13.59166 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雖膜之製造方法，係於聚醋膜 之早面或兩面所形成之防靜電層添加敗樹脂及丙烯酸樹脂 ，透明性與防靜電性優異'i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、 貪訊通訊領域及一般生活用品之廣泛領域中，因靜電產生 所致之哭害正增加中，該等機器及產業現場之防靜電成為 j重要之課題。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，為了防靜電，只要於製品表面形成使 所累積之電荷放電之防靜電層。特別是，於附著有雜質或 塵埃之薄膜之製造步驟、與力0卫薄膜之步驟巾會產生放 電，而若於該等步驟使用有機溶劑，則會產生著火的危險。 再者，當將該種薄膜作為電氣、電子零件等之材料使用的 情況下，會成為導致靜電損傷的原因，故於該等薄膜之使 用方面’附予防靜電性能成為必需要件。 上述之防靜電技術有：使用有機續酸及有機填酸醋那 樣的陰離子化合物之内部添加法、蒸鍍金屬化合物之方 塗佈導電性無機粒子之方法、塗佈低分子型陰離子性 或陽離子性化合物之方法、塗佈導電性高分子之方法等。 5 13.59166 ^述使用有機磺酸及有機磷酸酯那樣的陰離子化合物 之内部添加法，雖具有費用廉價、隨時間變化及安全:優 異之優點，但會損害薄膜支持體之固有特性、防靜電效果 有限、因輝散現象(blooming)使薄膜與積層間 低，是其問題。 牧f注降 f鍍金屬化合物之方法’防靜電性優異，最近廣泛使 用於¥電性膜，但由於製造費用非常高故僅使用於特定用 途0 而使用低分子型陰離子性或陽離子性化合物 法’防靜電效果較良好，於製造費用方面上亦有利，故可 :用於廣範圍，但由於防靜電效果有限，故無法得到1〇9 /叫以下之表面電阻，由於係與大氣中之水分 現防靜電特性，故於大氣中之水氣含量低的情況下，= 幅，低’溶劑抵抗性非常差，且有轉移至其他面的 〇此 疋其缺點，故其之使用大幅地受到限制。 目前係開發有溶解於水及有機溶劑之聚苯胺、聚 或聚°塞吩等導電性萬八； 電聚醋膜或其他高二m將其賦予導電性至防靜 门刀子表面之應用研究正熱烈進行中。 其中’-般之方法’係做出完成摻雜之導電性高分子 =法將其以適當之溶劑塗佈於含聚酯之各種高分子表面之 此時使其與適當之點結劑一同溶解以 接著力或表面硬度等之機械性^ ㈣層之 其之—例，於美國專利第4959430號，揭示導電性高 6 1359166 分子單體之一種即3,4-乙烯二氧噻吩（3 4_ ethylenedioxythiophene)與氧化劑即對甲苯磺酸（Ir〇n (ΙΠ) P-t〇iuenesuif〇nate)及與該等合成之導電性高分子即3 4聚 乙烯二氧噻吩（3,4-polyethylenedioxythiophene)，具體而 &，係將3，4-乙烯二氧噻吩與對甲苯磺酸以常溫混合後加 熱，製造成藍色之導電性高分子3，4_聚乙烯二氧嘆吩。 合成之3,4-聚乙烯二氧噻吩係以分散於水的形態市 售，但若將3,4-乙烯二氧噻吩與對甲苯磺酸混合而於常溫 放置長時間，則會產生聚合反應，故混合少量反應抑制劑 即°米°坐（imidazole)來防止之。 於日本特開平1-313521號提出一種導電性高分子，係 將3,4-一烷氧噻吩於聚陰離子存在下氧化聚合可製得聚 (3,4-一烷氧噻吩）與聚陰離子所構成之導電性聚合物，其具 有高導電性、高化學安全性及膜形成時之塗膜具有高透明 性。然而，當將含有如此之導電性高分子之塗佈液塗佈於 塑膠基材的情形時，無法簡單地得到可同時滿足對基材之 岔s J·生透明性、耐水性、耐溶劑性及導電性之所有性能 的塗膜。特別是為了提昇塗膜之耐水性而嘗試著將結合劑 樹脂以交聯劑交聯鍵結之方法等。 於曰本特開平6-73271號，基於提昇聚（3,4_二烷氧噻 % 聚陰離子所構成之導電性聚合物層和鄰接層之密合性 之目的，而使用具有環氧基之烷氧矽烷化合物，但難以賦 予塗膜耐水性。 上述之使用各種防靜電形式之防靜電製品方面，最近， 7 隨著包含LCD、PDP市場之IT事業的成長，防靜電膜之 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 月b但要製造於在線塗佈（in-line coating)時同時實現該兩 $能之薄膜係困難。又，視製品的用it，當將保護薄膜於 最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 濩膜無法良好地剝離、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 2優異光學用防靜電聚賴之製造方法，其係使用導電性 问刀子以實現優異之防靜電性能，使用丙烯酸樹脂以提昇 =帶之釗離力，同時使用適當之交聯劑調節交聯密度並提 汁耐冷劑性與塗膜性能，並添加氟樹脂以提昇防污功能。 用以達成上4目的之本發明防靜電聚醋膜之製 係包含： 將t 8曰基材膜做单轴拉伸之階段. 製造含有導電性高分子樹脂、丙稀酸樹脂、交聯劑及 氟樹脂之防靜電塗佈液之階段； 8 1359166 於該經單軸拉伸之聚酯膜的單面或兩面塗佈該塗佈液 以形成防靜電層之階段； 及將形成有該防靜電層之聚酯基材膜進行雙軸拉伸之 階段。 該防靜電層，較佳為，對於導電性高分子樹脂丨〇〇重 量份由丙稀酸樹脂200〜1000重量份、交聯劑2004 〇〇〇重 量份、及氟樹脂30〜300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 _之水分散體或聚陰離子與聚嗟吩衍生物之水分散體聚合來 製造，該丙烯酸樹脂，較佳為水分散乳膠形式，係丙烯酸 烷基酯與甲基丙烯酸烷基酯所共聚合之樹脂。 該交聯劑，較佳為，使用選自異氰酸酯系、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i 種以上之化合物。 該氟樹脂，較佳為’使用四氟乙烯系樹脂。 • 本發明之防靜電聚酯膜，保有優異之防靜電功能且即 使將混合有適當量之具有防污功能之氟樹脂與丙烯酸樹脂 之防靜電塗佈組成物塗佈於聚酯膜，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 者可明白亦可於本發明之技術思想的範圍内進行各種變形 及修正’並理解該等變形及修正亦屬於所附之申請專利之 範圍。 9 1359166 【實施方式】 以下，更詳細地說明本發明。 本發明之防靜電聚酯膜之製造方法，係包含： 將聚醋基材膜做單轴拉伸之階段； 製造含有導電性高分子樹脂、丙烯酸樹脂、交聯劑及 氟樹脂之防靜電塗佈液之階段；13.59166 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing an antistatic polyester film. More specifically, it relates to a method for producing an antistatic coating film, which is applied to a polyester film. The antistatic layer formed on the early or both sides is added with a resin and an acrylic resin, and has excellent transparency and antistatic properties. It improves the tape peeling resistance and antifouling performance and has an excellent function. [Prior Art] In recent years, with the progress of industrialization, the crying caused by static electricity is increasing in various fields of electronic and electrical equipment, the field of greedy communication, and general household goods. These machines and industrial sites Anti-static has become an important issue for j. The term "antistatic" is to discharge electricity accumulated on the surface of the insulator by an appropriate method. To prevent static electricity, an antistatic layer for discharging the accumulated electric charge is formed on the surface of the product. In particular, the production steps of the film to which the foreign matter or the dust adheres, and the step of the film with the force of the film are generated, and if the organic solvent is used in the steps, there is a risk of fire. Further, when such a film is used as a material such as an electric or electronic component, it causes a cause of electrostatic damage, and therefore, it is necessary to attach an antistatic property to the use of the film. The above antistatic technique includes an internal addition method using an anionic compound such as an organic acid-reserving or an organic acid-filled vinegar, a method of coating a conductive inorganic particle by vapor deposition of a metal compound, and coating a low molecular anionic or cationic substance. A