TW202014305A - 含填料膜 - Google Patents
含填料膜 Download PDFInfo
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- TW202014305A TW202014305A TW108119806A TW108119806A TW202014305A TW 202014305 A TW202014305 A TW 202014305A TW 108119806 A TW108119806 A TW 108119806A TW 108119806 A TW108119806 A TW 108119806A TW 202014305 A TW202014305 A TW 202014305A
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- resin layer
- insulating resin
- containing film
- film
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C09J11/04—Non-macromolecular additives inorganic
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- C09J171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C09J171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
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Abstract
於絕緣性樹脂層10保持填料2及微小固形物3,於俯視時填料2重複特定排列之含填料膜1A係:以平滑面夾著該含填料膜1A而以特定之熱壓接條件熱壓接之情形時,其熱壓接後之填料之重複間距相對於熱壓接前之比率為300%以內。該含填料膜1A之一製造方法具有如下步驟:於剝離基材20a上形成絕緣性樹脂層11之步驟;自絕緣性樹脂層11之與剝離基材20a相反側之面壓入填料2之步驟;將壓入有填料2之絕緣性樹脂層11及與該絕緣性樹脂層不同之絕緣性樹脂層12以將其等之剝離基材20a、20b設為外側的方式積層之步驟。根據該含填料膜1A,將該膜1A熱壓接於物品之情形時之填料排列之混亂得到抑制。
Description
本發明係關於一種含填料膜。
填料分散於樹脂層之含填料膜使用於消光膜、聚光器用膜、光學膜、標籤用膜、抗耐電用膜、導電膜、各向異性導電膜等各種用途(專利文獻1、專利文獻2、專利文獻3、專利文獻4)。於將含填料膜熱壓接至物品而使用之情形時,在光學特性、機械特性、或電特性之方面而言,較理想的是抑制形成含填料膜之樹脂於熱壓接時不必要地流動,抑制填料之偏集存在。特別是,作為填料而含有導電粒子,於將含填料膜用作供於安裝電子零件之各向異性導電膜之情形時,若為了可應對電子零件之高密度安裝而使導電粒子高密度地分散於絕緣性樹脂層,則由於安裝電子零件時之樹脂流動,導電粒子不必要地移動而偏集存在於端子間成為發生短路之因素,因此較理想的是抑制此種樹脂流動。
對此,進行使絕緣性樹脂層含有熔融黏度調整劑或搖變劑等微小固形物之情形(專利文獻5、6)。
又,為了兼顧使導電粒子高密度地分散於絕緣性樹脂層之情形時之電子零件之端子的導電粒子之捕捉性之提高及短路之抑制,進行規則地配置導電粒子之情形(專利文獻5、6)。
[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6187665號公報
專利文獻6:日本特開2016-031888號公報
[發明所欲解決之課題]
通常,含有微小固形物之絕緣性樹脂層係藉由分散有微小固形物之絕緣性樹脂層形成用組成物之塗佈乾燥而形成。然而,於藉由絕緣性樹脂層形成用組成物之塗佈乾燥形成高濃度地含有微小固形物之絕緣性樹脂層之情形時,在絕緣性樹脂層之乾燥面(即,絕緣性樹脂層形成用組成物之塗佈層中之包含於該組成物之溶劑逐漸蒸發之面)形成由微小固形物導致之粗糙,因此絕緣性樹脂層之黏著性下降,安裝電子零件時之暫時壓接並未均勻地進行,貼合狀態變得不穩定。又,有正式壓接時之熱壓接亦未均勻地進行而規則性地排列於絕緣性樹脂層之導電粒子發生排列之混亂,對提高電子零件之端子中之導電粒子之捕捉性或抑制短路造成不良影響之虞。該問題特別是於電子零件為小型且端子尺寸狹小化之情形時變明顯。又,亦存在如下情形:若使膜厚變薄,則含填料膜表面之黏著性下降之問題較上述膜厚較厚之情形變明顯。
對此,本發明之課題在於:於微小固形物以適當之摻合量分散於絕緣性樹脂層,導電粒子等填料藉由重複特定之排列而規則性地排列於該絕緣性樹脂層之含填料膜中,抑制於將含填料膜熱壓接於物品之情形時之填料之排列混亂。
[解決課題之技術手段]
本發明人發現如下情形從而完成本發明:於利用藉由塗佈含有微小固形物之絕緣性樹脂層形成用組成物而形成絕緣性樹脂層之步驟、及將填料壓入至絕緣性樹脂層之步驟製造於絕緣性樹脂層保持有導電粒子等填料、及形成素材與該填料不同之微小固形物之含填料膜之情形時,若不使含填料膜之表面產生絕緣性樹脂層之乾燥面,則將含填料膜熱壓接至物品時之填料之排列混亂減少。
即,本發明提供一種含填料膜,其於絕緣性樹脂層保持填料、及形成素材與填料不同之微小固形物,且於俯視下填料重複特定排列,
以平滑面夾著含填料膜而以特定之熱壓接條件熱壓接之情形時,其熱壓接後之填料之重複間距相對於熱壓接前之比率為300%以內,特別是提供絕緣性樹脂層由2層之絕緣性樹脂層之積層體形成之態樣、及30~200℃之範圍之最低熔融黏度低於絕緣性樹脂層之低黏度樹脂層積層於絕緣性樹脂層的態樣。
又,本發明提供一種作為該含填料膜之第1製造方法之含填料膜之製造方法,其具有如下步驟:將含有微小固形物之絕緣性樹脂層形成用組成物塗佈至剝離基材上,於剝離基材上形成絕緣性樹脂層之步驟;
自絕緣性樹脂層之與剝離基材相反側之面壓入填料之步驟;
將壓入有填料之絕緣性樹脂層及與該絕緣性樹脂層不同之絕緣性樹脂層以將其等之剝離基材設為外側的方式積層之步驟;
提供一種作為第2製造方法之含填料膜之製造方法,其具有如下步驟:將含有微小固形物之絕緣性樹脂層形成用組成物塗佈至剝離基材上,於剝離基材上形成絕緣性樹脂層之步驟;
藉由將2個絕緣性樹脂層以將其等之剝離基材設為外側之方式積層而形成絕緣性樹脂層之積層體的步驟;
將填料壓入至該絕緣性樹脂層之積層體之步驟;
提供一種作為第3製造方法之含填料膜之製造方法,其具有如下步驟:將含有微小固形物之絕緣性樹脂層形成用組成物塗佈至剝離基材上,於剝離基材上形成絕緣性樹脂層之步驟;
將30~200℃之範圍之最低熔融黏度低於絕緣性樹脂層之低黏度樹脂層的形成用組成物塗佈至剝離基材,於剝離基材上形成低黏度樹脂層之步驟;
藉由將絕緣性樹脂層及低黏度樹脂層以將其等之剝離基材設為外側之方式積層而形成絕緣性樹脂層與低黏度樹脂層之積層體的步驟;
剝離絕緣性樹脂層之剝離基材,自將剝離基材剝離之絕緣性樹脂層之面壓入填料之步驟;
提供一種作為第4製造方法之含填料膜之製造方法,其具有如下步驟:將含有微小固形物之絕緣性樹脂層形成用組成物塗佈至剝離基材上,於剝離基材上形成絕緣性樹脂層之步驟;
將30~200℃之範圍之最低熔融黏度低於絕緣性樹脂層之低黏度樹脂層的形成用組成物塗佈至剝離基材,於剝離基材上形成低黏度樹脂層之步驟;
