1269323 (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 料後形成生坏薄片（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〜1400 °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。 -6- (2) 1269323 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丨剝離的製程，但在於此 製程，會有：當由可撓形支承體剝默時，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_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， 或已經破損的生坪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 鼠j連里.的剝離性及密著性。 本案申請人針對此問題，在曰本特開平8 - 1 3 0 1 52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 -7- (3) 1269323 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$陷之虞。 面觀察的果、，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 ...........一-—…〜一· 塗料時也不會產生釉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 -8- (4) 1269323 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 腿以下之結構。 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。 -9 - 12693231269323 (1) Field of the Invention The present invention relates to a release film and a method for producing the same, and, in particular, to a release film for producing a laminated ceramic capacitor and a method for producing the same. [Prior Art] In the case of manufacturing a ceramic electronic component such as a capacitor, a piezoelectric component, a positive characteristic thermistor, a negative characteristic thermistor or a thermal resistor, etc., it is assumed that: on the flexible support, for example A doctor's blade method is applied to coat a ceramic coating containing a ceramic powder, an organic binder, a plasticizer, a solvent, etc. to form a green sheet (dielectric layer) on which dots are printed. A process for forming an electrode of palladium, silver, nickel, or the like. In the manufacturing process, in the case of obtaining a laminated structure, the obtained green sheets are laminated to form a desired laminated structure, and then subjected to a stamping and cutting process to obtain a ceramic. A green chip. The decarburization of the binder in the ceramic bare crystal thus obtained is fired at 1 000 ° C to 1400 ° C, and terminals of silver, silver-palladium, nickel, copper, etc. are formed on the obtained fired body. Electrodes to obtain ceramic electronic parts. Others have been proposed: a method in which a raw sheet is thermally transferred, and a flexible support is formed thereon (for example, Japanese Patent Laid-Open Publication No. SHO63-188926, etc.); or on a flexible support. A method of obtaining a laminate by repeatedly performing a process of forming a green sheet and a process of printing an electrode on a damaged sheet to obtain a laminate. -6- (2) 1269323 In the above-described method for manufacturing a ceramic electronic component, it is necessary to perform a process of peeling the formed green sheet from the flexible support body, but in this process, there may be: When the flexible support is peeled off, problems such as breakage are likely to occur on the damaged sheet. For example, in the case of a laminated ceramic capacitor, in order to reduce the size and capacity, a method of increasing the thickness of each dielectric layer to increase the number of laminations is used. The damage of bad flakes becomes more pronounced with this thinning. In the case where the damaged sheet is damaged, the final product has a large number of characteristic defects such as a short circuit, and the laminate yield is lowered. Therefore, it has been conventionally used for obtaining a smoothness between the flexible support and the raw sheet. _ off-the-shelf technology to study. In order to perform the peeling smoothly, it is possible to consider, for example, a total peeling treatment in advance on the ceramic coated surface of the flexible support. However, once the peeling property is excessively good, contrary to the above, it is caused that even if a very small force from the outside is received, the raw and broken sheets are peeled off from the flexible support, or the damaged flat sheet is formed. The foreign matter is interposed in the laminated interface to cause problems such as structural defects. Therefore, in order to obtain a good green sheet, the final product is further obtained, and the peeling property and the adhesion between the flexible support and the raw sheet must be obtained. In order to solve this problem, the applicant of the present application has proposed a field in which a peeling treatment is applied to a coated surface of a ceramic coating on a flexible support in the publication of Japanese Laid-Open Patent Publication No. Hei 8-133-52. And a technique in which the peeling treatment is not performed (the peeling layer uncoated portion). According to this technique, it is possible to obtain appropriate peelability and adhesion, and it is possible to obtain peeling difficulty or product characteristics even