200934660 五 本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無200934660 5 If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none
-4- 200934660 六、發明說明： 【發明所屬之技術領域】 本發明係關於脫模薄膜，更詳細而言，係關於可充分 地符合作爲陶瓷片製造時所使用的脫模薄膜所要求的性能 之脫模薄膜。 【先前技術】 i 以聚酯薄膜作爲基材之脫模薄膜，作爲製造層合陶瓷 ❹ 電容器'陶瓷基板等之各種陶瓷電子零件製造時所使用的 陶瓷片（綠帶（green sheet))等時的承載薄膜（carrier film )使用。 製造層合陶瓷電容器時所使用的陶瓷片，例如於承載 薄膜之上，藉由逆輥法等塗佈使陶瓷粉體與黏合劑等分散 於溶劑之陶瓷淤漿，加熱乾燥去除溶劑後形成陶瓷層後， 藉由蒸鏟或印刷等於該陶瓷層上形成成爲内部電極之金屬 φ 膜’製成金屬膜/陶瓷層/承載薄膜複合體，藉由從該相關 的複合體剝離去除承載薄膜而製造。 層合陶瓷電容器’係將如上述作法所製造的金屬膜/ 陶瓷層複合體，以所望的尺寸進行層合，熱壓後，藉由剪 斷成矩形狀而得到片狀的層合體，將此片狀的層合體進行 燒成，藉由於燒成體的所定的表面上形成外部電極而得 到。 但是，近年來，於層合陶瓷電容器等之電容器的領 域，隨著小型化•大容量化而要求電路零件的高密度化， -5- 200934660 故，必須令所使用的陶瓷片的厚度亦更薄膜化、使内部電 極更多層化。 惟，使陶瓷片的厚度變薄、增加層合片數，則連陶瓷 片之少許的厚度斑，都會成爲引起内部電極的位置偏移的 原因。 因此，提議減少陶瓷片製造時之承載薄膜的熱變形， 降低所製造的陶瓷片的厚度斑（參考專利文獻η 。專利 文獻1中記載著若於120°C之1.47MPa應力下的尺寸變化 率的絶對値在長邊方向及寬度方向皆爲0.3 %以下之脫模 薄膜，因爲加熱處理時的熱變形變得非常小，可抑制所得 到的陶瓷片的厚度斑。 惟，陶瓷片係通常l〇〇°C附近的溫度下，在寬度方向 未被把持下使其乾燥，因此，陶瓷片製造時所使用的承載 薄膜，於陶瓷乾燥時，在往寬度方向幾乎未施加下張力的 狀態下收縮，故，如專利文獻1所記載，僅使用在施加張 力的狀態之長邊方向與寬度方向的各自熱收縮率低的脫模 薄膜，一直到陶瓷的乾燥爲止的所有的步驟中之承載薄膜 的收縮斑無法消除，仍然會有所製造的陶瓷片中發生厚度 斑、層合時引起内部電極的位置偏移之問題殘留。 此外，陶瓷片的厚度薄時，承載薄膜的表面粗度高， 則發生因爲針孔發生所造成的不良、或陶瓷片剝離時陶瓷 片的斷裂等，引起生產性的降低。亦即，陶瓷片薄時，就 連先前技術未造成問題之程度的承載薄膜表面的擦傷或異 物等之微細的表面缺點，亦明顯地成爲所得到的陶瓷片的 -6- 200934660 針孔缺點等之原因。 故，近來隨著電容器領域的小型化•大容量化，對於 用於製造陶瓷片的承載薄膜，要求更高精度的尺寸安定 性，及，更高程度的表面凹凸的平滑化。 另一方面，使承載薄膜的表面平滑，則會有剝離帶電 變高的傾向，例如爲了生產性提昇而提高陶瓷淤漿的塗佈 速度，則於捲出承載薄膜的步驟中會有火花易發生，因此 A 而有火災易發生的之問題。此外，從承載薄膜剝離陶瓷片 時造成陶瓷片帶電，在接下來的步驟中層合該陶瓷片時， 因爲該帶電而發生内部電極的位置偏移。因此，對於作爲 具有更平滑的表面之承載薄膜，強烈要求抑制剝離帶電。 特別是厚度薄的（Ιμηι以下）陶瓷片的製造中，不僅 是如上述的高精度的尺寸安定性、及高程度的平滑化（所 謂表面粗度），更高度地控制薄膜的平坦性（亦稱爲平面 度）這點很重要。亦即，承載薄膜的平坦性差時，塗佈於 φ 其上的陶瓷淤漿的塗佈厚度斑變不良，因而陶瓷片的厚度 斑變不良，於層合陶瓷電容器中則變成容量不均勻者。 惟，如上述的承載薄膜，一般而言以捲取爲滾筒狀的 形態使用，但因爲表面具有脫模層，易發生易滑動、滾筒 於捲取中或運搬中等易捲取偏移等的問題。因此，先前技 術將如上述的承載薄膜捲取於滾筒狀時，爲了不發生捲取 偏離，採取使滾筒硬度提高的條件爲一般作法。惟，滾筒 硬度太高，則承載薄膜易追隨滾筒形狀，因爲微細的滾筒 形狀之不佳狀況而造成承載薄膜伸長，成爲平坦性劣化 200934660 者。 此外，特別是於厚度薄的（ΐμ™以下）陶瓷片的製造 中，更高度地控制薄膜的厚度斑這點很重要。亦即，承載 薄膜的厚度斑差時，塗佈於其上的陶瓷淤漿的塗佈厚度斑 變不良，因而陶瓷片的厚度斑變不良，於層合陶瓷電容器 中則變成容量不均勻者。 (專利文獻1)特開200 0-343663號公報 【發明內容】 本發明的目的係提供鑑於如此先前技術而完成者，於 製造陶瓷片時的加熱張力下具有適當的尺寸變化率、乾燥 陶瓷淤漿時的熱收縮平衡亦優異、可充分地符合作爲陶瓷 片製造時所使用的脫模薄膜所要求的性能之脫模薄膜。 本發明者係爲了解決上述課題進行精心檢討，其結 果，發現於特定的載重下具有特定的伸長率、於無載重下 具有特定的熱伸長率之脫模薄膜，可符合對於製造陶瓷片 時所使用的脫模薄膜所要求的性能，而達到完成本發明。 亦即，本發明係聚酯薄膜的至少一方的面上具有脫模 層之脫模薄膜，係 在脫模薄膜的長邊方向施加〇.2MPa以上4.0MPa以下 的張力時，於l〇〇°C之長邊方向的伸長率（SMD)符合下述 式（1 )， 在垂直於脫模薄膜的長邊方向的方向施加O.OIMPa的 張力時，於 1〇〇 °C之垂直於長邊方向的方向的伸長率 -8- 200934660 (STD)符合下述式（2)， 脫模薄膜在無載重下，於10(TC之長邊方向的熱伸長 率（HSMD)，符合下述式（3)， 脫模薄膜在無載重下，於100 °C之垂直於長邊方向的 方向的熱伸長率（HSTD)，符合下述式（4)， 長邊方向的熱伸長率（HSMD)與垂直於前述長邊方向 的方向的熱伸長率（HSTD )，符合下述式（5)之脫模薄 0.0961X-0.45 ^SMd^〇.〇961X-0.25 (1) (式（1)中，X係施加於薄膜單位面積的張力（MPa)， X表示0.2MPa以上4.0MPa以下之値。） -0.6 ^ STD ^-0.2 (2) -0.4^HSMd^-〇.1 (3) -0.6^HSTd^-〇.2 (4) HSmd>HSTd (5) 而且本發明的脫模薄膜，用脫模層表面的接觸式三維 表面粗度計所測量的最大高度（Rmax) ’爲100nm以上 600nm以下的範圍較佳。此外脫模層表面及不具有脫模層 之側的表面之用接觸式三維表面粗度計所測量的最大高度 (Rmax )，各自爲100nm以上600nm以下較佳。此外脫 200934660 模層係相對於脫模層的重量含有〇 · 5質量％以上1〇質量％ 以下的界面活性劑較佳。此外縱方向的厚度斑爲3.0%以 下，橫方向的厚度斑爲3.0%以下較佳。此外脫模層，藉 由於在一方向經延伸的聚酯薄膜上塗佈脫模層形成組成物 而形成較佳。 本發明的脫模薄膜，爲陶瓷片製造用較佳，特別佳爲 陶瓷電容器製造用。 本發明係將上述脫模薄膜捲成滾筒狀之薄膜滾筒，包 含滾筒表層的維氏硬度（Ην)爲0以上45 0以下的薄膜滾 筒。本發明係包括使用具備上述式（1)〜（5)的特性之 薄膜作爲陶瓷片用的脫模薄膜之方法。 [實施發明之最佳形態] 本發明中，會有將薄膜製膜的機械軸方向稱爲長邊方 向或縱方向的情況；此外，會有將垂直於長邊方向的方向 稱爲寬度方向或橫方向的情況。 <脫模薄膜> 本發明的脫模薄膜，係於聚酯薄膜的至少一側的面具 有脫模層之脫模薄膜，於特定的載重下具有特定的伸長 率、於無載重下具有特定的熱伸長率者。以下，說明關於 本發明的脫模薄膜的物性及構成。 [長邊方向的伸長率（SMD)] -10- 200934660 本發明的脫模薄膜，係於脫模薄膜的長邊方向施加 0.2MPa以上4.0MPa以下的張力時，於100°C之長邊方向 的伸長率（SMD)爲符合下述式（1)。陶瓷層/脫模薄膜 複合體，通常在loot附近的溫度下施加張力的狀態下搬 運。故，藉由選擇loot作爲溫度條件，可達到更符合實 際步驟的狀況判斷。 ❹ 0.0961X-0.45 ^Smd^〇.〇961X-0.25 (1) (式（1)中，X係施加於薄膜單位面積的張力（MPa )， X表示0.2MPa以上4.0MPa以下之値） 長邊方向的伸長率（SMD)小於上述式（1)的左邊之 値時，相對於陶瓷層/脫模薄膜複合體的搬運張力，薄膜 的長邊方向的收縮應力變大，其結果，係長邊方向上不均 勻地收縮，而引起陶瓷片的厚度斑。另一方面，長邊方向 φ 的伸長率（SMD )大於上述式（1)的右邊之値時，相對於 陶瓷層/脫模薄膜複合體的搬運張力，因爲薄膜的長邊方 向的收縮應力小，薄膜的平坦性變差，而引起陶瓷片的厚 度斑。長邊方向的伸長率（SMD)若符合上述式（1)的範 圍，相對於陶瓷層/脫模薄膜複合體的搬運張力，長邊方 向的收縮應力具有適當的均衡，可抑制所得到的陶瓷片的 長邊方向的厚度斑。由如此的觀點而言，本發明的脫模薄 膜，於脫模薄膜的長邊方向施加0.3 MPa以上2.5MPa以下 的張力時’於100 °C之長邊方向的伸長率（SMD)爲符合上 -11 - 200934660 述式（1 )的形態更佳。 再者，長邊方向的伸長率（SMD)及後述之寬度方向 的伸長率（STD )係由下述式所計算得到。式中，Mo表示 昇溫開始前的薄膜的長邊方向或寬度方向的長度，Μ表示 昇溫開始後到達1 00°c時的薄膜的同方向的長度。亦即， 伸長率（SMD )及伸長率（STD )，負時表示薄膜收縮，正 時表示薄膜伸長。 伸長率（SMD、Std) = (AM/M〇)x100(%) ΔΜ = Μ-Μ〇 [垂直於長邊方向的方向（寬度方向）的伸長率（sTD)] 本發明的脫模薄膜，於脫模薄膜的寬度方向施加 O.OIMPa的張力時，於lOOt：之寬度方向的伸長率（STD) 符合下述式（2 )。故，藉由選擇1 00°C作爲溫度條件，與 上述同樣，可達到更符合實際步驟的狀況判斷。再者，伸 長率（STD)係藉由上述式從熱處理前後的薄膜的寬度方 向的長度計算得到。 -0.6^Std^-0.2 (2 ) 寬度方向的伸長率（STD )小於-0.6%時，於陶瓷層/脫 模薄膜複合體的搬運步驟中，薄膜的寬度方向的收縮大， 而引起陶瓷片的厚度斑。另一方面，寬度方向的伸長率 -12- 200934660 (STD)大於-ο .2%時，伸長率（STD)大於0 (薄膜伸長） 時，陶瓷層/脫模薄膜複合體因爲於搬運中薄膜的寬度方 向的伸長，而使薄膜的平坦性失去’而引起陶瓷片的厚度 斑。此外，陶瓷層的收縮與脫模薄膜的伸長的平衡差，會 產生陶瓷層部分剝離而浮起等之問題。伸長率（STD )超 過-0.2%而0%以下時，陶瓷層的收縮與脫模薄膜的收縮的 平衡差，而產生陶瓷層從脫模薄膜產生部分剝離而浮起等 _ 之問題。 [長邊方向的熱伸長率（hsmd)及垂直於長邊方向的方向 (寬度方向）的熱伸長率（HStd)] 本發明的脫模薄膜，無載重下之於100 °C之長邊方向 的熱伸長率（HSMD )符合下述式（3)，同時，無載重下 之於100 °C之寬度方向的熱伸長率（HSTD)符合下述式 (4)，且，長邊方向的熱伸長率（HSMD)與寬度方向的 φ 熱伸長率（HSTD)符合下述式（5)。 -0.4^HSMd^-〇.1 (3) -0.6 ^ HStd ^-0.2 (4) HSmd>HStd (5) 薄膜的長邊方向的熱伸長率（hsmd)與寬度方向的熱 伸長率（HSTD )各自爲上述的範圍，且，藉由使長邊方向 的熱伸長率（hsmd )大於寬度方向的熱伸長率 -13- 200934660 (hstd )，於陶瓷淤漿塗佈後加熱乾燥去除陶瓷層所含有 的溶劑時，取得脫模薄膜的長邊方向的收縮與寬度方向的 收縮之平衡，其結果，可降低所得到的乾燥陶瓷層的厚度 斑。 再者，長邊方向的熱伸長率（HSmd )、及寬度方向的 熱伸長率（HStd)，係藉由下述式計算得到。式中、L0表 示熱處理前的薄膜的長邊方向或寬度方向的長度，L表示 熱處理後的薄膜的同方向的長度。亦即，熱伸長率 (HSmd )及熱伸長率（HSTD )，負時表示薄膜收縮，正 時表示薄膜伸長。 熱伸長率（HSmd、HStd) = (AL/L〇)x100 (%) Δ L = L' L 〇 [最大高度（Rmax )] 而且本發明的脫模薄膜，用脫模層表面的接觸式三維 表面粗度計所測量的最大高度（Rmax)，爲lOOnm以上 60 0nm以下較佳。最大高度（Rmax )，更佳爲200nm以 上550nm以下，特別佳爲300nm以上500nm以下。 最大高度（Rmax)係指依照JIS規格（B0601-2001 : 表面粗度·定義及表示、B0651-2001 :觸針表面粗度測量 器），從使用三維表面粗度計所計算得到的粗度曲線，去 掉基準長度的部分的最大高度。最大高度（Rmax )，係輪 廓曲線的最大高度（maximum height of profile )’基準 -14- 200934660 長度中之輪廓曲線的波峰高度的最大値與波谷深度的最大 値之和。B065 1 -200 1所記載的觸針式表面粗度測量機 (stylus instrument )’係可於表面上移動觸針而測量表 面的輪廓形狀的偏差，計算參數，記錄輪廓曲線之測量 機。 JIS B0601 -2001 係對應於 ISO 4287: 1997，又 JIS B0651-2001 爲對應於 ISO 3274: 1996。 ^ 最大高度（Rmax )表示最大突起高度，成爲陶瓷片的 ❹ 針孔缺點的指標。具體的而言，脫模層表面的最大高度 (Rmax)超過600nm時，形成於該最大高度（Rmax)超 過6OOnm的部分的陶瓷片的厚度變薄，結果易產生針孔缺 點。另一方面，脫模層表面的Rmax低於100nm時，會有 無法得到滑動性而捲取性變差、生產性變差的傾向。 亦即，本發明的脫模薄膜的脫模層表面的最大高度 (Rmax )爲上述數値範圍，因爲表面平滑性及滑動性優 φ 異，故可抑制所得到的陶瓷片的凹凸形狀，可得到厚度斑 受到抑制的陶瓷片。其結果，係使用所得到的陶瓷片製造 陶瓷電容器時，可得到内部電極的位置偏移更加受到抑制 的電容器。 此外，本發明的脫模薄膜，係與上述脫模層表面同 時，將不具有脫模層之側的表面用接觸式三維表面粗度計 所測量的最大高度（Rmax)爲100nm以上600nm以下較 佳。最大高度（Rmax )，更佳爲 200nm以上 550nm以 下，特別佳爲300nm以上500nm以下。 -15- 200934660 該相關的最大高度（Rmax ) ’係表示不具有脫模層之 側的表面中的最大突起高度，成爲陶瓷片的針孔缺點的指 標。具體而言，不具有脫模層之側的表面的最大高度 (Rmax)超過600nm時，將陶瓷派獎進行塗佈、乾燥後 捲取時，該最大高度（Rmax)超過600nm的部分壓往陶 瓷片，於陶瓷片表面形成了凹部，該凹部變薄，結果針孔 缺點易產生。此外，藉此雖然未達到針孔缺點，但因爲陶 瓷片中形成極端地薄的部分，而變成陶瓷電容器的缺點。 亦即，藉由使本發明的脫模薄膜之脫模層表面、及不 具有脫模層之側的表面的最大高度（Rmax)同時位在上述 數値範圍，因爲表面平滑性更優異，故更抑制所得到的陶 瓷片的表面凹凸形狀，可得到厚度斑更加受到抑制的陶瓷 片。其結果，係使用所得到的陶瓷片製造陶瓷電容器時， 可更抑制内部電極的位置偏移。此外，可抑制於陶瓷片之 針孔發生，且成爲陶瓷片的剝離性優良者。 再者，最大高度（Rmax)，可藉由調整過濾熔融聚合 物之條件、或聚酯薄膜所含有的粒子的形態等而達成。 [縱方向的厚度斑及橫方向的厚度斑] 本發明的脫模薄膜係縱方向的厚度斑爲3.0%以下較 佳，此外，本發明的脫模薄膜係橫方向的厚度斑爲3.0% 以下較佳。本發明之脫模薄膜，係縱方向的厚度斑與橫方 向的厚度斑同時在上述數値範圍較佳。特別是藉由使用厚 度斑優異的脫模薄膜’可更高度地抑制所得到的陶瓷片的 -16- 200934660 厚度斑。使用如此的脫模薄膜製造陶瓷片，使用該相關的 陶瓷片製造陶瓷電容器時，可得到容量更均勻的陶瓷電容 器。由如此的觀點而言，縱方向的厚度斑，較佳爲2.9% 以下，更佳爲2.5%以下，特別佳爲2.0%以下。由如此的 觀點而言，縱方向的厚度斑，較佳爲2.8%以下，更佳爲 2.6%以下，特別佳爲2.5%以下。 縱方向的厚度斑，可藉由縱延伸倍率而調整，此外， 調整縱延伸步驟中的補助加熱溫度、延伸溫度亦重要。橫 方向的厚度斑，可藉由縱延伸倍率、橫延伸倍率而調整， 此外，調整橫延伸步驟中的補助加熱溫度、延伸溫度調整 亦重要。 <脫模薄膜的製造方法> 關於製造具有如上述的物性之本發明的脫模薄膜之方 法，說明如下。本發明的脫模薄膜，藉由如下述之未延伸 φ 聚酯薄膜成形步驟、一次延伸步驟、線上（in line )塗佈 步驟、二次延伸步驟、及熱固定步驟而製造。 [未延伸聚酯薄膜成形步驟] 得到本發明的脫模薄膜時，首先，於未延伸聚酯薄膜 成形步驟，將後述的聚酯原料擠壓成形，得到未延伸聚酯 薄膜。 擠壓成形時，使用擠壓機，將藉由模具擠壓出的熔融 片用冷卻滾筒進行冷卻固化而得到未延伸聚酯薄膜。此 -17- 200934660 時，對於減少聚合物中的粗大粒子之目的，在熔融擠壓 前，先使用由線徑15 μίη以下的不鏽鋼細線所成的平均網 目大小爲ΙΟμιη以上30μιη以下的不織布型過濾器，較佳 爲ΙΟμιη以上20μιη以下的不織布型過濾器，過濾熔融聚 合物較佳。如上述，藉由減少聚合物中的粗大粒子的個 數，可使脫模薄膜之脫模層表面、及不具有脫模層之側的 表面的最大高度（Rmax)在lOOnm以上600nm以下的數 値範圍。 而且，該相關的濾過處理後，在模具的噴嘴的前方， 使用平均網目大小爲ΙΟμιη以上50μιη以下、較佳爲15μιη 以上30μιη以下的過濾器，過濾熔融擠壓聚合物，但由可 更高度地去掉聚酯的熱劣化物之觀點而言，可使最大高度 (Rmax )値在更佳的數値範圍。 此外，於提昇未延伸聚酯薄膜的平面性之觀點中，提 高藉由模具擠壓出的熔融片與冷卻滾筒的密著性較佳，例 如較佳爲採取靜電外加密著法及/或液體塗佈密著法。 [―次延伸步驟] 於一次延伸步驟中，藉由將藉由上述的未延伸聚酯薄 膜成形步驟所得到的未延伸聚酯薄膜，於長邊方向進行延 伸（以下，亦稱爲縱延伸），得到長邊方向一軸延伸聚酯 薄膜。 此時，在一次延伸步驟前，預先在（Tg-10) °C以上 (Tg-2 ) °C以下的溫度條件下預熱備用，因爲可得到具有 -18- 200934660 均勻的厚度，同時具有所望的長邊方向的伸長率（SMD) 及熱伸長率（HSmd)之脫模薄膜而較佳。再者，此處之 Tg，表示未延伸聚酯薄膜的玻璃轉化溫度（單位：°c)。 於一次延伸步驟中，將任意地施加預熱之未延伸聚酯 薄膜，在（Tg + 2 ) °c以上（Tg + 40 ) t以下的溫度條件 下，於長邊方向以3.3倍以上4.0倍以下的範圍進行延 伸。 延伸倍率小於3.3倍時，會有長邊方向的熱伸長率 HSMd成爲正値的傾向，亦即會有薄膜伸長的傾向而較不 佳。另一方面，延伸倍率大於4.0倍時，會有長邊方向的 伸長率（SMD )太小的傾向而較不佳，此外，會有長邊方 向的熱伸長率（HSMD )太小的傾向而較不佳。使延伸倍率 爲3.3倍以上4.0倍以下，對於爲了使長邊方向的伸長率 (Smd )及熱伸長率（HSMD )爲所望的數値範圍而言亦重 要。 此外，使未延伸聚酯薄膜在（Tg + 2 ) °C以上 (Tg + 40 ) °C以下的溫度條件下，於長邊方向以3.7倍以 上4.0倍以下的範圍進行延伸，則可使縱方向的厚度斑爲 3.0%以下。長邊方向的延伸倍率降太低，則會有縱方向的 厚度斑變差的傾向。由如此的觀點而言’長邊方向的延伸 倍率的下限，更佳爲3.8倍以上。另一方面’長邊方向的 延伸倍率太高，則於縱延伸步驟所得到的長邊方向一軸延 伸聚酯薄膜中，因爲有橫方向的厚度斑變差的傾向’此 外，因爲部分的配向結晶化部分被形成’故會有使脫模薄 -19- 200934660 膜的橫方向的厚度斑優良這點變困難的傾向。 [線上塗佈步驟] 於線上塗佈步驟中，於長邊方向一軸延伸聚酯薄膜的 至少一方的面，以線上，藉由塗佈脫模層形成組成物（以 下，亦稱爲塗劑），得到具有塗膜之聚酯薄膜。亦即，脫 模層係藉由於在一方向經延伸的聚酯薄膜上塗佈脫模層形 成組成物而形成。 作爲於線上塗佈步驟中所使用的塗劑，使用含有後述 之水系的熱硬化性聚矽氧烷樹脂組成物之水性塗液較佳。 此外，作爲塗佈方法，並沒有特別的限制，作爲水性 乳膠的塗佈方法，可使用既知的任意的塗佈技法，例如藉 由輥式塗佈、噴霧塗佈、照相凹版塗佈、逆照相凹版塗 佈，或，擠壓型塗佈等之方法，於一次延伸步驟所得到的 長邊方向一軸延伸聚酯薄膜上塗佈塗劑。 本發明的脫模薄膜，其特徵係以線上塗佈塗劑。本發 明的脫模薄膜，藉由使以線上塗佈塗劑，然後進行第二軸 的延伸，再進行熱固定，而完成對於脫模薄膜的熱處理。 而且，然後用線外（off line )而不施加熱。因此，可在決 定作爲脫模薄膜的製造的目標値之物性，特別是長邊方向 的伸長率（SMD)、寬度方向的伸長率（STD)、或長邊方 向的熱伸長率（HSmd)、寬度方向的熱伸長率 C HStd )，直接維持的狀態下，使用於實際的使用。亦 即，本發明的脫模薄膜因爲藉由以線上塗佈塗劑，脫模薄 -20- 200934660 膜製造的物性的目標値直接成爲脫模薄膜的最終的物性， 故成爲尺寸安定性優異的脫模薄膜。 另一方面，使用一度經製膜的聚酯薄膜，以線外塗佈 用於形成脫模層的塗劑之方法，係必須經由乾燥去除塗劑 所有的溶劑，使成爲脫模層的樹脂進行硬化之步驟。使成 爲脫模層的樹脂進行硬化之步驟，因爲必須施加1 5 0 °C附 近的溫度，故以線外形成脫模層的脫模薄膜，於脫模薄膜 ^ 的長邊方向及寬度方向的兩者，伸長率變大，在陶瓷層/ 〇 脫模薄膜複合體的搬運步驟中薄膜伸長而較不佳。 再者，本發明的脫模薄膜中，以線上塗佈塗劑得到塗 膜後，可僅藉由塗佈後的預熱、第二軸的延伸、及熱固定 的各步驟所施加的熱，乾燥去除來自塗膜的溶劑，使塗劑 所含有的樹脂硬化，而且，使成爲脫模層的樹脂密著於聚 酯薄膜。故，並不需要特別設置使塗膜乾燥硬化的步驟， 因此，不需要使爲了在得到尺寸安定性優異的脫模薄膜的 0 同時得到脫模薄膜之步驟變煩雜。 此外，本發明的脫模薄膜，其特徵係以線上將塗劑塗 佈於一軸延伸聚酯薄膜。藉由成爲如此的形態，可更提高 脫模層與聚酯薄膜的密著性。此外，調整脫模層所含有的 界面活性劑的種類、及添加量變容易，可提高剝離帶電防 止性的提昇效果。 再者，塗劑的固形分濃度，〇 · 5質量％以上3 0質量％ 以下較佳，1質量％以上1 5質量％以下更佳’ 1 · 5質量％以 上1 0質量％以下特別佳。塗劑的固形分濃度低於〇 · 5質量 -21 - 200934660 %時，於聚酯薄膜表面塗佈塗劑時，會有塗劑被聚酯薄膜 表面彈開，無法均勻地塗佈的傾向。另一方面，超過30 質量％時，會有發生所得到的脫模層產生混濁，此外，塗 劑易凝膠化，塗佈的費用較高但效果反而低的問題之情 況。 [二次延伸步驟] 於二次延伸步驟中，藉由將具有藉由線上塗佈步驟所 得到的塗膜之聚酯薄膜，於寬度方向進行延伸（以下，亦 稱爲橫延伸），得到二軸延伸聚酯薄膜。 此時，在二次延伸步驟前，預先在（Tg + 10 ) °c以上 (Tg + 3 0 ) °C以下的溫度條件下施加補助加熱，因爲可充 分地乾燥塗劑所含有的溶劑，然後於所進行的二次延伸步 驟中均勻地進行延伸而較佳。 二次延伸步驟中，在（Tg+10 ) °c以上（Tg+80 ) °C以 下，較佳爲補助加熱溫度以上（Tg + 70 ) °C以下的溫度條 件下，於寬度方向以3.0倍以上5.0倍以下的範圍進行延 伸。寬度方向的延伸倍率在上述數値範圍，則橫方向的厚 度斑優異。寬度方向的延伸倍率太低時，會有橫方向的厚 度斑變差的傾向。另一方面’寬度方向的延伸倍率太高 時，會有於製造中薄膜變得易斷裂的傾向。由如此的觀點 而言，寬度方向的延伸倍率’較佳爲3.5倍以上4.5倍以 下，更佳爲3 · 9倍以上4.3倍以下，特別佳爲4 · 0倍以上 4.2倍以下。 -22- 200934660 此外’本發明中，面延伸倍率（縱延伸倍率x橫延伸 倍率）爲15以上較佳，可使縱方向及橫方向的厚度斑更 佳，面延伸倍率，更佳爲16以上。 再者，本發明中一次延伸步驟的延伸倍率（以下，亦 稱爲縱延伸倍率）與二次延伸步驟的延伸倍率（以下，亦 稱爲橫延伸倍率）的關係，縱延伸倍率各橫延伸倍率較 佳。若是縱延伸倍率S橫延伸倍率的關係，使長邊方向的 伸長率（SMD )、寬度方向伸長率（STD)，及，長邊方向 的熱伸長率（HSMD)、寬度方向的熱伸長率（HStd)， 控制在所望之値這點變容易。 [熱固定步驟] 熱固定步驟中，將藉由二次延伸步驟所得到的二軸延 伸聚酯薄膜，藉由熱固定，而得到脫模薄膜。 熱固定的溫度條件，因構成聚酯薄膜之聚酯的種類而 φ 不同，但一般而言在（Tg + 7〇 )。(：以上（Tm )。(：以下的溫 度範圍進行較佳。例如聚酯爲聚對苯二甲酸乙二醇酯時’ 於180 °C以上235 Ό以下的溫度範圍進行熱固定較佳°此 外’聚酯爲聚2,6-萘二酸乙二醇酯時’以185 °C以上240 °C 以下的溫度範圍進行熱固定較佳。藉由於此溫度範圍進行 熱固定，可得到所望的伸長率（Smd及STD)、熱伸長率 (HSMD及HSTD)。再者’此處Tm表示聚醋的熔點（單 位：。。）。 此外，希望熱固定不僅在1區域實施’分成複數的區 -23- 200934660 域而段階地實施，較佳爲以3區域以上控制溫度進行。例 如熱固定於3區域實施時，第1區域爲180 °C以上210 °C以 下，第2區域設定爲高於第1區域，使其成爲3區域最大 的溫度。而且，使第3區域低於第2區域的溫度，設定在 18 0°C以上200 °C以下較佳。如上述可藉由使第2區域成爲 最高溫度，使第3區域爲低於此的溫度進行熱固定，優良 地保持所得到的脫模薄膜的平面性，可降低陶瓷片的厚度 斑。再者，熱固定時間，並沒有特別的限定，例如以1秒 以上60秒以下左右進行較佳。 此外，爲了使脫模薄膜的寬度方向的熱伸長率 (HSTD)成爲所望之値，於熱固定步驟的最後的區域，將 導軌寬度縮爲2%以上5%以下左右而弛緩處理薄膜較佳。 [冷卻步驟](任意步驟） 本發明的脫模薄膜，係可在熱固定步驟之後，任意地 設置冷卻步驟。藉由設置冷卻步驟，可優良地保持所得到 的脫模薄膜的平面性，降低陶瓷片的厚度斑。 冷卻步驟中，使冷卻溫度爲（Tg-30 ) t以上 (Tg + 2 0 ) °C以下的範圍而實施較佳，與上述的熱固定步 驟同樣，分成複數的區域進行較佳。冷卻溫度低於上述數 値範圍時，會有熱伸長率（HSMD、HSTD )皆太小的情 況。另一方面，冷卻溫度高於上述數値範圍時，即使薄膜 的長邊方向的中心線附近之物性在各方向皆均等，但長邊 方向的側緣部則產生斜面配向變強之現象而較不佳。再 -24- 200934660 者，長邊方向的側緣部成爲斜面配向之現象，即使於上述 的熱固定溫度的較適範圍的下限側亦可能引起，但其程度 比較小。 <聚酯薄膜> [聚酯] 作爲形成本發明所使用的聚酯薄膜之聚酯，可爲均聚 酯，亦可爲共聚合聚酯。 本發明所使用的聚酯薄膜由均聚酯所成時，芳香族二 羧酸與脂肪族二醇進行聚縮合而得到者較佳。其中，作爲 所使用的芳香族二羧酸，可列舉例如對苯二甲酸、2,6-萘 二甲酸等。此外，作爲所使用的脂肪族二醇，可列舉例如 乙二醇、二乙二醇、1,4-環己烷二甲醇等。作爲本發明所 使用的聚酯薄膜的代表均聚酯，可列舉聚對苯二甲酸乙二 醇酯（PET)、聚2,6-萘二酸乙二醇酯（PEN)等。 另一方面，形成本發明所使用的聚酯薄膜之聚酯，爲 共聚合聚酯時，相對於全酸成分，以使20莫耳％以下之成 爲第三成分的二羧酸及/或二醇進行共聚合之共聚合物較 佳。 作爲成爲共聚合聚醋的單體成分之二竣酸，可列舉例 如間苯二甲酸、對苯二甲酸、2,6-萘二甲酸、己二酸、癸 二酸、羥酸（例如P-羥基苯甲酸等）等，可使用此等的一 種或二種以上。此外，作爲成爲共聚合聚酯的單體成分之 二醇’可列舉乙二醇、二乙二醇、丙二醇、丁二醇、1，4- -25- 200934660 環己烷二甲醇、新戊二醇等，可使用此等的一種或二種以 上。 作爲本發明所使用的聚酯薄膜的材料，此等之中，又 以80莫耳％以上、較佳爲90莫耳％以上爲對苯二甲酸乙 二醇酯單位之聚對苯二甲酸乙二醇酯，或，80莫耳％以 上、較佳爲90莫耳％以上爲2,6 -萘二酸乙二醇酯單位之聚 2,6-萘二酸乙二醇酯較佳，以聚對苯二甲酸乙二醇酯爲特 別佳。一般而言聚對苯二甲酸乙二醇酯之Tg，因爲爲 78 °C附近之低溫，故使用聚對苯二甲酸乙二醇酯薄膜作爲 以1〇〇 °C附近的溫度進行處理之陶瓷片之製造用承載薄膜 時，於步驟中尺寸安定性並無特別的問題。相對於此，本 發明的脫模薄膜’因爲尺寸安定性優異，故即使於遠超過 Tg的溫度中使用，亦可充分地發揮作爲脫模薄膜的性 能。 [添加劑] 作爲本發明所使用的聚酯薄膜的材料之聚酯中，主要 以賦予作爲薄膜時的易滑性爲目的，摻合粒子較佳。作爲 所摻合的粒子的種類，只要是可賦予易滑性之粒子即可， 並沒有特別的限制，具體而言，可列舉例如二氧化矽、碳 酸鈣、碳酸鎂、碳酸鋇、硫酸鈣、磷酸鈣、磷酸鎂、高嶺 土、氧化鋁、氧化鈦等之粒子。 此外，可使用如特公昭59-52 1 6號公報、特開昭59-2 1 7755號公報等所記載之耐熱性的有機粒子。作爲耐熱性 -26- 200934660 有機粒子之其他例子’可列舉由聚砂氧院樹脂、熱硬化性 尿素樹脂、熱硬化性酚樹脂、熱硬化性環氧樹脂、苯並鳥 糞胺樹脂等所成的粒子。而且’於聚酯的製造步驟中’可 使用令觸媒等之金屬化合物的一部分沈殿、微分散之析出 粒子。 用於賦予如上述的易滑性之粒子的形狀’並無特別的 限制，可使用球狀、塊狀、棒狀、扁平狀等之任一者。此 @ 外，關於其硬度、比重、顏色等，亦無特別的限制。而 且，此等的粒子，必要時可倂用2種以上。 再者，粒子的平均粒徑，爲Ο.ίμι»以上Ιμιη以下較 佳，爲0.2μπι以上0.5μιη以下更佳。平均粒徑低於Ο.ίμιη 時，會有粒子易凝聚，分散性變不足之情況。另一方面， 超過1 μπι時，所得到的聚酯薄膜的表面粗度變太粗，使脫 模薄膜之脫模層表面的最大高度（Rmax )、及不具有脫模 層之側的表面的最大高度（Rmax)爲100nm以上60 0nm φ 以下變困難。 此外，爲了賦予易滑性所摻合的粒子的含量，於聚酯 薄膜中，爲〇_〇1質量％以上2質量％以下較佳，爲0.01質 量％以上1質量。/。以下爲更佳。粒子的含量低於0.01質量 %時，會有薄膜的易滑性變不足的傾向。另一方面，超過 2質量％時，會有薄膜表面的平滑性變不足的傾向。 作爲使聚酯薄膜中含有粒子之方法，並沒有特別的限 制’但可採用先前技術的方法。例如在製造聚酯之任意的 段階’雖然可添加欲摻合的粒子，但在酯化的段階、或酯 -27- 200934660 交換反應終了後摻合粒子，然後，進行聚縮合反應較佳。 此外，使用附有通風口的混練擠壓機，摻合被分散於乙二 醇或水等的粒子之淤漿與聚酯原料之方法，或，亦可使用 混練擠壓機，藉由摻合經乾燥的粒子與聚酯原料之方法等 進行》 [層構成] 本發明中之聚酯薄膜的構成，並無特別的限制，可爲 單層構成，亦可爲層合構成。此外，爲層合構成時，除了 2層、3層構成以外，只要未超越本發明的要旨，可爲4 層或4層以上的多層。層合構成亦無特別的限制，可列舉 例如 A/B、A/B/A、A/B/C、A/B/A，等之層合構成。其中， A、B、C各自表示由上述聚酯所成的層，可相同，亦可爲 相異。A’特別是表示由與A構造類似之聚酯所成之層。 [聚酯薄膜的厚度] 本發明中之聚酯薄膜全體的厚度，並沒有特別的限 制’但較佳爲9μιη以上50μιη以下，更佳爲15μπι以上 38μιη以下，特別佳爲25μιη以上31μπ1以下。 <脫模層> [聚砂氧烷樹脂組成物] 本發明中之脫模層，因爲以乳膠而言爲安定，故主要 砂氧烷樹脂組成物所形成較佳。聚矽氧烷樹脂組成 -28- 200934660 物，係由含有1分子中至少具有2個之不飽和基或羥基的 至少任一者之聚矽氧烷所成的主劑，及，由1分子中至少 具有2個之直接鍵結於矽原子之氫原子之氫聚矽氧烷所成 的交聯劑作爲構成成分者。本發明中，塗佈含有該相關的 聚矽氧烷樹脂組成物之水性塗液（塗劑），形成塗膜，使 該相關的塗膜硬化而形成脫模層。 本發明之聚矽氧烷樹脂組成物，爲水系的聚矽氧烷樹 φ 脂組成物較佳。水系的聚矽氧烷樹脂組成物，因爲作爲乳 膠時的安定性優異，結果可提高塗劑的安定性。此外，後 述之界面活性劑的選擇性變廣，例如可使用含有更多羥基 之界面活性劑’可提高剝離帶電防止性的提昇效果。再 者’使其成爲水系的塗劑，由環境面而言亦較佳。 此外，本發明中，作爲使聚矽氧烷樹脂組成物進行硬 化之方法’可列舉熱硬化、紫外線硬化、電子線硬化等， 其中又以熱硬化較佳，亦即作爲聚矽氧烷樹脂組成物，以 φ 熱硬化性聚矽氧烷樹脂組成物較佳。本發明中，如前述， 於線上塗佈步驟中得到具有塗膜之聚酯薄膜，於之後的熱 固定步驟中進行熱處理。聚矽氧烷樹脂組成物若爲熱硬化 性聚矽氧烷樹脂組成物，於該相關的熱固定步驟中使其藉 由熱處理促進交聯反應，可充分地進行聚矽氧烷樹脂組成 物的硬化’可得到具有脫模性優異等之優異特性之脫模 層。 由上述而言’本發明中作爲聚矽氧烷樹脂組成物，以 水系的熱硬化性聚矽氧烷樹脂組成物爲特別佳。再者，此 -29- 200934660 處之「主要」之意，係表示相對於脫模層的重量， 質量％以上爲聚矽氧烷樹脂組成物所形成。 作爲聚矽氧烷樹脂組成物，可爲加成聚合型（ 由1分子中具有至少2個不飽和基之聚矽氧烷所成 縮合型（主劑係由1分子中具有至少2個羥基之聚 所成時）的任一者，但爲加成聚合型時，爲塗劑中 爲觸媒之舶者，爲縮合型時，爲塗劑含有作爲觸媒 較佳。其中，由剝離特性優異之觀點而言，以加成 者較佳。此外，交聯劑，較佳爲可使用同時所使用 之製造者所推薦者。 以下，列舉於本發明中可適用之水系的熱硬化 氧烷樹脂組成物的具體例子。 1) Wacker Silicone (密西根州、A d r i a η )之 40 0E聚矽氧烷樹脂組成物，含有由聚矽氧烷、鉛 及，甲基氫聚矽氧烷所成的V20交聯劑系。 2) Dow Corning (密西根州、Midland)之水怕 7 72 0聚矽氧烷樹脂組成物，由含有甲基乙烯基聚砂 及，鉑聚矽氧烷所成的X2-772 1交聯劑系之甲基氫 烷所成。 3 ) PCL ( Phone-Poulenc Inc·，南卡羅萊納州 Hill)之水性的PC-1 05聚矽氧烷樹脂組成物，由含 乙烯基聚矽氧烷，及，鈾聚矽氧烷所成的PC-95的 分之甲基氫聚矽氧烷所成。 4) PCL PC-107水性之聚矽氧烷樹脂組成物（ 由75 主劑係 時）及 矽氧烷 含有作 的錫者 聚合型 的主劑 性聚矽 水性的 觸媒， :的 X2- 氧烷， 聚矽氧 、Rock 有甲基 觸媒成 與PC- 200934660 105類似），含有上述的PC-95交聯劑。 5) PCL PC-188水性之聚矽氧烷樹脂組成物（與pc-105 類似 ） ， 含有上述的 PC-95 交 聯劑。 再者’此等之水系的熱硬化性聚矽氧烷樹脂組成物， 藉由加入脫離子水等適當調整固形分濃度，可作爲塗劑使 用。 [矽烷偶合劑] 而且’本發明之脫模層，含有矽烷偶合劑較佳。作爲 矽烷偶合劑，聚酯樹脂及聚矽氧烷樹脂組成物之任一者， 或者具有與雙方鍵結的反應基之有機矽低分子化合物較 佳，作爲該相關的反應基，以具有甲氧基、乙氧基、矽烷 醇基、乙烯基、環氧基、（甲基）丙烯基、胺基、氫硫 基、氯基、羥基、羧基等之至少1種以上之有機矽低分子 化合物較佳。 該相關的矽烷偶合劑的含量，相對於脫模層的固形分 重量，爲〇· 1質量％以上20質量％較佳，1質量％以上1 〇 質量％以下爲更佳，3質量％以上7質量％以下爲特別佳。 藉由使含量爲上述數値範圍，可提高脫模層的密著性。 [界面活性劑] 本發明之脫模層，相對於脫模層的固形分重量，含有 0.5質量％以上10質量％以下的界面活性劑較佳。脫模層 藉由含有上述數値範圍的量之界面活性劑，可抑制在捲出 -31 - 200934660 滾筒狀的脫模薄膜時的剝離帶電、及從脫模薄膜剝離陶瓷 片時的剝離帶電。此外，製造層合陶瓷電容器時，可抑制 内部電極的位置偏移。而且，於塗劑中，藉由添加界面活 性劑，相對於聚酯薄膜表面之塗劑的濕潤性變優良，其結 果，塗劑的局部的彈開缺點等受到抑制，不但可得到均勻 的塗膜，亦可抑制剝離陶瓷片時所發生的針孔缺點。 由如此的觀點而言，界面活性劑的含量，以脫模層的 全乾燥重量爲基準，更佳爲1.0質量％以上7.0質量％以 下，特別佳爲2.0質量％以上5.0質量％以下。含量低於 0.5質量％時，造成剝離帶電變高。此外，相對於聚酯薄 膜表面，會有塗劑的濕潤性變不足的傾向。另一方面，超 過1 0質量％時，會有相對於陶瓷片之剝離力變成重剝離的 傾向，而較不佳。 作爲界面活性劑，可列舉離子系界面活性劑（陰離子 系界面活性劑、陽離子系界面活性劑、兩性離子系界面活 性劑）、及非離子系界面活性劑（nonionic surfactant )， 其中又以非離子系界面活性劑較佳。使用陰離子系界面活 性劑、陽離子系界面活性劑、兩性離子系界面活性劑等之 離子系界面活性劑時，此等的界面活性劑相對於用於形成 脫模層之聚矽氧烷樹脂組成物而言變成觸媒毒，會有聚矽 氧烷樹脂組成物未充分地硬化的情況。 作爲非離子系界面活性劑，可列舉聚氧化乙烯型、多 元醇脂肪酸酯型、多元醇烷基醚型、含氮型等之界面活性 劑、及非離子系的聚矽氧烷系界面活性劑、非離子系的氟 -32- 200934660 系界面活性劑等。 作爲聚氧化乙烯型界面活性劑，可列舉聚（氧化乙 烯）烷基醚、聚（氧化乙烯）烷基苯基醚、聚（氧化乙 烯）聚（氧化丙烯）烷基醚、聚（氧化乙烯）脂肪酸酯、 聚（氧化乙烯）山梨糖醇酐脂肪酸酯等。其中，作爲聚 (氧化乙烯）烷基醚，又較佳爲聚氧化乙烯月桂基醚、聚 氧化乙烯肉豆蔻基醚、聚氧化乙烯鯨蠟基醚、聚氧化乙烯 硬脂醯醚、聚氧化乙烯油醯基醚等之具有碳數12以上的 烷基的聚（氧化乙烯）烷基醚。該相關的烷基，可爲直鏈 狀，亦可爲支鏈狀。作爲多元醇脂肪酸酯型界面活性劑， 可列舉丙二醇脂肪酸酯、甘油脂肪酸酯、聚甘油脂肪酸 酯、山梨糖醇酐脂肪酸酯、蔗糖脂肪酸酯等。作爲多元醇 烷基醚型界面活性劑，可列舉烷基聚葡萄糖苷等。作爲含 氮型界面活性劑，可列舉烷基二乙醇醯胺、烷基胺氧化物 等。 作爲聚矽氧烷系界面活性劑，可列舉聚醚改性聚矽氧 烷、聚甘油改性聚矽氧烷等。此外，作爲該相關的改性聚 矽氧烷的構造，分類爲側鏈變形型、兩末端改性型（ABA 型）、單末端改性型（ΑΒ型）、兩末端側鏈改性型、直 鏈嵌段型（ΑΒη型）、支鏈型等，但可爲任一結構。 作爲本發明之界面活性劑，其中，又以聚氧化乙烯型 界面活性劑、聚矽氧烷系界面活性劑較佳。此等，較不易 變成聚矽氧烷樹脂組成物的觸媒毒，此外可表現出充分的 濕潤性。特別佳爲聚矽氧烷系界面活性劑，更不易變成 -33- 200934660 觸媒毒，可爲脫模特性更優異者，此外可更提高剝離帶電 防止性的提昇效果。 再者，本發明之脫模層的厚度（亦即乾燥後的厚 度），並沒有特別的限制，但較佳爲20nm以上90nm以 下。一般而言，低於20nm，發揮輕剝離力等之作爲脫模 層的效果變困難，另一方面，超過9Onm時，費用高但所 得到的效果反而變少。 <脫模薄膜的用途> 本發明的脫模薄膜，可作爲樹脂片、陶瓷片等之片成 形用薄膜，或，標簽用、醫療用、事務用品用等之黏著用 薄膜之分離器使用。 特別是本發明的脫模薄膜，因爲充分地符合陶瓷片製 造時對於脫模薄膜所要求的性能，故適合作爲陶瓷片製造 用的承載薄膜使用。使用本發明的脫模薄膜製造陶瓷片， 則可精度佳地得到薄膜的陶瓷片，此外，所得到的薄膜的 陶瓷片，可適用於隨著小型化•大容量化而要求内部電極 的多層化之層合陶瓷電容器。 再者，陶瓷片的製造時，將所準備的陶瓷淤漿，塗佈 於本發明的脫模薄膜的脫模層表面，可乾燥去除陶瓷淤漿 所含有的溶劑。此外，作爲陶瓷淤漿的塗佈方法，並沒有 特別的限制，可使用先前技術的塗佈方法。例如可使手將 使陶瓷粉體與黏合劑等分散於溶劑的陶瓷淤漿，藉由逆輥 法塗佈，藉由加熱乾燥去除溶劑之方法。作爲所使用的黏 -34- 200934660 合劑’並沒有特別的限制’例如可使用聚乙烯丁縮醛等。 此外’作爲所使用的溶劑，並沒有特別的限制，例如可使 用乙醇、甲苯等。 <薄膜滾筒> 本發明的薄膜滾筒，將上述所得到的脫模薄膜捲取於 滾筒狀者。作爲脫模薄膜滾筒，可爲藉由上述的脫模薄膜 @ 的製造步驟直接得到的母滾筒，亦可爲由該相關的母滾筒 切割成顧客要求的寬度及長度之切割滾筒（slit roll )。 本發明的薄膜滾筒，係滾筒表層的維氏硬度（Hv)爲 0以上450以下。藉由使滾筒表層的維氏硬度（Hv)在上 述數値範圍，可得到平坦性優異的脫模薄膜。此外，脫模 薄膜滾筒中，不易產生捲取偏移或皺褶。 維氏硬度，係將使用對面角爲136度的鑽石四角垂壓 頭，將於試験面造成角錐型的坑窪時的載重，除以由永久 φ 坑窪對角線的長度所計算得到的表面積之商數，以下述式 計算出。 Ην = (2 · Ρ · sin(a/2))/d2 P:載重（kg) 、d:坑窪的對角線的長度的平均 (mm ) 、a :對面角 因爲a=136度，故上式係如下述。 -35- 200934660-4- 200934660 VI. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a release film, and more particularly to a performance that is sufficiently compatible with a release film used in the manufacture of a ceramic sheet. Release film. [Prior Art] i A release film made of a polyester film as a substrate, and a ceramic sheet (green sheet) used in the production of various ceramic electronic parts such as a ceramic ❹ capacitor 'ceramic substrate. Used as a carrier film. The ceramic sheet used in the production of the laminated ceramic capacitor is, for example, coated on a carrier film, and the ceramic powder and the binder are dispersed in a ceramic slurry by a reverse roll method or the like, and dried by heating to remove the solvent to form a ceramic. After the layer, the metal film/ceramic layer/carrier film composite is formed by a steaming blade or a metal φ film which is formed as an internal electrode on the ceramic layer, and is manufactured by peeling off the carrier film from the related composite. . The laminated ceramic capacitor is obtained by laminating a metal film/ceramic layer composite produced as described above in a desired size, and after hot pressing, by cutting into a rectangular shape to obtain a sheet-like laminate, The sheet-like laminate is fired and obtained by forming an external electrode on a predetermined surface of the fired body. However, in recent years, in the field of capacitors such as laminated ceramic capacitors, the density of circuit components has been required to be reduced in size and capacity, and the thickness of the ceramic sheets to be used has to be increased. The film is thinned to make the internal electrodes more stratified. However, if the thickness of the ceramic sheet is made thinner and the number of laminated sheets is increased, even a small thickness of the ceramic sheet may cause a positional shift of the internal electrodes. Therefore, it is proposed to reduce the thermal deformation of the carrier film during the production of the ceramic sheet and to reduce the thickness of the ceramic sheet to be produced (refer to Patent Document η. Patent Document 1 describes the dimensional change rate at a stress of 1.47 MPa at 120 °C. The release film having an absolute width of 0.3% or less in both the longitudinal direction and the width direction is extremely small because the thermal deformation during heat treatment is small, and the thickness of the obtained ceramic sheet can be suppressed. At a temperature near 〇〇 ° C, it is dried without being held in the width direction. Therefore, the carrier film used in the production of the ceramic sheet shrinks when the ceramic is dried, and the tension is hardly applied in the width direction. Therefore, as described in Patent Document 1, only the release film having a low heat shrinkage rate in the longitudinal direction and the width direction in the state in which the tension is applied is used, and the film is carried out in all the steps up to the drying of the ceramic. The shrinkage spot cannot be eliminated, and there is still a problem that a thickness spot occurs in the ceramic piece to be manufactured, and a positional deviation of the internal electrode is caused when laminating. When the thickness is small, the surface roughness of the carrier film is high, and defects due to the occurrence of pinholes or breakage of the ceramic sheets when the ceramic sheets are peeled off occur, which causes a decrease in productivity. That is, when the ceramic sheets are thin, even The surface defects such as scratches or foreign matter on the surface of the carrier film which have not caused problems in the prior art are also apparently caused by the disadvantages of the pinholes of the obtained ceramic sheets, -6-200934660. The miniaturization and the large capacity require higher dimensional stability and higher surface unevenness for the carrier film used for the production of ceramic sheets. On the other hand, the surface of the carrier film is smoothed. In the case where the stripping electrification becomes high, for example, the coating speed of the ceramic slurry is increased for productivity improvement, sparks may occur in the step of unwinding the carrier film, so that A has a problem that fire is likely to occur. In addition, when the ceramic sheet is peeled off from the carrier film, the ceramic sheet is charged, and when the ceramic sheet is laminated in the next step, the internal portion is charged due to the charging. The position of the electrode is shifted. Therefore, it is strongly required to suppress peeling electrification as a carrier film having a smoother surface. In particular, in the manufacture of a thin (under Ιμηι) ceramic sheet, not only the high-precision dimensional stability as described above Sexuality, and a high degree of smoothing (so-called surface roughness), it is important to control the flatness (also called flatness) of the film more highly. That is, when the flatness of the carrier film is poor, it is applied to φ. The coating thickness of the ceramic slurry on the upper surface is poorly deformed, so that the thickness of the ceramic sheet is poorly changed, and in the laminated ceramic capacitor, the capacity is uneven. However, as described above, the carrier film is generally wound up. The drum-like shape is used, but since the surface has a release layer, it is easy to cause problems such as easy sliding, retracting of the drum during winding, or easy to take up the winding, etc. Therefore, the prior art winds the carrier film as described above to the drum. In the case of the shape, in order to prevent the winding deviation from occurring, it is a general practice to adopt a condition for increasing the hardness of the drum. However, if the hardness of the roller is too high, the carrier film tends to follow the shape of the roller, and the shape of the carrier film is elongated due to the poor shape of the fine roller, which deteriorates flatness. Further, it is important to control the thickness of the film more highly, particularly in the manufacture of a thin (under ΐμTM) ceramic sheet. That is, when the thickness of the load-bearing film is poor, the coating thickness of the ceramic slurry applied thereon is poor, and the thickness of the ceramic sheet is poor, and the capacity of the laminated ceramic capacitor becomes uneven. (Patent Document 1) JP-A-200-343663 SUMMARY OF THE INVENTION The object of the present invention is to provide a suitable dimensional change rate, dry ceramic silt under heating tension when manufacturing a ceramic sheet, in view of the prior art. The heat shrinkage balance at the time of the slurry is also excellent, and the release film which satisfies the properties required for the release film used in the production of the ceramic sheet can be sufficiently obtained. The inventors of the present invention have carefully reviewed the above-mentioned problems, and as a result, found that a release film having a specific elongation under a specific load and having a specific thermal elongation under no load can be obtained in accordance with the case of manufacturing a ceramic sheet. The properties required for the release film used are achieved to complete the present invention. In other words, the present invention is a release film having a release layer on at least one surface of the polyester film, and is applied at a tension of MPa2 MPa or more and 4.0 MPa or less in the longitudinal direction of the release film. The elongation in the longitudinal direction of C (SMD) conforms to the following formula (1), and when the tension of O.OIMPa is applied perpendicularly to the longitudinal direction of the release film, it is perpendicular to the long side at 1 °C. The elongation in the direction of direction -8- 200934660 (STD) conforms to the following formula (2). The release film has a thermal elongation (HSMD) of 10 in the long-side direction of the TC under no load, and conforms to the following formula ( 3) The thermal elongation (HSTD) of the release film at 100 ° C perpendicular to the longitudinal direction under no load, in accordance with the following formula (4), the thermal elongation (HSMD) in the longitudinal direction and The coefficient of thermal elongation (HSTD) perpendicular to the direction of the longitudinal direction is in accordance with the release mold of the following formula (5): 0.0961X-0.45 ^SMd^〇.〇961X-0.25 (1) (in the formula (1), X is applied to the tension per unit area of the film (MPa), and X is 0.2 MPa to 4.0 MPa.) -0.6 ^ STD ^-0.2 (2) -0.4^HSMd^-〇.1 (3) -0.6^ HSTd^-〇.2 (4) HSmd > HSTd (5) Further, in the release film of the present invention, the maximum height (Rmax) ' measured by the contact type three-dimensional surface roughness meter on the surface of the release layer is preferably in the range of 100 nm or more and 600 nm or less. The maximum height (Rmax) measured by the contact type three-dimensional surface roughness meter on the surface of the release layer and the surface on the side not having the release layer is preferably 100 nm or more and 600 nm or less. Further, the removal of the 200934660 mold layer is relative to the release. It is preferable that the weight of the mold layer is 5% by mass or more and 1% by mass or less of the surfactant. The thickness of the longitudinal direction is 3.0% or less, and the thickness of the transverse direction is preferably 3.0% or less. It is preferable to form a composition by coating a release layer on a polyester film which is stretched in one direction. The release film of the present invention is preferably used for the production of a ceramic sheet, and is particularly preferably used for the production of a ceramic capacitor. The invention relates to a film roll in which the release film is wound into a roll, and the film roll including a Vickers hardness (Ην) of the surface layer of the roll is 0 or more and 50 0 or less. The present invention includes the use of the above formulas (1) to (5). Characteristic A method of using a film as a release film for a ceramic sheet. [Best Mode for Carrying Out the Invention] In the present invention, the direction of the mechanical axis of the film formation may be referred to as a longitudinal direction or a longitudinal direction; The direction perpendicular to the longitudinal direction is referred to as the width direction or the lateral direction. <Release film> The release film of the present invention is a release film having a release layer on at least one side of the polyester film, has a specific elongation under a specific load, and has a load under no load. Specific heat elongation. Hereinafter, the physical properties and constitution of the release film of the present invention will be described. [Elongation in the longitudinal direction (SMD)] -10-200934660 The release film of the present invention is applied to the longitudinal direction of the release film at a tension of 0.2 MPa to 4.0 MPa in the longitudinal direction of the release film. The elongation (SMD) is in accordance with the following formula (1). The ceramic layer/release film composite is usually transported under tension at a temperature near the loot. Therefore, by selecting the loot as the temperature condition, it is possible to achieve a more realistic judgment of the actual steps. ❹ 0.0961X-0.45 ^Smd^〇.〇961X-0.25 (1) (In the formula (1), X is applied to the tension per unit area of the film (MPa), and X is 0.2 MPa or more and 4.0 MPa or less.) Long side When the elongation in the direction (SMD) is smaller than the enthalpy of the left side of the above formula (1), the shrinkage stress in the longitudinal direction of the film increases with respect to the conveyance tension of the ceramic layer/release film composite, and as a result, the longitudinal direction is long. The upper portion shrinks unevenly, causing a thickness spot of the ceramic sheet. On the other hand, when the elongation (SMD) in the longitudinal direction φ is larger than the 右边 on the right side of the above formula (1), the contraction stress in the longitudinal direction of the film is small with respect to the handling tension of the ceramic layer/release film composite. The flatness of the film is deteriorated, causing a thickness spot of the ceramic sheet. When the elongation in the longitudinal direction (SMD) satisfies the range of the above formula (1), the shrinkage stress in the longitudinal direction is appropriately balanced with respect to the conveyance tension of the ceramic layer/release film composite, and the obtained ceramic can be suppressed. The thickness of the sheet in the direction of the long side. From such a viewpoint, when the release film of the present invention is applied with a tension of 0.3 MPa or more and 2.5 MPa or less in the longitudinal direction of the release film, the elongation (SMD) in the longitudinal direction at 100 ° C is in accordance with the above. -11 - 200934660 The form of the formula (1) is better. Further, the elongation in the longitudinal direction (SMD) and the elongation in the width direction (STD) described later are calculated by the following formula. In the formula, Mo represents the length in the longitudinal direction or the width direction of the film before the start of the temperature rise, and Μ represents the length in the same direction of the film when the temperature rises to 100 °c. That is, elongation (SMD) and elongation (STD), when negative, indicate film shrinkage, and timing indicates film elongation. Elongation (SMD, Std) = (AM/M〇) x 100 (%) ΔΜ = Μ-Μ〇 [Elongation in the direction perpendicular to the longitudinal direction (width direction) (sTD)] The release film of the present invention, When a tension of O.OIMPa is applied in the width direction of the release film, the elongation (STD) in the width direction of 100 t: conforms to the following formula (2). Therefore, by selecting 100 ° C as the temperature condition, as in the above, it is possible to judge the condition more in line with the actual steps. Further, the elongation ratio (STD) is calculated from the length in the width direction of the film before and after the heat treatment by the above formula. -0.6^Std^-0.2 (2) When the elongation in the width direction (STD) is less than -0.6%, the shrinkage in the width direction of the film is large in the conveyance step of the ceramic layer/release film composite, and the ceramic sheet is caused. The thickness of the spot. On the other hand, when the elongation in the width direction is -12-200934660 (STD) is greater than -0.2%, when the elongation (STD) is greater than 0 (film elongation), the ceramic layer/release film composite is used in the handling film. The elongation in the width direction causes the flatness of the film to be lost, and the thickness of the ceramic sheet is caused. Further, the balance between the shrinkage of the ceramic layer and the elongation of the release film is poor, and there is a problem that the ceramic layer is partially peeled off and floated. When the elongation (STD) exceeds -0.2% and is 0% or less, the balance between the shrinkage of the ceramic layer and the shrinkage of the release film is poor, and there is a problem that the ceramic layer is partially peeled off from the release film and floated. [Thermal elongation (hsmd) in the longitudinal direction and the thermal elongation (HStd) in the direction perpendicular to the longitudinal direction (width direction)] The release film of the present invention has a long-side direction of 100 ° C under no load The thermal elongation (HSMD) conforms to the following formula (3), and the thermal elongation (HSTD) in the width direction at 100 °C under the load-free weight conforms to the following formula (4), and the heat in the longitudinal direction The elongation (HSMD) and the φ thermal elongation (HSTD) in the width direction satisfy the following formula (5). -0.4^HSMd^-〇.1 (3) -0.6 ^ HStd ^-0.2 (4) HSmd>HStd (5) Thermal elongation (hsmd) in the longitudinal direction of the film and thermal elongation (HSTD) in the width direction Each of them is in the above range, and the thermal elongation (hsmd) in the longitudinal direction is greater than the thermal elongation in the width direction -13-34646060 (hstd), and the ceramic slurry is coated by heating and drying to remove the ceramic layer. In the case of the solvent, the balance between the shrinkage in the longitudinal direction of the release film and the shrinkage in the width direction is obtained, and as a result, the thickness of the obtained dried ceramic layer can be reduced. Further, the thermal elongation (HSmd) in the longitudinal direction and the thermal elongation (HStd) in the width direction were calculated by the following formula. In the formula, L0 represents the length in the longitudinal direction or the width direction of the film before heat treatment, and L represents the length in the same direction of the film after heat treatment. That is, the thermal elongation (HSmd) and the thermal elongation (HSTD) indicate that the film shrinks at a negative time and the film elongation at a positive time. Thermal elongation (HSmd, HStd) = (AL/L〇) x 100 (%) Δ L = L' L 〇 [maximum height (Rmax )] and the release film of the present invention, contact type three-dimensional surface of the release layer The maximum height (Rmax) measured by the surface roughness meter is preferably from 100 nm to 60 nm. The maximum height (Rmax) is more preferably 200 nm or more and 550 nm or less, and particularly preferably 300 nm or more and 500 nm or less. The maximum height (Rmax) is the thickness curve calculated from the use of a three-dimensional surface roughness meter in accordance with JIS specifications (B0601-2001: Surface roughness, definition and representation, B0651-2001: stylus surface roughness measurer). , remove the maximum height of the part of the reference length. Maximum height (Rmax), the maximum height of profile of the profile curve. -14- 200934660 The sum of the maximum height of the peak height of the contour curve in the length and the maximum 波 of the valley depth. The stylus instrument described in B065 1 -200 1 is a measuring machine that can measure the deviation of the contour shape of the surface by moving the stylus on the surface, calculate the parameters, and record the contour curve. JIS B0601 -2001 corresponds to ISO 4287: 1997, and JIS B0651-2001 corresponds to ISO 3274: 1996. ^ The maximum height (Rmax) indicates the maximum protrusion height, which is an indicator of the defect of the pinhole of the ceramic piece. Specifically, when the maximum height (Rmax) of the surface of the release layer exceeds 600 nm, the thickness of the ceramic sheet formed at a portion where the maximum height (Rmax) exceeds 600 nm is reduced, and as a result, pinhole defects are likely to occur. On the other hand, when the Rmax of the surface of the release layer is less than 100 nm, the slidability is not obtained, and the windability is deteriorated, and the productivity tends to be deteriorated. That is, the maximum height (Rmax) of the surface of the release layer of the release film of the present invention is in the above range, and since the surface smoothness and the sliding property are excellent, the uneven shape of the obtained ceramic sheet can be suppressed. A ceramic sheet in which the thickness spot is suppressed is obtained. As a result, when a ceramic capacitor is produced using the obtained ceramic sheet, a capacitor in which the positional deviation of the internal electrode is further suppressed can be obtained. Further, the release film of the present invention has a maximum height (Rmax) measured by a contact type three-dimensional surface roughness meter of 100 mm or more and 600 nm or less on the surface of the release layer simultaneously with the surface of the release layer. good. The maximum height (Rmax) is more preferably 200 nm or more and 550 nm or less, and particularly preferably 300 nm or more and 500 nm or less. -15- 200934660 The relevant maximum height (Rmax)' indicates the maximum protrusion height in the surface of the side without the release layer, which is an indication of the pinhole defect of the ceramic sheet. Specifically, when the maximum height (Rmax) of the surface having no side of the release layer exceeds 600 nm, when the ceramic prize is applied and dried, and the coil is taken up, the portion having the maximum height (Rmax) exceeding 600 nm is pressed against the ceramic. The sheet has a concave portion formed on the surface of the ceramic sheet, and the concave portion is thinned, and as a result, pinhole defects are easily generated. Further, although the pinhole defect is not achieved by this, the extremely thin portion is formed in the ceramic sheet, which becomes a disadvantage of the ceramic capacitor. In other words, by setting the maximum height (Rmax) of the surface of the release layer of the release film of the present invention and the surface having no release layer side in the above range, since the surface smoothness is more excellent, Further, the surface unevenness of the obtained ceramic sheet is suppressed, and a ceramic sheet having more suppressed thickness is obtained. As a result, when a ceramic capacitor is produced using the obtained ceramic sheet, the positional shift of the internal electrode can be further suppressed. Further, it is possible to suppress the occurrence of pinholes in the ceramic sheet and to improve the peelability of the ceramic sheet. Further, the maximum height (Rmax) can be achieved by adjusting the conditions for filtering the molten polymer or the form of particles contained in the polyester film. [Thickness in the longitudinal direction and thickness in the lateral direction] The release film of the present invention is preferably 3.0% or less in the longitudinal direction, and the release film of the present invention has a thickness in the transverse direction of 3.0% or less. Preferably. In the release film of the present invention, the thickness of the longitudinal direction and the thickness of the transverse direction are preferably in the above range. In particular, the thickness of -16-200934660 of the obtained ceramic sheet can be more highly suppressed by using a release film having excellent thickness spots. When a ceramic sheet is produced by using such a release film, and a ceramic capacitor is produced using the related ceramic sheet, a ceramic capacitor having a more uniform capacity can be obtained. From such a viewpoint, the thickness of the longitudinal direction is preferably 2.9% or less, more preferably 2.5% or less, and particularly preferably 2.0% or less. From such a viewpoint, the thickness of the longitudinal direction is preferably 2.8% or less, more preferably 2.6% or less, and particularly preferably 2.5% or less. The thickness of the longitudinal direction can be adjusted by the longitudinal stretching ratio, and it is also important to adjust the auxiliary heating temperature and the stretching temperature in the vertical stretching step. The thickness of the horizontal direction can be adjusted by the longitudinal stretching ratio and the lateral stretching magnification. It is also important to adjust the auxiliary heating temperature and the extension temperature in the lateral stretching step. <Method for Producing Release Film> A method for producing a release film of the present invention having the above physical properties will be described below. The release film of the present invention is produced by the following unstretched φ polyester film forming step, primary stretching step, in line coating step, secondary stretching step, and heat setting step. [Unstretched Polyester Film Forming Step] When the release film of the present invention is obtained, first, a polyester raw material to be described later is extrusion-molded in the unstretched polyester film forming step to obtain an unstretched polyester film. At the time of extrusion molding, the melted sheet extruded by the die was cooled and solidified by a cooling drum using an extruder to obtain an unstretched polyester film. At the time of -17-200934660, for the purpose of reducing coarse particles in the polymer, a non-woven type filter having an average mesh size of ΙΟμηη or more and 30 μm or less is formed by using a stainless steel thin wire having a wire diameter of 15 μίη or less before melt extrusion. Preferably, the filter is preferably a non-woven filter of ΙΟμηη or more and 20 μm or less, and the molten polymer is preferably filtered. As described above, by reducing the number of coarse particles in the polymer, the maximum height (Rmax) of the surface of the release layer of the release film and the surface having no release layer can be set to be 100 nm or more and 600 nm or less.