TW201331252A - 各向異性導電膜組成物、各向異性導電膜及半導體裝置 - Google Patents

各向異性導電膜組成物、各向異性導電膜及半導體裝置 Download PDF

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TW201331252A
TW201331252A TW101146081A TW101146081A TW201331252A TW 201331252 A TW201331252 A TW 201331252A TW 101146081 A TW101146081 A TW 101146081A TW 101146081 A TW101146081 A TW 101146081A TW 201331252 A TW201331252 A TW 201331252A
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Taiwan
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conductive film
anisotropic conductive
group
film composition
formula
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TW101146081A
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TWI482793B (zh
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Arum Yu
Nam-Ju Kim
Kyoung-Soo Park
Young-Woo Park
Joon-Mo Seo
Kyung-Il Sul
Dong-Seon Uh
Hyun-Min Choi
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Cheil Ind Inc
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Abstract

本發明所揭露的是一種各向異性導電膜組成物，包含一以式1來表示之經氫化的雙酚A環氧單體或一以式2來表示之經氫化的雙酚A環氧寡聚體，該各向異性導電膜組成物顯示優異的抗濕性與抗熱性，且可在低溫下快速固化；本發明亦揭露包含有該組成物的一種各向異性導電膜，以及一種半導體裝置。□□其中n是一自1至50的整數。

Description

各向異性導電膜組成物、各向異性導電膜及半導體裝置 發明領域
本發明是有關於一種各向異性導電膜組成物，其使用一經氫化之雙酚A環氧單體(hydrogenated bisphenol A epoxy monomer)與一鋶固化劑(sulfonium curing agent)的陽離子固化系統，本發明亦有關於一種包含有該系統的各向異性導電膜。更具體地，本發明是有關於一種堅硬且顯示優異之抗濕性(moisture resistance)和抗熱性(heat resistance)的各向異性導電膜組成物，其藉此而可用於各向異性導電膜，尤其是利用在玻璃覆晶基板技術(chip-on-glass,COG)上；本發明亦具體地有關於一包含該組成物的各向異性導電膜。
發明背景
一般說來，各向異性導電膜(anisotropic conductive films,ACFs)指的是一種膜狀的接著劑，其中，諸如金屬粒子(包含鎳粒子或金粒子，或是塗佈有金屬的聚合物粒子)的導電粒子被分散在諸如環氧樹脂的樹脂中。各 向異性導電膜提供了具有介電各向異性(electric anisotropy)與黏著性的聚合物層體，且該層體在厚度方向上顯示導電性，而在其表面方向上顯示絕緣性。該等各向異性導電膜被廣泛地使用於將液晶顯示器(liquid crystal display,LCD)平板或印刷電路板電性連接於捲帶承載封裝(tape carrier packages,TCPs)。
