JP3915604B2 - One-part epoxy resin composition and cured product - Google Patents
One-part epoxy resin composition and cured product Download PDFInfo
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- JP3915604B2 JP3915604B2 JP2002168189A JP2002168189A JP3915604B2 JP 3915604 B2 JP3915604 B2 JP 3915604B2 JP 2002168189 A JP2002168189 A JP 2002168189A JP 2002168189 A JP2002168189 A JP 2002168189A JP 3915604 B2 JP3915604 B2 JP 3915604B2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- 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
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
- H01L2224/8319—Arrangement of the layer connectors prior to mounting
- H01L2224/83192—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on another item or body to be connected to the semiconductor or solid-state body
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/01—Chemical elements
- H01L2924/01019—Potassium [K]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/01—Chemical elements
- H01L2924/01079—Gold [Au]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/013—Alloys
- H01L2924/0132—Binary Alloys
- H01L2924/01322—Eutectic Alloys, i.e. obtained by a liquid transforming into two solid phases
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Description
【０００１】
【発明の属する技術分野】
この発明は、無溶剤型の一液性エポキシ樹脂組成物およびその硬化物に関し、さらに詳しくは、エポキシ樹脂とイミド単位を有し末端に酸無水物基を有するイミド系オリゴマーである酸無水物系硬化剤とを含有してなり、２５℃において２５０ポイズを越える粘度を有し、高温発泡性が抑制され、加熱硬化して得られる硬化物の２５℃における引張弾性率が２５０ｋｇ／ｍｍ２以下であり、チップ部品と配線回路基板との間隙の封止充填剤として好適に使用される一液性エポキシ樹脂組成物、および。該組成物を硬化してなる硬化物に関する。
【０００２】
【従来の技術】
電子機器の小型軽量化や薄膜化が進むにつれ、半導体チップ部品を配線回路基板上に実装する方法として、チップ部品と配線回路基板とをバンプで導通させるフリップチップ実装が用いられている。
フリップチップ実装は、チップ部品の電極と配線回路基板の電極部とをハンダや共晶金属からなるバンプで接合する方法であるが、チップ部品と配線回路基板とは熱膨張率が異なるために、使用時の熱膨張や熱収縮によって長期信頼性が不確実になる。このため、フリップチップ実装では、チップ部品と配線回路基板との間隙に例えばエポキシ樹脂組成物のような熱硬化性樹脂組成物からなる封止充填剤を充填し、熱膨張や熱収縮により接合部分に集中する応力歪を吸収、緩和、及び、低減させることによって、信頼性を高めて用いられている。
従来、この充填剤は、まずチップ部品と配線回路基板との電極間を接合し、次いで、その間隙に低粘度の液状樹脂組成物を毛管現象によって注入した後硬化させる方法によって形成されていた。しかし、この方法では、チップ部品と配線回路基板との間隙が更に狭まると、液状樹脂組成物の注入工程の作業効率が低下したり、均一に注入することが難しくなってボイドが発生し易くなったり、更に、充填そのものが困難になるという問題があった。
【０００３】
そのため、近年、予め液状樹脂組成物の適量をチップ部品又は配線回路基板の表面の所定位置に塗布あるいは滴下して配置しておき、その後で、チップ部品の電極と配線回路基板の電極部とをバンプで加熱圧着することによって、チップ部品と配線回路基板との間隙に封止充填剤を形成する方法が検討されている。
一方で、電子機器の小型軽量化や薄膜化が進むにつれ、配線回路基板も従来のガラスエポキシなどのリジッドな材料からポリイミドフィルムなどのフレキシブルな材料へと移行しつつある。
このような状況から、フリップチップ実装において、予め液状樹脂組成物の適量をチップ部品又は配線回路基板の表面の所定位置に塗布あるいは滴下して配置しておき、次いで、そのチップ部品と配線回路基板とをバンプで加熱接合することによって、チップ部品と配線回路基板との間隙に封止充填剤を形成する方法に好適に用いることができる封止充填剤が求められていた。すなわち、チップ部品又は配線回路基板の表面に塗布あるいは滴下して所定位置に適当な盛り上りを持った形態で配置することができ、次いで、それらのチップ部品と配線回路基板とを加熱接合する時に、所定位置の範囲を越えて流れ出したり飛び散ったりしないでチップ部品と配線回路基板との間隙を空隙なく充填でき、加熱によって発泡や沸騰や分解がなく、適当な速度でゲル化又は硬化が進行し、更に、硬化物としたときに、弾性率が小さく、電気絶縁性が高く、ポリイミドフィルム及びシリコンウエハーに対する密着性が高く、ハンダや金属共晶などのフラックス処理に耐える耐熱性がある液状樹脂組成物からなる封止充填剤が求められていた。
【０００４】
特開平９−１５３５７０号公報には、低弾性率充填材料を提供するものとして、ブタジエン系ゴム粒子を含有するものが開示されているが、均一分散が困難であり長期間の信頼性は満足するものではない。
特開２０００−１９８８３１号公報には、低発泡性のエポキシ樹脂組成物が開示されているが、ＬＳＩの封止用に用いられるものであって、低弾性率のものではない。
特開２０００−１００８７０号公報には、予め樹脂組成物を配線回路基板の表面に真空雰囲気下で印刷して配置し、次いで、そのチップ部品と配線回路基板とをバンプで加熱接合することによって、チップ部品と配線回路基板との間隙に封止充填剤を形成する半導体部品の製造方法が提案されている。ここでは、アミン系硬化剤等からなる一液性のエポキシ樹脂組成物を用いているが、イミド単位を有し末端に酸無水物基を有するイミド系オリゴマーである酸無水物系硬化剤を用いることについては、全く言及されていない。
【０００５】
【発明が解決しようとする課題】
本発明の目的は、液状樹脂組成物であって、チップ部品又は配線回路基板の表面に塗布あるいは滴下して指定位置に適当な盛り上りを持った形態で配置することができ、次いで、それらのチップ部品と配線回路基板とを加熱接合する時に、所定位置の範囲を越えて流れ出したり飛び散ったりしないでチップ部品と配線回路基板との間隙を空隙なく充填することができ、加熱時に発泡や沸騰や分解がなく、適当な速度でゲル化又は硬化が進行し、更に、硬化物としたときに、弾性率が小さく、電気絶縁性が高く、ポリイミドフィルム及びシリコンウエハーに対する密着性が高く、ハンダや金属共晶などのフラックス処理に耐える耐熱性がある、新たな無溶剤型の一液性エポキシ樹脂組成物と、それを加熱硬化して得られる硬化物を提供することである。
すなわち、フリップチップ実装において、予めチップ部品又は配線回路基板の表面に塗布あるいは滴下して配置しておき、次いで、チップ部品と配線回路基板とをバンプで加熱接合することによって、チップ部品と配線回路基板との間隙に封止充填剤を好適に形成することができる無溶剤型の一液性エポキシ樹脂組成物と、それを加熱硬化して得られる硬化物からなる封止充填剤を提供することである。
【０００６】
【課題を解決するための手段】
本発明は、２以上の芳香環を有するエポキシ樹脂、２以上の脂肪族環を有するエポキシ樹脂、２以上の複素環を有するエポキシ樹脂、又はそれらの混合物からなるエポキシ樹脂と、水洗浄及び真空乾燥後の下記式（１）で示されるイミド単位を有し末端に酸無水物基を有するイミド系オリゴマーである酸無水物系硬化剤とを含有してなり、２５℃において２５０ポイズを超える粘度を有し、３００℃での高温発泡性が抑制された、チップ部品と配線基板との間隙の封止充填材として使用され２８５℃以上に加熱処理してゲル化又は硬化を進めるフリップチップ実装用一液性エポキシ樹脂組成物に関する。
