201137025 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種薄膜用組成物。具體而言，係關於 適合於電性/電子用途的接著薄膜或印刷配線板的覆蓋薄 膜之薄膜用組成物。 此外，本發明係關於使用該薄膜用組成物所製作之接 著薄膜及覆蓋薄膜。 【先前技術】 近年來，電性/電子機器中所使用之印刷配線板，隨 著機器的小型化、輕量化、及高性能化，尤其對多層印刷 配線板’更進而要求高多層化、高密度化、薄型化、輕量 化、高可靠度、及成形加工性等。 此外’伴隨著近來對印刷配線板之傳輸訊號的高速化 要求’使得傳輸訊號的高頻化顯著地進行。藉此，對於印 刷配線板所使用之材料’係要求在高頻區域，具體而言在 頻率1〜10GHz的區域中可減少電訊號損失者。 對於用作爲印刷配線板的層間接著劑或表面保護膜（ 亦即覆蓋薄膜）之接著薄膜’係要求在高頻區域可顯示出 較佳電特性（低介電率（ε )、低介電正切（tan 6 )) 者。 上述用途中所使用之接著薄膜的材料，由於本質上爲 可燃性’用作爲工業用材料時’除了均衡地滿足一般的化 學、物理特性外，較多亦要求相對於火焰之安全性，亦即 -5- 201137025 難燃性。尤其使用在家電用途時，較多均要求「UL94V規 格的V - 0、U L 9 4 V Τ Μ的V τ Μ - 0規格」等之高度的難燃性。 一般而言，將難燃性賦予至接著薄膜般的樹脂材料之方法 ，可列舉出於樹脂中添加鹵素系有機化合物作爲難燃劑， 並添加銻化合物作爲難燃輔助劑之方法。 然而’此方法乃具有燃燒時會產生腐蝕性的鹵素氣體 或劇毒性的戴奧辛之問題。因此，近年來爲了排除鹵素系 難燃劑對環境所造成的不良影響，係強烈要求採用完全不 含鹵素之無鹵素難燃劑者。 關於無鹵素的難燃處方，例如可採用磷系難燃劑的調 配。然而，以磷酸酯等之含磷添加劑來賦予難燃性時，必 須大量地調配於樹脂內，不僅使接著性、耐熱性、耐焊性 等之樹脂特性降低，亦會產生難燃劑在高溫環境下滲出之 問題。 因此，專利文獻1~3係提出下列由含磷高分子化合物 所構成之難燃性樹脂組成物。 專利文獻1中係提出一種難燃性樹脂組成物，其特徵 係由分子中含有磷之數量平均分子量爲3000以上的樹脂（ A )、與含磷量爲3重量％以上的含磷化合物（B )所構成 ，且該調配比以固形重量比計爲（A )/( B ) =1〇〇/1〜60而 成。. 專利文獻2中係提出一種難燃性聚胺基甲酸酯樹脂組 成物，其係包含：含有以使特定結構的含磷羧酸或該酯化 物進行共聚合所得之含磷聚酯多元醇作爲構成成分、且酸 -6 - 201137025 價爲50當量/10 6g以上之聚胺基甲酸酯，以及環氧化合物。 專利文獻3中係提出一種難燃性樹脂組成物，爲調配 有熱硬化性樹脂、硬化劑、含磷多元醇、及聚異氰酸酯而 成之難燃性樹脂組成物，其特徵爲：前述含磷多元醇中的 磷，相對於前述熱硬化性樹脂及前述硬化劑的合計量，係 以0.93重量％以上的比率所含有。 然而，專利文獻1~3中，在高頻區域之電訊號損失未 被重視，當將此等文獻所記載之樹脂組成物使用在上述用 途的接著薄膜時，可視爲在高頻區域之電特性會劣化。 此外，專利文獻1所記載之難燃性樹脂組成物，含磷 化合物（B )係含有聚磷酸銨。此係用做爲磷系難燃劑。 因此，專利文獻1所記載之難燃性樹脂組成物，可視爲具 有上述由於磷系難燃劑的調配所造成之問題點。專利文獻 1所記載之難燃性樹脂組成物中，除了分子中含有磷之樹 脂（A )之外必須使用含磷化合物（B )之理由，如該文獻 段落號碼〔0020〕所記載般，是由於當單獨以樹脂（A ) 賦予高度難燃性時，必需使大量磷化合物進行共聚合，而 產生樹脂本身的水解或接著性降低等問題之故。 〔先前技術文獻〕 〔專利文獻〕 〔專利文獻1〕日本特開200 1 -293 1號公報 〔專利文獻2〕日本特開2005 -6048 9號公報 〔專利文獻3〕日本特開2005- 1 8 7 8 1 0號公報 201137025 【發明內容】 (發明所欲解決之課題） 本發明係爲了解決上述以往技術的問題點而創作出之 發明，目的在於提供一種可達成在高頻區域，具體而言在 頻率1〜5 GHz的區域之低介電率化及低介電損失化，並且 難燃性佳之電性/電子用途的接著薄膜與覆蓋薄膜，以及 此等薄膜的製作中所使用之薄膜用組成物。 (用以解決課題之手段） 爲了達成上述目的，本發明係提供一種薄膜用組成物 ’其特徵爲含有：（A)不含羥基之環氧樹脂、（B)含有 含磷多元醇作爲構成成分之胺基甲酸酯樹脂、（C)具有 馬來醯亞胺基之化合物、以及（D )硬化劑，且 相對於前述（A)成分1〇〇質量份，係含有1〇〇〜975質 量份的前述（B)成分、含有25〜100質量份的前述（C)成 分、含有有效Μ的前述（D)成分，磷相對於前述（a)〜 (D)的合計之質量百分率爲2〜7 %。 本發明之薄膜用組成物，較佳更含有有效量的（Ε ) 硬化促進劑。 本發明之薄膜用組成物中，前述（Β)成分之胺基甲 酸酯樹脂中所含有之含磷多元醇’較佳係由下述式表示之 結構的含磷多元醇。 201137025 【化1】 (R1)· (R2)： ο P—(GH2)n_ Io CHCOOR3CHCOOR4 (式中，R1及R2互相獨立地表示氫原子及由碳數6以下的 烴基所組成群組中選出的任一個；R3及r4互相獨立地表示 氫原子、由碳數6以下的烴基及可含有雜原子之碳數6以下 的羥基經取代之烴基所組成群組中選出的任一個；1及m互 相獨立地表示〇~4之整數；η表示卜20之整數）。 本發明之薄膜用組成物中’前述（Α)成分之環氧樹 脂較佳爲聯苯型環氧樹脂。 本發明之薄膜用組成物中，前述（D )成分之硬化劑 較佳爲苯酚系硬化劑。 本發明之薄膜用組成物中，前述（Ε )成分之硬化促 進劑較佳爲咪唑系硬化促進劑。 此外，本發明係提供一種接著薄膜’其係使用本發明 之薄膜用組成物所製成。 此外，本發明係提供一種覆蓋薄膜，其係使用本發明 之薄膜用組成物所製成。 此外，本發明係提供一種清漆，其係含有本發明之薄 膜用組成物。 -9- 201137025 發明之效果： 本發明之接著薄膜及覆蓋薄膜，在加熱硬化後，在高 頻區域可顯示出較佳電特性，具體而言在頻率1〜10GHz的 區域之低介電率（ε)、及低介電正切（tan(5)，故可 達成在高頻區域之低介電率化及低介電損失化，並且難燃 性良好。 此外’本發明之接著薄膜及覆蓋薄膜，在加熱硬化後 ’對於聚醯亞胺、液晶聚合物、陶瓷等之印刷配線板中所 使用之有機材料或無機材料可顯示出較佳接著強度。 再者’本發明之接著薄膜及覆蓋薄膜，在加熱硬化後 可撓性較佳，所以適合用作爲可撓性印刷配線板用的接著 薄膜及覆蓋薄膜。本發明之薄膜，即使在加熱硬化前，可 撓性亦佳，所以在薄膜的加工步驟中，其作業性良好。 此外，本發明之接著薄膜及覆蓋薄膜，由於賦予薄膜 難燃性之磷，是由樹脂成分的聚胺基甲酸酯所納入，並且 被納入於在薄膜的熱硬化時藉由使該聚胺基甲酸酯與薄膜 中的環氧樹脂進行共聚合所形成之共聚物中，所以在將磷 系難燃劑添加於接著薄膜或覆蓋薄膜時，並不會產生難燃 劑成分在高溫環境下滲出之情形。 本發明之接著薄膜及覆蓋薄膜，可使用本發明之薄膜 用組成物而製成。 本發明中，亦可將含有本發明之薄膜用組成物之清漆 塗佈於薄膜形成面後，進行乾燥而成薄膜化，以取代預先 形成爲薄膜之形態。 -10- 201137025 【實施方式】 以下詳細說明本發明。 本發明之薄膜用組成物，係含有下列所示之（A )〜（ D)成分作爲必要成分。 (A)成分：不含羥基之環氧樹脂。 本發明之薄膜用組成物中，（A )成分，亦即環氧樹 脂’主要是對使用該薄膜用組成物所製成之接著薄膜及覆 蓋薄膜賦予熱硬化性、難燃性、及接著性。 惟使用該薄膜用組成物所製成之接著薄膜及覆蓋薄膜 ’在加熱硬化後，爲了在高頻區域可顯示出較佳電特性， 具體而言在頻率1〜10GHz的區域之低介電率（ε )、及低 介電正切（tan 5 )，必須使用不含羥基之環氧樹脂。 用作爲（A)成分之環氧樹脂，可從不含羥基之環氧 樹脂中廣泛地選擇，可使用聯苯型環氧樹脂、甲酚型酚醛 環氧樹脂、環戊二烯型環氧樹脂等。此等當中，聯苯型環 氧樹脂’就使用薄膜用組成物所製成之接著薄膜及覆蓋薄 膜的難燃性理由來看爲較佳。 用作爲（A)成分之環氧樹脂，數量平均分子量（Μη )爲100〜1 000者，就與薄膜用組成物中所含有之其他成分 的相溶性之理由來看爲較佳，尤佳爲3〇〇〜9〇〇，更佳爲 400〜700 〇 用作爲（Α)成分之環氧樹脂，環氧當量較佳爲 50〜500’尤佳爲150〜450，更佳爲200〜350。 -11 - 201137025 (B)成分：含有含磷多元醇作爲構成成分之胺基甲 酸酯樹脂。 本發明之薄膜用組成物中，（B )成分主要是對使用 該薄膜用組成物所製成之接著薄膜或覆蓋薄膜賦予難燃性 及可撓性。 當將磷系難燃劑添加於接著薄膜或覆蓋薄膜時，必須 調配大量的難燃劑，所以在薄膜的使用時會有難燃劑滲出 之問題。 此外，由於需調配大量的難燃劑，所以會有薄膜的接 著性、耐熱性、耐焊性、在高頻區域之電特性等降低之問 題。 本發明之接著薄膜及覆蓋薄膜，由於賦予薄膜難燃性 之磷，是由樹脂成分的聚胺基甲酸酯所納入，並且被納入 於在薄膜的熱硬化時藉由使該聚胺基甲酸酯與薄膜中的環 氧樹脂進行共聚合所形成之共聚物中，所以在將磷系難燃 劑添加於接著薄膜或覆蓋薄膜時，並不會產生難燃劑成分 在高溫環境下滲出之情形。 此外，如上述般，由於賦予薄膜難燃性之磷被納入於 樹脂成分（聚胺基甲酸酯、聚胺基甲酸酯與環氧樹脂之共 聚物），所以在將磷系難燃劑添加於接著薄膜或覆蓋薄膜 時，薄膜的接著性、耐熱性、耐焊性、在高頻區域之電特 性等並不會降低。 使用本發明之薄膜用組成物所製成之接著薄膜及覆蓋 薄膜，在加熱硬化後，爲了滿足此等薄膜所要求之難燃性 -12- 201137025 ，以及薄膜所要求之其他特性，如薄膜的接著性、耐熱性 、耐焊性、在高頻區域之電特性，必須以使磷相對於薄膜 組成物的合計質量，亦即（A )〜（D )成分的合計質量之 質量百分率成爲2~7 %之方式，調配（B)成分。 當磷相對於（A) ~(D)成分的合計質量之質量百分 率未達2 %時，使用薄膜用組成物所製成之接著薄膜及覆蓋 薄膜，在加熱硬化後，難燃性不足。另一方面，當磷相對 於（A)〜（D)成分的合計質量之質量百分率超過7 %時， 使用薄膜用組成物所製成之接著薄膜及覆蓋薄膜，在加熱 硬化後，接著性、耐熱性 '耐焊性、在高頻區域之電特性 不足。 本發明之薄膜用組成物中，（B )成分，亦即胺基甲 酸酯樹脂的構成成分之多元醇，只要是分子中至少含有1 個以上的磷原子之多元醇即可，並無特別限制，例如可列 舉出含有磷之聚酯多元醇、聚醚多元醇、聚碳酸酯多元醇 、及此等成分的複合物等。 此般含磷多元醇中，特佳爲下列式所示之結構的含磷 多元醇。 【化2】 (R1)— p—(CH2)n — CHCOOR3 0 CHCOOR4 (R2)-- -13- 201137025 上述式中，R1及R2互相獨立地表示氫原子及由甲基、 乙基、丙基、苯基等之碳數6以下的烴基所組成群組中選 出的任一個。此等當中，較佳爲氫原子及甲基，尤佳爲氫 原子。 上述式中，R3及R4互相獨立地表示氫原子、由甲基、 乙基、丙基、丁基、苯基、苄基等之碳數6以下的烴基、 及2·羥乙基、2-羥丙基、3-羥丙基、4-羥丁基、2-羥乙基 氧基乙基等之可含有雜原子之碳數6以下的羥基經取代之 烴基所組成群組中選出的任一個。此等當中，較佳爲氫原 子。 上述式中，1及m互相獨立地表示0〜4之整數，η表示 1〜20之整數。1及m較佳係分別爲1» η較佳爲1。 (Β)成分之胺基甲酸酯樹脂，可藉由使上述多元醇 ’亦即分子中至少含有1個以上的磷原子之多元醇，與聚 異氛酸酯類進行共聚合而得。 共聚合中所使用之聚異氰酸酯類，只要是可藉由與分 子中至少含有1個以上的磷原子之多元醇進行共聚合而形 成胺基甲酸酯樹脂即可，並無特別限制，例如可列舉出亞 甲二異氛酸酯系（MDI)、甲苯二異氰酸酯系（TDI)、 六亞甲二異氰酸酯系（HDI)、萘二異氰酸酯系（NDI) 、二甲苯二異飫酸酯系（XDI )等之各種聚異氰酸酯等。 當中’就使用薄膜用組成物所製成之接著薄膜及覆蓋薄膜 的耐熱性及可撓性、以及與分子中至少含有1個以上的磷 原子之多元醇進行共聚合時的反應性之觀點來看，特佳爲 -14- 201137025 MDI系聚異氰酸酯。 藉由上述以結構式所示之含磷多元醇、與聚異氰酸酯 類之共聚合所得之胺基甲酸酯樹脂的具體例，有UR3 5 70 ( 東洋紡社公司製）。 (B)成分之胺基甲酸酯樹脂，除了上述含磷多元醇 之外，亦可將不含磷的多元醇用作爲構成成分。 當將不含磷的多元醇用作爲構成成分時，製成胺基甲 酸酯樹脂時所使用之全部多元醇的合計量，係設爲與聚異 氰酸酯大致相同之當量。在此，所謂當量，是指滿足下列 式之量。 (當量）=(多元醇的OH價）x7.49/(NCO(%):異 氰酸酯價） NCO ( % ) 名亦稱爲異氰酸酯價。 不含磷的多元醇，除了不含磷之點外，可使用與前述 含磷多元醇爲相同種類（例如聚酯多元醇等）或是不同種 類者等之各種多元醇。 (B)成分之胺基甲酸酯樹脂，數量平均分子量（Μη )較佳爲3000以上。當數量平均分子量未達3000時，使用 本發明之薄膜用組成物所製成之接著薄膜及覆蓋薄膜，在 加熱硬化後，機械強度不足，接著性、耐熱性、各種耐久 性有惡化之疑慮。此外，當數量平均分子量超過1 00000時 ，由於薄膜用組成物的黏度增高，使用薄膜用組成物來製 成接著薄膜或覆蓋薄膜時的作業性有惡化之疑慮。 (Β )成分之胺基甲酸酯樹脂的數量平均分子量較佳 -15- 201137025 爲 3 000~3 0000，更佳爲 8000〜1 8000。 本發明之薄膜用組成物，當以上述（A )成分爲100質 量份時，係含有1〇〇~975質量份的上述（B)成分。 上述（B )成分未達100質量份時，使用本發明之薄膜 用組成物所製成之接著薄膜及覆蓋薄膜，在加熱硬化後， 難燃性不足。此外，使用薄膜用組成物所製成之接著薄膜 及覆蓋薄膜，其可撓性惡化。 另一方面，上述（B)成分超過975質量份時，使用薄 膜用組成物所製成之接著薄膜及覆蓋薄膜，在加熱硬化後 ，耐熱性不足。 本發明之薄膜用組成物，當以上述（A)成分爲1 00質 量份時，較佳係含有1 〇〇〜600質量份的上述（B)成分。 (C)成分：具有馬來醯亞胺基之化合物 本發明之薄膜用組成物中，（C )成分主要是對使用 該薄膜用組成物所製成之接著薄膜或覆蓋薄膜賦予難燃性 及接著性。 本發明之薄膜用組成物中，（C )成分只要是具有馬 來醯亞胺基之化合物即可，並無特別限制，例如可列舉出 雙馬來醯亞胺、乙烯苯基馬來醯亞胺、4,4 -雙馬來醯亞胺 二苯基醚、4,4-雙馬來醯亞胺二苯基甲烷、4,4-雙馬來醯 亞胺-3, 3'-二甲基-二苯基甲烷、4,4_雙馬來醯亞胺二苯基 颯、4,4 -雙馬來醯亞胺二苯基硫化物、4,4 -雙馬來醯亞胺 二苯基酮、2，2’-雙（4-雙馬來醯亞胺苯基）丙烷、3,4_雙 馬來醯亞胺二苯基氟甲烷、1，1，1，3,3,3-六氟-2,2-雙（4-雙 -16- 201137025 馬來醯亞胺苯基）丙烷等。當中，雙馬來醯亞胺、乙烯苯 基馬來醯亞胺，就使用薄膜用組成物所製成之接著薄膜或 覆蓋薄膜的難燃性及接著性之理由來看爲較佳’尤佳爲雙 馬來醯亞胺。 本發明之薄膜用組成物，當以上述（A)成分爲100質 量份時，係含有25~ 100質量份的上述（C)成分。 上述（C )成分未達25質量份時，使用薄膜用組成物 所製成之接著薄膜及覆蓋薄膜，在加熱硬化後，接著性及 難燃性不足。 另一方面，上述（C)成分超過100質量份時，與薄膜 用組成物中所含有之其他成分的相溶性降低，難以達成薄 膜用組成物的薄膜化。 (D )成分：硬化劑 本發明之薄膜用組成物，係含有有效量的硬化劑作爲 (D )成分。 用作爲（D )成分之硬化劑並無特別限定，可使用苯 酚系硬化劑、胺系硬化劑、酸酐系硬化劑等之各種硬化劑 〇 苯酚系硬化劑的具體例，是指具有苯酚性羥基之單體 、低聚物、聚合物全體，例如可列舉出苯酚酚醛樹脂、甲 酚酚醛樹脂、苯酚芳烷（含有伸苯、聯苯烯骨架）樹脂、 萘酚芳烷樹脂、三苯酚甲烷樹脂、二環戊二烯型苯酚樹脂 等。 胺系硬化劑的具體例，可列舉出2，4 -二胺基· 6 -〔 2，-甲 -17- 201137025 基咪唑基-(1')〕乙基-二級三嗪等之三嗪化合物、1，8-二 氮雜雙環〔5,4,0〕十一烯- 7(DBU)、三乙烯二胺、苄基 二甲基胺、三乙醇胺等之三級胺化合物。 酸酐系硬化劑的具體例，可列舉出鄰苯二甲酸酐、馬 來酸酐、十二烯琥珀酸酐、偏苯三甲酸酐、二苯基酮四羧 酸二酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐。 上述硬化劑中，可使用任一種或是倂用2種以上。 此等當中，苯酚系硬化劑及酸酐系硬化劑，就使用本 發明之薄膜用組成物所製成之接著薄膜或覆蓋薄膜的電特 性之觀點來看爲較佳，尤佳爲苯酚系硬化劑。 硬化劑的有效量因硬化劑的種類而不同，因應硬化劑 種類的不同，該有效量係顯示如下。 爲苯酚系硬化劑時，該有效量，相對於（A )成分之 環氧樹脂的環氧基1當量，硬化劑爲〇.〇1〜5當量，較佳爲 0.04〜1.5當量，尤佳爲0.08〜0.8當量。 爲胺系硬化劑時，該有效量，相對於（A )成分之環 氧樹脂的環氧基1當量，硬化劑爲0.001 ~1當量，較佳爲 0.005〜0.05當量，尤佳爲0.007-0.25當量。 