200419604 (1) 玖、發明說明 【發明所屬之技術領域】 本發明是關於剝離薄膜及其製造方法，特別是關於用 來進行疊層陶瓷電容器製造的剝離薄膜及其製造方法。 【先前技術】 在製造電容器、壓電零件、正特性熱阻器、負特性熱 阻器或熱變電阻器等之陶瓷電子零件的情況時，有採取： 在可撓性支承體上，以例如刮刀（doctor blade )法來塗 佈包含有陶瓷粉、有機黏合劑、可塑劑、溶劑等之陶瓷塗 料後形成生坪薄片（green sheet )(介電質層），在其上 利用網點印刷來形成鈀、銀、鎳等的電極之製程。 在於此製造製程，於獲得疊層構造的情況時，將所獲 得到的生坏薄片（green sheet ) —片片地疊層，來形成期 望的疊層構造，再經過沖壓切斷製程，獲得陶瓷空白晶片 (green chip )。將如此所獲得的陶瓷裸晶中的黏合劑脫 臘，以1 000 °C〜1 400°C進行燒成，在所或得到的燒成體 上形成銀、銀-鈀、鎳、銅等的端子電極，來獲得陶瓷電 子零件。 其他尙有被提出：將生坏薄片進行熱轉印，使可撓性 支承體形成在其之上的方法（如日本特開昭63-188926號 公報等）；或在可撓性支承體上，對所必要的疊層數目， 利用反覆進行形成生坏薄片的製程、與在生坏薄片上印刷 電極的製程，來獲得疊層體的方法等。 (2) (2)200419604 在上述的陶瓷電子零件的製造方法，均需要進行將已 被成形的生坏薄片由可撓性支承體剝離的製程，但在於此 製程，會有：當由可撓形支承體剝離時，在生坏薄片上容 易產生破損等之問題點。例如，在疊層陶瓷電容器的情況 時，爲了要求小型化及大容量化，有採用：將每1層的介 電質層的厚度做小，來增加疊層數的方法的情況，但，生 坏薄片的損傷是隨著這種薄膜化，而變得更顯著。由於一 旦生坏薄片損傷，則在於最終製品會大量產生短路等的特 性不良，使得疊層良率降低，故，以往以來一直針對用來 在可撓性支承體與生坏薄片之間獲得圓滑的剝離性之技術 進行硏究。 爲了圓滑地進行剝離，可考量：例如預先在可撓性支 承體的陶瓷塗佈面的全面施行剝離處理。但，一旦將剝離 性做得過度良好，則與上述相反地，會引起：即使受到由 外部來的極微小的力量，生坏薄片由可撓性支承體脫落， 或已經破損的生坏薄片形成異物而介裝於疊層界面導致構 造缺陷等的問題。因此，爲了獲得良好的生坏薄片，進一 步獲得最終製品，而必須在可撓性支承體與生坏薄片之間 賦予適度的剝離性及密著性。 本案申請人針對此問題，在日本特開平8 - 1 3 0 1 5 2號 公報，提出：在可撓性支承體上的陶瓷塗料塗佈面設置實 施有剝離處理的領域（剝離層塗佈部）、與未實施剝離處 理的領域（剝離層未塗佈部）的技術。若利用此技術的話 ，能夠獲得適當的剝離性及密著性，且能夠獲得：即使將 (3) (3)200419604 生坏薄片的厚度做薄的情況，也不易產生剝離困難或製品 特性不良的可撓性支承體（剝離薄膜）。 【發明內容】 【發明所欲解決之課題】 但，當使用在前述技術所獲得的剝離薄膜來製作生坏 薄片的時，特別是在將陶瓷塗料於剝離薄膜的剝離層塗佈 部塗佈成作用於剝離層未塗佈部地形成生坏薄片的情況時 ，會有在剝離層的寬度方向端部附近於薄膜長方向（縱方 向）上產生線條狀的缺陷之虞。 面觀察的結果，在此線條部分可推測到陶瓷塗料被薄 薄地塗佈，其原因爲有在剝離層端部作成剝離層隆起而形 成較厚的部分（第3圖中的剝離層12中的圖號A所顯示 的隆起部），在此部分陶瓷塗料被釉縮（在第3圖中於介 電質層13內之所產生的以圖號B所示的空洞部）。一旦 發生此現象，則在將鈀、銀、鎳等的電極印刷於生坏薄片 後由剝離薄膜剝離時，生坏薄片的端部（耳端形狀）無法 形成直線狀，而以具有凹凸的波紋狀剝離，凹凸部甚至到 達形成在生坏薄片端部附近的電極，使得在完成的製品上 發生短路等的不良情況之可能性變高。 因此，本發明的目的是在於：提供，利用謀求習知技 術之剝離塗佈層條件的最適當化，來在剝離層上塗佈陶瓷 塗料時也不會產生釉縮（crawling )，其結果，獲得：在 由剝離薄膜剝離後具有良好的尺寸形狀（特別是在於寬度 (4) (4)200419604 方向端部）之陶瓷生坏薄片的剝離薄膜及其製造方法。 【用以解決課題之手段】 本發明者們，爲了解決前述課題，而注目於剝離層端 部領域進行詳細硏究的結果，發現能利用特定剝離層的未 塗佈部與塗佈部的境界部的形狀及寬度方向的長度，達到 前述目的，而開發完成本發明。 即，本發明的剝離薄膜，是一種剝離薄膜，是在基材薄膜 的至少單面上利用塗佈來設置剝離層的剝離薄膜，其特徵 爲. 在前述基材薄膜的寬度方向的兩端部具有前述剝離層 的未塗佈部，當塗佈油性墨水，使包含有前述剝離層的以 目視可認識的端部與該未塗佈部時，該油性墨水被釉縮的 部分是由前述以目視可認識的端部到前述未塗佈部，於寬 度方向爲2.0 mm以下的長度。再者，如此的剝離薄膜的結 構，是前述剝離層具有朝前述未塗佈部於寬度方向膜厚逐 漸減少的境界部，並且該境界部的寬度方向的長度爲2.0 mm以下之結構。 本發明的剝離薄膜是使用聚酯薄膜作爲前述基材薄膜 爲佳。 又，本發明的剝離薄膜的製造方法，是利用有機溶劑 來將剝離劑液稀釋後塗佈於基材薄膜的製程之剝離薄膜的 製造方法，其特徵爲： 將前述有機溶劑的表面張力作成〇·〇2 7N/m以下。 (5) (5)200419604 【實施方式】 以下，說明關於本發明的具體實施形態。 在於本發明的剝離薄膜，如第2圖之部分平面圖所示 ，在基材薄膜1的至少單面上，作成在寬度方向的兩端部 具有寬度方向長度w i的未塗佈部5，利用塗佈來設置剝 離層2，在形成剝離層2後的剝離薄膜上，塗佈油性墨水 9形成包含有以目視所確認之剝離層2的端部4與未塗佈 部5時，釉縮油性墨水9的部分8爲由端部4至未塗佈部 5在寬度方向型2.0min以下的長度。藉此，獲得適度的剝 離性，變得容易將生坏薄片由剝離薄膜剝離，並且也可確 保適度的密著性，亦不會產生生坏薄片由剝離薄膜脫落或 混入異物等。 再者，上述的「以目視所確認」是具體而言具有下述 的意思。β卩，由於由第2圖所示之端部4至未塗佈部5爲 止的部分6是較具有預定厚度的剝離層2的本體部分薄地 塗佈著剝離劑液，故與剝離層2的本體部分的色相不同， 反而與未塗佈部5的色相大致相同。因此，在於「目視」 ，無法看見形成剝離層2，因此，將端部4作爲以目視所 確認的「端部」。 在於本發明，利用將由油性墨水9被釉縮的部分8之 端部4至未塗佈部5爲止的寬度方向長度Di抑制於2.0 腿以下，理想爲1.0腿以下，能夠防止剝離層端部之剝離 層2的隆起，而抑制在陶瓷塗料發生釉縮，且不會產生線 條，而獲得特別是寬度方向的尺寸形狀良好之生坏薄片。 / ί -10- (6) (6)200419604 相對於此，一旦由油性墨水9被釉縮的部分8之端部 4至未塗佈部5爲止的寬度方向長度Di超過2.0腿時’則 如第3圖所示，鄰接境界部1 6的部分之剝離層1 2會局部 地隆起，形成隆起部A，由於此隆起部A而陶瓷塗料13 產生如圖所示的釉縮，而形成了空洞部B。如此的隆起部 A之空洞部B的產生原因如下所述。即，當使用在塗佈於 基材薄膜1 1的剝離層1 2之塗料的溶劑之表面張力大時， 則塗佈後至乾燥爲止之間，塗佈面爲了縮小，而如圖所示 ，剝離層端部的形狀是在最端部極薄地殘存，並且從該處 形成於略內部側隆起成山形狀的隆起部A。 因此，在於本發明的剝離薄膜的製造方法，著眼於使 用在剝離層2的塗料之溶劑的表面張力，爲了在端部不會 產生隆起部地形成剝離層2，則必須使用以表面張力 0.02 7N/m以下、理想爲0.02 5N/m以下的有機溶劑所調製 的剝離層塗料。有機溶劑是若具有前述範圍的表面張力者 的話，不會有種類、單獨或混合類之限制，能適宜使用一 般被使用的環己烷、η-己烷、庚烷、甲苯等的各種溶劑。 在於本發明的剝離薄膜，如第1圖的寬度方向斷面圖 所示’剝離層2是具有朝未塗佈部5於寬度方向逐漸減少 膜厚之寬度方向長度〇1的境界部6。如上所述，在由油 性墨水9被釉縮的部分8的端部4至未塗佈部5爲止於寬 度方向爲2.0 mm以下的長度的情況時，如圖所示的境界部 6之寬度方向長度Di形成2.0mm以下。 相對於此，如第4圖所示，由以目視所確認的剝離層 -11 - (7) (7)200419604 的端部14至未塗佈部丨5爲止，油性墨水1 9被釉縮的部 分18中，境界部16的寬度D2超過2腿的情況下，於剝 離層12上塗佈陶瓷塗料時發生了釉縮。