【化２】
また、前記一液性エポキシ樹脂組成物において、加熱硬化して得られる硬化物の２５℃における引張弾性率が２５０ｋｇ／ｍｍ２以下であること、硬化剤が、前記式（１）で示される酸無水物系硬化剤と、フェノール樹脂系硬化剤、及び／又は、２以上の芳香族環あるいは脂肪族環を有する酸無水物系硬化剤とを含んでなり、硬化剤全成分総量でエポキシ基総量に対して１当量以下の濃度で含有されてなることに関する。
更に、基板に配線回路が形成された配線回路基板上に前記いずれかの一液性エポキシ樹脂組成物を適当な盛り上がりを持った形態で配置し、続いてバンプが設けられたチップ部品用電極を有するチップ部品を、チップ部品のバンプを配線回路基板の電極の位置と整合させて前記チップ部品を前記配線回路基板に押圧しながら２８５℃以上に加熱処理して、前記一液性エポキシ樹脂組成物をゲル化又は硬化を進めると同時に前記バンプを溶融又は共晶化して電極間を接合することを特徴とするチップ部品の実装方法に関する。
また、前記一液性エポキシ樹脂組成物を加熱硬化してなる硬化物に関する。
更に、チップ部品と配線回路基板との間隙が前記硬化物によって充填されているフリップチップ実装品に関し、チップ部品と配線回路基板との間隙に充填された前記硬化物の厚さが０．０２〜０．５ｍｍであることに関する。
【０００７】
【発明の実施の形態】
以下に、この発明の好ましい実施形態を列記する。
１）式（１）で示されるイミド単位を有し末端に酸無水物基を有するイミド系オリゴマーである酸無水物系硬化剤が、Ａ成分とＢ成分とのモル組成比（Ａ／Ｂ）が１．２〜５、好ましくは１．２〜３、特に１．２〜２の範囲内にある前記一液性エポキシ樹脂組成物。
２）２５℃における粘度が２５０ポイズを越えている、好ましくは４００ポイズ〜２０００ポイズである前記一液性エポキシ樹脂組成物。
３）加熱硬化して得られる硬化物の２５℃における引張弾性率が２５０ｋｇ／ｍｍ２以下、好ましくは２００ｋｇ／ｍｍ２以下である前記一液性エポキシ樹脂組成物。
４）２００℃に加熱した時に、特に３００℃に加熱した時に発泡しない程度に高温発泡性が抑制された前記一液性エポキシ樹脂組成物。
５）エポキシ樹脂が、２以上の芳香環を有するエポキシ樹脂、２以上の脂肪族環を有するエポキシ樹脂（縮合脂環式エポキシ樹脂を含む）、２以上の複素環を有するエポキシ樹脂、または、それらの混合物である前記一液性エポキシ樹脂組成物。
６）エポキシ樹脂が、ビスフェノール型エポキシ樹脂、水添ビスフェノール型エポキシ樹脂、ノボラック型エポキシ樹脂、２以上の複素環を有する複素環式エポキシ樹脂、および、それらの混合物からなるからなる前記一液性エポキシ樹脂組成物。
７）硬化剤が、式（１）で示される酸無水物系硬化剤と、フェノール樹脂系硬化剤、及び／又は、２以上の芳香族環あるいは脂肪族環を有する酸無水物系硬化剤（縮合脂環式酸無水物も含む）とを含んでなり、硬化剤全成分総量でエポキシ基総量に対して１当量以下の濃度で含有されている前記一液性エポキシ樹脂組成物。
８）硬化剤が、硬化剤全成分合計１００モル％中、式（１）で示されるイミド単位を有し末端に酸無水物基を有するイミド系オリゴマーが１〜９９モル％、特に５〜５０モル％であり、フェノール樹脂系硬化剤、及び／又は、２以上の芳香族環あるいは脂肪族環を有する酸無水物系硬化剤（縮合脂環式酸無水物も含む）が９９〜１モル％、特に９５〜５０モル％である前記一液性エポキシ樹脂組成物。９）さらに、シランカップリング剤、顔料、染料が含有されてなる前記一液性エポキシ樹脂組成物。
１０）チップ部品と配線回路基板との間隙の封止充填剤として使用される前記一液性エポキシ樹脂組成物。
１１）予めチップ部品又は配線回路基板の表面に塗布あるいは滴下して指定位置に適当な盛り上りを持った平面状に凸状の形態で配置することができ、次いで、それらのチップ部品と配線回路基板とをバンプで加熱接合する時に、所定位置の範囲を越えて流れ出したり飛び散ったりしないでチップ部品と配線回路基板との間隙を空隙なしに充填でき、適当な速度でゲル化又は硬化が進行し、更に、硬化物としたときに、弾性率が小さく、電気絶縁性が高く、ポリイミドフィルム及びシリコンウエハーに対する密着性が高く、ハンダや金属共晶などのフラックス処理に耐える耐熱性がある前記一液性エポキシ樹脂組成物。
１２）チップ部品と配線回路基板との間隙を封止充填した前記一液性エポキシ樹脂組成物の加熱硬化物。
１３）チップ部品と配線回路基板との間隙が前記一液性エポキシ樹脂組成物の加熱硬化物によって充填されているフリップチップ実装品。
１４）チップ部品と配線回路基板との間隙に充填された前記硬化物の厚さが０．０２〜０．５ｍｍ、特に０．０２〜０．０５ｍｍであるフリップチップ実装品。
【０００８】
本発明のエポキシ樹脂組成物は、エポキシ樹脂に、硬化剤として少なくとも前記式（１）で示される末端に酸無水物基を有するイミド系オリゴマーの酸無水物系硬化剤とを混合して得られる。
【０００９】
前記のエポキシ樹脂としては、２以上の芳香族環を有するエポキシ樹脂、２以上の脂肪族環を有するエポキシ樹脂、２以上の複素環を有するエポキシ樹脂、および、それらの混合物が好適である。
特に、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、ビスフェノールＳ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、ジアリルビスフェノールＡ型エポキシ樹脂、ジアリルビスフェノールＦ型エポキシ樹脂、ジアリルビスフェノールＳ型エポキシ樹脂、ジアリルビスフェノールＡＤ型エポキシ樹脂などのビスフェノール型エポキシ樹脂、前記ビスフェノール型エポキシ樹脂の芳香族環が水添された水添ビスフェノール型エポキシ樹脂、ジアミノジフェニルメタン型エポキシ樹脂などのグリシジルアミン型エポキシ樹脂、テトラメチルビフェノール型エポキシ樹脂などのビフェノール型エポキシ樹脂、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、及び、テトラキス（グリシジルオキシフェニル）エタンなどが好適である。
エポキシ樹脂が、上記以外のエポキシ樹脂、例えば、フタル酸、テトラヒドロフタル酸、及び、ヒドロフタル酸などの二塩基酸のジグリシジルエステル類や、ブタンジオールのジグリシジルエーテルなどのエポキシ樹脂では、高温では、特に３００℃では激しく発泡するので用いることはできない。
【００１０】
本発明において、硬化剤として用いられる前記式（１）で示されるイミド単位を有し末端に酸無水物基を有するイミド系オリゴマーのＡ成分を与えるテトラカルボン酸二無水物としては、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物、３，３’，４，４’−ビフェニルエーテルテトラカルボン酸二無水物などの対称芳香族テトラカルボン酸二無水物、２，３，３’，４’−ビフェニルテトラカルボン酸などの非対称芳香族テトラカルボン酸二無水物、前記対称芳香族テトラカルボン酸二無水物や前記非対称芳香族テトラカルボン酸二無水物の水素還元化物、例えばジシクロヘキシル３，３’，４，４’−テトラカルボン酸二無水物〔３，３’，４，４’−ビフェニルテトラカルボン酸テトラメチルを水素還元−加圧加熱加水分解−無水化して得られる。〕、５−（２，５−ジオキソテトラヒドロ−３−フラニル）−３−メチル−３−シクロヘキセン−１，２−ジカルボン酸無水物などが挙げられる。
【００１１】
また、硬化剤として用いられる前記式（１）で示されるイミド単位を有し末端に酸無水物基を有するイミド系オリゴマーのＢ成分を与えるジアミノポリシロキサンとしては、下記式（３）で示されるジアミノポリシロキサンが挙げられる。
【化３】
Ｈ2Ｎ-Ｒ-[Ｓｉ(Ｒ１)(Ｒ２)-Ｏ-]ｎ-Ｓｉ(Ｒ３)(Ｒ４)-Ｒ-ＮＨ２ 式（３）
（但し、式中Ｒは炭素数２〜６のメチレン基又はフェニレン基からなる２価の炭化水素残基を示し、Ｒ１、Ｒ２、Ｒ３およびＲ４は炭素数１〜５の低級アルキル基又はフェニル基を示し、ｎは３〜６０の整数を示す。）
【００１２】
前記ジアミノポリシロキサンの具体的化合物の例としては、α，ω−ビス（２−アミノエチル）ポリジメチルシロキサン、α，ω−ビス（３−アミルプロピル）ポリジメチルシロキサン、α，ω−ビス（４−アミノフェニル）ポリジメチルシロキサン、α，ω−ビス（４−アミノ−３−メチルフェニル）ポリジメチルシロキサン、α，ω−ビス（３−アミノプロピル）ポリジフェニルシロキサン、α，ω−ビス（４−アミノブチル）ポリジメチルシロキサンなどが挙げられる。
本発明において、発明の効果を損なわない範囲内でジアミノポリシロキサンの一部を他の種類のジアミンで置き換えてもよい。
【００１３】
本発明において、硬化剤として用いられる前記式（１）で示されるイミド単位を有し末端に酸無水物基を有するイミド系オリゴマーのＡ成分とＢ成分との組成比（モル比）は、好ましくはＡ／Ｂ＝１．２〜５、好ましくは１．２〜３、特に１．２〜２の範囲内にあるものである。
【００１４】
