TW201224100A - Adhesive composition and adhesive film - Google Patents

Adhesive composition and adhesive film Download PDF

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Publication number
TW201224100A
TW201224100A TW100123849A TW100123849A TW201224100A TW 201224100 A TW201224100 A TW 201224100A TW 100123849 A TW100123849 A TW 100123849A TW 100123849 A TW100123849 A TW 100123849A TW 201224100 A TW201224100 A TW 201224100A
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Taiwan
Prior art keywords
resin
adhesive
adhesive composition
film
group
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TW100123849A
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Chinese (zh)
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TWI529232B (en
Inventor
Takahiro Asai
Koki Tamura
Hirofumi Imai
Takahiro Yoshioka
Atsushi Kubo
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Tokyo Ohka Kogyo Co Ltd
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Publication of TW201224100A publication Critical patent/TW201224100A/en
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Publication of TWI529232B publication Critical patent/TWI529232B/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

The purpose of the present invention is to provide an adhesive composition, which is used to adhere to wafer and has an increased softening temperature. The solution is to provide an adhesive composition, which is used to adhere to wafer and contains an adhesive resin and a filler, and also provide an adhesive layer containing the said adhesive composition.

Description

201224100 六、發明說明： 【發明所屬之技術領域】 本發明關於接著晶圓用的接著劑組成物及接著薄膜。 【先前技術】 作爲接著劑組成物，專利文獻'1中記載一種含有烴樹 脂的接著劑。又，專利文獻2中記載一種接著性樹脂組成 物，其含有在表面具有與接著劑樹脂成分進行化學反應的 有機基之矽石微粉末，專利文獻3中記載一種在主劑中加 有塡料而成的接著劑。 [先前技術文獻] [專利文獻] [專利文獻1]特開2010-10 9.3 24號公報（2010年5 月1 3日公開） [專利文獻2]特開平10-2 87854號公報（ 1998年10 月27日公開） [專利文獻3]特開平8-319466號公報（1996年12 月3日公開） 【發明內容】 [發明所欲解決的問題] 然而，使用如上述的習知技術之接著劑來接著晶圓與 玻璃基板等後，例如若在2 5 0 °C附近進行高溫製程，則接 201224100 著劑會自晶圓的端面溶出，發生所謂的脫層（接著劑自晶 圓的端面溶出）。因此，要求進一步提高（更提高）接著 劑組成物的軟化溫度。 本發明係鑒於上述習知技術所具有的問題而完成者， 其目的在於提供一種接著晶圓用的軟化溫度經進一步提高 (更高）之接著劑組成物及一種接著薄膜》 [解決問題的手段] 爲了解決上述問題，本發明的接著劑組成物係一種接 著晶圓用的接著劑組成物，其特徵爲含有具備接著性的樹 脂、與塡料。 又’於本發明的接著劑組成物中，相對於上述樹脂而 言’上述塡料的含有率較佳爲20重量％以上70重量％以下 〇 另外’於本發明的接著劑組成物中，上述塡料的平均 粒徑較佳爲〇·5μηι以上5μηι以下。 還有’於本發明的接著劑組成物中，上述塡料較佳爲 無機塡料。 又’於本發明的接著劑組成物中，上述塡料的耐熱性 較佳爲300°C以上。 另外’於本發明的接著劑組成物中，上述樹脂較佳爲 烴樹脂。 還有’於本發明的接著劑組成物中，上述烴樹脂較佳 爲選自由環嫌烴系聚合物、萌嫌樹脂、松香系樹脂及石油 -6- 201224100 樹脂所成之群組。 爲了解決上述問題，本發明的接著薄膜之特徵爲在薄 膜上具備如上述中任一個接著劑組成物之接著劑層。 [發明的效果] 本發明的接著劑組成物係如以上，爲接著晶圓用的接 著劑組成物，其含有具備接著性的樹脂、與塡料。因此， 可提供軟化溫度經進一步提高（更高）的接著劑組成物及 接著薄膜。 【實施方式】 [實施發明的形態] 以下詳細說明本發明的一實施形態。 [接著劑組成物] 本實施形態的接著劑組成物係一種接著晶圓用的接著 劑組成物，其含有具備接著性的樹脂、與塡料。 本實施形態的接著劑組成物，由於含有塡料而物理地 抑制在高溫的溶解，故軟化溫度進一步升高（變高）。因 此，若使用此接著劑組成物，使晶圓接著於玻璃基板等， 則於其後的高溫製程（PVD、CVD等的蒸鏟步驟等）之際 ，可抑制接著劑自晶圓的端面溶出（脫層）。因此’本實 施形態的接著劑組成物係可適用於晶圓的接著。 以下說明含有接著劑組成物的各構成要素。 201224100 <塡料> 塡料係沒有特別的限定’例如較佳爲無機塡料。作爲 無機塡料，可舉出矽石、氧化鋁、氧化鋅、氧化鈦、氧化 鈣、氧化鎂、氧化鐵、氧化錫、氧化銻、肥粒鐵類、氫氧 化錦、氫氧化鎂、氫氧化鋁、鹼式碳酸鎂、碳酸鈣'碳酸 鋅、碳酸鋇、片鈉銘石（dowsonite)、水滑石、硫酸銘 、硫酸鋇、矽酸鈣、滑石、黏土、雲母、蒙脫石、膨土、 海泡石、絲狀鋁英石、絹雲母、玻璃纖維、玻璃珠、矽石 系氣球、氮化鋁、氮化硼、氮化矽、碳黑、石墨 '碳纖維 '碳氣球、硼酸鋅、各種磁性粉等。 又，無機塡料亦可藉由矽烷系、鈦酸酯系等的各種偶 合劑而施予表面處理。作爲表面處理的方法，可舉出乾式 法、淤漿法或噴霧法等，藉由各種偶合劑直接處理無機塡 料的方法、直接法、母料混合法等的整體摻合法，或乾濃 縮法等方法。 作爲塡料可使用的市售品，例如可舉出信越化學公司 製的聚矽氧樹脂粉、聚矽氧複合粉、聚矽氧橡膠粉等。 相對於樹脂而言，塡料的含有率較佳爲20重量％以上 7 0重量％以下。塡料的含有率若爲2 0重量％以上，則由於 接著劑的軟化溫度充分變高，而可抑制脫層。又，若爲7〇 重量％以下，則可保持充分的接著力。此處，「相對於樹 脂而言，塡料的含有率」係指以樹脂爲1 00重量％時的含 有率。 -8- 201224100 再者，塡料的含有率，只要是能避免接著劑組成物所 接著的晶圓之剝離的量即可，從接著劑的軟化溫度之上升 及應力的緩和之觀點來看，愈高愈佳。因此，塡料的含量 更佳爲50重量％以上70重量％以下。 塡料的平均粒徑較佳爲0.5μηι以上5μιη以下。因此’ 由於在接著組成物內不沈降而可分散，可充分發揮其機能 。又，塡料的平均粒徑，從緩和晶圓的應力之觀點來看’ 較佳爲0.5 μιη以上Ιμιη以下。若使用含有如此平均粒徑的 塡料之接著劑組成物，則在使晶圓接著於玻璃基板等後， 供應給高溫製程時，可減輕晶圓的翹曲量。因此，其後的 製程流動係成爲可能。 又，塡料的耐熱性較佳爲3 0 0 °C以上。藉此，可有效 地抑制脫層。再者，本說明書中所謂的「具有3001以上 的耐熱性」’係指由室溫加熱到3 0 0 °C時的重量變化率爲 1%以下。 <樹脂> 作爲樹脂，只要是具備接著性者即可，例如可舉出烴 樹脂、丙烯酸-苯乙烯系樹脂、馬來醯亞胺系樹脂等。 (烴樹脂） 作爲烴樹脂，可舉出環烯烴系聚合物（以下亦稱爲「 樹月曰（A)」）’以及選自由蔽燒樹脂、松香系樹脂及石 油樹脂所成之群組中的至少一種樹脂（以下亦稱爲「樹脂 -9 - 201224100 (B)」）等’惟不受此所限定。 作爲樹脂（A)，可爲將含有環烯烴系單體的單體成 分聚合而成的樹脂。具體地，可舉出使含有環烯烴系單體 的單體成分之開環（共）聚合物、含有環烯烴系單體的單 體成分進行加成（共）聚合而成的樹脂等。 作爲構成樹脂（A)的單體成分中所含有的前述環烯 烴系單體’例如可舉出降冰片烯、降冰片二烯等的二環體 、二環戊二烯、二羥基戊二烯等的三環體、四環十二烯等 的四環體、環戊二烯三聚物等的五環體、四環戊二烯等的 七環體、或此等多環體的.院基（甲基、乙基 '丙基、丁基 等）取代物、烯基（乙烯基等）取代物、亞烷基（亞乙基 等）取代物、芳基（苯基、甲苯基、萘基等）取代物等。 於此等之中，特佳爲選自由降冰片烯、四環十二烯或此等 烷基取代物所成之群組的降冰片烯系單體。 作爲構成樹脂（A)的單體成分，亦可含有能與上述 環烯烴系單體共聚合的其它單體，例如較佳爲含有烯單體 。作爲烯單體，例如可舉出乙烯、丙烯、1-丁烯、異丁烯 、1-己烯、a-烯烴等。烯單體係可爲直鏈狀，也可爲支鏈 狀。 構成樹脂（A)的單體成分，較佳爲其50質量％以上 係前述環烯烴系單體，更佳爲60質量％以上係前述環烯烴 系單體。環烯烴系單體若爲單體成分全體的5 0質量％以上 ，則在高溫環境下的接著強度變良好。 再者，樹脂（A)例如是如由使環烯烴系單體與烯單 -10- 201224100 體所成的單體成分聚合而成的樹脂，爲不具有極性基的樹 脂’此在抑制高溫下的氣體發生之方面係較佳》 將單體成分聚合時的聚合方法或聚合條件等係沒有特 別的限制，可依照常用方法來適宜設定。 作爲樹S曰（A)可用的市售品，例如可舉出p〇iypiastics 公司製的「T0PAS」、三井化學公司製的「APEL」、日 本Zeon公司製的「ZE0N0R」及「ZE0NEX」、JSR公司製 的「ARTON」等。 樹脂（A )的玻璃轉移點（Tg )較佳爲6(rc以上。特 佳爲樹脂（A )的玻璃轉移點係7 0 °C以上。若樹脂（A ) 的玻璃轉移點爲60°C以上，則當接著劑組成物暴露在高溫 環境時，可進一步抑制接著層的軟化。 樹fl曰（B)係選自由蔽嫌系樹脂、松香系樹脂及石油 樹脂所成之群組中的至少一種樹脂。具體地，作爲萜烯系 樹脂’例如可舉出萜烯樹脂、萜烯苯酚樹脂、改性萜烯樹 脂' 氫化萜烯樹脂 '氫化萜烯苯酚樹脂等。作爲松香系樹 脂，例如可舉出松香、松香酯、氫化松香、氫化松香酯、 聚合松香、聚合松香酯、改性松香等。作爲石油樹脂，例 如可舉出脂肪族或芳香族石油樹脂、氫化石油樹脂、改性 石油樹脂、脂環族石油樹脂、色滿•茚石油樹脂等。於此 等之中，較佳爲氫化萜烯樹脂、氫化石油樹脂。 樹脂（B )的軟化點係沒有特別的限定，較佳爲8 0〜 1 6 0 °C。樹脂（B )的軟化點若爲8 0 °c以上，則當接著劑組 成物暴露在高溫環境時’可抑制軟化，不發生接著不良。 -11 - 201224100 另一方面，樹脂（B )的軟化點若爲1 60 °C以下，則在剝離 接著劑組成物之際，剝離速度變良好。 樹脂（B)的分子量係沒有特別的限定，較佳爲300〜 3 000。樹脂（B)的分子量若爲3 00以上，則耐熱性變充分 ，在高溫環境下的脫氣量變少。另一方面，樹脂（B)的 分子量若爲300 0以下，則在剝離接著劑組成物之際，剝離 速度變良好。再者，本實施形態的樹脂（B)之分子量係 意味以凝膠滲透層析術（GPC )所測定的聚苯乙烯換算之 分子量。 再者，作爲樹脂，亦可使用樹脂（A )樹脂（B )的 混合者。藉由混合，耐熱性及剝離速度變良好。例如，樹 脂（A)與樹脂（B)的混合比例爲（A) ： ( B ) =80 ： 20 〜5 5 : 45 (質量比），係剝離速度、高溫環境時的熱耐性 及柔軟性優異而較佳》 (丙烯酸-苯乙烯系樹脂） 作爲丙烯酸-苯乙烯系樹脂，例如可舉出使用苯乙烯 或苯乙烯的衍生物與（甲基）丙烯酸酯等當作單體所聚合 的樹脂。 