200932860 九、發明說明 【發明所屬之技術領域】 本發明係關於黏著劑組成物及使用其之電路連接材料 、以及電路構件的連接方法及藉此所得到的電路連接體。 【先前技術】 作爲於液晶顯示器用的玻璃面板實裝液晶驅動用1C φ 之方法，CHIP-ON-GLASS實裝（以下，稱爲「COG實裝 」）廣泛地被使用，COG實裝係將液晶驅動用1C直接接 合於玻璃面板上之方法。 上述COG實裝中，一般而言，作爲電路連接材料， 係使用具有異方導電性之黏著劑組成物。此黏著劑組成物 ，係含有黏著劑成分、與必要時所摻合的導電粒子，將由 該相關的黏著劑組成物所成的電路連接材料配置於形成玻 璃面板上的電極的部分，藉由於其上壓著1C、LSI等的半 ❹ 導體元件或封裝（package )等，在相對的電極彼此保持 . 在導通狀態，保持鄰接的電極彼此的絕緣下進行電的連接 _ 與機械的固著。 惟，作爲黏著劑組成物的黏著劑成分，自以前來利用 環氧樹脂及咪唑系硬化劑的組合，摻合此等的成分之黏著 劑組成物，通常藉由溫度2 0 (TC維持5秒左右，使環氧樹 脂硬化，進行1C晶片的COG實裝。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composition, a circuit connecting material using the same, a method of connecting circuit members, and a circuit connector obtained thereby. [Prior Art] CHIP-ON-GLASS mounting (hereinafter referred to as "COG mounting") is widely used as a method of mounting 1C φ for liquid crystal driving on a glass panel for liquid crystal displays. The COG mounting system will be widely used. The method of directly bonding the 1C to the glass panel for liquid crystal driving. In the above COG mounting, generally, as the circuit connecting material, an adhesive composition having an anisotropic conductivity is used. The adhesive composition is characterized in that it contains an adhesive component and, if necessary, conductive particles, and a circuit connecting material formed of the related adhesive composition is disposed on a portion of an electrode forming a glass panel, A semi-turned conductor element such as 1C or LSI, a package, or the like is pressed to hold the opposing electrodes. In the on state, the adjacent electrodes are electrically insulated and electrically connected to each other. However, as an adhesive component of the adhesive composition, an adhesive composition in which these components are blended by a combination of an epoxy resin and an imidazole-based hardener has been conventionally maintained at a temperature of 2 0 (TC for 5 seconds). On the left and right sides, the epoxy resin was hardened, and the COC mounting of the 1C wafer was performed.
惟，近年隨著液晶面板的大型化及薄厚度化的發展， 使用先前技術的黏著劑組成物在上述溫度條件進行COG 200932860 實裝，則因爲加熱時的溫度差所產生的熱膨張及收縮差而 內部應力產生，而會有1C晶片或玻璃面板發生翹曲的問 題。 作爲降低電路構件產生翹曲之手段，專利文獻1中， , 記載著作爲環氧樹脂的硬化劑之含有由毓鹽所成的潛在性 硬化劑之電路連接用黏著薄膜；記載著藉由使用此黏著薄 膜，可將實裝時的加熱溫度低溫化至16(TC以下，可降低 D 於電路構件的電路連接體所產生的內部應力之要旨（參考 專利文獻1的段落[0019])。 [專利文獻1]特開2004-22 1 3 1 2號公報 【發明內容】 [發明所欲解決之課題] 惟，專利文獻1中所記載的黏著薄膜，雖然在加熱溫 度的低溫化方面發揮優異的效果，但因爲使用特殊的潛在 G 性硬化劑，故會有適用期比較短的課題。因此，現狀係此 . 黏著薄膜，與摻合先前技術的咪唑系硬化劑者比較下，其 用途受到限制。 本發明係有鑑於此實際情況而完成，其目的在於提供 即使於200°C左右的高溫條件進行電路構件彼此的連接時 ，可充分地抑制電路構件的翹曲之黏著劑組成物及使用其 之電路連接材料。 此外，本發明目的在於提供以低連接電阻連接電路構 件的電路連接體、以及爲了得到其之電路構件的連接方法 -5- 200932860 [用以解決課題之手段] 本發明的黏著劑組成物，其係用於在黏著電路構件彼 _ 此的同時以電連接各電路構件所具有的電路電極彼此之黏 著劑組成物，其特徵係含有環氧樹脂、與環氧樹脂硬化劑 、與具有交聯結構且重量平均分子量爲30000〜80000之 φ 丙烯酸系共聚物。其中，丙烯酸系共聚物的重量平均分子 量，係藉由凝膠滲透色譜法所測量，基於使用標準聚苯乙 烯所製成的檢量線所換算得到之値。 於本發明的黏著劑組成物，上述丙烯酸系共聚物儘到 應力緩和劑的作用，因此，使用微膠囊型或加成化合物型 潛在性硬化劑等之咪唑系硬化劑作爲環氧樹脂的硬化劑， 即使在200°C左右進行硬化處理時，可有效果地緩和內部 應力，可充分地抑制電路構件的翹曲。 〇 本發明的黏著劑組成物，再含有導電粒子較佳，基於 . 黏著劑成分中分散有導電粒子的黏著劑組成物，可製造具 有優異的連接信賴性之電路連接體。 上述丙烯酸系共聚物的玻璃轉化溫度爲-4 0〜4 01較佳 ’丙烯酸系共聚物的玻璃轉化溫度在上述範圍內，則可得 到具有適度的黏著性之黏著劑組成物。此外，黏著劑組成 物的硬化物的玻璃轉化溫度，由連接部的連接信賴性之觀 點而言，爲1 00〜1 50°C較佳。 此外，上述丙烯酸系共聚物，係藉由使原料所含有的 -6- 200932860 單體成分進行共聚合而得到者，相對於該原料所含有的單 體成分質量份之丙嫌酸縮水甘油醋及甲基丙烯酸縮水 甘油酯的合計量爲1~7質量份較佳。藉由將於上述範圍由 含有丙烯酸縮水甘油酯及/或甲基丙烯酸縮水甘油酯之原 , 料所製造的丙烯酸系共聚物摻合於黏著劑組成物，可達成 優異的應力緩和性，可更充分地抑制電路構件的翹曲。 本發明中該相關的黏著劑組成物，以溫度2 0 0 °C加熱 φ 1小時所得到的硬化物，其於-5 0 °c的貯藏彈性率爲2.0〜 3.0GPa且於100°C的貯藏彈性率爲1.0〜2.0GPa，同時於-50 〜100°C的範圍的貯藏彈性率的最大値與最小値的差距爲 2 · 0 GPa以下較佳。依據符合該相關的條件之黏著劑組成物 的硬化物，可在廣泛的溫度範圍中抑制貯藏彈性率的低下 ，將此黏著劑組成物使用於電路構件彼此的連接則可製造 具有連接信賴性的電路連接體。 本發明的電路連接材料，其係具備薄膜狀的基材、與 © 黏著劑層； - 該黏著劑層係由本發明該相關的黏著劑組成物所成， . 被設置於該基材一側的面上。依據該相關之構成的電路連 接材料，可於電路構件上輕易地配置黏著劑層，可提高作 業效率。再者，使用電路連接材料時，薄膜狀的基材可適 當地被剝離。 本發明的電路連接體，其特徵係具備被對向配置的一 對的電路構件、與連接部；該連接部係由本發明該相關的 黏著劑組成物的硬化物所成，介於該一對的電路構件之間 200932860 ，黏著該電路構件彼此使各電路構件所具有的電路電極彼 此以電連接。 本發明的電路連接體中，該一對的電路構件的至少一 方可爲1C晶片。此外，於該電路連接體中，該一對的電 _ 路構件各自所具有的電路電極的至少一側的表面，可由金 、銀、錫、釕、铑、鈀、餓、銥、鉑及銦錫氧化物所選出 的至少1種所構成 〇 此外，本發明的電路連接體中，抵接於該連接部之該 一對的電路構件的該抵接面的至少一側，可具有由氮化矽 、聚矽氧烷化合物及感光性或非感光性聚醯亞胺樹脂所選 出的至少1種以上的素材所構成的部分。 本發明的電路構件的連接方法，其係藉由在被對向配 置的一對的電路構件之間，使本發明該相關的黏著劑組成 物介於其間，加熱及加壓整體，形成由該黏著劑組成物的 硬化物所成，黏著該電路構件彼此使介於該一對的電路構 Ο 件之間的各電路構件所具有的電路電極彼此以電連接之連 接部，得到具備該一對的電路構件及該連接部之電路連接 體。 [發明的效果] 依據本發明，即使於200°C左右的高溫條件下進行電 路構件彼此的連接時，可充分地抑制電路構件的翹曲。 [實施發明之最佳形態] -8 - 200932860 以下，一邊參照附件圖面一邊詳細地說明本發明的較 適的實施形態。再者，圖面的說明中同一要素附上同一符 號，省略重複說明，此外，圖面於方便上，圖面的尺寸比 率不一定與說明者一致。 . 本明細書中「（甲基）丙烯酸酯」之意係指「丙烯酸 酯」及對應其之「甲基丙烯酸酯」；「（甲基）丙烯酸」 之意係指「丙烯酸」及對應其之「甲基丙烯酸」。 〇 <電路連接材料> 首先，說明關於該本實施形態該相關的電路連接材料 。圖1係表示本實施形態相關的電路連接材料5之截面圖 ，電路連接材料5係具備薄膜狀的基材6、與被設置於基 材6的一側面上之黏著劑層8。黏著劑層8係由含有含（a )環氧樹脂、（b)環氧樹脂硬化劑、及（c)丙烯酸系共 聚物之黏著劑成分9，與分散於黏著劑成分9中的導電粒 Q 子i〇A之黏著劑組成物所成。 _ 電路連接材料5係藉由於薄膜狀的基材6上使用塗佈 裝置塗佈黏著劑組成物的溶液，所定時間熱風乾燥後形成 黏著劑層8而製作。藉由形成由黏著劑組成物所成的黏著 劑層8，例如與以膏狀直接使用黏著劑組成物狀況比較， 使用於1C晶片等的COG實裝或COF實裝（CHIP-ON-FLEX實裝）時，具有作業效率提高的優點。 作爲基材6，可使用由聚對苯二甲酸乙二醇酯（PET )、聚萘二甲酸乙二醇酯（polyethylene naphthalate )、 200932860 聚間苯二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯、聚烯烴 、聚乙酸酯、聚碳酸酯、聚苯硫醚、聚醯胺、乙烯•乙酸 乙烯酯共聚物、聚氯乙烯、聚偏氯乙烯、合成橡膠系、液 晶聚合物等所成的各種膠帶。惟，構成基材6的材質並不 . 限定於此等，此外，作爲基材6，可使用與黏著劑層8抵 接面等被施以電暈放電處理、增黏塗層處理、防靜電處理 等者。 〇 此外，使用電路連接材料5時，亦可於基材6的表面 上塗佈剝離處理劑後使用，使黏著劑層8可容易地從基材 6剝離。作爲剝離處理劑，亦可使用聚矽氧烷樹脂、聚矽 氧烷與有機系樹脂的共聚物、醇酸樹脂、胺基醇酸樹脂、 具有長鏈烷基之樹脂、具有氟烷基之樹脂、蟲膠樹脂等之 各種剝離處理劑。 基材6的厚度，並沒有特別的限制，但考量電路連接 材料5的保管、使用時的便利性等，較佳爲4〜2 0 0 μιη ,更 © 進一步地考量材料成本或生產性，更佳爲1 5〜75 μηι。 - 黏著劑層8的厚度，可依所連接的電路構件的形狀等 • 適當調整，但較佳爲5〜50μιη。黏著劑層8的厚度低於 5μπι，則會有塡充於電路構件間之黏著劑組成物的量變不 足的傾向，另一方面，超過50μιη，則會有確保應連接的 電路電極間的導通變困難的傾向。 形成黏著劑層8的黏著劑組成物，以溫度2 0 0 °C加熱 1小時，則成爲符合以下的條件之硬化物較佳。亦即，黏 著劑組成物的硬化物，由連接信賴性的觀點而言，以動態 -10- 200932860 黏彈性測量裝置所測量之於-50°C的貯藏彈性率爲 2.0〜3.0GPa，且於100°C的貯藏彈性率爲1.0〜2.0GPa較佳 。此外，該硬化物於-5 0〜100 °C的範圍的貯藏彈性率的最大 値與最小値的差爲2.0GPa以下較佳。 , 使用如硬化物的貯藏彈性率於所定的溫度條件下顯著 地降低之黏著劑組成物作爲電路連接材料時，會有電路構 件的連接信賴性惡化的問題，但如上述，藉由在-5 0〜1 0 0 °C Q 的廣泛的溫度範圍中抑制貯藏彈性率的降低，可製造具有 優異的連接信賴性之電路連接體。再者，黏著劑組成物的 硬化物的玻璃轉化溫度，由連接部的連接信賴性的觀點而 言，以 100〜150°C爲佳，1 10〜140°C較佳，1 10〜130°c更佳 〇 本實施形態相關的黏著劑組成物的硬化物可達成貯藏 彈性率相關的優異特性的主因，推測爲黏著劑成分9含有 (c)丙烯酸共聚物，因爲此丙烯酸共聚物產生作爲應力 〇 緩和劑的功能。 _ (黏著劑成分） 接著，說明關於黏著劑成分9所含有的（a)環氧樹 脂、（b)環氧樹脂硬化劑、及（c)丙烯酸系共聚物。 作爲（a)環氧樹脂’可列舉雙酚A型環氧樹脂、雙 酚F型環氧樹脂、雙酚S型環氧樹脂、酚酚醛漬漆型環氧 樹脂、甲酚酚醛漬漆型環氧樹脂、雙酚A酚醛漬漆型環氧 樹脂、雙酚F酚醛漬漆型環氧樹脂、脂環式環氧樹脂、縮 -11 - 200932860 水甘油酯型環氧樹脂、縮水甘油胺型環氧樹脂、海因型環 氧樹脂、三聚異氰酸酯型環氧樹脂、脂肪族鏈狀環氧樹脂 等。此等的環氧樹脂，可被鹵化，亦可被氫化，此等的環 氧樹脂，可單獨使用1種’或組合2種以上使用。 作爲（b )環氧樹脂硬化劑，可列舉胺系、酚系、酸 酐物系、咪唑系、醯肼系、雙氰胺、三氟化硼-胺錯合物 、毓鹽、碘鑰鹽、胺醯亞胺等。此等之中，由硬化性及適 @ 用期的觀點而言’使用咪唑系硬化劑較佳。作爲咪唑系硬 化劑，可列舉2-乙基-4-甲基咪唑、2-甲基咪唑、1-氰基乙 基-2-苯基咪唑等。此等可單獨使用或混合2種以上使用， 亦可混合分解促進劑、抑制劑等後使用。再者，爲了高水 準地達成長的適用期及速硬化性雙方，使用潛在性硬化促 進劑較佳，具體而言使用咪唑與環氧樹脂的加成化合物（ 微膠囊型或加成化合物型潛在性硬化劑等）較佳。 (c)丙烯酸系共聚物，具有交聯結構且重量平均分 〇 子量爲3 0000〜80000。含有重量平均分子量低於3 0000的 . 丙烯酸系共聚物之黏著劑組成物，薄膜形成性變不足的同 時，應力緩和效果亦變不足。另一方面，重量平均分子量 超過80000則含有丙烯酸系共聚物之黏著劑組成物的流動 性變不足，電路塡充性變不足的同時，會有與環氧樹脂的 相溶性降低的傾向。丙烯酸系共聚物的重量平均分子量爲 40000〜70000 較佳，40000〜60000 爲更佳。 (c)丙烯酸系共聚物可藉由具有交聯反應性基的單 體與其他的單體的共聚合而得到，作爲具有交聯反應性基 -12- 200932860 之單體，可列舉（甲基）丙烯酸縮水甘油酯、丙烯醯胺、 羥基丁基丙烯酸酯、羥基乙基甲基丙烯酸酯等。 作爲（C)丙烯酸系共聚物的較佳具體例子，可列舉 藉由將相對於單體成分1〇〇質量份之丙烯酸縮水甘油酯及 • 甲基丙烯酸縮水甘油酯的合計量爲1〜7質量份（更佳爲 2〜6質量份）的原料供給至共聚合反應而製造者。藉由（ 甲基）丙烯酸縮水甘油酯的合計量低於1質量份的單體成 〇 分的共聚合而得到的丙烯酸系共聚物，交聯結構未充分地 發展，含有如此的丙烯酸系共聚物之黏著劑組成物，會有 應力緩和性變不足的傾向。另一方面，含有藉由（甲基） 丙烯酸縮水甘油酯的合計量超過7質量份之單體成分的共 聚合所得到的丙烯酸系共聚物之黏著劑組成物，會有貯藏 彈性率易變高而應力緩和性變不足的傾向。 (c)丙烯酸系共聚物的玻璃轉化溫度（Tg)爲-40〜40°C 較佳’含有玻璃轉化溫度低於-40 °C的丙烯酸系共聚物之黏 〇 著劑組成物，會有黏著性（貼附性）變得過大的傾向。另 . 一方面，含有玻璃轉化溫度超過40°C之丙烯酸系共聚物之 黏著劑組成物，會有黏著性變不足的傾向。（c)丙烯酸 系共聚物的玻璃轉化溫度爲-20~20°C較佳。 製造（c)丙烯酸系共聚物時，作爲與（甲基）丙烯 酸縮水甘油酯共聚合的其他單體，可列舉丁基丙烯酸酯、 丙烯腈、羥基甲基丙烯酸酯、苯乙烯、丁基甲基丙烯酸酯 、丙烯醯胺等。此等的單體中，藉由調整丁基丙烯酸酯及 /或丙烯腈的摻合量，可使所得到的丙烯酸系共聚物的玻 -13- 200932860 璃轉化溫度成爲較適合者。更具體而言，相對於原料所含 有的單體成分100質量份，使丁基丙烯酸酯及丙烯腈的合 計量爲80質量份以上較佳。 (a)環氧樹脂的含量，以黏著劑成分9的全質量爲 , 基準’以3〜50質量％爲佳，1 〇〜30質量％較佳。（a )環氧 樹脂的含量低於3質量％，則硬化反應的進行變不足，會 有得到優良的黏著強度或連接電阻値變困難的傾向。另一 0 方面，超過50質量％，則會有黏著劑成分9的流動性降低 ，適用期變短的傾向，此外，會有電路連接體的連接部的 連接電阻値變高的傾向。 (b )環氧樹脂硬化劑的含量，以黏著劑成分9的全 質量爲基準’以5〜60質量％爲佳，10〜40質量％較佳。（b )環氧樹脂硬化劑的含量低於5質量％，則會有硬化反應 的進行變不足’得到優良的黏著強度或連接電阻値變困難 的傾向。另一方面，超過60質量％，則會有黏著劑成分9 〇 的流動性降低，適用期變短的傾向。此外，會有電路連接 . 體的連接部的連接電阻値變高的傾向。 (c)丙烯酸系共聚物的含量，以黏著劑成分9的全 質量爲基準，以3〜30質量％爲佳，8~25質量％較佳。（c )丙烯酸系共聚物的含量低於3質量％，則會有應力緩和 效果變不足的傾向，另一方面，超過25質量％，則會有黏 著劑成分9的流動性降低，適用期變短的傾向。此外，會 有電路連接體的連接部的連接電阻値變高的傾向。 黏著劑成分9亦可再含有薄膜形成性高分子，以黏著 -14- 200932860 劑成分9的全質量爲基準，薄膜形成性高分子的含量， 2〜80質量％爲佳，5〜70質量％較佳，1〇〜60質量％更佳 作爲薄膜形成性高分子，可使用聚苯乙烯、聚乙烯、聚 烯丁縮醛、聚乙烯甲縮醛、聚醯亞胺、聚醯胺、聚酯、 . 氯乙烯、聚二苯醚、尿素樹脂、三聚氰胺樹脂、酚樹脂 二甲苯樹脂、聚異氰酸酯樹脂、苯氧樹脂、聚醯亞胺樹 、聚酯胺基甲酸乙酯樹脂等。 〇 (導電粒子） 導電粒子10A，分散於黏著劑成分9中，作爲導電 子 1 0A，可列舉例如 Au、Ag、Pt、Ni、Cu、W、Sb、 、焊劑等之金屬或碳的粒子。導電粒子10A的平均粒徑 分散性、導電性的觀點而言爲1〜1 8 μιη較佳。 導電粒子10Α的摻合比例，相對於黏著劑層8中所 有的黏著劑成分1〇〇體積份，以0.1〜30體積份爲佳 〇 〇.1~1〇體積份較佳。此摻合比例低於0.1體積份則會有 . 向的電極間的連接電阻變高的傾向，超過3 0體積份則 有鄰接的電極間的短路變易發生的傾向。 而且，形成黏著劑層8之黏著劑組成物，可含有塡 材、軟化劑、促進劑、抗老化劑、著色劑、難燃化劑、 變劑、偶合劑、三聚氰胺樹脂、異氰酸酯類等。含有塡 材時，因爲連接信賴性等可提高而較佳，作爲塡充材， 其最大徑低於導電粒子的粒徑者較適合，此外，塡充材 含量，以黏著劑組成物的全體積基準而言，爲5~60體積 以 〇 乙 聚 、 脂 粒 Sn 由 含 ， 對 會 充 觸 充 以 的 ：% -15- 200932860 的範圍較佳，超過60體積％，則會有發生連接信賴性與密 著性的降低的傾向。再者，作爲偶合劑，以含有由乙烯基 、丙烯基、胺基、環氧基及異氰酸酯基所成的群所選出的 1種以上的基之化合物，由黏著性的提高的觀點而言較佳 <電路連接體> Ο 接著，說明關於使用電路連接材料5所製造的電路連 接體。圖2係表示電路電極彼此經連接的電路連接體之槪 略截面圖’圖2所表示的電路連接體1〇〇，具備相互對向 的第1電路構件30及第2電路構件40，第1電路構件30 與第2電路構件40之間，設置了連接此等的連接部5 0a。 第1電路構件30，具備電路基板31、與形成於電路 基板31的主面31a上的電路電極32。第2電路構件40, 具備電路基板41、與形成於電路基板41的主面41a上的 〇 電路電極42。 - 作爲電路構件的具體例子，可列舉半導體晶片（1C晶 _ 片）、電阻體晶片、電容器晶片等的晶片零件等。