201137020 六、發明說明： 【發明所屬之技術領域】 本發明係關於-種包含環氧樹脂、環氧樹脂用硬化劑、 含環氧基之丙烯酸系樹脂及填料之硬化性組合物，更詳細 而言，本發明係關於一種例如可用於在半導體晶片之單 形成用以接著該半導體晶片的黏接著劑層之用途等之硬化 性組合物、及使用該硬化性組合物之切晶·黏晶帶、連接 構造體及附帶黏接著劑層之半導體晶片之製造方法。 【先前技術】 半導體裝置等電子設備之小型化及高性能化進一步發 展。對應於此，開發有各種硬化性組合物作為電子設備用 接著劑。作為該硬化性組合物之材料，而廣泛使用環氧樹 脂。 作為包含環氧樹脂之硬化性組合物之一例，於下述專利 文獻1中，揭示有包含環氧樹脂、丙烯酸系橡膠及潛伏性 硬化劑之硬化性組合物。 又，具體而言，上述硬化性組合物例如用於將半導體晶 片接著於基板或其他半導體晶片上》為使該接著操作容易 進行，已知藉由稱作磨削前切晶法（dicing bef()re gHnding method)之切晶法將半導體晶圓分割成各個半導體晶片 後’使用硬化性組合物獲得附帶接著劑層之半導體晶片之 方法。 關於上述磨削前切晶法，首先於半導體晶圓表面以不分 割該半導體晶圓之方式形成切口。其次，於形成有切口之 154861.doc 201137020 半導體晶圓表面貼附保護片材。其後，磨削半導體晶圓之 背面直至達到切口部分為止，使半導體晶圓之厚度變薄， 而分割成各個半導體晶片。通常，於分割成各個半導體晶 片之分割後半導體晶圓表面貼附有保護片材。 為使用藉由磨削前切晶法獲得之分割後半導體晶圓來獲 付附帶接著劑層之半導體晶片，而使用切晶_點晶帶。例 如於下述專利文獻2、3中揭示有接著片材與基材（切晶保 δ蒦务帶）積層而成之切晶·黏晶帶。該切晶-黏晶帶中之接著 片材為黏晶層，即用以於半導體晶片上積層接著劑層而獲 得附帶接著劑層之半導體晶片的片材。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利第3342703號公報 [專利文獻2]日本專利特開2005-260204號公報 [專利文獻3]日本專利特開2006-080142號公報 【發明内容】 [發明所欲解決之問題] 於使用專利文獻2、3中所記載之切晶-黏晶帶而獲得附 帶接著劑層之半導體晶片時，將切晶-黏晶帶自接著片材 側貼附於分割後半導體晶圓上。其次，照射雷射光、或者 進行加熱或冷卻等而使接著片材改質。繼而，拉伸經改質 之接著片材而將該接著片材沿著分割後半導體晶圓之切割 部分進行切割’並且將各個半導體晶片分離，而於半導體 晶片之下表面形成經切割之接著劑層。其後，將附帶接著 I54861.doc 201137020 劑層之半導體晶片自基材剝離、抽出。抽出 層之半導體晶片係自接著劑層側安裝於基板上附帶接著劑 t利文獻2中所記載之切晶.黏晶帶必f於切 之刖，藉由加熱或冷卻而使接著片材改質。專矛 • 戶“己載之切晶-黏晶帶必需於切割接著片枋」文獻3中 * 雷射光錢接W材改質。因此，專利文獻2、3中 所5己載之切晶-黏晶帶必需用以使接著片材改質之步驟。 因而，無法高效地獲得附帶接著劑層之半導體晶片j =’專利文獻2、3中所記載之切晶·黏晶帶存在當拉 妾者片材時’未於所需之位置適當切割該接著片材之情 況。例如，存纟接著劑層未埃實地配置於半導體晶片下方 之情況。因此，於將附帶接著劑層之半導體晶片接著於接 :對象構件之情形時，半導體晶片會傾斜或未充分地接 著。 進而，於將使用專利文獻2、3中所記載之切晶_黏晶帶 而獲得之附帶接著劑層之半導體晶片積層並接著於接著對 象構件之情形時，存在接著性較低之情況。進而’存在接 著後於半導體晶片上產生翹曲，或於經硬化之接著劑層 . 中產生龜裂之情況。 , 本發明之目的在於提供一種硬化後之硬化物之接著性優 異的硬化性組合物。 本發明之限定目的在於提供一種於獲得附帶黏接著劑層 之半導體晶片之情形時’於分割後半導體晶圓之單面積層 由硬化性組合物所形成之黏接著劑層後拉伸該黏接著劑層 15486I.doc 201137020 寺叮精度良好地切害j黏接著劑層的硬化性組合物；及使 用該硬化性組合物之切晶_黏晶帶、連接構造體及附帶黏 接著劑層之半導體晶片之製造方法。 本發明之進而限；t之目的在於提供—種於使用由硬化性 組合物所形成之黏接著劑層將半導體晶片積層並接著於接 著對象構件上之情形時，可抑制半導體晶片之赵曲，且可 抑制於經硬化之黏接著劑層中產生龜裂的硬化性組合物； 及使用該硬化性組合物之切晶·黏晶帶、連接構造體及附 帶黏接著劑層之半導體晶片之製造方法。 [解決問題之技術手段] 根據本發明之較廣之態樣’可提供一種硬化性組合物， 其包含：環氧樹脂；J裒氧樹脂用硬化劑；重量平均分子量 為10萬以上、40萬以下，且玻璃轉移溫度為6〇t以上之第 1之含環氧基之丙烯酸系樹脂；重量平均分子量為丨萬以 上、2萬以下，且玻璃轉移溫度為6〇。〇以上之第2之含環氧 基之丙婦酸系樹脂；及奈米填料；並且於上述環氧樹脂、 上述第1之含環氧基之丙烯酸系樹脂及上述第2之含環氧基 之丙烯酸系、樹脂的合計⑽重量％中，上述^之含環氧基 之丙烯酸系樹脂之含量為10〜4〇重量％，且上述第2之含環 氧基之丙稀酸系樹脂之含量為1〜3 $重量％。 於本發明之硬化性組合物之某特定態樣中，於使硬化性 組合物成形為片狀而獲得片材時，硬化前之該片材於23t 下之斷裂應力為6 MPa以下，且硬化前之上述片材於23。〇 下之斷裂伸長率為200%以下。 I5486I.doc -6 - 201137020 於本發明之硬化性組合物之其他特定態樣中，於使硬化 性組合物成形為片狀而獲得片材時，當使硬化前之上述片 材以5°C/min之升溫速度自40eC升溫至200eC時，40〜20〇t 下之最低熔融黏度為1000 pa.s以上。 於本發明之硬化性組合物之進而其他之特定態樣中，硬 化後之硬化物於180。(：下之儲存彈性模數為40 MPa以上。 於本發明之硬化性組合物之進而其他之特定態樣中上 述環氧樹脂包含具有極性基之環氧樹脂。 於本發明之硬化性組合物之另一特定態樣中，硬化性組 合物成形為片狀。 於本發明之硬化性組合物之進而另一特定態樣中，硬化 性組合物為用以將半導體晶片接著於接著對象構件上之黏 接著劑。 本發明之切晶-黏晶帶包含由根據本發明所構成之硬化 性組合物而形成的黏接著劑層、與積層於該黏接著劑層之 單面之基材層。 本發明之連接構造體包含半導體晶片、接著對象構件、 及配置於該半導體晶片與該接著對象構件之間之硬化物 層，且上述硬化物層係藉由使根據本發明所構成之硬化性 組合物硬化而形成。 本發明之附帶黏接著劑層之半導體晶片之製造方法包括 如下步驟：使用由根據本發明所構成之硬化性組合物而形 成之黏接著劑層、及分割成各個半導體晶片之分割後半導 體晶圓，力上述分割後半導體晶圓之單面積層上述黏接著 154861.doc 201137020 劑層，拉伸上述點接著劑層 上述分割後半導體晶圓之切 割後半導體晶圆中之各個半 上述黏接著劑層之狀態下抽 體晶片。 ’藉此將上述黏接著劑層沿著 割部分進行切割，且使上述分 導體晶片分離；以及於積層有 出上述附帶黏接著劑層之半導 於本發明之附帶黏接著劑層之半導體晶片之製造方法的 其他特定L樣中’使用包含上述黏接著劑層、及積層於該 黏接著劑層之單面之基材層的切晶·黏晶帶。 於本發明之附帶黏接著劑層之半導體晶片之製造方法的 其他特定態樣中，於上述黏接著劑層拉伸之前或拉伸期 間不對上述黏接著劑層進行改質。 於本發明之附帶黏接著劑層之半導體晶片之製造方法的 進而其他特定態樣中，於上述黏接著劑層拉伸之前或拉伸 期間，不進行為了使上㈣接著騎對上述黏接著 劑層加熱及冷卻及照射雷射光。 [發明之效果] 本發明之硬化性組合物包含：環氧樹脂；環氧樹脂用硬 化劑；重量平均分子量為⑽以上、4G萬以下，且玻璃轉 移溫度為6(TC以上之第！之含環氧基之丙烯酸系樹脂；重 量平均分子量為1萬以上、2萬以下，且玻璃轉移溫度為 60 C以上之第2之含環氧基之丙婦酸系樹脂；及奈米填 料，並且上述第1、第2之含環氧基之丙烯酸系樹脂的含量 為特定範圍内，故硬化後之硬化物之接著性優異。因此， 例如於使用本發明之硬化性組合物將半導體晶片接著於接 】54861,d〇c 201137020 著對象構件時’可提高半導體曰 卞等體日日片與接著對象構件之接合 可靠性。 進而，於使用本發明 之更化性組合物獲得附帶黏接著劑 層之半導體晶片之情形時·，热八丨从 哥於刀割後半導體晶圓之單面積 層由上述硬化性組合物所形成之純著劑層後拉伸該黏接 著劑層時，可沿著分割後半"㈣之切㈣㈣度良好 地切割黏接著劑層。 【實施方式】 以下，對本發明之詳細情況進行說明。 (硬化性組合物） 本發明之硬化性組合物包含環氧樹脂、環氧樹脂用硬化 劑、第1之含環氧基之丙稀酸系樹脂、第2之含環氧基之丙 稀酸系樹脂、及奈米填料。上述^之含環氧基之丙稀酸 系樹脂之重量平均分子量為1G萬以上、4G萬以下，且上述 第1之含環氧基之丙烯酸系樹脂之玻璃轉移溫度為6〇t>c以 上。上述第2之含環氧基之丙烯酸系樹脂之重量平均分子 量為1萬以上、2萬以下，且上述第2之含環氧基之丙烯酸 系樹脂之玻璃轉移溫度為60t：以上。於上述環氧樹脂、上 述第1之含環氧基之丙烯酸系樹脂及上述第2之含環氧基之 丙稀酸系樹脂的合計1 00重量％中，上述第1之含環氧基之 丙烯酸系樹脂之含量為1 0~40重量。/。，且上述第2之含環氧 基之丙烯酸系樹脂之含量為卜35重量。/。。由於本發明之硬 化性組合物具有上述組成’因此硬化後之硬化物之接著性 較高。進而，於分割後半導體晶圓之單面積層由上述硬化 154861.doc 201137020 性組合物所形成之黏接著劑層後拉伸該黏接著劑層時，可 精度良好地切割黏接著劑層。進而，於使用由硬化性組合 物所形成之黏接著劑層將半導體晶片積層並接著於接著對 象構件上之情形時，可抑制半導體晶片之翹曲，並且可抑 制於經硬化之黏接著劑層中產生龜裂。 [環氧樹脂] 本發明之硬化性組合物中所含之環氧樹脂並無特別限 定。上述環氧樹脂較佳為主鏈上具有環狀烴骨架者。藉由 使用主鏈上具有環狀烴骨架之環氧樹脂，可使硬化性組合 物硬化後之硬化物變得剛直，可抑制硬化物中之分子運 動。進而，硬化物表現出優異之機械強度及耐熱性，並且 由於吸水性亦降低，故而亦表現出優異之耐濕性。 作為上述環氧樹脂，並無特別限定，例如可列舉：二環 戊二稀型環氧樹脂、萘型環氧樹脂、四㈣苯乙烧型:氧 樹脂、四（縮水甘油氧基苯基）乙烧、及3,4_環氧_6_甲基環 己基甲基.3,4_環氧·6_甲基環己院碳酸0旨等。上述環氧樹 脂可僅使用1種，亦可併用2種以上。 作為上述二環戊二烯型環氧樹脂，可列舉二氧化二環戍 二烯及具有二環戊二浠骨架之苯㈣路清漆環氧樹脂等。 作為上述萘型環氧樹脂，可列舉：丨·縮水甘油基萘、2縮 水甘油基萘、i，2-二縮水甘油基萘、】，5二縮水甘油基 萘、1，6-二縮水甘油基蔡、1>7•二縮水甘油基萘、2 7 ,二縮 水甘油基萘、三縮水甘油基萘及咖四縮水甘油：萘 等。 、 15486 丨.doc -10· 201137020 當進一步提高硬化物之接著性，且拉伸積層於分割後半 導體晶圓之單面的黏接著劑層時，就精度更加良好地切割 黏接著劑層之觀點而言，上述環氧樹脂較佳為包含具有極 性基之環氧樹脂。再者，當拉伸積層於上述分割後半導體 晶圓之單面的黏接著劑層時，有時將切割該黏接著劑層之 性質稱作割裂性。 上述環氧樹脂較佳為具有極性基且具有環狀烴骨架者。 作為上述環氧樹脂之上述極性基，可列舉：羥基、胺 基、亞胺基、醯胺基、腈基、羧基及羰基等。就進一步提 高黏接著劑層、與半導體晶片及接著對象構件之接著力之 觀點而έ，上述極性基較佳為羥基、亞胺基或腈基。藉由 使用具有羥基、亞胺基及腈基之環氧樹脂，可於黏接著層 使用則之保管時使硬化反應性降低，於保管後容易維持極 性基。 上述環氧樹脂較佳為具有自由之極性基。所謂上述「自 由」，係指極性基不作為主鏈中之鍵骨架之一部分而存 在’而存在於側鏈或末端。 就進一步提高硬化物之接著性及黏接著劑層之割裂性之 觀點而§，上述環氧樹脂較佳為包含於23<>(：(常溫）下為液 狀之環氧樹脂。 就更進一步提高硬化物之接著性及黏接著劑層之割裂性 之觀點而言，上述環氧樹脂較佳為包含具有上述極性基之 衣氧枒脂、及上述於23勺下為液狀之環氧樹脂。 又上述環氧樹脂之分子量較佳為未達1萬。所謂上述 I54861.doc 201137020 環氧樹脂之「分子量」，於上述環氧樹脂並非聚合物之情 形、及可確定上述環氧樹脂之結構式之情形時，係指可^ 據該結構式算出之分子量，於上述環氧樹脂為聚合物之情 形時’係指重量平均分子量。 月 於上述環氧樹脂100重量％中，具有上述極性基之環氧 樹脂之含量較佳為10〜100重量％。上述環氧樹脂亦可全部 為具有上述極性基之環氧樹脂。於上述環氧樹脂100重量 %中，具有上述極性基之環氧樹脂之含量的更佳下限為30 重量/〇，更佳上限為80重量❶/。。若具有上述極性基之環氧 樹脂之含量滿足上述下限及上限，則可進一步提高硬化物 之接著性及黏接著劑層之割裂性。 於上述環氧樹脂100重量％中，上述於23<)(：下為液狀之 環氧樹脂之含量較佳為10〜100重量％。上述環氧樹脂亦可 全部為上述於23°c下為液狀之環氧樹脂。於上述環氧樹脂 100重量。/。中，上述於23。。下為液狀之環氧樹脂之含量的 更佳下限為10重量％，更佳上限為40重量％ ^若上述於 23 C下為液狀之環氧樹脂之含量滿足上述下限及上限，則 可進一步提高硬化物之接著性及黏接著劑層之割裂性。 [第1、第2之含環氧基之丙稀酸系樹脂] 本發明之硬化性組合物中所含之第〗之含環氧基之丙烯 酸系樹脂只要重量平均分子量為1〇萬以上、4〇萬以下且 玻璃轉移溫度為6〇t以上，則並無特別限定。本發明之硬 化性組合物中所含之第2之含環氧基之丙烯酸系樹脂只要 重量平均分子量為1萬以上、2萬以下，且玻璃轉移溫度為 154861.doc •12· 201137020 60°C以上，則並無特別限定。上述第}、第2之含環氧基之 丙烯酸系樹脂可於末端具有環氧基，亦可於側鏈（側位）具 有環氧基。上述第1、第2之含環氧基之丙烯酸系樹脂各自 可僅使用1種，亦可併用2種以上。 藉由不但使用重量平均分子量相對較大之上述第1之含 裱氧基之丙烯酸系樹脂，而且進而使用重量平均分子量相 對較小之上述第2之含環氧基之丙烯酸系樹脂，並且藉由 使第1、第2之含環氧基之丙烯酸系樹脂之含量為上述特定 範圍内，可於拉伸貼附於分割後半導體晶圓上之黏接著劑 層時，於所需之位置精度良好地切割黏接著劑層。即便於 常溫（23°C)下拉伸黏接著劑層，亦可精度良好地切割黏接 著劑層。進而，藉由使用上述第2之含環氧基之丙烯酸系 樹脂，於將由上述硬化性組合物所形成之黏接著劑層積層 並接著於接著對象構件之情形時，可提高接著性，且可抑 制於半導體晶片上產生翹曲，或於經硬化之黏接著劑層中 產生龜裂。 又，藉由使用上述第1、第2之含環氧基之丙烯酸系樹 月曰，可使硬化前之製膜性升高，又，可使硬化物之機械強 度、耐熱性及可撓性升高。 上述含環氧基之丙烯酸系樹脂例如藉 之丙稀酸系單體與不具有環氧基之丙稀酸系化 獲得。 作為上述具有環氧基之丙烯酸系單體，可列舉丙烯酸縮 水甘油醋及甲基丙烯酸縮水甘油酯等。 I54861.doc •13- 201137020 作為上述不具有環氧基之丙稀酸系化合物，可列舉：丙 烯酸乙酯、丙烯酸丁酯、丙烯酸—2-乙基己酯、丙烯酸羥乙 酯及丙烯酸異指酯等。 通常，丙烯酸系樹脂（丙烯酸系聚合物）大多藉由以溶劑 作為介質之溶液聚合法而製造。於溶液聚合法中，於生成 高分子量之丙烯酸系樹脂時，有溶液之黏度極度上升或根 據情形而產生凝膠化之虞。因此，難以獲得高分子量之丙 烯酸系樹脂。又，於溶液聚合法中，由於容易殘留未反應 之單體’故而必需將殘留單體與溶劑一起去除，而使製造 步驟變得繁雜。 例如’若使用甲基丙烯酸縮水甘油酯（GMA，Glycidyi methacrylate)作為具有環氧基之丙烯酸系單體於其他丙 烯酸系單體中添加大量GMA而進行溶液聚合，則藉由環氧 基自身之凝集力僅可獲得分子量相對較低（未達1〇〇〇〇)之含 環氧基之丙烯酸系樹脂。若欲獲得高分子量之含環氧基之 丙烯酸系樹脂，則容易產生如上所述之極度之黏度上升或 凝膠化。 另一方面，若使用上述GMA等，藉由以水或非溶劑作為 介質之懸浮聚合法製造含環氧基之丙烯酸系樹脂，則可獲 得含有大量環氧基、分子量分佈狹窄且為高分子量之含環 氧基之丙烯酸系樹脂。該含環氧基之丙烯酸系樹脂為幾乎 未殘留單體之潔淨之樹脂。進而，於上述方法中’自聚合 系統之分離操作亦較容易，製造步驟變得簡單。 因此，上述第1之含環氧基之丙烯酸系樹脂較佳為藉由 154861.doc •14- 201137020 懸浮聚合法而獲得之含環氧基之丙烯酸系樹脂。藉由使用 由懸浮聚合法獲得之第1之含環氧基之丙烯酸系樹脂，可 進一步提高硬化物之機械強度、耐熱性及可撓性。 上述第1之含環氧基之丙烯酸系樹脂之重量平均分子量 A1G萬以上、4G萬以下。若上述第1之含環氧基之丙稀酸 : 系樹脂之重量平均分子量未達10萬’則製膜性變差，難以 以片狀之狀態處理由硬化性組合物所形成之片材或黏接著 劑層。若上述第丨之含環氧基之丙烯酸系樹脂之重量平均 分子量超過40萬，則硬化前之片材或黏接著劑層變得過 硬。因此，黏接著劑層之割裂性惡化。又，硬化物變得過 硬，容易於硬化物中產生龜裂。上述第丨之含環氧基之丙 烯酸系樹脂之重量平均分子量的較佳下限為2〇萬，較佳上 限為30萬。 上述第2之含環氧基之丙烯酸系樹脂之重量平均分子量 為1萬以上、2萬以下。若上述第2之含環氧基之丙烯酸系 樹脂之重量平均分子量未達〗萬，則製膜性變差，難以以 片狀之狀態處理由硬化性組合物所形成之片材或黏接著劑 層。若上述第2之含環氧基之丙烯酸系樹脂之重量平均分 子量超過2萬’則硬化前之片材或黏接著劑層變得過硬。 因此，黏接著劑層之割裂性惡化。又，硬化物變得過硬， 容易於硬化物中產生龜裂。 上述第1、第2之含環氧基之丙烯酸系樹脂的玻璃轉移溫 度為60°C以上。若上述第丨、第2之含環氧基之丙烯酸系樹 月日的玻璃轉移溫度未達6〇°c，則由硬化性組合物所形成之 154861.doc •15- 201137020 片材或黏接著劑層之拉伸伸長特性下降。具體而言，斷裂 應力變得過高或斷裂伸長率變得過高。上述第丨、第2之含 裱氧基之丙烯酸系樹脂之玻璃轉移溫度的較佳下限為 70 C。上述第1、帛2之含環氧基之丙稀酸系樹脂之玻璃轉 移溫度較佳為l〇〇t以下。若上述第丨、第2之含環氧基之 丙烯酸系樹脂之玻璃轉移溫度滿足上述上限，則可適度拉 伸上述片材或黏接著劑層，而切割上述片材或黏接著劑 層。例如於獲得附帶黏接著劑層之半導體晶片之情形時， 田拉伸積層於分割後半導體晶圓之單面之黏接著劑層時， 可精度良好地切割黏接著劑層。 上述第1、第2之含環氧基之丙烯酸系樹脂之環氧當量較 佳為200〜咖。若上述第丨、第以含環氧基之㈣酸系樹 脂之環氧當量超過200,則硬化物之可換性充分提高。若 上述第1、第2之含環氧基之丙烯酸系樹脂之環氧當量為 〇〇以下，則硬化物之耐熱性及可撓性進一步提高。 於上述環氧樹脂、上述第1之含環氧基之丙烯酸系樹脂 及上述第2之含環氧基之丙稀酸系樹脂的成分X的合計100 重量％中，±述第！之含環氧基之丙稀酸系樹脂之含量為 10〜40重量份。於上述成分χ之合計⑽重量％中上述第1 。3衣氧基之丙烯酸系樹脂之含量的更佳下限為15重量 % ’更佳上限為35重量％β若上述^之含環氧基之丙稀酸 =樹脂的含量滿足上述下限及上限，則可進—步提高硬化 則之片材製膜性、片材之處理性及硬化後之硬化物之接著 進而’可適度拉伸上述片材或黏接著劑層，而切割上 I5486I.doc 201137020 述片材或黏接著劑層。進而，於使用由上述硬化性組合物 所形成之黏接著劑層將半導體晶片積層並接著於接著對象 構件上之情形時’半導體晶片難以發生麵曲而剝離，硬化 物之機械強度、耐熱性及可撓性進一步提高，可抑制於經 硬化之黏接著劑層中產生龜裂。 於上述環氧樹脂、上述第丨之含環氧基之丙烯酸系樹脂 上述第2之含環氧基之丙稀酸系樹脂的合計1 〇〇重量％之 成刀X令，上述第2之含環氧基之丙烯酸系樹脂的含量為 重量4。於上述成分X之合計重量％ _，上述第2 之3裒氧基之丙烯酸系樹脂之含量的更佳下限為5重量 % ’士更佳上限為30重量％。若上述第2之含環氧基之丙稀酸 系樹脂的含量滿足上述下限及上限，則可進—步提高硬化 前之片材製膜性、片材之處理性及硬化後之硬化物之接著 性。進而，可適度拉伸上述片材或黏接著劑層，而切割上 述片材或黏接著劑層。進而，於使用由上述硬化性組合物 所形成之黏接㈣層將半導體晶片積層並接著於接著對象 構件上之清形時，帛導體晶片難以產生翹曲而剝離，硬化 物之機械強度及耐熱性及可撓性進—步提高，可抑制於經 硬化之黏接著劑層中產生龜裂。 [奈米填料] ^明之硬化性組合物包含奈㈣料。該奈料料只要 尺寸，則並無特別限I上述奈米填料可僅使用i 種’亦可併用2種以上。 上述奈米填料具有增黏作用 亦作為增黏劑發揮功能。 I54861.doc 201137020 由於使用上述第2之含環氧基之丙烯酸系樹脂，而存在硬 化性組合物及由該硬化性組合物所形成之片材或黏接著劑 層於加熱熔融時容易過度流動之傾向。於本發明之硬化性 組合物中，除了使用上述第2之含環氧基之丙烯酸系樹脂 以外，亦使用奈米填料，故而可將硬化性組合物及由該硬 化性組合物所形成之片材或黏接著劑層於加熱熔融時之流 動性控制於較佳之範圍。因此，於使用硬化性組合物或黏 接著劑層進行接著時，可將黏接著劑層於加熱熔融時之流 動性控制於較佳之範圍，故而可提高硬化前之半導體晶片 之約束性，可提高硬化後之硬化物之接著性。 作為上述奈米填料，可列舉二氧化矽、氧化鋁及碳酸鈣 等。上述奈米填料較佳為鹼金屬或過渡金屬等雜質較少之 二氧化矽。 上述奈米填料之平均粒徑為1 nm以上且未達1 〇〇〇 nm。 上述奈米填料之平均粒徑之較佳下限為5 nm，較佳上限為 300 nm ’更佳上限為100 nm，進而更佳之上限為5〇 nm。 上述奈米填料之平均粒徑尤佳為1 〇〇 nm以下。若上述奈米 填料之平均粒徑滿足上述下限，則於使用硬化性組合物或 黏接著劑層進行接著時，可將黏接著劑層於加熱熔融時之 流動性控制於較佳之範圍，故而可提高硬化前之半導體晶 片之約束性，可提高硬化後之硬化物之接著性。若上述奈 米填料之平均粒徑滿足上述上限，則可減少由硬化性組合 物所形成之片材或黏接著劑層之厚度不均。又，若上述奈 米填料之平均粒徑為300 nm以下，則割裂性進一步提高， 154861.doc -18- 201137020 二述不米填料之平均粒徑為1〇〇⑽以下則割裂性明顯 &。進而’可與上述片材或黏接著劑層之薄型化相對 應。例如即便上述片材或勒接著劑層之厚度為1㈣〜20 叫，亦可減少厚度不均，可表現較高之接著性。 月上述+均粒禮」，係指利用穿透式電子顯微鏡所 測量之平均1次粒徑。上述奈米填料之「平均粒徑」係藉 由利用穿透式電子顯微鏡觀察任意则個奈米填料，算出 所測量之粒徑之平均個數而求出。又，藉由利用穿透式電 子顯微鏡之觀察而測量之粒徑係指將奈米填料近似為圓形 時之近似圓之直徑（直徑）。 相對於上述環氧樹脂100重量份，上述奈米填料之含量 較佳為1〜30重量份。相對於上述環氧樹脂1〇〇重量份，上 述奈米填料之含量之更佳下限為5重量份，更佳上限為2〇 重量份。若上述奈米填料之含量滿足上述下限及上限，則 可將硬化性組合物及由該硬化性組合物所形成之片材或黏 接著劑層於加熱熔融時之流動性控制於更佳之範圍，可進 一步提高硬化物之接著性。於使用硬化性组合物或黏接著 劑層進行接著時，可將黏接著劑層於加熱熔融時之流動性 控制於較佳之範圍，故而可提高硬化前之半導體晶片之約 束性’可提高硬化後之硬化物之接著性。 [環氧樹脂用硬化劑] 作為上述環氧樹脂用硬化劑，例如可列舉：三烷基四氫 鄰苯二曱酸針等加熱硬化型酸酐系硬化劑、酚系硬化劑、 胺系硬化劑及雙氰胺等潛伏性硬化劑、及陽離子系觸媒型 154861.doc • 19· 201137020 硬化劑等。上述硬化劑可僅使用丨種亦可併用2種以上。 作為上述於常溫下為液狀之加熱硬化型酸酐系硬化劑之 具體例，例如可列I:甲基四氫鄰苯二曱酸酐、甲基六氫 鄰苯二甲酸酐、甲基耐地酸酐及三烷基四氫鄰苯二甲酸酐 等酸酐系硬化劑。其中，由於進行疏水化，因此可較佳地 使用曱基耐地酸酐及三烷基四氫鄰苯二甲酸酐。 為調整硬化速度或硬化物之物性等，亦可併用上述硬化 劑與硬化促進劑。 上述硬化促進劑並無特別限定。作為上述硬化促進劑， 例如可列舉咪唑系硬化促進劑及三級胺系硬化促進劑等。 ’、中可較佳地使用咪嗤系硬化促進劑◎於使用咪哇系硬 化促進劑之情形時，可容易地調整硬化速度及硬化物之物 性等。上述硬化促進劑可僅使用丨種，亦可併用2種以上。 上述咪唑系硬化促進劑並無特別限定。作為上述咪唑系 硬化促進劑，例如可列舉：以氰乙基保護咪唑之丨位之^ 氰乙基-2-苯咪唑、及以異三聚氰酸保護鹼性之商品名 「2MAOK-P W」（四國化成工業公司製造）等。上述咪唑系 硬化促進劑可僅使用丨種，亦可併用2種以上。 上述硬化劑係根據環氧樹脂及硬化劑之種類、及環氧當 量等而以適當之含量使用。硬化劑之添加量、及併用酸酐 系硬化劑與例如咪唑系硬化促進劑等硬化促進劑之情形時 之酸酐系硬化劑之添加量較佳為相對於環氧基為理論上所 需之當量之60〜100% ’更佳為70〜9〇%。若酸酐系硬化劑之 添加量超出需要地過剩，則有氯離子藉由水分自硬化物中 154861.doc -20- 201137020 溶出之虞。藉由使上述硬化劑之含量為適當之範圍，可使 硬化性組合物有效地硬化，且可使硬化物中難以產生源自 硬化劑之殘渣。 相對於上述硬化劑100重量份，硬化促進劑之含量較佳 為0.5〜20重量份。若硬化促進劑之含量為上述下限以上， 則可使硬化性組合物有效地硬化。若硬化促進劑之含量為 上述上限以下，則硬化促進劑難以殘留，可提高硬化物之 接合可靠性。 [其他成分] 本發明之硬化性組合物視需要亦可含有橡膠粒子、熱塑 性樹脂、環氧樹脂以外之熱硬化性樹脂、密接性改善劑、 pH值調整劑、離子捕捉劑、黏度調整劑、觸變性賦予劑、 抗氧化劑、熱穩定劑、光穩定劑、料線吸收劑、著色 劑脫水劑、難燃劑、抗靜電劑、防黴劑、防腐劑及溶劑 專各種添加劑。 [硬化性組合物之詳細情況] 本發明之硬化性組合物較佳為黏接著劑。包含上述環氧 树月曰、上述環氧樹脂用硬化劑、上述第丨、第2之含環氧基 之丙烯酸系樹脂及上述奈米填料的硬化性組合物較佳為於 硬化前具有黏著性且於硬化後表現接著性之黏接著劑。 本發明之硬化性組合物由於處理性優異，因此較佳為成 形為片狀，較佳為片狀之黏接著劑（黏接著劑層）。 當使本發明之硬化性組合物成形為片狀而獲得片材時， 硬化則之該片材於23°C下之斷裂應力較佳為6 MPa以下。 154S61.doc -21 · 201137020 該斷裂應力之更佳上限為4 MPae另一方面，上述斷裂應 力較佳為1 MPa以上，若上述斷裂應力滿足上述上限，則 可進一步提高片材或黏接著劑層之割裂性。若上述斷裂應 力滿足上述下限，則可提高片材或黏接著劑層之製膜效 率，進而可進一步提高片材或黏接著劑層之處理性。 當使本發明之硬化性組合物成形為片狀而獲得片材時， 硬化則之該片材於23°C下之斷裂伸長率較佳為2〇〇%以 下。該斷裂伸長率之更佳上限為1〇0%，進而更佳之上限 為50%。另一方面，上述斷裂伸長率較佳為1%以上。若上 述斷裂伸長率滿足上述上限，則可進一步提高片材或黏接 著劑層之割裂性。若上述斷裂伸長率滿足上述下限，則可 提高片材或黏接著劑層之製膜效率，進而可進一步提高片 材或黏接著劑層之處理性。 於使本發明之硬化性組合物成形為片狀而獲得片材時， 當使硬化前之該片材以5°C /min之升溫速度自4〇°c升溫至 200°C時，40〜200°C下之最低熔融黏度較佳為1〇〇〇 Pa.s以 上。該40〜200°C下之最低熔融黏度更佳為15〇〇 Pa.s以上， 進而更佳為2000 Pa.s以上。另一方面’上述最低熔融黏度 較佳為20000 Pa.s以下。若上述最低溶融黏度滿足上述下 限’則於使用硬化性組合物或黏接著劑層進行接著時，可 將硬化性組合物或黏接著劑層於加熱熔融時之流動性控制 於較佳之範圍，故而可提高硬化前之半導體晶片之約束 性，可提高硬化後之硬化物之接著性。尤其是，若上述 40〜200°C下之最低熔融黏度為1500 pa_s以上，則硬化物之 154861.doc -22· 201137020 接者性明顯提高。若上述最低熔融黏度滿足上述上限，則 可進一步提高硬化物之接著性。進而，於接著對象構件表 面具有凹凸之情形時’可於該表面之凹部充分填充由硬化 性組合物所形成之片材或黏接著劑層，而可使 以產生空隙。 上述最低溶融黏度為40〜細。c下之值。設為該溫度範圍 之原因在於：於使硬化性組合物及由該硬化性組合物所形 成之片材或黏接著劑層硬化時，冑等係自常溫加轨至 200°C左右。 本發明之硬化性組合物之硬化後之硬化物於丨8 〇它下之 儲存彈性模數較佳為40 MPa以上。該儲存彈性模數之更佳 下限為100 MPa。另一方面，上述儲存彈性模數較佳為 1000 MPa以下。若上述儲存彈性模數滿足上述上限則硬 化物不會變得過硬，可進一步提高可撓性與接合可靠性。 若上述儲存彈性模數滿足上述下限，則可藉由硬化物之高 彈性化而提高黏接著劑層之硬化物與半導體晶片之積層體 的剛性，可高效地進行打線接合步驟中之超音波接合。 本發明之硬化性組合物可用於接合各種接著對象構件之 用途。本發明之硬化性組合物可較佳地用於將半導體晶片 接著於接著對象構件上之用途。 作為上述接者對象構件，可列舉基板.、半導體晶片及導 線架專。上述接著對象構件較佳為基板或半導體晶片。作 為上述基板’可列舉陶究基板、樹脂基板、碎基板、半導 體基板及玻璃基板等。 154861.doc •23- 201137020 (連接構造體） 如上所述，本發明之硬化性組合物可較佳地用於將半導 體晶·片接著於接著對象構件上之用途。 於圖6中，以剖面圖模式地表示使用本發明之一實施形 態之硬化性組合物的連接構造體。 圖ό所示之連接構造體51包含半導體晶片52、接著對象 構件53、配置於半導體晶片52與接著對象構件53之間之硬 化物層54 ^硬化物層54係藉由使上述硬化性組合物硬化而 形成。於硬化物層54上接著有半導體晶片52與接著對象構 件5 3。於獲得連接構造體5 1時，上述硬化性組合物可成形 為片狀而以片材之形式使用’亦可以液狀或片狀之黏接著 劑之形式使用。 於連接構造體51中’硬化物層54係藉由使上述硬化性組 合物硬化而形成，由於硬化物層54之接著性較高，故而連 接可靠性優異。 (切晶-黏晶帶） 本發明之切晶-黏晶帶包含由上述硬化性組合物所形成 之黏接著劑層、及積層於該黏接著劑層之單面之切晶層。 圖1(a)及（b)係模式地表示本發明之第1實施形態之切晶_ 黏晶帶的圖。圖1 (a)為部分缺失平面圖，圖丨（b)為沿著圖 1(a)中之I-Ι線的部分缺失前視剖面圖。 圖1(a)及（b)所不之切晶-黏晶帶1具有長條狀之脫模層 2。於脫模層2之上表面2a依序積層有黏接著劑層3、基材 層4、切晶層5。於黏接著劑層3之單面即第1表面3a積層有 154861.doc • 24· 201137020 基材層4。基材層4之第1表面4a貼附於黏接著劑層3，基材 層4之第1表面4a之相反側的第2表面4b貼附於切晶層5。黏 接著劑層3之第1表面3a之相反側的第2表面3b為貼附有半 導體晶圓之面。 於長條狀之脫模層2之上表面2a等間隔地配置有包含黏 接著劑層3、基材層4及切晶層5之複數個積層物。亦可於 該積層物之側方，於脫模層2之上表面2a設置保護片材。 黏接著劑層3、基材層4及切晶層5之平面形狀為圓形。 俯視時’黏接著劑層3較脫模層2、基材層4及切晶層5更 小。俯視時’基材層4較脫模層2及切晶層5更小。俯視 時，切晶層5較脫模層2更小。脫模層2具有向較黏接著劑 層3、基材層4及切晶層5之外周側面更側方突出之區域。 於本實施形態中，基材層4具有非黏著性。因此，無需 照射UV(Ultravi〇let，紫外線）而降低黏著力等使黏接著劑 層改質之步驟，便可容易地自基材層4剝離附帶黏接著劑 層3之半導體晶片。 上述「非黏著性」不僅包括表面不具有黏著性之情形， 亦包括以手指觸摸表面時具有不黏手之程度的黏著性之情 況2具體而言，所謂「非黏著」，係指將基材層之具有非 黏著之部分貼附於不鏽鋼板上而以則匪/論之剝離速度 將，基材層剥離時，黏著力為〇 〇5ν/25_幅度以下。又 切曰b層5包含基材5 a與積層於基材5 a之單面之黏著劑層 切晶層5具有較黏接著劑層3及基材層4之外周側面更 突出之區域。切晶層5係自黏著劑層5關，於突出之區域 154861.doc •25· 201137020 貼附於脫模層2之上表面2a ’且於中央區域貼附於基材層4 之第2表面4b。於切晶時，在切晶層5之黏著劑層5B貼附有 切晶環。 圖2係模式地表示本發明之第2實施形態之切晶-黏晶帶 的圖。圖2(a)為部分缺失平面圖，圖2(b)為沿著圖2(a)中之 I-Ι線的部分缺失前視剖面圖。 圖2(a)及（b)所示之切晶-黏晶帶11除基材層及切晶層不 同以外，以與切晶-黏晶帶i相同之方式構成。 切晶-黏晶帶11包含基材層1 2與切晶層1 3。於脫模層2之 上表面2a依序積層有黏接著劑層3、基材層12與切晶層 13»於黏接著劑層3之單面即第1表面3a積層有基材層12。 基材層12之第1表面12a貼附於黏接著劑層3，基材層12之 第1表面12a之相反側的第2表面12b貼附於切晶層13。 基材層12及切晶層13之平面形狀為圓形。俯視時，黏接 著劑層3較脫模層2、基材層1 2及切晶層13更小。俯視時， 基材層1 2之大小與切晶層1 3之大小大致相同。俯視時，基 材層12及切晶層13較脫模層2更小。脫模層2具有向較黏接 著劑層3、基材層12及切晶層13之外周侧面更側方突出之 區域。 