TW200417794A

TW200417794A - Polarizing plate, production process for polarizing plate, and liquid crystal display device

Info

Publication number: TW200417794A
Application number: TW093102079A
Authority: TW
Inventors: Keiichi Taguchi
Original assignee: Fuji Photo Film Co Ltd
Priority date: 2003-01-31
Filing date: 2004-01-30
Publication date: 2004-09-16
Also published as: KR20040069948A; TWI313772B; JP2004233871A

Abstract

The invention provides a polarizing plate in which the thickness of polarizing film at polarizing plate is thin, and can prevent the light leakage at short and long wavelengths of visible light during cross Nichol, and also exhibits excellent hue. Also, the invention provides a polarizing plate with a polarizing film which using polymer film formed by oblique orientation with enhanced yield in punching process of polarizing plate, and having high performance and inexpensive. The production process for the said polarizing plate and the liquid crystal display device using the said polarizing plate are also provided. The polarizing plate of this invention is characterized in that during cross Nichol, the transmission rate for wavelength 700 nm is from 0.001% to 0.3%, and for wavelength 410 nm is from 0.001% to 0.3%, and the thickness of polarizing film at the said polarizing plate is from 5μm to 22μm.

Description

200417794 玖、發明說明一、發明所屬之技術領域本發明係關於偏光板、該偏光板之製造方法、具有該偏光板之液晶顯示裝置。二、先前技術隨著液晶顯示裝置（下稱爲L C D )之普及化，偏光板之需求在快速劇增。偏光板一般係在具有偏光能的偏光層之兩面或單面，經由黏著劑層貼合保護膜所製成。偏光層之材料主要係使用聚乙烯醇（下稱爲PVA )，將 PVA膜予以單軸向拉伸後，以碘或二色性染料染色或經染色後予以拉伸，再以硼化合物加以交聯化，藉此即可形成偏光層用之偏光膜。偏光膜之吸收軸，由於一般向長度方向施加單軸向拉伸，所以將成爲與長度方向大致平行。此外，其他拉伸方法則有：邊使塑膠薄膜向橫向或縱向作單軸向拉伸，邊使其拉伸方向之左右在不同速率下向與前期拉伸方向不同的縱向或橫向牽引拉伸，以使配向軸對於上述單軸向拉伸方向傾斜之方法（先前例1 ;請參閱專利文獻1 )，藉由在連續的薄膜之左右兩邊緣端具有數對與行進方向成β角度的左右成對之薄膜保持點，可隨著薄膜的行進而使各個成對的點向0方向拉伸之結構，以製造對於薄膜行進方向具有任意角度0之拉伸軸的薄膜之方法 (先前例2 ;請參閱專利文獻2)，將薄膜兩端部抓住於在配置成使特定行進區間內的夾頭之行進距離互不相同的拉幅機軌道上兩排夾頭間以使其行進，藉以向與薄膜長度方 200417794 向成斜交的方向拉伸之製造方法（先前例3 ;請參閱專利文獻3 )，以及斜向拉伸法（先前例4 ;請參閱專利文獻4 )等。該_方法’雖然可使聚合物配向軸對於薄膜搬送方向傾斜所希求之角度，但是先前例1至3之方法卻會在膜造成伴紋、皺紋、拉伸不均，如欲緩和其則必須將拉伸製程延長成非常長，以致有設備成本增大之缺點，可解決該等缺點、問題者就是先前例4之方法。該方法係一種藉由將吸收軸予以傾斜45度，即可特別是對於大尺寸之偏光板，提商生產良率之優越方法。〔專利文獻1〕日本國專利特開第2 〇〇〇 _ 9 9 1 2號公報〔專利文獻2〕曰本國專利特開平第3_ 1 8270 1號公報〔專利文獻3〕曰本國專利特開平第2- 1 1 3920號公報〔專利文獻4〕曰本國專利特開第2002-86554號公報三、發明內容發明所欲解決之誤頴以先前之單軸向拉伸法所製得之偏光板，其偏光膜之厚度爲約2 5微米左右，特別是在大於1 5英寸的液晶監視器 ’由於偏光膜會因時效變化而收縮，因此從會造成由監視器周邊部光漏之故障（框緣故障），及在可攜性用途上需 200417794 要偏光板構件輕量化的觀點來考慮，對於偏光膜厚度薄膜化則有迫切期望。然而，已逐漸地淸楚愈使偏光膜趨於薄膜化’卻會導致在可見光之短波及長波側在正交尼科耳時之光漏將變大，以致色相（hue )偏離中性灰色是足以構成問題之所在。具體而言，偏光膜厚度若爲小於20微米，則上述問題將變得顯著，目前已上市之偏光板，最薄者爲 22.5微米。在正交尼科耳時之光漏會變大之問題，依照上述先前例 1至4之拉伸方法，仍然不能使其改善，因此逐漸地淸楚其爲無論是拉伸方法是一種共同的問題。有鑑於此，本發明之目的係提供一種偏光板，其偏光膜之厚度薄，且在正交尼科耳時可防止可見光在短波及長波側之光漏、可顯現良好的色相者。並且，提供一種偏光板 ’其係經由斜向拉伸法所製得，以可提高在偏光板沖切製程時之良率，經斜向拉伸之聚合物薄膜作爲偏光膜，並具有高性能且價廉者。本發明之其他目的係提供一種上述偏光板之製造方法及具有上述偏光板之液晶顯示裝置。解決課顆之方法若依照本發明，則可提供下述結構之聚合物薄膜之拉伸方法、偏光板、及液晶顯示裝置，以達成上述目的。 1. 一種偏光板，其特徵爲：在正交尼科耳時，在700奈米之透射率爲從0.001 %至〇·3 %，在410奈米之透射率爲從0.001 %至0.3 %，且偏光膜之膜厚爲從5微米 200417794 至22微米。 2. 如上述第1項之偏光板，其中偏光膜之膜厚爲從5微米至20微米。 3. 如上述第1或2項之偏光板，其中在正交尼科耳時在 4 1 0奈米之透射率爲從0.0 0 1 %至0.0 8 %。 4. 如上述第1至3項中任一項之偏光板，其中單板透射率爲從41 %至50 %，偏光度爲從99.9 %至100 %。 5 .如上述第1至4項中任一項之偏光板，其中在偏光膜之至少單面具有保護膜，且該保護膜之遲相軸與偏光膜之吸收軸之角度爲從10°至90。。 6 ·如上述第1至5項中任一項之偏光板，其中具有偏光膜之長尺寸的偏光板，且偏光膜之吸收軸係與長度方向非爲成平行、也非爲成垂直。 7* 一種偏光板之製造方法，其係用以製造如上述第1至 6項中任一項之偏光板，其特徵爲··包含連續地供給偏光膜用聚合物薄膜’並向該薄膜之搬送方向作單軸向拉伸以形成偏光膜之步驟。 8.如上述第7項之製造方法，其中拉伸放大率爲從4倍至1 2倍。 9· 一種偏光板之製造方法，其係用以製造如上述第1至 6項中任一項之偏光板，其特徵爲：包含連續地供給 ί扁光fl吴用聚合物薄膜’並邊向該薄膜之搬送方向作單軸向拉伸’或在經單軸向拉伸後，邊向與搬送方向成垂直方向拉伸以形成偏光膜之步驟。 1200417794 1 0. —種偏光板之製造方法，其係用以製造如_ 6項中任一項之偏光板，其特徵爲：包含保持連續地供給之偏光膜用聚合物薄膜之使該保持裝置向薄膜長度方向行進邊賦予以形成偏光膜之步驟，其中該步驟係以：自偏光膜用聚合物薄膜之一保持開始點起至實質保持解除點的保持裝及自聚合物薄膜之另一側端的實質保持開質保持解除點的保持裝置之軌跡L2，與兩解除點之距離W，係符合下述式（1 )之條持聚合物薄膜之支持性、使揮發分率爲10 態存在下作拉伸，其後以乾燥使其收縮10 使揮發分率下降之方法所實施：式（1): |L2-L1| >〇.4W。 1 1 · 一種液晶顯示裝置，其特徵爲：將上述第任一項之偏光板，使用於配置在液晶胞（c 兩片偏光板中至少一者。本發明之偏光板係具有至少具有偏光能之偏厚爲從5微米至22微米，且在正交尼科耳時在透射率爲從0.001 %至〇·3 %，在410奈米之 0.001 %至〇·3 %。偏光膜之膜厚係以從5微米至20微米爲佳。耳時在7 0 0奈米之透射率上限係以0.3 %爲佳，更佳。在410奈米之透射率上限係以0.3 %以二述第1至以保持裝置兩端，並邊張力作拉伸側端的實質 t之軌跡L 1 始點起至實個實質保持件，且在保 %以上之狀 %以上同時【至6項中 e 11 )兩側之光膜，其膜 700奈米之透射率爲從在正交尼科以0.2 %爲下爲佳，以 -10- 200417794 0 ·0 8 %以下爲更佳，以0· 0 5 %以下爲最佳。本發明之偏光板，係在正交尼科耳時之色調係在CIE ( 國際照明技術委員會）色空間（color* space)中X値將爲從0.2至0.35，Y値將爲從0.2至0.35，呈帶藍色較少之中性灰色的色彩，可提供良好品質。另外，單板透射率及偏光度係以較高者爲佳，單板透射率係以從41 %至50 %爲佳，偏光度係以從99.9 %至100 % 爲佳。單板透射率係以從42 %至5 0 %，偏光度係以從 99.95 %至1 00 %爲更佳。進一步較佳的形態是該偏光膜之吸收軸係非平行也非垂直於長度方向，而較佳爲該吸收軸與長度方向形成之角度爲從20°至70°範圍，更佳爲從40°至50°範圍。由於偏光膜之吸收軸係與長度方向非成平行也非成垂直，且保護膜之遲相軸與偏光膜之吸收軸所形成之角度爲從 10°至90°，所以在偏光板沖切製程可在高良率下由長尺寸之偏光板獲得單板。具有上述特徵之偏光板，係經設法改變以拉伸製造偏光膜時的色相調整劑之種類選擇與添加方法，及調節偏光板用聚合物薄膜之膨潤並設法改變二色性物質及固膜劑之添加方法，即可製得。本發明人等爲防止予以薄膜化時所產生在正交尼科耳時的色相之帶藍色化，經專心硏討結果，發現在正交尼科耳時在7 00奈米之透射率設定爲小於〇.3 % ’使在410奈米之透射率設定爲小於〇. 3 %，即可得接近於中性灰色之色相。 -11 - 200417794 並且，發現降低在正交尼科耳時在700奈米之透射率及在4 1 0奈米之透射率之方法，則以對於偏光膜添加碘等二色性物質再加上以在對應的波長領域具有吸收之二色性色素添加入作爲色相調整劑、及在添加碘等二色性物質時〜起添加硼酸等固膜劑等之方法爲有效。而且組合該等而實施也是有效。 <色相調整劑之種類與添加方法> 茲就在本發明採用之色相調整劑之種類與添加方法說明如下。可供作爲色相調整劑使用之二色性色素之具體例，係包括例如：C.I.直接紅37、剛果紅（C.I·直接紅28 ) ，C.I.直接紫12、C.I·直接藍90、C.I·直接藍22、C.I.直接藍1、 C.I·直接藍151、C.I·直接綠1等之聯苯胺系；C.I·直接黃 44、C.I.直接紅23、C.I.直接紅79等之二苯基脲系；C.I. 直接黃12等之二苯乙烯系；C.I.直接紅31等之二基胺系 ;C.I·直接紅81、C.I.直接紫9、C.I·直接藍78等之J酸系〇除此以外，也可使用：C.I·直接黃8、C.I·直接黃28、 C.I.直接黃86、C.I.直接黃87、C.I·直接黃142、C.I.直接橙26、C.I·直接橙39、C.I·直接橙72、C.I·直接橙106、 C . I.直接橙1 0 7、C . I.直接紅2、C · I ·直接紅3 9、C · I.直接紅 83、C.I.直接紅 89、C.I·直接紅 240、C.I.直接紅 242、C.I. 直接紅247、C.I.直接紫48、C.I·直接紫51、C.I.直接紫98 、C.I.直接藍15、C.I.直接藍67、C.I.直接藍71、C.I.直接 - 12 - 200417794 藍98、C.I.直接藍i68、c.I.直接藍202、C.I.直接藍236、 C.I.直接藍249、C.I.直接藍270、C.I·直接綠59、C.I·直接綠85、C.I·直接棕44、C.I.直接棕106、C.I.直接棕195、 C . I ·直接棕2 1 〇、c . I ·直接棕2 2 3、C · I ·直接棕2 2 4、C . I ·直接黑1、C.I.直接黑17、C.I.直接黑19、C.I.直接黑54等 ;以及日本國專利特開昭第6 2 - 7 0 8 0 2號、特開平第1 -1 6 1 202號、特開平第^72906號、特開平第卜1 729〇7號、特開平第1 - 1 8 3 602號、特開平第1-248 1 05號、特開平第1_265 2〇5號、特開平第7_261〇24號之各公報記載之二色性色素等也可適合使用。其中，以偶氮系色素爲佳，特別是以雙偶氮系與參偶氮系色素爲佳。二色性色素係以水溶性者爲佳，因此在二色性分子導入磺酸基、胺基、羥基等親水性取代基，以用作爲游離酸、或鹼金屬鹽、銨鹽、胺類之鹽。上述色相調整劑也可混合兩種以上。可供添加之色素係只要在410奈米或700奈米具有吸收即可達成本發明之目的，但是較佳爲在從380奈米至500奈米或從600奈米至 7 2 0奈米具有主吸收。另外，可供添加之色素量係可視所使用的色素之吸光度、二色比而任意決定。只要在正交尼科耳時7 0 0奈米之透射率能成爲低於0.3 %、且4 1 0奈米之透射率能成爲低於0 · 3 %則無特殊限制。另外，將上述色相調整劑添加於偏光膜之方法，雖然可使用浸漬、塗佈、噴霧等所有方法，但是其中係以浸漬法爲佳。添加之步驟係可爲在拉伸前、拉伸後中任一者皆可 -13 - 200417794 ’但是從提高偏光性能之觀點來考慮，則以拉伸前爲佳。可以單獨設置添加步驟，也可在後述染色步驟或固膜劑添加步驟中任一者或是在兩者中實施。 <偏光板用聚合物薄膜之膨潤調節、二色性物質及固膜劑之添加方法>200417794 (1) Description of the invention 1. Technical field to which the invention belongs The present invention relates to a polarizing plate, a method for manufacturing the same, and a liquid crystal display device having the same. 2. Prior Technology With the popularization of liquid crystal display devices (hereinafter referred to as LCD), the demand for polarizing plates is rapidly increasing. A polarizing plate is generally made on both sides or one side of a polarizing layer having polarizing energy, and a protective film is bonded through an adhesive layer. The material of the polarizing layer is mainly polyvinyl alcohol (hereinafter referred to as PVA). After the PVA film is uniaxially stretched, it is dyed with iodine or dichroic dye or stretched after dyeing. In this way, a polarizing film for a polarizing layer can be formed. The absorption axis of a polarizing film is generally parallel to the longitudinal direction because uniaxial stretching is generally applied to the longitudinal direction. In addition, other stretching methods include: while the plastic film is uniaxially stretched in the transverse or longitudinal direction, the stretched direction of the plastic film is stretched at different rates in the longitudinal or transverse direction that is different from the previous stretching direction. In order to incline the alignment axis with respect to the uniaxial stretching direction (previous example 1; please refer to Patent Document 1), the left and right edge ends of the continuous film have a number of pairs of left and right sides that make an angle β with the direction of travel. The film holds points in pairs, and the structure in which each pair of points can be stretched toward the 0 direction as the film advances, and a method for manufacturing a film having a stretching axis with an arbitrary angle of 0 with respect to the film traveling direction (previous example 2) (See Patent Document 2), the two ends of the film are grasped between two rows of chucks on a tenter track configured to make the chucks travel in different distances different from each other so that they travel, thereby A manufacturing method of stretching in a direction oblique to the length of the film 200417794 (previous example 3; see patent document 3), and an oblique stretching method (previous example 4; see patent document 4). Although this method can tilt the polymer alignment axis to the desired direction of the film conveying direction, the methods of the previous examples 1 to 3 will cause unevenness, wrinkles, and uneven stretching in the film. Extending the stretching process to a very long length has the disadvantage of increasing the cost of the equipment. The shortcomings can be solved by using the method of Example 4 above. This method is an excellent method to improve production yield by tilting the absorption axis by 45 degrees, especially for large-size polarizing plates. [Patent Document 1] Japanese Patent Laid-Open No. 2000- 9 9 1 2 [Patent Document 2] Japanese Patent Laid-Open No. 3_ 1 8270 1 [Patent Document 3] Japanese Patent Laid-Open No. 1 2- 1 1 3920 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2002-86554 III. SUMMARY OF THE INVENTION Errors to be Solved by the Invention The polarizing plate obtained by the previous uniaxial stretching method, The thickness of the polarizing film is about 25 micrometers, especially for LCD monitors larger than 15 inches. Because the polarizing film shrinks due to aging, it will cause light leakage from the periphery of the monitor (frame edge Failure), and the need for portable applications for 200417794 to reduce the weight of polarizing plate members, there is an urgent expectation for the thickness of the polarizing film. However, it has gradually become clear that the polarizing film is becoming thinner, but it will cause the light leakage when the Nicols are crossed at the short and long wavelengths of visible light, so that the hue deviates from the neutral gray. Enough to pose the problem. Specifically, if the thickness of the polarizing film is less than 20 micrometers, the above problems will become significant. The thinnest polarizing plate currently on the market is 22.5 micrometers. The problem of large light leakage when orthogonal Nicols are not improved according to the stretching method of the previous examples 1 to 4 above, so gradually it is understood that it is a common regardless of the stretching method problem. In view of this, an object of the present invention is to provide a polarizing plate whose polarizing film has a thin thickness and can prevent visible light from leaking on the short-wave and long-wave sides when Nicols are crossed, and can develop a good hue. In addition, a polarizing plate is prepared by an oblique stretching method, which can improve the yield rate during the blanking process of the polarizing plate. The obliquely stretched polymer film serves as a polarizing film and has high performance. And cheap. Another object of the present invention is to provide a method for manufacturing the above-mentioned polarizing plate and a liquid crystal display device having the above-mentioned polarizing plate. Method for solving class particles According to the present invention, a method for stretching a polymer film having the following structure, a polarizing plate, and a liquid crystal display device can be provided to achieve the above-mentioned object. 1. A polarizing plate characterized in that when the Nicols are crossed, the transmittance at 700 nm is from 0.001% to 0.3%, and the transmittance at 410 nm is from 0.001% to 0.3%, The thickness of the polarizing film is from 5 microns 200417794 to 22 microns. 2. The polarizing plate according to item 1 above, wherein the film thickness of the polarizing film is from 5 μm to 20 μm. 3. The polarizing plate as described in item 1 or 2 above, wherein the transmittance at 4 10 nm when crossed Nicols is from 0.01 to 0.08%. 4. The polarizing plate according to any one of items 1 to 3 above, wherein the single-plate transmittance is from 41% to 50%, and the polarization degree is from 99.9% to 100%. 5. The polarizing plate according to any one of items 1 to 4 above, wherein a protective film is provided on at least one side of the polarizing film, and the angle between the retardation axis of the protective film and the absorption axis of the polarizing film is from 10 ° to 90. . 6. The polarizing plate according to any one of items 1 to 5 above, wherein the polarizing plate has a long size of the polarizing film, and the absorption axis of the polarizing film is not parallel or perpendicular to the length direction. 7 * A method of manufacturing a polarizing plate, which is used to manufacture the polarizing plate according to any one of items 1 to 6 above, characterized in that it includes: ... The carrying direction is a step of uniaxial stretching to form a polarizing film. 8. The manufacturing method according to item 7 above, wherein the stretching magnification is from 4 times to 12 times. 9. A method of manufacturing a polarizing plate, which is used to manufacture the polarizing plate according to any one of items 1 to 6 above, characterized in that it comprises: continuously supplying a thin polymer film for flat and fl The film is transported in a uniaxial direction, or after the film is uniaxially stretched, the film is stretched in a direction perpendicular to the transport direction to form a polarizing film. 1200417794 1 0. A method of manufacturing a polarizing plate, which is used to manufacture a polarizing plate as in any of 6 items, and is characterized in that the holding device includes a polymer film for holding a continuously supplied polarizing film. A step of forming a polarizing film by applying a film along the length of the film, wherein the step includes: holding from a holding start point of a polymer film for a polarizing film to a substantial holding release point, and from the other side of the polymer film The trajectory L2 of the holding device that holds the release point at the end of the substance and the distance W from the two release points is in accordance with the support of the polymer film in accordance with the following formula (1), so that the volatile content is 10 It is stretched and then dried by shrinking it by 10 to reduce the volatile fraction: Formula (1): | L2-L1 | > 0.4W. 1 1 · A liquid crystal display device, characterized in that: the above-mentioned polarizing plate is used in at least one of two polarizing plates (c). The polarizing plate of the present invention has at least polarizing energy. The partial thickness is from 5 micrometers to 22 micrometers, and the transmittance is 0.001% to 0.3% at cross Nicols, and 0.001% to 0.3% at 410 nm. Film thickness of polarizing film It is preferably from 5 microns to 20 microns. The upper limit of transmittance at 700 nm at ear is preferably 0.3%, more preferably. The upper limit of transmittance at 410 nm is 0.3%. Keep the two ends of the device and stretch the trajectory L 1 of the substantial t at the side end from the starting point to the actual substantial holding member, and keep it more than %% at the same time [to 6 items in e 11) two Side light film, the transmittance of 700 nm of the film is preferably from 0.2% at Cross Nico, more preferably -10- 200417794 0 · 0 8% or less, more preferably 0. 05% or less For the best. In the polarizing plate of the present invention, the color tone of the cross-Nicol system is in the CIE (International Commission on Illumination Technology) color space (X 値 will be from 0.2 to 0.35, and Y 値 will be from 0.2 to 0.35. , With a neutral blue color with less blue, providing good quality. In addition, the veneer transmittance and polarization degree are preferably higher, the veneer transmittance is preferably from 41% to 50%, and the polarization degree is preferably from 99.9% to 100%. The veneer transmittance is from 42% to 50%, and the polarization is more preferably from 99.95% to 100%. A further preferred form is that the absorption axis of the polarizing film is not parallel or perpendicular to the length direction, and it is preferable that the angle formed by the absorption axis and the length direction is in a range from 20 ° to 70 °, and more preferably from 40 ° Up to 50 °. Because the absorption axis of the polarizing film is not parallel or perpendicular to the length direction, and the angle formed by the late phase axis of the protective film and the absorption axis of the polarizing film is from 10 ° to 90 °, the blanking process is performed in the polarizing plate. Single boards can be obtained from long polarizers at high yields. The polarizing plate having the above characteristics is to change the selection and addition method of the hue adjusting agent when manufacturing the polarizing film by stretching, to adjust the swelling of the polymer film for polarizing plate, and to change the dichroic substance and the film fixing agent. It can be prepared by the addition method. In order to prevent the blueness of the hue at the time of crossed Nicols when the film was thinned, the inventors have intensively discussed the results and found that the transmittance at 700 nanometers is set at the time of crossed Nicols If the transmittance at 410 nm is less than 0.3%, the hue close to neutral gray can be obtained. -11-200417794 Furthermore, it was found that the method of reducing the transmittance at 700 nm and the transmittance at 4 10 nm in crossed Nicols is to add a dichroic substance such as iodine to the polarizing film and add It is effective to add a dichroic pigment having absorption in a corresponding wavelength range as a hue adjuster, and when adding a dichroic substance such as iodine to a solid film agent such as boric acid. It is also effective to combine these. < Types and adding methods of hue adjusting agents > The types and adding methods of hue adjusting agents used in the present invention are described below. Specific examples of dichroic pigments that can be used as hue adjusting agents include, for example, CI Direct Red 37, Congo Red (CI · Direct Red 28), CI Direct Purple 12, CI · Direct Blue 90, and CI · Direct Blue. 22, CI Direct Blue 1, CI · Direct Blue 151, CI · Direct Green 1 and other benzidine series; CI · Direct Yellow 44, CI Direct Red 23, CI Direct Red 79 and other diphenylurea series; CI Direct Yellow 12 grade stilbene; CI Direct Red 31 and other diamines; CI · Direct Red 81, CI Direct Violet 9, CI · Direct Blue 78, etc. J acid series. In addition, CI can also be used: CI Direct Yellow 8, CI Direct Yellow 28, CI Direct Yellow 86, CI Direct Yellow 87, CI Direct Yellow 142, CI Direct Orange 26, CI Direct Orange 39, CI Direct Orange 72, CI Direct Orange 106, C. I. Direct Orange 1 0 7, C. I. Direct Red 2, C · I · Direct Red 3 9, C · I. Direct Red 83, CI Direct Red 89, CI Direct Red 240, CI Direct Red 242 , CI Direct Red 247, CI Direct Violet 48, CI Direct Violet 51, CI Direct Violet 98, CI Direct Blue 15, CI Direct Blue 67, CI Direct Blue 71, CI Direct-12-200417794 98, CI direct blue i68, cI direct blue 202, CI direct blue 236, CI direct blue 249, CI direct blue 270, CI direct green 59, CI direct green 85, CI direct brown 44, CI direct brown 106, CI Direct Brown 195, C. I · Direct Brown 2 1 0, c. I · Direct Brown 2 2 3, C · I · Direct Brown 2 2 4, C. I · Direct Black 1, CI Direct Black 17, CI Direct Black 19, CI Direct Black 54, etc .; and Japanese Patent Laid-Open No. 6 2-7 0 8 0 2; Japanese Patent Laid-Open No. 1 -1 6 1 202; Japanese Patent Laid-Open No. ^ 72906; Japanese Patent Laid-Open No. 1 The dichroism described in the respective gazettes of No. 729〇7, JP-A No. 1-1 8 3 602, JP-A No. 1-248 1 05, JP-A No. 1-265 2 05, and JP-A No. 7_261〇24 Pigments and the like are also suitable for use. Among them, azo-based pigments are preferred, and especially disazo-based and ginseng-based pigments are preferred. A dichroic pigment is preferably a water-soluble one. Therefore, a sulfonic acid group, an amine group, a hydroxyl group and other hydrophilic substituents are introduced into a dichroic molecule for use as a free acid, or an alkali metal salt, an ammonium salt, or an amine. salt. These hue adjusting agents may be mixed in two or more kinds. The pigments that can be added can achieve the purpose of the invention as long as they have absorption at 410 nanometers or 700 nanometers, but it is preferable to have the pigments from 380 nanometers to 500 nanometers or from 600 nanometers to 720 nanometers. Master absorption. The amount of the pigment to be added can be arbitrarily determined depending on the absorbance and dichroic ratio of the pigment to be used. There is no particular limitation as long as the transmittance of 700 nm can be lower than 0.3% and the transmittance of 4 100 nm can be lower than 0.3% in crossed Nicols. In addition, as the method for adding the hue adjusting agent to the polarizing film, all methods such as dipping, coating, and spraying can be used, but the dipping method is preferred. The addition step may be either before stretching or after stretching. -13-200417794 ′ However, from the viewpoint of improving polarizing performance, it is better to stretch before. The addition step may be provided separately, or it may be performed in either of the dyeing step or the fixing agent adding step described later, or both. < Swelling adjustment of polymer film for polarizing plate, addition method of dichroic substance and film fixing agent >

