TW202307162A - 異向性導電膜 - Google Patents

異向性導電膜 Download PDF

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Publication number
TW202307162A
TW202307162A TW111137860A TW111137860A TW202307162A TW 202307162 A TW202307162 A TW 202307162A TW 111137860 A TW111137860 A TW 111137860A TW 111137860 A TW111137860 A TW 111137860A TW 202307162 A TW202307162 A TW 202307162A
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Taiwan
Prior art keywords
anisotropic conductive
conductive film
conductive particles
repeating unit
insulating resin
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TW111137860A
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English (en)
Inventor
阿久津恭志
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 JP2017085743A external-priority patent/JP7274810B2/ja
Application filed by 日商迪睿合股份有限公司 filed Critical 日商迪睿合股份有限公司
Publication of TW202307162A publication Critical patent/TW202307162A/zh

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    • C09J7/10Adhesives in the form of films or foils without carriers
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    • H01B5/00Non-insulated conductors or conductive bodies characterised by their form
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Abstract

提供一種能夠應對窄間距之凸塊,且與以往之異向性導電膜相比能夠降低導電粒子之個數密度的異向性導電膜。於異向性導電膜1A中,於絕緣性樹脂黏合劑3配置有導電粒子2,於俯視下沿縱橫方向重複配置有多角形之重複單元5,該多角形之重複單元5係將複數個導電粒子2之中心依序連結而形成。重複單元5之多角形之邊與異向性導電膜之長邊方向或短邊方向斜交。

Description

異向性導電膜
本發明係關於一種異向性導電膜。
使導電粒子分散於絕緣性樹脂黏合劑中而成之異向性導電膜於將IC晶片等電子零件安裝於配線基板等時被廣泛使用。於異向性導電膜中,強烈要求藉由伴隨電子零件之高密度安裝的凸塊之窄間距化,而提高凸塊中之導電粒子的捕捉性,且避免相鄰之凸塊間之短路。
針對此種要求,提出有將異向性導電膜中之導電粒子的配置設為晶格狀之排列,且使該排列軸相對於異向性導電膜之長邊方向傾斜(專利文獻1、專利文獻2)。
專利文獻1:日本專利4887700號公報 專利文獻2:日本特開平9-320345號公報
[發明所欲解決之課題]
如專利文獻1、2記載,於將導電粒子配置為簡單之晶格狀之情形時,藉由排列軸之傾斜角或導電粒子間之距離應對凸塊之佈局。因此,若凸塊成為窄間距,則必須縮小導電粒子間之距離,導電粒子之個數密度增加,導致異向性導電膜之製造成本增加。
又,為了縮小導電粒子間之距離且可避免短路,必須抑制於異向性導電連接時導電粒子因絕緣性樹脂黏合劑之樹脂流動而隨之流走,對絕緣性樹脂黏合劑之設計亦有制約。
因此,本發明之課題在於能夠應對窄間距之凸塊,且與以往之異向性導電膜相比降低了導電粒子之個數密度。 [解決課題之技術手段]
本發明人發現,不將異向性導電膜之俯視下的導電粒子設為簡單之晶格狀排列,而藉由由複數個導電粒子構成的多角形之單元的重複而沿縱橫方向重複配置導電粒子,且使形成該多角形之邊相對於異向性導電膜之長邊方向或短邊方向而斜交,藉此可解決上述之課題,從而思及本發明。
即,本發明提供一種異向性導電膜,其於絕緣性樹脂黏合劑中配置有導電粒子,且 於俯視下重複配置多角形之重複單元,該多角形之重複單元係將複數個導電粒子之中心依序連結而形成, 重複單元之多角形具有與異向性導電膜之長邊方向或短邊方向斜交之邊。 [發明之效果]
根據本發明之異向性導電膜,由於未將各導電粒子設為簡單之晶格狀之排列,而設為重複配置由複數個導電粒子形成之重複單元,因此導電粒子之粒子間距離經縮短之部分均勻地存在於膜整體中。又,由於重複單元之多角形具有與異向性導電膜之長邊方向或短邊方向斜交之邊,因此凸塊中之導電粒子的捕捉性高。因此能夠在不引起短路之情況下將窄間距之凸塊進行連接。
另一方面,根據本發明之異向性導電膜,由於導電粒子之粒子間距離經擴大之部分亦均勻地存在於膜整體中,因此能夠抑制異向性導電膜整體之導電粒子的個數密度增加,抑制伴隨導電粒子之個數密度增加而製造成本之增加。又,藉由抑制導電粒子之個數密度增加,亦可抑制異向性導電連接時按壓夾具必需之推力的增加。因此,能夠減小異向性導電連接時自按壓夾具對電子零件施加之壓力,防止電子零件之變形。
以下,一邊參照圖式一邊對本發明之異向性導電膜進行詳細說明。再者,各圖中,相同之符號表示相同或同等之構成要素。
<異向性導電膜之整體構成> 圖1A係表示本發明之實施例之異向性導電膜1A的導電粒子之配置的俯視圖,圖1C係其剖面圖。 該異向性導電膜1A具有如下結構:將導電粒子2以單層配置於絕緣性樹脂黏合劑3之表面或其附近,並於其上積層有絕緣性接著層4。
再者,作為本發明之異向性導電膜,亦可設為省略絕緣性接著層4,而將導電粒子2埋入至絕緣性樹脂黏合劑3之構成。
<導電粒子> 作為導電粒子2,可適當選擇公知之異向性導電膜中使用者而使用。例如可列舉:鎳、銅、銀、金、鈀等金屬粒子;以鎳等金屬被覆聚醯胺、聚苯胍口井(polybenzoguanamine)等樹脂粒子之表面而成之金屬被覆樹脂粒子等。配置之導電粒子的大小較佳為1 μm以上且30 μm以下,更佳為1 μm以上且10 μm以下,進而較佳為2 μm以上且6 μm以下。