將填料壓入至絕緣性樹脂層之與剝離基材相反側之面之步驟;
將壓入有填料之絕緣性樹脂層及形成於剝離基材上之低黏度樹脂層以將其等之剝離基材設為外側的方式積層之步驟。
[發明之效果]
根據本發明之含填料膜之製造方法,即便於絕緣性樹脂層以於調整黏度等方面而言適當之摻合量含有微小固形物,亦不於含填料膜之表面形成粗糙,因此膜表面對各種物品具有良好之黏著性。因此,藉由熱壓接而貼附於物品之含填料膜之填料可大致維持熱壓接前之特定排列。
例如,於本發明之含填料膜之填料為導電粒子之情形時,若將本發明之含填料膜使用於電子零件彼此之各向異性導電連接,則可良好地進行暫時壓接,於正式壓接時導電粒子之排列亦難以發生混亂,故而可大致維持熱壓接前之特定排列。藉此,於電子零件為小型且端子尺寸狹小化之情形時,亦可良好地將電子零件彼此各向異性導電連接。
以下,一面參照圖式,一面詳細地對本發明之含填料膜之一例進行說明。再者,於各圖中,相同符號表示相同或等同之構成要素。
<含填料膜1A之整體構成>
圖1A係表示實施例之含填料膜1A之填料配置之俯視圖,圖1B係其X-X剖面圖。該含填料膜1A係含有導電粒子作為填料2且用作各向異性導電膜者,以導電粒子重複特定排列之規則性之配置保持於絕緣性樹脂層10。絕緣性樹脂層10除填料2以外含有微小固形物3。於如下所述般以平滑面夾著以往之含填料膜進行熱壓接之情形時,熱壓接前之規則性之填料之配置於熱壓接後擴展,排列之重複間距相對於熱壓接前變寬,重複間距之不均亦變大,填料之排列發生混亂,但本發明之含填料膜係填料之移動量或排列之混亂較少,熱壓接後之填料之重複間距相對於熱壓接前之比率為300%以內、較佳為250%以內、更佳為200%以內。換言之,根據本發明之含填料膜,藉由在熱壓接前後維持填料配置之相對位置關係,可相對於熱壓接前之最相近填料之中心間距離而將熱壓接後之最相近填料之中心間距離設為3倍以內、2.5倍以內、2倍以內。
本發明之含填料膜具有熱壓接前後之重複間距之比率成為上述數值以下之熱壓接條件。認為其原因在於:根據本發明之含填料膜之製造方法,含填料膜1A之表面為來自剝離基材之剝離面,故而即便絕緣性樹脂層10大量地含有微小固形物3,含填料膜1A之表面亦不粗糙而為平滑面,若將該平滑面貼合至物品而進行加熱加壓,則均勻地按壓含填料膜,微小固形物不阻礙按壓力均勻地施加至在膜內規則性地排列之填料而抑制填料之排列不均勻地混亂,加熱加壓後之填料之配置成為均勻地擴展最初之排列而成者,熱壓接前後之填料之重複間距之比率局部地變大的部分減少。
再者,因該熱壓接產生之填料之移動量或排列之混亂較少係藉由使構成含填料膜的樹脂層之層厚變薄而進一步變明顯。
又,於不以平滑面進行熱壓接之情形時,因熱壓接產生之填料之移動量或排列之混亂產生不均勻性。因此,於將含填料膜構成為各向異性導電膜之情形時,存在如下情形:若以各向異性導電膜熱壓接微間距之凸塊排列,則填料排列之混亂相對變大。
<填料>
於本發明中,作為填料2,根據含填料膜之用途,自公知之無機系填料(金屬粒子、金屬氧化物粒子、金屬氮化物粒子等)、有機系填料(樹脂粒子、橡膠粒子等)、混合存在有機系材料與無機系材料之填料(例如,核心由樹脂材料形成且表面被金屬鍍覆之粒子(金屬被覆樹脂粒子)、於導電粒子之表面附著絕緣性微粒子而成者,對導電粒子之表面進行絕緣處理而成者等),根據硬度、光學性能等用途所要求之性能適當地選擇。例如,於光學膜或消光膜中,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。於聚光器用膜中,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。於接著膜中,可含有聚合物系橡膠粒子、聚矽氧橡膠粒子等。於導電膜或各向異性導電膜中含有導電粒子。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、於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,於如下方面而言,金屬被覆樹脂粒子較佳:於連接後樹脂粒子反彈,因此變得易於維持與端子之接觸,導通性能穩定。又,亦可藉由公知之技術對導電粒子之表面實施不對導通特性造成障礙之絕緣處理。
<填料之粒徑>
於本發明中,可根據含填料膜之用途決定填料2之粒徑。例如,於將含填料膜用作各向異性導電膜之情形時,為了提高製造含填料膜時之填料之壓入精度,較佳為1 μm以上、更佳為2.5 μm以上。又,為了抑制製造含填料膜時之填料之位置偏移之影響,較佳為200 μm以下、更佳為50 μm以下。此處,粒徑係指平均粒徑。可根據平面圖像或剖面圖像求出含填料膜之填料之平均粒徑。又,可使用濕式流式粒徑、形狀分析裝置FPIA-3000(Malvern公司)求出作為含有於含填料膜前之原料粒子之填料之平均粒徑。再者,於在填料附著有絕緣性微粒子等微粒子之情形時,將不含微粒子之直徑設為粒徑。
對於含填料膜之填料之粒徑D之不均,較佳為將CV值(標準偏差/平均)設為20%以下。藉此,於向物品壓接含填料膜時變得易於均勻地按壓含填料膜,可防止按壓力局部地集中。因此,於將含填料膜構成為各向異性導電膜之情形時,提高連接之穩定性,又,於連接後可藉由觀察壓痕或填料之夾持狀態而精確地進行連接狀態之評價。具體而言,於使用各向異性導電膜將電子零件彼此各向異性導電連接後之檢查中,無論為端子尺寸相對較大者(FOB等)、或是相對較小者(COG等)均可藉由觀察壓痕或導電粒子之夾持狀態而精確地進行連接狀態之確認。因此,各向異性連接後之檢查變容易,可期待提高連接步驟之生產性。
<填料之排列>
於俯視本發明之含填料膜時,填料呈重複特定排列之規則性之配置,於圖1A所示之實施例之含填料膜1A中,填料2之配置呈6方晶格排列。於本發明中,作為填料之規則性之配置之例,可列舉正方晶格、長方晶格、斜方晶格等晶格排列。亦可為組合複數個不同形狀之晶格而成者。亦可使填料以特定間隔排列成直線狀之粒子行按照特定之間隔並列。亦可規則性地重複緻密地配置有填料之區域與稀疏地配置之區域。亦可由填料彼此接觸之單元構成填料之規則性之重複單元。於將含填料膜製成各向異性導電膜之情形時,為了兼顧端子之捕捉穩定性及短路之抑制,更佳為將導電粒子設為彼此不接觸之規則性之排列。再者,例如可藉由觀察填料之特定之配置是否於膜之長度方向(將含填料膜製成卷裝體之情形時之捲取方向)上重複而判別填料是否呈規則性的排列。
於規則性地排列填料之情形時,該排列之晶格軸或排列軸可相對於含填料膜之長度方向及與長度方向正交之方向中的至少一者平行,亦可交叉,可根據壓接含填料膜之物品決定。
於含填料膜中,可根據連接之物品或用途決定填料間之距離,填料之個數密度係通常可於10個/mm2
以上且100000個/mm2
以下、較佳為30個/mm2
以上且70000個/mm2
以下之範圍適當地決定。例如,於將含填料膜製成各向異性導電膜之情形時,可根據以各向異性導電膜連接之端子之尺寸、形狀、端子間距適當地決定作為填料2之導電粒子的粒子間距離。又,於將含填料膜製成各向異性導電膜之情形時,導電粒子之個數密度只要為30個/mm2
以上即可,較佳為150~70000個/mm2
。特別是,於微間距用途之情形時,較佳為6000~42000個/mm2
、更佳為10000~40000個/mm2
、進而更佳為15000~35000個/mm2
。又,於導電粒子之粒徑為10 μm以上之情形時,導電粒子之個數密度較佳為30~6000個/mm2