作爲（甲基）丙烯酸酯，例如可舉出由鏈式構造所成 的（甲基）丙烯酸烷酯、具有脂肪族環的（甲基）丙烯酸 酯、具有芳香族環的（甲基）丙烯酸酯。作爲由鏈式構造 所成的（甲基）丙烯酸烷酯，可舉出具有碳數15〜20的烷 基之丙烯酸系長鏈烷酯、具有碳數1〜14的烷基之丙烯酸 -12- 201224100 系烷酯等。作爲丙烯酸系長鏈烷酯，可舉出烷基爲正十五 基、正十六基、正十七基、正十八基、正十九基、正二十 基等的丙烯酸或甲基丙烯酸之烷酯。再者，該烷基亦可爲 支鏈狀。 作爲具有碳數1〜14的烷基之丙烯酸系烷酯，可舉出 既存的丙烯酸系接著劑中所用的眾所周知之丙烯酸系烷酯 。例如，可舉出烷基爲甲基、乙基、丙基、丁基、2-乙基 己基、異辛基、異壬基、異癸基、十二基、月桂基、十三 基等所成的丙烯酸或甲基丙烯酸之烷酯。 作爲具有脂肪族環的（甲基）丙烯酸酯，可舉出（甲 基）丙烯酸環己酯、（甲基）丙烯酸環戊酯、（甲基）丙 烯酸1-金剛烷酯、（甲基）丙烯酸降冰片酯、（甲基）丙 烯酸異冰片酯、（甲基）丙烯酸三環癸酯、（甲基）丙烯 酸四環十二酯、（甲基）丙烯酸二環戊酯等，更佳爲甲基 丙烯酸異冰片酯、（甲基）丙烯酸二環戊酯。 作爲具有芳香族環的（甲基）丙烯酸酯，並沒有特別 的限定，作爲芳香族環，例如可舉出苯基、苄基、甲苯基 、二甲苯基、聯苯基、萘基、蒽基、苯氧基甲基、苯氧基 乙基等。又，芳香族環亦可爲碳數1〜5的鏈狀或支鏈狀烷 基。具體地，較佳爲丙烯酸苯氧基乙酯。 (馬來醯亞胺系樹脂） 作爲馬來醯亞胺系樹脂，例如可舉出將作爲單體的N -甲基馬來醯亞胺、N-乙基馬來醯亞胺、N -正丙基馬來醯亞 -13- 201224100 胺、N-異丙基馬來醯亞胺、N-正丁基馬來醯亞胺、N-異丁 基馬來醯亞胺、N-第二丁基馬來醯亞胺、N-第三丁基馬來 醯亞胺、N-正戊基馬來醯亞胺、N-正己基馬來醯亞胺、N-正庚基馬來醯亞胺、N-正辛基馬來醯亞胺、N-月桂基馬來 醯亞胺、N-硬脂基馬來醯亞胺等之具有烷基的馬來醯亞胺 、N-環丙基馬來醯亞胺、N-環丁基馬來醯亞胺、N-環戊基 馬來醯亞胺、N-環己基馬來醯亞胺、N-環庚基馬來醯亞胺 、N-環辛基馬來醯亞胺等之具有脂肪族烴基的馬來醯亞胺 、N-苯基馬來醯亞胺、N-間甲基苯基馬來醯亞胺、N-鄰甲 基苯基馬來醯亞胺、N-對甲基苯基馬來醯亞胺等之具有芳 基的芳香族馬來醯亞胺等聚合而得之樹脂。 <接著劑組成物之調製方法> 本實施形態的接著劑組成物係可使用眾所周知的方法 ，混合上述樹脂與塡料而調製。作爲樹脂，亦可使用視需 要經有機溶劑稀釋的溶液（樹脂溶液）。 作爲有機溶劑，例如可舉出丙酮、甲基乙基酮、環己 酮、甲基異戊基酮、2-庚酮等的酮類；乙二醇、乙二醇單 乙酸酯、二乙二醇、二乙二醇單乙酸酯、丙二醇、丙二醇 單乙酸酯、二丙二醇或二丙二醇單乙酸酯的單甲基醚、單 乙基醚、單丙基醚、單丁基醚或單苯基醚等的多元醇類及 其衍生物；二噁烷等的環式醚類；乳酸甲酯、乳酸乙酯' 醋酸甲酯、醋酸乙酯 '醋酸丁酯 '丙酮酸甲酯、丙酮酸乙 酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯等的酯類；及萜烯 -14- 201224100 系溶劑等。此等可單獨使用，也可混合2種以上使用。 作爲萜烯系溶劑，例如可舉出（X-蒎烯、莰烯、蒎烷、 香葉烯、二氫化香葉烯、對蓋烷、3-蒈烯、對蓋二烯、α_ 萜品烯、β-萜品烯、α-水芹烯、羅勒烯、檸檬烯、對傘花 烴、γ-萜品烯、萜品二烯、1,4-桉樹腦、1，8-桉樹腦、氧 化玫瑰、氧化里哪醇、葑酮、α-環檸檬醛、羅勒醇、四氫 里哪醇、里哪醇、四氫別羅勒烯醇、異蒲勒醇、二氫里哪 醇、異二氫薰衣草醇、β-環檸檬醛、香茅醛、L-荖酮、甲 酸里哪酯' 二氫萜品醇、β-萜品醇、蓋醇、香葉醇' L-蓋 醇、松香芹醇、α-萜品醇、γ-萜品醇、諾甫醇、桃金娘烯 醇、二氫香芹烯醇、香茅醇、桃金娘烯醛、二氫香芹酮、 d-蒲勒酮、香葉基乙基醚、甲酸香葉酯、甲酸橙花酯、甲 酸萜品酯、乙酸異二氫雜薰衣草酯、乙酸萜品酯、乙酸里 哪酯、乙酸香葉烯酯、乙酸降冰片酯、丙酸蓋酯、丙酸里 哪酯、橙花醇、香芹醇、紫蘇醇、香葉醇、番紅花醛、檸 檬醛、紫蘇醛、香茅基含氧乙醛、羥基香茅醛、馬鞭烯酮 、d-香芹酮、L-香芹酮、薄荷酮、薄荷烯酮、甲酸香茅酯 、乙酸異冰片基、乙酸蓋酯、乙酸香茅酯、乙酸胩酯、乙 酸二甲基辛酯、乙酸橙花酯、乙酸異長葉薄荷醇、乙酸二 氫卡必酯、乙酸諾卜酯、乙酸香葉基、丙酸降冰片酯、丙 酸橙花酯、丙酸卡必酯、丙酸萜品酯、丙酸香茅酯、丙酸 異冰片酯、異丁酸里哪酯、異丁酸橙花酯、丁酸里哪酯、 丁酸燈花酯、異丁酸萜品酯、丁酸萜品酯、異丁酸香葉酯 、丁酸香茅酯 '己酸香茅酯、異戊酸蓋酯、β_石竹烯、雪 -15- 201224100 松烯、紅沒藥烯、羥基香茅醇、法呢醇及 。於此等之中，從溶解性的觀點來看，較 蓬烷，特佳爲對荖烷。 [接著薄膜] 上述本實施形態的接著劑組成物係可 各式各樣的利用方法。例如，可使用液狀 體晶圓等被加工體上而形成接著劑層之方 本實施形態的接著薄膜，即預先在可繞性 成含有上述中任一接著劑組成物的接著劑 將此薄膜（接著薄膜）黏貼於被加工體而 著薄膜法）。 如此地，本實施形態的接著薄膜係在 如上述中任一接著劑組成物的接著劑層。 劑組成物的軟化溫度高，可抑制高溫製程 接著薄膜亦可在此接著劑層上更被覆 。此時，剝離接著劑層上的保護薄膜，在 已露出的接著劑層後，自接著劑層剝離薄 工體上容易地設置接著劑層》 因此，若使用本實施形態中的接著薄 工體上直接塗佈接著劑組成物而形成接著 下，可形成膜厚均勻性及表面平滑性良好 作爲接著薄膜之製造時所使用的薄膜 膜上所製膜的接著劑層自薄膜剝離，而能 異丁酸玻瑰酯等 佳爲檸檬烯及對 按照用途而採用 直接塗佈於半導 法，也可使用於 薄膜等薄膜上形 層後，使乾燥， 使用之方法（接 薄膜上具備含有 因此，由於接著 中的脫層。 保護薄膜而使用 被加工體上重疊 膜，而可在被加 膜，則與在被加 劑層的情況比較 的層。 ，只要是可將薄 將接著劑層轉印 -16- 201224100 到保護基板或晶圓等被處理面上之脫模薄膜，則沒有 。例如，可舉出由膜厚15〜125μιη的聚對苯二甲酸乙 、聚乙烯、聚丙烯、聚碳酸酯、聚氯乙烯等的合成樹 膜所成之可撓性薄膜。對於薄膜，爲了使容易轉印， 爲進行脫模處理。 作爲在薄膜上形成接著劑層的方法，可按照所欲 著劑層之膜厚或均勻性，適宜地使用眾所周知的方法 沒有限定’例如可舉出使用塗抹機、桿塗機、線桿塗 、輥塗機、簾幕流動式塗佈機等，以在薄膜上的接著 之乾燥膜厚成爲10〜ΙΟΟΟμηι的方式，塗佈本發明的 劑組成物之方法。其中，較佳爲輥塗機，因爲膜厚的 性優異’而且可有效率地形成厚的厚膜。 又’使用保護薄膜時，作爲保護薄膜，只要可自 劑層剝離，則沒有限定，例如較佳爲聚對苯二甲酸乙 薄膜、聚丙烯薄膜、聚乙烯薄膜。再者，各保護薄膜 容易自接著劑層剝離的觀點來看，較佳爲塗佈或燒附 保護薄膜的厚度係沒有特別的限定，從確保具備保護 的接著薄膜之柔軟性的觀點來看，較佳爲15〜125μιη 接著薄膜的使用方法係沒有特別的限定，例如可 使用保護薄膜時’在剝離其剝離後，於被加工體上重 露出的接著劑層’於薄膜上（接著劑層的形成面之背 使加熱輥移動，而將接著劑層熱壓黏於被加工體的表 方法。此時’自接著薄膜所剝離的保護薄膜，若依順 捲繞輥等捲繞成輥狀，則可保存而再利用。 限定 二酯 脂薄 較佳 的接 ，而 佈機 劑層 接著 均勻 接著 二酯 ，從 砂。 薄膜 9 舉出 疊所 面） 面之 序被 -17- 201224100 [接著劑組成物及接著薄膜之用途] 本發明的接著劑組成物及接著薄膜之用途，只要是使 用於晶圓的接著用途，則沒有特別的限定，但可合適地使 用於使半導體晶圓的精密加工用保護基板接著於半導體晶 圓等的基板之用途。 本發明係不受上述實施形態所限定，在申請專利範圍 所示的範圍內，各種的變更係可能。即，關於將在申請專 利範圍所示的範圍內適宜變更之技術手段組合而得的實施 形態，亦包含於本發明的技術範圍內。 [實施例] [接著劑組成物之調製] 將具備接著性的樹脂溶解於對盏烷中，而形成成樹脂 固體成分濃度爲3 0質量％的樹脂溶液。然後，於此樹脂溶 液中添加塡料（以樹脂固體成分爲基準），使用行星式混 合機來混合，而調製實施例1〜10的接著劑組成物。 作爲塡料，使用聚矽氧粒子的塡料1或塡料2中之任一 者。作爲塡料1，使用聚有機倍半矽氧烷（RSi3/2 ) η的三 次元交聯品之聚矽氧樹脂粉（「ΚΜΡ-70 1」（製品名）； 粒徑3.5μηι，粒度分布1〜6μηι，400°C以上的耐熱性，信 越化學公司製）。作爲塡料2，使用聚矽氧經矽樹脂所被 覆的聚矽氧複合粉（「X-5 2-703 0」（製品名）；粒徑 0.8μιη，粒度分布〇·2〜2μηι，300°C以上的耐熱性，信越化 -18- 201224100 學公司製）。 作爲具備接著性的樹脂，使用樹脂1或樹脂2中的任一 者。作爲樹脂1，使用環稀烴共聚物（「TOPAS」（商品 名）8007，Polyplastics公司製）。又’作爲樹脂2，使用 環烯烴共聚物（「APEL」（商品名）8008，三井化學公 司製）。 作爲比較例的接著劑組成物，使用樹脂1，調製不含 塡料的接著劑組成物。 下述表1中顯示實施例1〜1 0及比較例的接著劑組成物 之組成。 [表1] 塡料 塡料含量 (重量％ ) 樹脂 實施例1 塡料1 10% 樹脂1 實 實®Γ~ 實 ~~ 實施廠〜 20% 50% 70% 塡料2 --------- 10% 20% 實~~~ 50% 70% 50% 樹脂2 實βϋ' 70% 比®Γ 0% 樹脂1 %轉移點及軟化點之測定] ' π ’測定各接著劑組成物的玻璃轉移點及軟化點。 將名士 ' Θ'接著劑組成物塗佈在1 25mm的晶圓上後，於 11〇°C、15〇。「 、20(TC各使乾燥3分鐘，而形成塗膜。對於 -19- 201224100 所形成的塗膜，使用Τ Μ A (熱機械分析裝置），分別測定 接著劑組成物的玻璃轉移點（Tg )及軟化點（SP )。測( 定條件係荷重爲800mN/cm2、升溫方式爲常溫〜200°C ( 5 °C /分鐘）。於此條件下，將下降開始點當作玻璃轉移點 ，將更大下降開始點當作軟化點》 圖1〜6各自顯示對於本發明的實施例3、4、7、8、9 或1 〇的接著劑組成物，使用TM A的測定結果之曲線圖。又 ，圖7係顯示對於本發明的比較例之接著劑組成物，使用 TMA的測定結果之曲線圖。另外，下述表2中顯示由此等 測定結果所得之玻璃轉移點及軟化點。 [表2] 玻璃轉移點 軟化點 (°c ) (°C ) 實施例3 73.2 166 實施例4 6 6.0 164 實施例7 68.0 154 實施例8 68.6 177 實施例9 60.9 163 實施初1 0 60.9 194 比較例 68.0 153 如表2中所示，實施例3、4、7、8、9及1 0的接著劑組 成物，與比較例相比，係顯示軟化點高，軟化溫度升高。 又，此效果係顯示與所使用的樹脂之種類無關而可獲得。 實施例3、4、7、8、9及1 0的接著劑組成物之使用 Τ Μ A的測定結果（圖1〜6 ) ’係顯示與比較例（圖7 )不 同的舉動。於含有粒徑爲3.5μηι的塡料1之實施例3及4的接 -20- 201224100 著劑組成物中，在1 2 0 °C〜1 5 0 °C的下降係緩和。 又，於含有粒徑爲〇.8μιη的塡料2之實施例7及8的接著 劑組成物中，與比較例、實施例3及4相比，自室溫到約 1 70 °C爲止的下降係小。因此，暗示接著劑組成物中所含 有的塡料之粒徑愈小，軟化溫度愈升高。 [應力之測定] 其次，測定使用各接著劑組成物時的應力（膜應力） 〇 將此等接著劑組成物塗佈在125 mm的晶圓上，於 1 10°C、150°C、200°C各使乾燥3分鐘，而形成接著劑層後 ，在此接著劑層上接著玻璃基板。然後，使用翹曲·膜應 力測定裝置（FLX-2908，KLA-Tencor公司製）’測定在 2 3 °C的應力。 圖8及下述表3中顯示其結果。圖8係顯示在使用本發 明的各實施例之接著劑組成物時，塡料含量與應力之關係 的曲線圖。如圖8及表3中所示，尤其在使用含有塡料2的 接著劑組成物（實施例5〜8 )時，塡料的含量愈多，則應 力愈減少。 -21 - 201224100 [表3] 膜厚 (μιη ) 翹曲 (μιη ) 應力 (MPa) 實施例1 12.4 13.56 8.3 實施例2 12.6 18.80 9.0 實施例3 34.2 46.26 9.3 實施例4 36.5 46.49 8.4 實施例5 12.7 16.23 8.0 實施例6 14.1 18.34 7.9 實施例7 55.9 55.10 6.3 實施例8 54.3 48.89 3.2 比較例 1 1.4 19.25 9.3 因此’顯示藉由使用含塡料的接著劑組成物，可緩如 應力’可減輕晶圓的翹曲量。特別地，可知藉由含有5 0重 量％以上的塡料，與應力的緩和有關，可得到更高的效果 。