TWI651192B - 異向性導電膜及其製造方法 - Google Patents

異向性導電膜及其製造方法 Download PDF

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TWI651192B
TWI651192B TW102130402A TW102130402A TWI651192B TW I651192 B TWI651192 B TW I651192B TW 102130402 A TW102130402 A TW 102130402A TW 102130402 A TW102130402 A TW 102130402A TW I651192 B TWI651192 B TW I651192B
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Taiwan
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connection layer
layer
insulating resin
conductive particles
connection
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TW102130402A
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English (en)
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TW201431674A (zh
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篠原誠一郎
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日商迪睿合股份有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
    • B32B37/025—Transfer laminating
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/263—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer having non-uniform thickness
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
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    • B32B2307/00—Properties of the layers or laminate
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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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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Abstract

本發明之異向性導電膜具有第1連接層被主要由絕緣性樹脂所構成之第2連接層與第3連接層夾持之3層構造。第1連接層具有導電粒子以單層排列於絕緣性樹脂層之第2連接層側之平面方向之構造，且鄰接之導電粒子間之中央區域之絕緣性樹脂層厚度薄於導電粒子附近之絕緣性樹脂層厚度。

Description

異向性導電膜及其製造方法
本發明係關於一種異向性導電膜及其製造方法。
異向性導電膜廣泛地用於IC晶片等電子零件之安裝，近年來，就應用於高安裝密度之觀點而言，以連接可靠性或絕緣性之提高、粒子捕捉效率之提高、製造成本之降低等為目的，而提出有使異向性導電連接用之導電粒子以單層排列於絕緣性接著層而成之異向性導電膜(專利文獻1)。
該異向性導電膜係以如下方式製成。即，首先，使導電粒子保持於具有開口之轉印模之該開口，自其上壓抵轉印用之形成有黏著層之黏著膜，使導電粒子一次轉印於黏著層。繼而，對附著於黏著層之導電粒子壓抵成為異向性導電膜之構成要素之高分子膜，並進行加熱加壓，藉此，使導電粒子二次轉印於高分子膜表面。繼而，於二次轉印有導電粒子之高分子膜之導電粒子側表面以覆蓋導電粒子之方式形成接著層，藉此，製成異向性導電膜。
專利文獻1：日本特開2010-33793號公報
然而，於使用具有開口之轉印模製成之專利文獻1之異向性導電膜之情形時，只要一次轉印以及二次轉印順利進行，則對異向性導電膜之連接可靠性、絕緣性、粒子捕捉效率或許能夠期待某種程度之提高，但通常而言，為了易於進行二次轉印，而使用黏著力相對較低者作為一次轉印用之黏著膜，而且縮小導電粒子與黏著膜之接觸面積。因此，於一次轉印操作至二次轉印操作時，產生如下情況：產生未進行一次轉印之導電粒子，一次轉印後導電粒子自黏著膜剝落或導電粒子於黏著膜上位置偏移等，而有整體之作業效率降低之顧慮。
另一方面，若欲某種程度地增強黏著膜之黏著力而使導電粒子穩定地保持於黏著膜，以使一次轉印作業進一步高速且順利地進行，則向高分子膜之二次轉印變得困難，若為了避免此種情況而增強高分子膜之膜性，則有異向性導電膜之導通電阻增大、導通可靠性亦降低之問題。如此，即便欲使用具有開口之轉印模製成異向性導電膜，實際上一次轉印以及二次轉印亦不一定順利進行，因此，現狀為對異向性導電膜依然強烈地要求同時實現良好之連接可靠性、良好之絕緣性、及良好之粒子捕捉效率。
本發明之目的在於解決以上先前技術之問題，於使用具有開口之轉印模製成之導電粒子以單層排列之異向性導電膜中，實現良好之連接可靠性、良好之絕緣性、及良好之粒子捕捉效率。
