201105698 六、發明說明 【發明所屬之技術領域】 本發明關於適合於電子零件的密封用之電子零件用液 狀樹脂組成物及由其所密封的電子零件裝置， 【先前技術】 向來，於以電晶體、1C等的電子零件裝置爲對象的 元件密封之領域中，從生產性、成本等的方面來看，樹脂 密封係成爲主流，廣泛使用環氧樹脂組成物。其理由爲環 氧樹脂可以在操作性、成形性、電特性、耐濕性、耐熱 性、機械特性、與插入品的黏著性等諸特性中取得平衡。 C OB (Chip on Board)、COG(Chip on Glass)、TCP(Tape Carrier Package)等的裸晶組裝之半導體裝置中，廣泛使 用電子零件用液狀樹脂組成物當作密封材。近年來，作爲 液晶等的顯示器驅動用1C之組裝方法，使用於將半導體 元件直接以凸塊連接於電路基板的組裝形態（覆晶連接方 式），已知此組裝中所用的電子零件用液狀樹脂組成物係 當作底部塡充材。 此底部塡充材係在上述覆晶連接方式的導體組裝方法 中，以凸塊間的絕緣保持及機械強度保持用之密封爲目 的，塡充於電路基板與半導體裝置之間所產生的空間內。 因此，於底部塡充材中，（1)在常溫爲低黏度的液體，（2) 爲了避免塡充後的樹脂在熱硬化過程中發生氣泡（空洞）， 樹脂組成物係無溶劑，（3)爲了避免黏度的增加、滲透性 -5- 201105698 的降低，儘可能避免含有塡料等的固體成分，（4)含有固 體成分時’保持電子零件用液狀樹脂組成物中的固體成分 之均一分散性，做不損害黏度、流動性、滲透性等的粒度 分布、塡充量之管理的適切配合等之條件係爲必要項目。 於上述電路基板及半導體裝置中，配線間的間隔變 窄，於最尖端的覆晶半導體裝置中，配線間距亦可能 3 0 μιη以下。因此，經由在窄間距化的配線間施加高的電 壓，對於電子零件用液狀樹脂組成物而言，作爲損害絕緣 可靠性的不良現象之一，有遷移現象大的問題。特別地， 由於在高溫高濕下促進樹脂及配線金屬的劣化，遷移變容 易發生，半導體裝置的不良發生之虞有更升高的傾向。 爲了避免該不良，事先對於電子零件所使用的樹脂組 成物，進行以遷移抑制爲目的之對策。例如，作爲金屬離 子補捉劑，眾所周知配合有無機離子交換體的樹脂組成物 (例如參照專利文獻1〜4)、配合有苯并三哄、苯并三唑或 此等的異氰尿酸加成物之樹脂組成物（例如參照專利文獻 5〜10)、於硬化促進劑中配合有含硼酸鹽的化合物之樹脂 組成物（例如參照專利文獻1 1 )、配合有抗氧化劑的樹脂組 成物（例如參照專利文獻1 2〜1 3 )等，係作爲供應給密封 材、黏著劑、預浸物等的用途之樹脂組成物。 於前述眾周知例之中，專利文獻12〜13例示的配合 有抗氧化劑之樹脂組成物，已知在以預浸物爲代表的印刷 基板用樹脂組成物中，除了防止樹脂劣化的效果，還有耐 遷移性特別優異。於印刷基板用樹脂組成物中配合時，由 -6- 201105698 於使用甲基乙基酮（MEK)或甲苯等的溶劑，一般常溫爲固 體（粉末狀）的各種抗氧化劑可與環氧樹脂、硬化劑、硬化 促進劑一起混合、溶解，按照用途或特性，可選擇任意的 抗氧化劑》 [專利文獻1]特開平6-158492號公報 [專利文獻2]特開平9_3丨4758號公報 [專利文獻3]特開2000- 1 83470號公報 [專利文獻4]特開2007-63549號公報 [專利文獻5]特開2001 -6769號公報 [專利文獻6]特開2001 -203462號公報 [專利文獻7]日本發明專利第3 8 8 1 2 8 6號 [專利文獻8]特開2005-72275號公報 [專利文獻9]特開2005-333085號公報 [專利文獻10]特許第363 3422號 [專利文獻1 1]特開2008-7577號公報 [專利文獻12]特開平3 -3 93 20號公報 [專利文獻13]特開平1 0-279779號公報 【發明內容】 發明所欲解決的問題 對於此，作爲底部塡充材使用的電子零件用液狀樹脂 組成物，如前述地，在塡充後的樹脂之熱硬化過程中，爲 了避免氣泡（空洞）的發生，不使用溶劑。因此，於無溶劑 的電子零件用液狀樹脂組成物中，將習知的抗氧化劑均勻 201105698 地溶解，且不損^低黏度性、高流動性'高滲透性或速硬 化性、低吸水性、高黏著性等之作爲底部塡充材的必要諸 特性而得到ρ遷移性優異的電子零件用液狀樹脂組成物係 困難。 目前，藉由減低電子零件用液狀樹脂組成物中的雜質 而謀求耐遷移性的提高。然而，例如在細線化、窄間距化 顯著的代表性半導體裝置之COF(Chip On Film)中，更要 求耐遷移性的提高，僅電子零件用液狀樹脂組成物的高純 度化係難以對應。 本發明係鑒於如此的狀況而完成者，提供耐遷移性良 好，其它成形性、可靠性亦優異的電子零件用液狀樹脂組 成物及經由其所密封的電子零件裝置。 解決問題的手段 本發明者們爲了解決上述問題，重複專心致力的檢 討’結果發現藉由採用半導體元件等的電子零件與電路基 板的黏著性良好，吸水率小，抑制氧化降解、低黏度且流 動性優異的高純度電子零件用液狀樹脂組成物，可達成上 述目的，終於完成本發明。 本發明關於以下（1)〜（15)。 (1) 一種電子零件用液狀樹脂組成物，其含有（A)環氧 樹脂' (B)常溫液體的環狀酸酐、（〇偶合劑、（D)抗氧化 劑。 (2) 如前述（1)記載的電子零件用液狀樹脂組成物，其 201105698 中（D)抗氧化劑含有在酚核的鄰位至少具有1個烷基的酚 化合物。 (3 )如前述（1)記載的電子零件用液狀樹脂組成物，其 中（D)抗氧化劑含有在酚核的鄰位具有1個甲基的酚化合 物。 (4) 如前述（2)或（3)記載的電子零件用液狀樹脂組成 物，其中（D)抗氧化劑在雙酚F型環氧樹脂中的飽和溶解 量爲5重量％以上。 (5) 如前述（1)記載的電子零件用液狀樹脂組成物，其 中（D)抗氧化劑含有二環己基胺或其衍生物。 (6) 如前述（1)〜（5)中任一項記載的電子零件用液狀樹 脂組成物，其中更含有無機塡充劑，而且無機塡充劑的配 合量爲10質量％以下。 (7) 如前述（1)〜（6)中任一項記載的電子零件用液狀樹 脂組成物，其中更含有橡膠粒子。 (8) 如前述（1)〜（7)中任一項記載的電子零件用液狀樹 脂組成物，其中更含有聚矽氧改性環氧樹脂。 (9) 如前述（1)〜（8)中任一項記載的電子零件用液狀樹 脂組成物，其中更含有離子捕捉劑。 (10) 如（1)〜（9)中任一項記載的電子零件用液狀樹脂 組成物，其中更含有促進（A)與（B)之反應的潛在性硬化促 進劑。 [S] (1 1)如前述（1)〜（10)中任一項記載的電子零件用液狀 樹脂組成物，其中更且有機溶劑含有率爲1 %以下》 -9 - 201105698 (12) 如前述（1)〜（1 i)中任一項記載的電子零件用液狀 樹脂組成物，其中（B)常溫液體的環狀酸酐之酸酐當量爲 200以上。 (13) 如前述（1)〜（12)中任一項記載的電子零件用液狀 樹脂組成物，其使用EMD型旋轉黏度計在^«^的黏度爲 1 · 2 P a . s 以下。 (14) 如前述（1)〜（13)中任一項記載的電子零件用液狀 樹脂組成物，其係使用於在以薄膜當作基材的電路基板上 直接凸塊連接有電子零件之電子零件裝置。 (15) —種電子零件裝置，其使用前述（1)〜（14)中任一 項記載的電子零件用液狀樹脂組成物來密封。 發明的效果 本發明的電子零件用液狀樹脂組成物，由於係耐遷移 性良好’半導體元件等的電子零件與電路基板之黏著性良 好，吸水率小’抑制氧化降解、低黏度且流動性優異的高 純度電子零件用液狀樹脂組成物，故其工業價値大。尤 其，特別適用作爲藉由凸塊連接半導體元件於剛性電路板 及撓性電路板玻璃上所形成的配線之覆晶接合的半導體裝 置，具體地覆晶BGA或COF等之半導體裝置用的底部塡 充材。 【實施方式】 實施發明的形態 -10- 201105698 本發明中所用的（A)環氧樹脂，只要是硬化可能的在 1分子中具有2個以上的環氧基之環氧樹脂，則沒有特別 的限制，可舉出使用電子零件用液狀樹脂組成物中所一般 使用的環氧樹脂，組成物若爲液狀，可使用固體、液狀的 任一者，亦可倂用兩者。例如可舉出由雙酚A、雙酚F、 雙酚AD、雙酚S、萘二酚、氫化雙酚A等與環氧氯丙烷 之反應所得的縮水甘油醚型環氧樹脂，以鄰甲酚酚醛清漆 型環氧樹脂爲首的使酚類與醛類縮合或共縮合而得之酚醛 清漆樹脂經環氧化的酚醛清漆型環氧樹脂，由苯二甲酸、 二聚酸等的多元酸與環氧氯丙烷之反應所得的縮水甘油醚 型環氧樹脂，由二胺基二苯基甲烷、異氰尿酸等的多胺與 環氧氯丙烷之反應所得的縮水甘油基胺型環氧樹脂，以過 乙酸等的過酸將烯烴鍵氧化而得之線狀脂肪族環氧樹脂、 脂環族環氧樹脂等，可單獨使用此等，亦可組合2種以上 使用。 其中，從低黏度化的觀點來看，較佳爲液狀環氧樹 脂，從與環狀酸酐的反應性之觀點來看，更佳爲雙酚型液 狀環氧樹脂。 又，此等環氧樹脂係經充分精製者，較佳爲離子性雜 質少者。例如，游離 Na離子及游離 C1離子更佳爲 500ppm 以下。 本發明中所用的（B)常溫液體的環狀酸酐係沒有特別 的限制，例如可舉出苯二甲酸酐、馬來酸酐、甲基海明克 酸酐、海明克酸酐、琥珀酸酐、四氫苯二甲酸酐、六氫苯 -11 - 201105698 二甲酸酐、氯菌酸酐、甲基四氫苯二甲酸酐、3 -甲基六氫 苯二甲酸酐、4·甲基六氫苯二甲酸酐、三烷基四氫苯二甲 酸酐馬來酸加成物、甲基六氫苯二甲酸、二苯甲酮四羧酸 酐、偏苯三酸酐、苯均四酸酐、甲基四氫苯二甲酸酐、氫 化甲基納狄克酸酐、由馬來酸酐與二烯化合物經由狄-阿 (Diels-Alder)反應所得之具有複數的烷基之三烷基四氫苯 二甲酸酐、十二烯基琥珀酸酐等之各種環狀酸酐。 所謂的「環狀酸酐」，就是如苯二甲酸酐所代表地， 「-C0-0-C0-」的二個碳原子C各自與其它二個碳原子進 行化學鍵結而形成環狀者。又，「酸酐當量」係以（酸酐 的分子量）/(酸酐分子內的酸酐基之數）表示。 作爲酸酐當量爲200以上的化合物，例如酸酐當量爲 234的日本環氧樹脂股份公司製商品名jERcure YH306等 係以市售品可取得。 於酸酐的酸酐當量未達200時，由於硬化物中的酯鍵 變多，故在高溫高濕下容易受到水解的影響，容易發耐濕 性尤其耐遷移性的降低。又，於酸酐的酸酐當量未達200 時，由於酯基的影響而吸水率亦變高，此亦成爲耐遷移性 降低的原因。即，與酸酐當量小的環狀酸酐相比，由於酸 酐當量大的環狀酸酐係酯基濃度變小，其硬化物爲吸水率 低，故可減低在水中所溶出的C1等之離子性雜質量。 酸酐當量較佳爲200〜400，更佳爲200〜300。 (B)成分的環狀酸酐之構造係沒有特別的限制，從耐 遷移性之觀點來看，較佳爲在分子中不含有氯、溴等的鹵 -12- 201105698 素原子、酯鍵。 於本發明中，可適宜地使用（B)成分以外的硬化劑， 作爲環氧樹脂的硬化劑，可使用一般使用者。例如可舉出 二伸乙三胺 '三伸乙三胺、四伸乙五胺、間二甲苯二胺、 三甲基六亞甲基二胺、2-甲基五亞甲基二胺、二乙基胺基 丙基胺、異佛爾酮二胺、1,3-雙胺甲基環己烷、雙（4-胺基 環己基）甲烷、原冰片烯二胺、1,2-二胺基環己烷、拉若明 (Laromin)、二胺基二苯基甲烷、間苯二胺、二胺基二苯 基碾、聚環氧丙烷二胺、聚環氧丙烷三胺、聚環己基聚胺 混合物、N·胺基乙基哌哄等的胺化合物、2-乙基-4-甲基咪 唑、2-苯基咪唑、1-(2-氰乙基）-2-乙基-4-甲基咪唑、2,4-二胺基-6-(2-甲基咪唑基-(1))乙基-s-三哄、2-苯基咪唑 啉、2,3-二氫-1H-吡咯并（1，2-a)苯并咪唑等的咪唑化合 物、3級胺、DBU、氰胍、有機酸二醯肼' N，N-二甲基脲 衍生物等。其中從低黏度化的觀點來看，較佳爲胺化合 物。 (B)成分之常溫液體的液狀酸酐之配合量，爲了發揮 其性能，相對於含有（B)成分的硬化劑全量而言，較佳爲 30質量％以上，更佳爲40質量％以上，尤佳爲60質量％ 以上。 (A)環氧樹脂與含有（B)成分之常溫液體的環狀酸酐之 全部硬化劑的當量比係沒有特別的限制，爲了壓低各自的 未反應部分，較佳爲相對於環氧樹脂而言，將硬化劑設定 在0.6〜1.6當量的範圍，更佳爲0.7〜1.4當量，尤佳爲 -13- 201105698 0.8〜1.2當量。若偏離0.6〜1.6當量的範圍時，則硬化反 應變不充分，可靠性有降低的傾向。此處，當量係反應當 量，例如酸酐的酸酐當量係相對於1個環氧基而言，將1 個酸酐基當作反應者計算，酚樹脂的當量係相對於1個環 氧基1而言，將1個酚性羥基當作反應者計算，芳香族胺 的當量係相對於1個環氧基而言，將1個胺基的活性氫當 作反應者計算。 本發明中所用的（C)偶合劑係沒有特別限制，可使用 習知者，例如可舉出具有1級及/或2級及/或3級胺基的 矽烷化合物、環氧矽烷、锍基矽烷、烷基矽烷、脲基矽 烷、乙烯基矽烷等的各種矽烷系化合物、鈦系化合物、鋁 螯合物類、鋁/鍩系化合物等。 若例示此等，可舉出乙烯基三氯矽烷、乙烯基三乙氧 基矽烷、乙烯基三（β-甲氧基乙氧基）矽烷、γ-甲基丙烯醯 氧基丙基三甲氧基矽烷、β-(3,4-環氧基環己基）乙基三甲 氧基矽烷、γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧 基丙基甲基二甲氧基矽烷、乙烯基三乙醯氧基矽烷、γ-锍 基丙基三甲氧基矽烷、γ-胺基丙基三甲氧基矽烷、γ-胺基 丙基甲基二甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ-胺 基丙基甲基二乙氧基矽烷、γ-苯胺基丙基三甲氧基矽烷、 γ-苯胺基丙基三乙氧基矽烷、γ-(Ν，Ν-二甲基）胺基丙基三 甲氧基矽烷、γ-(Ν，Ν-二乙基）胺基丙基三甲氧基矽烷、γ-(Ν，Ν-二丁基）胺基丙基三甲氧基矽烷、γ-(Ν-甲基）苯胺基 丙基三甲氧基矽烷、γ-(Ν-乙基）苯胺基丙基三甲氧基矽 -14- 201105698 烷、γ-(Ν,Ν-二甲基）胺基丙基三乙氧基矽烷、γ-(Ν，Ν-二乙 基）胺基丙基三乙氧基矽烷、γ-(Ν,Ν-二丁基）胺基丙基三乙 氧基矽烷、γ-(Ν-甲基）苯胺基丙基三乙氧基矽烷、γ-(Ν-乙 基）苯胺基丙基三乙氧基矽烷、γ-(Ν，Ν-二甲基）胺基丙基甲 基二甲氧基矽烷、γ-(Ν，Ν-二乙基）胺基丙基甲基二甲氧基 矽烷、γ-(Ν,Ν-二丁基）胺基丙基甲基二甲氧基矽烷、γ-(Ν-甲基）苯胺基丙基甲基二甲氧基矽烷、γ-(Ν-乙基）苯胺基丙 基甲基二甲氧基矽烷、Ν-(三甲氧基矽烷基丙基）乙二胺、 Ν-(二甲氧基甲基矽烷基異丙基）乙二胺、甲基三甲氧基矽 烷、二甲基二甲氧基矽烷、甲基三乙氧基矽烷、γ_氯丙基 三甲氧基矽烷、六甲基二矽烷、乙烯基三甲氧基矽烷、γ-毓基丙基甲基二甲氧基矽烷等的矽烷系偶合劑、異丙基三 異硬脂醯基鈦酸酯、異丙基三（二辛基氫磷酸酯）鈦酸酯、 異丙基三（Ν-胺乙基-胺乙基）鈦酸酯、四辛基雙（二個十三 基亞磷酸酯）鈦酸酯、四（2,2-二烯丙氧基甲基-1-丁基）雙 (二個十三基）亞磷酸酯鈦酸酯、雙（二辛基氫磷酸酯）氧基 醋酸酯鈦酸酯、雙（二辛基氫磷酸酯）乙烯鈦酸酯、異丙基 三辛醯基鈦酸酯、異丙基二甲基丙醯基異硬脂醯基鈦酸 酯、異丙基十三基苯磺醯基鈦酸酯、異丙基異硬脂醯基二 丙烯醯基鈦酸酯、異丙基三（二辛基磷酸酯）鈦酸酯、異丙 基三枯基苯基鈦酸酯、四異丙基雙（二辛基亞磷酸酯）鈦酸 酯等的鈦酸酯系偶合劑等。可以單獨使用此等的1種，也 可組合2種類以上使用。 相對於液狀樹脂組成物而言，（C)偶合劑的全部配合 -15- 201105698 量較佳爲0.037〜5.0質量％，更佳爲0.05〜4.75質量％， 尤佳爲0.1〜2,5質量％。若未達〇 _ 〇 3 7質量％，則基板與 液狀樹脂組成物的硬化物之密接性有降低的傾向，而若超 過5 · 0質量％，則玻璃轉移溫度或彎曲強度等的物性有降 低的傾向。 作爲本發明中所用的（D)抗氧化劑，可使用習知者。 例如作爲酚化合物系抗氧化劑之在酚核的鄰位至少具有個 1個烷基的化合物，可舉出2,6-二-t-丁基-4-甲基苯酚、η-十八基-3-(3,5-二-t-丁基-4-羥基苯基）丙酸酯、2,2’-亞甲 基雙-(4-甲基- 6-t-丁 基苯酚）、3,9-雙[2-[3-(3-t-丁基-4-羥 基-5-甲基苯基）丙醯氧基]-1，1-二甲基乙基]-2，4,8,10-四氧 雜螺[5.5]十一烷、4,4’-亞丁基雙-(6-t-丁基-3-甲基苯 酚）、4,4’-硫代雙（6-t-丁基-3-甲基苯酚）、四[亞甲基-3-(3,5-二_t-丁基-4-羥基苯基）丙酸酯]甲烷、2,2-硫代-二亞 乙基雙[3-(3,5-二-t-丁基-4-羥基苯基）丙酸酯]、N，N’-六亞 甲基雙[3-(3,5-二-t-丁基-4-羥基苯基）丙醯胺]、異辛基- 3-(3,5-二-t-丁基-4-羥基苯基）丙酸酯、1，3,5-三甲基-2,4,6-三（3,5-二-t-丁基-4-羥基苄基）苯、4,6-雙（十二基硫甲基ίο-甲酚 、雙 （3,5-二 -t-丁基 -4-羥基苄 基磺酸 乙基）鈣、 2,4-1 雙[(辛硫基）甲基]-〇-甲酚、1，6-己二醇·雙[3-(3,5-二-t-丁 基_4 一經基苯基）丙酸醋]、6-[3-(3-t -丁基·4_經基-5-甲基 苯基）丙氧基]-2,4,8，10-四-t-丁基二苯并[d，f][l，3, 2]二氧 雜膦烷、2-t-丁基-6-(3-t-丁基-2-羥基-5 —甲基苄基）-4-甲 基苯基丙烯酸酯、2-[1-(2_羥基-3,5-二-t-戊基苯基）乙基]- -16- 201105698 酚 4,6-二-t-戊基苯基丙稀酸酯、2,2’-亞甲基雙_(4_乙基_6_t_ 丁基本酣）、2,6 - 一 - t-丁基-4-乙基苯酌、1，丨，3_三（2-甲基_ 4-經基-5-t-丁基苯基）丁院、三乙二醇-雙[3_(3t 丁基-4_ 羥基-5-甲基苯基）丙酸酯] '三（3,5-二_t_丁基_4經基节基） 異氰尿酸酯、二乙基[[卩^-雙^’丨-二甲基乙基）4經基苯 基]甲基]磷酸酯、2,5,7,8-四甲基_2(4，，8’，12，_三甲基十三 基）色滿-6-醇、2,4-雙-(η-辛硫基）·6_(4_經基-3,5二小丁 基本fee基）-1,3,5-二哄等。作爲—環己基胺，新日本理化 股份公司製商品名D-CHA-T等係以市售品可取得，作爲 其衍生物，可舉出亞硝酸二環己基胺銨、N,N_: (3_甲基_ 環己基胺）、N，N-二（2-甲氧基-環己基）胺、N N-二（4_溴_ 環己基）胺等。作爲有機硫化合物系抗氧化劑，可舉出二 月桂基_3,3’-硫代二丙酸醋、二肉豆寇基_3,3，_硫代二丙酸 酯、二硬脂基-3，3’-硫代二丙酸酯、季戊四醇基四（3-月桂 基硫代丙酸酯）、二個十三基-3,3’-硫代二丙酸酯、2-锍基 苯并咪唑、4,4’-硫代雙（6-t-丁基-3-甲基苯酚）、2,2-硫代-二伸乙基雙[3-(3,5-二-t-丁基-4-羥基苯基）丙酸酯]、4,6-雙（十二基硫甲基）-〇-甲酚、2,4-1雙[(辛硫基）甲基]甲 2,4-雙- (η-辛硫基）-6-(4-羥基- 3,5-二-t-丁基苯胺基）- 1，3,5-三哄等，作爲胺化合物系抗氧化劑，可舉出N，N’-二 烯丙基-P-苯二胺、N，N’-二-sec-丁基-P-苯二胺、辛基化二 苯基胺、2,4-雙-(n-辛硫基）-6-(4-羥基-3,5-二-t-丁基苯胺 基）-1,3,5-三哄等，作爲磷化合物系抗氧化劑，可舉出三 壬基苯基亞磷酸酯、三苯基亞磷酸酯、雙（3,5-二-t-丁基· -17- 201105698 4-羥基苄基磺酸乙基）鈣、三（2,4-二-t-丁基苯基）亞磷酸 酯、2-[[2,4,8，10-四（1，1-二甲基醚）二苯并[d, f][l，3，2]二 氧雜膦烷-6-基]氧基]-N，N-雙[2-{[2,4,8，10-四（1，1二甲基 乙基）二苯并[d，f][l，3，2]二氧雜膦烷-6-基]氧基}-乙基] 乙胺、6-[3-(3-t- 丁基-4-羥基-5-甲基苯基）丙氧基]-2,4,8,10-四-t-丁基二苯并[d，f][l，3，2]二氧雜膦烷、二乙 基[[3,5-雙（1，1-二甲基乙基）-4-羥基苯基]甲基]磷酸酯等。 可單獨使用此等的1種，也可組合2種類以上使用。再 者，於前述酚化合物系抗氧化劑之中，除了酚性羥基，在 同一分子中亦含有至少一個以上的磷原子、硫原子、胺的 任一個以上的化合物係重複列舉。 於前述抗氧化劑之中，從耐遷移性提高的觀點來看， 尤其更佳爲在酚核的鄰位至少具有1個烷基的酚化合物系 抗氧化劑與二環己基胺。茲認爲於在酚核的鄰位至少具有 1個烷基的酚化合物系抗氧化劑中，由於鄰位的烷基係供 電子基，故在酚性羥基的氧原子之不成對電子部位中，電 子濃度升高，抗氧化劑配位於陽極金屬表面，而且於二環 己基胺中，由於胺的氮原子之不成對電子部位配位於陽極 金屬表面，金屬表面上所配位的抗氧化劑抑制金屬的氧化 降解，而耐遷移性升高。 再者，前述在酚核的鄰位至少具有1個烷基的酚化合 物系抗氧化劑，一般已知係固體、粉末的性狀之化合物， 但是作爲電子零件用液狀樹脂組成物，爲了避免黏度、滲 透性、流動性的降低，在電子零件用液狀樹脂組成物的一 -18- 201105698 成分之（A)環氧樹脂中’電子零件用液狀樹脂組成物的硬 化物更佳爲溶解到具有充分耐遷移性的程度。具體地，在 —般的環氧樹脂中，例如本發明中作爲液狀環氧樹脂使用 的周知之雙酚F型環氧樹脂中，飽和溶解量較佳爲5質量 %以上’更佳的範圍爲1 〇質量％以上。其理由爲藉由將具 有前述較佳範圍的飽和溶解量之酚化合物系抗氧化劑溶解 在環氧樹脂中，酚化合物系抗氧化劑可均勻地分散在電子 零件用液狀樹脂組成物中，而提高耐遷移性。此處，前述 飽和溶解量，由於液狀樹脂組成物的塗佈通常在室溫進 行，考慮該液狀組成物的安定性，係在室溫的値。於前述 在酚核的鄰位至少具有1個烷基的酚化合物系抗氧化劑 中，作爲具有如此溶解性的酚化合物系抗氧化劑之例，可 舉出4,4’-亞丁基雙-(6-t-丁基-3-甲基苯酚）、四[亞甲基-3-(3,5-二-t-丁基-4-羥基苯基）丙酸酯]甲烷、3,9-雙[2-[3-(3-t-丁基-4-羥基-5-甲基苯基）丙醯氧基]-i，i-二甲基乙基]_ 2,4,8，10-四 氧雜螺 [5_5] 十一烷 、三乙 二醇雙 [3-(3-t-丁基-4-羥基-5-甲基苯基）丙酸酯]等。 再者，於溶解在前述環氧樹脂中的酚化合物系抗氧化 劑之中，更佳爲在酚核的鄰位具有1個甲基的酚化合物系 抗氧化劑。茲認爲此係因爲：甲基係立體障礙少且是供電 子基，抗氧化劑的酚性羥基之不成對電子更容易配位在陽 極金屬表面。