200914504 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種防靜電聚酯膜之製造方法，更詳而 言之，係關於一種防靜電聚酯膜之製造方法，係於聚酯膜 之單面或兩面所形成之防靜電層添加氟樹脂及聚胺酯樹脂 而透明性與防靜電性優異、且改善膠帶剝離力及防污性 能、具有優異功能。 【先前技術】 近年來’伴隨產業化的進行，各種電子及電氣機器、 資訊通訊領域及一般生活用品之廣泛領域中，因靜電產生 所致之災害正增加中，該等機器及產業現場之防靜電成為 ㈣要之課題。所謂防靜電，係將累積於絕緣體表面之電 何以適當方法放電，為了卩六巍 马了防靜電，只要於製品表面形成使 所累積之電荷放電之防靜雷居。 β 罨層特別疋，於附著有雜質或 塵埃之薄膜之製造步驟、 鄉與加工溥膜之步驟中會產生放 電，而若於該等步驟伤用古办、— ^ 用有機溶劑，則會產生著火的危險。 再者，§將該種薄膜作為電 ,) 主、WIT H 電子零件等之材料使用的 二 靜電損傷的原因，故於該等薄膜之使 用方面、，料防靜純能成“需要件。U膜之使 上述之防靜電技術有： 樣的陰離子化合物吏用有機崎酸及有機磷酸醋那 ρ添加法、蒸鍍金屬化人物之方 法、塗布導電性無機粒 屬化口物之方 或陽離子性化合物之方 、 L布低刀子型陰離子性 上述使用有機二 布導電性高分子之方法等。 吏用有機㈣及有機鱗酸醋那樣的陰離子化合物 200914504 之内β添加法，雖具有費用廉價、隨時間變化及安全性優 異之優點，但會損害薄膜支持體之固有特性、防靜電效果 有界限、因輝散現象（blooming)使薄膜與積層間之接著性 降低，是其問題。 蒸鍍金屬化合物之方法，防靜電性優異，於最近廣泛 使用於導電性膜’ t由於製造費用非常高故僅使用於特定 用途。 ί 、而使用低分子型陰離子性或陽離子性化合物之塗布 法’防靜電效果較良好，於製造費用方面上亦有利，故可 使用於廣|a圍’但由於防靜電效果有限’故無法得到… :以下之表面電阻’由於係與大氣中之水分結 :防靜電特性，故於大氣中之水氣含量低的情況下，防靜 =幅，低’溶劑抵抗性非常差，且有轉移至其他面的 &其缺點，故其之使用大幅地受到限制。 :前係開發有溶解於水及有機溶劑之聚笨胺、 =吩等導電性高分子’且用以將其賦予導電 電=膜或其他高分子表面之應用研究正熱烈進行中。 後，將甘 ^ 係做出-成摻雜之導電性高分子 後將其以適當之溶劑塗布於含聚酯之& 于 方法。 1曰之各種雨分子表面之 此時’使其與適當之黏結劑—同溶解以 著力或表面硬度等之機械性質。 1 ^ 0之 分子T:之於T㈣495943°號，揭示導電性高 刀卞早體之一種即 q 6 1 ,4-乙烯二氧噻吩（3,4_ 200914504 ethyienedi〇xythiophene)與氧化劑即對甲苯磺酸（ir⑽（iii) P-t〇iuenesuif〇nate)及與該等合成之導電性高分子之3,4_ 聚乙烯二氧嗟吩（3,4_polyethylenedi〇xythi〇ph叫，具體而 言，係將3,4-乙稀二氧嚷吩與對甲苯確酸以常溫混合後， 加熱’而製造成藍色之導電性高分子聚乙烯二氧嗟吩。 口成之3,4-聚乙稀二氧嗟吩係以分散於水的形態市 售，但若將3,心乙稀二氧嗟吩與對甲苯石黃酸混合而於常溫 放置長時間，則會產生聚合反應，故混合少量反應抑制劑 即咪唑（imidazole)來防止之。 於日本特開平卜阳⑵號提出一種導電性高分子，係 將二烧氧嗟吩於聚陰離子存在下氧化聚合可製得聚 (3,4-二烧氧。塞吩）與聚陰離子所構成之導電性聚合物，立且 :高導電性、高化學安全性及膜形成時之塗膜具有高透明 當將含有如此之導電性高分子之塗布液塗布於 2基材的情形時，無法簡單地得到可同時滿足對基材之 i. I;二明性、耐水性、耐溶劑性及導電性之所有性能 是為了提昇塗膜之耐水性而嘗試將結合劑樹 知以乂聯劑交聯鍵結之方法等。 於曰本特開平6_73271號，基於提昇 吩）與聚陰離子所構成之導電性 ，一烷軋噻 職之^ Μ合物層和鄰接層之密合性 而使用具有環氧基之院氧石夕燒化人札 予塗膜耐水性。 夕烷化“勿，但難以賦 隨著靜電形式之防靜電製品方面，最近， d、pdp市場之ιτ事㈣成長，防靜電膜之 200914504 需求急遽增加。 本用途主要所使用之防靜電膜，最廣為人知者係陽離 子防靜電形式，而使用導電性高分子之薄膜亦作為高級薄 膜進入市場。 / 最終之狀況係要求具有優異之防靜電性能及防污功 能，但要製造於在線塗佈（in_line coating)時同時實現該兩 功能之薄膜係困難。又，視製品的用途，當將保護薄膜於 取後之步驟剝離的情況下，係以機械自動方式貼上膠帶後 剝離，但此時，若膠帶與防靜電面之接著力低，則會有保 護膜無法良好地剝離、或剝離途中對製品造成影響之問題 點，而要求與膠帶之剝離力高之製品。 【發明内容】 本發明係用於解決上述問題點者，其目的在於提供一 種優異光學用防靜電聚醋膜之製造方法，其係使用導電性 南分子以實現優異之防靜 ^ ^ 電此，使用聚胺酯樹脂以提昇 Γ ，同—使用適當之交聯劑調節交聯密度並提 歼、冷劑性與塗膜性能，並添加氟樹脂以提昇防污功能。 用以達成上述目的之本發明防靜電聚醋膜之製造方法 係包含： 將聚酯基材膜做單軸拉伸之階段； 製造含有導電性离八上枝^ 间刀子樹月曰、聚胺酯樹脂、交聯劑及 齓树知之防靜電塗布液之階段； 布、、广、；二單轴拉伸之聚醋基材膜的單面或兩面塗布該塗 布液以形成防靜電層之階段； 200914504 及將形成有該防靜電層之聚g旨基材膜進行雙轴拉伸之 階段。 該防靜電層’較佳為，對於導電性高分子樹脂1〇〇重 ，份由聚胺酯樹脂ι00〜1000重量份、交聯劑100〜1000重 董份、及氟樹脂30〜3〇〇重量份所構成。 該導電性高分子樹脂，較佳為，將聚陰離子與聚噻吩 或其之何生物聚合來製造，該聚胺酯樹脂，較佳為呈水分 放形式且係至少含有經基、胺基、叛基等官能基之^種 :上之樹脂。肖交聯劑，較佳為，使用選自異氰酸醋系、 羰基醯亞胺系、噁唑啉系、環氧系及三聚氰胺系所構成群 中之任1種以上之化合物。 該氟樹脂，較佳為，使用四氟乙烯系樹脂。 以本發明之防靜電聚酯膜之製造方法所製造之防靜電 Λ 保有優異之防靜電功能且即使將混合有適當量之 :、有防/亏功此之氟樹脂與聚胺酯樹脂之防靜電塗布組成物 土布於♦酯膜，並以水或乙醇洗淨，該防靜電層之防靜電 劑不會脫離或溶解。且可具優異之防污功能並提昇與黏著 膠帶之密合力。 ~' 本發明，舉具體之實施例來說明，但該領域所屬之業 者可明白 耶可於本發明之技術思想的範圍内進行各種變形 乂 亚理解該等變形及修正亦屬於所附之申請專利之 範圍。 【貫施方式】 -*r* ’更詳細地說明本發明。 200914504 本發明之防靜電聚酯膜之製造方法，係包含： 將聚醋基材膜做單軸拉伸之階段； 造含有導電性高分子樹脂、聚胺醋樹脂、交聯劑及 樹θ之防靜電塗布液之階段； 於该經單軸拉伸之聚酿基材膜的單面或 布液以形成防靜電層之階段； ㈣"亥塗 階段及將形成有該防靜電層之聚酉旨基材膜進行雙軸拉伸之 Γ' “ 兒月將聚醋基材膜做單轴拉伸之階段。 存之使用之聚醋膜’其種類並無限制，可使用既 存之已知作為防靜電塗布之基材膜者。 酸丁二ϋ月聚：以聚對苯二甲酸乙二醇酿、聚對苯二甲 明，但本發明之^甲酸乙二醇醋等聚酷系樹脂為中心説 係指將芳香旌… 並不限定於此。構成該臈之聚醋， g， 、一羧酸與脂肪族二醇縮聚 族二缓酸，可舉 ：传之“。方香 族二醇，可舉例如乙：醇 ，6萘-羧酸等’脂肪 等。螯酯之仲主 并 1，4- %己烷二甲和 U日之代表’有 萘二叛酸乙二醇Λ 6 —M(PET)、聚认 成分之共聚物。 ，。该聚酯，亦可使用含有第3 該共聚合聚酯之_ 鄰苯二甲酸、對苯鍰酸成分’可舉例如間苯二甲酸、 酸、㈣酸（例如:Γ、2,6·蔡二_、己二酸、癸> 例如乙二醇、二！經基苯甲酸等）；二醇成分，# 醇丙—醇、丁二醇、Μ-環己嫁> 10 200914504 甲醇、新戊一醇等。該等二緩酸成分及二醇成分，亦可併 用2種以上。 將上述構成之聚酯樹脂於真空乾燥後於擠製機熔融， 以T模具（T-DIE)擠壓成片狀，將該片於冷卻輥以施加靜電 法（pinning)密合並冷卻固化，藉此製得未拉伸聚酯片。於 加熱至聚酯樹脂之玻璃轉移溫度以上之輥，藉輥與輥間之 周轉速度比之差將其進行2.5-4.5倍之單轴拉伸，製造單 軸拉伸聚酯膜。 接著’說明製造防靜電塗布液之階段。 本發明之防靜電塗布液，係塗布於聚酯膜之單面或兩 面以形成防靜電層者，詳而言之，係含有固體成分之導電 |·生同刀子樹知、聚胺酯樹脂、交聯劑、氟樹脂與溶劑，更 洋而5之，係由相對於導電性高分子樹脂丨〇〇重量份含有 來胺酯樹脂1〇〇〜1〇〇〇重量份、交聯劑1〇〇〜1〇〇〇重量份、 及說樹脂30〜3〇〇重量份所構成。 八體而s，該防靜電塗布液所含之導電性高分子樹脂， 為了賦予防靜電性，較佳為使用聚陰離子與聚噻吩之水分 政體或聚陰離子與聚噻吩衍生物之水分散體。 *該聚陰離子，係酸性聚合物，含高分子羧酸或高分子 Ά ♦乙烯磺酸等。高分子羧酸，有聚丙烯酸、聚甲基 丙烯駄來馬來酸等，高分子磺酸，有聚苯乙烯磺酸等。 ’子於4嘆吩或聚D塞吩衍生物，由導電性之觀點，聚 陰離子W g]體成分重量％過剩地存在為佳’相對於聚嘆吩 或聚°塞吩衍生物1重量％，聚陰離子以1重量％〜5重量％ 11 200914504 為佳。更佳為’ 1重量％〜3重量％。 另方面，於本發明，係使用含有聚（3,4-乙烯二氧噻 吻）0.5重篁％與聚苯乙烯磺酸（分子量Mn= 15〇〇〇〇) 〇 8 重夏°/〇之聚合物之水分散體。 接著’說明聚胺酯樹脂。 本發明所使用之聚胺酯樹脂，係塗布於聚酯膜，其之 添加係用以增大上述膜之膠帶剝離力，該聚胺醋樹脂，以 王X刀散形式為佳’且係使用至少含有羥基、胺基、羧基、 異氮酸酿基、環氧基、㈣琳基等官能基t 1種以上之樹 脂。 另方面，所添加之聚胺酯樹脂之量，係相對於導電 !·生冋刀子樹月日1 〇〇重罝份添加聚胺酯樹脂丨⑽〜1 〇⑼重量 份。若聚胺醋樹脂之添加量未滿1〇〇重量份，則膠帶剝離 力降低，而難以發揮功能，#丄 平’、力月匕 右超過1000重量份，則雖 可充分地確保膠帶剝離力作合太丄 刀會產生防靜電性能降低之問 題。 ( 接著，說明交聯劑。 本發明所使用之交聯 膜之耐溶劑性及塗膜性能 叛基酿亞胺系、σ惡唾琳系 以上之化合物。 劑’係用以提昇防靜電層與聚酯 ’較佳為使用選自異氰酸酯系、 、環氣系及三聚氰胺系之任1種 另一方面，戶斤添力口之夺脾土， _ 乂如*劑之量，係相對於導電性高 分子樹脂 100重量份添加夺碑七，i 又％劑樹脂100〜1 000重量份。 若交聯劑樹脂之添加量未滿 1 〇〇重罝份，則會有防靜電性 12 200914504 難以發揮之情形，由於耐溶劑性弱而產生白化現象。又， 若超過1 000重量份，則雖透明性良好，但有難以發揮防 靜電性之問題。 