1334880 六、發明說明： 【發明所屬之技術領域】 本發明係有關異向性導電電路連接用黏著劑、使用該 黏著劑之電路板的連接方法與電路連接構造體，更詳細地 說，係有關低溫快速硬化性優異，且保存安定性也良好、 連接電阻亦安定之異向性導電電路連接用黏著劑，及使用 該黏著劑之電路板的連接方法以及連接構造體者。 【先前技術】 近年，在半導體或液晶顯示器等範疇中，為了固定電 子零件，或為了進行電路連接而使用各種黏著材料，在此 等用途中，越來越邁向高密度化、高精細化，黏著劑方面 也要求有高黏著力或高可信賴度。 尤其做為電路連接材料者，在使用液晶顯示器與TCP 或是FPC與TCP之連接，FPC與印刷配線板之連接，是使 用在黏著劑中分散有導電粒子之異向性導電電路連接用黏 著劑。最近在基板上構裝半導體矽晶片時，並不是採用傳 統的導線連結，而是進行使半導體矽晶片之正面朝下直接 構裝在基板上之所謂壓著晶片（flip chip)構裝，在此也開 始使用異向性導電電路連接用黏著劑（特開昭59-120436 號、特開昭60-191228號、特開平1-251787號、特開平 7-90237號公報）。 又，近年在精密電子機器範疇中，電路正邁向高密度 化，電極幅寬及電極間隔變得極為狹窄，為此，在一向使 用環氧樹脂系之電路連接用黏著劑之連接條件下，會產生 4 313294D1D1 ::線脫洛、剝離、位置不吻合等問題。為了提高生， 力要求連接時間需脑在丨G秒鐘町，低溫快速硬 因而成為不可或缺之要求。 Jr^Fnjr, in 性 公報中揭示❹自由基聚合性物質之^連翻號 U而，含有（甲基）丙烯酸酯、磷酸酯化合物等之白 =聚合性物質與導電粒子之黏著劑若放置在中 接後之連接電阻會有上昇之問^ 則連 【發明内容】 連接供低溫快料聽優異、赫衫性良好、1334880 6. Technical Field of the Invention The present invention relates to an adhesive for connecting an anisotropic conductive circuit, a connection method of a circuit board using the adhesive, and a circuit connection structure, and more particularly, related to An adhesive for connecting an anisotropic conductive circuit, which has excellent low-temperature rapid hardenability, good storage stability, and a stable connection resistance, and a connection method of a circuit board using the adhesive and a connection structure. [Prior Art] In recent years, in the field of semiconductors, liquid crystal displays, etc., in order to fix electronic components or to use various adhesive materials for circuit connection, in these applications, more and more high density and high definition have been achieved. Adhesives also require high adhesion or high reliability. In particular, as a circuit connection material, the connection between the liquid crystal display and TCP or FPC and TCP is used, and the connection between the FPC and the printed wiring board is an adhesive for connecting an anisotropic conductive circuit in which conductive particles are dispersed in an adhesive. . Recently, when a semiconductor germanium wafer is mounted on a substrate, instead of using a conventional wire bond, a so-called flip chip package in which the front surface of the semiconductor chip is directly mounted on the substrate is performed. The adhesive for the connection of the anisotropic conductive circuit is also used (JP-A-59-120436, JP-A-60-191228, JP-A No. 1-251787, JP-A-7-90237). In recent years, in the field of precision electronic equipment, the circuit is moving toward higher density, and the electrode width and the electrode spacing are extremely narrow. Therefore, under the connection conditions of the epoxy resin-based circuit-connecting adhesive, Will produce 4 313294D1D1 :: line detachment, peeling, position mismatch and other issues. In order to improve the life, the force requires the connection time to be in the 秒钟G second town, and the low temperature is fast and hard and thus becomes an indispensable requirement. Jr^Fnjr, in the publication of the ❹ ❹ ❹ ❹ 聚合 ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ After the connection, the connection resistance will rise. ^ Even the [invention] The connection is excellent for low temperature and good material, and the hood is good.
黏著劑之電路板連接方W 狀生導電粒子均勻分散而―薄膜 導電電路連接用黏著^下成分所構成為其特徵之異向性 子、（）在表面不露出報、金、m卜之過渡金屬的導電粒 (2)自由基聚合性物質、 ⑶由加熱或光產生游離基之硬化劑。 薄膜狀生:::是導=子均句分散而成之樹腊 向性導電電路構減其特徵之異 子、在表面不露出報、金、細外之献金屬的導電粒 313294D1D1 1334880 (2) 自由基聚合性物質、 (3) 由加熱或光產生游離基之硬化劑，及 (4 )鱗酸自旨化合物 本發明亦有關將上述異向性導電電路連接用黏著劑介 入具有相對向電路電極的基板間，加壓具有相對向電路電 極的基板，同時，依場合不同，照射光（活性能源）將加壓 方向之電極間以電氣連接電路板之連接方法。 本發明又有關將上述異向性導電電路連接用黏著劑介 入具有相對向電路電極的基板間’加壓具有相對向電路電 極的基板後，將加壓方向之電極間以電氣連接之連接構造 體。 本發明之異向性導電電路連接用黏著劑，即使放置在 室溫高濕度下，在連接初期經耐濕試驗、冷熱循環等各種 信賴性試驗後，也能夠抑制連接電阻之上昇或連接強度之 下降，顯示具有優異連接可信度。 異向性導電電路連接用黏著劑，是在薄膜、被黏著體 表面形成之異向性導電樹脂。 本發明又有關介入具有相對向電路電極的基板間，加 壓具有相對向電路電極的基板後，將加壓方向之電極間以 電氣連接之異向性導電電路連接用黏著劑，上述黏著劑係 以含有經由選自（1)自由基聚合性化合物，及（2)鹼性化合 物及至少有1個環氧基之化合物所成組群中至少一種化合 物進行表面處理後之導電粒子為特徵之異向性導電電路連 接用黏著劑。上述異向性導電電路連接用黏著劑，係以含 6 313294D1D1 1334880 , 有由光或加熱產生自由基之化合物或鱗酸酷化合物者為 佳。再者，本發明之異向性導電電路連接用黏著劑，係以 % 表面處理中使用之鹼性化合物為胺系化合物者為佳。 ·· 又，本發明之另一種形態，是將異向性導電電路連接 - 用黏著劑介入在具有相對向電路電極的基板間，加壓具有 相對向電路電極的基板後，將加壓方向之電極間以電氣連 接而成之連接構造體，異向性導電電路連接用黏著劑係有 關含有經由選自（1)自由基聚合性化合物，及（2)鹼性化合 I 物及至少有1個環氧基之化合物所成組群中至少一種化合 ' 物進行表面處理後之導電粒子之黏著劑的異向性導電電路 連接構造體。 【實施方式】 本發明的異向性導電電路連接用黏著劑，是使用在導 電粒子表面上不露出銀、金、鉑以外之鎳等過渡金屬的導 電粒子。為了可以充分得到耐濕保存期限及連接可信度， |最表面之金屬必需是銀、金、始族之貴金屬，而以金較佳。 在本發明的異向性導電電路連接用黏著劑中使用之導 電粒子，只要有可以得到電氣連接之導電性即可，而無特 別限定，但可以列舉如金、銀、鎳、銅、鈷、錫等之金屬 粒子或碳等。又，也可以使用以上述金屬導電物質被覆之 非導電性之玻璃、陶瓷、塑膠等。此時，被覆金屬層之厚 度，為了可以得到充分之導電性，以10 0 A以上為宜。在钻、 鋅、銅、鎳等過渡金屬上設置貴金屬類層時，因貴金屬類 層之缺損或導電粒子混合分散時所產生之貴金屬類層缺損 7 313294D1D1 1334880 等所產生的氧化還原作用，會產生游離基而引起保存期限 減短，所以導電粒子需經表面處理。導電粒子之使用範圍 為相當於電路連接用黏著劑成分之0. 1至30體積％，最好 使用0. 1至20體積％之範圍。 做為導電粒子表面處理之化合物，以對酸性物質具有 反應性之化合物來處理為宜，依此處理可以顯著提高上述 異向性導電電路連接用黏著劑之保存安定性。 做為導電粒子表面處理之化合物，以驗性化合物或至 少具有1個環氧基之化合物為宜，尤其做為驗性化合物者 以胺系化合物為佳。 做為胺系化合物者，液體、固體都可以，固體需先溶 解到有機溶劑或水等然後使用。又，液體之化合物中，也 以溶解在有機溶劑等然後使用為宜。做為有機溶劑者，只 要能溶解氨系化合物而不與氨系化合物反應者即可，無特 別限制，但以曱醇、乙醇、異丙醇、曱乙酮、醋酸乙酯、 甲笨等處理後能乾燥導電粒子者為宜。 處理液中所含胺系化合物之濃度，以0. 05至20重量°/〇 為宜，未滿0. 05重量％時不能有效進行表面處理，超過20 重量％時導電粒子表面被覆之氨系化合物量變多，連接電阻 變高。 做為至少具有1個環氧基之化合物者，液體、固體都 可以，固體之場合需使溶解在有機溶劑或水等然後使用。 又，液體之化合物也以使用溶解到有機溶劑等然後使用為 宜。做為有機溶劑者，只要能溶解至少具有1個環氧基之 8 313294D1D1 ί:::ΓΓ少具有1個環氧基之化合物反應者即可， :广但q醇、乙醇、異丙醇、甲乙闕、醋酸乙 曰、〒本4表面處理後能乾燥導電粒子者為宜。 處理液中所含至少具有〗個環氧基之化合物濃度 7至20重量％為宜，未滿0.05重量辦不能有效進行表 面处超過2〇重量％時，導電粒子表面被覆之至少具有 1個環氧基之化合物量變多，連接電阻變高。 著面處理時間等處理條件，並無特別限制， 但處理溫度是以室溫（肌）至lore、處理時間是以10秒 至1小時之範圍為宜。 又’處理後之導電粒子是經過濾後乾燥才使用，乾燥 條件隨使用之有機溶劑而作適當之選擇，但在室溫⑶ 至100°C中進行。 本發明之表面處理所使用之鹼性化合物，尤其做為氨 系化合物者可以列舉如，三乙胺、二乙胺、丁胺、乙二胺、 %六甲基二胺、苯胺、胺基丙基三甲氧基矽烷、咪唑、2-乙 基―4—甲基咪唑、2—笨基-1-氰基乙基咪唑、苯乙基咪唑、 苯乙基咬等，㈣中可關舉i級、2級、3級胺，也可 以使用混合2種類以上者。 本發明之表面處理所使用之至少具有丨個環氧基之化 合物，可以使用苯基縮水甘油醚、（曱基）丙烯酸縮水甘油 酯、1r-環氧丙氧基丙基三甲氧基矽烷、7_環氧丙氧基丙 基三乙氧基矽烷、r-環氧丙氧基丙基甲基二甲氧基矽烷、 r-環氧丙氧基丙基二乙氧基矽烷、^—(3，4環氧環己基） 9 313294D1D1 1334880 ί基ί: t基残、雙齡A型環氧樹脂、雙紛F型環氧樹 月曰、雙酚S型環氧樹脂、酚醛、.主孑刑 清漆型環氧樹脂、雔酚“二一伽曰、f酚酚醛 藤清漆型環氧樹= %氧樹脂、雙紛 衣式哀氧树脂、縮水甘油酯型環 :脂、縮水甘油胺型環氧樹脂、乙内《環氧樹脂I : 酸醋型環氧樹脂、脂肪族鍵狀環氧樹脂等，此等環氧樹： 也可以鹵化，也可以禾知气u 寸衣乳祕月曰 氧化合物。 添加虱。也可以併用2種以上此等環 本發明之異向性導電電路連接用翁著劑中使用之 基聚合性化合物，係具有由自由基誘發聚合之官能基之化 合物，有（甲基）丙騎醋樹脂、馬來酸酐縮亞胺樹脂、宏 康酿亞胺樹脂、萘紛二亞胺樹脂等，也可以使用2種類： 上之/tD S物又自由基聚合性化合物也可以使用單體、寡 聚合物中之任一種狀態，也可以使用單體與寡聚合物之混 合物，在此『（f基）丙烯酸醋』是指丙烯酸酯及其相 之甲基丙烯酸酯。 & 做為（甲基）丙烯酸酯樹脂者，是使（甲基）丙烯酸酯進 行自由基聚合而得者，做為（甲基）丙烯酸酯者，可列舉如 (甲基）丙烯酸曱酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸異 丙酯、（甲基）丙烯酸異丁酯、二（甲基）丙烯酸乙二醇酯、 二（甲基）丙烯酸二乙二醇酯、三（甲基）丙烯酸三曱醇丙烷 酯、四（甲基）丙烯酸四甲基乙二醇酯、2-羥基-丨，3一二丙缚 醯丙烷、2, 2-雙[4-(丙烯醯曱氧基）笨基]丙烷、2, 2-雙 [4-（丙稀酿乙氧基）本基]丙院、（甲基）丙稀酸二環戊稀 313294D1D1 10 1334880 酯、（甲基）丙烯酸三環癸烷、異氰酸三（丙烯醯乙基）酯、（甲 基）丙烯酸胺酯'異氰酸環乙烷改質二氰酸等，可單獨使用 也可以使用兩種以上混合者。又，由於必要，在不損及硬 .化性範圍下也可以使用氫醌、甲基醚氫醌等之自由基聚合 • 禁止劑。 ° 再者，使用磷酸酯化合物做為自由基聚合性化合物之 琢&針對金屬荨無機物可以提高接著力。此磷酸醋化合 物之使用量是相對於接著劑成分1〇〇重量份的〇.丨至1〇重 置份，較佳為〇. 5至5重量份。磷酸酯化合物是由無水磷 酸和（甲基）丙烯酸2-羥基乙酯之反應生成物而得。具體的 有單（曱基丙烯醯乙基）酸磷酸、二（甲基丙晞醯乙基）酸磷 酸等’可單獨或混合使用。 做為馬來酸軒縮亞胺樹脂者，是分子中至少含有1個 馬來酸酐縮亞胺者，例如苯基馬來酸酐縮亞胺、甲基 -2, 4-馬來酸酐縮亞胺隻苯、N，Ν’-m-苯基雙馬來酸肝縮亞 •胺、Ν，Ν’-ρ-苯基雙馬來酸酐縮亞胺、Ν，Ν，—4,4_雙苯基雙 馬來酸酐縮亞胺、Ν，Ν’ -4, 4-(3, 3-二曱基二笨基）雙馬來酸 酐縮亞胺、Ν，Ν’ -4, 4-(3, 3-二曱基二苯基甲烷）雙馬來酸酐 縮亞胺、Ν，Ν’ -4, 4-(3, 3-二乙基雙苯基曱烷）雙馬來酸酐縮 亞胺、Ν, Ν’ -4, 4-二苯基乙烷雙馬來酸酐縮亞胺、ν，Ν，-4, 4-二苯基丙烧雙馬來酸針縮亞胺、Ν，Ν’ -4, 4-雙苯基乙謎雙馬 來酸酐縮亞胺、Ν，Ν’-4, 4-雙苯基磺基雙馬來酸酐縮亞胺、 2,2-雙（4-(4-馬來酸酐縮亞胺苯氧基）苯基）丙烷、2,2-雙 (3-s-丁基-3, 4-(4-馬來酸酐縮亞胺苯氧基）苯基）丙烷、 11 313294D1D1 1334880 1，1-雙（4-(4-馬來酸酐縮亞胺苯氧基）苯基）癸烷、4, 4-環 亞己基-雙（1-(4-馬來酸酐縮亞胺苯氧基）苯氧基）-2-環己 基苯、2,2-雙（4-(4-馬來酸酐縮亞胺苯氧基）苯基）六氟丙 烧等，可單獨使用也可以使用兩種以上混合。 