於本實施形態中，基材層12包含具有非黏著性之非黏著 部12A。非黏著部12A係設置於基材層12之中央區域。非 黏著部12A係設置於與黏接著劑層3之貼附有半導體晶圓之 位置相對應之部分。非黏著部12A之平面形狀為圓形。俯 視時，非黏著部12A較黏接著劑層3更大。因此，非黏著部 154861.doc •26· 201137020 12 A具有向較黏接著劑層3之外周側面更側方突出之區域。 因此’當於分割後半導體晶圓之單面貼附黏接著劑層3 時’可將分割後半導體晶圓準確對準黏接著劑層3之貼附 有非黏著部12A之部分。貼附後，可將非黏著部12A確實 地配置於分割後半導體晶圓上所貼附之黏接著劑層3之第2 表面3b。因此’於切割黏接著劑層3後，無需對附帶黏接 著劑層3之半導體晶片進行UV照射而降低黏著力等使黏接 著劑層改質之步驟，便可自基材層12之非黏著部12A容易 地剝離。因此，可降低生產損失，而可提昇良率。 基材層12於非黏著部12A之外側部分之區域包含具有黏 著性之黏著部12B。黏著部12B為環狀。基材層12被覆黏 接著劑層3。基材層12之非黏著部12A貼附於黏接著劑層3 之第1表面3a，基材層12之黏著部12B貼附於脫模層2之上 表面2a。於黏接著劑層3之整個表面積層有基材層12之非 黏著部12A。於黏接著劑層3之表面未積層有黏著部12B。 於切晶時，在基材層12之黏著部12B貼附有切晶環。 基材層12之非黏著部12A與黏著部12B係形成為一體》 非黏著部12A與黏著部12B係由相同材料所形成，並非由 不同材料所形成。 切晶層13僅由基材所構成，不包含黏著劑層。亦可使用 切晶層5代替切晶層π。 脫模層2例如為脫模膜。脫模層2係用於保護黏接著劑層 3之貼附有半導體晶圓之第2表面3b。再者，脫模層2亦可 不必使用。 154861.doc -27- 201137020 作為構成脫模層2之材料，可列舉：聚對苯二曱酸乙二 S曰樹脂等聚酯系樹脂；聚四氟乙烯樹脂、聚乙烯樹脂、聚 丙，樹脂、聚曱基戊稀樹脂、聚乙酸乙稀醋樹脂等聚稀煙 系知N曰，聚氣乙烯樹脂及聚醯亞胺樹脂等塑膠樹脂等。 脫模層2之表面亦可進行脫模處理。脫模層可為單層， 亦可為複數層。於脫模層為複數層之情形時’各層亦可由 不同樹脂所形成》 就進一步提高脫模層2之處理性或剝離性之觀點而言， 脫模層2之厚度較佳為1〇〜1〇〇 μπΐ2範圍内，更佳為25〜5〇 μπι之範圍内。 黏接著劑層3為半導體晶片之黏晶中所使用之層。黏接 著劑層3係用於將半導體晶片接著於基板或其他半導體晶 片等上。 黏接著劑層3係由上述硬化性組合物所形成。切晶-黏晶 帶1、11係用於獲得附帶黏接著劑層3之半導體晶片。於獲 得附帶黏接著劑層3之半導體晶片後，將所得之附帶黏接 著劑層3之半導體晶片自黏接著劑層3側積層於基板等接著 對象構件上。其後，給予熱或光之能量，使黏接著劑層3 硬化，藉此可經由黏接著劑層3於接著對象構件上牢固地 接合半導體晶片。 黏接者劑層3之厚度並無特別限定。黎接著劑層3之厚度 較佳為1〜100 μπι之範圍内。黏接著劑層3之厚度之更佳下 限為3 μπι，更佳上限為60 μηι。若黏接著劑層3之厚度為上 述範圍内，則半導體晶片之貼附較為容易，進而可與半導 154861.doc • 28 - 201137020 體裝置之薄型化相對應。 基材層4、12例如可使用活性能量線硬化型或熱硬化型 之具有黏著性之組合物而形成。於使用活性能量線硬化型 組合物之情形時，局部調整活性能量線對組合物之照射 量’藉此可使基材層4、12之黏著性存在局部差異。為使 基材層具有非點著性，只要增加活性能量線之照射量即 可。為使基材層具有黏著性，只要不照射活性能量線，或 者減少活性能量線之照射量即可。 基材層4、12較佳為由包含丙烯酸系聚合物之組合物所 形成。基材層4、12較佳為由使包含丙烯酸系聚合物之組 合物交聯而成之交聯體所形成。此時，可進一步提高黏接 著劑層之割裂性。又，可容易地控制及設計基材層4、1 2 之極性、儲存彈性模數或斷裂伸長率。 上述丙烯酸系聚合物並無特別限定。上述丙烯酸系聚合 物較佳為（甲基）丙烯酸烷基酯聚合物。作為（曱基）丙烯酸 烷基酯聚合物’可較佳地使用具有碳數1〜18之烷基者。藉 由使用具有碳數1〜18之烷基之（曱基）丙烯酸烷基酯聚合 物’可充分降低基材層4、12之極性，可降低基材層4、12 之表面能量，且可提高黏接著劑層3自基材層4、12之剝離 性。 上述組合物較佳為包含活性能量線反應起始劑及熱反應 起始劑中之至少一者，更佳為包含活性能量線反應起始 劑。活性能量線反應起始劑較佳為光反應起始劑。 上述活性能量線包括紫外線、電子束、α射線、β射線、 154861.doc -29· 201137020 γ射線、x射線、紅外線及可見光線。於該等活性能量線 中，由於硬化性優異且硬化物難以劣化，故而較佳為紫外 線或電子束。 作為上述光反應起始劑，例如可使用光自由基產生劑或 光陽離子產生劑等。作為上述熱反應起始劑，可列舉熱自 由基產生劑等。於上述組合物中，亦可為控制黏著力而添 加異氰酸酯系交聯劑。 基材層4、12之厚度並無特別限定。基材層4、12之厚度 較佳為1〜1〇〇 μιη之範圍内。基材層4、12之厚度之更佳下 限為5 μηι，更佳上限為60 μηι。若基材層4 ' 1 2之厚度滿足 上述較佳下限，則可進一步提高切晶時之割裂性、及延伸 陡若基材層4、12之厚度滿足上述較佳上限，則厚度變 得更加均勻，可進一步提高切晶之精度。 曰切晶層5、13例如為切晶膜。作為切晶層5之基材5Α及切 晶層13之材料，可列舉：聚對笨二甲酸乙二酯樹脂等聚酯 系樹脂；聚四氟乙烯樹脂、聚乙烯樹脂、聚丙烯樹脂、聚 曱基戊烯樹脂、聚乙酸乙烯酯樹脂等聚烯烴系樹脂；聚氯 乙烯樹脂及聚醯亞胺樹脂等塑膠樹脂等。其中，由於延伸 性優異，環境負荷較小’故而可較佳地使用聚稀烴系樹 脂。 作為切晶層5之黏著劑層5Β之材料，可列舉：丙浠酸系 黏著劑、特殊合成橡膠系黏著劑、合成樹脂系黏著劑或橡 +系黏著劑等。其中’較佳為丙烯酸系黏著劑或橡膠系黏 著劑，更佳為丙稀酸系黏著劑，進而更佳為感壓型丙稀酸 154861.doc 201137020 系黏著劑。於使用丙烯酸系黏著劑之情形時，可提高黏著 劑層5B對基材層4之黏著力、以及黏著劑層5B對切晶環之 貼附性及自切晶環之再剝離性。進而，可降低黏著劑層5B 之製造成本。 切晶層5、13之厚度並無特別限定。切晶層$、丨3之厚度 較佳為10〜200 μιη之範圍内。切晶層5、1 3之厚度之更佳下 限為6 0 μπι，更佳上限為1 5 0 μηι。若切晶層5、13之厚度為 上述範圍内，則可進一步提高自脫模層2之剝離性及切晶 層5、13之延伸性。再者，切晶層5之厚度係表示基材5八與 黏著劑層5Β之合計厚度。 於切晶-黏晶帶1、11中可使用切晶層5、i 3。亦可省略 切晶層5、13，而使基材層4、12兼作切晶層。尤其是，於 切晶-黏晶帶11中，可於基材層12之黏著部12Β貼附切晶 環，故而無需於切晶層13貼附切晶環。由於無需於切晶層 13貼附切晶環，因此切晶層13亦可不具有黏著力。因此， 可自更廣泛之範圍内選擇構成切晶層13之材料及組成。 於切晶時，可更有效地防止半導體晶片之飛散等，且可 獲得更加均勻之延伸性，因此較佳為於基材層4、12之貼 附有黏接著劑層3之側之相反側的表面貼附切晶層5。 (附帶黏接著劑層之半導體晶片之製造方法） 其次，對使用圖1(a)、（b)所示之切晶_黏晶帶丨之情形時 的附帶黏接著劑層之半導體晶片t製造方法的一例進行以 下說明。 首先，準備切晶-黏晶帶1與積層體21。 154861.doc -31· 201137020 如圖3⑷所示’積層體21包含保護片材辦積層於保護 片材22之單面❿之分割後半導體晶圓23。保護片材22積 層於分割後半導體晶圓23之單面即表面23”分割後半導 體晶圆23係分割成各個半導體晶片。分割後半導體晶圓η 之平面形狀為圓形。 積層體2丨可經由圖3(a)〜(d)所示之各步驟，以如下方式 獲得。 首先，如圖3(a)所示，準備半導體晶圓23八。半導體晶 圓23A為分割前半導體晶圓。半導體晶圓23八之平面形狀 為圓形。半導體晶圓23A之表面23a於藉由界道（stree〇劃分 成矩陣狀之各區域，形成有用以構成各個半導體晶片之電 路。 如圖3(b)所示，自表面23a側對所準備之半導體晶圓23A 進行切晶。於切晶後，半導體晶圓23 A未被分割》於半導 體晶圓23 A之表面23a形成有用以將其分割為各個半導體晶 片之切口 23c。切晶係例如使用具有高速旋轉之刀片的切 晶裝置等而進行。 其次’如圖3(c)所示，於半導體晶圓23A之表面23a貼附 保護片材22。其後’磨削半導體晶圓23 A之背面23b，使半 導體晶圓23 A之厚度變薄。此處，半導體晶圓23 A之背面 23b係磨削至切口 23c部分為止。如此般，可獲得圖3(d)所 示之積層體21。 半導體晶圓23A之背面23b較佳為磨削至切口 23c部分為 止。磨削係使用例如具有磨削磁鐵等之研磨機等磨削機而 154861.doc -32- 201137020 進行。於進行磨削時’在半導體晶圓23 A之表面23a貼附有 保護片材22，因此於電路中未附著磨削屑。又，即便半導 體晶圓23 A於磨削後分割為各個半導體晶片，複數個半導 體晶片仍未分開，而為貼附於保護片材22之狀態。 於獲得積層體21後，如圖4(a)所示，將積層體21自保護 片材22側置於平台25上。於平台25上，在與分割後半導體 晶圓23之外周側面隔開固定間隔之位置設置有圓環狀切晶 環26。於剝離切晶-黏晶帶1之脫模層2之同時或剝離脫模 層2後’將露出之黏接著劑層3之第2表面扑貼附於分割後 半導體晶圓23之背面23b。藉此，於分割後半導體晶圓23 之單面即背面23b積層黏接著劑層3。又，將露出之切晶層 5之黏著劑層5B貼附於切晶環26上。 其次，如圖4(b)所示，將貼附有黏接著劑層3之分割後 半導體a曰圓2 3自平台2 5抽出並倒置。此時，將切晶環2 6以 貼附於黏著劑層5B之狀態抽出。將抽出之分割後半導體晶 圓23以表面23a成為上方之方式倒置，並置於另一平台27 上。 其次，如圖5(a)所示，自分割後半導體晶圓23之表面 剝離保護片材22。於分割後半導體晶圓23之背面2补積層 黏接著劑層3後，且於拉伸黏接著劑層3之前剝離保護片材 22。於剝離保護片材22時，為容易進行剝離，視需要亦可 加熱保護片材22。其中，較佳為於加熱保護片材22時不對 黏接著劑層3進行改質。 其次，如圖5(b)所示，拉伸黏接著劑層3而進行切割。 154861.doc •33· 201137020 此時，沿著分割後半導體晶圓23之切割部分23c進行切 割，且使分割後半導體晶圓23中之各個半導體晶片分離。 由於黏接著劑層3貼附於分割後半導體晶圓23之背面23b， 故而可沿著分割後半導體晶圓23之切割部分23c即切晶線 切割黏接著劑層3。切割黏接著劑層3後，於黏接著劑層3 形成有切割部分3 c。 再者，於本說明書中，亦將拉伸黏接著劑層3而進行切 割稱作割裂。於拉伸黏接著劑層3而進行切割之操作（割裂） 中，亦包括切晶’切晶-黏晶帶丨可用於拉伸黏接著劑層3 而進行切割（割裂ρ換s之，切晶_黏晶帶丨為割裂黏晶 帶。 作為拉伸黏接著劑層3之方法，例如可列舉自黏接著劑 層3之下方往上頂起而對黏接著劑層3、基材層*及切晶層^ 賦予圖5(b)所示之力A之方法。藉由賦予力A，結果可對黏 接著劑層3、基材層4及切晶層5賦予朝外側拉伸之力bi、 B2 ’從而可拉伸黏接著劑層3。 黏接著劑層3係由上述硬化性組合物所形成，該硬化性 組合物包含環氧樹脂、環氧樹脂用硬化劑、特定之第丄之 3環氧基之丙烯酸系樹脂、特定之第2之含環氧基之丙烯 酸系樹脂、及奈米填料’上述糾、第2之含環氧基之丙烯 酸系樹脂之含量為上述特定之範圍内。因此，藉由拉伸黏 接著劑層3’可沿著分割後半導體晶圓23之切割部分仏精 度良好地切割黏接著劑層3。因此，於半導體晶片之下 難以產生黏接著劑層3之缺失。由於可精度良好地切 154861.doc -34- 201137020 1毐接著劑層3’故而可提高附帶黏接著劑層3之半導體晶 扣取〖生。由於難以產生黏接著劑層3之缺失，因此於 將附帶黏接著㈣之半導體晶片積層並接著於接著對象構 件上^情形時’可抑制半導體晶片發生傾斜，且可提高半 '曰S片之接σ可罪性。進而，可抑制於接著後之半導體 晶片上產生翹曲，且可抑制於經硬化之黏接著劑層中產生 藉由使用切晶-黏晶帶！，於切割黏接著劑層3時，即便 f黏接著劑層3進仃改質，亦可精度良好地切割黏接著 劑層3。例如，卽你X ;佳> 進仃為了使黏接著劑層3改質而對黏 接著劑層3加熱及冷卻及照射雷射光，亦可精度良好地切 割黏接著劑層3。較佳為於黏接著劑層3拉伸之前或拉伸期 間’不對黏接著劑層3進行改質。較佳為於黏接著劑層3拉 伸之前或拉伸期間，不推& 進仃為了使黏接著劑層3改質而對 黏接著劑層3加熱及冷卻及昭 π钟及照射雷射光。較佳為於黏接著 劑層3拉伸之前或拉伸期問，τ ^ & 不進行為了使黏接著劑層3改 質而對黏接著劑層3加埶（用本丨祕，& ‘、、、（用以剝離保護片材22之加熱除外） 及冷卻及照射雷射光。彳θ a 尤仁疋’亦可使黏接著劑層3改質。 於不對黏接著劑層3進行改晳夕达…士 貝之情形時，可提高附帶黏接 著劑層3之半導體晶片之製造效率。 於切割黏接著劑層3後，於 於積層有黏接著劑層3之狀態 下，將半導體晶片連同點接著齋 考劑層3 一起自基材層4剝離並 抽出。如此般，可搏得附趣 歿仵附帶黏接著劑層3之半導體晶片。 於使用切晶-黏晶帶1之情开彡g本 屯時’於貼附有分割後半導體晶 15486I.doc •35· 201137020 圓23之黏接著劑層3部分之下方存在具有非黏著性之基材 層4 ’因此可提高附帶黏接著劑層3之半導體晶片之拾取 性。於使用切晶-黏晶帶11之情形時，於貼附有分割後半 導體晶圓2 3之黏接著劑層3部分之下方存在基材層12之非 黏著部12A，因此亦可提高附帶黏接著劑層3之半導體晶片 之拾取性。於切割黏接著劑層3後，將附帶黏接著劑層3之 半導體晶片自基材層4剝離前，亦可拉伸切晶層5，進一步 擴大各個半導體晶片間之間隔。 再者’於以單體之形式使用由上述硬化性組合物所形成 之黏接著劑層來代替切晶-黏晶帶丨之情形時，藉由上述硬 化性組合物於分割後半導體晶圓23之單面積層黏接著劑層 後，亦可於黏接著劑層上積層基材層4、丨2。視需要亦可 於基材層4、12進而積層切晶層5、 以下，藉由列舉實施例及比較例，對本發明進行具體說 明。本發明並不限定於以下實施例。 為形成硬化性組合物而準備以下材料。 (1)環氧樹脂 笨氧基系固體環氡樹脂（三菱化學（舊Japan Ep〇xy ReShlS)公司製造之「l〇〇4F」，環氧當量為925 g/eq，分子 量未達1萬，具有自由之極性基即羥基） 一環戍一稀系固體環氧樹脂（DIC公司製造之「HP- 7200HH」’環氧當量為282 g/eq，分子量未達！萬無極性 基） ， 雙酚A型液狀環氧樹脂（DIC公司製造之「ΕχΑ_ 154861.doc •36· 201137020 850CRP」’環氧當量為172 g/eq，分子量未達1萬，無極性 基） (2) 環氧樹脂用硬化劑 酸Sf系硬化劑（三菱化學（舊Japan Epoxy Resins)公司製 造之「YH-309」） (3) 硬化促進劑 咪。坐系硬化劑（四國化成公司製造之「2MAOK-PW」） (4) 第1之含環氧基之丙烯酸系樹脂 含環氧基之丙烯酸系樹脂（日油公司製造之「Marproof G-2050M」’環氧當量：34〇 g/eq，重量平均分子量：20 萬，玻璃轉移溫度：74t ) 含環氧基之丙稀酸系樹脂（日油公司製造之「Marproof G-1005SA」’環氧當量：3300 g/eq，重量平均分子量：10 萬’玻璃轉移溫度：98°C) (5) 其他含環氧基之丙烯酸系樹脂 含環氧基之丙稀酸系樹脂（長瀨化成（Nagase ChemteX)公 司製造之「SG-80H」，環氧當量：14700 g/eq，重量平均 分子量：35萬，玻璃轉移溫度：11°C) (6) 第2之含環氧基之丙烯酸系樹脂 含環氧基之丙烯酸系樹脂（曰油公司製造之「Marproof G-0250S」，環氧當量：310 g/eq，重量平均分子量：2萬， 玻璃轉移溫度：74°C) 含環氧基之丙烯酸系樹脂（曰油公司製造之「Marproof G-0150M」，環氧當量：310 g/eq，重量平均分子量：1 15486丨.doc •37· 201137020 萬’玻璃轉移溫度：7 Γ(：) (7) 奈米填料 無水超微細無疋形二氧化石夕（德山（T〇kUyama)公司製造 之「Μτ-10」’平均1次粒徑為15 nm) 無水超微細無定形二氧化矽（德山公司製造之「Dm_ 10」’平均1次粒徑為15 nm) SO C^2(Admatechs 公司製造之 Admafine Silica，平均一 次粒徑未達1000 nm ’平均粒徑為〇·5 μπι) S〇-C6(Admatechs公司製造之 Admafine Silica，平均粒 徑為 2.2 μπι) 再者，ΜΤ-10、DM-10及SO-C2之平均一次粒徑係藉由 利用穿透式電子顯微鏡進行觀察並算出所測量之粒徑之平 均值而求出之值。又，SO-C2及SO-C6之平均粒徑係表示 利用雷射繞射式粒度分佈計所測定之中值徑。 (8) 其他成分 胺基石夕院偶合劑（Chisso公司製造之「S320)) (實施例1) 對作為環氧樹脂之苯氧基系環氧樹脂（三菱化學（舊Japan Epoxy Resins)公司製造之「1004F」）45重量份及雙酚a型 液狀環氧樹脂（DIC公司製造之「EXA-850CRP」）20重量 伤 作為環氧樹脂用硬化劑之酸酐系硬化劑（三菱化學（舊 Japan EpOXy Resins)&司製造之 ΓγΗ_3〇9」）35 重量份、作 為環氧樹脂用硬化促進劑之咪唑系硬化促進劑（四國化成 公司製造之「2MA0K-PW」）5重量份、作為第1之含環氧 154861.doc -38- 201137020 基之丙烯酸系樹脂之Marproof G-2050M(日油公司製造）15 重量伤、作為第2之含環氧基之丙烤酸系樹脂之Marpr〇 〇f G-0150M(日油公司製造）20重量份、作為奈米填料之無水 超微細無定形二氧化矽（德山公司製造之「ΜΤ-10」）ι〇重 量份、及胺基碎烧偶合劑（Chisso公司製造之「S320」）1重 量伤進行§周配而獲付調配物。以固形物成分成為5〇重量％ 之方式將所得之調配物添加至曱基乙基酮（MEK，Methyl ethyl ketone)中並攪拌’而獲得作為黏接著劑之硬化性組 合物。 (實施例2〜4及比較例1〜3) 如下述表1所示變更獲得上述調配物時所使用之材料之 種類及調配量，除此以外’以與實施例丨同樣之方式獲得 作為黏接著劑之硬化性組合物。 (評價） (1)斷裂應力、斷裂伸長率及最低熔融黏度之評價 使用棒式塗佈機，以乾燥後之厚度成為10 方式將 實施例及比較例之硬化性組合物塗佈於表面經脫模處理之 厚度50 μηι之聚對苯二曱酸乙二酯（pet，Polyethylene terephthalate)片材的脫模處理面上。其後，於100°c下乾 燥3分鐘’使硬化性組合物成形為片狀，而獲得片材。藉 由熱式層壓積層該片材，製作斷裂應力及斷裂伸長率測定 用試片（縱向50 mmx橫向1〇 mmx厚度〇.1 mm)及熔融黏度 測定用試片（直徑20 mmx厚度0.5 mm)。 使用拉伸s式驗器（Orientec公司製造之「Tensilon RTC- 154861.doc •39- 201137020 13 l〇」），於23°C、標線間距25 mm及拉伸速度300 mm/min 之條件下，測定所得之試片之斷裂應力及斷裂伸長率。 使用流變計（Reologica Instrument AB公司製造之 「VAR100」），於直徑20 mm之平行板、頻率1 Hz、變形 0· 1 %、40°C〜200°C及升溫速度5°C /min之條件下，測定試 片之黏度。於40°C〜200°C之範圍内讀取熔融黏度之最小 值，設為最低熔融黏度。 (2) 儲存彈性模數之評價 使用棒式塗佈機，以乾燥後之厚度成為10 μπΐ2方式將 實施例及比較例之硬化性組合物塗佈於表面經脫模處理之 厚度50 μπι之聚對苯二甲酸乙二酯（pet)片材的脫模處理面 上。其後’於100。(：下乾燥3分鐘，使硬化性組合物成形為 片狀’而獲付片材。藉由熱式層壓積層該片材而製作試片 (縱向50 mmx橫向3 mmx厚度0.5 mm)。藉由在17〇。〇下加 熱60分鐘使該試片硬化，而獲得硬化物。使用動態黏彈性 裝置（IT Meter, and Control公司製造之「DVA-200」），於 25〜300°C、5°C/min及10 Hz之條件下測定所得之硬化物於 180°C下之拉伸儲存彈性模數E，。 (3) 切晶-黏晶帶之製作 製作圖1所示之形狀之切晶-黏晶帶。 使丙烯酸2-乙基己酯95重量份、丙稀酸2_經基乙酯5重 量份、作為光自由基產生劑之irgacure 65丨（Ciba_Geigy公 司製造’ 500/。之乙酸乙酯溶液）〇 2重量份及月桂硫醇 (Lauryl merCaptan)0.01重量份溶解於乙酸乙酯中，而獲得 154861.doc -40· 201137020 溶液。對該溶液照射紫外線進行聚合，而獲得聚合物之乙 酸乙醋溶液。進而，使該溶液之固形物成分丨〇〇重量份與 2-甲基丙烯醯氧基乙基異氰酸酯（昭和電工公司製造， Karenz ΜΟΙ)3·5重量份進行反應，獲得作為（曱基）丙烯酸 系樹脂交聯體之丙烯酸共聚物。丙烯酸共聚物之重量平均 分子量為70萬，酸值為〇.86(mgKOH/g)。 對所得之丙烯酸共聚物1〇〇重量份、U-324A(新中村化學 工業公司製造，胺基甲酸酯丙烯酸酯低聚物）2重量份及作 為光自由基產生劑之lrgacure 651(Ciba-Geigy公司製造）1重 量份進行調配，將其溶解於乙酸乙酯中，而獲得組合物。 使用敷料器將該組合物塗佈於脫模PET膜上，於1〗〇〇c下加 熱乾燥3分鐘’而形成厚度5〇 之膜狀組合物層。於該組 合物層上貼附脫模PET膜。其後，於高壓水銀燈下，以 2000 mJ/cm2對上述組合物層照射365 nm之紫外線，於脫 模PET膜上形成具有非黏著性之基材層（厚度5〇 μιη)。 又，利用敷料器’以厚度成為40 μηι之方式將實施例及 比較例中獲得之硬化性組合物塗佈於琳得科公司製造之 PET3 8CS上，於110°C下加熱乾燥3分鐘，而獲得黏接著劑 層（厚度40 μιη)。 將上述基材層之兩面所貼附之脫模PET膜之一者剝離而 獲得直徑306.8 mm之圓形基材層。將上述pET38cs上之黏 接著劑層加工成直徑305.8 mm之圓形》以對準圓之令心之 方式貼合基材層與黏接著劑層。將貼附於基材層之單面之 脫模PET膜剝離’並將切晶層（PE tape#6318-B(積水化學工 I54861.doc •41 - 201137020 業公司製造之黏著膜，於厚度70 μπι之聚乙烯基材之單面 形成有厚度ίο哗之橡膠系黏著劑層之點著膜))自黏著劑 層側貼附於基材層…將向較切晶層之黏接著劑層及基 材層之外周側面更側方突出之區域貼附於上述pET38cs 上。如此般獲得依序積層有脫模層、黏接著劑層、基材層 及切日日層之切晶-黏晶帶。 (4)割裂性、拾取性及接著性之評價 作為具有經磨削前切晶之分割後半導體晶圓之材料，而 使用保護片材、與磨削前切晶成10 mm見方之晶片尺寸之 半導體晶圓（矽鏡面晶圓，直徑為3〇〇 mm，厚度為4〇 的積層體。 將上述（3)切晶·黏晶帶之製作中所獲得之切晶·黏晶帶之 脫模PET膜自黏接著劑層及基材層剝離，露出黏接著劑 層、及基材層之外周部分。於60〇c之溫度下，於積層體之 分割後半導體晶圓之背面層壓黏接著劑層，而將切晶層之 黏著劑層貼附於切晶環上。 其次，將貼附有黏接著劑層之分割後半導體晶圓自平台 抽出並倒置，置於另一平台上。其後，於6〇t下自分割後 半導體晶圓之表面剝離保護片材。此時，不使黏接著劑層 改質。 其次’使用黏晶機（Canon-machinery公司製造之 「bestem D-02」）’於23°C及延伸量5 mm之條件下拉伸黏 接著劑層、基材層及切晶層’而沿著分割後半導體晶圓之 切割部分切割黏接著劑層，且使分割後半導體晶圓中之各 154861.doc -42- 201137020 個半導體晶片分離。 其次，於橡膠夾頭尺寸9 @ 了 9 mm見方、銷頂出量0.3 mm及 銷頂出速度4 mm/sec之條株丁，4線& 未件下，連續拾取20個附帶黏接著 晶於201137020 VI. Description of the Invention: [Technical Field] The present invention relates to a curable composition comprising an epoxy resin, a hardener for an epoxy resin, an epoxy resin containing an epoxy group, and a filler, and more specifically The present invention relates to a curable composition which can be used, for example, for forming a single semiconductor wafer to adhere to an adhesive layer of the semiconductor wafer, and a dicing/bonding ribbon using the curable composition. A method of manufacturing a semiconductor wafer with a connection structure and an adhesive layer. [Prior Art] The miniaturization and high performance of electronic devices such as semiconductor devices have been further developed. In response to this, various curable compositions have been developed as a binder for electronic devices. As the material of the curable composition, an epoxy resin is widely used. As an example of the curable composition containing an epoxy resin, Patent Document 1 below discloses a curable composition containing an epoxy resin, an acrylic rubber, and a latent curing agent. Further, in particular, the above-mentioned curable composition is used, for example, to attach a semiconductor wafer to a substrate or other semiconductor wafer. In order to facilitate the subsequent operation, it is known by a method called dicing bef (dicing bef) Refining method) A method of obtaining a semiconductor wafer with an adhesive layer using a curable composition after dividing a semiconductor wafer into individual semiconductor wafers. Regarding the above-described pre-grinding dicing method, first, a slit is formed on the surface of the semiconductor wafer so as not to divide the semiconductor wafer. Next, a protective sheet is attached to the surface of the semiconductor wafer formed with a slit 154861.doc 201137020. Thereafter, the back surface of the semiconductor wafer is ground until the slit portion is reached, and the thickness of the semiconductor wafer is thinned to be divided into individual semiconductor wafers. Generally, a protective sheet is attached to the surface of the divided semiconductor wafer which is divided into individual semiconductor wafers. In order to obtain a semiconductor wafer with an adhesive layer using the divided semiconductor wafer obtained by the pre-grinding dicing method, a dicing-dotted ribbon is used. For example, in the following Patent Documents 2 and 3, a dicing/adhesive tape in which a sheet and a substrate (cut granules) are laminated is disclosed. The next sheet in the diced-bonded ribbon is a viscous layer, i.e., a sheet of semiconductor wafer with an adhesive layer formed by laminating an adhesive layer on a semiconductor wafer. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Publication No. 3 342 703 [Patent Document 2] Japanese Patent Laid-Open No. Hei. No. 2005-260204 (Patent Document 3) Japanese Patent Laid-Open No. 2006-080142 [Problems to be Solved by the Invention] When a semiconductor wafer with an adhesive layer is obtained by using the dicing-bonding ribbon described in Patent Documents 2 and 3, the dicing-bonding ribbon is attached to the sheet side. Attached to the divided semiconductor wafer. Next, the laser beam is irradiated, or heating or cooling is performed to reform the subsequent sheet. Then, the modified succeeding sheet is stretched to cut the succeeding sheet along the cut portion of the divided semiconductor wafer and separate the respective semiconductor wafers, and a cut-off adhesive is formed on the lower surface of the semiconductor wafer. Floor. Thereafter, the semiconductor wafer attached to the I54861.doc 201137020 agent layer was peeled off from the substrate and taken out. The semiconductor wafer of the extraction layer is mounted on the substrate from the side of the adhesive layer, and the dicing described in the adhesive article 2 is attached. The adhesive layer must be cut, and the sheet is changed by heating or cooling. quality. Special Spear • The “Cut-Crystal-Crystal Tape of the Load must be cut and then smashed” in Document 3 * The laser light material is upgraded. Therefore, the diced-bonded ribbons contained in 5 of Patent Documents 2 and 3 are necessary for the step of modifying the sheet. Therefore, the semiconductor wafer with the adhesive layer cannot be efficiently obtained. j = 'The dicing and the viscous ribbon described in Patent Documents 2 and 3 are present when the sheet is pulled, and the dicing is not properly cut at the desired position. The condition of the sheet. For example, the case where the adhesive layer is not disposed under the semiconductor wafer. Therefore, when the semiconductor wafer with the adhesive layer is attached to the object member, the semiconductor wafer may be inclined or insufficiently attached. Further, when the semiconductor wafer with the adhesive layer obtained by using the dicing-bonded ribbon described in Patent Documents 2 and 3 is laminated and then in the case of the subsequent object member, there is a case where the adhesion is low. Further, there is a case where warpage occurs on the semiconductor wafer or cracks are formed in the cured adhesive layer. An object of the present invention is to provide a curable composition which is excellent in adhesion of a cured product after hardening. A limited object of the present invention is to provide a method for obtaining a semiconductor wafer with an adhesive layer and stretching the adhesive layer after the single-layer layer of the semiconductor wafer is formed of a curable composition. Agent layer 15486I.doc 201137020 Temple 叮 叮 叮 叮 j j j j j j j j j j j j j j j j j j j j j j j j j ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; 370 370 370 370 370 Wafer manufacturing method. The present invention is further limited; the purpose of t is to provide a method for suppressing the semiconductor wafer by laminating a semiconductor wafer using an adhesive layer formed of a curable composition and then adhering to the object member. And a curable composition capable of suppressing cracking in the cured adhesive layer; and a semiconductor wafer using the cleavage/adhesive tape, the connection structure, and the adhesive layer with the adhesive layer using the curable composition method. [Technical means for solving the problem] According to a broader aspect of the present invention, a curable composition comprising: an epoxy resin; a hardener for a J oxirane resin; and a weight average molecular weight of 100,000 or more and 400,000 Hereinafter, the first epoxy group-containing acrylic resin having a glass transition temperature of 6 〇t or more; the weight average molecular weight is 10,000 or more and 20,000 or less, and the glass transition temperature is 6 Å. And a second aspect of the epoxy group-containing acrylic acid-based resin; and a nanofiller; and the epoxy resin, the first epoxy group-containing acrylic resin, and the second epoxy group-containing resin The content of the epoxy group-containing acrylic resin in the total amount (10% by weight) of the acrylic resin or the resin is 10 to 4% by weight, and the content of the second epoxy group-containing acrylic resin is For 1~3 $% by weight. In a specific aspect of the curable composition of the present invention, when the curable composition is formed into a sheet form to obtain a sheet, the sheet has a breaking stress of 6 MPa or less at 23 t before hardening, and is hardened. The above sheet is at 23. The elongation at break under 〇 is 200% or less. I5486I.doc -6 - 201137020 In other specific aspects of the curable composition of the present invention, when the curable composition is formed into a sheet form to obtain a sheet, when the sheet before hardening is made 5 ° C When the heating rate of /min is raised from 40eC to 200eC, the lowest melt viscosity at 40~20〇t is 1000 pa.s or more. In still other specific aspects of the curable composition of the present invention, the hardened material after hardening is at 180. (The storage elastic modulus below is 40 MPa or more. In still other specific aspects of the curable composition of the present invention, the epoxy resin comprises an epoxy resin having a polar group. The curable composition of the present invention In another specific aspect, the curable composition is formed into a sheet. In still another specific aspect of the curable composition of the present invention, the curable composition is for adhering the semiconductor wafer to the subsequent member member. The dicing-adhesive tape of the present invention comprises an adhesive layer formed of the curable composition according to the present invention and a substrate layer laminated on one side of the adhesive layer. The connection structure of the present invention includes a semiconductor wafer, a subsequent target member, and a cured layer disposed between the semiconductor wafer and the succeeding member, and the cured layer is formed by a hardening composition according to the present invention. The method of manufacturing a semiconductor wafer with an adhesive layer of the present invention comprises the steps of: using a hardenable composition composed according to the present invention Forming an adhesive layer and dividing the semiconductor wafer into individual semiconductor wafers, and bonding the single-layer layer of the divided semiconductor wafer to the 154861.doc 201137020 layer, and stretching the dot-layer layer Extending the wafer in a state in which each of the adhesive layers in the semiconductor wafer after the dicing of the semiconductor wafer is etched. 'The thereby, the adhesive layer is cut along the cut portion, and the above-mentioned sub-conductor wafer is separated; And using in the other specific L-like method of manufacturing the semiconductor wafer with the adhesive layer of the present invention attached to the adhesive layer of the present invention, using the adhesive layer and laminating the adhesive layer A cleavage/polycrystalline ribbon of a substrate layer on one side of the agent layer. In other specific aspects of the method for fabricating a semiconductor wafer with an adhesive layer of the present invention, before or after stretching of the adhesive layer The adhesive layer is not modified during stretching. In still other specific aspects of the method for fabricating a semiconductor wafer with an adhesive layer of the present invention, Before the stretching of the adhesive layer or during the stretching, the heating and cooling of the adhesive layer and the irradiation of the laser light are not performed in order to ride the upper (four). [Effect of the Invention] The curable composition of the present invention comprises: a ring Oxygen resin; hardener for epoxy resin; an epoxy group-containing acrylic resin having a weight average molecular weight of (10) or more and 4 G000 or less, and a glass transition temperature of 6 (TC or more; weight average molecular weight of 10,000 or more a second epoxy group-containing acrylic acid-based resin having a glass transition temperature of 60 C or more; and a nano filler, and the first and second epoxy group-containing acrylic resins Since the content is within a specific range, the cured material after hardening is excellent in adhesion. Therefore, for example, when the semiconductor wafer is bonded to the object member by using the curable composition of the present invention, the semiconductor can be improved. The reliability of the joint between the body day and the next object member. Further, when a semiconductor wafer with an adhesive layer is obtained by using the improved composition of the present invention, the single-layer layer of the semiconductor wafer after the dicing is formed of the above-mentioned curable composition When the adhesive layer is stretched after the pure agent layer, the adhesive layer can be well cut along the cut (four) (four) of the second half of the division. [Embodiment] Hereinafter, the details of the present invention will be described. (Curable composition) The curable composition of the present invention comprises an epoxy resin, a curing agent for an epoxy resin, a first epoxy group-containing acrylic resin, and a second epoxy group-containing acrylic acid. Resin, and nano filler. The weight average molecular weight of the epoxy group-containing acrylic resin is 1 G 10,000 or more and 4 G 10,000 or less, and the glass transition temperature of the first epoxy group-containing acrylic resin is 6 〇 t > c or more . The second epoxy group-containing acrylic resin has a weight average molecular weight of 10,000 or more and 20,000 or less, and the second epoxy group-containing acrylic resin has a glass transition temperature of 60 t: or more. In the total of 100% by weight of the epoxy resin, the first epoxy group-containing acrylic resin, and the second epoxy group-containing acrylic resin, the first epoxy group-containing The content of the acrylic resin is from 10 to 40% by weight. /. Further, the content of the second epoxy group-containing acrylic resin is 35 weight. /. . Since the hardening composition of the present invention has the above composition', the cured product after hardening is highly adhesive. Further, when the single-layer layer of the semiconductor wafer after the division is stretched by the adhesive layer formed of the above-mentioned cured composition of 154861.doc 201137020, the adhesive layer can be cut with high precision. Further, when the semiconductor wafer is laminated using the adhesive layer formed of the curable composition and then on the object member, the warpage of the semiconductor wafer can be suppressed, and the cured adhesive layer can be suppressed. Cracks occur in the middle. [Epoxy Resin] The epoxy resin contained in the curable composition of the present invention is not particularly limited. The above epoxy resin preferably has a cyclic hydrocarbon skeleton in the main chain. By using an epoxy resin having a cyclic hydrocarbon skeleton in the main chain, the cured product obtained by hardening the curable composition can be made rigid, and the molecular motion in the cured product can be suppressed. Further, the cured product exhibits excellent mechanical strength and heat resistance, and also exhibits excellent moisture resistance due to a decrease in water absorbability. The epoxy resin is not particularly limited, and examples thereof include a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin, and a tetrakis(tetra) phenethyl type: an oxygen resin, and a tetrakis (glycidoxyphenyl group). Ethylene and 3,4_epoxy_6_methylcyclohexylmethyl.3,4_epoxy·6_methylcyclohexyl carbonate 0. These epoxy resins may be used alone or in combination of two or more. Examples of the dicyclopentadiene type epoxy resin include dicyclononadiene diene and a benzene (tetra) varnish epoxy resin having a dicyclopentadiene skeleton. Examples of the naphthalene type epoxy resin include hydrazine glycidyl naphthalene, 2 glycidyl naphthalene, i,2-diglycidyl naphthalene, 5, diglycidyl naphthalene, and 1,6-diglycidyl. Kecai, 1 > 7 • diglycidyl naphthalene, 2 7 , diglycidyl naphthalene, triglycidyl naphthalene and glyceryl diglycidyl: naphthalene and the like. 15486 丨.doc -10· 201137020 When the adhesion of the cured material is further improved and the adhesive layer is laminated on one side of the divided semiconductor wafer, the viewpoint of cutting the adhesive layer more accurately is obtained. In general, the above epoxy resin preferably contains an epoxy resin having a polar group. Further, when the adhesive layer laminated on one side of the divided semiconductor wafer is stretched, the property of cutting the adhesive layer may be referred to as splitting property. The above epoxy resin is preferably one having a polar group and having a cyclic hydrocarbon skeleton. The polar group of the epoxy resin may, for example, be a hydroxyl group, an amine group, an imido group, a decylamino group, a nitrile group, a carboxyl group or a carbonyl group. The polar group is preferably a hydroxyl group, an imido group or a nitrile group, from the viewpoint of further improving the adhesion of the adhesive layer to the semiconductor wafer and the subsequent member. By using an epoxy resin having a hydroxyl group, an imido group and a nitrile group, the curing reactivity can be lowered during storage in the adhesive layer, and the polar group can be easily maintained after storage. The above epoxy resin preferably has a free polar group. The above-mentioned "freedom" means that the polar group does not exist as a part of the bond skeleton in the main chain and exists in the side chain or the end. The epoxy resin is preferably included in the viewpoint of further improving the adhesion of the cured product and the splitting property of the adhesive layer. <> (: (at room temperature) is a liquid epoxy resin. From the viewpoint of further improving the adhesion of the cured product and the splitting property of the adhesive layer, the epoxy resin preferably contains the above The polar base of the epoxy resin and the epoxy resin which is liquid in the form of 23 scoops. The molecular weight of the epoxy resin is preferably less than 10,000. The so-called I54861.doc 201137020 epoxy resin "molecular weight" When the epoxy resin is not a polymer and the structural formula of the epoxy resin is determined, it means a molecular weight which can be calculated according to the structural formula, when the epoxy resin is a polymer. Refers to the weight average molecular weight. The content of the epoxy resin having the above polar group is preferably 10 to 100% by weight in the 100% by weight of the epoxy resin. The epoxy resin may all be a ring having the above polar group. Oxygen resin. A preferred lower limit of the content of the epoxy resin having the above-mentioned polar group is 30% by weight or more, and more preferably 80% by weight or more, based on 100% by weight of the epoxy resin. Oxygen tree The content satisfy the aforementioned lower and upper limits, it can be further improved adhesive properties of the cured product of the adhesive and the sticky layers separated. To 100% by weight of the epoxy resin, to above 23 <) (The