値 range. Further, after the relevant filtration treatment, a filter having an average mesh size of ΙΟμηη or more and 50 μm or less, preferably 15 μm or more and 30 μm or less is used in front of the nozzle of the mold to filter the melt-extruded polymer, but it is more highly From the viewpoint of removing the heat deterioration of the polyester, the maximum height (Rmax) can be made to be in the range of a better number. Further, in terms of improving the planarity of the unstretched polyester film, it is preferable to improve the adhesion between the molten sheet extruded by the mold and the cooling drum, for example, it is preferable to adopt an electrostatic external encryption method and/or a liquid. Coating the adhesion method. [Sub-Extension Step] In the first stretching step, the unstretched polyester film obtained by the above-described unstretched polyester film forming step is stretched in the longitudinal direction (hereinafter, also referred to as longitudinal stretching) A longitudinally oriented polyester film is obtained in the longitudinal direction. At this time, preheating is carried out at a temperature of (Tg - 10) ° C or more (Tg - 2 ° ° C or less) before the first stretching step, because a uniform thickness of -18 - 200934660 is obtained, and it is expected It is preferable to use a release film having a long-direction elongation (SMD) and a thermal elongation (HSmd). Further, Tg herein represents the glass transition temperature (unit: °c) of the unstretched polyester film. In the first stretching step, the preheated unstretched polyester film is arbitrarily applied, and at a temperature of (Tg + 2 ) ° C or more (Tg + 40 ) t or less, it is 3.3 times or more and 4.0 times in the longitudinal direction. The following ranges are extended. When the stretching ratio is less than 3.3 times, the thermal elongation HSMd in the longitudinal direction tends to be positive, that is, the film tends to elongate and is less preferable. On the other hand, when the stretching ratio is more than 4.0 times, the elongation in the longitudinal direction (SMD) tends to be too small, which is less preferable, and the thermal elongation (HSMD) in the longitudinal direction tends to be too small. Less good. The stretching ratio is 3.3 times or more and 4.0 times or less, and it is also important for the elongation in the longitudinal direction (Smd) and the thermal elongation (HSMD) to be in the desired range. Further, when the unstretched polyester film is stretched in the range of 3.7 times or more and 4.0 times or less in the longitudinal direction at a temperature of (Tg + 2 ) ° C or more (Tg + 40 ) ° C or less, the longitudinal direction can be made longitudinal. The thickness of the direction is 3.0% or less. If the stretching ratio in the longitudinal direction is too low, the thickness of the longitudinal direction tends to be deteriorated. From such a viewpoint, the lower limit of the stretching ratio in the longitudinal direction is more preferably 3.8 times or more. On the other hand, when the stretching ratio in the long-side direction is too high, the polyester film having a longitudinal direction in the longitudinal direction obtained in the longitudinal stretching step tends to be inferior in thickness in the transverse direction. It is difficult to make the release layer thin -19-200934660 thick in the transverse direction of the film. [On-line coating step] In the in-line coating step, at least one surface of the polyester film is stretched in one direction in the longitudinal direction, and a composition is formed on the line by applying a release layer (hereinafter, also referred to as a coating agent). A polyester film having a coating film is obtained. That is, the release layer is formed by coating a release layer on the stretched polyester film in one direction to form a composition. As the coating agent used in the in-line coating step, an aqueous coating liquid containing a thermosetting polyoxyalkylene resin composition of a water system to be described later is preferably used. Further, the coating method is not particularly limited, and as the coating method of the aqueous emulsion, any known coating technique can be used, for example, by roll coating, spray coating, gravure coating, and reverse photography. A method of gravure coating, or extrusion coating, or the like, is applied to the long-side direction-axially stretched polyester film obtained in one stretching step. The release film of the present invention is characterized in that the coating agent is applied on a line. The release film of the present invention is subjected to heat treatment for the release film by coating the coating agent on the line, then stretching the second shaft, and then thermally fixing it. Moreover, the off line is then used without applying heat. Therefore, it is possible to determine the physical properties of the target of the production of the release film, in particular, the elongation in the longitudinal direction (SMD), the elongation in the width direction (STD), or the thermal elongation in the longitudinal direction (HSmd), The thermal elongation in the width direction C HStd ) is used in actual use in a state of direct maintenance. In other words, the release film of the present invention has a physical property of being released from the film by the application of the coating agent on the line, and the target property of the release film is directly reduced to the final physical properties of the release film, so that it is excellent in dimensional stability. Release film. On the other hand, a method of applying a coating agent for forming a release layer by using a film-formed polyester film once is necessary to remove all the solvent of the coating agent by drying, and to carry out the resin which becomes a release layer. The step of hardening. The step of hardening the resin to be the release layer, since it is necessary to apply a temperature in the vicinity of 150 ° C, the release film of the release layer is formed outside the line, in the longitudinal direction and the width direction of the release film ^ Both of them have an increased elongation, and the film is elongated and is less preferable in the conveyance step of the ceramic layer/tantalum release film composite. Further, in the release film of the present invention, after the coating film is applied by applying the coating agent on the line, the heat applied by only the steps of preheating after application, extension of the second axis, and heat fixation can be performed. The solvent from the coating film is dried to remove the resin contained in the coating agent, and the resin serving as the release layer is adhered to the polyester film. Therefore, it is not necessary to provide a step of drying and hardening the coating film. Therefore, it is not necessary to make the step of obtaining a release film at the same time as obtaining a release film having excellent dimensional stability. Further, the release film of the present invention is characterized in that the coating agent is applied to the one-axis stretched polyester film in a line. By such a form, the adhesion between the release layer and the polyester film can be further improved. Further, it is easy to adjust the type and amount of the surfactant contained in the release layer, and the effect of improving the peeling electrification resistance can be improved. Further, the solid content concentration of the coating agent is preferably 5% by mass or more and 30% by mass or less, more preferably 1% by mass or more and 15% by mass or less, and more preferably 1 5% by mass or more. When the solid content concentration of the coating agent is less than 〇 · 5 mass -21 - 200934660%, when the coating agent is applied to the surface of the polyester film, the coating agent is bounced off the surface of the polyester film, and the coating tends not to be uniformly applied. On the other hand, when it exceeds 30% by mass, turbidity of the obtained release layer may occur, and the coating may be easily gelled, and the cost of coating is high, but the effect is rather low. [Secondary Extension Step] In the secondary stretching step, the polyester film having the coating film obtained by the in-line coating step is stretched in the width direction (hereinafter, also referred to as lateral stretching) to obtain two Axial stretch polyester film. At this time, before the secondary stretching step, the auxiliary heating is applied in advance at a temperature of (Tg + 10 ) ° C or more (Tg + 30 ° C) or less, because the solvent contained in the coating agent can be sufficiently dried, and then It is preferred to carry out the stretching uniformly in the second stretching step performed. In the second stretching step, it is preferably 3.0 times in the width direction at a temperature of (Tg + 10 ) ° C or more (Tg + 80 ° ° C or less), preferably a heating temperature of not more than (Tg + 70 ) ° C or less. The range of 5.0 times or less is extended. When the stretching ratio in the width direction is in the above range, the thickness in the lateral direction is excellent. When the stretching ratio in the width direction is too low, the thickness of the lateral direction tends to be deteriorated. On the other hand, when the stretching ratio in the width direction is too high, the film tends to be easily broken during production. From such a viewpoint, the stretching ratio in the width direction is preferably 3.5 times or more and 4.5 times or less, more preferably 3 · 9 times or more and 4.3 times or less, and particularly preferably 4 · 0 times or more and 4.2 times or less. -22- 200934660 Further, in the present invention, the plane stretching ratio (longitudinal stretching ratio x the lateral stretching ratio) is preferably 15 or more, and the thickness in the longitudinal direction and the transverse direction is better, and the surface stretching ratio is more preferably 16 or more. . Further, in the present invention, the stretching ratio of the primary stretching step (hereinafter, also referred to as longitudinal stretching ratio) and the stretching ratio of the secondary stretching step (hereinafter also referred to as transverse stretching ratio), and the longitudinal stretching ratio of each of the transverse stretching ratios Preferably. The elongation in the longitudinal direction (SMD), the elongation in the width direction (STD), and the thermal elongation in the longitudinal direction (HSMD) and the thermal elongation in the width direction (the longitudinal elongation ratio S). HStd), Control is easy at this point. [Heat-fixing step] In the heat-fixing step, the biaxially stretched polyester film obtained by the second stretching step is thermally fixed to obtain a release film. The temperature condition for heat fixation differs depending on the type of the polyester constituting the polyester film, but is generally (Tg + 7 〇 ). (: above (Tm). (: The following temperature range is preferred. For example, when the polyester is polyethylene terephthalate, it is preferably heat-fixed at a temperature range of from 180 ° C to 235 °. 'When the polyester is polyethylene-2,6-naphthalate, it is preferably heat-fixed at a temperature range of from 185 ° C to 240 ° C. By means of this temperature range, the desired elongation can be obtained. Rate (Smd and STD), thermal elongation (HSMD and HSTD). In addition, 'Tm here indicates the melting point of the vinegar (unit: .). In addition, it is desirable to perform heat fixation not only in the 1 area but also into the plural-area- 23- 200934660 The domain is implemented in stages, preferably at a temperature of three or more. For example, when the heat is fixed in the three regions, the first region is 180 ° C or higher and 210 ° C or lower, and the second region is set higher than the second region. In the first region, it is preferable to set the temperature in the third region to be lower than the temperature in the third region to be 18 ° C or higher and 200 ° C or lower. The maximum temperature is such that the third region is thermally fixed at a temperature lower than this, and is excellently The flatness of the obtained release film can be reduced, and the thickness of the ceramic sheet can be reduced. Further, the heat setting time is not particularly limited, and is preferably, for example, about 1 second to 60 seconds. The thermal elongation (HSTD) in the width direction of the mold film is expected, and in the final region of the heat setting step, the width of the guide rail is reduced to about 2% or more and 5% or less, and the treatment film is preferably relaxed. [Cooling step] ( Any step) The release film of the present invention can be arbitrarily provided with a cooling step after the heat fixing step. By providing a cooling step, the planarity of the obtained release film can be excellently maintained, and the thickness of the ceramic sheet can be reduced. In the cooling step, it is preferred to set the cooling temperature to a range of (Tg - 30) t or more (Tg + 2 0 ) ° C or less, and it is preferable to divide into a plurality of regions in the same manner as the above-described heat-fixing step. When the temperature is lower than the above range, the thermal elongation (HSMD, HSTD) is too small. On the other hand, when the cooling temperature is higher than the above range, even the center line of the long side direction of the film The near-physical properties are uniform in all directions, but the side edges in the longitudinal direction are less likely to be slanted, and the side edges in the long-side direction become inclined. Even at the lower limit side of the above-described range of the heat-fixing temperature, the degree may be small. <Polyester film> [Polyester] The polyester which forms the polyester film used in the present invention may be a homopolymer or a copolymerized polyester. When the polyester film used in the present invention is a homopolyester, it is preferred that the aromatic dicarboxylic acid and the aliphatic diol are polycondensed. In addition, examples of the aromatic dicarboxylic acid to be used include terephthalic acid and 2,6-naphthalene dicarboxylic acid. Further, examples of the aliphatic diol to be used include ethylene glycol, diethylene glycol, and 1,4-cyclohexane dimethanol. The representative polyester of the polyester film used in the present invention may, for example, be polyethylene terephthalate (PET) or polyethylene-2,6-naphthalate (PEN). On the other hand, when the polyester which forms the polyester film used in the present invention is a copolymerized polyester, a dicarboxylic acid and/or a second component which is 20 mol% or less as a third component with respect to the total acid component. The copolymer in which the alcohol is copolymerized is preferred. Examples of the dinonanoic acid which is a monomer component of the copolymerized polyacetate include isophthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid, adipic acid, sebacic acid, and hydroxy acid (for example, P-). One or two or more of these may be used, for example, hydroxybenzoic acid or the like. Further, examples of the diol which is a monomer component of the copolymerized polyester include ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, 1,4- 25-200934660 cyclohexane dimethanol, and neopenta-2. One or two or more of these may be used. As the material of the polyester film used in the present invention, among these, more than 80 mol% or more, preferably 90 mol% or more, is polyethylene terephthalate unit of polyethylene terephthalate. a glycol ester, or 80 mol% or more, preferably 90 mol% or more, of polyethylene-2,6-naphthalenedicarboxylate unit of ethylene-2,6-naphthalenedicarboxylate is preferably Polyethylene terephthalate is particularly preferred. In general, the Tg of polyethylene terephthalate is a low temperature in the vicinity of 78 ° C, so a polyethylene terephthalate film is used as a ceramic treated at a temperature around 1 ° C. When the carrier film for manufacturing a sheet is used, there is no particular problem in dimensional stability in the step. On the other hand, since the release film of the present invention is excellent in dimensional stability, even when it is used at a temperature far exceeding Tg, the performance as a release film can be sufficiently exhibited. [Additive] The polyester which is a material of the polyester film used in the present invention is preferably a blended particle for the purpose of imparting smoothness as a film. The type of the particles to be blended is not particularly limited as long as it can impart smoothness, and specific examples thereof include cerium oxide, calcium carbonate, magnesium carbonate, barium carbonate, and calcium sulfate. Particles such as calcium phosphate, magnesium phosphate, kaolin, alumina, and titanium oxide. In addition, heat-resistant organic particles described in, for example, Japanese Patent Publication No. 59-52166, and JP-A-59-2177755 can be used. Other examples of the heat-resistant -26-200934660 organic particles include a polysoda resin, a thermosetting urea resin, a thermosetting phenol resin, a thermosetting epoxy resin, and a benzoguanamine resin. particle of. Further, in the step of producing the polyester, a part of the metal compound such as a catalyst or a finely dispersed precipitated particle can be used. The shape of the particles for imparting the above-described slipperiness is not particularly limited, and any of a spherical shape, a block shape, a rod shape, and a flat shape can be used. There are no special restrictions on the hardness, specific gravity, color, etc. of this @. Further, these particles may be used in combination of two or more kinds as necessary. Further, the average particle diameter of the particles is preferably Ο. ίμι» or more Ιμιη, and more preferably 0.2 μπι or more and 0.5 μιη or less. When the average particle diameter is lower than Ο.