TW201631609A - 異向性導電膜 - Google Patents

異向性導電膜 Download PDF

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Publication number
TW201631609A
TW201631609A TW104135768A TW104135768A TW201631609A TW 201631609 A TW201631609 A TW 201631609A TW 104135768 A TW104135768 A TW 104135768A TW 104135768 A TW104135768 A TW 104135768A TW 201631609 A TW201631609 A TW 201631609A
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Taiwan
Prior art keywords
conductive particles
conductive film
anisotropic conductive
particles
lattice
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TW104135768A
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English (en)
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TWI747809B (zh
Inventor
Seiichiro Shinohara
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Dexerials Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
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    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
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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
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
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    • H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
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Abstract

本發明係下述構造之異向性導電膜：將絕緣性接著基底層與絕緣性接著覆蓋層積層並於其等之界面附近將導電粒子配置於平面格子圖案之格子點；其中，於任意基準區域假定之平面格子圖案中，未配置導電粒子之格子點相對於全部格子點之比率為25%以下，配置於平面格子圖案之格子點之導電粒子之一部分相對於對應格子點沿異向性導電膜之長邊方向偏移配置，以偏移配置之導電粒子之平面投影中心與對應格子點之間之距離來定義之偏移量未達導電粒子之平均粒徑之50%。

Description

異向性導電膜
本發明係關於一種異向性導電膜。
於絕緣性樹脂黏合劑中分散有導電粒子之異向性導電膜被廣泛用於將IC晶片等電氣零件安裝於配線基板等時，已知於此種異向性導電膜中，導電粒子彼此以連結或凝聚之狀態存在。因此，於將異向性導電膜應用於隨著電子機器之輕量小型化而窄間距化之IC晶片之端子與配線基板之端子之連接時，有鄰接之端子間因於異向性導電膜中以連結或凝聚之狀態存在之導電粒子而發生短路之情形。
先前，作為應對此種窄間距化之異向性導電膜，提出有使導電粒子規則排列於膜中者。例如提出有於可延伸之膜上形成黏著層，於該黏著層表面以單層密集地填充導電粒子後，對該膜進行雙軸延伸處理直至導電粒子間距離成為所期望之距離而使導電粒子規則排列，其後，對導電粒子抵壓成為異向性導電膜之構成要素之絕緣性接著基底層，使導電粒子轉印至絕緣性接著基底層而獲得之異向性導電膜(專利文獻1)。又，亦提出有「將導電粒子散佈於表面具有凹部之轉印模具之凹部形成面，刮刷凹部形成面而使導電粒子保持於凹部，自其上抵壓形成有轉印用黏著層之黏 著膜，使導電粒子一次轉印至黏著層，其次，對附著於黏著層之導電粒子抵壓成為異向性導電膜之構成要素之絕緣性接著基底層，使導電粒子轉印至絕緣性接著基底層」而獲得之異向性導電膜(專利文獻2)。關於該等異向性導電膜，通常於導電粒子側表面以覆蓋導電粒子之方式積層有絕緣性接著覆蓋層。
