201245323 六、發明說明： 【發明所屬之技術領域】 本發明係關於由液晶聚酯構成的太陽電池用基板。又 、本發明係關於使用本太陽電池用基板而成的太陽電池元 件〇 【先前技術】 圖1係將太陽電池元件之例以模式表示之剖面圖。此 例中，於太陽電池用基板1上，藉由依序層合裏面電極層 2、光電變換層3及表面電極層4而構成太陽電池元件5。 又、光電變換層3係由p型半導體層3a、i型半導體層3b 及η型半導體層3c而構成。接著，太陽電池元件5通常 由多數個連結，如圖2所示，爲密封層7所密封，於其表 側（受光面側）配置表面保護薄片6，於其相反側（與受光面 相反面側）配置有背膜8，表面保護薄片6及背膜8之周圍 部以框架9固定，藉此構成太陽電池模組10。 在太陽電池用基板，爲了防止電極層或光電變換層腐 蝕等的劣化，要求水蒸氣阻隔性。在此，作爲太陽電池用 基板的材料，由得到水蒸氣阻隔性優良的太陽電池基板， 探討液晶聚酯。例如於專利文獻]，具體揭示作爲太陽電 池用基板的材料，使用含有來自p-羥基安息香酸的重複單 元60莫耳％、來自對苯二甲酸的重複單元15莫耳％、來自 間苯二甲酸的重複單元5莫耳％、及來自4,4-二羥基聯苯的 重複單元20莫耳％的液晶聚酯。又、專利文獻2中，具體 -5- 201245323 揭示作爲太陽電池用基板材料，使用特定的液晶聚酯商品（ 住友化學（股）的「SUMIKA SUPER E6000」或 Polyplastics(股 )的厂 Vectra A950」）。 [先前技術文獻] [專利文獻] [專利文獻〗]日本特開2002-64213號公報 [專利文獻2]日本特開2004-140143號公報 【發明內容】 [發明所欲解決的課題] 本發明的目的係，提供由液晶聚酯構成，且水蒸氣阻 隔性更優良的太陽電池用基板。 [解決課題的方法] 爲達成前述之目的，本發明提供具有以下述式（1)所表 示的重複單元，以下述式（2)所表示的重複單元，和以下述 式（3)所表示的重複單元，且含有2,6-伸萘基的重複單元之 含有Μ，相對於全部重複單元之合計量爲40莫耳％以上的 液晶聚酯所構成之太陽電池用基板。 -O-Ar'-CO- (1) -C0-Ar2-C0- (2) -0-Ar3-0- (3) (Ar1表示2,6-伸萘基、I,4-伸苯基或4,4’-伸聯苯基。Ar2 及Ar3各自獨立表示2,6-伸萘基、】，4-仲苯基、】，3·伸苯基 201245323 或4,4’-伸聯苯基。Ar1、Ar2或Ar3所表示的前述基中的氫 原子各自獨立，可被鹵素原子、烷基或芳基取代）。 又、本發明提供由液晶聚酯所構成，且在溫度40°C及 相對濕度90%測定的水蒸氣透過率爲〇.〇〇5g/m2,24h以下 的太陽電池用基板。 更且，本發明提供其特徵係由作成厚度50 μπι之薄膜 時於溫度40°C及相對濕度90%時測定之水蒸氣透過度爲 0.005g/m2 · 24h以下的液晶聚酯所構成之太陽電池用基板 〇 此外，本發明提供在前述任一的太陽電池用基板上， 依序設置裏面電極層、光電轉換層及表面電極層而成的太 陽電池元件。 [發明效果] 本發明之太陽電池用基板之水蒸氣阻隔性優良，藉由 使用此可得到有效防止電極層或光電變換層腐蝕等劣化的 太陽電池元件。 [實施發明之最佳形態] 構成本發明之太陽電池用基板的液晶聚酯，係溶融時 顯示光學異向性之聚酯，宜具有以下述式（1)表示的重複單 元（以下、可稱爲重複單元（1))，與以下述式（2)表示的重 複單元（以下、可稱爲重複單元（2))，與以下述式（3)表示 的重複單元（以下、可稱爲重複單元（3)) ° 201245323 -0-Ar1 -CO- (1) -CO-Ar2-CO- (2) -O-Ar^-O- (3) (八1>|表示2,6-伸萘基、1，4-伸苯基或4,4，-伸聯苯基。八1·2 及Ar3各自獨立表示2,6-伸萘基、1，4-伸苯基、1，3-伸苯基 或4,4’-伸聯苯基。Ar1、Ar2或Ar3所表示之前述基中的氫 原子各自獨立，可被鹵素原子、碳數1〜1〇的烷基或碳數 6〜20的芳基取代p 作爲前述的鹵素原子，可舉例有氟原子、氯原子、溴 原子及碘原子。前述烷基之例，可舉例有甲基、乙基、n-丙基、異丙基、η-丁基、異丁基、s-丁基、t-丁基、η-己 基、2-乙基己基、η-辛基、及η-癸基，其碳數通常爲1〜 10。前述芳基之例，可舉例有苯基、〇-甲苯基、m·甲苯基 、p-甲苯基、1-萘基及2-萘基，其碳原子數通常爲6〜20 。前述氫原子以這類的基取代之場合，其數目在以Ar1、 Ar2又Ar3表示的前述每個基中，各自獨立，通常爲2個 以下，以1個以下爲佳。 重複單元（1)係來自所指定芳香族羥基羧酸的重複單元 。作爲重複單元（])，Ar1爲2,6-伸萘基，亦即以來自6-羥 基-2-萘甲酸之重複單元爲佳。 重複單元（2)係來自所指定芳香族二羧酸之重複單元。 作爲重複單元（2)，Ar2爲2,6-伸萘基者，亦即以來自2,6-萘二羧酸之重複單元，及Ar2爲1，4-伸苯基者，亦即以來 自對苯二甲酸之重複單元爲佳。 -8- 201245323 重複單元（3)係來自所指定芳香族二醇之重複單元。重 複單元（3)，以Ar3爲伸苯基者’亦即以來自對苯二酚 之重複單元，及Ar3爲4,4’-伸聯苯基、亦即以來自4,4’-二羥基聯苯之重複單元爲佳。 液晶聚酯中，包含2,6-伸萘基之重複單元含有量、亦 即Ar1爲2,6-伸萘基之重複單元（1)、Ar2爲2,6-伸萘基之 重複單元（2)、及Ar3爲2,6-伸萘基之重複單元（3)的合計 含有量，相對於全重複單元之合計量（由構成液晶聚酯之 各重複單元之質量除以各重複單元之式量求得各重複單元 之物質量相當量（莫耳），這些的合計値）爲40莫耳％以上 。藉由將具有所指定重複單元組成之液晶聚酯薄膜化，可 獲得水蒸氣阻隔性優良的液晶聚酯薄膜。此2,6-伸萘基之 含有量’以5 0莫耳％以上爲佳、6 0莫耳％以上更佳、7 0 莫耳％以上又更佳。 又、液晶聚酯中，重複單元（1)之含有量，相對於全重 複單元之合計量以30〜80莫耳％爲佳、40〜70莫耳％更佳 、45〜65莫耳％又更佳’重複單元（2)之含有量，相對於全 重複單元之合計量以10〜35莫耳％爲佳、15〜30莫耳％更 佳、17.5〜27.5莫耳％又更佳，重複單元（3)之含有量，相 對於全重複單元之合計量以10〜35莫耳％爲佳、15〜3〇 莫耳％更佳、1 7.5〜2 7 · 5莫耳％又更佳。如此般具有所指 定之重複單元組成的液晶聚酯，具有優良的耐熱性與成型 性之平衡。尙且、重複單元（2)的含有量與重複單元（3)的 含有量實際上以相等爲佳。又、液晶聚酯於必要時具有重 -9- 201245323 複單兀（1)〜（3)以外之重複單元亦可，但其含有量相對於 全重複單兀之合計量通常& ! 〇莫耳％以下、5莫耳％以下 爲佳。 耐熱性或溶融張力高的液晶聚酯之典型的例，相對於 全重複單兀之合計量，Ari爲2,6伸萘基之重複單元（丨）、 亦即來自6-羥基-2-萘甲酸之重複單元，以具有4〇〜74 8 莫耳％爲佳、40〜64.5莫耳％更佳、5〇〜58莫耳％又更佳 ，Ar2爲2,6-伸萘基之重複單元（2) '亦即來自2,6萘二羧 酸之重複單兀，以具有12.5〜30莫耳％爲佳、17.5〜30莫 耳％更佳、20〜25莫耳％又更佳，Ar2爲丨，4_伸苯基之重複 單兀（2)’亦即來自對苯二甲酸之重複單元，以具有〇2〜 1 5莫耳。/〇爲佳、〇 · 5〜丨2莫耳％更佳、2〜1 〇莫耳％又更佳 ’Ar爲丨，4_伸苯基之重複單元（3)、亦即來自對苯二酚之 重複單元’以具有12.5〜30莫耳％爲佳、丨7·5〜30莫耳％ 更佳’ 20〜25莫耳％又更佳，且Ar2爲2，6_伸萘基之重複 單元（2)的含有量，相對於Ar2爲2,6-伸萘基之重複單元 (2)及Ar2爲1，4-伸苯基之重複單元（2)的合計含有量以〇 5 莫耳倍以上爲佳、0.6莫耳倍以上者更佳。 將構成重複單元（1)單體、亦即所指定之芳香族羥基羧 酸’與構成重複單元（2)單體、亦即所指定之芳香族二羧酸 ’與構成重複單元（3)單體’亦即所指定之芳香族二醇，以 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-萘二羧酸及2,6·萘二醇之合計量，相對於全單體之 合計量在40莫耳％以上之方式，通過聚合反應（縮聚反應） -10- 201245323 ’可製造液晶聚酯。此時，芳香族羥基羧酸、芳香族二羧 酸及芳香族二醇’各自獨立，可將其中一部份或全部替換 使用可聚合之衍生物。芳香族羥基羧酸及芳香族二羧酸般 的具有羧基之化合物之可聚合的衍生物之例，可舉例如轉 換羧基爲烷氧羰基或芳氧羰基而成者、轉換羧基爲鹵代甲 醯基而成者、轉換羧基爲醯氧羰基而成者。芳香族羥基羧 酸及芳香族二醇般的具有羥基之化合物的可聚合衍生物之 例，可舉例如將羥基醯化爲醯氧基而成者。 此外’以將單體溶融聚合，並將所得聚合物（預聚物） 通過固相聚合，製造液晶聚酯爲佳。由此，可操作性良好 地製造耐熱性或溶融張力高的液晶聚酯。溶融聚合，可於 觸媒存在下進行’作爲這一種觸媒的例子，如醋酸鎂、醋 酸錫、鈦酸四丁酯、醋酸鉛、醋酸鈉、醋酸鉀、三氧化二 銻等之金屬化合物、或N，N-二甲基胺基吡啶、N-甲基咪 唑等含氮雜環化合物，以使用含氮雜環化合物爲佳。如此 得到之具有前述所指定之重複單元組成之液晶聚酯，具有 優良的水蒸氣阻隔性’可適用作爲本發明之太陽電池用基 板之材料。 液晶聚酯，其流動開始溫度以2 8 0 t以上爲佳、2 9 0 °C 以上更佳、295 °C以上又更佳，又、通常在38(TC以下、 3 5 0 °C以下爲佳。雖然流動開始溫度越高，耐熱性或溶融 張力容易提高’但過高時溶融需要高溫、成型時容易熱劣 化。 尙且、流動開始溫度，也被稱爲fl〇vv temperature或 -11 - 201245323 流動溫度，爲使用具有內徑lmm、長l〇mm噴嘴的毛細管 流變儀，在9.8MPa(100kg/cm2)的荷重下，以4°C/分昇溫 速度將液晶聚酯之加熱溶融體自噴嘴擠出時，顯示溶融黏 度爲4 800Pa*s(48,000poise)時之溫度，係成爲液晶聚酯分 子S的基準者（小出直之編、「液晶聚合物-合成·成型·應 用-」、CMC Publishing Co.，Ltd、1987 年 6 月 5 日、ρ·95 作參考）。 本發明之液晶聚酯，較佳爲製成厚度50μη!之薄膜時 在溫度40°C及相對濕度90%測定之水蒸氣透過度，以0.05 g/m2_24h 以下爲佳、0.01g/m2_24h 以下更佳、0.005g/m2‘24h 以下又更佳。 液晶聚酯，必要時可配合其他成分作爲組成物。其他 成分之例，如塡充材料、液晶聚酯以外的熱可塑性樹脂及 添加劑。組成物全體中占有的液晶聚酯之比例，以8 0質 量％以上爲佳、90質量％以上更佳。 塡充材料之例，可舉例如磨碎玻纖（milled glass fiber) 、細切玻璃纖維等之玻璃纖維、鈦酸鉀晶須、氧化鋁晶須 、硼酸鋁晶須、碳化矽晶須、氮化矽晶須等之金屬或非金 屬系晶須類、玻璃珠、中空玻璃球、玻璃粉末、雲母、滑 石粉、黏土、二氧化矽' 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 、硫酸鈣、硫酸鋇、亞硫酸鈣、氫氧化鋁、氫氧化鎂、氣 氧化鈣、矽酸鈣、石英砂、石英石、石英、二氧化鈦、氧 化鋅、氧化鐵石墨、鉬、石綿、二氧化砂氧化鋁纖維、氧 -12- 201245323 化鋁纖維、石膏纖維、碳纖維、碳黑、白碳黑、矽藻土、 膨潤土、絹雲母、白砂及石墨，於必要時可使用這些2種 以上。其中、以玻璃纖維、雲母、滑石粉及碳纖維較宜使 用。 塡充材料於必要時可爲於表面處理過者，此類表面處 理劑之例，可舉例如矽烷系偶聯劑、鈦酸酯系偶聯劑、硼 烷系偶聯劑等之反應性偶聯劑、及高級脂肪酸、高級脂肪 酸酯、高級脂肪酸金屬鹽、氟碳化合物系界面活性劑等潤 滑劑。 