1284137 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係有關具有良好防止靜電性能、防止灰塵之附 著、光學性缺陷少之經塗敷之薄膜者。 【先前技術】 雙軸延伸聚酯薄膜由於具有機械性強度、尺寸安定性 、平坦性、耐熱性、耐藥性、透明性等良好特性，因此， 被廣泛做爲磁性記錄媒體之基礎薄膜，製版用薄膜、光學 用薄膜之使用。 惟，做成塑料薄膜之共通問題點如：靜電之產生易有 靜電之缺點，造成薄膜加工時，或加工製品走行性不良， 周圍灰塵四起之問題產生。 一般做爲聚酯薄膜靜電之防止方法者如：煉入有機磺 酸鹽等低分子量陰離子性界面活性劑型之化合物方法、蒸 鍍金屬化合物之方法、表面上塗佈陰離子性化合物、陽離 子性化合物、或導電性化合物之方法等。 煉入陰離子性化合物之方法具有可以廉價製造之優點 者，惟，防止靜電效果卻極有限。更且，因使用低分子量 化合物，而藉由白化後使陰離子性化合物聚集於聚酯薄膜 表面，降低聚酯薄膜與其塗層表面之粘著力降低，陰離子 性化合物轉沈薄膜，搬運滾輥等問題點產生。因此，亦降 低防靜電性能之耐久性。 蒸鍍金屬化合物之方法具良好靜電防止性能，因此， -6 - (2) 1284137 近來廣泛被做爲透明導電性薄膜之使用，惟，其製造成本 高，做爲特定用途時使用，而不易做爲一般之防止靜電薄 膜者。 塗佈導電性碳等之導電性化合物之方法其防止靜電效 果較爲理想，同時較可以低價製造之優點存在，惟，薄膜 透明性有惡化之缺點。 因此，做爲防靜電劑者以塗佈高分子量陰離子性化合 物、高分子量陽離子性化合物於薄膜之方法被廣泛做爲防 止聚酯薄膜靜電之方法使用者。 做爲具有塗佈層之雙軸延伸聚酯薄膜的製造方法者， 特別是其於薄膜製造步驟中進行塗佈之方法由經濟面及其 特性面較被廣泛進行者。做爲典型例者如：於縱延伸後橫 延伸前進行塗佈，進行橫延伸及熱固定之方法者。 又，特別是近年聚酯薄膜之用途呈多樣化連帶著薄膜 之加工，使用條件亦多樣化，如：使聚酯薄膜放置於100 °c以上之高溫時，於薄膜表面由內部滲出低聚物被析出後 ，此條件下進行加工或使用將產生各種問題。 先行做爲防止低聚物析出之方法者意圖藉由固相聚合 降低含於原料中之低聚物，又，使用末端感壓劑提昇聚酯 薄膜之耐水解性者，惟，無法滿足更嚴格條件下低聚物析 出之防止作用，或，製造成本太高等問題存在。 又，雖被提出以改善上述聚酯薄膜表面爲目的’進行 各種經塗敷之薄膜者，惟，依其塗佈組成，卻產生促進低 聚物析出之問題。 -7- (3) 1284137 本發明者鑑於上述問題而提供一種解決該課題後之具 良好防止靜電性能、防止灰塵附著、光學性缺陷少之聚酯 薄膜者。 【發明內容】 本發明者針對該課題進行精密硏討後結果發現，藉由 設定特別構成之塗佈層後，可解決該課題，進而完成本發 明。 亦即，本發明主旨係於單面具有塗佈層之聚酯薄膜者 ，塗佈層表面之表面固有電阻爲lx 1013Ω以下者，於180 °C下，進行熱處理該薄膜3 0分鐘後，該塗佈層表面之聚 酯低聚物量爲同熱處理前聚酯低聚物量之8倍以下者爲其 特徵之經塗敷之薄膜。 以下，詳細說明本發明。 構成本發明聚酯薄膜之聚酯係指二羧酸成份與二醇成 份相互縮聚後取得之聚酯者。做爲此等二羧酸成份者如·· 對苯二甲酸、異苯二甲酸、酞酸、2，6-萘二羧酸、己二 酸、癸二酸、4，4’-二苯基二羧酸、1，4-環己二羧酸等 者，做爲二醇成份例者如：乙二醇、二乙二醇、三乙二醇 、丙二醇、丁二醇、三亞甲基二醇、四亞甲基二醇、新戊 基二醇、1，4_環己烷二甲醇等例。 做爲本發明所使用之聚酯之代表例如··聚乙烯對苯二 甲酸酯、聚乙烯-2，6-萘二甲酸酯、聚-1，4-環己烷二亞 甲基對苯二甲酸酯等例，而，其他亦可共聚該酸成分，二 -8- (4) 1284137 醇成份之聚酯者，必要時，亦可含其他成份、添加劑者。 本發明聚酯薄膜中，爲易於使用，亦可含有附潤滑性 之粒子者。做爲該目的所使用之粒子例如：二氧化矽、碳 酸鈣、碳酸鎂、磷酸鈣、陶土、滑石、氧化鋁、氧化鈦、 礬土、硫酸鋇、氟化鈣、氟化鋰、沸石、硫化鉬等無機粒 子、交聯高分子粒子、草酸鈣等有機粒子、更可使用聚酯 製造工程時之析出粒子等。 所使用粒子粒徑，含量依其薄膜之用途、目的進行選 取之，一般平均粒徑爲 0.005〜5.0// m者宜，較佳者爲 0.0 1〜3.0 // m。當平均粒徑超出5.0 // m時，則薄膜表面粗 細度變得太粗，粒子是由薄膜表面脫落。反之，平均粒徑 低於0 · 0 0 5 μ m則表面粗細度太細，無法取得充份的易滑 性。粒子含量通常爲聚酯之〇 . 0 0 1〜3 0.0重量％者宜，較佳 者爲0.0 1〜1 0.0重量％。當粒子量變多時，則損及薄膜之 機械特性、透明性者、太少則易滑性變差。 又’除上記粒子之外’必要時亦可添加添加劑。做爲 此添加劑者如：靜電防止劑、安定劑、潤滑劑、交聯劑、 防連粘劑、防氧化劑、染料、顏料、遮光劑、紫外線吸收 劑等例。 本發明聚酯薄膜只要滿足本發明要件者亦可爲多層結 構者，多層結構時，亦可含非聚酯層者。又，塗佈層可設 定於薄膜單面、或雙面均可，當然含本發明槪念者，至少 單面塗佈層爲滿足本發明要件即可。 本發明聚酯薄膜係以其塗佈層表面固有電阻爲1 x -9- (5) 1284137 1 〇13以下者爲其特徵之經塗敷之薄膜者，較佳之表 電阻爲1 X 1 〇 12 Ω以下，更佳者爲1 X 1 0 1G Ω以下。 固有電阻爲超出1 X 1 0 13 Ω時，則捲呈滾筒狀之薄 捲出時，使重疊之單片狀薄膜依序搬運時將產生相 之密合、加工不良、附著異物、灰塵等問題。 又，本發明聚酯薄膜中，於180°C下進行熱處 3 〇分鐘後塗佈層表面之聚酯低聚物量爲相同處理 的8倍以下者，18(TC下熱處理薄膜30分鐘後之塗 面聚酯低聚物量爲3.0mg/m2以下者宜。 當熱處理後塗佈層表面之聚酯低聚物量超出此 ，則聚酯薄膜之用途將受限。如：設置粘著層於設 層之聚酯薄膜後，粘貼於其他部材後，使聚酯薄膜 層分離做爲脫模薄膜使用時，由薄膜析出之低聚物 層中進行結晶化後，產生亮度等光學缺陷問題爲公 其他透明薄膜亦藉由濁度增加損及外觀，設定表塗 時，降低與表塗層之密合性，或污染加工裝置降低 之問題產生。 爲解決上述各種問題，於本發明聚酯薄膜中設 降低表面固有電阻與密封低聚物之析出性能之塗佈 發明中做爲構成設置於薄膜之塗佈層成份者以具有 基之化合物、聚乙烯醇爲較佳使用者。 具有季銨鹽基之化合物係指於分子中之主鏈、 具有含季銨鹽基之構成要素者謂之。做爲該構成要 如：吡咯烷嗡環、烷胺之4級化物、更將此等與丙 面固有 當表面 膜進行 互薄膜 理薄膜 前之値 佈層表 範圍時 有脫模 與脫模 於粘著 知者。 層使用 生產性 置具有 層。本 季銨鹽 側鏈中 素例者 烯酸、 -10- (6) 1284137 甲基丙烯酸共聚者、N-烷胺丙烯醯胺之4級化物、乙烯苄 基三甲銨鹽、2-羥基3-甲基丙烯氧丙基三甲銨鹽等例。更 有此等組合者，或與其他樹脂共聚者亦無妨。另外，做爲 此等季銨鹽呈對離子之陰離子者如··鹵素、烷基硫酸鹽、 烷基磺酸鹽、硝酸等離子例者。又，本發明中，具有季銨 鹽基之化合物以高分子化合物者宜。分子量太低時，由塗 佈層容易去除後，經時性出現降低性能，恐有塗佈層粘腻 之虞。又，分子量低則耐熱安定性變差。爲防止不產生此 不良點，該具季銨鹽基化合物之數平均分子量通常爲 1 000以上者宜，更以2000以上、特別以5 000以上爲最 佳。反之，該化合物之分子量太高時，將產生塗佈液粘度 太高等不良狀態。爲防止此不良點產生，其數平均分子量 爲500000以下者宜。 本發明所使用之聚乙烯醇一般藉由聚合反應後合成之 ，爲水溶性者宜。 聚乙烯醇之聚合度並未限定，一般爲1 〇〇以上、較佳 者爲300〜40000者。當聚合度不足100時，則有降低塗佈 層之耐水性傾向。聚乙烯醇之皂化度並未特別限定，一般 爲70莫耳％以上，較佳者爲80莫耳％以上，99.9莫耳％ 以下之聚醋酸乙烯酯皂化物爲實用者。 更於塗佈層中必要時可倂用1種或2種以上上記以外 之水溶性或水分散性之粘合劑樹脂者。做爲該粘合劑樹脂 例者如··聚酯、聚胺酯、丙烯樹脂、乙烯樹脂、環氧樹脂 、醯胺樹脂等例。此等分別骨架結構藉由共聚等後’實質 -11 - (7) 1284137 上具有複合結構亦可。做爲具有複合結構之 如：丙烯樹脂接枝聚酯、丙烯樹脂接枝聚胺 接枝聚酯、乙烯樹脂接枝聚胺酯等例。 必要時亦可含交聯反應性化合物。交聯 係主要與含於塗佈層構成成份中之官能基進 ，改善塗佈層之凝聚性、表面硬度、耐擦傷 、耐水性者爲宜。 本發明薄膜塗佈層亦可含有界面活性劑 佈性改良劑、增粘劑、靜電防止劑、有機系 粒子、無機粒子、氧化防止劑、紫外線吸收 染料、顏料等添加劑。此等添加劑可單獨使 亦可倂用2種以上者。 塗佈層構成成份中所佔具季銨鹽基化· 10〜99重量％、較佳者爲20〜95重量％者。 此範圍時，則將無法取得所期之靜電防止性 出防止性能。 本發明所使用塗佈液於使用上、作業環 或水分散液者宜，以水做爲主要媒體者，在 主旨範圍下，亦可含有機溶劑。 塗佈液之固形份濃度並未特別限定，_ 重量％、較佳者爲0.5〜30重量％、更佳者爲 。當濃度不在此範圍內則爲取得足夠機能下 厚度之塗佈層。 塗佈層之厚度於乾燥厚度下，一般爲 粘合劑樹脂者 酯、乙烯樹脂 反應性化合物 行交聯反應後 性、耐溶劑性 、消泡劑、塗 潤滑劑、有機 劑、發泡劑、 用之’必要時 合物之比率爲 該比率若不在 能、低聚物析 境上、水溶液 不超出本發明 一般爲 〇·3〜65 1〜2 〇重量％者 不易設置必要 〇 〇〇3 〜1.5// m -12- (8) 1284137 、較佳者爲0.005〜0.5// m、更佳者爲0.01〜0.3// m。當塗 佈層厚度不足0.003 // m時，恐無法取得足夠之性能，反 之，超出1 . 5 // m則薄膜相互產生連粘。 