TWI459054B - Polarizing plate and manufacturing method thereof - Google Patents
Polarizing plate and manufacturing method thereof Download PDFInfo
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Description
本發明係關於一種偏光板及其製造方法。又，本發明係關於一種使用該偏光板之光學膜，以及液晶顯示裝置、有機EL(Electro Luminescence，電致發光)顯示裝置、PDP(Plasma Display Panel，電漿顯示器)等圖像顯示裝置。The present invention relates to a polarizing plate and a method of manufacturing the same. Further, the present invention relates to an optical film using the polarizing plate, and an image display device such as a liquid crystal display device, an organic EL (Electro Luminescence) display device, or a PDP (Plasma Display Panel).
先前，作為液晶顯示裝置等圖像顯示裝置中所使用之偏光板，因兼具較高之穿透率及偏光度，故而使用將由經碘染色之聚乙烯醇系膜所構成之偏光元件、與三乙醯纖維素膜等保護膜積層而成者。Conventionally, as a polarizing plate used in an image display device such as a liquid crystal display device, since a polarizing plate having a high transmittance and a degree of polarization is used, a polarizing element composed of a polyvinyl alcohol film dyed with iodine is used. A protective film such as a triacetonitrile cellulose film is laminated.
近年來，液晶顯示裝置隨著其廣泛利用，在高溫條件下等長時間使用之情形增多，故業者正謀求對應其所利用之用途的畫質變化較小之液晶顯示裝置。隨之，對於偏光板，業者亦謀求在高溫條件下放置時或在高溫高濕條件下放置時之光學特性不發生劣化的耐久性。In recent years, liquid crystal display devices have been widely used, and they have been used for a long period of time under high temperature conditions. Therefore, the liquid crystal display device is required to be used in accordance with the use of the liquid crystal display device. Accordingly, in the case of a polarizing plate, the durability of the polarizing plate is not deteriorated when the optical property is placed under high temperature conditions or under high temperature and high humidity conditions.
例如揭示有：藉由使用高聚合度之聚乙烯醇膜或控制偏光元件之延伸方法，或者積層保護膜之後進而進行乾燥處理，而提昇在高溫高濕條件下之耐久性(例如參照專利文獻1)。又，揭示有：在積層保護膜之後，實施高溫及加濕處理，藉此提昇耐久性(例如參照專利文獻2)。For example, it is disclosed that, by using a polyvinyl alcohol film having a high degree of polymerization or a method of controlling a polarizing element, or by laminating a protective film and then performing a drying treatment, durability under high temperature and high humidity conditions is improved (for example, refer to Patent Document 1) ). Further, it is disclosed that high temperature and humidification treatment are performed after the protective film is laminated, thereby improving durability (for example, refer to Patent Document 2).
然而，上述專利文獻中所記載之偏光板存在耐久性不充分，或缺乏中性色調之情形。隨著圖像顯示裝置之利用領域之擴大，業者要求偏光板具有更高之耐久性。However, the polarizing plate described in the above patent document has insufficient durability or lacks a neutral color tone. With the expansion of the field of use of image display devices, operators have demanded higher durability of polarizing plates.
先前技術文獻Prior technical literature
專利文獻Patent literature
專利文獻1：日本專利特開平9-197127號公報Patent Document 1: Japanese Patent Laid-Open No. Hei 9-197127
專利文獻2：日本專利特開2006-23573號公報Patent Document 2: Japanese Patent Laid-Open Publication No. 2006-23573
本發明之目的在於提供一種由聚乙烯醇系膜所構成之耐久性優異之偏光板及其製造方法。An object of the present invention is to provide a polarizing plate which is excellent in durability and which is composed of a polyvinyl alcohol film and a method for producing the same.
又，本發明之目的在於提供一種使用該偏光板之光學膜，進而使用該偏光板、光學膜之圖像顯示裝置。Moreover, an object of the present invention is to provide an image display apparatus using the optical film of the polarizing plate and further using the polarizing plate or the optical film.
本申請案發明者等人積極研究，結果發現：藉由包含在厚度方向上具有拉曼分光峰值強度分布之偏光元件的偏光板，可解決上述課題，從而完成了本發明。As a result of active research by the inventors of the present invention, it has been found that the above problem can be solved by a polarizing plate including a polarizing element having a Raman spectroscopic peak intensity distribution in the thickness direction, and the present invention has been completed.
即，本發明係關於一種偏光板，其係於利用碘將聚乙烯醇系膜染色之偏光元件之兩面上具有保護膜者，該偏光元件剖面之厚度方向中心部以拉曼分光法所測得在105±5cm-1 範圍內之最大峰值強度T1 、與該偏光元件之厚度方向端部以拉曼分光法所測得在105±5cm-1 範圍內之最大峰值強度T2 之比滿足下述關係：That is, the present invention relates to a polarizing plate which is provided with a protective film on both sides of a polarizing element which dyes a polyvinyl alcohol-based film with iodine, and the central portion in the thickness direction of the cross section of the polarizing element is measured by Raman spectroscopy. maximum peak intensity in the range of 105 ± -1 5cm of T 1, the end portion in the thickness direction of the polarizing element Raman spectroscopy measured maximum peak intensity in the range of 105 ± -1 5cm ratio of T 2 satisfying Relationship:
0.920≦T2 /T1 ≦0.985。0.920 ≦ T 2 / T 1 ≦ 0.985.
進而，本發明係關於一種上述偏光板之製造方法。Further, the present invention relates to a method of manufacturing the above polarizing plate.
本發明之偏光板之製造方法具有對聚乙烯醇系膜至少依序實施碘染色步驟及交聯步驟而獲得偏光元件之步驟、以及在所獲得之偏光元件上積層保護膜之步驟，較好的是碘染色步驟中之染色浴浸漬時間(tB )與交聯步驟中之交聯浴浸漬時間(tC )之比(tC /tB )為1.30~3.90。The method for producing a polarizing plate of the present invention comprises the steps of: at least sequentially performing an iodine dyeing step and a crosslinking step to obtain a polarizing element, and a step of laminating a protective film on the obtained polarizing element. The ratio (t C /t B ) of the dye bath immersion time (t B ) in the iodine dyeing step to the cross-link bath immersion time (t C ) in the crosslinking step is 1.30 to 3.90.
進而，於本發明之偏光板之製造方法中，較好的是在交聯步驟之後，實施浸漬於碘化鉀濃度為1~5重量%之溶液中之步驟(色調調整步驟)。Further, in the method for producing a polarizing plate of the present invention, it is preferred to carry out a step of immersing in a solution having a potassium iodide concentration of 1 to 5% by weight after the crosslinking step (color tone adjusting step).
又，本發明係關於一種光學膜、以及使用上述偏光板或上述光學膜之圖像顯示裝置，該光學膜之特徵在於：其使用至少1片上述偏光板。Furthermore, the present invention relates to an optical film, and an image display device using the above polarizing plate or the optical film, which is characterized in that at least one of the above polarizing plates is used.
藉由拉曼分光法所測得在105cm-1 附近之峰值，係與聚乙烯醇與I3 - 離子之錯合物(PVA-I3 - 錯合物)之拉曼散射相對應。於本發明中，藉由包含如下之偏光元件，可提高偏光板之耐久性，該偏光元件係厚度方向中央部與端部以拉曼分光法所測得之峰值強度為特定比值，即PVA-I3 - 錯合物在厚度方向上具有規定之濃度分布者。By Raman spectroscopy peak measured in the vicinity of 105cm -1, with a polyvinyl alcohol-based and I 3 - ions complexes (PVA-I 3 - complexes) of Raman scattering, respectively. In the present invention, the durability of the polarizing plate can be improved by including a polarizing element which is a specific ratio of the peak intensity measured by Raman spectroscopy in the central portion and the end portion in the thickness direction, that is, PVA- The I 3 - complex has a defined concentration distribution in the thickness direction.
本發明之偏光板係在對聚乙烯醇系膜實施碘染色處理之偏光元件之兩面積層保護膜者。本發明之偏光板滿足如下關係，即偏光板剖面中，上述偏光元件剖面之厚度方向中心部以拉曼分光法所測得在105cm-1 附近之最大峰值強度T1 、與該偏光元件之厚度方向端部以拉曼分光法所測得在105cm-1 附近之最大峰值強度T2 之比為0.920≦T2 /T1 ≦0.985。峰值強度比T2 /T1 較好的是0.930以上，更好的是0.950以上，更好的是0.955以上。若峰值強度比在上述範圍之外，則有偏光板之耐久性下降之傾向。再者，拉曼分光光譜可藉由激發波長為514.5nm之Ar+ 雷射照射來測定。再者，所謂105cm-1 附近之最大峰值強度係指在105±5cm-1 範圍內之峰頂之拉曼散射強度。The polarizing plate of the present invention is a two-layer protective film of a polarizing element which is subjected to iodine dyeing treatment on a polyvinyl alcohol-based film. The polarizing plate of the present invention satisfies the relationship that the maximum peak intensity T 1 in the vicinity of 105 cm -1 and the thickness of the polarizing element measured by Raman spectroscopy in the central portion in the thickness direction of the cross section of the polarizing element in the cross section of the polarizing plate The ratio of the maximum peak intensity T 2 around 105 cm -1 measured by Raman spectroscopy at the direction end was 0.920 ≦ T 2 / T 1 ≦ 0.985. The peak intensity ratio T 2 /T 1 is preferably 0.930 or more, more preferably 0.950 or more, still more preferably 0.955 or more. When the peak intensity ratio is outside the above range, the durability of the polarizing plate tends to decrease. Further, the Raman spectroscopic spectrum can be measured by an Ar + laser irradiation having an excitation wavelength of 514.5 nm. Furthermore, the term maximum peak intensity of 105cm -1 near 105 ± means the peak intensity of Raman scattering within the range of 5cm -1.