又’顯示塡料的粒徑愈小，則緩和應力的效果愈高。 [產業上的利用可能性] 本發明的接著劑組成物及接著薄膜係可適用於半導體 晶圓等的加工步驟。 【圖式簡單說明】 圖1係顯示對於本發明的實施例3之接著劑組成物，使 用TMA (熱機械分析裝置）的測定結果之曲線圖。 圖2係顯示對於本發明的實施例4之接著劑組成物，使 用TMA的測定結果之曲線圖。 圖3係顯示對於本發明的實施例7之接著劑組成物，使 用TMA的測定結果之曲線圖。 -22- 201224100 圖4係顯示對於本發明的實施例8之接著劑組成物’使 用TMA的測定結果之曲線圖。 圖5係顯示對於本發明的實施例9之接著劑組成物’使 用TMA的測定結果之曲線圖。 圖6係顯示對於本發明的實施例1 〇之接著劑組成物’ 使用TM A的測定結果之曲線圖。 圖7係顯示對於本發明的比較例之接著劑組成物’使 用TMA的測定結果之曲線圖。 圖8係顯示使用本發明的各實施例之接著劑組成物時 ，應力與塡料含量的關係之曲線圖。 -23-201224100 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to an adhesive composition for a subsequent wafer and a bonding film. [Prior Art] As an adhesive composition, Patent Document '1 describes an adhesive containing a hydrocarbon resin. Further, Patent Document 2 describes an adhesive resin composition containing an organic fine base fine powder having a chemical reaction with an adhesive resin component on the surface, and Patent Document 3 discloses that a raw material is added to the main component. Made of an adhesive. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2010-10 9.3-24 (published on May 13, 2010) [Patent Document 2] JP-A-10-2 87854 (1998) [Patent Document 3] JP-A-H08-319466 (published on Dec. 3, 1996) [Disclosure] [Problems to be Solved by the Invention] However, an adhesive using a conventional technique as described above is used. After the wafer and the glass substrate are next, for example, if a high-temperature process is performed at around 250 ° C, the 201224100 agent will be eluted from the end face of the wafer, so-called delamination occurs (the adhesive is eluted from the end face of the wafer). ). Therefore, it is required to further increase (improve) the softening temperature of the adhesive composition. The present invention has been made in view of the problems of the above-mentioned prior art, and an object thereof is to provide a further improved (higher) adhesive composition for a wafer and a film for subsequent use. In order to solve the above problems, the adhesive composition of the present invention is an adhesive composition for a subsequent wafer, which is characterized by containing a resin having an adhesive property and a coating material. Further, in the adhesive composition of the present invention, the content of the above-mentioned chopping material is preferably 20% by weight or more and 70% by weight or less based on the above resin, and the above-mentioned adhesive composition of the present invention is as described above. The average particle diameter of the dip material is preferably 〇·5 μηι or more and 5 μηι or less. Further, in the adhesive composition of the present invention, the above-mentioned dip material is preferably an inorganic dip. Further, in the adhesive composition of the present invention, the heat resistance of the above-mentioned dip material is preferably 300 ° C or higher. Further, in the adhesive composition of the present invention, the above resin is preferably a hydrocarbon resin. Further, in the adhesive composition of the present invention, the hydrocarbon resin is preferably selected from the group consisting of a ring-like hydrocarbon polymer, a germicidal resin, a rosin-based resin, and a petroleum -6-201224100 resin. In order to solve the above problems, the adhesive film of the present invention is characterized in that an adhesive layer of any one of the above-mentioned adhesive compositions is provided on the film. [Effects of the Invention] The adhesive composition of the present invention is, as described above, a binder composition for a subsequent wafer, which contains a resin having an adhesive property and a crucible. Therefore, it is possible to provide a further improved (higher) adhesive composition and a subsequent film having a softening temperature. [Embodiment] [Embodiment of the Invention] Hereinafter, an embodiment of the present invention will be described in detail. [Adhesive Composition] The adhesive composition of the present embodiment is a binder composition for a subsequent wafer, which contains a resin having an adhesive property and a crucible. Since the adhesive composition of the present embodiment contains a dip material and physically inhibits dissolution at a high temperature, the softening temperature is further increased (higher). Therefore, when the adhesive composition is used to cause the wafer to adhere to a glass substrate or the like, it is possible to suppress elution of the adhesive from the end face of the wafer during a subsequent high-temperature process (such as a steaming step such as PVD or CVD). (delamination). Therefore, the adhesive composition of the present embodiment can be applied to the subsequent bonding of wafers. Each constituent element containing the adhesive composition will be described below. 