導電粒子2之平均粒徑可藉由圖像型或雷射式粒度分佈計進行測量。亦可俯視觀察異向性導電膜,而測量粒徑並求出。於該情形時,較佳為測量200個以上,更佳為測量500個以上,進而更佳為測量1000個以上。
導電粒子2之表面較佳藉由絕緣塗佈或絕緣粒子處理等而被覆。此種被覆容易自導電粒子2之表面剝離,且不會阻礙異向性導電連接。又,亦可於導電粒子2之整個表面或一部分設置有突起。突起之高度為導電粒徑之20%以內,較佳為10%以內。
<導電粒子之配置> 於以下之圖1A至圖7中,作為一例,對多角形之重複單元5為梯形之情形時的重複單元之配置例進行說明。 圖1A所示之異向性導電膜1A之俯視下的導電粒子2之配置係如下狀態:依序連結複數個導電粒子2a、2b、2c、2d之中心形成之多角形之重複單元5沿正交之2個方向(X方向、Y方向)重複而配置於異向性導電膜1之一面(即,整個面)。再者,本發明之異向性導電膜可視需要具有未配置導電粒子之區域。
該導電粒子2之配置亦可視為於無間隙地排列正三角形之情形時之正三角形的頂點之一部分(或無間隙地排列正六角形之情形時之正六角形的頂點)配置導電粒子。進一步換言之,可認為係自導電粒子存在於六方晶格之各晶格點之配置中規則地除去特定晶格點之導電粒子而成之配置。因此,由導電粒子2a、2b、2c、2d構成之重複單元5之梯形的頂點成為組合有正三角形之正六角形之一部分,存在於六方晶格之晶格點。若以該梯形之一邊2a、2b為中心使其反轉,則邊2c、2d與鄰接之梯形之重複單元(即,由導電粒子2e、2f、2g、2h構成之重複單元)之邊2g、2h重疊。
再者,於考慮該導電粒子2之重複單元之情形時,亦可如圖1B所示,視為由導電粒子2p、2q、2r、2s、2t、2u構成之正六角形之重複單元5x沿X方向重疊一邊並且重複,沿Y方向於邊與頂點均不重疊之情況下重複,於本發明中重複單元較佳視為由4個以上之導電粒子構成之多角形,且為在不重疊該多角形之邊的情況下沿異向性導電膜之縱橫方向重複之最小單位之多角形。
重複單元5(圖1A)之梯形的各邊均與異向性導電膜1A之長邊方向及短邊方向斜交。藉此,導電粒子2a之異向性導電膜之長邊方向的外切線L1貫穿導電粒子2b,該導電粒子2b於異向性導電膜之長邊方向與該導電粒子2a鄰接。又,導電粒子2a之異向性導電膜之短邊方向的外切線L2貫穿導電粒子2d,該導電粒子2d於異向性導電膜之短邊方向與該導電粒子2a鄰接。由於通常於異向性導電連接時,異向性導電膜之長邊方向成為凸塊之短邊方向,因此若重複單元5之多角形之邊與異向性導電膜1A之長邊方向或短邊方向斜交,則可防止複數個導電粒子沿凸塊之緣而排列成直線狀,藉此可避免排列成直線狀之複數個導電粒子一齊脫離端子而變得無助於導通之現象,故而可提高導電粒子2之捕捉性。
再者,於本發明中,重複單元可未必其全部邊與異向性導電膜之長邊方向或短邊方向斜交,於各凸塊之短邊方向成為異向性導電膜之長邊方向之情形時,就導電粒子之捕捉性之方面而言,較佳重複單元之各邊與異向性導電膜之長邊方向或短邊方向斜交。
與此相對,於凸塊之排列圖案為放射狀之情形時(所謂扇出凸塊),較佳形成重複單元之多角形具有異向性導電膜之長邊方向或短邊方向之邊。即,為了實現應連接之凸塊彼此即使熱膨脹亦不會錯位,存在使凸塊之排列圖案成為放射狀之情形(例如,日本特開2007-19550號公報、日本特開2015-232660號公報等),於該情形時,各凸塊之長邊方向與異向性導電膜之長邊方向及短邊方向所成之角度逐漸變化。因此,即使不使重複單元5之多角形之邊與異向性導電膜之長邊方向或短邊方向斜交,重複單元5之多角形之邊亦與呈放射狀排列之各凸塊之長邊方向之邊緣斜交。因此,可避免於異向性導電連接時附於凸塊之緣的多數導電粒子不被該凸塊捕捉,導致導電粒子之捕捉性降低之現象。
另一方面,凸塊之放射狀之排列圖案通常形成為左右對稱。因此,就藉由異向性導電連接後之壓痕容易確認連接狀態之良好與否之方面而言,較佳形成重複單元5之多角形具有異向性導電膜之長邊方向或短邊方向之邊,尤其是形成重複單元5之多角形具有異向性導電膜之長邊方向或短邊方向之邊,且為以異向性導電膜之短邊方向或長邊方向為對稱軸之對稱形狀,並且該重複單元5沿異向性導電膜之長邊方向或短邊方向重複配置。例如,可如圖2A所示之異向性導電膜1Ba般,將重複單元5之梯形設為具有異向性導電膜之短邊方向之對稱軸的梯形,使其底邊及上邊與異向性導電膜之長邊方向平行,又,亦可如圖2B所示之異向性導電膜1Bb般,使同樣之梯形之重複單元之底邊及上邊與異向性導電膜之短邊方向平行。
於本發明中,重複單元5中之導電粒子2之配置、或重複單元5之縱橫的重複間距可根據作為異向性導電連接之連接對象之端子的形狀或間距而適當變更。因此,與將導電粒子2設為簡單的晶格狀之排列之情形相比,異向性導電膜整體可以較少之導電粒子數達成較高之捕捉性。例如,針對上述異向性導電膜1Ba,為了提高異向性導電膜之長邊方向之導電粒子的個數密度,亦可設為如下配置:如圖3A所示之異向性導電膜1Ca般,沿異向性導電膜之寬度方向將梯形之重複單元5以其形狀之狀態重複,且沿異向性導電膜之長邊方向將梯形之重複單元5及重複單元5B交替重複,該重複單元5B係使該梯形之重複單元沿膜之長邊方向之軸反轉而成之形狀。於該情形時,亦可設為如下配置:如圖4A所示之異向性導電膜1Da般,沿異向性導電膜之短邊方向亦交替重複梯形之重複單元5及使其反轉而成之形狀之重複單元5B。
同樣地,針對上述異向性導電膜1Bb,為了提高異向性導電膜之短邊方向之導電粒子的個數密度,亦可設為如下配置:如圖3B所示之異向性導電膜1Cb般,沿異向性導電膜之長邊方向將梯形之重複單元5以其形狀之狀態重複,且沿異向性導電膜之寬度方向將重複單元5及重複單元5B交替重複,該重複單元5B係使該重複單元沿異向性導電膜之短邊方向之軸反轉而成之形狀。又,亦可設為如下配置:如圖4B所示之異向性導電膜1Db般,沿異向性導電膜之長邊方向及短邊方向均將重複單元5及使其反轉而成之形狀之重複單元5B交替重複。
進而,針對上述異向性導電膜1Ca,為了降低異向性導電膜之短邊方向的個數密度,可如圖5A所示之異向性導電膜1Ea般,擴大重複單元5、5B之異向性導電膜之長邊方向的重複列彼此之間隔,為了降低異向性導電膜之長邊方向的個數密度,可如圖5B所示之異向性導電膜1Eb般,擴大重複單元5、5B之異向性導電膜之寬度方向的重複列彼此之間隔。
又,亦可如圖6所示之異向性導電膜1F般,針對圖1A所示之異向性導電膜1A之導電粒子之配置,擴大重複單元5之Y方向的重複間距。於圖1A所示之導電粒子2之配置中,各導電粒子2與無間隙地排列正六角形之情形時之正六角形的頂點之任一者重疊,但於圖6所示之導電粒子之配置中,未必全部導電粒子成為無間隙地排列正六角形之情形時之正六角形的頂點,於該方面與圖1A所示之導電粒子之配置不同。
又,亦可如圖7所示之異向性導電膜1G般,進一步擴大Y方向之重複間距,並且於Y方向鄰接之重複單元5之間配置單獨之導電粒子2p,亦可進而配置其他重複單元。又,亦可適當變更重複單元5之X方向之重複間距,亦可於X方向之重複間距之間配置單獨之導電粒子或其他重複單元。