ίμιη, there are cases where the particles are easily aggregated and the dispersibility is insufficient. On the other hand, when it exceeds 1 μm, the surface roughness of the obtained polyester film becomes too coarse, the maximum height (Rmax) of the surface of the release layer of the release film, and the surface of the side having no release layer. It is difficult to have a maximum height (Rmax) of 100 nm or more and 60 0 nm φ or less. In addition, in the polyester film, the content of the particles to be blended with the slipperiness is preferably 质量_〇1% by mass or more and 2% by mass or less, and is preferably 0.01% by mass or more and 1% by mass. /. The following is better. When the content of the particles is less than 0.01% by mass, the slipperiness of the film tends to be insufficient. On the other hand, when it exceeds 2% by mass, the smoothness of the surface of the film tends to be insufficient. The method of containing particles in the polyester film is not particularly limited, but a prior art method can be employed. For example, in the step of producing any of the polyesters, although the particles to be blended may be added, the particles are blended after the end of the esterification step, or after the end of the exchange reaction of the esters -27 to 200934660, and then the polycondensation reaction is preferably carried out. Further, a kneading extruder equipped with a vent may be used to blend a slurry of particles dispersed in ethylene glycol or water with a polyester raw material, or a kneading extruder may be used, by blending The layered structure of the polyester film of the present invention is not particularly limited, and may be a single layer or a laminate. Further, in the case of the lamination configuration, in addition to the two-layer or three-layer configuration, as long as the gist of the present invention is not exceeded, four or more layers may be used. The laminated structure is not particularly limited, and examples thereof include a laminated structure of A/B, A/B/A, A/B/C, A/B/A, and the like. Here, each of A, B, and C represents a layer formed of the above polyester, and may be the same or different. A' particularly indicates a layer formed of a polyester similar in structure to A. [Thickness of the polyester film] The thickness of the entire polyester film of the present invention is not particularly limited, but is preferably 9 μm or more and 50 μm or less, more preferably 15 μm or more and 38 μm or less, and particularly preferably 25 μm or more and 31 μπ 1 or less. <Mold release layer> [Polysilyl oxide resin composition] Since the release layer in the present invention is stable in the form of a latex, the main sand oxide resin composition is preferably formed. Polyoxymethane resin composition -28-200934660, which is a main component comprising at least one of a polyoxyalkylene having at least two unsaturated groups or hydroxyl groups in one molecule, and one molecule A cross-linking agent having at least two hydrogen polyoxyalkylene groups directly bonded to a hydrogen atom of a halogen atom as a constituent component. In the present invention, an aqueous coating liquid (coating agent) containing the composition of the related polyoxyalkylene resin is applied to form a coating film, and the relevant coating film is cured to form a release layer. The polydecane resin composition of the present invention is preferably a water-based polyoxyalkylene tree φ lipid composition. The water-based polyoxyalkylene resin composition is excellent in stability when used as a latex, and as a result, the stability of the coating agent can be improved. Further, the selectivity of the surfactant to be described later is widened, and for example, a surfactant containing more hydroxyl groups can be used to improve the effect of preventing peeling electrification. Further, it is preferable to make it a water-based paint. Further, in the present invention, as a method of curing the polyoxyalkylene resin composition, heat hardening, ultraviolet curing, electron beam hardening, etc. may be mentioned, and among them, thermal hardening is preferred, that is, it is composed of a polyoxyalkylene resin. Preferably, the composition of φ thermosetting polyoxyalkylene resin is preferred. In the present invention, as described above, a polyester film having a coating film is obtained in the in-line coating step, and heat treatment is performed in the subsequent heat fixing step. The composition of the polyoxyalkylene resin is a thermosetting polyoxyalkylene resin composition, and in the related heat setting step, the crosslinking reaction is promoted by heat treatment, and the composition of the polyoxyalkylene resin can be sufficiently performed. The hardening' can obtain a release layer having excellent characteristics such as excellent mold release property. In the above, the composition of the polyoxysiloxane resin in the present invention is particularly preferably a water-based thermosetting polyoxyalkylene resin composition. Further, the meaning of "mainly" in the above-mentioned -29-200934660 means that the mass% or more is formed of a polyoxyalkylene resin composition with respect to the weight of the release layer. The polydecane oxide resin composition may be an addition polymerization type (a condensation type formed from a polyoxyalkylene having at least two unsaturated groups in one molecule (the main agent system has at least two hydroxyl groups in one molecule) In the case of the addition polymerization, it is preferred that the additive is a catalyst, and when it is a condensation type, it is preferable that the coating agent contains a catalyst as a catalyst. In view of the above, it is preferred that the additive is used. Further, the crosslinking agent is preferably one which can be used by the manufacturer used at the same time. Hereinafter, the water-based thermosetting oxyalkylene resin which is applicable to the present invention is listed. Specific examples of the composition 1) Wacker Silicone (Michigan, A dria η) 40 0E polyoxyalkylene resin composition containing polyoxane, lead and methyl hydrogen polyoxyalkylene V20 crosslinker system. 2) The water of Dow Corning (Midland, Midland) is afraid of the 7 72 0 polyoxyalkylene resin composition, which is composed of X2-772 1 crosslinker containing methyl vinyl poly sand and platinum polyoxyalkylene. Made from methylhydroalkane. 3) PCL (Phone-Poulenc Inc., Hill, South Carolina) aqueous PC-1 05 polyoxyalkylene resin composition consisting of vinyl-containing polyoxane and uranium polyoxyalkylene The PC-95 is formed by the methyl hydrogen polyoxyalkylene. 4) PCL PC-107 waterborne polyoxyalkylene resin composition (from 75 main agent system) and oxime oxide containing tin-polymerized main-agent polyhydric aqueous catalyst, : X2-oxygen The alkane, polyoxynium, and rock have a methyl catalyst to be similar to PC-200934660 105, and contain the above-mentioned PC-95 crosslinking agent. 5) PCL PC-188 aqueous polyoxyalkylene resin composition (similar to pc-105) containing the above PC-95 crosslinking agent. Further, the water-based thermosetting polyoxyalkylene resin composition can be used as a coating agent by appropriately adjusting the solid content concentration by adding deionized water or the like. [Centane coupling agent] Further, the release layer of the present invention preferably contains a decane coupling agent. As the decane coupling agent, any one of a polyester resin and a polyoxymethane resin composition, or an organic hydrazine low molecular compound having a reactive group bonded to both of them, as the related reactive group, having a methoxy group At least one organic hydrazine low molecular compound having at least one of a group, an ethoxy group, a stanol group, a vinyl group, an epoxy group, a (meth) propylene group, an amine group, a thiol group, a chloro group, a hydroxyl group, and a carboxyl group good. The content of the related decane coupling agent is preferably 〇·1% by mass or more and 20% by mass based on the solid content of the release layer, and more preferably 1% by mass or more and 1% by mass or less, and more preferably 3% by mass or more. The mass % or less is particularly good. By setting the content to the above range, the adhesion of the release layer can be improved. [Interacting Agent] The release layer of the present invention preferably contains 0.5% by mass or more and 10% by mass or less of the surfactant, based on the solid content of the release layer. The release layer can suppress the peeling electrification when the roll-shaped release film is rolled out and the peeling electrification when peeling off the ceramic sheet from the release film by the surfactant containing the amount in the range of the above-mentioned number. Further, when the laminated ceramic capacitor is manufactured, the positional deviation of the internal electrodes can be suppressed. Further, in the coating agent, by adding a surfactant, the wettability with respect to the coating agent on the surface of the polyester film is excellent, and as a result, the local elastic opening disadvantage of the coating agent is suppressed, and not only uniform coating can be obtained. The film can also suppress pinhole defects that occur when the ceramic sheet is peeled off. From such a viewpoint, the content of the surfactant is more preferably 1.0% by mass or more and 7.0% by mass or less, and particularly preferably 2.0% by mass or more and 5.0% by mass or less based on the total dry weight of the release layer. When the content is less than 0.5% by mass, the peeling electrification becomes high. Further, the wettability of the coating agent tends to be insufficient with respect to the surface of the polyester film. On the other hand, when it exceeds 10% by mass, the peeling force with respect to the ceramic sheet tends to become heavy peeling, which is less preferable. Examples of the surfactant include an ion-based surfactant (an anionic surfactant, a cationic surfactant, and a zwitterionic surfactant) and a nonionic surfactant, in which a nonionic surfactant is used. A surfactant is preferred. When an ionic surfactant such as an anionic surfactant, a cationic surfactant or a zwitterionic surfactant is used, these surfactants are used with respect to the polyoxyalkylene resin composition for forming the release layer. In the case of catalyst poisoning, the polyoxyalkylene resin composition may not be sufficiently cured. Examples of the nonionic surfactant include a surfactant such as a polyoxyethylene type, a polyhydric alcohol fatty acid ester type, a polyhydric alcohol alkyl ether type, and a nitrogen-containing type, and a nonionic polyoxyalkylene-based interfacial activity. Agent, non-ionic fluorine-32-200934660 is a surfactant. Examples of the polyoxyethylene type surfactant include poly(ethylene oxide) alkyl ether, poly(ethylene oxide) alkylphenyl ether, poly(ethylene oxide) poly(oxypropylene) alkyl ether, and poly(ethylene oxide). Fatty acid ester, poly(ethylene oxide) sorbitan fatty acid ester, and the like. Among them, as the poly(ethylene oxide) alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyethylene oxide stearyl ether, polyethylene oxide are preferable. A poly(ethylene oxide) alkyl ether having an alkyl group having 12 or more carbon atoms such as oleyl ether. The related alkyl group may be linear or branched. Examples of the polyol fatty acid ester type surfactant include propylene glycol fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, and sucrose fatty acid ester. Examples of the polyol alkyl ether type surfactant include alkyl polyglucosides and the like. The nitrogen-containing surfactant may, for example, be an alkyldiethanolamine or an alkylamine oxide. Examples of the polyoxyalkylene-based surfactant include a polyether modified polysiloxane, a polyglycerin modified polyoxyalkylene, and the like. Further, as the structure of the related modified polyoxyalkylene, it is classified into a side chain deformable type, a two-end modified type (ABA type), a single-end modified type (ΑΒ type), and a two-terminal side chain modified type. A linear block type (ΑΒη type), a branched type, or the like, but may be any structure. Further, as the surfactant of the present invention, a polyoxyethylene type surfactant and a polyoxyalkylene type surfactant are preferable. These are less likely to become catalogue poisons of the polyoxyalkylene resin composition, and further exhibit sufficient wettability. It is particularly preferable to use a polyoxyalkylene-based surfactant, and it is more difficult to become -33-200934660 Catalytic toxicity, which is superior to the release model, and further improves the peeling electrification prevention effect. Further, the thickness of the release layer of the present invention (i.e., the thickness after drying) is not particularly limited, but is preferably 20 nm or more and 90 nm or less. In general, when it is less than 20 nm, it is difficult to exhibit a light release force or the like as a release layer. On the other hand, when it exceeds 9 Onm, the cost is high, but the effect obtained is rather small. <Application of Release Film> The release film of the present invention can be used as a film for sheet molding such as a resin sheet or a ceramic sheet, or as a separator for an adhesive film for labels, medical, and business articles. . In particular, the release film of the present invention is suitably used as a carrier film for the production of a ceramic sheet because it sufficiently satisfies the properties required for the release film during the production of the ceramic sheet. When the ceramic sheet is produced by using the release film of the present invention, the ceramic sheet of the film can be obtained with high precision, and the obtained ceramic sheet of the film can be applied to multilayering of internal electrodes in accordance with miniaturization and large capacity. Laminated ceramic capacitors. Further, in the production of the ceramic sheet, the prepared ceramic slurry is applied onto the surface of the release layer of the release film of the present invention, and the solvent contained in the ceramic slurry can be dried and removed. Further, as a coating method of the ceramic slurry, there is no particular limitation, and a coating method of the prior art can be used. For example, a method in which a ceramic powder, a binder, or the like is dispersed in a solvent of a ceramic slurry by a reverse roll method and a solvent is removed by heat drying can be used. The adhesive-34-200934660 mixture used is not particularly limited. For example, polyvinyl butyral or the like can be used. Further, the solvent to be used is not particularly limited, and for example, ethanol, toluene or the like can be used. <Film Roller> The film roll of the present invention has the above-mentioned release film taken up in a roll shape. The release film roll may be a mother roll directly obtained by the above-described production step of the release film @, or may be a slit roll which is cut into a width and a length required by the customer by the related mother roll. In the film roll of the present invention, the Vickers hardness (Hv) of the surface layer of the roll is 0 or more and 450 or less. By setting the Vickers hardness (Hv) of the surface layer of the roll to the above range, a release film excellent in flatness can be obtained. Further, in the release film roll, winding offset or wrinkles are less likely to occur. Vickers hardness, using a diamond apex head with a face angle of 136 degrees, will load the crucible pits in the test face, divided by the surface area calculated from the length of the permanent φ pit diagonal The quotient is calculated by the following formula. Ην = (2 · Ρ · sin(a/2))/d2 P: load (kg), d: average of the length of the diagonal of the pothole (mm), a: the opposite angle is a = 136 degrees, so The above formula is as follows. -35- 200934660
Hv=l ,854xP/d2 一般而言，將薄膜捲成滾筒狀，則薄膜厚度爲厚的部 分，隨著捲取徑增大而捲緊，會有成爲所謂帶狀缺點的情 況。該相關的部分中，造成薄膜伸長，薄膜的平坦性受 損。此傾向，係隨著滾筒表層的維氏硬度（Hv)變高而變 得更顯著。亦即，滾筒表層的維氏硬度（Ην )超過450 時，捲得太緊，而成爲薄膜的伸長太大，薄膜的平坦性亦 劣者。由如此的觀點而言，滾筒表層的維氏硬度（Ην)的 上限，較佳爲430以下，更佳爲420以下，特別佳爲410 以下。另一方面，滾筒表層的維氏硬度（Ην)太低時，會 有變得易產生捲取偏移的傾向，但在不會產生如此問題下 愈低愈好。由如此的觀點而言，滾筒表層的維氏硬度 (Ην)的下限，較佳爲340以上，更佳爲360以上，特別 佳爲3 80以上。 如上述的滾筒表層的維氏硬度（Ην)，可藉由捲取脫 模薄膜時捲取張力或隙壓（nip pressure )等之捲取條件而 達成。 作爲捲取張力，必須使初期張力爲49N/m以下。藉由 使初期張力爲上述數値範圍，可使滾筒表層的維氏硬度 (Ην)爲450以下。此外，捲取中之捲入空氣量爲適度的 量，可降低薄膜的厚度斑的影響，亦即可抑制捲緊，平坦 性更優異，此外可抑制捲取偏移。初期張力太高時，會有 滾筒表層的維氏硬度（Ην)變太高的傾向。此外，會有捲 200934660 取中之捲入空氣量變少的傾向，而會有平坦性差的傾向。 由如此的觀點而言，初期張力的上限，較佳爲48N/m以 下，更佳爲47N/m以下。另一方面，初期張力降過低時， 會有捲取變不安定，薄膜易變成蛇行的傾向，會有滾筒端 面變得不整齊，皺褶發生，切割變不良之傾向，但在不會 產生此等的問題下愈低愈好。由如此的觀點而言，初期張 力的下限，較佳爲30N/m以上。再者，該相關的初期張 φ 力’係表示將實質上成爲製品之脫模薄膜開始捲成滾筒狀 時的張力’並非一定表示開始捲於卷芯後的張力。亦即， 一般而言，爲了減少卷芯表面的異物或傷等的影響之目 的，使用令開始捲於卷芯後直到數m乃至數十m的長度 爲止的捲取張力特別高之手法’並非表示如此部分中之捲 取張力。 此外，施加張力錐度（tension taper )，必須對於初 期張力降低最後張力。具體而言，必須使相封於初期張力 φ 之最後張力的比率（張力錐度率）爲80%以下。藉由使張 力錐度率在上述數値範圍’可在降低滾筒表層的維氏硬度 (Hv)下，抑制捲取偏移。張力錐度率太高時，會有滾筒 表層的維氏硬度（Ην)變太高的傾向。由如此的觀點而 言’張力錐度率的上限’較佳爲70%以下，更佳爲6〇%以 下。另一方面，由滾筒硬度的觀點而言，張力錐度率低較 佳，但張力錐度率太低時，最後張力變太低，會有變得易 產生滾筒端面偏移等之問題的傾向。由如此的觀點而言， 張力錐度率的下限’較佳爲30 %以上。本發明中，從初期 -37- 200934660 張力至最後張力爲止之間，只要在捲取張力不超過4 9N/m ，亦可有捲取張力増加的部分，於滾筒的主要部分中，以 使捲取張力連續地漸減之形態較佳，以一定的比例使其連 續地漸減之形態較佳。藉由使張力錐度成爲如上述的形 態，於滾筒中，可使捲取方向的内部應力經常爲0以上， 可抑制橫方向的折皺狀缺點（T-B AR )或間隙等之不佳狀 況。再者，其中，滾筒之主要部分，係表示於滾筒徑方 向，距離卷芯的表層爲5mm以上外側，且距離滾筒的表 層爲5mm以上内側的部分。 由如上述的初期張力及張力錐度率而言，最後張力必 須爲39N/m以下。藉由使最後張力在上述數値範圍，可使 滾筒表層的維氏硬度（Hv)爲450以下。最後張力太高 時，會有滾筒表層的維氏硬度（Ην)變太高的傾向。由如 此的觀點而言，最後張力的上限，較佳爲3 8N/m以下，更 佳爲30N/m以下。另一方面，由滾筒硬度的觀點而言，最 後張力低較佳，但最後張力太低時，會有捲取變不安定， 薄膜變得易蛇行的傾向，會有滾筒端面偏移等之問題易產 生的傾向。由如此的觀點而言，最後張力的下限，較佳爲 ΙΟΝ/m以上，更佳爲15N/m以上。 隙壓，必須使初期隙壓爲20 ON/m以下。藉由使初期 隙壓在上述數値範圍，可使滾筒表層的維氏硬度（Hv)爲 450以下。此外，捲取中之捲入空氣量成爲適度量，可降 低薄膜的厚度斑的影響，亦即可抑制捲緊，平坦性更優 異，此外可抑制捲取偏移。初期隙壓太高時，會有滾筒表 -38- 200934660 層的維氏硬度（Hv)變太高的傾向。此外，會有捲取中之 捲入空氣量變少的傾向，而會有平坦性差的傾向。由如此 的觀點而言，初期隙壓的上限，較佳爲1 8 ON/m以下，更 佳爲160N/m以下，特別佳爲uON/m以下。另一方面， 初期隙壓太低時’會有捲取變不安定的傾向，會有捲取偏 移或皺褶變得易發生的傾向。由如此的觀點而言，初期隙 壓的下限，較佳爲50N/m以上，更佳爲80N/m以上。 φ 此外’隙壓錐度，不增添亦可，但藉由以-；! 0%以上 1 以下的隙壓錐度率增添隙壓錐度，可抑制皺褶或疙瘩 的發生、滾筒的端面偏移。 由如上述的初期隙壓及隙壓錐度率，最終隙壓爲 220N/m以下即可’但最終隙壓太高時，會有滾筒表層的 維氏硬度（Hv)變太高的傾向。由如此的觀點而言，最終 隙壓的上限’較佳爲170N/m以下，更佳爲150Ν/ιη以 下’特別佳爲140N/m以下。另一方面，最終隙壓太低 φ 時’會有捲取變不安定的傾向。由如此的觀點而言，最終 隙壓的下限，較佳爲50N/m以上，更佳爲70N/m以上， 特別佳爲90N/m以上。 【實施方式】 實施例 以下’列舉實施例及比較例更具體地說明本發明，但 本發明只要未超越其要旨，並不限定於此等。 -39- 200934660 <測量•評估方法> 實施例及比較例中，關於以下的項目’藉由以下的方 法實施各測量•評估。 (1 )粒子的平均粒徑 使用島津製作所製、商品名：CP-5〇型離心式粒度分 析器（Centrifugal Particle Size Analyzer)進行測量。由 以藉由測量所得到的離心沈降曲線爲基礎所算出的各粒徑 的粒子、與其存在量的累積曲線，讀取相當於50質量百 分比的粒徑之「等價球直徑」，將此値作爲粒子的平均粒 徑（單位：μιη ) ( Book「粒度測量技術」日刊工業新聞 發行、1 975年、頁242〜頁247參照）。 (2 )最大高度（Rmax ) 依據 JIS規格（B0601 :表面粗度-定義及表示、 B065 1 :觸針表面粗度測量器），藉由3次元表面粗度計 (小坂硏究所公司製、商品名：SE-3 AK )，以倍率：2萬 倍、掃描間距：2μιη、掃描長度：1mm、掃描條數：1〇〇 條、截止（cut-off) : 0.25mm的條件，計算得到其面積 的最大高度，測量1〇處的結果的平均値作爲Rmax (單 位：nm ) ° (3)載重下的伸長率（Smd、Std) 使用 TMA ( Seiko Instruments (股）製、商品名 -40- 200934660 SS6000 )，於濕度：50%RH下，以試樣寬度：4mm、夾頭 (chuck )間距：20mm，於長邊方向施加每單位面積各爲 0.3MPa、l.OMPa、2.5MPa 的載重，從開始溫度：30°C， 以昇溫速度：l〇°C/分鐘使其昇溫，從達到100°C時的薄膜 的伸縮舉動，以下述式計算得到於 0.3 MPa、1.0MP a、 2.5MPa的各載重條件下的伸長率（SMD )(單位：％ )。 同樣於寬度方向施加〇·〇1 MPa的載重實施測量，計算得到 φ 於該相關的載重條件下之伸長率（STD )(單位：％ )。再 者，伸長率（SMD、STD )，係對各10片的試料測量，計 算其平均値。 伸長率（Smd、Std) = (AM/M〇)x100 (%) ΔΜ = Μ-Μ〇 上述式中’ Μ〇表示熱處理前的薄膜的長邊方向或寬 φ 度方向的長度’ Μ表示熱處理後的薄膜的同方向的長度。 亦即，伸長率（SMD )及伸長率（STD)，負時表示薄膜收 縮，正時表示薄膜伸長。 (4)無載重下的熱伸長率（HSmd、HStd) 在被設定於溫度100°(：的烘箱中’懸垂預先測量正確 的長度之長度約30cm四方的薄膜試樣’在無載重下進行 3〇分鐘保持處理。30分鐘經過後’從烘箱取出薄膜試 樣，回復至室溫後’測量其尺寸變化’以下述式計算得到 -41 - 200934660 熱伸長率（HSmd、HStd )(單位：％ )。再者，伸長率 (HSMD、HSTD)，係對10片的試料各自採集數據，計算 其平均値。 熱伸長率（HSmd、HStd) = (AL/L〇)x100 (%) Δ L = L - L 〇 上述式中，LQ表示熱處理前的薄膜的長邊方向或寬度 方向的長度，L表示熱處理後的薄膜的同方向的長度。亦 即，熱伸長率（HSMD )及熱伸長率（HSTD ) 、負時表 示薄膜收縮，正時表示薄膜伸長。 (5)陶瓷片的表面平滑性評估（實用特性代用評估） (條件1 )於脫模薄膜的脫模層側之面，將由下述組 成所成的陶瓷淤漿用擠壓式塗佈（die coater)塗佈，形成 乾燥後的厚度成爲5 μιη之陶瓷層，捲取2 00m。 (條件2 )準備寬度450mm、長度2,000m的脫模薄 膜的滾筒。於該相關的脫模薄膜之脫模層側的表面，將由 下述組成所成的陶瓷淤漿，使用擠壓式塗佈，以60m/分 鐘的薄膜搬運速度進行塗佈，形成乾燥後的厚度成爲5 μιιι 的陶瓷層，得到長度l，9〇〇m的陶瓷層/脫模薄膜複合體， 捲成滾筒狀。 然後，由條件1及2所得到的陶瓷層/脫模薄膜複合 體中，藉由從脫模薄膜剝離陶瓷層而得到陶瓷片。對於所 -42- 200934660 得到的陶瓷片（測量對象面積：1 m2 )的兩面，使用掃描 型雷射顯微鏡（LASERTEC公司製）進行表面觀察，依下 述的評估基準實施表面平滑性的評估。 [陶瓷淤漿組成] •鈦酸鋇（富士鈦公司製、平均粒徑：〇.7μιη) ： 1〇〇 份 φ ·聚乙烯丁縮醛樹脂（積水化學公司製、商品名：8- LEC BM-S ) : 30 份 •可塑劑（苯二甲酸二辛酯）·· 5份 •甲苯/乙醇混合溶劑（混合比率：6 : 4 ) : 200份 [表面平滑性評估基準] 〇：深度〇·5μιη以上的陷坑（凹陷）爲2個/m2以下 (實用上，無問題的程度） ❹ △:深度〇·5μιη以上的陷坑（凹陷）爲超過2個/m2 低於6個/m2 (實用上，會有成爲問題之情況的程度） X :深度0.5 μηα以上的陷坑（凹陷）爲6個/m2以上 (實用上，無問題的程度） (6)脫模薄膜的剝離帶電評估 實施上述（5 )(條件2 )的評估時，測量捲出脫模薄 膜的滾筒時的剝離帶電量。距離從滾筒剛捲出的後的脫模 -43- 200934660 薄膜表面（滾筒中’捲取内側的表面），在垂直上方之距 離5cm的位置，設置集中電位測量器（春日電機（股） 製、商品名：靜電電位測量器S V -1 0 )，於溫度：2 2。(：、 濕度：44%RH的氣體環境下測量剝離帶電量。捲出脫模薄 膜的滾筒的全長2,000m之間，每i〇〇m，測量至少15處 剝離帶電量’將此等的平均値作爲脫模薄膜的剝離帶電量 (單位：kV)。或’藉由下述的評估基準實施評估。 [脫模薄膜剝離帶電評估基準] 〇：剝離帶電量爲2. OkV以下（剝離帶電良好） X:剝離帶電量超過2.0kV (剝離帶電不良） (7 )陶瓷片的剝離帶電評估 用與上述（5)(條件2)同樣的方法，得到陶瓷層/ 脫模薄膜複合體。於所得到的陶瓷層/脫模薄膜複合體的 陶瓷層的表面，藉由網版印刷法，形成膜乾燥後的厚度爲 3 μπι之經圖型化的Ni電極印刷層，作爲金屬。接著，將 所得到的金屬膜/陶瓷層/脫模薄膜複合體，裁剪成3 00mm X 3 0 Omm的大小，得到片狀的試樣。關於所得到的片狀的 試樣，以20m/分鐘的剝離速度’從脫模薄膜剝離金屬膜/ 陶瓷層複合體，測量該相關的剝離之剝離帶電量。經剝離 的金屬膜/陶瓷層複合體之距離陶瓷層的表面爲5cm的位 置，設置集中電位測量器（春日電機（股）製、商品名： 靜電電位測量器S V -1 0 )，於溫度：2 2 °C、濕度：4 4 % R Η 200934660 的氣體環境下測量剝離帶電量。測量係對片狀的試樣100 片實施，此等的平均値作爲陶瓷片的剝離帶電量（單位： kV )，或，藉由下述的評估基準實施評估。 [陶瓷片剝離帶電評估基準] 〇：剝離帶電量爲20kV以下（剝離帶電良好） X:剝離帶電量爲超過2 0kV (剝離帶電不良） ❹ (8)陶瓷片的剝離評估 關於上述（7)中片狀的試樣，從脫模薄膜剝離金屬 膜/陶瓷層複合體時’該相關的剝離的狀況藉由下述的評 估基準實施評估。 [剝離評估基準] ◎:剝離力適度，金屬膜/陶瓷層未斷裂，未看到陶瓷 0 層的殘存於脫模薄膜（實用上完全無問題的程度） 〇：剝離力稍重，或金屬膜/陶瓷層看到稍微的斷 裂，或看到陶瓷層的稍微殘存於脫模薄膜（實用上完全無 問題的程度） X:剝離力過重’金屬膜/陶瓷層看到斷裂，看到陶瓷 層的殘存於脫模薄膜（實用上有問題的程度） (9-1)陶瓷片的層合評估i (實用特性代用評估） 於上述（5 )(條件1 )所得到的陶瓷片的上，層合經 -45- 200934660 圖型印刷的Ni電極印刷層（乾燥後的厚度爲3 μιη )。使 用所得到的陶瓷片/電極層合體，以單側的端部爲基準層 合10層，對於此時的電極印刷層的位置偏移的程度，藉 由下述的評估基準實施位置偏移評估。 [位置偏移評估基準] ◎:位置偏移爲低於200μιη (實用上完全無問題的程 度） 〇：位置偏移爲200μηι以上且低於400μιη (實用上無 問題的程度） X:位置偏移爲400μιη以上（實用上有問題的程度） (9-2 )陶瓷片的層合評估2 (實用特性代用評估） 將用與上述（7)同樣的方法所得到之裁剪及剝離後 的金屬膜/陶瓷層複合體，使用藉由CCD相機檢測出位置 之方式的叠膜機層合層，得到層合體。關於所得到的 層合體，以第1層的金屬膜/陶瓷層複合體作爲基準’各 層的偏移量，用顯微鏡測量’所得到的値作爲位置偏移 (單位：μπι)。評估係藉由下述的評估基準實施。再者’ 層合係剝離脫模薄膜後，馬上實施° [位置偏移評估基準] ◎:位置偏移爲低於(實用上完全無問題的程 200934660 〇：位置偏移爲200μιη以上且低於400μιη (實用上無 問題的程度） X :位置偏移爲400 μιη以上（實用上有問題的程度） (1〇)滾筒表層的維氏硬度（Ην) 依據JIS Ζ2244 ( 1961)的手法用以下的方法測量。 測量係於實施例所得到的脫模薄膜滾筒的表層，去除距離 φ 端面5mm的部分，在寬度方向測量1〇處，將最大値作爲 滾筒表層的維氏硬度（Ην)。 (Π )捲取偏移 關於於實施例所得到的脫模薄膜滾筒，端面的捲取偏 移的狀況，藉由下述的評估基準進行評估。 [捲取偏移評估基準] 0 ◎:捲取偏移爲1 mm以下（可完全無問題地適切地使 用之程度） 〇：捲取偏移爲超過1mm且2mm以下（可無問題地 使用之程度） △:捲取偏移爲超過2mm且3mm以下（有稍微的問 題但可使用之程度） X:捲取偏移爲超過3mm (有問題而無法使用之程 度） -47- 200934660 (1 2 )平坦性 從脫模薄膜滾筒，採集長度2m的薄膜試樣，捲於滾 筒時使滾筒的表面側之側往上，水平地攤開在平坦的台 上。10分靜置後，觀察薄膜試樣的全表面，測量殘留於該 表面之皴褶（flute、薄膜浮出高於上述台的部分）的長度 (單位：cm )，將合計除以測量面積（單位：m2 )而算出 平坦度（單位：cm/m2 )。平坦性的評估，藉由下述的評 估基準實施。 [平坦性評估基準] ◎:平坦度爲28cm/m2以下（實用上完全無問題的程 度） 〇：平坦度爲超過28cm/m2、33cm/m2以下（實用上 無問題的程度） X :平坦度爲超過33cm/m2 (實用上有問題的程度） (13 )薄膜的厚度斑 使用測微計（Anritsu (股）製、商品名「K-402B」 型），於薄膜的縱方向以1 Ocin間隔測量1 〇處，該相關的 縱方向1 〇處的測量，係於橫方向以1 〇cm間隔測量1 0 列、全部爲1 00處的薄膜厚度，計算出所得到的1 〇〇處的 薄膜厚度的平均値作爲薄膜厚度（單位：Pm) ° 接著，使用電子測微計（Anritsu (股）製、商品名 「K-312A」型，以針壓30g、進行速度25mm/秒，於薄膜 200934660 的縱方向lm、橫方向4 5 0mm的長度範圍進行測量，得到 連續厚度圖表。從所得到的圖表，讀取縱方向、橫方向各 自的最大厚度（單位：μη!)與最小厚度（單位：μιη)， 配合上述的薄膜厚度，由下述式計算得到厚度斑（單位： % )。 厚度斑（％) = ((最大厚度-最小厚度）/薄膜厚度）χ 1〇〇 i ( 1 4 )陶瓷片的厚度斑 ❹ 對於用上述（5 )(條件2 )所得到的陶瓷層/脫模薄 膜複合體，使用測微計（Anritsu (股）製、商品名「K-402B」型）測量厚度，接著完全地剝離經測量厚度之處的 陶瓷層，於同一處所中再度測量厚度，將此等相差的數値 當作陶瓷片厚度而計算。該相關的操作，係於縱方向以 1 m間隔測量1 〇處，該相關的縱方向1 〇處的測量，係於 橫方向以1cm間隔測量10列、全部爲100處的薄膜實 φ 施，將所得到的1〇〇處的陶瓷片厚度的平均値作爲陶瓷片 厚度（單位：μιη )。 接著，上述100處的測量中，最大者作爲最大厚度 (單位：μιη )、最小者作爲最小厚度（單位：μπι ) ’由 下述式計算得到厚度斑（單位：％) ° 厚度斑（％) = ((最大厚度-最小厚度）/陶瓷片厚度）χ10〇 評估係藉由下述的評估基準實施。 -49- 200934660 [厚度斑評估基準] ◎:厚度斑爲2.0%以下（厚度斑非常優異’實用上完 全無問題的程度） 〇：厚度斑爲超過2.0°/。、3.0%以下（厚度斑優異， 實用上無問題的程度） X:厚度斑爲超過3.0% (厚度斑差’實用上有問題的 實施例1 [聚酯的製造] 於對苯二甲酸甲二醇酯100份與乙二醇7〇份之混合 物中，添加作爲酯交換觸媒之乙酸錳· 4水鹽’使所得到 的聚酯中之錳的元素量成爲80ppm，一邊將内溫從150°C 慢慢地提高一邊進行酯交換反應。在酯交換反應變成95% 時，添加作爲安定劑之亞磷酸〇·〇1份，充分攪拌後，添 加三氧化銻0.03份。接著’於混入系統内的水充分地蒸 餾出後，添加作爲内添塡充劑（易滑劑）之平均粒徑 0.6μηι的合成碳酸鈣粒子，使其相對於所得到的聚酯的質 量成爲0.2質量％，充分地攪拌。接著，將反應生成物移 至聚合反應器，藉由於高溫真空下（最終内溫295 〇C )進 行聚縮合’得到固有黏度0.65(35 °C、鄰氯酣中）的聚對 苯二甲酸乙二醇酯組成物。 -50- 200934660 [塗劑的調製] 藉由於88.5份的脫離子水、10份的聚矽氧烷乳膠 400E ( Wacker Silicones公司製、添加具有聚矽氧烷：乙 烯基之甲基聚矽氧烷、交聯劑時，倂用用於防止與鉑觸媒 之早熟的反應之禁止劑）、1份的交聯劑V72 ( Wacker Silicones公司製、甲基氫聚矽氧烷之乳膠，於甲基矽氧烷 之中與雙鍵反應）中，添加0.5份的矽烷偶合劑（信越聚 _ 矽氧烷公司製、商品名：KB Μ-4 03 )而得到塗劑。再者， 固形分重量爲5質量％。 [未延伸聚酯薄膜成形步驟] 將上述所得到的聚對苯二甲酸乙二醇酯組成物，以 170 °C乾燥5小時，使聚合物的水分率成爲0.05質量％爲 止。接著，將經乾燥的聚對苯二甲酸乙二醇酯組成物供給 至擠壓機’以熔融溫度2 80〜3 00°C進行熔融擠壓’使用平 0 均網目大小Ιίμιη的鋼線過滅器進行高精度過'濾後’使用 擠壓模具，藉由用靜電密著法使其接觸冷卻轉筒令其急 冷，得到厚度450μιη的未延伸聚酯薄膜。 [一次延伸步驟] 將所得到的未延伸聚酯薄膜，以75 °C預熱’接著’於 低速·高速的滾筒之間以薄膜溫度在長邊方向延伸 3.6倍，然後，藉由急冷而得到長邊方向（縱方向）延伸 聚酯薄膜 -51 - 200934660 [線上塗佈步驟] 接著，於所得到的長邊方向延伸聚酯薄膜，塗佈上述 所調製的塗劑，使乾燥後的厚度成爲40nm，得到具有塗 膜之聚酯薄膜。 [二次延伸步驟] 接著，將所得到之具有塗膜的聚酯薄膜供給定型機 (ST ENTER)，於105 °C、115 °C的2區域中，各自預備加 熱 2 秒後，於 1 2 0 °C、1 3 0 °C、1 4 5 °C、1 5 5 °C 的 4 區域中， 各自均勻地延伸2秒，合計爲垂直於長邊方向的方向（寬 度方向）的延伸倍率（橫延伸倍率）成爲4.1倍，製成二 軸延伸聚酯薄膜。 [熱固定步驟] 針對所得到的二軸延伸聚酯薄膜，於210°C、225 t、 195 °C的3區域，實施各自2秒、合計6秒的熱固定，於 最後的195 °C的熱固定區域，藉由於長邊方向與垂直的方 向（寬度方向）實施2.5%的弛緩處理，得到全厚度31μηι 的脫模薄膜。使用所得到的脫模薄膜，進行各種的測量· 評估。結果列示於表1。 實施例2 於二次延伸步驟，除了使垂直於長邊方向的方向（寬 -52- 200934660 度方向）的延伸倍率爲4.5倍，熱固定步驟的第3區域中 之弛緩量爲4.0 %以外，與實施例1同樣作法而得到脫模 薄膜。使用所得到的脫模薄膜，進行各種的測量·評估的 結果列示於表1。 比較例1 於脫模薄膜的製造中，除了不以線上塗佈由水系的熱 _ 硬化型聚矽氧烷組成物所成的脫模劑塗液以外，與實施例 1同樣作法，得到不具有脫模層的二軸延伸聚酯薄膜。 此外，於加成型聚矽氧烷系化合物（東芝聚矽氧烷公 司製、商品名：TPR-6721)的甲苯溶液（固形分濃度：3 質量％ )中，加入Pt觸媒（東芝聚矽氧烷公司製、商品 名：CM670 )，使其相對於加成型聚矽氧烷型化合物的固 形分1 〇〇質量份成爲1質量份，調製脫模劑塗液。 接著，將上述所得到之不具有脫模層的二軸延伸聚酯 φ 薄膜滾筒捲出，被捲出的二軸延伸聚酯薄膜之垂直於長邊 方向的方向（寬度方向）中之中央部上，塗佈上述之經調 整的脫模劑塗液，使塗佈量爲（wet ) 6g/m2，使用下方及 上方的空氣流吹出口的間隔各自爲38cm的空氣浮上搬運 式乾燥裝置，以搬運張力：2,000kPa、乾燥溫度：160°C使 其乾燥1 6秒而形成脫模層，得到脫模層的乾燥硬化後的 重量爲0.2g/m2的脫模薄膜。使用所得到的脫模薄膜，進 行各種的測量•評估的結果列示於表1。 -53- 200934660 比較例2 於一次延伸步驟中，除了使長邊方向（縱方向）的延 伸倍率爲3 . 〇倍以外，與實施例i同樣作法，得到脫模薄 膜。使用所得到的脫模薄膜，進行各種的測量•評估的結 果列不於表1。 比較例3 除了於一次延伸步驟中除了長邊方向（縱方向）的延 伸倍率爲4,8倍，於二次延伸步驟中垂直於長邊方向的方 向（寬度方向）的延伸倍率爲3.0倍以外，與實施例1同 #作法而得到脫模薄膜。使用所得到的脫模薄膜，進行各 種的測量•評估的結果列示於表i。 -54- 200934660 ο❹ 比較例3 -0.48 -0.38 ο ( Ο in ο 〇 寸 〇 jrj 465 X 〇 比較例2 (Ν 〇 -0.14 0.05 -0.62 Ο 卜 〇 VsD 〇 440 450 X 〇 [比較例1 -0.05 0.02 0.13 Ο -0.05 〇 -0.05 <N 464 X 〇 實施例2 -0.28 -0.19 -0.08 -0.43 -0.18 〇 0.32 OO 455 ◎ 〇 :實施例1 -0.31 -0.24 ί-Η Ο -0.39 CN| ο 寸 〇 CN 〇 o 460 ◎ 〇 i i 載重0.3MPa 載重l.OMPa 載重2.5MPa 載重 0.01 MPa 1 無載重 無載重 MD-TD 脫模層表面 不具有脫模層之側 位置偏移 (層合評估1) 表面平滑性 (條件1) 伸長率(Smd) 伸長率(Std) 熱伸長率(hsmd) 熱伸長率(hstd) HSmd-HStd Rmax 陶瓷片評估 -55- 200934660 實施例3 [聚酯的製造] 與實施例1同樣作法，得到固有黏度〇 6 5 ( 3 5 <=c、鄰 氯S&中）的聚對苯二甲酸乙二醇酯組成物。 [塗劑的調製] 藉由於87份的脫離子水中，攪拌下，添加作爲主劑 之10份的聚矽氧烷乳膠400E(Wacker Silicones公司 製、添加具有聚矽氧烷：乙烯基之甲基聚矽氧烷、交聯劑 時，倂用用於防止與鉛觸媒之早熟的反應之禁止劑，固形 分濃度50質量％)、1份的交聯劑V72(Wacker Silicones 公司製、甲基氫聚矽氧烷的乳膠，於甲基矽氧烷之中與雙 鍵反應，固形分濃度50質量％ )、0.3份的矽烷偶合劑 (信越聚矽氧烷（股）製、商品名：KBM-403 )，及，作 爲非離子系的界面活性劑之〇. 1 5份的聚氧化乙烯油醯基 醚（花王（股）製、商品名：Emul gen 404 ) ( S1成分） 而得到塗劑。再者，塗劑的固形分重量爲6 · 0質量％。此 外，由此塗劑所得到的脫模層1〇〇質量％中之各成分的固 形分比率，如下述。 主劑：8 4.1質量％ 交聯劑：8.4質量％ 矽烷偶合劑：5.0質量％ 界面活性劑：2.5質量％ -56- 200934660 [未延伸聚酯薄膜成形步驟] 將上述所得到的聚對苯二甲酸乙二醇酯組成物’以 1 70 °C乾燥5小時，使聚對苯二甲酸乙二醇酯組成物的水 分率成爲0.05質量％以下爲止，接著，將經乾燥的聚對苯 二甲酸乙二醇酯組成物供給至擠壓機，於熔融溫度 280〜300 °C進行熔融擠壓，使用平均網目大小Ιίμηι的鋼線 過濾器進行高精度過濾後，藉由模具進行擠壓製成熔融 片，藉由將該相關的溶融片用靜電密著法接觸於冷卻轉筒 令其急冷，得到厚度450μηι的未延伸聚酯薄膜。 [—次延伸步驟] 使用所得到的未延伸聚酯薄膜，與實施例1同樣作 法，得到長邊方向一軸延伸聚酯薄膜。 [線上塗佈步驟] 接著，於所得到的長邊方向一軸延伸聚酯薄膜，藉由 塗佈上述所調製的塗劑，使得到的脫模薄膜中之脫模層的 厚度成爲40nm，得到具有塗膜之聚酯薄膜。再者’塗劑 的塗佈，係在於未延伸聚酯薄膜成形步驟中未接觸冷卻轉 筒之面上實施。 [二次延伸步驟] 接著，將具有所得到的塗膜之聚酯薄膜供給至定型 機，與實施例1同樣作法，製成二軸延伸聚酯薄膜。 -57- 200934660 [熱固定步驟] 針對所得到的二軸延伸聚酯薄膜’與實施例1同樣作 法，得到全厚度3 1 μιη的脫模薄膜。使用所得到的脫模薄 膜，進行各種的測量•評估。結果列示於表2。 實施例4 各步驟中的各條件如下述以外，與實施例3同樣作法 而得到脫模薄膜。使用所得到的脫模薄膜’進行各種的測 量·評估的結果列示於表2。 [塗劑的調製] 作爲界面活性劑，使用0.06份的非離子系的聚矽氧 烷系界面活性劑之聚氧化乙烯•甲基聚矽氧烷共聚合物 (日本乳膠（股）製、商品名：EMALEX SS_505 1 ) ( S2 成分），取代聚氧化乙烯油醯基醚。再者’塗劑的固形分 重量爲6.0質量％。此外’由此塗劑所得到的脫模層1 〇 〇 質量％中之各成分的固形分比率，如下述。 主劑：8 5 · 4質量％ 交聯劑：8 · 5質量％ 矽烷偶合劑：5 · 1質量％ 界面活性劑：1 · 〇質量％ [二次延伸步驟] -58- 200934660 使橫延伸倍率爲4 · 5倍。 [熱固定步驟] 使弛緩處理中的弛緩量爲4.0%。 實施例5 於各步驟之各條件如下述以外，與實施例4同樣作法 而得到脫模薄膜。使用所得到的脫模薄膜，進行各種的測 量·評估的結果列示於表2。 [塗劑的調製] 作爲界面活性劑，使用0.15份的非離子系的聚矽氧 烷系界面活性劑之聚氧化乙烯•甲基聚矽氧烷共聚合物 (日本乳膠（股）製、商品名：EMALEX SS-5051) (S2 成分）。再者，塗劑的固形分重量爲6.0質量％。此外， Λ 由此塗劑所得到的脫模層100質量％中之各成分的固形分 〇 比率，如下述。 主劑：8 4.1質量％ 交聯劑：8.4質量％ 矽烷偶合劑：5.0質量％ 界面活性劑：2.5質量％ 實施例6 於各步驟之各條件如下述以外，與實施例4同樣作法 -59- 200934660 而得到脫模薄膜。使用所得到的脫模薄膜，進行各種的測 量·評估的結果列示於表2。 [塗劑的調製] 作爲界面活性劑，使用0.3份的非離子系的聚矽氧烷 系界面活性劑之聚氧化乙烯•甲基聚矽氧烷共聚合物（曰 本乳膠（股）製、商品名·· EMALEX SS-5051) (S2成 分）。再者，塗劑的固形分重量爲6.2質量％。此外，由 此塗劑所得到的脫模層1 00質量％中之各成分的固形分比 率，如下述。 主劑：8 2.0質量％ 交聯劑：8.2質量％ 矽烷偶合劑：4.9質量％ 界面活性劑：4.9質量％Hv = l, 854xP / d2 In general, when the film is wound into a roll shape, the thickness of the film is thick, and as the winding diameter increases, the tape becomes tight, which may cause a band-like defect. In the relevant portion, the film is elongated and the flatness of the film is impaired. This tendency becomes more remarkable as the Vickers hardness (Hv) of the surface layer of the drum becomes higher. That is, when the Vickers hardness (?ν) of the surface layer of the drum exceeds 450, the winding is too tight, and the elongation of the film is too large, and the flatness of the film is also inferior. From such a viewpoint, the upper limit of the Vickers hardness (?v) of the surface layer of the drum is preferably 430 or less, more preferably 420 or less, and particularly preferably 410 or less. On the other hand, when the Vickers hardness (?v) of the surface layer of the roller is too low, there is a tendency that the winding bias tends to occur, but the lower the problem, the lower the better. From such a viewpoint, the lower limit of the Vickers hardness (?ν) of the surface layer of the drum is preferably 340 or more, more preferably 360 or more, and particularly preferably 380 or more. The Vickers hardness (?v) of the surface layer of the above-mentioned roller can be achieved by winding up conditions such as winding tension or nip pressure when winding the release film. As the winding tension, the initial tension must be 49 N/m or less. By setting the initial tension to the above range, the Vickers hardness (?ν) of the surface layer of the drum can be made 450 or less. Further, the amount of air entrained in the winding is a moderate amount, which can reduce the influence of the thickness of the film, and can suppress the winding, and the flatness is more excellent, and the winding offset can be suppressed. When the initial tension is too high, the Vickers hardness (Ην) of the surface layer of the roller tends to be too high. In addition, there is a tendency that the amount of air to be taken in the roll 200934660 is reduced, and the flatness tends to be poor. From such a viewpoint, the upper limit of the initial tension is preferably 48 N/m or less, more preferably 47 N/m or less. On the other hand, when the initial tension drop is too low, the coiling may become unstable, and the film tends to become meandering, and the end surface of the drum may become irregular, wrinkles may occur, and the cutting tends to be poor, but it does not occur. The lower the problem, the better. From such a viewpoint, the lower limit of the initial tensile force is preferably 30 N/m or more. In addition, the initial initial φ force ' indicates that the tension when the release film which is substantially the product is rolled into a roll shape' does not necessarily indicate the tension after starting to be wound around the core. In other words, in order to reduce the influence of foreign matter, injury, and the like on the surface of the core, a method of making the winding tension to a length of a few m or even several tens of m after the winding of the core is used is particularly high. Indicates the take-up tension in this section. In addition, to apply a tension taper, the final tension must be reduced for the initial tension. Specifically, the ratio (tension taper ratio) of the final tension of the phase seal to the initial tension φ must be 80% or less. The winding offset can be suppressed by lowering the Vickers hardness (Hv) of the surface layer of the roll by making the tension taper rate in the above range. When the tension taper ratio is too high, the Vickers hardness (Ην) of the surface layer of the drum tends to become too high. From such a viewpoint, the upper limit of the tension taper ratio is preferably 70% or less, more preferably 6% or less. On the other hand, from the viewpoint of the hardness of the drum, the tension taper ratio is preferably low, but when the tension taper ratio is too low, the final tension becomes too low, and there is a tendency that problems such as offset of the end surface of the drum tend to occur. From such a viewpoint, the lower limit ' of the tension taper ratio is preferably 30% or more. In the present invention, from the initial tension of -37-200934660 to the final tension, as long as the take-up tension does not exceed 4 9 N/m, the portion where the tension is applied may be added to the main portion of the drum to make the roll. The form in which the tension is continuously decreased is preferable, and the form in which the tension is continuously decreased in a certain ratio is preferable. By setting the tension taper to the above-described state, the internal stress in the winding direction can be often 0 or more in the drum, and the wrinkle-like defect (T-B AR ) or the gap in the lateral direction can be suppressed. Further, the main portion of the drum is shown in the direction of the diameter of the drum, and the surface layer of the core is 5 mm or more outside, and the surface of the drum is 5 mm or more. From the initial tension and the tension taper ratio as described above, the final tension must be 39 N/m or less. By setting the final tension within the above range, the Vickers hardness (Hv) of the surface layer of the drum can be made 450 or less. When the final tension is too high, there is a tendency that the Vickers hardness (Ην) of the surface layer of the drum becomes too high. From this point of view, the upper limit of the final tension is preferably 3 8 N/m or less, more preferably 30 N/m or less. On the other hand, from the viewpoint of the hardness of the drum, the final tension is preferably low, but when the tension is too low, the winding may become unstable, the film tends to be easy to snake, and there may be problems such as offset of the end surface of the drum. A tendency to produce. From such a viewpoint, the lower limit of the final tension is preferably ΙΟΝ/m or more, and more preferably 15 N/m or more. The gap pressure must be such that the initial gap pressure is 20 ON/m or less. By setting the initial gap to the above range, the Vickers hardness (Hv) of the surface layer of the drum can be made 450 or less. In addition, the amount of air entrained in the coiling is appropriately measured, which can reduce the influence of the thickness of the film, and can suppress the winding, and the flatness is more excellent, and the winding offset can be suppressed. When the initial gap pressure is too high, there is a tendency that the Vickers hardness (Hv) of the roller-38-200934660 layer becomes too high. Further, there is a tendency that the amount of entrained air in the winding tends to decrease, and the flatness tends to be poor. From such a viewpoint, the upper limit of the initial gap pressure is preferably 18 ON/m or less, more preferably 160 N/m or less, and particularly preferably uON/m or less. On the other hand, when the initial gap pressure is too low, the winding tends to be unstable, and the winding bias or wrinkles tend to occur. From such a viewpoint, the lower limit of the initial gap pressure is preferably 50 N/m or more, and more preferably 80 N/m or more. φ In addition, the 'gap pressure taper may not be added. However, by increasing the gap taper at a gap pressure ratio of -1% or less, the occurrence of wrinkles or flaws and the end surface offset of the drum can be suppressed. From the initial gap pressure and the gap pressure ratio as described above, the final gap pressure is 220 N/m or less. However, when the final gap pressure is too high, the Vickers hardness (Hv) of the surface layer of the roll tends to be too high. From such a viewpoint, the upper limit ' of the final gap pressure is preferably 170 N/m or less, more preferably 150 Å/ι or less, and particularly preferably 140 N/m or less. On the other hand, when the final gap pressure is too low φ, there is a tendency for the coiling to become unstable. From such a viewpoint, the lower limit of the final gap pressure is preferably 50 N/m or more, more preferably 70 N/m or more, and particularly preferably 90 N/m or more. [Embodiment] Hereinafter, the present invention will be described more specifically by way of examples and comparative examples. However, the present invention is not limited thereto as long as it does not exceed the gist thereof. -39-200934660 <Measurement and Evaluation Method> In the examples and comparative examples, the following items were used to perform each measurement and evaluation by the following method. (1) Average particle diameter of particles The measurement was carried out using a Centrifugal Particle Size Analyzer manufactured by Shimadzu Corporation under the trade name: CP-5〇. By reading the cumulative curve of the particles of each particle diameter calculated based on the centrifugal sedimentation curve obtained by the measurement, the "equivalent spherical diameter" corresponding to a particle diameter of 50% by mass is read. The average particle diameter of the particles (unit: μιη) (Reviewed by the book "Graphology Measurement Technology", Nikkan Kogyo Shimbun, 1 975, pages 242 to 247). (2) Maximum height (Rmax) According to JIS standard (B0601: surface roughness - definition and representation, B065 1 : stylus surface roughness measuring device), by a 3-dimensional surface roughness meter (manufactured by Kosho Corporation) Product name: SE-3 AK ), with magnification: 20,000 times, scanning pitch: 2μιη, scanning length: 1mm, number of scanning strips: 1 strip, cut-off: 0.25mm, calculate it The maximum height of the area, the average 値 of the result measured at 1 値 is taken as Rmax (unit: nm) ° (3) Elongation under load (Smd, Std) Using TMA (made by Seiko Instruments Co., Ltd., trade name -40- 200934660 SS6000 ), under the humidity: 50% RH, with a sample width of 4 mm and a chuck spacing of 20 mm, a load of 0.3 MPa, 1.0 MPa, 2.5 MPa per unit area is applied in the longitudinal direction. From the start temperature: 30 ° C, the temperature was raised at a temperature increase rate of 10 ° C / min, and the stretching behavior of the film at 100 ° C was calculated by the following formula at 0.3 MPa, 1.0 MP a, 2.5 MPa. Elongation (SMD) (unit: %) under each load condition. Similarly, a load of 〇·〇1 MPa was applied in the width direction, and the elongation (STD) (unit: %) of φ under the relevant load conditions was calculated. Further, the elongation (SMD, STD) was measured for each of 10 samples, and the average enthalpy was calculated. Elongation (Smd, Std) = (AM/M〇)x100 (%) ΔΜ = Μ-Μ〇 'In the above formula, 'Μ〇 denotes the length in the longitudinal direction or the width φ direction of the film before heat treatment' Μ means heat treatment The length of the film in the same direction. That is, elongation (SMD) and elongation (STD), when negative, indicate film shrinkage, and timing indicates film elongation. (4) Thermal elongation under no load (HSmd, HStd) In a oven set to a temperature of 100 ° (:: 'overhanging a film length of about 30 cm square length measuring the length of the square beforehand' under no load 3 After lapse of 30 minutes, the film sample was taken out from the oven, and after returning to room temperature, 'measured dimensional change' was calculated by the following formula -41 - 200934660 Thermal elongation (HSmd, HStd) (unit: %) Furthermore, the elongation (HSMD, HSTD) is obtained by collecting data for each of 10 samples, and calculating the average enthalpy. Thermal elongation (HSmd, HStd) = (AL/L 〇) x 100 (%) Δ L = L - L 〇 In the above formula, LQ represents the length in the longitudinal direction or the width direction of the film before heat treatment, and L represents the length in the same direction of the film after heat treatment, that is, the heat elongation (HSMD) and the heat elongation (HSTD). Negative time means film shrinkage, and timing means film elongation. (5) Evaluation of surface smoothness of ceramic sheet (evaluation of practical characteristics) (Condition 1) On the side of the release layer side of the release film, it will consist of the following The resulting ceramic slurry is extrusion coated (die coater) Coating to form a ceramic layer having a thickness of 5 μm after drying, and winding up to 200 m. (Condition 2) Preparing a roll of a release film having a width of 450 mm and a length of 2,000 m. The release layer of the relevant release film On the side surface, a ceramic slurry composed of the following composition was applied by extrusion coating at a film transport speed of 60 m/min to form a ceramic layer having a thickness of 5 μm after drying to obtain a length l. 9 μm of the ceramic layer/release film composite was rolled into a roll shape. Then, in the ceramic layer/release film composite obtained in Conditions 1 and 2, the ceramic layer was peeled off from the release film. The ceramic sheet was subjected to surface observation using a scanning laser microscope (manufactured by LASERTEC) on both sides of the ceramic sheet (measuring area: 1 m2) obtained in the period of -42-200934660, and surface smoothness was performed according to the following evaluation criteria. [Ceramic slurry composition] • Barium titanate (manufactured by Fuji Titanium Co., Ltd., average particle size: 〇.7μιη) : 1 〇〇 φ · Polyethylene butyral resin (product of Sekisui Chemical Co., Ltd., trade name: 8- LEC BM-S ) : 30 servings Plasticizer (dioctyl phthalate)··5 parts•Toluene/ethanol mixed solvent (mixing ratio: 6 : 4 ) : 200 parts [surface smoothness evaluation standard] 〇: crater (depression) of depth 〇·5μιη or more It is 2 / m2 or less (practical, no problem) ❹ △: The depth (〇 recess) of the depth 〇·5μιη or more is more than 2 / m2 and less than 6 / m2 (in practical terms, there will be problems) Degree) X: The number of pits (depressions) of a depth of 0.5 μηα or more is 6 pieces/m2 or more (practical, no problem) (6) Peeling electrification evaluation of the release film The evaluation of the above (5) (condition 2) is carried out. At the time, the peeling charge amount when the roll of the release film was taken out was measured. The distance is measured from the surface of the film immediately after the roll is rolled out -43- 200934660 (the surface on the inner side of the roll is taken up), and a concentrated potential measuring device (Kasuga Electric Co., Ltd.) is installed at a position 5 cm vertically above. Product name: Electrostatic potential measuring device SV -1 0 ), at temperature: 2 2 . (:, humidity: 44% RH in a gas atmosphere to measure the stripping charge. The total length of the roll of the release film is 2,000 m, and at least 15 peeling charges are measured every i〇〇m'.