TWI781119B - 含填料膜 - Google Patents
含填料膜 Download PDFInfo
- Publication number
- TWI781119B TWI781119B TW106137522A TW106137522A TWI781119B TW I781119 B TWI781119 B TW I781119B TW 106137522 A TW106137522 A TW 106137522A TW 106137522 A TW106137522 A TW 106137522A TW I781119 B TWI781119 B TW I781119B
- Authority
- TW
- Taiwan
- Prior art keywords
- filler
- resin layer
- containing film
- film
- anisotropic conductive
- Prior art date
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- 239000000945 filler Substances 0.000 title claims abstract description 472
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- 238000011156 evaluation Methods 0.000 description 17
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- 230000000694 effects Effects 0.000 description 10
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
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- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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Abstract
本發明之可以更低之推力精密地壓抵於電子零件之含填料膜係如下之膜,即,該膜具有於樹脂層中規則地配置有填料之填料分散層,且俯視下之填料之面積佔有率為25%以下,樹脂層之層厚La與填料之平均粒徑D的比La/D為0.3以上且1.3以下,相對於填料整體,填料彼此以相互不接觸之狀態存在之個數比率為95%以上。相對於填料整體,填料彼此以相互不接觸之狀態存在之個數比率較佳為99.5%以上。
Description
本發明係關於一種異向性導電膜等含填料膜。
於樹脂層中分散有填料之含填料膜被使用於消光膜、電容器用膜、光學膜、標籤用膜、抗靜電用膜、異向性導電膜等多種多樣之用途中(專利文獻1、專利文獻2、專利文獻3、專利文獻4)。
例如,提出有於使用作為含填料膜之一態樣的異向性導電膜進行異向性導電連接時,為了抑制端子所捕捉之導電粒子數之不均,而於異向性導電膜中使導電粒子形成特定之排列(專利文獻5),為了兼顧確保對向之端子之連接可靠性及抑制相鄰之端子間之短路,而於異向性導電膜中將相互分離之導電粒子之數量設為特定之比率以上(專利文獻6)等。
[先前技術文獻]
[專利文獻]
專利文獻1:日本特開2006-15680號公報
專利文獻2:日本特開2015-138904號公報
專利文獻3:日本特開2013-103368號公報
專利文獻4:日本特開2014-183266號公報
專利文獻5:日本專利4887700號公報
專利文獻6:日本特開2015-167106號公報
然而,以往並未對於使用按壓治具將異向性導電膜熱壓接於電子零件時,異向性導電膜中所含有之導電粒子之個數密度與按壓治具所需要之推力的關係進行詳細研究。
因此,即便從確保端子之連接可靠性及抑制短路之方面考慮而設定異向性導電膜中之導電粒子之個數密度,當將其實際設置於按壓治具並進行熱壓接以實現異向性導電連接時,為了將導電粒子壓入端子中而按壓治具所需要之推力增加,先前之按壓治具有無法因應之情況,於該情形時若進行按壓治具之改造等,則有增加成本之擔憂。
對此,本發明之課題在於:於將含填料膜連接於物品之情形時,例如於使用異向性導電膜來連接電子零件之情形時,提高端子中之導電粒子之捕捉性,改善導通特性,且使將異向性導電膜等含填料膜壓抵於電子零件之按壓治具所需要之推力不會過高。又,課題亦在於:可將含填料膜之填料之粒徑與保持其之層之厚度之間的關係作為指標,來調控該含填料膜之特性(上述異向性導電膜中之按壓治具所需要之推力的課題為其一例)。
本發明人發現:於將含填料膜壓接於物品時,藉由將填料之粒徑與保持其之層之厚度的比設為特定範圍、或者使填料規則地分散、提高填料彼此以不接觸之狀態存在之個數比率、以及調整填料之面積佔有率等,可調整含填料膜之特性,從而完成本發明。若以作為其一例之異向性導電膜進行具體說明,則發現:為了提高於將異向性導電膜熱壓接於電子零件時端子中之導電粒 子等填料之捕捉性,且降低按壓治具所需要之推力,有效的是使導電粒子等填料規則地分散於樹脂層(較佳為絕緣性樹脂層)中,提高導電粒子等填料彼此以不接觸之狀態存在之個數比率,將樹脂層之厚度與填料之平均粒徑的比設為特定範圍,及調整異向性導電膜等含填料膜中之填料之面積佔有率,從而完成本發明。
即,本發明提供一種含填料膜,其具有於樹脂層中規則地配置有填料之填料分散層,且俯視下之填料之面積佔有率為25%以下,樹脂層之層厚La與填料之粒徑D的比La/D為0.3以上且1.3以下,相對於填料整體,填料彼此以相互不接觸之狀態存在之個數比率為95%以上。尤其是,本發明作為含填料膜之較佳之一態樣而提供一種含填料膜,其中,填料為導電粒子,填料分散層之樹脂層為絕緣性樹脂層,且用作異向性導電膜。
又,本發明提供一種膜貼合體,其係將上述含填料膜貼合於物品;一種連接構造體,其係經由上述含填料膜將第1物品與第2物品連接;尤其是一種連接構造體,其係經由用作異向性導電膜之含填料膜將第1電子零件與第2電子零件進行異向性導電連接。進而,本發明提供一種連接構造體之製造方法,其係經由上述含填料膜將第1物品與第2物品進行壓接;以及一種連接構造體之製造方法,其係製造如下之連接構造體,該連接構造體係將第1物品、第2物品分別設為第1電子零件、第2電子零件,經由用作異向性導電膜之含填料膜將第1電子零件與第2電子零件進行熱壓接,藉此將第1電子零件與第2電子零件進行異向性導電連接而成。
