'200521503 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種將環烯烴系樹脂膜接著在聚乙烯醇 系樹脂所構成之偏光膜上所成之偏光板及其製造方法。 【先前技術】 偏光板通常係將透明樹脂膜（例如以三乙醯基纖維素 為代表之乙酸纖維素系保護膜）介由接著劑層，積層在吸附 定向有二色性色素之聚乙烯醇系樹脂所構成之偏光膜之單 面或兩面上而成。將其介由接著劑，視需要尚可以其他光 车膜，貼合於液晶晶元（1 iqUid cryStal cel 1)上，成為液 晶顯示裝置之構成零件。 液晶顯示裝置，隨著用途擴大，已可於各種 ------- 一 …、，cr ! J兄 τ 用，因而構成該液晶顯示裝置之零件被要求高耐環境性 例如’以仃動電話為代表之攜帶式（mQbile)液晶顯示裝] 上，期望在溼熱下亦可使用’縱使對此所使用之偏光板 高龍熱性及耐久性。然而，以往所製成之偏光板 右長㈣暴露於特靠熱之環境下，偏光性能容易降低 且有「偏光板與乙酸纖維素系膜之界面易於剝離」 針對此等問題，曾提出「 、 為偏弁塑性環烯烴系樹削 為偏先板之保4膜」。例如，曰本專利特開 公報（專利文獻η φ U828 4 (mb0rnene)系樹脂。片人將熱塑性飽和降冰片烯 乙烯醇系片之至少：面上;’由丙烯酸系接著劑，積層在聚 上，並加熱屡合以萝造值本 專利特開千6-511Π號公報（專利文獻2)中記載··厂將熱 316533 5 ,200521503 .塑性飽和降冰片㈣所構成之保護 光板之至少-面上以製 、積層在*乙_系偏 劑，則可列舉如··戈胺其 /至於其所使用之接著 、脂溶液混合而成趣 - 取 <乾式積層用接著劑、1 膠系接著劑及環氧系二液硬了—烯橡 特開跡她號公報(專利文獻 烴系樹脂所構成之俘1 載將％狀烯 创η 4膜’介由聚乙稀醇系接著劑虚1 型接者劑之混合物所成之 I、—液 光膜之至少-面上以製造偏：：層。：層在聚乙_系偏 2000-321432號公報（專利#」者，日本專利特開 專利文獻4)中記載··「將聚乙烯醇李 介由聚胺基心=:稀系樹脂所構成之保護膜 曰系接者劑接著，以製造偏光板」。 然㈣酸轉接著劑（亦被 =為丨…。心，而其厚度非達到某種程度不者::本身 乾切層用接著劑、苯乙稀—丁二烯橡膠系接著劑及 —液硬化型接著劑等接著劑 — /、 作業者之健康上的問題。再:=二=，上及 著劑用於以往從未使用有機、— ' ' '、岭劑之接 帶來防爆光板製造設備，則將 :末防暴6又備之新設等設傷改造的繁雜。再 :知，聚：稀醇系、胺基甲酸醋系、丙稀酸系或乙酸二 :二ί接：劑’如將聚乙烯醇系偏光膜與環烯烴系樹脂膜 接者％，視兩膜之組合，接著性卻未必充分。 另一方面’主要意圖以以往之三乙醯基纖維素等做為 …又、’而對於其與聚乙稀醇系偏光膜之接著提出各種方 316533 6 200521503 案。例如，日本專利特開平8-101307號公報（專利文獻5) 中記載聚乙烯醇系偏光膜與支樓體（保護膜），介由聚西旨多 -元醇及脂肪族多元異氰酸酉旨所組成之接著劑進行積層而成 之偏光板。 [專利文獻1]曰本專利特開平5_212828號公報 [專利文獻2]曰本專利特開平6_51117號公報 [專利文獻3]曰本專利特開2〇〇〇_32143〇號公報 [專利文獻4]日本專利特開2〇〇〇_321432號公報 [專利文獻5]日本專利特開平8_1G13()7號公報 【發明内容】 曼明所欲解決之誤韻 在Ρ Γ 2之目的烯烴系樹脂所組成之保護膜積層 、θ二糸偏光膜上，製成偏光板時，使用適當之接著 Μ，以提而兩者之接著六 、接者力。本發明之另一個目的，係使用 ^ ^ 3機，合劑之水系接著劑，製造聚乙烯醇系偏光 膜與=煙系樹脂膜強力接著而成之偏光板。 現將由I::人等根據該目的之起源而專心研究之結果，發 =:㈣系樹脂所組成之保護膜積層在聚乙稀醇系偏 劑，可：刭：由使用以特定成分調配成之混合物做為接著 成本發el膜與保護膜之接著性優良之偏光板，而完 將環根據本發明便可提供一種偏光板’該偏光板係 將％~烴系樹脂膜攸你 由接者劑層積層在由聚乙烯醇系樹 316533 7 200521503 脂所構成之偏光膜之至少一面上所成之偏光板，該接著劑 層至少含有氧雜環丁烷（oxetane)化合物。 其中，構成接著劑層之胺基甲酸酯樹脂以聚酯 物型胺基甲酸g旨樹脂為佳。環烯烴系樹脂膜可配置於Z 膜之單面，亦可g己詈於值古B替令； 浐厚㈣丄 將環烯烴系樹脂膜 牙貝層於偏光膜之單面時’可將環稀烴系樹脂以外之樹脂所 構成之保護膜（例如乙酸纖維素系膜）積層於另—面。 ，根據本發明，提供一種製造偏光板之方法，其中 將％烯烴系樹脂膜介由以胺基甲酸酯樹脂、氧雜環丁尸籲 合物及環氧化合物所調配成之水系接著劑 : 貝貝上不含有機溶劑之形式者。 - 依照本發明’與使用以往接著劑之情況相較，可製 朴:乙烯_系偏光膜與環烯烴系樹脂所構成之保護膜間'200521503 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a polarizing plate formed by bonding a cycloolefin resin film to a polarizing film composed of a polyvinyl alcohol resin and a method for manufacturing the same. [Prior art] Polarizing plates are usually made of a transparent resin film (such as a cellulose acetate-based protective film represented by triethylsulfonyl cellulose) through an adhesive layer, and laminated with polyvinyl alcohol having a dichroic pigment in an orientation direction. One or both sides of a polarizing film made of resin. It can be bonded to the liquid crystal cell (1 iqUid cryStal cel 1) through the adhesive through other adhesive films as needed, and become a component of a liquid crystal display device. As the liquid crystal display device expands, it can be used in a variety of ------- one, cr! J brother τ, so the components constituting the liquid crystal display device are required to have high environmental resistance, such as the On the mobile (mQbile) liquid crystal display device typified by a telephone, it is expected that the polarizing plate used for this purpose can also be used under moist heat even though it has high heat resistance and durability. However, in the past, the right polarizer of the polarizing plate was exposed to a particularly hot environment, and the polarization performance was easily reduced. There was "the interface between the polarizing plate and the cellulose acetate film is easy to peel off". In response to these problems, " To protect the plastic film of partial cyclic olefins, it is cut into the first sheet. " For example, Japanese Patent Laid-Open Gazette (Patent Document η φ U828 4 (mb0rnene) -based resin. The filmmaker has thermoplastic saturated norbornene vinyl alcohol-based tablets at least: the surface; 'Acrylic adhesive is laminated on the polymer , And heating repeatedly combined with the value of this patent is disclosed in Japanese Patent Laid-Open No. 6-511Π (Patent Document 2). The factory will heat 316533 5, 200521503. At least one side of the protective light plate composed of plastic saturated norbornene ㈣ Based on the above-mentioned system and layered in * B_ series polarizers, you can list, for example, Gamine / the adhesive used for it, and the fat solution is mixed to make it interesting-take < dry-layer laminating adhesive, 1 glue-based adhesive And epoxy-based two-liquids are hardened-olefin rubber traces her gazette (patent document 1 made up of hydrocarbon-based resin containing 1% ene-based η 4 film 'via a polyvinyl-based adhesive virtual type 1 I, formed by the mixture of the contact agent, at least-the surface of the liquid-light film to make a partial :: layer.: The layer is in the polyethylene-series publication 2000-321432 (patent #), Japanese Patent Laid-Open Patent Document 4) states that "" Polyvinyl alcohol via a polyamine-based core =: The film is connected with a bonding agent to manufacture a polarizing plate. "However, the acid conversion agent (also = = 丨 ... heart, and its thickness does not reach a certain level or not :: itself as a cutting agent for dry cutting layer) , Styrene-butadiene rubber-based adhesives, and—adhesives such as liquid-curing adhesives— /, health problems of the operator. Again: = 二 =, the above is used for organic materials that have never been used before. , — '' ', The connection of lingering agents brings explosion-proof light board manufacturing equipment, and it will be complicated to modify the damages such as the latest anti-riot 6 and the new equipment. Further: know, poly: dilute alcohol, urethane, Acrylic acid-based or acetic acid-two: two-linking: agents "If the polyvinyl alcohol-based polarizing film is connected with a cycloolefin-based resin film%, depending on the combination of the two films, the adhesiveness may not be sufficient. On the other hand, the main intention Based on the conventional triethyl cellulose, etc., and “there are various proposals