設置塗佈層於聚酯薄膜之方法以採用使聚酯薄膜於製 造步驟中進行塗佈塗層液之方法者宜。如：於未延伸薄膜 上進行塗佈後，進行延伸之方法，於單軸延伸薄膜進行塗 佈後’進行延伸之方法，於雙軸延伸薄膜進行塗佈後，進 行延伸之方法等。特別是於未延伸、或單軸延伸薄膜上進 行塗佈塗層液後，於拉幅器同時進行乾燥及延伸之方法爲 較經濟者。 於聚酯薄膜上進行塗佈塗層劑之方法例如：原崎勇次 著、稹書店、1 979年發行、「塗佈方式」所示之塗佈技 術可使用之。具體而言如：氣動刮塗、刮板塗佈、棒塗佈 、刮刀塗佈、擠壓塗佈、浸漬塗佈、逆輥塗佈、轉輥塗佈 、影寫版塗佈、滾觸塗佈、鑄造塗佈、噴霧塗佈、簾流塗 佈、壓延塗佈、擠壓塗佈、條狀塗佈等技術。 【實施方式】 以下例舉實施例進行本發明更詳細之說明，惟，本發 明在不超出其主旨下，其不限於以下實施例者。又，實施 例及比較例之評定方法、樣品處理方法如下。 (1)表面固有電阻値： 使用日本 hulet · pacard 公司製高電阻測定器 -13- (9) 1284137 (HP43 3 9B)及測定電極（HP 1 6008B)，於 23t：，50%RH 之 測定氣氛下使樣品充份調濕後，以外加電壓1 00V測定1 分鐘後塗佈層表面固有電阻値。 (2) 薄膜之熱處理方法： 將A4繪圖紙與熱處理之聚酯薄膜重疊。此時，將測 定低聚物量之面以外側四個角別上迴紋針，固定繪圖紙與 聚酯薄膜。於氮氣氛、1 8 (TC之烤箱中，放置該聚酯薄膜 3 〇分鐘後進行熱處理。 (3) 薄膜表面低聚物量測定法： 放開上部，底邊面積呈250cm2折疊聚酯薄膜，作成 四方型箱。設置塗佈層時，塗佈層面向內側。 再於該方法所作成之箱子中置入l〇ml DMF(二甲基甲 醯胺）放置3分鐘後回收DMF。將回收之DMF供入液體層 析法（島津LC-7A)後求取DMF中之聚酯低聚物量，此低 聚物量之値除以接觸DMF之薄膜面積後，做爲薄膜表面 低聚物量（mg/m2)。 (4) 薄膜表面低聚物量評定i : 準備未經熱處理之薄膜，與上記（2)所示方法於1 8 〇艺 熱處理30分鐘之薄膜。再以該（3)所示方法，分別測定雙 方薄膜表面低聚物量後，以熱處理前之値除以熱處理後之 値、求取比率。 -14 - (10) 1284137 (5) 薄膜表面低聚物量評定2: 以該（2)所示方法，180°C下熱處理薄膜3〇分鐘。再 以該（3)所示方法，測定該薄膜表面之低聚物量。 (6) 灰塵附著性評定（Ash test): 2 3 C、5 0 % RH之測定氣氛下充份調濕聚酯薄膜後， 以棉布重覆進行i 〇次塗佈層。將此，悄悄站上碎香煙灰 ’依以下基準評定附著煙灰之狀況。 〇：薄膜即使接觸煙灰仍未附著。 △:薄膜接觸煙灰後少許附著之。 X :薄膜僅稍接觸煙灰後即大量附著之。 (7) 光學缺陷檢查： 聚酯薄膜表面（下記實施例、比較例中設置塗佈層之 面）以塗佈量爲0. lg/m2(乾燥後）設置如下記（R-1)所示之脫 模層後，取得脫模薄膜。再於脫模層上進行塗佈丙烯系粘 著劑，於180 °C下乾燥5分鐘後設置厚度20 // m之粘著層 。將此粘著於玻璃板後，去除脫模薄膜取得之粘著層樣品 放置於偏光顯微鏡台之上，挾住樣品之2片偏光子設定成 交叉尼爾棱晶觀察亮度等光學異常缺陷。光學缺陷計算大 小爲0.5 // m以上者，其個數換算成粘著層面積後，依以 下基準進行評定。 〇：光學缺陷爲0.5個/m2以下（實用上沒問題） △:光學缺陷爲0.5個/m2以上、1.0個/m2以下（實用 -15- (11) 1284137 上稍有問題） X :光學缺陷爲1.0個/m2以上（實用上有問題） <脫模層（R-1)組成〉 硬化型聚矽氧樹脂/硬化觸媒/溶媒之重量比爲 1 00/5/2000、惟，溶媒係甲苯/MEK以1/1之比率所混合 之溶媒者。 〔比較例1〕 充份乾燥固有粘度0.65之聚乙烯對苯二甲酸酯之碎 片，於28 0〜3 00°C下進行加熱熔融後，由T字型接頭擠出 薄片狀，利用靜電密接法密接於表面溫度40〜50°C之鏡面 冷卻轉筒之同時進行冷卻固化後，作成未延伸之聚乙烯對 苯二甲酸酯薄膜。此薄膜通過8 5 °C之加熱滾筒群同時往 縱方向延伸3.7倍，做成單軸定向薄膜。此單軸定向薄膜 藉由拉幅延伸機於l〇〇t下往橫方向延伸4.0倍，更於 230°C下進行熱處理後，取得薄膜厚度爲50// m之雙軸延 伸定向聚乙烯對苯二甲酸酯薄膜。 〔實施例1〕 於薄膜製造步驟中進行經塗敷之薄膜與乾燥。具體例 如：藉由相同於比較例之順序，製造薄膜之步驟中，於縱 延伸後，橫延伸前之單軸定向薄膜單面上，進行塗佈如下 記（A)所示之塗佈液。再於拉幅延伸機中利用熱進行乾燥 -16- (12) 1284137 。以下與比較例1同法取得厚度5〇//m之基材薄膜上設 置0.0 5 g/m2量塗佈層之層合雙軸延伸定向聚乙烯對苯二 甲酸酯薄膜。 <塗佈液（A)〉 主鏈上具有吡咯烷嗡環聚合物之第1工業製藥公司製 sharoll DC-303P/皂化度=88莫耳％、聚合度= 500之聚乙 烯醇/平均粒徑0.0 5/zm之二氧化矽熔膠之固形份換算重 量組成比含85/10/5比例之水性塗佈液。 〔實施例2〜4〕 實施例1中，除變更塗佈液內容爲下記（B)、（C)、 (D)之外，同法取得厚度50 // m基材薄膜上設置〇.〇5g/m2 量之塗佈層層合雙軸延伸定向聚乙烯對苯二甲酸酯薄膜， 分別做成實施例2、實施例3、實施例4。 <塗佈液（B)> 主鏈中具有吡咯烷嗡環之聚合物第1工業製藥公司製 sharoll DC-303P/皂化度=88莫耳。/〇、聚合度= 500之聚乙 烯醇/甲氧基羥甲基蜜胺、大日本油墨化學工業製 becamin/平均粒徑0.05/zm之二氧化矽熔膠之固形份換算 重量組成比含4 〇 / 2 0 / 3 5 / 5比例之水性塗佈液者。 <塗佈液（C)> 聚三甲胺乙基甲基丙烯酸酯4級化物/皂化度=88莫 -17- (13) 1284137 耳％、聚合度=500之聚乙烯醇/甲氧基羥甲基蜜胺、大日 本油墨化學工業製bee am in/平均粒徑0.05// m之二氧化矽 熔膠含固形份換算重量組成比40/20/3 5/5比例之水性塗佈 液0 <塗佈液（D)> 依常法，取得三甲胺乙基甲基丙烯酸酯4級化物/甲 基丙烯酸甲酯之重量組成比6 5/3 5比例共聚之化合物（D-1)。利用此化合物D-l、D-1/皂化度=88莫耳％、聚合度 = 5 00之聚乙烯醇/甲氧基羥甲基蜜胺、大日本油墨化學工 業製bee am in/平均粒徑0.05 // m之二氧化矽熔膠含固形份 換算重量組成比70/10/15/5比例之水性塗佈液。 〔比較例2〜3〕 實施例1中除變更塗佈液內容爲下記（E)、（F)之外， 同法取得厚度50#m基材薄膜上設置〇.〇5g/m2量塗佈層 之層合雙軸延伸定向聚乙烯對苯二甲酸酯薄膜，分別做成 比較例2、比較例3。 <塗佈液（E)> 皂化度=88莫耳％、聚合度=500之聚乙烯醇/甲氧基 羥甲基蜜胺、大日本油墨化學工業製 becami η/平均粒徑 0.0 5 // m之二氧化矽熔膠含固形份換算重量組成比 85/1〇/5比例之水性塗佈液。 -18- (14) 1284137 <塗佈液（F)> 聚三甲胺乙基甲基丙烯酸酯4級化物/丙烯酸烷酯與 甲基丙烯酸烷酯共聚後，Tg爲40 °C之丙烯樹脂、日本 Carbaid工業製nicasol/甲氧基羥甲基蜜胺、大日本油墨 化學工業製becami η/平均粒徑0.05// m之二氧化矽熔膠含 固形份換算重量組成比4 0 / 2 0 / 3 5 / 5比例之水性塗佈液。 以上所取得薄膜之特性及實用特性如下記表1及2所 示0 表11284137 (1) Field of the Invention The present invention relates to a coated film which has good antistatic properties, prevents adhesion of dust, and has few optical defects. [Prior Art] Biaxially stretched polyester film is widely used as a base film for magnetic recording media because of its mechanical strength, dimensional stability, flatness, heat resistance, chemical resistance, transparency, and the like. Use of film and optical film. However, the common problem of making a plastic film is that the generation of static electricity is liable to have the disadvantage of static electricity, resulting in poor film running during processing of the film or the problem of dust around the film. Generally, it is used as a method for preventing static electricity of a polyester film, such as a method of compounding a low molecular weight anionic surfactant type such as an organic sulfonate, a method of vapor-depositing a metal compound, and coating an anionic