根據本發明之含填料膜(作為其一態樣之異向性導電膜),由於導電粒子等填料規則地分散於樹脂層(較佳為絕緣性樹脂層)中,相對於填料 整體,填料彼此以相互不接觸之狀態存在之個數比率為95%以上,故而於將異向性導電膜等含填料膜熱壓接於電子零件時按壓均等地施加於各填料,又,由於樹脂層之層厚La與填料之平均粒徑D之比La/D為0.3以上且1.3以下,故而將異向性導電膜等含填料膜熱壓接於電子零件時,不易引起填料之位置偏移,因此可將壓接部位中之填料之排列或分散狀態維持為壓接前之狀態。因此,異向性導電膜之填料變得容易被端子捕捉。其於異向性導電膜以外之連接中,亦可獲得相同之傾向。
進而,根據本發明之含填料膜(作為其一態樣之異向性導電膜),由於導電粒子等填料之面積佔有率為25%以下,故而可確保將填料以低壓壓抵於物品(電子零件),於將異向性導電膜等含填料膜壓接於電子零件時,可防止按壓治具所需要之推力變得過高。又,作為其他態樣,例如有光學膜,藉由調整填料於樹脂層中於厚度方向及俯視下以不接觸之狀態獨立之個數比率,可調整填料之光學性能。對於消光膜等直接關係到外觀者,亦可謂相同。
1‧‧‧填料(導電粒子)
2‧‧‧樹脂層(絕緣性樹脂層)
2b‧‧‧凹陷(傾斜)
2c‧‧‧凹陷(起伏)
3‧‧‧填料分散層(導電粒子分散層)
4‧‧‧第2樹脂層
10A、10B、10C、10D、10E、10F、10G、10H、10I‧‧‧含填料膜(作為其一態樣之異向性導電膜)
La‧‧‧樹脂層之層厚
Lb‧‧‧鄰接之填料間之中央部之切平面與填料之最深部的距離
Lc‧‧‧傾斜或起伏中之填料之露出(正上方)部分的直徑
Ld‧‧‧填料周圍或正上方之樹脂層之傾斜或起伏的最大直徑
Le‧‧‧填料周圍之樹脂層中之傾斜的最大深度
Lf‧‧‧填料正上方之樹脂層中之起伏的最大深度
圖1A係表示實施例之含填料膜(作為其一態樣之異向性導電膜)10A中之填料(導電粒子)之配置的俯視圖。
圖1B係實施例之含填料膜(作為其一態樣之異向性導電膜)10A的剖面圖。
圖2係實施例之含填料膜(作為其一態樣之異向性導電膜)10B的剖面圖。
圖3係實施例之含填料膜(作為其一態樣之異向性導電膜)10C的剖面圖。
圖4係實施例之含填料膜(作為其一態樣之異向性導電膜)10D的剖面圖。
圖5係實施例之含填料膜(作為其一態樣之異向性導電膜)10E的剖面圖。
圖6係實施例之含填料膜(作為其一態樣之異向性導電膜)10F的剖面圖。
圖7係實施例之含填料膜(作為其一態樣之異向性導電膜)10G的剖面圖。
圖8係實施例之含填料膜(作為其一態樣之異向性導電膜)10H的剖面圖。
圖9係實施例之含填料膜(作為其一態樣之異向性導電膜)10I的剖面圖。
以下,一面參照圖式一面主要對作為本發明之含填料膜之一態樣的異向性導電膜進行詳細說明。再者,於各圖中,同一符號表示同一或同等之構成元件。
<含填料膜之整體構成>
圖1A係針對本發明之含填料膜(作為其一態樣之異向性導電膜)10A,說明填料(或導電粒子)1之配置的俯視圖。又,圖1B係含填料膜10A之X-X剖面圖。
於該含填料膜10A之填料分散層(或導電粒子分散層)3中,於樹脂層2(或絕緣性樹脂層)之單面以規則之排列狀態分散有填料1,該樹脂層2係由最低熔融黏度為相對高黏度之樹脂所形成。
<填料>
填料1可根據含填料膜之用途,自公知之無機系填料(金屬、金屬氧化物、金屬氮化物等)、有機系填料(樹脂粒子、橡膠粒子等)、有機系材料與無機系材料混合存在之填料(例如,核由樹脂材料形成且表面經金屬鍍覆之粒子(金屬被覆樹脂粒子)、於導電粒子之表面附著有絕緣性微粒子者、導電粒子之表面經絕緣處理者等)中,根據硬度、光學性能等用途所要求之性能而適當選擇。例如,若為光學膜或消光膜,則可使用氧化矽填料、氧化鈦填料、苯乙烯填料、丙烯酸填料、三聚氰胺填料或各種鈦酸鹽等。若為電容器用膜,則可使用氧化鈦、鈦酸鎂、鈦酸鋅、鈦酸鉍、氧化鑭、鈦酸鈣、鈦酸鍶、鈦酸鋇、鈦酸鋯酸鋇、鈦酸鋯酸鉛及該等之混合物等。若為接著膜,則可含有聚合物系之橡膠粒 子、矽酮橡膠粒子等。若為異向性導電膜,則可含有導電粒子。作為導電粒子,可列舉:鎳、鈷、銀、銅、金、鈀等金屬粒子、焊料等合金粒子、金屬被覆樹脂粒子、表面附著有絕緣性微粒子之金屬被覆樹脂粒子等。亦可併用2種以上。其中,就連接後藉由樹脂粒子反彈而變得容易維持與端子之接觸,從而導通性能穩定之方面而言,較佳為金屬被覆樹脂粒子。又,亦可藉由公知之技術於導電粒子之表面實施不會對導通特性造成阻礙之絕緣處理。按上述用途所列舉之填料並不限定於該用途,視需要亦可含有於其他用途之含填料膜中。又,於各用途之含填料膜中,視需要可併用2種以上之填料。
填料之形狀可根據含填料膜之用途,自球形、橢圓球、柱狀、針狀、其等之組合等中適當選擇而確定。就容易確認填料配置,且容易維持均等之狀態之方面而言,較佳為球形。尤其是,於使含填料膜構成為異向性導電膜之情形時,作為填料之導電粒子較佳為大致真球。藉由使用大致真球者作為導電粒子,例如於如日本特開2014-60150號公報中所記載般,使用轉印模具來製造使導電粒子排列之異向性導電膜時,由於導電粒子於轉印模具上順暢地滾動,故而可將導電粒子高精度地填充至轉印模具上之特定位置。因此,可精確地配置導電粒子。
為了能夠因應配線高度之不均,又,為了抑制導通電阻之上升且抑制短路,填料1之粒徑D較佳為1μm以上且30μm以下,更佳為3μm以上且9μm以下。分散於樹脂層2之前之填料之粒徑可藉由一般之粒度分佈測定裝置進行測定,又,平均粒徑亦可使用粒度分佈測定裝置而求出。作為測定裝置,可列舉FPIA-3000(Malvern公司)作為一例。異向性導電膜等含填料膜中之導電粒子等填料之粒徑D可根據SEM等電子顯微鏡觀察而求出。於該情形時,較理想為將測定填料之粒徑D的樣品數設為200以上。又,於填料之形狀不為球形之情形時,可基於含填料膜之平面圖像或剖面圖像,將最大長度或模擬球形之形狀之直徑 設為填料之粒徑D。
<填料之排列>
於本發明之含填料膜(作為其一態樣之異向性導電膜)中,導電粒子等填料1於膜之俯視下規則地配置而並非為無規。較佳為於膜之俯視下填料1相互不接觸地存在,且於膜厚方向上填料1亦相互不重疊地存在。因此,相對於填料整體,填料1彼此以相互不接觸之狀態存在之個數比率為95%以上,較佳為98%以上,更佳為99.5%以上。又,較佳為各填料1之膜厚方向之位置亦一致。例如,可如圖1A所示般將填料1設為六方晶格排列,如下所述般使填料1之膜厚方向之埋入量Lb一致。再者,於填料彼此以相互不接觸之狀態存在之個數比率為95%以上之填料之分散狀態下,亦可存在相對於填料之特定之規則配置而填料脫落之部位Px(圖1A)。該填料之脫落可藉由下述情況來確認:於特性可容許之範圍內,於膜之特定之方向上規則地存在。又,藉由使填料之脫落重複存在於膜之長邊方向上,或者使填料脫落之部位於膜之長邊方向上逐漸增加或減少,可進行批次管理,亦可對含填料膜及使用其之連接構造體賦予追蹤能力(可追蹤之性質)。其對含填料膜或使用其之連接構造體之防偽造、判定真假、防不法利用等亦有效。
