201033273 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種可作爲偏光性能優異之偏光薄膜的 原料使用的聚乙烯醇薄膜。 【先前技術】 液晶顯示裝置（LCD)於其開發初期係使用於電子計 算機及手錶等小型機器，惟近年，則廣泛使用於筆記型電 腦、液晶螢幕、液晶彩色投影機、液晶電視、車內用導航 0 系統、行動電話、室內外用之計測機器等。另一方面，特 別在液晶電視等用途，顯示品質之提升例如提高對比，愈 發需求，對於LCD零件之一的偏光板，強烈需求偏光性能 之提升。 先前，一般使用的偏光板係具有對聚乙烯醇（以下稱 爲PVA )而成的生膜材料，實施單軸延伸、使用碘或二色 性染料之染色處理、藉由硼化合物之固定處理等，於製得 的偏光薄膜之單面或二面上，黏貼有三醋酸纖維素薄膜或 φ 醋酸-丁酸纖維素薄膜等保護膜之構成。提升此類偏光板 的偏光性能之手段，提案有改良原料PVA的結構之手法、 控制PVA薄膜的物性之方法、設計偏光板的製造條件之方 法等各種手段，有助於提升LCD之對比。 例如’專利文獻1記載由具有2 5 0 0以上' 較佳爲 6000-1 0000聚合度的PVA所形成之偏光薄膜，係光學特性 優異。使用高聚合度的PVA ’係提升偏光性能之有效手段， 惟，不易於工業操作。 又’提升偏光性能之其他方法，例如專利文獻2記載， 201033273 生膜材料係使用熱水中的完全溶解溫度（X)和平衡膨潤度 (Y)的關係在下式範圍的PVA系薄膜之偏光薄膜之製造 方法。 Y> - 0.0667Χ+ 6.73 ........ (I) 65 ........ ( II) 惟，使用於上述發明的PVA之聚合度較佳爲3500-5000 之範圍’即使直接將此製造方法應用於高聚合度PVA，如 後述的比較例所述般，製得的偏光薄膜之偏光性能不足。 亦即，以工業方法來製造由高聚合度的PVA形成之偏光薄 膜時，必須全方位考量關於PVA的結構、PVA薄膜的物性 等資訊，而找出最適當之原料條件。 先前技術文獻 專利文獻1 特開平1-105204號公報 專利文獻2 特開平7 - 1 206 1 6號公報 【發明內容】 發明所欲解決之課題 本發明之目的係提供一種由高聚合度的PVA形成之薄 膜’其係可作爲用於製造具有髙偏光性能的偏光薄膜之原 料。 解決課題之手段 本發明者等，爲盡其所能地發現關於PVA結構及PVA 薄膜的物性之資訊而進行探討。其結果發現聚合度爲 5100〜1 0000的PVA而形成，膨潤度爲2.00〜240%，且寬度 方向的中央部位的阻滯値爲l〇~40nm之PVA薄膜係符合上 述目的’而終至完成本發明。 此時，上述PVA之皂化度較佳爲98莫耳％以上。 201033273 PVA薄膜之厚度較佳爲10〜12〇从m。[Technical Field] The present invention relates to a polyvinyl alcohol film which can be used as a raw material of a polarizing film excellent in polarizing performance. [Prior Art] Liquid crystal display devices (LCDs) were used in small computers such as electronic computers and watches in the early days of development. In recent years, they have been widely used in notebook computers, LCD screens, liquid crystal color projectors, LCD TVs, and in-vehicles. Navigation 0 system, mobile phone, measuring instrument for indoor and outdoor use, etc. On the other hand, in particular, for LCD TVs and the like, the display quality is improved, for example, the contrast is increased, and the demand for polarizing plates, which is one of the LCD parts, is strongly required to be improved. Conventionally, a polarizing plate generally used has a green film material (hereinafter referred to as PVA), which is subjected to uniaxial stretching, dyeing treatment using iodine or a dichroic dye, fixing treatment with a boron compound, and the like. A protective film such as a cellulose triacetate film or a φ acetate-butyric acid cellulose film is adhered to one side or both sides of the obtained polarizing film. In order to improve the polarizing performance of such a polarizing plate, proposals have been made to improve the structure of the raw material PVA, the method of controlling the physical properties of the PVA film, and the method of designing the manufacturing conditions of the polarizing plate, which contribute to the improvement of the contrast of the LCD. For example, Patent Document 1 discloses a polarizing film formed of PVA having a polymerization degree of 2,500 or more, preferably 6,000 to 10,000, which is excellent in optical characteristics. The use of a high degree of polymerization PVA's is an effective means of improving the polarization performance, but it is not easy to industrially operate. Further, another method of improving the polarizing performance is disclosed in Patent Document 2, 201033273. The film material is a polarizing film of a PVA film having a relationship between a complete dissolution temperature (X) and a balance swelling degree (Y) in hot water. Manufacturing method. Y> - 0.0667 Χ + 6.73 ........ (I) 65 . . . (II) However, the degree of polymerization of the PVA used in the above invention is preferably in the range of 3,500 to 5,000. Even if this manufacturing method is directly applied to the high polymerization degree PVA, the polarizing performance of the obtained polarizing film is insufficient as described in the comparative example described later. That is, when a polarizing film formed of a high polymerization degree PVA is produced by an industrial method, information on the structure of the PVA, the physical properties of the PVA film, and the like must be comprehensively considered, and the most suitable raw material conditions can be found. CITATION LIST OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The object of the present invention is to provide a PVA having a high degree of polymerization. The film can be used as a raw material for producing a polarizing film having a ruthenium polarization property. MEANS FOR SOLVING THE PROBLEMS The present inventors have found that information on the physical properties of the PVA structure and the PVA film is found to the best of its ability. As a result, it was found that the degree of polymerization was 5,100 to 10,000 PVA, and the degree of swelling was 2.00 to 240%, and the PVA film having a retardation 中央 of 10 to 40 nm in the central portion in the width direction satisfies the above purpose and was completed. this invention. At this time, the degree of saponification of the PVA is preferably 98 mol% or more. The thickness of the 201033273 PVA film is preferably from 10 to 12 Å from m.
本發明亦包含了以含有聚合度爲5100~ 1 0000的PVA 和水之製膜原液作爲原料而進行製膜的上述PVA薄膜之製 造方法。 本發明更包含了將上述PVA薄膜染色、延伸而製得之 偏光薄膜。 發明效果 本發明的PVA薄膜’係可使用作爲偏光性能優異的偏 光薄膜之原料。所製得的偏光薄膜，係可有效地使用於製 造電子計算機、手錶、筆記型電腦、液晶.螢幕、液晶彩色 投影機、液晶電視、車內用導航系統、行動電話、室內外 用之計測機器等液晶顯示裝置的構成零件之偏光板。 【實施方式】 實施發明之形態 以下，詳細地說明本發明。 使用於本發明的PVA之聚合度，爲因應本發明的目的 之偏光薄膜之良好偏光性能，必須爲5 10 1 0 000，較佳爲 5 200〜9 5 00，尤佳爲 5400〜9200。若 PVA之聚合度低於 5100,則製造偏光薄膜時，不易具有高偏光性能。另一方 面，若PVA之聚合度超過10000，則PVA之生產性降低。 本發明中的PVA之聚合度，係指依據後述實施例的方法所 測得之聚合度（黏度平均聚合度）》 又，PVA之皂化度，較佳爲98莫耳％以上，更較佳爲 99莫耳％以上，尤佳爲99.5莫耳％以上，最佳爲99.8莫 耳％以上。若PVA之皂化度低於98莫耳％，在偏光薄膜 之製造工程中，PVA易於溶出’而溶出的PVA則附著於薄 201033273 膜，恐有降低偏光薄膜的性能之虞。 使用於本發明的PVA’可藉由將乙烯酯聚合所得的聚 乙烯酯系聚合物皂化而製得。.乙烯酯例如醋酸乙烯醋、甲 酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、三甲基乙酸乙稀酯、 叔碳酸乙烯酯、月桂酸乙烯酯、硬脂酸乙烯酯、苯甲酸乙 烯酯等，從其中選擇1種或2種以上。從取得的容易性、 PVA製造的容易性、成本等觀點，宜使用其中的醋酸乙烯 酯。聚合溫度無特別之限制，使用甲醇爲聚合溶劑時，聚 合溫度較佳爲甲醇的沸點附近之60 °C左右。 在不破壞本發明的效果之範圍內，乙烯酯的同元聚合 物之皂化物不受限制。例如不飽和羧酸或其衍生物、不飽 和磺酸或其衍生物、碳數2〜30的α -烯烴等，以低於5莫 耳％之比例接枝共聚於PVA之改性PVA ;乙烧酯與不飽和 羧酸或其衍生物、不飽和磺酸或其衍生物、碳數2〜30的α _烯烴等，以低於15莫耳％之比例進行共聚之改性聚乙烯 醋之巷化物；以甲酵水、丁醒、苯甲醒等醋類，於PVA的 部份羥基進行交聯之聚乙烯縮醛系聚合物。 藉由製膜上述的PVA而製得本發明的PVA薄膜。製膜 方法除將含水PVA熔融擠壓的方法之外，可採用流延製膜 法、濕式製膜法（釋出於弱溶劑中）、凝膠製膜法（使PVA 水溶液暫時冷卻凝膠化後，抽出去除溶劑）、澆鑄製膜法（使 PVA水溶液流動於基盤上，並乾燥）、及其組合之方法等。 其中’熔融擠壓製膜法及流延製膜法，因可製得優異之PVA 薄膜，故較適用。使用於製膜時之溶劑，宜使用水。 主要由PVA和溶劑形成的製膜原液之揮發分率，係依 據製膜方法或PVA之分子量而變化，較佳爲5〇〜95質量 201033273 %。若揮 製膜時不 薄膜。若 ，不易製 。可塑劑 可塑劑之 PVA，爲 熱風之乾 等。可單 用。乾燥 又，此時 件，約爲 fC率）後， 邊固定， 少而發生 使薄膜具 ί圭爲1〜1 5 %。