content of the liquid epoxy resin is preferably 10 to 100% by weight. The epoxy resin may be all epoxy resin which is liquid at 23 ° C. The resin is 100% by weight, and the above is in the range of 23. The lower limit of the content of the liquid epoxy resin is 10% by weight, and the upper limit is more preferably 40% by weight. ^ If the above is liquid at 23 C When the content of the epoxy resin satisfies the above lower limit and the upper limit, the adhesion of the cured product and the splitting property of the adhesive layer can be further improved. [The first and second epoxy group-containing acrylic resins] The present invention The epoxy group-containing acrylic resin contained in the curable composition is not particularly limited as long as the weight average molecular weight is 100,000 or more, 40,000 or less, and the glass transition temperature is 6 Torr or more. The second epoxy group-containing acrylic resin contained in the curable composition of the invention has a weight average molecular weight of 10,000 or more and 20,000 or less, and a glass transition temperature of 154,861. Doc •12· 201137020 Above 60°C, there is no special limit. The above-mentioned second and second epoxy group-containing acrylic resins may have an epoxy group at the terminal or an epoxy group in the side chain (lateral position). Each of the first and second epoxy group-containing acrylic resins may be used alone or in combination of two or more. By using not only the above-mentioned first oxy group-containing acrylic resin having a relatively large weight average molecular weight but also the above second epoxy group-containing acrylic resin having a relatively small weight average molecular weight, and by using When the content of the first and second epoxy group-containing acrylic resins is within the above specific range, the positional accuracy can be improved when the adhesive layer attached to the divided semiconductor wafer is stretched. The adhesive layer is cut. That is, it is convenient to stretch the adhesive layer at normal temperature (23 ° C), and the adhesive layer can be cut with high precision. Further, by using the second epoxy group-containing acrylic resin, when the adhesive layer formed of the curable composition is laminated and subsequently adhered to the target member, the adhesion can be improved, and It suppresses warpage on the semiconductor wafer or cracks in the hardened adhesive layer. Further, by using the first and second epoxy group-containing acrylic tree lanthanum, the film forming property before curing can be increased, and the mechanical strength, heat resistance and flexibility of the cured product can be obtained. Raise. The epoxy group-containing acrylic resin is obtained, for example, by an acrylic acid monomer and an acrylic acid having no epoxy group. Examples of the acrylic monomer having an epoxy group include glycidol acrylate and glycidyl methacrylate. I54861. Doc • 13-201137020 The above-mentioned acrylic acid-free compound having no epoxy group may, for example, be ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate or isopropyl acrylate. Usually, an acrylic resin (acrylic polymer) is often produced by a solution polymerization method using a solvent as a medium. In the solution polymerization method, when a high molecular weight acrylic resin is produced, the viscosity of the solution is extremely increased or gelation occurs depending on the case. Therefore, it is difficult to obtain a high molecular weight acrylic resin. Further, in the solution polymerization method, since the unreacted monomer tends to remain, it is necessary to remove the residual monomer together with the solvent, which complicates the production steps. For example, if Glycidyl methacrylate (GMA, Glycidyi methacrylate) is used as an acrylic monomer having an epoxy group and a large amount of GMA is added to other acrylic monomers to carry out solution polymerization, agglutination by the epoxy group itself is carried out. Only the epoxy group-containing acrylic resin having a relatively low molecular weight (less than 1 Å) can be obtained. If a high molecular weight epoxy group-containing acrylic resin is to be obtained, it is likely to cause an extremely high viscosity increase or gelation as described above. On the other hand, when the above-mentioned GMA or the like is used, an epoxy group-containing acrylic resin is produced by a suspension polymerization method using water or a non-solvent as a medium, whereby a large amount of epoxy groups can be obtained, a molecular weight distribution is narrow, and a high molecular weight is obtained. An epoxy-based acrylic resin. The epoxy group-containing acrylic resin is a clean resin in which almost no monomer remains. Further, in the above method, the separation operation from the polymerization system is also easy, and the manufacturing steps are simplified. Therefore, the first epoxy group-containing acrylic resin is preferably 154861. Doc •14- 201137020 An epoxy-based acrylic resin obtained by suspension polymerization. By using the first epoxy group-containing acrylic resin obtained by the suspension polymerization method, the mechanical strength, heat resistance and flexibility of the cured product can be further improved. The weight average molecular weight of the first epoxy group-containing acrylic resin is A1G or more and 4 million or less. When the weight average molecular weight of the first epoxy group-containing acrylic acid is less than 100,000 Å, the film forming property is deteriorated, and it is difficult to treat the sheet formed of the curable composition in a sheet form or Adhesive layer. When the weight average molecular weight of the epoxy group-containing acrylic resin of the above second layer exceeds 400,000, the sheet or the adhesive layer before curing becomes too hard. Therefore, the splitting property of the adhesive layer is deteriorated. Further, the cured product becomes too hard and cracks are likely to occur in the cured product. The lower limit of the weight average molecular weight of the epoxy group-containing acryl-based resin of the above second embodiment is preferably 20,000, preferably 300,000. The second epoxy group-containing acrylic resin has a weight average molecular weight of 10,000 or more and 20,000 or less. When the weight average molecular weight of the second epoxy group-containing acrylic resin is less than 10,000, the film formability is deteriorated, and it is difficult to treat the sheet or the adhesive formed of the curable composition in a sheet form. Floor. When the weight average molecular weight of the second epoxy group-containing acrylic resin exceeds 20,000', the sheet or the adhesive layer before curing becomes too hard. Therefore, the splitting property of the adhesive layer is deteriorated. Further, the cured product becomes too hard, and cracks are likely to occur in the cured product. The glass transition temperature of the first and second epoxy group-containing acrylic resins is 60 °C or higher. If the glass transition temperature of the second and second epoxy group-containing acrylic trees is less than 6 ° C, the curable composition is formed by 154861. Doc •15- 201137020 The tensile elongation characteristics of the sheet or adhesive layer are reduced. Specifically, the fracture stress becomes too high or the elongation at break becomes too high. A preferred lower limit of the glass transition temperature of the above-mentioned second and second oxy-containing acrylic resins is 70 C. The glass transition temperature of the epoxy group-containing acrylic resin of the above first and second groups is preferably 10 Torr or less. When the glass transition temperature of the second and second epoxy group-containing acrylic resins satisfies the above upper limit, the sheet or the adhesive layer can be appropriately stretched to cut the sheet or the adhesive layer. For example, in the case of obtaining a semiconductor wafer with an adhesive layer, when the laminate is laminated on the adhesive layer on one side of the divided semiconductor wafer, the adhesive layer can be accurately cut. The epoxy resin equivalent of the first and second epoxy group-containing acrylic resins is preferably 200 to ffe. When the epoxy equivalent of the above-mentioned third and the epoxy group-containing (tetra) acid-based resin exceeds 200, the exchangeability of the cured product is sufficiently improved. When the epoxy equivalent of the first or second epoxy group-containing acrylic resin is 〇〇 or less, the heat resistance and flexibility of the cured product are further improved. In the total of 100% by weight of the component X of the epoxy resin, the first epoxy group-containing acrylic resin, and the second epoxy group-containing acrylic resin, the above is stated! The content of the epoxy group-containing acrylic resin is 10 to 40 parts by weight. The first one is the total (10% by weight) of the above components. A lower limit of the content of the epoxy group-containing acrylic resin is 15% by weight. The upper limit is preferably 35% by weight. If the content of the epoxy group-containing acrylic acid = resin exceeds the above lower limit and upper limit, It is possible to further improve the film-forming property of the hardened sheet, the rationality of the sheet, and the hardened material after hardening, and then the sheet or the adhesive layer can be appropriately stretched, and the I5486I is cut. Doc 201137020 A sheet or adhesive layer. Further, when the semiconductor wafer is laminated using the adhesive layer formed of the curable composition and then adhered to the target member, the semiconductor wafer is less likely to be surface-baked and peeled off, and the mechanical strength and heat resistance of the cured product are The flexibility is further improved to suppress cracking in the cured adhesive layer. In the epoxy resin, the epoxy group-containing acrylic resin, the second epoxy group-containing acrylic resin, the total amount of the 5% by weight of the epoxy resin, and the second The content of the epoxy group-containing acrylic resin is 4 by weight. The lower limit of the total content of the above-mentioned component X is _, and the lower limit of the content of the second methoxy group-containing acrylic resin is 5% by weight. The upper limit is more preferably 30% by weight. When the content of the second epoxy group-containing acrylic resin satisfies the above lower limit and the upper limit, the sheet formability before the hardening, the rationality of the sheet, and the cured product after the hardening can be further improved. Follow-up. Further, the sheet or the adhesive layer may be appropriately stretched to cut the above-mentioned sheet or adhesive layer. Further, when the semiconductor wafer is laminated using the bonding (four) layer formed of the curable composition and then the clearing of the target member, the germanium conductor wafer is hard to be warped and peeled off, and the mechanical strength and heat resistance of the cured product are hardened. Increased flexibility and flexibility can inhibit cracking in the hardened adhesive layer. [Nano Filler] The hardening composition of Ming has a naphthene (four) material. The material is not particularly limited as long as it is a size. The above-mentioned nano fillers may be used alone or in combination of two or more. The above nano filler has a viscosity-increasing effect and also functions as a tackifier. I54861. Doc 201137020 The use of the second epoxy group-containing acrylic resin described above tends to cause a hardening composition and a sheet or an adhesive layer formed of the curable composition to easily flow excessively during heating and melting. In the curable composition of the present invention, in addition to the use of the second epoxy group-containing acrylic resin, a nano filler is also used, so that the curable composition and the sheet formed of the curable composition can be used. The fluidity of the material or adhesive layer during heating and melting is controlled within a preferred range. Therefore, when the curable composition or the adhesive layer is used in the subsequent step, the fluidity of the adhesive layer during heating and melting can be controlled to a preferred range, so that the binding of the semiconductor wafer before curing can be improved, and the adhesion can be improved. The adhesion of the hardened material after hardening. Examples of the above nano filler include ceria, alumina, and calcium carbonate. The above nano filler is preferably cerium oxide having less impurities such as an alkali metal or a transition metal. The average particle diameter of the above nano filler is 1 nm or more and less than 1 〇〇〇 nm. A preferred lower limit of the average particle diameter of the above nano filler is 5 nm, a preferred upper limit is 300 nm', and a higher limit is 100 nm, and a more preferred upper limit is 5 〇 nm. The average particle diameter of the above nano filler is preferably 1 〇〇 nm or less. When the average particle diameter of the above-mentioned nano filler satisfies the above lower limit, when the curable composition or the adhesive layer is used in the subsequent step, the fluidity of the adhesive layer during heating and melting can be controlled to a preferred range. Increasing the binding of the semiconductor wafer before hardening can improve the adhesion of the cured product after hardening. When the average particle diameter of the above-mentioned nanofiller satisfies the above upper limit, the thickness unevenness of the sheet or the adhesive layer formed of the curable composition can be reduced. Further, if the average particle diameter of the above nano filler is 300 nm or less, the splitting property is further improved, 154,861. Doc -18- 201137020 The average particle size of the two non-rice fillers is less than 1〇〇(10) and the splitting is obvious & Further, it can correspond to the thinning of the above-mentioned sheet or adhesive layer. For example, even if the thickness of the sheet or the adhesive layer is 1 (four) to 20, the thickness unevenness can be reduced, and a high adhesion can be exhibited. The above-mentioned + uniformity of the month refers to the average primary particle size