201228826 六、發明說明： 【發明所屬之技術領域】 本專利申請案係以日本專利申請案第2 0 1 0 - 2 2 8 3 1 9號 (2010年10月8日申請）爲基準，主張巴黎條約之優先 權’藉由引用於此處，上述申請案中所記載的全體內容， 皆記載於本說明書中。 本發明係有關一種具有由液晶聚酯所構成的基材層與 離型層之離型薄膜。 【先前技術】 於電子零件製造時或保管時或加工時，爲保護電子零 件或其構件時使用的離型薄膜，企求在高溫下不會變形且 軟化之耐熱性。耐熱性優異的離型薄膜，以液晶聚酯薄膜 爲基材，且於其上設置離型層所成者，於專利文獻1中揭 示’具體而言揭示作爲構成前述液晶聚酯薄膜之液晶.聚酯 ’具有來自P -羥基苯甲酸之重複單位 60莫耳％、來自對 苯二甲酸之構造單位15莫耳％ '來自異對苯二甲酸之構 造單位5莫耳。/。及來自4,4_二羥基聯苯之構造單位2〇莫 耳％。 [專利文獻] 專利文獻1:日本特開2001-315261號公報 【發明內容】 -5- 201228826 如專利文獻1中揭示，習知具有由液晶聚酯所構成的 基材層與離型層之離型薄膜，由於耐水性不充分，容易因 吸水而變形且容易產生離型層剝離的情形。此處，本發明 之目的，係提供一種具有由液晶聚酯所構成的基材層與離 型層，且耐水性優異的離型薄膜。 爲達成前述目的時，本發明係提供一種離型薄膜，其 係具有由以下述式（1)所示之重複單位、以下述式（2) 所示之重複單位與以下述式（3)所示之重複單位，且含 2,6_伸萘基之重複單位的含量相對於全部重複單位之合計 量而言爲40莫耳％以上之液晶聚酯所構成的基材層，與離 型層之離型薄膜。 —Ο — Αγ^—CO — (1) 一CO-A r2 — CO- (2) —Ο — Ar3 — Ο — (3) (八1*1係表示2,6-伸萘基、1，4-伸苯基或4,4’-聯苯基。八1·2 及Ar3係各獨立表示2,6-伸萘基、1,4-伸苯基、1,3-伸苯基 或4,4’-聯苯基。以Ar1、Ar2或Ar3所示之前述基的氫原 子可各獨立被鹵素原子、烷基或芳基取代）。 [發明效果] 本發明之離型薄膜，耐水性優異。 [爲實施發明之最佳形態] 構成本發明之離型薄膜的基材層之液晶聚酯，係於熔 融時展現光學各向異性之聚酯，具有由以下述式（1)所 -6- 201228826 示之重複單位（以下稱爲重複單位（1))、以下述式（2 )所示之重複單位（以下稱爲重複單位（2))、與以下 述式（3)所示之重複單位（以下稱爲重複單位（3))。 一 〇-Ari—C〇一 (1) 一CO — A r2 —CO — (2) 一 Ο — Ar3 — Ο — (3) (Ar1係表示2,6-伸萘基、l，4-伸苯基或4,4，_聯苯基。Αγ2 及八1*3係各獨1£表不2,6-伸萘基、1，4-伸苯基、1，3_伸苯基 或4,4’·聯苯基。以Ar1、Ar2或Ar3所示之前述基的氫原 子可各獨立被鹵素原子、碳數1〜1〇之烷基或碳數6〜20 之芳基取代）。 前述鹵素原子例如氟原子、氯原子、溴原子及碘原 子。前述烷基之例’如甲基、乙基、正丙基、異丙基、正 丁基、異丁基、第2-丁基、第3-丁基、正己基、2_乙基己 基、正辛基及正癸基，其碳數通常爲1〜10。前述芳基之 例’如苯基、〇 -甲苯基、m -甲苯基、p_甲苯基、ι_萘基及 2 -萘基，其碳數通常爲6〜20。前述氫原子以此等之基取 代時’其數係Ar1、Ar2或Ar3所示之每一個前述基，通常 各獨立爲2個以下，較佳者爲1個以下。 重複單位（1)係來自一定的芳香族羥基羰基之重複 單位。重複單位（1 )以Ar1爲2,6·伸萘基 '即來自6_經 基-2-萘甲酸之重複單位較佳。 重複單位（2)係來自一定的芳香族二羧酸之重複單 位。重複單位（2)以Ar2爲2，6 -伸萘基（即來自2,6 -萘 二羧酸之重複單位）、及Ar2爲1，4 -伸苯基（即來自對苯 201228826 二甲酸之重複單位）較佳。 重複單位（3)係來自一定的芳香族二醇之重複單位 。重複單位（3 )以Ar3爲1，4-伸苯基（即來自氫醌之重 複單位）、及Ar3爲4,4’-聯苯基（即來自4,4’-二羥基聯 苯之重複單位）較佳。 於液晶聚酯中，相對於含2,6-伸萘基之重複單位的含 量、即Ar1爲2,6-伸萘基之重複單位（1 ) 、Ar2爲2,6-伸 萘基之重複單位（2)、與Ar3爲2,6-伸萘基之重複單位 (3 )之合計含量，除以全部重複單位之合計量（藉由以 構成液晶聚酯之各重複單位的質量除以各重複單位之式量 ，求取各重複單位之物質相當量（莫耳），合計此等之値 )而言，爲40莫耳％以上》藉由使該具有一定的重複單位 之單位組成之液晶聚酯予以薄膜化，可製得水蒸氣阻障性 優異的液晶聚酯薄膜。該2,6-伸萘基之含量，較佳者爲5〇 莫耳％以上，更佳者爲6 0莫耳％以上，最佳者爲7 0莫耳〇/0 以上。 而且，於液晶聚酯中重複單位（1)之含量，相對於 全部重複單位之合計量而言，較佳者爲30〜80莫耳％，更 佳者爲40〜70莫耳％，最佳者爲45〜65莫耳％ ;重複單 位（2)之含量’相對於全部重複單位之合計量而言，較 佳者爲1 〇〜3 5莫耳％，更佳者爲1 5〜3 0莫耳％，最佳者 爲17.5〜27.5莫耳％ :重複單位（3)之含量，相對於全 部重複單位之合計量而言，較佳者爲10〜35莫耳％，更;f圭 者爲15〜30莫耳％，最佳者爲17.5〜27.5莫耳％。該具有· -8 - 201228826 一定重複單位組成之液晶聚酯，耐熱性與成形性之平衡性 優異。而且’重複單位（2)之含量與重複單位（3)之含 量’以實質上相等較佳。而且，液晶聚酯視其所需亦可具 有除重複單位（1)〜（3)以外之重複單位，惟其含量相 對於全部重複單位之合計量而言，通常爲10莫耳％以下， 較佳者爲5莫耳％以下。 耐熱性或熔融張力高的液晶聚酯之典型例，相對於全 部重複單位之合計量而言，具有Ar1爲2,6-伸萘基之重複 單位（1 )(即來自6-羥基-2-苯甲酸之重複單位，較佳者 爲40〜74_8莫耳％，更佳者爲40〜64_5莫耳％，最佳者爲 50〜58莫耳％)，具有Ar2爲2,6-伸萘基之重複單位（2 )(即來自2,6-萘二羧酸之重複單位，較佳者爲12.5〜30 莫耳％，更佳者爲17.5〜30莫耳％，最佳者爲20〜25莫耳 %)，具有Ar2爲1，4-伸苯基之重複單位（2 )(即來自對 苯二甲酸之重複單位，較佳者爲0.2〜15莫耳。/。，更佳者 爲0.5〜12莫耳％，最佳者爲2〜10莫耳％)，及具有Ar3 爲1，4-伸苯基之重複單位（3 )(即來自氫醌之重複單位 ’較佳者爲1 2 · 5〜3 0莫耳％，更佳者爲1 7.5〜3 0莫耳％， 最佳者爲20〜25莫耳％)，且Ar2爲2,6-伸萘基之重複單 位（2 )的含量，相對於Ar2爲2，6-伸萘基之重複單位（2 )及Ar2爲1,4-伸苯基之重複單位（2)之合計含量而言 ，較佳者爲0.5莫耳倍以上，更佳者爲0.6莫耳倍以上。 液晶聚酯係可藉由使具有重複單位（1 )之單體（即 一定的芳香族羥基羧酸）、具有重複單位（2)之單體（ -9 - 201228826 即一定的芳香族二羧酸）、與具有重複單位（3)之單體 (即一定的芳香族二醇）’以具有2,6 -伸萘基之單體的合 計量（即6 -羥基-2-萘甲酸、2，6 -萘二羧酸及2,6-萘二醇之 合計量），相對於全部單體之合計量而言爲40莫耳％以上 之條件，予以聚合（聚縮合）而製得。此時，芳香族羥基 羧酸、芳香族二羧酸及芳香族二醇之各獨立的部分或全部 ，亦可使用可聚合的衍生物取代。如芳香族羥基羧酸及芳 香族二羧酸之具有羧基的化合物的可聚合的衍生物之例， 使羧基變換成烷氧基羰基或芳氧基羰基所成者、使羧基變 換成鹵化甲醯基所成者、使羧基變換成醯氧基羰基所成者 。如芳香族羥基羧酸及芳香族二醇之具有羥基的化合物的 可聚合的衍生物之例，如使羥基醯基化而變換成醯氧基所 成者。 另外，液晶聚酯係以藉由使單體熔融聚合，將所得的 聚合物（預聚物）予以固相聚合而製造較佳。藉此，可以 良好的操作性製造耐熱性或熔融張力高的液晶聚酯。熔融 聚合可在觸媒存在下進行，該觸媒例如醋酸鎂、醋酸錫、 鈦酸四丁酯、醋酸鉛、醋酸鈉、醋酸鉀、三氧化銻等之金 屬化合物、或N，N -二甲基胺基吡啶、N -甲基咪唑等之含 氮雜環式化合物，以使用含氮雜環式化合物較佳。 液晶聚酯之流動開始溫度爲28 0°C以上較佳、更佳者 爲290°C以上、最佳者爲29 5 °C以上，而且，通常爲3 8 0°C 以下、較佳者爲35(TC以下。流動開始溫度愈高時，耐熱 性或熔融張力愈爲容易提高，惟相當高時，爲使熔融時必 -10- 201228826 須使用高溫，且於成形時容易產生熱惡化情形。 而且，流動開始溫度亦稱爲流溫（flow temperature ) 或流動溫度，係使用具有內徑1mm、長度10mm之噴嘴的 毛細管電流計，在 9.8MPa ( 100kg/cm2 )之荷重下，以 * 4 °C /分鐘之昇溫速度使液晶聚酯之加熱熔融物自噴嘴押出 '時，展現熔融黏度爲4 800Pa · s ( 48,000泊）之溫度，爲 容易形成液晶聚酯之分子量者（參照小出直之編、「液晶 聚合物-合成•成形應用-」、CMC股份有限公司、1987年 6 月 5 日、p95)。 