201245853 六、發明說明： 【發明所屬之技術領域】 本發明係關於藉由光壓印（imprint)之光硬化物之製 造方法。 【先前技術】 光壓印係下述方法：使光硬化性組成物塗佈於基板所 形成的光硬化性組成物層與形成有凹凸圖形之模具接觸， 並於模具之凹凸圖形充填光硬化性組成物層，將光硬化性 組成物層曝光而為光硬化物後，將模具由光硬化物脫模， 藉此可得到經前述凹凸圖形轉印之光硬化物。由於經凹凸 圖形轉印之光硬化物可簡便地製作，故為近年來受注目的 技術（參照專利文獻1)。 但是，光壓印中，在將模具由光硬化物脫模之脫模步 驟時’會有模具無法由光硬化物脫模，而是光硬化物由基 板剝離之問題，以及光硬化物雖未由基板剝離光硬化物 -部份部附著於模具，而有無法獲得具有所求凹凸圖形的 光更物之題。尤其是若模具重複使用，則該 更為顯著。 [先前技術文獻] (專利文獻） 專利文獻1 :美國專利第6334960號說明書 【發明内容】 (發明欲解決的課題） 有鑑於該等情事，本發明之課題為提供一光硬化物之 324027 4 201245853 製造方法’其係藉由光壓印而製造光硬化物之方法，可良 * 好地重複進行將模具由光硬化物脫模之脫模步驟。 . (解決課題之手段） 本發明者們為了解決上述課題而專心致志進行檢討， 結果發現壓印用光硬化性組成物經曝光而硬化之試驗物對 於具有與模具相同的表面之構件之每單位面積的附著力為 15niN/mm2以下時，可解決上述問題，從而完成本發明。 換句話說，本發明之光硬化物之製造方法係具有：將 壓印用光硬化性組成物形成之光硬化性組成物層爽入於基 板與形成有凹凸圖形的模具之間而成形之成形步驟；將前 述光硬化性組成物層曝光為光硬化物之光硬化步驟；以及 將前述模具由光硬化物脫模之脫模步驟，其中，前述壓印 用光硬化性組成物經曝光而硬化之試驗物對於具有與前述 模具相同的表面之構件之每單位面積的附著力為i5mN/_2 以下。 (發明的效果） 根據本發明’壓印用光硬化性組成物經曝光而硬化之 試驗物對於具有與模具相同的表面之構件之每單位面積的 附著力為15mN/mm2以下時，可良好地重複進行模具由光硬 化物脫模之脫模步驟，並可防止模具無法由光硬化物脫模 而使光硬化物由基板剝離之問題，以及光硬化物未由基板 剝離而使得光硬化物之-部份附著於模具之問題。接著， 僅以測定所使用之麼印用光硬化性組成物經曝光而硬化之 試驗物的附著力之簡便操作，即可判斷脫模步驟可否良好 324027 201245853 進行。 【實施方式] 以下參照第1圖至第4圖而詳細說明本發明。第i圖 係表示本發明之光硬化物之製造方法之一例的截面圖。第 2圖係表示測定附著力之裝置之概略構成的圖。第3圖係 概略表示附著力之測定方法的圖。第4圖係表示附著力之 測定結果之一例的圖。 本發明之光硬化物之製造方法係具有：將以壓印用光 硬化性組成物形成之光硬化性組成物層2夾入於基板1與 形成有凹凸圖形之模具3之間而成形之成形步驟；將光硬 化性組成物層2曝光為光硬化物4之光硬化步驟；以及將 模具3由該光硬化物4脫模之脫模步驟，其中，前述壓印 用光硬化性組成物，係該光硬化性組成物經曝光而硬化之 試驗物對於具有與模具3相同的表面之構件之每單位面積 的附著力為15mN/mm2以下。 具體來說’首先如第1圖（a)所示般，將光壓印用光硬 化性組成物塗佈於基板1上等，藉此在基板丨上形成光硬 化性組成物層2。另外，第1圖（a)中將光硬化性組成物塗 佈於基板1上’但也可將光硬化性組成物塗佈於模具3上。 基板1只要為可設置光硬化性組成物層2者即可，例 如可為通常之光壓印中所使用的基板。具體來說可舉出玻 璃、石夕玻璃、石英、藍寶石等透明無機基板、聚碳酸酯、 聚對苯二甲酸乙二酯（PET)、三醋酸纖維素等透明合成樹脂 基板；以及石夕晶圓等半導體基板、GaAs、InAs、GaN等化 324027 6201245853 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method of producing a photocured material by photoimprinting. [Prior Art] Photo-imprinting is a method in which a photocurable composition layer formed by applying a photocurable composition onto a substrate is brought into contact with a mold having a concave-convex pattern, and the light-curing property is filled in the concave-convex pattern of the mold. In the composition layer, after exposing the photocurable composition layer to a photocured material, the mold is released from the photocured material, whereby a photocured material transferred by the uneven pattern can be obtained. Since the photocured material transferred by the uneven pattern can be easily produced, it has been attracting attention in recent years (see Patent Document 1). However, in the photo-imprinting, when the mold is released from the photo-cured material, the mold may not be released from the photo-cured material, but the photo-cured material is peeled off from the substrate, and the photo-cured material is not The photocured material is peeled off from the substrate - the portion is attached to the mold, and there is a problem that the light having the desired uneven pattern cannot be obtained. This is especially true if the mold is reused. [Prior Art Document] (Patent Document) Patent Document 1: U.S. Patent No. 6,334,960 [Invention] [Problems to be Solved by the Invention] In view of such circumstances, the object of the present invention is to provide a photocured material 324027 4 201245853 The manufacturing method 'is a method of producing a photocured material by photoimprinting, and the demolding step of demolding the mold from the photocured material can be repeated well. (Means for Solving the Problems) The inventors of the present invention have focused their efforts on the above-mentioned problems, and have found that the test material hardened by exposure to the photocurable composition for imprinting has a unit area per unit having the same surface as the mold. When the adhesion is 15 niN/mm 2 or less, the above problems can be solved, thereby completing the present invention. In other words, the method for producing a photocured material according to the present invention comprises: forming a photocurable composition layer formed of a photocurable composition for imprinting between a substrate and a mold having a concavo-convex pattern; a step of exposing the photocurable composition layer to a photocured material; and a demolding step of demolding the mold from the photocured material, wherein the photocurable composition for imprinting is hardened by exposure The adhesion of the test piece per unit area of the member having the same surface as the mold was i5 mN/_2 or less. (Effects of the Invention) According to the present invention, when the test material hardened by exposure to the photocurable composition for imprinting has an adhesion per unit area of a member having the same surface as the mold of 15 mN/mm 2 or less, it is excellent. The demolding step of demolding the mold from the photohardenable material is repeated, and the problem that the mold cannot be released from the photocured material to peel off the photocured material from the substrate, and the photocured material is not peeled off from the substrate to cause the photocured material to be cured - Part of the problem of attaching to the mold. Next, it is judged whether or not the demolding step can be performed 324027 201245853 by simply performing the simple operation of measuring the adhesion of the test article which is cured by exposure using the photocurable composition. [Embodiment] Hereinafter, the present invention will be described in detail with reference to Figs. 1 to 4 . Fig. i is a cross-sectional view showing an example of a method for producing a photocured material of the present invention. Fig. 2 is a view showing a schematic configuration of an apparatus for measuring adhesion. Fig. 3 is a view schematically showing a method of measuring adhesion. Fig. 4 is a view showing an example of the measurement result of the adhesion. In the method of producing a photocured material of the present invention, the photocurable composition layer 2 formed of the photocurable composition for imprinting is formed by sandwiching between the substrate 1 and the mold 3 on which the uneven pattern is formed. a step of exposing the photocurable composition layer 2 to a photocured material 4; and a demolding step of demolding the mold 3 from the photocured material 4, wherein the photocurable composition for imprinting, The test piece hardened by exposure of the photocurable composition to the member having the same surface as the mold 3 had an adhesion per unit area of 15 mN/mm 2 or less. Specifically, the photohardenable composition layer 2 is formed on the substrate 1 by applying a photohardenable composition for photoimprinting onto the substrate 1 as shown in Fig. 1(a). Further, in Fig. 1(a), the photocurable composition is coated on the substrate 1', but the photocurable composition may be applied to the mold 3. The substrate 1 may be any one that can provide the photocurable composition layer 2, and may be, for example, a substrate used in usual photoimprinting. Specific examples thereof include transparent inorganic substrates such as glass, stone glass, quartz, and sapphire, and transparent synthetic resin substrates such as polycarbonate, polyethylene terephthalate (PET), and cellulose triacetate; and Shi Xijing Semiconductor substrate such as a circle, GaAs, InAs, GaN, etc. 324027 6