當一各向異性導電膜被設置在電路板之間來做為連接，並在特定條件下加熱及壓合時，電路板的電路端子經由導電粒子而被電性連接，且一絕緣黏著性樹脂被填充於相鄰電路端子之間的空間內，以讓該等導電粒子彼此隔絕，而在該等電路端子間達成了高度的絕緣表現。
就使用於各向異性導電膜的絕緣樹脂而言，最常被使用的是熱固性樹脂。熱固性樹脂在受熱而固化時會散熱，同時熱固性樹脂的溫度會因所施加之溫度的消除而降低，並在固化過程結束時，藉由所散發的熱量而提升溫度。因此，該熱固性樹脂會因為溫度差所造成的體積變化而承受固化收縮(curing shrinkage)。當固化收縮發生時，該各向異性導電膜的尺寸安定性即會惡化，造成瑕疵率的增加。尤其是，一般用以做為熱固性樹脂的環氧樹脂具有極佳的黏著力、抗熱性，與抗濕性，但具有顯著高的接合溫度(bonding temperature)與顯然很久的接合時間(bonding time)，因而造成了膜形成後瑕疵率增加的可能性。因此，已有各種不同的嘗試被形成來發展出一快速之可低溫固化的各向異性導電膜，其可在低溫下即快速地固化。
同時，玻璃覆晶基板技術(COG)是用於在一種具有形成於其上的薄膜電路(thin film circuit)之玻璃基板上安裝晶片的一種晶片安裝技術，而可使一IC直接安裝在液晶顯示器中的一液晶玻璃平板上。用於COG的的各向異性導電膜需要有至少30 MPa以上的黏著力與接線電阻(connection resistance)，而得以不僅在一開始時，甚至在信賴度測試之後，都能確實地固持住驅動IC(drive IC)與平板。然而，一般用於COG的各向異性導電膜在固化後即具有低模數，且易因熱與濕度而受損，因而使其難以製出可信任之已接著產品。
韓國專利公開號10-2011-0074320案(已於2011年6月30日公開)揭露一種可於低溫下快速固化之各向異性導電膜組成物，其包含一環己烷環氧樹脂(cyclohexane epoxy resin)，該環己烷環氧樹脂在其結構中的環己烷與環氧結構是彼此直接銜接的；如此，該環氧結構的鍵結強度(bond strength)即顯然地低於其他一般的環氧化合物，且藉由固化劑(curing agent)的酸攻擊(acid attack)所引起的開環反應，也會開始得比其他環氧化合物的開環反應快。因此，該各向異性導電膜組成物可於低溫下被快速固化。然而，該各向異性導電膜組成物在經固化後會具有較低的模數而會由於低可信度之故，相較於使用在薄膜覆晶技術(chip-on-film,COF)、玻璃上膜技術(film-on-glass,FOG)、外引腳接合技術(outer-lead-bonding,OLB)上，該各向異性導電膜組成物並不適宜使用在COG技術(其平板是接合於 驅動IC上)。
日本專利公開號2001-261780案(已於2001年9月26日公開)揭露一種環氧樹脂組成物，其包含經氫化的雙酚A環氧樹脂。然而，此種環氧樹脂組成物是可藉紫外線而固化，但不能被熱所固化，而須在90℃下接受初次固化2小時，接而在140℃下接受二次固化4小時。因此，該環氧樹脂組成物即不適用於要求在150~170℃下固化5秒鐘的ACF(各向異性導電膜)。此外，此公開案的環氧樹脂組成物提供了在可撓性與黏著性之間的優異平衡，但本發明的各向異性導電膜組成物則是在固化之後呈現出堅硬的結構。
作為解決前述問題的延伸性研究成果，本發明的發明人發展出於低溫下可快速固化之各向異性導電膜組成物；其非常堅硬，且顯示優異的抗熱性與抗濕性，並適用於COG。本發明亦發展出包含該組成物的各向異性導電膜。
發明概要
本發明的目的在於提供一種用於玻璃覆晶基板技術(COG)的各向異性導電膜組成物，該組成物堅硬且顯示優異的抗濕性與抗熱性，並改善了連接可靠性(connection reliability)。本發明另以提供一種包含該組成物的各向異性導電膜為目的。
此外，本發明的目的在於提供一種可在低溫下快速固化的各向異性導電膜組成物，以及包含該組成物的各向異性導電膜。
本發明的一方面提供一種各向異性導電膜組成物，其包含：(a)一以式1來表示之經氫化的雙酚A環氧單體，或是一以式2來表示之經氫化的雙酚A環氧寡聚體；(b)一鋶固化劑；(c)一黏著劑樹脂；以及(d)導電粒子。
其中n是一自1至50的整數。