此等的 電路構件，具備電路電極，具備多數的電路電極者爲—般 狀況。作爲上述電路構件經連接之另一方的電路構件的具 體例子’可列舉具有金屬配線之可撓膠帶、可撓印刷電路 板、銦錫氧化物（ITO )經蒸鍍的玻璃基板等之電路基板 〇 主面31a及/或主面41a，可塗佈氮化矽、聚矽氧烷化 -16- 200932860 合物及聚矽氧烷樹脂，以及感光性或非感光性的聚 樹脂等的有機絕緣物質。此外’主面31a及/或主面 可爲部分地具有由上述材質所成的區域者，而且’ 板31及/或電路基板41自體可爲由上述材質所成 面31a，41a，可用上述材質1種構成，亦可用2種 成，藉由適當選擇黏著劑成分9的組成，具有由上 質所成的部分之電路基板彼此亦可適切連接。 φ 各電路電極32，42的表面，可用由金、銀、 、铑、鈀、餓、銥、鉑及銦錫氧化物（ITO )所選 種構成，可用2種以上構成。此外，電路電極32, 表面的材質，在所有的電路電極中相同亦可，相異Z 連接部5〇a具備黏著劑層8中所含有的黏著劑 的硬化物9A、與分散於其的導電粒子l〇A。然後 路連接體1〇〇中’對向的電路電極32與電路電極 由導電粒子10A以電連接。亦即，導電粒子10A 〇 觸於電路電極32 ’42的雙方，因此，電路電極32 • 的連接電阻被充分地減低，電路電極32，42間的 電的連接變可能。另一方面，硬化物9A爲具有電 者’確保鄰接的電路電極彼此的絕緣性。故，可使 極32’ 42間的電流的流動順利，可充分地發揮電 有的功能。 <電路連接體的製造方法> 接著’說明關於電路連接體100的製造方法。 醯亞胺 41a， 電路基 者。主 以上構 述的材 錫、釕 出的1 42的 $可。 成分9 ，於電 42，介 直接接 ，42間 優良的 絕緣性 電路電 路所具 圖3係 -17- 200932860 藉由槪略截面圖表示本發明該相關的電路連接體的製造方 法之一實施形態的步騾圖。本實施形態，係使電路連接材 料5的黏著劑層8進行熱硬化，最後製造電路連接體100 〇 _ 首先，將電路連接材料5以所定的長度進行切斷的同 時，黏著劑層8朝向下方載置於第1電路構件30的電路 電極32被形成的面上（圖3(a))。此時，從黏著劑層 φ 8剝離基材6。 接著，在圖3(b)的箭頭A及B方向上加壓，將黏 著劑層8暫時連接於第1電路構件30 (圖3(c))。此 時的壓力只要是在不會對電路構件帶來損傷的範圍即可， 並沒有特別的限制，但一般而言爲0.1 ~3.0MPa較佳。此 外，一邊加熱一邊加壓亦可，加熱溫度定在實質地不使黏 著劑層8硬化的溫度。加熱溫度一般而言爲50〜100 °C較佳 ，此等的加熱及加壓在0.1-10秒的範圍內進行較佳。 〇 接下來，如圖3(d)所示，將第2電路構件40，在 . 第2電路電極42朝向第1電路構件30之側下載置於黏著 劑層8上。然後，一邊加熱黏著劑層8，一邊在圖3(d) 的箭頭A及B方向上加壓全體。此時的加熱溫度，定在黏 著劑層8的黏著劑成分9可硬化的溫度。加熱溫度以 150〜230°C爲佳，170〜210°C較佳，180〜200°C更佳。加熱溫 度低於150°C則會有硬化速度變慢的傾向，超過230°C則會 有不希望發生的副反應易進行的傾向。加熱時間以0.1~30 秒爲佳，1~25秒較佳，2〜20秒更佳。 -18- 200932860 藉由黏著劑成分9的硬化形成連接部50a，得到如圖 2所示的電路連接體100。連接的條件，可依所使用的用 途、黏著劑組成物、電路構件而適當選擇。再者，作爲黏 著劑層8的黏著劑成分，摻合藉由光而硬化者時，對黏著 . 劑層8適當照射活性光線或能量線亦可。作爲活性光線， 可列舉紫外線、可見光、紅外線等；作爲能量線，可列舉 電子線、X射線、γ線、微波等。 @ 以上，說明關於本發明的適切的實施形態，但本發明 並不限定於上述實施形態，本發明在不脫離其要旨的範圍 內可有各種的變形。 例如，於上述實施形態中，列舉含有導電粒子1 0 Α的 黏著劑組成物，但依所實裝的電路構件的形狀等，黏著劑 組成物亦可爲不含有導電粒子10A者。此外，取代導電粒 子10A，可使用由具有導電性的核粒子、與被設置於此核 粒子的表面上的複數的絕緣性粒子所構成的導電粒子。 〇 圖4所示的導電粒子10B，具備具有導電性的核粒子 . 1及被設置於此核粒子1的表面上的複數的絕緣性粒子2 ，然後，核粒子1係由構成中心部分的基材粒子la及被 設置於此基材粒子la的表面上的導電層lb所構成，以下 ，說明關於導電粒子10B。 作爲基材粒子la的材質，可列舉玻璃、陶瓷、有機 高分子化合物等。此等的材質中，經加熱及/或加壓而變 形者（例如玻璃、有機高分子化合物）較佳。若爲基材粒 子la變形者，導電粒子10B被電路電極32，42按壓時， -19- 200932860 與電路電極的接觸面積增加，此外’可吸收電路電極32 ’ 42的表面的凹凸，所以，電路電極間的連接信賴性提高。 由如上述的觀點而言，適合作爲構成基材粒子la的 材質者，例如丙烯酸樹脂、苯乙烯樹脂、苯並鳥糞胺樹脂 ^ 、聚矽氧烷樹脂、聚丁二烯樹脂或此等的共聚物，及’交 聯此等者。基材粒子la，粒子間可爲相同或相異種類的材 質，相同粒子中可單獨使用1種的材質，或混合2種以上 φ 的材質後使用。 基材粒子la的平均粒徑，可依用途等適當設計，但 0.5~20μιη爲佳，1~10μιη較佳，2〜5μιη更佳。使用平均粒 徑低於0.5 μιη的基材粒子製作導電粒子，則會有粒子的二 次凝聚產生，鄰接的電路電極間的絕緣性變不足的傾向， 使用超過2 0 μιη的基材粒子製作導電粒子，則因爲其大小 而會有引起鄰接的電路電極間的絕緣性變不足的傾向。 導電層lb，係被設置於被覆基材粒子la的表面之由 〇 具有導電性的材質所成的層，由充分地確保導電性之觀點 . 而言，導電層lb被覆基材粒子la的全表面較佳。 作爲導電層1 b的材質，可列舉例如金、銀、鉑、鎳 、銅及此等的合金、含有錫的焊劑等的合金，以及，具有 碳等的導電性之非金屬。相對於基材粒子la，因爲可藉由 無電解鍍敷的被覆，故導電層lb的材質爲金屬較佳。此 外，爲了得到充分的適用期，以金、銀、鉑或此等的合金 較佳’金更佳。再者，此等可單獨使用1種，或組合2種 以上使用。 -20- 200932860 導電層lb的厚度，可依其所使用的材質或 適當設計，以50~200nm爲佳，80~150nm較佳。 5 Onm，會有無法得到連接部的充分低的電阻値的 一方面，超過200nm則厚度的導電層lb，會有 . 降低的傾向。 導電層lb，可用一層或二層以上構成，在任 ，由使用其所製作的黏著劑組成物的保存性的觀 〇 核粒子1的表面層，皆用金、銀、鉛或此等的合 較佳，用金構成更佳。導電層lb用由金、銀、 的合金（以下，稱爲「金等的金屬」）所成的一 時，爲了得到連接部分充分低的電阻値，3 10~200nm 較佳。 另一方面，導電層lb用二層以上所構成時 lb的最外層用金等的金屬所構成較佳，但最外層 子la之間的層，例如可用含有鎳、銅、錫或此 Ο 之金屬層所構成，此時，構成導電層lb的最外 . 的金屬所成的金屬層的厚度，由黏著劑組成物的 觀點而W，爲30~200nm較佳。鎮、銅、錫或此 ，會有因爲氧化還原作用而發生游離自由基的情 ，由金等的金屬所成的最外層的厚度低於30nm 具有自由基聚合性的黏著劑成分時，會有充分地 自由基的影響變困難的傾向。 作爲使導電層lb形成於基材粒子la表面上 可列舉無電解鍍敷處理或物理的塗佈處理，由笔 用途等而 厚度低於 傾向，另 製造效率 一種情況 點而言， 金所構成 鉛或此等 層所構成 ί厚度爲 ，導電層 與基材粒 等的合金 層之金等 保存性的 等的合金 況，因此 ，則倂用 防止游離 之方法， ί電層lb -21 - 200932860 的形成的容易性之觀點而言，將由金屬所成的導電層1b 藉由無電解鍍敷處理後形成於基材粒子1a的表面上較佳 〇 絕緣性粒子2，由有機高分子化合物所構成’作爲有 . 機高分子化合物，以具有熱軟化性者較佳。絕緣性粒子的 適合的素材，例如聚乙烯、乙烯一乙酸共聚物、乙烯一（ 甲基）丙烯酸共聚物、乙烯一（甲基）丙烯酸共聚物、乙 Q 烯-（甲基）丙烯酸酯共聚物、聚酯、聚醯胺、聚胺基甲 酸乙酯、聚苯乙烯、苯乙烯一二乙烯基苯共聚物、苯乙烯 一異丁烯共聚物、苯乙烯-丁二烯共聚物、苯乙烯-（甲 基）丙烯酸共聚物、乙烯-丙烯共聚物' (甲基）丙烯酸 酯系橡膠、苯乙烯-乙烯-丁烯共聚物、苯氧樹脂、固形 環氧樹脂等。此等可單獨使用，亦可組合2種以上使用。 再者，由粒度分布的分散度、耐溶劑性及耐熱性的觀點而 言，以苯乙烯-(甲基）丙烯酸共聚物特別適合，作爲絕 ❹ 緣性粒子2的製造方法，可列舉種子（seed )聚合法等。 . 構成絕緣性粒子2的有機高分子化合物的軟化點，爲 電路構件彼此的連接時的加熱溫度以上較佳，軟化點低於 連接時的加熱溫度，則會有因爲連接時絕緣性粒子2因爲 過度地變形，而無法得到優良的電的連接的傾向。 絕緣性粒子2的平均粒徑，可依用途等適當設計，但 50〜500nm爲佳，50~400nm較佳，100〜300nm更佳。平均 粒徑低於5 Onm，則會有鄰接的電路間的絕緣性變不足的 傾向，另一方面，超過5 0 0 nm，則會有達成連接部分的充 -22- 200932860 分低的初期電阻値及抑制電阻値的經時的上昇雙方變 的傾向。 此外，本發明該相關的電路連接材料，如上述實 態中的電路連接材料5，不限定於在基材6上形成單 _ 黏著劑層8的單層構造，亦可爲於基材6上層合複數 著劑層之多層構造。多層構造的電路連接材料，可藉 數層合黏著劑成分及導電粒子的種類或此等的含量不 U 層而製造，例如電路連接材料可具備含有導電粒子的 導電粒子之層、與設置於此含有導電粒子之層的至少 的面上之不含有導電粒子的非含有導電粒子之層。 圖5所示的電路連接材料15，具備二層構造的黏 層7、與各自被覆此黏著劑層7的兩側最外面之基材 6b。電路連接材料10的黏著劑層7，由含有導電粒子 有導電粒子之層7a及不含有導電粒子的非含有導電 之層7b所構成。電路連接材料15，於基材6a的表面 〇 成含有導電粒子之層7a，另一方面，於基材6b的表 . 形成非含有導電粒子之層7b，可藉由使用先前技術的 機等貼合此等的層而製作，使用電路連接材料15時 當地剝離基材6a，6b。 依據電路連接材料15，於電路構件彼此的接合時 充分地抑制因爲黏著劑成分的流動所造成的電路電極 導電粒子的個數的減少。因此，例如將1C晶片藉由 實裝或COF實裝連接於基板上時’可充分地確保1C 的金屬凸塊上的導電粒子的個數。此時’具備IC晶 困難 施形 層的 的黏 由複 同的 含有 一方 著劑 6a， 的含 粒子 上形 面上 層壓 ，適 ，可 上中 COG 晶片 片的 -23- 200932860 金屬凸塊之面與非含有導電粒子之層7b’另一方面，應實 裝1C晶片的基板與含有導電粒子之層7a，各自抵接下配 置電路連接材料7較佳。 . 【實施方式】 [實施例] (實施例1 ) @ 如下述作法製造具有導電性的核粒子，亦即，準備作 爲基材粒子之交聯聚苯乙烯粒子（總硏化學製、商品名： SX系列、平均粒徑：4μιη )，於此粒子的表面上，藉由無 電解鍍敷處理設置Ni層（厚度0.08 μιη)，而且，於此Ni 層的外側上藉由無電解鍍敷處理設置Au層（厚度0.03 μιη )，得到具有由Ni層及Au層所成的導電層之核粒子。 作爲被覆核粒子的表面用的有機高分子化合物（絕緣 被覆），準備交聯丙烯酸樹脂（總硏化學製、商品名： Q MP系列），將此交聯丙烯酸樹脂4g與核粒子20g導入至 . hybridizer (股份有限公司奈良機械製作所製、商品名： NHS系列），製作導電粒子，再者，於hybridizer的處理 條件，定爲旋轉速度1 6000/分鐘、反應槽溫度60°C。 接著，使用雙酚A型環氧樹脂與9、9’-雙（4-羥基苯 基）芴，合成玻璃轉化溫度爲80°C的苯氧樹脂，將此苯氧 樹脂50g溶解於溶劑，調製固體成分40質量％的溶液，再 者，作爲溶劑，使用甲苯與乙酸乙酯的混合溶劑（兩者的 混合質量比=1 : 1 )。 -24- 200932860 另一方面，藉由使表1所示的組成的單體原料共聚合 ，製造具有交聯結構之丙烯酸系共聚物，本實施例中所製 造的丙烯酸系共聚物的平均分子量爲4 0 0 0 0 (聚苯乙烯換 算），玻璃轉化溫度Tg爲-10°C，將此丙烯酸系共聚物溶 . 解於乙酸乙酯，調製固體成分40質量％的溶液。 混合苯氧樹脂45質量份（固體成分）、與丙烯酸系 共聚物15質量份（固體成分）、與含有微膠囊型潛在性 Q 硬化劑（咪唑系硬化劑）之液狀環氧樹脂40質量份（固 體成分）而得到黏著劑成分的溶液，相對於黏著劑成分 100體積份摻合上述導電粒子5體積份，藉由於溫度2 3 °c 中攪拌，得到黏著劑組成物的溶液。 藉由剝離處理劑（聚矽氧烷樹脂）經施加表面處理之 PET薄膜（帝人杜邦薄膜股份有限公司製、商品名： Purex、厚度：50μηι )的面上，塗佈黏著劑組成物的溶液 而進行塗佈，然後，藉由使其進行熱風乾燥（以8 0 °C進行 Ο 5分鐘），得到受到PET薄膜所支持之厚度ΙΟμιη的含有 . 導電粒子之層。 _ 此外，混合苯氧樹脂40質量份（固體成分）、與丙 烯酸系共聚物15質量份（固體成分）、與含有微膠囊型 潛在性硬化劑（咪唑系硬化劑）之液狀環氧樹脂45質量 份（固體成分），得到不含有導電粒子的黏著劑成分的溶 液。將此黏著劑成分的溶液，塗佈於藉由剝離處理劑（聚 矽氧烷樹脂）經施以表面處理的PET薄膜（帝人杜邦薄膜 股份有限公司製、商品名：Purex、厚度：50μιη)之面上 -25- 200932860 而塗佈。然後，藉由將其進行熱風乾燥（以80 °C進行5分 鐘），得到受到PET薄膜支持的厚度15 μηι的非含有導電 粒子之層。 將此等的黏著薄膜彼此，使用先前技術習知的層壓機 貼合’藉此，得到如圖5所示的二層構成的電路連接材料 0 (電路連接體的製作） 使用如上述作法所製造的電路連接材料，連接ΙΤΟ基 板（厚度〇.7mm、表面電阻<20Ω/〇 )與1C晶片（厚度 0.55mm)，形成電路連接體。1C晶片係使用其備凸塊面 積 2500μηι2(50μιηχ50μιη)、間距 ΙΟΟμιη、高度 20μιη 的 金凸塊者，ΙΤΟ基板係使用於厚度1.1mm的玻璃板的表面 上藉由蒸鍍形成ITO者。 1C晶片與ITO基板之間，介由電路連接材料，使用 ❾ 壓著裝置（Tor ay Engineering股份有限公司製、商品名： . FC-1200 )進行連接。具體而言，首先，剝離含有導電粒 子之層側的PET薄膜，於IT Ο基板上配置電路連接材料 使含有導電粒子之層與ITO基板抵接，然後，使用壓著裝 置進行暫時壓著（以溫度75°C、壓力l.OMPa進行2秒） ，然後，剝離非含有導電粒子之層側的PET薄膜後，載置 1C晶片使金凸塊與非含有導電粒子之層抵接。藉由於基座 上使用石英玻璃，以溫度200°C、壓力80MPa加熱加壓5 秒，得到具備連接部的電路連接體。 -26- 200932860 (翹曲量的測量） 關於實裝1C晶片後的ITO基板的翹曲量，使用非接 觸式雷射型3次元形狀測量裝置（KEYENCE製、商品名 . :LT-9000 )測量。使1C晶片側朝向下方，使ITO基板的 裏面朝向上方而將電路連接體放置在平坦的台上。然後， 測量ITO基板的裏面的中心部、與距離此ITO基板的裏面 U 中1C晶片的兩端爲5mm之處的高度的差距，將此高度的 差距定爲玻璃基板的翹曲量。 (初期連接電阻的測量）However, in recent years, with the development of the enlargement and thinning of the liquid crystal panel, the adhesive composition of the prior art is subjected to COG 200932860 at the above temperature conditions, and the thermal expansion and contraction difference due to the temperature difference during heating is poor. Internal stress is generated, and there is a problem that the 1C wafer or the glass panel is warped. As a means for reducing warpage of a circuit member, Patent Document 1 describes an adhesive film for circuit connection in which a curing agent for an epoxy resin contains a latent curing agent made of a cerium salt, and it is described that by using this By adhering the film, the heating temperature at the time of mounting can be lowered to 16 (TC or less, and the internal stress generated by the circuit connector of the circuit member can be reduced (refer to paragraph [0019] of Patent Document 1). [Problem to be Solved by the Invention] The adhesive film described in Patent Document 1 exhibits excellent effects in lowering the heating temperature. However, because of the use of a special latent G-hardener, there is a problem that the application period is relatively short. Therefore, the current situation is this. The adhesive film is limited in its use compared with the prior art imidazole-based hardener. The present invention has been made in view of the above circumstances, and an object thereof is to provide a circuit member that can be sufficiently suppressed even when a circuit member is connected to each other at a high temperature condition of about 200 ° C. a warped adhesive composition and a circuit connecting material using the same. Further, an object of the present invention is to provide a circuit connector for connecting a circuit member with a low connection resistance, and a connection method for obtaining the circuit member thereof - 5, 2009, 280, 60 Means for Solving the Problem The adhesive composition of the present invention is used for electrically connecting the circuit electrodes of the circuit members to each other while adhering the circuit member, and the feature is a ring. An oxy-resin, an epoxy resin hardener, and an acryl-based copolymer having a crosslinked structure and having a weight average molecular weight of 30,000 to 80,000. The weight average molecular weight of the acrylic copolymer is determined by gel permeation chromatography. The measurement is based on the calibration