TW201144072A

TW201144072A - Mold release film and method for manufacturing mold release film

Info

Publication number: TW201144072A
Application number: TW100108641A
Authority: TW
Inventors: Yohsuke Nakao; Hirotake Matsumoto; Yasushi Goto; Masahiro Tsuchiya
Original assignee: Sekisui Chemical Co Ltd
Priority date: 2010-03-12
Filing date: 2011-03-14
Publication date: 2011-12-16
Also published as: JP5719290B2; JP5837976B2; KR20130043623A; CN102791480A; CN102791480B; JP2015083379A; JPWO2011111826A1; WO2011111826A1; KR101873071B1; TWI540051B

Abstract

Disclosed is a mold release film, which has excellent mold releasability and excellent conforming characteristics to the substrate surface, and which can suppress flow out of an adhesive in heat press molding. The mold release film has a surface layer, and a mold release layer is observed only in a region within a thickness of 50-300 nm from the surface of the surface layer.

Description

201144072 六、發明說明：【發明所屬之技術領域】本發明係關於一種離型性優異且對於基板表面之追隨性優異、可抑制熱壓成形時之接著劑之流出的離型膜。【先前技術】於印刷配線基板、可撓性印刷基板、多層印刷配線板等之製U步驟中，§經由預浸體(prepreg)或耐熱膜而將覆銅積層板或銅结熱壓於基板上時使用離型膜。又，於可撓性印刷基板之製造步驟中，當藉由熱硬化型接著劑或熱硬化型接著片而將覆蓋膜熱壓接著於形成有銅電路之可撓性印刷基板本體上時，為防止覆蓋臈與熱壓板接著，亦廣泛使用離型膜。對於離型膜，例如要求如下等性能：可承受熱壓成形之耐熱性、對於印刷配線基板及熱壓板之離型性、廢棄處理之合易性。又，為了提高熱壓成形時之產品良率，對於銅電路之非污染性亦重要。、先前，作為離型膜，一直使用氣㈣、塗佈有聚石夕氧之聚對苯二甲酸乙二s旨膜1甲基戊稀膜、及聚丙稀膜等 (例如，專利文獻1 )。然而，氟系臈雖然耐熱性、離型性、非污染性優異，但價格昂f 且在廢棄處理中進行焚燒時難以燃燒並會產生有毒氣體。又’塗佈有聚矽氧之聚對苯二甲酸乙二酯膜及聚甲基戊稀膜存在因聚石夕氧或構成成分中之低分子量日體轉移，而引起印刷配線基板，尤其銅電路之污染，從而 201144072 損害品質的可能性。又，聚丙烯膜的耐熱性欠佳，離亦不充分。又’業界亦對由聚對笨二甲酸丁二酯等聚酯系樹脂構成之離型膜進行了研究，此種離型膜雖然耐熱性、廢棄處理之容易性、非污染性優異，但在離型性方面存在改善之餘地。相對於此，本案申請人發明了由聚酯系樹脂與特定量之聚丙烯構成之離型膜作為非污染性優異、且離型性亦優異之離型膜’並將其揭示於專利文獻2。此處，為了使如專利文獻2中所記載之離型臈之離型性進一步飛躍性地提高’亦如專利文獻2中所記載般，較為有效的是對離型膜實施熱處理。係於鬲溫下進行，而且必需長之情形。進而，由於實施過熱柔軟性下降，故對於基板表面然而’由於此種熱處理時間’故存在導致成本增大處理之離型膜作為膜整體之之凹凸之追隨性（嵌入性下降’有時會產生如下不良情況：例如於熱壓成形時產生空隙，或者形成於覆蓋膜上之接著劑流出至可撓性印刷基板之電極部，而成為電極部之鍍敷處理之障㈣1此，#界正尋求—衫損害對於基板表面之凹凸之追隨性、具有更優異之離型性之離型膜。專利文獻1 :曰本特開平5·283862號公報專利文獻2 :曰本特開2〇〇9 1328〇6號公報【發明内容】本發明之目的在於提供一種離型性優異且對於基板表 4 201144072 面之追隨性優異、可抑制熱壓成型膜。 “時之接者劑之流出的離本發明之第1發明係一種離型 L ^ ± 土联具有表層並僅於自上述表層之表面起至厚度為50〜到離型處理層。。。―止之區域内觀察 &本發明之第2發明係-種離型膜，具有含有聚醋系樹月曰之表層，且在自上述表層之表面起至厚度為"m為止 t區域内’上述聚㈣樹脂所含之幾基之中相對於面平行地配向之羰基的比例為45%以上。本發明之第3發明係一種離型膜，其係具有表層者， :上迷表層之表面粗輪度以為25〇〜45〇_，表面之偏斜度Rsk為+0.3〜+1 1，日*品+ ,欠Λ -1且表面之峰度Rku為5〜η。以下，詳細敍述本發明。本發明者等人發現，具有以下之3層表層，即，⑴ 觀察到特定之離型處理層之表層 , 、z J相對於面平行地配向之#厌基之比例滿足特定之節图的I & 衧疋之範圍的表層，以及（3)表面粗 “度Rz、表面之偏斜度Rsk及表範圍的表層中之杯主a URku滿足特疋之 =層中之任一表層的離型膜不會損害對於基板表面現離並抑制熱咖時之接著劑之流出，同時可顯現優異之離型性，從而完成本發明。本發明之帛丨發明之離型膜具有表層，且僅於自上述表層之表面起至厚度為5〇〜3 型處理層。為止之區域内觀察到離本說明書中，所謂離型處理層，係指具有與表層中之 201144072 2區域相比不同之外觀之離型性優異的層。又書中’離型處理層不僅包括層整本說月亦包衽雜a. 體具有相同外觀之情形，括雖局部性地包含具有不同外觀之部布γ , 形成〗層之情形。，但作為整體於上述離型處理層中觀察到與上相比不同之圆案。作為於上述離型處理層中戶^家他區域案，例如可列舉相對於面平行之條紋狀之圓案等察=之圖表層令之其他區域内所觀察到之圖案並無特別限一、上述可列舉砂狀、渦狀等圖案义疋，例如国杀夂-亥專以外之不均勻之圖1、2及3係示意性地表矛太 ’、蹬夕主抵本發明之第1發明之離形獏之表層之-部分的剖面圖。於圊卜 1 屉之矣而 βη ^ J中’上側為表層之表面，即，離型膜之表面。圓^^ 3 _ 勹衣一部分具有於表面側觀察到相對之表層之之離型處理層！。於圖"，表層中之圆茶之圖案，於圖2中，表層中之i 具有砂狀 u a上八他£域2具有渴狀之圖案於圖3中，表層中之其他區域，、 LQ2具有其他不均勻之圖案。由於如上述般所觀察到之離型處理層為高密度且作為壁層而發揮作用’故上述表層在例如與環氧系接接 =之情形時可抑制環氧系接著劑之滲透。因此，本發明之第1發明之離型膜可顯現優異之離型性。觀察上述離型處理屉$古、土 #[Technical Field] The present invention relates to a release film which is excellent in release property and excellent in followability to a substrate surface and which can suppress elution of an adhesive at the time of hot press forming. [Prior Art] In the U step of manufacturing a printed wiring board, a flexible printed circuit board, or a multilayer printed wiring board, the copper-clad laminate or copper junction is heat-pressed to the substrate via a prepreg or a heat-resistant film. A release film is used on the top. Further, in the manufacturing step of the flexible printed circuit board, when the cover film is thermally pressed against the flexible printed circuit board body on which the copper circuit is formed by the thermosetting adhesive or the heat-curable adhesive sheet, Preventing the covering of the crucible and the hot platen. Next, the release film is also widely used. For the release film, for example, it is required to withstand the heat resistance of hot press forming, the release property of the printed wiring board and the hot press plate, and the ease of disposal. Moreover, in order to improve the yield of the product during hot press forming, it is also important for the non-contamination of the copper circuit. In the past, as a release film, a gas (4), a polyethylene terephthalate film coated with polyoxazine, a methyl pentane film, a polypropylene film, and the like have been used (for example, Patent Document 1) . However, the fluorine-based ruthenium is excellent in heat resistance, release property, and non-contamination property, but it is expensive and incinerated during waste disposal, and it is difficult to burn and generate toxic gas. Moreover, the poly(ethylene terephthalate) film coated with polyoxymethylene and the polymethylammonium film may cause a printed wiring board, especially copper, due to the low molecular weight transfer of the particles in the polyoxo oxygen or the constituent components. The pollution of the circuit, thus 201144072, the possibility of damage to quality. Further, the polypropylene film is inferior in heat resistance and is not sufficiently separated. Further, the industry has also studied a release film composed of a polyester resin such as polybutylene dicarboxylate, which is excellent in heat resistance, ease of disposal, and non-contamination. There is room for improvement in terms of release. On the other hand, the present inventors have invented a release film comprising a polyester resin and a specific amount of polypropylene as a release film which is excellent in non-contaminating property and excellent in release property, and is disclosed in Patent Document 2 . Here, in order to further improve the release property of the release crucible as described in Patent Document 2, as described in Patent Document 2, it is effective to heat-treat the release film. It is carried out at a temperature of 鬲 and must be long. Further, since the superheat softness is lowered, the follow-up property of the release film (deterioration of embedding) of the release film which causes the cost increase treatment due to the heat treatment time of the substrate surface may be generated. The following problems occur: for example, a void is generated during hot press forming, or an adhesive formed on the cover film flows out to the electrode portion of the flexible printed circuit board, and becomes a barrier to the plating treatment of the electrode portion (4). - A release film having a more excellent release property against the unevenness of the surface of the substrate. Patent Document 1: Japanese Patent Application Laid-Open No. Hei No. 5,283,862 Patent Document 2: 曰本特开2〇〇9 1328 〇〇【【【【【【〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇基板基板基板基板基板基板基板基板基板基板基板基板基板基板The first invention is a release type L ^ ± soil having a surface layer and only from the surface of the surface layer to a thickness of 50 〜 to the release treatment layer. The second invention of the present invention relates to a release film comprising a surface layer of a vinegar tree, and a poly(tetra) resin in the region from the surface of the surface layer to a thickness of "m The ratio of the carbonyl group which is aligned in parallel with respect to the surface is 45% or more. The third invention of the present invention is a release film which has a surface layer, and the surface roughness of the surface layer is 25 〇〇 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 , 表面 , , , , , , , , 表面表面表面表面表面表面表面表面表面表面表面表面表面表面表面表面表面表面表面表面表面表面表面表面表面It has been found that there are three layers of the following layers, that is, (1) the surface layer of a specific release treatment layer is observed, and the ratio of the ratio of the anti-formation of z J to the plane parallel to the surface satisfies the specific section I & The surface layer of the range of 疋, and (3) the surface roughness "Rz, the surface skewness Rsk, and the surface of the surface of the cup master a urku meet the characteristics = the release film of any of the layers will not Damage to the surface of the substrate and inhibit the outflow of the adhesive when hot coffee, while showing excellent release, so that The release film of the invention of the present invention has a surface layer and is only from the surface of the surface layer to a treatment layer having a thickness of 5 〇 3 to 3. The area in the area is observed to be away from the present specification. The treatment layer refers to a layer having excellent release properties different from the 201144072 2 region in the surface layer. In addition, the 'release coating layer includes not only the layer, but also the same layer. In the case of the appearance, a case where the layer γ having a different appearance is partially formed to form a layer is formed. However, as a whole, a round case different from the above is observed in the above-mentioned release treatment layer. In the case of the household area in the type of processing layer, for example, a stripe-shaped round case parallel to the surface may be cited, and the pattern observed in other areas of the pattern layer is not particularly limited, and the above-mentioned sand may be enumerated. Patterns such as snails and vortexes, such as the non-uniform patterns other than the National Killing 夂-Hai, are schematically illustrated as the spears, and the singularity of the first invention of the present invention A section view of the surface layer. In the middle of the tray, the upper side of the βη ^ J is the surface of the surface layer, that is, the surface of the release film. Round ^^ 3 _ 勹 A part of the coating has a release layer on the surface side that is opposite to the surface layer! . In Fig. 2, the pattern of the round tea in the surface layer, in Fig. 2, the i in the surface layer has a sand-like ua on the octah. The domain 2 has a thirsty pattern in Fig. 3, other areas in the surface layer, LQ2 Has other uneven patterns. Since the release treatment layer is observed to have a high density and functions as a wall layer as described above, the above-mentioned surface layer can suppress the penetration of the epoxy-based adhesive when it is bonded to, for example, an epoxy system. Therefore, the release film of the first invention of the present invention can exhibit excellent release properties. Observe the above-mentioned release treatment drawer $古,土#

^ 方法並無特別限定，但較佳A 曰由穿透式電子顯微鏡對使用切片機等在厚度方向行 :割所得之剖面進行觀察之方法。又，作為觀察上：處理層之方法’亦可利用藉由偏光顯微鏡、原子力顯微鏡 201144072 =吏=片機等在厚度方向上進行切割所得之剖面進行 =察之方法。上述穿透式電子顯微鏡（τεμ，τ⑽進_η 式電子顯微鏡（型號H-9500，曰立土山 u. u ^ , S立先端科技（Hitachi^ The method is not particularly limited, but a preferred method is to observe a section obtained by cutting a section in a thickness direction using a microtome or the like by a transmission electron microscope. Further, as a method of observing: a method of treating a layer, a method of observing a section obtained by cutting in a thickness direction by a polarizing microscope or an atomic force microscope 201144072 = 吏 = a sheet machine may be used. The above-mentioned transmission electron microscope (τεμ, τ(10) into _η-type electron microscope (Model H-9500, 曰立土山 u. u ^ , S Li Xian Technology (Hitachi