。
又,關於填料之個數密度,於表現出含有填料之效果之方面而言,較佳為將藉由下式算出之填料之面積佔有率設為0.3%以上。另一方面,於抑制為了將含填料膜壓接至物品而按壓治具所需之推力之方面而言,較佳為將填料之面積佔有率設為35%以下,更佳為設為30%以下。
填料之面積佔有率(%)=[俯視時之填料之個數密度]×[1個填料之俯視面積之平均值]×100
填料之個數密度係除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件(例如,WinROOF(三谷商事股份有限公司)、或Azokun(註冊商標)(旭化成工程股份有限公司)等)測量觀察圖像而求出。觀察方法或測量方法並不限定於上述內容。
另一方面,於沿膜厚方向切割含填料膜之剖面圖中(圖1B),較佳為膜厚方向之各填料之頂點與絕緣性樹脂層10之表面或平行於該表面的面對齊成同一平面。藉此,變得易於使含填料膜均勻地壓接至物品。
<微小固形物>
為了將不同於填料2之功能賦予至含填料膜1A,可於絕緣性樹脂層10中含有形成素材與填料2不同之各種微小固形物3。例如,於填料2為導電粒子之情形時,作為微小固形物3,可含有黏度調整劑、搖變劑、聚合起始劑、偶合劑、難燃劑等。更具體而言,例如作為黏度調整劑,可列舉氧化矽粉、氧化鋁粉等。
又,關於填料2與微小固形物3之區分,於使用導電粒子作為填料2且將含填料膜製成各向異性導電膜之情形時,在如專利文獻5中所記載般將微小固形物混練至絕緣性樹脂層,藉由將導電粒子壓入至絕緣性樹脂層而使該絕緣性樹脂層保持導電粒子時,導電粒子與微小固形物係可根據兩者於絕緣性樹脂層之分佈狀態而容易區分。
微小固形物3之粒徑較佳為小於填料2之粒徑,於將含填料膜製成各向異性導電膜之情形時,作為黏度調整劑而含有之微小固形物係較佳為可將平均粒徑設為未達1 μm、更佳為5 nm~0.3 μm,或者較佳為設為作為填料而含有之導電粒子之平均粒徑之1/3~1/2。
關於絕緣性樹脂層10之微小固形物3之含量,於如上述專利文獻5中所記載般藉由將微小固形物混練至絕緣性樹脂層,將導電粒子壓入至絕緣性樹脂層而製造各向異性導電膜之情形時,只要不阻礙導電粒子之壓入,則無特別限制,但就確保導電粒子之配置之精確性之方面而言,較佳為將微小固形物設為3質量%以上、更佳為設為5質量%以上,可按照需要以2個階段進行各向異性導電連接之壓入之程度使微小固形物3以高濃度於絕緣性樹脂層10中含有。另一方面,於為了連接電子零件而對膜確保所需之流動性之方面而言,微小固形物3之含量係相對於絕緣性樹脂層10而較佳為50質量%以下,更佳為40質量%以下,進而較佳為35質量%以下。
<絕緣性樹脂層>
於本發明中,絕緣性樹脂層可由單個絕緣性樹脂層所構成,亦可由複數個絕緣性樹脂層之積層體所構成。圖1A、圖1B所示之含填料膜1A之絕緣性樹脂層10係利用下文敍述之含填料膜之製造方法,將藉由將相同之絕緣性樹脂層形成用組成物塗佈至平滑的剝離基材上並進行乾燥而形成之絕緣性樹脂層11、12以將其等之乾燥面設為內側、將剝離基材側之面設為外側之方式積層而成者。於含填料膜1A中,可觀察到該等2層之絕緣性樹脂層11、12之界面。於塗佈絕緣性樹脂層形成用組成物並進行乾燥之面容易產生因該組成物所含有之微小固形物導致之粗糙,但若如圖1B所示般將絕緣性樹脂層11、12之塗佈乾燥面設為內側來重疊,則含填料膜之表面成為轉印剝離基材之平滑面之面,因此認為變得易於將含填料膜均勻地熱壓接至物品。
<形成絕緣性樹脂層之樹脂組成物>
形成絕緣性樹脂層10之樹脂組成物可根據含填料膜之用途適當地選擇,可由熱塑性樹脂組成物、高黏度黏著性樹脂組成物、硬化性樹脂組成物形成。例如,於將含填料膜製成各向異性導電膜之情形時,可與專利文獻5中記載之形成各向異性導電膜之絕緣性樹脂層之樹脂組成物相同地使用由聚合性化合物及聚合起始劑形成之硬化性樹脂組成物。於該情形時,作為聚合起始劑,可使用熱聚合起始劑,亦可使用光聚合起始劑,且亦可並用其等。例如,使用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。亦可使用熱陰離子聚合起始劑作為熱聚合起始劑。較佳為使用以咪唑改質體為核心且以聚胺酯(polyurethane)被覆其表面而成之微膠囊型潛伏性硬化劑作為熱陰離子聚合起始劑。
<絕緣性樹脂層之最低熔融黏度>
絕緣性樹脂層10之最低熔融黏度係只要可將填料壓入至絕緣性樹脂層,則並無特別限制,但為了抑制將含填料膜1A熱壓接至物品時之填料2之不必要之流動,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、特佳為3000~10000 Pa·s。作為一例,該最低熔融黏度係可使用旋轉式流變儀(TA instruments公司製造),以測定壓力5 g保持固定,使用直徑為8 mm之測定板求出,更具體而言,可藉由如下方式求出:於30~200℃之溫度範圍內,將升溫速度設為10℃/分鐘,將測定頻率設為10 Hz,將對上述測定板之負重變動設為5 g。再者,可藉由變更作為熔融黏度調整劑而含有之微小固形物之種類或摻合量、樹脂組成物之調整條件等而進行最低熔融黏度之調整。
<絕緣性樹脂層之層厚>
如上所述,於含填料膜中,絕緣性樹脂層可由單個絕緣性樹脂層構成,亦可由複數個絕緣性樹脂層之積層體構成,但無論於哪種情形時,為了於在含填料膜之製造步驟中將填料壓入至絕緣性樹脂層時均可穩定地進行填料之壓入,絕緣性樹脂層之層厚較佳為相對於填料2之粒徑而為0.3倍以上,更佳為0.6倍以上,進而較佳為0.8倍以上,特佳為1倍以上。又,絕緣性樹脂層之層厚之上限並無特別限制,絕緣性樹脂層之層厚係根據熱壓接含填料膜之物品適當地調整即可,但若絕緣性樹脂層之層厚變得過厚,則於將含填料膜熱壓接至物品時,填料2變得容易不必要地受到樹脂流動之影響,又,有因絕緣性樹脂層中所含之微小固形物之絕對量變多而阻礙物品之熱壓接之虞。因此,絕緣性樹脂層之層厚較佳為填料2之粒徑之20倍以下、更佳為15倍以下。
另一方面,如下所述,於將含填料膜製成埋入有填料之絕緣性樹脂層與低黏度樹脂層之積層體之情形時,低黏度樹脂層之層厚係根據含填料膜之用途適當地調整即可,但若變得過薄,則層厚之不均相對變大,因此較佳為填料2之粒徑之0.2倍以上、更佳為1倍以上。又,對於低黏度樹脂層之層厚之上限,若變得過厚,則與絕緣性樹脂層之積層之困難性增加,因此較佳為填料2之粒徑之50倍以下、更佳為15倍以下、進而較佳為8倍以下。
又,於將含填料膜製成埋入有填料之絕緣性樹脂層與低黏度樹脂層之積層體之情形時,該等樹脂層之總厚係於抑制將含填料膜熱壓接至物品時之填料2之不必要的流動之方面、抑制將含填料膜製成卷裝體之情形時之樹脂之滲出或黏連的方面、使含填料膜之單位重量之膜長變長之方面等而言,較佳為含填料膜之樹脂層之總厚較薄。然而,若變得過薄,則含填料膜之操作性變差。又,存在變得難以將含填料膜貼合至物品之情形,因此有於將含填料膜熱壓接至物品時之暫時壓接時無法獲得所需之黏著力之虞,且有於正式壓接時因樹脂量不足而亦無法獲得所需之接著力之虞。因此,含填料膜之樹脂層之總厚係相對於填料2之粒徑而較佳為0.6倍以上、更佳為0.8倍以上、進而較佳為1倍以上、特佳為1.2倍以上。