通常，經碘染色處理之偏光元件中，碘係以三碘離子(I3 - )及五碘離子(I5 - )與聚乙烯醇(PVA)之錯合物的形式存在，藉由拉曼分光法測得的在105cm-1 附近之峰值對應於PVA與I3 - 之錯合物(PVA-I3 - 錯合物)之拉曼散射。因此，所謂此峰值滿足特定比率，意指偏光元件中之PVA-I3 - 錯合物在厚度方向上具有規定之濃度分布。Usually, in the iodine-dyed polarizing element, iodine exists in the form of a complex of triiodide (I 3 - ) and penta-iodide (I 5 - ) and polyvinyl alcohol (PVA) by Raman. The peak near 105 cm -1 measured by the spectroscopic method corresponds to the Raman scattering of the complex of PVA and I 3 - (PVA-I 3 - complex). Therefore, the fact that this peak satisfies a specific ratio means that the PVA-I 3 - complex in the polarizing element has a prescribed concentration distribution in the thickness direction.
若本申請案發明之偏光板，於利用碘將聚乙烯醇系膜染色之偏光元件之兩面上具有保護膜，且拉曼分光之峰值強度比T2 /T1 在上述範圍內，則其他構成或製造方法並無特別限定，以下，詳細記述構成本發明偏光板之偏光元件、保護膜、及偏光板之製造方法之較好態樣。According to the polarizing plate of the invention of the present application, a protective film is provided on both sides of a polarizing element which dyes a polyvinyl alcohol film by using iodine, and the peak intensity ratio T 2 /T 1 of Raman splitting is within the above range, and other constitutions The production method is not particularly limited. Hereinafter, a preferred embodiment of the polarizing element, the protective film, and the method for producing the polarizing plate constituting the polarizing plate of the present invention will be described in detail.
作為構成本發明偏光板之偏光元件，係使用含有碘之聚乙烯醇系偏光元件。對於適用於偏光元件的聚乙烯醇系膜之材料，可使用聚乙烯醇或其衍生物。作為聚乙烯醇之衍生物，可列舉聚乙烯醇縮甲醛、聚乙烯醇縮乙醛等，此外可列舉經乙烯、丙烯等烯烴，丙烯酸、甲基丙烯酸、丁烯酸等不飽和羧酸及其烷基酯，丙烯醯胺等改性而成者。聚乙烯醇之聚合度較好的是100~10000左右，更好的是1000~10000，更好的是1000~8000，尤其好的是2000~6000。可較好地使用皂化度為80~100莫耳%左右者。As the polarizing element constituting the polarizing plate of the present invention, a polyvinyl alcohol-based polarizing element containing iodine is used. For the material of the polyvinyl alcohol-based film suitable for the polarizing element, polyvinyl alcohol or a derivative thereof can be used. Examples of the polyvinyl alcohol derivative include polyvinyl formal, polyvinyl acetal, and the like, and examples thereof include an olefin such as ethylene or propylene, and an unsaturated carboxylic acid such as acrylic acid, methacrylic acid or crotonic acid. Alkyl ester, acrylamide and the like are modified. The degree of polymerization of polyvinyl alcohol is preferably from about 100 to 10,000, more preferably from 1,000 to 10,000, more preferably from 1,000 to 8,000, and particularly preferably from 2000 to 6,000. A saponification degree of about 80 to 100 mol% can be preferably used.
又，偏光元件通常藉由碘染色及延伸而獲得，於構成本發明偏光板之偏光元件中，延伸前之原尺寸膜之膜厚較好的是20~100μm，更好的是40~75μm。Further, the polarizing element is usually obtained by iodine dyeing and stretching. In the polarizing element constituting the polarizing plate of the present invention, the film thickness of the original size film before stretching is preferably from 20 to 100 μm, more preferably from 40 to 75 μm.
上述聚乙烯醇系膜中亦可含有塑化劑等添加劑。作為塑化劑，可列舉多元醇及其縮合物等，例如可列舉：甘油、二甘油、三甘油、乙二醇、丙二醇、聚乙二醇等。塑化劑之使用量並無特別限制，較好的是在聚乙烯醇系膜中為20重量%以下。The polyvinyl alcohol-based film may further contain an additive such as a plasticizer. Examples of the plasticizer include a polyhydric alcohol and a condensate thereof, and examples thereof include glycerin, diglycerin, triglycerin, ethylene glycol, propylene glycol, and polyethylene glycol. The amount of the plasticizer to be used is not particularly limited, but is preferably 20% by weight or less in the polyvinyl alcohol-based film.
上述偏光元件之製造方法並無特別限定，但至少包含將上述聚乙烯醇系膜浸漬於含有碘及/或碘離子之溶液(染色浴)中的步驟(以下，有時稱為「碘染色步驟」)，以及在碘染色步驟之後將其浸漬於含有硼酸等交聯劑之溶液(交聯浴)中的步驟(以下，有時稱為「交聯步驟」)，碘染色步驟中之染色浴浸漬時間tB 與交聯步驟中之交聯浴浸漬時間tC 之比tC /tB 較好的是1.30~3.90，更好的是1.40~3.00，更好的是1.50~2.60。The method for producing the polarizing element is not particularly limited, and at least includes a step of immersing the polyvinyl alcohol-based film in a solution (dye bath) containing iodine and/or iodide ions (hereinafter, sometimes referred to as an "iodine dyeing step") And a step of immersing it in a solution (crosslinking bath) containing a crosslinking agent such as boric acid (hereinafter, referred to as "crosslinking step"), and a dye bath in the iodine dyeing step. The ratio t C /t B of the immersion time t B to the crosslinking bath immersion time t C in the crosslinking step is preferably 1.30 to 3.90, more preferably 1.40 to 3.00, more preferably 1.50 to 2.60.
當「碘染色步驟」與「交聯步驟」之浸漬時間之比tC /tB 在上述範圍內之情形時，存在如下之傾向：厚度方向中心部以拉曼分光法所測得在105cm-1 附近之最大峰值強度T1 、與該偏光元件之厚度方向端部以拉曼分光法所測得在105cm-1 附近之最大峰值強度T2 之比在上述較好的範圍內，且可抑制在高溫高濕下碘之褪色。When the ratio t C /t B of the immersion time of the "iodine dyeing step" and the "crosslinking step" is within the above range, there is a tendency that the center portion in the thickness direction is measured by Raman spectroscopy at 105 cm - The ratio of the maximum peak intensity T 1 in the vicinity of 1 to the maximum peak intensity T 2 in the vicinity of 105 cm -1 measured by Raman spectroscopy in the thickness direction end portion of the polarizing element is within the above preferred range, and can be suppressed Fading of iodine under high temperature and high humidity.
另一方面，於tC /tB 較小之情形時，存在如下傾向：偏光元件之厚度方向中心部之碘離子濃度變得相對大於偏光元件之表面附近之碘離子濃度，即T2 /T1 小於上述較好的範圍，耐久性下降。如此，雖然耐久性根據浸漬時間之比值而有所不同的原因尚不明確，但因「交聯步驟」中之浸漬時間tC 相對較短，故而認為其中一個原因係利用硼酸之PVA之交聯不充分。若PVA之交聯不充分，則在高溫高濕環境下碘離子(PVA-I3 - 錯合物)不穩定，故而推測光學特性之劣化較大，缺乏中性色調。又，因「碘染色步驟」中之浸漬時間tB 相對較長，故而推測碘在偏光元件之厚度方向上均勻存在之情形亦影響耐久性。On the other hand, when t C /t B is small, there is a tendency that the concentration of iodide ions in the central portion in the thickness direction of the polarizing element becomes relatively larger than the concentration of iodide ions in the vicinity of the surface of the polarizing element, that is, T 2 /T 1 is less than the above preferred range, and durability is lowered. Thus, although the reason why the durability differs depending on the ratio of the immersion time is not clear, since the immersion time t C in the "crosslinking step" is relatively short, it is considered that one of the reasons is crosslinking with PVA of boric acid. insufficient. When the crosslinking of the PVA is insufficient, the iodide ion (PVA-I 3 - complex) is unstable in a high-temperature and high-humidity environment, so that the deterioration of the optical characteristics is presumed to be large, and the neutral color tone is lacking. Further, since the immersion time t B in the "iodine dyeing step" is relatively long, it is estimated that iodine is uniformly present in the thickness direction of the polarizing element, and the durability is also affected.
相反，若tC /tB 較大，則因偏光元件之厚度方向中心部之碘離子濃度相對降低，故而存在如下傾向：T2 /T1 大於上述較好的範圍，耐久性下降。如此，認為浸漬時間影響耐久性的一個原因為：由於「交聯步驟」中之浸漬時間tC 相對較長，故而利用硼酸之PVA之交聯過度進行。如此，若交聯過度進行，則認為會生成更多之PVA-I3 - 錯合物，但由於PVA-I3 - 錯合物在高溫高濕環境下之相對穩定性不如PVA-I5 - 錯合物，故而推測光學特性之劣化較大，缺乏中性色調。又，因「碘染色步驟」中之浸漬時間tB 相對較短，故而推測：由於偏光元件之厚度方向端部(表面)比中心部更加選擇性地進行碘染色，而阻礙利用硼酸之交聯，由於交聯不充分，而使在高溫高濕環境下之光學特性之劣化加大。On the other hand, when t C /t B is large, the concentration of iodide ions in the central portion in the thickness direction of the polarizing element is relatively lowered. Therefore, T 2 /T 1 tends to be larger than the above-described preferable range, and durability is lowered. Thus, it is considered that one reason why the immersion time affects the durability is that since the immersion time t C in the "crosslinking step" is relatively long, the crosslinking by the PVA of boric acid is excessively performed. Thus, if the cross-linking is excessive, it is considered that more PVA-I 3 - complex is formed, but the relative stability of PVA-I 3 - complex in high temperature and high humidity environment is not as good as that of PVA-I 5 - Since it is a complex compound, it is presumed that the deterioration of optical characteristics is large and the neutral color tone is lacking. Further, since the immersion time t B in the "iodine dyeing step" is relatively short, it is presumed that the end portion (surface) in the thickness direction of the polarizing element is more selectively iodine-dyed than the central portion, thereby hindering the crosslinking by boric acid. Since the crosslinking is insufficient, the deterioration of the optical characteristics in a high-temperature and high-humidity environment is increased.
