201006873 九、發明說明： 【發明所屬之技術領域】 本發明係關於抗靜電聚酯膜的製造方法、因此而製得 的抗靜電聚酯膜以及該抗靜電聚酯膜的用途。更尤其，本 發明係關於一種用於製造絕佳抗靜電聚酯膜的方法，其係 藉由添加氟樹脂與聚胺基甲酸酯樹脂至形成在聚酯膜的_ 側或兩側上之抗靜電層，以獲得絕佳透明度與抗靜電特性 並且增進黏性膠帶黏附性、墨水黏附性及防污性能；因此 而製得的抗靜電聚酯膜；及其用途。 【先前技術】 隨著產業發展，在各種電子/電氣裝置、資訊與通訊領 域及一般生活必需品中由於靜電所導致的損害已增多。藉 此’在相關領域中對於靜電防護之需求已然増加。 在產業領域中由於靜電生成所導致的問題係在於因為 靜電存在於產品，所以雜質或灰塵會黏附至產品；而且隨 著製造或加工膜的製程當中發生放電，有機溶劑係使用於 該類製程中，由此增加引燃的危險。 此外’因為靜電存在於用於電氣/電子部件之材料中， 所以靜電成為產品損壞的主要原因。是以，有必要賦予電 子/電氣領域產品抗靜電性能。 「靜電防護」一詞的意思是經由適宜方法釋放累積在 絕緣體（絕緣材料）表面的電荷。為了達到靜電防護，抗 靜電層係形成在產品表面上，以便釋放累積在表面上的電 荷。 201006873 包含抗靜電層之形成的習知抗靜電技術係包括内部添 加方法，該方法係使用陰離子性化合物，例如有機續酸鹽 與有機碼酸鹽在表面上沈積金屬化合物的方法；塗佈導 Μ㈣mu塗佈低分子陰離子性或陽離子性化合 物的方法；以及塗佈導電聚合物的方法。 Ο 在上述方法中，内部添加方法具有節省成本以及絕佳 熟化特性與穩定性的優點’但㈣有膜特性變差、抗靜電 效果受限、難層之間由於散輝_(bl〇〇ming)所導致之 黏附性降低的問題。將金屬化合物塗佈至表面的方法展現 了絕佳的抗靜電性能’於是已經常用於導電膜，但由於高 生產成本的緣故’該方法係限於特殊應用。 此外，塗佈低分子陰離子性或陽離子性化合物的方法 係廣泛被使用’因為該方法具有相對良好抗靜電效果及人 理生產成本的優點。然而，使用此方法所形成的抗靜電層 係藉由和大氣中的水分結合而獲得抗靜電特性。因此，當 大氣的水分含量極低時，此方法會有缺點例如抗靜電特 性大大降低、極差的耐溶劑性及轉移至其他表面。為此， 此方法之應用係大大地受限。 為了克服上述問題，已發展出聚苯胺、聚n比唾、或聚 嘆吩導電聚合物且近年已用於眾多應用型調查研究办中， 以賦予抗靜電聚醋膜或其他聚合物之表面導電性。 在用於消除靜電的習知方法中…㈣常使用的 係包含：製備經摻雜之導電聚合物；將製備的聚合物溶於 適宜溶劑；以及將該溶液塗覆在各種聚合物，例如聚" 7 201006873 ，以增進塗覆 表面上此外適宜的黏合劑係溶於溶劑中 層的機械特性，例如_性或表面硬度。 舉例來說，美國專利第4 959 43〇號揭示 電性的3,4-聚乙烯-备* + 、有絕佳導 …人… 基噻吩聚合物，該聚合物係藉由在室 溫下混合3，4 -乙祕-客* & 主 對甲策墙酿雄— 一種導電單體〜與氧化劑 11)而合成。亦有販售分散於水中的人 聚乙稀二氧基嗟吩聚合物，當3,4·乙烯二氧基料舆對2 績酸鐵（叫㈣合物在室溫下長期靜置時，可能會發^ ❹ 聚合反應。為了防止此聚合反應，亦可添加少量反應抑制 劑味唾。 曰本專利公開案平1 313521號揭示了由聚〇,4·二燒 氧基噻吩）與聚陰離子所構成的導電聚合物。習知此導電 聚合物在t成膜時係具有冑度導電性、冑度化學穩定性及 極尚膜透明度。然而，當含有該導電聚合物的塗覆溶液塗 佈至塑膠基板時’則不易獲得滿足包括基板黏附性、透明 度、防水性、耐溶劑性及導電性之所有特性的塗覆膜。201006873 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing an antistatic polyester film, an antistatic polyester film thus obtained, and the use of the antistatic polyester film. More particularly, the present invention relates to a method for producing an excellent antistatic polyester film by adding a fluororesin and a polyurethane resin to form on the _ side or both sides of the polyester film. Antistatic layer for excellent transparency and antistatic properties and to improve adhesive tape adhesion, ink adhesion and antifouling properties; thus made antistatic polyester film; and its use. [Prior Art] With the development of the industry, damage due to static electricity has increased in various electronic/electrical devices, information and communication fields, and general necessities. By this, the demand for electrostatic protection in related fields has increased. The problem caused by static electricity generation in the industrial field is that impurities or dust adhere to the product because static electricity is present in the product; and organic solvents are used in such processes as discharge occurs during the process of manufacturing or processing the film. , thereby increasing the risk of ignition. Furthermore, since static electricity is present in materials for electrical/electronic parts, static electricity is a major cause of product damage. Therefore, it is necessary to give antistatic properties to products in the electronic/electrical field. The term "electrostatic protection" means to discharge the electric charge accumulated on the surface of the insulator (insulating material) by a suitable method. In order to achieve electrostatic protection, an antistatic layer is formed on the surface of the product to release the charge accumulated on the surface. 201006873 A conventional antistatic technique comprising the formation of an antistatic layer comprises an internal addition method using an anionic compound, such as a method of depositing a metal compound on a surface with an organic acid salt and an organic acid salt; coating a crucible (four) mu A method of coating a low molecular anionic or cationic compound; and a method of coating a conductive polymer. Ο In the above method, the internal addition method has the advantages of cost saving and excellent ripening characteristics and stability'. However, (4) there is deterioration of film properties, limited antistatic effect, and fading between hard layers _ (bl〇〇ming The resulting problem of reduced adhesion. The method of applying a metal compound to a surface exhibits excellent antistatic properties. Thus, it has been frequently used for a conductive film, but the method is limited to a specific application due to high production cost. Further, a method of coating a low molecular anionic or cationic compound is widely used because the method has an advantage of relatively good antistatic effect and human production cost. However, the antistatic layer formed by this method obtains antistatic properties by combining with moisture in the atmosphere. Therefore, when the moisture content of the atmosphere is extremely low, this method has disadvantages such as greatly reduced antistatic properties, extremely poor solvent resistance, and transfer to other surfaces. For this reason, the application of this method is greatly limited. In order to overcome the above problems, polyaniline, poly n-salt, or polystimene conductive polymers have been developed and have been used in numerous application research institutes in recent years to impart surface conduction to antistatic polyester films or other polymers. Sex. In a conventional method for eliminating static electricity... (4) commonly used systems include: preparing a doped conductive polymer; dissolving the prepared polymer in a suitable solvent; and coating the solution on various polymers, such as poly " 7 201006873 to improve the mechanical properties of a suitable binder on the coated surface which is soluble in the solvent layer, such as _ sex or surface hardness. For example, U.S. Patent No. 4,959,430 discloses an electrically conductive 3,4-polyethylene-prepared*, an excellent... human thiophene polymer which is mixed at room temperature. 3,4 - B secret - guest * & main to the wall of the wall - a conductive monomer ~ and oxidant 11) and synthesized. There are also people selling polyethylenedioxy porphin polymers dispersed in water. When 3,4·ethylene dioxyanthene is used, it is a long time when it is allowed to stand at room temperature for a long time. A polymerization reaction may be carried out. In order to prevent this polymerization reaction, a small amount of a reaction inhibitor may be added to the saliva. The disclosure of this patent publication No. 1 313521 discloses a polyanthracene, a tetra-oxy thiophene) and a polyanion. The conductive polymer formed. It is known that this conductive polymer has a haze conductivity, a chemical stability of the twist, and an excellent film transparency at the time of film formation at t. However, when the coating solution containing the conductive polymer is applied to the plastic substrate, it is difficult to obtain a coating film satisfying all the characteristics including substrate adhesion, transparency, water repellency, solvent resistance, and conductivity.