measured by a transmission electron microscope. The "average particle diameter" of the above-mentioned nanofiller was determined by observing an arbitrary number of nanofillers by a transmission electron microscope and calculating the average number of measured particle diameters. Further, the particle diameter measured by observation using a transmission electron microscope refers to the diameter (diameter) of an approximate circle when the nanofiller is approximated to a circular shape. The content of the above nano filler is preferably from 1 to 30 parts by weight based on 100 parts by weight of the epoxy resin. A lower limit of the content of the above nano filler is 5 parts by weight, more preferably 2 parts by weight, based on 1 part by weight of the epoxy resin. When the content of the above-mentioned nano filler satisfies the above lower limit and the upper limit, the fluidity of the curable composition and the sheet or the adhesive layer formed of the curable composition during heating and melting can be controlled to a better range. The adhesion of the cured product can be further improved. When the curable composition or the adhesive layer is used for the subsequent step, the fluidity of the adhesive layer during heating and melting can be controlled to a better range, so that the binding of the semiconductor wafer before curing can be improved, and the hardening can be improved. The adhesion of the hardened material. [Hardening Agent for Epoxy Resin] Examples of the curing agent for epoxy resin include a heat curing type acid anhydride type curing agent such as a trialkyltetrahydrophthalic acid needle, a phenol type curing agent, and an amine curing agent. And latent hardeners such as dicyandiamide, and cationic catalyst type 154861. Doc • 19· 201137020 Hardener, etc. The above-mentioned hardening agent may be used alone or in combination of two or more. Specific examples of the heat curing type acid anhydride-based curing agent which is liquid at normal temperature include, for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methylic acid anhydride. An acid anhydride-based curing agent such as trialkyltetrahydrophthalic anhydride. Among them, since hydrophobization is carried out, mercaptoic acid anhydride and trialkyltetrahydrophthalic anhydride are preferably used. The hardener and the hardening accelerator may be used in combination in order to adjust the curing speed or the physical properties of the cured product. The hardening accelerator is not particularly limited. Examples of the curing accelerator include an imidazole-based curing accelerator and a tertiary amine-based curing accelerator. In the case where the imidazole-based hardening accelerator is used, the curing rate and the physical properties of the cured product can be easily adjusted. The above-mentioned hardening accelerator may be used alone or in combination of two or more. The imidazole-based hardening accelerator is not particularly limited. Examples of the imidazole-based hardening accelerator include cyanoethyl-2-benzimidazole which is a cyanoethyl-protected imidazole, and a trade name "2MAOK-PW" which protects alkaline with iso-cyanuric acid. (Manufactured by Shikoku Chemical Industry Co., Ltd.). The imidazole-based hardening accelerator may be used alone or in combination of two or more. The above-mentioned curing agent is used in an appropriate amount depending on the type of the epoxy resin and the curing agent, the amount of the epoxy resin, and the like. The amount of the hardener to be added and the amount of the acid anhydride-based hardener to be used in combination with an acid anhydride-based curing agent such as an imidazole-based curing accelerator are preferably theoretically equivalent to the epoxy group. 60~100% 'better than 70~9〇%. If the addition amount of the acid anhydride hardener exceeds the required excess, there is chlorine ion from the hardened material by 154861. Doc -20- 201137020 Dissolution. By setting the content of the above-mentioned curing agent to an appropriate range, the curable composition can be effectively cured, and the residue derived from the curing agent can be hardly generated in the cured product. The content of the hardening accelerator is preferably 0% by weight based on 100 parts by weight of the above hardener. 5 to 20 parts by weight. When the content of the hardening accelerator is at least the above lower limit, the curable composition can be effectively cured. When the content of the curing accelerator is not more than the above upper limit, the curing accelerator is less likely to remain, and the bonding reliability of the cured product can be improved. [Other components] The curable composition of the present invention may contain rubber particles, a thermoplastic resin, a thermosetting resin other than an epoxy resin, an adhesion improving agent, a pH adjusting agent, an ion trapping agent, a viscosity adjusting agent, and the like, if necessary. Thixotropic agent, antioxidant, heat stabilizer, light stabilizer, wire absorbent, colorant dehydrating agent, flame retardant, antistatic agent, antifungal agent, preservative and solvent. [Details of Curable Composition] The curable composition of the present invention is preferably an adhesive. Preferably, the curable composition comprising the above epoxy eucalyptus, the above-mentioned epoxy resin hardener, the second and second epoxy group-containing acrylic resin, and the nano filler is adhesive before curing. And an adhesive that exhibits adhesion after hardening. Since the curable composition of the present invention is excellent in handleability, it is preferably formed into a sheet shape, and is preferably a sheet-like adhesive (adhesive layer). When the curable composition of the present invention is formed into a sheet form to obtain a sheet, the sheet has a breaking stress at 23 ° C of preferably 6 MPa or less. 154S61. Doc -21 · 201137020 The upper limit of the fracture stress is 4 MPae. On the other hand, the fracture stress is preferably 1 MPa or more. If the fracture stress satisfies the above upper limit, the sheet or the adhesive layer can be further split. Sex. If the above fracture stress satisfies the above lower limit, the film forming efficiency of the sheet or the adhesive layer can be improved, and the rationality of the sheet or the adhesive layer can be further improved. When the curable composition of the present invention is formed into a sheet form to obtain a sheet, the sheet has a degree of elongation at break at 23 ° C of preferably 2% or less. The upper limit of the elongation at break is preferably 1.0%, and more preferably the upper limit is 50%. On the other hand, the above-mentioned elongation at break is preferably 1% or more. If the above elongation at break satisfies the above upper limit, the splitting property of the sheet or the adhesive layer can be further improved. If the above-mentioned elongation at break satisfies the above lower limit, the film forming efficiency of the sheet or the adhesive layer can be improved, and the rationality of the sheet or the adhesive layer can be further improved. When the curable composition of the present invention is formed into a sheet form to obtain a sheet, when the sheet is cured, the sheet is heated from 4 ° C to 200 ° C at a temperature increase rate of 5 ° C /min, 40 ° The lowest melt viscosity at 200 ° C is preferably 1 〇〇〇 Pa. Above s. The minimum melt viscosity at 40 to 200 ° C is preferably 15 〇〇 Pa. More than s, and more preferably 2000 Pa. s above. On the other hand, the above minimum melt viscosity is preferably 20,000 Pa. s below. When the minimum melt viscosity satisfies the above lower limit ′, when the curable composition or the adhesive layer is used in the subsequent step, the fluidity of the curable composition or the adhesive layer during heating and melting can be controlled to a preferred range. The binding of the semiconductor wafer before hardening can be improved, and the adhesion of the cured product after hardening can be improved. In particular, if the lowest melt viscosity at 40 to 200 ° C above is 1500 pa_s or more, then the hardened material is 154861. Doc -22· 201137020 The attendance is significantly improved. When the minimum melt viscosity satisfies the above upper limit, the adhesion of the cured product can be further improved. Further, when the surface of the target member has irregularities, the sheet or the adhesive layer formed of the curable composition can be sufficiently filled in the concave portion of the surface to form a void. The above minimum melt viscosity is 40 to fine. The value under c. The reason for this temperature range is that when the curable composition and the sheet or the adhesive layer formed of the curable composition are cured, the crucible or the like is applied from a normal temperature to about 200 °C. The hardened product of the hardenable composition of the present invention preferably has a storage modulus of 40 MPa or more under the 丨8 〇. A lower limit of the storage elastic modulus is 100 MPa. On the other hand, the storage elastic modulus is preferably 1000 MPa or less. If the storage elastic modulus satisfies the above upper limit, the hardness does not become too hard, and the flexibility and the joint reliability can be further improved. When the storage elastic modulus satisfies the lower limit, the rigidity of the cured product of the adhesive layer and the laminated body of the semiconductor wafer can be improved by the high elasticity of the cured product, and the ultrasonic bonding in the wire bonding step can be efficiently performed. . The curable composition of the present invention can be used for joining various subsequent member members. The curable composition of the present invention can be preferably used for the purpose of following a semiconductor wafer to a subsequent object member. As the above-mentioned receiver member, a substrate can be cited. , semiconductor wafers and wire racks. The above-mentioned succeeding member is preferably a substrate or a semiconductor wafer. Examples of the substrate are ceramic substrates, resin substrates, broken substrates, semiconductor substrates, and glass substrates. 154861. Doc • 23- 201137020 (Connection structure) As described above, the curable composition of the present invention can be preferably used for the purpose of attaching a semiconductor wafer to a subsequent member. In Fig. 6, a connection structure using a curable composition of one embodiment of the present invention is schematically shown in a sectional view. The connection structure 51 shown in the figure includes a semiconductor wafer 52, a subsequent target member 53, and a cured layer 54 disposed between the semiconductor wafer 52 and the target member 53. The cured layer 54 is made of the curable composition. Formed by hardening. Next to the cured layer 54 is a semiconductor wafer 52 followed by a target member 53. When the joined structure 5 1 is obtained, the curable composition may be formed into a sheet form and used in the form of a sheet, which may also be used in the form of a liquid or sheet-like adhesive. In the bonded structure 51, the cured layer 54 is formed by curing the curable composition, and since the cured layer 54 has high adhesion, the connection reliability is excellent. (Cut-bonded-bonded ribbon) The diced-bonded ribbon of the present invention comprises an adhesive layer formed of the above-mentioned curable composition, and a dicing layer laminated on one side of the adhesive layer. Fig. 1 (a) and (b) are diagrams schematically showing a dicing-bonded crystal ribbon according to a first embodiment of the present invention. Fig. 1(a) is a partial missing plan view, and Fig. 1(b) is a partially missing front cross-sectional view along the I-Ι line in Fig. 1(a). The diced-adhesive ribbon 1 as shown in Figs. 1(a) and (b) has a strip-shaped release layer 2 . The adhesive layer 3, the substrate layer 4, and the dicing layer 5 are sequentially laminated on the upper surface 2a of the release layer 2. On the single side of the adhesive layer 3, that is, the first surface 3a is laminated with 154861. Doc • 24· 201137020 Substrate layer 4. The first surface 4a of the base material layer 4 is attached to the adhesive layer 3, and the second surface 4b on the opposite side of the first surface 4a of the base material layer 4 is attached to the crystal cutting layer 5. The second surface 3b on the opposite side of the first surface 3a of the adhesive layer 3 is a surface on which a semiconductor wafer is attached. A plurality of laminates including the adhesive layer 3, the base layer 4, and the crystal cut layer 5 are disposed at equal intervals on the upper surface 2a of the strip-shaped release layer 2. A protective sheet may be provided on the upper surface 2a of the release layer 2 on the side of the laminate. The planar shape of the adhesive layer 3, the base material layer 4, and the crystal cutting layer 5 is circular. The adhesive layer 3 is smaller than the release layer 2, the base material layer 4, and the crystal cutting layer 5 in plan view. The base material layer 4 is smaller than the release layer 2 and the crystal cut layer 5 in plan view. The cut layer 5 is smaller than the release layer 2 in plan view. The release layer 2 has a region which protrudes further laterally toward the outer peripheral side surfaces of the adhesive layer 3, the base material layer 4, and the crystal cutting layer 5. In the present embodiment, the base material layer 4 has non-adhesive properties. Therefore, the semiconductor wafer with the adhesive layer 3 can be easily peeled off from the base material layer 4 without irradiating UV (Ultravi〇let), reducing the adhesion and the like to modify the adhesive layer. The above-mentioned "non-adhesiveness" includes not only the case where the surface is not adhesive, but also the degree of adhesion which is not sticky when the surface is touched by the finger. 