curve prepared by using standard polystyrene. In the adhesive composition of the present invention, the above-mentioned acrylic copolymer functions as a stress relieving agent, and therefore, a microcapsule type or An imidazole hardener such as an additive compound type latent hardener is used as a hardener for an epoxy resin, even at about 200 ° C. In the hardening treatment, the internal stress can be effectively alleviated, and the warpage of the circuit member can be sufficiently suppressed. The adhesive composition of the present invention further contains conductive particles, based on the adhesion of the conductive particles dispersed in the adhesive component. The composition of the composition can produce a circuit connector having excellent connection reliability. The glass transition temperature of the above acrylic copolymer is -4 0 to 4 01. Preferably, the glass transition temperature of the acrylic copolymer is within the above range. In addition, the glass transition temperature of the cured product of the adhesive composition is preferably from 100 to 150 ° C from the viewpoint of connection reliability of the connection portion. Further, the acrylic copolymer is obtained by copolymerizing a monomer component of -6-200932860 contained in a raw material, and a propylene glycol vinegar and a mass fraction of a monomer component contained in the raw material. The total amount of glycidyl methacrylate is preferably 1 to 7 parts by mass. By blending the acrylic copolymer produced from the raw material containing glycidyl acrylate and/or glycidyl methacrylate in the above range, the adhesive composition can be excellent, and excellent stress relaxation can be achieved. The warpage of the circuit member is sufficiently suppressed. In the present invention, the related adhesive composition is obtained by heating φ for 1 hour at a temperature of 200 ° C, and the storage modulus at -50 ° C is 2.0 to 3.0 GPa and is at 100 ° C. The storage modulus is 1.0 to 2.0 GPa, and the difference between the maximum enthalpy and the minimum enthalpy of storage elasticity in the range of -50 to 100 ° C is preferably 2.0 gPa or less. According to the cured product of the adhesive composition conforming to the relevant conditions, the storage elastic modulus can be suppressed in a wide temperature range, and the adhesive composition can be used for the connection of the circuit members to manufacture the connection reliability. Circuit connector. The circuit connecting material of the present invention comprises a film-form substrate and an adhesive layer; - the adhesive layer is formed of the adhesive composition of the present invention, and is disposed on one side of the substrate On the surface. According to the circuit connecting material of the related configuration, the adhesive layer can be easily disposed on the circuit member, and the work efficiency can be improved. Further, when a circuit connecting material is used, the film-form substrate can be appropriately peeled off. The circuit connector of the present invention is characterized in that it has a pair of circuit members and a connecting portion that are disposed opposite each other, and the connecting portion is formed by a cured product of the adhesive composition according to the present invention. Between the circuit members 200932860, the circuit members are adhered to each other such that the circuit electrodes of the respective circuit members are electrically connected to each other. In the circuit connector of the present invention, at least one of the pair of circuit members may be a 1C wafer. Further, in the circuit connector, at least one surface of each of the circuit electrodes of the pair of electrical path members may be made of gold, silver, tin, antimony, bismuth, palladium, cesium, bismuth, platinum, and indium. At least one selected from the group consisting of tin oxides, in the circuit connector of the present invention, at least one side of the abutting surface of the pair of circuit members that are in contact with the connecting portion may have nitridation A portion composed of at least one selected material selected from the group consisting of a ruthenium, a polyoxyalkylene compound, and a photosensitive or non-photosensitive polyimide resin. A method of connecting circuit members according to the present invention, wherein the related adhesive composition of the present invention is interposed between a pair of circuit members disposed oppositely, and is heated and pressurized as a whole The cured portion of the adhesive composition is formed by bonding the circuit members to each other so that the circuit electrodes of the circuit members interposed between the pair of circuit components are electrically connected to each other, and the pair is provided. The circuit member and the circuit connector of the connection portion. [Effect of the Invention] According to the present invention, even when the circuit members are connected to each other under high temperature conditions of about 200 ° C, the warpage of the circuit member can be sufficiently suppressed. BEST MODE FOR CARRYING OUT THE INVENTION -8 - 200932860 Hereinafter, a preferred embodiment of the present invention will be described in detail with reference to the attached drawings. In the description of the drawings, the same elements are denoted by the same reference numerals, and the repeated description is omitted. Further, the drawings are convenient, and the dimensional ratio of the drawings is not necessarily the same as the explanation. In this book, "(meth)acrylate" means "acrylate" and its corresponding "methacrylate"; "(meth)acrylic" means "acrylic" and its corresponding "Methacrylate". 〇 <Circuit Connection Material> First, the circuit connection material related to the present embodiment will be described. Fig. 1 is a cross-sectional view showing a circuit connecting material 5 according to the present embodiment. The circuit connecting material 5 is provided with a film-form substrate 6 and an adhesive layer 8 provided on one surface of the substrate 6. The adhesive layer 8 is composed of an adhesive component 9 containing (a) an epoxy resin, (b) an epoxy resin hardener, and (c) an acrylic copolymer, and a conductive particle Q dispersed in the adhesive component 9. The adhesive composition of the sub-i〇A. The circuit connecting material 5 is produced by applying a solution of the adhesive composition to the film-form substrate 6 by using a coating device, and drying the air to form the adhesive layer 8 for a predetermined period of time. By forming the adhesive layer 8 formed of the adhesive composition, for example, compared with the case where the adhesive composition is directly used in the form of a paste, it is used for COG mounting or COF mounting of a 1C wafer or the like (CHIP-ON-FLEX When installed, it has the advantage of improved work efficiency. As the substrate 6, polyethylene terephthalate (PET), polyethylene naphthalate, 200932860 polyethylene isophthalate, polyterephthalic acid can be used. Butylene glycol ester, polyolefin, polyacetate, polycarbonate, polyphenylene sulfide, polyamine, ethylene/vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, synthetic rubber, liquid crystal polymer Wait for all kinds of tape. However, the material constituting the base material 6 is not limited to this, and the base material 6 may be subjected to corona discharge treatment, adhesion-promoting treatment, or antistatic treatment using a contact surface with the adhesive layer 8 or the like. Processing and so on. Further, when the circuit connecting material 5 is used, a release treatment agent may be applied to the surface of the substrate 6, and the adhesive layer 8 may be easily peeled off from the substrate 6. As the release treatment agent, a polydecane resin, a copolymer of a polysiloxane and an organic resin, an alkyd resin, an amino alkyd resin, a resin having a long-chain alkyl group, or a resin having a fluoroalkyl group can also be used. Various release treatment agents such as shellac resin. The thickness of the substrate 6 is not particularly limited. However, it is preferable to consider the storage of the circuit connecting material 5, the convenience in use, and the like, and it is preferably 4 to 200 μm, and further consider the material cost or productivity. Good for 1 5~75 μηι. - The thickness of the adhesive layer 8 can be appropriately adjusted depending on the shape of the circuit member to be connected, etc., but is preferably 5 to 50 μm. When the thickness of the adhesive layer 8 is less than 5 μm, the amount of the adhesive composition interposed between the circuit members tends to be insufficient. On the other hand, when the thickness exceeds 50 μm, the conduction between the circuit electrodes to be connected is ensured. Difficult tendency. When the adhesive composition forming the adhesive layer 8 is heated at a temperature of 200 ° C for 1 hour, it is preferable