TWI586784B - 加熱剝離型黏著片材 - Google Patents

加熱剝離型黏著片材 Download PDF

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TWI586784B
TWI586784B TW102110759A TW102110759A TWI586784B TW I586784 B TWI586784 B TW I586784B TW 102110759 A TW102110759 A TW 102110759A TW 102110759 A TW102110759 A TW 102110759A TW I586784 B TWI586784 B TW I586784B
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heat
adhesive layer
expandable
adhesive
acrylate
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TW201348391A (zh
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平山高正
村田秋桐
下川大輔
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日東電工股份有限公司
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    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
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    • C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
    • C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents
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    • H01L2021/60007—Attaching or detaching leads or other conductive members, to be used for carrying current to or from the device in operation involving a soldering or an alloying process
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Description

加熱剝離型黏著片材
本發明係關於一種可利用加熱處理降低接著力而使其能夠自被黏著體簡單地剝離之適用於電子零件等之加工步驟之加熱剝離型黏著片材。
另外，係關於一種作為產業上之利用領域之電子零件(例如半導體晶圓、積層陶瓷零件)等之加工用途(研磨用途、切割用途等)。
先前，已知有於基材上設置含發泡劑之黏著層而成之加熱剝離型黏著片材(專利文獻1~5)。該加熱剝離型黏著片材係實現可耐受被黏著體之切割加工之黏著保持力、與所形成之切割片之容易之剝離回收的兼顧者。即，該黏著片材具有如下特徵：在與被黏著體貼合時具有較高之黏著性，另一方面，於回收切割片時，藉由加熱而使含有熱膨脹性微球之發泡性感壓接著劑層發泡或膨脹，感壓接著劑層之表面變成凹凸狀，因與被黏著體之接著面積減少而導致黏著力降低或消失，因此可較容易地剝離上述切割片。尤其是於被黏著體較脆弱之情形時、或為薄層之情形時，採用在黏附有被黏著體之黏著片材上貼合支撐體而進行加工之所謂基座方式(專利文獻6)。
然而，此種基座方式中使用之先前之加熱剝離型黏著片材例如存在如下情況：由於對被黏著體進行加熱處理後之加熱剝離型黏著片材基材之熱收縮而產生收縮應力並於被黏著體上產生翹曲，其後之工序中之輸送性、加工性產生問題。該現象係被黏著體之面積越大，則 越明顯地顯現。對於該問題，一般認為，於熱剝離型黏著片材中不使用基材而僅利用黏著層黏附被黏著體與支撐體，藉此由基材之熱收縮引起之收縮應力減小並成為防止翹曲之效果。然而，於該情形時產生加熱剝離時之剝離力降低之問題。認為其原因在於，將加熱剝離型黏著片材加熱剝離時，由熱膨脹性微球之發泡引起之剝離應力由於無約束黏著劑之基材而向四面八方分散。
先前技術文獻 專利文獻
專利文獻1：日本專利特公昭51-024534號公報
專利文獻2：日本專利特開昭56-061468號公報
專利文獻3：日本專利特開昭56-061469號公報
專利文獻4：日本專利特開昭60-252681號公報
專利文獻5：日本專利特開2009-040930號報
專利文獻6：日本專利特開2003-292916號報
本發明之目的在於，提供一種防止由加熱處理後基材之收縮所導致之被黏著體之翹曲並且在加熱剝離時具有良好之剝離性的加熱剝離型黏著片材、使用該黏著片材之電子零件、半導體之製造方法。
本發明者等人為了解決上述問題而進行了深入研究，結果發現，一種加熱剝離型黏著片材，其特徵在於，其係將含有熱膨脹性微球之熱膨脹性黏著層及黏著層積層而成之無基材雙面黏著片材，進行加熱剝離之雙面黏著片材之黏著層具有較熱膨脹性黏著層更高之彈性模數，並且藉由使用該加熱剝離型黏著片材，可實現加工性與剝離性之兼顧。
根據本發明，藉由使用將含有熱膨脹性微球之熱膨脹性黏著層及彈性模數較該熱膨脹性黏著層更高之黏著層積層而成之無基材黏著片材，而於加熱步驟後被黏著體亦不產生翹曲，另外，藉由控制加熱剝離時之發泡應力之方向，可防止加熱剝離性之降低。
1‧‧‧熱膨脹性黏著層
2‧‧‧黏著層
3‧‧‧隔離膜
4‧‧‧彈性層
圖1係不具有彈性層之本發明之加熱剝離型黏著片材。
圖2係具有彈性層之本發明之加熱剝離型黏著片材。
本發明之加熱剝離型黏著片材包含具有至少一層含有熱膨脹性微球並藉由加熱而膨脹之熱膨脹性黏著層的兩層以上之積層黏著劑。將該例子示於圖1、圖2。1為熱膨脹性黏著層，2為黏著層。進而，可視需要設置隔離膜3及彈性層4。
而且，本發明之加熱剝離型黏著片材為無基材之黏著片材，其係不具有可藉由熱而收縮之基材層、即作為不具有黏著或熱膨脹性之作用併用以支撐熱膨脹性黏著層或黏著劑層之層的基材之加熱剝離型黏著片材，基本上由包含上述熱膨脹性黏著層及黏著層之積層體所構成。再者，基材層不包括所謂剝離片材。
(熱膨脹性黏著層)
熱膨脹性黏著層含有熱膨脹性微球並藉由加熱而膨脹，經由因該膨脹引起之凹凸變形，表面之黏著層亦凹凸變形，從而減小對於被黏著體之接著力。因此，對於接著於被黏著體上之加熱剝離型黏著片材，在任意時間對該熱膨脹性黏著層進行加熱處理，均可自被黏著體上簡單地剝離。