本發明者發現，於使用具有開口之轉印模製成異向性導電膜時，使導電粒子以未暫時一次轉印於黏著膜，而自轉印模直接以單層排列於構成異向性導電膜之絕緣性樹脂層之方式轉印，而且以鄰接之導電粒子間之中央之絕緣性樹脂層厚度薄於導電粒子附近之絕緣性樹脂層厚度的方式轉印，進而，由發揮作為接著層功能之絕緣性之樹脂層夾持導電粒子以單層排列之該絕緣性樹脂層之兩面，藉此可達成上述目的，從而完成本發 明。
即，本發明提供一種異向性導電膜，其係第1連接層被主要由絕緣性樹脂所構成之第2連接層與第3連接層夾持之3層構造者，第1連接層具有導電粒子以單層排列於絕緣性樹脂層之第2連接層側之平面方向之構造，且鄰接之導電粒子間之中央區域之絕緣性樹脂層厚度薄於導電粒子附近之絕緣性樹脂層厚度。
又，本發明提供一種上述之異向性導電膜之製造方法，並具有以下步驟(A)~(D)。
<步驟(A)>
於形成有開口之轉印模之開口內配置導電粒子，使形成於剝離膜上之絕緣性樹脂層對向於形成有開口之轉印模之表面之步驟。
<步驟(B)>
自剝離膜側對絕緣性樹脂層施加壓力，將絕緣性樹脂壓入至開口內而使導電粒子轉印於絕緣性樹脂層之表面，藉此形成第1連接層之步驟，該第1連接層係導電粒子以單層排列於絕緣性樹脂層之平面方向之構造，且鄰接之導電粒子間之中央區域之絕緣性樹脂層厚度薄於導電粒子附近之絕緣性樹脂層厚度。
<步驟(C)>
於第1連接層之導電粒子側表面形成主要由絕緣性樹脂所構成之第2連接層之步驟。
<步驟(D)>
於與第2連接層相反側之第1連接層之表面形成主要由絕緣性樹脂所構成之第3連接層之步驟。
又，本發明提供一種上述之異向性導電膜之另一製造方法，並具有以下步驟(a)~(c)。
<步驟(a)>
於形成有開口之轉印模之開口內配置導電粒子，使預先貼合有第3連接層之絕緣性樹脂層對向於形成有開口之轉印模之表面之步驟。
<步驟(b)>
自剝離膜側對絕緣性樹脂層施加壓力，將絕緣性樹脂壓入至開口內而使導電粒子轉印於絕緣性樹脂層之表面，藉此形成第1連接層之步驟，該第1連接層係導電粒子以單層排列於絕緣性樹脂層之平面方向之構造，且鄰接之導電粒子間之中央區域之絕緣性樹脂層厚度薄於導電粒子附近之絕緣性樹脂層厚度。
<步驟(c)>
於第1連接層之導電粒子側表面形成主要由絕緣性樹脂所構成之第2連接層之步驟。
又，本發明提供一種連接構造體，其係利用上述之異向性導電膜將第1電子零件異向性導電連接於第2電子零件而成。
又，本發明提供一種連接方法，其係利用上述之異向性導電膜將第1電子零件異向性導電連接於第2電子零件者，且將異向性導電膜自其第3連接層側暫貼於第2電子零件，將第1電子零件搭載於暫貼之異向性導電膜，並自第1電子零件側進行熱壓接。
第1連接層被絕緣性之第2連接層與第3連接層夾持之3層構造之本發明之異向性導電膜具有如下構造：第1連接層具有導電粒子以單層排列於絕緣性樹脂層之第2連接層側之平面方向之構造、鄰接之導電粒子間之中央之絕緣性樹脂層厚度薄於導電粒子附近之絕緣性樹脂層厚度之構造。因此，於導電粒子以單層排列之異向性導電膜中，可實現良好之連接可靠性、良好之絕緣性、及良好之粒子捕捉效率。
1‧‧‧第1連接層
1X‧‧‧第1連接層中之硬化率較低之區域
1Y‧‧‧第1連接層中之硬化率較高之區域
1d‧‧‧被覆層
2‧‧‧第2連接層
3‧‧‧第3連接層
3a‧‧‧第3連接層之表面
4‧‧‧導電粒子
10‧‧‧絕緣性樹脂層
20‧‧‧轉印模
21‧‧‧開口
22‧‧‧剝離膜
100‧‧‧異向性導電膜
L‧‧‧導電粒子間距離
P‧‧‧導電粒子間距離之中間點
t1、t2‧‧‧絕緣性樹脂層厚
圖1A係本發明之異向性導電膜之剖面圖。
圖1B係本發明之異向性導電膜之剖面圖。
圖1C係本發明之異向性導電膜之剖面圖。
圖2A係本發明之異向性導電膜之製造步驟(A)之說明圖。
圖2B係本發明之異向性導電膜之製造步驟(A)之說明圖。
圖3A係本發明之異向性導電膜之製造步驟(B)之說明圖。
圖3B係本發明之異向性導電膜之製造步驟(B)之說明圖。
圖3C係本發明之異向性導電膜之製造步驟之說明圖。
圖4係本發明之異向性導電膜之製造步驟(C)之說明圖。
圖5係本發明之異向性導電膜之製造步驟(D)之說明圖。
圖6A係本發明之異向性導電膜之製造步驟(a)之說明圖。
圖6B係本發明之異向性導電膜之製造步驟(a)之說明圖。
圖7A係本發明之異向性導電膜之製造步驟(b)之說明圖。
圖7B係本發明之異向性導電膜之製造步驟(b)之說明圖。
圖7C係本發明之異向性導電膜之製造步驟(b)之說明圖。
圖8係本發明之異向性導電膜之製造步驟(c)之說明圖。
以下，對本發明之異向性導電膜進行詳細說明。
<<異向性導電膜>>
如圖1A所示，本發明之異向性導電膜100具有第1連接層1被主要由絕緣性樹脂所構成之第2連接層2與第3連接層3夾持之3層構造。該第1 連接層1具有導電粒子4以單層排列於絕緣性樹脂層10之第2連接層2側之平面方向之構造。於該情形時，導電粒子4亦可於平面方向最密填充，但較佳為導電粒子4於平面方向隔開一定之間隔規則地(例如正方格子狀地)排列。又，具有鄰接之導電粒子4間之中央區域之絕緣性樹脂層厚t1薄於導電粒子4之附近之絕緣性樹脂層厚t2的構造。若絕緣性樹脂層厚t1薄於絕緣性樹脂層厚t2，則於異向性導電連接時未存在於應連接之端子間而未被利用之導電粒子4如圖1B所示，藉由異向性導電連接時之加熱加壓，導電粒子4間之絕緣性樹脂層熔斷，可被覆導電粒子4而形成被覆層1d，故而可抑制短路之產生。
此處，所謂鄰接之導電粒子4間之中央區域，如圖1A所示，係以鄰接之導電粒子間距離L之中間點P為中心±L/4以內之區域。又，所謂導電粒子附近係指於第1連接層1之層厚方向與導電粒子4接觸之線段附近之位置。
再者，絕緣性樹脂層厚t1與絕緣性樹脂層厚t2進而較佳為具有以下關係。其原因在於：若t1相對於t2過薄則有導電粒子4容易流動而使粒子捕捉效率降低之傾向，又，若過於接近t2之厚度，則有難以獲得本發明之效果之傾向。
