1355514 九、發明說明： 【發明所屬之技術領域】 本發明有關碘系偏光膜、其製造方法及使用該碘系偏 光膜的碘系偏光板。 【先前技術】 偏光膜一般係使屬於二色性色素的碘或二色性染料吸 附疋向於♦乙烯醇系樹脂薄膜而製成者。於此偏光膜之至 ^面，介由黏接劑層而貼合於由三乙醯基纖維素等製成 之保蠖版以作成偏光板，並用於液晶顯示裝置等。使用碘 2為二色性色素的偏光膜，稱為碘系偏光膜，使用二色性 f料作為二色性色素的偏光膜，則稱為染料系偏光膜。此 等=t ’由於峨系偏光膜較染料系偏光膜更具備高透射率 了偏光度/亦即可顯不南對比’因而被廣泛採用。雖然 石典系偏光膜在光學特性方面勝過染料系偏光膜，惟在光學 t久性t面則較染料系偏光膜為差，例如，將硬系偏光膜 放置於乾熱下時，則合發生诱 、 題〇 則θ么生透射率降低或偏光板變色等問 ，近年來由於液晶顯示裝置應用領域之擴大 及周邊技術之進步，對偏光板性能的要长更走—执 而言，需要透射率及偏光度均高，二=厭格。具體 及耐濕熱性亦優異的偏光 ：二耐熱性 58—麵號公報（相文獻υ中，提!^ ί專利特開昭 以單向拉伸’並將此作為基材的偏光；二醋糸樹脂加 性能與耐久性兩者均優的 、；，，一 ’欲得偏光 m堝九㈣仍感不足，&需要加以 316505 5 ⑴ 5514 更進—步改良。 本㈣特開2__35512號公釘專利文獻2) ，卞有#由將經蛾染色的聚乙稀醇系樹脂 卸的：酸水溶液，浸潰處理而使偏光膜4: 里之鋅’以提尚該偏光膜在高溫下的耐久性的作法。 本專利特開咖-助31號公報（專利文獻3)中， 膜二：：碘吸附定向的聚乙烯醇系樹脂膜及為貼合保護 1的黏接劑層中’使含有聚丙烯酸或其衍㈣，以改盖 偏光板之耐久性的作法。 。 昭58-68008號公報 2000-3551 2 號公報 2003-262731 號公報 [專利文獻1]日本專利特開 [專利文獻2 ]曰本專利特開 [專利文獻3 ]曰本專利特開 【發明内容】 [發明欲解決的課題] ^本案發明人#，採用與前述專利絲1至3不同的手 段，進行為提高由聚乙烯§?系樹脂所、偏光板的 :久性研究，終於達成本發明。因而，本發明之目的在於 提供=聚乙烯醇系樹脂作為基材之經改良其耐久性的蛾系 偏光膜’提供其製造方法，更提供使用該偏光膜之耐久性 優異的偏光板。 [用以解決課題的手段] 本案發明人等在此種目的之下進行研究，結果發現在 藉由聚乙烯醇系樹脂膜之拉伸、蛾染色、帛色後之石朋酸處 理及水洗等步H造㈣、偏光膜時，若使帛為㈣色之 316505 6 1355514 3有破的水*液1為棚酸處理之含有割㈣水溶液、以 及用為水洗處理之水巾之至少—者溶解含有g萄糖酸或其 鹽，亚使用該水溶液處理聚乙稀醇系樹脂膜，即可抑制偏 光膜在乾熱下變色等問題，而完成本發明。 亦即依據本發明，可提供一種由經蛾吸附定向的聚乙 烯醇系樹脂膜製成，而該聚乙烯醇系樹脂膜再含有選自醛 糖酸（aldornc acid)及醛糖酸鹽中的醛糖酸系化合物的诚 系偏光膜。 〃 又依據本發明，亦可提供該碘系偏光膜之製造方法，φ =該方法係在經過進行聚乙烯醇系樹脂膜之單向拉伸的過 程、於含有峨及峨化卸的水溶液中進行該聚乙締醇系樹脂 膜，染色的過程、於含有石朋酸的水溶液中進行染色後之聚. =稀醇系樹脂膜之浸潰處理的過程、以及在含有的水. 岭液中之浸 >責處理後進行水洗的過程以製造料偏光膜 %，使上述含有峨及埃化鉀的水溶液、上述含有石朋酸的水 溶液、以及上述水洗用水中之至少—者，溶解含有選自醛 糖酸及醛糖酸鹽中的醛糖酸系化合物者。 /再者，依據本發明，亦可提供一種於含有上述之醛糖 酸系化合物的峨系偏光膜之一面或兩面，貼合有保護膜的 硬系偏光板。 [發明之效果] /本發明之峨系偏光膜或經於至少—面貼合保護膜的蛾 系，光板，係可防止放置於乾熱下後之劣化而成為耐久性 俊丹者。又，此等偏光膜及偏光板之平行透射色相 316505 7 明 5514 (transmission hue)係較既有產品更為接近中性色 (neutral color)者。 【實施方式】 ^以下，對本發明加以詳細說明。碘系偏光膜係於聚乙 烯醇系樹脂膜上經碘吸附定向者，而本發明中，於此偏光 膜中含有醛糖酸系化合物。 構成偏光膜的聚乙蝉醇系樹脂，可藉由聚醋酸乙烯系 樹脂之矣化而製得。聚醋酸乙烯系樹脂除了醋酸乙烯之單 獨聚合物的聚醋酸乙稀之外，尚可例示醋酸乙稀與可與其 進行共聚合的其他單體之共聚合物。可與醋酸乙稀進= 聚合的其他單體，可例舉不飽和叛酸類、稀煙類、乙婦峻 類、不飽和石黃酸類等。聚乙稀醇系樹脂之息化度 85至1〇〇莫耳％程度’較佳為⑽至1〇〇莫耳％程度。此種 2烯醇系樹脂可為再加以改質者，例如亦可使_類 ?貝的聚乙烯醇縮甲醛或聚乙烯醇縮乙醛等。又，此種淑 =醇系樹脂之聚合度通常為uoo幻〇，_左右，較I 為聚合度1，500至5, 〇〇〇左右。 將此種聚乙烯..醇系樹脂加以製膜者，即可用為偏光膜 =原胚膜。聚乙稀醇系樹脂之製膜方法並無特別限定，可 :周知之方法製膜。由聚乙烯醇系樹脂製成原胚膜 =特別限定，惟以例如為5„至15〇“左右為 k為10y m至150y m左右。 碟系偏光膜可經由進行此種聚乙烯醇系樹脂膜之單向 伸的過程、使用㈣聚乙稀醇系樹脂膜染色以使該峨吸 316505 8 附的過程、使用硼酸水溶液處理 ^ 脂膜的過程、以及在令替t及附硬的永乙細醇系樹 而製成。 在δ亥狐水溶液處理後進行水洗的過裎 〜甘單向拉伸可於蛾染色前進行，亦可與石典染色同時進 :單：二峨染色後進行。如於峨染色後進行單向拉伸時， 该早2伸可於賴處理前進行，亦可於顯處理中進 二’亦走在此等複數個步驟中實施單向拉伸。實施 可於周速不相同的報輪間往單向拉伸，亦可 親：往單向拉伸。又’可為在大氣中實施拉伸的乾 伸。拉伸倍率通常為4至8倍左=下心拉伸的濕式拉 醇系樹脂膜之峨的吸附，可於含有撕溶 通^有衫糾㈣水溶液巾，浸潰 ==色之方式實施。聚乙稀醇系樹脂膜，較佳為！ ,u ^ 員先戶、細*水的浸潰處理。含有碘及蛐 化鉀的ΐ溶液令之峨含量，係對水每！。。重量份為〇.‘、 1重里伤左右’而峨化卸之含量，係對水每】⑽重量份 .5至2〇重量份左右。該水溶液之溫度為20至4(TC左 右’又’在該水溶液中的浸潰時間為2G至1，8GG秒鐘左右。 …蛾染色後之硼酸處理，可將經破染色的聚乙烯醇系樹 曰膜,又/貝於石朋@义水/谷液中之方式實施。石朋酸水溶液中的硼 ，含量’對水每刚重量份通常為2至15重量份左右，較 佳為5至12重量份左右。該·水溶液較佳為含有峨化卸 者朋酉义水岭液3有峨化钟時，該石典化奸之量對水每1 〇〇 316505 9 1355514 重量份通常為40重量份以下，較佳為30重量份以下。又， 該碘化鉀係對水每100重量份為0丨重量份以上，更佳為 含有1重量份以上。在硼酸水溶液中的浸潰時間，通常為 60至1，200秒鐘左右，較佳為15〇至β⑽秒鐘左右，更佳 為200至400秒鐘左右。 硼酸處理後之聚乙烯醇系樹脂膜，通常加以水洗處 理。水洗處理係將經硼酸處理的聚乙烯醇系樹脂膜潰浸於 水中而貫施者。水洗後實施乾燥處理，即可製得經碘吸附 定向的聚乙烯醇系樹脂膜’亦即埃系偏光膜。 本發明中，係使此種碘系偏光膜中含有醛糖酸系化合 物，具體而言’含有醛糖酸或其鹽。醛糖酸係將醛糖（a丨d 〇 s e) 之搭基氧化而得的多羥基羧酸，以一般式 H〇CH2(CHOH)nCOOH(其中i以上之整數）表示者。並型 的=糖酸可例舉葡萄糖酸、半乳糖酸（galact〇nicacid)、 甘露糖酸（mannoic acid)、塔龍酸（tal〇nic acid)、古洛 才-夂（guIonic acid)、艾杜酸Qd〇nic acid)、阿洛糖酸 (aii〇nicacid)、阿卓糖酸（altr〇nicacid)等。本發明所 用白=酸糖酸’並不特別限定於在此所具體例示者。酸糖酸 二刀別單獨使用，或組合複數種使用。