201235210 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種作為陶瓷電容器之製程用薄膜而較佳 之離型薄膜，更具體而言，本發明係關於一種未必添加帶電 防止劑而捲出時之非帶電性優異，可防止薄膜之捲曲，且表 面平滑性優異的離型薄膜。 【先前技術】 近年來，離型薄膜多用作陶瓷電容器之製程用薄膜。用作 該製程用薄膜之離型薄膜必需防止其製造時因離型薄膜之 捲出時產生之靜電（以下稱作「捲出帶電」）而導致陶瓷漿料 之收縮。進而，就製造時之安全性、即防止由於捲出帶電導 致於溶劑中著火等觀點而言，亦必需防止捲出帶電。 又，隨著陶瓷電容器之小型化、高性能化之進展，對上述 用作製程用薄膜之離型薄膜要求進一步之平滑性。又，就被 黏附體之損傷或污染防止之觀點而言，對製程用薄膜要求穩 定之剝離性。 因此，揭示有如下發明：包含合成樹脂薄膜、以電子束硬 化性聚矽氧樹脂作為主成分之離型層、及以電子束硬化性樹 脂作為主成分之增黏層，使上述合成樹脂薄膜之表面轉印至 離型層表面，藉此獲得平滑之離型層（專利文獻1)。 然而，於該發明中，由於使合成樹脂薄膜之表面轉印至離 型層表面，故而無法獲得超出合成樹脂薄膜之表面狀態之平 101101040 3 201235210 滑性，作為對陶瓷電容器之製程用薄膜所要求之平滑性而言 不可謂充分。 另外，就抑制離型層對黏著物質之剝離強度之經時變化的 觀點而言，提供一種包含基材、由紫外線硬化型填充劑形成 之填充層及由陽離子聚合性紫外線硬化型聚矽氧剝離劑形 成之聚矽氧剝離層的薄膜（專利文獻2)。 然而，於該發明中，捲出帶電電壓較大，有時因由該紫外 線硬化填充劑之聚合反應引起之硬化收縮而於薄膜中產生 捲曲。 進而，提出如下離型薄膜，即，為藉由防止陶瓷電容器之 製程用薄膜之剝離帶電而防止由剝離帶電引起之接著強度 之提高、及由灰塵等之附著引起之污染，而形成由黏合劑樹 脂與帶電防止劑構成之層作為包含聚酯薄膜與硬化性聚矽 氧樹脂之離型層之中間層（專利文獻3)。 然而，於該發明中，有可能由於構成中間層之帶電防止劑 經時地滲出，而導致對被黏附體之污染或剝離強度之不穩 定，因此要求進一步之改善。 [先前技術文獻] [專利文獻] 專利文獻1:曰本專利特開平6-064106號公報 專利文獻2 :曰本專利特開2002-240203號公報 專利文獻3 :曰本專利特開2002-192661號公報 101101040 4 201235210 【發明内容】 (發明所欲解決之問題） 本發明之目的在於提供一種可抑制滲出，具有捲出時之優 異之非帶電性能，亦可防止薄膜之捲曲，並且表面平滑性優 異的離型薄膜。 (解決問題之手段） 本發明係一種離型薄膜，其係於包含熱塑性樹脂之基材層 上經由丙烯酸系樹脂層而設置離型層者，其特徵在於，上述 丙烯酸系樹脂層包含具有3個以上之（曱基）丙烯醯基，且丙 烯酸基當量為2〇〇以下之自由基聚合型之多官能丙烯酸酯。 又，於本發明之較佳態樣中，尤佳為上述自由基聚合型之 夕B月b (曱基）丙烯酸酯為二季戊四醇六丙稀酸酯及/或二季 戊四醇五丙埽酸酯。 又，於本發明之其他較佳態樣中，尤佳為上述自由基聚合 i之夕S此（甲基）丙烯酸酯為乙氧基化異氰尿酸三丙稀酸 酉曰又，尤佳為乙氧基化異氰尿酸三丙稀酸酯與乙氧基化異 氰尿酸二丙烯酸酯之混合物。 進而，於本發明之其他較佳態樣中，尤佳為上述基材層係 以選自由聚_、聚乙烯、及聚酯所組成之群組中之任意者 作為主成分。 又’於本發明之其他態樣中，尤佳為上述基材層朝至少一 方向延伸。 101101040 201235210 進而，於本發明之尤佳之態樣中，尤佳為上述離型層包含 加成反應型聚矽氧樹脂。 (發明效果） 根據本發明，可降低薄膜之捲出帶電電壓，故可有效地防 止由於捲出時之帶電電壓較高導致陶瓷漿料塗佈時之收縮 或導致灰塵等吸附於薄膜上。又，可提高薄膜表面之平滑 性，故可降低作為被黏附體之陶瓷電容器之破損，因此可大 大有助於提高良品率。進而，根據本發明，由於不會產生薄 膜之捲曲，故可防止因該捲曲而使陶瓷漿料於成形時流動， 產生厚度不均。 又，由於可降低薄膜之捲出帶電電壓，故不會產生由放電 痕跡引起之陶瓷漿料之塗佈性之惡化。因此，可均勻地塗佈 陶瓷漿料，故而可形成厚度精度較高之陶瓷漿料層。又，可 防止因上述放電痕跡產生之重剝離化。 進而，根據本發明，即便未必使用界面活性劑等滲出型之 添加劑，捲出時之非帶電性亦優異，可於捲出時賦予優異之 非帶電性能，因此亦防止界面活性劑等之滲出，可防止由界 面活性劑引起之被黏附體之污損。 又，根據本發明，即便未必使用金屬微粒子等導電性微粒 子，亦可獲得非帶電性優異之性能，故亦可避免由於調配該 等金屬微粒子時之分散不良導致帶電防止性能變得不均一 或表面粗度變得極大。 101101040 6 201235210 【實施方式】 [丙烯酸系樹脂層] 本發明之離型薄膜之丙烯酸系樹脂層中使用的（曱基）丙 烯酸酯類係丙烯酸基當量為200以下之自由基聚合型多官 能（曱基）丙烯酸酯。 此處，所謂（甲基）丙烯酸酯類，分別表示丙烯酸酯類與甲 基丙烯酸酯類兩者，所謂（曱基）丙烯酸酯，分別表示丙烯酸 酯之情況與曱基丙烯酸酯之情況兩者之情況。 自由基聚合型之多官能（曱基）丙烯酸酯係於分子中具有 至少1個自由基聚合型之反應基之化合物，可為該反應基為 羥基之含有自由基聚合型羥基之多官能（甲基）丙烯酸酯。 本發明之離型薄膜之丙烯酸系樹脂層中使用的（曱基）丙 烯酸酯類即自由基聚合型之多官能（曱基）丙烯酸酯之特徵 在於含有於分子中具有3個以上、特別是3〜10個、尤其是 3〜6個之（曱基）丙烯醯基之化合物。 於所使用之自由基聚合型之多官能（曱基）丙烯酸酯中，在 分子中具有3個以上（甲基）丙烯醯基之化合物之比例較佳為 50質量％以上、尤其是70質量％以上、進而為90質量％以 上。 於所使用之自由基聚合型之多官能（曱基）丙烯酸酯均係 (曱基）丙烯醯基未滿3個之情況下，在離型層中使用聚矽氧 樹脂時，有時聚矽氧之移行過大，導致被黏附體之污染。 101101040 7 201235210 此處，所謂（甲基）丙烯醯基，係指選自丙烯醯基、丙烯醯 氧基、甲基丙烯醯氧基中之至少1種以上。 作為本發明中使用之多官能（曱基）丙烯酸酯之具體例，可 較佳地舉出：三羥曱基丙烷三丙烯酸酯、三羥曱基乙烷三丙 烯酸酯、四羥曱基曱烷三丙烯酸酯、四羥甲基曱烷四丙烯酸 v 酯、五甘油三丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四 丙烯酸酯、甘油三丙烯酸酯、二季戊四醇三丙烯酸酯、二季 戊四醇四丙烯酸g旨、二季戊四醇五丙烯酸g旨、二季戊四醇六 丙烯酸酯、二季戊四醇五丙烯酸酯、異氰尿酸三（2-丙烯醯 氧基乙基）酯（別名：乙氧基化異氰尿酸三丙烯艘酯）、三羥曱 基丙烷三甲基丙烯酸酯、三羥曱基乙烷三曱基丙烯酸酯、四 羥曱基甲烷三曱基丙烯酸酯、四羥曱基甲烷四曱基丙烯酸 酯、五甘油三曱基丙烯酸酯、季戊四醇三曱基丙烯酸酯、季 戊四醇四曱基丙烯酸酯、甘油三曱基丙烯酸酯、二季戊四醇 三曱基丙烯酸酯、二季戊四醇四甲基丙烯酸酯、二季戊四醇 五曱基丙烯酸酯、二季戊四醇六曱基丙烯酸酯、三丙烯酸異 葙酯、多官能（曱基）丙烯酸胺基曱酸酯等，就防止捲出帶電 之觀點、以及於剝離層中使用聚矽氧樹脂、尤其是加成反應 型聚矽氧樹脂之情況時防止硬化抑制之觀點而言，尤佳為舉 出二季戊四醇六丙烯酸酯、二季戊四醇五丙烯酸酯。 該等化合物可分別單獨使用或混合使用。該等之中，尤佳 為乙氧基化異氰尿酸三丙烯酸酯，又，尤佳為乙氧基化異氰 101101040 8 201235210 尿酸三丙烯酸酯與乙氧基化異氰尿酸二丙烯酸酯之混合 物，其就促進丙烯酸系樹脂層之聚合反應之觀點而言更佳。 再者，亦可為上述單體之二聚物、三聚物等低聚物。 作為自由基聚合型之多官能（甲基）丙烯酸g|，較佳為選自 由一季戊四醇多官能（甲基）丙烯酸酯、烷氧基化異氰尿酸多 官能（曱基）丙烯酸酯、季戊四醇多官能（甲基）丙烯酸酯、三 季戊四醇多官能（甲基）丙烯酸酯所組成之群組。 其中，作為二季戊四醇多官能（曱基）丙烯酸酯，較佳為二 季;^醇h能丙烯g㈣，作祕氧基化異氰尿酸多官能 (甲基）丙稀酸醋’較佳為乙氧基化異氰尿酸多官能（曱基）丙 烯18曰’進而較佳為乙氧基化異氰尿酸彡官能㈣酸醋。 —作為季戊四醇多官能（甲基）丙烯酸酯，較佳為季戊四醇多 烯酉文1曰。其中，尤佳為二季戊四醇六丙烯酸酯、或二 季戊四醇五丙歸酸酯。 卞為較佳態樣之―’較佳為併用二季戊四醇六丙烯酸 醋及二季戊四醇五丙稀酸g旨。 '务明之其他較佳態樣中，較佳為上述自由基聚合 t (甲基）丙烯酸酯為乙氧基化異氰尿酸三丙烯酸 '為進而與乙氧基化異氰尿酸三丙烯酸酯併用乙氧基 化異氰尿酸二丙烯酸酯。 又， 酯必需 本發明中使用之自由基聚合型之多官能（曱基）丙烯酸 、f於所使用之（甲基）丙稀酸⑤旨類之合計丙烯酸 101101040 201235210 基當量成為200以下之方式使用。若該丙烯酸基當量超出 200，則多官能（曱基）丙烯酸酯類之聚合反應變得不充分。 並且，於使用聚矽氧樹脂、尤其是加成反應型聚矽氧樹脂 作為離型層之情況時，有時會產生抑制該加成反應型聚矽氧 樹脂之加成反應之問題。其結果，有時無法獲得離型層之表 面所需之表面粗度（SRa)，導致被黏附體之破損等，或者進 而無法獲得捲出帶電電壓之降低效果。 自由基聚合型之多官能（曱基）丙烯酸酯等（曱基）丙烯酸酯 類之丙烯酸基當量係以如下方式計算。 將[(曱基）丙烯酸酯類之分子量]+[(甲基）丙烯醯基數]設為 Mx，其中所謂（曱基）丙烯醯基數，係同時表示丙烯酸酯中所 含之丙烯醯基數之情況、與曱基丙烯酸酯中所含之曱基丙烯 醯基數之情況。 將[(曱基）丙烯酸5旨類之重量之合計量總和]設為A(重量 份）、 [(曱基）丙烯酸酯之重量]設為Ax(重量份）， 關於丙烯酸基當量， 對（曱基）丙烯酸酯類中之各（甲基）丙烯酸酯求出 ΜχχΑχ+Α之值，其值為丙稀酸基當量。再者，於使用2種 以上化合物之情況下，可求出各自之丙烯酸基當量，以其等 之總和之形式求出。 本發明中使用之自由基聚合型多官能（曱基）丙烯酸酯之 101101040 10 201235210 丙埽k基當量為200以下， 15〇以下。 車又佳為180以下，進而較佳為 反;=圍内’則可順利地進行_系樹脂層中之聚合 於離型層中使用聚錢樹脂之情況下,可改良 a之加成反應之順觀及離 [光聚合起始劑] 4成本發明之離型薄狀丙㈣㈣脂層時，就促進 (甲基)丙_®旨等（曱基)丙烯酸§_之聚合亦提高生產效率 之觀點而§，較佳為添加光聚合起始劑。作為本發明中可使 用之光聚合㈣劑，可舉出：二笨甲酮、減二苯甲綱、雙 -N，N-二甲基胺基二笨甲酮、雙_N，N_二乙基胺基二笨甲酉同、 曱氧基-4-一曱基胺基二苯甲鲷等二苯曱酮類；9_氧硫 ‘星、2,4-二乙基-9-氧硫心星、異丙基冬氧·山嗟、氣： ^硫口山嗤、異丙氧基氣斗氧硫一等9_氧硫树類；乙基 恩酿、苯并㈣、胺基蒽酿、氯葱轉蒽賴；笨乙綱、笨 乙酮苯偶I缩酮等苯乙安息香甲料安息香 2,4’6-三鹵甲基三畊類；卜經基環已基苯基_、2_(鄰氣笨 基m，5-二苯基t坐二聚物、2_(鄰氣笨基)_4,5-二（間甲氧基 苯基)咪嗤二聚物，鄰氟苯基K5_苯基輕二聚物、_ 曱氧基苯奸4,5·苯㈣仏聚物、2•(對f氧絲基)·4 $ 二苯基咪仏聚物、2·二(對甲氣基苯基)·5-苯㈣唾二聚 物、2-(2,4一甲氧基苯基)_4,5_二笨基料二聚物之⑷ 101101040 11 201235210 三芳基咪唑二聚物、苯偶醯二甲基输納。 I縮啊、2-节基-2-二甲基胺 基-1-(4-口末琳基本基）-丁烧-1-@同、2田甘 △甲基-1-[4_(曱硫基）苯 基]-2-σ未淋基-1·丙嗣、2-經基-2-甲其1 ?基-1-笨基-丙烷-1-酮、 1-[4-(2撼乙氧基)-苯基]_2，基_2_甲基同、菲 @昆、9’10•菲醌、曱基安息香、乙基安息香等安息香類、9- 苯基雙定基)歧等σγ奸生物、雙酿基 氧化膦、及該等之混合物等，上述可單獨使用，亦可混合使 用。再者，上述化合物中，就自由基生成效率良好之方面而 言’較佳為苯乙酮、苯乙酮苯偶酿縮_所代表之苯乙嗣類。 光聚合起始劑亦可與色素增感賴合使^作為色素增感 劑’例如可舉出_星L星、香豆素、香豆素_等。作 為光聚合起始劑與色素增感劑之組合，例如可舉出：βττβ 與p山ρ星之組合、ΒΤΤΒ與硫Pilj ρ星之組合、βττβ與香豆素之 組合、ΒΤΤΒ與香豆素酮之組合等。 作為光聚合起始劑之市售品，例如可舉出分別由Ciba201235210 VI. Description of the Invention: [Technical Field] The present invention relates to a release film which is a film for a process of a ceramic capacitor, and more particularly, the present invention relates to a method in which a charge prevention agent is not necessarily added A release film which is excellent in non-chargeability, prevents curling of the film, and has excellent surface smoothness. [Prior Art] In recent years, release films have been widely used as processes for ceramic capacitors. The release film used as the film for the process must be prevented from shrinking due to static electricity generated during the production of the release film (hereinafter referred to as "winding electrification"). Further, it is necessary to prevent the charging from being ejected from the viewpoint of safety at the time of manufacture, that is, prevention of ignition in a solvent due to winding out of charge. Further, with the progress of miniaturization and high performance of ceramic capacitors, further smoothness is required for the above-mentioned release film used as a film for process. Further, from the viewpoint of damage or contamination prevention of the adherend, a stable peeling property is required for the film for process. Therefore, there has been disclosed a synthetic resin film comprising a synthetic resin film, a release layer containing an electron beam curable polyoxymethylene resin as a main component, and a tackifying layer containing an electron beam curable resin as a main component. The surface is transferred to the surface of the release layer, whereby a smooth release layer is obtained (Patent Document 1). However, in the invention, since the surface of the synthetic resin film is transferred to the surface of the release layer, the smoothness of the surface of the surface of the synthetic resin film is not obtained as a film for the process of the ceramic capacitor. The smoothness is not sufficient. Further, from the