接著，說明氟樹脂。 本發明所添加之氟樹脂，係塗布於聚酯膜，其之添加 係用以提昇該膜之防污性、水接觸角及耐溶劑性，有聚四 氟乙烯（Poly tetra fluoro ethylene)、四氟乙烯、全氟化烷 基乙烯 共聚物（perfluoro (alkyl vinyl ether) copolymer)、 二氟乙稀、六氟丙烯共聚物（Fluorinated ethylene copolymer propylene cop〇lymer)、乙烯、四氟乙烯共聚物、氯三氟乙 細、四氣乙烯共聚物（Ethylene tetra fluoro ethylene copolymer)、鼠二鼠乙細、四敗乙稀共聚物（p〇iy tetra fluoro ethylene cop〇lymer)、聚氟乙烯（p〇ly vinyU flu〇ride)、聚 偏一氟乙稀（P〇ly vinylidene fluoride)等，較佳為使用四氣 乙烯。 另一方面，所添加之氟樹脂之量，係相對於導電性高 分子樹脂100重量份添加氟樹脂30〜300重量份。若氟樹 脂之添加量未滿30重量份，則防污性降低，而若超過3〇〇 重量份，則有膜之透明性降低、且防靜電性能亦降低之問 題。 上述之本發明之防靜電塗布液，較佳係製造成相對於 整體塗布液100重量％，固體成分之含量為〇5〜1〇〇重量 %，更佳為係製造成固體成分之含量為10〜5 〇重量。= 該固體成分之含量未滿〇.5重量％，則塗布層之被里膜。形： 13 200914504 及防靜電功能發揮的不充分， 而右超過10.0重量％則有膜 之透明性降低之問題。 、 ^ φ 防靜電塗布液所使用之溶劑，較佳為實 貝上以水為主要介質之水 个 ^^ 复帝液。本發明所使用之塗布 液，於塗布性之提昇、透明性 JD 士丄心 风幵寺目的上’亦可以不 指。本發明效果的程度含有適當之有機 可使用異丙醇、丁基赛路蘇、二 — —級丁基赛路蘇、乙基賽路 广穌、丙嗣、乙醇、甲醇等。然而，當塗布液中含有大量之 、有機溶劑的情況下，若使用在線塗布法，則於乾燥'拉伸 及熱處理步驟會有爆炸的危險性，故其含量以為塗布液之 10重量。Λ以下為宜，5重量％以下為佳。 接著，於該單軸拉伸聚醋膜之至少一面塗布所製造之 防靜電塗布液以形成防靜電層。具體而言，塗布防靜電塗 布液之方法並無特別限制，可使用絲棒（Μα㈣方式、 '、、'相凹板方式等’較佳為’於塗布前將極性基導入膜的表 【面，進行電暈（C_a)放電處理以提昇塗布層與膜之接著 ' 性及塗布性。 又’為了提昇防靜電塗布液之安全性、濕；閏性（贈 及塗布時之平整（leveling)，可混合乙醇、異丙醇、異丙醇 等醇類、乙基赛路蘇、三級τ基赛路蘇等賴、f乙嗣、 丙嗣等酮類、二甲基乙醇胺等胺類或離子性/非離子性界面 活性劑之1種以上來使用。 最後’將形成有該防靜電層之單軸拉伸聚酯膜再拉伸 以製造雙軸拉伸聚酯膜。具體而言，係朝與單軸拉伸方向 14 200914504 垂直之方向拉伸，拉伸比以3.0〜7.0❺為佳。之後，藉由 熱固定等製造防靜電聚酯膜，聚酯膜之厚度通常為5〜300 # m、較佳為1〇〜25〇# m。 以上述方法所製造之防靜電聚酯膜，係透明且對防靜 電層之水接觸角為95。以上、具有3〇〇g/in以上之膠帶剝離 力即使以/凰水及乙醇擦拭表面，表面電阻亦為丨χ丨〇 11 Ω /sq 以下。 結果，本發明之保護膜，藉由於基材之單面或兩面塗 布該含氟樹脂與聚胺酯樹脂之防靜電塗布液所形成之防靜 電層，而具有撥水功能、耐乙醇性及容易去除黏著劑之性 貝’且具有膠帶剝離力高之性能，故可提供能因應晝面大 型化要求之聚酯膜。 以下，列舉實施例以更詳細說明本發明，但該等實施 例，係用以更具體地說明本發明所例示者，故本發明並不 限於該等實施例。 〈實施例1 >200914504 IX. Description of the Invention: [Technical Field] The present invention relates to a method for producing an antistatic polyester film, and more particularly to a method for producing an antistatic polyester film, which is based on a polyester film. The antistatic layer formed on one side or both sides is added with a fluororesin and a polyurethane resin, and is excellent in transparency and antistatic property, and has improved tape peeling resistance and antifouling performance, and has an excellent function. [Prior Art] In recent years, with the progress of industrialization, disasters caused by static electricity are increasing in various fields of electronic and electrical equipment, information communication, and general household goods, and the prevention of these machines and industrial sites Static electricity has become the subject of (4). The so-called anti-static is to discharge the electricity accumulated on the surface of the insulator in an appropriate manner. In order to prevent static electricity, it is necessary to form an anti-static charge on the surface of the product to discharge the accumulated electric charge. The β ruthenium layer is particularly flawed, and a discharge is generated in the steps of manufacturing a film to which impurities or dust are attached, and in the step of processing the ruthenium film, and if the organic solvent is used in the steps, the organic solvent is generated. The danger of fire. Furthermore, § this type of film is used as the cause of the two-electrostatic damage used for materials such as electric, WIT H electronic parts, etc. Therefore, in terms of the use of these films, anti-static purity can be made into a "required piece. U film The antistatic technique described above includes: an anionic compound, an organic acid and an organic phosphate, a method of adding a metallized person, a method of coating a conductive inorganic particle, or a cationic compound. The method of using the organic bismuth conductive polymer in the above-mentioned L-low knife-type anionic property, etc. The β-addition method of the anionic compound 200914504 such as organic (IV) and organic squash vinegar is inexpensive, and has a low cost. The advantages of the change and the safety are excellent, but the inherent characteristics of the film support, the antistatic effect are limited, and the adhesion between the film and the laminate is lowered by the blooming phenomenon, which is a problem. The method is excellent in antistatic property and has been widely used in conductive films recently because it is very expensive to manufacture and is used only for specific purposes. The coating method of the molecular type anionic or cationic compound has a good antistatic effect and is advantageous in terms of manufacturing cost, so that it can be used for wide-area, but it is impossible to obtain due to the antistatic effect. Since the resistance is due to the moisture in