TW201012890A - Acrylic dielectric adhesive - Google Patents

Acrylic dielectric adhesive Download PDF

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Publication number
TW201012890A
TW201012890A TW098131027A TW98131027A TW201012890A TW 201012890 A TW201012890 A TW 201012890A TW 098131027 A TW098131027 A TW 098131027A TW 98131027 A TW98131027 A TW 98131027A TW 201012890 A TW201012890 A TW 201012890A
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TW
Taiwan
Prior art keywords
insulating adhesive
parts
film
mass
acrylic
Prior art date
Application number
TW098131027A
Other languages
English (en)
Inventor
Daisuke Sato
Original Assignee
Sony Chem & Inf Device Corp
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Publication date
Application filed by Sony Chem & Inf Device Corp filed Critical Sony Chem & Inf Device Corp
Publication of TW201012890A publication Critical patent/TW201012890A/zh

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    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
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    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
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    • H05K3/303—Surface mounted components, e.g. affixing before soldering, aligning means, spacing means
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49117—Conductor or circuit manufacturing
    • Y10T29/49124—On flat or curved insulated base, e.g., printed circuit, etc.
    • Y10T29/49128—Assembling formed circuit to base
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49117—Conductor or circuit manufacturing
    • Y10T29/49124—On flat or curved insulated base, e.g., printed circuit, etc.
