201105762 六、發明說明： 【發明所屬之技術領域】 本發明係有關一種將壓印微影術（i m p r i n t 1 ithography)中所使用之模具予以固定之黏著片及黏著 帶、以及微細構造之製造方法。 【先前技術】 最近，可有效率地於基板表面形成微細圖案而提高生 產量（throughput)之壓印微影術係受到注目。壓印微影術 係於基板表面形成由硬化性樹脂組成物所構成之被膜，並 以模具將此被膜表面加壓，而將模具之微細圖案轉印，並 使經轉印微細圖案之被膜硬化，而於基板表面形成微細圖 案之方法（例如：參照非專利文獻1)。 由於由壓印微影術所形成之微細圖案係對應於所使用 之模具之微細圆案，故在壓印微影術中模具之重要性相當 高。模具通常係在經真空夾吸盤（vacuum chuck)或機械二 夾頭（mechanical chuck)等夾具（」·丨g)固定在台座之狀態 為了將真空夾吸盤機構設置於台座，必須對 :座實施微細加工，而有成本會增加之問題。此外，若 中^夾棚定模具外周部，料因其本衫量而在模 .m撓曲’而有無法確保模具之表面平滑性之 分的轉印精度 丁 ^微衫術’也無法得到 、本在面積大的模具中相當顯著。 面考慮若扭用黏著片或點著帶取代真空央s 321590 4 201105762 盤或機械式夾頭等夾具來做為模具之固定手段，則應可解 決前述夾具所造成之問題。 然而，由一般的丙稀酸系黏著劑所構成之黏著片或黏 著帶係有下述問題。換言之，當採用例如uv硬化性樹脂組 成物做為前述硬化性樹脂組成物時，通常是在照射UV使被 膜硬化後，從該硬化被膜將模具垂直剝離。然而，由於若 使被膜硬化，則難以將模具剝離，故在進行前述垂直剝離 時會對前述黏著片或黏著帶施加較大的負載。一般的黏著 片及黏著帶係對於模具之固定力不足，若受到前述負載， 則模具會從黏著片或黏著帶脫落。此外，由於一般的黏著 片及黏著帶係無法重複使用，故經濟性低。 [非專利文獻1]松井真二，「奈米壓印微影技術」，表 面科學，Vol25，No. 10，PP628- 634，2004 【發明内容】 (發明欲解決的課題） 本發明之課題係提供一種可將模具在確保其表面平滑 性之狀態下以高固定力固定之模具固定用黏著片及模具固 定用黏著帶、以及微細構造之製造方法。 (解決課題的手段） 本發明之模具固定用黏著片係含有側鏈結晶性聚合物 做為主成分。前述側鏈結晶性聚合物係在未達融點之溫度 結晶化，且在前述融點以上之溫度顯示流動性，並且在前 述融點+ 10°C之儲存彈性模數G’為lxlO2至lxl05Pa。 本發明之模具固定用黏著帶係於基材薄膜之兩面設置 5 321599 201105762 黏著劑層而成’且至少模具侧之黏著劑㈣由前述模且固 定用黏著片所構成。 —本發明之微細構造之製造方法係使用前述模具固定用 黏著片，並且包括下述（〇至（14之步驟： (i) 使前述黏著片介置於模具與台座之間之步驟； (ii) 在令前述黏著片之溫度成為前述側鏈結晶性聚合物 之融點以上之溫度後，令溫度成為未達前述融點:溫 度，經由該黏著片而將前述模具固定在台座之步驟； (ill)以經固定之模具將由硬化性樹脂組成物所構成之被 膜之表面加壓，而將模具之微細圖案轉印之步驟；以 及201105762 VI. Description of the Invention: [Technical Field] The present invention relates to an adhesive sheet and an adhesive tape for fixing a mold used in imprint lithography, and a method for manufacturing a fine structure. [Prior Art] Recently, an imprint lithography system which can efficiently form a fine pattern on a surface of a substrate to improve throughput has been attracting attention. The lithography method forms a film composed of a curable resin composition on the surface of the substrate, presses the surface of the film with a mold, transfers the fine pattern of the mold, and hardens the film of the transferred fine pattern. A method of forming a fine pattern on the surface of the substrate (for example, see Non-Patent Document 1). Since the fine pattern formed by the lithography corresponds to the fine round of the mold used, the importance of the mold in the imprint lithography is quite high. The mold is usually fixed to the pedestal by a vacuum chuck or a mechanical chuck ("·g"). In order to set the vacuum chuck mechanism to the pedestal, it is necessary to perform a fine Processing, and there is a problem that the cost will increase. In addition, if the middle part of the mold is fixed in the middle of the mold, it is not possible to obtain the transfer precision of the surface of the mold due to the amount of the shirt, and the transfer precision of the surface of the mold cannot be ensured. This is quite remarkable in the large-sized mold. If you consider the use of a sticky sheet or a belt to replace the vacuum s 321590 4 201105762 disc or mechanical chuck as a fixing means for the mold, the problems caused by the above clamps should be solved. However, an adhesive sheet or an adhesive tape composed of a general acrylic-based adhesive has the following problems. In other words, when a uv curable resin composition is used as the curable resin composition, the film is usually peeled off vertically from the cured film after the film is cured by UV irradiation. However, if the film is hardened, it is difficult to peel the mold, so that a large load is applied to the above-mentioned adhesive sheet or adhesive tape during the vertical peeling. In general, the adhesive sheet and the adhesive tape have insufficient fixing force to the mold, and if subjected to the aforementioned load, the mold may fall off from the adhesive sheet or the adhesive tape. In addition, since the general adhesive sheet and the adhesive tape system cannot be reused, the economy is low. [Non-Patent Document 1] Matsui Shinji, "Nano-imprinting lithography technology", Surface Science, Vol. 25, No. 10, PP628-6342004 [Disclosure] Problems to be solved by the present invention Provided is an adhesive sheet for mold fixing, an adhesive tape for mold fixing, and a method for producing a fine structure, which are capable of fixing a mold with a high fixing force while ensuring smoothness of the surface. (Means for Solving the Problem) The adhesive sheet for mold fixing of the present invention contains a side chain crystalline polymer as a main component. The side chain crystalline polymer is crystallized at a temperature not reaching the melting point, and exhibits fluidity at a temperature above the melting point, and the storage elastic modulus G' at the melting point + 10 ° C is lxlO2 to lx10 Pa . The adhesive tape for mold fixing of the present invention is provided with 5 321 599 201105762 adhesive layer on both sides of the base film, and at least the adhesive on the mold side (4) is composed of the above-mentioned mold and fixing adhesive sheet. - the manufacturing method of the fine structure of the present invention is the use of the above-mentioned mold fixing adhesive sheet, and includes the following (step of (14) (i) placing the aforementioned adhesive sheet between the mold and the pedestal; (ii) After the temperature of the adhesive sheet is equal to or higher than the melting point of the side chain crystalline polymer, the temperature is lowered to the melting point: temperature, and the mold is fixed to the pedestal via the adhesive sheet; (ill) a step of pressurizing the surface of the film composed of the curable resin composition by a fixed mold to transfer the fine pattern of the mold;