如此，在於本發 明的剝離薄膜，利用油性墨水9的塗佈，能容易地求出境 界部6的寬度方向長度Dl。再者，於本發明能夠使用的 墨水爲：例如萬能墨水（Magic Ink )公司製的No. 500 ( 油性）紅、大型（油性）紅、極粗（油性）紅；ZEBRA 公司製的馬奇（油性）紅、黑、藍；三菱鉛筆（股）公司 製的比絲[Pi : s](油性）黑粗字角芯+細字圓芯等。 在於本發明可使用的基材薄膜1無特別限制，但，理 想爲使用聚酯薄膜。特別是在被要求透明性的用途上，使 用透明性良好的聚酯薄膜爲佳，雙軸延伸聚酯薄膜爲更理 想。又，在被要求遮光性的用途上，使用配合有無機顏料 的聚酯薄膜爲佳，使用配合有Ti02、Si02等之顏料的雙 軸延伸聚酯薄膜爲更理想。 構成聚酯薄膜的聚酯是芳香族二元酸成分與二元醇成 分所構成的結晶性飽和聚酯爲佳。例如有聚對苯甲二酸乙 二醇酯、對苯甲二酸丙二醇酯、對苯甲二酸丁二醇酯、聚 2,6奈二甲酸乙二醇酯等。 本發明的基材薄膜是能夠以習知的方法來製造。例如 ’雙軸延伸聚酯薄膜是能夠利用將聚酯乾燥後，以押出機 熔融，由模具（例如τ-模具、Μ莫具）押出至旋轉冷卻滾 筒上，加以急冷後作爲未延伸薄膜，接著將此未延伸薄膜 於雙軸方向延伸，因應需要加以熱固定來製造。基材薄膜 -12- (8) (8)200419604 的厚度是並無特別限制，但5〜25 Ομπι爲佳。 又’使用以前述有機溶劑將矽樹脂特別是硬化型矽樹 脂稀釋之塗料作爲用來形成剝離層2所使用的剝離劑液。 硬化型矽樹脂是並無特別限定，例如能夠使用聚合反應型 '附加反應型、紫外線反應型、電子線硬化行等等者。 剝離層2是能夠以塗佈含有硬化型矽樹脂的塗料後， 加以乾燥、硬化來形成。能夠採用逆輥塗佈法、凹板輥 (gravure roll )塗佈法、氣動刮塗法等之習知的方法作爲 塗佈的方法。 塗佈後的硬化型矽樹脂塗料是能夠利用以熱進行乾燥 、硬化來形成硬化皮膜。在此情況時，利用在50〜1 8(TC 、理想爲80〜160°C的範圍之溫度下進行5秒以上、理想 爲1 〇秒以上的時間之加熱處理，來形成硬化皮膜爲佳。 硬化型矽樹脂的塗佈厚度爲1〜25g/m2、特別是 2〜 20g/m2的範圍爲佳，硬化後的矽樹脂塗佈膜的厚度爲 〇·〇5〜Ιμιη、特別是0.1〜0.5 μπι的範圍爲佳。在塗佈後的 塗佈厚度未滿〇.〇5 μιη的情況時，會有剝離性能降低的傾 向。又，在硬化後的塗佈厚度超過Ιμιη的情況時，會有 塗佈膜的硬化變得不充分的傾向，而剝離性能隨著時間變 化的情況產生。 【實施例】 以下，利用具體的實施例詳述本發明。 -13- 200419604 Ο) (實施例1〜4及比較例1〜3 ) [剝離層塗料的調製] 將在具有乙烯基的聚氧烷與矽烷化氫矽化合物之混合 物加入白金系觸媒後使之附加反應型的硬化型矽樹脂（信 越化學工業（股）公司製之KS-84 7H)溶解於下述表1所 示的各種有機溶劑中，製作作爲剝離層塗料的全體之固態 分濃度爲3%的矽樹脂塗料。各材料的配合量如下所述。200419604 (1) (ii) Description of the invention [Technical field to which the invention belongs] The present invention relates to a release film and a method for manufacturing the same, and more particularly, to a release film for manufacturing a multilayer ceramic capacitor and a method for manufacturing the same. [Prior art] In the case of manufacturing ceramic electronic parts such as capacitors, piezoelectric parts, positive-characteristic thermal resistors, negative-characteristic thermal resistors, or thermal rheostats, there have been adopted: On a flexible support, for example, A doctor blade method is used to apply a ceramic coating containing ceramic powder, organic binders, plasticizers, solvents, etc. to form a green sheet (dielectric layer), which is formed by dot printing. Manufacturing process of palladium, silver, nickel and other electrodes. In this manufacturing process, when a laminated structure is obtained, the obtained green sheet is laminated one by one to form a desired laminated structure, and then a stamping and cutting process is performed to obtain ceramics. Blank chip (green chip). The binder in the ceramic bare crystals thus obtained is dewaxed and fired at 1 000 ° C to 1 400 ° C to form silver, silver-palladium, nickel, copper, etc. on the obtained or obtained fired body. Terminal electrode to obtain ceramic electronic parts. Others have been proposed: a method for thermally transferring raw and broken sheets to form a flexible support (eg, Japanese Patent Application Laid-Open No. 63-188926); or on a flexible support For the required number of laminations, a method of obtaining a laminated body by repeatedly performing a process of forming raw and bad sheets and a process of printing electrodes on the raw and bad sheets is used. (2) (2) 200419604 In the above-mentioned manufacturing methods of ceramic electronic parts, a process of peeling the formed raw and bad sheets from a flexible support is required, but in this process, there will be: When the support is peeled off, problems such as breakage easily occur in the raw and damaged sheets. For example, in the case of a multilayer ceramic capacitor, in order to reduce the size