TW201340811A - 各向異性導電膜及半導體元件 - Google Patents
各向異性導電膜及半導體元件 Download PDFInfo
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- TW201340811A TW201340811A TW101149049A TW101149049A TW201340811A TW 201340811 A TW201340811 A TW 201340811A TW 101149049 A TW101149049 A TW 101149049A TW 101149049 A TW101149049 A TW 101149049A TW 201340811 A TW201340811 A TW 201340811A
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- H01L23/482—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of lead-in layers inseparably applied to the semiconductor body
- H01L23/4827—Materials
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- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
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- Adhesives Or Adhesive Processes (AREA)
Abstract
本文中揭示一種各向異性導電膜及半導體元件。該膜使用一種陰離子可固化的化合物之茀取代的產物及of一種與該陰離子可固化的化合物實質不互溶的可自由基固化的化合物之茀取代的產物,藉此獲得茀取代的產物之互溶性。更特別地,該各向異性導電膜含有一種茀取代的苯氧樹脂和一種與該茀取代的苯氧樹脂互溶的茀取代的丙烯酸酯以展現出低溫下快速的固化性以及高的儲存模數,達成高可靠性。
Description
本發明係有關於一種各向異性導電膜,其使用一種陰離子可固化的(anionically curable)化合物之茀取代的產物和一種可自由基固化的化合物(radically curable)之茀取代的產物以獲得陰離子可固化的化合物和可自由基固化的化合物之互溶性(miscibility)。
更特別地,本發明係有關於一種各向異性導電膜,其含有一種茀取代的苯氧樹脂和一種茀取代的丙烯酸酯以具有的互溶性和低溫下的快速固化性(curability)以及高的儲存模數,達成高可靠性。
近年來,已經廣泛地使用利用各向異性導電膜來連接電氣組份或是半導體元件之間以及基板的終端之間為基礎之連接方法。此等各向異性導電連接方法廣泛地使用於平板顯示器之面板的生產方面之捲帶式載體封裝(TCP)終端和玻璃基板的透明電極之間的連接,介於驅動I/Cs和撓性印刷電路(FPC)板終端之間的連接以及介於驅動I/Cs和透明電極之間的連接。特別地,各向異性導電連接為有取代覆晶封裝之焊錫球連接的潛力之有希望的未來封裝的方法,以及其等之應用範圍越來越擴大。
於使用一種各向異性導電膜於高溫下接合驅動
I/Cs和透明電極的狀況中,在接合之後由於介於構成驅動I/Cs的矽晶圓和形成透明電極的玻璃之間的熱膨脹係數之差異而於熱固化後立即出現嚴重的畸變。此畸變導致終產品形成缺陷。因而,有需要發展一種於短時間之內在低溫下經受固化的各向異性導電膜。
另一方面,一種各向異性導電膜一旦於熱和壓力之下接合會膨脹以及在接合之後會收縮。由於膨脹和收縮,會產生氣泡來妨礙黏著劑組成物充分的充填,於膜內留下間隙。一些氣泡的產生導致各向異性導電膜低劣的黏著力,使得不可能使用一種包括各向異性導電膜作為連接材料的半導體元件歷時長的期間。此導致半導體元件之低的可靠性。