    • Y10T29/4913—Assembling to base an electrical component, e.g., capacitor, etc.
    • Y10T29/49146—Assembling to base an electrical component, e.g., capacitor, etc. with encapsulating, e.g., potting, etc.

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Description

201012890 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種用以將ic晶片等電子零件接合至配 線基板之自由基聚合性丙烯酸系絕緣性接著劑、以該接著 劑之自由基聚合硬化物來將電子零件固定於配線基板所得 之連接構造體及其製造方法。 * 【先前技術】 〇 近年來，伴隨IC晶片之高集積化，ic晶片之凸塊間的 空間變得窄節距化’又凸塊面積也出現窄面積化。將IC晶 片接合於配線基板之際，雖廣泛使用異向性導電膜，但由 於導電性粒子之粒徑下限在2"m程度，所以適用於高集積 化之1C晶片與配線基板的接合上會發生困難。此外，當將 矛J用接合機所做成之柱形凸塊（stud bump)做為對應於窄節 距化與窄面積化之凸塊時’由於凸塊形狀會因其前端部傾 倒成為大致圓錐形狀，而有導電性粒子之捕獲性低之缺 © 點。是以’乃逐漸不使用異向性導電膜，而是使用絕緣性 接著劑將1C晶片之凸塊與配線基板之連接墊做直接接合 (NCF接合）。 於前述NCF接合所使用之絕緣性接著劑方面，以往， 為了利用熱硬化反應來產生羥基，乃使用了顯現高凝集 力、且對被接著體可確保高接著強度之熱硬化性環氧系樹 脂接著劑（專利文獻1)〇但是，熱硬化性環氧系樹脂接著劑 雖可確保良好凝集力以及對於被接著體之良好密接強度， 3 201012890 但另一方面聚合反應溫度為l8〇〜 25(rc相對較高，且需要 數小時的熱硬化時間，所以於熱硬化時IC晶片可能會受到 損害，且有接合生產性低的問題。 是以’乃有人嘗試將能於相對低溫與短時間進行自由 基聚合的丙烯酸系絕緣性接著劑利用在NCF接合上（專利文 獻2)。 專利文獻1特開2001-189346號公報 專利文獻2特開2003-82034號公報 【發明内容】 發明所欲解決之課題 但是，使用專利文獻2之丙烯酸系絕緣性接著劑的情 況’其自由基聚合硬化物的玻璃轉化溫度為_3〇〜1〇〇c相對 低’物性改善用之無機填料的含量相對於硬化樹脂成分1 〇〇 重量份為5〜40重量份也相對較少，所以雖然在接合部之 應力緩和方面具有優點’但凝集力與耐熱性不充分，尺寸 女疋性也發生問題’結果無法期待良好的連接可靠性。是 以，專利文獻2，如其實施例所揭示般，將ic晶片接合至 配線基板之際，不得不於接著劑配合環氧樹脂與環氧樹脂 硬化劑，接合時並非以自由基反應而是以陰離子開環聚合 反應來使得接著劑硬化’仍然必須採用14〇。(：、5小時之聚 合硬化條件。如此般，目前尚未實現使得丙烯酸系絕緣性 接著劑以低溫迅速進行自由基聚合硬化，來將1C晶片等電 子零件固定於配線基板，且以高連接可靠性來將1C晶片之 201012890 凸塊與配線基板之連接墊做直接接合。 本發明之目的在於提供一種自由基聚合性丙烯酸系絕 緣性接著劑，其做為將電子零件以NCF接合來接合至配線 基板的絕緣性接著劑，在低溫快速聚合硬化性優異，可實 現良好之連接可靠性。 用以解決課題之手段 i 本發明者發現在由（曱基）丙烯酸酯單體、成膜用樹脂、 無機填料、矽烷偶合劑以及自由基聚合起始劑所構成之丙 Ο 烯酸系絕緣性接著劑中，若無機填料之含量相較於以往以 較大量含有，且玻璃轉化溫度較以往來得非常高，且其玻 璃轉化溫度前後的線膨脹係數分別設定在特定範圍内，則 可達成本案發明之目的，從而完成了本發明。 