0.1×t2<t1<0.9×t2
又，作為絕緣性樹脂層厚t1之絕對厚度，若過薄則有難以形成第1連接層1之顧慮，因此較佳為0.5μm以上。另一方面，作為絕緣性樹脂層厚t2之絕對厚度，若過厚則有絕緣性樹脂層10於異向性導電連接時難以自連接區域排除而產生導通不良之顧慮，因此較佳為6μm以下。
再者，於如圖1C所示，包含導電粒子之樹脂層之厚度於平面方向大幅變動，其結果，該樹脂層以被分隔之方式存在之情形時，導電粒子4間之絕緣性樹脂層厚度亦可實質上為0。所謂實質上為0係指包含導 電粒子之絕緣性樹脂層各自獨立地存在之狀態。於此種情形時，不適用上述式，故而為了實現良好之連接可靠性、良好之絕緣性、及良好之粒子捕捉效率，可藉由控制通過導電粒子4之中心之垂線與絕緣性樹脂層厚度最薄之位置的最短距離L1、L2、L3、L4…而較佳地進行。即，若該最短距離L1、L2、L3…變長，則第1連接層1之樹脂量相對增大，生產性提高，可抑制導電粒子4之流動。另一方面，若該最短距離L1、L2、L3、L4…變短，則第1連接層1之樹脂量相對減少，可容易地控制粒子間距離。換言之，可提高導電粒子之位置對準之精度。較佳之距離L1、L2、L3、L4…為導電粒子4之粒徑之較佳為大於0.5倍且未達1.5倍、更佳為0.6~1.2倍之範圍。
又，亦可如圖1C所示，導電粒子4埋沒於第1連接層1。較淺地埋沒抑或較深地埋沒之埋沒程度係根據形成第1連接層1時之材料之黏度、或排列有導電粒子之轉印模之開口之形狀、大小等而變化，尤其是可利用開口之基底直徑與開口直徑之關係控制。例如，較佳為將基底直徑設為導電粒子直徑之1.1倍以上且未達2倍，將開口直徑設為導電粒子直徑之1.3倍以上且未達3倍。
再者，於不損害本發明之效果之範圍內，亦可如圖1C中虛線所示，於第2連接層2存在導電粒子4'。
<第1連接層>
作為構成此種第1連接層1之絕緣性樹脂層10，可適當採用公知之絕緣性樹脂層。例如，可採用包含丙烯酸酯化合物與熱或光自由基聚合起始劑之熱或光自由基聚合型樹脂層或者使其進行熱或光自由基聚合而成者、或者包含環氧化合物與熱或光陽離子或陰離子聚合起始劑之熱或光陽離子或陰離子聚合型樹脂層或者使其進行熱或光陽離子聚合或陰離子聚合而成者。
其中，作為構成第1連接層1之絕緣性樹脂層10，可採用 包含丙烯酸酯化合物與熱自由基聚合起始劑之熱自由基聚合型樹脂層，但較佳為採用包含丙烯酸酯化合物與光自由基聚合起始劑之光自由基聚合型樹脂層。藉此，可對光自由基聚合型樹脂層照射紫外線進行光自由基聚合而形成第1連接層1。於該情形時，若於形成第2連接層2前，自導電粒子側對光自由基聚合型樹脂層照射紫外線而進行光自由基聚合，則如圖1A所示，於第1連接層1中，可使位於導電粒子4與第3連接層3之表面3a之間之區域1X之硬化率低於位於相互鄰接之導電粒子間之區域1Y之硬化率。因此，可使第1連接層中硬化率較低之區域1X之最低熔融黏度小於第1連接層中硬化率較高之區域1Y之最低熔融黏度，而於異向性導電連接時，可防止導電粒子4之位置偏移，提高粒子捕捉效率，提高導電粒子4之壓入性，降低導通電阻值，實現良好之導通可靠性。
此處，硬化率係被定義為有助於聚合之官能基(例如乙烯基)之減少比率之數值。具體而言，若硬化後之乙烯基之存在量為硬化前之20%，則硬化率成為80%。乙烯基之存在量之測定可藉由紅外吸收光譜之乙烯基之特性吸收分析進行。
如此定義之區域1X之硬化率較佳為40~80%，另一方面，區域1Y之硬化率較佳為70~100%。
又，以流變儀測得之第1連接層1之最低熔融黏度較佳為高於第2連接層2及第3連接層3各自之最低熔融黏度。具體而言，若[第1連接層1之最低熔融黏度(mPa．s)]/[第2連接層2或第3連接層3之最低熔融黏度(mPa．s)]之數值過低，則有粒子捕捉效率降低、短路產生之概率上升之傾向，若過高則有導通可靠性降低之傾向，因此較佳為1~1000，更佳為4~400。再者，各自較佳之最低熔融黏度中，關於前者，若過低則有粒子捕捉效率降低之傾向，若過高則有導通電阻值變大之傾向，因此較佳為100~100000mPa．s，更佳為500~50000mPa．s。關於後者，若過低 則有於製成捲筒時產生樹脂之溢出之傾向，若過高則有導通電阻值變高之傾向，因此較佳為0.1~10000mPa．s，更佳為1~1000mPa．s。
<丙烯酸酯化合物>
作為構成第1連接層1之絕緣性樹脂層10所使用之丙烯酸酯化合物，可使用先前公知之自由基聚合性丙烯酸酯。例如可使用單官能(甲基)丙烯酸酯(此處，(甲基)丙烯酸酯包含丙烯酸酯與甲基丙烯酸酯)、二官能以上之多官能(甲基)丙烯酸酯。於本發明中，為了將接著劑設為熱硬化性，較佳為於丙烯酸系單體之至少一部分使用多官能(甲基)丙烯酸酯。
作為單官能(甲基)丙烯酸酯，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-甲基丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸正庚酯、(甲基)丙烯酸2-甲基己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸2-丁基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸異酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸啉-4-酯等。作為二官能(甲基)丙烯酸酯，可列舉：雙酚F-EO改質二(甲基)丙烯酸酯、雙酚A-EO改質二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、三環癸烷二羥甲基二(甲基)丙烯酸酯、二環戊二烯二(甲基)丙烯酸酯等。作為三官能(甲基)丙烯酸酯，可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基丙烷PO改質三(甲基)丙烯酸酯、異氰尿酸EO改質三(甲基)丙烯酸酯等。作為四官能以上之(甲基)丙烯酸酯，可列舉：二新戊四醇五(甲基)丙烯酸酯、新戊四醇六(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二-三羥甲基丙烷四丙烯酸酯等。此外，亦可使用 多官能(甲基)丙烯酸胺酯。具體而言，可列舉：M1100、M1200、M1210、M1600(以上為東亞合成(股))、AH-600、AT-600(以上為共榮社化學(股))等。