醛糖酸中以葡萄糖 酉欠4易以工業規模取得而較佳。醛糖酸之鹽可例舉鈉鹽、 鉀鹽、約鹽、鋅鹽等。其中又以鋅鹽抑制偏光膜或偏光板 在乾熱下的變色等問題之效果高而較佳。 人*醛糖酸在水溶液中，通常與醛糖内酯形成平衡關係， 曰口欠冷液中之pH而使醛糖酸與醛糖酸内酯之存在比發 316505 1355514 生變化。水溶液之鹼性愈強’醛糖酸之比例多；相反地， 水溶液之酸性愈強，醛糖酸内酯之比例會增多。又，如藉 由底縮醛糖酸水溶液等方式欲得固形物時，則可得醛糖酸 内酉曰。於疋，本發明之醛糖酸中，除醛糖酸本身之外，尚 可含有其内酯的醛糖酸内酯。如以與醛糖酸成為平衡關係 的醛糖酸内酯為例，對葡萄糖酸而言為葡萄糖酸内酯、對 半乳糖酸而言則成為半乳糖酸内酯，對其他醛糖酸亦同樣 會存在對應的搭糖酸内醋。 酸糖酸通常係藉由葡萄糖之發酵而製造，並以該形態 銷售。本發明所㈣糖㈣化合物，祇要是使偏光膜中^ 有即可顯現抑制乾熱下的變色等問題的效果者均可使用， 可為酸糖酸亦可為㈣酸鹽。又，在不妨礙此種 化合物之效果㈣圍内，亦可含有少量安定劑或防腐劑等 添加物。 ，本發明中，㉟糖酸系化合物通常係在前述的偏光膜戈 製造過程中，在使用含有峨的水溶液的染色以後之步驟今 :以導入。具體而言’如前述方式製造碘系偏光膜的過卷 :可採驗含有料料鉀的水溶液，含有用為餐虑 理的石朋酸的水溶液，以及用為_處理後之水洗的水之中 的任何-或複數種溶液中，使酸糖酸系化合物溶解的方 =其中較料於含有硼酸的水料巾轉 物使其含有的方法。 糸化σ 不管在任一步驟中使醛糖酸系化合物 水每1。。重量份，通常為。.01至60重量份左右:、= 316505 11 0*5重量{公 量份以下更佳為1重量份以上’又’較佳為30重 係對水每為15重量份以下。如搭糖酸系化合物之量 抑制所得偏#為ui重量份以下’則不能充分發揮 ^光膜在乾熱下的變色等問題的效果。 光月異中之酸·糖酸季化人你夕人旦 in w 30重量以士 裙文糸化口物之含里，—般為〇.001至 „ μ Q左右，較佳為〇·〇ι重量％以上，更佳為〇丨重旦y 以上，而較係 勹U· 1重里i 發揮抑制所°如含量過少’則不能充分 于偏光膜在乾熱下的變色等問題的效果。 旦，:聚乙稀醇系樹脂所成偏光膜中所含搭糖酸或其鹽之 =試揭依例如將偏光膜溶解於溶劑中’再使用酵素法分析 / Λ，的方法加以定量。酵素法. 國際(股)所銷售的“F —套,且…二？/了利用.J. Κ·. 内酯，，等。 右紋葡苟糖酸/右旋葡萄糖酸- 如此，使含有醛糖酸系化合物 制乾熱下的偏先腰具有抑 透射m 外’此種偏光膜之平行 相’具有較既有產品為更接近中 coior)的特徵。 | 所知·偏光膜，可於農— #知^ * /、面或兩面層合保護膜而作成偏 光板保έ又膜可例舉如三乙响美織έ# ·#· ·+、 * 基，·滅素或二乙醯基纖維素 丙烯酸樹脂膜、聚㈣脂膜、聚芳 楓樹脂膜、以例如降冰片稀等環狀稀煙作 為早脰的城等。保護膜之厚度通常為 m至200从111左右。 又’此種偏光板，亦可於一方之表面，亦即於保護膜 316505 12 1355514 硬質覆膜層、黏 之路出面，具有反射防止層或防閃光層 接層等周知之各種功能層。 [實施例] 以下，藉由實施例更詳細㈣本發明，惟本發明並不 ^寺實施例而有所限制。另外，财所示平行之色相， '1偏光膜Λ_射與其透射軸成為平行的直線偏光光線時 3射光之色相之意；而直交之色相，係指對偏光膜入射 ^其透射轴成為直交的直線偏光光線時之透射光之色相之 意。 貫施例1 將平均聚合度約2, 400、皂化度99·9莫耳％以上、厚 度75㈣之聚乙稀醇膜按乾式且拉伸倍率為5倍之方式^ ::向拉伸，再在維持緊張狀態之下浸潰於6(TC之純水! ^鐘。其次’於蛾/石典化鉀/水之重量比為〇· i5/5/⑽之水 ☆液中在28 C下浸潰48秒鐘。然後，於葡萄糖酸[5〇重量 ,溶液，從東京化成工業（股）取得]/換化卸/賴/水按重 置比10/21/9. 5/100混合的水溶液中在阶下浸潰3〇〇秒 鐘。再使用肌之純水洗淨丨.5秒鐘後在5(rc下乾燥，穿』 得聚乙_上吸附定向有破，並制有㈣糖酸的偏光、 膜。所得偏光膜依下述方法，進行在乾熱下的耐久性評估。 《耐久性之評估方法》 首先，使用分光光度針[島津製作所（股）製之 “UV-220G”]，測定偏光膜之分光穿透率r (λ )。從所得分 光透射率r (λ)，求出平行分光之透射光譜及直交分光之 316505 1355514 透射光譜，並從分別之分光透射光譜求出平行之色相L、 ，以及b*，和直交之色相L*' ?以及b*。其次，將此偏光 膜放置於1 0(TC之乾燥環境_ 14小時，以進行耐久性試 驗。就此耐久性試驗後之偏光膜重新測定分光透射率r (λ )，亚從此求出平行之色相L*、a*以及b*，和直交之色 相L、a以及b*。從耐久性試驗前後之色相〆以及^， 依下式（1)至（3)，求出分別之差△!/、△，以及Ab*，再依 下式（4)求出全體之色差^^；*。[Technical Field] The present invention relates to an iodine-based polarizing film, a method for producing the same, and an iodine-based polarizing plate using the iodine-based polarizing film. [Prior Art] The polarizing film is generally produced by absorbing iodine or a dichroic dye belonging to a dichroic dye to a ○ vinyl alcohol resin film. The surface of the polarizing film is bonded to a protective plate made of triacetyl cellulose or the like through a binder layer to form a polarizing plate, and is used in a liquid crystal display device or the like. A polarizing film in which iodine 2 is a dichroic dye is called an iodine-based polarizing film, and a dichroic dye is used as a polarizing film of a dichroic dye, and is called a dye-based polarizing film. These =t ' are widely used because the lanthanide polarizing film has a higher transmittance than the dye-based polarizing film and has a degree of polarization/contrast. Although the stone-based polarizing film outperforms the dye-based polarizing film in optical properties, it is inferior to the dye-based polarizing film in the optical t-long surface, for example, when the hard polarizing film is placed under dry heat, In the past, due to the expansion of the