熱處 爲5分鐘 %，更較佳爲60〜9 5質量％，尤佳爲7 0~9 5質量 發分率低於50質量％，則製膜原液之黏度過高， 易過濾或去泡，不易於製得無異物或缺陷之PVA 揮發分率超過95質量％，則製膜原液之黏度過低 得具有目標厚度和高厚度精度之PVA薄膜。 製造本發明的PVA薄膜時，亦可使用可塑劑 例如甘油、二甘油、乙二醇等，惟不受限於此。 用量亦無特別之限制，一般相對於1 〇〇質量份 10~15質量份之範圍內。 製膜後的PVA薄膜之乾燥方法，例如利用 燥、使用熱輥之接觸乾燥、紅外線加熱器之乾燥 獨採用其中1種方法，亦可組合2種類以上而使 溫度無特別之限制，較佳爲50〜70°C的範圍內。 之乾燥時間，係依據製膜原液的濃度或製膜條 45〜75分鐘° 將乾燥的PVA薄膜調濕，並調整水分率（含7」 僅將薄膜的平行的二邊，較佳爲僅寬度方向的二 藉由100-140 °C範圍內的熱處理，因伴隨水分減 應力，可給予薄膜穩定的延伸。藉此，可穩定地 有後述低程度之阻滯値。此時的薄膜之水分率較< 質量％，更較佳爲1~1〇質量％，尤佳爲2〜6質量 理之時間鮮特別之限制，依熱處理溫度而異，約 以內。 如此製得的本發明的P.VA薄膜之厚度，較佳爲10〜120 #m，更較佳爲12〜80/zm，尤佳爲15〜75//m，最佳爲20〜60 Am。若厚度小於10/ζιη，在後述的延伸步驟中，恐有薄膜 201033273 易於破裂之虞。若厚度超過120/zm，則延伸時薄膜的應力 過大，不易充分地延伸。 本發明的PVA薄膜之膨潤度必須爲200~240%，較佳 爲205〜235 % ’尤佳爲210〜230% »若膨潤度低於200%， 則延伸時的張力過大，不易充分地進行延伸。若膨潤度超 過240%，因吸水性高，在後述的偏光薄膜之製造步驟中， 薄膜易於發生皴摺或邊緣捲曲，即爲延伸時發生破裂之原 因。爲控制膨潤度於規定之範圍，例如可將製膜後的PVA I 薄膜之熱處理溫度或時間調整在上述範圍內。PVA薄膜之 膨潤度，係可藉由實施例項目的後述方法而測定。 本發明的PVA薄膜，寬度方向的中央部位之阻滯値必 須爲10〜40nm，更較佳爲13~37nm，尤佳爲17~33nm，最 佳爲20〜3 0nm。若阻滯値小於10nm，因製造偏光薄膜時的 染色速度變慢，故易於發生染色斑。若阻滯値超過40nm， 即使爲低延伸倍率，薄膜亦發生斷裂。PVA薄膜的阻滯値， 係可藉由實施例項目的後述方法而測定。 _ 爲將PVA薄膜的阻滯値控制於規定之範圍，除上述將 PVA薄膜調濕後進行熱處理的方法之外，例如以既知的方 法來延伸PVA薄膜之方法，惟不受限於此。從將已發生的 阻滯値固定之觀點，宜採用調濕後進行熱處理之方法。此 時，僅將PVA薄膜的平行的二邊，較佳爲僅寬度方向的二 邊固定並進行熱處理係重要之步驟。不固定薄膜或固定四 個角而加熱，爲使薄膜的應力均等，而不發生阻滯，無法 達成目的。 接著，說明使用本發明的PVA生膜材料的偏光薄膜之 製造方法。偏光薄膜之製造步驟，係包括水分調整、染色、 201033273 的濕式延伸。依 將製得的延伸薄 於含有硼酸及碘 得偏光薄膜。 或蒸餾水中而進 ! 25〜3 5°C，尤佳 的含水率降低， 光薄膜之偏光性 水性提高，在之 曲，即爲延伸時 料之時間，約爲 水溶液中進行。 化鉀濃度較佳爲 質量％，碘化鉀 t 0.03~0.06 質量 液之溫度無特別 .述水分調整或染 整用的水中或染 佳爲在染色用的 PVA生膜材料之 所表示之延伸倍 f，尤佳爲2.4〜2.8 延伸、色調整等步驟。此時，宜進行薄膜 需求’在濕式延伸步驟後，亦可更進一步 膜於硼酸水溶液中進行延伸。依需求，可 化鉀的水溶液中，進行色調整、乾燥而製The present invention also encompasses a method for producing the above PVA film which is formed by using a film forming solution of PVA having a degree of polymerization of 5,100 to 10,000 and water as a raw material. The present invention further comprises a polarizing film obtained by dyeing and stretching the above PVA film. EFFECTS OF THE INVENTION The PVA film of the present invention can be used as a raw material of a polarizing film which is excellent in polarizing performance. The polarizing film produced can be effectively used in the manufacture of electronic computers, watches, notebook computers, liquid crystal screens, liquid crystal color projectors, liquid crystal televisions, navigation systems for vehicles, mobile phones, measurement machines for indoor and outdoor use, etc. A polarizing plate that is a component of a liquid crystal display device. [Embodiment] Mode for Carrying Out the Invention Hereinafter, the present invention will be described in detail. The degree of polymerization of the PVA used in the present invention is required to be 5 10 1 0 000, preferably 5 200 to 9 5 00, particularly preferably 5400 to 9200, in order to achieve good polarizing properties of the polarizing film for the purpose of the present invention. When the degree of polymerization of PVA is less than 5,100, when a polarizing film is produced, it is difficult to have high polarizing performance. On the other hand, if the degree of polymerization of PVA exceeds 10,000, the productivity of PVA is lowered. The degree of polymerization of PVA in the present invention means the degree of polymerization (viscosity average degree of polymerization) measured according to the method of the examples described later. Further, the degree of saponification of PVA is preferably 98 mol% or more, more preferably 99% or more, more preferably 99.5% or more, and most preferably 99.8% or more. When the degree of saponification of PVA is less than 98 mol%, in the production process of a polarizing film, PVA is easily eluted, and the eluted PVA adheres to the thin film of 201033273, which may degrade the performance of the polarizing film. The PVA' used in the present invention can be obtained by saponifying a polyvinyl ester-based polymer obtained by polymerizing a vinyl ester. . Vinyl esters such as vinyl acetate vinegar, vinyl formate, vinyl propionate, vinyl butyrate, ethyl trimethyl acetate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate Etc., one or two or more kinds are selected from them. From the viewpoints of ease of availability, ease of PVA production, cost, and the like, it is preferred to use vinyl acetate. The polymerization temperature is not particularly limited. When methanol is used as the polymerization solvent, the polymerization temperature is preferably about 60 °C in the vicinity of the boiling point of methanol. The saponified product of the homopolymer of vinyl ester is not limited insofar as it does not impair the effects of the present invention. For example, an unsaturated carboxylic acid or a derivative thereof, an unsaturated sulfonic acid or a derivative thereof, an α-olefin having a carbon number of 2 to 30, or the like, graft-polymerized to a modified PVA of PVA at a ratio of less than 5 mol%; a modified polyethylene vinegar copolymerized with an ester of an unsaturated carboxylic acid or a derivative thereof, an unsaturated sulfonic acid or a derivative thereof, an α-olefin having a carbon number of 2 to 30, or the like at a ratio of less than 15 mol% Allergic compound; a polyvinyl acetal polymer crosslinked with a part of hydroxyl groups of PVA, such as methacrylate, waking up, and styrene. The PVA film of the present invention was obtained by forming the above PVA. In addition to the method of melt-extruding aqueous PVA, a film forming method, a wet film forming method (released in a weak solvent), and a gel film forming method (a temporary cooling of a PVA aqueous solution gel) may be employed. After the removal, the solvent is removed, the casting film forming method (the PVA aqueous solution is allowed to flow on the substrate, and dried), a combination thereof, and the like. Among them, the melt extrusion film forming method and the cast film forming method are suitable because an excellent PVA film can be obtained. Water is preferably used as the solvent for film formation. The volatile matter ratio of the film forming stock solution mainly formed of PVA and a solvent varies depending on the molecular weight of the film forming method or PVA, and is preferably from 5 〇 to 95% by mass of 201033273%. If the film is not filmed. If it is not easy to make. Plasticizer PVA for plasticizer, dry for hot air, etc. Can be used alone. Drying, at this time, about fC rate), the side is fixed, and the occurrence of the film is less than 1 to 15%. The heat is 5 minutes%, more preferably 60 to 9.5 