201224100 <Drying material> The material is not particularly limited. For example, it is preferably an inorganic material. Examples of the inorganic antimony include vermiculite, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrite iron, magnesium hydroxide, magnesium hydroxide, and hydroxide. Aluminum, basic magnesium carbonate, calcium carbonate 'zinc carbonate, barium carbonate, sodium dowsonite, hydrotalcite, sulfate, barium sulfate, calcium citrate, talc, clay, mica, montmorillonite, bentonite, Sepiolite, filamentous aluminite, sericite, glass fiber, glass beads, vermiculite balloons, aluminum nitride, boron nitride, tantalum nitride, carbon black, graphite 'carbon fiber' carbon balloon, zinc borate, various Magnetic powder, etc. Further, the inorganic mash may be subjected to surface treatment by various coupling agents such as decane-based or titanate-based. Examples of the surface treatment method include a dry method, a slurry method, a spray method, a method of directly treating an inorganic tantalum by various coupling agents, a bulk blending method such as a direct method or a master batch method, or a dry concentration method. And other methods. As a commercially available product which can be used as a material, for example, a polyoxyn resin powder, a polyoxyn composite powder, a polyoxymethylene rubber powder, etc., manufactured by Shin-Etsu Chemical Co., Ltd., may be mentioned. The content of the tantalum is preferably 20% by weight or more and 70% by weight or less based on the resin. When the content of the tantalum is 20% by weight or more, the softening temperature of the subsequent agent is sufficiently increased to suppress delamination. Moreover, if it is 7 重量% by weight or less, a sufficient adhesion can be maintained. Here, "the content of the dip in relation to the resin" means the content when the resin is 100% by weight. -8- 201224100 Further, the content of the dip material may be such that the amount of peeling of the wafer following the adhesive composition can be avoided, from the viewpoint of the increase in the softening temperature of the adhesive and the relaxation of the stress. The higher the better. Therefore, the content of the dip material is more preferably 50% by weight or more and 70% by weight or less. The average particle diameter of the dip material is preferably 0.5 μm or more and 5 μmη or less. Therefore, since it can be dispersed without sedimentation in the subsequent composition, its function can be fully exerted. Further, the average particle diameter of the tantalum is preferably 0.5 μm or more and Ιμηη or less from the viewpoint of alleviating the stress of the wafer. When an adhesive composition containing a coating material having such an average particle diameter is used, the amount of warpage of the wafer can be reduced when the wafer is applied to a high-temperature process after being applied to a glass substrate or the like. Therefore, the subsequent process flow is possible. Further, the heat resistance of the dip material is preferably 300 ° C or higher. Thereby, delamination can be effectively suppressed. In the present specification, "having heat resistance of 3001 or more" means that the weight change rate when heated from room temperature to 300 ° C is 1% or less. <Resin> The resin may be a binder, and examples thereof include a hydrocarbon resin, an acrylic-styrene resin, and a maleic imine resin. (hydrocarbon resin) The hydrocarbon resin may, for example, be a cycloolefin polymer (hereinafter also referred to as "tree (A)") and a group selected from the group consisting of a fire-retardant resin, a rosin-based resin, and a petroleum resin. At least one type of resin (hereinafter also referred to as "resin-9 - 201224100 (B)"), etc. is not limited thereto. The resin (A) may be a resin obtained by polymerizing a monomer having a cycloolefin-based monomer. Specifically, a resin obtained by addition (co)polymerization of a ring-opened (co)polymer containing a monomer component of a cycloolefin-based monomer and a monomer component containing a cycloolefin-based monomer can be mentioned. Examples of the cycloolefin-based monomer which is contained in the monomer component constituting the resin (A) include a bicyclic ring such as norbornene and norbornadiene, dicyclopentadiene, and dihydroxypentadiene. a tetracyclic ring such as a tricyclic or tetracyclododecene, a pentacyclic ring such as a cyclopentadiene terpolymer, a heptacyclic ring such as tetracyclopentadiene, or a polycyclic ring. Substituents (methyl, ethyl 'propyl, butyl, etc.), alkenyl (vinyl, etc.), alkylene (ethylene, etc.), aryl (phenyl, tolyl, naphthalene) Substrate, etc.). Among these, a norbornene-based monomer selected from the group consisting of norbornene, tetracyclododecene or such alkyl substituents is particularly preferred. The monomer component constituting the resin (A) may further contain another monomer copolymerizable with the above cycloolefin-based monomer, and for example, preferably contains an olefin monomer. Examples of the olefin monomer include ethylene, propylene, 1-butene, isobutylene, 1-hexene, and a-olefin. The olefinic system may be linear or branched. The monomer component constituting the resin (A) is preferably 50% by mass or more. The cycloolefin-based monomer is more preferably 60% by mass or more of the above-mentioned cycloolefin-based monomer. When the cycloolefin-based monomer is 50% by mass or more of the entire monomer component, the adhesion strength in a high-temperature environment is improved. In addition, the resin (A) is, for example, a resin obtained by polymerizing a monomer component composed of a cycloolefin monomer and an alkene-10-201224100 body, and is a resin having no polar group. The gas generation method is preferably a polymerization method or a polymerization condition in which the monomer component is polymerized, and is not particularly limited, and can be appropriately set according to a usual method. As a commercially available product of the tree S (A), for example, "T0PAS" manufactured by P〇iypiastics Co., Ltd., "APEL" manufactured by Mitsui Chemicals Co., Ltd., "ZE0N0R" and "ZE0NEX" manufactured by Zeon Corporation of Japan, and JSR are mentioned. "ARTON" made