200800598 七、發明說明： 【發明所屬之技術領域】 本餐明係有關偏光片用表面保濩膜’藉由在聚合物膜上涂佈的 方法產生具有防污抗靜電的薄膜，而此塗佈液主要包括聚噻$及界 面活性劑。 土 【先前技術】200800598 VII. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a surface-protecting film for a polarizer, which produces a film having antifouling and antistatic by a method of coating on a polymer film, and this coating The liquid mainly includes polythiophene and a surfactant. Soil [prior art]
液晶顯示器的製造係將各類光學元件加以積層化，其中層 的偏光片（板)係以表面保護膜加以覆蓋，以避免在組裝步驟及偏^ 片配運過程中，受到灰塵沾黏導致光學檢測誤判，或靜電累導致 液晶元件受損以及吸收水分導致偏光片受潮影響可靠度二’、貝、 一般抗靜電塗佈的薄膜，用途非常廣泛，&如照^ 带 ^裝=及ΐ他包裝材，此抗靜電塗佈液係以傳統已知的各種界ΐ活 1分子型料紐填料权，但t赫在 2至於取，的V电尚/刀子聚苯胺及聚吡咯 者，亦有薄膜透光率差的問題。. ^ ) 以聚噻吩(polythiophene)為主的塗佈薄膜，雖妙 仍存在著與聚合物膜接著不良、添加比例#過高、用二 及溶劑相容等問題存在著。 …、法舁一般連結劑 【發明内容】 •八’本發明利用特殊水_結劑及界面活性劑，降低聚 使能緊密地與聚合物膜接著。 /、有防5私水效果， 活性ΐ發日種包括聚輕、水性連結劑及界面 保護」。“ _用的塗佈液’特別是在偏光片（板)用的表面 。本發明之另-目的係在提供一種有防污抗靜電塗佈的聚合物膜 本發明之又-目的係在提供一種具有高透光率的塗佈液。 4 200800598 但相對低成本的塗佈液的係在提供—種具有㈣污性及抗靜電性， 液。本u之再另-目的係在提供—種與聚合物赌密接著的塗佈 佈液。之又再#目的係在提供一種不含有機溶劑的環保型塗 本發明之又再另-目的係在提 具 ，可適用於線上塗佈（in如…·、f低物係數的塗佈液 表面擦傷。 oamg)加工袅程，減輕轴向延伸之 【發明内容】 fi.供形成偏光片用表面保護膜而用的塗佈液，其主要特 敛疋匕括水唼㊉、水性連結劑及界面活性劑。 發ϊΐΐ之塗佈液，其中聚嗟吩提供表面保護膜主要之抗 二兒Γ·丨而取宜的聚嗟吩係聚乙烯基二氧嗟吩(P0ly(3,4-ethy㈣ , .XTffiSPEDT) . 子材料，即HC Stark(拜耳公司的一個部門)所稱的邮舰p，乃第 二個已商業化應用於攝影技術上的抗靜電薄膜材料，利用聚苯乙烯 石頁$ ^Polystyrene sulfonic acid，以下簡稱PSS)與PEDT形成離子型 的阿分子複合物，加水混合後即形成高分子微膠體顆粒的分散溶液 透過i次分放膠體顆粒之水溶液型態，使Baytr〇n p於塗饰過程中， 可展現優越的成膜效果。其係將Baytr〇n p中的聚苯乙烯石黃酸(PM) /與醇類化合物、氯醯化合物、環氧化合物或三聚氰胺化合物，進 行交聯反應而增加塗佈液之耐水及耐溶劑等耐化學藥劑性。 在本發明塗佈液中的聚嗟吩(Baytron P)之含量宜為〇·〇5〜〇·5重 量％，較宜為0.08〜0.25重量％。 與本發明有關之塗佈液，其中抗靜電塗佈液亦包括界面活性劑 或界面活性劑的混合物，一般界面活性劑有陰離子型、陽離子型、 非離子型及兩性離子型等，與本發明有關之塗佈液以採用陰離子型 5 200800598 ^非離子型時有較㈣顯能力，且對聚麵有較 塗膜外觀較為透明及平坦。中丰贸文此力’ ==更=與=:關之^== 材料不易起泡，又降低表面張力的效離卞型 屬環保材料。常用的氟素界面活性劑有3^八加讀少’ 業製造公司）的襲30及_^==、=7明尼蘇達礦 ⑽、日本大金（DaikinCG.，）公司的邦以的Ζ_跡SN_ 在本發明塗佈液中的氟素界面活性之 %，較宜為0.05〜0.2重量％。 狀己里且為〇.〇1〜0.5重量 抒ΪΪΓ有關之塗佈液’其中不包括有明顯量的有機溶劑，屬 里的水性連結劑，經過特殊改良的水 ' 有，之塗佈液’其中水性連結劑包括2-4G重量爾脂 加劑，盆理劑^過之填充粒子及G.⑽重量％添 克〜有襲重量％的成分c，其成分C健 之樹Ϊ 如1^=樹脂為—在，鏈及側鏈中具有酯鏈 酯樹脂可任立切=羽二0卜3 a、_03NH4等水溶性的基團。該聚 1彳思砥自笔知的水溶性或水分散型聚酯樹脂。 聚氰胺i甲改ί樹脂/’如三聚氛胺、三 工Τ 土文貝的—ΛΚ氧胺衍生物、低級醇之 200800598 聚氰胺與曱醛經予縮合之羥曱基改質的三聚氰胺衍生物、低級醇之 反應局部或完全醚化成羥甲基改質的三聚氰胺之化合物及其混合物 、。二聚氰胺可為單體或含二聚物或以上的聚合物之縮合物，另亦可 為其混合物，以三聚氰胺為主成分之用量宜為5-40重量％，較宜為 10-30重量％。 /成分C為壓克力樹脂，可利用傳統的乳化聚合法製備，其成分 不，特殊限制。例如丙烯酸曱酯、甲基丙烯酸曱酯、丙浠酸乙酯、 丙丁酯、丙烯酸異辛酯、丙烯酸羥乙酯、甲基丙烯酸羥乙酯、 醯胺、甲基丙烯醯胺、；^羥甲基丙烯醯胺或队羥甲基曱基丙烯 醯胺等，壓克力樹脂成分之用量宜為2〇_9〇重量％，較宜為3〇_8〇重 量％ 〇 —水性連結劑另含有表面處理劑經改質的填充粒子，其處理劑係 t夕化合物或分散劑或高分子聚合物，或此三者中的—種、兩種或 全部之組合物，經予處理的填充粒子，與水性連結劑之樹脂間有良 好ϋ目容性，，填充粒子可充分分散於樹脂中；填充粒子係氧化銘 、，氧化銘、氧化石夕、二氧化鈦、氧化錯、碳酸約、·碳酸 鋇等之無機粒子。 夂 水性連結劑之添加劑可為流展助劑、觸媒及共溶劑等。其中之 ^展助劑可提升塗膜的平坦度，觸制可控制塗層的反應速^，觸 某;=，諸如乙醇、正丙醇、異丙醇、異谓、了基纖維素等 制液態成份的揮發速率。 水性連結劑中因為含有水溶性基團的聚醋樹脂，容易與水互溶 朽ίϊΐί氰咖旨容易與聚合膜接著；含有高透明的壓克力 光學性質，如透光率及曇霧度；又因為添加 處ί，'的奈米級填充粒子，使其極容易與樹脂相容不會 量愈多可以增加聚合膜的滑性，卻不會使 ，連結劑在塗佈液中’扮演非常重要的角色 7 200800598 在本發明塗佈液中的水性連結劑之含量宜為i〜職量❶/ 為1〜5重量％。 一it發明有關之塗佈液，可另含已知廣泛使用的添加物，例如 料或染料，其他抗靜電劑、·劑、其他流展劑 、可塑劑、抗氧化劑及填充劑。 ，本發明有關之塗佈液，經塗佈於聚_職，具有高透明性 、氐務度、優良的接著性及滑性等特性，適用於光學用之基材。 