S 201245853 合物半導體、金屬或金屬氧化物等。接著，基板丨之表面 * 係為了提升與光硬化性組成物層2之接著性及改善光硬化 • 性組成物層2之塗佈狀態等，而可實施前處理。前處理的. 具體例子可舉出藉由濕式表面洗淨或電漿、臭氧洗淨等之 表面改質藉由石夕烧偶合劑之類之接著劑提升劑的處理等。 模具3只要可在表面形成所求之凹凸圖形即可。模具 3的材質的例子可舉出石英玻璃、合成石英玻璃、石夕玻璃、、 及透明鐵氟龍（註冊商標）樹脂、環烯烴聚合物、聚石夕氧橡 膠等合成樹脂等-般光壓印所使用之對於紫外線顯示穿透 性者，此外可舉出石夕、碳化石夕、氧化石夕、鎳等金屬及金屬 氧化物等對於其他活性能量線顯示穿透性者。模具3的外 觀可為與-般的光壓印中所使用之模具 例如外觀可為長方體或捲狀。 门者 此外，在模具3表面所形成之凹凸圖形只要為與一般 光壓印中所使用之模具表面所形成的凹凸圖形相同者即 可，但並不限定於此。例如可為藉由在模具之材料表面形 成凹陷而形成凹部之模具3，此時，相對地凸出於表面侧 的部份為凸部。此外，也可為藉由在模具3之材料表面設 置凸起而形成凸部之模具3,此時，相對而凹陷於内側的 部份為凹部。再者’可使用具有藉由在原版材料表面設置 凹陷或凸起而形成之凹凸圖形的原版，並將該原版作為缚 模而形成之模具3。凹凸圖形之各凹部之截面的形狀可為 正方形、長方形、半圓形或類似該等形狀之形狀等。 此外，為了使光硬化性組成物層2硬化之光硬化物4 324027 ^ 201245853 與模具3的脫模性良好，可在模具3表面實施脫模處理。 脫模處理可藉由氣相法或液相法而使用全氟系或烯烴系之 高分子化合物、烷氧矽烷化合物或三氯矽烷化合物、類鑽 碳（Diamond-Like Carbon)等例示之公知的脫模處理劑而 進行。 形成光硬化性組成物層2之壓印用光硬化性組成物， 係含有具有聚合性基、並藉由紫外線或活性能量線等之曝 光而反應硬化之化合物之硬化性單體者’可為藉由曝光而 陽離子聚合並硬化之光陽離子硬化型、藉由曝光而自由基 聚合並硬化之自由基硬化型、以及併用該等的型式之任一 種。 光陽離子硬化型之壓印用光硬化性組成物可使用之硬 化性單體（陽離子硬化性單體）可舉出具有環氧基、乙烯基 或氧雜環丁基（oxetanyl)等顯示光陽離子聚合性之官能基 的化合物。 此外’自由基硬化型之壓印用光硬化性組成物可使用 之硬化性單體（自由基硬化性單體）可舉出（曱基）丙烯酸 酯、苯乙烯系化合物、丙烯酸系矽烷化合物或多官能單體 等。 壓印用光硬化性組成物可含有感應活性能量線之陽離 子聚合起始劑。感應活性能量線之陽離子聚合起始劑只要 疋以公知之活性能量線照射會產生酸者即可，而可無特別 限制地利用’例如可舉出疏鹽（sulf〇nium salt)、鏘鹽、 鱗鹽或比咬鹽（pyridinium salt)等。 324027 8S 201245853 Compound semiconductor, metal or metal oxide. Then, the surface of the substrate * is preliminarily treated to improve the adhesion to the photocurable composition layer 2, to improve the coating state of the photo-curable composition layer 2, and the like. Specific examples of the pretreatment include surface treatment by wet surface cleaning, plasma cleaning, ozone cleaning, and the like, and treatment with a binder enhancer such as a sulphur coupling agent. The mold 3 may be formed into a desired uneven pattern on the surface. Examples of the material of the mold 3 include quartz glass, synthetic quartz glass, Shishi glass, and transparent Teflon (registered trademark) resin, a synthetic resin such as a cycloolefin polymer or a polyoxo rubber, and the like. The ultraviolet light-transmitting property used for printing may include those exhibiting penetration of other active energy rays, such as a metal such as Shixia, carbonized stone, oxidized stone, and nickel, and a metal oxide. The appearance of the mold 3 can be a mold used in a general photoimprint, for example, the appearance can be a rectangular parallelepiped or a roll. Further, the uneven pattern formed on the surface of the mold 3 may be the same as the uneven pattern formed on the surface of the mold used in general photolithography, but is not limited thereto. For example, it may be a mold 3 in which a concave portion is formed by forming a depression on the surface of the material of the mold, and at this time, a portion which is relatively convex from the surface side is a convex portion. Further, a mold 3 in which a convex portion is formed by providing a projection on the surface of the material of the mold 3 may be used, and at this time, a portion recessed to the inner side is a concave portion. Further, a mold 3 having a concave-convex pattern formed by providing depressions or projections on the surface of the original material and using the original plate as a mold can be used. The shape of the cross section of each concave portion of the concave-convex pattern may be a square, a rectangle, a semicircle or a shape similar to the shape or the like. Further, in order to improve the mold release property of the photocured material 4324027^201245853 which is cured by the photocurable composition layer 2 and the mold 3, a mold release treatment can be performed on the surface of the mold 3. The mold release treatment can be carried out by a gas phase method or a liquid phase method using a perfluoro or olefin-based polymer compound, an alkoxysilane compound, a trichloromethane compound, a diamond-like carbon, or the like. The release treatment agent is carried out. The photocurable composition for imprinting forming the photocurable composition layer 2 is a curable monomer containing a polymerizable group and reacting and curing by ultraviolet light or an active energy ray, etc. A photocationic curing type which is cationically polymerized and hardened by exposure, a radical curing type which is radically polymerized and cured by exposure, and any of these types. The curable monomer (cation-curable monomer) which can be used for the photo-cation hardening type photocurable composition for imprinting has a photocation cation such as an epoxy group, a vinyl group or an oxetanyl group. A polymerizable functional group compound. In addition, the curable monomer (radical curable monomer) which can be used for the photocurable composition for radical curing is exemplified by a (fluorenyl) acrylate, a styrene compound, an acrylic decane compound or Polyfunctional monomers and the like. The photocurable composition for imprint may contain a cationic polymerization initiator which induces an active energy ray. The cationic polymerization initiator which induces an active energy ray can be produced by irradiation with a known active energy ray, and can be used without particular limitation. For example, sulfonium salt, strontium salt, Scale salt or pyridinium salt. 324027 8
