201134904 六、發明說明： 【發明所屬之技術領域】 本發明關於電路連接材料及使用其之電路構件之連接 構造。 【先前技術】 作爲半導體元件或液晶顯示元件用的黏著劑，使用黏 著性優異且顯示高的可靠性之環氧樹脂等的熱硬化性樹脂 (例如參照專利文獻1 )。作爲上述黏著劑的構成成分， 一般使用環氧樹脂、與環氧樹脂有反應性的酚樹脂等之硬 化劑、促進環氧樹脂與硬化劑的反應之熱潛在性觸媒。熱 潛在性觸媒係決定黏著劑的硬化溫度及硬化速度之重要因 子，從室溫的儲存安定性及加熱時的硬化速度之觀點來看 ，使用各種的化合物。 又，最近著眼於由丙烯酸酯衍生物或甲基丙烯酸酯衍 生物等的自由基聚合性化合物與自由基聚合引發劑的過氧 化物所構成的自由基硬化型黏著劑。自由基硬化型黏著劑 係可在低溫且短時間進行硬化（例如參照專利文獻2〜4 ) 先前技術文獻 專利文獻 專利文獻1 :特開平1 - 1 1 3 48 0號公報 專利文獻2 :特開2002-203427號公報 201134904 專利文獻3 :國際公開第98/044067號小冊 專利文獻4:特開2005 -3 1 469 6號公報 【發明內容】 發明所欲解決的問題 此等技術主要係在液晶面板等的扁平面板顯示器（ Flat Panel Display，以下稱爲「FPD」）的領域中普及’ 開始用於印刷配線板（Printed Wiring Board，以下視情況 稱爲「PWB」）與捲帶載體封裝（Tape Carrier Package， 以下稱爲「TCP」）或軟膜覆晶接合（Chip On Flex，以 下稱爲「COF」）的連接。於FPD的領域之撓性配線板（ Flexible Printed Circuits，以下視情況稱爲「FPC」）與 PWB之連接中，使用電路連接材料，一般對電路施予鍍金 處理。另一方面，於安裝晶片或電容器等的零件之PWB中 ，藉由焊料的安裝係爲主流。爲了得到良好的焊接性，作 爲電路的表面處理，嘗試形成含咪唑化合物的樹脂被膜之 處理。又，於大型的母板等中，由於不使用金而可削減成 本，一般藉由咪唑化合物等之含有有機樹脂的溶液進行處 理（以下視情況稱爲「OSP處理」），而形成有機被膜（ 以下視情況稱爲「OSP膜」）。於經如此OSP處理的電路 基板之安裝中，亦正在檢討上述電路連接材料之使用。 若爲使用環氧樹脂的陰離子聚合系之黏著劑，則對，經 OSP處理的基板，也可給予良好的黏著力與連接可靠性。 然而，從高密度安裝的潮流來看，.電路基板的構造係以& -6- 201134904 層構造爲主流’爲了散逸連接時的熱，在連接部的附近設 有通孔或貫穿孔等。由於此通孔或貫穿孔，而在陰離子聚 合系的黏著劑之硬化時無法給予充分的熱量。若花費充分 的時間而給予必要的熱量，則必須長時間的連接，使用陰 離子聚合系的黏著劑者係在生產效率上不實際。另一方面 ，自由基硬化型黏著劑係在使用FPD領域的FPC與PWB之 連接時，即使未達1〇秒的短時間也可硬化，採用於經OSP 處理的基板時，與採用於經鍍金處理的基板時比較下，有 連接電阻容易上升的問題。此係因爲OSP膜本身係非導電 性。 因此，本發明之目的爲提供能在低溫且短時間進行硬 化，而且採用於經OSP處理的基板時，可給予充分高的連 接可靠性之電路連接材料，及使用其的電路構件之連接構 造。 解決問題的手段 本發明提供一種電路連接材料，其爲將對向之電路電 極彼此電連接之電路連接材料，其含有黏著劑組成物與導 電粒子’導電粒子爲具有維氏硬度300〜1〇〇〇之金屬所形 成之核體’與被覆該核體之表面之由貴金屬所形成之最表 層’且平均粒徑爲5〜20 μηι。 又’本發明提供一種電路連接材料，其爲將對向之電 路電極之間以電連接之電路連接材料，其含有黏著劑組成 物與導電粒子，導電粒子爲具有鎳所形成之核體，與被覆 201134904 該核體之表面之由貴金屬所形成之最表層，且平均粒徑爲 5 〜20μιη ° 本發明的電路連接材料藉由同時含有如上述的導電粒 子與黏著劑組成物，可在低溫且短時間進行硬化，而且對 經OSP處理的基板亦可顯示良好的連接可靠性。 從可更短時間進行硬化的觀點來看，於本發明的電路 連接材料中，黏著劑組成物較佳爲含有自由基聚合性物質 與經由加熱會發生游離自由基之硬化劑。 又，當黏著劑組成物含有環氧樹脂與潛在性硬化劑時 ，可進一步提髙使用電路連接材料的電路構件之連接構造 的連接可靠性。 本發明提供一種電路構件之連接構造，其爲具備有： 第一之電路基板之主面上形成有第一之電路電極的第 一之電路構件，與 第二之電路基板之主面上形成有第二之電路電極，第 二之電路電極與第一之電路電極爲以對向配置方式配置之 第二之電路構件，與 設置於第一之電路基板與第二之電路基板之間，使第 一與第二之電路電極形成電連接之連接第一之電路構件與 第二之電路構件的電路連接部， 其中電路連接部爲上述本發明的電路連接材料之硬化 物，第一及第二之電路電極中的至少一者具有由咪唑化合 物所形成之被膜。 於使用以往的短時間硬化型之電路連接材料的電路構 -8- 201134904 件之連接構造中，當電路電極具有OSP膜時，以未達10秒 的短時間，係在提高連接性上有困難的傾向。相對於此， 本發明的電路構件之連接構造，由於電路連接部爲上述本 發明的電路連接材料之硬化物，故即使未達10秒的連接時 間，也可得到良好的連接性。 本發明的電路構件之連接構造，由於以含有有機樹脂 的材料所成的被膜來形成電路電極表面，故保護電路電極 防止氧化，可得到良好的焊接性。又，本發明的連接構造 ，由於藉由上述本發明的電路連接材料來連接電路構件彼 此，故具有充分高的黏著強度及連接可靠性。 發明的效果 若依照本發明，可提供能在低溫且短時間進行硬化， 而且採用於經OSP處理的基板時，可給予充分高的連接可 靠性之電路連接材料，及使用其的電路構件之連接構造。 【實施方式】 實施發明的形態 以下’按照需要一邊參照圖面，一邊詳細說明本發明 的適宜實施形態。惟，本發明係不受以下的實施形態所限 定。再者，圖面中，對相同要素係附有相同符號，重複的 說明係省略。又，只要沒有特別預先指明，則上下左右等 的位置關係以圖面所示的位置關係爲基礎。再者，圖面的 尺寸比率係不受圖示的比率所限定。 -9 - 201134904 本實施形態的電路連接材料係將電路電極彼此電連接 用的黏著劑。圖1係顯示電路連接材料的一實施形態之截 面圖。圖1所示的電路連接材料1係由樹脂層3與在樹脂層3 內分散的複數之導電粒子5所構成，且具有薄膜狀之形狀 〇 以下說明電路連接材料1的各構成材料。 (導電粒子） 導電粒子5係具有由維氏硬度300〜1 000的金屬所形成 的核體，與被覆該核體的表面之由貴金屬所形成的最表層 ，且平均粒徑爲5〜20μηι。又，導電粒子5係具有由鎳所形 成的核體，與被覆該核體的表面之由貴金屬所形成的最表 層，且平均粒徑爲5〜20μηι。如此的導電粒子係容易貫通 電路電極的非導電性被膜，容易抑制連接電阻的上升。因 此，使用含有上述導電粒子的電路連接材料，可製作連接 可靠性優異的電路構件之連接構造。 導電粒子5的核體較佳爲由鎳、鉻、鉬、錳、鈷、鐵 、錳、釩、鈦、鉑、銥、餓、鎢、鉬、鈮、锆、鈀等的過 渡金屬中選出的至少一種金屬所構成，更佳爲由鎳所構成 〇 構成核體的金屬對維氏硬度爲300〜1000，尤佳爲400 〜800，更佳爲500〜700。核體的維氏硬度未達300時，導 電粒子容易變形，電極上的osp膜之排除性有降低的傾向 。超過1 000時，粒子不易變形，雖以確保充分的接觸面積 -10- 201134904 以便給予良好的連接可靠性。 導電粒子5的最表層較佳爲由金、銀、鉑、鈀、铑、 銥、釕、餓等的貴金屬中選出的至少一種金屬所構成，尤 佳爲由金或鉑所構成，更佳爲由金所構成。藉由以此等金 屬構成導電粒子5的最表層，可充分增長電路連接材料1的 使用期限。 導電粒子5的最表層之厚度較佳爲0.03〜0.4μιη，更佳 爲0.08〜0·2μιη。最表層的厚度未達0.03μηι時，導電粒子 的導電性降低，連接電阻有增加的傾向，超過0.4 μιη時， 於核體上形成最表層之際，成本變高，有便宜性差的傾向 。再者，核體更佳爲其全面係被貴金屬形成的最表層所被 覆，惟在不脫離本發明的效果之範圍內，核體的一部亦可 露出。 導電粒子的平均粒徑爲5〜20μπι，較佳爲8〜20μηι， 更佳爲8〜15μηι。導電粒子的平均粒徑未達5μιη時，於導 電粒子與電極接觸之前，樹脂層3進行硬化，超過20 μιη時 ，由於導電粒子的曲率半徑大，電極上的OSP膜之排除性 降低，在任一情況下皆變難以取得電的導通。再者，本案 所規定的導電粒子之平均粒徑，係使用「S A LD - 1 0 0 0」（ 島津製作所製，商品名）所測定的雷射繞射方式之測定値 〇 導電粒子5的配合量係按照用途而適宜設定，但通常 相對於1〇〇體積份的黏著劑層3 (即，電路連接材料1中的 導電粒子5以外之部分）而言，爲〇.1〜30體積份的範圍內 -11 - 201134904 。再者，從在同一電路基板上防止相鄰的電路 短路的觀點來看，導電粒子的配合量更佳爲< 份。 (黏著劑組成物） 樹脂層3較佳爲含有會發生游離自由基的 由基聚合性物質。換言之，電路連接材料1較 生游離自由基之硬化劑、含自由基聚合性物質 成物、與導電粒子5。當電路連接材料1被加熱 由基聚合性物質的聚合而在樹脂層3中形成交 成電路連接材料1的硬化物。此時，電路連接;f 作爲自由基硬化型的黏著劑之機能。 電路連接材料1中所用的發生游離自由基 係藉由過氧化化合物、偶氮系化合物等的加熱 生游離自由基，可按照目的之連接溫度、連接 期限等來適宜選定。配合量係以電路連接材米 量爲基準，較佳爲0.05〜10質量％，更佳爲0.1 以電路連接材料1的全體質量爲100質量份，較 10質量份，更佳爲0.1〜5質量份）。發生游離 化劑，具體地可由二醯基過氧化物、過氧二碳 酯、過氧縮酮、二烷基過氧化物、氫過氧化物 又，爲了抑制電路構件的連接端子之腐蝕，較 酯、二烷基過氧化物、氫過氧化物中選擇，更 高反應性的過氧酯中選擇。 電極彼此之 .1〜1 0體積 硬化劑與自 佳爲含有發 的黏著劑組 時，藉由自 聯構造，形 才料1係具有 之硬化劑， 而分解，發 時間、使用 + 1的全體質 〜5質量％ ( :佳爲〇. 〇 5〜 自由基的硬 酸酯、過氧 等中選擇。 佳爲由過氧 佳爲由得到 -12- 201134904 作爲二醯基過氧化物類，例如可舉出2,4 -二氯苯甲醯 基過氧化物、3，5,5 -三甲基己醯基過氧化物、辛醯基過氧 化物、月桂醯基過氧化物 '硬脂醯基過氧化物、琥珀醯基 過氧化物、苯甲醯基過氧甲苯及苯甲醯基過氧化物。 作爲過氧二碳酸酯類’例如可舉出二正丙基過氧二碳 酸酯、二異丙基過氧二碳酸酯、雙（4-第三丁基環己基） 過氧二碳酸酯、二-2-乙氧基甲氧基過氧二碳酸酯類、二（ 2-乙基己基過氧）二碳酸酯、二甲氧基丁基過氧二碳酸酯 及一（3 -甲基-3-甲氧基丁基過氧）二碳酸醋。 作爲過氧酯類，例如可舉出1，1，3,3-四甲基丁基過氧 新癸酸酯、1-環己基-1-甲基乙基過氧壬酸酯、第三己基過 氧新癸酸酯、第三丁基過氧三甲基乙酸酯、1，1，3,3 -四甲 基丁基過氧-2-乙基己酸醋、2,5 -二甲基- 2,5 -二（2 -乙基己 醯基過氧）己烷、1-環己基-1-甲基乙基過氧2-乙基己酸酯 、第三己基過氧-2-乙基己酸酯、第三丁基過氧-2-乙基己 酸酯、第三丁基過氧異丁酸酯、1,1-雙（第三丁基過氧） 環己烷、第三己基過氧異丙基單碳酸酯、第三丁基過氧-3，5,5-三甲基己酸酯、第三丁基過氧月桂酸酯、2,5-二甲 基-2,5-二（間甲苯醯基過氧）己烷、第三丁基過氧異丙基 單碳酸酯、第三丁基過氧-2-乙基己基單碳酸酯、第三己基 過氧苯甲酸酯及第三丁基過氧乙酸酯。 作爲過氧縮酮類，例如可舉出1，1_雙（第三己基過氧 )-3,3,5·三甲基環己烷、1，卜雙（第三己基過氧）環己烷 、1,1-雙（第三丁基過氧）-3，3,5-三甲基環己烷、1,1-( -13- 201134904 第三丁基過氧）環十二烷及2,2-雙-(第三丁基過氧）癸烷 〇 作爲二烷基過氧化物類，例如可舉出α，α’雙（第三丁 基過氧）二異丙基苯、二異丙苯過氧化物、2,5-二甲基- 2,5-二（第三丁基過氧）己烷及第三丁基異丙苯過氧化物 〇 作爲氫過氧化物類，例如可舉出二異丙基苯氫過氧化 物及異丙苯氫過氧化物。 此等發生游離自由基的硬化劑係可單獨或混合使用， 亦可混合分解促進劑、抑制劑等而使用。又，此等硬化劑 經聚胺甲酸酯系、聚酯系的高分子物質等被覆而成爲微膠 囊化者，由於延長可使用時間而較佳。 電路連接材料1中所用的自由基聚合性物質，係具有 藉由自由基進行聚合的官能基之物質，可舉出丙烯酸酯、 甲基丙烯酸酯、馬來醯亞胺化合物、檸康醯亞胺樹脂、納 迪醯亞胺樹脂等。自由基聚合性物質的配合量，以電路連 接材料1的全體質量爲100質量份，較佳爲20〜50質量份， 更佳爲30〜40質量份。自由基聚合性物質係可以單體及寡 聚物的任一狀態使用，亦可倂用單體與寡聚物。 作爲JL述丙烯酸酯（含有對應的甲基丙烯酸酯，以下 相同）’例如可舉出丙烯酸甲酯、丙烯酸乙酯、丙烯酸異 丙酯、丙烯酸異丁酯、乙二醇二丙烯酸酯、二乙二醇二丙 烯酸酯、三羥甲基丙烷三丙烯酸酯、四羥甲基甲烷四丙烯 酸酯、2-羥基-1，3-二丙烯氧基丙烷、2,2-雙[4-(丙烯氧基 -14- 201134904 甲氧基）苯基]丙烷、2，2-雙[4-(丙烯氧基聚乙氧基）苯 基]丙烷、丙烯酸二環戊酯、丙烯酸三環癸酯、三（丙烯 醯氧基乙基）異三聚氰酸酯及胺基甲酸乙酯丙烯酸酯。此 等可爲單獨或組合2種類以上使用，按照需要亦可適宜使 用氫醌、甲基醚氫醌類等的聚合抑制劑。又，當具有二環 戊烯基及/或三環癸基及/或三哄環時，由於耐熱性提高而 較佳。 上述馬來醯亞胺化合物係在分子中含有至少2個以上 的馬來醯亞胺基者，例如可舉出1-甲基-2，4-雙馬來醯亞胺 苯、N，N’-間伸苯基雙馬來醯亞胺、N，N’-對伸苯基雙馬來 醯亞胺、N，N’-間伸甲苯基雙馬來醯亞胺、N，N’-4,4-伸聯 苯基雙馬來醯亞胺、N，N’-4,4- ( 3,3’-二甲基伸聯苯基）雙 馬來醯亞胺、^：^’-4,4-(3,3’-二甲基二苯基甲烷）雙馬來 醯亞胺、Ν,Ν’-4，4-( 3，3’-二乙基二苯基甲烷）雙馬來醯亞 胺、Ν，Ν’-4,4-二苯基甲烷雙馬來醯亞胺、1^氺’-4,4-二苯基 丙烷雙馬來醯亞胺、Ν,Ν’-3,3’-二苯基楓雙馬來醯亞胺、 Ν，Ν-4,4-二苯基醚雙馬來醯亞胺、2,2-雙（4-(4-馬來醯亞 胺苯氧基）苯基）丙烷、2，2-雙（3-第二丁基-4,8- (4-馬 來醯亞胺苯氧基）苯基）丙烷、1，1-雙（4-(4-馬來醯亞 胺苯氧基）苯基）癸烷、4,4’-亞環己基-雙（1_( 4-馬來醯 亞胺苯氧基）-2 -環己基苯及2,2 -雙（4- (4_馬來醯亞胺苯 氧基）苯基）六氟丙烷。此等可爲單獨或組合2種類以上 使用。 上述檸康醯亞胺樹脂係將分子中具有至少1個檸康醯 -15- 201134904 亞胺基的檸康醯亞胺化合物聚合者，作爲檸康醯亞胺化合 物，例如可舉出苯基檸康醯亞胺、1-甲基-2，4-雙檸康醯亞 胺苯、N，N’-間伸苯基雙檸康醯亞胺、N，N’-對伸苯基雙檸 康醯亞胺、N，N-4,4-伸聯苯基雙檸康醯亞胺、N，N’-4,4-( 3,3-二甲基伸聯苯基）雙檸康醯亞胺、：^，：^’-4,4-(3,3-二 甲基二苯基甲烷）雙檸康醯亞胺、N，N’-4,4-(3,3-=ZS 二苯基甲烷）雙檸康醯亞胺、N，N’-4,4-二苯基甲烷雙檸康 醯亞胺、：^川’-4,4-二苯基丙烷雙檸康醯亞胺、>|，>4’-4,4-二 苯基醚雙檸康醯亞胺、N，N’-4,4-二苯基颯雙檸康醯亞胺、 2，2-雙（4-(4-檸康醯亞胺苯氧基）苯基）丙烷、2，2_雙（ 3 -第二丁基-3,4- (4 -檸康酿亞胺苯氧基）苯基）丙院、 1，卜雙（4-(4·檸康醯亞胺苯氧基）苯基）癸烷、4,4，-亞 環己基-雙檸康醯亞胺苯氧基）苯氧基）-2_環己 基苯及2,2-雙（4- ( 4·檸康醯亞胺苯氧基）苯基）六氟丙 烷。此等可爲單獨或組合2種類以上使用。 上述納迪醯亞胺（nadimide)樹脂係將分子中具有至 少1個納迪醯亞胺基的納迪醯亞胺化合物聚合者，作爲納 迪醯亞胺化合物，例如可舉出苯基納迪醯亞胺、丨_甲基_ 2，4-雙納迪醯亞胺苯、N，N’-間伸苯基雙納迪醯亞胺、 N，N ’ -對伸苯基雙納迪醯亞胺、N，N ’ - 4，4 -伸聯苯基雙納迪 醯亞胺、N，N’- 4,4- (3, 3 -二甲基伸聯苯基）雙納迪醯亞胺 、>1，>1’-4,4-(3,3-二甲基二苯基甲院）雙納迪醯亞胺、 叱：^’-4,4-(3,3-二乙基二苯基甲烷）雙納迪醯亞胺、1^，1^，_ 4，4_二苯基甲院雙納迪酿亞胺、N，N’- 4,4 -二苯基丙院雙納 -16- 201134904 迪醯亞胺、Ν,Ν’-4,4·二苯基醚雙納迪醯亞胺、N，N，.-4 苯基颯雙納迪醯亞胺、2，2 -雙（4 - ( 4 -納迪醯亞胺苯 )苯基）丙烷、2,2-雙（3-第二丁基-3,4- (4-納迪醯 苯氧基）苯基）丙烷、1,1-雙（4- (4 -納迪醯亞胺苯 )苯基）癸烷、4,4’-亞環己基-雙（1- ( 4-納迪醯亞胺 基）苯氧基）-2-環己基苯及2,2-雙（4-(4-納迪醯亞 氧基）苯基）六氟丙烷。此等可爲單獨或組合2種類 使用。 電路連接材料1(樹脂層3)除了含有發生游離自 的硬化劑及自由基聚合性物質，還可含有其它成分。 ’可含有熱塑性樹脂及熱硬化性樹脂。 作爲熱塑性樹脂，可使用聚乙烯樹脂、聚醯亞胺 、聚氯乙烯樹脂、聚苯醚樹脂、聚乙烯縮丁醛樹脂、 烯縮甲醛樹脂、聚醯胺樹脂、聚酯樹脂、苯氧樹脂、 乙烯樹脂、二甲苯樹脂、聚胺甲酸酯樹脂等。 又，作爲熱塑性樹脂，較佳可使用Tg (玻璃轉移 )爲40°C以上且分子量1 0000以上之含羥基的樹脂， 可適宜使用苯氧樹脂。苯氧樹脂係藉由使二官能酚類 氧氯丙烷反應直到成爲高分子量爲止，或使二官能環 脂與二官能酚類進行聚加成反應而得。 作爲熱硬化性樹脂，例如可舉出尿素樹脂、蜜胺 、酚樹脂、二甲苯樹脂、環氧樹脂及聚異氰酸酯樹脂 含有上述熱塑性樹脂時，由於操作性良好、硬化 應力緩和優異而較佳。又，上述熱塑性樹脂及熱硬化 ，4-二 氧基 亞胺 氧基 苯氧 胺苯 以上 由基 例如 樹脂 聚乙 聚苯 溫度 例如 與環 氧樹 樹脂 〇 時的 性樹 -17- 201134904 脂具有羥基等的官能基時，由於黏著性提高而更佳，亦可 經由含環氧基的彈性體、自由基聚合性的官能基所改性。 較佳爲經自由基聚合性的官能基所改性者，因爲耐熱性提 高。 從製膜性等的觀點來看，上述熱塑性樹脂的重量平均 分子量較佳爲1 0000以上，但若爲1000000以上則混合性有 變差的傾向。再者，本案所規定的重量平均分子量係指依 照以下的條件，藉由凝膠滲透層析法（GPC )，使用標準 聚苯乙烯的校正曲線所測定者。 < G P C條件> 使用的機器：日立L-6000型（日立製作所（股）製） 管柱：Gelpack GL-R420 + Gelpack GL-R43 0 + Gelpack GL-R440 (計3支）（日立化成工業（股）製） 溶析液：四氫呋喃 測定溫度：40°C 流量：1 .75mL/分鐘 檢測器：L-3 3 00RI (日立製作所（股）製） 又，樹脂層3除了含有發生游離自由基的硬化劑及自 由基聚合性物質，亦可含有環氧樹脂與潛在性硬化劑。即 ，電路連接材料1係可含有含環氧樹脂與潛在性硬化劑的 黏著劑組成物，與導電粒子5。電路連接材料1係在加熱時 藉由環氧樹脂的硬化，而在樹脂層3中形成交聯構造，以 形成電路連接材料1的硬化物。