碘染色步驟可藉由在聚乙烯醇系膜上使碘及/或碘離子吸附、配向而進行。染色係藉由將上述聚乙烯醇系膜浸漬於含有碘溶液之染色浴中而進行。用作碘溶液之碘水溶液，可使用利用碘、及碘化鉀等助溶劑而含有碘離子之水溶液等。碘濃度較好的是0.01~0.5重量%左右，更好的是0.02~0.4重量%。又，碘化鉀濃度較好的是0.01~10重量%左右，更好的是0.02~8重量%。The iodine dyeing step can be carried out by adsorbing and aligning iodine and/or iodide ions on a polyvinyl alcohol-based film. The dyeing is carried out by immersing the polyvinyl alcohol-based film in a dye bath containing an iodine solution. As the aqueous solution of iodine used as the iodine solution, an aqueous solution containing an iodide ion using a cosolvent such as iodine or potassium iodide can be used. The iodine concentration is preferably from about 0.01 to 0.5% by weight, more preferably from 0.02 to 0.4% by weight. Further, the concentration of potassium iodide is preferably from about 0.01 to 10% by weight, more preferably from 0.02 to 8% by weight.
當進行碘染色處理時，染色浴中之碘溶液之溫度通常為20~50℃左右，較好的是25~40℃。在染色浴中之浸漬時間tB ，通常較好的是10~300秒左右，更好的是20~240秒之範圍，更好的是20~200秒，尤其好的是25~120秒。When the iodine dyeing treatment is carried out, the temperature of the iodine solution in the dyeing bath is usually about 20 to 50 ° C, preferably 25 to 40 ° C. The immersion time t B in the dyeing bath is usually preferably about 10 to 300 seconds, more preferably 20 to 240 seconds, more preferably 20 to 200 seconds, and particularly preferably 25 to 120 seconds.
在碘染色步驟中，較好的是在上述染色溶液中進行單軸延伸處理。進行延伸時之延伸倍率，以完全未延伸狀態之聚乙烯醇系膜長度(以下，有時稱為「原長度」)為基準，通常為3.5倍以下，較好的是3.3倍以下，更好的是3倍以下。再者，就防止染色不均或防止起皺之方面而言，在供於碘染色步驟之前，較好的是以原長度為基準以2倍以上、進而以2.5倍以上之延伸倍率預先進行延伸。In the iodine dyeing step, it is preferred to carry out the uniaxial stretching treatment in the above dyeing solution. The stretching ratio at the time of stretching is preferably 3.5 times or less, preferably 3.3 times or less, based on the length of the polyvinyl alcohol film (hereinafter referred to as "original length") in a completely unstretched state. It is 3 times or less. Further, in terms of preventing uneven dyeing or preventing wrinkles, it is preferred to perform the stretching in advance at a stretching ratio of 2 times or more and further 2.5 times or more based on the original length before the iodine dyeing step. .
在供於上述碘染色步驟之前，視需要亦可將聚乙烯醇系膜浸漬於水等中而使其膨潤。藉由上述膨潤步驟，可水洗聚乙烯醇系膜，可清洗膜表面之污垢或抗結塊劑。此外，亦具有藉由使聚乙烯醇系膜膨潤而防止染色不均等不均勻的效果。Before the iodine dyeing step, the polyvinyl alcohol-based film may be immersed in water or the like to be swollen, if necessary. By the above swelling step, the polyvinyl alcohol-based film can be washed, and the dirt or anti-caking agent on the surface of the film can be cleaned. Further, there is also an effect of preventing unevenness in dyeing unevenness by swelling the polyvinyl alcohol film.
作為對聚乙烯醇系膜進行膨潤處理之膨潤浴，主要使用水，較好的是進而含有塑化劑。藉由使膨潤浴中含有塑化劑，可於膨潤步驟中，控制自聚乙烯醇膜之塑化劑之溶出量，而使膜膨潤量均勻化。當膨潤浴中含有塑化劑之情形時，其含量並無特別限制，相對於水溶液總量，較好的是含有0.5~15質量%之塑化劑，更好的是含有0.5~5.0質量%之塑化劑。當塑化劑含量過少之情形時，存在膜之膨潤作用不充分的情況；當含量過多之情形時，存在變得難以進行僅滿足作為偏光板之光學特性之延伸的情況。As the swelling bath which swells the polyvinyl alcohol-based film, water is mainly used, and it is preferable to further contain a plasticizer. By including a plasticizer in the swelling bath, the amount of elution of the plasticizer from the polyvinyl alcohol film can be controlled in the swelling step, and the amount of film swelling can be made uniform. When the swelling bath contains a plasticizer, the content thereof is not particularly limited, and it is preferably 0.5 to 15% by mass of the plasticizer, more preferably 0.5 to 5.0% by mass based on the total amount of the aqueous solution. Plasticizer. When the content of the plasticizer is too small, there is a case where the swelling effect of the film is insufficient; when the content is too large, it may become difficult to carry out only the extension of the optical characteristics as the polarizing plate.
在此，作為塑化劑，若係可使聚乙烯醇系膜塑化者，則無特別限定，可使用先前公知者。例如可列舉：乙二醇、二乙二醇、丙二醇、低分子量之聚乙二醇(Mw：200~400)等二元醇類，甘油、二甘油或三甘油等甘油衍生物等。其中，就與聚乙烯醇之相互作用較強且相溶性較大之方面而言，較好的是甘油衍生物，尤其好的是甘油。Here, the plasticizer is not particularly limited as long as it can plasticize the polyvinyl alcohol film, and a conventionally known one can be used. For example, glycols such as ethylene glycol, diethylene glycol, propylene glycol, low molecular weight polyethylene glycol (Mw: 200 to 400), glycerin derivatives such as glycerin, diglycerin or triglycerin, and the like can be given. Among them, a glycerin derivative is preferred in terms of a strong interaction with polyvinyl alcohol and a high compatibility, and glycerin is particularly preferred.
膨潤步驟中之聚乙烯醇系膜浸漬在膨潤浴中之浸漬時間，較好的是設為20秒以上、70秒以下，更好的是設為30秒以上、60秒以下。在浸漬時間未達20秒之情形時，存在膨潤效果不充分的情況；若浸漬時間超過70秒，則存在過度膨潤而在生產性方面不佳的情況。膨潤浴中之水溶液之溫度通常設為20~60℃之範圍。The immersion time of the polyvinyl alcohol-based film in the swelling step in the swelling bath is preferably 20 seconds or longer and 70 seconds or shorter, more preferably 30 seconds or longer and 60 seconds or shorter. When the immersion time is less than 20 seconds, the swelling effect may be insufficient; if the immersion time exceeds 70 seconds, excessive swelling may occur and productivity may be poor. The temperature of the aqueous solution in the swelling bath is usually set in the range of 20 to 60 °C.
又，膨潤步驟除如上所述浸漬於膨潤浴中以外，亦可採用如下方法：一面將水或者含有塑化劑之水溶液，塗佈、噴霧在聚乙烯醇系膜上，一面實施膨潤處理。Further, in addition to the immersion in the swelling bath as described above, the swelling step may be carried out by applying a water or a solution containing a plasticizer to a polyvinyl alcohol-based film while applying a swelling treatment.
進而，亦可在膨潤步驟中，以上述之方式進行延伸。當在膨潤步驟中進行延伸之情形時，其延伸倍率，如上所述以原長度為基準，較好的是2倍以上，更好的是2.5倍以上。Further, in the swelling step, the stretching may be carried out in the above manner. When the stretching is carried out in the swelling step, the stretching ratio is preferably 2 times or more, more preferably 2.5 times or more, based on the original length as described above.
經染色處理之聚乙烯醇系膜，較好的是進行交聯處理。作為進行交聯處理之交聯溶液，通常較好的是使用單獨使用硼酸、硼砂、乙二醛、戊二醛等交聯劑或將該等混合而成的交聯劑之濃度為1~15重量%之水溶液，更好的是使用2~10重量%之水溶液，更好的是使用2~7重量%之水溶液，尤其好的是使用3~6重量%之水溶液。交聯劑之濃度係可考慮光學特性或聚乙烯醇系膜所發生之由延伸力所產生之偏光板收縮的平衡來決定。The dyed polyvinyl alcohol-based film is preferably subjected to a crosslinking treatment. As the crosslinking solution to be subjected to the crosslinking treatment, it is usually preferred to use a crosslinking agent such as boric acid, borax, glyoxal or glutaraldehyde alone or a mixture of the crosslinking agents having a concentration of 1 to 15 The aqueous solution of the weight % is more preferably an aqueous solution of 2 to 10% by weight, more preferably 2 to 7% by weight of an aqueous solution, and particularly preferably an aqueous solution of 3 to 6% by weight. The concentration of the crosslinking agent can be determined in consideration of the optical characteristics or the balance of the shrinkage of the polarizing plate by the stretching force generated by the polyvinyl alcohol film.
較好的是以濃度達到0.05~15重量%，更好的是達到0.5~8重量%，更好的是達到2~5重量%的方式，於交聯浴中添加碘化鉀、碘化鋰、碘化鈉、碘化鋅、碘化鋁、碘化鉛、碘化銅、碘化鋇、碘化鈣、碘化錫、碘化鈦等碘化物等助劑。藉由含有該等添加劑，可使偏光元件之特性在面內均勻化。水溶液之溫度通常為20~70℃左右，較好的是25~65℃，更好的是30~60℃之範圍。浸漬時間並無特別限定，通常為15秒~900秒左右，較好的是30秒~600秒，更好的是30~250秒，更好的是50~150秒。又，就提高偏光板之耐久性之觀點而言，較好的是如上所述將上述染色浴浸漬時間tB 與交聯步驟中之交聯浴浸漬時間tC 之比tC /tB 設定在規定之範圍內。對於交聯浴，作為溶劑，除了水以外，亦可少量含有與水具有相溶性之有機溶劑。Preferably, the concentration is 0.05 to 15% by weight, more preferably 0.5 to 8% by weight, more preferably 2 to 5% by weight, and potassium iodide, lithium iodide and iodine are added to the crosslinking bath. Additives such as sodium, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, and titanium iodide. By containing these additives, the characteristics of the polarizing element can be made uniform in the plane. The temperature of the aqueous solution is usually about 20 to 70 ° C, preferably 25 to 65 ° C, more preferably 30 to 60 ° C. The immersion time is not particularly limited and is usually from 15 seconds to 900 seconds, preferably from 30 seconds to 600 seconds, more preferably from 30 to 250 seconds, and even more preferably from 50 to 150 seconds. Further, from the viewpoint of improving the durability of the polarizing plate, it is preferred to set the ratio t C /t B of the dyeing bath immersion time t B to the crosslinking bath immersion time t C in the crosslinking step as described above. Within the scope of the regulations. As the solvent, the crosslinking bath may contain a small amount of an organic solvent compatible with water in addition to water.