S 201245853 此外’壓印用光硬化性組成物係可含感應活性能量線 之自由基聚合起始劑。感應活性能量線之自由基聚合起始 劑可舉出安息香（benzoin)/安息香烷醚類、苯乙酮 (acetophenone)、蒽藏（antraquinone)、嗔0頓酮 (thioxanthone)、縮酮（ketal)、二苯基酮（benzophenone)、 氧蒽S同（xanthone)等公知慣用之感應活性能量線之自由基 聚合起始劑’並可與公知慣用之增敏劑組合使用。 此外’壓印用光硬化性組成物係可含有其他添加劑。 該其他添加劑可舉出溶劑、抗氧化劑、紫外線吸收劑、光 安定劑、矽烷偶合劑、塗面改良劑、附著力降低劑、熱聚 合抑制劑、調平劑（leveling agent)、界面活性劑、保存 安定劑、塑化劑、潤滑劑、填充劑、抗老化劑、濕潤性改 良劑等。 此外’壓印用光硬化性組成物之黏度較佳為lmPa · s 至 l〇Pa · s ’ 更佳為 5mpa · s 至 5Pa · s，特佳為 5mPa · s 至30〇〇pa · s。此係為了使壓印用光硬化性組成物更易於 填充於模具3之圖形。 接著’本發明中，該壓印用光硬化性組成物經曝光而 硬化之試驗物對於具有與模具3相同的表面之構件之每單 位面積的附著力為15mN/min2以下。如此曝光而硬化之試驗 物對於具有與模具3相同的表面之構件之每單位面積的附 著力為15mN/mm2以下，藉由使用15mN/mm2以下之壓印用光 硬化性組成物而以光壓印製造光硬化物，而如後述實施例 所不般可良好地進行模具3由光硬化物4脫模之脫模步 324027 Λ 201245853 驟’且不會有模具3與光硬化物4無法脫模而使光硬化物 4由基板1剝離之情形’此外，也不會有光硬化物*雖未 ”板1制離而光硬化物之一部份卻附著於模具之情形。 接者’若將以往模具3重複使用，即重複進行複數次脫模 步驟’則模具3與光硬化物4之密著力提升，因此會有光 硬化物4 1份附著於模具3之問題，但根據本發明之光 硬化物之製造方法，即使模具3使用例如1_次以上，也 不會產生光硬化物4 —部份附著於模具3而無法獲得具有 所f凹凸圖形之光硬化物之問題。此外，因每單位面積之 附著力在15mN/mm2以τ，故脫模步驟中對於模具3之應力 極小，因此不會破壞模具3。如此之附著力大小推測係根 據模具3之表面狀態與光硬化性組成物而決定，其原因還 不明確三如此限定附著力之大小係未見於以往之壓印法， 3由使母單仇面積之附著力在15mN/mm2以下而可使脫模步 驟極為良好’此知識係本發明者們所初次發現。接著，所 使用之壓印用光硬化性組成物經曝光而硬化找驗物，其 附著力係簡由下述規定之裝置而敎之簡便方法，即可 易於進行脫模步驟之方法。 在此，以下說明壓印用光硬化性組成物經曝光而硬化 之試驗物對於具有與模具3相同的表面之構件之每單位面 積的附著力。測定附著力之裝置為「光硬化性樹脂剝離特 性之力學評價裝置」（島津製作所股份公司製）。此裝置如 表示其概略構成之第2圖所示般，具有：載置基板21並可 方疋轉之平台11，具有支架13之支撐器14,支架13係設置 324027S 201245853 Further, the photocurable composition for imprinting may contain a radical polymerization initiator which induces an active energy ray. The radical polymerization initiator of the inductive active energy ray may be benzoin/benzoin ether, acetophenone, antraquinone, thioxanthone, ketal. A free radical polymerization initiator of a known active energy ray, such as benzophenone or xanthone, can be used in combination with a conventionally known sensitizer. Further, the photocurable composition for imprint may contain other additives. Examples of the other additives include a solvent, an antioxidant, an ultraviolet absorber, a photostabilizer, a decane coupling agent, a coating surface modifier, an adhesion reducing agent, a thermal polymerization inhibitor, a leveling agent, a surfactant, and The stabilizer, the plasticizer, the lubricant, the filler, the anti-aging agent, the wettability improver, and the like are stored. Further, the viscosity of the photocurable composition for imprinting is preferably from lmPa · s to l 〇 Pa · s ', more preferably from 5 mPa · s to 5 Pa · s, particularly preferably from 5 mPa · s to 30 〇〇 pa · s. This is to make it easier to fill the pattern of the mold 3 with the photocurable composition for imprint. Next, in the present invention, the test article which is cured by exposure of the photocurable composition for imprinting has an adhesion force per unit area of the member having the same surface as the mold 3 of 15 mN/min 2 or less. The test piece hardened by such exposure has an adhesion per unit area of the member having the same surface as the mold 3 of 15 mN/mm 2 or less, and is light-pressed by using a photocurable composition for imprinting of 15 mN/mm 2 or less. The photocured material is printed, and the mold 3 is released from the photocured material 4 by the demolding step 324027 Λ 201245853, and the mold 3 and the photocured material 4 cannot be released. In the case where the photocured material 4 is peeled off from the substrate 1, "there is no photocured material*, although the plate 1 is not separated, and a part of the photocured material is attached to the mold. Conventionally, the mold 3 is repeatedly used, that is, the plurality of demolding steps are repeated, and the adhesion between the mold 3 and the photocured material 4 is increased. Therefore, there is a problem that the photocured material adheres to the mold 3 in part, but the light according to the present invention In the method for producing a cured product, even if the mold 3 is used for, for example, 1 or more times, the photocured material 4 does not partially adhere to the mold 3, and the problem of the photocured material having the uneven pattern is not obtained. The adhesion per unit area is 15mN/m Since m2 is τ, the stress on the mold 3 in the demolding step is extremely small, so that the mold 3 is not broken. The magnitude of the adhesion is estimated based on the surface state of the mold 3 and the photocurable composition, and the reason is not clear. The size of the adhesion is not found in the past embossing method. 3 The release step is excellent in the adhesion of the mother-only area to 15 mN/mm2 or less. This knowledge was first discovered by the inventors. Then, the photocurable composition for imprinting used is subjected to exposure to harden the object to be examined, and the adhesion is simplified by a simple method as described below, whereby the demolding step can be easily performed. Here, the adhesion of the test piece hardened by the photocurable composition for imprinting to the unit surface having the same surface as the mold 3 will be described below. The apparatus for measuring the adhesion is "photocurable resin peeling property". "Mechanical evaluation device" (made by Shimadzu Corporation). As shown in Fig. 2 showing a schematic configuration thereof, the apparatus has a platform 11 on which the substrate 21 is placed and can be rotated, a support 14 having a bracket 13, and a bracket 13 is provided 324027
S 201245853 於旋轉之平台11上之基板21的正上方，可維持具有與模 具3相同表面之構件（透鏡）12並可昇降者；以及介由構件 12而使基板21表面曝光之光照射手段。該光照射手段係 由光源15與設置於對於垂直方向之45。之鏡面16所成， 鏡面16係反射由光源15所照射的光並穿透構件12,而照 射在平台11上所載置之基板21的表面。接著在構件12 連接測力器（load cell)(圖上無標示），係在構件12於垂 直方向移動時可測定其力之構造。 接著’在該裝置中，使用具有與光硬化物製造方法所 實際使用之模具3相同表面之構件，該構件係特定形狀的 透鏡’具體來說以直徑30Φ、中心厚度12. 3mm、邊緣厚度 2. Omm、曲率半徑16. 10顏、焦點距離35mm之透鏡作為構 件12而使用，在基板21上滴下上述塵印用光硬化性組成 物，並求附著力。另外，具有與模具3相同表面之構件12 係指，模具3在使用未脫模處理者時，係具有上述形狀且 與模具3相同材質之透鏡’模具3在使用經脫模處理者時， 係具有上述形狀且與模具3相同材質之構件的表面實施與 模具3相同之脫模處理者。 如概略表不附者力之測疋方法之第3圖所示般，首先 製作壓印光硬化性組成物’並例如使用微吸管等滴下預定 量之壓印用光硬化性組成物22於平台i]_上載置之基板21 上（第3圖（a)及第3圖（b))。接者’以使所滴下之壓印用 光硬化性組成物22位於支架13所支撐之構件12之垂直方 向下側之方式，而旋轉平台1K第3圖（c))。接著使支架 324027 11 201245853 13下降’並以使構件12與基板21之距離為預定值之方式， 而使構件12與壓印用光硬化性組成㈣接觸（第3圖⑷）。 接著再度使支架13下降，使構件12.與支架13為未接觸的 狀態（第3圖⑼。接著由光源15照射光’使壓印用光硬 化性組成物22硬化並形成試驗物23(第3圖（〇)。之後將 支架丨3以特定速度上升（第3圖（8))，並將試驗物23由構 件12剝離（第3圖（h))。將構件12由該試驗物23剝離時 以測力器所測定的力（附著力）F，除以試驗物23與構件12 之接觸面積的值’即為每單位面積之附著力。第4圖表示 附著力測定結果的一例。另外，若試驗物23由基板i剝離， 則試驗物23無法由構件12剝離而無法測定附著力。因此， 每單位面積之附著力為15mN/mm2以下之規定，亦成為試驗 物23未由基板1剝離之狀態者之規定。 使用壓印用光硬化性組成物而在基板1或模具3形成 光硬化性組成物層2之方法並無特別限定，例如可塗佈或 滴下光硬化性組成物，具體來說可舉出旋轉塗布（Spin coating)、輥式塗布（roll coating)、浸潰塗布（dip coating)、凹版塗佈（gravure coating)、剛模塗佈（die coating)、簾幕式塗佈（curtain coating)、喷墨塗佈及點 膠塗佈（dispensing coat)等。 接著如第1圖（b)所示般以基板1與模具3夾著光硬化 性組成物層2而成形（成形步驟）。在此，可將基板1向模 具3擠壓，也可將模具3向基板1擠壓’也可將基板1及 模具3兩者擠壓。擠壓基板1及模具3的力可例如為〇. 