另外,作為填料之規則配置之態樣,可列舉長方晶格、斜方晶格、正方晶格、其他矩形晶格等晶格排列。又,亦可使填料以特定間隔排列成直線狀之粒子列以特定之間隔並列。規則配置只要為於膜之長邊方向上重複者,則並無特別限制。於該等規則配置中,於填料配置為六方晶格、正方晶格或斜方晶格(即,菱形晶格)之情形時,以與任意之填料P0之距離較近之順序選擇3個填料P1、P2、P3時,該3個填料P1、P2、P3與上述填料P0之距離L1、L2、L3中,最大距離(Lmax)與最小距離(Lmin)之比(Lmax/Lmin)較佳為1以上且1.2以下,更佳為1.1以下,進而更佳為1.05以下(圖1A)。尤其是,於填料排列為六 方晶格之情形時,以與任意之填料P0之距離較近之順序選擇5個填料P1、P2、P3、P4、P5,與上述同樣地,求出最大距離(Lmax)與最小距離(Lmin)之比(Lmax/Lmin)時,該比較佳為1以上且1.1以下。於填料配置為六方晶格、正方晶格或斜方晶格(菱形晶格)之情形時,最大距離與最小距離之比(Lmax/Lmin)於設計上為1,但實際上於異向性導電膜等含填料膜之製造時會產生微小之位置偏移,又,若將含填料膜製成捲裝體,則有根據含填料膜之厚度不同而亦會因捲緊而產生微小之位置偏移之虞。因此,上述比(Lmax/Lmin)之上限為本發明中之填料之位置偏移之容許範圍。於本發明中,藉由將該容許範圍抑制為較低,填料彼此相互不接觸且均等地配置。因此,於使含填料膜構成為異向性導電膜之情形時,於異向性導電連接時,可對各填料1即導電粒子均等地施加壓力,從而實際地降低導通電阻之不均。再者,作為如此般亦抑制微小之位置偏移而配置填料之方法,較佳為於如下所述般製造異向性導電膜等含填料膜之情形時,預先製作規定有應配置填料之部位之模具,且於該部位配置填料,並將該填料轉印至樹脂層。
於本發明中,於填料1之排列中有晶格軸或排列軸之情形時,該晶格軸或排列軸可相對於含填料膜之長邊方向平行,亦可與含填料膜之長邊方向交叉。例如,於將含填料膜製成異向性導電膜之情形時,可根據連接之端子寬度、端子間距等而確定。例如,於將含填料膜製成微間距用之異向性導電膜之情形時,較佳為如圖1A所示般使填料1之至少一個晶格軸A相對於含填料膜10A之長邊方向傾斜,且將藉由含填料膜10A連接之端子20之長邊方向與晶格軸A所成之角度θ設為16°~74°。即便於異向性導電膜以外之用途中,藉由如此般傾斜,亦可期待使捕捉狀態穩定之效果。
於本發明中,導電粒子等填料1之粒子間距離係以如下所述般異向性導電膜等含填料膜中之填料1之面積佔有率為25%以下,較佳為0.5%以上且 23%以下,更佳為1.4%以上且未達20%之方式進行設定。又,以填料之個數密度較佳為30~32000個/mm2之方式進行設定。
即,於將面積佔有率設為25%以下之範圍內,填料1之粒子間距離根據藉由含填料膜所連接之端子之大小或端子間距而適當確定。例如,於使含填料膜構成為異向性導電膜之情形時,使異向性導電膜對應微間距之COG(Chip On Glass)時,就抑制短路之方面而言,較佳為將最接近粒子間距離設為填料之粒徑D之0.5倍以上,更佳為設為大於0.7倍。另一方面,就填料1之捕捉性之方面而言,較佳為將最接近粒子間距離設為填料之粒徑D之4倍以下,更佳為設為3倍以下。進而,就穩定地抑制短路之方面而言,無論填料之粒徑如何,均較佳為將填料間之最接近距離設為0.5μm以上。
<填料之個數密度>
於本發明中,填料之個數密度可藉由任意地設定多個部位(5個部位以上,較佳為10個部位以上)之1邊為100μm以上之矩形區域,且將測定區域之合計面積設為2mm2以上而求出。各個區域之大小或數量可根據個數密度之狀態而適當調整。作為微間距用途之個數密度相對較大之情形之一例,可藉由以下方式而獲得,即,針對自含填料膜10A中任意選擇之面積100μm×100μm之區域中之200個部位,使用利用金屬顯微鏡等所得之觀測圖像測定個數密度,並將其平均。面積100μm×100μm之區域為於凸塊間間隔50μm以下之連接對象物中存在1個以上之凸塊之區域。
導電粒子等填料之個數密度除如上述般使用金屬顯微鏡進行觀察而求出以外,亦可藉由圖像解析軟體(例如,WinROOF,三谷商事(股份有限公司)等)測量觀察圖像而求出。
於作為含填料膜之一態樣的異向性導電膜中,於填料之面積佔有率為25%以下之範圍內,導電粒子等填料之個數密度根據填料之粒徑、硬度等進 行設定。即,於異向性導電膜之情形時,若填料之個數密度過小,則無法應對微間距之電子零件之連接,若過大,則會導致短路,故而於粒徑1~30μm之情形時,較佳為30~32000個/mm2,更佳為280~28000個/mm2。
<填料之面積佔有率>
於作為本發明之含填料膜之一態樣的異向性導電膜中,就使異向性導電連接時等之按壓治具所需要之推力不會變得過大之方面而言,導電粒子等填料之面積佔有率為25%以下,較佳為23%以下,更佳為未達20%。又,就確保導通可靠性之方面而言,較佳為0.5%以上,更佳為1%以上,進而較佳為2%以上。填料之面積佔有率係藉由「=[俯視下之填料之個數密度]×[1個填料之俯視面積之平均數]×100」而算出。含填料膜之面積佔有率根據其用途而適當選擇即可,只要不對製造造成阻礙則無限制,但即便於異向性導電連接以外之連接中,亦可謂如上述之穩定性,故而較佳為與上述相同之範圍。
式中,填料之個數密度係藉由上述方法而求出,1個填料之俯視面積之平均數可藉由測量根據膜面之利用金屬顯微鏡等所得之觀測圖像而求出。亦可使用上述圖像解析軟體(WinROOF,三谷商事(股份有限公司))等。
於本發明中,於作為含填料膜之一態樣的異向性導電膜中,將填料之面積佔有率作為熱壓接於電子零件時按壓治具所需要之推力之指標,以填料之面積佔有率成為25%以下之方式,設定填料之粒徑、填料之個數密度等。習知,根據電子零件之端子寬度、端子間距離、填料之粒徑、及填料之排列等,而確定填料之粒子間距離或個數密度,但於本發明中,進而以填料之面積佔有率成為25%以下之方式確定填料之粒子間距離或個數密度。藉此,將異向性導電膜壓接於電子零件時,可消除需要過高之推力之情況。又,作為另一態樣,例如有光學膜,藉由如上述般調整填料之面積佔有率等,可調整填料之光學性能。對於消光膜等直接關係到外觀者,亦可謂相同。
<樹脂層>
(樹脂層之黏度)
樹脂層2之最低熔融黏度並無特別限制,可根據含填料膜之用途或含填料膜之製造方法等而適當確定。例如,只要可形成下述凹陷2b、2c,則根據含填料膜之製造方法,亦可設為1000Pa‧s左右。另一方面,作為含填料膜之製造方法,進行使填料以特定之配置保持於樹脂層之表面,並將該填料壓入樹脂層之方法時,就樹脂層可進行膜成形之方面而言,較佳為將樹脂層之最低熔融黏度設為1100Pa‧s以上。
又,如於下述之含填料膜之製造方法中所說明般,就如圖1B所示般於壓入至樹脂層2中之填料1之露出部分之周圍形成凹陷2b,或者如圖6所示般於壓入樹脂層2中之填料1之正上方之樹脂層2之表面形成凹陷2c之方面而言,較佳為1500Pa‧s以上,更佳為2000Pa‧s以上,進而較佳為3000~15000Pa‧s,進而更佳為3000~10000Pa‧s。作為一例,該最低熔融黏度可使用旋轉式流變計(TA instruments公司製造),於測定壓力5g下保持為固定,使用直徑8mm之測定板而求出,更具體而言,可藉由設為於溫度範圍30~200℃,升溫速度10℃/分鐘,測定頻率10Hz,對上述測定板之荷重變動5g而求出。