爲酸酐系硬化劑時，該有效量，相對於環氧樹脂的環 氧基1當£，硬化劑爲0.05-10當量，較佳爲0.1〜5當量，尤 佳爲〇.5~1.8當量。 此外，苯酚系硬化劑、胺系硬化劑、酸酐系硬化劑中 ，當倂用2種以上時，係以各環氧硬化劑成爲上述有效量 之方式添佳。 -18 - 201137025 本發明之薄膜用組成 了上述（A) ~(D)成分 進劑作爲（E )成分。 用作爲（E )成分之: 用咪唑系硬化促進劑等之 當中，咪唑系硬化促進劑 之相溶性、以及薄膜用組 佳。 咪唑系硬化促進劑的 2_十一烷咪唑、2 -十七烷 基咪唑、2 -苯基-4-甲基咪 硬化促進劑的有效量 應硬化促進劑種類的不同 爲咪唑系硬化促進劑 100質量份，硬化硬化： 0.005~8質量份，尤佳爲〇. 本發明之薄膜用組成 )〜（E )以外的成分。此 起始劑、黏著性賦予劑、 劑、分散輔助劑、塡充材 本發明之薄膜用組成 例如在溶劑的存在或非存 來混合上述（A)〜（D) )成分或其他任意成分時: 物，爲了得到適當的硬化性’除 之外，亦可含有有效量的硬化促 更化促進劑並無特別限定’可使 各種硬化促進劑。硬化性促進劑 ，就與薄膜用組成物的其他成分 成物的硬化速度之方面來看爲較 具體例，可列舉出2-甲基咪唑、 米唑、2-乙基-4-甲基咪唑、2-苯 哩等之咪唑化合物等。 因硬化促進劑的種類而不同，因 ，該有效量係顯示如下。 時，該有效量，相對於環氧樹脂 IU爲0.001〜10質量份，較佳爲 〇 1〜5質量份。 物，亦可因應必要含有上述（A 般成分的具體例，可列舉出聚合 消泡劑、流動調整劑、成膜輔助 、導電性粒子等。 物，可藉由慣用的方法來製造。 在下，藉由加熱真空混合捏揉機 成分（當薄膜用組成物含有（E i更包含此等任意成分）。 -19- 201137025 以使上述成分（A)〜（D)成爲期望的含有比率之方 式（當薄膜用組成物含有成分（E)或上述成分（A)〜（ E)以外的成分時，使成分（E)或該其他成分成爲期望的 含有比率之方式）溶解成既定的溶劑濃度，將此等投入既 定量於加溫至10〜60°C之反應爐，一邊在轉數5 00〜lOOOprm 下旋轉，並進行常壓混合30分鐘後，於真空下（最大 lTorr)再混合搅拌30〜60分鐘。 本發明之接著薄膜或覆蓋薄膜，可藉由一般所知的方 法，從本發明之薄膜用組成物來製得。例如，以溶劑稀釋 本發明之薄膜用組成物來形成清漆，並將此塗佈於支撐體 的至少單面上，乾燥後可提供附有支撐體之薄膜，或是從 支撐體所剝離之薄膜。 可用做爲清漆之溶劑，可列舉出丁酮、甲基異丁酮等 之酮類；甲苯、二甲苯等之芳香族溶劑；鄰苯二甲酸二辛 酯、鄰苯二甲酸二丁酯等之高沸點溶劑等。溶劑的使用量 並無特別限制，可設爲以往所使用的量，較佳係相對於固 形份爲20〜90質Μ %。 支撐體，可藉由薄膜製造方法之期望形態來適當地選 擇，並無特別限定，例如可列舉出銅、鋁等之金屬箔，聚 酯、聚乙烯等之樹脂的載體薄膜等。當以從支撐體所剝離 之薄膜的形態來提供本發明之接著薄膜時，支撐體較佳係 經由聚矽氧烷化合物等施以脫模處理者。 塗佈清漆之方法並無特別限定，例如可列舉出狹縫方 式、凹版方式、刮刀塗佈方式等，可因應期望的薄膜厚度 -20- 201137025 等來適當地選擇，尤其是凹版方式可將薄膜設計較薄，故 較佳。塗佈，較佳是以使乾燥後所形成之薄膜厚度成爲期 望厚度之方式來進行。此般厚度，對該業者而言可從溶劑 含有量中導出。 本發明之接著薄膜或覆蓋薄膜的厚度，是根據因應用 途所要求之機械強度等特性來適當地設計，一般爲 1〜ΙΟΟμηι，在要求薄膜化時，較佳爲1〜30μιη。 乾燥的條件，可因應清漆所使用之溶劑的種類或量、 清漆使用量或塗佈厚度等來適當地設計，並無特別限定， 例如可在6 0〜1 2 0 °C、大氣壓下進行。 本發明之接著薄膜的使用步驟如下所述。 使用本發明之接著薄膜來接著之對象物中，將本發明 之接著薄膜載置於一方對象物的被接著面後，載置另一方 對象物以使該被接著面與接著薄膜的暴露面接觸。在此， 胃使用附有支撐體之薄膜時，以使接著薄膜的暴露面接觸 方令-方對象物的被接著面接觸之方式載置接著薄膜，並將 該接著薄膜轉印至被接著面。在此，轉印時的溫度，例如 可設爲8 0 °C。 接著，於轉印時，在藉由剝離支撐體所暴露出之接著 薄膜的面上，載置另一方對象物以使該被接著面與接著薄 膜的暴露面接觸。實施此等步驟後，在既定溫度及既定時 間’具體而言，在18(TC下進行60~90分鐘之依據模壓所進 行的熱壓著。藉由模壓進行熱壓著時，本發明之接著薄膜 被加熱而硬化。 -21 - 201137025 本發明之覆蓋薄膜的使用步驟基本上亦相同 明之覆蓋薄膜載置於印刷配線板的既定位置，亦 薄膜所被覆之位置後，藉由模壓進行熱壓著。藉 行熱壓著時，本發明之覆蓋薄膜被加熱而硬化。 此外，亦可將以溶劑稀釋本發明之薄膜用組 漆，塗佈於一方接著對象物的被接著面（覆蓋薄 覆蓋薄膜所被覆之位置）並進行乾燥後，實施將 對象物載置之步驟（覆蓋薄膜時爲依據模壓所進 著）。 以下說明本發明之接著薄膜或覆蓋薄膜的特' 本發明之接著薄膜及覆蓋薄膜，在加熱硬化 頻下的電特性佳。具體而言，加熱硬化後的覆蓋 頻率1〜10GHz的區域之介電率（ε )較佳爲3.0以 爲2,5以下。此外，在頻率1〜10GHz的區域之介 tan δ )，尤佳爲0.01以下。 藉由使在頻率1〜10GHz的區域之介電率（ε 正切（tan (5 )位於上述範圍內，可降低在頻率1 區域之電訊號損失。 本發明之接著薄膜及覆蓋薄膜，在加熱硬化 充分的接著強度。具體而言，加熱硬化後的接著 蓋薄膜，依據ns C647 1所測定之相對於聚醯亞 剝離強度（180度剝離），較佳爲lON/cm以上 15N/cm以上，更佳爲20N/cm以上。 本發明之接著薄膜及覆蓋薄膜，在加熱硬化 ，將本發 即以覆蓋 由模壓進 成物之清 膜時爲以 上述一方 行的熱壓 後’在商 薄膜，在 下，尤佳 ®正切（ )及介電 d 0GHz的 後，具有 薄膜及覆 暖薄膜之 ，尤佳爲 後，具有 -22- 201137025 充分的機械強度。具體而言，加熱硬化後的接著薄膜及覆 蓋薄膜，藉由後述實施例所記載的方法來測定之拉伸斷裂 強度，較佳爲3 0 Μ P a以上，尤佳爲4 0 Μ P a以上，更佳爲 4 5 MPa以上° 此外，加熱硬化後的接著薄膜及覆蓋薄膜，藉由後述 實施例所記載的方法來測定之拉伸斷裂伸長度，較佳爲 2mm以上，尤佳爲3mm以上，更佳爲4mm以上。 此外，加熱硬化後的接著薄膜及覆蓋薄膜，藉由後述 實施例所記載的方法來測定之拉伸彈性率，較佳爲 lOOOMPa以上，尤佳爲1200MPa以上，更佳爲1300MPa以 上。 本發明之接著薄膜及覆蓋薄膜，在加熱硬化後，具有 充分的可撓性。具體而言，加熱硬化後的接著薄膜及覆蓋 薄膜，依據〗IS P81 15實施MIT試驗時的耐折次數，較佳爲 1〇〇〇次以上。 本發明之接著薄膜及覆蓋薄膜，在加熱硬化後’具有 充分的耐熱性。具體而言，加熱硬化後的接著薄膜及覆蓋 薄膜，藉由後述實施例所記載的方法來測定之5%質量減少 溫度，較佳爲3 00°C以上。 本發明之接著薄膜及覆蓋薄膜’在加熱硬化後’具有 充分的難燃性。具體而言’加熱硬化後的接著薄膜及覆蓋 薄膜，在依據UL94V的難燃性規格所實施之難燃性試驗中 ，較佳係在難燃性等級下爲合格。此外’加熱硬化後 的接著薄膜及覆蓋薄膜’在依據UL9 4 VTM的難燃性規格所 -23- 201137025 實施之難燃性試驗中’較佳係在難燃性等級V Τ Μ - 0下爲合 格。 〔實施例〕 以下藉由實施例來更詳細說明本發明，但本發明並不 限定於此等。 (實施例1〜8、比較例1〜4 ) 將各成分溶解於溶劑（丁酮）以成爲既定的溶劑濃度 後，以成爲下列表所示之調配比率（質量份）之方式將此 等投入於加溫至25°C之反應爐，一邊在轉數300rpm下旋轉 並進行常壓混合1小時。 將如此製得之溶液（含有薄膜用組成物之清漆）塗佈 於基材（施以脫模處理後之PET薄膜）後，加熱基材以去 除溶劑，然後從基材中去除而得薄膜。 表中的略稱分別表示如下。 (A )成分 NC3 000H :聯苯型環氧樹脂（曰本化藥股份有限公司 製） Μη 590 (Β )成分 UR3 5 70 :以含磷多元醇作爲構成成分之胺基甲酸酯樹 脂（東洋紡社公司製） Μη 1 5000 -24- 201137025 (C)成分 B ΜI - 7 0 :雙馬來醯亞胺、KI化成股份有限公司製 (D )成分 BRM553:苯酚系硬化劑（苯酚樹脂）、昭和高分子 股份有限公司製 (E )成分 2E4MZ:咪唑系硬化促進劑（2 -乙基-4 -甲基咪唑、四 國化成工業股份有限公司製） 對製成的薄膜實施下列評估。結果如下列表所示。 介電率（ε)、介電正切（tan6):將藉由上述順 序所得之薄膜進行150 °Cxlh的加熱硬化後’從該薄膜裁切 出試驗片（40±0.5mmxl00±2mm)並測定厚度。將試驗片 捲成長度l〇〇mm、直徑2mm以下的筒狀，藉由空腔共振擾 動法（2GHz、5GHz、1 OGHz )來測定介電率（ε )及介 電正切（tan (5 )。 剝離強度：將藉由上述步驟所得之薄膜熱壓著於聚醯 亞胺薄膜（K100EN、T0ray DuPont股份有限公司製、 25μηι)並使其硬化後，依據〗IS C647 1來測定剝離強度（ 180度剝離）。 拉伸斷裂強度、拉伸斷裂伸長度：將藉由上述步驟所 得之薄膜進行1 5 〇 °C X 1 h的加熱硬化後，從該薄膜中，在 MD方向上裁切出5片的試驗片（15x150mm)並測定該厚 度。藉由Autograph精密萬能試驗機來測定拉伸斷裂強度 。此外’讀取至斷裂爲止之行程，並設爲拉伸斷裂伸長度 -25- 201137025 (% )。根據此等結果，計算出N = 5之平均値。 拉伸彈性率：將藉由上述步驟所得之薄膜進行1 5 0。(： X lh的加熱硬化後’從該薄膜中，在MD方向上裁切出5片的 試驗片（2 5 ± 0.5 mm X 2 5 0mm )並測定該厚度。在下列條件 下藉由Autograph精密萬能試驗機來測定拉伸彈性率。 抓取間隔1 70mm、拉伸速度lmm/min。 對於測定結果，係計算出N = 5之平均値。 耐熱性：將藉由上述步驟所得之薄膜進行1 5 0 °C X 1 h的 加熱硬化後，從該薄膜中裁切出試驗片（3mmx3mm )，使 用TG-DTA法來進行測定。此時係將5%質量減少溫度設爲 耐熱性之値。201137025 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a composition for a film. Specifically, it relates to a film composition for a cover film of a film or a printed wiring board suitable for electrical/electronic use. Further, the present invention relates to a film and a cover film which are produced using the film composition. [Prior Art] In recent years, the printed wiring board used in electric/electronic equipment has become more compact and higher in terms of miniaturization, weight reduction, and high performance of the multilayer printed wiring board. Densification, thinning, light weight, high reliability, and formability. In addition, with the recent demand for higher speed of transmission signals of printed wiring boards, the high frequency of transmission signals has been remarkably performed. Therefore, the material used for the printed wiring board is required to reduce the loss of the electric signal in the high frequency region, specifically, in the region of the frequency of 1 to 10 GHz. The adhesive film used as an interlayer adhesive or a surface protective film (i.e., a cover film) used as a printed wiring board is required to exhibit preferable electrical characteristics (low dielectric constant (ε), low dielectric tangent in a high frequency region). (tan 6 )). The material of the adhesive film used in the above-mentioned applications is inherently flammable. When used as an industrial material, in addition to satisfying the general chemical and physical properties in a balanced manner, it is required to be safe relative to the flame, that is, -5- 201137025 Flame retardant. In particular, when it is used in home appliances, it is required to have a high degree of flame retardancy such as "V94 of UL94V specification, V τ Μ - 0 specification of U L 9 4 V Μ 」". In general, a method of imparting flame retardancy to a film-like resin material is a method in which a halogen-based organic compound is added as a flame retardant to a resin, and a ruthenium compound is added as a flame retardant auxiliary. However, this method has a problem of causing corrosive halogen gas or highly toxic dioxin when burned. Therefore, in recent years, in order to eliminate the adverse effects of halogen-based flame retardants on the environment, it is strongly required to use a halogen-free flame retardant which is completely halogen-free. Regarding the halogen-free flame retardant prescription, for example, a phosphorus-based flame retardant can be used. However, when the flame retardancy is imparted by a phosphorus-containing additive such as a phosphate ester, it is necessary to mix a large amount of the resin into the resin, and not only the resin properties such as adhesion, heat resistance, and solder resistance are lowered, but also the flame retardant is generated at a high temperature. The problem of seepage in the environment. Therefore, Patent