〇1S 201245853 directly above the substrate 21 on the rotating platform 11, the member (lens) 12 having the same surface as the mold 3 can be maintained and lifted, and the light irradiation means for exposing the surface of the substrate 21 via the member 12 can be maintained. The light irradiation means is provided by the light source 15 and 45 in the vertical direction. The mirror surface 16 is formed. The mirror surface 16 reflects the light irradiated by the light source 15 and penetrates the member 12 to illuminate the surface of the substrate 21 placed on the stage 11. Next, a load cell (not shown) is attached to the member 12 to determine the force configuration of the member 12 as it moves in the vertical direction. Next, in the apparatus, a member having the same surface as the mold 3 actually used in the photocurable material manufacturing method is used, which is a lens having a specific shape, specifically, a diameter of 30 Φ, a center thickness of 12.3 mm, and an edge thickness of 2 A lens having an Omm, a radius of curvature of 16.10, and a focal length of 35 mm is used as the member 12, and the photocurable composition for dust printing is dropped on the substrate 21, and adhesion is obtained. Further, the member 12 having the same surface as the mold 3 means that the mold 3 has the same shape as the mold 3 and the mold 3 is the same material as the mold 3 when the mold is removed. The surface of the member having the above-described shape and the same material as that of the mold 3 is subjected to the same mold release process as the mold 3. As shown in Fig. 3 of the method for measuring the force of the non-attached force, first, an imprinted photocurable composition is produced, and a predetermined amount of the photocurable composition for imprinting 22 is dropped on the platform, for example, using a micropipette or the like. i] _ placed on the substrate 21 (Fig. 3 (a) and Fig. 3 (b)). The carrier is rotated so that the embossed photocurable composition 22 is placed on the lower side of the member 12 supported by the holder 13 to rotate the stage 1K (Fig. 3). Next, the holder 324027 11 201245853 13 is lowered ′ and the member 12 is brought into contact with the photocurable composition (4) for imprinting so that the distance between the member 12 and the substrate 21 is a predetermined value (Fig. 3 (4)). Then, the holder 13 is lowered again, and the member 12 and the holder 13 are not in contact with each other (Fig. 3 (9). Then, the light is irradiated by the light source 15 to harden the photocurable composition 22 for imprinting and form the test object 23 (the 3 (〇). The stent 丨 3 is then raised at a specific speed (Fig. 3 (8)), and the test object 23 is peeled off from the member 12 (Fig. 3 (h)). The member 12 is used for the test article 23 The force (adhesion) F measured by the force measuring device at the time of peeling is divided by the value of the contact area between the test piece 23 and the member 12, that is, the adhesion per unit area. Fig. 4 shows an example of the measurement result of the adhesion. Further, when the test piece 23 is peeled off from the substrate i, the test piece 23 cannot be peeled off by the member 12, and the adhesion cannot be measured. Therefore, the adhesion per unit area is 15 mN/mm 2 or less, and the test piece 23 is not used as the substrate. The method of forming the photocurable composition layer 2 on the substrate 1 or the mold 3 by using the photocurable composition for imprinting is not particularly limited, and for example, the photocurable composition can be applied or dropped. Specifically, spin coating and rolls are mentioned. Roll coating, dip coating, gravure coating, die coating, curtain coating, inkjet coating, and dispensing (dispensing coat), etc. Next, as shown in Fig. 1(b), the substrate 1 and the mold 3 are sandwiched between the photocurable composition layer 2 (forming step). Here, the substrate 1 can be extruded toward the mold 3. Pressing, the mold 3 can also be pressed toward the substrate 1. It is also possible to press both the substrate 1 and the mold 3. The force for pressing the substrate 1 and the mold 3 can be, for example, 〇. 〇1
324027 12 S 201245853 至lOOMPa左右。為了防止異物混入而造成模具3的損壞， 擠壓的力即使在前述擠壓範圍内也是越小越好。此外可不 施加力’而藉由模具3及基板1本身重量而擠壓。藉由如 此對於基板1而擠壓模具3，可使光硬化性組成物層2充 填於模具3之凹凸圖形而成形。較佳為光硬化性組成物層 2與模具3共同維持水平並使光硬化性組成物層2與模具3 相接觸’但若會使所得圖形產生不良，也並非限定要保持 水平。成形步驟中可使用以往光壓印之裝置。 接著，如第1圖（c)所示般，在光硬化性組成物層2 充填於模具3之凹凸圖形而成形之狀態下，使光硬化性組 成物層2曝光並硬化而為光硬化物4(光硬化步驟）^曝光 所使用之光源如為可照射使光硬化性組成物層2硬化之波 長的光即可，光源之例可舉出低壓水銀燈、高壓水銀燈、 超面壓水銀燈、金屬鹵素燈、氙氣燈、碳弧燈、汞氙燈、 XeCl、KrF或ArF等之準分子雷射（excimer iaser)、紫外 線或可見光雷射、以及紫外線或可見光LED等。光的照射 量只要為可使光硬化性組成物層2硬化的量即可。在工業 上貫施本發明時，通常可選定1 〇j/cm2以下範圍内之照射 量。另外，基板1及模具3中’從對於照射的光為實質透 明之構件侧將光照射至光硬化性組成物層2。 之後如第1圖（d)所示般，藉由將模具3由光硬化物4 脫模’而可得轉印有模具3之凹凸圖形之光硬化物4(脫模 步驟）。本發明中’因上述每單位面積之附著力為15mN/mm2 以下’故可良好地進行該脫模步驟，並不會有模具3與光 324027 13 201245853 硬化物4無法脫模而使光硬化物4由基板1剝離之情形， 此外，也不會有光硬化物4雖未由基板丨剝離卻使光硬化 物一部份附著於模具之情形。此外，即使使用同樣的模具 3進行複數次光壓印，也可形成具有模具3之凹凸圖形經 精密轉印之凹凸圖形的光硬化物4。脫模時較佳為基板1 與模具3共同維持水平而脫模，但不必限定要維持水平。 (實施例） 以下基於實施例說明本發明’但本發明並不限定於該 等實施例。 〈實施例1至21及比較例1至6之壓印用光硬化性組成物 之調製> 對於表1及表2所示之硬化性單體1〇〇質量份，添办 表1及表2所示預訂量之感應活性能量線之聚合起始_ 增敏劑，並在室溫下獅而轉後，添加表丨及表2所弃 預訂量之附著力降低劑並在室溫H㈣製液狀之屬 印用光硬化性組成物實施例丨至21及比較例丨至6。表 及表4表示硬化性單體、附著力降低劑、感應活性能量姨 之聚合起始劑及增敏劑之具體内容。另外，如表1所示舟 實施例1至U及比較例丨至2係光陽離子硬化型之壓 光硬化性組成物，如表2所示般實施例12至21及比較合 3至6係自由基硬化型之壓印用光硬化性組成物。 ^實施例i至及比較例i至6之壓印用光硬化性組幻 經曝光而硬化之試驗物的評價> <壓印用光硬化性組成物轉光而硬化之試驗物的評價〉 324027 14 201245853 (實施例1至20及比較例1至6用之構件12的製作） 將石英透鏡（sigma光學股份公司製、商品編號SLSQ-30-35、直徑30mm、中心厚度12. 3mm、邊緣厚度2. 〇mm、 曲率半徑16. 10mm、焦點距離35mm)置於氯仿中，以超音波 洗淨器洗淨5分鐘後取出並乾燥，在壓力ikpa下，以氣氣 準分子光照射單元（USHIO電機股份公司製、UER-20-172VA) 所放射之波長172nm之真空紫外線（VUV線）曝光30分鐘。 之後使用紫外線（UV)/臭氧清潔機（Sen Lights股份公司製 PL16-110)將該石英透鏡洗淨15分鐘。接著浸潰於全氟謎 系脫模劑（Daikin工業股份公司製、〇pt〇〇1 hd—uoozm 分鐘。之後取出並在6(TC下放置1小時，以溶劑（Daikin 工業股份公司製、optoolHD_zv)洗淨吹以氮氣乾燥，製作 以脫模劑施行脫模處理之石英透鏡，並作為構件12。 (實施例21用之構件12的製作）324027 12 S 201245853 to about 100MPa. In order to prevent the damage of the mold 3 caused by the incorporation of foreign matter, the force of the pressing is as small as possible within the aforementioned extrusion range. Further, it can be pressed by the weight of the mold 3 and the substrate 1 without applying a force. By pressing the mold 3 on the substrate 1 as described above, the photocurable composition layer 2 can be formed by filling the uneven pattern of the mold 3. It is preferable that the photocurable composition layer 2 is maintained horizontally with the mold 3 and the photocurable composition layer 2 is brought into contact with the mold 3. However, if the resulting pattern is defective, it is not limited to be maintained. A conventional optical imprinting apparatus can be used in the forming step. Then, as shown in Fig. 1(c), the photocurable composition layer 2 is exposed and formed in a concave-convex pattern of the mold 3, and the photocurable composition layer 2 is exposed and cured to be a photocured material. 