TW202228159A - 異向性導電膜、連接構造體及連接構造體之製造方法 - Google Patents

異向性導電膜、連接構造體及連接構造體之製造方法 Download PDF

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TW202228159A
TW202228159A TW111109675A TW111109675A TW202228159A TW 202228159 A TW202228159 A TW 202228159A TW 111109675 A TW111109675 A TW 111109675A TW 111109675 A TW111109675 A TW 111109675A TW 202228159 A TW202228159 A TW 202228159A
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conductive particles
hardness
resin layer
insulating resin
particles
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TW111109675A
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TWI806494B (zh
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江島康二
平山堅一
尾怜司
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日商迪睿合股份有限公司
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Priority claimed from JP2017160655A external-priority patent/JP7039883B2/ja
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Abstract

本發明之異向性導電膜具有如下構造:於絕緣性樹脂層2中分散有作為導電粒子的20%壓縮彈性率為8000~28000 N/mm 2之高硬度導電粒子1A及20%壓縮彈性率低於該高硬度導電粒子1A之低硬度導電粒子1B。導電粒子整體之個數密度為6000個/mm 2以上,低硬度導電粒子1B之個數密度為導電粒子整體之10%以上。

Description

異向性導電膜、連接構造體及連接構造體之製造方法
本發明係關於一種異向性導電膜。
對於IC晶片等電子零件之安裝,廣泛使用使導電粒子分散於絕緣性樹脂層中而成之異向性導電膜。然而,若於利用異向性導電膜進行連接之電子零件之端子之表面形成氧化皮膜,則連接電阻變高。對此,提出有藉由使用粒徑不同之導電粒子刺破氧化皮膜而實現低電阻化(專利文獻1),或者藉由使用較硬之導電粒子而使導電粒子沒入至配線中,增大連接面積而實現低電阻化(專利文獻2)等。 先前技術文獻 專利文獻
專利文獻1:日本特開2013-182823號公報 專利文獻2:日本特開2012-164454號公報
[發明所欲解決之課題]
若如專利文獻1所記載般使用粒徑不同之導電粒子,則比粒徑大之粒子小之粒子沒入端子中,藉此難以充分地實現低電阻化。另外,若如專利文獻2所記載般使用較硬之導電粒子,則於異向性導電連接時必須於高壓下壓接,有藉由異向性導電連接所獲得之基板與IC晶片之連接構造體產生變形或龜裂之情形。
為了防止變形或龜裂之產生,有減少導電粒子之方法,但若減少導電粒子,則端子之導電粒子之捕捉數減少,反而高電阻化,或引起連接後之導通電阻之上升。
對此,本發明之目的在於,以即便為形成有氧化皮膜之端子亦可連接之方式使用高硬度之導電粒子,且能夠實現低壓條件下之壓接,並且容易確認端子之導電粒子之捕捉,確實地實現低電阻化。 [解決課題之技術手段]
本發明者發現下述情事從而想到本發明,即,若混合硬度不同之導電粒子而使用,則於異向性導電連接時,接壓會集中於高硬度導電粒子,高硬度導電粒子刺破氧化皮膜;低硬度導電粒子利用“高硬度導電粒子於氧化皮膜所形成之龜裂”而有助於導通;因此即便降低高硬度導電粒子之粒子密度,高硬度導電粒子及低硬度導電粒子兩者亦有助於端子之導電,故而可降低導通電阻;另外,可降低高硬度導電粒子之粒子密度,因此於異向性導電連接時無需高壓下之壓接,可消除連接構造體產生變形或龜裂之問題;進而藉由混合使用高硬度導電粒子與低硬度導電粒子,容易觀察到導電粒子之壓痕。
即,本發明提供一種異向性導電膜,其於絕緣性樹脂層中分散有作為導電粒子的20%壓縮彈性率為8000~28000 N/mm 2之高硬度導電粒子及20%壓縮彈性率低於該高硬度導電粒子之低硬度導電粒子,並且導電粒子整體之個數密度為6000個/mm 2以上,低硬度導電粒子之個數密度為導電粒子整體之10%以上。 [發明之效果]
根據本發明之異向性導電膜,即便於電子零件之端子之表面形成氧化皮膜,高硬度導電粒子亦會沒入氧化皮膜中,另外,利用由高硬度導電粒子在氧化皮膜所形成之龜裂,低硬度導電粒子亦有助於端子之導通,因此可降低導通電阻。
另外,藉由在高硬度導電粒子中混合有低硬度導電粒子,與導電粒子僅由高硬度導電粒子所構成之情形相比,可降低異向性導電連接時所需之壓接力。因此,可防止異向性導電連接之連接構造體產生變形或龜裂。
進而,於經異向性導電連接之連接構造體中,可觀察到高硬度導電粒子之壓痕及低硬度導電粒子之壓痕,尤其可清楚地觀察到高硬度導電粒子之壓痕,因此可準確地評價端子的導電粒子之捕捉數。因此,可確實地實現低電阻化。
以下,參照圖式詳細地說明本發明之異向性導電膜。此外,各圖中,相同符號表示相同或同等的構成要素。
<異向性導電膜之整體構成> 圖1A係對本發明之一實施例之異向性導電膜10A說明導電粒子1A、1B之配置的俯視圖。另外,圖1B係異向性導電膜10A之x-x剖視圖。
該異向性導電膜10A係由導電粒子分散層3形成,該導電粒子分散層3係使20%壓縮彈性率為8000~28000 N/mm 2之高硬度導電粒子1A及20%壓縮彈性率低於該高硬度導電粒子1A之低硬度導電粒子1B兩者分散於絕緣性樹脂層2中而成。將高硬度導電粒子1A與低硬度導電粒子1B合併之導電粒子整體的個數密度為6000個/mm 2以上,其中低硬度導電粒子1B之個數密度占導電粒子整體之10%以上。導電粒子整體成為正方格子排列,但關於在各格子點存在高硬度導電粒子1A與低硬度導電粒子1B之何者並無規則性。
<導電粒子> 於導電粒子分散層3中存在高硬度導電粒子1A及低硬度導電粒子1B兩者作為導電粒子。其中,高硬度導電粒子1A之20%壓縮彈性率為8000~28000 N/mm 2
此處,20%壓縮彈性率係測定“使用微小壓縮試驗機(例如Fischer Instruments公司製造,Fischerscope H-100)對導電粒子施加壓縮荷重時的導電粒子之壓縮變量”,使用藉由下述算式所算出之K值: 20%壓縮彈性率(K)(N/mm 2)=(3/2 1 2)・F・S 3 2・R 1 2。 式中, F:導電粒子發生20%壓縮變形時之荷重值(N) S:導電粒子發生20%壓縮變形時之壓縮位移(mm) R:導電粒子之半徑(mm)。
藉由將高硬度導電粒子之20%壓縮彈性率設為8000 N/mm 2以上,即便於電子零件之端子表面形成氧化皮膜,亦可藉由高硬度導電粒子而刺破該氧化皮膜,另外,藉由設為28000 N/mm 2以下,異向性導電連接時所需之壓接力不會變得過高,可使用習知之按壓治具進行異向性導電連接。
關於高硬度導電粒子1A之粒徑,為了抑制導通電阻之上升,且抑制短路之產生,較佳為1 μm以上且30 μm以下,更佳為3 μm以上且未達10 μm。分散於絕緣性樹脂層之前的導電粒子之粒徑可利用一般之粒度分佈測定裝置進行測定,另外,亦可使用粒度分佈測定裝置求出平均粒徑。可為圖像式,亦可為雷射式。作為圖像式測定裝置,作為一例可列舉濕式浮式粒徑/形狀分析裝置FPIA-3000(Malvern公司)。測定平均粒徑D之樣品數(導電粒子個數)較佳為1000個以上。異向性導電膜之導電粒子之粒徑可由SEM等電子顯微鏡觀察求出。於該情形時,較理想為將測定平均粒徑之樣品數設為200以上。
此外,於使用在其表面附著有絕緣性微粒子者作為導電粒子之情形時,本發明中之導電粒子之粒徑係指不含表面之絕緣性微粒子之粒徑。
另一方面,低硬度導電粒子1B之20%壓縮彈性率低於高硬度導電粒子,較佳為高硬度導電粒子之20%壓縮彈性率的10%以上且70%以下。若低硬度導電粒子1B之20%壓縮彈性率過低,則變成難以有助於導通之狀態,反之,若過高,則與高硬度導電粒子之硬度差變得不足,無法獲得本發明之效果。
低硬度導電粒子1B之粒徑較佳為1 μm以上且30 μm以下,只要相對於高硬度導電粒子之粒徑為80%以上,則於實際應用中無問題,較佳為設為同等以上。藉由將低硬度導電粒子之粒徑設為相對於高硬度導電粒子之粒徑為同等以上,則低硬度導電粒子會利用高硬度導電粒子於端子表面所形成之氧化皮膜的龜裂而容易有助於導通。
具有上述硬度及粒徑之高硬度導電粒子1A及低硬度導電粒子1B可自公知之異向性導電膜所使用之導電粒子中適當選擇。例如可列舉: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。金屬被覆樹脂粒子之金屬層之厚度較佳為50 nm~250 nm。另外,導電粒子亦可為表面設置有突起者。於為金屬被覆樹脂粒子之情形時,亦可使用日本特開2016-89153號公報所列舉者。