on 316533 6 200521503 for the subsequent polarized film with polyethylene.” For example, Japanese Patent Laid-Open No. 8-101307 (Patent Reference 5) describes a polyvinyl alcohol-based polarizing film and a supporting structure (protective film) via a polysilicon -A polarizing plate formed by laminating an adhesive composed of an alcohol and an aliphatic polyisocyanate. [Patent Literature 1] Japanese Patent Laid-Open No. 5_212828 [Patent Literature 2] Japanese Patent Laid-Open No. 6_51117 Gazette [Patent Document 3] Japanese Patent Laid-Open No. 2000-321430 [Patent Document 4] Japanese Patent Laid-Open No. 2000-321432 [Patent Document 5] Japanese Patent Laid-Open No. 8_1G13 () 7 No. [Summary of the Invention] The wrong rhyme that Manmin wants to solve is a protective film laminate composed of an olefinic resin of the purpose of P Γ 2 and a θ-two polarizing film. The next two are the sixth. Another object of the present invention is to use a ^ 3 machine and a water-based adhesive for the mixture to manufacture a polarizing plate made of a polyvinyl alcohol-based polarizing film and a tobacco resin film. The results of intensive research by I :: people and others based on the origin of the purpose will be published. The protective film layer consisting of: ㈣ resin is laminated with a polyvinyl-based polarizer. It can be: 刭: formulated by using specific ingredients The mixture is used as a polarizing plate with excellent adhesion between the film and the protective film, and the polarizing plate according to the present invention can provide a polarizing plate. The polarizing plate is based on a hydrocarbon resin film. The adhesive layer is a polarizing plate formed on at least one side of a polarizing film composed of a polyvinyl alcohol tree 316533 7 200521503 grease, and the adhesive layer contains at least an oxetane compound. Among them, the urethane resin constituting the adhesive layer is preferably a polyester-type urethane resin. The cycloolefin-based resin film can be arranged on one side of the Z film, or can be used as a substitute for the value of B .; 浐 When the cycloolefin-based resin film tooth layer is layered on one side of the polarizing film, A protective film (for example, a cellulose acetate film) made of a resin other than the dilute hydrocarbon resin is laminated on the other side. According to the present invention, a method for manufacturing a polarizing plate is provided, in which a% olefin-based resin film is prepared through a water-based adhesive formulated with a urethane resin, an oxetane compound, and an epoxy compound: Babe does not contain organic solvents. -According to the present invention, compared with the case where a conventional adhesive is used, it can be made simple: between a protective film made of an ethylene-based polarizing film and a cycloolefin-based resin
I優異之偏光板H該偏光板之製造時，由於無 :有機溶劑’因此除了在環境方面及安全衛生方面優 之相ρΓ %可用以往之透明保護膜/由偏光膜構成之偏光 之相同設備製造’而無需大金額的設備投資。 【實施方式】 、I Excellent polarizing plate H In the manufacture of this polarizing plate, there is no: organic solvent, so except for environmental and safety and health aspects, ρΓ% can be manufactured with the same transparent protective film / polarizing film composed of polarizing film 'Without the need for large amounts of equipment investment. [Embodiment]
講瞪人 將°羊細地s兒明本發明。偏光板係藉由將透明保 :膜：Ϊ接者劑層’積層在由聚乙烯醇系樹脂所構成之偏 、早面或兩面上而製造。由聚乙烯醇系樹脂所構成之 316533 8 200521503 偏光膜，具體而言，係在單轴 *附二色性色素並加以定向而㈣上 積層於上述偏光膜之至少一面上之保護膜係採用 樹脂：’以及接著劑層係從以胺基甲酸酯樹脂、：雜：二 烷化合物及環氧化合物所調配成之組合物而得者。义 。構成偏光膜之聚乙烯醇系、樹脂，係藉由將聚乙酸乙稀 :糸樹脂皂化而得。聚乙酸乙烯醋系樹脂除了係屬乙酸乙 烯酯之早一聚合物之聚乙酸乙烯酯外，係例如：乙酸乙烯 :旨與可和其共聚之其他單體之共聚物等。可與乙酸乙烯醋 八聚合之其他單體’可列舉例如：不飽和羧酸類、不飽和 :頁酸類、烯烴類、乙烯醚類、具有銨基之丙烯醯胺類等。 聚乙烯醇系樹脂之皂化度通常約為85至1〇〇莫耳％，而以 9 8莫耳％以上為佳。該聚乙浠醇系樹脂亦可再進行改質， =如亦可使用藉由酸類改質之聚乙烯甲縮盤或聚乙烯乙縮 醛等而得。又，聚乙烯醇系樹脂之聚合度通常約為1，〇〇〇 至10, 000，而以約1，500至5, 000為佳。 以3亥聚乙稀醇系樹脂製膜，可被使用作為偏光膜之原 料膜。以聚乙烯醇系樹脂製膜之方法並無特別限定，可藉 由習知之方法製膜。聚乙烯醇系原料膜之膜厚並無特別限 疋’例如可約為1 〇 # m至15 0 // m。 偏光膜之製造’一般係經由·精由將此種聚乙稀醇系 Μ脂膜以單軸延伸之製程；將聚乙烯醇系樹脂膜以二色性 色素染色，並使該二色性色素吸附之製程；將吸附有二色 性色素之聚乙烯醇系樹脂膜以硼酸水溶液處理之製程；以 316533 9 200521503 及由該硼酸水溶液經處理後進行水洗之製程。 延伸可在染色前進行，或與染色同時進行，亦可 ，色後進行。在染色後進行單軸延料，該單轴延伸可 ^酸處理前進行，亦可在顯處理中進行。當然，亦可 2寺複數個階段進行單輛延伸。當進行單軸延伸時，可 =速：=進行單轴延伸，亦可使用熱觀進行單轴 ，可為在大氣中進行延伸等之乾式延伸，亦可為 在浴劑中以膨潤狀態進行延伸之澄式常 約為3至8倍。 、乳羊通书丨 士，稀醇系樹脂膜以二色性色素染色時，舉例而 ::要將“稀醇系樹脂膜浸潰於含有二 /、體而$，可使用碘或二色性染料作為二色 脂膜色性色素時’通常採用將聚乙稀醇系樹 水溶=‘含ί及=卸之水溶液中以染色之方法。該罐 0.0Α重旦八里诚 每100重量份之水，通常約為 水，通常約^V 之含量，相對於每100重量份之 、、’、為0.5至20重量份。毕色所用夕k、6、— 通常約為2 0至4 〇。「 所用之水溶液之溫度 n Vs C，又，在該水溶液中之浸潰時 日寸間）通常約為20至1，800秒。 、卞巴 採用=二it色性染料作為二色性色素時，通常 水溶液中以心::膜浸潰在含有水溶性二色性染料之 木色之方法。該水溶液中二色性染料之含量， 316533 10 200521503 相對於每100重量份之水，約為ΐχΐ(Γ4至1G重 以約lx 10-3至i重量份為 里知，而 無機鹽作為染色助劑。毕色所用、九;酸鋼等 ‘約為2。爾，又在=料水溶液之溫度，通常 ‘、g ln 在该水洛液中之浸潰時間（染色時間） 通常約為10至1，8〇〇秒。 才1 ) 使用一色性色素染色後之石朋酸處理，係 之聚乙烯醇系樹脂膜、兮、主认人丄 肝、、工木色 曰肤次貝於含有硼酸之水溶液中而進行。 含有棚酸之水溶液Φ別0缺 田Speaking of dazzling people will clearly explain the invention. The polarizing plate is manufactured by laminating a transparent protective film: an adhesive agent layer 'on a polarized, early surface, or both surfaces made of a polyvinyl alcohol resin. 316533 8 200521503 polarizing film made of polyvinyl alcohol resin, specifically, a protective film based on uniaxial * with dichroic pigments and orientation and laminated on at least one side of the above polarizing film uses resin : 'And the adhesive layer are obtained from a composition prepared from a urethane resin, a: hetero: dioxane compound, and an epoxy compound. Righteousness. The polyvinyl alcohol-based and resin constituting the polarizing film are obtained by saponifying a polyvinyl acetate: fluorene resin. In addition to polyvinyl acetate, which is an early polymer of vinyl acetate, polyvinyl acetate resins are, for example, vinyl acetate: copolymers intended to copolymerize with other monomers. Examples of other monomers that can be polymerized with vinyl acetate and vinegar include unsaturated carboxylic acids, unsaturated carboxylic acids, olefins, vinyl ethers, and acrylamides having an ammonium group. The saponification degree of the polyvinyl alcohol-based resin is usually about 85 to 100 mol%, and more