4 (Photohardening step) ^ The light source used for the exposure may be light that can illuminate the wavelength at which the photocurable composition layer 2 is cured. Examples of the light source include a low pressure mercury lamp, a high pressure mercury lamp, an ultra surface pressure mercury lamp, and a metal. Halogen lamps, xenon lamps, carbon arc lamps, mercury xenon lamps, excimer iapers such as XeCl, KrF or ArF, ultraviolet or visible lasers, and ultraviolet or visible LEDs. The amount of light to be irradiated may be an amount that can cure the photocurable composition layer 2. When the present invention is applied industrially, it is usually possible to select an irradiation amount in the range of 1 〇 j/cm 2 or less. Further, in the substrate 1 and the mold 3, light is irradiated to the photocurable composition layer 2 from the side of the member which is substantially transparent to the light to be irradiated. Thereafter, as shown in Fig. 1(d), the photocured material 4 on which the uneven pattern of the mold 3 is transferred is obtained by demolding the mold 3 from the photocured material 4 (mold release step). In the present invention, the "release force per unit area is 15 mN/mm2 or less", so that the mold release step can be favorably performed, and there is no mold 3 and light 324027 13 201245853. The cured product 4 cannot be released from the mold to make the light cured product. 4 When the substrate 1 is peeled off, there is no case where the photocured material 4 is not peeled off from the substrate but a part of the photocured material is attached to the mold. Further, even if a plurality of photoimprints are carried out using the same mold 3, the photocured material 4 having the uneven pattern of the uneven pattern of the mold 3 which is precisely transferred can be formed. In the case of demolding, it is preferred that the substrate 1 and the mold 3 are horizontally released to release the mold, but it is not necessary to maintain the level. (Examples) Hereinafter, the present invention will be described based on examples, but the present invention is not limited to the examples. <Preparation of photocurable composition for imprinting of Examples 1 to 21 and Comparative Examples 1 to 6> Table 1 and Tables were added to 1 part by mass of the curable monomer shown in Tables 1 and 2 2 The amount of the active energy line of the indicated amount of the activation is shown as a sensitizer, and after the lion is turned at room temperature, the adhesion reduction agent of the watch and the reserved amount of the table 2 is added and is made at room temperature H (four). The liquid-like photocurable composition examples 丨 to 21 and comparative examples 丨 to 6. Tables and Table 4 show the specific contents of the curable monomer, the adhesion reducing agent, the polymerization initiator of the induction active energy 及, and the sensitizer. Further, as shown in Table 1, the calendering compositions of the boat examples 1 to U and the comparative examples to 2 were photocation-hardening type, as shown in Table 2, Examples 12 to 21 and Comparative 3 to 6 series. A photocurable composition for imprinting of a radical hardening type. ^Evaluation of Test Articles Cured by Photocuring Group of Imprinting Photocuring Groups of Examples I to and Comparative Examples i to 6><Evaluation of Test Articles Cured by Light Curing Compositions for Embossing and Curing 324027 14 201245853 (Production of members 12 for Examples 1 to 20 and Comparative Examples 1 to 6) A quartz lens (manufactured by Sigma Optical Co., Ltd., product number SLSQ-30-35, diameter 30 mm, center thickness 12.3 mm, Edge thickness 2. 〇mm, radius of curvature 16.10mm, focal length 35mm) was placed in chloroform, washed with ultrasonic cleaner for 5 minutes, taken out and dried, under air pressure excimer light irradiation unit under pressure ikpa (USHIO Electric Co., Ltd., UER-20-172VA) Vacuum ultraviolet light (VUV line) of a wavelength of 172 nm emitted was exposed for 30 minutes. Thereafter, the quartz lens was washed for 15 minutes using an ultraviolet (UV)/ozone cleaner (PL16-110 manufactured by Sen Lights Co., Ltd.). Then, it was immersed in a perfluoromyceumatic release agent (manufactured by Daikin Industries Co., Ltd., 〇pt〇〇1 hd-uoozm minutes. After that, it was taken out and placed at 6 (TC for 1 hour, with solvent (Daikin Industrial Co., Ltd., optoolHD_zv). The washing and blowing were dried with nitrogen to prepare a quartz lens which was subjected to mold release treatment with a releasing agent, and was used as the member 12. (Production of member 12 for Example 21)
與則述相同，將放入以氯仿洗淨、以真空紫外線曝光、 以紫外線（UV)/臭氧清潔劑洗淨之石英透鏡，以及 (microliter)之2-(全象己基）乙基三甲氧基石夕烧（FAS13) (Gelest么司製）之3mL玻璃瓶放入容積⑽此之聚對笨二 :^乙-gaCPTFE；；)製容器後加以密封。接著將密封之pTFE 放人預先加熱至15代的烤箱。卜!、時後取出PTFE ^並取tU；5域具’製作以F聰施行脫模處理之石 英透鏡，並作為構件12。 (附著力之測定） 使用將上迷所製作之構件12載置於支架13之「光硬 324027 15 201245853 化性樹脂剝離特性之力4¾ % > ,tJ . 予砰彳貝裴置」（島津製作所股份公司 製），測疋壓印用光硬化性 ^ 〇 庄、、、且成物經曝光而硬化之試驗物 23的母单位面積之附著力。 @ men 附者力測定進行10次，將第6 久起至第1〇久所求之备显 #早位面積之附著力的平均值，作為 壓印用光硬化性組成物經曝^硬化之試驗物Μ的每單 位面積之附著力。具體來說，以微吸管滴下40"L之各壓 印用光硬錄組絲於Η切晶圓上，並㈣平台U 使壓印用級化性組成物配置於構们2的正下方。接著， 以使支架13最下面兩度為距離石夕晶圓表面Q 5⑼顏之方式 維持30秒後，卩㈣収附著力，並開始使核13下降。 支架13最下面高度為距離石夕晶圓表面〇〇5〇賴時，紫外線 光源（汞氣燈、三永電機製作所製、Sup⑽心⑹所放射 之波長35〇nm以上的紫外線，以光照射量〇 65J/cm2(測定 波長364mn之紫外線強度65mW/cm2、照射1〇秒鐘）照射， 硬化壓印用光硬化性組成物而製作為試驗物23。之後以 0.60mm/秒之速度開始使支架13上升，以1〇微秒之間隔測 定施於測力器的力’並測定構件12由試驗物23剝離時的 最大力（附著力）F。重複10次該等操作，並在第6次至第 10次測定分別測定試驗物23與構件12之接觸面的直徑而 求平均值，作為構件12與試驗物23之接觸面的直經（mm)。 由構件12與試驗物23之接觸面的直徑而算出構件12與試 驗物23之接觸面積（mm2)。