液晶聚酯以外的熱可塑性樹脂之例，可舉例如聚碳酸 酯、聚醯胺、聚颯、聚苯硫醚、聚苯醚、聚醚酮及聚醚醯 亞胺樹脂。 添加劑之例，可舉例如氟樹脂、金屬皂類等改善脫模 劑、成核劑、防止氧化劑、安定劑、可塑劑、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。 由如此得到的液晶聚酯或其組成物薄膜化，可得到成 爲本發明之太陽電池用基板的液晶聚酯薄膜。薄膜化的方 法方面，可舉例如擠出成型法、加壓成型法、溶液流延法 及射出成型法，以擠出成型法爲佳。擠出成型法，可舉例 如T-模具法或膨脹法（inflation method)可舉爲例，以T-模 具法而言、可以一軸延伸、二軸延伸亦可。 一軸延伸薄膜之延伸倍數（draft ratio)，通常爲1 .1〜 40、以10〜40爲佳、15〜35更佳。二軸薄膜之MD方向（ -13- 201245323 擠出方向）的延伸倍數、通常爲1.2〜40倍，二軸薄膜之 TD方向（與擠出方向垂直的方向）的延伸倍數、通常爲1.2 〜20倍。膨脹薄膜之MD方向的延伸倍數（Drawdown比= 氣泡收取速度/樹脂吐出速度），通常爲1.5〜50、以5〜30 爲佳，膨脹薄膜之TD的延伸倍數（吹氣比=氣泡直徑/環狀 細縫直徑），通常爲1 .5〜1 0、以2〜5爲佳。 液晶聚酯薄膜之厚度以5〜100 μπι爲佳、10〜75 μηι更 佳、1 5〜7 5 μηι又更佳。太薄則強度變得不足，太厚則可 撓性變得不足。 由如此得到之液晶聚酯薄膜，水蒸氣阻隔性優良，可 使用作爲本發明之太陽電池用基板。此液晶聚酯薄膜，於 溫度40°C及相對濕度90%測定之水蒸氣透過度，以0.05 g/m2_24h 以下爲佳、0.01g/m2‘24h 以下更佳、0.005g/m2* 24h以下又更佳。 尙且、將液晶聚酯薄膜多片層合，將熱可塑性樹脂薄 膜等其他薄膜層合於液晶聚酯薄膜而獲得之層合薄膜，亦 可使用作爲本發明之太陽電池用基板。又、欲將液晶聚酯 薄膜或前述層合薄膜進一步提高水蒸氣阻隔性，設置水蒸 氣阻隔層、設置其他機能層而獲得之層合薄膜，亦可作爲 本發明之太陽電池用基板使用。 水蒸氣阻隔層，至少設置於液晶聚酯薄膜的一面上。 如設置於液晶聚酯薄膜之單面上，則以設置於液晶聚酯薄 膜之裡面（與設置電極層面相反面）上爲佳。 作爲構成水蒸氣阻隔暦的物質，以選擇自鋁、矽、鈦 -14 - 201245323 、鉻、鐵、鈷、鎳、銅、鋅、銀及金所組成群中的至少— 種元素單體、氧化物、氮化物和氮氧化物爲佳、於必要時 亦可使用其中的2種以上。 作爲水蒸氣阻隔層的形成方法之例’可舉例如蒸鍍法 、濺鍍法、離子濺鍍法等之PVD法、電漿CVD法、熱 CVD法、雷射CVD法等之CVD法、及溶膠凝膠法、鍍敷 法、塗佈法等之濕式法。又、將另外調製、取得的鋁箔貼 合於液晶聚酯薄膜亦可。 如此而獲得水蒸氣阻隔性優良的太陽電池用基板，藉 由使用其可獲得有効防止電極層或光電轉換層之腐蝕等劣 化之太陽電池元件。 太陽電池元件之典型如圖1所顯示，太陽電池基板】 上、依序設置裏面電極層2、光電轉換層3及表面電極層 4而獲得。 裏面電極層2的材料，以光線反射率高的導電體爲佳 ，可舉例有銀、鋁、銅、金、鉑金、鎳、錫、鐵等金屬； 不銹鋼、鋁合金等合金；及氧化銦錫、氧化鋁、氧化錫等 金屬氧化物。裏面電極層2的形成方法，可舉例有真空蒸 鍍法、濺鍍法、CVD法、電解鍍敷法及無電解鍍敷法。201245323 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a substrate for a solar cell composed of a liquid crystal polyester. Further, the present invention relates to a solar cell element using the substrate for a solar cell. [Prior Art] Fig. 1 is a cross-sectional view showing a solar cell element as an example. In this example, the solar cell element 5 is formed by sequentially laminating the back electrode layer 2, the photoelectric conversion layer 3, and the surface electrode layer 4 on the solar cell substrate 1. Further, the photoelectric conversion layer 3 is composed of a p-type semiconductor layer 3a, an i-type semiconductor layer 3b, and an n-type semiconductor layer 3c. Next, the solar cell elements 5 are usually connected by a plurality of them, and as shown in FIG. 2, the sealing layer 7 is sealed, and the surface protective sheet 6 is disposed on the front side (the light receiving surface side) on the opposite side (the side opposite to the light receiving surface). The back film 8 is disposed, and the peripheral portions of the surface protective sheet 6 and the back film 8 are fixed by the frame 9, thereby constituting the solar cell module 10. In the solar cell substrate, in order to prevent deterioration of the electrode layer or the photoelectric conversion layer, etc., water vapor barrier properties are required. Here, as a material of the solar cell substrate, a liquid crystal polyester is examined from a solar cell substrate having excellent water vapor barrier properties. For example, in the patent document, a material for a substrate for a solar cell is specifically disclosed, and a repeating unit containing 60 mol% from p-hydroxybenzoic acid, a repeating unit of 15 ppm from terephthalic acid, and isophthalic acid are used. The repeating unit is 5 mol%, and the repeating unit derived from 4,4-dihydroxybiphenyl is 20 mol% of the liquid crystal polyester. In the patent document 2, the specific liquid crystal polyester product (Sumitomo Chemical Co., Ltd. "SUMIKA SUPER E6000" or Polyplastics (stock) Vectra A950") is disclosed as a substrate material for solar cells. . [PRIOR ART DOCUMENT] [Patent Document] [Patent Document] Japanese Laid-Open Patent Publication No. 2002-64213 [Patent Document 2] JP-A-2004-140143 SUMMARY OF INVENTION [Problems to be Solved by the Invention] The present invention The object of the invention is to provide a substrate for a solar cell which is composed of a liquid crystal polyester and which is more excellent in water vapor barrier properties. [Means for Solving the Problem] In order to achieve the above object, the present invention provides a repeating unit having a repeating unit represented by the following formula (1), represented by the following formula (2), and represented by the following formula (3) A substrate for a solar cell comprising a liquid crystal polyester having a repeating unit of 2,6-anthranyl group and having a total amount of 40% by mole or more based on the total of all repeating units. -O-Ar'-CO- (1) -C0-Ar2-C0- (2) -0-Ar3-0- (3) (Ar1 represents 2,6-anthranyl, I,4-phenylene or 4,4'-Extended biphenyl. Ar2 and Ar3 each independently represent 2,6-anthranyl,], 4-sec-phenyl,], 3-phenylene 201245323 or 4,4'-extended biphenyl The hydrogen atoms in the aforementioned groups represented by Ar1, Ar2 or Ar3 are each independently and may be substituted by a halogen atom, an alkyl group or an aryl group. Further, the present invention provides a substrate for a solar cell which is composed of a liquid crystal polyester and has a water vapor transmission rate of 