application field of liquid crystal display devices and the advancement of peripheral technologies, the performance of polarizing plates has become longer and longer. Both transmittance and polarization are high, and second = anamorphism. Specific and heat-resistant and excellent polarizing: two heat-resistance 58-surface publication (in the literature, 提 ^ 专利 专利 专利 专利 以 以 以 单向 单向 单向 单向 单向 单向 单向 单向 单向 单向 单向 单向 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; Resin addition performance and durability are both excellent;;, a 'desired polarization m埚 nine (four) still lack of sense, & need to be 316505 5 (1) 5514 more advanced - step improvement. This (four) special open 2__35512 male nail Patent Document 2), 卞有# is discharged from a polyether-based resin dyed with moth: an aqueous acid solution, impregnated to make zinc in the polarizing film 4: to improve the durability of the polarizing film at a high temperature. Sexual practice. In Japanese Laid-Open Patent Publication No. 31 (Patent Document 3), the film 2: an iodine-adsorbed oriented polyvinyl alcohol-based resin film and an adhesive layer for the bonding protection 1 are made to contain polyacrylic acid or Yan (4), to change the durability of the polarizing plate. . Japanese Patent Publication No. 2003-262731 [Patent Document 1] Japanese Patent Laid-Open Patent Publication No. JP-A No. JP-A No. JP-A- No [Problem to be Solved by the Invention] The inventor of the present invention finally achieved the present invention by improving the long-term study of a polyethylene-based resin and a polarizing plate by means different from the above-mentioned Patent Wires 1 to 3. In view of the above, it is an object of the present invention to provide a moth-based polarizing film having a modified polyvinyl alcohol-based resin as a substrate, and a method for producing the same, and a polarizing plate excellent in durability using the polarizing film. [Means for Solving the Problems] The inventors of the present invention conducted research under such a purpose, and as a result, found that the polyvinyl alcohol-based resin film was stretched, moth-dyed, tarnished, and treated with water and washing. In the case of step H (4), when the polarizing film is used, if the crucible is (four) color, 316505 6 1355514 3 has broken water * liquid 1 is a shed acid treatment containing a cut (four) aqueous solution, and at least one of the water towels used for washing is dissolved. The present invention can be accomplished by containing glucosic acid or a salt thereof and subliminarily treating the polyethylene glycol-based resin film with the aqueous solution to suppress problems such as discoloration of the polarizing film under dry heat. That is, according to the present invention, it is possible to provide a polyvinyl alcohol-based resin film which is oriented by a moth adsorption, and the polyvinyl alcohol-based resin film further contains an acid salt selected from the group consisting of aldornic acid and aldonic acid. The uronic acid-based compound is a polarizing film. Further, according to the present invention, a method for producing the iodine-based polarizing film may be provided, and φ = the method is carried out in a uniaxial stretching process of a polyvinyl alcohol-based resin film in an aqueous solution