viewpoint of suppressing the temporal change of the release strength of the release layer to the adhesive material, a filler layer comprising a base material, an ultraviolet curable filler, and a cationically polymerizable ultraviolet curable polyfluorene oxide are provided. A film of a polyoxynitride layer formed by a solvent (Patent Document 2). However, in the invention, the winding-up charging voltage is large, and curling occurs in the film due to hardening shrinkage caused by the polymerization reaction of the ultraviolet-curing filler. Further, a release film is proposed in which adhesion of a film for a process for preventing a ceramic capacitor is prevented from being peeled off, and adhesion strength due to peeling electrification and contamination due to adhesion of dust or the like are prevented. The layer composed of the resin and the charge preventing agent is an intermediate layer containing a release layer of a polyester film and a curable polyoxynoxy resin (Patent Document 3). However, in the invention, there is a possibility that the antistatic agent constituting the intermediate layer bleeds out over time, resulting in instability of the adherend or peeling strength, and thus further improvement is required. [Prior Art Document] [Patent Document] Patent Document 1: Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. 2002-240203. SUMMARY OF THE INVENTION (Problems to be Solved by the Invention) An object of the present invention is to provide an excellent non-charging property at the time of winding out, which can prevent bleed out, prevent curling of a film, and have excellent surface smoothness. Release film. (Means for Solving the Problem) The present invention is a release film which is provided on a base material layer containing a thermoplastic resin and which is provided with a release layer via an acrylic resin layer, wherein the acrylic resin layer contains three The above-mentioned (fluorenyl) acrylonitrile group, and a radical polymerization type polyfunctional acrylate having an acryl group equivalent of 2 Å or less. Further, in a preferred aspect of the present invention, it is particularly preferred that the above-mentioned radically polymerized type B-b (mercapto) acrylate is dipentaerythritol hexaacrylate and/or dipentaerythritol pentapropionate. Further, in another preferred aspect of the present invention, it is particularly preferred that the (meth) acrylate is ethoxylated isocyanuric acid tripropionate, and more preferably A mixture of ethoxylated isocyanuric acid triacrylate and ethoxylated isocyanuric acid diacrylate. Further, in another preferred aspect of the present invention, it is preferable that the substrate layer is selected from any one selected from the group consisting of poly-, polyethylene, and polyester as a main component. Further, in another aspect of the invention, it is preferred that the substrate layer extends in at least one direction. Further, in a particularly preferred aspect of the invention, it is preferred that the release layer comprises an addition reaction type polyoxynoxy resin. (Effect of the Invention) According to the present invention, it is possible to reduce the charging voltage of the film, and it is possible to effectively prevent the shrinkage of the ceramic slurry or the adsorption of dust or the like on the film due to the high charging voltage at the time of winding out. Further, since the smoothness of the surface of the film can be improved, the damage of the ceramic capacitor as the adherend can be reduced, so that the yield can be greatly improved. Further, according to the present invention, since the curl of the film is not generated, it is possible to prevent the ceramic slurry from flowing during molding due to the curl, resulting in thickness unevenness. Further, since the charging voltage of the film can be reduced, the coating property of the ceramic slurry caused by the discharge trace does not deteriorate. Therefore, the ceramic slurry can be uniformly applied, so that a ceramic slurry layer having a high thickness precision can be formed. Further, it is possible to prevent heavy peeling due to the above discharge marks. Further, according to the present invention, even if an additive such as a surfactant such as a surfactant is not necessarily used, the non-charging property at the time of unwinding is excellent, and excellent non-charging performance can be imparted at the time of unwinding, so that leakage of a surfactant or the like is also prevented. It can prevent the stain of the adherend caused by the surfactant. Moreover, according to the present invention, even if it is not necessary to use conductive fine particles such as metal fine particles, it is possible to obtain a performance excellent in non-chargeability, and it is also possible to prevent the charge prevention performance from becoming uneven or surface due to poor dispersion when the metal fine particles are blended. The thickness becomes enormous. 101101040 6 201235210 [Acrylic resin layer] The (mercapto) acrylate-based radical-polymerizable polyfunctional group having an acryl group equivalent of 200 or less used in the acrylic resin layer of the release film of the present invention. Base) acrylate. Here, the (meth) acrylates each represent both an acrylate and a methacrylate, and the so-called (mercapto) acrylate represents both the case of an acrylate and the case of a methacrylate. Happening. The radically polymerizable polyfunctional (fluorenyl) acrylate is a compound having at least one radical polymerization type reactive group in the molecule, and may be a polyfunctional group containing a radical polymerizable hydroxyl group in which the reactive group is a hydroxyl group. Base) acrylate. The (mercapto) acrylate which is used in the acrylic resin layer of the release film of the present invention, that is, a radical polymerization type polyfunctional (fluorenyl) acrylate, is characterized by having three or more, particularly 3, molecules contained in the molecule. ~10, especially 3 to 6, (fluorenyl) propylene fluorenyl compounds. In the radical polymerization type polyfunctional (fluorenyl) acrylate to be used, the proportion of the compound having three or more (meth) acryl fluorenyl groups in the molecule is preferably 50% by mass or more, particularly 70% by mass. The above is further 90% by mass or more. In the case where the radically polymerizable polyfunctional (fluorenyl) acrylate used is less than three (fluorenyl) acrylonitrile groups, when polyfluorene resin is used in the release layer, sometimes polyfluorene is used. The migration of oxygen is too large, resulting in contamination of the adherend. 