201030083 六、發明說明： 【發明所屬之技術領域】 本發明係關於對於零件内藏基板之製造有用之熱硬化 性樹脂組成物、及具有使用該熱硬化性樹脂組成物之接著 層的接著薄膜，以及使用該接著薄膜之零件内藏基板的製 造方法。 @ 【先前技術】 於印刷電路板中，現要求著輕薄短小化而成之高密度 化。於零件内藏基板中，被嵌入之零件變小，而於嵌入時 之高位置精度則爲必要。又，由必需將基板全體之大小縮 小一事，於嵌入之零件與零件周邊之電路之間具有高絕緣 性之材料則成爲必要。 作爲零件内藏基板之製造方法，雖有揭示藉由薄片劑 (sheet agent )與附黏著劑之薄片劑將零件予以假固定， φ 將零件以樹脂密封後，將薄片除去之方法（專利文獻1) ，但並無揭示具體之組成。又，由於零件密封後有將黏著 劑除去之必要而使步驟數增加。 又，有揭示在芯基板之電子零件實際裝載面上，藉由 黏著材將零件假固定，將零件以樹脂密封之方法（專利文 獻2)。作爲黏著材，以具有電絕緣性，進而加上高熱時 ，會蒸發或成爲氣體之材料較佳，而使用之高分子的具體 例，可單獨使用丙烯酸樹脂、聚酯樹脂、馬來化油樹脂、 聚丁二烯樹脂、環氧樹脂等或將其任意組合之混合物。又 -5- 201030083 ’用以賦予此些高分子樹脂黏著性之松香系、萜系、石油 樹脂系等之賦予黏著之樹脂可依據需要而添加。然而，其 並無揭示黏著材之具體組成。 又，將接著層不僅在電子零件之接著場所，在全面具 備絕緣性基材上將零件假固定，將零件以樹脂進行密封之 方法（專利文獻3)。作爲接著層，可例示環氧樹脂系、 聚胺基甲酸酯系、反應性丙烯酸系、紫外線硬化型或聚矽 氧系，而作爲例子則有揭示對環氧樹脂系或聚矽氧系等予 以混合酚樹脂、有機酸酐、胺或硬化促進劑等之硬化劑而 使用。其次，揭示爲了將零件固定，在硬化溫度之加熱或 藉由照射紫外線照射等使其硬化之手法。但，其並無揭示 接著層之具體組成。又，藉由接著層之熱硬化而將電子零 件固定之情況，則有因爲接著層之熔融而使零件之固定位 置精度降低之問題。並且有紫外線所成之硬化其步驟爲複 雑之問題。 [專利文獻1]特開2002-204045號公報 [專利文獻2]特開2004-296562號公報 [專利文獻3]特開2007-42829號公報 【發明內容】 [發明所欲解決之課題] 本案發明之課題在於提供對於藉由接著層之黏著性（ tack性）而將電子零件固定於接著層，使該接著層熱硬化 之情況，可製造零件之固定位置精度及絕緣信賴性爲高之 -6- 201030083 零件内藏基板的熱硬化性樹脂組成物。 [用以解決課題之手段] 本發明者們爲了解決上述課題而進行銳意檢討之結果 ，藉由使用含有液狀環氧樹脂、酚系硬化劑、無機塡料及 丙烯酸樹脂之特定的熱硬化性樹脂組成物而完成本發明。 即，本發明爲含有以下之内容者。 φ [1] 一種熱硬化性樹脂組成物，其係零件内藏基板 之零件固定及絕緣層形成所用之熱硬化性樹脂組成物，其 特徵爲在熱硬化性樹脂組成物之不揮發份設爲1 00重量％ 之情況時，含有25 °c下液狀之環氧樹脂25〜40重量％、丙 烯酸樹脂〇.1~5重量％、酚系硬化劑5~30重量％及無機塡 料2 0〜70重量％。 [2] 如上述Π]記載之熱硬化性樹脂組成物，其中丙 烯酸樹脂爲丙烯酸酯共聚物。 φ [3] 如上述Π]或[2]記載之熱硬化性樹脂組成物， 其中丙烯酸樹脂爲含有丙烯酸甲酯、丙烯酸丁酯、丙烯腈 之丙烯酸酯共聚物。 [4] 如上述[1]~[3]記載之熱硬化性樹脂組成物，其 中丙烯酸樹脂含有選自環氧基、羥基、羧基之1種以上之 基。 [5] 如上述[U〜[4] (C記載之熱硬化性樹脂組成物， 其中丙烯酸樹脂爲含有羥基及羧基。 [6] —種接著薄膜，其特徵爲於支持體上具有由上 201030083 述[1]〜[5]記載之熱硬化性樹脂組成物所形成之接著層，其 係爲零件内藏基板之零件固定及絕緣層形成所用之接著薄 膜。 [7] 如上述[6]記載之接著薄膜，其中接著層之厚度 爲 5〜ΙΟΟμιη [8] 如上述[6]或[7]記載之接著薄膜，其中支持體 爲塑膠薄膜。 [9] 如上述[6]〜[8]之任一項記載之接著薄膜，其中 支持體之接著層側之面爲經離型處理者。 [10] —種零件内藏基板之製造方法，其特徵爲包含 如上述[1]~[ 9]中任一項記載之接著薄膜之接著層上將電子 零件固定之步驟及使該接著層熱硬化而形成絕緣層之步驟 [發明之效果] 依據本發明，藉由使用含有液狀環氧樹脂、酚系硬化 劑、無機塡料及丙烯酸樹脂之特定的熱硬化性樹脂組成物 ，可提供對於藉由接著層之黏著性（tack性）將電子零件 固定於接著層，使該接著層熱硬化之情況時，可製造零件 之固定位置精度及絕緣信賴性爲高之零件内藏基板的熱硬 化性樹脂組成物。 【實施方式】 [25°C下液狀之環氧樹脂] -8 - 201030083 本發明中「25 °C下液狀之環氧樹脂」，主要係同時提 高硬化物之耐熱性及絕緣性’賦予熱硬化性樹脂組成物之 黏著性。作爲25°C下液狀之環氧樹脂，具體上有，雙酚a 型環氧樹脂、雙酚F型環氧樹脂、酚醛清漆型環氧樹脂、 萘型環氧樹脂、三級丁基兒茶酚型環氧樹脂、具有丁二烯 構造之環氧樹脂、脂肪族系環氧丙基酸、醇類之環氧丙基 醚化物’以及此些之環氧樹脂之鹵化物及加氫物等。此些 φ 可1種或將2種以上組合使用。 此些之中’由耐熱性、絕緣信賴性之觀點，以雙酚A 型環氧樹脂、萘酚型環氧樹脂、萘型環氧樹脂、脂肪族系 環氧丙基醚、具有丁二烯構造之環氧樹脂爲佳。環氧樹脂 之具體例，可舉出液狀雙酚A型環氧樹脂（Japan Epoxy Resin (股）製「Epikote 828EL」）、液狀雙酚F型環氧 樹脂（Japan Epoxy Resin (股）製「Epikote 807」）、萘 型2官能環氧樹脂（大日本油墨化學工業（股）製「 φ HP4032」、「HP4032D」）、脂肪族系環氧丙基醚（東都 化成（股）製「ZX-1658」）、具有丁二烯構造之環氧樹 脂（Daicel化學工業（股）製「PB-3600」）等。「25°C 下液狀之環氧樹脂」亦可將2種以上組合使用。 將熱硬化性樹脂組成物之不揮發成分設爲100重量％ 之情況，25 °C下液狀之環氧樹脂之含有量之上限値，由防 止黏著力變大而覆蓋薄膜之剝離性變差，又防止於薄膜硬 化時容易產生零件之位置偏差之觀點，以40重量％爲佳 ，35重量％爲更佳。另一方面，將熱硬化性樹脂組成物之 -9 · 201030083 不揮發成分設爲100重量％之情況時’ 25 °c下液狀之環氧 樹脂之含有量的下限値，由防止零件變得難以固定於接著 薄膜之觀點，以25重量％爲佳’ 30重量％爲更佳。 [丙烯酸樹脂] 本發明中之「丙烯酸樹脂」主要係寄予熱硬化性樹脂 組成物之黏著性。作爲丙烯酸樹脂可舉出，聚丙烯酸、聚 甲基丙烯酸、聚丙烯酸酯、聚甲基丙烯酸酯、聚丙烯酸酯 共聚物、聚甲基丙烯酸酯共聚物等。又，丙烯酸樹脂以具 有優良黏著性之丙烯酸酯共聚物爲佳，更以丙烯酸甲酯共 聚物、丙烯酸乙酯共聚物爲佳。作爲共聚化合物，可舉出 丙烯酸甲酯、丙烯酸丁酯、乙酸乙烯酯、丙烯腈、丙烯醯 胺等，其中以丙烯酸甲酯、丙烯酸丁酯、丙烯腈爲佳。且 ，丙烯酸甲酯·共聚物或丙烯酸乙酯共聚物以更含有選自環 氧基、羥基、羧基之1種以上之基爲佳，特別以含有羥基 及/或羧基爲佳》此些可1種或2種以上組合使用。 將熱硬化性樹脂組成物之不揮發成分設爲100重量％ 之情況，丙烯酸樹脂之含有量之上限値，由防止黏著力變 大而覆蓋薄膜之剝離性變差、操作性拙劣之觀點，以5重 量％爲佳，3重量％爲更佳。另一方面，將熱硬化性樹脂 組成物之不揮發成分設爲100重量％之情況，丙烯酸樹脂 之含有量之下限値，由防止因爲黏著性之降低所造成之難 以固定零件之觀點，以〇·1重量％爲佳，0.5重量％爲更佳 201030083 丙烯酸樹脂之重量平均分子量的上限値，由防止對溶 劑及環氧樹脂之溶解性降低而製作均勻熱硬化性樹脂組成 物變得困難之觀點，以1,200,000爲佳，以900,000爲更 佳。另一方面，丙烯酸樹脂之重量平均分子量的下限値， 由防止組成物之黏著性降低而固定零件變得困難之觀點， 以400,000爲佳，500,000爲更佳。尙，本發明中之重量 平均分子量係以凝膠滲透層析（GPC )法（以聚苯乙烯換 φ 算）所測定。GPC法所得之重量平均分子量，具體而言係 以（股）島津製作所製之LC-9A/RID-6A作爲測定裝置， 以昭和電工（股）公司製 Shodex K-800P/K-804L/K-804L 作爲管柱，使用氯仿等作爲流動相，管柱溫度40°C中進行 測定，使用標準聚苯乙烯之標準曲線而可算出。 作爲市售之丙烯酸樹脂，具體可舉出人1"〇|^&(^8-1511L、S-1511X、S-1515、S-1517C 東亞合成（股）公司 製）Toaacron AR-601、AR-602、AR-603 ((股）TOHPE φ 製）NIPOL AR-31、AR-51、AR-54 (日本 ΖΕΟΝ (股）公 司製·）、Noxtite PA-301、PA-501、PA-502 ( NOK (股） 公司製）、丁613&111168111\\^-022、评8-023 '8〇-51'3〇-70L、SG-80 ( Nagase ChemteX (股）公司製）、KH-LT、 KH-CT (日立化成工業（股）公司製）等。「丙烯酸樹脂 」可將2種以上組合使用。 [酚系硬化劑] 本發明中之「酚系硬化劑」主要係作爲環氧樹脂之硬 -11 - 201030083 化劑運用。作爲酚系硬化劑，只要係可作爲具有酚性羥基 之環氧樹脂之硬化劑運用則無特別限定。一般而言’使用 分子内具有2個以上之酚性羥基的酚化合物，具體可舉出 苯酚酚醛清漆樹脂、甲酚酚醛清漆樹脂等。市售之之酚系 硬化劑，可舉出例如 MEH-7700、MEH-7810、MEH-785 1 (明和化成（股）製）、NHN、CBN、GPH (日本化藥（ 股）製）、SN170 、 SN180 、 SN190 、 SN475 、 SN485 、 SN495、SN3 75、SN3 95 (東都化成（股）製）、TD2090 · 、TD2093 、KA1160、KA1163 、 LA7052 、 LA7054、 LA3018、LA1356C大曰本油墨化學工業（股）製）等。 「酚系硬化劑」可2種以上組合使用。 將熱硬化性樹脂組成物之不揮發成分設爲100重量％ 之情況，酚系硬化劑之含有量的上限値，由防止黏著力之 低下或防止硬化劑成分變得過剩，引起耐熱性、絕緣性等 之作爲絕緣材料之重要特性的降低之觀點，以30重量％ 爲佳，25重量％爲更佳，以20重量％爲更佳，1 5重量％ ❹ 爲特佳。另一方面，將熱硬化性樹脂組成物之不揮發成分 設爲1 00重量％之情況，酚系硬化劑之含有量的下限値， 由防止引起硬化劑成分變得過少，樹脂之硬化變得非常慢 以外，且防止耐熱性、絕緣性等之作爲絕緣材料之重要特 性的降低之觀點，以5重量％爲佳，1 〇重量％爲更佳。 [無機塡料] 本發明中之「無機塡料」主要係使形成之絕緣層的熱 -12- 201030083 膨張率降低而作爲目的使用。無機塡充材具體可舉出二氧 化矽、氧化鋁、硫酸鋇、滑石、白土、雲母粉、氫氧化鋁 、氫氧化鎂、碳酸鈣、碳酸錶、氧化鎂、氮化硼、硼酸鋁 、鈦酸鋇、鈦酸緦、鈦酸鈣、鈦酸鎂、鈦酸鉍、氧化鈦、 銷酸鋇、锆酸鈣等，此些之中以無定形二氧化矽、熔融二 氧化矽、結晶二氧化矽、合成二氧化矽等之二氧化矽爲特 別適合。二氧化矽以球狀者爲佳。此些可1種或2種以上 φ 組合使用。 無機塡料之平均粒徑的上限値，由絕緣信賴性之觀點 ，以3μηι以下爲佳，以1·5μιη以下爲更佳。另一方面， 無機塡料之平均粒徑的下限値，由在將熱硬化性樹脂組成 物作爲樹脂清漆之情況，防止清漆之黏度上昇而操作性降 低之觀點，以0.05 μιη以上爲佳。無機塡料之最大粒子徑 ，由絕緣性之觀點，以5 μιη以下爲佳。 無機塡料之平均粒徑係可藉由依據Mie散射理論之雷 φ 射繞射·散射法而測定。具體而言，可藉由雷射繞射式粒 度分佈測定裝置，將無機塡充材之粒度分佈以體積基準製 作，以其之中間粒徑作爲平均粒徑而測定。測定樣品較佳 可使用將無機塡充材藉由超音波分散於水中者。雷射繞射 式粒度分佈測定裝置可使用（股）堀場製作所製LA-500 等。 將熱硬化性樹脂組成物之不揮發成分設爲100重量％ 之情況，無機塡料之含有量的上限値，由防止接著薄膜之 流動性降低而在真空層合機等之層合變得困難，接著薄膜 -13- 201030083 硬化物之柔軟性受到大損傷，而引起原本之硬化物特性降 低之觀點，以70重量％爲佳，60重量％爲更佳。另一方 面，將熱硬化性樹脂組成物之不揮發成分設爲100重量％ 之情況，無機塡料之含有量的下限値，由防止樹脂清漆之 流動性變得過高，操作性惡化且薄膜化變得困難之觀點， 以3 0重量％爲佳，2 0重量％爲更佳。 尙且，爲使耐濕性提升，無機塡充材以藉由環氧矽烷 耦合劑、胺基矽烷耦合劑、鈦酸酯系耦合劑等之表面處理 劑經表面處理者爲佳。此些可1種或2種以上組合使用。 [25°C下固形狀之環氧樹脂] 對於本發明之熱硬化性樹脂組成物，以伴隨著樹脂硬 化物之交聯密度之提升而硬化物之Tg、斷裂強度之提升 等之目的，亦可配合25 t下固形狀之環氧樹脂。25 °C下固 形狀之環氧樹脂，例如可舉出4官能萘型環氧樹脂、2官 能二環戊二烯型環氧樹脂、參酚環氧樹脂等。市售者可舉 出大日本油墨化學工業（股）製EXA4700、EXA7200、日 本化藥（股）EPPN-502H等。「25°C下固形狀之環氧樹脂 」亦可2種以上組合使用。配合25 t：下固形狀之環氧樹脂 之情況的含有量，將熱硬化性樹脂組成物之不揮發成分設 爲100重量％之情況，以30重量％以下爲佳，較佳爲20 重量％以下。若含有量過大，接著薄膜在常溫中變脆，其 操作性惡化。 -14- 201030083 [熱可塑性樹脂] 對於本發明之熱硬化性樹脂組成物，以賦予硬化後之 熱硬化性樹脂組成物適度之可撓性等爲目的，可配合熱可 塑性樹脂。作爲熱可塑性樹脂，例如可舉出苯氧樹脂、聚 乙烯縮醛樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚醚 颯樹脂、聚碾樹脂等。「熱可塑性樹脂」可2種以上組合 使用。熱硬化性樹脂組成物中之熱可塑性樹脂的含有量， φ 以〇·5〜60重量％之比進行配合爲佳，以3〜50重量％之比 進行配合爲更佳。 苯氧樹脂之市售品，例如可舉出東都化成（股）製 FX2 80、FX293、Japan Epoxy Resin (股）製 YX8100、 YL6954、YL6974 等。 聚乙烯縮醛樹脂，以聚乙烯丁醛樹脂爲佳，聚乙烯縮 醛樹脂之市售品，例如可舉出電氣化學工業（股）製、電 化丁醛 4000-2、5000-A ' 6000-C、6000-EP、積水化學工 業（股）製S-Lec BH系列、BX系列、KS系列、BL系列 、BM系列等。 聚醯亞胺之市售品，例如可舉出新日本理化（股）製 之聚醯亞胺「Rikacoat SN20」及「Rikacoat PN20」。又 ’使2官能性羥基末端聚丁二烯、二異氰酸酯化合物及四 鹼基酸酐而得之線狀聚醯亞胺（於日本特開2006-3 7083 號公報所記載者）、含有聚矽氧烷骨架之聚醯亞胺（於日 本特開2002- 12667號公報 '特開2000-3 1 93 86號公報等 所記載者）等之變性聚醯亞胺。 -15- 201030083 聚醯胺醯亞胺之市售品，例如可舉出東洋紡績（股） 製之聚醯胺醯亞胺「Vylomax HR11NN」及「Vylomax HR16NN」。又，日立化成工業（股）製之含有聚矽氧烷 骨架的聚醯胺醯亞胺「KS9100」、「KLS9300」等之變性 聚醯胺醯亞胺。 聚醚颯之市售品，例如可舉出住友化學（股）公司製 之聚醚楓「PES5003P」。 聚礙之市售品，例如可舉出 Solvay Advanced Polymers (股）公司製之聚颯「P1700」、「P3500」等。 [硬化促進劑] 對於本發明之熱硬化性樹脂組成物，以加入硬化劑使 硬化時間縮短等之目的，可使其更含有硬化促進劑。作爲 硬化促進劑，例如可舉出咪唑系化合物、有機膦系化合物 等，具體例可舉出2 -甲基咪唑、三苯基膦等。此些可i 種或2種以上組合使用。使用硬化促進劑之情況，較佳以 硬化促進劑相對於環氧樹脂的0. 1 ~3 · 0質量％之範圍內使 用。 [添加劑] 本發明之熱硬化性樹脂組成物，依據需要可更使其含 有其他之成分。其他成分，例如可舉出有機磷系難燃劑、 含有有機系氮之磷化合物、氮化合物、聚矽氧系難燃劑、 金屬氫氧化物等之難燃劑；聚矽氧粉末、耐隆粉末、氟粉 -16- 201030083 末等之有機充塡劑；〇rben、Benton等之增黏劑；聚矽氧 系、氟系等之高分子系消泡劑或調平劑；咪唑系、噻唑系 、三唑系、矽烷系耦合劑等之密著性賦予劑；酞花青藍、 酞花青綠、碘綠、重氮黃、碳黑等之著色劑等。此些可1 種或2種以上組合使用。 [有機溶劑] φ 作爲調製清漆之情況的有機溶劑，例如可舉出丙酮、 甲基乙基酮、環己酮等之酮類、乙酸乙酯、乙酸丁酯、溶 纖劑乙酸酯、丙二醇單甲基醚乙酸酯、卡必醇乙酸酯等之 乙酸酯類、溶纖劑、丁基卡必醇等之卡必醇類、甲苯、茬 等之芳香族烴類、二甲基甲醯胺、二甲基乙醯胺、N-甲基 吡略啶酮等。此些可1種或2種以上組合使用。 [接著薄膜] φ 本發明之接著薄膜係由支持體層、於該支持體層上藉 由熱硬化性樹脂組成物所形成之具有黏著性的接著層所構 成。接著層亦可形成於支持體層之兩面。 支持體層可適宜使用塑膠薄膜。除塑膠薄膜以外，離 型紙或銅箔、鋁箔等之金屬箔等也可作爲支持體層使用。 塑膠薄膜，可舉出聚對酞酸乙二酯（以下有略稱爲「PET 」）、聚萘二甲酸乙二酯等之聚酯、聚碳酸酯、丙烯、環 狀聚烯烴' 三乙醯纖維素、聚醚硫化物、聚醚酮、聚醯亞 胺等。其中，以聚對酞酸乙二酯薄膜、聚萘二甲酸乙二酯 -17- 201030083 薄膜爲佳’特別係以便宜之聚對酞酸乙二酯薄膜爲佳。於 支持體中’特別係使用塑膠薄膜之情況，爲了可由熱硬化 性樹脂組成物之硬化物層剝離，以使用熱硬化性樹脂組成 物層之被形成面經離型處理而具有離型層之支持體爲佳。 金屬箔雖也可藉由蝕刻溶液進行去除，將塑膠薄膜作爲支 持體而使熱硬化性樹脂組成物熱硬化之情況，如無離型層 ’由硬化物將塑膠薄膜剝離則變得困難。作爲離型處理所 使用之離型劑，只要係可將硬化物由支持體剝離者則無特 別限定，例如可舉出聚矽氧系離型劑、醇酸樹脂系離型劑 等。尙，亦可使用市售之附離型層的塑膠薄膜，較佳者例 如可舉出具有將醇酸樹脂系離型劑作爲主成分之離型層的 PET 薄膜，Lintec (股）製之 SK-1、AL-5、AL-7 等。又 ，塑膠薄膜可施以拋光處理、電暈處理，亦可在該處理面 上形成離型層。並且，將銅箔作爲支持體使用之情況，可 無剝離地將該銅箔作爲導體層使用。支持體之厚度並無特 別限定，以10〜15 0μιη爲佳，較佳使用25〜5 0μιη。 熱硬化性樹脂組成物之接著層的厚度以1~200μιη爲 佳，而作爲適合薄型化之絕緣樹脂薄片，以5~100μπι之 範圍爲較佳’ 5〜40μ之範圍爲更佳，5〜30μιη之範圍爲特 佳。接著層之厚度若過薄，則有電子零件之外部端子與電 路之絕緣變得不足之傾向，又也有製造變得困難之傾向。 且’接著層之厚度若過厚，則有多層印刷電路板之薄型化 變得困難之傾向。 本發明之接著薄膜係首先將熱硬化性樹脂組成物溶解 -18- 201030083 於有機溶劑作成樹脂清漆後，將此塗佈於支持體層上’藉 由吹熱風等使溶劑乾燥，而可以既述之既定之厚度形成。 接著層之保護薄膜可防止接著層表面上之灰塵等之附 著或傷痕，且有效於提升使用絕緣樹脂薄片而製造之印刷 電路板的信賴性。在此，作爲保護薄膜可舉出聚乙烯 '聚 丙烯、聚氯乙烯等之聚烯烴、聚對酞酸乙二酯等之聚酯、 聚碳酸酯、聚醯亞胺，更且可舉出離型紙、鋁箔等。尙， Φ 保護薄膜亦可施予拋光處理、電暈處理、設置聚矽氧系離 型薄膜層等之離型處理。又，保護薄膜之厚度以作爲 1 ~ 4 0 μ m 爲佳。 [零件内藏基板之製造方法] 藉由本發明之接著薄膜製造零件内藏基板之方法，其 至少包含，（A)於接著薄膜之接著層上將電子零件固定 之步驟、（B)使該接著層熱硬化形成絕緣層之步驟。本 φ 發明之接著薄膜，其特徵爲具有可強固地進行固定零件的 黏著力。 具體而言，經過（A)於接著薄膜之接著層上將電子 零件或電子零件與電路基板予以固定之步驟、（B)將該 接著層熱硬化而形成絕緣層之步驟、（C)藉由密封用樹 脂組成物、接著薄膜或預浸體，將電子零件或電子零件與 電路基板予以密封之步驟，而製造出零件内藏基板。 首先’在（A)於接著薄膜之接著層上將電子零件， 或電子零件與電路基板固定之步驟中，將電子零件及依據 -19- 201030083 需要之電路基板固定於具有黏著性之接著層表面的既定位 置。