<導電粒子之個數密度> 低硬度導電粒子1B之個數密度設為導電粒子整體之10%以上,可根據欲連接之端子的種類或連接條件而適當調整。作為一例,較佳為20%以上且80%以下,更佳為30%以上且70%以下。無論低硬度導電粒子相對於導電粒子整體之個數密度過低亦或過高,均難以獲得藉由混合高硬度導電粒子與低硬度導電粒子所產生的本發明之效果。
另外,導電粒子整體之個數密度並無特別限定,作為一例,於導電粒子1A、1B整體之平均粒徑D未達10 μm之情形時,較佳為6000個/mm 2以上且42000個/mm 2以下。於平均粒徑成為10 μm以上之情形時,並不限定於該範圍。作為一例,為20個/mm 2以上且2000個/mm 2以下。
於導電粒子1A、1B整體之平均粒徑D未達10 μm之情形時,若導電粒子整體之個數密度變得過高,則根據下式所算出之導電粒子之面積佔有率亦變得過高。 面積佔有率 =[俯視下之導電粒子之個數密度(個/mm 2)]×[1個導電粒子之俯視面積之平均值(mm 2/個)]×100
面積佔有率為為了將異向性導電膜熱壓接至電子零件而對於按壓治具而言所需之推力的指標。藉由將該面積佔有率設為較佳為35%以下、更佳為0.3~30%之範圍,可將為了將異向性導電膜熱壓接至電子零件而對於按壓治具而言所需之推力抑制為較低。
此外,導電粒子之個數密度可使用藉由金屬顯微鏡等所獲得之觀測圖像而測定。另外,亦可藉由圖像解析軟體(例如WinROOF,三谷商事股份有限公司等)對觀察圖像進行計測而求出。求出導電粒子之個數密度之情形時之測定區域較佳為將一邊為100 μm以上之矩形區域任意地設定多個部位(較佳為5個部位以上,更佳為10個部位以上),將測定區域之合計面積設為2 mm 2以上。各個區域之大小或數量根據個數密度之狀態適當調整即可。另外,1個導電粒子之俯視面積之平均值可藉由計測利用金屬顯微鏡或SEM等電子顯微鏡等所獲得之膜面的觀測圖像而求出。亦可使用圖像解析軟體。觀察方法或計測方法並不限定於上述方法。
此外,作為導電粒子1A、1B整體之粒子間距離Lg係於達成上述導電粒子1A、1B之面積佔有率後,依照特定之個數密度及粒子配置來適當設定。
<導電粒子之配置> 於本發明之異向性導電膜中,含有高硬度導電粒子1A及低硬度導電粒子1B之導電粒子整體之膜於俯視下之配置可為規則配置,亦可為無規配置。作為規則配置之態樣,除圖1A所示之正方格子以外,亦可列舉六角格子、斜方格子、長方格子等格子排列。另外,作為導電粒子整體之粒子配置,亦可使導電粒子1A或1B以特定間隔呈直線狀排列而成之粒子行以特定之間隔並列。於本發明中規則之配置只要為於膜之長邊方向上重複者,則無特別限制。
另一方面,高硬度導電粒子1A及低硬度導電粒子1B之各者亦可規則地配置。例如可如圖2A及圖2B所示之異向性導電膜10B般將低硬度導電粒子1B之個數密度設為導電粒子整體之50%,將高硬度導電粒子1A及低硬度導電粒子1B各者設為正方格子排列。於圖2A中,高硬度導電粒子1A及低硬度導電粒子1B交替地配置,但本發明既包含此種嚴格之配置,亦包含並非如此之配置。
於作為導電粒子整體之粒子排列具有格子軸或排列軸之情形時,該格子軸或排列軸可相對於異向性導電膜10A之長邊方向平行,亦可與異向性導電膜之長邊方向交叉,可根據欲連接之端子寬度、端子間距等而決定。例如於製成微間距用異向性導電膜之情形時,較佳為如圖1A所示,使導電粒子1A、1B之至少一個格子軸A相對於異向性導電膜10A之長邊方向斜行,將利用異向性導電膜10A進行連接之端子20之長邊方向與格子軸A所成之角度θ設為16°~74°。
另外,較佳為於膜之俯視下,導電粒子1A、1B互不接觸地存在,且於膜厚方向上導電粒子1A、1B亦互不重疊地存在。因此,相對於導電粒子整體,導電粒子1A、1B彼此互不接觸地存在之個數比率為95%以上,較佳為98%以上,更佳為99.5%以上。該情況無論對於規則配置亦或無規配置而言均相同。若如下所述使用轉印模使導電粒子1A、1B規則地配置,則可容易地控制導電粒子1A、1B彼此互不接觸地存在之比率,故而較佳。於無規配置之情形時,容易於絕緣性樹脂中混練導電粒子1A、1B而製作異向性導電膜,因此亦可基於與性能或成本之平衡,而選擇利用轉印模之製造方法與利用混練之製造方法任一者。
於各導電粒子1A、1B互不接觸地存在之情形時,較佳為其膜厚方向之位置對齊。例如於高硬度導電粒子1A與低硬度導電粒子1B之粒徑相等之情形時,如圖1B所示,可使導電粒子1A、1B之膜厚方向之埋入量Lb一致。即,可使與絕緣性樹脂層2之一界面之距離一致,因此端子之導電粒子之捕捉性容易穩定。
另外,於高硬度導電粒子1A與低硬度導電粒子1B之粒徑不同之情形時,若藉由導電粒子1A、1B向絕緣性樹脂層2之埋入而使該絕緣性樹脂層2之表面至導電粒子1A、1B之距離相同,則因與上述相同之原因,端子之導電粒子之捕捉性容易穩定。另一方面,於如圖3所示般使導電粒子1A、1B自絕緣性樹脂層2露出之情形時,亦可使高硬度導電粒子1A及低硬度導電粒子1B之各導電粒子自絕緣性樹脂層2露出之頂部之膜厚方向的位置對齊。此外,關於絕緣性樹脂層2之層厚La與導電粒子1A、1B之平均粒徑D之比(La/D)之關係於下文加以說明。
於高硬度導電粒子1A與低硬度導電粒子1B之粒徑相等之情形時及不同之情形時,若導電粒子1A、1B自絕緣性樹脂層2露出,則連接時所施加之壓力均容易傳遞至導電粒子1A、1B。若以金屬被覆樹脂粒子之情形為例進行詳細說明,則與下述之凹陷2b、2c之作用同樣地,當導電粒子1A、1B自絕緣性樹脂層2露出,則於異向性導電連接時利用按壓治具壓入金屬被覆樹脂粒子而產生之絕緣性樹脂層2針對該金屬被覆樹脂粒子變形的阻力降低,因此連接後之壓痕之狀態容易變得均勻。藉此,變得容易確認連接後之狀態。
此處,埋入量Lb係指如下所述之距離,即,埋入有導電粒子1A、1B之絕緣性樹脂層2之表面(絕緣性樹脂層2之正、背面中,露出導電粒子1A、1B之側之表面,或者於導電粒子1A、1B完全埋入至絕緣性樹脂層2之情形時,與導電粒子1A、1B之距離較近之表面)且鄰接之導電粒子間之中央部之切平面2p與導電粒子1A、1B之最深部的距離。於將導電粒子1A、1B之埋入量Lb相對於平均粒徑D之比率設為埋入率(Lb/D)之情形時,埋入率較佳為30%以上且105%以下。
若將埋入率(Lb/D)設為30%以上且未達60%,則粒子自保持導電粒子之相對較高黏度之樹脂露出之比率變高,因此更容易進行低壓構裝。藉由設為60%以上,而容易利用絕緣性樹脂層2將導電粒子1A、1B維持為特定之粒子分散狀態或特定之配置。另外,藉由設為105%以下,可減少異向性導電連接時,以端子間之導電粒子不必要地流動之方式發揮作用之絕緣性樹脂層之樹脂量。此外,導電粒子1A、1B亦可貫通絕緣性樹脂層2,該情形時之埋入率(Lb/D)成為100%。
此外,於本發明中,埋入率(Lb/D)之數值係指異向性導電膜中所含之總導電粒子數之80%以上、較佳為90%以上、更佳為96%以上成為該埋入率(Lb/D)之數值。因此,埋入率為30%以上且105%以下係指異向性導電膜中所含之總導電粒子數之80%以上、較佳為90%以上、更佳為96%以上之埋入率為30%以上且105%以下。藉由如此地使所有導電粒子之埋入率(Lb/D)一致,使按壓之負重均勻地施加至導電粒子,因此端子之導電粒子之捕捉狀態變得良好,可期待導通可靠性。為了進一步提高精度,亦可對200個以上之導電粒子進行計測而求出。
另外,埋入率(Lb/D)之計測可藉由在面視野圖像中進行焦點調整而一次求出某程度之個數。或者,亦可將雷射式判別位移感測器(KEYENCE股份有限公司製造等)用於埋入率(Lb/D)之計測。
<絕緣性樹脂層> (絕緣性樹脂層之黏度) 於本發明之異向性導電膜中,絕緣性樹脂層2之最低熔融黏度並無特別限制,可根據異向性導電膜之使用對象或異向性導電膜之製造方法等而適當決定。例如,只要可形成下述之凹陷2b(圖4)、2c(圖5),則根據異向性導電膜之製造方法,亦可設為1000 Pa・s左右。另一方面,作為異向性導電膜之製造方法,進行使導電粒子以特定之配置保持於絕緣性樹脂層之表面,並將該導電粒子壓入至絕緣性樹脂層之方法,此時,就絕緣性樹脂層能夠實現膜成形之方面而言,較佳為將絕緣性樹脂層之最低熔融黏度設為1100 Pa・s以上。
另外,如下述之異向性導電膜之製造方法所說明,如圖4所示,於壓入至絕緣性樹脂層2之導電粒子1A、1B之露出部分之周圍形成凹陷2b,或如圖5所示,於壓入至絕緣性樹脂層2之導電粒子1A、1B之正上方形成凹陷2c,就該方面而言,較佳為1500 Pa・s以上,更佳為2000 Pa・s以上,進而較佳為3000~15000 Pa・s,進而更佳為3000~10000 Pa・s。作為一例,該最低熔融黏度可使用旋轉式流變儀(TA instruments公司製造),於測定壓力5 g下保持固定,使用直徑8 mm之測定板而求出,更具體而言,可藉由在溫度範圍30~200℃下,設為升溫速度10℃/分鐘、測定頻率10 Hz、相對於上述測定板之荷重變動5 g而求出。
藉由將絕緣性樹脂層2之最低熔融黏度設為1500 Pa・s以上之高黏度,可抑制異向性導電膜對物品之壓接中導電粒子之無用之移動,尤其可防止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。