亦即’本發明係提供一種丙烯酸系絕緣性接著劑，其 含有（甲基）丙烯酸酯單體、成膜用樹腊'無機填料、矽烷偶 合劑以及自由基聚合起始劑，用以將電子零件固定於配線 基板者； 〇 無機填料相對於（甲基）丙烯酸酯單體以及成膜用樹脂 之合計100質量份係含有70〜16〇質量份； 丙稀酸系絕緣性接著劑之自由基聚合硬化物顯示150 〜185°C之玻璃轉化溫度，且在低於玻璃轉化溫度的溫度區 域顯示30〜35Ppm之線膨脹係數（α υ，在玻璃轉化溫度以 上之溫度區域顯示1 〇5〜125ppm之線膨脹係數（α 2)，並滿 足下述式（1) a 2/a 3.4 ...(1) 5 201012890 再者，本發明提供該丙烯酸系絕緣性接著劑之自由基 聚合硬化物。 再者’本發明提供一種連接構造體，係電子零件與配 線基板以上述自由基聚合性之丙烯酸系絕緣性接著劑的自 由基聚合硬化物做固定，該電子零件的凸塊直接接合於配 線基板之連接墊者。 再者’本發明係上述連接構造體之製造方法，係對配 線基板供應上述自由基聚合性之丙烯酸系絕緣性接著劑， 並對配線基板之連接墊進行電子零件凸塊之對位，然後將 電子零件加熱加壓以使得丙烯酸系絕緣性接著劑做自由基 聚合硬化而將電子零件固定於配線基板，且將電子零件之 凸塊與配線基板之連接墊加以直接接合。 發明效果 抑本發明之丙烯酸系絕緣性接著劑，係由（甲基）丙稀酸醋 單體、成膜用樹脂、無機填料、矽烷偶合劑以及自由基聚 合起始劑所構成，且無機填料之含量較以往來得多，再y 其玻璃轉化溫度較以往來得非常地高，且其玻璃轉化溫产 前後之線膨脹係數分別設定於特定範圍所以能以 = 200。。之相對低溫、5〜10秒之加熱時間進行自由人〜 化。再者，應力緩和性也優異’戶斤以可實現良好：連：； 靠性。 心運接可 【實施方式】 本發明之自由基聚合性之丙烯酸系 絕緣性接著劑 係 201012890 用以將電子零件固定於配線基板上之接著劑，其特徵在於 含有（甲基）丙烯酸酯單體、成膜用樹脂、無機填料、矽烷偶 合劑以及自由基聚合起始劑。 本發明之丙烯酸系絕緣性接著劑之構成成分之一的（甲 基）丙烯酸酯單體，主要係對於接著劑的聚合硬化物賦予凝 ： 集力，可賦予機械特性。此處，所說之（甲基）丙烯酸酯單體 意指丙烯酸酯單體或是甲基丙烯酸酯單體。 在（曱基）丙稀酸酯單體方面，可使用單官能（甲基）丙稀 0 酸g曰單體、多官能（曱基）丙烯酸酯單體、或是於該等當中導 入環氧基、胺基曱酸酯基、胺基、氧化乙烯基、氧化丙烯 基等而成之變性單官能或多官能（曱基）丙烯酸酯單體。又， 於本發明中，亦可僅使用單官能（甲基）丙烯酸酯單體做為 (甲基）丙烯酸酯單體，但為了使得接著劑之聚合硬化物的玻 璃轉化溫度設定為較高、且提高凝集力，較佳為至少一部 刀更佳為全部皆使用多官能（曱基）丙烯酸酯單體。 在單官能（甲基）丙烯酸酯單體方面，可舉出至少丨分子 © ^具有1個以上（曱基）丙烯醯基之（甲基）丙稀酸s旨樹脂或該 等之變性物等。又，該等變性物可舉出丙稀酸四氣擁醋、 丙烯酸異冰片酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、三 f六烷一甲醇二丙烯酸酯、三環癸烷二甲醇二曱基丙烯酸 δ曰匕乙氧基化雙酚A二丙烯酸酯、丙氧基化雙酚A二丙烯 酸6日季戊四醇三丙烯酸酯、乙氧基化三聚異氰酸三丙烯 酸醋等。 於本發明之丙烯酸系絕緣性接著劑中，可在不致損及 7 201012890 本發明效果的前提下，併用可和（子基）丙烯酸酯單體做自由 基聚合之其它單體。此種其它單體可舉出（甲基）丙烯酸、乙 酸乙烯酯、苯乙烯、氣乙烯等。 本發明之丙烯酸系絕緣性接著劑係含有成膜用樹脂。 成膜用樹脂乃玻璃轉化溫度為5(rc以上之在常溫下固體之 樹脂，為與（甲基）丙烯酸酯單體互溶之樹脂，用以使得丙烯 酸系絕緣性接著劑之自由基聚合硬化物的玻璃轉化溫度上 升。