此時，電路連接材料1係具 -18- 201134904 有作爲環氧硬化型的黏著劑之機能。 作爲環氧樹脂，雙酚A、F、AD等的雙酚的環氧 醚之雙酚型環氧樹脂及苯酚酚醛清漆或甲酚酚醛清漆 生的環氧酚醛清漆樹脂係代表的環氧樹脂。作爲其它 可舉出具有萘骨架的萘型環氧樹脂、環氧丙基胺型環 脂、環氧丙基酯型環氧樹脂、脂環式環氧樹脂及雜環 氧樹脂。此等可爲單獨或混合2種以上使用。 於上述環氧樹脂之中，雙酚型環氧樹脂爲分子量 的等級，由於可廣泛取得，可任意設定黏著性或反應 而較佳。於雙酚型環氧樹脂之中，特佳爲雙酚F型環 脂。雙酚F型環氧樹脂的黏度係低，藉由與苯氧樹脂 合使用，可容易地在廣範圍中設定電路連接材料的流 。又，雙酚F型環氧樹脂亦具有容易對電路連接材料 良好的黏著性之優點。 爲了防止電子遷移，較佳爲使用雜質離子（Na + 等）濃度或水解性氯爲300ppm以下的環氧樹脂。 作爲潛在性硬化劑，只要是可使環氧樹脂硬化者 。又’潛在性硬化劑係可爲與環氧樹脂反應而倂入交 造中的化合物，也可爲促進環氧樹脂的硬化反應之觸 硬化劑。亦可倂用兩者。 作爲觸媒型硬化劑，例如可舉出促進環氧樹脂的 子聚合之陰離子聚合型潛在性硬化劑，及促進環氧樹 陽離子聚合之陽離子聚合型潛在性硬化劑。 作爲陰離子聚合型潛在性硬化劑，例如可舉出咪 丙基 所衍 例， 氧樹 式環 不同 性等 氧樹 的組 動性 賦予 ' cr 即可 聯構 媒型 陰離 脂的 唑系 • 19 - 201134904 、醯肼系、三氟硼-胺錯合物、胺醯亞胺、聚胺的鹽 '氰 胍及此等的改性物。咪唑系的陰離子聚合型潛在性硬化劑 例如係將咪唑或其衍生物附加於環氧樹脂而形成。 作爲陽離子聚合型潛在性硬化劑，例如較佳爲經由能 量線照射而使環氧樹脂硬化的感光性鑰鹽（主要使用芳香 族重氮鑰鹽、芳香族锍鹽等）。又，作爲能量線照射以外 經由加熱活性化而使環氧樹脂硬化者，有脂肪族毓鹽。此 種硬化劑由於具有速硬化性的特徵而較佳。 此等潛在性硬化劑經聚胺甲酸酯系、聚酯系等的高分 子物質、鎳、銅等的金屬薄膜及矽酸鈣等的無機物被覆而 成爲微膠囊化者，由於能延長可使用時間而較佳。 相對於1 〇〇質量份的環氧樹脂而言，潛在性硬化劑的 配合量較佳爲30〜60質量份，更佳爲40〜55質量份。潛在 性硬化劑的配合量若未達30質量份，則電路連接材料的硬 化收縮所致的對被附體之緊固力係降低。結果，不保持導 電粒子5與電路電極之接觸，可靠性試驗後的連接電阻有 變容易上升的傾向。另一方面，潛在性硬化劑的配合量若 超過60質量份，則由於緊固力變過強，電路連接材料的硬 化物中的內部應力變大，有容易導致黏著強度的降低之傾 向。 當電路連接材料爲環氧樹脂系的黏著劑時，較佳爲含 有薄膜形成材。薄膜形成材係在將液狀物固形化而使構成 組成物成爲薄膜形狀時，使該薄膜的操作成爲容易，賦予 不容易裂開、破裂或發黏的機械特性等，可在通常的狀態 -20- 201134904 (常溫常壓）下作爲薄膜操作著。 作爲薄膜形成材，可使用上述的熱塑性樹脂，從黏著 性、相溶性、耐熱性及機械強度優異來看，較佳爲使用苯 氧樹脂。 苯氧樹脂係藉由使2官能性酚類與氧氯丙烷反應直到 高分子化爲止’或使2官能性環氧樹脂與2官能性酚類進行 聚加成而得之樹脂。苯氧樹脂例如可藉由使1莫耳的2官能 性酚類與0.985〜1.015莫耳的環氧氯丙烷在鹼金屬氫氧化 物等的觸媒之存在下，於非反應性溶劑中，在40〜120 °C 的溫度進行反應而得。 又’作爲苯氧樹脂，從樹脂的機械特性或熱的特性之 觀點來看，特佳爲使2官能性環氧樹脂與2官能性酚類的配 合當量比成爲環氧基/酚性羥基=1/0.9〜1/1.1，在鹼金屬化 合物、有機磷系化合物、環狀胺系化合物等的觸媒之存在 下，於沸點爲1 20°C以上的醯胺系、醚系、酮系、內酯系 、醇系等之有機溶劑中，在反應固體成分爲50質量％以下 的條件下’加熱至50〜200°C ’使進行聚加成反應而得者 〇 作爲2官能性環氧樹脂’可使用雙酚a型環氧樹脂 '雙 酚F型環氧樹脂、雙酚AD型環氧樹脂、雙酚s型環氧樹脂 。2官能性酚類係具有2個酚性羥基者，例如可舉出氫醌類 、雙酚A、雙酚F、雙酚AD、雙酚S等之雙酚化合物。 苯氧樹脂亦可經由自由基聚合性的官能基所改性。苯 氧樹脂可爲單獨1種或混合2種以上使用。 "21 - 201134904 再者’電路連接材料1 (樹脂層3)亦可含有塡充材、 軟化材、促進劑、防老化劑、著色劑、難燃化劑、搖變劑 、偶合劑及異氰酸酯類等。含有塡充材時，由於得到連接 可靠性等的提高而較佳。塡充材的最大直徑只要是未達導 電粒子5的粒徑則可使用，配合量較佳爲5〜60體積％的範 圍。若超過60體積％ ’則可靠性提高的效果係飽和。作爲 偶合劑，從黏著性的提高之點來看，較佳爲具有乙烯基、 丙烯醯基、胺基、環氧基或異氰酸酯基的化合物。按照需 要，亦可適宜使用氫醌、甲基醚氫醌類等的聚合抑制劑。 其次’說明使用電路連接材料1的本發明之電路構件 之連接構造。電路連接材料1係適用於形成如半導體晶片 、電阻體晶片及電容器晶片等的晶片零件、以及如印刷配 線板之具有1或2個以上的電路電極（連接端子）之電路構 件彼此連接的連接構造。 圖2係顯示電路構件的連接構造之一實施形態的截面 圖。圖2中所示的電路構件之連接構造1〇〇係具備：具有第 —之電路基板11及在其主面上形成的第一之電路電極13的 第一之電路構件10;與，具有第二之電路基板21及在其主 面上形成的第二之電路電極23，以第二之電路電極23與第 —之電路電極13呈對向的方式所配置的第二之電路構件20 :與，介於第一之電路構件10與第二之電路構件20之間存 在的電路連接部la。 連接部la係將電路連接材料1硬化所形成的硬化物’ 由已硬化的樹脂層3a與導電粒子5所構成。連接部la係以 -22- 201134904 電連接對向的第一之電路電極13與第二之電路電極23之方 式，黏合第一之電路構件10與第二之電路構件20。對向的 第一之電路電極13與第二之電路電極23係經由導電粒子5 而電連接。再者，即使連接部不含有導電粒子5時，也可 經由電路連接材料1來電連接第一之電路電極13與第二之 電路電極23。 第一基板11係含有由聚酯對苯二甲酸酯、聚醚碾、環 氧樹脂、丙烯酸樹脂及聚醯亞胺樹脂所成之群中選出的至 少一種樹脂之樹脂薄膜。第一之電路電極13係由具有能作 爲電極機能之程度的導電性之材料（較佳爲由金、銀、錫 、鉑族的金屬及銦-錫氧化物所成之群中選出的至少一種 )所形成。 第二基板2 1係半導體晶片類的矽或鎵•砷等、或玻璃 、陶瓷、玻璃•環氧複合物、塑膠等的絕緣基板所形成的 多層配線板。第二之電路電極23係具有導體部23a，與在 電路電極23的表面中形成與連接部la相接部分的被膜23b 。導體部23a係由具有電路電極23能作爲電極機能的程度 之導電性的材料（較佳爲由金、銀、錫、鉑族的金屬及 銦-錫氧化物所成之群中選出的至少一種）所形成。 被膜23b係由含有有機樹脂的材料所形成的被膜，較 佳爲含有咪唑化合物等的有機樹脂。被膜23b係藉由對第 二基板 21 進行 OSP ( Organic Solderability Preservative) 處理而形成。此處所謂的0SP處理，就是亦稱爲水溶性預 助熔劑的基板之處理方法，一般以含有咪唑化合物的溶液 -23- 201134904 來處理基板而形成OSP膜。所謂含有咪唑化合物的被膜， 就是由咪唑系衍生物與金屬所產生的錯合物在電極表面上 互相結合而形成的膜。即，含有咪唑化合物的被膜，係可 藉由對形成有電路電極的基板，用含有咪唑化合物的溶液 進行OSP處理而形成。作爲咪唑化合物，從耐熱性的觀點 來看，較宜使用苯并咪唑系衍生物。OSP處理例如係可使 用市售者的四國化成（股）製的商品名「Tufence F2」、 「Tufence F2 ( LX )」、（股）三和硏究所製的商品名「 Cu Coat GVII」、Enthone. Inc製的商品名「Entek 106A」 、「Entek 106A ( X )」，或ΜEC (股）製的商品名「 Mecseal CL-5 8 24S」、「Mecseal CL-5018」、「Mecseal CL-5018S」來進行。此等可爲單獨或組合2種類以上使用 〇 本發明的電路連接材料係第一及第二之電路電極中的 至少一者可用於連接具有由含有有機樹脂的材料所成的被 膜之電路構件。再者，如圖3中顯示電路構件的連接構造 之一實施形態的截面圖，不僅第二之電路電極23，而且第 一之電路電極13亦可具有導體部13a、與在電路電極13的 表面中形成與連接部la相接部分之被膜13b。被膜13 b係藉 由與被膜23b同樣的方法來形成。 電路構件之連接構造100，例如係可藉由依順序層合 第一之電路構件10、上述薄膜狀的電路連接材料1與第二 之電路構件20，以使得第一之電路電極13與第二之電路電 極23呈對峙，將所得之層合體加熱及加壓或照射光，以第 -24- 201134904 —之電路電極13與第二之電路電極23被電連接的方式，連 接第一之電路構件10與第二之電路構件20之方法而獲得。 於此方法中，可首先於使支持薄膜上所形成的薄膜狀 之電路連接材料1貼合在第二之電路構件20上之狀態下， 進行加熱及加壓而暫時黏著電路連接材料1，剝離支持薄 膜後，以電路電極呈對向的方式，邊定位邊載置第一之電 路構件10，而準備層合體。爲了防止連接之際的加熱所產 生的揮發成分對連接的影響，於連接步驟之前較佳爲將電 路構件預先加熱處理。 將上述層合體加熱及加壓的條件，係按照電路連接材 料中的組成物之硬化性等來適宜調整，以使得電路連接材 料進行硬化而得到充分的黏著強度。 構成連接構造的電路構件所具有之基板，係可爲@及 鎵•砷等的半導體晶片，以及玻璃、陶瓷、玻璃•環氧複 合物及塑膠等之絕緣基板》 實施例 以下使用實施例來更具體說明本發明的內容。惟，本 發明不受此等實施例所限定。 (1 )電路連接材料之製作 (1-1)構成黏著劑組成物的各成分之準備 「Perhexa 250」：2,5-二甲基-2,5-二（2-乙基己醯基 過氧）己烷（日本油脂製，商品名） -25- 201134904 ^ UN5 5 00」：胺基甲酸乙酯丙烯酸酯寡聚物（根上 工業製，商品名） 「DCP-A」：二環戊二烯型二丙烯酸酯（東亞合成製 •商品名） 「M-215」：異三聚氰酸EO改性二丙烯酸酯（東亞合 成製，商品名） 「P-2M」：2-甲基丙烯醯氧基乙基酸式磷酸酯（共榮 社化學製，商品名） 「HX3 94 1 HP-SS」：含有陰離子聚合型潛在性硬化劑 的環氧樹脂（含有35質量％的咪唑系微膠囊型硬化劑，旭 化成化學製，商品名） 「UR-800」：聚酯胺基甲酸乙酯（東洋紡績製，商品 名） 「EV40W」：乙烯-醋酸乙烯基共聚物（三井•杜邦 聚化學製，商品名） 「PKHC」：雙酚A型苯氧樹月旨（Mw45000，INCHEM 公司製’商品名） 「丙烯酸橡膠A」：40質量份的丙烯酸丁酯-30質量份 的丙烯酸乙酯-30質量份的丙烯腈-3質量份的甲基丙烯酸環 氧丙酯之共聚物（重量平均分子量約85萬） 「SH6040」：矽烷偶合劑（γ-環氧丙氧基丙基三甲氧 基矽烷，東麗•道康寧•聚矽氧製，商品名） (1-2)導電粒子之準備 -26- 201134904 作爲「導電粒子A」，準備一種導電粒子，其具有由 平均粒徑9μιη的Ni粒子所成之核體，與對該核體施予鍍金 而形成的由金所成之最表層。又，作爲「導電粒子B」， 準備由平均粒徑9μιη的Ni粒子所成之導電粒子。再者，作 爲「導電粒子C」，準備在表面具有多數的突起部，由平 均粒徑4μιη的Ni粒子所成之導電粒子。 (實施例1 ) 配合8質量份（以不揮發份換算爲4質量份）的「 Perhexa 25〇」之5〇質量％烴溶劑溶液、60質量份（以不揮 發份換算爲30質量份）當作自由基聚合性物質的「 UN5 5 00」之50質量％甲苯溶液、8質量份的「DCP-A」、8 質量份的「M-215」、2質量份的「P-2M」、150質量份（ 以不揮發份換算爲45質量份）的「UR-8200」之30質量％ 甲基乙基酮/甲苯（=50/50 )溶液及50質量份（以不揮發份 換算爲10質量份）的「EV4 0W」之20質量％甲苯溶液，再 配合10質量份的「導電粒子A」。用塗佈機將此混合溶液 塗佈於PET薄膜上，藉由70 °C 10分鐘的熱風乾燥，而得到 黏著劑層的厚度爲35 μπι的薄膜狀之電路連接材料。 (實施例2 ) 除了將導電粒子Α的配合量變更爲5質量份以外，與實 施例1同樣地得到薄膜狀之電路連接材料。 -27- 201134904BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a connection structure of a circuit connecting material and a circuit member using the same. [Prior Art] As the adhesive for a semiconductor element or a liquid crystal display element, a thermosetting resin such as an epoxy resin which is excellent in adhesion and exhibits high reliability is used (for example, see Patent Document 1). As a constituent component of the above-mentioned adhesive, a hardener such as an epoxy resin, a phenol resin reactive with an epoxy resin, or a thermal latent catalyst which promotes a reaction between an epoxy resin and a curing agent is generally used. The thermal latent catalyst is an important factor in determining the hardening temperature and the hardening speed of the adhesive, and various compounds are used from the viewpoints of storage stability at room temperature and curing speed at the time of heating. In the meantime, attention has been paid to a radical-curable adhesive comprising a radical polymerizable compound such as an acrylate derivative or a methacrylate derivative and a peroxide of a radical polymerization initiator. The radical-curing type adhesive can be hardened at a low temperature for a short period of time (for example, refer to Patent Documents 2 to 4). PRIOR ART DOCUMENT Patent Document Patent Document 1: JP-A No. 1 - 1 1 3 48 No. Patent Document 2: Special Opening JP-A-2002-203427 Patent Document 3: International Publication No. 98/044067, PCT Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Flat panel display (hereinafter referred to as "FPD") is popular in the field of 'Printed Wiring Board (hereinafter referred to as "PWB") and tape carrier package (Tape) Carrier Package (hereinafter referred to as "TCP") or a connection of Chip On Flex (hereinafter referred to as "COF"). In the connection between the Flexible Printed Circuits (hereinafter referred to as "FPC") and the PWB in the field of FPD, circuit connection materials are used, and the circuit is generally subjected to gold plating. On the other hand, in the PWB in which a component such as a wafer or a capacitor is mounted, the mounting system by solder is the mainstream. In order to obtain good solderability, as a surface treatment of the circuit, an attempt was made to form a resin film containing an imidazole compound. Further, in a large-sized mother board or the like, since the cost can be reduced without using gold, the organic film is usually formed by treatment with a solution containing an organic resin such as an imidazole compound (hereinafter referred to as "OSP treatment"). Hereinafter, it is called "OSP film" as the case may be. The use of the above-mentioned circuit connecting materials is also being reviewed in the installation of circuit boards subjected to such OSP processing. In the case of an anionic polymerization-based adhesive using an epoxy resin, the OSP-treated substrate can also impart good adhesion and connection reliability. However, in view of