另外,於藉由將導電粒子1A、1B壓入至絕緣性樹脂層2而形成異向性導電膜10A之導電粒子分散層3之情形時,關於壓入導電粒子1A、1B時之絕緣性樹脂層2,於以導電粒子1A、1B自絕緣性樹脂層2露出之方式將導電粒子1A、1B壓入至絕緣性樹脂層2時,成為如絕緣性樹脂層2發生塑性變形而於導電粒子1A、1B之周圍之絕緣性樹脂層2形成凹陷2b(圖4)般之高黏度之黏性體,或者於以導電粒子1A、1B未自絕緣性樹脂層2露出而掩埋於絕緣性樹脂層2之方式壓入導電粒子1A、1B時,成為如於導電粒子1A、1B之正上方之絕緣性樹脂層2之表面形成凹陷2c(圖5)般之高黏度之黏性體。因此,絕緣性樹脂層2於60℃下之黏度之下限較佳為3000 Pa・s以上,更佳為4000 Pa・s以上,進而較佳為4500 Pa・s以上,上限較佳為20000 Pa・s以下,更佳為15000 Pa・s以下,進而較佳為10000 Pa・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,抽取溫度為60℃之值而求出。
關於將導電粒子1A、1B壓入至絕緣性樹脂層2時之該絕緣性樹脂層2之具體黏度,根據欲形成之凹陷2b、2c之形狀或深度等,下限較佳為3000 Pa・s以上,更佳為4000 Pa・s以上,進而較佳為4500 Pa・s以上,上限較佳為20000 Pa・s以下,更佳為15000 Pa・s以下,進而較佳為10000 Pa・s以下。另外,較佳為於40~80℃、更佳為於50~60℃下獲得此種黏度。
如上所述,藉由在自絕緣性樹脂層2露出之導電粒子1A、1B之周圍形成凹陷2b(圖4),相對於異向性導電膜對物品之壓接時所產生之導電粒子1A、1B之扁平化而自絕緣性樹脂所受到之阻力較無凹陷2b之情形時降低。因此,於異向性導電連接時導電粒子變得容易受到端子夾持,藉此導通性能提高,另外,捕捉性提高。
另外,藉由在未自絕緣性樹脂層2露出而掩埋的導電粒子1A、1B之正上方的絕緣性樹脂層2之表面形成凹陷2c(圖5),與無凹陷2c之情形相比,異向性導電膜對物品之壓接時之壓力容易集中於導電粒子1A、1B。因此,異向性導電連接時導電粒子變得容易受到端子夾持,由此捕捉性提高,導通性能提高。
<代替凹陷之「傾斜」或「起伏」> 如圖4、5所示之異向性導電膜之「凹陷」2b、2c亦可基於「傾斜」或「起伏」之觀點進行說明。以下,一面參照圖式(圖8~15)一面進行說明。
異向性導電膜100A係由導電粒子分散層3構成(圖8)。於導電粒子分散層3中,高硬度導電粒子1A、低硬度導電粒子1B以於絕緣性樹脂層2之單面露出之狀態規則地分散。於膜之俯視下,導電粒子1A、1B互不接觸,且於膜厚方向,導電粒子1A、1B亦互不重疊而規則地分散,構成導電粒子1A、1B之膜厚方向之位置對齊之單層之導電粒子層。
於各個導電粒子1A、1B之周圍之絕緣性樹脂層2之表面2a,相對於鄰接之導電粒子間之中央部之絕緣性樹脂層2之切平面2p形成有傾斜2b。此外,亦可如下所述,於本發明之異向性導電膜中,於埋入至絕緣性樹脂層2之導電粒子1A、1B之正上方之絕緣性樹脂層之表面形成起伏2c(圖11、圖13)。
於本發明中,所謂「傾斜」係指於導電粒子1A、1B之附近絕緣性樹脂層之表面的平坦性受損,樹脂層之一部分相對於上述切平面2p發生缺損而樹脂量減少之狀態。換言之,關於傾斜,導電粒子之周圍的絕緣性樹脂層之表面相對於切平面發生缺損。另一方面,所謂「起伏」係指藉由在導電粒子之正上方的絕緣性樹脂層之表面具有波動,存在如波動般具有高低差之部分,而使樹脂減少之狀態。換言之,導電粒子正上方之絕緣性樹脂層之樹脂量較導電粒子正上方之絕緣性樹脂層之表面位於切平面時變少。該等可將相當於導電粒子之正上方之部位與導電粒子間之平坦之表面部分(圖11、圖13之2f)進行對比而辨識。此外,亦有起伏之起始點作為傾斜而存在之情形。
如上所述,藉由在自絕緣性樹脂層2露出之導電粒子1A、1B之周圍形成傾斜2b(圖8),相對於異向性導電連接時導電粒子1A、1B夾持於端子間時所產生之導電粒子1A、1B之扁平化而自絕緣性樹脂層所受到之阻力較無傾斜2b之情形時降低,因此變得容易於端子夾持導電粒子,藉此導通性能提高,另外,捕捉性提高。該傾斜較佳為沿著導電粒子之外形。其原因在於,除了更容易表現出連接之效果以外,亦變得容易辨識導電粒子,藉此容易進行製造異向性導電膜時之檢查等。另外,該傾斜及起伏有因“對絕緣性樹脂層進行熱壓等”而導致其一部分消失之情形,本發明包括該情形。於該情形時,導電粒子有於絕緣性樹脂層之表面以1點露出之情形。此外,關於異向性導電膜,在所連接之電子零件多種多樣並且根據該等進行調整之情況下,因此較理想為設計自由度較高以便滿足各種要件,故而無論使傾斜或起伏減少或局部地消失,均可使用。
另外,藉由在未自絕緣性樹脂層2露出而被掩埋之導電粒子1A、1B的正上方之絕緣性樹脂層2之表面形成起伏2c(圖11、圖13),與傾斜之情形同樣地,於異向性導電連接時來自端子之按壓力容易施加至導電粒子。另外,藉由具有起伏,導電粒子之正上方之樹脂量較樹脂平坦地堆積之情形時減少,因此容易產生連接時之導電粒子正上方之樹脂之排除,端子與導電粒子容易接觸,因此端子之導電粒子之捕捉性提高,導通可靠性提高。
(絕緣性樹脂層之厚度方向上之導電粒子之位置) 考慮到「傾斜」或「起伏」之觀點之情形時之絕緣性樹脂層2之厚度方向上之導電粒子1A、1B之位置係與上述同樣地,導電粒子1A、1B可自絕緣性樹脂層2露出,亦可不露出而埋入至絕緣性樹脂層2內,自鄰接之導電粒子間之中央部之切平面2p起至導電粒子之最深部為止的距離(以下稱為埋入量)Lb與導電粒子之平均粒徑D之比(Lb/D)(以下稱為埋入率)較佳為30%以上且105%以下。
藉由將埋入率(Lb/D)設為30%以上,可利用絕緣性樹脂層2將導電粒子1A、1B維持為特定之粒子分散狀態或特定之配置,另外,藉由設為105%以下,可減少異向性導電連接時以端子間之導電粒子不必要地流動之方式發揮作用之絕緣性樹脂層之樹脂量。
此外,埋入率(Lb/D)之數值係指異向性導電膜中所含之總導電粒子數之80%以上、較佳為90%以上、更佳為96%以上成為該埋入率(Lb/D)之數值。因此,所謂埋入率30%以上且105%以下係指異向性導電膜中所含之總導電粒子數之80%以上、較佳為90%以上、更佳為96%以上之埋入率為30%以上且105%以下。藉由如此使所有導電粒子之埋入率(Lb/D)一致,使按壓之負重均勻地施加至導電粒子,因此端子之導電粒子之捕捉狀態變得良好,導通可靠性提高。
埋入率(Lb/D)可藉由下述方法求出:自異向性導電膜任意地抽出10處以上之面積30 mm 2以上之區域,利用SEM圖像對該膜剖面之一部分進行觀察,計測合計50個以上之導電粒子。為了進一步提高精度,亦可計測200個以上之導電粒子而求出。
另外,埋入率(Lb/D)之計測可藉由在面視野圖像中進行焦點調整,一次求出某程度之個數。或者亦可將雷射式判別位移感測器(KEYENCE股份有限公司製造等)用於埋入率(Lb/D)之計測。
(埋入率30%以上且未達60%之態樣) 作為埋入率(Lb/D)30%以上且未達60%之導電粒子1A、1B之更具體之埋入態樣,首先,可列舉如圖8所示之異向性導電膜100A般,導電粒子1A、1B以自絕緣性樹脂層2露出之方式埋入率30%以上且未達60%地被埋入之態樣。該異向性導電膜100A具有傾斜2b,該傾斜2b係絕緣性樹脂層2之表面中與自該絕緣性樹脂層2露出之導電粒子1A、1B相接之部分及其附近相對於鄰接之導電粒子間之中央部之絕緣性樹脂層之表面2a之切平面2p而成為大致沿著導電粒子之外形之稜線者。
此種傾斜2b或下述之起伏2c於藉由將導電粒子1A、1B壓入至絕緣性樹脂層2而製造異向性導電膜100A之情形時,可藉由在40~80℃下以3000~20000 Pa・s、更佳為4500~15000 Pa・s之黏度進行導電粒子1A、1B之壓入而形成。
(埋入率60%以上且未達100%之態樣) 作為埋入率(Lb/D)60%以上且未達100%之導電粒子1A、1B之更具體之埋入態樣,首先可列舉如圖8所示之異向性導電膜100A般導電粒子1A、1B以自絕緣性樹脂層2露出之方式以60%以上且未達100%之埋入率被埋入之態樣。該異向性導電膜100A具有傾斜2b,該傾斜2b係絕緣性樹脂層2之表面中與自該絕緣性樹脂層2露出之導電粒子1A、1B相接之部分及其附近相對於鄰接之導電粒子間之中央部之絕緣性樹脂層之表面2a之切平面2p而成為大致沿著導電粒子之外形之稜線者。
關於此種傾斜2b或下述之起伏2c,於藉由將導電粒子1A、1B壓入至絕緣性樹脂層2而製造異向性導電膜100A之情形時,壓入導電粒子1A、1B時之黏度之下限較佳為3000 Pa・s以上,更佳為4000 Pa・s以上,進而較佳為4500 Pa・s以上,上限較佳為20000 Pa・s以下,更佳為15000 Pa・s以下,進而較佳為10000 Pa・s以下。另外,較佳為於40~80℃、更佳為於50~60℃下獲得此種黏度。此外,可為傾斜2b或起伏2c之一部分因對絕緣性樹脂層進行熱壓等而消失,亦可為傾斜2b變化為起伏2c,另外,亦可為具有起伏2c之導電粒子以其頂部之1點露出於絕緣性樹脂層2。
(埋入率100%之態樣) 其次,作為本發明之異向性導電膜中埋入率(Lb/D)100%之態樣,可列舉:如圖9所示之異向性導電膜100B般,於導電粒子1A、1B之周圍具有“成為大致沿著與圖8所示之異向性導電膜100A相同之導電粒子之外形之稜線的傾斜2b”,自絕緣性樹脂層2露出之導電粒子1A、1B之露出直徑Lc小於導電粒子之平均粒徑D者;如圖10A所示之異向性導電膜100C般,導電粒子1A、1B之露出部分之周圍之傾斜2b陡峭地出現於導電粒子1A、1B之附近,導電粒子1A、1B之露出直徑Lc與導電粒子之平均粒徑D大致相等者;如圖11所示之異向性導電膜100D般,於絕緣性樹脂層2之表面具有較淺之起伏2c,導電粒子1A、1B以其頂部1a之1點自絕緣性樹脂層2露出者。