熱膨脹性黏著層例如可作為熱膨脹性微球與結合劑之混合層等而形成。作為該結合劑，可使用容許由熱膨脹性微球之加熱導致之發 泡及/或膨脹之聚合物類或蠟類等較佳者。其中，較佳為儘可能不約束熱膨脹性微球之發泡及/或膨脹者。就上述熱膨脹性微球之加熱膨脹性、對被黏著體之經由黏著層之接著力等黏著特性之控制性等方面而言，可尤其較佳地使用之結合劑為黏著劑。
作為上述熱膨脹性黏著層所使用之黏著劑，並無特別限定，例如可使用如下較佳之黏著劑中之一種或兩種以上：使用橡膠系或丙烯酸系、乙烯基烷基醚系或聚矽氧系、聚酯系或聚醯胺系、胺基甲酸酯系或氟系、苯乙烯-二烯嵌段共聚物系等之聚合物者；調配熔點約200℃以下等之熱熔融性樹脂而改良蠕變特性者；放射線硬化型者；於該等中視需要調配有例如交聯劑或黏著賦予劑、塑化劑或軟化劑、填充劑或顏料、著色劑或抗老化劑、界面活性劑等各種添加劑者等。
作為該等黏著劑之例子，可列舉日本專利特開昭56-61468號公報、日本專利特開昭63-30205號公報、日本專利特開昭63-17981號公報、日本專利特公昭56-13040號公報等。
就經由黏著層之對被黏著體之加熱前之適度之接著力的控制性及由加熱導致之接著力的減小性之平衡等方面而言，較佳之上述黏著劑係以常溫至150℃之溫度區域中之動態彈性模數為5萬~1000萬dyn/cm2之聚合物作為基礎聚合物者，但不限定於此。
此種黏著劑例如為於基礎聚合物中使用如天然橡膠、聚異戊二烯橡膠、苯乙烯-丁二烯橡膠、苯乙烯-異戊二烯-苯乙烯嵌段共聚物橡膠、苯乙烯-丁二烯-苯乙烯嵌段共聚物橡膠、再生橡膠、丁基橡膠、聚異丁烯、NBR(Nitrile Butadiene Rubber，丁腈橡膠)之橡膠系聚合物之橡膠系黏著劑，於基礎聚合物中使用以丙烯酸及/或甲基丙烯酸之烷基酯為成分之丙烯酸系聚合物之丙烯酸系黏著劑等。
再者，作為上述丙烯酸系聚合物，例如可列舉：使用具有如甲基、乙基、丙基、丁基、戊基、己基、庚基、2-乙基己基、異辛基、 異壬基、異癸基、十二烷基、月桂基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、十九烷基、二十烷基之碳數為1~20、尤其是4~18之直鏈或支鏈之烷基之丙烯酸或甲基丙烯酸之酯中之一種或兩種以上者。
尤其是作為主成分之丙烯酸系單體，可較佳地使用丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯、丙烯酸異辛酯、丙烯酸異壬酯、甲基丙烯酸甲酯等。
另外，所使用之丙烯酸系聚合物亦可為以凝聚力、耐熱性、交聯性等之改善等為目的而使一種或兩種以上之適宜之單體共聚合而成者。對於該共聚單體，並無特別限定，只要為可與上述丙烯酸系烷基酯共聚合之單體即可。
此外，作為上述共聚單體之例子，可列舉：如丙烯酸或甲基丙烯酸、丙烯酸羧乙酯或丙烯酸羧戊酯、衣康酸或馬來酸、富馬酸或巴豆酸之含羧基單體；如馬來酸酐、衣康酸酐之酸酐單體；如(甲基)丙烯酸羥乙酯、(甲基)丙烯酸羥丙酯、(甲基)丙烯酸羥丁酯、(甲基)丙烯酸羥己酯、(甲基)丙烯酸羥辛酯、(甲基)丙烯酸羥癸酯、(甲基)丙烯酸羥基月桂酯、甲基丙烯酸(4-羥基甲基環己基)甲酯之含羥基單體。