Documents 1 to 3 propose the following flame retardant resin compositions composed of a phosphorus-containing polymer compound. Patent Document 1 proposes a flame-retardant resin composition characterized by a resin (A) having a number average molecular weight of phosphorus of 3,000 or more in a molecule, and a phosphorus-containing compound having a phosphorus content of 3% by weight or more (B) The composition is formed by (A)/(B)=1〇〇/1~60 in a solid weight ratio. Patent Document 2 proposes a flame-retardant polyurethane resin composition comprising: a phosphorus-containing polyester polyol obtained by copolymerizing a phosphorus-containing carboxylic acid having a specific structure or the esterified product. As a constituent component, the acid-6-201137025 is a 50-equivalent/10 6 g or more polycarbamate, and an epoxy compound. Patent Document 3 proposes a flame retardant resin composition which is a flame retardant resin composition prepared by blending a thermosetting resin, a curing agent, a phosphorus-containing polyol, and a polyisocyanate, and is characterized in that the phosphorus is contained. The phosphorus in the polyol is contained in a ratio of 0.93% by weight or more based on the total amount of the thermosetting resin and the curing agent. However, in Patent Documents 1 to 3, the electric signal loss in the high frequency region is not taken seriously, and when the resin composition described in these documents is used in the adhesive film for the above use, it can be regarded as an electrical characteristic in a high frequency region. Will deteriorate. Further, in the flame-retardant resin composition described in Patent Document 1, the phosphorus-containing compound (B) contains ammonium polyphosphate. This system is used as a phosphorus-based flame retardant. Therefore, the flame retardant resin composition described in Patent Document 1 can be considered to have problems due to the above-described blending of the phosphorus-based flame retardant. In the flame retardant resin composition described in Patent Document 1, the reason why the phosphorus-containing compound (B) is used in addition to the phosphorus-containing resin (A) in the molecule is as described in the paragraph number [0020] of the document. When a high flame retardancy is imparted by the resin (A) alone, it is necessary to copolymerize a large amount of the phosphorus compound, resulting in problems such as hydrolysis or deterioration of the resin itself. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. 2005-6048 No. 2005-Patent Document No. 2005-6048 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The present invention has been made in order to solve the above problems of the prior art, and an object of the invention is to provide a high frequency region, specifically A film and a cover film for low dielectric constant and low dielectric loss in a frequency range of 1 to 5 GHz, and which are excellent in flame retardancy for electrical/electronic use, and films used in the production of such films Composition. (Means for Solving the Problem) In order to achieve the above object, the present invention provides a film composition characterized by: (A) an epoxy resin containing no hydroxyl group, and (B) a phosphorus-containing polyol as a constituent component a urethane resin, (C) a compound having a maleimide group, and (D) a hardener, and containing 1 to 975 parts by mass based on 1 part by mass of the component (A). The component (B), the component (C) containing 25 to 100 parts by mass, and the component (D) containing an effective hydrazine, the mass percentage of phosphorus to the total of the above (a) to (D) is 2 〜 7 %. The composition for a film of the present invention preferably further contains an effective amount of a (?) hardening accelerator. In the film composition of the present invention, the phosphorus-containing polyol contained in the urethane resin of the above (Β) component is preferably a phosphorus-containing polyol having a structure represented by the following formula. 201137025 [R1] (R2): ο P—(GH2)n_ Io CHCOOR3CHCOOR4 (wherein R1 and R2 independently of each other represent a hydrogen atom and a group consisting of a hydrocarbon group having 6 or less carbon atoms; Any one of R3 and r4 independently of each other, and one selected from the group consisting of a hydrogen atom, a hydrocarbon group having 6 or less carbon atoms, and a hydrocarbon group having 6 or less carbon atoms which may contain a hetero atom; Independently represents an integer of 〇~4; η represents an integer of 卜20). In the film composition of the present invention, the epoxy resin of the above (Α) component is preferably a biphenyl type epoxy resin. In the film composition of the present invention, the curing agent of the component (D) is preferably a phenol-based curing agent. In the film composition of the present invention, the hardening accelerator of the above (Ε) component is preferably an imidazole-based hardening accelerator. Further, the present invention provides an adhesive film which is produced using the composition for a film of the present invention. Further, the present invention provides a cover film which is produced using the composition for a film of the present invention. Further, the present invention provides a varnish which comprises the composition for a film of the present invention. -9- 201137025 Effect of the Invention: The adhesive film and the cover film of the present invention exhibit good electrical characteristics in a high frequency region after heat hardening, specifically, a low dielectric constant in a region of a frequency of 1 to 10 GHz ( ε) and low dielectric tangent (tan(5), so that low dielectric constant and low dielectric loss in the high frequency region can be achieved, and the flame retardancy is good. Further, the adhesive film and the cover film of the present invention. After heating and hardening, the organic material or inorganic material used in the printed wiring board of polyimide, liquid crystal polymer, ceramics, etc. can exhibit a good bonding strength. Further, the adhesive film and the cover film of the present invention It is suitable for use as a bonding film and a cover film for a flexible printed wiring board after heat curing. Therefore, the film of the present invention has good flexibility even before heat curing, so that it is in the film. In the processing step, the workability is good. Further, the adhesive film and the cover film of the present invention are incorporated by the resin component of the polyurethane because of the phosphorus which imparts flame retardancy to the film, and are incorporated. When the film is thermally cured, the copolymer formed by copolymerizing the polyurethane with the epoxy resin in the film, when a phosphorus-based flame retardant is added to the adhesive film or the cover film, The case where the flame retardant component is exuded in a high-temperature environment does not occur. The adhesive film and the cover film of the present invention can be produced by using the film composition of the present invention. In the present invention, the film of the present invention can also be contained. After the varnish of the composition is applied to the film-forming surface, it is dried and formed into a thin