201221560 • 六、發明說明： . 【發明所屬之技術領域】 本發明係關於一種積層膜’其具有由液蟲聚酯所構成 之基材層、與水蒸氣阻隔（barrier)層。此外，本發明係 關於使用此積層膜作為基板而成之附電極的積層膜以及有 機 EL (electroluminescence，電致發光）元件。 【先前技術】 有機EL元件通常具有於基板上配置一對電極並於此 一對電極間配置有機EL·層所成之構造，其例子示於第1 圖。在該例子中，於基板1上依序配置陰極4A、有機EL 層5及陽極4B ’再於其上配置密封層6，且以密封材7密 封基板1與密封層6之間的周圍部。此外，有機EL層5 係由發光層5b、於其陰極4A侧所配置之電子輸送層5a、 及於其陽極48侧所配置之電洞輸送層5c所構成。 基板1通常係使用玻璃基板，但因其缺乏可撓性 (flexilnhty)故難以連續生產有機EL元件，此外’有 不耐衝擊、重量重之缺點。於是，檢討使用樹脂膜作為基 板1 ’但與玻璃板相比，樹脂膜有氣體阻隔性及尺寸安定 性低之問題。為了解決該等問題，而檢討使用液晶聚醋膜 作為樹月曰膜並於其上配置氣體阻隔層所成之積層膜。例如 專利文獻1揭不構成前述液晶聚醋膜之液晶聚合物係下述 #·具有源自4’4’-二減聯苯之重複單元、源自鄰苯二 甲酸之重複單7C、及源自對經基苯甲酸之重複單元的聚 -曰八有源自6輕基-2-萘曱酸（6-hydroxy-2-naphthoic 4 323490 201221560 acid)之重複單元及源自對羥基苯曱酸之重複單元的聚 酯；具有源自乙二醇之重複單元、源自對苯二甲酸之重複 單元、及源自對羥基苯甲酸之重複單元的聚酯；以及具有 源自6-羥基-2-萘曱酸之重複單元、源自對胺基酚之重複 單兀、及源自對苯二曱酸之重複單元的聚酯醯胺 (polyesteramide)° [先前技術文獻] (專利文獻） 專利文獻1 :日本特開2009-32464號公報 【發明内容】 (發明欲解決之課題） 如專利文獻1所揭示，以往之具有由液晶聚酯或液晶 聚酯醯胺所構成之基材層與氣體阻隔層的積層膜，係因基 材層的水蒸氣阻隔性不一定充足，故會根據氣體阻隔層之 種類不同，而可能有水蒸氣阻隔性不足之情形。於是，本 發明之目的係提供一種水蒸氣阻隔性優異之積層膜，其具 有由水蒸氣阻隔性優異之液晶聚酯所構成之基材層、及水 蒸氣阻隔層。 (解決課題之手段） 為了達成前述目的，本發明提供一種積層膜，其具有 由液晶聚酯所構成之基材層、以及於前述基材層的至少一 面上所配置之水蒸氣阻隔層；前述液晶聚酯具有下述式（1 ) 所不之重複單元、下述式（2)所示之重複單元、及下述式 (3)所示之重複單元；式及.所示重複單 5 323490 201221560 元中之至少—者含有2 6—伸萘基，相對於全重複單元合計 量’含有該2,6~伸萘基之重複單元的含量為40莫耳％以 上。 —0— Ar1 —CO— (1) —CO —Ar2 —CO— (2) -0-Ar3-〇- (3) —式=’ Arl表示2, 6-伸萘基、1，4-伸苯基或4, 4，-伸聯 苯基Ar及Ar各自獨立地表示2, 6_伸萘基、1，伸苯基、 1 ’ 3-伸苯基或4, 4’ -伸聯苯基。2, 6_伸萘基、丨，4—伸苯基、 1，3-伸苯基或4, 4,-伸聯苯基巾的氫料可各自獨立地經 鹵素原子、烷基或芳基取代。 本發明提供一種積層膜，其具有：基材層，其係由液 晶聚酯所構成，且該基材層係在溫度4(rc及相對溼度9〇 %所測定的水蒸氣穿透度為〇 〇〇5g/m2· 24h以下者；以及 水蒸氣阻隔層，其係配置於前述基材層的至少一面上。 此外，本發明提供一種積層膜，其具有：由液晶聚酯 所構成之基材層，該液晶聚酯係在製成厚度5〇/zm的膜 時’在溫度4(TC及相對溼度90%所測定的水蒸氣穿透度為 〇.〇〇5g/m2 · 24h以下者；以及水蒸氣阻隔層，其係配置於 前述基材層的至少一面上。 另外’本發明提供一種附電極的積層膜，其具有：前 述任一積層膜、以及於前述積層膜的至少一面上所配置之 電極。 再者，本發明提供一種有機EL元件，其具有：前述任 6 323490 201221560 一積層膜、於前述積層膜上所配置之一對電極、以及於前 述一對電極間所配置之有機EL層。 (發明之效果） 本發明之積層膜因具有由水蒸氣阻隔性優異之液晶聚 酉曰所構成之基材層及水蒸氣阻隔層，故水蒸氣阻隔性優 異，適合使用作為有機EL元件之基板。 【實施方式】 構成本實施型態之積層膜之基材層的液晶聚酯，係在 熔融時會展現光學異向性（opticalanis〇tr〇py)之聚酯， 且具有下述式（1)所示之重複單元（以下亦稱為「重複單 兀（1)」）、下述式（2)所示之重複單元（以下亦稱為「重 複單元（2)」）、及下述式（3)所示之重複單元（以下亦稱 為「重複單元（3)」）。 —0 —Ar 丨-CO- (1) —CO —Ar2-C0— (2) —0 — Ar3 — 〇— (3)201221560 • Technical Description of the Invention The present invention relates to a laminated film which has a substrate layer composed of a liquid insect polyester and a water vapor barrier layer. Further, the present invention relates to a laminated film using an electrodeposited film as a substrate and an organic EL (electroluminescence) element. [Prior Art] The organic EL device usually has a structure in which a pair of electrodes are arranged on a substrate and an organic EL layer is disposed between the pair of electrodes, and an example thereof is shown in Fig. 1. In this example, the cathode 4A, the organic EL layer 5, and the anode 4B' are disposed on the substrate 1 in this order, and the sealing layer 6 is disposed thereon, and the peripheral portion between the substrate 1 and the sealing layer 6 is sealed with a sealing material 7. Further, the organic EL layer 5 is composed of a light-emitting layer 5b, an electron transport layer 5a disposed on the cathode 4A side thereof, and a hole transport layer 5c disposed on the anode 48 side thereof. Although the glass substrate is usually used for the substrate 1, it is difficult to continuously produce an organic EL element because of its lack of flexibility, and there is a disadvantage that it is not resistant to impact and heavy. Then, the resin film was used as the substrate 1', but the resin film has a problem that gas barrier properties and dimensional stability are lower than those of the glass plate. In order to solve such problems, a laminated film formed by using a liquid crystal polyester film as a sapphire film and having a gas barrier layer disposed thereon was reviewed. For example, Patent Document 1 discloses a liquid crystal polymer which does not constitute the liquid crystal polyacetal film, and has a repeating unit derived from 4'4'-disubstituted biphenyl, a repeating single 7C derived from phthalic acid, and a source. The poly-p-octane from the repeating unit of p-benzoic acid has a repeating unit derived from 6-hydroxy-2-naphthoic 4 323490 201221560 acid and is derived from p-hydroxybenzoic acid. a polyester of a repeating unit; a polyester having a repeating unit derived from ethylene glycol, a repeating unit derived from terephthalic acid, and a repeating unit derived from p-hydroxybenzoic acid; and having a source derived from 6-hydroxy-2 - a repeating unit of naphthoic acid, a repeating monoquinone derived from a p-aminophenol, and a polyesteramide derived from a repeating unit of terephthalic acid. [Prior Art Document] (Patent Literature) Patent Literature (Patent Disclosure of the Invention) As disclosed in Patent Document 1, a substrate layer composed of a liquid crystal polyester or a liquid crystal polyester decylamine is conventionally blocked from a gas. The laminated film of the layer is not necessarily sufficient due to the water vapor barrier property of the substrate layer. Therefore, depending on the type of gas barrier layer, there may be a situation in which the water vapor barrier property is insufficient. Accordingly, an object of the present invention is to provide a laminated film excellent in water vapor barrier property, which has a base material layer composed of a liquid crystal polyester excellent in water vapor barrier properties, and a water vapor barrier layer. In order to achieve the above object, the present invention provides a laminated film comprising a base material layer composed of a liquid crystal polyester and a water vapor barrier layer disposed on at least