作爲如此的酚化合物系抗氧化劑，可舉出 3,9-雙[2-[3-(3-t-丁基-4-羥基-5-甲基苯基）丙醯氧基]-1，1-二甲基乙基]-2，4,8,10-四氧雜螺[5.5]十一烷、三乙二醇雙t -19- 201105698 [3-(3-t-丁基-4·羥基·5_甲基苯基）丙酸酯]等。 又，二環己基胺係常溫的性狀爲液體，與固體、粉末 的抗氧化劑比較下，具有不損害電子零件用液狀樹脂組成 物的黏度、滲透性、流動性，可均勻地分散之優點。 前述酚化合物系抗氧化劑的配合量係相對於（Α)環氧 樹脂而言，較佳爲0.1〜10質量％，更佳爲0.5〜5.0質量 %。未達0.1質量％時，遷移的抑制效果降低，而若超過 1 0質量％，則電子零件用液狀樹脂組成物的流動性有降低 的傾向。再者，前述酚化合物系抗氧化劑在（Α)環氧樹脂 中的飽和溶解量D係5質量％<〇<10質量％時之配合 量，較佳爲〇. 1〜D質量％，更佳爲0 · 5〜5 · 0質量％。 前述二環己基胺的配合量係相對於（Α)環氧樹脂而 言，較佳爲0.1〜30質量％，更佳爲0.5〜10質量％。未達 0.1質量％時，遷移的抑制效果降低，而若超過30質量 %，則電子零件用液狀樹脂組成物的保存安定性及硬化物 的玻璃轉移溫度有降低的傾向。 採用本發明的電子零件用液狀樹脂組成物的電路板及 半導體裝置之配線間或凸塊間的間隙爲20μπι以下時，爲 了使間隙間的塡充性或流動性成爲良好，電子零件用液狀 樹脂組成物中不溶的固體化合物之配合量較佳爲10質量 %以下，更佳爲5質量％以下。另一方面，採用本發明的 電子零件用液狀樹脂組成物的電路板及半導體裝置之配線 間或凸塊間間隙超過20μιη時，更且需要耐遷移性的提高 時，以彌補電路板與半導體裝置的熱膨張係數差爲目的， -20- 201105698 在不損害間隙間的塡充性或流動性之範圍內，可配合無機 塡充劑。作爲無機塡充劑，可爲電子零件用液狀樹脂組成 物中所一般使用者，並沒有特別的限制限，例如可舉出熔 融矽石、結晶矽石、合成矽石等的矽石、碳酸鈣、滑石、 黏土、氧化鋁等的礬土、氮化矽、碳化矽、氮化硼、矽酸 鈣、鈦酸鉀' 氮化鋁、氧化鈹、氧化锆、鍩石、鎂橄欖 石、塊滑石、尖晶石、模來石、二氧化鈦等的粉體、或此 等經球形化的珠、玻璃纖維等。再者，亦可使用烷氧化物 化合物之經由水解·縮合反應所得的奈米矽石等之無機奈 米粒子當作塡充劑。此等無機塡充劑可單獨使用，也可組 合2種以上使用。 無機塡充劑的形狀，從流動性等的成形性之觀點來 看，較佳爲接近球形。無機塡充劑的平均粒徑較佳爲5nm 至ΙΟμιη的範圍。若超過ΙΟμιη，則有容易發生塡料沈降 的傾向，或電子零件用液狀樹脂組成物對微細間隙的滲透 性·流動性降低，有容易造成空洞·未塡充的傾向。又， 此等塡充劑亦可按照需要使用表面經偶合處理者。無機塡 充劑的配合量較佳爲電子零件用液狀樹脂組成物的1 0質 量％以下，更佳爲5質量％以下。超過10質量％時，電子 零件用液狀樹脂組成物的硬化物與使用薄膜基板的撓性電 路板之線膨張係數差變大，在兩者的界面容易發生剝離。 又，無機塡充劑量若多，則電子零件用液狀樹脂組成物之 黏度變高，由於表面張力升高，流動性有降低的傾向。 於本發明的電子零件用液狀樹脂組成物中，較佳爲按 -21 - 201105698 照需要使用促進（A)成分的環氧樹脂與含（B)成分的硬化劑 之反應的硬化促進劑。作爲硬化促進劑，爲了使硬化性與 適用期（pot life)並存，較佳爲潛在性硬化促進劑。所謂的 潛在性硬化促進劑，就是在某一特定的溫度等條件下展現 硬化促進機能者，例如通常的硬化促進劑可舉出經微膠囊 等保護或各種化合物與附加的鹽之構造者。於此情況下， 若超過特定的溫度，則由微膠囊或加成物釋放出硬化促進 劑。 作爲潛在性硬化促進劑之例，可舉出以常溫固體的具 有胺基之化合物當作芯，被覆常溫固體的環氧化合物之殻 而成的芯-殼粒子，作爲市售品，可使用 Amicure(味之素 股份公司製，註冊商標）、或使經微膠囊化的胺分散在雙 酚A型環氧樹脂、雙酚F型環氧樹脂中的Novacure (旭化 成化學股份公司製，註冊商標）等。 再者，不溶於電子零件用液狀樹脂組成物系中的固體 粒子而在加熱成形時進行解離以展現硬化促進作用的胺化 合物或磷化合物的鹽類及於彼等附加具有π鍵的化合物所 成的具有分子內極化之化合物，係可作爲潛在性硬化促進 劑使用。 若例示此等，可舉出1,8-二氮雜-雙環（5，4，0)十一 烯-7、1，5-二氮雜-雙環（4，3，0)壬烯、5,6-二丁基胺基― 1,8-二氮雜-雙環（5，4，0)十一烯-7等的環脒化合物與附加 有具π鍵的化合物所成的具有分子內極化之化合物、三乙 二胺、苄基二甲基胺、三乙醇胺、二甲基胺基乙醇、三 -22- 201105698 (二甲基胺基甲基）苯酸等的三級胺化合物的衍生物、2 -甲 基咪唑、2_乙基-4-甲基咪唑、2-苯基咪唑、2·苯基_4_甲 基咪唑、2-十七基咪唑等的咪唑化合物之衍生物、三丁基 膦、甲基二苯基膦、三苯基膦、二苯基膦、苯基膦等的有 機膦化合物中附加馬來酸酐、1，4-苯醌、2,5-甲苯醌、 1，4-萘醌、2,3-二甲基苯醌、2,6-二甲基苯醌、2,3-二甲氧 基-5-甲基-1，4-苯醌、2,3-二甲氧基-1,4-苯醌 '苯基-l，4-苯醌等的醌化合物、重氮苯基甲烷、酚樹脂等之具有π鍵 的化合物所成的具有分子內極化之磷化合物、及此等的衍 生物 '三苯基膦三苯基硼、四苯基鳞四苯基硼酸酯' 2-乙 基-4-甲基咪唑四苯基硼酸酯、Ν-甲基嗎啉四苯基硼酸酯 等的苯基硼鹽及此等衍生物等，可單獨使用此等的1種， 也可組合2種以上使用。 其中，從保存安定性、速硬化性的觀點來看，較佳爲 使微膠囊化的胺分散在雙酚Α型環氧樹脂、雙酚F型環 氧樹脂中者。 硬化促進劑的配合量，只要是達成硬化促進效果之 量，則沒有特別的限制，以亦含有非潛在性者的全量計， 相對於（A)環氧樹脂而言，較佳爲0.1〜40質量％，更佳爲 0.5〜30質量％。未達0.1質量％時，則有短時間的硬化性 差之傾向，而若超過4 0質量％ ’則硬化速度過快而控制 變困難，或適用期、擱置壽命（shelf life)等的保存安定性 有變差的傾向。 於本發明的電子零件用液狀樹脂組成物中’爲了謀求t 3 -23- 201105698 環氧樹脂硬化物的強韌化或低彈性模數化，較佳爲配合眾 所周知的各種橡膠粒子。該橡膠粒子雖然與環氧樹脂呈非 相溶性，但是不降低硬化物的玻璃轉移溫度（耐熱性），而 有效於降低彈性模數。具體地，例如可舉出丁二烯.丙烯 腈♦苯乙烯系共聚合物或在該聚合物的末端或側鏈具有環 氧基、胺基、羧基、羥基等之改性共聚合物、在末端或側 鏈具有環氧基、胺基、羧基、羥基等之改性聚矽氧系彈性 體等。從操作性或樹脂成分的分散性之點來看，橡膠粒子 較宜使用微粉末狀且預先細分散在環氧樹脂或硬化劑中 者。從可一樣地混合在樹脂組成物中來看，較佳爲常溫是 液狀的橡膠改性環氧樹脂（將液狀環氧樹脂與橡膠粒子加 熱熔融者）。藉由含有橡膠粒子，而提高電子零件用液狀 樹脂組成物的硬化物與基板等的密接性，謀求耐高溫高濕 性等的可靠性提高。 又，於本發明的電子零件用液狀樹脂組成物中，採用 於電路板及半導體裝置時，在不損害塡充性或流動性之範 圍內，從提高耐遷移性、耐濕性及高溫放置特性的觀點來 看，較佳爲視需要更含有離子捕捉劑。離子捕捉劑係沒有 特別的限制，可以使用習知者，特佳爲下述組成式（I)所 示的水滑石或（II)所示的鉍之水合氧化物。 (化1) Μ gi-χΑΙχ (OH) 2 (C03)x/2 *ιηΗ2〇 (I) (式（I)中，0<XS0.5，m係正數） (化2) -24- 201105698 B i O, (OH) y (NO3 ) , (II) (式（II)，0.9$xSl.l、0.6SyS0.8、0.2Sz$0.4) 此等離子捕捉劑之添加量，只要是可捕捉鹵離子等的 陰離子之充足量即可，並沒有特別的限定，從耐遷移性的 觀點來看，相對於電子零件用液狀樹脂組成物而言，較佳 爲0.1〜3.0質量％，更佳爲0.3〜1.5質量％。離子捕捉劑 的平均粒徑較佳爲0.1〜3.0μιη，最大粒徑較佳爲ΙΟμιη以 下。再者，上述式（I)化合物係以市售品的協和化學工業 股份公司製商品名DHT-4A可取得。又，上述式（II)的化 合物係以市售品的東亞合成股份公司製商品名ΙΧΕ500可 取得。又，按照需要，亦可添加其它離子捕捉劑。例如， 可舉出由鎂、鋁、鈦、銷、銻等所選出的元素之水合氧化 物等，可單獨或組合2種以上使用此等。 還有，於本發明的電子零件用卓夜狀樹脂組成物中， 按照需要，較佳爲添加與上述（Α)環氧樹脂成分不同的聚 矽氧改性環氧樹脂。藉由添加聚矽氧改性環氧樹脂，而在 電子零件用液狀樹脂組成物的均平性、內圓角（fillet)形成 性、空洞減低上具有效果。聚矽氧改性環氧樹脂係可作爲 具有與環氧基反應的官能基之聚有機矽烷氧與環氧樹脂之 反應物獲得，較佳在常溫爲液狀。聚矽氧改性環氧樹脂係 可在液體的表面局部存在化，而減低液體的表面張力。藉 此’提高潤濕性、容易流動，故在對窄間隙的滲透性提高 或捲入的空洞之減低上具有效果。 此處，若例示具有與環氧基反應的官能基之聚有機矽 -25- 201105698 烷氧，可舉出1分子中具有1個以上的胺基、羧基'羥 基、酚性羥基、锍基等之二甲基矽氧烷、二苯基矽氧烷、 甲基苯基矽氧烷等。聚有機矽烷氧的重量平均分子量較佳 爲5 00〜5 000的範圍。此理由爲若未達500，則與樹脂系 的相溶性過度良好，不能充分發揮作爲添加劑的效果，而 若超過5000，則與樹脂系變不相溶，故聚矽氧改性環氧 樹脂在成形時會發生分離•滲出，而損害黏著性或外觀。 作爲用於得到聚矽氧改性環氧基樹脂的環氧樹脂，只 要是與電子零件用液狀樹脂組成物的樹脂系相溶者，則沒 有特別的限制，可使用電子零件用液狀樹脂組成物中所一 般使用的環氧樹脂，例如可舉出由雙酚A、雙酚F、雙酚 AD、雙酚S、萘二酚、氫化雙酚A等與環氧氯丙烷之反 應所得的縮水甘油醚型環氧樹脂，以鄰甲酚酚醛清漆型環 氧樹脂爲首的使酚類與醛類縮合或共縮合而得之酚醛清漆 樹脂經環氧化的酚醛清漆型環氧樹脂，由苯二甲酸、二聚 酸等的多元酸與環氧氯丙烷之反應所得的縮水甘油醚型環 氧樹脂’由二胺基二苯基甲烷、異氰尿酸等的多胺與環氧 氯丙烷之反應所得的縮水甘油基胺型環氧樹脂，以過乙酸 等的過酸將烯烴鍵氧化而得之線狀脂肪族環氧樹脂、脂環 族環氧樹脂等，可單獨使用此等，亦可組合2種以上使 用，較佳爲常溫液狀者。 於本發明的電子零件用液狀樹脂組成物中，作爲其它 添加劑，於不損害對電路板及半導體裝置的適用時之塡充 性或流動性的範圍內，可以按照需要配合染料、碳黑、氧 -26- 201105698 化鈦、鉛丹等的著色劑、難燃劑、稀釋劑、其它均平劑、 其它應力鬆弛劑、消泡劑'黏著促進劑等。 作爲難燃劑，可以使用溴化環氧樹脂或三氧化銻，較 佳爲使用非鹵素、非銻的難燃劑。例如，可舉出紅磷、經 酚樹脂等的熱硬化性樹脂等被覆的紅磷、磷酸酯、氧化三 苯膦等的磷化合物、三聚氰胺、三聚氰胺衍生物、三聚氰 胺改性酚樹脂、具有三哄環的化合物、氰尿酸酸衍生物、 異氰尿酸衍生物等的含氮化合物、環磷腈等之含磷和氮的 化合物、二環戊二烯基鐵等的金屬錯合物化合物、氧化 鋅、錫酸鋅、硼酸鋅、鉬酸鋅等的鋅化合物、氧化鐵、氧 化鉬等的金屬氧化物、氫氧化鋁、氫氧化鎂等的金屬氫氧 化物、下述組成式（III)所示的複合金屬氫氧化物等。 (化3) p (M1 a Ob ) · q (M2 c 〇d ) * r (M3 c 〇 d ) · mH 2 O (III) (組成式（ΠΙ)中，Μ1、M2及M3表示互相不同的金屬 元素，8、1?、《；、<1、？、9及111表示正數，1'表示〇或正 數）。 上述組成式（ΠΙ)中的M1、！^2及M3只要是互相不同 的金屬元素即可，而沒有特別的限制，但從難燃性的觀點 來看，M1較佳爲選自屬於第3週期的金屬元素、IIA族的 鹼土類金屬元素、IVB族、IIB族、VIII族、IB族、IIIA 族及IVA族的金屬元素，M2較佳爲選自於IIIB〜IIB族 -27- 201105698 的過渡金屬元素，Μ1更佳爲選自於鎂、鈣、鋁、錫、 鈦、鐵、銘、鎳、銅及鋅，Μ2更佳爲選自於鐵、鈷、 鎳、銅及鋅。從流動性的觀點來看，Μ1爲鎂、Μ2爲鋅或 鎳、r = 〇者係較宜。p、q及r的莫耳比係沒有特別的限 制，但較佳爲 r = 0、p/q=l/99〜1/1。再者，金屬元素的分 類係以典型元素當作A亞族、過渡元素當作b亞族的長 週期型之週期表爲基礎進行。上述難燃劑係可單獨使用1 種’也可組合2種以上使用。 作爲稀釋劑，可混合黏度調整用之具有環氧基的反應 性稀釋劑。作爲具有環氧基的反應性稀釋劑，例如可舉出 正丁基縮水甘油酸、叔碳（versatic)酸縮水甘油酸、氧化 苯乙嫌、乙基己基縮水甘油酸、苯基縮水甘油酸、丁基苯 基縮水甘油醚、1,6·己二醇二縮水甘油醚、新戊二醇二縮 水甘油醚、二乙二醇二縮水甘油醚、三羥甲基丙烷三縮水 甘油醚。可單獨使用此等的1種，也可組合2種以上使 用。 本發明的電子零件用液狀樹脂組成物，只要可均勻分 散混合各種成分，亦可以使用任何手法來調製。作爲一般 的手法，可藉由秤量指定配合量的成分，使用擂潰機、混 合輥、行星式混合機等進行混合、混煉，視需要進行脫泡 而得。 作爲經由本發明所得之電子零件用液狀樹脂組成物將 元件密封而得之電子零件裝置，可舉出於引線框、完成配 線的載帶、剛性及撓性電路板、玻璃、矽晶圓等的支持構 28 - 201105698 件上，搭載半導體晶片、電晶體、二極體、閘流體等的主 動元件、電容器、電阻器、電阻陣列、線圈、開關等的被 動元件等之元件，以本發明的電子零件用液狀樹脂組成物 將必要部分密封而得之電子零件裝置等。特別地，較佳爲 使用於在以薄膜爲基材的電路基板上直接以凸塊連接有電 子零件的電子零件裝置之密封。例如，對象爲在形成於剛 性及撓性電路板或玻璃上的配線上，以凸塊連接半導體元 件的覆晶接合之半導體裝置。作爲具體例，可舉出覆晶 BGA或COF(Chip On Film)等的半導體裝置，本發明所得 之電子零件用液狀樹脂組成物係特別適合作爲耐遷移性優 異的COF用之底部塡充材。又，本發明的電子零件用液 狀樹脂組成物亦可有效地使用於印刷電路板。 作爲使用本發明的電子零件用液狀樹脂組成物將元件 密封的方法，可舉出分配（dispense)方式、鑄模方式、印 刷方式等。 [實施例] 接著，藉由實施例來說明本發明，惟本發明的範圍不 受此等實施例所限定。 (實施例1〜5及比較例） 作爲（A)環氧樹脂，準備： 環氧基當量160的雙酚F型液狀環氧樹脂（東都化成 股份公司製商品名YDF-817〇C)、 -29 - 201105698 環氧基當量140的萘型環氧樹脂（大曰本油墨工業股 份公司製商品名HP-4032)， 作爲橡膠粒子成分，準備： 預先以1/4的質量比使丙稀腈.丁二燃.甲基丙稀酸 •二乙烯基苯共聚物（JSR股份公司製商品名xer-91P)熱 熔融、微分散在雙酚F型液狀環氧樹脂（YDF-8170C)中而 成的橡膠改性環氧樹脂， 作爲均平劑，準備： 將羥基當量750的酚改性聚矽氧（東麗•道康寧聚矽 氧製商品名 BY 1 6-799)與雙酚F型液狀環氧樹脂（YDF-8 1 70C)以1/1的質量比進行加熱混熔而得之聚矽氧改性環 氧樹脂， 作爲（B)環狀酸酐，準備： 常溫液體且酸酐當量234的環狀酸酐（日本環氧樹脂 股份公司製商品名jERcure YH306)， 作爲（C)偶合劑，準備： γ-環氧丙氧基丙基三甲氧基矽烷（信越化學工業股份 公司製商品名ΚΒΜ-403)， 作爲（D)抗氧化劑，準備： 4，4’-亞丁基雙-(6-t-丁基-3-甲基苯酚）（股份公司API Corporation 製商品名 YoshinoxBB;抗氧化劑 1)、 四[亞甲基- 3-(3,5-二-t-丁基-4-羥基苯基）丙酸酯]甲烷 (股份公司API Corporation製商品名Tominox TT:抗氧 化劑2)、 -30- 201105698 3,9-雙[2-[3-(3-1-丁基-4-羥基-5-甲基苯基）丙醯氧基]_ 1,1-二甲基乙基]-2，4,8,10-四氧雜螺[5.5]十一烷（股份公司 ADEKA製商品名AO-80;抗氧化劑3)、三乙二醇雙[3_(3-t- 丁基-4-經基-5-甲基苯基）丙酸醋](股份公司 API corporation 製商品名 Yoshinox 917;抗氧化劑 4)、 二環己基胺（新日本理化股份公司製商品名D-CHA-T ;抗氧化劑5)， 作爲硬化促進劑，準備： 2-乙基-4-甲基咪唑（四國化成工業股份公司製商品名 2E4MZ) > 作爲塡充劑，準備： 比表面積lm2/g、平均粒徑4μηι的球狀合成矽石。 此等係各自以下述表1所示的質量份進行配合，於擂 潰機中混煉分散後，進行真空脫泡，製作實施例1〜5及 比較例的電子零件用液狀樹脂組成物。 -31 - 201105698 [表i] 配合成份 實施例 比較例 1 2 3 4 5 雙酚F型環氧樹脂 50 50 50 50 50 50 萘型環氧樹脂 20 20 20 20 20 20 橡膠改性環氧樹脂 30 30 30 30 30 30 聚矽氧改性環氧樹脂 1 1 1 1 1 1 環狀酸酐 130 130 130 130 130 130 偶合劑 1 1 1 1 1 1 抗氧化劑1 1 抗氧化劑2 1 抗氧化劑3 1 抗氧化劑4 1 抗氧化劑5 1 硬化促進劑 1 1 1 1 1 1 (單位：質量份） 藉由以下的各試驗來評價所製作的實施例1〜5及比 較例之電子零件用液狀樹脂組成物。下述表2中顯示評價 結果。 (1) 黏度 使用EMD型旋轉黏度計（股份公司TOKIMEC製），對 於在25±1°C保持的電子零件用液狀樹脂組成物，實施例1 〜5、比較例係以1 OOrpm旋轉I分鐘時的刻度乘以換算係 數0.0125，將其當作黏度。 (2) 膠化時間 於150°C的熱板上滴下0.1克電子零件用液狀樹脂組 成物，以不過度展開的方式，用刮勺攪拌。滴下後，電子 零件用液狀樹脂組成物的黏度上升，將向上拿起刮勺時不 -32- 201105698 牽絲而斷裂爲止的時間當作膠化時間。 (3 )吸水率 使電子零件用液狀樹脂組成物在1 50°C、2小時的條 件下硬化，以製作50mmx5〇mmxlmm的試驗片。測定本 試驗片的初期重量Wi後，置入85°C/85%的高溫高濕槽 中，測定1 〇 〇小時後的重量W 2 ’藉由下式求得吸水率。 (吸水率 ^{(Ws-Wd/Wt } X 1 00 (%) (4) 黏著力 於聚醯亞胺薄膜（東麗·杜邦股份公司商品名Kapton) 上，使電子零件用液狀樹脂組成物在1 5 0°C、2小時的條 件下硬化，切斷成寬度l〇mm的長方形狀。對其，使用拉 伸張試驗器（島津製作所製），以90度向上剝離聚醯亞胺 薄膜的剝離強度當作黏著力。 (5) 侵入性 用2片玻璃夾住厚度2 0 μπι的SUS製間隔物，以製作 寬度5mm的流路。將其水平地放置在7(TC的加熱板上 後，滴下電子零件用液狀樹脂組成物，測定在間隙之間侵 入2 0mm爲止的時間。未達3分鐘爲良，3分鐘以上爲不 良。 (6) 耐遷移性評價 於聚醯亞胺薄膜上藉由經鍍錫的銅配線形成有配線寬 度15μιη、配線間15μιη的相對向梳形電極之撓性電路板 之相對向電極部上，以分配方式塗佈電子零件用液狀樹脂 組成物，將在1 50°C、2小時硬化者當作試驗片。對此試 -33- 201105698 驗片’在120°C/85%的高溫高濕下施予直流60V的電壓， 連續地測定電阻値，在電阻値成爲1 〇6Q以下的時間，判 斷爲發生拽漏。測定係進行到5 0 0小時爲止，將電阻値未 成爲1 0 6 Ω以下的電子零件用液狀樹脂組成物當作> 5 〇 〇小 時。 (7)外觀評價 實體顯微鏡的透射光觀察耐遷移性評價結束後的試驗 片’觀察聚醯亞胺薄膜上鍍錫的銅配線之腐蝕程度。若發 生遷移’則看到自陽極側，配線金屬進行腐蝕，在樹脂中 溶出的現象。因此若以透射光來觀察，則如圖i所示地， 對應於遷移的進行程度，看到陽極配線的寬度比試驗前 粗。最腐蝕的配線寬度與試驗前的配線寬度作比較，將 1·0〜1.1倍當作◎，將1.1〜1.2倍者當作〇，將1.2〜i ·3 倍者當作△，將1 .3倍以上者當作X。 [表2][Technical Field] The present invention relates to a liquid resin composition for electronic components suitable for sealing electronic parts and an electronic component device sealed thereby, [Prior Art] In the field of component sealing of an electronic component device such as a crystal or a 1C, a resin sealing system is in the mainstream from the viewpoints of productivity, cost, and the like, and an epoxy resin composition is widely used. The reason for this is that the epoxy resin can be balanced in various properties such as workability, moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to an insert. In a semiconductor device in which bare crystals are assembled, such as C OB (Chip on Board), COG (Chip on Glass), and TCP (Tape Carrier Package), a liquid resin composition for electronic components is widely used as a sealing material. In recent years, an assembly method of 1C for display driving such as liquid crystal is used in an assembly form in which a semiconductor element is directly connected to a circuit board by a bump (a flip chip connection method), and a liquid shape for an electronic component used in the assembly is known. The resin composition is used as a bottom crucible. In the above-described flip-chip bonding method of the conductor assembly method, the underfill material is filled in a space between the circuit board and the semiconductor device for the purpose of sealing between the bumps and holding the mechanical strength. . Therefore, in the bottom crucible, (1) a liquid having a low viscosity at normal temperature, (2) in order to prevent bubbles (voids) from occurring in the thermosetting process of the resin after charging, the resin composition is solvent-free, (3) In order to avoid the increase in viscosity and the decrease in permeability -5,010,056,98, it is possible to avoid solid components containing materials such as sputum, and (4) to maintain the uniformity of solid components in the liquid resin composition for electronic components when solid components are contained. Dispersibility, conditions such as the particle size distribution that does not impair viscosity, fluidity, permeability, etc., and the appropriate coordination of the management of the charge are necessary items. In the above circuit board and semiconductor device, the interval between wirings is narrowed, and in the flip chip semiconductor device of the tip end, the wiring pitch may be 30 μm or less. Therefore, the application of a high voltage between the narrow-pitch wirings has a problem that the liquid resin composition for electronic components has a large migration phenomenon as one of the defects that impair the reliability of insulation. In particular, since deterioration of the resin and the wiring metal is promoted under high temperature and high humidity, migration and varnishing tend to occur, and the occurrence of defects in the semiconductor device tends to increase. In order to avoid this defect, the resin composition used for the electronic component has been previously prepared for the purpose of suppressing migration. For example, as a metal ion-carrying agent, a resin composition containing an inorganic ion exchanger (for example, refer to Patent Documents 1 to 4), a benzotriazine, a benzotriazole or an isocyanuric acid addition is known. A resin composition (for example, refer to Patent Documents 5 to 10), a resin composition containing a borate-containing compound in a curing accelerator (for example, see Patent Document 1 1), and a resin composition containing an antioxidant (for example) Refer to Patent Document 1 2 to 1 3) and the like as a resin composition for use in applications such as a sealing material, an adhesive, a prepreg, and the like. In the above-mentioned conventional examples, the resin composition containing an antioxidant exemplified in the patent documents 12 to 13 is known, in addition to the effect of preventing deterioration of the resin, in the resin composition for a printed circuit board typified by a prepreg. It is particularly excellent in migration resistance. When it is blended in a resin composition for a printed circuit board, it is used in a solvent such as methyl ethyl ketone (MEK) or toluene from -6 to 201105698, and various antioxidants which are generally solid at room temperature (powder) can be used together with an epoxy resin. The hardening agent and the hardening accelerator are mixed and dissolved, and any antioxidant can be selected according to the use or characteristics. [Patent Document 1] JP-A-6-158492 [Patent Document 2] Japanese Patent Laid-Open No. Hei 9_3丨4758 (Patent Literature) [Patent Document 5] JP-A-2001-63549 [Patent Document 5] JP-A-2001-203462 [Patent Document 7] Japanese Patent Laid-Open No. Hei. No. 2005-722075 [Patent Document No. 2005-333085] [Patent Document 10] Patent No. 363 3422 [Patent Literature] [Patent Document 12] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. a liquid resin composition for electronic parts used as a bottom enamel material, As described above, in the heat hardening of the resin after the filling, in order to avoid the occurrence of bubbles (voids), no solvent is used. Therefore, in the solvent-free liquid resin composition for electronic parts, the conventional antioxidant is uniformly dissolved in 201,105,698, and does not impair the low viscosity, high fluidity, high permeability or rapid hardening property, and low water absorption. It is difficult to obtain a liquid resin composition for an electronic component excellent in ρ mobility, which is a necessary property of the underfill material, such as high adhesion. At present, the migration resistance is improved by reducing impurities in the liquid resin composition for electronic parts. However, in the COF (Chip On Film) of a representative semiconductor device having a fine line and a narrow pitch, for example, it is required to improve the migration resistance, and it is difficult to cope with the high purity of the liquid resin composition for electronic parts. The present invention has been made in view of such a situation, and provides a liquid resin composition for an electronic component which is excellent in migration resistance and excellent in moldability and reliability, and an electronic component device sealed therewith. Means for Solving the Problems In order to solve the above problems, the inventors of the present invention have repeatedly conducted an intensive review. As a result, it has been found that an electronic component such as a semiconductor element has good adhesion to a circuit board, and has a small water absorption rate, and suppresses oxidative degradation, low viscosity, and flow. The liquid resin composition for high-purity electronic parts excellent in the properties can achieve the above object, and finally the present invention has been completed. The present invention relates to the following (1) to (15). (1) A liquid resin composition for an electronic component comprising (A) an epoxy resin' (B) a cyclic acid anhydride of a normal temperature liquid, (a coupling agent, and (D) an antioxidant. (2) as described above (1) In the liquid resin composition for an electronic component, the (D) antioxidant of the above-mentioned (D) antioxidant contains a phenol compound having at least one alkyl group in the ortho position of the phenol nucleus. (3) The electronic component according to the above (1) In the liquid resin composition, the (D) antioxidant contains a phenol compound having one methyl group in the ortho position of the phenol nucleus. (4) The liquid resin composition for electronic parts according to the above (2) or (3) (D) The liquid-based resin composition for electronic parts according to the above (1), wherein (D) the anti-oxidant is a 5% by weight or more. (2) The liquid resin composition for an electronic component according to any one of the above-mentioned (1) to (5), further comprising an inorganic chelating agent and an inorganic hydrazine The amount of the agent is 10% by mass or less. (7) The electron zero according to any one of the above (1) to (6) The liquid resin composition for an electronic component according to any one of the above aspects (1) to (7), further comprising a polyoxymethylene-modified epoxy resin. (9) The liquid resin composition for an electronic component according to any one of the above (1), wherein the ion scavenger is further contained. (10) Any one of (1) to (9) The liquid resin composition for an electronic component according to the invention further contains a latent curing accelerator for promoting the reaction between (A) and (B). [S] (1 1) as in the above (1) to (10) The liquid resin composition for an electronic component according to any one of the above (1) to (1), wherein the electronic component is more than 1%. The liquid resin composition for an electronic component according to any one of the above (1) to (12), wherein the liquid resin composition for the electronic component according to any one of the above (1) to (12) is a liquid resin composition. The viscosity of the ^X^ using the EMD type rotational viscometer is 1 · 2 P a . s or less. (14) As described in any one of the above (1) to (13) A liquid resin composition for an electronic component, which is used in an electronic component device in which an electronic component is directly bump-bonded to a circuit board on which a film is used as a substrate. (15) An electronic component device using the above (1) The liquid resin composition for electronic components according to any one of the above-mentioned (14) is sealed. The liquid resin composition for electronic components of the present invention is excellent in migration resistance, and electronic components such as semiconductor elements. The liquid resin composition for a high-purity electronic component which is excellent in adhesion to a circuit board and has a small water absorption rate and which suppresses oxidative degradation, low viscosity, and fluidity is expensive. In particular, it is particularly suitable for a flip-chip bonded semiconductor device which is a wiring formed by connecting a semiconductor element to a rigid circuit board and a flexible circuit board glass by bumps, and specifically, a bottom plate for a semiconductor device such as a BGA or COF. Filling material. [Embodiment] The invention of the present invention is not limited to the epoxy resin (A) used