containing hydrazine and hydrazine The polyethylene glycol resin film is subjected to a dyeing process, a process of dyeing in an aqueous solution containing salicylic acid, a process of impregnation of a dilute alcohol resin film, and a water solution containing water. The immersion process is followed by a water washing process to produce a material polarizing film %, and the aqueous solution containing cerium and potassium ethoxide, the aqueous solution containing the sphagic acid, and at least the water for washing are dissolved and contained. From aldonic acid and aldonic acid compounds in aldonic acid salts. Further, according to the present invention, a hard polarizing plate in which a protective film is bonded to one side or both surfaces of the fluorene-based polarizing film containing the above-mentioned aldonic acid-based compound may be provided. [Effects of the Invention] The bismuth-based polarizing film of the present invention or the moth-based or light-shielding sheet which is bonded to at least the surface of the protective film can prevent deterioration after being placed under dry heat and become durable. Moreover, the parallel transmission hue of these polarizing films and polarizing plates is 316505 7 and the transmission hue is closer to the neutral color than the existing products. [Embodiment] The present invention will be described in detail below. The iodine-based polarizing film is oriented by iodine adsorption on a polyvinyl alcohol-based resin film, and in the present invention, the polarizing film contains an aldonic acid-based compound. The polyethylene glycol-based resin constituting the polarizing film can be obtained by deuteration of a polyvinyl acetate-based resin. Polyvinyl acetate-based resin In addition to polyvinyl acetate, a single polymer of vinyl acetate, a copolymer of ethylene acetate and another monomer copolymerizable therewith can be exemplified. Other monomers which can be mixed with ethyl acetate = polymerization, such as unsaturated tracism, dilute smoke, Emerald, and unsaturated rhein. The degree of recombination of the polyvinyl alcohol-based resin is from 85 to 1% by mole, and is preferably from (10) to 1% by mole. Such a 2-enol-based resin may be further modified, and for example, polyvinyl formal or polyvinyl acetal may be used. Moreover, the degree of polymerization of such an alcohol-based resin is usually uoo illusion, about _, and I is about 1,500 to 5, about 聚合. When such a polyethylene: alcohol resin is used for film formation, it can be used as a polarizing film = primordial membrane. The film forming method of the polyvinyl alcohol-based resin is not particularly limited, and a film can be formed by a known method. The virgin membrane made of a polyvinyl alcohol-based resin is particularly limited, and is, for example, 5 Å to 15 Å, and k is about 10 μm to 150 μm. The dish-based polarizing film can be subjected to a process of uniaxial stretching of the polyvinyl alcohol-based resin film, and dyed with a (iv) polyethylene resin film to cause the process of attaching the 316505 8 to be treated with an aqueous solution of boric acid. The process, as well as the preparation of the t- and hard-filled cells. The 单向 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘For example, when the uniaxial stretching