此外,亦可與導電粒子之露出部分之周圍之絕緣性樹脂層2之傾斜2b、或導電粒子之正上方之絕緣性樹脂層之起伏2c鄰接地形成微小之突出部分2q。將該一例示於圖10B。
該等異向性導電膜100B(圖9)、100C(圖10A)、100D(圖11)由於埋入率為100%,故而導電粒子1A、1B之頂部1a與絕緣性樹脂層2之表面2a對齊為同一面。若導電粒子1A、1B之頂部1a與絕緣性樹脂層2之表面2a對齊為同一面,則具有如下效果:與如圖8所示般導電粒子1A、1B自絕緣性樹脂層2突出之情形相比,於異向性導電連接時,於各個導電粒子之周邊,膜厚方向之樹脂量不易變得不均勻,可減少因樹脂流動所引起的導電粒子之移動。此外,即便埋入率嚴格上並非100%,若埋入至絕緣性樹脂層2之導電粒子1A、1B之頂部1a與絕緣性樹脂層2之表面2a對齊至成為同一面之程度,則亦可獲得該效果。換言之,於埋入率(Lb/D)大致為80~105%、尤其90~100%之情形時,可認為埋入至絕緣性樹脂層2之導電粒子1A、1B之頂部1a與絕緣性樹脂層2之表面2a為同一面,可減少因樹脂流動所引起的導電粒子之移動。
於該等異向性導電膜100B(圖9)、100C(圖10A)、100D(圖11)中,100D由於導電粒子1A、1B之周圍之樹脂量不易變得不均勻,故而可消除因樹脂流動所引起的導電粒子之移動,另外,雖然為頂部1a之1點,但導電粒子1A、1B自絕緣性樹脂層2露出,因此可期待如下效果:端子之導電粒子1A、1B之捕捉性亦良好,亦不易產生導電粒子之略微之移動。因此,該態樣尤其對於微間距或凸塊間空間狹小之情形有效。
此外,傾斜2b、起伏2c之形狀或深度不同之異向性導電膜100B(圖9)、100C(圖10A)、100D(圖11)可藉由如下所述變更壓入導電粒子1A、1B時之絕緣性樹脂層2之黏度等而製造。
(埋入率超過100%之態樣) 於本發明之異向性導電膜中,於埋入率超過100%之情形時,可列舉:如圖12所示之異向性導電膜100E般導電粒子1A、1B露出,且具有該露出部分之周圍之絕緣性樹脂層2的相對於切平面2p之傾斜2b或導電粒子1A、1B之正上方之絕緣性樹脂層2的相對於切平面2p之起伏2c(圖13)。
此外,於導電粒子1A、1B之露出部分之周圍之絕緣性樹脂層2具有傾斜2b的異向性導電膜100E(圖12)與於導電粒子1A、1B之正上方之絕緣性樹脂層2具有起伏2c的異向性導電膜100F(圖13)可藉由變更製造其等時壓入導電粒子1A、1B時之絕緣性樹脂層2之黏度等而製造。
此外,若將圖12所示之異向性導電膜100E用於異向性導電連接,則由於導電粒子1A、1B被端子直接按壓,故而端子之導電粒子之捕捉性提高。另外,若將圖13所示之異向性導電膜100F用於異向性導電連接,則導電粒子1A、1B不直接按壓端子,而是隔著絕緣性樹脂層2進行按壓,但按壓方向上所存在之樹脂量與圖15之狀態(即,導電粒子1A、1B超過100%之埋入率地被埋入,導電粒子1A、1B未自絕緣性樹脂層2露出,且絕緣性樹脂層2之表面平坦之狀態)相比變少,因此按壓力容易施加至導電粒子,且可防止異向性導電連接時端子間之導電粒子1A、1B因樹脂流動而不必要地移動。
就容易獲得上述導電粒子之露出部分之周圍之絕緣性樹脂層2之傾斜2b(圖8、圖9、圖10A、圖12)、或導電粒子之正上方之絕緣性樹脂層之起伏2c(圖11、圖13)的效果之方面而言,傾斜2b之最大深度Le與導電粒子1A、1B之平均粒徑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與導電粒子1A、1B之平均粒徑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與導電粒子1A、1B之平均粒徑D之比(Lf/D)大於0,較佳為未達10%,更佳為5%以下。
此外,傾斜2b或起伏2c之導電粒子1A、1B之露出(正上方)部分之直徑Lc可設為導電粒子1A、1B之平均粒徑D以下,較佳為平均粒徑D之10~90%。可以導電粒子1A、1B之頂部之1點露出,亦可將導電粒子1A、1B完全掩埋於絕緣性樹脂層2內,使直徑Lc成為零。
此外,如圖14所示,於埋入率(Lb/D)未達60%之異向性導電膜100G中,導電粒子1A、1B容易於絕緣性樹脂層2上轉動,因此就提高異向性導電連接時之捕捉率之方面而言,較佳為將埋入率(Lb/D)設為60%以上。
另外,於埋入率超過100%之態樣(Lb/D)中,當如圖15所示之比較例之異向性導電膜100X般絕緣性樹脂層2之表面平坦之情形時,介置於導電粒子1A、1B與端子之間之樹脂量變得過多。另外,由於導電粒子1A、1B不直接接觸端子地按壓端子,而是隔著絕緣性樹脂層按壓端子,故而由此導電粒子亦容易因樹脂流動而流動。
於此種本發明中,絕緣性樹脂層2之表面存在傾斜2b、起伏2c之情況可藉由利用掃描式電子顯微鏡對異向性導電膜之剖面進行觀察而確認,亦可於面視野觀察中進行確認。亦可利用光學顯微鏡、金屬顯微鏡觀察傾斜2b、起伏2c。另外,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。即便於如上所述般因熱壓而使傾斜或起伏減少後亦相同。其原因在於有時會殘留痕跡。
(絕緣性樹脂層之組成) 絕緣性樹脂層2較佳為由硬化性樹脂組成物形成,例如可由含有熱聚合性化合物及熱聚合起始劑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。
於將熱聚合起始劑與光聚合起始劑併用之情形時,可使用既作為熱聚合性化合物發揮功能亦作為光聚合性化合物發揮功能者,亦可除熱聚合性化合物以外,亦含有光聚合性化合物。較佳為除熱聚合性化合物以外,亦含有光聚合性化合物。例如使用熱陽離子系聚合起始劑作為熱聚合起始劑,使用環氧化合物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,亦可含有會對波長不同之光發生反應之多種。藉此,可將製造異向性導電膜時之構成絕緣性樹脂層之樹脂的光硬化與於異向性導電連接時用以接著電子零件彼此之樹脂的光硬化中所使用之波長分開使用。
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光硬化。藉由該光硬化,可保持絕緣性樹脂層2中之導電粒子1A、1B之配置或使其固定化,期待短路之抑制與捕捉之提高。另外,亦可藉由該光硬化而適當調整異向性導電膜之製造步驟中之絕緣性樹脂層之黏度。尤其是,該光硬化較佳為於絕緣性樹脂層2之層厚La與導電粒子1A、1B之平均粒徑D之比(La/D)未達0.6之情形時進行。其原因在於,於絕緣性樹脂層2之層厚相對於導電粒子直徑而較薄之情形時,亦於絕緣性樹脂層2中更確實地進行導電粒子之配置之保持或固定化,並且進行絕緣性樹脂層2之黏度調整,於使用異向性導電膜之電子零件彼此之連接中抑制良率之降低。
絕緣性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,更佳為未達2質量%。其原因在於,若光聚合性化合物過多,則連接時之壓入所施加之推力增加。
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。另外,只要無特別阻礙,則亦可將多種聚合性化合物併用。作為併用例,可列舉陽離子聚合性化合物與自由基聚合性化合物之併用等。
此處,作為(甲基)丙烯酸酯化合物,可使用先前公知之熱聚合型(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會產生成為氣泡之原因之氮氣之有機過氧化物。
關於熱自由基聚合起始劑之使用量,若過少則變得硬化不良,若過多則導致製品壽命降低,因此相對於(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,可將該等之2種以上併用。另外,亦可除氧環丁烷化合物以外併用環氧化合物。
作為熱陽離子聚合起始劑,可採用公知者作為環氧化合物之熱陽離子聚合起始劑,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於溫度顯示出良好之潛伏性之芳香族鋶鹽。
關於熱陽離子聚合起始劑之使用量,若過少則有變得硬化不良之傾向,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。
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,可將該等之2種以上併用。於該等中,就成膜性、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。另外,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。
於熱聚合性組成物中,為了調整熔融黏度,除上述導電粒子1A、1B以外,亦可含有絕緣性填料。作為該絕緣性填料,可列舉二氧化矽粉或氧化鋁粉等。較佳為絕緣性填料粒徑20~1000 nm之微小之填料,另外,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。
