TWI247031B - Adhesive material and circuit connection method - Google Patents

Adhesive material and circuit connection method Download PDF

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Publication number
TWI247031B
TWI247031B TW089115770A TW89115770A TWI247031B TW I247031 B TWI247031 B TW I247031B TW 089115770 A TW089115770 A TW 089115770A TW 89115770 A TW89115770 A TW 89115770A TW I247031 B TWI247031 B TW I247031B
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TW
Taiwan
Prior art keywords
inorganic particles
electronic component
electrode
height
particle diameter
Prior art date
Application number
TW089115770A
Other languages
English (en)
Inventor
Motohide Takeichi
Junji Shinozaki
Original Assignee
Sony Chemicals Corp
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Publication of TWI247031B publication Critical patent/TWI247031B/zh

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    • 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
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • 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
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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Wire Bonding (AREA)
  • Adhesive Tapes (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)

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1247031 A7 B7 五、發明說明（I ) 【發明所屬之技術領域】 本發明係關於一種用以將具有突起狀電極的半導體元 件等電子零件的該突起狀電極、用來搭載該電子零件的配 線基板之端子電極加以連接的接著材料。 【習知技術】 以往，在行動電話等的攜帶用電子機器的主機板上， 組裝著1C構裝體，該1C構裝體係將半導體元件安裝在具 有較半導體元件大的表面積之構裝用基板上而成。惟，近 來，隨著電子機器的輕薄短小化和高功能化的進展，乃取 代先前的1C構裝體，將處於裸晶片狀態之半導體元件覆晶 組裝在主機板上，或使用晶片尺寸封裝(CSP)(其安裝在與 半導體元件大約相同大小的封裝用基板上）。在這些情形下 ，當將裸晶片或CSP的突起狀電極(凸塊)連接到主機板的 連接端子上時，係使用著液狀、糊狀或薄膜狀的絕緣性接 著劑，或是使用讓導電性粒子分散在這些的絕緣性接著劑 中所構成的糊狀或薄膜狀的各向異性導電接著劑。 但是，在藉由這種接著劑來連接的連接部中，由於在 裸晶片（或CSP)和主機板間有熱線膨脹率的差，故應力會 集中在裸晶片的突起狀電極，往往在突起狀電極處發生浮 起或剝離，導致導通電阻的增大與連接不良的發生，而有 連接可靠性大幅地降低的問題。 又，由於裸晶片的突起狀電極的高度不均等，在對向 的裸晶片的突起狀電極與主機板的連接端子之間的距離上 也會發生不均，從而亦有連接可靠性無法提昇的問題。 4 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公f ) (請先閱讀背面之注意事項再填寫本頁) ---------訂---------線 _. 經濟部智慧財產局員工消費合作社印製 A7 1247031 B7_____ 五、發明說明（x ) 是以，爲了確保裸晶片和主機板的連接可靠性’乃提 出在絕緣性接著劑或各向異性導電接著劑中，以相對於接 著樹脂組成物100重量份爲5〜200重量份的比例的方式來 配合平均粒徑3/zm以下的無機質充塡材，藉以增大黏度 、提高其密接力(特開平11 一 061088號公報）。 