做為寧康醯亞胺樹脂者，是將分子中至少含有1個寧 康醯亞胺基之寧康醯亞胺化合物聚合而成者，做為寧康醯 亞胺化合物者，例如有苯基寧康醯亞胺、卜曱基-2, 4-雙寧 康醯亞胺笨、N，Ν’-m-苯基雙寧康醯亞胺苯、N, Ν’ -p-苯基 雙寧康醯亞胺苯、Ν, Ν’ -4, 4-雙苯基雙寧康醯亞胺、Ν，Ν’ -4,4-(3,3-二曱基二苯基）雙寧康醯亞胺、^犷-4,4-(3,3-二甲基二苯基曱烷）雙寧康醯亞胺、Ν，Ν’ -4, 4-(3, 3-二乙基 二笨基曱烷）雙寧康醯亞胺、Ν，Ν’-4, 4-二苯基曱烷雙寧康 醯亞胺、Ν, Ν’ -4, 4-二苯基丙烷雙寧康醯亞胺、Ν, Ν’ -4, 4-二苯基乙醚雙寧康醯亞胺、Ν，Ν’ -4, 4-雙笨基磺基雙寧康醯 亞胺、2, 2-雙（4-(4-寧康醯亞胺苯氧基）苯基）丙烷、2, 2-雙（3_s - 丁基-3,4-(4 -寧康酸亞胺笨氧基）苯基）丙烧、1，1_ 雙（4-(4-寧康醯亞胺苯氧基）苯基）癸烷、4,4-環亞己基-雙（1-(4-寧康酸亞胺苯氧基）苯氧基）-2-環己基苯、2,2-雙（4-(4-寧康醯亞胺苯氧基）笨基）六氟丙烷等，可單獨使 用也可以使用兩種以上混合。 做為萘酚二亞胺樹脂者，是將分子中至少含有1個萘 酚二亞胺基之萘酚二亞胺化合物聚合者，做為萘酚二亞胺 化合物者，例如有萘酚二亞胺、卜曱基-2, 4-雙萘酚二亞 胺、N，Ν’-m-苯基雙萘酚二亞胺、N, Ν’ -P-苯基雙萘酚二亞 12 313294D1D1 1334880 , 胺苯、Ν，Ν’-4, 4-雙苯基雙萘酚二亞胺、Ν，Ν’-4, 4-(3, 3-二曱基二苯基）雙萘酚二亞胺、Ν，Ν’ -4, 4-(3, 3-二甲基二苯 基曱烷）雙萘酚二亞胺、Ν，Ν’ -4, 4-(3, 3-二乙基二苯基甲烷） ·- 雙萘酚二亞胺、Ν，Ν’ -4, 4-二苯基曱烷雙萘酚二亞胺、Ν，Ν’-- 4, 4-二苯基丙烷雙萘酚二亞胺、Ν，Ν’ -4, 4-二苯基乙醚雙萘 酚二亞胺、Ν,Ν’-4, 4-雙苯基磺基雙萘酚二亞胺、2, 2-雙 (4-(4-萘酚二亞胺苯氧基）苯基）丙烷、2,2-雙（3-s-丁基 -3, 4-(4-萘酚二亞胺苯氧基）苯基）丙烷、1，1-雙（4-(4-萘 I酚二亞胺苯氧基）笨基）癸烷、4, 4-環亞己基-雙（1-(4-萘酚 二亞胺苯氧基）苯氧基）-2-環己基苯、2, 2-雙（4-(4-萘酚二 亞胺苯氧基）苯基）六氟丙烷等，可單獨使用也可以使用兩 種以上混合。 使用上述自由基聚合性化合物之場合，是使用聚合起 始劑作為由加熱或光產生游離基之硬化劑。做為聚合起始 劑者，只要能由加熱或光產生自由基之化合物即可，而無 |特別限制。有過氧化物、偶氮化合物等，可隨接著溫度、 接著時間、保存安定性等目的適當選擇，但從高反應性和 保存安定性之觀點來看，以半衰期為10小時之溫度為40 °C以上，半衰期為1分鐘之溫度為180°C以下之有機過氧 化物為佳。半衰期為10小時之溫度為40°C以上，半衰期 為1分鐘之溫度為170°C以下之有機過氧化物尤佳。接著 時間為10秒之場合，為了得到充分反應率之聚合起始劑的 配合量，相對於接著劑之總量，以1至20重量％為佳，以 2至15重量％為特佳。做為具體使用之有機過氧化物者， 13 313294D1D1 1334880 可以選自二醯過氧化物、二碳酸過氧化物、過氧化物δ旨、 過氧化物酮縮醇、二烧基過氧化物、氫過氧化物、甲石夕烧 基過氧化物等，但是過氧化物酯、二烷基過氧化物、氫過 氧化物、甲矽烷基過氧化物等，因為起始劑中之氯離子或 有機酸在5000 ppm以下，分解後產生之有機酸很少，可以 抑制電路構材之接著端子之腐蝕，所以特佳。由可得高反 應性之過氧化物酯來選定更佳，此等可以適當混合使用。 做為二醯過氧化物類者，可列舉如異丁基過氧化物、 2,4-二氯苯醯過氧化物、3, 5, 5-三甲基己醯過氧化物、辛 酸過氧化物、十二基酿過氧化物、硬脂酿過氧化物、繞拍 酸過氧化物、過氧化物、苯酿過氧化物曱苯、苯酸過氧化 物等。 做為二碳酸過氧化物類者，可列舉如二-η-丙基過氧化 物二碳酸鹽、二異丙基二碳酸鹽過氧化物二碳酸鹽、雙（4-三級-丁基環己基）過氧化物二碳酸鹽、二-2-乙氧基曱氧基 過氧化物二碳酸鹽、二（2-乙基己基過氧化物）二碳酸鹽、 二曱氧基丁基二碳酸過氧化物二碳酸鹽、二（3-甲基-3-乙 氧基丁基過氧化物）二碳酸鹽等。 做為過氧化物S旨者，可列舉如丙基過氧化物新癸酸 酯、1, 1，3, 3-四曱基丁基過氧化物新癸酸酯' 1-環己基-1-甲基乙基過氧化物新癸酸酯、三級-己基過氧化物新癸酸 酯、三級-丁基過氧化物新癸酸酯、1，1，3, 3-四曱基丁基過 氧化物-2-乙基己酸酯、2, 5-二曱基-2, 5-二（2-乙基己醯基 過氧化物）己烷、1-環己基-1-甲基乙基過氧化-2-乙基己酸 14 313294D1D1 1334880 西曰、二級-己基過氧化物_2_乙基己酸醋、三級—丁義過氧化 物-2-乙基已酸酯、三級_丁基過氧化物異丁酸_、丄卜（二 級過氧化物）環己烷、三級-己基過氧化物異丙單碳酸越、The circuit board of the adhesive is connected to the W-shaped conductive particles uniformly dispersed. The thin-film conductive circuit is connected with the adhesive component, which is characterized by the anisotropy, and () the transition metal of the report, gold, and m is not exposed on the surface. Conductive particles (2) radically polymerizable substances, (3) hardeners which generate radicals by heating or light. Film-like raw::: is a conductive particle with a characteristic of the derivative of the tree-to-small-segmented structure, which is reduced in its characteristics, and does not expose the conductive particles of the metal, 313294D1D1 1334880 (2) a radically polymerizable substance, (3) a hardener which generates a radical by heating or light, and (4) a scaly acid self-acting compound. The present invention also relates to the above-mentioned anisotropic conductive circuit connecting adhesive having a relative circuit Between the substrates of the electrodes, the substrate having the opposing electrode electrodes is pressurized, and depending on the case, the irradiation light (active energy source) is a method of electrically connecting the electrodes in the pressurizing direction to the circuit board. Further, the present invention relates to a connection structure in which an adhesive for connecting an anisotropic conductive circuit is interposed between a substrate having a surface opposite to a circuit electrode and a substrate having a surface opposite to the circuit electrode, and electrically connecting the electrodes in a pressurization direction. . The adhesive for connecting an anisotropic conductive circuit of the present invention can suppress an increase in connection resistance or a connection strength even after being subjected to various reliability tests such as a moisture resistance test and a thermal cycle at the initial stage of connection, even when placed at room temperature and high humidity. Decrease, showing excellent connection reliability. The adhesive for connecting an anisotropic conductive circuit is an anisotropic conductive resin formed on the surface of a film or an adherend. Further, the present invention relates to an adhesive for connecting an anisotropic conductive circuit for electrically connecting between electrodes having a surface opposite to a circuit electrode and having a substrate facing the circuit electrode, and electrically connecting the electrodes in a pressurizing direction, the adhesive system Conductive particles characterized by containing at least one compound selected from the group consisting of (1) a radically polymerizable compound, and (2) a basic compound and at least one epoxy group are characterized by a difference Adhesive for connecting conductive conductive circuits. The above-mentioned anisotropic conductive circuit-bonding adhesive is preferably a compound containing 6 313294D1D1 1334880 which has a radical or a scalar compound which generates light by heating or heating. Further, in the adhesive for connecting an anisotropic conductive circuit of the present invention, it is preferred that the basic compound used in the surface treatment is an amine compound. Further, another aspect of the present invention is to connect an anisotropic conductive circuit with an adhesive interposed between the substrates having the opposing circuit electrodes, pressurizing the substrate having the opposing circuit electrodes, and pressurizing the direction a connection structure in which the electrodes are electrically connected to each other, and the adhesive for the anisotropic conductive circuit connection is selected from the group consisting of (1) a radically polymerizable compound, and (2) a basic compound and at least one An anisotropic conductive circuit-connecting structure of an adhesive of conductive particles in which at least one of the compounds of the epoxy group is subjected to surface treatment in a group of epoxy groups. [Embodiment] The adhesive for connecting an anisotropic conductive circuit of the present invention is a conductive particle which does not expose a transition metal such as nickel other than silver, gold or platinum on the surface of the conductive particles. In order to fully obtain the moisture-resistant shelf life and the reliability of the connection, the metal of the outermost surface must be a precious metal of silver, gold, and the first group, and gold is preferred. The conductive particles used in the adhesive for connecting an anisotropic conductive circuit of the present invention are not particularly limited as long as they have electrical conductivity capable of electrical connection, and examples thereof include gold, silver, nickel, copper, and cobalt. Metal particles such as tin or carbon. Further, a non-conductive glass, ceramic, plastic or the like coated with the above-mentioned metal conductive material may be used. In this case, the thickness of the metal layer to be coated is preferably 100 A or more in order to obtain sufficient conductivity. When a noble metal layer is provided on a transition metal such as drill, zinc, copper or nickel, a redox effect generated by a defect of the noble metal layer or a noble metal layer defect generated by mixing and dispersing the conductive particles 7 313294D1D1 1334880 may occur. The free radicals cause a short shelf life, so the conductive particles need to be surface treated. 1至20体积%的范围内。 