另一方面,組合絕緣性樹脂層與低黏度樹脂層而成之樹脂層之總厚之上限並無特別限制,只要根據熱壓接含填料膜之物品適當地調整即可,但若樹脂層之總厚變得過厚,則於將含填料膜熱壓接至物品時,填料2變得容易不必要地受到樹脂流動之影響,又,有因樹脂層中所含之微小固形物之絕對量變多而阻礙物品之熱壓接之虞,因此樹脂層之總厚較佳為填料2之粒徑之50倍以下、更佳為15倍以下、進而較佳為8倍以下。認為藉由設為4倍以下、較佳為3倍以下,可使樹脂流動對填料配置之影響為最小限度。
於將含填料膜構成為各向異性導電膜之情形時,導電粒子可埋入於絕緣性樹脂層,亦可露出。於將含填料膜構成為各向異性導電膜,設置絕緣性樹脂層及低黏度樹脂層作為樹脂層之情形時,樹脂層之總厚可設為上述範圍,但就於在連接之電子零件中應對凸塊之低高度化之方面而言,較佳為使樹脂層之總厚薄於上述內容。又,藉由使樹脂層較薄,導電粒子與凸塊之接觸變容易。就此種方面而言,樹脂層之總厚之下限較佳為導電粒子之粒徑之0.6倍以上、更佳為0.8倍以上、進而較佳為1倍以上。對於上限,若過高則壓入時所需之推力變得過高,故而可設為導電粒子之粒徑之4倍以下,較佳為3倍以下、更佳為2倍以下、進而較佳為1.8倍以下、特佳為1.5倍以下。絕緣性樹脂層與低黏度樹脂層之厚度之比率係根據導電粒子之粒徑與凸塊高度或謀求之接著力等的關係適當地調整即可。
<絕緣性樹脂層之黏著力>
絕緣性樹脂層較佳為具有可對熱壓接含填料膜之物品實現熱壓接前之暫時壓接之黏著力。含填料膜之黏著力可依據JIS Z 0237測定,又,亦可依據JIS Z 3284-3或ASTM D 2979-01,藉由探針法而作為黏著力測定。無論於含填料膜具有絕緣性樹脂層及低黏度樹脂層作為樹脂層之情形時,或是於僅具有絕緣性樹脂層之情形時,含填料膜之正面及背面各面之藉由探針法測得之黏著力係例如於以探針之壓抵速度30 mm/min、加壓力196.25 gf、加壓時間1.0 sec、剝離速度120 mm/min、測定溫度23℃±5℃測量時,均可將正面及背面中之至少一者設為1.0 kPa(0.1 N/cm2
)以上,較佳為設為1.5 kPa(0.15 N/cm2
)以上,更佳為高於3 kPa(0.3 N/cm2
)。於該情形時,亦可藉由將含填料膜之一面貼附至毛坯玻璃而測定另一面之黏著力。亦可貼附至具有柔軟性之熱塑性樹脂膜(例如,厚度為20 μm以下之未進行脫模處理之PET膜、矽橡膠等)進行測定,而並非貼附至毛坯玻璃。藉由反轉含填料膜之貼附之面,能夠以相同之條件測定含填料膜之正面及背面之黏著力。
特別是,於含填料膜於正面及背面兩面具有剝離基材時,較佳為以與先貼附於電子零件之面相反側之面表現出上述黏著力之方式使用含填料膜的正面及背面,於如製成卷裝體之含填料膜般,含填料膜於其單面具有剝離基材時,較佳為剝離基材側之面表現出上述黏著力。又,於含填料膜具有絕緣性樹脂層及低黏度樹脂層時,較佳為低黏度樹脂層之表面具有上述黏著力。另一方面,含填料膜於正面及背面兩面具有剝離基材時之先貼附於電子零件之面、含填料膜於其單面具有剝離基材時之無剝離基材之側之面、或含填料膜具有絕緣性樹脂層及低黏度樹脂層時之絕緣性樹脂層側之面並非必須具有上述黏著力,但較理想的是具有上述黏著力。如上所述般含填料膜之正面及背面之較佳之黏著力不同的原因如下。即,於將含填料膜構成為各向異性導電膜之情形時,通常各向異性導電膜係進行如下情形:於使用其時將與剝離基材相反側之面貼附至基板等第2電子零件,其次將剝離基材剝離,於將剝離基材剝離之面(即,剝離基材側之面)搭載第1電子零件。其原因在於,此時需確保可精確地固定搭載零件之黏著性能。
再者,推測為於搭載零件較小時,在搭載時即便發生輕微之偏移亦不容許,但即便搭載時所需之黏著力針對更大之搭載零件相對性地下降亦容許。因此,亦可根據搭載零件決定所需之黏著力。
含填料膜之黏著力亦可依據日本特開2017-48358號公報中記載之接著強度試驗求出。於該接著強度試驗中,例如於以2片玻璃板夾著含填料膜,固定一玻璃板且以剝離速度10 mm/min、試驗溫度50℃逐漸剝離另一玻璃板之情形時,可藉由預先增強固定之玻璃板與含填料膜之接著狀態而測定逐漸剝離之玻璃板與和該玻璃板黏合的含填料膜之面之黏著力。可將以此方式測定之黏著力設為較佳為1 N/cm2
(10 kPa)以上、更佳為10 N/cm2
(100 kPa)以上。
此外,含填料膜之黏著力亦可藉由如下試驗求出:對齊試片之一端而黏合,藉由提拉另一端而剝離試片。藉由該試驗方法測量之黏著力亦可為與上述接著強度試驗等同(1 N/cm2
(10 kPa)以上)之結果。於藉由上述接著強度試驗測得之黏著力足夠大時(例如10 N/cm2
(100 kPa)以上),可將藉由該試驗方法測得之黏著力設為藉由上述接著強度試驗測得之黏著力之10%以上。
藉由含填料膜具有上述黏著力,即便熱壓接之物品例如為小於通常之IC晶片之最大尺寸未達0.8 mm的電子零件,亦可消除暫時壓接時之位置偏移之問題,且即便為與大型TV相同程度之最大尺寸為450 cm左右之電子零件,亦可使貼合穩定。
此種黏著性可藉由如下方式賦予至絕緣性樹脂層:適當地調整構成絕緣性樹脂層之樹脂組成,又,藉由下文敍述之含填料膜之製造方法提高構成含填料膜之外表面的絕緣性樹脂層之平滑性。
<含填料膜1A之製造方法>
可如下所述般製造含填料膜1A。首先,進行如下步驟:藉由在PET膜等表面平滑之剝離基材20a塗佈含有上述微小固形物之絕緣性樹脂層形成用組成物並進行乾燥而形成絕緣性樹脂層11(圖2A)。
其次,進行如下步驟:如專利文獻5中記載之各向異性導電膜之製造方法般,於與填料2之規則性的配置對應地形成有凹部之模具21之凹部填充填料2(圖2B),轉印至上述絕緣性樹脂層11之乾燥面(與剝離基材20a相反側之面)11a(圖2C),將該填料2壓入至絕緣性樹脂層11(圖2D)。
另一方面,進行如下步驟:預先與絕緣性樹脂層11相同地於剝離基材20b上形成絕緣性樹脂層12,使該絕緣性樹脂層12與壓入有上述填料之絕緣性樹脂層11以其等之剝離基材20a、20b成為外側之方式對向(圖2E),將該等絕緣性樹脂層積層(圖2F)。以此方式,可獲得含填料膜1A(圖1A)。
<含填料膜之表面之平滑性及熱壓接前後之填料的重複間距之比率>
如上所述般製造之含填料膜1A之表面為剝離基材20a、20b側之絕緣性樹脂層之面11b、12b,因此該面11b、12b係轉印剝離基材20a、20b之表面之平滑性而變平滑。因此,於將含填料膜1A熱壓接至物品時,絕緣性樹脂層11、12對物品之黏著性提高,又,可均勻地按壓含填料膜。藉此,因熱壓接而填料2不均勻地流動之情形得到抑制,熱壓接後之填料2之配置成為最初之規則性的配置均勻地擴大而成者。藉此,於以平滑面夾著含填料膜1A,以與該絕緣性樹脂層之組成等對應之特定之加熱加壓條件熱壓接面積的情形時,熱壓接後之填料之重複間距相對於熱壓接前之比率成為300%以內,與使絕緣性樹脂層之乾燥面11a、12a構成含填料膜之表面之情形相比明顯變小。
關於該填料之重複間距之比率成為300%以內之熱壓接條件,可根據該絕緣性樹脂層之通常之加熱加壓條件適當地選擇溫度、壓力、時間,故而可容易地發現。
可使用玻璃板等作為於調查熱壓接前後之填料之重複間距之比率時夾著含填料膜的平滑面,但亦可使用作為含填料膜之熱壓接對象之物品之平滑面。例如,於將含填料膜構成為各向異性導電膜之情形時,可使用作為連接對象之電極、凸塊等之平滑面。藉此,可評價作為連接對象之該電子零件之熱壓接前後之導電粒子的重複間距之比率。
