201043427 六、發明說明： ^ 【發明所屬之技術領域】 本發明係關於一種印紋用模板及其製造方法。 【先前技術】 近來’已有一種可將微細圖案以良好效率形成於基板 表面而提高生產量（throughpu1:)之印紋微影技術（imprint lithography)受到矚目。印紋微影技術係在基板表面形成 由硬化性樹脂組成物所構成之皮膜，且用模板將此皮膜表 面加C而將模板之微細圖案進行轉印，且使轉印有微細圖 案之皮膜硬化，而將微細圖案形成於基板表面之方法。 以印紋微影方式形成之微細圖案，為了與所使用之模 板之微細圖案對應，印紋微影之模板之重要性極高。為了 防止則述樹脂組成物之附著，模板之微細圖案通常係施有 藉由 έ 氣自組化膜（fluorinated self-assembled monolayer)等所作脫模處理。 、一“而’當重複進行印紋微影時，會有施於微細圖案之 、二处里劣化之問題（參照例如非專利文獻1 )。若以脫模 王军 /L· ^ * 棋叛進行印紋微影，則不僅轉印精確度會降 低，模板本身亦會破損。 右對核板之微細圖案施行再脫模處理，則又會損及屬 文微影技術特徵之一的高產量化。此外，模板之微細 圖案通常传+ 、9 電子束（EB : electron beam)微影來形成。 由於EB微影俞θ、 ^ 私疋焚雜的圖案愈需要時間來形成，因此模板 ---日 yr|> 貝就热法簡單重現。因此’乃希望開發一種不 4 321598 201043427 需施行脫模處理或再脫模處理而可簡單重現之模板。 [非專利文獻 1] Y. Tada，H. Yoshida，and A. Miyauchi, J. Photopolym. Sci. Technol., 20, p545, 2007 ^ 【發明内容】 [發明所欲解決之課題] 本發明之目的係提供一種具有高度脫模性，而且可簡 單重現之印紋用模板及其製造方法。 [解決問題之方案] 〇 本發明之印紋用模板係具備：表面層，在表面具有微 細圖案；及支撐層，用以支撐該表面層之與前述表面相反 之背面；前述表面層係由側鏈結晶性聚合物所構成。 本發明之印紋用模板之製造方法係包括：在支撐層上 疊層由侧鏈結晶性聚合物所構成之表面層之步驟；將該表 =層之表面，以具有微細圖案之主模，在前述側鏈結晶性 聚合物之熔點以上之溫度加壓之步驟；及接著將前述表面 〇層之溫度設在未達侧鏈結晶性聚合物之溶點之溫度，將主 、從剛述表面層之表面剝離，而將主模之前述微細圖案轉 印至表面層之表面之步驟。 [發明之功效] 依據本發明之印紋用模板，由於模板之微細圖案係由 二有優異餘性之側鏈結晶性聚合物所構成，因此不需對 模板之微細圖案施行脫模處理。因此，亦不需對模板之微 圖木施行1知之再脫模處理，而不會損及印紋微影之高 產量化。 321598 5 201043427 依據本發明之印紋用模板之製造方法，係將主模之微 細圖案予以熱印紋至側鏈結晶性聚合物而形成模板之微細 圖案。由於對於侧鏈結晶性聚合物之熱印紋可在相對較低 溫下進行，因此可在短時間内以良好效率進行熱印紋而獲 得本發明之模板。而且，藉由重複使用主模，即可簡單重 現前述模板。 【實施方式】 以下參照第1圖詳細說明本發明之印紋用模板之一實 施形態。如第1圖所示，本實施形態之印紋用模板10係具 備表面層1與支撐層5。 表面層1係由侧鏈結晶性聚合物所構成。該側鏈結晶 性聚合物係在未達熔點之溫度結晶化，而且是在前述熔點 以上溫度顯示流動性之聚合物。亦即，前述側鏈結晶性聚 合物係與溫度變化對應而可逆性地產生結晶狀態與流動狀 態。 由前述側鏈結晶性聚合物所構成之表面層1係在其表 面la形成有微細圖案2,而該微細圖案2亦為由侧鏈結晶 性聚合物所構成。前述結晶狀態之侧鏈結晶性聚合物係具 有高度脫模性。因此，微細圖案2亦具有高度脫模性，因 此不需對微細圖案2施行習知之脫模處理。 前述熔點係意指由於某平衡過程，使起初調整為有秩 序之排列之聚合物之特定部分成為無秩序狀態之溫度，其 為藉由示差掃描熱量計（differential scanning ca 1 or imetry ) ( DSC)以10°C /分鐘之測定條件測量所獲 6 321598 201043427 得之值。模板ίο係在側鏈結晶性聚合物處於結晶狀態下未 達熔點之溫度使用。因此，以前述熔點而言，係以以 上為較佳’ 50至60。(：為尤佳。 另一方面，若前述熔點太低，模板1〇之可使用溫度 範圍變窄，故不理想。此外，模板1〇之微細圖案2，如後 所述，係以熱印紋方式成形。因此，若前述炫點太高，則 難以進行熱印紋，故不理想。要將前述熔點設為預定值， 〇可藉由改變侧鏈結晶性聚合物之組成等來任意進行。 以前述侧鏈結晶性聚合物之組成而言’可列舉例如使 具有碳數16以上之直鏈狀烷基（alkyl)之（甲基）丙烯酸 酯（（meth)aCrylate) 20至1〇〇重量份、具有碳數〗至6 之烷基之（甲基）丙烯酸酯〇至7〇重量份、及極性單體〇 至10重量份予以聚合所獲得之聚合物等。 以前述具有碳數16以上之直鏈狀烷基之（甲基）丙烯 酸酯而言，可列舉例如（甲基）丙烯酸十六烷酯、（甲基）丙 ❹烯酸十八烷酯、（甲基）丙烯酸二十烷酯、（甲基）丙烯酸二 十一烷酯等具有碳數16至22之線狀烷基之（曱基）丙烯酸 酯，以前述具有碳數i至6之烷基之（罗基么兩爆酸酯而言，… 係可列舉例如（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲 基）丙烯酸丁酯、（甲基）丙烯酸已酯等，以前述極性單體而 s係可列舉例如丙烯酸、甲基丙烯酸、丁烯酸、衣康酸、 馬來酸、富馬酸等含羧基之乙烯不飽和單體、（甲基）丙烯 酸2~羥乙酯、（甲基）丙烯酸2-羥丙酯、（甲基）丙烯酸2_ 羥己酯等具有羥基之乙烯不飽和單體等，而此等亦可使用 321598 7 201043427 1種或混合2種以上來使用。 以聚合方法而言，並未特別限制，可採用例如溶液聚 &法、塊狀聚合法、懸浮聚合法、乳化聚合法等。採用例 如溶液聚合法時，係將前述所例示之單體混合於溶劑，並 在40至90°C左右下攪拌2至1〇小時左右，藉此即可使前 述單體聚合。 前述側鏈結晶性聚合物之重量平均分子量係可為 100’ 000以上，較佳為400, 〇〇〇至800, 〇〇〇。若前述重量平 均分子量太小，則微細圖案2之強度會降低而有容易損傷 之虞。此外，若前述重量平均分子量太大，則即使將側鍵 結晶性聚合物設在熔點以上之溫度亦難以顯示流動性，因 此難以進行熱印紋。前述重量平均分子量係以凝膠渗透層 析儀（gel permeati〇n chr〇mat〇graphy)(Gpc)來測量側 鍵結晶性聚合物，且將所獲得之測量值換算為聚苯乙稀之 值。 以表面層1之厚度而言，係以〇· 01至1，000 /z m左右 為適田匕所明表面層丨之厚度係指表面“和與該表面& =反之背面lb之間之距離達到最大之厚度。此外，微細圖 木2係以奈米乃至微米級為較佳。微細圖案2之形狀並無 特別限定，可採用所希望者。 …、 方面支擇層5係用以支樓表面層1之背面 1’，^為對模板10賦予剛性者。以構成支撐層5之材料而 0歹!舉例如石夕、石夕酮、（$丨&)玻璃等。以支撐層5之 旱又而0係以至lOOOgm左右為適當。 321598 8 201043427 此外在支撐表面層1之支撑層5之表面5a係以施 行表面處理較佳。藉此，可使表面％粗面化，而提升夫撐 層5與表面層1之密著性。以前述表面處理而言，可列舉 例如輝光放電處理、電漿處理、喷砂處理、化學蝕刻處理、 底塗層（primer)處理等。 在此，由前述側鏈結晶性聚合物所構成之表面層1通 常係具有uv穿透性。對uv硬化性樹脂組成物進行印紋微 衫牯，係以藉由具有穿透性之材料來構成支撐層5較 〇佳。藉此，模板10整體即具有UV穿透性，因此可隔著該 模板10將UV照射於uv硬化性樹脂組成物。 接著參照第2圖詳細說明模板1〇之製造方法。如第2 圖（a)所示，首先，在支撐層5上疊層由側鏈結晶性聚合 物所構成之表面層1。疊層有表面層1之支撐層5之表面 5a’在提升與表面層1之密著性方面，係以施行表面處理 使之粗面化較佳。此外，前述疊層係藉由將塗佈液塗佈於 〇支樓層5上且使之乾燥來進行，該塗佈液係為將前述侧鏈 結晶性聚合物加入溶劑而成者。 前述塗佈一般係可藉由刮刀塗佈機（kni f e coater)、 滾筒塗佈機（rol 1 coater )、壓輥塗佈機（calendar coater )、缺角輪塗佈機（co顏a coater)等來進行。此外， 依據塗佈厚度及塗佈液之黏度不同，亦可藉由凹版塗佈機 (gravure coater )、棒塗佈機（r〇d coater)、旋塗機（spin coater)等來進行。 另外，除前述塗佈以外，表面層1之疊層尚可藉由例 9 321598 201043427 如以擠出成形及壓延加工成形為片體 1疊層於支撐層5上來進行。 —，專骐狀之表面層 在支撐層5上疊層表面層i之後，如 不，在表面層i上方配置主模2〇。以）所 料而言，係以對賴結晶性聚合物親和^才 佳，例切、㈣、⑶⑹玻璃等。^低之材枓為較 …在與表面層1之表面la相對向之主模 形成有微細圖案21。該微細圖荦21 g 、 a 板1◦之微細圖案2。因此，微細圖1幸之 所希望之微細圖案2相反之圖孝者狀係採用與 或微米級較佳，其可藉由EB微影來形成。 ”、 —將此主模20朝箭頭八方向移動，且如第⑽ =將表面層！之表面la以主模2G_。此加壓係^ =側鏈結晶性聚合物之熔點以上溫度進行。藉此，前述側 鏈'w曰性聚合物即成為流動狀態，而可進行將主模2〇之微 細圖案21轉印至表面層！之表面匕之熱印紋作業。 。