mass%, and particularly preferably 70 to 9.5. The mass fraction is less than 50% by mass, and the viscosity of the film forming solution is too high, and it is easy to filter or defoam. When it is not easy to obtain a PVA having a foreign matter-free or defective content of more than 95% by mass, the viscosity of the film-forming stock solution is too low to obtain a PVA film having a target thickness and a high thickness precision. When the PVA film of the present invention is produced, a plasticizer such as glycerin, diglycerin, ethylene glycol or the like may be used, but is not limited thereto. The amount is also not particularly limited and is generally in the range of 10 to 15 parts by mass relative to 1 part by mass. The drying method of the PVA film after the film formation is, for example, dry drying, contact drying using a hot roll, and drying of an infrared heater, and one type of the method may be used alone, or two or more types may be combined, and the temperature is not particularly limited, and it is preferably 50 to 70 ° C range. The drying time is based on the concentration of the film forming solution or the film strip 45~75 minutes. The dried PVA film is conditioned and the moisture content is adjusted (including 7). Only the two sides of the film are parallel, preferably only the width. The second direction of the direction is imparted to the film by a heat treatment in the range of 100-140 ° C, which is accompanied by a water stress reduction, thereby stably extending the film to a low degree of hindrance. It is less than the mass %, more preferably 1 to 1% by mass, and particularly preferably 2 to 6 by mass, and is particularly limited depending on the heat treatment temperature. The P of the present invention thus obtained. The thickness of the VA film is preferably 10 to 120 #m, more preferably 12 to 80/zm, still more preferably 15 to 75//m, most preferably 20 to 60 Am. If the thickness is less than 10/ζιη, In the extension step described later, there is a fear that the film 201033273 is easily broken. When the thickness exceeds 120/zm, the stress of the film during stretching is too large, and it is difficult to sufficiently extend. The PVA film of the present invention must have a swelling degree of 200 to 240%. Preferably, it is 205 to 235% 'More preferably 210 to 230%» If the degree of swelling is less than 200%, the extension is If the degree of swelling is more than 240%, the water absorption property is high, and in the manufacturing process of the polarizing film to be described later, the film is liable to collapse or edge curl, which is a cause of cracking during stretching. The degree of swelling is controlled within a predetermined range, and for example, the heat treatment temperature or time of the PVA I film after film formation can be adjusted within the above range. The degree of swelling of the PVA film can be measured by a method described later in the examples. The PVA film has a retardation 中央 of 10 to 40 nm, more preferably 13 to 37 nm, and particularly preferably 17 to 33 nm, and most preferably 20 to 30 nm in the central portion in the width direction. If the retardation is less than 10 nm, When the polarizing film is produced, the dyeing speed is slow, so that the dyeing spots are likely to occur. If the retardation exceeds 40 nm, the film is broken even at a low stretching ratio. The retardation of the PVA film can be described later by the example project. Measured by the method. _ In order to control the retardation P of the PVA film to a predetermined range, in addition to the method of heat-treating the PVA film after the above-mentioned conditioning, for example, the method of extending the PVA film by a known method is used. The method is not limited thereto. From the viewpoint of fixing the retardation that has occurred, it is preferable to use a method of heat treatment after conditioning, and in this case, only the parallel sides of the PVA film are preferably only in the width direction. Fixing and heat-treating the two sides is an important step. Heating is not fixed or fixed at four corners, so that the stress of the film is uniform without blocking, and the object cannot be achieved. Next, the use of the PVA film of the present invention will be described. A method for producing a polarizing film of a material. The manufacturing step of the polarizing film includes moisture adjustment, dyeing, and wet stretching of 201033273. The elongation obtained is thinner than a polarizing film containing boric acid and iodine. Or in distilled water! 25~3 5 °C, especially the water content is lowered, the polarizing property of the light film is improved, and the time is the time of stretching, which is about to be carried out in an aqueous solution. The potassium concentration is preferably % by mass, and the temperature of the potassium iodide t 0.03 to 0.06 mass liquid is not particularly specific. The water used for moisture adjustment or dyeing or dyeing is preferably a stretching ratio f expressed by the PVA film material for dyeing, Especially good is 2.4~2.8 extension, color adjustment and other steps. At this time, it is preferable to carry out the film demand. After the wet stretching step, the film may be further extended in an aqueous boric acid solution. According to the demand, in the aqueous solution of potassium, color adjustment and drying are carried out.
PVA薄膜之水分調整，宜浸漬於純水 行。此時之溫度較佳爲20〜4 (TC，更較佳焉 爲27~33°C。若溫度低於20°C，生膜材料 其後延伸時的薄膜之張力升高，製得的偏 能降低。若溫度超過40°C，生膜材料的吸 後的步驟中，薄膜易於發生皺摺或邊緣捲 發生破裂之原因。另一方面，浸漬生膜材 3 0~120秒之範圍內。 PVA薄膜之染色，例如於碘一碘化鉀 此時，碘濃度較佳爲0.01〜0.1質量％，碘 1~10質量％，碘濃度更較佳爲0.02〜0.08 濃度更較佳爲2~8質量％，碘濃度尤佳爲 %，碘化鉀濃度尤佳爲3~6質量％。水溶 之限制，較佳爲25〜40°C。 PVA生膜材料之濕式延伸，亦可於上 色之外的步驟進行，惟’宜在上述水分調 色用的水溶液中進行，因其效率較佳，尤 水溶液，亦即碘-碘化鉀水溶液中進行。 濕式延伸’以延伸前後的薄膜的長度比 率，較佳爲2.0-2.9倍，更較佳爲2_2〜2.8传 倍。 將PVA薄膜進行濕式延伸時之溫度，從可製得偏光性 201033273 能更佳的偏光薄膜之觀點，較佳爲2 0〜4 0 °C，更較佳爲 25〜40°C，尤佳爲25〜35它，最佳爲27~33。(：。 如上述般，將PVA薄膜進行濕式延伸的步驟之後，亦 可將製得的延伸薄膜於硼酸水溶液中更進一步進行延伸。 此時的延伸倍率較佳爲3倍以下，更較佳爲1.2〜3倍，尤 佳爲1.3〜2·9倍，最佳爲1.4〜2.8倍。 此時的水溶液中的硼酸濃度，較佳爲2〜6質量％，更 較佳爲2〜5質量％，尤佳爲2~4質量％。若硼酸的濃度小 於2質量％，製得的偏光薄膜的色斑增多。若硼酸的濃度 超過6質量％，則起因於硼酸之p VA的交聯過剩，不易以 高倍率來延伸薄膜。 爲使偏光薄膜之色相接近於非彩色（中性灰），宜於硼 酸水溶液中添加碘化鉀。碘化鉀之濃度較佳爲3〜10質量 %，尤佳爲4〜8質量％。若碘化鉀濃度小於3質量％，則 製得的偏光薄膜偏藍色。另一方面，若碘化鉀濃度超過10 質量％，則製得的偏光薄膜偏紅色。硼酸水溶液亦可含有 其他成分，例如鐵、锆等金屬化合物。 上述延伸中，水溶液的溫度無特別之限制，惟較佳爲 50~60°C，更較佳爲55〜60°C，尤佳爲57〜60°C。若延伸溫 度低於5 0°C，則無法充分延伸，製得的偏光薄膜之偏光度 降低。若延伸溫度超過60°C，則製得的偏光薄膜之透過度 降低。 通過全部步驟之延伸倍率，較佳爲4.5~7.0倍，更較佳 爲4.7〜6.5倍，尤佳爲5.0~6.0倍。