〇. 5 g/m 2 and 24 hours or less as measured at a temperature of 40 ° C and a relative humidity of 90%. Furthermore, the present invention provides a solar crystal composed of a liquid crystal polyester having a water vapor permeability of 0.005 g/m 2 · 24 h or less measured at a temperature of 40 ° C and a relative humidity of 90% when a film having a thickness of 50 μm is formed. In addition, the present invention provides a solar cell element in which a back electrode layer, a photoelectric conversion layer, and a surface electrode layer are sequentially provided on the solar cell substrate. [Effect of the Invention] The solar cell substrate of the present invention is excellent in water vapor barrier property, and by using this, a solar cell element which can effectively prevent deterioration of the electrode layer or the photoelectric conversion layer or the like can be obtained. [Best Mode for Carrying Out the Invention] The liquid crystal polyester which is a substrate for a solar cell of the present invention is a polyester which exhibits optical anisotropy when it is melted, and preferably has a repeating unit represented by the following formula (1) (hereinafter, it can be called The repeating unit (1)) is a repeating unit represented by the following formula (2) (hereinafter, may be referred to as a repeating unit (2)), and a repeating unit represented by the following formula (3) (hereinafter, may be referred to as repeating) Unit (3)) ° 201245323 -0-Ar1 -CO- (1) -CO-Ar2-CO- (2) -O-Ar^-O- (3) (八1>| indicates 2,6-anthracene Base, 1,4-phenylene or 4,4,-extended biphenyl. Octa 2·2 and Ar3 each independently represent 2,6-anthranyl, 1,4-phenylene, 1,3-extension Phenyl or 4,4'-biphenyl. The hydrogen atoms in the above-mentioned groups represented by Ar1, Ar2 or Ar3 are each independently, and may be a halogen atom, an alkyl group having a carbon number of 1 to 1 Å or a carbon number of 6 to 20. The aryl group-substituted p may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Η-butyl, isobutyl, s-butyl, t-butyl, η-hexyl, 2-B The hexyl group, the η-octyl group, and the η-fluorenyl group have a carbon number of usually 1 to 10. Examples of the aryl group include a phenyl group, a fluorenyl-tolyl group, an m. tolyl group, and a p-tolyl group. 1-naphthyl and 2-naphthyl, the number of carbon atoms is usually 6 to 20. When the above hydrogen atom is substituted with such a group, the number is in each of the aforementioned groups represented by Ar1, Ar2 and Ar3, respectively. Independently, it is usually 2 or less, preferably 1 or less. The repeating unit (1) is a repeating unit derived from the specified aromatic hydroxycarboxylic acid. As a repeating unit (]), Ar1 is a 2,6-naphthyl group. That is, a repeating unit derived from 6-hydroxy-2-naphthoic acid is preferred. The repeating unit (2) is a repeating unit derived from the specified aromatic dicarboxylic acid. As a repeating unit (2), Ar2 is 2,6-extension The naphthyl group, that is, the repeating unit derived from 2,6-naphthalenedicarboxylic acid, and the Ar2 is 1,4-phenylene group, that is, the repeating unit derived from terephthalic acid is preferred. -8- 201245323 The repeating unit (3) is a repeating unit derived from the specified aromatic diol. The repeating unit (3), with Ar3 as a phenylene group, is a repeating unit derived from hydroquinone, and A R3 is 4,4'-biphenyl, that is, a repeating unit derived from 4,4'-dihydroxybiphenyl. The liquid crystal polyester contains a repeating unit content of 2,6-anthranyl group, That is, Ar1 is a repeating unit of 2,6-anthranyl group (1), Ar2 is a repeating unit of 2,6-anthranyl group (2), and Ar3 is a repeating unit of 2,6-anthranyl group (3) The total amount of the total amount of the repeating unit is determined by dividing the mass of each repeating unit constituting the liquid crystal polyester by the amount of each repeating unit, and determining the mass of each repeating unit (mole). The total 値) is 40% or more. By thinning a liquid crystal polyester having a specified repeating unit composition, a liquid crystal polyester film excellent in water vapor barrier properties can be obtained. The content of the 2,6-anthracene group is preferably 50% by mole or more, more preferably 60% by mole or more, still more preferably 70% by mole or more. Further, in the liquid crystal polyester, the content of the repeating unit (1) is preferably 30 to 80 mol%, more preferably 40 to 70 mol%, and more preferably 45 to 65 mol%, based on the total amount of the repeating units. More preferably, the content of the repeating unit (2) is preferably 10 to 35 mol%, more preferably 15 to 30 mol%, more preferably 17.5 to 27.5 mol%, more preferably than the total repeating unit. The content of the unit (3) is preferably 10 to 35 mol%, more preferably 15 to 3 mol%, and even more preferably 1 7.5 to 27.5 cm%, based on the total amount of the total repeating unit. The liquid crystal polyester thus having the composition of the repeating unit specified has a