compound or a cationic compound on the surface. Or a method of a conductive compound or the like. The method of refining an anionic compound has the advantage of being inexpensive to manufacture, but the effect of preventing static electricity is extremely limited. Furthermore, by using a low molecular weight compound, the anionic compound is aggregated on the surface of the polyester film by whitening, and the adhesion of the polyester film to the surface of the coating is lowered, and the anionic compound is transferred to the film, and the roller is conveyed. Point generation. Therefore, the durability of the antistatic property is also lowered. The method of vapor-depositing a metal compound has good static electricity prevention performance. Therefore, -6 - (2) 1284137 has recently been widely used as a transparent conductive film, but its manufacturing cost is high, and it is used as a specific use, and is not easy to be used. For general anti-static film. A method of applying a conductive compound such as conductive carbon prevents the electrostatic effect and is advantageous in that it can be produced at a low cost, but the transparency of the film is deteriorated. Therefore, as an antistatic agent, a method of applying a high molecular weight anionic compound or a high molecular weight cationic compound to a film is widely used as a method for preventing static electricity of a polyester film. As a method for producing a biaxially stretched polyester film having a coating layer, in particular, the method of coating it in the film production step is widely carried out from an economical surface and a characteristic surface thereof. As a typical example, a method of coating and performing lateral stretching and heat fixation before longitudinal stretching and horizontal stretching is employed. In addition, especially in recent years, the use of polyester film is diversified with a film processing, and the use conditions are also diverse, such as: when the polyester film is placed at a high temperature of 100 ° C or higher, the oligomer is oozing from the inside of the film surface. After being precipitated, processing or use under such conditions will cause various problems. First, as a method for preventing the precipitation of oligomers, it is intended to reduce the oligomer contained in the raw material by solid phase polymerization, and to improve the hydrolysis resistance of the polyester film by using a terminal pressure sensitive agent, but it is not possible to satisfy the stricter The prevention of the precipitation of the oligomer under the conditions, or the manufacturing cost is too high, and the like exists. Further, although it has been proposed to carry out various coated films for the purpose of improving the surface of the above-mentioned polyester film, there is a problem that the deposition of the oligomer is promoted depending on the coating composition. -7- (3) 1284137 In view of the above problems, the inventors of the present invention have provided a polyester film which has excellent antistatic properties, prevents dust adhesion, and has few optical defects. SUMMARY OF THE INVENTION The inventors of the present invention have found that the problem can be solved by setting a coating layer having a special configuration, and the present invention has been completed. That is, the present invention is directed to a polyester film having a coating layer on one side, and the surface specific resistance of the surface of the coating layer is 1×10 13 Ω or less, and after heat treatment of the film at 180 ° C for 30 minutes, The amount of the polyester oligomer on the surface of the coating layer is a coated film characterized by being 8 times or less the amount of the polyester oligomer before the heat treatment. Hereinafter, the present invention will be described in detail. The polyester constituting the polyester film of the present invention is a polyester obtained by mutually polycondensing a dicarboxylic acid component and a diol component. For such dicarboxylic acid components, such as terephthalic acid, isophthalic acid, citric acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, 