以加壓溫度而言，係以前述侧鏈結晶性聚合物之溶點 + 1〇(：至絲+ 3()。(：之溫度較佳。藉此，前述側鏈結晶性 聚合物即絲適度之流純態，喊升域2()之轉印精確 度，且達成在相對較低溫度之熱印紋作業。相對於此，若 前述加壓溫度太低，則側鏈結晶性聚合物之流動狀態變 低’而會有主模20之轉印精確度降低之虞。此外，若前述 加壓溫度太高，則會將側鏈結晶性聚合物過度加熱，而耗 費較多熱能，不具經濟性。 321598 20 201043427 前述加壓溫度之調整，係可藉由例如在與主模20之 表面20a相反之背面20b配設加熱器等加熱手段，且以該 加熱手段將微細圖案21之表面溫度加熱至預定溫度、或將 雾圍溫度調整至前述側鏈結晶性聚合物之熔點以上溫度等 來進行。至於其他加壓條件，係以壓力為0.1至lOOMPa 左右、加壓時間為5至300秒左右較佳。 在以主模20將表面層1之表面la加壓之後，維持此 狀態，並且使用風扇等冷卻手段將表面層1之溫度冷卻至 〇 未達前述侧鏈結晶性聚合物之熔點之溫度。藉此，前述側 鏈結晶性聚合物即成為結晶狀態。 再者，如第2圖（d)所示，使主模20朝箭頭B方向 移動，從由結晶狀態之側鏈結晶性聚合物所形成之表面層 1之表面la將主模20剝離。此時，結晶狀態之側鏈結晶 性聚合物係如前所述具有較高之脫模性。因此，即使不對 主模20之微細圖案21施行脫模處理，亦可將主模20從表 0面層1剝離，而可提高生產力。 若將主模20從表面層1剝離，主模20之微細圖案21 就會轉印至表面層1之表面la，而可獲得具有與微細圖案 21相反圖案之微細圖案2之模板10。再者，只要使用主模 20重複進行前述之各步驟，即可簡單重現模板10。 接著以使用UV硬化性樹脂組成物在硬化性樹脂組成 物之情形為例，參照第3圖詳細說明使用模板10製造微細 構造之一實施形態。如第3圖（a)所示，首先，在基板 51表面形成皮膜52。 11 321598 201043427 以構成基板51之材料而言，除發、（以⑹玻璃等之 ，例如尚有聚乙烯、聚對苯二甲酸乙二醋、 ::、聚_、聚酿亞胺、聚碳酸醋、乙烯贈酸乙婦醋共： 物、乙烯丙稀酸乙醋共聚物、乙稀聚氣 烤等合成樹脂。基板W具有可触為較佳，以^产 而言，係例如為5〇至__，較佳為⑽至15〇_左^ 皮膜52係由UV硬化性樹脂組成物所構成。該肝硬 化性樹脂組成物係藉由照射uv (紫外線）而硬化者，可採 ::種:知者。皮膜52之形成係例如將肝硬化性樹脂： 成物加在預定的溶劑來獲得塗佈液，且將此塗佈液塗佈於 基板51表面使之乾燥即可。前述塗佈係可藉由例如旋塗、 細縫塗佈（sht咖㈣）、噴射塗佈、滾筒塗佈等來進行。 未硬化之賴52之厚度係例如為Q. Q1幻，⑽^ 為0.01至500#m左右。 _在基板51表面形成皮膜52之後，如第3圖⑴ 不，在皮膜52上方配置模板1〇。此配置係以使模板 細圖案2與皮膜52相對向之方式進行。接著，將此模板 1。朝箭頭C方向移動，如第3圖⑷所示，將皮膜52、表 面以拉板10加>1。藉此，模板1G之微細圖案2即轉印至 士以加麼條件而言，虔力為O.lSlOOMPa左右，加屋 時間為5 i 3GG秒左右。經轉印有微細圖案2之皮膜犯 之硬化，係在以模板10加屢皮膜52表面之狀態下，亦即 對第3圖（C)所示之狀態之皮膜52照射UV來進行。 321598 12 201043427 以UV照射方向而言，只要可對皮膜52照射ϋν，則無 特別限定。亦即，基板51具有υν穿透性時，只要從基板 51之者面侧對皮膜52照射UV即可。此外，以具有uv穿 透性之材料構成模板1Q之支撐層5時，由於模板1 〇整體 係如前所述地具有UV穿透性，因此可隔著該模板10對皮 臈52照射UV。 接著’如第3圖（d)所示，使模板1〇朝箭頭d方向 〇移動，將模板10從已硬化之被膜53剝離。此時，雖未對 模板10之微細圖案2施行脫模處理，惟由於前述之理由該 微細圖案2具有較高脫模性，因此剝離時對硬化被膜53 所施加之負載較小。因此，若將模板1〇從硬化被膜剝 離，則可獲得由優異精確度轉印微細圖案2之硬化被膜 53、與基板51所構成之微細構造5〇。另外，以硬化被膜 53之厚度而言，係例如為〇. 〇1至1〇〇〇，較佳為〇 〇1 至500 # m左右。 Ο 所獲得之微細構造50係可以例如氧反應離子蝕刻等 方式將其殘膜54去除，且於使基板51表面從鄰接之硬化 被膜53、53間露出之後，以硬化被膜53為遮罩進行钱刻 處理，或將鋁等進行剝離（lift off)加工而利用於配線 等。 另外，在前述實施形態中，雖係以uv硬化性樹脂組 成物作為硬化性樹脂組成物為例進行了說明，惟以其他硬 化性樹脂組成物而言，亦可使用例如聚曱基丙烯酸甲酯 (Polymethyl methacrylate) (PMMA)等熱可塑性樹脂組 321598 13 201043427 成物。此外，在前述實施形態中，雖係針對在以模板加壓 之狀態進行業經轉印微細圖案之皮膜之硬化之情形進行了 說明，惟前述皮膜之硬化亦可在將模板剝離之後進行。 以下將以實施例為例進一步詳細說明本發明，惟本發 明並不限定於以下之實施例。 [實施例] 以下實施例中所使用之側鏈結晶性聚合物之製造係 如下所述。 〈合成例> 依丙烯酸二十二烷酯（日油公司製）50份、丙烯酸甲 酯（日本觸媒公司製）45份、丙烯酸5份及perbutyl ND (日油公司製）0.2份之比例，分別加在醋酸乙酯230份 予以混合，在55°C下攪拌4小時，而使此等單體聚合。所 獲得之共聚物（側鏈結晶性聚合物）之重量平均分子量係 為60萬，熔點為55°C。前述重量平均分子量係為藉由GPC 測量共聚物，且將所獲得之測量值換算成聚苯乙烯之值。 此外，前述熔點係為使用DSC以10°C/分鐘之測量條件所 測量之值。 <印紋用模板之製作> 如第2圖所示方式製作本發明之印紋用模板。所使用 之各構件如下。 表面層：使用在前述合成例中所獲得之側鏈結晶性聚 合物。 支撐層：使用厚度為625 //Π1之矽。對於支撐前述表 14 321598 201043427 面層之支撐層之表面施行乾蝕刻處理作為表面處理。前述 乾蝕刻處理係以SFe氣體進行。 主模：使用由矽所構成之模，該模係在表面具有以EB 微影方式所形成之奈米級之微細圖案。 主模之前述微細圖案係作成並設有複數條凸條之形 狀。前述凸條之寬度為490nm，間距間隔為180nm。另外， 前述寬度及間距間隔均係n= 10之平均值。對於主模之前 述微細圖案未施行脫模處理。 ❹ 加壓條件如下。 加壓溫度：70°C (側鏈結晶性聚合物之熔點+ 15°C) 壓力：5MPa 加壓時間：60秒 另外，前述加壓溫度之調整係藉由在主模背面配設加 熱器，且以該加熱器加熱使微細圖案之表面溫度成為70°C 方式進行。 Q 模板之製作係以下列方式進行。首先，在支撐層上疊 層表面層（參照第2圖（a))。此疊層係藉由將塗佈液以旋 塗機塗佈於支撐層上，且在100°C之雾圍溫度使之乾燥方 式進行，該塗佈液係為將前述側鏈結晶性聚合物加在醋酸 乙酉旨而成者。所疊層之表面層之厚度係為1/zm。 接著在表面層上方配置主模（參照第2圖（b))，藉 由該主模將表面層之表面以前述加壓條件進行加壓（參照 第2圖（c))。保持該主模之加壓狀態，並且使用風扇將表 面層之溫度冷卻至未達前述側鏈結晶性聚合物之熔點之溫 15 321598 201043427 度之至/皿（23 C )。然後，將主模從表面 得模板（參照第2圖⑷）。 表面漏而獲 針對所獲得之模板之微細圖案，藉由掃描型電子 鏡進鏡觀察（倍率：12，_倍結果如以圖所 :地Π圖可得知’在模板之表面層之表面，精確度良 轉印有主模之微細圖案之相反圖案。具體而古，可得 知具有180nm之寬度dl之仏仫qn 篮而口 了付 d2 凸條30，以490nm之間距間隔 平均值 寬度以及間距間隔d2均係為之 並未：二：目視觀察剝離後之主模之微細圖案之結果， 將主_結晶性聚合物。從此等結果可得知，藉由 物 微細圖案予以熱（奈米）印紋於側鏈結晶性聚合 物，可形成膜板之料细岡安ll , Β ^ ^ σ 不需施杆妝H 外’對於主模之微細圖案 得之模板，2理，可謂具有優異生產力。只要使用所獲 印紋微影。、_板之微細圖案施行脫模處理亦可進行 【圖式簡單說明】 略側=圖係為顯示本發明印紋用模板之-實施形態之概 之¥造方Γ之t)至⑷係為顯示第1圖所示印紋用模板 表以万法之步驟圖。 製補田構造之-實施形態之步驟圖。 弟4圖係為以實施例所獲得之印紋用模板之掃描型電 321598 16 201043427 子顯微鏡相片。 