若構成第1連接層1之絕緣性樹脂層10中之丙烯酸酯化合物之含量過少，則有變得難以賦予其與第2連接層2之最低熔融黏度差之傾向，若過多，則有硬化收縮變大而作業性降低之傾向，因此較佳為2~70質量%，更佳為10~50質量%。
<光自由基聚合起始劑>
作為光自由基聚合起始劑，可自公知之光自由基聚合起始劑中適當選擇而使用。例如可列舉：苯乙酮系光聚合起始劑、苯偶醯縮酮系光聚合起始劑、磷系光聚合起始劑等。具體而言，作為苯乙酮系光聚合起始劑，可列舉：2-羥基-2-環己基苯乙酮(IRGACURE 184，BASF Japan(股))、α-羥基-α,α'-二甲基苯乙酮(DAROCUR 1173，BASF Japan(股))、2,2-二甲氧基-2-苯基苯乙酮(IRGACURE 651，BASF Japan(股))、4-(2-羥基乙氧基)苯基(2-羥基-2-丙基)酮(DAROCUR 2959，BASF Japan(股))、2-羥基-1-{4-[2-羥基-2-甲基-丙醯基]-苄基}苯基}-2-甲基-丙烷-1-酮(IRGACURE 127，BASF Japan(股))等。作為苯偶醯縮酮系光聚合起始劑，可列舉：二苯甲酮、茀酮、二苯并環庚酮、4-胺基二苯甲酮、4,4'-二胺基二苯甲酮、4-羥基二苯甲酮、4-氯二苯甲酮、4,4'-二氯二苯甲酮等。又，亦可使用2-苄基-2-二甲胺基-1-(4-啉基苯基)-丁酮-1(IRGACURE 369，BASF Japan(股))。作為磷系光聚合起始劑，可列舉：雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦(IRGACURE 819，BASF Japan(股))、(2,4,6-三甲基苯甲醯基)-二苯基氧化膦(DAROCURE TPO，BASF Japan(股))等。
若光自由基聚合起始劑之使用量相對於丙烯酸酯化合物100質量份過少，則有光自由基聚合未充分進行之傾向，若過多，則有成為剛 性降低之原因之顧慮，因此較佳為0.1~25質量份，更佳為0.5~15質量份。
<熱自由基聚合起始劑>
又，作為熱自由基聚合起始劑，例如可列舉有機過氧化物或偶氮系化合物等，可較佳地使用不產生成為氣泡之原因之氮氣之有機過氧化物。
作為有機過氧化物，可列舉：過氧化甲基乙基酮、過氧化環己酮、過氧化甲基環己酮、過氧化乙醯丙酮、1,1-雙(第三丁基過氧化)3,3,5-三甲基環己烷、1,1-雙(第三丁基過氧化)環己烷、1,1-雙(第三己基過氧化)3,3,5-三甲基環己烷、1,1-雙(第三己基過氧化)環己烷、1,1-雙(第三丁基過氧化)環十二烷、異丁基過氧化物、過氧化月桂醯、過氧化琥珀酸、過氧化3,5,5-三甲基己醯、過氧化苯甲醯、過氧化辛醯、過氧化硬脂醯、過氧化二碳酸二異丙酯、過氧化二碳酸二正丙酯、過氧化二碳酸二-2-乙基己酯、過氧化二碳酸二-2-乙氧基乙酯、過氧化二碳酸二-2-甲氧基丁酯、過氧化二碳酸雙-(4-第三丁基環己基)酯、(α,α-雙-新癸醯過氧化)二異丙基苯、過氧化新癸酸異丙苯酯、過氧化新癸酸辛酯、過氧化新癸酸己酯、過氧化新癸酸第三丁酯、過氧化新戊酸第三己酯、過氧化新戊酸第三丁酯、2,5-二甲基-2,5-雙(2-乙基己醯基過氧化)己烷、過氧化-2-乙基己酸-1,1,3,3-四甲基丁酯、過氧化-2-乙基己酸第三己酯、過氧化-2-乙基己酸第三丁酯、過氧化-3-甲基丙酸第三丁酯、過氧化月桂酸第三丁酯、過氧化-3,5,5-三甲基己酸第三丁酯、過氧化異丙基單碳酸第三己酯、過氧化異丙基碳酸第三丁酯、2,5-二甲基-2,5-雙(苯甲醯基過氧化)己烷、過乙酸第三丁酯、過苯甲酸第三己酯、過苯甲酸第三丁酯等。亦可於有機過氧化物中添加還原劑而作為氧化還原系聚合起始劑使用。
作為偶氮系化合物，可列舉：1,1-偶氮雙(環己烷-1-腈)、2,2'-偶氮雙(2-甲基-丁腈)、2,2'-偶氮雙丁腈、2,2'-偶氮雙(2,4-二甲基-戊腈)、2,2'-偶氮雙(2,4-二甲基-4-甲氧基戊腈)、2,2'-偶氮雙(2-脒基-丙烷)鹽酸鹽、2,2'-偶 氮雙[2-(5-甲基-2-咪唑啉-2-基)丙烷]鹽酸鹽、2,2'-偶氮雙[2-(2-咪唑啉-2-基)丙烷]鹽酸鹽、2,2'-偶氮雙[2-(5-甲基-2-咪唑啉-2-基)丙烷]、2,2'-偶氮雙[2-甲基-N-(1,1-雙(2-羥基甲基)-2-羥基乙基)丙醯胺]、2,2'-偶氮雙[2-甲基-N-(2-羥基乙基)丙醯胺]、2,2'-偶氮雙(2-甲基-丙醯胺)二水合物、4,4'-偶氮雙(4-氰基-戊酸)、2,2'-偶氮雙(2-羥基甲基丙腈)、2,2'-偶氮雙(2-甲基丙酸)二甲酯(dimethyl-2,2'-azobis(2-methyl propionate))、氰基-2-丙基偶氮甲醯胺等。
若熱自由基聚合起始劑之使用量過少，則硬化不良，若過多，則製品壽命降低，因此相對於丙烯酸酯化合物100質量份，較佳為2~60質量份，更佳為5~40質量份。
<環氧化合物>
又，亦可使構成第1連接層1之絕緣性樹脂層10由含有環氧化合物與熱或光陽離子或陰離子聚合起始劑之熱或光陽離子或陰離子聚合型樹脂層、或者使該等進行熱或光陽離子聚合或陰離子聚合而成者構成。