to obtain a cured product which satisfies the following conditions. That is, the cured product of the adhesive composition has a storage modulus of 2.0 to 3.0 GPa at -50 ° C as measured by a dynamic 10-200932860 viscoelasticity measuring device from the viewpoint of connection reliability. The storage modulus at 100 ° C is preferably 1.0 to 2.0 GPa. Further, the difference between the maximum enthalpy and the minimum enthalpy of the storage modulus of the cured product in the range of -5 0 to 100 ° C is preferably 2.0 GPa or less. When the adhesive composition having a storage modulus of the cured material which is remarkably lowered under a predetermined temperature condition is used as a circuit connecting material, there is a problem that the connection reliability of the circuit member is deteriorated, but as described above, by -5 In the wide temperature range of 0 to 1 0 0 °CQ, the decrease in storage modulus is suppressed, and a circuit connector having excellent connection reliability can be manufactured. Further, the glass transition temperature of the cured product of the adhesive composition is preferably 100 to 150 ° C, preferably 1 10 to 140 ° C, and 1 10 to 130 ° from the viewpoint of connection reliability of the connection portion. More preferably, the cured product of the adhesive composition according to the present embodiment can achieve the main cause of the excellent properties relating to the storage modulus, and it is presumed that the adhesive component 9 contains (c) an acrylic copolymer because the acrylic copolymer is generated as a stress. The function of the hydrating agent. _ (Adhesive component) Next, (a) epoxy resin, (b) epoxy resin curing agent, and (c) acrylic copolymer contained in the adhesive component 9 will be described. Examples of the (a) epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type ring. Oxygen resin, bisphenol A phenolic paint epoxy resin, bisphenol F phenolic paint epoxy resin, alicyclic epoxy resin, shrink-11 - 200932860 water glycidyl ester epoxy resin, glycidylamine ring Oxygen resin, hydantoin epoxy resin, trimeric isocyanate type epoxy resin, aliphatic chain epoxy resin, and the like. These epoxy resins may be halogenated or hydrogenated, and these epoxy resins may be used singly or in combination of two or more. Examples of the (b) epoxy resin curing agent include an amine system, a phenol type, an acid anhydride type, an imidazole type, an anthraquinone type, a dicyandiamide, a boron trifluoride-amine complex, a phosphonium salt, and an iodine salt. Amine amide and the like. Among these, it is preferred to use an imidazole-based curing agent from the viewpoint of curability and suitability. Examples of the imidazole-based hardening agent include 2-ethyl-4-methylimidazole, 2-methylimidazole, and 1-cyanoethyl-2-phenylimidazole. These may be used singly or in combination of two or more kinds, and may be used after mixing a decomposition accelerator, an inhibitor, or the like. Furthermore, in order to achieve both a long pot life and a rapid hardening property at a high level, it is preferred to use a latent curing accelerator, specifically, an addition compound of an imidazole and an epoxy resin (a microcapsule type or an additive compound type potential). Sex hardeners, etc.) are preferred. (c) An acrylic copolymer having a crosslinked structure and having a weight average molecular weight of from 30,000 to 80,000. When the adhesive composition of the acrylic copolymer having a weight average molecular weight of less than 30,000 is used, the film formability is insufficient, and the stress relaxation effect is also insufficient. On the other hand, when the weight average molecular weight exceeds 80,000, the fluidity of the adhesive composition containing the acrylic copolymer is insufficient, and the circuit chargeability is insufficient, and the compatibility with the epoxy resin tends to be lowered. The weight average molecular weight of the acrylic copolymer is preferably from 40000 to 70,000, more preferably from 40,000 to 600,000. (c) The acrylic copolymer can be obtained by copolymerization of a monomer having a crosslinking reactive group with another monomer, and as a monomer having a crosslinking reactive group of 12 to 200932860, (methyl group) Glycidyl acrylate, acrylamide, hydroxybutyl acrylate, hydroxyethyl methacrylate, and the like. A preferred example of the (C) acrylic copolymer is a mass of 1 to 7 by weight of glycidyl acrylate and glycidyl methacrylate in an amount of 1 part by mass based on the monomer component. A part (more preferably 2 to 6 parts by mass) of a raw material is supplied to a copolymerization reaction to be produced by a manufacturer. An acrylic copolymer obtained by copolymerization of a monomer having a total amount of glycidyl (meth)acrylate of less than 1 part by mass of the monomer, the crosslinked structure is not sufficiently developed, and the acrylic copolymer is contained. In the adhesive composition, the stress relaxation property tends to be insufficient. On the other hand, the adhesive composition of the acrylic copolymer obtained by copolymerization of a monomer component having a total amount of more than 7 parts by mass of glycidyl (meth)acrylate may have a high storage modulus. However, the tendency of stress relaxation is insufficient. (c) The glass transition temperature (Tg) of the acrylic copolymer is -40 to 40 ° C. Preferably, the adhesive composition containing an acrylic copolymer having a glass transition temperature of less than -40 ° C is adhesive. Sex (adhesion) tends to become too large. On the other hand, an adhesive composition containing an acrylic copolymer having a glass transition temperature of more than 40 °C tends to have insufficient adhesiveness. (c) The glass transition temperature of the acrylic copolymer is preferably -20 to 20 °C. When the (c) acrylic copolymer is produced, examples of the other monomer copolymerized with glycidyl (meth)acrylate include butyl acrylate, acrylonitrile, hydroxymethacrylate, styrene, and butyl methacrylate. , acrylamide and the like. Among these monomers, the glass transition temperature of the obtained acrylic copolymer can be made suitable by adjusting the blending amount of butyl acrylate and/or acrylonitrile. More specifically, the total amount of the butyl acrylate and the acrylonitrile is preferably 80 parts by mass or more based on 100 parts by mass of the monomer component contained in the raw material. (a) The content of the epoxy resin is preferably from 3 to 50% by mass based on the total mass of the adhesive component 9, and preferably from 1 to 30% by mass. (a) When the content of the epoxy resin is less than 3% by mass, the progress of the curing reaction is insufficient, and excellent adhesion strength or connection resistance entanglement tends to be difficult. On the other hand, when the amount is more than 50% by mass, the fluidity of the adhesive component 9 is lowered, the pot life is shortened, and the connection resistance of the connection portion of the circuit-connecting body tends to be high. (b) The content of the epoxy resin hardener is preferably 5 to 60% by mass, and preferably 10 to 40% by mass based on the total mass of the adhesive component 9. (b) When the content of the epoxy resin hardener is less than 5% by mass, the progress of the curing reaction may be insufficient, and it is difficult to obtain excellent adhesion strength or connection resistance. On the other hand, when it exceeds 60% by mass, the fluidity of the adhesive component 9 降低 decreases, and the pot life tends to be short. In addition, there is a tendency for the circuit to be connected. The connection resistance of the connection portion of the body tends to be high. The content of the (c) acrylic copolymer is preferably 3 to 30% by mass, and preferably 8 to 25% by mass based on the total mass of the adhesive component 9. (c) When the content of the acrylic copolymer is less than 3% by mass, the stress relaxation effect tends to be insufficient. On the other hand, when the content exceeds 25% by mass, the fluidity of the adhesive component 9 is lowered, and the pot life is changed. Short tendency. Further, the connection resistance of the connection portion of the circuit connector tends to be high. The adhesive component 9 may further contain a film-forming polymer, and the content of the film-forming polymer is preferably from 2 to 80% by mass, based on the total mass of the component of the adhesive agent-14-200932860, and is 5 to 70% by mass. Preferably, 1 to 60% by mass is more preferably used as the film-forming polymer, and polystyrene, polyethylene, polybutene acetal, polyvinyl acetal, polyimide, polyamine, polyester can be used. . Vinyl chloride, polydiphenyl ether, urea resin, melamine resin, phenol resin xylene resin, polyisocyanate resin, phenoxy resin, polyimide tree, polyester urethane resin, and the like. 