1273105 九、發明說明： 【發明所屬之技術領域】 本發明係有關於-種薄膜，特別是有關於一種薄型偏光膜 及其製造方法。 【先前技術】 近年來，由於液晶顯示裝置廣泛應用於例如文書處理器、 ，、手機或液晶電視等電子產品，使得相關元件：偏光：的 需求日益增加，特別是，家庭影音娛樂設備普及化之後，造就 了大尺寸液晶電視的發展趨勢，因此，確有必要加速開發薄型 且大面積範圍的偏光膜，以滿足市場需求。 目前’聚乙稀醇偏光膜大致分成三大類，第—類為含填的 $ w ’第二類為含雙色性染料(diehrc>ie咖)的聚乙婦醇 膜卬苐一顯則為經部分脫水的聚乙烯醇膜。 上述含破的聚乙_膜由於製㈣單且具有較佳的光學 ^，遂成為目前使用率最高的偏光膜一般來說，偏絲 由一延伸的聚乙烯醇膜與至少—例如為三醋酸纖維⑻肛邮 =:TAC)的保護層所組成，其中延展、染色後的聚乙婦i 為20〜35微米，延伸倍率約為5〜6，最常見的為η 二：，這些較厚、寬度窄且延伸倍率低的偏光膜，大大汚 ==可利用率，不符成本考量，甚至有拉伸前後偏光· ^度比㊣達2〜2.5的情形發生，完全無法滿足大尺寸面板的需1273105 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a film, and more particularly to a thin polarizing film and a method of manufacturing the same. [Prior Art] In recent years, since liquid crystal display devices are widely used in electronic products such as word processors, mobile phones, or liquid crystal televisions, the demand for related components: polarized light has been increasing, in particular, after the popularization of home audio-visual entertainment devices. This has created a trend in large-size LCD TVs. Therefore, it is necessary to accelerate the development of thin and large-area polarizing films to meet market demand. At present, the 'polyethylene glycol polarizing film is roughly divided into three categories, the first type is filled with $w' and the second type is a dichromatic dye containing a dichroic dye (diehrc>ie coffee). Partially dehydrated polyvinyl alcohol film. The above-mentioned broken poly-ethylene film has the highest optical transmittance film because of the (4) single and has better optical properties. Generally, the partial filament is composed of an extended polyvinyl alcohol film and at least, for example, triacetic acid. Fiber (8) anal mail =: TAC) consists of a protective layer, wherein the stretched and dyed poly-wife is 20 to 35 microns, the stretching ratio is about 5 to 6, and the most common is η 2:, these are thicker, The polarizing film with narrow width and low stretching ratio is greatly detrimental == availability, which is not cost-effective. Even before and after stretching, the degree of polarization is more than 2 to 2.5, which is completely unable to meet the needs of large-sized panels.
〇659~A21197TWF(N2)；M05023；DAViD 1273105 習知有揭露如何增加膜光學特性或利用乾式製程 均勾度的方法（美國專利第6,760，156與M55,276號/其延伸 倍率可達5〜7。然而，卻少有針對如何增加偏光膜延伸产率、 見度或縮減厚度的討論，因此’仿必要發展出—種可 到縮減厚度、增加延伸倍率及寬度的方法，以提高材料利用^ 【發明内容】 有鑑於此，本發明係提供—種薄膜之製造方法，包括·將 表面帶有《之薄膜置於—含雙㈣之水槽中並拉伸之。 本發明另提供一種由上述方法所製得之薄膜。 一為使本發明之上述目的及特徵能更明顯易懂，下文特舉較 佳實施例，並配合所附圖式，作詳細說明如下。 " 【實施方式】 ，本發明提供—種薄膜，係由下列方法所製得：將-表面帶 有羥基之薄膜置於一含雙羧酸之水槽中並拉伸之。 此表面帶有羥基的薄膜可為一聚乙烯醇膜。 本發明製作薄膜的步驟更包括對薄膜進行膨潤及染色處 理。染色時，可藉由-包含破分子舆埃離子的含埃溶液進行染 色，、中蛾刀子的重畺百分比大體介於〇·〇1〜〇•丄。〆〇之間，碘離 0659- A21197TWF(N2);M05023;DAVID . 1273105 子的重量百分比大體介於0.1〜10%之間。 上述雙羧酸可為碳數4〜6的雙羧酸，例如己二酸（adipic acid)，其於水槽（延伸槽）藥液中的重量百分比大體介於1〜10% 之間，較佳為2〜5%之間。延伸槽中更包括添加例如鋅離子的 過渡金屬離子、鹽酸、硫酸或硼酸，其中過渡金屬離子的重量 百分比大體介於0.1〜3%之間，硼酸的重量百分比大體介於 1〜3%之間。延伸槽的操作溫度大體控制在攝氏40〜60度之間。 ί 本發明係以雙羧酸取代習知的硼酸作為與聚乙烯醇膜表 面鍵結的分子（請參閱第1圖），由於雙羧酸具有親水性的酸基 末端，遂很容易與聚乙烯醇膜表面的羥基形成酯鍵鍵結，且其 長碳鏈（4〜6個碳）的骨架在空間上可旋轉、彎曲，與習知無法 彎曲的硼酸相比，更可增加整體材料的堅韌度與延展性，使其 在拉伸過程中不致輕易斷裂，有助於產出更薄的偏光膜。此 外，為了提高化學反應性、膜的拉伸性質及防止掉色，本發明 g 亦在延伸槽中加入其他例如過渡金屬離子、強酸或硼酸等的添 加劑。 本發明藉由改變例如操作溫度、穿膜路徑、槽内夾輪轉 速、雙羧酸濃度或添加劑濃度等的延伸槽參數，而獲得一厚度 薄、寬度廣且延伸倍率高的偏光膜。 本發明於偏光膜完成製作後，更可包括貼合至少一層例如 為三酷酸纖維（triacetyl cellulose，TAC).、聚酯(polyester，PET) 0659-A21197TWF(N2)；M05023；DAVID 7 1273105 或來冰片稀(pQlyn()rb_ne)的光學膜於此偏光膜上。 