the trend of high-density mounting, the structure of the circuit board is mainly in the structure of & -6- 201134904. In order to dissipate heat during connection, a through hole or a through hole or the like is provided in the vicinity of the connecting portion. Due to this through hole or through hole, sufficient heat cannot be given when the adhesive of the anionic polymerization system hardens. If necessary heat is supplied for a sufficient period of time, it is necessary to connect for a long period of time, and it is not practical to use an anionic polymer-based adhesive. On the other hand, when the FPC-based FPC is connected to the PWB, the radical-curable adhesive can be cured even in a short period of time of less than 1 second, and is used in the OSP-treated substrate and in the gold plating. When the substrate to be processed is compared, there is a problem that the connection resistance is likely to rise. This is because the OSP film itself is non-conductive. Accordingly, it is an object of the present invention to provide a circuit connecting material which can be sufficiently hardened at a low temperature and for a short period of time, and which can be used for an OSP-treated substrate, and a connection structure of a circuit member using the same. Means for Solving the Problems The present invention provides a circuit connecting material which is a circuit connecting material for electrically connecting opposing circuit electrodes to each other, which comprises an adhesive composition and a conductive particle having a Vickers hardness of 300 to 1 〇〇. The core body formed by the metal of the crucible has the outermost layer formed of a noble metal covering the surface of the core body and has an average particle diameter of 5 to 20 μη. Further, the present invention provides a circuit connecting material which is a circuit connecting material for electrically connecting opposite circuit electrodes, which comprises an adhesive composition and conductive particles, and the conductive particles are a core body formed of nickel, and Covering 201134904 The surface layer of the surface of the core body formed of a noble metal, and having an average particle diameter of 5 to 20 μm η. The circuit connecting material of the present invention can be at a low temperature by simultaneously containing the conductive particles and the adhesive composition as described above. Hardening is performed for a short time, and the substrate treated with OSP can also exhibit good connection reliability. From the viewpoint of curing in a shorter period of time, in the circuit connecting material of the present invention, the adhesive composition preferably contains a radical polymerizable substance and a hardener which generates free radicals by heating. Further, when the adhesive composition contains an epoxy resin and a latent curing agent, the connection reliability of the connection structure of the circuit member using the circuit connecting material can be further improved. The present invention provides a connection structure for a circuit member, comprising: a first circuit member having a first circuit electrode formed on a main surface of a first circuit substrate; and a main surface of the second circuit substrate is formed a second circuit electrode, wherein the second circuit electrode and the first circuit electrode are second circuit members arranged in an opposing arrangement, and are disposed between the first circuit substrate and the second circuit substrate a circuit connecting portion connecting the first circuit member and the second circuit member to the second circuit electrode, wherein the circuit connecting portion is a hardened material of the circuit connecting material of the present invention, first and second At least one of the circuit electrodes has a film formed of an imidazole compound. In the connection structure of the circuit configuration of the conventional short-time hardening type circuit connecting material -8-201134904, when the circuit electrode has the OSP film, it is difficult to improve the connection in a short time of less than 10 seconds. Propensity. On the other hand, in the connection structure of the circuit member of the present invention, since the circuit connecting portion is a cured product of the above-described circuit connecting material of the present invention, good connectivity can be obtained even if the connection time is less than 10 seconds. In the connection structure of the circuit member of the present invention, since the surface of the circuit electrode is formed by a film made of a material containing an organic resin, the protection circuit electrode is prevented from being oxidized, and good solderability can be obtained. Further, in the connection structure of the present invention, since the circuit members are connected to each other by the circuit connecting material of the present invention, it has sufficiently high adhesive strength and connection reliability. Advantageous Effects of Invention According to the present invention, it is possible to provide a circuit connecting material which can be hardened at a low temperature and for a short period of time, and which can be used for an OSP-treated substrate, and which can provide a sufficiently high connection reliability, and a connection of circuit members using the same structure. [Embodiment] Mode for Carrying Out the Invention Hereinafter, a preferred embodiment of the present invention will be described in detail with reference to the drawings, as needed. However, the present invention is not limited by the following embodiments. In the drawings, the same elements are denoted by the same reference numerals, and the repeated description is omitted. Further, as long as there is no particular specification, the positional relationship such as up, down, left, and right is based on the positional relationship shown on the drawing. Furthermore, the dimensional ratio of the drawings is not limited by the ratios shown. -9 - 201134904 The circuit connecting material of this embodiment is an adhesive for electrically connecting circuit electrodes to each other. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an embodiment of a circuit connecting material. The circuit connecting material 1 shown in Fig. 1 is composed of a resin layer 3 and a plurality of conductive particles 5 dispersed in the resin layer 3, and has a film shape. 〇 Each constituent material of the circuit connecting material 1 will be described below. (Electrically conductive particles) The conductive particles 5 have a core body formed of a metal having a Vickers hardness of 300 to 1,000, and an outermost layer formed of a noble metal on the surface of the core body, and have an average particle diameter of 5 to 20 μm. Further, the conductive particles 5 have a core body formed of nickel and an outermost layer formed of a noble metal covering the surface of the core body, and have an average particle diameter of 5 to 20 μm. Such a conductive particle is likely to penetrate the non-conductive film of the circuit electrode, and it is easy to suppress an increase in the connection resistance. Therefore, by using a circuit connecting material containing the above-mentioned conductive particles, a connection structure of a circuit member excellent in connection reliability can be obtained. The core of the conductive particles 5 is preferably selected from transition metals of nickel, chromium, molybdenum, manganese, cobalt, iron, manganese, vanadium, titanium, platinum, rhodium, tungsten, tungsten, molybdenum, cerium, zirconium, palladium, and the like. More preferably, the metal is composed of nickel, and the metal having a nucleus composed of nickel has a Vickers hardness of 300 to 1,000, more preferably 400 to 800, still more preferably 500 to 700. When the Vickers hardness of the core is less than 300, the conductive particles are easily deformed, and the exclusion property of the osp film on the electrode tends to be lowered. Above 1 000, the particles are not easily deformed, although to ensure a sufficient contact area -10- 201134904 in order to give good connection reliability. Preferably, the outermost layer of the conductive particles 5 is made of