在一具體例中，該各向異性導電膜組成物包含：(a)1到50重量份的該以式1來表示之經氫化的雙酚A環氧單體或是該以式2來表示之經氫化的雙酚A環氧寡聚體；(b)1到20重量份的鋶固化劑；(c)20到60重量份的黏著劑樹脂；以及(d)10到50重量份的導電粒子，以上是以100重量份的各向異性導電膜組成物為基礎。
在一具體例中，該鋶固化劑(b)為芳香族鋶鹽(aromatic sulfonium salt)。
在一具體例中，該芳香族鋶鹽是以式3來表示。
其中R1是選自於由氫、烷基、烷氧基、甲氧羰基，與 乙氧羰基所構成的群組；R2是選自於由甲基、乙基、丙基，與丁基所構成的群組；而R3是選自於由硝基苄基(nitrobenzyl group)、二硝基苄基(dinitrobenzyl group)、三硝基苄基(trinitrobenzyl group)，與萘甲基(naphthylmethyl group)所構成的群組。
在一具體例中，該芳香族鋶鹽是以式5來表示。
其中R1是選自於由羥基，R5O-，，與所構成的群組；R5是選自於由芳香族碳氫化合物、經取代的芳香族碳氫化合物、脂肪族碳氫化合物、經取代的脂肪族碳氫化合物、羧基，與磺醯基(sulfonyl group)所構成的群組；而R2則是選自於由氫與C1到C6烷基所構成的群組。
在一具體例中，該黏著劑樹脂(c)包含一茀環氧樹脂(fluorene epoxy resin)。
在一具體例中，該各向異性導電膜組成物具有 120℃以上的玻璃轉移溫度。
在一具體例中，該各向異性導電膜組成物是使用於COG。
本發明的另一方面提供了一種各向異性導電膜，其包含一以式1來表示之經氫化的雙酚A環氧單體或是一以式2來表示之經氫化的雙酚A環氧寡聚體，並於150℃至170℃之間固化5至10秒時，具有70%以上的固化速率(curing rate)；該各向異性導電膜亦具有120℃以上的玻璃轉移溫度：
其中n是一自1至50的整數。
在一具體例中，該各向異性導電膜具有當於150℃被固化5至10秒時70%以上的固化速率，與120℃以上的玻璃轉移溫度。
在一具體例中，該各向異性導電膜是使用於COG。
根據本發明之又一方面，其係提供一種半導體裝置，其包含：一配線基板；以及一半導體晶片，其中該半導體裝置是經由該各向異性導電膜而連接。
以下將詳述本發明。
本發明的一方面提供一種各向異性導電膜組成物，其包含：(a)一以式1來表示之經氫化的雙酚A環氧單體，或是一以式2來表示之經氫化的雙酚A環氧寡聚體；(b)一鋶固化劑；(c)一黏著劑樹脂；以及(d)導電粒子。
其中n是一自1至50的整數。
該以式1來表示之經氫化的雙酚A環氧單體或是該以式2來表示之經氫化的雙酚A環氧寡聚體，形成了較雙酚A環氧樹脂更為緊緻的結構，因此明顯地堅硬。再者，不像揭露在於韓國專利公開案10-2011-0074320號的環己烷環氧樹脂，該經氫化的雙酚A環氧單體或者是該經氫化的雙酚A環氧寡聚體，具有一呈直線延伸的結構，因而顯示較堅硬的性質。因此，該各向異性導電膜組成物具有優異的抗濕性與抗熱性以及經改善的連接可靠性。
該以式1來表示之經氫化的雙酚A環氧單體或是該以式2來表示之經氫化的雙酚A環氧寡聚體，在以100重量份的各向異性導電膜組成物為基礎時，存在有1到50重量份，較佳地為5到30重量份。在此範圍內，一較堅硬且具有 優異之抗濕性與抗熱性的各向異性導電膜組成物，可被形成。
該鋶固化劑未被予任何特殊限制，可為此領域中被通常使用之任何鋶固化劑。
該鋶固化劑之範例可包括以式4或5表示之鋶鹽(sulfonium salts)： 其中R1是選自於由苯甲基、經取代的苯甲基、苯甲醯甲基(phenacyl group)、經取代的苯甲醯甲基、烯丙基、經取代的烯丙基、烷氧基、經取代的烷氧基、芳氧基，與經取代的芳氧基所構成的群組；R2與R3則各自與R1相同，或是選自於由氟、氯、溴、羥基、羧基、硫氫基(mercapto group)、氰基、硝基，與經疊氮基(azido group)所取代的C1到C18之直鏈狀、分支狀，或環狀之烷基所構成的群組。R1與R2、R1與R3、或R2與R3，可彼此接合為一環狀結構。
其中，R1是選自於由羥基，R5O-，，與所構成的群組；R5是選自於由芳香族碳氫化合物、經取代的芳香族碳氫化合物、脂肪族碳氫化合物、經取代的脂肪族碳氫化合物、羧基，與磺醯基(sulfonyl group)所構成的群組；R2則是選自於由氫與C1到C6烷基所構成的群組。
式5的範例可包含