method of a compound, a method of coating a conductive polymer, and the like. 5 13.59166 The internal addition method using an anionic compound such as an organic sulfonic acid or an organic phosphate ester has the advantages of being inexpensive, changing with time, and being safe: excellent in that it impairs the inherent characteristics of the film support and has an antistatic effect. The problem is that the film and the laminate are low due to blooming. The method of immigrating f metallization compounds is excellent in antistatic property. Recently, it has been widely used in electric films. However, since it is very expensive to manufacture, it is only used for specific applications and uses low molecular anionic or cationic compounds. 'The anti-static effect is good, and it is also advantageous in terms of manufacturing cost. Therefore, it can be used for a wide range. However, due to the limited anti-static effect, it is impossible to obtain the surface resistance of 1〇9 / below, due to the moisture in the atmosphere. Now it has anti-static properties, so when the moisture content in the atmosphere is low, the width, low 'solvent resistance is very poor, and there are some disadvantages of transferring to other surfaces, so its use is greatly limited. . At present, the development of polyaniline, poly or poly(ephedrine) dissolved in water and organic solvents is extremely conductive; the application of electropolymerized vinegar film or other high-m2 to impart conductivity to the surface of anti-static knives is enthusiastic. processing. The 'general method' is to make a doped conductive polymer = method to apply it to a surface of various polyester-containing polymers in a suitable solvent, and dissolve it together with a suitable spotting agent. For example, in the mechanical (4) layer of the adhesive force or surface hardness, for example, U.S. Patent No. 4,594,430 discloses a highly conductive 6 1359166 molecular monomer, 3,4-ethylenedioxythiophene (3 4 - ethylenedioxythiophene). And the oxidizing agent, p-toluenesulfonic acid (Ir〇n (ΙΠ) Pt〇iuenesuif〇nate) and the synthetic conductive polymer, 3,4-polyethylenedioxythiophene, specifically & The mixture was heated at room temperature with 3,4-ethylenedioxythiophene and p-toluenesulfonic acid to produce a blue conductive polymer 3,4_polyethylenedioxan. The synthesized 3,4-polyethylenedioxythiophene is commercially available in the form of being dispersed in water, but if 3,4-ethylenedioxythiophene is mixed with p-toluenesulfonic acid and left at room temperature for a long period of time, polymerization occurs. Therefore, a small amount of reaction inhibitor, ie, imidazole, is mixed to prevent it. A conductive polymer is proposed in Japanese Patent Laid-Open No. 1-313521, which is obtained by oxidative polymerization of 3,4-alkoxythiophene in the presence of a polyanion to produce poly(3,4-alkoxythiophene) and polyanion. The conductive polymer is composed of high conductivity, high chemical safety, and high transparency of the coating film at the time of film formation. However, when a coating liquid containing such a conductive polymer is applied to a plastic substrate, it is not easy to obtain a transparency, water resistance, and solvent resistance which can simultaneously satisfy the substrate. And coatings of all properties of conductivity. In particular, in order to improve the water resistance of the coating film, a method of crosslinking and bonding a binder resin with a crosslinking agent has been attempted. U.S. Patent No. 6-73271, based on the purpose of enhancing the adhesion of a conductive polymer layer composed of a poly(3,4-dioxane thiophene polyanion and an adjacent layer, using an epoxy group. Alkoxysilane compound, but it is difficult to impart water resistance to the coating film. In the above-mentioned antistatic products of various antistatic forms, recently, 7 With the growth of the IT business including the LCD and PDP markets, the demand for antistatic films has rapidly increased. The antistatic film mainly used in this application is the most widely known cationic antistatic form, and the film using conductive polymer also enters the market as a high-grade film. ^The final condition requires excellent antistatic properties and antifouling properties. It is difficult to realize the two-capacity film at the same time as in the case of in-line coating. Also, depending on the product, when the protective film is peeled off in the last step, The mechanical automatic method is applied to the tape and peeled off. However, if the adhesive force between the tape and the antistatic surface is low, the protective film may not be peeled off