交聯步驟中之聚乙烯醇系膜之延伸倍率，較好的是設為原長度之4~8倍左右，更好的是設為5~7倍左右。若延伸倍率過高，則有膜容易破裂之傾向。又，若延伸倍率過低，則存在偏光板之偏光度不充分的情況。The stretching ratio of the polyvinyl alcohol-based film in the crosslinking step is preferably about 4 to 8 times the original length, more preferably about 5 to 7 times. If the stretching ratio is too high, the film tends to be easily broken. Moreover, when the stretching ratio is too low, the degree of polarization of the polarizing plate may be insufficient.
又，於交聯步驟中，亦可使用溶液中之溶解物之種類或濃度不同之複數種交聯浴。當使用複數種交聯浴之情形時，較好的是後一交聯浴之硼酸等交聯劑之濃度及碘化鉀等助劑之濃度高於前一交聯浴。藉由提高越後面之交聯浴之濃度，越可製成均勻性及耐久性優異之偏光板。又，交聯步驟之延伸，可於前一交聯浴、後一交聯浴中之任意一者或兩者中進行，亦可於兩個交聯浴中以不同之倍率進行延伸。尤其是，如上所述，較好的是使相對提高交聯劑或助劑之濃度的後一交聯浴中之延伸倍率大於前一交聯浴中之延伸倍率。藉由如此調整延伸倍率，可製成偏光度較高之偏光板。Further, in the crosslinking step, a plurality of cross-linking baths having different types or concentrations of dissolved substances in the solution may be used. When a plurality of cross-linking baths are used, it is preferred that the concentration of the cross-linking agent such as boric acid in the latter crosslinking bath and the concentration of the auxiliary agent such as potassium iodide are higher than those of the previous cross-linking bath. By increasing the concentration of the crosslinking bath in the later stage, a polarizing plate excellent in uniformity and durability can be obtained. Further, the extension of the crosslinking step may be carried out in either or both of the previous crosslinking bath and the latter crosslinking bath, or may be carried out at different magnifications in the two crosslinking baths. In particular, as described above, it is preferred that the stretching ratio in the latter crosslinking bath in which the concentration of the crosslinking agent or the auxiliary agent is relatively increased is larger than the stretching ratio in the previous crosslinking bath. By adjusting the stretching ratio in this way, a polarizing plate having a high degree of polarization can be obtained.
又，延伸亦可於一個浴中分多階段進行。多階段延伸例如係在浴中設置複數對夾送輥(夾棍)，在各對輥之間進行延伸。當以多階段進行延伸之情形時，亦可藉由控制各對夾送輥之周邊速度，而使每個階段之延伸倍率不同。Moreover, the extension can also be carried out in multiple stages in one bath. The multi-stage extension is, for example, by providing a plurality of pairs of pinch rolls (clips) in the bath and extending between the pairs of rolls. When the stretching is performed in multiple stages, the stretching ratio of each stage can be made different by controlling the peripheral speed of each pair of pinch rolls.
又，經碘吸附配向處理之聚乙烯醇系膜，較好的是進而供於浸漬在碘化鉀等碘化物水溶液(碘含浸浴)中之色調調整步驟。含浸浴中所使用之碘化物較好的是碘化鉀。又，就充分進行含浸之觀點而言，碘化鉀濃度較好的是1~5重量%，更好的是2~4重量%。碘含浸浴中之液體溫度，通常為10~60℃，較好的是15~40℃左右，更好的是20~30℃。又，含浸浴之浸漬時間較好的是1秒~60秒，更好的是1~30秒，更好的是3~30秒，尤其好的是3~15秒。將含浸浴之浸漬時間或碘化物濃度設為上述範圍，就將偏光板正交配置時之色調調整之觀點而言較好。Further, the polyvinyl alcohol-based film which has been subjected to the iodine adsorption alignment treatment is preferably further supplied to a color tone adjusting step of being immersed in an aqueous iodide solution (iodine-impregnated bath) such as potassium iodide. The iodide used in the bath is preferably potassium iodide. Further, from the viewpoint of sufficiently impregnating, the potassium iodide concentration is preferably from 1 to 5% by weight, more preferably from 2 to 4% by weight. The temperature of the liquid in the iodine impregnation bath is usually 10 to 60 ° C, preferably 15 to 40 ° C, more preferably 20 to 30 ° C. Moreover, the immersion time of the impregnation bath is preferably from 1 second to 60 seconds, more preferably from 1 to 30 seconds, more preferably from 3 to 30 seconds, and particularly preferably from 3 to 15 seconds. When the immersion time or the iodide concentration of the impregnation bath is set to the above range, it is preferable from the viewpoint of adjusting the color tone when the polarizing plates are arranged orthogonally.
進而，除上述各步驟以外，亦可實施金屬離子處理。金屬離子處理係藉由在含有金屬鹽之水溶液中浸漬聚乙烯醇系膜而進行。藉由金屬離子處理，亦可使各種金屬離子包含於聚乙烯醇系膜中。Further, in addition to the above steps, metal ion treatment may be performed. The metal ion treatment is carried out by immersing a polyvinyl alcohol-based film in an aqueous solution containing a metal salt. Various metal ions can also be contained in the polyvinyl alcohol-based film by metal ion treatment.
作為金屬離子，尤其就色調調整或賦予耐久性之方面而言，可較好地使用鈷、鎳、鋅、鉻、鋁、銅、錳、鐵等過渡金屬之金屬離子。該等金屬離子之中，就色調調整或賦予耐熱性等方面而言，較好的是鋅離子。作為鋅鹽，可列舉：氯化鋅、碘化鋅等鹵化鋅，硫酸鋅，乙酸鋅等。As the metal ion, in particular, in terms of color tone adjustment or durability, metal ions of a transition metal such as cobalt, nickel, zinc, chromium, aluminum, copper, manganese or iron can be preferably used. Among these metal ions, zinc ions are preferred in terms of color tone adjustment or heat resistance. Examples of the zinc salt include zinc halides such as zinc chloride and zinc iodide, zinc sulfate, and zinc acetate.
在金屬離子處理中，可使用金屬鹽溶液。以下，在金屬離子處理中，作為使用鋅鹽水溶液時之代表例，對鋅含浸處理進行說明。In the metal ion treatment, a metal salt solution can be used. Hereinafter, in the metal ion treatment, a zinc impregnation treatment will be described as a representative example when a zinc salt aqueous solution is used.
鋅鹽水溶液中之鋅離子之濃度，較好的是0.1~10重量%左右，更好的是0.3~7重量%。又，鋅鹽溶液使用藉由碘化鉀等而含有鉀離子及碘離子之水溶液，容易含浸鋅離子，故而較好。鋅鹽溶液中之碘化鉀濃度較好的是設為0.1~10重量%左右，更好的是設為0.2~5重量%。就相關觀點而言，較好的是於上述交聯步驟或色調調整步驟中進行金屬離子處理。The concentration of zinc ions in the aqueous zinc salt solution is preferably from about 0.1 to 10% by weight, more preferably from 0.3 to 7% by weight. Further, the zinc salt solution is preferably an aqueous solution containing potassium ions and iodide ions by potassium iodide or the like, and is easily impregnated with zinc ions. The concentration of potassium iodide in the zinc salt solution is preferably about 0.1 to 10% by weight, more preferably 0.2 to 5% by weight. From a related point of view, it is preferred to carry out the metal ion treatment in the above crosslinking step or color tone adjustment step.
如此而獲得之偏光元件，較好的是最後實施乾燥步驟。乾燥步驟可視所獲得之偏光元件所需之水分率，而適當設定乾燥時間及乾燥溫度。乾燥溫度通常為20~150℃之範圍，較好的是40~100℃之範圍。若乾燥溫度過低，則存在乾燥時間延長，製造效率下降的情況。若乾燥溫度過低，則存在所獲得之偏光元件發生劣化，光學特性及色調變得不充分的情況。加熱乾燥時間通常為1~5分鐘左右。In the polarizing element thus obtained, it is preferred to carry out the drying step last. The drying step can appropriately set the drying time and the drying temperature depending on the moisture content required for the obtained polarizing element. The drying temperature is usually in the range of 20 to 150 ° C, preferably 40 to 100 ° C. If the drying temperature is too low, the drying time may be prolonged and the production efficiency may be lowered. When the drying temperature is too low, the obtained polarizing element may be deteriorated, and optical characteristics and color tone may be insufficient. The heating and drying time is usually about 1 to 5 minutes.
偏光元件之厚度並無特別限制，通常為5~80μm左右。若偏光元件之厚度變薄，則在將其與保護膜貼合時之乾燥步驟等中，偏光元件中之水分會變得容易揮發。The thickness of the polarizing element is not particularly limited and is usually about 5 to 80 μm. When the thickness of the polarizing element is reduced, the moisture in the polarizing element is easily volatilized in a drying step or the like when the protective film is bonded to the protective film.
所獲得之偏光元件，可依據常法在其兩面積層透明保護膜，而製成偏光板。作為構成透明保護膜之材料，例如可使用透明性、機械強度、熱穩定性、遮水性、等向性等優異之熱塑性樹脂。作為如此之熱塑性樹脂的具體例，可列舉：三乙醯纖維素等纖維素樹脂、聚酯樹脂、聚醚碸樹脂、聚碸樹脂、聚碳酸酯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、聚烯烴樹脂、(甲基)丙烯酸系樹脂、環狀聚烯烴樹脂(降冰片烯系樹脂)、聚芳酯樹脂、聚苯乙烯樹脂、聚乙烯醇樹脂及該等之混合物。再者，偏光元件上通常藉由接著劑層而貼合透明保護膜，作為透明保護膜，可使用(甲基)丙烯酸系、胺基甲酸酯系、丙烯酸胺基甲酸酯系、環氧系、聚矽氧系等熱固性樹脂或紫外線硬化型樹脂。The obtained polarizing element can be made into a polarizing plate by a transparent protective film in its two-layer layer according to a conventional method. As the material constituting the transparent protective film, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, water repellency, and isotropic properties can be used. Specific examples of such a thermoplastic resin include cellulose resins such as triacetonitrile cellulose, polyester resins, polyether oxime resins, polyfluorene resins, polycarbonate resins, polyamide resins, and polyimide resins. A polyolefin resin, a (meth)acrylic resin, a cyclic polyolefin resin (norbornene-based resin), a polyarylate resin, a polystyrene resin, a polyvinyl alcohol resin, and a mixture thereof. Further, the polarizing element is usually laminated with a transparent protective film by an adhesive layer, and as the transparent protective film, (meth)acrylic, urethane-based, urethane-based, epoxy can be used. A thermosetting resin such as a polysiloxane or an ultraviolet curable resin.