when the thickness of the -7-(3) 1269323 smashed sheet is made thin. Poor flexible support (release film). [Problem to be Solved by the Invention] However, when a green sheet is produced by using the release film obtained by the above technique, in particular, the ceramic coating material is applied to the release layer coating portion of the release film. When the raw sheet is formed on the uncoated portion of the peeling layer, it may be generated in the longitudinal direction (longitudinal direction) of the film in the vicinity of the end portion in the width direction of the peeling layer. As a result, it is presumed that the ceramic coating is thinly coated because the peeling layer is embossed at the end of the peeling layer to form a thick portion (Fig. A in the peeling layer 12 in Fig. 3). In the ridge portion shown, the ceramic coating is glazed (the cavity portion shown in Figure B in the dielectric layer 13 in Fig. 3). Once this occurs, When an electrode such as palladium, silver, or nickel is printed on a raw sheet and then peeled off by a release film, the end portion (ear shape) of the raw sheet cannot be formed linearly, and is peeled off in a corrugated shape having irregularities, and the uneven portion is even reached. Formed in raw sheets The electrode in the vicinity of the end portion is highly likely to cause a problem such as a short circuit in the finished product. Therefore, an object of the present invention is to provide an optimum use of the conditions of the peeling coating layer which is a conventional technique. To coat the peeling layer with ceramics...........one--...~1· Paint does not produce glazing crawling), and as a result, it is obtained: it is good after being peeled off by the peeling film. A peeling film of a ceramic green sheet having a dimensional shape (especially in the width - 8 - (4) 1269323 direction end portion) and a method of manufacturing the same. [Means for Solving the Problem] In order to solve the above problems, the inventors of the present invention have focused on the results of detailed examination of the end portion of the peeling layer, and found that the boundary between the uncoated portion and the coated portion of the specific peeling layer can be utilized. The shape of the portion and the length in the width direction achieve the aforementioned objects, and the present invention has been developed. In other words, the release film of the present invention is a release film which is a release film provided with a release layer by coating on at least one surface of the base film, and is characterized in that both ends of the base film in the width direction are formed. In the uncoated portion having the peeling layer, when the oil-based ink is applied to the end portion of the peeling layer which is visually recognizable and the uncoated portion, the portion in which the oil-based ink is embossed is The end portion which is visually recognizable to the uncoated portion has a length of 2.0 mm or less in the width direction. In the structure of the release film, the release layer has a boundary portion in which the thickness of the uncoated portion gradually decreases in the width direction, and the length of the boundary portion in the width direction is 2.0 legs or less. The release film of the present invention is preferably a polyester film as the base film. Moreover, the method for producing a release film of the present invention is a method for producing a release film which is obtained by diluting a release agent solution with an organic solvent and applying the film to a base film, and is characterized in that the surface tension of the organic solvent is used as a crucible. .〇2 7N/m or less. -9 - 1269323
【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Wi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 · 0 mill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。即，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D1抑制於2.0 mm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。 •10- (6) 1269323 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.Omm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、理想爲〇.〇2 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: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) 1269323 的端部1 4至未塗佈部1 5爲止，油性墨水1 9被釉縮的部 分1 8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Di。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T-模具、；[_模具）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) 1269323 的厚度是並無特別限制，但5〜25 Ομιη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50〜180°C 、理想爲80〜16(TC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 1〜25 g/m2、特別是 2〜 2〇g/m2的範圍爲佳，硬化後的矽樹脂塗佈膜的厚度爲 〇.〇5〜Ιμηι、特別是〇.1〜〇.5 μιη的範圍爲佳。在塗佈後的 塗佈厚度未滿0.05 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1 μπι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。 (9) 1269323 (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。[Embodiment] Hereinafter, specific embodiments of the present invention will be described. In the peeling film of the present invention, as shown in a partial plan view of Fig. 2, the uncoated portion 5 having the width direction Wi in the width direction at both end portions in the width direction is formed on at least one surface of the base film 1. The release layer 2 is provided on the release film 2, and the oil-based ink 9 is applied to the release film after the release layer 2 is formed, and the enamel oil-reducing ink is formed when the end portion 4 and the uncoated portion 5 including the peeling layer 2 visually confirmed are formed. The portion 8 of 9 is a length from the end portion 4 to the uncoated portion 5 in the width direction type of 2·0 mill or less. Thereby, moderate peeling property is obtained, and it is easy to peel off the raw and succeeded sheets from the release film, and it is also possible to ensure appropriate adhesion, and it is not caused that the raw sheets are peeled off from the release film or foreign matter is mixed. In addition, the above-mentioned "confirmed by visual observation" specifically has the following meaning. That is, since the portion 6 from the end portion 4 to the uncoated portion 5 shown in Fig. 2 is a thin portion of the body portion of the peeling layer 2 having a predetermined thickness, the body of the peeling layer 2 is applied. The color of the portion is different, and is substantially the same as the hue of the uncoated portion 5. Therefore, in the "visual view", the peeling layer 2 cannot be seen, and therefore, the end portion 4 is regarded as the "end portion" which is visually confirmed. In the present invention, the length D1 in the width direction from the end portion 4 of the portion 8 to which the oil-based ink 9 is glazed to the uncoated portion 5 is suppressed to 2.0 mm or less, preferably 1 or less, and the peeling layer end can be prevented. The swell of the peeling layer 2 of the portion suppresses the occurrence of glazing in the ceramic coating, and does not generate a line, and obtains a raw sheet having a good dimensional shape particularly in the width direction. 10 - (6) 1269323 In contrast, when the length direction Di in the width direction from the end portion 4 of the portion 8 of the oil-impregnated ink 9 to the uncoated portion 5 exceeds 2.0 mm, as shown in Fig. 3 It is shown that the peeling layer 12 of the portion adjacent to the boundary portion 16 is locally swelled to form the ridge portion A, and the ceramic paint 13 is glazed as shown by the ridge portion A to form the cavity portion B. The cause of the cavity portion B of such a ridge portion A is as follows. That is, when the surface tension of the solvent applied to the coating of the release layer 1 2 of the base film 1 1 is large, the coated surface is reduced between the application and the drying, as shown in the drawing. The shape of the end portion of the peeling layer is extremely thin at the most end portion, and from this portion, a raised portion A which is formed in a mountain shape on the slightly inner side is formed. Therefore, in the method for producing a release film of the present invention, attention is paid to the surface tension of the solvent used in the coating of the release layer 2, and in order to form the release layer 2 without generating a ridge at the end portion, it is necessary to use a surface tension of 0.02 7N. A peeling layer coating prepared by an organic solvent of /m or less, preferably 〇.〇2 5 N/m or less. When the organic solvent has a surface tension in the above range, there is no limitation on the type, alone or in combination, and various solvents such as cyclohexane, η-hexane, heptane, and toluene which are generally used can be suitably used. In the peeling film of the present invention, as shown in the cross-sectional view in the width direction of Fig. 1, the peeling layer 2 is a boundary portion 6 having a length 〇 in the width direction which gradually decreases in the width direction toward the uncoated portion 5. As described above, in the case where the width direction is 2.0 mm or less in the width direction from the end portion 4 to the uncoated portion 5 of the portion 8 to which the oil-based ink 9 is embossed, the width direction of the boundary portion 6 as shown in the drawing is as shown. The length Di is formed to be 2.0 mm or less. On the other hand, as shown in Fig. 4, the oily ink 19 is glazed by the end portion 14 to the uncoated portion 15 of the peeling layer -11 - (7) 1269323 which is visually confirmed. In the case where the width D2 of the boundary portion 16 exceeds two legs, the glaze is generated when the ceramic coating material is applied to the peeling layer 12. As described above, in the