200422187 (1) 玖、發明說明 【發明所屬之技術領域] 本發明係關於具有表面防污 作爲光學元件保護用之聚膜薄膜 【先前技術】 聚對苯二甲酸乙二醇酯或聚 膜薄膜，因機械性強度、尺寸穩 耐藥品性、光學特性等優異，價 各種用途之基材 其用途之一例，如作爲保護 面損傷、污染之保護膜，於聚膜 膜用，聚膜薄膜因摩擦、黏著層 爲光學元件之保護膜之用之各步 靜電、黏附異物或塵埃、妨礙靜 對於黏貼保護膜，於再剝離 手作業之步驟，保護膜表面膜易 著劑等污染，須具備耐污染性之 對表面保護膜附與防靜電性 性樹脂之方法（特開平 6- 1 23 806 面附與防靜電性，認爲有於黏著 法，於設有防靜電性樹脂層之I (特開平6-123806號公報、特開 開 200 1 -2754 1 0號公報），但包> 性及兩面防靜電性，適於 萘酸乙二醇酯爲代表之聚 定性、平坦性、耐熱性、 格性能比亦優異，被用於 偏光板等之光學元件之表 薄膜基材塗佈黏著劑之薄 剝離等時易產生靜電，作 驟，產生摩擦靜電或剝離 電放電等問題。 作業步驟、檢查步驟等用 受油脂、溢出或貼附之黏 表面特性。 ，一般於表面塗佈防靜電 號公報）。又，對黏著劑 劑層中添加防靜電劑之方 :材塗佈黏著劑之方法等 2000-8 03 3 6號公報、特 含成本、品質無法有效實 (2) (2)200422187 施。 此用以得到必備之防靜電性，須於黏著層中含大量之 防靜電成分，理由爲改變再剝離性黏著劑之塗料特性，失 去原本之性狀，或自黏著劑層之防靜電成分於黏附物經時 移動，易污染被黏附等。 另方面，總合性解決此類問題點，須於各個附於基材 聚膜薄膜不足之功能，爲此，若對各個要求進行塗佈加 工，增加用以解決各個問題之加工步驟，以致惡化價格性 鲁 能比。 本發明係鑑於上述實情，其解決課題爲以低成本提供 單面側具有防污染性，其裏面側具有再剝離性黏著性黏著 性層，且兩面皆具有防靜電性之保護膜。 【發明內容】 〔發明之揭示〕 本發明者爲鑑於上述實情，再三檢討之結果，找出具 鲁 有特定結構之薄膜爲有用之保護膜，以致完成本發明。 即’本發明之要點，光學元件表面保護膜，其特徵爲 爲以聚膜薄膜爲基材，其兩面具有樹脂層，一面之樹脂層 表面具有黏著劑之薄膜，露出之樹脂層表面之水滴接觸角 爲80度以上，表面外加10kV直流電壓時之飽和靜電兩 面皆爲2kV以下，外加停止後之飽和靜電量之半衰時間 兩面皆爲1 5秒以下。 以下，再詳細說明本發明。 (3) (3)200422187 本發明所用之聚酯，係將如芳族二羧酸與脂肪族乙二 醇縮聚所得者。芳族二羧酸舉出，對苯二甲酸、2,6-萘二 羧酸等，脂肪族乙二醇舉出，乙二醇、二乙二醇、1,4-環 己烷二甲醇等。代表性之聚酯可例示，聚對苯二甲酸乙二 醇酯（PET)、聚乙烯-2,6-萘二羧酸酯（PEN)等。 聚酯亦可爲均聚酯之共聚聚酯。爲共聚聚酯時，通常 含30莫耳％以下之第三成分之共聚物。 有關共聚聚酯之二羧酸成分，可舉出間苯二甲酸、隣 苯二甲酸、對苯二甲酸、2,6_萘二羧酸、己二酸、癸二 酸、壬二酸及 '羥酸之一種或二種以上，乙二醇成分，可 舉出乙二醇、二乙二醇、丙二醇、丁二酸、1，4-環己烷二 甲醇、新戊二醇等之一種或二種以上。 本發明所用之聚酯，可爲以熔融聚合反應製得者，或 熔融聚合後，將一度片化之聚酯固相聚合者 本發明可爲具有將異種之聚酯共擠壓積層結構之薄 膜。 本發明所用之聚酯，於無損及本發明要點之範圍，可 摻合防靜電劑。按實施需要，用以改良薄膜之滑動性或耐 摩損性爲目的等，可於聚酯摻合微量之惰性無機或有機之 微粒子等。 摻合之粒子，可舉出氧化矽、氧化鋁、碳酸鈣、磷酸 鈣、陶土、酸化鈦、硫酸鋇、氟化鋰、滑石、交聯高分子 微粉體等。此類粒子可單獨或2種成分以上同時使用，其 含量通常爲1重量％以下，以〇 · 〇 1〜1重量％爲宜，較佳 (4) (4)200422187 爲0.〇2〜ο·5重量％之範圍。粒子含量少時，薄膜表面平 坦化，於膜製造步驟有捲繞特性劣化之傾向，又，粒子含 量若超過1重量1%時，薄膜表面之粗糙化程度過大，薄 膜成霧化，不宜作爲期待透明性之保護膜之用途。 聚膜薄膜中所含粒子之平均粒徑無特別限定，通常爲 0.02〜5μηι之範圍，以0.02〜3μιη爲宜，較佳爲0.02〜 2μπι之範圍。 本發明之聚膜薄膜之製造方法之例，可以使用聚對苯 鲁 二甲酸乙二醇酯爲例，依使用聚酯製造條件而有不同，本 發明未必限定於此。 依照常法，自對苯二甲酸與乙二醇酯化，或將對苯二 甲酸二甲基與乙二醇經酯交換，製得雙-β -對苯二甲酸羥 乙酯（ΒΗΤ)。再將此ΒΗΤ移至聚合槽之同時，於真空下以 2 8 0 °C加熱進行聚合反應製得聚酯。 將此聚酯原料，用擠押機機自噴嘴擠押成熔融片，至 冷卻輥冷卻凝固製得未拉伸片。將此未拉伸片用輕或拉幅 鲁 方法之延伸機進行第一段之拉伸。拉伸溫度通常爲7 0〜 1 2 0°C，以80〜1 10t爲宜，拉伸倍率通常爲2.5〜7倍， 以3 . 〇〜6倍爲宜。接著再進行與第一段拉伸方向正交方 向之拉伸。拉伸溫度通常爲70〜l2〇°C，以S0〜U5°C爲 宜，拉伸倍率通常爲3.0〜6倍，以3 · 5〜5倍爲宜。連續 以1 3 0〜2 5 0 °C範圍之溫度以3 0 %以內之無張力下處理熱 處理，製得雙軸拉伸片。 作爲本發明薄膜基材聚膜薄膜之厚度，一般使用2 5 "7 (5) (5)200422187 〜5 0 μ m者。 於本發明薄膜設置樹脂層之方法，可舉出如（1)於未 拉伸片表面塗佈塗液以乾燥之方法，（2)於單軸拉伸薄膜 表面表面塗佈塗液以乾燥之方法，（3)於雙軸拉伸薄膜表 面表面塗佈塗液以乾燥之方法等，以用縱橫逐次拉伸法同 時進行兩面塗佈之（2)之方法，以用縱橫同時拉伸法時以 (1)之方法爲宜。不論如何本發明薄膜之樹脂層之至少一 側，以於薄膜製造步驟內設置者爲宜。 肇 構成樹脂層之成分，得自防靜電樹脂或導電性樹脂等 具有任何之防靜電能之高分子等適當選擇。 此防靜電劑，如第4級銨鹽、吡啶鑰鹽、第1〜3級 氨基等具有陽離子性官能基之陽離子性防靜電劑，磺酸鹽 基、硫酸酯鹽基、磷酸酯鹽基、膦酸酯鹽基等具有陰離子 性官能基之陰離子性防靜電劑，氨基酸系、氨基酸硫酸酯 等兩性防靜電劑，多元醇系、聚甘油系、聚乙二酯系等具 有非離子性官能性之防靜電劑等各種高分子型防靜電劑， · 或具有第1級氨或第4級銨鹽基，利用電離放射線可聚合 之單體或低聚物，如N，N-二烷基氨烷基（甲基）丙烯酸酯單 體、此類第4級化合物等之聚合性防靜電劑，再亦得使用 聚苯胺、聚吡咯、聚噻吩等導電性聚合等。其中以第4級 銨鹽基型具有陽離子性官能性之高分子型防靜電劑爲宜。 用以構成本發明薄膜之樹脂層之黏合劑，可例示聚酯 類、聚氨基甲酸酯、丙烯酸樹脂類、聚乙烯樹脂類、聚烯 烴類等熱可塑性樹脂及□或熱硬化性丙烯酸樹脂、三聚氰 (6) (6)200422187 胺樹脂 '環氧樹脂、矽酮丙烯酸共聚物樹脂、矽酮氨基甲 酸乙酯系樹脂等熱硬化性樹脂。 本發明用以進一步改良樹脂層之耐溶劑性之交聯劑， 以含有至少1種選自羥甲基化或烷氧基甲基化之三聚氰胺 系化合物、脲系化合物、環氧系化合物、異氰酸酯系化合 物、碳化二亞胺化合物、噁唑啉系化合物、有機矽烷偶合 劑系化合物爲宜。 用以提高樹脂層表面之防污性，於黏合劑成分中含有 聚烯烴類、矽酯系樹脂等爲宜。 構成上述之層之防靜電劑、黏合劑、交聯劑之量比， 因依所選擇化合物之最適値而不同無特別規定，以滿足下 述之層特性之量比者爲宜。 樹脂層中之防靜電性之含量通常爲5重量％以上，以 1 0〜90%之範圍爲宜，防靜電性爲具有陰離子性官能基化 合物之聚合物時爲1 5〜9 0重量％，以2 0〜9 0重量％之範 圍爲宜。 防靜電性之比率若太少，很難達成完全之防靜電效 果，反之防靜電性之比率若過多，有對醇類、MEK(甲基 乙基甲酮）等有機溶劑之耐溶劑性惡化之情況。 本發明之薄膜，樹脂層之厚度通常爲0.001〜0.5 μιη， 以0.01〜Ο.ΐμπι爲宜，尤佳爲0.02〜0.07μηι之範圍。樹 脂層之厚度若低於0.001，得不到完全之防靜電效果，反 之若超過〇 . 5 μπι，管路塗佈性惡化且有不符經濟性之傾 (7) (7)200422187 構成本發明薄膜之樹脂層，用以適用於薄膜製膜管路 之管路塗佈，爲塗佈水性塗液所形成者，亦可爲塗佈含少 量有機溶劑之水性塗液所形成者。 所用之有機溶劑，可例示乙醇、異丙醇、乙二醇、甘 油等醇類，乙基溶纖劑、叔丁基溶纖劑、丙二醇一甲基 醚、四氫呋喃等醚類，丙酮、甲基乙基甲酮等酮類，乙酸 乙酯等酯類，二甲胺基乙醇等胺類等。此類得單獨或組合 複數使用，按實際需要於水性塗液選擇適當有機溶劑使其 · 含有，得有助於塗液之穩定性、塗佈性或塗膜特性。 本發明所用塗液之固體成分濃度，通常爲3 0重量％ 以下，以5〜15重量爲宜，尤佳爲1〜1〇重量％之範圍。 塗液之固體成分若太薄，易生塗佈不沾等易產生塗佈面均 勻性之問題。塗液之固體成分濃度若超過3 0重量％時， 有塗佈液黏度趨局之傾向，因此惡化塗佈外觀。 本發明適當選擇樹脂層之塗液於設基材薄膜之兩面， 至少單面側用附與防污性與防靜電性之塗液爲宜。 · 對基材薄膜之塗液之塗佈方法，有輥筒塗佈法、照相 凹版塗佈法、顯微照相凹版塗佈法、逆輥塗佈法、條狀塗 佈法、輥筒塗刷法、氣動刮刀塗佈法、簾流塗佈法、壓模 塗佈法等任何之塗佈方法等選擇適宜單獨或組合使用之。 