The conductive particles are used in a range of from 0.1 to 30% by volume, preferably from 0.1 to 20% by volume. It is preferable to treat the compound which is a surface treatment of the conductive particles with a compound which is reactive with an acidic substance, and the treatment stability of the above-mentioned anisotropic conductive circuit-bonding adhesive can be remarkably improved. As the compound for surface treatment of the conductive particles, it is preferred to use an intrinsic compound or a compound having at least one epoxy group, and particularly preferably an amine compound. As the amine compound, liquid or solid can be used, and the solid needs to be dissolved in an organic solvent or water and then used. Further, in the liquid compound, it is preferably dissolved in an organic solvent or the like and then used. As an organic solvent, as long as it can dissolve an ammonia compound and does not react with an ammonia compound, it is not particularly limited, but it is treated with decyl alcohol, ethanol, isopropanol, acetophenone, ethyl acetate, and stupid. It is preferred to dry the conductive particles afterwards. The concentration of the amine compound contained in the treatment liquid is preferably 0.05 to 20 weight % / 〇, and the surface treatment is not effective when the content is less than 0.05% by weight, and the ammonia coating of the surface of the conductive particle is more than 20% by weight. The amount of the compound increases, and the connection resistance becomes high. As the compound having at least one epoxy group, a liquid or a solid may be used, and in the case of a solid, it may be dissolved in an organic solvent or water and then used. Further, the liquid compound is preferably dissolved in an organic solvent or the like and then used. As an organic solvent, as long as it can dissolve at least one epoxy group, 8 313294D1D1 ί::: reduce the reaction of a compound having one epoxy group: wide but q alcohol, ethanol, isopropanol, It is advisable to dry conductive particles after surface treatment with ethyl acetamidine, ethyl acetate and hydrazine. The concentration of the compound having at least one epoxy group contained in the treatment liquid is preferably from 7 to 20% by weight, and when it is less than 0.05% by weight, the surface of the conductive particles is coated with at least one ring. The amount of the compound of the oxy group increases, and the connection resistance becomes high. The treatment conditions such as the surface treatment time are not particularly limited, but the treatment temperature is preferably from room temperature (muscle) to lore, and the treatment time is in the range of 10 seconds to 1 hour. Further, the treated conductive particles are used after being dried by filtration, and the drying conditions are appropriately selected depending on the organic solvent to be used, but are carried out at room temperature (3) to 100 °C. The basic compound used in the surface treatment of the present invention, particularly as an ammonia compound, may, for example, be triethylamine, diethylamine, butylamine, ethylenediamine, %hexamethyldiamine, aniline or aminepropylamine. Trimethoxy decane, imidazole, 2-ethyl-4-methylimidazole, 2-phenyl-1-cyanoethylimidazole, phenethyl imidazole, phenethyl bite, etc. For the second or third grade amines, it is also possible to use two or more types. As the compound having at least one epoxy group used in the surface treatment of the present invention, phenyl glycidyl ether, glycidyl (mercapto) acrylate, 1r-glycidoxypropyltrimethoxydecane, 7 may be used. _Glycidoxypropyltriethoxydecane, r-glycidoxypropylmethyldimethoxydecane, r-glycidoxypropyldiethoxydecane, ^—(3 , 4 epoxy cyclohexyl) 9 313294D1D1 1334880 ί基ί: t base residue, double age A type epoxy resin, double F type epoxy tree moon 曰, bisphenol S type epoxy resin, phenolic, main suffrage Varnish type epoxy resin, decyl phenol "two gamma bismuth, f phenol phenol vine varnish type epoxy tree = % oxygen resin, double-dissolved sulphur oxide resin, glycidyl ester type ring: fat, glycidylamine type epoxy Resin, B. "Epoxy resin I: vinegar-type epoxy resin, aliphatic bond-like epoxy resin, etc., such epoxy tree: can also be halogenated, but also can be used to know the gas Addition of ruthenium. It is also possible to use two or more of these rings in combination with the base polymerizable compound used in the anisotropic conductive circuit of the present invention. a compound having a functional group derived by a radical, and having a (meth) propyl vinegar resin, a maleic anhydride imide resin, a macro-enamine resin, a naphthalene diimide resin, or the like The above-mentioned /tD S-radical polymerizable compound may be used in any of a monomer or an oligo polymer, or a mixture of a monomer and an oligo polymer may be used. Here, "(f-based) acrylic vinegar" It refers to methacrylate of acrylate and its phase. & As a (meth) acrylate resin, it is obtained by radical polymerization of (meth) acrylate as (meth) acrylate. Examples thereof include decyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, isobutyl (meth)acrylate, and ethylene glycol di(meth)acrylate. Diethylene glycol di(meth)acrylate, trimethylolpropane tris(meth)acrylate, tetramethylethylene glycol tetra(meth)acrylate, 2-hydroxy-indole, 3-12 diacyl bond Propane, 2,2-bis[4-(acryloxy)phenyl]propane, 2, 2-bis[4-(propylene ethoxy) benzyl] propyl, (meth) acrylate dicyclopentene 313294D1D1 10 1334880 ester, trimethyl decane (meth) acrylate, isocyanide Acid tris(propylene sulfonyl ethyl) ester, (meth) methacrylate amide 'isocyanate cyclohexane modified dicyanic acid, etc., may be used singly or in combination of two or more. In the range of damage and hardness, a radical polymerization or a prohibiting agent such as hydroquinone or methyl ether hydroquinone may be used. Further, a phosphate compound is used as a radically polymerizable compound. The inorganic substance may increase the adhesion. The amount of the phosphoric acid vinegar compound is 〇. 丨 to 1 〇 of the replacement part, preferably 〇. 5 to 5 parts by weight, based on 1 part by weight of the adhesive component. The phosphate compound is obtained by reacting anhydrous phosphoric acid with 2-hydroxyethyl (meth)acrylate. Specifically, it may be used singly or in combination as a single (mercaptopropenylethyl) acid phosphoric acid, bis(methylpropionylethyl)phosphoric acid or the like. As a maleimide resin, it contains at least one maleic anhydride imide in the molecule, such as phenyl maleic anhydride, imine, methyl-2,4-maleic anhydride. Benzene, N, Ν'-m-phenyl bismaleate, amine, hydrazine, Ν'-ρ-phenyl bis-maleic anhydride, imine, hydrazine, 4, 4,4 bis benzene Bis-maleic anhydride imide, hydrazine, Ν'-4, 4-(3,3-dimercapto-diphenyl) bis-maleic anhydride imine, hydrazine, Ν'-4, 4-(3, 3-dimercaptodiphenylmethane) bis-maleic anhydride imide, hydrazine, Ν'-4, 4-(3,3-diethyl bisphenyldecane) bis-maleic anhydride imide, hydrazine , Ν' -4, 4-diphenylethane bis-maleic anhydride imide, ν, Ν, -4, 4-diphenylpropanin bismaleimine, imine, Ν' -4 , 4-bisphenyl-bi-mystery double maleic anhydride imide, hydrazine, Ν'-4, 4-bisphenylsulfobismaleic acid imide, 2,2-bis(4-(4-horse Anhydride acetal phenoxy)phenyl)propane, 2,2-bis(3-s-butyl-3,4-(4-maleic anhydride) phenyloxy)phenyl)propane, 11 313294D1D1 1334880 1,1-bis(4-(4-maleic