Gv)使經轉印微細圖案之被膜硬化而得到微細構造之步 驟。 。再者，本發明中之前述「片」，並非僅限於片狀，只要 不損及本發明之效果，即包含片（she⑷狀或膜（film)狀之 概念。 (發明的效果） 根據本發明，由於以黏著片或黏著帶將模具固定在台 座上，故無須如以往般將台座加工，因此可降低成本，並 可將模具在確保其表面平滑性之狀態下固定在台座上。 π而且，本發明之黏著片或黏著帶之黏著劑層係會對應 於溫度變化而可逆性地成為結晶狀態與流動狀態，且含有 狀態下之儲存彈性模數G’具有肢值之麟結晶性 聚口物做為主成分。由於此側鏈結晶性聚合物係在流動狀 321599 201105762 態下顯示高流動性，故以該側鏈結晶性聚合物做為主成分 之前述黏著片或黏著帶會良好地滲入存在於模具或台座之 表面之微細的凹凸或空隙内，而可在從流動狀態變成結晶 狀態之過程中顯現所謂定錫效應（anchor ef f ect )，得到高 固定力。因此，若藉由前述黏著片或黏著帶，則即使在從 硬化被膜將模具垂直剝離之過程中受到較大的負載，也可 抑制模具脫落。並且，前述黏著片或黏著帶由於為利用側 鏈結晶性聚合物之相變化者，故可重複使用。 【實施方式】 <模具固定用黏著片> 本發明之模具固定用黏著片（以下有時稱為「黏著片」） 係含有側鏈結晶性聚合物做為主成分。前述側鏈結晶性聚合 物係在未達融點之溫度結晶化，且在融點以上之溫度進行相 轉移而顯示流動性。換言之，前述側鏈結晶性聚合物係會對 應於溫度變化而可逆性地成為結晶狀態與流動狀態。 前述側鏈結晶性聚合物係在前述融點+ 10°C之儲存彈 性模數G’為lxio2至lxl05Pa，且以2xl02至9xl04Pa為佳。 藉此，流動狀態下之側鏈結晶性聚合物會顯示高流動性， 而含有該側鏈結晶性聚合物做為主成分之前述黏著片也會 顯示高流動性。結果，前述黏著片會無缝隙地滲入存在於 模具或台座之表面之微細的凹凸或空隙内。由於若將此狀 態之黏著片冷卻至未達前述融點之溫度，則前述側鏈結晶 性聚合物會因結晶化而顯現定錨效應，故可得到高固定力。 另一方面，若在前述融點+ 10°C之儲存彈性模數G’小 7 321599 201105762 於lxl02Pa，則黏著片之凝聚力會降低而固定力也隨之 降低此外，由於若刖述储存彈性模數G，大於ixi〇1pa， 則側鏈結晶性聚合物之流動性會降低，故難以得到前述定 錦效應，而使固定力降低。 刖述側鏈結晶性聚合物以在前述融點—} 01之儲存彈 性模數 G’為 lxl〇5 至 lxl〇!)Pa 為佳、以 lxl〇4 ixi〇8pa 較 佳。藉此，可確保用以使前述定錯效應顯現所需的彈性。 此外’由於結晶狀態下之側鏈結晶性聚合物會具有適度的 彈性，故前述黏著片可發揮做為緩衝材之機能。因此，可 追隨基板之彎曲或微小凸起等，而可防止轉印不良。 另一方面，若在前述融點—丨01之儲存彈性模數G，過 小’則結晶狀態下之側鏈結晶性聚合物之彈性會不足，而 有難以得到前述定㈣應之虞。此外，若前述儲存彈性模 數G’過大，則黏著片難以發揮做為緩衝材之機能，故不 佳。前述儲存彈性模數G，係如後述之合成例中所記載，係 以動態黏彈性測定裝置測定而得之值。 在此 顺結晶性聚合物之前述融點，係意指藉由譯 平衡程序而使最初整合成有秩序之某種排列的聚合物^ 寺疋部分成為無秩序狀態之溫度，係藉由示差掃描熱量封 )在10 C/分鐘之測定條件下測得之值。 前述融點以3〇至m:為佳、以3G至6(rc較佳。若前 ，融點過低，則在進行模㈣料之環境溫度變化而使溫 二上升時，環境溫度容易超過前述融點，使側鏈結晶性聚 321599 8 1 物顯示流動性，因此固定力降低，而有模具會從黏著片 201105762 •脫落之虞。此外’若前述融點過高，料了使側鏈結晶性 •聚&物成為Λιι_動狀態而需要大量的熱能，因而在經濟性上 為不利。 若欲令前述儲存彈性模數G，及融點成為特定值，係可 經由改變側鏈結晶性聚合物之組成或分子量等來任意進 行。前述側鏈結晶性聚合物之組成可舉例如：使具有碳數 16以上之直鏈狀烧基之（甲基）丙烯酸酯至重量 份、具有碳數1至6之烷基之（甲基）丙烯酸酯〇至7〇重量 份、以及極性單體〇至10重量份聚合而得之聚合物等。里 前述具有碳數16以上之直鏈狀烷基之（甲基）丙烯酸 酯可舉例如：（甲基）丙烯酸鯨蠟酯、（甲基）丙烯酸硬脂酯、 (甲基）丙烯酸二十烷酯、（甲基）丙烯酸二十二烷酯等具有 石反數16至22之線狀烷基之（甲基）丙烯酸酯，前述具有碳 數1至6之烷基之（甲基）丙烯酸醋可舉例如··（甲基）丙烯 酸曱酯、（甲基）丙烯酸乙酯、（曱基）丙烯酸丁酯、（甲基） 丙烯酸己酯等，前述極性單體可舉例如：丙烯酸、曱基丙 烯酸、巴豆酸、伊康酸、馬來酸、富馬酸等含有羧基之乙 烯不飽和單體；（甲基）丙烯酸2-羥基乙酯、（甲基）丙烯酸 2-羥基丙酯、（甲基）丙烯酸2-羥基己酯等具有羥基之乙烯 不飽和單體，此等可使用丨種或混合2種以上使用。 上述所例示之單體中，具有碳數16以上之直鏈狀烷基 之（曱基）丙烯酸酯係對前述儲存彈性模數G’及融點造成 之影響相當大。若大量使用該（甲基）丙烯酸酯中之具有碳 數低之直鏈狀烷基之（甲基）丙烯酸酯，則有前述儲存彈性 321599 9 201105762 杈數G及融點容易成為前述之特定值之傾向。直體而古， =30重量份以上、較佳為3G至4()重量份之比例使隸 石厌數16至18之直鏈狀院基之（甲基）丙稀酸酿…具體例 =例如:使丙稀酸二十二以旨5至15重量份、丙稀酸硬 月曰酯30至40重量份、丙烯酸甲醋朽至55重量份、以及 丙烯酸0至10重量份聚合而得之共聚物等。 “此外，在具有碳數之燒基之（甲基）丙稀酸醋中， 右使:丙烯酸丁醋，則有前述儲存彈性模數g，及融點容易 成為前述之特定值之傾向。具體例可舉例如：使丙婦酸二 十二烧酉140至50重量份、丙烯酸丁酿45至55重量份、 以及丙烯酸0至10重量份聚合而得之共聚物等。 聚合方法並無特別限定，可採用例如：溶液聚合法、 塊狀聚合法、懸浮聚合法、乳化聚合法等。例如當採用溶 液聚合法時，可經由依需要將前述所例示之單體與溶劑混 合，並在40至90ΐ左右難2至1〇小時左右，而使前述 單體聚合。 前述側鏈結晶性聚合物之重量平均分子量以5,〇〇〇以 上為佳、以5, 000至900, 〇〇〇較佳。若前述重量平均分子 量過小或過大’則有前述儲存彈性模數G,及融點會脫離前 述之特定值之範圍之虞。此外，若前述重量平均分子量過 小’則有凝聚力降低且固定力降低之虞，若前述重量平均 分子量過大，則有即使令黏著片成為前述融點以上之溫 度，側鏈結晶性聚合物也難以顯示流動性之虞。前述重= 平均分子量係以凝勝滲透層析法（GPC)測定側鍵結晶性5 321599 10 201105762 -口物j將所知之測定值換算成聚苯乙稀而得之值。 . 則述黏著片之厚度以15至400 /^為佳、以丨2〇至15〇 _較佳。若前述黏著片之厚度過薄，則有固定力降低之 一义二且也難以發揮做為緩衝材之機能，故不佳。此外， :剛述黏著片之厚度過厚’則難以調製厚度均 片，故不佳。 ▲於削述黏著片之兩面，以設置經實施離型處理之薄 膜亦即離型薄膜為佳。前述離型薄膜可舉例如：於由聚 酸乙二酷等所構成之薄膜表面塗佈聚梦氧（silic〇ne) 型劑而成者。在黏著片之兩面設置離型薄膜時，只要 溶劑中添加有側鏈結晶性聚合物之塗佈液塗佈於離 ^ '上並使其錢而得難著#，並於 配㈣。 之表面 在前述塗佈液t，可添加例如：交聯劑、增黏劑 ★ 可塑劑、抗老化劑、紫外線吸收劑等各種添 〜。別逑塗佈—般可藉由刮刀塗佈ItCkiiife ooate二 ，塗佈器1延塗佈器（carlendar c〇ater)、逗點式塗佈 =TTater)等來進行。此外，依塗佈厚度和塗佈液 等來‘=由Γ版㈣器、桿式塗佈器（r°d⑽的 , 丁 者，則述黏著片除了前述塗佈以外，也可婉 ㈣如擠m成形、歷延加工而成形為片狀。 ，- <模具固定用黏著帶〉 本發明之模具固定用黏著帶（以 係於基材薄膜之Ml W, #者T」） ㈣膜之兩面设置黏著劑層 321599 11 201105762 = = 之本發，之模具固定用黏著片所構成。 材薄膜:了:： ^之”片同樣的效果，並關含有基 =膜’故可件到剛性較黏著片更高且處理性也更優良之 效果。 前述基材薄膜可舉例如：聚乙埽、聚fmn、 w烯、聚醋、聚酿胺、聚酿亞胺、聚碳酸醋、乙婦-乙酸 =旨共聚物、乙烯_㈣酸乙§旨共聚物、乙稀_聚丙稀共 聚物、聚氣乙烯等合成樹脂薄膜。 前述基材薄膜可為由單層體或複層體所構成者，厚产 ㈣為25至250㈣左右。為了提高相對於黏著劑層之ς 者性’可對基材薄膜之表面實施例如：電暈處理、電聚處 理、嘴砂處理、化學_處理、底漆處理等表面處理。 在位於模具側之基材薄膜之單面設置黏著劑層時，只 要將於，劑中添加有前述侧鏈結晶性聚合物之塗佈液㈣ 於基材薄膜之單面並使其乾燥即可1著綱之厚度以$ 至6〇_為佳、以10至6〇_較佳、以1〇至4〇_更佳。 另一面之黏著劑層並無特別限定，例如也可與單面之 黏著劑層同樣地由前述之本發明之模具固定用黏著片所構 成。此時，單面之黏著劑層之側鏈結晶性聚合物與另一面 之黏著劑層之側鏈結晶性聚合物可為相同組成，也可分別 為不同組成。 此外，另一面之黏著劑層也可使用含有感壓性接著劑 之黏著劑層。前述感壓性接著劑係具有黏著性之聚合物， 例如：天然橡膠接著劑、合成橡膠接著劑、苯乙烯/丁二 321599 \2 201105762 稀乳膠接著劑、丙烯酸系接著料。單面之黏著劑層之厚 度與另-面之黏著劑層之厚度可為相同厚度，也可分別 不同厚度。 … <微細構造之製造方法> 其次，關於本發明之微細構造之製造方法之一實施型 態，=舉使用前述之本發明之模具固定用黏著片進行模具 之固疋並❹uv硬化性翻組成物做為硬化性樹腊組成 物的情形做為例子，參照第1圖而詳細說明。 =第1圖（a)所示，首先，使前述之本發明之模具固定 用黏著片1介置於模具10與台座15之間。構成模具1〇 之材科可舉例如：梦、聚石夕氧、二氧化石夕⑸⑻玻璃、錄、Gv) A step of curing the film of the transferred fine pattern to obtain a fine structure. . In addition, the "sheet" in the present invention is not limited to a sheet shape, and includes a sheet (she (4) shape or a film shape concept without impairing the effects of the present invention. (Effect of the invention) According to the present invention Since the mold is fixed to the pedestal by the adhesive sheet or the adhesive tape, it is not necessary to process the pedestal as in the past, so that the cost can be reduced, and the mold can be fixed on the pedestal while ensuring the smoothness of the surface. The adhesive layer of the adhesive sheet or the adhesive tape of the present invention reversibly becomes a crystalline state and a flowing state corresponding to a change in temperature, and the storage elastic modulus G' in the state of containing has a limb crystalline crystalline agglomerate As the main component, since the side chain crystalline polymer exhibits high fluidity in the state of flow 321599 201105762, the aforementioned adhesive sheet or adhesive tape containing the side chain crystalline polymer as a main component penetrates well. It exists in the fine irregularities or voids on the surface of the mold or pedestal, and the so-called anchor effect (anchor ef f ect ) can be obtained during the process from the flow state to the crystalline