亦可如圖8所示之異向性導電膜1H般,沿異向性導電膜之短邊方向或長邊方向重複梯形之重複單元5或使其反轉而成之重複單元5B,並且於重複單元5之異向性導電膜之寬度方向之列與重複單元5B之異向性導電膜之寬度方向之列之間配置單獨之導電粒子2p之列。藉此,成為導電粒子2以斜方晶格之方式排列,且單獨之導電粒子2p存在於單位晶格中心之配置。於使導電粒子以斜方晶格之方式排列之情形時,為了降低導電粒子的個數密度,亦可如圖9所示之異向性導電膜1I般將重複單元5本身形成為菱形。藉由如圖8及圖9所示般將導電粒子2配置為斜方晶格狀,導電粒子2於異向性導電膜之長邊方向、短邊方向及相對於該等方向傾斜之方向存在,因此變得容易兼顧異向性導電連接時之導電粒子的捕捉性之提高及短路之抑制。
又,亦可設為如下排列:如圖10所示之異向性導電膜1J般,將由4個導電粒子構成之菱形之重複單元5的長方晶格狀之排列,與使該重複單元5沿異向性導電膜之長邊方向或短邊方向反轉而成之菱形之重複單元5B的長方晶格狀之排列以該等之晶格點不重合之方式重複。亦可如圖11所示之異向性導電膜1K般,為與圖10之異向性導電膜1J同樣之粒子配置,且擴大膜短邊方向之重複單元5、5B之排列彼此之間隔。
重複單元並不限定於導電粒子佔據無間隙地排列正三角形之情形時之正六角形的頂點(即,六方晶格之晶格點)之一部分的配置。亦可設為導電粒子佔據正方晶格之晶格點之一部分。例如,可將與如圖5A所示之導電粒子之配置同樣的沿異向性導電膜之長邊方向與短邊方向交替重複梯形之重複單元5與使其反轉而成之重複單元5B之配置如圖12所示之異向性導電膜1L般形成於正方晶格之晶格點上。
又,形成重複單元之多角形的頂點個數並不限於4個,可為5以上,亦可為6以上,亦可為7以上。但是於異向性導電膜製造之設計或生產步驟中,為了容易識別重複單元之形狀,較佳將重複單元的頂點個數設為偶數。
形成重複單元之多角形之形狀可為正多角形,亦可不為正多角形,就容易識別重複單元之形狀之方面而言,較佳為具有對稱軸之形狀。於該情形時,構成重複單元之各導電粒子亦可不存在於六方晶格或正方晶格之晶格點。例如,亦可如圖13所示之異向性導電膜1M般,由位於正八角形的頂點之導電粒子構成重複單元5。重複單元之多角形之形狀可根據進行異向性導電連接之凸塊或端子之形狀、間距、凸塊或端子之長邊方向相對於異向性導電膜之膜長邊方向之傾斜角、異向性導電膜中之絕緣性樹脂黏合劑之樹脂組成等而適當決定。
再者,作為本發明中之導電粒子之配置,並不限於圖示之重複單元之排列,例如,亦可為使圖示之重複單元之排列傾斜而成者。於該情形時,亦包括使其傾斜90°而成者、即交換膜之長邊方向與短邊方向而成之態樣。又,亦可為變更重複單元之間隔或重複單元內的導電粒子之間隔而成者。
<導電粒子之最短粒子間距離> 導電粒子之最短粒子間距離於重複單元內鄰接之導電粒子間及重複單元間鄰接之導電粒子間,均較佳為導電粒子之平均粒徑之0.5倍以上。若該距離過短,則變得容易因導電粒子之相互接觸而引起短路。鄰接之導電粒子的距離之上限根據凸塊形狀或凸塊間距而決定。例如,於凸塊寬度為200 μm、凸塊間空間為200 μm之情形時,於使導電粒子於凸塊寬度或凸塊間空間之任一者中存在最少1個時,導電粒子之最短粒子間距離設為未達400 μm。就使導電粒子之捕捉性變得確實之方面而言,較佳設為未達200 μm。
<導電粒子之個數密度> 導電粒子之個數密度就抑制異向性導電膜之製造成本之方面,及避免於異向性導電連接時使用之按壓夾具必需之推力過大之方面而言,於導電粒子之平均粒徑未達10 μm之情形時,較佳為50000個/mm 2以下,更佳為35000個/mm 2以下,進而較佳為30000個/mm 2以下。另一方面,若導電粒子之個數密度過少,則有因端子未充分捕捉導電粒子導致導通不良之虞,故而較佳為300個/mm 2以上,更佳為500個/mm 2以上,進而較佳為800個/mm 2以上。
又,於導電粒子之平均粒徑為10 μm以上之情形時,較佳為15個/mm 2以上,更佳為50個/mm 2以上,進而較佳為160個/mm 2以上。其原因在於,若導電粒徑變大,則導電粒子之佔有面積率亦提高。就同樣之理由而言,較佳為1800個/mm 2以下,更佳為1100個/mm 2以下,進而較佳為800個/mm 2以下。
再者,導電粒子之個數密度亦可局部(作為一例,200 μm×200 μm)性地偏離上述個數密度。
<絕緣性樹脂黏合劑> 作為絕緣性樹脂黏合劑3,可適當選擇公知之異向性導電膜中用作絕緣性樹脂黏合劑之熱聚合性組成物、光聚合性組成物、光熱併用聚合性組成物等而使用。其中,作為熱聚合性組成物,可列舉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組成物、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組成物、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組成物等,作為光聚合性組成物,可列舉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組成物等。只要不特別產生問題,則亦可併用多種聚合性組成物。作為併用例,可列舉熱陽離子聚合性組成物與熱自由基聚合性組成物之併用等。
此處,作為光聚合起始劑,亦可含有對波長不同之光進行反應之多種起始劑。藉此,可區分使用異向性導電膜之製造時構成絕緣性樹脂層之樹脂之光硬化與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中使用之波長。
於使用光聚合性組成物形成絕緣性樹脂黏合劑3之情形時,藉由異向性導電膜之製造時之光硬化,可使絕緣性樹脂黏合劑3所含的光聚合性化合物之全部或一部分光硬化。藉由該光硬化,可保持或固定絕緣性樹脂黏合劑3中的導電粒子2之配置,而期待短路之抑制與捕捉之提高。又,藉由調整該光硬化之條件,可調整異向性導電膜之製造步驟中之絕緣性樹脂層的黏度。
絕緣性樹脂黏合劑3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,進而較佳為未達2質量%。其原因在於,若光聚合性化合物過多,則異向性導電連接時之壓入施加之推力會增加。
另一方面,熱聚合性組成物含有熱聚合性化合物與熱聚合起始劑,作為該熱聚合性化合物,可使用亦作為光聚合性化合物發揮功能者。又,於熱聚合性組成物中亦可除熱聚合性化合物以外另行含有光聚合性化合物,並且含有光聚合性起始劑。較佳除了熱聚合性化合物以外另行含有光聚合性化合物與光聚合起始劑。例如,使用熱陽離子系聚合起始劑作為熱聚合起始劑,使用環氧樹脂作為熱聚合性化合物,使用光自由基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。亦可於絕緣性黏合劑3中含有該等聚合性組成物之硬化物。
作為用作熱或光聚合性化合物之丙烯酸酯化合物,可使用以往公知之熱聚合型(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。