balance of excellent heat resistance and moldability. Further, the content of the repeating unit (2) and the content of the repeating unit (3) are preferably equal. Further, the liquid crystal polyester may have a repeating unit other than the weight of -9-201245323, if necessary, except for the repeating unit (1) to (3), but the total amount of the liquid crystal polyester is usually & It is preferably less than or equal to 5% of the ear. A typical example of a liquid crystal polyester having high heat resistance or a high melt tension, Ari is a repeating unit of 2,6-naphthyl group (丨), that is, from 6-hydroxy-2-naphthalene, relative to the total repeating unit. The repeating unit of formic acid is preferably 4 to 74 8 mol%, more preferably 40 to 64.5 mol%, more preferably 5 to 58 mol%, and Ar2 is a repeating unit of 2,6-anthranyl group. (2) 'that is, repeating monoterpene from 2,6-naphthalenedicarboxylic acid, preferably having 12.5 to 30 mol%, more preferably 17.5 to 30 mol%, more preferably 20 to 25 mol%, and more preferably Ar2 For the crucible, the repeating unit (2) of the 4-phenylene group is also a repeating unit derived from terephthalic acid to have 〇2 to 15 mole. /〇为佳,〇·5~丨2mol% is better, 2~1 〇mol% is better. 'Ar is 丨, 4_ phenyl repeating unit (3), that is, from benzene The repeating unit of phenol is preferably 12.5 to 30 mol%, 丨7·5 〜30 mol%, more preferably 20 20 25 mol%, and Ar 2 is a repeat of 2,6 _naphthyl group. The content of the unit (2) is 〇5 摩尔 with respect to the repeating unit (2) in which Ar2 is 2,6-anthranyl group and the repeating unit (2) in which Ar2 is 1,4-phenylene group. More than twice, preferably more than 0.6 moles. The monomer constituting the repeating unit (1), that is, the designated aromatic hydroxycarboxylic acid 'and the monomer constituting the repeating unit (2), that is, the designated aromatic dicarboxylic acid, and the repeating unit (3) The body 'is the specified aromatic diol, which is the total amount of the monomer having a 2,6-anthranyl group, that is, 6-hydroxy-2_naphthoic acid, 2,6-naphthalenedicarboxylic acid and 2, The total amount of 6-naphthalenediol can be produced by a polymerization reaction (polycondensation reaction) -10- 201245323' in a total amount of 40 mol% or more based on the total monomer. In this case, the aromatic hydroxycarboxylic acid, the aromatic dicarboxylic acid, and the aromatic diol are each independently, and a part or all of them may be replaced with a polymerizable derivative. Examples of the polymerizable derivative of a compound having a carboxyl group such as an aromatic hydroxycarboxylic acid and an aromatic dicarboxylic acid include a conversion of a carboxyl group to an alkoxycarbonyl group or an aryloxycarbonyl group, and conversion of a carboxyl group to a halogenated formamidine. The base is formed by converting the carboxyl group to a fluorinated carbonyl group. Examples of the polymerizable derivative of the aromatic hydroxycarboxylic acid and the aromatic diol-like compound having a hydroxyl group include those obtained by deuteration of a hydroxy group into a decyloxy group. Further, it is preferred to polymerize the monomer and polymerize the obtained polymer (prepolymer) by solid phase polymerization to produce a liquid crystal polyester. Thereby, the liquid crystal polyester having high heat resistance or high melt tension can be produced with good operability. The melt polymerization can be carried out in the presence of a catalyst as an example of such 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 A nitrogen-containing heterocyclic compound such as N,N-dimethylaminopyridine or N-methylimidazole is preferably a nitrogen-containing heterocyclic compound. The liquid crystal polyester having the repeating unit composition specified above has excellent water vapor barrier properties and can be suitably used as a material for the solar cell substrate of the present invention. The liquid crystal polyester preferably has a flow initiation temperature of more than 280 m, more preferably 290 ° C or more, more preferably 295 ° C or more, and is usually 38 (TC or less, 350 ° C or less). Preferably, although the flow start temperature is higher, the heat resistance or the melt tension is easily increased. ' However, when the temperature is too high, the melting requires high temperature, and the molding tends to be thermally deteriorated. The flow start temperature is also called fl〇vv temperature or -11 - 201245323 Flow temperature, using a capillary rheometer with a nozzle of inner diameter lmm and length l〇mm, heating the liquid crystal polyester at a heating rate of 4.8 MPa (100 kg/cm 2 ) at a heating rate of 4 ° C / minute When the nozzle is extruded, the temperature at which the melt viscosity is 4 800 Pa*s (48,000 poise) is displayed, which is the basis for the liquid crystal polyester molecule S (Small and straight, "Liquid crystal polymer - Synthesis, molding, application -" , CMC Publishing Co., Ltd., June 5, 1987, ρ·95 for reference.) The