High-Technol〇gies )公司製造）別限定，例如可列舉滑動式ζ/機二上述切片機並無特理化公司製造）等。 •戒SM2000-R，池田又，本發明之第1發明之離型膜由於僅在自上述表層 :表面起至厚度為50〜300 nm為止之區域内具有離型處理層，故與為了離型性之改善而實施例如熱處理等之先前之離型膜不同，具有優里$ #开彳w + 軟性。因此，本:::第it亦可維持作為膜整體第發明之離型臈對於基板表面之追心性優異，可抑制熱壓成形時之接著劑之流出。若上述離型處理層之厚度自上述表層之表面起未達5〇 ⑽’則上述表層在例如與環氧轉著劑接觸之情形時益法充分地抑制環氧系接著劑之滲透，所獲得之離型膜之離型性下降。若上述離型處理層之厚度自上述表層之表面起超過3〇、〇 _，則所獲得之離型膜之柔軟性下降，對於基板表面之追隨ϋ下降，難以抑制熱壓成形時之接著劑之流出。上述離型處理層之厚度較佳為自上述表層之表面起70 X上且較佳為自上述表層之表面起250 nm以下。本發明之第2發明之離型膜具有含有聚酿系樹脂之表層。於本發明之第2發明之離型膜中，在自上述表層之表 201144072 面起至厚度為1 _為止之區域内，上述聚Μ樹脂所含之羰基之中相對於面平行地配向之羰基的比例為45%以上。 ^本說明書中，聚酯系樹脂所含之羰基之中相對於面平行地配向之羰基的比例X係藉由下述式算出。 x=: (A/ ( Α+ B ) }xl〇〇 ( 1 ) 式（1 )中，A表示藉由χ射線分析所得之相對於面平行地配向之㈣之波峰強度，B表示藉由χ射線分析所得之相對於面垂直地配向之羰基之波峰強度。本說明書中，所謂相對於面平行或垂直，係指_於_型膜之表面朝向平行方向或垂直方向。藉由上述相對於面平行地配向之羰基之比例為上述範圍内，本發明之第2發明之離型膜可顯現優異之離型性。推測其原因在於：在自上述表層之表面起至厚度為1 ” 為止之區域内’相對於面平行地配向之幾基之比例增加，藉此上述表層之表面之疏水性增大。、，又於本發明之第2發明之離型膜中，上述相對於面平行地配向之幾基之比例為上述範圍内4區域係自上述表層之表面起至厚度為1鋒為止之區域，因此與為了離型性之改善而實施例如熱處理等之先前之離型膜不同，具有優異之離型性亦可維持作為膜整體之柔軟性。因此，本發明之第2發明之離型膜對於基板表面之追隨性優異，可抑制熱壓成形時之接著劑之流出。右上述相對於面平行地配向之羰基之比例未達45%，、述表層之表面之疏水性會下降，因此所獲得之離型膜 8 201144072 之離型性下降。上述相對於面平行地配向之減之比例較佳&训以上0 上述相對於面平行地配向基 ^ Λ Π又叛丞之比例之上限並無特二二二 ’但較佳為90%以下。若上述相對於面離：臈二：碳基之比例超過90%’則有時會因例如製造型膜產生無冑處理之作功能量變得過大而使所獲得之離孓膜產生皺褶、傷痕等損傷。上述相對於面平行地配向之縣之比例更佳為观以 Γ ° 入作為進行上述χ射線分析之方法，例如可列舉對斜射一表層之表面之X射線之繞射進行測定的方法分析裝广又，用以進行上述χ射線分析之Χ射線型X㈣1 限定，例如可列舉薄膜評價用試樣水平射線繞射裝置（型號smartLab，製造）等。理干（Rigaku)公司表面月之第3發明之離型膜具有表層，且上述表層之表面粗糙度RZ之下限為2 洁9<Λ m右上述表面粗糙度RZ未 =广，則所獲得之表層變得平滑，表層之接觸面積增大，離型性下降。上述表面粗 nm。忙厌Kz之較佳之下限為280 粗述表面之上限為45〇咖。若上述表面又Z超過45〇nm，則所獲得之表層之凹凸會增加，在例如相對於環氧接著劑等流動性 A系軟性較尚之被黏附體 9 201144072 而使用之情形時，成為與被黏附體之接觸面積增大、離型性下降之原因。本說明書中，所謂表面粗糙度Rz，係指針對表層之表面，將基準長IL中自最高之山頂起至第5高度為止之山頂之標高分別設為Υρ1、γρ2、γρ3 ' γρ4及γρ5，將自最深之谷底起至第5深度為止之谷底之標高分別設為γν广 Yd、^、Υν…ν5時，根據下述式（2)所求出之值，且表不值越大、表面之整體越粗縫，值越小、表面之整體 -=c I VD1 +Yd2 + Y〇3 + Yd4 + Yd5 , + , yv1 +Yv2 + Yv3 + Yv4 + Yv5 ( )/5 (2) 上述表層之表面之偏斜度Rsk的下限為+〇3。若上述表面之偏斜度Rsk未達+〇 3，則所猝 ⑴π後仔之表層之凸成分減少，表層之接觸面積增大，離型性表層之外觀不良。上述表面I::/會產生所獲得之 +0 s ,,, 面之偏斜度Rsk之較佳之下限為 + 〇.5，更佳之下限為+〇 8。又’上述表面之偏斜度Rsk之上限為+1卜之偏斜度Rsk超過1.丨，則所獲 ⑴所攫仔之表層之凸成分合在例如相對於環氧接荖蒯笪X刀s增加，體而#…動性或柔軟性較高之被黏附體而使用之情㈣，成為與被_體之接型性下降之原因。田積增大、離本㈣書中’所謂表面之偏斜度歸，係指針表面，將均方根粗輪度 $ 攄下… '、將山之高度設為W時，根據下述式（3)所求出之值，》裉且表不右為正值，則相對於表 10 201144072 201144072 若為負值，則相對於表面之平 (3) 面之平均線、凸成分較多均線、凹成分較多。 [數2]High-Technol〇gies) (manufactured by the company), for example, a sliding type machine/machine 2, the above-mentioned slicer is not manufactured by a specializing company, and the like. • SM2000-R, Ikeda, the release film of the first invention of the present invention has a release treatment layer only in the region from the surface layer to the thickness of 50 to 300 nm, and is therefore intended to be released. The improvement of the property is different from the previous release film such as heat treatment, and has a good value of ##开彳w + softness. Therefore, the present invention can be maintained as a film as a whole. The release liner of the first invention is excellent in the chasing property of the substrate surface, and can suppress the flow of the adhesive during hot press forming. If the thickness of the release treatment layer is less than 5 〇 (10)' from the surface of the surface layer, the surface layer is sufficiently inhibited from permeating the epoxy-based adhesive when it is in contact with, for example, an epoxy transfer agent. The release property of the release film is lowered. When the thickness of the release treatment layer exceeds 3 〇 and 〇_ from the surface of the surface layer, the flexibility of the release film obtained is lowered, and the follow-up of the surface of the substrate is lowered, and it is difficult to suppress the adhesive at the time of hot press forming. Outflow. The thickness of the release coating layer is preferably 70 X from the surface of the surface layer and preferably 250 nm or less from the surface of the surface layer. The release film of the second invention of the present invention has a surface layer containing a polyolefin resin. In the release film of the second aspect of the invention, the carbonyl group which is aligned in parallel with respect to the surface among the carbonyl groups contained in the polyfluorene resin in the region from the surface of the surface of the surface layer 201144072 to the thickness of 1 _ The ratio is more than 45%. In the present specification, the ratio X of the carbonyl groups which are aligned with respect to the surface in the carbonyl group contained in the polyester resin is calculated by the following formula. x=: (A/ ( Α+ B ) }xl〇〇( 1 ) In the formula (1), A represents the peak intensity of (4) aligned with respect to the plane by χ ray analysis, and B is represented by χ The peak intensity of the carbonyl group which is perpendicularly aligned with respect to the surface obtained by the ray analysis. In the present specification, the term "parallel or perpendicular to the plane" means that the surface of the _type film faces the parallel direction or the vertical direction. In the above range, the release film of the second aspect of the invention exhibits excellent release properties. It is presumed that the reason is that the surface is from the surface of the surface layer to a thickness of 1 ”. In the release film of the second aspect of the invention, the surface of the surface layer is increased in parallel with the surface. The ratio of the number of the bases is such that the four regions in the above range are from the surface of the surface layer to the thickness of the first layer. Therefore, the ratio is excellent unlike the prior release film which is subjected to, for example, heat treatment for the improvement of the release property. Release Therefore, the release film of the second invention of the present invention is excellent in followability to the surface of the substrate, and can suppress the outflow of the adhesive during hot press forming. The right side is aligned in parallel with the surface. The ratio of the carbonyl group is less than 45%, and the hydrophobicity of the surface of the surface layer is lowered, so that the release property of the release film 8 201144072 is reduced. The ratio of the above-mentioned parallel alignment is preferably & Above 0, the upper limit of the ratio of the above-mentioned parallel to the base and the rebellion is not particularly 222' but preferably 90% or less. If the above is relative to the face: 臈 2: the ratio of the carbon base exceeds 90%' may cause wrinkles, scars, and the like to be obtained from the ruthenium film due to, for example, an excessive amount of function of the flawless treatment of the manufactured film. The ratio of the above-mentioned counties parallel to the surface is more佳观入作为作为作为作为作为作为作为作为作为作为作为进行进行进行进行进行进行进行进行进行进行进行进行进行进行进行进行进行进行进行进行进行进行进行进行进行进行进行进行进行进行进行进行进行进行进行进行进行进行进行The linear type X (four) 1 is limited, for example, a sample horizontal ray diffraction apparatus for film evaluation (manufactured by SmartLab, etc.). The release film of the third invention of Rigaku Co., Ltd. has a surface layer, and the surface of the surface layer is rough. The lower limit of the degree RZ is 2 clean 9 < Λ m right above the surface roughness RZ is not = wide, the surface layer obtained is smooth, the contact area of the surface layer is increased, and the release property is lowered. The above surface is thick nm. The preferred lower limit is 280. The upper limit of the rough surface is 45 。. If the surface Z exceeds 45 〇 nm, the surface roughness of the surface layer is increased, for example, with respect to the fluidity of the epoxy adhesive, etc. When it is used in the case of the adherend 9 201144072, it becomes a cause of an increase in the contact area with the adherend and a decrease in the release property. In the present specification, the surface roughness Rz is the surface of the surface layer, and the elevation of the peak from the highest peak to the fifth height in the reference length IL is Υρ1, γρ2, γρ3 'γρ4, and γρ5, respectively. When the elevation of the bottom of the valley from the deepest bottom to the fifth depth is γν wide Yd, ^, Υν...ν5, the value obtained by the following formula (2) is obtained, and the surface value is larger, and the surface is The coarser the whole, the smaller the value, the overall surface -=c I VD1 +Yd2 + Y〇3 + Yd4 + Yd5 , + , yv1 +Yv2 + Yv3 + Yv4 + Yv5 ( )/5 (2) Surface of the above surface layer The lower limit of the skewness Rsk is +〇3. If the skewness Rsk of the above surface does not reach +〇3, the convex component of the surface layer after 猝(1)π is decreased, the contact area of the surface layer is increased, and the appearance of the release surface layer is poor. The above surface I::/ will produce the obtained +0 s , , and the preferred lower limit of the skewness Rsk of the surface is + 〇.5, and the lower limit is preferably +〇 8. Moreover, the upper limit of the skewness Rsk of the above surface is +1, and the skewness Rsk exceeds 1. 丨, then the convex component of the surface layer obtained by (1) is combined, for example, with respect to the epoxy joint X knife. s increase, body and #... the use of the viscous or softer adherent body (4), which is the reason for the decline in the connection with the _ body. The increase of the field product, from the book (4), the so-called surface skewness, the surface of the pointer, the root mean square coarse rotation $ 摅 ... ..., when the height of the mountain is set to W, according to the following formula (3) If the value obtained, 》 and the table is not positive, is a positive value with respect to Table 10 201144072 201144072. If the value is negative, the average line of the flat (3) plane and the convex component are more mean and concave. More. [Number 2]

Rsk= 1 /Rq3 -1 /η Σ Yi3 i=1 上述表層之表面之峰度Rku之下限為％峰度^未達5’則所獲得之表層之凸形狀變得平緩= ^接觸面積增大，離型性下降。上述表面之峰《叫之較佳之下限為6 ’更佳之下限為7。 ^又，上述表面之峰度Rku之上限為11。若上述表面之峰度Rku超過U，則所獲得之表層變得平滑，表層面積增大，離型性下降。本說明書中’所謂表面之峰度Rku，係指針對表層之表面’將均方根⑽度設為Rq、將山之高度設為Y1日/㈣下述式（4)所求出之值，且袅亍佶勒以表不值越大，凸形狀變得越陡肖，並且相料平均料坦之部分增加，值料，凸形狀變得越平緩，並且相對於平均線平坦之部分減少。 [數3]Rsk= 1 /Rq3 -1 /η Σ Yi3 i=1 The lower limit of the kurtosis Rku of the surface of the above surface layer is %. The kurtosis ^ is less than 5', the convex shape of the surface layer obtained becomes gentle = ^The contact area increases , the release is reduced. The lower limit of the above-mentioned surface peak "the lower limit of 6" is better. ^ Again, the upper limit of the kurtosis Rku of the above surface is 11. When the kurtosis Rku of the above surface exceeds U, the obtained surface layer becomes smooth, the surface area increases, and the release property is lowered. In the present specification, the term "the kurtosis of the surface Rku, the surface of the surface of the surface layer" is set to the root mean square (10) degree as Rq, and the height of the mountain is set to Y1 day/(4). Moreover, the larger the value of the 袅亍佶 , , , , , , , , 凸凸凸凸凸凸凸凸凸凸凸凸凸凸凸凸凸凸凸凸凸凸凸凸凸凸凸凸凸凸凸凸凸凸[Number 3]

Rku=1/Rq4 ·ΐ/ηΣΥί4 (4) i=i 為了於本發明之第I發明之離型臈中，僅在自上述表層之表面起至厚度為50〜谓nm為止之區域内觀察到離型處理層，較佳為例如對上述表層進行摩擦處理等表面處理。又’為了於本發明之第2發明之離型膜中將上述相對於面平行地配向之羰基之比例設定為上述範圍内，且為了於本發明之第3發明之離型膜.中賦予滿足上述範圍之表面 201144072 較佳為亦同樣地對上述表層進行粗糙度Rz等之表面形狀摩擦處理等表面處理。但較佳為以使由下述式成為50〜500 KJ之方式上述摩擦處理並無特別限定 (5 )所表示之作功能量En ( KJ ) 進行。Rku=1/Rq4·ΐ/ηΣΥί4 (4) i=i In the release liner of the first invention of the present invention, it is observed only in the region from the surface of the surface layer to a thickness of 50 to nm. The release treatment layer is preferably subjected to a surface treatment such as rubbing treatment on the surface layer. In addition, in the release film of the second invention of the present invention, the ratio of the carbonyl group which is aligned in parallel with respect to the surface is set within the above range, and the content of the release film of the third invention of the present invention is satisfied. The surface of the above-mentioned range 201144072 is preferably subjected to surface treatment such as surface shape rubbing treatment such as roughness Rz in the surface layer. However, it is preferable that the rubbing treatment is performed in a manner that the following formula is 50 to 500 KJ. The rubbing treatment is not particularly limited to the functional amount En (KJ) indicated by (5).