於本發明之異向性導電膜中,除上述絕緣性填料以外,亦可含有填充劑、軟化劑、促進劑、防老化劑、著色劑(顏料、染料)、有機溶劑、離子捕捉劑等。
(絕緣性樹脂層之層厚) 於本發明之異向性導電膜中,就下述原因而言,可將絕緣性樹脂層2之層厚La與導電粒子1A、1B之平均粒徑D之比(La/D)之下限設為0.3以上,可將上限設為10以下。因此,該比較佳為0.3~10,更佳為0.6~8,進而較佳為0.6~6。此處,導電粒子1A、1B之平均粒徑D係指其平均粒徑。若絕緣性樹脂層2之層厚La過大,則於異向性導電連接時導電粒子1A、1B容易因樹脂流動而發生位置偏移,端子之導電粒子1A、1B之捕捉性降低。若該比(La/D)超過10,則該傾向顯著,因此更佳為8以下,進而較佳為6以下。反之,若絕緣性樹脂層2之層厚La過小而該比(La/D)未達0.3,則難以利用絕緣性樹脂層2將導電粒子1A、1B維持為特定之粒子分散狀態或特定之配置,因此比(La/D)較佳為0.3以上,就利用絕緣性樹脂層2確實地維持特定之粒子分散狀態或特定之配置之方面而言,更佳為0.6以上。另外,於欲連接之端子為高密度COG之情形時,絕緣性樹脂層2之層厚La與導電粒子1A、1B之平均粒徑D之比(La/D)較佳為0.8~2。
另一方面,於平均粒徑D為10 μm以上之情形時,關於La/D之上限設為3.5以下,較佳設為2.5以下,更佳設為2以下,關於下限為0.8以上,較佳為1以上,更佳為大於1.3。
不論平均粒徑D之大小如何,若絕緣性樹脂層2之層厚La過大而該比變得過大,則於異向性導電連接時導電粒子1A、1B難以壓抵於端子,並且導電粒子容易因樹脂流動而流動。因此,導電粒子容易發生位置偏移,端子之導電粒子之捕捉性降低。另外,為了將導電粒子壓抵於端子而對按壓治具所需之推力亦增大,阻礙低壓構裝。反之,若絕緣性樹脂層2之層厚La過小而該比變得過小,則難以利用絕緣性樹脂層2將導電粒子1A、1B維持為特定之配置。
<變形態樣> 作為本發明之異向性導電膜,可於導電粒子分散層3上積層最低熔融黏度低於構成絕緣性樹脂層2之樹脂的第2絕緣性樹脂層4(圖6、圖7)。該第2絕緣性樹脂層4可於異向性導電連接時填充由電子零件之凸塊等端子所形成之空間,而提高對向之電子零件彼此之接著性。即,為了能夠實現使用異向性導電膜之電子零件之低壓構裝,且抑制異向性導電連接時之絕緣性樹脂層2之樹脂流動而提高導電粒子1A、1B之粒子捕捉性,較理想為提高絕緣性樹脂層2之黏度,並且於導電粒子1A、1B不發生位置偏移之範圍內減薄絕緣性樹脂層2之厚度,但若絕緣性樹脂層2之厚度變得過薄,則導致使對向之電子零件彼此接著之樹脂量之不足,因此有接著性降低之虞。對此,藉由在異向性導電連接時設置黏度低於絕緣性樹脂層2之第2絕緣性樹脂層4,亦可提高電子零件彼此之接著性,由於第2絕緣性樹脂層4之流動性高於絕緣性樹脂層2,故而可不易阻礙利用端子之導電粒子1A、1B之夾持或壓入。
於導電粒子分散層3上積層第2絕緣性樹脂層4之情形時,無論第2絕緣性樹脂層4是否位於凹陷2b之形成面上,均較佳為將第2絕緣性樹脂層4貼於利用工具進行加壓之電子零件(將絕緣性樹脂層2貼於載置於載台之電子零件)。藉此,可避免導電粒子的無用之移動,可提高捕捉性。
絕緣性樹脂層2與第2絕緣性樹脂層4之最低熔融黏度比越具有差異,由電子零件之電極或凸塊所形成之空間越容易被第2絕緣性樹脂層4填充,越可提高電子零件彼此之接著性。另外,越具有該差異,存在於導電粒子分散層3中之絕緣性樹脂層2之移動量變得相對越少,端子間之導電粒子1A、1B越不易因樹脂流動而流動,藉此端子之導電粒子1A、1B之捕捉性提高,故而較佳。於實際應用中,絕緣性樹脂層2與第2絕緣性樹脂層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,則於將長條之異向性導電膜製成捲裝體之情形時,有樹脂之溢出或黏連之虞,因此於實際應用中較佳為15以下。更具體而言,第2絕緣性樹脂層4的較佳之最低熔融黏度滿足上述比,且為3000 Pa・s以下,較佳為2000 Pa・s以下,尤其為100~2000 Pa・s。
此外,第2絕緣性樹脂層4可藉由在與絕緣性樹脂層2相同之樹脂組成物中調整黏度而形成。
另外,第2絕緣性樹脂層4之層厚較佳為4~20 μm。或者,相對於導電粒子1A、1B之平均粒徑D,較佳為1~8倍。
另外,將絕緣性樹脂層2與第2絕緣性樹脂層4合併而成之異向性導電膜10F、10G整體之最低熔融黏度於實際應用中為8000 Pa・s以下,較佳為200~7000 Pa・s,更佳為200~4000 Pa・s。
作為第2絕緣性樹脂層4之具體積層態樣,例如於如圖6所示之異向性導電膜10F般導電粒子1A、1B自絕緣性樹脂層2之單面突出之情形時,可於該突出之面積層第2絕緣性樹脂層4,使導電粒子1A、1B沒入至第2絕緣性樹脂層4中。於導電粒子1A、1B之埋入率(Lb/D)為0.95以下之情形時,較佳為如此積層第2絕緣性樹脂層4,於為0.9以下之情形時更佳。另外,於平均粒徑D未達10 μm之情形時,有較理想為如此積層之情形。
另一方面,亦可如圖7所示之異向性導電膜10G般於“與埋入有導電粒子1A、1B之絕緣性樹脂層2之面為相反側之面”積層第2絕緣性樹脂層4。
(第3絕緣性樹脂層) 亦可於隔著絕緣性樹脂層2而與第2絕緣性樹脂層4相反之側設置第3絕緣性樹脂層。可使第3絕緣性樹脂層作為黏性層發揮功能。亦可與第2絕緣性樹脂層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絕緣性樹脂層之樹脂組成、黏度及厚度可與第2絕緣性樹脂層4相同,亦可不同。將絕緣性樹脂層2、第2絕緣性樹脂層4及第3絕緣性樹脂層合併而成之異向性導電膜之最低熔融黏度並無特別限制,於實際應用中為8000 Pa・s以下,較佳為200~7000 Pa・s,更佳為200~4000 Pa・s。
<異向性導電膜之製造方法> 本發明之異向性導電膜例如可藉由如下方式製造,即,使導電粒子1A、1B以分別獨立之特定規則之配置或無規之分散狀態保持於絕緣性樹脂層2之表面,並利用平板或滾筒將該導電粒子1A、1B壓入至絕緣性樹脂層2。
此處,絕緣性樹脂層2中之導電粒子1A、1B之埋入量Lb可藉由壓入導電粒子1A、1B時之按壓力、溫度等進行調整,另外,凹陷2b、2c之有無、形狀及深度可藉由壓入時之絕緣性樹脂層2之黏度、壓入速度、溫度等進行調整。
另外,作為使導電粒子1A、1B保持於絕緣性樹脂層2之方法,並無特別限定,於將導電粒子1A、1B設為規則之配置之情形時,例如使用轉印模使以特定之比率混合之導電粒子1A、1B保持於絕緣性樹脂層2中。作為轉印模,例如可使用如下者,即,對於矽、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之轉印模材料藉由光微影法等公知之開口形成方法而形成有開口者。此外,轉印模可採用板狀、輥狀等形狀。
作為獲得絕緣性樹脂層2之導電粒子1A、1B於無規之分散狀態下各自不獨立之方法,亦可藉由將導電粒子1A、1B以特定之比率混練(混合)至形成絕緣性樹脂層2之樹脂組成物中,並將其塗佈於剝離膜上,而獲得導電粒子1A、1B位於無規之位置之絕緣性樹脂層。
為了使用異向性導電膜經濟地進行電子零件之連接,異向性導電膜較佳為某程度之長條。因此,異向性導電膜之長度較佳製造為5 m以上,更佳製造為10 m以上,進而較佳製造為25 m以上。另一方面,若使異向性導電膜變得過長,則無法使用習知之連接裝置,該習知之連接裝置為利用異向性導電膜進行電子零件之製造之情形時使用者,操作性亦較差。因此,異向性導電膜之長度較佳為製造為5000 m以下,更佳為製造為1000 m以下,進而較佳為製造為500 m以下。就操作性優異之方面而言,較佳為將異向性導電膜之此種長條體製成捲成捲芯之捲裝體。
<異向性導電膜之使用方法> 本發明之異向性導電膜可於將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電子零件異向性導電連接時較佳地使用,尤其作為塑膠基板,可列舉於藉由在高壓下進行壓接而容易產生變形或龜裂之PET基材形成有端子者。此外,該PET基材亦可為經由接著劑積層有聚醯亞胺基材者。作為一例,該等之總厚可設為0.15 mm以下。亦可使用本發明之異向性導電膜將IC晶片或晶圓堆疊而多層化。此外,利用本發明之異向性導電膜進行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。本發明亦包括使用本發明之異向性導電膜將電子零件彼此異向性導電連接之連接構造體。另外,亦包括連接構造體之製造方法,其具有於第1電子零件與第2電子零件之間配置本發明之異向性導電膜而將該等進行異向性導電連接之步驟。
作為使用異向性導電膜之電子零件之連接方法,於異向性導電膜之樹脂層由導電粒子分散層3之單層構成之情形時,可藉由如下方式製造:對於各種基板等第2電子零件,自異向性導電膜之表面埋入有導電粒子1A、1B之側暫時貼附並暫時壓接,於經暫時壓接之異向性導電膜之表面未埋入導電粒子1A、1B之側,將IC晶片等第1電子零件對準並進行熱壓接。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,且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,亦可為將光與熱併用之壓接方法。如此,可將導電粒子的意料外之移動抑制為最小限度。另外,亦可將未埋入導電粒子之側暫時貼附於第2電子零件而使用。此外,亦可將異向性導電膜暫時貼附於第1電子零件而非第2電子零件。