為了增進塗覆膜的防水性，已嘗試摻有交聯劑之交聯 樹脂的方法"在日本專利公開案平6-73271號中，一種具有 環氧基團的烷氧基矽烷化合物係用於增進由聚（3，4-二烷氧 基喧吩）與聚陰離子所構成的導電層及其毗鄰層之間的黏 附性’但該方法就賦予塗覆膜防水性而言仍有不足。 隨著包括液晶顯示器（此後稱作"LCDs")與電漿顯示 面板（此後稱作"PDPs")之IT產業的近年成長，對於抗靜 電膜的需求快速地增加。在上述各式各樣抗靜電技術中’ 8 201006873 陽離子性抗靜電技術係通常用於電氣/電子領域，而且使用 導電聚α物的抗靜電技術已引進頂級膜市場。 因 ill· 在需要抗靜電性能的產業領域中，有發展展現 絕佳抗靜電特性，同時展現在黏性膠帶黏附性、墨水黏附 14及防，亏性能方面改良的抗靜電膜的急迫需求。 也就是說，該抗靜電膜係用作為保護膜且假使膠帶 抗靜雷类石 、 面之間的黏附性很低’在卸除保護膜的最終製程 ❸ 中就無法卸除保護臈或者影響卸除製程中的產品。為此， 黏陡膠帶與抗靜電膜之間的黏附性必須要高。 此外’墨水在製程期間係塗覆在保護膜表面上，以評 估對產品的接受與拒絕。此時，假使墨水與保護膜表面之 間的黏附性很低，墨水會從保護膜脫落。為此，墨水與保 5蔓膜之間的黏附性必須要高。 【發明内容】 本發明之目的係提供一種用於製造聚酯膜的方法，其 Φ 係藉由將氟樹脂與聚胺基甲酸酯樹脂塗佈至形成在聚酯膜 一側或兩側上之抗靜電層，以獲得絕佳的透明度與抗靜電 特性，同時增進黏性膠帶黏附性、墨水黏附性及防污性能。 本發明另一目的係提供一種根據該方法製造的抗靜電 聚酯膜。 本發明又一目的係提供該抗靜電聚酯膜的用途。 為了達成上述目的，在一態樣中，本發明係提供一種 用於製造抗靜電聚酯膜的方法，該方法係包含下列步驟： 製造經單軸拉伸之聚酯膜；將抗靜電溶液塗佈至經單轴定 9 201006873 向之聚酯膜的一側或兩側，以形成抗靜電層；再拉伸該上 面形成有抗靜電層之聚酯膜，以製造經雙軸拉伸之聚酯膜。 在本發明中，抗靜電溶液含有導電聚合物樹脂以及以 100重量份導電聚合物樹脂為基準之100-1000重量份聚胺 基甲酸酯樹脂、100-1000重量份交聯樹脂、及30-300重量 份氟樹脂。 塗覆溶液内的導電聚合物樹脂係選自於由聚陰離子與 聚噻吩所構成之水性分散液型樹脂或是由聚陰離子與聚嗟 吩衍生物所構成之水性分散液型樹脂。 抗靜電溶液内的聚胺基曱酸酯樹脂係較佳為含有選自 於由經基、胺基及羧基所構成之官能基之至少一基的水性 分散液型樹脂。 抗靜電溶液内的交聯樹脂較佳為選自於由異氰酸醋、 羰基醯亞胺、聘唑啉、環氧及三聚氰胺所構成群組的至少一 化合物。 抗靜電溶液内的氟樹脂較佳為選自於由下列所構成3In order to improve the water repellency of the coating film, a method of using a cross-linking resin doped with a crosslinking agent has been attempted. In the Japanese Patent Laid-Open No. Hei 6-73271, an alkoxydecane compound having an epoxy group is used. In order to enhance the adhesion between the conductive layer composed of poly(3,4-dialkoxy porphin) and the polyanion and its adjacent layer, the method is still insufficient in imparting water repellency to the coating film. With the recent growth of the IT industry including liquid crystal displays (hereinafter referred to as "LCDs") and plasma display panels (hereinafter referred to as "PDPs"), the demand for antistatic films has rapidly increased. Among the above various antistatic technologies, '8 201006873 cationic antistatic technology is commonly used in the electrical/electronic field, and antistatic technology using conductive polyalphaphages has been introduced into the top film market. Ill· In the industrial field where antistatic properties are required, there is an urgent need to develop an antistatic film that exhibits excellent antistatic properties while exhibiting improved adhesion to adhesive tape, ink adhesion, and resistance to loss. That is to say, the antistatic film is used as a protective film and if the tape is resistant to static ray-like stones and the adhesion between the faces is low, it is impossible to remove the protective 臈 or affect the unloading in the final process of removing the protective film. In addition to the products in the process. For this reason, the adhesion between the adhesive tape and the antistatic film must be high. In addition, the ink is applied to the surface of the protective film during the process to evaluate acceptance and rejection of the product. At this time, if the adhesion between the ink and the surface of the protective film is low, the ink may fall off from the protective film. For this reason, the adhesion between the ink and the film must be high. SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a polyester film, which is formed by coating a fluororesin and a polyurethane resin on one side or both sides of a polyester film. The antistatic layer for excellent transparency and antistatic properties, while improving the adhesion of adhesive tape, ink adhesion and antifouling properties. Another object of the present invention is to provide an antistatic polyester film produced according to the method. A further object of the invention is to provide the use of the antistatic polyester film. In order to achieve the above object, in one aspect, the present invention provides a method for producing an antistatic polyester film, the method comprising the steps of: producing a uniaxially stretched polyester film; coating an antistatic solution The cloth is uniaxially fixed to one side or both sides of the polyester film to form an antistatic layer; the polyester film having the antistatic layer formed thereon is further stretched to produce a biaxially stretched poly Ester film. In the present invention, the antistatic solution contains a conductive polymer resin and 100-1000 parts by weight of a polyurethane resin based on 100 parts by weight of the conductive polymer resin, 100-1000 parts by weight of a crosslinked resin, and 30- 300 parts by weight of a fluororesin. The conductive polymer resin in the coating solution is selected from an aqueous dispersion type resin composed of a polyanion and polythiophene or an aqueous dispersion type resin composed of a polyanion and a polyphenylene derivative. The polyamino phthalate resin in the antistatic solution is preferably an aqueous dispersion-type resin containing at least one selected from the group consisting of a trans group, an amine group and a carboxyl group. The crosslinked resin in the antistatic solution is preferably at least one compound selected from the group consisting of isocyanate, carbonyl quinone, oxazoline, epoxy and melamine. The fluororesin in the antistatic solution is preferably selected from the group consisting of 3