and increase the capacity, a method of reducing the thickness of a dielectric layer per layer to increase the number of stacked layers may be used. The damage of the bad lamella becomes more significant with this thin film formation. Once the raw and damaged sheets are damaged, short-circuiting and other shortcomings occur in the final product, which reduces the yield of the laminate. Therefore, in the past, it has been aimed at obtaining smoothness between the flexible support and the raw and bad sheets. Research on peeling technology. For smooth peeling, it may be considered that, for example, the entire surface of the ceramic-coated surface of the flexible support is subjected to a peeling treatment in advance. However, once the peelability is made excessively good, contrary to the above, it may cause that even if it receives a very small force from the outside, the raw and damaged sheet is detached from the flexible support or the damaged and damaged sheet is formed. Foreign matter that is interposed at the laminated interface causes problems such as structural defects. Therefore, in order to obtain a good raw and bad sheet and further obtain a final product, it is necessary to provide a moderate peeling and adhesion between the flexible support and the raw and bad sheet. In response to this problem, the applicant of this case proposed in Japanese Patent Application Laid-Open No. 8-1 3 0 1 5 2 that the ceramic coating surface on the flexible support should be provided with an area subjected to a peeling treatment (release layer coating section). ), And technology for areas where no peeling treatment is performed (uncoated part of the peeling layer). If this technology is used, appropriate peelability and adhesion can be obtained, and even if the thickness of (3) (3) 200419604 thin sheet is made thin, it is difficult to produce peeling difficulties or poor product characteristics. Flexible support (release film). [Summary of the Invention] [Problems to be Solved by the Invention] However, when using the release film obtained in the aforementioned technology to produce a raw and damaged sheet, a ceramic coating is particularly applied to a release layer coating portion of the release film to In the case where a raw or damaged sheet is formed while acting on the uncoated portion of the release layer, there may be a line-like defect in the film longitudinal direction (longitudinal direction) near the widthwise end portion of the release layer. As a result of surface observation, it can be presumed that the ceramic coating is applied thinly in this line portion. The reason is that a thicker portion is formed by forming a peeling layer at the end of the peeling layer (in the peeling layer 12 in FIG. 3). The raised portion shown in Figure A), in which the ceramic coating is glazed (the hollow portion shown in Figure 3 in the dielectric layer 13 in Figure 3 is shown in Figure B). Once this phenomenon occurs, when electrodes such as palladium, silver, and nickel are printed on the green sheet and peeled off by the release film, the end (ear-end shape) of the green sheet cannot be formed into a straight line, and it has corrugations with irregularities. It is peeled off, and the uneven portion reaches even the electrode formed near the end portion of the raw and damaged sheet, so that the possibility of occurrence of a short circuit or the like on the finished product is high. Therefore, an object of the present invention is to provide optimization of conditions