固定時之溫度的上限値，由效率良好進行作業之觀點 ，以70°C爲佳，60°C爲較佳，55°C爲更佳，50°C爲又更 佳，45°C爲特佳，40°C爲最佳。另一方面，固定時之溫度 的下限値，由使黏著性降低之觀點，以-2 0°C爲佳，-l〇°C 爲較佳，-5°C爲更佳，〇°C爲又更佳，5°C爲特佳，l〇°C爲 最佳。 其次，藉由（B)使該接著層熱硬化而形成絕緣層之 步驟，電子零件或電路基板被更強固地固定於所形成之絕 緣層上。熱硬化之硬化溫度以140〜200°C爲佳，150〜180°C 爲更佳。又，硬化時間以15分〜2小時爲佳，30〜90分之 範圍爲更佳。 其後，（C)藉由密封用樹脂組成物、接著薄膜或預 浸體將電子零件或電子零件與電路基板予以密封。密封可 採用對當業者而言公知之方法。例如可舉出，於支持體上 將已形成熱硬化性樹脂組成物層的接著薄膜藉由真空層合 機等之層合機進行層合而後熱硬化之方法，將預浸體藉由 加壓層合而層合後熱硬化之方法等。 藉由使用本發明之接著薄膜，（A)步驟、（B)步 驟、（C)步驟中，以使用可伴隨振動之運送機帶爲佳。 又，藉由使用本發明之接著薄膜，可使接著層可直接作爲 熱硬化層。且，藉由使用本發明之接著薄膜，在高位置精 度下將電子零件予以密封則成爲可能。另外，由於步驟數 也受到削減，成爲也可更便宜地製造零件内藏基板。 -20- 201030083 [實施例] 以下，展不實施例更加詳細說明本發明，而此無論在 任何意義中皆非係爲限制本發明者。尙，以下之記載中， 「份」則係指「重量份」。 (實施例1 ) φ 將雙酚型環氧樹脂（東都化成（股）製「ZX 1 05 9」 、環氧當量約1 65 ) 20重量份、環氧化聚丁二烯（Daicel 化學（股）製「PB360 0M」、不揮發份80重量％之MEK 溶液）8重量份、萘型4官能環氧樹脂（大日本油墨（股 )製「HP-4700」）14重量份、酚醛清漆型酚樹脂（大日 本油墨（股）製「LA7054」、羥基當量約125、不揮發份 60重量％之甲基乙基酮（以下略稱爲MEK)溶液）25重 量份、球形二氧化矽（（股）Admatechs製「S〇-C4」） φ 40重量份、難燃塡料（三光（股）製「HCA-HQ」）6重 量份、有機塡料（Ganz化成（股）製「AC3816N」）3重 量份、丁醛樹脂（將積水化學（股）製「BL_1」與甲苯及 甲醇以1 : 1進行稀釋而成之不揮發份爲1 5 %之溶液者） 10重量份，及以丙烯酸酯共聚樹脂作爲丙嫌酸樹脂（（ 股）Nagase ChemteX (股）製「SG_70L」、不揮發份 12.5重量％之MEK與甲苯之丨·3: 1混合溶液）〇·85重量 份，與石油腦（純正化學（股）製「IP solvent 15〇」）5 重量份及MEK21重量份一起進行混合’以局速回轉混合 201030083 機均句分散，製成熱硬化性樹脂組成物清漆（樹脂組成物 (不揮發份）中之液狀環氧樹脂2 5重量％、酚系硬化劑 14.2重量％、丙烯酸樹脂0.10重量％)。其次，將樹脂組 成物清漆在經離型處理之聚對酞酸乙二酯薄膜（厚度 38μιη) ( Lintec (股）製 AL-5 )(以下，略稱爲 3 8μηι 離 型PET )上，以刮條塗佈機進行均勻塗佈使其乾燥後之樹 脂組成物層（接著層）之厚度成爲40 μπι，在65〜120 °C ( 平均100°C )下乾燥1〇分鐘（樹脂組成物層中之殘留溶劑 量：約1重量％)。在乾燥後之樹脂組成物層表面上貼合 經離型處理之聚酞酸乙二酯薄膜（厚度25μιη ) ( Lintec (股）製AL-5)(以下，略稱爲25μιη離型PET)，製成 薄片狀之具有3層構造的接著薄膜。 (實施例2) 除了將實施例1之雙酚型環氧樹脂（東都化成（股） 製「ZX1 059」、環氧當量約165)變更爲21重量份，丙 烯酸酯共聚樹脂（Nagase ChemteX (股）製「SG-70L」 、不揮發份12.5重量％之MEK與甲苯之1.3: 1混合溶液 )變更爲17.2重量份（樹脂組成物（不揮發份）中之液 狀環氧樹脂25.0重量％、酚系硬化劑13.9重量％、丙烯酸 樹脂2重量％ )以外，其他藉由與實施例1相同之方法得 到接著薄膜。 (實施例3 ) -22- 201030083 除了將實施例1之雙酚型環氧樹脂（東都化成（股） 製「ZX1059」、環氧當量約165)變更爲22重量份’萘 型4官能環氧樹脂（大日本油墨（股）製「HP·4700」） 變更爲13重量份，更將丙烯酸酯共聚樹脂（Nagase ChemteX (股）製「SG-70L」、不揮發份12.5重量％之 MEK與甲苯之I.3: 1混合溶液）變更爲44.5重量份（樹 脂組成物（不揮發份）中之液狀環氧樹脂2 5 . 〇重量％、酚 φ 系硬化劑1 3.5重量％、丙烯酸樹脂5重量％ )以外’其他 藉由與實施例1相同之方法得到接著薄膜。 例 施 實 除了將實施例1之雙酚型環氧樹脂（東都化成（股） 製「ZX1059」、環氧當量約165)變更爲26重量份，更 將萘型4官能環氧樹脂（大日本油墨（股）製「HP_4700 」）變更爲9重量份（樹脂組成物（不揮發份）中之液狀 φ 環氧樹脂3 0重量％、酚系硬化劑〗4 2重量％、丙烯酸樹 脂〇. 1重量％ )以外’其他藉由與實施例1相同之方法得 到接著薄膜。 (實施例5) 除了將實施例1之雙酚型環氧樹脂（東都化成（股） 製「ZX1 059」、環氧當量約ι65)變更爲26重量份，萘 型4官能環氧樹脂（大日本油墨（股）製「hP_47〇〇j ) 變更爲8重量份’更將丙烯酸酯共樹脂（Nagase -23- 201030083[Technical Field] The present invention relates to a thermosetting resin composition useful for the production of a component-embedded substrate, and an adhesive film having an adhesive layer using the thermosetting resin composition. And a method of manufacturing a substrate in which the component of the adhesive film is used. @ [Prior Art] In printed circuit boards, high density is required for thinness and thinning. In the built-in substrate of the part, the embedded part becomes smaller, and the high positional accuracy at the time of embedding is necessary. Further, it is necessary to reduce the size of the entire substrate, and it is necessary to have a high insulating property between the embedded component and the circuit around the component. As a method of manufacturing a component-embedded substrate, a method of temporarily fixing a component by a sheet agent and a sheet of an adhesive is disclosed, and φ is used to seal the component and then removing the sheet (Patent Document 1) ), but did not reveal the specific composition. Moreover, the number of steps is increased by the necessity of removing the adhesive after the parts are sealed. Further, there is disclosed a method in which a part is pseudo-fixed by an adhesive material and the part is sealed with a resin on the actual mounting surface of the electronic component of the core substrate (Patent Document 2). As the adhesive material, it is preferable to use a material which is electrically insulating and further heated, and which evaporates or becomes a gas, and a specific example of the polymer to be used may be an acrylic resin, a polyester resin or a maleic oleoresin. , a polybutadiene resin, an epoxy resin, or the like, or a mixture of any combination thereof. -5-201030083 The resin to which the rosin, lanthanide, petroleum resin or the like which imparts adhesion to the polymer resin is added may be added as needed. However, it does not reveal the specific composition of the adhesive. Further, the adhesive layer is a method in which the adhesive layer is fixed by a resin on the entire insulating substrate, and the component is sealed with a resin (Patent Document 3). Examples of the adhesive layer include an epoxy resin system, a polyurethane film type, a reactive acrylic type, an ultraviolet curing type, and a polyoxymethylene type. Examples of the adhesive layer include an epoxy resin system, a polyfluorene oxide system, and the like. A curing agent such as a phenol resin, an organic acid anhydride, an amine or a curing accelerator is used. Next, a method for hardening a part, heating it at a hardening temperature, or hardening it by irradiation with ultraviolet rays or the like is disclosed. However, it does not reveal the specific composition of the subsequent layers. Further, when the electronic component is fixed by thermal curing of the adhesive layer, there is a problem that the accuracy of the fixing position of the component is lowered due to the melting of the adhesive layer. And there is a problem that the step of hardening by ultraviolet rays is a remedy. [Patent Document 1] JP-A-2004-296562 (Patent Document 3) JP-A-2007-42829 (Summary of the Invention) [Problems to be Solved by the Invention] An object of the present invention is to provide a method of fixing an electronic component to an adhesive layer by adhesiveness of a bonding layer, and thermally curing the adhesive layer, thereby achieving high fixed position accuracy and insulation reliability of the manufactured component. - 201030083 Thermosetting resin composition of the built-in substrate of the part. [Means for Solving the Problems] As a result of intensive review, the inventors of the present invention have used a specific thermosetting resin containing a liquid epoxy resin, a phenolic curing agent, an inorganic coating material, and an acrylic resin. The composition was completed to complete the present invention. That is, the present invention is intended to contain the following contents. Φ [1] A thermosetting resin composition which is a thermosetting resin composition for fixing a part of a substrate and forming an insulating layer, and is characterized in that a non-volatile content of the thermosetting resin composition is set. In the case of 100% by weight, it contains 25 to 40% by weight of a liquid epoxy resin at 25 ° C, 丙烯酸1 to 5% by weight of an acrylic resin, 5 to 30% by weight of a phenolic curing agent, and 20% by weight of an inorganic coating. ~70% by weight. [2] The thermosetting resin composition according to the above-mentioned item, wherein the acrylic resin is an acrylate copolymer. Φ [3] The thermosetting resin composition according to the above [2], wherein the acrylic resin is an acrylate copolymer containing methyl acrylate, butyl acrylate or acrylonitrile. [4] The thermosetting resin composition according to the above [1] to [3], wherein the acrylic resin contains one or more selected from the group consisting of an epoxy group, a hydroxyl group, and a carboxyl group. [5] The above-mentioned [U~[4] (C-described thermosetting resin composition, wherein the acrylic resin contains a hydroxyl group and a carboxyl group. [6] A film which is characterized in that it has a support on the surface of 201030083 The adhesive layer formed of the thermosetting resin composition described in [1] to [5] is a film for fixing a component of a component-embedded substrate and forming an insulating layer. [7] As described in the above [6] And a film having a thickness of 5 to ΙΟΟμιη [8], wherein the support film is a plastic film, [9] as described in [6] to [8] above. The film according to any one of the preceding claims, wherein the surface of the support layer on the side of the support layer is a release type process. [10] A method for manufacturing a built-in component substrate, characterized by comprising [1]~[9] The step of fixing the electronic component on the adhesive layer of the adhesive film and the step of thermally curing the adhesive layer to form the insulating layer, according to the present invention, Specific thermosetting properties of phenolic hardeners, inorganic pigments and acrylic resins The fat composition can provide a high-fixing position accuracy and insulation reliability of the manufactured component when the electronic component is fixed to the adhesive layer by the adhesiveness