藉由將樹脂層2之最低熔融黏度設為1500Pa‧s以上之高黏度,可抑制將含填料膜壓接於物品時填料之不必要之移動,尤其是,於將含填料膜製成異向性導電膜之情形時,可防止於異向性導電連接時應夾持於端子間之導電粒子因樹脂流動而流動。
又,於藉由將填料1壓入樹脂層2中而形成含填料膜10A之填料分散層3之情形時,關於壓入填料1時之樹脂層2,於以填料1自樹脂層2露出之方式將填料1壓入樹脂層2中時,樹脂層2發生塑性變形而於填料1之周圍之樹脂層2形成凹陷2b(圖1B)的高黏度之黏性體,或者於以填料1不自樹脂層2露出而埋入 樹脂層2中之方式壓入填料1時,於填料1之正上方之樹脂層2之表面形成凹陷2c(圖6)的高黏度之黏性體。因此,樹脂層2之於60℃之黏度之下限較佳為3000Pa‧s以上,更佳為4000Pa‧s以上,進而較佳為4500Pa‧s以上,上限較佳為20000Pa‧s以下,更佳為15000Pa‧s以下,進而較佳為10000Pa‧s以下。該測定可藉由與最低熔融黏度相同之測定方法進行,抽選溫度為60℃之值而求出。
將填料1壓入樹脂層2時之該樹脂層2之具體黏度根據所形成之凹陷2b、2c之形狀或深度等,下限較佳為3000Pa‧s以上,更佳為4000Pa‧s以上,進而較佳為4500Pa‧s以上,上限較佳為20000Pa‧s以下,更佳為15000Pa‧s以下,進而較佳為10000Pa‧s以下。又,較佳為於40~80℃,更佳為於50~60℃獲得此種黏度。
如上所述,藉由於自樹脂層2露出之填料1之周圍形成有凹陷2b(圖1B),針對將含填料膜壓接於物品時所產生之填料1之扁平化,自樹脂所受之阻力與無凹陷2b之情形相比降低。因此,於將含填料膜製成異向性導電膜之情形時,於異向性導電連接時導電粒子變得容易由端子夾持,藉此導通性能提高,又,捕捉性提高。
又,藉由於不自樹脂層2露出而埋入之填料1之正上方之樹脂層2之表面形成有凹陷2c(圖6),與無凹陷2c之情形相比,於將含填料膜壓接於物品時之壓力容易集中於填料1。因此,於將含填料膜製成異向性導電膜之情形時,於異向性導電連接時導電粒子變得容易由端子夾持,藉此捕捉性提高,導通性能提高。此種捕捉性之提高並不限定於異向性導電膜,對於異向性導電膜以外之含填料膜,亦可期待相同之效果。
<代替凹陷之“傾斜”或“起伏”>
如圖1B、圖6所示之含填料膜(作為其一態樣之異向性導電膜)之「凹陷」2b、2c亦可根據「傾斜」或「起伏」之觀點進行說明。以下一面參照圖式一面 進行說明。
含填料膜(作為其一態樣之異向性導電膜)10A係由填料分散層3所構成(圖1B)。於填料分散層3中,填料1以露出之狀態規則地分散於樹脂層2之單面。構成於膜之俯視下填料1相互不接觸,且於膜厚方向上填料1亦相互不重疊地規則分散,填料1之膜厚方向之位置一致的單層之填料層。
於各個填料1之周圍之樹脂層2之表面2a,相對於鄰接之填料間之中央部之樹脂層2之切平面2p形成有傾斜2b。再者,如下所述,於本發明之含填料膜中,亦可於埋入樹脂層2中之填料1的正上方之樹脂層之表面形成起伏2c(圖6)。
於本發明中,所謂「傾斜」,意指於填料1之附近,樹脂層之表面之平坦性受損,而相對於上述切平面2p,樹脂層之一部分缺失而樹脂量減少之狀態。換言之,藉由傾斜,填料周圍之樹脂層之表面相對於切平面缺失。另一方面,所謂「起伏」,意指於填料正上方之樹脂層之表面有起伏,因存在如起伏般具有高低差之部分而樹脂減少之狀態。換言之,填料正上方之樹脂層之樹脂量與填料正上方之樹脂層之表面處於切平面時相比變少。該等情況可將相當於填料正上方之部位與填料間之平坦之表面部分(圖1B、圖6)進行對比而識別。再者,亦有起伏之起點作為傾斜而存在之情況。
如上所述,藉由於自樹脂層2露出之填料1之周圍形成有傾斜2b(圖1B),於使含填料膜構成為異向性導電膜之情形時,針對異向性導電連接時於端子間夾持填料1時所產生之填料1之扁平化,自樹脂所受之電阻與無傾斜2b之情形相比而降低,故而變得容易將填料夾持於端子中,藉此導通性能提高,又,捕捉性提高。該傾斜較佳為沿著填料之外形。原因在於:除變得更容易表現連接中之效果以外,亦變得容易識別填料,藉此變得容易進行異向性導電膜等含填料膜之製造中之檢查等。又,該傾斜及起伏有因對樹脂層進行熱壓等而 其一部分消失之情況,本發明包含此種情況。於該情形時,填料有於樹脂層之表面以1點露出之情況。再者,於使含填料膜構成為異向性導電膜之情形時,連接之電子零件多種多樣,為了與該等相應地進行調整且滿足各種要件,而期望設計之自由度較高,故而亦可使傾斜或起伏減少、或者使其部分消失而使用。
又,藉由於不自樹脂層2露出而埋入之填料1之正上方之樹脂層2之表面形成有起伏2c(圖6),與傾斜之情形同樣地,於使含填料膜構成為異向性導電膜之情形時,於異向性導電連接時來自端子之按壓力容易施加於填料。又,藉由具有起伏,填料正上方之樹脂量較樹脂平坦地堆積之情形減少,故而變得容易排除連接時之填料正上方之樹脂,端子與填料變得容易接觸,因此端子中之填料之捕捉性提高,導通可靠性等導通性能提高。
就容易獲得上述之填料之露出部分之周圍之樹脂層2之傾斜2b(圖1B)、或填料正上方之樹脂層之起伏2c(圖6)之效果之方面而言,傾斜2b之最大深度Le與填料1之粒徑D之比(Le/D)較佳為未達50%,更佳為未達30%,進而較佳為20~25%,傾斜2b或起伏2c之最大直徑Ld與填料1之粒徑D之比(Ld/D)較佳為100%以上,更佳為100~150%,起伏2c之最大深度Lf與填料1之粒徑D之比(Lf/D)大於0,較佳為未達10%,更佳為5%以下。
再者,傾斜2b或起伏2c中之填料1之露出(正上方)部分之直徑Lc可設為填料1之粒徑D以下,較佳為粒徑D之10~90%。又,可於填料1之頂部之1點露出,亦可使粒徑D完全埋入樹脂層2內,直徑Lc成為零。
於此種本發明中,樹脂層2之表面之傾斜2b、起伏2c之存在可藉由利用掃描式電子顯微鏡觀察異向性導電膜等含填料膜之剖面而進行確認,於面視野觀察中亦可確認。亦可利用光學顯微鏡、金屬顯微鏡觀察傾斜2b、起伏2c。又,傾斜2b、起伏2c之大小亦可藉由圖像觀察時之焦點調整等進行確認。如上所述,藉由熱壓而減少傾斜或起伏後亦相同。原因在於:有痕跡殘留之情況。
(樹脂層之組成)
根據含填料膜之用途,樹脂層2可為導電性,亦可為絕緣性,又,可為塑化性,亦可為硬化性,較佳可由絕緣性之硬化性樹脂組成物形成,例如可由含有熱聚合性化合物與熱聚合起始劑之絕緣性之熱聚合性組成物形成。熱聚合性組成物中視需要亦可含有光聚合起始劑。作為由絕緣性之硬化性樹脂組成物形成者,可列舉異向性導電膜。
於將熱聚合起始劑與光聚合起始劑併用之情形時,可使用作為熱聚合性化合物及作為光聚合性化合物均發揮功能者,亦可與熱聚合性化合物分開另外含有光聚合性化合物。較佳為與熱聚合性化合物分開另外含有光聚合性化合物。例如,使用陽離子系熱硬化起始劑作為熱聚合起始劑,使用環氧樹脂作為熱聚合性化合物,使用光自由基聚合起始劑作為光聚合起始劑,使用丙烯酸酯化合物作為光聚合性化合物。