state. Therefore, if the adhesive sheet or the adhesive tape is used, the mold can be prevented from falling off even if a large load is applied during the process of vertically peeling the mold from the hardened film, and the adhesive sheet or the adhesive tape is When the phase change of the side chain crystalline polymer is used, it can be reused. [Embodiment] <Adhesive sheet for mold fixing> The adhesive sheet for mold fixing of the present invention (hereinafter sometimes referred to as "adhesive sheet") The side chain crystalline polymer is contained as a main component, and the side chain crystalline polymer is crystallized at a temperature at which the melting point is not reached, and phase transition is performed at a temperature higher than the melting point to exhibit fluidity. In other words, the aforementioned side chain The crystalline polymer is reversibly in a crystalline state and a flowing state in response to a change in temperature. The side chain crystalline polymer has a storage elastic modulus G' at the melting point of +10 ° C of 1 x 2 2 to 1 x 10 5 Pa, and It is preferable that 2xl02 to 9xl04Pa is used. Thereby, the side chain crystalline polymer in a flowing state exhibits high fluidity, and the aforementioned viscosity containing the side chain crystalline polymer as a main component The sheet also exhibits high fluidity. As a result, the adhesive sheet penetrates seamlessly into the fine irregularities or voids existing on the surface of the mold or the pedestal, since the adhesive sheet in this state is cooled to a temperature at which the melting point is not reached. When the side chain crystalline polymer exhibits a anchoring effect due to crystallization, a high fixing force can be obtained. On the other hand, if the melting point + 10 ° C is stored, the elastic modulus G' is small 7 321599 201105762 At lxl02Pa, the cohesive force of the adhesive sheet is lowered and the fixing force is also lowered. Further, if the storage elastic modulus G is larger than ixi 〇 1 Pa, the fluidity of the side chain crystalline polymer is lowered, so that it is difficult to obtain the foregoing. The setting effect is reduced, and the fixing force is lowered. The side chain crystalline polymer is preferably such that the storage elastic modulus G' of the melting point - 01 is lxl 〇 5 to lxl 〇 !) Pa, and lxl 〇 4 Ixi〇8pa is preferred. Thereby, it is ensured that the aforementioned fixing effect is exhibited to exhibit the required elasticity. Further, since the side chain crystalline polymer in the crystalline state has moderate elasticity, the above-mentioned adhesive sheet can function as a cushioning material. Therefore, it is possible to follow the bending or micro bumps of the substrate, and it is possible to prevent transfer failure. On the other hand, if the storage elastic modulus G of the melting point - 丨 01 is too small, the elasticity of the side chain crystalline polymer in the crystalline state will be insufficient, and it is difficult to obtain the above-mentioned (4). Further, if the storage elastic modulus G' is too large, it is difficult for the adhesive sheet to function as a cushioning material, which is not preferable. The storage elastic modulus G is a value measured by a dynamic viscoelasticity measuring device as described in the synthesis example described later. The aforementioned melting point of the crystalline polymer means that the temperature of the polymer portion which is initially integrated into an orderly arrangement is changed to an unordered state by a translation balance program, and the heat is scanned by differential scanning. Sealed) The value measured under the measurement conditions of 10 C/min. Preferably, the melting point is from 3 〇 to m: and preferably from 3 GHz to 6 (rc is preferred. If the melting point is too low, the ambient temperature is likely to be exceeded when the temperature of the mold (four) material is changed to increase the temperature. The above melting point causes the side chain crystalline poly 321599 8 1 to exhibit fluidity, so the fixing force is lowered, and the mold is peeled off from the adhesive sheet 201105762. Further, if the melting point is too high, the side chain is made Crystallinity • Poly & material becomes a Λιι_ state and requires a large amount of heat energy, so it is economically disadvantageous. If the storage elastic modulus G and the melting point are to be specific values, the crystal can be crystallized by changing the side chain. The composition of the polymer, the molecular weight, and the like may be arbitrarily carried out. The composition of the side chain crystalline polymer may be, for example, a (meth) acrylate having a linear alkyl group having 16 or more carbon atoms, and having carbon. a polymer of from 1 to 6 alkyl (meth) acrylate to 7 parts by weight, and a polymer obtained by polymerizing from 10 to 10 parts by weight of a polar monomer. The above-mentioned linear alkane having a carbon number of 16 or more The base (meth) acrylate may, for example: ( a cetyl acrylate, a stearyl (meth) acrylate, an eicosyl (meth) acrylate, a behenyl (meth) acrylate or the like having a linear alkyl group of 16 to 22 (Meth) acrylate, the (meth)acrylic acid vinegar having the alkyl group having 1 to 6 carbon atoms, for example, decyl (meth) acrylate, ethyl (meth) acrylate, (mercapto) acrylate a butyl ester, a (meth) hexyl acrylate or the like, and the polar monomer may, for example, be an ethylenically unsaturated monomer having a carboxyl group such as acrylic acid, mercaptoacrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid; Ethylene-unsaturated monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate or 2-hydroxyhexyl (meth)acrylate, which can be used or mixed In the above-exemplified monomers, the (fluorenyl) acrylate having a linear alkyl group having 16 or more carbon atoms has a considerable influence on the storage elastic modulus G' and the melting point. Large use of the (meth) acrylate has a low carbon number The (meth) acrylate of the alkyl group has the storage elasticity of 321599 9 201105762. The number of turns G and the melting point tend to be the specific values described above. Straight and ancient, = 30 parts by weight or more, preferably 3G to The ratio of 4 parts by weight is such that the linear (M) acrylic acid of 16 to 18 is a specific example of the formula = for example, the acrylic acid is 22 to 15 parts by weight. a copolymer of 30 to 40 parts by weight of succinoic acid acrylate, 55 parts by weight of methyl acrylate, and 0 to 10 parts by weight of acrylic acid, etc. "In addition, in a base having a carbon number ( In the case of methyl acrylate vinegar, butyl acrylate vinegar has the above-mentioned storage elastic modulus g, and the melting point tends to be a specific value as described above. Specific examples include: benzoic acid 22 140 to 50 parts by weight of bismuth, 45 to 55 parts by weight of butyl acrylate, and 0 to 10 parts by weight of acrylic acid to obtain a copolymer or the like. The polymerization method is not particularly limited, and examples thereof include a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and an emulsion polymerization method. For example, when the solution polymerization method is employed, the above-mentioned monomer can be polymerized by mixing the above-exemplified monomer with a solvent and if it is difficult to be about 40 to 90 Torr for about 2 to 1 hour. The above-mentioned side chain crystalline polymer preferably has a weight average molecular weight of 5 or more, preferably 5,000 to 900, 〇〇〇. If the weight average molecular weight is too small or too large, the storage elastic modulus G is present, and the melting point is deviated from the range of the specific value described above. In addition, when the weight average molecular weight is too small, the cohesive force is lowered and the fixing power is lowered. If the weight average molecular weight is too large, the side chain crystalline polymer is hard to be displayed even if the pressure-sensitive adhesive sheet has a temperature equal to or higher than the melting point. The shackles of liquidity. The weight = average molecular weight is a value obtained by converting the measured value of the side bond crystallinity 5 321 599 10 201105762 - the mouth material j into a polystyrene by a condensate osmosis chromatography (GPC). The thickness of the adhesive sheet is preferably 15 to 400 /^, preferably 丨2〇 to 15〇. If the thickness of the adhesive sheet is too thin, the fixing force is lowered and it is difficult to function as a cushioning material, which is not preferable. Further, it is difficult to prepare a thickness uniform when the thickness of the adhesive sheet is too thick, which is not preferable. ▲In order to cut off both sides of the adhesive sheet, it is preferable to provide a release film which is subjected to release treatment, that is, a release film. The release film may be, for example, a coating of a silicin-type agent on the surface of a film composed of urethane or the like. When a release film is provided on both sides of the adhesive sheet, it is difficult to apply a coating liquid in which a side chain crystalline polymer is added to the solvent and make it difficult to make it (#). Surface The coating liquid t may be added with various additives such as a crosslinking agent, a tackifier, a plasticizer, an anti-aging agent, and an ultraviolet absorber. Do not apply the coating - it can be coated with a knife, ItCkiiife ooate II, applicator 1 (carlendar c〇ater), comma coating = TTater). In addition, depending on the coating thickness and the coating liquid, etc., it is also possible to use the stencil (4) or the rod coater (r°d (10). m is formed and formed into a sheet shape by the processing. - <Adhesive tape for mold fixing> The adhesive tape for mold fixing of the present invention (for Ml W, #T of the base film) (4) Both sides of the film Set the adhesive layer 321599 11 201105762 = = the original hair, the mold is fixed with the adhesive sheet. The material film: the same effect of the :: ^" piece, and the base = film ', so the piece can be rigid to the adhesive The film is higher and more excellent in handleability. The base film may, for example, be polyethylene, polyfmn, w-ene, polyester, polyamine, poly-imine, polycarbonate, or acetic acid. = a synthetic resin film such as a copolymer, an ethylene-(tetra) acid-based copolymer, an ethylene-polypropylene copolymer, or a polyethylene gas. The base film may be composed of a single layer or a laminate, and is thick. Production (4) is about 25 to 250 (four). In order to improve the adhesion to the adhesive layer, the surface of the substrate film can be For example, surface treatment such as corona treatment, electropolymerization treatment, mouth sand treatment, chemical treatment, primer treatment, etc. When an adhesive layer is provided on one side of the substrate film on the mold side, as long as the agent is added The coating liquid of the side chain crystalline polymer (4) is applied to one side of the base film and dried to a thickness of from 1 to 6 〇, preferably from 10 to 6 〇, preferably 1 The