4,4'-diphenyl Dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc., as diol components such as: ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, trimethylene glycol Examples of tetramethylene glycol, neopentyl glycol, and 1,4-cyclohexane dimethanol. Representative of the polyester used in the present invention, for example, polyethylene terephthalate, polyethylene-2,6-naphthalate, poly-1,4-cyclohexanedimethylene pair Examples of phthalic acid esters and the like, and other polyesters which are copolymerized with the acid component, the di-8-(4) 1284137 alcohol component, and if necessary, may contain other components and additives. In the polyester film of the present invention, it is also easy to use and may contain particles having lubricity. Particles used for this purpose are, for example, cerium oxide, calcium carbonate, magnesium carbonate, calcium phosphate, clay, talc, alumina, titania, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, sulfurization. Organic particles such as molybdenum, crosslinked polymer particles, and organic particles such as calcium oxalate, and precipitated particles in the case of polyester production engineering can be used. The particle size and content of the particles to be used are selected according to the purpose and purpose of the film, and the average particle diameter is generally 0.005 to 5.0//m, preferably 0.0 1 to 3.0 // m. When the average particle diameter exceeds 5.0 // m, the film surface roughness becomes too coarse, and the particles are peeled off from the surface of the film. On the other hand, if the average particle diameter is less than 0 · 0 0 5 μ m, the surface roughness is too fine to obtain sufficient slipperiness. The particle content is usually 聚酯 of the polyester. 0 0 1 to 3 is preferably 0.0% by weight, preferably 0.01 to 10.0% by weight. When the amount of particles is increased, the mechanical properties and transparency of the film are impaired, and the slipperiness is deteriorated when the amount is too small. Further, an additive may be added as needed in addition to the above-mentioned particles. As such additives, such as: an antistatic agent, a stabilizer, a lubricant, a crosslinking agent, an anti-adhesion agent, an antioxidant, a dye, a pigment, an opacifier, and an ultraviolet absorber. The polyester film of the present invention may be a multilayer structure as long as it satisfies the requirements of the present invention, and may also contain a non-polyester layer in a multilayer structure. Further, the coating layer may be provided on one side of the film or on both sides, and of course, the present invention may be provided, and at least the one-side coating layer may satisfy the requirements of the present invention. The polyester film of the present invention is a coated film characterized by having a coating layer having a surface specific resistance of 1 x -9 - (5) 1284137 1 〇 13 or less, preferably having a surface resistance of 1 X 1 〇12. Below Ω, more preferably 1 X 1 0 1G Ω or less. When the inherent resistance is more than 1 X 1 0 13 Ω, when the roll is rolled in a thin roll shape, the overlapping single-piece film is sequentially transported, causing problems such as close contact, poor processing, adhesion of foreign matter, dust, etc. . Further, in the polyester film of the present invention, after the heat is applied at 180 ° C for 3 minutes, the amount of the polyester oligomer on the surface of the coating layer is 8 times or less of the same treatment, and 18 (the film is heat-treated for 30 minutes after TC). The amount of the polyester oligomer to be coated is preferably 3.0 mg/m2 or less. When the amount of the polyester oligomer on the surface of the coating layer exceeds this after heat treatment, the use of the polyester film is limited. For example, an adhesive layer is provided. After the polyester film of the layer is adhered to another member and the polyester film layer is separated and used as a release film, the crystallization is performed in the oligomer layer deposited by the film, and an optical defect such as brightness is generated. The transparent film