201245376 六、發明說明： 【發明所屬之技術領域】 本發明關於能量線硬化型黏著劑及黏著片，更詳細地 說，關於可經三維伸長而立體成形的能量線硬化型黏著劑 及黏著片。 【先前技術】 樹脂成型品具有輕量性、透明性'容易成型等的優點， 使用於汽車元件及電器製品等的領域。但是，在將光學基 板等具有微細凹凸構造的片以樹脂成型而製作時，習知的 樹脂難以精確地良好成型微米層級的微細形狀。 適合形成微米層級的微細形狀之黏著劑，可列舉例如 專利文獻1、2所記載之放射線硬化性黏著劑。 專利文獻1提出由含有黏著性聚合物與放射線硬化性 成分為主成分之黏著劑所構成，具有黏著劑在23r的儲藏 彈I·生率（G )為IxlOPa以下、放射線硬化後在23^的儲藏 彈〖生率（G )為5xl〇6Pa以上之放射線硬化型黏著片。 專利文獻2提出由含有黏著性聚合物與放射線硬化性 成分為主成分之黏著劑所構成，具有黏著劑在23°C的線斷 儲藏彈性率（G，）為1xl〇6Pa以下、放射線硬化後在4(TC的 :伸儲藏彈性率(E )為2X1。7pa以上、放射線硬化後的黏 #片在8〇ς加熱1〇分鐘時的來自光聚合起始劑所產生的氣 體里為20 ν g/g(黏著劑）以下之放射線硬化型黏著片。 【先行技術文獻】 【專利文獻】 201245376 【專利文獻1】日本特開2003_30 1 147號公報 【專利文獻2】曰本特開2〇〇5_1 1 2966號公報 【發明内容】 【發明所欲解決之問題】 根據上述的放射線硬化型黏著片，將稜鏡片狀之具有 特定圖案形狀的片層積於黏著片，該圖案形狀轉印於點著 片，可獲得微細的凹凸形狀。然而，將此述之放射線硬化 型黏著片貼附於基台’依所欲之方法使黏著劑三維伸長進 行立體成型（包含凹凸構造的形成。以下相同。）的情形時， 會發生該黏著片自基台剝離的問題。又假設使用黏著片不 剝離的表面能量大的基台時，黏著劑在伸長過程中内聚破 壞（coheSlve faiiure)，產生無法獲得目標形狀的問題。 本發明鑒於此述之實際狀況，以提供適合三維伸長而立 體成型之能量線硬化型黏著劑及黏著片為目的。 【解決問題之技術手段】 為了達成上述目的，第一，本發明提供能量線硬化前 的斷裂延伸㈣2_%以上，能量線硬化前的應力鬆弛率 為7〇〜95%，能量線硬化前的凝膠分率為作為特徵之 能量線硬化型黏著劑（發明1 )。 上述發明（發明1)所述之能量線硬化型黏著劑滿足上 述物性，在該黏著劑貼附於基台而三維伸長立體成型之 時，抑制從基台的剝落或於成型過程中因内聚破壞的斷 裂’可成型為目標形狀。 上述發明（發明1)中，該能量線硬化型黏著劑較佳包 4 201245376 含（曱基）丙烯酸酯共聚物及能量線硬化型氨酯丙烯酸酯 (發明2)。 上述發明（發明2 )中，上述能量線硬化型氨酯丙烯酸 醋的含量’相對於上述（甲基）丙烯酸酯共聚物1〇〇質量 部’較佳為50~200質量部（發明3)。 上述發明（發明2、3 )中’上述（曱基）丙烯酸酯共聚物 的此量線硬化前的玻璃轉移溫度為-5〇~〇β(：，上述能量 線硬化型氨S旨丙稀酸自旨的能量線硬化前的玻璃轉移溫度 (Tg)為-40〜20C者為佳（發明4)。 上述發明（發明2〜4)中，上述能量線硬化型氨醋丙烯 iSs的旎量線硬化後的鉛筆硬度較佳為B~5B(發明㈧。 上述發明（發明2〜5)中，上述能量線硬化型黏著劑較 佳更包括交聯劑（發明6)。 上述發明（發明6)中，上述交聯劑的含量，相對於上 述（曱基）丙烯酸醋共聚物⑽質量部，較佳& uh.4 f 量部（發明7)。 上述發鳴明6、7)中，上述交聯劑較佳為異氰酸醋 系交聯劑（發明8)。 上述發明（發明2〜8)中，該能量線硬化型黏著劑較佳 更包括光聚合起始劑（發明9)。 上述發明（發明1〜9)所述之能量線硬化型黏著劑較佳 用於立體成型（發明1〇)。 ^述發明（發日月10)中，上述能量線硬化型黏著劑較佳 經由三維伸長後立體成型（發明11)。 201245376 第二，本發明提供以具有 ,1。 ’由上述量線硬化型黏著劑 (發明1〜11)所構成的黏著劑 別增為特徵之黏著片（發明12)。 第三’本發明提供以具有 ，由上述此量線硬化型黏著劑 (發明1〜11 )所構成的黏著劑層 有削層興包夾該黏著劑層的兩個剝 離片為特徵之黏著片（發明13)。 【發明效果】 根據本發明之能量線硬化型黏著劑，在貼附於基台的 黏者劑經三維伸長而立體成型之時，可抑制因黏著劑從基 台的剝落或於成型過程中因黏著劑的内聚破壞(cohere failure)所產生的斷裂，而可成型為目標形狀。 【實施方式】 以下對於本發明之實施型態進行說明。 [能量線硬化型黏著劑] 本實施型態所述之能量線硬化型黏著劑在能量線硬化 前的斷裂延伸率、應力鬆弛率及凝膠分率滿足下列要件， 根據此點，成為適合經三維伸長而立體成型（以下稱為「伸 長成型j )者。 具體地，本實施型態所述之能量線硬化型黏著劑的斷 裂延伸率為2000%以上，較佳為2200~4000%，特佳為 2400〜3500%。當斷裂延伸率為2〇〇〇%以上，在伸長成型之 時’黏著劑難以破裂。 此述斷裂延伸率的測定係以不具有基材等的單獨黏著 劑層進行，具體為，將成形為厚度5〇〇// m、寬15mm、長 55mm(其令測定的範圍為25mm)的黏著劑，在23°C、50%Rff 6 201245376 的環境下’以200mm/分的速度伸長來進行。 本實施型態所述之能量線硬化型點著劑的應力鬆地率 為70〜95%，較佳為75〜93%，特佳為8〇〜9ι%。當應力鬆” 為m以上時，容易保持黏著劑伸長的狀態，因此容易成型 為目標形狀。而當應力鬆弛率為95%以下時，可抑制在黏著 劑保持伸長狀態時除了用於伸長的力量以外的外力（例如 重力）使形狀更變形。 本說明書中所述之應力鬆他率為黏著劑在拉伸試驗中 伸長3議維持3〇〇秒後的應力鬆他率。具體地說，拉伸試 驗以成形為厚度50(^m、El5随、長55mm(其中測定的範 圍為25ram)的黏著劑，在23。〇、5〇%咄的環境下，以 分的速度伸長來進行。應力鬆弛率係基於3〇⑽伸長時 的應力A與伸長停止後的3〇〇秒的應力B，以下式算出。 應力鬆弛率（％) = { (A-B)/A}xl〇〇(%) 本實施態樣所述之能量線硬化型黏著劑的凝膠分率為 1〜30%，較佳為2〜2〇%，更佳為3〜1〇%。凝膠分率為1%以上 時，可抑制伸長成型時因内聚破壞所造成的黏著劑分裂。 當凝膠分率為3〇%以下時，可確保黏著劑的伸長。< 此述黏著劑的凝膠分率為貼附時（經過蝕刻期後）的 值。具體地說，將能量線硬化型黏著劑塗佈於剥離片，加 熱處理後二在23t、5〇%RH的環境下保存7日後的凝膠分 率。又霉占著劑的凝膠分率係測定钮刻期過後安定者，因此 在是否經過蝕刻期之不明確的情形時，可改以在23r、 50%RH的環境下保存7日後測定。 201245376 滿足上述各要件的能量線硬化型黏著劑較佳包含 (1)(甲基）丙烯酸酯共聚物及（2)能量線硬化型氨酯丙烯酸 酯’更佳為更包括（3)交聯劑及/或（4)光聚合起始劑。 (1)(曱基）丙烯酸酯共聚物 (曱基）丙烯酸酯共聚物沒有特別限制，可從習知作為 丙烯酸系黏著劑的樹脂成分之慣用的（曱基）丙烯酸酯共聚 物中適當選擇。此述（曱基）丙烯酸酯共聚物可列舉，例如 酯部分為碳數1 ~20烷基之（曱基）丙烯酸酯、與具有活性氫 的官能基之單體' 與視需要使用的其他單體之共聚物。本 說明書中，（曱基）丙烯酸酯表示丙烯酸酯與甲基丙烯酸酯 兩者。其他的類似用語也相同。 酯部分為碳數1〜20烷基之（曱基）丙烯酸酯可例如（曱 基）丙烯酸曱酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯、 (甲基）丙烯酸異丙酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸 辛酯、（曱基）丙烯酸異丁酯、（曱基）丙烯酸戊酯、（曱基） 丙烯酸己酯、（甲基）丙烯酸環己酯、（曱基）丙烯酸2-乙基 己酯、（曱基）丙烯酸異辛酯、（甲基）丙烯酸癸酯、（曱基） 丙烯酸十二酯、（甲基）丙烯酸十四酯、（甲基）丙烯酸十六 酯、（曱基）丙烯酸十八酯等。這些可1種單獨使用，也可 組合2種以上使用。 另一方面’具有活性氫的官能基之單體可例如（甲基） 丙烯酸2 -羥基乙酯、（甲基）丙烯酸2 -羥基丙酯、（曱基）丙 烯酸3-羥基丙酯、（甲基）丙烯酸2-羥基丁酯、（甲基）丙烯 酸3-羥基丁酯、（曱基）丙烯酸4-羥基丁酯等的（甲基）丙烯 8 201245376 酸羥基烷酯、（曱基）丙烯酸單甲基胺基乙酯、（曱基）丙稀 酸單乙基胺基乙酯、（甲基）丙烯酸單甲基胺基丙酯、（甲基） 丙烯酸單乙基胺基丙酯等的（曱基）丙烯酸單烷基胺基烧 酯；丙烯酸、甲基丙烯酸、巴豆酸、順丁烯二酸、衣康酸、 檸康酸等的乙烯性不飽和羧酸等。這些單體可單獨使用， 也可組合2種以上使用。 視需要使用的其他單體可例如乙酸乙烯酯、丙酸乙稀 酯等的乙烯酯類；乙烯、丙烯、異丁烯等的烯烴類；氯乙 烯' 二氣乙烯等的鹵化稀烴類；苯乙烯、α -甲基苯乙稀等 的苯乙烯系單體；丁二烯、異戊二烯、氣丁二稀 (chl〇roprene)等的二烯系單體；丙烯腈、甲基丙烯腈等的 腈系單體；丙烯醯胺、N-甲基丙烯醯胺、n，N-二曱基丙稀 醯胺等的丙烯醯胺類等。這些可單獨使用，也可組合2種 以上使用。 上述（曱基）丙烯酸酯共聚物之中，特別以分子内具有 能量線聚合性基者（所謂的加合（adduct)聚合物）為佳。使 (甲基）丙烯酸酯共聚物的分子内具有能量線聚合性基的方 法沒有特別限定，但例如可經由使具有含官能基的單體單 位之（曱基）丙烯酸酯共聚物（al)與具有與該官能基反應的 取代基之含不飽和基的化合物（a2)反應而得到。 (al)成分所包含的含官能基的單體單位較佳為丙烯酸 2-羥基乙酯、曱基丙烯酸2-羥基乙酯、丙烯酸2-羥基丙酯、 曱基丙烯酸2 -羥基丙酯等的含羥基的丙烯酸酯。 (a2)成分較佳為具有與（ai)成分的經基反應的官能基 201245376 以及具有聚合性雙鍵的化合物，例如曱基丙烯醯氧基乙基 異氰酸酯、異丙基-α，α-二甲基苄基異氰酸酯、甲基丙稀 醯基異氰酸酯、異氰酸烯丙酯、（曱基）丙烯酸縮水甘油酯； (曱基）丙烯酸等。 使用分子中具有能量線聚合性基之（曱基）丙烯酸酯共 聚物時，因為低分子量成分的能量線硬化型氨酯丙稀酸s旨 的使用量可減少，因此可抑制該低分子量成分從黏著劑印 出（print out)。一旦抑制印出，則黏著劑的组成不發生變 化，因此可維持設計整體的黏著力，抑制黏著劑從基台的 剝離。 上述（曱基）丙烯酸酯共聚物的共聚合型態沒有特別限 定，也可為無規共聚物、嵌段共聚物、接枝共聚物任一者。 (曱基）丙稀酸S旨共聚物的分子量較佳為重量平均分子 量30萬以上，更佳為35萬~250萬。重量平均分子量未滿 30萬時’則與被貼附體的黏合性及耐久黏合性恐不充分。 考慮黏合性及耐久黏合性，（甲基）丙烯酸酯共聚物的重量 平均分子量較佳為40萬〜180萬。又本說明書中所述之重量 平均分子量為以膠體滲透層析（GPC)法測定之標準聚苯乙 稀的換算值。 (曱基）丙烯酸酯共聚物的能量線硬化前的玻璃轉移溫 度（Tg)較佳為一 50〜〇t，更佳為_4〇〜〇艽。（甲基）丙烯酸酯 共聚物的玻璃轉移溫度（Tg)在此範圍内者可圖黏著力及斷 裂延伸率的適度平衡。 (2 )能量線硬化型氨酯丙烯酸酯 201245376 能量線硬化型氨酯丙烯酸酯為具有（曱基）丙烯醯基與 氨酯鍵結的寡聚物化合物’因為分子内具有（甲基）丙烯醯 基，所以經能量線照射可聚合硬化而成型。 能量線硬化型氨酯丙烯酸酯可由例如聚異氰酸酯化合 物與具有羥基或異氰酸酯基的（甲基）丙烯酸酯與多元醇化 合物反應而獲得。此述能量線硬化型氨酯丙烯酸酯可例 如’由多元醇化合物與聚異氰酸酯化合物反應，得到末端 含有異氰酸酯基之氨酯預聚物’再與具有羥基之（甲基）丙 烯酸酯反應’得到氨酯丙烯酸酯，或者由多元醇化合物與 聚異氰酸酯化合物反應’得到末端含經基之氧酯預聚物， 再與具有異氰酸酯基的（曱基）丙烯酸酯反應，得到氨酯丙 烯酸酯。 聚異氰酸酯化合物’例如，異佛爾酮二異氰酸酯、2, 4-甲苯二異氰酸酯、2, 6 -曱苯二異氰酸酯、1，3 -二曱苯二異 氰酸酯、1，4-二曱苯二異氰酸酯、二笨基曱烷-4, 4，-二異 氰酸酯等的二異氰酸酯。 具有經基之（曱基）丙稀酸自旨，例如，（甲基）丙稀酸2-羥基乙酯、（甲基）丙烯酸2-羥基丙酯、（甲基）丙烯酸2-羥 基丁酯、（曱基）丙烯酸4-羥基丁酯、聚乙二醇（曱基）丙缔 酸酯等。具有異氰酸酯基之（甲基）丙烯酸酯，例如，異氰 酸甲基丙烯醯氧基乙酯。 多元醇化合物例如烯烴型、聚碳酸酯型、聚醋型或聚 醚型等的多元醇化合物’具體例如聚乙二醇、聚丙二醇、 5^丁 一醇、聚碳酸醋二醇、聚醋二醇、聚越二醇等。 201245376 能量線硬化型氨酯丙烯酸酯也可使用市售者。例如紫 光系列 UV-6100B、UV-3210EA、UV-6010EA、UV-6020EA(上 述為日本合成化學工業公司製）等。 上述能量線硬化型氨酯丙烯酸酯可丨種單獨使用，也 可2種以上組合使用。 倉b量線硬化型氨醋丙稀酸醋的重量平均分子量較佳為 1，000〜12,000 ，更佳為2,500〜10, 〇〇〇 ，再更佳為 4, 000〜8, 000。重量平均分子量為1〇〇〇以上者，所得的黏 著劑具有充分的斷裂延伸率，在i2, 〇〇〇以下者，被發現為 黏著劑薄片化時最適合的黏度。 能量線硬化型氨酯丙烯酸酯的能量線硬化後之玻璃轉 移溫度（Tg)較佳為-40〜20X：，更佳為-2(M〇°C。能量線硬 化型氨酯丙烯酸酯的玻璃轉移溫度（Tg)在此述範圍内者， 可圖黏著力與斷裂延伸率的適度平衡。該能量線硬化型氨 醋丙稀酸醋的玻璃轉移溫度（Tg)雖為能量線硬化後的值， 但其係根據示差掃描熱量測定（DSC)法測定紫外線（照度 80mW/cm ’績算光量800mJ/cm2)照射後的值。 能量線硬化型氨酯丙烯酸酯的能量線硬化後之鉛筆硬 度較佳為B〜5B，更佳為3B〜5B ’再更佳為4B〜5B，最佳為 5B。該鉛筆硬度為5B及同等以上硬度時’硬化後黏著劑變 得具有充分的硬度’因此形狀可良好保持。當鉛筆硬度較 5B軟時’無法保持形狀’恐無法立體成型。又當該鉛筆硬 度為β及同等以下之軟度時，硬化後的黏著劑不會過硬變 脆’因此可抑制黏著劑剝離時的脆性破壞（brittle 12 201245376 fracture) 〇 本實施形態所述之能量線硬化型黏著劑中能量線硬化 型氨酯丙烯酸酯的含量（以固型份為基準），相對於（甲基） 丙烯酸酯共聚物100質量部，較佳為50〜2〇〇質量部，更佳 為70〜180質量部’再更佳為80〜150質量部。能量線硬化 型氨醋丙烯酸醋的含量為50 f量部以上時，所得:黏著劑 可具有充分的硬化性，為200質量部以下時，可充分確保 高分子量成分之（曱基）丙烯酸酯共聚物的含量，在黏著劑 以薄片狀態保存時可維持形狀。 (3)交聯劑 . 本實施形態所述之能量線硬化型黏著劑適量含有交聯 劑，容易滿足上述的斷裂延伸率、應力鬆他率及凝膠分率 的要件。 交聯劑沒有特別限制，可適當選擇習知的丙烯系樹月t :慣用作為交聯劑之任意一種。此述交聯劑例如聚異氰‘ 日化合物、環氧樹脂、三聚氰胺樹脂、尿素樹脂、二醛類、 :甲基聚合物、氮丙^(aziridine)系化合物 '金屬螯合化 :物、金屬烷氧化物、金屬鹽等’其中較佳使用聚里氰酸 酯化合物。 〃 聚異氰酸S旨化合物，例如，f苯二異氰酸能、二苯基 酯二異：酉“曰、2甲苯二異氰酸酯等的芳香族聚異氰酸 :-異氰酸己酯等的脂肪族聚異氰酸酯；異佛 亂酸酉旨、鱼化-贫宜兩 、 本基甲烧二異氰酸醋等的脂環式聚異氰酸 ，以及此迷化合物之雙縮脲體（biuret)、異氰腺酸體 13 201245376 (isocyanurate);更有與乙二醇、丙二醇、新戊二醇、三 羥甲基丙烷、t麻油等的低分子含活性氫之化合物反應之 反應物的加合物（adduct)等。這些交聯劑可丄種單獨使用， 也可組合2種以上使用。 本實施形態所述之能量線硬化型黏著劑中，交聯劑的 含量（以固型分為基準）’相對於（甲基）丙烯酸酯共聚物1〇〇 質量部，較佳為〇.〇1〜0.4質量部，更佳為0 03〜0 3質量 部’再更佳為0. 〇5~〇· 25質量部。 (4)光聚合起始劑 本實施形態所述之旎量線硬化型黏著劑含有光聚合起 始劑，可減少能量線硬化型氨酯丙烯酸醋的聚合硬化時必 要的能量線照射量及照射時間。 光聚合起始劑沒有特別限制，例如苯酚、苯乙酮、安 息香（benzoin)、安息香曱基醚、安息香乙基醚、安息香異 丙基醚、安息香異丁基醚、笨甲醯基苯曱酸酯、苯甲醯基 笨曱酸曱酯、安息香二曱基酮、2, 4-二乙基噻吨酮、卜羥 基環己基苯基酮、苯曱基二苯基亞硫酸鹽、四曱基秋蘭姆 (thiuram)單亞硫酸鹽、偶氮二異丁腈、2_氣蒽、二笨基 (2, 4, 6-三甲基苯甲醯基）氧化磷等。這些光聚合起始劑可^ 種單獨使用，也可組合2種以上使用。 本實施形態所述之能量線硬化型黏著劑中的光聚合起 始劑的含量（以固型份為基準），相對於能量線硬化型氨酯 丙烯酸酯100質量部，較佳為〇.〇5~1〇 〇質量部，更佳為 0·1〜6.0質量部，再更佳為〇·5〜4.〇質量部。 201245376 (5 )其他成分 本實施形態所述之能量線硬化型黏著劑，在無損於本 發明之目的之範圍内’也可視需要含有各種添加劑，例如 矽烷系偶合劑、黏著賦予劑、抗氧化劑、紫外線吸收劑、 光安定劑、軟化劑、填充劑、著色劑等。 