為了解決前述的問題,注意力已經指向發展經受低溫下的快速固化之高度可靠的各向異性導電膜。
例示韓國專利案號10-0642445 B1,其係於2006年十一月2日公開,作為本發明相關的先前技藝。
該先前技藝係有關於一種用於各向異性導電黏著劑之樹脂組成物,其使用一種羥基係被其他的官能基所取代的環氧樹脂,以及一種與該取代之前的環氧樹脂實質為不互溶的可自由基聚合性(radically polymerizable)樹脂。該先前技藝具有重要性因為兩個幾乎不相容的樹脂變成彼此互溶的。儘管此重要性,緩慢的低溫固化性以及低的可靠性仍然是有問題的。
本發明人已經認真且集中地引領研究來解決前面提及的問題。結果,本發明人已經成功發展出一種各向異性導電膜,其含有一種茀取代的苯氧樹脂和一種茀取代的丙烯酸酯來達成於低溫下快速的固化性以及高的可靠性。
本發明的一個目的是要提供一種各向異性導電膜,其使用一種陰離子可固化的化合物之茀取代的產物以及一種可自由基固化的化合物之茀取代的產物以獲得該陰離子可固化的化合物和該可自由基固化的化合物之互溶性。
本發明的另一個目的是要提供一種各向異性導電膜,其含有一種茀取代的苯氧樹脂和一種茀取代的丙烯酸酯以具有互溶性和低溫下快速的固化性以及高的儲存模數,達成高可靠性。
本發明的一個態樣提供一種各向異性導電膜。於一具體例中,該各向異性導電膜含有一種茀取代的苯氧樹脂和一種茀取代的丙烯酸酯。
於一具體例中,該各向異性導電膜含有,a)一種苯氧樹脂,其包括茀取代的苯氧樹脂;以及b)一種可自由基聚合性樹脂,其包括一種茀取代的丙烯酸酯。
於一具體例中,以100重量份的該各向異性導電膜之固體含量為基準,該各向異性導電膜含有,
a)20至60重量份的苯氧樹脂,該苯氧樹脂包括茀取代的苯氧樹脂;以及b)40至80重量份的可自由基聚合性樹脂,該可自由基聚合性樹脂包括茀取代的丙烯酸酯。
於一具體例中,以100重量份的該各向異性導電膜之固體含量為基準,該各向異性導電膜含有,a)5至50重量份的茀取代的苯氧樹脂;以及b)5至40重量份的茀取代的丙烯酸酯。
於一具體例中,該各向異性導電膜進一步含有丙烯酸修飾的環氧樹脂。
於一具體例中,該各向異性導電膜進一步含有胺甲酸酯丙烯酸酯。
於一具體例中,該各向異性導電膜當在160℃和3 MPa歷時5秒的壓製之後測量時,具有700 gf/cm或是更大的黏著強度。
於一具體例中,該各向異性導電膜具有60至200 gf/mm2的抗拉強度。
本發明的另一個態樣提供一種各向異性導電膜含有苯氧樹脂和一種可自由基聚合性樹脂,以及具有a)當在160℃和3 MPa歷時5秒的壓製之後測量時,為700 gf/cm或是更大的黏著強度,以及b)於90%或是更大的固化程度為1,000 MPa或是更大的儲存模數。
本發明的另一個態樣提供一種半導體元件。於一
具體例中,該半導體元件包括一配線基板和半導體晶片,其中該配線基板係經由該各向異性導電膜而連接至該半導體晶片。
本發明之具體例現在將詳細地描述。熟悉此藝者會容易地辨認及明瞭本文未含括之揭示,以及因而省略其等之說明。而且於本文中,定冠詞“一(a)”、“一(an)”以及其之衍生物不會把複數排除在外。
於一具體例中,該各向異性導電膜含有,a)一種苯氧樹脂,其包括茀取代的苯氧樹脂;以及b)一種可自由基聚合性樹脂,其包括一種茀取代的丙烯酸酯。
a)苯氧樹脂
本發明中使用的苯氧樹脂特徵在於包括茀取代的苯氧樹脂。
茀取代的苯氧樹脂不特別受限制只要其為以茀取代的。
本發明中可以使用本技藝中已知的任何苯氧樹脂,連同茀取代的苯氧樹脂,無特別限制。
適用於本發明之較佳的苯氧樹脂之實例包括雙
酚A型苯氧樹脂。
b)可自由基聚合性樹脂
本發明中使用的可自由基聚合性樹脂特徵在於包括一種茀取代的丙烯酸酯。