is also damaged by the increase in turbidity, and when the surface coating is set, the adhesion to the surface coating is lowered, or the problem of contamination of the processing device is reduced. To solve the above various problems, the polyester film of the present invention is provided. In the coating method for reducing the surface specific resistance and the precipitation performance of the sealing oligomer, it is preferable to use a compound having a base or polyvinyl alcohol as a component constituting the coating layer provided on the film. Compound means The main chain in the molecule and the constituent element having a quaternary ammonium salt group are referred to as the pyrrolidinium ring, the alkylate compound, and the like. In the range of the surface layer of the inter-membrane film, there are mold release and demoulding in the adhesive. The layer is made of a productive layer. The quaternary acid in the side chain of the ammonium salt in this season is -10- (6) 1284137 methacrylic acid copolymerizer, N-alkylamine acrylamide quaternary compound, ethylene benzyl trimethylammonium salt, 2-hydroxy 3-methyl propylene oxypropyl trimethyl ammonium salt, etc., etc. Or, it may be combined with other resins. In addition, the quaternary ammonium salt is an anion of a counter ion such as halogen, alkyl sulfate, alkyl sulfonate, nitric acid, etc. Further, the present invention Among them, a compound having a quaternary ammonium salt group is preferably a polymer compound. When the molecular weight is too low, the coating layer is easily removed, and the properties are deteriorated with time, and the coating layer is sticky. The heat stability is deteriorated. To prevent this from happening, the quaternary ammonium The number average molecular weight of the base compound is usually preferably 1,000 or more, more preferably 2,000 or more, particularly preferably 5,000 or more. Conversely, when the molecular weight of the compound is too high, a problem occurs in that the viscosity of the coating liquid is too high. It is preferable to prevent the occurrence of such a defect, and the number average molecular weight is preferably 50000 or less. The polyvinyl alcohol used in the present invention is generally synthesized by a polymerization reaction, and is preferably water-soluble. The degree of polymerization of polyvinyl alcohol is not limited, generally When the degree of polymerization is less than 100, the water repellency of the coating layer tends to be lowered. The degree of saponification of the polyvinyl alcohol is not particularly limited, and is generally 70% by mole. The above is preferably 80 mol% or more, and 99.9 mol% or less of polyvinyl acetate saponified product is practical. Further, one or two or more kinds of water-soluble or water-dispersible binder resins other than the above may be used in the coating layer. Examples of the binder resin include polyester, polyurethane, acryl resin, vinyl resin, epoxy resin, and guanamine resin. These respective skeleton structures may have a composite structure by copolymerization, etc., after the substance -11 - (7) 1284137. As a composite structure, such as: propylene resin grafted polyester, propylene resin grafted polyamine grafted polyester, vinyl grafted polyurethane and the like. If necessary, a cross-linking reactive compound may also be included. The crosslinking system is mainly composed of a functional group contained in the constituent component of the coating layer, and it is preferred to improve the cohesiveness, surface hardness, scratch resistance, and water resistance of the coating layer. The film coating layer of the present invention may further contain an additive such as a surfactant-based improver, a thickener, an antistatic agent, organic particles, inorganic particles, an oxidation preventive agent, an ultraviolet absorbing dye, or a pigment. These additives may be used alone or in combination of two or more. The coating layer constituent component has a quaternary ammonium salt content of 10 to 99% by weight, preferably 20 to 95% by weight. In this range, the expected static electricity prevention prevention performance