at least one metal selected from the group consisting of gold, silver, platinum, palladium, rhodium, ruthenium, osmium, or the like, and is preferably composed of gold or platinum. It is made up of gold. By forming the outermost layer of the conductive particles 5 with such a metal, the life of the circuit connecting material 1 can be sufficiently increased. The thickness of the outermost layer of the conductive particles 5 is preferably 0.03 to 0.4 μm, more preferably 0.08 to 0.2 μm. When the thickness of the outermost layer is less than 0.03 μm, the conductivity of the conductive particles is lowered, and the connection resistance tends to increase. When the thickness exceeds 0.4 μm, the cost becomes high when the outermost layer is formed on the core body, and the cost tends to be poor. Further, the core body is more preferably covered by the outermost layer formed of the noble metal, but a part of the core body may be exposed without departing from the effects of the present invention. The conductive particles have an average particle diameter of 5 to 20 μm, preferably 8 to 20 μm, more preferably 8 to 15 μm. When the average particle diameter of the conductive particles is less than 5 μm, the resin layer 3 is hardened before the conductive particles are in contact with the electrode. When the conductive particles exceed 20 μm, the radius of curvature of the conductive particles is large, and the exclusion property of the OSP film on the electrode is lowered. In the case, it becomes difficult to obtain electrical conduction. In addition, the average particle diameter of the conductive particles specified in the present invention is measured by the laser diffraction method measured by "SA LD - 1 0 0 0" (trade name, manufactured by Shimadzu Corporation). The amount is suitably set according to the use, but is usually 1 to 30 parts by volume with respect to 1 part by volume of the adhesive layer 3 (that is, a portion other than the conductive particles 5 in the circuit connecting material 1). Scope -11 - 201134904. Furthermore, from the viewpoint of preventing short-circuiting of adjacent circuits on the same circuit substrate, the amount of conductive particles is more preferably < (Adhesive Composition) The resin layer 3 preferably contains a radical polymerizable substance which generates free radicals. In other words, the circuit connecting material 1 is made of a free radical free hardener, a radical polymerizable substance, and conductive particles 5. When the circuit connecting material 1 is heated, a cured product of the circuit connecting material 1 is formed in the resin layer 3 by polymerization of a base polymerizable substance. At this time, the circuit is connected; f is a function of a radical hardening type of adhesive. The free radical generated in the circuit connecting material 1 is heated by a peroxy compound or an azo compound to generate free radicals, and can be appropriately selected depending on the intended connection temperature, the bonding period, and the like. The amount of the compounding is based on the amount of the circuit connecting material, preferably 0.05 to 10% by mass, more preferably 0.1. The total mass of the circuit connecting material 1 is 100 parts by mass, more preferably 10 parts by mass, more preferably 0.1 to 5 parts by mass. Share). The dissolving agent is generated, in particular, by didecyl peroxide, peroxydicarbonate, peroxyketal, dialkyl peroxide, hydroperoxide, and in order to suppress corrosion of the connecting terminal of the circuit member. Choose from esters, dialkyl peroxides, hydroperoxides, and higher reactivity peroxyesters. When the electrodes are between 1 and 10 volumes of the hardener and the adhesive group containing the hair, the self-linking structure, the shape 1 material has a hardener, and the decomposition, the time of use, the use of + 1 Physique ~ 5 mass% ( :佳为〇. 〇5~ free radicals such as hard acid ester, peroxygen, etc.. Good by peroxygen as a result of -12- 201134904 as a dimercapto peroxide, for example 2,4-dichlorobenzhydryl peroxide, 3,5,5-trimethylhexyl peroxide, octyl peroxide, lauryl peroxide peroxide Oxide, amber-based peroxide, benzamidine peroxytoluene, and benzammonium peroxide. Examples of peroxydicarbonates are di-n-propyl peroxydicarbonate and diiso. Propyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di-2-ethoxymethoxy peroxydicarbonate, di(2-ethylhexyl) Oxygen dicarbonate, dimethoxybutyl peroxydicarbonate and mono (3-methyl-3-methoxybutyl peroxy) dicarbonate. As peroxyesters, for example 1,1,3,3-tetramethylbutyl peroxy neodecanoate, 1-cyclohexyl-1-methylethyl peroxydecanoate, third hexyl peroxy neodecanoate, Tributyl peroxytrimethyl acetate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoic acid vinegar, 2,5-dimethyl-2,5-di 2-ethylhexyl peroxy)hexane, 1-cyclohexyl-1-methylethylperoxy 2-ethylhexanoate, third hexylperoxy-2-ethylhexanoate, third Butyl peroxy-2-ethylhexanoate, tert-butylperoxy isobutyrate, 1,1-bis(t-butylperoxy)cyclohexane, third hexylperoxyisopropylidene Carbonate, tert-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di(m-toluene) Base peroxy)hexane, tert-butylperoxyisopropylmonocarbonate, tert-butylperoxy-2-ethylhexylmonocarbonate, third hexylperoxybenzoate and tert-butyl Peroxyacetic acid. Examples of the peroxy ketals include 1,1 bis (third hexylperoxy)-3,3,5·trimethylcyclohexane, and 1, bis (third Hexylperoxy)cyclohexane, 1,1-double (p. Butyl peroxy)-3,3,5-trimethylcyclohexane, 1,1-( -13- 201134904 tert-butylperoxy)cyclododecane and 2,2-bis-(third butyl The base peroxy) decane oxime is a dialkyl peroxide, and examples thereof include α,α' bis(t-butylperoxy)diisopropylbenzene, diisopropylbenzene peroxide, and 2,5. -Dimethyl-2,5-di(t-butylperoxy)hexane and tert-butylperoxypropoxide oxime as hydroperoxides, for example, diisopropylbenzene hydrogen peroxide Oxide and cumene hydroperoxide These hardeners which generate free radicals may be used singly or in combination, or may be used by mixing a decomposition accelerator, an inhibitor, or the like. Further, these curing agents are coated with a polyurethane material, a polyester-based polymer material or the like to form a microcapsule, and it is preferable to extend the usable time. The radically polymerizable substance used in the circuit connecting material 1 is a substance having a functional group which is polymerized by a radical, and examples thereof include an acrylate, a methacrylate, a maleimide compound, and a citrate imine. Resin, Nadiimide resin, etc. The blending amount of the radically polymerizable material is 100 parts by mass, preferably 20 to 50 parts by mass, more preferably 30 to 40 parts by mass, based on the total mass of the circuit connecting material 1. The radically polymerizable substance can be used in any of a monomer and an oligomer, and a monomer and an oligomer can also be used. Examples of the acrylate (containing the corresponding methacrylate, the same applies hereinafter) as the JL include, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, ethylene glycol diacrylate, and diethyl phthalate. Alcohol diacrylate, trimethylolpropane triacrylate, tetramethylol methane tetraacrylate, 2-hydroxy-1,3-dipropoxypropane, 2,2-bis[4-(acryloxy- 14- 201134904 methoxy)phenyl]propane, 2,2-bis[4-(acryloxypolyethoxy)phenyl]propane, dicyclopentanyl acrylate, tricyclodecyl acrylate, tris(propylene fluorene) Oxyethyl) isomeric isocyanate and ethyl urethane acrylate. These may be used singly or in combination of two or more kinds, and a polymerization inhibitor such as hydroquinone or methyl ether hydroquinone may be suitably used as needed. Further, when it has a dicyclopentenyl group and/or a tricyclodecanyl group and/or a triterpene ring, it is preferable because heat resistance is improved. The above-described maleated imine compound is one having at least two or more maleimine groups in the molecule, and examples thereof include 1-methyl-2,4-bismaleimide benzene, N,N'. -Interstituted phenyl bismaleimide, N,N'-p-phenylene bismaleimide, N,N'-m-tolyl-p-maleimide, N,N'-4 , 4-extended biphenyl bis-maleimine, N,N'-4,4-(3,3'-dimethyl extended phenyl) bismaleimide, ^:^'-4 , 4-(3,3'-dimethyldiphenylmethane) bismaleimide, hydrazine, Ν'-4,4-(3,3'-diethyldiphenylmethane) bismale醯iamine, hydrazine, Ν'-4,4-diphenylmethane