TWI724765B - 可雷射離型的組成物、其積層體和雷射離型方法 - Google Patents

可雷射離型的組成物、其積層體和雷射離型方法 Download PDF

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TWI724765B
TWI724765B TW109102238A TW109102238A TWI724765B TW I724765 B TWI724765 B TW I724765B TW 109102238 A TW109102238 A TW 109102238A TW 109102238 A TW109102238 A TW 109102238A TW I724765 B TWI724765 B TW I724765B
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TW202128791A (zh
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邱士芸
李政緯
林季延
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達興材料股份有限公司
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Priority to TW109102238A priority Critical patent/TWI724765B/zh
Priority to JP2021005034A priority patent/JP7133047B2/ja
Priority to CN202110075829.8A priority patent/CN113214588B/zh
Priority to US17/152,819 priority patent/US11794381B2/en
Priority to KR1020210008796A priority patent/KR102537045B1/ko
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Abstract

本發明提供一種可雷射離型的組成物，包含：壓克力樹脂、遮光材、添加劑和溶劑；其中前述之壓克力樹脂包含含有選自叔胺基和仲胺基之群中至少一種之含氮有機基、含有環醚基之有機基和含有羥基之有機基，前述之添加劑至少包含一種密著促進劑。所述可雷射離型的組成物具有優異的基材密著性、可貼合性和耐溶劑性。

Description

可雷射離型的組成物、其積層體和雷射離型方法
本發明係關於一種組成物，特別係關於一種可雷射離型的組成物、使用其所形成的積層體和利用所述組成物或所述積層體的雷射離型方法。
近年來，為了因應市場要求效能更快速、更便宜以及尺寸更小的電子產品，扇出型晶圓級封裝(Fan Out Wafer Level Package, FOWLP)、2.5維度積體電路(2.5D IC)以及三維積體電路(3D IC)等技術早已成為半導體封裝的主流。為了不讓薄化矽晶圓的翹曲以及易脆等特性影響後續的製程，載體(Carrier)的使用已變成不可或缺的一個步驟。然而，在產品尺寸更小的需求下，載體最終必須要移除，因此封裝技術時常伴隨著離型層(releasing layer)的使用，也因此創造了離型層的市場。雷射離型雖有較昂貴的設備需求，但有在低溫下快速將載體脫離裝置的優點，使其躍身為現今主流的離型技術。