前記式（１）で示されるイミド単位を有し末端に酸無水物基を有するイミド系オリゴマーは、好適には、Ａ成分を与えるテトラカルボン酸二無水物を一旦エステル化剤、特に炭素数４以下の一級アルコールを用いて、好適には０．５〜２４時間程度還流した後反応混合物を冷却してハーフエステル化し、得られた反応液にＢ成分を与えるジアミノポリシロキサンを両成分のモル組成比（Ａ／Ｂ）が１．２〜５、好ましくは１．２〜３、特に１．２〜２の範囲内となるように加え、不活性ガス流通下、初期においてはハーフエステル化用の一級アルコールを留去し、最終的に１３０℃以上２５０℃未満の温度、特に１６０℃〜２１０℃にて、０．５〜２４時間程度攪拌下に加熱するワンポット反応にて脱水反応させ、次いで、反応混合物を冷却して実質的に溶媒が残存しない反応物として得ることができる。
前記のハーフエステル化剤としては、アルコール性ＯＨ基を１個有する化合物、例えば、メタノール、エタノール、イソプロパノール、ブタノール、エチルセロソルブ、ブチルセロソルブ、プロピレングリコールエチルエーテル、エチルカルビトールなど、特に炭素数４以下である脂肪族アルコールが挙げられ、それらの中でも一級アルコールが好ましい。前記エステル化剤の使用量は、Ａ成分を与えるテトラカルボン酸二無水物１００重量部に対して２０〜１０００重量部程度が好ましい。
【００１５】
本発明のエポキシ樹脂組成物では、硬化剤として、前記式（１）で示されるイミド単位を有し末端に酸無水物基を有するイミド系オリゴマーに加えて、フェノール樹脂系硬化剤、及び／又は、２以上の芳香族環または脂肪族環を有する酸無水物系硬化剤（縮合脂環式酸無水物も含む）を含んだものが好適である。
すなわち、硬化剤が、硬化剤全成分合計１００モル％中、式（１）で示されるイミド単位を有し末端に酸無水物基を有するイミド系オリゴマーが１〜９９モル％、特に好ましくは５〜５０モル％であり、フェノール樹脂系硬化剤、及び／又は、２以上の芳香族環または脂肪族環を有する酸無水物系硬化剤が９９〜１モル％、特に好ましくは９５〜５０モル％とからなる混合物であると、組成物を適当な粘度に調整するのが容易であって、チップ部品又は配線回路基板の表面に塗布あるいは滴下して、指定位置に適当な盛り上りを持った形態で安定して配置することができ、チップ部品と配線回路基板とを過熱圧着する時に、所定位置の範囲を越えて流れ出したり飛び散ったりしないでチップ部品と配線回路基板との間隙を空隙なく充填することが容易になる。また、高温加熱による発泡や沸騰や分解が抑制され、適当な速度でゲル化や硬化が進行し、更に、硬化物としたときに、弾性率が小さく、電気絶縁性が高く、ポリイミドフィルムやシリコンウエファーに対する密着性が高く、ハンダや金属共晶などのフラックス処理に耐える耐熱性を持った組成物を容易に得る事ができる。
硬化剤が、前記式（１）で示されるイミド単位を有し末端に酸無水物基を有するイミド系オリゴマーに、フェノール樹脂系硬化剤、及び／又は、２以上の芳香族環または脂肪族環を有する酸無水物系硬化剤以外の硬化剤を加えると、高温での発泡を抑制することができなるので好ましくない。
本発明のエポキシ樹脂組成物では、硬化剤として、前記式（１）で示されるイミド単位を有し末端に酸無水物基を有するイミド系オリゴマーとフェノール樹脂系硬化剤、及び／又は、２以上の芳香族環または脂肪族環を有する酸無水物系硬化剤との混合物が特に好適である。
【００１６】
本発明のエポキシ樹脂組成物では、硬化剤として、前記式（１）で示されるイミド単位を有し末端に酸無水物基を有するイミド系オリゴマーと、ノボラック型フェノール樹脂またはレゾール型フェノール樹脂との混合物が、加熱時の発泡や沸騰や分解を容易に抑制することができるので、更に好適である。
【００１７】
本発明の一液性エポキシ樹脂組成物には、硬化剤として、更に、前記式（１）で示されるイミド単位を有し末端に酸無水物基を有するオリゴマーのＡ成分を構成するモノマー成分のテトラカルボン酸二無水物が含まれても構わない。すなわち、前記式（１）で示されるイミド単位を有し末端に酸無水物基を有するオリゴマーの製造時に、原料として酸Ａ成分を構成するモノマー成分のテトラカルボン酸二無水物を過剰量加えて反応し、オリゴマーと酸二無水物の混合物が得られた場合には、前記混合物を本発明の一液性エポキシ樹脂組成物の硬化剤として用いることができる。
本発明の一液性エポキシ樹脂組成物には、ヒドラジン類やイミダゾール類などの硬化促進剤を含有させてもよい。
更に、他の添加剤、例えば各種消泡剤、シランカップリング剤、無機あるいは有機フィラー、顔料などを所定量含有させてもよい。
【００１８】
本発明の一液性のエポキシ樹脂組成物において、各成分の割合は、溶剤を使用しないで室温（２５℃）程度の比較的低温で組成物が液状に保たれる割合を基準にして各成分の量が決められる。式（１）で示されるイミド単位を有し末端に酸無水物基を有するオリゴマーがこの一液性エポキシ樹脂組成物中５重量％以上であることが好ましく、また、エポキシ樹脂１００重量部に対して、式（１）で示されるイミド単位を有し末端に酸無水物基を有するオリゴマーを含む酸無水物系硬化剤合計が約１００〜５００重量部であることが好ましい。また、この一液性エポキシ樹脂組成物では、酸無水物系硬化剤全成分総量は、エポキシ基総量に対して１当量以下、特に０．９〜１当量の濃度で含有されていることが好ましい。前記硬化促進剤を含有させる場合は、エポキシ樹脂量に対して０．１〜１０重量部であることが好ましい。
前記シランカップリング剤を含有させる場合には、エポキシ樹脂量に対して０．１〜２５重量部程度が好ましい。また、他の添加剤を使用する場合には、公知の一液性エポキシ樹脂組成物に適用される量を基に決めればよい。
【００１９】
本発明のエポキシ樹脂組成物の粘度は、２５℃において２５０ポイズ以上、好ましくは４００ポイズ以上であり、２０００ポイズ以下の粘度を有する。２５０ポイズ未満の低粘度では、容易に流れ出し易く且つ飛び散り易いので、チップ部品又は配線回路基板の表面に塗布あるいは滴下して配置し次いでチップ部品と配線回路基板とを押圧且つ加熱してフリップチップ実装をおこなうと、配置された一液性エポキシ樹脂組成物は所定領域外に流れ出したり飛び散ったりするので好ましくない。また、本発明のエポキシ樹脂組成物の粘度が２０００ポイズを越えると、フリップチップ実装時にチップ部品又は配線回路基板の表面に印刷装置を用いて塗布したりあるいはニードル付きのシリンジから空気圧で押し出して滴下して配置するのが困難になったり長時間が必要になるので好ましくない。
【００２０】
本発明の一液性エポキシ樹脂組成物は、予め適量をチップ部品又は配線回路基板の表面の所定位置に塗布あるいは滴下して配置しておき、その後で、チップ部品の電極と配線回路基板の電極部とをバンプで加熱接合するフリップチップ実装に好適に用いることができる。
本発明の一液性エポキシ樹脂組成物を用いたフリップチップ実装の一例について図１によって説明する。尚、本発明の一液性エポキシ樹脂組成物の適用は以下の一例に限定されるものではない。
【００２１】
図１（ａ）で示すように、先ず、基板１に配線回路２が形成された配線回路基板上に本発明の一液性エポキシ樹脂組成物４をニードル３から所定位置に所定量を滴下して、適当な盛り上りを持った形態で配置する。続いて図１（ｂ）で示すように、バンプが設けられたチップ部品用電極を有するチップ部品を、チップ部品のバンプを配線回路基板の電極の位置と整合させて前記チップ部品を前記配線回路基板に押圧する。
そうすると、図１（ｃ）で示すように、押圧された一液性エポキシ樹脂組成物４は、チップ部品の下面と配線回路基板との間隙を水平方向に放射状に流れて、チップ部品と配線回路基板との間隙を空隙なく充填する。言い換えれば、一液性エポキシ樹脂組成物は、押圧後にチップ部品の下面の全領域が充填されるように、位置（通常は該領域の略中心）や量や形状が決められて、印刷あるいは滴下によって配置される。
この工程において、一液性液状のエポキシ樹脂組成物４が、封止充填されるべきチップ部品の下面領域以外へ飛び散ったり流れ出してしまわないことが重要である。本発明において、形態保持性が良好とは、このような工程において、一液性エポキシ樹脂組成物が、適当な盛り上りを持った形態で配置することができ、押圧し加熱接着しても、チップ部品の下面領域以外へ飛び散ったり流れ出してしまわないで、チップ部品と配線回路基板との間隙を空隙なく充填することが容易であることを意味する。
通常は、図１（ｃ）の状態で押圧しながら加熱処理して、前記エポキシ樹脂組成物をゲル化又は硬化を進めると同時に、前記バンプを溶融又は共晶化して電極間を接合する。この加熱温度は、バンプがハンダの場合は、１８０℃〜２４０℃程度であり、バンプが金−スズ共晶生成の場合は、２８５℃〜３００℃程度あるいはそれ以上である。このため、前記のエポキシ樹脂組成物が高温での発泡性が抑制されていない場合や前記温度に耐え得る耐熱性がない場合には、ボイドが生じたり、樹脂成分の分解や劣化が起る。
【００２２】
本発明のエポキシ樹脂組成物は、加熱処理後、チップ部品と配線回路基板との間隙を封止充填した硬化物となって、チップ部品と配線回路基板との熱膨張又は収縮によって生ずる影響を緩和する役目を果たす。通常、この硬化物の厚さは、０．０２〜０．５ｍｍ程度である。例えば、金−スズ共晶で接合する場合は０．０２〜０．１０ｍｍ程度であり、特に０．０２〜０．５０ｍｍ程度であり、例えば、ハンダボールを用いるような場合は０．０５〜０．５ｍｍ程度である。本発明のエポキシ樹脂組成物の硬化物は、基板材料であるポリイミドフィルム、エポキシ樹脂、及び、シリコンウエハーとの密着強度が良好であり、且つ、２５℃における引張弾性率が２５０ｋｇ／ｍｍ２以下、特に０．１〜２００ｋｇ／ｍｍ２であるので、チップ部品と配線回路基板とを信頼性高く接合し、しかも、チップ部品と配線回路基板との熱膨張又は収縮によって生じる影響を緩和する効果が極めて優れている。