of the adhesive layer and the adhesive layer is thermally cured. [The embodiment of the present invention] [Liquid epoxy resin at 25 ° C] -8 - 201030083 In the present invention, "liquid epoxy resin at 25 ° C", mainly At the same time, the heat resistance and insulation of the cured product are improved, and the adhesion to the thermosetting resin composition is imparted. As a liquid epoxy resin at 25 ° C, specifically, a bisphenol a type epoxy resin or a bisphenol F type Epoxy resin, novolak type epoxy resin, naphthalene type epoxy resin, tertiary butyl catechol type epoxy resin, epoxy resin having butadiene structure, aliphatic glycidyl acid, alcohol The epoxy propyl etherate of the above-mentioned epoxy resin and the hydrogenated product of the epoxy resin, etc. These φ may be used singly or in combination of two or more. Among these, 'heat resistance and insulation reliability' Bisphenol A type epoxy resin, naphthol type epoxy tree A naphthalene type epoxy resin, an aliphatic epoxypropyl ether, and an epoxy resin having a butadiene structure are preferable. Specific examples of the epoxy resin include liquid bisphenol A type epoxy resin (Japan Epoxy) Resin (Epikote 828EL), liquid bisphenol F epoxy resin (Epikote 807 made by Japan Epoxy Resin), naphthalene type 2-functional epoxy resin (Daily Ink Chemical Industry Co., Ltd.) "φ HP4032", "HP4032D"), aliphatic glycidyl ether ("ZX-1658" manufactured by Tohto Kasei Co., Ltd.), epoxy resin with butadiene structure (Daicel Chemical Industry Co., Ltd.) "PB-3600") and so on. "Liquid epoxy resin at 25 ° C" may be used in combination of two or more kinds. When the non-volatile content of the thermosetting resin composition is 100% by weight, the upper limit of the content of the liquid epoxy resin at 25 ° C is deteriorated by preventing the adhesion from being increased, and the peeling property of the cover film is deteriorated. Further, from the viewpoint of easily causing positional deviation of the component when the film is cured, it is preferably 40% by weight, more preferably 35% by weight. On the other hand, when the non-volatile content of the thermosetting resin composition -9 · 201030083 is 100% by weight, the lower limit of the content of the liquid epoxy resin at 25 ° C is prevented. It is difficult to fix it to the viewpoint of the film, and it is more preferable that it is 30% by weight, preferably 30% by weight. [Acrylic resin] The "acrylic resin" in the present invention mainly imparts adhesion to a thermosetting resin composition. The acrylic resin may, for example, be polyacrylic acid, polymethacrylic acid, polyacrylate, polymethacrylate, polyacrylate copolymer or polymethacrylate copolymer. Further, the acrylic resin is preferably an acrylate copolymer having excellent adhesion, and more preferably a methyl acrylate copolymer or an ethyl acrylate copolymer. The copolymerization compound may, for example, be methyl acrylate, butyl acrylate, vinyl acetate, acrylonitrile or acrylamide. Among them, methyl acrylate, butyl acrylate or acrylonitrile is preferred. Further, the methyl acrylate copolymer or the ethyl acrylate copolymer is preferably one or more groups selected from the group consisting of an epoxy group, a hydroxyl group and a carboxyl group, and particularly preferably a hydroxyl group and/or a carboxyl group. It is used in combination of two or more kinds. When the non-volatile content of the thermosetting resin composition is 100% by weight, the upper limit 含有 of the content of the acrylic resin is improved from the viewpoint of preventing the adhesion from being increased, and the peeling property of the cover film is deteriorated, and the workability is poor. 5 wt% is preferred, and 3 wt% is more preferred. On the other hand, when the non-volatile component of the thermosetting resin composition is 100% by weight, the lower limit of the content of the acrylic resin is prevented from being fixed due to the decrease in adhesiveness. 1% by weight is preferable, and 0.5% by weight is more preferable. The upper limit of the weight average molecular weight of the 201030083 acrylic resin is difficult to produce a uniform thermosetting resin composition by preventing the solubility in a solvent and an epoxy resin from being lowered. It is preferably 1,200,000 and more preferably 900,000. On the other hand, the lower limit 重量 of the weight average molecular weight of the acrylic resin is preferably 400,000 or more, and 500,000 is more preferable from the viewpoint of preventing the adhesion of the composition from being lowered and fixing the component. That is, the weight average molecular weight in the present invention is determined by a gel permeation chromatography (GPC) method (calculated by polystyrene for φ). The weight average molecular weight obtained by the GPC method is, in particular, LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P/K-804L/K-made by Showa Denko Co., Ltd. 804L is used as a column, and chloroform or the like is used as a mobile phase, and the column temperature is measured at 40 ° C, and can be calculated using a standard curve of standard polystyrene. Specific examples of the commercially available acrylic resin include Toacron AR-601 and AR, which are 1"〇|^&(^8-1511L, S-1511X, S-1515, S-1517C East Asia Synthetic Co., Ltd.) -602, AR-603 (made by TOHPE φ) NIPOL AR-31, AR-51, AR-54 (manufactured by Nippon Co., Ltd.), Noxtite PA-301, PA-501, PA-502 ( NOK (share) company system), Ding 613 &111168111\\^-022, rating 8-023 '8〇-51'3〇-70L, SG-80 (made by Nagase ChemteX Co., Ltd.), KH-LT, KH-CT (manufactured by Hitachi Chemical Co., Ltd.). Two or more types of "acrylic resin" can be used in combination. [Phenolic curing agent] The "phenolic curing agent" in the present invention is mainly used as a hardening agent for epoxy resins. The phenolic curing agent is not particularly limited as long as it can be used as a curing agent for an epoxy resin having a phenolic hydroxyl group. In general, a phenol compound having two or more phenolic hydroxyl groups in the molecule is used, and specific examples thereof include a phenol novolak resin and a cresol novolak resin. For example, MEH-7700, MEH-7810, MEH-785 1 (made by Megumi Kasei Co., Ltd.), NHN, CBN, GPH (made by Nippon Kayaku Co., Ltd.), SN170, may be mentioned. , SN180, SN190, SN475, SN485, SN495, SN3 75, SN3 95 (Dongdu Chemical Co., Ltd.), TD2090 ·, TD2093, KA1160, KA1163, LA7052, LA7054, LA3018, LA1356C Otsuka Ink Chemical Industry Co., Ltd. System) and so on. The "phenolic curing agent" may be used in combination of two or more kinds. When the non-volatile content of the thermosetting resin composition is 100% by weight, the upper limit of the content of the phenol-based curing agent is such that the adhesion is lowered or the curing agent component is prevented from becoming excessive, thereby causing heat resistance and insulation. The viewpoint of reducing the important characteristics of the insulating material is preferably 30% by weight, more preferably 25% by weight, still more preferably 20% by weight, and particularly preferably 15% by weight. On the other hand, when the non-volatile content of the thermosetting resin composition is 100% by weight, the lower limit of the content of the phenolic curing agent is less, and the hardening agent is prevented from becoming too small, and the curing of the resin becomes In addition to the fact that it is very slow, it is preferable that 5% by weight is preferable, and 1 〇% by weight is more preferable from the viewpoint of preventing deterioration of important characteristics of the insulating material such as heat resistance and insulation. [Inorganic Bismuth] The "inorganic coating" in the present invention is mainly used for the purpose of lowering the expansion ratio of heat -12-201030083 of the formed insulating layer. Specific examples of the inorganic cerium filling material include cerium oxide, aluminum oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, carbonic acid, magnesium oxide, boron nitride, aluminum borate, titanium. Barium strontium, barium titanate, calcium titanate, magnesium titanate, barium titanate, titanium oxide, barium strontium hydride, calcium zirconate, etc., among which amorphous cerium oxide, molten cerium oxide, crystalline dioxide Cerium oxide such as cerium or synthetic cerium oxide is particularly suitable. It is preferred that the cerium oxide is spherical. These may be used in combination of one type or two or more types of φ. The upper limit 平均 of the average particle diameter of the inorganic cerium is preferably 3 μm or less from the viewpoint of insulation reliability, and more preferably 1. 