作為環氧化合物，較佳為列舉於分子內具有2個以上環氧基之化合物或樹脂。該等可為液狀亦可為固體狀。具體而言，可列舉：使雙酚A、雙酚F、雙酚S、六氫雙酚A、四甲基雙酚A、二烯丙基雙酚A、對苯二酚、鄰苯二酚、間苯二酚、甲酚、四溴雙酚A、三羥基聯苯、二苯甲酮、雙間苯二酚、雙酚六氟丙酮、四甲基雙酚F、三(羥基苯基)甲烷、聯二甲苯酚、苯酚酚醛清漆、甲酚酚醛清漆等多酚與表氯醇反應而獲得之環氧丙醚，或者使甘油、新戊二醇、乙二醇、丙二醇、丁二醇、己二醇、聚乙二醇、聚丙二醇等脂肪族多元醇與表氯醇反應而獲得之聚環氧丙醚；使對羥基苯甲酸、β-羥基萘甲酸之類之羥基羧酸與表氯醇反應而獲得之環氧丙醚酯，或者由鄰苯二甲酸、甲基鄰苯二甲酸、間苯二甲酸、對苯二甲酸、四氫鄰苯二甲酸、六氫鄰苯二甲酸、內亞甲基四氫鄰苯二甲酸、內亞甲基六氫鄰苯二甲酸、偏苯三甲酸、聚合脂肪酸之類之多羧酸獲得之聚環氧丙 酯；由胺基苯酚、胺基烷基苯酚獲得之環氧丙基胺基環氧丙醚；由胺基苯甲酸獲得之環氧丙基胺基環氧丙酯；由苯胺、甲苯胺、三溴苯胺、苯二甲胺(Xylylenediamine)、二胺基環己烷、雙胺基甲基環己烷、4,4'-二胺基二苯基甲烷、4,4'-二胺基二苯基碸等獲得之環氧丙胺；環氧化聚烯烴等公知之環氧樹脂類。又，亦可使用3',4'-環氧環己烯羧酸3,4-環氧環己烯基甲酯等脂環式環氧化合物。
<熱陽離子聚合起始劑>
作為熱陽離子聚合起始劑，可採用作為環氧化合物之熱陽離子聚合起始劑所公知者，例如為藉由熱而產生可使陽離子聚合型化合物進行陽離子聚合之酸者，可使用公知之錪鹽、鋶鹽、鏻鹽、二茂鐵類等，可較佳地使用對溫度顯示良好之潛伏性之芳香族鋶鹽。作為熱陽離子系聚合起始劑之較佳例，可列舉：六氟銻酸二苯基錪、六氟磷酸二苯基錪、六氟硼酸二苯基錪、六氟銻酸三苯基鋶、六氟磷酸三苯基鋶、六氟硼酸三苯基鋶。具體而言，可列舉：ADEKA(股)製造之SP-150、SP-170、CP-66、CP-77；日本曹達(股)製造之CI-2855、CI-2639；三新化學工業(股)製造之San-Aid SI-60、SI-80；Union Carbide公司製造之CYRACURE-UVI-6990、UVI-6974等。
若熱陽離子聚合起始劑之調配量過少，則有未充分進行熱陽離子聚合之傾向，若過多，則有成為剛性降低之原因之顧慮，因此相對於環氧化合物100質量份，較佳為0.1~25質量份，更佳為0.5~15質量份。
<熱陰離子聚合起始劑>
作為熱陰離子聚合起始劑，可採用作為環氧化合物之熱陰離子聚合起始劑所公知者，例如為藉由熱而產生可使陰離子聚合性化合物進行陰離子聚合之鹼者，可使用公知之脂肪族胺系化合物、芳香族胺系化合物、二級或三級胺系化合物、咪唑系化合物、多硫醇系化合物、三氟化硼-胺錯合物、雙氰胺、有機醯肼等，可較佳地使用對溫度顯示良好之潛伏性之膠囊化咪 唑系化合物。具體而言，可列舉ASAHI KASEI E-MATERIALS(股)製造之Novacure HX3941HP等。
若熱陰離子聚合起始劑之調配量過少，則有硬化不良之傾向，若過多，則有製品壽命降低之傾向，因此相對於環氧化合物100質量份，較佳為2~60質量份，更佳為5~40質量份。
<光陽離子聚合起始劑及光陰離子聚合起始劑>
作為環氧化合物用之光陽離子聚合起始劑或光陰離子聚合起始劑，可適當使用公知者。
<導電粒子>
作為構成第1連接層1之導電粒子4，可自先前公知之異向性導電膜所使用者中適當選擇而使用。例如可列舉：鎳、鈷、銀、銅、金、鈀等金屬粒子、金屬被覆樹脂粒子等。亦可併用2種以上。
作為導電粒子4之平均粒徑，若過小，則有無法應對配線高度之不均，導通電阻上升之傾向，若過大，則有成為短路之產生原因之傾向，因此較佳為1~10μm，更佳為2~6μm。平均粒徑可藉由通常之粒度分佈測定裝置進行測定。
若此種導電粒子4於第1連接層1中之存在量過少，則粒子捕捉效率降低而變得難以進行異向性導電連接，若過多，則有產生短路之顧慮，因此較佳為每1平方mm為50~40000個，更佳為200~20000個。
<第1連接層中之其他成分>
於第1連接層1，可視需要併用苯氧基樹脂、環氧樹脂、不飽和聚酯樹脂、飽和聚酯樹脂、胺酯樹脂、丁二烯樹脂、聚醯亞胺樹脂、聚醯胺樹脂、聚烯烴樹脂等膜形成樹脂。
於構成第1連接層1之絕緣性樹脂層10為使由丙烯酸酯化合物與光自由基聚合起始劑所構成之光自由基聚合型樹脂層進行光自由基 聚合而成者之情形時，較佳為於絕緣性樹脂層10進而含有環氧化合物與熱陽離子聚合起始劑。於該情形時，較佳為如下所述亦將第2連接層2以及第3連接層3設為含有環氧化合物與熱陽離子聚合起始劑之熱陽離子聚合型樹脂層。藉此，可提高層間剝離強度。
於第1連接層1中，較佳為如圖1A所示，導電粒子4沒入至第2連接層2(換言之，導電粒子4於第1連接層1之表面露出)。其原因在於：若導電粒子4全部埋沒於第1連接層1，則有因絕緣性樹脂層10之排除不足而導致導通電阻降低之顧慮。若沒入之程度過小，則有粒子捕捉效率降低之傾向，若過大，則有導通電阻上升之傾向，因此較佳為導電粒子4之平均粒徑之10~90%，更佳為20~80%。
第1連接層1之形成可藉由如下方式進行：於形成有開口之模之開口內配置導電粒子4，使形成於剝離膜上之成為第1連接層1之絕緣性樹脂層10對向於形成有開口21之模之表面，並一面視需要加熱一面加壓至絕緣性樹脂未進入至開口底部之頂端之程度。
<第2連接層及第3連接層>
第2連接層2及第3連接層3均主要由絕緣性樹脂形成。作為絕緣性樹脂，可自公知之絕緣性樹脂中適當選擇而使用。可由與第1連接層1之絕緣性樹脂層10相同之材質形成。
第2連接層2係位於第1連接層1之導電粒子4側者，通常為配置於IC晶片之凸塊等必需以較高之位置精度對準之端子側之層。另一方面，第3連接層3通常為配置於玻璃基板之固體電極等未要求相對較高之對準精度之端子側者。