與本發明有關之塗佈液塗佈於聚合物膜上之乾燥後的产 為0.001〜0·5/ζιη(微米），較宜為001〜01//m。 又 ^本發明有關之塗佈液，其抗靜電雜主要取決 的聚合物膜之表面阻抗，可利用傳統的表面 有以 ADVANTEST、刪0A)檢測，適用於本發明之表面阻抗The manufacture of liquid crystal displays is to laminate various types of optical components. The polarizers (plates) of the layers are covered with a surface protective film to avoid the adhesion of dust during the assembly process and the dispensing process. Detection of misjudgment, or electrostatic damage caused by damage to the liquid crystal element and absorption of moisture, causing the polarizer to be affected by moisture. Reliability, 'Bei, general antistatic coating film, very versatile, & Packaging material, this antistatic coating liquid is made of traditionally known various kinds of materials, such as a kind of material, but the T is in the range of 2 to get, the V electric / knife polyaniline and polypyrrole, also The problem of poor transmittance of the film. ^ ) Polythiophene-based coating film, although it still has problems with polymer film defects, excessive addition ratio #, and compatibility with solvents and solvents. ..., 舁 舁 连结 【 【 【 【 • • • • • • • • 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本/, anti-5 private water effect, active hair types include poly light, water-based bonding agent and interface protection. "The coating liquid for use" is particularly on the surface for a polarizer (plate). Another object of the present invention is to provide a polymer film having antifouling and antistatic coating. A coating liquid having high light transmittance. 4 200800598 However, the relatively low-cost coating liquid is provided with a kind of (four) stain and antistatic property, and the liquid is further provided. The application of the coating liquid with the polymer gambling. The purpose of the invention is to provide an environmentally friendly coating which does not contain an organic solvent. The invention is further applied to the coating, which is suitable for in-line coating (in For example, the surface of the coating liquid with a low material coefficient is scratched. oamg) The processing step is to reduce the axial elongation. [Invention] The coating liquid for forming a surface protective film for a polarizer is mainly used. Convergence includes water hydrazine, water-based bonding agent and surfactant. The coating liquid of hairpin, which provides a surface protective film, which is mainly resistant to bismuth and bismuth. Dioxophene (P0ly (3,4-ethy(iv), .XTffiSPEDT). Sub-material, HC Stark (Bayer) One of the divisions, the so-called cruise ship p, is the second antistatic film material that has been commercialized in photographic technology, using polystyrene stone sheet $ ^Polystyrene sulfonic acid (hereinafter referred to as PSS) and PEDT to form an ion type. The molecular complex of the molecular compound, which is mixed with water, forms a dispersion solution of the polymer