5 μm or less. On the other hand, the lower limit of the average particle diameter of the inorganic binder is preferably 0.05 μm or more from the viewpoint of preventing the viscosity of the varnish from increasing and reducing the workability when the thermosetting resin composition is used as the resin varnish. The maximum particle diameter of the inorganic tantalum is preferably 5 μm or less from the viewpoint of insulation. The average particle size of the inorganic tantalum can be determined by the Ray φ diffraction and scattering method according to the Mie scattering theory. Specifically, the particle size distribution of the inorganic cerium material can be measured on a volume basis by a laser diffraction type particle size distribution measuring apparatus, and the intermediate particle diameter can be measured as an average particle diameter. It is preferable to use a sample in which the inorganic cerium is dispersed in the water by ultrasonic waves. For the laser diffraction type particle size distribution measuring apparatus, the LA-500 manufactured by Horiba Ltd. can be used. When the non-volatile content of the thermosetting resin composition is 100% by weight, the upper limit of the content of the inorganic binder is difficult to prevent lamination of the film by a vacuum laminator or the like by preventing the fluidity of the film from being lowered. Then, from the viewpoint that the softness of the cured product is greatly impaired, and the original hardened property is lowered, 70% by weight is preferable, and 60% by weight is more preferable. On the other hand, when the non-volatile content of the thermosetting resin composition is 100% by weight, the lower limit of the content of the inorganic coating material is too high, and the fluidity of the resin varnish is prevented from being excessively high, and the workability is deteriorated and the film is deteriorated. The viewpoint of becoming difficult is preferably 30% by weight, and more preferably 20% by weight. Further, in order to improve the moisture resistance, the inorganic ruthenium is preferably subjected to surface treatment by a surface treatment agent such as an epoxy decane coupling agent, an amino decane coupling agent or a titanate coupling agent. These may be used alone or in combination of two or more. [Embedded Epoxy Resin at 25 ° C] The thermosetting resin composition of the present invention is also used for the purpose of improving the Tg of the cured product and the breaking strength with an increase in the crosslinking density of the cured resin. It can be used with epoxy resin with a solid shape of 25 t. Examples of the epoxy resin having a solid shape at 25 ° C include a tetrafunctional naphthalene type epoxy resin, a two-functional dicyclopentadiene type epoxy resin, and a phenol epoxy resin. Commercially available persons include EXA4700, EXA7200, and Japan Chemicals Co., Ltd. EPPN-502H manufactured by Dainippon Ink Chemical Industry Co., Ltd. "Epoxy resin having a solid shape at 25 ° C" may be used in combination of two or more kinds. When the content of the epoxy resin in the form of a lower solidification is 25 t, the non-volatile content of the thermosetting resin composition is 100% by weight, preferably 30% by weight or less, preferably 20% by weight. the following. If the content is too large, then the film becomes brittle at normal temperature, and its workability is deteriorated. -14-201030083 [Thermoplastic resin] The thermosetting resin composition of the present invention can be blended with a thermoplastic resin for the purpose of imparting appropriate flexibility to the thermosetting resin composition after curing. Examples of the thermoplastic resin include a phenoxy resin, a polyvinyl acetal resin, a polyimide resin, a polyamidoximine resin, a polyether oxime resin, and a polydastic resin. "The thermoplastic resin" can be used in combination of two or more kinds. The content of the thermoplastic resin in the thermosetting resin composition is preferably φ at a ratio of 5% to 60% by weight, more preferably 3 to 50% by weight. Examples of commercially available phenoxy resins include FX2 80 manufactured by Tohto Kasei Co., Ltd., FX293, and YX8100, YL6954, and YL6974 manufactured by Japan Epoxy Resin Co., Ltd. The polyvinyl acetal resin is preferably a polyvinyl butyral resin, and a commercially available product of a polyvinyl acetal resin, for example, an electrochemistry industry, a butadialdehyde 4000-2, a 5000-A '6000- C, 6000-EP, Sekisui Chemical Industry Co., Ltd. S-Lec BH series, BX series, KS series, BL series, BM series, etc. As a commercial product of the polyimine, for example, Rikacoat SN20 and Rikacoat PN20 manufactured by Nippon Chemical and Chemical Co., Ltd. can be cited. Further, a linear polyimine obtained by using a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (described in JP-A-2006-3 7083) contains polyfluorene oxide. A polyacrylonitrile of a polyalkylene imine, such as those described in JP-A-2002- 12667 (JP-A-2000-3 1 93 86, etc.). -15- 201030083 For the commercial products of polyamidoximine, for example, Polyamide imidate "Vylomax HR11NN" and "Vylomax HR16NN" manufactured by Toyobo Co., Ltd. are mentioned. In addition, the polyacrylamide imines such as polyacrylamide skeletons "KS9100" and "KLS9300", which are manufactured by Hitachi Chemical Co., Ltd., are polyamines. As a commercial product of the polyether oxime, for example, polyether maple "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. can be cited. For example, the "P1700" and "P3500" manufactured by Solvay Advanced Polymers Co., Ltd. may be mentioned. [Curing accelerator] The thermosetting resin composition of the present invention may further contain a curing accelerator for the purpose of shortening the curing time by adding a curing agent. Examples of the curing accelerator include an imidazole compound and an organic phosphine compound. Specific examples thereof include 2-methylimidazole and triphenylphosphine. These may be used in combination of two or more kinds. In the case of using a hardening accelerator, it is preferably used in the range of 0.1 to 3.0% by mass based on the epoxy resin. [Additive] The thermosetting resin composition of the present invention may further contain other components as needed. Examples of the other components include an organophosphorus-based flame retardant, a phosphorus compound containing an organic nitrogen, a nitrogen compound, a polyoxygenated flame retardant, and a metal hydroxide; and a polyfluorene oxide powder and an anthracene Powder, fluorine powder-16- 201030083 The last organic filler; 增rben, Benton and other tackifiers; polymerized defoamers or levelers for polyoxane, fluorine, etc.; imidazole, thiazole A tackifier such as a triazole system or a decane-based coupling agent; a coloring agent such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, or carbon black. These may be used alone or in combination of two or more. [Organic solvent] φ The organic solvent in the case of preparing a varnish may, for example, be a ketone such as acetone, methyl ethyl ketone or cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate or propylene glycol. Acetate such as monomethyl ether acetate or carbitol acetate, cellosolve, carbitol such as butyl carbitol, aromatic hydrocarbon such as toluene or hydrazine, and dimethyl group Indoleamine, dimethylacetamide, N-methylpyridinone, and the like. These may be used alone or in combination of two or more. [Continuous film] φ The adhesive film of the present invention is composed of a support layer and an adhesive adhesive layer formed of a thermosetting resin composition on the support layer. Subsequent layers may also be formed on both sides of the support layer. A plastic film can be suitably used for the support layer. In addition to plastic film, metal foil such as release paper or copper foil or aluminum foil can also be used as a support layer. Examples of the plastic film include polyesters of polyethylene terephthalate (hereinafter abbreviated as "PET"), polyethylene naphthalate, polycarbonate, propylene, and cyclic polyolefins. Cellulose, polyether sulfide, polyether ketone, polyimine, and the like. Among them, polyethylene terephthalate film and polyethylene naphthalate -17-201030083 film are preferred, especially in the case of inexpensive polyethylene terephthalate film. In the case where the plastic film is used in the support, in order to be peeled off from the cured layer of the thermosetting resin composition, the formed surface of the thermosetting resin composition layer is subjected to release treatment to have a release layer. The support is better. The metal foil may be removed by an etching solution, and the plastic film may be used as a support to thermally cure the thermosetting resin composition. If the release layer is not peeled off, it is difficult to peel off the plastic film. The release agent to be used for the release treatment is not particularly limited as long as the cured product can be peeled off from the support, and examples thereof include a polyfluorene-based release agent and an alkyd-based release agent.