one surface of the base material layer; The liquid crystal polyester has a repeating unit of the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula (3); and a repeating single 5 323490 At least one of the elements of 201221560 contains a 6-n-naphthyl group, and the content of the repeating unit containing the 2,6-strandyl group is 40 mol% or more with respect to the total repeat unit. —0— Ar1 —CO— (1) —CO —Ar—CO—(2) —0—Ar3-〇— (3) —Formula=' Arl denotes 2,6-anthranyl, 1,4-phenylene The group or 4, 4,-extended biphenyl group Ar and Ar each independently represent 2,6-anthracene, 1, phenyl, 1 '3-phenyl or 4,4'-biphenyl. The hydrogen materials of 2,6_anthylene, anthracene, 4-phenylene, 1,3-phenylene or 4,4,-extended biphenyl can each independently pass through a halogen atom, an alkyl group or an aryl group. Replace. The present invention provides a laminated film comprising: a substrate layer composed of a liquid crystal polyester, and the substrate layer is at a temperature of 4 (rc and a relative humidity of 9〇%, the water vapor permeability is 〇 〇〇5g/m2·24h or less; and a water vapor barrier layer disposed on at least one side of the base material layer. Further, the present invention provides a laminated film having a substrate composed of liquid crystal polyester a layer, the liquid crystal polyester is formed at a thickness of 5 〇 / zm 'at a temperature of 4 (TC and relative humidity of 90% measured by water vapor permeability of 〇. 〇〇 5g / m2 · 24h or less; And a water vapor barrier layer disposed on at least one surface of the base material layer. The present invention provides a laminated film with an electrode, comprising: any one of the laminated films, and at least one side of the laminated film Further, the present invention provides an organic EL device comprising: a laminated film of the above-mentioned 6 323 490 201221560, a counter electrode disposed on the laminated film, and an organic layer disposed between the pair of electrodes EL layer. (The effect of the invention) Since the laminated film of the present invention has a base material layer and a water vapor barrier layer composed of a liquid crystal polymer having excellent water vapor barrier properties, it is excellent in water vapor barrier property, and is preferably used as a substrate of an organic EL device. The liquid crystal polyester constituting the base material layer of the laminated film of the present embodiment is a polyester which exhibits optical anisotropy upon melting and has a repetition represented by the following formula (1). The unit (hereinafter also referred to as "repeated unit (1)"), the repeating unit represented by the following formula (2) (hereinafter also referred to as "repeating unit (2)"), and the following formula (3) Repeat unit (hereinafter also referred to as "repeating unit (3)"). -0 - Ar 丨 - CO - (1) - CO - Ar2-C0 - (2) - 0 - Ar3 - 〇 - (3)
Ar1表示2, 6-伸萘基、1，4-伸苯基或4, 4, _伸聯苯基。 Ar及Ar3各自獨立地表示2, 6-伸萘基、1，4-伸苯基、丨，3一 伸苯基或4,4’-伸聯苯基。紅1、^2或人1'3所示之前述基中 的氫原子，亦即2, 6-伸萘基、ι，4-伸苯基、1，3-伸苯基或 4, 4’ -伸聯苯基中的氫原子，係可各自獨立地經齒素原子、 碳數1至10之烧基或碳數6至2〇之芳基取代。 前述鹵素原子可列舉如氟原子、氯原子、溴原子及碘 原子。前述烷基之例可列舉：甲基、乙基、正丙基、異丙 323490 7 201221560 基、異丁基、第二丁基、第三丁基正己基、2— 基、正辛基及正癸基’其碳數通常為… ^。 甲本基、間甲苯基、對甲苯基、 奈基及2-萘基，其碳數通常為6 等基取代時，於每個“、^ 2(^心原子經此 ^批 Ar或Ar3所示之前述基，取代 土之目係各自獨立地通常為2個以下，較佳為丨個以下。 —⑴係源自預定之芳香_基紐之重複單 ( 1 )較佳係A""為2, 6~伸萘基者(亦即源自 6-羥基-2-萘甲酸之重複單元）。 _ f複單元⑴係源自狀之料族二㈣之重複單. ^複早70 ( 2 )較佳係：紅2為2, 6-伸萘基者（亦即源 ，6一伸善基二紐之重複單元）、以及Ar24 1，4-伸苯 基者（亦即源自對苯二甲酸之重複單元）。 重複單元⑺係源自預定之芳香族二醇之重複 錢單以3)較佳係：ΑΓ3為1 士伸笨基者（亦即源自對 本二酚（hydroquinone)之重複單元）、以及 伸聯苯基者（亦即源自4,4，_二祕聯苯之重複單元）’。4_ 本實施形態之液晶聚酯係在式（1)、（2)及（3) 重複單元中之至少-者含有2,6_伸萘基，相對於全重複= 疋合計量，含有該2, 6-伸萘基之重複單元的含量為* 耳％以上。 、 液晶聚醋中，相對於全重複單元合計量（.將構成液曰 聚醋之各重複單元的質量除以各重複單元的式量，而求曰日 各重複單元的物質量相當量（莫耳），並將該等值予以人士十 323490 8 201221560 之值），含有2, 6-伸萘基之重複單元的含量（亦即Ar1為 2, 6-伸萘基之重複單元（1)、Ar2為2, 6-伸萘基之重複單 元（2)、及Ar3為2, 6-伸萘基之重複單元（3)的合計含量） 為40莫耳％以上。藉此可提高基材層之水蒸氣阻隔性。此 2, 6-伸萘基之含量較佳為50莫耳％以上，更佳為60莫耳 %以上，又更佳為70莫耳％以上。 此外，液晶聚酯中，相對於全重複單元合計量，重複 單元（1)的含量較佳為30至80莫耳％，更佳為40至70 莫耳％，又更佳為45至65莫耳％。此外，相對於全重複 單元合計量，重複單元（2)的含量較佳為10至35莫耳％， 更佳為15至30莫耳％，又更佳為17. 5至27. 5莫耳％。 再者，相對於全重複單元合計量，重複單元（3)的含量較 佳為10至35莫耳％，更佳為15至30莫耳％，又更佳為 17.5至27.5莫耳％。具有此等預定的重複單元組成之液 晶聚酯，其耐熱性與成形性之平衡優異。此外，重複單元 (2)的含量與重複單元（3)的含量較佳為實質上相等。 此外，液晶聚酯可視需要而含有重複單元（1)至（3) 以外之重複單元，但相對於全重複單元合計量，其含量通 常為10莫耳％以下，較佳為5莫耳％以下。從更加提升水 蒸氣阻隔性的觀點來看，液晶聚酯較佳為不具有醯胺鍵及 酿亞胺鍵。 耐熱性及熔融張力高之液晶聚酯之典型的例子為：相 對於全重複單元合計量，具有Ar1為2, 6-伸萘基之重複單 元（1)(亦即源自6-羥基-2-萘曱酸之重複單元）較佳為 9 323490 201221560 . 40至74. 8莫耳％，承社在^ 50至58苴1〇/更佳為40至64.5莫耳％，又更佳為 (亦m 9°且具有V為2,6—伸萘基之重複單元（2) (亦即源自2, 6-伸萘基二幾酸 — 至抑編，更佳為175===佳為12-5 25莫耳％，且具有心14二莫:％’又更佳為2。至 虿A為丨，4-伸本基之重複單元（2)(亦 二甲酸之重複單元)較佳為。.2幻咖， Γί:·丨f12莫耳％’又更佳為2至10莫福，且具 二為口 1 一’4-伸苯基之重複單元（3)(亦即源自對苯二紛 3〇/=兀）較佳為12.5至30莫耳％ ’更佳為17.5至 ? 贫0又更佳為2〇至25莫耳％ ;並且相對於Al*2為 :—申蔡基之重複單元⑴及紅2為1，4-伸苯基之重複單 =(2)的合5十篁，Ar2為2, 6_伸萘基之重複單元⑵的 含量較佳為0.5倍莫耳數以上，更佳為0.6倍莫耳數以上。 时液晶聚醋可藉由下述製程而製造：將賦予重複單元⑴ 之單體（亦即預定之芳香族經基竣酸）、賦予重複單元⑺ 之，體（亦即預定之芳香族二叛酸）、以及賦予重複單元⑺ 之單體（亦即預定之芳香族二醇），以使具有2,6_伸萘基 之單體的合計量（亦即6-羥基-2-萘甲酸、2, 6_伸萘基二 緩酉夂及2’ 6-伸蔡基二醇之合計量）相對於全單體合計量而 成為40莫耳％以上之方式，藉由進 (一d一n))而可製造液晶聚w 可聚合之衍生物，以分別取代一部分或全部之芳香族經基 緩酉夂、方香族二_及芳香族二醇。芳香族經基竣酸及芳 香族二竣酸等具有幾基的化合物之可聚合的衍生物，其例 323490 10 201221560 子可列舉：將羧基轉換為烷氧基羰基或芳氧基羰基者、將 緩基轉換為鹵化曱醯基（haloformyl)者、將敌基轉換醯 氧基裁基（acyl oxy carbonyl)者。芳香族經基叛酸及芳香 族二醇等具有羥基的化合物之可聚合的衍生物，其例子可 列舉：將經基予以醯化而轉換為醯氧基者。 此外’液晶聚酯較佳為藉由將單體進行熔融聚合，並 將所得聚合物（預聚合物（prep〇lymer))進行固相聚合而 製造者。藉此’可操作性良好地製造耐熱性及熔融張力高 之液晶聚酯。熔融聚合可在觸媒存在下進行。此觸媒可列 舉：醋酸鎂、醋酸錫（n )、鈦酸四丁酯（tetrabutyl titanate)、醋酸鉛、醋酸鈉、醋酸鉀、三氧化銻等金屬化 合物及N’N-二甲基胺基吡啶、N一曱基咪唑等含氮雜環式化 合物，較佳為使用含氮雜環式化合物。 液晶聚酯之流動起始溫度較佳為28〇Qc以上，更佳為 2赃以上’又更佳為295。€以上，此外，通常在·。㈢ 下’較佳為在·。(：以下。流動起始溫度越高，則越容易 提^耐熱性及㈣張力’但若過高，則為了使其炫融而需 要高溫，而使成形時容易熱劣化。 