【主要元件符號說明】201043427 VI. Description of the Invention: ^ Technical Field of the Invention The present invention relates to a template for printing and a method of manufacturing the same. [Prior Art] Recently, an imprint lithography which can form a fine pattern on a substrate surface with good efficiency and increase throughput (throughpu1:) has been attracting attention. The lithography technique forms a film composed of a curable resin composition on the surface of the substrate, and applies a C to the surface of the film to transfer the fine pattern of the template, and hardens the film transferred with the fine pattern. A method of forming a fine pattern on the surface of the substrate. The fine pattern formed by the lithography method is extremely important in order to correspond to the fine pattern of the template to be used. In order to prevent adhesion of the resin composition, the fine pattern of the template is usually subjected to a release treatment by a fluorinated self-assembled monolayer or the like. "When the lithography is repeated, there is a problem that the fine pattern is applied to the two places (see, for example, Non-Patent Document 1). If the demolished Wang Jun/L·^* is rebellious When printing lithography, not only the transfer accuracy will be reduced, but also the template itself will be damaged. The right re-release of the fine pattern of the nuclear plate will damage the high yield of one of the characteristics of the genre lithography. In addition, the fine pattern of the template is usually formed by the EB: electron beam lithography. Since the EB lithography θ, ^ privately burned pattern takes time to form, the template -- -Day yr|> The heat method is simply reproduced. Therefore, 'I hope to develop a template that can be easily reproduced without the mold release treatment or the mold release treatment. [Non-Patent Document 1] Y. Tada, H. Yoshida, and A. Miyauchi, J. Photopolym. Sci. Technol., 20, p545, 2007 ^ [Summary of the Invention] [Problem to be Solved by the Invention] An object of the present invention is to provide a highly releasable property. And the template for printing and its manufacturing method can be simply reproduced. Solution to the problem] The template for printing of the present invention comprises: a surface layer having a fine pattern on the surface; and a support layer for supporting a back surface of the surface layer opposite to the surface; the surface layer is formed by a side chain The method for producing a template for printing according to the present invention comprises the step of laminating a surface layer composed of a side chain crystalline polymer on a support layer; a main mold having a fine pattern, a step of pressurizing at a temperature higher than a melting point of the side chain crystalline polymer; and then setting a temperature of the surface layer to a temperature at a melting point of the side chain crystalline polymer The main film is peeled off from the surface of the surface layer, and the fine pattern of the master mold is transferred to the surface of the surface layer. [Effect of the Invention] The template for printing according to the present invention is due to the fine pattern of the template. It is composed of two side chain crystalline polymers with excellent reciprocity. Therefore, it is not necessary to perform demolding treatment on the fine pattern of the template. Therefore, it is not necessary to perform a re-demolition of the micro-pattern of the template. 321598 5 201043427 The method for producing a pattern for printing patterns according to the present invention is characterized in that a fine pattern of a master mold is hot-printed to a side chain crystalline polymer to form a pattern. Fine pattern of template. Since the hot print for the side chain crystalline polymer can be carried out at a relatively low temperature, the template of the present invention can be obtained by performing hot stamping with good efficiency in a short time. Moreover, by repeating The template can be easily reproduced by using the master mold. [Embodiment] Hereinafter, an embodiment of the template for printing of the present invention will be described in detail with reference to Fig. 1. As shown in Fig. 1, the pattern template 10 of the present embodiment has a surface layer 1 and a support layer 5. The surface layer 1 is composed of a side chain crystalline polymer. The side chain crystalline polymer is crystallized at a temperature not reaching the melting point, and is a polymer exhibiting fluidity at