TWI421323B - Anisotropic conductive adhesive - Google Patents

Anisotropic conductive adhesive Download PDF

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Publication number
TWI421323B
TWI421323B TW097134811A TW97134811A TWI421323B TW I421323 B TWI421323 B TW I421323B TW 097134811 A TW097134811 A TW 097134811A TW 97134811 A TW97134811 A TW 97134811A TW I421323 B TWI421323 B TW I421323B
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Taiwan
Prior art keywords
anisotropic conductive
conductive adhesive
electronic component
connection
pressure
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TW097134811A
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English (en)
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TW200918637A (en
Inventor
Hiroyuki Kumakura
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Dexerials Corp
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Publication of TW200918637A publication Critical patent/TW200918637A/zh
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Publication of TWI421323B publication Critical patent/TWI421323B/zh

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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Description

異向性導電接著劑
本發明係關於一種用以將電子零件以無壓力至低壓力異向性導電連接於配線板之異向性導電接著劑、以及使用其之異向性導電連接方法。
於環氧樹脂與硬化劑所構成之黏結劑樹脂組成物中分散有球狀導電粒子之異向性導電接著劑係廣泛使用於將可撓性印刷電路膜或IC晶片等電子零件連接於硬性基板等配線板之際(例如，專利文獻1)。於該場合，使異向性導電接著劑夾設於配線板與電子零件之間，將電子零件以熱壓機(Heat Bonder)加熱至黏結劑樹脂之硬化溫度(例如，150℃)以上，並且，為確保良好之連接可靠性而施加1MPa以上之壓力。其係為了確保一定程度之寬廣度的接觸面積，必須將球狀之導電粒子埋入配線板或電子零件之連接端子區域，因此需要較大之加壓。
專利文獻1：日本專利特公平5－47922號公報。
然而，將可撓性印刷電路膜等異向性導電連接於硬性基板之際，結果亦施加壓力了於配線板，故配線板有受到損害的情形。特別是，為了實現高密度構裝，而於配線板的背面亦構裝有電子零件時，不僅配線板，背面之電子零件或連接該等的配線亦會受到損害。
本發明之目的在於提供一種異向性導電接著劑，其可 解決以上之以往的技術課題，可將電子零件藉由無壓力或施加低壓力而異向性導電連接於配線板。
本發明人發現，藉由使用具有特定大小、厚度、及長寬比之金屬薄片(flake)粉，作為異向性導電接著劑所使用之導電粒子，可達成上述目的，而完成本發明。
亦即，本發明係一種異向性導電接著劑，其係用以將電子零件以無壓力至低壓力異向性導電連接於配線板者，，其係導電粒子分散於黏結劑樹脂組成物所構成者，其特徵在於，導電粒子為長徑10~40 μm、厚度為0.5~2 μm、長寬比為5~50之金屬薄片粉，且導電粒子於異向性導電接著劑中之含量，為5~35質量%。