bismaleimide, 1^氺'-4,4-diphenylpropane bismaleimide, hydrazine, Ν'-3 , 3'-diphenyl maple bismaleimide, hydrazine, hydrazine-4,4-diphenyl ether bismaleimide, 2,2-bis(4-(4-maleimide) Phenoxy)phenyl)propane, 2,2-bis(3-secondbutyl-4,8-(4-maleimidophenoxy)phenyl)propane, 1,1-double (4 -(4-maleimide phenoxy)phenyl)decane, 4,4'-cyclohexylene-bis(1_(4-maleimide phenoxy) -2 - cyclohexylbenzene and 2,2-bis(4-(4-maleimidophenoxy)phenyl)hexafluoropropane. These may be used alone or in combination of two or more. The imine resin is a mercapine imine compound having at least one citracin-15-201134904 imine group in the molecule, and as a citrate imine compound, for example, phenyl citrate , 1-methyl-2,4-bis-citraconazole, N,N'-meta-phenyl-sodium citrate, N,N'-p-phenyl-p-sodium citrate, N,N-4,4-Exbiphenyl bis-citraconazole, N,N'-4,4-(3,3-dimethylexetylene) bis citraconin, :^ ,:^'-4,4-(3,3-dimethyldiphenylmethane) bis citrate, N,N'-4,4-(3,3-=ZS diphenylmethane) Sodium citrate, N,N'-4,4-diphenylmethane bis citrate, hydrazine '-4,4-diphenylpropane bis citrate, >| ,>4'-4,4-diphenyl ether bis citrate, N,N'-4,4-diphenyl bis bis quinone, 2,2- bis (4-( 4- citrate iminophenoxy)phenyl)propane, 2,2_bis (3 - second Benzyl-3,4-(4-cylylene-iminophenoxy)phenyl)propane, 1, bis(4-(4. citrate), phenyloxy)phenyl) decane, 4 ,4,-cyclohexylene-bis-citraconazole, phenoxy)phenoxy)-2_cyclohexylbenzene and 2,2-bis(4-(4. citracone) phenoxy)benzene Base) hexafluoropropane. These may be used alone or in combination of two or more types. The nadimide resin is a polymer of a dinadiimide compound having at least one nadimide group in the molecule, and as a dinadiimide compound, for example, a phenyl nadi醯iamine, 丨_methyl _ 2,4-double nadirimine benzene, N,N'-meta-phenylene dipyridinium imine, N,N '-p-phenylene dipyridinium Imine, N,N ' - 4,4 -Exbiphenyl double nadirimine, N,N'- 4,4-(3,3-dimethylexidine) double nadiya Amine, >1,>1'-4,4-(3,3-dimethyldiphenyl), double nadirimine, 叱:^'-4,4-(3,3- Diethyldiphenylmethane) double nadirimine, 1^,1^,_ 4,4_diphenyl ketone double nadiimide, N,N'- 4,4-diphenyl丙院双纳-16- 201134904 Diimine, hydrazine, Ν'-4,4·diphenyl ether double nadirimine, N,N,.-4 phenyl fluorene double nadirimine, 2,2-bis(4-(4-nadiquinazolin)phenyl)propane, 2,2-bis(3-secondbutyl-3,4-(4-nadidecylphenoxy) Phenyl)propane, 1,1-bis(4-(4-nadiquinium phenyl)phenyl)decane, 4,4'- Cyclohexyl-bis(1-(4-nadifluorenylene)phenoxy)-2-cyclohexylbenzene and 2,2-bis(4-(4-nadiphosphonio)phenyl) Fluoropropane. These can be used alone or in combination of two types. The circuit connecting material 1 (resin layer 3) may contain other components in addition to a hardening agent and a radical polymerizable substance which are free. The thermoplastic resin and the thermosetting resin may be contained. As the thermoplastic resin, a polyethylene resin, a polyimide, a polyvinyl chloride resin, a polyphenylene ether resin, a polyvinyl butyral resin, an ene formal resin, a polyamide resin, a polyester resin, a phenoxy resin, or the like can be used. Vinyl resin, xylene resin, polyurethane resin, and the like. Further, as the thermoplastic resin, a hydroxyl group-containing resin having a Tg (glass transfer) of 40 ° C or more and a molecular weight of 1,000,000 or more is preferably used, and a phenoxy resin can be suitably used. The phenoxy resin is obtained by reacting a difunctional phenol oxychloropropane until it becomes a high molecular weight, or a polyaddition phenol and a difunctional phenol are subjected to a polyaddition reaction. Examples of the thermosetting resin include urea resin, melamine, phenol resin, xylene resin, epoxy resin, and polyisocyanate resin. When the thermoplastic resin is contained, it is excellent in workability and excellent in hardening stress relaxation. Further, the above-mentioned thermoplastic resin and thermosetting, 4-dioxyimidophenoxyphene benzene have a hydroxyl group from a base such as a resin polyphenylene benzene temperature, for example, when it is oxime with an epoxy resin, -17-201134904 When the functional group is used, it is more preferable because the adhesiveness is improved, and it may be modified by an epoxy group-containing elastomer or a radical polymerizable functional group. It is preferably modified by a radical polymerizable functional group because heat resistance is improved. The weight average molecular weight of the thermoplastic resin is preferably 1,000,000 or more from the viewpoint of film forming properties and the like, but if it is 1,000,000 or more, the mixing property tends to be inferior. Further, the weight average molecular weight specified in the present invention is determined by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene according to the following conditions. <GPC condition> Machine used: Hitachi L-6000 type (manufactured by Hitachi, Ltd.) Pipe column: Gelpack GL-R420 + Gelpack GL-R43 0 + Gelpack GL-R440 (3 pieces) (Hitachi Chemical Industry Co., Ltd. (Stock) system: Eluent: Tetrahydrofuran Measurement temperature: 40 ° C Flow rate: 1.75 mL / min Detector: L-3 3 00 RI (manufactured by Hitachi, Ltd.) In addition, the resin layer 3 contains free radicals. The hardener and the radical polymerizable substance may also contain an epoxy resin and a latent hardener. Namely, the circuit connecting material 1 may contain an adhesive composition containing an epoxy resin and a latent curing agent, and conductive particles 5. The circuit connecting material 1 is formed by a hardening of an epoxy resin during heating to form a crosslinked structure in the resin layer 3 to form a cured product of the circuit connecting material 1. At this time, the circuit connecting material 1 is -18-201134904 and has an function as an epoxy hardening type adhesive. An epoxy resin represented by an epoxy resin, a bisphenol epoxy resin such as bisphenol A, F or AD, and a phenol novolak or a cresol novolac resin. Other examples thereof include a naphthalene type epoxy resin having a naphthalene skeleton, a glycidylamine type epoxy resin, a glycidyl acrylate type epoxy resin, an alicyclic epoxy resin, and a heterocyclic oxyresin. These may be used alone or in combination of two or more. Among the above epoxy resins, the bisphenol type epoxy resin has a molecular weight grade, and since it can be widely obtained, it is preferable to set the adhesion or reaction arbitrarily. Among the bisphenol type epoxy resins, a bisphenol F type ring grease is particularly preferred. The bisphenol F type epoxy resin has a low viscosity, and by using it in combination with a phenoxy resin, the flow of the circuit connecting material can be easily set in a wide range. Further, the bisphenol F type epoxy resin also has an advantage of being easy to adhere to a circuit connecting material. In order to prevent electron migration, it is preferred to use an epoxy resin having a concentration of impurity ions (Na + or the like) or hydrolyzable chlorine of 300 ppm or less. As the latent curing agent, any one can cure the epoxy resin. Further, the latent curing agent may be a compound which is reacted with an epoxy resin to be incorporated into the crosslinking, or may be a contact curing agent which accelerates the curing reaction of the epoxy resin. You can also use both. Examples of the catalyst-type curing agent include an anionic polymerization type latent curing agent which promotes sub-polymerization of an epoxy resin, and a cationic polymerization type latent curing agent which promotes cationic polymerization of an epoxy resin. Examples of the anionic polymerization type latent curing agent include an example of a propyl group, an oxo group of an oxygen tree such as a difference in oxygen tree type, and an azole group which can be a conjugated medium type cation-free grease. - 201134904, a lanthanide, a trifluoroboron-amine complex, an amidoximine, a polyamine salt, a cyanamide, and the like. The imidazole-based anionic polymerization type latent curing agent is formed, for example, by adding an imidazole or a derivative thereof to an epoxy resin. As the cationic polymerization type latent curing agent, for example, a photosensitive key salt which hardens an epoxy resin by irradiation with an energy ray (mainly