anhydride) Phenyl) decane, 4, 4-cyclohexylidene-bis(1-(4-maleic anhydride acetimidate) oxy)-2-cyclohexylbenzene, 2,2-bis (4) -(4-maleic anhydride imide phenoxy)phenyl)hexafluoropropane or the like may be used singly or in combination of two or more. As a Ningkang imine resin, a compound containing at least one Ningkang imino group in the molecule is polymerized as a Ningkang imine compound, for example, a phenyl group. Ningkang imine, diterpenoid-2, 4-shuangning Kangxiuimine stupid, N, Ν'-m-phenyl bispyrene, imipenem, N, Ν'-p-phenyl shuangning Kangxi Imine benzene, hydrazine, Ν'-4, 4-bisphenyl bis-quinone quinone imine, hydrazine, Ν'-4,4-(3,3-dimercaptodiphenyl) bispyretin ,^犷-4,4-(3,3-dimethyldiphenyldecane) bispyretinium, anthracene, Ν'-4,4-(3,3-diethyldiphenyl) Alkane, succinimide, hydrazine, hydrazine, -4'-4, 4-diphenyl decane, quinone, hydrazine, hydrazine, Ν'-, 4-diphenylpropane, quinone Ν, Ν' -4, 4-diphenylethyl ether bis quinone quinone, hydrazine, Ν' -4, 4-bis-phenylsulfonyl bispyramine, 2, 2- bis (4-( 4-Ningkang iminophenoxy)phenyl)propane, 2,2-bis(3_s-butyl-3,4-(4-n-conne acid imino)phenyl)propane, 1 ,1_bis(4-(4-Ningkangimine phenoxy)phenyl)decane, 4,4-cyclohexylene-double 1-(4-Nykine iminophenoxy)phenoxy)-2-cyclohexylbenzene, 2,2-bis(4-(4-Ningkangimine phenoxy)phenyl) hexafluoro Propane or the like may be used singly or in combination of two or more. As a naphthol diimine resin, a naphthol diimine compound containing at least one naphthol diimine group in a molecule is polymerized as a naphthol diimine compound, for example, naphthol di Amine, dimercapto-2, 4-bis-naphthol diimine, N, Ν'-m-phenyl bis-naphthol diimine, N, Ν'-P-phenyl bis-naphthol diol 12 313294D1D1 1334880 , amine Benzene, anthracene, Ν'-4, 4-bisphenyl bis-naphthol diimine, anthracene, Ν'-4, 4-(3, 3-dimercaptodiphenyl) bis naphthol diimine, hydrazine ,Ν' -4, 4-(3,3-dimethyldiphenylnonane) bis-naphthol diimine, anthracene, Ν' -4, 4-(3, 3-diethyldiphenylmethane ) - bis-naphthol diimine, hydrazine, Ν' -4, 4-diphenyldecane bis-naphthol diimine, hydrazine, Ν'-- 4, 4-diphenylpropane bis-naphthol diol Amine, hydrazine, Ν'-4, 4-diphenylether bis-naphthol diimine, hydrazine, Ν'-4, 4-bisphenyl sulfonabisnaphthol diimine, 2, 2-double (4 -(4-naphthol diimine phenoxy)phenyl)propane, 2,2-bis(3-s-butyl-3, 4-(4-naphthyldiimide phenoxy)phenyl) Propane, 1,1-bis(4-(4-naphthalene I phenol diimine phenoxy) phenyl) decane, 4, 4-cyclohexylidene-bis(1-(4-naphthol diimine phenoxy)phenoxy)-2-cyclohexylbenzene, 2,2-bis(4-(4-naphthol diimine benzene) Oxy)phenyl)hexafluoropropane or the like may be used singly or in combination of two or more. In the case of using the above radical polymerizable compound, a polymerization initiator is used as a curing agent which generates a radical by heating or light. As the polymerization initiator, as long as it can generate a radical-free compound by heating or light, it is not particularly limited. There are peroxides, azo compounds, etc., which can be appropriately selected for the purpose of temperature, subsequent time, storage stability, etc., but from the viewpoint of high reactivity and storage stability, the temperature at a half-life of 10 hours is 40 °. Above C, an organic peroxide having a half-life of 1 minute and a temperature of 180 ° C or less is preferred. An organic peroxide having a half-life of 10 hours and a temperature of 40 ° C or more and a half-life of 1 minute and a temperature of 170 ° C or less is particularly preferable. When the time is 10 seconds, the amount of the polymerization initiator to be sufficiently reacted is preferably from 1 to 20% by weight, particularly preferably from 2 to 15% by weight, based on the total amount of the adhesive. As a specific organic peroxide, 13 313294D1D1 1334880 may be selected from the group consisting of diterpenoid peroxide, dicarbonate peroxide, peroxide δ, peroxide ketal, dialkyl peroxide, hydrogen Peroxide, methacrylate, etc., but peroxide esters, dialkyl peroxides, hydroperoxides, formyl peroxides, etc., because of the chloride ion or organic in the initiator When the acid is at most 5,000 ppm, the organic acid generated after decomposition is small, and it is possible to suppress corrosion of the subsequent terminals of the circuit member, which is particularly preferable. It is preferably selected from the highly reactive peroxide esters, and these can be suitably mixed. As the diterpenoid peroxide, for example, isobutyl peroxide, 2,4-dichlorophenylhydrazine peroxide, 3,5,5-trimethylhexyl peroxide, octanoic acid peroxidation , twelve base brewing peroxide, hard fat brewing peroxide, circling acid peroxide, peroxide, benzene brewing peroxide, benzene, benzoic acid peroxide, etc. As the dicarbonate peroxide, there may be mentioned, for example, di-n-propyl peroxide dicarbonate, diisopropyl dicarbonate peroxide dicarbonate, bis(4-tertiary-butyl ring). Hexyl)peroxide dicarbonate, di-2-ethoxyhydroxyperoxide dicarbonate, di(2-ethylhexyl peroxide) dicarbonate, dimethoxybutyl phthalate Oxide dicarbonate, bis(3-methyl-3-ethoxybutyl peroxide) dicarbonate, and the like. As the peroxide S, for example, propyl peroxide neodecanoate, 1,1,3, 3-tetradecyl butyl peroxide neodecanoate ' 1-cyclohexyl-1- Methyl ethyl peroxide neodecanoate, tertiary-hexyl peroxide neodecanoate, tertiary-butyl peroxide neodecanoate, 1,1,3, 3-tetradecylbutyl Peroxide-2-ethylhexanoate, 2, 5-dimercapto-2, 5-di(2-ethylhexyl peroxide) hexane, 1-cyclohexyl-1-methyl Base peroxy-2-ethylhexanoic acid 14 313294D1D1 1334880 samarium, di-hexyl peroxide _2_ethylhexanoic acid vinegar, tertiary-butyric peroxide-2-ethyl hexanoate, three Grade _ butyl peroxide isobutyric acid _, 丄 ( (secondary peroxide) cyclohexane, tertiary hexyl peroxide isopropyl monocarbonate,
三級-丁基過氧化物_3, 5, 5-三曱基己酸酯、三級—丁基過氧 化物月桂酸酉旨、2, 5-二甲-2, 5-二（m-曱苯酸過氧化物）己 烧、三級-丁基過氧化物異丙烷單碳酸酯、三級—丁基過氧 化物-2-乙基己基單碳酸酯、三級-己基過氧化物苯酸酯、 三級-丁基過氧化物乙酸酯等。 做為過氧化酮縮醇類者，可列舉如1，1-(三級-己基過 氧化物）-3, 3, 5-三甲基環己烧、1，1-(三級-己基過氧化物°) 環己烷、1，1-(三級-丁基過氧化物）-3,3,5~三甲基環己 烧、1，1-(三級-丁基過氧化物）環癸烷、2, 2-雙（三級—丁基 過氧化物）癸烷等。 做為二烷基過氧化物類者可列舉如，ο:，α，-雙（三級_ 丁基過氧化物）二異丙笨、二異苯丙基過乳化物、2 5 _二曱 _基-2 5-二（三級-丁基過氧化物）己烷、三級_丁基異苯丙基 過氧化物等。 做為氫過氧化物類者可列舉如，二異丙基笨氫過氧化 物、異苯丙烷氫過氧化物等。 做為甲石夕烧基過氧化物類者可列舉如，三級-丁基三甲 基甲矽烷基過氧化物、雙（三級-丁基）二甲基曱矽烷基過氧 化物、三級-丁基三乙烯基甲矽烷基過氧化物、雙（三級一 丁基）一乙細基曱石夕烧基過氧化物、三（三級-丁基）二乙婦 基曱石夕烷基過氧化物、三級-丁基三丙烯基甲石夕烧基過氧化 15 313294D1D1 1334880 物、雙（三級-丁基）二丙烯基曱矽烷基過氧化物、三（三級-丁基）丙婦基曱發烧基過氧化物等。 又，為了抑制電路構材之連接端子之腐蝕，游離基發 生劑（硬化劑）中所含之氯離子或有機酸是以在5000 ppm以 下為宜，再者，加熱分解後產生之有機酸以少者為佳。又， 在提高製成電路連接材料之安定性上，以室溫（25°C)、常 壓下開放放置24小時後仍具有20重量％以上之重量保持率 者為宜，此等可適當混合使用。 此等游離基發生劑可以單獨或混合使用，也可以與分 解促進劑、抑制劑等混合使用。 ， 又，此等游離基發生劑以聚胺酯系、聚酯系之高分子 物質等覆蓋後使之微膠囊化之產物，因能延長可使用時 間，所以較佳。 自由基聚合性化合物以外，也可以配入做為熱硬化性 樹脂之環氧樹脂。做為環氧樹脂者，有雙酚A型環氧樹脂、 雙酚F型環氧樹脂、雙酚S型環氧樹脂、酚醛清漆型環氧 樹脂、曱酚酚醛清漆型環氧樹脂、雙酚A酚醛清漆型環氧 樹脂、雙酚F酚醛清漆型環氧樹脂、脂環式環氧樹脂、縮 水甘油S旨型環氧樹脂、縮水甘油胺型環氧樹脂、乙内蕴脲 環氧樹脂、異氰酸酯型環氧樹脂、脂肪族鏈狀環氧樹脂等， 此等環氧樹脂也可以ii素化、也可以加氫。此等環氧樹脂 也可以併用2種以上。 又，做為上述環氧樹脂之硬化劑者，可使用如胺類、 酚類、酸酐類、咪唑類、二氰二醯胺等通常做為環氧樹脂 16 313294D1D1 1334880 . 硬化劑者。再者，做為硬化促進劑者，通常可以適當使用 3級胺、有機磷系化合物。 又，做為使環氧樹脂反應之方法者，在使用上述硬化 ·- 劑以外，也可以使用四價硫（sulfonium ;硫鐃）鹽、蛾鐵鹽 - 等，使陽離子聚合也可以。 在本發明之電路接著用黏著劑或異向性導電樹脂薄膜 ' 狀生成物中，為了賦與薄膜形成性、黏著性、硬化時之應 力緩和性，一般要使用聚乙烯丁縮醛樹脂、聚乙烯甲縮醛 ®樹脂、聚酯樹脂、聚醯胺樹脂、聚亞醯胺樹脂、二甲苯樹 脂、聚胺S旨樹脂、尿素樹脂等高分子成分，此等高分子成 分是以分子量為10, 〇〇〇至1 0, 000, 000者為宜。又，此等 樹脂，也可以是自由基聚合性之官能基所變成，在此場合 耐熱性提高。再者，也可以是用自由基聚合性之官能基或 環氧基，羧基等所變成，在此場合耐熱性會提高。高分子 成分之配合量為2至80重量％，以5至70重量％為宜，以 | 10至60重量％最好。不滿2重量％時，應力缓和或黏著力 不足，超過80重量％時流動性下降。 本發明之異向性導電電路連接用黏著劑中，也可以添 加適當之充填劑、軟化劑、促進劑、老化防止劑、著色劑、 難燃劑、偶合劑。 