又，本發明亦提供一種異向性導電連接方法，其係將上述之異向性導電接著劑供給於配線板之連接端子，再將電子零件之連接端子，於夾設有異向性導電接著劑之狀態下，暫時連接於基板之連接端子，於不對電子零件施加壓力或施加低壓力之下進行加熱，藉此連接基板與電子零件。
本發明之異向性導電接著劑，導電粒子係使用具有特定大小、厚度、長寬比之金屬薄片粉。導電粒子為如此之形狀、尺寸之金屬薄片粉，即使不將金屬薄片粉埋入配線板或電子零件之各連接端子，亦可於連接端子與導電粒子之間面接觸。因此，將配線板之連接端子與電子零件之連接端子，於夾設有異向性導電接著劑之狀態下對位，以比較低之壓力暫時連接後，以無壓力(亦即，不施加壓力)或施加比以往低之壓力的條件下加熱，藉此可成為展現良好連 接可靠性之異向性導電連接。
本發明係用以將電子零件以無壓力至低壓力異向性導電連接於配線板之異向性導電接著劑，其係於黏結劑樹脂組成物分散導電粒子所構成者。本發明之特徵在於，導電粒子係使用長徑10~40 μm、厚度為0.5~2 μm、長寬比為5~50之金屬薄片粉。
金屬薄片粉可使用鎳、銀等金屬之薄片粉，其中，由低成本與良好導電性的觀點，較佳為使用鎳薄片粉。
本發明所使用之金屬薄片粉，其長徑10~40 μm、較佳為10~30 μm，厚度為0.5~2 μm、較佳為0.5~1.5 μm。關於長徑，若未滿10 μm則連接後之傳導電阻(conduction resistance)有增高的傾向，而若超過40 μm則絕緣電阻有降低的傾向。又，關於厚度，若未滿0.5 μm則絕緣電阻有降低的傾向，而若超過2 μm則連接後之傳導電阻有增高的傾向。金屬薄片粉之長徑、厚度，係以電子顯微鏡等之外觀觀察所測定之數值。又，金屬之薄片粉的短徑通常為長徑之10~50%左右之長度。
再者，本發明所使用之金屬薄片粉，係使用長寬比(即長徑除以厚度之數值)為5~50、較佳為5~42者。關於長寬比，若未滿5則連接後之傳導電阻有增高的傾向，而若超過50則絕緣電阻有降低的傾向。
於本發明中，導電粒子於異向性導電接著劑中之含量為5~35質量%、較佳為7~30質量%。其之含量若未滿5質 量%，則連接可靠性不充分，若超過35質量%則導電連接之異向性有損失之虞或連接強度會降低。
構成本發明之異向性導電接著劑之黏結劑樹脂組成物，可從以往之異向性導電接著劑中所使用之熱硬化性黏結劑樹脂組成物之中適當地選擇使用。可舉例如，於熱硬化性環氧樹脂、熱硬化型尿素樹脂、熱硬化型三聚氰胺樹脂、熱硬化型酚樹脂等配合有咪唑系硬化劑、胺系硬化劑等硬化劑而成之黏結劑樹脂組成物。其中，若由硬化後之接著強度為良好的觀點考量，較佳可使用使用熱硬化型環氧樹脂作為黏結劑樹脂之黏結劑樹脂組成物。
如此之熱硬化型環氧樹脂可為液狀、亦可為固體狀，較佳為，環氧當量為通常100~4000左右，分子中具有2個以上之環氧基者。較佳可使用例如雙酚A型環氧化合物、酚醛清漆型環氧化合物、甲酚酚醛清漆型環氧化合物、酯型環氧化合物、脂環型環氧化合物等。又，於該等化合物亦可含有單體或寡聚物。
於本發明之黏結劑樹脂組成物，亦可視需要含有二氧化矽、雲母等填充劑、顏料、抗靜電劑等。亦可配合著色料、防腐劑、聚異氰酸酯系交聯劑、矽烷耦合劑等。
又，亦可配合周知之球狀導電粒子。若除金屬薄片粉之外亦配合球狀導電粒子，則可獲得能使傳導電阻值更安定化之效果、及減少金屬薄片粉之使用量而可抑制異向性導電接著劑之製造成本的效果。該球狀導電粒子之大小，較佳為，平均粒徑為1~10 μm者且較導電粒子之長徑小 者。又，球狀導電粒子之配合量，較佳為金屬薄片粉之配合量(質量份)之0.1~1倍。
本發明之異向性導電接著劑之黏度，若過低則由暫時壓接至正式硬化之製程中會流動而容易引起連接不良。而過高則塗佈時容易產生不良情形，故以錐板式黏度計(cone－plate viscometer )所測定之25℃下之黏度，較佳為50~200Pa．s、更佳為50~150Pa．s。
本發明之異向性導電接著劑，可藉由將導電粒子之金屬薄片粉，以一般方法均勻地分散至熱硬化性黏結劑樹脂組成物中來製造。
本發明之異向性導電接著劑，如以下之說明，較佳可使用於將配線板與電子零件加以異向性導電接著之際。
首先，將該異向性導電接著劑供給於該配線板之連接端子。此處，配線板可舉例如形成有透明電極之玻璃配線基板、玻璃環氧配線基板、聚醯亞胺印刷電路膜基板等。連接端子可利用分別適於各基板之端子。
又，異向性導電接著劑之供給方法，一般係由注射器供給之方法，但並不限定於此。亦可將異向性導電接著劑成膜，作為異向性導電膜來供給。所供給之異向性導電接著劑之厚度通常為30~50 μm。