in the present invention, as long as it is an epoxy resin having two or more epoxy groups in one molecule. The epoxy resin which is generally used in the liquid resin composition for electronic components is used, and if the composition is liquid, either solid or liquid can be used, and both can be used. For example, a glycidyl ether type epoxy resin obtained by reacting bisphenol A, bisphenol F, bisphenol AD, bisphenol S, naphthalenediol, hydrogenated bisphenol A, etc. with epichlorohydrin may be mentioned. A novolac type epoxy resin obtained by epoxidizing or co-condensing a phenolic aldehyde-based varnish with a phenol novolac type epoxy resin, and a polybasic acid such as phthalic acid or a dimer acid A glycidyl ether type epoxy resin obtained by the reaction of epichlorohydrin, a glycidyl amine type epoxy resin obtained by reacting a polyamine such as diaminodiphenylmethane or isocyanuric acid with epichlorohydrin, A linear aliphatic epoxy resin or an alicyclic epoxy resin obtained by oxidizing an olefin bond with a peracid such as peracetic acid may be used singly or in combination of two or more. Among them, from the viewpoint of low viscosity, a liquid epoxy resin is preferable, and a bisphenol liquid epoxy resin is more preferable from the viewpoint of reactivity with a cyclic acid anhydride. Further, in the case where these epoxy resins are sufficiently purified, those having less ionic impurities are preferred. For example, the free Na ion and the free C1 ion are more preferably 500 ppm or less. The cyclic acid anhydride of the (B) room temperature liquid used in the present invention is not particularly limited, and examples thereof include phthalic anhydride, maleic anhydride, methylheimeric anhydride, heiming anhydride, succinic anhydride, and tetrahydrogen. Phthalic anhydride, hexahydrobenzene-11 - 201105698 Dicarboxylic anhydride, chloric anhydride, methyltetrahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4·methylhexahydrophthalic anhydride , trialkyltetrahydrophthalic anhydride maleic acid adduct, methyl hexahydrophthalic acid, benzophenone tetracarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, methyl tetrahydrophthalic anhydride, hydrogenation Methylnadic anhydride, a trialkyltetrahydrophthalic anhydride having a plurality of alkyl groups obtained by a reaction of maleic anhydride and a diene compound via Diels-Alder, dodecenyl succinic anhydride, etc. Various cyclic anhydrides. The term "cyclic anhydride" means that, as represented by phthalic anhydride, two carbon atoms C of "-C0-0-C0-" are chemically bonded to the other two carbon atoms to form a ring. Further, the "anhydride equivalent" is represented by (the molecular weight of the acid anhydride) / (the number of the acid anhydride groups in the acid anhydride molecule). A compound having an acid anhydride equivalent of 200 or more, for example, a product name of JERCure YH306 manufactured by Nippon Epoxy Co., Ltd. having an acid anhydride equivalent of 234, is commercially available. When the acid anhydride equivalent of the acid anhydride is less than 200, since the ester bond in the cured product is increased, it is easily affected by hydrolysis under high temperature and high humidity, and moisture resistance and migration resistance are likely to be lowered. Further, when the acid anhydride equivalent of the acid anhydride is less than 200, the water absorption rate is also increased by the influence of the ester group, which also causes a decrease in migration resistance. In other words, the concentration of the cyclic acid anhydride ester group having a large acid anhydride equivalent is smaller than that of the cyclic acid anhydride having a small acid anhydride equivalent, and the cured product has a low water absorption rate, so that the ionic impurity such as C1 dissolved in water can be reduced. quality. The acid anhydride equivalent is preferably from 200 to 400, more preferably from 200 to 300. The structure of the cyclic acid anhydride of the component (B) is not particularly limited, and from the viewpoint of migration resistance, it is preferred that the molecule does not contain a halogen-12-201105698 atom or an ester bond such as chlorine or bromine. In the present invention, a curing agent other than the component (B) can be suitably used, and as a curing agent for the epoxy resin, a general user can be used. For example, diethylenetriamine 'tris-ethyltriamine, tetra-ethylenepentamine, m-xylylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, and the like Ethylaminopropylamine, isophoronediamine, 1,3-diaminemethylcyclohexane, bis(4-aminocyclohexyl)methane, ornidyldiamine, 1,2-diamine Cyclohexane, Laromin, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenyl milling, polypropylene oxide diamine, polypropylene oxide triamine, polycyclohexyl Polyamine mixture, amine compound such as N-aminoethylpiperidin, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4 -methylimidazole, 2,4-diamino-6-(2-methylimidazolyl-(1))ethyl-s-triterpene, 2-phenylimidazoline, 2,3-dihydro-1H An imidazole compound such as pyrrolo(1,2-a)benzimidazole, a tertiary amine, DBU, a cyanogenic hydrazine, an organic acid di-n'N,N-dimethylurea derivative or the like. Among them, from the viewpoint of low viscosity, an amine compound is preferred. In order to exhibit the performance, the amount of the liquid anhydride of the component (B) is preferably 30% by mass or more, and more preferably 40% by mass or more, based on the total amount of the curing agent containing the component (B). More preferably, it is 60% by mass or more. (A) The equivalent ratio of the epoxy resin to all the hardeners of the cyclic acid anhydride containing the ambient temperature liquid of the component (B) is not particularly limited, and in order to lower the respective unreacted portions, it is preferably relative to the epoxy resin. The hardener is set in the range of 0.6 to 1.6 equivalents, more preferably 0.7 to 1.4 equivalents, and particularly preferably -13 to 201105698 0.8 to 1.2 equivalents. When the deviation is in the range of 0.6 to 1.6 equivalents, the hardening strain is insufficient and the reliability tends to be lowered. Here, the equivalent reaction equivalent, for example, the anhydride equivalent of the acid anhydride, is calculated as one reactor for one epoxy group, and the equivalent of the phenol resin is relative to one epoxy group. One phenolic hydroxyl group was calculated as a reactor, and the equivalent of an aromatic amine was calculated as one reactor with respect to one epoxy group. The (C) coupling agent used in the present invention is not particularly limited, and a conventional one may be used, and examples thereof include a decane compound having a primary and/or secondary and/or tertiary amine group, an epoxy decane, and a decyl group. Various decane-based compounds such as decane, alkyl decane, ureido decane, and vinyl decane, titanium compounds, aluminum chelates, aluminum/antimony compounds, and the like. Examples of such examples include vinyltrichlorodecane, vinyltriethoxydecane, vinyltris(β-methoxyethoxy)decane, and γ-methylpropenyloxypropyltrimethoxy. Decane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropylmethyldimethoxy Base decane, vinyl triethoxy decane, γ-mercaptopropyl trimethoxy decane, γ-aminopropyl trimethoxy decane, γ-aminopropyl methyl dimethoxy decane, γ- Aminopropyltriethoxydecane, γ-aminopropylmethyldiethoxydecane, γ-anilinopropyltrimethoxydecane, γ-anilinopropyltriethoxydecane, γ-( Ν,Ν-dimethyl)aminopropyltrimethoxydecane, γ-(Ν,Ν-diethyl)aminopropyltrimethoxydecane, γ-(Ν,Ν-dibutyl)amine Propyltrimethoxydecane, γ-(Ν-methyl)anilinopropyltrimethoxydecane, γ-(Ν-ethyl)anilinopropyltrimethoxyphosphonium-14- 201105698 alkane, γ-(Ν , Ν-dimethyl)aminopropyl triethoxy decane, γ-(Ν, Ν-Diethyl)aminopropyltriethoxydecane, γ-(Ν,Ν-dibutyl)aminopropyltriethoxydecane, γ-(Ν-methyl)anilinopropyltri Ethoxy decane, γ-(Ν-ethyl)anilinopropyl triethoxy decane, γ-(Ν, Ν-dimethyl)aminopropylmethyldimethoxydecane, γ-(Ν , Ν-diethyl)aminopropylmethyldimethoxydecane, γ-(Ν,Ν-dibutyl)aminopropylmethyldimethoxydecane, γ-(Ν-methyl) Anilinopropylmethyldimethoxydecane, γ-(Ν-ethyl)anilinopropylmethyldimethoxydecane, Ν-(trimethoxydecylpropyl)ethylenediamine, Ν-( Dimethoxymethyl decyl isopropyl) ethylene diamine, methyl trimethoxy decane, dimethyl dimethoxy decane, methyl triethoxy decane, γ chloropropyl trimethoxy decane, a decane coupling agent such as hexamethyldioxane, vinyltrimethoxydecane or γ-mercaptopropylmethyldimethoxydecane, isopropyl triisostearate titanate or isopropyl trisole (dioctylhydrogen phosphate) titanate, isopropyl tris(fluorene-amine ethyl-amine ethyl) titanate, Octyl bis(twenth trisylphosphite) titanate, tetrakis(2,2-diallyloxymethyl-1-butyl)bis(tiiitridecyl)phosphite titanate , bis(dioctylhydrogen phosphate)oxyacetate titanate, bis(dioctylhydrogen phosphate)vinyl titanate, isopropyl trioctadecyl titanate, isopropyldimethylpropyl decyl Isostearyl phthalocyanate, isopropyltridecyl benzene sulfonate titanate, isopropylisostearyl decyl bisacryl decyl titanate, isopropyl tris(dioctyl phosphate) A titanate coupling agent such as titanate, isopropyltricumylphenyl titanate or tetraisopropylbis(dioctylphosphite) titanate. One type of these may be used alone or two or more types may be used in combination. With respect to the liquid resin composition, the total amount of the (C) coupling agent is preferably from -15 to 