the atmosphere: anti-static property, in the case of low moisture content in the atmosphere, anti-static = amplitude, low 'solvent resistance is very poor, and there is a transfer to other surfaces & The disadvantages are greatly limited, and the use thereof is limited to the development of a conductive polymer such as polystyrene or = phenanthrene dissolved in water and an organic solvent, and is used to impart a conductive electric film or other polymer. The application of the surface is underway. After that, the conductive polymer is made into a doped conductive polymer and then applied to the polyester-containing compound in a suitable solvent. The surface at this time 'make it with the appropriate binder - the same mechanical properties such as force or surface hardness. 1 ^ 0 of the molecule T: to T (four) 495943 °, revealing a kind of conductive high-knife early body q 6 1 ,4-ethylene II Thiophene (3,4_200914504 ethyienedi〇xythiophene) and oxidant, p-toluenesulfonic acid (ir(10)(iii) Pt〇iuenesuif〇nate) and 3,4_polyethylenedioxyphene (3) with the synthetic conductive polymer 4_polyethylenedi〇xythi〇ph, specifically, 3,4-ethylenedioxyphene and p-toluene acid are mixed at room temperature, and heated to produce a blue conductive polymer polyethylene dioxygen嗟. The 3,4-polyethylenedioxy porphin is commercially available in the form of dispersion in water, but if 3, ethylenedioxy porphin is mixed with p-toluene citrate and placed at room temperature. For a long period of time, a polymerization reaction occurs, so that a small amount of a reaction inhibitor, imidazole, is mixed to prevent it. A conductive polymer is proposed in Japanese Unexamined Buyang (2), which is obtained by oxidative polymerization of di-o-oxygen porphin in the presence of polyanion to form poly(3,4-di-oxygen. The conductive polymer has high conductivity, high chemical safety, and high transparency of the coating film at the time of film formation. When the coating liquid containing such a conductive polymer is applied to the two substrates, it is not simple. The ground property can satisfy all the properties of the substrate i. I; two clarity, water resistance, solvent resistance and electrical conductivity in order to improve the water resistance of the coating film and try to crosslink the binder with the chelating agent. The method of bonding, and the like. U.S. Patent No. 6_73271, based on the electrical conductivity of the elevated phenanthrene and the polyanion, the adhesion of the alkane ruthenium complex layer and the adjacent layer, and the use of the epoxy group The burnt person is given a water resistance of the coating film. "Alternation", but it is difficult to assign antistatic products in the form of static electricity. Recently, the growth of d, pdp market (4), the demand for antistatic film 200914504 has increased rapidly. The antistatic film used mainly for this purpose, The most widely known is the cationic antistatic form, and the film using the conductive polymer also enters the market as a high-grade film. / The final condition requires excellent antistatic properties and antifouling properties, but is manufactured in-line coating (in_line) In the case of coating, it is difficult to realize the film of the two functions at the same time. Also, depending on the use of the product, when the protective film is peeled off in the step of taking off, the tape is peeled off by mechanical automatic means, but at this time, if When the adhesion between the tape and the antistatic surface is low, there is a problem that the protective film is not peeled off well or the product is affected during the peeling, and a product having a high peeling force with the tape is required. In order to solve the above problems, the object of the invention is to provide an excellent method for producing an antistatic polyacetal film for optics, which uses conductivity. The molecule is used to achieve excellent anti-static properties. The polyurethane resin is used to enhance the enthalpy. The same crosslinking agent is used to adjust the crosslink density and improve the coldness and film properties, and the fluororesin is added to enhance the protection. The method for manufacturing the antistatic polyacetal film of the present invention for achieving the above object comprises: a step of uniaxially stretching a polyester base film; and manufacturing a knife containing a conductive strip from the arbor, The stage of the polyurethane resin, the crosslinking agent and the antistatic coating liquid of the eucalyptus; the