另外動起始溫度又稱為流動溫度（fl〇W temperature) ’其係使用具有内#丨咖、長度丨〇腿的喷嘴 (nozzle)之毛細管流變計（capiUary在 9.8MPa (IGOkg/on 3之荷重下，以似分鐘之升溫速度 將液晶聚S旨之加熱熔融體從喷嘴擠壓㈣，、熔融黏度顯示 為4_Pa · s (侧0泊（p〇ise))之溫度，該溫度係液晶 11 323490 201221560 聚酯之分子量之指標。（請參照小出直之編輯之「液晶聚合 物-合成、成形、應用-」，CMC有限公司、i987年6月5 曰、95頁）。 如此所得之具有前述預定重複單元組成的液晶聚醋， 其水蒸氣阻隔性優異，較佳係當製成厚度5〇iam的膜時， 在溫度40°C及相對溼度90%下所測定的水蒸氣穿透度為 〇· 005g/m2 · 24h 以下者。 液晶聚酯可視需要調配其他成份以製成組成物。其他 成伤可列舉如充填材、液晶聚酯以外的熱可塑性樹脂及添 加劑。液晶聚酯在組成物整體中所佔之比例較佳為質量 %以上，更佳為90質量％以上。 充填材可列舉：磨碎玻璃纖維（milledglass fiber)、 切碎玻璃纖維（chopped glass fiber)等玻璃纖維；鈦酸 鉀日日鬚（potassium titanate whisker)、氧化鋁晶鬚、硼 =晶鬚、碳切晶鬚、氮化發晶鬚等金屬或非金屬系晶 鬚類；玻璃片（glass piece)、中空玻璃球、玻璃粉末、 :母π石、黏土、二氧化矽（silica)、氧化鋁、鈦酸鉀、 f又石（wollastonite)、碳酸鈣（重質、輕質、膠質等）、 碳酸鎂：鹼性碳酸鎂、硫酸鈉、硫酸鈣、硫酸鋇、亞硫酸 气氧化風氧化鎂、氫氧化|弓、石夕酸妈、>5夕砂、石夕 _好石英 '氧化欽、氧化鋅、氧化鐵、石墨、在目、石錦、 :氧化石夕-氧化銘纖維（siHca_alumina⑽小氧化铭 、准、石膏纖維、碳纖維、碳黑（carb〇n b丨扣让）、白碳（wh 土 te b〇n)、石夕藻土、'^土（bentonite)、絹雲母（sericite)、 12 323490 201221560 白砂及黑鉛，可視需要而使用兩種以上該等充填材。其中 較佳為使用玻璃纖維、雲母、滑石及碳纖維作為充填材。 充填材亦可視需要而經表面處理。表面處理劑可列 舉：石夕烧系偶合劑（si lane coupl ing agent )、鈦酸酯 (titanate)系偶合劑、硼烷（borane)系偶合劑等反應性 偶合劑、以及高級脂肪酸、高級脂肪酸酯、高級脂肪酸金 屬鹽、敗碳化物（f luorocarbon)系界面活性劑等潤滑劑。 相對於液晶聚酯1〇〇質量份，充填材之調配量通常為 1至20質量份’較佳為〇. 5至15質量份，更佳為〇. 5至 10質量份。 液晶聚酯以外的熱可塑性樹脂可列舉：聚碳酸酯、聚 醯胺、聚砜（polysulfone)、聚笨硫醚 (polyphenylenesulfide)、聚苯醚（polyphenylene oxide)、聚醚酮（polyetherketone)及聚趟醯亞胺 (polyetherimide)樹月旨。 添加劑可列舉如：氣樹脂、金屬皂（metallie soap) 等離型改良劑、成核劑（nucleating agent)、抗氧化劑 (antioxidant)、安定劑（stabilizing agent)、塑化劑 (plasticizer)、抗著色劑、著色劑、紫外線吸收劑 (ultraviolet absorber)、抗靜電劑（antistatic agent )、潤滑劑（lubricant)及阻燃劑（flame retarder)。 將如此所得之液晶聚酯或其組成物進行膜化，而可得 到成為本實施型態之積層膜的基材的液晶聚酯膜。膜化方 法可列舉如撥壓成形法、加塵（press )成形法、溶液流延 13 323490 201221560 法及射出成形法，較佳為擠壓成形法。擠壓成形法可列舉 如T模具（T-dies)法及吹膨（inflation)法，於T模具 法中，可進行單軸延伸，亦可進行雙軸延伸。 單軸延伸膜的延伸倍率（牽伸比（draft ratio))通 常為1. 1至40，較佳為1〇至40，更佳為13至35。雙轴 延伸膜之MD方向（擠壓方向）的延伸倍率通常為丨.2至 40倍，雙軸延伸膜之TD方向（與擠壓方向垂直之方向） 的延伸倍率通常為1. 2至20倍。吹膨膜之MD方向的延伸 倍率（洩降比（drawdown ratio)=氣泡（bubble)吸取速 度/樹脂吐出速度）通常為1.5至50，較佳為5至30，吹 脹膜之TD的延伸倍率（流動比（f l〇w rati〇)=氣泡徑/ 環狀狹縫徑）通常為15至10，較佳為2至5。 液晶聚酯膜的厚度較佳為5至1〇〇em，更佳為1〇至 75/zra ’又更佳為15至75"m。若過薄則強度不足，若過 厚則可撓性不足。 如此所得之液晶聚酯膜係因由具有 組成之液峨而構成，故其水蒸氣阻隔性優異重= 在溫度4GC及相雌度9G%下所測定的水蒸氣穿透度為 0. 005g/m2 · 24h 以下者 在液晶聚醋膜之至少-面上形成水蒸氣阻隔層，而可 得到本實施·之積祕。此積相之水蒸氣阻隔性，係 較基材層之液晶聚酯膜為更優異。 構成水蒸氣阻隔層之物質較佳為從由、 鐵、钻、錄、銅、鋅、銀及金所成群組中選出之至少一種 323490 14 201221560 元素之單體、氧化物、氮化物、氮氧化物，亦可視需要而 使用兩種以上。 形成水蒸氣阻隔層之方法可列舉如：蒸鍍法、濺鍍法 (sputtering)、離子鑛法（ion plating)等 PVD 法；電 漿CVD法、熱CVD法、雷射CVD法等CVD法；以及溶膠凝 膠（sol-gel)法、鍍覆法、塗佈法等濕式法。此外，亦可將 另外調製或獲得之箔貼合於液晶聚酯膜。 水蒸氣阻隔層的厚度較佳為5至250 # m，更佳為4至 100仁m 〇水蒸氣阻隔層若過薄貝|J水蒸氣阻隔性不足，若過 厚則可撓性不足。 如此所得之本實施型態之積層膜係因基材層之水蒸氣 阻隔性優異，故使積層膜整體之水蒸氣阻隔性優異，較佳 為在溫度40°C及相對溼度90%所測定的水蒸氣穿透度為 0. 0001g/m2 · 24h 以下者。 本實施型態之積層膜係因基材層之水蒸氣阻隔性優 異，且積層膜整體之水蒸氣阻隔性優異，故可適用在要求 水蒸氣阻隔性之各種用途。其中，可適合使用作為有機EL 元件之基板。 於前述積層膜之至少一面上形成電極，而得到本實施 型態之附電極的積層膜。 於積層膜上形成之電極可為透明電極，但並非必須為 透明。透明電極一般可由含有Al、Cu等金屬及碳等導電物 質之導電膏（paste)，或是Al、Cu等金屬等而形成。 形成電極之方法並無特別限制，可使用蒸鍍、濺鍍、 15 323490 201221560 離子鐘、ϋ覆、塗佈、印刷等公知之形成方法。此外，電 極的厚度並無特別限制，一般可為50至lG〇〇"m。 。形成電極時之過程溫度並無特別限定，但較佳為15〇 ^以上更佳為180°C以上，又更佳為250〇C以上。若在此 聋巳圍中可使涛片電阻（sheet resistance)變小。 使用本實施型態之積層膜作為有機EL元件之基板 時通兩在積層膜上配置一對電極，且在此一對電極間配 置有機此層°如第1圖所示’積層膜1僅於基材層2的- 面上具有水蒸氣阻隔層3時，較佳為在基材層2之與配置 有水蒸氣阻隔層3之面相反側的面上，配置-對電極4A、 4B及有機EL層5。 此外，雖然第1圖中，於積層膜1上依照陰極4A、有 機EL層5及陽極4B之順序配置，但亦可於積層膜}上依 照陽極4B、有機EL層5及陰極4A之順序配置。此外 1圖中，有機EL層5雖然是由發光層％、於其陰極4八側 所配置之電子輸送層5a、於其陽極4β侧所配置之電洞輸 送層5c所構成’但發光層5b及電子輸送層5&可用具有: 者機月b之發光層兼電子輸送層取代，發光層％及電洞輸送 層5c可用具有兩者機能之發光層兼電洞輸送層取代。阳 發光層5b的材料可為高分子型，也可為低分子型。此 外，陰極4A及陽極4B的材料可各自獨立地為銘、銅等金 屬，也可為氧化銦錫、氧化鋅錫等金屬氧化物，但為了 從發光層5b發出的光穿透，故對至少—者要求要有透明 性。本實施型態之積_ i中，基材層係由液晶聚醋所構 323490 16 201221560 • 成，通常其透明性為不佳，故以此作為基板之有機Ει元件 . 較佳為頂發光型（t〇P emission type)，該頂發光型係使 光從發光層5b在與積層膜1為相反側之方向發光。接， 有機EL元件為頂發光型時，以發光層5b為基準，對於在 與積層膜1相反側所配置之電極（第i圖中為陽極4B)係 要求透明性，且對於在其上所配置之密封層6亦要求透明 性。 以水蒸氣阻隔性的觀點來看，密封層6較佳為玻璃 板’以可撓性的觀點來看則較佳為樹脂膜。密封材7較佳 為使用紫外線硬化型樹脂。此外，密封層6亦可不用= 板及樹脂膜之類的板狀材料，而以紫外線硬化型樹脂等六 封材覆蓋一對電極與有機EL層。 费 如此所得之有機EL元件係因使用水蒸氣阻隔性優異 之本發明積層體作為基板，故可抑制水蒸氣所造成之發光 層及電極的劣化，其性能之維持性優異。 (實施例） [測定流動起始溫度] 使用流動測試儀（島津製作所股份有限公司製 「CFT-500型」）’將約2g試料充填於裳設有内徑丨咖、長 度10麵的模具（dies)之毛細管型流變計，在9.8Mpa UOOkg/on 2)之荷重下，α 4口分鐘之升溫速度將試料 熔融且同時擠壓出，測定熔融黏度顯示為48〇〇Pa.s(48〇〇〇 泊）時之溫度。 [評價水蒸氣阻隔性] 323490 17 201221560 . 以JISK7129C法為基準，藉由氣體穿透率/透濕度測 . 定裝置（GTR Tec股份有限公司之「GTR-30X」），以溫度4〇 °C、相對溼度90%之條件測定水蒸氣穿透度。 [測定ΙΤ0膜之表面電阻率] 藉由4探針法電阻測定裝置（三菱化學製Loresta AP) 測定ΙΤ0膜之表面電阻率（薄片電阻）。 (製造例1) 於具備攪拌裝置、轉矩計（torcluemeter)、氮氣導入 管、溫度計及回流冷卻器之反應器内，加入6-羥基-2-萘 曱酸1034.99g(5.5莫耳）、2,6-伸萘基二羧酸378.33g (1.75莫耳）、對苯二甲酸83. 07S(〇.5莫耳）、對苯二酚 272. 52g( 2. 475莫耳：較2, 6-伸萘基二羧酸及對苯二曱酸 合計量多0. 225莫耳）、醋酸酐1226· 87g( 12莫耳）、及作 為觸媒之1-曱基咪唑0. 17§ ’以氮氣置換反應器内之氣體 後，於氮氣氣流下一邊攪拌一邊花費15分鐘將溫度由室溫 升溫至145°C，並於l45°c回流1小時。接著’蒸餾去除副 庫物醋酸及未反應之醋酸酐’同時花費3小時30分將溫度 由145°C升溫至31〇°C，於310°C維持3小時後，將内容物 取出並冷卻至室溫。以粉碎機將所得固形物粉碎成粒徑約 0 · 1至1 mm，在氮氣環境下’花費1小時將溫度由室溫升 溫至25(TC，並花費10小時將溫度由25〇°C升溫至310。(：， 於310。(：維持5小時’藉此以進行固相聚合。固相聚合後 將其冷卻，而得到粉末狀之液晶聚酯。相對於全重複單元 合計量，此液晶聚酯具有Arl為2, 6-伸萘基之重複單元〇) 323490 18 201221560 55莫耳％、Ar為2, 6-伸萘基之重複單元（？）17 5莫耳 %、Ar2為1，4-伸苯基之重複單元（2) 5莫耳％、及Ar3 為1，4-伸苯基之重複單元（3) 22.5莫耳％，此液晶聚酯 之流動起始溫度為333。(：。 (製造例2) 於與製造例1相同之反應器内，加入對羥基苯曱酸 911g (6.6莫耳）、間苯二甲酸gig (0.55莫耳）、對苯二 甲酸274g( 1.65莫耳>4, 4’ -二羥基聯苯4〇9g( 2. 2莫耳）、 醋酸酐1235g(12.1莫耳）、及作為觸媒之卜曱基咪唑 〇. 17g’以氮氣置換反應器内之氣體後，於氮氣氣流下一邊 攪拌一邊花費15分鐘將溫度由室溫升溫至丨5〇。〇，並於15〇 C回流1小時。接著添加卜曱基咪唑h 7g，然後蒸餾去除 副產物醋酸及未反應之醋酸酐，同時花費2小時5〇分將溫 度由150°C升溫至320°C，當確認到轉矩（torque)上升時， 將内容物取出並冷卻至室溫。以粉碎機將所得固形物粉碎 成粒徑約0.1至1 mm後，在氮氣環境下，花費丨小時將溫 度由室溫升溫至250Ϊ，並花費5小時將溫度由250°C升溫 至285 C，在285°C維持3小時，藉此以進行固相聚合。固 相聚合後將其冷卻，而得到粉末狀之液晶聚酯。此液晶聚 酯之流動起始溫度為327°C。 (實施例1) 將製造例1所得之粉末狀液晶聚酯以雙軸擠壓機（池 貝股份有限公司製「P C M _ 3 〇」）造粒並製成粒狀後，供給至 單轴擠壓機（螺桿徑5〇mm)並熔融，從τ模具（模唇（Ηρ) 19 323490 201221560 長度300腿，模唇間隙1臟，模具溫度35(TC )擠壓為膜 狀並冷卻’而得到厚度50 // m之液晶聚酯。此液晶聚g旨膜 之水蒸氣穿透度為0. 0030g/m2 · 24h。 於所得之液晶聚酯膜之單面，藉由濺錢法形成厚度 20nm之氧化鋁薄膜以作為氣體阻隔層，而得到積層膜。此 積層膜之水蒸氣穿透度未達〇.〇〇〇lg/m2 · 24h (未達檢測 下限值）。 、 (實施例2) 針對實施例1所得之積層膜，於形成有氣體阻隔層之 相反之面’在基板溫度為18(TC下使用ITO (氧化銦錫）藉 由離子錢法而形成厚度200nm之透明電極（ITO膜）。