201105698, preferably from 0.037 to 5.0% by mass, more preferably from 0.05 to 4.75 mass%, still more preferably from 0.1 to 2,5 mass. %. When it is less than 73〇% by mass, the adhesion between the substrate and the cured product of the liquid resin composition tends to be lowered, and when it exceeds 0.000% by mass, the physical properties such as the glass transition temperature or the bending strength are The tendency to decrease. As the (D) antioxidant used in the present invention, a conventional one can be used. For example, as a phenol compound-based antioxidant, a compound having at least one alkyl group in the ortho position to the phenol nucleus may, for example, be 2,6-di-t-butyl-4-methylphenol or η-octadecyl- 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2'-methylenebis-(4-methyl-6-t-butylphenol), 3 ,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propenyloxy]-1,1-dimethylethyl]-2,4, 8,10-Tetraoxaspiro[5.5]undecane, 4,4'-butylenebis-(6-t-butyl-3-methylphenol), 4,4'-thiobis(6- T-butyl-3-methylphenol), tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 2,2-thio - Diethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylene bis[3-(3,5- Di-t-butyl-4-hydroxyphenyl)propanamide], isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 1,3, 5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 4,6-bis(dodecylthiomethylίο-cresol, Bis(3,5-di-t-butyl-4-hydroxybenzylsulfonateethyl)calcium, 2,4-1 bis[(octylthio)methyl]-indole-cresol, 1 ,6-hexanediol·bis[3-(3,5-di-t-butyl-4 tetraphenyl)propionic acid vinegar], 6-[3-(3-t-butyl·4_ 5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenzo[d,f][l,3,2]dioxaphosphane, 2 -t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5 -di-t-pentylphenyl)ethyl]- -16- 201105698 Phenol 4,6-di-t-pentylphenyl acrylate, 2,2'-methylene double _ (4_B Base_6_t_butyl basic 酣), 2,6-mono-t-butyl-4-ethylbenzene, 1, hydrazine, 3_tris(2-methyl-4-trans--5-t-butyl Phenyl) butyl, triethylene glycol-bis[3_(3t butyl-4_hydroxy-5-methylphenyl)propionate] 'tris(3,5-di-t-butyl-4-yl) Amino acid, isocyanurate, diethyl [[卩^-bis^'丨-dimethylethyl) 4-phenylphenyl]methyl]phosphate, 2,5,7,8-tetramethyl Base 2 (4,,8',12,_trimethyltridecyl)chroman-6-ol, 2,4-bis-(η-octylthio)·6_(4_carbyl-3, 5 dibutyl butyl presente) -1,3,5-dioxin, and the like. As the cyclohexylamine, the product name D-CHA-T manufactured by Shin-Nippon Chemical Co., Ltd. is commercially available, and examples of the derivative thereof include dicyclohexylamine nitrite and N,N_: (3) _Methyl_cyclohexylamine), N,N-bis(2-methoxy-cyclohexyl)amine, N N-bis(4-bromo-cyclohexyl)amine, and the like. Examples of the organic sulfur compound-based antioxidant include dilauryl-3,3'-thiodipropionic acid vinegar, dimyristyl-3,3,-thiodipropionate, and distearyl- 3,3'-thiodipropionate, pentaerythritol tetrakis(3-laurylthiopropionate), two thirteenyl-3,3'-thiodipropionate, 2-mercaptobenzene And imidazole, 4,4'-thiobis(6-t-butyl-3-methylphenol), 2,2-thio-di-extension ethyl bis[3-(3,5-di-t- Butyl-4-hydroxyphenyl)propionate], 4,6-bis(dodecylthiomethyl)-indole-cresol, 2,4-1 bis[(octylthio)methyl]methyl 2 , 4-bis-(η-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, etc., as an amine compound antioxidant Examples thereof include N,N'-diallyl-P-phenylenediamine, N,N'-di-sec-butyl-P-phenylenediamine, octylated diphenylamine, 2,4- Bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, etc., as a phosphorus compound-based antioxidant, Triamyl phenyl phosphite, triphenyl phosphite, bis(3,5-di-t-butyl· -17- 201105698 4-hydroxybenzyl sulfonate ethyl) calcium Tris(2,4-di-t-butylphenyl)phosphite, 2-[[2,4,8,10-tetrakis(1,1-dimethylether)dibenzo[d,f] [l,3,2]dioxaphosphino-6-yl]oxy]-N,N-bis[2-{[2,4,8,10-tetra(1,1 dimethylethyl) Dibenzo[d,f][l,3,2]dioxaphosphino-6-yl]oxy}-ethyl]ethylamine, 6-[3-(3-t-butyl-4- Hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenzo[d,f][l,3,2]dioxaphosphane, two Ethyl [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphate or the like. One type of these may be used alone or two or more types may be used in combination. Further, among the phenol compound-based antioxidants, in addition to the phenolic hydroxyl group, at least one or more compounds containing at least one of a phosphorus atom, a sulfur atom and an amine in the same molecule are repeatedly enumerated. Among the above-mentioned antioxidants, from the viewpoint of improvement in migration resistance, a phenol compound-based antioxidant having at least one alkyl group in the ortho position to the phenol nucleus and dicyclohexylamine are more preferable. It is considered that in the phenol compound-based antioxidant having at least one alkyl group in the ortho position of the phenol nucleus, since the ortho-position alkyl group is an electron-donating group, in the unpaired electron portion of the oxygen atom of the phenolic hydroxyl group, The electron concentration is increased, the antioxidant is located on the surface of the anode metal, and in the dicyclohexylamine, since the unpaired electron sites of the nitrogen atom of the amine are located on the surface of the anode metal, the coordinated antioxidant on the metal surface inhibits oxidation of the metal. Degradation and increased migration resistance. In addition, the phenol compound-based antioxidant having at least one alkyl group in the ortho position of the phenolic core is generally known as a solid or powdery compound, but as a liquid resin composition for electronic parts, in order to avoid viscosity, In the (A) epoxy resin of the component -18-201105698 of the liquid resin composition for electronic parts, the cured product of the liquid resin composition for electronic parts is more preferably dissolved to have The degree of full resistance to migration. Specifically, in the general epoxy resin, for example, in the well-known bisphenol F-type epoxy resin used as the liquid epoxy resin in the present invention, the saturated dissolved amount is preferably 5% by mass or more. It is 1% by mass or more. The reason for this is that the phenol compound-based antioxidant having a saturated solubility in the above preferred range is dissolved in the epoxy resin, and the phenol compound-based antioxidant can be uniformly dispersed in the liquid resin composition for electronic parts, thereby improving Resistance to migration. Here, the above-mentioned saturated dissolved amount is usually carried out at room temperature due to the application of the liquid resin composition, and is considered to be enthalpy at room temperature in consideration of the stability of the liquid composition. In the phenol compound-based antioxidant having at least one alkyl group in the ortho position of the phenol nucleus, 4,4'-butylene bis-(6) is exemplified as the phenol compound-based antioxidant having such solubility. -t-butyl-3-methylphenol), tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 3,9-double [2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propanyloxy]-i,i-dimethylethyl]_ 2,4,8,10- Tetraoxaspiro[5_5]undecane, triethylene glycol bis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate] and the like. Further, among the phenol compound-based antioxidants dissolved in the epoxy resin, a phenol compound-based antioxidant having one methyl group in the ortho position to the phenol core is more preferable. It is considered that this is because the methyl group has few steric obstacles and is a power supply group, and the unpaired electrons of the phenolic hydroxyl group of the antioxidant are more easily coordinated to the surface of the anode metal. As such a phenol compound-based antioxidant, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propenyloxy]-1 is exemplified. 1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, triethylene glycol double t -19- 201105698 [3-(3-t-butyl-4 ·Hydroxy-5-methylphenyl)propionate]. Further, the dicyclohexylamine is a liquid at room temperature, and has an advantage of being able to be uniformly dispersed without impairing the viscosity, permeability, and fluidity of the liquid resin composition for an electronic component, as compared with the antioxidant of the solid or powder. The amount of the phenol compound-based antioxidant is preferably from 0.1 to 10% by mass, more preferably from 0.5 to 5.0% by mass, based on the (?) epoxy resin. When the amount is less than 0.1% by mass, the effect of suppressing migration is lowered, and when it is more than 10% by mass, the fluidity of the liquid resin composition for electronic parts tends to be lowered. Further, the saturated solvating amount D of the phenol compound-based antioxidant in the (Α) epoxy resin is 5% by mass. <〇 The blending amount at the time of 10% by mass is preferably 〇. 1 to D% by mass, more preferably 0·5 to 5 · 0% by mass. The amount of the dicyclohexylamine to be added is preferably from 0.1 to 30% by mass, more preferably from 0.5 to 10% by mass, based on the (?) epoxy resin. When the amount is less than 0.1% by mass, the effect of suppressing the migration is lowered. When the amount is more than 30% by mass, the storage stability of the liquid resin composition for electronic parts and the glass transition temperature of the cured product tend to be lowered. When the gap between the wiring boards or the bumps of the semiconductor device of the semiconductor device of the present invention is 20 μm or less, the liquidity for electronic components is good in order to improve the compatibility between the