做為此種成膜用樹脂，可舉出苯氧樹脂 '聚乙烯縮醛 樹知丙烯酸樹月曰、本乙烯樹脂、胺s旨樹脂、聚對苯二甲 酸乙二醇酯樹脂等。當中，又以分子量10000〜1〇〇〇〇〇、分 子中具有芴骨架之苯氧樹脂為佳。此種具有芴骨架之成膜 用樹脂之具體例可舉出FX293(東都化成公司製造）等。、 於本發明中，成膜用樹脂之使用量若過少則丙烯酸系 絕緣性接著劑之成膜性會不充分，若過多則相對地（甲基） 丙烯酸醋單體的使用量會過度減少而損及凝集力，所以^目 對於（甲基）丙烯酸酯單體100質量份較佳為5〇〜1〇〇質量 份。 本發明之丙烯酸系絕緣性接著劑為了調整熔融黏度、 改善難燃性、改善尺寸安定性等而含有無機填料。此種無 機填料可使用氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、矽 酸鈣、矽酸鎂、氧化鈣、氧化鎂、氧化鋁粉末、結晶性氧 化石夕、非結晶性氧化石夕、氮化铭、氣化蝴粉末、棚酸銘晶 鬚等。當巾’可較佳使用非結晶性氧切。該等亦可為球 狀等定形或不定形者。 201012890 無機填料之粒徑若過小則會引發黏結劑之增黏而無法 進行良好的塗佈，若過大則會成為填料攻擊（mier 的原因’是以較佳為0.005〜15"m、更佳為OH心。 於本發明中’若無機填料之使用量過少無法得到良好 之導通可靠性，若過多會引發黏結劑之增黏而無法進行良 好的塗佈’所以相對於（甲基）丙稀酸s旨單體與成膜用樹脂: 合計100質量份，較佳A 70〜16() f量份、或是相對於所 使用之樹脂100質量份為50〜150質量份。 ❺ 本發明之丙烯酸系絕緣性接著劑為了改善接著劑之聚 合硬化物與1C晶片或配線基板或無機填料之密合性，係含 有石夕烧偶合劑。切烧偶合劑方面可舉出r_縮水甘油基丙 基三甲氧基㈣、卜婆基丙基三甲氧基㈣、卜胺基丙基 三乙氧基矽烷、卜胺曱醯胺丙基三乙氧基矽烷、N{胺基 乙基个胺基丙基三甲氧基钱、7_甲基丙烯氧基丙基三 甲氧基㈣等。當中又以使用卜曱基丙稀氧基丙基三甲氧 基碎院為佳。 〇 於本發明中，矽烷偶合劑之使用量若過少則接著力變 得不充分，若過多則會成為加熱硬化時之氣泡產生原因， 所以相對於（甲基）丙烯酸醋單體與成膜用樹脂之合計ι〇〇 質量份較佳為0· 1〜5質量份。 本發明之丙稀㈣絕緣性接著劑係含有（甲基）丙稀酸 醋單體、用以進行自由基聚合之自由基聚合起始劑。在自 由基聚合起始劑方面可舉出過氧化苯酿、二枯基過氧化 物、二丁基過氧化物等有機過氧化物、偶氣雙異丁猜、偶 9 201012890 氮雙戊腈等偶氮系化合物等。當中又以使用過氧化笨醯為 佳。 於本發明中’自由基聚合起始劑之使用量若過少則無 法短時間硬化，若過多則硬化物會變硬造成密合性降低， 疋以相對於（曱基）丙烯酸酯單體以及成膜用樹脂之合計100 質量份較佳為1〜10質量份。 本發明之丙烯酸系絕緣性接著劑除了以上所說明之成 刀以外，為了提高連接可靠性以含有應力緩和劑為佳。在 應力緩和劑方面可使用與成膜樹脂、（甲基）丙烯酸單體之聚 合硬化物相溶之橡膠或熱塑性彈性體。此種橡膠、熱塑性 彈性體可舉出丙烯酸橡膠、丁腈橡膠（NBR)、丁二烯橡膠（PB) 等’亦可併用兩種類以上。 於本發明中使用應力緩和劑之情況，其使用量若過少 則無法得到充分之應力緩和效果，若過多則成為非相溶狀 態，是以相對於（甲基）丙烯酸酯單體以及成膜用樹脂之合計 1〇〇質量份較佳為1〜1〇質量份。 本發明之丙烯酸系絕緣性接著劑除了以上成分尚可視 情況含有甲苯、甲乙酮、乙酸乙酯等之溶劑、著色劑、抗 氧化劑、抗老化劑等。 本發明之丙烯酸系絕緣性接著劑其自由基聚合硬化物 顯示150〜185t：、較佳為155〜175七之玻璃轉化溫度。若 玻璃轉化溫度未滿150。(：，會損及加熱時之連接可靠性。此 處，自由基聚合硬化條件可從較低溫之13(rc左右起，但就 獲得實用性聚合速度之觀點，可舉出16〇〜2〇〇t：2加熱溫 201012890 度。此時之加熱時間為5〜1 〇秒。 