liquid crystal polyester of the present invention is preferably made into a film having a thickness of 50 μm at a temperature of 40 ° C and a relative humidity of 90%. The measured water vapor transmission rate is preferably 0.05 g/m2_24h or less, and 0.01g/m2_24h or less. More preferably, it is more preferably 0.005 g/m2 '24h or less. Liquid crystal polyester, if necessary, can be combined with other components as a composition. Examples of other components, such as a thermoplastic material and a thermoplastic resin other than a liquid crystal polyester, and an additive. The proportion of the liquid crystal polyester which is contained in the entire material is preferably 80% by mass or more, more preferably 90% by mass or more. Examples of the filling material include, for example, milled glass fiber and finely cut glass fiber. Metal or non-metallic whiskers such as glass fiber, potassium titanate whisker, alumina whisker, aluminum borate whisker, tantalum carbide whisker, tantalum nitride whisker, glass beads, hollow glass spheres, glass Powder, mica, talcum powder, clay, cerium oxide 'alumina, potassium titanate, ash stone, calcium carbonate (heavy, light, colloid, etc.), magnesium carbonate, basic magnesium carbonate, sodium sulfate, calcium sulfate , barium sulfate, calcium sulfite, aluminum hydroxide, magnesium hydroxide, calcium oxide, calcium citrate, quartz sand, quartz, quartz, titanium dioxide, zinc oxide, iron oxide graphite, molybdenum, asbestos, alumina sand oxide Fiber, oxygen-12- 201245 323 Aluminized fiber, gypsum fiber, carbon fiber, carbon black, white carbon black, diatomaceous earth, bentonite, sericite, white sand and graphite, if necessary, more than two of these may be used. Among them, glass fiber, mica, talcum powder And carbon fiber is preferably used. The filler material may be surface treated if necessary, and examples of such a surface treatment agent include, for example, a decane coupling agent, a titanate coupling agent, and a borane coupling. A reactive coupling agent such as a reagent, and a lubricant such as a higher fatty acid, a higher fatty acid ester, a higher fatty acid metal salt, or a fluorocarbon surfactant. Examples of the thermoplastic resin other than the liquid crystal polyester include polycarbonate, polyamine, polyfluorene, polyphenylene sulfide, polyphenylene ether, polyether ketone, and polyether oxime resin. Examples of the additive include, for example, a fluororesin, a metal soap, and the like, a mold release agent, a nucleating agent, an antioxidant, a stabilizer, a plasticizer, a slip agent, a color preventive agent, a colorant, an ultraviolet absorber, an antistatic agent, and the like. Lubricants and flame retardants. The liquid crystal polyester or the composition thereof thus obtained is made into a film, and a liquid crystal polyester film which is a substrate for a solar cell of the present invention can be obtained. Examples of the method for forming the film include an extrusion molding method, a pressure molding method, a solution casting method, and an injection molding method, and an extrusion molding method is preferred. The extrusion molding method may, for example, be a T-die method or an expansion method, and may be one-axis extension or two-axis extension in the T-die method. The draw ratio of the one-axis stretch film is usually from 1.1 to 40, preferably from 10 to 40, more preferably from 15 to 35. The stretching ratio of the MD direction of the biaxial film (-13-201245323 extrusion direction) is usually 1.2 to 40 times, and the stretching ratio of the TD direction (direction perpendicular to the extrusion direction) of the biaxial film is usually 1.2 to 20 Times. The stretching ratio of the expanded film in the MD direction (Drawdown ratio = bubble collection speed / resin discharge speed), usually 1.5 to 50, preferably 5 to 30, and the stretching ratio of the TD of the expanded film (blowing ratio = bubble diameter / ring) The diameter of the slit is usually 1.5 to 10, preferably 2 to 5. The thickness of the liquid crystal polyester film is preferably 5 to 100 μm, more preferably 10 to 75 μη, and more preferably 1 5 to 7 5 μη. If it is too thin, the strength becomes insufficient, and if it is too thick, the flexibility becomes insufficient. The liquid crystal polyester film thus obtained is excellent in water vapor barrier property, and can be used as a substrate for a solar cell of the present invention. The liquid crystal polyester film has a water vapor permeability measured at a temperature of 40 ° C and a relative humidity of 90%, preferably 0.05 g / m 2 / 24 h or less, more preferably 0.01 g / m 2 ' 24 h or less, 0.005 g / m 2 * 24 h or less. Better. Further, a laminated film obtained by laminating a liquid crystal polyester film in a plurality of sheets and laminating another film such as a thermoplastic resin film to a liquid crystal polyester film can also be used as the substrate for a solar cell of the present invention. Further, the liquid crystal polyester