本實施形態所述之能量線硬化型黏著劑為立體成型 用，特別是適合黏著劑經三維伸長的立體成型用。本說明 書中所述「伸長」之用語也包含膨脹的概念。將黏著劑三維 伸長的方法沒有特別限定’可例如氣體注入方式、含有發 泡劑的方式、推出突起的方式、減壓膨脹的方式等。立體 成型的形狀沒有特別限定’也可為例如球狀、半球狀、柱 狀等，也可為這些的連續凹凸構造。 根據本實施形態所述之能量線硬化型黏著劑，在將該 黏著劑貼附於基台進行上述之立體成型時，伸長至目標形 狀、大小，沒有從基台剝落，又伸長至目的標形狀、大小 時，可抑制因内聚破壞所造成的斷裂。 在進行上述立體成型的情形時，當能量線硬化型黏著 劑伸長至目標形狀、大小之時，照射能量線使其硬化，可 進行立體成型。 此時照射的能量線可使用由各種能量線發生裝置所產 生的能量線，通常使用紫外線、電子束等。例如，紫外線 通常使用從紫外線燈輻射的紫外線。此述紫外線燈使用在 通常波長300〜40〇nm範圍具有光譜分布之紫外線發光的高 壓水銀燈、光固基燈（fusi〇n H lamp)、氙氣燈等的紫外線 15 201245376 燈，照射量通常為50〜3000mJ/Cin2較佳。為電子束時，照射 量較佳為l〇~l〇〇〇krad 。 [黏著片] 如第1圖所示，第1實施形態所述之黏著片1A，由向 I依次順序為，剝離片12、層積於剝離片12的剝離面之黏 著劑層11、及層積於黏著劑層U之基材13所構成。 如第2圖所示，第2實施形態所述之黏著片1B，由2 個剝離片123、1213’與該2個剝離片123、121)的剝離面接 合而由該2個剝離片12a、12b包失的黏著劑層u所構成。 本說明書中所述之剝離片之剝離面為剝離片中具有剝離性 之表面，不論是進行剝離處理的表面與未進行剝離處理之 表面，只要是顯示剝離性的表面皆包含於此。 $著片ΙΑ、1B巾’黏著劑層u皆為上述能量線硬化 型黏著劑形成片狀者。黏著劑層n的厚度可視黏著片（的 成型方法等適當決定，但是通常& "。〇"，較佳為 5 100从m，更佳為1〇〜5〇em的範圍。 基材13沒有特別限制，通常作為黏著片之基材片皆可 例如聚對笨二甲酸二乙醋、聚對苯二甲酸二丁酿、 聚奈二甲酸乙二醇醋等的聚輯膜；三乙醯基纖維素等的纖 維素膜；…旨膜、聚乙稀膜、聚丙稀膜、聚氣乙稀膜、 1 —氣乙稀膜、聚乙稀醇膜、乙烯-乙酸乙稀醋共聚物膜、 聚本乙稀膜、聚碳_、丙稀樹脂膜、降冰片稀系樹脂 膜、環烯烴樹脂膜等的塑豚 乳曰發泡體、聚乙烯發泡 體專發泡體；道林紙、玻璃紙、浸潰紙、塗佈紙等的紙類； 16 201245376 鋁、銅等的金屬箔；使用嫘縈、丙烯酸、聚酯等纖維的織 布或不織布；上述2種以上的層積體等。塑膠膜也可為單 軸延伸或二軸延伸者。又當黏著劑層11與基材13同時立 體成型的情形時，基材13較佳具有可立體成型之程度的柔 軟性。 基材13的厚度視材料種類或黏著片1的目的而異，沒 有特別限制，但是通常為1〇〜3〇〇#m，較佳為 更佳為35〜80# m。 剝離片1 2、1 2a、1 2b可使用例如聚乙烯膜、聚丙烯膜、 聚丁烯膜、聚丁二烯膜、聚甲基戊烯膜、％氣乙烯膜、氣 乙烯共聚物膜、聚對苯二甲酸二乙酯膜、聚萘二甲酸乙二 醇酯膜、聚對苯二甲酸二丁酯膜、聚氨酯帛、乙烯乙酸乙 烯醋膜、離子聚合物樹脂膜、乙烯.（甲基）丙烯酸共聚物 膜、乙稀·（甲基）丙烯酸醋共聚才分、聚$乙稀膜、聚碳酸醋 膜、聚醯亞胺膜、氟系樹脂膜等。這些的交聯臈也可使用。 也可使用這些的層積膜。 上述剝離片的剝離面（特別是與黏著劑層丨丨接合的表 面I較佳施^以剝離處理。剝離處理所使用之剝離劑可例如烴 基系、珍乳系、氟纟、不飽和聚s旨系、聚稀煙系、峨系的 剝離劑。 在第2實施形態所述之黏著片1β使用兩個剝離片 12a、12b的情形時，兩個剝離片…、⑽的材料可為相同， 也可為㈣’但較佳調整為剝離片⑵與制離片…的剝 離力差不@ ’亦即i個為重剝離型剝離片，另】個為輕剝 17 201245376 離型剝離片。 剝離片12、12a、12b的厚度沒有 9n 1c.n 将別限定，但通常為 約20〜150从m。 製造上述黏著片1A為’在剝離片 比人士 月12的剝離面上，塗 佈含有上述能量線硬化型黏著劑之务 私—^ W〉谷液，使乾燥形成 黏者劑層11後，於該黏著劑層u層積基材 製造上述黏著片1B為’在1個制雜口 ^ 1因剌離片12a(或12b)的 剝離面上’塗佈含有上述能量線硬 ^化坦黏著劑之塗佈溶 液’使乾燥形成黏著劑層11後，使該 仗·兩黏者劑層11與另一 個剝離片12b(或12a)的剝離面疊合。 塗佈上述塗佈溶液的方法，可利用例如棒塗法、刀塗 法、輕塗法、平塗法、模具塗佈法、凹版塗佈法等。 使用本實施形態所述之黏著片丨，可經由三維伸長而立 體成型，特別是容易成型為球狀、半球狀、柱狀等的連續 凹凸構造。 上述說明之實施形態係為了容易理解本發明所記載， 並非為了限定本發明而記載。因&，上述實施形態所揭示 之各要件為包含屬於本發明之技術範圍全部的技術變更或 均等物之旨趣。 例如點著片1A的剝離片12也可省略，黏著片1 b中 的剝離片12a、1 2b的任一方也可省略。 【實施例】 以下由實施例等更具體說明本發明，但本發明之範圍 不限定於此述之實施例等。 201245376 [實施例1] (1) 黏著劑的調製 混合由丙烯酸丁酯52質量部、曱基丙烯酸甲酯20質 量部及丙烯酸2 -經基乙酯28質量部共聚合所形成的（甲基） 丙烯酸酯共聚物（以相對於（曱基）丙烯酸酯共聚物的經基 100當量’添加90當量的曱基丙烯醯氧基乙基異氰酸酉旨 (MOI )反應，重量平均分子量58萬，乙酸乙酯/曱笨混合溶 劑’玻璃轉移溫度-22°C，固形分濃度35質量％) 1〇〇質量 部（固形分）’與能量線硬化型氨酯丙烯酸系募聚物（日本合 成化學工業公司製，UV-61 00B，重量平均分子量6700，玻 璃轉移溫度0°C，硬化後鉛筆硬度5B) 1 〇〇質量部（固形 分），與異氰酸酯系交聯劑（東洋油墨製造公司製，〇ribain BHS8518，固形分濃度37_5質量％) 〇1質量部（固形分）， 與作為光聚合起始劑之卜羥基—環己基-笨基—酮（ciba[Technical Field] The present invention relates to an energy ray-curable adhesive and an adhesive sheet, and more particularly to an energy ray-curable adhesive and an adhesive sheet which can be three-dimensionally elongated and three-dimensionally formed. [Prior Art] The resin molded article has the advantages of being lightweight and transparent, and is easy to mold, and is used in the fields of automotive components and electrical appliances. However, when a sheet having a fine concavo-convex structure such as an optical substrate is formed by resin molding, it is difficult for a conventional resin to accurately shape a micron-order fine shape. For example, the radiation-curable adhesive described in Patent Documents 1 and 2 can be used. Patent Document 1 proposes an adhesive comprising a tackifying polymer and a radiation curable component as a main component, and has a storage elastic property I (greenness) at 23 r of IxlOPa or less, and radiation hardening at 23 cm. The storage elastic 〖the birth rate (G) is a radiation hardening type adhesive sheet of 5xl 〇 6Pa or more. Patent Document 2 proposes an adhesive comprising a tackifying polymer and a radiation curable component as a main component, and has a line breaking storage modulus (G) of 23° C., which is 1×10 6 or less, and after radiation hardening. At 4 (TC): the storage elastic modulus (E) is 2X1. 7pa or more, and the viscous film after radiation hardening is 20 ν in the gas generated by the photopolymerization initiator when heated at 8 Torr for 1 Torr. </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> According to the radiation-curable pressure-sensitive adhesive sheet described above, a sheet having a specific pattern shape in a sheet shape is laminated on an adhesive sheet, and the pattern shape is transferred to a point. When the sheet is formed, a fine uneven shape can be obtained. However, the radiation-curable pressure-sensitive adhesive sheet described above is attached to the base. The adhesive is three-dimensionally elongated and three-dimensionally formed (including the formation of the uneven structure). In the case of the same.), the problem of peeling of the adhesive sheet from the abutment occurs. It is also assumed that when the abutment having a large surface energy which is not peeled off by the adhesive sheet is used, the adhesive is cohesively destroyed during elongation (coheSlve faiiure), The present invention has been made in view of the actual situation described above, and is intended to provide an energy ray-curable adhesive and an adhesive sheet suitable for three-dimensional stretching and three-dimensionally formed. [Technical means for solving the problem] In order to achieve the above object, First, the present invention provides a fracture extension before energy beam hardening (4) of 2% or more, a stress relaxation rate before energy line hardening of 7 〇 to 95%, and a gel fraction before energy ray hardening as a characteristic energy ray-curable adhesive. (Embodiment 1) The energy ray-curable adhesive according to the above invention (Invention 1) satisfies the above physical properties, and when the adhesive is attached to a base and is three-dimensionally elongated and three-dimensionally formed, the peeling off from the base or the like is suppressed. The fracture due to cohesive failure during molding can be molded into a target shape. In the above invention (Invention 1), the energy ray-curable adhesive is preferably packaged 4 20124537 (6) A (fluorenyl) acrylate copolymer and an energy ray-curing urethane acrylate (Invention 2). In the invention (Invention 2), the content of the energy ray-curing urethane acrylate vinegar is relative to the above (methyl) The acrylate mass portion 1 〇〇 mass portion ' is preferably 50 to 200 parts by mass (Invention 3). In the above invention (Inventions 2 and 3), the amount of the above-mentioned (fluorenyl) acrylate copolymer before curing The glass transition temperature is -5 〇 〇 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( In the above invention (Inventions 2 to 4), the pencil hardness of the energy ray-curable vinegar propylene iSs after the enthalpy is hardened is preferably B to 5B (Invention (VIII). In the above invention (Inventions 2 to 5), the energy ray-curable adhesive preferably further comprises a crosslinking agent (Invention 6). In the above invention (Invention 6), the content of the crosslinking agent is preferably & uh.4 f (part 7) with respect to the mass portion of the (meth)acrylic acid vinegar copolymer (10). In the above-mentioned Ming Ming 6 and 7), the crosslinking agent is preferably an isocyanate-based crosslinking agent (Invention 8). In the above invention (Inventions 2 to 8), the energy ray-curable adhesive preferably further comprises a photopolymerization initiator (Invention 9). The energy ray-curable adhesive described in the above invention (Inventions 1 to 9) is preferably used for three-dimensional molding (Invention 1). In the invention (Day 10), the energy ray-curable adhesive is preferably three-dimensionally stretched and then three-dimensionally formed (Invention 11). 