先前技術文獻
專利文獻
專利文獻1：WO2005/054388號
專利文獻2：日本特開2010-33793號公報
然而，由於導電粒子容易因靜電等發生凝聚而二次粒子化，故而難以使導電粒子以一次粒子之形式經常單獨地存在。因此，於專利文獻1或專利文獻2之技術中產生如下所述之問題。即，於專利文獻1之情形時，存在如下問題：難以於可延伸之膜之整個面無缺陷地以單層密集地填充導電粒子，導電粒子於凝聚狀態下被填充至可延伸之膜，而成為短路之原因，或者產生未填充之區域(所謂「遺漏」)，而成為導通不良之原因。又，於專利文獻2之情形時，存在如下問題：若將轉印模具之凹部利用粒徑較大之導電粒子覆蓋，則會因其後之刮刷而去除導電粒子，產生未保持有導電粒子之凹部，於異向性導電膜中產生導電粒子之「遺漏」，而成為導 通不良之原因，或者相反地若於凹部配置較小之導電粒子，則於轉印至絕緣性接著基底層時，應配置導電粒子之位置與實際配置之導電粒子之中心不重合而發生位置偏移，結果規則排列受損，而成為短路或導通不良之原因。
如此，實際情況是於專利文獻1或2中，並未充分地考慮應如何控制欲於異向性導電膜中以規則圖案排列之導電粒子之「遺漏」及「配置偏移」。
本發明之目的在於解決以上之先前技術之問題，提供一種就欲以規則圖案排列之導電粒子之「遺漏」及「配置偏移」之觀點而言大幅地抑制短路或導通不良之產生的異向性導電膜。
本發明者發現：藉由在將導電粒子配置於平面格子之格子點時，對在異向性導電膜之任意基準區域假定之平面格子圖案之相對於全部格子點的「未配置導電粒子之格子點之比率」及「導電粒子相對於格子點之配置偏移」進行控制，可達成上述目的，從而完成本發明。又，發現：此種異向性導電膜可藉由使導電粒子附著於表面形成有柱狀之凸部之轉印體之該凸部之前端而非將導電粒子配置於轉印體之凹部，並進行轉印而製造，從而完成本發明之製造方法。
即，本發明提供一種異向性導電膜，其構造為：絕緣性接著基底層與絕緣性接著覆蓋層積層，並於其等之界面附近，導電粒子配置於平面格子圖案之格子點；並且，於異向性導電膜之任意基準區域假定之平面格子圖案中，未配置導電 粒子之格子點相對於全部格子點之比率為25%以下，配置於平面格子圖案之格子點之導電粒子之一部分相對於對應格子點沿異向性導電膜之長邊方向偏移配置，以偏移配置之導電粒子之平面投影中心與對應格子點之間之距離來定義之偏移量未達導電粒子之平均粒徑之50%。
又，本發明提供一種異向性導電膜之製造方法，其係上述異向性導電膜之製造方法，並且包括以下步驟(甲)~(戊)：<步驟(甲)>準備於表面形成有相當於平面格子圖案之格子點的柱狀凸部之轉印體；<步驟(乙)>將該轉印體之凸部之至少頂面形成為微黏著層；<步驟(丙)>使導電粒子附著於該轉印體之凸部之微黏著層；<步驟(丁)>藉由在該轉印體之附著有導電粒子之側之表面重疊絕緣性接著基底層並按壓，而使導電粒子轉印至絕緣性接著基底層；及<步驟(戊)>對轉印有導電粒子之絕緣性接著基底層自導電粒子轉印面側積層絕緣性接著覆蓋層的步驟。
進而，本發明提供一種連接構造體，其係第1電氣零件之端子與第2電氣零件之端子藉由本發明之異向性導電膜進行異向性導電連接 而成。
於本發明之異向性導電膜中，於任意基準區域假定之平面格子圖案中，「未配置導電粒子之格子點」相對於全部格子點之比率係設定為25%以下，而且配置於平面格子圖案之格子點之導電粒子之一部分相對於對應格子點沿異向性導電膜之長邊方向偏移地配置，以偏移地配置之導電粒子之中心與對應格子點之間之距離來定義之「導電粒子之偏移量」係設定為未達導電粒子之平均粒徑之50%。該沿長邊方向之偏移成為沿長邊方向之一個方向之偏移。因此，於將本發明之異向性導電膜應用於異向性導電連接之情形時，可實現良好之初期導通電阻值與時效(aging)後之良好之導通可靠性，亦可抑制短路之產生。
又，於本發明之異向性導電膜之製造方法中，使用「於表面形成有相當於平面格子圖案之格子點之柱狀凸部之轉印體」，使導電粒子附著於該凸部之頂面所形成之微黏著層後，使該導電粒子轉印至絕緣性接著基底層。因此，於「將在異向性導電膜之任意基準區域假定之平面格子圖案中「未配置導電粒子之格子點」相對於全部格子點之比率設為25%以下，且配置於平面格子圖案之格子點之導電粒子之一部分相對於對應格子點沿異向性導電膜之長邊方向偏移地配置」之情形時，可將以偏移地配置之導電粒子之中心與對應格子點之間之距離來定義之「導電粒子之偏移量」設為未達導電粒子之平均粒徑之50%。因此，若使用藉由本發明之製造方法所獲得之異向性導電膜，則對於窄間距化之IC晶片與配線基板，可大幅地抑制短路或導通不良之產生，並且實現異向性導電連接。
10、200‧‧‧異向性導電膜
11、104‧‧‧絕緣性接著基底層
12、105‧‧‧絕緣性接著覆蓋層
13、103‧‧‧導電粒子
100‧‧‧轉印體
101‧‧‧凸部
102‧‧‧微黏著層
A‧‧‧未於格子點配置導電粒子之位置(遺漏導電粒子之位置)
B‧‧‧沿異向性導電膜之長邊方向偏移地配置之導電粒子
圖1係本發明之異向性導電膜之剖面圖。