stage of coating the coating liquid on one or both sides of the uniaxially stretched polyester substrate film to form the antistatic layer 200914504 and a step of biaxially stretching the base film formed with the antistatic layer. The antistatic layer 'preferably, the conductive polymer resin 1 is heavy, and the fraction is made of polyurethane resin ι00 It is composed of -1000 parts by weight, a crosslinking agent of 100 to 1000 parts by weight, and a fluororesin of 30 to 3 parts by weight. The conductive polymer resin preferably has a polyanion and a polythiophene or a living organism thereof. Polymerized to produce the polyurethane Preferably, the lipid is in the form of a moisture release and contains at least a functional group such as a base group, an amine group, a thiol group, etc., a Schiffon crosslinker, preferably, selected from the group consisting of isocyanate, Any one or more of the group consisting of a carbonyl quinone imine, an oxazoline, an epoxy, and a melamine. The fluororesin is preferably a tetrafluoroethylene resin. Antistatic 制造 manufactured by the method for producing a polyester film. It has an excellent antistatic function and even if it is mixed with an appropriate amount: an antistatic coating composition of a fluororesin and a polyurethane resin having an anti-/defective effect The film is washed with water or ethanol, and the antistatic agent of the antistatic layer is not detached or dissolved, and has excellent antifouling function and improved adhesion with the adhesive tape. ~' The present invention is embodied For example, those skilled in the art can understand that various modifications can be made without departing from the scope of the invention. [Comprehensive Mode] - *r* ' The present invention will be described in more detail. 200914504 The method for producing an antistatic polyester film of the present invention comprises: a step of uniaxially stretching a polyester substrate film; forming a conductive polymer resin, a polyurethane resin, a crosslinking agent, and a tree θ a stage of the antistatic coating liquid; a stage of forming the antistatic layer on the one side or the cloth liquid of the uniaxially stretched base material film; (4) " the stage of coating and the gathering of the antistatic layer to be formed The biaxial stretching of the base film is carried out. The "polyester film of the polyester substrate is uniaxially stretched. The type of the polyester film used is not limited, and the existing known one can be used. Antistatic coating substrate film. Acid bismuth sulphate: Polyethylene terephthalate brewed, polyparaphenylene phthalate, but the invention of the formic acid glycol vinegar and other polyurethane resin The center means that the aromatic sputum is not limited thereto. The condensed vinegar, g, monocarboxylic acid and aliphatic diol polycondensation group which constitute the hydrazine are referred to as "transfer". The scented diol may, for example, be a fat such as B: alcohol or 6 naphthalene-carboxylic acid. The main component of the chelating ester and 1,4-% hexane dimethyl ketone and U-day represents a copolymer of naphthalene di-neuric acid ethylene glycol Λ 6 - M (PET) and a poly-identifying component. ,. As the polyester, a phthalic acid or a terephthalic acid component containing the third copolymerized polyester may be used, for example, isophthalic acid, an acid, or a (tetra) acid (for example, ruthenium, 2, 6 · Cai Di-, adipic acid, hydrazine> For example, ethylene glycol, di-!-benzoic acid, etc.; diol component, #醇丙-ol, butanediol, Μ-cyclohexane Marriage> 10 200914504 Methanol, new Pentanol and the like. These two acid-lowering components and diol components may be used in combination of two or more kinds. The polyester resin having the above composition is vacuum-dried, melted in an extruder, extruded into a sheet shape by a T-die (T-DIE), and the sheet is cooled and solidified by applying a static method to a cooling roll. This produced an unstretched polyester sheet. The uniaxially stretched polyester film was produced by subjecting the roll heated to a temperature above the glass transition temperature of the polyester resin to a uniaxial stretching of 2.5 to 4.5 times by the difference between the rolls and the rolls. Next, the stage of manufacturing the antistatic coating liquid will be described. The antistatic coating liquid of the present invention is applied to one side or both sides of a polyester film to form an antistatic layer, and more specifically, is a conductive material containing a