此外’本發明之偏光板係可經由膨潤步驟、染色步驟、固膜步驟 '拉伸步驟、乾燥步驟、保護膜貼合步驟、貼合後乾燥步驟來製造。也可將上述染色步驟、固膜步驟、拉伸步驟之順序任意改變，或也可組合數個步驟而同時進行。尤其是以下述方式實施上述膨潤步驟、染色步驟、及乾燥步驟，即可順利製得本發明之偏光板。 (甲）在上述膨潤步驟，若偏光板用聚合物薄膜爲PVA 膜，則爲促進二色性物質的碘之染色，通常須預先浸漬於水等，惟此時之溫度則宜設定爲從30 °C 至50°C，較佳爲從35°C至45°C。In addition, the polarizing plate of the present invention can be produced through a swelling step, a dyeing step, a film-fixing step, a stretching step, a drying step, a protective film bonding step, and a post-drying step. The order of the above-mentioned dyeing step, film-fixing step, and stretching step can also be arbitrarily changed, or several steps can be combined and performed simultaneously. In particular, the above-mentioned swelling step, dyeing step, and drying step are carried out in the following manner, and the polarizing plate of the present invention can be smoothly produced. (A) In the above swelling step, if the polymer film for polarizing plates is a PVA film, in order to promote the dyeing of iodine of dichroic substances, it is usually necessary to immerse it in water in advance, but the temperature at this time should be set from 30 ° C to 50 ° C, preferably from 35 ° C to 45 ° C.