有關黏著劑層之塗佈，於經由兩面管路塗佈製得之薄 膜一側之樹脂層面，用黏著劑塗佈機塗佈黏著劑後，通過 烘乾爐使黏著劑層乾燥•硬化捲繞。 用以防止捲繞時黏著，於乾燥·硬化後之黏著面壓貼 (8) (8)200422187 具有脫模性之隔膜，以附分離器之薄膜輥筒捲繞爲宜。隔 膜係於厚度25〜3 8μπι之聚膜薄膜基材之單面塗佈各種硬 化型矽酮樹塗液，得使用乾燥•硬化者，此時矽脫膜層之 厚度使用一般爲0.05〜0.2 μηι者。 黏著劑層乾燥後之厚度適當爲5〜3 5 μιη，以1 0〜 30μιη爲宜，尤佳爲15〜25μηι。 對於黏著層大多利用以各種丙烯酸酯或甲基丙烯酸酯 爲主要成分，再於此共聚各種單體者，於此加上異氰酸酯 參 系硬化劑進行硬化處理所形成者，具有再剝離性之黏著劑 層以選定弱黏著型者爲宜。但爲弱黏著型之黏著劑層時， 厚度爲5 μηι以下，黏著力不足，易導致隔層浮起、黏著 性不佳等麻煩。若爲4 0 μιη以上，因對防靜電面之黏著劑 之被覆層過厚，結果無法產生對黏著劑面性之防靜電效 果。 本發明薄膜之露出樹脂層表面之水滴接觸角須爲80 度以上。水滴接觸角若低於8〇度防污性差。在此所言之 φ 防污性係指表面難污染或即使沾污其污染得易於脫落。 再者，本發明之薄膜於表面外加1 0 k V直流電壓時之 飽和靜電兩面皆爲2 k V以下，以丨k v以下爲宜，外加停 止後之飽和靜電量之減半時間兩面皆爲1 5秒以下，以1 0 秒以下爲宜。飽和靜電量若超過2 k V，瞬間性靜電放電 大，放電阻礙大故不。電荷之半衰期若超過1 5秒，防靜 電效果差故不宜。 -. 200422187 Ο) 〔用以實施發明之形態〕 以下根據實施例進一步詳細說明，本發明若無超過其 要點，並不限定以下之實施例。本發明特性之測定方法如 下述。 (1)飽和電帶及電荷衰減半衰期 用 Shishido 靜電（股）之 STATIC HONESTMETER TYPE H-01 10，自距離20mm外加直流10kV至靜電飽和 · 止，計測靜電飽和時之靜電量爲飽和靜電量（kV)。靜電飽 和後停止外加，計測自外加終止至靜電量半衰之時間，將 此時間爲電荷衰減半衰期。 (2) 水滴接觸角200422187 (1) Description of the invention [Technical field to which the invention belongs] The present invention relates to a polyfilm film having a surface antifouling for protecting optical elements. [Prior art] Polyethylene terephthalate or polyfilm film, Due to its excellent mechanical strength, dimensional stability, chemical resistance, optical properties, etc., it is an example of its use as a substrate for various applications, such as a protective film for protecting the surface from damage and contamination, and for a poly film. The adhesive layer is the protective film of the optical element. The static electricity at each step, the adhesion of foreign matter or dust, and the obstruction of static electricity. For the step of re-peeling the protective film, the surface film of the protective film is easy to be contaminated, and it must have pollution resistance. The method of attaching an antistatic resin to a surface protective film (Japanese Patent Application Laid-Open No. Hei 6- 1 23 806). -123806, JP-A 200 1 -2754 10)), but the package > properties and antistatic properties on both sides are suitable for the polymerization, flatness, heat resistance, and quality as represented by ethylene naphthalate. performance It is also excellent, and it is easy to generate static electricity when it is used for thin peeling of the adhesive on the surface film substrate of optical elements such as polarizing plates, etc., causing problems such as frictional static electricity or peeling electric discharge. Characteristics of sticky surface affected by grease, spillage or sticking. Generally, the surface is coated with antistatic bulletin). In addition, the method of adding an antistatic agent to the adhesive agent layer: a method for applying an adhesive agent to a material, etc. 2000-8 03 3 6, special cost, quality cannot be effectively implemented (2) (2) 200422187. This is to obtain the necessary antistatic properties. It is necessary to contain a large amount of antistatic ingredients in the adhesive layer. The reason is to change the coating characteristics of the re-peelable adhesive and lose its original properties, or the antistatic ingredients of the self-adhesive layer are adhered to the adhesive. Objects move over time and are prone to contamination and adhesion. On the other hand, in order to solve such problems, the overall function of the poly film attached to the substrate must be inadequate. For this reason, if coating processing is required for each requirement, processing steps are added to solve each problem, which deteriorates the situation. Price Lunengbi. In view of the above-mentioned facts, the present invention solves the problem of providing a single-sided side with anti-pollution property at a low cost, a back-peelable adhesive adhesive layer on its inner side, and an antistatic protective film on both sides. [Disclosure of the invention] [Disclosure of the invention] In view of the above-mentioned facts, the