本發明之丙烯酸系絕緣性接著劑之自由基聚合硬化物 在低於玻璃轉化溫度的溫度區域（亦即適用自由基聚合硬化 物之連接構造體的使用溫度）、具體而言在〇〜50°C顯示30 〜3 5ppm之線膨脹係數（α 1);在玻璃轉化溫度以上之溫度 區域（亦即焊料熔焊處理溫度）、具體而言在185〜2〇(rc顯 不105〜125ppm之線膨脹係數（α 2)。若線膨脹係數（α υ 超過35ppm，會損及連接可靠性故不佳。又，若線膨脹係數 Ο (α 2)超過125ppm ’會損及連接可靠性故不佳。 又’本發明之丙烯酸系絕緣性接著劑必須進一步滿足 下述式（1) α 2/α 1 ^ 3.4 ...(1) 此乃由於’若α 2/ α 1未滿3.4會損及連接可靠性之故。 具有前述特性之本發明之丙烯酸系絕緣性接著劑之自 由基聚合硬化物亦為本發明之一部分。 本發明之丙烯酸系絕緣性接著劑在將1C晶片對配線基 板進行NCF接合之際適合使用。具體而言，可適用於一種 連接構造體，該連接構造體之電子零件與配線基板係以本 發明之丙烯酸系絕緣性接著劑的自由基聚合硬化物做固 疋、該電子零件之凸塊係直接接合於配線基板之連接墊。 此種連接構造體亦為本發明之一態樣。 在電子零件方面’可舉出具備凸塊之1C晶片、具備凸 塊之發光二極體晶片等。在凸塊方面並無特別限定，可較 11 201012890 佳使用有助於窄節距、窄面積化之柱形凸塊。此種柱形凸 塊之較佳高度為30〜1〇〇”。又，在配線基板方面可舉出 具備銅或鋁等連接墊之玻璃環氧配線基板、玻璃基板、可 撓性配線基板等。 此種連接構造體之製造方式，係將本發明之丙烯酸系 絕緣性接著劑以分配器（dispenser)等公知之供應手段來供 應於配線基板，對配線基板之連接墊，將電子零件之凸塊 以公知之手法做對位，對電子零件進行加熱加壓來使得丙 烯酸系絕緣性接著劑產生自由基聚合硬化而將電子零件固 ⑩ 定於配線基板，且使得電子零件之凸塊與配線基板之連接 墊做直接接合。此處，較佳之加熱加壓條件可舉出i 6〇〜2〇〇 C之加熱溫度、5〜10秒之加熱時間、1〇〜1〇〇g/凸塊之壓 力。 (實施例） 以下以實施例來具體說明本發明。 實施例1〜4、比較例1〜6 (1) 丙烯酸系絕緣性接著劑之調製 φ 將表1所示之配合成分以混合機做均句混合來調製丙 烯酸系絕緣性接著劑。其中，在比較例5係調製環氧系絕 緣性接著劑。此外，在比較例6係調製丙烯酸系異向性導 電接著劑。 (2) 玻璃轉化溫度之測定 以190°C-30分鐘之熱壓來製作完全硬化樣品，製作出 長20mm、寬2mm、高〇.〇5mm之測試件。所得到之測士式件 12 201012890 係依照JISK7244來測定玻璃轉化溫度。所得之結果示於表 (3)線膨脹係數之測定 以19〇。(：一 30分鐘之熱壓來製作完全硬化之樣品，針 對長5mm、直徑l.5mm之圓柱測試件，依照JISK7197來測 定較玻璃轉化溫度為低之〇〜5〇〇c的溫度區域下之線膨脹 係數（α 1)、以及較玻璃轉化溫度為高之i85〜2〇〇<t之溫度 區域下之線膨脹係數（〇： 2) »所得之結果示於表1。 〇 (4)連接構造體之製作 對形成有連接銅墊之0.5 mm厚之評價用玻璃環氧基板 之連接塾面貼合接著劑。另一方面，於形成有可靠性用 TEG(Test Element Group)之〇.4mm厚之評價用ic晶片表面 以接合機來形成高度70/zm之柱狀金凸塊。使得此評價用 1C晶片之柱形凸塊面與評價用玻璃環氧基板之連接面相對 向，將凸塊與連接墊進行對位之後，以5〇；^m厚之全氟乙 稀片來挾持並以下述熱壓接條件A或B來進行熱壓接。 ❹ 熱麼接條件A. 190C、5秒、12·8kgf/tip(80gf/凸塊） 熱壓接條件 B : 19〇t、10 秒 ' I2.8kgf/tip(80gf/凸塊） <評價1 (連接可靠性評價）> 以4端子法測定了連接構造體之初期、吸濕熔焊處理 後（於85 C、85%RH環境下放置24小時，接著使其通過最 尚溫度260 C之熔烊爐3次後）、以及pct試驗後（於121 °C 之飽和水蒸氣環境中放置96小時後）之連接電阻值。 