gaps and the fluidity. The amount of the solid compound insoluble in the resin composition is preferably 10% by mass or less, more preferably 5% by mass or less. On the other hand, when the circuit board of the liquid resin composition for electronic components of the present invention and the gap between the wirings or the bumps of the semiconductor device exceed 20 μm, the migration resistance is required to compensate for the circuit board and the semiconductor. For the purpose of the difference in thermal expansion coefficient of the device, -20-201105698 can be combined with an inorganic hydrazine agent within a range that does not impair the entanglement or fluidity between the gaps. The inorganic chelating agent can be a general user of the liquid resin composition for electronic components, and is not particularly limited, and examples thereof include vermiculite, carbonic acid such as molten vermiculite, crystalline vermiculite, and synthetic vermiculite. Alumina such as calcium, talc, clay, alumina, etc., tantalum nitride, tantalum carbide, boron nitride, calcium niobate, potassium titanate' aluminum nitride, tantalum oxide, zirconium oxide, vermiculite, forsterite, block Powders such as talc, spinel, mullite, titanium dioxide, or the like, or such spheroidized beads, glass fibers, and the like. Further, inorganic nanoparticles such as nano vermiculite obtained by a hydrolysis/condensation reaction of an alkoxide compound can also be used as a chelating agent. These inorganic chelating agents may be used singly or in combination of two or more. The shape of the inorganic chelating agent is preferably close to a spherical shape from the viewpoint of moldability such as fluidity. The average particle diameter of the inorganic chelating agent is preferably in the range of 5 nm to ΙΟμηη. When it exceeds ΙΟμηη, the sedimentation tends to occur, and the liquid resin composition for electronic components tends to have poor permeability and fluidity to the fine gap, and tends to cause voids and unfilling. Moreover, such sputum agents can also be used as needed for surface coupling treatment. The amount of the inorganic hydrazine filler is preferably 10% by mass or less, more preferably 5% by mass or less, based on the liquid resin composition for electronic parts. When the amount is more than 10% by mass, the difference between the linear expansion coefficient of the cured product of the liquid resin composition for an electronic component and the flexible circuit board using the film substrate becomes large, and peeling tends to occur at the interface between the two. Further, when the amount of the inorganic cerium charge is large, the viscosity of the liquid resin composition for electronic parts becomes high, and the fluidity tends to decrease due to an increase in surface tension. In the liquid resin composition for an electronic component of the present invention, it is preferred to use a curing accelerator which promotes the reaction of the epoxy resin of the component (A) and the curing agent containing the component (B) as needed in the range of -21 to 201105698. As the curing accelerator, a latent curing accelerator is preferred in order to coexist the curability with the pot life. The latent curing accelerator is a one which exhibits a hardening promoting function under conditions such as a specific temperature. For example, a usual curing accelerator may be a structure protected by microcapsules or the like, or a structure of various compounds and additional salts. In this case, if the temperature exceeds a certain temperature, the hardening accelerator is released from the microcapsule or the adduct. An example of the latent curing agent is a core-shell particle obtained by coating a shell of an epoxy compound having a normal temperature solid as a core at a normal temperature, and a commercially available product, Amicure can be used. (available from Ajinomoto Co., Ltd., registered trademark), or Novacure (registered trademark of Asahi Kasei Chemicals Co., Ltd.) in which a microencapsulated amine is dispersed in a bisphenol A epoxy resin or a bisphenol F epoxy resin. Wait. Further, the solid compound which is insoluble in the liquid resin composition for the electronic component and which is dissociated at the time of heat molding to exhibit the hardening-promoting amine compound or the phosphorus compound salt and the compound having the π bond A compound having intramolecular polarization can be used as a latent accelerator. If exemplified, 1,8-diaza-bicyclo(5,4,0)undecene-7, 1,5-diaza-bicyclo(4,3,0)nonene, 5 a cyclophosphonium compound such as 6-dibutylamino- 1,8-diaza-bicyclo(5,4,0)undecene-7 and an intramolecular electrode formed by a compound having a π bond Derivatization of tertiary amine compounds such as compound, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tri-22-201105698 (dimethylaminomethyl)benzoic acid a derivative of an imidazole compound such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-imidazole or 2-pyridylimidazole, An organic phosphine compound such as tributylphosphine, methyl diphenylphosphine, triphenylphosphine, diphenylphosphine or phenylphosphine is added with maleic anhydride, 1,4-benzoquinone, 2,5-toluene, 1,4-naphthoquinone, 2,3-dimethylphenylhydrazine, 2,6-dimethylphenylhydrazine, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2, a compound having a π bond such as a ruthenium compound such as 3-dimethoxy-1,4-benzoquinium phenyl-l, 4-benzoquinone or the like, a diazophenylmethane or a phenol resin; Internally polarized phosphorus compound, and derivatives such as 'triphenylphosphine triphenyl boron, tetraphenyl quaternary tetraphenyl borate' 2-ethyl-4-methylimidazolium tetraphenyl borate The phenyl boron salt such as hydrazine-methylmorpholine tetraphenylborate or the like may be used alone or in combination of two or more. Among them, from the viewpoint of storage stability and rapid hardenability, it is preferred that the microencapsulated amine is dispersed in a bisphenol fluorene type epoxy resin or a bisphenol F type epoxy resin. The amount of the hardening accelerator is not particularly limited as long as it is a curing-promoting effect, and is preferably 0.1 to 40 in terms of the total amount of the non-potential. The mass% is more preferably 0.5 to 30% by mass. When it is less than 0.1% by mass, the curing property tends to be poor for a short period of time, and if it exceeds 40% by mass, the curing rate is too fast and the control becomes difficult, or the storage stability such as the pot life and shelf life is maintained. There is a tendency to change. In the liquid resin composition for an electronic component of the present invention, in order to obtain the toughness or low elastic modulus of the cured epoxy resin of t 3 -23-201105698, it is preferred to incorporate various rubber particles known in the art. Although the rubber particles are incompatible with the epoxy resin, they do not lower the glass transition temperature (heat resistance) of the cured product, and are effective for lowering the elastic modulus. Specifically, for example, a butadiene. acrylonitrile ♦ styrene copolymer or a modified copolymer having an epoxy group, an amine group, a carboxyl group, a hydroxyl group or the like at the terminal or side chain of the polymer may be mentioned. The terminal or side chain has a modified polyoxosiloxane elastomer such as an epoxy group, an amine group, a carboxyl group or a hydroxyl group. From the viewpoint of workability or dispersibility of the resin component, the rubber particles are preferably used in the form of a fine powder and finely dispersed in an epoxy resin or a hardener in advance. From the viewpoint of being similarly mixed in the resin composition, it is preferably a rubber-modified epoxy resin which is liquid at normal temperature (heating and melting the liquid epoxy resin and the rubber particles). By containing the rubber particles, the adhesion between the cured product of the liquid resin composition for an electronic component and the substrate is improved, and reliability such as high temperature and high humidity resistance is improved. Further, in the liquid resin composition for an electronic component of the present invention, when used in a circuit board or a semiconductor device, the migration resistance, moisture resistance, and high temperature are improved without impairing the compatibility or fluidity. From the viewpoint of characteristics, it is preferred to further contain an ion trapping agent as needed. The ion scavenger is not particularly limited, and a conventional one may be used. Particularly, it is a hydrotalcite represented by the following composition formula (I) or a hydrous oxide of hydrazine represented by (II). (1) Μ gi-χΑΙχ (OH) 2 (C03)x/2 *ιηΗ2〇 (I) (in formula (I), 0 <XS0.5, m is a positive number) (Chem. 2) -24- 201105698 B i O, (OH) y (NO3), (II) (Formula (II), 0.9$xSl.l, 0.6SyS0.8, 0.2Sz$0.4) The amount of the ionic scavenger to be added is not particularly limited as long as it can capture an anion such as a halide ion, and is a liquid resin for electronic parts from the viewpoint of migration resistance. The composition is preferably from 0.1 to 3.0% by mass, more preferably from 0.3 to 1.5% by mass. The ion-trapping agent preferably has an average particle diameter of 0.1 to 3.0 μm, and the maximum particle diameter is preferably ΙΟμηη or less. Further, the compound of the above