well, or the product may be affected during the peeling. The present invention is directed to a method for solving the above problems, and an object of the invention is to provide a method for producing an excellent antistatic coating for optical use, which uses conductive Scratch the knife to achieve excellent anti-static properties, use acrylic resin to improve the belt release force, and at the same time use appropriate cross-linking agent to adjust the cross-linking density and improve the cold resistance and film properties, and add fluororesin to The anti-staining function of the present invention for achieving the above four purposes includes: a step of uniaxially stretching a t 8 曰 base film. Manufactured with a conductive polymer resin, acrylic acid a stage of an antistatic coating liquid of a resin, a crosslinking agent, and a fluororesin; 8 1359166 a stage of applying the coating liquid on one side or both sides of the uniaxially stretched polyester film to form an antistatic layer; The polyester substrate film on which the antistatic layer is formed is subjected to biaxial stretching. The antistatic layer preferably has a weight of 200 to 1000 by weight of the acrylic resin for the conductive polymer resin. Parts, cross-linking agent 2004 The conductive polymer resin preferably has a water dispersion of a polyanion and an aqueous dispersion of a polythiophene or a polyanion and a polyphenanthene derivative, and is preferably composed of 30 parts by weight to 300 parts by weight of the fluororesin. The acrylic resin, preferably in the form of a water-dispersible latex, is a resin copolymerized with an alkyl acrylate and an alkyl methacrylate. The crosslinking agent is preferably selected from the group consisting of isocyanates. Any one or more of the group consisting of a carbonyl quinone imine, an oxazoline type, an epoxy type, and a melamine type. The fluororesin is preferably a 'tetrafluoroethylene type resin. The polyester film retains an excellent antistatic function and even applies an antistatic coating composition of a fluororesin and an acrylic resin mixed with an appropriate amount of antifouling function to the polyester film, and is washed with water or ethanol. The antistatic agent of the antistatic layer does not detach or dissolve. It also has excellent anti-fouling properties and improves adhesion to adhesive tape. The present invention will be described with reference to the specific embodiments, but those skilled in the art can understand that various modifications and changes can be made within the scope of the technical idea of the present invention. The scope. 9 1359166 [Embodiment] Hereinafter, the present invention will be described in more detail. The method for producing an antistatic polyester film of the present invention comprises: a step of uniaxially stretching a polyester substrate film; and manufacturing an antistatic coating containing a conductive polymer resin, an acrylic resin, a crosslinking agent, and a fluororesin Stage of cloth liquid;
於該經單轴拉伸之聚酯基材膜的單面或兩面塗佈該塗 佈液以形成防靜電層之階段； 及將形成有該防靜電層之聚酯基材膜進行雙軸拉伸之 階段。 通常，將於雙轴拉伸所得之聚酯膜之單面進行塗佈者 稱為離線塗佈（off-line coating)，如上述之聚酯膜之製造過 程’亦即於單軸拉伸與雙軸拉伸步驟之間施行塗佈者稱為 在線塗佈。 Λ 在線塗佈的優點在於，可於聚酯膜之製造過程中確保 離線塗佈步驟所得之塗佈物性，藉此，沒有追加之塗佈步 驟所產生之製造費料負擔，故可確保具競爭力之製品。 首先，說明將聚酯基材膜做單軸拉伸之階段。 本發明所使用之聚醋膜，其種類並無限制，可使用既 子之已知作為防靜電塗佈之基材膜者。 酸丁 ΓΓί明’，係以聚對苯二甲酸乙二醇自旨、聚對苯二^ 明，伸本:曰、“二f酸乙二醇醋等聚酯系樹脂為中心說 仁本發明之聚酯膜，並不限定於此。 135.9166Coating the coating liquid on one side or both sides of the uniaxially stretched polyester base film to form an antistatic layer; and biaxially drawing the polyester base film on which the antistatic layer is formed Stretching stage. Generally, the coating of one side of the polyester film obtained by biaxial stretching is called off-line coating, and the manufacturing process of the above-mentioned polyester film is also uniaxially stretched. The application of the coating between the biaxial stretching steps is referred to as in-line coating. Λ The advantage of on-line coating is that the coating properties obtained in the off-line coating step can be ensured during the production process of the polyester film, thereby ensuring competition without the manufacturing cost burden caused by the additional coating step. Product of force. First, the stage in which the polyester base film is uniaxially stretched will be described. The type of the polyester film used in the present invention is not limited, and those known as the substrate film for antistatic coating can be used. Acid butyl ΓΓ 明 , 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 The polyester film is not limited thereto. 135.9166