a temperature higher than the above melting point. That is, the side chain crystalline polymer is reversibly generated in a crystalline state and a fluid state in accordance with a change in temperature. The surface layer 1 composed of the above-mentioned side chain crystalline polymer has a fine pattern 2 formed on the surface la, and the fine pattern 2 is also composed of a side chain crystalline polymer. The side chain crystalline polymer of the above crystalline state has a high releasability. Therefore, the fine pattern 2 also has a high mold release property, so that it is not necessary to perform a conventional mold release treatment on the fine pattern 2. The aforementioned melting point means a temperature at which a specific portion of the polymer which is initially adjusted to an ordered arrangement becomes disordered due to a certain balancing process, which is by differential scanning ca 1 or imetry (DSC) The measured conditions of 10 ° C / min measured the value obtained by 6 321 598 201043427. The template ίο is used at a temperature at which the side chain crystalline polymer is in a crystalline state and does not reach the melting point. Therefore, in terms of the aforementioned melting point, the above is preferably '50 to 60'. On the other hand, if the melting point is too low, the usable temperature range of the template 1 变 is narrow, which is not preferable. Further, the fine pattern 2 of the template 1 , is hot stamped as described later. Therefore, if the smudge point is too high, it is difficult to perform hot stamping, which is not preferable. The melting point is set to a predetermined value, and 〇 can be arbitrarily changed by changing the composition of the side chain crystalline polymer or the like. In the composition of the aforementioned side chain crystalline polymer, for example, a (meth) acrylate having a linear alkyl group having 16 or more carbon atoms ((meth) a Crylate) 20 to 1 〇〇 can be cited. a polymer obtained by polymerizing a (meth) acrylate having a carbon number of 1-6 to 6 to 7 Å by weight, and a polar monomer 〇 to 10 parts by weight, etc. Examples of the above linear alkyl (meth) acrylate include hexadecyl (meth) acrylate, octadecyl (meth) acrylate, and (meth) acrylate. An alkyl ester, a behenyl (meth) acrylate, etc. having a carbon number of 16 to 22 As the alkyl (mercapto) acrylate, the above-mentioned alkyl group having a carbon number of i to 6 (for the rhodium bismuth acrylate), for example, methyl (meth) acrylate, (methyl) Ethyl acrylate, butyl (meth) acrylate, (meth) acrylate, etc., and s of the above-mentioned polar monomer, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid a hydroxyl group-containing ethylenically unsaturated monomer such as fumaric acid, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate or 2-hydroxyhexyl (meth)acrylate The unsaturated monomer or the like may be used in the form of 321598 7 201043427 or a mixture of two or more. The polymerization method is not particularly limited, and for example, a solution polymerization method, a bulk polymerization method, or the like may be employed. By suspension polymerization method, emulsion polymerization method, etc., for example, when the solution polymerization method is used, the monomer exemplified above is mixed in a solvent, and stirred at about 40 to 90 ° C for about 2 to 1 hour, whereby Polymerization of the aforementioned monomer. The weight of the aforementioned side chain crystalline polymer is flat The molecular weight may be 100'000 or more, preferably 400, 〇〇〇 to 800, 〇〇〇. If the weight average molecular weight is too small, the strength of the fine pattern 2 may be lowered to cause damage. When the weight average molecular weight is too large, it is difficult to exhibit fluidity even if the side bond crystalline polymer is set at a temperature higher than the melting point, and thus it is difficult to perform hot stamping. The above weight average molecular weight is a gel permeator (gel permeati). 