for peeling a coating layer using a conventional technique, so that a ceramic coating may not be applied to the peeling layer when a ceramic coating is applied, and as a result, Obtained: A release film of a ceramic green sheet having a good size and shape (especially at the end in the direction of the width (4) (4) 200419604) after being peeled from the release film, and a manufacturing method thereof. [Means to Solve the Problem] In order to solve the aforementioned problems, the present inventors paid close attention to the area of the end portion of the release layer and conducted detailed research, and found that the boundary between the uncoated portion and the coated portion of the specific release layer can be used. The shape of the part and the length in the width direction achieve the aforementioned objects, and the present invention has been developed. That is, the release film of the present invention is a release film, which is a release film in which a release layer is provided by coating on at least one side of a base film, and is characterized in that: both ends in the width direction of the base film When an uncoated portion having the release layer is coated with an oil-based ink such that a visually recognizable end portion including the release layer and the uncoated portion are included, a portion of the oil-based ink that has been glazed is formed by the foregoing. The length from the end which can be recognized visually to the said uncoated part is 2.0 mm or less in the width direction. The structure of such a release film is such that the release layer has a boundary portion in which the film thickness gradually decreases in the width direction toward the uncoated portion, and the width direction length of the boundary portion is 2.0 mm or less. The release film of the present invention preferably uses a polyester film as the substrate film. Moreover, the manufacturing method of the peeling film of this invention is a manufacturing method of the peeling film which uses the organic solvent to dilute a release agent liquid and apply | coats to a base film, It is characterized by making the surface tension of the said organic solvent into 0. 〇2 7N / m or less. (5) (5) 200419604 [Embodiment] Hereinafter, a specific embodiment of the present invention will be described. In the release film of the present invention, as shown in a partial plan view in FIG. 2, an uncoated portion 5 having a width direction length wi at both ends in the width direction is formed on at least one side of the base film 1, and is applied by coating. When the release layer 2 is provided with a cloth, and an oil-based ink 9 is applied to the release film after forming the release layer 2 to form the end portion 4 and the uncoated portion 5 of the release layer 2 which are visually confirmed, the glaze-based ink is formed. The portion 8 of 9 is a length from the end portion 4 to the uncoated portion 5 in a width direction type of 2.0 min or less. Thereby, a moderate peeling property is obtained, it becomes easy to peel the raw and damaged sheet from the peeling film, and moderate adhesion can be ensured, and no peeling of the raw and bad sheet from the peeling film or mixing of foreign matter can be caused. In addition, the above-mentioned "confirmed visually" has the following meanings. β 卩, since the portion 6 from the end portion 4 to the uncoated portion 5 shown in FIG. 2 is coated with a release agent liquid thinner than the body portion of the release