preferably 98 mol% or more. The polyethylene glycol-based resin can also be modified, if it is obtained by using an acid-modified polyethylene methylation disk or polyethylene acetal. The degree of polymerization of the polyvinyl alcohol resin is usually about 1,000 to 10,000, and preferably about 1,500 to 5,000. A film made of a polyethylenic resin can be used as a base film for a polarizing film. The method for forming a film from a polyvinyl alcohol resin is not particularly limited, and a film can be formed by a conventional method. The film thickness of the polyvinyl alcohol-based raw material film is not particularly limited 疋 ′ may be, for example, about 10 # m to 15 0 // m. The manufacture of polarizing film is generally a process of uniaxially extending such a polyethylene-based M lipid film through a fine process; the polyvinyl alcohol-based resin film is dyed with a dichroic pigment, and the dichroic pigment is dyed. Adsorption process; a process of treating a polyvinyl alcohol-based resin film having a dichroic pigment adsorbed with an aqueous boric acid solution; a process of 316533 9 200521503 and washing the boric acid aqueous solution after treatment. Extension can be performed before dyeing, or at the same time as dyeing, or after dyeing. Uniaxial stretching is performed after dyeing, and the uniaxial stretching may be performed before the acid treatment, or may be performed during the display treatment. Of course, a single vehicle can also be extended in multiple stages at 2 temples. When performing uniaxial extension, you can = speed: = perform uniaxial extension, or use thermal view to perform uniaxial extension. It can be dry extension such as extension in the atmosphere, or extension in a swelling state in the bath. The Cheng formula is often about 3 to 8 times. When you dilute the alcohol-based resin film with dichroic pigment, for example: To dip the "dilute alcohol-based resin film" into the body containing di /, you can use iodine or two-color When the dye is used as the dichroic pigment of the dichroic lipid film, the method of dyeing the polyvinyl alcohol-based tree in an aqueous solution containing 'water' and 'unloading' is usually used. This tank contains 0.0A heavy denim per 100 parts by weight. Water, usually about water, usually about ^ V, is 0.5 to 20 parts by weight per 100 parts by weight. The color k, 6, and-used by Bicolor are usually about 20 to 40. "The temperature of the aqueous solution used is n Vs C, and the time when it is immersed in the aqueous solution) is usually about 20 to 1,800 seconds. When 卞 bar uses a dichroic dye as a dichroic dye Generally, the method of immersing a water-soluble film in a wood solution containing a water-soluble dichroic dye. The content of the dichroic dye in the aqueous solution is 316533 10 200521503 per 100 parts by weight of water, which is about ΐχΐ (Γ4 to 1G weighs about 1 x 10-3 to i parts by weight, and inorganic salts are used as dyeing aids. Acid steel, etc. 'is about 2. Er, and at the temperature of the raw material solution, usually, the impregnation time (dyeing time) of g ln in the water solution is usually about 10 to 1,800 seconds. 1) Use a monolithic pigment dyed lithonic acid treatment, the polyvinyl alcohol resin film, Xi, the main human liver, and wood-colored skin subshellfish are carried out in an aqueous solution containing boric acid. Aqueous solution of shed acid
人合/夜中硼酸之量，相對於水100重量份，iS 常約為2至15 #旦彳八 里切通 重里份，以約5至12重量份為佳。在使用 碘做為二色性g夸技 _ . ^ 牡使用 ” ^έ有硼酸之水溶液以含有峨化细 為佳。含有石朋酸之太、、六 /、钟 曰 /合液中蛾化鉀之量，相對於水1 〇 0重 置份，通常約為0 1 5G 里 .1至15重$份，以約5至12重量份為 土。在3有賴之水溶液中之浸潰時間，通常約為60至 ’ 200 t以約15〇至6〇〇秒為佳，以約別〇至4〇〇秒為 更么3有爛酸之水溶液之溫度通常為50°C以上，以50 至85°C為佳，以60至欧為更佳。 理、工朋酉夂處理後之聚乙稀醇系樹脂膜通常進行水洗處 * X先處理，例如可藉由將經硼酸處理之聚乙烯醇系樹 脂膜浸潰於水中而進行。水洗處理中水之溫度通常約為5 ，4〇c，浸潰時間通常約為2至12〇秒。水洗後施行乾燥 :里便可知到偏光膜。乾燥處理通常使用 熱風乾燥機或 退紅外線加熱器而進行。乾燥處理之溫度通常約為3〇至 而以50至8〇 c為佳。乾燥處理之時間通常約為6〇 至_秒，而以約12〇至_秒為佳。 316533 11 200521503 因此，對聚乙烯醇系樹脂膜施行單 色素染色及硼酸處理，便 申用一色性 約為5至40“。在本㈣偏光膜。該偏光膜之厚度 接著劑層積層在該偏=中至少 環烯煙系樹脂係指例如：且成偏光板。 片稀系單體之由環狀肿Γγ ;、有如降水片~、多環降冰 元的熱塑性樹脂nr H。。丨eiln)所構成單體之單 聚合物或使用：種:糸脂除τ上述環稀烴之開環 外，二： 婦烴之開環共聚物之加氯產物 物之加成共聚物。又，導入極性基香族化合 物之=讀:與鏈狀稀烴或具有乙稀基之芳香族化合 又具有乙烯基之芳 1 了列舉如.乙稀及丙稀等， mw 例，可列舉如：苯乙稀、 甲基本乙細或核以烧基取代之苯 二經所構成之單體單元為5。莫耳%以下:如 具有乙稀基之芳香族化合物形成在 狀:可比此量少。該三元共聚物中，由鍵 狀从所構成之單體單元通f約為5至 =。之芳香族化合物所構成之單體單元通常約為 塑性環稀㈣樹脂之例係如：德國 :太7 口 卿」’ JSR股份有限公司銷售之「Arton」， 日本W股份有限公㈣售之「ZE_R」及「咖Μ」， 316533 12 '200521503 =井化學股份有限公司銷售之「Apel」#。可將此等環 =糸樹脂製成膜，在製膜方面宜使用溶_造法及炫融 :出法寻習知方法。製成膜之環烯烴系樹脂膜在市面上亦 有販售’例如：積水化學工業股份有限公司銷售之「咖」 ，SCA40」’或0ptes股份有限公司銷售之「z_a f^ 寺。 」 保護膜之厚度雖以薄者為佳，然而若太薄則強度降 低加工性變差，另一方面如過厚，一則透明性降低，再 則發生偏光板之重量變大等問題。因此，保護膜（尤其環稀 您系樹脂臈）之適當厚度，例如約$5至2〇〇"，以約1〇 至150//m為佳，以2〇至1〇〇//m為更佳。 由該環稀烴系樹脂所構成之保護膜，可貼合在偏光膜 之早面上’亦可貼合在兩面上。將由環浠烴系樹脂所構成 之保濩膜貼合在偏光膜之兩面上時，兩片保護膜可為相同 種類’亦可為不同種類。將由環烯烴系樹脂所構 膜貼合在偏光膜之單面時，在其之反面可貼合由環稀煙^ 樹=以外之樹脂所構成之保護膜。由環烯烴系樹脂以外之 樹脂所構成之保護膜之例，可列舉如：—直以來所廣泛使 用，偏光板之保護膜的乙酸纖維素系樹脂膜。乙酸纖維素 系:樹脂膜可為例如：三乙酿基纖維素膜或二乙酸基纖維素 膜等。三1酸基纖維素膜可為例如富士軟#股份有限公司 (Fun Photo Film Co.)銷售之「Fuj.iTac TD8〇」、「FujiTac F」及 FujiTac TD80UZ」，及 Konica Minolta Opto 股份有限公司銷售之「KC8UX2M」及「Κ8ϋγ」等。乙酸纖 316533 ,200521503 維素系保護膜之厚度約為20至200 , 樹脂以外樹脂所構成之保護膜之其他：:：列:，烴系 對苯…乙二醋、聚對苯二甲酸』;：：由聚 丁二醋等聚醋系樹脂所構成之膜七士/ 對本二甲酸 構成之膜等光學透明性優異之^或以碳酸醋系樹脂所 再者’上述保護膜中，貼附偏光 ::施行防眩處理、強一_處理: = 表面處理。又’〜二： 戶或被化合物等構成之被覆層。此等表面處理 2=在將環烯煙系樹赌所構成之保護媒 :::::::膜之一表面;又’在將_ 脂所構成之保=:::m面而將其”之樹 膜之表面。 於另-面如，可施加於任-方保護 在本發明中，將如以上說明之環烯烴系樹脂膜，介由 ^ ^積層於如以上說明之聚乙烯醇系樹脂所構成之鲁 至v面上，形成偏光板。亦可將環烯烴系樹脂 膜積層在偏光膜之單面上，而將環烯烴系樹脂以外之樹脂 所構成之保護膜積層於另—面上。其中所使用之接著劑， 、/、/、展婦火二系树脂膜接著所使用之接著劑，係以胺基甲 -、-曰樹知氧雜環丁烧化合物及環氧化合物調配而成之組 成物*將環烯烴系樹脂以外之樹脂所構成之保護膜積層在 偏光膜之單面時，所使用之接著劑非必須為此處所規定 者而從施工容易度等而言，一般以在兩面使用相同的 14 316533 200521503 接著劑較為有利。 胺基甲酸酯樹脂，可列舉如··㈣系胺基甲酸酯樹脂、 *酉曰系月女基甲酸酯樹脂或壓克力系胺基甲酸酯樹脂等，然 而其中以聚醋系離聚物型胺基甲酸醋樹脂為佳。聚醋系離 ♦物型版基甲酸酯樹脂，係指具有聚酯骨架之胺基甲酸醋 樹脂，並在其中導入少量離子性成分（親水成分）。該離聚 物型月女基甲酸醋樹脂，由於可在無需使用乳化劑下直接在 水中礼化’形成膠乳’因而適合作為水系接著劑。聚酯系 離水物型月女基甲酸酯樹脂本身為習知，例如在日本專利特 開平7-97504號公報中即記載使酚系樹脂在水性介質中分 政之南分子分散劑之例。此種聚酯系離聚物型胺基甲酸酯 樹脂，可藉由例如以下之方法製造。 (1)使含有親水性基之化合物（A)、聚酯多元醇（B)及聚 /、氰1點（C)反應，將所得之含有親水性基之聚胺基曱酸酯 樹脂在水中乳化，而得到離聚物樹脂之方法；（2)使含有親 水性基之化合物（A)、聚酯多元醇及聚異氰酸酯（[)反 應，然後將親水性基經導入且末端含有異氰酸酯基之胺基 甲酸酯聚合物分散在水中並與多元胺反應，得到離聚物樹 月曰之方法等。 