硬化物の引張り弾性率が２５０ｋｇ／ｍｍ２を越えるものは、チップ部品と配線回路基板との熱膨張又は収縮によって生ずる影響を緩和する役目を十分に果たすことができない。また、硬化物とポリイミドフィルム及びシリコンウエハーとの密着強度が低いと、使用中に剥離を起こし易く、チップ部品と配線回路基板とを信頼性高く接合することができなくなる。また、そのために、チップ部品と配線回路基板との熱膨張又は収縮によって生じる影響を緩和する役割を十分果たすことができなくなる。
【００２３】
図２に、本発明の一液性エポキシ樹脂組成物を用いたチップ部品を配線回路基板にフリップチップ実装したときの一態様の概略図を示す。図２中、７は本発明の一液性エポキシ樹脂組成物の硬化物、４はチップ部品、１はポリイミドフィルム基板、６はバンプ、２は配線回路である。
【００２４】
【実施例】
以下、本発明を実施例によって説明する。尚、本発明は該実施例に限定されるものではない。
尚、実施例中の粘度、高温発泡性、硬化物の引張弾性率、硬化物の密着強度の測定および評価は、次のようにおこなった。
【００２５】
〔エポキシ樹脂組成物の粘度〕
Ｅ型粘度計を用いて２５℃で測定した。
〔高温発泡性〕
エポキシ樹脂組成物からなる試料を厚さ０．２ｍｍ程度のガラス板上に滴下して配置する。所定温度に加熱した熱板上に、前記の試料を滴下して配置したガラス板を、試料が熱板と接触するように試料面を下にして熱板に重ねる。ガラス板を通して目視によりエポキシ樹脂組成物からなる試料を観察し、発泡が見られないものを○、発泡が見られたものを×と判定した。
〔硬化物の引張弾性率〕
硬化物の引張弾性率は、幅４ｍｍのダンベル状に打ち抜いた試験片について、ＡＳＴＭ Ｄ８８２に準じ、ＴＯＹＯ ＢＯＬＤＷＩＮ社製ＴＥＮＳＩＯＮ ＵＴＭ５Ｔを用い、温度２５℃、チャック間３０ｍｍ、引張速度２ｍｍ／分の条件で測定した。
〔硬化物の密着強度〕
エポキシ樹脂組成物を、長さ１０ｃｍ、幅１ｃｍ、厚さ２５μｍのポリイミドフィルム上の中央部へ滴下し、１ｃｍ×１ｃｍにへき開した表面に窒化珪素膜を形成したシリコンウエハーを、窒化珪素膜が組成物と接するようにのせ、１３５℃のホットプレート上で２０分間熱処理後、続けて１８０℃のオーブン中で１時間熱処理し、図３のような試験片を作製した。作製した試験片を、図４に示すように、ポリイミドフィルム面を上面として、シリコンウエハーが上側の押え板より２ｍｍ出るように挟み込み、引張試験機によって引張速度２ｍｍ／分で９０度剥離試験をおこなった。密着強度の評価は、次の通りである。
○：ポリイミドフィルムがシリコンウエハーから剥離せず、シリコンウエハーは破断したもの
×：ポリイミドフィルムがシリコンウエハーから剥離したもの
尚、図３及び図４中、７はエポキシ樹脂組成物の硬化物、２０はシリコンウエハー、３０はポリイミドフィルム、４０は押え板、５０は治具、６０はスペーサーである。
【００２６】
（参考例１）
窒素ガスで置換した四つ口フラスコに、攪拌機、窒素ガス導入管、還流冷却器、共栓を取りつけ、５−（２，５−ジオキソテトラヒドロ−３−フラニル）−３−メチル−３−シクロヘキセン−１，２−ジカルボン酸無水物（大日本インキ化学工業株式会社製 エピクロン Ｂ４４００）１８７ｇとメタノール３００ｇを入れ、還流した。３時間後、室温まで冷却し、還流冷却器を水分離器付きの還流冷却器に換え、消泡剤（ダウコーニングアジア株式会社製 ＦＳアンチフォームＤＢ−１００）０．５ｇ、α，ω−ビス（３−アミノプロピル）ポリジメチルシロキサン（東レ・ダウコーニングシリコーン株式会社製 アミン当量４６０）３２６ｇを加え、１時間かけてメタノールを留去した。続けて、２００℃まで昇温し、水を留去しながら、６時間反応させ、４９６ｇの茶褐色の粘稠物を得た。得られた生成物のうち２００ｇをキシレン１リットルに溶解させ水８００ミリリットルで３回洗浄した後、２００℃で１時間真空乾燥した。
この生成物（以下、ＳｉＢと略記することもある。）の８０℃での粘度は５０ポイズであった。
【００２７】
（実施例１）
参考例１で得たＳｉＢ１０８ｇ、ノボラック型フェノール樹脂（明和化成株式会社製 Ｈ−５）３８ｇとを８０℃で均一になるまで混合した後、室温まで冷却し、ビスフェノールＡ型エポキシ樹脂（バンティコ株式会社製、ＭＹ７９０−１）１００ｇと、硬化促進剤（２−エチル−４−メチルイミダゾールテトラフェニルボレート）４ｇと、シランカップリング剤（信越化学工業株式会社製 ＫＢＭ３０３）５ｇとを加え、ロール混練し、一液性エポキシ樹脂組成物を得た。得られた組成物の粘度は９１０ポイズであった。
この組成物を試料として、３００℃の高温発泡性を評価したが、発泡は見られなかった。
この組成物を１３５℃でホットプレート上で３０分、更に１８０℃のオーブン中で１時間硬化し、硬化物を得た。この硬化物の引張弾性率は１７１ｋｇ／ｍｍ２であった。
硬化物の密着強度を測定したところ、○であった。
【００２８】
（比較例１）
ブタンジオール型エポキシ樹脂（バンディコ株式会社製 アラルダイトＤＹ０２６ＳＰ）１００ｇと、参考例１で得たＳｉＢ１４０ｇと、酸無水物硬化剤（ジャパンエポキシレジン株式会社製 エピキュア ＹＨ３０６）１４１ｇと、硬化促進剤（２−エチル−４−メチルイミダゾール）１ｇと、シランカップリング剤（信越化学工業株式会社製 ＫＢＭ４０３）７．６ｇとを室温で攪拌混合し、一液性エポキシ樹脂組成物を得た。この組成物の粘度は３．１ポイズであった。
この組成物を試料として、３００℃の高温発泡性を評価したところ、激しく発泡した。
【００２９】
【発明の効果】
本発明は以上説明したようなものであるから、以下のような効果を奏する。
すなわち、本発明は、チップ部品又は配線回路基板の表面に塗布あるいは滴下して指定位置に適当な盛り上りを持った形態で配置することができ、次いで、それらのチップ部品と配線回路基板とを加熱接合する時に、所定位置の範囲を越えて流れ出したり飛び散ったりしないでチップ部品と配線回路基板との間隙を空隙なく充填することができ、加熱時に発泡や沸騰や分解がなく、適当な速度でゲル化又は硬化が進行し、更に、硬化物としたときに、弾性率が小さく、電気絶縁性が高く、ポリイミドフィルム及びシリコンウエハーに対する密着性が高く、ハンダや金属共晶などのフラックス処理に耐える耐熱性がある、無溶剤型の一液性エポキシ樹脂組成物と、それを加熱硬化して得られる硬化物を提供すること駕できる。
【図面の簡単な説明】
【図１】本発明の一液性エポキシ樹脂組成物を用いたフリップチップ実装の方法を示す概略図である。
【図２】本発明の一液性エポキシ樹脂組成物を用いたチップ部品を配線回路基板にフリップチップ実装したときの一態様を示す概略図である。
【図３】硬化物の密着強度を測定する試験片を示す概略図である。（ａ）は試験片の平面図であり、（ｂ）は試験片の断面図である。
【図４】硬化物の密着強度を測定する状態を示す概略図である。
【符号の説明】
１：基板、又は、ポリイミド基板
２：配線回路
３：一液性エポキシ樹脂組成物を供給するためのニードル
４：一液性エポキシ樹脂組成物
５：チップ部品
６：バンプ
７：一液性エポキシ樹脂組成物の硬化物
２０：シリコンウエハー
３０：ポリイミドフィルム
４０：押え板
５０：治具
６０：スペーサー[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a solvent-free one-component epoxy resin composition and a cured product thereof, and more specifically, an acid anhydride system which is an imide oligomer having an epoxy resin and an imide unit and an acid anhydride group at the terminal. A curing agent, having a viscosity of more than 250 poise at 25 ° C., suppressing high-temperature foaming properties, and having a cured product obtained by heat curing having a tensile elastic modulus at 25 ° C. of 250 kg / mm. 2 A one-component epoxy resin composition that is preferably used as a sealing filler for the gap between the chip component and the printed circuit board; The present invention relates to a cured product obtained by curing the composition.
