TWI312354B

TWI312354B - Protective film for a polarizing plate,manufacturing method thereof, and polarizing plate using the same

Info

Publication number: TWI312354B
Application number: TW92123415A
Authority: TW
Inventors: Hironobu Shinohara
Original assignee: Nitto Denko Corporatio
Priority date: 2003-08-26
Filing date: 2003-08-26
Publication date: 2009-07-21

Description

1312354 玖、發明說明：【發明所屬之技術領域】本發明係關於一種聚合物薄膜，其具有黏著於其表導電聚合物。詳而言之，本發明係關於一種導電聚合膜，其包含聚合物薄膜及黏著於其表面之導電聚合物聚合物薄膜包含乙醯纖維素材料或降冰片烯材料，且電聚合物層之厚度為3#m或以下。該導電聚合物薄膜見光穿透度為78%或以上，且其表面電阻率為103〜10 平方面積。該導電聚合物薄膜具高透明性及抗靜電功電磁波遮蔽功能，且被使用於例如液晶顯示器（L C D ) 示器。該導電聚合物薄膜特別適合使用作為偏光板之薄膜。【先前技術】偏光板所具有之構造，係例如將聚乙烯醇（P V A ) 延伸，於該延伸薄膜上黏著並固定碘或染料而製備偏膜，並於該偏光薄膜之兩側黏著含有三乙醯纖維素（之薄膜，藉此強化PVA薄膜之強度，並防止PVA薄膜水而造成性質改變。TAC之透明性極佳且雙折射低，易黏著於P V A。因此，T A C薄膜向來被使用作為偏光薄保護薄膜。近年來，隨著液晶顯示器尺寸之增加，即使於TAC 亦有因吸水所造成之某種程度的尺寸改變之問題發生此，具有良好之透明性、低雙折射且低吸水性之降冰材料被研究來取代TAC。 312/發明說明書(補件)/92-11 /92123415 面之物薄。該該導之可 ΙΖΩ / 能或之顯保護薄膜光薄 TAC ) 因吸並容膜之中，。因片稀 5 1312354 另一方面，在顯示器中（例如CRT、EL或PDP，包括該類顯示器所發射出來之電磁波對人體具有不良影此，必須遮蔽這些電磁波。另外，當具有前述之電蔽功能之薄膜被裝設於顯示器内部或外部時，該薄具有極佳之透明性、低雙折射、高強度、高耐熱性吸水性。因此，尋找具有電磁波遮蔽功能以及上述薄膜的需求一直存在著。顯示器之電磁波可藉由於顯示器前方裝設具有之材料來遮蔽。一般而言，高透明度且導電材料可或沉積之方法，將I T 0或類似之物質黏著於聚合物而獲得。然而，該等方法之生產性低，且材料本身造成導入導電性之薄膜高價之問題。此外，I T 0之黃。隨著LCD顏色之進展，上述之顏色亦成為問題當將導入導電性之材料裝設於如L C D、E L或P D P 器時，因靜電造成之灰塵附著於此類材料是一大問此，其抗靜電功能亦進一步被要求著。習知之導電聚合物材料為聚苯胺衍生物、聚吡咯以及聚噻吩衍生物。當嘗試自該等衍生物取得高時，會產生聚苯胺顏色變綠及聚°比咯顏色變灰等問【發明内容】本發明乃著眼於上述問題而提出者。緣是，本發明之目的在於提供一種低價之導電薄可克服先前技術中之問題點，即便使用於例如LCD 器亦無透明性之問題，同時兼備抗靜電功能與電磁 312/發明說明書(補件)/92-11 /½ 123415 LCD )-響。因磁波遮膜必須以及低性質之導電性由錢鍍薄膜上昂貴，色調偏點0 等顯示題。因衍生物電阻率題。膜，其之顯示波遮蔽 6 1312354 功能。本發明提供一種導電聚合物薄膜，其包含聚合物薄膜及黏著於其表面之導電聚合物。此種導電聚合物薄膜具有 78%或以上之可見光透光度，且其表面電阻率為 103-1012 Ω /平方面積。本發明之目的可藉由以下方法達成：使用聚噻吩材料作為導電聚合物，並控制導電聚合物層之厚度在 3 # m或其以下，且使用乙醯纖維素材料或降冰片烯材料作為聚合物薄膜材料。【實施方式】以下詳細說明本發明。本發明中所使用之導電聚合物係由將噻吩及/或噻吩衍生物聚合所得之均聚物或共聚物。導電聚合物係為均聚物或共聚物，其包含至少一個由下述化學式（1)、（ II)、（ III) 及（VI)所示之聚合單元。該導電聚合物可為含有少量除上述之聚合單元之外的聚合單元之共聚物，以作為共聚合1312354 发明Inventive Description: TECHNICAL FIELD The present invention relates to a polymer film having a conductive polymer adhered thereto. More specifically, the present invention relates to a conductive polymer film comprising a polymer film and a conductive polymer polymer film adhered to the surface thereof comprising an acetaminophen material or a norbornene material, and the thickness of the electropolymer layer It is 3#m or below. The conductive polymer film showed a light transmittance of 78% or more and a surface resistivity of 103 to 10 square meters. The conductive polymer film has high transparency and antistatic work electromagnetic wave shielding function, and is used, for example, in a liquid crystal display (L C D ) display. The conductive polymer film is particularly suitable for use as a film of a polarizing plate. [Prior Art] The polarizing plate has a structure in which, for example, polyvinyl alcohol (PVA) is stretched, an iodine or a dye is adhered to the stretched film to prepare a polarizing film, and three sides of the polarizing film are adhered thereto.薄膜 Cellulose (the film, which strengthens the strength of the PVA film and prevents the PVA film from changing the properties of the water. TAC has excellent transparency and low birefringence, and is easy to adhere to PVA. Therefore, TAC film has been used as polarized light. Thin protective film. In recent years, with the increase in the size of liquid crystal displays, even TAC has a certain degree of dimensional change due to water absorption, which has good transparency, low birefringence and low water absorption. The ice-reducing material was studied to replace the TAC. 312/Invention Manual (Supplement)/92-11 /92123415 The surface of the material is thin. The guide can be ΙΖΩ / can or the protective film thin film TAC) Among them, On the other hand, in the display (such as CRT, EL or PDP, including the electromagnetic waves emitted by such displays have adverse effects on the human body, these electromagnetic waves must be shielded. In addition, when having the aforementioned electrical shielding function When the film is mounted inside or outside the display, the film has excellent transparency, low birefringence, high strength, and high heat resistance. Therefore, there has been a demand for finding an electromagnetic wave shielding function and the above film. The electromagnetic wave of the display can be shielded by the material provided in front of the display. Generally, a highly transparent and conductive material can be deposited or deposited by adhering IT 0 or the like to the polymer. However, such methods The productivity is low, and the material itself causes a problem of high cost of introducing a conductive film. In addition, the yellow color of IT 0. As the color of the LCD progresses, the above-mentioned color also becomes a problem when a material into which conductivity is introduced is mounted on, for example, an LCD. , EL or PDP, dust caused by static electricity attached to such materials is a big question, its anti-static function is also Further, it is required that the conductive polymer materials are polyaniline derivatives, polypyrroles, and polythiophene derivatives. When attempting to obtain high from such derivatives, polyaniline color becomes green and polypyrene color changes. The present invention has been made in view of the above problems. It is an object of the present invention to provide a low-cost conductive thin that overcomes the problems of the prior art even when used, for example, in an LCD device. The problem of transparency, together with antistatic function and electromagnetic 312 / invention manual (supplement) / 92-11 / 1⁄2 123415 LCD) - ring. Because of the magnetic wave mask and the low conductivity, the conductivity is expensive, and the color tone is 0. Due to the derivative resistivity problem. The membrane, which exhibits a wave shield 6 1312354 function. The present invention provides a conductive polymer film comprising a polymer film and a conductive polymer adhered to the surface thereof. The conductive polymer film has a visible light transmittance of 78% or more and a surface resistivity of 103 to 1012 Ω / square. The object of the present invention can be attained by using a polythiophene material as a conductive polymer and controlling the thickness of the conductive polymer layer to be 3 #m or less, and using an acetonitrile cell material or a norbornene material as a polymerization. Film material. [Embodiment] Hereinafter, the present invention will be described in detail. The conductive polymer used in the present invention is a homopolymer or copolymer obtained by polymerizing thiophene and/or thiophene. The conductive polymer is a homopolymer or a copolymer comprising at least one polymerized unit represented by the following chemical formulas (1), (II), (III) and (VI). The conductive polymer may be a copolymer containing a small amount of polymerized units other than the above-mentioned polymerized unit, as a copolymerization