by the company. The glass transition point (Tg) of the resin (A) is preferably 6 (rc or more. Particularly preferably, the glass transition point of the resin (A) is 70 ° C or higher. If the resin (A ) has a glass transition point of 60 ° C In the above, when the adhesive composition is exposed to a high temperature environment, softening of the adhesive layer can be further suppressed. The tree fl曰 (B) is selected from at least a group consisting of a masking resin, a rosin resin, and a petroleum resin. Specific examples of the terpene-based resin include a terpene resin, a terpene phenol resin, a modified terpene resin, a hydrogenated terpene resin, a hydrogenated terpene phenol resin, etc. As the rosin-based resin, for example, Examples of the rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, modified rosin, etc. Examples of the petroleum resin include aliphatic or aromatic petroleum resins, hydrogenated petroleum resins, and modified petroleum resins. The alicyclic petroleum resin, the color sulphonic acid resin, etc. Among these, a hydrogenated terpene resin and a hydrogenated petroleum resin are preferable. The softening point of the resin (B) is not particularly limited, and is preferably 8 0~ 1 6 0 °C When the softening point of the resin (B) is 80 ° C or more, when the adhesive composition is exposed to a high temperature environment, the softening can be suppressed, and the subsequent failure does not occur. -11 - 201224100 On the other hand, the softening of the resin (B) When the point is 1 60 ° C or less, the peeling speed becomes good when the adhesive composition is peeled off. The molecular weight of the resin (B) is not particularly limited, but is preferably 300 to 3,000. The molecular weight of the resin (B) When it is 300 or more, the heat resistance is sufficient, and the amount of degassing in a high-temperature environment is small. On the other hand, when the molecular weight of the resin (B) is 300 or less, the peeling speed is removed when the adhesive composition is peeled off. Further, the molecular weight of the resin (B) of the present embodiment means a molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC). Further, as the resin, a resin (A) may be used. The mixture of the resin (B) is improved in heat resistance and peeling speed by mixing. For example, the mixing ratio of the resin (A) and the resin (B) is (A): (B) = 80: 20 to 5 5 : 45 (mass ratio), when peeling speed, high temperature environment It is preferable that it is excellent in resistance and flexibility. (Acrylic-styrene-based resin) Examples of the acrylic-styrene-based resin include a derivative of styrene or styrene and a (meth)acrylate. The (meth) acrylate may, for example, be an alkyl (meth) acrylate formed from a chain structure, a (meth) acrylate having an aliphatic ring, or an aromatic ring ( Methyl acrylate. Examples of the alkyl (meth) acrylate formed by the chain structure include an acrylic long-chain alkyl ester having an alkyl group having 15 to 20 carbon atoms and an alkyl group having 1 to 14 carbon atoms. Based on acrylic acid-12- 201224100 alkyl ester and the like. Examples of the acrylic long-chain alkyl ester include acrylic acid or methacrylic acid having an alkyl group of a n-pentadecyl group, a n-hexadecyl group, a n-heptadecyl group, a n-octadecyl group, a n-nonyl group, a n-octadecyl group or the like. Alkyl ester. Further, the alkyl group may also be branched. The acrylic alkyl ester having an alkyl group having 1 to 14 carbon atoms is a well-known acrylic alkyl ester used in the existing acrylic adhesive. For example, an alkyl group may be a methyl group, an ethyl group, a propyl group, a butyl group, a 2-ethylhexyl group, an isooctyl group, an isodecyl group, an isodecyl group, a dodecyl group, a lauryl group, a thirteen group or the like. An alkyl acrylate or methacrylate. Examples of the (meth) acrylate having an aliphatic ring include cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, 1-adamantyl (meth)acrylate, and (meth)acrylic acid. Norbornyl ester, isobornyl (meth)acrylate, tricyclodecyl (meth)acrylate, tetracyclododecyl (meth)acrylate, dicyclopentanyl (meth)acrylate, etc., more preferably methyl Isobornyl acrylate, dicyclopentanyl (meth)acrylate. The (meth) acrylate having an aromatic ring is not particularly limited, and examples of the aromatic ring include a phenyl group, a benzyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, and a fluorenyl group. , phenoxymethyl, phenoxyethyl and the like. Further, the aromatic ring may be a chain or branched alkyl group having 1 to 5 carbon atoms. Specifically, phenoxyethyl acrylate is preferred. (Malay ylide-based resin) Examples of the maleic imine-based resin include N-methyl maleimide, N-ethyl maleimide, and N-positive monomer. Propyl Malayan-13- 201224100 Amine, N-isopropylmaleimide, N-n-butylmaleimide, N-isobutylmaleimide, N-second Kamalyzide, N-tert-butylmaleimide, N-n-pentylmaleimide, N-n-hexylmaleimide, N-n-heptylmaleimide , N-n-octylmaleimide, N-lauryl maleimide, N-stearyl mercapine, etc., maleic imine having an alkyl group, N-cyclopropyl horse醯imine, N-cyclobutylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, N- An aromatic hydrocarbon group-containing maleic imine, N-phenylmaleimide, N-m-methylphenylmaleimide, N-o-methylbenzene, such as cyclooctylmaleimide A resin obtained by polymerization of an aromatic maleic imine having an aryl group such as carbamazepine or N-p-methylphenylmaleimide. <Preparation Method of Adhesive Composition> The adhesive composition of the present embodiment can be prepared by mixing the above resin and dip material using a well-known method. As the resin, a solution (resin solution) which is diluted with an organic solvent as needed may also be used. Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, ethylene glycol monoacetate, and diethyl benzene. Monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or a diol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol or dipropylene glycol monoacetate Polyols such as monophenyl ether and derivatives thereof; cyclic ethers such as dioxane; methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, acetone An ester such as ethyl acetate, methyl methoxypropionate or ethyl ethoxypropionate; and a terpene-14-201224100 solvent. These may be used alone or in combination of two or more. Examples of the terpene-based solvent include (X-pinene, decene, decane, geranyl, dihydrogeranene, p-captan, 3-decene, p-diene, and α-terpinene. , β-terpinene, α-phellandene, basilene, limonene, para-cymene, γ-terpinene, terpinene, 1,4-cineole, 1,8-cineole, oxidized rose , linalool, anthrone, alpha-cyclic citral, basilol, tetrahydrolinalol, linalool, tetrahydro-bilerolol, isopulegol, dihydrolinalol, isohydrohydrolavender Alcohol, β-ring citral, citronellal, L-fluorenone, linalyl lactate, dihydroterpineol, β-terpineol, capitol, geraniol L-caprolol, rosin,萜-terpineol, γ-terpineol, nodecyl alcohol, myrtenol, dihydrocarvacenol, citronellol, myrtenal, dihydrocarvone, d-propalone , geranyl ethyl ether, geranyl formate, neryl formate, decyl formate, iso-dihydro lavender acetate, decyl acetate, linalyl acetate, geranyl acetate, norbornic acetate Ester, propionate propionate, linalyl propionate, nerol, fragrant Celery, perillyl alcohol, geraniol, saffron aldehyde, citral, perillaldehyde, citronellyl oxyacetaldehyde, hydroxycitronellal, verbenone, d-carvone, L-carvone, mint Ketone, menthone, citronellyl formate, isobornyl acetate, capsid acetate, citronellyl acetate, decyl acetate, dimethyl octyl acetate, neryl acetate, isomentyl acetate, acetic acid Hydrocarbamide, norbyl acetate, geranyl acetate, norbornyl propionate, neryl propionate, carbitol propionate, terpene propionate, citronellate propionate, isobornyl propionate , linalyl isobutyrate, neroliate isobutyrate, linalyl butyrate, butyl succinate, terephthalate isobutyrate, terpene butyrate, geranyl isobutyrate, citronella butyrate Ester' citronellyl caproate, capric acid isovalerate, β_caryophyllene, snow-15- 201224100 pinene, erythro- diol, hydroxy citronellol, farnesol and, among them, dissolved From the viewpoint of the nature, it is particularly preferred to be decane. [Next film] The above-described adhesive composition of the present embodiment can be used in various ways. For example, a film which is formed on a workpiece such as a liquid wafer to form an adhesive layer, that is, a film which is rewritable in advance to form an adhesive containing any of the above-mentioned adhesive compositions (subsequent film) Adhesive to the object to be processed and film method). As described above, the adhesive film of the present embodiment is an adhesive layer of any of the above-described adhesive compositions. The softening temperature of the agent composition is high, and the high temperature process can be suppressed. Then, the film can be further coated on the adhesive layer. At this time, the protective film on the adhesive layer is peeled off, and after the exposed adhesive layer, the adhesive layer is easily provided on the adhesive layer from the adhesive layer. Therefore, if the adhesive thin body in the present embodiment is used, The adhesive composition is applied directly to the top to form a film thickness uniformity and surface smoothness. The adhesive layer formed on the film film used in the production of the film is peeled off from the film, and the difference is different. It is preferably a limonene butyrate and a direct application to a semi-conductive method according to the use, and can also be used for forming a film on a film or the like, and then drying and using the method (the film is provided with a film, therefore, Next, the layer is delaminated, and the film is laminated on the object to be processed, and the layer can be applied to the layer to be compared with the case of the layer to be added. 16-201224100 There is no release film to the surface to be treated such as a protective substrate or a wafer. For example, polyethylene terephthalate, polyethylene, polypropylene, and polycarbonate having a film thickness of 15 to 125 μm can be cited. A flexible film made of a synthetic resin film such as an ester or a polyvinyl chloride. The film is subjected to a release treatment in order to facilitate the transfer. As a method of forming an adhesive layer on the film, the film can be used as desired. The film thickness or uniformity of the layer is suitably determined by a well-known method. For example, an applicator, a bar coater, a wire bar coater, a roll coater, a curtain flow coater, or the like may be used for the film. The method of applying the agent composition of the present invention in the form of a dry film thickness of 10 to ΙΟΟΟμηι. Among them, a roll coater is preferred because of its excellent film thickness, and a thick thick film can be efficiently formed. Further, when the protective film is used, the protective film is not limited as long as it can be peeled off from the