En= ( Arxj) / ( WxLS) ( 5) :(5)中’ Ar表示摩擦處理裝置進行摩擦處理之面積 J表示用以進行摩擦處理之每單位時間之作功且 _(KJ/min)’ W表示受到摩擦處理之膜之寬度（m)，Ls : 不文到摩擦處理之膜之線速（m/min ) 〇上述式（5)中，上述摩擦處理裝置進行摩擦處理之面積斛（心係摩擦處理裝置進行摩擦處理之膜之面積。又，上述用以進行摩擦處理之每單位時間之作功量了 (KJ/min )係藉由將每單位時間之負荷能量（因摩擦處理裝置對膜施加壓力而產生之施加於摩擦處理裝置之動力源的負荷能量）與進行摩擦處理之次數相乘而求出。、又，上述受到摩擦處理之膜之寬度w(m)係摩擦處理裝置進行摩擦處理之臈之寬度。、進而，上述受到摩擦處理之膜之線速LS(m/min)係膜通過摩擦處理裝置之速度。若上述作功能量En ( KJ )未達5〇 KJ，則存在如下情形，即未能在如上所述之自上述表層之表面起至厚度為5〇〜3〇〇 nm為止之區域内觀察到離型處理層、或者無法將上述相對於面平行地配向之羰基之比例設定為上述範圍内、 12 201144072 狀，因此右滿足上述範圍之表面粗糙度Rz #之表面形 —、. 時無法對所獲得之離型膜賦予優異之離型性。右上述作功忐置En ( KJ)超過5〇〇 kj 因所獲得之離型腔夕矛从α 卜席心. 道、柔軟性下降’或者會產生皺褶、傷痕，導致對於基板表面之追隨性下降，盔法充八地抑制熱壓成形時之接著劑之流出。 …、充刀地旦述摩“處理更佳為以使由上述式（5)所表示之作功能罝如（KJ)之上限成為300 KJ之方式進行。於上述摩擦處理中，摩擦處理材料之表面之素材中所使用的織物之纖維之拉伸強度的較佳之下限為i 〇g/d，較佳之上限為5.〇_。若上述纖維之拉伸強度未達L0g/d，則存在纖維於上述摩擦處理中伸長而斷裂，所獲得之離型膜上附著纖維之情形。若上述纖維之拉伸強度超過5〇 ⑼，則存在如下情形：所獲得之離型膜上產生皺褶、傷痕專損傷，對於基板表面之追隨性下降，無法充分地抑㈣壓成形時之接著劑之流出。上述纖維之拉伸強度 2 上限為3.0 g/d。再者，本說明書中，所謂纖維之拉伸強度，係指藉由以JIS-L.5為依據之方法所求出之—根纖維之拉伸強曰卢上述纖維之伸長率之較佳之下限為1%，較佳之上：屬。若上述纖維之伸長率未達1%，則存在纖維於上^摩擦處理中伸長而斷裂’所獲得之離型膜上附著纖維形。若上述纖維之伸長率超㉟3〇%，則存在如下情形./ 獲得之離型膜上產生皺褶、傷痕等損傷’對於基板表面所 13 201144072 追隨性下降，無法夺公# & 77地抑制熱壓成形時之接著劑之泣En= ( Arxj) / ( WxLS) ( 5) : (5) where 'Ar is the area J where the friction treatment device performs the rubbing treatment, and the work per unit time for performing the rubbing treatment is _(KJ/min)' W represents the width (m) of the film subjected to the rubbing treatment, and Ls: the line speed (m/min) of the film which is not subjected to the rubbing treatment. In the above formula (5), the area of the rubbing treatment apparatus is subjected to rubbing treatment (heart) The area of the film subjected to the rubbing treatment by the rubbing treatment device. Further, the amount of work per unit time (KJ/min) for performing the rubbing treatment is performed by the load energy per unit time (by the friction processing device pair) The load energy of the power source applied to the friction processing device generated by the pressure applied by the film is multiplied by the number of times of the rubbing treatment. Further, the width w (m) of the film subjected to the rubbing treatment is performed by the friction processing device. The width of the rubbing treatment. Further, the linear velocity LS (m/min) of the film subjected to the rubbing treatment passes through the speed of the rubbing treatment device. If the functional amount En (KJ) is less than 5 KJ, There is a situation where the failure is as above It is described that the release treatment layer is observed from the surface of the surface layer to a thickness of 5 〇 to 3 〇〇 nm, or the ratio of the carbonyl group which is aligned with the surface in parallel with the surface is not set within the above range, 201144072, so the surface shape of the surface roughness Rz # satisfying the above range is right, and the release film obtained is not excellent in release property. The above-mentioned work device En (KJ) exceeds 5 〇〇. Kj due to the obtained release cavity, the spear from the α 卜席 heart. The road, the softness decreased, or wrinkles and scratches will occur, resulting in a decrease in the followability of the substrate surface, and the helmet method will suppress the hot press forming. Then, the flow of the agent is carried out. The process is more preferably performed so that the upper limit of the function (KJ) represented by the above formula (5) is 300 KJ. The lower limit of the tensile strength of the fiber of the fabric used in the material of the surface of the rubbing treatment material is i 〇g / d, preferably the upper limit is 5. 〇 _. If the tensile strength of the above fiber is less than L0g / d, there is fiber at the above friction If the tensile strength of the above-mentioned fiber exceeds 5 〇 (9), there is a case where wrinkles and scratches are generated on the release film obtained, for the case where the fiber is attached to the release film and the fiber is attached to the release film. The followability of the surface of the substrate is lowered, and the flow of the adhesive at the time of press forming cannot be sufficiently suppressed. The upper limit of the tensile strength 2 of the fiber is 3.0 g/d. Further, in the present specification, the tensile strength of the fiber is The preferred lower limit of the elongation of the above-mentioned fibers, which is determined by the method based on JIS-L.5, is 1%, preferably above: If the elongation of the fiber is less than 1%, the fiber may be attached to the release film obtained by stretching and breaking the fiber during the rubbing treatment. If the elongation of the fiber exceeds 353〇%, the following situation may occur. / The damage of the obtained release film such as wrinkles, scratches, etc. 'For the surface of the substrate 13 201144072 The followability is degraded, and it is impossible to suppress the ##### Weeping of the adhesive during hot forming

出。上述纖維之伸長率之更佳 "_L 尺1主之上限為29% 〇 A去，士相明書中，所謂纖維之伸長率 § 诚夕十、t 係私藉由以JIS-L-1095為依據之方法所求出之一根纖維之拉伸伸長率。 M i m具體^ ’例如可列舉ΡΕΤ 二一一lene terephthalate，聚對笨二甲酸乙 D、螺縈、棉、羊毛、乙酸鹽等。其中， ’、 ' 就可藉由進行摩擰虛王里而進一步抑制離型膜上所產生 ’、聛"+私且4 ± 皺褶、傷痕等損傷，從而獲付對於基板表面之追隨性優異之離型膜，以著於離型膜上之纖維而言，較佳為嫘營、羊毛。又，上述摩擦處理材料之表面之素材中所使用的織物之摩擦係數之較佳之下限為〇丨，千乂往义上限為0 8。述織物之摩擦係數未達〇· 1，則存 ⑷仔在所獲得之離型膜之離型性下降之情形。若上述織物之摩擦係數超過08，則獲得之離型膜上產生敏褶、傷痕等損傷，對於基板表面之追隨性下降’無法充分地抑制熱壓成形時之接著劑之之情形。上述織物之摩擦係數之更佳：上限為0.7。更佳之 ’係指藉由 mm之聚碳再者，本說明書中，所謂織物之摩擦係數以JIS-K-7125為依據之方法所求出之相對於2 酸酯板之織物的摩擦係數。Out. The elongation of the above fiber is better "_L The upper limit of the ruler 1 is 29% 〇A goes, in the book, the elongation of the fiber § Cheng Xi 10, t system private by JIS-L-1095 The tensile elongation of one of the fibers was determined according to the method. The M i m specific ^ ' can be exemplified by ΡΕΤ 2 1 lene terephthalate, poly-p-dibenzoate D, snail, cotton, wool, acetate, and the like. Among them, ', ' can further suppress the damage caused by the ', 聛 " + private and 4 ± wrinkles, scars, etc. on the release film by performing the winding of the virtual king, thereby obtaining the followability to the substrate surface. The excellent release film is preferably camping or wool for the fiber on the release film. Further, the lower limit of the friction coefficient of the fabric used in the material of the surface of the above-mentioned friction-treated material is 〇丨, and the upper limit of the 乂乂 is 0 8 . When the coefficient of friction of the fabric is less than 〇·1, then (4) the release of the release film obtained is reduced. When the friction coefficient of the woven fabric exceeds 08, damage such as pleats and scratches is formed on the release film, and the followability to the surface of the substrate is lowered. The case of the adhesive at the time of hot press forming cannot be sufficiently suppressed. The above fabric has a better coefficient of friction: the upper limit is 0.7. More preferably, the term "polycarbon" by mm, in this specification, the coefficient of friction of the fabric is determined by the method based on JIS-K-7125, and the coefficient of friction of the fabric relative to the 2 acid plate.