値The stripping charge amount (unit: kV) of the release film. Or 'Evaluation by the following evaluation criteria. [Release film stripping electrification evaluation standard] 〇: Stripping charge amount is 2. OkV or less (peeling is good) X: peeling charge amount exceeds 2.0 kV (peeling electrification failure) (7) Evaluation of peeling electrification of ceramic sheet The ceramic layer/release film composite was obtained by the same method as (5) (condition 2) above. The surface of the ceramic layer of the ceramic layer/release film composite is formed into a patterned Ni electrode printed layer having a thickness of 3 μm by screen printing, and then obtained as a metal. The metal film/ceramic layer/release film composite was cut into a size of 300 mm X 3 0 Omm to obtain a sheet-like sample. With respect to the obtained sheet-like sample, the peeling speed was 20 m/min. Release film peeling metal film / ceramic layer composite, The amount of the stripped stripping power of the stripped metal film/ceramic layer composite is 5 cm from the surface of the ceramic layer, and a concentrated potential measuring device (manufactured by Kasuga Electric Co., Ltd., trade name: electrostatic potential measurement) SV -1 0 ), the stripping charge was measured in a gas atmosphere at a temperature of 2 2 ° C, humidity: 4 4 % R Η 200934660. The measurement was carried out on a sheet of 100 specimens, and the average enthalpy was used as The peeling charge amount of the ceramic sheet (unit: kV), or evaluation by the following evaluation criteria. [Catalyst stripping electrification evaluation standard] 〇: Stripping charge amount is 20kV or less (peeling is good) X: Stripping power amount In the case of the peeling of the ceramic sheet of the above-mentioned (7), the peeling of the metal film/ceramic layer composite from the release film is evaluated in the case of the peeling of the ceramic sheet (8). The evaluation was carried out by the following evaluation criteria. [Exfoliation evaluation criteria] ◎: The peeling force was moderate, the metal film/ceramic layer was not broken, and the ceramic 0 layer remained in the release film (the degree of practically no problem): The peeling force is slightly heavier, or the metal film/ceramic layer sees a slight break, or the ceramic layer is slightly left in the release film (the degree of practically no problem) X: The peeling force is too heavy 'Metal film/ceramic layer to see When the fracture is broken, the ceramic layer remains in the release film (the degree of practical problem) (9-1) Lamination evaluation of the ceramic sheet i (utility evaluation evaluation) is obtained in the above (5) (Condition 1) On the ceramic sheet, laminated with -45- 200934660 Ni-electrode printed layer (3 μιη thickness after drying). Using the obtained ceramic sheet/electrode laminate, based on the one-side end Ten layers were laminated, and the degree of positional shift of the electrode printed layer at this time was evaluated by the following evaluation criteria. [Position offset evaluation criterion] ◎: The positional shift is less than 200 μm (the degree of practically no problem) 〇: The positional shift is 200 μηι or more and less than 400 μm (the degree of practical problem-free) X: Positional shift 400 μm or more (practical problem) (9-2) Evaluation of lamination of ceramic sheets 2 (evaluation of practical characteristics) The metal film after cutting and peeling obtained by the same method as (7) above / As the ceramic layer composite, a laminator laminate layer in such a manner that a position was detected by a CCD camera was used to obtain a laminate. With respect to the obtained laminate, the obtained metal layer/ceramic layer composite was used as a reference, and the amount of enthalpy obtained by microscopic measurement was measured as a positional shift (unit: μπι). The evaluation is carried out by the following evaluation criteria. In addition, the laminate is peeled off immediately after the release film is released. [Location shift evaluation standard] ◎: The positional deviation is lower than (the practically problem-free process is 200934660. 位置: The positional deviation is 200 μmη or more and lower than 400μιη (degree of practical problem) X : Positional deviation is 400 μm or more (practical problem) (1〇) Vickers hardness (Ην) of the surface of the drum According to JIS Ζ 2244 (1961), the following The measurement was carried out. The measurement was performed on the surface layer of the release film roll obtained in the example, and the portion having a distance of 5 mm from the end face of φ was removed, and the width was measured at 1 ,, and the maximum 値 was taken as the Vickers hardness (Ην) of the surface layer of the roller. Winding Offset With regard to the release film roll obtained in the example, the condition of the winding offset of the end face was evaluated by the following evaluation criteria. [Winning Offset Evaluation Criteria] 0 ◎: Coiling bias The shift is 1 mm or less (the degree of use can be used without problems). 卷: The take-up offset is more than 1 mm and 2 mm or less (the degree of use can be used without problems) △: The take-up offset is more than 2 mm and less than 3 mm. (There is a slight problem The degree of use can be used. X: The take-up offset is more than 3 mm (there is a problem that cannot be used) -47- 200934660 (1 2 ) Flatness From the release film roll, a film sample of 2 m in length is taken and rolled onto the roll. When the side of the surface side of the drum is raised upward, it is spread horizontally on a flat table. After standing for 10 minutes, the entire surface of the film sample is observed, and the crepe remaining on the surface is measured (flute, film floating high) In the length (unit: cm) of the above-mentioned stage, the flatness (unit: cm/m2) is calculated by dividing the total by the measurement area (unit: m2). The evaluation of the flatness is carried out by the following evaluation criteria. [Flatness evaluation criteria] ◎: Flatness is 28 cm/m2 or less (the degree of practically no problem) 〇: Flatness is more than 28 cm/m2, 33 cm/m2 or less (practical problem-free degree) X: Flat The degree is more than 33 cm/m2 (there is a problem in practical use). (13) The thickness of the film is measured by a micrometer (manufactured by Anritsu Co., Ltd., trade name "K-402B"), and 1 Ocin in the longitudinal direction of the film. Interval measurement 1 〇, the relevant longitudinal measurement at 1 ,, The film thickness of 10 columns and all 100 points was measured at intervals of 1 〇cm in the lateral direction, and the average 値 of the film thickness at the obtained 1 〇〇 was calculated as the film thickness (unit: Pm). Then, electronic micrometering was used. Measured by Anritsu Co., Ltd., product name "K-312A", with a needle pressure of 30 g and a speed of 25 mm/sec, measured in the longitudinal direction of the film 200934660 in the longitudinal direction lm and the transverse direction of 450 mm to obtain a continuous thickness. chart. From the obtained graph, the maximum thickness (unit: μη!) and the minimum thickness (unit: μιη) in the longitudinal direction and the lateral direction are read, and the thickness of the film is calculated in accordance with the thickness of the film described above (unit: %) ). Thickness spot (%) = ((maximum thickness - minimum thickness) / film thickness) χ 1〇〇i (1 4 ) Thickness of ceramic sheet ❹ For the ceramic layer obtained by the above (5) (Condition 2) The film composite was measured using a micrometer (manufactured by Anritsu Co., Ltd., trade name "K-402B"), and then the ceramic layer at the thickness of the measurement was completely peeled off, and the thickness was measured again in the same place. The number of these differences is calculated as the thickness of the ceramic sheet. The related operation is measured at a distance of 1 m in the longitudinal direction at a distance of 1 m, and the measurement in the longitudinal direction of 1 〇 is measured in the horizontal direction at 10 cm intervals, and all of the film is measured at 100 intervals. The average 値 of the thickness of the obtained ceramic sheet at one turn was taken as the thickness of the ceramic sheet (unit: μιη). Next, among the above-mentioned measurements, the largest one is the maximum thickness (unit: μιη), and the smallest is the minimum thickness (unit: μπι). The thickness spot is calculated by the following formula (unit: %) ° Thickness spot (%) = ((maximum thickness - minimum thickness) / ceramic sheet thickness) χ 10 〇 evaluation is carried out by the following evaluation criteria. -49- 200934660 [Criteria for evaluation of thickness spot] ◎: The thickness of the spot is 2.0% or less (the thickness is very excellent, and the degree of practical use is completely no problem). 〇: The thickness is more than 2.0 °/. , 3.0% or less (excellent in thickness, practically problem-free) X: thickness spot is more than 3.0% (thickness difference in thickness) Example 1 which is practically problematic [manufacture of polyester] In a mixture of 100 parts of an alcohol ester and 7 parts by weight of ethylene glycol, a manganese acetate · 4 water salt as a transesterification catalyst was added to make the amount of manganese in the obtained polyester 80 ppm, and the internal temperature was 150. °C slowly increases the transesterification reaction. When the transesterification reaction becomes 95%, 1 part of bismuth phosphite phosphine is added as a stabilizer, and after stirring, 0.03 parts of antimony trioxide is added. After the water in the inside was sufficiently distilled, the synthetic calcium carbonate particles having an average particle diameter of 0.6 μm as an internal filler (slip agent) were added so as to be 0.2% by mass based on the mass of the obtained polyester. Stirring. Then, the reaction product was transferred to a polymerization reactor, and poly(p-benzene) having an intrinsic viscosity of 0.65 (35 ° C, o-chloropurine) was obtained by polycondensation under high temperature vacuum (final internal temperature 295 〇C). Composition of ethylene glycol dicarboxylate. -50- 2009346 60 [Preparation of paint agent] By 88.5 parts of deionized water, 10 parts of polyoxyalkylene latex 400E (manufactured by Wacker Silicones, added with polyoxyalkylene: vinyl methyl polyoxyalkylene, crosslinked In the case of the agent, a forcing agent for preventing premature reaction with the platinum catalyst, and one part of the crosslinking agent V72 (a latex of methyl hydrogen polyoxyalkylene manufactured by Wacker Silicones Co., Ltd.) In the middle of the reaction with the double bond, 0.5 part of a decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KB Μ-4 03) was added to obtain a coating agent. Further, the solid content was 5% by mass. [Unstretched Polyester Film Forming Step] The polyethylene terephthalate composition obtained above was dried at 170 ° C for 5 hours to set the water content of the polymer to 0.05% by mass. The dried polyethylene terephthalate composition is supplied to an extruder "melt-squeezing at a melting temperature of 2 80 to 300 ° C" using a steel wire passer with a flat mesh size of Ιίμιη Accuracy after 'filtering' using an extrusion die, by contact with cold by electrostatic sealing The drum was quenched to obtain an unstretched polyester film having a thickness of 450 μm. [One-step stretching step] The obtained unstretched polyester film was preheated at 75 ° C 'then' between the low speed and high speed rollers. The film temperature is extended by 3.6 times in the longitudinal direction, and then the polyester film of the longitudinal direction (longitudinal direction) is obtained by quenching -51 - 200934660 [Online coating step] Next, the polyester is stretched in the obtained long side direction The film was coated with the above-prepared coating agent to have a thickness of 40 nm after drying to obtain a polyester film having a coating film. [Secondary Extension Step] Next, the obtained polyester film having a coating film was supplied to a setting machine (ST ENTER), and each of the two regions at 105 ° C and 115 ° C was preheated for 2 seconds, and then at 1 2 In the 4 regions of 0 °C, 1 30 °C, 1 4 5 °C, and 1 5 5 °C, each of them is uniformly extended for 2 seconds, and the total is the stretching ratio in the direction perpendicular to the longitudinal direction (width direction) ( The transverse stretch ratio was 4.1 times, and a biaxially stretched polyester film was produced. [Heat-fixing step] The obtained biaxially stretched polyester film was heat-fixed for 2 seconds in a total of 2 seconds at 210 ° C, 225 t, and 195 ° C for 6 seconds in total, at the last 195 ° C. In the heat-fixed region, a release film having a full thickness of 31 μm was obtained by performing a 2.5% relaxation treatment in the longitudinal direction and the vertical direction (width direction). Various measurement and evaluation were performed using the obtained release film. The results are shown in Table 1. Embodiment 2 In the second stretching step, except that the stretching ratio in the direction perpendicular to the longitudinal direction (width - 52 - 200934660 degrees) is 4.5 times, and the relaxation amount in the third region of the heat fixing step is 4.0%, A release film was obtained in the same manner as in Example 1. The results of various measurements and evaluations using the obtained release film are shown in Table 1. Comparative Example 1 In the production of the release film, the same procedure as in Example 1 was carried out except that the release agent coating liquid composed of the water-based heat-curable polysiloxane composition was not applied on the line. A biaxially stretched polyester film of the release layer. Further, a Pt catalyst (Toshiba polyoxyl) was added to a toluene solution (solid content concentration: 3 mass%) of an addition polysiloxane compound (manufactured by Toshiba Polyoxane Co., Ltd., trade name: TPR-6721). The product of the alkane company, trade name: CM670, was prepared in an amount of 1 part by mass based on 1 part by mass of the solid content of the addition-molding polyoxyalkylene type compound to prepare a release agent coating liquid. Next, the biaxially stretched polyester φ film roll having the release layer obtained as described above is taken up, and the center portion of the biaxially stretched polyester film which is wound up in the direction perpendicular to the longitudinal direction (width direction) is taken up. Applying the above-mentioned adjusted release agent coating liquid to a coating amount of (wet) 6 g/m 2 , and using an air floating conveyance drying device having a space of 38 cm each of the air flow outlets below and above, The conveyance tension: 2,000 kPa, drying temperature: 160 ° C, and drying for 16 seconds to form a release layer, and a release film having a weight of 0.2 g/m 2 after dry curing of the release layer was obtained. The results of various measurements and evaluations using the obtained release film are shown in Table 1. -53-200934660 Comparative Example 2 A release film was obtained in the same manner as in Example i except that the elongation in the longitudinal direction (longitudinal direction) was 3 〇 times. The results of various measurements and evaluations using the obtained release film are shown in Table 1. Comparative Example 3 Except that the stretching ratio in the longitudinal direction (longitudinal direction) was 4, 8 times in the primary stretching step, and the stretching magnification in the direction (width direction) perpendicular to the longitudinal direction in the secondary stretching step was 3.0 times. A release film was obtained in the same manner as in Example 1. The results of various measurements and evaluations using the obtained release film are shown in Table i. -54- 200934660 ο❹ Comparative Example 3 -0.48 -0.38 ο ( Ο in ο 〇 inch 〇jrj 465 X 〇 Comparative Example 2 (Ν 〇-0.14 0.05 -0.62 Ο Bu 〇 VsD 〇 440 450 X 〇 [Comparative Example 1 -0.05 0.02 0.13 Ο -0.05 〇-0.05 <N 464 X 〇Example 2 -0.28 -0.19 -0.08 -0.43 -0.18 〇0.32 OO 455 ◎ 〇: Example 1 -0.31 -0.24 ί-Η Ο -0.39 CN| 〇 〇CN 〇o 460 ◎ 〇 ii Load 0.3MPa Load l.OMPa Load 2.5MPa Load 0.01 MPa 1 No load No load MD-TD The surface of the release layer does not have the lateral displacement of the release layer (Layer evaluation 1) Surface smoothness (Condition 1) Elongation (Smd) Elongation (Std) Thermal elongation (hsmd) Thermal elongation (hstd) HSmd-HStd Rmax Ceramic sheet evaluation -55- 200934660 Example 3 [Manufacture of polyester] In the same manner as in Example 1, a polyethylene terephthalate composition having an intrinsic viscosity of 56 5 (3 5 <=c, o-chloride S&) was obtained. [Preparation of a coating agent] By 87 parts In the deionized water, 10 parts of polyoxyxane latex 400E (manufactured by Wacker Silicones Co., Ltd., added with polyfluorene) was added as a main component under stirring. Oxane: vinyl methyl polyoxyalkylene, cross-linking agent, anti-allergic agent for preventing premature reaction with lead catalyst, solid content concentration 50% by mass), 1 part cross-linking agent V72 (Wacker Silicones, a methyl hydrogen polyoxyalkylene latex, reacted with a double bond in methyloxane, a solid concentration of 50% by mass), and 0.3 parts of a decane coupling agent (Shinjuku polyoxyalkylene ( )), trade name: KBM-403), and as a nonionic surfactant. 