will not be obtained. The coating liquid to be used in the present invention is preferably used in the operation, the working ring or the aqueous dispersion, and water as the main medium, and may contain an organic solvent in the scope of the main purpose. The solid content concentration of the coating liquid is not particularly limited, and is preferably from 0.5 to 30% by weight, more preferably from 0.5 to 30% by weight. When the concentration is not within this range, it is a coating layer having a sufficient thickness. The thickness of the coating layer is generally a binder resin, a resin reactive compound, a cross-linking reaction, a solvent resistance, an antifoaming agent, a lubricant, an organic agent, a foaming agent, and the like. When the ratio of the compound is used as the ratio, if the ratio is not in the energy, the oligomer is precipitated, and the aqueous solution does not exceed the present invention, generally 〇·3~65 1~2 〇% by weight. It is not easy to set the necessary 〇〇〇3 〜 1.5// m -12- (8) 1284137, preferably 0.005 to 0.5//m, more preferably 0.01 to 0.3//m. When the thickness of the coating layer is less than 0.003 // m, sufficient performance may not be obtained. Conversely, if the thickness of the coating layer exceeds 1.5 / m, the films are mutually viscous. The method of applying the coating layer to the polyester film is preferably carried out by using a method of coating the polyester film in the production step. For example, a method of stretching after coating on an unstretched film, a method of stretching after uniaxially stretching the film, and a method of stretching after coating the biaxially stretched film, and the like. In particular, after the coating liquid is applied to the unstretched or uniaxially stretched film, the method of simultaneously drying and stretching the tenter is economical. The coating method for applying a coating agent to a polyester film can be used, for example, in the coating technique shown by "Sakasaki", published in the 1979 issue, "The Coating Method". Specifically, for example: pneumatic blade coating, blade coating, bar coating, blade coating, extrusion coating, dip coating, reverse roll coating, roll coating, image coating, roller coating Techniques such as cloth, cast coating, spray coating, curtain coating, calender coating, extrusion coating, strip coating, and the like. BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in more detail by way of examples. However, the present invention is not limited to the following examples. Further, the evaluation methods and sample processing methods of the examples and comparative examples are as follows. (1) Surface specific resistance 値: Measurement atmosphere of 23t:, 50% RH using a high-resistance measuring device 13-(9) 1284137 (HP43 3 9B) and a measuring electrode (HP 1 6008B) manufactured by Japan hulet · pacard After the sample was sufficiently conditioned, the surface specific resistance 値 of the coating layer was measured after applying the voltage of 100 V for 1 minute. (2) Heat treatment method of the film: The A4 drawing paper is overlapped with the heat-treated polyester film. At this time, the surface of the oligomer is measured and the paper is fixed at the outer four corners to fix the drawing paper and the polyester film. The polyester film was placed in a nitrogen atmosphere at 18 °C in an oven for 3 minutes, and then heat-treated. (3) Measurement of the amount of oligomer on the surface of the film: The upper portion was opened, and the bottom surface area was 250 cm2, and the polyester film was formed. Square box. When the coating layer is set, the coating layer faces inward. DMF is then placed in a box made by this method for 3 minutes, and DMF is recovered. The recovered DMF will be recovered. After the liquid chromatography (Shimadzu LC-7A) was supplied, the amount of the polyester oligomer in the DMF was determined. The amount of the oligomer was divided by the area of the film contacting the DMF, and the amount of the oligomer on the surface of the film (mg/m2). (4) Evaluation of the amount of oligomer on the surface of the film i: Prepare a film which has