群組之一者：聚四氟乙烯共聚物、四氟乙烯、全氟烷基Y 烯醚共聚物、三氟乙烯、六氟丙烯共聚物、乙烯、氣三_ 乙烯共聚物、四氟乙烯共聚物、氣三氟乙烯、聚四氟二 共聚物、聚氟乙烯及聚二氟亞乙烯。更佳 尺佳的是使用四氟2 烯樹脂。 本發明的抗靜電溶液係較佳含有05_10赠。固體含量 並額外含有以100重量份抗靜電溶液為基準之001_1重 份乳劑型含氟界面活性劑。 201006873 在另一態樣中，本發明係提供一種根據該方法製造的 抗靜電聚酯膜，該抗靜電聚酯膜係具有少於l〇w β/sq之表 面電阻率，而因此展現抗靜電特性》 本發明的抗靜電聚酯膜係使用最佳化抗靜電溶液所製 得，於是具有絕佳的抗靜電特性，同時展現在黏性膠帶黏 附性、墨水黏附性、防污性能及耐溶劑性方面之改良。 此外，該抗靜電聚酯膜係具有150-2000 g/in之膠帶黏 附性以及大於90。之水接觸角，而因此展現絕佳的墨水黏附 • 性。 在另一具體實例中，本發明係提供用於顯示裝置之表 面保護膜，該表面保護膜係應用至選自於由LCDs、PDPs、 個人數位助理（此後稱作"PDAs")及導航系統所構成之群 組的任一顯示裝置。 根據本發明，藉由在經單軸拉伸之聚酯膜上形成抗靜 電層並再次拉伸該經拉伸之聚酯膜，本發明的方法可賦予 φ 穩定的抗靜電特性並且一同時一經由減少製程步驟降低製 造成本。此外’藉由將含有導電聚合物樹脂、聚胺基甲酸 酉曰黏δ劑樹爿曰、交聯樹脂、含氣防污樹脂及含敦界面活性 劑樹脂之抗靜電溶液塗佈至經單轴拉伸之聚酯膜的—側或 兩側’本發明可提供具有絕佳抗靜電特性，且同時展現在 黏性膠帶黏附性、墨水黏附性、防污性能及耐溶劑性方面 改良的抗靜電聚酯膜。 根據本發明方法所製得的抗靜電聚酯膜係應用至顯示 裝置’包括了 LCDs、PDPs、PDAs及導航系統，於是可有 201006873 利地用作為用於顯示裝置之表面保護膜。 【實施方式】 此後，將詳細地說明本發明。 本發明係提供一種抗靜電聚酯膜的製造方法，該方法 包含了下列步驟：1)製造經單軸拉伸之聚酯膜；2)將抗 靜電溶液塗佈至該經單軸拉伸之聚酯膜的一側或兩側上， 以形成抗靜電層；以及3)再拉伸該上面形成有抗靜電層之 聚酯膜’以製造經雙轴拉伸之聚酯膜。 該抗靜電聚酯膜製造方法的第一特徵係在於抗靜電層 係形成在經單轴拉伸之聚酯膜上並在於該上方形成有抗靜 電層之聚酯膜係經再次拉伸。由於抗靜電層在製造過程中 係以線上方式形成，所以製程步驟減少了並且—同時—賦予 該膜穩定的抗靜電特性；因此，可製得具有所欲物理特性 的產品。 用於製造聚酯膜之方法的步驟1)係包含製造經單軸拉 伸之聚酯膜。 在本發明中，在先前技藝用於抗靜電塗覆的任何膜可 用作為聚酯膜，並無特別限制。較佳使用聚酯基樹脂。 形成該膜的聚酯基樹脂係藉由縮合芳族二羧酸和脂族 二醇來製備。對苯二甲酸、2,6-萘二甲酸或類似者係用作為 芳族二羧酸，乙二醇、二乙二醇、1,4-環己二甲醇或類似者 係用作為脂族二醇。較佳地，聚對苯二曱酸乙二酯（PET )、 聚對苯二甲酸丁二酯（PBT)或聚2,6-萘二曱酸乙二酯（PEN) 係用作為聚酯基樹脂。 12 201006873 含有第三種成分的共聚物亦可用作為聚酯樹脂。共聚 化聚醋的二羧酸成分可為選自於由下列所構成之群組之一 者或是二或多者之組合：間苯二曱酸、鄰苯二甲酸、對苯 一甲酸、2,6-萘二曱酸、己二酸、癸二酸及對羥苯甲酸。乙 二醇成分可為選自於由下列所構成之群組之一者或是二或 多者之組合：乙二醇、二乙二醇、丙二醇、丁二醇、14_ 環己二甲醇及新戊二醇。 上述聚酯樹脂組成物可在真空中乾燥，然後在擠出機 _ 内熔融。熔融材料可經由τ型模具擠出，以形成薄片。可 使用釘扎方法讓該薄片和冷卻輥筒緊密接觸以使薄片冷卻 並固化’於是獲得未經拉伸之聚酯薄片。 未經拉伸之聚醋薄片係於加熱超過聚酯樹脂之玻璃轉 化溫度的輥筒之間被拉伸’根據輥筒之間的運行速度差 異，該聚酯薄片被單轴拉伸至原始尺寸之2.5_45倍，於是 製造經單軸拉伸之聚酯膜。 φ 抗靜電聚酯膜製造方法的第二特徵係在於含有導電聚 合物樹脂、聚胺基甲酸酯黏合劑樹脂、含氟防污樹脂及交 聯樹脂之抗靜電溶液係塗佈至抗靜電層，以增進抗靜電性 能、膠帶黏附性、墨水黏附性及防污性能。 明確地說，本發明之製造方法所使用的抗靜電溶液係 塗佈至經單轴拉伸之聚酯膜的一側或兩側，以形成抗靜電 層該抗靜電，容液含有導電聚合物樹脂以及以1〇〇重量份 導電聚合物樹脂為基準之1G(M_重量份聚胺基甲酸醋樹 月日、100_10G0重1份交聯樹脂及3G.则重量份氟樹脂。 13 201006873 抗靜電溶液内的導電聚合物樹脂係賦予抗靜電特性且 係較佳選自於由聚陰離子與聚噻吩所構成之水性分散液型 樹脂或是由聚陰離子與聚噻吩衍生物所構成之水性分散液 型樹脂。 聚陰離子為酸性聚合物’例如聚合叛酸、聚合確酸、 聚乙婦確酸或類似者。聚合羧酸的例子包括了聚丙烯酸、 聚曱基丙烯酸、聚順丁烯二酸等等，而聚合磺酸的例子則 包括聚苯乙稀績酸等等。 本發明的導電聚合物樹脂係較佳含有以固體含量為基 準之相對於聚噻吩或聚噻吩衍生物的過量聚陰離子，以賦 予導電性。 當聚噻吩或聚噻吩衍生物係以1 wt%之份量使用時，聚 陰離子則以至少1 wt%、較佳wt%及更佳1-3 wt%之份 量被包含在内。 在本發明的實施例中，包含〇.5 wt〇/o聚（3 4_乙烯二氧 基嘆吩）與0.8 wt%聚苯乙烯磺酸（分子量（Mn)=150,000 ) 之水性分散液型樹脂係用作為導電聚合物樹脂。 本發明之抗靜電溶液内的聚胺基甲酸酯樹脂係塗佈至 聚S旨膜’以增加膠帶與膜表面之間的黏附性以及墨水與膜 表面之間的黏附性β 含有選自於由羥基、胺基及羧基所構成之官能基之至 少一基的水性分散液型樹脂係用作為聚胺基甲酸酯樹脂。 本發明的一較佳具體實例係使用陰離子性聚醚-聚胺基甲酸 醋分散液’但本發明之範疇並不受其限制。 201006873 此外，聚胺基曱酸酯樹脂係以以100重量份導電聚合 物樹知為基準之100-1000重量份的份量添加。當聚胺基甲 酸醋樹脂的含量少於100重量份時，膠帶與膜之間的黏附 性會降低或者墨水附著至膜的黏附性並無改善。另一方 面’當含量超過1000重量份時，膠帶黏附性與墨水黏附性 改善了，但防污性能與抗靜電特性會下降。 本發明之抗靜電溶液内的交聯樹脂係用於增進防水性 以及抗靜電層與聚酯膜之間的塗覆性能。One of the groups: polytetrafluoroethylene copolymer, tetrafluoroethylene, perfluoroalkyl Y-ether copolymer, trifluoroethylene, hexafluoropropylene copolymer, ethylene, gas triethylene copolymer, tetrafluoroethylene copolymer , gas trifluoroethylene, polytetrafluoroethylene copolymer, polyvinyl fluoride and polydifluoroethylene. More preferred is the use of tetrafluoroethylene resin. The antistatic solution of the present invention preferably contains a gift of 05_10. The solid content additionally contained 001_1 parts by weight of the emulsion type fluorine-containing surfactant based on 100 parts by weight of the antistatic solution. 201006873 In another aspect, the present invention provides an antistatic polyester film produced according to the method, the antistatic polyester film having a surface resistivity of less than 10 〇 w β / sq, and thus exhibiting antistatic Characteristics The antistatic polyester film of the present invention is obtained by using an optimized antistatic solution, so that it has excellent antistatic properties, and exhibits adhesion to an adhesive tape, ink adhesion, antifouling property and solvent resistance. Improvement in sexuality. Further, the antistatic polyester film has a tape adhesion of 150 to 2000 g/in and a density of more than 90. The water contacts the corners and thus exhibits excellent ink adhesion. In another embodiment, the present invention provides a surface protective film for a display device that is applied to selected from LCDs, PDPs, personal digital assistants (hereinafter referred to as "PDAs"), and navigation systems Any of the display devices of the group formed. According to the present invention, the method of the present invention imparts stable antistatic properties to φ by forming an antistatic layer on the uniaxially stretched polyester film and stretching the stretched polyester film again. Reduce manufacturing costs by reducing process steps. In addition, by applying an antistatic solution containing a conductive polymer resin, a ruthenium polycarboxylate tartar, a crosslinked resin, a gas-containing antifouling resin, and a resin containing a surfactant, to the uniaxial - Side or both sides of the stretched polyester film. The present invention provides an antistatic property which has excellent antistatic properties and at the same time exhibits improved adhesion to adhesive tape, ink adhesion, antifouling property and solvent resistance. Polyester film. The antistatic polyester film produced by the method of the present invention is applied to a display device' including LCDs, PDPs, PDAs, and a navigation system, and thus 201006873 can be advantageously used as a surface protective film for a display device. [Embodiment] Hereinafter, the present invention will be described in detail. The present invention provides a method for producing an antistatic polyester film, which comprises the steps of: 1) producing a uniaxially stretched polyester film; 2) applying an antistatic solution to the uniaxially stretched film One side or both sides of the polyester film to form an antistatic layer; and 3) re-stretching the polyester film on which the antistatic layer is formed to produce a biaxially stretched polyester film. The first feature of the method for producing an antistatic polyester film is that the antistatic layer is formed on the uniaxially stretched polyester film and the polyester film having the antistatic layer formed thereon is stretched again. Since the antistatic layer