調查熱壓接前後之填料之重複間距之比率時的平滑面之面積係設為可確認填料之排列之面積即可。於填料配置成晶格狀、或形成具有特定之形狀之群之情形時,可設為存在至少一個單位晶格或特定之形狀之重複單元之面積。較佳為於填料配置成晶格狀之情形時,設為於填料間之間距最小之排列軸上存在較佳為3個以上、更佳為5個以上、進而較佳為10個以上之單位晶格之面積,測量存在於其等之中心之重複單元之距離(例如,於6方晶格排列之情形時為粒子之中心間距離)作為重複間距。於特定之形狀之重複單元之情形時,亦可相同地求出。另一方面,若使熱壓接面積過大,則於測量重複間距時不必要地花費時間,因此設為含有較佳為1000個以下、更佳為500個以下、進而較佳為200個以下、特佳為50個以下之填料之面積。
為了作為平滑面而確保此種面積,於將含填料膜製成各向異性導電膜,評價熱壓接前後之導電粒子之重複間距之比率的情形時,例如可使用進行COG連接之電子零件之面積相對較大之輸入端子作為平滑面。於作為連接對象之電子零件無具有此種面積之端子之情形時,亦可利用存在具有此種面積之端子之電子零件進行評價。作為一例,使用最小之1邊為30 μm以上、較佳為40 μm以上之端子之平滑面。
重複間距之測量數量(N數量)較佳為50以上、更佳為100以上。然而,此種N數量係難以與填料之個數密度對應,故而亦可低於上述填料之個數密度。
重複間距之測量方向較佳為設為熱壓接前後之重複間距之比率變大的方向。藉此,於熱壓接前後之重複間距之比率於測量方向上不均之情形時,亦可將實際之重複間距之比率設為測量出之間距的比率以下,可確認填料配置之精確度。另一方面,於在複數個區域測量重複間距之情形時,亦可於各測量區域內藉由抽樣求出測量部位。例如於1個區域測量特定之N數量之10%之個數,於其他9個區域亦相同地測量N數量之10%之個數,並將該等平均。N數量或於幾個區域測量N數量係可根據熱壓接之對象物而適當地調整。
於使用電子零件之平滑面調查熱壓接前後之導電粒子之重複間距的比率時,存在因樹脂流動而導電粒子之移動量於端子排列方向及與其正交之方向上不同之情形。於該情形時,較佳為於導電粒子之移動量較大之方向上測量間距。
又,於在電子零件之平滑面混合存在尺寸不同之端子之情形時,較佳為選擇端子尺寸或端子間距離較大且端子排列方向上之導電粒子之移動量與正交於上述端子排列方向之方向上的導電粒子之移動量之差較小之部位來測量間距。例如,於COG連接之情形時,輸入端子與輸出端子之端子尺寸或端子間距離不同。於該情形時,利用端子尺寸或端子間距離較大之輸入端子測量間距。藉此,變得易於對導電粒子之移動量及排列之混亂進行評價。
即便含填料膜為除各向異性導電膜以外者,亦可使調查熱壓接前後之填料之重複間距之比率時的上述間距之測量方向、測量部位等相同。又,即便利用作為連接對象之該物品調查熱壓接前後之填料之重複間距的比率,於該物品不存在平滑面之情形時,亦能夠以平滑之玻璃板彼此來代替。於該情形時,熱壓接條件較佳為以成為與連接之物品之熱壓接條件(含填料膜之極限溫度、壓力、壓接時間等)同等之方式調整。
作為間距之測量手段,可列舉光學顯微鏡或金屬顯微鏡、電子顯微鏡等公知之圖像觀察裝置、或WinROOF或Azokun(註冊商標)等測量系統,該等可適當地組合。
根據本發明之含填料膜,提高表面之平滑性,提高對物品之黏著性,藉此可如上所述般將熱壓接後之填料之重複間距相對於熱壓接前之比率減少至300%以下。因此,於將含填料膜1A構成為各向異性導電膜之情形時,提高各向異性導電膜對電子零件之暫時壓接性,於正式壓接時,亦提高電子零件之端子之導電粒子之捕捉性,短路得到抑制。因此,於電子零件之端子尺寸狹小化之情形時,亦可確實地導通且抑制短路。又,藉由提高黏著性,因此無論於大型電子零件中或是小型電子零件中,連接之電子零件之搭載均穩定,連接體之製造變容易,可謀求提高生產性。特別是,端子狹小化之電子零件中,精確地進行對準之必要性提高,因此本發明之含填料膜獲得較大之效果。
<含填料膜1B>
本發明之含填料膜可採用各種態樣。例如,圖3所示之含填料膜1B係相對於上述含填料膜1A於如下方面存在差異:填料2之膜表面側之位置與含填料膜1B之表面(絕緣性樹脂層12之剝離基材側之面12b)於膜厚方向上對齊成同一平面。
該含填料膜1B可藉由與含填料膜1A之製造方法相同地進行如下步驟而製造:形成分別形成於剝離基材20a、20b之絕緣性樹脂層11、12之步驟(圖4A);藉由將剝離基材20a、20b設為外側來積層該等絕緣性樹脂層11、12而形成絕緣性樹脂層之積層體之步驟(圖4B);剝離一剝離基材20b,自剝離後之絕緣性樹脂層12之面12b壓入填料2之步驟(圖4C)。
該含填料膜1B係構成其表面之絕緣性樹脂層之表面11b、12b亦因轉印有剝離基材20a、20b之表面的平滑性而平滑,發揮與含填料膜1A相同之效果。
<含填料膜1C>
圖5所示之含填料膜1C係於上述含填料膜1B之填料之壓入面(剝離基材側之絕緣性樹脂層之面12b)(圖4C)積層低黏度樹脂層15而成者。
低黏度樹脂層15係30~200℃之範圍之最低熔融黏度低於絕緣性樹脂層10之樹脂層。藉由將低黏度樹脂層15積層至絕緣性樹脂層10,於熱壓接介隔含填料膜1C而面對之2個物品之情形時,可提高其等之接著性,特別是,於將填料2設為導電粒子、將含填料膜1C用作各向異性導電膜、將電子零件進行各向異性導電連接時,能夠以低黏度樹脂層15填充由電子零件之電極或凸塊形成之空間而提高電子零件彼此之接著性。
又,絕緣性樹脂層10之最低熔融黏度與低黏度樹脂層15之最低熔融黏度之差越大,則越易於以低黏度樹脂層15填充介隔含填料膜1C連接之2個物品間之空間。因此,於將填料2設為導電粒子,將含填料膜1C用作各向異性導電膜之情形時,變得易於以低黏度樹脂層15填充由電子零件之電極或凸塊形成之空間,變得易於提高電子零件彼此之接著性。又,該差越大則保持填料2之絕緣性樹脂層10之熱壓接時之移動量相對於低黏度樹脂層15相對性地變小,故而變得易於提高端子之導電粒子之捕捉性。
絕緣性樹脂層10之最低熔融黏度A1與低黏度樹脂層15之最低熔融黏度A2之比(A1/A2)係於實用上亦與絕緣性樹脂層10與低黏度樹脂層15之層厚之比率對應,但較佳為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卷裝體之情形時,有發生樹脂之滲出或黏連之虞,因此於實用上較佳為30以下、更佳為15以下。更具體而言,低黏度樹脂層15之較佳之最低熔融黏度滿足上述比且為3000 Pa·s以下、更佳為2000Pa·s以下,特佳為100~2000 Pa·s。
再者,低黏度樹脂層15可藉由在與絕緣性樹脂層10相同之樹脂組成物中調整黏度而形成。亦可視需要而於低黏度樹脂層15中含有微小固形物。
作為低黏度樹脂層15向壓入有填料2之絕緣性樹脂層10之積層方法,如圖6所示,可於剝離膜等剝離基材20c上塗佈低黏度樹脂層形成用組成物並進行乾燥而形成低黏度樹脂層15,使其乾燥面15a與絕緣性樹脂層10之填料2之壓入面對向,於絕緣性樹脂層10積層低黏度樹脂層15。又,於低黏度樹脂層15之微小固形物之含量較低,低黏度樹脂層15之乾燥面15a之黏著性與其相反側之面15b的黏著性無實質性之差異之情形時,亦可於絕緣性樹脂層10之填料2之壓入面直接塗佈低黏度樹脂層形成用組成物而形成低黏度樹脂層15。
<含填料膜1D>
圖7所示之含填料膜1D係填料2之頂部與絕緣性樹脂層10及低黏度樹脂層15之乾燥面彼此對向的積層體之該絕緣性樹脂層10之外表面對齊成同一平面而配置者,可根據以下步驟製造。