[0002]
[Prior art]
As electronic devices become smaller and lighter and thinner, flip-chip mounting is used in which semiconductor chip components are mounted on a printed circuit board by conducting the chip components and the printed circuit board with bumps.
Flip chip mounting is a method of joining the electrode of the chip component and the electrode part of the printed circuit board with bumps made of solder or eutectic metal, but the thermal expansion coefficient differs between the chip component and the printed circuit board. Long-term reliability becomes uncertain due to thermal expansion and contraction during use. For this reason, in flip-chip mounting, the gap between the chip component and the printed circuit board is filled with a sealing filler made of a thermosetting resin composition such as an epoxy resin composition, and bonded portions are formed by thermal expansion or thermal contraction. It is used with increased reliability by absorbing, mitigating, and reducing stress strain concentrated on the surface.
Conventionally, this filler has been formed by a method in which the electrodes of the chip component and the printed circuit board are first joined, and then a low-viscosity liquid resin composition is injected into the gap by capillary action and then cured. However, in this method, when the gap between the chip component and the printed circuit board is further narrowed, the working efficiency of the liquid resin composition injection process is lowered, or it is difficult to uniformly inject, and voids are likely to occur. Furthermore, there is a problem that filling itself becomes difficult.
[0003]
Therefore, in recent years, an appropriate amount of the liquid resin composition is previously applied or dropped at a predetermined position on the surface of the chip component or the printed circuit board, and then the chip component electrode and the electrode portion of the printed circuit board are connected to each other. A method of forming a sealing filler in the gap between the chip component and the printed circuit board by thermocompression bonding with bumps has been studied.
On the other hand, as electronic devices become smaller and lighter and thinner, printed circuit boards are also shifting from conventional rigid materials such as glass epoxy to flexible materials such as polyimide films.
In such a situation, in flip chip mounting, an appropriate amount of the liquid resin composition is previously applied or placed at a predetermined position on the surface of the chip component or the printed circuit board, and then the chip component and the printed circuit board are placed. Thus, there has been a demand for a sealing filler that can be suitably used in a method of forming a sealing filler in the gap between the chip component and the printed circuit board. That is, it can be applied or dripped onto the surface of a chip component or a printed circuit board and arranged in a form having an appropriate rise at a predetermined position, and then when the chip component and the printed circuit board are heated and joined. The gap between the chip component and the printed circuit board can be filled without gaps without flowing out or scattering beyond the range of the predetermined position, and there is no foaming, boiling or decomposition by heating, and gelation or curing proceeds at an appropriate speed. Furthermore, when it is made into a cured product, it has a low elastic modulus, high electrical insulation, high adhesion to polyimide films and silicon wafers, and a heat-resistant liquid resin composition that can withstand flux processing such as solder and metal eutectic. There has been a demand for a sealing filler made of a material.
[0004]
Japanese Patent Laid-Open No. 9-153570 discloses a material containing butadiene rubber particles as a material for providing a low elastic modulus filling material. However, uniform dispersion is difficult and long-term reliability is satisfied. It is not a thing.
Japanese Patent Application Laid-Open No. 2000-198831 discloses a low-foaming epoxy resin composition, but it is used for LSI sealing and not a low elastic modulus.
JP-A-2000-10090 discloses that a resin composition is preliminarily printed and arranged in a vacuum atmosphere on the surface of a printed circuit board, and then the chip component and the printed circuit board are heated and bonded with bumps. A method for manufacturing a semiconductor component has been proposed in which a sealing filler is formed in the gap between the chip component and the printed circuit board. Here, a one-component epoxy resin composition comprising an amine curing agent or the like is used, but an acid anhydride curing agent that is an imide oligomer having an imide unit and an acid anhydride group at the terminal is used. There is no mention of that at all.
[0005]
[Problems to be solved by the invention]
An object of the present invention is a liquid resin composition, which can be applied or dropped onto the surface of a chip component or a printed circuit board and arranged in a form having an appropriate rise at a designated position, and then When heat-bonding the chip component and the printed circuit board, the gap between the chip component and the printed circuit board can be filled without gaps without flowing out or splashing beyond the range of the predetermined position. There is no decomposition, gelation or curing proceeds at an appropriate rate, and when it is made into a cured product, it has a low elastic modulus, high electrical insulation, high adhesion to polyimide films and silicon wafers, solder and metal To provide a new solvent-free one-component epoxy resin composition that is heat resistant to withstand flux processing such as eutectic and a cured product obtained by heating and curing the composition. A.
That is, in flip chip mounting, the chip component and the wiring circuit board are preliminarily applied or dropped on the surface of the chip component or the wiring circuit board, and then the chip component and the wiring circuit board are heat-bonded with bumps. To provide a solvent-free one-component epoxy resin composition capable of suitably forming a sealing filler in a gap with a substrate, and a sealing filler comprising a cured product obtained by heating and curing the composition. It is.
[0006]
[Means for Solving the Problems]
The present invention relates to an epoxy resin having two or more aromatic rings, an epoxy resin having two or more aliphatic rings, an epoxy resin having two or more heterocyclic rings, or a mixture thereof, water washing and vacuum drying And an acid anhydride curing agent which is an imide oligomer having an imide unit represented by the following formula (1) and having an acid anhydride group at the terminal, and has a viscosity exceeding 250 poise at 25 ° C. Yes And High temperature foaming property at 300 ° C. was suppressed, For flip chip mounting that is used as a sealing filler for the gap between the chip component and the wiring board, and is heat-treated at 285 ° C. or higher to promote gelation or curing. One-part epoxy resin Relates to the composition.
[Chemical 2]
In the one-component epoxy resin composition, the cured product obtained by heat curing has a tensile elastic modulus at 25 ° C. of 250 kg / mm. 2 A curing agent is an acid anhydride curing agent represented by the formula (1), a phenol resin curing agent, and / or an acid anhydride having two or more aromatic rings or aliphatic rings. A total amount of all components of the curing agent and not more than 1 equivalent with respect to the total amount of epoxy groups. Ru About that.
Furthermore, on the printed circuit board on which the printed circuit is formed on the board Said Any one-part epoxy resin A chip component having an electrode for a chip component in which the composition is arranged in an appropriate swell and subsequently provided with a bump is aligned with the position of the electrode on the printed circuit board by aligning the bump of the chip component with the chip component. Heat treatment to 285 ° C. or higher while pressing against the printed circuit board Then, the one-component epoxy resin composition is gelled or cured, and at the same time, the bumps are melted or eutectic to join the electrodes. The present invention relates to a chip component mounting method.
Moreover, it is related with the hardened | cured material formed by heat-curing the said one-component epoxy resin composition.
Furthermore, regarding the flip chip mounting product in which the gap between the chip component and the printed circuit board is filled with the cured product, the thickness of the cured product filled in the gap between the chip component and the printed circuit board is 0.02 to 0.02. It relates to being 0.5 mm.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The preferred embodiments of the present invention are listed below.