【發明所欲解決之課題】 但是，即使如特開平11 一 061088號公報所記載，也僅 規定無機質充塡材的粒徑和配合量，仍有不能確保裸晶片 和主機板間的充分之連接可靠性的問題。 本發明係用以解決以上之習知技術的問題所得者，其 目的在於將具有突起狀電極之半導體元件等電子零件的該 突起狀電極與主機板等配線基板的端子電極，以可消除其 間之距離不均、並可藉良好的連接可靠性來連接的方式加 以設定。 【用以解決課題之手段】 本案發明人等發現到，將具有突起狀電極的半導體元 件等電子零件的該突起狀電極、用來搭載該電子零件的配 線基板之端子電極以含有至少一種之硬化性樹脂與無機系 粒子的接著材料來進行連接之際，不僅規定所使用的無機 系粒子的平均粒徑與配合量，同時將無機系粒子的比表面 積設定在既定範圍內，且將其最大粒徑設定在電子零件的 突起狀電極高度與配線基板之端子電極高度之總和的一半 以下，藉此，能達成上述的目的，如此便完成了本發明。 亦即，本發明係提供一種接著材料，係用以將具有突 5 本紙張尺度適用中國國家^準（CNS)A4規格（210 X 297公' 一 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 Φ--------訂---------線丨·----------------------- 1247031 A7 經濟部智慧財產局員工消費合作社印製 B7 五、發明說明（> ) 起狀電極之電子零件（較佳爲裸晶片等之半導體元件）之該 突起狀電極、用來搭載該電子零件的配線基板之端子電極 加以連接；其特徵在於，於含有至少一種之硬化性樹脂與 無機系粒子的接著材料中’無機系粒子之比表面積S(m2/g) 滿足以下式（1)、平均粒徑DK/zm)與最大粒徑D2(//m)分別 滿足以下式(2)及(3) ·’ 3<S^17 (1) D^5 (2) D2^0.5(h! + h2) (3) (式中，h係電子零件之突起狀電極高度（//m)，h2係 配線基板之端子電極高度（//m)) ，且接著材料中包含10〜60%體積之無機系粒子。 又，本發明係提供一種電路連接方法，係將具有突起 狀電極之電子零件（較佳爲裸晶片等之半導體元件）之該突 起狀電極、用來搭載該電子零件的配線基板之端子電極， 以含有至少一種之硬化性樹脂與無機系粒子的接著材料來 連接；其特徵在於，作爲接著材料，係將比表面積 滿足以下式（1)、平均粒徑DJ/zm)與最大粒徑D2(//m)分別 滿足以下式(2)及(3) 3<S^17 ⑴ 〇1-5 (2) D2^0.5(h! + h2) (3) (式中’ h係電子零件之突起狀電極高度（//m)，^係 配線基板之端子電極高度（、 6 本紙張尺度適用中國國豕標準（CNS)A4規格（21〇 X 297公釐） --------^--------- (請先閱讀背面之注意事項再填寫本頁) 1247031 A7 B7 五、發明說明（斗） 的無機系粒子，以成爲10〜60體積％的方式分散於硬 化性樹脂中所得之接著材料。 【發明之實施形態】 以下，詳細說明本發明。 本發明的接著材料是用來將具有突起狀電極的電子零 件之該突起狀電極與用來搭載該電子零件的配線基板之端 子電極加以連接之物，其含有至少一種的硬化性樹脂與無 機系粒子。在此，就無機系粒子而言，所需使用之物係： 採用BET法所測定的比表面積S(m2/g)必須滿足以下式（1) ，採用庫爾特計數器(Coulter counter)法所量測的平均粒徑( 將10萬個粒子測定3次所得結果的平均)DK/zm)和最大粒 徑D2(//m)必須分別滿足以下式(2)及(3)。 3<S^17 (1) Di‘5 (2) D2^0.5(h1 + h2) (3) (式中，h係電子零件的突起狀電極高度（//m)，h2是 配線基板的端子電極高度（//m))此乃由於，當無機系粒子 的比表面積S爲3m2/g以下時，粒子直徑會變得太大，恐 有損傷電子零件之連接面側的保護膜之虞，當比表面積S 超過17m2/g時，接著材料的流動性會降低，故連接時需要 較大的壓力，接著作業性也會降低，其結果，不易將具有 突起狀電極的電子零件之該突起狀電極與主機板等配線基 板之端子電極之間的距離不均加以消除。又，當無機系粒 子的平均粒徑Dl(//m)超過5//m時，夾在突起狀電極與配 7 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ------------1 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製