adhesive layer on the other side is not particularly limited. For example, it may be composed of the above-described adhesive sheet for mold fixing of the present invention, similarly to the adhesive layer of one side. The side chain crystalline polymer of the adhesive layer and the side chain crystalline polymer of the other adhesive layer may have the same composition or different compositions. In addition, the adhesive layer on the other side may also have a sense of containing. Adhesive layer of pressure-sensitive adhesive. The pressure-sensitive adhesive is an adhesive polymer such as natural rubber adhesive, synthetic rubber adhesive, styrene/butadiene 321599 \2 201105762 thin latex adhesive, acrylic Attachment. Single-sided adhesive layer The thickness of the adhesive layer of the thickness and the other surface may be the same thickness or different thicknesses. <Manufacturing method of fine structure> Next, one embodiment of the manufacturing method of the fine structure of the present invention, = The case where the mold is fixed and the ❹ uv hardening composition is used as the curable wax composition using the above-described adhesive sheet for mold fixing of the present invention will be described in detail with reference to Fig. 1 = Fig. 1 (a) First, the above-described mold fixing adhesive sheet 1 of the present invention is interposed between the mold 10 and the pedestal 15. The material constituting the mold 1 can be, for example, a dream, a poly stone, or a second. Oxide Ox (5) (8) glass, recorded,
Hit 1乙一ga等。於模具之表面施係形成有預定之 f細圖案u。該微細圖案11以奈米（rnn)至微米Uno級為 佳。模具10之厚度宜為10至2,000 /zm左右。所謂模具 之厚度，係意指其表面10a與背面1〇b之間之距離成為 最大之厚度。 /冓成台座15之材料可舉例如：二氧化矽玻璃等。台座 15係女定地支樓模具1〇者，其厚度以例如1 至2.nmi為佳。 斗使黏著片1介置於模具10與台座15之間後，經由黏 者片1將模具10固定在台座15。此固定係經由先令黏著 片1之恤度成為前述側鏈結晶性聚合物之融點以上之溫 f ϋέ為融點+ 1(rca上之溫度後，再令溫度成為未達 别述融點之溫度、較佳為融點-HTC 以下之溫度而進行。 由於若經過如此之特定之溫度變化 ，則侧鏈結晶性聚 13 321599 ς： 201105762 合物會從流動狀態進行相變化成為結晶狀態，藉此，因前 述之理由而顯現定錦效應，故可在確保表面平滑性之狀態 下以高固定力將模具10固定在台座15。黏著片1之溫度 调整可經由使用例如氣體、風扇、加熱器等溫度調整手段 調整環境溫度和台座】5之溫度來進行。 ▲另一方面，如第1圖（b)所示，於基板20之表面形成 被膜21。構成基板2〇之材料可舉例如石夕、二氧化石夕玻璃 等，除此以外’還可舉例如聚乙稀、聚對献酸乙二醋、聚 丙烯、聚酯、聚醯胺、聚醯亞胺、聚碳酸酯、乙烯—乙酸乙 稀醋共聚物、乙稀'丙烯酸乙®旨共聚物、乙稀-聚丙稀共聚 物t氣乙晞等合成樹脂。基板2〇之厚度以5〇至獅⑽ 為':MOO 1 150# m較佳t，基板2〇以具有可換性為佳。 被膜21 h由[JV硬化性樹脂組成物所構成。該—硬化 性樹脂組成物係經由照射ϋν(紫外線）而硬化者可採用各 種白1知物。被膜21之形成只要例如將UV硬化性樹脂组成 物加入預定溶劑中而得到塗佈液，並將此塗佈液塗佈於基 板2〇表面且使其乾燥即可。前述塗佈可藉由例如旋轉塗佈 法、狹縫塗佈法、喷霧塗佈法、輕塗佈法等來進行。未硬 化之被膜21之厚度以G.G1至麵_為佳、以〇 〇1至 500 /z m 較佳。 於基板20表面形成被膜21後，於該被膜21上方配置 此配置係以使模具1Q之微細與被膜21 = 式進行。接著，使此模具Μ與台座15 -起 朝前頭“向移動’如第崎)所示，以模具1〇將被膜 321599 14 201105762 21表面加壓。藉此，將模具10之微細圖案轉印至被膜21。 前述加壓條件係壓力為0. 1至10(^?8左右，加壓時間 為5至300秒左右。經轉印微細圖案11之被膜21之硬化 係經由對於在以模具10將被膜21表面加壓之狀態、亦即 在第1圖（c)所示之狀態下之被膜21照射UV來進行。 UV照射方向係只要可對被膜21照射UV，即並無特別 限定。換言之，當基板20具有UV穿透性時，只要從基板 20之背面側對被膜21照射UV即可。此外，黏著片1通常 係具有UV穿透性。因此，若以具有UV穿透性之材料構成 台座15及模具10，則可從台座15之背面側隔著該台座 15、黏著片1及模具10而對被膜21照射UV。 其次，如第1圖（d)所示，使模具10與台座15—起朝 箭頭B方向移動，從硬化被膜22將模具10剝離。此剝離 係為了抑制硬化被膜22之損傷，通常以垂直剝離之方式進 行。在進行此垂直剝離時，對黏著片1施加較大的負載。 黏著片1由於因前述理由而以高固定力將模具10固定，故 即使受到前述負載，也可抑制模具10之脫落。 若從硬化被膜22將模具10剝離，則可得到由經轉印 微細圖案11之硬化被膜22與基板20所構成的微細構造 25。硬化被膜22之厚度以0. 01至1000 /zm為佳、以0· 01 至500 // m較佳。 所得之微細構造25可藉由例如氧氣反應性離子蝕刻 法（reactive ion etching)等將殘膜26去除，使基板20 表面從鄰接之硬化被膜22、22間露出後，以硬化被膜22 15 321599 201105762 做為遮罩進躲刻處理、或將料進行掀的if 工，而利用於線路等。此外.，當持續製造新穎的微造 25時，只要重複進行前述之步驟即可。 偁t 另一方面，當模具；1〇破損時、或當製造微細圖 之其他微細構造時，必須將模具1Q從台座15卸下了 : 其他模具。此時，只要使用前述溫度調整手段將黏著片^ 加熱至前述側鏈結晶性聚合物之融點以上之溫度即可。藉 此於前述側鏈結晶性聚合物顯示流動性而使黏著片] 之固定力降低，故可較簡單地將模具丨〇卸下。黏著片1 係藉由進行與前述⑽之操作而可錢使料多:^。 —以上，顯示本發明之較佳的實施形態，但本發明並不 限定於以上之實施形態，在巾請專利範圍中所記載之範圍 内、，可進行各種改良和變更。例如：在前述之微細構造之 製造=法之一實施形態中，雖說明使用本發明之模具固定 用黏著片製造微細構造的情形，但前述微細構造也可藉由 使用本發明之模具固定用黏著帶取代前述黏著片，來^行 製造。此時，以使含有側鏈結晶性聚合物之單面之黏著劑 層朝向模具側之方式，經由另一面之黏著劑層而將黏著帶 貼者於台座。 此外，在前述實施形態中雖列舉以⑽硬化性樹脂組成 物做為硬化性樹脂組成物之例子進行說明，但也可使用做 為其他硬化性樹脂組成物之例如聚曱基丙烯酸曱酯（p_A) 等熱塑性樹脂組成物。在前述實施形態中雖說明在以模具 加壓之狀態下進行經轉印微細圖案之被膜之硬化的情形， 321599 16 201105762 但前述被膜之硬化也可在將模具剝離後進行。 以下，列舉合成例及實施例詳細說明本發明，但本發 . 明並不僅限定於以下之合成例及實施例。再者，在以下之 說明中，「份」係意指重量份。 (合成例1) 首先，以丙烯酸二十二烷酯45份、丙烯酸丁@旨'5〇份、 丙烯酸5份、做為聚合起始劑之PERBUTYLND(日油公司製） 〇· 5份、及做為鏈轉移劑之N_十二烷硫醇 (1(1(^6〇711^1^^^&11)(日本油脂）6份之比例混合，並在 8〇°C攪拌4小時，使此等單體聚合。所得之共聚物之重量 平均刀子里為7, 000，融點為371。此外，在前述融點+ i〇°c之儲存彈性模數G，為3xl02Pa，在融點—1(rc之儲存 彈性模數G’為5xl01Pa。 (合成例2) 首先’以丙烯酸二十二烷酯45份、丙烯酸丁酯50份、 =烯酸2份、及做為聚合起始劑之PERBUTYLND(日油公司 製）〇.。5伤之比例混合，並在託艽攪拌4小時。其次，升溫 ^ 8〇C後，添加做為聚合起始劑之PERHEXYLPV(日油公司 幻0 j伤輕拌2小時，使此等單體聚合。所得之共聚物 ^重量平均分子量為67萬融點為赃。此外，在前述 17 321599 1 (合成例3) 、先以丙婦酸二十二烷酯15份、丙烯酸硬脂酯30 2 點+ 1〇<：之儲存彈性模數G，為7xl03Pa，在融點-lOt 之儲存彈性模數G，為lxl〇6pa。 201105762 份、丙稀酸曱酯50份、丙烯酸5份、及做為聚合起始劑之 PERBUTYL ND(日油公司製）〇· 5份之比例混合，並在55。[授 拌4小時。其次，升溫至80°C後，添加做為聚合起始劑= PERHEXYLPV(日油公司製）〇乃份並攪拌2小時，使此等單 體聚合。所得之共聚物之重量平均分子量為65萬，融點為 41°C。此外，在前述融點+ 1〇。(：之儲存彈性模數G，為8χ 104Pa ’在融點一l〇°C之儲存彈性模數G’為2χ1〇^。 (比較合成例1) 首先，以丙烯酸二十二烷酯20份、丙烯酸硬脂醋25 份、丙烯酸甲酯50份、丙烯酸5份、做為聚合起始劑之 PERBUTYL ND(日油公司製）〇. 5份、及做為鏈轉移劑之n_ 十一烧硫醇（日本油脂）6份之比例混合，並在8 〇 槐掉4 小時，使此專單體聚合。所得之共聚物之重量平均分子量 為7, 000，融點為40°C。此外，在前述融點+ 1〇〇c之儲存 彈性模數G’為5x10^8，在融點一1〇艺之儲存彈性模數G， 為 5xl07Pa。 (比較合成例2) 首先，以曱基丙烯酸二十二烷酯65份、曱基丙烯酸丁 酉曰30伤、甲基丙烯酸5份、及做為聚合起始劑之 ND(日油公司製）〇.5份之比例混合，並在55<t攪拌4小時。 其-人，升/皿至8 0 C後，添加做為聚合起始劑之perhexyl PV(日油公司製）〇· 5份並攪拌2小時，使此等單體聚合。 所得之共聚物之重量平均分子量為25萬，融點為35t。 此外，在前述融點+ 1(TC之儲存彈性模數G，為5xl〇5pa， 321599 201105762 在融點一10°C之儲存彈性模數G，為9xl05Pa。 前述合成例1至3及比較合成例1、2之各共聚物如表 1所示。再者’前述重量平均分子量係以GPC測定共聚物 後’將所得之測定值換算成聚苯乙烯而得之值。前述融點 係使用DSC在1 〇°C /分鐘之測定條件下測得之值。前述儲 存彈性模數G係使用Seiko Instruments Inc.製之動熊黏 彈性測定裝置「MS 6100」，在10Hz、5°C/分鐘、—^1〇〇 至400°C之升溫過程中，測定在融點±l(Tc之儲存彈性模數 G’而得之值。 