101101040 7 201235210 Here, the (meth) acrylonitrile group means at least one selected from the group consisting of an acryloyl group, an acryloxy group, and a methacryloxy group. Specific examples of the polyfunctional (fluorenyl) acrylate used in the present invention include trishydroxypropyl propane triacrylate, trihydroxydecylethane triacrylate, and tetrahydroquinone decane. Triacrylate, tetramethylol decane tetraacrylate, pentaglycerol triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerin triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylic acid g, two Pentaerythritol pentaacrylic acid g, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, tris(2-propenyloxyethyl) isocyanurate (alias: ethoxylated isocyanuric acid tripropenyl ester), three Hydroxymercaptopropane trimethacrylate, trihydroxydecylethane tridecyl acrylate, tetrahydromethane methane tridecyl acrylate, tetrahydromethane methane tetradecyl acrylate, pentaglyceryl tridecyl acrylate Ester, pentaerythritol tridecyl acrylate, pentaerythritol tetradecyl acrylate, glyceryl tridecyl acrylate, dipentaerythritol tridecyl acrylate, dipentaerythritol tetramethyl Acrylate, dipentaerythritol pentadecyl acrylate, dipentaerythritol hexamethylene acrylate, isodecyl methacrylate, polyfunctional (fluorenyl) amide phthalate, etc., to prevent the charge from being unwound, and to be stripped From the viewpoint of preventing the hardening inhibition in the case of using a polyoxyxylene resin in the layer, in particular, an addition reaction type polyoxynoxy resin, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate are particularly preferable. These compounds may be used singly or in combination. Among these, ethoxylated isocyanuric acid triacrylate is preferred, and ethoxylated isocyanide 101101040 8 201235210 is a mixture of uric acid triacrylate and ethoxylated isocyanuric acid diacrylate. It is more preferable from the viewpoint of promoting the polymerization reaction of the acrylic resin layer. Further, it may be an oligomer such as a dimer or a trimer of the above monomer. The polyfunctional (meth)acrylic acid g| as a radical polymerization type is preferably selected from the group consisting of a pentaerythritol polyfunctional (meth) acrylate, an alkoxylated isocyanuric acid polyfunctional (fluorenyl) acrylate, and pentaerythritol. A group consisting of a functional (meth) acrylate and a tripentaerythritol polyfunctional (meth) acrylate. Wherein, as the dipentaerythritol polyfunctional (fluorenyl) acrylate, preferably two seasons; ^ alcohol h can be propylene g (four), as the oxylated isocyanuric acid polyfunctional (meth) acrylate vinegar 'preferably ethoxylated The polyisocyanuric acid poly(indenyl)propene 18 曰' is further preferably an ethoxylated isocyanuric acid hydrazine functional (tetra) vinegar. - As the pentaerythritol polyfunctional (meth) acrylate, pentaerythritol polyene oxime is preferred. Among them, dipentaerythritol hexaacrylate or dipentaerythritol pentapropylate is particularly preferred. Preferably, ― is preferably used in combination with dipentaerythritol hexaacrylate vinegar and dipentaerythritol penta acrylate acid. In other preferred embodiments of the invention, it is preferred that the above-mentioned radically polymerized t (meth) acrylate is ethoxylated isocyanuric acid triacrylate 'and further ethoxylated isocyanuric acid triacrylate and used Oxylated isocyanuric acid diacrylate. In addition, the ester is required to be used in the form of a radical polymerization type polyfunctional (fluorenyl) acrylic acid used in the present invention, and a total amount of acrylic acid 101101040 201235210 equivalent of 200% or less of the (meth)acrylic acid used. . If the acryl group equivalent exceeds 200, the polymerization reaction of the polyfunctional (fluorenyl) acrylate becomes insufficient. Further, when a polyoxyxylene resin, particularly an addition reaction type polyoxyxylene resin, is used as the release layer, there is a problem that the addition reaction of the addition reaction type polyoxyxylene resin is suppressed. As a result, the surface roughness (SRa) required for the surface of the release layer may not be obtained, resulting in breakage of the adherend or the like, or the effect of reducing the voltage of the coiled-out charging voltage may not be obtained. The acrylic group equivalent of a (meth) acrylate such as a radical polymerization type polyfunctional (fluorenyl) acrylate is calculated in the following manner. The molecular weight of [(fluorenyl) acrylate] + [(meth) propylene fluorenyl group] is defined as Mx, wherein the number of the (fluorenyl) acrylonitrile group is the same as the number of acrylonitrile groups contained in the acrylate. And the number of mercaptopropenyl groups contained in the mercapto acrylate. The total sum of the weights of [(indenyl)acrylic acid 5] is A (parts by weight), and the weight of [(fluorenyl)acrylate is Ax (parts by weight), and Each of the (meth) acrylates in the fluorenyl esters was determined to have a value of ΜχχΑχ + ,, which is an acrylic acid equivalent. Further, when two or more kinds of compounds are used, the respective acrylic acid equivalents can be obtained and obtained as the sum of the above. The radically polymerizable polyfunctional (fluorenyl) acrylate used in the present invention 101101040 10 201235210 The fluorene k group equivalent is 200 or less and 15 Å or less. It is preferable that the car is preferably 180 or less, and further preferably reversed; in the case of "inside", the polymerization in the resin layer can be smoothly carried out, and in the case where polylactic acid is used in the release layer, the addition reaction of a can be improved. When the photopolymerization initiator 4 is used to reduce the release of the thin C (iv) (iv) lipid layer of the invention, the polymerization of (meth) propyl _ _ 旨 曱 曱 亦 亦 亦 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ From the viewpoint of §, it is preferred to add a photopolymerization initiator. Examples of the photopolymerizable (four) agent which can be used in the present invention include dimercaptoketone, benzophenone, bis-N,N-dimethylaminodibenzophenone, and bis-N,N_ Diphenyl ketones such as ethylaminodiphenylcarbamate, decyloxy-4-mercaptoaminobenzophenone; 9-oxysulfide's star, 2,4-diethyl-9-oxygen Sulfur heart, isopropyloxan, hawthorn, gas: ^ sulfur sulphate, isopropoxy oxysulfide, sulfur, sulfur, etc. 9_ oxysulfide tree; ethyl enrichment, benzo (tetra), amine hydrazine Stuffed, scallions, simmering, stupid, acetophenone, benzophenone, ketal, benzophenone, benzoin, benzoin, benzoin, 2,4'6-trihalomethyl, three-till, basal phenyl, phenyl, phenyl (o-gas stupid m, 5-diphenyl t sit dimer, 2_(o-stupyl)_4,5-di(m-methoxyphenyl)imidate dimer, o-fluorophenyl K5_ Phenyl light dimer, _ methoxy benzoic acid 4,5 benzene (tetra) fluorene, 2 • (for f-oxygen) · 4 $ diphenyl mercaptopolymer, 2 · two (for gas (Phenyl)-5-benzene (tetra) saladimer, 2-(2,4-methoxyphenyl)-4,5-diphenyl base dimer (4) 101101040 11 201235210 Triaryl imidazole dimer, Benzene 醯 dimethyl transport. I缩, 2-Pheptyl-2-dimethylamino-1-(4-endoline basic)-butylate-1-@同,2 田甘△methyl-1-[4_(曱 曱Phenyl]-2-σ unleaded-l-propionium, 2-carbyl-2-methyl-1-yl-1-phenyl-propan-1-one, 1-[4-(2撼Ethoxy)-phenyl]_2, yl-2-ylmethyl, phenanthrene, quinone, 9'10, phenanthrenequinone, hydrazine benzoin, ethyl benzoin, etc., benzoin, 9-phenylbisdentyl) The above-mentioned organisms, double-branched phosphine oxides, and the like may be used singly or in combination. Further, among the above compounds, phenethyl hydrazine represented by acetophenone or acetophenone styrene is preferred in terms of good radical generation efficiency. The photopolymerization initiator may be used as a dye sensitizer in association with dye sensitization, for example, _ star L star, coumarin, coumarin, and the like. Examples of the combination of the photopolymerization initiator and the dye sensitizer include a combination of βττβ and p-mountain, a combination of ruthenium and sulphur Pilj ρ, a combination of βττβ and coumarin, and ruthenium and coumarinone. Combination, etc. Commercial products as a photopolymerization initiator are exemplified by Ciba, respectively.