於液晶聚酯中，視其所需亦可配合其他的成分，作爲 組成物。其他成分之例，如塡充材、除液晶聚酯外之熱可 塑性樹脂及添加劑。組成物全體中所佔的液晶聚酯之比例 ，較佳者爲80質量％以上，更佳者爲90質量％以上。 塡充材之例，如磨碎玻璃纖維、短玻璃纖維等之玻璃 纖維、鈦酸鉀晶鬚、氧化鋁晶鬚、硼酸鋁晶鬚、碳化矽晶 鬚、氮化矽晶鬚等之金屬或非金屬系晶鬚類、玻璃珠、中 空玻璃球、玻璃粉末、雲母、滑石、黏土、二氧化砂、氧 化鋁、鈦酸鉀、矽灰石、碳酸鈣（重質、輕質 '膠質等） 、碳酸鎂、鹼性碳酸鎂、硫酸鈉、硫酸鉀、硫酸鋇、亞硫201228826 VI. Description of the invention: [Technical field to which the invention pertains] This patent application claims Paris based on Japanese Patent Application No. 2 0 1 0 - 2 2 8 3 1 9 (applicant on October 8, 2010) The priority of the treaty is hereby incorporated by reference in its entirety. The present invention relates to a release film having a substrate layer and a release layer composed of a liquid crystal polyester. [Prior Art] In the manufacture of electronic components, during storage or processing, the release film used to protect electronic parts or their components is designed to be heat-resistant without being deformed and softened at high temperatures. A release film having excellent heat resistance is a liquid crystal polyester film as a base material, and a release layer is provided thereon. Patent Document 1 discloses that it specifically discloses a liquid crystal which constitutes the liquid crystal polyester film. The polyester 'has 60 mol% from the repeating unit of P-hydroxybenzoic acid and 15 mol% from the structural unit of terephthalic acid' 5 mols from the structural unit of isophthalic acid. /. And the structural unit derived from 4,4_dihydroxybiphenyl is 2% by mole. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2001-315261. SUMMARY OF THE INVENTION - 5 - 201228826 As disclosed in Patent Document 1, it is known that a substrate layer and a release layer composed of a liquid crystal polyester are separated from each other. The film of the type is easily deformed by water absorption due to insufficient water resistance and is likely to cause peeling of the release layer. Here, an object of the present invention is to provide a release film having a base material layer and a release layer composed of a liquid crystal polyester and having excellent water resistance. In order to achieve the above object, the present invention provides a release film which has a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a formula (3) a substrate unit composed of a liquid crystal polyester having a repeating unit of 2,6_anthylene group and a content of a repeating unit of 2,6-extended naphthyl group of 40 mol% or more based on the total amount of all repeating units, and a release layer Release film. —Ο — Αγ^—CO — (1) A CO-A r2 — CO— (2) —Ο — Ar3 — Ο — (3) (Eight 1*1 represents 2,6-anthranyl, 1,4 - phenyl or 4,4'-biphenyl. The VIII and 2 are independently represented by 2,6-anthranyl, 1,4-phenylene, 1,3-phenyl or 4, 4'-biphenyl. The hydrogen atom of the above-mentioned group represented by Ar1, Ar2 or Ar3 may be independently substituted by a halogen atom, an alkyl group or an aryl group). [Effect of the Invention] The release film of the present invention is excellent in water resistance. [Best Mode for Carrying Out the Invention] The liquid crystal polyester constituting the base material layer of the release film of the present invention is a polyester which exhibits optical anisotropy upon melting, and has a -6- of the following formula (1) 201228826 The repeating unit (hereinafter referred to as repeating unit (1)), the repeating unit shown by the following formula (2) (hereinafter referred to as repeating unit (2)), and the repeating unit shown by the following formula (3) (hereinafter referred to as repeating unit (3)).