若第2連接層2之層厚度過薄，則有產生因樹脂填充不足所導致之導通不良之顧慮，若過厚，則有於壓接時產生樹脂之溢出而污染壓接裝置之顧慮，因此較佳為5~20μm，更佳為8~15μm。另一方面，若 第3連接層3之層厚度過薄，則有產生暫貼於第2電子零件時之貼附不良之顧慮，若過厚，則有導通電阻值變大之傾向，因此較佳為0.5~6μm，更佳為1~5μm。
<<異向性導電膜之製造方法>>
繼而，對本發明之異向性導電膜之製造方法之一例進行說明。該製造方法具有以下步驟(A)~(D)。以下對每個步驟進行說明。
<步驟(A)>
如圖2A所示，於形成有開口21之轉印模20之開口21內配置導電粒子4，如圖2B所示，使形成於剝離膜22上之絕緣性樹脂層10對向於形成有開口21之轉印模20之表面。
作為轉印模20，例如為利用光微影法等公知之開口形成方法而於矽、各種陶瓷、玻璃、不鏽鋼等金屬等無機材料、或各種樹脂等有機材料等形成開口者。此種轉印模20可採用板狀、輥狀等形狀。
轉印模20之開口21於其內部收容導電粒子4。作為開口21之形狀，可例示圓柱狀、四角柱等多角柱狀、四角錐等角錐狀等。
作為開口21之排列，較佳為設為格子狀、鋸齒狀等規則之排列。
再者，轉印模20之開口21之直徑與深度可利用雷射顯微鏡測定。
作為將導電粒子4收容於轉印模20之開口21內之方法，並無特別限定，可採用公知之方法。例如，於將已乾燥之導電粒子粉末或使其分散於溶劑中而成之分散液散佈或塗佈於轉印模20之開口形成面上之後，使用毛刷或刮刀等擦拭開口形成面之表面即可。
就轉印性提高與導電粒子保持性之平衡而言，導電粒子4之平均粒徑相對於開口21之深度之比(=導電粒子之平均粒徑/開口之深 度)較佳為0.4~3.0，更佳為0.5~1.5。
又，就導電粒子之易收容性、絕緣性樹脂之易壓入性等之平衡而言，開口21之直徑相對於導電粒子4之平均粒徑之比(=開口之直徑/導電粒子之平均粒徑)較佳為1.1~2.0，更佳為1.3~1.8。
再者，於與開口21之直徑相比，其基底側之直徑較小之情形時，較佳為將基底直徑設為導電粒子直徑之1.1倍以上未達2倍，將開口直徑設為導電粒子直徑之1.3倍以上未達3倍。
<步驟(B)>
繼而，如圖3A所示，自剝離膜22側對絕緣性樹脂層10施加壓力，將絕緣性樹脂壓入至開口21內而使導電粒子4以埋入之方式轉印於絕緣性樹脂層10之表面。藉此，形成如圖3B所示之第1連接層1，該第1連接層1係導電粒子4以單層排列於絕緣性樹脂層10之平面方向之構造，且鄰接之導電粒子4間之中央區域之絕緣性樹脂層厚度薄於導電粒子附近之絕緣性樹脂層厚度。於該情形時，於鄰接之導電粒子4間，絕緣性樹脂層厚度亦可實質上成為0(參照圖1C)。若實質上成為0，則連接後之各導電粒子之獨立性增高，變得容易防止導電粒子於連接時互相連結。
<步驟(C)>
繼而，如圖4所示，於第1連接層1之導電粒子4側表面形成主要由絕緣性樹脂構成之第2連接層2。藉此，第1連接層與第2連接層之邊界成為起伏之狀態，換言之其形狀成為波型或凹凸型。藉由如此對存在於膜內之層應用具有起伏之形狀，可提高使接合時主要相對於凸塊之接觸面積增加的概率，其結果，可期待接著強度之提高。
<步驟(D)>
繼而，於去除剝離膜22後，於與第2連接層2相反側之第1連接層1之表面形成主要由絕緣性樹脂構成之第3連接層3。藉此，可獲得圖5所示 之異向性導電膜100。
再者，較佳為於步驟(B)與步驟(C)之間，如圖3C所示自導電粒子4側對第1連接層1照射紫外線UV。藉此，可使導電粒子4固定於第1連接層1，而且可使導電粒子4之下方之第1連接層1之硬化率與其周圍相比相對降低，可提高異向性導電連接時之導電粒子之壓入性。
<<異向性導電膜之製造方法>>
又，對本發明之異向性導電膜之另一製造方法之例進行說明。該製造方法係使用第3連接層3來代替剝離膜22之態樣，並具有以下步驟(a)~(c)。以下對每個步驟進行說明。
<步驟(a)>
如圖6A所示，於形成有開口21之轉印模20之開口21內配置導電粒子4，如圖6B所示，使預先貼合有第3連接層3之絕緣性樹脂層10對向於形成有開口21之轉印模20之表面。
<步驟(b)>
繼而，如圖7A所示，自第3連接層3側對絕緣性樹脂層10施加壓力，將絕緣性樹脂壓入至開口21內而使導電粒子4轉印於絕緣性樹脂層10之表面。藉此，形成如圖7B所示之第1連接層1，該第1連接層1係導電粒子4以單層排列於絕緣性樹脂層10之平面方向之構造，且鄰接之導電粒子4間之中央區域之絕緣性樹脂層厚度薄於導電粒子附近之絕緣性樹脂層厚度。於該情形時，於鄰接之導電粒子4間，絕緣性樹脂層厚度亦可實質上成為0(參照圖1C)。若實質上成為0，則連接後之各導電粒子之獨立性增高，變得容易防止導電粒子於連接時互相連結。
<步驟(c)>
繼而，於第1連接層1之導電粒子4側表面形成主要由絕緣性樹脂構成之第2連接層2。藉此，可獲得圖8所示之異向性導電膜100。
再者，較佳為於步驟(b)與步驟(c)之間，如圖7C所示自導電粒子4側對第1連接層1照射紫外線UV。藉此，可使導電粒子4固定於第1連接層1，而且可使導電粒子4之下方之第1連接層1之硬化率與其周圍相比相對降低，可提高異向性導電連接時之導電粒子之壓入性。
然而，於圖8所示之異向性導電膜中，導電粒子4主要包含於第1連接層1。於該情形時，於對一個導電粒子進行觀察時，包裹其之第1連接層1之區域於第2連接層2側成為凸形狀，因此，該區域之第3連接層側之寬度比第2連接層側之寬度寬。該寬度寬側之導電粒子4之厚度方向端部(粒子之下側端部)與至第2連接層2為止之水平方向之最短距離p有助於連接時之導電粒子之穩定性。即，p具有相當於固定部分之基座之作用。換言之，導電粒子附近之樹脂成為山型可使包含於其中之粒子留在其內部並孤立化。其原因在於：於導電粒子因按壓而被壓縮時，藉由包裹該導電粒子之第1連接層之緩坡部分之存在，而增高相對地抑制導電粒子向平面方向之流動之概率。該效果係如已說明般，即便於導電粒子間中央區域不存在第1連接層之厚度，本質上亦顯示相同之效果。其原因在於：如上所述，粒子流動之抑制係由其附近樹脂之形狀所擔負，無論其端部為封閉或略微開放均無本質性之差異。因此，作為防止導電粒子間之連結之效果，結果可期待大致相同之表現。根據以上情況，p表示相當於至山型之緩坡之長度、即至可期待作用效果之長度。於該情形時，導電粒子之厚度方向端部與至第2連接層2為止之水平方向之最短距離p較佳為導電粒子直徑之0.5~1.5倍，更佳為0.55~1.25倍。