using an aromatic diazo salt or an aromatic sulfonium salt) is preferable. Further, as the epoxy resin is cured by heating activation other than the energy ray irradiation, there is an aliphatic sulfonium salt. Such a hardener is preferred because of its rapid hardening characteristics. These latent curing agents are coated with a polymer material such as a polyurethane or a polyester, a metal thin film such as nickel or copper, or an inorganic material such as calcium citrate to form a microencapsulated one. Time is better. The amount of the latent hardener is preferably from 30 to 60 parts by mass, more preferably from 40 to 55 parts by mass, per part by mass of the epoxy resin. If the blending amount of the latent hardener is less than 30 parts by mass, the fastening force to the adherend due to the hardening shrinkage of the circuit connecting material is lowered. As a result, the contact resistance between the conductive particles 5 and the circuit electrode is not maintained, and the connection resistance after the reliability test tends to increase. On the other hand, when the amount of the latent curing agent is more than 60 parts by mass, the internal force of the hardening of the circuit-connecting material becomes large, and the tendency of the adhesive strength is lowered. When the circuit connecting material is an epoxy resin adhesive, it is preferred to contain a film forming material. When the liquid material is solidified and the constituent material is formed into a film shape, the operation of the film is facilitated, and mechanical properties such as cracking, cracking, or stickiness are not provided, and the film can be in a normal state. 20- 201134904 (normal temperature and normal pressure) is operated as a film. As the film forming material, the above thermoplastic resin can be used, and from the viewpoint of excellent adhesion, compatibility, heat resistance and mechanical strength, a phenoxy resin is preferably used. The phenoxy resin is a resin obtained by subjecting a bifunctional phenol to an oxychloropropane until it is polymerized, or a polyfunctional epoxy resin and a bifunctional phenol. The phenoxy resin can be, for example, a non-reactive solvent in the presence of a catalyst such as an alkali metal hydroxide in the presence of a catalyst of 0.985 to 1.015 mol of epichlorohydrin in a molar amount of 1 mol of the bifunctional phenol. It is obtained by reacting at a temperature of 40 to 120 °C. Further, as the phenoxy resin, it is particularly preferable that the compounding equivalent ratio of the bifunctional epoxy resin to the bifunctional phenol is an epoxy group/phenolic hydroxyl group from the viewpoint of mechanical properties or thermal properties of the resin. 1/0.9 to 1/1.1, in the presence of a catalyst such as an alkali metal compound, an organophosphorus compound or a cyclic amine compound, an amide group, an ether system or a ketone system having a boiling point of 1 20 ° C or higher. In an organic solvent such as a lactone type or an alcohol type, the mixture is heated to 50 to 200 ° C under the conditions of a reaction solid content of 50% by mass or less, and a polyaddition reaction is carried out to obtain a bifunctional epoxy resin. 'Can use bisphenol a type epoxy resin' bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol s type epoxy resin. The bifunctional phenol type has two phenolic hydroxyl groups, and examples thereof include a bisphenol compound such as hydroquinone, bisphenol A, bisphenol F, bisphenol AD, and bisphenol S. The phenoxy resin can also be modified via a radical polymerizable functional group. The phenoxy resin may be used alone or in combination of two or more. "21 - 201134904 Furthermore, 'circuit connection material 1 (resin layer 3) may also contain enamel, softener, accelerator, anti-aging agent, colorant, flame retardant, shaker, coupling agent and isocyanate Classes, etc. When the ruthenium is contained, it is preferable to improve the connection reliability and the like. The maximum diameter of the ruthenium filler material can be used as long as it does not reach the particle diameter of the conductive particles 5, and the blending amount is preferably in the range of 5 to 60% by volume. If it exceeds 60% by volume, the effect of reliability improvement is saturated. As the coupling agent, a compound having a vinyl group, an acryl group, an amine group, an epoxy group or an isocyanate group is preferred from the viewpoint of improving the adhesion. A polymerization inhibitor such as hydroquinone or methyl ether hydroquinone may be suitably used as needed. Next, the connection structure of the circuit member of the present invention using the circuit connecting material 1 will be described. The circuit connecting material 1 is suitable for forming a wafer component such as a semiconductor wafer, a resistor wafer, and a capacitor wafer, and a connection structure in which circuit members having one or two or more circuit electrodes (connection terminals) such as a printed wiring board are connected to each other . Fig. 2 is a cross-sectional view showing an embodiment of a connection structure of a circuit member. The connection structure 1 of the circuit member shown in FIG. 2 includes a first circuit member 10 having a first circuit substrate 11 and a first circuit electrode 13 formed on the main surface thereof; The second circuit board 21 and the second circuit electrode 23 formed on the main surface thereof, and the second circuit member 20 disposed so that the second circuit electrode 23 and the first circuit electrode 13 face each other: a circuit connection portion 1a existing between the first circuit member 10 and the second circuit member 20. The connection portion la is formed of a cured resin layer 3a and conductive particles 5 which are formed by curing the circuit connecting material 1. The connecting portion 1a is electrically connected to the first circuit electrode 13 and the second circuit electrode 23 opposite to each other by -22-201134904, and the first circuit member 10 and the second circuit member 20 are bonded. The first circuit electrode 13 and the second circuit electrode 23 that are opposed to each other are electrically connected via the conductive particles 5. Further, even when the connecting portion does not contain the conductive particles 5, the first circuit electrode 13 and the second circuit electrode 23 can be electrically connected via the circuit connecting material 1. The first substrate 11 is a resin film containing at least one resin selected from the group consisting of polyester terephthalate, polyether mill, epoxy resin, acrylic resin, and polyimide resin. The first circuit electrode 13 is at least one selected from the group consisting of a conductive material capable of functioning as an electrode (preferably a metal of gold, silver, tin, a platinum group, and an indium-tin oxide). ) formed. The second substrate 21 is a multilayer wiring board formed of an insulating substrate such as tantalum or gallium arsenic of a semiconductor wafer or glass, ceramic, glass epoxy composite or plastic. The second circuit electrode 23 has a conductor portion 23a, and a film 23b which is formed in a portion in contact with the connecting portion 1a on the surface of the circuit electrode 23. The conductor portion 23a is at least one selected from the group consisting of a conductive material (preferably a metal of gold, silver, tin, a platinum group, and an indium-tin oxide) having a circuit electrode 23 capable of functioning as an electrode. ) formed. The film formed by the material containing the organic resin is preferably an organic resin containing an imidazole compound or the like. The film 23b is formed by performing OSP (Organic Solderability Preservative) treatment on the second substrate 21. The 0SP treatment referred to herein is a method of treating a substrate which is also referred to as a water-soluble preflux. The substrate is generally treated with a solution containing an imidazole compound -23-201134904 to form an OSP film. The film containing an imidazole compound is a film formed by bonding a complex compound of an imidazole-based derivative and a metal to each other on the surface of the electrode. That is, the film containing the imidazole compound can be formed by subjecting the substrate on which the circuit electrode is formed to OSP treatment with a solution containing an imidazole compound. As the imidazole compound, a benzimidazole-based derivative is preferably used from the viewpoint of heat resistance. For the OSP processing, for example, the trade name "Tufence F2", "Tufence F2 (LX)", "Shares", and the product name "Cu Coat GVII" manufactured by Shikoku Kasei Co., Ltd., which are commercially available from the company. The product names "Entek 106A" and "Entek 106A (X)" manufactured by Enthone. Inc., or the product names "Mecseal CL-5 8 24S", "Mecseal CL-5018", and "Mecseal CL-" manufactured by EC (stock). 