201245376 Second, the present invention provides with 1, . The adhesive sheet composed of the above-mentioned wire-curing type adhesive (Inventions 1 to 11) is characterized by an adhesive sheet (Invention 12). The third invention provides an adhesive sheet characterized in that the adhesive layer composed of the above-mentioned wire-curable adhesive (Inventions 1 to 11) has two release sheets which are sandwiched and sandwiched with the adhesive layer. (Invention 13). [Effect of the Invention] According to the energy ray-curable adhesive of the present invention, when the adhesive adhered to the base is three-dimensionally elongated and three-dimensionally formed, the peeling of the adhesive from the base or the molding process can be suppressed. The fracture caused by the cohere failure of the adhesive can be formed into a target shape. [Embodiment] Hereinafter, embodiments of the present invention will be described. [Energy ray-curable adhesive] The energy-expandable adhesive of the present embodiment has an elongation at break, a stress relaxation rate, and a gel fraction before the energy ray hardening satisfy the following requirements, and according to this, it becomes suitable Specifically, the energy ray-curable adhesive of the present embodiment has an elongation at break of 2000% or more, preferably 2,200 to 4,000%, in particular, three-dimensionally elongated and three-dimensionally formed (hereinafter referred to as "elongation molding"). It is preferably 2400 to 3500%. When the elongation at break is 2% or more, the adhesive is difficult to be broken at the time of elongation molding. The elongation at break is measured by a separate adhesive layer having no substrate or the like. Specifically, an adhesive which is formed into a thickness of 5 〇〇//m, a width of 15 mm, and a length of 55 mm (which has a measurement range of 25 mm) is set to 200 mm/at 23 ° C, 50% Rff 6 201245376. The rate of elongation of the energy-hardening type of the agent of the present embodiment is 70 to 95%, preferably 75 to 93%, particularly preferably 8 to 99%. When the stress relaxation is m or more, it is easy to maintain the state in which the adhesive is elongated, so that it is easy Type into a desired shape. On the other hand, when the stress relaxation rate is 95% or less, it is possible to suppress the deformation of the shape by an external force (e.g., gravity) other than the force for elongation when the adhesive is kept in an extended state. The stress relaxation rate described in this specification is the rate of stress relaxation after the adhesive is stretched for 3 seconds in the tensile test. Specifically, the tensile test was carried out to form an adhesive having a thickness of 50 (^m, El5, and a length of 55 mm (the range of which was measured to be 25 ram), in the environment of 23 〇, 5 〇% ,, at a sub-speed The stress relaxation rate is calculated by the following equation based on the stress A at 3 〇 (10) elongation and the stress B at 3 sec after the elongation is stopped. Stress relaxation rate (%) = { (AB) / A} xl 〇 〇 (%) The energy ray-curable adhesive according to the embodiment has a gel fraction of 1 to 30%, preferably 2 to 2% by weight, more preferably 3 to 1% by weight. When it is 1% or more, the adhesion of the adhesive due to cohesive failure during elongation molding can be suppressed. When the gel fraction is 3% or less, the elongation of the adhesive can be ensured. < Gel of the adhesive described above The fraction is the value at the time of attachment (after the etching period). Specifically, the energy ray-curable adhesive is applied to the release sheet, and after the heat treatment, it is stored in an environment of 23t, 5〇% RH for 7 days. Gel fraction. The gel fraction of the mold-occupying agent is determined by the stability of the button after the engraving period. Therefore, when the etching period is not clear, it can be changed to 23 r, 50% RH in the environment after 7 days of storage. 201245376 The energy ray-curable adhesive satisfying the above requirements preferably comprises (1) (meth) acrylate copolymer and (2) energy ray-curing urethane acrylate The ester 'more preferably includes (3) a crosslinking agent and/or (4) a photopolymerization initiator. (1) The (fluorenyl) acrylate copolymer (fluorenyl) acrylate copolymer is not particularly limited and can be derived from It is conventionally selected as a conventional (fluorenyl) acrylate copolymer which is a resin component of an acrylic pressure-sensitive adhesive. The (meth) acrylate copolymer may, for example, be an ester moiety having a carbon number of 1 to 20 alkyl groups. a copolymer of (mercapto) acrylate, a monomer having a functional group having an active hydrogen with other monomers as needed. In the present specification, (mercapto) acrylate means both acrylate and methacrylate. Other similar terms are also the same. The ester moiety is a (decyl) acrylate having a carbon number of 1 to 20 alkyl groups, for example, (decyl) decyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate. , (isopropyl) (meth)acrylate, ( Butyl acrylate, octyl (meth) acrylate, isobutyl (meth) acrylate, amyl (meth) acrylate, hexyl acrylate, cyclohexyl (meth) acrylate, (曱2-ethylhexyl acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl acrylate, tetradecyl (meth) acrylate, (meth) acrylate Hexadecyl ester, decyl (decyl) octadecyl acrylate, etc. These may be used alone or in combination of two or more. On the other hand, the monomer having a functional group having an active hydrogen may be, for example, (meth)acrylic acid 2 -hydroxyethyl ester, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, (Meth) propylene 8 such as 4-hydroxybutyl acrylate, 201245376 acid hydroxyalkyl ester, (mercapto)acrylic acid monomethylaminoethyl ester, (mercapto) acrylic acid monoethylaminoethyl ester , (meth)acrylic acid monomethylaminopropyl acrylate, (meth)acrylic acid monoethylamine Propyl and the like (Yue-yl) acrylic acid esters of mono alkylamino burning; ethylene acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid and the like unsaturated carboxylic acids and the like. These monomers may be used singly or in combination of two or more. Other monomers which may be used, for example, may be vinyl esters such as vinyl acetate or ethyl propionate; olefins such as ethylene, propylene, and isobutylene; halogenated dilute hydrocarbons such as vinyl chloride and ethylene; a styrene monomer such as α-methyl styrene; a diene monomer such as butadiene, isoprene or cholestrel; acrylonitrile or methacrylonitrile; A nitrile-based monomer; an acrylamide such as acrylamide, N-methylpropenylamine or n,N-dimercaptopropylamine. These may be used alone or in combination of two or more. Among the above (fluorenyl) acrylate copolymers, those having an energy ray polymerizable group in the molecule (so-called adduct polymer) are preferred. The method of having an energy ray