經濟部智慧財產局員工消費合作社印製 1247031 A7 B7 五、發明說明（y) 線基板之間的無機系粒子之妨礙電連接的機率會變高，又 ，當無機系粒子的最大粒徑超過電子零件的突起 狀電極高度hK/^m)與配線基板的端子電極高度h2(//m)之 總和的一半時，無機系粒子會變得太大，有損傷電子零件 之連接面側的保護膜之虞。 還有，一般說來，無機系粒子的最大粒徑D2(/zm)最 好不要超過15 // m。 又，就無機系粒子而言，最好使用其平均粒徑Di滿足 以下式(4)之物。 0.1(h1 + h2)^D1 (4) 這種無機系粒子在接著材料中的配合量爲10〜60體 積％、較佳爲2〇〜50體積％。此乃由於，若未滿10體積％ ，則不易得到電氣上連接可靠性，若超過60體積％，則連 接時的連接材料之流動性會明顯地惡化，不易得到良好的 連接。 就以上所說明的無機系粒子之材質而言，能使用氧化 鋁、二氧化矽等之金屬氧化物、氮化鋁、氮化矽等之金屬 氮化物等。對這些材質，也能施以眾所周知的耐水性處理 〇 就構成接著材料的硬化性樹脂而言，可使用以往以來 將半導體兀件覆晶組裝在主機板時作爲接著成分所使用的 熱硬化性樹脂，例如，環氧樹脂、聚氨酯樹脂、不飽和聚 酯樹脂等。又，亦可舉出具有會依據紫外線等之特定波長 而反應的官能基的硬化性樹脂，例如，有丙烯酸酯系樹脂 8 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) --------訂—------丨' A7 1247031 _ _ B7____ 五、發明說明（。） 、甲基丙烯酸酯系樹脂。這些也可將至少二種混合使用。 在本發明中，作爲硬化性樹脂的至少一種，從確保接 著材料的作業性(塗佈性等)之觀點來看，以使用在100°c下 展現500cps以下(較佳爲200cps以下）之黏度的液狀之硬化 性樹脂爲佳。這種在l〇〇°C展現500cps以下的硬化性樹脂 在硬化性樹脂整體中的配合量以至少20重量％爲佳。 在本發明的接著材料中，能配合硬化劑，其中，能使 用咪唑系硬化劑、酸酐系硬化劑、聯氨系硬化劑、雙氰胺 系硬化劑等。其中，以使用讓這些硬化劑潛在化的潛在性 硬化劑爲佳。 在本發明的接著材料中，也能進一步含有平均粒徑0.5 〜的導電性粒子。藉此，能使用接著材料來作爲各 向異性導電接著劑。就這種導電性粒子而言，能使用以往 在各向異性導電接著劑上所利用的導電性粒子，例如，有 焊錫、鎳等之金屬粒子、在樹脂粒子表面形成金屬電鎪層 的複合粒子、在這些的粒子表面形成絕緣皮膜的粒子等。 導電性粒子的配合量，能根據導電性粒子的種類和接著劑 的用途來適宜決定。 以上所述的接著材料係設定成在85t、85%RH的周圍 環境下其吸濕率爲1.5重量％以下。藉此，能防止水分侵入 具有突起狀電極之電子零件與配線基板之連接端子間的接 合部（係本發明接著材料的適用對象），能提高連接可靠性 〇 又’接著材料的吸濕率，係由例如成型爲圓筒形(直徑 9 氏張尺度適用中國國家標準（CNS)A4 -- (請先閱讀背面之注意事項再填寫本頁) ---------訂---------I - 經濟部智慧財產局員工消費合作社印製 1247031 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（9 ) 5mm，高度15mm)的接著材料在13(rc下乾燥丨小時，然後 在85°C、85%RH的周圍環境下放置168小時之時的重量變 化所算出。 本發明的接著材料係藉由將硬化性樹脂、無機系粒子 以及視需要而配合的各種添加劑均勻混合來製造。這種情 形’藉由調整在硬化性樹脂的全體中之液狀的硬化性樹脂 之配合比例，能將接著材料製成液狀〜糊狀的形態。又， 當成爲薄膜狀的形態時，只要將硬化性樹脂、無機系粒子 以及視需要而配合的各種添加劑均勻地混合於溶劑中，調 製成塗佈液，將該塗佈液塗佈在剝離薄片上，並加以乾燥 即可。 又’就用來搭載電子零件的配線基板而言，沒有特別 的限制，能使用以往的剛性基板、可撓性基板等。 以上所說明的本發明的接著材料，可適切地用在將具 有突起狀電極的電子零件之該突起狀電極與用來搭載該電 子零件的配線基板之端子電極的電路加以連接之連接方法 中。 【實施例】 以下，具體地說明本發明。 實施例1〜8及比較例1〜7 在環氧系樹脂(4032D(黏度200cPs/100°C));大日本油 墨工業公司製造）20重量份、環氧系樹脂（EP828(黏度 150cps/100°C));油化殼牌環氧公司製造)20重量份、苯氧 系樹脂(YP50 ;東都化成公司製造）20重量份及咪唑系硬化 10 本紙張尺度適用中國國家標準（CNS)A4規格（21(^ 297公釐） ---------------------訂---------I. (請先閱讀背面之注意事項再填寫本頁) -I I I I I I— I I I I I I I I I I I I I I _ 1247031 Α7 Β7 五、發明說明（又） 劑(HX3941 ;旭化成公司製造)4〇重量份所成的混合物中， 將表1所示的二氧化矽以表2及3所示的配合量及體積含 有率(％)與甲苯同時混合，調製成接著材料的塗佈液後，以 乾燥厚度成爲40#m的方式塗佈在剝離薄片上 # 風循環式爐中乾燥製作成薄膜狀的接著材料 ί女者在熱 著薄膜）。 、（以卞，簡稱接 【表 使用之二輕^_ 平均粒徑 Di( β m) 最大 β m) 助T比表面積 二氧化矽1 0.5 二氧化矽2 0.5 8 - 二氧化矽3 3.0 8 17 二氧化石夕4 1.5 8 95 二氧化石夕5 0.5 35 H 二氧化石夕6 0.5 10 4 20 (杜叫先閱4頃背面之注意事項再填寫本頁) t 訂---------線！ 經濟部智慧財產局員工消費合作社印製 【表2】 (重量份）