microcolloid particles, and passes through the aqueous solution form of the sub-dispersed colloidal particles, so that Baytr〇np can exhibit a superior film-forming effect during the coating process. The polystyrene (PM) in Baytr〇np is cross-linked with an alcohol compound, a chlorinated compound, an epoxy compound or a melamine compound to increase the chemical resistance of the coating liquid to water and solvent. The content of the polybenzazole (Baytron P) in the coating liquid of the present invention is preferably 〇·〇5 to 〇·5 wt%, more preferably 0.08 to 0.25 wt%. The coating liquid according to the present invention The antistatic coating liquid also includes a mixture of a surfactant or a surfactant. Generally, the surfactant has an anionic type, a cationic type, a nonionic type, a zwitterionic type, etc., and the coating liquid related to the present invention is used. Anionic type 5 200800598 ^There is more (four) display ability in the non-ionic type, and the coating surface is more transparent and flat on the surface of the coating. Zhongfeng Trading has the power of '==more = and =: Guanzhi ^== The effect of foaming and lowering the surface tension is an environmentally friendly material. The commonly used fluorine surfactants are 3^8 plus less (industry manufacturing company) hit 30 and _^==, =7 Minnesota mine (10), The amount of the fluorine interface activity in the coating liquid of the present invention is preferably 0.05 to 0.2% by weight in the coating liquid of the Japanese Daikin (Daikin CG.,) company, and is preferably 0.05 to 0.2% by weight. ~0.5 weight 抒ΪΪΓ related coating liquid 'which does not include a significant amount of organic solvent, the water-based bonding agent in the genus, specially modified water 'yes, the coating liquid' wherein the aqueous bonding agent includes 2-4G weight Alkali fat addition agent, potting agent ^ over filled particles and G. (10) wt% gram ~ attack weight % of the component c, its composition C health tree Ϊ such as 1 ^ = resin is - in, chain and side chain The ester chain ester resin may be a water-soluble group such as a cleavage=feather 2 ab, a _03NH4. The water-soluble or water-dispersible polyester resin is known from the prior art. Melamine i-modified resin / 'such as trimeric amine, Sangong Τ 文 的 的 ΛΚ ΛΚ ΛΚ 2008 2008 2008 2008 2008 2008 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 A reaction of a melamine derivative or a lower alcohol, which is partially or completely etherified into a methylol-modified melamine compound and a mixture thereof. The melamine may be a condensate of a monomer or a polymer containing a dimer or more, or a mixture thereof, and the melamine-based component is preferably used in an amount of 5 to 40% by weight, preferably 10 to 30% by weight. weight%. /Component C is an acrylic resin which can be prepared by a conventional emulsion polymerization method, and its composition is not particularly limited. For example, decyl acrylate, decyl methacrylate, ethyl propyl acrylate, butyl acrylate, isooctyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, decylamine, methacrylamide, hydroxymethyl The amount of the acrylic resin component is preferably 2〇_9〇% by weight, more preferably 3〇_8〇% by weight, based on the acrylamide or the group of hydroxymethyl decyl acrylamide, etc. 