透明保護膜之厚度可適當決定，就強度或操作性等作業性、薄層性等方面而言，通常為1~500μm左右。尤其好的是1~300μm，更好的是5~200μm。透明保護膜尤其適宜的是厚度為5~150μm之情形。The thickness of the transparent protective film can be appropriately determined, and is usually about 1 to 500 μm in terms of workability such as strength and workability, and thinness. Particularly preferably, it is 1 to 300 μm, more preferably 5 to 200 μm. The transparent protective film is particularly preferably in the case of a thickness of 5 to 150 μm.
再者，在偏光元件之兩側設置透明保護膜時，可使用在其表裏包含相同之聚合物材料的保護膜，亦可使用包含不同之聚合物材料等的保護膜。Further, when a transparent protective film is provided on both sides of the polarizing element, a protective film containing the same polymer material in the front surface thereof may be used, or a protective film containing a different polymer material or the like may be used.
作為本發明之透明保護膜，較好的是使用選自纖維素樹脂、聚碳酸酯樹脂、環狀聚烯烴樹脂及(甲基)丙烯酸系樹脂之任意至少一種。又，透明保護膜亦可為兼用作下述相位差板者。As the transparent protective film of the present invention, it is preferred to use at least one selected from the group consisting of a cellulose resin, a polycarbonate resin, a cyclic polyolefin resin, and a (meth)acrylic resin. Further, the transparent protective film may also be used as a phase difference plate as described below.
作為相位差板，可列舉對高分子原材料進行單軸或雙軸延伸處理而成之雙折射性膜、液晶聚合物之配向膜、利用膜支撐液晶聚合物之配向層而成者等。相位差板之厚度亦無特別限制，通常為20~150μm左右。Examples of the retardation film include a birefringent film obtained by subjecting a polymer material to uniaxial or biaxial stretching treatment, an alignment film of a liquid crystal polymer, and an alignment layer supporting a liquid crystal polymer by a film. The thickness of the phase difference plate is also not particularly limited, and is usually about 20 to 150 μm.
作為高分子原材料，例如可列舉：聚乙烯醇、聚乙烯醇縮丁醛、聚甲基乙烯醚、聚丙烯酸羥乙酯、羥乙基纖維素、羥丙基纖維素、甲基纖維素、聚碳酸酯、聚芳酯、聚碸、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚醚碸、聚苯硫醚、聚苯醚、聚芳碸、聚醯胺、聚醯亞胺、聚烯烴、聚氯乙烯、纖維素樹脂、環狀聚烯烴樹脂(降冰片烯系樹脂)或該等之二元系、三元系之各種共聚物、接枝共聚物、混合物等。該等高分子原材料藉由延伸等而成為配向物(延伸膜)。Examples of the polymer material include polyvinyl alcohol, polyvinyl butyral, polymethyl vinyl ether, polyhydroxyethyl acrylate, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, and poly. Carbonate, polyarylate, polyfluorene, polyethylene terephthalate, polyethylene naphthalate, polyether oxime, polyphenylene sulfide, polyphenylene ether, polyaryl fluorene, polyamine, polyfluorene Imine, polyolefin, polyvinyl chloride, cellulose resin, cyclic polyolefin resin (norbornene-based resin) or various binary, ternary copolymers, graft copolymers, mixtures, and the like. These polymer raw materials become an alignment material (stretching film) by stretching or the like.
作為液晶聚合物，例如可列舉：在聚合物之主鏈或側鏈導入賦予液晶配向性之共軛性直線狀原子團(液晶原)而成的主鏈型或側鏈型之各種液晶聚合物等。作為主鏈型液晶聚合物之具體例，可列舉：在賦予彎曲性之間隔部鍵結液晶原基之結構之，例如向列排列性之聚酯系液晶性聚合物、圓盤狀聚合物或膽固醇狀聚合物等。作為側鏈型液晶聚合物之具體例，可列舉：以聚矽氧烷、聚丙烯酸酯、聚甲基丙烯酸酯或聚丙二酸酯為主鏈骨架，且經由包含共軛性之原子團之間隔部，而具有包含向列排列賦予性之對位取代環狀化合物單元之液晶原部作為側鏈者等。對於該等液晶聚合物，例如可在對形成於玻璃板上之聚醯亞胺或聚乙烯醇等之薄膜的表面進行摩擦處理者、對氧化矽進行斜向蒸鍍者等之配向處理面上，展開液晶性聚合物之溶液並進行熱處理。Examples of the liquid crystal polymer include a main chain type or a side chain type liquid crystal polymer in which a conjugated linear atomic group (liquid crystal original) which imparts liquid crystal alignment properties is introduced into a main chain or a side chain of a polymer. . Specific examples of the main chain type liquid crystal polymer include a structure in which a liquid crystal nucleus is bonded to a spacer which imparts flexibility, and for example, a nematically aligned polyester liquid crystalline polymer or a discotic polymer or Cholesterol-like polymers, etc. Specific examples of the side chain type liquid crystal polymer include a polyoxyalkylene oxide, a polyacrylate, a polymethacrylate, or a polymalonate as a main chain skeleton, and a partition portion containing a conjugated atomic group. Further, the liquid crystal original portion having a para-substituted cyclic compound unit containing a nematic arrangement is used as a side chain or the like. For the liquid crystal polymer, for example, a surface of a film of a polyimide film or a polyvinyl alcohol formed on a glass plate may be subjected to a rubbing treatment, or an oxidized ruthenium may be subjected to oblique vapor deposition. A solution of the liquid crystalline polymer is developed and heat-treated.
關於相位差板，例如亦可為具有與以各種波長板或液晶層之雙折射所引起之著色或視角等之補償為目的者等之使用目的相對應之適當相位差者，亦可為積層2種以上之相位差板而控制相位差等光學特性者等。The phase difference plate may be, for example, a suitable phase difference corresponding to the purpose of use for the purpose of compensation such as coloring or viewing angle caused by birefringence of various wavelength plates or liquid crystal layers, or may be laminated layer 2 The above-described phase difference plate is used to control optical characteristics such as phase difference.
相位差板可視各種用途選擇使用滿足nx=ny>nz、nx>ny>nz、nx>ny=nz、nx>nz>ny、nz=nx>ny、nz>nx>ny、nz>nx=ny之關係者。再者，所謂ny=nz，不僅指ny與nz完全相同之情形，亦包括ny與nz實質相同之情形。The phase difference plate can be selected and used for various purposes to satisfy nx=ny>nz, nx>ny>nz, nx>ny=nz, nx>nz>ny, nz=nx>ny, nz>nx>ny, nz>nx=ny Relationship. Furthermore, the so-called ny=nz means not only the case where ny and nz are completely the same, but also the case where ny and nz are substantially the same.
上述透明保護膜亦可在塗佈接著劑之前進行表面改質處理。作為具體處理，可列舉電暈處理、電漿處理、底層處理、皂化處理等。The transparent protective film may also be subjected to surface modification treatment before the application of the adhesive. Specific examples of the treatment include corona treatment, plasma treatment, bottom treatment, and saponification treatment.
上述透明保護膜不與偏光元件接著之面，可為硬塗層，或實施抗反射處理、以防黏或擴散乃至防眩為目的之表面處理者。The transparent protective film may be a hard coat layer or a surface treatment agent for anti-reflection treatment, anti-adhesion or diffusion, or anti-glare, without being in contact with the polarizing element.
上述偏光元件與透明保護膜之接著處理可使用接著劑。作為接著劑，可例示：異氰酸酯系接著劑、聚乙烯醇系接著劑、明膠系接著劑、乙烯基系乳膠系、水系聚酯等。上述接著劑通常使用含有水溶液之接著劑，其通常含有0.5~60重量%之固體成分。上述以外，作為偏光元件與透明保護膜之接著劑，可列舉：紫外硬化型接著劑、電子束硬化型接著劑等。電子束硬化型偏光板用接著劑對上述各種透明保護膜表現出較好之接著性。尤其是，對難以滿足接著性之丙烯酸樹脂亦表現出良好之接著性。An adhesive can be used for the subsequent treatment of the above polarizing element and the transparent protective film. Examples of the adhesive agent include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl-based latex, and an aqueous polyester. The above-mentioned adhesive usually uses an adhesive containing an aqueous solution, which usually contains 0.5 to 60% by weight of a solid component. In addition to the above, examples of the adhesive for the polarizing element and the transparent protective film include an ultraviolet curable adhesive and an electron beam curable adhesive. The electron beam-curable polarizing plate exhibits good adhesion to the above various transparent protective films by an adhesive. In particular, the acrylic resin which is difficult to satisfy the adhesion also exhibits good adhesion.
本發明之偏光板係藉由使用上述接著劑，使上述透明保護膜與偏光元件相貼合而製造。可在透明保護膜、偏光元件之任意一者上塗佈接著劑，亦可在兩者上塗佈接著劑。在貼合之後，實施乾燥步驟，形成由塗佈乾燥層所構成之接著層。偏光元件與透明保護膜之貼合亦可利用覆膜機等來進行。接著層之厚度並無特別限制，通常為30~1000nm左右。The polarizing plate of the present invention is produced by laminating the transparent protective film and a polarizing element by using the above-mentioned adhesive. The adhesive may be applied to either the transparent protective film or the polarizing element, or the adhesive may be applied to both. After the bonding, a drying step is performed to form an adhesive layer composed of the dried coating layer. The bonding of the polarizing element and the transparent protective film can also be performed by a laminator or the like. The thickness of the layer is not particularly limited and is usually about 30 to 1000 nm.