含有充填劑之場合，因可以提高黏著可信度等，所以 較好，填充材之最大粒徑只要不超過導電粒子之粒徑就可 以使用，以5至60體積％範圍為宜，超過60體積％時，可 信度提高效果就達到飽和。做為偶合劑者，以含有乙烯基、 17 313294D1D1 1334880 丙烯基、胺基、環氧基、醯胺基及異氰酸基者，因可以提 高黏著性所以較佳。 又，將本發明之異向性導電電路連接用黏著劑做為硬 化時之Tg(玻璃轉移度），也可以為不同之2種類以上之層 所成之多層構造。 使用本發明之異向性導電電路連接用黏著劑之黏著基 板，只要有形成必要之電氣黏接電極者就可以，而無特別 限制，例如有在液晶顯示器中使用之ΙΤ0等形成電極之玻 璃或塑膠基板、PDP平板、EL平板等晝像顯示基板、印刷 配線板、陶瓷配線板、可撓配線板、半導體晶片、申阻晶 片、電容器晶片等晶片組件、磁帶包裝、C0F等之電路零 件半導體矽晶片等，必要時可以組合使用。 黏著時之條件並無特別限制，但黏接溫度為90至250 °C、黏著時間為1秒鐘至10分鐘之間，使用之用途可以依 黏著劑、基板之不同而作適當選擇，視需要也可以使用熱 以外之能源，例如光、超音波、電磁波等。 實施例 以下，以實施例來具體說明本發明，但本發明之範圍 並不限定於該等實施例。 (實施例1) 將50g之苯氧樹脂（Union carbide公司製，商品名 PKHC，平均分子量45, 000)溶解於MEK(曱乙酮，沸點79. 6 °C)，成為固形分50重量％之溶液。 自由基聚合性物質使用異氰酸環氧乙烷改質之二丙烯 18 313294D1D1 1334880 . »· 酸酯（東亞合成公司製，商品名M-215)及磷酸酯型丙烯酸 酯（共榮社油脂株式公司製、商品名P-2M)。 加熱或光產生游離基之硬化劑，使用2, 5-二曱基-2, 5--- 雙（2-乙基己醯基過氧化物）己烷之50重量％碳化氫溶液 - (日本油脂公司製，品名Perhexa 250)。 導電粒子係使用在以聚苯乙烯當作核心的粒子（壓縮 彈性率480 kg/mm2)表面上，設置厚度為0. 09//m之銀層 而成之平均粒子徑5 /z m之導電粒子。 ® 固形重量比係以苯氧基樹脂50g，異氰酸環氧乙烷改 質之二丙烯酸酯50g，磷酸酯型丙烯酸酯2 g，2, 5-二曱基 _2, 5-雙（2-乙基己酿基過氧化物）己烧5 g之模式配入，再 將導電粒子3體積％配入分散，再以塗抹裝置塗布於單面經 表面處理之厚度80/zm的PET(聚對苯二曱酸乙酯）薄膜， 經7(TC、10分鐘之熱風乾燥，可得黏著劑層厚度為35/zm 之異向性導電電路連接用黏著劑。 φ (實施例2) 導電粒子係使用在以聚苯乙烯當作核心的粒子（壓縮 彈性率366 kg/匪2)表面上，設置厚度0.1/zm之銀層而成 之平均粒子徑6. 15/zm之導電粒子，與實施例1相同處理 後可得異向性導電電路連接用黏著劑。 (實施例3) 導電粒子係使用在以聚苯乙烯當作核心的粒子（壓縮 彈性率480 kg/mm2)表面上，設置厚度0,4#»^之銀層^，在 此銀層之外側，設置厚度0. 04 // m之金層而成之平均粒子 19 313294D1D1 1334880 虹5 M m之導電粒子，經與實施例1相同處理後可得昱向 導電電路連接用黏著劑。 ” (實施例4) 導電粒子係使用在以聚苯乙烯當作核心的粒子（壓縮 彈性率480 kg/mm2)表面上，設置厚度〇1//m之鎳層，在 /此鎳層之外側，設置厚度〇.〇5 μ m之銀層而成之平均粒子 & m之導電粒子，經與實施例1相同處理後可得異向性 導電電路連接用黏著劑。 (比較例1) 導電粒子係使用在以聚苯乙烯當作核心的粒子（壓縮 彈性卞480 kg/mm )表面上，設置厚度0.2^0!之鎳層而成 之:均粒子徑5#m之導電粒子，經與實施例1相同處理後 可得異向性導電電路連接用黏著劑。 (比較例2) 導電粒子係使用在以聚笨乙烯當作核心的粒子（壓縮 彈性率480 kg/mm2)表面上，設置厚度〇 2//m之鎳層，在 此鎳層之外側，設置厚度〇. 〇4//m之金層而成之平均粒子 徑5/zm之導電粒子，經與實施例丨相同處理後可得異向性 導電連接用黏著劑。 (電路之連接） 使用上述異向性導電樹脂薄膜狀形成物，對具有5〇條 線I 30 /z m、間距3〇 # m、厚度18 # m之鋼電路的磁帶套組 (tcp)和ιΤ0玻璃（Diomerteck公司製，表面電阻至如 歐姆/每平方米（〇/□)，厚度1· ΙιηπΟ以14(TC，3MPa加 313294D1D1 20 熱加壓15秒鐘，可得連接寬2咖之連 預先在ΙΤΟ玻璃上，將異向性導體。此時， r貼付後，在，。屬加熱 後，將PET薄膜剝離即與TCp完成連接。 便連接，之 (連接電阻之測定） 將製成之異向性導電電路連接 及在 3〇°C、85%RH 之 π、·* & 2〇C 保存 進行上述之電路連Γι 分別保存叫、時後， 之辨& 路連接，3上述連接部之TCP的鄰接♦ 之連接電阻值，以容t 接电路間 接電跋R 夕功此測试益測定，連接電阻值是和Tertiary-butyl peroxide _3, 5, 5-tridecyl hexanoate, tertiary butyl peroxide lauric acid, 2, 5-dimethyl-2, 5-di (m- Benzoic acid peroxide) calcined, tertiary-butyl peroxide isopropane monocarbonate, tertiary-butyl peroxide-2-ethylhexyl monocarbonate, tertiary-hexyl peroxide benzene Acid ester, tertiary-butyl peroxide acetate, and the like. As the peroxy ketal, for example, 1,1-(tertiary-hexyl peroxide)-3,3,5-trimethylcyclohexene, 1,1-(tri-hexyl) Oxide °) cyclohexane, 1,1-(tertiary-butyl peroxide)-3,3,5-trimethylcyclohexene, 1,1-(tertiary-butyl peroxide) Cyclodecane, 2, 2-bis(tertiary-butyl peroxide) decane, and the like. As the dialkyl peroxides, for example, ο:, α, - bis (tertiary _ butyl peroxide) diisopropyl, diisophenyl propyl perm emulsion, 2 5 _ bis _ base-2 5-di(tertiary-butyl peroxide) hexane, tertiary _butyl isophenyl propyl peroxide, and the like. Examples of the hydroperoxides include diisopropyl hydroperoxide and isopropanol hydroperoxide. Examples of the cerium oxide-based peroxides include, for example, tertiary butyl trimethyl methacrylate peroxide, bis (tertiary-butyl) dimethyl decyl peroxide, and three. Grade-butyltrivinylformamidinyl peroxide, bis(tertiary-tert-butyl)-ethene-based ruthenium-based peroxide, tris(tertiary-butyl)diethoxylate Alkyl peroxide, tertiary butyl tripropylene methacrylate peroxidation 15 313294D1D1 1334880, bis(tertiary-butyl)dipropenyl decyl peroxide, tris(tris-butyl) Base) B-based bismuth-based fever-based peroxides. Further, in order to suppress corrosion of the connection terminal of the circuit member, the chloride ion or the organic acid contained in the radical generator (hardener) is preferably 5,000 ppm or less, and further, the organic acid produced by heat decomposition is The less is better. Further, in order to improve the stability of the circuit-connecting material, it is preferable to have a weight retention ratio of 20% by weight or more after standing at room temperature (25 ° C) for 24 hours under normal pressure, and these may be appropriately mixed. use. These radical generators may be used singly or in combination, or may be used in combination with a decomposition accelerator, an inhibitor, or the like. Further, it is preferable that the radical generating agent is coated with a polyurethane-based or polyester-based polymer material to form a microencapsulated product, since the usable time can be prolonged. In addition to the radically polymerizable compound, an epoxy resin which is a thermosetting resin may be blended. As epoxy resin, there are bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, novolak epoxy resin, nonylphenol novolak epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, glycidyl S-type epoxy resin, glycidylamine type epoxy resin, Benecosidine urea epoxy resin, An isocyanate type epoxy resin or an aliphatic chain epoxy resin may be used for hydrogenation or hydrogenation. These epoxy resins may be used in combination of two or more kinds. Further, as the hardener of the above epoxy resin, those which are generally used as an epoxy resin such as an amine, a phenol, an acid anhydride, an imidazole or a dicyandiamide may be used as an epoxy resin. Further, as the curing accelerator, a tertiary amine or an organophosphorus compound can be usually used as appropriate. Further, as a method of reacting the epoxy resin, in addition to the above-mentioned curing agent, a cation may be used by using a tetravalent sulfur (sulfonium) salt or a moth iron salt. In the circuit of the present invention, in the form of an adhesive or an anisotropic conductive resin film, in order to impart film formability, adhesion, and stress relaxation during hardening, polyethylene butyral resin and poly are generally used. a polymer component such as an ethylene methyl acetal resin, a polyester resin, a polyamide resin, a polyamidene resin, a xylene resin, a polyamine S resin, or a urea resin, and these polymer components have a molecular weight of 10, It is appropriate to reach 10 000 000. Further, these resins may be formed by radical polymerizable functional groups, and in this case, heat resistance is improved. Further, it may be formed by a radical polymerizable functional group, an epoxy group, a carboxyl group or the like, and in this case, heat resistance is improved. The blending amount of the polymer component is from 2 to 80% by weight, preferably from 5 to 70% by weight, most preferably from 10 to 60% by weight. When the content is less than 2% by weight, the stress relaxation or the adhesion is insufficient, and when it exceeds 80% by weight, the fluidity is lowered. In the adhesive for connecting an anisotropic conductive circuit of the present invention, a suitable filler, a softener, an accelerator, an aging preventive agent, a colorant, a flame retardant, and a coupling agent may be added. When the filler is contained, it is preferable because the reliability of adhesion can be improved, and the maximum particle diameter of the filler can be used as long as it does not exceed the particle diameter of the conductive particles, and is preferably in the range of 5 to 60% by volume, more than 60% by volume. When % is used, the credibility improvement effect is saturated. As the coupling agent, those