coating layer. For example, a polyethylene terephthalate film, a polypropylene film, or a polyethylene film is preferable. Further, each protective film is easy. The thickness of the coating or baking protective film is preferably not particularly limited from the viewpoint of peeling off the adhesive layer, and is preferably 15 from the viewpoint of ensuring the flexibility of the protective adhesive film. 125 μιηη The method of using the film is not particularly limited. For example, when the protective film is used, the adhesive layer which is exposed on the object after peeling off is peeled off on the film (the back surface of the formation layer of the adhesive layer) The heat roller is moved to adhere the adhesive layer to the object to be processed. At this time, the protective film peeled off from the film can be stored in a roll shape by a winding roller or the like. The use of a thin diester ester is preferred for thinning, and the cloth layer is followed by a uniform diester from the sand. The film 9 is stacked on the surface. The order of the surface is -17-201224100 [adhesive composition and subsequent film The use of the adhesive composition and the adhesive film of the present invention is not particularly limited as long as it is used for the subsequent use of the wafer, but can be suitably used to adhere the protective substrate for precision processing of the semiconductor wafer. Use of a substrate such as a semiconductor wafer. The present invention is not limited to the above embodiments, and various modifications are possible within the scope of the claims. In other words, the embodiment in which the technical means that are appropriately changed within the range indicated by the scope of the patent application is combined is also included in the technical scope of the present invention. [Examples] [Preparation of adhesive composition] A resin having an adhesive property was dissolved in p-tropane to form a resin solution having a resin solid content concentration of 30% by mass. Then, a crucible (based on the resin solid content) was added to the resin solution, and the mixture was mixed using a planetary mixer to prepare the adhesive compositions of Examples 1 to 10. As the material, either one of the raw material 1 or the raw material 2 of the polyoxygenated particles is used. As the dip material 1, a poly-oxygen resin powder of a three-dimensional crosslinked product of polyorganosilsesquioxane (RSi3/2) η ("ΚΜΡ-70 1" (product name); particle size 3.5 μηι, particle size distribution) 1~6μηι, heat resistance above 400 °C, manufactured by Shin-Etsu Chemical Co., Ltd.). As the coating material 2, a polyfluorene-oxygen composite powder ("X-5 2-703 0" (product name)) coated with a polyfluorene gas by a cerium resin; a particle size of 0.8 μm, a particle size distribution of 〜 2 to 2 μηι, 300 ° Heat resistance above C, Shin-Etsu -18-201224100 company system). As the resin having the adhesive property, either of the resin 1 or the resin 2 is used. As the resin 1, a cycloaliphatic copolymer ("TOPAS" (trade name) 8007, manufactured by Polyplastics Co., Ltd.) was used. Further, as the resin 2, a cycloolefin copolymer ("APEL" (trade name) 8008, manufactured by Mitsui Chemicals Co., Ltd.) was used. As the adhesive composition of the comparative example, the resin 1 was used to prepare a binder composition containing no mash. The composition of the adhesive compositions of Examples 1 to 10 and Comparative Examples is shown in Table 1 below. [Table 1] Dipping Content (% by weight) Resin Example 1 Dipping 1 10% Resin 1 Real® Γ~ Real ~~ Implementation Plant ~ 20% 50% 70% 2料 2 ------ --- 10% 20% 实~~~ 50% 70% 50% Resin 2 实βϋ' 70% Γ Γ 0% Resin 1% transfer point and softening point determination] ' π 'determination of each adhesive composition Glass transfer point and softening point. The celebrity ' Θ ' adhesive composition was applied to a 25 mm wafer at 15 ° C and 15 Torr. ", 20 (TC each dried for 3 minutes to form a coating film. For the coating film formed by -19-201224100, use Τ Μ A (thermomechanical analyzer) to measure the glass transition point of the adhesive composition (Tg And softening point (SP).Measured (the conditional load is 800mN/cm2, and the temperature rise mode is normal temperature ~200°C (5 °C / min). Under this condition, the starting point of the drop is regarded as the glass transition point. A larger drop starting point is taken as a softening point. Figs. 1 to 6 each show a graph of the measurement result using TM A for the adhesive composition of Example 3, 4, 7, 8, 9, or 1 本 of the present invention. Further, Fig. 7 is a graph showing the results of measurement using TMA for the adhesive composition of the comparative example of the present invention. Further, the glass transition point and the softening point obtained by the measurement results are shown in Table 2 below. [Table 2] Glass transition point softening point (°c) (°C) Example 3 73.2 166 Example 4 6 6.0 164 Example 7 68.0 154 Example 8 68.6 177 Example 9 60.9 163 Implementation Initial 1 0 60.9 194 Comparison Example 68.0 153 As shown in Table 2, Examples 3, 4, 7, 8, 9 and 10 The composition of the primer showed a higher softening point and a higher softening temperature than the comparative example. Moreover, this effect was obtained regardless of the kind of the resin to be used. Examples 3, 4, 7, and 8. Use of the adhesive composition of 9 and 10 Τ The measurement result of Μ A (Figs. 1 to 6) ' shows a different behavior from the comparative example (Fig. 7). The implementation of the mash 1 containing a particle size of 3.5 μm In the primer compositions of Examples 3 and 4, the composition of the composition of -20-201224100 was moderated at a temperature of 120 ° C to 150 ° C. Further, an example of the material 2 containing a particle size of 〇 8 μm In the adhesive compositions of 7 and 8, the decrease from room temperature to about 1 70 ° C was smaller than that of the comparative examples, Examples 3 and 4. Therefore, it was suggested that the binder contained in the adhesive composition was The smaller the particle size, the higher the softening temperature. [Measurement of Stress] Next, measure the stress (membrane stress) when each of the adhesive compositions is used. 