一〇-Ari-C〇一(1) A CO—A r2 —CO — (2) One—Ar3 — Ο — (3) (Ar1 represents 2,6-anthranyl, 1,4-benzene Base or 4,4,_biphenyl. Αγ2 and 八1*3 are each unique, not 2,6-anthranyl, 1,4-phenylene, 1,3_phenyl or 4, 4'-biphenyl. The hydrogen atom of the above-mentioned group represented by Ar1, Ar2 or Ar3 may be independently substituted by a halogen atom, an alkyl group having 1 to 1 carbon number or an aryl group having 6 to 20 carbon atoms. The aforementioned halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the aforementioned alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-butyl, 3-butyl, n-hexyl, 2-ethylhexyl, The n-octyl group and the n-decyl group have a carbon number of usually 1 to 10. Examples of the above aryl group such as phenyl, anthracene-tolyl, m-tolyl, p-tolyl, iotaphthyl and 2-naphthyl have a carbon number of usually 6 to 20. When the hydrogen atom is substituted with such a group, the number of each of the above-mentioned groups represented by Ar1, Ar2 or Ar3 is usually two or less, preferably one or less. The repeating unit (1) is a repeating unit derived from a certain aromatic hydroxycarbonyl group. The repeating unit (1) is preferably a repeating unit of 6-carbamoyl-naphthoic acid in which Ar1 is 2,6. The repeating unit (2) is derived from a repeating unit of a certain aromatic dicarboxylic acid. The repeating unit (2) is Ar2 as a 2,6-anthranyl group (i.e., a repeating unit derived from 2,6-naphthalenedicarboxylic acid), and Ar2 is a 1,4-phenylene group (i.e., from p-phenylene 201228826 dicarboxylic acid). Repeat unit) is preferred. The repeating unit (3) is a repeating unit derived from a certain aromatic diol. The repeating unit (3) is Ar3 as 1,4-phenylene (ie, repeating unit derived from hydroquinone), and Ar3 is 4,4'-biphenyl (ie, repeating from 4,4'-dihydroxybiphenyl) Unit) is preferred. In the liquid crystal polyester, the content of the repeating unit with respect to the 2,6-extended naphthyl group, that is, the repetition unit (1) in which Ar1 is a 2,6-anthranyl group, and the repetition of 2,6-anthranyl group in Ar2. The total content of the unit (2) and the repeating unit (3) in which Ar3 is 2,6-anthranyl group is divided by the total amount of all repeating units (by dividing the mass of each repeating unit constituting the liquid crystal polyester by each The amount of the unit of the repeating unit is determined by taking the equivalent amount of the substance of each repeating unit (mole), and in total, 40 mol% or more, by making the liquid crystal having a unit of a certain repeating unit. The polyester is thinned to obtain a liquid crystal polyester film excellent in water vapor barrier properties. The content of the 2,6-anthracene group is preferably 5 莫 mol% or more, more preferably 60 摩尔% or more, and most preferably 70 摩尔/0 or more. Further, the content of the repeating unit (1) in the liquid crystal polyester is preferably from 30 to 80 mol%, more preferably from 40 to 70 mol%, based on the total amount of all repeating units. The ratio is 45 to 65 mol%; the content of the repeating unit (2) is preferably 1 〇 to 3 5 mol%, and more preferably 1 5 to 3 0 with respect to the total amount of all repeating units. Molar%, the best is 17.5~27.5 mol%: the content of the repeating unit (3) is preferably 10 to 35 mol%, more than the total amount of all repeating units. For 15~30 mol%, the best is 17.5~27.5 mol%. The liquid crystal polyester having a repeating unit composition of -8 - 201228826 is excellent in balance between heat resistance and formability. Further, the content of the 'repeating unit (2) and the content of the repeating unit (3)' are substantially equal. Further, the liquid crystal polyester may have a repeating unit other than the repeating units (1) to (3) as needed, but the content thereof is usually 10 mol% or less with respect to the total amount of all repeating units, preferably The amount is 5 mol% or less. A typical example of a