film or the laminated film may be further improved in water vapor barrier properties, and a water vapor barrier layer or a laminated film obtained by providing another functional layer may be used as the substrate for a solar cell of the present invention. The water vapor barrier layer is disposed on at least one side of the liquid crystal polyester film. If it is provided on one side of the liquid crystal polyester film, it is preferably provided on the inside of the liquid crystal polyester film (opposite to the surface on which the electrode is provided). As a substance constituting the water vapor barrier iridium, at least one element monomer selected from the group consisting of aluminum, tantalum, titanium-14 - 201245323, chromium, iron, cobalt, nickel, copper, zinc, silver, and gold, is oxidized. The material, the nitride, and the oxynitride are preferred, and two or more of them may be used as necessary. Examples of the method for forming the water vapor barrier layer include, for example, a PVD method such as a vapor deposition method, a sputtering method, or an ion sputtering method, a plasma CVD method, a thermal CVD method, or a CVD method such as a laser CVD method, and A wet method such as a sol-gel method, a plating method, or a coating method. Further, it is also possible to bond the aluminum foil separately prepared and obtained to the liquid crystal polyester film. In this way, a substrate for a solar cell having excellent water vapor barrier properties can be obtained, and a solar cell element which is effective in preventing corrosion of the electrode layer or the photoelectric conversion layer and the like can be obtained by using it. A typical solar cell element is obtained as shown in Fig. 1 on a solar cell substrate, in which the inner electrode layer 2, the photoelectric conversion layer 3, and the surface electrode layer 4 are sequentially disposed. The material of the electrode layer 2 is preferably a conductor having a high light reflectance, and examples thereof include metals such as silver, aluminum, copper, gold, platinum, nickel, tin, and iron; alloys such as stainless steel and aluminum alloy; and indium tin oxide. Metal oxides such as alumina and tin oxide. The method of forming the inner electrode layer 2 may, for example, be a vacuum evaporation method, a sputtering method, a CVD method, an electrolytic plating method, or an electroless plating method.
光電轉換層3的材料以矽爲佳，光電轉換層3可以爲 非晶砂層 '亦可爲微晶砂層。又、光電轉換層3爲圖i顯 示之mp型構姐者之場合，包含於p型半導體層h之不 純物以硼爲佳’包含於n型半導體層之不純物以磷或 氮爲佳轉換® 3 β形成，施行容量偶聯電發CVD -15- 201245323 法或感應偶聯電漿CVD法之CVD法爲佳。 表面電極層4之材料，以透明性高的導電體爲佳，可 舉例有氧化錫、氧化銦錫、FTO及氧化鋅。表面電極層4 之形成方法，可舉例有真空蒸鍍法、濺鍍法及CVD法。 【實施方式】 由此獲得的太陽電池元件5，例如圖2所示，藉由使 多數個連結’以密封層7密封，於其表側（受光面側）配置 表面保護薄片6、於其裡側配置背膜8、表面保護薄片6 及背膜8周圍以框架9固定，而可構成太陽電池模組。又 '本發明之太陽電池用基板、亦可作爲積體型構造之太陽 電池模組的基板使用。 [實施例] [流動開始溫度之測定] 使用flow tester((股）島津製作所「CFT-5 00型」），將 樣本約2g，充塡於安裝有內徑1mm、長10mm模具（dies)之 毛細管型流變儀，於荷重9.8MPa(100kgf/cm2)下’以昇溫 速度4°C/分將樣本溶融同時擠出，測定溶融黏度達4800Pa-s (48000泊（poise))時之溫度。 [水蒸氣阻隔性評估] 以JISK7129C法爲標準，由氣體透過率·透濕度測定 裝置（GTR TEC技術（股）之「GTR-3 0X」），於溫度40°C ' -16- 201245323 相對濕度90%之條件下，測定水蒸氣透過度。 [氧化銦錫膜表面電阻率測定] 氧化銦錫膜表面電阻率（薄膜電阻），藉由4探針法電 阻測定裝置（三菱化學製LORESTA AP)測定。 製造例1 於具備攪拌裝置、扭力測試儀、氮氣導入管、溫度計 及迴流冷卻器之反應器，放入6-羥基-2-萘甲酸1 034.99g (5.5莫耳）、2,6-萘二羧酸3 78.3 3 8(1.75莫耳）、對苯二甲 酸83.0 7g(0.5莫耳）、對苯二酚272.52g(2.475莫耳：相對 2，6_萘二羧酸及對苯二甲酸之合計量，過量0.225莫耳）、 醋酸酐1 226.8 7g(12莫耳）、及作爲觸媒之1-甲基咪唑 〇.17g，反應器內氣體被氮氣取代後，氮氣氣流下、—邊 攪拌、一邊使室溫在15分鐘昇溫到145t，在145°C迴流 1小時。接著，一邊將副生成物醋酸及未反應的醋酸酐餾 去’一邊在3小時30分鐘將145°C昇溫到310°C，在310Ϊ： 保持3小時後，取出內容物並冷卻至室溫。獲得之固體以 粉碎機粉碎爲粒徑約0 · 1〜1 m m後，氮環境下、花費1小 時由室溫昇至250 °C，花費10小時由250 °C升溫至310。(：， 並在31〇°C保持5小時，以進行固相聚合。固相聚合後、 冷卻’獲得粉末狀液晶聚酯。此液晶聚酯具有相對於全重 複單元之合計量Ar1爲2,6 -伸萘基之重複單元（1)55莫耳％ 、Ar2爲2,6-伸萘基之重複單元（2)17.5莫耳。/。、Ar2爲1，4- 201245323 伸苯基之重複單元（2)5莫耳％、及Ar3爲1,4 -伸苯基之重 複單元（3)22.5%，且其流動開始溫度爲3 3 3。(：。 製造例2 在與製造例1同樣之反應器，放入p -羥基安息香酸 91 lg(6.6莫耳）、對苯二甲酸2 74g(1 .65莫耳）、間苯二甲 酸91g(0.55莫耳）、4,4，-二羥基聯苯409g(2.2莫耳）' 醋 酸酐1 2 3 5 g(12.I莫耳）、及作爲觸媒之！-甲基咪唑〇.17g ’反應器內氣體被氮氣取代後，氮氣氣流下、一邊攪拌、 一邊花费1 5分鐘將室溫昇溫至！ 5 〇 °c並在1 5 0 °C迴流1小 時。接著，添加1-甲基咪唑1.7g後，一邊將副生成物醋 酸及未反應之醋酸酐餾去，一邊花費2小時50分鐘由 150°C昇溫至320°C，確認扭矩上昇之時，取出內容物，冷 卻至室溫。獲得之固形物以粉碎機粉碎爲粒徑約〇」〜 1mm後，氮環境下、花費1小時將室溫昇溫至25 、花 費5小時將25 0°C昇溫至285°C、保持28 5 °C3小時以進行 固相聚合。固相聚合後，冷卻，獲得粉末狀液晶聚酯。此 液晶聚酯’具有Ar1爲1，4 -伸苯基之重複單元（1)60莫耳。/。 、Ar2爲1，4-伸苯基之重複單元（2)15莫耳％ ' Ar2爲丨，3_ 伸苯之重複單元（2)5莫耳％、及Ar3爲4，4’-伸聯苯基之重 複單元（3)20%，且其流動開始溫度爲327 °C。 實施例1 將製造例1獲得之液晶聚酯，以二軸擠出機（（股）池貝 -18- 201245323 「PCM-30」）粒化，成爲顆粒狀後，以一軸擠出機（螺旋徑 50mm)溶融，由T模具（唇閥長300mm、唇閥間隙lmm、 模具溫度3 5 0°C)擠出爲薄膜狀後冷卻，獲得厚度25μηι之 液晶聚酯薄膜。此液晶聚酯薄膜之水蒸氣透過度爲0.011 g/m2 · 24h，作爲太陽電池用基板，水蒸氣阻隔性優良。 實施例2 將於製造例1所獲得之液晶聚酯，以二軸擠出機（（股） 池貝「PCM-3 0」）粒化，成爲顆粒狀後，以一軸擠出機（螺 旋徑50mm)溶融’由T模具（唇閥長3 00mm、唇閥間隙 1 mm、模具溫度3 5 (TC )擠出爲薄膜狀後冷卻，獲得厚度 5 0 μηι之液晶聚酯。此液晶聚酯薄膜之水蒸氣透過度爲 0.00 3 g/m2‘24h ’作爲太陽電池用基板，水蒸氣阻隔性優良 實施例3 於實施例2獲得之層合薄膜，藉由離子濺鍍法在形成 氣體阻隔層之相反面使用ITO(氧化銦錫）在基板溫度180 °C 形成厚度200nm之透明電極（氧化銦錫膜）。測定此層合薄 膜上形成之透明電極的薄膜電阻爲9.1 Ω/Ε]。 比較例1 使製造例2獲得之液晶聚酯，以二軸擠出機（（股）池貝 「P C Μ - 3 0」）粒化’成爲顆粒狀後，供給至一軸擠出機（螺 -19- 201245323 旋徑50mm)使其溶融，由τ模具（唇閥長3 00mm、唇閥間 隙lmm、模具溫度3 50°C)擠出爲薄膜狀後冷卻，獲得厚度 2 5 μπι之液晶聚酯薄膜。此液晶聚酯薄膜之水蒸氣透過度 爲0.3 43 g/m2 · 24h ’作爲太陽電池用基板，水蒸氣阻隔性 不足夠。 