表Hit 1 B, ga, etc. A predetermined fine pattern u is formed on the surface of the mold. The fine pattern 11 is preferably in the range of nnn to micron Uno. The thickness of the mold 10 is preferably about 10 to 2,000 /zm. The thickness of the mold means the thickness at which the distance between the surface 10a and the back surface 1b is the largest. The material of the pedestal 15 can be, for example, cerium oxide glass or the like. The pedestal 15 series is a female floor slab mold, and its thickness is preferably, for example, 1 to 2. nmi. After the adhesive sheet 1 is placed between the mold 10 and the pedestal 15, the mold 10 is fixed to the pedestal 15 via the adhesive sheet 1. The fixing is based on the temperature of the sinter-adhesive sheet 1 being the melting point of the side chain crystalline polymer, and the temperature f ϋέ is the melting point + 1 (after the temperature on the rca, the temperature is not reached the melting point The temperature is preferably a temperature below the melting point - HTC. Since such a specific temperature change occurs, the side chain crystalline poly 13 321599 ς: 201105762 will change from a flowing state to a crystalline state. With this reason, the brocade effect is exhibited for the reason described above, so that the mold 10 can be fixed to the pedestal 15 with a high fixing force while ensuring the smoothness of the surface. The temperature adjustment of the adhesive sheet 1 can be performed by using, for example, a gas, a fan, or a heating. The temperature adjustment means such as the temperature adjustment means adjusts the ambient temperature and the temperature of the pedestal 5. On the other hand, as shown in Fig. 1(b), the film 21 is formed on the surface of the substrate 20. The material constituting the substrate 2 is, for example, Shi Xi, sulphur dioxide, glass, etc., in addition to, for example, polyethylene, polyethylene terephthalate, polypropylene, polyester, polyamide, polyimine, polycarbonate, ethylene - acetic acid ethyl acetate Synthetic resin such as ethylene acetonitrile copolymer, ethylene-polypropylene copolymer, gas acetonitrile, etc. The thickness of the substrate 2〇 is 5〇 to lion (10) is ':MOO 1 150# m preferably t, The substrate 2 is preferably made of a moldable material. The film 21 h is composed of a [JV curable resin composition. The curable resin composition is cured by irradiation of ϋν (ultraviolet rays), and various white materials can be used. The coating film 21 is formed by, for example, adding a UV curable resin composition to a predetermined solvent to obtain a coating liquid, and applying the coating liquid to the surface of the substrate 2 and drying it. The coating can be performed by, for example, The spin coating method, the slit coating method, the spray coating method, the light coating method, and the like are performed. The thickness of the unhardened film 21 is preferably G.G1 to No. _, and 〇〇1 to 500 /zm. Preferably, after the film 21 is formed on the surface of the substrate 20, the arrangement is disposed above the film 21 to make the mold 1Q fine and the film 21 =. Then, the mold Μ and the pedestal 15 are moved toward the front. 'As shown in the first place, the surface of the film 321599 14 201105762 21 is pressurized with a mold 1 。. The fine pattern having the fine pattern of 10 is transferred to the film 21. The pressurization condition is a pressure of 0.1 to 10 (about 8 or so, and the pressurization time is about 5 to 300 seconds. The hardening of the film 21 by transferring the fine pattern 11 The film 21 is irradiated with UV in a state in which the surface of the film 21 is pressed by the mold 10, that is, in the state shown in Fig. 1(c). The UV irradiation direction is such that the film 21 can be irradiated with UV. In other words, when the substrate 20 has UV transmittance, it is only necessary to irradiate the film 21 with UV from the back side of the substrate 20. Further, the adhesive sheet 1 usually has UV transmittance. Therefore, when the pedestal 15 and the mold 10 are made of a material having UV permeability, the film 21 can be irradiated with UV from the back side of the pedestal 15 via the pedestal 15, the adhesive sheet 1, and the mold 10. Next, as shown in Fig. 1(d), the mold 10 and the pedestal 15 are moved in the direction of the arrow B, and the mold 10 is peeled off from the cured film 22. This peeling is usually carried out in a vertical peeling manner in order to suppress the damage of the hardened film 22. When this vertical peeling is performed, a large load is applied to the adhesive sheet 1. Since the adhesive sheet 1 fixes the mold 10 with a high fixing force for the above reasons, even if the load is applied, the falling of the mold 10 can be suppressed. When the mold 10 is peeled off from the cured film 22, the fine structure 25 composed of the cured film 22 and the substrate 20 of the transferred fine pattern 11 can be obtained. The thickness of the hardened film 22 is preferably from 0.01 to 1000 /zm, preferably from 0.01 to 500 // m. The obtained fine structure 25 can be removed by, for example, oxygen reactive ion etching or the like, and the surface of the substrate 20 is exposed from the adjacent hardened films 22 and 22 to harden the film 22 15 321599 201105762 It is used as a mask for the engraving process, or for the material to be used for the work. Further, when the novel microfabrication 25 is continuously manufactured, it is only necessary to repeat the aforementioned steps. On the other hand, when the mold is broken, or when other fine structures of the fine pattern are manufactured, the mold 1Q must be detached from the pedestal 15: other molds. In this case, the adhesive sheet may be heated to a temperature higher than the melting point of the side chain crystalline polymer by using the temperature adjusting means. As a result, the