1) An acid anhydride curing agent, which is an imide oligomer having an imide unit represented by the formula (1) and having an acid anhydride group at the terminal, is a molar composition ratio (A / B) between the A component and the B component. The one-component epoxy resin composition wherein is in the range of 1.2 to 5, preferably 1.2 to 3, particularly 1.2 to 2.
2) The said one-part epoxy resin composition whose viscosity in 25 degreeC exceeds 250 poise, Preferably it is 400 poise-2000 poise.
3) The cured product obtained by heat curing has a tensile elastic modulus at 25 ° C. of 250 kg / mm. 2 Below, preferably 200 kg / mm 2 The said one-component epoxy resin composition which is the following.
4) The said one-part epoxy resin composition by which high temperature foaming property was suppressed to such an extent that it would not foam when heated to 200 degreeC, especially when heated to 300 degreeC.
5) An epoxy resin having two or more aromatic rings, an epoxy resin having two or more aliphatic rings (including condensed alicyclic epoxy resins), an epoxy resin having two or more heterocyclic rings, or those The one-component epoxy resin composition, which is a mixture of
6) The one-component epoxy, wherein the epoxy resin is composed of a bisphenol type epoxy resin, a hydrogenated bisphenol type epoxy resin, a novolac type epoxy resin, a heterocyclic epoxy resin having two or more heterocyclic rings, and a mixture thereof. Resin composition.
7) The curing agent is an acid anhydride curing agent represented by formula (1), a phenol resin curing agent, and / or an acid anhydride curing agent having two or more aromatic rings or aliphatic rings ( The one-component epoxy resin composition is also contained in a total amount of the curing agent in a concentration of 1 equivalent or less with respect to the total amount of epoxy groups.
8) The curing agent is 1 to 99 mol%, particularly 5 to 50 mol of the imide-based oligomer having an imide unit represented by the formula (1) and having an acid anhydride group at the terminal in a total of 100 mol% of the curing agent. 99% to 1% by mole of a phenol resin-based curing agent and / or an acid anhydride-based curing agent having two or more aromatic rings or aliphatic rings (including condensed alicyclic acid anhydrides) The one-part epoxy resin composition, particularly 95 to 50 mol%. 9) The one-component epoxy resin composition further comprising a silane coupling agent, a pigment, and a dye.
10) The said one-component epoxy resin composition used as a sealing filler of the gap | interval of a chip component and a printed circuit board.
11) It can be applied in advance or dropped onto the surface of a chip component or a printed circuit board, and can be arranged in a convex shape in a flat shape with an appropriate rise at a specified position, and then the chip component and the printed circuit When heat-bonding to the board with bumps, the gap between the chip component and the printed circuit board can be filled without gaps without flowing out or scattering beyond the range of the predetermined position, and gelation or curing proceeds at an appropriate speed. Furthermore, when it is made into a cured product, the one liquid has a low elastic modulus, high electrical insulation, high adhesion to a polyimide film and a silicon wafer, and heat resistance that can withstand flux processing such as solder and metal eutectic. Epoxy resin composition.
12) A heat-cured product of the one-component epoxy resin composition in which the gap between the chip component and the printed circuit board is sealed and filled.
13) A flip chip mounting product in which a gap between the chip component and the printed circuit board is filled with a heat-cured product of the one-component epoxy resin composition.
14) A flip chip mounted product in which the thickness of the cured product filled in the gap between the chip component and the printed circuit board is 0.02 to 0.5 mm, particularly 0.02 to 0.05 mm.
[0008]
The epoxy resin composition of the present invention is obtained by mixing an epoxy resin with an acid anhydride curing agent of an imide oligomer having an acid anhydride group at the terminal represented by the formula (1) as a curing agent. .
[0009]
As the epoxy resin, an epoxy resin having two or more aromatic rings, an epoxy resin having two or more aliphatic rings, an epoxy resin having two or more heterocyclic rings, and a mixture thereof are suitable.
In particular, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, diallyl bisphenol A type epoxy resin, diallyl bisphenol F type epoxy resin, diallyl bisphenol S type epoxy resin, diallyl bisphenol AD Bisphenol type epoxy resin such as epoxy resin, hydrogenated bisphenol type epoxy resin in which the aromatic ring of the above bisphenol type epoxy resin is hydrogenated, glycidylamine type epoxy resin such as diaminodiphenylmethane type epoxy resin, tetramethylbiphenol type epoxy resin Novolak type epoxy resin such as biphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin And, tetrakis (glycidyloxyphenyl) ethane are preferred.
When the epoxy resin is an epoxy resin other than the above, for example, an epoxy resin such as diglycidyl esters of dibasic acids such as phthalic acid, tetrahydrophthalic acid, and hydrophthalic acid, or diglycidyl ether of butanediol, Particularly at 300 ° C., it cannot be used because it foams vigorously.
[0010]
In the present invention, tetracarboxylic dianhydrides that give the A component of an imide oligomer having an imide unit represented by the above formula (1) and having an acid anhydride group at the terminal used as a curing agent are 3, 3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride Symmetric aromatic tetracarboxylic dianhydrides such as 2,3,3 ′, 4′-biphenyltetracarboxylic acid, symmetric aromatic tetracarboxylic dianhydrides such as Hydrogen reduction product of the asymmetric aromatic tetracarboxylic dianhydride such as
[0011]
Moreover, as diaminopolysiloxane which gives B component of the imide-type oligomer which has an imide unit shown by the said Formula (1) used as a hardening | curing agent, and has an acid anhydride group at the terminal, it shows by following formula (3). Diaminopolysiloxane may be mentioned.
[Chemical 3]
H 2 N-R- [Si (R 1 ) (R 2 ) -O-] n-Si (R 3 ) (R 4 ) -R-NH 2 Formula (3)
(In the formula, R represents a divalent hydrocarbon residue composed of a methylene group or a phenylene group having 2 to 6 carbon atoms; 1 , R 2 , R 3 And R 4 Represents a lower alkyl group having 1 to 5 carbon atoms or a phenyl group, and n represents an integer of 3 to 60. )
[0012]
Specific examples of the diaminopolysiloxane include α, ω-bis (2-aminoethyl) polydimethylsiloxane, α, ω-bis (3-amylpropyl) polydimethylsiloxane, α, ω-bis (4 -Aminophenyl) polydimethylsiloxane, α, ω-bis (4-amino-3-methylphenyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydiphenylsiloxane, α, ω-bis (4- Aminobutyl) polydimethylsiloxane and the like.
In the present invention, a part of diaminopolysiloxane may be replaced with another kind of diamine within a range not impairing the effects of the invention.
[0013]
In the present invention, the composition ratio (molar ratio) between the A component and the B component of the imide oligomer having an imide unit represented by the formula (1) used as a curing agent and having an acid anhydride group at the terminal is preferably A / B = 1.2-5, preferably 1.2-3, especially 1.2-2.
[0014]
The imide-based oligomer having an imide unit represented by the formula (1) and having an acid anhydride group at the terminal is preferably an esterifying agent, particularly a carbon number of 4 The following primary alcohol is used, and the mixture is preferably refluxed for about 0.5 to 24 hours, and then the reaction mixture is cooled and half-esterified, and diaminopolysiloxane that gives B component to the resulting reaction solution is composed of the molar composition of both components. The ratio (A / B) is 1.2-5, preferably 1.2-3, especially 1.2-2, and in the presence of an inert gas, it is initially used for half-esterification. The primary alcohol is distilled off, and finally the dehydration reaction is performed in a one-pot reaction heated at a temperature of 130 ° C. or higher and lower than 250 ° C., particularly 160 ° C. to 210 ° C. with stirring for about 0.5 to 24 hours, Cool reaction mixture Substantially can be obtained as a reaction product the solvent does not remain Te.
Examples of the half esterifying agent include compounds having one alcoholic OH group, such as methanol, ethanol, isopropanol, butanol, ethyl cellosolve, butyl cellosolve, propylene glycol ethyl ether, ethyl carbitol and the like, particularly those having 4 or less carbon atoms. A certain aliphatic alcohol is mentioned, Among these, primary alcohol is preferable. The amount of the esterifying agent used is preferably about 20 to 1000 parts by weight with respect to 100 parts by weight of tetracarboxylic dianhydride giving component A.
[0015]
In the epoxy resin composition of the present invention, as the curing agent, in addition to the imide oligomer having an imide unit represented by the formula (1) and having an acid anhydride group at the terminal, a phenol resin curing agent, and / or Those containing an acid anhydride curing agent having two or more aromatic rings or aliphatic rings (including condensed alicyclic acid anhydrides) are preferred.