而為了使離型層上方能進行不同製程，例如：線路重佈(Redistribution Layer)、銲晶(Die bonding)、封膠(Molding)、晶圓研磨、晶片翻轉等，且因應各種不同的製程需求，形成離型層之材料需要有優異的基材密著性以及耐溶劑性。然而，在現今技術中，含有遮光材的材料往往因為材料的不連續面增加，而會導致耐溶劑特性下降。
因此，針對上述問題，本發明提供一種具有優異的基材密著性、可貼合性和耐溶劑性的可雷射離型組成物。
本發明之一目的在於提供一種可雷射離型的組成物。前述之可雷射離型的組成物包含:壓克力樹脂、遮光材、添加劑和溶劑；其中前述之壓克力樹脂包含含有選自叔胺基和仲胺基之群中至少一種之含氮有機基 、含有環醚基之有機基和含有羥基之有機基，前述之添加劑至少包含一種密著促進劑。
在本發明的一實施方式中，前述之壓克力樹脂的酸價為小於4mg/g。
在本發明的一實施方式中，前述之密著促進劑為包含選自乙烯性基團、環氧基和異氰酸酯基中至少一種的矽氧烷化合物。
在本發明的一實施方式中，前述之含有選自叔胺基和仲胺基之群中至少一種之含氮有機基 ，可為但不限於2-(烴基)胺基烴基酯基團、二烴基胺基烴基酯基團、胺基甲酸酯基團、吡啶、哌嗪和嗎啉基團中的至少一種。
在本發明的一實施方式中，前述之壓克力樹脂包含至少兩種以上具有不同碳數的環的環醚基。
在本發明的一實施方式中，前述之環醚基為氧雜環丁烷基、環氧丙基或其組合。
在本發明的一實施方式中，前述之遮光材為可使可雷射離型的組成物吸收可見光、紅外光或紫外光中至少一波段或阻擋可見光、紅外光或紫外光中至少一波段通過的材料。
本發明之另一目的在於提供一種積層體。所述之積層體包含一支撐材及以如上述之可雷射離型的組成物在所述支撐材上所形成的膜。
本發明之另一目的在於提供一種雷射離型方法，包含以下步驟: S1:提供一支撐材；S2:以如上述之可雷射離型的組成物塗布在所述支撐材上並硬化成膜；S3:可在前述膜上形成一加工元件；及S4:以雷射將所述支撐材移除。
在本發明的一實施方式中，前述之加工元件為裸晶或線路重佈層。
在詳細說明本發明的至少一實施例之前，應當理解的是本發明並非必要受限於其應用在以下描述中的多個示例所舉例說明的多個細節，例如，實施例的數量或採用之特定混合比例等。本發明能夠爲其他的實施例或者以各種方式被實施或實現。
[可雷射離型組成物]
本發明提供一種具有優異的基材密著性、可貼合性、轉印性和耐溶劑性的可雷射離型組成物，其包含壓克力樹脂、遮光材、添加劑和溶劑。以下將就各成分進行詳細說明:
[壓克力樹脂]
為了達成上述功效，本發明所揭露之一種實施方式，其中壓克力樹脂至少包含含有選自叔胺基和仲胺基之群中至少一種之含氮有機基 、含有環醚基之有機基和含有羥基之有機基。
前述含有選自叔胺基和仲胺基之群中至少一種之含氮有機基可為但不限於 吡啶基團、哌嗪基團、嗎啉基團、2-(烴基)胺基烴基酯基團、二烴基胺基烴基酯基團、胺基甲酸酯基團等，其中前述烴基中任一-CH 2-亦可以各自獨立為-NH-、-O-或-S-取代，其中各取代基彼此不相連接，具體而言，可使用含有選自叔胺基或仲胺基之群中至少一種之單體進行樹脂合成，例如、丙烯醯嗎啉、甲基丙烯醯嗎啉、4-乙烯基吡啶、2-乙烯基吡啶、5-乙基-2-乙烯基吡啶、N-丙烯醯基哌嗪、2-(叔丁基氨基)甲基丙烯酸乙酯、丙烯酸二甲基胺基乙基酯、甲基丙烯酸二甲基胺基乙基酯、丙烯酸二乙基胺基乙基酯、甲基丙烯酸二乙基胺基乙基酯、丙烯酸二乙基胺基丙基酯、甲基丙烯酸二乙基胺基丙基酯、丙烯酸胺基甲酸酯、甲基丙烯酸胺基甲酸酯等。