having a vinyl group, 17 313294D1D1 1334880 propylene group, an amine group, an epoxy group, a decylamino group and an isocyanate group are preferred because they can improve adhesion. Further, the Tg (glass transition degree) at the time of hardening the adhesive for connecting an anisotropic conductive circuit of the present invention may be a multilayer structure of two or more different layers. The adhesive substrate to which the anisotropic conductive circuit of the present invention is bonded is used as long as it forms a necessary electrode for electrical bonding, and is not particularly limited. For example, there is a glass for forming an electrode such as ΙΤ0 used in a liquid crystal display or A semiconductor substrate such as a plastic substrate, a PDP panel, or an EL panel, such as a display substrate, a printed wiring board, a ceramic wiring board, a flexible wiring board, a semiconductor wafer, a resist wafer, a capacitor chip, and the like, a magnetic tape package, a circuit component such as a COF, and the like. Wafers, etc., can be used in combination if necessary. The conditions for adhesion are not particularly limited, but the bonding temperature is 90 to 250 ° C, and the adhesion time is between 1 second and 10 minutes. The use can be appropriately selected depending on the adhesive and the substrate, as needed. It is also possible to use energy sources other than heat, such as light, ultrasonic waves, electromagnetic waves, and the like. EXAMPLES Hereinafter, the present invention will be specifically described by examples, but the scope of the present invention is not limited to the examples. (Example 1) 50 g of a phenoxy resin (manufactured by Union Carbide, trade name: PKHC, average molecular weight: 45,000) was dissolved in MEK (anthraquinone, boiling point: 79. 6 ° C) to obtain a solid content of 50% by weight. Solution. The radically polymerizable material is a dipropylene propylene modified with isocyanate oxirane 18 313294D1D1 1334880 . »· acid ester (manufactured by Toagosei Co., Ltd., trade name M-215) and phosphate ester acrylate (Kyoeisha oil company) Company system, trade name P-2M). Heating or photo-generated free radical hardener, using 2, 5-dimercapto-2, 5--bis(2-ethylhexyl peroxide) hexane 50% by weight hydrocarbon solution - (Japan Made by the grease company, the name Perhexa 250). Conductive particles are used on the surface of particles with a polystyrene as the core (compression elastic modulus: 480 kg/mm2), and a conductive particle having an average particle diameter of 5 /zm formed by a silver layer having a thickness of 0.99/m. . ® solid weight ratio is 50g of phenoxy resin, 50g of diacrylate modified by isocyanate oxirane, 2g of phosphate ester type acrylate, 2, 5-dimercapto-2, 5-double (2 -ethylhexyl peroxide peroxide) is blended in a 5 g mode, and then 3% by volume of the conductive particles are dispersed, and then coated on a single-sided surface-treated PET having a thickness of 80/zm by an application device. A film of ethyl phthalate) was dried by hot air at 7 (TC, 10 minutes) to obtain an adhesive for connecting an anisotropic conductive circuit with a thickness of the adhesive layer of 35/zm. φ (Example 2) Conductive particles Conductive particles having an average particle diameter of 6.15/zm and having a thickness of 0.1/zm on a surface of a particle having a thickness of 0.1/zm on a surface of a particle having a polystyrene as a core (compression elastic modulus: 366 kg/匪2) The adhesive for the anisotropic conductive circuit connection was obtained in the same manner as in Example 1. (Example 3) Conductive particles were used on the surface of particles (compression elastic modulus: 480 kg/mm2) having polystyrene as a core, and thickness was set. 0,4#»^ The silver layer ^, on the outer side of the silver layer, the average particle of the thickness of 0. 04 // m is set. 19 313294D1D1 1334880 The conductive particles of the rainbow 5 M m were subjected to the same treatment as in Example 1 to obtain an adhesive for connecting the conductive circuits." (Example 4) Conductive particles were used for particles having polystyrene as a core (compression elasticity) On the surface of the 480 kg/mm2), a nickel layer having a thickness of 〇1//m is provided, and on the outer side of the nickel layer, an average particle & m conductive particle is formed by a silver layer having a thickness of 〇.〇5 μm. An adhesive for connecting an anisotropic conductive circuit was obtained by the same treatment as in Example 1. (Comparative Example 1) Conductive particles were used on a surface of a particle having a polystyrene as a core (compression elastic 卞 480 kg/mm). On the other hand, a conductive layer having a thickness of 0.2^0! was used, and the conductive particles having a uniform particle diameter of 5#m were obtained by the same treatment as in Example 1 to obtain an adhesive for connecting an anisotropic conductive circuit. (Comparative Example 2) The conductive particles are used on the surface of particles (compressive elastic modulus: 480 kg/mm2) having polystyrene as a core, and a nickel layer having a thickness of 〇2//m is disposed, and a thickness 〇 is set on the outer side of the nickel layer. 〇4 The conductive particles having an average particle diameter of 5/zm formed by the gold layer of //m can be treated in the same manner as in the embodiment. Adhesive for anisotropic conductive connection. (Connection of circuit) Using the above-mentioned anisotropic conductive resin film-like formation, a steel circuit having 5 turns of line I 30 /zm, pitch 3〇# m, thickness 18 #m Tape set (tcp) and ιΤ0 glass (manufactured by Diomerteck, surface resistance to ohms per square meter (〇/□), thickness 1· ΙιηπΟ with 14 (TC, 3MPa plus 313294D1D1 20 heat press for 15 seconds, It is possible to connect the wide 2 coffee to the front of the glass, and the anisotropic conductor. At this time, after r is posted, it is. After heating, the PET film is peeled off and connected to the TCp. Connected, (measurement of connection resistance) The prepared anisotropic conductive circuit is connected and stored at 3 °C, 85% RH, π, ·* & 2〇C, and the above-mentioned circuit connection is saved separately. After the time, the identification and the connection of the road, the connection resistance value of the TCP adjacent to the connection portion of the above-mentioned connection portion is measured by the indirect power supply of the circuit, and the connection resistance value is