經測 定’在此積層膜上形成之透明電極的薄片電阻為9.1Ω/ 〇 (實施例3) 針對實施例1所得之積層膜，於形成有氣體阻隔層之 相反之面’在基板溫度為25(TC下使用ΙΤΟ (氧化銦锡）並 藉由離子鑛法而形成厚度200nm之透明電極（ITO膜）。經 /則定’在此積層膜上形成之透明電極的薄片電阻為6. 3Ω/ 〇 (比較例1 ) 將製造例2所得之粉末狀液晶聚酯以雙轴擠壓機（池 貝版份有限公司製「PCM-30」）造粒並製成粒狀後’供給至 單轴掩壓機（螺桿徑50麵）並熔融，從T模具（模唇長度 300聰1 ’模唇間隙1 mm，模具溫度35(TC )擠壓為膜狀並冷 20 323490 201221560 - 卻，而得到厚度5 0 // m之液晶聚酯。此液晶聚S旨膜之水蒸 . 氣穿透度為0. 080g/m2 · 24h。 於所得之液晶聚酯膜之單面，藉由濺鍍法形成厚度 20nm之氧化鋁薄膜以作為氣體阻隔層，而得到積層膜。此 積層膜之水蒸氣穿透度為0. 0020g/m2 · 24h。 (比較例2) 針對比較例1所得之積層膜，於形成有氣體阻隔層之 相反之面，在基板溫度為180°C下使用ITO (氧化銦錫）並 藉由離子鍍法而形成厚度200nm之透明電極（ITO膜）。經 測定，在此積層膜上形成之透明電極的薄片電阻為12. 3Ω /□。 (產業上之可利用性） 本發明之積層膜係因具有由水蒸氣阻隔性優異之液晶 聚酯所構成之基材層、及水蒸氣阻隔層，故水蒸氣阻隔性 優異，適合使用作為有機EL元件之基板。 【圖式簡單說明】 第1圖係示意性地表示有機EL元件構造之例之截面 圖。 [ 主要元件符號說明】 1 積層膜（基板） 2 基材層 3 水蒸氣阻隔層 4A 陰極 4B 陽極 21 323490 201221560 5 有機EL層 5a 電子輸送層 5b 發光層 5c 電洞輸送層 6 密封層 7 密封材Ar1 represents 2,6-anthracene, 1,4-phenylene or 4,4, _biphenyl. Ar and Ar3 each independently represent 2,6-anthracene, 1,4-phenylene, anthracene, 3-phenylene or 4,4'-extended biphenyl. a hydrogen atom in the aforementioned group represented by red 1, 2 or human 1'3, that is, 2, 6-anthranyl, iota, phenyl, 1,3-phenyl or 4, 4' The hydrogen atoms in the biphenyl group may be independently substituted by a dentate atom, a carbon number of 1 to 10 or an aryl group having 6 to 2 carbon atoms. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, and isopropyl group 323490 7 201221560 base, isobutyl group, second butyl group, tert-butyl-n-hexyl group, 2-base group, n-octyl group, and癸基's carbon number is usually ... ^. A methyl group, m-tolyl group, p-tolyl group, n-yl group and 2-naphthyl group, when the carbon number is usually 6 or the like, in each of the ", ^ 2 (^ heart atom by this batch of Ar or Ar3 In the above-mentioned basis, the order of the substituted soils is usually 2 or less, preferably less than or equal to each other. - (1) is derived from a predetermined aromatic _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ It is a 2, 6~ anthranyl group (that is, a repeating unit derived from 6-hydroxy-2-naphthoic acid). The _f complex unit (1) is a repeating single derived from the group II (4). ^ 复早70 ( 2) Preferred system: red 2 is 2,6-anthranyl group (ie, source, repeating unit of 6-extension base), and Ar24 1,4-phenylene (ie, derived from benzene) The repeating unit of dicarboxylic acid). The repeating unit (7) is derived from a repeating bill of the predetermined aromatic diol to 3) preferably: ΑΓ3 is a one-strength base (ie, derived from a hydroquinone) a repeating unit), and a biphenyl group (that is, a repeating unit derived from 4,4,_di-biphenyl). 4_ The liquid crystal polyester of the present embodiment is in the formulas (1), (2), and 3) At least one of the repeating units contains 2 , 6_ stretching naphthyl group, the content of the repeating unit containing the 2,6-strandyl group is *ear% or more relative to the total repeat = compositing meter. In the liquid crystal polycondensation, the total repeat unit is measured ( Dividing the mass of each repeating unit constituting the liquid helium vinegar by the formula amount of each repeating unit, and obtaining the equivalent mass of each repeating unit on the next day (mole), and assigning the equivalent value to the person ten 323490 8 201221560 The value of the repeating unit containing 2,6-anthranyl group (that is, the repeating unit (1) in which Ar1 is a 2,6-anthracenyl group, and the repeating unit in which Ar2 is a 2,6-anthranyl group (2) And the total content of the repeating unit (3) in which Ar3 is 2,6-anthranyl group is 40 mol% or more. Thereby, the water vapor barrier property of the base material layer can be improved. This 2,6-stretching naphthyl group The content is preferably 50% by mole or more, more preferably 60% by mole or more, and still more preferably 70% by mole or more. Further, in the liquid crystal polyester, the repeating unit (1) is compared with the total repeating unit. The content is preferably from 30 to 80 mol%, more preferably from 40 to 70 mol%, still more preferably from 45 to 65 mol%, and, in addition, to the total repeat unit total amount, The content of the repeating unit (2) is preferably from 10 to 35 mol%, more preferably from 15 to 30 mol%, still more preferably from 17. 5 to 27. 5 mol%. The total amount of the repeating unit (3) is preferably from 10 to 35 mol%, more preferably from 15 to 30 mol%, still more preferably from 17.5 to 27.5 mol%, and has such predetermined repeating unit composition. The liquid crystal polyester is excellent in balance between heat resistance and moldability, and the content of the repeating unit (2) and the content of the repeating unit (3) are preferably substantially equal. Further, the liquid crystal polyester may contain a repeating unit other than the repeating units (1) to (3) as needed, but the content thereof is usually 10 mol% or less, preferably 5 mol% or less, based on the total repeat unit total amount. . From the viewpoint of further enhancing the water vapor barrier property, the liquid crystal polyester preferably does not have a guanamine bond or a ruthenium bond. A typical example of a liquid crystal polyester having high heat resistance and high melt tension is a repeating unit (1) having an Ar1 of 2,6-anthranyl group relative to a total repeat unit (i.e., derived from 6-hydroxy-2) - repeating unit of naphthoic acid) is preferably 9 323490 201221560 . 40 to 74. 8 mol %, the carrier is in the range of 50 to 58 苴 1 〇 / more preferably 40 to 64.5 mol %, and more preferably ( a repeating unit (2) having a V of 2,6-stretching naphthyl group (i.e., derived from 2,6-exetylene naphthoic acid) to a suppression, more preferably 175 === 12-5 25 mol%, and has a heart 14 dioxin: %' is more preferably 2. 