其中所使用之含有親水性基之化合物，例如可列舉 如：2-羥基乙磺酸、磺酸基琥珀酸、對胺基苯磺酸或2, 4一 一月女基曱本石黃酸之含石黃酸基化合物，如2，2 -二經曱基丙 酸、二經基馬來酸或3, 4-二胺基苯甲酸之含羧酸基化合 物’或聚合物中至少具有1個活性氫之聚氧伸乙基二醇、 316533 15 200521503 聚氧伸乙基〜聚氧伸丙基共聚物二醇等。 聚酯多元醇（B)除藉由二元 縮合反應得到之聚醋外，可列舉與酸成分進行脫水 己内n«合反應所得到之 醋。聚醋多元醇中所使用之 成彼寻之共聚合聚 -？5$ 醇成刀，可為乙二醇、1¾ 广、U-丙二醇、U—丁二醇、戊二醇、3_甲：丙 戊一％、1，6-己二醇、新戊二醇、二乙二醇、二土 ， 四：二醇、聚乙二醇(分子量3〇。至6，_)、：-:、 二丙二醇、2,2 —二乙基二醇、2_ 丁 二： 丙：％、2-乙基-i，3-己二醇、貳羥基乙氧基苯、“―環己 等：二4r%己烷一曱醇、雙酚A、氫化雙酚A、氫醌及彼 …麻成物等。X’酸成分，可列舉如：琥終 己一酸、壬二酸、癸二酸、十二烷二羧酸、馬來酸、富馬 酸、1，3-環戊烷二羧酸、丨，4_環己烷二羧酸、對苯二甲酸、 鄰苯：曱酸、苯二曱酸、萘二羧酸、2, 5-萘二羧酸、 2, 6-奈二羧酸、一萘二甲酸、聯苯二羧酸、l 2_貳（苯氧 基）乙烷-p，P’-二羧酸及彼等之二羧酸酐或酯形成性衍生 物，對經基苯甲酸、對-(2-經基乙氧基）笨曱酸及該等經基 羧酸之酯形成性衍生物等。 再者，聚酯系離聚物型胺基曱酸酯樹脂除上述聚酯多 元醇之外，在不阻礙本發明效果之範圍内，亦可併用其他 问刀子里多元醇成分或低分子量之含活性氫化合物。高分 子1夕元醇，可為例如聚酯多元醇、聚碳酸酯多元醇、聚 316533 16 200521503 縮醛多元醇、聚丙烯酸酯多元醇、聚酯醯胺多元醇或聚硫 醚多元醇等。又，低分子量之含活性氫化合物，例如可為 如乙二醇、新戊二醇、1，6—己二醇、甘油、三羥甲基丙烷 之多羥基化合物；如乙二胺或暖哄之二胺化合物等。其中， 以併用低分子量之含有活性氫之化合物為較佳之形態。 上述之聚異氰酸酯（C)為分子内至少具有2個異氰酸 酯基之化合物，具體而言，例如：2, 4_甲苯二異氰酸酯、 苯基二異氰酸醋、4, 4，-二苯基甲烷二異氰酸醋、丨，6—六亞 甲基二異氰酸酯或異佛爾酮（is〇ph〇r〇ne):異氰酸酯等。 此等含有親水性基之化合物（A)、聚酯多元醇（b9)及聚 異氰酸S旨⑹之反應，雖可在無溶劑下進行，然而在有機溶 = '進行亦無妨。將得到之樹脂，用氫氧化納或氫氧化鉀 j不揮發性驗，或如三乙胺或二甲基乙醇胺之胺類，或氨 中和，再於其中加水，可得到聚醋系離聚 樹脂之水性分散液。 溶劑胺基甲酸㈣脂，當反應中使用有機 由基餾等二：有機浴劑之狀態時，以將該有機溶劑藉 w式去除後再使用較為有利。該胺基甲酸浐 由於為離聚物型，可在水中形成極微 "曰 製成不含有機溶劑之水系接著劑。’而 聚醋系離聚物型胺基甲酸酯樹脂 5, 〇〇〇以上為較佳，而、，去θ 里里十均分子罝以 _，〇〇〇以下為更户1 均分子量為10,〇0〇以上， 下，則接著芦血、/ ° /、之重量平均分子量若為5,刪以 者層無法得到充分之強度，又若高於職_以 316533 17 200521503 上，則將其製成水分散液時之黏 '嶋物型胺基㈣二== 作。 狀m製成水系接著劑。該水系接著月、7中之 而言，以2 Qflf) mP J之站度，從操作觀點 2，_ mPa·咖以下為較佳 s…為更佳，尤其以500 mPa. 特“ :· 越低，接著劑之塗布變得越W :度 板之外觀亦變得良好。該水：：,先 基甲酸酯樹脂之固形份^ ^ 曰系料物型胺 言，以1〇至70重!;度，從黏度與接著強度之觀點而 重里％之靶圍為較佳，而以20重量％以卜《 5〇重量％以下為特佳。 υ重里心乂上， 再予Γίί離聚物型胺基甲酸醋樹脂之水分散液中，亦可 ^ -醇或聚環氧乙烷等，以及界 可添加聚甲基丙輪乙醋、聚丙稀酸經乙U 丙細酸或聚乙稀醇系樹脂等水溶性樹脂。 乙酉日來 本發明中使用之較佳 酸酉旨樹脂，可_ / 聚糸離聚物型胺基甲 銷售之「 μ 。·大日本油墨化學工業股份有限公司 y ran ΑΡ-20」或「Hydran ΑΡ-101Η」等。 在本發明中，降 樹脂(以S有如以上說明之胺基曱酸酯 使用含有氧二？型坡基甲酸㈣脂為佳)之外，同時 藉由與氧雜^、卜兀化合物及環氧化合物之水系接著劑。 光膜=凡化合物及環氧化合物併用，便可提高 九馭,％烯烴系樹脂膜之接著性。 每 環丁 ^衣丁燒化合物為分子内具有四員環醚（亦即氧雜 凡衣之化合物。其例可列舉如：3-乙基-3-羥曱基氧 316533 18 200521503 ，環丁m如（3—乙基}氧雜環丁基）甲氧美 本、3-乙基-3-(苯氧甲基）氧雜環丁烧 土 =基)甲基]，一(2_乙基己氧基(甲^ 丁m雜/ 1 烧基丙氧基）甲基]氧雜環 #产丰"衣丁土矽倍半氧烷（311%3卩1^〇別时）、及西分搭 樹脂氧雜環丁焓笙 ^^ ^ 由將呈右〜4 、八，㈣環丁基石夕倍半氧烧意指藉 /、有乳濰環丁基之矽烷化合物(例如上述之3_乙基 合 =到三之乙且氧古基錢基丙氧基）甲基]氧雜環丁焼）水土解縮 /、有後數個祕環丁基之網狀聚⑪氧烧化合 乙匆美此寺，j燒化合物中，以對水之分散性優良之3_ 口土 ？工甲基氧雜環丁烷為佳。氧雜環丁烷化合物之市售 東亞合成股份有限公司銷售之Γ〇χΤ-101」等。 人你1化°物為分子内具有三員環亦即環氧環）之化 口 八例可列舉如：聚乙二醇二縮水甘油醚、聚丙二醇 —、，、侣水甘油喊、聚四亞甲基二醇二縮水甘油喊、新戊二醇 :縮水甘油喊、二甘油二縮水甘油喊、乙二醇二縮水甘油 、丙一醇二縮水甘油醚、U—丁二醇二縮水甘油醚、u_ —醇二縮水甘油醚、雙酚A二縮水甘油醚、雙酚F二縮 2油醚、間苯二驗二縮水甘油趟、甘油三縮水甘油謎、 /工曱基丙烧二縮水甘油_、山梨醇多縮水甘油趟、山梨 酵軒多縮水甘油ϋ、季戊四醇多縮水甘油謎、聚甘油多縮 ^甘油ϋ、2-(3,4-乙氧基環己基）乙基三曱氧基石夕烧、3_ 甘油氧基丙基三曱氧基石夕烧、3_縮水甘油氧基丙基三 乙軋基石夕垸或3-縮水甘油氧基丙基曱基二乙氧基石夕烷 316533 19 ,200521503 1 :對水分散性優良者為佳。環氧化合物之市隹 「CR 5丨 本油墨化學工業股份有限公司銷售之 ' 」，分別由共榮化學股份有限公 4〇E」及「Epolite 8〇mf 肖。之 EP〇ilte *銷售之「ΚΒΜ3(Π 「^越化學股份有限公司 均。之 ΚΒΜ-303」、「ΚΒΜ_4〇3」及「κβε_4〇3」等。 關於胺基甲酸酯樹脂、惫雜 物之W 烧化合物及環氧化合 =之:,比，相對於胺基甲酸醋樹脂之固形们 二番 =肅合物及環氧化合物以分別選擇至約5至 仆人里彳π之Μ為佳，再者，氧雜環頂化合物及淨氧 化合物以分別選擇至約5至6〇曹旦彳八+ μ 虱 選擇至約5…量份之範=之:圍為 物及環氧化合物之比率過低，則：c化合 产，又#让j”，、z去侍到充分之接著強 = 右^率過大’除接著狀安定性降低之外，接著 別之黏度變咼，操作將變得困難。 如以上說明，本發明之最大特徵為使用含有胺基甲酸 醋樹脂、氧雜環丁烧化合物及環氧化合物之水系 該水系接著劑由於實質上盔需使用右 d B貝上'、、、而使用有機溶劑，因此在環境 及在作t人狀㈣上丨會造絲冑，_ 雜環丁烧化合物及環氧化合物，而可得到高接著力。开用乳 “將偏光膜與由環稀烴系樹脂構成之保護膜以接著劑接 =之方法’或將由環烯烴系以外之樹脂所構成之保護膜積 層在偏光板之單面上之方法，可為—般習知之方法，例如 猎由.流延法、梅爾棒（Meier bar)塗布法、凹版塗布法、 模頭塗布法、浸潰塗布法或喷霧法等，於偏光膜及二或保護 316533 20 200521503 ，之接著面塗布接著劑，再料者疊合之方法。流延法音 心使為被塗布物之偏光膜或保護膜，朝大致垂直方向、大 致水平方向或兩者間之傾斜方向移動，同時令接著劑流下 至f面而使其塗布之方法。將接著劑塗布後，將偏光膜盘 保護膜藉由壓輥(nip roUs)夾緊，使其貼合。 ，、 又’為提高密著性，亦可在偏光膜及/保護膜之接著表 面，適宜地實施電漿處理、電暈處理、紫外線照射處理、 火焰⑴繼）處理或4化處理等表面處理。4化處理可列舉 如：浸潰於氫氧化納或氫氧化鉀等驗性水溶液之方法。 將偏光膜與保護膜積層後，施行乾燥處理。乾燥處理 可藉由吹送熱風之方式進行，其溫度可從約4()至⑽。〔之 較佳60至_之範圍内適宜地選擇。乾燥時間約 為20至！，秒。乾燥後以在室溫或比其稱高 如約20至抓之溫度）進行調和（⑽仙咖⑽約^至】 600小時為佳。乾燥後接著層之厚度通f約為g⑽至$ P，以0.0—以上為佳；又以2"以下為更佳，以） "以下為最佳。如接著層之厚度比一厚時， 之外觀容易變差。 本發明之偏光板中，亦可在保護膜之表面，瘦 劑貼附光學機能性膜。光學機能性膜可為例如在基材表面 塗覆液晶性化合物並加以定向之光學補償膜，透過某種偏 光光（polarized light)並反射顯示與其相反之性質之偏 光光之反射型偏光分離膜’由聚碳_系樹脂所構成之相 位差（Phase difference)膜，環狀聚稀烴系樹脂所構成之 316533 21 200521503 相位差膜，表面具有凹凸形“时 防止表面反射處理之膜， 祛此之肤，經趨 同時具有反射機能與穿透 表:!覆液晶性化合物並加以定向之光學 之帀售品，如富士赴H 本 u卞仰禎月昇 日本石油股份有限公司銷售之「簡膜”戈「二」(任了 -項均為商品名)等。相當於穿透某種 、」/_何 其相反之性質之偏先去夕 、’射頒示與 、 之反射型偏光分離膜之市隹。j 明尼蘇達礦業製造公麵公娜曰本 銷售之「DBEF」（商口文、笙 Μ A刁） 〇口名）專。又，相當於環狀聚烯烴手抖 脂所構成之相位差膜之市隹σ ^ τ〇π ^ Η 之「」、積水化R股份有限公司鱗售 、 子業月又伤有限公司銷售之「SCNA 、 ::pteS股份有限公司銷售之「〜_膜」 二、 為商品名）等。 貝勺 貫施例 、'以下，藉由實施例更詳細地說明本發明，然而本發明 亚二受此等實施例之限定。實施例中，表示含量或使用量 之「％」及「份」，若無特別指明，係以重量為基準。 i施例1 將平均聚合度為約2,400，皂化度為99·9%以上且厚度 為75 // m之聚乙烯醇膜，以乾式法單軸延伸約5倍，在保 持原張力狀態下，浸潰於60°C純水中1分鐘後，浸潰於碘 /碘化鉀/水之重量比為〇 〇5/5/1〇〇之28t：水溶液中6〇 秒。然後，浸潰於碘化鉀/硼酸/水之重量比為8. 5/8. 5/1〇〇 316533 22 200521503 之72°C水溶液中300秒。繼而用26°C之純水洗淨20秒後， 於65T：乾燥，得到在聚乙烯醇上吸附碘並經定向之偏光 膜。 另一方面，在聚酯系離聚物型胺基甲酸酯樹脂之水性 膠乳（大日本油墨化學工業股份有限公司製之「办打⑽ AP-20」，固形份濃度30%，黏度3〇mPa · sec)1〇〇份中，添 加氧雜裱丁烷化合物之東亞合成股份有限公司製之 L〇XT-101」（化學名稱：3 一乙基一 3 一羥甲基氧雜環丁烷 份及環氧化合物之信越化學工業股份有限公司製之 〆KBM-303」（化學名稱：2 —(3, 4—乙氧基環己基）乙基三甲 氧土夕烷）5伤，製成接著劑。在先前所得之偏光膜之兩 面，將經施行電暈處理且由降冰片稀系樹脂所構成之· m厚之保護膜（0ptes股份有限公司製之「以_膜」）藉 由上述接著劑貼合，於8 〇龄燁5 g 5刀^而得偏光板。然後， 2 ^周和6日。在該偏光板之表面，沿透過軸方向（相 =錢之法線方向（n〇〇]al vel〇city)偏斜45。角之方 姓果置^Γ刀之刀4 ’試驗偏光膜與該保護膜之剝離情況， 、、、口禾元全未剝離。 實施彳 且由I:::於偏光膜之保護膜’-面施行經電暈處理 -面施行夺：所構成之⑽㈣厚「Ze〇_膜」，另 80“厚膜H4化處理且由三乙酿基纖維素所構成之 -^ ^f " '7 ^ ^ ^ 51 ^ Γ ^ ,), 間為40c，8日以外，以與實施例1同樣之方 316533 23 ,200521503 式製造偏光板。對於所得之偏光板，以與實施例1同樣之 方式進行剝離试驗，結果兩面皆未剝離。 實施例3 除了使用別種環氧化合物之大日本油墨化學工 rre 呆奴份 义A 5衣之「CR-5L」（多官能縮水甘油醚）以取代環氧化 合物「KBM-303」以外，以與實施例i同樣之方式製造偏光 板。對於所得之偏光板，以與實施例丨同樣之方 離試驗，結果全部未剝離。 仃剝 比較例1 一除了不添加環氧化合物「KBM-303」以外，以與實施例 1同樣之方式製造偏光板。所得之偏光板，為易於 保護膜者。 ^ i 比較例2 除了使用在水100份中添加經羧基改質之聚乙烯醇 加叫股份有限公㈣之Ku加ay PQvai Kui8)3^ 水洛性聚醯胺環氧樹脂(住友化學工業股份有限公司制之 s_lrez樹脂650)(固形份濃度為3〇%之水 衣 接著劑，且調和時間為4rc，“以外，以與實 樣之方式製造偏光板。所得 ."N ° 膜者。 偏先板，為易於剝離之保護 316533 24The amount of boric acid in Renhe / Ye, relative to 100 parts by weight of water, iS is usually about 2 to 15 # deniers, eight parts, and preferably about 5 to 12 parts by weight. In the use of iodine as a dichroic g _ ^ ^ use ^ ^ d aqueous solution containing boric acid is better to contain Ehua fine. Contains lithopentic acid, hexa, /, Zhong Yue / hydration in the mixture The amount of potassium relative to 100 replacement parts of water, usually about 0 1 5G. 1 to 15 parts by weight, about 5 to 12 parts by weight as soil. The immersion time in 3 depends on the aqueous solution, It is usually about 60 to '200 t, preferably about 150 to 600 seconds, and more preferably about 0 to 400 seconds. 