〇 (conductive particles) The conductive particles 10A are dispersed in the adhesive component 9, and examples of the conductive material 10A include metals such as Au, Ag, Pt, Ni, Cu, W, Sb, and flux, or particles of carbon. The average particle diameter of the conductive particles 10A is preferably from 1 to 18 μm from the viewpoint of dispersibility and conductivity. The blending ratio of the conductive particles 10 Å is preferably 0.1 to 30 parts by volume, based on 1 part by volume of the total of the adhesive component in the adhesive layer 8. When the blending ratio is less than 0.1 part by volume, the connection resistance between the electrodes tends to be high, and if it exceeds 30 parts by volume, the short circuit between adjacent electrodes tends to occur. Further, the adhesive composition forming the adhesive layer 8 may contain a bismuth material, a softener, an accelerator, an anti-aging agent, a colorant, a flame retardant, a varnish, a coupling agent, a melamine resin, an isocyanate or the like. When the coffin is contained, it is preferable because the connection reliability and the like can be improved, and as the ruthenium material, the maximum diameter is smaller than the particle diameter of the conductive particles, and the ruthenium content is the full volume of the adhesive composition. In terms of the benchmark, it is 5 to 60 volumes, and the lipid particles are contained. The range of % -15-200932860 is better, and when it exceeds 60% by volume, connection reliability occurs. The tendency to decrease with adhesion. Further, as a coupling agent, a compound containing one or more kinds of groups selected from a group consisting of a vinyl group, a propenyl group, an amine group, an epoxy group, and an isocyanate group is improved from the viewpoint of improving adhesion. Good <Circuit Connector> Next, a circuit connector manufactured using the circuit connecting material 5 will be described. 2 is a schematic cross-sectional view showing a circuit connecting body in which circuit electrodes are connected to each other. The circuit connecting body 1 shown in FIG. 2 includes first and second circuit members 30 and 40, which are opposed to each other. A connection portion 50a that connects these is provided between the circuit member 30 and the second circuit member 40. The first circuit member 30 includes a circuit board 31 and a circuit electrode 32 formed on the main surface 31a of the circuit board 31. The second circuit member 40 includes a circuit board 41 and a 电路 circuit electrode 42 formed on the main surface 41a of the circuit board 41. - Specific examples of the circuit member include wafer parts such as a semiconductor wafer (1C wafer), a resistor wafer, and a capacitor wafer. These circuit components are provided with circuit electrodes, and those having a large number of circuit electrodes are in a general condition. Specific examples of the circuit member to which the other circuit member is connected include a circuit board such as a flexible tape having a metal wiring, a flexible printed circuit board, or a glass substrate on which an indium tin oxide (ITO) is vapor-deposited. The main surface 31a and/or the main surface 41a may be coated with an organic insulating material such as tantalum nitride, polyoxyalkylene-16-200932860 and a polyoxyalkylene resin, and a photosensitive or non-photosensitive poly resin. . Further, the main surface 31a and/or the main surface may have a region partially formed of the above materials, and the 'plate 31 and/or the circuit substrate 41 may be formed by the above-mentioned materials 31a, 41a. One type of material may be used, and two types of materials may be used. By appropriately selecting the composition of the adhesive component 9, the circuit boards having the portions formed of the upper layers may be appropriately connected to each other. φ The surface of each of the circuit electrodes 32 and 42 may be selected from gold, silver, rhodium, palladium, ruthenium, rhodium, platinum, and indium tin oxide (ITO), and may be composed of two or more kinds. Further, the material of the surface of the circuit electrode 32 may be the same in all of the circuit electrodes, and the dissimilar Z connecting portion 5a includes the cured product 9A of the adhesive contained in the adhesive layer 8, and the conductive material dispersed therein. Particle l〇A. Then, the opposite circuit electrode 32 and the circuit electrode are electrically connected by the conductive particles 10A. That is, the conductive particles 10A are in contact with both of the circuit electrodes 32'42, and therefore, the connection resistance of the circuit electrodes 32 is sufficiently reduced, and the electrical connection between the circuit electrodes 32, 42 becomes possible. On the other hand, the cured product 9A has an electric insulator to ensure insulation between adjacent circuit electrodes. Therefore, the current flow between the poles 32' 42 can be made smooth, and the function of electricity can be sufficiently exerted. <Method of Manufacturing Circuit Connector> Next, a method of manufacturing the circuit connector 100 will be described. Yttrium 41a, circuit based. The material of the main and the above is tin and the price of 1 42 is ok. Component 9 is directly connected to electricity 42 and has 42 excellent insulating circuit circuits. FIG. 3 is a schematic diagram showing an embodiment of a method for manufacturing the related circuit connector of the present invention by a schematic cross-sectional view. Step diagram. In the present embodiment, the adhesive layer 8 of the circuit connecting material 5 is thermally cured, and finally the circuit connecting body 100 is manufactured. First, the circuit connecting material 5 is cut at a predetermined length, and the adhesive layer 8 faces downward. It is placed on the surface on which the circuit electrode 32 of the first circuit member 30 is formed (Fig. 3(a)). At this time, the substrate 6 is peeled off from the adhesive layer φ 8 . Then, the pressure is applied in the directions of arrows A and B in Fig. 3(b), and the adhesive layer 8 is temporarily connected to the first circuit member 30 (Fig. 3(c)). The pressure at this time is not particularly limited as long as it does not cause damage to the circuit member, but is generally preferably 0.1 to 3.0 MPa. Further, it may be pressurized while being heated, and the heating temperature is set to a temperature which does not substantially cure the adhesive layer 8. The heating temperature is generally preferably 50 to 100 ° C, and such heating and pressurization are preferably carried out in the range of 0.1 to 10 seconds. Next, as shown in Fig. 3(d), the second circuit member 40 is placed on the adhesive layer 8 on the side of the second circuit electrode 42 facing the first circuit member 30. Then, while the adhesive layer 8 is heated, the entire pressure is applied in the directions of arrows A and B in Fig. 3(d). The heating temperature at this time is set at a temperature at which the adhesive component 9 of the adhesive layer 8 can be hardened. The heating temperature is preferably 150 to 230 ° C, preferably 170 to 210 ° C, and more preferably 180 to 200 ° C. When the heating temperature is lower than 150 °C, the curing rate tends to be slow, and when it exceeds 230 °C, undesired side reactions tend to proceed. The heating time is preferably 0.1 to 30 seconds, preferably 1 to 25 seconds, and more preferably 2 to 20 seconds. -18- 200932860 The connecting portion 50a is formed by hardening of the adhesive component 9, and the circuit connecting body 100 shown in Fig. 2 is obtained. The conditions of the connection can be appropriately selected depending on the use, the adhesive composition, and the circuit member. Further, when the adhesive component of the adhesive layer 8 is blended and cured by light, the adhesive layer 8 may be appropriately irradiated with active light or energy rays. Examples of the active light include ultraviolet rays, visible light, and infrared rays; and examples of the energy rays include electron beams, X-rays, γ rays, and microwaves. The above is a description of the preferred embodiments of the present invention, and the present invention is not limited to the embodiments described above, and various modifications may be made without departing from the spirit and scope of the invention. For example, in the above embodiment, the adhesive composition containing the conductive particles 10 Α is exemplified, but the adhesive composition may be such that the conductive particles 10A are not contained depending on the shape of the circuit member to be mounted or the like. Further, in place of the conductive particles 10A, conductive particles composed of conductive core particles and a plurality of insulating particles provided on the surface of the core particles can be used. The conductive particles 10B shown in FIG. 4 are provided with conductive core particles. 