201026750 六、發明說明： 【發明所屬之技術領域】 本發明係關於新穎的聚醯胺醯亞胺樹脂、使用其之黏 著劑組成物、耐熱性印墨、黏著劑片、覆蓋薄膜、玻璃絲 網含浸預浸漬物及使用此等之印刷電路基板。特別是關於 適合於加濕後耐焊性與高溫彎曲性優異之印刷電路板的耐 熱性印墨、黏著劑組成物。 【先前技術】 φ 迄今，做爲耐熱性黏著劑雖然可使用以聚醯亞胺系樹 月旨、環氧樹脂等爲主成分之材料，但是在使用此等樹脂上 有著若干的問題。 其中之一，可舉例如耐熱性與低溫黏著性的兼具。至 今，聚醯亞胺因耐熱性優異，所以對於高溫下黏著之強力 設備是必要的，而可在低溫下黏著之環氧系黏著劑則有著 所謂耐熱性變差的問題。 針對兼具上述的低溫黏著性與耐熱性的具體方法已有 ® 若干的揭示。例如，有使用耐熱性環氧樹脂、馬來醯亞胺 樹脂等的方法，惟由於此等樹脂因爲其硬化密度高而脆弱 ’所以用途受限。又，專利文獻1中雖然揭示使具有特定構 造之聚醚醯亞胺與環氧樹脂摻混，可兼具低溫黏著性與耐 熱性’但是根據其内容，黏著時間若是使用數分鐘的話， 黏著溫度必須爲2〇〇°c，則難請有充分的低溫黏著性。 又’亦有提案聚醯胺醯亞胺系的耐熱黏著劑，例如專 利文獻2、專利文獻3係提案有使丙烯腈-丁二烯共聚合之聚 醯胺醯亞胺及使用其之半導體用黏著劑，又專利文獻4、專 -4- 201026750 利文獻5係提案有使二聚酸共聚合之聚醯胺醯亞胺及使用 其之半導體用黏著劑，但是完全均無法得到滿足低溫黏著 性、耐熱性、特別是加濕後的耐焊性、與在高溫高濕下在 銅箔的電路部分生成樹枝狀晶體所引起的抗滲移性。 先行技術文獻 專利文獻 專利文獻1 特開昭63-99280 專利文獻2 特開平11 — 0 21455 φ 專利文獻3 特開2001-011421 專利文獻4 特開平11-021454 專利文獻5 特開2001-011420 【發明內容】 發明所欲解決之課題 本發明係有鑑於該迄今技術的現狀而發明者，其目的 係提供含有低溫黏著性、抗滲移性與耐熱性、特別是加濕 後的耐焊性優異之聚醯胺醯亞胺樹脂的黏著劑組成物、特 別是有用於印刷電路板的黏著劑組成物及使用其之印墨、 黏著劑片、覆蓋薄膜、以及使用彼等之印刷電路基版、適 合使用於此等的聚醯胺醯亞胺樹脂。 用於解決課題之手段 本發明者係爲了達成該目的，經專心一意硏究的結果 而完成本發明。亦即本發明係： —種聚醯胺醯亞胺樹脂，其特徵係對數黏度爲0.2 dl/g 以上，酸價爲400當量/i〇6g~ 1000當量/i〇6g，且在側鏈 201026750 * 上具有竣基。 (2) 如U)記載之聚醯胺醯亞胺樹脂，其中在聚醯胺 樹脂的全部酸成分當作1 0 0莫耳。/。之情形中’酸, 3~30莫耳％爲偏苯三酸。 (3) 如（2)記載之聚醯胺醯亞胺樹脂，其中前述偏苯 藉由加水至偏苯三酸酐中而使得偏苯三酸酐被開環: • (4) 如（1)記載之聚醯胺醯亞胺樹脂，其中在聚醯胺 樹脂的全部酸成分當作1 0 0莫耳。/。之情形中，酸 3~30莫耳％爲二羥甲基丁酸。 (5) 如（1)記載之聚醯胺醯亞胺樹脂，其中藉由使偏 酐及/或四羧酸酐與二胺成分及/或二異氰酸酯成分 形成預聚物之後，利用伸烷二醇使該預聚物鏈延長 (6) 如（5)記載之聚醯胺醯亞胺樹脂，其中前述伸烷 由數量平均分子量4 00~10000的聚乙二醇、聚丙二 四亞甲基二醇所構成群組中所選出之1種以上。 (7) 一種黏著劑組成物，其特徵係在如（1)~(6)項中 之聚醯胺醯亞胺樹脂中，含有由多官能環氧化合物 能異氰酸酯化合物及三聚氰胺化合物所構成群組中 醯亞胺 成分的 三酸係 醯亞胺 成分的 苯三酸 反應而 而得到 二醇係 醇及聚 任一項 、多官 所選出 201026750 之1種以上的化合物。 (8) 如（7)記載之黏著劑組成物，其係含有相對於黏著劑組 成物的總固體含量之磷含量爲1重量％以上、3重量％以下的 有機磷化合物。 (9) 一種印刷電路基板用印墨’其特徵係在如（7 )或（8 )記載 之黏著劑組成物中，含有無機及/或有機微粒子，且搖變指 φ 數爲1.2以上3.0以下。 (10) 一種覆蓋薄膜，其係使用如（7)或（8)記載之黏著劑組成 物而成的。 (11) 一種黏著劑片，其係使如（7)或（8)記載之黏著劑組成物 塗布、乾燥於聚丙烯薄膜、脫膜紙或脫膜薄膜上而成的。 (12) # 一種印刷電路基板，其係使用如（7 )或（8)記載之黏著劑 組成物而成的。 發明的效果 根據本發明的話’可容易得到對於金屬與聚醯亞胺薄 膜的低溫黏著性與耐焊性、特別是加濕處理後的耐焊性及 在高溫高濕下的耐滲移特性優異之黏著劑組成物、有用於 印刷電路基板的印墨、黏著劑片、及覆蓋薄膜以及使用此 等之印刷電路基板、及適合於使用此等的聚醯胺醯亞胺樹 脂。 201026750 【實施方式】 實施發明之最佳形態 本發明係關於可低溫黏著、抗滲移性及耐熱性、特別 是加濕後的耐焊性優異之黏著劑組成物及將其成形之黏著 劑片、覆蓋薄膜、玻璃絲網含浸預浸漬物、印刷電路基板 用印墨，以及使用此等之印刷電路基板、而且適合於此等 的聚醯胺醯亞胺樹脂。 1.聚醯胺醯亞胺樹脂 本發明中所使用之聚醯胺醯亞胺樹脂係可利用醯氯法 或異氰酸酯法等眾所周知的方法而製造。 做爲聚醯胺醯亞胺樹脂的製造中所使用的酸成分係除 了偏苯三酸及其酸酐、氯化物以外，可舉例如焦蜜石酸、 聯苯基四羧酸、二苯碾四羧酸、二苯基酮四羧酸、聯苯基 醚四羧酸、乙二醇雙偏苯三酸酯、丙二醇雙偏苯三酸酯等 的四羧酸及此等的酸酐、草酸、己二酸、丙二酸、癸二酸 、壬二酸、十二烷二羧酸、二羧基聚丁二烯、二羧基聚（丙 烯腈-丁二烯）、二羧基聚（苯乙烯-丁二烯）等的脂肪族二羧 酸、1，4環己烷二羧酸、1,3環己烷二羧酸、4,4‘二環己基 甲烷二羧酸、二聚酸等的脂環族二羧酸、對苯二甲酸、間 苯二甲酸、二苯碾二羧酸、二苯基醚二羧酸、萘二羧酸等 的芳香族二羧酸。在此等之中，從反應性、耐熱性、黏著 性、溶解性等的點而言，偏苯三酸酐爲最佳、其一部分爲 偏苯三酸、二羧基聚（丙烯腈-丁二烯）、二聚酸所取代者爲 更佳。 做爲聚醯胺醯亞胺樹脂的製造中所使用之二胺或二異 201026750 氰酸酯，可舉例如乙二胺、丙二胺、六亞甲基二胺等的脂 肪族二胺及此等的二異氰酸酯、i4-環己烷二胺、1，3_環 己烷二胺、異佛酮二胺、4,4’-二環己基甲烷二胺等的脂環 族二胺及此等的二異氰酸酯、m-苯二胺、P-苯二胺、4，4’_ 二胺基二苯基甲烷、4，4’-二胺基二苯基醚、4，4’-二胺基二 苯碾、聯苯胺、〇-聯甲苯胺、2,4_甲苯二胺、2,6-甲苯二 胺、苯二甲基二胺等的芳香族二胺、二胺基聚（丙烯腈-丁 二烯）及此等的二異氰酸酯；此等之中’從耐熱性、黏著性 φ 、溶解性等而言，較佳爲4,4’-二胺基二苯基甲烷或4,4’-二苯基甲烷二異氰酸酯、異佛酮二胺或異佛酮二異氰酸酯 、及二胺基聚（丙烯腈-丁二烯）等。 在本發明的聚醯胺醯亞胺樹脂係除了上述的酸成分與 二胺或二異氰酸酯成分以外，還可以共聚合多元醇成分。 多元醇成分係可舉例如乙二醇、二甘醇、三乙二醇、二羥 甲基丁酸、聚乙二醇、丙二醇、聚丙二醇、四亞甲基二醇 、聚四亞甲基二醇、聚酯二醇、碳酸酯二醇等的二醇與季 ❹ 戊四醇等的三官能以上的醇；此等之中，從黏著性、溶解 性而言’較佳爲聚酯二醇、聚乙二醇、聚丙二醇、聚四亞 甲基二醇。於側鏈導入羧基之情形係以二羥甲基丁酸與數 量平均分子量爲400~10000的聚乙二醇、聚丙二醇與聚四 亞甲基二醇爲佳。 本發明的聚醯胺醯亞胺樹脂係爲了滿足使用於印刷電 路基板時的耐熱性、特別是加濕後的耐焊特性、低溫黏著 性與抗滲移性的全部’係有必要爲高分子量體且爲高酸價 。具體而言’作爲分子量基準的聚醯胺醯亞胺樹脂之對數 201026750 黏度爲0.2dl/g以上。對數黏度低於0.2dl/g的話，形成膜 時的強度與伸度低，所以得不到充分的黏著力。上限係沒 有特別地限制，惟對數黏度變得過大時，在混合硬化劑與 難燃劑、其他的添加劑之情形中，與彼等的相溶性降低， 又溶液黏度變高，而有作業性降低的情形，實質上，若爲 1.5dl/g以下爲佳。較佳爲0.3〜l.Odl/g、更佳爲 0.3~0.5dl/g ° 對數黏度通常係可依照酸成分與二胺成分（二異氰酸 φ 酯成分）的進料比或聚合溫度、濃度、觸媒的添加等進行調 整，可藉由增多二胺成分（二異氰酸酯成分）、又提高聚合 溫度或濃度、添加觸媒等，來增大對數黏度。 本發明的聚醯胺醯亞胺樹脂的酸價係在400當量 /l〇6g~l〇〇〇當量/l〇6g的範圍，較佳爲450當量 /l〇6g~l〇〇〇 當量 / i〇6g，更佳爲 500 當量 / l〇6g~1000 當量 /l〇6g。酸價超過上述上限時，即使用後述之多官能環氧 化合物、多官能異氰酸酯化合物、三聚氰胺化合物等使黏 著劑組成物硬化之後，亦有羧基殘存的可能性，且抗滲移 性、加濕後耐焊性係爲降低。又酸價低於上述下限的話， 與多官能環氧化合物、多官能異氰酸酯化合物及三聚氰胺 化合物等的反應點變少、硬化密度降低、加濕後的耐耐焊 性性變得不充分。 如下述（1)~(4)般，藉由在聚醯胺醯亞胺樹脂的側鏈上 具有羧基，可得到具有前述範圍之酸價的聚醯胺醯亞胺樹 脂。但是，並不限定於下述的方法。 (1)在聚醯胺醯亞胺樹脂的全部酸成分當作100莫耳。/。 -10- 201026750 之情形’爲了含有酸成分的3~30莫耳。爲偏苯三酸而進行 聚醯胺醯亞胺的聚合。 例如’若使用偏苯二酸酐作爲酸成分的話，將偏苯三 酸酐的3~30莫耳。/。取代爲偏苯三酸以進行聚合。該情形下 ，預先準備偏苯三酸與該偏苯三酸爲0.9~1.2倍當量的二異 氰酸酯化合物，且在80 °C以下使其反應之後，加入殘留的 原料（酸成分與二異氰酸酯成分）以進行聚合爲佳。從一開 始就同時進料偏苯三酸酐與偏苯三酸及二異氰酸醋化合物 φ ’所以在高溫聚合時會有凝膠化之情形。又，前述偏苯三 酸可以直接使用市售的偏苯三酸而沒有關係，惟藉由在聚 合前或聚合中加入相當於偏苯三酸酐的3 ~30莫耳％的水， 使偏苯三酸酐予以開環’以生成與水相當之當量的偏苯三 酸’亦可使其與二異氰酸酯反應而使用。該情形下，預先 準備偏苯三酸酐與水且在80 °C以下的溫度使其反應之後， 加入二異氰酸酯化合物以聚合聚醯胺醯亞胺樹脂爲佳。 聚醯胺醯亞胺樹脂的全部酸成分當作1 〇 〇莫耳。/。之情 • 形中，藉由含有酸成分的3~30莫耳％爲偏苯三酸，可使羧 基載持於聚醯胺醯亞胺樹脂的側鏈上，且有效地進行多官 能環氧化合物、多官能異氰酸酯化合物及三聚氰胺化合物 等的與多官能化合物的反應，並提昇加濕焊錫等的耐熱性 。低於3莫耳％的話，由於聚醯胺醯亞胺樹脂的酸價低，且 在加入多官能環氧化合物、多官能異氰酸酯與三聚氰胺化 合物等的多官能化合物之情形中無法進行充分的交聯，會 有耐熱性不足之情形，在超過30莫耳％之情形中，則有膜 變硬變脆且密合性降低，又羧基變得過剩，且抗滲移性降 -11- 201026750 低之情形。 (2) 在聚醯胺醯亞胺樹脂的全部酸成分當作1〇〇莫胃％ 之情形中，爲了含有酸成分的3 ~30莫耳％爲二羥甲基丁酸 而進行聚合。 例如，用二羥甲基丁酸取代偏苯三酸酐的3~30莫耳％ 以與二異氰酸酯進行反應。該情形下，可以將二羥甲基了 酸與一開始的其他原料同時加入進行聚合，亦可以預先在 80 °C以下使二羥甲基丁酸與其0_9~1.2倍莫耳的二異氰酸 φ 酯化合物反應之後，追加其他的原料並進行聚合。將二經 甲基丁酸與一開始的其他原料同時加入進行聚合之情形， 較佳係起先在80 °C以下進行聚合且使二羥甲基丁酸與二異 氰酸酯化合物反應之後，在100 °C以上的溫度下進行聚合 〇 聚醯胺醯亞胺樹脂的全部酸成分當作100莫耳％之情 形’藉由含有酸成分的3~30莫耳％爲二羥甲基丁酸，可使 羧基載持在聚醯胺醯亞胺樹脂的側鏈上，且有效地進行多 Φ 官能環氧化合物、多官能異氰酸酯化合物及三聚氰胺化合 物等的與多官能化合物的反應，並可提昇加濕焊錫等的耐 熱性。低於3莫耳％的話’由於聚醯胺醯亞胺樹脂的酸價低 ’且在加入多官能環氧化合物、多官能異氰酸酯與三聚氣 胺化合物等的多官能化合物之情形中無法進行充分的交聯 ’所以會有耐熱性不足的情形，在超過30莫耳。/。以上之情 形’則有膜變硬變脆且密合性降低’又羧基變得過剩，抗 滲移性降低的情形。 (3) 使偏苯三酸酐及/或四羧酸物與二胺成分及/或二 -12- 201026750 異氰酸酯成分反應以合成預聚物之後’加入伸烷二醇使其 反應殘存的酸酐，鏈延長的同時將羧基導入於側鏈中。 預聚物的分子量係沒有特別地限制，惟數量平均分子 量爲10,000以下爲佳，更佳係5000以下。在聚合預聚物之 際，酸成分與二胺成分的比率使酸成分多一些爲佳，聚醯 胺醯亞胺的情形則優先使醯胺結合形成之後進行爲佳。預 聚物合成較佳係在8 (TC以下進行。 作爲伸烷二醇而言，係可使用乙二醇、丙二醇、四亞 φ 甲基二醇及此等的寡聚物，此等之中，從黏著性等點而言 ，較佳係使用由數量平均分子量爲400〜10000、較佳係數 量平均分子量600~2000的聚乙二醇、聚丙二醇及聚四亞甲 基二醇所構成群組中所選出之1種以上的伸烷二醇。此時， 亦可利用二羥甲基丁酸使鏈延長。此外，爲了使聚醯胺醯 亞胺樹脂全體的酸價成爲400當量/106g~ 1000當量/ l〇6g ，亦可調節伸烷二醇的添加量而進行聚合。 (4)亦可以組合上述（1}、（2)、（3)的方法，調整作爲全 • 體之聚醯胺醯亞胺的酸價之方法。 根據上述的方法，可得到在側鏈具有羧基之本案發明 的聚醯胺醯亞胺樹脂。一般的話，由於凝膠化引起交聯等 的聚醯胺醯亞胺樹脂係爲可期料的，所以在聚合中加入如 偏苯三酸般的三官能化合物係爲該業者一般進行的操作， 但是本發明人等係針對溫度控制等的聚合條件重覆專心一 意硏究的結果，發現若預先使偏苯三酸與該偏苯三酸的 〇·9~1·2倍當量之二異氰酸酯化合物在80°C以下反應之後 ’加入殘留的原料（酸成分與二異氰酸酯成分）以進行聚合 -13- 201026750 之方法的話，可得到抑制凝膠化且在側鏈具有羧基之聚醯 胺醯亞胺樹脂。藉由在本發明的聚醯胺醯亞胺樹脂中，加 入由多官能環氧化合物、多官能異氰酸酯化合物及三聚氰 胺化合物所構成群組中所選出之1種以上的化合物使其反 應’可得到低溫黏著性、在高溫高濕下的抗滲移性及耐熱 性、特別是加濕後的耐焊性優異的黏著劑組成物。尤其是 在高溫高濕下的抗滲移性及加濕後的耐焊性係特別優異。 藉由新發現的在聚醯胺醯亞胺樹脂之側鏈上導入羧基的聚 Φ 合法，則變成可增加聚醯胺醯亞胺樹脂的交聯點。交聯點 的增加係認爲對於密合性提昇有貢獻，藉此可大幅地改良 耐濕性，且抗滲移性、加濕後的耐焊性係爲優異。 本發明的聚醯胺醯亞胺樹脂係可在N，N’-二甲基乙醯 胺與N-甲基-2-吡咯啶酮、N，Ν’-二甲基甲醯胺、7·-丁內酯 等的極性溶劑中，一邊加熱至60~200°C、一邊進行攪拌， 而能容易地製造。該情形下，可按照需要使用觸媒。做爲 觸媒係使用甲醇鈉、氟化鉀等的金靥鹽、三乙胺、三乙二 φ 胺、二氮雜雙環十一碳烯等的胺類。又，上述的聚合溶劑 係可將其一部分置換成其他比較便宜且沸點較低的溶劑。 做爲彼等溶劑係可舉出甲醇、乙醇、丁醇等的醇類、丙酮 、丁酮、環己嗣等的酮類、乙酸甲酯、乙酸乙酯等的酯類 、甲苯、二甲苯等的烴類等，較佳係用此等的溶劑置換全 體爲約40重量％的聚合溶媒。 又，可將上述聚合溶液投入不與聚合溶液混合的溶劑 、較佳係丙酮或水之中，除去、洗淨、乾燥聚合溶劑，且 再溶解於其他的溶劑中而使用。使用於再溶解的溶劑係可 -14- 201026750 舉出甲醇、乙醇、丁醇等的醇類、甲苯、二甲苯等的芳香 族烴類、四氫呋喃、二噁烷等的醚類、環戊酮、環己酮等 的酮類等。 2 .黏著劑組成物 本發明的黏著劑組成物係在對數黏度爲0.2dl/g以上 、酸價爲400當量/106g~10〇0當量/106g、且側鏈上具有 羧基聚醯胺醯亞胺樹脂中’含有由多官能環氧化合物、多 官能異氰酸酯化合物及三聚氰胺化合物所構成群組中所選 φ 出之1種以上的化合物。藉由在前述聚醯胺醯亞胺樹脂中’ 摻混、加熱、硬化由多官能環氧化合物、多官能異氰酸酯 化合物及三聚氰胺化合物所構成群組中所選出之1種以上 的化合物，可形成高度的交聯構造，且發現有優異的密合 性與加濕耐焊性等。 於本發明的聚醯胺醯亞胺樹脂中所組合的多官能環氧 化合物係沒有特別地限制，可舉出雙酚A縮水甘油醚類、苯 酚酚醛清漆型環氧化合物、胺型環氧化合物等。從與聚醯 • 胺醯亞胺樹脂的相溶性、交聯密度的觀點而言，特佳爲苯 酚酚醛清漆型環氧化合物。 又，多官能異氰酸酯化合物係沒有限制，可舉出三羥 甲基丙烷的甲苯二異氰酸酯與異佛酮二異氰酸酯、二苯基 甲烷二異氰酸酯、六亞甲基二異氰酸酯的三加成物、六亞 甲基二異氰酸酯的環狀三聚物等。從密合性、交聯密度之 觀點而言，特佳係六亞甲基二異氰酸酯的環狀三聚物。 三聚氰胺化合物係可舉出三羥甲基三聚氰胺的甲基醚 、丁基醚等。 -15- 201026750 此等的多官能環氧化合物、多官能異氰酸酯化合物、 三聚氰胺化合物等的多官能化合物係相對於聚醯胺醯亞胺 樹脂100重量份，以3~200重量份的範圍摻混爲佳，更佳係 以10~100重量份的範圍摻混。多官能化合物的摻混量低於 3重量份的話，則有加濕焊錫等的耐熱性與耐藥品性不足的 情形，又超過200重量份時，由於膜變硬、變脆而有相反 地降低密合性的情形。 進一步詳細設計的話，在使其硬化反應的前階段中， φ 多官能環氧化合物、多官能異氰酸酯化合物、三聚氰胺化 合物等的多官能化合物的環氧基或NCO基的個數/聚醯胺 醯亞胺樹脂之羧基的個數=1~50爲佳，更佳係在3~25的範 圍。由於被摻混的環氧化合物一般並非未必全部都參與硬 化反應，所以相對於聚醯胺醯亞胺樹脂的羧基而言，加入 等量或過剩的量爲佳。相對於羧基而言，環氧基低於1的話 ，會有硬化不充分且加濕後的耐焊性、抗滲移性不足的情 形，又超過50時則有硬化後的黏著劑層脆弱且密合性降低 φ 的傾向。 經硬化反應之後的聚醯胺醯亞胺樹脂的酸價係以1 〇 〇 當量/ 106g以下爲佳、更佳係30當量/ 106g以下。 