本發明中使用的茀取代的丙烯酸酯不特別受限制,只要其為以茀取代的。
適用於本發明之茀取代的丙烯酸酯之非限制性實例包括茀取代的環氧(甲基)丙烯酸酯和茀取代的胺甲酸酯(甲基)丙烯酸酯。
本發明中可以使用本技藝中已知的任何可自由基聚合性樹脂,連同茀取代的丙烯酸酯,無特別限制。
適用於本發明的可自由基聚合性樹脂之非限制性實例包括丙烯酸酯、甲基丙烯酸酯和馬來亞醯胺化合物。亦可以使用單體、寡聚體或是其等之組合。
適用於本發明的丙烯酸酯和甲基丙烯酸酯之實例包括,但不限於,丙烯酸甲酯、丙烯酸乙酯、丙烯酸異丙酯、丙烯酸異丁酯、二丙烯酸乙二醇酯、二丙烯酸二乙二醇酯、三羥甲丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、四羥甲甲烷四丙烯酸酯、2-羥基-1,3-二丙烯酸氧丙烷(2-hydroxy-1,3-diacryloxypropane)、2,2-雙[4-(丙烯氧聚甲氧基)苯基]丙烷、2,2-雙[4-(丙烯氧聚乙氧基)苯基]丙烷、二環戊烯基丙烯酸酯、三環癸基丙烯酸酯以及參(丙烯醯氧乙基)
三聚異氰酸酯。此等丙烯酸酯或甲基丙烯酸酯可以單獨或是以其等之2者或更多者之混合物來使用。
亦可以使用具有磷酸酯結構之丙烯酸酯或甲基丙烯酸酯、三聚異氰酸酯為基的丙烯酸酯或是雙酚A型環氧丙烯酸酯樹脂來改善各向異性導電膜的黏著強度和室溫穩定性。
本發明中使用的馬來亞醯胺化合物可以為分子內含有至少2個馬來亞醯胺基團的該等。此等馬來亞醯胺化合物之實例包括,但不限於,1-甲基-2,4-雙馬來亞醯胺苯、N,N’-間-伸苯基雙馬來亞醯胺、N,N’-對-伸苯基雙馬來亞醯胺、N,N’-間-甲伸苯基雙馬來亞醯胺、N,N’-4,4-伸聯苯基雙馬來亞醯胺、N,N’-4,4-(3,3’-二甲基伸聯苯基)雙馬來亞醯胺、N,N’-4,4-(3,3’-二甲基二苯甲烷)雙馬來亞醯胺、N,N’-4,4-(3,3’-二乙基二苯甲烷)雙馬來亞醯胺、N,N’-4,4-二苯甲烷雙馬來亞醯胺、N,N’-4,4-二苯丙烷雙馬來亞醯胺、N,N’-4,4-二苯醚雙馬來亞醯胺、N,N’-3,3-二苯碸雙馬來亞醯胺、2,2-雙(4-(4-馬來亞醯胺苯氧基)苯基)丙烷、2,2-雙(3-s-丁基-4-s-(4-馬來亞醯胺苯氧基)苯基)丙烷、1,1-雙(4-(4-馬來亞醯胺苯氧基)苯基)癸烷、4,4’-亞環己基雙(1-(4-馬來亞醯胺苯氧基)-2-環己基苯,以及2,2-雙(4-(4-馬來亞醯胺苯氧基)苯基)六氟丙烷。此等馬來亞醯胺化合物可以單獨或是以其等之2者或更多者之混合物來使用。
以100重量份的該各向異性導電膜之固體含量為
基準,較佳含有20至60重量份的量之本發明中使用的苯氧樹脂。
本發明中使用的苯氧樹脂內之茀取代的苯氧樹脂之含量,以100重量份的該各向異性導電膜之固體含量為基準,較佳為於5至50重量份的的範圍內。於此範圍之內,可得到高的可靠性。
以100重量份的該各向異性導電膜之固體含量為基準,較佳含有40至80重量份的量之本發明中使用的可自由基聚合性樹脂。
本發明中使用的可自由基聚合性樹脂內之該茀取代的丙烯酸酯之含量以100重量份的該各向異性導電膜之固體含量為基準,較佳為於5至40重量份的範圍內。於此範圍之內,可得到充分的低溫快速的固化性。
本發明的各向異性導電膜除了組份a)和b)之外,還可以包括一固化起始劑以及導電粒子。
本發明中使用的固化起始劑不特別受限制以及可以為本技藝中通常使用的該等之任一者。適用於本發明的固化起始劑之非限制性實例包括過氧化物起始劑與偶氮起始劑。
適用於本發明的過氧化物起始劑之實例包括,但不限於,苯甲醯過氧化物、過氧化月桂醯、過月桂酸三級丁酯、1,1,3,3-四甲基丁基過氧-2-乙基已酸酯以及氫過氧化
異丙苯(cumene hydroperoxide)。