本發明另提供-種由上述方法所製得之薄膜，其可應用於 各式的液晶顯示器，例如可應用在車輛GPS系統的螢幕顯示。 鱗人本I月I拉伸後的偏光膜，其延伸倍率（Streichingrati〇)大 體介於6〜9之間，厚度大體介於1〇〜2〇微米之間，拉伸前後的 旱度比大幻f於4〜8之間，以及拉伸前後的寬度比大體介於 1.5〜2之間。 以下藉由數個實施例來更進一步說明本發明之特徵及優 點。 【實施例】 實施例1 將一見度6:>0耄米、厚度75微米的聚乙烯醇膜置於一水 鲁槽中進仃膨潤，接著，卩-含織溶液對聚乙烯醇膜進行染色， 之後，如第3圖所示，將聚乙烯醇膜30置;含3%己二酸、 -1%硼酸與（M5%轉子的延伸# 1〇巾進行拉伸，以製作完成 • 一延伸的聚乙烯醇偏光膜。此延伸槽1〇内的三對夾輪（nip ，r〇ller)20其轉速比分別為丨：15 : 155，而偏光膜刈在槽内的 延伸路徑如圖所示。槽内拉伸溫度為攝氏53度。最後，經拉 伸、乾煉後的偏先膜，其延伸倍率為7·24，厚度為12微米， 寬度為3 8 0毫米。〇659~A21197TWF(N2);M05023;DAViD 1273105 It is known to disclose how to increase the optical properties of the film or to use the dry process to achieve the hooking degree (US Patent Nos. 6,760,156 and M55,276/the extension ratio can reach 5~) 7. However, there is little discussion on how to increase the yield, visibility or thickness reduction of the polarizing film. Therefore, it is necessary to develop a method to reduce the thickness, increase the stretching ratio and width to improve the material utilization. SUMMARY OF THE INVENTION In view of the above, the present invention provides a method for manufacturing a film comprising: placing a film on a surface in a water tank containing a double (four) and stretching it. The present invention further provides a method as described above. The above-mentioned objects and features of the present invention will be more apparent and understood. The following detailed description of the preferred embodiments, together with the accompanying drawings, will be described in detail below. " The invention provides a film obtained by placing a film having a hydroxyl group on a surface in a water tank containing a dicarboxylic acid and stretching it. The film having a hydroxyl group on the surface may be a polyethylene. The film forming step of the invention further comprises swelling and dyeing the film. When dyeing, the film may be dyed by an eucalyptus solution containing a broken molecular ionic ion, and the percentage of heavy mites of the middle moth knife is substantially between 膜. · 〇1~〇•丄.Between 〆〇, iodine is 0659- A21197TWF(N2); M05023; DAVID. The weight percentage of 1273105 is generally between 0.1 and 10%. The above dicarboxylic acid can be carbon number 4 ～6 of a dicarboxylic acid, such as adipic acid, in a water tank (extending trough) solution, the weight percentage is generally between 1 and 10%, preferably between 2 and 5%. The tank further includes a transition metal ion such as zinc ion, hydrochloric acid, sulfuric acid or boric acid, wherein the weight percentage of the transition metal ion is generally between 0.1 and 3%, and the weight percentage of boric acid is substantially between 1 and 3%. The operating temperature of the stretching tank is generally controlled between 40 and 60 degrees Celsius. ί The present invention replaces the conventional boric acid with a dicarboxylic acid as a molecule bonded to the surface of the polyvinyl alcohol film (see Fig. 1), due to the double The carboxylic acid has a hydrophilic acid-based end, which is very accommodating It is easy to form an ester bond with the hydroxyl group on the surface of the polyvinyl alcohol film, and the skeleton of the long carbon chain (4 to 6 carbons) is spatially rotatable and curved, and can be increased compared with the conventional unbaked boric acid. The toughness and ductility