(乙）在染色步驟，則將二色性物質之碘染色於偏光膜用聚合物薄膜，惟此時則應將固膜劑之硼酸對於碘添加以質量比計爲從1至30倍。 (丙）在乾燥步驟則將進行經拉伸的偏光膜之乾燥，惟此時之溫度應設定爲低於80 °C，較佳爲低於70 0C。有關上述各步驟之說明，則容後說明。 <使偏光膜厚度變薄之方法> 使偏光膜厚度變薄之方法’係藉由使用在傳統拉伸法中 -14- 200417794 經提高拉伸放大率的膜厚較薄之PVA膜等即可達成。通常使用的PVA §吴之膜厚雖然是75微米（例如可樂麗（ Kurarey)公司製VF-P、VF-PS等），但是此種情形下，若以長度方向之縱單軸向拉伸法拉伸8倍左右以上，則偏光膜膜厚即可成爲20微米以下。若以拉幅方式等之橫單軸向拉伸法拉伸4倍以上，則偏光膜膜厚即可成爲2〇微米以下。另外，將PVA膜之膜厚變薄爲50微米以下，並以單軸向拉伸法拉伸6倍以上，偏光膜膜厚即可成爲2〇微米以下〇在本發明中，除該等單軸向拉伸法之外，也可使用邊將偏光膜用聚合物薄膜向搬送方向作單軸向拉伸，或經單軸向拉伸後，向橫向拉伸以製造之方法。該方法就是一般稱爲雙軸向拉伸法。該方法中較具一般性者則以藉由拉幅方式之同時雙軸向拉伸法或藉由管筒（tubular )方式之同時雙軸向拉伸法等已爲眾人皆知。若依照此等方式，將膜厚爲7 5微米之P V A膜向縱向約4倍以上，向橫向約1 · 5倍以上拉伸時，偏光膜膜厚即可成爲20微米以下。在本發明中較佳的拉伸方式爲在日本國專利特開第 2 0 0 2 - 8 6 5 5 4號公報所記載之斜向拉伸法。依照該拉伸法，若將PVA膜之膜厚爲125微米以下之PVA膜予以拉伸4 倍以上，偏光膜膜厚即可成爲20微米以下。在本發明中，從會產生光漏的故障（框緣故障）、及偏光板構件的輕量化之觀點來考慮，偏光膜厚度雖然是以愈薄爲佳，但是若太薄，則將造成膜在拉伸中斷裂，對於在 - 15 - 200417794 浸漬於染色液、固膜液時之搬送造成不良影響，在拉伸後之乾燥中產生龜裂等問題。因此，在本發明中較佳的偏光膜厚度爲從5微米至22微米，更佳爲從8微米至20微米 <各步驟之說明> 茲就製造本發明之偏光板時之各步驟說明如下。 (膨潤步驟）(B) In the dyeing step, the dichroic substance iodine is dyed on the polymer film for polarizing film, but at this time, the boric acid of the film-fixing agent should be added to the iodine in a mass ratio from 1 to 30 times. (C) In the drying step, the stretched polarizing film is dried, but the temperature at this time should be set below 80 ° C, preferably below 70 0C. The description of the above steps will be described later. < Method for reducing thickness of polarizing film > Method for reducing thickness of polarizing film 'is a thin film thickness of PVA film, etc., which is increased by using a conventional stretching method -14-200417794 which has increased stretching magnification. That's it. Generally used PVA § Although the film thickness of Wu is 75 microns (for example, VF-P, VF-PS manufactured by Kurarey, etc.), in this case, if the longitudinal uniaxial stretching method is used in the longitudinal direction When it is stretched about 8 times or more, the thickness of the polarizing film can be 20 μm or less. If it is stretched 4 times or more by a transverse uniaxial stretching method such as a tenter method, the thickness of the polarizing film can be 20 μm or less. In addition, if the film thickness of the PVA film is reduced to 50 micrometers or less and stretched by more than 6 times by a uniaxial stretching method, the polarizing film thickness may be 20 micrometers or less. In the present invention, except for these In addition to the axial stretching method, a method in which the polymer film for a polarizing film is uniaxially stretched in the conveying direction or uniaxially stretched and then stretched in the transverse direction may be used. This method is generally called the biaxial stretching method. The more general ones in this method are the simultaneous biaxial stretching method by the tenter method or the simultaneous biaxial stretching method by the tubular method, etc., are well known. According to these methods, when a PVA film having a thickness of 75 micrometers is stretched about 4 times or more in the longitudinal direction and about 1.5 times or more in the transverse direction, the film thickness of the polarizing film can be 20 microns or less. The preferred stretching method in the present invention is the oblique stretching method described in Japanese Patent Laid-Open No. 2002-8 6 554. According to this stretching method, if a PVA film having a film thickness of 125 μm or less is stretched 4 times or more, the polarizing film thickness can be 20 μm or less. In the present invention, from the viewpoints of failure (frame edge failure) where light leakage occurs and weight reduction of the polarizing plate member, although the thickness of the polarizing film is preferably thinner, if it is too thin, it will cause the film Breaking during stretching has an adverse effect on the transport when immersed in the dyeing solution and solid film solution, and problems such as cracks occur during drying after stretching. Therefore, the preferred thickness of the polarizing film in the present invention is from 5 micrometers to 22 micrometers, and more preferably from 8 micrometers to 20 micrometers. &Lt; Description of each step > Here is a description of each step when manufacturing the polarizing plate of the present invention as follows. (Swelling step)

膨潤步驟雖然是僅以水實施爲佳，但是如日本國專利特開平第1 0- 1 5 3 709號公報所記載，爲使光學性能安定化及避免在生產線上所產生偏光膜基材皺紋，也可藉由硼酸水溶液來膨潤偏光膜基材，以控制偏光膜基材之膨潤度。另外’膨潤步驟之溫度及時間雖可任意決定，但是較佳爲10 °C至50 °C、5秒鐘以上爲佳，若未使用二色性色素，則較佳爲如上述從3 0。C至5 0。C，更佳爲在從3 5。C至 4 5 °C之溫度下設定爲從5秒鐘至600秒鐘，較佳爲從i 5 秒鐘至300秒鐘。Although the swelling step is preferably performed only with water, as described in Japanese Patent Laid-Open No. 10- 1 5 3 709, in order to stabilize optical performance and avoid wrinkles of the polarizing film substrate on the production line, The polarizing film substrate can also be swelled with an aqueous boric acid solution to control the degree of swelling of the polarizing film substrate. In addition, although the temperature and time of the 'swelling step can be arbitrarily determined, it is preferably 10 ° C to 50 ° C, preferably 5 seconds or longer. If a dichroic pigment is not used, it is preferably from 30 as described above. C to 50. C, more preferably from 3 to 5. The temperature of C to 4 5 ° C is set from 5 seconds to 600 seconds, preferably from i 5 seconds to 300 seconds.

(染色步驟）染色步驟係可使用日本國專利特開第2002-865 54號公報所記載之方法。另外，染色方法係不只是浸漬法，也可爲碘或染料溶液之塗佈或噴霧法等之任意方法。可供使用於染色之二色性物質雖然並無特殊限制，但是爲獲得高對比的偏光板’則以使用碘爲佳。而且，染色步驟以在液相下實施爲佳。若使用碘，則將PVA膜浸漬於碘-碘化鉀水溶液中實施 ^ 16- 200417794 。碘係以〇·〇5至20克/公升、碘化鉀係以3至2〇〇克/公升、碘與碘化鉀之質量比係以1至2 5 0 0 〇爲佳。染色時間係以10至1,200秒鐘爲佳，液溫度係以1〇至6〇。(^爲佳。並且，較佳爲將碘設定爲0.5至2克/公升、碘化鉀爲3〇至 i20克/公升、碘與碘化鉀之質量比爲30至120，染色時間則設定爲30至600秒鐘，液溫度爲20至50 °C。如上述，添加硼酸、硼砂等硼化合物以作爲固膜劑，並將染色步驟與後述固膜步驟同時進行也是有效。使用硼酸時’則以對於砩添加以質量比計爲1至3 0倍爲佳。另外，在本步驟添加二色性色素也是有效，其量則以〇 . 〇〇丨至1 克/公升爲佳。此外，使水溶液中之添加物量維持成恆定，乃在維持偏光性能上是重要，所以以連續方式製造時，應以一面補充碘、碘化鉀、硼酸、二色性色素等一面製造爲佳。補充係以溶液、固態中任一狀態均可實施。以溶液狀態添加時’也可作成爲高濃度，然後必要時逐滴地添加。 (固膜步驟）固膜步驟係以採取浸漬於交聯劑溶液，或塗佈溶液以使其含有交聯劑之方法爲佳。另外，如日本國專利特開平第 11-52130號公報所記載，也可將固膜步驟分成爲數次來實施。交聯劑可使用美國再發行專利第2 3 2，8 9 7號說明書所記載者，且如專利第3,3 5 7,1 09號公報所記載，爲提高尺寸穩定性，交聯劑雖然也可使用多元醛’但是最好是使用硼酸類。 -17- 200417794 f 固膜步驟所使用之交聯劑，若使用硼酸，則也可將金屬離子添加於硼酸-碘化鉀水溶液。金屬離子係以氯化鋅爲佳，但是如日本國專利特開第2000-3 5 5 1 2號公報所記載，也可使用碘化鋅等鹵化鋅、硫酸鋅、醋酸鋅等鋅鹽，以取代碘化鋅。(Dyeing step) The dyeing step can be performed by the method described in Japanese Patent Laid-Open No. 2002-865 54. The dyeing method is not limited to the dipping method, and may be any method such as coating or spraying with iodine or a dye solution. Although there are no particular restrictions on the dichroic materials that can be used for dyeing, it is preferable to use iodine in order to obtain a polarizing plate with high contrast. The dyeing step is preferably performed in a liquid phase. If iodine is used, the PVA film is immersed in an aqueous solution of iodine-potassium iodide to implement 16-200417794. The iodine content is from 0.05 to 20 g / L, the potassium iodide content is from 3 to 2000 g / L, and the mass ratio of iodine to potassium iodide is preferably from 1 to 25,000. The dyeing time is preferably 10 to 1,200 seconds, and the liquid temperature is 10 to 60. (^ Is better. Also, it is preferable to set iodine to 0.5 to 2 g / liter, potassium iodide to 30 to 20 g / liter, mass ratio of iodine to potassium iodide from 30 to 120, and dyeing time to 30 to 600. In seconds, the liquid temperature is 20 to 50 ° C. As described above, it is also effective to add boron compounds such as boric acid and borax as a film-fixing agent, and to perform the dyeing step and the film-fixing step described later at the same time. It is better to add 1 to 30 times by mass ratio. In addition, it is also effective to add a dichroic pigment in this step, and its amount is preferably from 0.00 to 1 g / liter. In addition, the amount of It is important to maintain a constant amount of additives in order to maintain polarizing performance. Therefore, when manufacturing in a continuous manner, it is better to manufacture while supplementing iodine, potassium iodide, boric acid, dichroic pigments, etc. The supplement is made of solution or solid It can be implemented in any state. When it is added in the solution state, it can also be made into a high concentration, and then added dropwise if necessary. (Film-Fixing Step) The film-fixing step is performed by immersing in a crosslinking agent solution or coating the solution to Make it cross-linked The method of the agent is preferred. In addition, as described in Japanese Patent Application Laid-Open No. 11-52130, the solid film step may be divided into several times for implementation. The cross-linking agent may be reissued by the U.S. Reissue Patent No. 232, As described in the No. 8 9 7 specification, and as disclosed in the Patent No. 3, 3 5 7, 1 09, in order to improve the dimensional stability, although a polyvalent aldehyde may be used as the cross-linking agent, boric acid is preferably used. -17- 200417794 f The cross-linking agent used in the solid film step, if boric acid is used, metal ions can also be added to the boric acid-potassium iodide aqueous solution. The metal ion is preferably zinc chloride, but as described in Japanese Patent Laid-Open No. As described in JP 2000-3 5 5 1 2, zinc halides such as zinc iodide, zinc sulfate, and zinc salts such as zinc acetate may be used instead of zinc iodide.

最好是以先製備添加氯化鋅之硼酸-碘化鉀水溶液，然後使PVA膜浸漬以實施固膜爲佳。硼酸係以1至1〇〇克/公升，碘化鉀係以1至120克/公升，氯化鋅係以〇.〇1至10 克/公升，固膜時間係以10至1，2 0 0秒鐘爲佳，液溫度係以10至60 °C爲佳。進一步更佳爲：硼酸爲10至80克/公升，碘化鉀爲5至100克/公升，氯化鋅爲0.02至8克/公升，固膜時間爲30至600秒鐘爲佳，液溫度爲20至50 。如上所述，在本步驟中也可添加二色性色素以同時進行染色步驟，關於其詳細已經說明。 (拉伸步驟）Preferably, a boric acid-potassium iodide aqueous solution to which zinc chloride is added is first prepared, and then the PVA film is immersed to implement the solid film. Boric acid is 1 to 100 g / L, potassium iodide is 1 to 120 g / L, zinc chloride is 0.01 to 10 g / L, and the solid film time is 10 to 1,200 seconds. A bell is preferred, and the liquid temperature is preferably 10 to 60 ° C. Even more preferably: 10 to 80 g / L of boric acid, 5 to 100 g / L of potassium iodide, 0.02 to 8 g / L of zinc chloride, preferably 30 to 600 seconds of film fixing time, and 20 liquid temperature Up to 50. As described above, a dichroic dye may be added in this step to perform the dyeing step at the same time, and the details have been described. (Stretching step)