作為光聚合起始劑,亦可含有與波長不同之光反應之多個種類。藉此,可區分使用:於製造異向性導電膜等含填料膜時構成樹脂層之樹脂之一次光硬化、及於異向性導電連接時用以將電子零件彼此接著之樹脂之光硬化等二次光硬化中所使用的波長。亦可應用於異向性導電膜以外之用途。
於製造異向性導電膜時之光硬化中,可使絕緣性樹脂層中所含之光聚合性化合物之全部或一部分發生光硬化。藉由該光硬化而保持或固定絕緣性樹脂層2中之導電粒子1之配置,有望抑制短路及提高導電粒子之捕捉。又,亦可藉由該光硬化,對異向性導電膜之製造步驟中之絕緣性樹脂層的黏度進行適當調整。該光硬化尤佳為於絕緣性樹脂層2之層厚La與導電粒子1之平均粒徑D之比(La/D)未達0.6之情形時進行。原因在於:於絕緣性樹脂層2之層厚相對於導電粒徑較薄之情形時,亦更確實地保持或固定絕緣性樹脂層2中之導電粒子之配置,並且進行絕緣性樹脂層2之黏度調整,從而抑制於使用異向性導電膜之 電子零件彼此之連接中良率之降低。
樹脂層中之光聚合性化合物之摻合量較佳為30質量%以下,更佳為10質量%以下,進而更佳為未達2質量%。原因在於:若光聚合性化合物過多,則連接時之壓入所需之推力增加。
作為熱聚合性組成物之例,可列舉:含有(甲基)丙烯酸酯化合物及熱自由基聚合起始劑之熱自由基聚合性丙烯酸酯系組成物、含有環氧化合物及熱陽離子聚合起始劑之熱陽離子聚合性環氧系組成物等。亦可使用含有熱陰離子聚合起始劑之熱陰離子聚合性環氧系組成物,代替含有熱陽離子聚合起始劑之熱陽離子聚合性環氧系組成物。又,只要未特別造成阻礙,則亦可併用多種聚合性化合物。作為併用例,可列舉併用熱陽離子聚合性化合物與熱自由基聚合性化合物等。
此處,作為(甲基)丙烯酸酯化合物,可使用習知公知之熱聚合型(甲基)丙烯酸酯單體。例如,可使用單官能(甲基)丙烯酸酯系單體、二官能以上之多官能(甲基)丙烯酸酯系單體。
作為熱自由基聚合起始劑,例如可列舉:有機過氧化物、偶氮系化合物等。尤其可較佳地使用不產生成為氣泡之氮之有機過氧化物。
熱自由基聚合起始劑之使用量若過少,則硬化不良,若過多,則製品壽命降低,故而相對於(甲基)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。
作為環氧化合物,可列舉:雙酚A型環氧樹脂、雙酚F型環氧樹脂、酚醛清漆型環氧樹脂、其等之改質環氧樹脂、脂環式環氧樹脂等,可併用該等之2種以上。又,除環氧化合物以外,亦可併用氧雜環丁烷化合物。
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而公知者,例如可使用藉由熱而產生酸之錪鹽、鋶鹽、鏻鹽、二茂鐵 類等,尤其可較佳地使用對溫度顯示良好之潛伏性之芳香族鋶鹽。
熱陽離子聚合起始劑之使用量過少則有硬化不良之傾向,過多則有製品壽命降低之傾向,故而相對於環氧化合物100質量份,較佳為2~60質量份,更佳為5~40質量份。
熱聚合性組成物較佳為含有膜形成樹脂或矽烷偶合劑。作為膜形成樹脂,可列舉: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,可併用該等之2種以上。於該等中,就製膜性、加工性、連接可靠性之觀點而言,可較佳地使用苯氧基樹脂。重量平均分子量較佳為10000以上。又,作為矽烷偶合劑,可列舉:環氧系矽烷偶合劑、丙烯酸系矽烷偶合劑等。該等矽烷偶合劑主要為烷氧基矽烷衍生物。
為了調整熔融黏度,熱聚合性組成物中亦可與上述之填料1分開另外含有絕緣性填料。其可列舉氧化矽粉或氧化鋁粉等。較佳為絕緣性填料粒徑20~1000nm之微小之填料,又,摻合量較佳為相對於環氧化合物等熱聚合性化合物(光聚合性化合物)100質量份設為5~50質量份。與填料1分開另外含有之絕緣性填料可較佳地用於含填料膜之用途為異向性導電膜之情形,根據用途亦可不為絕緣性,例如亦可含有導電性之微小之填料。於使含填料膜構成為異向性導電膜之情形時,形成填料分散層之樹脂層中視需要可適當含有與填料1不同之更微小之絕緣性填料(所謂奈米填料)。
本發明之含填料膜中,亦可與上述絕緣性或導電性之填料分開另外含有填充劑、軟化劑、促進劑、抗老化劑、著色劑(顏料、染料)、有機溶劑、離子捕捉劑等。
(樹脂層之層厚)
於作為本發明之含填料膜之一態樣的異向性導電膜中,樹脂層2之層厚La與 填料1之粒徑D之比(La/D)為0.3以上且1.3以下。此處,填料1之粒徑D意指其平均粒徑。若樹脂層2之層厚La過大而該比變得過大,則於異向性導電連接時填料變得難以壓抵於端子,並且填料變得容易因樹脂流動而流動。因此,填料容易發生位置偏移,端子中之填料之捕捉性降低。又,為了將填料壓抵於端子而按壓治具所需要之推力亦增大,成為低壓構裝之妨礙。相反,若樹脂層2之層厚La過小而該比變得過小,則難以藉由樹脂層2將填料1維持為特定之配置。尤其是,就維持樹脂層2中之填料1之配置之方面而言,該比(La/D)較佳為大於0.3,更佳為設為0.4以上。又,就抑制異向性導電連接時之過度之樹脂流動及實現低壓構裝之方面而言,較佳為1以下。就容易使填料1自樹脂層2露出,且更容易進行低壓構裝之方面而言,較佳為將該比(La/D)設為未達1,更佳為未達0.6,進而較佳為0.5以下。於該情形時,填料1亦可貫通樹脂層2。
(樹脂層中之填料之埋入狀態)
於本實施例之含填料膜(作為其一態樣之異向性導電膜)10A中,如圖1B所示,填料1係以埋入率(Lb/D)為30%以上且100%以下,且以填料1自樹脂層2之單面突出之方式埋入。另外,作為本發明之含填料膜,可列舉以下態樣:如圖2所示之含填料膜(作為其一態樣之異向性導電膜)10B,以埋入率100%或者其附近,且以填料1自樹脂層2之單面露出,其膜面與填料1之頂部1a成為大致同一平面之方式埋入的態樣;如圖3所示之含填料膜(作為其一態樣之異向性導電膜)10C,於樹脂層2之單面,填料1與其膜面成為大致同一平面,且於相反面,填料1自膜面不露出地突出的態樣;如圖4所示之含填料膜(作為其一態樣之異向性導電膜)10D,於樹脂層2之單面,填料1埋入膜面以下並露出,且自相反面填料1不露出地自膜面突出的態樣;如圖5所示之含填料膜(作為其一態樣之異向性導電膜)10E,於樹脂層2之表面無凹陷,且填料1以其頂部1a之1點自樹脂層2露出的態樣;如圖6所示之含填料膜(作為其一態樣之異向性導電膜)10F, 填料1不自樹脂層2露出,且於填料1之正上方之樹脂層2之表面具有凹陷(較周圍之樹脂層之表面凹陷之部分)2c的態樣等。
此處,所謂埋入率,係於將埋入有填料1之樹脂層2之表面2a(樹脂層2之正面及背面中填料1露出之側之表面、或者於填料完全埋入樹脂層2中之情形時與填料之距離較近之表面)中鄰接之填料間之中央部之切平面2p與填料1之最深部之距離設為埋入量Lb的情形時,填料1之埋入量Lb相對於填料1之粒徑D之比率(Lb/D)(圖1B)。因此,如圖4所示,於填料1較膜面更深地埋入之情形時,埋入率(Lb/D)變得大於100%,作為一例,可列舉105%以下。填料1正好貫通樹脂層2之情形時之埋入率(Lb/D)為100%。