前述含環醚基之有機基可為但不限於氧雜環丁烷基團、環氧丙基等，具體而言，可使用例如含環醚基之單體進行樹脂合成，例如(甲基)丙烯酸縮水甘油酯、烯丙基縮水甘油基醚、α－乙基丙烯酸縮水甘油酯、巴豆醯基縮水甘油基醚、(異)巴豆酸縮水甘油基醚、甲基丙烯酸氧雜環丁烷酯、丙烯酸氧雜環丁烷酯等。
前述含有羥基之有機基，可使用含有羥基之單體進行樹脂合成，包含但不限於(甲基)丙烯酸羥基烷基酯，具體可例舉如:甲基丙烯酸羥基乙酯、丙烯酸羥基乙酯、甲基丙烯酸羥基丙酯、丙烯酸羥基丙酯、甲基丙烯酸羥基丁酯、丙烯酸羥基丁酯、甲基丙烯酸羥基己酯、丙烯酸羥基己酯等。前述含有羥基之有機基亦可透過接枝聚合的方式形成。例如先使樹脂主鏈帶有羧基而形成具有羧基之樹脂，再使用環氧化合物接枝聚合，使羧基與環氧基反應而產生羥基；具體而言，前述之具有羧基之樹脂並不特別限制，一般而言係使含有羧基之聚合性單體進行聚合而得，亦可以多元酸和多元醇聚合而成的含有羧基之聚酯作為前述具有羧基之樹脂。所述含有羧基之聚合性單體包含但不限於(甲基)丙烯酸，順丁烯二酸或順丁烯二酐，巴豆酸，亞甲基丁二酸，反丁烯二酸，2－(甲基)丙烯醯氧乙基丁二酸，2－丙烯醯氧乙基己二酸，2－(甲基)丙烯醯氧乙基酞酸，2－(甲基)丙烯醯氧乙基六氫酞酸，2－(甲基)丙烯醯氧乙基順丁烯二酸，2－(甲基)丙烯醯氧丙基丁二酸，2－丙烯醯氧丙基己二酸，2－(甲基)丙烯醯氧丙基氫酞酸，2－(甲基)丙烯醯氧丙基酞酸，2－(甲基)丙烯醯氧丙基順丁烯二酸，2－(甲基)丙烯醯氧丁基丁二酸，2－丙烯醯氧丁基己二酸，2－(甲基)丙烯醯氧丁基氫酞酸，2－(甲基)丙烯醯氧丁基酞酸，2－(甲基)丙烯醯氧丁基順丁烯二酸等。所述用於接枝聚合的環氧化合物只要具有環氧基皆可，可例舉如下: 環氧乙烷、環氧丙烷、(甲基)丙烯酸縮水甘油酯、烯丙基縮水甘油基醚、α－乙基丙烯酸縮水甘油酯、巴豆醯基縮水甘油基醚、(異)巴豆酸縮水甘油基醚等，但不限於此；除此之外，羥基亦可由醛、酮或羧酸還原得到。
較佳地，本發明之壓克力樹脂包含至少兩種以上具有不同碳數的環的環醚基；更佳地，所述至少兩種以上具有不同碳數的環的環醚基為氧雜環丁烷基團和環氧丙基之組合。
本發明所揭露之實施方式所含有選自叔胺基和仲胺基之群中至少一種之含氮有機基 、含有環醚基之有機基和含有羥基之有機基的比例沒有一定的限制，只要不影響本發明之密著性和耐溶劑性皆可。具體而言，以壓克力樹脂整體之固含量為100重量%，含有選自叔胺基或仲胺基之群中至少一種之含氮有機基之單體為1~50重量%，較佳為3~35重量%，更佳為5~20重量%；含有環醚基之單體為5~65重量%，較佳為10~50重量%，更佳為15~35重量%；含有羥基之單體為1~75重量%，較佳為3~60重量%，更佳為5~45重量%。
進一步地，在壓克力樹脂中，所述含有環醚基之有機基和所述含氮有機基之重量比為1:0.015~1:10，較佳為1:0.05~1:3.5，更佳為1:0.17~1:0.67；所述含有環醚基之有機基和所述含有羥基之有機基之重量比為1:0.015~1:25，較佳為1:0.05~1:6，更佳為1:0.17~1:2.3；所述含氮有機基和所述含有羥基之有機基之重量比為1:0.02~1:60，較佳為1:0.1~1:20，更佳為1:1~1:6。
在不影響本發明的特性下，本發明所揭露的壓克力樹脂可進一步包含其他官能基團，如芳香環基團、脂環基團、矽氧烷基團、羧酸基團等，但不限於此。具體而言，具有芳香環基團的單體如苯乙烯、鄰苯基苯氧乙基丙烯酸酯等；具有脂環基團的單體如甲基丙烯酸三環[5.2.1.02,6]癸-8-基酯等；具有矽氧烷基團的單體如甲基丙烯醯氧基丙基三甲氧基矽烷等；具有羧酸基團的單體如甲基丙烯酸、丙烯酸等。其他官能基團的比例沒有一定的限制，只要不影響本發明之密著性和耐溶劑性皆可。具體而言，以壓克力樹脂整體之固含量為100重量%，具有其他官能基團之單體為0~80重量%，較佳為0~60重量%，更佳為20~50重量%。