liquid crystal polyester having high heat resistance or high melt tension has a repeating unit (1) in which Ar1 is a 2,6-anthranyl group relative to the total of all repeating units (i.e., from 6-hydroxy-2- The repeating unit of benzoic acid, preferably 40 to 74_8 mol%, more preferably 40 to 64_5 mol%, and most preferably 50 to 58 mol%), having Ar2 as 2,6-anthranyl group The repeating unit (2) (i.e., the repeating unit derived from 2,6-naphthalenedicarboxylic acid, preferably 12.5 to 30 mol%, more preferably 17.5 to 30 mol%, and most preferably 20 to 25) Mohr%), having a repeating unit of Ar2 as a 1,4-phenylene group (2) (i.e., a repeating unit derived from terephthalic acid, preferably 0.2 to 15 mol. /, more preferably 0.5) ~12mol%, the best is 2~10mol%), and the repeating unit (3) with Ar3 being 1,4-phenylene (ie repeating unit from hydroquinone) is preferably 1 2 · 5~3 0 mol%, more preferably 1 7.5~3 0 mol%, the best is 20~25 mol%), and Ar2 is a repeating unit of 2,6-strandyl (2) The content of the repeating unit (2) of 2,6-anthranyl group with respect to Ar2 and the 1,4-benzene extending of Ar2 The total content of the repeating units (2) of the base is preferably 0.5 mol or more, more preferably 0.6 mol or more. The liquid crystal polyester can be a monomer having a repeating unit (1) (that is, a certain aromatic hydroxycarboxylic acid) and a monomer having a repeating unit (2) ( -9 - 201228826 is a certain aromatic dicarboxylic acid And a monomer having a repeating unit (3) (ie, a certain aromatic diol)' in a total amount of a monomer having a 2,6-anthranyl group (ie, 6-hydroxy-2-naphthoic acid, 2, The total amount of 6-naphthalenedicarboxylic acid and 2,6-naphthalenediol is 40 mol% or more based on the total amount of all the monomers, and is obtained by polymerization (polycondensation). In this case, a part or all of each of the aromatic hydroxycarboxylic acid, the aromatic dicarboxylic acid, and the aromatic diol may be substituted with a polymerizable derivative. Examples of polymerizable derivatives of a compound having a carboxyl group of an aromatic hydroxycarboxylic acid and an aromatic dicarboxylic acid, which convert a carboxyl group into an alkoxycarbonyl group or an aryloxycarbonyl group, and convert a carboxyl group into a halogenated formamidine. The group is formed by converting a carboxyl group into a decyloxycarbonyl group. Examples of the polymerizable derivative of a compound having a hydroxyl group of an aromatic hydroxycarboxylic acid and an aromatic diol are those obtained by thiolation of a hydroxy group to conversion to a decyloxy group. Further, the liquid crystal polyester is preferably produced by solid-phase polymerization of the obtained polymer (prepolymer) by melt polymerization of a monomer. Thereby, a liquid crystal polyester having high heat resistance or high melt tension can be produced with good workability. The melt polymerization can be carried out in the presence of a catalyst such as a metal compound such as magnesium acetate, tin acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate or antimony trioxide, or N,N-dimethyl The nitrogen-containing heterocyclic compound such as aminopyridine or N-methylimidazole is preferably a nitrogen-containing heterocyclic compound. The flow start temperature of the liquid crystal polyester is preferably 28 ° C or higher, more preferably 290 ° C or higher, and most preferably 29 5 ° C or higher, and usually 380 ° C or lower, preferably 35 (TC or less. The higher the flow start temperature, the more easily the heat resistance or the melt tension is increased, but when it is relatively high, it is necessary to use a high temperature in order to melt, and it is easy to cause heat deterioration during molding. Moreover, the flow start temperature, also