TlO 一早7L 。TlO is 7L early.

7 312/發明說明書(補件)/92-11 /92123415 13123547 312/Invention Manual (supplement)/92-11 /92123415 1312354

m=l- 4 — (Ill)m=l- 4 — (Ill)

m=l- 4 於化學式（I )及（I I )中，R 1及R2分別表示：氫原子、碳數2 0或以下之脂肪族烴基、碳數2 0或以下之脂環族烴基、碳數2 0或以下之芳香族烴基、羥基、具末端羥基之基團、烷氡基、具末端烷氧基之基團、羧基、具末端羧基之基團、羧酯基、具末端羧酯基之基團、酯基、具末端酯基之基團、ί黃酸基、具末端績酸基之基團、績si基、具末端磺醯基之基團、亞磺醯基、具末端亞磺醯基之基團、醯基、具末端醯基之基團、胺基、具末端胺基之基團、具部份或全部氫原子被取代之胺基的基團、具部份或全部氫原子被取代之末端胺基的基團、具末端胺曱醯基之基團、具部份或全部氫原子被取代之胺曱醯基的基團、具部份或全部氫原子被取代之末端胺甲醯基的基團、鹵原子、磷酸基、具末端磷酸基之基團、環氧乙烷基、或具末端環氧乙烷基之基團。於化學式（I I )及（V I )中，Y _表示陰離子。陰離子可例示如齒離子、磺酸離子及羧酸離子。 8 312/發明說明書(補件)/92-11/92123415 1312354 為進一步增加導電性，可於導電聚合物中加入摻雜物，例如於每1 0 0重量份之導電聚合物中加入0 . 1 ~ 5 0 0重量份之噻吩。摻雜物可列舉如：L i C 1、R3 C 0 0 L i ( R3 :具 1 ~ 3 0 個碳原子之飽和烴基；以下亦同）、R3S〇3Li、R3C00Na、 R3S〇3Na、R3COOK、R3S〇3K、四乙基銨、I2、BF3Na、BFda、 HCl〇4、CF3SO3H、FeCls、四氰嗜琳、Na2Bi〇Cli。、酜青素、卟啉、麩胺酸、磺酸烷鹽、聚苯乙烯磺酸鹼式鹽共聚物、聚苯乙烯磺酸陰離子、苯乙烯磺酸以及苯乙烯磺酸陰離子聚合物。該等可單獨使用或混合兩種以上使用。導電聚合物中可調配接著劑樹脂，以更進一步增進聚合物薄膜及導電聚合物間之黏著性。接著劑樹脂無特別限定，只要適當選擇對於該種聚合物薄膜有極佳黏著性者即可。使用之接著劑樹脂可列舉如：聚酯樹脂、丙烯酸系樹脂、丙烯酸系改質之聚酯樹脂、胺基甲酸酯樹脂、乙烯醋酸酯、氣乙烯、聚乙烯醇、聚乙烯乙烯醋酸酯及有機矽酸鹽。該等接著劑樹脂可單獨使用或混合兩種以上使用。本發明中之導電聚合物層係具有 1 0 3 ~ 1 0 12 Ω /平方面積之表面電阻率的塗層，其可經由將含有由噻吩及/或噻吩衍生物聚合而得的導電聚合物之水溶性塗層液塗布於聚合物薄膜，並將該塗布層乾燥並硬化而得。其表面電阻率以 104~108Ω /平方面積為佳。若表面電阻率低於 103Ω /平方面積，則必須增加塗層之厚度，否則接著劑之量會不足而使得塗層易裂開。相反地，若表面電阻率大於1 0 12 Q /平方面積，則其抗靜電效果或電磁波遮蔽效果變得不足。 9 312/發明說明書(補件)/92- η /92123415 1312354 由塗布法所形成之導電聚合物層，最好以下述方法製備：塗布含有組成為1〜9 5 %重量比（較佳為2 ~ 7 0 %重量比）之導電聚合物水溶液以及5 ~ 9 9 %重量比（較佳為3 0 ~ 9 8 %重量比）之接著劑樹脂，再將之乾燥並硬化。當導電聚合物與接著劑樹脂之比例位在上述之範圍内時，聚合物薄膜與導電聚合物間之黏著性佳，因此其抗靜m=l - 4 In the chemical formulae (I) and (II), R 1 and R 2 each represent a hydrogen atom, an aliphatic hydrocarbon group having a carbon number of 20 or less, an alicyclic hydrocarbon group having a carbon number of 20 or less, and carbon. Number of 20 or less aromatic hydrocarbon groups, hydroxyl groups, groups having terminal hydroxyl groups, alkanoyl groups, groups having terminal alkoxy groups, carboxyl groups, groups having terminal carboxyl groups, carboxyl ester groups, terminal carboxyl ester groups a group, an ester group, a group having a terminal ester group, a leucovorin group, a group having a terminal acid group, a group having a terminal sulfonyl group, a sulfinyl group, and a terminal arylene group a group of a sulfonyl group, a fluorenyl group, a group having a terminal thiol group, an amine group, a group having a terminal amino group, a group having a partial or all hydrogen atom substituted, and a part or all of a group in which a hydrogen atom is substituted with a terminal amine group, a group having a terminal amine sulfhydryl group, a group having an amine sulfhydryl group partially or wholly substituted with a hydrogen atom, and a part or all of hydrogen atoms are substituted a terminal group of a terminal mercapto group, a halogen atom, a phosphate group, a group having a terminal phosphate group, an oxirane group, or a group having a terminal oxirane group. In the chemical formulas (I I ) and (V I ), Y _ represents an anion. The anion can be exemplified by a tooth ion, a sulfonate ion, and a carboxylic acid ion. 8 312 / invention specification (supplement) / 92-11/92123415 1312354 To further increase the conductivity, a dopant may be added to the conductive polymer, for example, 0.10 parts by weight of the conductive polymer is added to 0.1. ~ 500 parts by weight of thiophene. Examples of the dopant include: L i C 1 , R 3 C 0 0 L i ( R 3 : a saturated hydrocarbon group having 1 to 30 carbon atoms; the same applies hereinafter), R 3 S 〇 3 Li, R 3 C 00 Na, R 3 S 〇 3 Na, R 3 COOK, R3S〇3K, tetraethylammonium, I2, BF3Na, BFda, HCl〇4, CF3SO3H, FeCls, tetracyanoline, Na2Bi〇Cli. Anthraquinone, porphyrin, glutamic acid, sulfonic acid alkyl salt, polystyrene sulfonate basic salt copolymer, polystyrene sulfonate anion, styrene sulfonic acid, and styrene sulfonic acid anionic polymer. These may be used alone or in combination of two or more. An adhesive resin may be blended in the conductive polymer to further enhance the adhesion between the polymer film and the conductive polymer. The binder resin is not particularly limited as long as it is appropriately selected to have excellent adhesion to the polymer film. Examples of the binder resin to be used include a polyester resin, an acrylic resin, an acrylic modified polyester resin, a urethane resin, an ethylene acetate, a gas ethylene, a polyvinyl alcohol, a polyethylene vinyl acetate, and the like. Organic citrate. These adhesive resins may be used singly or in combination of two or more. The conductive polymer layer in the present invention is a coating having a surface resistivity of an area of from 1 0 3 to 1 0 12 Ω/square, which can be via a conductive polymer obtained by polymerizing a thiophene and/or a thiophene derivative. The water-soluble coating liquid is applied to a polymer film, and the coating layer is dried and hardened. The surface resistivity is preferably 104 to 108 Ω / square. If the surface resistivity is less than 103 Ω / square area, the thickness of the coating must be increased, otherwise the amount of the adhesive will be insufficient to cause the coating to crack. On the contrary, if the surface resistivity is larger than 10 12 Q / square area, the antistatic effect or the electromagnetic wave shielding effect becomes insufficient. 9 312 / invention specification (supplement) / 92- η /92123415 1312354 The conductive polymer layer formed by the coating method is preferably prepared by the following method: the coating contains a composition of 1 to 95% by weight (preferably 2) ~ 70% by weight of the aqueous conductive polymer solution and 5 to 99% by weight (preferably 30 to 98% by weight) of the adhesive resin, which are dried and hardened. When the ratio of the conductive polymer to the adhesive resin is within the above range, the adhesion between the polymer film and the conductive polymer is good, so that it is resistant to static