圖2係本發明之異向性導電膜之俯視透視圖。
圖3A係本發明之製造方法之步驟說明圖。
圖3B係本發明之製造方法之步驟說明圖。
圖3C係本發明之製造方法之步驟說明圖。
圖3D係本發明之製造方法之步驟說明圖。
圖3E係本發明之製造方法之步驟說明圖。
圖3F係本發明之製造方法之步驟說明圖，同時係本發明之異向性導電膜之概略剖面圖。
以下，一面參照圖式一面詳細說明本發明之異向性導電膜。
<異向性導電膜>
如圖1(剖面圖)及圖2(俯視透視圖)所示，本發明之異向性導電膜10具有將絕緣性接著基底層11與絕緣性接著覆蓋層12積層並於其等之界面附近將導電粒子13配置於平面格子圖案(圖2之虛線)之格子點的構造。於圖1及圖2中，平面格子圖案係沿異向性導電膜10之長邊方向及與其正交之方向(短邊方向)而假定，亦可相對於長邊方向及短邊方向整體傾斜而假定。此處，箭頭A表示未於平面格子之格子點配置導電粒子之位置，即表示「遺漏」導電粒子之位置。箭頭B表示相對於對應格子點沿異向性 導電膜之長邊方向偏移地配置之導電粒子。此處，作為偏移地配置之導電粒子之中心(具體而言為將導電粒子投影至平面之影子之重心)與對應格子點之間之距離而定義之偏移量係考慮規則排列性而未達導電粒子之平均粒徑之50%。再者，該偏移起因於製法，僅相對於膜之長邊方向而產生。如此藉由使導電粒子於特定範圍內偏移，而產生於異向性導電連接時導電粒子容易被凸塊捕捉之效果。相對於凸塊之寬度方向(與膜之長邊方向正交之方向)，即便導電粒子於凸塊之端部被捕捉，亦適度地散亂，因此與沿格子點串列、即與膜之長邊方向大致正交之方向上之導電粒子之外切線一致之情況相比，若以上述外切線不一致之方式配置，則容易捕捉任一粒子，可期待捕捉數穩定之效果。此尤其於微間距之情形時發揮效果。
再者，較佳為相對於格子點沿異向性導電膜之長邊方向偏移地配置之導電粒子之偏移量之最大值大於與長邊方向正交之方向之偏移量。
又，就連接之穩定性之方面而言，導電粒子沿異向性導電膜之長邊方向偏移地配置之格子點相對於配置有導電粒子之全部格子點的比率較佳為90%以上。換言之，導電粒子以未達粒徑之50%之距離接近之個數成為導電粒子個數之10%以下。例如於圖2之情形時，偏移偏於長邊方向之一個方向(右側)。由於90%以上偏於一方，故而作為整體可保持粒徑之1倍以上之排列距離。因此，接近之個數成為總個數之10%以下。因此，由於大致所有導電粒子沿一個方向於特定範圍內偏移，故而保持格子形狀，而消除短路之主要原因即凝聚。如此，可見沿膜之長邊方向之規則性高於沿與膜之長邊方向正交之方向之規則性之傾向。此意指例如於圖2之 情形時，導電粒子於膜之長邊方向上有於直線上整齊排列之傾向，於與長邊方向正交之方向上有容易偏離直線上之傾向。進而，若詳細說明，膜平面方向之粒子沿膜之長邊方向之一方整體地偏移，意味著觀察到相對於排列之格子點，粒子之中心點主要沿膜之長邊方向側偏移，又，觀察到於與膜之長邊方向正交之方向上蜿蜒。
(導電粒子之「遺漏」)
於本發明之異向性導電膜中，將於異向性導電膜之任意基準區域假定之平面格子圖案中「未配置導電粒子之格子點」(圖2之A)相對於全部格子點之比率(遺漏導電粒子之格子點之比率)設定為25%以下、較佳為10~25%。藉此，於將本發明之異向性導電膜應用於異向性導電連接之情形時，可實現良好之初期導通電阻與時效後之良好之導通可靠性，亦可抑制短路之產生。
再者，就初期導通電阻與導通可靠性之觀點而言，較佳為「遺漏」導電粒子之格子點於異向性導電膜之平面方向上不連續，於實用上只要「遺漏」導電粒子之格子點不連續9個以上即可。
(平面格子圖案)
作為平面格子圖案，可列舉：斜方格子、六方格子、正方格子、矩形格子、平行體格子。其中，較佳為能夠進行最密填充之六方格子。
此處，作為異向性導電膜之基準區域，亦可選擇異向性導電膜之整個面，通常較佳為選擇異向性導電膜之平面中央部之由滿足以下關係式(A)、較佳為關係式(1)與關係式(2)及(3)之邊X及邊Y所構成之大致方形之區域作為基準區域。
X+Y=100D (1)
再者，應用於可相對較大地採用連接面積之FOG連接之情形時，可減少膜中之導電粒子之存在量，於此種情形時，如下所示，較佳為分別增大X與Y之值，較佳為設為20D以上，較佳為將「X+Y」之數值亦設為100D至400D附近之數值，最大設為400D。
X+Y=400D
X20D
Y20D
於式(A)及(1)~(3)中，D為導電粒子之平均粒徑。導電粒子之平均粒徑可利用圖像型粒度分佈計進行測定。又，邊Y為相對於異向性導電膜之長邊方向(參照圖2)未達±45°之範圍之直線，邊X為垂直於邊Y之直線。
藉由如此規定基準區域，可使基準區域與按壓導電粒子之凸塊之形狀相似或近似，結果可增大導電粒子自平面格子圖案之偏移之容許範圍，可經濟且穩定地進行異向性導電連接。換言之，藉由將該基準區域之最小邊設為導電粒子直徑之5倍以上，即便於在該範圍內假定之範圍內存在導電粒子之位置偏移或遺漏、接近，亦會於任一凸塊被捕捉，且不會 於凸塊間之空間過度地凝聚，因此可確實地進行異向性導電連接。