本發明之偏光板，於實際使用時亦可用作與其他光學層積層而成的光學膜。該光學層並無特別限定，例如可使用1層或2層以上之反射板或半穿透板、相位差板(包括1/2或1/4等之波長板)、視角補償膜等形成液晶顯示裝置等時所使用之光學層。尤其好的是：在本發明之偏光板上進而積層反射板或半穿透反射板而成之反射型偏光板或半穿透型偏光板、在偏光板上進而積層相位差板而成之橢圓偏光板或圓偏光板、在偏光板上進而積層視角補償膜而成之廣視角偏光板、或者在偏光板上進而積層增亮膜而成之偏光板。The polarizing plate of the present invention can also be used as an optical film laminated with other optical layers in actual use. The optical layer is not particularly limited. For example, one or two or more layers of a reflector or a semi-transmissive plate, a phase difference plate (including a wavelength plate of 1/2 or 1/4, etc.), a viewing angle compensation film, or the like can be used to form a liquid crystal. The optical layer used when displaying the device or the like. Particularly preferably, a reflective polarizing plate or a semi-transmissive polarizing plate in which a reflecting plate or a semi-transmissive reflecting plate is laminated on the polarizing plate of the present invention, and an ellipse formed by laminating a phase difference plate on the polarizing plate A polarizing plate or a circular polarizing plate, a wide viewing angle polarizing plate formed by laminating a viewing angle compensation film on a polarizing plate, or a polarizing plate formed by laminating a brightness enhancing film on a polarizing plate.
反射型偏光板係於偏光板上設置反射層者，其係用於形成藉由反射來自視覺辨識側(顯示側)之入射光而進行顯示之類型的液晶顯示裝置等者，其具有可省略內藏背光等光源而容易實現液晶顯示裝置之薄型化等優點。反射型偏光板之形成，亦可視需要藉由經由透明保護膜等而於偏光板之單面設置包含金屬等之反射層的方式等適當方式而進行。The reflective polarizing plate is provided with a reflective layer on a polarizing plate, and is used for forming a liquid crystal display device of a type that performs display by reflecting incident light from a visual recognition side (display side). It is easy to realize the thinning of the liquid crystal display device by hiding a light source such as a backlight. The formation of the reflective polarizing plate may be carried out by a suitable method such as providing a reflective layer containing a metal or the like on one surface of the polarizing plate via a transparent protective film or the like.
再者，半穿透型偏光板可上述製成以反射層反射光且穿透光之半反射鏡等半穿透型之反射層。半穿透型偏光板通常設置於液晶單元之背面側，可形成如下類型之液晶顯示裝置：於比較亮之環境下使用液晶顯示裝置等之情形時，反射來自視覺辨識側(顯示側)之入射光而顯示圖像，並於比較暗之環境下，使用內藏在半穿透型偏光板之背面的背光等內藏光源而顯示圖像。Further, the semi-transmissive polarizing plate can be made into a semi-transmissive reflective layer such as a half mirror that reflects light and penetrates the light. The semi-transmissive polarizing plate is usually disposed on the back side of the liquid crystal cell, and can form a liquid crystal display device of the type that reflects the incident from the visual recognition side (display side) when a liquid crystal display device or the like is used in a relatively bright environment. The image is displayed by light, and in a relatively dark environment, an image is displayed using a built-in light source such as a backlight built in the back surface of the semi-transmissive polarizing plate.
對在偏光板上進而積層相位差板而成之橢圓偏光板或圓偏光板進行說明。當將直線偏光變為橢圓偏光或圓偏光，或者將橢圓偏光或圓偏光變為直線偏光，或者改變直線偏光之偏光方向之情形時，可使用相位差板等。尤其是，作為將直線偏光變為圓偏光或者將圓偏光變為直線偏光的相位差板，可使用所謂1/4波長板(亦稱為λ/4板)。1/2波長板(亦稱為λ/2板)通常在改變直線偏光之偏光方向時使用。An elliptically polarizing plate or a circularly polarizing plate in which a phase difference plate is laminated on a polarizing plate will be described. When the linearly polarized light is changed to elliptically polarized or circularly polarized light, or the elliptically polarized or circularly polarized light is changed to linearly polarized light, or the polarized direction of the linearly polarized light is changed, a phase difference plate or the like can be used. In particular, a so-called quarter-wave plate (also referred to as a λ/4 plate) can be used as a phase difference plate that converts linearly polarized light into circularly polarized light or circularly polarized light into linearly polarized light. The 1/2 wavelength plate (also known as the λ/2 plate) is usually used when changing the polarization direction of the linearly polarized light.
橢圓偏光板可有效地使用於如下情形：補償(防止)由超扭轉向列(STN，Super Twisted Nematic)型液晶顯示裝置之液晶層之雙折射所產生的著色(藍色或黃色)，而進行無上述著色之黑白顯示等。進而，控制三維折射率者，亦可補償(防止)自傾斜方向觀察液晶顯示裝置之畫面時所產生之著色，故而較好。圓偏光板例如可有效地用於調整圖像成為彩色顯示之反射型液晶顯示裝置之圖像的色調情形等，又，亦具有抗反射功能。作為上述相位差板之具體例，可列舉：對包含如聚碳酸酯、聚乙烯醇、聚苯乙烯、聚甲基丙烯酸甲酯、聚丙烯或其他聚烯烴、聚芳酯、聚醯胺般適當聚合物之膜進行延伸處理而成之雙折射性膜或液晶聚合物之配向膜、利用膜支撐液晶聚合物之配向層而成者等。關於相位差板，例如亦可為具有與以各種波長板或液晶層之雙折射所引起之著色或視角等之補償為目的者等之使用目的相對應之適當相位差者，亦可為積層2種以上之相位差板而控制相位差等光學特性者等。The elliptically polarizing plate can be effectively used in the case of compensating (preventing) coloring (blue or yellow) caused by birefringence of a liquid crystal layer of a super twisted nematic (STN) type liquid crystal display device. There is no black and white display of the above coloring. Further, it is preferable to control the three-dimensional refractive index to compensate (prevent) the coloring which occurs when the screen of the liquid crystal display device is viewed from the oblique direction. The circularly polarizing plate can be effectively used, for example, to adjust the color tone of an image of a reflective liquid crystal display device in which an image is displayed in color, and also has an anti-reflection function. Specific examples of the phase difference plate include a mixture of, for example, polycarbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polypropylene or other polyolefin, polyarylate, and polyamide. The alignment film of the birefringence film or the liquid crystal polymer obtained by stretching the film of the polymer, and the alignment layer supporting the liquid crystal polymer by the film. The phase difference plate may be, for example, a suitable phase difference corresponding to the purpose of use for the purpose of compensation such as coloring or viewing angle caused by birefringence of various wavelength plates or liquid crystal layers, or may be laminated layer 2 The above-described phase difference plate is used to control optical characteristics such as phase difference.
又，上述橢圓偏光板或反射型橢圓偏光板係以適當組合將偏光板或反射型偏光板與相位差板積層而成者。相關橢圓偏光板等，亦可藉由以成為(反射型)偏光板與相位差板之組合之方式在液晶顯示裝置之製造過程中依序各別地對該等進行積層而形成，但如上所述預先製成橢圓偏光板等光學膜者，具有品質穩定性或積層作業性等優異且可提高液晶顯示裝置等之製造效率之優點。Further, the elliptically polarizing plate or the reflective elliptically polarizing plate is formed by laminating a polarizing plate or a reflective polarizing plate and a phase difference plate in an appropriate combination. The elliptically polarizing plate or the like may be formed by sequentially laminating the liquid crystal display device in the manufacturing process of the liquid crystal display device in a combination of a (reflective) polarizing plate and a phase difference plate, but as described above. When an optical film such as an elliptically polarizing plate is prepared in advance, it is excellent in quality stability, laminating workability, and the like, and the manufacturing efficiency of a liquid crystal display device or the like can be improved.
視角補償膜係以自不與畫面垂直而稍有傾斜之方向觀看液晶顯示裝置之畫面時，為了比較清晰地觀看圖像而擴大視角的膜。作為如此之視角補償相位差板，例如包含相位差膜、液晶聚合物等之配向膜、或在透明基材上支撐液晶聚合物等之配向層而成者等。通常之相位差板係使用沿其面方向進行單軸延伸且具有雙折射之聚合物膜，相對於此，用作視角補償膜之相位差板，係使用沿面方向雙軸延伸且具有雙折射之聚合物膜，或者使用如沿面方向單軸延伸並沿厚度方向延伸之控制厚度方向之折射率且具有雙折射的聚合物或傾斜配向膜的雙向延伸膜等。作為傾斜配向膜，例如可列舉：在聚合物膜上接著熱收縮膜，在由加熱所產生之收縮力的作用下對聚合物膜進行延伸處理或/及收縮處理而成者，或使液晶聚合物傾斜配向而成者等。相位差板之原料聚合物係使用與先前之相位差板中所說明之聚合物相同者，可使用適用於防止由基於液晶單元之相位差之視覺辨識角之變化所引起之著色等或擴大良好視覺辨識之視角等目的者。The viewing angle compensation film expands the film of the viewing angle in order to view the image relatively clearly when the screen of the liquid crystal display device is viewed from a direction that is not inclined perpendicularly to the screen. Such a viewing angle compensation retardation plate includes, for example, an alignment film such as a retardation film or a liquid crystal polymer, or an alignment layer that supports a liquid crystal polymer or the like on a transparent substrate. In general, a phase difference plate uses a polymer film which is uniaxially stretched in the plane direction thereof and has birefringence. In contrast, a phase difference plate used as a viewing angle compensation film is biaxially extended in the plane direction and has birefringence. The polymer film or a biaxially stretched film which has a refractive index which is uniaxially extended in the plane direction and which extends in the thickness direction and which has a refractive index in the thickness direction and which has birefringence or a tilted alignment film. Examples of the oblique alignment film include a method in which a polymer film is followed by a heat shrink film, and the polymer film is subjected to stretching treatment and/or shrinkage treatment by a contraction force generated by heating, or liquid crystal polymerization is carried out. The object is inclined and the like. The raw material polymer of the phase difference plate is the same as the polymer described in the previous phase difference plate, and it is possible to use a coloring or the like suitable for preventing a change in the visual recognition angle based on the phase difference of the liquid crystal cell, or to expand well. The purpose of visual recognition and other purposes.