is carried out after the dyeing of the enamel, the early stretching can be carried out before the treatment, and the uniaxial stretching can also be carried out in the plurality of steps. Implementation It can be stretched in one direction between the different rounds of the weekly speed, or it can be stretched in one direction. Further, it can be a dry stretch which is stretched in the atmosphere. The draw ratio is usually 4 to 8 times. The left side = lower core stretched wet pull alcohol resin film is adsorbed by a mash, and can be carried out by means of a dipping solution, a bathing solution, and a dipping == color. Polyethylene glycol resin film, preferably! , u ^ staff first, fine * water impregnation treatment. The bismuth solution containing iodine and potassium hydride gives the strontium content, which is right for water! . . The parts by weight are ‘. ‘, 1 heavy injury is left and right’, and the content of sputum unloading is about 5 parts by weight to about 5 parts by weight of water. The temperature of the aqueous solution is 20 to 4 (about TC 'and' the dipping time in the aqueous solution is about 2G to 1,8 GG seconds. ... The boric acid treatment after moth dyeing can be used to break the dyed polyvinyl alcohol The tree decidua is also carried out in the form of bismuth in Shipeng@义水/谷液. The content of boron in the aqueous solution of Shipeng acid is usually about 2 to 15 parts by weight, preferably 5, per part by weight of water. Up to about 12 parts by weight. The aqueous solution preferably contains the hydrazine decanter, the 水 水 水 3 3 3 3 3 3 3 , , , 化 化 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 40 parts by weight or less, preferably 30 parts by weight or less. Further, the potassium iodide is 0 parts by weight or more, more preferably 1 part by weight or more per 100 parts by weight of water. The immersion time in an aqueous boric acid solution is usually It is about 60 to 1,200 seconds, preferably 15 to about (10) seconds, more preferably about 200 to 400 seconds. The polyvinyl alcohol-based resin film after boric acid treatment is usually washed with water. The boric acid-treated polyvinyl alcohol-based resin film is immersed in water and applied. After washing By applying a drying treatment, a polyvinyl alcohol-based resin film which is oriented by iodine adsorption, that is, an eigen-based polarizing film can be obtained. In the present invention, the iodine-based polarizing film contains an aldonic acid-based compound, specifically 'containing aldonic acid or a salt thereof. The aldonic acid is a polyhydroxycarboxylic acid obtained by oxidizing a aldose (a丨d 〇se) group, and has a general formula of H〇CH2(CHOH)nCOOH (where i or more Integer) indicates that the type of sugar acid can be exemplified by gluconic acid, galact〇nic acid, mannoic acid, tal〇nic acid, and guluo-夂( guIonic acid), iduric acid Qd〇nic acid, aii nic acid, altogic acid, and the like. The white = acid sugar acid used in the present invention is not particularly limited to those specifically exemplified herein. Acidic acid can be used alone or in combination. Among the aldonic acids, glucose oxime is easily obtained on an industrial scale. The salt of aldonic acid may, for example, be a sodium salt, a potassium salt, an about salt or a zinc salt. Among