再者，將最小邊設為導電粒子直徑之5倍以上之原因在於：一般而言，為了於異向性導電連接之凸塊之至少1邊確實地進行捕捉，必須使其大於導電粒子之平均粒徑，而且基於對於凸塊間之空間亦防止短路之理由，較理想為必須設為導電粒子之平均粒徑之2倍以上之大小。換言之，其原因在於：於著眼於一個成為基準之圓形之導電粒子時，認為只要於以該導電粒子之平均粒徑D加上其直徑之4倍之長度(4D)所得之長度(即5D)作為直徑之同心圓內不產生預料外之不良，則可滿足上述必要條件。又，其原因亦有作為一例，設為微間距之情形時之凸塊間之最小距離未達導電粒子直徑之4倍。
(導電粒子之配置)
導電粒子較佳為於與膜之長邊方向垂直之方向上連續配置6個以上，更佳為連續配置8個以上。其原因在於：若相對於凸塊之長邊方向產生導電粒子之缺漏，則會產生對異向性導電連接造成影響之擔憂。於該情形時，較佳為沿膜之長邊方向連續之7行中有3行滿足上述條件，更佳為7行中有5行滿足上述條件。藉此，可使被凸塊捕捉之導電粒子數成為一定以上，可進行穩定之異向性導電連接。
又，導電粒子之缺漏較佳為沿膜之長邊方向連續4個以上者與沿與膜之長邊方向垂直之方向連續4個以上者不交叉，更佳為連續4個以上之任一缺漏介隔一個以上之成為格子點之導電粒子而未鄰接，進而更佳為連續4個以上之任一缺漏介隔兩個以上之成為格子點之導電粒子而未鄰接。此種缺漏之交叉即便對於長邊之一個方向之缺漏同時交叉至3行亦 無問題。其原因在於：只要不存在其以上程度之缺漏，則其附近之導電粒子會被凸塊捕捉。
導電粒子於膜之長邊方向上之缺漏只要於任意之連續之50個格子點中合計為12個以內，則於實用上無問題。其只要於與連續之缺漏之行鄰接之行之任一者中均無缺漏，則即便自缺漏之中途亦可計數。
(粒子面積佔有率)
進而，關於相對於異向性導電膜之任意基準區域之面積的存在於該面積中之全部導電粒子之粒子面積佔有率，對於如FOG連接般凸塊尺寸或凸塊間距離相對較大者，通常有效為0.15%以上，較佳為0.35%以上，更佳為1.4%以上。該情形時之上限較佳為35%以下，更佳為32%以下。又，於凸塊尺寸或凸塊間距離相對變小之情形時(例如COG連接)，進而較佳為10~35%，尤佳為14~32%。若為該範圍內，則於將本發明之異向性導電膜應用於異向性導電連接之情形時，亦可實現更良好之初期導通性與時效後之導通可靠性，亦可進一步抑制短路之產生。此處，粒子面積佔有率係相對於任意基準區域之面積S的存在於該基準區域內之全部導電粒子所佔有之面積之比率。所謂全部導電粒子所佔有之面積，於將導電粒子之平均粒徑設為R，將導電粒子數設為n時，以(R/2)2×π×n表示。因此，以粒子面積佔有率(%)=[{(R/2)2×π×n}/S]×100表示。
再者，設導電粒子之平均粒徑2μm、個數密度500個/mm2(0.0005個/μm2)、X=Y=200D、X+Y=400D之情形時之計算上之粒子面積佔有率為0.157%。設導電粒子之平均粒徑3μm、個數密度500個/mm2(0.0005個/μm2)、X=Y=200D、X+Y=400D之情形時之計算上之 粒子面積佔有率為0.35325%。設導電粒子之平均粒徑3μm、個數密度2000個/mm2(0.002個/μm2)、X=Y=200D、X+Y=400D之情形時之計算上之粒子面積佔有率為1.413%。又，設導電粒子之平均粒徑30μm、個數密度500個/mm2(0.0005個/μm2)、X=Y=200D、X+Y=400D之情形時之計算上之粒子面積佔有率為35.325%。
(導電粒子)
作為導電粒子，可適當選擇使用於公知異向性導電膜中所使用者。例如可列舉：鎳、銅、銀、金、鈀等金屬粒子、利用鎳等金屬被覆聚醯胺、聚苯胍胺等樹脂粒子之表面而成之金屬被覆樹脂粒子等。又，關於導電粒子之平均粒徑，就製造時之操作性之觀點而言，較佳為1~30μm，更佳為1~10μm，尤佳為2~6μm。如上所述般，可利用圖像型粒度分佈計測定平均粒徑。
異向性導電膜中之導電粒子之存在量係取決於平面格子圖案之格子間距以及導電粒子之平均粒徑，通常為300~40000個/mm2。
(鄰接格子點間距離)
又，較佳為於異向性導電膜中假定之平面格子圖案中之鄰接格子點間距離為導電粒子之平均粒徑之0.5倍以上，更佳為1倍以上，進而較佳為1倍以上且20倍以下。若為該範圍內，則於將本發明之異向性導電膜應用於異向性導電連接之情形時，亦可實現更良好之初期導通性與時效後之導通可靠性，亦可進一步抑制短路之產生。
(絕緣性接著基底層)
作為絕緣性接著基底層11，可適當選擇使用於公知之異向性導電膜中 用作絕緣性接著基底層者。例如可使用含有丙烯酸酯化合物與光自由基聚合起始劑之光自由基聚合性樹脂層、含有丙烯酸酯化合物與熱自由基聚合起始劑之熱自由基聚合性樹脂層、含有環氧化合物與熱陽離子聚合起始劑之熱陽離子聚合性樹脂層、含有環氧化合物與熱陰離子聚合起始劑之熱陰離子聚合性樹脂層等、或其等之硬化樹脂層。又，於該等樹脂層中，可視需要適當選擇而含有矽烷偶合劑、顏料、抗氧化劑、紫外線吸收劑等。