V 電效果佳，而其黏著性與抗磨損性亦改善。含有導電聚合物與接著劑樹脂之組成物可由周知之混合法獲得。亦可使用以導電聚合物覆蓋極細之接著劑樹脂顆粒表面之方法，或使用將導電聚合物之官能基與接著劑樹脂之官能基進行化學鍵結之方法。當以調整黏著性、耐溶劑性、耐水性及其同類為目的時，可於導電聚合物層中選擇性地加入環氧樹脂、乙烯樹脂、聚醚樹脂、水溶性樹脂或類似物作為成分之一。此外，為增加塗層之滑動性、抗結塊性等，亦可加入0 . 0 0 1 ~ 5 %重量比之平均粒徑約 0 . 0 1 ~ 2 0 // m之無機或有機極細粒子作為潤滑劑。該種極細粒子包括：如石夕石、礬土、氧化鈦、碳黑、高嶺土或碳酸鈣等無機極細粒子，以及聚苯乙烯樹脂、交聯聚苯乙烯樹脂、丙烯酸系樹脂、交聯丙烯酸系樹脂、三聚氰胺樹脂、碎氧樹脂、氟樹脂、尿素樹脂或苯11 瓜胺 (benzoguanamine)樹脂等有機極細粒子。該等有機極細粒子可為熱塑性樹脂或熱固性樹脂，只要係在塗布步驟中可保持某種程度之極細粒子狀態者即可。亦可於導電聚合 10V electricity is good, and its adhesion and wear resistance are also improved. The composition containing the conductive polymer and the adhesive resin can be obtained by a well-known mixing method. It is also possible to use a method in which the surface of the extremely fine binder resin particles is covered with a conductive polymer, or a method in which a functional group of the conductive polymer is chemically bonded to a functional group of the adhesive resin. When the purpose of adjusting adhesion, solvent resistance, water resistance, and the like is selected, an epoxy resin, a vinyl resin, a polyether resin, a water-soluble resin or the like may be selectively added to the conductive polymer layer as a component. One. In addition, in order to increase the slidability and anti-caking property of the coating, an inorganic or organic fine particle having an average particle diameter of about 0. 0 1 to 2 0 // m may be added in a weight ratio of 0.001 to 5%. As a lubricant. The ultrafine particles include inorganic fine particles such as Shishishi, bauxite, titanium oxide, carbon black, kaolin or calcium carbonate, and polystyrene resin, crosslinked polystyrene resin, acrylic resin, and crosslinked acrylic acid. Organic fine particles such as resin, melamine resin, hydroxy resin, fluororesin, urea resin or benzoguanamine resin. These organic ultrafine particles may be a thermoplastic resin or a thermosetting resin as long as they are capable of maintaining a certain degree of extremely fine particle state in the coating step. Can also be used in conductive polymerization 10

麟 312/發明說明書(補件)/92-11/92123415 1312354 物層加入導電性填料，例如氧化錫極細粒子或氧化銦極細粒子，以增加其導電性。如果需要，亦可加入上述極細粒子以外之界面活性劑、抗氧化劑、著色劑、顏料、螢光性亮光劑、塑化劑、交聯劑、有機潤滑劑、紫外線吸收劑、抗靜電劑等。導電聚合物層係以含有導電聚合物之水性塗布液形成，該水性塗布液視需要亦可含有接著劑、摻雜物、及其他添加劑。水性塗布液之固體成分濃度一般而言係為 0 .卜3 0 %重量比，以卜2 0 %重量比為佳。當固體成分濃度界於該範圍内時，水性塗布液之黏度適合進行塗布。水性塗布液可以水溶液、水性分散液、乳化液等之任一形式使用。可藉由於水性塗布液中加入水溶性溶劑以增加溶劑之揮發速率，例如加入醇類（如甲醇、乙醇、異丙醇或乙二醇）或酮類（如丙酮或丁酮）。特別自醇類與水具有高相容性且可改善潤滑性質之觀點而言，以使用醇類為佳。在對水性塗布液不具不利影響之前提下，亦可含有其它溶劑。聚合反應亦可以如下方式進行：於導電聚合物層形成之基材表面塗布氧化劑，塗布程度為數# m，並於氣體狀態下使單體與該氧化劑塗布層接觸，藉以於該基材上形成導電聚合物層。在本發明中，導電聚合物層係以於透明聚合物薄膜上塗布上述塗布液之方法而形成。該黏著有導電聚合物層之聚合物薄膜（亦即導電聚合物薄膜）係被使用作為光學薄膜，特別是偏光板之保護膜。因此，該被使用之導電聚合物薄 11Lin 312/Invention Manual (Supplement)/92-11/92123415 1312354 A conductive filler such as tin oxide fine particles or indium oxide fine particles is added to the layer to increase its conductivity. If necessary, a surfactant other than the above ultrafine particles, an antioxidant, a colorant, a pigment, a fluorescent brightener, a plasticizer, a crosslinking agent, an organic lubricant, an ultraviolet absorber, an antistatic agent, or the like may be added. The conductive polymer layer is formed of an aqueous coating liquid containing a conductive polymer, and the aqueous coating liquid may further contain an adhesive, a dopant, and other additives as needed. The solid content concentration of the aqueous coating liquid is generally 0. The weight ratio of 30% by weight is preferably 0.2% by weight. When the solid content concentration is within this range, the viscosity of the aqueous coating liquid is suitable for coating. The aqueous coating liquid can be used in any form such as an aqueous solution, an aqueous dispersion, or an emulsion. The rate of volatilization of the solvent can be increased by adding a water-soluble solvent to the aqueous coating liquid, for example, an alcohol such as methanol, ethanol, isopropanol or ethylene glycol or a ketone such as acetone or methyl ethyl ketone. It is preferable to use an alcohol from the viewpoint of high compatibility with alcohol and water and improvement of lubricating properties. It may be added before it has an adverse effect on the aqueous coating liquid, and may contain other solvents. The polymerization reaction can also be carried out by applying an oxidizing agent to the surface of the substrate on which the conductive polymer layer is formed, the degree of coating is several #m, and contacting the monomer with the oxidizing agent coating layer in a gaseous state, thereby forming a conductive layer on the substrate. Polymer layer. In the present invention, the conductive polymer layer is formed by a method of coating the above coating liquid on a transparent polymer film. The polymer film (i.e., a conductive polymer film) to which the conductive polymer layer is adhered is used as an optical film, particularly a protective film for a polarizing plate. Therefore, the conductive polymer used is thin 11