前述之壓克力樹脂之重量平均分子量為6萬以上，較佳為7~14萬，更佳為8~10萬，以達成優異之密著性和耐溶劑性。於本發明之可雷射離型組成物之整體固含量中，壓克力樹脂之比例並無特別限制，只要不影響本發明之密著性和耐溶劑性皆可。具體而言，壓克力樹脂佔可雷射離型組成物之整體固含量為5~70重量%，較佳為7~55重量%，更佳為10~40重量%。
且較佳地，前述之壓克力樹脂之酸價為小於4mg/g，以達成本發明優異之密著性和耐溶劑性。
[遮光材]
本發明所揭露的遮光材只要可使所述可雷射離型組成物吸收可見光、紅外光或紫外光中至少一波段或阻擋可見光、紅外光或紫外光中至少一波段通過的材料皆可。藉由遮光材的添加，可利用對應其特定波段之雷射將可雷射離型的組成物所形成之薄膜與支撐材分離。作為遮光材的材料可列舉如下，包含但不限於: 碳黑、鈦黑、氧化鈦、氧化鐵、鈦氮化物、矽灰、有機顏料、無機顏料、染料或其組合等。
較佳地，前述之遮光材不含金屬離子。
遮光材之比例並無特別限制，只要不影響本發明之密著性和耐溶劑性皆可；具體而言，遮光材佔可雷射離型組成物之整體固含量為20~90重量%，較佳為35~85重量%，更佳為50~70重量%。另外，本發明所揭露之樹脂可使遮光材的添加比例高於50重量%，適用上可降低雷射離型所需的能量。
[添加劑]
添加劑如密著促進劑、交聯劑等。密著促進劑可為矽烷類、矽氧烷類的化合物或界面活性劑；較佳地，密著促進劑為包含乙烯性基團、環氧基、胺基、酸酐、硫醇基或異氰酸酯基等的矽氧烷化合物，更佳地，密著促進劑為包含具有乙烯性基團的矽氧烷化合物。交聯劑較佳為熱交聯劑；熱交聯劑可為含封端型或非封端型異氰酸酯基之化合物、如二乙烯基醚之含有烯基醚基之化合物、含烴氧基烴基之化合物、含雙酸酐基之化合物、含雙硫醇基之化合物、環氧樹脂、三聚氰胺化合物、酚化合物等。添加劑可為一種或兩種以上之組合。
較佳地，添加劑至少包含一種密著促進劑；更佳地，添加劑至少包含一種密著促進劑和一種交聯劑。
具體而言，密著促進劑可例舉為[3-(2,3-環氧丙氧)-丙基]三甲氧基矽烷、3-異氰酸酯基丙基三甲氧基矽烷、3-(甲基丙烯醯氧基)丙基三甲氧基矽烷等；熱交聯劑可例舉為六羥甲基三聚氰胺、六甲氧基甲基三聚氰胺、三羥甲基酚、3,3',5,5'-四甲氧甲基聯苯二酚、酚醛環氧樹脂等。
添加劑之比例並無特別限制，只要不影響本發明之密著性和耐溶劑性皆可。具體而言，添加劑佔可雷射離型組成物之整體固含量為5~35重量%，較佳為7~25重量%，更佳為10~15重量%。
[溶劑]
溶劑可為醯胺類、環醯胺類、酯類、醚類、醇類或是上述溶劑任意比例之混合溶劑。可列舉如下，包含但不限於: N-甲基吡咯烷酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基己內醯胺、二甲基亞碸、四甲基尿素、六甲基磷醯胺、γ-丁內酯、吡啶、甲醇、乙醇、異丙醇、正丁醇、環己醇、乙二醇、乙二醇甲基醚、乙二醇單乙基醚、乙二醇單丁基醚、乙二醇二甲基醚、乙二醇二乙基醚、二乙基醚、丙酮、甲基乙基酮、環己酮、乙酸甲酯、乙酸乙酯、四氫呋喃、二氯甲烷、三氯甲烷、1,2-二氯乙烷、苯、甲苯、二甲苯、正己烷、正庚烷、正辛烷等。溶劑之比例並無特別限制，只要不影響本發明之密著性和耐溶劑性，且可塗布成膜皆可。
[複合膜]
本發明的可雷射離型組成物亦可用於形成具有轉印功能的複合膜；前述之複合膜包含可離型支撐膜及由本發明的可雷射離型組成物所形成的暫時黏著膜，其中，暫時黏著膜設置於可離型支撐膜之一表面。詳細來說，將可雷射離型的組成物塗布於支撐材之表面，並加熱去除部分或全部溶劑後而得，且複合膜中的暫時黏著膜可被剝離。