〇 Apply these adhesive compositions to a 125 mm wafer. Drying at 10 ° C, 150 ° C, and 200 ° C for 3 minutes to form an adhesive layer, followed by a glass substrate on the adhesive layer Then, the stress at 23 ° C was measured using a warpage/film stress measuring device (FLX-2908, manufactured by KLA-Tencor Co., Ltd.). The results are shown in Fig. 8 and Table 3 below. Fig. 8 shows the use of the present invention. A graph showing the relationship between the content of the tantalum and the stress in the composition of the adhesive of each embodiment of the invention. As shown in Fig. 8 and Table 3, especially in the use of the adhesive composition containing the coating 2 (Example 5~ 8) When the content of the tanning material is increased, the stress is reduced. -21 - 201224100 [Table 3] Film thickness (μιη) Warpage (μιη) Stress (MPa) Example 1 12.4 13.56 8.3 Example 2 12.6 18.80 9.0 Example 3 34.2 46.26 9.3 Example 4 36.5 46.49 8.4 Example 5 12.7 16.23 8.0 Example 6 14.1 18.34 7.9 Example 7 55.9 55.10 6.3 Example 8 54.3 48.89 3.2 Comparative Example 1 1.4 19.25 9.3 Therefore 'shows that by using a binder-containing adhesive composition, stress can be relieved' The amount of warpage. In particular, it has been found that by containing 50% by weight or more of the tantalum, it is possible to obtain a higher effect in connection with the relaxation of stress. Further, the smaller the particle size of the dip, the higher the effect of relieving the stress. [Industrial Applicability] The adhesive composition and the adhesive film of the present invention can be applied to a processing step of a semiconductor wafer or the like. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the results of measurement using a TMA (thermomechanical analyzer) for the adhesive composition of Example 3 of the present invention. Fig. 2 is a graph showing the results of measurement using TMA for the adhesive composition of Example 4 of the present invention. Fig. 3 is a graph showing the results of measurement using TMA for the composition of the adhesive of Example 7 of the present invention. -22-201224100 Fig. 4 is a graph showing the results of measurement using TMA for the adhesive composition of Example 8 of the present invention. Fig. 5 is a graph showing the results of measurement using TMA for the adhesive composition of Example 9 of the present invention. Fig. 6 is a graph showing the results of measurement using TM A for the adhesive composition of Example 1 of the present invention. Fig. 7 is a graph showing the results of measurement using TMA for the adhesive composition of the comparative example of the present invention. Fig. 8 is a graph showing the relationship between stress and the content of the crucible when the composition of the adhesive of each embodiment of the present invention is used. -twenty three-

Claims (1)

201224100 七、申請專利範圍： 1 ·—種接著劑組成物，其係接著晶圓用的接著劑組成 物，其特徵爲含有具備接著性的樹脂、與塡料。 2 ·如申請專利範圍第1項之接著劑組成物，其中相對 於上述樹脂而言，上述塡料的含有率爲20重量％以上70重 量％以下。 3 .如申請專利範圍第1或2項之接著劑組成物，其中上 述塡料的平均粒徑爲0.5μηι以上5μιη以下。 4.如申請專利範圍第1〜3項中任一項之接著劑組成物 ，其中上述塡料係無機塡料。 5 ·如申請專利範圍第1〜4項中任一項之接著劑組成物 ，其中上述塡料的耐熱性爲30(TC以上。 6 _如申請專利範圍第1〜5項中任一項之接著劑組成物 ，其中上述樹脂係烴樹脂。 7 ·如申請專利範圍第6項之接著劑組成物，其中上述 烴樹脂係選自由環烯烴系聚合物、萜烯樹脂、松香系樹脂 及石油樹脂所成之群組。 8.—種接著晶圓用的接著薄膜，其特徵爲在薄膜上具 備含有如申請專利範圍第1〜7項中任一項之接著劑組成物 的接著劑層。 -24-201224100 VII. Patent Application Range: 1 - An adhesive composition, which is an adhesive composition for a wafer, which is characterized by containing a resin having an adhesive property and a coating material. The adhesive composition according to the first aspect of the invention, wherein the content of the above-mentioned dip is 20% by weight or more and 70% by weight or less based on the resin. 3. The adhesive composition according to claim 1 or 2, wherein the above-mentioned pigment has an average particle diameter of 0.5 μm or more and 5 μm or less. 4. The adhesive composition according to any one of claims 1 to 3, wherein the above-mentioned tanning material is an inorganic tanning material. The adhesive composition according to any one of claims 1 to 4, wherein the heat resistance of the above-mentioned material is 30 (TC or more. 6 _ as claimed in any one of claims 1 to 5) The composition of the above-mentioned resin-based hydrocarbon resin. The adhesive composition according to claim 6, wherein the hydrocarbon resin is selected from the group consisting of a cyclic olefin polymer, a terpene resin, a rosin resin, and a petroleum resin. 8. The adhesive film for the subsequent wafer, characterized in that the film is provided with an adhesive layer containing the adhesive composition according to any one of claims 1 to 7 of the patent application. twenty four-
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