塑胶, a commercially available release film of a release layer may be used. For example, a PET film having a release layer containing an alkyd resin release agent as a main component, and a SK made by Lintec Co., Ltd. may be used. -1, AL-5, AL-7, etc. Further, the plastic film may be subjected to a buffing treatment or a corona treatment, and a release layer may be formed on the treated surface. Further, when the copper foil is used as a support, the copper foil can be used as a conductor layer without peeling. The thickness of the support is not particularly limited, and is preferably 10 to 15 μm, and preferably 25 to 50 μm. The thickness of the adhesive layer of the thermosetting resin composition is preferably from 1 to 200 μm, and the insulating resin sheet suitable for thinning is preferably in the range of 5 to 100 μm, preferably in the range of 5 to 40 μ, preferably 5 to 30 μm. The range is particularly good. If the thickness of the layer is too thin, the insulation between the external terminals of the electronic component and the circuit tends to be insufficient, and the manufacturing tends to be difficult. Further, if the thickness of the subsequent layer is too thick, the thickness of the multilayer printed wiring board tends to be thin. In the adhesive film of the present invention, the thermosetting resin composition is first dissolved in an organic solvent to form a resin varnish, and then applied to the support layer. The solvent is dried by blowing hot air or the like. The established thickness is formed. The protective film of the next layer can prevent adhesion or scratches of dust or the like on the surface of the adhesive layer, and is effective for improving the reliability of a printed circuit board manufactured using the insulating resin sheet. Here, examples of the protective film include a polyolefin such as polyethylene 'polypropylene or polyvinyl chloride, a polyester such as polyethylene terephthalate, a polycarbonate, or a polyimide, and more specifically Type paper, aluminum foil, etc.尙, Φ The protective film can also be subjected to a polishing treatment, a corona treatment, a release treatment of a polyfluorinated release film layer, and the like. Further, the thickness of the protective film is preferably 1 to 40 μm. [Manufacturing Method of Part-Containing Substrate] A method of manufacturing a component-embedded substrate by the adhesive film of the present invention, comprising at least (A) a step of fixing an electronic component on a subsequent layer of the film, and (B) making the subsequent step The step of thermally hardening the layer to form an insulating layer. The succeeding film of the invention of φ is characterized in that it has an adhesive force capable of firmly fixing a component. Specifically, (A) a step of fixing an electronic component or an electronic component to a circuit board on a subsequent layer of the film, (B) a step of thermally curing the adhesive layer to form an insulating layer, and (C) The resin composition for sealing, the film or the prepreg, and the step of sealing the electronic component or the electronic component and the circuit board to produce the component-embedded substrate. First, in the step of (A) fixing the electronic component or the electronic component to the circuit substrate on the subsequent layer of the film, the electronic component and the circuit substrate required according to -19-201030083 are fixed on the adhesive adhesive layer surface. The established location. The upper limit of the temperature at the time of fixing is preferably 70 ° C, 60 ° C is preferred, 55 ° C is better, 50 ° C is better, 45 ° C is special. Good, 40 ° C is the best. On the other hand, the lower limit 温度 of the temperature at the time of fixing is preferably -2 0 ° C from the viewpoint of lowering the adhesion, - l 〇 ° C is preferable, -5 ° C is more preferable, 〇 ° C is Even better, 5 ° C is particularly good, l 〇 ° C is the best. Next, the step of forming the insulating layer by (B) thermally curing the adhesive layer, the electronic component or the circuit substrate is more firmly fixed to the formed insulating layer. The hardening temperature of the heat hardening is preferably 140 to 200 ° C, and more preferably 150 to 180 ° C. Further, the hardening time is preferably 15 minutes to 2 hours, and the range of 30 to 90 minutes is more preferable. Thereafter, (C) the electronic component or the electronic component is sealed to the circuit board by the resin composition for sealing, the film or the prepreg. The seal can be carried out by a method known to the practitioner. For example, a film obtained by laminating a film of a thermosetting resin composition layer on a support by a laminator such as a vacuum laminator and then thermally hardening may be used to pressurize the prepreg by pressurization. A method of laminating and laminating and then thermally hardening. By using the adhesive film of the present invention, in the steps (A), (B), and (C), it is preferred to use a conveyor belt that can accompany vibration. Further, by using the adhesive film of the present invention, the adhesive layer can be directly used as the heat hardened layer. Moreover, by using the adhesive film of the present invention, it is possible to seal the electronic component at a high positional accuracy. Further, since the number of steps is also reduced, it is also possible to manufacture the component built-in substrate more inexpensively. -20- 201030083 [Examples] Hereinafter, the present invention will be described in more detail with reference to the accompanying Examples, which are not intended to limit the invention.尙 In the following description, “parts” means “parts by weight”. (Example 1) φ bisphenol type epoxy resin ("ZX 1 05 9" manufactured by Tohto Kasei Co., Ltd., epoxy equivalent: about 1 65) 20 parts by weight, epoxidized polybutadiene (Daicel Chemical Co., Ltd.) 8 parts by weight of "PB360 0M" and a non-volatile 80% by weight MEK solution), 14 parts by weight of a naphthalene type tetrafunctional epoxy resin ("HP-4700" manufactured by Dainippon Ink Co., Ltd.), and a novolak type phenol resin (LA7054 manufactured by Dainippon Ink Co., Ltd.), a methyl ether ketone (hereinafter abbreviated as MEK) solution having a hydroxyl equivalent of about 125 and a nonvolatile content of 60% by weight, 25 parts by weight, spherical cerium oxide ((share) "S〇-C4" manufactured by Admatechs) φ 40 parts by weight, 6 parts by weight of non-flammable materials ("HCA-HQ" manufactured by Sanko Co., Ltd.), and organic materials ("AC3816N" manufactured by Ganz Chemical Co., Ltd.) 3 weight And a butyral resin (a solution of "BL_1" made from Sekisui Chemical Co., Ltd. and a toluene and methanol diluted to 1:1 with a nonvolatile content of 15%) 10 parts by weight, and an acrylate copolymer resin As a acrylic acid resin ("Negaase ChemteX" ("SG_70L"), non-volatile content of 12.5% by weight of MEK and Benzene·3:1 mixed solution) 〇·85 parts by weight, mixed with 5 parts by weight of petroleum brain ("IP solvent 15" manufactured by Pure Chemical Co., Ltd.) and MEK 21 parts by weight 'mixed at a local speed of 201030083 The machine was dispersed to form a thermosetting resin composition varnish (25 wt% of a liquid epoxy resin in a resin composition (nonvolatile matter), 14.2 wt% of a phenol type hardener, and 0.10 wt% of an acrylic resin). Next, the resin composition varnish was applied to a release-treated polyethylene terephthalate film (thickness 38 μm) (AL-5 manufactured by Lintec Co., Ltd.) (hereinafter, abbreviated as 3 8 μηι release PET). The thickness of the resin composition layer (adhesive layer) after uniform coating by the bar coater is 40 μm, and drying at 65 to 120 ° C (average 100 ° C) for 1 minute (resin composition layer) Amount of residual solvent: about 1% by weight). On the surface of the dried resin composition layer, a release-treated polyethylene phthalate film (thickness 25 μm) (AL-5 manufactured by Lintec Co., Ltd.) (hereinafter, abbreviated as 25 μm release PET) was attached. A sheet-like adhesive film having a three-layer structure was formed. (Example 2) An acrylate copolymer resin (Nagase ChemteX) was prepared by changing the bisphenol type epoxy resin ("ZX1 059" manufactured by Tosho Kasei Co., Ltd., epoxy equivalent: 165) of Example 1 to 21 parts by weight. ) "SG-70L", a non-volatile