1 and a plurality of insulating particles 2 provided on the surface of the core particles 1, and then the core particles 1 are composed of a base portion. The material particles la and the conductive layer 1b provided on the surface of the substrate particles 1a are formed. Hereinafter, the conductive particles 10B will be described. Examples of the material of the substrate particles 1a include glass, ceramics, and organic polymer compounds. Among these materials, those which are deformed by heating and/or pressurization (e.g., glass, organic polymer compound) are preferred. When the substrate particles la are deformed, when the conductive particles 10B are pressed by the circuit electrodes 32, 42, the contact area with the circuit electrode is increased by -19-200932860, and the surface of the circuit electrode 32'42 is absorbing the unevenness of the surface of the circuit electrode 32'42. The connection reliability between the electrodes is improved. From the viewpoint of the above, it is suitable as a material constituting the substrate particles 1a, for example, an acrylic resin, a styrene resin, a benzoguanamine resin, a polyoxyalkylene resin, a polybutadiene resin, or the like. Copolymers, and 'crosslinking these. The substrate particles la may be of the same or different types of materials, and one material may be used alone or two or more materials of φ may be used in the same particles. The average particle diameter of the substrate particles la can be appropriately designed depending on the application, etc., but 0.5 to 20 μm is preferable, 1 to 10 μm is preferable, and 2 to 5 μm is more preferable. When conductive particles are produced using substrate particles having an average particle diameter of less than 0.5 μm, secondary aggregation of particles occurs, and insulation between adjacent circuit electrodes tends to be insufficient, and conductive particles of more than 20 μm are used to form conductive particles. The size of the particles tends to cause insufficient insulation between adjacent circuit electrodes due to their size. The conductive layer 1b is a layer made of a conductive material on the surface of the coated substrate particle 1a, and the conductive layer lb covers the entire surface of the substrate particle la. The surface is preferred. The material of the conductive layer 1 b may, for example, be an alloy of gold, silver, platinum, nickel, copper or the like, an alloy containing tin or the like, or a non-metal having conductivity such as carbon. Since the substrate particles la can be coated by electroless plating, the material of the conductive layer 1b is preferably metal. In addition, in order to obtain a sufficient pot life, it is preferable to use gold, silver, platinum or the like. In addition, these may be used alone or in combination of two or more. -20- 200932860 The thickness of the conductive layer lb can be preferably 50~200nm or 80~150nm depending on the material used or suitable. 5 Onm, there is a case where a sufficiently low resistance 连接 of the connection portion cannot be obtained. On the one hand, the conductive layer lb having a thickness exceeding 200 nm tends to be lowered. The conductive layer 1b may be composed of one layer or two or more layers, and the surface layer of the orthostatic core particle 1 which is preserved by the adhesive composition prepared by using the same may be made of gold, silver, lead or the like. Good, with gold is better. When the conductive layer 1b is made of an alloy of gold or silver (hereinafter referred to as "metal such as gold"), in order to obtain a sufficiently low resistance 连接 of the connection portion, 3 10 to 200 nm is preferable. On the other hand, when the conductive layer 1b is formed of two or more layers, the outermost layer of lb is preferably made of a metal such as gold, but the layer between the outermost layers la may be, for example, nickel, copper, tin or the like. In the case of the metal layer, the thickness of the metal layer formed by the outermost metal constituting the conductive layer 1b is preferably 30 to 200 nm from the viewpoint of the adhesive composition. In the case of town, copper, tin, or the like, free radicals may occur due to redox reaction. When the thickness of the outermost layer made of a metal such as gold is less than 30 nm, there is a radical polymerizable adhesive component. The tendency of fully free radicals becomes difficult. The conductive layer 1b is formed on the surface of the substrate particle 1a by electroless plating treatment or physical coating treatment, and the thickness is lower than the tendency of the pen use or the like, and the production efficiency is also a case where gold constitutes lead. Or the thickness of the layers is such that the thickness of the alloy layer such as the conductive layer and the substrate grain is preserved or the like, and therefore, the method for preventing the liberation is used, and the method of preventing the liberation is lb - 21 - 200932860 From the viewpoint of easiness of formation, the conductive layer 1b made of a metal is preferably formed on the surface of the substrate particle 1a by electroless plating, and is preferably composed of an organic polymer compound. As the organic polymer compound, it is preferred to have a thermosoftening property. Suitable materials for insulating particles, such as polyethylene, ethylene-acetic acid copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-methene-(meth)acrylate copolymer , polyester, polyamide, polyurethane, polystyrene, styrene-divinylbenzene copolymer, styrene-isobutylene copolymer, styrene-butadiene copolymer, styrene-(A (Acrylic acid) copolymer, ethylene-propylene copolymer '(meth)acrylate rubber, styrene-ethylene-butene copolymer, phenoxy resin, solid epoxy resin, and the like. These may be used alone or in combination of two or more. Further, the styrene-(meth)acrylic copolymer is particularly suitable from the viewpoints of the degree of dispersion of the particle size distribution, the solvent resistance, and the heat resistance, and examples of the method for producing the insulating particles 2 include seeds. Seed) polymerization method, etc. The softening point of the organic polymer compound constituting the insulating particles 2 is preferably a heating temperature or more when the circuit members are connected to each other, and the softening point is lower than the heating temperature at the time of connection, because the insulating particles 2 are connected because of Excessive deformation, and the tendency to obtain excellent electrical connections is not obtained. The average particle diameter of the insulating particles 2 can be appropriately designed depending on the application, etc., preferably 50 to 500 nm, more preferably 50 to 400 nm, and still more preferably 100 to 300 nm. When the average particle diameter is less than 5 Onm, the insulation between adjacent circuits tends to be insufficient. On the other hand, when the average particle size exceeds 500 nm, the initial resistance of the connection portion is reduced to 22-200932860. Both the enthalpy and the suppression of the rise in resistance 値 tend to change. Further, the circuit connecting material of the present invention, such as the circuit connecting material 5 in the above-described embodiment, is not limited to the single layer structure in which the single-adhesive layer 8 is formed on the substrate 6, and may be on the upper layer of the substrate 6. The multilayer structure of the composite layer is combined. The circuit connecting material of the multilayer structure may be manufactured by using a plurality of layers of the adhesive component and the type of the conductive particles or the content of the conductive particles, for example, the circuit connecting material may be provided with a layer of conductive particles containing conductive particles, and disposed thereon. A layer containing no conductive particles on at least the surface of the layer containing the conductive particles. The circuit connecting material 15 shown in Fig. 5 has a two-layered adhesive layer 7 and the outermost substrate 6b on both sides of which the adhesive layer 7 is coated. The adhesive layer 7 of the circuit connecting material 10 is composed of a layer 7a containing conductive particles and conductive particles 7b and a non-conductive layer 7b containing no conductive particles. The circuit connecting material 15 is formed on the surface of the substrate 6a to form a layer 7a containing conductive particles, and on the other hand, on the surface of the substrate 6b, a layer 7b containing no conductive particles is formed, which can be attached by using a prior art machine or the like. When the circuit connecting material 15 is used, the base materials 6a, 6b are locally peeled off. According to the circuit connecting material 15, the number of conductive particles of the circuit electrode due to the flow of the adhesive component is sufficiently suppressed when the circuit members are joined to