〇—the aqueous binder further contains The surface treatment agent is a modified filler particle, and the treatment agent is a compound or a dispersant or a high molecular polymer, or a combination of two, all or a combination of the three, the pretreated filler particles, Good compatibility with the resin of the aqueous binder, the filler particles can be sufficiently dispersed in the resin; the filler particles are oxidized, oxidized, oxidized, oxidized, carbonated, carbonated, etc. Inorganic particles.添加剂 The additives for the water-based binder can be a flow aid, a catalyst, a co-solvent, and the like. Among them, the additive can improve the flatness of the coating film, and the reaction speed of the controllable coating can be controlled, and it can be touched; =, such as ethanol, n-propanol, isopropanol, iso-synthesis, cellulose, etc. The rate of volatilization of liquid components. In the water-based binder, because of the water-soluble group-containing polyester resin, it is easy to dissolve with water, and it is easy to adhere to the polymer film; it contains high transparent acrylic optical properties such as light transmittance and haze; Because of the addition of ί, 'the nano-sized filler particles make it extremely easy to be compatible with the resin. The more the amount can increase the slipperiness of the polymer film, but it does not make the bonding agent play a very important role in the coating liquid. Role 7 200800598 The content of the aqueous binder in the coating liquid of the present invention is preferably from 1 to 5 % by weight. The coating liquid relating to the invention may further contain additives which are widely used, such as materials or dyes, other antistatic agents, agents, other flow agents, plasticizers, antioxidants and fillers. The coating liquid according to the present invention is applied to a substrate for optics by being applied to a poly-position, having high transparency, flexibility, excellent adhesion and slip properties. The coating liquid to which the present invention is applied is dried on a polymer film to have a yield of 0.001 to 0.5 Å / η η (micrometer), preferably 001 to 01 / / m. Further, the coating liquid according to the present invention has an antistatic residue mainly depending on the surface resistance of the polymer film, and can be detected by using the conventional surface with ADVANTEST, deleted 0A), and is suitable for the surface impedance of the present invention.