inventor has repeatedly reviewed the results and found that a film with a specific structure is a useful protective film, so that the present invention is completed. That is, the gist of the present invention, the optical element surface protection film is characterized in that a poly film is used as a substrate, a resin film is provided on both sides thereof, and a resin film is provided on the surface of the resin layer on one side. The angle is above 80 degrees, and both sides of the saturated static electricity when the 10kV DC voltage is applied to the surface are less than 2kV, and the half-life time of the saturated electrostatic quantity after stopping is 15 seconds or less on both sides. Hereinafter, the present invention will be described in detail. (3) (3) 200422187 The polyester used in the present invention is obtained by polycondensing, for example, an aromatic dicarboxylic acid and an aliphatic ethylene glycol. Examples of aromatic dicarboxylic acids include terephthalic acid and 2,6-naphthalenedicarboxylic acid. Examples of aliphatic glycols include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol. . Representative polyesters include polyethylene terephthalate (PET), polyethylene-2,6-naphthalene dicarboxylate (PEN), and the like. The polyester may also be a copolyester of a homopolyester. When it is a copolyester, it is usually a copolymer containing a third component of 30 mol% or less. Examples of the dicarboxylic acid component of the copolyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, azelaic acid, and ' One or two or more kinds of hydroxy acids. Examples of the ethylene glycol component include ethylene glycol, diethylene glycol, propylene glycol, succinic acid, 1,4-cyclohexanedimethanol, neopentyl glycol, and the like. More than two. The polyester used in the present invention may be obtained by melt polymerization reaction, or a solid-phase polymerized polyester which is once pelletized after melt polymerization. The present invention may be a film having a co-extruded laminated structure of heterogeneous polyesters. . The polyester used in the present invention may be blended with an antistatic agent within a range that does not damage the gist of the present invention. In order to improve the sliding properties or abrasion resistance of the film, etc., a small amount of inert inorganic or organic micro-particles can be blended in the polyester according to the needs of implementation. Examples of the particles to be blended include silica, alumina, calcium carbonate, calcium phosphate, clay, titanium acidate, barium sulfate, lithium fluoride, talc, and crosslinked polymer fine powder. Such particles can be used singly or in combination of two or more components, and the content is usually 1% by weight or less, preferably 〇1 ～ 1% by weight, and preferably (4) (4) 200422187 is 0.02 ~ ο -A range of 5% by weight. When the content of particles is small, the surface of the film is flattened, and the winding characteristics tend to be deteriorated during the film manufacturing process. When the content of particles exceeds 1% by weight, the surface roughness of the film is too large, and the film is fogged, which is not suitable as an expectation. Use of transparent protective film. The average particle diameter of the particles contained in the polymembrane film is not particularly limited, but is usually in the range of 0.02 to 5 μm, preferably 0.02 to 3 μm, and more preferably in the range of 0.02 to 2 μm. As an example of the method for producing the poly film of the present invention, polyethylene terephthalate can be used as an example, and it varies depending on the production conditions of the polyester, and the present invention is not necessarily limited to this. Esterification of terephthalic acid with ethylene glycol or transesterification of dimethyl terephthalate with ethylene glycol according to a conventional