each other. Therefore, for example, when the 1C wafer is attached to the substrate by mounting or COF mounting, the number of conductive particles on the 1C metal bump can be sufficiently ensured. At this time, the adhesive having the IC crystal hard coating layer is laminated on the upper surface of the particle containing the coating agent 6a, and the surface of the -23-200932860 metal bump of the COG wafer can be applied. On the other hand, the substrate 7b which does not contain conductive particles is preferably provided with a substrate of a 1C wafer and a layer 7a containing conductive particles, and the circuit connecting material 7 is disposed in contact with each other. [Embodiment] [Examples] (Example 1) @ A conductive particle having a conductivity, that is, a crosslinked polystyrene particle as a substrate particle (manufactured by Toray Chemical Co., Ltd., trade name: SX series, average particle diameter: 4 μm), on the surface of the particles, a Ni layer (thickness: 0.08 μm) was provided by electroless plating treatment, and an electroless plating treatment was provided on the outer side of the Ni layer. The Au layer (thickness 0.03 μmη) was obtained as a core particle having a conductive layer made of a Ni layer and an Au layer. As an organic polymer compound (insulating coating) for coating the surface of the core particle, a crosslinked acrylic resin (trade name: Q MP series) was prepared, and 4 g of the crosslinked acrylic resin and 20 g of the core particle were introduced. Hybridizer (manufactured by Nara Machinery Co., Ltd., trade name: NHS series), conductive particles were produced, and the processing conditions of the hybridizer were set at a rotation speed of 16,000/min and a reaction tank temperature of 60 °C. Next, using a bisphenol A type epoxy resin and 9,9'-bis(4-hydroxyphenyl)fluorene, a phenoxy resin having a glass transition temperature of 80 ° C was synthesized, and 50 g of the phenoxy resin was dissolved in a solvent to prepare A solution having a solid content of 40% by mass, and a solvent of a mixed solvent of toluene and ethyl acetate (mixing mass ratio of both = 1 : 1 ) was used as a solvent. -24- 200932860 On the other hand, an acrylic copolymer having a crosslinked structure was produced by copolymerizing a monomer raw material having the composition shown in Table 1, and the average molecular weight of the acrylic copolymer produced in the present example was 4 0 0 0 0 (in terms of polystyrene), the glass transition temperature Tg was -10 ° C, and the acrylic copolymer was dissolved in ethyl acetate to prepare a solution having a solid content of 40% by mass. 45 parts by mass (solid content) of the mixed phenoxy resin, 15 parts by mass (solid content) with the acrylic copolymer, and 40 parts by mass of the liquid epoxy resin containing the microcapsule-type latent Q hardener (imidazole-based curing agent) (Solid component) The solution of the adhesive component was obtained by mixing 5 parts by volume of the above-mentioned conductive particles with respect to 100 parts by volume of the adhesive component, and stirring was carried out at a temperature of 23 ° C to obtain a solution of the adhesive composition. A solution of the adhesive composition was applied to a surface of a surface-treated PET film (manufactured by Teijin DuPont Film Co., Ltd., trade name: Purex, thickness: 50 μm) by a release treatment agent (polyoxyalkylene resin). After coating, it was subjected to hot air drying (Ο at 80 ° C for 5 minutes) to obtain a layer containing conductive particles supported by a thickness of PET film. _ 40 parts by mass (solid content) of mixed phenoxy resin, 15 parts by mass (solid content) with acrylic copolymer, and liquid epoxy resin containing microcapsule-type latent curing agent (imidazole-based curing agent) A part by mass (solid content), and a solution containing an adhesive component containing conductive particles is obtained. The solution of the adhesive component was applied to a PET film (manufactured by Teijin DuPont Film Co., Ltd., trade name: Purex, thickness: 50 μm) which was subjected to surface treatment by a release treatment agent (polyoxane resin). On the surface -25- 200932860 and coated. Then, by subjecting it to hot air drying (at 80 ° C for 5 minutes), a layer of non-conductive particles having a thickness of 15 μm supported by a PET film was obtained. These adhesive films are bonded to each other using a laminator known in the prior art, thereby obtaining a circuit connecting material 0 of a two-layer structure as shown in FIG. 5 (production of a circuit connecting body) using the above-described method. Manufactured circuit connecting material, connecting ΙΤΟ substrate (thickness 〇.7mm, surface resistance) <20 Ω/〇) and a 1C wafer (thickness 0.55 mm) to form a circuit connector. For the 1C wafer, a gold bump having a bump area of 2500 μm 2 (50 μm η 50 μm), a pitch ΙΟΟμηη, and a height of 20 μm was used, and the ruthenium substrate was used for forming ITO by vapor deposition on the surface of a glass plate having a thickness of 1.1 mm. The 1C wafer and the ITO substrate were connected via a circuit-connecting material using a press-clamping device (manufactured by Tor ay Engineering Co., Ltd., trade name: FC-1200). Specifically, first, the PET film on the layer side containing the conductive particles is peeled off, and a circuit connecting material is placed on the IT Ο substrate, and the layer containing the conductive particles is brought into contact with the ITO substrate, and then temporarily pressed using a pressing device ( The temperature was 75 ° C and the pressure was 1.0 MPa for 2 seconds. Then, the PET film on the side of the layer not containing the conductive particles was peeled off, and then the 1 C wafer was placed so that the gold bumps abutted against the layer containing no conductive particles. By using quartz glass on the susceptor, the substrate was heated and pressurized at a temperature of 200 ° C and a pressure of 80 MPa for 5 seconds to obtain a circuit connecting body having a connection portion. -26- 200932860 (Measurement of the amount of warpage) The amount of warpage of the ITO substrate after mounting the 1C wafer was measured using a non-contact laser type 3 dimensional shape measuring device (manufactured by KEYENCE, trade name: LT-9000). . The 1C wafer side was placed downward, and the inside of the ITO substrate was placed upward to place the circuit connector on a flat stage. Then, the difference between the height of the center portion of the inner surface of the ITO substrate and the height at which the both ends of the 1C wafer in the inner surface U of the ITO substrate was 5 mm was measured, and the difference in height was defined as the amount of warpage of the glass substrate. (Measurement of initial connection resistance)
將如上述作法所製作的電路連接體的連接部的初期電 阻使用電阻測量機（股份有限公司ADV ANTE ST製、商品 名：數位電表）測量，再者，測量係於電極間流動1mA 的電流而進行。 . (連接信賴性的評估） 關於電路連接體的連接部的連接信賴性，藉由進行溫 度循環試驗而評估，溫度循環試驗係藉由將電路連接體收 納於溫度循環槽（ETAC製、商品名：NT 1 020 )內’從室 溫降溫至-40°C、從-40°C昇溫至1〇〇°C及從l〇〇°C降溫至室 溫的溫度循環重複進行5 00次而進行。_40°c及100乞中保 持時間，皆爲30分鐘，溫度循環試驗後的連接部分的電 阻的測量，與初期電阻的測量同樣地進行。 -27- 200932860 (鄰接電極間的絕緣性的評估） 將鄰接的電極間的絕緣電阻使用電阻測量機（股份有 限公司ADVANTEST製、商品名：數位電表），用以下的 順序測量。首先，對電路連接體的連接部外加1分鐘的直 流（DC ) 5 0V的電壓，然後，絕緣電阻的測量，係對電壓 印加後的連接部藉由2端子測量法進行。再者，上述的電 φ 壓的外加，使用電壓計（股份有限公司ADVANTEST製、 商品名：ULTRA HIGH RESISTANCE METER )。 (貯藏彈性率與玻璃轉化溫度的測量） 使本實施例所製作的二層構成的電路連接材料以 2〇〇°C加熱1小時而硬化，由電路連接材料的硬化物切取 出被測量試料（寬度5mm、長度20mm、膜厚25 μιη )，如 下述作法測量貯藏彈性率及玻璃轉化溫度，亦即，關於被 Ο 測量試料的動態黏彈性，使用動態黏彈性測量裝置RASII . (TAINSTRUMENTS製），以昇溫速度5。(： /分鐘、周波數 1 0Hz、振幅3 μιη、拉伸模式的條件進行測量，然後，由所 得到的結果，計算得到於-5 0。(：及1 0 01：的貯藏彈性率、與 tanS的最大値（玻璃轉化溫度；Tg )。 表3中列示被測量試料（電路連接材料的硬化物）之 於-5〇°C及100它的貯藏彈性率、於-50〜100。(：的範圍的被測 里試料的貯藏彈性率的最大値及最小値、以及、玻璃轉化 溫度。此外’表4中列示ITO基板的翹曲量、連接電阻値 -28- 200932860 、絕緣電阻値的測量結果。 (實施例2) 除了取代重量平均分子量4〇xl〇3的丙烯酸系共聚物 ，使用由表1的實施例2的攔中所表示的單體原料所製造 的重量平均分子量5 0 X 1 03的丙烯酸系共聚物之外，與實 施例1同樣地製作二層構成的電路連接材料及電路連接體 (實施例3 ) 除了取代重量平均分子量4〇χ103、玻璃轉化溫度-l〇°C 的丙烯酸系共聚物，使用由表1的實施例3的欄位所表示 的單體原料所製造的重量平均分子量70 χΙΟ3、玻璃轉化溫 度_5°C的丙烯酸系共聚物之外，與實施例1同樣作法，製 作=層構成的電路連接材料及電路連接體。 (實施例4) 除了取代重量平均分子量40χ103、玻璃轉化溫度-10¾ 酸系共聚物，使用由表丨的實施例4的欄位所表示 的單體原料所製造的重量平均分子量60x1 〇3、玻璃轉化溫 度〇°C的丙烯酸系共聚物之外，與實施例1同樣作法，製 ί乍成的電路連接材料及電路連接體。 (實施例5 ) -29- 200932860 除了取代重量平均分子量40χ103、玻璃轉化溫度-i(TC 的丙烯酸系共聚物，使用由表1的實施例5的欄位所表示 的單體原料所製造的重量平均分子量7〇χ103、玻璃轉化溫 度l〇°C的丙烯酸系共聚物之外，與實施例1同樣作法，製 作二層構成的電路連接材料及電路連接體。 (比較例1 ) φ 製作二層構成的電路連接材料時，除了各溶液中未摻 合具有交聯結構的丙烯酸系共聚物，以表2所表示的摻合 比率形成含有導電粒子之層及非含有導電粒子之層之外， 與實施例1同樣作法，製作二層構成的電路連接材料及電 路連接材料。 [表1] 實施例1 實施例2 實施例3 實施例4 實施例5 丙烯酸系共聚物的 製造所使用的單體 原料的組成 (質量份） 甲基丙烯酸縮水甘 油酯 5 5 6 7 3 丁基丙烯酸酯/ 苯乙烯柄烯腈 95 95 94 93 97 丙烯酸系共聚物的窜暈平均分子量 (聚苯乙烯換算） 4〇χ103 5〇χ103 7〇xl03 6〇xl03 7〇χ103 丙烯酸系共聚物的玻璃轉化溫度 -10 -10 -5 0 10 -30- 200932860 [表2] 實施例1〜5 比較例1 含有導電粒子之層的組成 苯氧樹脂 45質量份 5〇質量份 丙烯酸系共聚物 15質量份 液狀環氧樹脂(含硬化劑） 40質量份 5〇質量份 導電粒子 5體積份 5體積份 非含有導電粒子之層的組 成 苯氧樹脂 40質量份 40質量份 丙烯酸系共聚物 15質量份 纖環氧樹脂(含硬化劑） 45質量份 6〇質量份 [表3] 電路連接材料的硬化物 的物性 實施例1 實施例2 實施例3 實施例4 實施例5 比較例1 於-50。。