TW200918637A - Anisotropically conductive adhesive - Google Patents

Anisotropically conductive adhesive Download PDF

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Publication number
TW200918637A
TW200918637A TW097134811A TW97134811A TW200918637A TW 200918637 A TW200918637 A TW 200918637A TW 097134811 A TW097134811 A TW 097134811A TW 97134811 A TW97134811 A TW 97134811A TW 200918637 A TW200918637 A TW 200918637A
Authority
TW
Taiwan
Prior art keywords
anisotropic conductive
conductive adhesive
connection
electronic component
adhesive
Prior art date
Application number
TW097134811A
Other languages
English (en)
Other versions
TWI421323B (zh
Inventor
Hiroyuki Kumakura
Original Assignee
Sony Chemical & Inf Device
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Filing date
Publication date
Application filed by Sony Chemical & Inf Device filed Critical Sony Chemical & Inf Device
Publication of TW200918637A publication Critical patent/TW200918637A/zh
Application granted granted Critical
Publication of TWI421323B publication Critical patent/TWI421323B/zh

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Classifications

    • 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
    • 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
    • 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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    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K19/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic element specially adapted for rectifying, amplifying, oscillating or switching, covered by group H10K10/00
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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Conductive Materials (AREA)
  • Wire Bonding (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)

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200918637 九、發明說明： 【發明所屬之技術領域】 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f連接於配線板之異向性導電接㈣、以及使用 其之異向性導電連接方法。 【先前技術】 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 撓性印刷電路膜或以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υ。於該場合，使異向性導電接 者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，15〇以 以上’並且’為確保良好之連接可#性而施加iMpa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。 【發明内容】 d而將可撓丨生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，&配線板有受到 損害的情形。特別是1 了實現高密度構裳，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。 本發月之目的在於提供一種異向性導電接著劑，其可 200918637 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以爪、厚度為〇 5〜2# m、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 較低之磨力暫時連接後，以無麼力（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 6 200918637 接可靠性之異向性導電連接。 【實施方式】 本發明係用以將電子愛 电十零件以無壓力至低壓力異向性 電連接於配線板之異向性 扭赤蘇八與、蓄 導電接者劑，其係於黏結劑樹脂 ，.且成物刀政導電粒子所構成 调1风#。本發明之特徵在於，導雷 粒子係使用長徑10〜40 序度马0.5〜2 // m、長寬比為 5〜50之金屬薄片粉。 金屬薄片粉可使用鋅、鉬镗^ 把“ 文用螺銀等金屬之薄片粉，其中，由 低成本與良好導電性 觀‘黏較佳為使用鎳薄片粉。 本發明所使用之金屬薄片 项，寻月恭，其長徑10〜40/z m、較佳 為1〇〜30// m，厚度為〇 5〜2 較佳為0.5~1.5Am。關於 長徑，若未滿10 " m則連接祛夕质# 要後之傳導電阻（conduction resistance)有增高的傾向， 右超過40 a m則絕緣電阻有降 低的傾向。又，關於厚度， 右禾渴〇 · 5 “ m則絕緣電阻有降 低的傾向，而若超過2 β m則 j連接後之傳導電阻有增高的傾 向。金屬薄片粉之長徑、厚声，4 ^ ^ 又係以電子顯微鏡等之外觀 觀察所測定之數值。又，金屬夕噠y也、 复屬之薄片粉的短徑通常為長徑 之10〜5 0%左右之長度。 再者本發月所使用之金屬薄片粉，係使用長寬比（即 控除以厚度之數值）為5〜5G、較佳為5〜42者。關於長寬 比，右未％ 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，導電粒子於里 卞於異向性導電接著劑中之含量 為5〜35質量％、較佳為7〜3〇皙晉 貝量/〇。其之含量若未滿5質 200918637 量％，則連接可靠x ^ χ 菲性不充分，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。 構成本發明之異向姓道曾拉盆杰丨 . 導電接著劑之黏結劑樹脂組成 二可從以往之異向性導電接著劑中所使用之熱硬化性黏 1組絲之巾適當地選擇使用。可舉例如，於執硬 匕性：氧樹脂、熱硬化型尿素樹腊、熱硬化型三聚氛胺樹 二?Γ型盼樹脂等配合㈣唾系硬化劑、胺系硬化劑 L更化心叙黏結_驗成物。