2 Specifically, the term "non-adhesive" means the substrate. The non-adhesive portion of the layer is attached to the stainless steel plate so that the peeling speed of the layer is such that when the substrate layer is peeled off, the adhesive force is 〇〇5ν/25_ amplitude or less. Further, the c layer 5 includes a substrate 5a and an adhesive layer laminated on one side of the substrate 5a. The dicing layer 5 has a region which is more prominent than the outer peripheral side of the adhesive layer 3 and the substrate layer 4. The dicing layer 5 is closed from the adhesive layer 5, in the protruding area 154861. Doc • 25· 201137020 is attached to the upper surface 2a' of the release layer 2 and attached to the second surface 4b of the base material layer 4 in the central region. At the time of dicing, a dicing ring is attached to the adhesive layer 5B of the dicing layer 5. Fig. 2 is a view schematically showing a diced-bonded ribbon according to a second embodiment of the present invention. Fig. 2(a) is a partial missing plan view, and Fig. 2(b) is a partially missing front cross-sectional view along the I-Ι line in Fig. 2(a). The dicing-bonding ribbon 11 shown in Figs. 2(a) and 2(b) is formed in the same manner as the dicing-bonding ribbon i except for the base layer and the diced layer. The diced-bonded ribbon 11 comprises a substrate layer 12 and a dicing layer 13. The adhesive layer 3, the base material layer 12 and the dicing layer 13 are sequentially laminated on the upper surface 2a of the release layer 2, and the base material layer 12 is laminated on the first surface 3a which is a single surface of the adhesive layer 3. The first surface 12a of the base material layer 12 is attached to the adhesive layer 3, and the second surface 12b on the opposite side of the first surface 12a of the base material layer 12 is attached to the crystal cutting layer 13. The planar shape of the base material layer 12 and the crystal cutting layer 13 is circular. The adhesive layer 3 is smaller than the release layer 2, the substrate layer 12, and the dicing layer 13 in plan view. The size of the base material layer 12 is substantially the same as the size of the crystal cutting layer 13 in plan view. The base layer 12 and the dicing layer 13 are smaller than the release layer 2 in plan view. The release layer 2 has a region which protrudes further laterally toward the outer peripheral side of the adhesive layer 3, the base material layer 12, and the crystal cutting layer 13. In the present embodiment, the base material layer 12 includes a non-adhesive non-adhesive portion 12A. The non-adhesive portion 12A is provided in a central region of the base material layer 12. The non-adhesive portion 12A is provided at a portion corresponding to the position of the adhesive layer 3 to which the semiconductor wafer is attached. The planar shape of the non-adhesive portion 12A is circular. The non-adhesive portion 12A is larger than the adhesive layer 3 when viewed from the top. Therefore, the non-adhesive part 154861. Doc •26· 201137020 12 A has a region that protrudes laterally toward the outer peripheral side of the more adhesive layer 3 . Therefore, when the adhesive layer 3 is attached to one side of the divided semiconductor wafer, the divided semiconductor wafer can be accurately aligned with the portion of the adhesive layer 3 to which the non-adhesive portion 12A is attached. After the attachment, the non-adhesive portion 12A can be surely disposed on the second surface 3b of the adhesive layer 3 attached to the divided semiconductor wafer. Therefore, after the adhesive layer 3 is cut, the step of modifying the adhesive layer without lowering the adhesion or the like to the semiconductor wafer with the adhesive layer 3 can be carried out, and the non-adhesive layer from the substrate layer 12 can be removed. The portion 12A is easily peeled off. Therefore, the production loss can be reduced, and the yield can be improved. The base material layer 12 includes an adhesive portion 12B having adhesiveness in a region of the outer portion of the non-adhesive portion 12A. The adhesive portion 12B is annular. The substrate layer 12 is coated with the adhesive layer 3. The non-adhesive portion 12A of the base material layer 12 is attached to the first surface 3a of the adhesive layer 3, and the adhesive portion 12B of the base material layer 12 is attached to the upper surface 2a of the release layer 2. The non-adhesive portion 12A of the substrate layer 12 is provided over the entire surface area of the adhesive layer 3. The adhesive portion 12B is not laminated on the surface of the adhesive layer 3. At the time of dicing, a dicing ring is attached to the adhesive portion 12B of the base material layer 12. The non-adhesive portion 12A of the base material layer 12 and the adhesive portion 12B are integrally formed. The non-adhesive portion 12A and the adhesive portion 12B are formed of the same material and are not formed of different materials. The dicing layer 13 is composed only of a substrate and does not include an adhesive layer. Instead of the dicing layer π, a dicing layer 5 can also be used. The release layer 2 is, for example, a release film. The release layer 2 is for protecting the second surface 3b of the adhesive layer 3 to which the semiconductor wafer is attached. Further, the release layer 2 may not be used. 154861. Doc -27- 201137020 The material constituting the release layer 2 is a polyester resin such as polyethylene terephthalate resin; polytetrafluoroethylene resin, polyethylene resin, polypropylene, resin, and polyfluorene. Polystyrenes such as ketone resin and polyethylene acetate vinegar resin are known as N曰, plastic resins such as polystyrene resin and polyimine resin. The surface of the release layer 2 can also be subjected to mold release treatment. The release layer may be a single layer or a plurality of layers. In the case where the release layer is a plurality of layers, the layers may be formed of different resins. The thickness of the release layer 2 is preferably from 1 to 1 in terms of further improving the rationality or releasability of the release layer 2. Within the range of 〇〇μπΐ2, more preferably within the range of 25~5〇μπι. The adhesive layer 3 is a layer used in the die bond of a semiconductor wafer. The adhesive layer 3 is used to bond the semiconductor wafer to a substrate or other semiconductor wafer or the like. The adhesive layer 3 is formed of the above curable composition. The diced-bonded ribbons 1, 11 are used to obtain a semiconductor wafer with an adhesive layer 3. After the semiconductor wafer with the adhesive layer 3 is obtained, the obtained semiconductor wafer with the adhesive layer 3 is laminated on the substrate member such as the substrate from the adhesive adhesive layer 3 side. Thereafter, heat or light is applied to harden the adhesive layer 3, whereby the semiconductor wafer can be firmly bonded to the subsequent target member via the adhesive layer 3. The thickness of the adhesive layer 3 is not particularly limited. The thickness of the adhesive layer 3 is preferably in the range of 1 to 100 μm. The lower limit of the thickness of the adhesive layer 3 is 3 μπι, and the upper limit is 60 μηι. If the thickness of the adhesive layer 3 is within the above range, the attachment of the semiconductor wafer is relatively easy, and thus the semiconductor 154861. Doc • 28 - 201137020 The thinning of the body device corresponds. The base material layers 4 and 12 can be formed, for example, by using an active energy ray-curing type or a thermosetting type adhesive composition. In the case of using an active energy ray-curable composition, the amount of exposure of the active energy ray to the composition is locally adjusted, whereby local differences in the adhesion of the substrate layers 4, 12 can be caused. In order to make the substrate layer non-dot, it is sufficient to increase the amount of exposure of the active energy ray. In order to make the base material layer adhesive, it is sufficient that the active energy ray is not irradiated or the amount of irradiation of the active energy ray is reduced. The base material layers 4, 12 are preferably formed of a composition comprising an acrylic polymer. The base material layers 4 and 12 are preferably formed of a crosslinked body obtained by crosslinking a composition containing an acrylic polymer. At this time, the splitting property of the adhesive layer can be further improved. Moreover, the polarity of the substrate layers 4, 1 2, the storage elastic modulus or the elongation at break can be easily controlled and designed. The acrylic polymer is not particularly limited. The above acrylic polymer is preferably an alkyl (meth)acrylate polymer. As the (fluorenyl)alkyl acrylate polymer, a group having an alkyl group having 1 to 18 carbon atoms can be preferably used. By using a (mercapto)alkyl acrylate polymer having an alkyl group having 1 to 18 carbon atoms, the polarity of the substrate layers 4 and 12 can be sufficiently reduced, and the surface energy of the substrate layers 4 and 12 can be lowered. The peelability of the adhesive layer 3 from the substrate layers 4, 12 is improved. The above composition preferably comprises at least one of an active energy ray reaction initiator and a thermal reaction initiator, and more preferably an active energy ray reaction initiator. The active energy ray reaction initiator is preferably a photoreaction initiator. The above active energy rays include ultraviolet rays, electron beams, alpha rays, beta rays, 154861. Doc -29· 201137020 γ ray, x ray, infrared and visible light. Among these active energy rays, since the curability is excellent and the cured product is hard to deteriorate, it is preferably an ultraviolet ray or an electron beam. As the photoreaction initiator, for example, a photoradical generator, a photocation generator, or the like can be used. Examples of the thermal reaction initiator include a thermal radical generator and the like. In the above composition, an isocyanate crosslinking agent may be added to control the adhesion. The thickness of the base material layers 4 and 12 is not particularly limited. The thickness of the substrate layers 4, 12 is preferably in the range of 1 to 1 〇〇 μιη. The lower limit of the thickness of the substrate layers 4, 12 is 5 μηι, and the upper limit is 60 μηι. When the thickness of the base material layer 4' 1 2 satisfies the above preferred lower limit, the splitting property at the time of crystal cutting can be further improved, and if the thickness of the base material layers 4, 12 satisfies the above preferred upper limit, the thickness becomes more Uniformity can further improve the precision of the crystal cutting. The bismuth crystal layers 5, 13 are, for example, dicing films. Examples of the material of the base material 5Α and the dicing layer 13 of the dicing layer 5 include a polyester resin such as a polyethylene terephthalate resin; a polytetrafluoroethylene resin, a polyethylene resin, a polypropylene resin, and a poly A polyolefin resin such as a decylpentene resin or a polyvinyl acetate resin; a plastic resin such as a polyvinyl chloride resin or a polyimide resin. Among them, a polyolefin resin is preferably used because it has excellent elongation and a small environmental load. Examples of the material of the adhesive layer 5 of the dicing layer 5 include a propionic acid-based adhesive, a special synthetic rubber-based adhesive, a synthetic resin-based adhesive, and an rubber-based adhesive. Wherein ' is preferably an acrylic adhesive or a rubber adhesive, more preferably an acrylic adhesive, and more preferably a pressure sensitive acrylic acid 154861. Doc 201137020 Adhesive. When an acrylic adhesive is used, the adhesion of the adhesive layer 5B to the base material layer 4, the adhesion of the adhesive layer 5B to the dicing ring, and the re-peelability of the self-cutting ring can be improved. Further, the manufacturing cost of the adhesive layer 5B can be reduced. The thickness of the crystal cutting layers 5 and 13 is not particularly limited. The thickness of the dicing layer $ and 丨3 is preferably in the range of 10 to 200 μm. The lower limit of the thickness of the dicing layers 5 and 13 is 60 μm, and the upper limit is preferably 150 ηη. When the thickness of the dicing layers 5 and 13 is within the above range, the releasability from the release layer 2 and the elongation of the diced layers 5 and 13 can be further improved. Further, the thickness of the crystal cut layer 5 indicates the total thickness of the substrate 5 8 and the adhesive layer 5 . The dicing layer 5, i 3 can be used in the dicing-mucosity strips 1, 11. The dicing layers 5 and 13 may be omitted, and the substrate layers 4 and 12 may also serve as a dicing layer. In particular, in the dicing-bonding ribbon 11, the dicing ring can be attached to the adhering portion 12 of the base material layer 12, so that it is not necessary to attach the dicing ring to the dicing layer 13. Since the dicing ring is not attached to the dicing layer 13, the dicing layer 13 may not have an adhesive force. Therefore, the material and composition constituting the crystal cutting layer 13 can be selected from a wider range. In the case of dicing, the semiconductor wafer can be more effectively prevented from scattering and the like, and more uniform elongation can be obtained. Therefore, it is preferable to be on the opposite side of the side of the substrate layers 4 and 12 to which the adhesive layer 3 is attached. The surface is attached with a dicing layer 5. (Method for Producing Semiconductor Wafer with Adhesive Layer) Next, a semiconductor wafer t with an adhesive layer in the case of using the dicing-adhesive tape layer shown in Figs. 1(a) and 1(b) An example of the method will be described below. First, the dicing-bonding ribbon 1 and the laminated body 21 are prepared. 