is formed in an in-line manner during the manufacturing process, the process steps are reduced and - at the same time - impart a stable antistatic property to the film; therefore, a product having desired physical properties can be obtained. The step 1) of the method for producing a polyester film comprises the production of a uniaxially stretched polyester film. In the present invention, any film which has been previously used for antistatic coating can be used as the polyester film, and is not particularly limited. A polyester-based resin is preferably used. The polyester-based resin forming the film is prepared by condensing an aromatic dicarboxylic acid and an aliphatic diol. Terephthalic acid, 2,6-naphthalenedicarboxylic acid or the like is used as an aromatic dicarboxylic acid, ethylene glycol, diethylene glycol, 1,4-cyclohexanedimethanol or the like as an aliphatic two. alcohol. Preferably, polyethylene terephthalate (PET), polybutylene terephthalate (PBT) or polyethylene-2,6-naphthalene dicarboxylate (PEN) is used as the polyester base. Resin. 12 201006873 A copolymer containing a third component can also be used as a polyester resin. The dicarboxylic acid component of the copolymerized polyacetate may be selected from one of the group consisting of or a combination of two or more of the following: isophthalic acid, phthalic acid, p-benzoic acid, 2 , 6-naphthalenedicarboxylic acid, adipic acid, sebacic acid and p-hydroxybenzoic acid. The ethylene glycol component may be selected from one or a combination of two or more of the following groups: ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, 14-cyclohexanedimethanol, and new Pentylene glycol. The above polyester resin composition can be dried in a vacuum and then melted in an extruder. The molten material can be extruded through a τ-type die to form a sheet. The sheet can be brought into intimate contact with the chill roll by a pinning method to allow the sheet to cool and solidify' to obtain an unstretched polyester sheet. The unstretched polyester flaky sheet is stretched between rolls heated above the glass transition temperature of the polyester resin. The polyester sheet is uniaxially stretched to the original size depending on the difference in running speed between the rolls. 2.5_45 times, then a uniaxially stretched polyester film was produced. The second feature of the φ antistatic polyester film manufacturing method is that an antistatic solution containing a conductive polymer resin, a polyurethane binder resin, a fluorine-containing antifouling resin, and a crosslinked resin is applied to the antistatic layer. To improve antistatic properties, tape adhesion, ink adhesion and antifouling properties. Specifically, the antistatic solution used in the manufacturing method of the present invention is applied to one side or both sides of the uniaxially stretched polyester film to form an antistatic layer which is antistatic, and the liquid contains a conductive polymer. Resin and 1G based on 1 part by weight of conductive polymer resin (M_part by weight of polyurethane vinegar, 100_10G0 by 1 part of crosslinked resin and 3G. by weight of fluororesin. 13 201006873 Antistatic The conductive polymer resin in the solution imparts antistatic properties and is preferably selected from an aqueous dispersion type resin composed of a polyanion and polythiophene or an aqueous dispersion type composed of a polyanion and a polythiophene derivative. Resin. The polyanion is an acidic polymer such as polymeric tracism, polymeric acid, poly-tanoic acid or the like. Examples of polymeric carboxylic acids include polyacrylic acid, polyacrylic acid, polymaleic acid, and the like. Examples of the polymerization sulfonic acid include polystyrene, etc. The conductive polymer resin of the present invention preferably contains an excess polyanion relative to the polythiophene or polythiophene derivative based on the solid content. To impart conductivity. When the polythiophene or polythiophene derivative is used in an amount of 1 wt%, the polyanion is included in an amount of at least 1 wt%, preferably wt%, and more preferably 1-3 wt%. In an embodiment of the invention, an aqueous dispersion comprising 〇.5 wt〇/o poly(3 4_ethylenedioxy sinter) and 0.8 wt% polystyrene sulfonic acid (molecular weight (Mn)=150,000) The resin is used as a conductive polymer resin. The polyurethane resin in the antistatic solution of the present invention is applied to the poly film to increase the adhesion between the tape and the film surface as well as the ink and film surface. The adhesive phase β contains an aqueous dispersion type resin selected from at least one group of a functional group composed of a hydroxyl group, an amine group, and a carboxyl group, and is used as a polyurethane resin. The example uses an anionic polyether-polyurethane vinegar dispersion 'but the scope of the present invention is not limited thereto. 201006873 Further, the polyamino phthalate resin is based on 100 parts by weight of a conductive polymer tree. 100-1000 parts by weight of the addition. When the polyurethane vinegar resin When the content is less than 100 parts by weight, the adhesion between the tape and the film may be lowered or the adhesion of the ink to the film may not be improved. On the other hand, when the content exceeds 1000 parts by weight, the adhesion of the tape and the adhesion of the ink are improved. However, the antifouling property and the antistatic property are degraded. The crosslinked resin in the antistatic solution of the present invention is used for improving the water repellency and the coating property between the antistatic layer and the polyester film.