<<異向性導電膜之用途>>
以上述方式獲得之異向性導電膜可較佳地用於利用熱或光將IC晶片、IC模組等第1電子零件與撓性基板、玻璃基板等第2電子零件進行異向性導電連接之時。以上述方式所獲得之連接構造體亦為本發明之一部分。於 該情形時，就提高連接可靠性之方面而言，較佳為將異向性導電膜自其第3連接層側暫貼於配線基板等第2電子零件，將IC晶片等第1電子零件搭載於暫貼之異向性導電膜，並自第1電子零件側進行熱壓接。又，亦可利用光硬化進行連接。
實施例
以下，藉由實施例具體說明本發明。
實施例1~10
依據表1或表2中所記載之組成，利用乙酸乙酯或甲苯將丙烯酸酯及光自由基聚合起始劑等以固形物成分成為50質量%之方式製備成混合液。將該混合液以乾燥厚度成為5μm之方式塗佈於厚度50μm之聚對苯二甲酸乙二酯膜(PET膜)，並於80℃之烘箱中乾燥5分鐘，藉此，形成成為第1連接層之光自由基聚合型之絕緣性樹脂層。
繼而，準備以縱橫9μm間距設置有直徑5.5μm深度4.5μm之圓柱狀之開口的不鏽鋼製之轉印模，將平均粒徑4μm之導電粒子(鍍Ni/Au樹脂粒子，AUL704，積水化學工業(股))逐一收容於各開口。藉由使第1連接層用之絕緣性樹脂層與該轉印模之開口形成面相對向，並自剝離膜側以60℃0.5 MPa之條件加壓，而將導電粒子壓入至絕緣性樹脂層。藉此，形成鄰接之導電粒子間之中央區域之絕緣性樹脂層厚度薄於導電粒子附近之絕緣性樹脂層厚度的絕緣性樹脂層。
繼而，自該導電粒子側對光自由基聚合型之絕緣性樹脂層照射波長365nm、累積光量4000mL/cm2之紫外線，藉此形成導電粒子固定於表面之第1連接層。
利用乙酸乙酯或甲苯將熱硬化性樹脂及潛伏性硬化劑等以固形物成分成為50質量%之方式製備成混合液。將該混合液以乾燥厚度成為12μm之方式塗佈於厚度50μm之PET膜，並於80℃之烘箱中乾燥5 分鐘，藉此，形成第2連接層。藉由相同之操作而形成乾燥厚度3μm之第3連接層。
以導電粒子成為內側之方式以60℃、0.5MPa之條件對以此種方式所獲得之第1連接層層疊第2連接層，接著對相反面同樣地層疊第3連接層，藉此獲得異向性導電膜。
再者，關於實施例7~10，係以導電粒子間之第1連接層之厚度實質上成為0之方式製成異向性導電膜。具體而言，於使第1連接層用之絕緣性樹脂層對向，並自剝離膜側於60℃0.5MPa之條件下加壓後，以60℃1.0MPa之條件再加壓，除此以外，以與實施例1相同之條件製成異向性導電膜。
比較例1
依據表1中所記載之組成，與實施例1同樣地形成作為第1連接層之前驅層之光自由基聚合型之絕緣性樹脂層。
繼而，準備以縱橫9μm間距設置有直徑5.5μm深度4.5μm之圓柱狀之開口的不鏽鋼製之轉印模，將平均粒徑4μm之導電粒子(鍍Ni/Au樹脂粒子，AUL704，積水化學工業(股))逐一收容於各開口。藉由使第1連接層用之絕緣性樹脂層與該轉印模之開口形成面相對向，並自剝離膜側以40℃0.1MPa之相對較弱之條件加壓，而將導電粒子轉印於絕緣性樹脂層表面。取出轉印有導電粒子之該膜，以樹脂層之表面變得平坦之方式將導電粒子完全壓入至絕緣性樹脂層中。
繼而，對埋入有導電粒子之光自由基聚合型之絕緣性樹脂層照射波長365nm、累積光量4000mL/cm2之紫外線，藉此形成平坦之第1連接層。
對該第1連接層層疊與實施例1同樣地製成之12μm厚之第2連接層與3μm厚之第3連接層，藉此獲得異向性導電膜。
比較例2
由表1之第1連接層用之樹脂組成物中以每1平方mm為20000個之方式均勻地分散有與實施例1中使用者相同之導電粒子的混合物製成厚度6μm之含導電粒子之樹脂膜。以60℃0.5MPa之條件對該膜貼附與實施例1同樣地製成之厚度12μm之第2連接層，藉此製成2層構造之異向性導電膜。
<評價>
關於所獲得之異向性導電膜中導電粒子間之平面方向均等排列，於形成平面均等排列之情形時設為有其應用(有)，將除此以外設為未應用(無)。又，關於導電粒子附近之絕緣性樹脂層厚度，於大於導電粒子間之中間區域之絕緣性樹脂層厚度(層厚度0亦包含在內)之情形時，設為有導電粒子附近之絕緣性樹脂層厚度之增大(有)，將除此以外之情形設為沒有(無)。將其結果示於表1或表2。再者，亦一併表示異向性導電膜之構成層數。
使用所獲得之異向性導電膜，以180℃、80MPa、5秒之條件將0.5×1.8×20.0mm之大小之IC晶片(凸塊尺寸30×85μm，凸塊高度15μm，凸塊間距50μm)安裝於0.5×50×30mm大小之Corning公司製造之玻璃配線基板(1737F)，獲得連接構造試樣體。利用電子顯微鏡觀察該連接構造試樣體之連接部之剖面，結果可確認如圖1A所示，於導電粒子之周圍存在絕緣性樹脂層。
針對獲得之連接構造試樣體，如以下說明般，對「最低熔融黏度」、「粒子捕捉效率」、「導通可靠性」及「絕緣性」進行試驗評價。將所獲得之結果示於表1或表2。
「最低熔融黏度」
使用旋轉式流變儀(TA Instruments公司)，以升溫速度10℃/分鐘、測 定壓力固定為5g、使用測定板直徑8mm之條件測定構成連接構造試樣體之第1連接層及第2連接層各自之最低熔融黏度。
「粒子捕捉效率」
依據以下數式，求出“加熱、加壓後(實際安裝後)之連接構造試樣體之凸塊上實際捕捉到之粒子量”相對於“存在於加熱、加壓前之連接構造試樣體之凸塊上之理論粒子量”的比率。於實際使用上較理想為50%以上。
粒子捕捉效率(%)= {[加熱加壓後之凸塊上之粒子數]/[加熱加壓前之凸塊上之粒子數]}×100
「導通可靠性」