若延伸倍率低於4.5倍， 則製得的偏光薄膜之偏光性能降低。若延伸倍率超過7.0 倍，薄膜常於延伸中破裂，不易安定地製造偏光薄膜。 -10- 201033273 延伸後之色調整，宜於含有硼酸和碘化鉀之水溶液中 進行。此時，亦可於水溶液中添加氯化鋅、碘化鋅等金屬 化合物。爲預防偏光性能降低，水溶液之溫度宜低於延伸 溫度，具體而言，較佳爲20〜50°C，尤佳爲30〜40°C。色調 整之時間無特別之限制。 製得的偏光薄膜之乾燥，係可使用各種乾燥機，以批 式、連續連接式、連續輥上接觸式等方法進行。爲預防偏 光薄膜中的碘昇華，又爲抑制與PVA交聯的硼酸之脫離反 應，乾燥溫度較佳爲40〜80°C，更較佳爲45~70°C，尤佳爲 5 0〜6 0 °C。乾燥時間無特別之限制，依裝置或乾燥溫度而 異，例如3〜6分鐘之範圍內。 實施例 以下，以實施例等更具體地說明本發明，惟本發明不 受限於以下之實施例。實施例中，PVA之黏度平均聚合度 P、PVA薄膜之膨潤度、PVA薄膜之阻滯値Re、偏光薄膜 之透過率Y及偏光度V，係以下述之方法進行評價。 (1 ) PVA的黏度平均聚合度P之測定 將0.28gPVA、70g蒸餾水及攪拌子放入100mL的共栓 磨口玻璃三角燒瓶。將加栓的上述三角燒瓶浸漬於95 °C恆 溫槽，以攪拌子邊攪拌邊溶解PVA，製作0.4% PVA水溶 液。以布赫納漏斗形玻璃過濾器3 G來過濾該PVA水溶液， 於3 0 °C的恆溫水槽中冷卻，作爲聚合度測定用試驗品。參 考試驗品係於其他的1 OOmL共栓磨口玻璃三角燒瓶中，放 入7〇g蒸餾水並加上栓，浸漬於30°C的恆溫水槽。 將已於105 °C的乾燥機中加熱1小時之蒸發皿放入乾 燥器中冷卻30分鐘，測定蒸發皿的質量a(g)。以無刻度 -11 - 201033273 吸管將10mL的聚合度測定用試驗品移至此蒸發皿，並於 105 °C的乾燥機中乾燥16小時後，於乾燥器中冷卻30分 鐘’測定質量b ( g )。聚合度測定用試驗品之濃度c ( g/L )， 係依據下述通式而算出。 c= ΙΟΟΟχ ( b- a) /10 以lOmL無刻度吸管將聚合度測定用試驗品或蒸餾水 放入奧氏黏度計，於30 °C的恆溫水槽中，使其穩定15分 鐘。測定投入的聚合度測定用試驗品之落下秒數11 ( s )與 0 蒸餾水之落下秒數to (S)，依據下述通式算出黏度平均聚 合度P。 V r= ti/ to [η ] = 2.303xLog ( η r/c )The moisture adjustment of the PVA film should be immersed in pure water. The temperature at this time is preferably 20 to 4 (TC, more preferably 27 to 33 ° C. If the temperature is lower than 20 ° C, the tension of the film when the film material is extended is increased, and the obtained bias is obtained. If the temperature exceeds 40 ° C, the film is prone to wrinkles or cracks in the edge roll during the step of sucking the film material. On the other hand, the film is impregnated within the range of 30 to 120 seconds. The dyeing of the PVA film, for example, in the case of iodine-potassium iodide, the iodine concentration is preferably 0.01 to 0.1% by mass, the iodine is 1 to 10% by mass, the iodine concentration is more preferably 0.02 to 0.08, and the concentration is more preferably 2 to 8% by mass. The iodine concentration is particularly preferably %, and the potassium iodide concentration is particularly preferably 3 to 6% by mass. The limitation of water solubility is preferably 25 to 40 ° C. The wet stretching of the PVA film material can also be performed outside the coloring step. This is preferably carried out in an aqueous solution for water grading, and is preferably carried out in an aqueous solution, that is, an iodine-potassium iodide aqueous solution. The wet stretching is preferably a length ratio of the film before and after stretching. 2.0-2.9 times, more preferably 2_2~2.8 times. The temperature of the PVA film during wet extension is from The viewpoint of obtaining a polarizing film of 201033273 is preferably 20 to 40 ° C, more preferably 25 to 40 ° C, particularly preferably 25 to 35, and most preferably 27 to 33. (: As described above, after the step of wet-extending the PVA film, the obtained stretched film may be further extended in an aqueous boric acid solution. The stretching ratio at this time is preferably 3 times or less, more preferably It is 1.2 to 3 times, preferably 1.3 to 2·9 times, and most preferably 1.4 to 2.8 times. The concentration of boric acid in the aqueous solution at this time is preferably 2 to 6 mass%, more preferably 2 to 5 mass. %, particularly preferably 2 to 4% by mass. If the concentration of boric acid is less than 2% by mass, the color unevenness of the obtained polarizing film increases. If the concentration of boric acid exceeds 6% by mass, the crosslinking of p VA due to boric acid is excessive. It is not easy to extend the film at a high magnification. In order to make the hue of the polarizing film close to achromatic (neutral gray), it is preferable to add potassium iodide to the aqueous boric acid solution. The concentration of potassium iodide is preferably 3 to 10% by mass, particularly preferably 4~ 8 mass%. If the potassium iodide concentration is less than 3% by mass, the obtained polarizing film is bluish. The other side When the potassium iodide concentration exceeds 10% by mass, the obtained polarizing film is reddish. The boric acid aqueous solution may contain other components such as a metal compound such as iron or zirconium. In the above extension, the temperature of the aqueous solution is not particularly limited, but is preferably 50 to 60 ° C, more preferably 55 to 60 ° C, and particularly preferably 57 to 60 ° C. If the extension temperature is lower than 50 ° C, the elongation cannot be sufficiently extended, and the polarizing film obtained has a lower degree of polarization. If the elongation temperature exceeds 60 ° C, the transmittance of the obtained polarizing film is lowered. The stretching ratio by all the steps is preferably 4.5 to 7.0 times, more preferably 4.7 to 6.5 times, and particularly preferably 5.0 to 6.0 times. . If the stretching ratio is less than 4.5 times, the polarizing performance of the obtained polarizing film is lowered. If the stretching ratio exceeds 7.0 times, the film is often broken during stretching, and it is difficult to stably produce a polarizing film. -10- 201033273 The color adjustment after stretching is preferably carried out in an aqueous solution containing boric acid and potassium iodide. At this time, a metal compound such as zinc chloride or zinc iodide may be added to the aqueous solution. In order to prevent a decrease in polarizing performance, the temperature of the aqueous solution is preferably lower than the stretching temperature, and specifically, it is preferably 20 to 50 ° C, particularly preferably 30 to 40 ° C. There is no special limit to the color tone. The drying of the obtained polarizing film can be carried out by a batch, a continuous connection, a continuous roll contact method or the like using various dryers. In order to prevent iodine sublimation in the polarizing film and to suppress the decoupling reaction of boric acid cross-linked with PVA, the drying temperature is preferably 40 to 80 ° C, more preferably 45 to 70 ° C, and particularly preferably 5 0 to 6 0 °C. The drying time is not particularly limited and varies depending on the apparatus or drying temperature, for example, in the range of 3 to 6 minutes. EXAMPLES Hereinafter, the present invention will be specifically described by way of Examples and the like, but the present invention is not limited to the examples below. In the examples, the viscosity average degree of polymerization P of PVA, the degree of swelling of the PVA film, the retardation 値Re of