content of 12.5% by weight of a 1.3:1 mixed solution of MEK and toluene) was changed to 17.2 parts by weight (25.0% by weight of the liquid epoxy resin in the resin composition (nonvolatile matter), An adhesive film was obtained by the same method as in Example 1 except that the phenolic curing agent was 13.9% by weight and the acrylic resin was 2% by weight. (Example 3) -22-201030083 In addition to changing the bisphenol type epoxy resin ("ZX1059" manufactured by Tosho Kasei Co., Ltd., epoxy equivalent: 165) of Example 1 to 22 parts by weight of 'naphthalene type 4-functional epoxy resin Resin ("HP·4700" manufactured by Dainippon Ink Co., Ltd.) was changed to 13 parts by weight, and acrylate copolymer resin ("SG-70L" manufactured by Nagase ChemteX Co., Ltd., MEK and toluene having a nonvolatile content of 12.5% by weight) I.3: 1 mixed solution) was changed to 44.5 parts by weight (liquid epoxy resin in the resin composition (nonvolatile matter) 2 5 % by weight, phenol φ-based hardener 1 3.5% by weight, acrylic resin 5 The adhesive film was obtained by the same method as in Example 1 except for % by weight. In addition, the bisphenol type epoxy resin (ZX1059, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent: 165) of Example 1 was changed to 26 parts by weight, and a naphthalene type 4-functional epoxy resin (large Japan) was added. Ink (manufactured by the ink) "HP_4700") was changed to 9 parts by weight (liquid φ epoxy resin in the resin composition (nonvolatile matter) 30% by weight, phenolic curing agent 242% by weight, acrylic resin 〇. The film was obtained by the same method as in Example 1 except for 1% by weight. (Example 5) A naphthalene type 4-functional epoxy resin (large) was prepared by changing the bisphenol type epoxy resin ("ZX1 059" manufactured by Tosho Kasei Co., Ltd., epoxy equivalent: ι65) of Example 1 to 26 parts by weight. Japanese ink (share) system "hP_47〇〇j" changed to 8 parts by weight 'more acrylate common resin (Nagase -23- 201030083
ChemteX (股）製「SG-70L」、不揮發份 12.5重量％之 MEK與甲苯之1.3: 1混合溶液）變更爲17.3重量份（樹 脂組成物（不揮發份）中之液狀環氧樹脂3〇重量％、酚 系硬化劑1 3.9重量％、丙烯酸樹脂2重量％ )以外，其他 藉由與實施例1相同之方法得到接著薄膜。 (實施例6 ) 除了將實施例1之雙酚型環氧樹脂（東都化成（股） 製「ZX 1 059」、環氧當量約1 65 )變更爲27重量份，萘 型4官能環氧樹脂（大日本油墨（股）製「HP-4700」） 變更爲 7重量份，更將丙烯酸酯共聚樹脂（Nagase ChemteX (股）製「SG-70L」、不揮發份12.5重量％之 MEK與甲苯之1.3: 1混合溶液）變更44.5重量份（樹脂 組成物（不揮發份）中之液狀環氧樹脂30重量％、酚系 硬化劑1 3.5重量％、丙烯酸樹脂5重量％ )以外’其他藉 由與實施例1相同之方法得到接著薄膜。 (實施例7) 除了將實施例1之雙酚型環氧樹脂（東都化成（股） 製「ZX1 059」、環氧當量約165)變更爲35重量份’去 除萘型4官能環氧樹脂（大日本油墨（股）製「HP_4700 」）’將球形二氧化砍（（股）Admatechs製「s〇-C4」 )變更爲 37重量份’丙烯酸酯共聚樹脂（NaSase"SG-70L" manufactured by ChemteX Co., Ltd., a 1.3:1 mixed solution of non-volatiles of 12.5% by weight of MEK and toluene) was changed to 17.3 parts by weight (liquid epoxy resin 3 in a resin composition (nonvolatile matter)) An adhesive film was obtained by the same method as in Example 1 except that the weight % of hydrazine, the phenolic curing agent 1 3.9% by weight, and the acrylic resin 2% by weight. (Example 6) A naphthalene type 4-functional epoxy resin was changed to 27 parts by weight, except that the bisphenol type epoxy resin ("ZX 1 059" manufactured by Tohto Kasei Co., Ltd., epoxy equivalent: about 1 65) was changed to 27 parts by weight. ("HP-4700" manufactured by Dainippon Ink Co., Ltd.) was changed to 7 parts by weight, and acrylate copolymer resin ("SG-70L" manufactured by Nagase ChemteX Co., Ltd., MEK and toluene having a nonvolatile content of 12.5% by weight) 1.3: 1 mixed solution) 44.5 parts by weight (30% by weight of the liquid epoxy resin in the resin composition (nonvolatile matter), 3.5% by weight of the phenolic curing agent, and 5% by weight of the acrylic resin) An adhesive film was obtained in the same manner as in Example 1. (Example 7) The bisphenol type epoxy resin ("ZX1 059" manufactured by Tohto Kasei Co., Ltd., epoxy equivalent: 165) of Example 1 was changed to 35 parts by weight of 'removing naphthalene type tetrafunctional epoxy resin ( "Japan Japan Ink (")" "HP_4700") 'Changes the spherical dioxide ("A〇-C4" made by Admatechs) to 37 parts by weight of 'Acrylate Copolymer Resin (NaSase)
ChemteX (股）製「SG-70L」、不揮發份12·5重量％之 •24- 201030083 MEK與甲苯之1·3: 1混合溶液）變更爲0.83重量份，更 將ΜΕΚ變更爲5量份（樹脂組成物（不揮發份）中之液 狀環氧樹脂39·8重量％、酚系硬化劑14.5重量％、丙烯酸 樹脂〇. 1重量％)以外，其他藉由與實施例1相同之方法 得到接著薄膜。 (實施例8 ) φ 除了將實施例1之雙酚型環氧樹脂（東都化成（股） 製「ΖΧ1 05 9」、環氧當量約165 )變更爲35重量份，去 除萘型4官能環氧樹脂（大日本油墨（股）製「HP-4 7 00 」），將球形二氧化矽（（股）Admatechs製「SO-C4」 )變更 35重量份，更將丙烯酸酯共聚樹脂（Nagase ChemteX (股）製「SG-70L」、不揮發份12.5重量％之 Μ EK與甲苯之1.3: 1混合溶液）變更爲16·4重量份，更 將ΜΕΚ變更爲5量份（樹脂組成物（不揮發份）中之液 φ 狀環氧樹脂3 9.8重量％、酚系硬化劑1 4.6重量％、丙烯酸 樹脂1.99重量％ )以外，其他藉由與實施例1相同之方法 得到接著薄膜。 (實施例9) 除了將實施例1之雙酚型環氧樹脂（東都化成（股） 製「ΖΧ1059」、環氧當量約165)變更35重量份’去除 萘型4官能環氧樹脂（大日本油墨（股）製「ΗΡ_4700」 )，將球形二氧化矽（（股）Admatechs製「SO-C4」） -25- 201030083 變更爲32重量份，且將丙烯酸酯共聚樹脂（Nagase ChemteX (股）製「SG-70L」、不揮發份12.5重量％之 MEK與甲苯之1.3: 1混合溶液）變更爲41重量份，更將 MEK變更爲5量份（樹脂組成物（不揮發份）中之液狀 環氧樹脂40重量％、酚系硬化劑14.6重量％、丙烯酸樹 脂4.99重量％ )以外，其他藉由與實施例1相同之方法得 到接著薄膜。 (比較例1 ) 除了將實施例1之丙烯酸酯共聚樹脂（Nagase ChemteX (股）製「SG-70L」、不揮發份 12.5重量％之 MEK與甲苯之1.3: 1混合溶液）變更爲0.43重量份（樹 脂組成物（不揮發份）中之液狀環氧樹脂25重量％、酚 系硬化劑14.2重量％、丙烯酸樹脂〇.〇5重量％)以外，其 他藉由與實施例1相同之方法得到接著薄膜。 (比較例2) 除了將實施例1之雙酚型環氧樹脂（東都化成（股） 製「ZX1 059」、環氧當量約165)變更爲22重量份，萘 型4官能環氧樹脂（大日本油墨（股）製「HP-4700」） 變更13重量份’更將丙烯酸酯共聚樹脂（Nagase ChemteX (股）製「SG-70L」、不揮發份12.5重量％之 MEK與甲苯之1.3: 1混合溶液）變更爲53.9重量份（樹 脂組成物（不揮發份）中之液狀環氧樹脂25重量％、酚 -26- 201030083 系硬化劑1 3.4重量％、丙烯酸樹脂6重量°/β )以外’其他 藉由與實施例1相同之方法得到接著薄膜° (比較例3 ) 除了將實施例1之雙酚型環氧樹脂（東都化成（股） 製「ZX1059」、環氧當量約165)變更爲26重量份’蔡 型4官能環氧樹脂（大日本油墨（股）製「ΗΡ_47()ί)」> φ 變更爲9重量份，更將丙烯酸酯共聚樹脂（NagaSe ChemteX (股）製「SG-70L」、不揮發份12·5重量％之 MEK與甲苯之1·3: 1混合溶液）變更爲〇.43重量份（樹 脂組成物（不揮發份）中之液狀環氧樹脂30 系硬化劑14.2重量％、丙烯酸樹脂0.05重量°/°)以外’其 他藉由與實施例1相同之方法得到接著薄膜° (比較例4 ) φ 除了將實施例1之雙酚型環氧樹脂（東都化成（股） 製「ZX1 059」、環氧當量約165 )變更爲28重量份’萘 型4官能環氧樹脂（大日本油墨（股）製「HP-4700」） 變更爲7重量份，更將丙烯酸酯共聚樹脂（Nagase ChemteX (股）製「SG-70L」、不揮發份12·5重量％之 ΜEK與甲苯之1·3: 1混合溶液）變更爲54重量份（樹脂 組成物（不揮發份）中之液狀環氧樹脂30重量％ '酣系 硬化劑1 3.3重量％、丙烯酸樹脂6重量％ )以外’其他藉 由與實施例1相同之方法得到接著薄膜。 -27- 201030083 (比較例5) 除了將實施例1之雙酚型環氧樹脂（東都化成（股） 製「ZX1059」、環氧當量約165)變更爲35重量份’去 除萘型4官能環氧樹脂（大日本油墨（股）製「HP-47 00 j )，將球形二氧化矽（（股）Admatechs製「SO-C4」 )變更爲37重量份，更將丙烯酸酯共聚樹脂（NaSase ChemteX (股）製「SG-70L」、不揮發份12.5重量％之 . MEK與甲苯之1.3: 1混合溶液）變更爲〇·4重量份’更 將MEK變更5量部（樹脂組成物（不揮發份）中之液狀 環氧樹脂40重量％、酚系硬化劑14.6重量％、丙烯酸樹 脂〇. 〇 5重量％)以外，其他藉由與實施例1相同之方法得 到接著薄膜。 (比較例6) 除了將實施例1之雙酚型環氧樹脂（東都化成（股） 0 製「ZX1059」、環氧當量約165)變更爲35重量份’去 除萘型4官能環氧樹脂（大日本油墨（股）製「HP-4700 」），將球形二氧化矽（（股）Admatechs製「SO-C4」 )變更爲30重量份，且將丙烯酸酯共聚樹脂（Nagase ChemteX (股）製「SG-70L」、不揮發份12.5重量％之 MEK與甲苯之1.3: 1混合溶液）變更爲49.2重量份，更 將MEK變更爲5量份（樹脂組成物（不揮發份）中之液 狀環氧樹脂4 0重量％、酣系硬化劑1 4.6重量％、丙稀酸 -28- 201030083 樹脂6重量％ )，其他與藉由實施例1相同之方法得到接 著薄膜。 (比較例7) 除了將實施例1之雙酚型環氧樹脂（東都化成（股） 製「ZX 1059」、環氧當量約165)變更爲16重量份，萘 型4官能環氧樹脂（大日本油墨（股）製「HP-4700」） φ 變更爲 19重量份，更將丙烯酸酯共聚樹脂（Nagase"SG-70L" manufactured by ChemteX Co., Ltd., 12.5% by weight of nonvolatiles, 24-201030083, mixed solution of MEK and toluene (1:3:1) was changed to 0.83 parts by weight, and ΜΕΚ was changed to 5 parts. (The same method as in Example 1 except for the liquid epoxy resin 39.8% by weight in the resin composition (nonvolatile matter), the phenolic curing agent 14.5% by weight, and the acrylic resin 〇. 1% by weight) A follow-up film is obtained. (Example 8) φ In addition to changing the bisphenol type epoxy resin ("Dongdu Chemical Co., Ltd.", "ΖΧ1 05 9", epoxy equivalent: 165) of Example 1 to 35 parts by weight, the naphthalene type 4-functional epoxy was removed. Resin ("HP-4 7 00" made by Dainippon Ink Co., Ltd.), 35 parts by weight of spherical cerium oxide ("SO-C4" manufactured by Admatechs), and acrylate copolymer resin (Nagase ChemteX ( SG-70L, a non-volatile content of 12.5% by weight of 1.3 and a 1.3:1 mixed solution of EK and toluene) was changed to 6.4 parts by weight, and ΜΕΚ was changed to 5 parts (resin composition (non-volatile An adhesive film was obtained by the same method as in Example 1 except that the liquid φ-like epoxy resin 3 9.8 wt%, the phenol-based curing agent 1 4.6 wt%, and the acrylic resin 1.99 wt%. (Example 9) The bisphenol type epoxy resin of the first embodiment ("1059" manufactured by Tohto Kasei Co., Ltd., epoxy equivalent: 165) was changed by 35 parts by weight. 