I r 本發明所使用的交聯樹脂係為選自於由異氱酸酯、羰 基醯亞胺、聘唑啉、環氧及三聚氰胺所構成之群組的至少一 化合物，交聯樹脂的含量係較佳為以1〇〇重量份導電聚合 物樹脂為基準之100-1000重量份。 當交聯樹脂的含量少於100重量份時，該膜展現極差 的抗靜電特性’而且由於膜的低耐溶劑性所致，該膜會發 生白化現象。另一方面’當含量超過1〇〇〇重量份時，該膜 係展現良好的透明度，但抗靜電特性不足。 p 本發明之抗靜電溶液内的氟樹脂係塗佈至聚酯膜，以 增進該膜的防污特性與耐溶劑特性。較佳的氟樹脂係包括 聚四氟乙烯共聚物、四氟乙烯、全氟烷基乙烯醚共聚物、 三敗乙烯、六氟丙烯共聚物、乙烯、氯三氟乙烯共聚物、 四氟乙烯共聚物、氣三氟乙烯、聚四氟乙烯共聚物、聚氟 乙烯、聚一氟亞乙烯等等。較佳地，使用聚四氟乙稀或其 共聚物。 該抗靜電溶液含有以100重量份導電聚合物樹脂為基 15 201006873 準之30 300重量伤氟樹脂。當氟樹脂的含量少於重量份 時，膜的防污特性會下降，而當氟樹脂的含量超過3〇〇重 量份時，膜的透明度與抗靜電特性會下降。 本發明的抗靜電溶液可又含有界面活性劑，以增進塗 覆溶液的穩定性、濕潤與平整特性。習用的界面活性劑係 包括醇類，例如乙醇、異丙醇（is〇pr〇pan〇1 )或異丙基醇 (isopropylalcohol );醚類，例如乙基赛路蘇（e師 cellosolve)或三級丁基赛路蘇；酮類，例如甲基乙基酮或 丙酮；以及胺類，例如二甲基乙醇胺。較佳地，乳劑型含 ❹ 氟界面活性劑係使用於本發明。 含氟界面活性劑亦可和一或多種習用界面活性劑合併 使用。 較佳地，含氟界面活性劑係以以100重量份抗靜電溶 液為基準之G.G1-1重量份之份量添加，以增進塗覆溶液的 防污與濕潤特性。當抗靜電溶液中的界面活性劑含量少於 〇.〇 1重量份時，塗覆溶液的濕潤特性會下降。另一方面 當界面活性劑的含量㈣丨重量份時，塗覆膜之膠帶黏W 〇 性會減低且塗覆膜外觀會因為塗覆溶液内的細小泡泡而發 生缺陷。 本發明之抗靜電溶液的固體含量係較祛 干x m 馮 0.5-10.0 wt%，更佳為1.〇_5.〇 wt〇/〇。當固體含量少於〇 玉 / υ·5 wt0/〇時，塗 覆層的膜形成特性與抗靜電特性將會不足，卷 田固體含量 超過10.0 wt%時，膜的透明度會變差。 此外，本發明的抗靜電溶液是含有水作 邛為溶劑的水性 16 201006873 塗覆办液。可添加適宜的有機溶劑至抗靜電溶液，以増進 塗覆/谷液之塗佈特性與透明度，只要該溶劑不會損害本發 明的效果即可β 有機溶劑的較佳例子包括有異丙基醇、丁基赛路蘇、 一級丁基賽路蘇、乙基赛路蘇、丙酮、乙醇、甲醇等等。 在線上塗覆方法的情況中，當塗覆溶液含有過量有機溶劑 時’於乾燥、拉伸與熱處理製程中發生***的危險會增加。 為此’抗靜電溶液内的有機溶劑含量係較佳少於10 wt%， 曝 1佳少於5 wt%。 聚酯膜製造方法的步驟2)係包含將抗靜電溶液塗佈至 經單軸拉伸之聚酯膜的一側或兩側，以形成抗靜電層。並 無明確限定將抗靜電溶液塗佈至經單軸拉伸之膜的至少一 側的方法，但較佳為梅爾桿（meyer bar )方法、凹版方法 或類似方法。更佳地，為了增進塗佈特性或塗覆層與膜之 間的黏附性，聚酯膜的表面可藉由在塗佈抗靜電溶液之前 p 將極性引進膜表面來進行電暈放電處理。 抗靜電聚酯膜製造方法的步驟3)為再拉伸該上面形成 有抗靜電層之聚酯膜的步驟，以製造經雙軸拉伸之聚醋膜。 明確地說，聚酯膜係以垂直於單軸拉伸方向的方向被 拉伸。聚酯臈的拉伸比例係較佳為膜原始尺寸的3 〇_7 〇倍。 在步驟3)之後，聚酯膜可投至習用熱處理製程，例如 熱固定，藉此製造抗靜電聚酯膜。所製得聚酯膜的厚度係 較佳為 5-300 /im，更传為 10-250 μπι。 抗靜電聚酯膜製造方法的特徵在於經單軸拉伸之聚醋 17 201006873 膜係於抗靜電層形成在該聚酯膜上之後再次被拉伸，所以 不需進行習用離線塗覆製程即可獲得所欲特性，藉此，根 據減少製程步驟製得具價格競爭性之抗靜電聚酯膜。 在另一態樣中’本發明係提供一種根據該方法製造的 抗靜電聚酯膜，該抗靜電聚酯膜係包含藉由將抗靜電溶液 塗佈至聚酯膜的一側或兩側所形成的抗靜電層，該抗靜電 溶液係包含導電聚合物樹脂以及以100重量份導電聚合物 樹脂為基準之100_1000重量份聚胺基甲酸酯樹脂、 100-1000重量份交聯樹脂、及30_30〇重量份氟樹脂。 ◎ 本發明之抗靜電聚酯膜係具有在該聚酯膜製造過程期 間以線上方式形成的抗靜電層，因為減少製程步驟，於是 具有價格競爭性。此外，該抗靜電聚酯膜係具有絕佳的抗 靜電特性，同時展現在黏性膠帶黏附性、墨水黏附性、及 防污性能方面之改良。於是，本發明之抗靜電聚酯膜係用 作為用於光學應用之絕佳抗靜電聚酯膜。 本發明之抗靜電聚酯膜係具有少於l〇1G Ω/sq之表面 電阻率’於是展現絕佳的抗靜電特性。 ◎ 再者’本發明之抗靜電聚酯膜展現了絕佳的透明度與 抗靜電特性以及一同時—具有滿足150-2000 g/in範圍之膠 帶黏附性。 根據本發明的實施例，本發明之抗靜電聚酯膜係顯現 就黏性膠帶（Nitto Denko Corp.所製造）而言之1000-1500 g/in的膠帶黏附性以及就黏性膠帶（3M Corporation所製 造）而言之200-300 g/18 mm的絕佳膠帶黏附性。 18 201006873 此外，本發明之抗靜電聚酯膜係顯現大於9〇。之水接觸 角’而因此展現絕佳的墨水黏附性及防污特性。 在本發明中，聚酯膜係藉由使用具有最佳化組成與含 量之抗靜電溶液獲仟抗靜電特性。該抗靜電溶液係使用導 電聚合物樹脂達到絕佳的抗靜電特性並藉由使用聚胺基甲 酸酯樹脂增進黏性膠帶與膜之間的黏附性和墨水與膜之間 的黏附性以及一同時一藉由使用適宜交聯樹脂調整抗靜電 層的交聯密度來增進抗靜電層的耐溶劑性與膜性能。此 ® 外’氟樹脂係添加至抗靜電溶液，以增進該膜的防污性能 以及附著至具有低剝離強度之膠帶的黏附性，於是提供用 於光學應用之絕佳抗靜電聚酯膜。 更明確地說，該抗靜電溶液的特徵係在於含有導電聚 合物樹脂以及以100重量份導電聚合物樹脂為基準之 100-1000重量份聚胺基甲酸酯樹脂、1〇〇_1〇〇〇重量份交聯 樹月曰及30-300重量份乱樹脂’而且，含有以1〇〇重量份抗 靜電溶液為基準之0.01-1重量份含氟界面活性劑，以更進 Θ —步增進塗覆溶液的防污與濕潤特性。 在此將省略抗靜電溶液的詳細說明，因為本發明之抗 靜電聚醋膜係根據上述製造方法製造且抗靜電溶液之組成 與含量係和以上製造方法中所說明者相同。 如上所述，本發明可提供用於光學應用之絕佳抗靜電 膜’該抗靜電膜具有絕佳的抗靜電特性，同時展現在黏性 膠帶黏附性、墨水黏附性及防污性能方面之改良。本發明 之抗靜電聚6曰膜係應用至顯不農置，包括了 lcd、pdp、pda 19 201006873 及導航系統，於是可有利地用作為用於顯示裝置之表面保 護膜。 此後，本發明將參照實施例更進一步詳細說明。然而， 可理解到的是該等實施例係僅供例示，本發明之範脅並不 受其限制。 實施例1 步驟1 :製造經單軸拉伸之聚酷眩 使具有固有黏度0.625 i///g並含有20 ppm具有平均粒 子直徑2_5 μιη之球狀二氧化矽粒子的聚對苯二曱酸乙二酯 丸粒於160 °C真空中充份乾燥7小時，然後使乾燥丸粒熔 融、經由T型模具擠出機擠壓並使用釘扎方法和冷卻鼓輪 緊密接觸，以製造非晶質之未經拉伸薄片。該薄片被再次 加熱並於95 °C以薄片移動方向拉伸至其原始長度的3.5 倍’依此製造經單轴拉伸之聚酯膜。然後，對欲塗覆之膜 表面進行電暈放電處理，依此製造經單轴拉伸之聚酯膜。 步驟2 :製造經螯軸拉伸之聚酯膜 在水中混合100重量份導電聚合物樹脂（Nagase Chemtex Corporation 所製造；DENATRON #5002SZ ;含有 0.5 wt%聚-3,4-乙烯二氧基噻吩與0.8 wt%聚苯乙烯磺酸的 水性分散液）以及200重量份聚胺基曱酸酯樹脂（Hepce Chem Co.，Ltd.所製造，HWU-1123A ;含有羥基的陰離子性 聚醚-聚胺基甲酸酯分散液）與200重量份三聚氰胺交聯樹 脂（Cytec Industries所製造；CYMEL385 )與作為氟樹脂的 100重量份四氟乙稀（DuPont所製造；SLA-NEW)，以製 201006873 備抗靜電溶液。以100重量份塗覆溶液為基準，將15重量 份具有分子量3000-5000之乳劑型含氟界面活性劑（DuPont 所製造；乾式膜Ra/W )加至製備的塗覆溶液。以抗靜電溶 液重量為基準，抗靜電溶液的固體含量為1.5 wt〇/〇。使用梅 爾桿將該抗靜電溶液塗佈至步驟1製得的經單軸拉伸之聚 酉曰膜。然後’所塗佈的塗覆溶液係於拉幅區以l〇5_i4〇 0C 乾燥，以垂直於膜移動方向的方向將該聚醋膜拉伸至其原 始尺寸的3.5倍並於240 °C熱處理4秒，藉此製造具有厚 β 度3 8 μιη的經雙軸拉伸之聚酯膜。 實施例2 除了藉由在水中混合100重量份導電聚合物樹脂 (Nagase Chemtex Corporation)、400 重量份聚胺基甲酸醋 樹脂（Hepce Chem Co·，Ltd.)、作為交聯樹脂的3〇〇重量I r The crosslinking resin used in the present invention is at least one compound selected from the group consisting of isononanoate, carbonyl ruthenium, oxazoline, epoxy, and melamine, and the content of the crosslinked resin is It is preferably 100-1000 parts by weight based on 1 part by weight of the conductive polymer resin. When the content of the crosslinked resin is less than 100 parts by weight, the film exhibits extremely poor antistatic properties' and the film may be whitened due to the low solvent resistance of the film. On the other hand, when the content exceeds 1 part by weight, the film exhibits good transparency but insufficient antistatic properties. p The fluororesin in the antistatic solution of the present invention is applied to a polyester film to improve the antifouling property and solvent resistance of the film. Preferred fluororesins include polytetrafluoroethylene copolymer, tetrafluoroethylene, perfluoroalkyl vinyl ether copolymer, sulphur ethylene, hexafluoropropylene copolymer, ethylene, chlorotrifluoroethylene copolymer, tetrafluoroethylene copolymer , gas trifluoroethylene, polytetrafluoroethylene copolymer, polyvinyl fluoride, polyvinylidene fluoride and the like. Preferably, polytetrafluoroethylene or a copolymer thereof is used. The antistatic solution contains 30 300 weight of fluororesin based on 100 parts by weight of the conductive polymer resin. When the content of the fluororesin is less than parts by weight, the antifouling property of the film may be lowered, and when the content of the fluororesin exceeds 3 parts by weight, the transparency and antistatic property of the film may be lowered. The antistatic solution of the present invention may further contain a surfactant to enhance the stability, wetting and leveling properties of the coating solution. Conventional surfactants include alcohols such as ethanol, isopropanol (is〇pr〇pan〇1) or isopropylalcohol; ethers such as ethyl celec (e-master cellosolve) or three Butyl butyl sulphone; ketones such as methyl ethyl ketone or acetone; and amines such as dimethylethanolamine. Preferably, an emulsion type ruthenium containing fluorosurfactant is used in the present invention. The fluorosurfactant can also be used in combination with one or more conventional surfactants. Preferably, the fluorosurfactant is added in an amount of from 0.1 part by weight to 100 parts by weight based on 100 parts by weight of the antistatic solution to enhance the antifouling and wetting characteristics of the coating solution. When the surfactant content in the antistatic solution is less than 1 part by weight, the wetting characteristics of the coating solution may be lowered. On the other hand, when the content of the surfactant is (4) by weight, the adhesiveness of the film of the coating film is lowered and the appearance of the coating film is defective due to the fine bubbles in the coating solution. The solid content of the antistatic solution of the present invention is 0.5-10.0% by weight, more preferably 1.