接著，將電子零件之連接端子於夾設有異向性導電接著劑之狀態下暫時連接於配線板之連接端子。具體而言，係將電子零件之連接端子於夾設有異向性導電接著劑之狀態下對位於配線板之連接端子。而對電子零件施加較佳為 0.1~1MPa之壓力以暫時連接。於該場合，亦可加熱至不會使黏結劑樹脂組成物完全硬化的程度。此處，電子零件，可舉例如IC晶片、可撓性印刷電路膜等。
接著，對電子零件，於不施加壓力或施加低壓力(亦即，1MPa以下)之下加熱，使黏結劑樹脂組成物大致完全至完全硬化。藉此，可成為安定且展現良好連接可靠性之異向性導電連接。
本發明之異向性導電接著劑，不僅上述之異向性導電連接用途，亦可使用於不需要異向性之導電連接用途。可舉例如電阻、或電容器、壓電元件等電子零件之連接。
實施例
以下，以實施例更具體地說明本發明。
實施例1~7、比較例1~9
將表1之成分以混合機均勻地混合，以調製異向性導電接著劑。使用流變計(哈克公司製錐板式黏度計)，以溫度25℃、剪應力(shear stress)10(1/s)測定所得之異向性導電接著劑之黏度。所得之結果示於表1。又，所使用之鎳薄片及球狀鎳粒子之大小，將以電子顯微鏡直接觀察之結果示於表1。
(異向性導電連接評估)
又，將所得之異向性導電接著劑，於硬性印刷配線基板(玻璃環氧基材1.1mm厚/Cu配線35 μm厚/表面鍍金：2mm間距、L/S＝1/1)之連接端子，由注射器以厚度為35 μm的方式塗佈。從該異向性導電接著劑的上方，將可撓性 配線電路膜(聚醯亞胺膜基材22 μm厚/Cu配線18 μm厚/表面鍍金：2mm間距、L/S＝1/1)之連接端子對位於硬性印刷配線基板之連接端子，以常溫施加0.5MPa之壓力以暫時連接。
將暫時連接而成者置入120℃之烘箱中，於不對連接部施加壓力之下加熱10分鐘，使黏結劑樹脂組成物硬化，藉此進行異向性導電連接，對所得之連接構造體，如以下之說明，對傳導電阻值、絕緣電阻值、剝離強度進行試驗評估。
<傳導電阻值>
對異向性導電連接所得之連接構造體，使用數位萬用電表(digital multimeter，愛德萬測試公司)以4端子法測定傳導電阻值(最大(Max.)、最小(Min.)、平均(Ave.))。所得之結果示於表1。實用上，較佳為最大值為10Ω以下、最小值為0.5Ω以下、平均為1~5Ω。
<絕緣電阻值>
以施加20V之條件下，測定異向性導電連接所得之連接構造體之相鄰端子間之絕緣電阻。絕緣電阻值為108 Ω以上評估為A、107 ~108 Ω評估為B、未滿107 評估為C。實用上，較佳為評估為A或B。
<剝離強度>
固定異向性導電連接所得之連接構造體之硬性印刷配線基板，將可撓性配線電路膜朝90度之方向，以50mm/分鐘之速度剝下，使用拉伸試驗機測定此時之剝離強度。所 得之結果示於表1。實用上較佳為5N/cm以上。
由表1可知，使用具有特定大小與長寬比之金屬薄片粉作為導電粒子之本發明之異向性導電接著劑，於傳導電阻值、絕緣電阻值及剝離強度展現實用上無問題的特性。另一方面，比較例1之異向性導電接著劑，鎳薄片之含量低於5質量%，故傳導電阻值(最大)過高為不適於實際使用者。比較例2~6之異向性導電接著劑，由於鎳薄片之含量超過35質量%，故無法保持在相鄰端子間之絕緣電阻，為不適於實際使用者。比較例7之異向性導電接著劑，所使用之金屬薄片之長寬比低於5，故傳導電阻值(最大)過高為不適於實際使用者。又，比較例8之異向性導電接著劑，所使用之金屬薄片之長寬比超過50，故無法保持相鄰端子間之絕緣電阻，為不適於實際使用者。而比較例9之異向性導電接著劑，未使用金屬薄片而使用球狀導電粒子，故傳導電阻值(最大)高，無法供以實際使用。
實施例8、比較例10
使用實施例4或比較例9之異向性導電接著劑，於暫時連接後之異向性導電連接時，以固定熱壓機(寬度2mm)，以180℃、10秒鐘，及下述表2所示之連接壓力將可撓性印刷電路加以異向性導電連接。對所得之連接構造體，以與實施例1相同之方式，對傳導電阻值及絕緣電阻進行試驗評估。所得之結果示於表2。
由表2可知，本發明之異向性導電接著劑，即使在未對連接部施加壓力、或施以1MPa以下(特別是0.5MPa以下)之低壓條件下，亦可確保良好之連接可靠性。相對於此，使用球狀導電粒子之比較例10與實施例8相比，傳導電阻值高、以低壓條件難以確保良好之連接可靠性。
本發明之異向性導電接著劑，導電粒子係使用具有特定大小、厚度、長寬比之金屬薄片粉。因此，將配線板之連接端子與電子零件之連接端子於夾設有該異向性導電接著劑之狀態下對位，以比較低壓進行暫時連接後，於不施加壓力或施加比以往低之壓力的條件下加熱，藉此可成為展現良好連接可靠性之異向性導電連接。因此，本發明之異向性導電接著劑適用於對連接部以無壓力至低壓施加條件之異向性導電連接。