method yields bis-β-hydroxyethyl terephthalate (BHT). While moving the BHT to the polymerization tank, the polyester was obtained by polymerization under heating at 280 ° C under vacuum. This polyester raw material was extruded from a nozzle into a molten sheet by an extruder, and cooled to a cooling roller to solidify to obtain an unstretched sheet. This unstretched sheet was stretched with a light or tenter stretcher in the first stage. The stretching temperature is usually 70 ~ 120 ° C, preferably 80 ~ 1 10t, and the stretching ratio is usually 2.5 ~ 7 times, preferably 3.0 ~ 6 times. Then, it is stretched in a direction orthogonal to the first stretch direction. The stretching temperature is usually 70 to 120 ° C, preferably S0 to U5 ° C, and the stretching ratio is generally 3.0 to 6 times, and preferably 3.5 to 5 times. Continuously heat-treated at a temperature in the range of 130 to 250 ° C and within 30% without tension to obtain a biaxially stretched sheet. As the thickness of the polyimide film of the film base material of the present invention, 2 5 " 7 (5) (5) 200422187 ~ 50 μm is generally used. The method for providing a resin layer in the film of the present invention includes, for example, (1) a method of applying a coating liquid on the surface of an unstretched sheet to dry, and (2) a method of applying a coating liquid on the surface of a uniaxially stretched film to dry. Method, (3) a method of applying a coating liquid on the surface of a biaxially stretched film to dry, etc., and (2) a method of simultaneously applying double-sided coating by a vertical and horizontal sequential stretching method, and using a vertical and horizontal simultaneous stretching method The method of (1) is appropriate. In any case, at least one side of the resin layer of the film of the present invention is preferably provided in the film manufacturing step. The components constituting the resin layer are appropriately selected from polymers having any antistatic energy, such as antistatic resin or conductive resin. This antistatic agent is a cationic antistatic agent having a cationic functional group such as a 4th ammonium salt, a pyridinium salt, a 1st to 3rd amino group, a sulfonate group, a sulfate ester group, a phosphate ester group, Anionic antistatic agents with anionic functional groups such as phosphonate salts, amphoteric antistatic agents such as amino acids, amino acid sulfates, etc. Polyols, polyglycerols, polyethylene glycols, etc. have nonionic functionality Antistatic agents and other polymer-based antistatic agents, or monomers or oligomers that have a level 1 ammonia or a level 4 ammonium salt and are polymerizable by ionizing radiation, such as N, N-dialkyl ammonia For polymerizable antistatic agents such as alkyl (meth) acrylate monomers and such fourth-grade compounds, conductive polymers such as polyaniline, polypyrrole, and polythiophene can be used. Among them, a fourth-order ammonium salt-based polymer type antistatic agent is preferable. Examples of the adhesive used to constitute the resin layer of the film of the present invention include thermoplastic resins such as polyesters, polyurethanes, acrylic resins, polyethylene resins, polyolefins, and thermosetting acrylic resins, Melamine (6) (6) 200422187 Thermosetting resins such as amine resins, epoxy resins, silicone acrylic copolymer resins, and silicone urethane resins. The cross-linking agent for further improving the solvent resistance of the resin layer of the present invention contains at least one kind of melamine-based compound, urea-based compound, epoxy-based compound, isocyanate selected from methylolation or alkoxymethylation. The compound is preferably a system compound, a carbodiimide compound, an oxazoline compound, or an organosilane coupling agent system compound. In order to improve the antifouling property of the surface of the resin layer, it is preferable to include