藉由將埋入率較佳地設為30%以上,可藉由樹脂層2將填料1維持為特定之粒子分散狀態或者特定之排列,又,藉由將埋入率設為100%以下,較佳為70%以下,更佳為未達60%,可降低於構成樹脂層2之樹脂中,於使含填料膜構成為異向性導電膜之情形時,以於異向性導電連接時使填料流動且使捕捉率降低之方式發揮功能的樹脂之量。又,藉由無用之樹脂層2變少,而變得容易壓入填料。相對於此,若埋入率未達30%,則於異向性導電連接時填料1容易於樹脂層2上滾動,而難以將填料1維持在特定之位置,故而捕捉率降低。又,若埋入率超過100%而填料完全埋沒於樹脂層2中,則有於異向性導電連接時填料1因樹脂層2之樹脂流動而流動,捕捉性降低,引起短路之情況。又,藉由使填料自樹脂層2露出之程度一致,有望其特性提高之效果。作為一例,於光學膜之性能依賴於填料之情形時,若於俯視下之分散性(獨立性)與露出之程度具有一定以上之規則性,則推測較塗佈單純混練之黏合劑等所得者,可獲得性能之提高或品質之穩定性。
再者,於本發明中,埋入率(Lb/D)之數值係指作為含填料膜之一態樣的異向性導電膜中所含之總填料數之99%以上,較佳為99.9%以上,更 佳為99.99%以上為該埋入率(Lb/D)之數值。因此,所謂埋入率為30%以上且100%以下,係指異向性導電膜等含填料膜中所含之總填料數之99%以上,較佳為99.9%以上,更佳為99.99%以上之埋入率為30%以上且100%以下。如上所述,藉由總填料之埋入率(Lb/D)一致,於異向性導電膜之情形時,由於對填料之按壓均勻地增加,故而端子中之填料之捕捉狀態良好,導通之可靠性提高。推測即便於僅單純使含填料膜貼合之情形時,亦可獲得較塗佈單純混練之黏合劑等所得者以上之如上述般之效果。
於上述之含填料膜10B(圖2)、10C(圖3)、10E(圖5)中,樹脂層2之膜面與填料1之頂部1a成為大致同一平面,藉此與填料1自樹脂層2突出之含填料膜10A(圖1B)相比,於使含填料膜構成為異向性導電膜之情形時,可帶來以下優點:於異向性導電連接時各個填料1周邊之膜厚方向之樹脂量變得均勻。尤其是,於含填料膜10E(圖5)中,異向性導電連接時將填料壓入端子或凸塊時,由於填料1之頂部1a周邊之樹脂量均勻,故而填料1變得難以移動,而可期待捕捉性增高,可抑制短路之效果。其尤其對微間距或凸塊間間隔狹小之情形有效。
又,於上述之含填料膜10A(圖1B)、10B(圖2)、10C(圖3)、10D(圖4)中,樹脂層2之正面及背面之表面中埋入有填料1之面之與填料1接觸的部分及其附近與周圍平坦之表面2a相比而凹陷。該凹陷2b有於製造含填料膜時將填料1壓入樹脂層2中之情形時,壓入時之樹脂層之黏度為上述較佳黏度範圍內時形成之情況。藉由於樹脂層2之表面具有凹陷2b,於使含填料膜構成為異向性導電膜之情形時,可期待針對異向性導電連接時於端子間夾持填料1時所產生之填料1之扁平化,自樹脂層2所受之電阻與無凹陷2b之情形相比降低,端子中之填料之壓入容易變得均勻之效果。如上所述,作為含填料膜,較塗佈單純混練之黏合劑等所得者,於填料與樹脂之狀態具有特異性,故而可期待於性能 或品質產生特徵(性能提高或品質穩定化等)。
又,含填料膜(作為其一態樣之異向性導電膜)10F(圖6)中之凹陷2c亦於製造含填料膜時將填料1壓入樹脂層2中之情形時,壓入時之樹脂層2為上述較佳黏度範圍內之情形時形成。藉由於樹脂層2之表面形成有凹陷2c,與無凹陷2c之情形相比,於使含填料膜構成為異向性導電膜之情形時,可期待異向性導電連接時之壓力變得容易集中於填料1,端子中之填料之壓入容易變得均勻之效果。如上所述,作為含填料膜,與塗佈單純混練之黏合劑等所得者之差異亦與上述相同。
再者,樹脂層2之表面之凹陷2b、2c之存在可藉由利用掃描式電子顯微鏡觀察含填料膜之剖面進行確認,亦可於利用掃描式電子顯微鏡之面視野觀察中進行確認。又,亦可利用光學顯微鏡、金屬顯微鏡進行觀察。
<變形態樣>
作為本發明之含填料膜,可於填料分散層3積層較佳為最低熔融黏度低於構成樹脂層2之樹脂之第2樹脂層4(圖7~圖9)。該第2樹脂層4由於最低熔融黏度低於樹脂層2,故而於使含填料膜構成為異向性導電膜之情形時,可填充於異向性導電連接時由電子零件之凸塊等端子所形成之空間,提高對向之電子零件彼此之接著性。即,為了實現使用異向性導電膜之電子零件之低壓構裝,及為了抑制異向性導電連接時之樹脂層2之樹脂流動而提高填料1之粒子捕捉性,較理想為提高樹脂層2之黏度,且於不引起填料1之位置偏移之範圍內使樹脂層2之厚度變薄,但若過度減薄樹脂層2之厚度,則會導致使對向之電子零件彼此接著之樹脂量不足,故而有接著性降低之擔憂。相對於此,藉由於異向性導電連接時設置黏度低於樹脂層2之第2樹脂層4,亦可提高電子零件彼此之接著性,由於第2樹脂層4之流動性較高,故而不易阻礙利用端子夾持或壓入填料。
於填料分散層3積層第2樹脂層4之情形時,無論第2樹脂層4是否 於凹陷2b之形成面上,均較佳為於利用工具加壓之電子零件上貼合第2樹脂層4(將樹脂層2貼合於載置於載台上之電子零件)。藉由此種方式,可避免填料之不經意之移動,從而可提高捕捉性。推測除異向性導電膜以外亦相同。
樹脂層2與第2樹脂層4之最低熔融黏度比之差異越大,由電子零件之電極或凸塊所形成之空間變得越容易被第2樹脂層4填充,從而可提高電子零件彼此之接著性。又,該差異越大,填料分散層3中所存在之樹脂之移動量越相對變少,端子間之填料1越不易因樹脂流動而流動,藉此端子中之填料之捕捉性提高,故而較佳。於實際使用時,樹脂層2與第2樹脂層4之最低熔融黏度比較佳為2以上,更佳為5以上,進而較佳為8以上。另一方面,若該比過大,則於將長條之含填料膜製成捲裝體之情形時,有樹脂之滲出或黏連之虞,故而於實際使用時較佳為15以下。更具體而言,第2樹脂層4之較佳最低熔融黏度滿足上述之比,且為3000Pa‧s以下,更佳為2000Pa‧s以下,尤其是100~2000Pa‧s。
再者,第2樹脂層4可藉由於與樹脂層2相同之樹脂組成物中調整黏度而形成。
又,第2樹脂層4之層厚較佳為4~20μm。或者,相對於填料之粒徑,較佳為1~8倍。
又,合併樹脂層2與第2樹脂層4之含填料膜10G、10H、10I整體之最低熔融黏度較佳為200~4000Pa‧s。
作為第2樹脂層4之具體積層態樣,例如可如圖7所示之含填料膜10G般,於填料分散層3之單面積層第2樹脂層4。於該情形時,填料1之粒徑D與樹脂層2之層厚La的關係如上所述將La/D設為0.3以上且1.3以下。
如圖8所示之含填料膜10H般,於填料1自樹脂層2之單面突出之情形時,亦可於其突出之面積層第2樹脂層4,使填料1沒入第2樹脂層4中。於填料1之埋入率為95%以下之情形時,較佳為以此種方式積層樹脂層4,於90%以下 之情形時更佳。
如圖9所示之含填料膜101般,亦可於與埋入有填料1之樹脂層2之面的相反側之面積層第2樹脂層4。
(第3樹脂層)