154861. Doc -31· 201137020 As shown in Fig. 3 (4), the laminated body 21 includes a divided semiconductor wafer 23 which is a protective sheet material layer formed on one side of the protective sheet 22. The protective sheet 22 is laminated on the single surface 23A of the divided semiconductor wafer 23, and the semiconductor wafer 23 is divided into individual semiconductor wafers. The planar shape of the semiconductor wafer η after the division is circular. Each of the steps shown in FIGS. 3(a) to 3(d) is obtained as follows. First, as shown in FIG. 3(a), a semiconductor wafer 23 is prepared. The semiconductor wafer 23A is a semiconductor wafer before division. The planar shape of the semiconductor wafer 23 is circular. The surface 23a of the semiconductor wafer 23A is divided into a matrix by stree 〇 to form a circuit for constituting each semiconductor wafer. As shown, the prepared semiconductor wafer 23A is diced from the surface 23a side. After dicing, the semiconductor wafer 23A is not divided" on the surface 23a of the semiconductor wafer 23A to form a useful portion to divide it into The slit 23c of each semiconductor wafer is used, for example, by a crystal cutting device having a blade that rotates at a high speed, etc. Next, as shown in FIG. 3(c), a protective sheet 22 is attached to the surface 23a of the semiconductor wafer 23A. Then 'grinding the semiconductor crystal The back surface 23b of the circle 23A thins the thickness of the semiconductor wafer 23 A. Here, the back surface 23b of the semiconductor wafer 23 A is ground to the portion of the slit 23c. Thus, as shown in Fig. 3(d), The laminated body 21. The back surface 23b of the semiconductor wafer 23A is preferably ground to the portion of the slit 23c. For the grinding, for example, a grinding machine such as a grinding machine having a grinding magnet or the like is used, 154861. Doc -32- 201137020 proceed. When the grinding is performed, the protective sheet 22 is attached to the surface 23a of the semiconductor wafer 23A, so that no grinding debris adheres to the circuit. Further, even if the semiconductor wafer 23A is divided into individual semiconductor wafers after grinding, the plurality of semiconductor wafers are not separated, but are attached to the protective sheet 22. After the laminated body 21 is obtained, as shown in Fig. 4 (a), the laminated body 21 is placed on the stage 25 from the side of the protective sheet 22. On the stage 25, an annular dicing ring 26 is provided at a position spaced apart from the outer circumferential side of the divided semiconductor wafer 23. The second surface of the exposed adhesive layer 3 is attached to the back surface 23b of the divided semiconductor wafer 23 while peeling off the release layer 2 of the dicing-bonding ribbon 1, or after peeling off the release layer 2. Thereby, the adhesive layer 3 is laminated on the one surface of the semiconductor wafer 23 after the division, that is, the back surface 23b. Further, the adhesive layer 5B of the exposed dicing layer 5 is attached to the dicing ring 26. Next, as shown in Fig. 4 (b), the divided semiconductor a circle 2 3 to which the adhesive layer 3 is attached is taken out from the stage 25 and inverted. At this time, the dicing ring 26 is taken out in a state of being attached to the adhesive layer 5B. The extracted semiconductor wafer 23 is inverted so that the surface 23a becomes upward, and placed on the other stage 27. Next, as shown in Fig. 5 (a), the protective sheet 22 is peeled off from the surface of the semiconductor wafer 23 after the division. After the adhesive layer 3 is adhered to the back surface 2 of the semiconductor wafer 23 after the division, the protective sheet 22 is peeled off before the adhesive layer 3 is stretched. When the protective sheet 22 is peeled off, it is easy to peel off, and the protective sheet 22 may be heated as needed. Among them, it is preferred that the adhesive layer 3 is not modified when the protective sheet 22 is heated. Next, as shown in FIG. 5(b), the adhesive layer 3 is stretched and cut. 154861. Doc • 33· 201137020 At this time, cutting is performed along the cut portion 23c of the divided semiconductor wafer 23, and the respective semiconductor wafers in the divided semiconductor wafer 23 are separated. Since the adhesive layer 3 is attached to the back surface 23b of the divided semiconductor wafer 23, the adhesive layer 3 can be cut along the dicing line 23c of the divided semiconductor wafer 23, that is, the dicing line. After the adhesive layer 3 is cut, a cut portion 3c is formed on the adhesive layer 3. Further, in the present specification, the stretching of the adhesive layer 3 is also referred to as cutting. In the operation of cutting (stretching) by stretching the adhesive layer 3, the dicing 'cut-grain-adhesive tape 丨 can also be used for stretching the adhesive layer 3 to perform cutting (cutting ρ for s, cutting) The crystal-adhesive ribbon is a splitting adhesive layer. As a method of stretching the adhesive layer 3, for example, the adhesive layer 3 and the substrate layer are lifted up from the lower side of the adhesive layer 3. And the dicing layer ^ is a method of imparting the force A shown in Fig. 5 (b). By imparting the force A, the adhesive layer 3, the base material layer 4, and the dicing layer 5 can be imparted with a force to the outside. Bi, B2' can stretch the adhesive layer 3. The adhesive layer 3 is formed of the above curable composition, and the curable composition contains an epoxy resin, a hardener for epoxy resin, and a specific third layer. The content of the 3 epoxy group-containing acrylic resin, the specific second epoxy group-containing acrylic resin, and the nano filler 'the above-mentioned correction and the second epoxy group-containing acrylic resin are the above specific ranges. Therefore, the stretched adhesive layer 3' can be accurately along the cut portion of the divided semiconductor wafer 23 The adhesive layer 3 is cut. Therefore, it is difficult to produce a defect of the adhesive layer 3 under the semiconductor wafer. Since it can be accurately cut, 154861. Doc -34- 201137020 1 The adhesive layer 3' can be used to improve the semiconductor crystal with the adhesive layer 3. Since it is difficult to produce the defect of the adhesive layer 3, it is possible to suppress the tilt of the semiconductor wafer by laminating the semiconductor wafer with the bonding (4) and then proceeding to the subsequent object member, and it is possible to improve the connection of the semiconductor wafer. σ is sinful. Further, it is possible to suppress warpage on the succeeding semiconductor wafer, and it is possible to suppress generation in the hardened adhesive layer by using the diced-bonded ribbon! When the adhesive layer 3 is cut, even if the adhesive layer 3 is modified, the adhesive layer 3 can be cut accurately. For example, in order to heat the adhesive layer 3, to heat and cool the adhesive layer 3, and to irradiate the laser light, the adhesive layer 3 can be cut accurately with high precision. It is preferred that the adhesive layer 3 is not modified before or during the stretching of the adhesive layer 3. Preferably, before or during stretching of the adhesive layer 3, the adhesive layer 3 is heated and cooled in order to modify the adhesive layer 3, and the laser light is irradiated and irradiated. . Preferably, before or during the stretching of the adhesive layer 3, τ ^ & does not perform the bonding of the adhesive layer 3 in order to modify the adhesive layer 3 (using this secret, & ',, (except for heating to peel off the protective sheet 22) and cooling and illuminating the laser light. 彳θ a 尤仁疋' can also modify the adhesive layer 3. The adhesive layer 3 is not modified. In the case of the singularity, the manufacturing efficiency of the semiconductor wafer with the adhesive layer 3 can be improved. After the adhesive layer 3 is diced, the semiconductor wafer is placed in the state in which the adhesive layer 3 is laminated. It is peeled off from the base material layer 4 together with the point and the test agent layer 3. Thus, the semiconductor wafer with the adhesive layer 3 can be attached to the adhesive layer 3. The use of the dicing-bonded ribbon 1 is used.彡g本屯's attached to the split semiconductor crystal 15486I. Doc • 35· 201137020 There is a non-adhesive substrate layer 4 ′ below the portion of the adhesive layer 3 of the circle 23, so that the pick-up property of the semiconductor wafer with the adhesive layer 3 can be improved. When the dicing-bonding ribbon 11 is used, the non-adhesive portion 12A of the substrate layer 12 is present under the portion of the adhesive layer 3 to which the divided semiconductor wafer 23 is attached, thereby also improving the adhesion. The pick-up property of the semiconductor wafer of the layer 3 is then followed. After the adhesive layer 3 is diced, the dicing layer 5 can be stretched before the semiconductor wafer with the adhesive layer 3 is peeled off from the substrate layer 4, thereby further increasing the interval between the semiconductor wafers. Further, when the adhesive layer formed of the above-described curable composition is used in the form of a monomer instead of the dicing-bonding ribbon, the above-mentioned curable composition is applied to the semiconductor wafer 23 after division. After the single-layer adhesive layer is laminated, the substrate layer 4 and the crucible 2 may be laminated on the adhesive layer. The present invention will be specifically described by way of examples and comparative examples, as needed, in the base layers 4 and 12, and further on the layered layer 5. The invention is not limited to the following examples. The following materials were prepared to form a curable composition. (1) epoxy resin stupoxy-based solid cyclic oxime resin ("M〇〇4F" manufactured by Mitsubishi Chemical (formerly Japan Ep〇xy ReShlS), having an epoxy equivalent of 925 g/eq and a molecular weight of less than 10,000. A free polar group, ie, a hydroxyl group, a ring-shaped solid epoxy resin ("HP-7200HH" manufactured by DIC Corporation has an epoxy equivalent of 282 g/eq, a molecular weight of less than 10,000 Å, no polar group), bisphenol A Liquid epoxy resin (" ΕχΑ 154861. Doc •36· 201137020 850CRP”'epoxy equivalent is 172 g/eq, molecular weight is less than 10,000, no polar group) (2) Hardener Sf-based hardener for epoxy resin (Mitsubishi Chemical (Old Japan Epoxy Resins) "YH-309" manufactured by the company) (3) Hardening accelerator. (2MAOK-PW) manufactured by Shikoku Chemicals Co., Ltd. (4) The epoxy resin containing epoxy group of the first epoxy group ("Marproof G-2050M" manufactured by Nippon Oil Co., Ltd. 'Epoxy equivalent: 34〇g/eq, weight average molecular weight: 200,000, glass transition temperature: 74t) Epoxy-based resin containing epoxy group ("Marproof G-1005SA"" epoxy manufactured by Nippon Oil Co., Ltd. Equivalent: 3300 g/eq, weight average molecular weight: 100,000 'glass transition temperature: 98 ° C) (5) Other epoxy-containing acrylic resin containing epoxy-based acrylic resin (Nagase) "SG-80H" manufactured by ChemteX), epoxy equivalent: 14700 g/eq, weight average molecular weight: 350,000, glass transition temperature: 11 ° C) (6) The 2nd epoxy group-containing acrylic resin contains Epoxy-based acrylic resin (Marproof G-0250S, manufactured by Oyster Oil Co., Ltd., epoxy equivalent: 310 g/eq, weight average molecular weight: 20,000, glass transition temperature: 74 ° C) Epoxy group-containing acrylic acid Resin (Marproof G-0150M, manufactured by Oyster Oil Co., Ltd., epoxy equivalent: 310 g/eq, Weight average molecular weight: 1 15486 丨. Doc •37· 201137020 Million 'glass transition temperature: 7 Γ(:) (7) Nano-filled water-free ultra-fine fine-grained bismuth dioxide eve (TΜkUyama company's "Μτ-10"' average Primary particle size 15 nm) Anhydrous ultrafine amorphous cerium oxide ("Dm_ 10" manufactured by Tokuyama Co., Ltd.' average primary particle size is 15 nm) SO C^2 (Admafine Silica, manufactured by Admatechs Inc., average once The particle size is less than 1000 nm 'the average particle size is 〇·5 μπι) S〇-C6 (Admafine Silica manufactured by Admatechs, the average particle size is 2. 2 μπι) Further, the average primary particle diameters of ΜΤ-10, DM-10 and SO-C2 were obtained by observing with a transmission electron microscope and calculating the average value of the measured particle diameters. Further, the average particle diameter of SO-C2 and SO-C6 means the median diameter measured by a laser diffraction type particle size distribution meter. (8) Other components Amine stone sheds coupling agent ("S320" manufactured by Chisso Co., Ltd.) (Example 1) A phenoxy-based epoxy resin (manufactured by Mitsubishi Chemical Corporation (formerly Japan Epoxy Resins) Co., Ltd.) "1004F") 45 parts by weight and bisphenol a type liquid epoxy resin ("EXA-850CRP" manufactured by DIC Corporation) 20 weight damage as an acid anhydride hardener for epoxy resin hardener (Mitsubishi Chemical (old Japan EpOXy Resins) amp Η 〇 〇 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑Containing epoxy 154861. Doc -38- 201137020 Marproof G-2050M based on acrylic resin (manufactured by Nippon Oil Co., Ltd.) 15 weight injury, Marpr〇〇f G-0150M as the second epoxy-containing acrylic acid resin (manufactured by the company) 20 parts by weight of anhydrous ultrafine amorphous cerium oxide ("ΜΤ-10" manufactured by Tokuyama Co., Ltd.) ι 重量 by weight of the nano filler, and an amine-based sinter coupling agent ("Chisso") S320") 1 weight injury was carried out by § weekly matching. The obtained formulation was added to mercaptoethyl ketone (MEK, Methyl ethyl ketone) so that the solid content became 5 wt%, and stirred to obtain a curable composition as an adhesive. (Examples 2 to 4 and Comparative Examples 1 to 3) The types and the amounts of the materials used in obtaining the above-mentioned formulations were changed as shown in the following Table 1, except that the results were obtained in the same manner as in Example 作为. A hardening composition of the subsequent agent. (Evaluation) (1) Evaluation of fracture stress, elongation at break, and minimum melt viscosity The curable composition of the examples and the comparative examples was applied to the surface by using a bar coater to have a thickness of 10 after drying. A mold-treated surface of a 50 μηι polyethylene terephthalate (pet, polyethylene terephthalate) sheet. Thereafter, it was dried at 100 ° C for 3 minutes to form a sheet into a sheet, and a sheet was obtained. The sheet was fabricated by thermal lamination to prepare a test piece for breaking stress and elongation at break (longitudinal 50 mm x transverse direction 1 mm x thickness 〇. 1 mm) and melt viscosity test piece (diameter 20 mmx thickness 0. 