又，此等的多官能化合物中，做爲各自的硬化助劑與 觸媒係例如在環氧化合物的情形中可使用多元羧酸與彼等 之酸酐、咪唑化合物、胺系觸媒，在異氰酸酯化合物的情201026750 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a novel polyamidoximine resin, an adhesive composition using the same, a heat-resistant ink, an adhesive sheet, a cover film, and a glass mesh impregnation A prepreg and a printed circuit board using the same. In particular, it relates to a heat-resistant ink and an adhesive composition suitable for a printed circuit board excellent in solder resistance and high-temperature bending property after humidification. [Prior Art] φ As a heat-resistant adhesive, a material mainly composed of a polyimine-based resin or an epoxy resin can be used, but there are some problems in using these resins. One of them may be, for example, a combination of heat resistance and low-temperature adhesion. Since polyiminoimide is excellent in heat resistance, it is necessary for a strong device to be adhered at a high temperature, and an epoxy-based adhesive which can be adhered at a low temperature has a problem that heat resistance is deteriorated. There have been several disclosures on specific methods that combine the above-mentioned low temperature adhesion and heat resistance. For example, there is a method of using a heat-resistant epoxy resin, a maleidene resin, or the like, but since these resins are weak due to their high hardening density, their use is limited. Further, in Patent Document 1, it is disclosed that a polyether sulfimine having a specific structure is blended with an epoxy resin, and both low-temperature adhesion and heat resistance can be combined. However, depending on the content, if the adhesion time is several minutes, the adhesion temperature is used. Must be 2 〇〇 °c, then it is difficult to have sufficient low temperature adhesion. Further, there is also proposed a polyamidoximine-based heat-resistant adhesive. For example, Patent Document 2 and Patent Document 3 propose a polyamidoximine which copolymerizes acrylonitrile-butadiene and a semiconductor using the same. Adhesives, Patent Document 4, and -4-201026750. The literature 5 proposes a polyamido quinone imine copolymerizing a dimer acid and a semiconductor adhesive using the same, but it is impossible to satisfy the low temperature adhesion. Heat resistance, in particular, solder resistance after humidification, and bleed resistance caused by dendrites formed in a circuit portion of a copper foil under high temperature and high humidity. PRIOR ART DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PRIORARY SUMMARY OF THE INVENTION The present invention has been made in view of the current state of the art, and an object of the present invention is to provide low-temperature adhesion, impermeability and heat resistance, and particularly excellent solder resistance after humidification. An adhesive composition of a polyamidoximine resin, particularly an adhesive composition for a printed circuit board, and an ink, an adhesive sheet, a cover film, and a printed circuit board using the same, which are suitable for use in a printed circuit board The polyamidoximine resin used herein is used. Means for Solving the Problems The inventors of the present invention have completed the present invention by focusing on the results in order to achieve the object. That is, the present invention is: a polyamidoquinone imine resin characterized by a logarithmic viscosity of 0.2 dl/g or more, an acid value of 400 equivalent/i〇6g~1000 equivalent/i〇6g, and in the side chain 201026750 * Has a sputum base. (2) A polyamidoximine resin as described in U), wherein all of the acid component of the polyamide resin is regarded as 100 moles. /. In the case of 'acid, 3 to 30 mol% is trimellitic acid. (3) The polyamidoximine resin according to (2), wherein the trimellitic benzene is subjected to ring-opening by adding water to trimellitic anhydride: (4) The polyamidoquinone imine described in (1) A resin in which all the acid components in the polyamide resin are regarded as 1 0 0 mole. /. In the case, the acid 3 to 30 mol% is dimethylolbutanoic acid. (5) The polyamidoximine resin according to (1), wherein the meta-anhydride and/or the tetracarboxylic anhydride and the diamine component and/or the diisocyanate component are used to form a prepolymer, and then the alkylene glycol is used. The prepolymer chain is extended (6), wherein the alkane is a polyethylene glycol or a polytetramethylene glycol having a number average molecular weight of from 00 to 10,000. One or more selected ones of the group. (7) An adhesive composition characterized by comprising a polyfunctional epoxy compound isocyanate compound and a melamine compound in the polyamidoquinone imine resin as in (1) to (6) The trimellitic acid of the tribasic quinone imine component of the quinone imine component is reacted to obtain a diol-based alcohol, and one or more compounds selected from 2010-0650. (8) The adhesive composition according to (7), which contains an organic phosphorus compound having a phosphorus content of 1% by weight or more and 3% by weight or less based on the total solid content of the adhesive composition. (9) The ink composition for a printed circuit board is characterized in that the adhesive composition according to (7) or (8) contains inorganic and/or organic fine particles, and the number of the rocking fingers is 1.2 or more and 3.0 or less. (10) A cover film obtained by using the adhesive composition as described in (7) or (8). (11) An adhesive sheet obtained by coating and drying an adhesive composition as described in (7) or (8) on a polypropylene film, a release paper or a release film. (12) # A printed circuit board obtained by using the adhesive composition as described in (7) or (8). Advantageous Effects of Invention According to the present invention, it is easy to obtain low-temperature adhesion and solder resistance to a metal and a polyimide film, particularly, solder resistance after humidification treatment and excellent resistance to bleeding under high temperature and high humidity. The adhesive composition includes an ink for a printed circuit board, an adhesive sheet, a cover film, a printed circuit board using the same, and a polyimide amide resin suitable for use. BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to an adhesive composition which is excellent in low-temperature adhesion, bleed resistance, heat resistance, and particularly excellent solder resistance after humidification, and an adhesive sheet which is formed by the same. A cover film, a glass mesh impregnated prepreg, an ink for a printed circuit board, and a polyacrylamide imide resin which is suitable for use in such a printed circuit board. 1. Polyamidamine imine resin The polyamidoximine resin used in the present invention can be produced by a known method such as a ruthenium chloride method or an isocyanate method. The acid component used in the production of the polyamidoximine resin is, for example, pyromellitic acid, biphenyltetracarboxylic acid, diphenyl milling, in addition to trimellitic acid, its anhydride, and chloride. a tetracarboxylic acid such as a carboxylic acid, a diphenyl ketone tetracarboxylic acid, a biphenyl ether tetracarboxylic acid, an ethylene glycol trimellitate, or a propylene glycol trimellitate, and an acid anhydride, oxalic acid, or the like Diacid, malonic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, dicarboxy polybutadiene, dicarboxy poly(acrylonitrile-butadiene), dicarboxy poly(styrene-butadiene) An alicyclic group such as an aliphatic dicarboxylic acid such as an alkene, a 1,4-cyclohexanedicarboxylic acid, a 1,3-cyclohexanedicarboxylic acid, a 4,4'-dicyclohexylmethanedicarboxylic acid or a dimer acid An aromatic dicarboxylic acid such as dicarboxylic acid, terephthalic acid, isophthalic acid, diphenyl or dicarboxylic acid, diphenyl ether dicarboxylic acid or naphthalene dicarboxylic acid. Among these, trimellitic anhydride is preferred from the viewpoints of reactivity, heat resistance, adhesion, solubility, etc., and a part thereof is trimellitic acid, dicarboxy poly(acrylonitrile-butadiene), and It is better to replace the polyacid. The diamine or diiso 201026750 cyanate used in the production of a polyamidoximine resin may, for example, be an aliphatic diamine such as ethylenediamine, propylenediamine or hexamethylenediamine. An alicyclic diamine such as a diisocyanate, i4-cyclohexanediamine, 1,3-cyclohexanediamine, isophoronediamine or 4,4'-dicyclohexylmethanediamine, and the like Diisocyanate, m-phenylenediamine, P-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diamino Aromatic diamines such as diphenyl milling, benzidine, hydrazine-tolidine, 2,4-toluenediamine, 2,6-toluenediamine, benzenedimethyldiamine, diamine poly(acrylonitrile- Butadiene) and such diisocyanates; among these, '4,4'-diaminodiphenylmethane or 4,4' is preferred from the viewpoints of heat resistance, adhesion φ, solubility, and the like. - Diphenylmethane diisocyanate, isophorone diamine or isophorone diisocyanate, and diamine poly (acrylonitrile-butadiene). In the polyamidoximine resin of the present invention, in addition to the above acid component and the diamine or diisocyanate component, the polyol component may be copolymerized. Examples of the polyol component include ethylene glycol, diethylene glycol, triethylene glycol, dimethylol butyric acid, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, and polytetramethylene. a diol such as an alcohol, a polyester diol or a carbonate diol, or a trifunctional or higher alcohol such as quaternary pentaerythritol; among these, a polyester diol is preferred from the viewpoint of adhesion and solubility. , polyethylene glycol, polypropylene glycol, polytetramethylene glycol. In the case where a carboxyl group is introduced into the side chain, dimethylol butyric acid and a plurality of polyethylene glycol, polypropylene glycol and polytetramethylene glycol having an average molecular weight of 400 to 10,000 are preferred. The polyamidoximine resin of the present invention is required to have high molecular weight in order to satisfy heat resistance when used in a printed