release film of the present invention, the width Di of the boundary portion 6 in the width direction can be easily obtained by the application of the oil-based ink 9. Further, the ink that can be used in the present invention is, for example, No. 500 (oily) red, large (oily) red, and extremely coarse (oily) red manufactured by Magic Ink Co., Ltd.; Oily) red, black, blue; Mitsubishi pencil (stock) company made of silk [Pi: s] (oily) black thick core core + thin core. The base film 1 which can be used in the present invention is not particularly limited, but it is desirable to use a polyester film. In particular, in applications requiring transparency, it is preferred to use a polyester film having good transparency, and a biaxially stretched polyester film is more desirable. Further, in the case where the light-shielding property is required, a polyester film containing an inorganic pigment is preferably used, and a biaxially stretched polyester film containing a pigment such as TiO 2 or SiO 2 is more preferably used. The polyester constituting the polyester film is preferably a crystalline saturated polyester composed of an aromatic dibasic acid component and a diol component. For example, polyethylene terephthalate, propylene terephthalate, butylene glycol benzoate, polyethylene glycol 2,6 naphthalate, and the like. The base film of the present invention can be produced by a known method. For example, the biaxially stretched polyester film can be dried by an extruder and then extruded by a die (for example, a T-die, a [_ die] onto a rotary cooling drum, and then quenched as an unstretched film. This unstretched film is then stretched in the biaxial direction and heat-fixed as needed. The thickness of the base film -12-(8) 1269323 is not particularly limited, but 5 to 25 Ομηη is preferable. Further, a coating material obtained by diluting a cerium resin, particularly a curable eucalyptus resin, with the above-mentioned organic solvent is used as a release agent liquid for forming the release layer 2. The curable resin is not particularly limited, and for example, a polymerization type, an additional reaction type, an ultraviolet reaction type, an electron beam hardening line, or the like can be used. The release layer 2 can be formed by applying a coating containing a curable resin, drying it, and curing it. A conventional method such as a reverse roll coating method, a gravure roll coating method, or a pneumatic doctor blade method can be employed as the coating method. The hardened type resin coating material after application can be dried and hardened by heat to form a hardened film. In this case, it is preferable to form a hardened film by heat treatment at a temperature of 50 to 180 ° C, preferably 80 to 16 (at a range of TC for 5 seconds or more, preferably 1 〇 seconds or more). The coating thickness of the ruthenium resin is preferably in the range of 1 to 25 g/m 2 , particularly 2 to 2 〇 g/m 2 , and the thickness of the ruthenium resin coating film after hardening is 〇.〇5 to Ιμηι, especially 〇. The range of .1 to 〇.5 μιη is preferable. When the coating thickness after coating is less than 0.05 μm, the peeling performance tends to be lowered. Further, the coating thickness after hardening exceeds 1 μm. In the case where the curing of the coating film is insufficient, the peeling performance tends to change with time. [Examples] Hereinafter, the present invention will be described in detail by way of specific examples. (9) 1269323 (Example) 1 to 4 and Comparative Examples 1 to 3) [Preparation of release layer coating] A mixture of a polyoxyalkylene having a vinyl group and a ruthenium hydroquinone compound is added to a platinum-based catalyst to add a reactive type of resin. (KS-84 7H manufactured by Shin-Etsu Chemical Co., Ltd.) is dissolved in the following 1 shown in various organic solvents, the release layer paint prepared as solid content concentration of 3% based on the whole silicon resin coating. The amount of each material are 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 3 8 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〇.15μιη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 0°C、40 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. 1〜1.〇μιη程度的鈦酸鋇、氧化鉻、氧化 釔、碳酸錳、碳酸鋇、氧化矽等的粉末後，以BaTiO3100 莫耳，混合成：換算成 Ci*2O30.3莫耳、MnOO.4莫耳、 -14- (10) 1269323Resin-based resin KS-847H 300g (Shin-Etsu Chemical Co., Ltd. · Solids concentration 30%, resin 90g) Platinum catalyst CAT-PL-50T (Shin-Etsu Chemical Co., Ltd.) 3.0g Organic solvent 2700g The obtained resin coating material was formed on a biaxially-oriented polyethylene terephthalate (PET) having a thickness of 3 8 μm as a base film, and the thickness of the coating film after drying was 〇.15 μιη to a rod. The material applicator was coated with an uncoated portion of 1 cm at both ends, and dried and hardened at a heating temperature of 110 ° C for 40 seconds to form a peeling layer 2, and the wound was formed into a roll. Stripping film. [Preparation of dielectric (ceramic) coating] Baking particle size 〇. 1~1. 〇μιη degree of barium titanate, chromium oxide, cerium oxide, manganese carbonate, barium carbonate, cerium oxide, etc., after BaTiO3100 Mo Ear, mixed into: converted into Ci*2O30.3 m, MnOO.4 m, -14- (10) 1269323