〇_5.〇 wt〇/〇. When the solid content is less than that of 〇玉 / υ·5 wt0 / ,, the film formation characteristics and antistatic properties of the coating layer will be insufficient, and when the volume of the solids exceeds 10.0 wt%, the transparency of the film will be deteriorated. Further, the antistatic solution of the present invention is an aqueous solution containing water as a solvent. A suitable organic solvent may be added to the antistatic solution to impart coating characteristics and transparency to the coating/trough solution as long as the solvent does not impair the effects of the present invention. Preferred examples of the β organic solvent include isopropyl alcohol. , butyl 赛路苏, first-grade butyl 赛路苏, ethyl 赛路苏, acetone, ethanol, methanol and so on. In the case of the on-line coating method, when the coating solution contains an excessive amount of an organic solvent, the risk of explosion in the drying, stretching and heat treatment processes increases. For this reason, the content of the organic solvent in the antistatic solution is preferably less than 10% by weight, and preferably less than 5% by weight. The step 2) of the polyester film producing method comprises applying an antistatic solution to one side or both sides of the uniaxially stretched polyester film to form an antistatic layer. The method of applying the antistatic solution to at least one side of the uniaxially stretched film is not specifically defined, but is preferably a meyer bar method, a gravure method or the like. More preferably, in order to improve the coating property or the adhesion between the coating layer and the film, the surface of the polyester film may be subjected to a corona discharge treatment by introducing a polarity into the surface of the film before applying the antistatic solution. The step 3) of the method for producing an antistatic polyester film is a step of re-stretching the polyester film on which the antistatic layer is formed to produce a biaxially stretched polyester film. Specifically, the polyester film is stretched in a direction perpendicular to the uniaxial stretching direction. The stretch ratio of the polyester crucible is preferably 3 〇 7 7 times the original size of the film. After the step 3), the polyester film can be applied to a conventional heat treatment process such as heat setting, whereby an antistatic polyester film is produced. The thickness of the polyester film produced is preferably from 5 to 300 / im, more preferably from 10 to 250 μm. The antistatic polyester film manufacturing method is characterized in that the uniaxially stretched polyester vinegar 17 201006873 film is stretched again after the antistatic layer is formed on the polyester film, so that it is not necessary to carry out the conventional offline coating process. The desired characteristics are obtained, whereby a price competitive antistatic polyester film is produced according to the reduced process steps. In another aspect, the present invention provides an antistatic polyester film produced according to the method, which comprises coating an antistatic solution to one side or both sides of a polyester film. Forming an antistatic layer comprising a conductive polymer resin and 100-1000 parts by weight of a polyurethane resin based on 100 parts by weight of the conductive polymer resin, 100-1000 parts by weight of a crosslinked resin, and 30-30 〇 Parts by weight of fluororesin. The antistatic polyester film of the present invention has an antistatic layer formed in an in-line manner during the production process of the polyester film, and is therefore cost competitive because the process steps are reduced. In addition, the antistatic polyester film has excellent antistatic properties and exhibits improvements in adhesion of adhesive tape, ink adhesion, and antifouling properties. Thus, the antistatic polyester film of the present invention is used as an excellent antistatic polyester film for optical applications. The antistatic polyester film of the present invention has a surface resistivity of less than 10 Ω / Ω / thus exhibits excellent antistatic properties. ◎ Further, the antistatic polyester film of the present invention exhibits excellent transparency and antistatic properties as well as a simultaneous adhesive tape having a range of 150 to 2000 g/in. According to an embodiment of the present invention, the antistatic polyester film of the present invention exhibits tape adhesion of 1000-1500 g/in in terms of an adhesive tape (manufactured by Nitto Denko Corp.) and a sticky tape (3M Corporation) Excellent tape adhesion of 200-300 g/18 mm for the manufacture). 18 201006873 Furthermore, the antistatic polyester film of the present invention appears to be greater than 9 Å. The water contacts the corners and thus exhibits excellent ink adhesion and antifouling properties. In the present invention, the polyester film obtains antistatic properties by using an antistatic solution having an optimized composition and content. The antistatic solution uses a conductive polymer resin to achieve excellent antistatic properties and promotes adhesion between the adhesive tape and the film and adhesion between the ink and the film by using a polyurethane resin and At the same time, the solvent resistance and film properties of the antistatic layer are improved by adjusting the crosslinking density of the antistatic layer by using a suitable crosslinking resin. This ® outer fluororesin is added to an antistatic solution to improve the antifouling properties of the film and the adhesion to tapes with low peel strength, thus providing an excellent antistatic polyester film for optical applications. More specifically, the antistatic solution is characterized by containing a conductive polymer resin and 100-1000 parts by weight of a polyurethane resin based on 100 parts by weight of the conductive polymer resin, 1〇〇_1〇〇 〇 Weighing cross-linked tree sorghum and 30-300 parts by weight of chaotic resin' and containing 0.01-1 part by weight of fluorosurfactant based on 1 〇〇 part by weight of antistatic solution, to further improve Antifouling and wetting properties of the coating solution. Detailed description of the antistatic solution will be omitted herein because the