另外,於異向性導電膜由導電粒子分散層3與第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暫時貼附於各種基板等第2電子零件並暫時壓接,將IC晶片等第1電子零件對準於“經暫時壓接之異向性導電膜之第2絕緣性樹脂層4側”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側暫時貼附於第1電子零件。另外,亦可將導電粒子分散層3側暫時貼附於第1電子零件而使用。 實施例
以下,基於實施例對本發明進行具體說明。
實施例1~4、比較例1、2 (1)異向性導電膜之製造 以表1所示之組成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3000 Pa・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。
另一方面,準備於樹脂核心粒子之表面具有約70個氧化鋁粒子(平均粒徑150 nm),且於最外層具有Ni層(厚度100 nm)的高硬度導電粒子(20%壓縮彈性率22000 N/mm 2,平均粒徑3 μm,積水化學工業股份有限公司製造)(藉由日本特開2006-269296號公報所記載之方法所製造者),另外,準備構造與高硬度導電粒子相同之低硬度導電粒子(20%壓縮彈性率6000 N/mm 2,平均粒徑3 μm,積水化學工業股份有限公司製造)。此外,於以下之實施例1~24及比較例1~10中,亦準備同樣地製造之積水化學工業股份有限公司製造之導電粒子。
將高硬度導電粒子與低硬度導電粒子以其等之個數密度成為表2所示之比率之方式混合至絕緣性樹脂層(高黏度樹脂層)形成用樹脂組成物中,並利用棒式塗佈機將其塗佈於膜厚度50 μm之PET膜上,於80℃之烘箱中乾燥5分鐘,而形成於PET膜上無規地分散有高硬度導電粒子及低硬度導電粒子的導電粒子分散層。該導電粒子分散層之絕緣性樹脂層之厚度為6 μm。另外,藉由利用棒式塗佈機將第2絕緣性樹脂層形成用樹脂組成物塗佈於膜厚度50 μm之PET膜上,並於80℃之烘箱中乾燥5分鐘,而於PET膜上形成成為厚度12 μm之第2絕緣性樹脂層之樹脂層。將該樹脂層積層於上述導電粒子分散層,製成異向性導電膜。
[表1]
   組成 質量份
絕緣性樹脂層(高黏度樹脂) 苯氧基樹脂(新日鐵住金化學股份有限公司YP-50) 40
二氧化矽填料(日本Aerosil股份有限公司,Aerosil R805) 25
液狀環氧樹脂(三菱化學股份有限公司,jER828) 30
矽烷偶合劑(信越化學工業股份有限公司,KBM-403) 2
熱陽離子聚合起始劑(三新化學工業股份有限公司,SI-60L) 3
第2絕緣性樹脂層 苯氧基樹脂(新日鐵住金化學股份有限公司YP-50) 40
二氧化矽填料(日本Aerosil股份有限公司,Aerosil R805) 5
液狀環氧樹脂(三菱化學股份有限公司,jER828) 50
矽烷偶合劑(信越化學工業股份有限公司,KBM-403) 2
熱陽離子聚合起始劑(三新化學工業股份有限公司,SI-60L) 3
(2)異向性導電膜之評價 將(1)中所製造之實施例及比較例之異向性導電膜裁剪為對於連接而言充分之面積,使用所獲得者製作電子零件之連接構造體,以如下方式評價(a)捕捉效率、(b)壓痕、(c)粒子壓扁率、(d)電阻值。將結果示於表2。
(a)捕捉效率 針對以下所示之評價用IC及端子圖案與該評價用IC對應之玻璃基板(Ti/Al配線),隔著異向性導電膜而於200℃下以表2所記載之加壓力進行5秒之加熱加壓,而獲得評價用連接構造體。
評價用IC: 外形 1.8×20.0 mm 厚度 0.5 mm 凸塊規格 尺寸30×85 μm,凸塊間距離20 μm,凸塊之表面材質Au
針對加熱加壓後之100個端子對,計測高硬度導電粒子及低硬度導電粒子之捕捉數,並求出其平均值。另外,預先根據[100個端子之端子面積]×[導電粒子之個數密度]算出加熱加壓前存在於端子上之高硬度導電粒子及低硬度導電粒子之理論值,求出所計測之導電粒子之捕捉數相對於理論值之比率,根據如下基準進行評價。於實際應用中,較佳為B評價以上。
捕捉效率評價基準 A:30%以上 B:15%以上且未達30% C:未達15%
(b)壓痕 利用金屬顯微鏡觀察(a)中所製造之評價用連接構造體之高硬度導電粒子及低硬度導電粒子之壓痕,針對加熱加壓後之5個端子對,使用圖像解析軟體WinROOF(三谷商事股份有限公司)對高硬度導電粒子及低硬度導電粒子之壓痕(捕捉)數進行計測,求出其平均值。另外,預先根據[5個端子之端子面積]×[導電粒子之個數密度]算出加熱加壓前存在於端子上之高硬度導電粒子及低硬度導電粒子之理論值,求出所計測之導電粒子之壓痕(捕捉)數相對於理論值之比率,根據如下基準進行評價。此外,關於所確認到之壓痕,於無規地配置有導電粒子之分散型異向性導電膜中,5個凸塊之壓痕之合計為100個左右,於下述之導電粒子呈正方格子排列之整齊排列型異向性導電膜中,5個凸塊之壓痕之合計為200個左右。
壓痕評價基準 OK:理論值之50%以上能夠辨識為壓痕之情形 NG:未達理論值之50%能夠辨識為壓痕之情形
(c)粒子壓扁率 關於(a)中所製造之評價用連接構造體之剛製造後(初期)、及將(a)中所製造之評價用連接構造體於溫度85℃、濕度85%RH之恆溫槽中放置500小時後(500 h)之各者,計測對向之端子間之距離作為壓接後之粒徑,求出其平均粒徑。另一方面,亦預先求出壓接前之平均粒徑,根據下式算出粒子壓扁率,根據如下基準進行評價。於實際應用中,較佳為B評價以上。
粒子壓扁率(%) =([壓接前之平均粒徑]-[壓接後之平均粒徑])×100/[壓接前之平均粒徑]
初期及500 h時之粒子壓扁率評價基準 A:10%以上 B:5%以上且未達10% C:未達5%
(d)電阻值 關於(a)中所製造之評價用連接構造體之剛製造後(初期)、及將(a)中所製造之評價用連接構造體於溫度85℃、濕度85%RH之恆溫槽中放置500小時後(500 h)之各者,藉由四端子法測定導通電阻,根據如下基準進行評價。電阻值於實際應用中較佳為B評價以上。
初期時之電阻值評價基準 A:未達3 Ω B:3 Ω以上且未達5 Ω C:5 Ω以上且未達10 Ω D:10 Ω以上
500 h時之電阻值評價基準 A:未達3 Ω B:3 Ω以上且未達5 Ω C:5 Ω以上且未達10 Ω D:10 Ω以上
實施例5~8、比較例3、4 準備與實施例1相同之導電粒子。其中,藉由調整樹脂核心粒子之20%壓縮彈性率,而準備20%壓縮彈性率為14000 N/mm 2之導電粒子(平均粒徑3 μm)作為高硬度導電粒子,準備20%壓縮彈性率為6000 N/mm 2之導電粒子(平均粒徑3 μm)作為低硬度導電粒子。
將該高硬度導電粒子與低硬度導電粒子以成為表3所示之比率之方式混合至絕緣性樹脂層(高黏度樹脂層)形成用樹脂組成物中,除此以外,以與實施例1相同之方式,製造無規地分散有高硬度導電粒子與低硬度導電粒子之異向性導電膜。
另外,以與實施例1相同之方式評價(a)捕捉效率、(b)壓痕、(c)粒子壓扁率、(d)電阻值。將結果示於表3。
實施例9~12、比較例5 準備與實施例1相同之導電粒子。其中,藉由調整樹脂核心粒子之20%壓縮彈性率,而準備20%壓縮彈性率為9000 N/mm 2之導電粒子(平均粒徑3 μm)作為高硬度導電粒子,準備20%壓縮彈性率為6000 N/mm 2之導電粒子(平均粒徑3 μm)作為低硬度導電粒子。
將該高硬度導電粒子與低硬度導電粒子以成為表4所示之比率之方式混合至絕緣性樹脂層(高黏度樹脂層)形成用樹脂組成物中,除此以外,以與實施例1相同之方式,製造無規地分散有高硬度導電粒子與低硬度導電粒子之異向性導電膜。
另外,以與實施例1相同之方式評價(a)捕捉效率、(b)壓痕、(c)粒子壓扁率、(d)電阻值。將結果示於表4。
實施例13~16、比較例6、7 以表1所示之摻合組成,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,利用棒式塗佈機將其塗佈於膜厚度50 μm之PET膜上,於80℃之烘箱中乾燥5分鐘,於PET膜上形成絕緣性樹脂層。該絕緣性樹脂層之厚度為6 μm。另外,以表1所示之組成製備第2絕緣性樹脂層形成用樹脂組成物,以相同之方式形成厚度12 μm之樹脂層。
另外,準備與實施例1相同之20%壓縮彈性率為22000 N/mm 2之高硬度導電粒子及20%壓縮彈性率為6000 N/mm 2之低硬度導電粒子。
另一方面,藉由以導電粒子如圖1A所示般成為正方格子排列,高硬度導電粒子及低硬度導電粒子之整體之個數密度成為表5所示之數值之方式製作模具,使公知之透明性樹脂之顆粒以熔融之狀態流入該模具中,進行冷卻並固化,而形成凹部為圖1A所示之排列圖案之樹脂模具。
藉由將高硬度導電粒子與低硬度導電粒子以成為表5所示之比率之方式混合並填充至該樹脂模具之凹部,於其上覆蓋上述絕緣性樹脂層,於60℃下以0.5 MPa按壓而使其貼合。繼而,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℃、0.5 MPa)下壓入至該絕緣性樹脂層內,形成導電粒子分散層。於該情形時,埋入率設為99.9%。於埋入有導電粒子之導電粒子分散層之表面,積層由上述第2絕緣性樹脂層形成用樹脂組成物所形成之樹脂層,而製造高硬度導電粒子與低硬度導電粒子整體呈正方格子排列之異向性導電膜。