m 312/發明說明書(補件)/92-11/92123415 1312354 膜之可見光透光度以及雙折射係重要之性質。可見光透光度愈高愈佳。可見光透光度通常在 78%或以上，而以 82% 或以上較佳，8 5 %或以上更佳。雙折射則愈低愈佳。雙折射通常在lOOnm或以下，而以50nm或以下更佳。導電聚合物薄膜以同時具有該等性質者為佳。由於乙醯纖維素薄膜與降冰片烯薄膜具可見光透光度、雙折射及黃色色調，因此被用來作為上述聚合物薄膜。乙醯纖維素薄膜可舉例如三乙醯纖維素薄膜（T A C 薄膜）、使用纖維素纖維作為原料之二醋酸纖維素薄膜、以及該等之改質薄膜。該等薄膜通常例如以下述方法製得：將纖維素纖維溶解於適當之溶劑中，如亞甲基氣，將所得之溶液塗布於不銹鋼片或適當之聚合物薄膜上，除去溶劑並乾燥該薄膜。適用於本發明之降冰片烯薄膜並無特別限制，只要係以至少一種具降冰片烯結構之單體所製得之聚合物即可。例如，該聚合物可由將具有降冰片烯結構之單體予以開環聚合而得，亦可在氫化觸媒之存在下將殘存雙鍵之一部份或全部氫化而得。聚合物之典型的例子包括：由如 J P - A 63-218726、5-25220 或 9-183832 中所述方法製得之 ZE0NEX 或ZEONOR(商品名，NipponZeon(股）製）’以及由如JP-A 5 - 9 7 9 78或1 - 2 4 0 5 1 7中所述方法製得之ART0N (商品名， J S R公司製）。該聚合物之另一例為，將具降冰片烯結構之單體及複數種具雙鍵之其他單體以周知方法進行加成聚合所得之聚合 12 312/發明說明書(補件)/92-11/92123415 1312354 物。此種聚合物的例子包括由如JP-A 6-107735、62-252406 或 8-259629中所述方法製得之APEL(商品名，三井化學 (股）製）以及TOPAS (商品名，Hoechst AG製）。由上述聚合物製得薄膜之方法可為周知之方法。例如，薄膜可以洗鑄法製造，將聚合物溶於可充分溶解聚合物之溶劑中（特別係鹵系溶劑，例如亞甲基氣，或芳香族或丙烯酸系溶劑），再將所得之聚合物溶液塗布於金屬（例如不銹鋼）製板或聚合物（如聚酯）薄膜上，將溶劑除去後再予以乾燥。此薄膜亦可以擠壓成形法製造，以熱將聚合物熔融，並將熔融聚合物擠出於金屬板，再將其乾燥。於製造乙醯纖維素薄膜或降冰片烯薄膜時，可視需要於聚合物中加入各種添加劑，例如抗氧化劑、紫外線吸收劑、紫外線安定劑、著色劑、潤滑劑、抗靜電劑、顏料、染料、纖維或分散劑等。當薄膜係被使用作為偏光板之保護膜時，以使用含有抗氧化劑、紫外線吸收劑及/或紫外線安定劑之薄膜為佳。所製得之薄膜之表面可視目的而塗布適當之材料。可於薄膜表面塗布例如丙烯酸系、胺基甲酸酯或丙烯酸胺基曱酸酯之U V硬化劑或熱固性硬膜（h a r d c 〇 a t )材料、環氧系硬膜材料、以及聚矽氧烷系硬膜材料等，以防止其表面刮傷。亦可使用於其表面塗布該等含S i 0 2或礬土等極細粒子之硬膜材料所得的薄膜，藉以降低眩光性，亦即，使用具有反強光硬膜的薄膜。當薄膜被用作為偏光板之保護膜時，以使用具有上述硬膜或反強光硬膜之薄膜較佳。 13 312/發明說明書(補件)/92-11/92123415 1312354 將塗布液塗布於聚合物薄膜之方法可使用周知之塗布法。塗布方法之例包括：輥塗布、凹版塗布、網版印刷、膠版（〇 f f - s e t )印刷、微凹版塗布、反相塗布、輥刷、喷霧塗布、氣刀塗布、充注法及簾狀塗布。該等方法可單獨使用或結合兩種或以上使用。導電聚合物層之厚度為 0.005~3仁111，以 0.01~l/ztn為佳，又以0 . 0 2 ~ 0 . 5 /z m更佳。若厚度過小，無法獲得充分之抗靜電效果。相反地，若厚度過大，則塗布薄膜可能碎裂，或抗結塊性質可能降低。導電聚合物層可形成於聚合物薄膜之單面或兩面。上述硬膜材料或反強光硬膜可塗布於所獲得之形成有導電聚合物層之聚合物薄膜。另外，亦可視所欲之目的而使用各種周知之塗布，如抗屈光膜、抗污膜或感壓性黏著膜。當導電聚合物層形成於薄膜之單面，可視目的而於相反面使用硬膜、反強光硬膜、抗屈光膜、抗污膜或感壓性黏著膜。該等塗布法可單獨使用或組合兩種或以上而使用。於LCD中，通常於液晶前後各裝設兩片偏光板。本發明之薄膜可使用作為兩片偏光板之四片保護膜。然而，並不是必定要使用四片薄膜，依據目的亦可使用一、二或三片薄膜作為保護膜。當使用複數片薄膜時，該等薄膜不需具有相同之電阻率，可根據目的選擇適用之聚合物薄膜。若考慮電磁波遮蔽功能，則自效果和成本之觀點而言，將薄膜使用於最外層之保護膜為佳。以下參照實施例，更詳盡地說明本發明之内容，但本發 14 312/發明說明書(補件)/92-11 /92123415 1312354 明並不僅限於該等實施例。 (實施例1 ) 於 1 kg之含 20重量％異丙醇的水中，溶解：於以1:1 之莫耳比將聚苯乙烯磺酸離子與聚苯乙烯磺酸共聚合所得之材料 3 0重量份中，滴入 1 6重量份之二氧乙烯聚噻吩 (Baytron P Η，拜耳公司製）而製得之導電聚合物 2 0 g ; 以1 : 1 : 1重量比之比例混合丙烯酸系樹脂、胺基甲酸酯樹脂以及聚乙烯醇所得之接著劑1 0 0 g ;以及作為非離子型界面活性劑之聚氧乙烯壬基苯酚醚5g ;獲得水性塗布液1。將此塗布液以溝槽式塗布機塗布於厚度為8 0 # m之三乙醯纖維素薄膜（T AC薄膜），並於1 0 (TC下進行乾燥。所製得之導電聚合物薄膜之厚度為 0.11/im。該薄膜之性質示於下表1中。與下述未塗布該導電聚合物溶液之比較例1進行比較，很明顯地看出，雖經塗布後，1 0 Μ Ω /平方面積以上之表面電阻率降低至8 X 1 05 Ω /平方面積，因而導電度增加，但總太陽能透明度及雙折射大致上並未減低，而黃度則相反地降低。上述情事表示，即使該薄膜被設置於LCD内部，特別是即使被用作為偏光板之保護膜，該薄膜對光學性質並無不利影響，黃度甚至受到改善，且因此導致電磁波遮蔽功能或抗靜電功能增加。 (比較例1 ) 在未塗布導電聚合物溶液之情形下，測定實施例1中之 TAC薄膜之諸性質。所得到之結果示於下表1中。 15 312/發明說明書(補件)/92-11/92123415 1312354 (實施例2 ) 將分散有極細矽石之紫外線可硬化丙烯酸系硬膜材料塗布至厚度 8 0 /z m之 T A C薄膜上，以製備經抗眩光處理 (antiglare-treated)之薄膜，使得該薄膜之霧值（Haze value)為 27.1%，以及於60°角之亮度為 34.3%。將實施例1中所獲得之水性塗布液1，以相同於實施例1之方法塗布於上述製得之薄膜表面。所得之導電聚合物層之厚度為0 . 1 2 // m。此薄膜之諸性質示於下表2。下述比較例2中顯示當未塗布導電聚合物溶液時之各特徵值。與比較例2進行比較，很明顯地看出，雖經塗布後， 10Ι4Ω /平方面積以上之表面電阻率降低至 7χ 105Ω /平方面積，因而導電度增加，但總太陽能透明度及雙折射大致上並未改變，而黃度則改善。此外，尚可很明顯地看出，即便於抗眩光處理層上塗布導電聚合物溶液，霧值與亮度大致上並未改變。從該等結果中可知，即使將塗布有本發明之導電聚合物的抗眩光處理 TAC薄膜設置於 LCD之内部，抗眩光處理效果仍可維持，而光學性質未受不良影響，且可表現出電磁波遮蔽功能及抗靜電功能，黃度則相反地被改善。 (比較例2 ) 在未塗布導電聚合物溶液之情形下，測定實施例2中之抗眩光處理TAC薄膜之諸性質。所得到之結果示於下表2 中。 (實施例3 ) 16 312/發明說明(補件)/92-11 /92123415 1312354 除了所使用之導電聚合物改變為 1 〇 g，其餘均如同實施例1之方法來製備塗布薄膜。所得之導電聚合物層厚度為 0 . 1 2 // m。此薄膜之諸性質示於下表1中。 (實施例4 ) 除了導電聚合物層厚度改變為其餘均如同實施例1之方法來製備塗布薄膜。所得之此薄膜之諸性質示於下表1中。 (實施例5 ) 於降冰片烯材料（商品名「A R Τ Ο N」，J S R公司製）製、厚度1 0 0 /z m之薄膜上塗布實施例1中所使用之相同水性塗布液1。所得之導電聚合物層厚度為0.10/zm。此薄膜之諸性質示於下表1中。 (比較例3 ) 在未塗布水性塗布液之情形下，測定實施例5中所使用薄膜之諸性質。所得到之結果示於下表1中。 (實施例6 ) 除了薄膜改變為厚度 100/zm之抗眩光處理 ARTON薄膜，以相同於實施例5之方法塗布水性塗布液。所得之導電聚合物厚度為O.ll/zm。此薄膜之諸性質示於下表2中。 (比較例4 ) 在未塗布水性塗布液之情形下，測定實施例6中所使用薄膜之諸性質。所得到之結果示於下表2中。 (實施例7 ) . 除了將薄膜改變為厚度1 0 0 /2 m、以降冰片烯材料（商品 17 312/發明說明書(補件)/92-l 1/92123415 1312354 名「ZEONOA」，Nippon Zeon (股）製）製成、並以如同實施例6之方法進形抗眩光處理，其餘均如同實施例6之方法製得塗布薄膜。所得之導電聚合物層厚度為〇 . 1 2 /z m。此薄膜之性質示於下表2中。 (比較例5 ) 在未塗布水性塗布液之情形下，測定實施例7中所使用薄膜之諸性質。所得到之結果示於下表2中。表1 實施例1 實施例3 實施例4 比較例1 實施例5 比較例3 薄膜 TAC TAC TAC TAC ART0N ART0N 導電聚合物層厚度 (Αί Π1 ) 0. 11 0.12 1. 2 無 0.10 無表面電阻率 (Ω /平方面積） 8x 105 4x 109 6x 104 > 1 014 2x 106 > 1 014 黃度b* 0.25 0.35 0.17 0.40 0. 30 0.45 總太陽能量透明度（％ ) 92. 1 92. 3 90.0 92.3 92. 7 92.6 雙折射 (nm ) 10 10 12 10 15 16 表2 實施例2 比較例2 實施例6 比較例4 實施例7 比較例5 薄膜 TAC TAC ART0N ART0N ZEN0R ZEN0R 導電聚合物層厚度 (# m ) 0. 12 無 0. 1 1 無 0.12 無表面電阻率 (Ω /平方面積） 7x 105 > 1 014 7x 105 >10“ 6x 105 > 1 014 黃度b* 0. 50 0.65 0.55 0.71 0.77 0. 93 總太陽能量透明度（％ ) 91.3 91.4 92. 0 92. 2 91.5 91.9 雙折射 (nm ) 11 12 16 17 17 19 霧值（％ ) 25.9 27. 1 26. 6 27. 3 25.3 26.4 60°角亮度 (% ) 34. 3 34.0 35. 1 35. 0 34. 7 34. 5 312/發明說明書(補件)/92-11/92123415 18 1312354 (比較例6 ) 除了將導電聚合物聚噻吩改以聚吡咯取代之外，其餘以相同於實施例1之方法製作導電聚合物薄膜。此薄膜之諸性質示於下表3中。 (比較例7 ) 除了將導電聚合物聚噻吩改以聚苯胺取代之外，其餘以相同於實施例1之方法製作導電聚合物薄膜。此薄膜之諸性質示於下表3中。表 3 比較例6 比較例7 薄膜 TAC TAC 導電聚合物層厚度 (β m) 0. 10 0. 10 表面電阻率（Ω/平方面積） lx 105 108 總太陽能量透明度（％ ) 75 50 雙折射 (nm ) 10 10 熟習本發明所屬技術領域者應可自如上詳述内容推衍出各種變化。