作為可離型支撐膜之材料可包含但不限於聚對苯二甲酸乙二酯(PET)、聚乙烯、聚丙烯、聚碳酸酯、聚氯乙烯等之膜厚15~200 μm的合成樹脂薄膜；暫時黏著膜遠離可離型支撐膜的另一表面亦可設置保護膜覆蓋。
另外，前述塗布方式可包含但不限於旋轉塗布、狹縫塗布、線棒塗布、網版印刷等。
[積層體]
本發明更提供一種積層體。本發明之積層體包含支撐材及如上所述之可雷射離型的組成物在支撐材上所形成的暫時黏著膜。詳細來說，將可雷射離型的組成物塗布於支撐材之表面，並加熱去除部分或全部溶劑後而得；亦可將前述之複合膜以轉印的方式形成於支撐材之表面。
作為本發明之支撐材並不限定，只要可被雷射穿透的材料皆可。例舉如: 玻璃、矽晶圓等。
利用本發明之可雷射離型組成物在支撐材上形成膜的塗布方式並不限定，只要能在支撐材上塗布成膜皆可，如:旋轉塗布、刮刀式塗布等。
塗布完成後，以40°C ~100°C之預烘烤溫度在熱板上加熱5~20分鐘以去除溶劑，再以200°C ~300°C加熱30~60分鐘以固化成膜。
[雷射離型方法]
本發明更提供一種雷射離型方法。包含以下步驟:
S1:提供支撐材1；
S2:以上述之可雷射離型的組成物塗布在前述之支撐材上並硬化成膜2；
S3:在膜2上形成加工元件3；及S4:以雷射將支撐材1移除。
具體而言，步驟S1和S2即為上述積層體之提供步驟。且進一步地，步驟S2亦可用轉印之方法完成，即以前述之可雷射離型的組成物所形成的暫時黏著膜轉印在前述支撐材之一表面上。
具體而言，步驟S3所述之加工元件可為裸晶(KGD)或線路重佈層(RDL)；且進一步地，所述之加工元件若為裸晶(KGD)，則步驟S3更包含封膠(molding)；所述之加工元件若為線路重佈層(RDL)，則步驟S3更包含焊晶(die bonding)、封膠(molding)等步驟。
具體而言，步驟S4所使用之雷射種類並無特別限制，可包含YAG雷射、紅寶石雷射、YVO4雷射、光纖雷射等之固體雷射、色素雷射等之液體雷射、CO2雷射、準分子雷射、Ar雷射、He-Ne雷射等氣體雷射、半導體雷射、半導體激發固體雷射（Diode Pump Solid State Laser，DPSSL）、自由電子雷射等。
且進一步地，步驟S4更可包含以雷射將支撐材1去除後的清潔步驟以去除本發明之可雷射離型組成物所形成的殘膜，和焊錫(solder printing)等步驟。所述清潔步驟具體而言，如使用電漿之乾式蝕刻、使用化學藥劑之溼式蝕刻等。
因應其應用領域之不同，除了半導體領域的應用之外，只要任一基板、材料或加工元件需藉由本發明之積層體，而後進行一或多道製程，最後再利用雷射分離本發明之積層體與基板、材料或加工元件，皆為本發明之雷射離型方法之範疇。
[實施例]
壓克力樹脂的合成:
於1 L反應釜中，架設溫度計、滴定管、氮氣入氣孔以及攪拌棒裝置。首先加入150克的丙二醇甲基醚醋酸酯(PGMEA)於釜底以轉速200 rpm攪拌升溫至85°C，接著將不同重量比例的單體以及0.005 mol的偶氮二異丁腈混於150克的PGMEA中，以滴定的方式滴入反應釜中，接著保持溫度攪拌4小時，即可降至室溫完成反應，可得固含量為40%的樹脂。
可雷射離型組成物的配製:
首先將密著促進劑以及交聯劑加入具有20% N,N-二乙基甲醯胺(DEF)及80%丙二醇甲基醚醋酸酯(PGMEA)之混和溶劑，確認混合均勻後，再將樹脂加入並混合均勻後，最後加入遮光材(自達興材料購入，PK260)並攪拌1小時，可得固含量為20%的組成物。
積層體的形成:
將表1~表3中所示比例之組成物，以可形成1.3µm膜厚之轉速，旋轉塗佈於一玻璃支撐體上，經由50°C和90°C各5分鐘之預烘烤去除溶劑後，待膜表面乾燥後，再以230°C加熱30分鐘以固化成膜，而形成積層體。
耐溶劑性測試: 於80°C浸泡光阻去除劑(AT7880P，從品化購入)，分別於不同時間點進行百格測試，測試手法遵循ASTM D3359來進行判斷剝落情況。AT7880P組成為二甲基亞碸、乙醇胺和氫氧化四甲基銨。(表中: ◎代表浸泡時間大於10分鐘後進行百格測試為5B；O 代表浸泡10分鐘後進行百格測試為5B；△代表浸泡5分鐘後進行百格測試為5B；X代表不論浸泡時間皆未達5B。)
密著性測試: 使用拉力機進行拉力測試 (Pull off test)。首先利用框膠(723K1，從AUO購入)定量點於塗佈試片上，上層黏著玻璃，以355nm的UV燈照射169秒進行光固化之步驟，且熱固化120度1小時，最後進行拉力測試，確認塗層與剝離所需的力，且將其除以框膠之面積，即為拉應力(tensile stress)。此處以玻璃對貼片拉應力數值作為標準品，定義為2 N/mm 2，將所有拉應力的樣品規格化後，即可得到數值。
可雷射離型測試: 使用1瓦或1瓦以上能量之355nm雷射進行連續掃描後，可利用黏著紙(protect film)撕起之材料，稱之可雷射離型。
下列實施例均為可雷射離型。
樹脂成分說明:
OXMA: 甲基丙烯酸氧雜環丁烷酯；GMA: 甲基丙烯酸缩水甘油酯；ACMO: 丙烯醯嗎啉；HEMA: 甲基丙烯酸羥基乙酯；FA513M: 甲基丙烯酸三環[5.2.1.02,6]癸-8-基酯；EM2105: 鄰苯基苯氧乙基丙烯酸酯；EM50: 苯乙烯；A174: 甲基丙烯醯氧基丙基三甲氧基矽烷；DMAEMA：丙烯酸二甲基胺基乙基酯。
添加劑成分說明:
X-12-1050:具有二個以上壓克力官能基之矽氧烷聚合物(從信越購入)；Alink: 3-異氰酸酯基丙基三甲氧基矽烷；AD124: [3-(2,3-環氧丙氧)-丙基]三甲氧基矽烷；N740: 酚醛環氧樹脂；TMOM-BP: 3,3',5,5'-四甲氧甲基聯苯二酚；HMMM: 六甲氧基甲基三聚氰胺。
表1:實施例1~實施例6
固體組成 實施例 1 實施例 2 實施例 3 實施例 4 實施例 5 實施例 6
樹脂組成 (wt%) OXMA 15 30 30 15 25 -
GMA - - - - - 35
ACMO 10 10 10 20 5 20
HEMA 35 40 40 20 30 45
FA513M 15 - - 15 25 -
EM2105 25 - - 25 15 -
EM50 - 20 20 - - -
A174 - - - 5 - -
樹脂 wt% 13 23 42 23 29 23
遮光材 wt% 73 63 44 63 57 63
添加劑 wt% 14 14 14 14 14 14
添加劑組成 (wt%) X-12-1050 27 27 27 27 27 27
Alink 40 40 40 40 40 40
AD124 - - - - - -
N740 - - - - - -
TMOM-BP - - - - - -
HMMM 33 33 33 33 33 33
耐溶劑性 ◎ ◎ ◎ ◎ ◎ ◎
密著性 0.589 0.618 1.087 0.528 0.929 0.589
表2:實施例7~實施例13
固體組成 實施例 7 實施例 8 實施例 9 實施例 10 實施例 11 實施例 12 實施例 13
樹脂組成 (wt%) OXMA 17 35 35 25 25 25 15
GMA 17 - - - - - -