拉伸係如上述，經調整成在拉伸後能成爲小於22微米之偏光膜後，即可使用如美國專利第2,454,5 1 5號說明書等所記載之單軸向拉伸法。在本發明中，也可使用如日本國專利特開第2002-865 54號公報所記載之依照拉幅方式之斜向拉伸法。以下就本發明所使用之斜向拉伸法說明如下。第1圖係以槪括俯視圖展示將聚合物薄膜予以斜向拉伸的方法之典型例。本發明所使用之斜向拉伸法係包括以（a )所示將成卷薄膜向箭頭標記（甲）方向導入之步驟，以 -18- 200417794 (b)所示寬度方向拉伸步驟，以及以（c)所不將拉伸薄膜送往次步驟’即（乙）方向之步驟。下稱爲「拉伸步驟」時，係指包括該等（a )至（c )步驟在內，爲實施本發明之斜向拉伸法所需之全部步驟。薄膜係由（甲）方向連續導入，由上游側看在B1點始爲左側之保持裝置所保持。在此時刻，另一邊之薄膜端並未受到保持，因此在寬度方向不會產生張力。換言之，B 1點不等於本發明之實質性的保持開始點（下稱爲「實質保持開始點」）。在本發明所使用之方法中，實質保持開始點係定義爲薄膜兩端初次受到保持之點。實質保持開始點係可以由下述兩點來表示，即更下游側之保持開始點A 1，與自A 1向導入側薄膜之2 1 大致以垂直連接之直線會與相反側保持裝置之軌跡23交叉之點C1之兩點。以該點爲起點，當使兩端保持裝置以實質上之等速度搬送時，每單位時間A1就向A2、A3、、、An 移動’Cl也同樣地會向C2、C3、、、Cn移動。換言之，將在同一時刻作爲基準之保持裝置會通過之點An與Cn連接起來之直線，即等於在其時刻下之拉伸方向。在斜向拉伸法，由於如第1圖般An將相對於Cn而逐漸地落後’拉伸方向將由垂直於搬送方向緩慢地變成傾斜。本發明之實質性保持解除點（下稱爲「實質保持解除點」 )係可以下述兩點來定義，即會在更上游由保持裝置脫離的C X點’與自c x大致垂直於由C X送往次步驟的薄膜之中心線22所拉伸之直線將與相反側保持裝置之軌跡24相父之點Ay。最終的薄膜之拉伸方向角度，係取決於：在實 -19- 200417794 質性拉伸步驟之終點（實質保持解除點）之左右保持裝置之行程差Ay - Αχ (即| Ll - L2 | )，與實質保持開始點之距離W ( Cx與Ay之距離）之比率。因此，拉伸方向對於向次步驟之搬送方向所形成之傾斜角0爲tan 0 = W / ( Ay - Αχ)，即能符合tan 0 = W / I LI - L2 I之角度。第1 圖之上側薄膜端，係經過Ay點之後雖然也會保持至28，但是因爲另一端並未受到保持，所以不會產生新的寬度方向拉伸，因此1 8及28並非本發明之實質保持解除點。如上所陳，在斜向拉伸法中，在薄膜兩端之實質保持開始點係並非爲對於左右各個保持裝置之單純的咬入點。二實質保持開始點，若將經上述所定義者更嚴格地加以說明，就是連接左右任一保持點與另一保持點之直線係與被導入於保持薄膜的步驟之薄膜中心線大致成正交之點，並且該等二保持點可定義爲最位於上游者。同樣地，在本發明中二實質保持解除點，就是連接左右任一保持點與另一保持點之直線係和將送往次步驟之薄膜中心線大致成正交之點，而且該二保持點可定義爲最位於下游者。其中大致成正交，係意謂著連接薄膜中心線與左右之實質保持開始點、或實質保持解除點之直線，係在90 ±0.5°。若使用拉幅方式之拉伸機來賦予左右行程差，則由於軌道長度等之機械性限制，雖然每每會發生對於保持裝置之咬入點與實質保持開始點之較大偏差，或從保持裝置之脫離點與實質保持解除點將發生較大偏差，但是只要上述所定義之實質保持開始點與實質保持解除點間之步驟能符合 -20- 200417794 計算式（1)〔式（1): |L2-L1|>0.4W〕之條件，即可達成本發明之目的。 (乾燥步驟）乾燥條件係依照日本國專利特開第2002-865 5 4號公報所記載之方法，但是如上述，宜將溫度設定爲低於8 〇。(：，較佳爲設定爲低於70 °C。較佳的乾燥時間爲30秒鐘至60分鐘。 (保護膜貼合步驟）經由本發明製造之偏光膜，係在兩面或單面貼合保護膜以用作爲偏光板。保護膜之種類並無特殊限制，可使用纖維素醋酸酯、纖維素醋酸-丁酸酯、纖維素丙酸酯等之纖維素酯類，聚碳酸酯，聚烯烴，聚苯乙烯，聚酯等。市售品則有··富士照相膠卷公司製Fujitack，Konica公司製之三乙釀基纖維素薄3旲，日本Zeon公司製Zeonoa，日本合成橡膠公司製Arton等。其他則有例如日本國專利特開平第 8- 1 1 0402號公報或特開平第1 1 -293 1 1 6號公報所記載之非雙折射率性光學樹脂材料。對於偏光板之保護膜，係要求如透明性、適當的透濕度、低雙折射率、適當的剛性之物理性質，膜厚係從使用方便性或耐久性之觀點來考慮，則以5至5 0 〇微米爲佳，以 20至200微米爲更佳，以20至100微米爲特別佳。偏光膜與保護膜的黏著劑並無特殊限制，但是可使用 PVA系樹脂（包括導入乙醯乙醯基、磺酸基 '羧基、氧化烯等之改性PVA )或硼化合物水溶液，其中以PVA系樹脂 -21 - 200417794 爲較佳。偏光膜與保護膜之貼合，係以在即將要貼合之前供給黏著液，並以疊合偏光膜與保護膜之方式，以一對滾輪來貼合爲佳。乾燥後的黏著劑層之厚度係以〇 . 0 0〗至5微米爲佳，以0 · 0 0 5至3微米爲更佳。此外，如日本國專利特開第2001-296426號公報及特開第2 0 0 2 - 8 6 5 5 4號公報所記載，如欲抑制偏光膜之起因於拉伸的唱片之溝狀凹凸，則以調整貼合時之偏光膜水份率爲佳，在本發明則以設定爲0.1 %至30 %爲佳。 (貼合後之乾燥步驟）貼合後之乾燥條件係按照日本國專利特開第2002-865 54 號公報所記載之方法，但是較佳的溫度範圍爲3 0。C至1 0 0 °C，較佳的乾燥時間爲30秒鐘至60分鐘。經由上述步驟所製得之偏光板，其偏光膜中之元素含量，較佳爲：碘爲0.1至3.0 g/m2，硼爲0.1至5.0 g/m2，鉀爲〇·1至2.0 g/m2，鋅爲0.001至2.0 g/m2。特別是如欲使單板透射率成爲超過41 %，則應以降低碘含量爲重要，較佳的碘含量爲0.1至1.0 g/m2。 <偏光膜用聚合物薄膜> 可在本發明使用之偏光膜用聚合物薄膜，係以PVA膜爲佳。 PVA雖然爲將聚醋酸乙烯予以皂化所製成者，但是也可含有例如可與如不飽和羧酸、不飽和磺酸、烯烴類、乙烯醚類之醋酸乙烯進行共聚合的成份。另外，也可使用含有 -22- 200417794 乙醯乙醯基、磺酸基、羧基、氧化烯基等之改性pVA。 PVA之皂化度雖然並無特殊限制，但是從溶解性等之觀點來考慮，則以8 0至1 0 0莫耳％爲佳，以9 〇至1 〇〇莫耳％爲特別佳。另外’ PVA之聚合度雖然並無特殊限制，但是以1，〇〇〇至1〇,〇〇〇爲佳，以1，500至5,000爲特別佳。 p v A膜之結晶化度並無特殊限制。舉一個實例，可使用如日本國專利第32S 1 073號公報所記載之平均結晶化度（ Xc)爲50至75質量％之PVA膜。另外，如特開平第14-236214號公報所記載，爲減少面內之色相不勻度，也可使用結晶化度低於3 8 %之PVA膜。 P V A膜之雙折射率（△ η )係以小爲佳，如日本國專利第 3 3425 1 6號公報所記載，可使用雙折射率爲低於i.o X 10·3 之PVA膜。但是如日本國專利特開第2002-228 8 3 5號公報所記載，爲在避免拉伸時的PVA膜斷裂下獲得高偏光度，也可將PVA膜之雙折射率設定爲從0.02至0.01。如日本國專利第29782 1 9號公報所記載，PVA膜之對排性係爲改良耐久性也可使用5 5 %以上之PV A膜，也可使用如日本國專利第3 3 1 7494號公報所記載氧化烯爲45至5 2.5 莫耳％之P V A膜。除此以外，對於本發明偏光板之偏光膜，可使用：如日本國專利第302 1 494號公報所記載之1，2-二醇鍵結量爲小於1 .5莫耳％之PVA膜、如日本國專利特開平第1 3 -3 1 6492 號公報所記載之超過5微米之光學異物爲每1〇〇 cm2爲少於5 00個之pVA膜，如日本國專利特開平第Μ-03 0 1 63號 -23- 200417794 公報所記載之薄膜的TD方向之熱水切斷溫度不勻度爲低於1.5 °C之PVA膜，以及由混合u質量％如日本國專利特開平第06-2 8 9225號公報所記載之增塑劑的溶液所製成爲膜的PVA膜。 PVA膜之製造方法，一般使用將PvA系樹脂溶解於水或有機溶劑所製成之原液予以澆鑄成膜之方法。原液中聚乙稀醇系樹脂之濃度，通常爲5至20質量％，將此原液以澆鑄法製膜，即可製造膜厚爲10至200微米之PVA膜。 PVA膜之製造可參考日本國專利第3 3425 1 6號、特開平第 09-3 2 85 93 號、特開第 200 1 -3028 1 7 號、特開第 2002-14440 1號之各公報來實施。 <偏光板之結構> 在本發明偏光板之保護膜表面，可設置：反射性偏光器、或例如在日本國專利特開平特開平第4-229828號、第6-75115號、特開平第8-50206號等各公報所記載LCD之用以補償視野角的光學各向異性層，或顯示器之用以提高視認性之防眩層或抗反射層，用以提高偏光板耐擦傷性之硬質塗層、用以抑制水份或氧擴散之氣體障壁性、偏光膜或黏著劑、用以提高與黏著劑的黏著力之易接著層、用以賦予潤滑性之層等之任意機能層。機能層也可設在偏光膜側，也可設在與偏光膜相反面’ 即可按照目的作適當選擇。偏光膜之保護膜，可將上述保護膜一片或將數片予以積層來使用。在偏光膜兩面也可貼合相同的保護膜，在兩面 -24- 200417794 也可分別貼合具有不同的機能、物性之保護膜。另外，也可探取只在單面貼合上述保護膜，在相反面則爲供直接貼合液晶胞’也可直接設置黏著劑層而不予貼合保護膜之方式。在此種情形下，在黏著劑外側則以設置可剝離的分離膜爲佳。 <黏著劑層> 爲供本發明之偏光板直接貼合於液晶胞所設置之上述黏著劑層’當然是必須爲光學透明，也應具有適當的黏彈性或黏著特性之層。本發明之黏著劑層，係將例如由丙烯酸系共聚物、環氧系樹脂 '聚胺甲酸酯、矽氧系聚合物、聚醚、縮丁醛系樹脂、聚醯胺系樹脂、聚乙烯醇系樹脂、含有合成橡膠等之聚合物組成物所構成之塗佈液塗在偏光膜上，並以乾燥法、化學固化法、熱固化法、熱熔融法、光固化法等使塗佈層固化即可形成。其中丙烯酸系共聚物，由於其係最易於控制其黏著物性，且具有優越的透明性、耐候性或耐久性，因此較適合於使用。 <沖切處理> 第2圖係展示先前之偏光板沖切實例，第3圖係展示具有斜向拉伸的偏光膜之本發明偏光板之沖切實例。以往之偏光板係如第2圖所示，其偏光之吸收軸7 1，即拉伸軸係與長度方向7 2 —致，與此相對，斜向拉伸之偏光板則如第 3圖所示，偏光之吸收軸，即拉伸軸係對於長度方向傾斜 45°，且該角度係與貼合於LCD中液晶胞時之偏光板吸收軸，與液晶胞本身之縱或橫向所形成之角度一致，因此可 -25- 200417794 不再需要在沖切步驟中作傾斜的沖切作業。而且，由第3 圖即可知，本發明之偏光板係由於切斷係沿長度方向成一直線，故可不必使用沖切而藉由沿長度方向之剪切即也可製造，因此具有格外優越的生產性。而且也可以捲裝進出方式與其他光學材料作貼合，使得在製造高機能光學構件時也可期待高生產性。 <用途等> 本發明之偏光板可供使用於各種用途。例如在液晶顯示裝置方面，可適合使用於配置在液晶胞兩側的兩片偏光板中至少一者。另外，特別是使配向軸之傾斜角度對於長度方向傾斜40 至5 〇°之偏光板，係適合使用於液晶顯示裝置用偏光板（例如TN (扭轉向列型）、STN (超扭轉向列型）、OCB ( 光學補償彎曲型）、R〇CB ( R-光學補償彎曲型）、ECB ( 電控雙折射型）、CPA (連續式針孔配向型）、iPS (水平電場驅動型）、VA (垂直分子排列型）之液晶模式中透射型、半透射型、反射型等顯示方式中）、有機EL顯示器之抗反射用圓偏光板等。另外，也適合與各種光學構件，例如λ /4板、λ /2板等相位差膜、視野角擴大膜、防眩性膜、硬質塗層膜等組合使用。四、實施方式〔實施例〕茲爲具體說明本發明，舉實施例說明如下，但是本發明 -26- 200417794 並非受限於此等。比較例1 將平均聚合度爲2，4〇0、膜厚爲125微米之PVA膜以15 ° C離子交換水作預膨潤4 8秒鐘，並以不銹鋼製刮刀刮除表面水份後，邊以能使濃度成爲一定之方式校正濃度，邊使PVA膜以40 °C浸漬於碘0.9克/公升、碘化鉀60.0克/ 公升之水溶液5 5秒鐘，並且邊以能使濃度成爲一定之方式校正濃度，邊使PVA膜以40 °C浸漬於硼酸42.5克/公升、碘化鉀3 0克/公升之水溶液9 0秒鐘後，以不銹鋼製刮刀刮除膜兩面之多餘水份，然後導入於第1圖形態之拉幅拉伸機。將搬送速率設定爲4公尺/分鐘，送出1〇〇公尺，在 6 0 °C、95 %氣氛下拉伸至4.12倍後，使拉幅機對於拉伸方向彎曲成如第1圖所示之狀態，以後則將寬度保持於一定，邊使其收縮邊以75 °C氣氛予以乾燥後，由拉幅機脫離。此時之偏光膜厚度爲29微米，含水率爲4.〇 %。其後以截斷器從寬度方向切除邊緣3公分後，用PVA (可樂麗公司製PVA-124H) 3 %水溶液作爲黏著劑，與經皂化處理之富士照相膠卷公司製Fujitack (纖維素三醋酸酯、面內遲滯値爲3.0奈米、膜厚爲80微米）相貼合，再進一步在 70 °C加熱10分鐘以製造有效寬度650毫米、長度1〇〇公尺之捲筒形態之偏光板P-1。對於該偏光板，以島津自動記錄分光光度計UV3 1 00測定單板透射率、偏光度、在正交尼科耳時的CIE色空間之色相X、y。 -27- 200417794 偏光度係以HO代表使兩片偏光板使其吸收軸一致而相疊時之透射率（％ )，以Η 1代表使吸收軸正交而相疊時之透射率（％ )，並以下式求得： P = 〔（H0-H1)/(H0 + H1)〕W2 X 100。單板透射率、偏光度係加以視靈敏度校正，其結果展示於表1。比較例2 除將PVA膜之膜厚改爲75微米以外，其餘則與比較例1 同樣地製造偏光板P-2。此時之偏光膜厚度爲17.5微米，含水率爲3 %。實施與比較例1相同測定，其結果展示於表1。 -28 - 200417794 Π CIE色相 0.28 0.16 0.28 0.19 在正交尼科耳時之透射率 410奈米透射率 % 0.07 0.30 700奈米透射率 % 0.03 0.35 •4HC 擊偏光度 % 99.97 99.85 單板透射率 % 43.5 43.2 偏光膜膜厚微米 17.5 實施內容偏光膜乾燥溫度 oc 75 °C 75 °C 在固膜液添加二色性色素壊壊染色液添加硼酸壊偏光板 r-H P-2 比較例1 比較例2The stretching system is as described above, and the uniaxial stretching method described in the specification of U.S. Patent No. 2,454,515 can be used after the polarizing film is adjusted to be less than 22 microns after stretching. In the present invention, an oblique stretching method according to a tenter method as described in Japanese Patent Laid-Open No. 2002-865 54 may also be used. The oblique stretching method used in the present invention will be described below. Fig. 1 shows a typical example of a method of obliquely stretching a polymer film in an enclosed plan view. The oblique stretching method used in the present invention includes a step of introducing the roll film in the direction of arrow mark (a) as shown in (a), a widthwise stretching step as shown in -18-200417794 (b), and Send the stretched film to step (b) as shown in (c). When it is referred to as "stretching step" hereinafter, it means all the steps required to implement the diagonal stretching method of the present invention, including the steps (a) to (c). The film is continuously introduced from the direction (a), and it is held by the holding device on the left side from point B1 when viewed from the upstream side. At this moment, the film end on the other side is not held, so there is no tension in the width direction. In other words, the point B 1 is not equal to the substantial holding start point of the present invention (hereinafter referred to as the "substantial holding start point"). In the method used in the present invention, the substantial holding start point is defined as the point at which both ends of the film are first held. The substantial holding start point can be expressed by the following two points, that is, the holding start point A 1 on the further downstream side, and the straight line that is approximately perpendicularly connected from A 1 to the film 2 on the introduction side will follow the trajectory of the holding device on the opposite side. 23 Two points of intersection C1. With this point as the starting point, when the holding devices at both ends are transported at substantially the same speed, A1 moves to A2, A3 ,, An every unit time, and Cl also moves to C2, C3 ,, and Cn. . In other words, the straight line connecting the point An and Cn that the holding device which is the reference at the same time passes will be the stretching direction at that time. In the oblique stretching method, since An will gradually fall behind Cn as shown in Fig. 1, the stretching direction will gradually change from perpendicular to the conveying direction to oblique. The substantial holding release point of the present invention (hereinafter referred to as the "substantially holding release point") can be defined by the following two points, that is, the CX point that will be detached from the holding device further upstream from the cx point is substantially perpendicular to the CX feed The straight line stretched by the center line 22 of the film in the next step will be the point Ay that is the parent of the trajectory 24 of the holding device on the opposite side. The final stretching direction angle of the film depends on the stroke difference Ay-Αχ (ie | Ll-L2 |) of the holding device at the end of the qualitative stretching step (substantially holding the release point). , The ratio to the distance W (distance between Cx and Ay) from the starting point of substantial maintenance. Therefore, the inclination angle 0 formed by the stretching direction with respect to the conveying direction to the next step is tan 0 = W / (Ay-Αχ), that is, an angle that can meet tan 0 = W / I LI-L2 I. The upper film end in Figure 1 is maintained to 28 after passing through the Ay point, but because the other end is not maintained, no new widthwise stretching will occur, so 18 and 28 are not the essence of the present invention. Keep the release point. As described above, in the oblique stretching method, the substantial holding starting points at both ends of the film are not the simple biting points for the left and right holding devices. The starting point of substantive retention, if more strictly defined by the above definition, is that the straight line connecting any one of the left and right holding points and the other holding point is approximately orthogonal to the center line of the film introduced into the holding film step. Point, and these two holding points can be defined as the most upstream. Similarly, in the present invention, the two substantial holding release points are the points where the line system connecting any one of the left and right holding points and the other holding point is approximately orthogonal to the center line of the film to be sent to the next step, and the two holding points Can be defined as the most downstream. It is roughly orthogonal, which means the line connecting the center line of the film and the left and right substantial retention start points, or the substantial retention release point, at 90 ± 0.5 °. If a tenter-type stretching machine is used to impart a left-right stroke difference, due to mechanical restrictions such as the length of the track, a large deviation between the bite point of the holding device and the starting point of the substantial holding occurs, or from the holding device. There will be a large deviation between the break-off point and the substantial retention release point, but as long as the steps between the substantial retention start point and the substantial retention release point defined above can meet -20- 200417794 calculation formula (1) [formula (1): | L2 -L1 | > 0.4W] can achieve the purpose of the invention. (Drying step) The drying conditions are in accordance with the method described in Japanese Patent Laid-Open No. 2002-865 54, but as described above, it is preferable to set the temperature to less than 80 °. (:, It is preferably set below 70 ° C. The preferred drying time is 30 seconds to 60 minutes. (Protective film bonding step) The polarizing film manufactured by the present invention is bonded on both sides or on one side. The protective film is used as a polarizing plate. The type of the protective film is not particularly limited, and cellulose acetates such as cellulose acetate, cellulose acetate-butyrate, cellulose propionate, polycarbonate, and polyolefin can be used. , Polystyrene, polyester, etc. Commercial products include: Fujitack made by Fuji Photo Film Co., Ltd., Triethyl cellulose based thin film made by Konica Co., Zeonoa made by Zeon Co. of Japan, Arton made by Japan Synthetic Rubber Co. Others include, for example, the non-birefringent optical resin materials described in Japanese Patent Laid-Open No. 8-1 1 0402 or Japanese Patent Laid-Open No. 1-293 1 16. For protective films for polarizing plates, Physical properties such as transparency, proper moisture permeability, low birefringence, and appropriate rigidity are required. The thickness of the film is considered from the viewpoint of ease of use or durability, and it is preferably 5 to 500 microns. 20 to 200 microns is more preferred, and 20 to 100 microns Micron is particularly preferred. Adhesives for polarizing films and protective films are not particularly limited, but PVA-based resins (including modified PVA introduced with acetamidine, sulfonate 'carboxyl, alkylene oxide, etc.) or boron compounds can be used. Aqueous solution, of which PVA resin-21-200417794 is preferred. The bonding of polarizing film and protective film is to supply adhesive solution immediately before laminating, and superimpose the polarizing film and protective film in a way that It is better to adhere to the roller. The thickness of the dried adhesive layer is preferably from 0.00 to 5 microns, and more preferably from 0.5 to 3 microns. In addition, as disclosed in Japanese Patent Application In Japanese Patent Publication No. 2001-296426 and Japanese Patent Application Laid-Open No. 2 0 2-8 6 5 5 4, if the groove-like unevenness of a polarized film due to stretched records is to be suppressed, the polarized light at the time of bonding is adjusted. The film moisture content is good, and in the present invention, it is preferably set to 0.1% to 30%. (Drying step after bonding) The drying conditions after bonding are in accordance with Japanese Patent Laid-Open No. 2002-865 54 The method described, but the preferred temperature range is 30 ° C to 100 ° C, preferably dry The time is 30 seconds to 60 minutes. For the polarizing plate obtained through the above steps, the element content in the polarizing film is preferably: 0.1 to 3.0 g / m2 for iodine, 0.1 to 5.0 g / m2 for boron, and potassium 0.001 to 2.0 g / m2, zinc is 0.001 to 2.0 g / m2. In particular, if the veneer transmittance is to exceed 41%, it is important to reduce the iodine content. The preferred iodine content is 0.1 to 1.0 g / m2. &Lt; Polymer film for polarizing film > The polymer film for polarizing film which can be used in the present invention is preferably a PVA film. Although PVA is made by saponifying polyvinyl acetate, it may contain, for example, a component copolymerizable with vinyl acetate such as unsaturated carboxylic acid, unsaturated sulfonic acid, olefins, and vinyl ethers. In addition, modified pVA containing -22-200417794 acetamidine, sulfonate, carboxyl, oxyalkylene and the like can also be used. Although there is no particular limitation on the degree of saponification of PVA, from the viewpoint of solubility and the like, it is preferably 80 to 100 mol%, and particularly preferably 90 to 100 mol%. In addition, although the degree of polymerization of PVA is not particularly limited, it is preferably 1,000 to 10,000, and particularly preferably 1,500 to 5,000. The crystallinity of the p v A film is not particularly limited. As an example, a PVA film having an average crystallinity (Xc) of 50 to 75% by mass as described in Japanese Patent No. 32S 1 073 can be used. In addition, as described in Japanese Patent Application Laid-Open No. 14-236214, in order to reduce unevenness in hue in a plane, a PVA film having a degree of crystallinity of less than 38% may be used. The birefringence (Δ η) of the P V A film is preferably small. As described in Japanese Patent No. 3 3425 16, a PVA film having a birefringence lower than i.o X 10 · 3 can be used. However, as described in Japanese Patent Laid-Open No. 2002-228 8 35, in order to obtain a high degree of polarization while avoiding breakage of the PVA film during stretching, the birefringence of the PVA film can also be set from 0.02 to 0.01. . As described in Japanese Patent No. 29782 19, the opposite property of PVA film is to improve the durability. PV A film with more than 55% can also be used. Japanese Patent No. 3 3 1 7494 can also be used. The stated alkylene oxide is 45 to 5 2.5 mol% of PVA film. In addition, for the polarizing film of the polarizing plate of the present invention, a PVA film having a 1,2-diol bond content of less than 1.5 mol%, as described in Japanese Patent No. 302 1 494, As described in Japanese Patent Laid-Open No. 1 3 -3 1 6492, optical foreign substances exceeding 5 microns are pVA films with less than 5000 per 100 cm2, such as Japanese Patent Laid-open No. M-03. 0 1 63-23- 200417794 The thin film in the TD direction of the film described in the TD direction has a hot water cut temperature unevenness of less than 1.5 ° C, and a mixed u mass% such as Japanese Patent Laid-Open No. 06- A PVA film made from a solution of the plasticizer described in Japanese Patent No. 2 9225. The manufacturing method of the PVA film is generally a method in which a stock solution made by dissolving a PvA-based resin in water or an organic solvent is cast into a film. The concentration of the polyethylene resin in the dope is usually 5 to 20% by mass. Using this dope to form a film by a casting method, a PVA film having a film thickness of 10 to 200 m can be produced. For the production of PVA film, refer to the publications of Japanese Patent Nos. 3 3425 1 6, JP-A No. 09-3 2 85 93, JP-A No. 200 1 -3028 1 7 and JP-A No. 2002-14440 1. Implementation. < Structure of polarizing plate > On the surface of the protective film of the polarizing plate of the present invention, a reflective polarizer may be provided, or, for example, in Japanese Patent Laid-open Nos. Hei 4-Ki828, No. 6-75115, Hei-Kai Optical anisotropic layer for compensating viewing angle of LCDs described in various publications such as No. 8-50206, or anti-glare layer or anti-reflection layer for display for improving visibility, and for improving scratch resistance of polarizing plates Any functional layer such as a hard coating, a gas barrier to suppress the diffusion of moisture or oxygen, a polarizing film or an adhesive, an easy-adhesive layer to improve the adhesion with the adhesive, a layer to impart lubricity, etc. The functional layer may be provided on the polarizing film side or on the opposite side of the polarizing film ', and it can be appropriately selected according to the purpose. The protective film for a polarizing film can be used by laminating one or more of the above protective films. The same protective film can be attached to both sides of the polarizing film, and protective films with different functions and physical properties can also be attached to both sides. In addition, the method of laminating the above-mentioned protective film on only one side, or directly adhering to the liquid crystal cell on the opposite side can also be explored. Alternatively, an adhesive layer can be directly provided without attaching the protective film. In this case, it is preferable to provide a peelable separation membrane on the outside of the adhesive. < Adhesive layer > The above-mentioned adhesive layer 'provided for the polarizing plate of the present invention to be directly attached to a liquid crystal cell is, of course, a layer that must be optically transparent and also have appropriate viscoelasticity or adhesion characteristics. The adhesive layer of the present invention is made of, for example, an acrylic copolymer, an epoxy resin, a polyurethane, a silicone polymer, a polyether, a butyral resin, a polyamide resin, or polyethylene. A coating liquid composed of an alcohol-based resin, a polymer composition containing synthetic rubber, etc. is applied to the polarizing film, and the coating layer is formed by a drying method, a chemical curing method, a thermal curing method, a thermal melting method, a light curing method, or the like Can be formed by curing. Among them, the acrylic copolymer is more suitable for use because it is the easiest to control its adhesive properties and has excellent transparency, weather resistance, or durability. < Punching process > Fig. 2 shows an example of the prior polarizing plate punching, and Fig. 3 shows an example of the polarizing plate of the present invention having a polarizing film stretched diagonally. The conventional polarizing plate is shown in FIG. 2, and the polarizing light absorption axis 7 1, that is, the stretching axis system is consistent with the length direction 7 2. In contrast, the obliquely stretched polarizing plate is as shown in FIG. 3. As shown, the absorption axis of polarized light, that is, the stretching axis is inclined 45 ° with respect to the length direction, and the angle is the angle formed by the absorption axis of the polarizing plate when it is attached to the liquid crystal cell in the LCD and the liquid crystal cell itself Consistent, so -25- 200417794 no longer need to do inclined punching in the punching step. In addition, as can be seen from FIG. 3, the polarizing plate of the present invention is straight because it is cut along the longitudinal direction, so it can be manufactured by cutting along the longitudinal direction without using punching. Productive. In addition, it can be laminated with other optical materials in a roll-in and roll-out manner, so that high productivity can also be expected when manufacturing high-performance optical members. < Application etc. > The polarizing plate of the present invention can be used in various applications. For example, in the case of a liquid crystal display device, it can be suitably used for at least one of two polarizing plates arranged on both sides of a liquid crystal cell. In addition, particularly polarizing plates that tilt the inclination angle of the alignment axis by 40 to 50 ° in the longitudinal direction are suitable for use in liquid crystal display device polarizing plates (eg, TN (twisted nematic), STN (super twisted nematic) ), OCB (optically compensated bending type), ROCB (R-optically compensated bending type), ECB (electrically controlled birefringence type), CPA (continuous pinhole alignment type), iPS (horizontal electric field drive type), VA (Vertical molecular alignment type) in the liquid crystal mode (transmissive, semi-transmissive, reflective, and other display modes), organic EL display anti-reflection circular polarizers, etc. It is also suitable for use in combination with various optical components, such as retardation films such as λ / 4 plates and λ / 2 plates, viewing angle widening films, anti-glare films, and hard coating films. 4. Embodiments [Examples] The present invention will be described in detail. Examples are described below, but the present invention is not limited to these. Comparative Example 1 A PVA film having an average degree of polymerization of 2,400 and a film thickness of 125 microns was pre-swelled with ion-exchanged water at 15 ° C for 4 8 seconds, and the surface water was scraped off with a stainless steel blade. Correct the concentration so that the concentration becomes constant, while immersing the PVA film at 40 ° C in an aqueous solution of 0.9 g / L of iodine and 60.0 g / L of potassium iodide for 5 5 seconds, and correct it so that the concentration becomes constant. Concentration, while immersing the PVA film at 40 ° C in an aqueous solution of 42.5 g / L of boric acid and 30 g / L of potassium iodide for 90 seconds, scrape off excess water on both sides of the film with a stainless steel scraper and then introduce it into the first Tenter drawing machine. Set the transfer rate to 4 meters / minute, send out 100 meters, and stretch to 4.12 times at 60 ° C, 95% atmosphere, and then bend the tenter to the stretching direction as shown in Figure 1. In the state shown, the width is kept constant in the future, and it is dried in an atmosphere of 75 ° C while shrinking, and then detached by a tenter. At this time, the thickness of the polarizing film was 29 μm, and the water content was 4.0%. After cutting off the edge by 3 cm from the width direction with a cutter, a 3% aqueous solution of PVA (Kuraray Co., Ltd.) 3% aqueous solution was used as an adhesive, and Fujitack (cellulose triacetate, cellulose triacetate, The in-plane hysteresis is 3.0 nanometers and the film thickness is 80 microns), and it is further heated at 70 ° C for 10 minutes to produce a polarizing plate P- in the form of a roll with an effective width of 650 mm and a length of 100 meters 1. For this polarizing plate, the Shimadzu automatic recording spectrophotometer UV3 1 00 was used to measure the veneer transmittance, polarization, and hue X, y of the CIE color space when the Nicols were crossed. -27- 200417794 Polarization refers to the transmittance (%) when HO is used to make two polarizing plates have their absorption axes aligned and overlapped, and Η 1 is the transmittance (%) when the absorption axes are made orthogonal and overlapped. , And obtain it by the following formula: P = [(H0-H1) / (H0 + H1)] W2 X 100. The board transmittance and polarization are corrected for visual acuity. The results are shown in Table 1. Comparative Example 2 A polarizing plate P-2 was produced in the same manner as in Comparative Example 1 except that the film thickness of the PVA film was changed to 75 μm. The thickness of the polarizing film at this time was 17.5 micrometers, and the moisture content was 3%. The same measurement as in Comparative Example 1 was performed, and the results are shown in Table 1. -28-200417794 Π CIE hue 0.28 0.16 0.28 0.19 Transmission 410 nm transmittance% when crossed Nicols 0.07 0.30 700 nm transmittance% 0.03 0.35 4HC polarized light% 99.97 99.85 43.5 43.2 Polarizing film thickness in micrometers 17.5 Contents of implementation Polarizing film drying temperature oc 75 ° C 75 ° C Adding dichroic pigment 壊壊 dyeing solution to solid film solution Adding boric acid 壊 polarizing plate rH P-2 Comparative example 1 Comparative example 2

