JPWO2010016305A1 - 接着剤組成物、フィルム状接着剤、接着シート及び半導体装置 - Google Patents
接着剤組成物、フィルム状接着剤、接着シート及び半導体装置 Download PDFInfo
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- JPWO2010016305A1 JPWO2010016305A1 JP2010523790A JP2010523790A JPWO2010016305A1 JP WO2010016305 A1 JPWO2010016305 A1 JP WO2010016305A1 JP 2010523790 A JP2010523790 A JP 2010523790A JP 2010523790 A JP2010523790 A JP 2010523790A JP WO2010016305 A1 JPWO2010016305 A1 JP WO2010016305A1
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Abstract
Description
温度計、攪拌機、冷却管、及び窒素流入管を装着した300mLフラスコ中に、1,3−ビス(3−アミノプロピル)テトラメチルジシロキサン(信越化学工業株式会社製、商品名:LP−7100)12.42g、ポリオキシプロピレンジアミン(BASF株式会社製、商品名:D400、分子量:452.4)22.62g、及び、N−メチル−2−ピロリドン140gを仕込み、この反応液を攪拌した。ジアミンが溶解した後、フラスコを氷浴中で冷却しながら、予め無水酢酸からの再結晶により精製した4,4’−オキシジフタル酸二無水物32.62gを少量ずつ添加した。室温(25℃)で8時間反応させた後、キシレン80.5gを加え、窒素ガスを吹き込みながら180℃で加熱することにより、水と共にキシレンを共沸除去してポリイミド樹脂(PI−1)ワニスを得た。得られたポリイミド樹脂のGPCを測定したところ、ポリスチレン換算で、数平均分子量Mn=14000、重量平均分子量Mw=35000であった。また、得られたポリイミド樹脂のTgは45℃であった。
温度計、攪拌機、冷却管、及び窒素流入管を装着した300mLフラスコ中に、モノマーとして、2,2−ビス(4−アミノフェノキシフェニル)プロパン20.52g及び4,9−ジオキサデカン−1,12−ジアミン10.20g、並びに有機溶媒としてN−メチル−2−ピロリドン193.5gを仕込んで撹拌することで、有機溶媒中に上記各ジアミンが溶解した反応液を得た。次いで、反応液にデカメチレンビストリメリテート二無水物52.20gを少量ずつ添加すると共に、窒素ガスを吹き込みながら180℃で5時間加熱して反応を進行させて、発生する水を系外に除去することで、ポリイミド樹脂(PI−2)ワニスを得た。得られたポリイミド樹脂の分子量をGPCにより測定したところ、ポリスチレン換算で、数平均分子量Mn=28900、重量平均分子量Mw=88600であった。また、得られたポリイミド樹脂のTgは73℃であった。
温度計、攪拌機、冷却管、及び窒素流入管を備えた500mlフラスコ中に、2,2−ビス(4−アミノフェノキシフェニル)プロパン41.00g、及びN−メチル−2−ピロリドン279.6gを仕込み、攪拌した。ジアミンの溶解後、フラスコを氷浴中で冷却しながら、予め無水酢酸で再結晶精製したデカメチレンビストリメリテート二無水物52.20gを少量ずつ添加した。室温で8時間反応させた後、キシレン186.4gを加え、窒素ガスを吹き込みながら180℃で加熱し、水と共にキシレンを共沸除去した。その反応液を大量の水中に注ぎ、沈澱したポリマーを濾過により採り、乾燥してポリイミド樹脂(PI−3)を得た。得られたポリイミド樹脂のGPCを測定した結果、ポリスチレン換算で、数平均分子量Mn=22800、重量平均分子量Mw=121000、であった。また、得られたポリイミド樹脂のTgは120℃であった。
上記で得たポリイミド樹脂(PI−1〜3)をそれぞれ用い、下記表1〜2に示す組成比(単位:質量部)にて各成分を配合し、接着剤組成物(接着剤層形成用ワニス)を得た。
BPA−CA:小西化学工業株式会社製、2,2’−ビス(3−アリル−4−ヒドロキシフェニル)プロパン、
RE−810NM:日本化薬株式会社製、ジアリルビスフェノールAジグリシジルエーテル、
BANI−X:丸善石油化学株式会社製、キシリレン型ビスアリルナジイミド、
DA−MGIC:四国化成工業株式会社製、1,3−ジアリル−5−グリシジルイソシアヌレート、
BMI−1:東京化成工業株式会社製、4,4’−ビスマレイミドジフェニルメタン、
BMI−2:ケイ・アイ化成株式会社製、2,2’−ビス−[4−(4−マレイミドフェノキシ)フェニル]プロパン(BMI−80)、
ESCN−195:住友化学株式会社製、クレゾールノボラック型固体状エポキシ樹脂(エポキシ当量:200)、
TrisP−PA:本州化学工業株式会社製、α,α,α’−トリス(4−ヒドロキシフェニル)−1−エチル−4−イソプロピルベンゼン(OH当量:141)、
TPPK:東京化成工業株式会社製、テトラフェニルホスホニウムテトラフェニルボラート、
HP−P1:水島合金鉄株式会社製、窒化ホウ素フィラー、
NMP:関東化学株式会社製、N−メチル−2−ピロリドン。