虿A is 丨, 4- repeating unit repeating unit (2) (repetitive unit of dicarboxylic acid) is preferred For .2 magic coffee, Γί:·丨f12 mole%' is more preferably 2 to 10 mofu, and has two for the mouth of a '4-phenylene repeating unit (3) (ie from Benzene is 3 〇 / = 兀) preferably 12.5 to 30 mol % 'more preferably 17.5 to? Poor 0 and more preferably 2 〇 to 25 mol %; and relative to Al * 2 is: - Shen The repeating unit of Cai Ji (1) and red 2 are repeating units of 1,4-phenylene group = (5), and the repeating unit of Ar2 is 2, 6_strandyl. The content of the liquid is preferably 0.5 times or more, more preferably 0.6 times or more. The liquid crystal polyacetate can be produced by the following process: a monomer which imparts a repeating unit (1) (that is, a predetermined aromatic a monomer (ie, a predetermined aromatic di-rebel acid) imparted to the repeating unit (7), and a monomer (ie, a predetermined aromatic diol) imparted to the repeating unit (7) so as to have 2,6 _ The total amount of monomers of the naphthyl group (that is, the total amount of 6-hydroxy-2-naphthoic acid, 2,6-naphthyl dioxime and 2' 6-extension diol) relative to the total By adding a total amount of monomers to 40 mol% or more, a liquid crystal poly-w polymerizable derivative can be produced by substituting (a d-n)) to replace a part or all of the aromatic radicals, respectively. , Fangxiang Group II and aromatic diol. A polymerizable derivative of a compound having a plurality of groups such as a carboxylic acid and an aromatic dicarboxylic acid. Examples of 323490 10 201221560 include: converting a carboxyl group into Alkoxycarbonyl or aryloxycarbonyl, conversion of a slow group to a haloformyl group, conversion of an enemy group An acyl oxy carbonyl group. A polymerizable derivative of a compound having a hydroxyl group such as an aromatic tetreic acid or an aromatic diol, and examples thereof may be exemplified by converting a thiol group into a hydrazine group. Further, the liquid crystal polyester is preferably produced by melt-polymerizing a monomer and solid-phase polymerizing the obtained polymer (prep〇lymer), whereby the operability is good. A liquid crystal polyester having high heat resistance and high melt tension is produced. The melt polymerization can be carried out in the presence of a catalyst. Examples of the catalyst include metal oxides such as magnesium acetate, tin (n) acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide, and N'N-dimethylaminopyridine. A nitrogen-containing heterocyclic compound such as N-mercaptoimidazole is preferably a nitrogen-containing heterocyclic compound. The flow initiation temperature of the liquid crystal polyester is preferably 28 〇 Qc or more, more preferably 2 Å or more and still more preferably 295. More than €, in addition, usually in. (3) The next 'is better. (The following: The higher the flow initiation temperature, the easier it is to improve the heat resistance and (4) the tension. However, if it is too high, a high temperature is required to make it melt, and it is easy to thermally degrade during molding. Also known as flow temperature (fl〇W temperature) 'It is a capillary rheometer with a nozzle with a length of #丨咖, length 丨〇 leg (capiUary at 9.8 MPa (IGOkg/on 3 load, to The heating rate of the liquid crystal polymerization is squeezed from the nozzle (4), and the melt viscosity is displayed as 4_Pa · s (side 0 poise). The temperature is liquid crystal 11 323490 201221560 polyester Index of molecular weight. (Refer to "Liquid Crystal Polymer-Synthesis, Forming, Application--" by Cum., C., Ltd., June 5, pp. 95, pp. 95). The thus obtained predetermined repeating unit composition The liquid crystal polyacetate has excellent water vapor barrier property, and is preferably a water vapor permeability of 〇·005g/ measured at a temperature of 40 ° C and a relative humidity of 90% when a film having a thickness of 5 μm is formed. M2 · 24h or less. Liquid crystal polyester can be adjusted Other components are used to form a composition. Other examples of the wounds include thermoplastic materials such as fillers and liquid crystal polyesters, and additives. The proportion of the liquid crystal polyester in the entire composition is preferably at least mass%, more preferably 90% by mass or more. Filling materials include glass fibers such as milled glass fiber and chopped glass fiber; potassium titanate whisker, alumina whisker, and boron. = metal or non-metal whiskers such as whiskers, carbon-cut whiskers, nitrided whiskers; glass pieces, hollow glass spheres, glass powder, mother π stone, clay, cerium oxide (silica) ), alumina, potassium titanate, f-stone (wollastonite), calcium carbonate (heavy, light, colloid, etc.), magnesium carbonate: alkaline magnesium carbonate, sodium sulfate, calcium sulfate, barium sulfate, sulfurous acid gas oxidation Wind magnesium oxide, hydrogen hydroxide|bow, Shixi acid mother, >5 Xisha, Shi Xi _ good quartz 'oxidation Qin, zinc oxide, iron oxide, graphite, in the eyes, stone Jin,: oxidized stone eve - oxidation Ming Fiber (siHca_alumina (10) small oxidation, , gypsum fiber, carbon fiber, carbon black (carb〇nb丨), white carbon (wh earth te b〇n), Shixiazao soil, '^ soil (bentonite), sericite (sericite), 12 323490 201221560 white sand And black lead, two or more such fillers may be used as needed. Among them, glass fiber, mica, talc and carbon fiber are preferably used as the filler. Filling materials can also be surface treated as