將如此獲得之異向性導電膜裁剪為對於連接而言充分之面積,使用經裁剪之異向性導電膜,以與實施例1相同之方式製作評價用連接構造體,評價(a)捕捉效率、(b)壓痕、(c)粒子壓扁率、(d)電阻值。將結果示於表5。
實施例17~20、比較例8、9 準備與實施例5相同之20%壓縮彈性率為14000 N/mm 2之高硬度導電粒子、及20%壓縮彈性率為6000 N/mm 2之低硬度導電粒子。
將該高硬度導電粒子與低硬度導電粒子以成為表6所示之比率之方式混合並填充至樹脂模具,除此以外,以與實施例13相同之方式,製造高硬度導電粒子與低硬度導電粒子整體呈正方格子排列之異向性導電膜。
另外,與實施例1同樣地裁剪為對於連接而言充分之面積,使用經裁剪之異向性導電膜評價(a)捕捉效率、(b)壓痕、(c)粒子壓扁率、(d)電阻值。將結果示於表6。
實施例21~24、比較例10 準備與實施例9相同之20%壓縮彈性率為9000 N/mm 2之高硬度導電粒子、及20%壓縮彈性率為6000 N/mm 2之低硬度導電粒子。
將該高硬度導電粒子與低硬度導電粒子以成為表7所示之比率之方式混合並填充至樹脂模具,除此以外,以與實施例13相同之方式,製造高硬度導電粒子與低硬度導電粒子整體呈正方格子排列之異向性導電膜。
另外,與實施例1同樣地裁剪為對於連接而言充分之面積,使用經裁剪之異向性導電膜評價(a)捕捉效率、(b)壓痕、(c)粒子壓扁率、(d)電阻值。將結果示於表7。
[表2]
   比較例1 實施例1 實施例2 實施例3 實施例4 比較例2
作為導電粒子整體之配置 無規 無規 無規 無規 無規 無規
高硬度導電粒子K值(N/mm 2 22000 22000 22000 22000 22000 22000
低硬度導電粒子K值(N/mm 2 6000 6000 6000 6000 6000 6000
個數密度比率(高:低) 100:0 90:10 70:30 50:50 30:70 0:100
個數密度合計(個/mm 2 56000 56000 56000 56000 56000 56000
評價 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值
初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h
壓力90 MPa B NG B C B C B OK A B A B B OK A A A B B OK B B A B B OK A A A A B NG A A A A
壓力120 MPa B OK B B A A B OK A A A A B OK A A A A B OK A A A A B OK A A A A B NG A A A A
[表3]
   比較例3 實施例5 實施例6 實施例7 實施例8 比較例4
作為導電粒子整體之配置 無規 無規 無規 無規 無規 無規
高硬度導電粒子K值(N/mm 2 14000 14000 14000 14000 14000 14000
低硬度導電粒子K值(N/mm 2 6000 6000 6000 6000 6000 6000
個數密度比率(高:低) 100:0 90:10 70:30 50:50 30:70 0:100
個數密度合計(個/mm 2 56000 56000 56000 56000 56000 56000
評價 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值
初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h
壓力60 MPa B NG B C B C B OK B B B B B OK A A A B B OK A A A B B OK A A A B B NG A A A B
壓力90 MPa B NG A A A A B OK A A A A B OK A A A A B OK A A A A B OK A A A A B NG A A A A
壓力120 MPa B OK A A A A B OK A A A A B OK A A A A B OK A A A A B OK A A A A B NG A A A A
[表4]
   實施例9 實施例10 實施例11 實施例12 比較例5
作為導電粒子整體之配置 無規 無規 無規 無規 無規
高硬度導電粒子K值(N/mm 2 9000 9000 9000 9000 9000
低硬度導電粒子K值(N/mm 2 6000 6000 6000 6000 6000
個數密度比率(高:低) 90:10 70:30 50:50 30:70 0:100
個數密度合計(個/mm 2 28000 28000 28000 28000 28000
評價 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值
初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h
壓力60 MPa B OK A A A A B OK A A A A B OK A A A A B OK A A A A B NG A A A B
壓力90 MPa B OK A A A A B OK A A A A B OK A A A A B OK A A A A B NG A A A A
[表5]
   比較例6 實施例13 實施例14 實施例15 實施例16 比較例7
作為導電粒子整體之配置 正方格子 正方格子 正方格子 正方格子 正方格子 正方格子
高硬度導電粒子K值(N/mm 2 22000 22000 22000 22000 22000 22000
低硬度導電粒子K值(N/mm 2 6000 6000 6000 6000 6000 6000
個數密度比率(高:低) 100:0 90:10 70:30 50:50 30:70 0:100
個數密度合計(個/mm 2 28000 28000 28000 28000 28000 28000
評價 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值
初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h
壓力90 MPa A NG B C B C A OK A B A B A OK A A A B A OK A B A B A OK A B A A A NG A A A A
壓力120 MPa A OK B B A A A OK A A A A A OK A A A A A OK A A A A A OK A A A A A NG A A A A
[表6]
   比較例8 實施例17 實施例18 實施例19 實施例20 比較例9
作為導電粒子整體之配置 正方格子 正方格子 正方格子 正方格子 正方格子 正方格子
高硬度導電粒子K值(N/mm 2 14000 14000 14000 14000 14000 14000
低硬度導電粒子K值(N/mm 2 6000 6000 6000 6000 6000 6000
個數密度比率(高:低) 100:0 90:10 70:30 50:50 30:70 0:100
個數密度合計(個/mm 2 28000 28000 28000 28000 28000 28000
評價 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值
初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h
壓力60 MPa A NG B C B C A OK B B B B A OK A B A B A OK A A A B A OK A A A B A NG A A A B
壓力90 MPa A NG A A A A A OK A A A A A OK A A A A A OK A A A A A OK A A A A A NG A A A A
壓力120 MPa A OK A A A A A OK A A A A A OK A A A A A OK A A A A A OK A A A A A NG A A A A
[表7]
   實施例21 實施例22 實施例23 實施例24 比較例10
作為導電粒子整體之配置 正方格子 正方格子 正方格子 正方格子 正方格子
高硬度導電粒子K值(N/mm 2 9000 9000 9000 9000 9000
低硬度導電粒子K值(N/mm 2 6000 6000 6000 6000 6000
個數密度比率(高:低) 90:10 70:30 50:50 30:70 0:100
個數密度合計(個/mm 2 28000 28000 28000 28000 28000
評價 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值 捕捉效率 壓痕 粒子壓扁率 電阻值
初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h 初期 500 h
壓力60 MPa A OK A A A A A OK A A A A A OK A A A A A OK A A A A A NG A A A B