polymerizable group in the molecule of the (meth) acrylate copolymer is not particularly limited, but, for example, it is possible to pass a (mercapto) acrylate copolymer (al) having a monomer unit having a functional group. It is obtained by reacting the unsaturated group-containing compound (a2) having a substituent reactive with the functional group. The functional group-containing monomer unit contained in the (al) component is preferably 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate or the like. A hydroxyl group-containing acrylate. The component (a2) is preferably a functional group having a radical reaction with the (ai) component 201245376 and a compound having a polymerizable double bond, such as mercaptopropenyloxyethyl isocyanate, isopropyl-α, α-di Methylbenzyl isocyanate, methyl acrylonitrile isocyanate, allyl isocyanate, glycidyl (mercapto) acrylate; (mercapto) acrylic acid. When a (fluorenyl) acrylate copolymer having an energy ray polymerizable group in a molecule is used, since the amount of the energy ray-curing urethane acrylate which is a low molecular weight component can be reduced, the low molecular weight component can be suppressed from The adhesive is printed out. Once the printing is suppressed, the composition of the adhesive does not change, so that the overall adhesion of the design can be maintained, and the peeling of the adhesive from the base can be suppressed. The copolymerization type of the above (fluorenyl) acrylate copolymer is not particularly limited, and may be any of a random copolymer, a block copolymer, and a graft copolymer. The molecular weight of the (mercapto)acrylic acid S copolymer is preferably a weight average molecular weight of 300,000 or more, more preferably 350,000 to 2,500,000. When the weight average molecular weight is less than 300,000, the adhesion to the adherend and the durability adhesiveness may be insufficient. The weight average molecular weight of the (meth) acrylate copolymer is preferably from 400,000 to 1.8 million in consideration of adhesiveness and durability. Further, the weight average molecular weight described in the present specification is a converted value of a standard polystyrene measured by a colloidal permeation chromatography (GPC) method. The glass transition temperature (Tg) before the energy ray hardening of the (fluorenyl) acrylate copolymer is preferably from 50 to 〇t, more preferably from _4 〇 to 〇艽. The glass transition temperature (Tg) of the (meth) acrylate copolymer in this range allows for a moderate balance of adhesion and elongation at break. (2) Energy line hardening urethane acrylate 201245376 Energy line hardening urethane acrylate is an oligomer compound having a (fluorenyl) acrylonitrile group and a urethane bond 'because of having (meth) acrylonitrile in the molecule Base, so it can be formed by polymerized by energy beam irradiation. The energy ray-curing urethane acrylate can be obtained, for example, by reacting a polyisocyanate compound with a (meth) acrylate having a hydroxyl group or an isocyanate group and a polyol compound. The energy ray-curing urethane acrylate can be, for example, 'reacted from a polyol compound and a polyisocyanate compound to obtain a urethane prepolymer having an isocyanate group at the end and reacting with a (meth) acrylate having a hydroxyl group to obtain ammonia. The ester acrylate, or by reacting a polyol compound with a polyisocyanate compound, to obtain a terminal thioester-containing prepolymer, and then reacting with a (mercapto) acrylate having an isocyanate group to obtain a urethane acrylate. a polyisocyanate compound 'for example, isophorone diisocyanate, 2, 4-toluene diisocyanate, 2,6-nonyl diisocyanate, 1,3-diphenylene diisocyanate, 1,4-diphenylene diisocyanate, Diisocyanate of diphenyl decane-4,4,-diisocyanate or the like. Has a thiol-based acrylic acid, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate , (fluorenyl) 4-hydroxybutyl acrylate, polyethylene glycol (mercapto) propionate, and the like. A (meth) acrylate having an isocyanate group, for example, methacryloxyethyl methacrylate. Polyol compounds such as olefin type, polycarbonate type, polyester type or polyether type polyol compound 'specifically, for example, polyethylene glycol, polypropylene glycol, 5 butyl alcohol, polycarbonate diol, polyester vine Alcohol, polyglycol and the like. 201245376 Energy line hardening urethane acrylate can also be used by a commercial one. For example, the violet light series UV-6100B, UV-3210EA, UV-6010EA, UV-6020EA (described above by Nippon Synthetic Chemical Industry Co., Ltd.) and the like. The above-mentioned energy ray-curing urethane acrylate may be used singly or in combination of two or more kinds. The weight average molecular weight of the b-line-cured type Aminoacetic acid vinegar is preferably 1,000 to 12,000, more preferably 2,500 to 10, and most preferably 4 to 8,000 to 8,000. When the weight average molecular weight is 1 Å or more, the obtained adhesive has a sufficient elongation at break, and it is found to be the most suitable viscosity when the adhesive is flaky at i2 or less. The glass transition temperature (Tg) of the energy ray-curing urethane acrylate after energy line hardening is preferably -40 to 20X:, more preferably -2 (M 〇 ° C. Energy ray-curing urethane acrylate glass) The transfer temperature (Tg) is within the range described herein, and the adhesion between the adhesion and the elongation at break is moderately balanced. The glass transition temperature (Tg) of the energy ray-hardened Aminoacetic acid vinegar is the value after the energy ray hardening. However, it is a value measured by ultraviolet light (illuminance 80 mW/cm 'yield light amount 800 mJ/cm 2 ) by differential scanning calorimetry (DSC) method. The pencil hardness of the energy ray-curing urethane acrylate is hardened by the energy ray. Preferably, it is B~5B, more preferably 3B~5B' is more preferably 4B~5B, and most preferably 5B. When the pencil hardness is 5B and the hardness is equal or more, the adhesive becomes sufficiently hard after hardening. It can be well maintained. When the pencil hardness is softer than 5B, the 'cannot maintain the shape' may not be three-dimensionally formed. When the hardness of the pencil is β and the softness of the same or less, the hardened adhesive will not be too hard and brittle 'so it can be suppressed Brittle failure when adhesive is peeled off (br Ittle 12 201245376 fracture) The content of the energy ray-curing urethane acrylate in the energy ray-curable adhesive according to the present embodiment (based on the solid content), relative to the mass of the (meth) acrylate copolymer 100 The portion is preferably 50 to 2 〇〇 mass portion, more preferably 70 to 180 parts by mass, and more preferably 80 to 150 parts by mass. When the content of the energy ray-cured ammonia vinegar vinegar is 50 f or more, It is obtained that the adhesive can have sufficient curability, and when it is 200 parts by mass or less, the content of the (mercapto) acrylate copolymer of the high molecular weight component can be sufficiently ensured, and the shape can be maintained when the adhesive is stored in a sheet state. Cross-linking agent. The energy ray-curable adhesive according to the present embodiment contains a crosslinking agent in an appropriate amount, and it is easy to satisfy the above-mentioned requirements of elongation at break, stress relaxation rate, and gel fraction. The crosslinking agent is not particularly limited. A conventional propylene-based tree t: conventionally used as a crosslinking agent can be appropriately selected. The crosslinking agent is, for example, a polyisocyanide compound, an epoxy resin, a melamine resin, a urea resin, a dialdehyde, and the like: A base polymer, an aziridine compound 'metal chelate: a metal alkoxide, a metal salt, etc.' wherein a polycyanate compound is preferably used. 