該鋶固化劑可包含芳香族鋶鹽，較佳地為以式3所表示的芳香族鋶鹽，此係有鑑於其能藉由熱活化能而高效率地產生陽離子，以達到使膜在低溫下之快速固化： 其中，R1是選自於由氫、烷基、烷氧基、甲氧羰基， 與乙氧羰基所構成的群組；R2是選自於由甲基、乙基、丙基，與丁基所構成的群組；而R3則是選自於由硝基苄基、二硝基苄基、三硝基苄基，與萘甲基所構成的群組。
該鋶固化劑可使該各向異性導電膜組成物充分地達成在低溫下之快速固化。
以100重量份的各向異性導電膜組成物為基礎，該鋶固化劑存在有1到20重量份，較佳地為1到10重量份。在此範圍中，該各向異性導電膜組成物可實現足夠的低溫快速固化，並被避免在室溫或低於室溫下被固化。
該黏著劑樹脂可包含在本領域中一般被使用之任一種黏著劑樹脂，尤其是只要它不會阻礙該經氫化的雙酚A環氧單體或寡聚體的固化即可。黏著劑樹脂的範例可包含聚醯亞胺樹脂(polyimide resin)、聚醯胺樹脂(polyamide resin)、苯氧基樹脂(phenoxy resin)、環氧樹脂、聚甲基丙烯酸酯樹脂(polymethacrylate resin)、聚丙烯酸酯樹脂(polyacrylate resin)、聚胺基甲酸酯樹脂(polyurethane resin)、聚酯樹脂(polyester resin)、聚酯胺基甲酸酯樹脂(polyester urethane resin)、聚乙烯丁醛樹脂(polyvinyl butyral resin)、苯乙烯/丁二烯/苯乙烯(styrene-butylene-styrene，SBS)樹脂與其之環氧化改質物、苯乙烯/乙二烯/丁二烯/苯乙烯(styrene-ethylene-butylene-styrene，SEBS)樹脂與其之改質物，以及丙烯腈-丁二烯橡膠(acrylonitrile butadiene rubber，NBR)與其之氫化物；其等可被單獨使用或作為混 合物使用。
另外，就黏著劑樹脂而言，較佳地是使用熱固性環氧樹脂，例如，一具有90到5,000 g/eq之環氧當量(epoxy equivalent weight)且至少有兩個環氧基的環氧樹脂。
該熱固性環氧樹脂可為至少一選自於由雙酚環氧樹脂(bisphenol epoxy resin)、酚醛環氧樹脂(novolac epoxy resin)、環氧丙基環氧樹脂(glycidyl epoxy resin)、脂肪族環氧樹脂(aliphatic epoxy resin)、脂環環氧樹脂(alicyclic epoxy resin)，以及芳香族環氧樹脂(aromatic epoxy resin)所構成的群組，但不限於其等。另外，一在室溫下呈固態之環氧樹脂與一在室溫下呈液態之環氧樹脂，可被組合地使用，且一具可撓性的環氧樹脂可進一步地被添加於該組合中。
該在室溫下呈固態之環氧樹脂的範例，可包含但不限於苯酚酚醛型環氧樹脂(phenol novolac epoxy resin)、甲酚酚醛型環氧樹脂(cresol novolac epoxy resin)、具有雙環戊二烯(dicyclopentadiene)骨架之環氧樹脂、雙酚A或F環氧樹脂，以及經改質的環氧樹脂。該在室溫下呈液態之環氧樹脂的範例，可包含但不限於雙酚A環氧樹脂、雙酚F環氧樹脂，或者是其等混合之環氧樹脂。
該具可撓性的環氧樹脂之範例可包含但不限於經二聚物酸改質之環氧樹脂、具有丙二醇骨架之環氧樹脂，與經胺基甲酸酯改質之環氧樹脂。該芳香族環氧樹脂可為至少一選自由萘樹脂(naphthalene resins)、蒽樹脂 (anthracene resins)，與芘(pyrene resins)所構成的群組，但不限於其等。
此外，就該黏著劑樹脂而言，茀環氧樹脂是可被使用的。當該黏著劑樹脂包含茀環氧樹脂時，該膜組成物可輕易獲得高玻璃轉移溫度與優異的耐久性。
若以膜形成之簡易化來考量，該黏著劑樹脂可具有高重量平均分子量，但不特別受限於此；例如，該黏著劑樹脂具有5,000到150,000 g/mol，較佳地為10,000 to 80,000 g/mol的重量平均分子量。在此範圍內，該黏著劑樹脂與該膜組成物的其他組分之間具有優越的相容性，而使膜形成被簡易化。
在以100重量份的各向異性導電膜組成物為基礎下，該茀環氧樹脂存在有0到30重量份，較佳地為1到15重量份之量。