作為官能基單體，尤其是考慮到與環氧交聯劑之反應，較佳為丙烯酸、甲基丙烯酸，於與異氰酸酯交聯劑之反應中，較佳為含羥基單體，例如，含羥基單體可使用(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸4-羥丁酯、(甲基)丙烯酸6-羥己酯、(甲基)丙烯酸8-羥辛酯、(甲基)丙烯酸10-羥癸酯、(甲基)丙烯酸12-羥基月桂酯、及(甲基)丙烯酸(4-羥基甲基環己基)甲酯。
另外，作為共聚單體之例子，亦可列舉：如苯乙烯磺酸或烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸或(甲基)丙烯醯胺丙磺酸、 (甲基)丙烯酸磺丙酯或(甲基)丙烯醯氧基萘磺酸之含磺酸基單體；如2-羥乙基丙烯醯基磷酸酯(2-hydroxyethyl acryloyl phosphate)之含磷酸基單體；如(甲基)丙烯醯胺或N,N-二甲基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺或N-羥甲基(甲基)丙烯醯胺、N-羥甲基丙烷(甲基)丙烯醯胺之(N-取代)醯胺系單體；如(甲基)丙烯酸胺基乙酯或(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸第三丁基胺基乙酯之(甲基)丙烯酸胺基烷基酯系單體；如(甲基)丙烯酸甲氧基乙酯或(甲基)丙烯酸乙氧基乙酯之(甲基)丙烯酸烷氧基烷基酯系單體；如N-環己基馬來醯亞胺或N-異丙基馬來醯亞胺、N-月桂基馬來醯亞胺或N-苯基馬來醯亞胺之馬來醯亞胺系單體；如N-甲基衣康醯亞胺或N-乙基衣康醯亞胺、N-丁基衣康醯亞胺或N-辛基衣康醯亞胺、N-2-乙基己基衣康醯亞胺或N-環己基衣康醯亞胺、N-月桂基衣康醯亞胺之衣康醯亞胺系單體；如N-(甲基)丙烯醯氧基亞甲基琥珀醯亞胺或N-(甲基)丙烯醯基-6-氧基六亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-8-氧基八亞甲基琥珀醯亞胺之琥珀醯亞胺系單體等。
進而，作為共聚單體之例子，亦可列舉：如乙酸乙烯酯、丙酸乙烯酯、N-乙烯基吡咯烷酮、甲基乙烯基吡咯烷酮、乙烯基吡啶、乙烯基哌啶酮、乙烯基嘧啶、乙烯基哌嗪、乙烯基吡嗪、乙烯基吡咯、乙烯基咪唑、乙烯基噁唑、乙烯基嗎啉、N-乙烯基羧酸醯胺類、苯乙烯、α-甲基苯乙烯、N-乙烯基己內醯胺之乙烯基系單體；如丙烯腈、甲基丙烯腈之氰基丙烯酸酯系單體；如(甲基)丙烯酸縮水甘油酯之含環氧基丙烯酸系單體；如(甲基)丙烯酸聚乙二醇酯、(甲基)丙烯酸聚丙二醇酯、(甲基)丙烯酸甲氧基聚乙二醇酯、(甲基)丙烯酸甲氧基聚丙二醇酯之二醇系丙烯酸酯單體；如(甲基)丙烯酸四氫糠酯、氟代(甲基)丙烯酸酯、聚矽氧(甲基)丙烯酸酯、丙烯酸2-甲氧基乙酯之丙烯酸酯系單體；如己二醇二(甲基)丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸 酯、(聚)丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、環氧丙烯酸酯、聚酯丙烯酸酯、胺基甲酸酯丙烯酸酯、二乙烯基苯、丁基二丙烯酸酯、己基二丙烯酸酯之多官能單體；異戊二烯、丁二烯、異丁烯、乙烯基醚等。
另一方面，作為調配於熱膨脹性黏著層中之熱膨脹性微球，例如可列舉：藉由凝聚法、界面聚合法等適宜之方式而使如異丁烷、丙烷、戊烷般容易氣化並顯示熱膨脹性之適宜之物質內含於包含殼形成物質、例如如偏二氯乙烯-丙烯腈共聚物、聚乙烯醇、聚乙烯基縮丁醛、聚甲基丙烯酸甲酯、聚丙烯腈、聚偏二氯乙烯、聚碸之熱熔融性物質、或因熱膨脹而破壞之物質等的殼之內部而成之微膠囊等。