side chain crystalline polymer exhibits fluidity and the fixing force of the adhesive sheet is lowered, so that the mold can be easily removed. The adhesive sheet 1 can be made more expensive by performing the operation of the above (10): ^. The preferred embodiments of the present invention are shown in the above, but the present invention is not limited to the above embodiments, and various modifications and changes can be made within the scope of the claims. For example, in the embodiment of the manufacturing method of the fine structure described above, the case of using the mold fixing adhesive sheet of the present invention to produce a fine structure is described. However, the fine structure may be adhered by using the mold of the present invention. The tape is replaced by the aforementioned adhesive sheet. At this time, the adhesive tape is attached to the pedestal via the adhesive layer on the other side so that the adhesive layer containing the one side of the side chain crystalline polymer faces the mold side. In the above-described embodiment, the (10) curable resin composition is used as the curable resin composition. However, as the other curable resin composition, for example, polydecyl acrylate (p_A) may be used. ) A thermoplastic resin composition. In the above-described embodiment, the case where the film of the transferred fine pattern is cured while being pressed by the mold is described. 321599 16 201105762 However, the curing of the film may be performed after the mold is peeled off. Hereinafter, the present invention will be described in detail by way of Synthesis Examples and Examples, but the present invention is not limited to the following Synthesis Examples and Examples. In the following description, "parts" means parts by weight. (Synthesis Example 1) First, PERBUTYLND (manufactured by Nippon Oil Co., Ltd.) 5 parts, and 5 parts of butyl acrylate, 5 parts of acrylonitrile, 5 parts of acrylic acid, and polymerization initiator N-dodecyl mercaptan (1 (1 (^6〇711^1^^^&11)) is mixed as a chain transfer agent in 6 parts, and stirred at 8 ° C for 4 hours. The monomers are polymerized. The obtained copolymer has a weight average knife of 7,000 and a melting point of 371. In addition, the storage elastic modulus G at the above melting point + i〇°c is 3xl02Pa, in the melting Point-1 (the storage elastic modulus G' of rc is 5xl01Pa. (Synthesis Example 2) First, '45 parts of behenyl acrylate, 50 parts of butyl acrylate, 2 parts of enoic acid, and as a polymerization start The PERBUTYLND (made by Nippon Oil Co., Ltd.) 混合. 5 wound ratio is mixed and stirred in the sputum for 4 hours. Secondly, after heating at 8 〇C, PERHEXYLPV is added as a polymerization initiator (Nippon Oil Company illusion 0) J-lightly mixed for 2 hours to polymerize the monomers. The obtained copolymer had a weight average molecular weight of 670,000, and the melting point was 赃. In addition, in the above-mentioned 17 321,599 1 (Synthesis Example 3), first with propylene fosinate 15 parts of alkyl ester, stearyl acrylate 30 2 points + 1 〇 <: storage elastic modulus G, 7xl03Pa, storage elastic modulus G at melting point - lOt, lxl 〇 6pa. 201105762 parts, propylene 50 parts of decyl acrylate, 5 parts of acrylic acid, and PERBUTYL ND (manufactured by Nippon Oil Co., Ltd.) as a polymerization initiator, mixed in a ratio of 5 parts, and at 55. [4 hours of mixing. Next, the temperature is raised to 80°. After C, the polymerization initiator was added as a polymerization initiator = PERHEXYLPV (manufactured by Nippon Oil Co., Ltd.) and stirred for 2 hours to polymerize the monomers. The obtained copolymer had a weight average molecular weight of 650,000 and a melting point of 41 °. C. In addition, in the above melting point + 1 〇. (: The storage elastic modulus G is 8 χ 104 Pa 'the storage elastic modulus G' at the melting point of 1 〇 ° C is 2 χ 1 〇 ^. (Comparative Synthesis Example 1 First, PERBUTYL ND (manufactured by Nippon Oil Co., Ltd.), which is 20 parts by weight of behenyl acrylate, 25 parts of stearyl acrylate, 50 parts of methyl acrylate, and 5 parts of acrylic acid, is used as a polymerization initiator. And as a chain transfer agent, the mixture of n_ eleven-burning mercaptan (Japanese fat) is mixed in 6 parts, and is immersed in 8 for 4 hours to polymerize the monomer. The copolymer has a weight average molecular weight of 7,000 and a melting point of 40° C. In addition, the storage elastic modulus G′ at the aforementioned melting point + 1 〇〇c is 5×10^8, at the melting point of 1 The storage elastic modulus G was 5 x 10 07 Pa. (Comparative Synthesis Example 2) First, 65 parts of behenyl methacrylate, 30 parts of butyl hydrazide, 5 parts of methacrylic acid, and as a polymerization initiator The ND (manufactured by Nippon Oil Co., Ltd.) was mixed in a ratio of 5 parts, and stirred at 55 < t for 4 hours. After the addition of the human/liters to the 80 ° C, perhexyl PV (manufactured by Nippon Oil Co., Ltd.) as a polymerization initiator was added and stirred for 2 hours to polymerize the monomers. The resulting copolymer had a weight average molecular weight of 250,000 and a melting point of 35t. In addition, in the above-mentioned melting point + 1 (the storage elastic modulus G of TC is 5xl 〇 5pa, 321599 201105762, the storage elastic modulus G at a melting point of 10 ° C is 9xl05Pa. The above synthesis examples 1 to 3 and comparative synthesis The copolymers of Examples 1 and 2 are shown in Table 1. The above-mentioned weight average molecular weight is a value obtained by converting the obtained measured value into polystyrene after measuring the copolymer by GPC. The melting point is DSC. The value measured under the measurement conditions of 1 ° C / min. The storage elastic modulus G was a viscoelasticity measuring device "MS 6100" manufactured by Seiko Instruments Inc. at 10 Hz, 5 ° C / min, - During the temperature rise from ^1〇〇 to 400 °C, the value obtained by melting the point ±1 (the stored elastic modulus G' of Tc is determined.