體積含有率(％) 35 11 二氧化矽1 二氧化石夕2 二氧化石夕4 本紙張尺度適用巾s ® _準(CNS)A4規格（210 X 297公釐） 1247031 五、發明說明（气） 【表3】 A7 B7 比較例 15 二氧化矽3 二氧化矽5 二氧化矽6 體積含有率(％) 7.6 30 14 100 4 ----- 100 S 35 ;〇 100 14 35 經濟部智慧財產局員工消費合作社印製
【評價】 分別評價各實施例及各比較例之接養:： 連接可靠性及作業性(壓入）。 (吸濕率(％)) 將各實施例及各比較例的接著材料成刑 次场W同形（直柯 5mm，高度15mm)，在130°C下乾燥1小時，择^ J吋，接者秤宜重 量後，在85°C、85%RH環境下，放置168小時後，再产，、 其重量，根據這些測量結果的差（重量變化），算出吸 。將所得的結果表示在表4。 (連接可靠性） 在裏面設有160個高度20//m的鍍金凸塊(高度hl = 20//m/150/zm間距)的石夕1C晶片(6.3mm平方/0.4mm厚度) 、經施以鍍鎳-金形成銅配線(厚度(電極高度)h2= 12/zm)的 玻璃環氧基板(40mm平方/0.6mm厚度）之間，配置各實施 例及各比較例的接著薄膜，並進行對位，採用覆晶接合機 (bonder)，將兩者加以連接，得到連接體(連接條件：18〇°C 材料的吸 濕率、 (請先閱讀背面之注咅？事項再填寫本頁) 訂 . 線— 一 12 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1247031 A7 B7 五、發明說明（…）
5 1.7 0.39/0 6 1.3 0.18/0 7 1.1 0.09/0 8 0.8 0.07/0 比較例1 2.2 1.31/X 2 1.7 2.95/X 3 1.6 * /X 4 1.9 1.64/X 5 1.6 0.84/X 6 2.0 2.16/X 7 1.5 * /X *自初期連接時起即無法導通。【表5】 (請先閱讀背面之注意事項再填寫本頁) 接著薄膜 壓入力 (kgf) 壓入量 (//m) 實施例1 2 20 實施例2 1 10 2 18 4 29 實施例3 2 12 比較例3 1 7 2 15 4 24 比較例7 1 1 2 3 4 7 經濟部智慧財產局員工消費合作社印製 由表4可知，滿足式（1)〜（3)關係的實施例1〜實施例 8的接著薄膜顯示良好的連接可靠性。又，由表5可知， 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） A7 1247031 B7___ 五、發明說明（Q ) 至少實施例1〜實施例3的接著薄膜作業性也良好。 在另一方面，二氧化矽的體積含有率低於下限（10%)的 比較例1之接著薄膜，不但吸濕率較高，且連接可靠性也 不足。又，採用bet比表面積遠超過上限（I7m2/g)的二氧 化矽的比較例2及比較例3的接著薄膜在連接可靠性不足 。又，採用最大粒徑不能滿足式(3)的二氧化矽的比較例4 及比較例5的接著薄膜在連接可靠性上也不足。又，採用 BET比表面積稍微超過上限（17m2/g)的二氧化矽之比較例6 及比較例7的接著薄膜在連接可靠性也不足。 還有，關於比較例3及比較例7的接著薄膜，由表5 的結果可知，藉由使用比表面積17m2/g以下的無機系粒子 ，能確保連接時的作業性。 【發明效果】 依據本發明的接著材料，可將具有突起狀電極之半導 體元件等電子零件的該突起狀電極與主機板等配線基板之 端子電極之間之距離不均加以消除、並可藉良好的連接可 靠性來連接。 【圖式之簡單說明】 1 接著材料 2 虛晶片 3 玻璃基板 15 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 Φ--------訂---------線—_-----------------------

Claims (1)

1247031 ^ C8 D8 __ 六、申請專利範圍 件之該突起狀電極、用來搭載該電孑零件的配線基板之端 子電極以含有至少一種之硬化性樹脂與無機系粒子的接著 材料來連接；其特徵在於，作爲接箸材料，係將比表面積 S(m2/g)滿足以下式（1)、平均粒徑DiO111)與最大粒徑 m)分別滿足以下式(2)及(3): 3< S^17 (1) D^5 (2) D2^〇.5(hi + h2) (3) (式中，h係電子零件之突起狀電極高度（//m)，h2係 配線基板之端子電極高度（//m)) 的無機系粒子，以成爲10〜60體積％的方式分散於硬 化性樹脂中所得之接著材料；無機系粒子的平均粒徑D!係 進一步滿足以下式(4): 0· 1 (hi + li2)2Di (4) 〇 6.如申請專利範圍第5項之電路連接方法，其中，電 子零件爲半導體元件。 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ...................裝-..... (請先閱讀背面之注意事項再塡寫本頁) 、π*" ·
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Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005195690A (ja) * 2003-12-26 2005-07-21 Toshiba Corp 金属含有樹脂粒子、樹脂粒子、及び電子回路の製造方法