needed. Examples of the surface treatment agent include a reactive agent such as a si lane coupl ing agent, a titanate coupling agent, and a borane coupling agent, and a higher fatty acid and a higher fat. Lubricants such as acid esters, higher fatty acid metal salts, and f-roorocarbon-based surfactants. The amount of the filler is usually from 1 to 20 parts by mass, preferably from 0.5 to 15 parts by mass, more preferably from 5 to 10 parts by mass, based on 1 part by mass of the liquid crystal polyester. Examples of the thermoplastic resin other than the liquid crystal polyester include polycarbonate, polyamine, polysulfone, polyphenylenesulfide, polyphenylene oxide, polyetherketone, and polyfluorene. Polyetherimide tree. Examples of the additives include a gas resin, a metallie soap release modifier, a nucleating agent, an antioxidant, a stabilizering agent, a plasticizer, and an anti-staining agent. Agents, colorants, ultraviolet absorbers, antistatic agents, lubricants, and flame retarders. The liquid crystal polyester or the composition thereof thus obtained is film-formed to obtain a liquid crystal polyester film which is a substrate of the laminated film of the present embodiment. The film formation method may, for example, be a press forming method, a press forming method, a solution casting method, and a spray casting method, and is preferably an extrusion molding method. Examples of the extrusion molding method include a T-dies method and an inflation method. In the T-die method, uniaxial stretching or biaxial stretching can be performed. The stretching ratio (draft ratio) of the uniaxially stretched film is usually from 1.1 to 40, preferably from 1 to 40, more preferably from 13 to 35. 2至20。 The stretching ratio of the stretching direction of the biaxially extending film is generally 丨. 2 to 40 times, the stretching ratio of the TD direction of the biaxially extending film (the direction perpendicular to the extrusion direction) is usually 1.2 to 20 Times. The stretch ratio in the MD direction of the blown film (drawdown ratio = bubble picking speed / resin discharge speed) is usually from 1.5 to 50, preferably from 5 to 30, and the stretching ratio of the TD of the inflation film (Flow ratio (fl〇w rati〇) = bubble diameter / annular slit diameter) is usually 15 to 10, preferably 2 to 5. The thickness of the liquid crystal polyester film is preferably from 5 to 1 〇〇em, more preferably from 1 〇 to 75/zra ' and still more preferably from 15 to 75 Å. If it is too thin, the strength is insufficient, and if it is too thick, the flexibility is insufficient. 005g/米2 The water vapor permeability of the liquid crystal polyester film is 0. 005g/m2. The water vapor permeability is 0. 005g/m2 measured at a temperature of 4GC and a phase of 9G%. • A water vapor barrier layer is formed on at least the surface of the liquid crystal polyester film for 24 hours or less, and the present embodiment can be obtained. The water vapor barrier property of this phase is superior to that of the liquid crystal polyester film of the substrate layer. The substance constituting the water vapor barrier layer is preferably at least one monomer, oxide, nitride, nitrogen selected from the group consisting of iron, diamond, diamond, copper, zinc, silver and gold. The oxide may be used in combination of two or more kinds as needed. Examples of the method for forming the water vapor barrier layer include a PVD method such as a vapor deposition method, a sputtering method, or an ion plating method; a CVD method such as a plasma CVD method, a thermal CVD method, or a laser CVD method; And a wet method such as a sol-gel method, a plating method, or a coating method. Further, a foil prepared or obtained may be attached to the liquid crystal polyester film. The thickness of the water vapor barrier layer is preferably from 5 to 250 # m, more preferably from 4 to 100 Å. If the water vapor barrier layer is too thin, the water vapor barrier property is insufficient, and if it is too thick, the flexibility is insufficient. Since the laminated film of the present embodiment thus obtained is excellent in water vapor barrier property of the base material layer, the entire laminated film is excellent in water vapor barrier property, and is preferably measured at a temperature of 40 ° C and a relative humidity of 90%. The water vapor permeability is 0. 0001g/m2 · 24h or less. The laminated film of the present embodiment is excellent in water vapor barrier property of the base material layer, and is excellent in water vapor barrier property of the entire laminated film, and thus can be applied to various applications requiring water vapor barrier properties. Among them, a substrate which is an organic EL element can be suitably used. An electrode is formed on at least one surface of the laminated film to obtain a laminated film of the electrode of the present embodiment. The electrode formed on the laminate film may be a transparent electrode, but it is not necessarily required to be transparent. The transparent electrode can be generally formed of a conductive paste containing a conductive material such as a metal such as Al or Cu or carbon, or a metal such as Al or Cu. The method of forming the electrode is not particularly limited, and a known formation method such as vapor deposition, sputtering, ion treatment of 15 323 490 201221560, coating, coating, and printing can be used. Further, the thickness of the electrode is not particularly limited and may generally be 50 to 1 G 〇〇 " m. . The temperature at which the electrode is formed is not particularly limited, but