ACMO 21 20 20 5 5 5 20
HEMA 45 45 45 30 30 30 25
FA513M - - - 25 25 25 15
EM2105 - - - 15 15 15 25
EM50 - - - - - - -
A174 - - - - - - -
樹脂 wt% 23 23 7 23 24 23 23
遮光材 wt% 63 63 79 63 66 63 63
添加劑 wt% 14 14 14 14 10 14 14
添加劑組成 (wt%) X-12-1050 27 27 27 27 - 27 27
Alink 40 40 40 - 55 - 40
AD124 - - - 40 - 40 -
N740 - - - - - - 33
TMOM-BP - - - - - 33 -
HMMM 33 33 33 33 45 - -
耐溶劑性 ◎ ◎ ◎ ◎ ◎ ◎ O
密著性 1.103 0.696 0.862 0.536 0.503 0.803 0.608
表3:實施例14~實施例16&比較例1~比較例4
固體組成 實施例 14 實施例 15 實施例 16 比較例 1 比較例 2 比較例 3 比較例 4
樹脂組成 (wt%) OXMA 25 30 - - 20 - 58
GMA - - 15 - - - -
ACMO 5 5 10 - - 38 42
HEMA 30 5 25 - 35 62 -
FA513M 25 30 25 - 20 - -
EM2105 15 30 25 - 25 - -
EM50 - - - - - - -
A174 - - - - - - -
樹脂 wt% 23 31 31 0 13 23 23
遮光材 wt% 63 60 60 82 73 63 63
添加劑 wt% 14 9 9 18 14 14 14
添加劑組成 (wt%) X-12-1050 27 0.4 0.4 27 27 27 27
Alink 40 0.6 0.6 40 40 40 40
AD124 - - - - - - -
N740 33 - - - - - -
TMOM-BP - - - - - - -
HMMM - - - 33 33 33 33
耐溶劑性 ◎ ◎ O X O ◎ ◎
密著性 0.647 1.196 1.037 0.281 0.398 0.271 0.279
表4:實施例17~實施例19
固體組成 實施例 17 實施例 18 實施例 19
樹脂組成 (wt%) OXMA 25 25 25
GMA - - -
ACMO 5 5 -
HEMA 30 30 30
FA513M 25 25 25
EM2105 15 15 15
EM50 - - -
DMAEMA - - 5
樹脂 wt% 24 24 23
遮光材 wt% 66 66 63
添加劑 wt% 10 10 14
添加劑組成 (wt%) X-12-1050 55 - 27
Alink - - 40
AD124 - 55 -
N740 - - -
TMOM-BP - - -
HMMM 45 45 33
耐溶劑性 ◎ ◎ O
密著性 0.829 0.572 1.64
從實施例和比較例1~4可知，沒有同時包含含有選自叔胺基和仲胺基之群中至少一種之含氮有機基 、環醚基和羥基的樹脂，無法達成本發明優異的耐溶劑性或密著性；從實施例7和實施例8可知，樹脂具有兩種環醚基團的組成物，具有較佳之密著性；從實施例11、實施例17和實施例18可知，包含具有乙烯性基團的矽氧烷化合物的組成物具有較佳的密著性，包含具有環氧基的矽氧烷化合物或具有異氰酸酯基的矽氧烷化合物則次之。
[應用領域]