該等變化只要不脫離本發明申請專利範圍所記載之精神和範圍，均包含於本發明中。 19 312/發明說明書(補件)/92-11/92123415m 312/Invention Manual (Supplement)/92-11/92123415 1312354 The visible light transmittance of the film and the important properties of the birefringence system. The higher the visible light transmittance, the better. The visible light transmittance is usually 78% or more, and preferably 82% or more, and 85% or more is more preferable. The lower the birefringence, the better. The birefringence is usually at 100 nm or less, and more preferably 50 nm or less. The conductive polymer film is preferably one having the same properties. Since the acetaminophen film and the norbornene film have visible light transmittance, birefringence, and yellow hue, they are used as the above polymer film. The acetaminophen film may, for example, be a triacetyl cellulose film (T A C film), a cellulose diacetate film using cellulose fibers as a raw material, and the modified film. The films are typically prepared, for example, by dissolving the cellulosic fibers in a suitable solvent, such as methylene gas, applying the resulting solution to a stainless steel sheet or a suitable polymeric film, removing the solvent and drying the film. . The norbornene film to be used in the present invention is not particularly limited as long as it is a polymer obtained by using at least one monomer having a norbornene structure. For example, the polymer may be obtained by subjecting a monomer having a norbornene structure to ring-opening polymerization, or hydrogenating a part or all of the remaining double bond in the presence of a hydrogenation catalyst. Typical examples of the polymer include: ZEONEX or ZEONOR (trade name, manufactured by Nippon Zeon) manufactured by the method described in JP-A 63-218726, 5-25220 or 9-183832, and by, for example, JP- ART0N (trade name, manufactured by JSR Corporation) obtained by the method described in A 5 - 9 7 9 78 or 1 - 2 4 0 5 1 7 . Another example of the polymer is a polymerization obtained by addition polymerization of a monomer having a norbornene structure and a plurality of other monomers having a double bond by a known method. 12 312 / invention specification (supplement) / 92-11 /92123415 1312354 Things. Examples of such a polymer include APEL (trade name, manufactured by Mitsui Chemicals Co., Ltd.) and TOPAS (trade name, Hoechst AG) obtained by the method described in JP-A 6-107735, 62-252406 or 8-259629. system). The method of producing a film from the above polymer can be a well-known method. For example, the film can be produced by a die-casting method, and the polymer is dissolved in a solvent capable of sufficiently dissolving the polymer (particularly a halogen-based solvent such as methylene gas or an aromatic or acrylic solvent), and the obtained polymer is obtained. The solution is applied to a metal (e.g., stainless steel) plate or a polymer (e.g., polyester) film, and the solvent is removed and then dried. The film can also be produced by extrusion molding, heat-melting the polymer, and extruding the molten polymer onto a metal plate, which is then dried. When manufacturing an acetonitrile film or a norbornene film, various additives such as an antioxidant, an ultraviolet absorber, an ultraviolet stabilizer, a colorant, a lubricant, an antistatic agent, a pigment, a dye, etc. may be added to the polymer as needed. Fiber or dispersant, etc. When the film is used as a protective film for a polarizing plate, it is preferred to use a film containing an antioxidant, an ultraviolet absorber, and/or an ultraviolet stabilizer. The surface of the resulting film can be coated with a suitable material for the purpose. A UV hardener or a thermosetting hard film (hardc 〇at) material, an epoxy hard film material, and a polyoxyalkylene hard material such as an acrylic, urethane or amide phthalate may be applied to the surface of the film. Membrane materials, etc., to prevent surface scratches. It is also possible to use a film obtained by coating a hard film material containing such ultrafine particles such as S0 0 or alumina on the surface thereof, thereby reducing glare, that is, using a film having an anti-glare hard film. When the film is used as a protective film for a polarizing plate, it is preferred to use a film having the above hard film or anti-glare hard film. 13 312/Invention Manual (Supplement)/92-11/92123415 1312354 A method of applying a coating liquid to a polymer film can be carried out by a known coating method. Examples of the coating method include roll coating, gravure coating, screen printing, offset printing (〇ff-set) printing, micro gravure coating, reverse phase coating, roll brushing, spray coating, air knife coating, filling method, and curtain shape. Coating. These methods may be used singly or in combination of two or more. The thickness of the conductive polymer layer is 0.005~3, 111, preferably 0.01~l/ztn, and more preferably 0. 