5018S" is coming. These may be used alone or in combination of two or more types. 电路 At least one of the circuit connecting materials of the present invention, the first and second circuit electrodes, may be used to connect a circuit member having a film made of a material containing an organic resin. Further, as shown in FIG. 3, a cross-sectional view showing an embodiment of the connection structure of the circuit member, not only the second circuit electrode 23 but also the first circuit electrode 13 may have the conductor portion 13a and the surface of the circuit electrode 13. A film 13b is formed in a portion in contact with the connecting portion la. The film 13 b is formed by the same method as the film 23b. The connection structure 100 of the circuit member, for example, by sequentially laminating the first circuit member 10, the film-like circuit connecting material 1 and the second circuit member 20, so that the first circuit electrode 13 and the second The circuit electrode 23 is opposed to each other, and the obtained laminate is heated and pressurized or irradiated with light, and the first circuit member 10 is connected in such a manner that the circuit electrode 13 of the second to the second circuit electrode 23 is electrically connected. Obtained from the method of the second circuit member 20. In this method, first, the film-like circuit connecting material 1 formed on the support film is bonded to the second circuit member 20, and heating and pressurization are performed to temporarily adhere the circuit connecting material 1 and peel off. After the film is supported, the first circuit member 10 is placed while positioning the circuit electrodes in such a manner that the circuit electrodes are opposed to each other, and the laminate is prepared. In order to prevent the influence of the volatile component generated by the heating at the time of connection, it is preferable to heat-treat the circuit member before the connecting step. The conditions for heating and pressurizing the above-mentioned laminate are appropriately adjusted in accordance with the hardenability of the composition in the circuit connecting material, etc., so that the circuit connecting material is hardened to obtain sufficient adhesive strength. The substrate of the circuit member constituting the connection structure may be a semiconductor wafer such as @ and gallium arsenic, or an insulating substrate such as glass, ceramic, glass epoxy composite or plastic. EMBODIMENT The content of the present invention will be specifically described. However, the invention is not limited by the embodiments. (1) Preparation of circuit connecting material (1-1) Preparation of each component constituting the adhesive composition "Perhexa 250": 2,5-dimethyl-2,5-di(2-ethylhexyl fluorenyl) Oxygen) hexane (manufactured by Nippon Oil & Fats, trade name) -25- 201134904 ^ UN5 5 00": Amino acrylate acrylate oligomer (manufactured by K.K., Ltd., trade name) "DCP-A": Dicyclopentane E-type diacrylate (manufactured by Toagosei Co., Ltd.) "M-215": EO-modified diacrylate of isocyanuric acid (manufactured by Toagos Corporation, trade name) "P-2M": 2-methyl propylene oxime Ethoxyethyl acid phosphate (trade name, Kyoeisha Chemical Co., Ltd.) "HX3 94 1 HP-SS": epoxy resin containing an anionic polymerization type latent curing agent (containing 35 mass% of imidazole microcapsule type) "Resistance, manufactured by Asahi Kasei Chemicals, trade name" "UR-800": polyester urethane (produced by Toyobo Co., Ltd., trade name) "EV40W": ethylene-vinyl acetate copolymer (manufactured by Mitsui & DuPont Poly Chemical Co., Ltd.) Product name) "PKHC": bisphenol A type phenoxy tree month (Mw45000, 'CHECK name by INCHEM company') A": 40 parts by mass of butyl acrylate - 30 parts by mass of ethyl acrylate - 30 parts by mass of acrylonitrile - 3 parts by mass of a copolymer of glycidyl methacrylate (weight average molecular weight of about 850,000) "SH6040 ”: Decane coupling agent (γ-glycidoxypropyltrimethoxy decane, manufactured by Toray Dow Corning • Polyfluorene, trade name) (1-2) Preparation of conductive particles -26- 201134904 A", a conductive particle having a core body made of Ni particles having an average particle diameter of 9 μm and a gold-plated outermost layer formed by gold plating on the core body is prepared. Further, as the "conductive particles B", conductive particles made of Ni particles having an average particle diameter of 9 μm were prepared. Further, as the "conductive particles C", conductive particles having a plurality of protrusions on the surface and having Ni particles having an average particle diameter of 4 μm were prepared. (Example 1) 8 parts by mass of a "Perhexa 25" 5 〇 mass% hydrocarbon solvent solution and 60 parts by mass (30 parts by mass in terms of nonvolatile content) when 8 parts by mass (4 parts by mass in terms of nonvolatile content) 50% by mass toluene solution of "UN5 500" as a radical polymerizable substance, 8 parts by mass of "DCP-A", 8 parts by mass of "M-215", 2 parts by mass of "P-2M", 150 30 parts by mass of "UR-8200" in a mass fraction (45 parts by mass of non-volatile matter), methyl ethyl ketone/toluene (=50/50) solution and 50 parts by mass (10 mass in terms of non-volatile content) A 20% by mass toluene solution of "EV4 0W" was added in an amount of 10 parts by mass of "conductive particles A". This mixed solution was applied onto a PET film by a coater, and dried by hot air at 70 ° C for 10 minutes to obtain a film-like circuit connecting material having a thickness of the adhesive layer of 35 μm. (Example 2) A film-like circuit connecting material was obtained in the same manner as in Example 1 except that the amount of the conductive particles Α was changed to 5 parts by mass. -27- 201134904
XI/ 3 例 施 配合50質量份的「HX3941HP-SS」、37.5質量份（以 不揮發份換算爲15質量份）的「PKHC」之40質量％甲苯/ 醋酸乙酯（=5 0/5 0 )溶液、3 50質量份（以不揮發份換算 爲35質量份）的「丙烯酸橡膠A」之10質量％甲苯/醋酸乙 醋（=50/50 )溶液及1質量份的「SH6040」，再配合10質 量份的「導電粒子A」。用塗佈機將此混合溶液塗佈於 PET薄膜上，藉由70°C 10分鐘的熱風乾燥，而得到黏著劑 層的厚度爲35μπι的薄膜狀之電路連接材料。 (比較例1 ) 除了將10質量份的「導電粒子Α」變更爲10質量份的 「導電粒子Β」以外，與實施例1同樣地得到電路連接材料 〇 (比較例2 ) 除了將10質量份的「導電粒子A」變更爲10質量份的 「導電粒子C」以外，與實施例1同樣地得到電路連接材料 (比較例3 ) 除了將10質量份的「導電粒子A」變更爲5質量份的「 導電粒子C」以外，與實施例1同樣地得到電路連接材料。 -28- 201134904 (比較例4 ) 除了將10質量份的「導電粒子A」變更爲10質量份的 「導電粒子B」以外，與實施例3同樣地得到電路連接材料 (比較例5 ) 除了將「導電粒子A」10質量份變更爲10質量份的「 導電粒子C」以外，與實施例3同樣地得到電路連接材料。 表1中以質量份（不揮發份換算）顯示實施例丨〜3的 電路連接材料之組成，表2中以質量份（不揮發份換胃> 顯示比較例1〜5的電路連接材料之組成。 [表1] 材料物質 實施例1 實施例2 實施例3 發生游離自由基的 硬化劑 Perhexa 250 4 4 — 自由基聚合性物質 UN-5500 30 30 — DCP-A 8 8 — M-215 8 8 — P-2M 1 . 2 一 環氧樹脂 HX3941HP-SS — 一 _ 50 熱塑性樹脂 UR-8200 45 45 — EV40W 10 10 — PKHC — — _ 15 丙烯酸橡膠A — — 35 矽烷偶合劑 SH-6040 — — 2 導電粒子 導電粒子A 10 5 10 導電粒子B — — 一 導電粒子c — — — -29 ~ 201134904 [表2] 材料物質 比較例1 比較例2 比較例3 比較例4 比較例5 發生游離自由 基的硬化劑 Perhexa 250 4 4 4 — — 自由基聚合性 物質 UN-5500 30 30 30 — — DCP-A 8 8 8 — — M-215 8 8 8 一 — P-2M 2 2 2 — — 環氧樹脂 HX3941HP-SS — — — 50 50 熱塑性樹脂 UR-8200 45 45 45 — — EV40W 10 10 10 — 一 PKHC — — — 15 15 丙烯酸橡膠A — 一 — 35 35 矽烷偶合劑 SH-6040 — ~ — 2 2 導電粒子 導電粒子A — — — — — 導電粒子B 10 — 一 10 — 導電粒子c — 10 5 — 10 (2)電路構件的連接構造之製作 (2-1)經OSP處理的印刷配線板（PWB)之製作 於玻璃•環氧樹脂多層印刷配線板上，形成線寬1 ΟΟμιη 、間距400μπι、厚度35μπι的銅電路電極（以下將此稱爲「 PWB」）》再者，對PWB的銅電路電極表面，使用苯并咪 唑化合物（四國化成（股）製，商品名「Tufence」）， 進行OSP處理，而形成厚度0.10〜〇.32μπι的苯并咪唑系樹 脂錯合物之被膜（以下將此稱爲「OSP-PWB」）。 (2-2 )經OSP處理的撓性印刷配線板（FPC )之製作 準備於厚度25 μιη的聚醯亞胺薄膜上，直接形成有線寬 -30- 201134904 ΙΟΟμηι、間距400μιη、厚度18μιη的銅電路電極之撓性印刷 配線板（以下將此稱爲「FPC」）。對此，與上述同樣地 施予OSP處理，而形成厚度0.10〜〇·32μπι的苯并咪唑系樹 脂錯合物之被膜（以下將此稱爲「OSP-FPC」）。 (2-3)電路電極之連接（PWB與FPC之連接） 於OSP-PWB上，黏貼上述薄膜狀的電路連接材料之黏 著面後，在7〇°C於IMPa下加熱及加壓2秒而暫時連接，然 後剝離PET薄膜。