SqUare(Q/〇) ’ 較宜為1()9 Qhms Per Ν·(Ω/〇) ’ 最宜為 10 ohms per square( Ω /□) 〇 明有f之塗佈液’其防污撥水特性主要取決於塗有塗佈 合物蚊表面水接觸角，▼利用水接觸角分析脑（協和界 ’適用於本發明之表面水接觸角宜為狀〇以上 ’幸父且為90〜100，最宜為ι〇〇〇以上。 聚从料性主縣祕㈣塗佈液的 水口物朕之透先率及雲務度，可以利用光曇 NIPPON DENSHOKU、TC-MDPK)檢測，適用於太：；】 ，及曇霧度宜為8編上及5%以下，較宜為9()%以上及撕以^， 隶宜為92%以上及1%以下。 構成本發明之保護膜的聚合物膜，主要 ’以例如尼龍薄膜、聚苯乙稀薄膜、聚甲基丙稀酸酯薄;; ，二膜、聚丙烯薄膜、聚氯乙烯薄膜、聚對笨1甲酸 乙n猶寺具有透光率、價廉、可回收 ， 中最宜使用者為聚對苯二曱酸乙二酯薄膜。 1吏用/、 本發明所用的塗佈方法可採用傳統的滾塗（關副ing)、逆 8 200800598 ，向滾塗（Reverse roll coating )、輪轉凹印滾塗（Gravure roll coating ) • 、逆向輪轉凹印滾塗（Reverse gravure roll coating)、刷塗（Brush coating)、線桿拉塗（Wire_w_d r〇d(Meyer r〇d) c〇ating)、喷塗（ Spray coating)、氣刀塗佈（Air knife coating)及沾塗（Dipping)的 塗佈方式。除上述所謂離線（off_line)的傳統塗佈方式外，本發明 所採j塗佈方式亦可使用所謂線上（inline)的塗佈方式，以PET( 聚對苯二曱酸乙二酯薄膜)的生產方式為例，聚合物膜製造過程中 ，在聚合物膜尚未熱定型之前，塗佈以與本發明有關之塗佈液，塗 佈後聚合物膜進行定向延伸及加熱定型之步驟。以上述兩種塗佈方 • 法皆可得透光率在90%以上、曇霧度在3%以下，表面阻抗在1〇9〇/ □以下，表面水接觸角在90〇以上的聚合物處理膜。 【實施方式】 使用以下的貫施例，可更明確的說明本發明，然而本發明之 範疇並不受限於此等例子。 實施例及比較例 、，依照表一的組成物，其中所使用之量以重量％為基礎，藉由攪 _ 拌機充分攪拌後，可得塗佈液。如此而得的塗佈液，藉由逆向輪轉 凹印滾塗方式塗佈於南亞塑膠工業股份有限公司製造的ρΕΤ膜（型 號BS-21厚度38//m)，以熱風乾燥機在1〇〇。〇乾燥特定時間，而得 〇·〇3〜0·3μιη厚度之聚合物處理膜。 200800598SqUare(Q/〇) ' is preferably 1 () 9 Qhms Per Ν · (Ω / 〇) ' Best 10 ohms per square ( Ω / □) 〇 有 有 之 之 涂布 ' ' ' ' ' ' ' The characteristics mainly depend on the water contact angle of the coated surface of the coated mosquito, and the brain is analyzed by the water contact angle. The surface water contact angle suitable for the present invention is suitable for the above-mentioned father and is 90 to 100. It is most suitable for ι〇〇〇. The permeability and cloud degree of the sluice of the coating agent of the main county (4) coating liquid can be detected by the optical NIPPON DENSHOKU, TC-MDPK), suitable for: ;], and the haze should be 8 or less and 5% or less, more preferably 9 ()% or more and torn ^, should be more than 92% and less than 1%. The polymer film constituting the protective film of the present invention is mainly made of, for example, a nylon film, a polystyrene film, a polymethyl acrylate thin film; a second film, a polypropylene film, a polyvinyl chloride film, and a poly-pair. 1 Formic acid yueju Temple has light transmittance, low cost and recyclability. The most suitable user is polyethylene terephthalate film. The coating method used in the present invention can be carried out by conventional roll coating (off ing), reverse 8 200800598, reverse roll coating, Gravure roll coating, and reverse. Reverse gravure roll coating, brush coating, wire drawing (Wire_w_d r〇d (Meyer r〇d) c〇ating), spray coating, air knife coating (Air knife coating) and Dipping coating method. In addition to the above-mentioned so-called off-line conventional coating method, the coating method of the present invention can also use a so-called inline coating method with PET (polyethylene terephthalate