縮聚所得之聚酯。芳香族二羧酸，可舉例如對苯二曱酸 2,6-萘二羧酸等；脂肪族二醇，可舉例如乙二醇、二 醇等。聚酯之代表，有聚對苯二曱酸 2,6-萘二羧酸乙二醇酯（ΡΕΝ)等。該聚 醇、1，4-環己烷二甲醇等 乙二醇酯（PET)、聚2 6· 醋’亦可使用含有第3成分之共聚物。 該共聚合聚酯之二羧酸成分，可舉例如間苯二甲酸、 鄰苯二甲酸、對笨二甲酸、2,6_萘二羧酸、己二酸、癸二 #酸、羥羧酸（例如，對羥基苯甲酸等二醇成分，可舉例The resulting polyester is polycondensed. The aromatic dicarboxylic acid may, for example, be terephthalic acid 2,6-naphthalene dicarboxylic acid or the like; and the aliphatic diol may, for example, be ethylene glycol or diol. Representative of the polyester are poly(p-phenylene terephthalate) ethylene glycol 2,6-naphthalene dicarboxylate (oxime) and the like. A copolymer containing the third component may be used as the polyethylene glycol, PET or 1,4-cyclohexanedimethanol or the like. The dicarboxylic acid component of the copolymerized polyester may, for example, be isophthalic acid, phthalic acid, p-dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, hydrazine acid, or hydroxycarboxylic acid. (For example, a diol component such as p-hydroxybenzoic acid can be exemplified
丁二醇、1，4-環己院二甲 醇、新戊二醇等。該等二羧酸成分及二醇成分，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炫融， 以Τ模具（Τ-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 加熱至聚醋樹脂之玻璃轉移溫度以上之輥，藉輥與觀間之 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’說明製造防靜電塗佈液之階段。 本發明之防靜電塗佈液’係塗佈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 性咼分子樹脂、丙烯酸樹脂、交聯劑、氟樹脂與溶劑，更 詳而言之’係相對於導電性高分子樹脂1〇〇重量份由丙婦 酸樹脂200〜1〇〇〇重量份、交聯劑2〇〇〜1〇〇〇重量份、及氟 1359166 樹脂30〜300重量份所構成β 具體而言，該防靜電塗佈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 散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 嶒酸、聚乙烯磺酸等。高分子羧酸，有聚丙烯酸、聚甲基 丙烯酸、聚馬來酸等，高分子磺酸，有聚苯乙烯磺酸等。 相對於聚噻吩或聚噻吩衍生物，由導電性之觀點，聚 陰離子以固體成分重量％過剩地存在為佳，相對於聚噻吩 或聚。塞吩衍生物1重量％，聚陰離子以1重量％〜5重量％ 為佳。更佳為，1重量％〜3重量0/〇。 另一方面，於本發明’係使用含有聚，4_乙烯二氧噻 力）〇·5重里/0與聚本乙稀績酸（分子量Μη = 150000)0.8重 量％之聚合物之水分散體。 接著，說明丙稀酸樹脂。 本發明所使用之丙烯酸樹脂，係塗佈於聚酯膜，其之 添加係用以提昇與上述膜之密合力，且將膠帶自偏光板剝 離時增大膠帶剝離力》 丙稀酸乳膠之製造與製品，通常係由丙烯酸乙酯、丙 烯酸丁酯、甲基丙烯酸、甲基丙烯酸曱酯 '丙烯酸2_丁基 己酯等成分中，上述2成分以上之共聚合形態構成來製造， 較佳為，使用將丙烯酸烷基酯與曱基丙烯酸烷基酯共聚合 之樹脂。 另一方面，所添加之丙烯酸樹脂之量，係相對於導電 12 1359166 性高分子樹脂100重量份添加丙烯酸樹脂200〜1〇 量 份。若丙烯酸樹脂之添加量未滿200重量份，則膠帶韌士 力降低，而難以發揮其功能，若超過！000重量份，則雖 可充分地確保膠帶剝離力但會產生防靜電性能降低之 題。 接著，說明交聯劑。 本發明所使用之交聯劑，係用以提昇防靜電層與聚酉旨 膜之耐溶劑性及塗膜性能，較佳為使用選自異氰酸酯系、 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。 另一方面，所添加之交聯劑之量，係相對於導電性高 分子樹脂100重量份添加交聯劑樹脂1004 〇〇〇重量份。 若交聯劑樹脂之添加量未滿100重量份，則會有防靜電性 難以發揮之情形，此時，由於耐溶劑性弱而產生白化現象。 又，若超過1000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，係塗佈於聚酯膜，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 氣乙稀（Poly tetra fluoro ethylene)、四氟乙烯、全氟化烷 基乙烯趟共聚物（perflu〇r〇 (alkyl vinyl ether) c〇p〇lymer)、 一說乙稀，、氟丙稀共聚物（Fluorinated ethylene copolymer propylene cop〇lymer)、乙烯、四氟乙烯共聚物、氣三氟乙 稀 四氣乙稀共聚物（Ethylene tetra fluoro ethylene 13 χ359ΐ66 copolymer)、氣三氟乙烯、四氟乙烯共聚物（p〇iy fh。⑺ ethylene cop〇lymer)、聚氟乙烯（p〇ly vinyU fiu〇ride)、聚 偏二氟乙烯（Poly vinylidene flU0ride)等，較佳為使用四氟 乙烯。 另一方面，所添加之氟樹脂之量，係相對於對導電性 尚分子樹脂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卯 重量份’則有膜之透明性降低、且防靜電性能亦降低 題0 上述之本發明之防靜電塗佈液，較佳係製造成相對於 整體塗佈& 1〇〇重量％，固體成分之含量為〇 5〜⑽重量 ’更佳係製造成固體成分之含量$ i 〇〜5 〇重量％。若該 固體成分之含量未％ G.5重量則塗佈層之被膜形成^ 防靜電功能發揮料充分’而若超過⑽重量％則有膜之 透明性降低之問題。 为一Butylene glycol, 1,4-cyclohexyl dimethyl alcohol, neopentyl glycol, and the like. These dicarboxylic acid components and diol components may be used in combination of two or more kinds. The polyester resin having the above composition is vacuum-dried, then smelted in an extruder, extruded into a sheet shape by a Τ-DIE, and the sheet is cooled and solidified by applying a pinning method to a cooling roll. Thereby, an unstretched polyester sheet was obtained. The uniaxially stretched polyester film was produced by subjecting the roll heated to the glass transition temperature of the polyester resin to a uniaxial stretching of 2.5 to 4.5 times by the difference between the roll and the viewing speed. 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. Specifically, it is a conductive cerium molecular resin containing a solid component, an acrylic resin, and a crosslinking agent. The fluororesin and the solvent, more specifically, are 1 part by weight of the conductive polymer resin, and the weight of the potassium acrylate resin is 200 to 1 part by weight, and the crosslinking agent is 2 〇〇 to 1 〇〇〇. In particular, the conductive polymer resin contained in the antistatic coating liquid is preferably a polyanion and a polythiophene, in order to impart antistatic properties, in terms of a part by weight and a fluorine-containing 1359166 resin. An aqueous dispersion or an aqueous dispersion of a polyanion and a polythiophene derivative. The polyanion 'acid polymer' contains a polymer carboxylic acid, a polymer citric acid, a polyvinyl sulfonic acid or the like. The polymer carboxylic acid includes polyacrylic acid, polymethacrylic acid, polymaleic acid, etc., a polymer