適用於本發明的偶氮起始劑之實例包括,但不限於,2,2’-偶氮雙(4-甲氧基-2,4-二甲基戊腈)、二甲基-2,2’-偶氮雙(2-甲基丙酸酯),以及2,2’-偶氮雙(N-環己基-2-甲基丙酸酯)。
本發明中使用的導電粒子不特別受限制以及可以為本技藝中通常使用的該等之任一者。
本發明中可使用的導電粒子之非限制性實例可例示的有金屬顆粒,包括,Au、Ag、Ni、Cu及焊錫顆粒;碳顆粒;樹脂顆粒包括,例如鍍金屬或塗覆金屬,譬如,Au、Ag與Ni的樹脂顆粒,例如聚乙烯、聚丙烯、聚酯、聚苯乙烯和聚乙烯醇和其之經修飾的樹脂之顆粒;以及藉由進一步塗覆絕緣顆粒於塗覆金屬的聚合物樹脂顆粒之上而獲得的經絕緣的導電粒子。
導電粒子的特定直徑可以端視要應用的電路間距來決定以及根據意欲的應用而於2至30 μm的範圍內。
以100重量份的該各向異性導電膜之固體含量為基準,較佳含有0.1至10重量份的量之本發明中使用的導電粒子。設若導電粒子的含量低於0.1重量份,在連接的過程中接頭之間未對準可能引起接頭連接區的縮小,造成低劣連接的風險。同時,設若導電粒子的含量超過10重量份,可能有低劣絕緣的風險。
於另一具體例中,本發明的各向異性導電膜除了組份a)和b)之外,還進一步含有環氧或苯氧樹脂。
適用於本發明的環氧或苯氧樹脂之實例包括,但不限於,酚醛型環氧樹脂、表鹵醇(epihalohydrin)修飾的環氧樹脂、丙烯酸修飾的環氧樹脂、乙烯修飾的環氧樹脂、表鹵醇修飾的苯氧樹脂、丙烯酸修飾的苯氧樹脂以及乙烯修飾的苯氧樹脂。
表鹵醇修飾的環氧樹脂可以經由使分子內含羥基的環氧樹脂與表鹵醇反應來製備。丙烯酸修飾的環氧樹脂可以經由使分子內含羥基的環氧樹脂與丙烯酸單體反應來製備。乙烯修飾的環氧樹脂可以經由使分子內含羥基的環氧樹脂與乙烯單體反應來製備。
另一方面,環氧樹脂可以為環氧分子內以橡膠樹脂修飾的該等。舉例而言,用於修飾環氧樹脂的橡膠樹脂可以選自於以下所構成的群組:丁二烯聚合物、丙烯酸聚合物、聚醚胺甲酸酯橡膠、聚酯胺甲酸酯橡膠、聚醯胺胺甲酸酯橡膠、矽橡膠、二體酸、矽樹脂,以及其等之混合物。
此等環氧或苯氧樹脂可以單獨或是以其等之2者或更多者之混合物來使用。
可用橡膠樹脂來修飾的環氧樹脂之實例包括:雙酚A型樹脂、雙酚F型樹脂、雙酚AD型樹脂、雙酚S型樹脂、烯化氧加成物(alkylene oxide adduct)、其之鹵化物(舉例而言,四溴雙酚型環氧樹脂)和氫化產物(舉例而言,氫化雙酚
型環氧樹脂);及脂環環氧樹脂、脂環鏈環氧樹脂,以及其之鹵化物和氫化產物。
經修飾的環氧樹脂之商業上可得到的產品之實例包括:KD-1011、KD-1012及KD-1014,其等全部可得自於Kukdo Chemical Co.;以及EP-5100R、EP-5200R及EP-5400R,其等全部可得自於ADEKA。
環氧或苯氧樹脂的含量以100重量份的該各向異性導電膜之固體含量為基準,較佳為於0至40重量份的範圍內,更佳為10至40重量份的範圍內。於此範圍之內,能確保該茀取代的苯氧樹脂和該茀取代的丙烯酸酯之間進一步改進的互溶性,以及可得到向異性導電膜高的黏著性和可靠性。
於另一具體例中,本發明的各向異性導電膜進一步含有胺甲酸酯丙烯酸酯。
本發明中可使用的胺甲酸酯丙烯酸酯可以經由異氰酸酯、丙烯酸酯、多元醇及/或是二醇之聚合作用來製備。
可以使用,舉例而言,芳香族二異氰酸酯、脂肪族二異氰酸酯、脂環族二異氰酸酯或其等之組合來作為異氰酸酯。明確地,異氰酸酯可以選自於以下所構成的群組,但不限於:異佛酮二異氰酸酯(IPDI)、四亞甲基-1,4-二異氰酸酯、六亞甲基-1,6-二異氰酸酯、二苯甲烷二異氰酸酯、伸環己基-1,4-二異氰酸酯、亞甲基雙(4-環己基異氰酸酯)、二甲苯二異氰酸酯、氫化二苯甲烷二異氰酸酯、萘二異氰
酸酯、2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯及其等之混合物。芳香族異氰酸酯為較佳的。
丙烯酸酯可以為,舉例而言,羥基丙烯酸酯或胺基丙烯酸酯,但不限於該等。