formula (I) is commercially available under the trade name DHT-4A manufactured by Kyowa Chemical Industry Co., Ltd., which is a commercial product. Further, the compound of the above formula (II) is commercially available under the trade name ΙΧΕ500 manufactured by Toagos Corporation of the commercial product. Further, other ion trapping agents may be added as needed. For example, a hydrated oxide of an element selected from magnesium, aluminum, titanium, pin, ruthenium, or the like may be used, and these may be used alone or in combination of two or more. Further, in the night-like resin composition for electronic parts of the present invention, it is preferred to add a polyoxymethylene-modified epoxy resin different from the above (Α) epoxy resin component as needed. By adding a polyoxymethylene-modified epoxy resin, it is effective in the leveling property, the fillet formation property, and the void reduction of the liquid resin composition for electronic parts. The polyoxymethylene-modified epoxy resin can be obtained as a reaction product of a polyorganodecane oxygen having an epoxy group-reactive functional group and an epoxy resin, and is preferably liquid at normal temperature. The polyoxymethylene-modified epoxy resin can be locally present on the surface of the liquid to reduce the surface tension of the liquid. By this, the wettability is improved and the flow is easy, so that the permeability to the narrow gap is improved or the void which is entrapped is reduced. Here, examples of the polyorganoindole-25-201105698 alkoxy group having a functional group reactive with an epoxy group include one or more amine groups, a carboxyl group 'hydroxy group, a phenolic hydroxyl group, a thiol group, and the like in one molecule. Dimethyl methoxy oxane, diphenyl siloxane, methyl phenyl oxa oxide, and the like. The weight average molecular weight of the polyorganodecane oxygen is preferably in the range of from 50,000 to 5,000. The reason is that if it is less than 500, the compatibility with the resin is excessively good, and the effect as an additive cannot be sufficiently exhibited. If it exceeds 5,000, the resin is incompatible with the resin, so the polyoxyl modified epoxy resin is Separation and oozing occur during forming, which impairs adhesion or appearance. The epoxy resin used for the polyoxymethylene-modified epoxy resin is not particularly limited as long as it is compatible with the resin of the liquid resin composition for electronic components, and a liquid resin for electronic components can be used. Examples of the epoxy resin generally used in the composition include those obtained by reacting bisphenol A, bisphenol F, bisphenol AD, bisphenol S, naphthalenediol, hydrogenated bisphenol A, and epichlorohydrin. A glycidyl ether type epoxy resin obtained by condensing or co-condensing a phenolic aldehyde with an o-cresol novolak type epoxy resin to obtain a phenolic varnish type epoxy resin obtained by epoxidizing or co-condensing a phenolic aldehyde resin The glycidyl ether type epoxy resin obtained by the reaction of a polybasic acid such as dicarboxylic acid or a dimer acid with epichlorohydrin is reacted with a polyamine such as diaminodiphenylmethane or isocyanuric acid and epichlorohydrin. The obtained glycidylamine type epoxy resin may be a linear aliphatic epoxy resin or an alicyclic epoxy resin obtained by oxidizing an olefin bond with a peracid such as peracetic acid, and may be used singly or in combination. Two or more types are used, and it is preferably a liquid at room temperature. In the liquid resin composition for an electronic component of the present invention, as a further additive, a dye, carbon black, or the like may be blended as needed within a range that does not impair the compatibility or fluidity when applied to a circuit board or a semiconductor device. Oxygen-26- 201105698 Tin, lead and other coloring agents, flame retardants, thinners, other leveling agents, other stress relaxation agents, defoamers 'adhesive accelerators, etc. As the flame retardant, a brominated epoxy resin or antimony trioxide can be used, and a non-halogen or non-fluorene flame retardant is preferably used. For example, red phosphorus, a phosphorus compound such as a red phosphorus, a phosphate ester or a triphenylphosphine oxide coated with a thermosetting resin such as a phenol resin, a melamine, a melamine derivative, a melamine-modified phenol resin, and a triterpenoid may be mentioned. a ring-containing compound, a cyanuric acid derivative, a nitrogen-containing compound such as an isocyanuric acid derivative, a phosphorus- and nitrogen-containing compound such as cyclophosphazene, a metal complex compound such as dicyclopentadienyl iron, or zinc oxide. a zinc compound such as zinc stannate, zinc borate or zinc molybdate, a metal oxide such as iron oxide or molybdenum oxide, a metal hydroxide such as aluminum hydroxide or magnesium hydroxide, or the following composition formula (III) Composite metal hydroxides, etc. (3) p (M1 a Ob ) · q (M2 c 〇d ) * r (M3 c 〇d ) · mH 2 O (III) (In the composition formula (ΠΙ), Μ1, M2 and M3 are different from each other Metal elements, 8, 1?, ";, <1? , 9 and 111 indicate positive numbers, and 1' indicates 〇 or positive numbers). M1 in the above composition formula (ΠΙ)! ^2 and M3 are not particularly limited as long as they are mutually different metal elements, but from the viewpoint of flame retardancy, M1 is preferably selected from the metal elements belonging to the third cycle and the alkaline earth metals of the IIA group. The metal element of the element, group IVB, group IIB, group VIII, group IB, group IIIA and group IVA, M2 is preferably a transition metal element selected from group IIIB to IIB -27-201105698, and Μ1 is more preferably selected from Magnesium, calcium, aluminum, tin, titanium, iron, indium, nickel, copper and zinc, more preferably selected from the group consisting of iron, cobalt, nickel, copper and zinc. From the viewpoint of fluidity, it is preferred that Μ1 is magnesium, Μ2 is zinc or nickel, and r = 〇. The molar ratio of p, q and r is not particularly limited, but is preferably r = 0, p/q = 1/99 to 1/1. Furthermore, the classification of metal elements is based on the periodic table of the long-period type in which the typical element is regarded as the A subfamily and the transition element is regarded as the b subfamily. The above-mentioned flame retardant may be used singly or in combination of two or more. As the diluent, a reactive diluent having an epoxy group for viscosity adjustment can be mixed. Examples of the reactive diluent having an epoxy group include n-butyl glycidic acid, versatic carbonic acid, styrene oxide, ethylhexyl glycidic acid, and phenyl glycidic acid. Butyl phenyl glycidyl ether, 1,6·hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, diethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether. One type of these may be used alone or two or more types may be used in combination. The liquid resin composition for an electronic component of the present invention can be prepared by any method as long as it can uniformly disperse and mix various components. As a general method, it is possible to carry out mixing and kneading using a kneader, a mixing roll, a planetary mixer or the like by weighing a component of a predetermined amount, and defoaming as necessary. The electronic component device obtained by sealing the device with the liquid resin composition for an electronic component obtained by the present invention may be a lead frame, a carrier tape for completing the wiring, a rigid and flexible circuit board, a glass, a germanium wafer, or the like. In the support structure 28 - 201105698, an active component such as a semiconductor wafer, a transistor, a diode, a thyristor, a passive element such as a capacitor, a resistor, a resistor array, a coil, a switch, or the like is mounted, and the like An electronic component device or the like obtained by sealing a necessary portion of a liquid resin composition for an electronic component. In particular, it is preferably used for sealing of an electronic component device in which an electronic component is directly connected by bumps on a circuit substrate on a film substrate. For example, the object is a flip-chip bonded semiconductor device in which a semiconductor element is bump-connected on a wiring formed on a rigid and flexible circuit board or glass. Specific examples include a semiconductor device such as a flip chip BGA or a COF (Chip On Film), and the liquid resin composition for an electronic component obtained by the present invention is particularly suitable as a bottom filler for COF having excellent migration resistance. . Further, the liquid resin composition for an electronic component of the present invention can be effectively used for a printed circuit board. The method of sealing the element using the liquid resin composition for an electronic component of the present invention includes a dispensing method, a molding method, a printing method, and the like. [Examples] Next, the present invention is illustrated by the examples, but the scope of the invention is not limited by the examples. (Examples 1 to 5 and Comparative Example) As the (A) epoxy resin, a bisphenol F-type liquid epoxy resin having an epoxy group equivalent of 160 (trade name YDF-817〇C manufactured by Tohto Kasei Co., Ltd.) was prepared. -29 - 201105698 A naphthalene