of the monolithic material are such that they do not easily break during stretching, contributing to the production of a thinner polarizing film. Furthermore, in order to improve chemical reactivity, tensile properties of the film, and prevention of color loss, the present invention g also adding other additives such as transition metal ions, strong acids or boric acid to the stretching tank. The invention extends the groove by changing, for example, operating temperature, film path, pinch speed in the tank, dicarboxylic acid concentration or additive concentration. The parameter is obtained to obtain a polarizing film having a small thickness, a wide width, and a high stretching ratio. After the polarizing film is completed, the present invention may further comprise at least one layer of, for example, triacetyl cellulose (TAC), polyester (PET) 0659-A21197TWF (N2); M05023; DAVID 7 1273105 or An optical film of borneol thin (pQlyn() rb_ne) is applied to the polarizing film. The present invention further provides a film produced by the above method, which is applicable to various liquid crystal displays, for example, to a screen display of a GPS system of a vehicle. The polarizing film of the scaled human I-I stretch has a stretching ratio (Streichingrati〇) of generally between 6 and 9, and a thickness of substantially between 1 〇 and 2 〇 micrometers, and the dryness ratio before and after stretching is large. The magic f is between 4 and 8, and the width ratio before and after stretching is generally between 1.5 and 2. The features and advantages of the present invention are further illustrated by the following examples. [Examples] Example 1 A polyvinyl alcohol film having a visibility of 6:>0 mm and a thickness of 75 μm was placed in a water-lubrication tank to be swelled, and then a ruthenium-containing woven solution was applied to the polyvinyl alcohol film. Dyeing, and then, as shown in Fig. 3, the polyvinyl alcohol film 30 is placed; 3% adipic acid, -1% boric acid and (M5% rotor extension #1 wipes are stretched to complete) The extended polyvinyl alcohol polarizing film has three rotation speeds (nip, r〇ller) 20 in the extension groove 1 which are respectively 丨: 15: 155, and the extension path of the polarizing film 刈 in the groove is as shown in the figure As shown in the figure, the stretching temperature in the tank is 53 degrees Celsius. Finally, the stretched and dried film has a stretching ratio of 7.24, a thickness of 12 μm, and a width of 380 mm.
0659-Α2119丌 WF(N2);M05023;DAVID 1273105 實施例2 將一寬度650毫米、厚度乃微米的聚乙烯醇膜置於一水 槽中進行膨潤，接著，以一含碘溶液對聚乙烯醇膜進行染色， 之後，如第3圖所示，將聚乙烯醇膜30置於一含3°/。己二酸、 1 /〇硼敲與〇· 15 %鋅離子的延伸槽丨〇中進行拉伸，以製作完成 延伸的聚乙烯醇偏光膜。此延伸槽1〇内的三對夾輪 roller)20其轉速比分別為丨：145 : 15，而偏光膜在槽内的 延伸路徑如圖所示。槽内拉伸溫度為攝氏53度。最後，經拉 伸、乾燥後的偏光膜，其延伸倍率為6 77，厚度為17微求， 寬度為342毫米。 實施例3 將一寬度650毫米、厚度75微米的聚乙烯醇膜置於一水 ' 槽中進行膨潤，接著，以一含碘溶液對聚乙烯醇膜進行染色， • 之後，如第4圖所示，將聚乙烯醇膜60置於一含3%己二酸、 1 /〇硼1與〇·15 %鋅離子的延伸槽4〇中進行拉伸，以製作完成 Φ 一延伸的聚乙烯醇偏光膜。此延伸槽40内的三對夾輪（nip roller)D〇其轉速比分別為丨·· h5 ·· 15，而偏光膜6〇在槽内的 延伸路徑如圖所示。槽内拉伸溫度為攝氏53度。最後，經拉 - 伸、乾燥後的偏光膜，其延伸倍率為7.00，厚度為11.5微米， 、 見度為418宅米。 實施例4 將一寬度650毫米、厚度75微米的聚乙烯醇膜置於一水 槽中進行膨潤，接著，以一含碘溶液對聚乙烯醇膜進行染色， 0659-A21197TWF(N2)；M05023；DAVID q 1273105 之後，如第4圖所示，將聚乙烯醇膜60置於一含3%己二酸、 1 °/〇硼酸與0.15 %鋅離子的延伸槽40中進行拉伸，以製作完成 一延伸的聚乙稀醇偏光膜。此延伸槽40内的三對夾輪（nip roller)5 0其轉速比分別為1 : 1·45: 1.5，而偏光膜60在槽内的 延伸路徑如圖所示。