曰之电阻之150點平均值，測定結果如表1所示一 〜 表， τ ° 8於具％例1所得之連接構造體，於_2{rc保存及在3〇。〇、 下^RH之恒溫恒濕槽中保存者，任一者都顯示在2· 以 也同二好連接可信度。又，實施例2、3之連接構造禮中， 中保=顯示於_2(^保存及在3(rc、肋％ rh之恒温慎濕糟 呆存者，任一者都得到12. 5Ω以下之良好連接矸信度。 2】 3]3294DiD1 1334880 相對於此，比較例1及2，在-20°C保存之連接構造體 中，雖可得良好連接可信度，但在30°C、85% RH之恒溫恒 濕槽中保存者，連接電阻大幅上昇到10Ω以上。 (連接強度之測定） 在實施例1至3中，於-20°C或在30°C、85% RH之恒 溫恒濕槽中保存者，任一者個都可得1000 N/m左右之良 好連接強度。另一方面，比較例1及2中，連接強度於-20 °C或在30°C、85% RH之恒溫恒濕槽中保存者，任一者都得 到1000 N/m左右之良好連接強度。 (絕緣性之評估） 使用所得之異向性導電電路連接用黏著劑，將具有相 互交叉配置250條線寬50/zm、間距100//m、厚度18//m 之銅電路的櫛形電路印刷電路基板，和具有500條線寬50 //m、間距100//m、厚度18//m之銅電路的磁帶套組（TCP)， 以140°C，3MPa加熱加壓15秒鐘，連接幅寬2mm。此連接 體之櫛形電路外加100V之電壓，在85°C、85% RH之高溫 高濕下試驗500小時後測定絕緣電阻值。 任一者都可得到109Ω以上之良好絕緣性，觀察不出有 絕緣性下降現象。 (流動性之評估） 使用厚度35 # m、5mm x5mm之異向性導電電路連接用 黏著劑，將其夾持於厚度〇· 7# m、15mm xl5匪之玻璃中， 在140°C，3MPa下進行加熱加壓15秒鐘，使用初期之面積 (A )和加熱加壓後面積（B)，求得流動性（B ) / ( A )值時，實 22 313294D1D1 1334880 施例1至3是1. 9至2. 0之範圍内，另一方面，比較例1 及2則為1. 8及1. 9。 (硬化後之彈性率） • 測定實施例1之異向性導電電路連接用點著劑在硬化 後40°C之彈性率，為1. 5GPa。 由上述之連接強度、絕緣性、流動性、硬化後之彈性 率等觀之，本發明之實施例之值和比較例之值，雖顯示幾 乎相同之值，但如表1所示般，連接電阻值有很大之差異。 _由實施例和比較例之連接強度、絕緣性、流動性等顯示有 相同之特性觀之，導電粒子表面之覆蓋層被認為極薄，但 對連接電阻有明顯之影響。如本發明，在表面並不露出銀、 金鉑以外之過渡金屬的導電粒子中，於導電粒子表面並無 促進自由基聚合性物質之聚合現象，顯示連接電阻極低之 良好數值。如實施例4使用鎳等過渡金屬時，只要在其外 側覆蓋500A以上之銀、金、鉑等使内侧之過渡金屬不露 φ出，則雖經溫度或溫濕度處理均具有優異之保存安定性， 連接電阻不會增加。 (表面處理粒子A之製作） 三乙胺之1重量％曱醇溶液中，放入在以聚苯乙烯為核 心之粒子表面上，設置0. 2 /z m厚度之錄層，在此錄層外 側，設置0. 04 // m厚度之金層而成之平均粒徑4 μ m之導電 粒子，於25t攪拌10分鐘，過濾出導電粒子，在50°C下 乾燥15分鐘，得到表面處理粒子A。 (表面處理粒子B之製作） 23 313294D1D1 1334880 月女基丙基三石夕院之 置醇溶液中，放入 乙晞為核心之粒子表面上’設置0.2"m厚度之鎳居，：： 側’設置0.04，厚度之金層而成之a 。，導電粒子’於5『C授拌5分鐘，過渡出導電粒子，在： C下乾& 5分鐘，得到表面處理粒子b。 (表面處理粒子C之製作） 六r-環氧丙氧基丙基曱基二甲氧基傾之 洛液中’放人在以聚苯乙稀為核心之粒子表面上，設置 μ厚度之鎳層’在此鎳層外側，設置〇 ()4_厚产之金 =成之平均粒徑4„之導·子，於饥鮮^鐘.， 導電粒子…rc下乾燥15分鐘，得到表面處理 (表面處理粒子之製作） #雙齡A型環氧樹脂之3重量％甲醇溶液中，放入在以聚 本乙烯為核心之粒子表面上，設置G. 2以m厚度之鎳層，在 此鎳層外側’設置〇.〇4/ζιη厚度之金層而成之平均粒徑$ β 電粒子，於50c攪拌5分鐘，過濾出導電粒子， 在80 C下乾燥5分鐘，得到表面處理粒子D。 使用此等導電粒子A、B、c及D，分別配入下面所示 之配合’以簡易之塗工機（TESTER產業公司製），在表面處 理過之PET(聚對苯二甲酸乙醋）薄膜單面上塗佈別㈣厚 度，在70°C、經10分鐘之熱風乾燥，製成電路連接用黏 著劑。 (實施例5) 313294D1D1 24 1334880 將苯氧基樹脂（PKHC，Union carbide公司製商品名、 平均分子量45, 000)50g，做為自由基聚合性化合物之甲基 丙烯酸二環己酯48g，磷酸酯丙烯酸酯2g，2，5-二甲基-2, 5-雙（2-乙基己醯過氧化物）己烷3g，溶解在做為溶劑之曱 乙酮中，再將3體積％之表面處理粒子A配入分散，在表面 處理過之聚對苯二曱酸乙酯薄膜單面上，以簡易塗工機塗 • 佈50/im厚度，在70°C、經10分鐘之熱風乾燥，製得厚 度為30//m之異向性導電電路連接用黏著劑。 •(實施例6) 將苯氧基樹脂（PKHC，Union carbide公司製商品名、 平均分子量45,000)50g，異氰酸環氧己酯改質二丙烯酸酯 46g，磷酸酯丙烯酸酯4g，2, 5-二甲基-2, 5-雙（2-乙基己 ϋ過氧化物）己烧3g，溶解配入做為溶劑之甲乙酮中，再 將3體積％之表面處理粒子B配入分散，在表面處理過之聚 對苯二曱酸乙酯薄膜單面上以簡易塗工機塗佈50 # m厚 φ度，在70°C、經10分鐘之熱風乾燥，製得厚度為30/im 之異向性導電電路連接用黏著劑。 (實施例7) 將苯氧基樹脂（PKHC，Union carbide公司製商品名、 平均分子量45, 000)25g，聚胺酯樹脂25g，甲基丙烯酸二 環己酯48g，磷酸酯丙烯酸酯2g，2,5-二甲基-2,5-雙（2-乙基己ii過氧化物）己烧3g，溶解配入做為溶劑之甲乙酮 中，再將3體積％之表面處理粒子B配入分散，在表面處理 過之聚對苯二甲酸乙酯薄膜單面上以簡易塗工機塗佈50# 25 313294D1D1 1334880 m厚度，在70°C、經10分鐘之熱風乾燥，製得厚度為30 A m之異向性導電電路連接用黏著劑。 (實施例8) 將苯氧基樹脂（PKHC，Union carbide公司製商品名、 平均分子量45, 000)50g，做為自由基聚合性物之甲基丙烯 酸二環己酯48g，磷酸酯丙烯酸酯2g，2, 5-二曱基-2, 5-雙（2-乙基已醯過氧化物）已烷3g，溶解配入做為溶劑之甲 乙酮中，再將3體積％之表面處理粒子C配入分散，在表面 處理過之聚對苯二甲酸乙酯薄膜單面上以簡易塗工機塗佈 50/zm厚度，在70°C、經10分鐘之熱風乾燥，製得厚度為 30/zm之異向性導電電路連接用黏著劑。 (實施例9) 將苯氧基樹脂（PKHC，Union carbide公司製商品名、 平均分子量45, 000)50g，異氰酸環氧己酯改質二丙烯酸酯 46忌，填酸酉旨丙稀酸酷48，2,5-二甲基-2,5-雙（2-乙基已 醯過氧化物）已烷3g，溶解配入做為溶劑之曱乙酮中，再 將3體積％之表面處理粒子D配入分散，在表面處理過之聚 對苯二甲酸乙酯薄膜單面上以簡易塗工機塗佈50 // m厚 度，在70°C、經10分鐘之熱風乾燥，製得厚度為30//m 之異向性導電電路連接用黏著劑。 (實施例10) 將苯氧基樹脂（PKHC，Union carbide公司製商品名、 平均分子量45, 000)25g，聚胺酯樹脂25g，曱基丙烯酸二 環己酯48g，磷酸酯丙烯酸酯2g，2, 5-二曱基-2, 5-雙（2- 26 313294D1D1 1334880 1 乙基己醯過氧化物）己烷3g，溶解配入做為溶劑之曱乙酮 中，再將3體積％之表面處理粒子D配入分散，在表面處理 過之聚對苯二甲酸乙酯薄膜單面上以簡易塗工機塗佈50# m厚度，在7G°C、經10分鐘之熱風乾燥，製得厚度為30 # m之異向性導電電路連接用黏著劑。 (比較例3) • 除了將實施例5之表面處理粒子A改為未處理粒子以 外，其餘與實施例5同樣處理，製得異向性導電電路連接 _用黏著劑。 (電路連接構造體之製作） 將上述異向性導電電路連接用黏著劑，縱割成1. 5匪 幅寬，在已形成ITO電極之玻璃基板上，於80°C、5秒、 IMPa之條件下暫時連接，剝離PET支持基材，將此對齊電 極寬50/zm、間距50/zm之TCP電極位置，在150°C、20 秒、4MPa之條件下，製成本連接電路連接構造體。 0 (特性評估方法） 連接電阻：使用ADVANTEST公司製多功能測試儀 TR6848，以1mA之定電流測定電路間之電阻。連接電阻是 測定連接後之初期與30°C、60% RH、放置100小時後之值。 其結果在表2中表示。 27 313294D1D1 1334880 向性導電電路連接用黏著劑之連接溫度170°C，可以在更 低溫之150°C連接，黏著劑保存後的連接電阻差異小之良 好連接構造體。 【圖式簡單說明】 無。 【主要元件符號說明】 無0The average value of the resistance of 曰 is 150 points, and the measurement results are shown in Table 1. Table τ ° 8 is the connection structure obtained in % Example 1, and is stored at _2 {rc and at 3 〇.保存, the lower ^RH in the constant temperature and humidity tank saver, either show in 2 · with the same good connection reliability. In addition, in the connection structure of the second and third embodiments, the mediation = is displayed in _2 (^ is saved and is in the case of 3 (rc, rib % rh constant temperature, wet and wet), either of them is 12. 5 Ω or less. Good connection reliability. 2] 3] 3294DiD1 1334880 In contrast, in Comparative Examples 1 and 2, in the connection structure stored at -20 ° C, good connection reliability was obtained, but at 30 ° C, In the constant temperature and humidity chamber of 85% RH, the connection resistance is greatly increased to 10 Ω or more. (Measurement of joint strength) In Examples 1 to 3, at -20 ° C or at 30 ° C, 85% RH Any one of the holders in the constant humidity tank can obtain a good joint strength of about 1000 N/m. On the other hand, in Comparative Examples 1 and 2, the joint strength is -20 ° C or 30 ° C, 85%. The holder of the RH constant temperature and humidity chamber has a good connection strength of about 1000 N/m. (Evaluation of insulation) The adhesive for the connection of the anisotropic conductive circuit obtained will have a cross-over arrangement of 250. A 电路-shaped circuit printed circuit board having a copper line of 50/zm, a pitch of 100//m, and a thickness of 18//m, and having 500 line widths of 50 // m, a pitch of 100//m, and a thickness 18//m copper circuit tape set (TCP), heated and pressurized at 140 ° C, 3 MPa for 15 seconds, connecting width 2mm. This connector's 电路-shaped circuit plus 100V voltage, at 85 ° C, 85 The insulation resistance value was measured after 500 hours of high temperature and high humidity test of RH. Any of them can obtain good insulation of 109 Ω or more, and no insulation degradation can be observed. (Evaluation of fluidity) Thickness 35 # m, 5mm x 5mm anisotropic conductive circuit connection adhesive, which is clamped in glass of thickness 〇·7# m, 15mm xl5匪, heated and pressurized at 140°C, 3MPa for 15 seconds, in the initial stage of use The area (A) and the area after the heat and pressure (B), when the fluidity (B) / (A) is obtained, the actual 22 313294D1D1 1334880, the examples 1 to 3 are in the range of 1. 9 to 2.0, On the one hand, Comparative Examples 1 and 2 are 1.8 and 1.9 (elasticity after hardening). • The modulus of elasticity of the anisotropic conductive circuit connecting agent of Example 1 at 40 ° C after hardening was measured. The value of the embodiment of the present invention is compared with the above-mentioned connection strength, insulation property, fluidity, elastic modulus after hardening, and the like. The values of the examples show almost the same value, but as shown in Table 1, the connection resistance values are greatly different. _ The connection strength, insulation, fluidity, etc. of the examples and comparative examples show the same characteristics. In view of the fact, the coating layer on the surface of the conductive particles is considered to be extremely thin, but has a significant influence on the connection resistance. As in the present invention, in the conductive particles of the transition metal which are not exposed to silver or gold or platinum, the surface of the conductive particles is There is no polymerization which promotes the polymerization of a radically polymerizable substance, and shows a good value in which the connection resistance is extremely low. When a transition metal such as nickel is used in Example 4, if the outer side of the transition metal is not covered with silver, gold, platinum, or the like by 500 A or more, the storage stability is excellent after temperature or temperature and humidity treatment. , the connection resistance does not increase. (Preparation of surface-treated particles A) In a 1% by weight decyl alcohol solution of triethylamine, placed on the surface of the particles having a polystyrene as a core, and a recording layer having a thickness of 0.2 / zm is disposed outside the recording layer. , a conductive particle having an average particle diameter of 4 μm formed by a gold layer of 0. 