them, the effect of suppressing the discoloration of the polarizing film or the polarizing plate under dry heat by the zinc salt is high and preferable. Human * aldonic acid in aqueous solution, usually in equilibrium with aldose lactone, the pH of the sputum is less than the pH of the cold liquid and the presence of aldonic acid and aldonic acid lactone changes 316505 1355514. The stronger the basicity of the aqueous solution, the greater the proportion of aldonic acid; conversely, the stronger the acidity of the aqueous solution, the greater the proportion of aldonic acid lactone. Further, if a solid matter is desired by means of an aqueous solution of a acetal acid or the like, an aldonic acid ruthenium can be obtained. In the aldonic acid of the present invention, in addition to the aldonic acid itself, the aldonic acid lactone of the lactone may be contained. For example, an aldonic acid lactone in a balanced relationship with aldonic acid is a gluconolactone for gluconic acid and a galactotactone for galactonic acid, and the same is true for other aldonic acids. There will be a corresponding vinegar in the sucrose. The acid sugar acid is usually produced by fermentation of glucose and is sold in this form. In the fourth aspect of the present invention, the compound of the sugar (tetra) may be used as long as it is effective in suppressing discoloration under dry heat, and the acid acid may be a (tetra) acid salt. Further, it may contain a small amount of an additive such as a stabilizer or a preservative, without impeding the effect of the compound (4). In the present invention, the 35-glyco-acid compound is usually introduced in the above-mentioned polarizing film production process, after the dyeing using an aqueous solution containing hydrazine. Specifically, the over-rolling of the iodine-based polarizing film is carried out as described above: an aqueous solution containing potassium of the material can be examined, an aqueous solution containing shiban acid used as a meal, and water washed with _ treated water In any of the - or a plurality of solutions, the acid acid-based compound is dissolved in a method in which the water-containing towel-containing material containing boric acid is contained. Deuteration σ The aldonic acid compound water per one in either step. . Parts by weight, usually. .01 to 60 parts by weight:, = 316505 11 0*5 by weight, more preferably 1 part by weight or more, and more preferably 30 parts by weight per 15 parts by weight or less. If the amount of the tartrate-based compound is suppressed to be less than or equal to the ui part by weight, the effect of the problem of discoloration of the film under dry heat cannot be sufficiently exerted. The lunar eclipse of acid and sugar acid quaternization in your eve of the sun in w 30 weights in the skirt of the literary sputum, the general 〇.001 to „ μ Q or so, preferably 〇·〇 Ig% by weight or more, more preferably 〇丨 旦 y or more, and it is more effective than the U 1 1 里 里 ° ° ° ° ° ° ° 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如:: The glycosic acid or its salt contained in the polarizing film formed by the polyvinyl alcohol resin = The test method is based on, for example, dissolving the polarizing film in a solvent, and then using the method of enzyme analysis/Λ, to quantify the method. . International (shares) sales of "F - sets, and ... two? / Use .J. Κ·. Lactone, etc.