film). For example, in the production process of the polymer film, before the polymer film is not heat-set, the coating liquid related to the present invention is applied, and the polymer film is subjected to the steps of orientation extension and heat setting. Polymers with a light transmittance of 90% or more, a haze of 3% or less, a surface impedance of 1〇9〇/□ or less, and a surface water contact angle of 90〇 or more can be obtained by the above two coating methods. Treat the film. [Embodiment] The present invention will be more specifically described by the following examples, but the scope of the invention is not limited thereto. EXAMPLES AND COMPARATIVE EXAMPLES According to the composition of Table 1, the amount of the composition used was sufficiently stirred by a stirrer based on the weight % to obtain a coating liquid. The coating liquid thus obtained is applied to a ρ ΕΤ film (model BS-21 thickness 38//m) manufactured by Nanya Plastics Co., Ltd. by reverse rotogravure roll coating, with a hot air dryer at 1 〇〇. . The concrete was dried for a specific period of time to obtain a polymer treated film having a thickness of 〜·3 to 0.3 μm. 200800598
實施例 氣素界面活性劑 02 1.8 水性連結劑Examples Gasoline surfactant 02 1.8 Aqueous linker
9.51 xlO9 0.25 02 L8 4.78χ 109 1·86χ ιλ9 106 106 4 0.25 0·1 1·8 Ι.22χ 1Λ9 104 0.25 0.05 0.06 02 0.06 0.05 比較例 2 0.12 0.1 0.25 0.2 1.8 9·1χ ΙΟ8 102 0.45/ 0.36 5.0 1.58χ ΙΟ9 8.54χ 105 103 3.71χ ΙΟ9 104 1·07χ λ9 1069.51 xlO9 0.25 02 L8 4.78χ 109 1·86χ ιλ9 106 106 4 0.25 0·1 1·8 Ι.22χ 1Λ9 104 0.25 0.05 0.06 02 0.06 0.05 Comparative Example 2 0.12 0.1 0.25 0.2 1.8 9·1χ ΙΟ8 102 0.45/ 0.36 5.0 1.58χ ΙΟ9 8.54χ 105 103 3.71χ ΙΟ9 104 1·07χ λ9 106
表面阻抗(Ω/Ε]) ' ----- 水接觸角(度） 光透過率(％) 106 90.5 90.2Surface impedance (Ω/Ε]) ' ----- Water contact angle (degrees) Light transmittance (%) 106 90.5 90.2
與聚合物膜之接著性 摩擦係數(靜摩擦/動摩檫） 〇 〇 89.5 89.7 89.7 92.0 88.1 89.2 89.7 1.8 1.6 1.4 1.8 1.4 1.5 1.6 〇 〇 〇 〇 0.44/ 0.35 0.45/ 0.35 0.42/ 0.32 0.40/ 0.31 0.41/ 0.31 0.45/ 0.36 0.47/ 0.38 0.52/ 0.41 的塗佈液中之g嗔二f P 返著本电明之供偏光片用表面保護膜而用 氟素界面活性劑^ ^trcn p)用量的增加，表面阻抗隨之降低， 水性連結劑在塗騎巾，·===觸肖即㈣顯效果；而其中的 學性質如透光率及曇不。’聚合物膜之接著性，並且使光 ίοAdhesive coefficient of friction with polymer film (static friction / dynamic friction) 〇〇89.5 89.7 89.7 92.0 88.1 89.2 89.7 1.8 1.6 1.4 1.8 1.4 1.5 1.6 〇〇〇〇0.44/ 0.35 0.45/ 0.35 0.42/ 0.32 0.40/ 0.31 0.41/ 0.31 0.45 / 0.36 0.47 / 0.38 0.52 / 0.41 in the coating liquid g 嗔 2 f P returned to the surface of the surface of the polarizer for the polarizer for the use of fluorochemical surfactant ^ ^ trcn p) increase in the amount of surface The impedance is reduced, and the water-based bonding agent is applied to the riding towel, and the effect is such as light transmittance and ambiguity. 'The adhesion of the polymer film, and make the light ίο