〇n chr〇mat〇graphy) (Gpc) to measure the side bond crystalline polymer, and convert the obtained measurement value to the value of polystyrene. In terms of the thickness of the surface layer 1, it is 〇· 01 To a thickness of about 1,000 /zm, the thickness of the surface layer of the surface of the field refers to the thickness of the surface "and the distance between the surface & Further, the fine wood 2 is preferably in the nanometer or even micron order. The shape of the fine pattern 2 is not particularly limited, and a desired one can be employed. The aspect selection layer 5 is used for the back surface 1' of the surface layer 1 of the branch building, and is used to impart rigidity to the template 10. The material constituting the support layer 5 is exemplified by, for example, Shi Xi, Li Qi Ke, ($ 丨 &) glass, and the like. It is appropriate to use the support layer 5 for drought and 0 to about 1000 gm. 321598 8 201043427 Further, it is preferable to perform surface treatment on the surface 5a of the support layer 5 of the support surface layer 1. Thereby, the surface % can be made rough, and the adhesion of the layer 5 to the surface layer 1 can be improved. The surface treatment may, for example, be a glow discharge treatment, a plasma treatment, a sandblasting treatment, a chemical etching treatment, a primer treatment or the like. Here, the surface layer 1 composed of the aforementioned side chain crystalline polymer generally has uv permeability. It is preferable that the uv hardenable resin composition is printed with a micro-shirt, and the support layer 5 is formed by a material having a penetrating property. Thereby, the template 10 as a whole has UV transparency, so that UV can be irradiated to the uv curable resin composition via the template 10. Next, a method of manufacturing the template 1A will be described in detail with reference to FIG. As shown in Fig. 2(a), first, a surface layer 1 composed of a side chain crystalline polymer is laminated on the support layer 5. The surface 5a' of the support layer 5 on which the surface layer 1 is laminated is preferably surface-treated to be roughened in terms of adhesion to the surface layer 1. Further, the above-mentioned lamination is carried out by applying a coating liquid to the crucible floor 5 and drying it, and the coating liquid is obtained by adding the side chain crystalline polymer to a solvent. The coating is generally carried out by a knife coater, a rol 1 coater, a calendar coater, a corner coater (co a coater). Waiting for it. Further, depending on the coating thickness and the viscosity of the coating liquid, it may be carried out by a gravure coater, a bar coater, a spin coater or the like. Further, in addition to the above-described coating, the lamination of the surface layer 1 can be carried out by laminating and forming the sheet 1 by lamination and rolling to a support layer 5 by way of Example 9 321598 201043427. —Special surface layer After the surface layer i is laminated on the support layer 5, if not, the main mold 2 is disposed above the surface layer i. In view of the above, it is preferable to affinity with the crystalline polymer, for example, (4), (3) (6) glass, and the like. The material of the lower portion is formed with a fine pattern 21 on the main mold opposite to the surface la of the surface layer 1. The fine pattern 荦21 g , a plate 1 ◦ fine pattern 2 . Therefore, it is preferable that the fine pattern 2 which is desirably used in the fine pattern 1 is preferably of the order of micron or micron, which can be formed by EB lithography. "," the main mold 20 is moved in the direction of the arrow eight, and as in the (10) = surface la of the surface layer! is the main mold 2G_. This pressurization system = the temperature above the melting point of the side chain crystalline polymer. Therefore, the side chain 'w曰 polymer is in a flowing state, and the hot stamping operation of transferring the fine pattern 21 of the main mold 2 to the surface layer of the surface layer can be performed. The melting point of the side chain crystalline polymer is + 1 〇 (: to silk + 3 (). (The temperature is preferably used. Thus, the side chain crystalline polymer is a moderately pure flow of the wire, The transfer precision of the ascending domain 2 () is called, and the hot stamping operation at a relatively low temperature is achieved. On the other hand, if the pressurizing temperature is too low, the flow state of the side chain crystalline polymer becomes low. On the other hand, if the pressurization temperature is too high, the side chain crystalline polymer is excessively heated, which consumes more heat and is not economical. 