本發明的可雷射離型組成物、及其積層體除了半導體封裝領域的應用之外，只要任一支撐材或材料需藉由一暫時載體乘載，而後進行一或多道製程，最後再利用雷射分離載體與支撐材或材料，皆為本發明可適用之範圍。例如：軟性支撐材或是太陽能電池製作。
雖然本發明已以實施方式揭露如上，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍內，皆可作各種更動與潤飾，因此本發明之保護範圍，當視後附之申請專利範圍所界定者為準。
S1:步驟1 S2:步驟2 S3:步驟3 S4:步驟4 1:支撐材 2:膜 3:加工元件
[圖1]為根據本發明的一實施例之雷射離型方法的流程示意圖。

Claims (12)

  1. 一種可雷射離型的組成物，包含：一壓克力樹脂、一遮光材、一添加劑和一溶劑；其中該壓克力樹脂包含含有選自叔胺基和仲胺基之群中至少一種之含氮有機基、含有環醚基之有機基和含有羥基之有機基，該添加劑至少包含一種密著促進劑；其中，在該壓克力樹脂中，該含有環醚基之有機基和該含氮有機基之重量比為1：0.015~1：10，該含有環醚基之有機基和該含有羥基之有機基之重量比為1：0.015~1：25，該含氮有機基和該含有羥基之有機基之重量比為1：0.02~1：60。
  2. 如申請專利範圍第1項所述之可雷射離型的組成物，其中，該壓克力樹脂的酸價為小於4mg KOH/g。
  3. 如申請專利範圍第1項或第2項所述之可雷射離型的組成物，其中，該密著促進劑為包含選自乙烯性基團、環氧基和異氰酸酯基之群中至少一種的矽氧烷化合物。
  4. 如申請專利範圍第1項或第2項所述之可雷射離型的組成物，其中，該含有選自叔胺基和仲胺基之群中至少一種之含氮有機基為2-(烴基)胺基烴基酯基團、二烴基胺基烴基酯基團、胺基甲酸酯基團、吡啶、哌嗪和嗎啉基團中的至少一種，其中該烴基中任一-CH2-亦可以各自獨立為-NH-、-O-或-S-取代，其中各取代基彼此不相連接。
  5. 如申請專利範圍第1項或第2項所述之可雷射離型的組成物，其中，該壓克力樹脂包含至少兩種以上具有不同碳數的環的環醚基。
  6. 如申請專利範圍第1項或第2項所述之可雷射離型的組成物，其中，該環醚基為氧雜環丁烷基、環氧丙基或其組合。
  7. 如申請專利範圍第1項或第2項所述之可雷射離型的組成物，其中，該遮光材為可使該組成物吸收可見光、紅外光或紫外光中至少一波段或阻擋可見光、紅外光或紫外光中至少一波段通過的材料。
  8. 如申請專利範圍第1項或第2項所述之可雷射離型的組成物，其中，該添加劑進一步包含一交聯劑。
  9. 一種積層體，其包含一支撐材及以如申請專利範圍第1項或第2項所述之可雷射離型的組成物在該支撐材上所形成的膜。
  10. 一種複合膜，包含一可離型支撐膜及以如申請專利範圍第1項或第2項所述之可雷射離型的組成物所形成的暫時黏著膜；其中，該暫時黏著膜設置於該可離型支撐膜之一表面。
  11. 一種雷射離型方法，包含以下步驟：提供一支撐材；將以如申請專利範圍第1項或第2項所述之可雷射離型的組成物所形成的暫時黏著膜轉印至該支撐材之一表面；及一以雷射將該支撐材移除之步驟。
  12. 一種雷射離型方法，包含以下步驟：提供一支撐材；以如申請專利範圍第1項或第2項所述之可雷射離型的組成物塗布在該支撐材上並硬化成膜；及一以雷射將該支撐材移除之步驟。
TW109102238A 2020-01-21 2020-01-21 可雷射離型的組成物、其積層體和雷射離型方法 TWI724765B (zh)

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