藉由使用熱膨脹性微球，可穩定地抑制由加熱導致之被黏著體之污染度之增大。未微膠囊化之發泡劑等由於對形成表面之黏著層進行凝聚破壞，故缺乏污染度增大之抑制效果。就由加熱導致之接著力減小之操作性、尤其是該接著力減小之穩定之達成性等方面而言，可較佳地使用直至破裂為止之體積膨脹為5倍以上、特別是7倍以上、尤其是10倍以上之熱膨脹性微球。
所使用之熱膨脹性微球之平均粒徑可適當地確定，通常為100μm以下、特別是80μm以下、尤其是1~50μm，但並不限定於此。再者，作為熱膨脹性微球，可使用微球(Matsumoto Microsphere F-50D，Matsumoto Yushi-Seiyaku股份有限公司製造)等市售品。
熱膨脹性微球之使用量可根據熱膨脹性黏著層之膨脹倍率、接著力之減小性等而適當確定。通常，於為上述結合劑、黏著劑之情形時，每100重量份其基礎聚合物使用1~150重量份、特別是10~130重量份、尤其是25~100重量份之熱膨脹性微球。
熱膨脹性黏著層之形成例如可藉由如下方式等而進行：視需要使用溶劑將熱膨脹性微球與結合劑等調配成分混合，以塗佈方式等適宜方式使該混合物展開而形成片狀之層等。該層之厚度可根據接著力之減小性等而適當確定。
關於熱膨脹性黏著層之厚度，就因由厚度過小所導致之基於熱膨脹性微球之表面之凹凸化而使設置於其上之黏著層亦凹凸化並表現不出充分的接著力之情況之防止、加熱處理時設置於其上之黏著層凝聚破壞而使被黏著體的污染度增大之情況之防止、由厚度過大所導致之基於加熱變形不良之接著力減小不足之防止等方面而言，較佳為300μm以下、特別是2~200μm、尤其是5~150μm之厚度。進而較佳為，熱膨脹性黏著層之彈性模數於下述AFM(Atomic Force Microscopy，原子力顯微鏡)力曲線法中較佳為300MPa以下、更佳為100MPa以下、進而較佳為50MPa以下。
(黏著層)
作為構成黏著層2之黏著劑，可採用上述熱膨脹性黏著層中使用之黏著劑，進而亦可使用能量射線硬化性黏著劑、熱固性黏著劑。作為此種黏著劑，可使用於具有黏著性之母劑中調配能量射線硬化性化合物(或能量射線硬化性樹脂)、熱聚合性化合物而成者。或者，亦可使用利用碳-碳雙鍵等能量射線反應性官能基對具有黏著性之母劑進行化學修飾而成者。
黏著層2之厚度較佳為10~150μm，更佳為10~100μm，進而較佳為20~60μm。
(彈性模數)
關於熱膨脹性黏著層或黏著劑層之彈性模數測定，有各種方法，可藉由使用AFM力曲線法而測定層狀黏著層之彈性模數。AFM力曲線法可將微小之壓頭壓入試樣中並根據由此時之位移、應力所獲 得之卸荷曲線而算出彈性模數。
黏著層2之彈性模數只要高於熱膨脹性黏著層之彈性模數即可，一般認為過高時黏著層2之熱收縮會成為翹曲之原因，故而於上述AFM力曲線法中較佳為500MPa以下，進而較佳為300MPa以下，更佳為100MPa以下。
而且，較佳為黏著層之彈性模數與熱膨脹性黏著層相比高0.3~500MPa、進而較佳為高10~400MPa、更佳為高50~350MPa。
藉由使黏著層之彈性模數高於熱膨脹性黏著層之彈性模數，從而以於晶圓或薄膜等被黏著體表面依序重疊熱膨脹性黏著層與黏著層之方式進行貼合後，對該被黏著體進行加工等。於該加工後將該被黏著體自熱膨脹性黏著層剝離之情形時，藉由將該熱膨脹性黏著層加熱而使其熱膨脹。於該熱膨脹時，該熱膨脹性黏著層之體積增加，其增加部分成為朝向該黏著層及該被黏著體之擠壓力。此時，該黏著層之彈性模數高於熱膨脹性黏著層，因此該擠壓力受到控制而主要朝向該被黏著體。