solid component|·生同刀子树, polyurethane resin, cross-linking The agent, the fluororesin and the solvent are more than 5 parts by weight, and the crosslinking agent 1 〇〇 is contained in an amount of 1 to 1 part by weight of the amine ester resin relative to the conductive polymer resin. It is composed of 1 part by weight and 30 to 3 parts by weight of the resin. In order to impart antistatic properties, the conductive polymer resin contained in the antistatic coating liquid is preferably a water hydrate of polyanion and polythiophene or an aqueous dispersion of a polyanion and a polythiophene derivative. * The polyanion is an acidic polymer containing a high molecular weight carboxylic acid or a polymer Ά ♦ vinyl sulfonic acid. The polymer carboxylic acid includes polyacrylic acid, polymethyl propylene oxime, maleic acid, etc., polymer sulfonic acid, polystyrene sulfonic acid, and the like. 'Sub-4 singular or poly-D-cetin derivative, from the viewpoint of electrical conductivity, polyanion W g] body component weight% is excessively present as 'relative to polythiophene or polythiophene derivative 1% by weight The polyanion is preferably from 1% by weight to 5% by weight of 11 200914504. More preferably, it is '1% by weight to 3% by weight. On the other hand, in the present invention, it is used to contain poly(3,4-ethylenedioxythiophene) 0.5% by weight and polystyrenesulfonic acid (molecular weight Mn = 15 〇〇〇〇) 〇8 heavy summer ° / 〇 An aqueous dispersion of the polymer. Next, the polyurethane resin will be described. The polyurethane resin used in the present invention is applied to a polyester film, which is added to increase the tape peeling force of the film. The polyurethane resin is preferably in the form of Wang X knife and contains at least One or more kinds of functional groups t such as a hydroxyl group, an amine group, a carboxyl group, an isonialt acid base group, an epoxy group, or a (tetra) linyl group. On the other hand, the amount of the polyurethane resin to be added is added to the weight of the polyurethane resin 丨(10)~1 〇(9) by weight relative to the conductive · 冋 knife tree. When the amount of the polyamine vinegar resin added is less than 1 part by weight, the tape peeling force is lowered, and it is difficult to function, and if the weight is more than 1000 parts by weight, the tape peeling force can be sufficiently ensured. Heta knives can cause problems with reduced antistatic performance. (Next, the cross-linking film used in the present invention has solvent resistance and coating film properties. The compound is used to enhance the antistatic layer and the compound. The polyester is preferably one selected from the group consisting of an isocyanate type, a ring gas system, and a melamine system, and the amount of the spleen, such as the amount of the agent, is relative to the conductivity. 100 parts by weight of the polymer resin is added to the tablet 7 and i is 100% to 1 000 parts by weight of the resin. If the amount of the crosslinking agent resin is less than 1 〇〇, the antistatic property is 12 200914504 In the case where the solvent resistance is weak, the whitening phenomenon occurs. When the amount is more than 1,000 parts by weight, the transparency is good, but the problem of the antistatic property is hard to be exhibited. Next, the fluororesin will be described. The resin is applied to a polyester film, which is added to enhance the antifouling property, water contact angle and solvent resistance of the film, and has polytetrafluoroethylene, tetrafluoroethylene, and perfluorination. Alkyl ethylene copolymer (perfluoro (alkyl vi Nyl ether) copolymer), difluoroethylene, hexafluoropropylene copolymer (Fluorinated ethylene copolymer propylene cop〇lymer), ethylene, tetrafluoroethylene copolymer, chlorotrifluoroethylene, tetraethylene ethylene copolymer (Ethylene tetra fluoro ethylene Copolymer), p〇iy tetra fluoro ethylene cop〇lymer, polyvinyl alcohol (p〇ly vinyU flu〇ride), polyvinylidene fluoride (P〇ly) The vinyl fluororesin is preferably used in an amount of 30 to 300 parts by weight based on 100 parts by weight of the conductive polymer resin. When the amount is less than 30 parts by weight, the antifouling property is lowered, and if it exceeds 3 parts by weight, the transparency of the film is lowered and the antistatic property is also lowered. The antistatic coating liquid of the present invention described above is more preferable. Preferably, the content is 100% by weight based on the total coating liquid, and the solid content is 〇5 to 1% by weight, more