200417794 由表1即可知，愈使偏光板偏光膜趨於薄膜化，則在可見光的短波側及長波側在正交尼科耳時之光漏將變得愈大，使得色相由中性灰色脫離。實施例1 將平均聚合度爲2,400、膜厚爲100微米之PVA膜以40 ° C離子交換水作預膨潤6 0秒鐘，並以不銹鋼製刮刀刮除表面水份後，邊以能使濃度成爲一定之方式校正濃度，邊使PVA膜以40 °C浸漬於碘0·7克/公升、碘化鉀60.0克/ 公升、硼酸5.0克/公升之水溶液55秒鐘，並且邊以能使濃度成爲一定之方式校正濃度，邊使PVA膜以40 °C浸漬於硼酸42.5克/公升、碘化鉀30克/公升之水溶液90秒鐘後，以不銹鋼製刮刀刮除膜兩面之多餘水份，然後導入於第1圖形態之拉幅拉伸機。將搬送速率設定爲4公尺/分鐘，送出100公尺，在60 °C、95 %氣氛下拉伸至5倍後，使拉幅機對於拉伸方向彎曲成如第1圖所示之狀態，以後則將寬度保持於一定，邊使其收縮邊在70 °C氣氛下予以乾燥後，由拉幅機脫離。此時之偏光膜厚度爲1 9微米，含水率爲4 %。其後以截斷器從寬度方向切除邊緣3公分後，用PVA(可樂麗公司製PVA-124H) 3 %水溶液作爲黏著劑，與經皂化處理之富士照相膠卷公司製Fujitack (纖維素三醋酸酯、面內遲滯値爲3 · 0奈米、膜厚爲8 0微米）相貼合，再進一步在7〇 °C加熱10分鐘以製得有效寬度65 ◦毫米、長度1〇〇公尺之捲筒形態之偏光板P-3。然後實施與比較例1相同測定，其結果係展示於表2。 -30 - 200417794 實施例2 將平均聚合度爲2,400、膜厚爲75微米之PVA膜以40 Y離子交換水作預膨潤60秒鐘，並以不銹鋼製刮刀刮除表面水份後，邊以能使濃度成爲一定之方式校正濃度，邊使PVA膜以40 °C浸漬於碘0.7克/公升、碘化鉀60.0克/ 公升、硼酸1克/公升之水溶液5 5秒鐘，並且邊以能使濃度成爲一定之方式校正濃度，邊使PVA膜以40浸漬於硼酸42.5克/公升、碘化鉀30克/公升之水溶液90秒鐘後，以不銹鋼製刮刀刮除膜兩面之多餘水份，然後導入於第 1圖形態之拉幅拉伸機。將搬送速率設定爲4公尺/分鐘，送出100公尺，在60 °C、95 %氣氛下拉伸至4.5倍後，使拉幅機對於拉伸方向彎曲成如第1圖所示之狀態，以後則將寬度保持於一定，邊使其收縮邊以65 °C氣氛予以乾燥後’由拉幅機脫離。此時之偏光膜厚度爲1 6微米，含水率爲3 %。其後以截斷器從寬度方向切除邊緣3公分後，用 PVA(可樂麗公司製PVA-124H ) 3 %水溶液作爲黏著劑，與經皂化處理之富士照相膠卷公司製Fuji tack (纖維素三醋酸酯、面內遲滯値爲3·0奈米、膜厚爲80微米）相貼合，再進一步在70 °C加熱10分鐘以製得有效寬度65 0毫米、長度100公尺之捲筒形態之偏光板P-4。然後實施與比較例1相同測定，其結果係展示於表2。實施例3 將平均聚合度爲2,4〇0、膜厚爲75微米之PVA膜以40 ° C離子交換水作預膨潤6 0秒鐘，並以不銹鋼製刮刀刮除 -31 - 200417794 表面水份後’邊以能使濃度成爲一*定之方式校正濃度，邊使PVA膜以40 °C浸漬於碘0.7克/公升、碘化鉀60.0克/ 公升、硼酸1克/公升之水溶液5 5秒鐘，並且邊以能使濃度成爲一定之方式校正濃度，邊使PVA膜以40 °C浸漬於硼酸42.5克/公升、碘化鉀30克/公升、C.I.直接黃44( λ200417794 It can be seen from Table 1 that the more the polarizing film of the polarizing plate becomes thinner, the larger the light leakage on the short-wave and long-wave sides of visible light when the Nicols are crossed, causing the hue to escape from neutral gray. . Example 1 A PVA film having an average degree of polymerization of 2,400 and a thickness of 100 micrometers was pre-swelled with ion-exchanged water at 40 ° C for 60 seconds, and the surface water was scraped off with a stainless steel scraper. Correct the concentration in a certain way, while immersing the PVA film at 40 ° C in an aqueous solution of 0.7 g / L of iodine, 60.0 g / L of potassium iodide, and 5.0 g / L of boric acid for 55 seconds, and make the concentration constant. Correct the concentration by immersing the PVA film in an aqueous solution of 42.5 g / liter of boric acid and 30 g / liter of potassium iodide at 40 ° C for 90 seconds, then scrape off excess water on both sides of the film with a stainless steel scraper, and then introduce it into the first section. Tenter drawing machine in the form of 1 picture. Set the conveying rate to 4 meters / minute, send out 100 meters, and stretch to 5 times at 60 ° C, 95% atmosphere, and then bend the tenter to the state of drawing as shown in Figure 1. After that, the width is kept constant, and it is dried in a 70 ° C atmosphere while shrinking, and then detached by a tenter. The thickness of the polarizing film at this time was 19 μm, and the water content was 4%. After cutting off the edge from the width direction by 3 cm with a cutter, a 3% aqueous solution of PVA (Kuraray Co., Ltd.) 3% aqueous solution was used as an adhesive, and Fujitack (cellulose triacetate, cellulose triacetate, The in-plane hysteresis is 3.0 nanometers and the film thickness is 80 micrometers), and it is further heated at 70 ° C for 10 minutes to obtain a roll with an effective width of 65 mm and a length of 100 meters. Morphological polarizer P-3. Then, the same measurement as in Comparative Example 1 was performed. The results are shown in Table 2. -30-200417794 Example 2 A PVA film with an average degree of polymerization of 2,400 and a film thickness of 75 microns was pre-swelled with 40 Y ion-exchanged water for 60 seconds, and the surface water was scraped off with a stainless steel blade. Correct the concentration so that the PVA film is immersed in an aqueous solution of 0.7 g / L of iodine, 60.0 g / L of potassium iodide, and 1 g / L of boric acid for 5 5 seconds at a temperature of 40 ° C. Correct the concentration in a certain way. While immersing the PVA film in a solution of boric acid 42.5 g / liter and potassium iodide 30 g / liter for 90 seconds, scrape off excess water on both sides of the film with a stainless steel scraper, and then introduce it into the first Tenter drawing machine. Set the transfer rate to 4 meters / minute, send out 100 meters, and stretch to 4.5 times at 60 ° C, 95% atmosphere, and then bend the tenter to the stretching direction as shown in Figure 1. After that, keep the width constant and dry it in an atmosphere of 65 ° C while shrinking it. At this time, the thickness of the polarizing film was 16 microns, and the moisture content was 3%. After cutting off the edges by 3 cm from the width direction with a cutter, a 3% aqueous solution of PVA (Kuraray Co., Ltd.) 3% aqueous solution was used as an adhesive, and the saponified Fuji Photo Film Co., Ltd. Fuji tack (cellulose triacetate) was used. , In-plane hysteresis is 3.0 nm, film thickness is 80 microns), and then further heated at 70 ° C for 10 minutes to obtain polarized light in the form of a roll with an effective width of 65 mm and a length of 100 meters Board P-4. Then, the same measurement as in Comparative Example 1 was performed. The results are shown in Table 2. Example 3 A PVA film with an average degree of polymerization of 2,400 and a thickness of 75 microns was pre-swelled with ion-exchanged water at 40 ° C for 60 seconds, and the surface water was scraped with a stainless steel doctor blade -31-200417794 After adjusting the concentration so that the concentration becomes constant, the PVA film was immersed in an aqueous solution of 0.7 g / liter of iodine, 60.0 g / liter of potassium iodide, and 1 g / liter of boric acid for 5 5 seconds at 40 ° C. And while correcting the concentration so that the concentration becomes constant, the PVA film was immersed in boric acid 42.5 g / liter, potassium iodide 30 g / liter, CI Direct Yellow 44 (λ at 40 ° C