即,進行藉由將含有微小固形物之絕緣性樹脂層形成用組成物塗佈至剝離基材20a上並進行乾燥而形成絕緣性樹脂層10之步驟,並且進行藉由將低黏度樹脂層形成用組成物塗佈至剝離基材20c上並進行乾燥而形成低黏度樹脂層15之步驟(圖8A),其次,進行藉由將絕緣性樹脂層10及低黏度樹脂層15以將其等之剝離基材20a、20c設為外側之方式(即,使乾燥面彼此對向)積層而形成絕緣性樹脂層10與低黏度樹脂層15之積層體的步驟(圖8B),進行自該積層體剝離絕緣性樹脂層10之剝離基材20a,自將剝離基材剝離之絕緣性樹脂層之面壓入填料2之步驟(圖8C)。
於以此方式獲得之含填料膜1D中,構成其表面之絕緣性樹脂層之表面10b與低黏度樹脂層15之表面15b係因轉印有剝離基材20a、20c的表面之平滑性而平滑,發揮與含填料膜1A相同之效果。
<含填料膜1E>
圖9所示之含填料膜1E係填料2之頂部與「絕緣性樹脂層10之乾燥面與低黏度樹脂層15的乾燥面對向之積層體」之該絕緣性樹脂層10之乾燥面對齊成同一平面而配置者,可根據以下步驟製造。
即,與製造上述含填料膜1D之情形相同地,首先進行藉由將含有微小固形物之絕緣性樹脂層形成用組成物塗佈至剝離基材20a上並進行乾燥而形成絕緣性樹脂層10之步驟,並且進行藉由將低黏度樹脂層形成用組成物塗佈至剝離基材20c上並進行乾燥而形成低黏度樹脂層15之步驟(圖8A)。其次,進行自絕緣性樹脂層10之與剝離基材20a相反側之面(乾燥面10a)壓入填料2之步驟(圖10A),藉此使填料2之膜厚方向之頂部與絕緣性樹脂層10之乾燥面10a對齊成同一平面(圖10B)。接著,使該乾燥面10a與上述低黏度樹脂層之乾燥面15a對向而積層(圖10C)。
於以此方式獲得之含填料膜1E中,構成其表面之絕緣性樹脂層之表面10b與低黏度樹脂層15之表面15b亦因轉印有剝離基材20a、20c的表面之平滑性而平滑,發揮與含填料膜1A相同之效果。
<含填料膜之卷裝體>
含填料膜就其製品形態而言可製成卷裝體。卷裝體之長度並無特別限制,但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。另一方面,就卷裝體之量產性之方面而言,較佳為5 m以上。
卷裝體亦可為將短於其全長之含填料膜連結而成者。連結部位可規則性或無規地存在於複數個部位。
卷裝體之膜寬並無特別限制,但於將寬幅之含填料膜切割成長條而製造卷裝體之情形時之長條寬度的下限之方面而言,較佳為將膜寬設為0.3 mm以上,就使長條寬度穩定之方面而言,更佳為設為0.5 mm以上。膜寬之上限並無特別限制,但就搬運或操作之觀點而言,較佳為700 mm以下,更佳為600 mm以下。
又,於將含填料膜製成各向異性導電膜之情形時,就實用之操作性之方面而言,較佳為根據連接對象而於0.3~400 mm之間選擇膜寬。即,於各向異性導電膜使用於連接之電子物品之端部之情形時,膜寬較多設為數mm左右以下,於直接貼附至相對較大之電子零件(於一面設置有電極配線及安裝部之基板或切削前之晶圓等)而使用之情形時,存在需要400 mm左右之膜寬之情形。通常,各向異性導電膜之膜寬較多使用0.5~5 mm。
<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相同地黏合至物品而使用,黏合之物品並無特別限制。因此,可介隔含填料膜連接各種第1零件與第2零件而獲得第1物品與第2物品之連接體。例如,於將含填料膜構成為各向異性導電膜之情形時,可使用熱壓接工具將各向異性導電膜使用於利用PN接合之半導體元件(太陽電池等發電元件、CCD等攝像元件、發光元件、帕耳帖元件)、其他各種半導體元件、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電子零件之各向異性導電連接,又,亦可將該含填料膜以除各向異性導電連接以外之用途使用於電子零件。再者,黏合含填料膜之物品之面可平滑,亦可具有階部或凸形狀。
以各向異性導電膜連接之第1電子零件及第2電子零件之形狀、尺寸、用途等並無特別限制。該等電子零件可為小型且端子尺寸狹小化,亦可於搭載電子零件時要求高精度之對準。例如,亦可將凸塊面積極小化成數十μm2
~數千μm2
之電子零件設為連接對象。另一方面,可使用各向異性導電膜進行外形尺寸較大之電子零件之安裝。又,亦可藉由分割所安裝之電子零件而小片化來使用。又,於使用於大型TV等之情形時,亦存在將含填料膜於1個邊貼合1 m以上、例如4.5 m以上之情形。於該情形時,除將含填料膜用作各向異性導電膜以外,亦可用作以填料為間隔物之間隔膜等。
亦可使用本發明之各向異性導電膜堆疊IC晶片或晶圓而多層化。再者,以本發明之各向異性導電膜連接之電子零件並不限定於上述電子零件之示例。近年來,可使用於多樣化之各種電子零件。本發明包含特別是於各種物品黏合本發明之含填料膜而成之膜貼合體,特別是包含介隔各向異性導電膜連接第1電子零件與第2電子零件而成之連接體。
將含填料膜黏合至物品之方法可根據含填料膜之用途而設為壓接、較佳為熱壓接,亦可於黏合時利用光照射。
作為將含填料膜構成為各向異性導電膜之情形時之更具體之使用方法,例如於第1電子零件為IC晶片、第2電子零件為基板之情形時,通常將第1電子零件載置至加壓工具側,將第2電子零件載置至與第1電子零件對向之載置台,預先將各向異性導電膜貼合至第2電子零件,使用加壓工具進行第1電子零件與第2電子零件之熱壓接。於該情形時,亦可預先將各向異性導電膜貼合至第1電子零件,又,第1電子零件並不限定於IC晶片。
於藉由熱壓接連接第1電子零件與第2電子零件時,亦可視需要而於熱壓接前預先排除導電粒子周邊之樹脂來進行暫時壓接。藉此,可減少將各向異性導電膜熱壓接至電子物品時發生之樹脂流動之影響,抑制導電粒子之不必要之流動。具體而言,藉由如下方式將電子零件彼此連接:於進行將連接之一電子零件貼合至各向異性導電膜之一面、將另一電子零件貼合至各向異性導電膜之另一面之暫時壓接時,利用加壓工具按壓電子零件,局部地排除電子零件間之樹脂,其次,作為正式壓接而進行熱壓接(以下,將不僅於正式壓接時進行熱壓接,而且於暫時壓接中亦進行按壓之連接方法稱為藉由2階段壓入實現之連接)。於WO2016/143789中,記載有使用無規地分散有導電粒子之各向異性導電膜進行藉由2階段壓入實現之連接,但若如本發明般於利用規則性地排列有導電粒子之各向異性導電膜連接電子零件彼此之情形時進行此種藉由2階段壓入實現之連接,則可大幅減少熱壓接時之導電粒子之不必要之流動。
於連接第1電子零件與第2電子零件時,該等之個數並不限定於1對1,例如亦可對1個第2電子零件連接複數個第1電子零件。本發明亦包含介隔各向異性導電膜連接第1電子零件與第2電子零件之連接體之製造方法。
實施例
以下,藉由試驗例而更具體地對本發明進行說明。
作為含填料膜,製作比較例1及實施例1~4之各向異性導電膜。
比較例1
(1)絕緣性樹脂層之形成
按照表1所示之成分製備絕緣性樹脂層形成用組成物,塗佈至PET膜並進行乾燥,獲得表2所示之厚度之絕緣性樹脂層(以下,稱為高黏度樹脂層)。該高黏度樹脂層之最低熔融黏度(旋轉式流變儀(TA instruments公司製造)、測定壓力5 g、溫度範圍30~200℃、升溫速度10℃/分鐘、測定頻率10 Hz、測定板直徑8 mm、對測定板之負重變動5 g)為9000 Pa·s。
(2)導電粒子之壓入
使用專利文獻5之實施例中記載之金屬被覆樹脂粒子(積水化學工業(股),AUL703,平均粒徑為3 μm)作為導電粒子,藉由專利文獻5之實施例中記載之方法將該導電粒子貼合至(1)之高黏度樹脂層的乾燥面並進行按壓(60℃、0.5 MPa),藉此將導電粒子壓入至高黏度樹脂層之乾燥面(粒子密度為28000個/mm2