5 mm). Use the tensile s tester (Tensilon RTC- 154861 by Orientec). Doc •39- 201137020 13 l〇”), the fracture stress and elongation at break of the obtained test piece were measured at 23 ° C, a line spacing of 25 mm and a tensile speed of 300 mm/min. Using a rheometer ("VAR100" manufactured by Reologica Instrument AB), a parallel plate with a diameter of 20 mm, a frequency of 1 Hz, a deformation of 0·1%, a temperature of 40 °C to 200 °C, and a heating rate of 5 °C / min. Under the conditions, the viscosity of the test piece was measured. The minimum value of the melt viscosity was read in the range of 40 ° C to 200 ° C to be the lowest melt viscosity. (2) Evaluation of Storage Elastic Modulus The curable composition of the examples and the comparative examples was applied to a surface having a thickness of 50 μm by a release treatment using a bar coater in a thickness of 10 μπΐ2 after drying. A release treated surface of a polyethylene terephthalate (pet) sheet. Thereafter, at 100. (: drying for 3 minutes, forming the curable composition into a sheet shape, and obtaining a sheet. A test piece was prepared by laminating the sheet by thermal lamination (longitudinal 50 mm x lateral 3 mm x thickness 0. 5 mm). With 17 〇. The test piece was hardened by heating under the arm for 60 minutes to obtain a cured product. The obtained cured product was measured at 180 ° C using a dynamic viscoelastic device ("DVA-200" manufactured by IT Meter, and Control Co., Ltd.) at 25 to 300 ° C, 5 ° C / min, and 10 Hz. Stretch storage elastic modulus E,. (3) Fabrication of dicing-bonded ribbon The dicing-bonded ribbon of the shape shown in Fig. 1 was produced. 95 parts by weight of 2-ethylhexyl acrylate, 5 parts by weight of acrylic acid 2-ethylidene ethyl ester, and irgacure 65 作为 as a photo radical generating agent ("500/. ethyl acetate solution manufactured by Ciba_Geigy Co., Ltd.") 2 parts by weight and lauryl mercaptan (Lauryl merCaptan) 0. 01 parts by weight was dissolved in ethyl acetate to obtain 154,861. Doc -40· 201137020 Solution. The solution was irradiated with ultraviolet rays to carry out polymerization to obtain a solution of the polymer in ethyl acetate. Further, the solid content of the solution was adjusted to a weight ratio of 2 parts by weight to 2 parts by weight of 2-methacryloxyethyl isocyanate (Karenz®, manufactured by Showa Denko Co., Ltd.) to obtain (mercapto)acrylic acid. An acrylic copolymer of a resin crosslinked body. The acrylic copolymer has a weight average molecular weight of 700,000 and an acid value of 〇. 86 (mgKOH/g). 1 part by weight of the obtained acrylic copolymer, 2 parts by weight of U-324A (manufactured by Shin-Nakamura Chemical Co., Ltd., urethane acrylate oligomer), and lrgacure 651 (Ciba- as a photo-radical generating agent) 1 part by weight of Geigy Co., Ltd. was formulated, and it was dissolved in ethyl acetate to obtain a composition. This composition was applied onto a release PET film using an applicator, and dried by heating at 3 ° C for 3 minutes to form a film-like composition layer having a thickness of 5 Å. A release PET film was attached to the composition layer. Thereafter, the composition layer was irradiated with ultraviolet rays of 365 nm at 2000 mJ/cm 2 under a high pressure mercury lamp to form a non-adhesive substrate layer (thickness 5 〇 μηη) on the release PET film. Further, the curable composition obtained in the examples and the comparative examples was applied to PET3 8CS manufactured by Linde Co., Ltd. at a thickness of 40 μm by an applicator, and dried by heating at 110 ° C for 3 minutes. A layer of adhesive (thickness 40 μιη) was obtained. One of the release PET films attached to both sides of the substrate layer is peeled off to obtain a diameter of 306. 8 mm round substrate layer. The adhesive layer on the above pET38cs is processed into a diameter of 305. The 8 mm circle is attached to the substrate layer and the adhesive layer in a manner similar to the center of the circle. The release PET film adhered to one side of the substrate layer was peeled off and the crystal layer was cut (PE tape #6318-B (Shuishui Chemical I54861. Doc •41 - 201137020 Adhesive film made by the company, which is formed on the single side of a polyethylene substrate with a thickness of 70 μm, with a thickness of 橡胶 哗 rubber-based adhesive layer))) attached to the base from the adhesive layer side The material layer is attached to the pET38cs on the side of the adhesive layer of the dicing layer and the outer side surface of the substrate layer. Thus, a cleavage-bonded ribbon having a release layer, an adhesive layer, a substrate layer, and a day-cut layer is sequentially laminated. (4) Evaluation of splitting property, pick-up property and adhesion property As a material of a semiconductor wafer having a divided crystal before being ground, a protective sheet material and a wafer size of 10 mm square before grinding were used. A semiconductor wafer (a mirror-finished wafer having a diameter of 3 mm and a thickness of 4 Å. The crystallization of the dicing and viscous ribbon obtained in the above (3) dicing and viscous ribbon production The PET film is peeled off from the adhesive layer and the substrate layer to expose the adhesive layer and the outer peripheral portion of the substrate layer. At a temperature of 60 ° C, the back surface of the semiconductor wafer is laminated and adhered at a temperature of 60 ° C. The layer of the adhesive layer is attached to the dicing ring. Next, the divided semiconductor wafer to which the adhesive layer is attached is taken out from the platform and inverted, and placed on another platform. After that, the protective sheet is peeled off from the surface of the semiconductor wafer after the division at 6 〇t. At this time, the adhesive layer is not modified. Secondly, the use of a die bonder (bestem D-02 manufactured by Canon-machinery) ")" stretching the adhesive layer and substrate layer at 23 ° C and an extension of 5 mm Cut crystal layer 'and along the rear portion of the divided semiconductor wafer dicing cut adhesion adhesive layer, and each semiconductor wafer after 154,861 divided. Doc -42- 201137020 Semiconductor wafer separation. Secondly, the rubber collet size is 9 @ 9 mm square, the pin top output is 0. 3 mm and pin ejector speed 4 mm/sec strip, 4 wire & unloaded, continuously picking up 20 sticks with glue
劑層之半導體晶片後，於1 〇〇。广、s M + A 、woe、5 N之條件下將其黏 厚度1 mm之玻璃板上。 利用光學顯微鏡（倍率200倍）自玻璃板背面側觀察經黏 晶之晶片之黏接著劑層’以下述判定基準判定黏接著劑層 之割裂性（切割狀態）。 [割裂性①判定基準] 〇〇：於半導體晶片之下方，黏接著劑層無缺失 〇··於半導體晶片之下方，黏接著劑層梢有缺失(缺失 之最大長度未達50 μιη) ^ χ :於半導體晶片之下方，黏接著劑層稍有缺失（缺失之 最大長度為50 μηι以上且未達1〇〇 μιη) .於半導體ΒΒ片之下方，黏接著劑層存在缺失（缺失 之最大長度為100 μηι以上） X X X :無法割裂 又，拾取性係以下述判定基準進行判定。 [拾取性之判定基準] 〇 :不存在無法拾取之附帶黏接著劑層之半導體晶片 Χ:存在無法拾取之附帶黏接著劑層之半導體晶片 其次，將以上述方法拾取之27個附帶黏接著劑層之半導 體晶片於100°C ' 5 Ν之條件下，自黏接著劑層側黏晶於玻 璃環氧基板（大昌電子公司製造之「TPWB-S02」）上。其 154861.doc •43- 201137020 後，於170 C之太共箱内放置60分鐘，使黏接著劑層硬化而 形成硬化物層，獲得連接構造體。 將所得之連接構造體於30°C及70%之恆溫恆濕槽令放置 168小時後，利用回焊爐（Antom公司製造之「 5〇16F」）’於預熱160»c、最高255〇c之條件下，進行連接 構造體之耐回焊試驗。其後，利用超音波探傷裝置SAT(超 音波斷層掃描攝影裝置’ Scanning Acoustic Tomography) (Hitachi Kenki Fine Tech公司製造之「mi_scope」）觀察連 接構造體之黏接著劑層有無剝離，測量發現剝離之個數。 以下述判定基準判定所得連接構造體之接著性。關於此處 所見之剝離’由半導體晶片產生翹曲所引起之剝離係浮起 於半導體晶片之外周部，因此進行光學觀察，另一方面由 回焊熱所引起之剝離係產生於硬化物層之接著界面，因此 藉由上述SAT進行圖像觀察。 [接著性之判定基準] 〇.未產生半導體晶片之紐曲及硬化物層之龜裂，不存 在剝離之附帶黏接著劑層（硬化物層）之半導體晶片 x :產生半導體晶片之翹曲或硬化物層之龜裂，存在剝 離之附帶黏接著劑層（硬化物層）之半導體晶片 將結果示於下述表1中。再者，於下述表1中，「_」表示 未進行評價。 15486 丨.doc -44- 201137020 【1<】 比較例3 ΓΟ o — rn § 1200 X 〇 X 比較例2 >〇 v-i fO »n — rn 270 〇 〇 XX 〇 〇 比較例1 ro m m m 一 On ο <*<> 1200 XXX 1 1 實施例4 »T) m *r> VI o 一 σ\ CN ο ·—· 2000 g 〇 〇 〇 實施例3 m S «〇 o — 卜 νΐ s 3200 g 〇〇 〇 〇 實施例2 〇 »〇 m »n o (Ν 〇 o 一 rn 4200 ο 〇〇 〇 〇 實施例1 jn v> »Τϊ o - 〇 (N i 1 2430 σ\ 〇〇 〇 〇 1004F HP-7200HH EXA-850CRP YH-309 2MAOK-PW G-2050M G-1005SA SG-80H G-0250S ί G-0150M MT-10 ! DM-10 ,SO-C2 S0-C6 S320 MPa Pas MPa 割裂性 拾取性 接著性 環氧樹脂 環氧樹脂用硬化劑 1 硬化促進劑 第1之含環氧基之丙烯酸系樹脂 其他含環氧基之丙烯酸系樹脂 第2之含環氧基之丙烯酸系樹脂 填料 胺基矽烷偶合劑 斷裂應力 斷裂伸長率 最低熔融黏度 儲存彈性模數 調配成分(重 量份） 評價 -45- 154861.doc 201137020 【圖式簡單說明】 圖1 (a)及（b)係表示本發明之第1實施形態之切晶-黏晶帶 的部分缺失平面圖及部分缺失前視剖面圖。 圖2(a)及（b)係表示本發明之第2實施形態之切晶-黏晶帶 的部分缺失平面圖及部分缺失前視剖面圖。 圖3(a)〜(d)係用以對獲得製造附帶黏接著劑層之半導體 晶片時所使用之積層體之各步驟的一例進行說明之部分缺 失前視剖面圖。 圖4(a)〜(b)係用以對使用本發明之第丨實施形態之切晶_ 黏晶帶製造附帶黏接著劑層之半導體晶片之方法的—例進 行說明之部分缺失前視剖面圖。 圖5(a)〜(b)係用以對使用本發明之第丨實施形態之切晶_ 黏晶帶製造附帶黏接著劑層之半導體晶片之方法的一例進 行說明之部分缺失前視剖面圆。 圖6係模式地表示使用本發明之一實施形態之硬化性組 合物之連接構造體的剖面圖。 【主要元件符號說明】 1 ' 11 切晶-黏晶帶 2 脫模層 2a 上表面 3 黏接著劑層 3a、4a、12a 第1表面 3b、4b、12b 第2表面 3c 、 23c 切割部分 154861.doc 46- 201137020 4、12 基材層 5、13 切晶層 5A 基材 5B 黏著劑層 12A 非黏著部 12B 黏著部 21 積層體 22 保護片材 22a 單面 23 分割後半導體晶圓 23A 半導體晶圓 23a 表面 23b 背面 25、27 平台 26 切晶壤 51 連接構造體 52 半導體晶片 53 接著對象構件 54 硬化物層 154861.doc -47-After the semiconductor wafer of the layer, it is 1 〇〇. Wide, s M + A, woe, 5 N under the conditions of the thickness of 1 mm on the glass plate. The adhesive layer of the adhesive wafer was observed from the back side of the glass plate by an optical microscope (magnification: 200 times). The splitting property (cut state) of the adhesive layer was determined by the following criteria. [Cracking 1 criterion] 〇〇: Below the semiconductor wafer, there is no defect in the adhesive layer. · Below the semiconductor wafer, there is a defect in the adhesive layer (the maximum length of the defect is less than 50 μm) ^ χ : Below the semiconductor wafer, the adhesive layer is slightly missing (the maximum length of the defect is 50 μηι or more and less than 1 μμηη). Below the semiconductor wafer, the adhesive layer is missing (maximum length of the missing layer) It is 100 μηι or more) XXX : It cannot be split, and the pick-up property is judged based on the following criteria. [Criteria for Judging the Pickup] 〇: There is no semiconductor wafer with an adhesive layer that cannot be picked up. There are semiconductor wafers with an adhesive layer that cannot be picked up. Next, 27 adhesives will be picked up by the above method. The semiconductor wafer of the layer was adhered to a glass epoxy substrate ("TPWB-S02" manufactured by Dachang Electronics Co., Ltd.) from the adhesive layer side at 100 ° C '5 Ν. After 154861.doc •43-201137020, it was placed in a 170 C slab for 60 minutes to harden the adhesive layer to form a hardened layer to obtain a joined structure. The resulting joined structure was placed in a constant temperature and humidity chamber at 30 ° C and 70% for 168 hours, and then used in a reflow oven ("5〇16F" manufactured by Antom) to preheat 160»c, up to 255〇. Under the condition of c, the reflow-resistant test of the joined structure was carried out. Then, using the ultrasonic flaw detection apparatus SAT (Scanning Acoustic Tomography) ("mi_scope" manufactured by Hitachi Kenki Fine Tech Co., Ltd.), the adhesive layer of the bonded structure was observed for peeling, and the peeling was measured. number. The adhesion of the obtained joined structure was determined by the following criteria. Regarding the peeling seen here, the peeling caused by the warpage of the semiconductor wafer floats on the outer peripheral portion of the semiconductor wafer, so that optical observation is performed, and on the other hand, the peeling caused by the reflow heat is generated in the cured layer. Following the interface, image observation is performed by the SAT described above. [Criteria for determination of adhesion] 未. The crack of the semiconductor film and the crack of the cured layer are not generated, and the semiconductor wafer x with the adhesive layer (hardened layer) which is not peeled off is generated: warpage of the semiconductor wafer is generated or A semiconductor wafer having a cracked cured layer and a peeled adhesive layer (hardened layer) was shown in Table 1 below. Further, in Table 1 below, "_" indicates that evaluation was not performed. 15486 丨.doc -44- 201137020 [1<] Comparative Example 3 ΓΟ o — rn § 1200 X 〇X Comparative Example 2 >〇vi fO »n — rn 270 〇〇XX 〇〇Comparative example 1 ro mmm One On ο <*<> 1200 XXX 1 1 Example 4 »T) m *r> VI o a σ\ CN ο ·-· 2000 g 〇〇〇Example 3 m S «〇o — Bu ΐ s 3200 g 〇〇〇〇Example 2 〇»〇m »no (Ν 〇o rn 4200 ο 〇〇〇〇Example 1 jn v> »Τϊ o - 〇 (N i 1 2430 σ\ 〇〇〇〇1004F HP- 7200HH EXA-850CRP YH-309 2MAOK-PW G-2050M G-1005SA SG-80H G-0250S ί G-0150M MT-10 ! DM-10 ,SO-C2 S0-C6 S320 MPa Pas MPa Split picking continuity Epoxy resin epoxy resin hardener 1 hardening accelerator first epoxy group-containing acrylic resin other epoxy group-containing acrylic resin second epoxy group-containing acrylic resin filler amine decane coupling agent Fracture stress, elongation at break, lowest melt viscosity, storage elastic modulus, blending Ingredients (parts by weight) Evaluation -45-154861.doc 201137020 [Brief Description of the Drawings] Fig. 1 (a) and (b) show a partially missing plan and a portion of the dicing-bonded ribbon of the first embodiment of the present invention. Fig. 2 (a) and (b) show a partial missing plan view and a partially missing front cross-sectional view of the diced-adhesive tape according to the second embodiment of the present invention. Fig. 3 (a) ~ ( d) is a partially missing front cross-sectional view for explaining an example of each step of obtaining a laminate used in the production of a semiconductor wafer with an adhesive layer. Fig. 4 (a) to (b) are used for A partially missing front cross-sectional view for explaining a method of manufacturing a semiconductor wafer with an adhesive layer using a dicing-adhesive tape according to a third embodiment of the present invention. Fig. 5 (a) to (b) A portion of the method for producing a semiconductor wafer with an adhesive layer using the dicing-bonded ribbon of the embodiment of the present invention is partially omitted. Fig. 6 is a cross-sectional view schematically showing a connection structure using a curable composition according to an embodiment of the present invention. [Description of main components] 1 '11 dicing-bonded ribbon 2 Release layer 2a Upper surface 3 Adhesive layer 3a, 4a, 12a First surface 3b, 4b, 12b Second surface 3c, 23c Cutting portion 154861. Doc 46- 201137020 4,12 Substrate layer 5, 13 Cleavage layer 5A Substrate 5B Adhesive layer 12A Non-adhesive portion 12B Adhesive portion 21 Laminated body 22 Protective sheet 22a Single-sided 23 Divided semiconductor wafer 23A Semiconductor wafer 23a Surface 23b Back surface 25, 27 Platform 26 Cut grain 51 Connection structure 52 Semiconductor wafer 53 Next object member 54 Hardened layer 154861.doc -47-