That is, the curing agent is 1 to 99 mol%, particularly preferably 5 of the imide oligomer having an imide unit represented by the formula (1) and having an acid anhydride group at the terminal in 100 mol% of the total components of the curing agent. 99 to 1 mol%, particularly preferably 95 to 50 mol% of a phenol resin curing agent and / or an acid anhydride curing agent having two or more aromatic rings or aliphatic rings. When the composition is composed of the above, it is easy to adjust the composition to an appropriate viscosity, and it is applied or dripped onto the surface of a chip component or a printed circuit board to form an appropriate swell at a specified position. When the chip component and the printed circuit board are overheat-compressed, the gap between the chip component and the printed circuit board is filled without any gaps without flowing out or scattering over a predetermined range. This It becomes easy. In addition, foaming, boiling, and decomposition due to high-temperature heating are suppressed, gelation and curing proceed at an appropriate rate, and when cured, the elastic modulus is low, electrical insulation is high, polyimide film and silicon It is possible to easily obtain a composition having high adhesion to the wafer and having heat resistance capable of withstanding flux treatment such as solder or metal eutectic.
The curing agent is an imide oligomer having an imide unit represented by the formula (1) and having an acid anhydride group at the terminal, a phenol resin curing agent, and / or two or more aromatic rings or aliphatic rings. It is not preferable to add a curing agent other than the acid anhydride-based curing agent having the above because foaming at high temperatures can be suppressed.
In the epoxy resin composition of the present invention, as a curing agent, an imide oligomer having an imide unit represented by the formula (1) and having an acid anhydride group at the terminal, a phenol resin curing agent, and / or two or more. A mixture with an acid anhydride-based curing agent having an aromatic ring or an aliphatic ring is particularly suitable.
[0016]
In the epoxy resin composition of the present invention, as a curing agent, an imide oligomer having an imide unit represented by the above formula (1) and having an acid anhydride group at the terminal, and a novolac type phenol resin or a resol type phenol resin The mixture is more preferable because it can easily suppress foaming, boiling and decomposition during heating.
[0017]
In the one-component epoxy resin composition of the present invention, as a curing agent, a monomer component constituting an A component of an oligomer having an imide unit represented by the formula (1) and having an acid anhydride group at the terminal is further included. Tetracarboxylic dianhydride may be included. That is, when an oligomer having an imide unit represented by the formula (1) and having an acid anhydride group at the terminal is produced, an excess amount of a tetracarboxylic dianhydride as a monomer component constituting the acid A component is added as a raw material. When the mixture of oligomer and acid dianhydride is obtained by reacting, the mixture can be used as a curing agent for the one-component epoxy resin composition of the present invention.
The one-component epoxy resin composition of the present invention may contain a curing accelerator such as hydrazines and imidazoles.
Further, other additives such as various antifoaming agents, silane coupling agents, inorganic or organic fillers, pigments and the like may be contained in a predetermined amount.
[0018]
In the one-component epoxy resin composition of the present invention, the proportion of each component is based on the proportion that the composition is kept in a liquid state at a relatively low temperature of about room temperature (25 ° C.) without using a solvent. The amount of is determined. It is preferable that the oligomer having an imide unit represented by the formula (1) and having an acid anhydride group at the terminal is 5% by weight or more in the one-part epoxy resin composition, and with respect to 100 parts by weight of the epoxy resin. In addition, the total amount of the acid anhydride curing agent including the oligomer having an imide unit represented by the formula (1) and having an acid anhydride group at the terminal is preferably about 100 to 500 parts by weight. Further, in this one-part epoxy resin composition, the total amount of the acid anhydride-based curing agent is preferably 1 equivalent or less, particularly 0.9 to 1 equivalent, based on the total amount of the epoxy group. . When it contains the said hardening accelerator, it is preferable that it is 0.1-10 weight part with respect to the amount of epoxy resins.
When the silane coupling agent is contained, the amount is preferably about 0.1 to 25 parts by weight with respect to the amount of epoxy resin. Moreover, what is necessary is just to determine based on the quantity applied to a well-known one-component epoxy resin composition, when using another additive.
[0019]
The viscosity of the epoxy resin composition of the present invention is 250 poise or more, preferably 400 poise or more at 25 ° C., and has a viscosity of 2000 poise or less. When the viscosity is less than 250 poise, it is easy to flow out and splatter easily, so that it is applied or dropped onto the surface of the chip component or the printed circuit board and then pressed and heated to flip chip mounting. If it is carried out, the one-component epoxy resin composition arranged flows out of the predetermined region or scatters, which is not preferable. Moreover, when the viscosity of the epoxy resin composition of the present invention exceeds 2000 poise, it is applied to the surface of a chip component or a printed circuit board by using a printing device at the time of flip chip mounting, or it is dropped by extruding with a pneumatic pressure from a syringe with a needle. Therefore, it is not preferable because it becomes difficult to arrange and requires a long time.
[0020]
An appropriate amount of the one-component epoxy resin composition of the present invention is preliminarily applied or dropped at a predetermined position on the surface of the chip component or the printed circuit board, and then the chip component electrode and the printed circuit board electrode It can be suitably used for flip chip mounting in which the part is heated and bonded with bumps.
An example of flip chip mounting using the one-component epoxy resin composition of the present invention will be described with reference to FIG. The application of the one-component epoxy resin composition of the present invention is not limited to the following example.
[0021]
As shown in FIG. 1A, first, a predetermined amount of the one-component epoxy resin composition 4 of the present invention is dropped from a
Then, as shown in FIG. 1 (c), the pressed one-component epoxy resin composition 4 flows radially in the gap between the lower surface of the chip component and the printed circuit board in the horizontal direction. Fill the gap with the substrate without any gaps. In other words, the one-component epoxy resin composition is printed or dripped at a position (usually approximately the center of the area), amount, and shape so that the entire area of the lower surface of the chip part is filled after pressing. Arranged by.
In this step, it is important that the one-component liquid epoxy resin composition 4 does not scatter or flow out to other than the lower surface region of the chip part to be sealed and filled. In the present invention, good shape retention means that in such a process, the one-part epoxy resin composition can be arranged in a form with an appropriate swell, even if pressed and heat-bonded, This means that it is easy to fill the gap between the chip component and the printed circuit board without a gap without splashing or flowing outside the lower surface region of the chip component.
Usually, it heat-processes, pressing in the state of FIG.1 (c), and simultaneously progresses gelatinization or hardening of the said epoxy resin composition, fuse | melts or eutectoids the said bump, and joins between electrodes. This heating temperature is about 180 ° C. to 240 ° C. when the bump is solder, and about 285 ° C. to 300 ° C. or more when the bump is gold-tin eutectic. For this reason, when the said epoxy resin composition is not suppressed in the foaming property at high temperature, or when there is no heat resistance which can endure the said temperature, a void will arise or a decomposition | disassembly and deterioration of a resin component will arise.
[0022]
After the heat treatment, the epoxy resin composition of the present invention becomes a cured product that seals and fills the gap between the chip component and the printed circuit board, thereby mitigating the effects caused by thermal expansion or contraction between the chip component and the printed circuit board. To play a role. Usually, the thickness of the cured product is about 0.02 to 0.5 mm. For example, in the case of bonding with a gold-tin eutectic, the thickness is about 0.02 to 0.10 mm, particularly about 0.02 to 0.50 mm. For example, in the case where a solder ball is used, 0.05 to 0 is used. About 5 mm. The cured product of the epoxy resin composition of the present invention has good adhesion strength with the polyimide film, epoxy resin, and silicon wafer, which are substrate materials, and has a tensile elastic modulus at 25 ° C. of 250 kg / mm. 2 Hereinafter, particularly 0.1 to 200 kg / mm 2 Therefore, the chip component and the printed circuit board are bonded with high reliability, and the effect of reducing the influence caused by thermal expansion or contraction between the chip component and the printed circuit board is extremely excellent.
The tensile modulus of the cured product is 250 kg / mm 2 Those exceeding the range cannot sufficiently fulfill the role of mitigating the effects caused by thermal expansion or contraction between the chip component and the printed circuit board. Further, if the adhesion strength between the cured product, the polyimide film and the silicon wafer is low, peeling is likely to occur during use, and the chip component and the printed circuit board cannot be bonded with high reliability. For this reason, it is impossible to sufficiently fulfill the role of mitigating the influence caused by thermal expansion or contraction between the chip component and the printed circuit board.
[0023]
FIG. 2 shows a schematic view of one embodiment when a chip component using the one-component epoxy resin composition of the present invention is flip-chip mounted on a printed circuit board. In FIG. 2, 7 is a cured product of the one-component epoxy resin composition of the present invention, 4 is a chip component, 1 is a polyimide film substrate, 6 is a bump, and 2 is a wiring circuit.
[0024]
【Example】
Hereinafter, the present invention will be described by way of examples. The present invention is not limited to the examples.
In addition, the measurement and evaluation of the viscosity in an Example, high temperature foamability, the tensile elasticity modulus of hardened | cured material, and the adhesive strength of hardened | cured material were performed as follows.