)。於該情形時,導電粒子呈6方晶格排列,使膜厚方向之頂部與高黏度樹脂層之乾燥面成為同一平面。
實施例1
與比較例1相同地於PET膜上形成高黏度樹脂層(層厚為3 μm)。
另一方面,按照表1所示之成分製備低黏度樹脂層形成用組成物,塗佈至PET膜並進行乾燥而形成層厚為3 μm之低黏度樹脂層。該低黏度樹脂層之最低熔融黏度(旋轉式流變儀(TA instruments公司製造)、測定壓力5 g、溫度範圍30~200℃、升溫速度10℃/分鐘、測定頻率10 Hz、測定板直徑8 mm、對測定板之負重變動5 g)為300 Pa·s。
將PET膜上之高黏度樹脂層與PET膜上之低黏度樹脂層之乾燥面彼此黏合而形成該等高黏度樹脂層與低黏度樹脂層之積層體,剝離該高黏度樹脂層側之PET膜,與比較例11相同地於剝離PET膜之高黏度樹脂層之表面貼合導電粒子並壓入。
實施例2
與比較例1相同地於PET膜上形成高黏度樹脂層,於其乾燥面壓入導電粒子。
另一方面,與實施例1相同地於PET膜上形成低黏度樹脂層,將該乾燥面黏合於高黏度樹脂層之乾燥面。
實施例3
與比較例1相同地於PET膜上形成高黏度樹脂層(層厚為3 μm),自其乾燥面壓入導電粒子。
此外,於別的PET膜上另外形成高黏度樹脂層(層厚為3 μm),將兩個高黏度樹脂層之乾燥面彼此黏合。
實施例4
與比較例1相同地於PET膜上形成高黏度樹脂層(層厚為3 μm)。另外形成相同之高黏度樹脂層(層厚為3 μm),將該等高黏度樹脂層之乾燥面彼此黏合,形成高黏度樹脂層為2層之積層體。剝離該積層體之一PET膜,與比較例1相同地於剝離PET膜之高黏度樹脂層之表面貼合導電粒子並壓入。
評價
對各實施例及比較例之各向異性導電膜進行以下(1)~(4)之評價試驗。將(1)~(4)之結果示於表2。然而,由於比較例1係(2)膜表面之黏著性(暫時壓接試驗)之評價結果為NG,故而於(3)導通電阻試驗及(4)導通可靠性試驗中選擇可正常地製造評價用連接物者作為評價對象。
(1)熱壓接前後之粒子排列之重複間距之比率(%)
使用以下之電子零件(a)、(b)作為熱壓接前後之粒子排列之重複間距的比率之評價用電子零件,利用該等電子零件(a)、(b)夾著於實施例及比較例中製作之各向異性導電膜,以溫度180℃、壓力60 MPa、5秒熱壓接含有至少50個以上之導電粒子之凸塊面積(0.0024 mm2
)。於該情形時,在表2所示之膜構成中,於圖中之下側配置電子零件(b)之玻璃基板,於上側配置電子零件(a)之評價用IC。
於凸塊面積之中心部,針對每個凸塊以2個軸測量該熱壓接前之導電粒子之重複間距P0及熱壓接後之導電粒子的重複間距P1(導電粒子之中心間距離)(圖1)。即,分別於角度相對於凸塊排列方向最淺(接***行)且樹脂之移動量較小之軸(A軸)、與角度相對於凸塊排列方向最深且樹脂之移動量較大之軸(B軸)測量熱壓接前之間距P0。對並列之20個以上之凸塊進行該測量,於A軸、B軸之各軸中將測量數量設為50,對各軸求出間距P0之平均值。又,對於熱壓接後之間距P1,亦相同地於A軸、B軸之各軸中將測量數量設為50,對各軸求出間距P1之平均值。並且,對A軸、B軸之各軸求出熱壓接前後之比率((P1/P0)×100%)。
(a)評價用電子零件:
評價用IC
外形:0.7×20.0 mm
厚度:0.2 mm
鍍金凸塊(Au-plated bump):尺寸40 μm×60 μm、凸塊間距離20 μm、凸塊高度5 μm
(b)評價用電子零件:
玻璃基板(ITO配線玻璃基板)
厚度:0.3 mm
(2)膜表面之黏著性
(2-1)暫時壓接試驗
將於實施例及比較例中製作之各向異性導電膜之導電粒子之壓入側表面或其相反側的表面貼附至評價用無鹼玻璃,使用50 μm厚之緩衝材(聚四氟乙烯)以各向異性導電膜之寬度1.5 mm、長度50 mm、壓接溫度70℃、壓接壓力1 MPa、壓接時間1秒進行暫時壓接。並且,於利用鑷子剝離與貼合面相反側之PET膜時,觀察各向異性導電膜是否與PET膜一併剝離。進行100次該剝離,按照以下基準進行評價。
評價基準
OK:於100次中,各向異性導電膜均未自玻璃基板剝離
NG:於100次中,各向異性導電膜自玻璃基板剝離1次以上
再者,於實施例1及實施例2中,載置至平面而利用手指確認觸感,結果低黏度樹脂層側之黏著力大於高黏度樹脂層側之黏著力。
(2-2)黏著力試驗1
依據日本特開2017-48358號公報中記載之接著強度試驗,如圖11所示般交替地重疊2片載玻片(26 mm×76 mm×1 mm)(松波硝子工業股份有限公司)30、31,於上述2片載玻片之間夾著於實施例中製作之各向異性導電膜1。於該情形時,各向異性導電膜使用沖裁成圓形(直徑為10 mm)者,首先使表2所示之「膜構成」之下側之面與下側的載玻片30重疊。接著,將下側之載玻片30載置至安裝時之暫貼之加熱成作為通常的載置台溫度之40~50℃之熱板,利用手指進行按壓而加熱30秒鐘並黏合,將下側之載玻片30與各向異性導電膜之下側之面設為所謂的暫貼狀態。此後,於表2所示之「膜構成」之上側之面載置上側的載玻片31而黏合,呈上側之載玻片31以各向異性導電膜之上側之面的黏著力貼合之狀態。
如上所述,於利用2片載玻片30、31夾著各向異性導電膜1之狀態下,使用島津製作所製造之AGS-X系列以治具固定下側之載玻片30,於溫度50℃如圖12所示般利用治具沿鉛垂方向以10 mm/min提拉上側之載玻片31之兩端部,測定下側之載玻片30與上側之載玻片31分離時之力,將該力之值除以各向異性導電膜1之面積而設為表2之「膜構成」的上側之面之黏著力。於該情形時,在各實施例中各進行2次接著強度試驗,將最低值示於表2。然而,由於實施例3、4難以測定,故而測定值之不均大於實施例1、2。比較例1係根據利用手指觸摸之觸感而黏著力小於實施例3、4,未進行接著強度試驗。
(2-3)黏著力試驗2
使用黏性試驗機(TACII,Rhesca股份有限公司)以如下方式於22℃之環境下測定黏著力(tack force)。首先,使於實施例中製作之各向異性導電膜(1 cm×1 cm)與毛坯玻璃(厚度為0.3 mm)黏合。於該情形時,在表2所示之膜構成中,使下側之面與毛坯玻璃黏合,將上側之面設為黏著力之測定面,將毛坯玻璃放置於試樣台之矽橡膠之承受台上。其次,將黏性試驗機之圓柱狀之直徑為5 mm之探針(不鏽鋼製鏡面拋光)設置至測定面的上方,以壓抵速度30 mm/min使探針與測定面接觸,以加壓力196.25 gf、加壓時間1.0 sec進行加壓,於以剝離速度120 mm/min自測定面剝離2 mm時測定探針因測定面之黏著力所受之阻力作為負重值,將自測定面剝離探針時之最大負重設為黏著力(tack force)。於各實施例中,各測定2次黏著力,將其最低值示於表2。然而,由於實施例3、4難以測定,故而測定值之不均大於實施例1、2。比較例1係根據利用手指觸摸之觸感而黏著力小於實施例3、4,未進行測定。
(3)導通電阻(初始導通電阻)
按照足以連接之面積裁切各實施例及比較例之各向異性導電膜,夾入至導通特性之評價用IC與玻璃基板之間,進行加熱加壓(180℃、60 MPa、5秒)而獲得各評價用連接物,利用4端子法測定所獲得之評價用連接物之導通電阻,按照以下之基準進行評價。於該情形時,亦與(1)相同地將表2所示之膜構成之下側貼附於玻璃基板。
導通特性之評價用IC
外形:1.8×20.0 mm
厚度:0.3 mm