not been heat-treated, and heat-treat the film for 30 minutes at the same time as the method shown in (2) above, and then use the method shown in (3). After measuring the amount of oligomer on both surfaces of the film, the enthalpy before heat treatment is divided by the enthalpy after heat treatment, and the ratio is determined. -14 - (10) 1284137 (5) Evaluation of the amount of oligomer on the surface of the film 2: As shown in (2) Method, heat-treating the film at 180 ° C for 3 minutes, and measuring the thin film by the method shown in (3) (6) Evaluation of dust adhesion (Ash test): 2 3 C, 50% RH After the measurement of the atmosphere, the polyester film was sufficiently moistened, and the coating layer was repeatedly coated with cotton. In this case, the condition of the attached soot is evaluated by the following criteria: 〇: The film is not attached even if it is in contact with the soot. △: The film is slightly attached after contact with the soot. X: The film is only slightly contacted with the soot. (1) Optical defect inspection: The surface of the polyester film (the surface of the coating layer in the following examples and comparative examples) is set to 0. lg/m2 (after drying) is set as follows (R-1) After the release layer shown, a release film was obtained, and a propylene-based adhesive was applied to the release layer, and dried at 180 ° C for 5 minutes, and then an adhesive layer having a thickness of 20 // m was set. After adhering to the glass plate, the adhesive layer sample obtained by removing the release film is placed on the polarizing microscope stage, and the two polarizers of the sample are set to observe optical anomalies such as brightness of the cross-earth prism. Calculate the size of 0.5 / m or more, the number of which is converted into the adhesion layer area After that, the evaluation is based on the following criteria: 〇: The optical defect is 0.5/m2 or less (there is no problem in practical use) △: The optical defect is 0.5/m2 or more and 1.0/m2 or less (utility-15-(11) 1284137 Slightly problem) X: Optical defect is 1.0/m2 or more (practical problem) <Release layer (R-1) composition> Hardened polyoxyl resin/hardening catalyst/solvent weight ratio is 00 /5/2000, except that the solvent is toluene/MEK mixed at a ratio of 1/1. [Comparative Example 1] A piece of polyethylene terephthalate having an intrinsic viscosity of 0.65 was sufficiently dried and heated and melted at 28 0 to 300 ° C, and then extruded into a sheet shape by a T-shaped joint, and electrostatically bonded thereto. The film was cooled and solidified while being attached to a mirror cooling drum having a surface temperature of 40 to 50 ° C to form an unstretched polyethylene terephthalate film. The film was stretched 3.7 times in the longitudinal direction by a heating roller group at 85 ° C to form a uniaxially oriented film. The uniaxially oriented film is extended by 4.0 times in the transverse direction by a tenter stretching machine, and further heat treated at 230 ° C to obtain a biaxially oriented polyethylene pair having a film thickness of 50 / / m. Phthalate film. [Example 1] A coated film was dried and dried in a film production step. Specifically, in the step of producing a film in the same manner as in the comparative example, the coating liquid shown in the following (A) is applied to one side of the uniaxially oriented film before the longitudinal stretching and after the longitudinal stretching. Further drying with a heat in a tenter stretching machine -16- (12) 1284137. In the same manner as in Comparative Example 1, a laminated biaxially oriented polyethylene terephthalate film having a coating layer of 0.05 g/m2 was formed on a substrate film having a thickness of 5 Å/m. <Coating liquid (A)> Sharoll DC-303P made by the first industrial pharmaceutical company having a pyrrolidinium ring polymer in the main chain/saponification degree = 88 mol%, polymerization degree = 500 polyvinyl alcohol / average particle The solid content of the cerium oxide melt having a diameter of 0.05/zm is converted into an aqueous coating liquid having a ratio of 85/10/5. [Examples 2 to 4] In Example 