又,用作聚合性化合物之環氧化合物係形成三維網狀結構,且賦予良好之耐熱性、接著性者,較佳併用固體環氧樹脂與液狀環氧樹脂。此處,所謂固體環氧樹脂意指於常溫為固體之環氧樹脂。又,所謂液狀環氧樹脂意指於常溫為液狀之環氧樹脂。又,所謂常溫意指JIS Z 8703規定之5~35℃之溫度範圍。於本發明中可併用2種以上之環氧化合物。又,除了環氧化合物以外,亦可併用氧環丁烷(oxetane)化合物。
作為固體環氧樹脂,只要與液狀環氧樹脂相容,於常溫為固體,則無特別限定,可列舉:雙酚A型環氧樹脂、雙酚F型環氧樹脂、多官能型環氧樹脂、二環戊二烯型環氧樹脂、酚醛清漆苯酚型環氧樹脂、聯苯型環氧樹脂、萘型環氧樹脂等,可自該等中單獨使用1種,或可組合2種以上而使用。該等中,較佳使用雙酚A型環氧樹脂。
作為液狀環氧樹脂,只要於常溫為液狀,則無特別限定,可列舉:雙酚A型環氧樹脂、雙酚F型環氧樹脂、酚醛清漆苯酚型環氧樹脂、萘型環氧樹脂等,可自該等中單獨使用1種,或可組合2種以上而使用。尤其是就膜之黏性、柔軟性等觀點而言,較佳使用雙酚A型環氧樹脂。
熱聚合起始劑中,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的有機過氧化物。
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,則製品壽命(Life)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表現出良好之潛伏性的芳香族鋶鹽。
熱陽離子聚合起始劑之使用量過少亦有變得硬化不良之傾向,過多亦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。
作為熱陰離子聚合起始劑,可使用通常使用之公知者。例如可列舉:有機酸二醯肼、二氰二胺、胺化合物、聚醯胺胺化合物、氰酸酯化合物、酚樹脂、酸酐、羧酸、三級胺化合物、咪唑、路易斯酸、布忍斯特酸鹽、聚硫醇系硬化劑、脲樹脂、三聚氰胺樹脂、異氰酸酯化合物、封端異氰酸酯化合物等,可自該等中單獨使用1種,或可組合2種以上而使用。該等中,較佳使用以咪唑改質體作為核,並且以聚胺酯被覆其表面而成之微膠囊型潛伏性硬化劑。
較佳於熱聚合性組成物中含有膜形成樹脂。膜形成樹脂相當於例如平均分子量為10000以上之高分子量樹脂,就膜形成性之觀點而言,較佳為10000~80000左右之平均分子量。作為膜形成樹脂,可列舉:苯氧基樹脂、聚酯樹脂、聚胺酯樹脂、聚酯胺酯樹脂、丙烯酸樹脂、聚醯亞胺樹脂、丁醛樹脂等各種樹脂,該等可單獨使用,亦可組合2種以上而使用。該等中,就膜形成狀態、連接可靠性等觀點而言,較佳適宜地使用苯氧基樹脂。
為了調整熔融黏度,亦可於熱聚合性組成物中含有絕緣填料。其可列舉二氧化矽粉或氧化鋁粉等。絕緣性填料之大小較佳為粒徑20~1000 nm,又,摻合量較佳相對於環氧化合物等熱聚合性化合物(光聚合性化合物)100質量份而設為5~50質量份。
進而,亦可含有與上述絕緣填料不同之填充劑、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(ion catcher agent)等。
又,亦可視需要摻合應力緩和劑、矽烷偶合劑、無機填料等。作為應力緩和劑,可列舉:氫化苯乙烯-丁二烯嵌段共聚物、氫化苯乙烯-異戊二烯嵌段共聚物等。又,作為矽烷偶合劑,可列舉:環氧系、甲基丙烯醯氧基系、胺基系、乙烯基系、巰基/硫醚系、醯脲(ureide)系等。又,作為無機填料,可列舉:二氧化矽、滑石、氧化鈦、碳酸鈣、氧化鎂等。
絕緣性樹脂黏合劑3可藉由利用塗佈法將含有上述樹脂之塗層組成物成膜並加以乾燥,或進而進行硬化,或者預先利用公知之手法進行膜化而形成。絕緣性樹脂黏合劑3亦可藉由視需要將樹脂層進行積層而獲得。又,絕緣性樹脂黏合劑3較佳形成於經剝離處理之聚對酞酸乙二酯膜等剝離膜上。
(絕緣性樹脂黏合劑之黏度) 絕緣性樹脂黏合劑3之最低熔融黏度可根據異向性導電膜之製造方法等而適當決定。例如,於作為異向性導電膜之製造方法而進行以特定之配置將導電粒子保持於絕緣性樹脂黏合劑之表面,並將該導電粒子壓入至絕緣性樹脂黏合劑中之方法時,就使絕緣性樹脂黏合劑實現膜成形之方面而言,較佳將樹脂之最低熔融黏度設為1100 Pa・s以上。又,如下文所述,就如圖14或圖15所示般,於壓入至絕緣性樹脂黏合劑3中之導電粒子2的露出部分之周圍形成凹部3b,或如圖16所示般於壓入至絕緣性樹脂黏合劑3中之導電粒子2的正上方形成凹部3c之方面而言,最低熔融黏度較佳為1500 Pa・s以上,更佳為2000 Pa・s以上,進而較佳為3000~15000 Pa・s,尤佳為3000~10000 Pa・s。關於該最低熔融黏度,作為一例,可使用旋轉式流變儀(TA instrument公司製造),於升溫速度為10℃/分鐘、測量壓力為5 g之條件下保持恆定,使用直徑8 mm之測量板而求出。又,於在較佳為40~80℃、更佳為50~60℃進行將導電粒子2壓入至絕緣性樹脂黏合劑3中之步驟之情形時,就與上述同樣地形成凹部3b或3c之方面而言,於60℃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。
藉由如上述般將構成絕緣性樹脂黏合劑3之樹脂的黏度設為高黏度,於使用異向性導電膜時,於在相對向之電子零件等連接對象物之間夾持著導電粒子2進行加熱加壓之情形時,可防止異向性導電膜內之導電粒子2因熔融之絕緣性樹脂黏合劑3之流動而隨之流走。
(絕緣性樹脂黏合劑之厚度) 絕緣性樹脂黏合劑3的厚度La較佳為1 μm以上且60 μm以下,更佳為1 μm以上且30 μm以下,進而較佳為2 μm以上且15 μm以下。又,絕緣性樹脂黏合劑3的厚度La就與導電粒子2的平均粒徑D之關係而言,較佳為該等之比(La/D)為0.6~10。若絕緣性樹脂黏合劑3的厚度La過大,則於異向性導電連接時導電粒子變得容易錯位,端子中之導電粒子之捕捉性降低。若La/D超過10,則該傾向顯著。因此,La/D較佳為8以下,更佳為6以下。反之,若絕緣性樹脂黏合劑3的厚度La過小而La/D未達0.6,則難以藉由絕緣性樹脂黏合劑3將導電粒子維持為特定之粒子分散狀態或特定之排列。尤其是於連接之端子為高密度COG之情形時,絕緣性樹脂黏合劑3的層厚La與導電粒子2的粒徑D之比(La/D)較佳為0.8~2。
(絕緣性樹脂黏合劑中之導電粒子之埋入態樣) 關於絕緣性樹脂黏合劑3中之導電粒子2之埋入狀態,並無特別限制,於藉由在相對向之零件之間挾持異向性導電膜並進行加熱加壓而進行異向性導電連接之情形時,較佳如圖14、圖15所示般,使導電粒子2自絕緣性樹脂黏合劑3露出一部分,相對於鄰接之導電粒子2間之中央部的絕緣性樹脂黏合劑之表面3a的切平面3p而於導電粒子2之露出部分之周圍形成凹部3b,或如圖16所示般,於壓入至絕緣性樹脂黏合劑3內之導電粒子2之正上方的絕緣性樹脂黏合劑部分,相對於與上述同樣之切平面3p而形成凹部3c,使導電粒子2之正上方的絕緣性樹脂黏合劑3之表面存在起伏。針對在相對向之電子零件之電極間挾持導電粒子2進行加熱加壓時產生之導電粒子2之扁平化,藉由存在如圖14、圖15所示之凹部3b,與不存在凹部3b之情形相比,導電粒子2受到之來自絕緣性樹脂黏合劑3的阻力有所減少。因此,變得容易於相對向之電極間挾持導電粒子2,導通性能亦提高。又,構成絕緣性樹脂黏合劑3之樹脂中,藉由在導電粒子2之正上方的樹脂之表面形成凹部3c(圖16),與不存在凹部3c之情形相比加熱加壓時之壓力變得容易集中於導電粒子2,而變得容易於電極中挾持導電粒子2,導通性能提高。