antistatic polyester film of the present invention is produced according to the above production method and the composition and content of the antistatic solution are the same as those described in the above manufacturing method. As described above, the present invention can provide an excellent antistatic film for optical applications. The antistatic film has excellent antistatic properties and exhibits improvement in adhesion of adhesive tape, ink adhesion and antifouling properties. . The antistatic poly 6 film of the present invention is applied to the display, including lcd, pdp, pda 19 201006873 and a navigation system, and thus can be advantageously used as a surface protective film for a display device. Hereinafter, the present invention will be described in further detail with reference to the embodiments. However, it is to be understood that the embodiments are for illustrative purposes only, and the scope of the invention is not limited thereto. Example 1 Step 1: Production of uniaxially-stretched poly-terophthalic acid having an intrinsic viscosity of 0.625 i//g and containing 20 ppm of spherical cerium oxide particles having an average particle diameter of 2 to 5 μηη The ethylenediester pellets were sufficiently dried in a vacuum at 160 ° C for 7 hours, and then the dried pellets were melted, extruded through a T-die extruder, and intimately contacted with a cooling drum using a pinning method to produce an amorphous material. Unstretched sheet. The sheet was again heated and stretched at a sheet moving direction at 95 ° C to 3.5 times its original length. Thus, a uniaxially stretched polyester film was produced. Then, the surface of the film to be coated was subjected to a corona discharge treatment, whereby a uniaxially stretched polyester film was produced. Step 2: Production of a chelate-stretched polyester film in which 100 parts by weight of a conductive polymer resin (manufactured by Nagase Chemtex Corporation; DENATRON #5002SZ; containing 0.5 wt% of poly-3,4-ethylenedioxythiophene) was mixed in water. 0.8 wt% aqueous dispersion of polystyrenesulfonic acid) and 200 parts by weight of polyamino phthalate resin (manufactured by Hepce Chem Co., Ltd., HWU-1123A; anionic polyether-polyamine group containing a hydroxyl group) Formate dispersion) with 200 parts by weight of melamine crosslinked resin (manufactured by Cytec Industries; CYMEL385) and 100 parts by weight of tetrafluoroethylene (manufactured by DuPont; SLA-NEW) as a fluororesin to prepare antistatic for 201006873 Solution. 15 parts by weight of an emulsion type fluorine-containing surfactant (manufactured by DuPont; dry film Ra/W) having a molecular weight of 3000 to 5,000 was added to the prepared coating solution based on 100 parts by weight of the coating solution. The antistatic solution had a solids content of 1.5 wt〇/〇 based on the weight of the antistatic solution. The antistatic solution was applied to the uniaxially stretched polyfluorene film obtained in the step 1 using a meter rod. Then, the coated coating solution was dried in a tentering zone at 10 i5_i4 〇0C, and the polyester film was stretched to 3.5 times its original size in a direction perpendicular to the film moving direction and heat-treated at 240 ° C. 4 seconds, thereby producing a biaxially stretched polyester film having a thickness of β 3 8 μm. Example 2 A weight of 3 Å as a crosslinked resin was mixed by mixing 100 parts by weight of a conductive polymer resin (Nagase Chemtex Corporation), 400 parts by weight of a polyurethane urethane resin (Hepce Chem Co., Ltd.) in water.
份環氧樹脂（Nagase ChemteX Corporation ; DENACOL EX-614)以及作為氟樹脂的150重量份四氟乙烯（Dupont)Epoxy resin (Nagase ChemteX Corporation; DENACOL EX-614) and 150 parts by weight of fluororesin (Dupont)
製備具有2.0 wt%固體含量的抗靜電溶液以外，經雙轴拉伸 A 之抗靜電聚酯膜係以如同實施例1之相同方式製得。以100 重量份塗覆溶液為基準’添加15重量份具有分子量 3000-5000之乳劑型含氟界面活性劑。 比較實施例1 除了在製備抗靜電溶液期間未添加氟樹脂以外，經雙 軸拉伸之抗靜電聚酯膜係以如同實施例1之相同方式製得。 比較實施例2 除了在製備抗靜電溶液期間未添加聚胺基甲酸醋樹月旨 21 201006873 以外’經雙軸拉伸之抗靜電聚酯膜係以如同實施例1之相 同方式製得。 比較實施例3 除了在製備抗靜電溶液期間使用烯烴界面活性劑代替 含氟界面活性劑以外，經雙轴拉伸之抗靜電聚酯膜係以如 同實施例1之相同方式製得。 實施例1-2與比較實施例1_3所製得之抗靜電聚酯膜的 特性係以下列方式測量，測量結果顯示於下方表1。 1·水接觸角 聚醋膜的水接觸角係使用藉由蒸餾離子交換水所得純 水以接觸角測角儀（Kyowa Interface Science Co_，Ltd.;型 號Dropmaster 30.0 )藉由無柄滴法測量，並於不同位置測量 五次，然後平均。 2. 抗靜電特性 根據JIS K7194 ’在溫度23 °C與相對濕度50%之條件 以電阻係數計（Mitsubishi Chemical Corporation 所製造； 型號MCP-T600 )測量媒的表面電阻係數。 3. 墨水黏附性 將墨水（Shachihata Inc.所製造）輕輕印到膜的塗覆表 面上並乾燥1为鐘，然後將赛藤凡（cell〇phane )勝帶 CRCT-18 ( Nichiban Co·，Ltd.所製造）附著至表面。以2公 斤輥筒壓過膜的塗覆表面一次，以按壓該膜。隨後，使該 膜靜置2分鐘，然後用剝離測試機以丨8〇度剝離角與0.5 m/min之剝離速度將膠帶剝離。 201006873 ο ·印在塗覆表面上的墨水未被剝離且未轉至赛路凡膠 帶；以及 X.印在塗覆表面上的墨水被剝離並轉至賽路凡膠帶。 4. 耐乙醇性 以乙醇弄濕布料（BEMCOT，Asahi Kasei Fibers Corporation所製造）’然後使i〇 kg荷重通過膜的塗覆表 面10次。然後’以下列標準為基準評估膜的塗覆表面： 〇:抗靜電特性的變化少於101;An antistatic polyester film which was biaxially stretched A was prepared in the same manner as in Example 1 except that an antistatic solution having a solid content of 2.0 wt% was prepared. 15 parts by weight of an emulsion type fluorine-containing surfactant having a molecular weight of 3000 to 5000 was added on the basis of 100 parts by weight of the coating solution. Comparative Example 1 A biaxially stretched antistatic polyester film was obtained in the same manner as in Example 1 except that no fluororesin was added during the preparation of the antistatic solution. Comparative Example 2 An antistatic polyester film which was biaxially stretched was prepared in the same manner as in Example 1 except that no polyurethane hydrate was added during the preparation of the antistatic solution. Comparative Example 3 A biaxially stretched antistatic polyester film was obtained in the same manner as in Example 1 except that an olefin surfactant was used instead of the fluorine-containing surfactant during the preparation of the antistatic solution. The characteristics of the antistatic polyester film obtained in Example 1-2 and Comparative Example 1-3 were measured in the following manner, and the measurement results are shown in Table 1 below. 1. Water Contact Angle The water contact angle of the polyacetal film is measured by a handleless goniometer using a pure water obtained by distilling ion-exchanged water by a contact angle goniometer (Kyowa Interface Science Co., Ltd.; model Dropmaster 30.0). And measured five times at different locations and then averaged. 2. Antistatic property The surface resistivity of the medium was measured in accordance with JIS K7194' under the conditions of a temperature of 23 ° C and a relative humidity of 50% in terms of a resistivity (manufactured by Mitsubishi Chemical Corporation; model: MCP-T600). 