又，就實現良好視覺辨識之較寬的視角方面等而言，可較好地使用利用三乙醯纖維素膜支撐包含液晶聚合物之配向層、尤其是圓盤狀液晶聚合物之傾斜配向層的光學各向異性層而成的光學補償相位差板。Further, in terms of achieving a wide viewing angle for good visual recognition, etc., it is preferable to use an inclined alignment layer which supports an alignment layer containing a liquid crystal polymer, particularly a discotic liquid crystal polymer, using a triacetyl cellulose film. An optically compensated phase difference plate made of an optically anisotropic layer.
將偏光板與增亮膜貼合而成的偏光板，通常設置於液晶單元之背面側而使用。增亮膜顯示出如下特性：當藉由來自液晶顯示裝置等之背光或背面側之反射等而入射自然光時，會反射規定偏光軸之直線偏光或規定方向之圓偏光，並透射其他光；因此，關於使增亮膜與偏光板積層之偏光板，對其入射來自背光等光源之光時可獲得規定偏光狀態之穿透光，並且可不使上述規定偏光狀態以外之光穿透而將其反射。使由該增亮膜面反射之光，進而經由設置在其後側之反射層等進行反轉，而再次入射至增亮膜，使其一部分或全部以規定偏光狀態之光的形式穿透而實現穿透增亮膜的光之增量，並且供給不易被偏光元件吸收之偏光而增大可用於液晶圖像顯示等之光量，藉此提高亮度。A polarizing plate in which a polarizing plate and a brightness enhancement film are bonded together is usually used on the back side of the liquid crystal cell. The brightness enhancement film exhibits a characteristic that when natural light is incident by reflection from a backlight or a back side of a liquid crystal display device or the like, linearly polarized light of a predetermined polarization axis or circularly polarized light of a predetermined direction is reflected, and other light is transmitted; A polarizing plate in which a brightness enhancement film and a polarizing plate are laminated, and when light is incident from a light source such as a backlight, a light having a predetermined polarization state can be obtained, and light can be reflected without being penetrated by the light other than the predetermined polarization state. . The light reflected by the brightness enhancement film surface is further inverted by a reflection layer or the like provided on the rear side thereof, and is again incident on the brightness enhancement film to partially or completely penetrate the light in a predetermined polarization state. The amount of light that penetrates the brightness enhancing film is increased, and the polarized light that is hardly absorbed by the polarizing element is supplied, and the amount of light that can be used for liquid crystal image display or the like is increased, thereby improving the brightness.
再者，於本發明中，上述形成偏光板之偏光元件或透明保護膜或光學膜等，另外黏著層等各層，例如可藉由利用水楊酸酯系化合物或苯并苯酚系化合物、苯并***系化合物或氰基丙烯酸酯系化合物、鎳錯合鹽系化合物等紫外線吸收劑進行處理之方式等方式，而使其成為具有紫外線吸收能力者等。Further, in the present invention, the polarizing element forming the polarizing plate, the transparent protective film, the optical film, or the like, and the respective layers such as the adhesive layer may be, for example, a salicylate-based compound or a benzophenol-based compound or a benzoic acid. A method of treating a UV absorber such as a triazole compound, a cyanoacrylate compound or a nickel complex salt compound to obtain an ultraviolet absorbing ability.
本發明之偏光板或光學膜，可較好地用於形成液晶顯示裝置等各種裝置等。液晶顯示裝置之形成可依據先前之方式來進行。即，液晶顯示裝置通常係藉由將液晶單元與偏光板或光學膜、及視需要之照明系統等構成零件適當組裝並裝入驅動電路的方式等而形成，但在本發明中，除使用本發明之偏光板或光學膜之方面以外，並無特別限定，可依據先前之方式。關於液晶單元，亦可使用例如TN(Twisted Nematic，扭轉向列)型或STN型、π型等之任意類型者。The polarizing plate or the optical film of the present invention can be suitably used for forming various devices such as a liquid crystal display device. The formation of the liquid crystal display device can be performed in accordance with the prior manner. In other words, the liquid crystal display device is usually formed by appropriately assembling a liquid crystal cell, a polarizing plate, an optical film, and an optional illumination system, and the like into a driving circuit. However, in the present invention, The aspect of the polarizing plate or the optical film of the invention is not particularly limited and may be in accordance with the prior art. As the liquid crystal cell, any type such as TN (Twisted Nematic), STN type, or π type can be used.
可形成在液晶單元之單側或兩側配置有偏光板或光學膜之液晶顯示裝置、或將背光或反射板用於照明系統者等適宜之液晶顯示裝置。於該情形時，本發明之偏光板或光學膜可設置在液晶單元之單側或兩側。在兩側設置偏光板或光學膜之情形時，該等可相同亦可不同。進而，在形成液晶顯示裝置時，例如可將擴散板、防眩層、抗反射膜、保護板、稜鏡陣列板、透鏡陣列板、光擴散板、背光等適宜之零件在適當之位置配置以1層或2層以上。A liquid crystal display device in which a polarizing plate or an optical film is disposed on one side or both sides of a liquid crystal cell, or a liquid crystal display device in which a backlight or a reflecting plate is used for an illumination system can be formed. In this case, the polarizing plate or optical film of the present invention may be disposed on one side or both sides of the liquid crystal cell. When the polarizing plate or the optical film is provided on both sides, the same may be the same or different. Further, when forming a liquid crystal display device, for example, suitable components such as a diffusion plate, an antiglare layer, an antireflection film, a protective plate, a 稜鏡 array plate, a lens array plate, a light diffusing plate, and a backlight can be disposed at appropriate positions. 1 or more layers.
就相位差板及偏光板而言，因具有使自外部入射並由金屬電極反射之光進行偏光之作用，故而具有藉由此偏光作用而無法自外部視覺辨識金屬電極之鏡面的效果。尤其是，若由1/4波長板構成相位差板，且將偏光板與相位差板之偏光方向所成之角度調整為π/4，則可完全遮蔽金屬電極之鏡面。Since the phase difference plate and the polarizing plate have a function of polarizing light incident from the outside and reflected by the metal electrode, there is an effect that the mirror surface of the metal electrode cannot be visually recognized from the outside by the polarizing action. In particular, when the retardation plate is formed of a quarter-wavelength plate and the angle formed by the polarization directions of the polarizing plate and the phase difference plate is adjusted to π/4, the mirror surface of the metal electrode can be completely shielded.
以下，列舉實施例說明本發明，但本發明並不限制於以下所示之實施例。再者，下述實施例及比較例之評價係藉由下述方法來進行。Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to the examples shown below. Further, the evaluations of the following examples and comparative examples were carried out by the following methods.
使用切片機(Leica製造，RM2155)，將玻璃刀片(日新EM股份有限公司製造，EM-25A型)沿著偏光板表面之法線方向切入，來切割偏光板，而獲得具有平滑剖面之厚度約為1mm之偏光板之薄片。Using a microtome (manufactured by Leica, RM2155), a glass blade (manufactured by Nisshin EM Co., Ltd., model EM-25A) was cut along the normal direction of the surface of the polarizing plate to cut the polarizing plate to obtain a thickness having a smooth profile. A sheet of polarizing plate of about 1 mm.
於顯微拉曼分光測定裝置(RENISHAW公司製造)之試料台上載置將所獲得之偏光板之薄片貼附在支撐體上而成者，對準焦點，藉由激發波長為514.5nm之Ar+ 雷射進行拉曼光譜之測定。測定係針對偏光元件之厚度方向之兩端部，在沿著偏光元件之厚度中心方向距離偏光元件保護膜與偏光元件之交界面(即，偏光元件之表面)2μm的位置，及厚度方向之中心部之共計3點進行。各測定係於曝光時間：1秒、累計次數：5次、雷射輸出：10%、測定直徑：2μm之條件下進行。On the sample stage of the micro Raman spectrometry apparatus (manufactured by RENISHAW Co., Ltd.), the obtained sheet of the polarizing plate was attached to the support, and the focus was focused by excitation of Ar + having a wavelength of 514.5 nm. The laser was measured for Raman spectroscopy. The measurement is performed at both ends in the thickness direction of the polarizing element, at a position along the center of the thickness of the polarizing element, at a position 2 μm from the interface between the polarizing element protective film and the polarizing element (that is, the surface of the polarizing element), and at the center of the thickness direction. A total of 3 points were carried out. Each measurement was carried out under the conditions of exposure time: 1 second, cumulative number of times: 5 times, laser output: 10%, and measurement diameter: 2 μm.
自所獲得之光譜，讀取105±5cm-1 範圍內之峰頂之拉曼散射強度，算出厚度方向中心部之散射強度(T1 )與厚度方向之兩端部2點之散射強度之平均值(T2 )之比T2 /T1 。From the obtained spectrum, the Raman scattering intensity at the peak top in the range of 105 ± 5 cm -1 was read, and the scattering intensity (T 1 ) at the center portion in the thickness direction and the scattering intensity at two points in the thickness direction were calculated. The ratio of the value (T 2 ) is T 2 /T 1 .
使用附帶積分球之分光光度計(日本分光製造，V7100)，算出單體穿透率Ts，用單體穿透率Ts之測定值減去表面反射，藉此算出經可見度修正之單體穿透率Ts(Y)。Using a spectrophotometer (manufactured by JASCO Corporation, V7100) with an integrating sphere, the monomer transmittance Ts was calculated, and the surface reflection was subtracted from the measured value of the monomer transmittance Ts, thereby calculating the visibility-corrected monomer penetration. Rate Ts (Y).
又，根據下式算出偏光板之雙色比DR。下式中，Ts(Y)表示上述經可見度修正之單體穿透率(%)，P表示偏光度(%)。Further, the two-color ratio DR of the polarizing plate was calculated from the following formula. In the following formula, Ts(Y) represents the above-described visibility corrected monomer transmittance (%), and P represents the degree of polarization (%).