circuit board, particularly solder resistance after humidification, low-temperature adhesion, and bleed resistance. The body is high in acid value. Specifically, the logarithm of the polyamidoximine resin as a molecular weight reference 201026750 has a viscosity of 0.2 dl/g or more. When the logarithmic viscosity is less than 0.2 dl/g, the strength and elongation at the time of film formation are low, so that sufficient adhesion cannot be obtained. The upper limit is not particularly limited, but when the logarithmic viscosity is too large, in the case of mixing a hardener, a flame retardant, or other additives, the compatibility with them is lowered, the viscosity of the solution is increased, and the workability is lowered. In the case of substantially, it is preferably 1.5 dl/g or less. Preferably, it is 0.3 to 1.0 dl/g, more preferably 0.3 to 0.5 dl/g. The logarithmic viscosity is usually based on the feed ratio or polymerization temperature of the acid component and the diamine component (diisocyanate φ ester component). The concentration and the addition of the catalyst are adjusted, and the logarithmic viscosity can be increased by increasing the diamine component (diisocyanate component), increasing the polymerization temperature or concentration, and adding a catalyst. The acid value of the polyamidoximine resin of the present invention is in the range of 400 equivalents / l 〇 6g 〇〇〇 〇〇〇 equivalent / l 〇 6g, preferably 450 equivalent / l 〇 6g ~ l 〇〇〇 equivalent / I 〇 6g, more preferably 500 equivalent / l 〇 6g ~ 1000 equivalent / l 〇 6g. When the acid value is more than the above upper limit, the adhesive composition may be cured by using a polyfunctional epoxy compound, a polyfunctional isocyanate compound or a melamine compound to be described later, and the carboxyl group may remain, and the migration resistance and the humidification resistance may be performed. The solder resistance is reduced. When the acid value is less than the lower limit, the reaction point with the polyfunctional epoxy compound, the polyfunctional isocyanate compound, the melamine compound or the like is small, the curing density is lowered, and the solder resistance after the humidification is insufficient. As in the following (1) to (4), a polyamidoquinone imine resin having an acid value in the above range can be obtained by having a carboxyl group in the side chain of the polyamidoximine resin. However, it is not limited to the method described below. (1) The total acid component of the polyamidoximine resin is regarded as 100 moles. /. -10- 201026750 The situation 'for 3 to 30 moles containing acid components. The polymerization of polyamidoximine is carried out for trimellitic acid. For example, if phthalic anhydride is used as the acid component, 3 to 30 moles of trimellitic anhydride is used. /. It is substituted with trimellitic acid to carry out polymerization. In this case, a diisocyanate compound having a trimeric acid and a trimellitic acid of 0.9 to 1.2 equivalents is prepared in advance, and after reacting at 80 ° C or lower, a residual raw material (acid component and diisocyanate component) is added. It is preferred to carry out the polymerization. Simultaneously, trimellitic anhydride, trimellitic acid and diisocyanate compound φ ' are fed at the same time, so that gelation occurs at high temperature polymerization. Further, the trimellitic acid may be directly used as a commercially available trimellitic acid, but the trimellitic anhydride may be opened by adding 3 to 30 mol% of water equivalent to trimellitic anhydride before or during the polymerization. The trimellitic acid' which produces an equivalent equivalent to water can also be used by reacting it with a diisocyanate. In this case, after the trimellitic anhydride and water are prepared in advance and reacted at a temperature of 80 ° C or lower, the diisocyanate compound is preferably added to polymerize the polyamidoximine resin. The entire acid component of the polyamidoximine resin is treated as 1 〇 〇 Mo. /. In the form, by adding 3 to 30 mol% of acid component to trimellitic acid, the carboxyl group can be supported on the side chain of the polyamidoximine resin, and the polyfunctional epoxy can be efficiently carried out. The reaction with a polyfunctional compound such as a compound, a polyfunctional isocyanate compound, or a melamine compound improves the heat resistance of the solder or the like. When the amount is less than 3 mol%, the acid value of the polyamidoximine resin is low, and sufficient crosslinking cannot be performed in the case of adding a polyfunctional compound such as a polyfunctional epoxy compound, a polyfunctional isocyanate or a melamine compound. In the case where the heat resistance is insufficient, in the case of more than 30% by mole, the film becomes hard and brittle and the adhesion is lowered, and the carboxyl group becomes excessive, and the migration resistance is lowered to 11 - 201026750. situation. (2) In the case where the total acid component of the polyamidoximine resin is 1%, the polymerization is carried out in order to contain 3 to 30 mol% of the acid component as dimethylolbutanoic acid. For example, 3 to 30 mol% of trimellitic anhydride is substituted with dimethylolbutanoic acid to react with the diisocyanate. In this case, the dimethylol acid can be added simultaneously with the other starting materials for polymerization, or the dimethylolbutyric acid and the 0-9-1.2 moles of diisocyanate can be preliminarily below 80 °C. After the reaction of the φ ester compound, another raw material is added and polymerization is carried out. When methyl butyl butyric acid is added to the other materials at the same time for polymerization, it is preferred to carry out the polymerization at 80 ° C or lower and react the dimethylol butyric acid with the diisocyanate compound at 100 ° C. At the above temperature, the total acid component of the polymerized polyamidoximine resin is regarded as 100 mol%. 'The carboxyl group can be obtained by using 3 to 30 mol% of the acid component as dimethylolbutanoic acid. It is supported on a side chain of a polyamidoximine resin, and efficiently reacts with a polyfunctional compound such as a poly-functional epoxy compound, a polyfunctional isocyanate compound, a melamine compound, etc., and can enhance humidification solder or the like. Heat resistance. When the amount is less than 3 mol%, 'the acid value of the polyamidoquinone imide resin is low' and it is not sufficient in the case of adding a polyfunctional compound such as a polyfunctional epoxy compound, a polyfunctional isocyanate or a trimeric gas amine compound. The cross-linking 'so there will be insufficient heat resistance in more than 30 moles. /. In the above case, the film becomes hard and brittle and the adhesion is lowered, and the carboxyl group becomes excessive and the bleed resistance is lowered. (3) reacting trimellitic anhydride and/or tetracarboxylic acid with a diamine component and/or a di-12-201026750 isocyanate component to synthesize a prepolymer, and then adding an alkylene glycol to cause an acid anhydride remaining in the reaction, and extending the chain The carboxyl group is introduced into the side chain. The molecular weight of the prepolymer is not particularly limited, but the number average molecular weight is preferably 10,000 or less, more preferably 5,000 or less. In the case of polymerizing the prepolymer, the ratio of the acid component to the diamine component is preferably such that the acid component is more preferred, and in the case of the polyamidoximine, it is preferred to carry out the formation of the guanamine. The prepolymer synthesis is preferably carried out at 8 (TC or less. As the alkylene glycol, ethylene glycol, propylene glycol, tetrakis φ methyl glycol, and the like are used, among which From the viewpoint of adhesion and the like, it is preferred to use a group consisting of polyethylene glycol, polypropylene glycol and polytetramethylene glycol having a number average molecular weight of 400 to 10,000 and a preferred molecular weight of 600 to 2000. One or more kinds of alkylene glycols selected from the group. In this case, the chain may be extended by dimethylolbutanoic acid. In addition, the acid value of the entire polyamidoquinone imide resin is 400 equivalents/106 g. ~ 1000 equivalent / l 〇 6g, can also be adjusted by adjusting the amount of alkylene glycol added. (4) The above methods (1}, (2), (3) can also be combined to adjust the concentration as a whole body. A method for the acid value of amidoxime. According to the above method, a polyamidoximine resin of the present invention having a carboxyl group in a side chain can be obtained. In general, a polyamine which is crosslinked by gelation is obtained. The quinone imine resin is expected, so a trifunctional compound such