Specialty Chemicals 出售之 IRGACURE 651、IRGACURE 184、IRGACURE 127、IRGACURE 500、IRGACURE 1000、 IRGACURE 2959、DAROCUR 1173、由 Lamberti 公司出售 之 ESACUREONE、ESACUREKIP150 等。該等起始劑、色 素增感劑較理想為避免形成聚矽氧樹脂層時之抑制硬化之 物質。例如於使用鉑觸媒之情況時，較理想為避免含有氮、 填、硫、錯、锡等之化合物。 101101040 12 201235210 [聚石夕氧樹脂] 本發明之離型薄膜之離型層中較佳為使用聚矽氧樹脂。所 使用之聚矽氧樹脂玎根據各種用途而選擇先前公知之各種 聚矽氧樹脂。例如就離塑薄膜對被黏附體之密接性、離型步 驟時之剝離強度之穩定性、及聚矽氧樹脂成分之非移行性之 觀點而言，較佳為藉由利用熱、紫外線、電子束等之硬化反 應而獲得之聚矽氧樹脂。其中，較佳態樣為使丨分子中具有 至少2個直接鍵結於矽原子上之烯基之有機聚矽氧烷、與ι 分子中具有至少2個直接鍵結於矽原子上之氣原子之有機 氫聚矽氧烷進行加成反應而獲得的聚矽氧樹脂，即，尤佳為 加成反應型聚矽氧樹脂。 作為具體之有機聚矽氧烷之例，可舉出：二甲基烯基矽浐 氧基封端二甲基聚矽氧烷、三甲基矽烷氧基封端甲基烯基矽 氧烷-二甲基矽氧烷共聚物、矽烷醇基封端甲基烯基矽氧烷_ j甲基石夕氧燒共聚物、二甲基烯基傾氧基封端甲基苯基二 乳燒-二甲基錢烧共㈣、二？料切糾基封端二苯 基石夕氧烷-二甲基矽氧烷共聚物等。 '”、八肌〜巧例:乳承吵乳炕之例，可舉出：二甲基 石夕貌氧基封m基切氧燒共聚物、三ί. ^氧基封切纽共㈣、二^ ^石夕3基封知―尹基梦氧貌·？基氫梦氧炫共聚物、」 燒氧基封端甲基氫聚石夕氧燒、環狀f基氳聚石夕氧力 101101040 201235210 等。 進而，形成離型層時，相對於上述有機聚石夕氣 _ =份’上述有機氫料纽成分通t4G2〜4L二， 加成反應而使該等與麵系觸媒等共存’藉此 了相對迅速地達成硬化反應。 [熱塑性樹脂] 料 =發明之離型薄臈之基材層的熱塑性樹脂並無特別 1種或摻合2種以上不關塑性樹脂使用。又， .、、、 較佳為聚乙稀樹脂、聚丙締樹脂、聚_脂、於 側鏈具有三級碳之α__系聚合物、尼龍樹脂、聚氮乙稀 樹脂、聚偏二氣乙稀樹脂、乙烯-乙烯醇樹脂，更佳為以聚 乙烯⑽、聚丙稀樹脂、聚轉脂之任意者作為主成分。 進而，就作為離型薄膜之素材之耐熱性等觀點而言，最佳 為聚酯樹脂。 藉由在上述聚_脂中例如以0 001〜5重量％之調配比 例含有有機或無機之微粒子作為滑劑，可使薄膜之平滑性變 得良好，提高加 工性。 一作為上述微粒子，可舉出碳酸辦、氧化轉、氧化欽、石墨、 高嶺土、二氧化矽、氧化鋁、氧化矽、氧化鋅、碳愛、碳化 石夕、氧化錫、丙烯酸系樹脂粒子、交聯聚苯乙烯樹脂粒子、 二聚氰胺樹脂粒子、交聯聚錢樹脂粒子等作為較佳例。 又，作為其他調配劑，可視需要添加帶電防止劑、抗氧化 101101040 14 201235210 劑、有機滑劑、觸媒、著色劑、顏料、螢光增白劑、塑化劑、 交聯劑、潤滑劑、紫外線吸收劑、其他樹脂等。 [聚酯樹脂] 於本發明中，較佳地用於基材層之聚酯系樹脂可為結晶性 聚s旨樹脂、非晶性聚酷樹脂之任一者。作為結晶性聚s旨樹 脂，就薄膜之加工性及機械強度之觀點而言，較佳為聚對苯 二曱酸乙二酯、聚對苯二曱酸丁二酯、聚萘二曱酸乙二酯、 聚萘二曱酸丁二酯，進而較佳為聚對苯二曱酸乙二酯、聚萘 二甲酸乙二酯。 [聚乙稀樹脂] 於本發明中，較佳地用於基材層之聚乙烯樹脂係以乙烯作 為主體之聚合物，指密度為895 kg/m3以上、較佳為900〜 970 kg/m3之範圍之超低密度聚乙烯、高壓法低密度聚乙 烯、線性低密度聚乙烯、中密度聚乙烯、高密度聚乙烯等乙 烯均聚物或乙烯與其他α-烯烴之嵌段共聚物及/或無規共聚 物，就鏡面輥之表面狀態對薄膜之轉印性等觀點而言，較佳 為高壓法低密度聚乙烯。再者，聚乙烯系樹脂可由上述樹脂 中任一種或二種以上構成。 又，作為形成上述乙烯之共聚物之乙烯與乙烯以外之α-烯烴之具體例，可舉出與碳數3〜20之α-烯烴之共聚物等。 此處，作為α-烯烴，可例示：丙烯、1-丁烯、1-戊烯、4-曱 基-1-戊烯、1-己烯、1-庚烯、1-辛烯、1-癸烯等。 101101040 15 201235210 [聚丙烯系樹脂] 於本發明中，較佳地用於基材層之聚丙烯系樹脂係指丙烯 均聚物、丙烯共聚物、及該等之混合物。作為丙烯均聚物， 通常係以聚丙烯之名稱製造、銷售之將丙烯作為主體之聚合 物’通常係在、度為 0.890〜0.930 g/cm3、MFR(Melt Flow Rate’熔融流動速率）(ASTMD 1238負重2160 g、溫度230。〇 為0.5〜60g/10min、較佳為〇 5〜1〇g/1〇min、進而較佳為 1〜5 g/10 min之丙烯之均聚物。又，作為丙烯共聚物，可 舉出丙烯與其他α-烯烴之無規共聚物、嵌段共聚物。丙烯 共聚物較佳為以1.5莫耳％以下之量含有由作為共聚單體之 α-烯烴衍生之單位。此處，作為α_烯烴，較佳為碳原子數2 〜20之丙烯以外之α-烯烴，具體可例示：乙烯、卜丁烯、 1-戊烯、1-己烯、1·庚烯、丨·辛烯、卜癸烯、丨_十二烯、κ 十六烯、4-甲基-1-戊烯等，尤佳為乙烯、丨_丁烯。 [離型薄膜] 本發明之離型薄膜係經由丙烯酸系樹脂層而設置離型層 及包含熱塑性樹脂之基材層者，且上述丙烯酸系樹脂層包含 具有3個以上（甲基）丙烯醯基，丙烯酸基當量為2〇〇以下之 自由基聚合型之多官能丙烯酸酯。本發明之離型薄膜較佳為 於包含熱塑性樹脂之基材層之表面設置包含自由基聚合型 之多官能丙烯酸酯之丙烯酸系樹脂層，進而於丙烯酸系樹月旨 層之表面形成離型層者。 101101040 16 201235210 於本發明之_薄财，藉由設置包含具有3個以上（甲 基）丙烯醯基’且丙埽酸基當量為2〇〇以下之自由基聚合型 之多官能丙烯酸酉旨的丙烯I系樹脂層，可提高表面^滑;生， 且可降低捲出帶電電壓。又，可呈現防止離型薄膜之捲曲或 重剝離化、及由喊漿料之塗佈性提高帶來生產效率之提高 等效果。又’對由成為構成本發明之離型_之基材層的執 塑性樹脂形成之薄膜（以下稱作「基材層薄膜」）使用朝至少 -方向延伸之薄膜，其就耐熱性之觀點而較佳僅上述基材 薄膜延伸時可僅進行單軸方向之延伸處理，較佳為朝雙袖方 向進行延伸處理。作為基材薄膜之—方向之延伸倍率，為 1.5〜12倍、較佳為2·〇〜8倍、更佳為2 5〜5倍。 構成基材層之熱塑性樹脂並無特別限定，較㈣以聚丙稀 樹脂、聚乙_脂、聚咖旨之任意者作為主成分，就对熱 性之觀點而言，進啸佳為以聚酯_作為主成分，最 聚對苯二甲酸乙二酯。 〜 又，於使用聚石夕氧樹脂作為離型層之情況時，就薄膜表面 之特性及加工性之觀點而言，其厚度較佳為〇〇1〜^ $㈣微 米），更佳為0.04〜0.10卿(微米）。即，藉由將離型声 度設為0.04㈣微米）以上，可於加工時提高㈣氧樹脂之 硬化性，藉由將厚度設為請_(微朴χτ，可最小限户 地抑制聚矽氧樹脂層表面之污染性。 又 101101040 就離型層之表面平滑性之觀點而言，丙婦酸系樹脂層之厚 17 201235210 ,車佳為0.1〜3.0帅(微米），進而較佳為〇 $〜2 〇 ,(微 5即’藉由將厚度設為0.1 μιη(微米）以上，可進—步提 高薄膜之表面平滑性。 就薄膜之加工性之觀點而言，基材層之厚度較佳1〜 1〇〇哗(微米），進而較佳為〜心m(微米），最佳為25〜 38 μΐΏ(微米）。即，藉由將厚度設為1 μη!(微米）以上，可有 效地防止於薄膜之加熱步驟中產生皴稽，藉由將厚度設為 100 μιη(微米）以下，可對薄膜賦予適度之柔軟性。 [離型薄膜之製造方法] 本發明之離型薄膜之較佳的製造方法如下所述。即’於成 為基材層之薄膜之單面塗佈具有3個以上（甲基)丙稀酿基， 且丙稀酸基當量為2GG以下之自由基聚合型之多官能丙稀 酸酯的有機溶劑溶液後，藉由活性能量線使其硬化，形成丙 烯酸系樹脂層。繼而，於該丙烯酸系樹脂層之表面上塗佈聚 石夕氧樹脂後，使其硬化，藉此成形。再者，於上述自由基聚 合型多官能丙烯酸酯之有機溶劑溶液之塗佈後且活性能量 線之照射前，視需要亦可進行乾燥。 上述自由基聚合型之多官能旨係以有機溶劑加以 稀釋而塗佈於成為基材層之薄膜之表面。稀釋之有機溶劑並 無特別限定，可較佳地使用苯、甲苯等芳香族烴、曱醇1乙 醇、異丙醇、2-乙氧基乙醇等醇類、甲基乙基綱、二丙基酉同、 二異丁基嗣等酮類、及該等之混合溶劑。 101101040 201235210 又，作為將上述自由基聚合型多官能丙烯酸酯之有機溶劑 溶液塗佈於聚酯薄膜之表面的（有時記載為塗敷）方法，例如 可使用氣刀塗佈機、直接凹版印刷塗佈機、凹版印刷套版塗 佈機（gravure offset coater)、電弧凹版印刷塗佈機（arc gravure coater)、凹版印刷反向塗佈機（gravure reverse coater) 及喷嘴方式等凹版印刷塗佈機、頂部加料反向塗佈機(top feed reverse coater)、底部加料反向塗佈機（bottom feed reverse coater)及喷嘴加料反向塗佈機(nozzie feed reverse coater)等反輥塗佈機、五輥塗佈機、唇口塗佈機、棒式塗佈 機、棒式反向塗佈機(bar reverse coater)、模塗佈機等各種公 知之塗敷機。 於使用光聚合起始劑之情況時，相對於上述自由基聚合型 之多官能丙烯酸酯1〇〇重量份，為1至15重量份左右。若 該使用量過少’則存在與不使用光聚合起始劑之情況相比硬 化速度未變大之傾向。 又，作為用以使上述自由基聚合型之多官能丙烯酸酯進行 自由基聚合之活性能量線，例如可舉出電子束、紫外線等， 可根據所使用之活性能量線或硬化性化合物之種類而適當 選擇。照射之活性能量線之強度及照射時間可根據所使用之 硬化性化合物之種類、含有硬化性化合物之塗膜之厚度等而 適當選擇。活性能量線亦可於惰性氣體環境中照射，作為該 惰性氣體，可例示氮氣、氬氣等。 101101040 19 201235210 形成丙烯酸系樹脂層後形成離型層。離型層之形成中可使 用先刖公知之材料，特別理想為使用聚矽氧樹脂。其中較佳 之聚石夕氧樹脂如上所述。其中，如上所述尤佳為加成反應 聚矽氧樹脂。 〜 使用聚石夕氧樹脂作為離型層之情況時可以先前公知之4 種方法形成。例如於塗佈具有溶劑型及乳膠型 化型聚石夕氧樹脂之情況時 〜的熱石』 分散液進入乾燥步驟，此時^之聚石夕氧樹脂之溶液& 範圍即可，較佳為6G〜^、溫度只要為5G〜120U 5〇°C，則熱硬化時間變長 之範圍。若乾燥溫度未沿 面，若超出120。。則存=4降低，故而欠佳。另-, 向。 #骐中產生皺褶，故欠佳之你 為提高聚石夕氧樹脂對丙歸 矽氧樹脂之塗佈前對丙歸 /脂層之密接性，亦可於聚 處理、火焰處理、臭氧處理等表⑽層之表面實施電暈放電 理劑之增黏塗佈處理。 面活化處理、或使用增黏處 離型層可藉由塗佈法而設置，、“ 言，可採用溶劑型、乳膠型、於该情況下時，就形態而 為均勾地形絲⑪氧料型之任意方法。其中， 型，就硬化型聚矽氧樹脂成分、，較理想為溶劑型或乳膠 或乳膠型亦較理想。之適用期之方面而言，溶劑型 對基材層薄膜塗佈聚 則_ 月曰之方法亦根據採取溶劑 201235210 型、乳膠型、無溶劑型之何種形態而不同，例如亦可採用輥 塗法、絲網印刷法、棒塗法、喷塗法等任意方法，其中輥塗 法作為高速且均勻地成形被膜之方法而較佳。 [實施例] (1)樣品之製備 將下述各樣品用之丙烯酸酯（聚合性化合物）與光聚合起 始劑分別製備成甲基乙基酮之溶液，使用邁耶棒（Meyer bar)No.4’將其塗敷於薄膜厚度為38 μιη(微米）、表面粗度（中 心面平均粗度SRa)為16奈米（nm)之PET(Polyethylene Terephthalate，聚對苯二曱酸乙二酯）薄膜（延伸倍率縱X橫 3倍x3倍）之單面上，於7〇。(：之烘箱中乾燥20秒，進而照 射紫外線(UV，Ultraviolet)(120 W><8 m/min)使其硬化，形成 塗敷膜作為丙烯酸系樹脂層。 [實施例1] 丙稀酸醋（聚合性化合物）： 乙氧基化異氰尿酸三丙烯酸酯化合物（*註1)(溶液中之濃 度10質量％) 光聚合起始劑： 二官能α-羥基酮（*註2)(溶液中之濃度1.5質量％) *註1 : NK Ester Α-9300(丙烯酸基當量141、丙烯醯基之 官能基數3)(新中村化學工業股份有限公司製） 主 2 . ESACURE ONE(Lamberti 公司製造） 101101040 21 201235210 [實施例2] 丙烯酸酯（聚合性化合物）： 乙氧基化異氰尿酸三丙烯酸酯化合物（*註1)(溶液中之濃 度9.7質量％)、 乙氧基化異氰尿酸二丙烯酸酯化合物（*註3)(溶液中之濃 度0.3質量％) 光聚合起始劑： 二官能（X-羥基酮註2)(溶液中之濃度1.5質量％) *註1 : NK Ester A-9300(丙烯酸基當量141、丙烯醯基之 官能基數3)(新中村化學工業股份有限公司製） *註3 : Aronix M-215(丙烯酸基當量184、丙烯醯基之官 能基數2)(東亞合成股份有限公司製） *註 2 : ESACURE ONE(Lamberti 公司製造） [實施例3] 丙稀酸酯（聚合性化合物）： 二季戊四醇六丙烯酸酯化合物（*註4)(溶液中之濃度10質 量％) 光聚合起始劑： 二官能α-羥基酮（*註2)(溶液中之濃度1.5質量％) *註4 : Aronix Μ-406(丙浠酸基當量96〜105、丙烯酿基 之官能基數5〜6)(東亞合成股份有限公司製） [實施例4] 101101040 22 201235210 丙烯酸酯（聚合性化合物）： 二季戊四醇六丙烯酸酯化合物（*註5)(溶液中之濃度10質 量％) 光聚合起始劑： 二官能α-羥基酮（*註2)(溶液中之濃度1.5質量°/〇) *註5 : Light Acrylate DPE-6A(丙烯酸基當量96、丙烯醮 基之官能基數6)(共榮化學股份有限公司製） [比較例1] 丙烯酸酯（聚合性化合物）： 甲酚酚醛清漆型環氧丙烯酸酯化合物（*註6)(溶液中之濃 度10質量％) 光聚合起始劑： 二官能α-羥基酮（*註2)(溶液中之濃度1.5質量％) 註6 : NK〇lig〇EA-7440(丙烯酸基當量370、丙烯醯基之 官能基數11)(新中村化學工業股份有限公司製） [比較例2] 丙烯酸酯（聚合性化合物）： 雙酚A型環氧丙烯酸酯系化合物（*註7)(溶液中之濃度1〇 質量％) 光聚合起始劑： 二官能a-羥基酮（*註2)(溶液中之濃度15質量％) *註7 : NK 〇ligo EA_1020(丙烯酸基當量祀、丙稀酸基 101101040 23 201235210 之B月b基數2)(新中村化學工業股份有限公司製） [比較例3] 丙烯酸酯（聚合性化合物）： 癸二醇二丙烯酸酯化合物（*註8)(溶液中之濃度1〇質量 %) 光聚合起始劑： 二官能α-羥基酮（*註2)(溶液中之濃度15質量％) *註8 : NKEsterA-DOD-N(丙烯酸基當量⑷、丙烯醯基 之官能基數2)(新中村化學工業股份有限公司製） 繼而’於f苯/曱基乙基酮(70/3〇容量比）之混合溶劑中溶 解聚石夕氧知丨脂（商品名：KS_36〇1(信越化學股份有限公司製)) 及銘觸媒(商品;g : PL_50T(信越化學股份有限公司製)），製 備塗敷液，使用邁耶棒Ν〇·4，於藉由實施例1〜3、及比較 例1〜3中記載之原材料而形成於ρΕΤ薄臈上的丙烯酸系樹 脂層之表面上塗敷上述塗敷液，於1〇〇ΐ之烘箱中乾燥2〇 秒，形成0·1 g/m2之塗敷臈作為包含聚矽氧樹脂之離型層 後，於溫度23〜60。(：下熟化，製成樣品。 [比較例4] 除未幵> 成丙稀酸系樹脂層以外，以與上述實施例及比較例 同樣之方法製成樣品。 (2)表面粗度（中心面平均粗度sRa ; nm) 於使薄膜表面輕微著色之程度下將上述各樣品以金(Au) 101101040 24 201235210 濺鍍於塗敷面上，使用Veeco公司製造之三維非接觸式表面 粗度測定器NT-1100，於以下條件下進行測定，求出表面粗 度(SRa)。 