在以100重量份的各向異性導電膜組成物為基礎下，該黏著劑樹脂存在有20到60重量份，較佳地為30到50重量份之量。
該導電粒子可包含金屬粒子，或者是塗佈有諸如金或銀之金屬的有機或無機粒子。此外，該導電粒子可包含經絕緣化的導電粒子，以在使用了過量的導電粒子時可有電絕緣之作用。導電粒子的範例可包含例如金粒子、銀粒子、鎳粒子、銅粒子，與鉛粒子的金屬粒子、碳粒子、塗佈金屬之樹脂粒子，例如塗佈金、銀、鎳之聚乙烯、聚丙烯、聚酯、聚苯乙烯、聚乙烯醇與及其等之經改質的樹 脂等；以及可進一步以絕緣粒子來塗佈而被絕緣化的導電粒子。
在以100重量份的各向異性導電膜組成物為基礎下，該導電粒子存在有10到50重量份，較佳地為20到40重量份之量。在此範圍內，該膜組成物可獲得足夠的導電性，且可避免因過量的導電粒子所造成的電性短路。
該各向異性導電膜組成物可進一步包含一適當的溶劑。該溶劑均勻地混合該經氫化的雙酚A環氧單體或寡聚體、該鋶固化劑、該黏著劑樹脂，與該導電粒子，並降低了該組成物的黏度，使該膜之形成更為簡易化。
該溶劑可包含在本領域中一般所使用的任何溶劑。例如，該溶劑可包含甲苯、二甲苯、丙二醇單甲醚乙酸酯(propylene glycol monomethyl ether acetate)、苯、丙酮、甲乙酮、四氫呋喃(tetrahydrofuran)、二甲基甲醛(dimethylformaldehyde)，以及環己酮(cyclohexanone)。
該各向異性導電膜組成物可進一步包含添加劑，例如聚合抑制劑(polymerization inhibitor)、抗氧化劑、熱穩定劑、固化促進劑(curing accelerator)，以及偶合劑(coupling agent)。該等添加劑可包含在本領域中一般所使用之任何添加劑。
該聚合抑制劑的例子可包含對苯二酚(hydroquinone)、對苯二酚單甲醚(hydroquinone monomethyl ether)、對苯二酮(p-benzoquinone)、硫二苯胺(phenothiazine)，及其等之混合物。
該抗氧化劑與熱穩定劑的例子可包含四-(亞甲基-(3,5-二第三丁基-4-氫肉桂酸酯)甲烷(tetrakis-(methylene-(3,5-di-terbutyl-4-hydrocinnamate)methane)、3,5-雙(1,1-二甲基乙基)-4-羥基苯丙酸硫醇二-2,1-乙二基酯(3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid thiol di-2,1-ethanediyl ester)、十八烷基3,5-二-第三丁基-4-羥基氫肉桂酸酯(octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate)(以上皆可自Ciba購得)，以及2,6-二-第三丁基-對甲酚(2,6-di-t-butyl-p-methylphenol)。
該固化促進劑的例子可包含固態咪唑固化促進劑(solid imidazole curing accelerators)、固態胺類固化促進劑(solid amine curing accelerators)，以及液態胺類固化促進劑。
該偶合劑的例子可包含乙烯三氯矽烷(vinyltrichlorosilane)、3-縮水甘油醚氧丙基三甲氧基矽烷(3-glycidoxypropyltrimethoxysilane)、3-甲基丙烯氧丙基三甲氧矽烷(3-methacryloxypropyltrimethoxysilane)、2-胺基乙基-3-胺基丙基甲基二甲氧基矽烷(2-aminoethyl-3-aminopropylmethyldimethoxysilane)，以及3-脲基丙基三乙氧基矽烷(3-ureidopropyltriethoxysilane)。
該各向異性導電膜組成物較佳地是使用於COG，此係有鑑於其在固化後具有高模數、高玻璃轉移溫度，與堅硬的質地。
本發明於另一方面提供了一種各向異性導電膜，其在150到170℃下固化5到10秒鐘具有70%以上之固化速率，且具有120℃以上的玻璃轉移溫度。
本發明於另一方面提供了一種各向異性導電膜，其在150℃下固化5到10秒鐘具有70%以上之固化速率，且具有120℃以上的玻璃轉移溫度。