聚 A polyisocyanate S compound, for example , F phenyl diisocyanate, diphenyl ester diisomer: an aromatic polyisocyanate such as fluorene or 2 toluene diisocyanate: an aliphatic polyisocyanate such as hexyl isocyanate; An alicyclic polyisocyanate such as hydrazine, a fish-poor, a carbaryl diisocyanate, and a biuret and an isocyanate 13 201245376 ( Isocyanurate); an adduct of a reactant which reacts with a low molecular weight active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or t sesame oil. These crosslinking agents may be used singly or in combination of two or more. In the energy ray-curable pressure-sensitive adhesive according to the present embodiment, the content of the crosslinking agent (based on the solid type) is preferably 〇.〇 with respect to the mass portion of the (meth) acrylate copolymer. 1 to 0.4 mass parts, more preferably 0 03~0 3 quality parts 'more preferably 0. 〇5~〇· 25 mass parts. (4) Photopolymerization initiator The ray-curable pressure-sensitive adhesive according to the present embodiment contains a photopolymerization initiator, which can reduce the amount of energy ray irradiation and irradiation necessary for the polymerization hardening of the energy ray-curing urethane acrylate vinegar. time. The photopolymerization initiator is not particularly limited, and examples thereof include phenol, acetophenone, benzoin, benzoin oxime, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoic acid benzoic acid. Ester, benzhydryl decyl decanoate, benzoin dimethyl ketone, 2, 4-diethyl thioxanthone, hydroxycyclohexyl phenyl ketone, phenyl fluorenyl diphenyl sulfite, tetradecyl Thiuram monosulfite, azobisisobutyronitrile, 2_gas, diphenyl (2,4,6-trimethylbenzylidene) phosphorus oxide, and the like. These photopolymerization initiators may be used singly or in combination of two or more. The content of the photopolymerization initiator in the energy ray-curable adhesive according to the present embodiment (based on the solid content) is preferably 〇.〇 with respect to 100 parts by mass of the energy ray-curing urethane acrylate. 5~1〇〇 quality part, more preferably 0·1~6.0 quality part, and even better 〇·5~4.〇Quality department. 201245376 (5) Other components The energy ray-curable adhesive according to the present embodiment may contain various additives such as a decane-based coupling agent, an adhesion-imparting agent, an antioxidant, and the like, as long as the object of the present invention is not impaired. A UV absorber, a light stabilizer, a softener, a filler, a colorant, and the like. The energy ray-curable adhesive according to the present embodiment is used for three-dimensional molding, and is particularly suitable for three-dimensional molding in which the adhesive is three-dimensionally elongated. The term "elongation" as used in this specification also includes the concept of expansion. The method of three-dimensionally elongating the adhesive is not particularly limited, and may be, for example, a gas injection method, a method containing a foaming agent, a method of pushing out a protrusion, a method of decompressing and expanding, or the like. The shape of the three-dimensional molding is not particularly limited, and may be, for example, a spherical shape, a hemispherical shape, a columnar shape, or the like, or a continuous uneven structure of these. According to the energy ray-curable adhesive according to the embodiment, when the adhesive is attached to the base to perform the above-described three-dimensional molding, the adhesive is stretched to a target shape and size, and is not peeled off from the base, and is extended to the target shape. At the time of size, the fracture caused by cohesive failure can be suppressed. In the case of the above-described three-dimensional molding, when the energy ray-curable adhesive is stretched to a target shape and size, the energy ray is irradiated to be hardened, and three-dimensional molding can be performed. The energy rays irradiated at this time can use energy rays generated by various energy ray generating devices, and ultraviolet rays, electron beams, and the like are usually used. For example, ultraviolet light usually uses ultraviolet rays radiated from an ultraviolet lamp. The ultraviolet lamp described above uses an ultraviolet ray 15 201245376 lamp such as a high-pressure mercury lamp, a photo-solid lamp (fusi〇n H lamp) or a xenon lamp having a spectral distribution of ultraviolet light in a wavelength range of 300 to 40 〇 nm, and the irradiation amount is usually 50. ~3000mJ/Cin2 is preferred. When it is an electron beam, the irradiation amount is preferably l〇~l〇〇〇krad. [Adhesive sheet] As shown in Fig. 1, the adhesive sheet 1A according to the first embodiment is in the order of I, the release sheet 12, the adhesive layer 11 laminated on the release surface of the release sheet 12, and the layer. The substrate 13 is formed on the adhesive layer U. As shown in Fig. 2, the adhesive sheet 1B according to the second embodiment is joined by the peeling surfaces of the two peeling sheets 123 and 1213' and the two peeling sheets 123 and 121), and the two peeling sheets 12a and 12b is composed of the adhesive layer u. The release surface of the release sheet described in the present specification is a surface having releasability in the release sheet, and the surface which is subjected to the release treatment and the surface which is not subjected to the release treatment are included in the surface which exhibits releasability. The film adhesive layer, the 1B towel, and the adhesive layer u are all formed by the above-mentioned energy ray-curable adhesive. The thickness of the adhesive layer n can be appropriately determined depending on the molding method, etc., but usually &"〇", preferably 5 100 from m, more preferably 1 〇 to 5 〇em. 13 is not particularly limited, and generally, as a substrate sheet of the adhesive sheet, for example, a poly-p-polyacetic acid diacetate, a polybutylene terephthalate, a polyethylene naphthalate, or the like; Cellulose film of sulfhydryl cellulose, etc.; film, polyethylene film, polypropylene film, polyethylene film, 1-ethylene film, polyethylene film, ethylene-ethylene acetate copolymer Film, polythene film, polycarbon_, propylene resin film, norbornene resin film, cycloolefin resin film, etc., plastic porpoise foam, polyethylene foam special foam; Paper, cellophane, impregnated paper, coated paper, etc.; 16 201245376 Metal foil such as aluminum or copper; woven or non-woven fabric using fibers such as enamel, acrylic, polyester, etc.; Etc. The plastic film can also be a uniaxial extension or a biaxial extension. Also when the adhesive layer 11 and the substrate 13 are simultaneously formed in three