因此，該被黏著體以不產生翹曲等而自該黏著層上舉起之方式移動，可將該被黏著體自該熱膨脹性黏著層上剝離。
另外，上述放射線硬化型黏著劑例如係於以使多官能單體等具有交聯性官能基之單體共聚合而成之聚合物作為成分之黏著劑、或調配有多官能單體等交聯性低分量化合物之黏著劑等中，調配光聚合起始劑等，而使其能夠藉由放射線照射進行交聯硬化者，可藉由該交聯硬化而謀求對被黏著體之污染物質之減少、並且視需要謀求接著力之降低。
作為於放射線硬化型黏著劑中調配之光聚合起始劑，例如可使用：如4-(2-羥基乙氧基)苯基(2-羥基-2-丙基)酮、α-羥基-α,α'-二甲基苯乙酮、甲氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基 苯乙酮、1-羥基環己基苯基酮、2-甲基-1-[4-(甲基硫代)-苯基]-2-嗎啉丙烷-1之苯乙酮系起始劑，如苯偶姻乙醚、苯偶姻異丙醚、茴香偶姻甲基醚之苯偶姻醚系起始劑，如2-甲基-2-羥基苯丙酮之α-酮醇系化合物，如苯偶醯二甲基縮酮之縮酮系化合物，如2-萘磺醯氯之芳香族磺醯氯系化合物，如1-苯基-1,1-丙二酮-2-(o-乙氧基羰基)肟之光活性肟系化合物，如二苯甲酮、苯甲醯苯甲酸、3,3'-二甲基-4-甲氧基二苯甲酮之二苯甲酮系化合物，如硫雜蒽酮、2-氯硫雜蒽酮、2-甲基硫雜蒽酮、2,4-二甲基硫雜蒽酮、異丙基硫雜蒽酮、2,4-二氯硫雜蒽酮、2,4-二乙基硫雜蒽酮、2,4-二異丙基硫雜蒽酮之硫雜蒽酮系化合物，以及樟腦醌、鹵代酮、醯基氧化膦、醯基膦酸酯等適宜之放射線硬化型光聚合起始劑。
此外，用於黏著層之形成之黏著劑亦可為如上所述調配有例如塑化劑、填充劑、界面活性劑、抗老化劑、黏著賦予劑等適宜之添加劑者，如期待上述低污染性之情形般，於該添加劑向被黏著體之轉印成為問題之用途中，亦可形成不調配添加劑之組成之黏著劑。
黏著層之形成例如可藉由將液狀黏著劑塗佈於熱膨脹性黏著層上之方式、根據該黏著層之塗佈方式將形成於隔離膜上之黏著層轉移到熱膨脹性黏著層上之方式等適宜方式而進行。黏著層之厚度可根據黏著片材之使用目的、由加熱導致之接著力之減小性等而適當確定。另外，於本發明中之熱膨脹性黏著層、或與該熱膨脹性黏著層不同之黏著層之表面，為了保護該等層，可積層剝離片材(隔離膜)等。
(隔離膜)
上述隔離膜例如可以如下之形式獲得：利用聚矽氧系、長鏈烷基系、氟系、硫化鉬等適宜之剝離劑對聚酯、烯烴系樹脂、聚氯乙烯等塑膠膜或片材進行表面處理而成者；包含如聚四氟乙烯、聚氯三氟乙烯、聚氟乙烯、聚偏二氟乙烯、四氟乙烯-六氟丙烯共聚物、三氟 氯乙烯-偏二氟乙烯共聚物之氟系聚合物之低接著性基材；包含如聚乙烯、聚丙烯及α烯烴之非極性聚合物之低接著性基材等。
(彈性層)
彈性層可包含合成橡膠或合成樹脂，另外，亦可藉由形成上述黏著層之黏著劑而形成，另外，亦可藉由以該成分為主體之發泡膜等多孔性膜而形成。彈性層之形成例如可藉由將上述形成劑之溶液塗佈於基材上之方式、或使包含上述形成劑之膜等與基材接著之方式等適宜之方式而進行，就上述作用等方面而言，更佳為設為使彈性層重疊於熱膨脹性黏著層之設有黏著層之側的相反側之形態。再者，於藉由放射線等對黏著層進行處理之情形時，設為可使該處理射線透過之中間層。