polyolefins, silicone resins, etc. in the adhesive component. The amount ratios of the antistatic agents, adhesives, and cross-linking agents constituting the above-mentioned layers are different according to the optimum of the selected compound, and there is no special rule, and it is preferable to satisfy the ratios of the layer characteristics described below. The content of the antistatic property in the resin layer is usually 5% by weight or more, preferably in the range of 10 to 90%. When the antistatic property is a polymer having an anionic functional group compound, it is 15 to 90% by weight. A range of 20 to 90% by weight is preferable. If the antistatic ratio is too small, it is difficult to achieve a complete antistatic effect. On the other hand, if the antistatic ratio is too large, the solvent resistance of organic solvents such as alcohols and MEK (methyl ethyl ketone) may deteriorate. Happening. In the film of the present invention, the thickness of the resin layer is usually 0.001 to 0.5 μm, preferably 0.01 to 0. μm, and more preferably 0.02 to 0.07 μm. If the thickness of the resin layer is less than 0.001, a complete antistatic effect cannot be obtained. On the other hand, if it exceeds 0.5 μm, the coating properties of the pipeline are deteriorated and there is an uneconomical tendency (7) (7) 200422187 to constitute the film of the present invention. The resin layer is used for pipeline coating suitable for thin film film-making pipelines. It is formed by applying an aqueous coating solution, or it can be formed by applying an aqueous coating solution containing a small amount of an organic solvent. Examples of the organic solvent used include alcohols such as ethanol, isopropanol, ethylene glycol, and glycerol, ethyl cellosolve, tert-butyl cellosolve, ethers such as propylene glycol monomethyl ether, and tetrahydrofuran, and acetone and methyl ethyl. Ketones such as methyl ketone, esters such as ethyl acetate, amines such as dimethylaminoethanol, and the like. This type can be used alone or in combination. Select an appropriate organic solvent in the aqueous coating solution according to the actual needs and include it. It can contribute to the stability, coating properties, or coating film properties of the coating solution. The solid content concentration of the coating liquid used in the present invention is usually 30% by weight or less, preferably 5 to 15% by weight, and particularly preferably 1 to 10% by weight. If the solid content of the coating liquid is too thin, the problem of uniformity of the coated surface is liable to occur, such as non-sticking. If the solid content concentration of the coating liquid exceeds 30% by weight, the viscosity of the coating liquid tends to be inferior, and therefore the coating appearance is deteriorated. In the present invention, the coating liquid of the resin layer is appropriately selected on both sides of the base film, and at least one side is preferably a coating liquid with antifouling and antistatic properties. · The coating method for the coating solution of the base film includes a roll coating method, a gravure coating method, a microphotogravure coating method, a reverse roll coating method, a strip coating method, and a roller coating method. Any suitable coating method, such as the air coating method, the pneumatic blade coating method, the curtain flow coating method, and the die coating method, etc., can be selected for use alone or in combination. Regarding the coating of the adhesive layer, the resin layer on one side of the film obtained by coating on both sides of the film is coated with an adhesive using an adhesive coating machine, and then the adhesive layer is dried and hardened by a drying furnace. . It is used to prevent sticking during winding, and it is pressed on the adhesive surface after drying and hardening. (8) (8) 200422187 It has a release film. It is