type epoxy resin having an epoxy group equivalent of 140 (trade name: HP-4032, manufactured by Otsuka Ink Industries Co., Ltd.). As a rubber particle component, prepare: acrylonitrile in a ratio of 1/4 by mass in advance. . Dingdi. Methyl acrylate acid / divinyl benzene copolymer (trade name xer-91P, manufactured by JSR Corporation) is hot melted and finely dispersed in bisphenol F type liquid epoxy resin (YDF-8170C) A rubber-modified epoxy resin, as a leveling agent, is prepared: a phenol-modified polyoxyl oxide having a hydroxyl equivalent weight of 750 (trade name BY 1 6-799 manufactured by Toray Dow Corning Co., Ltd.) and a bisphenol F type liquid Polyoxyethylene-modified epoxy resin obtained by heating and mixing the epoxy resin (YDF-8 1 70C) at a mass ratio of 1/1. As a (B) cyclic acid anhydride, preparation: normal temperature liquid and anhydride equivalent 234 A cyclic acid anhydride (trade name jERcure YH306, manufactured by Nippon Epoxy Co., Ltd.), as (C) coupling agent, prepared: γ-glycidoxy Propyltrimethoxydecane (trade name 信-403, manufactured by Shin-Etsu Chemical Co., Ltd.), as (D) antioxidant, prepared: 4,4'-butylidenebis-(6-t-butyl-3-methyl Phenol) (trade name YoshinoxBB, manufactured by the company API Corporation; antioxidant 1), tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane Company API Corporation's trade name Tominox TT: Antioxidant 2), -30- 201105698 3,9-bis[2-[3-(3-1-butyl-4-hydroxy-5-methylphenyl)propene Oxy]_ 1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane (trade name ADE-80, manufactured by the company ADEKA; antioxidant 3), three Ethylene glycol bis[3_(3-t-butyl-4-transyl-5-methylphenyl)propionic acid vinegar] (trade name API company, Yoshinox 917; antioxidant 4), dicyclohexylamine (D-CHA-T, manufactured by Shin-Nippon Chemical Co., Ltd.; Antioxidant 5), as a hardening accelerator, prepared: 2-ethyl-4-methylimidazole (trade name 2E4MZ, manufactured by Shikoku Chemical Industry Co., Ltd.) > As a sputum preparation, prepare: spherical surface with a specific surface area of lm2/g and an average particle size of 4μηι To Silica. Each of these was blended in a mass fraction shown in the following Table 1, and kneaded and dispersed in a pulverizer, followed by vacuum defoaming to prepare liquid resin compositions for electronic parts of Examples 1 to 5 and Comparative Examples. -31 - 201105698 [Table i] Formulation Example Comparative Example 1 2 3 4 5 Bisphenol F-type epoxy resin 50 50 50 50 50 50 Naphthalene type epoxy resin 20 20 20 20 20 20 Rubber-modified epoxy resin 30 30 30 30 30 30 Polyoxymethylene modified epoxy resin 1 1 1 1 1 1 Cyclic anhydride 130 130 130 130 130 130 Coupler 1 1 1 1 1 1 Antioxidant 1 1 Antioxidant 2 1 Antioxidant 3 1 Antioxidant 4 1 Antioxidant 5 1 Hardening accelerator 1 1 1 1 1 1 (Unit: parts by mass) The liquid resin compositions for electronic parts of Examples 1 to 5 and Comparative Examples produced were evaluated by the following tests. The evaluation results are shown in Table 2 below. (1) The viscosity was measured using an EMD type rotary viscometer (manufactured by the company TOKIMEC), and the liquid resin compositions for electronic parts held at 25 ± 1 ° C, Examples 1 to 5, and the comparative examples were rotated at 100 rpm for 1 minute. The scale of the time is multiplied by a conversion factor of 0.0125, which is taken as the viscosity. (2) Gelation time 0.1 g of a liquid resin composition for electronic parts was dropped on a hot plate at 150 ° C, and stirred with a spatula in a manner that was not excessively spread. After the dropping, the viscosity of the liquid resin composition for the electronic component rises, and the time until the wire is pulled up without picking up the spatula is taken as the gelation time. (3) Water absorption rate The liquid resin composition for electronic parts was hardened at 150 ° C for 2 hours to prepare a test piece of 50 mm x 5 mm x 1 mm. After the initial weight Wi of the test piece was measured, it was placed in a high-temperature and high-humidity bath of 85 ° C / 85%, and the weight W 2 ' after 1 hour of measurement was measured by the following formula. (Water absorption rate ^{(Ws-Wd/Wt } X 1 00 (%) (4) Adhesive strength on polyimide film (Toray Dupont Co., Ltd. under the trade name Kapton), making electronic parts composed of liquid resin The material was hardened at 150 ° C for 2 hours, and cut into a rectangular shape having a width of 10 mm. The tensile tester (manufactured by Shimadzu Corporation) was used to peel the polyimine at 90 degrees. The peeling strength of the film was used as the adhesive force. (5) The SUS spacer having a thickness of 20 μm was sandwiched between two sheets of glass to make a flow path with a width of 5 mm. Place it horizontally on a 7 (TC heating plate). After that, the liquid resin composition for electronic parts was dropped, and the time until the gap between the gaps was 20 mm was measured. It was not good for 3 minutes, and it was bad for 3 minutes or longer. (6) Evaluation of migration resistance to polyimine On the film, a liquid resin composition for an electronic component is applied by dispensing on a counter electrode portion of a flexible circuit board having a wiring width of 15 μm and a wiring interval of 15 μm by a tinned copper wiring. , will be used at 1 50 ° C, 2 hours hardened as a test piece. This test -33- 201105 In the 698 test piece, a voltage of 60 V DC was applied to a high temperature and high humidity of 120 ° C / 85%, and the resistance 値 was continuously measured. When the resistance 値 became 1 〇 6Q or less, it was judged that a leak occurred. The liquid resin composition for an electronic component having a resistance 値 of not less than 10 6 Ω was taken as > 5 〇〇 hours. (7) Appearance evaluation The transmission light of the solid microscope was observed and the migration resistance evaluation was completed. The subsequent test piece 'observed the degree of corrosion of the tinned copper wiring on the polyimide film. If migration occurred, it was observed that the wiring metal was corroded and dissolved in the resin from the anode side. Therefore, if it is transmitted light Observe, as shown in Figure i, corresponding to the extent of migration, see the width of the anode wiring is thicker than before the test. The most corroded wiring width is compared with the wiring width before the test, which will be 1·0~1.1 times. For ◎, 1.1 to 1.2 times as 〇, 1.2 to i · 3 times as △, and 1.3 times or more as X. [Table 2]
評價項目 實施例 比較例 1 2 3 4 5 黏度 Pa-S 0.6 0.6 0.6 0.6 0.6 0.6 膠化時間 min 0.9 0.9 0.9 0.9 0.9 0.9 吸水率 % 0.7 0.7 0.7 0.7 0.7 0.7 黏著力 N/m >1000 >1000 >1000 >1000 >1000 >1000 侵入性 良 良 良 良 良 良 耐遷移性 h 330-360 340-380 >500 480-490 460-470 270-280 外觀 Δ Δ ◎ ◎ 〇 X 實施例1〜5皆係配合有抗氧化劑的電子零件用液狀 -34- 201105698 樹脂組成物’若與沒有配合抗氧化劑的比較例作比較，係 不損害黏度、膠化時間、吸水率、黏著力、侵入性等之作 爲電子零件用液狀樹脂組成物所必要的諸特性，可提高耐 遷移性。其中，使用鄰位具有一個甲基的抗氧化劑之實施 例3、4’係絕緣可靠性、耐腐蝕性最優異，其次使用二 環己基胺的實施例5係絕緣可靠性、耐腐蝕性優異，顯示 高的耐遷移性。茲認爲此係因爲藉由抗氧化劑的配合，而 防止高溫高濕環境下的樹脂硬化物之氧化降解，抑制雜質 離子的生成或絕緣性的降低，同時作用於金屬表面而抑制 金屬的腐蝕。 產業上的利用可能性 本發明的電子零件用液狀樹脂組成物，係耐遷移性良 好，其它成形性、可靠性亦優異的電子零件用液狀樹脂組 成物，其工業價値大。特別地，適用作爲藉由凸塊連接半 導體元件於剛性電路板及撓性電路板玻璃上所形成的配線 之覆晶接合的半導體裝置，具體地覆晶BG A或COF等之 半導體裝置用的底部塡充材。 【圖式簡單說明】 圖1之（3)係顯示耐遷移性評價中試驗前的陽極附近 及配線寬度之圖。 圖1之（b)係顯示發生遷移後的陽極附近及配線寬度 之圖。 -35-Evaluation item Example Comparative Example 1 2 3 4 5 Viscosity Pa-S 0.6 0.6 0.6 0.6 0.6 0.6 Gelation time min 0.9 0.9 0.9 0.9 0.9 0.9 Water absorption % 0.7 0.7 0.7 0.7 0.7 0.7 Adhesion N/m > 1000 > 1000 >1000 >1000 >1000 >1000 Invasive good good good migration resistance h 330-360 340-380 >500 480-490 460-470 270-280 Appearance Δ Δ ◎ ◎ 〇X Examples 1 to 5 are liquid-based electronic components for antioxidants-34-201105698 Resin composition's comparison with comparative examples without antioxidants does not impair viscosity, gelation time, water absorption, adhesion The properties necessary for the liquid resin composition for electronic parts, such as force and intrusion, can improve migration resistance. Among them, Examples 3 and 4' using an antioxidant having one methyl group in the ortho position are most excellent in insulation reliability and corrosion resistance, and Example 5 using dicyclohexylamine is excellent in insulation reliability and corrosion resistance. Shows high migration resistance. It is considered that this is because the oxidation of the cured resin in a high-temperature and high-humidity environment is prevented by the action of the antioxidant, and the formation of the impurity ions or the decrease in the insulation property is suppressed, and the metal surface is suppressed to inhibit the corrosion of the metal. Industrial Applicability The liquid resin composition for electronic components of the present invention is a liquid resin composition for electronic parts which is excellent in migration resistance and excellent in moldability and reliability, and has an industrial price. In particular, it is applied to a flip-chip bonded semiconductor device which is a wiring formed by connecting a semiconductor element to a rigid circuit board and a flexible circuit board glass by bumps, and specifically, a bottom portion for a semiconductor device such as BG A or COF. Filling the material. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1(3) is a view showing the vicinity of an anode and a wiring width before the test in the migration resistance evaluation. Fig. 1(b) is a view showing the vicinity of the anode after the migration and the wiring width. -35-