再者，絕緣性接著基底層11可藉由利用塗佈法將含有如上所述之樹脂之塗佈組成物成膜並使之乾燥，或進而使之硬化而形成，或者藉由預先利用公知之方法進行膜化而形成。
此種絕緣性接著基底層11之厚度較佳為1~30μm，更佳為2~15μm。
(絕緣性接著覆蓋層)
作為絕緣性接著覆蓋層12，可適當選擇使用於公知之異向性導電膜中用作絕緣性接著覆蓋層者。又，亦可使用由與上文所說明之絕緣性接著基底層11相同之材料所形成者。
再者，絕緣性接著覆蓋層12可藉由利用塗佈法將含有如上所述之樹脂之塗佈組成物成膜並使之乾燥，或進而使之硬化而形成，或者藉由預先利用公知方法進行膜化而形成。
此種絕緣性接著覆蓋層12之厚度較佳為1~30μm，更佳為2~15μm。
進而，於絕緣性接著基底層11或絕緣性接著覆蓋層12中，亦可視需要添加二氧化矽微粒子、氧化鋁、氫氧化鋁等絕緣性填料。絕緣 性填料之摻合量較佳為相對於構成該等層之樹脂100質量份設為3~40質量份。藉此，即便於異向性導電連接時絕緣接著劑層10發生熔融，亦可抑制導電粒子13於熔融之樹脂中發生不需要之移動。
(絕緣性接著基底層與絕緣性接著覆蓋層之積層)
再者，於夾著導電粒子13而積層絕緣性接著基底層11與絕緣性覆蓋層12之情形時，可藉由公知方法進行。於該情形時，導電粒子13存在於該等層之界面附近。此處，所謂「存在於界面附近」，表示導電粒子之一部分沒入其中一層，其餘部分沒入另一層。
<異向性導電膜之製造>
其次，對「使絕緣性接著基底層與絕緣性接著覆蓋層積層，並於其等之界面附近將導電粒子配置於平面格子圖案之格子點之構造」的本發明之異向性導電膜之製造方法進行說明。該製造方法具有以下之步驟(甲)~(戊)。參照圖式對各步驟逐一進行詳細說明。
(步驟(甲))
首先，如圖3A所示，準備於表面形成有相當於平面格子圖案之格子點之柱狀之凸部101的轉印體100。此處，所謂柱狀係指圓柱狀或角柱狀(三角柱、四角柱、六角柱等)。較佳為圓柱狀。凸部101之高度可根據欲進行異向性導電連接之端子間距、端子寬度、間隔寬度、導電粒子之平均粒徑等來決定，較佳為為所使用之導電粒子之平均粒徑之2.5倍以上且未達5倍，更佳為2.5倍以上且3.5倍以下。又，凸部101之寬度(一半高度時之寬度)較佳為為導電粒子之平均粒徑之0.6倍以上且未達1.3倍，更佳為0.6倍以上且1.1倍以下。若該高度與寬度為該等範圍內，則可獲得避免連續地 產生脫落及遺漏之效果。
進而，凸部101具有使導電粒子穩定地附著之程度之大致平坦之頂面。
*轉印體之具體例
該步驟(甲)中欲準備之轉印體可藉由公知方法而製作，例如可對金屬板進行加工而製作母盤，於其上塗佈硬化性樹脂並使之硬化而製作。具體而言，亦對平坦之金屬板進行切削加工，而製作形成有與凸部對應之凹部之轉印體母盤，於該母盤之凹部形成面塗佈構成轉印體之樹脂組成物並使之硬化後，將其自母盤剝離，藉此獲得轉印體。
(步驟(乙))
其次，如圖3B所示，將於表面以平面格子圖案形成有數個凸部101之轉印體100之凸部101之至少頂面形成為微黏著層102。
*轉印體之微黏著層
微黏著層102係顯示出可暫時地保持導電粒子直至導電粒子被轉印至構成異向性導電膜之絕緣性接著基底層為止之黏著力的層，其形成於凸部101之至少頂面。因此，凸部101整體亦可為微黏著性。微黏著層102之厚度可根據微黏著層102之材質、導電粒子之粒徑等而適當確定。又，所謂「微黏著」，意指於將導電粒子轉印至絕緣性接著基底層時，黏著力弱於絕緣性接著基底層。
此種微黏著層102可應用公知之異向性導電膜中所使用之微黏著層。例如可藉由將聚矽氧系黏著劑組成物或與絕緣性接著基底層或絕緣性接著覆蓋層相同材質之黏著層塗佈於凸部101之頂面並進行乾燥而 形成。
(步驟(丙))
其次，如圖3C所示，使導電粒子103附著於轉印體100之凸部101之微黏著層102。具體而言，只要自轉印體100之凸部101之上方散佈導電粒子103，並使用吹風器將未附著於微黏著層102之導電粒子103吹飛即可。於該情形時，於一部分之凸部101，以某程度之頻度發生如下情況：於其側面因靜電等之作用而附著導電粒子，而且無法利用吹風器去除。
如此於利用吹風器將導電粒子吹飛時，可藉由改變吹風之次數而控制導電粒子之「遺漏」之產生量。例如若增加吹風之次數，則可增加導電粒子之「遺漏」。若增加導電粒子之「遺漏」，則結果可減少導電粒子之使用量，可降低異向性導電膜之製造成本。
再者，亦可自圖3C使面之方向反轉，使突起之頂面附著於一面鋪滿導電粒子之面。其原因在於不會對導電粒子施加不需要之應力。如此藉由僅使對於配置而言所需之導電粒子附著於突起頂面，而容易回收並再利用導電粒子，與在開口部填充並取出導電粒子之方法相比，經濟性亦優異。再者，於在開口部填充並取出導電粒子之方法之情形時，擔憂容易對未填充之導電粒子施加不需要之應力。
(步驟(丁))
其次，如圖3D所示，藉由在轉印體100之附著有導電粒子103之側之表面重疊欲構成異向性導電膜之絕緣性接著基底層104並按壓，而使導電粒子103轉印至絕緣性接著基底層104之單面(圖3E)。於該情形時，較佳為將轉印體100以其凸部101朝下之方式重疊於絕緣性接著基底層104並按 壓。其原因在於：藉由使其朝下並吹風，而易於去除未貼合於凸部之頂面之導電粒子。