preferably 10% by weight to the solid content. = The content of the solid component Not full 5% by weight, the coating layer is covered with a film. Shape: 13 200914504 and the antistatic function is insufficient, and when the right is more than 10.0% by weight, the transparency of the film is lowered. ^ φ Antistatic coating solution The solvent to be used is preferably water which is mainly composed of water on the solid shell. The coating liquid used in the present invention may not be used for the improvement of the coating property and the transparency of the JD. The degree of the effect of the present invention includes an appropriate organic use of isopropyl alcohol, butyl siroli, di-butyl butyl sulcata, ethyl celesta, acetonide, ethanol, methanol, and the like. However, when the coating liquid contains a large amount of an organic solvent, if the in-line coating method is used, there is a risk of explosion in the drying 'stretching and heat treatment step, so the content is 10% by weight of the coating liquid. Λ The following is suitable, preferably 5% by weight or less. Next, the produced antistatic coating liquid is applied to at least one side of the uniaxially stretched polyester film to form an antistatic layer. Specifically, the method of applying the antistatic coating liquid is not particularly limited, and a wire rod (Μα (four) method, ', '', a concave plate method, etc.' may be used, and it is preferable to introduce a polar group into the film before coating. Corona (C_a) discharge treatment is carried out to improve the adhesion and coating properties of the coating layer and the film. In order to improve the safety, wetness and entanglement of the antistatic coating liquid (gating and leveling) It can be mixed with alcohols such as ethanol, isopropanol and isopropanol, ethyl celecoxib, tertiary τ 赛赛路苏, ketones such as f acetamidine and propyl hydrazine, and amines or ions such as dimethylethanolamine. One or more kinds of non-ionic surfactants are used. Finally, the uniaxially stretched polyester film having the antistatic layer formed thereon is further stretched to produce a biaxially stretched polyester film. Specifically, Stretching in a direction perpendicular to the uniaxial stretching direction 14 200914504, the stretching ratio is preferably 3.0 to 7.0 Å. Thereafter, an antistatic polyester film is produced by heat fixing or the like, and the thickness of the polyester film is usually 5 to 300. #m, preferably 1〇~25〇# m. Antistatic polyester film manufactured by the above method, Transparent and the water contact angle of the antistatic layer is 95. Above, the tape peeling force of 3〇〇g/in or more, even if the surface is wiped with /water and ethanol, the surface resistance is 丨χ丨〇11 Ω /sq or less. As a result, the protective film of the present invention has a water-repellent function, ethanol resistance, and easy removal by applying an antistatic layer formed of the antistatic coating liquid of the fluorine resin and the polyurethane resin on one or both sides of the substrate. The adhesive has the property of high adhesive tape peeling force, so that a polyester film which can meet the requirements for large-sized kneading can be provided. Hereinafter, the present invention will be described in more detail by way of examples, but the examples are used. The present invention will be more specifically described, and the present invention is not limited to the embodiments. <Example 1 >
-階段1 :單軸拉伸聚酯膜夕誓地 將極限黏度為G_625dl/g的聚對苯二甲酸乙二醇醋顆粒 (Pellet)(此聚對苯二曱酸乙二醇酯顆粒係混入有汕卯⑺之 平均粒徑為2.5 之無定形球形氧化矽粒子），利用真空 乾燥機以7小時喊充分乾燥後熔融，以擠製τ模具： 冷卻筒以施加靜電法（pinning)使密合作成無定形未拉伸 片，將其再加熱以95t朝膜進行方向拉伸3 5倍製得單轴 拉伸聚S旨膜。之後’對所得之單軸拉伸聚醋膜的一面，實 15 200914504 施電暈放電處理。 _階段2 :雙軸拉伸聚酯膜之贺诰 於經電暈處理之面，將作為固體成分之導電性高分子 樹脂（Nagase ChemteX 公司 ’ DENATR〇N#5002SZ;含有 聚3，4-乙烯二氧嘆吩〇.5重量％與聚苯乙稀續酸〇.8重量％ 之水为散體）1 00重量份、聚胺醋樹脂（hepce chem公司， ΗΜΟΜΐ23Α :含有羥基、胺基、羧基等官能基之陰離子之 聚轉聚胺醋分散體）200重量份、三聚氰胺交聯劑（賽鐵 ί % 克公司，CYMEL385 ) 200重量份、四氟乙烯（杜邦公司， SLA-NE W ) 1 00重量份、界面活性劑樹脂（日信化學工業 公司，EXP405 1 ;乙炔二醇（acetylene di〇1)成分）2重量份 此合於水製造防靜電塗布液。此時，固體成分之含量，係 相對於整體防靜電塗布液含1·5重量％。 將該防靜電塗布液使用#6絲棒塗布於上述階段1所製 4之單軸拉伸聚酯膜。塗布後，於1〇5〜14〇〇c拉幅（tender) ( 區間使所塗布之塗布液乾燥’朝與膜之進行方向垂直之方 向拉伸3.5倍並以24(rc熱處理4秒鐘，藉此，製造38# m厚之雙軸拉伸防靜電聚酯膜。 〈霄施例2 > 使用導電性尚分子樹脂（Nagase ChemteX公司）1〇〇 重里知、胺酯樹脂（hepce ehem公司）4〇〇重量份、環氧 六聯M (Nagase ChemteX 公司，DENACOL EX-614) 300 =里份、氟樹脂（杜邦公司）15〇重量份、界面活性劑樹 曰（日彳§化學工業公司）2重量份，以使整體固體成分含 16 200914504 量為2.0重量％之方式製造防靜電塗布液，除此之外，以 與上述實施例1相同之方法製造雙軸拉伸防靜電聚酯膜。 <實施例3 > 將導電性南分子樹脂（Nagase ChemteX公司）1 〇〇重 量份、胺酯樹脂（hepce chem公司）300重量份、環氧交 聯劑（Nagase ChemteX公司）5〇〇重量份、氟樹脂（杜邦 公司）5 0重量份、界面活性劑樹脂（曰信化學工業公司） 2重量份加以混合使用’以使整體固體成分含量為2.5重 f 量％之方式製造防靜電塗布液，除此之外’以與上述實施 例1相同之方法製造雙軸拉伸防靜電聚g旨膜。 <比較例1〉 於製造防靜電塗布液時，不添加聚胺酯樹脂及氟樹脂， 除此之外，以與上述實施例1相同之方法製造雙軸拉伸防 靜電聚酯膜。 <比較例2 > ( 於製造防靜電塗布液時，不添加聚胺酯樹脂，除此之 外，以與上述實施例1相同之方法製造雙轴拉伸防靜電聚 酯膜。 <比較例3 > 於製造防靜電塗布液時，不添加氟樹脂，除此之外， 以與上述實施例i相同之方法製造雙軸拉伸防靜電聚醋 膜。 <試驗例> 對實施例卜3及比較例卜3所製得之防靜電聚酿膜評 17 200914504 價如下述之物性，其結果示於表1。 1. 水接i角 使用接觸角測定器（Ky0wa interface science c0 Ltd，；型號名稱Dr〇pmaster 3〇〇)以離子交換水經蒸餾所得 之純水以液滴法（sessile dr〇p meth〇d)測定水接觸角，在不 同位置測定5次後求出平均值。 2.防靜_電性 ^ 防靜電性測定機（三菱（股），模式名；MCP-T600 )於 % 溫度32<：、濕度50%ΚΙί之環境下設置試樣後，根據jIS K 7 1 9 4測定表面電阻。 3 · 耐水，H： 將膜放置於流動之自來水中i分鐘後，以5〇。〇乾燥w 分鐘後，以如下述之方式評價防靜電性與外觀。 〇.無白濁現象防靜電性無降低之情形 4 _ 耐乙醇忡 〔 以乙醇沾濕棉棒後，將棉棒之角度維持為牦度之狀況 k下，於上述經塗布處理之薄膜面，以IN負重、5cm/sec之 速度往返於5cm長度達10次後，以下述基準評價塗布面 之狀態。 〇：幾乎無防靜電功能之變化，無傷痕之情形 △防靜電功能降低或有些許傷痕之情形 X:防靜電功能消失、或塗布面被磨耗之情形 明性（濁唐） 試樣1片直放置於濁庶 18 200914504 1定機（AUTOMATIC DIGITAL HAZEMETER，日本電測 公司製）’測定於垂直放置之試驗之直角方向使具有 400〜700 波長之光穿透時之值。 此時’濁度（Haze)值，係以下述數學式1求得β 濁度（％)= (1 一（散射光之量/光之總穿透量》χ1〇〇 膠帶杀|_1離力- Stage 1: Uniaxially stretched polyester film, a polyethylene terephthalate granule (Pellet) having an ultimate viscosity of G_625dl/g (this polyethylene terephthalate particle system is mixed) An amorphous spherical cerium oxide particle having an average particle diameter of 2.5 in 汕卯(7), which is fully dried by a vacuum dryer for 7 hours and then melted to extrude a τ mold: a cooling cylinder is applied to apply a static method (pinning) to make a close cooperation The amorphous unstretched sheet was formed into a uniaxially stretched polystyrene film by reheating it at a pressure of 95 t in a direction of 35 times. After that, the side of the obtained uniaxially stretched polyester film was subjected to corona discharge treatment. _Phase 2: Biaxially stretched polyester film is applied to the surface of the corona treatment, and it will be used as a solid component conductive polymer resin (Nagase ChemteX's DENATR〇N#5002SZ; containing poly 3,4-ethylene Dioxin 〇 5 5 5 5 5 5 5 5 5 5 5 5 8 8 8 8 8 8 8 8 8 ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) he he he he he he 200 parts by weight of a functional anionic poly-transamine dispersion), melamine cross-linking agent (CYMEL385) 200 parts by weight, tetrafluoroethylene (DuPont, SLA-NE W) 100 weight 2 parts by weight of a surfactant resin (Japan Chemical Industry Co., Ltd., EXP405 1 ; acetylene dioxime) was combined with water to prepare an antistatic coating liquid. In this case, the content of the solid component was 1.5% by weight based on the total antistatic coating liquid. This antistatic coating liquid was applied to the uniaxially stretched polyester film of the above stage 1 using a #6 wire bar. After coating, the tenter was stretched at a thickness of 1 〇 5 to 14 〇〇c (the section was applied to dry the applied coating liquid) by 3.5 times in a direction perpendicular to the direction in which the film was carried out, and heat treated at 24 (rc for 4 seconds). Thus, a 38# m thick biaxially stretched antistatic polyester film was produced. <Example 2 > Using a conductive molecular resin (Nagase ChemteX) 1 〇〇重知, amine ester resin (hepce ehem 4 parts by weight, epoxy hexamethylene M (Nagase ChemteX, DENACOL EX-614) 300 = aliquot, fluororesin (DuPont) 15 parts by weight, surfactant tree 曰 (彳 § Chemical Industry Co., Ltd. A biaxially stretched antistatic polyester film was produced in the same manner as in the above Example 1 except that the antistatic coating liquid was produced in an amount of 0.2% by weight of the total solid content of 16 200914504 in an amount of 2 parts by weight. <Example 3> 1 part by weight of a conductive south molecular resin (Nagase ChemteX Co., Ltd.), 300 parts by weight of an amine ester resin (hepce chem), and an epoxy crosslinking agent (Nagase ChemteX) 5 〇〇 Parts by weight, fluororesin (DuPont) 50 parts by weight, bound 2 parts by weight of the active agent resin (Kyin Chemical Industry Co., Ltd.) was mixed and used to produce an antistatic coating liquid so that the total solid content was 2.5 wt%, and otherwise the same as in the above-mentioned Example 1. The method of producing a biaxially stretched antistatic polyg film was carried out. [Comparative Example 1] A method of manufacturing the antistatic coating liquid was carried out in the same manner as in the above Example 1 except that the polyurethane resin and the fluororesin were not added. Biaxially stretched antistatic polyester film. <Comparative Example 2 > (Biaxial stretching was produced in the same manner as in Example 1 except that the polyurethane resin was not produced in the production of the antistatic coating liquid. Antistatic polyester film. <Comparative Example 3> A biaxially stretched antistatic polyacetal film was produced in the same manner as in the above Example i except that the fluororesin was not added in the production of the antistatic coating liquid. <Test Example> The antistatic polystyrene film obtained in Example 3 and Comparative Example 3 was evaluated as the following physical properties, and the results are shown in Table 1. 