04 // m thickness, stirred at 25t for 10 minutes, and the conductive particles were filtered out and dried at 50 ° C for 15 minutes to obtain surface-treated particles A. . (Preparation of surface-treated particle B) 23 313294D1D1 1334880 In the alcohol solution of the female propyl propyl sulphate, place the nickel on the surface of the particles with the acetaminophen as the core, and set the nickel of the 0.2"m thickness, :: side' Set 0.04, the thickness of the gold layer is made of a. The conductive particles were mixed at 5 C for 5 minutes, and the conductive particles were transferred out, and dried at > C for 5 minutes to obtain surface-treated particles b. (Preparation of surface-treated particle C) hexa-r-glycidoxypropyl-decyldimethoxy-dehydration solution is placed on the surface of particles with polystyrene as the core, and a thickness of nickel is set. The layer 'on the outside of the nickel layer, set 〇() 4_ thickened gold = into the average particle size of 4 „ guides, in the hunger fresh clock., conductive particles ... rc drying for 15 minutes, surface treatment (Preparation of surface-treated particles) #3% by weight of a 3 wt% methanol solution of A-type epoxy resin, placed on the surface of particles having a core of polyethylene as a core, and a layer of nickel having a thickness of m. On the outer side of the nickel layer, the average particle size of the gold layer of 〇.〇4/ζιη thickness is set to $β. The particles are stirred at 50c for 5 minutes, and the conductive particles are filtered out and dried at 80 C for 5 minutes to obtain surface-treated particles D. Using these conductive particles A, B, c, and D, the surface-treated PET (polyethylene terephthalate) was prepared by the following combination of the simple coating machine (manufactured by TESTER Industries, Inc.). The film is coated on one side with a thickness of (4), and dried at 70 ° C for 10 minutes by hot air to form an adhesive for circuit connection. (Example 5) 313294D1D1 24 1334880 50 g of phenoxy resin (PKHC, trade name, manufactured by Union Carbide Co., Ltd., average molecular weight: 45,000), 48 g of dicyclohexyl methacrylate as a radical polymerizable compound, phosphate ester Acrylate 2g, 2,5-dimethyl-2, 5-bis(2-ethylhexyl peroxide) hexane 3g, dissolved in ethyl ketone as a solvent, and then 3 vol% surface The treated particles A are dispersed and dispersed on a single surface of the surface-treated polyethylene terephthalate film by a simple coating machine, cloth 50/im thickness, and dried at 70 ° C for 10 minutes. An adhesive for connecting an anisotropic conductive circuit having a thickness of 30/m was obtained. (Example 6) 50 g of a phenoxy resin (PKHC, trade name, manufactured by Union Carbide Corporation, average molecular weight: 45,000), isocyanate ring Oxygen hexyl ester modified diacrylate 46g, phosphate ester acrylate 4g, 2, 5-dimethyl-2, 5-bis(2-ethylhexyl peroxide) hexane 3g, dissolved and formulated as a solvent In the methyl ethyl ketone, 3% by volume of the surface-treated particles B are dispersed and dispersed, and the surface-treated polyethylene terephthalate film is single-sided. Applying 50 #m thick φ degree to a simple coating machine, drying at 70 ° C for 10 minutes, to obtain an adhesive for connecting anisotropic conductive circuits with a thickness of 30 / im. (Example 7) Phenoxy resin (PKHC, trade name, average molecular weight 45,000 by Union Carbide) 25g, polyurethane resin 25g, dicyclohexyl methacrylate 48g, phosphate acrylate 2g, 2,5-dimethyl-2 5-bis(2-ethylhexii peroxide) was calcined in 3 g, dissolved and dissolved in methyl ethyl ketone as a solvent, and 3 vol% of surface-treated particles B were dispersed and dispersed, and the surface-treated poly-pair was prepared. The phthalate film was coated on a single surface by a simple coating machine with a thickness of 50# 25 313294D1D1 1334880 m, and dried at 70 ° C for 10 minutes to obtain an anisotropic conductive circuit connection with a thickness of 30 A m. Use an adhesive. (Example 8) 50 g of a phenoxy resin (PKHC, trade name, manufactured by Union Carbide Corporation, average molecular weight: 45,000), 48 g of dicyclohexyl methacrylate as a radical polymerizable product, and 2 g of phosphoric acid ester acrylate , 2, 5-dimercapto-2, 5-bis(2-ethylhexyl peroxide) hexane 3g, dissolved and mixed into methyl ethyl ketone as a solvent, and then 3% by volume of surface-treated particles C Into the dispersion, on the surface of the surface treated polyethylene terephthalate film coated with a simple coater 50 / zm thickness, dried at 70 ° C, 10 minutes hot air, to a thickness of 30 / zm The anisotropic conductive circuit is connected with an adhesive. (Example 9) 50 g of a phenoxy resin (PKHC, trade name, manufactured by Union Carbide Co., Ltd., average molecular weight: 45,000), epoxy hexyl cyanate modified diacrylate 46, and acid anhydride Cool 48,2,5-dimethyl-2,5-bis(2-ethylhexanium peroxide) hexane 3g, dissolved in acetophenone as a solvent, and then 3 vol% surface The treated particles D are mixed and dispersed, and the surface of the surface-treated polyethylene terephthalate film is coated with a thickness of 50 // m on a simple coating machine, and dried at 70 ° C for 10 minutes. An adhesive for connecting an anisotropic conductive circuit having a thickness of 30/m. (Example 10) 25 g of a phenoxy resin (PKHC, trade name of Union Carbo, and an average molecular weight of 45,000), 25 g of a polyurethane resin, 48 g of dicyclohexyl acrylate, 2 g of phosphoric acid acrylate, 2, 5 - Dimercapto-2, 5-bis(2- 26 313294D1D1 1334880 1 ethylhexyl peroxide) 3 g of hexane, dissolved and dissolved in ethyl ketone as a solvent, and then 3% by volume of surface-treated particles D is dispersed, and the surface of the surface treated polyethylene terephthalate film is coated with a thickness of 50# m by a simple coating machine, and dried at 7G ° C for 10 minutes, to a thickness of 30 # m The anisotropic conductive circuit is connected with an adhesive. (Comparative Example 3) The anisotropic conductive circuit was bonded to the same as in Example 5 except that the surface-treated particles A of Example 5 were changed to untreated particles. (Production of circuit connection structure) The above-mentioned anisotropic conductive circuit-bonding adhesive was slit into a width of 1.5 匪 on a glass substrate on which an ITO electrode was formed, at 80 ° C, 5 seconds, and IMPa Under the conditions, the PET support substrate was peeled off, and the TCP electrode position of 50/zm in width and 50/zm in pitch was aligned, and the connection structure of the connection circuit was fabricated under the conditions of 150 ° C, 20 seconds, and 4 MPa. 0 (characteristic evaluation method) Connection resistance: Using a multi-function tester TR6848 manufactured by ADVANTEST, the resistance between the circuits was measured at a constant current of 1 mA. The connection resistance was measured at the initial stage after the connection, at 30 ° C, 60% RH, and after standing for 100 hours. The results are shown in Table 2. 27 313294D1D1 1334880 The connection temperature of the adhesive for the conductive conductive circuit is 170 °C, which can be connected at 150 °C at a lower temperature. The connection resistance after the adhesion of the adhesive is small is good. [Simple description of the diagram] None. [Main component symbol description] No 0
29 313294D1D129 313294D1D1