referred to as flow temperature or flow temperature, is a capillary ammeter using a nozzle having an inner diameter of 1 mm and a length of 10 mm, at a load of 9.8 MPa (100 kg/cm 2 ), at * 4 ° When the heating rate of C / min is such that the heated melt of the liquid crystal polyester is pushed out from the nozzle, the melt viscosity is 4 800 Pa · s (48,000 poise), which is a molecular weight of the liquid crystal polyester. "Liquid Crystal Polymers - Synthesis and Forming Applications -", CMC Corporation, June 5, 1987, p95). In liquid crystal polyesters, other components may be used as a composition depending on their needs. Examples of ingredients, such as sputum filling The thermoplastic resin and the additive other than the liquid crystal polyester. The proportion of the liquid crystal polyester in the entire composition is preferably 80% by mass or more, and more preferably 90% by mass or more. Grinding glass fibers, short glass fibers, etc., glass or potassium titanate whiskers, alumina whiskers, aluminum borate whiskers, tantalum carbide whiskers, tantalum nitride whiskers, etc., metal or non-metal whiskers, Glass beads, hollow glass spheres, glass powder, mica, talc, clay, silica sand, alumina, potassium titanate, ash, calcium carbonate (heavy, lightweight 'colloidal, etc.), magnesium carbonate, alkaline carbonic acid Magnesium, sodium sulfate, potassium sulfate, barium sulfate, sulfurous acid
V 酸鈣、氫氧化鋁、氫氧化鎂、氫氧化鈣、矽酸鈣、矽砂、 矽石、石英、氧化鈦、氧化鋅、氧化鐵、石墨、鉬、石綿 、二氧化矽氧化鋁纖維、氧化鋁纖維、石膏纖維、碳纖維 . '碳黑 '白碳、矽藻土、膨潤土、絹雲母、白砂及黑鉛， 視其所需亦可使用此等之2種以上。其中，以使用玻璃纖 -11 - 201228826 維、雲母、滑石及碳纖維較佳。 視其所需，塡充材亦可爲經表面處理者，該表面處理 劑例如矽烷系偶合劑、鈦酸酯系偶合劑、硼烷系偶合劑等 之反應性偶合劑、及高級脂肪酸、高級脂肪酸酯、高級脂 肪酸金屬鹽、氟碳系界面活性劑等之潤滑劑。 除液晶聚酯以外之熱可塑性樹脂之例，如聚碳酸酯、 聚醯胺、聚颯、聚硫化亞苯基、聚亞苯醚' 聚醚酮及聚醚 醯亞胺樹脂。 添加劑之例，如氟樹脂、金屬皂類等之離型改良劑、 核劑、抗氧化劑、安定劑、可塑劑、平滑劑、防止著色劑 、著色劑、紫外線吸收劑、抗靜電劑、潤滑劑及難燃劑。 藉由使該所得的液晶聚酯或其組成物予以薄膜化，可 製得形成本發明之離型薄膜的基材層之液晶聚酯薄膜。薄 膜化的方法，例如押出成形法、壓製成形法、溶液流延法 及射出成形法，以押出成形法較佳。押出成形法例如T塑 模法或膨脹法，爲T塑模法時，可爲一軸延伸、亦可爲二 軸延伸β —軸延伸薄膜之延伸倍率（拉伸率），通常爲1」〜 40、較佳者爲10〜40、更佳者爲15〜35。二軸薄膜之MD 方向（押出方向）的延伸倍率，通常爲1.2〜40倍，二軸 薄膜之TD方向（垂直於押出方向之方向）的延伸倍率， 通常爲1.2〜20倍。膨脹薄膜之MD方向的延伸倍率（下 引（draw down )比=氣泡引出速度/樹脂吐出速度），通 常爲1.5〜50、較佳者爲5〜30，膨脹薄膜之TD的延伸倍 -12- 201228826 率（吹出比=氣泡直徑/環狀隙縫直徑）’通常爲1.5〜10 、較佳者爲2〜5。 液晶聚酯薄膜之厚度’較佳者爲5〜1〇〇μπι、更佳者 爲10〜75μιη、最佳者爲15〜75μιη。相當薄時，強度變得 不充分，相當厚時，可撓性變得不充分。 該所得的液晶聚酯薄膜，藉由前述由具有一定的重複 單位組成之液晶聚酯所構成，耐水性優異，以溫度4 0 t及 相對濕度9 0 %所測定的水蒸氣透過率，較佳者爲〇. 1 g/m2 · 24h以下、更佳者爲0.05 g/m2 · 24h以下。 藉由在液晶聚酯薄膜之至少一面上設置離型層，可製 得本發明之離型薄膜。離型層以其水接觸角爲70°以上較 佳，以8 0 °以上更佳。 離型層通常由樹脂所構成，該樹脂之例如聚矽氧樹脂 、聚烯烴樹脂、醇酸樹脂、含長鏈烷基之樹脂及氟樹脂， 視其所需亦可使用此等之2種以上。其中，以使用聚矽氧 樹脂或氟樹脂較佳。 離型層係可使構成該層之樹脂或其原料之聚合性化合 物，視其所需予以溶解或分散於溶劑中，塗佈於液晶聚酯 薄膜，且使用溶劑時使其蒸發除去，使用聚合性化合物時 ，藉由光或熱以使該物聚合硬化而設置。而且，在轉印薄 膜上設置構成離型層之樹脂或其原料之聚合性化合物之層 ，然後，使該層轉印於液晶聚酯薄膜上，且使用聚合性化 合物時，亦可藉由使其藉由光或熱予以聚合硬化而設置。 該所得的本發明之離型薄膜，由於耐水性優異，於電 -13- 201228826 子零件製造時或保管時或加工時，適合使用作爲保護電子 零件或其構件時之薄膜。例如，於多層印刷基板之製造過 程中，在使芯基板與絕緣薄膜或貼銅積層板藉由熱壓製進 行積層的步驟時，適合作爲存在於壓製盤與絕緣薄膜或貼 銅積層板之間的保護薄膜。 【實施方式】 [實施例] [流動開始溫度之測定] 使用FLOW TESTER (島津製作所（股）之「CFT-500 型」）’將試料約2g塡充於設置有內徑1mm、長度10mm 之噴嘴的毛細管型電流計，在9.8MPa( 100kgf/cm3)之荷 重下，以昇溫速度4°C /分鐘將試料熔融且押出，測定展現 熔融黏度爲4800Pa.s( 48000泊）之溫度。 [耐水性之評估] 以JIS K7 126(A法：差壓法）爲基準，藉由氣體透 過率•透濕度測定裝置（GTR Tech (股）之「GTR-10X」 )’以溫度40°C、相對濕度90%之條件測定水蒸氣透過率 製造例1 在具備攪拌裝置、轉距測定器、氮氣導入管、溫度計 及回流冷卻器之反應器中，加入6_羥基·2·萘甲酸 -14- 201228826 1034.99g ( 5.5 莫耳）、2,6-萘二羧酸 378.33g ( 1.75 莫耳 )、對苯二甲酸83.07g(0.5莫耳）、氫醌272.52g( 2.475莫耳：相對於2,6 -萘二羧酸及對苯二甲酸之合計量 而言爲0.225莫耳之過剩量）、醋酸酐1226.87g ( 12莫耳 )及作爲觸媒之1-甲基咪唑〇」7g，使反應器內之氣體以 氮氣取代後，在氮氣氣流下進行攪拌’同時在15分鐘內 自室溫昇溫至145 °C爲止，且在145°C下進行回流1小時。 然後，餾去副生成醋酸及未反應的醋酸酐，再於3小時30 分鐘內自1 4 5 °C昇溫至3 1 0 °C爲止，且在3 1 0 t下保持3小 時後，取出內容物，冷卻至室溫。使所得的固成物以粉碎 機粉碎成粒徑約0.1〜1mm後，藉由在氮氣氣氛下，在1 小時內自室溫昇溫至25(TC爲止，且在10小時內自250°C 昇溫至3 10°C爲止，在310°C下保持5小時，進行固相聚合 。固相聚合後，予以冷卻，製得粉末狀液晶聚酯。該液晶 聚酯，相對於全部重複單位之合計量而言，具有Ar1爲 2,6-伸萘基之重複單位（1 ) 55莫耳％ ' Ar2爲2,6-伸萘基 之重複單位（2 ) 17.5莫耳％、Ar2爲1，4-伸苯基之重複單 位（2) 5莫耳％、及Ar3爲1，4-伸苯基之重複單位（3) 22.5莫耳％，且其流動開始溫度爲3 3 3 °C。 