as trimellitic acid is added to the polymerization. The inventors of the present invention have repeatedly conducted intent on the polymerization conditions such as temperature control, and found that if trimellitic acid and the trimellitic acid are used in advance, 〇·9~ When a 1.2-fold equivalent of a diisocyanate compound is added to a residual raw material (acid component and diisocyanate component) after the reaction at 80 ° C or lower to carry out the polymerization of -13 to 26,770, a gelation inhibition and a side chain can be obtained. A polyamidoximine resin having a carboxyl group, which is selected from the group consisting of a polyfunctional epoxy compound, a polyfunctional isocyanate compound, and a melamine compound in the polyamidoximine resin of the present invention. The above-mentioned compound reacts to obtain low-temperature adhesion, high-humidity resistance to migration and heat resistance, and particularly excellent adhesion resistance after humidification, especially at high temperature and high humidity. The next bleed resistance and the solder resistance after humidification are particularly excellent. By newly discovered poly Φ law in which a carboxyl group is introduced into the side chain of the polyamide amide resin, it becomes polyg Crosslinking point of the amine quinone imine resin. The increase in the crosslinking point is considered to contribute to the improvement of the adhesion, thereby greatly improving the moisture resistance, and the bleed resistance and the solder resistance after humidification It is excellent. The polyamidoximine resin of the present invention can be used in N,N'-dimethylacetamide and N-methyl-2-pyrrolidone, N, Ν'-dimethylformamide In a polar solvent such as 7-butyrolactone, it can be easily produced by stirring while heating to 60 to 200 ° C. In this case, a catalyst can be used as needed. Methanol is used as a catalyst. An amine such as a gold sulfonium salt such as sodium or potassium fluoride, a triethylamine, a triethylenediamine or a diazabicycloundecene. Further, the above-mentioned polymerization solvent can be partially replaced with other amines. The solvent having a low boiling point. Examples of the solvent system include alcohols such as methanol, ethanol, and butanol, ketones such as acetone, methyl ethyl ketone, and cyclohexanyl, and esters such as methyl acetate and ethyl acetate. It is preferred to use a solvent such as toluene or xylene to replace a polymerization solvent of about 40% by weight with the entire solvent. Further, the polymerization solution may be introduced into a solvent which is not mixed with the polymerization solution, preferably acetone or water, and the polymerization solvent is removed, washed, dried, and dissolved in another solvent. The solvent to be used for re-dissolution may be -14,267,670,50, an alcohol such as methanol, ethanol or butanol, an aromatic hydrocarbon such as toluene or xylene, an ether such as tetrahydrofuran or dioxane, or a cyclopentanone. Ketones such as cyclohexanone. 2. Adhesive Composition The adhesive composition of the present invention has a logarithmic viscosity of 0.2 dl/g or more, an acid value of 400 equivalents/106 g to 10 〇0 equivalent/106 g, and a carboxyl group on the side chain. The amine resin contains one or more compounds selected from the group consisting of a polyfunctional epoxy compound, a polyfunctional isocyanate compound, and a melamine compound. The height can be formed by blending, heating, and hardening one or more compounds selected from the group consisting of a polyfunctional epoxy compound, a polyfunctional isocyanate compound, and a melamine compound in the above polyamidoximine resin. The crosslinked structure was found to have excellent adhesion and wet solder resistance. The polyfunctional epoxy compound to be combined in the polyamidoximine resin of the present invention is not particularly limited, and examples thereof include bisphenol A glycidyl ether, phenol novolak epoxy compound, and amine epoxy compound. Wait. From the viewpoint of compatibility with the polyfluorene-amine imine resin and crosslinking density, a phenol novolac type epoxy compound is particularly preferred. Further, the polyfunctional isocyanate compound is not limited, and examples thereof include toluene diisocyanate of trimethylolpropane, isoformone diisocyanate, diphenylmethane diisocyanate, and hexamethylene diisocyanate. A cyclic trimer of methyl diisocyanate or the like. From the viewpoint of adhesion and crosslinking density, a cyclic trimer of hexamethylene diisocyanate is particularly preferred. The melamine compound may, for example, be a methyl ether or a butyl ether of trimethylol melamine. -15-201026750 The polyfunctional compound such as a polyfunctional epoxy compound, a polyfunctional isocyanate compound, or a melamine compound is blended in an amount of 3 to 200 parts by weight based on 100 parts by weight of the polyamidoximine resin. Preferably, it is preferably blended in a range of 10 to 100 parts by weight. When the blending amount of the polyfunctional compound is less than 3 parts by weight, the heat resistance and chemical resistance of the wet solder or the like may be insufficient. When the amount exceeds 200 parts by weight, the film becomes hard and becomes brittle and is inversely lowered. The case of adhesion. Further detailed design, in the pre-stage of the hardening reaction, the number of epoxy groups or NCO groups of the polyfunctional compound such as φ polyfunctional epoxy compound, polyfunctional isocyanate compound or melamine compound/polyamine amide The number of carboxyl groups of the amine resin is preferably from 1 to 50, more preferably from 3 to 25. Since the epoxy compound to be blended generally does not necessarily all participate in the hardening reaction, it is preferred to add an equivalent amount or an excess amount to the carboxyl group of the polyamidoximine resin. When the epoxy group is less than 1 with respect to the carboxyl group, the curing may be insufficient, and the solder resistance and the bleeding resistance after humidification may be insufficient. When the epoxy group is more than 50, the adhesive layer after curing may be weak. Adhesion reduces the tendency of φ. The acid value of the polyamidoximine resin after the hardening reaction is preferably 1 〇 / / 106 g or less, more preferably 30 equivalent / 106 g or less. Further, among these polyfunctional compounds, as the respective curing assistants and catalysts, for example, in the case of an epoxy compound, polycarboxylic acids and their anhydrides, imidazole compounds, amine catalysts, and isocyanates can be used. Compound condition
I 形中可使用二丁基錫二月桂酸酯等的金屬化合物，又在三 聚氰胺化合物的情形中可使用P-甲苯磺酸等的觸媒。 本發明的聚醯胺醯亞胺樹脂及於其中摻混多官能環氧 -16- 201026750 化合物、多官能異氰酸酯化合物、三聚氰胺化合物等的多 官能化合物之黏著劑組成物作爲黏著劑與塗布劑使用的情 形中，可摻混賦予難燃性用的有機或無機之磷化合物。磷 化合物係沒有特別地限制，可舉出紅磷、各種磷酸鈉、磷 酸鎂、磷酸鈣等的無機磷酸鹽、磷酸三乙酯、磷酸三苯酯 、磷酸三甲苯酚酯、磷酸酯縮合物等的磷酸酯與磷腈化合 物、次膦酸衍生物等，特別是從耐濕性之觀點而言，特佳 係磷腈化合物。相對於黏著劑組成物固體含量，可添加磷 φ 化合物以使得磷含量成爲1重量％以上3重量以下。低於1 重量％的話則有難以得到難燃性效果的傾向，超過3重量％ 時不僅過剩，而且會有樹脂的密合性、耐濕性下降的傾向 〇 在本發明的黏著劑組成物中，在不損及本發明的内容 之範圍內，可適當摻混矽石與碳酸鈣等的塡充劑、無機、 有機的顏料、染料、抗靜電劑、勻化劑、磷化合物以外的 作爲難燃劑之聚矽氧化合物、氫氧化鋁、尿素化合物等及 • 聚醯胺醯亞胺以外的樹脂，例如聚酯、聚醯胺、聚醯亞胺 、聚胺基甲酸酯等。 本發明的黏著劑組成物係可作爲將黏著劑組成物溶解 於溶劑之黏著劑溶液使用。例如，可將該黏著劑溶液塗布 、乾燥於被黏物之後，與另一方的被黏物重疊，利用加熱 輥或熱壓處理使其壓延，按照需要進行加熱硬化處理，藉 以作爲黏著劑使用。 前述溶劑可使用於聚醯胺醯亞胺樹脂的聚合中所使用 之N，N’-二甲基乙醯胺或N-甲基-2-吡咯啶酮、N，N’-二甲基 -17- 201026750 甲醯胺、r -丁內酯等的溶劑，惟在黏著劑層中殘留有溶劑 時，由於會在黏著加工時發泡、又耐熱性本身係爲降低而 成爲不好的結果，所以較佳係使用將高沸點的聚合溶劑置 換成甲醇、乙醇、丁醇等的醇類、乙酸甲酯、乙酸乙酯等 的酯類、甲苯、二甲苯等的芳香族烴類、醚、丙酮、丁酮 、環己酮等的酮類等的低沸點溶劑者。較佳係用此等溶劑 置換溶劑全體之40重量％左右的聚合溶媒。 黏著劑溶液中，固體含量濃度係可根據使用目的而適 φ 宜設定，惟較佳係20~60重量％、更佳係30~50重量％ » 本發明的聚醯胺醯亞胺樹脂及多官能環氧化合物、多 官能異氰酸酯化合物、三聚氰胺化合物等的摻混多官能化 合物之組成物的用途係沒有特別地限制，最有用的用途係 印刷電路板關連用黏著劑或電路保護的絶緣油墨。具體而 言，可舉例如聚醯亞胺薄膜與聚酯薄膜、玻璃環氧片、貼 合銅箔與鋁箔等於酚醛樹脂片等的絶緣基材上之黏著劑、 覆蓋薄膜用黏著劑、與覆蓋薄膜同樣地保護電路之絶緣油 • 墨、用增強板強化電路基板的一部分之情形的黏著劑、搭 載直接半導體晶片於電路基板上之情形的黏著劑等。 3 .印刷電路基板用絶緣油墨 使用本發明的聚醯胺醯亞胺樹脂作爲印刷電路基板用 絶緣油墨之情形，在聚醯胺醯亞胺樹脂及前述多官能化合 物的混合溶液中，相對於聚醯胺醯亞胺樹脂及前述多官能 化合物的混合溶液，較佳爲摻混分散0.5~10重量％、更佳 爲1~5重量％的氧化矽與硫酸鈣等的無機粒子及/或各種有 機的微粒子，BH型黏度計的回轉數爲4rpm/20rpm，以25 -18- 201026750 °C的黏度比所表示的搖變指數爲1.2以上3. 〇以下，且相對 於聚醯胺醯亞胺樹脂溶液及前述多官能化合物的混合，較 佳係可摻混使用〇_5~5重量％的聚矽氧系或丙烯酸系的消 泡劑與勻化劑。 4.覆蓋薄膜 本發明的覆蓋薄膜係將本發明的黏著劑組成物作爲黏 著劑層，由絶緣性薄膜層/黏著劑層的2層構成、或由絶緣 性薄膜層/黏著劑層/保護薄膜層的3層構成所構成的。所 φ 謂的絶緣性薄膜係由聚醯亞胺、聚酯、聚苯硫醚、聚醚颯 、聚醚醚酮、芳族聚醯胺、聚碳酸酯、聚芳酯等的塑膠薄 膜所構成的厚度爲5~200〆m的薄膜，‘亦可積層從此等所選 出之複數片的薄膜。 覆蓋薄膜的製造方法係將溶解本發明的黏著劑組成物 於溶劑之黏著劑溶液，塗布、乾燥於上述之絶緣性薄膜上 ，以形成黏著劑層。 該情形下，黏著劑層較佳係成爲經適度半硬化之狀態 © ’將乾燥後的黏著劑層浸漬於10(TC的N-甲基-2-吡咯啶酮 中2小時之後的溶解殘存量爲2~70%、較佳爲5~50%的範 圍。爲此’上述乾燥溫度係以1 0 0 ~ 1 7 0 °C、乾燥時間係 以1~1〇分鐘進行爲佳。再者，按照需要乾燥後，亦可在 50~100°C進行加熱處理1〇~24小時。上述黏著劑層在乾燥 後的厚度較佳爲約5~40^111。此外，形成用以保管等的3 層構成之情形，係可進一步層壓積層脫膜性保護薄膜。 5 .黏著劑片 所謂的黏著劑片係指將本發明的黏著劑組成物作爲黏 -19- 201026750 著劑層，且具有至少1層以上的可剝離之保護薄膜的構成者 。例如，保護薄膜層/黏著劑層的2層構成、或保護薄膜層 /黏著劑層/保護薄膜的3層構成爲符合。這裡所謂的保護 薄膜層若爲不損及黏著劑層的形態且可以剝離的話’沒有 特別地限制，可舉例如聚丙烯薄膜與聚酯薄膜 '聚矽氧與 經蠟處理之聚酯薄膜和紙等。又’亦可使用金屬、陶瓷等 ，不僅可賦予表面的絶緣性、以耐環境性爲目的之保護， 而且還有可賦予放熱、電磁屏蔽、增強、識別等的新功能 @ 之優點。 