1, except that the contents of the coating liquid were changed to the following (B), (C), and (D), the thickness of the substrate film was 50 Ω. A coated layer of 5 g/m 2 of the biaxially oriented polyethylene terephthalate film was laminated into Example 2, Example 3, and Example 4, respectively. <Coating liquid (B)> Polymer having a pyrrolidinium ring in the main chain Sharoll DC-303P/saponification degree = 88 mol. /〇, polymerization degree = 500 polyvinyl alcohol / methoxymethylol melamine, large Japanese ink chemical industry becamin / average particle size of 0.05 / zm of cerium oxide melt solid content conversion weight composition ratio of 4 〇 / 2 0 / 3 5 / 5 ratio of aqueous coating liquid. <Coating liquid (C)> Polytrimethylamine ethyl methacrylate grade 4/saponification degree = 88 Mo-17- (13) 1284137 Ear %, degree of polymerization = 500 polyvinyl alcohol / methoxy group Hydroxymethyl melamine, big Japanese ink chemical industry bee am in / average particle size 0.05 / / m cerium oxide melt solid content conversion weight composition ratio 40/20/3 5 / 5 ratio of aqueous coating liquid 0 <coating liquid (D)> A compound obtained by copolymerizing a weight ratio of trimethylamine ethyl methacrylate grade 4 / methyl methacrylate to a ratio of 6 5 / 3 5 by a usual method (D-1) ). Using this compound D1, D-1/saponification degree=88 mol%, polymerization degree=500 00 polyvinyl alcohol/methoxymethylol melamine, Dainippon ink chemical industry bee am in/average particle diameter 0.05 // m cerium oxide melt contains an aqueous coating solution with a solid content ratio of 70/10/15/5. [Comparative Examples 2 to 3] In Example 1, except that the contents of the coating liquid were changed to the following (E) and (F), the thickness of 50 μm of the base film obtained by the same method was set to 〇. 5 g/m 2 . The layered biaxially oriented polyethylene terephthalate film was laminated to Comparative Example 2 and Comparative Example 3, respectively. <Coating liquid (E)> Polyvinyl alcohol/methoxymethylol melamine having a degree of saponification = 88 mol%, degree of polymerization = 500, becami η / average particle diameter of 0.0 by Nippon Ink Chemical Industry Co., Ltd. // m cerium oxide melt containing solid parts converted to a weight ratio of 85/1 〇 / 5 ratio of aqueous coating solution. -18- (14) 1284137 <Coating liquid (F)> Poly(trimethylamine ethyl methacrylate) grade 4 / alkyl acrylate copolymerized with alkyl methacrylate, propylene resin having a Tg of 40 ° C , Japan carbaid industrial nicasol / methoxymethylol melamine, Dainippon ink chemical industry industry becami η / average particle size 0.05 / / m cerium oxide melt solid content conversion weight composition ratio 4 0 / 2 0 / 3 5 / 5 ratio of aqueous coating solution. The characteristics and practical characteristics of the film obtained above are shown in Tables 1 and 2 below. Table 1
>、袁 ^ — 灰塵附著性評價 光學缺陷檢查 實施jglL 1 〇 〇 實施JL2 …· 〇 〇 實施3 〇 〇 實施I4 〇 〇 比較i1 X X 比較 X △ 比較』ί 3 - 〇 X 19- (15) 1284137 表2 表面固有電阻値 (Ω ) 低聚物量評價 1 低聚物量評價2 (mg/m2) 實施例1 2x 109 1.2 0.6 實施例2 lx 1010 1.4 0.7 實施例3 3x 1011 1.2 0.6 實施例4 2x 1011 2.4 1.2 比較例1 5χ ΙΟ14 2 1 10.5 比較例2 5χ ΙΟ14 8.2 4.1 比較例3 4χ ΙΟ11 22.4 11.2 【產業上可利用性】 本發明係提供一種防止靜電產生沾污、高溫下使用藉 由析出低聚物後仍不致出現問題點之光學缺陷少之經塗敷 之薄膜、具極高工業之利用價値者。 -20->, Yuan^ — Dust adhesion evaluation Optical defect inspection implementation jglL 1 〇〇 Implementation JL2 ...· 〇〇 Implementation 3 〇〇 Implementation I4 〇〇 Comparison i1 XX Comparison X △ Comparison 』ί 3 - 〇X 19- (15) 1284137 Table 2 Surface intrinsic resistance 値 (Ω) Evaluation of oligomer amount 1 Evaluation of oligomer amount 2 (mg/m2) Example 1 2x 109 1.2 0.6 Example 2 lx 1010 1.4 0.7 Example 3 3x 1011 1.2 0.6 Example 4 2x 1011 2.4 1.2 Comparative Example 1 5χ ΙΟ14 2 1 10.5 Comparative Example 2 5χ ΙΟ14 8.2 4.1 Comparative Example 3 4χ ΙΟ11 22.4 11.2 [Industrial Applicability] The present invention provides a method for preventing static electricity from being contaminated, and using at a high temperature due to low precipitation. After the polymer, there is still no problem with the application of the film with less optical defects, and it has a very high industrial price. -20-