film instead of being formed into a film in advance. -10- 201137025 [Embodiment] The present invention will be described in detail below. The composition for a film of the present invention The component (A) to (D) shown below is contained as an essential component. (A) Component: an epoxy resin containing no hydroxyl group. In the composition for a film of the present invention, the component (A), that is, epoxy The resin is mainly used to impart thermosetting property, flame retardancy, and adhesion to the adhesive film and the cover film which are produced using the composition for a film. However, the adhesive film prepared using the composition for the film and The cover film 'after heat hardening, in order to exhibit better electrical characteristics in a high frequency region, specifically, a low dielectric constant (ε) and a low dielectric tangent (tan 5 ) in a region of a frequency of 1 to 10 GHz, An epoxy resin containing no hydroxyl group must be used. The epoxy resin as the component (A) can be widely selected from epoxy resins containing no hydroxyl group, and a biphenyl type epoxy resin or a cresol novolac epoxy resin can be used. Resin, cyclopentadiene type epoxy resin, etc. Among these, the biphenyl type epoxy resin is preferable in terms of the flame retardancy of the adhesive film and the cover film made of the film composition. The epoxy resin as the component (A) preferably has a number average molecular weight (?η) of from 100 to 1,000, and is preferably compatible with other components contained in the film composition. 〇〇~9〇〇, more preferably 400~700 〇Used as the (Α) component of the epoxy resin, the epoxy equivalent is preferably 50~500', especially preferably 150~450, more preferably 200~350. -11 - 201137025 (B) Component: A urethane resin containing a phosphorus-containing polyol as a constituent component. In the film composition of the present invention, the component (B) mainly imparts flame retardancy and flexibility to the adhesive film or the cover film produced by using the film composition. When a phosphorus-based flame retardant is added to the adhesive film or the cover film, a large amount of the flame retardant must be formulated, so that there is a problem that the flame retardant bleeds out during use of the film. Further, since a large amount of the flame retardant is required to be dispensed, there is a problem that the film is bonded, heat resistance, solder resistance, and electrical characteristics in a high frequency region are lowered. The adhesive film and the cover film of the present invention are incorporated by a polyurethane component of a resin component due to the phosphorus which imparts flame retardancy to the film, and are incorporated in the heat hardening of the film by making the polyamine group Since the acid ester is copolymerized with the epoxy resin in the film, when the phosphorus-based flame retardant is added to the adhesive film or the cover film, the flame retardant component does not ooze out in a high temperature environment. situation. Further, as described above, since phosphorus which imparts flame retardancy to the film is incorporated in the resin component (copolymer of polyurethane, polyurethane and epoxy resin), the phosphorus-based flame retardant is used. When added to the film or the cover film, the film is not deteriorated in adhesion, heat resistance, solder resistance, electrical characteristics in a high frequency region, and the like. The adhesive film and the cover film produced by using the film composition of the present invention, after heat curing, in order to satisfy the flame retardancy required by the film -12-201137025, and other characteristics required for the film, such as a film The quality, the heat resistance, the solder resistance, and the electrical properties in the high-frequency region must be such that the total mass of phosphorus relative to the film composition, that is, the mass percentage of the total mass of the components (A) to (D) becomes 2~ In the 7% way, the ingredients (B) are formulated. When the mass percentage of phosphorus to the total mass of the components (A) to (D) is less than 2%, the adhesive film and the cover film which are formed using the film composition are insufficient in flame retardancy after heat curing. On the other hand, when the mass percentage of phosphorus to the total mass of the components (A) to (D) exceeds 7%, the adhesive film and the cover film made of the composition for a film are used, and after heat curing, adhesion, Heat resistance 'weld resistance, and electrical characteristics in a high frequency region are insufficient. In the composition for a film of the present invention, the polyol of the component (B), that is, the constituent component of the urethane resin, may be any polyol as long as it contains at least one phosphorus atom in the molecule. The limitation includes, for example, a phosphorus-containing polyester polyol, a polyether polyol, a polycarbonate polyol, and a composite of these components. Among the phosphorus-containing polyols, a phosphorus-containing polyol having a structure represented by the following formula is particularly preferred. (R1) - p-(CH2)n - CHCOOR3 0 CHCOOR4 (R2)-- -13- 201137025 In the above formula, R1 and R2 independently of each other represent a hydrogen atom and a methyl group, an ethyl group, and a propyl group. Any one selected from the group consisting of a hydrocarbon group having a carbon number of 6 or less, such as a phenyl group. Among these, a hydrogen atom and a methyl group are preferred, and a hydrogen atom is particularly preferred. In the above formula, R3 and R4 each independently represent a hydrogen atom, a hydrocarbon group having 6 or less carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group or a benzyl group, and 2, hydroxyethyl group, or 2- Any one selected from the group consisting of a hydroxypropyl group, a 3-hydroxypropyl group, a 4-hydroxybutyl group, a 2-hydroxyethyloxyethyl group, and the like, which may contain a hetero atom having a carbon number of 6 or less and a substituted hydrocarbon group. One. Among these, a hydrogen atom is preferred. In the above formula, 1 and m each independently represent an integer of 0 to 4, and η represents an integer of 1 to 20. Preferably, 1 and m are each 1» η is preferably 1. The urethane resin of the (Β) component can be obtained by copolymerizing the polyhydric alcohol, that is, a polyhydric alcohol having at least one phosphorus atom in the molecule, with a polyisomeric acid ester. The polyisocyanate to be used in the copolymerization is not particularly limited as long as it can be copolymerized with a polyol having at least one phosphorus atom in the molecule to form a urethane resin, and is not particularly limited. Examples include methylene diisomeric acid ester (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), naphthalene diisocyanate (NDI), and xylene diisodecanoate (XDI). Various kinds of polyisocyanates and the like. In view of the reactivity of the adhesive film and the cover film produced by using the film composition, the heat resistance and flexibility of the film and the polyol having at least one phosphorus atom in the molecule are copolymerized. Look, especially good for -14-201137025 MDI polyisocyanate. UR3 5 70 (manufactured by Toyobo Co., Ltd.) is a specific example of the urethane resin obtained by copolymerization of a phosphorus-containing polyol and a polyisocyanate represented by the above formula. The urethane resin of the component (B) may contain, as a constituent component, a phosphorus-free polyol in addition to the above-mentioned phosphorus-containing polyol. When a phosphorus-free polyol is used as a constituent component, the total amount of all the polyols used in the preparation of the urethane resin is approximately the same equivalent as the polyisocyanate. Here, the equivalent means means an amount satisfying the following formula. (Equivalent) = (OH valence of polyol) x 7.49 / (NCO (%): isocyanate valence) NCO (%) is also called isocyanate valence. As the phosphorus-free polyol, various polyols of the same kind as the above-mentioned phosphorus-containing polyol (e.g., polyester polyol) or the like can be used in addition to the point of containing no phosphorus. The urethane resin of the component (B) preferably has a number average molecular weight (?