右 苟 苟 苟 右 右 右 右 - - - - - - - - - - - - - - - - - - - - - - 右 右 右 右 右 右 右 右 右 右 右 右 右 右 右 右 醛 醛 醛 醛 醛 醛Close to the characteristics of the coior). Known · Polarized film, can be made in the agricultural - #知^ * /, face or both sides of the protective film to create a polarizing plate to protect the film and film can be exemplified by Sanyi Xiangmei weaving # ·#· ·+, * base , a quercetin or a diacetyl cellulose acrylate resin film, a poly(tetra) sulphur film, a poly arsenic resin film, and a ring-shaped thin smoke such as a thin piece of ice icing as a city of early sputum. The thickness of the protective film is usually from m to 200 from about 111. Further, such a polarizing plate may be provided on one surface, that is, a protective film 316505 12 1355514 hard film layer or a viscous road surface, and has various functional layers known as an antireflection layer or an antiglare layer. [Examples] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples of the temples. In addition, the parallel color hue shown in the fiscal, '1 polarizing film Λ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The hue of the transmitted light when it is linearly polarized. Example 1 A polyethylene film having an average polymerization degree of about 2,400, a degree of saponification of 99.9% or more, and a thickness of 75 (four) was dried and the stretching ratio was 5 times. Under the tension, immerse in 6 (TC pure water! ^ clock. Secondly, the weight ratio of moth/shidian potassium/water is 〇·i5/5/(10) in water ☆ in 28 C Immersion for 48 seconds. Then, in gluconic acid [5 〇 weight, solution, obtained from Tokyo Chemical Industry Co., Ltd.] / changeover / sluice / water according to the reset ratio of 10/21/9. 5/100 mixed Dip in the aqueous solution for 3 sec. under the step. Wash the sputum with pure water of the muscle. After 5 seconds, dry at 5 (r, wear), get the adsorption orientation of the polyethylene _, and make (4) The polarizing film of the sugar acid and the film were obtained. The obtained polarizing film was evaluated for durability under dry heat according to the following method. "Evaluation Method of Durability" First, a spectrophotometric needle [UV-220G manufactured by Shimadzu Corporation) was used. "], measuring the spectral transmittance r (λ) of the polarizing film. From the scored light transmittance r (λ), the transmission spectrum of the parallel splitting and the transmission spectrum of the 316505 1355514 of the orthogonal splitting are obtained, and are respectively Spectral transmission spectra were used to determine the parallel hue L, and b*, and the orthogonal hue L*'? and b*. Secondly, the polarizing film was placed in a dry environment of TC for 14 hours for durability. Test. The polarizing film after the durability test is again measured for the spectral transmittance r (λ), from which the parallel hue L*, a* and b*, and the orthogonal hue L, a and b* are obtained. The hue 〆 and ^ before and after the test are determined according to the following equations (1) to (3), and the difference Δ!/, △, and Ab* are obtained, and the color difference of the whole is obtained according to the following formula (4); .