sulfonic acid, and polystyrene sulfonic acid. The polyanion is preferably present in an excess amount of the solid content by weight of the polythiophene or the polythiophene derivative, with respect to the polythiophene or poly. The phenanthrene derivative is 1% by weight, and the polyanion is preferably 1% by weight to 5% by weight. More preferably, it is 1% by weight to 3 parts by weight. On the other hand, in the present invention, an aqueous dispersion containing a polymer containing poly(4-ethylenedioxythiol) 〇·5 zhongli/0 and a polyethylidene acid (molecular weight Μη = 150,000) of 0.8% by weight is used. . Next, the acrylic resin will be described. The acrylic resin used in the present invention is applied to a polyester film, which is added to enhance the adhesion to the film, and to increase the tape peeling force when the tape is peeled off from the polarizing plate. Manufacture of acrylic latex The product is usually produced by a copolymerization form of two or more components selected from the group consisting of ethyl acrylate, butyl acrylate, methacrylic acid, methacrylic acid methacrylate, 2-butylhexyl acrylate, and the like. A resin which copolymerizes an alkyl acrylate with an alkyl methacrylate is used. On the other hand, the amount of the acrylic resin to be added is 200 to 1 part by weight based on 100 parts by weight of the conductive 12 1359166 polymer resin. If the amount of the acrylic resin added is less than 200 parts by weight, the tape has a reduced toughness and it is difficult to exert its function. When the amount is 10,000 parts by weight, the tape peeling force can be sufficiently ensured, but the problem of lowering the antistatic property occurs. Next, the crosslinking agent will be described. The crosslinking agent used in the present invention is used for improving the solvent resistance and coating film properties of the antistatic layer and the polyimide film, and is preferably selected from the group consisting of isocyanate, carbonyl quinone, oxazoline, Any one or more compounds selected from the group consisting of epoxy and melamine. On the other hand, the amount of the crosslinking agent to be added is 100 parts by weight based on 100 parts by weight of the conductive polymer resin. When the amount of the crosslinking agent resin added is less than 100 parts by weight, the antistatic property may be difficult to be exhibited. In this case, the whitening phenomenon occurs due to weak solvent resistance. On the other hand, when it exceeds 1,000 parts by weight, the transparency is good, but there is a problem that it is difficult to prevent the antistatic property. Next, the fluororesin will be described. The fluororesin added in the present invention 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 a poly tetra fluoro ethylene. , tetrafluoroethylene, perfluoro 〇 〇 alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl ), ethylene, tetrafluoroethylene copolymer, ethylene trifluoroethylene 13 χ 359ΐ66 copolymer, gas trifluoroethylene, tetrafluoroethylene copolymer (p〇iy fh. (7) ethylene cop 〇lymer), polyvinylidene fluoride, polyvinylidene flU0ride, etc., preferably tetrafluoroethylene. On the other hand, the amount of the fluororesin to be added is 30 to 300 parts by weight based on 100 parts by weight of the conductive resin. When the amount of the fluororesin added 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 cloth liquid is preferably produced in an amount of 〇5 to (10) by weight relative to the entire coating & 1% by weight, and the content of the solid component is more preferably 5% to 5% by weight. When the content of the solid component is not less than G.5 by weight, the film formation of the coating layer is sufficient to prevent the static electricity from functioning, and if it exceeds (10)% by weight, the transparency of the film is lowered. One
方面，該防靜電塗佈液所使用之溶劑，較佳為實 X Jc為主要介質之水性塗佈液。本發明所使用之塗佈 液：於塗佈性之提昇、透明性之提昇等目的方面，亦可以 知。本發明效果的程度含有適當之有機溶劑。例如，較 :可使用異丙醇、丁基赛路蘇、三級丁基赛路蘇、乙基赛 穌 ':酮、乙醇、甲醇等 '然而，當塗佈液令含有大量 有機命劑的情況下，若使用在線塗佈法，則於乾On the other hand, the solvent used for the antistatic coating liquid is preferably an aqueous coating liquid in which X Jc is a main medium. The coating liquid used in the present invention is also known for its purpose of improving coating properties and improving transparency. The extent of the effect of the present invention contains a suitable organic solvent. For example, it is possible to use isopropanol, butyl sirlo, tributyl butyl sulphate, ethyl sucrose: ketone, ethanol, methanol, etc. 'However, when the coating liquid contains a large amount of organic agents In the case, if the online coating method is used, it is dried.