求出由第6次至第1〇次共5 -欠 所測定之附著力F的平均值’並除以構件12與試驗物^ 之接觸面積’作為壓印用光硬化性組成物經曝光而硬化之 324027 16As described above, a quartz lens which is washed with chloroform, exposed to vacuum ultraviolet light, washed with an ultraviolet (UV)/ozone cleaner, and a (microliter) 2-(all-like hexyl)ethyltrimethoxy stone are placed. Xishao (FAS13) (Gelest's 3mL) glass bottle is placed in the volume (10). This is a pair of two: 乙B-gaCPTFE;;) After the container is sealed. The sealed pTFE was then preheated to the 15th generation oven. After that, PTFE ^ was taken out and tU was taken; 5 domain tool 'made a quartz lens which was subjected to mold release treatment by F. (Measurement of Adhesion) The force of the peeling characteristic of the light hard 324027 15 201245853-based resin placed on the holder 13 is 43⁄4 % >, tJ. (manufactured by the company), the adhesion of the mother unit area of the test piece 23 which is cured by exposure and photohardenability. @men Attached to the force measurement for 10 times, the average value of the adhesion of the early surface area from the 6th long to the 1st long time is used as the photocurable composition for imprinting. The adhesion per unit area of the test object. Specifically, a micro-sipper is used to drop 40"L for each of the embossing optical hard-recording wires on the diced wafer, and (4) the platform U is used to place the grading-level grading composition directly under the structure 2. Next, after the lowermost degree of the holder 13 is maintained for 30 seconds from the surface of the surface of the wafer, the 卩(4) receives the adhesion and starts to lower the core 13. When the height of the bottom of the holder 13 is 〇〇5 距离 〇 , , , , , , , , , 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线〇 65 J/cm 2 (ultraviolet intensity of measurement 364 mn, 65 mW/cm 2 , irradiation for 1 sec.) was irradiated, and the photocurable composition for embossing was cured to prepare test article 23. Then, the stent was started at a speed of 0.60 mm/sec. 13 is raised, and the force applied to the force measuring device is measured at intervals of 1 μ microsecond and the maximum force (adhesion force) F when the member 12 is peeled off from the test object 23 is measured. This operation is repeated 10 times and at the 6th time. The diameter of the contact surface between the test piece 23 and the member 12 was measured by the tenth measurement, and the average value was measured as the direct contact (mm) of the contact surface between the member 12 and the test piece 23. The contact surface of the member 12 and the test piece 23 was used. The contact area (mm2) between the member 12 and the test piece 23 was calculated from the diameter. The average value of the adhesion force F measured by the sixth to the first time was determined and divided by the member 12 and the test object. ^ The contact area 'as a photocurable composition for imprinting is hardened by exposure 324027 16
S 201245853 試驗物23的每單㈣積之_力。結果衫於表丨及表 2。另外，附著力的測定在大氣下進行。 (藉由壓印之光硬化物的製作及評價） 使用壓印裝置（明昌機工股份公司製、NM〇8〇1)，並藉 料壓印法而製作光硬化物4。具體來說，在與上述測定附 著力時所使用者相同之6时石夕晶圓上旋轉塗佈各壓印用光 硬化性組成物，而形成光硬化性組成物層2。接著將實施與 上述石英透鏡相同之脫模處理，深度35〇nm、35〇nm至1〇 //m(微米）之尺寸範圍，並形成有線&間隔（111^&邛狀6)、 孔（hole)、柱（pillar)之各圖案的1〇mm□之石英模具 (NTT-AT股份公司製、Nim-PH35〇)與光硬化性組成物層2 接觸，模具面積每100mm2施加100N的力（擠壓力iMPa)，紫 外線光源（采氙燈、三永電機製作所製、Supercure2〇3S) 所放射之波長350nm以上的紫外線，以光照射量〇. 2J/cm2 (測定波長365nm之紫外線強度l〇mW/cm2、照射20秒鐘） 照射’使光硬化性組成物層2硬化。之後藉由將模具3脫 模而製作光硬化物4，該藉由光硬化而製作光硬化物4之 操作進行1〇〇〇次，即使進行1〇〇〇次，光硬化物4也沒有 附著於模具3，且光硬化物不會由石夕晶圓剝落而良好地脫 权之情形判定為「〇」，有1次以上光硬化物4附著於模具 3或光硬化物4由矽晶圓剝落之情形判定為「X」，而評價 脫模步驟。結果表示於表1及表2。 該結果如表1及表2所示般’在使用壓印用光硬化性 組成物經曝光而硬化之試驗體23之每單位面積之附著力 324027 17 201245853 為15mN/mm2以下之實施例1至21時，即使以同一模具進 行1000次光壓印也可良好地進行脫模步驟。另一方面，使 用附著力大於15mN/mm2之比較例1至6時，光硬化物4之 全部或一部份附著於模具3,而無法良好地進行脫模步驟。 另外，若每單位面積之附著力為15mN/mm2以下，則脫模步 驟中實質上對於模具3的應力較少，因此難以引起模具3 之破壞，因以一般之光壓印而轉印，故即使是具有各種不 同之凹凸圖案之模具3，也可良好地重複進行脫模步驟。S 201245853 The force of each (four) product of the test object 23. The results are shown in Tables and Table 2. In addition, the measurement of the adhesion was carried out under the atmosphere. (Preparation and evaluation of embossed light-cured material) A photo-cured material 4 was produced by an imprint method using an imprint apparatus (manufactured by Mingchang Machinery Co., Ltd., NM 〇8〇1). Specifically, the photocurable composition layer 2 is formed by spin-coating each of the photocurable photocurable compositions on the same day as the user at the time of measuring the adhesion. Then, the same mold release treatment as that of the above quartz lens is carried out, and the depth ranges from 35 〇 nm to 35 〇 nm to 1 〇//m (micrometer), and a wire & interval (111^& A 1 mm-square quartz mold (manufactured by NTT-AT Co., Ltd., Nim-PH35®) of each of the holes and the pillars was placed in contact with the photocurable composition layer 2, and a mold area of 100 N was applied per 100 mm 2 . Force (extrusion force iMPa), ultraviolet light source (Supercure 2〇3S, manufactured by Sanyo Electric Co., Ltd.), ultraviolet light having a wavelength of 350 nm or more, and light irradiation amount 〇 2 J/cm 2 (measurement wavelength 365 nm ultraviolet intensity l 〇mW/cm2, irradiation for 20 seconds) Irradiation 'The photocurable composition layer 2 is cured. Thereafter, the photocured material 4 is produced by demolding the mold 3, and the operation of producing the photocured material 4 by photocuring is performed once, and the photocured material 4 is not adhered even once 1 time. In the case of the mold 3, and the photocured material is not peeled off by the Shixi wafer and is well deprived, it is judged as "〇", and the photocured material 4 is attached to the mold 3 or the photocured material 4 by the tantalum wafer once or more. The peeling condition was judged as "X", and the demolding step was evaluated. The results are shown in Tables 1 and 2. As shown in Table 1 and Table 2, the adhesion per unit area of the test piece 23 which was cured by exposure using the photocurable composition for imprinting was 324027 17 201245853, which was 15 mN/mm 2 or less. At 21 o'clock, the demolding step can be favorably performed even if 1000 times of photoimprinting is performed in the same mold. On the other hand, when Comparative Examples 1 to 6 having an adhesion of more than 15 mN/mm 2 were used, all or a part of the photocured material 4 adhered to the mold 3, and the demolding step could not be performed satisfactorily. Further, when the adhesion per unit area is 15 mN/mm 2 or less, the stress on the mold 3 is substantially small in the demolding step, so that it is difficult to cause the mold 3 to be broken, and the transfer is performed by ordinary photo imprinting. Even in the mold 3 having various uneven patterns, the demolding step can be well repeated.