'Removing naphthalene type 4-functional epoxy resin (Great Japan) Ink (manufactured by Nagase ChemteX Co., Ltd.) was changed to 32 parts by weight of spherical cerium oxide ("SO-C4" manufactured by Admatechs) -25-201030083, and acrylate copolymer resin (Nagase ChemteX) "SG-70L", a non-volatile content of 12.5% by weight of a 1.3:1 mixed solution of MEK and toluene) was changed to 41 parts by weight, and MEK was changed to 5 parts by weight (liquid content in a resin composition (nonvolatile matter)) An adhesive film was obtained by the same method as in Example 1 except that 40% by weight of the epoxy resin, 14.6% by weight of the phenolic curing agent, and 4.99% by weight of the acrylic resin. (Comparative Example 1) The acrylate copolymer resin of Example 1 ("SG-70L" manufactured by Nagase ChemteX Co., Ltd., a 1.3:1 mixed solution of 12.5% by weight of MEK and toluene) was changed to 0.43 parts by weight. (25% by weight of the liquid epoxy resin in the resin composition (nonvolatile matter), 14.2% by weight of the phenolic curing agent, and 5% by weight of the acrylic resin), the same method as in Example 1 was obtained. Then the film. (Comparative Example 2) A naphthalene type 4-functional epoxy resin (large) was prepared by changing the bisphenol type epoxy resin ("ZX1 059" manufactured by Tosho Chemical Co., Ltd., epoxy equivalent: 165) of Example 1 to 22 parts by weight. Nippon Ink Co., Ltd. "HP-4700") 13 parts by weight of 'more acrylate copolymer resin ("SG-70L" manufactured by Nagase ChemteX Co., Ltd., 12.5% by weight of MEK and toluene 1.3: 1) The mixed solution) was changed to 53.9 parts by weight (25% by weight of the liquid epoxy resin in the resin composition (nonvolatile matter), 3.4% by weight of the phenol-26-201030083-based curing agent, and 6% by weight of the acrylic resin). In the same manner as in Example 1, the film was obtained in the same manner as in Example 1 (Comparative Example 3) except that the bisphenol type epoxy resin ("ZX1059" manufactured by Tohto Kasei Co., Ltd., epoxy equivalent: 165) of Example 1 was changed. 26 parts by weight of 'Cai-type 4-functional epoxy resin ("ΗΡ_47() ))" made by Dainippon Ink Co., Ltd.> φ was changed to 9 parts by weight, and acrylate copolymer resin (made by NagaSe ChemteX Co., Ltd.) SG-70L", non-volatile content of 12.5% by weight of MEK and toluene 1:3: 1 mixed solution And changed to 43 parts by weight (the liquid epoxy resin 30-based curing agent in the resin composition (nonvolatile matter) is 14.2% by weight, and the acrylic resin is 0.05 weight%/°), and the other is the same as in the first embodiment. The film was obtained by the method (Comparative Example 4) φ except that the bisphenol type epoxy resin ("ZX1 059" manufactured by Tosho Chemical Co., Ltd., epoxy equivalent: about 165) of Example 1 was changed to 28 parts by weight of 'naphthalene type. 4-functional epoxy resin ("HP-4700" manufactured by Dainippon Ink Co., Ltd.) was changed to 7 parts by weight, and acrylate copolymer resin ("SG-70L" manufactured by Nagase ChemteX Co., Ltd., non-volatile fraction 12·5) The weight % of 混合 EK and toluene in a 1:3:1 mixed solution) was changed to 54 parts by weight (30% by weight of liquid epoxy resin in the resin composition (nonvolatile matter) '酣-based hardener 13.3% by weight, acrylic acid An adhesive film was obtained by the same method as in Example 1 except that the resin was 6% by weight. -27-201030083 (Comparative Example 5) The bisphenol type epoxy resin (ZX1059, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent: 165) was changed to 35 parts by weight, and the naphthalene type 4-functional ring was removed. Oxygen resin ("HP-47 00 j" manufactured by Dainippon Ink Co., Ltd.), spheroidal cerium oxide ("SO-C4" manufactured by Admatechs) was changed to 37 parts by weight, and acrylate copolymer resin (NaSase ChemteX) (SG-70L), non-volatiles (12.5 wt%), MEK and toluene 1.3:1 mixed solution) changed to 〇·4 parts by weight, and MEK was changed to 5 parts (resin composition (non-volatile An adhesive film was obtained by the same method as in Example 1 except that 40% by weight of the liquid epoxy resin, 14.6% by weight of the phenolic curing agent, and 5% by weight of the acrylic resin. (Comparative Example 6) The bisphenol-type epoxy resin ("ZX1059" manufactured by Tohto Kasei Co., Ltd., epoxy equivalent: 165) of Example 1 was changed to 35 parts by weight of 'removing naphthalene type 4-functional epoxy resin ( "Nippon Ink ("H4-4") made from spherical cerium oxide ("SO-C4" manufactured by Admatechs) was changed to 30 parts by weight, and acrylate copolymer resin (Nagase ChemteX) "SG-70L", a non-volatile content of 12.5% by weight of MEK and toluene in a 1.3:1 mixed solution) was changed to 49.2 parts by weight, and MEK was changed to 5 parts by weight (liquid composition in a resin composition (nonvolatile matter)) The adhesive film was obtained in the same manner as in Example 1 except that 40% by weight of the epoxy resin, 4.6 wt% of the lanthanum-based hardener, and 6% by weight of the acrylic acid -28-201030083 resin. (Comparative Example 7) A naphthalene type 4-functional epoxy resin (large) was prepared by changing the bisphenol type epoxy resin ("ZX 1059" manufactured by Tosho Kasei Co., Ltd., epoxy equivalent: 165) of Example 1 to 16 parts by weight. Japan ink (stock) "HP-4700") φ changed to 19 parts by weight, more acrylate copolymer resin (Nagase
ChemteX (股）製「SG-7 0L」、不揮發份12.5重量。/〇之 MEK與甲苯之1.3: 1混合溶液）變更爲17.2重量份（樹 脂組成物（不揮發份）中之液狀環氧樹脂20重量％、酚 系硬化劑1 3.9重量％、丙烯酸樹脂2重量％ )以外’其他 藉由與實施例1相同之方法得到接著薄膜。 (比較例8 ) φ 除了將實施例1之雙酚型環氧樹脂（東都化成（股） 製「ZX1059」、環氧當量約165 )變更爲35重量份，去 除萘型4官能環氧樹脂（大日本油墨（股）製「HP-4 700 j )，將球形二氧化矽（（股）Admatechs製「SO-C4」 )變更爲23重量份，且將丙烯酸酯共聚樹脂（Nagase ChemteX (股）製「SG-70L」、不揮發份12.5重量。/〇之 MEK與甲苯之1.3: 1混合溶液）變更爲14.5重量份，更 將MEK變更爲5量份（樹脂組成物（不揮發份）中之液 狀環氧樹脂45重量％、酚系硬化劑16.6重量％、丙烯酸 -29- 201030083 樹脂2重量％)以外，其他藉由與實施例1相同之方法得 到接著薄膜。 使用實施例及比較例之接著薄膜進行Tg (玻璃轉移 溫度）測定、絕緣電阻値之測定、黏著（tack )力之測定 、25μηι離型PET (覆蓋薄膜）剝離性之評價、零件固定 性之評價、最大零件位置偏差量之測定。 < Tg (玻璃轉移溫度）測定> 將實施例及比較例所作成之接著薄膜由25 μπι離型 PET剝離，藉由分批式真空加壓層合機（Nichigo-Morton (股）製，「MortoN-724」），層合於 200mmx200mm 之 聚醯亞胺薄膜（宇部興産（股）製，「UPILEX5 0S」）。 30秒鐘真空吸引後使用耐壓橡膠，30秒鐘lkg/cm2之壓 力下加壓之條件中進行。將以上述所作成之樣品的3 8 μιη 離型PET剝離，放入分批熱處理機在180°C中加熱90分 鐘，使樹脂組成物層（接著層）硬化。將本硬化物之Tg 藉由熱分析裝置（Seiko Instruments (股）製、「 DMS6100」）進行測定。 <絕緣電阻値之測定> 將實施例及比較例所作成之接著薄膜之25μιη離型 PET剝離，分批式真空加壓層合機（Nichigo-Morton (股 )製、「Morton-724」）層合於 L/S= 1 5 μιη/1 5 μιη 之 TAB 帶（三井金屬（股）製、「AJ-C0002-30/40」）。層合係 201030083 以30秒鐘真空吸引後使用耐壓橡膠，30秒鐘lkg/cm2之 壓力下加壓之條件中進行。將上述所作成之樣品的3 8μιη 離型PET剝離，分批熱處理機中在180°C中加熱90分鐘 ，使樹脂組成物層（接著層）硬化》測定硬化後之樣品的 電阻値，將其作爲初期電阻値。其次，在HAST試驗機（ 楠本化成（股）製、「ETAC PM422」）中以130°C、85 重量％Rh之條件下，放置100小時，測定其後電阻値（ H A S T電阻値）。 <黏著力之測定> 將實施例及比較例所製作之接著薄膜的25 μιη離型 PET剝離’裝上裝置専用之冶具，測定樹脂組成物層（接 者層）側之黏著力。裝置係使用 Probe Tack Tester ( Tester産業（股）製，TE6002) 、¢5.05mm不鏽鋼之針 ’ 25°C、荷重lkgf/cm2、接觸速度5mm / min下將探針壓 Φ 向接著薄膜之接著層面，且保持10秒鐘。其後，以剝離 速度1mm/ min使其剝離，測定此時之荷重。進行此測定 5次’將去除最大値與最小値的3個測定値之平均値作爲 黏著力。0.25N以下則爲測定誤差内記爲ND。 < 25 μπι離型PET (覆蓋薄膜）剝離性之評價> 將實施例及比較例所製作之接著薄膜切出一約1 〇cm 棱角，將38μιη之離型PET側固定於固定台（藉由減壓可 將薄片予以固定之台）。其次，僅將室溫（25。(：）下四角 -31 - 201030083 之1處之25 μηι離型PET以手捏起，對接著薄膜以90度 之角度垂直地拉起約5cm。在25μιη離型PET與接著層之 間若剝離之情況記爲〇，在接著層與38μπι離型PET之間 若剝離，或接著薄膜在在層間中無剝離而藉由固定台剝離 之情況記爲X。 <零件固定性之評價> 由實施例及比較例所製作之接著薄膜將25 μιη離型 PET剝離，藉由分批式真空加壓層合機（Nichigo-Morton (股）製，「MortoN-724」），層合於 26mmx76mm 之載 玻片單面上。層合係在室溫（25°C )中30秒鐘真空吸引 後使用耐壓橡膠，以30秒鐘lkg/cm2之壓力加壓之條件 下進行。 將上述所作成之樣品的38μιη離型PET剝離，將 1 608晶片電容器3個以小鎳子置於接著薄膜上。其次， 以分批式真空加壓層合機（Nichigo-Morton (股）製、「 Morton-724」），30秒鐘真空吸引後使用耐壓橡膠，在 室溫（25°C )中30秒鐘lkg/cm2之壓力加壓之條件下將 電容器固定於接著薄膜上。 於接著薄膜上將已固定之電容器以小鎳子朝垂直方向 剝離，觀察接著層表面所殘留之電容器的痕跡。如圖1所 示般，配合電容器之形狀於接著層表面有痕跡者記爲〇， 只有一部分痕跡者記爲△、無痕跡之情況記爲X。 -32- 201030083 <最大零件位置偏差量之測定> 與零件固定性之評價相同之方法作成零件經固定之載 玻片，以如圖2所示之要領進行測定電容器之隨及固定後 及硬化後中之位置偏差量。 零件固定後之零件位置之測定係藉由測距機（商品名 ，MF-UD2017B (股）Mitsutoyo 製），如圖 2所示般，決 定原點A、B，測定由原點至由零件之角落（4角）的距 血離（W、X、Y、Z)。 樣品之硬化係藉由將上述樣品在分批熱處理機中使樹 脂成爲垂直般而放入，在180 °C中加熱30分鐘，而使樹脂 組成物層（接著層）硬化。 硬化後之零件位置係由硬化前所定之原點A、B與硬 化後之零件的角（4角落）測定其距離（W’、X’、Y’、Z’ )。將（|W’-W卜|Χ’_Χ|、|Υ’-Υ卜丨Z’_Z丨）作爲零件位置 偏差量，將此等4個數値之最大値作爲最大零件位置偏差 φ 量。對於在硬化中零件由接著層剝離者記爲ND。 -33- 201030083 [表i] 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 Tg(°C) 196 195 194 177 181 182 149 155 157 初期電阻値 (Ω) 1.56E+12 2.46E+12 4.64E+12 9.29E+12 7.22E+12 3.36Ε+12 2.53Ε+12 4.18Ε+12 6.07Ε+12 HAST電阻値 (Ω) 1.01E+12 2.09E+12 3.64E+12 2.17E+11 2.80E+11 3.50Ε+11 4.81Ε+11 2.89Ε+11 5.02Ε+11 黏著力 (N) 1.5 2.5 3 2.1 3 3.4 2.6 3.3 4 覆蓋薄膜 剝離性 〇 〇 〇 〇 〇 〇 〇 〇 〇 零件固定性 〇 〇 〇 〇 〇 〇 〇 〇 〇 最大零件位 置偏差量 (#m) 24 20 22 18 7 10 9 8 9 [表2] 比較例1 比較例2 比較例3 比較例4 比較例5 比較例6 比較例7 比較例8 Tg(°C) 195 197 178 177 153 159 209 153 初期電阻値 (Ω) 2.67E+12 4.32E+12 5.38E+12 7.59E+12 6.49E+12 4.44E+12 1.14E+11 8.05E+12 HAST電阻値 (Ω) 9.34E+11 8.57E+11 5.38E+12 8.94E+11 9.51E+11 4.71E+11 2.16E+10 2.20E+11 黏著力 (N) ND 4.6 1 4.7 1.6 5 ND 6.7 覆蓋薄膜剝離性 〇 X 〇 X 〇 X 〇 X 零件固定性 X 〇 Δ 〇 Δ 〇 X 〇 最大零件位 置偏差量 (Aim) 153 27 81 9 55 7 ND 16ChemteX (stock) "SG-7 0L", non-volatile 12.5 weight. /1.3:1 mixed solution of MEK and toluene) changed to 17.2 parts by weight (20% by weight of liquid epoxy resin in resin composition (nonvolatile matter), 3.9% by weight of phenolic curing agent, acrylic resin 2 The adhesive film was obtained by the same method as in Example 1 except for % by weight. (Comparative Example 8) φ The bisphenol type epoxy resin (ZX1059, manufactured by Tosho Kasei Co., Ltd., epoxy equivalent: 165) of Example 1 was changed to 35 parts by weight to remove the naphthalene type tetrafunctional epoxy resin ( "HP-4 700 j" manufactured by