鍍金凸塊:尺寸30 μm×85 μm、凸塊間距離50 μm、凸塊高度5 μm
玻璃基板(ITO配線玻璃基板)
厚度:0.3 mm
初始導通電阻評價基準
OK:未達2.0 Ω
NG:2.0 Ω以上
(4)導通可靠性(85℃、85%RH、500 h)
與初始導通電阻相同地對在(3)中製作之評價用連接物測定於溫度85℃、濕度85%RH之恆溫槽內放置500小時後之導通電阻,按照以下之基準進行評價。
導通可靠性評價基準
OK:未達5.0 Ω
NG:5.0 Ω以上
根據表2可知,實施例1~4係相對於比較例1而(2)膜表面之黏著性(暫時壓接試驗)優異。
另一方面,可知無論實施例1~4或是比較例1,(3)初始導通電阻或(4)導通可靠性均無問題。
又,可確認到如下情形:無論實施例1~4或是比較例1,於A軸及B軸之兩者中熱壓接前後之間距之比率((P1/P0)×100%)均為300%以下,熱壓接前後之排列之混亂均較少。
(5)2階段壓入之連接試驗
為了於本發明之含填料膜中調查藉由2階段壓入實現之連接對填料之夾持產生的影響,使用實施例1~4之各向異性導電膜,將以下之評價用IC晶片及玻璃基板作為連接對象而製造藉由2階段壓入實現之連接體,測量以連接體之凸塊夾持之導電粒子之數量。
[評價用IC晶片]
周邊裝置型IC晶片
外形:6×6 mm
凸塊規格:ϕ36 μm(圓形之凸塊)、凸塊間距300 μm
凸塊高度較膜厚高3 μm以上。
[玻璃基板]
毛坯玻璃
外形15×15 mm、厚度150 μm
評價用IC晶片與玻璃基板係其等之凸塊及端子圖案對應。又,於連接評價用IC晶片與玻璃基板時,使各向異性導電膜之長度方向與凸塊之排列方向重合。以80℃、3秒進行2階段壓入之暫時壓接之按壓,以暫時壓接之2倍之壓力、180℃、10秒進行正式壓接之按壓。於自該暫時壓接向正式壓接推進步驟時,不解除施加於評價用IC晶片之壓力而升壓。作為接合機,使用倒裝晶片接合機(松下公司製造之FCB3,附有Pal heater),於暫時壓接及正式壓接中之任一者中均設為升溫0.5秒及升壓0.5秒。
又,為了進行比較,製造未藉由暫時壓接按壓而僅進行上述正式壓接而成之連接體。
於正式壓接後測量夾持於凸塊之導電粒子,結果確認到進行2階段壓入之(於暫時壓接後不解除壓力而升壓)連接體係相對於未藉由暫時壓接按壓之連接體而夾持於每個凸塊之導電粒子更多。
1、1A、1B、1C、1D、1E:含填料膜、各向異性導電膜
2:填料、導電粒子
3:微小固形物
10、11、12:絕緣性樹脂層
10a、11a、12a:乾燥面
10b、11b、12b:剝離基材側之絕緣性樹脂層之面
15:低黏度樹脂層
15a:低黏度樹脂層之乾燥面
15b:與低黏度樹脂層之乾燥面相反之面
20a、20b、20c:剝離基材
21:模具
30、31:載玻片
D:填料之粒徑
圖1A係表示實施例之含填料膜1A之填料配置之俯視圖。
圖1B係實施例之含填料膜1A之剖面圖。
圖2A係實施例之含填料膜1A之製造方法之說明圖。
圖2B係實施例之含填料膜1A之製造方法之說明圖。
圖2C係實施例之含填料膜1A之製造方法之說明圖。
圖2D係實施例之含填料膜1A之製造方法之說明圖。
圖2E係實施例之含填料膜1A之製造方法之說明圖。
圖2F係實施例之含填料膜1A之製造方法之說明圖。
圖3係實施例之含填料膜1B之剖面圖。
圖4A係實施例之含填料膜1B之製造方法之說明圖。
圖4B係實施例之含填料膜1B之製造方法之說明圖。
圖4C係實施例之含填料膜1B之製造方法之說明圖。
圖5係實施例之含填料膜1C之剖面圖。
圖6係實施例之含填料膜1C之製造方法之說明圖。
圖7係實施例之含填料膜1D之剖面圖。
圖8A係實施例之含填料膜1D之製造方法之說明圖。
圖8B係實施例之含填料膜1D之製造方法之說明圖。
圖8C係實施例之含填料膜1D之製造方法之說明圖。
圖9係實施例之含填料膜1E之剖面圖。
圖10A係實施例之含填料膜1E之製造方法之說明圖。
圖10B係實施例之含填料膜1E之製造方法之說明圖。
圖10C係實施例之含填料膜1E之製造方法之說明圖。
圖11係接著強度試驗之樣品之立體圖。
圖12係接著強度試驗方法之說明圖。
1A:含填料膜、各向異性導電膜
3:微小固形物
10、11、12:絕緣性樹脂層
11b、12b:絕緣性樹脂層之表面
Claims (12)
- 一種含填料膜,其於絕緣性樹脂層保持填料、及形成素材與填料不同之微小固形物,且於俯視時填料重複特定排列, 以平滑面夾著含填料膜而以特定之熱壓接條件熱壓接之情形時,其熱壓接後的填料之重複間距相對於熱壓接前之比率為300%以內。
- 如請求項1所述之含填料膜,其中,絕緣性樹脂層由2層之絕緣性樹脂層之積層體形成。
- 如請求項1或2所述之含填料膜,其中,30~200℃之範圍之最低熔融黏度低於絕緣性樹脂層之低黏度樹脂層積層於絕緣性樹脂層。
- 一種含填料膜之製造方法,其係請求項1所述之含填料膜的製造方法,具有如下步驟: 將含有微小固形物之絕緣性樹脂層形成用組成物塗佈至剝離基材上,於剝離基材上形成絕緣性樹脂層之步驟; 自絕緣性樹脂層之與剝離基材相反側之面壓入填料之步驟; 將壓入有填料之絕緣性樹脂層及與該絕緣性樹脂層不同之絕緣性樹脂層以將其等之剝離基材設為外側的方式積層之步驟。
- 一種含填料膜之製造方法,其係請求項1所述之含填料膜的製造方法,具有如下步驟: 將含有微小固形物之絕緣性樹脂層形成用組成物塗佈至剝離基材上,於剝離基材上形成絕緣性樹脂層之步驟; 藉由將2個絕緣性樹脂層以將其等之剝離基材設為外側之方式積層而形成絕緣性樹脂層之積層體的步驟; 將填料壓入至該絕緣性樹脂層之積層體之步驟。
- 一種含填料膜之製造方法,其係請求項3所述之含填料膜的製造方法,具有如下步驟: 將含有微小固形物之絕緣性樹脂層形成用組成物塗佈至剝離基材上,於剝離基材上形成絕緣性樹脂層之步驟; 將30~200℃之範圍之最低熔融黏度低於絕緣性樹脂層之低黏度樹脂層的形成用組成物塗佈至剝離基材,於剝離基材上形成低黏度樹脂層之步驟; 藉由將絕緣性樹脂層與低黏度樹脂層以將其等之剝離基材設為外側之方式積層而形成絕緣性樹脂層與低黏度樹脂層之積層體之步驟; 剝離絕緣性樹脂層之剝離基材,自將剝離基材剝離之絕緣性樹脂層之面壓入填料之步驟。
- 一種含填料膜之製造方法,其係請求項3所述之含填料膜的製造方法,具有如下步驟: 將含有微小固形物之絕緣性樹脂層形成用組成物塗佈至剝離基材上,於剝離基材上形成絕緣性樹脂層之步驟; 將30~200℃之範圍之最低熔融黏度低於絕緣性樹脂層之低黏度樹脂層的形成用組成物塗佈至剝離基材,於剝離基材上形成低黏度樹脂層之步驟; 將填料壓入至絕緣性樹脂層之與剝離基材相反側之面之步驟; 將壓入有填料之絕緣性樹脂層與形成於剝離基材上之低黏度樹脂層以將其等之剝離基材設為外側的方式積層之步驟。
- 一種膜貼合體,其係將請求項1至3中任一項所述之含填料膜黏合至物品而成。
- 一種連接體,其係介隔請求項1至3中任一項所述之含填料膜連接第1物品與第2物品而成。
- 一種連接體,其係介隔於請求項1至3中任一項所述之含填料膜中使用導電粒子作為填料之各向異性導電膜連接第1電子零件與第2電子零件而成。
- 一種連接體之製造方法,其係介隔請求項1至3中任一項所述之含填料膜連接第1物品與第2物品。
- 一種連接體之製造方法,其係介隔於請求項1至3中任一項所述之含填料膜中使用導電粒子作為填料之各向異性導電膜連接第1電子零件與第2電子零件。
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