其卜若由硬化後之 2度為良好的觀點考量，較佳可使用使用熱硬化型環 虱树知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， 環氧當量為通常100〜4000左右，分子中具有2個 齡路：：氧基者。較佳可使用例如雙朌Α型環氧化合物、 型产氧化ί環氧化合物、甲㈣盤清漆型環氧化合物、醋 衣氧化合物、脂環型環氧化合物等 亦可含有單體或寡聚物。 於該專化合物 於本發明之黏結劑樹脂組成物，亦可視 = '雲母等填充劑'顏料、抗靜電劑等。亦可配= 防腐劑、聚異氰酸醋系交聯劑、♦烷輕合劑等。 之外L’r配合周知之球狀導電粒子。若除金屬薄片粉 定化^效二粒子則可獲得能使傳導電阻值更安 導電接著金屬薄片粉之使用量而可抑制異向性 較2者劑之製造成本的效果。該球狀導電粒子之大小， 千均粒徑為者且較導電粒子之長徑小 200918637 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 過咼則塗佈時容易產生不良情形，故以錐板式黏度計 (cone-plate 所測定之25工下之黏度，較佳為 50〜200Pa.s、更佳為 50〜15〇Pas。 r 本發明之異向性導電接著劑，可藉由將導電粒子之金 屬溥片粉以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㈣電膜來供、給。所供給之異向性導電接 著劑之厚度通常為30〜5〇em。 著劑 係將 態下 接著冑電子零件之連接端子於夾設有異向性導電接 之狀態下暫時連接於配線板之連接端h具體而言， 電子零件之連接端f於夾設有異向性導電接著劑之狀 對位於配線板之連接端子。而對電子零件施加較佳為 200918637 ο·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， IMPa以下）之下加熱，使黏結劑樹脂組成物大致完全至完入 硬化。藉此，可成為安定且展現良好連接可靠性之異：： 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之成分以混合機均句地混合’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°c、剪應力（shear stress)l〇(1/s)測定所得之異向性導電^ 著劑之黏度。所得之結果示於表i。又，所使用之錄薄片及 球狀錦粒子之大小’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#m厚/表面铲 金：2mm間距、L/s = 1/1)之連接端子，由注射器以厚度為^ # m的方式塗佈。從該異向性導電接著劑的上方，將可撓性 200918637 配線電路膜（聚醯亞胺膜基材22"m厚心配線18"m厚/ 表面鍵金距、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，以常溫施加〇.5Mpa之壓力以暫時連 接。 將暫時連接而成者置人12代之烘箱中，；^不對連接部 施加壓力之下加熱〗〇分鐘，使黏結劑樹脂組成物硬化，藉 j進行異向性導電連接，對所得之連接構造體，如以下之 »兒月對傳導電阻值、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 muUimeter，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±，較佳為最大值為㈣以下、最小值 為0.5Ω以下、平均為1〜5Ω。 ί| <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。絕緣電阻值為咖以 上評估為Α、ίο7〜ι〇8Ω評估為Β、未滿1〇7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9〇度之方向，以分 鐘之速度剝下，使用拉伸試驗機測定此時之剝離強度。所 11 200918637 得之結果示於表1。實用上較佳為5N/cm以 12 200918637 6^^3 0£ Οϊοε 0寸
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Ml·^絮 S7y2!ii40r ^，日¾寸oir, sy.os!gi^6* 6(N寸ΰΊΐ- , STUO-ir,日=0£勃^8* 宕至鉍嶙，S3 ir, sy.o(Ntil-r· /..9^11- , sas.IB!!:, 6》01趔1- 9* r(N^1 ΐ-, ε¾CN.tNir, s alns^-ir ^ fM^S^ f ^<<ί*^^^ΐ¥,(ς9/>οε = ιιί^®ί_ί1Ηνα;9/φ^1Ε^^)«Ε^^$1^^ίδ(ιρ1β-ε3ιρ\04#ε*^^lsrtii^B ,J)nsfmfifHvda Γ -^ i ει 200918637 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，鎳薄月之含量 低於5質量％，故傳導電阻值（最大）過高為不適於實際使用 者。比較命"〜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5〇，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1 〇 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180X： ' 10秒鐘，及下述表2戶斤示之連接塵力將可挽性 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。 14 200918637 [表2]
實施例8 _接著劑 表1之實施例4之ACP 表1之fch赫也Ϊ Q夕ΔΓΊ> 連接壓力 IMPa 0.5MPa 0.2MPa O.IMPa IMPa 0.5MPa 0 21UPa Π 1 A/fD〇 傳導電阻Max. Ω 0.75 1.05 1.56 2.17 0.87 3.9 9.7 U.1IVIi a 23.55 Min. Ω 「0.27 0.29 0.31 0.33 0.35 J 0 63 1 Ο ΛΟ Ave. Ω 0.52 0.56 0.73 0.82 0.74 111 Z.Uo A 絕緣電阻 A A A A A A A A 由表2可知，本發明之異向性導電接著劑，即使在未 f 對連接部施加壓力、或施以1MPa以下（特別是〇 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 I 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。 【圖式簡單說明】 盎 【主要元件符號說a月】 無 15

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  1. 200918637 十、申請專利範困： I—種異向性導電接著劑，其係用以將電子零件以 力至低麼力異向性導電連接於配線板，其係導電粒子: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1〇〜4〇/Zm、厚度為〇·5力m、長寬比為5〜5〇之金 屬薄片（Me)粉’且導電粒子於異向性導電接著劑中之含量 為5〜35質量％。 含置 2.如申叫專利範圍第丨項之異向性導電接著劑，其中， s亥金屬薄片粉係鎳薄片粉。 ^如申請專利範圍第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㈣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 C之黏度為50〜2〇〇pa.s。 5·種異向性導電連接方法，其係將申請專利範圍第工 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1 MPa以下之低麼力。 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❹丨〜丨厘〜之壓力。 16
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