壓力90 MPa A OK A A A A A OK A A A A A OK A A A A A OK A A A A A NG A A A A
由表2可知,根據含有20%壓縮彈性率為22000 N/mm 2之高硬度導電粒子及20%壓縮彈性率為6000 N/mm 2之低硬度導電粒子兩者,且無規地配置導電粒子的實施例1~4之異向性導電膜,壓痕之評價均良好,導通特性(初期電阻值,500 h電阻值)亦良好。相對於此,關於僅含有20%壓縮彈性率為22000 N/mm 2之高硬度導電粒子的比較例1之異向性導電膜、及僅含有20%壓縮彈性率為6000 N/mm 2之低硬度導電粒子的比較例2之異向性導電膜,壓痕之評價均較差,進而僅含有高硬度導電粒子的比較例1之異向性導電膜之導通特性(500 h)較差。由此推斷,若導電粒子僅為低硬度導電粒子,則硬度不足,因此成為難以看到壓痕之狀態,另外,若導電粒子僅為高硬度導電粒子,則過硬而導電粒子之壓縮變得不充分,因此難以看到壓痕。此外,即便於僅為高硬度導電粒子之情形時壓痕之評價為OK之情形時,混合有高硬度導電粒子與低硬度導電粒子之實施例亦更容易觀察到壓痕。
由表5可知,於含有20%壓縮彈性率為22000 N/mm 2之高硬度導電粒子及20%壓縮彈性率為6000 N/mm 2之低硬度導電粒子兩者,且導電粒子呈正方格子排列的實施例13~16中,與上述實施例1~4同樣地,壓痕之評價均良好,導通特性(初期電阻值,500 h電阻值)亦良好。於僅含有高硬度導電粒子或低硬度導電粒子之任一種的比較例6、7中,於壓痕方面存在問題。
由表3可知,關於含有20%壓縮彈性率為14000 N/mm 2之高硬度導電粒子及20%壓縮彈性率為6000 N/mm 2之低硬度導電粒子兩者,且無規地配置導電粒子的實施例5~8之異向性導電膜,壓痕之評價均良好,導通特性(初期電阻值,500 h電阻值)亦良好。尤其是即便異向性導電連接時之壓力為60 MPa之低壓時亦良好。相對於此,僅含有20%壓縮彈性率為14000 N/mm 2之高硬度導電粒子的比較例3之異向性導電膜之壓痕之評價較差,進而若異向性導電連接時之壓力為60 MPa,則導通特性(500 h)亦較差。另外,僅含有低硬度導電粒子作為導電粒子的比較例4之異向性導電膜於壓痕方面存在問題。
由表6可知,於含有20%壓縮彈性率為14000 N/mm 2之高硬度導電粒子及20%壓縮彈性率為6000 N/mm 2之低硬度導電粒子兩者,且導電粒子呈正方格子排列的實施例17~20中,亦與上述實施例5~8同樣地,壓痕之評價均良好,導通特性(初期電阻值,500 h電阻值)亦良好。於僅含有高硬度導電粒子或低硬度導電粒子之任一者的比較例8、9中,於壓痕方面存在問題。
由表4亦可知,關於含有20%壓縮彈性率為9000 N/mm 2之高硬度導電粒子及20%壓縮彈性率為6000 N/mm 2之低硬度導電粒子兩者的實施例9~12之異向性導電膜,壓痕之評價均良好,導通特性(初期電阻值,500 h電阻值)亦良好,尤其是即便異向性導電連接時之壓力為60 MPa之低壓時亦良好。另外,僅含有低硬度導電粒子作為導電粒子的比較例5之異向性導電膜於壓痕方面存在問題。
由表7可知,於含有20%壓縮彈性率為9000 N/mm 2之高硬度導電粒子及20%壓縮彈性率為6000 N/mm 2之低硬度導電粒子兩者,且導電粒子呈正方格子排列的實施例21~24中,亦與上述實施例9~12同樣地,壓痕之評價均良好,導通特性(初期電阻值、500 h電阻值)亦良好,尤其是即便異向性導電連接時之壓力為60 MPa之低壓時亦良好。另外,僅含有低硬度導電粒子作為導電粒子的比較例10之異向性導電膜於壓痕方面存在問題。
1A:高硬度導電粒子 1B:低硬度導電粒子 2:絕緣性樹脂層 2b:凹陷(傾斜) 2c:凹陷(起伏) 3:導電粒子分散層 4:第2絕緣性樹脂層 10A、10B、10C、10D、10E、10F、10G:異向性導電膜 D:導電粒子之平均粒徑 La:絕緣性樹脂層之層厚 Lb:鄰接之導電粒子間之中央部之切平面與導電粒子最深部之距離 Lc:傾斜或起伏中之導電粒子之露出(正上方)部分之直徑 Ld:導電粒子之周圍或正上方之絕緣性樹脂層之傾斜或起伏之最大直徑 Le:導電粒子之周圍之絕緣性樹脂層中之傾斜之最大深度 Lf:導電粒子之正上方之絕緣性樹脂層中之起伏之最大深度
[圖1A]係表示本發明之一實施例之異向性導電膜10A之導電粒子之配置的俯視圖。 [圖1B]係實施例之異向性導電膜10A之剖視圖。 [圖2A]係表示本發明之一實施例之異向性導電膜10B之導電粒子之配置的俯視圖。 [圖2B]係實施例之異向性導電膜10B之剖視圖。 [圖3]係實施例之異向性導電膜10C之剖視圖。 [圖4]係實施例之異向性導電膜10D之剖視圖。 [圖5]係實施例之異向性導電膜10E之剖視圖。 [圖6]係實施例之異向性導電膜10F之剖視圖。 [圖7]係實施例之異向性導電膜10G之剖視圖。 [圖8]係實施例之異向性導電膜100A之剖視圖。 [圖9]係實施例之異向性導電膜100B之剖視圖。 [圖10A]係實施例之異向性導電膜100C之剖視圖。 [圖10B]係實施例之異向性導電膜100C'之剖視圖。 [圖11]係實施例之異向性導電膜100D之剖視圖。 [圖12]係實施例之異向性導電膜100E之剖視圖。 [圖13]係實施例之異向性導電膜100F之剖視圖。 [圖14]係實施例之異向性導電膜100G之剖視圖。 [圖15]係用於比較之異向性導電膜100X之剖視圖。
1A:高硬度導電粒子
1B:低硬度導電粒子
2:絕緣性樹脂層
10A:異向性導電膜
20:端子
A:格子軸
θ:角度

Claims (17)

  1. 一種異向性導電膜,其於絕緣性樹脂層中分散有作為導電粒子的20%壓縮彈性率為8000~28000 N/mm 2之高硬度導電粒子及20%壓縮彈性率低於該高硬度導電粒子之低硬度導電粒子,並且導電粒子整體之平均粒徑未達10 μm,低硬度導電粒子之個數密度為導電粒子整體之10%以上,導電粒子之膜厚方向之位置對齊, 包含高硬度導電粒子及低硬度導電粒子之導電粒子於俯視下規則地配置,且 高硬度導電粒子及低硬度導電粒子之附近的絕緣性樹脂層之表面相對於鄰接之導電粒子間之中央部的絕緣性樹脂層之切平面具有傾斜或起伏。
  2. 如申請專利範圍第1項之異向性導電膜,其中,導電粒子整體之個數密度為6000個/mm 2以上且42000個/mm 2以下。
  3. 如申請專利範圍第1或2項之異向性導電膜,其中,相對於導電粒子整體之平均粒徑D之絕緣性樹脂層之層厚La之比(La/D)為0.3以上。
  4. 如申請專利範圍第1或2項之異向性導電膜,其中,導電粒子之埋入率為30%以上且105%以下。
  5. 一種異向性導電膜,其於絕緣性樹脂層中分散有作為導電粒子的20%壓縮彈性率為8000~28000 N/mm 2之高硬度導電粒子及20%壓縮彈性率低於該高硬度導電粒子之低硬度導電粒子,並且導電粒子整體之平均粒徑為10 μm以上,導電粒子整體之個數密度為20個/mm 2以上且2000個/mm 2以下,低硬度導電粒子之個數密度為導電粒子整體之10%以上,導電粒子之膜厚方向之位置對齊, 包含高硬度導電粒子及低硬度導電粒子之導電粒子於俯視下規則地配置,且 高硬度導電粒子及低硬度導電粒子之附近的絕緣性樹脂層之表面相對於鄰接之導電粒子間之中央部的絕緣性樹脂層之切平面具有傾斜或起伏。
  6. 如申請專利範圍第5項之異向性導電膜,其中,相對於導電粒子整體之平均粒徑D之絕緣性樹脂層之層厚La之比(La/D)為3.5以下。
  7. 如申請專利範圍第5或6項之異向性導電膜,其中,導電粒子之埋入率為30%以上且105%以下。
  8. 如申請專利範圍第1、2、5、6項中任一項之異向性導電膜,其中,低硬度導電粒子之20%壓縮彈性率為高硬度導電粒子之20%壓縮彈性率的10%以上且70%以下。
  9. 如申請專利範圍第1、2、5、6項中任一項之異向性導電膜,其中,低硬度導電粒子之個數密度為導電粒子整體之20%以上且80%以下。
  10. 如申請專利範圍第1或5項之異向性導電膜,其中,包含高硬度導電粒子及低硬度導電粒子之導電粒子彼此互不接觸地存在之個數比率為95%以上。
  11. 如申請專利範圍第1、2、5、6項中任一項之異向性導電膜,其中,高硬度導電粒子與低硬度導電粒子無規地混合。
  12. 如申請專利範圍第1或5項之異向性導電膜,其中,於上述傾斜中,高硬度導電粒子及低硬度導電粒子之周圍的絕緣性樹脂層之表面相對於上述切平面發生缺損;於上述起伏中,高硬度導電粒子及低硬度導電粒子之正上方的絕緣性樹脂層之樹脂量較上述高硬度導電粒子及低硬度導電粒子之正上方之絕緣性樹脂層之表面位於該切平面時少。
  13. 一種連接構造體,其利用申請專利範圍第1至12項中任一項之異向性導電膜將第1電子零件與第2電子零件進行異向性導電連接。
  14. 如申請專利範圍第13項之連接構造體,其中,於第1電子零件中,於PET基材形成有端子。
  15. 一種連接構造體之製造方法,其利用申請專利範圍第1至12項中任一項之異向性導電膜將第1電子零件與第2電子零件進行異向性導電連接。
  16. 如申請專利範圍第15項之連接構造體之製造方法,其中,於第1電子零件中,於PET基材形成有端子。
  17. 一種捲裝體,其係將申請專利範圍第1至12項中任一項之異向性導電膜之長條體捲成捲芯而成之捲裝體。
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