亦可與第2樹脂層4夾持樹脂層2於相反側設置第3樹脂層。可使第3樹脂層作為黏著層而發揮功能。亦可與第2樹脂層4同樣地,為了填充由電子零件之電極或凸塊所形成之空間而設置。
第3樹脂層之樹脂組成、黏度及厚度可與第2樹脂層相同,亦可不同。合併樹脂層2、第2樹脂層4及第3樹脂層之含填料膜的最低熔融黏度並無特別限制,可設為200~4000Pa‧s。
(其他積層態樣)
根據含填料膜之用途,可積層多個填料分散層,亦可於積層之填料分散層間介置如第2樹脂層般不含有填料之層,亦可於最外層設置第2樹脂層或第3樹脂層。
<含填料膜之製造方法>
由填料分散層3之單層所形成之本發明之含填料膜例如使填料1以特定之排列保持於樹脂層2之表面,並將該填料1利用平板或滾筒壓入樹脂層2中。
此處,樹脂層2中之填料1之埋入量Lb可藉由壓入填料1時之按壓力、溫度等進行調整,又,凹陷2b、2c之有無、形狀及深度可藉由壓入時之樹脂層2之黏度、壓入速度、溫度等進行調整。
又,作為使填料1保持於樹脂層2之方法,並無特別限定,例如使用轉印模具使填料1保持於樹脂層2。作為轉印模具,例如可使用對矽、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之轉印模具材料,藉由光微影法等公知之開口形成方法形成有開口者。再者,轉印模具可採取板 狀、滾筒狀等形狀。
於使含填料膜構成為異向性導電膜之情形時,為了使用該異向性導電膜經濟地進行電子零件之連接,作為含填料膜之異向性導電膜較佳為某種程度之長條。因此,異向性導電膜較佳為將長度製造成5m以上,更佳為10m以上,進而較佳為25m以上。另一方面,若使異向性導電膜過長,則於使用異向性導電膜進行電子零件之製造之情形時所使用之先前之連接裝置變得無法再使用,操作性亦較差。因此,異向性導電膜較佳為將長度製造成5000m以下,更佳為1000m以下,進而較佳為500m以下。就操作性優異之方面而言,異向性導電膜之此種長條體較佳為製成捲繞於捲芯之捲裝體。於除異向性導電膜以外之用途中,亦因相同或者類似之理由,而認為上限與上述相同。
<含填料膜之使用方法>
本發明之含填料膜可與先前之含填料膜同樣地使用,只要可使含填料膜貼合,則物品並無特別限制。可藉由壓接,較佳為藉由熱壓接貼合於根據含填料膜之用途的各種物品。於該貼合時,可利用光照射,亦可併用熱與光。例如,於含填料膜之樹脂層對供該含填料膜貼合之物品具有充分之黏著性之情形時,可藉由將含填料膜之樹脂層輕輕壓抵於物品,而獲得將含填料膜貼合於一物品之表面而成的膜貼合體。於該情形時,物品之表面不限於平面,可具有凹凸,亦可整體上彎曲。於物品為膜狀或平板狀之情形時,可使用壓接滾筒將含填料膜貼合於其等物品。藉此,亦可使含填料膜之填料與物品直接接合。
又,亦可使對向之2個物品間介置含填料膜,利用熱壓接滾筒或壓接工具將對向之2個物品接合,而使填料夾持於該物品間。又,亦可藉由物品夾入含填料膜以不使填料與物品直接接觸。
尤其是,於將含填料膜設為異向性導電膜之情形時,使用熱壓接工具,經由該異向性導電膜將IC晶片、IC模組、FPC等第1電子零件、與FPC、 玻璃基板、塑膠基板、剛性基板、陶瓷基板等第2電子零件進行異向性導電連接時可較佳地使用。亦可使用異向性導電膜將IC晶片或晶圓堆疊而多層化。再者,藉由本發明之異向性導電膜連接之電子零件並不限定於上述電子零件。近年來,可用於多樣化之各種電子零件。
因此,本發明包含將本發明之含填料膜藉由壓接貼合於各種物品而成之連接構造體、或其製造方法。尤其是,於將含填料膜設為異向性導電膜之情形時,亦包含使用該異向性導電膜將電子零件彼此進行異向性導電連接之連接構造體之製造方法、或藉此獲得之連接構造體、即藉由本發明之異向性導電膜將電子零件彼此進行異向性導電連接之連接構造體。
作為使用異向性導電膜之電子零件之連接方法,於異向性導電膜由導電粒子分散層3之單層所構成之情形時,可藉由以下方式而製造,即,將異向性導電膜之表面埋入有導電粒子1之側暫時貼合於各種基板等第2電子零件而進行暫時壓接,於暫時壓接之異向性導電膜之表面未埋入有導電粒子1之側貼合IC晶片等第1電子零件,並進行熱壓接。於異向性導電膜之絕緣性樹脂層中不僅含有熱聚合起始劑及熱聚合性化合物,亦含有光聚合起始劑及光聚合性化合物(亦可與熱聚合性化合物相同)之情形時,亦可利用併用光與熱之壓接方法。若以此種方式進行,則可將導電粒子之不經意之移動抑制為最小限度。又,可將未埋入有導電粒子之側暫時貼合於第2電子零件而使用。再者,不僅可將異向性導電膜暫時貼合於第2電子零件,亦可將異向性導電膜暫時貼合於第1電子零件。
又,於異向性導電膜由導電粒子分散層3及第2絕緣性樹脂層4之積層體形成之情形時,將導電粒子分散層3暫時貼合於各種基板等第2電子零件而進行暫時壓接,於暫時壓接之異向性導電膜之第2絕緣性樹脂層4側將IC晶片等第1電子零件對準而載置,並進行熱壓接。亦可將異向性導電膜之第2絕緣性 樹脂層4側暫時貼合於第1電子零件。又,亦可將導電粒子分散層3側暫時貼合於第1電子零件而使用。
[實施例]
以下,藉由實施例對作為本發明之含填料膜之一態樣的異向性導電膜進行具體說明。
實施例1~5、比較例1
(1)異向性導電膜之製造
以表1所示之摻合,分別製備形成導電粒子分散層之絕緣性樹脂層形成用樹脂組成物、及第2絕緣性樹脂層形成用樹脂組成物。絕緣性樹脂層之最低熔融黏度為3000Pa‧s以上,該絕緣性樹脂層之最低熔融黏度與第2絕緣性樹脂層之最低熔融黏度之比為2以上。
將形成絕緣性樹脂層(高黏度樹脂層)之樹脂組成物藉由棒式塗佈機塗佈於膜厚度50μm之PET膜上,於80℃之烘箱中乾燥5分鐘,於PET膜上形成表2所示之厚度之絕緣性樹脂層。同樣地,以表2所示之厚度於PET膜上形成第2絕緣性樹脂層。
另一方面,以導電粒子(平均粒徑3.5μm)1於俯視下成為圖1A所示之六方晶格排列,且導電粒子之粒子間距離成為3.5μm,個數密度成為23600個/mm2之方式製作模具。使公知之透明性樹脂之顆粒以熔融之狀態流入該模具中,冷卻而凝固,藉此形成凹部為圖1A所示之排列圖案之樹脂模具。
於該樹脂模具之凹部填充導電粒子(積水化學工業(股份有限公司)製造,Ni/Au鍍覆樹脂粒子,平均粒徑3.5μm),並於其上覆蓋上述絕緣性樹脂層,於60℃、0.5MPa進行按壓,藉此使其貼合。並且,自模具剝離絕緣性樹脂層,將絕緣性樹脂層上之導電粒子於(按壓條件:60~70℃、0.5MPa)壓入該絕緣性樹脂層內,形成導電粒子分散層(實施例1~5)。
於比較例1中,於形成表1所示之絕緣性樹脂層之樹脂組成物中混合導電粒子,形成導電粒子以單層無規分散之絕緣性樹脂層(個數密度50000個/mm2)。
藉由金屬顯微鏡對各實施例及比較例之埋入率(Lb/D)及絕緣性樹脂層中之導電粒子之埋入狀態(導電粒子有無自絕緣性樹脂層露出)進行觀察,求出導電粒子之面積佔有率。又,相對於導電粒子整體,導電粒子彼此以相互不接觸之狀態存在之個數比率(導電粒子之不接觸比率)係藉由利用金屬顯微鏡對50μm×50μm範圍內之10個部位進行觀測而求出。示於表2。