製造例2 在與製造例1相同的反應器中，加入ρ·羥基苯甲酸 911g(6.6莫耳）、對苯二甲酸274g(1.65莫耳）、異苯 二甲酸91g( 0.55莫耳）、4,4’-二羥基聯苯409§(2.2莫 -15- 201228826 耳）、醋酸酐1235g(12.1莫耳）及作爲觸媒之1-甲基咪 哩0.17g，使反應器內之氣體以氮氣取代後，在氮氣氣流 下進行攪拌，同時在15分鐘內自室溫昇溫至15(TC爲止， 且在1 5 0 °C下進行回流1小時。然後，添加1 -甲基咪唑 1.7g後，餾去副生成醋酸及未反應的醋酸酐，再於2小時 50分鐘內自150 °C昇溫至32(TC爲止，於確認轉矩上昇時 ，取出內容物，冷卻至室溫。使所得的固成物以粉碎機粉 碎成粒徑約0.1〜1mm後，藉由在氮氣氣氛下，在1小時 內自室溫昇溫至2 5 0 °C爲止，且在5小時內自2 5 0 °C昇溫至 2 8 5 °C爲止，在28 5 °C下保持3小時，進行固相聚合。於固 相聚合後，予以冷卻，製得粉末狀液晶聚酯。該液晶聚酯 具有Ar1爲1，4-伸苯基之重複單位（1 ) 60莫耳％、Ar2爲 1,4-伸苯基之重複單位（2) 15莫耳％、Ar2爲1，3-伸苯基 之重複單位（2 ) 5莫耳％、及Ar3爲4,4’-聯苯基之重複單 位（3 ) 20莫耳％，且其流動開始溫度爲3 27°C。 實施例1 使以製造例1所得的液晶聚酯以二軸押出機（池貝（ 股）公司之「PCM-30」）進行造粒，形成粒料狀後，供 應給一軸押出機（螺旋直徑5 0mm )予以熔融，自T塑模 (端部長度300mm、端部間距 1mm、塑模溫度 350 °C) 以薄膜狀押出，予以冷卻，製得厚度2 5 μηι之液晶聚酯薄 膜。該液晶聚酯薄膜之水蒸氣透過率爲0.0 11 g/m2 · 24h以 下，作爲離型薄膜之基材層時，耐水性優異。 -16- 201228826 比較例1 除使用以！ 得的液晶聚酯d 2 5μιη之液晶衰 爲 0.3 43 g/m2 水性不充分。 ¥造例2所得的液晶聚酯取代以製造例1所 卜，進行與實施例1相同的操作，製得厚度 酯薄膜。該液晶聚酯薄膜之水蒸氣透過率 •24h以下，作爲離型薄膜之基材層時，耐 -17-V calcium acid, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium citrate, barium sand, vermiculite, quartz, titanium oxide, zinc oxide, iron oxide, graphite, molybdenum, asbestos, cerium oxide alumina fiber, Alumina fiber, gypsum fiber, carbon fiber, 'carbon black' white carbon, diatomaceous earth, bentonite, sericite, white sand and black lead, and two or more of these may be used as needed. Among them, it is preferable to use glass fiber-11 - 201228826 dimension, mica, talc and carbon fiber. Depending on the requirements, the ruthenium filler may be a surface treatment agent such as a cyclane coupling agent, a titanate coupling agent, a borane coupling agent, or the like, and a higher fatty acid or higher. A lubricant such as a fatty acid ester, a higher fatty acid metal salt, or a fluorocarbon surfactant. Examples of thermoplastic resins other than liquid crystal polyesters, such as polycarbonate, polyamide, polyfluorene, polysulfoxyphenylene, polyphenylene ether, polyetherketone, and polyetherimide resins. Examples of additives, such as release modifiers for fluororesins, metal soaps, nucleating agents, antioxidants, stabilizers, plasticizers, smoothing agents, colorants, colorants, UV absorbers, antistatic agents, lubricants And flame retardant. By subjecting the obtained liquid crystal polyester or a composition thereof to film formation, a liquid crystal polyester film which forms a base material layer of the release film of the present invention can be obtained. The film forming method, for example, the extrusion molding method, the press molding method, the solution casting method, and the injection molding method, is preferably carried out by extrusion molding. The extrusion molding method such as the T molding method or the expansion method may be a one-axis extension or a stretching ratio (stretching ratio) of the biaxially stretched β-axis stretching film, which is usually 1" to 40. Preferably, it is 10 to 40, and more preferably 15 to 35. The stretching ratio of the MD direction (extrusion direction) of the biaxial film is usually 1.2 to 40 times, and the stretching ratio of the TD direction (the direction perpendicular to the extrusion direction) of the biaxial film is usually 1.2 to 20 times. The stretching ratio in the MD direction of the expanded film (draw down ratio = bubble take-up speed / resin discharge speed) is usually 1.5 to 50, preferably 5 to 30, and the stretch of the TD of the expanded film is -12 - The ratio of 201228826 (blowing ratio = bubble diameter / annular slit diameter) 'is usually 1.5 to 10, preferably 2 to 5. The thickness of the liquid crystal polyester film is preferably 5 to 1 〇〇 μm, more preferably 10 to 75 μm, and most preferably 15 to 75 μm. When it is relatively thin, the strength is insufficient, and when it is relatively thick, the flexibility