is preferably 15 〇 ^ or more, more preferably 180 ° C or more, and still more preferably 250 〇 C or more. If this is the case, the sheet resistance can be made smaller. When the laminated film of the present embodiment is used as a substrate of an organic EL device, a pair of electrodes are disposed on the laminated film, and an organic layer is disposed between the pair of electrodes. As shown in Fig. 1, the laminated film 1 is only When the water vapor barrier layer 3 is provided on the surface of the base material layer 2, it is preferable to dispose the counter electrode 4A, 4B and organic on the surface of the base material layer 2 opposite to the surface on which the water vapor barrier layer 3 is disposed. EL layer 5. Further, in the first embodiment, the laminated film 1 is disposed in the order of the cathode 4A, the organic EL layer 5, and the anode 4B, but may be disposed on the laminated film in the order of the anode 4B, the organic EL layer 5, and the cathode 4A. . In addition, in the figure 1, the organic EL layer 5 is composed of the light-emitting layer %, the electron transport layer 5a disposed on the eight sides of the cathode 4, and the hole transport layer 5c disposed on the anode 4β side thereof, but the light-emitting layer 5b And the electron transport layer 5& can be replaced by a light-emitting layer and an electron transport layer having the same function, and the light-emitting layer % and the hole transport layer 5c can be replaced by a light-emitting layer and a hole transport layer having both functions. The material of the luminescent layer 5b may be either a polymer type or a low molecular type. In addition, the materials of the cathode 4A and the anode 4B may each independently be a metal such as indium or copper, or may be a metal oxide such as indium tin oxide or zinc tin oxide. However, in order to penetrate light emitted from the light-emitting layer 5b, at least - The request requires transparency. In the product of the present embodiment, the substrate layer is made of liquid crystal polycondensate 323490 16 201221560, and generally its transparency is not good, so it is used as the organic component of the substrate. Preferably, the top emission type (t〇P emission type), the top emission type emits light from the light-emitting layer 5b in a direction opposite to the laminated film 1. When the organic EL element is of the top emission type, the electrode disposed on the side opposite to the laminated film 1 (the anode 4B in the first drawing) is required to have transparency on the basis of the light-emitting layer 5b, and is required to be transparent thereto. The sealing layer 6 is also required to have transparency. From the viewpoint of water vapor barrier properties, the sealing layer 6 is preferably a glass plate. From the viewpoint of flexibility, a resin film is preferred. The sealing material 7 is preferably an ultraviolet curable resin. Further, the sealing layer 6 may be formed of a plate-shaped material such as a plate or a resin film, and a pair of electrodes and an organic EL layer may be covered with a six-layer material such as an ultraviolet curable resin. In the organic EL device, the laminate of the present invention having excellent water vapor barrier properties is used as the substrate. Therefore, deterioration of the light-emitting layer and the electrode due to water vapor can be suppressed, and the performance of the laminate is excellent. (Example) [Measurement of the flow initiation temperature] A flow tester ("CFT-500 type" manufactured by Shimadzu Corporation) was used to fill approximately 2 g of the sample into a mold having an inner diameter of 丨 coffee and a length of 10 faces. The capillary type rheometer of dies), under the load of 9.8Mpa UOOkg/on 2), melts the sample at a temperature of 4 minutes and simultaneously extrudes it, and the measured melt viscosity is 48 〇〇Pa.s (48). The temperature at the time of anchorage. [Evaluation of Water Vapor Barrier Property] 323490 17 201221560 . Based on the JIS K7129C method, the gas permeability/permeability measurement device (GTR Tec Co., Ltd. "GTR-30X") is used at a temperature of 4 °C. The water vapor permeability was measured under the condition of a relative humidity of 90%. [Measurement of Surface Resistivity of ΙΤ0 Film] The surface resistivity (sheet resistance) of the ΙΤ0 film was measured by a 4-probe resistance measuring apparatus (Loresta AP, manufactured by Mitsubishi Chemical Corporation). (Production Example 1) In a reactor equipped with a stirring device, a torque meter, a nitrogen gas introduction tube, a thermometer, and a reflux condenser, 6-hydroxy-2-naphthoic acid 103.49 g (5.5 m) was added, and 2 , 6-extended naphthyl dicarboxylic acid 378.33g (1.75 moles), terephthalic acid 83. 07S (〇.5 moles), hydroquinone 272. 52g ( 2. 475 moles: more than 2, 6 - a total of 0. 225 moles of the naphthyl dicarboxylic acid and terephthalic acid, 1226 · 87g (12 moles) of acetic anhydride, and 1-mercaptoimidazole as a catalyst 0. 17§ ' After replacing the gas in the reactor with nitrogen, the temperature was raised from room temperature to 145 ° C while stirring under a nitrogen gas stream, and refluxed at 1 45 ° C for 1 hour. Then, 'distilling off the secondary storage acetic acid and unreacted acetic anhydride', the temperature was raised from 145 ° C to 31 ° C for 3 hours and 30 minutes, and after maintaining at 310 ° C for 3 hours, the contents were taken out and cooled to Room temperature. The obtained solid matter was pulverized into a particle size of about 0.1 to 1 mm by a pulverizer, and the temperature was raised from room temperature to 25 (TC) under a nitrogen atmosphere for 1 hour, and the temperature was raised from 25 〇 ° C for 10 hours. To 310. (:, at 310. (: maintain for 5 hours) thereby performing solid phase polymerization. After solid phase polymerization, it is cooled to obtain a powdery liquid crystal polyester. This liquid crystal is compared with the total repeat unit. Polyester having a repeating unit of 2,6-anthranyl group of Arl) 323490 18 201221560 55 mole %, Ar is a repeating unit of 2,6-anthranyl group (?) 