better to roll with a film roll with a separator. The diaphragm is coated with various hardened silicone tree coating liquids on one side of a poly-film film substrate with a thickness of 25 ~ 38 μm, which can be dried and hardened. At this time, the thickness of the silicon release layer is generally 0.05 ~ 0.2 By. The thickness of the adhesive layer after drying is suitably 5 to 35 μm, preferably 10 to 30 μm, and particularly preferably 15 to 25 μm. For the adhesive layer, a variety of acrylates or methacrylates are used as the main component, and various monomers are copolymerized here, and those formed by adding an isocyanate sclerosing agent to the hardening treatment are re-peelable adhesives. It is advisable to select a weak adhesion type for the layer. However, when it is a weak-adhesive type adhesive layer, the thickness is less than 5 μηι, the adhesive force is insufficient, and it is easy to cause troubles such as floating of the spacer and poor adhesion. If it is 40 μm or more, the coating layer of the adhesive on the antistatic surface is too thick, and as a result, the antistatic effect on the surface properties of the adhesive cannot be produced. The contact angle of water droplets on the surface of the film of the present invention exposed on the resin layer must be 80 degrees or more. If the contact angle of the water drops is less than 80 degrees, the antifouling property is poor. The term "fouling resistance" as used herein means that the surface is difficult to be contaminated or that it is easy to fall off even if it is contaminated. Furthermore, both sides of the saturated static electricity of the film of the present invention when a DC voltage of 10 kV is applied are less than 2 kV, preferably below kv, and both sides of the saturated electrostatic quantity after stopping are 1 5 seconds or less, preferably 10 seconds or less. If the amount of saturated static electricity exceeds 2 kV, the instantaneous electrostatic discharge will be large, and the discharge will be hindered. If the half-life of the electric charge exceeds 15 seconds, the antistatic effect is poor and it is not suitable. -. 200422187 〇) [Forms for Implementing the Invention] The following is a further detailed description based on the examples. The present invention is not limited to the following examples unless it exceeds the gist thereof. The method for measuring the characteristics of the present invention is as follows. (1) The Shishido Electrostatic (Type) STATIC HONESTMETER TYPE H-01 10 for saturated electric band and charge decay half-life is applied from a distance of 20mm plus DC 10kV to static saturation. ). After the electrostatic saturation is completed, the application is stopped, and the time from the termination of the application to the half-life of the static charge is measured. This time is the charge decay half-life. (2) Water contact angle
使用協和界面科學（股）製接觸角計（CONTACT-ANGLE METER) ， 測定於 薄膜表 面滴液 蒸餾水 時水滴 /薄 膜表面之接觸角。 H (3) 防污性 磨光薄膜表面之黏著層面後，已黏附黏著層成分用滲 透乙醇之片狀棉花擦拭，以下述基準評估擦拭後之結果。 〇：於防污•防靜電層袠面層表面黏著劑很難黏附， 或得以易於擦拭已黏附之黏著劑。看不出擦拭後之防污· 防靜電層表面層表面之污垢、漬跡等外觀變化。 △ •’對於黏著劑之黏附、擦拭性或表面外觀變化介於 (10) (10)200422187 〇與χ中間。 X :黏著劑易黏附，或很難除去已黏附之黏著劑。擦 拭後表面外觀殘留污垢、漬跡。 本發明實施例所用之塗佈劑成分如下所載。 [防靜電層成分] 防靜電劑（A1):聚二烯丙基二甲基銨氯化物（平均分 子量：約3 00 00)水性樹脂（B1):水性丙烯酸樹脂（日本 鲁 carbide 工業公司製「Nicazole A-08」 水性樹脂（B 2):部份皂化型聚乙烯醇（皂化度：約88 莫耳％) 水性樹脂（B3):氧化聚乙烯水分散體（Johns〇n Polymer 公司製「Johnwax 26」） 交聯劑（Cl):甲氧基羥甲基尿素（大日本墨水公司製 「BekminJIOl」） 【實施方式】 實施例1 將特性黏度〇.65dl/g之聚對苯二甲酸乙二醇酯（含平 均粒徑約2.4μιη之二氧化矽粒子0.05%)之顆粒於180°C熱 風乾燥結晶化，供給於擠壓機，於2 8 0〜3 00 °C之溫度自 T壓模熔壓擠壓成片狀，倂用靜電黏合，於鏡面冷卻轉筒 上鑄造•急冷成厚度約7 2 0 μπι之未拉伸薄膜，連續將此 薄膜於8 5 °C朝長軸（縱）方向拉伸3.7倍，成單軸拉伸薄 -13- (11) (11)200422187 於此單軸拉伸薄膜，將由以下摻合所成之塗液（1)及 塗液（4)於製膜步驟橫拉伸前階段使用兩面塗佈裝置分別 於表面側/裏面側塗佈約5pm(wet厚）。 塗液（1):將4級胺鹽型陽離子性高分子防靜電劑 (A1)、氧化聚乙烯水分散體（B3)及三聚氰胺系化合物（C1) 以 4〇/ 4 0/ 20 (換算固體成分重量比）之比率混合，於 離子交換水稀釋調製成固體成分濃度3重量％之塗佈液 塗液（4):將4級胺鹽型陽離子性高分子防靜電劑 (A1)、丙烯酸樹脂（B1)及三聚氰胺系化合物（C1)以40/40 / 20 (換算固體成分重量比）之比率混合，於離子交換水 稀釋調製成固體成分濃度3重量％之塗佈液 於連續橫拉伸區域以1 1 0〜1 5 0 t：朝橫方向拉伸3.9 倍，以2 3 0 °C進行熱處理•固定，製得厚度38μπι之兩面 塗佈雙軸拉伸聚酯薄膜。 