各実施例及び各比較例で得られた、厚さ50μmのPET基材上に40μm厚に調整したBステージ状態のフィル状接着剤を形成させた接着シートを、10mm×10mmサイズに切断して試験片とした。この試験片を、2枚のスライドグラス(松浪硝子工業株式会社製、76mm×26mm×1.0〜1.2mm厚)の間に挟み、150℃又は200℃の熱盤上で全体に100kgf/cm2の荷重を加えながら90秒間加熱圧着した。加熱圧着後の上記PET基材の四辺からのフィルム状接着剤のはみ出し量をそれぞれ光学顕微鏡で計測し、それらの平均値をフロー量とした。なお、Bステージとは、接着剤層形成用ワニスをPET基材上に塗工後、オーブン中にて80℃で30分間、続いて120℃で30分間の条件で加熱した後の状態のことである。このフロー量の値が大きいほど、Bステージでの熱流動性に優れ、被着体表面の凹凸に対する充填性(埋め込み性)に優れている。結果を表1〜2に示す。
各実施例及び各比較例で得られた接着シートのフィルム状接着剤(10mm×10mm×40μm厚)を用いて、ガラスエポキシ基板(20mm×20mm×105μm厚)上に、シリコンチップ(10mm×10mm×75μm厚)を、実施例1〜3、5及び比較例1、3、4のフィルム状接着剤については150℃にて、実施例4のフィルム状接着剤については180℃にて、比較例2のフィルム状接着剤については250℃にて、荷重:1kgf/chip、時間:10秒間の条件で加熱圧着し、オーブン中にて150℃で1時間の条件で加熱硬化した後、株式会社小坂研究所製の表面粗さ測定器SE−2300を用いて、シリコンチップの対角線方向に測定距離10mmの条件で、室温におけるシリコンチップ面側の凸状の反り量を測定した。その結果を表1〜2に示す。
各実施例及び各比較例で得られた接着シートのフィルム状接着剤(5mm×5mm×40μm厚)を用いて、42アロイリードフレーム上にシリコンチップ(5mm×5mm×400μm厚)を、実施例1〜3、5及び比較例1、3、4のフィルム状接着剤については150℃にて、実施例4のフィルム状接着剤については180℃にて、比較例2のフィルム状接着剤については250℃にて、荷重:1kgf/chip、時間:5秒間の条件で加熱圧着し、オーブン中にて150℃で1時間、又は180℃で1時間の条件で加熱硬化した。
上記で得られた接着シートを、幅10mm、長さ40mmに切断して基材付きフィルム状接着剤を得た。この基材付きフィルム状接着剤を、支持台上に載せたシリコンウェハ(6インチ径、厚さ400μm)の裏面(支持台と反対側の面)に、フィルム状接着剤面がシリコンウェハ面側になるようにして、ロール(温度100℃、線圧4kgf/cm、送り速度0.5m/分)で加圧することにより積層した。
Claims (11)
- (A)Tgが100℃以下である熱可塑性樹脂と、(B)熱硬化性成分と、を含有し、
前記(B)熱硬化性成分が、(B1)アリル基を有する化合物、及び、(B2)マレイミド基を有する化合物を含む、接着剤組成物。 - 前記(A)熱可塑性樹脂がポリイミド樹脂である、請求項1記載の接着剤組成物。
- 前記(B1)アリル基を有する化合物がエポキシ基をさらに有する化合物である、請求項1又は2記載の接着剤組成物。
- 前記(B)熱硬化性成分がさらに(B3)エポキシ樹脂を含む、請求項1〜3のいずれか一項に記載の接着剤組成物。
- さらに(C)フィラーを含有する、請求項1〜4のいずれか一項に記載の接着剤組成物。
- 半導体素子を、他の半導体素子又は半導体素子搭載用支持部材に接着するために用いられる、請求項1〜5のいずれか一項に記載の接着剤組成物。
- 請求項1〜6のいずれか一項に記載の接着剤組成物をフィルム状に形成してなる、フィルム状接着剤。
- 支持基材と、該支持基材の主面上に形成された請求項7記載のフィルム状接着剤と、を備える、接着シート。
- 前記支持基材がダイシングシートである、請求項8記載の接着シート。
- 前記ダイシングシートが、基材フィルム及び該基材フィルム上に設けられた粘着剤層を有するものである、請求項9記載の接着シート。
- 請求項1〜6のいずれか一項に記載の接着剤組成物により、半導体素子と半導体素子搭載用支持部材とが接着された構造、及び/又は、隣接する半導体素子同士が接着された構造を有する、半導体装置。
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- 2009-04-30 CN CN2009801299215A patent/CN102112568A/zh active Pending
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US20110187009A1 (en) | 2011-08-04 |
KR20110034038A (ko) | 2011-04-04 |
TW201006901A (en) | 2010-02-16 |
WO2010016305A1 (ja) | 2010-02-11 |
JP5445455B2 (ja) | 2014-03-19 |
EP2311921A1 (en) | 2011-04-20 |
CN102112568A (zh) | 2011-06-29 |
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