Dainippon Ink Co., Ltd., changed spherical cerium oxide ("SO-C4" manufactured by Admatechs) to 23 parts by weight, and acrylate copolymer resin (Nagase ChemteX (share)) "SG-70L", a nonvolatile content of 12.5 wt. / / a mixed solution of MEK and toluene of 1.3:1) was changed to 14.5 parts by weight, and MEK was changed to 5 parts by weight (resin composition (nonvolatile matter) An adhesive film was obtained by the same method as in Example 1 except that the liquid epoxy resin was 45% by weight, the phenolic curing agent was 16.6 % by weight, and the acrylic acid -29-201030083 resin was 2% by weight. The Tg (glass transition temperature) measurement, the measurement of the insulation resistance 、, the measurement of the adhesion force, the evaluation of the peeling property of the 25 μηι release type PET (cover film), and the evaluation of the component fixing property were carried out using the adhesive films of the examples and the comparative examples. Determination of the maximum part position deviation. <Tg (glass transition temperature) measurement> The film formed in the examples and the comparative examples was peeled off from 25 μm of release PET by a batch type vacuum pressure laminator (manufactured by Nichigo-Morton Co., Ltd.). "MortoN-724"), laminated to a 200mm x 200mm polyimide film ("Ubetsu Hiroshi Co., Ltd.", "UPILEX5 0S"). After vacuum suction for 30 seconds, pressure-resistant rubber was used, and the pressure was applied under a pressure of lkg/cm 2 for 30 seconds. The 38 μηη release PET of the sample prepared above was peeled off, and placed in a batch heat treatment machine at 180 ° C for 90 minutes to harden the resin composition layer (the subsequent layer). The Tg of the cured product was measured by a thermal analysis apparatus ("DMS6100", manufactured by Seiko Instruments Co., Ltd.). <Measurement of Insulation Resistance &> The 25 μιη release PET of the film obtained in the examples and the comparative examples was peeled off, and a batch type vacuum pressure laminator (manufactured by Nichigo-Morton Co., Ltd., "Morton-724") A TAB tape (manufactured by Mitsui Metals Co., Ltd., "AJ-C0002-30/40") laminated at L/S = 1 5 μιη / 1 5 μηη. Laminating system 201030083 After vacuum suction for 30 seconds, pressure rubber was used, and the pressure was applied under a pressure of 30 lkg/cm2. The sample of the above-mentioned sample was stripped of 3 8 μm of the release PET, and heated in a batch heat treatment machine at 180 ° C for 90 minutes to harden the resin composition layer (adhesive layer). The resistance 値 of the sample after hardening was measured. As the initial resistance 値. Then, it was allowed to stand at 130 ° C and 85 wt% Rh under a HAST tester (manufactured by K., Ltd., "ETAC PM422") for 100 hours, and the subsequent resistance 値 (H A S T resistance 値) was measured. <Measurement of Adhesive Strength> The 25 μm release PET of the adhesive film produced in the examples and the comparative examples was peeled off into a device for mounting the device, and the adhesive force on the resin composition layer (contact layer) side was measured. The device uses Probe Tack Tester (Tester Industry Co., Ltd., TE6002), ¢5.05mm stainless steel needle '25°C, load lkgf/cm2, contact speed 5mm / min, and probe pressure Φ to the subsequent layer of the film. And keep it for 10 seconds. Thereafter, the film was peeled off at a peeling speed of 1 mm/min, and the load at this time was measured. This measurement was carried out 5 times, and the average enthalpy of the three measured enthalpy of the maximum enthalpy and the minimum enthalpy was removed as the adhesion. Below 0.25 N, the measurement error is recorded as ND. <25 μπι Release PET (Cover Film) Evaluation of Peelability> The adhesive film produced in the examples and the comparative examples was cut out to an edge of about 1 〇cm, and the release PET side of 38 μm was fixed on a fixed table. The sheet can be fixed by decompression). Secondly, only the 25 μηι release PET at room temperature (25. (:) lower four corners -31 - 201030083 is pinched by hand, and the film is pulled vertically by about 5 cm at an angle of 90 degrees. At 25 μιη The case where the PET is peeled off between the PET and the adhesive layer is referred to as 〇, and if the film is peeled off between the adhesive layer and the 38 μπι release PET, or the film is peeled off by the fixing table without peeling between the layers, it is referred to as X. Evaluation of part fixing property> The film obtained by the examples and the comparative examples was peeled off from the 25 μm release PET by a batch type vacuum pressure laminator (manufactured by Nichigo-Morton Co., Ltd., "MortoN- 724"), laminated on a single side of a 26mm x 76mm slide. The laminate is vacuum-sucked at room temperature (25 ° C) for 30 seconds and then pressurized with a pressure-resistant rubber at a pressure of 30 lkg/cm2. The 38 μιη detached PET of the above-mentioned sample was peeled off, and 3 volts of 1 608 wafer capacitors were placed on the adhesive film. Next, a batch vacuum pressure laminator (Nichigo- Morton ("Morton-724"), 30-second vacuum suction, use pressure-resistant rubber The capacitor was fixed on the adhesive film under the pressure of 30 lkg/cm 2 under room temperature (25 ° C). The fixed capacitor was peeled off in a vertical direction with a small nickel on the film. The trace of the capacitor remaining on the surface of the layer is as shown in Fig. 1. The shape of the capacitor is marked as 〇 on the surface of the adhesive layer, and only part of the trace is marked as △, and no trace is recorded as X. -32 - 201030083 <Measurement of the maximum part position deviation amount> The same method as the part fixation evaluation is performed to prepare the part-mounted slide glass, and the measurement capacitor is fixed and hardened as shown in Fig. 2 The positional deviation of the part is determined by the distance measuring machine (product name, MF-UD2017B (manufactured by Mitsutoyo), as shown in Fig. 2, and the origin A and B are determined. The origin is from the corner of the part (4 corners) away from the blood (W, X, Y, Z). The hardening of the sample is carried out by placing the above sample in a batch heat treatment machine to make the resin vertical. Heat at 180 °C for 30 minutes. The resin composition layer (adhesive layer) is hardened. The position of the hardened part is determined by the origins A and B determined before hardening and the angle (4 corners) of the hardened part (W', X', Y' , Z' ). (|W'-W Bu|Χ'_Χ|,|Υ'-Υ卜丨Z'_Z丨) as the part position deviation amount, the maximum number of these four numbers is the largest part The positional deviation φ is the amount of ND that is removed from the adhesive layer during hardening. -33- 201030083 [Table i] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Tg (°C) 196 195 194 177 181 182 149 155 157 Initial Resistance 値 (Ω) 1.56E+12 2.46E+12 4.64E+12 9.29E+12 7.22E+12 3.36Ε+12 2.53Ε+12 4.18Ε+12 6.07Ε+12 HAST resistance 値(Ω) 1.01E+ 12 2.09E+12 3.64E+12 2.17E+11 2.80E+11 3.50Ε+11 4.81Ε+11 2.89Ε+11 5.02Ε+11 Adhesion (N) 1.5 2.5 3 2.1 3 3.4 2.6 3.3 4 Cover film peeling Sexual component fixing degree 〇〇〇〇〇〇〇〇〇 Maximum part position deviation amount (#m) 24 20 22 18 7 10 9 8 9 [Table 2] Comparative example 1 Comparative example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Tg (°C) 195 197 178 177 153 159 209 153 Initial resistance 値 (Ω) 2.67E+12 4.32E+12 5.38E+12 7.59E+12 6.49E+12 4.44E+12 1.14E+11 8.05E+12 HAST resistance 値(Ω) 9.34E+11 8.57E+11 5.38E+12 8.94E+11 9.51E+11 4.71E+11 2.16E+10 2.20E+11 Adhesion (N) ND 4.6 1 4.7 1.6 5 ND 6.7 Cover film peelability 〇X 〇X 〇X Part fixability X X X square square square Δ Δ billion parts largest position deviation amount (Aim) 153 27 81 9 55 7 ND 16
由表1可知，實施例之接著薄膜其零件固定性爲良好 最大零件位置偏差量爲小，且覆蓋薄膜（25μπι離型PET 201030083 )之剝離性也爲良好一事。另一方面，比較例之接 ，於黏著力爲低之情況，因零件固定性拙劣其最大 置偏差爲大，若黏著力過強則覆蓋薄膜（25 μπι離 )剝離性降低。 【圖式簡單說明】 [圖1 ]於零件固定性評價試驗中之評價方法的 [圖2]於零件位置偏差評價試驗中之評價方法 圖。As is apparent from Table 1, the adhesiveness of the film of the example was good, and the maximum amount of positional deviation was small, and the peeling property of the cover film (25 μm off-type PET 201030083) was also good. On the other hand, in the case of the comparative example, when the adhesive force is low, the maximum deviation of the part is large due to poor fixing property, and if the adhesive force is too strong, the peeling property of the cover film (25 μm) is lowered. [Simplified illustration of the drawing] [Fig. 1] The evaluation method in the part fixing evaluation test [Fig. 2] The evaluation method in the part position deviation evaluation test.
著薄膜 零件位 型 PET 槪念圖 的槪念The memory of the film part type PET mourning
-35--35-