1)C22A :丙烯酸二十二烷酯、C4A :丙烯酸丁^7^八烯 酸、C18A :丙烯酸硬脂酯、C1A :丙烯酸甲酯、C22M :甲 .基丙稀酸一十二烧酯、C4MA :曱基丙烯酸丁酯、—A ·甲芙 丙稀酸 由表1得知，在合成例i、2中，因以丙烯酸丁酯做為 主成分，而將儲存彈性模數G，及融點控制在前述之特定 值。此外得知，在合成例3中，因以30重量份之比例調= 具有碳數16以上之直鏈狀烷基之（曱基）丙烯酸酯中碳數 321599 19 201105762 而將儲存彈性模數…點控制在 (實施例〗至3及比較例〗、2) <黏著片之製作> 首先使用乙酸乙醋將前述合成例】至3及比較合 H平2中所得之各共聚物調整成固形份為3⑽，而得到 ===著，相對於前述各共聚物咖 、”釈77為G. 5份之異氰酸醋系交聯劑而得黏著 翁液，將該黏著劑溶液塗佈於厚度為100"之聚㈣酸 :酯_⑽薄膜）之單面並使其乾燥，而分別製作形 成有厚度40/^〗之黏著劑層的黏著帶。 <評估> 述t所得之各黏著帶，評估垂直剝離強度。評 估方法如下述所示，結果如表2所示。 〔垂直剝離強度〕 首先，將前述黏著帶固定在丙烯酸系樹脂製之台板 此固定係經由使用丙職系接著劑（一方社油脂工業股 ^有限公司製之「AS5Q2Q」）將pET薄膜之與形成有前述黏 著剖層之單面相反側之另—面料接著固定在前述台板上 來進行。藉此，成為前述黏著劑層相對於前述台板係朝向 上方之狀態。 然後，以下述條件使一邊長l〇nim之不鏽鋼（SUS)製之 正立方體與則述黏著劑層密著並以加壓5秒後，以 300mm/分鐘之速度從前述黏著劑層將前述正立方體垂直 321599 20 201105762 ' 剝離。藉由荷重元（load cel 1)測定此時之垂直剝離強度。 (60°C ) ' 在60°C之環境溫度下將前述正立方體與前述黏著劑 層密著並加壓後，垂直剝離。 (60。。一23。〇 在60°C之環境溫度下將前述正立方體與前述黏著劑 層密著並加壓後，使環境溫度降低至23°C，並在此環境溫 度下靜置20分鐘後，垂直剝離。 表2 黏著劑層之 組成 融點 (0〇 儲存彈性模數G’（Pa) 垂直剝離強度（N/cm2) 融點+ 10°C 融點一 10°C 60°C 60—23。。 實施例1 合成例1 37 3xl02 5xl06 10 400 實施例2 合成例2 46 7xl03 lxlO6 20 300 實施例3 合成例3 41 8xl04 2xl07 20 250 比較例1 比較合成例1 40 5x10] 5x107 5 50 比較例2 比較合成例2 35 5xl05 9xl05 4 10 由表2得知，在60->23°C之垂直剝離強度方面，相較 於比較例1、2,實施例1至3顯現非常高的固定力。此外， 由60°C之垂直剝離強度之結果得知，實施例1至3係只要 加熱至融點以上之溫度，則可較簡單地將模具卸下。 【圖式簡單說明】 第1圖（a)至（d)係表示使用本發明之模具固定用黏著 片製造微細構造之一實施形態之步驟圖。 【主要元件符號說明】 1 模具固定用黏著片 10 模具 10a 模具之表面 21 321599 201105762 10b 模具之背面 11 :微細圖案 15 台座 20 基板 21 被膜 22 硬化被膜 25 微細構造 26 殘膜 3215091) C22A: behenyl acrylate, C4A: butyl succinate, C18A: stearyl acrylate, C1A: methyl acrylate, C22M: dimethyl acetonate, C4MA : butyl methacrylate, -A · ketopropionic acid is known from Table 1. In the synthesis examples i and 2, the butyl acrylate is used as a main component, and the elastic modulus G and the melting point are stored. Control is at the specific value described above. Further, it was found that in Synthesis Example 3, the storage elastic modulus was changed by the ratio of 30 parts by weight to the carbon number of 321599 19 201105762 having a linear alkyl group having a carbon number of 16 or more... Point control (Examples to 3 and Comparative Examples, 2) <Production of Adhesive Sheets> First, each of the copolymers obtained in the above Synthesis Examples to 3 and Comparative H Flat 2 was adjusted with ethyl acetate. The solid content is 3 (10), and the adhesive solution is coated with respect to the above copolymers, "釈77 is G. 5 parts of isocyanate-based cross-linking agent to obtain a binder solution. On one side of a poly(tetra) acid:ester_(10) film having a thickness of 100", and drying it, and separately forming an adhesive tape having a thickness of 40/μ.] <Evaluation> The adhesive strength was evaluated for each adhesive tape. The evaluation results are shown in Table 2. The results are shown in Table 2. [Vertical peel strength] First, the adhesive tape was fixed to a plate made of acrylic resin. Adhesive ("AS5Q2Q" by the company's Oils and Fats Industry Co., Ltd.) The formed film has the adhesion with the pET-sided cross-sectional layers of the side opposite to the other - the fabric is then secured to the platen. Thereby, the adhesive layer is placed upward with respect to the platen. Then, the positive cube made of stainless steel (SUS) having a length of l〇nim was adhered to the adhesive layer and pressed for 5 seconds, and then the positive pressure was obtained from the adhesive layer at a speed of 300 mm/min. Cube vertical 321599 20 201105762 ' Stripped. The vertical peel strength at this time was measured by a load cel 1 . (60 ° C) ' The positive cube was adhered to the above-mentioned adhesive layer at an ambient temperature of 60 ° C and pressurized, and then peeled off vertically. (60. 23.23. After the positive cube and the aforementioned adhesive layer are adhered and pressurized at an ambient temperature of 60 ° C, the ambient temperature is lowered to 23 ° C, and allowed to stand at this ambient temperature 20 After a minute, it is peeled off vertically. Table 2 Composition of the adhesive layer melting point (0〇 Storage elastic modulus G' (Pa) Vertical peel strength (N/cm2) Melting point + 10 °C Melting point - 10 ° C 60 ° C 60-23. Example 1 Synthesis Example 1 37 3xl02 5xl06 10 400 Example 2 Synthesis Example 2 46 7xl03 lxlO6 20 300 Example 3 Synthesis Example 3 41 8xl04 2xl07 20 250 Comparative Example 1 Comparative Synthesis Example 1 40 5x10] 5x107 5 50 Comparative Example 2 Comparative Synthesis Example 2 35 5xl05 9xl05 4 10 It is known from Table 2 that in the vertical peel strength of 60->23 ° C, Examples 1 to 3 appear very high compared to Comparative Examples 1 and 2. Further, from the results of the vertical peel strength of 60 ° C, it is known that the examples 1 to 3 can be easily removed by heating to a temperature higher than the melting point. [Simplified illustration] Fig. 1 (a) to (d) show an embodiment in which a fine structure is produced by using the adhesive sheet for mold fixing of the present invention. Step diagram. [Main component symbol description] 1 Adhesive sheet for mold fixing 10 Mold 10a Surface of mold 21 321599 201105762 10b Back side of mold 11: Fine pattern 15 pedestal 20 Substrate 21 Film 22 Hardened film 25 Fine structure 26 Residual film 321509