KR101215243B1 (ko) * 2004-12-17 2012-12-24 파나소닉 주식회사 플립 칩 실장용 수지 조성물 및 범프 형성용 수지 조성물
JP4428355B2 (ja) * 2006-03-30 2010-03-10 Ｔｄｋ株式会社 電子部品の評価方法
CN101755025B (zh) * 2007-08-10 2014-03-12 旭化成电子材料株式会社 粘合剂和接合体
WO2009072497A1 (ja) * 2007-12-03 2009-06-11 Hitachi Chemical Company, Ltd. 回路部材接続用接着剤及び半導体装置
JP2013038181A (ja) * 2011-08-05 2013-02-21 Nitto Denko Corp ダイシング・ダイボンドフィルム
CN116348563A (zh) * 2020-09-28 2023-06-27 株式会社力森诺科 电路连接用黏合剂薄膜、含无机填料组合物、以及电路连接结构体及其制造方法

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4818823A (en) * 1987-07-06 1989-04-04 Micro-Circuits, Inc. Adhesive component means for attaching electrical components to conductors
EP0361975B1 (en) * 1988-09-29 1995-05-24 Tomoegawa Paper Co. Ltd. Adhesive tapes
US5121190A (en) 1990-03-14 1992-06-09 International Business Machines Corp. Solder interconnection structure on organic substrates
US5288769A (en) * 1991-03-27 1994-02-22 Motorola, Inc. Thermally conducting adhesive containing aluminum nitride
JPH04366630A (ja) * 1991-06-13 1992-12-18 Sharp Corp 異方性導電接着テープ
JP3103956B2 (ja) 1993-06-03 2000-10-30 ソニーケミカル株式会社 異方性導電膜
US6140402A (en) 1993-07-30 2000-10-31 Diemat, Inc. Polymeric adhesive paste
US5814180A (en) * 1993-11-03 1998-09-29 W. L. Gore & Associates, Inc. Low temperature method for mounting electrical components
JP3611066B2 (ja) 1996-08-29 2005-01-19 株式会社ルネサステクノロジ 無機質充填剤及びエポキシ樹脂組成物の製造方法
JP3821173B2 (ja) * 1996-12-19 2006-09-13 信越化学工業株式会社 エポキシ樹脂組成物
JP4178565B2 (ja) 1997-08-25 2008-11-12 日立化成工業株式会社 回路部材接続用接着剤
JP3283451B2 (ja) 1997-10-09 2002-05-20 住友ベークライト株式会社 液状注入封止アンダーフィル材
DE69934153T2 (de) 1998-02-02 2007-09-20 Shin-Etsu Chemical Co., Ltd. Verfahren zur Montage von Flip-Chip-Halbleiterbauelementen
JPH11288979A (ja) 1998-02-02 1999-10-19 Shin Etsu Chem Co Ltd 半導体装置の製造方法
JP2001081438A (ja) * 1999-09-14 2001-03-27 Sony Chem Corp 接続材料
JP3371894B2 (ja) * 1999-09-17 2003-01-27 ソニーケミカル株式会社 接続材料
US6451875B1 (en) * 1999-10-12 2002-09-17 Sony Chemicals Corporation Connecting material for anisotropically electroconductive connection
JP2001164232A (ja) * 1999-12-09 2001-06-19 Sony Chem Corp 熱硬化性接着材料
JP3738655B2 (ja) * 2000-03-31 2006-01-25 ソニーケミカル株式会社 異方性導電接着材料及び接続方法

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