比較例2 將製造例2獲得之液晶聚酯，以二軸擠出機（（股）池貝 「PCM-3 0」）粒化’成爲顆粒狀，供給至一軸擠出機（螺旋 徑50mm)使其溶融，由T模具（唇閥長3 00mm、唇閥間隙 lmm、模具溫度3 5 0°C)擠出爲薄膜狀後冷卻，獲得厚度 5 〇μιη之液晶聚酯薄膜》此液晶聚酯薄膜之水蒸氣透過度 爲0.080g/m2 · 24h ’作爲太陽電池用基板，水蒸氣阻隔性 不足夠。 比較例3 於比較例2獲得之層合薄膜，藉由離子濺鍍法在形成 氣體阻隔層之相反面使用ITO(氧化銦錫）在基板溫度180°C 形成厚度200nm之透明電極。測定此層合薄膜上形成之透 明電極的薄膜電阻爲Ι2.3Ω/Ε1。 【圖式簡單說明】 [圖1 ]太陽電池元件之例以模式表示之剖面圖。 [圖2]太陽電池模組之例以模式表示之剖面圖。 -20- 201245323 【主要元件符號說明】 1 :太陽電池用基板 2 :裏面電極層 3 :光電轉換層 3a : p型半導體層 3b : i型半導體層 3c : η型半導體層 4 :表面電極層 5 :太陽電池元件 6 =表面保護薄片 7 :密封層 8 :背膜 9 :框架 1 〇 :太陽電池模組 -21The material of the photoelectric conversion layer 3 is preferably ruthenium, and the photoelectric conversion layer 3 may be an amorphous sand layer 'may also be a microcrystalline sand layer. Further, in the case where the photoelectric conversion layer 3 is the mp-type configuration shown in FIG. i, the impurity contained in the p-type semiconductor layer h is preferably boron. The impurity contained in the n-type semiconductor layer is preferably converted by phosphorus or nitrogen. The β formation is preferably performed by a volume-coupled electrophoresis CVD -15-201245323 method or an inductively coupled plasma CVD method. The material of the surface electrode layer 4 is preferably a highly transparent conductor, and examples thereof include tin oxide, indium tin oxide, FTO, and zinc oxide. The method of forming the surface electrode layer 4 may, for example, be a vacuum deposition method, a sputtering method, or a CVD method. [Embodiment] As shown in Fig. 2, the solar cell element 5 thus obtained has a surface protective sheet 6 disposed on the front side (light receiving surface side) by sealing a plurality of the joints 'sealed by the sealing layer 7 The backing film 8, the surface protection sheet 6, and the back film 8 are fixed by a frame 9 to form a solar cell module. Further, the substrate for a solar cell of the present invention can also be used as a substrate of a solar cell module having an integrated structure. [Examples] [Measurement of Flow Start Temperature] A flow tester ("CFT-5 00 type") was used to fill a sample of about 2 g, and was mounted on a die having an inner diameter of 1 mm and a length of 10 mm. A capillary rheometer was used to melt and simultaneously extrude the sample at a temperature increase rate of 4 ° C/min under a load of 9.8 MPa (100 kgf/cm 2 ), and the temperature at which the melt viscosity reached 4800 Pa-s (48,000 poise) was measured. [Water vapor barrier evaluation] Based on the JIS K7129C method, the gas permeability and moisture permeability measuring device (GTR TEC technology (GTR-3 0X)) at a temperature of 40 ° C ' -16 - 201245323 relative humidity The water vapor transmission rate was measured under conditions of 90%. [Measurement of surface resistivity of indium tin oxide film] The surface resistivity (thin film resistance) of the indium tin oxide film was measured by a 4-probe method of resistance measuring apparatus (LORESTA AP manufactured by Mitsubishi Chemical Corporation). Production Example 1 In a reactor equipped with a stirring device, a torque tester, a nitrogen gas introduction tube, a thermometer, and a reflux condenser, 6-hydroxy-2-naphthoic acid was added to 1 034.99 g (5.5 mol), 2,6-naphthalene. Carboxylic acid 3 78.3 3 8 (1.75 mol), terephthalic acid 83.0 7 g (0.5 mol), hydroquinone 272.22 g (2.475 mol: relative to 2,6-naphthalenedicarboxylic acid and terephthalic acid) Total amount, 0.225 moles), acetic anhydride 1 226.8 7g (12 moles), and 1-methylimidazolium.17g as a catalyst. After the gas in the reactor is replaced by nitrogen, the nitrogen gas stream is stirred under nitrogen gas. The temperature was raised to 145 t at room temperature for 15 minutes, and refluxed at 145 ° C for 1 hour. Subsequently, while the by-product acetic acid and unreacted acetic anhydride were distilled off, the temperature was raised to 310 ° C at 145 ° C for 3 hours and 30 minutes, and after holding for 3 hours at 310 ° C, the contents were taken out and cooled to room temperature. The obtained solid was pulverized by a pulverizer to have a particle diameter of about 0 · 1 to 1 m m, and it was taken from room temperature to 250 ° C in a nitrogen atmosphere for 1 hour, and it was heated from 250 ° C to 310 in 10 hours. (:, and kept at 31 ° C for 5 hours for solid phase polymerization. After solid phase polymerization, cooling 'to obtain a powdery liquid crystal polyester. This liquid crystal polyester has a total amount of Ar1 of 2 with respect to the total repeating unit. 6 - anthracene repeating unit (1) 55 mol %, Ar2 is a repeating unit of 2,6-anthranyl group (2) 17.5 mol. /, Ar2 is 1,4-201245323 The unit (2) 5 mol%, and the Ar3 is a repeating unit of the 1,4-phenylene group (2) 22.5%, and the flow initiation temperature thereof is 3 3 3 (:: Production Example 2 is the same as in Production Example 1. The reactor was charged with p-hydroxybenzoic acid 91 lg (6.6 mol), terephthalic acid 2 74 g (1.65 m), isophthalic acid 91 g (0.55 mol), 4,4,-two Hydroxybiphenyl 409g (2.2 moles) 'Acetic