324027 18 S 201245853 表 比較例 2 壓印用光硬化性組成物（質量份） 1 1 ! CQ s 1 1 σ<ο d 評價結果 optoo1 HD- 1100Z 1400 oo oo 61.4 OO CQ X 比較例| 1 1 ] 1 1 g s 1 1 c>a optoo1 HD- 1100Z s C3> 03 οό 53.3 » 1嶒 X 實施例 11 CO 1 1 1 1 1 芑 另 1 1 ΡΟ CN3 c5 optoo1 HD-1100Z s m M od 52.8 〇 CO 1 1 1 1 1 k/» Wi 1 1 o 1 eo CQ <=3 optoo1 El· 1100Z CO oo oo od 61.4 csi 〇 實施例 9 CO 1 1 1 1 I s 1 1 I o 1 CO d optoo1 HD-1100Z s CO 03 70.2 〇 實施例 8 1 1 1 1 1 1 s o 蠓 1 1 1 ci optoo1 HD- 1100Z ΙΛ 々 7α 7 〇〇 〇 實施例 7 OQ 1 1 1 1 I o ur> g 1 1 1 1 CQ c=5 optoo1 HD- 1100Z S σ% οό (Ο LA 〇 實施例 6 [ 1 1 1 oo I s 1 1 1 1 CNl c=S optoo1 HD- 1100Z i 〇〇 οό 62.6 〇 實施例 5 1 1 1 oo 1 1 s 1 1 I 1 1 cs3 c3 ! optoo1 HD- _z i ¢^- οά 61.2 〇d 〇 實施例 4 1 1 1 eo 1 1 1 s 1 1 1 1 1 cs) o optoo1 HD- 1100Z 茬 LO οό 1 57.8 卜 〇 實施例 3 1 1 1 1 1 s s 1 1 1 1 1 c>a o optoo1 HD- 1100Z s CM 〇> Ρ0 IS 〇 實施例 2 〇〇 1 ί 1 1 1 s s 1 1 1 1 ^—4 1 09 optoo1 HI>- 1100Z σ> οό 62.8 寸 〇 實施例 I CO 1 1 1 ! 1 s n 1 1 1 1 1 o optoo1 HD- 1100Z 〇 s oa οό 〇〇 〇 • * C|4 CQ Ln CO s CO da 1 IA CO oa Cj« 1« Λ 所使用之脫模劑 附著力F(eN) W ν ί 賴眉 鉬勃 紱Ή 破W Ϊ3 « 幸锘 班球 m CJ 鞀一> 鉬"目 % J 破淮 2 β 每單位面積之附著力 (aN/m2) 脫模步驟之評價 附著力 1 降低劑 硬化性單體 诸 增敏命1 324027 19 201245853 [表2] 比較例 6 壓印用光硬化性组成物（質量份） 1 ί 1 1 1 1 1 1 1 J 1 g CO iX^ 評價結果 optool HD- 1100Z ο O') 〇6 6a 〇 cn txi X 比較例 5 1 1 1 1 1 i 1 1 1 1 1 s eo LT» optool HD- 1100Z 芑 ΙΑ 9 4 〇> 66.0 , X 比較例 4 1 1 1 1 l l 1 1 1 oa 1 1 g eo optool! HD- 1100Z CO CO Q0 55.2 2α 2 X 比較例 3 1 1 1 1 1 1 1 1 1 1 1 1 2 CO U0 optool HD- 1100Z Μ CO od LO οό VT9 25.3 X 如： cr5 1 1 1 1 1 1 1 [ 1 1 J o CO ixi FAS13 CO CO οό 54.4 cs 〇 實施例 20 1 1 1 1 1 1 1 1 CO e^5 1 1 1 g eo IX$ optool HD- 11002 eg C<l οό tA an CO 〇 實施例 19 1 1 1 1 1 ] 1 s 1 1 1 1 s co uS optool HD- 1100Z 芑 LA era oi ιΗ Q ai ο 實施例 18 1 ] 1 1 s 1 I 1 1 1 1 s C〇 ui optool HI>- 11002 s CS> 00 丨緘 〇 實施例 17 1 1 o 1 1 1 1 l 1 1 g CO LT> optool 1 HD- nooz i U3 CO οό οό Lrt 〇 實施例 18 1 I C<l ] 1 1 1 1 1 o CQ Lri optool HD- liOOZ <=> Ψ < erf ••V4 〇 實施例 15 1 1 1 l CO CO l 1 1 s CQ optool HD- 1100Z g CO o oo 50.9 寸 CO 〇 實施例 14 1 1 1 1 1 g •丨 CO LA optool HD- I100Z C3 ua ΙΛ CO od 54 4 CQ 〇 實施例 13 1 cr$ 1 1 1 1 1 1 1 1 o CO tn optool HD- 1100Z s 〇> o O) 65. Z ! Q t£3 〇 實施例 12 CQ ι 1 l 1 1 [ 1 1 ] 1 1 g eo optool HD- 1100Z C3 oo CO CO CO 〇 CO tj- oo 4： A-10 A-ll U-12J A-13 £ CQ 所使用之脫模劑 附著力F (mK) V 鉬却 Ή 赛雄 CO 紱J 硃婼 亡β 锥球 每單位面積之附著力 in^/m2) 耽模步驟之評價 附著力 降低劑 硬化性單體 菹 «Μη 20 324027 s 201245853 [表3] 表記 商品名 公司名 物質名稱 'Ί A-1 - Daikin工業 2-(全氟己基）乙醇^ [F(CF2)6CH2CH2〇H] A-2 - Daikin工業 2-(全氟2 丁基）乙醇> [F(CF2)4CH£H2〇H] A-3 — Daikin工業 全氟乙基曱醇 ' [f(cf〇2ch2〇h] A-4 一 h光純鏟 丁醐 A-5 MMPGAC Uaicei化學工業股份公司 丙二醇甲醚醋酸醋 A-6 PolyFox PF3320 UM1NUVA Solutions Inc. 註1 〜 B-1 CELOXIDE 2021P Daicel化學工業股份公司 3, 4-環氧基環己烯甲基 -3’，4’ -環氧基環己烯破酸酯 B-2 ARONE OXETANE 0XT-121 東亞合成化學工業股份公司 1，4-雙[(3-乙基-3-氧雜環亍 基甲氧基)甲基]苯n-1 B-3 CELOXIDE 8000 Daicel化學工業股份公司 二環己基-3,3-二烯二氧化物 Β·4 TEGDVE 丸善石油化學 三乙二醇二乙嫌謎 Β-5 Aronix M-309 東亞合成化學工業股份公司 三羥甲基丙烷三丙烯酸酯 Β-6 Light acrylate 4E0-A 共榮社化學 CH2=CH-C0-(CH2CH2〇)4-C0-CH=C Ha C-l PI2074 Rhodia 錤鹽 C-2 Irgacure 651 BASF 2, 2-二甲氧基-1,2-二笨基乙 烷-1-酮 D-l AnthracureR UVS-1331 川崎化成 DBA二丁氧基蒽 註1) 〇ch2cf3324027 18 S 201245853 Table Comparative Example 2 Photocurable composition for embossing (parts by mass) 1 1 ! CQ s 1 1 σ<ο d Evaluation result optoo1 HD-1100Z 1400 oo oo 61.4 OO CQ X Comparative example | 1 1 ] 1 1 gs 1 1 c>a optoo1 HD- 1100Z s C3> 03 οό 53.3 » 1嶒X Example 11 CO 1 1 1 1 1 芑1 1 ΡΟ CN3 c5 optoo1 HD-1100Z sm M od 52.8 〇CO 1 1 1 1 1 k/» Wi 1 1 o 1 eo CQ <=3 optoo1 El· 1100Z CO oo oo od 61.4 csi 〇Example 9 CO 1 1 1 1 I s 1 1 I o 1 CO d optoo1 HD-1100Z s CO 03 70.2 〇Example 8 1 1 1 1 1 1 so 蠓1 1 1 ci optoo1 HD- 1100Z ΙΛ α7α 7 〇〇〇 Example 7 OQ 1 1 1 1 I o ur> g 1 1 1 1 CQ c= 5 optoo1 HD- 1100Z S σ% οό (Ο LA 〇 Example 6 [ 1 1 1 oo I s 1 1 1 1 CNl c=S optoo1 HD- 1100Z i 〇〇οό 62.6 〇Example 5 1 1 1 oo 1 1 s 1 1 I 1 1 cs3 c3 ! optoo1 HD- _z i ¢^- οά 61.2 〇d 〇Example 4 1 1 1 eo 1 1 1 s 1 1 1 1 1 cs) o optoo1 HD- 1100Z 茬LO οό 1 57.8 Di Example 3 1 1 1 1 1 ss 1 1 1 1 1 c>ao optoo1 HD-1100Z s CM 〇> Ρ0 IS 〇Example 2 〇〇1 ί 1 1 1 ss 1 1 1 1 ^—4 1 09 optoo1 HI>- 1100Z σ> οό 62.8 inch implementation Example I CO 1 1 1 ! 