3 The temperature of the aqueous solution with rotten acid is usually 50 ° C or more, and 50 to 85 ° C is preferred, and 60 to Europe is more preferred. Polyethylene resin film after physical and chemical treatment is usually washed with water. X First treatment, for example, by treating boric acid-treated polyethylene The alcohol-based resin film is immersed in water. The temperature of the water in the washing treatment is usually about 5, 40 ° C, and the immersion time is usually about 2 to 120 seconds. After the water is washed and dried, the polarizing film can be seen. The drying process is usually carried out using a hot air dryer or a de-infrared heater. The temperature of the drying process is usually about 30 to 50, and preferably 50 to 80c. The time is usually about 60 to _ seconds, and preferably about 120 to _ seconds. 316533 11 200521503 Therefore, if a single-pigment dyeing and boric acid treatment are performed on the polyvinyl alcohol-based resin film, the monochromaticity is about 5 to 40 ". Polarizing film in this frame. The thickness of the polarizing film is to be laminated in the polarizer at least. Cycloene-based resin means, for example, a polarizing plate. The thin-film monomer is composed of a ring-shaped swelling Γγ; such as a precipitation sheet ~, a multi-ring ice-cooling thermoplastic resin nr H. .丨 eiln) Monomers or monomers of monomers: Use: Species: In addition to τ, the ring-opening of the above-mentioned dilute hydrocarbons, and 2: Addition of chlorinated products of the ring-opening copolymers of feminine. In addition, the introduction of polar aromatic compounds = read: Combined with chain-like dilute hydrocarbons or aromatic compounds with ethylenic groups and aromatic compounds with vinyl groups 1 Listed such as ethylene and acrylic, mw examples, such as : The monomer unit composed of styrene, methylbenzene, or benzene, which is substituted with an alkyl group at the core, is 5. Molar% or less: If an aromatic compound with ethylene is formed, it can be less than this amount. In this terpolymer, the unit f of the monomer units constituted by a bond is about 5 to =. The monomer unit composed of an aromatic compound is usually about a plastic ring dilute resin. Examples are: Germany: 太 7 口 口 "" Arton "sold by JSR Co., Ltd., and" Won "ZE_R" and "CaM", 316533 12 '200521503 = "Apel" # sold by Well Chemical Co., Ltd. This kind of resin can be made into a film by using this kind of ring resin. It is better to use the solvent-making method and the bright-melting method to find out the known methods. Cyclic olefin resin films made into films are also sold on the market. 'For example: "Ka", SCA40 "sold by Sekisui Chemical Industry Co., Ltd. or" z_a f ^ temple. "Sold by Optes Co., Ltd. Although the thickness is preferably thin, if the thickness is too thin, the workability will be deteriorated. On the other hand, if the thickness is too thick, the transparency will be reduced and the weight of the polarizing plate will increase. Therefore, the appropriate thickness of the protective film (especially thinner resin 臈), for example, about $ 5 to 200 ", preferably about 10 to 150 // m, and 20 to 100 // m as Better. The protective film composed of the cyclodilute hydrocarbon resin may be bonded to the early surface of the polarizing film 'or may be bonded to both surfaces. When the fluorene-retaining film composed of a cyclofluorene-based resin is bonded to both sides of the polarizing film, the two protective films may be the same type or different types. When a film made of a cycloolefin-based resin is bonded to one side of a polarizing film, a protective film made of a resin other than ring thin smoke ^ tree = can be bonded on the opposite side. Examples of the protective film made of a resin other than a cycloolefin-based resin include:-a cellulose acetate-based resin film which has been widely used as a protective film for polarizing plates. Cellulose acetate: The resin film may be, for example, a triethyl cellulose film or a diacetate cellulose film. Tri 1 acid-based cellulose film may be, for example, "Fuj.iTac TD80", "FujiTac F" and FujiTac TD80UZ "sold by Fun Photo Film Co., Ltd., and Konica Minolta Opto Co., Ltd. "KC8UX2M" and "Κ8ϋγ". Acetate fiber 316533,200521503 The thickness of the vitamin-based protective film is about 20 to 200, and other protective films made of resin other than resin ::: column :, hydrocarbon-based terephthalate ... ethylene glycol, polyterephthalic acid "; ：: A film made of a polyacetate resin such as polybutylene diacetate, etc. / A film made of this dicarboxylic acid, such as a film with excellent optical transparency ^ or a carbonic acid vinegar based resin :: Implement anti-glare treatment, strong one_ treatment: = surface treatment. Also '~ 2: The coating layer composed of households or compounds. These surface treatments 2 = Protection medium made of cycloolefin tobacco tree :::::::: one surface of the film; and 'protected by the grease = ::: m surface The surface of the tree film. On the other side, it can be applied to any side. In the present invention, the cycloolefin resin film as described above is laminated on the polyvinyl alcohol system as described above via ^ ^ A polarizing plate is formed from the resin to the v-plane. A cycloolefin-based resin film can also be laminated on one side of the polarizing film, and a protective film composed of a resin other than the cycloolefin-based resin can be laminated on the other side. The adhesives used in the above, 、,,,,, and the second resin film are used for the adhesive, which are formulated with amino methyl-,-oxetane compounds and epoxy compounds. The resulting composition * When a protective film composed of a resin other than a cycloolefin-based resin is laminated on one side of the polarizing film, the adhesive used is not necessarily the one specified here. In