就容易獲得上述之凹部3b、3c之效果之方面而言,導電粒子2的露出部分周圍之凹部3b(圖14、圖15)的最大深度Le與導電粒子2的平均粒徑D之比(Le/D)較佳為未達50%,更佳為未達30%,進而較佳為20~25%,導電粒子2的露出部分周圍之凹部3b(圖14、圖15)的最大徑Ld與導電粒子2的平均粒徑D之比(Ld/D)較佳為100%以上,更佳為100~150%,導電粒子2之正上方的樹脂之凹部3c(圖14)的最大深度Lf與導電粒子2的平均粒徑D之比(Lf/D)較佳為大於0,且較佳為未達10%,更佳為未達5%。
再者,導電粒子2的露出部分之徑Lc可設為導電粒子2的平均粒徑D以下,較佳為粒徑D之10~90%。可設為於導電粒子2的頂部2t之1點處露出,亦可設為導電粒子2完全埋設於絕緣性樹脂黏合劑3內,而徑Lc成為零。
(絕緣性樹脂黏合劑之厚度方向之導電粒子之位置) 就容易獲得上述凹部3b之效果之方面而言,切平面3p距導電粒子2的最深部之距離(以下稱為埋入量)Lb與導電粒子2的平均粒徑D之比(Lb/D)(以下稱為埋入率)較佳為60%以上且105%以下。
<絕緣性接著層> 於本發明之異向性導電膜中,亦可於配置有導電粒子2的絕緣性樹脂黏合劑3上積層黏度或黏著性與構成絕緣性樹脂黏合劑3之樹脂不同的絕緣性接著層4。
於在絕緣性樹脂黏合劑3形成上述凹部3b之情形時,可如圖17所示之異向性導電膜1d般,絕緣性接著層4積層於絕緣性樹脂黏合劑3之形成有凹部3b之面,亦可如圖18所示之異向性導電膜1e般,積層於與形成有凹部3b之面為相反側之面。於絕緣性樹脂黏合劑3形成有凹部3c之情形時亦相同。藉由積層絕緣性接著層4,於使用異向性導電膜將電子零件進行異向性導電連接時,可填充由電子零件之電極或凸塊形成之空間,而提高接著性。
又,於將絕緣性接著層4積層於絕緣性樹脂黏合劑3之情形時,不論絕緣性接著層4是否位於凹部3b、3c之形成面上,均較佳為絕緣性接著層4位於IC晶片等第1電子零件側(換言之,絕緣性樹脂黏合劑3位於基板等第2電子零件側)。藉此,可避免導電粒子之不經意之移動,而可提高捕捉性。再者,通常將IC晶片等第1電子零件設為按壓夾具側,將基板等第2電子零件設為載台側,將異向性導電膜與第2電子零件暫時壓接後,將第1電子零件與第2電子零件正式壓接,但根據第2電子零件之熱壓接區域之尺寸等,而將異向性導電膜暫貼於第1電子零件後,將第1電子零件與第2電子零件正式壓接。
作為絕緣性接著層4,可適當選擇公知之異向性導電膜中用作絕緣性接著層者而使用。絕緣性接著層4亦可設為使用與上述絕緣性樹脂黏合劑3同樣之樹脂並進一步將黏度調整為較低者。絕緣性接著層4與絕緣性樹脂黏合劑3之最低熔融黏度越存在差異,則越容易以絕緣性接著層4填充由電子零件的電極或凸塊形成之空間,而可期待提高電子零件彼此之接著性之效果。又,越存在該差異,則異向性導電連接時構成絕緣性樹脂黏合劑3的樹脂之移動量相對變得越小,因此端子之導電粒子的捕捉性越容易提高。實用上而言,絕緣性接著層4與絕緣性樹脂黏合劑3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,則於將長尺寸的異向性導電膜製成捲裝體之情形時,有產生樹脂之溢出或黏連(blocking)之虞,因此實用上較佳為15以下。更具體而言,絕緣性接著層4之較佳之最低熔融黏度滿足上述之比,且為3000 Pa・s以下,更佳為2000 Pa・s以下,尤佳為100~2000 Pa・s。
作為絕緣性接著層4之形成方法,可藉由利用塗佈法將含有與形成絕緣性樹脂黏合劑3之樹脂同樣之樹脂的塗層組成物成膜並加以乾燥,或進而進行硬化,或者預先利用公知之手法進行膜化而形成。
絕緣性接著層4之厚度較佳為1 μm以上且30 μm以下,更佳為2 μm以上且15 μm以下。
又,合併絕緣性樹脂黏合劑3與絕緣性接著層4而成之異向性導電膜整體的最低熔融黏度亦取決於絕緣性樹脂黏合劑3與絕緣性接著層4的厚度之比率,實用上可設為8000 Pa・s以下,為了容易填充至凸塊間,可為200~7000 Pa・s,較佳為200~4000 Pa・s。
進而,亦可視需要於絕緣性樹脂黏合劑3或絕緣性接著層4中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相對於構成該等層之樹脂100質量份而設為3質量份以上且40質量份以下。藉此,於異向性導電連接時即使異向性導電膜熔融,亦可抑制熔融之樹脂導致導電粒子不必要地移動。
<異向性導電膜之製造方法> 作為異向性導電膜之製造方法,例如,製造用以將導電粒子配置為特定之排列的轉印模具,於轉印模具之凹部填充導電粒子,使形成於剝離膜上之絕緣性樹脂黏合劑3覆於其上並施加壓力,而將導電粒子2壓入至絕緣性樹脂黏合劑3中,藉此使導電粒子2轉接著於絕緣性樹脂黏合劑3。或進而將絕緣性接著層4積層於該導電粒子2上。如此可獲得異向性導電膜1A。
又,於轉印模具之凹部填充導電粒子後,使絕緣性樹脂黏合劑覆於其上,使導電粒子自轉印模具轉印至絕緣性樹脂黏合劑之表面,將絕緣性樹脂黏合劑上之導電粒子壓入至絕緣性樹脂黏合劑內,藉此亦可製造異向性導電膜。藉由該壓入時之按壓力、溫度等可調整導電粒子之埋入量(Lb)。又,藉由壓入時之絕緣性樹脂黏合劑之黏度、壓入速度、溫度等可調整凹部3b、3c之形狀及深度。例如,將導電粒子壓入時的絕緣性樹脂黏合劑之黏度設為下限較佳為3000 Pa・s以上,更佳為4000 Pa・s以上,進而較佳為4500 Pa・s以上,上限設為較佳為20000 Pa・s以下,更佳為15000 Pa・s以下,進而較佳為10000 Pa・s以下。又,可於較佳為40~80℃、更佳為50~60℃獲得此種黏度。更具體而言,於製造絕緣性樹脂黏合劑之表面具有圖14所示之凹部3b的異向性導電膜1a之情形時,較佳將導電粒子壓入時之絕緣性樹脂黏合劑之黏度設為8000 Pa・s(50~60℃),於製造具有圖16所示之凹部3c的異向性導電膜1c之情形時,較佳將導電粒子壓入時之絕緣性樹脂黏合劑之黏度設為4500 Pa・s(50~60℃)。
再者,作為轉印模具,除了於凹部中填充導電粒子者以外,亦可使用對凸部之頂面賦予微黏著劑並使導電粒子附著於該頂面而成者。
該等轉印模具可使用或應用機械加工、光蝕刻法、印刷法等公知之技術而製造。
又,作為將導電粒子配置為特定之排列之方法,亦可使用利用雙軸延伸膜之方法等代替利用轉印模具之方法。
<捲裝體> 異向性導電膜為了連續供於電子零件之連接,較佳製成捲繞於捲盤而成之膜捲裝體。膜捲裝體之長度為5 m以上即可,較佳為10 m以上。並不特別存在上限,就出貨物之操作性之方面而言,較佳為5000 m以下,更佳為1000 m以下,進而較佳為500 m以下。