Δ L =(L )after— (L*)before ( i n (2) (3) af ter係耐久性試驗 Δ a =(a )after— (a*)before Δ b =(b )after— (b*)before 在此，before#耐久性試驗前之值 後之值。 ΔΕ = { Δ (L*)2+ ( Δ a*)2 + ( δ b*)2}1/2 ⑷ *於是，可判斷如直交之色相b*之差Ab*與全體之色差 △E*之值愈大，則其乾熱下的變色之程度愈大。將对久性 試驗前.之平行色相^及b*，和耐久性試驗前後之直交之色 相差Ab*及全體之差△£*，表示於表1中。 實施例2 將：Η貝轭例1同樣方式進行單向拉伸，並浸潰於純水 後之聚乙烯醇膜，於碘/碘化鉀/水之重量比為〇 15/5/1〇〇 =水溶液中在28。〇下浸潰47秒鐘加以染色。然後，於葡 萄糖馱鋅[彳之東厅、化成工業（股）取得]/碘化鉀/硼酸/水按 重夏比5/10/9. 5/100混合的水溶液中在76。〇下浸潰3〇〇 316505 1355514 =，再使用饥之純水洗淨2秒鐘後在5以乾燥，製 乙烯醇上吸附定向有埃，並吸附有葡萄糖酸鋅的偏光 、所仔偏光膜依與實施例i同樣方法進料估，並將結 果表示於表1中。 比較例1 除蝴酸處理浴_夫沐力σ葡益祕_純μ , r禾从、加葡甸糖酸鋅以外，其餘與實施 同=樣操作’以製作偏光膜。所得偏光膜依實施例i之 R未K方法進行評估，並將結果表示於表丨中。 [表" 本1 實施例 編號 醛糖酸系 化合物 领酸水溶液 中之左列化 合物之量” 平行色相 * . t a b 乾熱耐久 試驗結果 直交△ b*首夺A E* 葡萄糖酸 葡萄糖酸鋅 --- 5重量份 5重量份 -1. 15 -1. 15 3. 88 3.47 0. 24 0. 07 0. 62 · 0.41 ~1. 18 4. 59 2. 1〇 5. 69 對水100重量份的量 [產業上之利用可能性] 。、本發明之碘系偏光膜係耐熱性優異者，而在行動電話 或車麵襄载用等’有可能曝露在高溫下的液晶顯示裝置方 ^有用。7 % ’由於此種偏光膜之平行色相會成為接近中性 色者之故’在電視等之液晶顯示裝置方面亦有用。 316505 15Δ L =(L )after— (L*)before ( in (2) (3) af ter durability test Δ a = (a )after— (a*)before Δ b =(b )after— (b *) before here, the value after the value before the durability test. ΔΕ = { Δ (L*)2+ ( Δ a*) 2 + ( δ b*) 2} 1/2 (4) * So, Judging that the difference between the aberration of the straight color b* and the color difference ΔE* of the whole is greater, the degree of discoloration under dry heat is greater. The parallel hue and b* of the longness test will be The color difference Ab* and the total difference Δ£* before and after the durability test are shown in Table 1. Example 2: Mussel yoke Example 1 was uniaxially stretched and immersed in pure water in the same manner. The polyvinyl alcohol film is then dyed in an iodine/potassium iodide/water weight ratio of 〇15/5/1〇〇=aqueous solution at 28. under the armpit for 47 seconds for dyeing. East Hall, Chemical Industry Co., Ltd. obtained] / potassium iodide / boric acid / water by weight ratio of summer 10/10/9. 5 / 100 mixed aqueous solution at 76. Underarm dipping 3 〇〇 316505 1355514 =, then use hunger After washing with pure water for 2 seconds, it is dried at 5, and it is adsorbed and oriented on the vinyl alcohol, and adsorbed. The polarized film with zinc gluconate and the polarized film were evaluated in the same manner as in Example i, and the results are shown in Table 1. Comparative Example 1 Treatment of the acid-free bath _ _ _ _ _ _ _ _ _ _ pure μ The same procedure as in the case of the addition of glucosinolate, and the same procedure was carried out to prepare a polarizing film. The obtained polarizing film was evaluated according to the R-K method of Example i, and the results were shown in the surface. [Table " The amount of the left-hand compound in the aqueous solution of the aldonic acid-based compound in the first embodiment. Parallel hue*. Tab Dry heat endurance test results Straight △ b* First AE* Gluconate zinc gluconate-- - 5 parts by weight - 1 15 -1. 15 3. 88 3.47 0. 24 0. 07 0. 62 · 0.41 ~ 1.18 4. 59 2. 1〇5. 69 100 parts by weight of water The amount of the iodine-based polarizing film of the present invention is excellent in heat resistance, and it is useful for a liquid crystal display device that may be exposed to high temperatures, such as a mobile phone or a vehicle. 7 % 'Because the parallel hue of such a polarizing film will become close to neutral color' It is also useful. 316505 15