上述織物之彈性模數之較佳之下限A 丨氏两ϋ· 1 Mpa，較佳之上限為4.0 Mpa。若上述織物之彈性模數未達〇 1 % 存在所獲得之離型膜之離型性下降之愔 3則障形。若上述織物之 201144072 彈性模數超過4.0 Mpa，則存在所獲得之離型膜上產生皺褶、傷痕等損傷，對於基板表面之追隨性下降，無法充分地抑制熱壓成形時之接著劑之流出之情形。上述織物之彈性模數之更佳之下限為〇.7Mpa，更佳之上限為3 9Mpa。再者，本說明書中，所謂織物之彈性模數，係指藉由以J1S-K-7127為依據之方法所求出之織物之硬度。上述織物之拉伸強度之較佳之下限為1.5 N/l〇mm,較佳之上限為2.5 N/10 mm。若上述織物之拉伸強度未達i 5 N/10mm，則存在纖維於上述摩擦處理中伸長而斷裂，所獲得之離型膜上附著纖維之情形。若上述織物之拉伸強度超過2.5N/1Gmm，則存在所獲得之離型膜上產生Μ褶、傷痕等損傷，對於基板表面之追隨性下降，無法充分地抑制执壓成形時之接著劑之流出之情形。上述織物之拉伸強度之更佳之下限為1.6 N/1〇麵，更佳之上限為2 3 _職，進而更佳之上限為UN/lOmm。再者，本說明書中，所謂織物之拉伸強度係指藉由以JIS-K_7127為依據之方法所求出之織物之拉伸強/ 上述用以進行摩擦處理之摩擦處理裝置並無特別限制’例如可列舉研磨處理裝置（型號_观械（Yamagau Machinery)公司製造）等。 …機於本發明之第2發明之離型膜中，上系樹脂。於本發明之第丨及第 έ有聚酯乃之弟1及帛3發明之離型膜中，卜+,主層並無特別限定’但較佳為含有聚醋系樹脂。迷表以下’對本發明之第卜第2及第3發明之離型膜中共 15 201144072 通之事項進料述。再者，本說明書中，於僅稱為本發明之離型膜時，表示適用於本發明之第丨、第2及第3發明之離型膜中之任一者。上述聚酯系樹脂並無特別限定。藉由使用上述聚酯系樹脂，所獲得之離型膜可顯現優異之機械性能、尤.其可於通常進仃熱壓成形《l70°c左右之溫度區域内顯現優異之機械性此。又，藉由使用上述聚酯系樹脂，而減輕對所獲得之離型膜進行焚燒處理時之環_，於經濟方面亦有利進而’由於上述聚醋系樹脂之低分子量成分較少，故所獲侍之離型膜之非污染性優異，亦可抑制因伴隨熱壓之低为子量成分之滲出而產生可撓性印刷基板之電極敷不良等問題。作為上述聚醋系樹脂’例如較佳為結晶性芳香族聚醋性方香族聚s旨樹脂並無特別限定，例如可列族二叛酸或其醋形成性衍生物與低分子量脂肪族 —%反應所得之結晶性芳香族聚酯樹脂等。作為上述結晶性芳香族聚醋樹脂，亦可列舉：使叛酸或其醋形成性衍生物與低分子量脂肪族二醇久阿刀子量二醇下，亦猫太「+ “ 族聚s旨樹脂（以方稱為「主鏈中具有聚醚骨架之脂丨）.,ν Ώ 日日性方香族聚酯樹，乂及於使芳香族二羧酸或其酯形子量胩V从注何生物與低分月曰肪族二醇反應所得之結晶性己内酯置挪Α ^ 万贷筷聚酯樹脂溶解於 •早體中後，使己内醋開環聚人日開衣^ 〇而獲得之結晶性芳香 201144072 族聚酯樹脂（以下，亦稱為「結晶性芳香族聚酯樹脂」）等。主鏈中具有聚己内酯骨架之低分子量脂肪族二醇反應所得之性芳=成性衍生物與情形相比，由於所獲得之離型方香族聚醋樹脂之離型性亦優異，因此較佳為主鏈中具有：熱：，柔軟性及芳香族聚酯樹脂、主鏈中I有二A醚骨架之結晶性族聚醋樹脂。鏈中“聚己㈣骨架之結晶性芳香作為上述方香族二羧酸或列I.料— 飞/、知形成性衍生物，例如可料.對本二甲、間苯二甲酸# 對苯二羧酸(paranh , _本-甲馱、奈二甲酸、岐（paraphenylene dicarb〇xylic acid)、料二二二:間苯：甲酸二甲酷、鄰苯二甲酸…、蔡二甲可你a對本-羧酸二甲酯等。該等既可單獨使用，亦可併用兩種以上。作為上述低分子量脂肪族二醇，例如可列舉：乙二醇、古’丙—醇、1,3-丙二醇、13-丁三醇、1，4-丁二醇、新戊二，戊一醇1，6-己一醇、1，4-環己院二甲醇等。該等既可單獨使用，亦可併用兩種以上。作為上述南分子量二醇’例如可列舉··聚乙二醇、聚醇 t 四亞甲基二醇（polytetramethylene glycol)、聚六亞甲基二醇（p〇lyhexamethyiene giyc〇1)等。該等既可單獨使用’亦可併用兩種以上。作為上述結晶性芳香族聚酯樹脂，更具體而言’例如可列舉·聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚 17 201144072 于本一甲酸已二酯（P〇lyhexamethylene terephthalate)、聚萘二曱酸乙二酯、聚萘二甲酸丁二酯、對苯二甲酸丁二醇-聚四亞甲基二醇共聚物、對苯二甲酸丁二醇_聚己内酯共聚物等。該等既可單獨使用，亦可併用兩種以上。其中，就所獲知之離型膜之非污染性及結晶性特別優異而言，較佳為聚對苯二甲酸丁二酯。上述結晶性芳香族聚酯樹脂之使用示差掃描熱析儀所測定之熔點較佳為200。(：以上。通常，熱壓成形係於未達200。匚下進行，因此藉由使用此種炼點較高之樹脂，所獲得之離型膜於熱麗成形時亦不會炼融而可具有離型性，從而使熱壓成形時之破壞得到抑制。再者，作為示差掃描熱析儀，例如可列舉DSC 2920( TA Instruments公司製造）等。 . 若上述結晶性芳香旗聚酉旨樹脂之使用示差掃描献析偉所測定之㈣未達2(m：，則存在所獲得之離型膜之耐熱姓下降’於熱壓成形時熔融之情形。上述結晶性芳香族聚酷樹脂之使用示差掃描熱析儀所測定之熔點更佳為2⑽以 I» η 便用上述示差掃描熱析儀所測定 ,，丨〜〜w邮啊 ζυυ匕以上之…曰性芳香族聚醋樹脂並無特別限定，例如可列舉對本甲馱乙一 SB、聚對苯二甲酸丁二酯、聚對苯二甲酸己二酷1萘二甲酸乙二顆、聚萘二甲酸丁二酯、對苯二甲酸丁二醇.聚四亞甲基二醇共聚物等。料既可單獨使用亦可併用兩種以上。該等之中，就所獲得之離型膜非 18 201144072 π染性及結晶性優異而言，較佳為聚對苯二甲醆丁一酽上述表層可含有穩定劑。上述穩定劑並無特別例如可列舉受阻酚系抗氧化劑、熱穩定劑等。上述受阻紛系抗氧化劑並無特別限定，例如三甲基_2,4,6-三(3,5-二-第三丁基-4,基节· 3鄉[3-(3-第三丁基·4一曱苯基…^ —甲基乙基}-2,4,8，1〇-四氧雜螺[5,5]十一烷等。土，上述熱穩定劑並無拉拓丨ftp 6 , (2 4-二帛- TAi其疋’例如可列舉：亞碟酸三，--第二丁基本基)酯、亞磷酸第—丁基，_(3-第三丁基_4，基苯基)_對異基苯基）S旨、3 3， r* Zb 、土雙（對壬本土)西曰3,3 代二丙酸雙十四烷酉旨、3 3，酸二硬脂基酯、新戊四醇瓜代一丙丄 _(3十—烧基硫代丙酸@旨）、3,3，砸代一丙酸雙十三烷酯等。 ’ 又，上述表層亦可於無損本纖維、無機填充劑、阻燃劑、紫J之效果之範圍内含有、系外線吸收劑、越 + …、機物、高級脂肪酸鹽等添加劑。几蜊、上述纖維即可為無機纖維， m m ik ^ ^ I 了為有機纖維。上μ & 機義維並無特別限定，例如可列舉玻上4無硼纖維、碳化石夕纖維、氧化紹纖維、非晶纖维.石石反纖維、纖維等。上述有機纖維並無特別，曰y、.、石夕-欽-碳系醯胺纖維等。 ’例如可列舉芳族聚上述無機填充劑並無特別限氧化鈦、雲母、滑石等。，例如可列舉··碳酸鈣、上述阻燃劑並無特別限疋例如可列舉··六漠環十二 19 201144072 炫、填酸三·(2,3·二氣丙基㈣ '五演笨基烯丙基上述紫外線吸收劑並無特別限定， ^ - -r ^ . 叱例如可列舉··水楊西文對第二丁基本基酯、2-經基_4-甲氧甚m w ^ w 礼丞—本甲鲖、2-羥基-4- 甲氧基-2 -羧基二苯甲酮、24<; _ ^ c . ’ I三羥基苯丁酮 (2,4,5-trihydroxybutyrophenone)等。上述抗靜電劑並無特別限定，例如 Ί j如可列舉：N，N-雙（羥基乙基）烧基胺、烧基稀丙基續酸鹽现烷基磺酸鹽等。上述無機物並無特別限定，例如 J夕】舉.硫酸鋇、氧化鋁、氧化矽等。 ’例如可列舉：硬脂質改質而含有熱塑性上述高級脂肪酸鹽並無特別限定酸鈉、硬脂酸鋇、棕櫚酸鈉等。上述表層係可為了使該表層之性樹脂及橡膠成分。例如可列舉：聚烯烴、聚醯胺、聚碳酸酯' 上述熱塑性樹脂並無特別限定改質聚烯烴、聚笨乙烯、聚氣乙烯聚礙、聚S旨等。上述橡膠成分並無特別限定，例如可列舉：天然橡膠、苯乙稀-丁二稀共聚物'聚丁二稀、$異戊二烯、丙稀猜_ 丁二烯共聚物、乙稀-丙稀共聚物（EPM( Ethylene -propylene polymer ，乙烯-丙稀共聚物； (Ethylene_propylene_diene _〇咖，三元乙丙橡膠）、聚氣平（P〇lyCh1〇r〇prene)' 丁基橡膠、丙烯酸橡膠、矽橡膠、胺酯橡膠、烯烴系熱塑性彈性體、笨乙㈣熱塑性彈性體、氣乙稀系熱塑性彈性體、S旨系熱塑性彈性體、醯胺系熱塑 201144072 性彈性體等。 -—^ Ίυ m 0 藉由含有上述縱橫比大之1秘之…、機化合物，所獲得之離型膜於南溫下之離型性坦古離U生提同’進而可抑制離型膜所含劑、低分子量物等向離型膜表面、' t ^ m 從而使熱壓成形時之潔淨性提高。 v崎上述縱橫比大之無機化合物並無特別限定，例如舉：點土等層狀石夕酸鹽、水滑石等層狀複合水合物等。上述表層之結晶度較佳為25%以下。若上述結晶度超過25%’則存在所獲得之離型膜之追隨性下降之情形。上述表層之結晶度更佳為2〇〜23 %。 ’係指根據藉由X射分之波峰強度比所求再者，本說明書中，所謂結晶度線繞射法所得之結晶部分與非結晶部出之值。為了進一性、離型性，實施熱處理。步提高所獲得之離型膜之耐熱性、尺寸穩定可於無損本發明之效果之範圍内對上述表層上述熱處理之方法並無特別限定，較佳為例如使膜於加熱至一定之溫度之輥之間通過的方法、#由加熱器對膜進行加熱之方法等。、又上述熱處理之溫度只要在上述聚酯系樹脂等上述表層所含之樹脂之玻璃轉移溫度以上且為熔點以下，則並無特別限定’較佳之下限為12〇〇c，較佳之上限為2〇〇它。若上述熱處理之溫度未達12(rc，則存在基本無法獲得利用 21 201144072 熱處理之。離型性之提高效果的情形。若上述熱處理之溫度超過2GGC，則存在於熱處理時上述表層變得易於變形而無法製造離型膜之情形。上述熱處理之溫度之更佳之下限為 1 70 C ’更佳之上限為19〇〇c。上述表層之厚度並無特別限定，但較佳之下限為$々 m’較佳之上限為2〇若上述表層之厚度未達5 “爪，則存在上述表層之強度受損，於錢成形時或離型膜離時破裂之情形。若上述表層之厚度超過2() ”，則存在所獲得之離型膜之柔軟性下降，對於基板表面之追隨性下降’無法充分地抑制熱壓成形時之接著劑之流出的情形。上述表層之厚度之更佳之下限為1〇，更佳之上限為b // m。 ”、、本發月之離型膜只要具有上述表層，則既可為單層膜’亦可為2層以上之多層膜。於本發明之離型膜為多層膜之情形時，可具有中間層。上述中間層較佳為含有使用示差掃描熱析儀所測定之熔點為6G°C以上且未達13()<t之聚烯烴系樹脂。藉由使用上述聚烯烴系樹脂’所獲得之中間層於覆蓋膜之接著劑開始溶融之溫度附近開始軟化，因此，具有此種中間層之離型膜對於基板表面之追隨性優異，對^例如具有100 以下等之微細之銅電路間距之可繞性印刷基板亦具有充分之追隨性，並可抑制接著劑之流出。右上述聚烯烴系樹脂之使用示差掃描熱析儀所測定之炫點未達机，則於離型膜之保管中、在環境溫度達到5〇 22 201144072 〜60°C之情形時’有時上述中間層樹脂會熔融並滲出，從而引起阻塞。若上述聚烯烴系樹脂之使用示差掃描熱析儀所測定之熔點為130X：以上，則存在所獲得之離型膜對於基板表面之追隨性下降之情形。上述聚烯烴系樹脂之使用示差掃描熱析儀所測定之熔點更佳為65°C以上、100〇C以下。作為上述聚烯烴系樹脂，具體而言，例如可列舉：聚乙烯、低密度聚乙烯、直鏈狀低密度聚乙烯、聚丙烯、乙烯-甲基丙烯酸曱酯共聚物、乙烯_乙酸乙烯酯共聚物、乙烯 -丙烯酸乙酯共聚物、乙烯·丙烯酸共聚物等。該等既可單獨使用，亦可併用兩種以上。其中，較佳為低密度聚乙烯、直鏈狀低密度聚乙烯、乙烯_甲基丙烯酸甲酯共聚物、乙烯_ 乙酸乙烯酯共聚物。上述中間層較佳為進而含有使用示差掃描熱析儀所測疋之溶點為13 0 °C以上之樹脂。A preferred lower limit of the elastic modulus of the above fabric is A ϋ·1 Mpa, preferably an upper limit of 4.0 MPa. If the elastic modulus of the above fabric is less than 〇1%, there is a decrease in the release property of the release film obtained. When the 201144072 elastic modulus of the above-mentioned fabric exceeds 4.0 Mpa, wrinkles, scratches, and the like are generated on the release film, and the followability to the surface of the substrate is lowered, and the flow of the adhesive at the time of hot press forming cannot be sufficiently suppressed. The situation. The lower limit of the elastic modulus of the above fabric is 〇.7Mpa, and the upper limit is more preferably 3 9Mpa. Further, in the present specification, the elastic modulus of the woven fabric refers to the hardness of the woven fabric determined by the method based on J1S-K-7127. A preferred lower limit of the tensile strength of the above fabric is 1.5 N/l 〇 mm, and a preferred upper limit is 2.5 N/10 mm. If the tensile strength of the woven fabric is less than i 5 N/10 mm, the fibers are elongated and broken during the above-mentioned rubbing treatment, and the obtained fibers are adhered to the release film. When the tensile strength of the woven fabric exceeds 2.5 N/1 Gmm, damage to the obtained release film such as creases and scratches may occur, and the followability to the surface of the substrate may be lowered, and the adhesive at the time of press forming may not be sufficiently suppressed. The situation of outflow. The lower limit of the tensile strength of the above fabric is 1.6 N/1 〇, and the upper limit is preferably 2 3 _, and the upper limit is more preferably UN/lOmm. Further, in the present specification, the tensile strength of the woven fabric means that the tensile strength of the woven fabric obtained by the method based on JIS-K_7127/the friction treatment device for performing the rubbing treatment is not particularly limited. For example, a polishing processing apparatus (Model_Yamagau Machinery Co., Ltd.) etc. are mentioned. In the release film of the second invention of the present invention, the resin is applied. In the release film of the inventions of the first and third aspects of the present invention, the main layer is not particularly limited, but preferably contains a polyester resin. The following is a description of the contents of the release film of the second and third inventions of the present invention. In the present specification, the release film of the present invention is applied to any of the release films of the second, third and third inventions of the present invention. The polyester resin is not particularly limited. By using the above polyester-based resin, the obtained release film can exhibit excellent mechanical properties, and in particular, it can exhibit excellent mechanical properties in a temperature range of about about 70 °C. Moreover, by using the above-mentioned polyester-based resin, it is economically advantageous to reduce the ring when the obtained release film is incinerated, and since the polyester resin has a small amount of low molecular weight components, The release film obtained is excellent in non-contaminating property, and it is also possible to suppress problems such as poor electrode coating of the flexible printed circuit board due to bleed out of the sub-component with low heat pressure. The above-mentioned polyester resin is preferably, for example, a crystalline aromatic aromatic scented scented resin, and is not particularly limited, and for example, a bismuth or a vinegar-forming derivative and a low molecular weight aliphatic- The crystalline aromatic polyester resin obtained by the reaction of %. The crystalline aromatic polyacetal resin may be exemplified by a tarenic acid or a vinegar-forming derivative thereof and a low molecular weight aliphatic diol, which is also a "+" polydisperse resin. (called "the lipid raft with a polyether skeleton in the main chain"., ν Ώ a Japanese-style fragrant polyester tree, and the amount of the aromatic dicarboxylic acid or its ester 胩V from the note The crystallized caprolactone obtained by the reaction between Hebi and the low-density ruthenium diol is placed in the body. After the polyester resin is dissolved in the body, the vinegar is opened in the open body. The obtained crystalline aromatic 201144072 polyester resin (hereinafter also referred to as "crystalline aromatic polyester resin") is obtained. The aryl=male derivative obtained by the reaction of the low molecular weight aliphatic diol having a polycaprolactone skeleton in the main chain is excellent in the release property of the obtained fragrant aromatic vinegar resin as compared with the case. Therefore, it is preferred that the main chain has a heat: a flexible and aromatic polyester resin, and a crystalline group of polyacetate resins having a di-A ether skeleton in the main chain. The crystalline aromatic condensate of the poly(()) skeleton in the chain is used as the above-mentioned scented dicarboxylic acid or sulphate I. - fly /, known derivative, for example, can be used. For the dimethyl, isophthalic acid # p-phenylene Carboxylic acid (paranh, _ben-methylhydrazine, naphthalene dicarboxylic acid, paraphenylene dicarb〇xylic acid, material 22:m-phenylene: dimethyl carboxylic acid, phthalic acid..., Cai Di can be a pair of Ben-carboxy Dimethyl acrylate, etc. These may be used alone or in combination of two or more. Examples of the low molecular weight aliphatic diol include ethylene glycol, an ancient 'propanol, 1,3-propanediol, and 13 - butyl triol, 1,4-butanediol, neopentyl, pentaerythritol 1,6-hexanol, 1,4-cyclohexyl dimethanol, etc. These may be used alone or in combination Examples of the above-mentioned south molecular weight diols include, for example, polyethylene glycol, polytetramethylene glycol, polyhexamethylene glycol (p〇lyhexamethyiene giyc〇1), and the like. These may be used alone or in combination of two or more. As the above crystalline aromatic polyester resin, more specifically ' For example, polyethylene terephthalate, polybutylene terephthalate, poly 17 201144072 in P〇lyhexamethylene terephthalate, polyethylene naphthalate, polynaphthalene Butylene dicarboxylate, butylene glycol terephthalate-polytetramethylene glycol copolymer, butylene terephthalate-polycaprolactone copolymer, etc. These may be used alone or in combination. Two or more of them. Among them, polybutylene terephthalate is preferred in terms of the non-contaminating property and crystallinity of the release film which is known. The use of the above-mentioned crystalline aromatic polyester resin for differential scanning heat The melting point measured by the analyzer is preferably 200. (: Above. Usually, the hot press forming is carried out at a temperature of less than 200. Therefore, by using a resin having a higher refining point, the release film obtained is obtained. In the case of hot-rolling, the mold is not smelted, and the release property can be suppressed, and the damage during hot press forming can be suppressed. Further, as the differential scanning calorimeter, for example, DSC 2920 (manufactured by TA Instruments Co., Ltd.) or the like can be mentioned. If the above crystalline aromatic flag is used, the resin is used. The differential scanning is determined by the analysis of the (4) less than 2 (m: there is a decrease in the heat-resistant surname of the obtained release film), which is melted during hot press forming. The differential scanning of the above crystalline aromatic poly-resin is used. The melting point measured by the pyrolyzer is preferably 2 (10) and I» η is measured by the above-mentioned differential scanning calorimeter, and 丨~~w mail ζυυ匕 ζυυ匕曰曰曰曰曰曰曰曰曰曰曰曰曰曰曰曰曰曰曰芳香族芳香族芳香族芳香族芳香族芳香族芳香族芳香族芳香族For example, it can be exemplified by the above-mentioned acetaminophen SB, polybutylene terephthalate, polyethylene terephthalate 1 naphthalene dicarboxylate, polybutylene naphthalate, butylene terephthalate. Polytetramethylene glycol copolymer and the like. The materials may be used singly or in combination of two or more. Among these, it is preferable that the release film obtained is excellent in π dyeing property and crystallinity. Preferably, the surface layer may contain a stabilizer. The stabilizer is not particularly limited, and examples thereof include hindered phenol-based antioxidants and heat stabilizers. The above-mentioned hindered antioxidants are not particularly limited, for example, trimethyl-2,4,6-tris(3,5-di-t-butyl-4, keel·3 township [3-(3-third) Butyl 4-ylphenyl...^-methylethyl}-2,4,8,1〇-tetraoxaspiro[5,5]undecane, etc. Soil, the above heat stabilizer is not extended丨 ftp 6 , (2 4-diindole - TAi 疋 ', for example, triphenyl acid tri-, -butylidene) ester, butyl phosphite, _ (3-tert-butyl _ 4, phenyl))-p-isophenyl)S, 3 3, r* Zb, bis (p. bismuth), oxime, 3,3 dipropane ditetradecane, 3 3, acid Distearyl ester, neopentyl alcohol, guaia-propyl hydrazine _ (3 - thiol thiopropionic acid @), 3, 3, deuterated propionic acid ditridecyl ester, etc. The surface layer may also contain, in addition to the effect of the fiber, the inorganic filler, the flame retardant, and the purple J, an external absorbent, an additive, an organic matter, a higher fatty acid salt, and the like. For the inorganic fiber, mm ik ^ ^ I is an organic fiber. The upper μ & machine-dimensional dimension is not particularly limited, for example, 4 on the glass without boron Fiber, carbonized stone, oxidized fiber, amorphous fiber, stone anti-fiber, fiber, etc. The above organic fiber is not particularly, 曰y, ., Shixi-Chin-carbon amide fiber, etc. The above-mentioned inorganic filler is not particularly limited to titanium oxide, mica, talc, etc., and examples thereof include calcium carbonate, and the flame retardant is not particularly limited, and for example, six desert rings twelve 19 201144072 Hyun, acid-filled three · (2,3 · di-propyl propyl (four) 'Five-exemplified isopropyl allylate The above ultraviolet absorber is not particularly limited, ^ - -r ^ . 叱 For example, ··········································· Dibutyl-based ester, 2-amino- 4-methoxyx, mw^w 本-benzyl, 2-hydroxy-4-methoxy-2-carboxybenzophenone, 24<; _ ^ c 'I, 3-hydroxybutanone (2,4,5-trihydroxybutyrophenone), etc. The above antistatic agent is not particularly limited, and for example, Ί j may, for example, be N,N-bis(hydroxyethyl)alkylamine, or burned. The base propyl propyl salt is an alkyl sulfonate, etc. The above inorganic substance is not particularly limited, and for example, samarium sulfate, aluminum oxide, cerium oxide, etc. The above-mentioned surface layer can be made into a resin and a rubber component of the surface layer, and the above-mentioned surface layer can be exemplified by the above-mentioned surface layer. Polyolefin, Polyamide, and Polycarbonate The thermoplastic resin is not particularly limited to modified polyolefin, polystyrene, polystyrene, or poly. The rubber component is not particularly limited, and examples thereof include, for example, Natural rubber, styrene-butadiene dilute copolymer 'polybutylene dilute, $ isoprene, propylene guess _ butadiene copolymer, ethylene-propylene polymer (EPM (Ethylene-propylene polymer, ethylene) -acrylic copolymer; (Ethylene_propylene_diene _ 〇 coffee, EPDM rubber), polygasping (P〇lyCh1〇r〇prene)' butyl rubber, acrylic rubber, ruthenium rubber, urethane rubber, olefin thermoplastic elastomer Body, stupid B (tetra) thermoplastic elastomer, ethylene-based thermoplastic elastomer, S-based thermoplastic elastomer, amide-based thermoplastic 201144072 elastomer, and the like. -—^ Ίυ m 0 By containing the above-mentioned aspect ratio of the 1st, the compound, the release film obtained at the south temperature, the release type of the tango is separated from the U and can further inhibit the release film. The content of the agent, the low molecular weight substance, and the like on the surface of the release film and 't ^ m improve the cleanliness during hot press forming. The above-mentioned inorganic compound having a large aspect ratio is not particularly limited, and examples thereof include layered composite hydrates such as layered oxalates such as point clay and hydrotalcites. The crystallinity of the above surface layer is preferably 25% or less. If the above crystallinity exceeds 25%', the followability of the obtained release film may be lowered. The crystallinity of the above surface layer is more preferably 2 〇 to 23%. The term "the intensity ratio of the peaks by the X-rays" is the value of the crystal portion and the amorphous portion obtained by the crystallinity diffraction method in the present specification. For the purpose of removability and release, heat treatment is carried out. The method of improving the heat resistance and dimensional stability of the release film obtained by the step can be carried out without departing from the effects of the present invention. The method for the heat treatment of the surface layer is not particularly limited, and it is preferably, for example, a roll which is heated to a certain temperature. A method of passing between, a method of heating a film by a heater, and the like. Further, the temperature of the heat treatment is not particularly limited as long as it is equal to or higher than the glass transition temperature of the resin contained in the surface layer such as the polyester resin, and the lower limit is preferably 12 〇〇c, and the upper limit is preferably 2 Look at it. If the temperature of the heat treatment is less than 12 (rc), there is a case where the effect of improving the release property by heat treatment of 21 201144072 is substantially impossible. If the temperature of the heat treatment exceeds 2 GGC, the surface layer is easily deformed during heat treatment. In the case where the release film cannot be produced, the lower limit of the temperature of the heat treatment is preferably 1 70 C', and the upper limit is 19 〇〇c. The thickness of the surface layer is not particularly limited, but the preferred lower limit is $々m'. The upper limit of the surface is 2 〇 If the thickness of the surface layer is less than 5 "claws, the strength of the surface layer is impaired, and the film is broken at the time of forming or leaving the film. If the thickness of the surface layer exceeds 2 ()", Further, the flexibility of the release film obtained is lowered, and the followability to the surface of the substrate is lowered. The case where the flow of the adhesive at the time of hot press forming cannot be sufficiently suppressed. The lower limit of the thickness of the surface layer is preferably 1 Torr. The upper limit of the film is b // m. The release film of the present invention may be a single layer film or a multilayer film of two or more layers as long as it has the above surface layer. When the film is a multilayer film, it may have an intermediate layer. The intermediate layer preferably contains a polyolefin resin having a melting point of 6 G ° C or more and less than 13 () < t as measured by a differential scanning calorimeter. The intermediate layer obtained by using the above polyolefin-based resin starts to soften at a temperature at which the adhesive of the cover film starts to melt, and therefore, the release film having such an intermediate layer is excellent in followability to the surface of the substrate, and For example, a flexible printed circuit board having a fine copper circuit pitch of 100 or less has sufficient followability and can suppress the outflow of the adhesive. The above-mentioned polyolefin-based resin is used as a bright spot measured by a differential scanning pyrolyzer. When the machine is not reached, in the storage of the release film, when the ambient temperature reaches 5〇22 201144072 to 60 °C, 'the above intermediate layer resin may melt and ooze out, causing clogging. If the above polyolefin resin When the melting point measured by the differential scanning calorimeter is 130X: or more, there is a case where the obtained release film has a decreased followability to the surface of the substrate. The melting point measured by the differential scanning calorimeter is preferably 65° C. or more and 100° C. or less. Specific examples of the polyolefin-based resin include polyethylene, low-density polyethylene, and linear low density. Polyethylene, polypropylene, ethylene-methyl methacrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene/acrylic acid copolymer, etc. These may be used alone or in combination. More preferably, it is low density polyethylene, linear low density polyethylene, ethylene methyl methacrylate copolymer, ethylene vinyl acetate copolymer. The intermediate layer preferably further comprises using differential scanning The melting point of the crucible measured by the pyrolyzer is a resin of 130 ° C or higher.