0 2 ~ 0. 5 /z m. If the thickness is too small, sufficient antistatic effect cannot be obtained. Conversely, if the thickness is too large, the coated film may be broken, or the anti-caking property may be lowered. The conductive polymer layer can be formed on one or both sides of the polymer film. The above hard film material or anti-glare hard film may be applied to the obtained polymer film on which the conductive polymer layer is formed. Further, various well-known coatings such as an anti-refractive film, an anti-fouling film or a pressure-sensitive adhesive film may be used as desired. When the conductive polymer layer is formed on one side of the film, a hard film, an anti-glare hard film, an anti-refractive film, an anti-fouling film or a pressure-sensitive adhesive film may be used on the opposite side for the purpose. These coating methods may be used singly or in combination of two or more. In the LCD, two polarizing plates are usually mounted in front of and behind the liquid crystal. The film of the present invention can be used as a four-piece protective film for two polarizing plates. However, it is not necessary to use four films, and one, two or three films may be used as the protective film depending on the purpose. When a plurality of films are used, the films do not need to have the same electrical resistivity, and a suitable polymer film can be selected depending on the purpose. When the electromagnetic wave shielding function is considered, it is preferable to use a thin film for the outermost protective film from the viewpoint of effect and cost. The present invention will now be described in more detail with reference to the examples, but the invention is not limited to the embodiments. (Example 1) Dissolved in 1 kg of water containing 20% by weight of isopropanol: a material obtained by copolymerizing polystyrenesulfonate ions with polystyrenesulfonic acid at a molar ratio of 1:1 3 0 In the parts by weight, 16 g of a conductive polymer obtained by dropping 16 parts by weight of dioxyethylene polythiophene (Baytron P®, manufactured by Bayer) was added; the acrylic resin was mixed in a ratio of 1:1:1 by weight. , a binder obtained from a urethane resin and a polyvinyl alcohol, 100 g; and a polyoxyethylene nonylphenol ether as a nonionic surfactant: 5 g; and an aqueous coating liquid 1 was obtained. The coating liquid was applied to a triacetone cellulose film (T AC film) having a thickness of 80 μm by a groove coater, and dried at 10 ° C. The obtained conductive polymer film was obtained. The thickness was 0.11/im. The properties of the film are shown in the following Table 1. Comparing with the following Comparative Example 1 in which the conductive polymer solution was not coated, it is apparent that, after coating, 10 Μ Ω / The surface resistivity above the square area is reduced to 8 X 1 05 Ω / square area, so the conductivity increases, but the total solar transparency and birefringence are not substantially reduced, while the yellowness is inversely reduced. The above case indicates that even The film is disposed inside the LCD, and particularly even if it is used as a protective film for a polarizing plate, the film does not adversely affect optical properties, and the yellowness is even improved, and thus the electromagnetic wave shielding function or the antistatic function is increased. 1) The properties of the TAC film of Example 1 were measured without applying a conductive polymer solution. The results obtained are shown in Table 1 below. 15 312 / Invention Specification (supplement) / 92-11/ 92123415 1312354 ( Example 2) An ultraviolet curable acrylic hard coat material in which fine fine vermiculite was dispersed was applied onto a TAC film having a thickness of 80 μm to prepare an antiglare-treated film to cause fogging of the film. The Haze value was 27.1%, and the brightness at an angle of 60° was 34.3%. The aqueous coating liquid 1 obtained in Example 1 was applied to the surface of the above-prepared film in the same manner as in Example 1. The thickness of the obtained conductive polymer layer was 0.12 // m. The properties of the film are shown in the following Table 2. The following Comparative Example 2 shows the characteristic values when the conductive polymer solution is not coated. Comparing Example 2, it is apparent that although the surface resistivity of 10 Ι 4 Ω / square area is reduced to 7 χ 105 Ω / square area after coating, the conductivity is increased, but the total solar transparency and birefringence are substantially unchanged. Moreover, the yellowness is improved. In addition, it is apparent that the application of the conductive polymer solution on the anti-glare treatment layer substantially does not change the haze value and the brightness. From these results, even if the coating is to be applied The anti-glare treatment TAC film of the conductive polymer of the invention is disposed inside the LCD, the anti-glare treatment effect can be maintained, and the optical properties are not adversely affected, and the electromagnetic wave shielding function and the antistatic function can be exhibited, and the yellowness is reversed. The ground was improved. (Comparative Example 2) The properties of the anti-glare-treated TAC film of Example 2 were measured without applying a conductive polymer solution. The results obtained are shown in Table 2 below. 