(步驟(戊))
如圖3F所示，對轉印有導電粒子103之絕緣性接著基底層104自導電粒子轉印面側積層絕緣性接著覆蓋層105。藉此，獲得本發明之異向性導電膜200。
<連接構造體>
本發明之異向性導電膜藉由配置於第1電氣零件(例如IC晶片)之端子(例如凸塊)與第2電氣零件(例如配線基板)之端子(例如凸塊、焊墊)之間，並自第1或第2電氣零件側藉由熱壓接進行正式硬化而進行異向性導電連接，可提供短路或導通不良得到抑制之所謂COG(chip on glass，玻璃覆晶)或FOG(film on glass，玻璃覆膜)等之連接構造體。
[實施例]
以下，具體地說明本發明。
實施例1
準備厚度2mm之鎳板，以四方格子圖案形成圓柱狀之凹部(內徑3μm，深度10μm)，作為轉印體母盤。鄰接凹部中心間距離為8μm。因此，凹部之密度為16000個/mm2。
於所獲得之轉印體母盤上，以乾燥厚度成為30mm之方式塗佈含有苯氧基樹脂(YP-50，新日鐵住金化學(股份有限公司))60質量份、環氧樹脂(jER828，三菱化學(股份有限公司))40質量份、及陽離子系硬化劑(SI-60L，三新化學工業(股份有限公司))2質量份之熱硬化性 樹脂組成物，並於80℃下加熱5分鐘，藉此製作轉印體。
將轉印體自母盤剝離，以凸部成為外側之方式捲繞至直徑20cm之不鏽鋼製輥上，一面使該輥旋轉，一面與使含有環氧樹脂(jER828，三菱化學(股份有限公司))70質量份及苯氧基樹脂(YP-50，新日鐵住金化學(股份有限公司))30質量份之微黏著劑組成物含浸於不織布中而成之黏著片接觸，使微黏著劑組成物附著於凸部之頂面，形成厚度1μm之微黏著層而獲得轉印體。
於該轉印體之表面散佈平均粒徑4μm之導電粒子(鍍鎳樹脂粒子(AUL704，積水化學工業(股份有限公司)))後，藉由吹風而去除未附著於微黏著層之導電粒子。
於溫度50℃、壓力0.5MPa下將附著有導電粒子之轉印體自其導電粒子附著面按壓於作為絕緣性接著基底層之厚度5μm之片狀之熱硬化型之絕緣性接著膜(由含有苯氧基樹脂(YP-50，新日鐵住金化學(股份有限公司))60質量份、環氧樹脂(jER828，三菱化學(股份有限公司))40質量份、陽離子系硬化劑(SI-60L，三新化學工業(股份有限公司))2質量份、及二氧化矽微粒子(Aerosil RY200，日本Aerosil(股份有限公司))20質量份之絕緣性接著組成物所形成之膜)，藉此使導電粒子轉印至絕緣性接著基底層。
於所獲得之絕緣性接著基底層之導電粒子轉印面重疊作為透明之絕緣性接著覆蓋層之厚度15μm之片狀之另一絕緣性接著膜(由含有苯氧基樹脂(YP-50，新日鐵住金化學(股份有限公司))60質量份、環氧樹脂(jER828，三菱化學(股份有限公司))40質量份、及陽離子系硬化 劑(SI-60L，三新化學工業(股份有限公司))2質量份之熱硬化性樹脂組成物所形成之膜)，於溫度60℃、壓力2MPa下進行積層。藉此獲得異向性導電膜。
實施例2
將用以去除未附著於微黏著層之導電粒子之吹風之次數設為實施例1之3倍，除此以外，重複實施例1，藉此獲得異向性導電膜。
實施例3
將轉印體母盤之凹部之內徑設為2μm，將凹部之深度設為9μm，將鄰接凹部中心間距離設為6μm，將凹部之密度設為28000個/mm2，且使用平均粒徑3μm之導電粒子(AUL703，積水化學工業(股份有限公司))代替平均粒徑4μm之導電粒子外，藉由重複實施例1，獲得異向性導電膜。
實施例4
將用以去除未附著於微黏著層之導電粒子之吹風之次數設為實施例3之3倍外，藉由重複實施例3，獲得異向性導電膜。
比較例1
將用以去除未附著於微黏著層之導電粒子之吹風之次數設為實施例1之10倍外，藉由重複實施例1，獲得異向性導電膜。
比較例2
將用以去除未附著於微黏著層之導電粒子之吹風之次數設為實施例3之10倍外，藉由重複實施例3，獲得異向性導電膜。
<評價>
(導電粒子之「遺漏」與「偏移量」)
對於實施例1~4及比較例1~2之異向性導電膜，自其透明之絕緣性接著覆蓋層側利用光學顯微鏡(MX50，Olympus(股份有限公司))觀察1cm見方之區域，調查於假定之平面格子圖案中未附著導電粒子之格子點相對於全部格子點之比率(遺漏[%])。將所獲得之結果示於表1。又，測定配置於假定之平面格子圖案之格子點之導電粒子自該格子點之偏移量。將所獲得之最大值示於表1。再者，除遺漏以外，未觀察到對連接產生明顯影響之狀態。
再者，實施例1~4、比較例1~2之異向性導電膜中之導電粒子之偏移方向為異向性導電膜之長邊方向之一方。又，關於導電粒子沿異向性導電膜之長邊方向之一方以未達粒徑之50%偏移地配置之格子點相對於配置有導電粒子之全部格子點的比率，於實施例1之情形時為4%，於實施例2之情形時為10%，於實施例3之情形時為5%，於實施例4之情形時為10%，於比較例1之情形時為15%，於比較例2之情形時為17%。於偏移量較大之情形時，難以於特定位置設置導電粒子，而容易產生不良端子。