[0025]
[Viscosity of epoxy resin composition]
It measured at 25 degreeC using the E-type viscosity meter.
[High temperature foaming]
A sample made of the epoxy resin composition is dropped and placed on a glass plate having a thickness of about 0.2 mm. On the hot plate heated to a predetermined temperature, the glass plate placed by dropping the sample is placed on the hot plate with the sample surface facing down so that the sample comes into contact with the hot plate. A sample made of an epoxy resin composition was visually observed through a glass plate, and a case where foaming was not observed was judged as ◯, and a case where foaming was seen was judged as x.
[Tensile modulus of cured product]
The tensile modulus of the cured product is a test piece punched into a 4 mm width dumbbell shape, using TENSION UTM5T manufactured by TOYO BOLDWIN, according to ASTM D882, at a temperature of 25 ° C., a chuck interval of 30 mm, and a tensile speed of 2 mm / min. It was measured.
[Adhesion strength of cured product]
An epoxy resin composition is dropped onto the central portion of a polyimide film having a length of 10 cm, a width of 1 cm, and a thickness of 25 μm, and a silicon wafer is formed by forming a silicon nitride film on the surface cleaved to 1 cm × 1 cm. The sample was placed in contact with the object, heat-treated on a hot plate at 135 ° C. for 20 minutes, and then heat-treated in an oven at 180 ° C. for 1 hour to produce a test piece as shown in FIG. As shown in FIG. 4, the prepared test piece is sandwiched with the polyimide film surface as the upper surface so that the silicon wafer protrudes 2 mm from the upper presser plate, and a 90 ° peel test is performed at a tensile speed of 2 mm / min with a tensile tester. It was. The evaluation of the adhesion strength is as follows.
○: The polyimide film did not peel from the silicon wafer, and the silicon wafer was broken
X: The polyimide film peeled off from the silicon wafer
3 and 4, 7 is a cured product of the epoxy resin composition, 20 is a silicon wafer, 30 is a polyimide film, 40 is a pressing plate, 50 is a jig, and 60 is a spacer.
[0026]
(Reference Example 1)
A four-necked flask substituted with nitrogen gas was equipped with a stirrer, nitrogen gas inlet tube, reflux condenser, and stopper, and 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene was attached. 187 g of -1,2-dicarboxylic acid anhydride (Dai Nippon Ink Chemical Co., Ltd., Epicron B4400) and 300 g of methanol were added and refluxed. After 3 hours, the mixture was cooled to room temperature, the reflux condenser was replaced with a reflux condenser with a water separator, and 0.5 g of an antifoaming agent (FS Antifoam DB-100 manufactured by Dow Corning Asia Co., Ltd.), α, ω-bis 326 g of (3-aminopropyl) polydimethylsiloxane (amine equivalent 460 manufactured by Toray Dow Corning Silicone Co., Ltd.) was added, and methanol was distilled off over 1 hour. Subsequently, the temperature was raised to 200 ° C., and the mixture was reacted for 6 hours while distilling off water to obtain 496 g of a brownish brown viscous product. 200 g of the obtained product was dissolved in 1 liter of xylene, washed with 800 ml of water three times, and then vacuum-dried at 200 ° C. for 1 hour.
The viscosity of this product (hereinafter sometimes abbreviated as SiB) at 80 ° C. was 50 poise.
[0027]
Example 1
108 g of SiB obtained in Reference Example 1 and 38 g of novolak type phenolic resin (M-5, manufactured by Meiwa Kasei Co., Ltd.) were mixed at 80 ° C. until uniform, then cooled to room temperature, and bisphenol A type epoxy resin (Bantico Co., Ltd.). Manufactured, MY790-1) 100 g, a curing accelerator (2-ethyl-4-methylimidazole tetraphenylborate) 4 g, and a silane coupling agent (KBM303, Shin-Etsu Chemical Co., Ltd.) 5 g are added, kneaded in a roll, A one-part epoxy resin composition was obtained. The viscosity of the obtained composition was 910 poise.
Using this composition as a sample, high temperature foaming property at 300 ° C. was evaluated, but no foaming was observed.
This composition was cured at 135 ° C. on a hot plate for 30 minutes and further in an oven at 180 ° C. for 1 hour to obtain a cured product. The cured product has a tensile modulus of 171 kg / mm. 2 Met.
The adhesion strength of the cured product was measured and found to be ◯.
[0028]
(Comparative Example 1)
Butanediol type epoxy resin (Bardico Co., Ltd. Araldite DY026SP) 100 g, SiB 140 g obtained in Reference Example 1, acid anhydride curing agent (Japan Epoxy Resin Co., Ltd. Epicure YH306) 141 g, and curing accelerator (2-ethyl) -4-methylimidazole) 1g and silane coupling agent (KBM403, Shin-Etsu Chemical Co., Ltd.) 7.6g were stirred and mixed at room temperature to obtain a one-pack epoxy resin composition. The viscosity of this composition was 3.1 poise.
When this composition was used as a sample and the high temperature foaming property at 300 ° C. was evaluated, it foamed vigorously.
[0029]
【The invention's effect】
Since the present invention is as described above, the following effects can be obtained.
That is, according to the present invention, the chip component or the printed circuit board can be applied or dropped onto the surface of the chip component or the printed circuit board and arranged in a form having an appropriate bulge at a specified position. When heating and joining, the gap between the chip parts and the printed circuit board can be filled without gaps without flowing out or splashing beyond the range of the predetermined position, and there is no foaming, boiling or decomposition during heating, and at an appropriate speed When gelation or curing progresses, and when cured, it has a low elastic modulus, high electrical insulation, high adhesion to polyimide films and silicon wafers, and withstands flux processing such as solder and metal eutectic. A heat-resistant, solvent-free one-component epoxy resin composition and a cured product obtained by heating and curing the composition can be provided.
[Brief description of the drawings]
FIG. 1 is a schematic view showing a flip chip mounting method using a one-component epoxy resin composition of the present invention.
FIG. 2 is a schematic view showing an embodiment when a chip component using the one-component epoxy resin composition of the present invention is flip-chip mounted on a printed circuit board.
FIG. 3 is a schematic view showing a test piece for measuring the adhesion strength of a cured product. (A) is a top view of a test piece, (b) is sectional drawing of a test piece.
FIG. 4 is a schematic diagram showing a state in which the adhesion strength of a cured product is measured.
[Explanation of symbols]
1: Substrate or polyimide substrate
2: Wiring circuit
3: Needle for supplying one-component epoxy resin composition
4: One-part epoxy resin composition
5: Chip parts
6: Bump
7: Cured product of one-part epoxy resin composition
20: Silicon wafer
30: Polyimide film
40: Presser plate
50: Jig
60: Spacer
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002168189A JP3915604B2 (en) | 2002-06-10 | 2002-06-10 | One-part epoxy resin composition and cured product |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002168189A JP3915604B2 (en) | 2002-06-10 | 2002-06-10 | One-part epoxy resin composition and cured product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004010810A JP2004010810A (en) | 2004-01-15 |
| JP3915604B2 true JP3915604B2 (en) | 2007-05-16 |
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| JP2002168189A Expired - Fee Related JP3915604B2 (en) | 2002-06-10 | 2002-06-10 | One-part epoxy resin composition and cured product |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007061037A1 (en) | 2005-11-25 | 2007-05-31 | Hitachi Chemical Co., Ltd. | Liquid resin composition for electronic component and electronic component device |
| JPWO2007116979A1 (en) * | 2006-04-12 | 2009-08-20 | 日立化成工業株式会社 | Resin composition for sealing filler, flip chip mounting method and flip chip mounting product using the same |
| JP5710099B2 (en) * | 2007-10-12 | 2015-04-30 | 日立化成株式会社 | Film sealing adhesive for semiconductor sealing, semiconductor device manufacturing method using the adhesive, and semiconductor device |
| JP2009260225A (en) * | 2008-03-21 | 2009-11-05 | Hitachi Chem Co Ltd | Method of manufacturing semiconductor device |
| JP2009260229A (en) * | 2008-03-21 | 2009-11-05 | Hitachi Chem Co Ltd | Method of dicing semiconductor wafer, and method of connecting semiconductor chip with substrate |
| JP5436827B2 (en) * | 2008-03-21 | 2014-03-05 | 日立化成株式会社 | Manufacturing method of semiconductor device |
| JP2009260232A (en) * | 2008-03-26 | 2009-11-05 | Hitachi Chem Co Ltd | Film-like adhesive for sealing semiconductor, and semiconductor apparatus and method of manufacturing the same |
| JP5710098B2 (en) * | 2008-03-27 | 2015-04-30 | 日立化成株式会社 | Manufacturing method of semiconductor device |
| SG11201610458WA (en) | 2014-06-26 | 2017-01-27 | Ev Group E Thallner Gmbh | Method for bonding substrates |
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