之樹脂的滲出。使用上述示差掃描熱析儀所測定之之樹脂並無特別限定，例如可列舉：聚丙烯、之溶點為13 〇以上結晶性芳香 23 201144072 族聚酯樹脂等。於上述中間層含有使用上述示差掃描熱析儀所測定之溶點為1 30°C以上之樹脂之情形時，此種樹脂之調配量並無特別限定，但於中間層中之較佳之下限為5重量％，較佳之上限為50重量❶/◦。若使用上述示差掃描熱析儀所測定之熔點為130t以上之樹脂之調配量未達5重量％，則存在無法充分地獲得抑制於熱壓成形時在離型膜之端部所產生之自上述中間層之樹脂之滲出之效果的情形。若使用上述示差掃描熱析儀所測定之熔點為13〇t以上之樹脂之調配量超過50重量％，則存在所獲得之離型膜對於基板表面之追隨性下降之情形。上述中間層可與上述表層同樣地含有纖維、無機填劑、阻燃劑、紫外線吸收劑、抗靜電劑、無機物、高級肪酸鹽等添加劑。上述中間層之厚度並無特別限定，但較佳之下限為 "m ’較佳之上限& 2〇〇 # m。若上述中間層之厚度未』The bleed out of the resin. The resin to be measured by the above-described differential scanning calorimeter is not particularly limited, and examples thereof include polypropylene, a melting point of 13 Å or more, and a crystalline aromatic granule 23 201144072-group polyester resin. When the intermediate layer contains a resin having a melting point of 130 ° C or higher as measured by the above-described differential scanning calorimeter, the amount of the resin is not particularly limited, but a preferred lower limit in the intermediate layer is The 5% by weight, preferably the upper limit is 50% by weight. When the blending amount of the resin having a melting point of 130 t or more as measured by the above-described differential scanning calorimeter is less than 5% by weight, the above-described occurrence at the end portion of the release film during hot press forming may not be sufficiently obtained. The effect of the effect of the resin oozing out of the intermediate layer. When the blending amount of the resin having a melting point of 13 Torr or more as measured by the above-described differential scanning calorimeter is more than 50% by weight, there is a case where the followability of the obtained release film to the surface of the substrate is lowered. The intermediate layer may contain an additive such as a fiber, an inorganic filler, a flame retardant, an ultraviolet absorber, an antistatic agent, an inorganic substance or a higher fatty acid salt in the same manner as the above surface layer. The thickness of the intermediate layer is not particularly limited, but a preferred lower limit is a preferred upper limit & 2 〇〇 # m. If the thickness of the above intermediate layer is not

iVT，則存在如下情形：若上述中間層過薄，於熱I 巧中間層軟化，則局部性地產生不存在中間層之部位 2無法將加壓壓力均勾地負荷於基板上。若上述中旧需旱200 ，則存在因上述中間層之厚度超“ 以抑㈣壓成形時於膜端部所產生之自上述中深 =樹脂之渗出的情形。上述，間層之厚度之更佳之下阳為2〇以01，更佳之上限為100 "m。本發明之離型膜之於1赃以3MPa之負荷加壓6〇分 24 201144072 鐘時的尺寸變化率較佳為i.5%以下。若上述尺寸變化率超過1.5%，則存在於熱壓成形時損壞可撓性印刷基板之電路圖案之情形。上述尺寸變化率更佳為1〇%以下。又，本發明之離型膜較佳為離型膜之寬度方向（以下稱為TD)與長度方向（以下稱為MD)之尺寸變化率為相同方向且為同等程度。於如一者（例如MD)收縮，另一者 (例如TD )伸長般縱橫之尺寸變化不同之情形時，存在因離型膜而於熱壓成形時損壞可撓性印刷基板之電路圖案之情形。本發明之離型膜之用途並無特別限定，例如，本發明之離型膜較佳為用於如下之用途：當經由預浸體或耐熱膜而將覆銅積層或銅錢壓成形於基板上，^製造印刷配線基板、可撓性印刷基板或多層印刷配線板時，防止熱壓板與所獲得之印刷配線基板、可撓性印刷基板或多層印' 刷配線板之接著。又，本發明之離型膜用於如下之用途亦較佳：當利用熱壓成形並經由熱硬化性接著劑而將覆蓋膜接著於^成有銅電路之基板上’ &而製造可撓性印刷基板時，防止熱壓板與上述覆蓋膜之接著、或上述覆蓋膜彼此之接著。進而，本發明之離型膜用於如下之用途亦較佳：當利用熱壓成形來製造半導體用模具(m〇ld)時，防止成形金：模具與模具樹脂（mold resin)之接著。製造本發明之離型膜之方法並無特別限定’但較佳為於製造具有上述表層之膜後、對上述表層進行如上所述之 25 201144072 摩擦處理等表面處理之方法，更具體而下之方法，該方法 °交佳為例如以面進行摩擦處理之步驟，上述摩擦處理材c之表強度為1.0〜5.0 g/d之纖維構成之織物，=In the case of iVT, if the intermediate layer is too thin and softens in the middle layer of the heat I, the portion where the intermediate layer is not present locally is generated. 2 The pressing pressure cannot be uniformly loaded on the substrate. If the above-mentioned medium and old droughts are 200, there is a case where the thickness of the intermediate layer exceeds the above-mentioned medium depth = resin bleed at the end portion of the film during press forming (four). The thickness of the interlayer is as described above. More preferably, the anode is 2 inches to 01, and the upper limit is 100 "m. The release film of the present invention is pressurized at a load of 3 MPa at a load of 3 MPa at a pressure of 3 MPa. The dimensional change rate at the time of 2011,440,72 is preferably i. When the dimensional change rate exceeds 1.5%, the circuit pattern of the flexible printed circuit board may be damaged during hot press forming. The dimensional change rate is preferably 1% or less. The release film preferably has a dimensional change rate in the width direction (hereinafter referred to as TD) and a length direction (hereinafter referred to as MD) of the release film in the same direction and is equivalent. In the case of one (for example, MD) shrinkage, the other When the dimensional change of the longitudinal and lateral directions is different (for example, TD), there is a case where the circuit pattern of the flexible printed circuit board is damaged during hot press forming due to the release film. The use of the release film of the present invention is not particularly limited. For example, the release film of the present invention is preferably used Use for the following: when a copper-clad laminate or a copper-clad laminate is formed on a substrate via a prepreg or a heat-resistant film, when a printed wiring substrate, a flexible printed substrate, or a multilayer printed wiring board is manufactured, the hot-pressed sheet is prevented from being obtained The printed wiring board, the flexible printed circuit board, or the multilayer printed wiring board is also used. Further, the release film of the present invention is preferably used for the following applications: by hot press forming and via a thermosetting adhesive. When the flexible printed circuit board is manufactured on the substrate on which the copper circuit is formed, the cover film is prevented from adhering to the cover film or the cover film is adhered to each other. Further, the present invention is separated from It is also preferred that the film is used for the following applications: when a mold for a semiconductor is produced by hot press forming, the forming gold is prevented from being bonded to a mold resin. The release film of the present invention is produced. The method is not particularly limited, but it is preferably a method of performing surface treatment such as the above-mentioned surface treatment of 25 201144072 after the film having the above surface layer, more specifically, The method is preferably a step of performing a rubbing treatment on the surface, for example, a fabric composed of fibers having a strength of 1.0 to 5.0 g/d as the friction-treated material c, =