the PVA film, the transmittance Y of the polarizing film, and the degree of polarization V were evaluated by the following methods. (1) Measurement of viscosity average degree of polymerization P of PVA 0.28 g of PVA, 70 g of distilled water and a stir bar were placed in a 100 mL coin-sealed glass Erlenmeyer flask. The plugged flask was immersed in a 95 ° C constant temperature bath, and PVA was dissolved while stirring with a stirrer to prepare a 0.4% PVA aqueous solution. The PVA aqueous solution was filtered through a Buchner funnel-shaped glass filter 3 G, and cooled in a constant temperature water bath at 30 ° C to obtain a test piece for measuring the degree of polymerization. The reference test strain was placed in another 100 mL co-plugged glass Erlenmeyer flask, and 7 g of distilled water was placed and stoppered, and immersed in a constant temperature water bath at 30 °C. The evaporating dish which had been heated in a dryer at 105 °C for 1 hour was placed in a desiccator and cooled for 30 minutes, and the mass a (g) of the evaporating dish was measured. 10 mL of the test piece for polymerization degree measurement was transferred to the evaporating dish with a graduated -11 - 201033273 pipette, and dried in a dryer at 105 ° C for 16 hours, and then cooled in a desiccator for 30 minutes 'measured mass b ( g ) . The concentration c (g/L) of the test article for measuring the degree of polymerization was calculated based on the following formula. c= ΙΟΟΟχ ( b- a) /10 The test piece or distilled water for polymerization degree measurement was placed in an Ou's viscometer in a 10 mL unscaled pipette and allowed to stand in a constant temperature water bath at 30 °C for 15 minutes. The drop number of seconds (s) of the test product for the measurement of the degree of polymerization to be measured and the number of seconds of the drop of the distilled water to (S) were measured, and the viscosity average degree of polymerization P was calculated according to the following formula. V r= ti/ to [η ] = 2.303xLog ( η r/c )
Log ( P ) = 1.61 3xLog ( [ η ]xl 04/8.29 ) (2 ) PVA薄膜的膨潤度之測定 將PVA薄膜裁剪成5Cmx5Cm，浸漬於30°C的1L蒸餾 水4小時。自蒸餾水中取出此PVA薄膜，將其夾於2張濾 @ 紙間以便吸收水滴後，測定質量D。更於1 0 5 °C的乾燥機中 乾燥16小時，再於乾燥器中冷卻3 0分鐘，測定質量E。 依據下述通式而算出PVA薄膜之膨潤度。 A= lOOxD/E ( % ) (3 ) PVA薄膜的膨潤度之測定 從PVA薄膜的中央部位取出寬度方向5cmx移動方向 10cm的長方形之試驗品，使用大塚電子公司製的光學材料 檢査裝置RETS— 1100，測定在測定波長5 5 0nm時之阻滯 値Re。 (4 )偏光薄膜的透過率Y之測定 -12- 201033273 自偏光薄膜的寬度方向之中央部位，採取2枚的延伸 方向4cmx寬度方向4cm之正方形試驗品，使用日立製作所 製的分光光度計U—4100(附有積分球），依據JISZ8 72 2 (物體色之測定方法），爲碳光源，2°視野的可見光領域之 可見度校正，1枚的偏光薄膜試驗品，係測定其相對於延 伸軸方向 45°傾斜時之光透過率與- 45°傾斜時之光透過 率，求其平均値Y1 (%)。另一枚偏光薄膜試驗品亦相同 作法，係測定45°傾斜時之光透過度與~ 45°傾斜時之光透 φ 過度，求其平均値Y2(%)。依下述通式，將Y1和Y2平 均，作爲偏光薄膜之透過率Υ(%)。 Y= ( Y1 + Υ2 ) /2 (5)偏光薄膜的偏光度V之測定 將上述（4)中採取的2枚偏光薄膜，和（4)透過率 同樣地，測定延伸方向平行而重疊時之光透過率 Y丨丨 (%)、延伸方向垂直而重疊時之光透過率 Y丄（％)，依 下述通式求出偏光度V(%)。 V={(Y|| — Y丄）/ (γ|| + Y 丄）}1/2χ1〇〇 (實施例1 ) 將含有聚合度5800、皂化度99.8莫耳％的PVA100質 量份、和作爲可塑劑的甘油12質量份之5.5質量％PVA水 溶液流延於60 °C的金屬輥上，乾燥60分鐘，製得厚度40 β m之PVA薄膜。將此薄膜置於2 6°C、2 0% RH條件下調 濕16小時，調整含水率爲3質量％後，將薄膜寬度方向的 二端固定於金屬框之平行的二邊，使薄膜的寬度方向不收 縮，並於120°C熱處理3分鐘。以上述（2)的方法來測定 熱處理後的PVA薄膜之膨潤度，結果爲230%。又以上述 -13- .201033273 (3 )的方法來測定PVA薄膜之阻滯値，結果爲29nm。 其次，將上述PVA薄膜剪裁成流動方向llcmx寬度方 向10cm，將流動方向安裝於延伸方向的夾頭間4cm之延伸 夾具，於30°C的純水中浸漬1分鐘，接著，浸漬於含有〇.〇3 質量％的碘、3質量％的碘化鉀之染色液（溫度30°C )’以 0.13m/min之速度延伸2.6倍，使碘被吸附。 其次，將此延伸薄膜浸漬於含有4質量％的硼酸、6 質量％的碘化鉀之延伸液（溫度57.5°C )，以〇.13m/inin之 0 速度延伸2.3倍後，固定於延伸方向，於50°C乾燥4分鐘 而製得偏光薄膜。依據上述（4)及（5)之方法來測定此 偏光薄膜之透過度及偏光度，結果分別爲44.0%、99·99 %，製得偏光性能良好之偏光薄膜。 (實施例2) 將含有聚合度5800、皂化度99.8莫耳％的PVA100質 量份、和作爲可塑劑的甘油12質量份之5.5質量％ PVA水 溶液流延於60°C的金屬輥上，乾燥60分鐘，製得厚度40 _ # m之PVA薄膜。將此薄膜置於26°C、20% RH條件下調 濕16小時，調整含水率爲3質量％後，將薄膜寬度方向的 二端固定於金屬框之平行的二邊，使薄膜的寬度方向不收 縮，並於115 °C熱處理3分鐘。以上述（2)的方法來測定 熱處理後的PVA薄膜之膨潤度，結果爲240%。又以上述 (3 )的方法來測定PVA薄膜之阻滯値，結果爲26nm。 其次，和實施例1相同作法，邊將上述PVA薄膜延伸， 邊使碘被吸附，更進一步進行延伸而製得偏光薄膜。依據 上述（4)及（5)之方法來測定此偏光薄膜之透過度及偏 光度，結果分別爲44.0%、99.96 %，製得偏光性能良好之 -14- 201033273 偏光薄膜。 (實施例3) 將含有聚合度9100、皂化度99·8莫耳％的PVA100 量份、和作爲可塑劑的甘油12質量份之5.5質量％PVA 溶液流延於60°C的金屬輥上，乾燥60分鐘，製得厚度 // m之PVA薄膜。將此薄膜置於26°C、20% RH條件下 濕16小時，調整含水率爲3質量％後，將薄膜寬度方向 二端固定於金屬框之平行的二邊，使薄膜的寬度方向不 @ 縮，並於110 °C熱處理3分鐘。以上述（2)的方法來測 熱處理後的PVA薄膜之膨潤度，結果爲230%。又以上 (3 )的方法來測定PVA薄膜之阻滯値，結果爲39nm。 其次，除延伸倍率爲2.5倍之外，和實施例1相同 法，邊將上述PVA薄膜延伸，邊使碘被吸附，更進一步 行延伸而製得偏光薄膜。依據上述（4)及（5)之方法 測定此偏光薄膜之透過度及偏光度，結果分別爲44.0% 9 9.95 %，製得偏光性能良好之偏光薄膜。 ^ (實施例4 ) 將含有聚合度5200、皂化度99.8莫耳％的PVA100 量份、和作爲可塑劑的甘油12質量份之5.5質量％PVA 溶液流延於60 °C的金屬輥上，乾燥60分鐘，製得厚度 # m之PVA薄膜。將此薄膜置於26°C、20% RH條件下 濕16小時，調整含水率爲3質量％後，將薄膜寬度方向 二端固定於金屬框之平行的二邊，使薄膜的寬度方向不 縮，並於135 °C熱處理3分鐘。以上述（2)的方法來測 熱處理後的PVA薄膜之膨潤度，結果爲205%。又以上 (3 )的方法來測定PVA薄膜之阻滯値，結果爲29nm。 質 水 20 調 的 收 定 述 作 進 來 質 水 40 調 的 收 定 述 -15- .201033273 其次，和實施例3相同作法’邊將上述PVA薄膜延伸 邊使碘被吸附，更進一步進行延伸而製得偏光薄膜。依 上述（4)及（5)之方法來測定此偏光薄膜之透過度及 光度，結果分別爲44.0%、99.95%，製得偏光性能良好 偏光薄膜。 (實施例5 )Log ( P ) = 1.61 3xLog ( [ η ]xl 04/8.29 ) (2) Measurement of swelling degree of PVA film The PVA film was cut into 5 cm x 5 cm, and immersed in 1 L of distilled water at 30 ° C for 4 hours. The PVA film was taken out from the distilled water and sandwiched between two sheets of filter paper to absorb water droplets, and the mass D was measured. The mixture was dried in a dryer at 105 ° C for 16 hours and then cooled in a desiccator for 30 minutes to determine the mass E. The degree of swelling of the PVA film was calculated according to the following formula. A= lOOxD/E (%) (3) Measurement of swelling degree of PVA film A rectangular test piece having a width of 5 cmx and a moving direction of 10 cm was taken out from the center of the PVA film, and an optical material inspection device RETS-1100 manufactured by Otsuka Electronics Co., Ltd. was used. The retardation 値Re at the measurement wavelength of 550 nm was measured. (4) Measurement of transmittance Y of polarizing film -12- 201033273 From the center of the width direction of the polarizing film, two square test pieces of 4 cm in the extending direction and 4 cm in the width direction were used, and a spectrophotometer U manufactured by Hitachi, Ltd. was used. 4100 (with integral sphere), according to JISZ8 72 2 (measurement method of object color), for carbon source, visibility correction in the visible field of 2° field of view, one polarizing film test product, measured relative to the direction of the extension axis The light transmittance at 45° tilt and the light transmittance at -45° tilt are averaged 値Y1 (%). The other polarizing film test article was also subjected to the same method of measuring the light transmittance at 45° tilt and the light transmission φ at ~45° tilt, and the average 値 Y2 (%). According to the following formula, Y1 and Y2 are averaged as the transmittance Υ (%) of the polarizing film. Y=( Y1 + Υ2 ) /2 (5) Measurement of the degree of polarization V of the polarizing film. When the two polarizing films taken in the above (4) are the same as (4) the transmittance is measured, the extending directions are parallel and overlapped. The light transmittance Y (%) and the light transmittance Y 丄 (%) when the extending direction is vertical and overlapped are obtained, and the degree of polarization V (%) is obtained by the following formula. V={(Y|| — Y丄)/(γ|| + Y 丄)}1/2χ1〇〇 (Example 1) 100 parts by mass of PVA containing a polymerization degree of 5800 and a degree of saponification of 99.8 mol% The plasticizer glycerin 12 parts by mass of a 5.5% by mass PVA aqueous solution was cast on a metal roll at 60 ° C and dried for 60 minutes to obtain a PVA film having a thickness of 40 β m. The film was conditioned at 16 ° C and 20% RH for 16 hours, and after adjusting the water content to 3% by mass, the two ends of the film width direction were fixed to the two sides of the metal frame to make the width of the film. The direction did not shrink and was heat treated at 120 ° C for 3 minutes. The degree of swelling of the PVA film after the heat treatment was measured by the method of the above (2), and it was 230%. Further, the retardation enthalpy of the PVA film was measured by the method of the above -13-.201033273 (3), and as a result, it was 29 nm. Next, the PVA film was cut into a flow direction of llcmx in the width direction of 10 cm, and the flow direction was attached to a stretching jig of 4 cm between the chucks in the extending direction, and immersed in pure water at 30 ° C for 1 minute, and then immersed in a crucible.染色3% by mass of iodine and 3% by mass of potassium iodide dyeing solution (temperature 30 ° C) 'extend 2.6 times at a rate of 0.13 m/min to adsorb iodine. Next, the stretched film was immersed in an extension liquid (temperature: 57.5 ° C) containing 4% by mass of boric acid and 6% by mass of potassium iodide, and was extended 2.3 times at a speed of 0.1 m/inin, and then fixed in the extending direction. The polarizing film was obtained by drying at 50 ° C for 4 minutes. According to the methods (4) and (5) above, the transmittance and the degree of polarization of the polarizing film were measured, and as a result, they were 44.0% and 99.9%, respectively, and a polarizing film having good polarizing performance was obtained. (Example 2) 100 parts by mass of PVA having a degree of polymerization of 5800 and a degree of saponification of 99.8 mol% and a 5.5% by mass of a PVA aqueous solution of 12 parts by mass of glycerin as a plasticizer were cast on a metal roll at 60 ° C, and dried. In minutes, a PVA film having a thickness of 40 _# m was obtained. The film was conditioned at 26 ° C and 20% RH for 16 hours, and after adjusting the water content to 3% by mass, the two ends of the film width direction were fixed to the parallel sides of the metal frame so that the width direction of the film was not Shrink and heat at 115 °C for 3 minutes. The degree of swelling of the PVA film after the heat treatment was measured by the method of the above (2), and it was 240%. Further, the retardation enthalpy of the PVA film was measured by the method (3) above, and as a result, it was 26 nm. Then, in the same manner as in the first embodiment, the PVA film was stretched, and iodine was adsorbed, and further extended to obtain a polarizing film. According to the methods (4) and (5) above, the transmittance and the degree of polarization of the polarizing film were measured, and the results were 44.0% and 99.96%, respectively, and a polarizing film of -14-201033273 having good polarizing performance was obtained. (Example 3) A PVA 100 portion having a polymerization degree of 9100 and a degree of saponification of 99. 8 mol% and a 5.5% by mass PVA solution of 12 parts by mass of glycerin as a plasticizer were cast on a metal roll of 60 ° C, After drying for 60 minutes, a PVA film having a thickness of / m was obtained. The film was wetted at 26 ° C, 20% RH for 16 hours, and after adjusting the water content to 3% by mass, the two ends of the film width direction were fixed to the parallel sides of the metal frame so that the width direction of the film was not @ Shrink and heat treatment at 110 °C for 3 minutes. The degree of swelling of the heat-treated PVA film was measured by the method of the above (2), and it was 230%. Further, the retardation enthalpy of the PVA film was measured by the method of the above (3), and as a result, it was 39 nm. Then, in the same manner as in Example 1, except that the stretching ratio was 2.5 times, the PVA film was stretched, and iodine was adsorbed, and further extended to obtain a polarizing film. The transmittance and the degree of polarization of the polarizing film were measured according to the methods (4) and (5) above, and the results were 44.0% and 9.99 %, respectively, to obtain a polarizing film having good polarizing performance. ^ (Example 4) A PVA 100 portion having a polymerization degree of 5,200, a degree of saponification of 99.8 mol%, and a 5.5% by mass PVA solution of 12 parts by mass of glycerin as a plasticizer were cast on a metal roll at 60 ° C, and dried. A Pm film of thickness #m was obtained in 60 minutes. The film was wetted at 26 ° C and 20% RH for 16 hours, and after adjusting the water content to 3% by mass, the two ends of the film were fixed to the parallel sides of the metal frame so that the width direction of the film was not reduced. And heat treated at 135 °C for 3 minutes. The degree of swelling of the heat-treated PVA film was measured by the method of the above (2), and it was 205%. Further, the retardation enthalpy of the PVA film was measured by the method of the above (3), and as a result, it was 29 nm. The acceptance of the quality water 20 is described as the acceptance of the incoming water 40. -15-201033273 Next, in the same way as in the third embodiment, the PVA film is stretched while the iodine is adsorbed, and further extended. A polarizing film is obtained. The transmittance and luminosity of the polarizing film were measured by the methods (4) and (5) above, and the results were 44.0% and 99.95%, respectively, and a polarizing film having good polarizing performance was obtained. (Example 5)