16 312 / Invention Description (Supplement) / 92-11 /92123415 1312354 A coating film was prepared as in Example 1 except that the conductive polymer used was changed to 1 〇g. The resulting conductive polymer layer has a thickness of 0.12 // m. The properties of this film are shown in Table 1 below. (Example 4) A coated film was prepared in the same manner as in Example 1 except that the thickness of the conductive polymer layer was changed to the balance. The properties of the resulting film are shown in Table 1 below. (Example 5) The same aqueous coating liquid 1 used in Example 1 was applied to a film of a thickness of 100 μm/z m made of a norbornene material (trade name "A R Τ Ο N", manufactured by J S R). The resulting conductive polymer layer had a thickness of 0.10/zm. The properties of this film are shown in Table 1 below. (Comparative Example 3) The properties of the film used in Example 5 were measured without applying an aqueous coating liquid. The results obtained are shown in Table 1 below. (Example 6) An aqueous coating liquid was applied in the same manner as in Example 5 except that the film was changed to an antiglare-treated ARTON film having a thickness of 100/zm. The resulting conductive polymer had a thickness of 0.11 / zm. The properties of this film are shown in Table 2 below. (Comparative Example 4) The properties of the film used in Example 6 were measured without applying an aqueous coating liquid. The results obtained are shown in Table 2 below. (Example 7). In addition to changing the film to a thickness of 1 0 0 /2 m, a norbornene material (product 17 312 / invention specification (supplement) / 92-l 1/92123415 1312354 "ZEONOA", Nippon Zeon ( The film was prepared and subjected to anti-glare treatment in the same manner as in Example 6, except that the coated film was obtained in the same manner as in Example 6. The resulting conductive polymer layer has a thickness of 〇 . 1 2 /z m. The properties of this film are shown in Table 2 below. (Comparative Example 5) The properties of the film used in Example 7 were measured without applying an aqueous coating liquid. The results obtained are shown in Table 2 below. Table 1 Example 1 Example 3 Example 4 Comparative Example 1 Example 5 Comparative Example 3 Thin film TAC TAC TAC TAC ART0N ART0N Conductive polymer layer thickness (Αί Π1 ) 0. 11 0.12 1. 2 No 0.10 No surface resistivity ( Ω / square area) 8x 105 4x 109 6x 104 > 1 014 2x 106 > 1 014 Yellowness b* 0.25 0.35 0.17 0.40 0. 30 0.45 Total solar energy transparency (%) 92. 1 92. 3 90.0 92.3 92. 7 92.6 Birefringence (nm) 10 10 12 10 15 16 Table 2 Example 2 Comparative Example 2 Example 6 Comparative Example 4 Example 7 Comparative Example 5 Thin film TAC TAC ART0N ART0N ZEN0R ZEN0R Conductive polymer layer thickness (# m ) 0 12 无 0. 1 1 无 0.12 No surface resistivity (Ω / square area) 7x 105 > 1 014 7x 105 >10" 6x 105 > 1 014 Yellowness b* 0. 50 0.65 0.55 0.71 0.77 0. 93 Total solar energy transparency (%) 91.3 91.4 92. 0 92. 2 91.5 91.9 Birefringence (nm) 11 12 16 17 17 19 Haze value (%) 25.9 27. 1 26. 6 27. 3 25.3 26.4 60° angular brightness (%) 34. 3 34.0 35. 1 35. 0 34. 7 34. 5 312/Inventive Manual (supplement)/92-11/92123415 18 1312354 (Comparative Example 6) A conductive polymer film was produced in the same manner as in Example 1 except that the conductive polymer polythiophene was replaced with polypyrrole. The properties of this film are shown in Table 3 below. (Comparative Example 7) In addition to the conductive polymer A conductive polymer film was produced in the same manner as in Example 1 except that polythiophene was replaced with polyaniline. The properties of this film are shown in Table 3 below. Table 3 Comparative Example 6 Comparative Example 7 Thin film TAC TAC Conductive polymerization Thickness of the layer (β m) 0. 10 0. 10 Surface resistivity (Ω/square area) lx 105 108 Total solar energy transparency (%) 75 50 Birefringence (nm) 10 10 Those skilled in the art should be able to Various changes have been derived from the details above. Such changes are intended to be included in the present invention without departing from the spirit and scope of the invention. 19 312/Invention Manual (supplement)/92-11/92123415