layer 2 having a predetermined thickness, The hue of the main body portion is different, but is substantially the same as that of the uncoated portion 5. Therefore, the formation of the release layer 2 cannot be seen by "visual inspection". Therefore, the end portion 4 is regarded as the "end portion" visually confirmed. In the present invention, by using the width direction length Di from the end portion 4 of the glazed portion 8 of the oil-based ink 9 to the uncoated portion 5 to be less than 2.0 legs, and preferably 1.0 legs or less, the end portion of the peeling layer can be prevented. The bulging of the peeling layer 2 suppresses the occurrence of glaze shrinkage in the ceramic coating, and does not generate lines, and obtains a fragile sheet having a particularly good size and shape in the width direction. / -10- (6) (6) 200419604 On the other hand, if the width direction length Di from the end 4 of the oil-based ink 9's glazed portion 8 to the uncoated portion 5 exceeds 2.0 legs, such as As shown in FIG. 3, the peeling layer 12 of the part adjacent to the boundary portion 16 will locally swell to form a swell A. The swell of the ceramic coating 13 due to the swell A and the cavity shown in the figure form a cavity. Department B. The cause of such a hollow portion B of the raised portion A is as follows. That is, when the surface tension of the solvent used in the coating material applied to the release layer 12 of the base film 11 is large, the coating surface is reduced as shown in the figure after the coating is applied until it is dried. The shape of the end portion of the peeling layer remains extremely thin at the extreme end portion, and from this point, a ridge portion A bulging into a mountain shape on the slightly inner side is formed. Therefore, in the method for producing a release film of the present invention, the surface tension of the solvent of the coating material used in the release layer 2 is focused on. In order to form the release layer 2 without generating a raised portion at the end, a surface tension of 0.02 7N must be used. / m or less, preferably 0.02 5 N / m or less of an organic solvent prepared by an organic solvent. If the organic solvent has a surface tension in the aforementioned range, there are no restrictions on the type, single or mixed type, and various solvents such as cyclohexane, η-hexane, heptane, and toluene which are generally used can be suitably used. In the release film of the present invention, as shown in the cross-sectional view in the width direction of Fig. 1, the 'release layer 2 is a boundary portion 6 having a width-direction length 0 of the film thickness which gradually decreases toward the uncoated portion 5 in the width direction. As described above, when the length from the end portion 4 of the glazed portion 8 to the uncoated portion 5 of the oil-based ink 9 is 2.0 mm or less in the width direction, the width direction of the boundary portion 6 is shown in the figure. The length Di is 2.0 mm or less. On the other hand, as shown in FIG. 4, the oil-based ink 19 is glazed from the end 14 of the peeling layer -11-(7) (7) 200419604 to the uncoated portion 5 visually confirmed. In the part 18, when the width D2 of the boundary portion 16 exceeds two legs, glaze shrinkage occurs when the ceramic coating is applied on the release layer 12. As described above, the release film of the present invention can easily obtain the width direction length D1 of the boundary portion 6 by applying the