可舉例如將黏著劑溶液塗布、乾燥於聚丙烯薄膜與聚 酯薄膜、聚矽氧與經蠟處理之聚酯薄膜和紙等的脫膜基材 上，較佳係用與上述之覆蓋薄膜同樣的方法，將經半硬化 之狀態的黏著劑薄膜與片插入2種類的被黏物中，且利用加 熱輥與熱壓處理進行加熱壓延，並可按照需要使其硬化。 該情形下亦可與塗布法同樣地，使用將不殘留溶劑的 片溶解於低沸點溶劑中而形成者爲較佳。 • 6 .印刷電路基板 可將本發明的黏著劑組成物作爲黏著劑層且在該黏著 劑層貼合絶緣性薄膜與銅箔，又可使用本發明的印刷電路 基板用印墨、覆蓋薄膜以製造印刷電路基板。銅箔係可使 用在印刷電路基板中以往所使用的壓延銅箔、電解銅箔。 所謂的絶緣薄膜係可使用作爲上述之覆蓋薄膜的絶緣性薄 膜所説明者。 實施例 以下係表示實施例以具體説明，惟本發明係不因此等 -20- 201026750 的實施例而受到任何的限制° 此外，實施例中的測定値係利用以下的方法來測定。 (1) 聚醯胺醯亞胺樹脂的酸價 在將聚醯胺醯亞胺〇.4g溶解於DMF2〇ml之溶液中’滴 下百里香酚酞2~3滴、及1/10規定之甲醇鈉的甲醇溶液’ 並從顏色的變化進行滴定而求得。 (2) 對數黏度 使用烏伯類德黏度管’在25 °C下測定將乾燥聚合物 φ Q.5g溶解於100mL的NMP中之溶液。 (3) 黏著力 用東洋Bald win公司製萬能拉力機且以剝離角度90度 ，測定實施例試樣的剝離強度。測定實施例1 ~ 1 0、比較例 4中聚醯亞胺薄膜與電解銅箔（消光面）的黏著力、及實施例 11~20、比較例卜3中聚醯亞胺薄膜與壓延銅箔（亮光面）的 黏著力、和實施例2卜28中聚醯亞胺薄膜與鋁板製增強板 的黏著力。 • (4)加濕後的耐焊性 將與測定黏著力同樣的試樣於4 0°C、80% RH的雰圍氣 下靜置48hr之後，觀察在26CTC的焊錫浴中漂浮30秒時的 狀態。判定係如以下所示來進行。 〇：觀察不到膨脹或剝離。 x :產生了膨脹或剝離。 (5)抗滲移性 蝕刻實施例1~1〇、比較例4中所作成之各種覆銅積層 板以形成線寬/間距（line/space)爲70/70/zm的電路，除 -21- 201026750 了接續端子部以外，以在150 °C中熱壓處理2分鐘貼合市售 聚醯亞胺覆蓋薄膜（NIKKAN工業製CISV)，且在150°C中使 其硬化2小時。對此等施加端子間電壓50V，且測定在85 °C、8 5%RH的雰圍氣中放置2週間之後的絶緣電阻値。 又另一方面，在實施例11~20、比較例1~3中，係在使 用絶緣層爲2〇vm且18；am壓延銅箱之覆銅積層板 VYLOFLEX(東洋紡製）上，形成線寬/間距爲70/70 #πι那 樣的電路，且將塗布使用各種聚醯胺醯亞胺樹脂溶液的黏 φ 著劑而成之覆蓋薄膜貼合於上述電路面上，並在試樣的端 子間施加50V的電壓之狀態下，測定於85°C、85%HR的雰 圍氣中放置2週之後的絶緣電阻値的變化。 判定方式係如以下所示。 〇：線間絶緣電阻値爲1Ε + 08Ω以上 x :線間絶緣電阻値爲1 E + 0 8 Ω以下 (6) 伸烷二醇的數量平均分子量 按照JISK-0070以測定羥基價，且利用以下的計算而 φ 求得。A metal compound such as dibutyltin dilaurate can be used for the I form, and a catalyst such as P-toluenesulfonic acid can be used in the case of the melamine compound. The polyamidoximine resin of the present invention and an adhesive composition of a polyfunctional compound in which a polyfunctional epoxy-16-201026750 compound, a polyfunctional isocyanate compound, a melamine compound or the like is blended as an adhesive and a coating agent are used. In this case, an organic or inorganic phosphorus compound imparting flame retardancy may be blended. The phosphorus compound is not particularly limited, and examples thereof include inorganic phosphates such as red phosphorus, various sodium phosphates, magnesium phosphates, and calcium phosphates, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, and phosphate condensates. Phosphate esters, phosphazene compounds, phosphinic acid derivatives, and the like are particularly preferred as phosphazene compounds from the viewpoint of moisture resistance. The phosphorus φ compound may be added in an amount of 1% by weight or more and 3 parts by weight or less based on the solid content of the adhesive composition. When the amount is less than 1% by weight, it is difficult to obtain a flame retardancy effect, and when it exceeds 3% by weight, it is not only excessive, but also has an adhesiveness of resin and a decrease in moisture resistance, and tends to be in the adhesive composition of the present invention. In addition, it is difficult to mix a filler such as vermiculite or calcium carbonate, an inorganic, an organic pigment, a dye, an antistatic agent, a leveling agent, or a phosphorus compound, as long as the content of the present invention is not impaired. Polysiloxanes of flammable agents, aluminum hydroxide, urea compounds, and the like, and resins other than polyamidoximine, such as polyester, polyamide, polyimine, polyurethane, and the like. The adhesive composition of the present invention can be used as an adhesive solution for dissolving an adhesive composition in a solvent. For example, the adhesive solution may be applied and dried to the adherend, and then overlapped with the other adherend, and calendered by a heating roll or a hot press treatment, and heat-hardened as necessary to be used as an adhesive. The foregoing solvent can be used for N,N'-dimethylacetamide or N-methyl-2-pyrrolidone, N,N'-dimethyl- used in the polymerization of polyamidoximine resin. 17-201026750 Solvents such as formamide and r-butyrolactone, but when a solvent remains in the adhesive layer, foaming during adhesion processing and heat resistance itself are reduced, which is a bad result. Therefore, it is preferred to use an alcohol having a high boiling point to be replaced with an alcohol such as methanol, ethanol or butanol, an ester such as methyl acetate or ethyl acetate, an aromatic hydrocarbon such as toluene or xylene, or an ether or acetone. A low-boiling solvent such as a ketone such as methyl ethyl ketone or cyclohexanone. It is preferred to replace the polymerization solvent of about 40% by weight of the entire solvent with these solvents. In the adhesive solution, the solid content concentration may be appropriately set according to the purpose of use, but preferably 20 to 60% by weight, more preferably 30 to 50% by weight. » Polyimine ylide resin of the present invention and more The use of the composition of the polyfunctional compound such as a functional epoxy compound, a polyfunctional isocyanate compound or a melamine compound is not particularly limited, and the most useful use is an adhesive for circuit board connection or an insulating ink protected by a circuit. Specifically, for example, a polyimide film, a polyester film, a glass epoxy sheet, an adhesive copper foil, an aluminum foil, an adhesive on an insulating substrate such as a phenol resin sheet, an adhesive for a cover film, and a cover can be used. The film similarly protects the insulating oil of the circuit, the ink, the adhesive for reinforcing a part of the circuit board with the reinforcing plate, and the adhesive for the case where the direct semiconductor wafer is mounted on the circuit board. 3. Insulating ink for printed circuit board, the polyamidoximine resin of the present invention is used as an insulating ink for a printed circuit board, in a mixed solution of a polyamidoximine resin and the above polyfunctional compound, relative to a poly The mixed solution of the amidoxime resin and the polyfunctional compound is preferably mixed with 0.5 to 10% by weight, more preferably 1 to 5% by weight of inorganic particles such as cerium oxide and calcium sulfate, and/or various organic substances. The number of revolutions of the BH type viscometer is 4 rpm/20 rpm, and the viscosity index expressed by the viscosity ratio of 25 -18 to 201026750 ° C is 1.2 or more 3. 〇 or less, and relative to the polyimide amide resin. The mixing of the solution and the above polyfunctional compound is preferably carried out by mixing 〇5 to 5% by weight of a polyfluorene-based or acrylic-based antifoaming agent and a leveling agent. 4. Cover Film The cover film of the present invention comprises the adhesive composition of the present invention as an adhesive layer, composed of two layers of an insulating film layer/adhesive layer, or an insulating film layer/adhesive layer/protective film. The three-layer structure of the layer is constructed. The insulating film of φ is composed of a plastic film of polyimide, polyester, polyphenylene sulfide, polyether oxime, polyetheretherketone, aromatic polyamine, polycarbonate, polyarylate, etc. A film having a thickness of 5 to 200 〆m, 'may also be laminated with a plurality of films selected from the above. The cover film is produced by dissolving the adhesive composition of the adhesive composition of the present invention in a solvent, coating and drying the above-mentioned insulating film to form an adhesive layer. In this case, the adhesive layer is preferably in a moderately semi-hardened state © 'the residual adhesive amount after immersing the dried adhesive layer in 10 (N-methyl-2-pyrrolidone in TC for 2 hours) It is in the range of 2 to 70%, preferably 5 to 50%. For this reason, the drying temperature is preferably from 100 to 170 ° C, and the drying time is preferably from 1 to 1 minute. After drying as needed, it may be heat-treated at 50 to 100 ° C for 1 to 24 hours. The thickness of the above-mentioned adhesive layer after drying is preferably about 5 to 40 ^ 111. Further, it is formed for storage and the like. In the case of layer constitution, a laminated release protective film may be further laminated. 