所得兩面塗佈薄膜經由塗液（1 )形成之塗膜面，塗佈 以下所示之黏著劑後，以1 3 0 °C 1分鐘使其乾燥•硬化， 乾燥後製得具有塗佈厚度20μηι黏著劑層之表面保護膜。 此表面保護膜之特性記於表2。 黏著劑組成：將丙烯酸系黏著劑（帝國化學（股）製 「SG-800」及異氰酸酯硬化劑（日本聚氨酯（股）製 「colonate HL」）以1〇〇/1〇(換算固體成分重量比）之比率 混合之塗佈液 -14- (12) 200422187 實施例2〜3、比較例1〜4 除將表1中塗液（1)(4)所載之組成物變更以外，以同 於實施例1之方法作成保護膜。變更塗液之塗佈結構並所 作成之保護膜特性示於表2。 比較例5 不進行管路塗佈，無塗佈之聚酯薄膜以同實施例1之 方法製膜，作成保護膜。 _A contact angle meter (CONTACT-ANGLE METER) manufactured by Kyowa Interface Science Co., Ltd. was used to measure the contact angle of water droplets / film surface when dripping distilled water on the surface of the film. H (3) Antifouling property After polishing the adhesive layer on the surface of the film, the components of the adhesive layer were wiped with a sheet of cotton saturated with ethanol, and the results after wiping were evaluated on the basis of the following. 〇: The adhesive on the surface of the antifouling and antistatic layer and the surface layer is difficult to adhere, or it is easy to wipe the adhered adhesive. No changes in appearance such as dirt and stains on the surface of the anti-fouling and anti-static layer surface after wiping. △ • ′ is between (10) (10) 200422187 〇 and χ for the change of adhesion, wiping property or surface appearance of the adhesive. X: The adhesive is easy to adhere, or it is difficult to remove the adhered adhesive. Dirt and stains remain on the surface after wiping. The coating agent components used in the examples of the present invention are as follows. [Antistatic layer composition] Antistatic agent (A1): polydiallyldimethylammonium chloride (average molecular weight: about 3 00 00) water-based resin (B1): water-based acrylic resin (manufactured by Japan Lucarbide Industrial Co., Ltd. " Nicazole A-08 "Water-based resin (B 2): Partially saponified polyvinyl alcohol (Saponification degree: about 88 mol%) Water-based resin (B3): Oxidized polyethylene water dispersion (" Johnwax manufactured by Johns On Polymer Corporation ") 26 ") Crosslinking agent (Cl): methoxymethylol urea (" BekminJIOl "manufactured by Dainippon Ink Co., Ltd.) [Embodiment] Example 1 Polyethylene terephthalate having an intrinsic viscosity of 0.65 dl / g Alcohol ester (containing silica dioxide particles with an average particle diameter of about 2.4 μm 0.05%) particles are dried and crystallized at 180 ° C in hot air, supplied to the extruder, and from T stamper at a temperature of 2 0 ~ 3 00 ° C Melt and extrude into a sheet shape, and then use electrostatic bonding to cast on a mirror cooling drum Stretched 3.7 times in the direction, making it uniaxially stretched. 13- (11) (11) 200422187 The uniaxially stretched film here will be made by The combined coating liquid (1) and coating liquid (4) were applied on the surface side / inside of each side at a thickness of about 5pm (wet thickness) using a two-sided coating device at the stage before the transverse stretching of the film formation step. : The grade 4 amine salt type cationic polymer antistatic agent (A1), the oxidized polyethylene aqueous dispersion (B3) and the melamine-based compound (C1) are divided by 40/4 0/20 (the weight ratio of solid content) Mixing ratio, diluted with ion-exchanged water to prepare a coating liquid coating solution with a solid content concentration of 3% by weight (4): Grade 4 amine salt type cationic polymer antistatic agent (A1), acrylic resin (B1) and melamine The compound (C1) is mixed at a ratio of 40/40/20 (converted weight ratio of solid content), and the coating solution is diluted with ion-exchanged water to prepare a solid content concentration of 3% by weight. In the continuous transverse stretching area, 1 1 0 to 15 0 t: Stretched 3.9 times in the transverse direction, and heat-treated and fixed at 230 ° C to produce a biaxially stretched polyester film with a thickness of 38 μm on both sides. The obtained