oil-based ink 9. In addition, the inks that can be used in the present invention are, for example, No. 500 (oily) red, large (oily) red, and extremely thick (oily) red made by Magic Ink, Inc .; Oily) red, black, blue; Mitsubishi Pencil (stock) company's Bisi [Pi: s] (oily) black thick corner corner + fine round core. The substrate film 1 usable in the present invention is not particularly limited, but a polyester film is preferably used. Especially for applications where transparency is required, a polyester film with good transparency is preferred, and a biaxially stretched polyester film is more preferred. For applications requiring light-shielding properties, it is preferable to use a polyester film blended with an inorganic pigment, and it is more preferable to use a biaxially stretched polyester film blended with pigments such as Ti02 and SiO2. The polyester constituting the polyester film is preferably a crystalline saturated polyester composed of an aromatic diacid component and a diol component. For example, there are polyethylene glycol terephthalate, propylene glycol terephthalate, butylene glycol terephthalate, polyethylene 2,6-naphthalate, and the like. The base film of the present invention can be produced by a known method. For example, 'biaxially stretched polyester film can be used to dry the polyester, melt it with an extruder, and extrude it from a mold (such as τ-mold, M Mogu) onto a rotary cooling drum, and then quench it as an unstretched film. This unstretched film is stretched in a biaxial direction, and heat-fixed as necessary to manufacture. The thickness of the substrate film -12- (8) (8) 200419604 is not particularly limited, but it is preferably 5 to 25 μm. Further, a coating material in which a silicone resin, particularly a hardened silicone resin is diluted with the aforementioned organic solvent, is used as a release agent liquid for forming the release layer 2. The hardening type silicone resin is not particularly limited, and examples thereof include a polymerization reaction type, an “additional reaction type”, an ultraviolet reaction type, and an electron beam curing type. The release layer 2 can be formed by applying a coating material containing a curable silicone resin and then drying and curing. As the coating method, a conventional method such as a reverse roll coating method, a gravure roll coating method, or a pneumatic blade coating method can be adopted. The hardened silicone resin coating after coating can be dried and hardened by heat to form a hardened film. In this case, it is preferable to use a heat treatment at a temperature in the range of 50 to 18 ° C., preferably 80 to 160 ° C. for 5 seconds or more, and preferably 10 seconds or more to form a hardened film. The coating thickness of the hardened silicone resin is preferably in the range of 1 to 25 g / m2, especially 2 to 20 g / m2, and the thickness of the cured silicone resin coating film is 0.05 to 1 μm, particularly 0.1 to 0.5. The range of μm is preferred. When the coating thickness after coating is less than 0.05 μm, the peeling performance tends to decrease. When the coating thickness after curing exceeds 1 μm, The hardening of the coating film tends to be insufficient, and the peeling performance changes with time. [Examples] Hereinafter, the present invention will be described in detail using specific examples. -13- 200419604 0) (Examples 1 to 1) 4 and Comparative Examples 1 to 3) [Preparation of coating for peeling layer] After adding a platinum-based catalyst to a mixture of a polyoxyalkylene group having a vinyl group and a silicon silane compound, a hardening type silicone resin with a reactive type (Shin-Etsu KS-84 7H manufactured by Chemical Industry Co., Ltd. is dissolved in He said various organic solvents shown in Table 1 to prepare a release layer coating the entire solid content concentration of 3% silicone resin coating. The blending amount of each material is as follows.
