times by IR reflow set at a maximum temperature of 265 ° C. after 30 ° C./65% RH / 192 hours, and further in an environment of PCT (121 ° C./2.1 atm) The peeling after 336 hours was confirmed by C-SAM (manufactured by SONIX).
[Thermal shock test]
A polyimide-coated 10 mm × 10 mm silicon chip was placed on a 30 mm × 30 mm FR-4 substrate with a spacer of about 100 μm, and the composition was intruded into the resulting gap, resulting in 120 ° C./0.5 hours + 165 ° C./3. It is cured under the conditions of time, and after 30 treatments with IR reflow set to a maximum temperature of 265 ° C after 30 ° C / 65% RH / 192 hours, -65 ° C / 30 minutes, 150 ° C / 30 minutes is one cycle. , 250 cycles, 500 cycles, 750 cycles, peeling after 1,000 cycles, cracks were confirmed.
ＲＥ３０３Ｓ−Ｌ：ビスフェノールＦ型エポキシ樹脂（日本化薬（株）製）
エピコート６３０Ｈ：下記式（５）で示される３官能型エポキシ樹脂（ジャパンエポキシレジン（株）製）
RE303S-L: Bisphenol F type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.)
Epicoat 630H: Trifunctional epoxy resin represented by the following formula (5) (manufactured by Japan Epoxy Resin Co., Ltd.)
芳香族アミン系硬化剤Ａ：ジエチルジアミノジフェニルメタン（日本化薬（株）製、カヤハードＡ−Ａ）
芳香族アミン系硬化剤Ｂ：テトラエチルジアミノフェニルメタン（日本化薬（株）製、Ｃ−３００Ｓ）
Aromatic amine curing agent A: diethyldiaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., Kayahard AA)
Aromatic amine curing agent B: Tetraethyldiaminophenylmethane (Nippon Kayaku Co., Ltd., C-300S)
共重合体：下記式（６）の化合物と下記式（７）の化合物との付加重合体
安息香酸のマイクロカプセル：安息香酸を２０質量％含有したメタクリル酸メチルの重合体，平均粒径が７μｍ，ｏ−クレゾール中で３０℃、１５分間の処理でマイクロカプセルから溶出する触媒の量は８７質量％
ｍ−フタル酸のマイクロカプセル：ｍ−フタル酸を２０質量％含有したメタクリル酸メチルの重合体，平均粒径が７μｍ，ｏ−クレゾール中で３０℃、１５分間の処理でマイクロカプセルから溶出する触媒の量は８９質量％
シランカップリング剤：γ−グリシドキシプロピルトリメトキシシラン（信越化学工業（株）製、ＫＢＭ４０３）
球状シリカ：最大粒径５３μｍ、平均粒径１０μｍの球状シリカ
Benzoic acid microcapsules: a polymer of methyl methacrylate containing 20% by weight of benzoic acid, an average particle size of 7 μm, and the amount of catalyst eluted from the microcapsules by treatment in o-cresol at 30 ° C. for 15 minutes was 87 mass%
m-phthalic acid microcapsules: a polymer of methyl methacrylate containing 20% by mass of m-phthalic acid, an average particle size of 7 μm, and a catalyst eluted from the microcapsules by treatment in o-cresol at 30 ° C. for 15 minutes The amount of is 89% by mass
Silane coupling agent: γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403)
Spherical silica: spherical silica with a maximum particle size of 53 μm and an average particle size of 10 μm
１ 有機基板
２ バンプ
３ 半導体チップ
４ アンダーフィル材
５ フィレット材
1
Claims (7)
（Ｂ）芳香族アミン系硬化剤、
（Ｃ）硬化触媒としてカルボキシル基を有する化合物をマイクロカプセル化したマイクロカプセル型硬化促進剤
を必須成分とすることを特徴とする液状エポキシ樹脂組成物。 (A) Liquid epoxy resin,
(B) an aromatic amine curing agent,
(C) A liquid epoxy resin composition comprising, as an essential component, a microcapsule type curing accelerator obtained by microencapsulating a compound having a carboxyl group as a curing catalyst.
A flip chip type semiconductor device in which a cured product of the liquid epoxy resin composition according to claim 1 is sealed as an underfill material.
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| WO2014103652A1 (en) * | 2012-12-25 | 2014-07-03 | 株式会社スリーボンド | Curable resin composition |
| CN106189079A (en) * | 2014-09-26 | 2016-12-07 | 三星电机株式会社 | Resin combination and dielectric film for dielectric film |
| CN114716953A (en) * | 2022-04-18 | 2022-07-08 | 上海燊量科技有限公司 | Resin adhesive for steel wire rope rigging pouring and preparation method and application thereof |
| CN115716908A (en) * | 2022-11-21 | 2023-02-28 | 武汉轻工大学 | Synthesis method of medium-high molecular weight alicyclic epoxy resin and application of medium-high molecular weight alicyclic epoxy resin in photoelectron packaging field |
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