最後，經拉伸、乾燥後的偏光膜，其延伸 倍率為6.77，厚度為14.5微米，寬度為3 85毫米。 此偏光膜進一步與钱刻後的兩層TAC膜點合並於攝氏70 > 度烘乾後成為一偏光板，然後，進行熱機械分析（thermal mechanical analysis，測試條件為攝氏90度、30分鐘），結杲發 現，偏光板收縮量（contraction quantity)為47·93微米（請參閱第 2圖），遠低於目前市面上同類產品的測量值（90〜110微米）。 比較實施例 將一寬度650毫米、厚度75微米的聚乙烯醇膜置於一水 槽中進行膨潤，接著，以一含碘溶液對聚乙烯醇膜進行染色， 之後，將聚乙烯醇膜置於一含5%硼酸的延伸槽中進行拉伸， 以製作完成一延伸的聚乙烯醇偏光膜。此延伸槽内的三對夹輪 (nip roller)其轉速比分別為1 ·· 1.4 : 1.33，且槽内拉伸溫度為攝 氏53度。最後，經拉伸、乾燥後的偏光膜，其延伸倍率為5.8， 厚度為24微米，寬度為340毫米。 以下係實施例1〜4與比較實施例製作的偏光膜，其在延伸 倍率、厚度、寬度、拉伸前後之厚度比及拉伸前後之寬度比上 的差異比較，如表一所示。 0659-A21197TWF(N2)；M05023；DAVID 10 12731050659-Α2119丌WF(N2); M05023; DAVID 1273105 Example 2 A polyvinyl alcohol film having a width of 650 mm and a thickness of micron was placed in a water bath for swelling, followed by an iodine-containing solution against a polyvinyl alcohol film. The dyeing was carried out, and then, as shown in Fig. 3, the polyvinyl alcohol film 30 was placed at a temperature of 3 °/. The adipic acid, 1 / 〇 boron knuckle and 〇 · 15% zinc ion are stretched in an extended groove to prepare a stretched polyvinyl alcohol polarizing film. The three pairs of pinch rollers 20 in the extension slot 1 have a rotational speed ratio of 145: 145: 15, respectively, and the extending path of the polarizing film in the groove is as shown. The stretching temperature in the tank was 53 degrees Celsius. Finally, the stretched and dried polarizing film has a stretching ratio of 6 77, a thickness of 17 micro, and a width of 342 mm. Example 3 A polyvinyl alcohol film having a width of 650 mm and a thickness of 75 μm was placed in a water bath to swell, and then the polyvinyl alcohol film was dyed with an iodine-containing solution, and then, as shown in Fig. 4 It is shown that the polyvinyl alcohol film 60 is stretched in an extension tank 4 of 3% adipic acid, 1 / 〇 boron 1 and 〇 15 % zinc ions to prepare a Φ-extended polyvinyl alcohol. Polarized film. The speed ratio of the three pairs of nip rollers D in the extending groove 40 is 丨··h5··15, and the extending path of the polarizing film 6〇 in the groove is as shown. The stretching temperature in the tank was 53 degrees Celsius. Finally, the stretched film after stretching and drying has a stretching ratio of 7.00, a thickness of 11.5 μm, and a visibility of 418 house meters. Example 4 A polyvinyl alcohol film having a width of 650 mm and a thickness of 75 μm was placed in a water bath for swelling, and then a polyvinyl alcohol film was dyed with an iodine-containing solution, 0659-A21197TWF(N2); M05023; DAVID q 1273105 Thereafter, as shown in Fig. 4, the polyvinyl alcohol film 60 is stretched in an extension tank 40 containing 3% adipic acid, 1 °/barium boric acid and 0.15% zinc ion to complete the production. Extended polyethylene glycol polarizing film. The speed ratio of the three pairs of nip rollers 50 in the extending groove 40 is 1:1·45:1.5, respectively, and the extending path of the polarizing film 60 in the groove is as shown. Finally, the stretched and dried polarizing film had a stretching ratio of 6.77, a thickness of 14.5 μm, and a width of 3,85 mm. The polarizing film is further combined with the two layers of TAC film after the engraving at a temperature of 70 ° C. After drying, it becomes a polarizing plate, and then subjected to thermal mechanical analysis (test conditions are 90 degrees Celsius, 30 minutes) According