將含有聚合度5500、皂化度99.8莫耳％的PVA 100 量份、和作爲可塑劑的甘油12質量份之5.5質量％PVA _ 溶液流延於60°C的金屬輥上，乾燥6〇分鐘，製得厚度 ❹ V m之PVA薄膜。將此薄膜置於26°C、20% RH條件下 濕16小時，調整含水率爲3質量％後，將薄膜寬度方向 二端固定於金屬框之平行的二邊，使薄膜的寬度方向不 縮，並於130 °C熱處理3分鐘。以上述（2)的方法來測 熱處理後的PVA薄膜之膨潤度，結果爲215%。又以上 (3 )的方法來測定PVA薄膜之阻滯値，結果爲29nrn。 其次，和實施例1相同作法，邊將上述PVA薄膜延 邊使碘被吸附，更進一步進行延伸而製得偏光薄膜。依 上述（4)及（5)之方法來測定此偏光薄膜之透過度及 光度，結果分別爲44.0%、99.99%，製得偏光性能良好 偏光薄膜。 (比較例1 ) 將含有聚合度4800、皂化度99.8莫耳％的PVA100 量份、和作爲可塑劑的甘油12質量份之6.5質量％PVA 溶液流延於60 °C的金屬輥上，乾燥60分鐘，製得厚度 从m之PVA薄膜。將此薄膜置於26°C、20% RH條件下 濕16小時’調整含水率爲3質量％後，將薄膜寬度方向 據 偏 之 質 水 30 調 的 收 定 述 據 偏 之 質 水 40 三田 的 -16- 201033273 二端固定於金屬框之平行的二邊，使薄膜的寬度方向不 縮，並於120 °C熱處理3分鐘。以上述（2)的方法來測 熱處理後的PVA薄膜之膨潤度，結果爲220 %。又以上 (3 )的方法來測定PVA薄膜之阻滯値，結果爲28nm。 其次，除延伸倍率爲2.7倍之外，和實施例1相同 法，邊將上述PVA薄膜延伸，邊使碘被吸附，更進一步 行延伸而製得偏光薄膜。依據上述（4)及（5)之方法 測定此偏光薄膜之透過度及偏光度，結果分別爲44.0% 99.92%，偏光薄膜之偏光度稍不足。 (比較例2 ) 將含有聚合度5800、皂化度99.8莫耳％的PVA100 量份、和作爲可塑劑的甘油1 2質量份之5 . 5質量％ PVA 溶液流延於60 °C的金屬輥上，乾燥60分鐘，製得厚度 Mm之PVA薄膜。將此薄膜置於26°C、20%RH條件下 濕16小時，調整含水率爲3質量％後，將薄膜寬度方向 二端固定於金屬框之平行的二邊，使薄膜的寬度方向不 縮，並於140°C熱處理3分鐘。以上述（2)的方法來測 熱處理後的PVA薄膜之膨潤度，結果爲195%。又以上 (3 )的方法來測定PVA薄膜之阻滯値，結果爲29nm。 其次，和實施例1相同作法，邊將上述PVA薄膜延 邊使碘被吸附，更進一步進行延伸而製得偏光薄膜。依 上述（4)及（5)之方法來測定此偏光薄膜之透過度及 光度’結果分別爲44.0%、99.92%，偏光薄膜之偏光度 不足。 (比較例3 ) 將含有聚合度5800、皂化度99.8莫耳％的PVA100 收 定 述 作 進 來 質 水 40 調 的 收 定 述 3， 據 偏 稍 質 -17- .201033273 量份、和作爲可塑劑的甘油1 2質量份之5.5質量％ PVA水 溶液流延於60°C的金屬輥上，乾燥60分鐘，製得厚度40 /z m之PVA薄膜。將此薄膜置於26°C、20% RH條件下調 濕16小時，調整含水率爲3質量％後，將薄膜寬度方向的 二端固定於金屬框之平行的二邊，使薄膜的寬度方向不收 縮，並於110 °C熱處理3分鐘。以上述（2)的方法來測定 熱處理後的PVA薄膜之膨潤度，結果爲25 0%。又以上述 (3 )的方法來測定PVA薄膜之阻滯値，結果爲28ηπι。 φ 其次，和實施例1相同作法，邊將上述PVA薄膜延伸， 邊使碘被吸附，更進一步進行延伸而製得偏光薄膜。依據 上述（4)及（5)之方法來測定此偏光薄膜之透過度及偏 光度，結果分別爲44.0%、99.87 %，偏光薄膜之偏光度稍 不足。 (比較例4) 將含有聚合度5800、皂化度99.8莫耳％的PVA100質 量份、和作爲可塑劑的甘油12質量份之5.5質量％ PVA水 A 溶液流延於60t的金屬輥上，乾燥60分鐘，製得厚度40 ；(/ m之PVA薄膜。將此薄膜置於26°C、20%RH條件下調 濕16小時，調整含水率爲3質量％後，固定於金屬框的全 部四邊，並於120 °C熱處理3分鐘。以上述（2)的方法來 測定熱處理後的PVA薄膜之膨潤度，結果爲23 0 %。又以 上述（3 )的方法來測定PVA薄膜之阻滯値，結果爲5nm。 其次，和實施例1相同作法，邊將上述PVA薄膜延伸， 邊使碘被吸附，更進一步進行延伸而製得偏光薄膜。依據 上述（4)及（5)之方法來測定此偏光薄膜之透過度及偏 光度，結果分別爲44.0%、99.97%，雖偏光性能良好，惟 -18- .201033273 使偏光薄膜垂直之狀態下，觀察到大的染色斑。 (比較例5) 將含有聚合度5 800、皂化度99.8莫耳％的PVA100 量份、和作爲可塑劑的甘油12質量份之5.5質量％ PVA 溶液流延於60°C的金屬輥上，乾燥60分鐘，製得厚度 m之PVA薄膜。將此薄膜置於26°C、65% RH條件下 濕16小時，調整含水率爲8質量％後，將薄膜寬度方向 二端固定於金屬框之平行的二邊，使薄膜的寬度方向不 φ 縮，並於120°C熱處理3分鐘。以上述（2)的方法來測 熱處理後的PVA薄膜之膨潤度，結果爲230%。又以上 (3 )的方法來測定PVA薄膜之阻滯値，結果爲70nm。 其次，和實施例1相同作法，邊將上述PVA薄膜延fE 邊使碘被吸附，更進一步，除延伸倍率爲1.8倍之外， 實施例1同樣地延伸而製得偏光薄膜。依據上述（4)及（ 之方法來測定此偏光薄膜之透過度及偏光度，結果分別 44.0%、99·20%，偏光薄膜之偏光度稍不足。爲改善偏 外 度而將延伸倍率之目標値由1.8倍改爲2.3倍，結果發生 Ο 伸斷裂，而無法製得偏光薄膜。 彙整上述的結果表示於第1表。 質 水 40 三田 m 的 收 定 述 3 > 和 5 ) 爲 光 延 -19- 201033273 第1表 PVA PVA薄膜 延伸 偏光1 奪膜 聚合度 厚度 熱處理 膨潤 阻滯値 延伸倍 延伸倍 總延伸 透過率 偏光度 m. 度A 率1 率2 倍率 μτα °c % nm 倍 倍 倍 % % 實施例1 5800 40 120 230 29 2.6 2.3 6.0 44.0 99.99 實施例2 5800 40 115 240 26 2.6 2.3 6.0 44.0 99.96 實施例3 9100 20 110 230 39 2.5 2.3 5.8 44.0 99.95 實施例4 5200 40 135 205 29 2.5 2.3 5.8 44.0 99.95 實施例5 5500 30 130 215 29 2.6 2.3 6.0 44.0 99.99 比較例1 4800 40 120 220 28 2.7 2.3 6.2 44.0 99.92 比較例2 5800 40 140 195 29 2.6 2.3 6.0 44.0 99.92 比較例3 5800 40 110 250 28 2.6 2.3 6.0 44.0 99.87 比較例4 5800 40 120 230 5 2.6 2.3 6.0 44.0 99.97* 比較例5 5800 40 120 230 70 2.6 1.8 4.7 44.0 99.20 延伸倍率1: 12 — ΚΙ水溶液中之延伸倍率 延伸倍率2:硼酸-ΚΙ水溶液中之延伸倍率 * :有染色斑The PVA 100 parts containing a polymerization degree of 5500, a degree of saponification of 99.8 mol%, and a 5.5% by mass PVA_ solution of 12 parts by mass of glycerin as a plasticizer were cast on a metal roll at 60 ° C, and dried for 6 minutes. A PVA film having a thickness ❹ V m was obtained. The film was wetted at 26 ° C and 20% RH for 16 hours, and after adjusting the water content to 3% by mass, the two ends of the film were fixed to the parallel sides of the metal frame so that the width direction of the film was not reduced. And heat treated at 130 °C for 3 minutes. The degree of swelling of the heat-treated PVA film was measured by the method of the above (2), and as a result, it was 215%. Further, the method of the above (3) was used to measure the retardation enthalpy of the PVA film, and the result was 29 nm. Then, in the same manner as in Example 1, the PVA film was stretched to make iodine adsorbed, and further extended to obtain a polarizing film. The transmittance and luminosity of the polarizing film were measured according to the methods (4) and (5) above, and the results were 44.0% and 99.99%, respectively, and a polarizing film having good polarizing performance was obtained. (Comparative Example 1) A PVA 100 portion having a polymerization degree of 4800 and a degree of saponification of 99.8 mol% and a 6.5% by mass PVA solution of 12 parts by mass of glycerin as a plasticizer were cast on a metal roll at 60 ° C, and dried. In minutes, a PVA film having a thickness of m was obtained. The film was placed at 26 ° C, 20% RH for 16 hours, and the water content was adjusted to 3% by mass. The film was adjusted to the width of the water 30 to determine the quality of the water. -16- 201033273 The two ends are fixed to the parallel sides of the metal frame so that the width direction of the film is not reduced and heat-treated at 120 °C for 3 minutes. The degree of swelling of the heat-treated PVA film was measured by the method of the above (2), and it was 220%. Further, the retardation enthalpy of the PVA film was measured by the method of the above (3), and the result was 28 nm. Then, in the same manner as in Example 1, except that the stretching ratio was 2.7 times, the PVA film was stretched, and iodine was adsorbed, and further extended to obtain a polarizing film. According to the methods (4) and (5) above, the transmittance and the degree of polarization of the polarizing film were measured, and the results were 44.0% and 99.92%, respectively, and the polarization degree of the polarizing film was slightly insufficient. (Comparative Example 2) A PVA 100 portion having a polymerization degree of 5,800, a degree of saponification of 99.8 mol%, and a 5% by mass of a glycerin as a plasticizer were cast on a metal roll at 60 ° C. After drying for 60 minutes, a PVA film having a thickness of Mm was obtained. The film was wetted at 26 ° C, 20% RH for 16 hours, and after adjusting the water content to 3% by mass, the two ends of the film were fixed to the parallel sides of the metal frame so that the width direction of the film was not reduced. And heat-treated at 140 ° C for 3 minutes. The degree of swelling of the heat-treated PVA film was measured by the method of the above (2), and it was 195%. Further, the