321598 20 The aforementioned adjustment of the pressurizing temperature can be performed by, for example, the back surface 20b opposite to the surface 20a of the main mold 20. A heating means such as a heater is disposed, and the surface temperature of the fine pattern 21 is heated to a predetermined temperature by the heating means, or the temperature of the mist is adjusted to a temperature equal to or higher than the melting point of the side chain crystalline polymer. The pressing condition is preferably about 0.1 to 100 MPa and a pressing time of about 5 to 300 seconds. After the surface of the surface layer 1 is pressed by the main mold 20, the state is maintained, and cooling means such as a fan is used. The temperature of the surface layer 1 is cooled to a temperature at which the melting point of the side chain crystalline polymer is not reached. Thereby, the side chain crystalline polymer is in a crystalline state. Further, as shown in Fig. 2(d) The main mold 20 is moved in the direction of the arrow B, and the main mold 20 is peeled off from the surface la of the surface layer 1 formed of the side chain crystalline polymer in a crystalline state. At this time, the side chain crystalline polymer system in a crystalline state As described above, the mold release property is high. Therefore, even if the mold release treatment is not performed on the fine pattern 21 of the master mold 20, the master mold 20 can be peeled off from the surface layer 1 of the watch 0, and productivity can be improved. Mold 20 is stripped from surface layer 1 The fine pattern 21 of the master mold 20 is transferred to the surface 1a of the surface layer 1, and a template 10 having a fine pattern 2 of a pattern opposite to the fine pattern 21 can be obtained. Further, the above-described method can be repeated by using the master mold 20. In each step, the template 10 can be easily reproduced. Next, an embodiment in which a fine structure is formed using the template 10 will be described in detail with reference to Fig. 3 by using a UV curable resin composition in the case of a curable resin composition. 3 (a), first, a film 52 is formed on the surface of the substrate 51. 11 321598 201043427 In terms of the material constituting the substrate 51, in addition to hair, (for (6) glass, etc., for example, polyethylene, poly-p-phenylene Ethyl formic acid, ::, poly_, poly-imine, polycarbonate, ethylene, acid, ethyl vinegar, synthetic resin, ethylene propylene glycol copolymer, ethylene gas grilled and other synthetic resins. The substrate W is preferably touchable, and is, for example, 5 Å to __, preferably (10) to 15 Å _ left film 52 is composed of a UV curable resin composition. The liver hardening resin composition is cured by irradiation of uv (ultraviolet light), and can be used: The film 52 is formed by, for example, adding a cirrhotic resin: a predetermined substance to a predetermined solvent to obtain a coating liquid, and applying the coating liquid to the surface of the substrate 51 to dry it. The coating system can be carried out, for example, by spin coating, slit coating (sht coffee), spray coating, roll coating, or the like. The thickness of the unhardened layer 52 is, for example, Q. Q1 illusion, and (10)^ is about 0.01 to 500 #m. After the film 52 is formed on the surface of the substrate 51, as shown in Fig. 3 (1), the template 1 is placed above the film 52. This arrangement is performed in such a manner that the template fine pattern 2 faces the film 52. Next, this template is 1. Moving in the direction of the arrow C, as shown in Fig. 3 (4), the film 52 and the surface are added to the pull plate 10 by > Thereby, the fine pattern 2 of the template 1G, that is, transferred to the condition of the squid, is about 0.1 Å to about 100 MPa, and the room for adding is about 5 i 3 GG seconds. The film which has been transferred with the fine pattern 2 is cured by applying UV to the film 52 of the state shown in Fig. 3(C) while the surface of the film 52 is applied to the surface of the film 52. 