dimensions The base material 13 preferably has a flexibility to be three-dimensionally formed. The thickness of the base material 13 varies depending on the type of the material or the purpose of the adhesive sheet 1, and is not particularly limited, but is usually 1 〇 to 3 〇〇 #m, More preferably, it is 35 to 80 # m. The release sheet 1 2, 1 2a, and 1 2b can be, for example, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, or a polymethylpentene film. ,% gas ethylene film, gas ethylene copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane enamel, ethylene vinyl acetate film , ionic polymer resin film, ethylene. (meth)acrylic copolymer film, ethylene (meth)acrylic acid vinegar copolymerization, poly$ethylene film, polycarbonate film, polyimine film, fluorine system A resin film or the like may be used. These laminated films may also be used. The laminated film of the release sheet (particularly the surface I bonded to the adhesive layer) is preferably subjected to a release treatment. The release agent used in the treatment may be, for example, a hydrocarbon-based system, a rare milk system, a fluorinated fluorene, an unsaturated polysole, or a poly In the case where the two release sheets 12a and 12b are used as the adhesive sheet 1β according to the second embodiment, the materials of the two release sheets... and (10) may be the same or may be (four)' However, it is preferable to adjust the peeling force difference between the release sheet (2) and the release sheet to be not '@, that is, i are heavy release type release sheets, and the other one is light peeling 17 201245376 release release sheet. Release sheets 12, 12a, 12b The thickness of 9n 1c.n is not limited, but is usually about 20 to 150 m. The above-mentioned adhesive sheet 1A is produced as "the above-mentioned energy ray-curable adhesive is applied on the release surface of the release sheet than the person 12". After the drying, the adhesive layer 11 is formed, and the adhesive sheet 1 is laminated on the adhesive layer to form the adhesive sheet 1B as 'in one making mouth ^ 1 due to the peeling piece 12a On the peeling surface of (or 12b), 'coating the coating solution containing the above-mentioned energy ray hardening agent' to dry to form the adhesive layer 11, and then to apply the coating layer 11 to the other peeling sheet The peeling surface of 12b (or 12a) is superposed. The method of applying the above coating solution can be, for example, a bar coating method, a knife coating method, a light coating method, a flat coating method, a die coating method, a gravure coating method, or the like. The adhesive sheet according to the present embodiment can be formed by three-dimensional stretching and can be formed into a continuous concave-convex structure such as a spherical shape, a hemispherical shape, or a columnar shape. The embodiments described above are described in order to facilitate the understanding of the present invention and are not intended to limit the invention. The components disclosed in the above embodiments are intended to encompass all technical changes or equivalents belonging to the technical scope of the present invention. For example, the release sheet 12 on which the sheet 1A is attached may be omitted, and either one of the release sheets 12a and 1 2b in the adhesive sheet 1 b may be omitted. [Examples] Hereinafter, the present invention will be specifically described by examples and the like, but the scope of the present invention is not limited to the examples and the like. 201245376 [Example 1] (1) Modification and mixing of an adhesive is carried out by copolymerization of 52 parts by mass of butyl acrylate, 20 parts by mass of methyl methacrylate, and 28 parts by mass of 2-ethyl acrylate. An acrylate copolymer (addition of 90 equivalents of mercaptopropenyloxyethyl isocyanate (MOI) to a base of 100 equivalents of the (fluorenyl) acrylate copolymer, weight average molecular weight of 580,000, Ethyl acetate / hydrazine mixed solvent 'glass transition temperature -22 ° C, solid content concentration 35 mass %) 1 〇〇 mass part (solids) 'and energy line hardening urethane acrylate polymer (Japanese synthetic chemistry Industrial company, UV-61 00B, weight average molecular weight 6700, glass transition temperature 0 ° C, pencil hardness after hardening 5B) 1 〇〇 mass part (solid content), and isocyanate cross-linking agent (Toyo Ink Manufacturing Co., Ltd., 〇ribain BHS8518, solid content concentration 37_5 mass%) 〇1 mass fraction (solid fraction), and hydroxy-cyclohexyl-styl-ketone (ciba) as photopolymerization initiator
Specialty Chemicals 公司製，irgacure 184) 3. 〇 質量部， 調製能量線硬化型點著劑。 (2) 黏著片的製作 將上述⑴所調製的能量線硬化型黏著劑，以乾燥厚度 成為20" m塗佈於以矽氧系剝離劑對聚對苯二甲酸二乙醋 膜-表面進行過剝離處理之重剝離型剝離片（―公司 製’ SP-PET38T103] ’厚度38”）的剝離處理面，在ιι〇 :乾燥鐘’形成黏著劑層。將以石夕氧系剝離劑對聚對 笨一甲西夂一乙醋膜一表面；隹；讲备丨施全 進仃匕幻離處理之輕剝離型剝離 片山晰公司製，SP销·31，厚度38一的剝離處 19 201245376 理面貼合於所得的黏著劑層，形成黏著劑層被2個剝離片 包夾的型態。之後，在23t、50%RH的條件下7天，進行 姓刻，作成黏著片。 [實施例2 ] 除改變異氰酸酯系交聯劑的調配量為〇. 2質量部（固 形分）以外’其餘同實施例i之方法製作黏著片。 [實施例3] 除改變異氰酸酯系交聯劑的調配量為〇. 3質量部（固 形分）以外，其餘同實施例1之方法製作黏著片。 [實施例4 ] 除改變氨酯丙烯酸系寡聚物的調配量為12 〇質量部 (固形分）及異氰酸酯系交聯劑的調配量為〇2質量部（固 形分）以外，其餘同實施例1之方法製作黏著片。 [實施例5 ] 除改變氨酯丙烯酸系寡聚物的調配量為8〇質量部（固 形分）及異氰酸酯系交聯劑的調配量為0 · 2 〇質量部（固形 分）以外’其餘同實施例1之方法製作黏著片。 [實施例6] 混合由丙烯酸丁酯80質量部及丙烯酸20質量部共聚 合所形成的（甲基）丙稀酸酯共聚物（以相對於（曱基）丙稀 酸酯共聚物的羧基100當量，添加30當量的甲基丙稀酿氧 基乙基異氰酸酯（MOI))反應’重量平均分子量60萬，乙酸 乙酯/曱苯/MEK混合溶劑，玻璃轉移溫度-34°C，固形分濃 度30質量％) 100質量部（固形分），與作為含有能量線聚 20 201245376 合性基的寡聚物之能量線硬化型丙烯酸酯系多官能基單體 及寡聚物所形成之組成物（日本化藥公司製，KAYARAD NKR-001 ) 80質量部（固形分）及能量線硬化型氨酯丙烯酸 系寡聚物（日本合成化學工業公司製，UV-3210EA，重量平 均分子量9 0 0 0 ’玻璃轉移溫度-2 7 °C，硬化後鉛筆硬度 6B~8B) 20質量部（固形分）’與異氰酸酯系交聯劑（東洋油 墨製造公司製’ Oribain BHS8515，固形分濃度37.5質量 %) 〇· 1質量部（固形分），與作為光聚合起始劑之卜羥基_ % 己基-本基-酮（Ciba Specialty Chemicals 公司製， Irgacure 184) 3.0質量部，調製能量線硬化型黏箸劑。 除使用此述之能量線硬化型黏著劑以外，其餘與實施例工 相同製作黏著片。 [比較例1] 除改變異氰酸酯系交聯劑的調配量為〇. 5質量部（固 形分）以外’其餘同實施例1之方法製作黏著片。 [比較例2 ] 除改變氨醋丙稀酸系寡聚物的調配量為12 〇質量邻 (固形分）及異氰酸酯系交聯劑的調配量為i 〇質量部（固 形分）以外，其餘同實施例1之方法製作黏著片。 [比較例3] 除改變氨酯丙烯酸系募聚物的調配量為8〇質量部（固 形分）及異氰酸酯系交聯劑的調配量為1〇質量部（固形分） 以外’其餘同實施例1之方法製作黏著片。 [比較例4 ] 21 201245376 混合由丙烯酸丁酯80質量部及丙烯酸20質量部共聚 合所形成的（曱基）丙烯酸酯共聚物（以相對於（曱基）丙稀 酸酯共聚物的羧基100當量’添加30當量的甲基丙烯醯氧 基乙基異氰酸酯（MOI)反應，重量平均分子量60萬，乙酸 乙酯/甲苯/MEK混合溶劑，玻璃轉移溫度-34。(：，固形分濃 度30質量％) 100質量部（固形分），與作為含能量線聚合 性基的寡聚物之三環癸烷二曱醇二丙烯酸酯（新中村化學 公司製，NK Ester ADCP) 52質量部（固形分）與環氧基（甲 基）丙烯酸酯寡聚物（新中村化學公司製，NK 01 ig〇 EA-1 020：) 28質量部（固形分），與異氰酸酯系交聯劑（東洋油墨製造 公司製’ Oribain BHS8515 ’固形分濃度37.5質量％) 0.1 質量部（固形分），與作為光聚合起始劑之1-經基-環己基_ 苯基-酮（Ciba Specialty Chemicals 公司製，irgacure 184) 3. 0質量部，調製能量線硬化型黏著劑。除使用此述之能 量線硬化型黏著劑以外’其餘與實施例1相同製作黏著片。 [比較例5 ] 除改變氨酯丙烯酸酯系寡聚物為能量線硬化型氨酯丙 烯酸酯系寡聚物（日本合成化學工業公司製，υν_32ΐ 〇εα， 重量平均分子量9000，玻璃轉移溫度-27t，硬化後鉛筆 硬度6B-8B) 100質量部（固形分）’及改變異氰酸酯系交聯 劑的調配量為0 · 4質量部以外，其餘與實施例1相同製作 黏著片。 [比較例6 ] 除改變氨酯丙烯酸酯系寡聚物為能量線硬化型氨酯丙 22 201245376 稀酸醋系寡聚物（日本人 » . ., yv ^ 。成化學工業公司製，UV-7000B，重 量35GG’破璃轉移溫度-unm 硬化後鉛筆硬度H〜F) 1〇〇 , 質夏部（固形分），及改變異氰酸 酯系交聯劑的調配量為〇 、 相同製作黏M。 4f量部以外，其餘與實施例1 [試驗例1](斷裂延長率測定） 使實施例或比較例所得的黏著片中的黏著劑層的總厚 又、為〇〇# m且以層積體的最表面層只有制離片的情形 層積複數層的上述黏著劑層，在饥、的氛圍氣下 放至2週。之後’將層積複數層上述黏著劑層的黏著片裁 切成 15mm 寬 x55nun# 的媒 〇 我的樣σ。，剝離層積於層積體最表面層 的剝離片’以樣品的測定範圍為15随寬乂25酿長，將樣品 放置於萬能拉伸試驗機（SHIMADZU公 刪⑻。然後在饥、5咖的環境下，以::Specialty Chemicals, irgacure 184) 3. 