膜捲裝體可為藉由連接帶將短於全長之異向性導電膜連結而成者。連結部位可存在多處,可規則地存在,亦可隨機地存在。連接帶之厚度只要不阻礙性能,則並無特別限制,但由於若過厚,則會影響到樹脂之溢出或黏連,因此較佳為10~40 μm。又,膜之寬度並無特別限制,作為一例,為0.5~5 mm。
根據膜捲裝體,可實現連續之異向性導電連接,有助於降低連接體之成本。
<連接結構體> 本發明之異向性導電膜於藉由熱或光將FPC、IC晶片、IC模組等第1電子零件與FPC、剛性基板、陶瓷基板、玻璃基板、塑膠基板等第2電子零件進行異向性導電連接時可較佳地應用。又,亦可將IC晶片或IC模組進行堆疊而將第1電子零件彼此進行異向性導電連接。由此獲得之連接結構體及其製造方法亦為本發明之一部分。
作為使用異向性導電膜的電子零件之連接方法,就提高連接可靠性之方面而言,較佳為例如將於異向性導電膜之膜厚方向導電粒子靠近存在之側的界面暫貼於配線基板等第2電子零件,對暫貼之異向性導電膜搭載IC晶片等第1電子零件,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。再者,於該連接中,就連接作業效率之方面而言,較佳將電子零件之端子之長邊方向與異向性導電膜之短邊方向對齊。 實施例
實驗例1~實驗例8 (異向性導電膜之製作) 關於用於COG連接之異向性導電膜,以如下方式研究絕緣性樹脂黏合劑之樹脂組成與導電粒子之配置對膜形成性能與導通特性造成之影響。
首先,以表1所示之組成分別製備形成絕緣性樹脂黏合劑及絕緣性接著層之樹脂組成物。於該情形時,藉由絕緣性樹脂組成物之製備條件調整樹脂組成物之最低熔融黏度。藉由棒式塗佈機將形成絕緣性樹脂黏合劑之樹脂組成物塗佈於膜厚50 μm之PET膜上,於80℃之烘箱中乾燥5分鐘,而於PET膜上形成表2所示之厚度La的絕緣性樹脂黏合劑層。以同樣之方式將絕緣性接著層以表2所示之厚度形成於PET膜上。
[表1] (質量份)
   COG用組成表 組成
A B C D
絕緣性樹脂黏合劑 苯氧基樹脂(YP-50,新日鐵住友化學股份有限公司) 50 45 40 37
二氧化矽填料(Aerosil R805,日本艾羅西爾股份有限公司) 20 10 10 8
液狀環氧樹脂(jER828,三菱化學股份有限公司) 25 40 45 50
矽烷偶合劑(KBM-403,信越化學工業股份有限公司) 2 2 2 2
熱陽離子聚合起始劑(SI-60L,三新化學工業股份有限公司) 3 3 3 3
絕緣性接著層 苯氧基樹脂(YP-50,新日鐵住友化學股份有限公司) 40
二氧化矽填料(Aerosil R805,日本艾羅西爾股份有限公司) 5
液狀環氧樹脂(jER828,三菱化學股份有限公司) 50
矽烷偶合劑(KBM-403,信越化學工業股份有限公司) 2
熱陽離子聚合起始劑(SI-60L,三新化學工業股份有限公司) 3
繼而,以導電粒子之俯視下之配置成為表2所示之配置,其重複單元中之最接近導電粒子的中心間距離成為6 μm之方式製作模具。將公知的透明性樹脂之顆粒以經熔融之狀態流入至該模具中,冷卻使其凝固,藉此形成凹部為表2所示之配置的樹脂模。此處,於實驗例8中將導電粒子之配置設為六方晶格排列(個數密度32000個/mm 2),使其晶格軸之一相對於異向性導電膜之長邊方向傾斜15°。
作為導電粒子而準備金屬被覆樹脂粒子(積水化學工業股份有限公司,AUL703,平均粒徑3 μm),將該導電粒子填充至樹脂模之凹部中,使上述絕緣性樹脂黏合劑覆於其上,於60℃、0.5 MPa進行按壓,藉此使其貼合。然後,將絕緣性樹脂黏合劑自模剝離,對絕緣性樹脂黏合劑上之導電粒子進行加壓(按壓條件:60~70℃、0.5 Mpa),藉此將其壓入至絕緣性樹脂黏合劑中,而製作將導電粒子以表2所示之狀態埋入至絕緣性樹脂黏合劑中之膜。於該情形時,導電粒子之埋入狀態係根據壓入條件加以控制。其結果,於實驗例4中,壓入導電粒子後膜形狀未得到維持,除此以外之實驗例中,可製作埋入有導電粒子之膜。於利用金屬顯微鏡之觀察中,如表2所示般於埋入之導電粒子的露出部分之周圍或埋入之導電粒子的正上方觀察到凹部。再者,於除實驗例4以外之各實驗例中觀察到導電粒子的露出部分周圍之凹部,及導電粒子正上方之凹部之兩者,於表4中按各實驗例示出最明確地觀察到凹部者之測量值。
藉由將絕緣性接著層積層於埋入有導電粒子之膜的壓入導電粒子之側,而製作樹脂層為2層型之異向性導電膜。但是於實驗例4中,壓入導電粒子後膜形狀未得到維持,因此未進行以下之評價。
(評價) 對於各實驗例之異向性導電膜,以如下方式測量(a)初始導通電阻與(b)導通可靠性。將結果示於表2。
(a)初始導通電阻 將各實驗例之異向性導電膜挾持於載台上之玻璃基板與按壓工具側之導通特性評價用IC之間,藉由按壓工具進行加熱加壓(180℃、5秒)而獲得各評價用連接物。於該情形時,將利用按壓工具而獲得之推力變為低(40 MPa)、中(60 MPa)、高(80 MPa)之3個階段,而獲得3種評價用連接物。
此處,關於導通特性評價用IC與玻璃基板,該等之端子圖案相對應,尺寸如下所述。又,於連結評價用IC與玻璃基板時,將異向性導電膜之長邊方向與凸塊之短邊方向對齊。
導通特性評價用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50 μm、凸塊高度15 μm
玻璃基板(ITO配線) 玻璃材質:康寧公司製造之1737F 外形:30×50 mm 厚度:0.5 mm 電極:ITO配線
測量獲得之評價用連接物之初始導通電阻,按照以下之3個階段之評價基準進行評價。 初始導通電阻之評價基準(實用上,只要未達2 Ω,則無問題) A:未達0.4 Ω B:0.4 Ω以上且未達0.8 Ω C:0.8 Ω以上
(b)導通可靠性 進行將(a)中製作之評價用連接物於溫度85℃、濕度85%RH之恆溫槽中放置500小時之可靠性試驗,與初始導通電阻同樣地測量之後的導通電阻,按照以下之3個階段之評價基準進行評價。
導通可靠性之評價基準(實用上,只要未達5 Ω,則無問題) A:未達1.2 Ω B:1.2 Ω以上且未達2 Ω C:2 Ω以上
[表2]
COG評價 實驗例1 實驗例2 實驗例3 實驗例4 實驗例5 實驗例6 實驗例7 實驗例8
樹脂之組成 A B C D A A A A
導電粒子壓入後之膜形狀 OK OK OK NG OK OK OK OK
導電粒子粒徑:D(μm) 3 3 3 3 3 3 3 3
導電粒子之配置 圖1A 圖1A 圖1A 圖1A 圖4A 圖8 圖10 六方晶格
最接近導電粒子之中心間距離(μm) 6 6 6 6 6 6 6 6
厚度 (μm) 絕緣性樹脂黏合劑層(La) 4 4 4 4 4 4 4 4
絕緣性接著層 14 14 14 14 14 14 14 14
La/D 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3