terms of ease of construction, etc., it is generally It is advantageous to use the same 14 316533 200521503 adhesive on both sides. Urethane resin can be Examples include: ㈣ series urethane resins, 酉 酉 month women's urethane resins or acrylic urethane resins, etc. Among them, polyacetate-based ionomer urethanes A vinegar resin is preferred. Polyacetate-based version of the formic ester resin refers to a urethane resin having a polyester skeleton, and a small amount of ionic components (hydrophilic components) are introduced therein. The ionomer type Crème-based formic acid vinegar resin is suitable as a water-based adhesive because it can be 'formed to form a latex' in water without the use of an emulsifier. Polyester-based water-based Crème-based ester resins are well known, such as Japanese Patent Laid-Open No. 7-97504 discloses an example of a molecular dispersant that divides a phenol-based resin in an aqueous medium. Such a polyester-based ionomer-type urethane resin can be used, for example, by It is produced by the following method: (1) A hydrophilic group-containing compound (A), a polyester polyol (B), and a poly / cyanide 1 point (C) are reacted, and the obtained polyamine group containing a hydrophilic group is reacted. Method for emulsifying ester resin in water to obtain ionomer resin; (2) The compound (A) containing a hydrophilic group, a polyester polyol and a polyisocyanate ([) are reacted, and then the hydrophilic group is introduced and the urethane polymer containing an isocyanate group at the terminal is dispersed in water and reacted with the polyamine , To obtain the method of ionomer tree month, etc. Among the compounds containing hydrophilic groups used therein, for example, 2-hydroxyethanesulfonic acid, sulfosuccinic acid, p-aminobenzenesulfonic acid, or 2, 4January Female compounds containing lutein acid of luteinic acid, such as carboxylic acid containing 2,2-di-fluorenylpropionic acid, di-maleic acid or 3,4-diaminobenzoic acid An acid-based compound 'or a polyoxyethylene glycol having at least one active hydrogen in the polymer, 316533 15 200521503 polyoxyethylene ~ polyoxypropylene copolymer diol, and the like. Examples of the polyester polyol (B) include polyacetate obtained by a binary condensation reaction, and vinegar obtained by dehydration of a caprolactone with an acid component. Copolymerization of polyisocyanate-? 5 $ alcohol into a knife, can be ethylene glycol, 1¾ radio, U-propylene glycol, U-butanediol, pentanediol, 3-methyl: 1% propylene glycol, 1,6-hexanediol, neopentyl glycol , Diethylene glycol, di earth, four: diol, polyethylene glycol (molecular weight 30. to 6, _),:-:, dipropylene glycol, 2,2-diethyl glycol, 2-butane: Propane:%, 2-ethyl-i, 3-hexanediol, hydroxyethoxybenzene, "-cyclohexyl, etc .: 2 4r% hexane monoethanol, bisphenol A, hydrogenated bisphenol A, hydroquinone And other ... hemp products, etc. Examples of the X 'acid component include: succinic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, 1,3- Cyclopentanedicarboxylic acid, 4-cyclohexanedicarboxylic acid, terephthalic acid, phthalic acid: osmic acid, phthalic acid, naphthalenedicarboxylic acid, 2, 5-naphthalenedicarboxylic acid, 2, Forming derivatization of 6-naphthalenedicarboxylic acid, mononaphthalenedicarboxylic acid, biphenyldicarboxylic acid, l 2_ 贰 (phenoxy) ethane-p, P'-dicarboxylic acid and their dicarboxylic anhydrides or esters Compounds, p-acrylic acid, p- (2-acylethoxy) benzic acid, and ester-forming derivatives of these acrylcarboxylic acids, etc. Furthermore, polyesters are isolated In addition to the above-mentioned polyester polyols, the physical amino resins can be used in combination with other polyol components or low-molecular-weight active hydrogen-containing compounds, as long as they do not hinder the effects of the present invention. The polyol may be, for example, polyester polyol, polycarbonate polyol, poly316533 16 200521503 acetal polyol, polyacrylate polyol, polyesteramine polyol, or polysulfide polyol. Also, low molecular weight The active hydrogen-containing compound may be, for example, a polyhydroxy compound such as ethylene glycol, neopentyl glycol, 1,6-hexanediol, glycerol, or trimethylolpropane; such as ethylenediamine or a warm diamine compound Etc. Among them, a low molecular weight compound containing active hydrogen is preferred. The aforementioned polyisocyanate (C) is a compound having at least two isocyanate groups in the molecule. Specifically, for example, 2, 4-toluene Isocyanate, phenyl diisocyanate, 4, 4, -diphenylmethane diisocyanate, hexamethylene diisocyanate or isophorone: Isocyanates, etc. These contain hydrophilic groups The reaction of the compound (A), the polyester polyol (b9) and the polyisocyanate S can be carried out in the absence of a solvent, but it may be carried out in an organic solvent = '. It is possible to use the obtained resin with hydroxide Sodium or potassium hydroxide j non-volatile test, or amines such as triethylamine or dimethylethanolamine, or ammonia neutralization, and then add water to it to obtain an aqueous dispersion of polyacetate ionomer resin. Solvent amine It is more advantageous to use the organic solvent such as organic distillation when the organic solvent is used in the reaction, such as organic distillation, to remove the organic solvent by using the w method. It can be formed in water very slightly " It can be made into water-based adhesive without organic solvents. 