17 5 mol%, Ar2 is 1, 4-cyclophenyl repeating unit (2) 5 mol%, and Ar3 is a repeating unit of 1,4-phenylene group (3) 22.5 mol%, and the liquid crystal polyester has a flow initiation temperature of 333. (Production Example 2) In the same reactor as in Production Example 1, 911 g (6.6 mol) of p-hydroxybenzoic acid, gig (0.55 mol) of isophthalic acid, and 274 g of terephthalic acid (1.65 mol) were added. Ears > 4, 4'-dihydroxybiphenyl 4〇9g (2 2 moles), acetic anhydride 1235g (12.1 moles), and as a catalyst, oxime imidazolium. 17g' replacement with nitrogen After the gas inside, the temperature was raised from room temperature to 丨5〇 while stirring under a nitrogen gas stream. 〇, and refluxed at 15 ° C for 1 hour, followed by addition of buckylimidazole h 7 g, and then distillation to remove by-product acetic acid And unreacted acetic anhydride, while taking 2 hours and 5 minutes to raise the temperature from 150 ° C to 320 ° C, when it is confirmed that the torque rises, the contents are taken out and cooled to room temperature. After the obtained solid matter is pulverized to a particle diameter of about 0.1 to 1 mm, it is taken to raise the temperature from room temperature to 250 Torr in a nitrogen atmosphere, and it takes 5 hours to raise the temperature from 250 ° C to 285 C at 285 °. C was maintained for 3 hours to carry out solid phase polymerization. After solid phase polymerization, it was cooled to obtain a powdery liquid crystal polyester. The liquid crystal polyester had a flow initiation temperature of 327 ° C. (Example 1) The powdery liquid crystal polyester obtained in Production Example 1 was granulated by a twin-screw extruder ("PCM _ 3 〇" manufactured by Chiba Co., Ltd.) and granulated, and then supplied to a uniaxial extruder (screw diameter 5 〇 mm). ) and melted from the τ mold (mould lip (Ηρ) 19 323490 201221560 Length 300 legs, lip gap 1 dirty, mold temperature 35 (TC) extruded into a film and cooled 'to obtain a thickness of 50 / m liquid crystal polyester. This liquid crystal polyg film water vapor permeability is 0 0030g/m2 · 24h An aluminum oxide film having a thickness of 20 nm was formed as a gas barrier layer by a sputtering method on one side of the obtained liquid crystal polyester film to obtain a laminated film. The water vapor permeability of this laminated film did not reach 〇.〇〇〇lg/m2 · 24h (the lower limit of detection was not reached). (Example 2) The laminate film obtained in Example 1 was formed on the opposite side of the gas barrier layer to have a substrate temperature of 18 (using ITO (indium tin oxide) under TC to form a thickness of 200 nm by ion-method method. Transparent electrode (ITO film). It was determined that the sheet resistance of the transparent electrode formed on the laminated film was 9.1 Ω / 〇 (Example 3) The laminated film obtained in Example 1 was reversed in the formation of the gas barrier layer. The surface of the transparent electrode (ITO film) having a thickness of 200 nm was formed by using an iridium (indium tin oxide) at a substrate temperature of 25 (the ITO film). The transparent electrode formed on the laminated film was The sheet resistance was 6.3 Ω / 〇 (Comparative Example 1) The powdery liquid crystal polyester obtained in Production Example 2 was granulated by a biaxial extruder ("PCM-30" manufactured by Ikebe Co., Ltd.) and granulated. 'Supply to a single-axis masking machine (screw diameter 50 faces) and melt it from the T-die (die length 300 Cong 1 'mould lip gap 1 mm, die temperature 35 (TC) squeezed into a film and cold 20 323490 201221560 - However, a liquid crystal polyester having a thickness of 50 // m is obtained. Water vapor. Gas permeability was 0.080 g/m2 · 24 h. On one side of the obtained liquid crystal polyester film, an aluminum oxide film having a thickness of 20 nm was formed by sputtering to obtain a laminated film. The water vapor permeability of the laminated film was 0. 0020 g/m 2 · 24 h. (Comparative Example 2) The laminated film obtained in Comparative Example 1 was formed on the opposite side of the gas barrier layer at a substrate temperature of 180 ° C. The ITO (indium tin oxide) was used to form a transparent electrode (ITO film) having a thickness of 200 nm by ion plating. The sheet resistance of the transparent electrode formed on the laminated film was 12.3 Ω / □. In the laminated film of the present invention, the base material layer composed of the liquid crystal polyester having excellent water vapor barrier properties and the water vapor barrier layer are excellent in water vapor barrier properties, and are suitable for use as an organic EL device. [Brief Description of the Drawings] Fig. 1 is a cross-sectional view schematically showing an example of the structure of an organic EL element. [Explanation of main element symbols] 1 laminated film (substrate) 2 base material layer 3 water vapor barrier layer 4A cathode 4B anode 21 323490 2012 21560 5 Organic EL layer 5a Electron transport layer 5b Light-emitting layer 5c Hole transport layer 6 Sealing layer 7 Sealing material