5. Adhesive sheet The so-called adhesive sheet means that the adhesive composition of the present invention is used as a binder layer of -19-201026750, and has at least A constituent of one or more layers of the peelable protective film. For example, the two-layer structure of the protective film layer/adhesive layer or the three layers of the protective film layer/adhesive layer/protective film are in conformity. Here, the protective film is used. The layer is not particularly limited as long as it does not damage the form of the adhesive layer and can be peeled off. Such as polypropylene film and polyester film 'polyoxyl and wax treated polyester film and paper. Also 'metal, ceramics, etc., can not only provide surface insulation, environmental protection for the purpose of protection, Moreover, there are advantages of a new function that can impart heat release, electromagnetic shielding, reinforcement, recognition, etc. For example, the adhesive solution is applied and dried on a polypropylene film and a polyester film, a polyfluorene oxide and a wax-treated polyester. On the release substrate such as a film or paper, it is preferable to insert the semi-hardened adhesive film and sheet into two types of adherends by the same method as the above-mentioned cover film, and use a heat roller and heat. The pressure treatment is carried out by heating and rolling, and it can be hardened as needed. In this case, it is preferable to use a sheet in which no solvent remains in the low-boiling solvent in the same manner as in the coating method. The substrate may be an adhesive composition of the present invention as an adhesive layer, and an insulating film and a copper foil may be bonded to the adhesive layer, and an ink or a cover film for a printed circuit board of the present invention may be used. For the copper foil, a rolled copper foil or an electrolytic copper foil which has been conventionally used in a printed circuit board can be used. The insulating film can be used as an insulating film as the above-mentioned cover film. The examples are shown to be specifically described, but the present invention is not limited to the examples of the examples -20-201026750. Further, the measurement enthalpy in the examples is determined by the following method: (1) Polyamine The acid value of the quinone imine resin is obtained by dissolving 2~3 drops of thymol, and 1/10 of a solution of sodium methoxide in methanol in a solution of polyamidoxime 〇.4g dissolved in DMF2〇ml and from color The change was determined by titration. (2) Logarithmic viscosity A solution of the dry polymer φ Q. 5 g dissolved in 100 mL of NMP was measured at 25 ° C using a Ubbel-type viscosity tube. (3) Adhesive strength The peel strength of the sample of the example was measured by a universal tensile machine manufactured by Toyo Baldwin Co., Ltd. and at a peeling angle of 90 degrees. The adhesion of the polyimide film and the electrolytic copper foil (matte surface) in Examples 1 to 10 and Comparative Example 4, and the polyimide film and the rolled copper foil in Examples 11 to 20 and Comparative Example 3 were measured. The adhesion of the (glossy surface) and the adhesion of the polyimide film to the reinforcing plate of the aluminum plate in Example 2-28. (4) Solderability after humidification The sample having the same adhesion as that of the measurement was allowed to stand in an atmosphere of 40 ° C and 80% RH for 48 hr, and then observed to float in a 26 CTC solder bath for 30 seconds. status. The determination is performed as follows. 〇: No swelling or peeling was observed. x : An expansion or peeling occurred. (5) Impermeability-resistant etching of various copper-clad laminates prepared in Examples 1 to 1 and Comparative Example 4 to form a circuit having a line/space of 70/70/zm, except -21. - 201026750 In addition to the connection terminal portion, a commercially available polyimide film (CISV manufactured by NIKKAN Co., Ltd.) was bonded to the laminate at 150 ° C for 2 minutes, and cured at 150 ° C for 2 hours. The voltage between the terminals was applied at 50 V, and the insulation resistance 之后 after being left for 2 weeks in an atmosphere of 85 ° C and 8 5% RH was measured. On the other hand, in Examples 11 to 20 and Comparative Examples 1 to 3, line widths were formed on a copper clad laminate VYLOFLEX (manufactured by Toyobo Co., Ltd.) having an insulating layer of 2 〇vm and 18;am rolled copper case. / A circuit having a pitch of 70/70 #πι, and a cover film coated with a viscous agent of various polyamidoximine resin solutions is applied to the above-mentioned circuit surface, and between the terminals of the sample In a state where a voltage of 50 V was applied, the change in the insulation resistance 之后 after standing for 2 weeks in an atmosphere of 85 ° C and 85% HR was measured. The determination method is as follows. 〇: Insulation resistance 线 between lines is 1Ε + 08Ω or more x: Insulation resistance 线 between lines is 1 E + 0 8 Ω or less (6) The number average molecular weight of alkylene glycol is determined according to JIS K-0070, and the following The calculation is obtained by φ.
Mn=56110x2/羥基價 (7) 磷原子含量：（利用濕式分解.鉬藍比色法之磷的定 量） 配合試料中的磷濃度將試料秤量於三角燒瓶中，加入 硫酸3m卜高氯酸〇.5ml及硝酸3.5ml，用電熱器花半天的 時間緩緩地加熱分解。如果溶液變成透明的，則進一步加 熱以使得硫酸白煙產生，且放冷至室溫，將該分解液移至 5〇ml量瓶中，加入2%鉬酸銨溶液5ml及0.2%硫酸肼溶液 -22- 201026750 2ml’用純水進行調液，並好好地混合内容物。浸漬燒瓶 於沸騰水浴中1 0分鐘使其加熱發色之後，水冷至室溫，利 用超音波進行脫氣，抽取溶液至吸收池10mm內，且使用 分光光度計（波長83 Onm)對照空試驗液以測定吸光度。從 先前事先作成的檢量線求得磷含量，以算出試料中的P濃度 (8)玻璃轉移溫度 將聚醯胺醯亞胺樹脂溶液塗布、乾燥於聚丙烯薄膜上 φ 以使得乾燥膜厚成爲約30 μ m之後，使用ITE計測控制（股） 公司製的動態黏彈性測定裝置，以1 10Hz頻率對從聚丙烯 薄膜上被剝離之薄膜進行測定，從儲藏彈性率的回折點而 求得。 〔實施例1 ~ 1 0〕 〔聚醯胺醯亞胺樹脂A的製造〕 在附有冷却管與氮氣導入口的4口燒瓶中，將偏苯三酸 酐（ΤΜΑ)〇· 87莫耳、偏苯三酸0.1莫耳、分子量3500的二羧 φ 基聚（丙烯腈· 丁二烯）（宇部興產CTBN1300xl3)0.03莫耳 與二苯基甲烷-4,4’-二異氰酸酯（MDI)l.02莫耳以固體含 量濃度成爲40%的方式，與Ν,Ν’-二甲基乙醯胺（DMAc) — 起進料’並一邊攪拌，一邊昇溫至8 0°C反應約2小時，然 後再昇溫至150°C以使其反應約3小時。一邊冷卻該溶液、 一邊追加甲苯，固體含量濃度爲30%。將其當作聚醯胺醯 亞胺樹脂A溶液。所得到的聚醯胺醯亞胺樹脂的玻璃轉移溫 度爲205°C、對數黏度爲〇.35dl/g、酸價爲588eq/l〇6g。 〔聚醯胺醯亞胺樹脂B的製造〕 -23- 201026750 在附有冷却管與氮氣導入口的4 口燒瓶中，將TM a Ο .97莫耳、與CTBN 1300x 13 0·03莫耳和水0.1莫耳以固 體含量濃度成爲40%的方式與DMAc —起進料，在6CTC下 加熱攪拌1小時使TMA的一部分被開環之後，將MDI 1.02 莫耳以固體含量濃度成爲40%的方式與DM Ac—起進料，並 —邊攪拌、一邊昇溫至80°C使其反應約2小時，且在150°C 下使其反應約3小時。一邊冷卻溶液、一邊加入甲苯，固體 含量濃度爲30%。將其當作聚醯胺醯亞胺樹脂B溶液。所得 φ 到的聚醯胺醯亞胺樹脂的玻璃轉移溫度爲2031、對數黏度 爲0.36dl/g、酸價爲578eq/l〇6g。 〔聚醯胺醯亞胺樹脂C的製造〕 在附有冷却管與氮氣導入口的4 口燒瓶中，將TMA 0.82莫耳、分子量850的聚四亞甲基二醇（PTG850)0.1莫 耳、CTBN1300X130.03 莫耳與二羥甲基丁酸（DMBA)0.05 莫耳和MDI 1.04莫耳以固體含量濃度成爲50%的方式與 DM Ac—起進料，一邊攪拌、一邊昇溫至60 °C使其反應2小 Φ 時，進一步昇溫至120°C使其反應約5小時之後，一邊冷却 、一邊以固體含量濃度成爲30 %的方式用甲苯加以稀釋。 將其當作聚醯胺醯亞胺樹脂C溶液。所得到的聚醯胺醯亞胺 樹脂的玻璃轉移溫度爲201°C、對數黏度爲〇.43dl/g、酸 價爲 488eq/ 106g。 〔聚醯胺醯亞胺樹脂D的製造〕 在製造聚醯胺醢亞胺樹脂C的方法中，除了 TMA爲 0.72莫耳、DMBA爲0.1 5莫耳以外，用相同的條件進行製 造，以得到聚醯胺醯亞胺樹脂D溶液》依此所得之聚醯胺 -24- 201026750 醯亞胺樹脂D的玻璃移轉溫度爲185 °C、對數黏度爲 0.48dl/g、酸價爲 736eq/l〇6g。 〔聚醯胺醯亞胺樹脂E的製造〕 在聚醯胺醯亞胺樹脂C的製造中，除了 TMA爲0.57莫 耳、DMBA爲0.3莫耳以外，用與聚醯胺醯亞胺樹脂C相同 的條件進行製造，以得到聚醯胺醯亞胺樹脂E溶液。依此所 得之聚醯胺醯亞胺樹脂E的玻璃轉移溫度爲177 °C、對數黏 度爲 0.37dl/g 且酸價爲 976eq/l〇6g。 φ 〔聚醯胺醯亞胺樹脂F〕 在附有冷却管與氮導入口之反應容器中，將TMA 0.97 莫耳、CTBN130〇xl3 0.03莫耳、MDI 0.9莫耳以固體含 量濃度成爲50%的方式與DMAc—起進料，在80°C下使其 反應2小時之後，以固體含量濃度成爲40%的方式追加 PTG850 0.1莫耳，昇溫至150 °C並使其反應3小時。一邊 冷却、一邊以固體含量濃度成爲3 0%的方式用甲苯加以稀 釋。將其當作聚醯胺醯亞胺樹脂F溶液。所得到的聚醯胺醯 〇 亞胺樹脂F的玻璃轉移溫度爲192°C、對數黏度爲0.36dl/g 、酸價爲 824eq/ 1 〇6g。 〔聚醯胺醯亞胺樹脂G〕 在聚醯胺醯亞胺樹脂C的製造中，除了 TMA爲0.84莫 耳、DMB A爲0.03莫耳以外，用與聚醯胺醯亞胺樹脂C相同 的條件進行製造，以得到聚醯胺醯亞胺樹脂G溶液。依此 所得之聚醯胺醢亞胺樹脂G的玻璃轉移溫度爲205°C、對數 黏度爲 0.5dl/g、酸價爲 410eq/l〇6g。 〔聚醯胺醯亞胺樹脂Η〕 -25- 201026750 在聚醯胺醯亞胺D的製造中，除了 MDI爲1.07莫耳以外 ’用與聚醯胺醯亞胺樹脂D相同的條件進行製造，以得至 聚醯胺醯亞胺樹脂Η溶液。所得到的聚醯胺醯亞胺樹脂Η的 玻璃轉移溫度爲188尤、對數黏度爲0.95dl/g、酸價爲 433eq/106g ° <黏著劑組成物的製造-l> 在上述所製造之聚醯胺醯亞胺樹脂A、B、C、D、E、 F、G、Η溶液100g中，摻混15g的苯酚酚醛清漆型環氧化 φ 合物（日本環氧製EPIKOTE 152)、1.5g的二胺基二苯颯、 l〇g的次膦酸衍生物（難燃劑BCA、三光（股）製）、5g的磷腈 化合物（難燃劑SPB 100L)，以作爲黏著劑組成物a、b、c 、d、e、f、g、h。相對於各黏著劑組成物的總固體含量之 磷含量係分別爲2.7重量％。 <黏著劑組成物的製造_2> 在聚醯胺醯亞胺樹脂A、B溶液100g中，摻混l〇g的3 官能異氰酸酯化合物CORONATE EH(日本聚胺基甲酸酯製 〇 )，以作爲黏著劑組成物a’、b’。 <覆銅積層板的製造> 以間隙1 〇〇 // m將黏著劑組成物a、b、c、d、e、f、g 、h、a’、b’塗布於l/2oz電解銅箔上，在60°C下5分鐘、 130 °C下10分鐘予以乾燥之後，使聚醯亞胺薄膜（KANAKA 製APICAL NPI 12.5；um)重疊於黏著劑面上，且用180°C 的輥壓層壓機使其貼合之後，在捲繞成輥的狀態下放置於 1 5 0 °C的烘箱中1 5小時，以得到可撓性覆銅積層板。表示 黏著力、加濕後的耐焊性、抗滲移性的測定結果於表1。 •26- 201026750 〔實施例1 1 ~ 2 Ο〕 <黏著劑組成物的製造-1> 在上述所製造之聚醯胺醯亞胺樹脂A、B、C、D、Ε、 F、G、Η溶液100g中，摻混i5g的苯酚酚醛清漆型環氧化 合物（日本環氧製EPIKOTE 152)、1.5g的二胺基二苯碾、 1 〇g的次膦酸衍生物（難燃劑BCA、三光（股）製）、5g的憐腈 化合物（難燃劑SPB100L)，以作爲黏著劑組成物a、b、c 、d、e、f、g、h。 φ <黏著劑組成物的製造-2> 在聚醯胺醯亞胺樹脂A、B溶液l〇〇g中，摻混i〇g的3 官能異氰酸酯化合物CORONATE EH(日本聚胺基甲酸酯製 )，以作爲黏著劑組成物a’、b’。 <覆蓋薄膜的製造> 以間隙1 50从m將黏著劑組成物a、b、c、d、e、f、g 、h、a’、b’塗布於12.5 的聚醯亞胺薄膜（KANAKA製 APICAL NPI 12.5^ m)上，使其在 60 °C 下 5 分鐘、130 °C 下 φ 5分鐘予以乾燥，以做成覆蓋薄膜。將該覆蓋薄膜重疊於使 用絶緣層20/zm、18 g m壓延銅箔之東洋紡製覆銅積層板 VYLOFLEX的電路面上，在150°C下進行2分鐘熱壓處理， 在150°C下進行2小時熱處理。此外，上述作成的覆蓋薄膜 之中，a、b、c、d、e、f、g、h係難燃水準符合UL規格的 VTM - 0。表示黏著力、力Π濕後的耐焊性、抗滲移性的測定 結果於表1。 〔實施例2 1 ~ 2 8〕 <黏著片的製造> -27- 201026750 將上述黏著劑組成物a、b、c、d、e、f、g、h塗布於 50;/ m的聚丙烯薄膜上，在6〇 t下5分鐘、130 °C下10分鐘 予以乾燥之後剝離，以得到膜厚20 v m的黏著片a，，、b，，、 c ’’、d’’、e，，、f，’、g，，、h，，。 接著，使用黏著劑組成物b，分別透過黏著片a，，、b，， d’’、e’’、f’’、g’’、h’’，使 〇.3mm 的鋁板製增強板 重疊於所作成之覆銅積層板的聚醯亞胺薄膜面上，使用 1 5 0°C的熱壓處理使其壓延2分鐘。然後，用相同的溫度在 φ 加壓下進行2小時熱處理。表示黏著力、加濕後的耐焊性、 抗滲移性的測定結果於表1。 〔比較例-1〕 使用在聚醯胺醯亞胺樹脂C的製造例中，除了原料的進 .料量TMA爲0·85莫耳、DMBA爲0.02莫耳以外，用與聚醯 胺醯亞胺樹脂製造例C相同的條件製造所得之玻璃轉移溫 度爲208°C、對數黏度爲0.50dl/g、酸價爲329eq/l〇6g的 聚醯胺醯亞胺樹脂I，以做成與實施例1中黏著劑組成物的 製造-1相同摻混的黏著劑組成物i，且與實施例11~20同樣 地做成覆蓋薄膜以進行測試。表示黏著力、加濕後的耐焊 性、抗滲移性的測定結果於表1。此外，相對於黏著劑組成 物的總固體含量之磷含量爲2.7重量％。 〔比較例-2〕 使用在聚醯胺醯亞胺樹脂C的製造例中，除了 TM A爲 0.47莫耳、DMBA爲0.40莫耳以外，用相同條件所製造的 玻璃轉移溫度爲169°C、對數黏度爲〇.29dl/g、酸價爲 1130eq/106g的聚醯胺醢亞胺樹脂J，以做成與實施例1中 -28- .201026750 黏著劑組成物的製造-ι相同摻混的黏著劑組成物j，且與實 施例1卜20同樣地做成覆蓋薄膜以進行測試。表示黏著力 、加濕後的耐焊性、抗滲移性的測定結果於表1。此外，相 對於黏著劑組成物的總固體含量之磷含量爲2.7重量％。 〔比較例-3〕 在聚醯胺醯亞胺樹脂A的製造中，除了 MDI的進料量爲 0.9 5莫耳以外，用與聚醯胺酿亞胺樹脂A相同的方法製造 聚醯胺醯亞胺樹脂K。所得樹脂的對數黏度爲0.13 dl/g、 ❿ 酸價爲1866eq/106g »該樹脂由於分子量低，不能形成薄 膜，所以無法測定玻璃轉移溫度。使用該聚醯胺醯亞胺樹 脂K，以做成與實施例1中黏著劑組成物的製造-1相同的黏 著劑組成物k，且以與實施例1 1 ~ 2 0同樣地做成覆蓋薄膜以 進行測試。