當對一物體施以上述條件時，一具有70%以上之固化速率的各向異性導電膜可將其初始的物理性質優異地維持至信賴度測試之後，且一具有120℃以上的玻璃轉移溫度之各向異性導電膜並不會在接合後被嚴重地變形，以避免接合時發生短路的情形。
在一具體例中，該各向異性導電膜包含有一以式1來表示之經氫化的雙酚A環氧單體，或是一以式2來表示之經氫化的雙酚A環氧寡聚體。
其中n是一自1至50的整數。
依據本發明之一種各向異性導電膜的形成方法，並無特殊限制，且本領域中所採用的任何方法，皆可被使用。
各向異性導電膜之形成方法中並未涉及任何特殊的儀器或設備；例如，一種各向異性導電膜可藉由下述程序而被製得：一黏著劑樹脂被溶解並液化於一有機溶劑中、剩餘的成分被添加入該溶液內並攪拌一段時間、該混合物被使用於形成膜至其具有適當厚度(例如10到50 μm)，並乾燥一段時間，以蒸發有機溶劑。
本發明的另一方面提供一種透過該各向異性導電膜而銜接之半導體裝置。
該半導體裝置可包含有一配線基板、一貼附於該配線基板之晶片安裝面上的各向異性導電膜，以及一安裝在該膜上的半導體晶片。
對於本發明中所使用的該配線基板與半導體晶片，並無特殊限制，可使用在本領域中一般所知的任何配線基板與半導體晶片。
如上所述，本發明提供了一種各向異性導電膜組成物，其包含有一經氫化的雙酚A環氧單體或寡聚體，以具有堅硬的質地；本發明亦提供包含有該組成物的各向異性導電膜。更明確地說，本發明提供了一種各向異性導電膜組成物，其適用於COG，質地堅硬且具有120℃以上的玻璃轉移溫度；本發明亦提供了一種包含有該組成物的各向異性導電膜。
另外，本發明提供了一種各向異性導電膜組成物，其包含有一鋶固化劑，以於低溫下快速地固化；本發明亦提供一種包含有該組成物的各向異性導電膜。詳言 之，本發明提供了一種各向異性導電膜組成物，其在150至170℃下固化5到10秒時，具有70%以上之固化速率；本發明亦提供一種包含有該組成物的各向異性導電膜。
此外，本發明提供一種各向異性導電膜組成物，其具有優異的抗濕性與抗熱性，來減少因溫度或濕度所造成的變形，以具有連接可靠性；本發明亦提供一種具有該組成物之各向異性導電膜。
較佳實施例之詳細說明
以下，將以關於下述實施例、比較例，與試驗例之更多細節來解釋本發明。這些例子皆僅供說明之目的而被提供，並非用以任何方式來限制本發明。
此處未包含的細節為熟習此領域者所能輕易辨別與察知，故而省略其等之說明。
實施例1
包含有經氫化的雙酚A環氧單體之各向異性導電膜組成物的製備
14重量份之經氫化的雙酚A環氧單體(見式1)、40重量份之雙酚A環氧樹脂(型號為YP-50，由國都化學株式會社(Kukdo Chemical Co.,Ltd.)出品)、2重量份的含多環芳香族環氧樹脂(型號為HP4032D，由大日本油墨化學工業股份有限公司(Dainippon Ink & Chemicals)出品)、5重量份之對 苯二甲酸二環氧丙酯(diglycidyl terephthalate)環氧樹脂(型號為EX-711，由長瀨化成股份有限公司(Nagase ChemteX)出品)、4重量份之乾燥二氧化矽(型號為R812，由德固薩(Degussa)公司出品)、5重量份之鋶陽離子固化劑(型號為SI-60L，由三信化學工業株式會社(Samshin Chemicals)出品)、29重量份之以鎳塗佈的聚合物粒子，以及1重量份之γ-縮水甘油醚氧丙基三甲氧基矽烷(γ-glycidoxypropyltrimethoxysilane)(型號為KBM403，由信越化學工業株式會社(Shin-Etsu Chemical)出品)，被混合以形成一各向異性導電膜組成物。該等組份與100重量份之作為溶劑的PGMA相混合，繼而被塗佈及乾燥。
實施例2
包含有茀環氧樹脂之各向異性導電膜組成物的製備