Claims (7)

  1. 一種異向性導電接著劑，其係用以將電子零件以無壓力至1MPa以下之低壓力異向性導電連接於配線板，其係導電粒子分散於黏結劑樹脂組成物所構成者；其特徵在於，該導電粒子為長徑10~40μm、厚度為0.5~2μm、長寬比為5~50之金屬薄片(flake)粉，且導電粒子於異向性導電接著劑中之含量為5~35質量%。
  2. 如申請專利範圍第1項之異向性導電接著劑，其中，該金屬薄片粉係鎳薄片粉。
  3. 如申請專利範圍第1或2項之異向性導電接著劑，其中，該黏結劑樹脂組成物係含有環氧樹脂與咪唑系硬化劑。
  4. 如申請專利範圍第1或2項之異向性導電接著劑，其於25℃之黏度為50~200Pa．s。
  5. 一種異向性導電連接方法，其係將申請專利範圍第1項之異向性導電接著劑供給於配線板之連接端子，再將電子零件之連接端子於夾設有異向性導電接著劑之狀態下暫時連接於基板之連接端子，於不對電子零件施加壓力或施加1MPa以下之低壓力之下進行加熱，藉此連接基板與電子零件。
  6. 如申請專利範圍第5項之異向性導電連接方法，其中，於加熱之際對電子零件施加1MPa以下之低壓力。
  7. 如申請專利範圍第5或6項之異向性導電連接方法，其中，於暫時連接之際對電子零件施加0.1~1MPa之壓力。
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US8092636B2 (en) 2012-01-10
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USRE45092E1 (en) 2014-08-26

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