表示黏著力、加濕後的耐焊性、抗滲移性的測 定結果於表1。此外，相對於黏著劑組成物的總固體含量之 磷含量爲2.7重量％ » 〔比較例4〕 Φ 在上述反應容器中，將TMA0.7莫耳、CTBN130〇xl3 0.03莫耳、二聚酸 0.25莫耳、MDI 1.02莫耳以固體含量 濃度成爲40%的方式與DMAc—起進料，使其在120°C下2 小時、1 5 0 °C下3小時予以反應之後，一邊冷却、一邊以固 體含量濃度成爲3 0 %的方式用甲苯加以稀釋。所得到的聚 醯胺醯亞胺樹脂L的玻璃轉移溫度爲164、對數黏度爲 〇·47 dl/g、酸價爲187eq/l〇6g〇使用該聚醯胺醯亞胺樹脂 L，以做成與實施例1中黏著劑組成物的製造-1相同摻混的 黏著劑組成物1，且與實施例1~1〇同樣地做成覆銅積層板以 -29- 201026750Mn=56110x2/hydroxyl price (7) Phosphorus atomic content: (Quantitative determination of phosphorus by wet decomposition. Molybdenum blue colorimetric method) The concentration of phosphorus in the sample is weighed in a conical flask, and 3 m of perchloric acid is added. 5. 5ml and 3.5ml of nitric acid, slowly heated and decomposed with an electric heater for half a day. If the solution becomes transparent, further heating to produce sulfuric acid white smoke, and let it cool to room temperature, transfer the decomposition liquid to a 5 〇ml volumetric flask, add 2% ammonium molybdate solution 5ml and 0.2% barium sulfate solution -22- 201026750 2ml' Mix with pure water and mix the contents well. The impregnation flask was heated to a color in a boiling water bath for 10 minutes, then cooled to room temperature, degassed by ultrasonic waves, and the solution was taken up to within 10 mm of the absorption cell, and a spectrophotometer (wavelength 83 Onm) was used to control the empty test solution. To determine the absorbance. The phosphorus content is obtained from a previously prepared calibration curve to calculate the P concentration in the sample. (8) Glass transition temperature The polyamidoximine resin solution is applied and dried on a polypropylene film to make the dried film thickness After about 30 μm, the film obtained by peeling off the polypropylene film was measured at a frequency of 10 10 Hz using a dynamic viscoelasticity measuring apparatus manufactured by ITE Measurement Control Co., Ltd., and was obtained from the point of return of the storage modulus. [Examples 1 to 10] [Production of Polyamide Amine Resin Resin A] In a 4-necked flask equipped with a cooling tube and a nitrogen gas introduction port, trimellitic anhydride (ΤΜΑ) 〇 87 mol, trimellitic acid 0.1 mol, a dicarboxyl φ group poly(acrylonitrile butadiene) having a molecular weight of 3,500 (Ube Hirsch CTBN1300xl3) 0.03 mol and diphenylmethane-4,4'-diisocyanate (MDI) 1.02 mol In a manner that the solid content concentration is 40%, the mixture is stirred with Ν, Ν'-dimethylacetamide (DMAc) and heated to 80 ° C for about 2 hours while stirring, and then heated to It was allowed to react at 150 ° C for about 3 hours. While cooling the solution, toluene was added thereto, and the solid content concentration was 30%. This was taken as a solution of polyamidoquinone imine resin A. The obtained polyamidoximine resin had a glass transition temperature of 205 ° C, a logarithmic viscosity of 〇.35 dl / g, and an acid value of 588 eq / l 〇 6 g. [Production of Polyamide Amine Resin B] -23- 201026750 In a 4-necked flask equipped with a cooling tube and a nitrogen inlet, TM a Ο .97 mol, and CTBN 1300x 13 0·03 Mo and The water 0.1 mol was fed with DMAc in such a manner that the solid content concentration became 40%, and the mixture was heated and stirred at 6 CTC for 1 hour to open a portion of the TMA, and then the MDI 1.02 molar was 40% solid concentration. The mixture was fed with DM Ac, and the mixture was heated to 80 ° C while stirring, and allowed to react for about 2 hours, and allowed to react at 150 ° C for about 3 hours. Toluene was added while cooling the solution, and the solid content concentration was 30%. This was taken as a solution of polyamidoquinone resin B. The glass transition temperature of the obtained φ to polyamidoximine resin was 2031, the logarithmic viscosity was 0.36 dl/g, and the acid value was 578 eq/l 〇 6 g. [Production of Polyamide Amine Resin C] In a 4-neck flask equipped with a cooling tube and a nitrogen inlet, TMA 0.82 mol, polytetramethylene glycol (PTG850) having a molecular weight of 850, 0.1 mol, CTBN1300X130.03 Mohr and dimethylolbutanoic acid (DMBA) 0.05 Mohr and MDI 1.04 Moore were fed with DM Ac in a solid content concentration of 50%, and the temperature was raised to 60 °C while stirring. When the reaction was carried out for 2 small Φ, the temperature was further raised to 120 ° C to carry out a reaction for about 5 hours, and then diluted with toluene so as to have a solid content concentration of 30% while cooling. This was taken as a polyamidoquinone resin C solution. The obtained polyamidoximine resin had a glass transition temperature of 201 ° C, a logarithmic viscosity of 43 43 d / g, and an acid value of 488 eq / 106 g. [Production of Polyamide Amine Resin D] The method for producing the polyamidimide resin C was carried out under the same conditions except that TMA was 0.72 mol and DMBA was 0.15 mol. Polyamide amide imine resin D solution according to the obtained polyamido-24- 201026750 bismuth imine resin D has a glass transition temperature of 185 ° C, a logarithmic viscosity of 0.48 dl / g, and an acid value of 736 eq / l 〇 6g. [Production of Polyamide Amine Resin E] In the production of polyamidoximine resin C, the same as polyamido ruthenium imide resin C except that TMA is 0.57 mol and DMBA is 0.3 mol. The conditions were manufactured to obtain a polyamidoximine resin E solution. The polyamidolimine resin E thus obtained had a glass transition temperature of 177 ° C, a logarithmic viscosity of 0.37 dl/g and an acid value of 976 eq/l 〇 6 g. Φ [polyamido amide imine resin F] In a reaction vessel with a cooling tube and a nitrogen inlet, TMA 0.97 Mo, CTBN130 〇xl3 0.03 mol, MDI 0.9 mol is 50% solids concentration In the same manner as the DMAc, the mixture was reacted at 80 ° C for 2 hours, and then PTG850 0.1 mol was added so that the solid content concentration became 40%, and the temperature was raised to 150 ° C and allowed to react for 3 hours. While cooling, it was diluted with toluene so that the solid content concentration became 30%. This was taken as a solution of polyamidoquinone resin F. The obtained polyamidoxime fluorene imine resin F had a glass transition temperature of 192 ° C, a logarithmic viscosity of 0.36 dl / g, and an acid value of 824 eq / 1 〇 6 g. [Polyamine Amine Resin G] In the production of polyamidoximine resin C, the same as polyamido ruthenium amide resin C except that TMA is 0.84 mol and DMB A is 0.03 mol. The conditions were made to obtain a polyamidoquinone resin G solution. The polyamidoximine resin G thus obtained had a glass transition temperature of 205 ° C, a logarithmic viscosity of 0.5 dl / g, and an acid value of 410 eq / l 〇 6 g. [Poly amidoxime resin Η] -25- 201026750 In the production of polyamidoximine D, except that the MDI is 1.07 moles, it is produced under the same conditions as the polyamidoximine resin D. To obtain a solution of polyamidoquinone imide resin. The obtained polyamidoximine resin ruthenium had a glass transition temperature of 188, a logarithmic viscosity of 0.95 dl/g, and an acid value of 433 eq/106 g ° <Production of Adhesive Composition-l> 15 g of phenol novolac type epoxidized φ compound (EPIKOTE 152, Japan Epoxy Co., Ltd.), 1.5 g of polyacrylamide imine resin A, B, C, D, E, F, G, bismuth solution Diaminodiphenyl hydrazine, 〇g phosphinic acid derivative (flammable agent BCA, manufactured by Sanguang Co., Ltd.), 5 g of phosphazene compound (flammable agent SPB 100L), as adhesive composition a , b, c, d, e, f, g, h. The phosphorus content relative to the total solid content of each of the adhesive compositions was 2.7% by weight, respectively. <Production of Adhesive Composition _2> In 100 g of a polyamidoximine resin A and B solution, 1 g of a trifunctional isocyanate compound CORONATE EH (manufactured by Japanese Polyurethane) was blended, Used as the adhesive composition a', b'. <Production of Copper Clad Laminate> The adhesive compositions a, b, c, d, e, f, g, h, a', b' were applied to l/2 oz electrolysis at a gap of 1 〇〇//m. On a copper foil, after drying at 60 ° C for 5 minutes and at 130 ° C for 10 minutes, a polyimide film (APANA NPI 12.5; um) was superposed on the adhesive surface, and 180 ° C was used. After the roll laminator was attached, it was placed in an oven at 150 ° C for 15 hours in a state of being wound into a roll to obtain a flexible copper clad laminate. The measurement results indicating the adhesion, the solder resistance after humidification, and the bleed resistance are shown in Table 1. • 26-201026750 [Example 1 1 to 2 Ο] <Production of Adhesive Composition-1> Polyamine amide imine resin A, B, C, D, Ε, F, G, produced as described above In 100 g of cerium solution, i5 g of a phenol novolac type epoxy compound (EPIKOTE 152 manufactured by Nippon Epoxy Co., Ltd.), 1.5 g of diaminobiphenyl oxide, and 1 g of a phosphinic acid derivative (flammable agent BCA, 3 g of a nitrile