之貯藏彈性率 (GPa) 2.1 2.3 2.4 2.6 2.8 3.5 於l〇〇°C之貯藏彈性率 (GPa) 1.1 1.3 1.5 1.6 1.8 2.2 玻璃轉化溫度(t：) 118 123 130 133 135 145 [表4] 實施例1 實施例2 實施例3 實施例4 實施例5 比較例1 ITO基板的翹曲(μιη) 5 6 6 7 8 14 連接電阻 値(Ω) 初期 <1 <1 <1 <1 <1 <1 溫度循環試驗後 <3 <3 <3 <3 <3 <3 鄰接電極間的絕緣電阻値 (Ω) >1013 >1013 >1013 >1013 >1013 >1012The initial resistance of the connection portion of the circuit connector produced as described above was measured using a resistance measuring machine (manufactured by ADV ANTE ST, trade name: digital electric meter), and the measurement was performed by flowing a current of 1 mA between the electrodes. get on. (Evaluation of connection reliability) The connection reliability of the connection portion of the circuit connector was evaluated by performing a temperature cycle test, and the temperature cycle test was performed by accommodating the circuit connection body in a temperature cycle groove (ETAC system, trade name) :NT 1 020 ) The temperature cycle from 'room temperature drop to -40 ° C, from -40 ° C to 1 ° ° C and from l ° ° C to room temperature is repeated for 500 times. . The holding time in _40 ° c and 100 , was 30 minutes, and the measurement of the resistance of the connection portion after the temperature cycle test was performed in the same manner as the measurement of the initial resistance. -27- 200932860 (Evaluation of the insulation between the adjacent electrodes) The insulation resistance between the adjacent electrodes was measured in the following order using a resistance measuring machine (manufactured by the company, ADVANTEST, trade name: digital electric meter). First, a direct current (DC) of 50 V is applied to the connection portion of the circuit connector, and then the measurement of the insulation resistance is performed by the 2-terminal measurement method for the connection portion after the voltage is applied. Further, the above-mentioned electric φ pressure is applied by using a voltmeter (manufactured by ADVANTEST Co., Ltd., trade name: ULTRA HIGH RESISTANCE METER). (Measurement of storage modulus and glass transition temperature) The circuit connecting material of the two-layer structure produced in the present example was cured by heating at 2 ° C for 1 hour, and the sample to be measured was cut out from the cured material of the circuit connecting material ( The width is 5 mm, the length is 20 mm, and the film thickness is 25 μm. The storage elastic modulus and the glass transition temperature are measured as follows. That is, regarding the dynamic viscoelasticity of the sample to be measured by the beryllium, a dynamic viscoelasticity measuring device RASII (manufactured by TAINSTRUMENTS) is used. At a heating rate of 5. The conditions of (:/min, the number of cycles of 10 Hz, the amplitude of 3 μιη, and the tensile mode were measured, and then, from the obtained results, the storage elastic modulus of -5 0 (: and 1 01::) was calculated. The maximum enthalpy of tanS (glass transition temperature; Tg). Table 3 shows the measured sample (hardened material of circuit connecting material) at -5 ° C and 100 its storage modulus, from -50 to 100. The range of the storage elastic modulus of the sample to be tested is the maximum 値 and minimum 値, and the glass transition temperature. In addition, the amount of warpage of the ITO substrate, the connection resistance 値-28-200932860, and the insulation resistance 値 are listed in Table 4. (Example 2) The weight average molecular weight manufactured by using the monomer raw material represented by the stopper of Example 2 of Table 1 was used, except that the acrylic copolymer having a weight average molecular weight of 4 〇 x 10 〇 3 was replaced. A circuit connecting material and a circuit connecting body having a two-layer structure were produced in the same manner as in Example 1 except for the acrylic copolymer of X 1 03 (Example 3) except that the weight average molecular weight was 4〇χ103, and the glass transition temperature was -10°. C acrylic copolymer, used by The same procedure as in Example 1 was carried out except that the weight average molecular weight of the monomer raw material represented by the column of Example 3 in Table 3 was 70 χΙΟ3 and the glass transition temperature was _5 °C. Circuit connection material and circuit connector. (Example 4) Except that a weight average molecular weight of 40 χ 103 and a glass transition temperature of -103⁄4 acid copolymer were used, the monomer raw material represented by the column of Example 4 of the Table 4 was used. In the same manner as in Example 1, except for the acrylic copolymer having a weight average molecular weight of 60x1 〇3 and a glass transition temperature of 〇 °C, a circuit connecting material and a circuit connecting body were produced. (Example 5) -29- 200932860 In addition to replacing the weight average molecular weight of 40χ103, glass transition temperature-i (TC of acrylic copolymer, the weight average molecular weight of 7〇χ103 produced by the monomer starting material represented by the column of Example 5 of Table 1, glass conversion A circuit connecting material and a circuit connecting body having a two-layer structure were produced in the same manner as in Example 1 except for the acrylic copolymer having a temperature of 10 ° C. (Comparative Example 1) φ A two-layer structure was produced. In the case of a circuit-connecting material, in addition to the acrylic copolymer having a crosslinked structure in each solution, a layer containing conductive particles and a layer containing no conductive particles are formed at a blending ratio shown in Table 2, and In the same manner as in Example 1, a circuit connecting material and a circuit connecting material having a two-layer structure were produced. [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 A monomer raw material used for the production of an acrylic copolymer Composition (parts by mass) Glycidyl methacrylate 5 5 6 7 3 Butyl acrylate / styrene styrene nitrile 95 95 94 93 97 Acrylic copolymer of halo average molecular weight (in terms of polystyrene) 4〇χ103 5 〇χ103 7〇xl03 6〇xl03 7〇χ103 Glass transition temperature of the acrylic copolymer -10 -10 -5 0 10 -30- 200932860 [Table 2] Examples 1 to 5 Comparative Example 1 Composition of a layer containing conductive particles Phenoxy resin 45 parts by mass of 5 parts by mass of acrylic copolymer 15 parts by mass of liquid epoxy resin (containing curing agent) 40 parts by mass of 5 parts by mass of conductive particles 5 parts by volume of 5 parts by volume of layer not containing conductive particles 40 parts by mass of phenoxy resin 40 parts by mass of acrylic copolymer 15 parts by mass of epoxy resin (containing curing agent) 45 parts by mass of 6 parts by mass [Table 3] Physical properties of cured product of circuit connecting material Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 was at -50. . Storage Elasticity (GPa) 2.1 2.3 2.4 2.6 2.8 3.5 Storage Elasticity (GPa) at l〇〇°C 1.1 1.3 1.5 1.6 1.8 2.2 Glass transition temperature (t:) 118 123 130 133 135 145 [Table 4] Implementation Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Warpage of an ITO substrate (μιη) 5 6 6 7 8 14 Connection resistance 値 (Ω) Initial <1 <1 <1 <1 <1 <1 After temperature cycle test <3 <3 <3 <3<3<3<3>3 Insulation resistance 値(Ω) between adjacent electrodes >1013 >1013 >1013 >1013 >1013 >1012
[產業上的可利用性] 依據本發明，即使以200。(3左右的高溫條件進行電路 構件彼此的連接時，亦可充分地抑制電路構件的翹曲。 -31 - 200932860 【圖式簡單說明】 [圖π係表示本發明該相關的電路連接材料之一實施 形態的截面圖。 . [圖2]係表示本發明該相關的電路連接材料被使用於 電路電極間，電路電極彼此經連接的狀態之截面圖。 [圖3]係藉由槪略截面圖表示本發明該相關的電路構 @ 件的連接方法之一實施形態之步驟圖。 [圖4]係表示導電粒子的其他形態之截面圖。 [圖5]係表示本發明該相關的電路連接材料的其他實 施形態之截面圖。 【主要元件符號說明】 5，15 :電路連接材料 6，6a，6b :基材 〇 7a:含有導電粒子之層 . 7b :非含有導電粒子之層 8 :黏著劑層 9 :黏著劑成分 10A，10B :導電粒子 30 :第1電路構件 40 :第2電路構件 50a :連接部 100 :電路連接體 -32-[Industrial Applicability] According to the present invention, it is even 200. (When the circuit members are connected to each other at a high temperature condition of about 3, the warpage of the circuit member can be sufficiently suppressed. - 31 - 200932860 [Simplified description of the drawings] [Fig. π shows one of the related circuit connecting materials of the present invention. Fig. 2 is a cross-sectional view showing a state in which the circuit connecting material of the present invention is used between circuit electrodes and circuit electrodes are connected to each other. [Fig. 3] is a schematic cross-sectional view Fig. 4 is a cross-sectional view showing another embodiment of the connection method of the circuit structure of the present invention. Fig. 4 is a cross-sectional view showing another form of the conductive particles. [Fig. 5] shows the related circuit connecting material of the present invention. Cross-sectional view of other embodiments. [Explanation of main component symbols] 5,15: circuit connection material 6,6a,6b: substrate 〇7a: layer containing conductive particles. 7b: layer 8 containing no conductive particles: adhesive Layer 9: Adhesive component 10A, 10B: Conductive particle 30: First circuit member 40: Second circuit member 50a: Connection portion 100: Circuit connector - 32-