所得之結果示於表1。 13 201012890 <評價2(吸濕剝離試驗評價）> 於連接構造體之初期、吸濕熔焊處理後（於85 〇c、 85%RH環境下放置24小時，接著使其通過最高溫度26〇(^ 之熔焊爐3次後）、以及PCT試驗後（於1 2 之飽和水蒸氣 環境中放置96小時後），以超音波映像裝置（SAT)觀察評價 用1C晶片是否發生剝離’未觀察到剝離者評價為[A]、觀察 到剝離者評價為[B]。所得之結果示於表1。 <綜合評價> 又’綜合上述評價1與評價2兩者結果，針對吸濕炫 焊後與PCT試驗後分別以下述基準來評價。所得結果示於 表1。 非常良好[Exc]:連接電阻值（評價1)在0.02Ω以下，未 觀察到剝離（評價2)之情況 良好[G]:觀察到一部分剝離（評價2)，連接電阻值（評 價1)在0.02 Ω以下，並無實用特性上問題之情況 不良[NG]:不論有無觀察到剝離（評價2)，但連接電阻 值（評價1)超過0.02Ω(包含open)之情況 14 201012890
201012890 SO· 02 1 ^0.02 1 open OQ Ql3 ο 1 ^0.02 1 ^0.02 1 Γ〇· 1 ο 1 ^0.02 1 0.06 1 0.12 1 -< OQ 〇 ο Ι^ο. 〇2 1 SO. 02 1 open CQ CQ o ο SO. 02 ! ^0.02 1 open -< CQ CQ e> ο SO. 02 ! ^o. 〇2 I open CQ CO o ο I ^0.02 1 1 ^0.02 open CO OQ o S 1 各 0.02 1 1 ^0.02 | | ^0.02 | -< < GO ο ^0. 02 ^0. 02 1 SO. 02 1 < -< < ο s <Τ5 vii ^0. 02 SO. 02 -< -< -«： ω S <=> VII SO. 02 SO. 02 -< ta ο ω I ^0.02 SO. 02 ^0. 02 -< o ο ΙΛ] 耜您ΐ S i « «= 2 i-1 a 雄 ?t * ^ ^ 1 s樓L ^ 洚 % 鍰 m 咳 Οί 寒 總合評價 吸濕熔焊後 PCT試驗後
tm*<<铖 Η 琳 qf^*< 屮4恕蛱給日7/>τ>φ : εΓ 1^吻釙^嗜^契二#^^喊寺蚩寒¥炔：31* 阳<<槳淚40二蘅^^砩-©冊)龚^^瓚奪坤：11* i<<(SI.2J31BsSUBUUOJJ3p-l3>lsulos)实本案砸画褙二敏^筚^备戚«ifi : 0Γ 阳<<輕H^qf^n-二敏命筚趔^餐' 溜潜费肊：6* 阳<<^靶蟬奪r< 日^.0郐4霄il·* 屮4泠^^聆 β 磡：8* 阳<<&抝釙^茱磾-龄#齧寰《蝴澈♦ : Γ 砣<<輕4噠^餘«(*餿寒^枓剧<态^:9* 阳勿雜H^qH?«4<槳荖碱蚪别$1 : Γ 1§<<鎪率碱一Ϊ4Β -獎率鰱蛘锻趄剧一螽鉍：寸* ^- I®潜竑砵鉍Μ :ε* 阳<<麵 H^^^-fl-案 * 遛盔裝«fs-M^你 ϊίΜ :(Ν* 砣<<釙与镞妹-槳i#遛，®ffi : U 201012890 由表1可知，實施例1〜5之情況，不論是熱壓接條件 A或B，就初期、吸濕熔焊處理後、Pct試驗後而言在連接 可靠性試驗之結果為良好，吸濕剝離試驗之結果並無實用 上之問題。