compound (flammable agent SPB100L) as an adhesive composition a, b, c, d, e, f, g, h. φ <Manufacture of Adhesive Composition-2> In the polyamidoquinone imine resin A, B solution l〇〇g, i〇g of a 3-functional isocyanate compound CORONATE EH (Japanese polyurethane) As a binder composition a', b'. <Production of Cover Film> The adhesive composition a, b, c, d, e, f, g, h, a', b' was applied to the 12.5 polyimine film from m at a gap of 150 ( KANAKA APICAL NPI 12.5^m) was dried at 60 ° C for 5 minutes and at 130 ° C for 5 minutes to form a cover film. This cover film was superposed on the circuit surface of the Toyobo copper-clad laminate VYLOFLEX using an insulating layer of 20/zm and 18 gm of rolled copper foil, and subjected to hot pressing treatment at 150 ° C for 2 minutes, and performed at 150 ° C. Hour heat treatment. Further, among the above-mentioned cover films, the flame retardant levels of a, b, c, d, e, f, g, and h are in accordance with the UL standard VTM-0. The results of measurement of adhesion resistance, weld resistance and bleed resistance after dampness are shown in Table 1. [Example 2 1 to 2 8] <Production of Adhesive Sheet> -27- 201026750 The above-mentioned adhesive compositions a, b, c, d, e, f, g, h were applied to 50; The propylene film was dried at 5 Torr for 5 minutes and at 130 ° C for 10 minutes, and then peeled off to obtain adhesive sheets a, , b, , c '', d'', and e of a film thickness of 20 vm. ,, f, ', g,,, h,,. Next, using the adhesive composition b, the adhesive sheets a, , b, d'', e'', f'', g'', h'' are respectively passed, so that the aluminum plate reinforcing plates of 〇.3 mm are overlapped. On the surface of the polyimide film of the copper-clad laminate which was formed, it was calendered for 2 minutes using a hot pressing treatment at 150 °C. Then, heat treatment was carried out for 2 hours under the same temperature at φ under pressure. The measurement results indicating the adhesion, the solder resistance after humidification, and the bleed resistance are shown in Table 1. [Comparative Example-1] In the production example of the polyamidoximine resin C, in addition to the feedstock amount TMA of 0.85 moles and DMBA of 0.02 moles, The polyamide resin obtained in the same conditions as in the production example C of the amine resin had a glass transition temperature of 208 ° C, a logarithmic viscosity of 0.50 dl / g, and an acid value of 329 eq / l 〇 6 g of polyamidoximine resin I. In the production of the adhesive composition of Example 1, the adhesive composition i was blended in the same manner as in Example 1, and a cover film was formed in the same manner as in Examples 11 to 20 to carry out the test. The measurement results indicating the adhesion, the solder resistance after humidification, and the bleed resistance are shown in Table 1. Further, the phosphorus content relative to the total solid content of the adhesive composition was 2.7% by weight. [Comparative Example-2] In the production example of the polyamidoximine resin C, the glass transition temperature produced under the same conditions was 169 ° C except that TM A was 0.47 mol and DMBA was 0.40 mol. A polyamidoquinoneimine resin J having a logarithmic viscosity of 〇.29 dl/g and an acid value of 1130 eq/106 g was blended as in the manufacture of the -28-.201026750 adhesive composition of Example 1. The adhesive composition j was formed into a cover film in the same manner as in Example 1 to test. The measurement results indicating the adhesion, the solder resistance after humidification, and the migration resistance are shown in Table 1. Further, the phosphorus content of the total solid content relative to the adhesive composition was 2.7% by weight. [Comparative Example-3] In the production of polyamidoximine resin A, polyamidoguanidine was produced in the same manner as polyacrylamide-based imine resin A except that the amount of MDI fed was 0.95 mol. Imine resin K. The obtained resin had a logarithmic viscosity of 0.13 dl/g and a valence of 1866 eq/106 g. The resin had a low molecular weight and could not form a film, so that the glass transition temperature could not be measured. The polyamidoximine resin K was used to form the same adhesive composition k as in the production-1 of the adhesive composition of Example 1, and was covered in the same manner as in Examples 1 to 2 0. The film was tested. The results of the measurements indicating the adhesion, the solder resistance after humidification, and the bleed resistance are shown in Table 1. Further, the phosphorus content relative to the total solid content of the adhesive composition was 2.7% by weight » [Comparative Example 4] Φ In the above reaction vessel, TMA 0.7 mol, CTBN130 〇 xl3 0.03 mol, dimer acid 0.25 Mohr and MDI 1.02 Moore were fed with DMAc in such a manner that the solid content concentration became 40%, and the reaction was carried out at 120 ° C for 2 hours and at 150 ° C for 3 hours, and then cooled while The solid content concentration was changed to 30% and diluted with toluene. The obtained polyamidoximine resin L had a glass transition temperature of 164, a logarithmic viscosity of 〇·47 dl/g, and an acid value of 187 eq/l 〇 6 g. The polyamine amide imine resin L was used to make The adhesive composition 1 was blended in the same manner as in the production-1 of the adhesive composition of Example 1, and a copper-clad laminate was produced in the same manner as in Examples 1 to 1 to -29-201026750.
進行測試。表示黏著力、加濕後的耐焊性、抗滲移性的測 定結果於表1。此外，相對於黏著劑組成物的總固體含量之 磷含量爲2.7重量％。 整理上述例的結果表示於表1。 -30- 201026750 表1 例 測試形狀 PAI 黏著劑 組成物 黏著片 黏著力 (g/cm) 加濕後的 耐焊性 抗滲移性 實施例1 覆銅積層板 A a 1320 〇 〇 實施例2 同上 A a. 1250 〇 〇 實施例3 同上 B b 1330 〇 〇 實施例4 同上 B b， 1275 Ο 〇 實施例5 •同上 c c 1620 〇 〇 實施例6 同上 D d 1620 〇 〇 實施例7 同上 E e 1335 〇 〇 實施例8 同上 F f 1545 〇 〇 實施例9 同上 G g 1210 〇 〇 實施例10 同上 H h 1690 〇 〇 實施例11 覆蓋薄膜 A a 815 〇 〇 實施例12 同上 A a. 760 〇 〇 實施例13 同上 B b 785 〇 〇 實施例14 同上 B b， 690 〇 〇 實施例15 同上 C c 695 〇 〇 實施例16 同上 D d 880 〇 〇 實施例17 同上 E e 790 〇 〇 實施例18 同上 F f 855 〇 〇 實施例19 同上 G g 680 〇 〇 實施例20 同上 H h 735 〇 〇 實施例21 黏結片 A a，， 1520 〇 — 實施例22 同上 B b，， 1435 〇 一 實施例23 同上 C c” 1345 〇 — 實施例24 同上 D d” 1640 〇 — 實施例25 同上 E e” 1440 〇 — 實施例26 同上 F 厂 1590 〇 — 實施例27 同上 G g" 1315 〇 - 實施例28 同上 H h” 1665 〇 - 比較例1 覆蓋薄膜 I i 690 X 〇 比較例2 同上 j j 335 X X 比較例3 同上 K k 120 X X 比較例4 覆銅積層板 L 1 890 X 〇carry out testing. The results of the measurements indicating the adhesion, the solder resistance after humidification, and the bleed resistance are shown in Table 1. Further, the phosphorus content relative to the total solid content of the adhesive composition was 2.7% by weight. The results of the above examples are shown in Table 1. -30- 201026750 Table 1 Example Test Shape PAI Adhesive Composition Adhesive Sheet Adhesion (g/cm) Solderability Impermeability after Humidification Example 1 Copper-clad laminate A a 1320 〇〇 Example 2 Same as above A a. 1250 〇〇 Example 3 Same as above B b 1330 〇〇 Example 4 Same as above B b, 1275 Ο 〇 Example 5 • Same as cc 1620 〇〇 Example 6 Same as above D d 1620 〇〇 Example 7 Same as above E e 1335 〇〇Example 8 Same as above F f 1545 〇〇Example 9 Same as above G g 1210 〇〇Example 10 Same as above H h 1690 〇〇Example 11 Cover film A a 815 〇〇Example 12 Same as above A a. 760 〇〇Implementation Example 13 Same as above B b 785 〇〇 Example 14 Same as above B b, 690 〇〇 Example 15 Same as above C c 695 〇〇 Example 16 Same as above D d 880 〇〇 Example 17 Same as above E e 790 〇〇 Example 18 Same as F f 855 〇〇 Example 19 Same as above G g 680 〇〇 Example 20 Same as above H h 735 〇〇 Example 21 Adhesive sheet A a,, 1520 〇 - Example 22 Same as above B b,, 1435 实施 Example 23 Same as above C c" 1345 〇 - Example 24 Same as above D d" 1640 〇 - Example 25 Same as above E e" 1440 〇 - Example 26 Same as F Factory 1590 〇 - Example 27 Same as above G g" 1315 〇 - Example 28 Same as H h" 1665 〇 - Comparative Example 1 Covering film I i 690 X 〇 Comparative Example 2 Same as above jj 335 XX Comparative Example 3 Same as above K k 120 XX Comparative Example 4 Copper-clad laminate L 1 890 X 〇
產業上的利用可能性 根據實施例的結果可明顯得知若根據本發明，可提供 對金屬與聚醯亞胺薄膜的低溫黏著性與耐熱性、特別是加 濕處理後的耐焊性及在高溫高濕下的耐滲移特性優異的、 有用於電路基板之印墨、黏著劑組成物及黏著片、覆蓋薄 膜、玻璃絲網含浸預浸漬物以及使用此等之印刷電路基板。 -31 - 201026750 【圖式簡單說明】 Μ 〇 【主要元件符號說明】 Μ 〇INDUSTRIAL APPLICABILITY According to the results of the examples, it is apparent that according to the present invention, low-temperature adhesion and heat resistance to a metal and a polyimide film, particularly, solder resistance after humidification treatment, and The ink, the adhesive composition and the adhesive sheet for a circuit board, the cover film, the glass mesh impregnated prepreg, and the printed circuit board using the same are excellent in the high-temperature and high-humidity resistance. -31 - 201026750 [Simple description of the diagram] Μ 〇 [Description of main component symbols] Μ 〇
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