硬化性矽樹脂 KS-847H 300g (信越化學工業（股）製：固態分濃度30%、樹脂90g) 白金觸媒 CAT-PL-50T (信越化學工業（股）製） 3.0g 有機溶劑 2700g 將所獲得的矽樹脂塗料，在作爲基材薄膜的厚度 38 μιη之雙軸延伸聚對苯甲二酸乙二醇酯（PET )上，乾 燥後的塗佈膜厚度形成〇 · 1 5 μπι地以棒材塗佈器由兩端設 置1 cm的未塗佈部而加以塗佈，再以加熱溫度1 1 〇 °c、4 0 秒進行乾燥及硬化反應後形成剝離層2，來製作捲繞呈滾 筒狀的剝離薄膜。 [介電質（陶瓷）塗料的調製] 焙燒粒徑〇· 1〜1.0μπι程度的鈦酸鋇、氧化鉻、氧化 ί乙、碳酸锰、碳酸鋇、氧化砂等的粉末後，以B a T i Ο 31 0 0 莫耳，混合成：換算成Cr2O30.3莫耳、ΜηΟΟ·4莫耳、300g of hardening silicone resin KS-847H (made by Shin-Etsu Chemical Industry Co., Ltd .: solid content of 30%, resin 90g) Platinum catalyst CAT-PL-50T (made by Shin-Etsu Chemical Industry Co., Ltd.) 3.0g 2700g organic solvent The obtained silicone resin coating was dried on a biaxially-stretched polyethylene terephthalate (PET) having a thickness of 38 μm as a base film, and the thickness of the dried coating film was 0.15 μm. The material applicator is coated by setting an uncoated portion of 1 cm at both ends, and then drying and hardening at a heating temperature of 110 ° C for 40 seconds to form a peeling layer 2 to make a rolled roll. Like peeling film. [Preparation of Dielectric (Ceramic) Coatings] After firing powders such as barium titanate, chromium oxide, oxidized ethylene, manganese carbonate, barium carbonate, and sand oxide with a particle size of 0.1 to 1.0 μm, B a T i Ο 31 0 0 Mor, mixed into: converted to Cr2O30.3 Mor, ΜηΟΟ · 4 Mor,
-14- (10) (10)200419604-14- (10) (10) 200419604
Ba02.4 莫耳、Ca01.6 莫耳、SiO20.4 莫耳、γ2Ο30·1 莫耳 的組成，利用球磨機混合24小時，加以乾燥後化得介電 質原料。將100重量部之此介電質原料、5重量部之丙烯 樹脂、40重量部之亞甲基二氯、25重量部之丙酮、6重 量部之礦油精加以配合，使用市面販賣的^ 10腿氧化鉻 珠利用鍋架台混合24小時後，獲得介電質（陶瓷）塗料 [有無剝離層塗佈端部附近之介電質塗料釉縮的產生] 將前述介電質塗料在各剝離薄膜上以棒材塗佈器突部 成乾燥後的塗層膜厚度爲4.5 μπι。介電質塗料是由剝離層 的端部塗佈成突出4〜5 mm程度。將所獲得的各薄片接近 螢光燈，來評價在剝離層塗佈端部有無產生介電質塗料釉 縮。評價基準爲：無介電質釉縮者以〇表示；有若干的介 電質釉縮，但在介電質剝離時耳端形狀不會變差者以△表 示；有介電質釉縮產生，且在介電質剝離時，耳端形狀變 差者以X表示。 [剝離層塗佈端部附近的油性墨水釉縮部的寬度方向長度] 又，在未形成有介電質層的各剝離薄膜上，由未塗佈 部5朝塗佈部塗佈油性墨水（萬能墨水（Magic Ink )公 司製、極粗（油性）紅）使得含有以目視可認識之剝離層 2的端部4與未塗佈部5，測量油性墨水被釉縮的部分的 長度（第2及4圖之D!及D2(mm))(參照第2圖）。 -15- (11) (11)200419604 將這些的結果一並表示於下述的表1。The composition of Ba02.4 Mohr, Ca01.6 Mohr, SiO20.4 Mohr, γ2030 · 1 Mohr was mixed with a ball mill for 24 hours, and dried to obtain a dielectric raw material. 100 parts by weight of this dielectric material, 5 parts by weight of acrylic resin, 40 parts by weight of methylene dichloride, 25 parts by weight of acetone, and 6 parts by weight of mineral spirits are used, using commercially available ^ 10 After the leg chrome oxide beads were mixed on the pot stand for 24 hours, a dielectric (ceramic) coating was obtained [with or without the occurrence of a glaze shrinkage of the dielectric coating near the coating end of the peeling layer] The aforementioned dielectric coating was applied to each release film The thickness of the coating film after drying with the bar applicator protrusion was 4.5 μm. The dielectric coating is applied from the end of the release layer so as to protrude by 4 to 5 mm. Each of the obtained sheets was brought close to a fluorescent lamp, and it was evaluated whether or not a dielectric coating glaze was generated at the coated end portion of the release