^、（）所表示之作功能量En(KJ)成為50〜s 之方式進行上述摩擦處理。 00 KJ 本發明之離型膜之製膜方法並無特舉：利用水冷式哎* 疋例如可列 7式次二冷式共擠壓膨脹法、共擠壓τ 膜之方法；於製作卜、f志s α 模法製製作上述表層後，利用擠壓疊層法將積層於該表層上之方法；對Α 間層云對為上述表層之膜與成為之膜進行乾式疊層之方法 a 削兜埼忐，熱壓成形法等。八中’於本發明之離型膜為多層膜之情形時，就各層之厚度控制優異而言，較佳為藉由共擠壓τ模法製膜之方法。於上述溶劑濟铸法中，例如於成為中間層之膜上對辦黏層進行底塗處理後，在該增黏層上㈣將例如上述㈣系樹脂等溶解於溶劑中而成之成為表層之樹脂組成物，缺後對塗膜均勻地加熱並乾燥，從而形成表層。又，於上述熱壓成形》去巾，例如將成為上述表層之膜與成為中間層之膜重疊並熱壓成形。根據本發明，可提供-種離型性優異且對於基板表面之追隨性優異、可抑制熱壓成形時之接著劑之流出的離型膜。【實施方式】以下，揭示實施例來更詳細地說明本發明之形態，但 26 201144072 本發明並不僅限定於該等實施例。再者，於以下之實施例及比較例中’用作摩擦處理材料之表面之素材之東麗公司製造的「Toraysee」及帝人纖維 (Teijin Fibers)公司製造的「Tetoron」係 PET。 (實施例1 ) 將作為表層用之結晶性芳香族聚酯樹脂之聚對苯二曱酸丁二酯（NOVADURAN5010R5，三菱工程塑料（Mitsubishi Engineering-Plastics)公司製造，熔點為224°C )，以及作為中間層用之聚烯烴系樹脂之直鏈狀低密度聚乙稀 (EXCELLEN FX ( CX5501 )，住友化學公司製造，熔點為 66C)、乙稀-曱基丙稀酸曱酯共聚物（ACRYFT ( WH401 )，住友化學公司製造’熔點為86°C)、及聚丙稀（ρ§2〇7Α，The above-described rubbing treatment is performed in such a manner that the function amount En (KJ) indicated by ^ and () becomes 50 s. 00 KJ The film forming method of the release film of the present invention is not specifically described: a water-cooled 哎* 疋, for example, a 7-second secondary co-extrusion expansion method or a method of co-extruding a τ film; After the above-mentioned surface layer is produced by the f-s s α method, the method of laminating the surface layer by the extrusion lamination method is performed; and the method for the dry lamination of the film of the surface layer and the film formed by the inter-layer cloud is performed.埼忐, hot press forming, etc. In the case where the release film of the present invention is a multilayer film, in terms of excellent thickness control of each layer, a method of forming a film by a co-extrusion τ mode is preferred. In the solvent casting method, for example, after the undercoating treatment is performed on the film which is the intermediate layer, the (4) resin or the like is dissolved in the solvent on the adhesion promoting layer (4) to form a surface layer. The resin composition is uniformly heated and dried on the coating film to form a surface layer. Further, in the above-described hot press forming, the film which is the surface layer is superposed on the film which becomes the intermediate layer, and is hot-pressed. According to the present invention, it is possible to provide a release film which is excellent in release property and excellent in followability to the surface of the substrate and which can suppress the outflow of the adhesive during hot press forming. [Embodiment] Hereinafter, embodiments of the present invention will be described in more detail with reference to the embodiments. However, the invention is not limited to the embodiments. Further, in the following examples and comparative examples, "Toraysee" manufactured by Toray Industries, Inc., which is used as a material for the surface of the friction-treated material, and "Tetoron"-based PET manufactured by Teijin Fibers Co., Ltd. (Example 1) Polybutylene terephthalate (NOVADURAN 5010R5, manufactured by Mitsubishi Engineering-Plastics Co., Ltd., melting point: 224 ° C) as a crystalline aromatic polyester resin for a surface layer, and Linear low-density polyethylene (EXCELLEN FX (CX5501), manufactured by Sumitomo Chemical Co., Ltd., melting point 66C), a polyolefin-based resin for the intermediate layer, and ethylene-mercapto acrylate copolymer (ACRYFT ( WH401), Sumitomo Chemical Co., Ltd. manufactures 'melting point of 86 ° C), and polypropylene (ρ§2〇7Α,

SunAUomer公司製造，熔點為i60t )投入至共擠壓成形機中，藉由τ模進行共擠壓成形，從而獲得表層之厚度為ι〇 m、中間層之厚度為80 μ m之膜。再者，熔點係使用示差知描熱析儀（DSC 292G ’ TA Instmments公司製造）進行測利用使用將由表i所示之纖維構成之織物作為表材之摩擦處理材料之摩擦處理裝置（研磨處理裝置％ YWM，山縣機械公司製造），以成為表 ^ 能量⑷）之方式對所獲得的膜之表層 ::作功理，從而獲得離型臈。進仃摩擦處棺田將厚擦處理裝置之面積Μ10、用以進行摩擦處理之每單位^ Μ "理平位時間之作功量 27 201144072 )又到摩擦處理之膜之寬度W ( m)及受到摩擰處理，膜之線速LS(m/min)應用於式⑸而算出。右針對所獲得之離型冑’藉由穿透型冑子顯微鏡 TEM)(型號Η·95〇〇，曰立先端科技公司製造）對使用滑式切片機（型號SM2〇〇〇R，池田理化公司製造）於厚度方向上進行切割所得之剖面進行觀察，則僅於自表層之：面起至表1所不之厚度（nm)為止之區域内觀察到離型處理層。將於實施例丨中藉由穿透型電子顯微鏡所觀察到之圖像示於圖4。又，根據藉由χ射線繞射法所得之結晶部分與非結晶部分之波峰強度比而算出表層之結晶度⑻。 (實施例2〜5 ) 除將摩擦處理材料之表面之素材與作功能量（kj)如表1所示般變更以外，以與實施例"目同之方式獲得離型膜。若針對所獲得之離型膜，藉由穿透型電子顯微鏡 (TEM )(型號h-9500 ’日立先端科技公司製造）對使用滑動式切片機（型號SM2〇〇〇r ,池田理化公司製造）於厚度方向進行切割所得之剖面進行觀察，則僅於自表層之表面起至表1所示之厚度（nm)為止之區域内觀察到離型處理層將於實施例2中藉由穿透型電子顯微鏡所觀察到之圖像示於圖5’將於實施例3中藉由穿透型電子顯微鏡所觀察到之圖像示於圖6，將於實施例5中藉由穿透型電子顯微鏡所觀察到之圖像示於圖7。又，以與實施例i相同之方式算出表層之結晶度（％)。 28 201144072 (比較例1 ) 除未進行摩擦處理以外，以與實得離型膜。仲HI万式獲 :針對所獲得之離型膜，藉由穿透式電子 ^ M)(型號H-9500,曰立先端科技公司製造）對使用巩 =十二片機（型號_嫩’池田理化公司製造）於厚二理層。：::：割所得之剖面進行觀察，則未觀察到離心又，… 型電子顯微鏡所觀察到之圖像示於圖8。 /、實施例1相同之方式算出表層之結晶度（％)。 (比較例2〜3 ) :將摩擦處理材料之表面之素材與作功能量⑴）如衣z所不般變更以外，以輿眚膜。卜興貫施例1相同之方式獲得離型 I針對所獲得之離型腺，1 £ (TEM)(型號H_95〇先㈣型電子顯微鏡无知科技公司製造）對使用滑 :刀片機（型號则00R，池田理化公司製造）於厚户方向上進行切割所得之剖面進行觀察，則僅於自表層之: ::至表2所示之厚度（―為止之區域内觀察到 3):又，以與實施例1相同之方式算出表層之結晶度 (實施例6) &將作為表層用之結晶性芳香族聚醋樹脂之聚對苯二甲酸丁二自旨（N〇VADURA刪1GR5，三菱工程塑料公司製造，溶點為2抑），以及作為中間層用之㈣烴㈣脂之直鍵 29 201144072 狀低密度聚乙烯（EXCELLEN FX (CX55〇1)，住友化學公司製造，炼點為66t：)、乙烯-甲基丙烯酸甲醋共聚物 (ACRYFT ( WH401 )，住友化學公司製造，炼點為86。匸）及聚丙嫦（PS207A’ SunAllomei^司製造，熔點為16〇〇c ) 投入至共擠Μ成形機中，藉ώ T模進行共擠麼成形，從而獲得表層之厚度為1〇、中間層之厚度為8() 之膜。再者，熔點係使用示差掃描熱析儀（DSC 292〇，TA Instruments公司製造）進行測定。利用使用將由表3所示之纖維構成之織物作為表面素材之摩擦處理材料的摩擦處理裝置（研磨處理裝置，型號 YCM-150M，山縣機械公司製造），以成為表3所示之作功能量（KJ)之方式對所獲得的膜之表層之表面進行摩擦處理，從而獲得離型膜。再者，作功能量係藉由將摩擦處理裝置進行摩擦處理之面積Ar ( m2 )、用以進行摩擦處理之每單位時間之作功量 J(Kj/min)、受到摩擦處理之膜之寬度w(m)及受到摩擦處理之膜之線速LS (m/min)應用於式（5)而算出。對於自所獲得之離型膜之表層之表面起至厚度為丨" m為止之區域，使用薄膜評價用試樣水平型X射線繞射裝置（型唬Smart Lab，理學公司製造）進行χ射線分析，從而求出相對於面平行地配向之羰基之比例（％ )。The film manufactured by SunAUomer Co., Ltd., having a melting point of i60t) was put into a co-extrusion molding machine, and co-extruded by a τ-die to obtain a film having a surface layer of ι〇 m and an intermediate layer having a thickness of 80 μm. In addition, the melting point is a rubbing treatment apparatus (grinding processing apparatus using the friction processing material which uses the fabric which consists of the fiber of the table i as the friction material of the sheet|s % YWM, manufactured by Shanxian Machinery Co., Ltd., to obtain the release enthalpy of the surface layer of the obtained film in the form of the surface energy (4)).仃仃棺棺将将将将将将将将将将将厚厚厚厚厚厚厚厚厚厚厚厚厚厚厚厚厚厚厚厚厚厚厚厚厚厚厚厚厚厚厚厚厚厚厚厚厚厚厚The wire speed LS (m/min) of the film was applied to the formula (5) and was calculated. Right for the obtained release 胄 'by penetrating scorpion microscope TEM) (model Η·95〇〇, manufactured by 先立先端科技) for the use of slide slicer (model SM2〇〇〇R, Ikeda physics When the cross section obtained by cutting in the thickness direction was observed, the release treatment layer was observed only in the region from the surface layer to the thickness (nm) which is not shown in Table 1. An image observed by a transmission electron microscope in the examples will be shown in Fig. 4. Further, the crystallinity (8) of the surface layer was calculated from the peak intensity ratio of the crystal portion to the amorphous portion obtained by the x-ray diffraction method. (Examples 2 to 5) A release film was obtained in the same manner as in Example " except that the material of the surface of the rubbing treatment material and the functional amount (kj) were changed as shown in Table 1. For the release film obtained, a slide-type microtome (Model: h-9500 'Hitachi Advanced Technology Co., Ltd.) is used for the slide type microtome (model SM2〇〇〇r, manufactured by Ikeda Chemical Co., Ltd.). When the cross section obtained by cutting in the thickness direction was observed, it was observed that the release treatment layer was observed in the region from the surface of the surface layer to the thickness (nm) shown in Table 1 by the penetration type in Example 2. The image observed by the electron microscope is shown in Fig. 5'. The image observed by the transmission electron microscope in Example 3 is shown in Fig. 6, and in Example 5 by the transmission electron microscope. The observed image is shown in Figure 7. Further, the crystallinity (%) of the surface layer was calculated in the same manner as in Example i. 28 201144072 (Comparative Example 1) A release film was obtained in addition to the rubbing treatment. Zhong HI Wanxuan: For the obtained release film, by using the transmissive electronic ^ M) (model H-9500, manufactured by 先立先端科技), the use of Gong = 12-piece machine (Model_嫩' Ikeda Physicochemical company manufacturing) in the thick two layers. :::: Observed section of the cut, no centrifugation was observed, and the image observed by a type electron microscope is shown in Fig. 8. / The crystallinity (%) of the surface layer was calculated in the same manner as in Example 1. (Comparative Examples 2 to 3): The film of the surface of the rubbing treatment material and the functional amount (1) were changed as in the case of the clothes z. In the same way as in Example 1, Buxing I obtained the release I for the obtained release gland, 1 £ (TEM) (model H_95 〇 first (four) type electron microscope ignorance technology company) for the use of slip: blade machine (model 00R, Ikeda Observed by the physicochemical company) The profile obtained by cutting in the direction of the thick household is only observed from the surface layer: :: to the thickness shown in Table 2 (the 3 is observed in the area): again, with the example (1) The crystallinity of the surface layer was calculated in the same manner (Example 6) & A polytetramethylene terephthalate (N〇VADURA deleted 1GR5, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) as a crystalline aromatic polyester resin for the surface layer , melting point is 2), and as a middle layer (4) hydrocarbon (four) fat direct bond 29 201144072 low density polyethylene (EXCELLEN FX (CX55〇1), manufactured by Sumitomo Chemical Co., Ltd., refining point 66t:), ethylene -Methyl methacrylate copolymer (ACRYFT ( WH401 ), manufactured by Sumitomo Chemical Co., Ltd., with a melting point of 86. 匸) and polypropylene (PS207A' manufactured by SunAllomei Co., Ltd., melting point 16〇〇c) In the machine, by means of the T-mode for co-extrusion , Thereby obtaining a surface layer of a thickness of 1〇, the thickness of the intermediate layer 8 () of the film. Further, the melting point was measured using a differential scanning calorimeter (DSC 292, manufactured by TA Instruments). A friction treatment device (grinding treatment device, model YCM-150M, manufactured by Yamato Machinery Co., Ltd.) using a woven fabric composed of the fibers shown in Table 3 as a surface material was used as the functional amount shown in Table 3 ( The surface of the surface layer of the obtained film was subjected to a rubbing treatment in a manner of KJ) to obtain a release film. Further, the functional amount is the area Ar (m2) of the rubbing treatment by the rubbing treatment apparatus, the work amount J (Kj/min) per unit time for performing the rubbing treatment, and the width of the film subjected to the rubbing treatment. The line speed LS (m/min) of w(m) and the film subjected to the rubbing treatment was calculated by applying the formula (5). For the area from the surface of the surface layer of the obtained release film to the thickness of 丨" m, a horizontal X-ray diffraction apparatus (type Smart Lab, manufactured by Rigaku Corporation) for film evaluation is used for X-ray irradiation. Analysis was carried out to determine the ratio (%) of the carbonyl group aligned in parallel with respect to the plane.