作為上述合成橡膠或合成樹脂，例如可列舉：腈系、二烯系、丙烯酸系等合成橡膠，如聚烯烴系、聚酯系之熱塑性彈性體，如乙烯-乙酸乙烯酯共聚物、聚胺基甲酸酯、聚丁二烯、軟質聚氯乙烯之具有橡膠彈性之合成樹脂。於本發明中，亦可使用藉由與塑化劑、柔軟劑等調配劑之組合而使如聚氯乙烯之本質上為硬質系之聚合物亦具有橡膠彈性者。
彈性層並非作為用以支撐該熱膨脹性黏著層及與該熱膨脹性黏著層不同之黏著層之所謂基材而發揮作用之層，而係為了於加熱步驟後使被黏著體不產生翹曲而用以對本發明之加熱剝離型黏著片材賦予更高彈性之層。考慮到其彈性模數、厚度，彈性層之厚度係顯示實質上未成為基材層之程度之性質的範圍。雖然根據彈性模數而不同，但該厚度為1μm~50μm、較佳為3~20μm、更佳為5~10μm。
(用途、使用方法)
本發明之加熱剝離型黏著片材可形成為片狀、帶狀、標籤狀等適宜之形態而用於被黏著體之接著等之依據先前之黏著片材之各種用 途，係可利用任意時期之加熱處理減小接著力而較容易地自被黏著體剝離者，藉此可要求發揮其優點而於被黏著體上接著規定時間後解除其接著狀態、或者較佳地用於所期望之用途。對於被黏著體，並無特別限定，例如可為包含金屬、陶瓷、塑膠、木材、紙等任意之原材料者，接著面亦可具有板狀、曲面狀、纖維狀等任意之形狀。
另外，作為上述用途之例子，可列舉：以包含兩種以上之物品、例如包含聚合物之物品與包含金屬、纖維或紙等之物品的再循環為目的之接著複合物之形成，以各種電氣裝置或電子裝置、顯示裝置等之組裝步驟中之零件之輸送用途或暫時固定用途等以載帶、暫時固定材料或固定材料、金屬板、塑膠板、玻璃板等之污染損傷防止為目的的表面保護材料、掩蔽材料等。
尤其是，本發明可經由黏著層而根據使用目的適當設定接著力等黏著特性，並且，伴隨於由加熱導致之接著力之減小處理之污染物質、尤其是微小之污染物質之增大較少，藉此可如半導體晶圓之背面研磨處理、切割處理般於加工時等藉由較強之接著力接著於被黏著體上，可較佳地用於解除該接著狀態時期望被黏著體中之污染較少之用途。
上述用以減小加熱剝離型黏著片材之接著力之加熱處理例如可經由熱板、熱風乾燥機、近紅外燈等適宜之加熱手段而進行。加熱處理之條件可根據基於被黏著體之表面狀態或熱膨脹性微球之種類等的接著面積之減少性、基材或被黏著體之耐熱性、熱容量或加熱手段等條件而適當確定。
通常為利用100~250℃之溫度的5~90秒(熱板等)或1~15分鐘(熱風乾燥機等)之加熱處理等，但並不限定於此。藉由上述條件下之加熱處理，通常使熱膨脹性微粒膨脹或/及發泡，熱膨脹性黏著層凹凸變形，黏著層亦隨之凹凸變形，使接著力降低或消失。
實施例
以下，根據實施例對本發明進行更詳細地說明，但本發明並非限定於該等實施例。
實施例1
調製於丙烯酸丁酯：丙烯酸(95重量份：5重量份)共聚物100重量份中調配有交聯劑(商品名「Tetrad C」，三菱瓦斯化學股份有限公司製造)3重量份之混合液1。以乾燥後之厚度為30μm之方式將該混合液1塗佈於經聚矽氧處理之50μm厚之聚酯薄膜上並進行乾燥而形成感壓黏著層1。再者，藉由AFM力曲線(Asylum Technology製造，使用Si製探針(R：10nm，彈簧常數：1.6nN/nm)，探針移動速度4μm/s，測定溫度23℃)對該黏著劑表面進行測定而獲得之彈性模數為3.2MPa。