'Polyester-based ionomer type urethane resin is more than 5,000, and it is better to go to θ Here, the average molecular weight is _, 〇00 or less, and the average molecular weight is 10,000 or more. Then, if the weight average molecular weight of reed blood, / ° /, is 5, it cannot be deleted. Get sufficient strength, and if it is higher than _ 533,533 17 200521503, make it into water dispersion The viscosity of the liquid when the type of amine type ㈣ = = works. The shape m is an aqueous adhesive. In terms of the water system, in terms of the month and the seventh, with a standing degree of 2 Qflf) mP J, from the operational point of view, _ mPa · c is preferably s ... is better, especially 500 mPa. Special ": · 越The lower, the coating of the adhesive becomes more W: the appearance of the plate also becomes good. The water ::, the solid content of the hexamethylformate resin ^ ^ refers to the material type amine, with 10 to 70 weight Degree; from the viewpoint of viscosity and adhesion strength, the target range of %% is better, and 20% by weight and less than 50% by weight are particularly preferred. On the heart, give the ionomer In the aqueous dispersion of type urethane resin, alcohols or polyethylene oxides can also be added, and polymethylpropane ethyl acetate, polyacrylic acid can be added with ethyl acrylic acid or polyethylene. Alcohol-based resins and other water-soluble resins. Acetyl is the preferred acid resin used in the present invention. It can be marketed as "μ" by polyamidoionomer type amino esters. · Dainippon Ink Chemical Industry Co., Ltd. "ran ΑΡ-20" or "Hydran ΑΡ-101Η", etc. In the present invention, in addition to reducing the resin (for the amino esters of S as described above, it is preferable to use oxygen-containing di-poroformic acid esters of grease), at the same time, by combining with oxo, oxo compounds and epoxy Water-based adhesive for compounds. Light film = All compounds and epoxy compounds can be used together to improve the adhesion of Jiuyu,% olefin resin film. Each cyclamidine compound is a compound having a four-membered cyclic ether (that is, oxanil) in its molecule. Examples include 3-ethyl-3-hydroxyfluorenyloxy 316533 18 200521503, cyclamidine Such as (3-ethyl} oxetanyl) methomeben, 3-ethyl-3- (phenoxymethyl) oxetanyl = methyl), one (2-ethyl Hexyloxy (methyl ^ buta / 1-alkenylpropoxy) methyl] oxetane # Production " Yibutin silsesquioxane (311% 3 卩 1 ^ 〇 other times), and Western Separating resin oxetane enthalpy ^^ ^ From the right to the 4th, the 8th, the cyclobutyl stone sesquioxane means to borrow /, the silane compounds with cyclic cyclobutyl (such as the 3-ethyl He = to the third ethyl and oxyglyceryl propoxy) methyl] oxetanium) water and soil shrinkage /, with a few mysterious cyclobutyl network polyfluorene oxygen fired compound Temple, J_ compound, to 3_ mouth soil with excellent dispersibility to water? Methyloxetane is preferred. Commercially available oxetane compounds Γχχ-101 "sold by East Asia Synthetic Co., Ltd. and the like. The human chemical compound is a three-membered ring (that is, an epoxy ring) in the molecule. The eight examples can be listed as: polyethylene glycol diglycidyl ether, polypropylene glycol — ,, glycerol, polytetramethylene Methylene glycol diglycidyl, neopentyl glycol: glycidol, diglycerol diglycidyl, ethylene glycol diglycidyl, glycerol diglycidyl ether, U-butanediol diglycidyl ether , U_ — alcohol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, resorcinol diglycidyl ether, glycerol triglyceride mystery, / glycyl propylene glycol diglycidyl _, Sorbitol polyglycidol, Sorbitol polyglycidol, Pentaerythritol polyglycidyl mystery, Polyglycerol polyglycidyl glycerol, 2- (3,4-ethoxycyclohexyl) ethyltrioxolite Yukiyaki, 3_glyceryloxypropyltrioxoyl oxalate, 3_glycidyloxypropyltriethyroyl oxalate or 3-glycidyloxypropylpyroxydiethoxylithane 316533 19, 200521503 1: Better for water dispersibility. The market for epoxy compounds "CR 5 丨" sold by Ben Ink Chemical Industry Co., Ltd. "is sold by Gongrong Chemical Co., Ltd. 40E" and "Epolite 8〇mf Shaw. EP〇ilte *" ΚΒΜ3 (Π "Etsuyoshi Chemical Co., Ltd. KKBM-303", "KBM_4〇3" and "κβε_4〇3", etc. About carbamate resins, W compounds and epoxidized compounds = :, compared to the solid form of the urethane resin = sulfonate and epoxy compound are preferably selected to about 5 to 彳 π of the servant, respectively, in addition, the oxetane compound And net oxygen compounds are selected to about 5 to 60 respectively. Cao Dan 彳 8 + μ lice are selected to about 5 ... part of the range = of: the ratio of Waiwei and epoxy compounds is too low, then: c chemical production, Also, let j ”, and z go to full strength and then strong = right ^ rate is too large 'in addition to reduced stability of the shape, and then other viscosity becomes high, the operation will become difficult. As explained above, the present invention The biggest feature is the use of urethane resin, oxetane compounds and epoxy compounds Because the water-based adhesive requires organic solvents to be used on the helmet, it will make silk in the environment and in humans. Heterocyclic compounds and rings Oxygen compounds can be used to obtain a high adhesive force. Opening the emulsion "the polarizing film and the protective film made of cyclodiene-based resins are bonded together" or the protective film made of resins other than cycloolefins is laminated The method on one side of the polarizing plate may be a conventional method, such as hunting, casting, Meier bar coating, gravure coating, die coating, dip coating, or Spray method, etc., on the polarizing film and two or protection 316533 20 200521503, followed by coating adhesive on the surface, or the method of superimposition. Casting method is to make the polarizing film or protective film of the object to be coated. A method of moving the adhesive in a vertical direction, a substantially horizontal direction, or an oblique direction therebetween while flowing the adhesive down to the f-side. After the adhesive is applied, the polarizing film disk protective film is passed through a nip roUs. Clamp to make it fit. ,, ' In order to improve adhesion, a surface treatment such as a plasma treatment, a corona treatment, an ultraviolet irradiation treatment, a flame curing treatment, or a chemical treatment may be suitably performed on the surface of the polarizing film and / or the protective film. Examples of the chemical conversion treatment include a method of dipping in a test aqueous solution such as sodium hydroxide or potassium hydroxide. After the polarizing film and the protective