layer. The evaluation criteria are: those with no dielectric glaze are represented by 0; those with some dielectric glaze, but the shape of the ear tip will not deteriorate when the dielectric is peeled off, are represented by △; there are dielectric glazes , And when the dielectric is peeled off, the shape of the ear tip deteriorates is represented by X. [Width-wise Length of Oil-based Ink Glaze Shrinkage Section Near Coating End of Peeling Layer] Further, on each peeling film on which no dielectric layer was formed, an oil-based ink was applied from the uncoated section 5 to the coating section ( The extremely thick (oily red) made by Magic Ink Co., Ltd. includes the end portion 4 and the uncoated portion 5 of the peeling layer 2 that can be visually recognized, and measures the length of the portion of the oily ink that has been glazed (second And D2 (mm) in Figure 4) (see Figure 2). -15- (11) (11) 200419604 These results are shown in Table 1 below.
有機溶劑的種類 混合比率 (% ) 有機溶劑的 表面張力 (N/m) 耳端部分有 無產生介電 質釉縮 墨水釉縮部 的寬度方向 長度（臟） 實施例1 己院 100 0.0179 〇 0.3 實施例2 己院/甲苯 55/45 0.0224 〇 0.5 實施例3 庚院/甲苯 60/40 0.0229 〇 0.5 實施例4 庚院/甲苯 50/50 0.0238 〇 1.0 實施例5 乙酸乙酯/甲苯 50/50 0.0259 Δ 2.0 比較例1 甲苯 100 0.0279 X 3.0 比較例2 庚院/環己烷 50/50 0.0274 X 2.5 【發明效果】 如上所述，若根據本發明的話，能夠獲得：在將陶瓷 塗料塗佈於剝離層上時，也不會產生釉縮，其結果，在由 剝離薄膜剝離後，特別是在寬度方向的端部，具有良好尺 寸形狀的生坏薄片之剝離薄膜及可提供其製造方法。 【圖式簡單說明】 第1圖是顯示剝離薄膜的剝離層端部附近的構造之部 分斷面圖。 9S3 -16- (12) 200419604 第2圖是顯示在剝離薄膜的剝離層端部附近已 '塗佈油 性墨水的情況之部分平面圖。 第3圖是顯示在陶瓷塗料產生釉縮的情況時之剝離薄 膜的剝離層端部附近的構造之部分斷面圖。 第4圖是顯示在剝離薄膜的剝離層端部附近突部油性 墨水的其他情況的部分平面圖。 【圖號說明】Type of organic solvent Mixing ratio (%) Surface tension (N / m) of organic solvent Presence or absence of dielectric glaze shrinkage Ink glaze shrinkage Width length (dirty) Example 1 己 院 100 0.0179 〇0.3 Implementation Example 2 Heyuan / Toluene 55/45 0.0224 〇0.5 Example 3 Geng Yuan / Toluene 60/40 0.0229 〇0.5 Example 4 Geng Yuan / Toluene 50/50 0.0238 〇1.0 Example 5 Ethyl acetate / Toluene 50/50 0.0259 Δ 2.0 Comparative Example 1 Toluene 100 0.0279 X 3.0 Comparative Example 2 Gengyuan / Cyclohexane 50/50 0.0274 X 2.5 [Effects of the Invention] As described above, according to the present invention, it is possible to obtain: when a ceramic coating is applied to a peeling layer No glaze shrinkage occurs when the layer is applied. As a result, after peeling off the release film, particularly at the end in the width direction, a release film having a good size and shape of the raw and damaged sheet and a method for producing the same can be provided. [Brief Description of the Drawings] Fig. 1 is a partial cross-sectional view showing a structure in the vicinity of an end portion of a release layer of a release film. 9S3 -16- (12) 200419604 Figure 2 is a partial plan view showing a state where an oil-based ink has been applied near the end of the release layer of the release film. Fig. 3 is a partial cross-sectional view showing a structure in the vicinity of an end portion of a release layer of a release film when a ceramic coating is glazed. Fig. 4 is a partial plan view showing other aspects of the oily ink projecting near the end of the release layer of the release film. [Illustration of drawing number]
11…基材薄膜 12…剝離層 I3…介電質層 1 4…剝離層的端部 1 5 ···未塗佈部 16···境界部 8、 1 8…墨水釉縮部11 ... substrate film 12 ... release layer I3 ... dielectric layer 1 4 ... end of release layer 1 5 ... uncoated portion 16 ... boundary area 8, 1 8 ... ink glaze shrinkage
9、 19···墨水塗佈部 A…隆起部 B…空洞部 -17-9, 19 ... Ink coating section A ... Bulge section B ... Hollow section -17-