另一方面，調製於丙烯酸2-乙基己酯：丙烯酸乙酯：甲基丙烯酸甲酯：丙烯酸2-羥乙酯(30重量份：70重量份：5重量份：2重量份)共聚物系感壓接著劑100重量份中調配交聯劑(商品名「Coronate L」，日本聚氨酯股份有限公司製造)2重量份及熱膨脹性微球A(Matsumoto Microsphere F-100D，Matsumoto Yushi-Seiyaku股份有限公司製造)30重量份而成之甲苯溶液而調製混合液2。
以乾燥後之厚度為45μm之方式將其塗佈於經聚矽氧處理之50μm厚之聚酯薄膜上並進行乾燥而形成熱膨脹性黏著層2。再者，該熱膨脹性黏著層2之藉由AFM力曲線測得之彈性模數為1.8MPa。將所獲得之熱膨脹性黏著層2黏附於感壓黏著層1上而獲得加熱剝離型黏著片材A。
實施例2
調製於含羥基丙烯酸系聚合物中調配加成甲基丙烯醯氧基伸乙基異氰酸酯之羥基之0.9當量的紫外線反應性聚合物(重量平均分子量50萬)100重量份、光反應起始劑3重量份、及交聯劑(商品名 「Coronate L」，日本聚氨酯股份有限公司製造)0.2重量份之混合液3。以乾燥後之厚度為50μm之方式將該混合液3塗佈於經聚矽氧處理之50μm厚之聚酯薄膜上並進行乾燥而形成紫外線硬化型黏著層3。再者，紫外線硬化型黏著層3之硬化前彈性模數為0.7MPa，照射300mJ/cm2之紫外線而硬化後之彈性模數為142MPa。將紫外線硬化型黏著層3黏附於實施例1所記載之熱膨脹性黏著層2上而獲得加熱剝離型黏著片材B。
比較例1
以乾燥後之厚度成為50μm之方式將混合液1塗佈於75μm厚之聚酯薄膜上並進行乾燥，於聚酯薄膜之相反側上以乾燥後之厚度成為45μm之方式塗佈混合液2並進行乾燥而獲得加熱剝離型黏著片材C。
比較例2
將在丙烯酸2-乙基己酯：丙烯酸(97重量份：3重量份)共聚物100重量份中調配交聯劑(商品名「Coronate L」，日本聚氨酯股份有限公司製造)2重量份之混合液用於感壓黏著層，除此以外，藉由與實施例1同樣之步驟而獲得黏著片材D。再者，黏著層之彈性模數為0.8MPa。
[評價試驗] 翹曲量
於實施例、比較例中製作之黏著片材之熱膨脹性黏著層上黏附50μm厚之聚醯亞胺薄膜(230mm見方)後，將黏著層側黏附於650μm厚之玻璃板(230mm見方)上。其後，使用熱風乾燥機於100℃下加熱1小時後測定放置冷卻至室溫時之翹曲量。
加熱剝離性
將實施例、比較例中製作之黏著片材之熱膨脹性黏著層黏附於SUS304BA板上後，將黏著層側黏附於650μm之玻璃板上，在80℃之熱風乾燥機中加熱12小時後，放置冷卻至室溫。於加熱至180℃之熱 板上對貼合樣品進行加熱，評價自SUS板上之剝離性。
評價結果
1‧‧‧熱膨脹性黏著層
2‧‧‧黏著層
3‧‧‧隔離膜

Claims (4)

  1. 一種加熱剝離型黏著片材，其特徵在於，其係將含有熱膨脹性微球之熱膨脹性黏著層及與該熱膨脹性黏著層不同之黏著層積層而成之無基材雙面黏著片材，黏著層包含能量射線硬化型黏著劑，且具有較熱膨脹性黏著層更高之彈性模數。
  2. 如請求項1之加熱剝離型黏著片材，其中黏著層之彈性模數為500MPa以下。
  3. 如請求項1或2之加熱剝離型黏著片材，其中於黏著層與熱膨脹性黏著層之間具有彈性層。
  4. 一種電子零件及半導體零件之製造方法，其特徵在於，使用如請求項1至3中任一項之加熱剝離型黏著片材實施電子零件及半導體零件之加工。
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