η) of 3,000 or more. When the number average molecular weight is less than 3,000, the adhesive film and the cover film which are produced by using the film composition of the present invention have insufficient mechanical strength after heat curing, and the adhesion, heat resistance and various durability are deteriorated. In addition, when the number average molecular weight is more than 100,000, the viscosity of the composition for a film is increased, and the workability in the case of using a film composition to form a film or a cover film is deteriorated. The number average molecular weight of the (Β) component urethane resin is preferably from -15 to 201137025, and is preferably from 3,000 to 30,000, more preferably from 8,000 to 1,8,000. The composition for a film of the present invention contains 1 to 975 parts by mass of the above component (B) when the component (A) is 100 parts by mass. When the component (B) is less than 100 parts by mass, the adhesive film and the cover film which are produced by using the film composition of the present invention have insufficient flame retardancy after heat curing. Further, the adhesive film and the cover film which are formed using the composition for a film are deteriorated in flexibility. On the other hand, when the component (B) exceeds 975 parts by mass, the adhesive film and the cover film which are formed using the composition for a film are insufficient in heat resistance after heat curing. In the composition for a film of the present invention, the component (B) is preferably contained in an amount of from 1 to 600 parts by mass per 100 parts by mass of the component (A). (C) component: a compound having a maleic imine group. The component (C) of the film composition of the present invention mainly imparts flame retardancy to an adhesive film or a cover film produced using the composition for a film. Follow-up. In the composition for a film of the present invention, the component (C) is not particularly limited as long as it is a compound having a maleimine group, and examples thereof include bismaleimide and vinylphenyl malayan. Amine, 4,4-dimaleimide diphenyl ether, 4,4-maleimide diphenylmethane, 4,4-bismaleimide-3, 3'-dimethyl Benzyl-diphenylmethane, 4,4-bismaleimide diphenyl sulfonium, 4,4-bismaleimide diphenyl sulfide, 4,4-bismaleimide diphenyl benzene Ketone, 2,2'-bis(4-bismaleimide phenyl)propane, 3,4-bis-maleimide diphenylfluoromethane, 1,1,1,3,3,3 - hexafluoro-2,2-bis(4-bis-16-201137025 maleimide phenyl)propane, and the like. Among them, bismaleimide and vinyl phenyl maleimide are preferred because of the flame retardancy and adhesion of the film or cover film made of the film composition. For the double horse to the imine. The composition for a film of the present invention contains 25 to 100 parts by mass of the above component (C) when the component (A) is 100 parts by mass. When the amount of the component (C) is less than 25 parts by mass, the adhesive film and the cover film which are formed using the film composition are insufficient in adhesion and flame retardancy after heat curing. On the other hand, when the amount of the component (C) exceeds 100 parts by mass, the compatibility with other components contained in the film composition is lowered, and it is difficult to achieve film formation of the film composition. (D) Component: Hardener The composition for a film of the present invention contains an effective amount of a curing agent as the component (D). The curing agent to be used as the component (D) is not particularly limited, and various examples of the curing agent such as a phenol curing agent, an amine curing agent, and an acid anhydride curing agent, such as a phenol-based curing agent, may be used. Examples of the monomer, oligomer, and polymer include phenol novolac resin, cresol novolak resin, phenol aralkyl (containing benzene, biphenylene skeleton) resin, naphthol aralkyl resin, and trisphenol methane resin. , a dicyclopentadiene type phenol resin or the like. Specific examples of the amine-based curing agent include a triazine such as 2,4-diamino-6-[2,-methyl-17-201137025-based imidazolyl-(1')]ethyl-di-triazine. A tertiary amine compound such as a compound, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), triethylenediamine, benzyldimethylamine or triethanolamine. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, maleic anhydride, dodecene succinic anhydride, trimellitic anhydride, diphenyl ketone tetracarboxylic dianhydride, and tetrahydrophthalic anhydride. Hexahydrophthalic anhydride. Any one of the above-mentioned hardeners may be used alone or in combination of two or more. Among these, the phenolic curing agent and the acid anhydride curing agent are preferably used from the viewpoint of electrical properties of the adhesive film or the cover film produced by using the film composition of the present invention, and particularly preferably a phenolic curing agent. . The effective amount of the hardener varies depending on the kind of the hardener, and the effective amount is as follows depending on the kind of the hardener. In the case of a phenol-based curing agent, the effective amount is 1 equivalent to the epoxy group of the epoxy resin of the component (A), and the curing agent is 〜1 to 5 equivalents, preferably 0.04 to 1.5 equivalents, particularly preferably 0.08 to 0.8 equivalents. In the case of an amine-based curing agent, the effective amount is 0.001 to 1 equivalent, preferably 0.005 to 0.05 equivalent, and particularly preferably 0.007 to 0.25, based on 1 equivalent of the epoxy group of the epoxy resin of the component (A). equivalent. In the case of an acid anhydride-based curing agent, the effective amount is 0.05 to 10 equivalents, preferably 0.1 to 5 equivalents, particularly preferably 0.5 to 1.8 equivalents, per mole of the epoxy group. In addition, when two or more types of the phenol-based curing agent, the amine-based curing agent, and the acid-based curing agent are used, the epoxy curing agent is preferably added in an amount effective as described above. -18 - 201137025 The film of the present invention comprises the above components (A) to (D) as the component (E). As the component (E): Among them, an imidazole-based hardening