目鏡：0.5倍、物鏡：20倍、測定面積：590 μιηχ450 μιη (3) 剝離力[N/50 mm] 將上述各樣品以塗敷膜朝上之方式載置於水平台上，於該 塗敷膜側貼附黏著帶「No.31B」（日東電工股份有限公司 製），切割成200 mmx50 mm之大小，進而自該黏著帶之上 以成為20 g/cm2之方式載置負重，於70。(：下熟化20小時。 其後，利用拉伸試驗機，以300 mm/min之拉伸速度進行 180°剝離，求出用剝離穩定之區域的平均剝離負重除以黏著 帶寬度所得之值作為剝離力。 (4) 聚矽氧移行量[〇/〇] 測定附著而移行至上述(2)剝離力測試中所得之黏著帶 「No.MB」（曰東電工股份有限公司製）之表面側的矽元素 量，以相對於附著於比較例4之剝離力測試中所得之黏著帶 之表面的矽元素量之比例（％)評價聚矽氡移行量。 石夕元素之敎係使_著於㈣帶表面之^素的榮光 X射線強度(單位：kcps)之值。再者，測定中使用之榮光χ 射線裝置係使用Rigaku公司製造之榮光χ射線分析裂置 ZSXPrimusII，於以下條件下進行測定。 光譜：Κα 101101040 25 201235210 濾光器：OUT 隔膜：30 mm 衰減器：1/1 狹縫：COARSE 分光晶體：PET 檢測器：PC PHA ： 100-340Specialty Chemicals sold IRGACURE 651, IRGACURE 184, IRGACURE 127, IRGACURE 500, IRGACURE 1000, IRGACURE 2959, DAROCUR 1173, ESACUREONE, ESACUREKIP150 sold by Lamberti. These initiators and color sensitizers are preferably used to prevent hardening when forming a polyoxyn resin layer. For example, in the case of using a platinum catalyst, it is preferred to avoid compounds containing nitrogen, filler, sulfur, sulphur, tin, and the like. 101101040 12 201235210 [Polystone Oxygen Resin] It is preferred to use a polyoxyxylene resin in the release layer of the release film of the present invention. The polyoxyxylene resin used is selected from various previously known polyoxyxylene resins depending on various uses. For example, from the viewpoints of the adhesion of the plastic film to the adherend, the stability of the peel strength at the time of the release step, and the non-migration property of the polyoxyxene resin component, it is preferred to utilize heat, ultraviolet rays, and electrons. A polyoxyl resin obtained by a hardening reaction of a bundle or the like. Wherein, the preferred aspect is an organopolyoxane having at least 2 alkenyl groups directly bonded to a ruthenium atom in the ruthenium molecule, and at least 2 gas atoms directly bonded to the ruthenium atom in the ι molecule; The polyanthracene resin obtained by subjecting the organic hydrogen polyoxyalkylene to an addition reaction, that is, an addition reaction type polyoxyxylene resin is particularly preferable. Specific examples of the organic polyoxane include dimethylalkenyloxy terminated dimethylpolydecane and trimethyldecyloxy-terminated methylalkenoxane- Dimethyl methoxy olefin copolymer, stanol alcohol terminated methyl alkenyl oxane _ j methyl oxalate copolymer, dimethyl alkenyloxy terminated methyl phenyl diacetate - Dimethyl money burned a total of (four), two? The material is chopped to block the diphenyl oxalyl-dimethyloxane copolymer and the like. '", eight muscles ~ smart case: examples of milk-bearing nipples, can be exemplified by: dimethyl sulphate oxygen-based m-cut oxy-copolymer, three ί. ^ oxy-cutting New Zealand (four), two ^^石夕3基封知—Yin Jimeng Oxygen·?-Based hydrogen dream oxygen copolymer,” alkoxy-terminated methyl hydrogen poly-stone oxy-oxygen, cyclic f-based 氲 石 氧 oxygen 101101040 201235210 and so on. Further, when the release layer is formed, the organic hydrogen-containing material component is passed through t4G2 to 4L with respect to the organic polylithic gas, and the addition reaction is carried out to cause coexistence with the surface catalyst or the like. The hardening reaction is achieved relatively quickly. [Thermoplastic resin] The thermoplastic resin of the base layer of the release liner of the invention is not particularly used, and two or more kinds of non-plastic resins are used. Further, . , , , preferably a polyethylene resin, a polypropylene resin, a poly-lipid, an α__ polymer having a tertiary carbon in a side chain, a nylon resin, a polyurethane resin, and a polyethylene dioxide. The dilute resin or the ethylene-vinyl alcohol resin is more preferably a main component of any of polyethylene (10), polypropylene resin, and polydextrose. Further, from the viewpoint of heat resistance of the material of the release film, etc., it is preferably a polyester resin. By using, for example, 0 to 0.001% by weight of the above-mentioned poly-lipid, the organic or inorganic fine particles are used as a lubricant to improve the smoothness of the film and improve the workability. Examples of the fine particles include carbonic acid, oxidation, oxidation, graphite, kaolin, cerium oxide, aluminum oxide, cerium oxide, zinc oxide, carbon, carbon carbide, tin oxide, acrylic resin particles, and Preferred examples of the biphenyl resin particles, the melamine resin particles, and the crosslinked polyvalent resin particles are exemplified. Further, as other mixing agents, a charge inhibitor, an antioxidant 101101040 14 201235210 agent, an organic slip agent, a catalyst, a colorant, a pigment, a fluorescent whitening agent, a plasticizer, a crosslinking agent, a lubricant, and the like may be added as needed. UV absorbers, other resins, etc. [Polyester Resin] In the present invention, the polyester-based resin which is preferably used for the base material layer may be either a crystalline polys-based resin or an amorphous poly-resin. As the crystalline polystyrene resin, polyethylene terephthalate, polybutylene terephthalate, and polynaphthalene B are preferable from the viewpoint of processability and mechanical strength of the film. The diester and polybutylene naphthalate are further preferably polyethylene terephthalate or polyethylene naphthalate. [Polyethylene Resin] In the present invention, the polyethylene resin preferably used for the substrate layer is a polymer mainly composed of ethylene, and has a density of 895 kg/m 3 or more, preferably 900 to 970 kg/m 3 . Range of ultra-low density polyethylene, high pressure low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene and other ethylene homopolymers or block copolymers of ethylene and other alpha-olefins and / Or a random copolymer is preferably a high-pressure method low-density polyethylene from the viewpoint of the surface state of the mirror roll to the transfer property of the film. Further, the polyethylene-based resin may be composed of any one or two or more of the above resins. Further, specific examples of the α-olefin other than ethylene and ethylene which are copolymers of the above-mentioned ethylene include a copolymer of α-olefin having a carbon number of 3 to 20, and the like. Here, as the α-olefin, propylene, 1-butene, 1-pentene, 4-mercapto-1-pentene, 1-hexene, 1-heptene, 1-octene, 1- Terpene and the like. 101101040 15 201235210 [Polypropylene resin] In the present invention, the polypropylene resin preferably used for the substrate layer means a propylene homopolymer, a propylene copolymer, and a mixture thereof. As a propylene homopolymer, a polymer having propylene as a main component, which is usually manufactured and sold under the name of polypropylene, is usually used at a degree of 0.890 to 0.930 g/cm3 and MFR (Melt Flow Rate 'melt flow rate) (ASTMD) 1238 is a weight of 2160 g, a temperature of 230. The enthalpy is a homopolymer of propylene of 0.5 to 60 g/10 min, preferably 〜5 to 1 〇g/1 〇 min, and further preferably 1 to 5 g/10 min. The propylene copolymer may, for example, be a random copolymer or a block copolymer of propylene and another α-olefin. The propylene copolymer preferably contains an α-olefin derived from a comonomer in an amount of 1.5 mol% or less. Here, as the α-olefin, an α-olefin other than propylene having 2 to 20 carbon atoms is preferable, and specific examples thereof include ethylene, butene, 1-pentene, 1-hexene, and 1·. Heptene, anthracene octene, decene, decene-dodecene, κ hexadecene, 4-methyl-1-pentene, etc., particularly preferably ethylene, hydrazine-butene. [release film] The release film of the invention is provided with a release layer and a base layer containing a thermoplastic resin via an acrylic resin layer, and the acrylic resin layer includes A radical polymerization type polyfunctional acrylate having three or more (meth) acrylonitrile groups and an acryl group equivalent of 2 Å or less. The release film of the present invention is preferably a surface of a substrate layer containing a thermoplastic resin. An acrylic resin layer containing a radical polymerizable polyfunctional acrylate is provided, and a release layer is formed on the surface of the acrylic resin layer. 