max 410奈米）〇·1克/公升、C.I·直接藍1 ( λ max 650奈米 )〇·1克/公升之水溶液90秒鐘後，以不銹鋼製刮刀刮除膜兩面之多餘水份，然後導入於第1圖形態之拉幅拉伸機，以實施橫單軸向拉伸。將搬送速率設定爲4公尺/分鐘，送出100公尺，在60 °C、95 %氣氛下拉伸至4.12倍後，以後則將寬度保持於一定，邊使其收縮邊以65 °C氣氛予以乾燥後，由拉幅機脫離。此時之偏光膜厚度爲1 7.5微米，含水率爲3 %。其後以截斷器從寬度方向切除邊緣3公分後，用PVA (可樂麗公司製PVA-124H) 3 %水溶液作爲黏著劑，與經皂化處理之富士照相膠卷公司製Fujitack (纖維素三醋酸酯、面內遲滯値爲3 · 0奈米、膜厚爲8 0微米）相貼合，再進一步在70 °C加熱10分鐘以製得有效寬度 65 0毫米、長度100公尺之捲筒形態之偏光板P-5。然後實施與比較例1相同測定，結果係展示於表2。 -32- 200417794 CIE色相 0.28 0.25 1 0.23 0.28 0.26 0.24 在正交尼科時之透射率 410奈米透射率 % 0.07 0.08 0.09 700奈米透射率 % 0.07 τ—Η Ο 0.15 <(ΠΠ 擊偏光度 % 99.97 99.94 99.96 單板透射率 % 42.7 42.9 42.0 ! 偏光膜膜厚微米 2 ν〇 17.5 實施內容偏光膜乾燥溫度 oc 70 °C 65 °C 65 °C 在固膜液添加二色性色素壊壊染色液添加硼酸偏光板 cn pIh P-4 實施例1 實施例2 實施例3max 410 nm) 0.1 g / L, CI · Direct Blue 1 (λ max 650 nm) 0.1 g / L aqueous solution for 90 seconds, scrape off excess water on both sides of the film with a stainless steel scraper, Then, it is introduced into the tenter drawing machine in the form shown in Fig. 1 to perform transverse uniaxial stretching. Set the transfer rate to 4 meters / minute, send out 100 meters, and stretch to 4.12 times at 60 ° C and 95% atmosphere. After that, keep the width constant and shrink it at 65 ° C. After being dried, it was detached by a tenter. At this time, the thickness of the polarizing film was 1 7.5 microns, and the moisture content was 3%. After cutting off the edge by 3 cm from the width direction with a cutter, a 3% aqueous solution of PVA (Kuraray Co., Ltd.) 3% aqueous solution was used as an adhesive, and Fujitack (cellulose triacetate, cellulose triacetate, The in-plane hysteresis is 3.0 nm and the film thickness is 80 micrometers), and then it is further heated at 70 ° C for 10 minutes to obtain polarized light in a roll form with an effective width of 65 mm and a length of 100 meters. Plate P-5. Then, the same measurement was performed as in Comparative Example 1. The results are shown in Table 2. -32- 200417794 CIE hue 0.28 0.25 1 0.23 0.28 0.26 0.24 Transmittance at Orthogonal Nico 410 nm Transmittance% 0.07 0.08 0.09 700 nm Transmittance% 0.07 τ—Η Ο 0.15 < (ΠΠ polarized light % 99.97 99.94 99.96 Transmittance of veneer% 42.7 42.9 42.0! Polarization film thickness micron 2 ν〇 17.5 Contents of implementation Polarizing film drying temperature oc 70 ° C 65 ° C 65 ° C Liquid-added boric acid polarizer cn pIh P-4 Example 1 Example 2 Example 3