多元醇或二醇可以為,舉例而言,乙二醇、丙二醇、己二醇、新戊二醇、二乙二醇、三乙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、二丙二醇、二丁二醇、2-甲基-1,3-戊二醇、2,2,4-三甲基-1,3-戊二醇或是1,4-環已烷二甲醇,但不限於該等。
聚合作用不特別受限制以及可以藉由來的之本技藝中已知的任何適當的方法來執行。舉例而言,聚合作用可以藉由以下方式來執行:於作為催化劑之二丁基二月桂酸錫的存在下、以50%體積計的甲基乙基酮作為溶劑來使60重量%的多元醇與羥基(甲基)丙烯酸酯和異氰酸酯(莫耳比1:1)反應於90℃和1 atm歷時5小時。
於另一具體例中,該各向異性導電膜具有60至200 gf/mm2的抗拉強度。
依據本發明之各向異性導電膜的抗拉強度較佳為於60至200 gf/mm2的範圍內,更佳為100至200 gf/mm2的範圍內。於此範圍之內,當在初步的壓製之後需要重加工時,可以不切割而剝離該膜。
對於測量抗拉強度的方法無特別的限制。抗拉強度可以藉由本技藝中通常使用的任何合適的方法予以測量。
舉例而言,在該各向異性導電膜切割成具有大約1.0 mm(寬度)×大約10 mm(長度)尺寸的樣本之後,樣本的抗拉強度係使用一種萬能試驗機(UTM)(H5K-T,Hounsfield)來測量。
本發明的態樣提供一種各向異性導電膜組成物,其含有一種苯氧樹脂和一種可自由基聚合性樹脂,以及具有a)當在160℃和3 MPa歷時5秒的壓製之後測量,為700 gf/cm或是更大的黏著強度,以及b)於90%或是更大的固化程度為1,000 MPa或是更大的儲存模數。
對於測量黏著強度的方法無特別的限制。黏著強度可以藉由本技藝中通常使用的任何合適的方法予以測量。
舉例而言,在各向異性導電膜在160℃和3 MPa歷時5秒的壓製之後,剝離強度係使用一種剝離強度測試器(H5KT,Tinius Olsen)以90°的剝離角度及50 mm/min的剝離速度來測量。
各向異性導電膜的黏著強度較佳為700 gf/cm或是更大。設若黏著強度為低於700 gf/cm,使用一種包括該各向異性導電膜作為連接材料的半導體元件歷時長的期間為不易的,表示為短壽命的半導體元件。
該各向異性導電膜的儲存模數定義為於90%或是更大的固化程度所測量的值。90%或是更大的固化程度表示當該各向異性導電膜實質完全固化的時的時間。
對於測量儲存模數的方法無特別的限制。儲存模
數可以藉由本技藝中通常使用的任何合適的方法予以測量。
舉例而言,在將各向異性導電膜的薄片一起層壓直到總厚度達到100 μm為止之後以及允許其處於150℃熱風烘箱內歷時2小時,使用動態機械分析儀(DMA)(Q800,TA)來測量層板的儲存模數。
各向異性導電膜的儲存模數較佳為1,000 MPa。設若儲存模數低於1,000 MPa,不會有效地控制熱收縮和膨脹,造成低可靠性的風險。
對於測量形成本發明之各向異性導電膜的方法無特別的限制。
本技藝中通常使用的任何合適的方法可以無特別限制地使用來形成各向異性導電膜。
不需要特定的儀器或是設備來形成各向異性導電膜。舉例而言,各向異性導電膜可以藉由以下方式來獲得,使黏結劑樹脂溶解於有機溶劑內,添加其他的組份至溶液,攪拌混合物歷時某個時間量,塗覆混合物至離形膜達適當的厚度(舉例而言,10-50 μm),以及使混合物乾燥歷時充分的時間以使有機溶劑蒸發。
本發明的態樣提供一種半導體元件,其包括該各向異性導電膜作為連接材料。
半導體元件可以包括一配線基板、一種附接至該配線基板的表面之各向異性導電膜;以及安裝於該膜之上的半導體晶片。
本發明中使用的配線基板與半導體晶片不特別受限制。配線基板與半導體晶片可以為本技藝中已知的該等。
製造半導體元件的方法無特別限制。半導體元件可以經由本技藝中已知的任何合適的方法來製造。