3. Ink Adhesion The ink (manufactured by Shachihata Inc.) was lightly printed on the coated surface of the film and dried for 1 hour, and then cell 〇 e (cell 〇 e 胜 CRC CRC CRC CRC CRC CRC CRC CRC CRC CRC CRC CRC CRC CRC CRC CRC CRC CRC CRC CRC CRC CRC CRC CRC CRC Ltd. manufactured by Ltd.) attached to the surface. The coated surface of the film was pressed once with a 2 kg roller to press the film. Subsequently, the film was allowed to stand for 2 minutes, and then the tape was peeled off by a peeling tester at a peeling angle of 丨8 〇 and a peeling speed of 0.5 m/min. 201006873 ο · The ink printed on the coated surface was not peeled off and was not transferred to the racetrack tape; and X. The ink printed on the coated surface was peeled off and transferred to the Sai Lufan tape. 4. Ethanol resistance The cloth was wetted with ethanol (BEMCOT, manufactured by Asahi Kasei Fibers Corporation)' and then the i〇 kg load was passed through the coated surface of the film 10 times. Then, the coated surface of the film was evaluated based on the following criteria: 〇: the change in antistatic properties was less than 101;
A Δ .抗靜電特性的變化介於1〇ι至1〇ιι之間；以及 X ··抗靜電特性的變化超過1 〇11。 5. 膠帶黏附性_ 1 使用Chemlnstruments黏附/釋放測試機AR1000於大氣 溫度23 ± 3 0C與相對濕度50 ± 5%將一黏性膠帶（Nitto Denko Co_，Ltd.所製造；膠帶編號31B ;寬度：25 mm)黏 附至膜之塗覆膜。然後，以具有荷重2 kg的橡膠輥筒壓過 藝膜的塗覆表面一次，以按壓表面，使該膜靜置丨小時。然 後’以180度角及ο」m/min之剝離速度將膠帶剝除，並測 量剝離強度。 6. 膠帶黏附性_2 使用Chemlnstruments黏附/釋放測試機AR1 〇〇〇於大氣 溫度23 ± 3 0C與相對濕度5〇 ± 5%將一黏性膠帶（3M Corp. 所製造，膠帶編號244 ;寬度：18 mm)黏附至膜的塗覆表 面。然後’以具有荷重2 kg的橡膠輥筒壓過膜的塗覆表面 一次’以按壓表面，使該膜靜置1小時。然後，以丨8〇度 23 201006873 角及0.3 m/min之剝離速度將膠帶剝除，並測量剝離強度。 [表1] 特性 實施例1 實施例2 比較 比較 比較 實施例1 實施例2 實施例3 表面電阻係數（Ω/sq) 6xl06 2xl〇7 3χ106 2χ106 5χ106 水接觸角（°) 100 107 68 110 97 墨水黏附性 0 0 0 X 〇 耐乙醇性 0 0 0 0 〇 穋帶黏附性-1 (g/in) 1120 1315 1432 87 736 膠帶黏附性-2 (g/18mm) 228 213 239 32 55 從上方表1可看到，不含氟樹脂的比較實施例顯現相 當低的水接觸角，不含聚胺基甲酸酯樹脂的比較實施例2 由於膠帶黏附性極低所致並未顯現所欲特性，而不含有含 氟界面活性劑的比較實施例3則由於3 M膠帶之剝離強度極 低所致，產業利用性低且未顯現所欲特性。 然而，在實施例1與2中使用含有導電聚合物樹脂、 聚胺基曱酸酯樹脂、交聯樹脂、氟樹脂及含氟界面活性劑 之抗靜電溶液所製得的抗靜電聚酯膜係具有絕佳防水性與 耐溶劑性以及絕佳的抗靜電特性，顯現少於丨χ ι〇9 Ω/平 方之表面電阻係數、大於95。之高水接觸角、大於i〇〇〇 g/in 之附著至Nitto Denk0黏性膠帶的黏附性及大於2〇〇 g/i8 mm之3M膠帶剝離強度，藉此增進墨水黏附性、防污性能 與耐溶劑性。 如上所述，首先’本發明具有降低製造成本的效用， 24 201006873 因為技*靜電層係形成在經單轴拉伸之聚酯膜上，然後該上 面形成有抗靜電層之膜被再次拉伸。此外，藉由將含有導 電聚合物樹脂、聚胺基f酸酯黏合劑樹脂及氟化物防污樹 月曰的抗靜電溶液塗佈至抗靜電層，抗靜電聚酯膜獲得絕佳 的抗靜電特性，同時展現在黏性膠帶黏附性、墨水黏附性 及防污性能方面之改良。A Δ. The change in antistatic properties is between 1〇ι and 1〇ι; and the change in X··antistatic properties exceeds 1〇11. 5. Adhesiveness of the tape _ 1 Using a Chemlnstruments adhesion/release tester AR1000 at a temperature of 23 ± 30 °C and a relative humidity of 50 ± 5%, a sticky tape (manufactured by Nitto Denko Co., Ltd.; tape number 31B; width: 25 mm) A film adhered to the film. Then, the coated surface of the film was pressed once with a rubber roller having a load of 2 kg to press the surface to allow the film to stand for an hour. Then, the tape was peeled off at a peeling speed of 180 degrees and ο"m/min, and the peel strength was measured. 6. Adhesiveness of the tape _2 Using the Chemlnstruments Adhesive/Release Tester AR1 at a temperature of 23 ± 30 °C and a relative humidity of 5 〇 ± 5% will be a sticky tape (manufactured by 3M Corp., tape number 244; width) : 18 mm) Adhesive to the coated surface of the film. Then, the coated surface of the film was pressed once with a rubber roller having a load of 2 kg to press the surface, and the film was allowed to stand for 1 hour. Then, the tape was peeled off at a peeling speed of 丨8 23 23 201006873 and a peeling speed of 0.3 m/min, and the peel strength was measured. [Table 1] Characteristic Example 1 Example 2 Comparative comparison Comparative Example 1 Example 2 Example 3 Surface resistivity (Ω/sq) 6xl06 2xl〇7 3χ106 2χ106 5χ106 Water contact angle (°) 100 107 68 110 97 Ink Adhesion 0 0 0 X 〇 Ethanol resistance 0 0 0 0 〇穋 Adhesive-1 (g/in) 1120 1315 1432 87 736 Adhesive tape-2 (g/18mm) 228 213 239 32 55 Table 1 from above It can be seen that the comparative example of the non-fluororesin exhibits a relatively low water contact angle, and the comparative example 2 which does not contain the polyurethane resin does not exhibit the desired characteristics due to the extremely low adhesiveness of the tape. In Comparative Example 3 which did not contain a fluorine-containing surfactant, the peel strength of the 3 M tape was extremely low, and the industrial applicability was low and the desired properties were not exhibited. However, in Examples 1 and 2, an antistatic polyester film system prepared by using an antistatic solution containing a conductive polymer resin, a polyamino phthalate resin, a crosslinked resin, a fluororesin, and a fluorine-containing surfactant was used. It has excellent water resistance and solvent resistance as well as excellent antistatic properties, showing a surface resistivity of less than 丨χ 〇 〇 9 Ω/square, greater than 95. High water contact angle, adhesion of more than i〇〇〇g/in to Nitto Denk0 adhesive tape and 3M tape peel strength of more than 2〇〇g/i8 mm, thereby improving ink adhesion and antifouling performance With solvent resistance. As described above, first of all, the present invention has the effect of reducing the manufacturing cost, 24 201006873 because the electrostatic layer is formed on the uniaxially stretched polyester film, and then the film on which the antistatic layer is formed is stretched again. . In addition, the antistatic polyester film obtains excellent antistatic properties by applying an antistatic solution containing a conductive polymer resin, a polyamine-based ester adhesive resin, and a fluoride antifouling resin to the antistatic layer. Characteristics, while showing improvements in adhesion of adhesive tape, ink adhesion and antifouling properties.
再者’根據上述方法所製 佳的抗靜電特性以及在黏性膠 污性能方面之改良，於是可用 面保護臈。 造的抗靜電聚酯膜係展現絕 帶黏附性、墨水黏附性及防 作為用於顯示裝置之絕佳表 雖然已例示說明本發明 者將能理解在不逸離隨附申 疇與精神的同時，各種修傅 【圖式簡單說明】 =較佳具體實例，但熟習此藝 月專利範圍所揭示之本發明範 、添加與置換是可行的。 無Further, according to the above-mentioned method, the antistatic property and the improvement in the viscous adhesive property are improved, so that the surface can be protected. The antistatic polyester film system exhibits excellent adhesion, ink adhesion and prevention as an excellent watch for display devices. Although it has been exemplified, the inventors will understand that while not escaping the accompanying domain and spirit Various repairs [simplified description of the drawings] = preferred specific examples, but the invention, addition and replacement disclosed in the patent scope of this art are feasible. no
【主要元件符號說明】 無 25[Main component symbol description] None 25