將聚合度2400、皂化度99.9%、厚度75μm之聚乙烯醇膜浸漬於30℃之溫水中(膨潤浴)，一面使其膨潤，一面以聚乙烯醇膜之長度達到原長度之2倍的方式進行自由端單軸延伸。接著，將其浸漬於碘與碘化鉀之混合物(重量比1：16)之濃度為0.3重量%之水溶液(染色浴)中，一面以聚乙烯醇膜長度達到原長度之3倍的方式進行自由端單軸延伸，一面對膜進行染色。其後，一面將其浸漬於硼酸3重量%、碘化鉀3重量%之水溶液(交聯浴1)中，一面以聚乙烯醇膜之長度達到原長度之4倍的方式進行延伸之後，於60℃之硼酸4重量%、碘化鉀5重量%之水溶液(交聯浴2)中，以聚乙烯醇膜之長度達到原長度之6倍的方式進行延伸。其後，於碘化鉀3重量%之水溶液(碘含浸浴)中進行碘離子含浸處理之後，在60℃之烘箱中乾燥4分鐘，而獲得偏光元件。所獲得之偏光元件之厚度為28μm。The polyvinyl alcohol film having a polymerization degree of 2400, a saponification degree of 99.9%, and a thickness of 75 μm was immersed in warm water (swelling bath) at 30 ° C, and swelled while being doubled to the original length by the length of the polyvinyl alcohol film. Perform a free end uniaxial extension. Next, it was immersed in an aqueous solution (dye bath) having a concentration of 0.3% by weight of a mixture of iodine and potassium iodide (weight ratio 1:16), and the free end was carried out so that the length of the polyvinyl alcohol film was three times the original length. Uniaxial extension, one facing the membrane for dyeing. Thereafter, the mixture was immersed in an aqueous solution (crosslinking bath 1) of 3% by weight of boric acid and 3% by weight of potassium iodide, and then stretched so that the length of the polyvinyl alcohol film was 4 times the original length, and then at 60 ° C. In the aqueous solution (crosslinking bath 2) of 4% by weight of boric acid and 5% by weight of potassium iodide, the length of the polyvinyl alcohol film was extended to 6 times the original length. Thereafter, the mixture was subjected to iodide ion impregnation treatment in an aqueous solution of 3 wt% potassium iodide (iodine impregnation bath), and then dried in an oven at 60 ° C for 4 minutes to obtain a polarizing element. The thickness of the obtained polarizing element was 28 μm.
將各步驟之浸漬時間及延伸倍率(以原長度為基準之倍率，以及各步驟之倍率)示於表1。The immersion time and the stretching ratio (the magnification based on the original length, and the magnification of each step) of each step are shown in Table 1.
使用厚度為80μm之三乙醯纖維素膜(FUJI FILM製造，商品名「Fujitac TD80UL」)。A triethylene glycol cellulose film (manufactured by FUJI FILM, trade name "Fujitac TD80UL") having a thickness of 80 μm was used.
相對於含有乙醯乙醯基之聚乙烯醇樹脂(平均聚合度1200，皂化度98.5莫耳%，乙醯乙醯化度5莫耳%)100重量份，將羥甲基三聚氰胺32重量份，於30℃之溫度條件下溶解於純水中，而製備將固體成分濃度調整為3.2重量%之接著劑水溶液。32 parts by weight of methylol melamine with respect to 100 parts by weight of a polyvinyl alcohol resin containing an ethyl acetonitrile group (average degree of polymerization 1200, degree of saponification 98.5 mol%, ethyl acetonitrile degree 5 mol%), After dissolving in pure water at a temperature of 30 ° C, an aqueous solution of an adhesive having a solid concentration adjusted to 3.2% by weight was prepared.
使用上述接著劑，於30℃之溫度條件下，利用輥貼合機於偏光元件之兩面貼合三乙醯纖維素膜之後，在60℃下乾燥4分鐘，而獲得厚度為188μm之偏光板。Using the above-mentioned adhesive, the triethylene fluorene cellulose film was bonded to both surfaces of the polarizing element by a roll bonding machine at a temperature of 30 ° C, and then dried at 60 ° C for 4 minutes to obtain a polarizing plate having a thickness of 188 μm.
上述實施例1中，如表1所示變更染色浴浸漬時間tB 及交聯浴之浸漬時間tC ，除此之外，以與實施例1相同之方式獲得偏光板。In the above-mentioned Example 1, a polarizing plate was obtained in the same manner as in Example 1 except that the dyeing bath immersion time t B and the immersion time t C of the crosslinking bath were changed as shown in Table 1.
將實施例及比較例中所獲得之偏光板之拉曼光譜之測定結果，以及將偏光板在溫度60℃、濕度95%之加熱加濕條件下放置250小時前後的經可見度修正之單體穿透率Ts(Y)之變化量ΔTs(Y)及波長410nm下之雙色比DR(410)之變化量ΔDR(410)示於表2。The results of the Raman spectrum measurement of the polarizing plate obtained in the examples and the comparative examples, and the visibility-corrected monomer before and after the polarizing plate was left to stand under the conditions of heating and humidification at a temperature of 60 ° C and a humidity of 95% for 250 hours. The amount of change ΔTs (Y) of the transmittance Ts (Y) and the amount of change ΔDR (410) of the two-color ratio DR (410) at a wavelength of 410 nm are shown in Table 2.
由表2可知：偏光元件之厚度方向中心部以拉曼分光法所測得在105cm-1 附近之最大峰值強度T1 、與該偏光元件之厚度方向端部以拉曼分光法所測得在105cm-1 附近之最大峰值強度T2 之比值在本發明之範圍內的實施例之偏光板，在高溫高濕環境下之光學特性之變化較小，且耐久性優異。It can be seen from Table 2 that the maximum peak intensity T 1 at a center portion in the thickness direction of the polarizing element measured by Raman spectroscopy at around 105 cm -1 and the end portion in the thickness direction of the polarizing element are measured by Raman spectroscopy. The ratio of the maximum peak intensity T 2 in the vicinity of 105 cm -1 The polarizing plate of the example in the range of the present invention has a small change in optical characteristics in a high-temperature and high-humidity environment, and is excellent in durability.
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| JP2009114772A JP2010026498A (en) | 2008-06-17 | 2009-05-11 | Polarizing plate and method of manufacturing the same |
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| KR101704555B1 (en) * | 2010-04-16 | 2017-02-08 | 동우 화인켐 주식회사 | Method for preparing polarizer |
| KR101718937B1 (en) * | 2010-06-21 | 2017-03-23 | 동우 화인켐 주식회사 | Method of preparing polarizer for led |
| TWI570472B (en) * | 2011-10-03 | 2017-02-11 | 三菱瓦斯化學股份有限公司 | Aromatic polycarbonate polarized lens |
| JP6114160B2 (en) * | 2012-10-22 | 2017-04-12 | 日東電工株式会社 | Polarizing film and manufacturing method of polarizing film |
| JP5615987B2 (en) * | 2013-02-07 | 2014-10-29 | 日東電工株式会社 | Optical laminate having polarizing film |
| JP5863053B2 (en) | 2013-09-06 | 2016-02-16 | 日東電工株式会社 | Polarizing film, manufacturing method of polarizing film, and image display device using the polarizing film |
| WO2015037553A1 (en) * | 2013-09-13 | 2015-03-19 | 株式会社クラレ | Polarizing film |
| KR101691691B1 (en) * | 2013-12-30 | 2016-12-30 | 제일모직주식회사 | Polarizer, method for preparing the same, polarizing plate comprising the same and optical display apparatus comprising the same |
| CN109917506B (en) * | 2014-03-04 | 2022-05-24 | 株式会社可乐丽 | Polarizing film |
| KR20160001513A (en) | 2014-06-27 | 2016-01-06 | 삼성전자주식회사 | Polarizing film and antireflection film and display device |
| US20160033699A1 (en) | 2014-08-04 | 2016-02-04 | Nitto Denko Corporation | Polarizing plate |
| JP6211488B2 (en) * | 2014-08-25 | 2017-10-11 | 富士フイルム株式会社 | Liquid crystal display device and method for producing polarizing plate |
| WO2016056600A1 (en) * | 2014-10-08 | 2016-04-14 | 株式会社クラレ | Polarizing film |
| JP6619619B2 (en) * | 2015-11-04 | 2019-12-11 | 日東電工株式会社 | Polarizer, polarizing plate, and method for producing polarizer |
| JP2023013221A (en) * | 2021-07-15 | 2023-01-26 | 住友化学株式会社 | Polarizing element, polarizing plate, and image display device |
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| TW200535466A (en) * | 2004-01-06 | 2005-11-01 | Nitto Denko Corp | Fabrication method for polarizing plate, polarizing plate, optical film and image display |
| TW200641009A (en) * | 2005-03-03 | 2006-12-01 | Fuji Photo Film Co Ltd | Cellulose acylate film, method for producing cellulose acylate film, polarizing plate and liquid crystal display device |
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| JP2003240945A (en) * | 2002-02-14 | 2003-08-27 | Nitto Denko Corp | Method for manufacturing polarizer, polarizer, polarizing plate, and image display device |
| JP2003240946A (en) * | 2002-02-14 | 2003-08-27 | Nitto Denko Corp | Method for manufacturing polarizer, polarizer, polarizing plate, and image display device |
| JP4150605B2 (en) * | 2003-02-04 | 2008-09-17 | 富士フイルム株式会社 | Polarizer |
| JP4562133B2 (en) * | 2005-04-14 | 2010-10-13 | 日本化薬株式会社 | Polarizing element film, polarizing plate, and manufacturing method thereof |
| JP4656522B2 (en) * | 2006-01-31 | 2011-03-23 | 日本化薬株式会社 | A polarizing plate with improved durability |
| JP4697964B2 (en) * | 2006-02-24 | 2011-06-08 | 日東電工株式会社 | Polarizer manufacturing method and cleaning apparatus |
| CN101101411A (en) * | 2006-07-07 | 2008-01-09 | 日东电工株式会社 | Liquid crystal panel and liquid crystal display |
| JP4707146B2 (en) * | 2006-10-18 | 2011-06-22 | 日東電工株式会社 | Manufacturing method of polarizer |
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| TW200535466A (en) * | 2004-01-06 | 2005-11-01 | Nitto Denko Corp | Fabrication method for polarizing plate, polarizing plate, optical film and image display |
| TW200641009A (en) * | 2005-03-03 | 2006-12-01 | Fuji Photo Film Co Ltd | Cellulose acylate film, method for producing cellulose acylate film, polarizing plate and liquid crystal display device |
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