伸及熱處理步翻#女L A 會有爆炸的危險性，故其含量以為塗佈 之1 0重量％ ^ 里。Μ下為宜，5重量％以下為佳。 1359166 接著’於該單軸拉伸聚酯膜之至少一面塗佈所製造之 防靜電塗佈液以形成防靜電層。具體而言’塗佈防靜電塗 佈液之方法並無特別限制，可使用絲棒（meyer bar)方式、 照相凹板方式等，較佳為，於塗佈前將極性基導入膜的表 面，進行電暈（corona)放電處理以提昇塗佈層與膜之接著 性及塗佈性。 又，為了提昇防靜電塗佈液之安全性、濕潤性（wetting) 及塗佈時之平整（leveUng)，可混合乙醇、異丙醇 (is〇pr〇pan〇i)、異丙醇（iso_propyl alc〇h〇丨）等醇類、乙基赛 路蘇、二級丁基賽路蘇等醚類、曱乙酮、丙酮等酮類、二 曱基乙醇胺等胺類或離子性/非離子性界面活性劑之丨種以 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 垂直之方向拉伸，拉伸比以3 〇〜7 〇倍為佳。之後，藉由 熱固疋等製造防靜電聚酯膜，聚酯膜之厚度通常為5〜3⑼ y γπ、車父佳為10〜250#πι。 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300g/in以上之膠帶剝離 力，即使以溫水及乙醇擦拭表面，表面電阻亦為ixi〇llQ /叫 以下。 、·-σ果’本發明之保護膜，藉由於基材之單面或兩面塗 佈該含氟樹脂與丙烯酸樹脂之防靜電塗佈液所形成之防靜 電層，而具有撥水功能、耐乙醇性及容易去除黏著劑之性 15 丄划166 貝，且具有夥帶剝離力高之性能’故可提供能因應晝面大 型化要求之聚自旨膜。 以下，列舉實施例以更詳細說明本發明，但該等實施 例係帛μ更具體地說明本發明而例示纟，故本發明並不 限於該等實施例。 <製造例1 >聚酯膜之製造 將極限黏度為〇.625dl/g的聚對苯二曱酸乙二醇酯顆粒 (Pellet)(此聚對苯二曱酸乙二醇酯顆粒係混入有20Ppm之 平均粒仅為2.5 /z m之無定形球形氧化石夕粒子），利用真空 乾燥機以7小時160°C充分乾燥後熔融，以擠製T模具於 冷部筒以施加靜電法（pinning)使密合作成無定形未拉伸 片’將其再加熱以95°C朝膜進行方向拉伸3.5倍》之後， 對經塗佈的一面，實施電暈放電處理以製造聚酯膜。 <貫施例1 > 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，DENATRON#5002SZ ;含有聚 3,4-乙烯二氧噻吩〇·5重量％與聚苯乙烯磺酸〇·8重量。/〇之 水分散體）100重量份、丙烯酸樹脂（日本佳拜德公司RX : 7013甲基丙烯酸甲酯、丙烯酸乙酯之共聚物）4〇〇重量份、 三聚氰胺交聯劑（赛鐵克公司，CYMEL385)200重量份、四 氟乙烯（杜邦公司，SLA-NEW)100重量份、界面活性劑樹 脂（曰信化學工業公司，EXP405 1 ;乙块二醇（acetylene di〇l) 成分）2重量份混合於水製造防靜電塗佈液。此時，固體成 分之含量，係相對於整體防靜電塗佈液含2.0重量°/〇。 16 1359166 將該防靜電塗佈液使用#8絲棒塗佈於上述製造例之聚 酯膜。塗佈後，於100〜13〇。(：拉幅（tender)區間使所塗佈之 塗佈液乾燥’朝與膜之進行方向垂直之方向拉伸3 5倍並 以240°C熱處理4秒鐘，藉此，製造25//m厚之雙轴拉伸 防靜電聚酯膜。 <實施例2 > 使用導電性向分子樹脂（Nagase ChemteX公司）ι〇〇重 量份、丙烯酸樹脂（日本佳拜德公司）7〇〇重量份、環氧交 •聯劑（Nagase ChemteX公司）300重量份、氟樹脂（杜邦公 司）200重量份、界面活性劑樹脂（曰信化學工業公司重 量份’以使整體固體成分含量為4〇重量％之方式製造防 靜電塗佈液，除此之外，以與上述實施例丨相同之方法製 造雙軸拉伸防靜電聚酯膜。 <實施例3 > 將導電性高分子樹脂（Nagase chemteX公司）1〇〇重量 份、丙烯酸樹脂（日本佳拜德公司）5〇〇重量份、三聚氰胺 ^交聯劑（赛鐵克公司）2〇〇重量份、氟樹脂（杜邦公司）50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3 〇重量％之方式製造 防靜電塗佈液，除此之外，以與上述實施例丨相同之方法 製造雙軸拉伸防靜電聚酯膜。 <比較例1 > 於製造防靜電塗佈液時，不添加丙烯酸樹脂及氟樹脂， 除此之外，以與上述實施例丨相同之方法製造雙軸拉伸防 17 静電聚酯膜。 <比較例2 > 於製造防靜電塗佈液時，不添加丙烯酸樹脂，除此之 卜’以與上述實施例1相同之方法製造雙轴拉伸防靜電聚 酯犋。 <比較例3 > 於製造防靜電塗佈液時，不添加氟樹脂，除此之外，Stretching and heat treatment step #女L A There is a risk of explosion, so the content is considered to be 10% by weight of coating. The armpit is suitable, and 5 wt% or less is preferred. 1359166 Next, the produced antistatic coating liquid was 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 meyer bar method, a gravure method, or the like can be used. Preferably, a polar group is introduced into the surface of the film before coating. A corona discharge treatment is performed to improve the adhesion between the coating layer and the film and the coatability. In addition, in order to improve the safety, wettability and flatness (leveUng) of the antistatic coating liquid, ethanol, isopropanol (is〇pr〇pan〇i), isopropanol (iso_propyl) may be mixed. Alc, such as alcohols, ethyl celecoxib, secondary butyl races, ketones such as acetophenone or acetone, amines such as dimercaptoethanolamine, or ionic/nonionic More than one type of surfactant is used. Finally, the uniaxially stretched polyester film on which the antistatic layer was formed was stretched to produce a biaxially stretched polyester film. Specifically, it is stretched in a direction perpendicular to the uniaxial stretching direction, and the stretching ratio is preferably 3 〇 to 7 〇. Thereafter, an antistatic polyester film is produced by thermosetting or the like, and the thickness of the polyester film is usually 5 to 3 (9) y γπ, and the car is preferably 10 to 250 #πι. The antistatic polyester film produced by the above method was transparent and had a water contact angle of 95 with respect to the antistatic layer. Above, with a tape peeling force of 300 g/in or more, even if the surface is wiped with warm water and ethanol, the surface resistance is ixi〇llQ / call below. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Ethanol and easy to remove the adhesive 15 166 166 shells, and the performance of the strip with high peeling force', so it can provide a special film for the large-scale requirements of the surface. Hereinafter, the present invention will be described in more detail by way of examples, but these examples are more specifically illustrated by the present invention, and the present invention is not limited to the examples. <Production Example 1> Production of polyester film Polyethylene terephthalate particles (Pellet) having an ultimate viscosity of 625.625 dl/g (this polyethylene terephthalate particle system) Incorporating an amorphous spherical oxidized oxide particle having an average particle size of only 2.5/zm at 20 Ppm, and drying it by a vacuum dryer at 7 hours and 160 ° C, and then extruding it to extrude a T mold in a cold cylinder to apply an electrostatic method ( After pinning), the densely stretched unstretched sheet was reheated by 3.5 times in the direction of film stretching at 95 ° C, and then the coated side was subjected to corona discharge treatment to produce a polyester film. <Example 1 > Conductive polymer resin as a solid component on a surface subjected to corona treatment (Nagase ChemteX, DENATRON #5002SZ; containing poly 3,4-ethylenedioxythiophene·5 wt% 100 parts by weight with a polystyrene sulfonate sulfonium sulfonate / 8 parts by weight of water dispersion, acrylic resin (Japan Cobade RX: 7013 methyl methacrylate, ethyl acrylate copolymer) 4 〇〇 weight 200 parts by weight of melamine cross-linking agent (CYMEL385), 100 parts by weight of tetrafluoroethylene (DuPont, SLA-NEW), surfactant resin (Jinxin Chemical Industry Co., Ltd., EXP405 1; 2 parts by weight of an alcohol (acetylene dioxime) component was mixed with water to prepare an antistatic coating liquid. At this time, the content of the solid component was 2.0 wt%/〇 with respect to the entire antistatic coating liquid. 16 1359166 This antistatic coating liquid was applied to the polyester film of the above production example using a #8 wire bar. After coating, at 100~13〇. (: The tenter section dries the applied coating liquid by '35 times in a direction perpendicular to the direction in which the film is made and heat-treated at 240 ° C for 4 seconds, thereby producing 25//m. Thick biaxially-stretched antistatic polyester film. <Example 2> Using conductivity to a molecular resin (Nagase ChemteX) ι by weight, acrylic resin (Jiabad), 7 parts by weight, 300 parts by weight of an epoxy crosslinking agent (Nagase ChemteX Co., Ltd.), 200 parts by weight of a fluororesin (DuPont), and a surfactant resin (a weight part of the company) so that the total solid content is 4% by weight. A biaxially stretched antistatic polyester film was produced in the same manner as in the above Example except that the antistatic coating liquid was produced in the same manner. <Example 3> A conductive polymer resin (Nagase ChemteX Co., Ltd.) 1 part by weight, acrylic resin (Japan Jabate) 5 parts by weight, melamine^crosslinking agent (Symantec) 2 parts by weight, fluororesin (DuPont) 50 parts by weight, interface Active resin (曰信化学Biaxial stretching prevention was carried out in the same manner as in the above Example 制造, except that 2 parts by weight was used in combination to prepare an antistatic coating liquid so that the total solid content was 3% by weight. Electrostatic polyester film. Comparative Example 1 > Biaxial stretching prevention was carried out in the same manner as in the above Example except that the acrylic resin and the fluororesin were not added in the production of the antistatic coating liquid. Electrostatic polyester film. <Comparative Example 2 > When an antistatic coating liquid was produced, no acrylic resin was added, and in addition, a biaxially stretched antistatic polyester was produced in the same manner as in the above Example 1.比较. Comparative Example 3 > When the antistatic coating liquid is produced, no fluororesin is added, and
以與上述實施例1相同之方法製造雙軸拉伸防靜電聚黯 膜。 S <試驗例> 對實施例1〜3及比較例1〜3所製得之防靜電聚酯膜評 估如下述之物性，其結果示於表1。 1.水接觸角 使用接觸角測定器（Ky〇wa Interfaee Seienee Cl Ltd，；型號名稱Dropmaster 3〇〇)以離子交換水經蒸餾所得 之純水以液滴法（sessile drop method)測定水接觸角，在不 同位置測定5次後求出平均值。 _2.防靜雷性 防靜電性測'定機（三篸05·@ 4 、 、变（版）核式名；MCP-T600)於溫 度3 2°C、濕度50%RH之環琦下执w 4t 衣兄下0又置忒樣後，根據JIS K7194 測定表面電阻。 3 . 而f水性 分鐘後，以5(TC乾燥10 電性與外觀。 將膜放置於流動之自來水中丄 分鐘後’以如下述之方式評估防靜 18 1359166 〇：無白濁現象防靜電性無降低之情形 耐乙酵性A biaxially stretched antistatic polyfluorene film was produced in the same manner as in the above Example 1. S <Test Example> The antistatic polyester films obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were evaluated for the following physical properties, and the results are shown in Table 1. 