最低熔融黏度 (Pa·s) 絕緣性樹脂黏合劑層 8000 2000 1500 800 8000 8000 8000 8000
絕緣性接著層 800 800 800 800 800 800 800 800
合計熔融黏度 1200 900 900 800 1200 1200 1200 1200
60℃黏度 (Pa·s) 絕緣性樹脂黏合劑層 12000 3000 2000 1100 12000 12000 12000 12000
導電粒子之埋入狀態                        
埋入率(100×Lb/D)% >80 >95 >95 - >80 >80 >80 >80
露出徑Lc(μm) <2.8 <2.5 <2.5 - <2.8 <2.8 <2.8 <2.8
凹部之有無 -
凹部之最大深度Le (相對於導電粒子粒徑D之比例) <50% <50% <50% - <50% <50% <50% <50%
凹部之最大徑Ld (相對於導電粒子粒徑D之比例) <1.3 <1.3 <1.3 - <1.3 <1.3 <1.3 <1.3
評價                        
推力:低 40 MPa 初始導通電阻 A A A - A A A B
導通可靠性 A A A - A A A B
推力:中 60 MPa 初始導通電阻 A A A - A A A B
導通可靠性 A A A - A A A B
推力:高 80 MPa 初始導通電阻 A A A - A A A A
導通可靠性 A A A - A A A A
根據表2可知,於絕緣性樹脂層之最低熔融黏度為800 Pa・s之實驗例4中難以形成於導電粒子附近之絕緣性樹脂黏合劑中具有凹部之膜。另一方面,可知於絕緣性樹脂黏合劑之最低熔融黏度為1500 Pa・s以上之實驗例中,藉由調整導電粒子之埋入時之條件而可於絕緣性樹脂黏合劑之導電粒子附近形成凸部,且如此獲得之異向性導電膜於用於COG時導通特性良好。又,可知與六方晶格排列之實驗例8相比,於導電粒子之個數密度較低的實驗例1~7中,可於更低之壓力下進行異向性導電連接。
(c)短路發生率 使用實驗例1~3與5~8之異向性導電膜,使用以下之短路發生率之評價用IC,於180℃、60 MPa、5秒之連接條件下獲得評價用連接物,測量獲得之評價用連接物之短路數,以測量之短路數相對於評價用IC之端子數之比例之形式求出短路發生率。
短路發生率之評價用IC(7.5 μm空間之梳齒TEG(test element group,測試元件組): 外形:15×13 mm 厚度:0.5 mm 凸塊規格:尺寸25×140 μm、凸塊間距離7.5 μm、凸塊高度15 μm
短路只要未達50 ppm,則於實用上較佳,實驗例1~3與5~8之異向性導電膜全部未達50 ppm。
再者,對於除實驗例4以外之各實驗例,測量由每個凸塊捕捉之導電粒子,結果均捕捉到10個以上之導電粒子。
實驗例9~16 (異向性導電膜之製作) 關於用於FOG連接之異向性導電膜,以如下方式研究絕緣性樹脂黏合劑之樹脂組成與導電粒子之配置對膜形成性能與導通特性造成之影響。
即,以表3所示之組成製備形成絕緣性樹脂黏合劑與絕緣性接著層之樹脂組成物,使用該等,以與實驗例1同樣之方式製作異向性導電膜。將該情形時之導電粒子之配置與最接近導電粒子之中心間距離示於表4。於實驗例16中將導電粒子之配置設為六方晶格排列(個數密度15000個/mm 2),使其晶格軸之一相對於異向性導電膜之長邊方向傾斜15°。
於該異向性導電膜之製作步驟中,將導電粒子壓入至絕緣性樹脂黏合劑中後,於實驗例12中膜形狀未得到維持,於除此以外之實驗例中膜形狀得以維持。因此,對於除實驗例12以外之實驗例之異向性導電膜,利用金屬顯微鏡觀察導電粒子之埋入狀態並進行測量,進而進行以下之評價。將各實驗例中之導電粒子之埋入狀態示於表4。表4所示之埋入狀態與表2同樣,為針對各實驗例最明確地觀察到絕緣性樹脂黏合劑之凹部者之測量值。
(評價) 對於各實驗例之異向性導電膜,以如下方式測量(a)初始導通電阻與(b)導通可靠性。將結果示於表4。
(a)初始導通電阻 將各實驗例中獲得之異向性導電膜按照2 mm×40 mm裁斷,挾持於導通特性之評價用FPC與玻璃基板之間,以工具寬度2 mm進行加熱加壓(180℃、5秒),而獲得各評價用連接物。於該情形時,將利用按壓工具而獲得之推力變為低(3 MPa)、中(4.5 MPa)、高(6 MPa)之3個階段,而獲得3種評價用連接物。與實驗例1同樣地測量獲得之評價用連接物之導通電阻,按照以下之基準以3個階段評價該測量值。
評價用FPC: 端子間距:20 μm 端子寬度/端子間空間:8.5 μm/11.5 μm 聚醯亞胺膜厚(PI)/銅箔厚(Cu)=38/8、鍍錫(Sn plating)
無鹼玻璃基板: 電極:ITO配線 厚度:0.7 mm
初始導通電阻之評價基準 A:未達1.6 Ω B:1.6 Ω以上且未達2.0 Ω C:2.0 Ω以上
(b)導通可靠性 將(a)中製作之評價用連接物於溫度85℃、濕度85%RH之恆溫槽中放置500小時,與初始導通電阻同樣地測量之後的導通電阻,按照以下之基準以3個階段評價該測量值。
導通可靠性之評價基準 A:未達3.0 Ω B:3.0 Ω以上且未達4 Ω C:4.0 Ω以上
根據表4可知,於絕緣性樹脂層之最低熔融黏度為800 Pa・s之實驗例12中,難以形成具有凹部之膜。另一方面,可知於絕緣性樹脂層之最低熔融黏度為1500 Pa・s以上之實驗例中,藉由調整導電粒子之埋入時之條件,可於絕緣性樹脂黏合劑之導電粒子附近形成凹部,且如此獲得之異向性導電膜於用於FOG時導通特性良好。
(c)短路發生率 對已測量初始導通電阻之評價用連接物之短路數進行測量,根據測量獲得之短路數與評價用連接物之間隙數求出短路發生率。只要短路發生率未達100 ppm,則於實用上無問題。 實驗例9~11與13~16之短路發生率均未達100 ppm。
再者,對於除實驗例12以外之各實驗例,測量由每個凸塊捕捉之導電粒子,結果均捕捉到10個以上之導電粒子。
[表3] (質量份)
   FOG用組成表 組成
E F G H
絕緣性樹脂黏合劑 苯氧基樹脂(YP-50,新日鐵住友化學股份有限公司) 55 45 25 5
苯氧基樹脂(FX-316ATM55,新日鐵住金化學股份有限公司)       20 40
2官能丙烯酸酯(A-DCP,新中村化學工業股份有限公司) 20 20 20 20
2官能丙烯酸胺酯低聚物(UN-9200A,根上工業股份有限公司) 25 35 35 35
矽烷偶合劑(A-187,Momentive Performance Materials股份有限公司) 1 1 1 1
磷酸甲基丙烯酸酯(KAYAMER PM-2,日本化藥股份有限公司) 1 1 1 1
過氧化苯甲醯(Nyper BW,日本油脂股份有限公司) 5 5 5 5
絕緣性接著層 苯氧基樹脂(FX-316ATM55,新日鐵住金化學股份有限公司) 50
2官能丙烯酸酯(A-DCP,新中村化學工業股份有限公司) 20
2官能丙烯酸胺酯低聚物(UN-9200A,根上工業股份有限公司) 30