接著，使OSP-FPC的電路電極與OSP-PWB的電路電極相向地定位後，在160°C於4MPa下加熱及 加壓6秒。FPC與PWB的基板間之寬度爲2mm。 (3)電路構件的連接構造之評價 (3 -1 )連接電阻之測定 使用數位多用電錶，以2端子法來測定所製作的連接 構造之含電路連接部的電路間之電阻値。連接電阻的測定 係在連接後立即、在8 5 °C 8 5 % RH的恆溫恆濕槽中進行1 〇〇〇 小時保持的高溫高濕處理後、及在進行-4〇°C〜+l〇〇°C的熱 衝撃試驗1 000次循環處理後分別測定。表3中顯示結果。 -31 - 201134904 [表3] 連接電阻（Ω) 連接後立即 筒溫筒濕處理後 熱衝撃試驗後 實施例1 0.2 0.4 0.5 實施例2 0.2 0.4 0.6 實施例3 0.2 0.4 0.5 比較例1 0.2 2.3 3.2 比較例2 0.2 0.5 1.4 比較例3 0.2 0.5 1.9 比較例4 0.3 1.8 2.9 比較例5 0.2 0.6 1.8 實施例1〜3的電路連接材料係在高溫高濕處理後及熱 衝撃試驗後，皆確認連接電阻的上升小，連接可靠性優異 。另一方面，使用僅由Ni粒子所成的導電粒子之比較例1 及4的電路連接材料，係各試驗後的接觸電阻大幅上升。 又，使用表面具有突起的由Ni粒子所成的導電粒子之比較 例2、3及5的電路連接材料，雖然高溫高濕試驗的連接電 阻之上升係比較小，但於熱衝撃試驗後，連接電阻係顯著 上升。 【圖式簡單說明】 圖1係顯示電路連接材料的一實施形態之截面圖。 圖2係顯示連接構造的一實施形態之截面圖。 圖3係顯示連接構造的一實施形態之截面圖。 【主要元件符號說明】 -32- 201134904 1 :電路連接材料 1 a :連接部 3 :樹脂層 3 a :已硬化的樹脂層 5 :導電粒子 1 〇 :第一之電路構件 1 1 :第一基板 13 :第一之電路電極 1 3 a :導體部 13b :被膜 20 :第二之電路構件 21 :第二基板 23:第二之電路電極 23a :導體部 23b :被膜 100 :電路構件之連接構造 -33XI/3 of 40 mass parts of "HX3941HP-SS" and 37.5 parts by mass (15 parts by mass in terms of non-volatile content) of 40% by mass of toluene/ethyl acetate (=5 0/5 0) of "PKHC" ) a solution of 30 parts by mass (35 parts by mass in terms of non-volatile content) of 10% by mass of toluene/acetic acid ethyl acetate (=50/50) solution and 1 part by mass of "SH6040" of "acrylic rubber A". 10 parts by mass of "conductive particle A" was blended. This mixed solution was applied onto a PET film by a coater, and dried by hot air at 70 ° C for 10 minutes to obtain a film-like circuit connecting material having a thickness of the adhesive layer of 35 μm. (Comparative Example 1) A circuit-connecting material 〇 (Comparative Example 2) was obtained in the same manner as in Example 1 except that 10 parts by mass of "conductive particles" was changed to 10 parts by mass of "conductive particles" (Comparative Example 2), except for 10 parts by mass. The circuit connecting material was obtained in the same manner as in Example 1 except that the conductive particles A were changed to 10 parts by mass of the "conductive particles C" (Comparative Example 3), except that 10 parts by mass of "conductive particles A" were changed to 5 parts by mass. A circuit connecting material was obtained in the same manner as in Example 1 except for "conductive particles C". -28-201134904 (Comparative Example 4) A circuit-connecting material (Comparative Example 5) was obtained in the same manner as in Example 3 except that 10 parts by mass of "conductive particles A" was changed to 10 parts by mass of "conductive particles B". A circuit connecting material was obtained in the same manner as in Example 3 except that 10 parts by mass of "conductive particles A" was changed to 10 parts by mass of "conductive particles C". Table 1 shows the composition of the circuit connecting material of Example 丨3 in parts by mass (in terms of non-volatile content), and the parts in Table 2 are in parts by mass (non-volatile parts are changed to stomach). The circuit connecting materials of Comparative Examples 1 to 5 are shown. Composition 1. [Table 1] Material Substance Example 1 Example 2 Example 3 Hardener which generates free radicals Perhexa 250 4 4 - Radical polymerizable substance UN-5500 30 30 — DCP-A 8 8 — M-215 8 8 — P-2M 1 . 2 Epoxy resin HX3941HP-SS — _ 50 Thermoplastic resin UR-8200 45 45 — EV40W 10 10 — PKHC — — _ 15 Acrylic rubber A — — 35 decane coupling agent SH-6040 — — 2 Conductive particle conductive particles A 10 5 10 Conductive particles B — — Conductive particles c — — — -29 ~ 201134904 [Table 2] Material substance Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Free radicals occurred Hardener Perhexa 250 4 4 4 — Free radically polymerizable material UN-5500 30 30 30 — — DCP-A 8 8 8 — — M-215 8 8 8 A — P-2M 2 2 2 — — Epoxy resin HX3941HP-SS — — — 50 50 Thermoplastic Resin UR-8200 45 45 45 — — EV40W 10 10 10 — A PKHC — — — 15 15 Acrylic rubber A — A — 35 35 Decane coupling agent SH-6040 — ~ — 2 2 Conductive particles Conductive particles A — — — — — Conductive particles B 10 — 10 - Conductive particles c - 10 5 - 10 (2) Production of connection structure of circuit members (2-1) Production of printed wiring boards (PWB) processed by OSP on glass/epoxy multilayer printed wiring boards, A copper circuit electrode having a line width of 1 ΟΟμιη, a pitch of 400 μm, and a thickness of 35 μm (hereinafter referred to as "PWB") is formed. Further, a benzimidazole compound (four countries) is used for the surface of the copper circuit electrode of the PWB. The product name "Tufence") is subjected to OSP treatment to form a film of a benzimidazole resin complex having a thickness of 0.10 to 32.32 μm (hereinafter referred to as "OSP-PWB"). (2-2) The flexible printed wiring board (FPC) processed by OSP is prepared on a polyimide film with a thickness of 25 μm, and directly forms a flexible printed circuit of a copper circuit electrode having a width of -30-201134904 ΙΟΟμηι, a pitch of 400 μm, and a thickness of 18 μm. Wiring board (hereinafter referred to as "FPC"). On the other hand, the OSP treatment was carried out in the same manner as above to form a film of a benzimidazole-based resin complex having a thickness of 0.10 to 〇32 μm (hereinafter referred to as "OSP-FPC"). (2-3) Connection of circuit electrodes (connection of PWB and FPC) After bonding the adhesive surface of the film-like circuit connecting material on the OSP-PWB, it is heated and pressurized at 1 °C for 1 second at 1 °C. Temporarily connected and then peeled off the PET film. Next, the circuit electrodes of the OSP-FPC were positioned opposite to the circuit electrodes of the OSP-PWB, and then heated and pressurized at 4 MPa for 6 seconds at 160 °C. The width between the substrates of the FPC and the PWB is 2 mm. (3) Evaluation of the connection structure of the circuit member (3 - 1) Measurement of the connection resistance The resistance 値 between the circuits including the circuit connection portion of the connection structure to be produced was measured by a two-terminal method using a digital multimeter. The connection resistance is measured immediately after the connection, in a constant temperature and humidity chamber at 8 5 ° C 8 5 % RH for 1 〇〇〇 hours, after high temperature and high humidity treatment, and at -4 ° ° C ~ + l The thermal enthalpy test of 〇〇 ° C was measured after 1 000 cycles of treatment. The results are shown in Table 3. -31 - 201134904 [Table 3] Connecting resistance (Ω) Immediately after the tube was wet-treated after the hot-pressing test, Example 1 0.2 0.4 0.5 Example 2 0.2 0.4 0.6 Example 3 0.2 0.4 0.5 Comparative Example 1 0.2 2.3 3.2 Comparative Example 2 0.2 0.5 1.4 Comparative Example 3 0.2 0.5 1.9 Comparative Example 4 0.3 1.8 2.9 Comparative Example 5 0.2 0.6 1.8 The circuit connecting materials of Examples 1 to 3 were confirmed to have a connection resistance after high temperature and high humidity treatment and after hot pressing test. The rise is small and the connection reliability is excellent. On the other hand, in the circuit connecting materials of Comparative Examples 1 and 4 using conductive particles formed only of Ni particles, the contact resistance after each test was greatly increased. Further, the circuit connecting materials of Comparative Examples 2, 3, and 5 in which conductive particles made of Ni particles having protrusions on the surface were used, although the connection resistance of the high-temperature and high-humidity test was relatively small, but after the thermal flushing test, the connection was made. The resistance system has risen significantly. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an embodiment of a circuit connecting material. Fig. 2 is a cross-sectional view showing an embodiment of a connection structure. Fig. 3 is a cross-sectional view showing an embodiment of a connection structure. [Description of main component symbols] -32- 201134904 1 : Circuit connection material 1 a : Connection portion 3 : Resin layer 3 a : Hardened resin layer 5 : Conductive particles 1 〇: First circuit member 1 1 : First substrate 13: first circuit electrode 1 3 a : conductor portion 13b : film 20 : second circuit member 21 : second substrate 23 : second circuit electrode 23 a : conductor portion 23 b : film 100 : connection structure of circuit member - 33