另一方面，若相對於（甲基）丙烯酸酯單體與成膜用樹脂 之合计100質量份’無機填料之使用量未滿70質量份，則 於吸濕熔焊處理後以及PCT試驗後會產生部分剝離，pcT 試驗後連接電阻值會上升成為〇pen，於實用特性上被評價 為不良。 又，並非使用丙烯酸系絕緣性接著劑而是使用環氧系 絕緣性接著劑之比較例5之情況，由於熱壓接時間不足， 所以在初期、吸濕熔焊後之連接電阻高，尤其是pcT試驗 後之連接電阻值超過〇·5Ω。此外，追加導電性粒子之比較 例6之匱况，由於被認為導電性粒子無法被充分捕捉於柱 形凸塊與電極凸塊之間，從而pCT試驗後之連接電阻值超 過 0·5Ω。 〇 產業上可利用性 本發明之自由基聚合性丙烯酸系絕緣性接著劑，可在 160〜20G°C此種相對低溫之加熱溫度條件下、5〜1()秒此種 加熱時間下進行自由基聚合硬化，且應力緩和性也優異， 故當作將1C晶片等電子零件以腳接合來接合至配線基板 時所使用之接著劑為有用者。 【圖式簡單說明】 17 201012890 (無） 【主要元件符號說明】 (無）
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Claims (1)

  1. 201012890 七、申請專利範圍： 1. 一種丙烯酸系絕緣性接著劑，含有（甲基）丙烯酸酯單 體、成膜用樹脂、無機填料、矽烷偶合劑以及自由基聚合 起始劑，用以將電子零件固定於配線基板者； 無機填料相對於（曱基）丙烯酸酯單體與成膜用樹脂之 合計100質量份係含有70〜160質量份； 丙烯酸系絕緣性接著劑之自由基聚合硬化物顯示15〇 〜185°C之玻璃轉化溫度，且在低於玻璃轉化溫度的溫度區 域顯示30〜35ppm之線膨脹係數（α 1)，在玻璃轉化溫度以 上之溫度區域顯示105〜125ppm之線膨脹係數（α 2)，並滿 足下述式（1) α 2/ α 1 ^ 3.4 ...(1) 。 2·如申請專利範圍第1項之丙烯酸系絕緣性接著劑，其 中’相對於（曱基）丙烯酸酯單體100質量份，成膜用樹脂含 有50〜1〇〇質量份；相對於（甲基）丙烯酸酯單體與成膜用樹 〇 脂之合計1 00質量份，矽烷偶合劑含有0.1〜5質量份；相 對於（曱基）丙烯酸酯單體與成膜用樹脂之合計丨00質量 份’自由基聚合起始劑含有1〜1〇質量份。 3 .如申請專利範圍第1或2項之丙烯酸系絕緣性接著 劑’係進一步相對於（曱基）丙烯酸酯單體與成膜用樹脂之合 計1 00質量份含有應力緩和劑1〜丨〇質量份。 4.如申請專利範圍第1或2項之丙烯酸系絕緣性接著 劑’其中，成膜用樹脂係笨氧樹脂。 201012890 5. 如申請專利範圍第3項之丙烯酸系絕緣性接著劑，其 中，成膜用樹脂係笨氧樹脂。 6. 如申請專利範圍第3項之丙烯酸系絕緣性接著劑，其 中’應力缓和劑係含有丙稀酸橡膠、丁腈橡膠（NBR)、丁二 烯橡膠（PB)之1種以上。 7_ —種自由基聚合硬化物，含有（甲基）丙烯酸酯單體、 成膜用樹脂、無機填料、矽烷偶合劑以及自由基聚合起始 劑’用以將電子零件固定於配線基板之丙烯酸系絕緣性接 著劑之自由基聚合硬化物； 無機填料相對於（甲基）丙烯酸酯單體與成膜用樹脂之 合計100質量份係含有70〜160質量份； 顯示150〜185°C之玻璃轉化溫度，且在低於玻璃轉化 溫度的溫度區域顯示30〜35ppm之線膨脹係數（αΐ)，在玻 璃轉化溫度以上之溫度區域顯示1〇5〜125ppm之線膨脹係 數（α 2)，並滿足下述式（1) a 21 a 1^3.4 ...(1) 。 8. —種連接構造體’係電子零件與配線基板以申請專利 範圍第1〜6項中任一項之丙烯酸系絕緣性接著劑的自由基 聚合硬化物做固定，該電子零件的凸塊直接接合於配線基 板之連接墊者。 9. 如申請專利範園第8項之連接構造體，其中，電子零 件係具備枉形凸塊之1C晶片。 10. —種連接構造艎之製造方法，用以製造申請專利範 201012890 t 圍第8項之連接構造體； 係對配線基板供應申請專利範圍第丨〜6項中任一項之 丙烯酸系絕緣性接著劑，對配線基板之連接墊進行電子零 件凸塊之對位，然後將電子零件加熱加壓以使得丙烯酸系 絕緣性接著劑做自由基聚合硬化而將電子零件固定於配線 基板’且將電子零件之凸塊與配線基板之連接塾加以直接 接合。 ❹ 八、圖式： 益
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