retardation enthalpy of the PVA film was measured by the method of the above (3), and as a result, it was 29 nm. Then, in the same manner as in Example 1, the PVA film was stretched to make iodine adsorbed, and further extended to obtain a polarizing film. According to the methods (4) and (5) above, the transmittance and the luminosity of the polarizing film were 44.0% and 99.92%, respectively, and the polarization degree of the polarizing film was insufficient. (Comparative Example 3) The PVA100 containing a polymerization degree of 5,800 and a saponification degree of 99.8 mol% was used as the condensed water 40, and the amount of the PVA 100 was adjusted to be 3, 201033273 parts, and as a plasticizer. The glycerin 12 parts by mass of the 5.5% by mass PVA aqueous solution was cast on a metal roll at 60 ° C and dried for 60 minutes to obtain a PVA film having a thickness of 40 /zm. The film was conditioned at 26 ° C and 20% RH for 16 hours, and after adjusting the water content to 3% by mass, the two ends of the film width direction were fixed to the parallel sides of the metal frame so that the width direction of the film was not Shrink and heat at 3 °C for 3 minutes. The degree of swelling of the PVA film after the heat treatment was measured by the method of the above (2), and it was 25%. Further, the retardation enthalpy of the PVA film was measured by the method of the above (3), and as a result, it was 28 ηπι. φ Next, in the same manner as in Example 1, while stretching the PVA film, iodine was adsorbed and further extended to obtain a polarizing film. According to the methods (4) and (5) above, the transmittance and the degree of polarization of the polarizing film were measured, and the results were 44.0% and 98.77%, respectively, and the polarizing degree of the polarizing film was slightly insufficient. (Comparative Example 4) A PVA water A solution containing 100 parts by mass of PVA having a degree of polymerization of 5800 and a degree of saponification of 99.8 mol% and 12 parts by mass of glycerin as a plasticizer was cast on a metal roll of 60 t, and dried. In a minute, a PVA film having a thickness of 40 ((m) was prepared. The film was conditioned at 26 ° C, 20% RH for 16 hours, adjusted to a moisture content of 3% by mass, and fixed to all four sides of the metal frame, and The heat treatment was carried out at 120 ° C for 3 minutes, and the degree of swelling of the PVA film after the heat treatment was measured by the method of the above (2), and as a result, it was 23%. The blockage of the PVA film was measured by the method of the above (3). In the same manner as in the first embodiment, the PVA film was stretched, and iodine was adsorbed, and further extended to obtain a polarizing film. The polarized light was measured according to the methods (4) and (5) above. The transmittance and the degree of polarization of the film were 44.0% and 99.97%, respectively. Although the polarizing performance was good, only -18-201033273 made the polarizing film vertical, and large stain spots were observed. (Comparative Example 5) PVA100 with a polymerization degree of 5 800 and a saponification degree of 99.8 mol% And a 5.5% by mass of a glycerin as a plasticizer, a 5.5% by mass PVA solution was cast on a metal roll at 60 ° C and dried for 60 minutes to obtain a PVA film having a thickness of m. The film was placed at 26 ° C, 65 ° After being wet for 16 hours under % RH conditions and adjusting the water content to 8 mass%, the two ends of the film width direction were fixed to the parallel sides of the metal frame so that the width direction of the film was not reduced, and heat treatment was performed at 120 ° C for 3 minutes. The swelling degree of the heat-treated PVA film was measured by the method of the above (2), and it was 230%. The retardation enthalpy of the PVA film was measured by the method of the above (3), and the result was 70 nm. Next, and Example 1 In the same manner, iodine was adsorbed while the PVA film was extended by fE, and further, in the same manner as in Example 1, except that the stretching ratio was 1.8 times, a polarizing film was obtained in the same manner as in the above (4) and (methods). The transmittance and the degree of polarization of the polarizing film were measured, and the results were 44.0% and 99.20%, respectively, and the polarizing degree of the polarizing film was slightly insufficient. To improve the degree of partiality, the target of the stretching ratio was changed from 1.8 times to 2.3 times. A rupture occurs and a polarizing film cannot be produced. The above results are shown in Table 1. Qualification water 40 Santian m's collection 3 > and 5) is light extension -19- 201033273 Table 1 PVA PVA film extension polarization 1 film formation polymerization thickness heat treatment swell block Extension magnification extension total extension transmittance polarization degree m. degree A rate 1 rate 2 magnification μτα °c % nm multiple times % % Example 1 5800 40 120 230 29 2.6 2.3 6.0 44.0 99.99 Example 2 5800 40 115 240 26 2.6 2.3 6.0 44.0 99.96 Example 3 9100 20 110 230 39 2.5 2.3 5.8 44.0 99.95 Example 4 5200 40 135 205 29 2.5 2.3 5.8 44.0 99.95 Example 5 5500 30 130 215 29 2.6 2.3 6.0 44.0 99.99 Comparative Example 1 4800 40 120 220 28 2.7 2.3 6.2 44.0 99.92 Comparative Example 2 5800 40 140 195 29 2.6 2.3 6.0 44.0 99.92 Comparative Example 3 5800 40 110 250 28 2.6 2.3 6.0 44.0 99.87 Comparative Example 4 5800 40 120 230 5 2.6 2.3 6.0 44.0 99.97* Comparative Example 5 5800 40 120 230 70 2.6 1.8 4.7 44.0 99.20 Extension ratio 1: 12 — Extension ratio in hydrazine aqueous solution Extension ratio 2: Extension ratio in boric acid-hydrazine aqueous solution*: staining spot
應用於產業之可能性 由本發明的PVA薄膜而製得之偏光薄膜，係可有效地 使用於電子計算機、手錶、筆記型電腦、液晶螢幕、液晶 彩色投影機、液晶電視、車內用導航系統、行動電話、室 內外用之計測機器等液晶顯示裝置的組成零件之偏光板之 製作。 【圖式簡單說明】 無。 【主要元件符號說明】 Μ 〇 -20-The possibility of being applied to the industry, the polarizing film produced by the PVA film of the present invention can be effectively used in electronic computers, watches, notebook computers, liquid crystal screens, liquid crystal color projectors, liquid crystal televisions, navigation systems for vehicles, The production of polarizing plates for components of liquid crystal display devices such as mobile phones and indoor and outdoor measuring devices. [Simple description of the diagram] None. [Main component symbol description] Μ 〇 -20-