to the knot, the contraction quantity of the polarizing plate is 47·93 μm (see Figure 2), which is much lower than the measured value of the similar products on the market (90 to 110 μm). Comparative Example A polyvinyl alcohol film having a width of 650 mm and a thickness of 75 μm was placed in a water bath for swelling, and then the polyvinyl alcohol film was dyed with an iodine-containing solution, and then the polyvinyl alcohol film was placed in a The stretching was carried out in an extension tank containing 5% boric acid to prepare a polyvinyl alcohol polarizing film which completed an extension. The speed ratio of the three pairs of nip rollers in the extension groove is 1 ·· 1.4 : 1.33, and the stretching temperature in the groove is 53 degrees Celsius. Finally, the stretched and dried polarizing film had a stretching ratio of 5.8, a thickness of 24 μm, and a width of 340 mm. The polarizing films produced in Examples 1 to 4 and Comparative Examples were compared with each other in the ratios of the stretching ratio, the thickness, the width, the thickness ratio before and after stretching, and the width ratio before and after stretching, as shown in Table 1. 0659-A21197TWF(N2); M05023; DAVID 10 1273105
延伸倍率 厚度(微米) 寬度(厘米） 拉伸前後 之厚度比 拉伸前後 之見度比 實施例1 7.24 12.0 380 6.25 1.72 實施例2 6.77 17.0 342 4.41 1.89 實施例3 7.00 11.5 418 6.52 1.56 實施例4 6.77 14.5 385 5.17 1.69 比較實施例 5.80 24.0 340 3.13 1.91 表一 由表一可看出，本發明偏光膜有較習知高的延伸倍率，其 厚度經拉伸後可控制在低於20微米以下，且寬度不會因長度 拉伸而大幅度縮減，因此，根據本發明製法可獲得一薄的且延 伸面積大的偏光膜，大大提升材料利用率。 雖然本發明已以較佳實施例揭露如上，然其並非用以限定 本發明之範圍，任何熟習此技藝者，在不脫離本發明之精神和 範圍内，當可作各種之更動與潤飾，因此本發明之保護範圍當 視後附之申請專利範圍所界定者為準。 0659-A2119 丌WF(N2);M05023;DAVID 11 1273105 【圖式簡單說明】 第1圖係為本發明雙羧酸與習知狐酸於聚乙烯醇膜表面之 鍵結情形。 _ 第2圖係為本發明實施例4製作之偏光板，其熱機械分析 之結果。 第3〜4圖係為本發明偏光膜於延伸槽中之延伸路徑。 【主要元件符號說明】 無。 'Extension Magnification Thickness (μm) Width (cm) Thickness before and after stretching than before and after stretching Example 1 7.24 12.0 380 6.25 1.72 Example 2 6.77 17.0 342 4.41 1.89 Example 3 7.00 11.5 418 6.52 1.56 Example 4 6.77 14.5 385 5.17 1.69 Comparative Example 5.80 24.0 340 3.13 1.91 Table 1 As can be seen from Table 1, the polarizing film of the present invention has a relatively high stretching ratio, and its thickness can be controlled to be below 20 μm after stretching. Moreover, the width is not greatly reduced by the length stretching. Therefore, according to the manufacturing method of the present invention, a thin polarizing film having a large extension area can be obtained, which greatly improves the material utilization rate. While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the scope of the present invention, and various modifications and changes may be made without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims. 0659-A2119 丌WF(N2); M05023; DAVID 11 1273105 [Simplified description of the drawings] Fig. 1 is a bonding state of a dicarboxylic acid of the present invention and a conventional cinnamic acid on the surface of a polyvinyl alcohol film. Fig. 2 is a result of thermomechanical analysis of a polarizing plate produced in Example 4 of the present invention. Figures 3 to 4 show the extension path of the polarizing film of the present invention in the extending groove. [Main component symbol description] None. '
0659-A21197TWF(N2)；M05023；DAVID 120659-A21197TWF(N2);M05023;DAVID 12