Claims

1312354拾、申請專利範圍：年月 -tft1312354 pick up, patent application scope: year-month -tft

OCf 2 8 2008 替换本 1. 一種偏光板用保護薄膜，其包含一聚合物薄膜及一黏著於其表面之導電聚合物，其中，該導電聚合物包含聚噻吩或聚噻吩衍生物，該聚合物薄膜包含乙醯纖維素材料或降冰片烯材料，而該導電聚合物之層厚度為3/zm或以下，且該導電聚合物薄膜之可見光透光度為 78%或以上，雙折射為lOOnm或以下，同時其表面電阻率為104~1012Ω /平方面積。 2 .如申請專利範圍第1項之偏光板用保護薄膜，其中，該導電聚合物層進一步包含一接著劑樹脂。 3. 如申請專利範圍第1項之偏光板用保護薄膜，其中，該導電聚合物層進一步包含一接雜物。 4. 如申請專利範圍第1項之偏光板用保護薄膜，其中，更包含一硬膜層。 5. —種偏光板，其包含一偏光膜，以及一形成於該偏光膜之至少一邊之如申請專利範圍第1項之偏光板用保護薄膜以作為保護膜。 6 · —種偏光板用保護薄膜之製造方法，係用以製造於聚合物薄膜之表面使導電聚合物黏著之偏光板用保護薄膜者，其中，該導電聚合物係聚噻吩或其衍生物；該聚合物薄膜為乙醢纖維素系薄膜；導電聚合物層之厚度為 3 m 或以下，可見光透光度為78 %或以上，雙折射為lOOnm或以下，且表面電阻率為104~1012Ω /平方面積；該方法具有藉由含聚噻吩或其衍生物作為導電聚合物之水性塗布液， 20OCf 2 8 2008 Replacement 1. A protective film for a polarizing plate comprising a polymer film and a conductive polymer adhered to the surface thereof, wherein the conductive polymer comprises a polythiophene or a polythiophene derivative, the polymer The film comprises an acetonitrile cell material or a norbornene material, and the conductive polymer has a layer thickness of 3/zm or less, and the conductive polymer film has a visible light transmittance of 78% or more and a birefringence of 100 nm or Hereinafter, the surface resistivity thereof is 104 to 1012 Ω / square. 2. The protective film for a polarizing plate according to claim 1, wherein the conductive polymer layer further comprises an adhesive resin. 3. The protective film for a polarizing plate according to claim 1, wherein the conductive polymer layer further comprises a dopant. 4. The protective film for a polarizing plate according to claim 1, wherein a hard coat layer is further included. A polarizing plate comprising a polarizing film, and a protective film for a polarizing plate according to the first aspect of the invention, which is formed on at least one side of the polarizing film, as a protective film. (6) A method for producing a protective film for a polarizing plate, which is a protective film for a polarizing plate which is formed on a surface of a polymer film to adhere a conductive polymer, wherein the conductive polymer is polythiophene or a derivative thereof; The polymer film is an acetonitrile cellulose film; the conductive polymer layer has a thickness of 3 m or less, a visible light transmittance of 78% or more, a birefringence of 100 nm or less, and a surface resistivity of 104 to 1012 Ω / Square area; the method has an aqueous coating liquid comprising a polythiophene or a derivative thereof as a conductive polymer, 20

92123415 1312354 " 於乙醯纖維素系薄膜之表面形成導電聚合物層之步驟；藉由形成導電聚合物層，使經導電處理之聚合物薄膜的黃度小於乙醯纖維素系薄膜的黃度。 7 .如申請專利範圍第6項之偏光板用保護薄膜之製造方法，其中，水性塗布液進一步含有接著劑樹脂" 8. 如申請專利範圍第6項之偏光板用保護薄膜之製造方法，其中，水性塗布液進一步含有摻雜物。 9. 如申請專利範圍第6項之偏光板用保護薄膜之製造方法，其中，水性塗布液之固體成分濃度為0 . 1 ~ 3 0重量％。 1 0 .如申請專利範圍第 6項之偏光板用保護薄膜之製造方法，其中，水性塗布液係含有可溶於水之溶劑。 1 1 .如申請專利範圍第6項之偏光板用保護薄膜之製造方法，其中，經導電處理之聚合物薄膜係進一步被硬膜 (hardcoat)化。 12. —種偏光板用保護薄膜之製造方法，係用以製造於聚合物薄膜之表面使導電聚合物黏著之偏光板用保護薄膜者，其中，該導電聚合物係聚噻吩或其衍生物；該聚合物薄膜為降冰片烯系薄膜；導電聚合物層之厚度為3 // m或以下，可見光透光度為78%或以上，雙折射為lOOnm或以下，且表面電阻率為104~1012Ω /平方面積；該方法具有藉由含聚噻吩或其衍生物作為導電聚合物之水性塗布液，於降冰片烯系薄膜之表面形成導電聚合物層之步驟；藉由形成導電聚合物層，使經導電處理之聚合物薄膜的黃度小於降冰片烯系薄膜的黃度。 21 92123415 1312354 1 3 .如申請專利範圍第1 2項之偏光板用保護薄膜之製造方法，其中，水性塗布液進一步含有接著劑樹脂。 1 4 .如申請專利範圍第1 2項之偏光板用保護薄膜之製造方法，其中，水性塗布液進一步含有掺雜物。 1 5 .如申請專利範圍第1 2項之偏光板用保護薄膜之製造方法，其中，水性塗布液之固體成分濃度為0 . 1〜3 0重量％。 1 6 .如申請專利範圍第1 2項之偏光板用保護薄膜之製造方法，其中，水性塗布液係含有可溶於水之溶劑。 1 7 .如申請專利範圍第1 2項之偏光板用保護薄膜之製造方法，其中，經導電處理之聚合物薄膜係進一步被硬膜化。 22 9212341592123415 1312354 " a step of forming a conductive polymer layer on the surface of the acetonitrile cellulose film; by forming a conductive polymer layer, the yellowness of the conductively treated polymer film is less than the yellowness of the acetaminocellulose film . 7. The method for producing a protective film for a polarizing plate according to claim 6, wherein the aqueous coating liquid further contains an adhesive resin, and 8. The method for producing a protective film for a polarizing plate according to claim 6 of the patent application, Among them, the aqueous coating liquid further contains a dopant. 9. The method for producing a protective film for a polarizing plate according to claim 6, wherein the aqueous coating liquid has a solid content concentration of 0.1 to 30% by weight. The method for producing a protective film for a polarizing plate according to the sixth aspect of the invention, wherein the aqueous coating liquid contains a solvent soluble in water. The method for producing a protective film for a polarizing plate according to claim 6, wherein the conductively treated polymer film is further hardcoated. 12. A method for producing a protective film for a polarizing plate, which is used for producing a protective film for a polarizing plate which is adhered to a surface of a polymer film to adhere a conductive polymer, wherein the conductive polymer is polythiophene or a derivative thereof; The polymer film is a norbornene-based film; the conductive polymer layer has a thickness of 3 // m or less, a visible light transmittance of 78% or more, a birefringence of 100 nm or less, and a surface resistivity of 104 to 1012 Ω. / square area; the method has the steps of forming a conductive polymer layer on the surface of the norbornene-based film by using an aqueous coating liquid containing polythiophene or a derivative thereof as a conductive polymer; by forming a conductive polymer layer, The yellowness of the conductively treated polymer film is less than the yellowness of the norbornene-based film. The method for producing a protective film for a polarizing plate according to claim 12, wherein the aqueous coating liquid further contains an adhesive resin. The method for producing a protective film for a polarizing plate according to claim 12, wherein the aqueous coating liquid further contains a dopant. The method of producing a protective film for a polarizing plate according to the invention of claim 12, wherein the solid coating concentration of the aqueous coating liquid is 0.1 to 30% by weight. The method for producing a protective film for a polarizing plate according to claim 12, wherein the aqueous coating liquid contains a solvent soluble in water. The method for producing a protective film for a polarizing plate according to claim 12, wherein the conductively treated polymer film is further densified. 22 92123415