1. Water contact angle The water contact angle was measured by a sessile drop method using a contact angle measuring device (Ky〇wa Interfaee Seienee Cl Ltd; model name Dropmaster 3〇〇) to purify the pure water obtained by ion-exchanged water. The average value was determined after measuring five times at different positions. _2. Anti-static lightning anti-static test 'setting machine (Sanhao 05·@ 4, , change (version) nuclear name; MCP-T600) at the temperature of 3 2 ° C, humidity 50% RH of the ring Qi w 4t After the brothers were placed in the same position, the surface resistance was measured according to JIS K7194. 3. After f water minute, take 5 (TC dry 10 electricity and appearance. Place the film in flowing tap water for a few minutes) to evaluate anti-static 18 1359166 as follows: No white turbidity anti-static Reduced conditions
用乙醇沾濕棉棒後，將棉棒之角度維持為45度之狀況 下’對上述經塗佈處理之薄膜面，以1N 只里、3cm/sec之 速度往返於5cm長度達10次後，以下述基準評估塗佈面 之狀態。 〇：幾乎沒有防靜電功能之變化，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、或塗佈面被磨耗之情形 k透明性Π截唐、 將取樣成lOcmxl 0cm大小之試樣1片垂直放置於濁度 測定機（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4〇〇〜7〇〇 从m波長之光穿透時之值。 此時，濁度（Haze)值，係以下述數學式！求得。 濁度（％)=(1 —（散射光之量/光之總穿透量）)χ1〇〇 i膠帶剝離力 於23°±3、相對濕度50±5%之環境氣氛下使用剝離力 測疋機即AR1000(Chem instruments公司）裝備，於上述所 得之膜之塗佈面貼附日東電工股份有限公司製膠帶N〇 3 1B(厚度：25/z m '寬度：25mm)後以2kg負重之橡膠滾 輪來回擠壓1次後，馬上以剝離速度0.3MPM進行18〇度 剝離。此時，測定所得之剝離力。 切166 【表1】 -_ 實施例1 實施例2 實施例3 比較例1 比較例2 比較例3 表面電阻Ω/sq 〜~~~--- 108 108 108 106 106 108 水接觸角（。） '--- 100 102 99 61 102 65 耐水性 〇 〇 〇 〇 〇 〇 耐乙醇性 〇 〇 〇 〇 〇 〇 透明性(Haze彡 3.3 3.2 3.5 3.2 3.3 3.4 修帶剝離力(g/in) — 465 388 587 48 61 515 由表1可知’未含丙烯酸樹脂之比較例2，由於膠帶 剝離力之值低故無法得到所欲之物性，而未含氟樹脂之比 較例3 ’由於水接觸角低故無法得到所欲之物性。 由具有含丙烯酸樹脂與氟樹脂之防靜電層之實施例 1〜3所製造之聚酯膜，可製造維持耐水性、耐溶劑性及表 面電阻為1χ1〇9 Ω /square以下之物性、且具有95。以上之 南水接觸角值與膠帶剝離力為3〇〇g/in以上之值的膜。 【圖式簡單說明】 無 【主要元件符號說明】 無 20After dampening the cotton swab with ethanol and maintaining the angle of the cotton swab at 45 degrees, the film surface of the above-mentioned coated film was transferred to a length of 5 cm at a speed of 1 N at a speed of 3 cm/sec for 10 times. The state of the coated surface was evaluated on the basis of the following criteria. 〇: There is almost no change in anti-static function, no scratches △: Anti-static function is reduced or there are some scratches X: Anti-static function disappears, or the coated surface is worn away k Transparency will be sampled One piece of a sample of 10 cm in size and 10 cm in size was placed vertically in a turbidity measuring machine (AUTOMATIC DIGITAL HAZEMETER, manufactured by Nippon Denshoku Co., Ltd.), and measured at a right angle to the vertical placement test to have a wavelength of 4 〇〇 to 7 〇〇 from the m wavelength. The value of light penetration. At this time, the turbidity (Haze) value is the following mathematical formula! Seek. Turbidity (%) = (1 - (the amount of scattered light / total penetration of light)) χ 1〇〇i tape peeling force measured at 23 ° ± 3, relative humidity 50 ± 5% ambient atmosphere using peel force The machine is equipped with AR1000 (Chem Instruments), and the rubber coated with Nitto Denko Co., Ltd. tape N〇3 1B (thickness: 25/zm 'width: 25mm) is applied to the coated surface of the film obtained above. After the roller was pressed back and forth for one time, it was immediately peeled off at a peeling speed of 0.3 MPM. At this time, the obtained peeling force was measured. Cut 166 [Table 1] -_ Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Surface resistance Ω/sq 〜~~~--- 108 108 108 106 106 108 Water contact angle (.) '--- 100 102 99 61 102 65 Water resistance, ethanol resistance, transparency (Haze彡3.3 3.2 3.5 3.2 3.3 3.4 Repair stripping force (g/in) — 465 388 587 48 61 515 It can be seen from Table 1 that in Comparative Example 2, which does not contain an acrylic resin, since the value of the tape peeling force is low, the desired physical properties cannot be obtained, and the comparative example 3 of the fluorine-free resin cannot be used because of the low water contact angle. The desired properties are obtained. The polyester film produced in Examples 1 to 3 having an antistatic layer containing an acrylic resin and a fluororesin can be manufactured to maintain water resistance, solvent resistance and surface resistance of 1 χ 1 〇 9 Ω / square. The following physical properties, and a film having a contact angle value of 95% or more and a tape peeling force of 3 〇〇g/in or more. [Simplified description of the drawing] No [Main component symbol description] No 20