accelerator or the like is used, and the compatibility of the imidazole-based hardening accelerator and the film are preferably used. The effective amount of 2 - undecylimidazole, 2 -heptadecylimidazole and 2-phenyl-4-methyl azo hardening accelerator of the imidazole-based hardening accelerator is an imidazole-based hardening accelerator depending on the type of the hardening accelerator 100 parts by mass, hardening and hardening: 0.005 to 8 parts by mass, particularly preferably 〇. The film of the present invention has a composition other than the component (e). The initiator, the adhesion-imparting agent, the dispersing aid, and the chelating material are used in the film composition of the present invention, for example, in the presence or absence of a solvent to mix the above components (A) to (D)) or other optional components. The material may contain an effective amount of a hardening accelerator in addition to the appropriate hardenability, and is not particularly limited to various curing accelerators. The curing accelerator is a specific example of the curing rate of the other components of the composition for a film, and examples thereof include 2-methylimidazole, imiazole, and 2-ethyl-4-methylimidazole. An imidazole compound such as 2-benzoquinone or the like. The amount of the curing accelerator varies depending on the type of the curing accelerator, and the effective amount is as follows. In this case, the effective amount is 0.001 to 10 parts by mass, preferably 1 to 5 parts by mass, based on the epoxy resin IU. The material may be contained as described above. Specific examples of the general component A include a polymeric antifoaming agent, a flow regulating agent, a film forming aid, and conductive particles. The product can be produced by a conventional method. Mixing the kneader components by heating under vacuum (when the film composition contains (E i further contains such optional components). -19- 201137025 in order to make the above components (A) to (D) into a desired content ratio (when When the composition for a film contains the component (E) or a component other than the components (A) to (E), the component (E) or the other component is dissolved in a desired solvent concentration, and is dissolved in a predetermined solvent concentration. The reaction is carried out in a reaction furnace heated to 10 to 60 ° C, rotated at a number of revolutions of 50,000 to 100 rpm, and mixed at atmospheric pressure for 30 minutes, and then mixed under vacuum (maximum 1 Torr) for 30 to 60. The adhesive film or cover film of the present invention can be obtained from the film composition of the present invention by a generally known method. For example, the film composition of the present invention is diluted with a solvent to form a varnish, and This coating On at least one side of the support, after drying, a film with a support or a film peeled off from the support may be provided. The solvent which can be used as the varnish may, for example, be butanone or methyl isobutyl ketone. A ketone; an aromatic solvent such as toluene or xylene; a high boiling point solvent such as dioctyl phthalate or dibutyl phthalate; the amount of the solvent used is not particularly limited, and can be used conventionally. The amount of the support is preferably from 20 to 90% by mass based on the solid content. The support can be appropriately selected from the desired form of the film production method, and is not particularly limited, and examples thereof include metals such as copper and aluminum. a carrier film of a resin such as a foil, a polyester or a polyethylene, etc. When the film of the present invention is provided in the form of a film peeled off from the support, the support is preferably applied via a polyoxyalkylene compound or the like. The method of applying the varnish is not particularly limited, and examples thereof include a slit method, a gravure method, and a blade coating method, and can be appropriately selected in accordance with a desired film thickness of -20 to 201137025, in particular, a gravure. It is preferred that the film has a thinner design, and the coating is preferably carried out in such a manner that the thickness of the film formed after drying becomes a desired thickness. The thickness can be from the solvent content to the manufacturer. The thickness of the adhesive film or the cover film of the present invention is appropriately designed according to characteristics such as mechanical strength required for the intended use, and is generally 1 to ΙΟΟμηι, and when it is required to be thinned, it is preferably 1 to 30 μm. The condition can be appropriately designed depending on the type or amount of the solvent used for the varnish, the amount of the varnish used, the thickness of the coating, and the like, and is not particularly limited, and can be carried out, for example, at 60 to 12 ° C under atmospheric pressure. The following steps of using the film are as follows: After the adhesive film of the present invention is applied to the object to be bonded, the adhesive film of the present invention is placed on the succeeding surface of one of the objects, and the other object is placed to make the object The surface is contacted with the exposed side of the film. Here, when the film with the support is used for the stomach, the adhesive film is placed so that the exposed surface of the film is in contact with the contact surface of the object, and the adhesive film is transferred to the bonded surface. . Here, the temperature at the time of transfer can be, for example, 80 °C. Next, at the time of transfer, the other object is placed on the surface of the adhesive film exposed by the peeling support so that the joined surface comes into contact with the exposed surface of the film. After performing these steps, at a predetermined temperature and a predetermined time, specifically, the hot pressing is performed at 18 (TC for 60 to 90 minutes depending on the molding. When the heat is pressed by molding, the present invention is followed. The film is heated and hardened. -21 - 201137025 The use step of the cover film of the present invention is basically the same as that of the cover film placed at a predetermined position of the printed wiring board, and after the film is covered, it is heat-pressed by molding. When the film is heat-pressed, the cover film of the present invention is heated and hardened. Further, the film paint for the film of the present invention may be diluted with a solvent and applied to the succeeding surface of one of the subsequent objects (covering the thin cover film). After the surface to be coated is dried, the step of placing the object is carried out (the film is covered in accordance with the molding process). The following describes the film and the film of the adhesive film or the cover film of the present invention. The film has good electrical characteristics at a heat curing frequency. Specifically, the dielectric constant (ε) of a region having a covering frequency of 1 to 10 GHz after heat curing is preferably 3.0 or less. Further, the tan δ dielectric 1~10GHz the frequency area), and particularly preferably 0.01 or less. By making the dielectric constant (ε (3) in the region of the frequency 1 to 10 GHz (tan (5) is within the above