〇 Mass, modulated energy line hardening type dosing agent. (2) Preparation of Adhesive Sheet The energy ray-curable adhesive prepared in the above (1) was applied to a surface of a polyethylene terephthalate film by a dry thickness of 20 " m. The peeling-treated surface of the peel-off peeling sheet ("Compact" 'SP-PET38T103' 'thickness 38") of the peeling treatment is formed into an adhesive layer in ιι〇: drying bell. Stupa one side, one side of a vinegar film, one surface; 隹; 讲 丨 全 全 全 全 全 全 仃匕 仃匕 仃匕 仃匕 仃匕 仃匕 仃匕 仃匕 仃匕 仃匕 仃匕 仃匕 仃匕 仃匕 仃匕 仃匕 仃匕 仃匕 SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP The obtained adhesive layer was formed into a form in which the adhesive layer was sandwiched between two release sheets, and then, under the conditions of 23 t and 50% RH for 7 days, the adhesive was applied to the original sheet to form an adhesive sheet. [Example 2] The amount of the isocyanate-based crosslinking agent was 〇. 2 parts by mass (solid content), and the same procedure as in Example i was used to prepare an adhesive sheet. [Example 3] The amount of the isocyanate-based crosslinking agent was changed to 〇. Other than the mass portion (solid fraction), the same method as in the first embodiment [Example 4] The addition amount of the urethane acrylate oligomer was changed to 12 〇 mass part (solid content) and the isocyanate type crosslinking agent was 〇 2 mass parts (solid content), The adhesive sheet was prepared in the same manner as in Example 1. [Example 5] The amount of the urethane-based acrylic oligomer was changed to 8 parts by mass (solid content) and the isocyanate-based crosslinking agent was adjusted to 0. 2 The adhesive sheet was produced in the same manner as in Example 1 except for the mass portion (solid fraction). [Example 6] Mixing (meth)acrylic acid formed by copolymerization of 80 parts by mass of butyl acrylate and 20 parts by mass of acrylic acid Ester copolymer (with 100 equivalents of carboxyl group relative to the carboxyl group of the (mercapto) acrylate copolymer, 30 equivalents of methyl propylene oxyethyl isocyanate (MOI)) was added to react 'weight average molecular weight 600,000, acetic acid B Ester/nonylbenzene/MEK mixed solvent, glass transition temperature -34 ° C, solid content concentration 30% by mass) 100 mass parts (solid content), and energy line as oligomer containing energy line poly 20 201245376 Hardened acrylate multi-functional A composition of a monomer and an oligomer (KAYARAD NKR-001, manufactured by Nippon Kayaku Co., Ltd.) 80 mass parts (solid content) and energy ray-curing urethane acrylate oligomer (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., UV-3210EA, weight average molecular weight 9000 'glass transition temperature -2 7 °C, pencil hardness after hardening 6B~8B) 20 mass parts (solids)' and isocyanate crosslinker (made by Toyo Ink Manufacturing Co., Ltd.) Oribain BHS8515, solid content concentration: 37.5 mass%) 〇·1 mass fraction (solid fraction), and hydroxy-% hexyl-benyl-ketone (manufactured by Ciba Specialty Chemicals, Irgacure 184) as a photopolymerization initiator Department, modulation energy line hardening type adhesive. An adhesive sheet was produced in the same manner as in the example except that the energy ray-curable adhesive described above was used. [Comparative Example 1] An adhesive sheet was produced in the same manner as in Example 1 except that the blending amount of the isocyanate-based crosslinking agent was changed to 5 parts by mass (solid content). [Comparative Example 2] Except that the blending amount of the aminoacetic acid-based oligomer was changed to 12 Å by mass (solid content) and the blending amount of the isocyanate-based crosslinking agent was i 〇 mass fraction (solid fraction), the same The adhesive sheet was produced by the method of Example 1. [Comparative Example 3] The same procedure as in the above except that the blending amount of the urethane acrylate-based polymer was 8 Å by mass (solid content) and the amount of the isocyanate-based crosslinking agent was 1 Å by mass (solid content) The method of 1 makes an adhesive sheet. [Comparative Example 4] 21 201245376 A (mercapto) acrylate copolymer (as a carboxyl group relative to a (fluorenyl) acrylate copolymer) was prepared by copolymerizing 80 parts by mass of butyl acrylate and 20 parts by mass of acrylic acid. Equivalent 'addition of 30 equivalents of methacryloxyethyl isocyanate (MOI), weight average molecular weight 600,000, ethyl acetate / toluene / MEK mixed solvent, glass transition temperature -34. (:, solid concentration 30 mass %) 100 mass parts (solids), and tricyclodecane dinonanol diacrylate (NK Ester ADCP, manufactured by Shin-Nakamura Chemical Co., Ltd.) as an oligomer containing an energy-line polymerizable group And epoxy-based (meth) acrylate oligomer (manufactured by Shin-Nakamura Chemical Co., Ltd., NK 01 ig〇EA-1 020:) 28 parts by mass (solid content), and isocyanate-based crosslinking agent (Toyo Ink Manufacturing Co., Ltd.) 'Oribain BHS8515' solid content concentration: 37.5 mass%) 0.1 mass fraction (solid fraction), and 1-fluoro-cyclohexyl phenyl-ketone (manufactured by Ciba Specialty Chemicals, irgacure 184) as a photopolymerization initiator 3. 0 quality department, An energy ray-curable adhesive was prepared. The adhesive sheet was prepared in the same manner as in Example 1 except that the energy ray-curable adhesive described above was used. [Comparative Example 5] The urethane acrylate oligomer was changed to energy line hardening. Type urethane acrylate oligomer (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., υν_32ΐ 〇εα, weight average molecular weight 9000, glass transition temperature -27t, pencil hardness after hardening 6B-8B) 100 mass parts (solids)' and change The adhesive sheet was prepared in the same manner as in Example 1 except that the amount of the isocyanate-based crosslinking agent was 0.4 mass%. [Comparative Example 6] The urethane acrylate oligomer was changed to the energy ray-curing urethane propionate 22 201245376 Diluted vinegar-based oligomer (Japanese » . . , yv ^. Made by Chemical Industry Co., Ltd., UV-7000B, weight 35GG' broken glass transfer temperature - unm hardened pencil hardness H~F) 1〇〇, quality In the summer part (solid content), and the amount of the isocyanate-based crosslinking agent to be changed, the amount of the isocyanate-based crosslinking agent is 〇, and the same viscosity is produced. The other parts are the same as in the first embodiment [Test Example 1] (Measurement of elongation at break). Comparative example The total thickness of the adhesive layer in the adhesive sheet is 〇〇#m, and in the case where the outermost layer of the laminated body is only the separation sheet, the above-mentioned adhesive layer is laminated in a plurality of layers, and is placed under hunger and atmosphere. 2 weeks. After that, the adhesive sheet of the above-mentioned adhesive layer of the laminated layer is cut into a sample of 15 mm width x 55nun#, and the release sheet laminated on the outermost layer of the laminate is sampled. The measurement range is 15 with a width of 25, and the sample is placed in a universal tensile tester (SHIMADZU public deletion (8). Then in the environment of hunger and 5 coffee, to:
的拉伸速度使n長，t # ^斷I 長率。結果如表丨所示。 說延 [§式驗例2 ](應力鬆弛率測定） 使實施例或比較例所得的黏著片中的黏著劑層的總厚 度成為500 且以層積體的最表面層只有制離片的情形 層積複數層的上述黏著劑層，在23t、5〇%RH的氛圍氣下 放至2週。之後，將層積複數層上述黏著劑層的黏著片裁 切成15mm寬x55mm長的樣品，剝離層積於層積體最表面層 的剝離片，以樣品的測定範圍為i 5mm寬x25mm長，將樣品 放置於萬能拉伸試驗機（SHIMADZU公司製，Aut〇graph 23 201245376 AG-删⑻。然後在23t、5_的環境下，以鳳/分 的拉伸速度使樣品伸長，測定在3〇〇%伸長時的應力 A(Pa) ’及伸長停止後的議秒時的應力B(pa)。根據所挪 得的應力A與應力B’以下式計算應力鬆弛率⑻。結果如 表1所示。 應力鬆弛率（％) =丨（A-BVAUIOOU) [試驗例3 ](凝膠分率測定） 將實施例或比較例所得的黏著片作為8Qmmx8()mm體積 的樣品化，將去除剝離片的黏著劑層覆蓋於聚酯製的篩(網 目數:20〇mesh/inCh)，w精密天平測量僅黏著劑的質量。 此時的質量定為Ml。 其次，將上述黏著劑樣品在室溫（23t )下浸潰於乙酸 乙酯溶劑24小時。之後取出黏著劑，在抓、5〇%RH的環 境下’風乾24小時’再於峨的烤箱中乾燥12小時。以 精密天平測量乾燥後僅黏著劑的質量。此時的質量定為 M2。凝膠分率（％)以（Μ2/Μ1)χ1〇()表示。結果如表i所示。 [試驗例4 ](伸長成型性評估） 將實施例或比較例所得的黏著片，如第3圖所示，進 仃伸長成型性評估。㈣^，剝離黏著片1B的輕剝離型剝 離片12a(第3(a)圖），將不鏽鋼（SUS3〇4)製的微注射器14 (Hami lton 公司製，容量 5 μ 1，95RN 型，針 22S PT-3)的 針頭前端壓入露出的黏著劑層u(第3(1))圖）。之後剝離重 剝離型剝離片12b，將微注射器14的針頭前端埋入黏著劑 層11至厚度1〇以m(第3(c)圖）。 24 201245376 其次’使用微注射器14，從針 1畔月'』％(將4 μ 1的空氣注 入黏著劑層11，使黏著劑層i i只有 、 男訂碩前端埋入的部分變 形（第3 (d)圖）。之後，使用紫外雏 用糸外線照射裝置15(FUSI0N公 司製，CV-110O-G)照射紫外線（昭产 匕'度12〇mW，光量70mJ)(第 3⑷圖），將硬化的黏著劑層u從針頭前端取出(第3⑴ 圖）。觀察黏著劑層U的變形部分的樹脂形狀結果如表】 所示。觀察樹脂形狀的評估基準如下所述。 〇：樹脂形狀維持約球狀。 △:樹脂形狀沒有鼓起至半球以上，或在鼓起成半球前 發生皺紋》 X :樹脂未膨脹，形狀不整齊。或者，從針頭取出時被 破壞，或鼓起前已從針頭前端剝離。 [表1 ] 黏著劑之組成 物枓 (甲基）丙烯酸酯 共聚物 (固型分質量部） 能量線硬化型氨 酯丙烯酸酯 (固型分質量部） 交聯劑 (固型分質t部） 斷裂延伸率 (%) 應力鬆弛率 «) 凝膠分牟 (%) 評估 伸長 成型性 實施例1 100 100 0.1 2700< 89 5 .實施例2 100 100 0.2 2700< 82 7 U Γ\ 贲施例3 100 100 0.3 2700< 77 26 D 實施例4 100 120 0.2 2642 84 6 r\ 實施例5 ίοο 80 0.2 2700< 78 ———. 6 實施例6 100 80/20 0.1 2700< 74 3 — — —Δ_ A 比較例1 100 100 0.5 1989 69 一 一 32 比較例2 100 120 1.0 1070 61 33 比較例3 100 80 1.0 1466 64 35 _比較例4 100 52/28 0.1 2700< 68 23 比較例5 100 100 0.4 1500 73 34 —A_ Lx_ 較例6 100 100 0.4 900 71 • 一 一 29 1 - ...... _— 如表1所示可知，滿足本發明要件之實施例所得的能 25 201245376 量線硬化型黏著劑為伸長成型性上優良者。 【產業利用性】 本發明之能量線硬化型黏著劑及黏著片可使用於成型 如微膠囊、特殊填充料、微透鏡膜等。 【圖式簡單說明】 第1圖為本發明之第1實施態樣之黏著片的剖 第2圖為本發明之第2實施態樣之黏著片之刮面。 第3(a)⑴圖為顯示試驗例4巾伸長成型 序之說明圖。 ° 1買的川員 【主要元件符號說明】 ΙΑ、1Β〜黏著片 1卜黏著劑層 12、12a、12b〜剝離片 1 3 ~基材 1[微注射器 15~紫外線照射t f 26The stretching speed makes n long, t #^break I long rate. The results are shown in the table. The extension [§ test example 2] (stress relaxation rate measurement) The total thickness of the adhesive layer in the adhesive sheet obtained in the example or the comparative example was 500 and the outermost layer of the laminate was only the separation sheet. The above-mentioned adhesive layer of a plurality of laminated layers was placed in an atmosphere of 23t and 5〇% RH for 2 weeks. Thereafter, the adhesive sheet of the plurality of layers of the adhesive layer is cut into a sample having a length of 15 mm and a length of 55 mm, and the release sheet laminated on the outermost layer of the laminate is peeled off, and the measurement range of the sample is i 5 mm wide by 25 mm long. The sample was placed in a universal tensile tester (manufactured by SHIMADZU Co., Ltd., Aut〇graph 23 201245376 AG-deleted (8). Then, in a 23t, 5_ environment, the sample was elongated at a stretching speed of phoenix/minute, and measured at 3〇. The stress A (Pa) ' at the time of 〇% elongation and the stress B (pa) at the second time after the elongation is stopped. The stress relaxation rate (8) is calculated from the obtained stress A and stress B' as follows. The results are shown in Table 1. Stress relaxation rate (%) = 丨 (A-BVAUIOOU) [Test Example 3] (measurement of gel fraction) The adhesive sheet obtained in the example or the comparative example was sampled in an 8Qmm x 8 () mm volume to remove the peeling. The adhesive layer of the sheet is covered with a polyester mesh (mesh number: 20 〇mesh/inCh), and the w precision balance measures the mass of only the adhesive. The mass at this time is determined as M1. Next, the above adhesive sample is placed in the chamber. Immerse in ethyl acetate solvent at temperature (23t) for 24 hours. Then remove the adhesive and grab it. In the environment of 5〇%RH, 'air-dry for 24 hours' and then dry in the oven for 12 hours. Measure the quality of the adhesive only after drying with a precision balance. The mass at this time is set to M2. The gel fraction (%) is (Μ2/Μ1) χ1〇() is shown. The results are shown in Table i. [Test Example 4] (Evaluation of elongation moldability) The adhesive sheet obtained in the example or the comparative example, as shown in Fig. 3, was stretched. Moldability evaluation. (4) ^, the light peeling release sheet 12a of the adhesive sheet 1B (Fig. 3(a)), and a micro syringe 14 made of stainless steel (SUS3〇4) (manufactured by Hamilton Co., Ltd., capacity 5 μ 1, The tip end of the needle of the 95RN type, needle 22S PT-3) is pressed into the exposed adhesive layer u (Fig. 3(1)). Thereafter, the heavy release type release sheet 12b is peeled off, and the tip end of the needle of the micro syringe 14 is embedded in the adhesive layer 11 to a thickness of 1 m m (Fig. 3(c)). 24 201245376 Next, 'Using the micro-injector 14 from the needle 1 month'』% (injecting 4 μl of air into the adhesive layer 11 to deform the adhesive layer ii only, the part where the male front end is buried (3rd ( d) Fig.). After that, ultraviolet light is applied to the external light irradiation device 15 (manufactured by FUSI0N Co., Ltd., CV-110O-G) to irradiate ultraviolet rays (12 〇mW, light quantity 70 mJ) (Fig. 3 (4)), which will harden. The adhesive layer u was taken out from the front end of the needle (Fig. 3(1)). The results of observing the resin shape of the deformed portion of the adhesive layer U are shown in the table. The evaluation criteria for observing the shape of the resin are as follows. 〇: The shape of the resin is maintained to be about the ball. △: The shape of the resin does not bulge above the hemisphere, or wrinkles occur before bulging into a hemisphere. X: The resin is not inflated and the shape is not neat. Or, it is broken when taken out from the needle, or has been removed from the front of the needle before bulging. Peeling. [Table 1] Adhesive composition 枓 (meth) acrylate copolymer (solid type mass part) Energy line hardening urethane acrylate (solid type mass part) Crosslinking agent (solid type partition) Part t) elongation at break (%) stress relaxation rate Gel fractionation (%) Evaluation Elongation Formability Example 1 100 100 0.1 2700<89 5 . Example 2 100 100 0.2 2700<82 7 U Γ\ 贲 Example 3 100 100 0.3 2700< 77 26 D Example 4 100 120 0.2 2642 84 6 r\ Example 5 ίοο 80 0.2 2700< 78 ———. 6 Example 6 100 80/20 0.1 2700< 74 3 — — —Δ_ A Comparative Example 1 100 100 0.5 1989 69 One by one 32 Comparative Example 2 100 120 1.0 1070 61 33 Comparative Example 3 100 80 1.0 1466 64 35 _Comparative Example 4 100 52/28 0.1 2700< 68 23 Comparative Example 5 100 100 0.4 1500 73 34 —A_ Lx_ Comparative Example 6 100 100 0.4 900 71 • One-to-one 29 1 - ... _ - As shown in Table 1, it is understood that the energy-curable adhesive obtained by the embodiment satisfying the requirements of the present invention is excellent in elongation moldability. [Industrial Applicability] The energy ray-curable adhesive and the adhesive sheet of the present invention can be used for molding such as microcapsules, special fillers, microlens films, and the like. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an adhesive sheet according to a first embodiment of the present invention. Fig. 2 is a view showing a scraping surface of an adhesive sheet according to a second embodiment of the present invention. Fig. 3(a)(1) is an explanatory view showing the elongation molding of the test piece 4. °1Chuanchuan bought [Main component symbol description] ΙΑ, 1Β~Adhesive sheet 1 Bubber layer 12, 12a, 12b~ Release sheet 1 3 ~ Substrate 1 [Micro syringe 15~ UV irradiation t f 26