101101040 16 201235210 In the present invention, the package contains 3 A propylene-based I resin layer of a polyfunctional acrylate having a (meth)acryl fluorenyl group and having a propionate group equivalent of 2 Å or less can improve surface smoothness, growth, and reduction The charging voltage is taken up, and the effect of preventing the curling or heavy peeling of the release film and the improvement of the productivity by the improvement of the coating property of the shouting slurry can be exhibited. The film formed of the plastic resin of the base material layer (hereinafter referred to as "base material layer film") is a film extending in at least the direction, and it is preferably only when the base film is extended from the viewpoint of heat resistance. It is preferable to carry out the stretching treatment in the uniaxial direction, and it is preferable to carry out the stretching treatment in the direction of the double sleeve. The stretching ratio of the direction of the base film is 1.5 to 12 times, preferably 2 to 8 times, more preferably 2 to 5 times. The thermoplastic resin constituting the base material layer is not particularly limited, and (4) is a main component of any of polypropylene resin, polyethylene glycol, and polyglycol, and it is a view of heat. It is mainly composed of polyester _ as the main component and the most polyethylene terephthalate. 〜 In addition, in the case of using polysulfide as the release layer, from the viewpoint of the characteristics and processability of the surface of the film The thickness thereof is preferably 〇〇1 to ^$(four) micrometers), more preferably 0.04 to 0.10 milier (micrometers). In other words, by setting the release sound to 0.04 (four) micrometers or more, the hardening property of the (IV) oxygen resin can be improved during processing, and the thickness can be set to _ (micro χ , τ, which can suppress the aggregation of the oxime Contamination of the surface of the oxygen resin layer. 101101040 From the viewpoint of the surface smoothness of the release layer, the thickness of the propylene glycol resin layer is 17 201235210, and the car is 0.1 to 3.0 (micrometer), and further preferably 〇. $~2 〇, (Micro 5 is 'by setting the thickness to 0.1 μm (micron) or more, the surface smoothness of the film can be further improved. The thickness of the substrate layer is higher in terms of the processability of the film. Preferably, it is 1 to 1 〇〇哗 (micrometer), and further preferably ～m (micrometer), preferably 25 to 38 μΐΏ (micrometer), that is, by setting the thickness to 1 μη! (micrometer) or more. It is effective to prevent the occurrence of defects in the heating step of the film, and to impart a moderate flexibility to the film by setting the thickness to 100 μm or less. [Method for Producing Release Film] The release film of the present invention A preferred method of manufacture is as follows: 'single-side coating of a film that becomes a substrate layer An organic solvent solution of a polyfunctional acrylate having three or more (meth) propylene groups and a radical acid group equivalent of 2 GG or less, which is cured by an active energy ray to form a solution An acrylic resin layer is formed by applying a polysulfide resin to the surface of the acrylic resin layer, followed by curing, and further forming an organic solvent solution of the above-mentioned radical polymerizable multifunctional acrylate. After the application and before the irradiation of the active energy ray, it may be dried as needed. The above-mentioned radical polymerization type is functionally diluted with an organic solvent and applied to the surface of the film to be the substrate layer. The solvent is not particularly limited, and an aromatic hydrocarbon such as benzene or toluene, an alcohol such as decyl alcohol, ethanol, isopropanol or 2-ethoxyethanol, or a methyl ethyl group or a dipropyl group can be preferably used. a ketone such as diisobutyl hydrazine, and a mixed solvent thereof. 101101040 201235210 Further, an organic solvent solution of the above-mentioned radical polymerizable polyfunctional acrylate is applied to the surface of a polyester film (may be described as coating). ) The method may, for example, use an air knife coater, a direct gravure coater, a gravure offset coater, an arc gravure coater, a gravure reverse coater. (gravure reverse coater) and gravure coating machine such as nozzle method, top feed reverse coater, bottom feed reverse coater and nozzle feed reverse coater Various methods such as a reverse roll coater, a five-roll coater, a lip coater, a bar coater, a bar reverse coater, and a die coater (nozzie feed reverse coater) A known coating machine. In the case of using a photopolymerization initiator, it is about 1 to 15 parts by weight based on 1 part by weight of the above-mentioned radically polymerizable polyfunctional acrylate. If the amount used is too small, there is a tendency that the hardening rate does not become larger than when the photopolymerization initiator is not used. Further, examples of the active energy ray for radically polymerizing the above-mentioned radically polymerizable polyfunctional acrylate include an electron beam, an ultraviolet ray, etc., depending on the type of active energy ray or curable compound to be used. Appropriate choice. The intensity of the active energy ray to be irradiated and the irradiation time can be appropriately selected depending on the type of the curable compound to be used, the thickness of the coating film containing the curable compound, and the like. The active energy ray may be irradiated in an inert gas atmosphere, and examples of the inert gas include nitrogen gas, argon gas, and the like. 101101040 19 201235210 A release layer is formed after forming an acrylic resin layer. A well-known material can be used for the formation of the release layer, and it is particularly preferable to use a polyoxymethylene resin. Among them, the preferred polyoxyl resin is as described above. Among them, as described above, it is particularly preferable to carry out an addition reaction polyoxymethylene resin. ~ When polyphosphoric acid is used as the release layer, it can be formed by four methods known in the prior art. For example, in the case of coating a solvent-type and latex-type polyoxo resin, the