film are laminated, a drying process is performed. The drying process can be carried out by blowing hot air, and the temperature can be from about 4 ° to ⑽. [The range of preferably 60 to _ is appropriately selected. The drying time is about 20 to! ,second. After drying, it is conditioned at room temperature or a temperature higher than its nominal value, such as about 20 to about 120 ° C (about 至 to】) for about 600 hours. After drying, the thickness of the subsequent layer is about g⑽ to $ P, It is better to be 0.0-above; and 2 " is better, and) " is best. If the thickness of the adhesive layer is thicker than one, the appearance is liable to deteriorate. In the polarizing plate of the present invention, a thin film may be attached to the surface of the protective film with an optical functional film. The optically functional film may be, for example, an optical compensation film that is coated with a liquid crystal compound on the surface of the substrate and oriented, and transmits a polarized light and reflects a polarized light that exhibits properties opposite to the polarized light. Phase difference film composed of polycarbonate resin, 316533 21 200521503 retardation film composed of cyclic polyolefin resin, the surface has a concave-convex film. The skin has both a reflective function and a penetrating surface :! Optical products that cover liquid crystal compounds and are oriented, such as Fuji Go to Japan, Japan, Japan, Japan and Japan. Two "(Ren Ren-items are trade names) and so on. It is equivalent to a kind of reflective polarizing separation film that penetrates a certain kind of "" / _ and what is the opposite of it. j Minnesota Mining Manufacturing Co., Ltd. "DBEF" (Shangkouwen, Sheng M A Diao), which is sold by the company. In addition, it is equivalent to the "」 "of the market 相位 σ ^ τ〇π ^ 相位 of the retardation film composed of cyclic polyolefin hand shake grease, sold by Sekisui R Co., Ltd., and sold by Ziye Yueyou Injury Co., Ltd. SCNA, "~ _membrane" sold by :: pteS Co., Ltd. (2, is the trade name), etc. In the following examples, the present invention will be described in more detail through examples, but the present invention is limited by these examples. In the examples, "%" and "parts" indicating content or usage amount are based on weight unless otherwise specified. Example 1 A polyvinyl alcohol film having an average degree of polymerization of about 2,400, a degree of saponification of more than 99.9%, and a thickness of 75 // m was uniaxially stretched about 5 times by a dry method. With the original tension maintained, After being immersed in pure water at 60 ° C for 1 minute, it was immersed in a 28t: water solution with a weight ratio of iodine / potassium iodide / water of 0.05 / 5/60 for 60 seconds. Then, it was immersed in a 72 ° C aqueous solution having a weight ratio of potassium iodide / boric acid / water of 8. 5/8. 5/100 316533 22 200521503 for 300 seconds. Then, it was washed with pure water at 26 ° C for 20 seconds, and then dried at 65T: to obtain a polarized film that adsorbed iodine on polyvinyl alcohol and was oriented. On the other hand, in the aqueous latex of polyester ionomer-type urethane resin ("Bandaru AP-20" manufactured by Dainippon Ink Chemical Industry Co., Ltd., the solid content concentration is 30%, and the viscosity is 30%. mPa · sec) in 100 parts, with the addition of oxabutane compounds, LOXXT-101 manufactured by Toa Synthesis Co., Ltd. (chemical name: 3 monoethyl-3 methylol oxetane及 KBM-303 "(chemical name: 2- (3, 4-ethoxycyclohexyl) ethyltrimethoxyxanthane) produced by Shin-Etsu Chemical Industry Co., Ltd. and epoxy compound, and then wound. On both sides of the previously obtained polarizing film, a m-thick protective film ("Teflon", manufactured by Optes Co., Ltd.) made of corona treatment and made of a norborne resin is used. The polarizers were bonded together at the age of 80 and 5 g and 5 knives to obtain a polarizing plate. Then, 2 weeks and 6 days. On the surface of the polarizing plate, along the direction of the transmission axis (phase = normal direction of money (n〇) 〇] al vel〇city) Deflection 45. The square surname of the corner is placed ^ Γ knife of the knife 4 'Test the peeling of the polarizing film and the protective film ,,,, And Kou Heyuan have not been peeled off. The protective film implemented by I ::: on the polarizing film'-face is subjected to corona treatment-the surface is subjected to capture: the thick "Ze〇_ 膜", Another 80 "thick film H4 treatment and composed of triethyl cellulose-^ ^ f " '7 ^ ^ 51 ^ 51 ^ Γ ^,), the time is 40c, except for 8 days, in accordance with Example 1 The same method was used to make a polarizing plate in 316533 23 and 200521503. The obtained polarizing plate was subjected to a peeling test in the same manner as in Example 1. As a result, neither side was peeled off. Example 3 Except for the use of a different type of epoxy compound, Dainippon Ink A polarizer was manufactured in the same manner as in Example i except that "CR-5L" (polyfunctional glycidyl ether) of chemical engineer rre A5 was used in place of the epoxy compound "KBM-303". The polarizing plate was subjected to the same separation test as in Example 丨, and all the results were not peeled. Comparative Example 1 A polarizing plate was produced in the same manner as in Example 1 except that the epoxy compound "KBM-303" was not added. The obtained polarizing plate is a film that is easy to protect. ^ I Comparative Example 2 Except for use In 100 parts of water, carboxyl-modified polyvinyl alcohol is added, which is called Ku and ay PQvai Kui8, which is a stock limited company. 3 ^ Hydroponic polyamine epoxy resin (s_lrez resin 650 manufactured by Sumitomo Chemical Industry Co., Ltd.) ) (Water-coating adhesive with a solid content concentration of 30%, and a blending time of 4rc, "other than that, the polarizing plate is manufactured in the same way as the actual sample. The obtained. &Quot; N ° film. The polarizing plate is easy to peel Protection 316 533 24