200417794 實施例4 將平均聚合度爲2,400、膜厚爲75微米之PVA膜以自 1 5至1 7 °C離子交換水作預膨潤60秒鐘，並以不銹鋼製刮刀刮除表面水份後，邊以能使濃度成爲一定之方式校正濃度，邊使PVA膜以40 °C浸漬於碘0.7克/公升、碘化鉀 6〇.〇克/公升之水溶液55秒鐘，並且邊以能使濃度成爲一定之方式校正濃度，邊使PVA膜以40 °C浸漬於硼酸42.5 克/公升、碘化鉀30克/公升、C.I.直接黃44 ( λ max 410奈米）1.0克/公升、C.I·直接藍1 ( λ max 650奈米）1·〇克/公升之水溶液9 0秒鐘後，以不銹鋼製刮刀刮除膜兩面之多餘水份，然後導入於第1圖形態之拉幅拉伸機。將搬送速率設定爲4公尺/分鐘，送出100公尺，在60 °C、95 %氣氛下拉伸至6倍後，使拉幅機對於拉伸方向彎曲成如第1圖之狀態，以後則使寬度保持於一定，邊使其收縮邊在7〇 °C 氣氛下予以乾燥後’由拉幅機脫離。此時之偏光膜厚度爲 1 2微米，含水率爲3 %。其後以截斷器從寬度方向切除邊緣3公分後，用PVA (可樂麗公司製PVA-124H ) 3 %水溶液作爲黏著劑，與經皂化處理之富士照相膠卷公司製 Fuji tack (纖維素三醋酸酯、面內遲滯値爲3.0奈米、膜厚爲80微米）相貼合，再進一步在70 °C加熱10分鐘以製得有效寬度650笔;米、長度100公尺之捲同形態之偏光板 P-6 ° 然後實施與比較例1相同測定，結果係展示於表3。實施例5 -34- 200417794 將平均聚合度爲2,400、膜厚爲75微米之PVA膜以自 15 °C至17。(：之離子交換水作預膨潤60秒鐘，並以不銹鋼製刮刀刮除表面水份後，邊以能使濃度成爲一定之方式校正濃度，邊使PVA膜以40 °C浸漬於碘〇·7克/公升、碘化鉀60.0克/公升之水溶液55秒鐘，並且邊以能使濃度成爲一定之方式校正濃度，邊使PVA膜以40 °C浸漬於硼酸 42.5克/公升、碘化鉀30克/公升、C.I.直接黃44 ( λ max 410奈米）1.5克/公升、C.I·直接藍1 ( Amax 650奈米）1.5 克/公升之水溶液90秒鐘後，以不銹鋼製刮刀刮除膜兩面之多餘水份，然後導入於第1圖形態之拉幅拉伸機。將搬送速率設定爲4公尺/分鐘，送出1〇〇公尺，在6〇。(：、95 %氣氛下拉伸至5倍後，使拉幅機彎曲成如第1圖之狀態，以後則將寬度保持於一定，邊使其收縮邊在70 °C氣氛下予以乾燥後，由拉幅機脫離。此時之偏光膜厚度爲9.5 微米，含水率爲2 %。其後以截斷器從寬度方向切除邊緣3 公分後，用PVA (可樂麗公司製PVA-124H ) 3 %水溶液作爲黏著劑，與經皂化處理之富士照相膠卷公司製Fujitack (纖維素三醋酸酯、面內遲滯値3.0奈米、膜厚爲8 0微米 )相貼合，再進一步在70 °C加熱1 〇分鐘以製得有效寬度 650毫米、長度100公尺之捲筒形態之偏光板P-7。然後實施與比較例1相同測定，結果係展示於表3。 200417794 CIE色相 0.23 ! 0.22 X 0.25 0.23 在正交尼科耳時之透過率 410奈米透射率 % 0.07 ! 0.08 700奈米透射率 % 0.15 0.17 征擊偏光度 % 99.97 99.94 單板透射率 % 41.8 41.2 偏光膜膜厚微米 (N in C\ 實施內容偏光膜乾燥溫度 0C 70 °C 70 °C 在固膜液添加二色性色素染色液添加硼酸壊摧偏光板 'Ο pL Oh 實施例4 實施例5200417794 Example 4 After pre-swelling a PVA film with an average degree of polymerization of 2,400 and a thickness of 75 microns with ion-exchanged water at 15 to 17 ° C for 60 seconds, and scraping the surface water with a stainless steel blade, While correcting the concentration so that the concentration becomes constant, the PVA film was immersed in an aqueous solution of 0.7 g / liter of iodine and 6.0 g / liter of potassium iodide at 40 ° C for 55 seconds, and the concentration was constant. Correct the concentration in a way that the PVA film is immersed in 42.5 g / L of boric acid, 30 g / L of potassium iodide, CI Direct Yellow 44 (λ max 410 nm) 1.0 g / L, CI · Direct Blue 1 (λ Max 650 nm) 1.0 g / L aqueous solution for 90 seconds, the excess water on both sides of the film was scraped off with a stainless steel scraper, and then introduced into a tenter stretcher as shown in Fig. 1. Set the transfer rate to 4 meters / minute, send out 100 meters, and stretch to 6 times at 60 ° C, 95% atmosphere, and then bend the tenter to the stretching direction as shown in Figure 1. Then, the width is kept constant, and it is dried in a 70 ° C atmosphere while being shrunk, and then it is detached from the tenter. At this time, the thickness of the polarizing film was 12 micrometers, and the moisture content was 3%. After cutting off the edge by 3 cm from the width direction with a cutter, a 3% aqueous solution of PVA (Kuraray Co., Ltd.) 3% aqueous solution was used as an adhesive, and the saponified Fuji Photo Film Co., Ltd. Fuji tack (cellulose triacetate) was used. , In-plane hysteresis is 3.0 nm, film thickness is 80 microns), and then heated at 70 ° C for 10 minutes to obtain an effective width of 650 pens; a 100-meter-long roll of the same shape of polarizing plate P-6 ° was then measured in the same manner as in Comparative Example 1. The results are shown in Table 3. Example 5 -34- 200417794 A PVA film having an average degree of polymerization of 2,400 and a film thickness of 75 micrometers was adjusted from 15 ° C to 17. (: Ion-exchanged water was pre-swelled for 60 seconds, and the surface water was scraped off with a stainless steel scraper. The PVA film was immersed in iodine at 40 ° C while the concentration was corrected to make the concentration constant. 7 g / litre, potassium iodide 60.0 g / litre aqueous solution for 55 seconds, and while calibrating the concentration so that the concentration becomes constant, the PVA film is immersed in boric acid 42.5 g / litre at 40 ° C, and potassium iodide 30 g / litre , CI Direct Yellow 44 (λ max 410 nm) 1.5 g / L, CI · Direct Blue 1 (Amax 650 nm) 1.5 g / L aqueous solution 90 seconds, scrape off excess water on both sides of the membrane with a stainless steel scraper It is then introduced into the tenter drawing machine in the form shown in Figure 1. The conveying rate is set to 4 meters / minute, 100 meters is sent out, and it is stretched to 5 times under 95% atmosphere. Then, the tenter is bent to a state as shown in Fig. 1, and thereafter the width is kept constant. After shrinking and drying in an atmosphere of 70 ° C, the tenter is released. The thickness of the polarizing film at this time 9.5 microns and 2% moisture content. Later cut off the edges by 3 cm with a cutter , Using a 3% aqueous solution of PVA (PVA-124H manufactured by Kuraray) as an adhesive, and Fujitack (cellulose triacetate, in-plane retardation 3.0 nm, film thickness 8 0) manufactured by Saponification Fuji Photo Film Co., Ltd. Micron), and further heated at 70 ° C for 10 minutes to obtain a roll-shaped polarizing plate P-7 having an effective width of 650 mm and a length of 100 meters. Then, the same measurement as in Comparative Example 1 was performed. Shown in Table 3. 200417794 CIE Hue 0.23! 0.22 X 0.25 0.23 Transmittance 410 nm Transmittance% at Cross Nicols 0.07! 0.08 700 nm Transmittance% 0.15 0.17 Strike Polarization% 99.97 99.94 Single Board Transmittance% 41.8 41.2 Polarization film thickness in micron (N in C \ Implementation content Polarizing film drying temperature 0C 70 ° C 70 ° C Add dichroic pigment staining solution to solid film liquid Add boric acid 壊 to destroy polarizing plate '0 pL Oh Implementation Example 4 Example 5

200417794 由表2及3即可知本發明之偏光板係膜厚爲小於22微米，在正交尼科耳時在7 0 0奈米之透射率爲小於0.3 %且在 4 1 〇奈米之透射率爲小於0.3 %，且單板透射率爲大於41 %，偏光度爲大於9 9.9 %，且在正交尼科耳時之色調係在 CIE (國際照明技術委員會）色空間中X値將爲從〇 · 2至 0 · 3 5，Y値將爲從0 · 2至〇 · 3 5，呈帶藍色較少之中性灰色的色調，故具有良好品質。而且實施例1及2、4及5係採用斜向拉伸，所以偏光板之良率會變得高。200417794 From Tables 2 and 3, it can be known that the film thickness of the polarizing plate of the present invention is less than 22 microns, and the transmittance at 700 nm is less than 0.3% and the transmission at 4 10 nm when Nicols are crossed. The rate is less than 0.3%, the veneer transmittance is greater than 41%, the polarization is greater than 99.9%, and the hue when crossed Nicols is in the CIE (International Commission on Illumination Technology) color space. X 値 will be From 0.2 to 0.35, Y 値 will be from 0.2 to 0.35, with a hue of neutral gray with less blue, so it has good quality. In addition, since Examples 1 and 2, 4 and 5 use oblique stretching, the yield of the polarizing plate becomes high.

接著，舉一例說明與視野角補償膜組合而成的液晶面板之實施例如下。實施例6 在直鏈烷基改性PVA ( MP-203，可樂麗公司製）30克加入水130克，甲醇40克，經攪拌、溶解後，以孔徑爲30 微米之聚丙烯製過濾器過濾，以調製配向層用塗佈液。Next, an example of a liquid crystal panel combined with a viewing angle compensation film will be described as an example. Example 6 To 30 g of linear alkyl-modified PVA (MP-203, manufactured by Kuraray) was added 130 g of water and 40 g of methanol. After stirring and dissolving, it was filtered through a polypropylene filter with a pore size of 30 μm. To prepare a coating liquid for an alignment layer.

在具有明膠薄膜（0.1微米）之打底塗層的厚度爲1〇〇微米之三乙醯基纖維素薄膜（富士照相膠卷公司製），用棒式塗佈機塗佈上述配向用塗佈液，以60 °C乾燥後，向對於MD方向成45度之方向施加摩擦處理，以形成厚度爲 0.5微米之配向層。接著，將下述結構之化合物LC-1 1.6克、苯氧基二伸乙甘醇丙烯酸酯（M-101，東亞合成公司製）〇·4克、纖維素醋酸-丁酸酯（CAB531-1、伊士曼（Eastman)化學公司製 )0.05 及光聚合引發劑（Irugacure-907、Ciba-Geigy 公司製）〇 . 〇 1克溶解於3 · 6 5克甲基乙基酮中，以作爲液晶性碟 -37- 200417794 狀化合物後，以孔徑爲1微米之聚丙烯製過濾器過濾，以調製光學各向異性層用塗佈液。〔化學式1〕On a primer layer having a gelatin film (0.1 micron), a triethyl cellulose film (manufactured by Fuji Photographic Film Co., Ltd.) having a thickness of 100 micrometers, the above-mentioned coating liquid for alignment was coated with a bar coater. After drying at 60 ° C, a rubbing treatment was applied in a direction of 45 degrees to the MD direction to form an alignment layer having a thickness of 0.5 micrometers. Next, 1.6 g of a compound of the following structure LC-1, phenoxydiethylene glycol acrylate (M-101, manufactured by Toa Synthesis) 0.4 g, cellulose acetate-butyrate (CAB531-1) , Eastman Chemical Co., Ltd.) 0.05 and photopolymerization initiator (Irugacure-907, Ciba-Geigy Co., Ltd.). 〇1 g was dissolved in 3.65 g of methyl ethyl ketone as a liquid crystal After the compound in the shape of a dish-37-200417794, it was filtered through a polypropylene filter having a pore size of 1 micron to prepare a coating solution for an optically anisotropic layer. [Chemical Formula 1]

R〇 OR 化合物LC-1 在上述配向層上，用棒式塗佈機塗佈上述光學各向異性層用塗佈液，以1 20 °C乾燥後再進一步加熱3分鐘，使液晶熟化以使碟狀化合物配向後，仍在1 20 °C之狀態下用 160 W/cm之空氣冷卻式鹵燈（Eyegraphix公司製），照射照度400 mW/cm2、照射量300 mJ/cm2之紫外線，使塗佈層固化，形成厚度爲1 · 8微米之光學各向異性層，以製得視野角補償膜。接著，以與實施例1相同方法製造偏光膜，並如第4圖所示在偏光膜9 1之一方的單面上貼合視野角補償膜94，在另一方的面上貼合經施加皂化處理之保護膜（富士照相膠卷公司製Fujitack，纖維素三醋酸酯，遲滯値爲3.〇奈米 )96、以製得偏光板92。然後’與實施例1相同方法製造偏光膜，在偏光膜9 1，之單面上貼合視野角補償膜94，，在另一方的面上貼合市售 -38- 200417794 之防眩性抗反射膜（Sanritz公司製）95，以製得偏光板93 。並且使偏光膜92、93的視野角補償膜之配向層摩擦方向與偏光層之拉伸方向成爲一致。然後，使偏光板92作爲在夾持LCD之液晶胞97的兩片偏光板中的背光98側之偏光板，使偏光板93作爲顯示側之偏光板，在視野角補償膜94、94’之光學各向異性層，均透過黏著劑而貼合液晶胞97，以製得LCD。Roor compound LC-1 on the above alignment layer, apply the coating solution for optically anisotropic layer with a bar coater, dry it at 120 ° C, and then heat it for 3 minutes to mature the liquid crystal. After the dish-like compound is aligned, the air-cooled halogen lamp (manufactured by Eyegraphix) at a temperature of 120 ° C is irradiated with 400 mW / cm2 and 300 mJ / cm2 of ultraviolet light to illuminate the coating. The cloth layer was cured to form an optically anisotropic layer having a thickness of 1.8 micrometers to prepare a viewing angle compensation film. Next, a polarizing film was manufactured in the same manner as in Example 1, and a viewing angle compensation film 94 was attached to one side of one of the polarizing films 91 as shown in FIG. 4, and the saponification was applied to the other side. The treated protective film (Fujitack manufactured by Fuji Photo Film Co., Ltd., cellulose triacetate, hysteresis ratio is 3.0 nm) 96 to obtain a polarizing plate 92. Then, a polarizing film was manufactured in the same manner as in Example 1. A viewing angle compensation film 94 was attached to one side of the polarizing film 91, and a commercially available anti-glare anti-glare film was attached to the other side. A reflective film (manufactured by Sanritz) 95 was used to obtain a polarizing plate 93. Furthermore, the rubbing direction of the alignment layer of the viewing angle compensation films of the polarizing films 92 and 93 and the stretching direction of the polarizing layer are made to coincide. Then, the polarizing plate 92 is used as the polarizing plate on the backlight 98 side of the two polarizing plates holding the LCD cell 97 of the LCD, the polarizing plate 93 is used as the polarizing plate on the display side, and the viewing angle compensation films 94, 94 ' The optically anisotropic layer is adhered to the liquid crystal cell 97 through an adhesive to obtain an LCD.