1 5 parts of polyoxyethylene oil decyl ether (King (stock), trade name: Emul gen 404) (S1 component) A coating agent is obtained. Further, the solid content of the coating agent is 6.00% by mass. Further, the solid content ratio of each component in the release layer of the release layer obtained by the coating agent is 1% by mass. As the following: Main agent: 8 4.1% by mass Crosslinking agent: 8.4% by mass Decane coupling agent: 5.0% by mass Surfactant: 2.5% by mass -56- 200934660 [Unstretched polyester film forming step] The above obtained Polyethylene terephthalate composition 'dry at 1 70 ° C for 5 hours to make polyterephthalic acid The moisture content of the diol ester composition is 0.05% by mass or less, and then the dried polyethylene terephthalate composition is supplied to an extruder and melt-extruded at a melting temperature of 280 to 300 °C. After high-precision filtration using a steel wire filter having an average mesh size of Ιίμηι, the molten sheet is extruded by a die, and the related melted sheet is cooled by contact with the cooling drum by electrostatic sealing. An unstretched polyester film having a thickness of 450 μm was obtained. [First Extension Step] Using the obtained unstretched polyester film, a longitudinal direction monoaxially stretched polyester film was obtained in the same manner as in Example 1. [On-line coating step] Next, the polyester film is stretched in one direction in the obtained longitudinal direction, and the thickness of the release layer in the release film obtained is 40 nm by applying the above-mentioned prepared coating agent. Film coated polyester film. Further, the application of the coating agent is carried out on the surface of the unstretched polyester film forming step which is not in contact with the cooling drum. [Secondary stretching step] Next, a polyester film having the obtained coating film was supplied to a sizing machine, and a biaxially stretched polyester film was produced in the same manner as in Example 1. -57-200934660 [Heat fixing step] The obtained biaxially stretched polyester film was treated in the same manner as in Example 1 to obtain a release film having a total thickness of 3 μm. Various measurement and evaluation were performed using the obtained release film. The results are shown in Table 2. Example 4 Each of the conditions in the respective steps was carried out in the same manner as in Example 3 except that the release film was obtained. The results of various measurements and evaluations using the obtained release film' are shown in Table 2. [Preparation of a coating agent] As a surfactant, 0.06 part of a nonionic polyoxyalkylene-based surfactant-based polyoxyethylene/methyl polyoxyalkylene copolymer (Japanese Latex Co., Ltd., product) Name: EMALEX SS_505 1 ) (S2 component), replacing polyoxyethylene oil decyl ether. Further, the solid content of the coating agent was 6.0% by mass. Further, the solid content ratio of each component in the release layer 1 〇 〇 mass % obtained by the coating agent is as follows. Main agent: 8 5 · 4 mass % Crosslinking agent: 8 · 5 mass % decane coupling agent: 5 · 1 mass % Surfactant: 1 · 〇 mass % [secondary extension step] -58- 200934660 Horizontal extension ratio It is 4 · 5 times. [Heat fixation step] The relaxation amount in the relaxation treatment was 4.0%. (Example 5) A release film was obtained in the same manner as in Example 4 except that the respective conditions of the respective steps were as follows. The results of various measurements and evaluations using the obtained release film are shown in Table 2. [Preparation of a coating agent] As a surfactant, 0.15 parts of a nonionic polyoxyalkylene-based surfactant-based polyoxyethylene/methyl polyoxyalkylene copolymer (Japanese Latex Co., Ltd., product) Name: EMALEX SS-5051) (S2 ingredient). Further, the solid content of the coating agent was 6.0% by mass. Further, the solid content ratio of each component in 100% by mass of the release layer obtained by the coating agent is as follows. Main agent: 8 4.1% by mass Crosslinking agent: 8.4% by mass Decane coupling agent: 5.0% by mass Surfactant: 2.5% by mass Example 6 The conditions in each step were the same as in Example 4 except for the following -59- A release film was obtained in 200934660. The results of various measurements and evaluations using the obtained release film are shown in Table 2. [Preparation of a coating agent] As a surfactant, 0.3 part of a nonionic polyoxyalkylene-based surfactant polyoxyethylene/methyl polyoxyalkylene copolymer (manufactured by 曰本乳胶) Product Name·· EMALEX SS-5051) (S2 component). Further, the solid content of the coating agent was 6.2% by mass. Further, the solid content ratio of each of the components of the release layer obtained by the coating agent in 100% by mass is as follows. Main agent: 8 2.0% by mass Crosslinking agent: 8.2% by mass Decane coupling agent: 4.9% by mass Surfactant: 4.9 mass%
實施例7 於各步驟之各條件如下述以外，與實施例4同樣作法 而得到脫模薄膜。使用所得到的脫模薄膜，進行各種的測 量·評估的結果列示於表2。 [塗劑的調製] 作爲界面活性劑’使用〇·6份的非離子系的聚矽氧烷 系界面活性劑之聚氧化乙烯•甲基聚矽氧烷共聚合物（曰 本乳膠（股）製、商品名：EMALEX SS-5 05 1 ) ( S2成 -60- 200934660 分）。再者，塗劑的固形分重量爲6.5質量❶。此外’由 此塗劑所得到的脫模層1 〇〇質量％中之各成分的固形分比 率，如下述。 主劑：7 8 · 1質量％ 交聯劑：7.8質量％ 矽烷偶合劑：4.7質量％ 界面活性劑：9.4質量％ e 比較例4 各步驟中之各條件如下述以外，與實施例4同樣作法 而得到脫模薄膜。使用所得到的脫模薄膜’進行各種的測 量·評估的結果列示於表2。 [塗劑的調製] 未使用界面活性劑，再者，塗劑的固形分重量爲5-9 φ 質量％，此外，由此塗劑所得到的脫模層1 〇 〇質量％中之 各成分的固形分比率，如下述。 主劑：86.2質量％ 交聯劑：8.6質量％ 矽烷偶合劑：5.2質量°/。 界面活性劑：〇質量％ [一次延伸步驟] 使縱延伸倍率爲3.0倍 -61 - 200934660 比較例5 各步驟中之各條件如下述以外，與比較例4同樣作法 而得到脫模薄膜。使用所得到的脫模薄膜’進行各種的測 量·評估的結果列示於表2。 [一次延伸步驟] 使縱延伸倍率爲4.8倍。 [二次延伸步驟] 使橫延伸倍率爲3.0倍。 比較例6 除了不塗佈塗劑外，與實施例3同樣作法，得到不具 有脫模層之二軸延伸聚酯薄膜。 接著，於加成型聚矽氧烷系化合物（東芝聚矽氧烷 (股）製、商品名：TPR-672 1 )的甲苯溶液（固形分濃 度：3質量％)中，加入Pt觸媒（東芝聚矽氧烷（股） 製、商品名：CM670 )，使其相對於加成型聚矽氧烷型化 合物的固形分1〇〇質量份成爲1質量份，調製脫模劑塗 液。再者，此脫模劑塗液中未含界面活性劑。 接著，將上述所得到之不具有脫模層的二軸延伸聚酯 薄膜滾筒捲出，被捲出的二軸延伸聚酯薄膜之寬度方向中 之中央部上，塗佈上述所調製的脫模劑塗液，使塗佈量爲 -62- 200934660(Example 7) A release film was obtained in the same manner as in Example 4 except that the respective conditions of the respective steps were as follows. The results of various measurements and evaluations using the obtained release film are shown in Table 2. [Preparation of a coating agent] As a surfactant, a polyethylene oxide/methyl polyoxane copolymer of 6 parts of a nonionic polyoxyalkylene surfactant is used (曰本乳(股) System, trade name: EMALEX SS-5 05 1) (S2 into -60- 200934660 points). Further, the solid content of the coating agent was 6.5 mass%. Further, the solid content ratio of each component in the release layer 1% by mass of the coating agent is as follows. Main agent: 7 8 · 1% by mass Crosslinking agent: 7.8% by mass Decane coupling agent: 4.7% by mass Surfactant: 9.4% by mass e Comparative Example 4 The conditions in each step were the same as in Example 4 except for the following. A release film was obtained. The results of various measurements and evaluations using the obtained release film' are shown in Table 2. [Preparation of the coating agent] The surfactant is not used, and the solid content of the coating agent is 5 to 9 φ% by mass, and the components of the release layer 1% by mass of the coating agent obtained by the coating agent The solid fraction ratio is as follows. Main agent: 86.2% by mass Crosslinking agent: 8.6% by mass Decane coupling agent: 5.2 mass ° /. Surfactant: 〇% by mass [One-step extension step] The longitudinal stretching ratio was 3.0 times -61 - 200934660 Comparative Example 5 The release film was obtained in the same manner as in Comparative Example 4 except for the following. The results of various measurements and evaluations using the obtained release film' are shown in Table 2. [One extension step] The longitudinal stretching ratio was 4.8 times. [Secondary stretching step] The lateral stretching ratio was 3.0 times. Comparative Example 6 A biaxially stretched polyester film having no release layer was obtained in the same manner as in Example 3 except that the coating agent was not applied. Next, a Pt catalyst (Toshiba) was added to a toluene solution (solid content concentration: 3% by mass) of a polysiloxane compound (Toshiba polyoxane (trade name: TPR-672 1)). The polysiloxane (manufactured by polyoxyalkylene) (trade name: CM670) was used to prepare a release agent coating liquid in an amount of 1 part by mass based on 1 part by mass of the solid content of the addition-molding polyoxyalkylene type compound. Further, the release agent coating solution does not contain a surfactant. Next, the above-obtained biaxially stretched polyester film roll having no release layer is taken up, and the center portion in the width direction of the rolled biaxially stretched polyester film is coated with the above-mentioned prepared release film. Coating solution, the coating amount is -62- 200934660
(wet ) 6g/m2，使 自爲 38cm的空I 2,000kPa 、乾燥溫 而形成脫模層， 〇.2g/m2的脫模薄 的測量.評估的結 佈，係於未延伸聚 上實施。 用下方及上方的空氣流吹出口的間隔各 L浮上搬運式乾燥装置，以搬運張力： 度：160°C、乾燥時間：16秒使其乾燥 得到脫模層的乾燥硬化後的重量爲 膜。使用所得到的脫模薄膜，進行各種 果列示於表2。再者，脫模劑塗液的塗 酯薄膜成形步驟中未接觸冷卻轉筒之面(wet) 6 g/m2, a release layer of 38 cm empty space of 2,000 kPa, drying temperature, and a measurement of release mold of 22 g/m2. The evaluation of the evaluation was carried out on the unstretched. The air was blown at the interval between the lower and upper air flow outlets to carry the tension: Degree: 160 ° C, drying time: 16 seconds to dry. The weight of the release layer after drying and hardening was obtained as a film. Using the obtained release film, various effects are shown in Table 2. Further, the surface of the release film of the release agent coating liquid is not in contact with the surface of the cooling drum
-63- 200934660 實施例7 CN 寸 Os -0.28 -0.19 -0.08 -0.43 -0.18 -0.50 0.32 448 ^Γ) 〇 00 〇 00 〇 ◎ 實施例6 CN 〇\ -0.28 -0.19 -0.08 -0.43 -0.18 -0.50 0.32 448 455 ◎ Os c> 〇 ◎ 實施例5 <N m in oi -0.28 -0.19 -0.08 -0.43 -0.18 -0.50 0.32 448 455 ◎ (N 〇 ◎ 實施例4 cs xn o -0.28 -0.19 -0.08 -0.43 -0.18 -0.50 0.32 448 ◎ t—η 寸 〇 〇 實施例3 CN -0.31 -0.24 -0.10 -0.39 -0.20 -0.40 0.20 450 460 ◎ ο 〇 〇 ◎ 單位 1 質量0/〇 1 i 1 > 1 1 測量•評估項目 種類 含量 載重0.3MPa 載重l.OMPa 載重2.5MPa 載重 0.01 MPa 無載重 無載重 1 脫模層表面 不具有脫模層之側的表面 1 脫模薄膜 陶瓷片 表面平滑性 (條件2) 層合評估2 (位置偏移評估） 1 ·： u H ί <i 1 1 a tH fe s i g Ψ |Q |< 長邊方向的伸長率(Smd) 寬度方向的伸長率(sTD) 長邊方向的熱伸長率(HSmd) 寬度方向的熱伸長率(hstd) 1 HSmd-HSjd 最大高度(Rmax) 剝離評估 剝離帶電評估 ^ i M. g {_ 脫模 -rf-fcrrwi? 隱丨 -64- 200934660 m 比較例ό 摧 1 -0.05 0.02 0.13 0.00 -0.05 0.00 -0.05 452 464 ◎ 00 〇 X 比較例5 揉 1 -0.48 -0.38 -0.30 -0.10 -0.50 -0.10 -0.40 4T) JO 寸 ◎ 〇〇 〇 X 比較例4 摧 1 -0.20 -0.14 0.05 -0.62 -0.10 -0.70 0.60 440 Ο ◎ in in 〇 X 單位 1 質量％ i i 1 > 1 1 測量•評估項目 種類 含量 載重0.3MPa 載重l.OMPa 載重2.5MPa 載重 0.01 MPa 無載重 無載重 1 脫模層表面 不具有脫模層之側的表面 1 脫模薄膜 陶瓷片 表面平滑性 (條件2) 層合評估2 (位置偏移評估） 1 5 Η 狂 J ί <ί i ϊ ϋ 5 i ra £ 1 § 長邊方向的伸長率(Smd) 寬度方向的伸長率(Std) 長邊方向的熱伸長率(HSmd) 寬度方向的熱伸長率(hstd) HSmd-HStd 最大高度(Rmax) 剝離評估 剝離帶電評估 ds 1 ,¾ p dc % _ S M. g g 脫模 ttfcthef 1! | ί -65- 200934660 實施例8 [聚酯的製造] 與實施例1同樣作法，得到固有黏度0.6 5 ( 3 5 °c、鄰 氯酚中）的聚對苯二甲酸乙二醇酯組成物。 [塗劑的調製] 與實施例3同樣作法，得到塗劑。再者，塗劑的固形 分重量爲6.0質量％。此外，由此塗劑所得到的脫模層 100質量％中之各成分的固形分比率，如下述。 主劑：8 4 · 1質量％ 交聯劑：8 · 4質量％ 矽烷偶合劑：5.0質量％ 界面活性劑：2.5質量％ [未延伸聚酯薄膜成形步驟] 使用上述所得到的聚對苯二甲酸乙二醇酯組成物，與 實施例3同樣作法，得到厚度4 5 0 μιη的未延伸聚酯薄膜。 [一次延伸步驟] 使用所得到的未延伸聚酯薄膜，與實施例1同樣作 法，得到長邊方向一軸延伸聚酯薄膜。 [線上塗佈步驟] 接著，於所得到的長邊方向一軸延伸聚酯薄膜’藉由 -66- 200934660 塗佈上述所調製的塗劑，使得到的脫模薄膜中之脫模層的 厚度成爲40nm，得到具有塗膜之聚酯薄膜。再者，塗劑 的塗佈，係在於未延伸聚酯薄膜成形步驟中未接觸冷卻轉 筒之面上實施。 [二次延伸步驟] 接著，將具有所得到的塗膜之聚酯薄膜供給至定型 機，與實施例1同樣作法，製成二軸延伸聚酯薄膜。 [熱固定步驟] 針對所得到的二軸延伸聚酯薄膜，與實施例1同樣作 法，得到全厚度31 μιη的脫模薄膜。使用此處所得到的脫 模薄膜作爲切割前的脫膜薄膜，進行各種的測量·評估的 結果列示於表3。 φ [切割步驟] 捲取條件，係初期張力47N/m、張力錐度率60% ( — 定）、隙壓 150N/m、隙壓錐度率 100%、速度1 80m/分 鐘，得到450mm寬度2,000m長的脫模薄膜滾筒。針對所 得到的脫模薄膜滾筒，進行各種的測量•評估的結果列示 於表3。 此外，距離所得到的脫模薄膜滾筒的表層爲500m的 位置上進行取樣，得到脫模薄膜。使用此處所得到的脫模 薄膜作爲切割後的脫膜薄膜，進行各種的測量•評估的結 -67- 200934660 果列示於表3。 實施例9 各步驟中之各條件如下述以外，與實施例8同樣{乍& 而得到脫模薄膜，得到切割前的脫模薄膜、脫模薄膜滾 筒、切割後的脫模薄膜。使用此等，進行各種的測量•評 估的結果列示於表3。 0 [塗劑的調製] 未使用界面活性劑，再者，塗劑的固形分重量爲5.9 質量％。此外，由此塗劑所得到的脫模層1 00質量％中之 各成分的固形分比率，如下述。 主劑：8 6.2質量％ 交聯劑：8.6質量％ 矽烷偶合劑：5.2質量％ 界面活性劑：〇質量％ ^ [二次延伸步驟] 使橫延伸倍率爲4.5倍。 [熱固定步驟] 使弛緩處理中的弛緩量爲4.0%。 實施例1 0 -68- 200934660 各步驟中之各條件如下述以外，與實施例9同樣作法 而，得到切割前的脫模薄膜、脫模薄膜滾筒、切割後的脫 模薄膜。使用此等’進行各種的測量•評估的結果列示於 表3。 [塗劑的調製] 作爲界面活性劑，使用〇.06份的非離子系的聚矽氧 烷系界面活性劑之聚氧化乙烯•甲基聚矽氧烷共聚合物 (日本乳膠股份有限公司製、商品名：EMALEX SS-505 1 ) (S2成分）。再者，塗劑的固形分重量爲6.0質量 %。此外，由此塗劑所得到的脫模層1 〇〇質量％中之各成 分的固形分比率，如下述。 主劑：8 5 · 4質量％ 交聯劑：8 · 5質量％ 矽烷偶合劑：5 . 1質量％ 界面活性劑：1 . 〇質量％ 實施例1 1 各步驟中之各條件如下述以外，與實施例1 0同樣作 法’得到切割前的脫模薄膜、脫模薄膜滾筒、切割後的脫 模薄膜。使用此等，進行各種的測量•評估的結果列示於 表3。 [塗劑的調製] -69- 200934660 使界面活性劑（S2成分）的添加量爲〇.15份。再 者’塗劑的固形分重量爲6.0質量％。此外，由此塗劑所 得到的脫模層1 〇 〇質量％中之各成分的固形分比率，如下 述。 主劑：84.1質量％ 交聯劑：8.4質量％ 矽烷偶合劑：5.0質量％ 界面活性劑：2 · 5質量％ ❹ [切割步驟] 切割步驟中的捲取條件，如表3所述。 實施例1 2〜1 5 除了使切割步驟中的捲取條件，如表3所述以外，與 實施例1 1同樣作法’得到切割前的脫模薄膜、脫模薄膜 滾筒、切割後的脫模薄膜。使用此等，進行各種的測量. 0 評估的結果列示於表3。 實施例16 各步驟中之各條件如下述以外，與實施例1 0同樣作 法，得到切割前的脫模薄膜、脫模薄膜滾筒、切割後的脫 模薄膜。使用此等，進行各種的測量.評估的結果列示於 表3。 -70- 200934660 [塗劑的調製] 使界面活性劑（S2成分）的添加量爲〇.3份。再者’ 塗劑的固形分重量爲6.2質量％。此外，由此塗劑所得到 的脫模層1〇〇質量％中之各成分的固形分比率，如下述。 主劑：8 2.0質量％ 交聯劑：8.2質量％ 矽烷偶合劑：4.9質量％ A 界面活性劑：4.9質量％ ◎ 實施例1 7 各步驟中之各條件如下述以外，與實施例1 0同樣作 法，得到切割前的脫模薄膜、脫模薄膜滚筒、切割後的脫 模薄膜。使用此等，進行各種的測量•評估的結果列示於 表3。 φ [塗劑的調製] 使界面活性劑（S2成分）的添加量爲0.6份。再者’ 塗劑的固形分重量爲6 · 5質量％。此外’由此塗劑所得到 的脫模層1〇〇質量％中之各成分的固形分比率’如下述。 主劑：78.1質量％ 交聯劑：7 · 8質量°/。 矽烷偶合劑：4.7質量％ 界面活性劑：9.4質量％ 200934660 比較例7 各步驟中之各條件如下述以外’與實施例9同樣作 法，得到切割前的脫模薄膜、脫模薄膜滾筒、切割後的脫 模薄膜。使用此等，進行各種的測量•評估的結果列示於 表3。 [―次延伸步驟] 使縱延伸倍率爲3.0倍。 ❹ 比較例8 各步驟中之各條件如下述以外，與實施例9同樣作 法，得到切割前的脫模薄膜、脫模薄膜滾筒、切割後的脫 模薄膜。使用此等，進行各種的測量•評估的結果列示於 表3。 [一次延伸步驟] 使縱延伸倍率爲4.8倍。 ® [二次延伸步驟] 使橫延伸倍率爲3.0倍。 比較例9 除了不塗佈塗劑以外，與實施例8同樣作法’得到不 具有脫模層之二軸延伸聚酯薄膜。 -72- 200934660 接著，於加成型聚矽氧烷系化合物（東芝聚矽氧烷公 司製、商品名：TPR-6721 )的甲苯溶液（固形分濃度·· 3 質量％ )中，加入Pt觸媒（東芝聚矽氧烷公司製、商品 名：CM670 )，使其相對於加成型聚矽氧烷型化合物的固 形分100質量份成爲1質量份，調製脫模劑塗液。再者， 此脫模劑塗液中未含有界面活性劑。 接著，將上述所得到之不具有脫模層的二軸延伸聚酯 A 薄膜滾筒捲出，被捲出的二軸延伸聚酯薄膜之寬度方向中 〇 之中央部上，塗佈上述之經調整的脫模劑塗液，使塗佈量 爲（wet ) 6g/m2，使用下方及上方的空氣流吹出口的間隔 各自爲38cm的空氣浮上搬運式乾燥装置，以搬運張力： 2,000kPa、乾燥溫度：160°C、乾燥時間：16秒使其乾燥 而形成脫模層，得到脫模層的乾燥硬化後的重量爲 0.2g/m2的脫模薄膜。此處所得到的脫模薄膜作爲切割前 的脫膜薄膜，進行各種的測量·評估的結果列示於表3。 φ 再者，脫模劑塗液的塗佈，係在於未延伸聚酯薄膜成形步 驟中未接觸冷卻轉筒之面上實施。 [切割步驟] 使切割步驟中的捲取條件，如表3所述，得到脫模薄 膜滾筒、切割後的脫模薄膜。使用此等，進行各種的測 量·評估的結果列示於表3。 參考例1 -73- 200934660 除了使切割步驟中的捲取條件，如表3所述以外，與 實施例11同樣作法，得到切割前的脫模薄膜、脫模薄膜 滾筒、切割後的脫模薄膜。使用此等，進行各種的測量· 評估的結果列示於表3。-63- 200934660 Embodiment 7 CN Inch Os -0.28 -0.19 -0.08 -0.43 -0.18 -0.50 0.32 448 ^Γ) 〇00 〇00 〇◎ Example 6 CN 〇\ -0.28 -0.19 -0.08 -0.43 -0.18 - 0.50 0.32 448 455 ◎ Os c> 〇 ◎ Example 5 <N m in oi -0.28 -0.19 -0.08 -0.43 -0.18 -0.50 0.32 448 455 ◎ (N 〇◎ Example 4 cs xn o -0.28 -0.19 - 0.08 -0.43 -0.18 -0.50 0.32 448 ◎ t-η inch 〇〇Example 3 CN -0.31 -0.24 -0.10 -0.39 -0.20 -0.40 0.20 450 460 ◎ ο 〇〇◎ Unit 1 Mass 0/〇1 i 1 > 1 1 Measurement and evaluation item type content load 0.3MPa load l.OMPa load 2.5MPa load 0.01 MPa no load no load 1 surface of the release layer without the side of the release layer 1 surface smoothness of the release film ceramic sheet ( Condition 2) Lamination evaluation 2 (positional offset evaluation) 1 ·: u H ί <i 1 1 a tH fe sig Ψ |Q |<Elongation in the longitudinal direction (Smd) Elongation in the width direction (sTD) ) Thermal elongation in the long-side direction (HSmd) Thermal elongation in the width direction (hstd) 1 HSmd-HSjd Maximum height (Rmax) Peel evaluation Stripping electrification Estimate ^ i M. g {_ Stripping-rf-fcrrwi? Concealing -64- 200934660 m Comparative Example 摧 1 -0.05 0.02 0.13 0.00 -0.05 0.00 -0.05 452 464 ◎ 00 〇X Comparative Example 5 揉1 -0.48 -0.38 -0.30 -0.10 -0.50 -0.10 -0.40 4T) JO inch ◎ 〇〇〇X Comparative Example 4 Destruction 1 -0.20 -0.14 0.05 -0.62 -0.10 -0.70 0.60 440 Ο ◎ in in 〇X Unit 1% by mass ii 1 > 1 1 Measurement and evaluation item type content load 0.3MPa load l.OMPa load 2.5MPa load 0.01 MPa no load no load 1 surface of the release layer without the release layer side 1 release film ceramic sheet surface smoothing Sex (Condition 2) Lamination Evaluation 2 (Position Offset Evaluation) 1 5 Η 狂 J ί <ί i ϊ ϋ 5 i ra £ 1 § Elongation in the longitudinal direction (Smd) Elongation in the width direction (Std) Thermal elongation in the long-side direction (HSmd) Thermal elongation in the width direction (hstd) HSmd-HStd Maximum height (Rmax) Peel evaluation Stripping electrification evaluation ds 1 , 3⁄4 p dc % _ S M. gg Release ttfcthef 1! | ί -65- 200934660 Example 8 [Production of Polyester] In the same manner as in Example 1, an intrinsic viscosity of 0.6 5 (3) was obtained. Polyethylene terephthalate composition at 5 °c, o-chlorophenol). [Preparation of paint agent] A paint was obtained in the same manner as in Example 3. Further, the solid content of the coating agent was 6.0% by mass. Further, the solid content ratio of each component in 100% by mass of the release layer obtained by the coating agent is as follows. Main agent: 8 4 · 1% by mass Crosslinking agent: 8 · 4% by mass Decane coupling agent: 5.0% by mass Surfactant: 2.5% by mass [Unstretched polyester film forming step] Using the polyparaphenylene obtained above The ethylene glycol formate composition was treated in the same manner as in Example 3 to obtain an unstretched polyester film having a thickness of 450 μm. [One-time extension step] Using the obtained unstretched polyester film, a longitudinal direction monoaxially stretched polyester film was obtained in the same manner as in Example 1. [On-line coating step] Next, the polyester film is stretched one-axis in the longitudinal direction obtained by applying the above-mentioned prepared coating agent by -66-200934660, so that the thickness of the release layer in the obtained release film becomes At 40 nm, a polyester film having a coating film was obtained. Further, the application of the coating agent is carried out on the surface of the unstretched polyester film forming step which is not in contact with the cooling drum. [Secondary stretching step] Next, a polyester film having the obtained coating film was supplied to a sizing machine, and a biaxially stretched polyester film was produced in the same manner as in Example 1. [Heat fixing step] A film having a total thickness of 31 μm was obtained in the same manner as in Example 1 with respect to the obtained biaxially stretched polyester film. The results of various measurements and evaluations using the release film obtained herein as a release film before dicing are shown in Table 3. φ [Cutting step] Winding conditions are initial tension 47N/m, tension taper rate 60% (-), gap pressure 150N/m, gap pressure taper rate 100%, speed 1 80m/min, and 450mm width 2,000m Long release film roll. The results of various measurements and evaluations for the obtained release film roll are shown in Table 3. Further, a sample was taken at a position of 500 m from the surface of the obtained release film roll to obtain a release film. The release film obtained here was used as a release film after dicing, and various measurements and evaluations were carried out. -67- 200934660 The results are shown in Table 3. Example 9 The conditions of the respective steps were as follows except that the release film was obtained in the same manner as in Example 8 to obtain a release film before dicing, a release film roll, and a release film after dicing. Using these, various measurements and evaluation results are shown in Table 3. 0 [Preparation of paint agent] The surfactant was not used, and the solid content of the paint was 5.9 mass%. Further, the solid content ratio of each of the components of the release layer obtained by the coating agent in 100% by mass is as follows. Main agent: 8 6.2% by mass Crosslinking agent: 8.6% by mass Decane coupling agent: 5.2% by mass Surfactant: 〇% by mass ^ [Secondary extension step] The lateral stretching ratio was 4.5 times. [Heat fixation step] The relaxation amount in the relaxation treatment was 4.0%. Example 1 0 - 68 - 200934660 Each of the conditions in the respective steps was carried out in the same manner as in Example 9 to obtain a release film before dicing, a release film roll, and a release film after dicing. The results of using these measurements to perform various measurements and evaluations are shown in Table 3. [Preparation of a coating agent] As a surfactant, a polyethylene oxide/methyl polyoxyalkylene copolymer of 0.001 parts of a nonionic polyoxyalkylene surfactant was used (manufactured by Nippon Latex Co., Ltd.) , trade name: EMALEX SS-505 1) (S2 component). Further, the solid content of the coating agent was 6.0% by mass. Further, the solid content ratio of each component in the release layer 1% by mass of the coating agent is as follows. Main agent: 8 5 · 4 mass% Crosslinking agent: 8 · 5 mass % decane coupling agent: 5.1 mass % Surfactant: 1. 