Ba02.4莫耳、Ca〇i.6莫耳、SiO20,4莫耳、γ2〇3〇丨莫耳 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重量部之丙嫌 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ρ 1 〇麵氧化鉻 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 μηι。介電質塗料是由剝離層 的端部塗佈成突出4〜5歷程度。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Di及D2(mm))(參照第2圖）。 -15- (11) 1269323 將這些的結果一並表示於下述的表1。The composition of Ba02.4 mol, Ca〇i.6 mol, SiO20, 4 mol, and γ2〇3〇丨mol was mixed by a ball mill for 24 hours, and dried to obtain a dielectric material. 100 parts by weight of the dielectric material, 5 parts by weight of the 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, and the commercially available ρ is used. 1 〇 氧化 氧化 珠 珠 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 介 介 介 介 介 介 介 介 介 介 介 介 介 介 介 介 介 介 介 介 介 介 介 介 介 介 介 介 介The thickness of the coating film after drying on the film by the bar coater protrusion was 4.5 μm. The dielectric coating is applied by the end of the release layer to a degree of protrusion of 4 to 5 degrees. Each of the obtained sheets was brought close to a fluorescent lamp to evaluate whether or not a dielectric coating glaze was generated at the end portion of the peeling layer. The evaluation criteria are: no dielectric enamel is represented by ;; there are several dielectric enamel, but the shape of the ear end does not deteriorate when the dielectric is peeled off, it is represented by △; there is dielectric glaze When the dielectric is peeled off, the shape of the ear tip is deteriorated by X. [The length in the width direction of the oil-based ink enamel portion near the end portion of the peeling layer application] Further, the oil-free ink is applied to the coating portion from the uncoated portion 5 on each of the release films on which the dielectric layer is not formed ( Manufactured by Magic Ink Co., Ltd., extremely thick (oily) red, including the end portion 4 and the uncoated portion 5 of the peeling layer 2 which is visually recognized, and measuring the length of the portion where the oily ink is condensed (2nd) And Di and D2 (mm) of Figure 4 (refer to Figure 2). -15- (11) 1269323 These results are shown together 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 墨水袖縮部 的寬度方向 長度（mm) 實施例1 己烷 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 庚烷/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 庚烷/環己烷 50/50 0.0274 X 2.5Type of organic solvent Mixing ratio (%) Surface tension of organic solvent (N/m) The length of the bulk end portion of the dielectric enamel ink shrinkage portion (mm) Example 1 Hexane 100 0.0179 〇0.3 Implementation Example 2 hexane/toluene 55/45 0.0224 〇0.5 Example 3 Gengyuan/toluene 60/40 0.0229 〇0.5 Example 4 Heptane/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 Heptane/cyclohexane 50/50 0.0274 X 2.5
【發明效果】 Φ 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。 -16- (12) 1269323 第2圖是顯示在剝離薄膜的剝離層端部附近已塗佈_ 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】 φ 1 1…基材薄膜 1 2…剝離層 13…介電質層 1 4…剝離層的端部 1 5…未塗佈部 1 6…境界部 8、 1 8…墨水釉縮部 9、 1 9…墨水塗佈部 鲁 A···隆起部 B…空洞部 -17-[Effect of the Invention] Φ As described above, according to the present invention, it is possible to obtain that when the ceramic coating material is applied onto the release layer, glaze does not occur, and as a result, after being peeled off from the release film, especially An end portion in the width direction, a release film having a good-sized shape of a green sheet, and a method of producing the same. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a partial cross-sectional view showing the structure in the vicinity of the end portion of the peeling layer of the release film. -16- (12) 1269323 Fig. 2 is a partial plan view showing a state in which the ink is applied in the vicinity of the end portion of the peeling layer of the release film. Fig. 3 is a partial cross-sectional view showing the structure in the vicinity of the end portion of the peeling layer of the peeling film in the case where the ceramic paint is glazed. Fig. 4 is a partial plan view showing another state in which the oily ink is projected in the vicinity of the end portion of the peeling layer of the release film. [Description of the figure] φ 1 1... base film 1 2... peeling layer 13... dielectric layer 1 4... end portion of the peeling layer 1 5 uncoated portion 1 6 ... boundary portion 8, 1 8... ink glaze Shrinkage 9, 9 9... ink coating part Lu A··· bulging part B... hollow part -17-