再者’相對於面平行地配向之羰基的比例（％ )係藉由將利用X射線分析所獲得之相對於面平行地配向之羰基之波峰強度A、及相對於面垂直地配向之羰基之波峰強度B 30 201144072 應用於式π)而算來。又表層之結晶度（％)。 (實施例7〜9 ) 以與實施例1相同之方式算出除將摩擦處理材料表3所示般變更以外，膜。之表面之素材與作功能量（KJ )如以與實施例6相同之方式獲得離型對於自所獲得之離型膜 1膘之表層之表面起至厚度為1 m為止之區域，使用薄 ™ . 、°乎知用3式樣水平型X射線繞射妒 ^號理學公司製造）進行X射線分析1 =出相對於面平行地配向之錄之比例（％)。又以與貫細例6相同之方式笪ψ主、Further, the ratio (%) of the carbonyl group which is aligned with respect to the surface in parallel is a peak intensity A of a carbonyl group which is aligned in parallel with respect to a plane obtained by X-ray analysis, and a carbonyl group which is vertically aligned with respect to the plane. The peak intensity B 30 201144072 is applied to the formula π). The crystallinity (%) of the surface layer. (Examples 7 to 9) Films were prepared in the same manner as in Example 1 except that the rubbing treatment materials were changed as shown in Table 3. The material of the surface and the functional amount (KJ) were obtained in the same manner as in Example 6 for the area from the surface of the surface layer of the release film 1 to a thickness of 1 m, using a thin TM . . . , X-ray analysis 1 = ratio (%) of the alignment with respect to the plane parallel to the surface is performed by X-ray horizontal X-ray diffraction 制造^. In the same way as the example 6, the master,

Jl万式异出表層之結晶度（％)。 (比較例4) 除未進行摩擦處理以外 Γ以興貫施例6相同之方式獲得離型膜。對於自所獲得之離型膜之表層之表面起至厚度為i " m為止之區域，使用薄膜評價用試樣水平型χ射線繞射裝置（型號Smart Lab，理學公司製造）進行χ射線分析，從 2求出相對於面平行地配向之羰基之比例（％)。又，以與實施例ό相同之方式算出表層之結晶度（％)。一 (實施例1 0 ) 將作為表層用之結晶性芳香族聚酯樹脂之聚對苯二曱酸丁二酯（N〇VADURAN5〇1〇R5，三菱工程塑料公司製造，熔點為224。〇,以及作為中間層用之聚烯烴系樹脂之直鏈狀低密度聚乙烯（EXCELLEN FX(CX5501 ),住友化學公 31 201144072 司製造，熔點為66它）、乙烯·甲基丙烯酸甲酯共聚物 (ACRYFT ( WH4G1 )，住友化學公司製造，炼點為航）、及聚丙烯（PS207A，SunAllomer公司製造，熔點為16(rc ) 投入至共擠虔成形冑中m才莫進行共擠墨成形，從而獲得表層之厚度為丨〇 em、中間層之厚度為8〇 “⑺之膜。再者炫點係使用示差掃描熱析儀（DSC 2920，TA Instruments公司製造）進行測定。使用摩擦處理裝置（型號YCM-15〇M，山縣機械公司製造）’以成為表4所示之作功能量⑻）之方式，藉由將由棉構成之織物作為表面素材之摩擦處理材料對所獲得之膜的表層進行摩擦處理，藉此獲得表層之表面祕度^為 25〇⑽、表面之偏斜度Rsk為+請、表面之峰度_為8 之離型臈。再者’表層之表面⑽度&、表面之偏斜度触及表面之峰度Rku係分別使用上述式⑺、⑴及⑷算出。又，以與實施例i相同之方式算出表層之結晶度（％)。 (實施例11 ) 施例表面又，除將作功能量（KJ )如 10相同之方式獲得表層表4所示般變更以外，以與實之表面粗糙度RZ為250 nm、之偏斜度Rsk為+〇.3〇、类* ~ 表面之峰度Rku為以與實施例10相同之方彳曾 <万式算出表層之結 (實施例1 2 ) 5之離型膜。曰日度（％ ) 〇除將作功能量（KJ ) 羊毛構成之織物作為表面構成之織物作為表面素材如表4所示般變更，並藉由將由素材之摩擦處理材料代替將由棉之摩擦處理材料來進行摩擦處理 32 201144072 ^卜，以與實施例1〇相同之方式獲得表層之表面粗縫度Rz ;二随、表面之偏斜度趾為後85、表面之峰度Rku為 7之離型膜。又，以與實施例1()相同之方式結晶度（％)。田衣層之 (實施例1 3 ) 材料將由羊毛構成之織物作為表面素材之摩擦處理 ^枓代替將由棉構成之織物作為表面素材之摩擦處理材料來進订摩擦處理以外，以與實施例1〇相同之方之表面以為430 nm、表面之偏斜度Rsk為+1⑺=田 !度跑為11之離型膜…以與實施例H)相同之方：鼻出表層之結晶度（％)。式 (比較例5) π除未進行摩擦處理以外，以與實施例ι〇相同之得表層之表面粗糖度R為2() ^The crystallinity (%) of the Jl-type surface layer. (Comparative Example 4) A release film was obtained in the same manner as in Example 6 except that the rubbing treatment was not carried out. For the area from the surface of the surface layer of the obtained release film to the thickness of i " m, the horizontal evaluation method for the film evaluation type horizontal ray-ray diffraction device (model Smart Lab, manufactured by Rigaku Corporation) was used for the ray analysis. From 2, the ratio (%) of the carbonyl group aligned in parallel with respect to the plane was determined. Further, the crystallinity (%) of the surface layer was calculated in the same manner as in Example 。. (Example 10) Polybutylene terephthalate (N〇VADURAN 5〇1〇R5, which is a crystalline aromatic polyester resin for the surface layer), manufactured by Mitsubishi Engineering Plastics Co., Ltd., has a melting point of 224. As well as a linear low-density polyethylene (EXCELLEN FX (CX5501), manufactured by Sumitomo Chemical Co., Ltd. 31 melting point 66), ethylene-methyl methacrylate copolymer (ACRYFT) (WH4G1), manufactured by Sumitomo Chemical Co., Ltd., and refining point is aerospace), and polypropylene (PS207A, manufactured by SunAllomer, melting point of 16 (rc) is put into the co-extruded crucible to form co-extruded ink. The thickness of the surface layer was 丨〇em, and the thickness of the intermediate layer was 8 〇 "(7). The bright point was measured using a differential scanning calorimeter (DSC 2920, manufactured by TA Instruments). Using a friction treatment device (Model YCM) -15〇M, manufactured by Yamato Machinery Co., Ltd.) 'By the function amount (8) shown in Table 4, the surface layer of the obtained film was rubbed by using a fabric made of cotton as a friction material for the surface material. The surface fissure of the surface layer is 25〇(10), the skewness of the surface is Rsk is +, and the kurtosis of the surface is _8. The surface of the surface layer (10) degree & The kurtosis Rku of the surface of the skewness was calculated using the above formulas (7), (1), and (4). Further, the crystallinity (%) of the surface layer was calculated in the same manner as in Example i. (Example 11) Except that the functional quantity (KJ) is changed as shown in Table 10 in the same manner as in Table 10, the surface roughness RZ is 250 nm, and the skewness Rsk is +〇.3〇, class* ~ The kurtosis Rku of the surface is the same as that of Example 10, and the release film of the surface layer (Example 1 2) 5 is calculated. 曰 Day (%) The function amount is removed ( KJ) The fabric composed of wool as the surface material is changed as shown in Table 4, and the friction treatment is performed by the friction treatment material of the material, and the friction treatment is performed by the friction treatment material of cotton. Example 1 获得 the same way to obtain the surface roughness Rz of the surface layer; The beveled toe is the release film of the back 85 and the kurtosis Rku of the surface is 7. Further, the crystallinity (%) is the same as in the case of Example 1 (). The material of the field layer (Example 13) will be made of wool. The woven fabric was used as a rubbing treatment for the surface material. Instead of the rubbing treatment using the woven fabric made of cotton as the surface material, the surface of the same surface as in Example 1 was 430 nm, and the surface was deflected. Degree Rsk is +1 (7) = Tian! Degree is 11 release film... in the same way as in Example H): crystallinity (%) of the nose surface layer. Formula (Comparative Example 5) The surface roughness of the surface layer R was 2 () ^ except that π was not subjected to the rubbing treatment, and the same as in Example ι.

又KZ馮200 nm、表面之偏斜度Rsk A ⑽、表面之峰度Rku為3之離型膜。又，又為相同之方式算出表層之結晶度（％)。與貫施例10 (比較例6) 除將作功能量（K j )如表 Μ構成之織物作為表面素表材更，並藉由將* 構成之織物作為表=棉以外，以與實施例仃摩擦處理為258_、表面之偏J =式獲-表層之表面粗链度h 偏斜度Rsk為_〇 34、志；ε；士々 3之離型膜以與實施例！〇相同 J=RkU為晶度（％)。方式鼻出表層之結 33 201144072 (比較例7) 除將作功能量（KJ)如矣4 & 表4所不般變更，並 PET構成之織物作為表面由將由 m ^ ^ ^ ^ ^ .、之摩扒處理材料代替將由棉構成之織物作為表面素材之麼換+油， ▼何之摩擦處理材料來進行摩以外，以與實施例H)㈣之心礼處理KZ von 200 nm, surface skewness Rsk A (10), surface kurtosis Rku is 3 release film. Further, the crystallinity (%) of the surface layer was calculated in the same manner. And Example 10 (Comparative Example 6) except that the fabric having the functional amount (K j ) as the surface Μ is used as the surface element material, and the fabric composed of * is used as the table = cotton, and the embodiment The rubbing treatment is 258_, the surface is biased J = the formula is obtained - the surface of the surface layer is thick chain degree h, the skewness Rsk is _〇34, 志; ε; the release film of gentry 3 and the embodiment! 〇 Same J=RkU is crystallinity (%). Method of nasal surface layer 33 201144072 (Comparative Example 7) except that the functional amount (KJ) is changed as shown in Table 4 & Table 4, and the fabric composed of PET as the surface is composed of m ^ ^ ^ ^ ^ . The rubbing treatment material replaces the fabric made of cotton as the surface material, and the oil is replaced by the friction treatment material, and the treatment with the embodiment H) (4)

^ 98Λ * _ 獲得表層之表面粗糙度RZ^ 98Λ * _ Get the surface roughness RZ of the surface layer