(粒子面積佔有率)
根據導電粒子之平均粒徑與轉印體母盤之凹部密度(=轉印體之凸部密度)，在考慮導電粒子之「遺漏」之基礎上，計算粒子面積佔有率。將所獲得之結果示於表1。
(初期導通電阻)
使用實施例及比較例之異向性導電膜，於180℃、60MPa、5秒之條件下將具有凸塊間間隔為12μm且高度15μm、直徑30×50μm之金凸塊之IC晶片與設置有12μm間隔之配線之玻璃基板進行異向性導電連接，而獲 得連接構造體。對於所獲得之連接構造體，使用電阻測定器(數位萬用錶，橫河電機(股份有限公司))測定初期導通電阻值。將所獲得之結果示於表1。期望為0.5Ω以下。
(導通可靠性)
將測定初期導通電阻值時所使用之連接構造體投入至設定為溫度85℃、濕度85%之時效試驗器中，並放置500小時後以和初期導通電阻相同之方式測定導通電阻值。將所獲得之結果示於表1。期望為5Ω以下。
(導通不良率)
製作與初期導通電阻中所使用者相同之連接構造體，並測定端子之導通不良率。將所獲得之結果示於表1。
根據表1之結果得知，使用實施例1~4之異向性導電膜之連接構造體於初期導通電阻、導通可靠性、導通不良率之各評價項目中顯示出良好之結果。
另一方面，於比較例1、2之異向性導電膜之情形時，導電 粒子之「遺漏」之比率較高，初期導通電阻值高於實施例，導通不良率未成為0%。
實施例5
為了使用凹部密度為500個/mm2之轉印母盤，而調整鄰接凹部中心間距離，除此以外，以與實施例2相同之方式製作轉印體，進而製作異向性導電膜。對於所獲得之異向性導電膜，以與實施例2相同之方式測定導電粒子之「遺漏」與「偏移量」，進而算出粒子面積佔有率。其結果為，導電粒子之「遺漏」與實施例2同等。「偏移量」亦獲得依照實施例2之結果。又，粒子面積佔有率為0.5%。
又，將所獲得之異向性導電膜夾於玻璃基板(ITO實體電極)與軟性配線基板(凸塊寬度：200μm，L(線)/S(間隙)=1，配線高度10μm)之間，以連接凸塊長度成為1mm之方式於180℃、80MPa、5秒之條件下進行異向性導電，而獲得評價用連接構造體。對於所獲得之連接構造體，關於其「初期導通電阻值」、及投入於溫度85℃且濕度85%RH之恆溫槽中500小時後之「導通可靠性」，使用數位萬用錶(34401A，Agilent Technology股份有限公司製造)以電流1A藉由4端子法而測定導通電阻，於「初期導通電阻值」之情形時，將測定值為2Ω以下之情形評價為良好，將超過2Ω者評價為不良，於「導通可靠性」之情形時，將測定值為5Ω以下之情形評價為良好，將5Ω以上之情形評價為不良。其結果為，本實施例之連接構造體均評價為「良好」。又，以與實施例2相同之方式測定「導通不良率」，結果與實施例2同樣地獲得良好之結果。
實施例6
為了使用凹部密度為2000個/mm2之轉印母盤，而調整鄰接凹部中心間距離，除此以外，以與實施例2相同之方式製作轉印體，進而製作異向性導電膜。針對所獲得之異向性導電膜，以與實施例2相同之方式測定導電粒子之「遺漏」與「偏移量」，進而算出粒子面積佔有率。其結果為，導電粒子之「遺漏」與實施例2同等。「偏移量」亦獲得依照實施例2之結果。又，粒子面積佔有率為1.9%。
又，將所獲得之異向性導電膜以與實施例5相同之方式夾於玻璃基板與可撓性配線基板之間並進行異向性導電連接，藉此獲得評價用連接構造體。針對所獲得之連接構造體，以與實施例5相同之方式評價「初期導通電阻值」、「導通可靠性」、「導通不良率」，結果均獲得良好之結果。
實施例7
使用為了將導電粒子之大小自實施例1之4μm設為10μm，且為了使凹部密度成為4400個/mm2而依照實施例1調整了凹部尺寸及鄰接凹部中心間距離等之轉印母盤，除此以外，以與實施例1大致相同之方式製作轉印體，進而將導電粒子直徑變更為10μm，將絕緣性接著基底層之厚度變更為12μm，將絕緣性接著覆蓋層之厚度變更為12μm，除此以外，以與實施例1相同之方式製作異向性導電膜。對於所獲得之異向性導電膜，以與實施例1相同之方式測定導電粒子之「遺漏」與「偏移量」，進而算出粒子面積佔有率。其結果為，導電粒子之「遺漏」與實施例1同等。「偏移量」亦獲得依照實施例1之結果。粒子面積佔有率為30.7%。
又，將所獲得之異向性導電膜夾於玻璃基板(ITO實體電極)與可撓性配線基板(凸塊寬度：100μm，L(線)/S(間隙)=1，配線 高度19μm)之間，以連接凸塊長度成為1mm之方式於180℃、80MPa、5秒之條件下進行異向性導電，而獲得評價用連接構造體。對於所獲得之連接構造體，關於其「初期導通電阻值」、及投入於溫度85℃且濕度85%RH之恆溫槽中500小時後之「導通可靠性」，使用數位萬用錶(34401A，Agilent Technology股份有限公司製造)以電流1A藉由4端子法而測定導通電阻，於「初期導通電阻值」之情形時，將測定值為2Ω以下之情形評價為良好，將超過2Ω者評價為不良，於「導通可靠性」之情形時，將測定值為5Ω以下之情形評價為良好，將5Ω以上之情形評價為不良。其結果為，本實施例之連接構造體均評價為「良好」。又，以與實施例1相同之方式測定「導通不良率」，結果與實施例1同樣地獲得良好之結果。