矽烷偶合劑(A-187,Momentive Performance Materials股份有限公司) 1
磷酸甲基丙烯酸酯(KAYAMER PM-2,日本化藥股份有限公司) 1
過氧化苯甲醯(Nyper BW,日本油脂股份有限公司) 5
[表4]
FOG評價 實驗例9 實驗例10 實驗例11 實驗例12 實驗例13 實驗例14 實驗例15 實驗例16
樹脂之組成 E F G H E E E E
導電粒子壓入後之膜形狀 OK OK OK NG OK OK OK OK
導電粒子粒徑:D(μm) 3 3 3 3 3 3 3 3
導電粒子之配置 圖1A 圖1A 圖1A 圖1A 圖4A 圖9 圖11 六方晶格
最接近導電粒子之中心間距離(μm) 9 9 9 9 9 9 9 9
厚度 (μm) 絕緣性樹脂黏合劑層(La) 4 4 4 4 4 4 4 4
絕緣性接著層 14 14 14 14 14 14 14 14
La/D 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3
最低熔融黏度 (Pa·s) 絕緣性樹脂黏合劑層 8000 2000 1500 800 8000 8000 8000 8000
絕緣性接著層 800 800 800 800 800 800 800 800
合計熔融黏度 1200 900 900 800 1200 1200 1200 1200
60℃黏度 (Pa·s) 絕緣性樹脂黏合劑層 12000 3000 2000 1100 12000 12000 12000 12000
導電粒子之埋入狀態                        
埋入率(100×Lb/D)% >80 >95 >95 - >80 >80 >80 >80
露出徑Lc(μm) <2.8 <2.5 <2.5 - <2.8 <2.8 <2.8 <2.8
凹部之有無 -
凹部之最大深度Le (相對於導電粒子粒徑D之比例) <50% <50% <50% - <50% <50% <50% <50%
凹部之最大徑Ld (相對於導電粒子粒徑D之比例) <1.3 <1.3 <1.3 - <1.3 <1.3 <1.3 <1.3
評價                        
推力:低 3 MPa 初始導通電阻 A A A - A A A B
導通可靠性 A A A - A A A B
推力:中 4.5 MPa 初始導通電阻 A A A - A A A B
導通可靠性 A A A - A A A B
推力:高 6 MPa 初始導通電阻 A A A - A A A A
導通可靠性 A A A - A A A A
1A、1Ba、1Bb、1Ca、1Cb、1Da、1Db、1Ea、1Eb、1F、1G、1H、1I、1J、1K、1L、1M、1a、1b、1c、1d、1e:異向性導電膜 2、2a、2b、2c、2d、2e、2f、2g、2h、2p、2q、2r、2s、2t、2u:導電粒子 3:絕緣性樹脂黏合劑 4:絕緣性接著層 5、5B:重複單元
[圖1A]係對實施例之異向性導電膜1A的導電粒子之配置進行說明的俯視圖。 [圖1B]係對實施例之異向性導電膜1A的導電粒子之配置進行說明的俯視圖。 [圖1C]係實施例之異向性導電膜1A的剖面圖。 [圖2A]係對實施例之異向性導電膜1Ba的導電粒子之配置進行說明的俯視圖。 [圖2B]係對實施例之異向性導電膜1Bb的導電粒子之配置進行說明的俯視圖。 [圖3A]係對實施例之異向性導電膜1Ca的導電粒子之配置進行說明的俯視圖。 [圖3B]係對實施例之異向性導電膜1Cb的導電粒子之配置進行說明的俯視圖。 [圖4A]係對實施例之異向性導電膜1Da的導電粒子之配置進行說明的俯視圖。 [圖4B]係對實施例之異向性導電膜1Db的導電粒子之配置進行說明的俯視圖。 [圖5A]係對實施例之異向性導電膜1Ea的導電粒子之配置進行說明的俯視圖。 [圖5B]係對實施例之異向性導電膜1Eb的導電粒子之配置進行說明的俯視圖。 [圖6]係對實施例之異向性導電膜1F的導電粒子之配置進行說明的俯視圖。 [圖7]係對實施例之異向性導電膜1G的導電粒子之配置進行說明的俯視圖。 [圖8]係對實施例之異向性導電膜1H的導電粒子之配置進行說明的俯視圖。 [圖9]係對實施例之異向性導電膜1I的導電粒子之配置進行說明的俯視圖。 [圖10]係對實施例之異向性導電膜1J的導電粒子之配置進行說明的俯視圖。 [圖11]係對實施例之異向性導電膜1K的導電粒子之配置進行說明的俯視圖。 [圖12]係對實施例之異向性導電膜1L的導電粒子之配置進行說明的俯視圖。 [圖13係對實施例之異向性導電膜1M的導電粒子之配置進行說明的俯視圖。 [圖14]係實施例之異向性導電膜1a的剖面圖。 [圖15]係實施例之異向性導電膜1b的剖面圖。 [圖16]係實施例之異向性導電膜1c的剖面圖。 [圖17]係實施例之異向性導電膜1d的剖面圖。 [圖18]係實施例之異向性導電膜1e的剖面圖。

Claims (10)

  1. 一種異向性導電膜,其於絕緣性樹脂黏合劑中配置有導電粒子,且 於俯視下重複配置多角形之重複單元,該多角形之重複單元係將複數個導電粒子之中心依序連結而形成, 重複單元之多角形具有與異向性導電膜之長邊方向或短邊方向斜交之邊。
  2. 如申請專利範圍第1項之異向性導電膜,其中,重複單元配置於異向性導電膜之一面。
  3. 如申請專利範圍第1或2項之異向性導電膜,其中,重複單元為梯形。
  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,形成重複單元之多角形之各邊與異向性導電膜之長邊方向或短邊方向斜交。
  5. 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,形成重複單元之多角形具有異向性導電膜之長邊方向或短邊方向之邊。
  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,於以構成重複單元之多角形之一邊為中心而使該多角形反轉之情形時,反轉後之重複單元之多角形之一邊與反轉前鄰接之重複單元之一邊重疊。
  7. 如申請專利範圍第1至6項中任一項之異向性導電膜,其中,導電粒子單元形成正多角形之一部分。
  8. 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,構成導電粒子單元之導電粒子之配置與無間隙地排列正六角形之情形時之六角形的頂點重疊。
  9. 一種連接結構體,其藉由申請專利範圍第1至8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。
  10. 一種連接結構體之製造方法,其藉由經由異向性導電膜將第1電子零件與第2電子零件進行熱壓接而製造第1電子零件與第2電子零件之連接結構體,且使用申請專利範圍第1至8項中任一項之異向性導電膜作為異向性導電膜。
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