hot stone dispersion may enter a drying step, and the solution of the polysulfide resin may be in a range, preferably. It is 6G~^, and if the temperature is 5G~120U 5〇°C, the thermal hardening time becomes longer. If the drying temperature is not in the surface, exceed 120. . Then save = 4 lower, so it is not good. Another -, to. #骐中############################################################################################### The surface of the layer (10) is subjected to a tackifying coating treatment of a corona discharge agent. The surface activation treatment or the use of the adhesion-promoting release layer can be set by a coating method, and “the solvent type or the latex type can be used. In this case, the morphology is the same as the topography. Any of the types, wherein the type is a hardening type polyoxymethylene resin component, preferably a solvent type or a latex type or a latex type, and the solvent type is applied to the substrate layer film in terms of pot life. The method of collecting _ 曰 曰 is also different depending on the form of the solvent 201235210 type, latex type, and solventless type. For example, any method such as roll coating, screen printing, bar coating, or spray coating may be used. The roll coating method is preferably a method of forming a film at a high speed and uniformly. [Examples] (1) Preparation of sample Each of the following samples was prepared by using an acrylate (polymerizable compound) and a photopolymerization initiator. A solution of methyl ethyl ketone was applied to a film thickness of 38 μm (micrometer) using a Meyer bar No. 4', and the surface roughness (central mean roughness SRa) was 16 nm. (nm) PET (Polyethylene Terephthalate, poly pair Ethylene diacetate film (3 times x 3 times magnification) 3 times on a single side, dried in an oven for 20 seconds, and then irradiated with ultraviolet light (UV, Ultraviolet) (120 W>< 8 m/min), it is hardened to form a coating film as an acrylic resin layer. [Example 1] Acrylic acid vinegar (polymerizable compound): Ethoxylated isocyanuric acid triacrylate compound (*Note 1 (concentration in solution: 10% by mass) Photopolymerization initiator: Difunctional α-hydroxyketone (*Note 2) (concentration in solution: 1.5% by mass) *Note 1: NK Ester Α-9300 (acrylic equivalent 141 (Functional base of propylene oxime) 3) (manufactured by Shin-Nakamura Chemical Co., Ltd.) Main 2. ESACURE ONE (manufactured by Lamberti Co., Ltd.) 101101040 21 201235210 [Example 2] Acrylate (polymerizable compound): ethoxylated Cyanuric acid triacrylate compound (*Note 1) (concentration in solution: 9.7% by mass), ethoxylated isocyanuric acid diacrylate compound (*Note 3) (concentration in solution: 0.3% by mass) Photopolymerization initiation Agent: Difunctional (X-hydroxyketone Note 2) (concentration in solution 1.5% by mass) *Note 1: NK Este r A-9300 (acrylic acid equivalent 141, propylene fluorenyl functional group number 3) (manufactured by Shin-Nakamura Chemical Co., Ltd.) *Note 3: Aronix M-215 (acrylic acid equivalent 184, propylene group functional group number 2) (manufactured by Toagosei Co., Ltd.) *Note 2: ESACURE ONE (manufactured by Lamberti Co., Ltd.) [Example 3] Acrylate (polymerizable compound): Dipentaerythritol hexaacrylate compound (*Note 4) (concentration in solution) 10% by mass) Photopolymerization initiator: Difunctional α-hydroxyketone (*Note 2) (concentration in solution: 1.5% by mass) *Note 4: Aronix Μ-406 (propionate equivalent: 96 to 105, acrylic Functional group number 5 to 6) (manufactured by Toagosei Co., Ltd.) [Example 4] 101101040 22 201235210 Acrylate (polymerizable compound): Dipentaerythritol hexaacrylate compound (*Note 5) (concentration in solution 10 mass) %) Photopolymerization initiator: Difunctional α-hydroxyketone (*Note 2) (concentration in solution 1.5 mass ° / 〇) *Note 5 : Light Acrylate DPE-6A (acrylic equivalent 96, propylene thiol functional Base 6) (manufactured by Kyoei Chemical Co., Ltd.) [Comparative Example 1] Acrylic acid (Polymerizable compound): Cresol novolac type epoxy acrylate compound (*Note 6) (concentration in solution: 10% by mass) Photopolymerization initiator: Difunctional α-hydroxyketone (*Note 2) (in solution The concentration is 1.5% by mass. Note 6: NK〇lig〇EA-7440 (acrylic acid equivalent 370, functional group number of propylene fluorenyl group 11) (manufactured by Shin-Nakamura Chemical Co., Ltd.) [Comparative Example 2] Acrylate (polymerization property) Compound): Bisphenol A type epoxy acrylate compound (*Note 7) (concentration in solution: 1% by mass) Photopolymerization initiator: Difunctional a-hydroxyketone (*Note 2) (concentration in solution) 15% by mass) *Note 7: NK 〇ligo EA_1020 (acrylic acid equivalent 祀, acrylic acid 101101040 23 201235210, B b base 2) (manufactured by Shin-Nakamura Chemical Co., Ltd.) [Comparative Example 3] Acrylate ( Polymerizable compound): decanediol diacrylate compound (*Note 8) (concentration in solution: 1% by mass) Photopolymerization initiator: Difunctional α-hydroxyketone (*Note 2) (concentration in solution 15 Mass %) *Note 8: NKEsterA-DOD-N (acrylic equivalent (4), number of functional groups of acrylonitrile 2) Chemical Industry Co., Ltd.) Then dissolved in a mixed solvent of f benzene / mercapto ethyl ketone (70 / 3 〇 capacity ratio), the product name: KS_36 〇 1 (Shin-Etsu Chemical Co., Ltd. Co., Ltd.) and Membrane (product: g: PL_50T (manufactured by Shin-Etsu Chemical Co., Ltd.)), preparing a coating liquid, using Meyer rod 4, by Examples 1 to 3, and Comparative Example The coating liquid was applied onto the surface of the acrylic resin layer formed on the ΕΤ ΕΤ thin layer by the raw materials described in 1 to 3, and dried in an oven for 2 sec to form a coating of 0·1 g/m 2 . After the application as a release layer containing a polyoxyl resin, the temperature is 23 to 60. (Complete aging to prepare a sample. [Comparative Example 4] A sample was prepared in the same manner as in the above Examples and Comparative Examples except that the acrylic resin layer was formed. (2) Surface roughness ( The average thickness of the center plane sRa; nm) The above samples were sputtered onto the coated surface with gold (Au) 101101040 24 201235210 to the extent that the surface of the film was slightly colored, using a three-dimensional non-contact surface roughness manufactured by Veeco. The measuring instrument NT-1100 was measured under the following conditions to obtain the surface roughness (SRa). Eyepiece: 0.5 times, objective lens: 20 times, measurement area: 590 μηη χ 450 μιη (3) Peeling force [N/50 mm] Each of the above-mentioned samples was placed on a water platform with the coating film facing upward, and an adhesive tape "No. 31B" (manufactured by Nitto Denko Corporation) was attached to the coating film side, and cut into a size of 200 mm x 50 mm. Further, a load was placed on the adhesive tape so as to be 20 g/cm 2 at 70°. (: 20 hours under aging. Thereafter, 180° was performed at a tensile speed of 300 mm/min using a tensile tester. Peeling, determining the average peeling weight of the area where the peeling is stable is divided by the adhesive tape The value obtained by the degree is used as the peeling force. (4) The amount of the polyether oxygen migration [〇/〇] is measured and adhered to the adhesive tape "No. MB" obtained in the above (2) peeling force test (Jidong Electric Co., Ltd. The amount of the lanthanum element on the surface side of the system was evaluated by the ratio (%) of the amount of the lanthanum element attached to the surface of the adhesive tape obtained in the peeling force test of Comparative Example 4. The glory X-ray intensity (unit: kcps) of the surface of the (4) surface is used. Further, the glory ray device used in the measurement is a glare ray analysis split ZSX Primus II manufactured by Rigaku Corporation. The measurement was carried out under the following conditions: Spectrum: Κα 101101040 25 201235210 Filter: OUT Diaphragm: 30 mm Attenuator: 1/1 Slit: COARSE Spectroscopic crystal: PET Detector: PC PHA: 100-340