two-sided coating film was passed through the coating solution (1 ) After forming the coating film surface, apply the adhesive shown below, and dry it at 130 ° C for 1 minute. After curing and drying, a surface protective film with a coating thickness of 20 μηι was obtained. The characteristics of this surface protective film are shown in Table 2. Adhesive composition: Acrylic adhesive ("SG-800" manufactured by Imperial Chemical Co., Ltd.) "And an isocyanate hardener (" colonate HL "manufactured by Japan Polyurethane Co., Ltd.) at a ratio of 100/1/10 (converted solid content weight ratio) coating liquid -14- (12) 200422187 Examples 2 to 3 Comparative Examples 1 to 4 A protective film was prepared in the same manner as in Example 1 except that the composition contained in the coating liquids (1) and (4) in Table 1 was changed. Table 2 shows the characteristics of the protective film produced by changing the coating structure of the coating solution. Comparative Example 5 Without coating the pipes, a non-coated polyester film was formed in the same manner as in Example 1 to form a protective film. _
表1 防靜電劑 水性樹脂 交聯劑 A1 B 1 B2 B3 C1 40 一 _ 40 20 40 10 _ 30 20 40 一 40 10 20 40 40 _ — 20 ]0 10 一 3 0 20 (13)200422187 表2 面-1 面·2 黏著 劑層 面-1 面-2 厚度 (μηι) 接觸角 (度） 防污性 飽和 帶電 (KV) 半衰期 (秒） 飽和靜 電 (KV) 半衰期 (秒） 實施例 1 塗液① 塗液④ 20 89 〇 0.1 ' 0.8 0.4 3 實施例 2 塗液② 塗液③ 20 88 〇 0.1 0.7 0.4 3 實施例 3 塗液② 塗液② 20 88 〇 0.1 0.7 0.6 6 比較例 1 塗液③ 塗液③ 20 81 Δ 0.1 0.6 0.4 3 比較例 2 塗液④ 塗液④ 20 79 X 0.1 0.7 0.5 5 比較例 3 塗液⑤ 塗液⑤ 20 89 〇 2以上 60以上 2以上 60以上 比較例 4 塗液① 塗液④ 40 89 〇 0.1 0.8 2以上 60以上 比較例 5 — — 20 70 X 2 30 2以上 50 (14) (14)200422187 上表中，面-2係黏著劑層側，面-1係其相反面。 實施例I〜3，於塗液中摻合適當之防污成分並防靜 電成分’且進行製膜時兩面管路塗佈，得以低成本製得以 防污•防靜電爲目的之保護膜。 比較例1、比較例2，因塗液中無或過少防污成分， 製得低成本之兩面防靜電保護膜無防污特性。比較例3， 因防靜電成分不足故防靜電性弱。比較例4因黏著劑層過 厚，故黏著劑層側之防靜電效果不佳。 · 〔產業上之可利用性〕 如上之詳述，本發明之保護膜，具有實用性有用之表 面防污性並兩面防靜電特性，且成本性亦優異，其工業性 價値高。Table 1 Antistatic agent water-based resin cross-linking agent A1 B 1 B2 B3 C1 40 _ 40 20 40 10 _ 30 20 40 _ 40 10 20 40 40 _ — 20] 0 10-3 0 20 (13) 200422187 Table 2 -1 surface · 2 Adhesive layer-1 surface-2 Thickness (μηι) Contact angle (degrees) Antifouling Saturation charge (KV) Half-life (seconds) Saturation static electricity (KV) Half-life (seconds) Example 1 Coating solution ① Coating Liquid ④ 20 89 〇0.1 '0.8 0.4 3 Example 2 Coating liquid ② Coating liquid ③ 20 88 〇0.1 0.7 0.4 3 Example 3 Coating liquid ② Coating liquid ② 20 88 〇0.1 0.7 0.6 6 Comparative Example 1 Coating liquid ③ Coating liquid ③ 20 81 Δ 0.1 0.6 0.4 3 Comparative Example 2 Coating liquid ④ Coating liquid ④ 20 79 X 0.1 0.7 0.5 5 Comparative Example 3 Coating liquid ⑤ Coating liquid ⑤ 20 89 〇2 or more 60 or more 2 or more 60 or more Comparative Example 4 Coating liquid ① Coating liquid ④ 40 89 〇0.1 0.8 2 or more 60 or more Comparative Example 5 — 20 70 X 2 30 2 or more 50 (14) (14) 200422187 In the table above, surface-2 is the side of the adhesive layer, and surface-1 is the side The opposite. In Examples I to 3, a suitable antifouling component and an antistatic component were added to the coating solution, and two-sided pipe coating was applied during film formation, so that a protective film for the purpose of antifouling and antistatic can be produced at low cost. In Comparative Example 1 and Comparative Example 2, the low-cost two-sided antistatic protective film had no antifouling properties because no or too little antifouling component was contained in the coating solution. Comparative Example 3 has insufficient antistatic properties due to insufficient antistatic components. In Comparative Example 4, since the adhesive layer was too thick, the antistatic effect on the adhesive layer side was not good. [Industrial Applicability] As described in detail above, the protective film of the present invention has practical antifouling properties and antistatic properties on both sides, and is also excellent in cost and has high industrial cost.