is insufficient. The obtained liquid crystal polyester film is composed of the liquid crystal polyester having a certain repeating unit composition, and is excellent in water resistance, and is preferably water vapor transmission rate measured at a temperature of 40 t and a relative humidity of 90%. It is 〇. 1 g/m2 · 24h or less, and more preferably 0.05 g/m2 · 24h or less. The release film of the present invention can be obtained by providing a release layer on at least one side of a liquid crystal polyester film. The release layer preferably has a water contact angle of 70 or more, more preferably 80 or more. The release layer is usually composed of a resin such as a polyoxyxylene resin, a polyolefin resin, an alkyd resin, a long-chain alkyl group-containing resin, and a fluororesin, and two or more kinds of these may be used as needed. . Among them, it is preferred to use a polyoxymethylene resin or a fluororesin. The release layer can be obtained by dissolving or dispersing a polymerizable compound constituting the resin of the layer or a raw material thereof in a solvent, applying it to a liquid crystal polyester film, and evaporating and removing it using a solvent, using polymerization. In the case of a compound, it is provided by light or heat to cure the substance by polymerization. Further, a layer of a polymerizable compound constituting the release layer or a raw material of the raw material is provided on the transfer film, and then the layer is transferred onto the liquid crystal polyester film, and when a polymerizable compound is used, It is provided by polymerization hardening by light or heat. The obtained release film of the present invention is excellent in water resistance, and is preferably used as a film for protecting an electronic component or a member thereof during the production of a sub-part of the electric device or during storage or processing. For example, in the manufacturing process of the multilayer printed substrate, when the core substrate and the insulating film or the copper-clad laminate are laminated by hot pressing, it is suitable to be present between the pressed disk and the insulating film or the copper-clad laminate. Protective film. [Embodiment] [Examples] [Measurement of Flow Start Temperature] Using FLOW TESTER ("CFT-500 Model" of Shimadzu Corporation), about 2 g of the sample was filled with a nozzle having an inner diameter of 1 mm and a length of 10 mm. The capillary galvanometer was melted and extruded at a temperature increase rate of 4 ° C /min under a load of 9.8 MPa (100 kgf/cm 3 ), and the temperature at which the melt viscosity was 4,800 Pa·s (48,000 poise) was measured. [Evaluation of water resistance] Based on JIS K7 126 (A method: differential pressure method), the gas permeability and moisture permeability measuring device (GTR-10X of GTR Tech) are at a temperature of 40 °C. Measurement of water vapor transmission rate under conditions of a relative humidity of 90% Production Example 1 In a reactor equipped with a stirring device, a torque measuring device, a nitrogen gas introduction tube, a thermometer, and a reflux condenser, 6-hydroxy-2 naphthoic acid-14 was added. - 201228826 1034.99g (5.5 mol), 378.33g (1.75 mol) of 2,6-naphthalenedicarboxylic acid, 83.07g (0.5 mol) of terephthalic acid, and 272.52g of hydroquinone (2475 mil: relative to 2 , the total amount of 6-naphthalenedicarboxylic acid and terephthalic acid is 0.225 mol, and the acetic anhydride is 1226.87 g (12 mol) and the 1-methylimidazolium as a catalyst is 7 g. After the gas in the reactor was replaced with nitrogen, it was stirred under a nitrogen gas stream while raising the temperature from room temperature to 145 ° C in 15 minutes, and refluxing at 145 ° C for 1 hour. Then, the by-produced acetic acid and unreacted acetic anhydride were distilled off, and the temperature was raised from 1 4 5 ° C to 3 10 ° C in 3 hours and 30 minutes, and kept at 3 10 t for 3 hours, and then the contents were taken out. Store to cool to room temperature. After the obtained solid product is pulverized into a particle diameter of about 0.1 to 1 mm by a pulverizer, the temperature is raised from room temperature to 25 (TC) in 1 hour under a nitrogen atmosphere, and the temperature is raised from 250 ° C in 10 hours. 