本發明將參照下列的實施例,包括比較實施例及實驗實施例予以更詳細地解釋。此等實施例僅為了闡明的目的而提供以及無論如何不會被解釋為限制本發明。
以待生產之100重量份的該各向異性導電膜之固體含量為基準,1)47重量份的茀取代的苯氧樹脂(FX293,New Japan Chemical),2)35重量份的茀取代的丙烯酸酯(BPF-022,Hannong Chemicals Inc.),3)5重量份的導電粒子(NIEYB00375,Sekisui),4)3重量份的黏著助劑(KBM-403,Shinetsu),以及5)10重量份的膠囊型咪唑固化劑(HXA-3941,Asahi Kasei)係使用來製備一種各向異性導電膜組成物。
以不使導電粒子粉碎的速率在室溫(25℃)下攪拌該組成物。將得到的溶液薄薄地塗覆至一種用矽脫模劑
處理的聚對酞酸乙二酯(PET)為基的膜表面之上以及使用熱風於70℃下來乾燥歷時5分鐘以形成為30 um厚的膜。膜成形係使用鑄刀。
一種各向異性導電膜係以如同實施例1中之相同的方式予以生產,除了使用32重量份的量之茀取代的苯氧樹脂,使用25重量份的量之茀取代的丙烯酸酯,以及使用25重量份的量之環氧樹脂(SG-80H,Nagase)之外。
以待生產之100重量份的該各向異性導電膜之固體含量為基準,1)20重量份的茀取代的苯氧樹脂,2)10重量份的茀取代的丙烯酸酯,3)20重量份的環氧樹脂(SG-80H,Nagase),4)10重量份的胺甲酸酯丙烯酸酯,5)12重量份的可自由基聚合性樹脂(80MFA,Kyoeisha Chemical Co.,Ltd.),6)5重量份的導電粒子(NIEYB00375,Sekisui),7)3重量份的黏著助劑(KBM403,Shinetsu),以及8)10重量份的過氧化物起始劑(BPO/LPO,Dongsung
Highchem)係使用來製備一種各向異性導電膜組成物。
一種各向異性導電膜組成物係使用如同實施例1中所述之相同的程序來形成。
一種各向異性導電膜係以如同實施例1中之相同的方式予以生產,除了茀取代的苯氧樹脂和茀取代的丙烯酸酯一個也沒使用,以及BPA苯氧樹脂(PKHH,Union Carbide)和環氧樹脂(SG-80H,Nagase)係分別以37重量份和45重量份來使用之外。
一種各向異性導電膜係以如同實施例3中之相同的方式予以生產,除了茀取代的苯氧樹脂和茀取代的丙烯酸酯一個也沒使用,以及胺甲酸酯丙烯酸酯和可自由基聚合性樹脂係分別以37重量份和45重量份的量來使用之外。
一種各向異性導電膜係以如同比較實施例1中之相同的方式予以生產,除了使用32重量份的BPA苯氧樹脂、25重量份的環氧樹脂以及25重量份的可自由基聚合性樹脂(80MFA,Kyoeisha Chemical Co.,Ltd.)之外。
一種各向異性導電膜係以如同比較實施例2中之
相同的方式予以生產,除了使用25重量份的胺甲酸酯丙烯酸酯、25重量份的可自由基聚合性樹脂以及32重量份的BPA苯氧樹脂(PKHH,Union Carbide)之外。
一種各向異性導電膜係以如同比較實施例4中之相同的方式予以生產,除了使用茀取代的苯氧樹脂代替BPA苯氧樹脂之外。
於表1和2中,實施例1-3以及比較實施例1-5中製備的各向異性導電膜組成物之組成的含量係以重量份來表示。
表2
將實施例1-3以及比較實施例1-5中製備的各向異性導電膜組成物之各者於糊混合機(paste mixer)內攪拌,允許處於25℃歷時1 hr,以及塗覆至一種具有形成於其上的離形層之聚對酞酸乙二酯(PET)膜。用肉眼觀察形成於離形層之上的膜之均勻性。
當膜為非常均勻的時,互溶性評估為‘優異的’,當膜一般均勻時,互溶性評估為‘良好的’,以及當膜不均勻時,互溶性評估為‘低劣的’。
將實施例1-3以及比較實施例1-5中生產的各向異性導電膜之各者切割成具有1.0 mm(寬度)×10 mm(長