321598 12 201043427 The UV irradiation direction is not particularly limited as long as the film 52 can be irradiated with ϋν. In other words, when the substrate 51 has the 穿透ν penetration property, the film 52 may be irradiated with UV from the surface side of the substrate 51. Further, when the support layer 5 of the template 1Q is formed of a material having uv permeability, since the template 1 is entirely UV-transmissive as described above, the skin 52 can be irradiated with UV through the template 10. Next, as shown in Fig. 3(d), the template 1 is moved in the direction of the arrow d, and the template 10 is peeled off from the cured film 53. At this time, although the mold release treatment is not performed on the fine pattern 2 of the template 10, the fine pattern 2 has a high mold release property for the reason described above, and therefore the load applied to the cured film 53 at the time of peeling is small. Therefore, when the template 1〇 is peeled off from the cured film, the cured film 53 of the fine pattern 2 and the fine structure 5〇 formed of the substrate 51 can be transferred with excellent precision. Further, the thickness of the cured film 53 is, for example, 〇1 to 1〇〇〇, preferably about 〇1 to 500#m.微 The obtained fine structure 50 can remove the residual film 54 by, for example, oxygen reactive ion etching, and after the surface of the substrate 51 is exposed from the adjacent hardened films 53 and 53, the hardened film 53 is used as a mask. The etching treatment or the aluminum or the like is subjected to lift off processing for use in wiring or the like. In the above-described embodiment, the uv curable resin composition is exemplified as the curable resin composition. However, other curable resin compositions may be used, for example, polymethyl methacrylate. (Polymethyl methacrylate) (PMMA) thermoplastic resin group 321598 13 201043427 product. Further, in the above-described embodiment, the case where the film of the fine pattern is transferred in a state where the template is pressurized is described. However, the curing of the film may be performed after the template is peeled off. The invention will now be described in further detail by way of examples, but the invention is not limited to the examples below. [Examples] The production of the side chain crystalline polymer used in the following examples is as follows. <Synthesis Example> 50 parts by weight of behenyl acrylate (manufactured by Nippon Oil Co., Ltd.), 45 parts of methyl acrylate (manufactured by Nippon Shokubai Co., Ltd.), 5 parts of acrylic acid, and 0.2 parts of perbutyl ND (manufactured by Nippon Oil Co., Ltd.) The mixture was added to 230 parts of ethyl acetate and mixed, and stirred at 55 ° C for 4 hours to polymerize the monomers. The obtained copolymer (side chain crystalline polymer) had a weight average molecular weight of 600,000 and a melting point of 55 °C. The aforementioned weight average molecular weight is a copolymer measured by GPC, and the obtained measurement value is converted into a value of polystyrene. Further, the above melting point is a value measured using DSC at a measurement condition of 10 ° C /min. <Production of Pattern for Printing> The template for printing of the present invention is produced as shown in Fig. 2 . The components used are as follows. Surface layer: The side chain crystalline polymer obtained in the above Synthesis Example was used. Support layer: Use a thickness of 625 //Π1. The surface of the support layer supporting the surface layer