anhydride 1 2 3 5 g (12.I mole), and as a catalyst! -Methylimidazolium.17g 'The gas in the reactor is replaced by nitrogen, nitrogen gas flow While stirring, it took 15 minutes to raise the room temperature to 5 〇 °c and reflux at 150 ° C for 1 hour. Then, after adding 1.7 g of 1-methylimidazole, the by-product acetic acid and Unreacted acetic anhydride While raising the temperature from 150 ° C to 320 ° C for 2 hours and 50 minutes, when the torque was increased, the contents were taken out and cooled to room temperature. The obtained solid matter was pulverized by a pulverizer to a particle size of about 〇1 to 1 mm, and then nitrogen was obtained. In the environment, it took 1 hour to raise the room temperature to 25, and it took 5 hours to raise the temperature to 285 ° C at 25 ° C and hold it at 28 5 ° C for 3 hours to carry out solid phase polymerization. After solid phase polymerization, it was cooled to obtain a powdery liquid crystal. Polyester. This liquid crystal polyester has a repeating unit of Ar1 of 1,4 -phenylene (1) 60 mol. / Ar2 is a repeating unit of 1,4-phenylene (2) 15 mol% 'Ar2 is hydrazine, 3_ benzene repeating unit (2) 5 mol%, and Ar3 is 4,4'-extended biphenyl repeating unit (3) 20%, and its flow initiation temperature is 327 °C. Example 1 The liquid crystal polyester obtained in Production Example 1 was granulated by a two-axis extruder ((Jibei-18-201245323 "PCM-30") to be pelletized, and then a one-axis extruder (spiral diameter) 50mm) melted, extruded by T mold (lip valve length 300mm, lip valve gap lmm, mold temperature 305 °C) into a film shape and then cooled to obtain a liquid crystal aggregate with a thickness of 25μηι The liquid crystal polyester film has a water vapor permeability of 0.011 g/m 2 · 24 h, and is excellent in water vapor barrier property as a substrate for a solar cell. Example 2 A liquid crystal polyester obtained in Production Example 1 is a two-axis. The extruder ((3) PCM-3 0) is granulated and becomes granulated. It is melted by a one-axis extruder (spiral diameter 50 mm). The T-die (lip valve length 300 mm, lip valve clearance 1 mm) The mold temperature was 3 5 (TC) extruded into a film form and then cooled to obtain a liquid crystal polyester having a thickness of 50 μm. The liquid crystal polyester film has a water vapor permeability of 0.003 g/m 2 '24 h ' as a substrate for a solar cell, and has excellent water vapor barrier properties. Example 3 The laminate film obtained in Example 2 was subjected to ion sputtering. A transparent electrode (indium tin oxide film) having a thickness of 200 nm was formed at a substrate temperature of 180 ° C using ITO (Indium Tin Oxide) on the opposite side to the gas barrier layer. The sheet resistance of the transparent electrode formed on this laminated film was measured to be 9.1 Ω/Ε]. Comparative Example 1 The liquid crystal polyester obtained in Production Example 2 was granulated by a two-axis extruder ("PC Μ - 30") into pellets, and then supplied to a one-axis extruder (spiral-19). - 201245323 Rotating diameter 50mm) is melted and extruded into a film shape by a τ mold (lip valve length 300 mm, lip valve gap lmm, mold temperature 3 50 ° C) and then cooled to obtain a liquid crystal polyester film having a thickness of 25 μm . The liquid crystal polyester film has a water vapor permeability of 0.343 g/m2 · 24h' as a substrate for a solar cell, and the water vapor barrier property is insufficient. Comparative Example 2 The liquid crystal polyester obtained in Production Example 2 was granulated by a two-axis extruder ("PCM-3 0") to be pelletized, and supplied to a one-axis extruder (spiral diameter: 50 mm). The molten metal is extruded into a film shape by a T-die (a lip valve length of 300 mm, a lip valve gap of 1 mm, and a mold temperature of 350 ° C), and then cooled to obtain a liquid crystal polyester film having a thickness of 5 μm. The water vapor permeability is 0.080 g/m 2 · 24 h 'as a substrate for a solar cell, and the water vapor barrier property is insufficient. Comparative Example 3 In the laminated film obtained in Comparative Example 2, a transparent electrode having a thickness of 200 nm was formed at a substrate temperature of 180 ° C by using an ITO (Indium Tin Oxide) on the opposite side of the gas barrier layer by ion sputtering. The sheet resistance of the transparent electrode formed on this laminated film was measured to be Ι2.3 Ω/Ε1. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] A cross-sectional view showing a state of a solar cell element in a mode. [Fig. 2] A cross-sectional view showing an example of a solar battery module in a mode. -20- 201245323 [Description of main component symbols] 1: Solar cell substrate 2: Inside electrode layer 3: Photoelectric conversion layer 3a: p-type semiconductor layer 3b: i-type semiconductor layer 3c: n-type semiconductor layer 4: surface electrode layer 5 : Solar battery element 6 = Surface protection sheet 7 : Sealing layer 8 : Back film 9 : Frame 1 〇: Solar battery module - 21