〇 mass % Example 1 1 Each condition in each step is as follows In the same manner as in Example 10, a release film before cutting, a release film roll, and a release film after cutting were obtained. Using these, various measurements and evaluation results are shown in Table 3. [Preparation of a coating agent] -69- 200934660 The amount of the surfactant (component S2) added was 〇.15 parts. Further, the solid content of the coating agent was 6.0% by mass. Further, the solid content ratio of each component in the release layer 1 〇 mass% obtained by the coating agent is as follows. Main agent: 84.1% by mass Crosslinking agent: 8.4% by mass Decane coupling agent: 5.0% by mass Surfactant: 2 · 5 mass% 切割 [Cutting step] The winding conditions in the cutting step are as described in Table 3. Example 1 2 to 1 5 In the same manner as in Example 1 except that the winding conditions in the cutting step were as described in Table 3, the release film before the cutting, the release film roll, and the release after cutting were obtained. film. Using these, various measurements were made. 0 The results of the evaluation are shown in Table 3. Example 16 The conditions of the respective steps were the same as in Example 10 except that the release film before the dicing, the release film roll, and the release film after the dicing were obtained. Using these, various measurements were made. The results of the evaluation are shown in Table 3. -70- 200934660 [Preparation of coating agent] The amount of the surfactant (component S2) added was 〇.3 parts. Further, the solid content of the coating agent was 6.2% by mass. Further, the solid content ratio of each component in the release layer of the release layer obtained by the coating agent is as follows. Main component: 8 2.0% by mass Crosslinking agent: 8.2% by mass Decane coupling agent: 4.9 mass% A Surfactant: 4.9 mass% ◎ Example 1 7 Each of the conditions in each step is the same as in Example 10 except In the method, a release film before cutting, a release film roll, and a release film after cutting are obtained. Using these, various measurements and evaluation results are shown in Table 3. φ [Preparation of paint agent] The amount of the surfactant (component S2) added was 0.6 part. Further, the solid content of the coating agent was 6.5 mass%. Further, the solid content ratio of the respective components in the release layer of the release layer obtained by the coating agent is as follows. Main agent: 78.1% by mass Crosslinking agent: 7 · 8 mass ° /. Decane coupling agent: 4.7 mass% Surfactant: 9.4 mass% 200934660 Comparative Example 7 Each of the conditions in each step was the same as in Example 9 to obtain a release film before cutting, a release film roll, and after cutting. Release film. Using these, various measurements and evaluation results are shown in Table 3. [―Sub-Extension Step] The vertical stretch ratio is 3.0 times. ❹ Comparative Example 8 The conditions of the respective steps were the same as in Example 9 except that the release film before the dicing, the release film roll, and the release film after the dicing were obtained. Using these, various measurements and evaluation results are shown in Table 3. [One extension step] The longitudinal stretching ratio was 4.8 times. ® [Secondary extension step] The lateral stretch ratio is 3.0 times. Comparative Example 9 A biaxially stretched polyester film having no release layer was obtained in the same manner as in Example 8 except that the coating agent was not applied. -72- 200934660 Next, a Pt catalyst was added to a toluene solution (solid content concentration··3 mass %) of a polyoxyalkylene-based compound (manufactured by Toshiba Polyoxane Co., Ltd., trade name: TPR-6721). (manufactured by Toshiba Polyoxane Co., Ltd., trade name: CM670), the amount of the solid component of the addition-molding polyoxyalkylene type compound was changed to 1 part by mass to prepare a release agent coating liquid. Further, the release agent coating solution does not contain a surfactant. Next, the biaxially stretched polyester A film roll having the release layer obtained above is taken up, and the center portion of the twisted biaxially stretched polyester film in the width direction is coated, and the above-mentioned adjustment is applied. The release agent coating liquid was applied to a coating amount of (wet) 6 g/m 2 , and an air floating transport drying device having a space of 38 cm each of the air flow outlets below and above was used to carry the tension: 2,000 kPa, drying temperature. : 160 ° C, drying time: 16 seconds, it was dried to form a release layer, and a release film having a weight of 0.2 g/m 2 after drying and hardening of the release layer was obtained. The release film obtained here was used as a release film before dicing, and various measurement and evaluation results are shown in Table 3. Further, the application of the release agent coating liquid is carried out on the surface of the unstretched polyester film forming step which is not in contact with the cooling drum. [Cutting Step] The winding conditions in the cutting step were as described in Table 3 to obtain a release film roll and a cut release film after cutting. The results of various measurements and evaluations using these are shown in Table 3. Reference Example 1 - 73 - 200934660 In the same manner as in Example 11, except that the winding conditions in the cutting step were as described in Table 3, a release film before cutting, a release film roll, and a release film after cutting were obtained. . The results of various measurements and evaluations using these are shown in Table 3.
-74- 200934660 ❹ο 實施例14 m in CN -0.28 -019 -0.08 I -0.43 -0.18 -0.50 0.32 1 00 ◎ (N T-H 〇 ◎ 實施例13 CN OQ (N -0.28 -0.19 -0.08 -0.43 -0.18 -0.50 0.32 oo 1 455 i 1 ◎ (N 〇 ◎ 實施例12 (N ΧΠ yr\ (N -0.28 -0.19 -0.08 -0.43 -0.18 -0.50 0.32 00 455 ◎ (N r·*^ 〇 ◎ 實施例11 (N χη in CA -0.28 -0.19 -0.08 -0.43 -0.18 -0.50 0.32 oo 455 ◎ r—( 〇 ◎ 實施例10 CN ζΛ O -0.28 -0.19 1 -0.08 -0.43 -0.18 -0.50 0.32 00 455 ◎ ί-Η 寸 〇 〇 實施例9 摧 1 -0.28 -0.19 1-0.08 -0.43 -0.18 -0.50 0.32 oo 455 ◎ in (N 〇 1 實施例8 iT) 04 -0.31 -0.24 -0.10 1 -0.39 -0.20 -0.40 0.20 450 460 ◎ p 〇 〇 ◎ 單位 I 質量％ i i 1 > a 1 測量•評估項@ 種類 含量 載重0.3MPa 載重1崖Pa 載重2.5MPa 1 載重 O.OIMPa 無載重 「無載重 !_ 1 脫模層表面 不具有脫模層之 側的表面 1 脫模薄膜 陶瓷片 表面平滑性 (條件2) 層合評估2 (位置偏移評估） 界面活性劑 長邊方向的伸 長率(Smd) 寬度方向的伸 長率(Std) m 3 侄® 111¾ 尼& m ¢( w f： 1 HSmd-HStd I 最大尚度 (Rmax) 剝離評估 剝離帶電評估 If® έ in 脫模層 切割前 的脫模 薄膜 -75- 200934660 i 實施例14 〇 Ο 1-H 360 〇 ◎ 實施例13 〇 〇 \〇 Ο 〇 r-H 100 380 ◎ ◎ 實施例12 % 〇〇 <N 400 ◎ ◎ 實施例11 g 00 CO g (N Ό 1-H 420 ◎ 〇 實施例10 00 (N iTi CO 400 ◎ ◎ 實施例9 oo CM 〇 沄 410 ◎ ◎ 實施例8 § oo (N 〇 泛 r*H 410 ◎ ◎ 單位 N/m N/m N/m N/m 1 測量•評估項@ 初期張力 張力錐度率 最後張力 初期隙壓 隙壓錐度率 最終隙壓 撮大値） 1 1 捲取條件 滾筒表層的維 氏硬度(Hv) 捲取偏移 平坦性 脫模薄 膜滾筒 切割後的 脫模薄膜 -76- 200934660 e (鵜)¾ 參考例1 (N K/1 Η -0.28 1 -0.19 -0.08 -0.43 -0.18 -0.50 0.32 I 〇〇 in ◎ CN 1—Η 〇 ◎ 比較例9 摧 1 -0.05 0.02 1 0-13 1 0.00 -0.05 0.00 -0.05 ! (N 寸 464 1 1 ◎ oo 〇 X 比較例8 摧 1 -0.48 -0.38 -0.30 -0.10 -0.50 -0.10 -0.40 in $ 465 ◎ 00 m <N 〇 X 比較例7 摧 1 -0.20 |_-0·14 I _0.05 -0.62 -0.10 -0.70 0.60 〇 450 ◎ 卜^ ^T) CA 〇 X 實施例17 CN 00 寸 -0.28 -0.19 -0.08 -0.43 1_ -0.18 -0.50 0.32 〇〇 455 〇 oo o oo 〇 ◎ 實施例16 <N m 寸· -0.28 -0.19 Γ -0.08 -0.43 -0.18 -0.50 Γ 0.32 00 455 ◎ 〇\ o Os 〇 ◎ 實施例15 (N CO (S -0.28 -〇·ΐ9 1 -0.08 1 -0.43 -0.18 -0.50 0.32 1 448 455 ◎ (N 〇 ◎ 單位 i 質量％ 1 1 1 1 t 測量•評估項目 種類 丨含量 載重0.3MPa 載重l.OMPa 載重2.5MPa 載重 0.01 MPa 無載重 無載重 1 脫模層表面 S e 释k ^ s 1 脫模薄膜 陶瓷片 表面平滑性 (條件2) £義 || 幽β 'w' 界面活性劑 長邊方向的伸 長率(Smd) 寬度方向的伸 長率(Std) m ^ S 00 1¾寒; § ^ •ϋ ® 侧瞰 HSmd-HStd 最大高度 (Rmax) 剝離評估 剝離帶電評估 担^ 1¾ ^ © tel | s s ^ Μ. ^ 脫模 切割 前的 脫模 薄膜 -77- 200934660 is 參考例1 in 〇 CS g 〇 § 460 ◎ X 比較例9 00 CN m 400 ◎ ◎ 比較例8 00 CN «η cn i-H 400 ◎ ◎ 比較例7 〇〇 (N V) cn r—^ 〇 〇 ◎ ◎ 實施例17 00 (N 〇 〇 ◎ ◎ 實施例16 00 (N 〇 ο ψ-Η ◎ ◎ 實施例15 〇 (N 〇 m <] ◎ 單位 N/m N/m N/m N/m 1 測量•評估項@ 初期張力 張力錐度率 最後張力 初期隙壓 隙壓錐度率 最終隙壓 (最大値） i 1 1 捲取條件 滾筒表層的維 氏硬度(Hv) 捲取偏移 平坦性 脫模薄 膜滾筒 切割後的 脫模薄膜 〇ο -78- 200934660 實施例18 [聚酯的製造] 與實施例1同樣作法，得到固有黏度0.65 ( 351 氯酚中）的聚對苯二甲酸乙二醇酯組成物。 [塗劑的調製] 與實施例3同樣作法，得到塗劑。再者，塗劑的 ^ 分重量爲6.0質量。/。。此外，由此塗劑所得到的脫 100質量％中之各成分的固形分比率，如下述。 主劑：8 4.1質量％ 交聯劑：8.4質量％ 矽烷偶合劑：5.0質量％ 界面活性劑：2.5質量％ [未延伸聚酯薄膜成形步驟] 0 將上述所得到的聚對苯二甲酸乙二醇酯組成物 物，以17(TC乾燥5小時，使聚對苯二甲酸乙二醇酯 物組成物的水分率成爲0.05質量％以下爲止，接著， 乾燥的聚對苯二甲酸乙二醇酯組成物組成物供給至 機，於熔融溫度280~300°C進行熔融擠壓，使用平均 大小1 1 μιη的鋼線過濾器進行高精度過濾後，藉由模 行擠壓製成熔融片，藉由將該相關的熔融片用靜電密 接觸於冷卻轉筒令其急冷，得到厚度48 Ομηι的未延伸 薄膜。 、鄰 固形 模層 組成 組成 將經 擠壓 網目 具進 著法 聚酯 -79- 200934660 [一次延伸步驟] 將所得到的未延伸聚酯薄膜，以75 °C預熱，接著，於 低速·高速的滾筒之間以薄膜溫度105 °C在長邊方向延伸 3.8倍，然後，藉由急冷而得到長邊方向一軸延伸聚酯薄 膜。 [線上塗佈步驟] 接著，於所得到的長邊方向一軸延伸聚酯薄膜，藉由 塗佈上述所調製的塗劑，使得到的脫模薄膜中之脫模層的 厚度成爲40nm，得到具有塗膜之聚酯薄膜。再者，塗劑 的塗佈，係在於未延伸聚酯薄膜成形步驟中未接觸冷卻轉 筒之面上實施。 [二次延伸步驟] 接著，將具有所得到的塗膜之聚酯薄膜供給至定型 機，與實施例1同樣作法，製成二軸延伸聚酯薄膜。 [熱固定步驟] 針對所得到的二軸延伸聚酯薄膜’與實施例1同樣作 法，得到全厚度3 1 μιη的脫模薄膜。使用所得到的脫模薄 膜，進行各種的測量•評估。結果列示於表4。 實施例1 9 -80- 200934660 各步驟中之各條件如下述以外，與實施例18同樣作 法而得到全厚度31 μιη的脫模薄膜。使用所得到的脫模薄 騰’進行各種的測量•評估。結果列示於表4。 [塗劑的調整] 作爲界面活性劑，使用0.06份的非離子系的聚矽氧 燒系界面活性劑之聚氧化乙烯•甲基聚矽氧烷共聚合物 〇 (日本乳膠（股）製、商品名：EMALEX SS-505 1 ) ( S2 成分），取代聚氧化乙烯油醯基醚。再者，塗劑的固形分 重量爲6.0質量％。此外，由此塗劑所得到的脫模層100 質量％中之各成分的固形分比率，如下述。 主劑：8 4.1質量％ 交聯劑：8.4質量％ 矽烷偶合劑：5.0質量％ 界面活性劑：2.5質量％ [〜次延伸步驟] 使縱延伸倍率爲4.0倍。 [熱固定步驟] 使驰緩處理中的弛緩量爲4.0%。 -81 - 200934660 寸漱 實施例19 (Ν Χ/1 r4 〇 — 16.4 -0.35 -0.29 -0.15 -0.37 -0.25 -0.39 0.14 (Ν 454 460 ◎ 〇 〇 〇 ◎ 實施例18 CN 00 — 15.6 -0.33 -0.26 -0.12 -0.38 -0.23 -0.40 0.17 〇\ (Ν ^Τ) CN 452 458 ◎ 〇 〇 〇 ◎ 單位 質量％ φ 1 1 1 1 1 1 1 1 測量•評估項目 種類 含量 長邊方向 寬度方向 Μ 1 載重0_3MPa 載重l.OMPa 載重2.5MPa 載重 0.01 MPa 無載重 無載重 1 縱方向 橫方向 脫模層表面 不具有脫模層之側的表面 1 脫模薄膜 陶瓷片 表面平滑性滌件2) 厚度斑 脫模層所含有的界面活性劑 延伸倍率 薄膜厚度 丨 長邊方向的伸長率(Smd) 寬度方向的伸長率(sTD) 長邊方向的熱伸長率(HSmd) 寬度方向的熱伸長率(HStd) HSmd-HStd 厚度斑 最大高度(Rmax) 剝離評估 剝離帶電評估 陶瓷片評估 (實用特性代用評估） 脫模薄膜 的特性 ο -82- 200934660 [發明的效果] 本發明的脫模薄膜，係於製造陶瓷片時的加熱張力下 具有適度的尺寸變化率，乾燥陶瓷淤漿時的熱收縮平衡優 異。亦即，充分地符合作爲陶瓷片製時所使用的脫模薄膜 所要求的性能。故，使用本發明的脫模薄膜作爲陶瓷片製 造用的承載薄膜時，因爲不僅在搬運步驟，於乾燥步驟中 承載薄膜的熱收縮平均亦優異，故可高度地抑制所得到的 Γ\ 陶瓷片的厚度斑。 此外，本發明中具有較佳的態樣之脫模薄膜，因爲表 面平滑性優異，可抑制所得到的陶瓷片中針孔發生。故， 若依據本發明中具有較佳的形態之脫模薄膜，可提高陶瓷 片及陶瓷電容器的生產性。 而且，本發明中具有較佳形態之脫模薄膜，可高度地 抑制於捲出承載薄膜之步驟、或從承載薄膜剝離陶瓷片之 步驟中所發生的剝離帶電。其結果，使用用本發明的脫模 ^ 薄膜所製造的陶瓷片，製造陶瓷電容器時，可高度地抑制 所得到的電容器的内部電極的位置偏移。 本發明的薄膜滾筒，可提供平坦性優異的脫模薄膜。 使用用該相關的脫模薄膜所製造陶瓷片，製造陶瓷電容器 時，可得到容量更均勻的陶瓷電容器。 -83--74- 200934660 ❹ο Example 14 m in CN -0.28 -019 -0.08 I -0.43 -0.18 -0.50 0.32 1 00 ◎ (N TH 〇◎ Example 13 CN OQ (N -0.28 -0.19 -0.08 -0.43 -0.18 -0.50 0.32 oo 1 455 i 1 ◎ (N 〇 ◎ Example 12 (N ΧΠ yr\ (N - 0.28 - 0.19 - 0.08 - 0.43 - 0.18 - 0.50 0.32 00 455 ◎ (N r · * ^ 〇 ◎ Example 11 (N χη in CA -0.28 -0.19 -0.08 -0.43 -0.18 -0.50 0.32 oo 455 ◎ r - ( 〇 ◎ Example 10 CN ζΛ O -0.28 -0.19 1 -0.08 -0.43 -0.18 -0.50 0.32 00 455 ◎ ί - Η 〇〇 〇〇 Example 9 Destroy 1 -0.28 -0.19 1-0.08 -0.43 -0.18 -0.50 0.32 oo 455 ◎ in (N 〇1 Example 8 iT) 04 -0.31 -0.24 -0.10 1 -0.39 -0.20 - 0.40 0.20 450 460 ◎ p 〇〇 ◎ Unit I% by mass ii 1 > a 1 Measurement • Evaluation item @ Type content Load 0.3MPa Load 1 Cliff Pa Load 2.5MPa 1 Load O.OIMPa No load “No load! _ 1 off Surface of the mold layer without the side of the release layer 1 Surface smoothness of the release film ceramic sheet (Condition 2) Lamination evaluation 2 (Position offset evaluation) Longitudinal elongation of the surfactant (Smd) Elongation in the width direction (Std) m 3 侄® 1113⁄4 尼 & m ¢ ( wf: 1 HSmd-HStd I maximum degree of refraction (Rmax) Peel evaluation Peeling electrification evaluation If® έ in before release layer cutting Release film-75- 200934660 i Example 14 〇Ο 1-H 360 〇 ◎ Example 13 〇〇 〇Ο H H H H H H H H H H H 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 N N N N N 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施CO g (N Ό 1-H 420 ◎ 〇 Example 10 00 (N iTi CO 400 ◎ ◎ Example 9 oo CM 〇沄 410 ◎ ◎ Example 8 § oo (N 〇 general r*H 410 ◎ ◎ Unit N/ m N/m N/m N/m 1 Measurement • Evaluation item @ Initial tension Tension rate Last tension Initial gap nip Pressure taper rate Final gap pressure 撮 1 1 1 Winding condition Vickers hardness of the surface of the roller (Hv ) Take-up offset flatness Release film after film release film-76- 200934660 e (鹈)3⁄4 Reference example 1 (NK/1 Η -0.28 1 -0.19 -0.08 -0.43 -0.18 -0.50 0.32 I 〇 〇in ◎ CN 1—Η 〇 ◎ Comparative Example 9 Destroy 1 -0.05 0.02 1 0-13 1 0.00 -0.05 0.00 -0.05 ! (N inch 464 1 1 ◎ oo 〇X Comparative Example 8 Destroy 1 -0.48 -0.38 -0.30 -0.10 -0.50 -0.10 -0.40 in $ 465 ◎ 00 m <N 〇X Comparative Example 7 Destroy 1 -0.20 |_-0·14 I _0.05 - 0.62 -0.10 -0.70 0.60 〇450 ◎ 卜 ^ ^T) CA 〇X Example 17 CN 00 inch -0.28 -0.19 -0.08 -0.43 1_ -0.18 -0.50 0.32 〇〇455 〇oo o oo 〇◎ Example 16 < ; N m inch · -0.28 -0.19 Γ -0.08 -0.43 -0.18 -0.50 Γ 0.32 00 455 ◎ 〇 \ o Os 〇 ◎ Example 15 (N CO (S -0.28 -〇·ΐ9 1 -0.08 1 -0.43 - 0.18 -0.50 0.32 1 448 455 ◎ (N 〇 ◎ Unit i% by mass 1 1 1 1 t Measurement • Evaluation item type 丨 Content load 0.3MPa Load l.OMPa Load 2.5MPa Load 0.01 MPa No load No load 1 Release layer surface S e Release k ^ s 1 Surface smoothness of release film ceramic sheet (Condition 2) £义|| ββ 'w' Elongation in the longitudinal direction of the surfactant (Smd) Elongation in the width direction (Std) m ^ S 00 13⁄4寒; § ^ •ϋ ® Side view HSmd-HStd Maximum height (Rmax) Peel evaluation Stripping charge evaluation ^ 13⁄4 ^ © tel | ss ^ Μ. ^ Release film before release cutting -77 - 200934660 is Reference Example 1 in 〇CS g 〇§ 460 ◎ X Comparative Example 9 00 CN m 400 ◎ ◎ Comparative Example 8 00 CN «η cn iH 400 ◎ ◎ Comparative Example 7 〇〇(NV) cn r—^ 〇〇 ◎ ◎ Example 17 00 (N 〇〇 ◎ ◎ Example 16 00 (N 〇ο ψ-Η ◎ ◎ Example 15 〇(N 〇m <] ◎ Unit N/m N/m N/m N/m 1 Measurement and evaluation item @ Initial tension Tension rate Last tension Initial gap nip Pressure taper rate Final gap pressure (maximum 値) i 1 1 Coiling condition Vickers hardness (Hv) of the surface of the roller Coil offset flatness release Release film after film roll dicing 〇ο-78- 200934660 Example 18 [Production of polyester] In the same manner as in Example 1, polyethylene terephthalate having an intrinsic viscosity of 0.65 (in 351 chlorophenol) was obtained. Composition. [Preparation of paint agent] A paint was obtained in the same manner as in Example 3. Further, the coating agent had a mass fraction of 6.0 mass. /. . Further, the solid content ratio of each component in 100% by mass of the obtained coating agent is as follows. Main agent: 8 4.1% by mass Crosslinking agent: 8.4% by mass Decane coupling agent: 5.0% by mass Surfactant: 2.5% by mass [Unstretched polyester film forming step] 0 The above-obtained polyethylene terephthalate The alcohol ester composition was dried at 17 (TC for 5 hours, and the water content of the polyethylene terephthalate composition was 0.05% by mass or less, followed by dried polyethylene terephthalate. The composition of the composition is supplied to the machine, melt-extruded at a melting temperature of 280 to 300 ° C, and subjected to high-precision filtration using a steel wire filter having an average size of 1 μm, and then extruded into a molten sheet by die extrusion. The related molten sheet is electrostatically contacted with the cooling drum to quench it to obtain an unstretched film having a thickness of 48 Ομηι. The composition of the adjacent solid mold layer is extruded into the polyester fabric-79-200934660 [One-step stretching step] The obtained unstretched polyester film was preheated at 75 ° C, and then extended 3.8 times in the longitudinal direction at a film temperature of 105 ° C between the low speed and high speed rolls, and then by Quenching and getting long sides The polyester film is stretched to one axis. [Online coating step] Next, the polyester film is stretched in one direction in the obtained longitudinal direction, and the release layer in the release film is obtained by applying the above-mentioned prepared coating agent. The thickness of the film was 40 nm to obtain a polyester film having a coating film. Further, the application of the coating agent was carried out on the surface of the unstretched polyester film forming step which was not in contact with the cooling drum. [Second Extension Step] The polyester film having the obtained coating film was supplied to a setting machine, and a biaxially stretched polyester film was produced in the same manner as in Example 1. [Heat fixing step] For the obtained biaxially stretched polyester film ' In the same manner as in Example 1, a release film having a total thickness of 3 μm was obtained. Various measurements and evaluations were carried out using the obtained release film. The results are shown in Table 4. Example 1 9 - 80 - 200934660 In each step Each of the conditions was the same as in Example 18, and a release film having a total thickness of 31 μm was obtained. Various measurements and evaluations were carried out using the obtained release liners. The results are shown in Table 4. Adjustment] As a surfactant, 0.06 parts of a nonionic polyoxynene-based surfactant-based polyoxyethylene/methyl polyoxyalkylene copolymer 〇 (made by Nippon Latex Co., Ltd., trade name: EMALEX SS-) 505 1 ) (S2 component), in place of polyoxyethylene oil decyl ether. Further, the solid content of the coating agent is 6.0% by mass. Further, the components of the release layer obtained by the coating agent are 100% by mass. The solid content ratio is as follows: Main agent: 8 4.1% by mass Crosslinking agent: 8.4% by mass Decane coupling agent: 5.0% by mass Surfactant: 2.5% by mass [~Extension step] The longitudinal stretching ratio is 4.0 times. [Heat fixing step] The amount of relaxation in the relaxation treatment was 4.0%. -81 - 200934660 漱 漱 Example 19 (Ν Χ /1 r4 〇 - 16.4 -0.35 -0.29 -0.15 -0.37 -0.25 -0.39 0.14 (Ν 454 460 ◎ 〇〇〇◎ Example 18 CN 00 — 15.6 -0.33 - 0.26 -0.12 -0.38 -0.23 -0.40 0.17 〇\ (Ν ^Τ) CN 452 458 ◎ 〇〇〇◎ Unit mass% φ 1 1 1 1 1 1 1 1 Measurement • Evaluation item type content Long-side direction width direction Μ 1 Load 0_3MPa Load l.OMPa Load 2.5MPa Load 0.01 MPa No load No load 1 Longitudinal direction of the surface of the release layer without the release layer on the surface 1 Release film thin film surface smoothness 2) Thickness spotted Surfactant stretch ratio film thickness contained in the mold layer 伸长 Elongation in the long-side direction (Smd) Elongation in the width direction (sTD) Thermal elongation in the long-side direction (HSmd) Thermal elongation in the width direction (HStd) HSmd -HStd Thickness spot maximum height (Rmax) Peel evaluation Peeling electrification evaluation Ceramic sheet evaluation (utility characteristic substitution evaluation) Characteristics of release film ο-82- 200934660 [Effects of the invention] The release film of the present invention is manufactured by The ceramic sheet has a moderate dimensional change rate under the heating tension, and is excellent in heat shrinkage balance when the ceramic slurry is dried, that is, sufficiently conforms to the performance required for the release film used in the production of the ceramic sheet. When the release film of the present invention is used as a carrier film for producing a ceramic sheet, since the heat shrinkage of the carrier film is excellent not only in the conveyance step but also in the drying step, the thickness of the obtained Γ\ceramic sheet can be highly suppressed. Further, in the present invention, the release film having a preferred aspect can suppress the occurrence of pinholes in the obtained ceramic sheet because of excellent surface smoothness, and therefore, if it is in accordance with the present invention, it has a preferred form of release. The film can improve the productivity of the ceramic sheet and the ceramic capacitor. Moreover, the release film having the preferred embodiment of the present invention can be highly suppressed in the step of unwinding the carrier film or in the step of peeling the ceramic sheet from the carrier film. The resulting peeling electrification. As a result, when the ceramic chip produced by using the release film of the present invention is used, the ceramic capacitor can be highly suppressed. The position of the internal electrode of the obtained capacitor is shifted. The film roll of the present invention can provide a release film having excellent flatness. When a ceramic chip is produced by using the relevant release film, a capacity can be obtained. Uniform ceramic capacitors. -83-