3重量份的茀BPA樹脂(型號為FX-293，由新日本製鐵株式會社(Shin Nippon Steel Corp.)出品)、11重量份之經氫化的雙酚A環氧單體(見式1)、40重量份之雙酚A環氧樹脂(型號為YP-50，由國都化學株式會社出品)、2重量份的含多環芳香族環氧樹脂(型號為HP4032D，由大日本油墨化學工業股份有限公司出品)、5重量份之對苯二甲酸二環氧丙酯環氧樹脂(型號為EX-711，由長瀨化成股份有限公司出品)、4重量份之乾燥二氧化矽(型號為R812，由德固薩公司出品)、5重量份之鋶陽離子固化劑(型號為SI-60L，由三信化學工業株式會社出品)、29重量份之塗佈有鎳的高分子聚合物粒子，以及1重量份之γ-縮水甘油醚氧丙基三甲氧基矽 烷(型號為KBM403，由信越化學工業株式會社出品)，被混合以形成一各向異性導電膜組成物。該等組份與100重量份之作為溶劑的PGEMA相混合，繼而被塗佈及乾燥。
實施例3
包含有經氫化之雙酚A環氧寡聚體的各向異性導電膜組成物之製備
除了以14重量份之經氫化之雙酚A環氧寡聚體(見式2)替換14重量份之經氫化的雙酚A環氧單體(見式1)之外，以相同於實施例1之方式製備一各向異性導電膜組成物。
實施例4
包含有經氫化的雙酚A環氧單體與經氫化的雙酚A寡聚體之各向異性導電膜組成物的製備
除了以10重量份之經氫化之雙酚A環氧單體(見式1)與4重量份之經氫化的雙酚A環氧寡聚體(見式2)替換14重量份之經氫化的雙酚A環氧單體(見式1)之外，以相同於實施例1之方式製備一各向異性導電膜組成物。
比較例1
各向異性導電膜組成物之製備
除了以16重量份的含多環芳香族環氧樹脂(型號為HP4032D，由大日本油墨化學工業股份有限公司出品)替換14重量份之經氫化的雙酚A環氧單體(見式1)與2重量份之含多環芳香族環氧樹脂(型號為HP4032D，由大日本油墨化學工業股份有限公司出品)之外，以相同於實施例1之方 式製備一各向異性導電膜組成物。
比較例2
各向異性導電膜組成物之製備
除了以19重量份的對苯二甲酸二環氧丙酯環氧樹脂(型號為EX-711，由長瀨化成股份有限公司出品)來替代3重量份之茀BPA樹脂(型號為FX-293，由新日本製鐵株式會社出品)、11重量份之經氫化的雙酚A環氧單體(見式1)，以及5重量份之對苯二甲酸二環氧丙酯環氧樹脂(型號為EX-711，由長瀨化成股份有限公司出品)之外，以相同於實施例2之方式製備一各向異性導電膜組成物。
實施例5
各向異性導電膜之製備
施用實施例1至4與比較例1和2之各組成物以形成一白色離型膜，且在80℃的乾燥箱中被乾燥，從而製出一具有20 μm之厚度的各向異性導電膜。
試驗例1
實施例5各向異性導電膜之固化速率的評定
一具有氧化銦錫(indium tin oxide,ITO)電路和2,000 μm2且厚度為5,000Å之凸塊區(bump area)的玻璃基板，與一具有2,000 μm2且厚度為0.7 mm之凸塊區的晶片，被予以接合，並使用在實施例5中所得的各向異性導電膜而上下壓合，繼而在170℃與90 MPa下壓合並加熱5秒鐘，從而製備出各向異性導電膜的樣品。在晶片被以一晶片剪切器(die shear)而切分後，依然位於該玻璃基板上之各向異性 導電膜則被刮下並使用IR來評定為固化速率。茲定義一位在1,540到1,480 cm-1範圍中的峰值為苯環吸收，而一位在930到889 cm-1範圍中的峰值為環氧環(epoxy ring)之吸收，固化速率則藉下述方程式來計算。
T(x)=E(x)/B(x)
E：環氧環之吸收
B：苯環之吸收度
T：環氧環吸收度相對於苯環吸收度之光譜強度比例
x=100：100%之已固化樣品0：0%之已固化樣品？：待測的反應速率樣品
固化速率={(T(？)-T(0))/(T(100)-T(0))}x 100(%)
固化速率之結果提供於表1。
試驗例2
實施例5各向異性導電膜之玻璃轉移溫度的評定
實施例5中所獲得的每一片各向異性導電膜被形成為具有厚度為60 μm的三層式膜，其繼而在190℃下固化1小時，並裁切為30 mm x 5 mm的樣品，接著使用動態熱機械分析儀(DMA)來評定玻璃轉移溫度。
玻璃轉移溫度之結果提供於表2。
試驗例3
實施例5各向異性導電膜之連接可靠性的評定
為了評定實施例5中所獲得的每一各向異性導電膜的連接可靠性，每一各向異性導電膜的電阻係以如下方式被量測。
(1)樣品之製備
一具有氧化銦錫(ITO)電路和2,000 μm2且厚度為5,000 Å之凸塊區的玻璃基板，與一具有2,000 μm2且厚度為1.7 mm之凸塊區的晶片，被予以接合，並使用在實施例5中所得的各向異性導電膜而上下壓合，繼而在170℃與90 MPa下壓合並加熱5秒鐘，從而製備五個具有每一各向異性導電膜的樣品。