結果，經如此所製得之LCD會顯現良好的亮度、視野角特性、及視認性，且在黑底白字顯示模式時之色相以目視評估是良好。發明之效果As a result, the LCD thus produced exhibits good brightness, viewing angle characteristics, and visibility, and the hue in the white text display mode on a black background is visually evaluated as being good. Effect of the invention

本發明之偏光板，係偏光膜之厚度薄，且可防止在可見光之短波及長波側之光漏，可對於液晶顯示裝置提供良好的色相。而且經使用本發明之斜向拉伸法所製得之偏光板，係具有以在偏光板沖切步驟中可提高良率，經斜向拉伸之聚合物薄膜所製成之偏光膜，因此具有高性能且價廉。並且具有本發明偏光板之液晶顯示裝置係具有良好的亮度、視野角特性、及視認性。五、圖式簡單說明第1圖係展示斜向拉伸聚合物薄膜之方法的一實例槪括俯視圖。第2圖係展示先前之沖切偏光板方式槪括俯視圖。第3圖係展示沖切經由斜向拉伸所得偏光板之方式槪括俯視圖。 -39- 200417794 第4圖係展示實施例6之液晶顯示裝置之層結構剖面圖〇元-^iL表符號說明 (^ ) 薄膜導入方向 (^ ) 往次步驟之薄膜搬送方向 (a ) 薄膜導入步驟 (b ) 薄膜拉伸步驟 (c) 拉伸薄膜送往次步驟之步驟 A 1 薄膜對於保持裝置之咬入位置與薄膜拉伸之起點位置（實質保持開始點：右） B 1 薄膜對於保持裝置之咬入位置（左） C 1 薄膜拉伸之起點位置（實質保持開始點：左 )The polarizing plate of the present invention has a thin polarizing film, can prevent light leakage on the short-wave and long-wave sides of visible light, and can provide a good hue for a liquid crystal display device. Moreover, the polarizing plate obtained by using the oblique stretching method of the present invention is a polarizing film made of a polymer film that can be increased in yield in the step of cutting the polarizing plate and is obliquely stretched. High performance and low price. In addition, the liquid crystal display device having the polarizing plate of the present invention has good brightness, viewing angle characteristics, and visibility. V. Brief Description of Drawings Figure 1 shows an example of a method for diagonally stretching a polymer film, including a top view. Fig. 2 is a plan view showing a conventional method of punching a polarizing plate. Fig. 3 is a plan view showing a method of punching the polarizing plate obtained by oblique stretching. -39- 200417794 Fig. 4 is a cross-sectional view showing the layer structure of the liquid crystal display device of Example 6. ○-iL table symbol description (^) Film introduction direction (^) Film transfer direction to the next step (a) Film introduction Step (b) Film stretching step (c) Stretching the film and sending it to the next step A 1 The bite position of the film to the holding device and the starting position of the film stretching (substantially holding start point: right) B 1 Device biting position (left) C 1 Starting position of film stretching (substantially holding starting point: left)

Cx 薄膜脫離位置與薄膜拉伸之終點基準位置（實質保持解除點：左）Cx Film detachment position and reference position of the end point of film stretching (substantially hold release point: left)

Ay 薄膜拉伸之終點基準位置（實質保持解除點 :右） | LI - L2 | 左右之薄膜保持裝置行程差 W 在薄膜拉伸步驟終端之實質寬度 Θ 拉伸方向與薄膜行進方向所形成之角 11 導入側薄膜中央線 12 送往次步驟之薄膜中央線 13 薄膜保持裝置軌跡（左） 14 薄膜保持裝置軌跡（右） -40- 200417794 15 導入側薄膜 16 送往次步驟之薄膜 17、 1 7 9 左右之薄膜保持開始 ( 咬入 ) 點 18、 1 8 5 從左右之薄膜保持裝置之脫離點 2 1 導入側薄膜中央線 22 送往次步驟之薄膜中央線 23 薄膜保持裝置軌跡 ( 左 ) 24 薄膜保持裝置軌跡 ( 右 ) 25 導入側薄膜 26 送往次步驟之薄膜 27、 27 5 左右之薄膜保持開始 ( 咬入 ) 點 28、 28 9 從左右之薄膜保持裝置之脫離點 7 1 吸收軸 ( 拉伸軸 ) 72 長度方向 8 1 吸收軸 ( 拉伸軸 ) 82 長度方向 90 液晶顯示裝置 91、 91 ’ 偏光膜 92、 93 偏光板 94、 94” 視野角補償膜 95 防眩性抗反射膜 96 保護膜 97 液晶胞 98 背光Ay The reference position of the end point of the film stretching (substantially holding release point: right) | LI-L2 | The difference in stroke of the left and right film holding devices W The substantial width at the end of the film stretching step Θ The angle formed by the stretching direction and the film traveling direction 11 Center line of the film on the introduction side 12 Center line of the film to the next step 13 Track of the film holding device (left) 14 Track of the film holding device (right) -40- 200417794 15 Film on the introduction side 16 Sending film to the next step 17, 1 7 9 Left and right film holding start (biting) points 18, 1 8 5 Disengagement point from left and right film holding devices 2 1 Leading film center line 22 Film center line to next step 23 Film holding device track (left) 24 Film holding device trajectory (right) 25 Leading-side film 26 Films sent to next step 27, 27 5 Left and right film holding start (biting) points 28, 28 9 Release points from left and right film holding devices 7 1 Absorption shaft ( Pull (Extend axis) 72 length direction 8 1 absorption axis (stretch axis) 82 length direction 90 liquid crystal display device 91, 91 'polarizing film 92, 93 polarizing plate 94, 94 ”viewing angle compensation film 95 anti-glare anti-reflection film 96 protection Film 97 LCD cell 98 backlight

-41 --41-

Claims

200417794 拾、申請專利範圍 1· 一種偏光板，其特徵爲：在正交尼科耳時在700奈米之透射率爲從0.001 %至0·3 %，在410奈米之透射率爲從0.00 1 %至0.3 %，且偏光膜之膜厚爲從5微米妾 22微米。 2. 如申請專利範圍第1項之偏光板，其中偏光膜之膜厚爲從5微米至20微米。 3 . 如申請專利範圍第1項之偏光板，其中在正交尼科耳時在4 1 0奈米之透射率爲從0 · 0 0 1 %至〇 . 〇 8 %。 4. 如申請專利範圍第2項之偏光板，其中在正交尼科耳時在410奈米之透射率爲從0.001 %至0.08 %。 5 . 如申請專利範圍第1項之偏光板，其中單板透射率爲從41 %至50 %，偏光度爲從99.9 %至100 %。 6. 如申請專利範圍第2項之偏光板，其中單板透射率爲從41 %至50 %，偏光度爲從99.9 %至100 %。 7 · 如申請專利範圍第3項之偏光板，其中單板透射率爲從41 %至50 %，偏光度爲從99.9 %至100 %。 8 · 如申請專利範圍第4項之偏光板，其中單板透射率爲從41 %至50 %，偏光度爲從99.9 %至100 %。 9. 如申請專利範圍第1至8項中任一項之偏光板，其中在偏光膜之至少單面具有保護膜，且該保護膜之遲相軸與偏光膜之吸收軸之角度爲從10°至9 0°。 1 0.如申請專利範圍第1至8項中任一項之偏光板，其係至少具有偏光膜之長尺寸的偏光板，且偏光膜之吸收 -42- 200417794 軸係與長度方向也非爲成平行也非爲成垂直。 1 1 *如申請專利範圍第9項之偏光板，其係至少具有偏光膜之長尺寸的偏光板，且偏光膜之吸收軸係與長度方向也非爲成平行也非爲成垂直。 1 2 · —種偏光板之製造方法，其係用以製造如申請專利範圍第1至9項中任一項之偏光板，其特徵爲：包含連續地供給偏光膜用聚合物薄膜，並向該薄膜之搬送方向作單軸向拉伸以形成偏光膜之步驟。 1 3 ·如申請專利範圍第1 2項之偏光板之製造方法，其中拉伸放大率爲從4倍至1 2倍。 1 4 · 一種偏光板之製造方法，其係用以製造如上述申請專利範圍第1至1 1項之偏光板，其特徵爲··包含連續地供給偏光膜用聚合物薄膜，並邊向該薄膜之搬送方向作單軸向拉伸，或在經單軸向拉伸後，邊向與搬送方向成垂直方向作拉伸以形成偏光膜之步驟。 15 · —種偏光板之製造方法，其係用以製造如申請專利範圍第1至1 1項中任一項之偏光板，其特徵爲：包含以保持裝置保持連續地供給之偏光膜用聚合物薄膜之兩端’並邊使該保持裝置向薄膜長度方向行進邊賦予張力作拉伸以形成偏光膜之步驟，其中該步驟係以··自偏光膜用聚合物薄膜之一側端的實質保持開始點起至實質保持解除點的保持裝置之軌跡L1 及自聚合物薄膜之另一側端的實質保持開始點起至實質保持解除點的保持裝置之軌跡L2，與兩個實質保持 -43- 200417794 解除點之距離w，係符合下述式（1)之條件，且在保持聚合物薄膜之支持性、使揮發分率爲丨〇 %以上之狀態存在下作拉伸，其後以乾燥使其收縮i 0 %以上同時使揮發分率下降之方法所實施：式（1 ) : I L2 - LI I > 0.4 W。 16. 一種液晶顯示裝置，其特徵爲：將如申請專利範圍第 1至1 1項中任一項之偏光板’使用於配置在液晶胞兩側之兩片偏光板中至少一者° -44-200417794 Patent application scope 1. A polarizing plate, characterized in that the transmittance at 700 nm is 0.001% to 0.3% when it is crossed with Nicols, and the transmittance at 410 nm is from 0.00 1% to 0.3%, and the film thickness of the polarizing film is from 5 μm to 22 μm. 2. For example, the polarizing plate of the scope of patent application, wherein the thickness of the polarizing film is from 5 microns to 20 microns. 3. The polarizing plate according to item 1 of the scope of patent application, in which the transmittance at 4 10 nm when crossed Nicols is from 0.01% to 0.08%. 4. For example, the polarizing plate of item 2 of the scope of patent application, in which the transmittance at 410 nm is 0.001% to 0.08% when Nicols are crossed. 5. For the polarizing plate of the first patent application, the single plate transmission is from 41% to 50%, and the polarization is from 99.9% to 100%. 6. For the polarizing plate of the second patent application, the single-plate transmittance is from 41% to 50%, and the polarization is from 99.9% to 100%. 7 · For the polarizing plate in the third item of the patent application, the single plate transmission is from 41% to 50%, and the polarization is from 99.9% to 100%. 8 · For the polarizing plate in the fourth item of the patent application, the single-plate transmittance is from 41% to 50%, and the polarization is from 99.9% to 100%. 9. The polarizing plate according to any one of the claims 1 to 8, wherein a protective film is provided on at least one side of the polarizing film, and the angle between the retardation axis of the protective film and the absorption axis of the polarizing film is from 10 ° to 90 °. 10. The polarizing plate of any one of items 1 to 8 of the scope of application for a patent, which is a polarizing plate having at least the long dimension of a polarizing film, and the absorption of the polarizing film is not in the axis system and length direction. Parallel or vertical. 1 1 * If the polarizing plate of item 9 of the patent application scope is a polarizing plate having at least the long dimension of the polarizing film, and the absorption axis of the polarizing film is not parallel or perpendicular to the length direction. 1 2 · —A method of manufacturing a polarizing plate, which is used to manufacture a polarizing plate as in any one of claims 1 to 9 of the scope of patent application, characterized in that it comprises a polymer film for a polarizing film that is continuously supplied, and The transporting direction of the film is a step of uniaxial stretching to form a polarizing film. 1 3 · The manufacturing method of the polarizing plate as described in item 12 of the patent application scope, wherein the stretching magnification is from 4 times to 12 times. 1 4 · A method of manufacturing a polarizing plate, which is used to manufacture a polarizing plate as described in the above claims 1 to 11 in the scope of the patent application, which is characterized by comprising: continuously supplying a polymer film for a polarizing film, and The film is uniaxially stretched in the conveying direction, or after being uniaxially stretched, it is stretched in a direction perpendicular to the conveying direction to form a polarizing film. 15 · —A method of manufacturing a polarizing plate, which is used to manufacture a polarizing plate as described in any one of claims 1 to 11 in the scope of patent application, characterized in that it includes polymerization for polarizing films that is continuously supplied by a holding device. A step of forming a polarizing film by applying tension to stretch the holding device toward the length of the film while forming the polarizing film at both ends of the film, wherein the step is to substantially maintain one side of the polymer film for the self-polarizing film The trajectory L1 of the holding device from the starting point to the substantial holding release point and the trajectory L2 of the holding device from the substantially holding starting point to the substantial holding release point on the other side of the polymer film, and two substantial holdings -43- 200417794 The distance w of the release point is in accordance with the condition of the following formula (1), and the polymer film is stretched while maintaining the supportability of the polymer film so that the volatile content is more than 0%, and then dried by drying. The method of shrinking i 0% or more and reducing the volatile content ratio is implemented: Formula (1): I L2-LI I > 0.4 W. 16. A liquid crystal display device, characterized in that the polarizing plate according to any one of claims 1 to 11 of the scope of patent application is used for at least one of two polarizing plates arranged on both sides of the liquid crystal cell ° -44 -