[產業上之可利用性]
於本發明之異向性導電膜中，於任意基準區域假定之平面格子圖案中「未配置導電粒子之格子點」相對於全部格子點之比率設定為25%以下，而且配置於平面格子圖案之格子點之導電粒子之一部分相對於對應格子點沿異向性導電膜之長邊方向偏移地配置，以偏移地配置之導電粒子之中心與對應格子點之間之距離來定義之偏移量未達導電粒子之平均粒徑之50%。因此，於將本發明之異向性導電膜應用於異向性導電連接之情形時，可實現良好之初期導通性與時效後之良好之導通可靠性，亦可抑制短路之產生，因此於將窄間距化之IC晶片與配線基板進行異向性導電連接之情形時有用。
10‧‧‧異向性導電膜
11‧‧‧絕緣性接著基底層
12‧‧‧絕緣性接著覆蓋層
13‧‧‧導電粒子
A‧‧‧未於格子點配置導電粒子之位置(遺漏導電粒子之位置)

Claims (13)

  1. 一種異向性導電膜，其構造為：絕緣性接著基底層與絕緣性接著覆蓋層積層，並於其等之界面附近，導電粒子配置於平面格子圖案之格子點；並且於異向性導電膜之任意基準區域假定之平面格子圖案中，未配置導電粒子之格子點相對於全部格子點之比率為25%以下，配置於平面格子圖案之格子點之導電粒子之一部分相對於對應格子點沿異向性導電膜之長邊方向偏移配置，以偏移配置之導電粒子之中心與對應格子點之間之距離來定義之偏移量未達導電粒子之平均粒徑之50%。
  2. 如申請專利範圍第1項之異向性導電膜，其中，基準區域係異向性導電膜之平面中央部之由滿足以下關係式(A)、(2)及(3)之邊X及邊Y所構成之大致方形之區域： 此處，D為導電粒子之平均粒徑，邊Y為相對於異向性導電膜之長邊方向未達±45°之範圍之直線，邊X為與邊Y垂直之直線。
  3. 如申請專利範圍第1項之異向性導電膜，其中，基準區域係異向性導電膜之平面中央部之由滿足以下關係式(1)~(3)之邊X及邊Y所構成之大致方形之區域：X+Y=100D (1) 此處，D為導電粒子之平均粒徑，邊Y為相對於異向性導電膜之長邊方向未達±45°之範圍之直線，邊X為與邊Y垂直之直線。
  4. 如申請專利範圍第1至3項中任一項之異向性導電膜，其中，相對於異向性導電膜之任意基準區域之面積，存在於該面積中之全部導電粒子之粒子面積佔有率為10~35%。
  5. 如申請專利範圍第1至4項中任一項之異向性導電膜，其中，導電粒子之平均粒徑為1~10μm，平面格子圖案之鄰接格子點間距離為導電粒子之平均粒徑之0.5倍以上。
  6. 如申請專利範圍第1至5項中任一項之異向性導電膜，其中，相對於格子點沿異向性導電膜之長邊方向偏移地配置之導電粒子之偏移量之最大值大於與長邊方向正交之方向之偏移量。
  7. 如申請專利範圍第1項之異向性導電膜，其中，基準區域係異向性導電膜之平面中央部之由滿足以下關係式之邊X及邊Y所構成之大致方形之區域：X+Y=400D X20D Y20D此處，D為導電粒子之平均粒徑，邊Y為相對於異向性導電膜之長邊方向未達±45°之範圍之直線，邊X為與邊Y垂直之直線。
  8. 如申請專利範圍第7項之異向性導電膜，其中，相對於異向性導電膜 之任意基準區域之面積，存在於該面積中之全部導電粒子之粒子面積佔有率為0.15%以上。
  9. 如申請專利範圍第7或8項之異向性導電膜，其中，導電粒子之平均粒徑為1~30μm，平面格子圖案之鄰接格子點間距離為導電粒子之平均粒徑之0.5倍以上。
  10. 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，並且包括以下步驟(甲)~(戊)：<步驟(甲)>準備於表面形成有相當於平面格子圖案之格子點的柱狀凸部之轉印體；<步驟(乙)>將轉印體之凸部之至少頂面形成為微黏著層；<步驟(丙)>使導電粒子附著於該轉印體之凸部之微黏著層；<步驟(丁)>藉由在該轉印體之附著有導電粒子之側之表面重疊絕緣性接著基底層並按壓，而使導電粒子轉印至絕緣性接著基底層；及<步驟(戊)>對轉印有導電粒子之絕緣性接著基底層自導電粒子轉印面側積層絕緣性接著覆蓋層。
  11. 如申請專利範圍第10項之異向性導電膜之製造方法，其中，步驟(甲)中所使用之轉印體係對金屬板進行加工而製作母盤，於其上塗佈硬化 性樹脂並使其硬化而製作者。
  12. 如申請專利範圍第10或11項之異向性導電膜之製造方法，其中，步驟(甲)之轉印體之凸部之高度為導電粒子之平均粒徑之2.5倍以上且未達5倍，凸部之寬度為導電粒子之平均粒徑之0.6倍以上且未達1.3倍。
  13. 一種連接構造體，其係將第1電氣零件之端子與第2電氣零件之端子藉由申請專利範圍第1至9項中任一項之異向性導電膜進行異向性導電連接而成。
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