(2)初始接線電阻(initial connection resistance)之量測
已完全接合的各樣品的接線電阻被量測5次，並計算出一平均接線電阻(average connection resistance)。
(3)可靠性測試之後的接線電阻量測
在量測初始接線電阻後，各樣品皆以高溫度與高濕度為條件，即85℃與85%的濕度，歷時100小時、250小時及500小時，繼而量測接線電阻並計算一平均接線電阻。
各樣品之該平均初始接線電阻與可靠性測試後的接線電阻被提供於表3。
如表3中所示，在高溫度與高濕度條件下進行可靠性測試後之依據比較例1而獲得的膜的電阻，相較於初始電阻係增加約5.33倍。依據比較例2而獲得的膜增加約11.3倍。然而，依據實施例1而獲得的膜增加約3.07倍，依據實施例2而獲得的膜，則增加約2.9倍。
因此，使用以式1來表示之經氫化的雙酚A環氧單體來製備的各向異性導電膜，相較於一般的各向異性導電膜，即具有緻密而堅硬的性質，因而具有優越的抗熱性與抗濕性及更高的可靠性。
雖然在此已提供了一些具體例，對於熟習此技藝之人士所顯見的是，該等實施例僅供例示之用，而各式各樣的修改、變化、替換，以及等效的具體例皆可在未脫離本發明之精神與範圍下而作成。本發明之範圍應僅受限於所附之申請專利範圍。

Claims (12)

  1. 一種各向異性導電膜組成物，包含：一以式1來表示之經氫化的雙酚A環氧單體，或是一以式2來表示之經氫化的雙酚A環氧寡聚體；一鋶固化劑；一黏著劑樹脂；及導電粒子； 其中n是一自1至50的整數。
  2. 如申請專利範圍第1項之各向異性導電膜組成物，其中以100重量份的各向異性導電膜組成物為基準，包含1到50重量份的該以式1來表示之經氫化的雙酚A環氧單體或是該以式2來表示之經氫化的雙酚A環氧寡聚體、1到20重量份的鋶固化劑、20到60重量份的黏著劑樹脂，以及10到50重量份的導電粒子。
  3. 如申請專利範圍第1項之各向異性導電膜組成物，其中該鋶固化劑包括一芳香族鋶鹽。
  4. 如申請專利範圍第3項之各向異性導電膜組成物，其中 該芳香族鋶鹽是以式3來表示： 其中，R1是選自於由氫、烷基、烷氧基、甲氧羰基，與乙氧羰基所構成的群組；R2是選自於由甲基、乙基、丙基，與丁基所構成的群組；而R3則是選自於由硝基苄基、二硝基苄基、三硝基苄基，與萘甲基所構成的群組。
  5. 如申請專利範圍第3項之各向異性導電膜組成物，其中該芳香族鋶鹽是以式5來表示： 其中，R1是選自於由羥基、R5O-，，與所構成的群組；R5是選自於由芳香族碳氫化合物、經取代的芳香族碳氫化合物、脂肪族碳氫化合物、經取代的脂肪族碳氫化合物、羧基，與磺醯基所 構成的群組；R2則是選自於由氫與C1到C6烷基所構成的群組。
  6. 如申請專利範圍第1項之各向異性導電膜組成物，其中該黏著劑樹脂包括一茀環氧樹脂。
  7. 如申請專利範圍第1到6項中任一項之各向異性導電膜組成物，其中，該各向異性導電膜組成物具有120℃以上的玻璃轉移溫度。
  8. 如申請專利範圍第1到6項中任一項之各向異性導電膜組成物，其中，該各向異性導電膜組成物是使用於玻璃覆晶基板技術(chip-on-glass，COG)。
  9. 一種各向異性導電膜，其包含一以式1來表示之經氫化的雙酚A環氧單體或一以式2來表示之經氫化的雙酚A環氧寡聚體；該各向異性導電膜當在150至170℃固化5到10秒時具有70%以上的固化速率，且具有120℃以上的玻璃轉移溫度； 其中n是一自1至50的整數。
  10. 如申請專利範圍第9項之各向異性導電膜，其中，該各向異性導電膜當在150℃下固化5到10秒時具有70%以 上之固化速率，且具有120℃以上的玻璃轉移溫度。
  11. 如申請專利範圍第9或10項之各向異性導電膜，其中，該各向異性導電膜是使用於玻璃覆晶基板技術(COG)。
  12. 一種半導體裝置，包含：一配線基板；一各向異性導電膜，其係貼附於該配線基板之晶片安裝面上；以及一半導體晶片，其係安裝在該各向異性導電膜上；其中，該各向異性導電膜包括了包含如申請專利範圍第1到8項中任一項之各向異性導電膜組成物的向異性導電膜，或者是如申請專利範圍第9到11項中任一項之各向異性導電膜。
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