進而,藉由於導電粒子分散層之表面積層第2絕緣性樹脂層,而製作2層型之異向性導電膜(實施例1~5、比較例1)。於該情形時,於實施例1~5中,於壓入有導電粒子之側之導電粒子分散層之表面積層第2絕緣性樹脂層。
(2)評價
對(1)中所製作之實施例及比較例之異向性導電膜,以對於連接而言充分之面積裁斷,按以下方式對(a)初始導通電阻、(b)導通可靠性、(c)平均粒子捕捉數、(d)短路率進行評價。將結果示於表2。
(a)初始導通電阻
將以下所示之評價用IC及玻璃基板於180℃、60MPa、5秒下經由異向性導電膜進行加熱加壓,獲得評價用連接物。此時,按壓治具所需之推力為125N。
評價用IC:
外形:1.8×20.0mm
厚度:0.5mm
凸塊規格:尺寸30×85μm,凸塊間距離50μm,凸塊高度15μm
玻璃基板
玻璃材質:Corning公司製造之1737F
外形:30×50mm
厚度:0.5mm
電極:ITO配線
藉由四端子法測定所得之評價用連接物之導通電阻。初始導通電阻於實際使用時較佳為2Ω以下,更佳為0.6Ω以下。
(b)導通可靠性
以與初始導通電阻相同之方式,測定將(a)所得之評價用連接物放置於溫度85℃、濕度85%RH之恆溫槽內500小時後之導通電阻。導通電阻於實際使用時較佳為5Ω以下。
(c)平均粒子捕捉數
使用與(a)相同之評價用IC,將該評價用IC與端子圖案對應之ITO圖案玻 璃基板於與(a)相同之條件下進行加熱加壓,對加熱加壓後之端子對100個計測導電粒子之捕捉數,求出其平均。平均粒子捕捉數於實際使用時較佳為每端子為3個以上。
(d)短路率
使用短路率之評價用IC,以與(a)初始導通電阻之評價相同之方式,獲得評價用連接物,計測所得之評價用連接物之短路數,並求短路率(即短路發生率),按以下基準進行評價。
短路率之評價用IC(7.5μm間隔之梳齒TEG(test element group))
外形:15×13mm
厚度:0.5mm
凸塊規格:尺寸25×140μm,凸塊間距離7.5μm,凸塊高度15μm
短路率評價基準
A:未達50ppm
B:50ppm以上且未達200ppm
C:200ppm以上
根據表2,實施例1~5之異向性導電膜由於絕緣性樹脂層2之層厚La與導電粒子之平均粒徑D之比La/D為0.3~1.3,故而初始導通電阻、導通可靠性、平均粒子捕捉數均良好,測定值之不均亦較少而穩定。尤其是,若考慮實施例1,則可知La/D較佳為大於0.3,且可知La/D為0.5之實施例2之初始導通電阻、導通可靠性及平均粒子捕捉數均優異。再者,容許0.3~1.3之範圍作為La/D之數值意指只要La/D為該範圍,則絕緣性樹脂層2之層厚亦可自設計時之特定之厚度發生變動,於異向性導電膜之製造成本方面有利,尤其是,於異向性導電膜為長條而有樹脂層之層厚發生變動之擔憂的情形有利。再者,於實施例3中,與實施例4及5同樣地,亦存在一部分絕緣性樹脂層與導電粒子成為同 一平面之部位。
相對於此,於比較例1中,導電粒子之個數密度較高,面積佔有率超過25%,基於按壓治具之推力不足,導通可靠性較差。平均粒子捕捉數之不均較大。又,短路率亦較差。
為了獲得初始導通電阻之評價用連接物而對評價用IC及玻璃基板進行加熱加壓時,藉由將加熱加壓條件設為溫度180℃、壓力30MPa、5秒而降低壓力,結果於實施例1及實施例2中初始導通電阻為0.2Ω,於比較例1中為1.2Ω。又,於加熱加壓條件下增加壓力,設為溫度180℃、壓力90MPa、5秒,結果實施例1、實施例2及比較例1之初始導通電阻均為0.2Ω。藉此,可知於比較例1中,為了達成初始導通電阻0.2Ω,需要90MPa之壓力,但於實施例1及實施例2中,以30MPa即可達成,可確認藉由本實施例之異向性導電膜,可進行低壓構裝。
1‧‧‧填料(導電粒子)
2‧‧‧樹脂層(絕緣性樹脂層)
10A‧‧‧含填料膜(作為其一態樣之異向性導電膜)
20‧‧‧端子
A‧‧‧晶格軸
L1、L2、L3、L4、L5‧‧‧距離
P0、P1、P2、P3、P4、P5‧‧‧填料
Px‧‧‧相對於填料之特定之規則配置而填料脫落之部位
θ‧‧‧角度
Claims (15)
- 一種含填料膜,其具有於樹脂層中規則地配置有填料之填料分散層,且俯視下之填料之面積佔有率為25%以下,於填料為球形之情形時,將填料之粒徑D定義為其直徑;於填料之形狀不為球形之情形時,將填料之粒徑D定義為基於含填料膜之平面圖像或剖面圖像之最大長度或模擬球形之形狀之直徑,此時,樹脂層之層厚La與填料之粒徑D之比(La/D)為0.3以上且1.3以下,相對於填料整體,填料彼此以相互不接觸之狀態存在之個數比率為95%以上,填料附近之樹脂層之表面相對於鄰接之填料間之中央部之樹脂層之切平面具有傾斜或起伏,藉由該傾斜,填料周圍之樹脂層之表面相對於上述切平面缺失,藉由該起伏,填料正上方之樹脂層之樹脂量與該填料正上方之樹脂層之表面處於上述切平面時相比變少。
- 如請求項1所述之含填料膜,其中,傾斜之最大深度Le與填料之粒徑D之比(Le/D)未達50%,或起伏之最大深度Lf與填料之粒徑D之比(Lf/D)未達10%。
- 如請求項1或2所述之含填料膜,其中,傾斜或起伏之最大直徑Ld與填料之粒徑D之比(Ld/D)為100%以上,傾斜或起伏中之填料之露出或正上方部分之直徑Lc與填料之粒徑D之比(Lc/D)為100%以下。
- 如請求項1或2所述之含填料膜,其中,樹脂層之層厚La與填料之粒徑D之比(La/D)未達1。
- 如請求項1或2所述之含填料膜,其中,相對於填料整體,填料彼 此以相互不接觸之狀態存在之個數比率為99.5%以上。
- 如請求項1或2所述之含填料膜,其中,填料配置成六方晶格、正方晶格或斜方晶格,於以與任意之填料P0之距離較近之順序選擇3個填料的情形時,該3個填料與填料P0之距離中最大距離與最小距離之比為1.2以下。
- 如請求項1或2所述之含填料膜,其中,於填料分散層積層有最低熔融黏度低於樹脂層之第2樹脂層。
- 如請求項7所述之含填料膜,其中,構成含填料膜之樹脂層整體的最低熔融黏度為200~4000Pa‧s。
- 如請求項7所述之含填料膜,其中,填料沒入第2樹脂層中。
- 如請求項1或2所述之含填料膜,其中,填料為導電粒子,填料分散層之樹脂層為絕緣性樹脂層,且用作異向性導電膜。
- 一種膜貼合體,其係將請求項1至10中任一項所述之含填料膜貼合於物品。
- 一種連接構造體,其係經由請求項1至9中任一項所述之含填料膜將第1物品與第2物品連接。
- 一種連接構造體,其係經由請求項10所述之含填料膜將第1電子零件與第2電子零件進行異向性導電連接。
- 一種連接構造體之製造方法,其係經由請求項1至9中任一項所述之含填料膜將第1物品與第2物品進行壓接。
- 一種連接構造體之製造方法,其係經由請求項10所述之含填料膜將第1電子零件與第2電子零件進行熱壓接,藉此將第1電子零件與第2電子零件進行異向性導電連接。
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