將連接構造試樣體放置於85℃、85%RH之高溫高濕環境下，測定初始與經過500小時後之導通電阻值。於實際使用上較理想為經過500小時後電阻值亦為10Ω以下。
「絕緣性」
求出7.5μm間隔之梳齒TEG圖案之短路產生率。於實際使用上較理想為100ppm以下。
由表1可知，關於實施例1~6之異向性導電膜，於粒子捕捉效率、導通可靠性、絕緣性之各評價項目中均顯示實際使用上較佳之結果。再者，由實施例1~4之結果可知，若第1、第2、第3連接層均為相同之硬化系統，則有由於該等層彼此進行反應，故而導電粒子之壓入性稍微降低而使導通電阻值上升之傾向。又，可知若第1連接層為陽離子聚合系統，則與自由基聚合系統相比，耐熱性改善，故而仍然有導電粒子之壓入性稍微降低而使導通電阻值上升之傾向。
與此相對，關於比較例1之異向性導電膜，由於在第1連接層中，鄰接之導電粒子間之中央區域之絕緣性樹脂層厚度未薄於導電粒子附近之絕緣性樹脂層厚度，故而導通可靠性大幅降低。關於先前之2層構造之比較例2之異向性導電膜，粒子捕捉效率大幅降低，絕緣性亦存在問題。
又，由表2可知，實施例7~10之異向性導電膜由於導電粒子間中央部之厚度為零，故而導電粒子之獨立性增高，關於粒子捕捉效率、導通可靠性、絕緣性之各評價項目均顯示實際使用上較佳之結果。
[產業上之可利用性]
第1連接層被絕緣性之第2連接層與第3連接層所夾持之3層構造之本發明之異向性導電膜具有如下構造：第1連接層具有導電粒子以單層排列於絕緣性樹脂層之第2連接層側之平面方向之構造、鄰接之導電粒子間之中央之絕緣性樹脂層厚度薄於導電粒子附近之絕緣性樹脂層厚度之構造。因此，於導電粒子以單層排列之異向性導電膜中，可實現良好之連接可靠性、良好之絕緣性、及良好之粒子捕捉效率。因此，可用於IC晶片等電子零件向配線基板之異向性導電連接。

Claims (12)

  1. 一種異向性導電膜，其係第1連接層被主要由絕緣性樹脂所構成之第2連接層與第3連接層夾持之3層構造者，第1連接層具有導電粒子以單層排列於絕緣性樹脂層之第2連接層側之平面方向之構造，且鄰接之導電粒子間之中央區域之絕緣性樹脂層厚度薄於導電粒子附近之絕緣性樹脂層厚度，且導電粒子沒入至第2連接層。
  2. 如申請專利範圍第1項之異向性導電膜，其中第1連接層為包含丙烯酸酯化合物與熱或光自由基聚合起始劑之熱或光自由基聚合型樹脂層或使其進行熱或光自由基聚合而成者、或者包含環氧化合物與熱或光陽離子或陰離子聚合起始劑之熱或光陽離子或陰離子聚合型樹脂層或使其進行熱或光陽離子聚合或陰離子聚合而成者。
  3. 如申請專利範圍第1或2項之異向性導電膜，其中於第1連接層中，位於導電粒子與第1連接層之第3連接層側表面之間的區域之第1連接層之硬化率低於位於相互鄰接之導電粒子間的區域之第1連接層之硬化率。
  4. 如申請專利範圍第1或2項之異向性導電膜，其中第1連接層之最低熔融黏度高於第2連接層及第3連接層各自之最低熔融黏度。
  5. 如申請專利範圍第4項之異向性導電膜，其中第1連接層之最低熔融黏度相對於第2連接層及第3連接層各自之最低熔融黏度的比為1：4~400，上述比為第2連接層及第3連接層各自之最低熔融黏度：第1連接層之最低熔融黏度。
  6. 如申請專利範圍第1或2項之異向性導電膜，其中導電粒子之下側端部與至第2連接層為止之水平方向之最短距離為粒徑之0.5~1.5倍。
  7. 一種異向性導電膜之製造方法，其係申請專利範圍第1項之異向性導電膜之製造方法，並具有以下步驟(A)~(D)：步驟(A)於形成有開口之轉印模之開口內配置導電粒子，使形成於剝離膜上之絕緣性樹脂層對向於形成有開口之轉印模之表面之步驟；步驟(B)自剝離膜側對絕緣性樹脂層施加壓力，將絕緣性樹脂壓入至開口內而使導電粒子轉印於絕緣性樹脂層之表面，藉此形成第1連接層之步驟，該第1連接層係導電粒子以單層排列於絕緣性樹脂層之平面方向之構造，且鄰接之導電粒子間之中央區域之絕緣性樹脂層厚度薄於導電粒子附近之絕緣性樹脂層厚度；步驟(C)於第1連接層之導電粒子側表面形成主要由絕緣性樹脂所構成之第2連接層之步驟；及步驟(D)於與第2連接層相反側之第1連接層之表面形成主要由絕緣性樹脂所構成之第3連接層之步驟。
  8. 如申請專利範圍第7項之製造方法，其中步驟(B)與步驟(C)之間進而具有自導電粒子側對第1連接層照射紫外線之步驟。
  9. 一種異向性導電膜之製造方法，其係申請專利範圍第1項之異向性導電膜之製造方法，並具有以下步驟(a)~(c)：<步驟(a)>於形成有開口之轉印模之開口內配置導電粒子，使預先貼合有第3連接層之絕緣性樹脂層對向於形成有開口之轉印模之表面之步驟；<步驟(b)>自第3連接層側對絕緣性樹脂層施加壓力，將絕緣性樹脂壓入至開口內而使導電粒子轉印於絕緣性樹脂層之表面，藉此形成第1連接層之步驟，該第1連接層係導電粒子以單層排列於絕緣性樹脂層之平面方向之構造，且鄰接之導電粒子間之中央區域之絕緣性樹脂層厚度薄於導電粒子附近之絕緣性樹脂層厚度；及<步驟(c)>於第1連接層之導電粒子側表面形成主要由絕緣性樹脂所構成之第2連接層之步驟。
  10. 如申請專利範圍第9項之製造方法，其中步驟(b)與步驟(c)之間進而具有自導電粒子側對第1連接層照射紫外線之步驟。
  11. 一種連接構造體，其係利用申請專利範圍第1至6項中任一項之異向性導電膜將第1電子零件異向性導電連接於第2電子零件而成。
  12. 一種連接方法，其係利用申請專利範圍第1至6項中任一項之異向性導電膜將第1電子零件異向性導電連接於第2電子零件者，將異向性導電膜自其第3連接層側暫貼於第2電子零件，將第1電子零件搭載於暫貼之異向性導電膜，並自第1電子零件側進行熱壓接。
TW102130402A 2012-08-24 2013-08-23 異向性導電膜及其製造方法 TWI651192B (zh)

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