度)的尺寸之樣本。樣本的抗拉強度係使用萬能試驗機(UTM)(H5K-T,Hounsfield)來測量。
將實施例1-3以及比較實施例1-5中生產的各向異性導電膜之各者的薄片一起層壓直到總厚度達到100 μm為止以及允許其處於150℃熱風烘箱內歷時2小時。之後,使用動態機械分析儀(DMA)(Q800,TA)來測量層板於40℃之儲存模數。
將實施例1-3以及比較實施例1-5之各向異性導電膜之各者係透過以於160℃和3 MPa下歷時5秒之壓製而連接至具有200個銅電路或是更多銅電路的撓性印刷電路(FPC)(行寬度=100 μm,間距=100 μm,厚度=18 μm)來製備樣本。
樣本之起始的黏著強度係使用一種剝離強度測試器(H5KT,Tinius Olsen)以90°的剝離角度及50 mm/min的剝離速度來測量。
關於高溫和高濕度可靠性評估,允許樣本處於85℃的溫度和85%的相對濕度歷時100小時。之後,樣本之可靠的黏著強度係藉由如以上所述相同的方式來測量。
將實施例1-3以及比較實施例1-5之各向異性導電膜之各者透過以於160℃和3 MPa下歷時5秒之壓製而連接至具有200個銅電路或是更多銅電路的撓性印刷電路(FPC)(行寬度=100 μm,間距=100 μm,厚度=18 μm)來製備樣本。
樣本之起始的連接電阻係使用4探針方法(ASTM F43-64T)來測量。
關於高溫和高濕度可靠性評估,將樣本留在85℃的溫度和85%的相對濕度歷時500小時。之後,樣本之可靠的連接電阻係依據ASTM D117來測量。
表3和4顯示實驗實施例1-5之測量結果。
表4
從前述的測量結果,確認使用茀取代的苯氧樹脂和茀取代的丙烯酸酯生產的各向異性導電膜顯示出優異的互溶性、高的抗拉強度以及高的儲存模數。此外,實施例1-3的膜於低溫的快速固化條件下有效地連接,說明其等在可靠的黏著強度和可靠的連接電阻以及起始的黏著強度和起始的連接電阻方面優異的物理性質。
比較實施例1、2和5的膜顯示出良好的互溶性但是於低溫的快速固化條件下不會有效地連接,顯露出其等之低黏著強度。特別地,該膜在可靠的黏著強度和可靠的連接電阻方面顯示較差的物理性質。從此等結果,確定當該膜連接至半導體膜時,使用該半導體膜歷時長的期間同時維持該膜的可靠性為困難的。
另一方面,比較實施例3和4的膜顯示低劣的互溶性以及於低溫的快速固化條件下不會實質連接,顯露出其等之非常低的黏著強度。結果,不可能評估該膜的黏著強
度和連接電阻。
因此,茀取代的苯氧樹脂和茀取代的丙烯酸酯於生產各向異性導電膜之組合使用確認會獲得膜之低溫的快速固化性以及高的可靠性。此外,適當的添加環氧樹脂及/或胺甲酸酯丙烯酸酯堅定各向異性導電膜較好的物理性質。
如由前述顯而易見的,本發明之各向異性導電膜由於存在茀取代的苯氧樹脂和茀取代的丙烯酸酯而於低溫下為可快速固化的以及為高度可靠的。
更特別地,本發明之各向異性導電膜使用陰離子可固化的化合物之茀取代的產物和與該陰離子可固化的化合物實質不互溶的可自由基固化的化合物之茀取代的產物,藉此獲得茀取代的產物之互溶性。
此外,本發明之各向異性導電膜含有茀取代的苯氧樹脂和互溶於茀取代的苯氧樹脂之茀取代的丙烯酸酯以展現出低溫下快速的固化性以及高的儲存模數,達成高可靠性。
雖然已經提供一些具體例結合附圖,熟悉此藝者顯然了解該等具體例僅僅提供作為實例,以及可以做出各種各樣的修飾、變化、改變,以及均等的具體例而不背離本發明的精神和範疇。本發明的範疇應該僅僅由附隨的申請專利範圍來限制。
Claims (16)
- 一種各向異性導電膜,其包含:a)苯氧樹脂,其包含茀取代的苯氧樹脂;以及b)可自由基聚合性(radically polymerizable)樹脂,其包含茀取代的丙烯酸酯。
- 如申請專利範圍第1項之各向異性導電膜,其中,以100重量份的該各向異性導電膜之固體含量為基準,該各向異性導電膜包含:a)20至60重量份的該苯氧樹脂,其包含該茀取代的苯氧樹脂;以及b)40至80重量份的該可自由基聚合性樹脂,其包含該茀取代的丙烯酸酯。