1. Water contact i-angle contact Angle measuring device (Ky0wa interface science c0 Ltd , Model name Dr〇pmaster 3〇〇) The water contact angle is determined by the droplet method (sessile dr〇p meth〇d) by pure water obtained by ion-exchanged water, and the average value is determined after 5 times at different positions. 2. Anti-static _ electrical ^ Anti-staticity measuring machine (Mitsubishi (share), mode name; MCP-T600) After setting the sample under the environment of % temperature 32 <:, humidity 50% ΚΙί, according to jIS K 7 1 9 4 Determine the surface resistance. 3 · Water resistant, H: Place the film in running tap water for 1 minute, 5 〇. After drying for 分钟 w minutes, the antistatic property and appearance were evaluated in the following manner. 〇. No white turbidity phenomenon, no anti-static effect 4 _ Ethanol-resistant 忡 [ After the cotton swab is wetted with ethanol, the angle of the cotton swab is maintained at a k-degree, on the coated film surface, After the IN load and the speed of 5 cm/sec were repeated to the length of 5 cm for 10 times, the state of the coated surface was evaluated by the following criteria. 〇: There is almost no change in anti-static function, no damage. △ Anti-static function is reduced or there are some scratches. X: The anti-static function disappears, or the coated surface is worn out. (Liang Tang) Sample 1 straight Placed in the turbidity 18 200914504 1 (AUTOMATIC DIGITAL HAZEMETER, manufactured by Nippon Denshoku Co., Ltd.) 'Measures the value when the light having a wavelength of 400 to 700 is penetrated in the direction perpendicular to the vertical placement test. At this time, the turbidity (Haze) value is obtained by the following mathematical formula 1: β turbidity (%) = (1 (the amount of scattered light / total penetration of light) χ 1 〇〇 tape kill | _1 force
於23 ±3、相對濕度5〇±5%之環境氣氛下使用剝離力 測疋機即ARl〇〇〇(chem instruments公司）裝備，於上述所 得之膜之塗布面貼附日東電工股份有限公司製膠帶n〇. 31B (厚度.25 " m、寬度·· 25mm)後以2kg負重之橡膠 滾輪來回擠壓！次後，馬上以剝離速度〇 進行 度剝離。此時，測定所得之剝離力。 L表。 —------ —_奏阻 Ω/sq 實施例1 實施例2 實施例3 比較例1 比較例2 比車交例3 105 105~~ 105— 105 105 105 —觸角(。） 101 102 98 64 103 51 —_____^水性 〇 Ο 1 〇 〇 〇 醇性 §^j±(Haze) Γ〇 2.5 .〇 〇 「〇 〇 〇 2.3 2.6 2.4 2.5 2.5 ^力(g/in) 388 L 355 __453 52 61 395 m由表1可知，未含聚胺_樹脂之比較例1、2，由於膠 ::離力之值低故無法得到所欲之物性，而未含氟樹脂之 乂例1、3,由於水接觸角低故無法得到所欲之物性。 由具有含聚胺酯接I· 0匕命@上士 t ^ , f月曰/、軋树脂之防靜電層之實施例 所製造之聚醋膜，可製造維持耐水性、财溶劑性及表 19 200914504 面電阻為 1x1 Ο6 Ω /square以下之物性、且具有95°以上之 高水接觸角值與膠帶剝離力為300g/in以上之值的膜。 【圖式簡單說明】 無 【主要元件符號說明】 無 f % 20It is equipped with a peeling force measuring machine (ARl〇〇〇 (chem instruments)) under an ambient atmosphere of 23 ± 3 and a relative humidity of 5 〇 ± 5%, and is attached to Nitto Denko Co., Ltd. on the coated surface of the film obtained above. Tape n〇. 31B (thickness .25 " m, width · · 25mm) and then squeeze back and forth with a 2kg weight rubber roller! After that, it was peeled off at the peeling speed 马上 immediately. At this time, the obtained peeling force was measured. L table. —------ — _ Actuation Ω/sq Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Example of car interchange 3 105 105~~ 105— 105 105 105 — Tentacle (.) 101 102 98 64 103 51 —_____^ Aqueous 〇Ο 1 sterol §^j±(Haze) Γ〇2.5 .〇〇 “〇〇〇2.3 2.6 2.4 2.5 2.5 ^力(g/in) 388 L 355 __453 52 61 395 m It can be seen from Table 1 that Comparative Examples 1 and 2, which do not contain polyamine-resin, cannot obtain the desired physical properties due to the low value of the gel: the dissociation force, and the examples 1 and 3 without the fluorine-containing resin. Since the water contact angle is low, the desired physical properties cannot be obtained. The polyester film produced by the embodiment having the antistatic layer containing the polyurethane, the sergeant, the sergeant, and the resin is It is possible to produce a film which maintains the water resistance and the solvent property and has a physical property of 1×1 Ο6 Ω /square or less and has a high water contact angle value of 95° or more and a tape peeling force of 300 g/in or more. [Simple description of the diagram] No [Main component symbol description] No f % 20