為280 nm、表面之偏斜度R W” k4+〇·29、表面之峰度Rku為 3之離型膜。又，以與眘尬興貫施例10相同之方式算晶度（0/。）。、丹衣層之結 (比較例8) 除將作功能量（KJ)如* 4邮_ ή 4 至主Μ占夕⑽表4所不般變更，並藉由將由椹忐之蚪物柞太、摩裇處理材料代替將由棉構成之、我物作為表面上以外心眘始擦處理材料來進行摩擦處理以外，以與實施例10相同為购m、表面之偏斜度R :表層之表面粗縫度 4之離型膜。又，以盘香為〇.25、表面之峰度Rku為之雕U又，以與實施例1〇結晶度（％)。乃式彳算出表層之 (比較例9) 除將作功能量（K T、1主^ 羊毛構成之織物作=:4:示般變更，並藉由將由構成之織物作為表= = ;Γ處理材料代替將由棉以外，以與實施例=方: .^ U之方式獲侍表層之表面粗糙度Rz 為460 ,表面之偏斜度⑽為+ι」又Rz 1 2之離型膜。又，以與又Rku為晶度（％)。肖實施例1〇相同之方式算出表層之結 34 201144072 (評價）對實施例、比較例中所獲得之離型膜進行以下之評價。將結果示於表1〜4。 (1)離型性（剝離力）將剪成200 mm見方之覆蓋膜（CISV_2535，Nikkan Industries公司製造）之環氧接著劑面與所獲得之離型膜之表層面重疊’使用滑動式真空熱壓機（MKp_3〇〇〇v-MH-ST， Mikad〇technos 公司製造），以壓力 3〇kgf、i8〇<t、6 分鐘進行加壓後，於23 C、50%RH之條件下固化i天。其後，自固化後之樣品中切出寬度3〇 mm、長度i 5〇 mm之評價樣口口針對該s平價樣品，使用丁ensil〇n ( STA l 15〇，A & D公司製k )以剝離速度500 mm/min、剝離角度i 8(Γ(：測定剝離力（N/3 0 mm )。 (2 )追隨性（嵌入性） •將覆銅積層板（20 cm><2〇 cm，聚醯亞胺厚25 銅箱18 _，以下稱為「CCL」）、覆蓋膜（2〇cmx2〇cm，聚醯亞胺厚12 ，環氧系樹脂接著劑層i5 "m)、及所獲得之離里膜自下而上地按該順序堆積，4吏用真空加壓機於160 C 30 kg/cm、30分鐘之條件進行加壓，從而製成由CCL與覆蓋臈構成之Fpc (〜训16叫㈣α㈣“，可 :1·生,刷電路）评價樣品。再者，於覆蓋膜上預先製作接著U里才貝用之圖案（鳩#爪間距，爪間距）。二、後取出FPC評價樣品及離型膜，藉由顯微鏡觀察覆蓋膜上之接著劑流出量評價用之孔，藉此測定所流出之 35 201144072 接著劑之長度。將所流出之接著劑之長度未達10 // m之情形評價為◎，將1 0 // m以上且未達20 # m之情形評價為〇，將20 # m以上且未達30 μ m之情形評價為△，將30 # m以上之情形評價為X。 36 201144072 實施例5 聚對苯二曱酸丁二酯〇 21% 200 羊毛 On «••Μ 0.33 fs VO 0.09 ◎ 實施例4 聚對苯二甲酸丁二酯 200 24% | 500 羊毛〇\ 0.33 CN v〇 0.04 〇實施例3 聚對笨二甲酸丁二酯| 〇 22% 250 羊毛甘· 〇\ 0.33 r4 <n v〇 0.08 ◎ 實施例2 聚對苯二曱酸丁二酯 250 | 22% 250 Toraysee (東麗公司製造）卜 — 寸 d 卜 ο m rs 0.09 〇實施例1 聚對苯二甲酸丁二酯〇 21% Toraysee (東麗公司製造）卜寸寸 d 卜 ο ΓΛ (N 0.11 ◎ 構成表層之樹脂離型處理層之厚度（nm) 結晶度（％) 作功能量（KJ) 種類拉伸強度（g/d) 伸長率（％) 摩擦係數彈性模數（MPa) 拉伸強度（N/10mm) 離型性（剝離力（N/30mm)) 追隨性纖維喊νθ 遊< 表層摩擦處理評價 201144072 【(Νί 比較例3 聚對笨二甲酸丁二酯 350 26% 550 〇寸· to 0.65 d 卜 0.04 0 比較例2 聚對苯二甲酸丁二酯 500 27% 550 Tetoron (帝人纖維公司製造）寸 On Ο (N m 0.08 X 比較例1 聚對苯二甲酸丁二酯〇 20% 〇無摩擦處理 0.40 ◎ 構成表層之樹脂離型處理層之厚度（nm) 結晶度（％) 作功能量（KJ) 種類拉伸強度（g/d) 伸長率（％) 摩擦係數彈性模數（Mpa) 拉伸強度（N/10mm) 離型性（剝離力（N/30mm)) 追隨性織維摩擦處理材料之表面之素材表層摩擦處理評價 201144072 鬥e<】比較例4 聚對苯二甲酸丁二酯 38% 19% 〇無摩擦處理 0.40 ◎ 實施例9 聚對笨二甲酸丁二酯 58% 23% 500 P — in 0.65 Ο 0.04 〇實施例8 聚對苯二甲酸丁二酯i 56% 23% 500 羊毛 σ\ 0.33 ίΝ v〇 0.04 〇實施例7 聚對苯二曱酸丁二酯 47% 21% 250 Toraysee (東麗公司製造） — d 卜 d fN 0.09 〇實施例6 聚對苯二曱酸丁二酯 45% 20% Toraysee (東麗公司製造）卜寸 d 卜 ο <N 0.11 ◎ 構成表層之樹脂相對於面平行地配向之羰基之比例（％) 結晶度（％) 作功能量（KJ) 種類拉伸強度（g/d) 伸長率（％) 摩擦係數彈性模數（MPa) 拉伸強度（N/10mm) 離型性（剝離力（N/30mm)) 追隨性纖維 w « ^ 验w + 表層摩擦處理評價 201144072 〔寸<】比較例9 1 _羊毛1 460 +1.15 <N 0.17 X 比較例8 1羊毛1 200 240 +0.25 对 0.15 ◎ 比較例7 PET 240 280 +0.29 <N <N 0.18 〇比較例6 PET 200 258 -0.34 ΓΛ (N 0.17 ◎ 比較例5 1 〇〇 CN +0.50 m 宕 0.33 ◎ 實施例13 L———羊毛1 〇 430 +1.10 ΓΟ (N 0.04 〇實施例12 1羊毛J 450 380 +0.85 卜 <N (N 0.04 〇實施例11 51 250 250 +0.30 S 0.08 〇實施例10 500 250 +0.80 00 is 0.06 〇摩擦處理材料之表面之素材作功能量（KJ) 表面粗链度Rz (nm) 表面之偏斜度Rsk 表面之峰度Rku 結晶度（％) 剝離力（離型性）（N/30mm) 追隨性摩擦處理表層評價 201144072 [產業上之可利用性j 據本發明’可提供-種離型性優異且對於基板表面之追隨性優異、可抑制熱屡成形時之接潛劑之流出的離型【圖式簡單說明】圖1係示意性地表示本發明之第層之一部分的剖面圖。發明之離型膜之表圖2係示意性地表示本發明之第層之一部分的剖面圖。 1發明之離型膜之表圖3係示意性地表示本發明之第層之一部分的剖面圖。 1發明之離型膜之表電面圖4係針對實施例1中所獲得之離型膜子顯微鏡對使用切片機於厚度方向上進行進行觀察而獲得之圖像。 ’藉由穿透型切割所得之剖圖5係針對實施例2中所獲電子顧料错i膜’藉由穿透型、佳 > 伽☆ 度方向進行切割所得之剖面進订觀察而獲得之圖像。于之。〗面圖6係針對實施例3中所獲得之離型膜電子顯微鏡對使用切片機在厚度方向進行切進行觀察而獲得之圖像。 ’藉由穿透型割所得之剖面圖7係針對實施例5中所獲得之離型膜電子顯微鏡對使用切片機在厚度方向進行切進行觀察而獲得之圖像。 ’藉由穿透型害，J所得之剖面It is a release film of 280 nm, the surface skewness RW" k4 + 〇 · 29, and the surface kurtosis Rku is 3. Further, the crystallinity (0/.) is calculated in the same manner as in the case of Shen Yan Xing. The knot of the denim layer (Comparative Example 8) is not changed except for the functional quantity (KJ) such as * 4 mail _ ή 4 to the main Μ Μ ( (10) Table 4, and The surface of the surface layer is the same as that of the embodiment 10 except that the material is made of cotton, and the material is made of cotton as the outer surface of the surface. A release film with a rough seam of 4. In addition, the disc scent is 〇.25, and the kurtosis Rku of the surface is etched U, and the crystallinity (%) of Example 1 is calculated. Example 9) In addition to the functional quantity (KT, 1 main ^ wool fabric made =: 4: as shown, and by the fabric made up of the table = =; Γ treatment material instead of cotton, and Example = square: .^ U is obtained by the surface layer roughness Rz of 460, the surface skewness (10) is +ι" and Rz 1 2 release film. Also, with Rku as crystal In the same manner as in the above, the surface layer of the surface layer was calculated. The evaluation of the release film obtained in the examples and the comparative examples was as follows. The results are shown in Tables 1 to 4. (1) Release type (peeling force) The epoxy adhesive surface cut into a 200 mm square cover film (CISV_2535, manufactured by Nikkan Industries Co., Ltd.) and the surface layer of the obtained release film were overlapped using a sliding vacuum heat press ( MKp_3〇〇〇v-MH-ST, manufactured by Mikad〇technos Co., Ltd., was pressurized at 3 〇 kgf, i8 〇 <t, 6 minutes, and then cured under conditions of 23 C and 50% RH for 1 day. Thereafter, an evaluation sample having a width of 3 〇 mm and a length of i 5 〇 mm was cut out from the sample after curing, and for the s parity sample, butyl ensil 〇n (STA l 15 〇, manufactured by A & D) was used. ) peeling speed of 500 mm/min, peeling angle i 8 (Γ (: measurement of peeling force (N/3 0 mm). (2) followability (embeddedness) • copper clad laminate (20 cm><2 〇cm, polyimine thick 25 copper box 18 _, hereinafter referred to as "CCL"), cover film (2〇cmx2〇cm, polytheneimide thickness 12, epoxy The grease adhesive layer i5 "m), and the obtained detachment film are stacked in this order from bottom to top, and are pressurized by a vacuum press at 160 C 30 kg/cm for 30 minutes. Thus, an Fpc (~Tong 16 (4) α (four) ", can be: 1 · raw, brush circuit) composed of CCL and cover 制成 is prepared. Further, a pattern for the U-shaped shell (鸠#claw pitch, claw pitch) is prepared in advance on the cover film. 2. The FPC evaluation sample and the release film were taken out, and the pores for evaluating the amount of the outflow of the adhesive on the cover film were observed by a microscope, thereby measuring the length of the eluted 35 201144072. The case where the length of the adhesive flowing out was less than 10 // m was evaluated as ◎, and the case where 10 0 m or more and less than 20 # m was evaluated as 〇, which was 20 # m or more and less than 30 μm The case was evaluated as Δ, and the case of 30 # m or more was evaluated as X. 36 201144072 Example 5 Polybutylene terephthalate 〇21% 200 Wool On «••Μ 0.33 fs VO 0.09 ◎ Example 4 Polybutylene terephthalate 200 24% | 500 Wool 〇 \ 0.33 CN V〇0.04 〇Example 3 Poly(p-butylene dicarboxylate)|〇22% 250 wool Gan·〇\ 0.33 r4 <nv〇0.08 ◎ Example 2 Polybutylene terephthalate 250 | 22% 250 Toraysee (made by Toray Industries) Bu-inch d Bu ο m rs 0.09 〇Example 1 Polybutylene terephthalate 〇21% Toraysee (manufactured by Toray Industries, Inc.) 卜寸 inch d ο ΓΛ ΓΛ (N 0.11 ◎ constituting the surface layer Thickness of resin release layer (nm) Crystallinity (%) Functional quantity (KJ) Type tensile strength (g/d) Elongation (%) Friction coefficient elastic modulus (MPa) Tensile strength (N/ 10mm) Release (peeling force (N/30mm)) Follow-up fiber shouting νθ swim < Surface friction treatment evaluation 201144072 [(Νί Comparative example 3 poly(p-butylene dicarboxylate) 350 26% 550 〇 inch to 0.65 d 卜 0.04 0 Comparative Example 2 Polybutylene terephthalate 500 27% 550 Tetoron Manufactured by 司 On Ο (N m 0.08 X Comparative Example 1 Polybutylene terephthalate 〇 20% 〇 No rubbing treatment 0.40 ◎ Thickness (nm) of crystallinity treatment layer constituting the surface layer Crystallinity (%) Functional quantity (KJ) Type tensile strength (g/d) Elongation (%) Friction coefficient Elastic modulus (Mpa) Tensile strength (N/10mm) Release property (peeling force (N/30mm)) Follow-up weaving Material surface friction treatment evaluation of the surface of the friction treatment material 201144072 Bucket e<] Comparative Example 4 Polybutylene terephthalate 38% 19% 〇 No rubbing treatment 0.40 ◎ Example 9 Polybutylene dicarboxylate 58 % 23% 500 P — in 0.65 Ο 0.04 〇 Example 8 Polybutylene terephthalate i 56% 23% 500 Wool σ\ 0.33 ίΝ v〇0.04 〇 Example 7 Polybutylene terephthalate 47 % 21% 250 Toraysee (Toray Industries, Inc.) — d Bu d fN 0.09 〇Example 6 Polybutylene terephthalate 45% 20% Toraysee (Toray Industries, Inc.) Bu inch d Bu ο <N 0.11 ◎ Ratio of the carbonyl group constituting the surface layer to the carbonyl group aligned in parallel with the surface (%) Crystallization (%) Function amount (KJ) Type Tensile strength (g/d) Elongation (%) Friction coefficient Elastic modulus (MPa) Tensile strength (N/10mm) Release property (peeling force (N/30mm) ) Follow-up fiber w « ^ Test w + Surface rubbing treatment evaluation 201144072 [Inch <] Comparative Example 9 1 _wool 1 460 +1.15 <N 0.17 X Comparative Example 8 1 Wool 1 200 240 +0.25 Pair 0.15 ◎ Comparative Example 7 PET 240 280 +0.29 <N <N 0.18 〇Comparative Example 6 PET 200 258 -0.34 ΓΛ (N 0.17 ◎ Comparative Example 5 1 〇〇CN +0.50 m 宕0.33 ◎ Example 13 L--wool 1 〇 430 +1.10 ΓΟ (N 0.04 〇Example 12 1wool J 450 380 +0.85 卜<N (N 0.04 〇Example 11 51 250 250 +0.30 S 0.08 〇Example 10 500 250 +0.80 00 is 0.06 〇friction treatment The material of the surface of the material is the functional amount (KJ) The surface is thickly chained Rz (nm) The skewness of the surface Rsk The kurtosis of the surface Rku Crystallinity (%) Peeling force (release property) (N/30mm) Follow-up friction Treatment surface evaluation 201144072 [Industrial availability] According to the present invention, it is provided that the release property is excellent and for the substrate The surface is excellent in followability and can suppress the outflow of the submersible agent during hot forming. [Brief Description of the Drawings] Fig. 1 is a cross-sectional view schematically showing a part of the first layer of the present invention. Table of the release film of the invention Fig. 2 is a cross-sectional view schematically showing a part of the first layer of the present invention. Fig. 3 is a cross-sectional view schematically showing a part of the first layer of the present invention. The surface of the release film of the invention Fig. 4 is an image obtained by observing the thickness direction of the slicer using the release film microscope obtained in Example 1. 'The cross-sectional view 5 obtained by the through-cutting is obtained by observing the cross-section of the electronically-corrected i-film obtained in Example 2 by cutting in the direction of penetration, good > The image. Because of it. Fig. 6 is an image obtained by observing the thickness direction of the slicer with respect to the release film electron microscope obtained in Example 3. Section obtained by penetrating cutting Fig. 7 is an image obtained by observing the thickness direction of the slicer with respect to the release film electron microscope obtained in Example 5. 'by the penetration type, the profile obtained by J

係針對比較例1中所獲得之離型膜藉由穿透型 201144072 電子顯微鏡對使用切片機在厚度方向進行切割所得之剖面進行觀察而獲得之圖像。【主要元件符號說明】離型處理層表層中之其他區域 1 2 ' 2 42The release film obtained in Comparative Example 1 was obtained by observing a cross section obtained by cutting a thickness of a microtome by a penetration type 201144072 electron microscope. [Description of main component symbols] Release processing layer Other areas in the surface layer 1 2 ' 2 42

Claims

201144072 七、申請專利範圍： !•一種離型膜，具有表層，並僅於自該表層之表面起至厚度為50〜300nm為止之區域内觀察到離型處理層。 2.-種離型膜，具有含有聚醋系樹脂之表層，於自該表 a表面起至厚度為i" m為止之區域内，該聚酯系樹脂所含之羰基之中相對於面平行地配向之羰基的比例為抓以上0 3.-種離型膜，具有表層，該表層之表面㈣度^為 250〜450,表面之偏斜度Rsk為+〇3〜+ι」，且表面之峰度Rku為5〜1 1。 4·如申叫專利範圍帛i項或第3項之離型膜，其中，表層含有聚酯系樹脂。 5.如申請專利範圍第w、第2項、第3項或第4項之離型膜，其中，表層之結晶度為25%以下。 6·如申請專利範圍第【項、第2項、第3項、第4項或第5項之離型膜，係用於如下之用途：當隔著預浸體（prepreg)或耐熱膜將覆銅積層板或銅箱熱壓成形於基板，來製造印刷配線基板、可撓性印刷基板或多層印刷配線板時，防止熱壓板與所獲得之印刷配線基板、可撓性印刷基板或多層印刷配線板之接著。 7.如申請專利範圍第！項、第2項、第3項、第4項或第5項之離型膜，係用於如下之用途：當藉由熱硬化性接著劑以熱壓成形將覆蓋膜接著於形成有銅電路之基板，來製造可撓性印刷基板時，防止熱壓 43 201144072 板與該覆蓋膜之接著、或防止該覆蓋膜彼此之接著。 8.如申請專利範圍第1項、第2項、第3項、第4項或第5項之離型膜，係用於如下之用途：當利用熱壓成形來製造半導體用模具（mold)時，防止成形金屬模具與模具樹脂（mold resin)之接著。201144072 VII. Patent application scope: • A release film with a surface layer, and the release treatment layer is observed only in the region from the surface of the surface layer to a thickness of 50 to 300 nm. 2.- A release film having a surface layer containing a polyester resin, wherein the carbonyl group contained in the polyester resin is parallel to the surface in a region from the surface of the surface a to the thickness i" The proportion of the carbonyl group in the ground direction is the above-mentioned 0.- kinds of release film, having a surface layer, the surface of the surface layer (four) degrees ^ 250 ~ 450, the surface skewness Rsk is + 〇 3 ~ + ι", and the surface The kurtosis Rku is 5 to 1 1. 4. The release film of the patent scope 帛i item or item 3, wherein the surface layer contains a polyester resin. 5. The release film of claim w, item 2, item 3 or item 4, wherein the surface layer has a crystallinity of 25% or less. 6. If the release film of the [Scope, Item 2, Item 3, Item 4 or Item 5 of the patent application scope is used for the following purposes: When prepreg or heat resistant film is interposed When a copper clad laminate or a copper box is thermoformed on a substrate to produce a printed wiring board, a flexible printed board, or a multilayer printed wiring board, the hot platen and the obtained printed wiring board, the flexible printed board, or the multilayer are prevented. The printed wiring board is followed. 7. If you apply for a patent range! The release film of item 2, item 3, item 4 or item 5 is used for the following purposes: when the film is formed by hot press forming with a thermosetting adhesive followed by formation of a copper circuit In the case of manufacturing a flexible printed circuit board, the substrate is prevented from being thermally pressed 43 201144072, and the cover film is prevented from adhering to the cover film. 8. A release film as claimed in claim 1, item 1, item 3, item 4 or item 5, for use in the following applications: When manufacturing a semiconductor mold by hot press forming At the same time, the forming metal mold is prevented from coming on with the mold resin.