3, 10 ° C, held at 310 ° C for 5 hours, solid phase polymerization. After solid phase polymerization, cooling, to obtain a powdery liquid crystal polyester. The liquid crystal polyester, relative to the total of all repeat units That is, the repeat unit having Ar1 is 2,6-anthranyl group (1) 55 mol% 'Ar2 is a repeating unit of 2,6-anthranyl group (2) 17.5 mol%, Ar2 is 1,4-stretch Repeating unit of phenyl group (2) 5 mol %, and Ar3 is a repeating unit of 1,4-phenylene group (3) 22.5 mol%, and its flow initiation temperature is 3 3 3 ° C. Production Example 2 In the same reactor as in Production Example 1, 911 g (6.6 mol) of p-hydroxybenzoic acid, 274 g (1.65 mol) of terephthalic acid, 91 g (0.55 mol) of isophthalic acid, and 4,4'- were added. Dihydroxybiphenyl 409 § (2.2 Mo-15 - 201228826 ears), acetic anhydride 1235 g (12.1 mol) and 1-methyl oxime 0.17 g as a catalyst, after the gas in the reactor was replaced by nitrogen, nitrogen The mixture was stirred under a gas stream, and the temperature was raised from room temperature to 15 (TC) in 15 minutes, and refluxed at 150 ° C for 1 hour. Then, after adding 1.7 g of 1-methylimidazole, the by-produced acetic acid was distilled off. The unreacted acetic anhydride was heated from 150 ° C to 32 (TC) in 2 hours and 50 minutes. When the torque was increased, the contents were taken out and cooled to room temperature. The obtained solid product was pulverized by a pulverizer. After the particle size is about 0.1 to 1 mm, the temperature is raised from room temperature to 250 ° C in 1 hour in a nitrogen atmosphere, and the temperature is raised from 2500 ° C to 2 8 5 ° C in 5 hours. The solid phase polymerization was carried out at 28 ° C for 3 hours, and after solid phase polymerization, it was cooled to obtain a powdery liquid crystal polyester having a repeating unit of Ar 1 being a 1,4-phenylene group. (1) 60 mol%, Ar2 is a repeating unit of 1,4-phenylene (2) 15 mol%, Ar2 is a repeating unit of 1,3-phenylene (2) 5 mol%, and Ar3 It is a repeating unit of 4,4'-biphenylyl group (3) 20 mol%, and its flow initiation temperature is 3 27 ° C. Example 1 The liquid crystal polyester obtained in Production Example 1 was subjected to two-axis press The machine (Chiba (stock) company's "PCM-30") is granulated and formed into pellets, and then supplied to a one-axis extruder (spiral diameter 50 mm) to be melted, from T mold (end length 300 mm, end) The pitch was 1 mm and the mold temperature was 350 ° C. The film was extruded and cooled to obtain a liquid crystal polyester film having a thickness of 25 μm. The liquid crystal polyester film has a water vapor transmission rate of 0.01 g/m2 · 24 hours or less, and is excellent in water resistance when used as a base layer of a release film. -16- 201228826 Comparative Example 1 In addition to use! The liquid crystal polyester d 2 5 μιη obtained had a liquid crystal decay of 0.343 g/m2 and the water content was insufficient. The liquid crystal polyester obtained in the production example 2 was replaced by the production example 1, and the same operation as in the example 1 was carried out to obtain a thickness ester film. The liquid crystal polyester film has a water vapor transmission rate of 24 hours or less, and is used as a base layer of a release film to resist -17-