range, the electrical signal loss in the frequency 1 region can be reduced. The adhesive film and the cover film of the present invention are hardened by heat. In particular, the adhesive film after heat curing is preferably 1 ON/cm or more and 15 N/cm or more, as measured by ns C647 1 with respect to the polyimide peel strength (180 degree peeling). Preferably, it is 20 N/cm or more. The adhesive film and the cover film of the present invention are heat-hardened, and the present invention covers the film formed by molding into a film, and is subjected to hot pressing of the above-mentioned one line. , especially after tangential ( ) and dielectric d 0 GHz, with film and warm film, especially good, with sufficient mechanical strength of -22- 201137025. Specifically, the film and cover after heat hardening The tensile strength at break of the film measured by the method described in the examples below is preferably 30 Å or more, more preferably 40 Å or more, more preferably 4 5 MPa or more. Thinning after hardening And the cover film, the tensile elongation at break measured by the method described in the examples below is preferably 2 mm or more, more preferably 3 mm or more, still more preferably 4 mm or more. Further, the film and the cover film after heat curing The tensile modulus of the film measured by the method described in the examples below is preferably 1,000 MPa or more, more preferably 1200 MPa or more, and still more preferably 1300 MPa or more. The adhesive film and the cover film of the present invention are cured by heat. In addition, the adhesive film and the cover film after heat curing are preferably subjected to the number of times of folding in the MIT test according to IS P81 15, preferably one or more times. The film and the cover film have sufficient heat resistance after heat curing. Specifically, the heat-cured adhesive film and the cover film are preferably 5% mass-reduced temperature measured by the method described in the examples below. It is 300 ° C or more. The adhesive film and cover film of the present invention have sufficient flame retardancy after heat hardening. Specifically, the heat-cured adhesive film The cover film is preferably in the flame retardancy test according to the flame retardancy specification of UL94V, and is preferably qualified at the flame retardancy level. In addition, the 'heat-hardened adhesive film and cover film' are in accordance with UL9 4 VTM. Inflammability specification -23- 201137025 In the flame-retardant test carried out, it is preferable to pass the flame-retardant grade V Τ Μ - 0. [Examples] Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to these. (Examples 1 to 8 and Comparative Examples 1 to 4) After dissolving each component in a solvent (butanone) to have a predetermined solvent concentration, the ratio is shown in the following table. (Parts by mass) These were placed in a reaction furnace heated to 25 ° C, and rotated at a number of revolutions of 300 rpm and mixed at normal pressure for 1 hour. After the solution (the varnish containing the composition for a film) thus applied is applied to a substrate (a PET film subjected to a release treatment), the substrate is heated to remove a solvent, and then removed from the substrate to obtain a film. The abbreviations in the table are respectively indicated as follows. (A) Ingredient NC3 000H: Biphenyl type epoxy resin (manufactured by Sakamoto Chemical Co., Ltd.) Μη 590 (Β) component UR3 5 70 : urethane resin containing phosphorus polyol as a constituent (Toyobo社η 1 5000 -24- 201137025 (C) Component B ΜI - 7 0 : Bismaleimide, KI Chemical Co., Ltd. (D) component BRM553: phenolic curing agent (phenol resin), Showa (E) component 2E4MZ manufactured by Polymer Co., Ltd.: imidazole-based hardening accelerator (2-ethyl-4-methylimidazole, manufactured by Shikoku Chemicals Co., Ltd.) The following evaluation was performed on the produced film. The results are shown in the following list. Dielectric ratio (ε), dielectric tangent (tan6): After the film obtained by the above procedure was heat-hardened at 150 ° C×lh, the test piece (40±0.5 mm×100±2 mm) was cut out from the film and the thickness was measured. . The test piece was rolled into a cylindrical shape having a length of l〇〇mm and a diameter of 2 mm or less, and the dielectric constant (ε) and the dielectric tangent (tan (5) were measured by a cavity resonance perturbation method (2 GHz, 5 GHz, 1 OGHz). Peeling strength: The film obtained by the above procedure was heat-pressed on a polyimide film (K100EN, manufactured by T0ray DuPont Co., Ltd., 25 μηι) and hardened, and the peel strength was measured according to IS C647 1 (180). Tensile breaking strength, tensile elongation at break: After the film obtained by the above step is subjected to heat hardening at 15 ° C C 1 h, 5 pieces of the film are cut out in the MD direction. Test piece (15x150mm) and measure the thickness. The tensile breaking strength was measured by Autograph precision universal testing machine. In addition, the stroke until the fracture was read and set to tensile elongation at break -25-201137025 (%) Based on these results, the average enthalpy of N = 5 was calculated. Tensile modulus: The film obtained by the above procedure was subjected to 150. (: X lh after heat hardening 'from the film, in the MD direction Cut 5 test pieces (2 5 ± 0.5 mm) X 2 5 0 mm ) and the thickness was measured. The tensile modulus was measured by an Autograph precision universal tester under the following conditions: The gripping interval was 1 70 mm, and the stretching speed was 1 mm/min. For the measurement results, N = Heat resistance: After the film obtained by the above procedure was subjected to heat hardening at 150 ° C for 1 h, the test piece (3 mm x 3 mm) was cut out from the film and measured by TG-DTA method. At this time, the 5% mass reduction temperature was set as the heat resistance.
使用裝置：Bruker AXS公司製 TG-DTA2020SA 測定範圍：溫度範圍2 0 °C〜5 0 0 °C 升溫速度10°C /min 測定環境空氣 難燃性：將藉由上述步驟所得之薄膜進行1 5 0 °C X 1 h的 加熱硬化後，從該薄膜中裁切出試驗片（125mm xl 2.5mm )’根據UL94V及UL94VTM來評估難燃性。以在難燃性等 級V-0下合格者爲〇，不合格者爲x。 -26- 201137025 【表1】 實施例1 實施例2 實施例3 實施例4 (A)成分 NC3000H 100 100 100 100 (B)成分 UR3570 100 150 250 450 (C)成分 BMI-70 70 70 70 70 (D)成分 BRM553 18.75 18.75 18.75 18.75 ⑹成分 2E4MZ 3.75 3.75 3.75 3.75 硬化劑當量< D)/^氧基當量(A) 0.5 0.5 0.5 0.5 ε 2GHz 3.1 3.1 3 3 5GHz 3.1 3 3 3 10GHz 2.9 2.9 2.9 2.9 tan δ 2GHz 0.025 0.022 0.02 0.012 5GHz 0.022 0.019 0.017 0.011 10GHz 0.02 0.018 0.016 0.01 剝離強度 ΡΙ/ΡΐΓΝ/cm] >1000 >1000 >1000 >1000 拉伸強度 斷裂強度[MPal 51 49 50 73 斷裂择長S [mm] 5 4 4 5 拉伸彈性率[Mpa] 1390 1416 1390 2159 耐熱性 5%質量減少溫度r°Cl 336 330 329 333 難燃性 UL94V 〇 〇 〇 〇 UL94VTM 〇 〇 〇 〇 【表2】 實施例5 實施例6 實施例7 實施例8 (A)成分 NC3000H 100 100 100 100 (B)成分 UR3570 600 450 450 100 (C)成分 ΒΜΙ-70 70 25 100 70 (D)成分 BRM553 18.75 18.292 18.75 18.75 (E)成分 2Ε4ΜΖ 3.75 3.659 3.75 — 硬化劑當量(D)/^氧基當量(A) 0.5 0.5 0.5 0.5 ε 2GHz 3 3 3 3 5GHz 3 3 3 3 10GHz 2.9 2.9 2.8 2.8 tan δ 2GHz 0Ό12 0.013 0.011 0.011 5GHz 0.01 0.011 0.011 0.011 10GHz 0.01 0.011 0.01 0.01 剝離強度 ΡΙ/ΡΐΓΝ/cml >1000 >1000 >1000 >1000 拉伸強度 斷裂強度「MPal 61 62 76 77 [mm] 7 4 5 5 拉伸弓. |性率[MPa] 1679 2089 2309 1712 耐熱性 5%質量減少溫度「°C1 325 331 338 322 難燃性 UL94V 〇 〇 〇 〇 UL94VTM 〇 〇 〇 〇 -27- 201137025 【表3】 比較例1 比較例2 比較例3 比較例4 (A)成分 NC3000H 100 100 100 100 ⑻成分 UR3570 50 975.61 450 450 (C)成分 BM 卜 70 70 70 20 105 (D)成分 BRM553 18.75 18.75 18.75 18.75 (E)成分 2E4MZ 3.75 3.75 2.97 3.75 硬化劑當S(D)顧氧基當量(A) 0.5 0.5 0.5 0.5 ε 2GHz 3.2 3 3.1 - 5GHz 3.1 3 3 - 10GHz 2.9 2.8 2.9 - tan δ 2GHz 0.028 0.011 0.016 - 5GHz 0.024 0.009 0.014 - 10GHz 0.021 0.009 0.013 - 剝離強度 PI/PI[N/cml >1000 >1000 2.3 - 拉伸強度 斷裂強度CMPal 52 53 70 - 斷裂伸長度[mm] 5 7 5 - mm 單性率[MPa] 1190 1250 1920 - 耐熱性 5〇/o質fl減少溫度「°C1 341 299 334 - 難燃性 UL94V X 〇 〇 - UL94VTM X 〇 〇 - 從表中可得知，實施例1〜8之薄膜，在加熱硬化後， 在高頻區域之電特性（介電率e 、介電正切tan (5 )、剝 離強度、拉伸強度（拉伸斷裂強度、拉伸斷裂伸長度）、 拉伸彈性率、耐熱性、難燃性均佳。 (B)成分含量較少之比較例1之薄膜，在加熱硬化後 ，難燃性惡化。 (B )成分含量過多之比較例2之薄膜，在加熱硬化後 ，耐熱性惡化。 (C )成分含量較少之比較例3之薄膜，在加熱硬化後 ，剝離強度惡化。 (C )成分含量過多之比較例4之薄膜，相溶性惡化而 無法薄膜化。 -28- 201137025 (實施例9、比較例5 ) 對於以與實施例4相同之步驟所製成之薄膜（實施例9 )、與市售的聚醯亞胺薄膜（Kapton、Toray DuPont股份 有限公司製）（比較例5 )實施下列評估。薄膜厚度均爲 2 5 μηι 0 剝離強度··將使薄膜組成物夾持於聚醯亞胺薄膜（ Kapton 100Η、Toray DuPont股份有限公司製、厚度 25μιη )並藉由真空模壓使其硬化（180°C下lhr、IMPa、真空度 < 10kPa)之試樣裁切爲l〇mm寬，並藉由萬能試驗機（島 津製作所公司製A G -1S )來測定剝離強度（1 8 0度剝離、速 度 50mm/min ) 〇 耐折性：對於進行1 5 0 °c X 1 h的加熱硬化後之薄膜，依 循JIS P8 1 1 5來實施MIT試驗（R=1 . MD )。下列表係顯示 薄膜斷裂之時點的折彎次數。 插入損失：在聚醯亞胺基板上製作微帶線，藉由真空 模壓（180°C下Ihr、IMPa、真空度<10kPa)來貼附薄膜 組成物作爲覆蓋薄膜，而製作出試驗片。 對所製作之試驗片’藉由20GHz S參數向量網路分析 器（Agilent 8720ES)，在S21下測定該插入損失（ 〜20GHz)。 29- 201137025 表4 實施例9 比較例5 ε (10GHz) 2.9 3.4 tan (5 (10GHz) 0.01 0.035 剝離強度 〇 〇 耐折性（MIT試驗）〔次〕 >1000 703 插入損失（10GHz)〔dB〕 -7.04 -8.29 從表中可得知，實施例9之薄膜，與比較例5之聚醯亞 胺薄膜相比，在加熱硬化後，在高頻區域之電特性（介電 率ε 、介電正切tan (5 )較佳。其結果可得知在高頻區域 之插入損失較小。關於耐折性，與比較例5之聚醯亞胺薄 膜相比爲較佳。關於剝離強度，顯示出與比較例5之聚醯 亞胺薄膜相比毫不遜色之結果。 ^ 產業上之可利用性： 本發明之薄膜用組成物，乃適合於製造電性/電子用 途的接著薄膜或印刷配線板的覆蓋薄膜。 -30-Equipment used: TG-DTA2020SA manufactured by Bruker AXS Co., Ltd. Measurement range: Temperature range 2 0 °C~5 0 0 °C Heating rate 10 °C /min Determination of ambient air flame retardancy: The film obtained by the above procedure is carried out 1 5 After heat hardening at 0 °CX for 1 h, a test piece (125 mm x l 2.5 mm) was cut out from the film. The flame retardancy was evaluated according to UL94V and UL94VTM. Those who pass the test at the flame retardancy level V-0 are 〇, and those who fail are x. -26- 201137025 [Table 1] Example 1 Example 2 Example 3 Example 4 (A) component NC3000H 100 100 100 100 (B) component UR3570 100 150 250 450 (C) component BMI-70 70 70 70 70 ( D) Component BRM553 18.75 18.75 18.75 18.75 (6) Component 2E4MZ 3.75 3.75 3.75 3.75 Hardener equivalent < D) / oxy equivalent (A) 0.5 0.5 0.5 0.5 ε 2 GHz 3.1 3.1 3 3 5 GHz 3.1 3 3 3 10 GHz 2.9 2.9 2.9 2.9 Tan δ 2GHz 0.025 0.022 0.02 0.012 5GHz 0.022 0.019 0.017 0.011 10GHz 0.02 0.018 0.016 0.01 Peel strength ΡΙ/ΡΐΓΝ/cm] >1000 >1000 >1000 >1000 Tensile strength breaking strength [MPal 51 49 50 73 Length S [mm] 5 4 4 5 Tensile modulus [Mpa] 1390 1416 1390 2159 Heat resistance 5% mass reduction temperature r°Cl 336 330 329 333 Flame retardant UL94V 〇〇〇〇UL94VTM 〇〇〇〇 [Table 2 Example 5 Example 6 Example 7 Example 8 (A) component NC3000H 100 100 100 100 (B) component UR3570 600 450 450 100 (C) component ΒΜΙ-70 70 25 100 70 (D) component BRM553 18.75 18.292 18.75 18.75 (E) Composition 2Ε4ΜΖ 3.75 3.659 3.75 Hardener equivalent (D) / oxy equivalent (A) 0.5 0.5 0.5 0.5 ε 2GHz 3 3 3 3 5GHz 3 3 3 3 10GHz 2.9 2.9 2.8 2.8 tan δ 2GHz 0Ό12 0.013 0.011 0.011 5GHz 0.01 0.011 0.011 0.011 10GHz 0.01 0.011 0.01 0.01 Peel strength ΡΙ/ΡΐΓΝ/cml >1000 >1000 >1000 >1000 Tensile strength breaking strength "MPal 61 62 76 77 [mm] 7 4 5 5 Stretching bow. |Sexuality [MPa] 1679 2089 2309 1712 Heat resistance 5% mass reduction temperature "°C1 325 331 338 322 flame retardant UL94V 〇〇〇〇UL94VTM 〇〇〇〇-27- 201137025 [Table 3] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 ( A) Ingredients NC3000H 100 100 100 100 (8) Ingredients UR3570 50 975.61 450 450 (C) Ingredients BM Bu 70 70 70 20 105 (D) Ingredient BRM553 18.75 18.75 18.75 18.75 (E) Ingredients 2E4MZ 3.75 3.75 2.97 3.75 Hardener when S(D) )Ethyl equivalent (A) 0.5 0.5 0.5 0.5 ε 2GHz 3.2 3 3.1 - 5GHz 3.1 3 3 - 10GHz 2.9 2.8 2.9 - tan δ 2GHz 0.028 0.011 0.016 - 5GHz 0.024 0.009 0.014 - 10GHz 0.021 0.009 0.013 - Peel strength PI/PI [N/cml >1000 >1000 2.3 - Stretching Strength breaking strength CMPal 52 53 70 - Elongation at break [mm] 5 7 5 - mm Parthenogenous rate [MPa] 1190 1250 1920 - Heat resistance 5〇/o quality fl reduced temperature "°C1 341 299 334 - Flame retardant UL94V X 〇〇- UL94VTM X 〇〇 - As can be seen from the table, the electrical properties of the films of Examples 1 to 8 in the high frequency region after heat hardening (dielectric rate e, dielectric tangent tan (5), Peel strength, tensile strength (tensile breaking strength, tensile elongation at break), tensile modulus, heat resistance, and flame retardancy are all good. The film of Comparative Example 1 in which the content of the component (B) was small was deteriorated in flame retardancy after heat curing. The film of Comparative Example 2 in which the content of the component (B) was excessively deteriorated after heat curing. The film of Comparative Example 3 in which the content of the component (C) was small was deteriorated after the heat curing. In the film of Comparative Example 4 in which the content of the component (C) was too large, the compatibility was deteriorated and the film formation was impossible. -28-201137025 (Example 9, Comparative Example 5) A film produced in the same manner as in Example 4 (Example 9), and a commercially available polyimide film (Kapton, Toray DuPont, Inc.) (Comparative Example 5) The following evaluations were carried out. Film thickness is 2 5 μηι 0 Peel strength · The film composition is sandwiched between a polyimide film (Kapton 100®, manufactured by Toray DuPont Co., Ltd., thickness 25 μm) and hardened by vacuum molding (180°) The sample of lhr, IMPa, and vacuum (10 kPa) was cut to a width of 10 mm, and the peel strength (180 ° peeling speed) was measured by a universal testing machine (AG-1S manufactured by Shimadzu Corporation). 50 mm/min) 〇 folding resistance: For the film which was heat-hardened at 150 ° C for 1 h, the MIT test (R = 1.0 m) was carried out in accordance with JIS P8 1 15 . The lower list shows the number of bends at the time the film breaks. Insertion loss: A microstrip line was formed on a polyimide substrate, and a film composition was attached as a cover film by vacuum molding (Ihr, IMPa, vacuum degree < 10 kPa at 180 ° C) to prepare a test piece. The insertion loss (~20 GHz) was measured at S21 for the prepared test piece by a 20 GHz S-parameter vector network analyzer (Agilent 8720ES). 29- 201137025 Table 4 Example 9 Comparative Example 5 ε (10 GHz) 2.9 3.4 tan (5 (10 GHz) 0.01 0.035 Peel strength 〇〇 folding resistance (MIT test) [times] > 1000 703 insertion loss (10 GHz) [dB -7.04 - 8.29 As can be seen from the table, the film of Example 9 has electrical properties in the high frequency region after heat hardening as compared with the polyimide film of Comparative Example 5 (dielectric ratio ε, 介The electric tangent tan (5) is preferable, and as a result, it is found that the insertion loss in the high frequency region is small. The folding endurance is better than that of the polyimide film of Comparative Example 5. The result is not inferior to that of the polyimide film of Comparative Example 5. ^ Industrial Applicability: The film composition of the present invention is suitable for the production of an adhesive film or printed wiring for electrical/electronic use. Cover film of the board. -30-