1 sn 1 1 1 1 1 o optoo1 HD- 1100Z 〇s oa οό 〇〇〇• * C|4 CQ Ln CO s CO da 1 IA CO oa Cj« 1« Λ Moulding agent adhesion F(eN) W ν ί Lai Mei Mo-Bo 绂Ή Broken W Ϊ3 « Fortunately, the class ball M CJ 鼗一> Molybdenum " M % Breaking Huai 2 β Adhesion per unit area (aN/ M2) Evaluation of the release step Adhesion 1 Reducing agent hardening monomer sensitization life 1 324027 19 201245853 [Table 2] Comparative Example 6 Photocurable composition for embossing (parts by mass) 1 ί 1 1 1 1 1 1 1 J 1 g CO iX^ Evaluation result optool HD-1100Z ο O') 〇6 6a 〇cn txi X Comparative example 5 1 1 1 1 1 i 1 1 1 1 1 s eo LT» optool HD- 1100Z 芑ΙΑ 9 4 〇> 66.0 , X Comparative Example 4 1 1 1 1 ll 1 1 1 oa 1 1 g eo optool! HD- 1100Z CO CO Q0 55.2 2α 2 X Comparative Example 3 1 1 1 1 1 1 1 1 1 1 1 1 2 CO U0 optool HD- 1100Z Μ CO od LO οό VT9 25.3 X Cr5 1 1 1 1 1 1 1 [ 1 1 J o CO ixi FAS13 CO CO οό 54.4 cs 〇 Example 20 1 1 1 1 1 1 1 1 CO e^5 1 1 1 g eo IX$ optool HD- 11002 eg C< ;l οό tA an CO 〇Example 19 1 1 1 1 1 ] 1 s 1 1 1 1 s co uS optool HD- 1100Z 芑LA era oi ιΗ Q ai ο Example 18 1 ] 1 1 s 1 I 1 1 1 1 s C〇ui optool HI>- 11002 s CS> 00 丨缄〇Example 17 1 1 o 1 1 1 1 l 1 1 g CO LT> optool 1 HD- nooz i U3 CO οό οό Lrt 〇Example 18 1 I C<l ] 1 1 1 1 1 o CQ Lri optool HD- liOOZ <=> Ψ < erf ••V4 〇Example 15 1 1 1 l CO CO l 1 1 s CQ optool HD- 1100Z g CO o oo 50.9 inch CO 〇Example 14 1 1 1 1 1 g •丨CO LA optool HD- I100Z C3 ua ΙΛ CO od 54 4 CQ 〇Example 13 1 cr$ 1 1 1 1 1 1 1 1 o CO tn optool HD-1100Z s 〇> o O) 65. Z ! Q t£3 〇Example 12 CQ ι 1 l 1 1 [ 1 1 ] 1 1 g eo optool HD- 1100Z C3 oo CO CO CO 〇CO tj- oo 4: A-10 A-ll U-12J A-13 £ CQ Used release agent adhesion F (mK) V Molybdenum CO 绂J Zhu Yu death β cone cone adhesion per unit area in^/m2) Evaluation of the mold step adhesion reducing agent hardening monomer 菹«Μη 20 324027 s 201245853 [Table 3] Table name product name company name substance Name 'Ί A-1 - Daikin Industrial 2-(Perfluorohexyl)ethanol^ [F(CF2)6CH2CH2〇H] A-2 - Daikin Industrial 2-(Perfluoro-2-butyl)ethanol> [F(CF2) 4CH£H2〇H] A-3 — Daikin Industrial Perfluoroethyl Sterol Alcohol' [f(cf〇2ch2〇h] A-4 H H Pure Pure Shovel A-5 MMPGAC Uaicei Chemical Industry Co., Ltd. Propylene Glycol Methyl Acetate Vinegar A-6 PolyFox PF3320 UM1NUVA Solutions Inc. Note 1 ~ B-1 CELOXIDE 2021P Daicel Chemical Industry Co., Ltd. 3, 4-Epoxycyclohexene Methyl-3',4'-Epoxycyclohexene Ester B-2 ARONE OXETANE 0XT-121 East Asia Synthetic Chemical Industry Co., Ltd. 1,4-bis[(3-ethyl-3-oxaheteromethoxymethyl)methyl]benzene n-1 B-3 CELOXIDE 8000 Daicel Chemical Industry Co., Ltd. Dicyclohexyl-3,3-diene dioxide Β·4 TEGDVE Maruzen Petrochemical Triethylene glycol II B. A-5 Aronix M-309 East Asia Synthetic Chemical Industry Co., Ltd. Trimethylolpropane triacrylate Β-6 Light acrylate 4E0-A Gongrongshe Chemical CH2=CH-C0-(CH2CH2〇)4-C0-CH=C Ha Cl PI2074 Rhodia 錤 salt C-2 Irgacure 651 BASF 2 , 2-dimethoxy-1,2-diphenylethane-1-one Dl AnthracureR UVS-1331 Kawasaki Chemically DBA dibutoxy oxime Note 1) 〇ch2cf3
324027 21 201245853 表4 表記 商品名 公司名 物質名稱 A-7 - ABCR GmbH 氟化三乙二醇單曱醚 [CF3〇(CF2CF2〇)2CFzCH2〇H] A-8 - ABCR GmbH 1H, 1H，2H, 2H-全氟十二烷-1-醇 [F(CF2).〇CH2CH2〇H] A-9 MMPG Daicel化學工業股份公司 1-甲氧基-2-丙醇 A-10 - ABCR GmbH 1H, 1H-全氟辛醇[F(CF2)7CH2〇H] A-11 - ABCR GmbH 2, 2, 3, 3,4,4, 5, 5,-八氣-1，6-二醇 [HOCH2(CF2)4CH2〇H] A-12 - 東京化成 卜辛醇[H(CF2)8〇H] A-13 - Aldrich 1,1,1-三氟-5, 5-二甲基-2,4-己二酮 [(CH3)£C0CH£0CF3] B-7 Epoxy Ester 70PA 共榮社化學 丙二醇二縮水甘油醚之丙烯酸加成物 C-3 Irgacure 907 BASF 2-甲基-1~(4-甲基硫基苯基)-2-嗎琳基 丙烷-1-酮 【圖式簡單說明】 第1圖（a)至（d)係表示之光硬化物之製造方法的一例 的截面圖。 第2圖係表示測定附著力之試驗裝置之概略構成的圖。 第3圖係概略表示附著力之測定方法的圖。 第4圖係表示附著力之測定結果之一例的圖。 【主要元件符號說明】 1 ' 21 基板 2 光硬化性組成物層 3 模具 4 光硬化物 11 平台 12 構件 13 支架 14 支撐器 15 光源 16 鏡面 22 壓印用光硬化性組成物 23 試驗物 324027 22324027 21 201245853 Table 4 Product name Company name Substance name A-7 - ABCR GmbH Fluorinated triethylene glycol monoterpene ether [CF3〇(CF2CF2〇)2CFzCH2〇H] A-8 - ABCR GmbH 1H, 1H, 2H, 2H-perfluorododecan-1-ol [F(CF2).〇CH2CH2〇H] A-9 MMPG Daicel Chemical Industry Co., Ltd. 1-methoxy-2-propanol A-10 - ABCR GmbH 1H, 1H -Perfluorooctyl alcohol [F(CF2)7CH2〇H] A-11 - ABCR GmbH 2, 2, 3, 3,4,4, 5, 5,-octane-1,6-diol [HOCH2(CF2 ) 4CH2〇H] A-12 - Tokyo Chemically converted to octanol [H(CF2)8〇H] A-13 - Aldrich 1,1,1-Trifluoro-5, 5-dimethyl-2,4-hexyl Diketone [(CH3)£C0CH£0CF3] B-7 Epoxy Ester 70PA Acne Chemicals Propylene Glycol Diglycidyl Ether Acrylate Additive C-3 Irgacure 907 BASF 2-Methyl-1~(4-Methyl Sulfur Phenylphenyl)-2-morphinylpropan-1-one [Simplified description of the drawings] Fig. 1 (a) to (d) are cross-sectional views showing an example of a method for producing a photocured material. Fig. 2 is a view showing a schematic configuration of a test apparatus for measuring adhesion. Fig. 3 is a view schematically showing a method of measuring adhesion. Fig. 4 is a view showing an example of measurement results of adhesion. [Description of main component symbols] 1 ' 21 Substrate 2 Photocurable composition layer 3 Mold 4 Photocured material 11 Platform 12 Member 13 Bracket 14 Supporter 15 Light source 16 Mirror 22 Photocurable composition for imprint 23 Test object 324027 22