施加電壓、電流：50 kV-60 mA (5) 捲出帶電電壓[kV] 將使上述各樣品於外徑 90 mm 之 ABS(Acrylonitrile-Butadiene-Styrene，丙稀腈-丁二稀-苯乙 烯）管上捲取成約50 m輥狀之製品輥靜置於23°C、50%Rh 之環境下後，以15 m/min之速度捲出。此時，於自製品幸昆 捲出離型薄膜之部分、與導輥之中間部位（離捲出部約30 cm 之部位），使用春日電機股份有限公司製之靜電電位測定器 KSD-0103，測定高度10 cm之位置之捲出帶電電壓。 (6) 薄膜之捲曲[mm] 自上述各製品輥，將寬度方向之大致中心附近切割成A4 尺寸作為樣品（樣品之長邊為薄膜之行進方向），將使塗敷膜 側朝上載置於水平台上時之薄膜之捲曲作為自台之浮起高 度進行測定。 [實施例及比較例] 101101040 26 201235210 使用藉由上述實施例1〜4、及比較例1〜4獲得之樣品’ 對上述(2)至（6)之各試驗項目進行測定。 將結果不於表1。 [表1] 單位 實施例 1 實施例 2 實施例 3 實施例 4 比較例 1 比較例 2 比較例 3 比較例 4 丙稀酿基 當量 - 141 141〜184 96 〜105 96 370 242 141 - 官能基數 個 3 3(—部分 包含2) 5〜6 6 11 2 2 - 表面粗度 (SRa) nm 4.1 3.4 2.8 3.2 43.5 4.5 - 16 剝離力 N/50 mm 0.5 0.68 0.51 0.52 0.53 0.75 _ 0.48 移行量 % 100 120 100 100 120 280 - 100 捲出帶電 電壓 kV -0.6 -0.6 0.2 0 -2.5 -2.7 - 0 薄膜之捲曲 mm 0 0 0.8 0.6 0.8 0 _ 0 於比較例3中，在上述樣品製備法中聚合性化合物未發生 硬化，無法獲得作為丙烯酸系樹脂層之塗敷膜。 根據實施例1〜4及比較例1〜3，可知：丙烯酸系樹脂層 之丙烯酸基當量為200以下，且（甲基）丙烯醯基之官能基數 為3以上之樣品的表面粗度(SRa)、剝離力較小’聚石夕氧之 移行量、捲出帶電電壓較少’此外薄膜之捲曲為無問題之水 準（1.0 mm以下）。可知’實施例1〜3之表面粗度(SRa)為 2.8〜4.1 nm，小於比較例之4.5〜43.5 nm，表面平滑性優 異。再者’表面粗度(SRa)及剝離力係電容器等被黏附體之 破損防止之尺度之一，存在表面粗度（SRa)及剝離力越大， 被黏附體越容易破損之傾向。 27 101101040 201235210 於實施例1中’與比較例相比，尤其是捲出帶電電壓及薄 膜之捲曲優異。可知’於實施例1中，由於薄膜之捲曲優異， 故可最有效地防止薄臈之硬化收縮。 於實施例2中，與比較例相比，尤其是捲出帶電電壓及薄 膜之捲曲優異。 於實施例3中，與比較例相比，尤其是表面粗度(SRa)較 小，被黏附體之破損防止效果優異。 於實施例4中’與比較例相比，尤其是捲出帶電電壓較 小，捲出非帶電性優異。 可知，於比較例1中，丙烯酸系樹脂層之丙烯酸基當量遠 遠超出200，為370，故結果表面粗度(SRa)為43.5 nm，捲 出帶電電壓亦遠遠大於實施例，為-2.5 kV。 可知，於比較例2中，丙烯酸系樹脂層之丙烯酸基當量超 出200,為242,（曱基）丙烯醯基之官能基數亦為2即未滿3, 故結果聚矽氧之移行量為280%，捲出帶電電壓亦遠遠大於 實施例，為-2.5 kV，剝離力亦較大，故重剝離化之降低效 果亦較小。 於比較例3中，丙烯酸基當量為200以下之141 ’（曱基) 丙稀醯基之官能基數為未滿3之2，故發生丙稀酸系樹脂之 硬化不良，無法形成丙烯酸系樹脂層。 於比較例4中，由於未設置丙烯酸系樹脂層，故相比實施 例，表面粗度(SRa)較大為16.0 nm。 101101040 28Applying voltage and current: 50 kV-60 mA (5) Unwinding the charged voltage [kV] will make each sample above ABS (Acrylonitrile-Butadiene-Styrene, acrylonitrile-butadiene-styrene) with an outer diameter of 90 mm. The product roll wound into a roll of about 50 m on the tube was placed in an environment of 23 ° C and 50% Rh, and then rolled out at a speed of 15 m/min. At this time, the electrostatic potential meter KSD-0103 manufactured by Kasuga Electric Co., Ltd. was used in the portion where the release film was taken out from the product and the intermediate portion of the guide roller (about 30 cm from the unwinding portion). The coiled-out charging voltage at a position of 10 cm in height was measured. (6) Curl of film [mm] From the above-mentioned respective product rolls, the vicinity of the center of the width direction is cut into an A4 size as a sample (the long side of the sample is the traveling direction of the film), and the coated film side is placed on the loading side. The curl of the film on the water platform was measured as the floating height of the self-stage. [Examples and Comparative Examples] 101101040 26 201235210 Samples obtained by the above Examples 1 to 4 and Comparative Examples 1 to 4 were used. The respective test items of the above (2) to (6) were measured. The results will not be as shown in Table 1. [Table 1] Unit Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Propylene base equivalent - 141 141~184 96 〜 105 96 370 242 141 - Several functional groups 3 3 (-part contains 2) 5~6 6 11 2 2 - surface roughness (SRa) nm 4.1 3.4 2.8 3.2 43.5 4.5 - 16 peeling force N/50 mm 0.5 0.68 0.51 0.52 0.53 0.75 _ 0.48 movement amount % 100 120 100 100 120 280 - 100 Unwinding electrification voltage kV -0.6 -0.6 0.2 0 -2.5 -2.7 - 0 Film curl mm 0 0 0.8 0.6 0.8 0 _ 0 In Comparative Example 3, the polymerizable compound in the above sample preparation method Hardening did not occur, and a coating film as an acrylic resin layer could not be obtained. According to Examples 1 to 4 and Comparative Examples 1 to 3, the surface roughness (SRa) of the sample having an acrylic group equivalent of 200 or less and the number of functional groups of the (meth)acrylinyl group of 3 or more was found. The peeling force is smaller 'the amount of migration of the poly-stone oxygen is less, and the coiling voltage is less.' In addition, the curl of the film is no problem (1.0 mm or less). It is understood that the surface roughness (SRa) of Examples 1 to 3 is 2.8 to 4.1 nm, which is smaller than 4.5 to 43.5 nm of the comparative example, and the surface smoothness is excellent. Further, one of the dimensions of the surface roughness (SRa) and the peeling force-based capacitor to prevent breakage of the adherend, the larger the surface roughness (SRa) and the peeling force, the more likely the adherend is to be damaged. 27 101101040 201235210 In the first embodiment, the crimping voltage and the curl of the film are particularly excellent as compared with the comparative example. It can be seen that in Example 1, since the curl of the film is excellent, the shrinkage and shrinkage of the sheet can be most effectively prevented. In Example 2, in particular, the crimping voltage and the curl of the film were excellent as compared with the comparative example. In Example 3, in comparison with the comparative example, the surface roughness (SRa) was small, and the damage prevention effect by the adherend was excellent. In the fourth embodiment, in comparison with the comparative example, in particular, the unwinding electrification voltage is small, and the unwinding non-charging property is excellent. It can be seen that in Comparative Example 1, the acrylic group equivalent of the acrylic resin layer far exceeds 200, which is 370, so that the surface roughness (SRa) is 43.5 nm, and the coiled-out charging voltage is also much larger than the embodiment, which is -2.5. kV. In Comparative Example 2, the acrylic group equivalent of the acrylic resin layer exceeded 200, which was 242, and the number of functional groups of the (fluorenyl) acrylonitrile group was also 2, that is, less than 3, so that the migration amount of polyfluorene was 280. %, the coiled-out charging voltage is also much larger than the embodiment, which is -2.5 kV, and the peeling force is also large, so the effect of reducing the peeling is small. In Comparative Example 3, the number of functional groups of the 141 '(fluorenyl) acrylonitrile group having an acrylic group equivalent of 200 or less was less than 2, so that the curing of the acrylic resin was poor, and the acrylic resin layer could not be formed. . In Comparative Example 4, since the acrylic resin layer was not provided, the surface roughness (SRa) was as large as 16.0 nm as compared with the examples. 101101040 28