- 如申請專利範圍第2項之各向異性導電膜,其中,以100重量份的該各向異性導電膜之固體含量為基準,該各向異性導電膜包含5至50重量份的該茀取代的苯氧樹脂和5至40重量份的該茀取代的丙烯酸酯。
- 如申請專利範圍第1至3項中任一項之各向異性導電膜,其進一步包含丙烯酸修飾的環氧樹脂。
- 如申請專利範圍第1至3項中任一項之各向異性導電膜,其進一步包含胺甲酸酯丙烯酸酯。
- 如申請專利範圍第1至3項中任一項之各向異性導電膜,其中該各向異性導電膜具有當在160℃和3 MPa歷時5秒的壓製之後測量時,為700 gf/cm或是更大的黏著強度。
- 如申請專利範圍第1至3項中任一項之各向異性導電膜,其中該各向異性導電膜具有60至200 gf/mm2的抗拉強度。
- 一種各向異性導電膜,其包含一苯氧樹脂和一可自由基聚合性樹脂,其中該膜具有,a)當在160℃和3 MPa歷時5秒的壓製之後測量時,為700 gf/cm或是更大的黏著強度;以及b)於90%或是更大的固化程度下為1,000 MPa或是更大的儲存模數。
- 如申請專利範圍第8項之各向異性導電膜,其中該苯氧樹脂包含茀取代的苯氧樹脂。
- 如申請專利範圍第8項之各向異性導電膜,其中該可自由基聚合性樹脂包含茀取代的丙烯酸酯。
- 如申請專利範圍第9項之各向異性導電膜,其中,以100重量份的該各向異性導電膜之固體含量為基準,該各向異性導電膜包含5至50重量份的該茀取代的苯氧樹脂。
- 如申請專利範圍第10項之各向異性導電膜,其中,以100重量份的該各向異性導電膜之固體含量為基準,該各向異性導電膜包含5至40重量份的該茀取代的丙烯酸酯。
- 如申請專利範圍第8至12項中任一項之各向異性導電膜,其進一步包含丙烯酸修飾的環氧樹脂。
- 如申請專利範圍第8至12項中任一項之各向異性導電膜,其進一步包含胺甲酸酯丙烯酸酯。
- 如申請專利範圍第8至12項中任一項之各向異性導電 膜,其中該各向異性導電膜具有60至200 gf/mm2的抗拉強度。
- 一種半導體元件,其包含:a)一配線基板;b)一附接至該配線基板的表面之各向異性導電膜;以及c)安裝於該膜之上的半導體晶片;其中該各向異性導電膜為如申請專利範圍第1至15項中任一項之膜。
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JP6408759B2 (ja) * | 2013-11-08 | 2018-10-17 | デクセリアルズ株式会社 | 接着剤組成物、及びフィルム巻装体 |
KR101893248B1 (ko) * | 2015-11-26 | 2018-10-04 | 삼성에스디아이 주식회사 | 이방 도전성 필름 및 이를 이용한 접속 구조체 |
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JP2001049228A (ja) * | 1999-08-12 | 2001-02-20 | Sony Chem Corp | 低温硬化型接着剤及びこれを用いた異方導電性接着フィルム |
JP4265140B2 (ja) * | 2002-02-28 | 2009-05-20 | 日立化成工業株式会社 | 異方導電性接着剤組成物、それを用いた回路端子の接続方法及び接続構造体 |
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TWI498065B (zh) | 2015-08-21 |
CN103173143A (zh) | 2013-06-26 |
CN103173143B (zh) | 2015-05-20 |
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