of the aforementioned Table 14 321598 201043427 was subjected to a dry etching treatment as a surface treatment. The aforementioned dry etching treatment is performed with SFe gas. Main mode: A mold composed of tantalum is used, which has a nano-scale fine pattern formed by EB lithography on the surface. The aforementioned fine pattern of the master mold is formed and provided with a plurality of ridges. The aforementioned ribs have a width of 490 nm and a pitch interval of 180 nm. In addition, the aforementioned width and spacing intervals are average values of n=10. The mold release treatment was not performed on the fine pattern described above in the master mold.加压 The pressurization conditions are as follows. Pressurization temperature: 70 ° C (melting point of side chain crystalline polymer + 15 ° C) Pressure: 5 MPa Pressurization time: 60 seconds In addition, the above-mentioned pressurization temperature is adjusted by disposing a heater on the back side of the main mold. This was carried out by heating the heater so that the surface temperature of the fine pattern was 70 °C. The production of the Q template is performed in the following manner. First, a surface layer is laminated on the support layer (see Fig. 2(a)). This lamination is carried out by applying a coating liquid onto a support layer by a spin coater and drying it at a temperature of 100 ° C, which is a side chain crystalline polymer. Add to the purpose of acetic acid ethyl acetate. The thickness of the surface layer to be laminated is 1/zm. Next, a master mold is placed above the surface layer (see Fig. 2(b)), and the surface of the surface layer is pressurized by the master mold under the above-described pressurization conditions (see Fig. 2(c)). The pressurized state of the master mold was maintained, and the temperature of the surface layer was cooled using a fan to a temperature of 15 321 598 201043427 degrees to / (23 C ) which did not reach the melting point of the aforementioned side chain crystalline polymer. Then, the master mold is obtained from the surface (see Fig. 2 (4)). The surface is leaked and the fine pattern for the obtained template is observed by a scanning electron microscope (magnification: 12, _ times the result is as shown in the figure: the map on the surface of the surface layer of the template, The accuracy is good to transfer the opposite pattern of the fine pattern of the main mold. Specifically, it can be seen that the nqn basket having a width dl of 180 nm and the d2 rib 30 are paid at intervals of 490 nm and the average width and The spacing interval d2 is not the same: 2: visually observing the result of the fine pattern of the main mold after peeling, the main crystalline polymer. From these results, it can be known that the fine pattern is used for heat (nano) ) Printing on the side chain crystalline polymer, which can form the material of the film plate, Β ^ ^ σ without the need to apply the makeup H, the template for the fine pattern of the main mold, 2, can be said to have excellent productivity As long as the obtained print lithography is used, the fine pattern of the _ plate can be subjected to the mold release treatment. [Simplified description of the drawing] The side = the figure is the template for displaying the print of the present invention - the outline of the embodiment The t) to (4) of the recipe are shown in Figure 1. The template for printing is shown in the steps of the method. Step diagram of the embodiment of the field structure. Fig. 4 is a scanning electron 321598 16 201043427 submicrograph of the template for printing obtained in the examples. [Main component symbol description]
1 表面層 la 表面 lb 背面 2 微細圖案 5 支撐層 5a 表面 10 模板 20 主模 20a 表面 20b 背面 21 微細圖案 30 凸條 50 微細構造 51 基板 52 皮膜 53 硬化被膜 54 殘膜 A-D 箭頭 dl 寬度 d2 間距間隔1 Surface layer la Surface lb Back surface 2 Fine pattern 5 Support layer 5a Surface 10 Template 20 Main mold 20a Surface 20b Back surface 21 Fine pattern 30 Reed 50 Fine structure 51 Substrate 52 Film 53 Hardened film 54 Residual film A-D arrow dl Width d2 Pitch interval