TW201310087A - Elongated polarization plate and liquid crystal display device - Google Patents

Abstract

The present invention provides an elongated polarization plate which has an absorption axis in a width direction and can be easily reworked. Further, the present invention provides a liquid crystal display device whereby contrast inconsistency when displaying a black screen is minimized. The elongated polarization plate according to the present invention is comprised of at least an elongated transparent protection film, polarizer, and optical compensation film laminated in this order. Said polarizer has an absorption axis in a width direction and the Nz coefficient of said polarizer is within the range of 1.05 to 1.20. Further, the film thickness (d) of said optical compensation film is within a range satisfying the following formula (1): Formula (1): 10 μm < d < 40 μm.

Description

長條狀偏光板及液晶顯示裝置 Long strip polarizer and liquid crystal display device

本發明係關於長條狀偏光板及具備該長條狀偏光板之液晶顯示裝置。 The present invention relates to a long-length polarizing plate and a liquid crystal display device including the long-length polarizing plate.

液晶顯示裝置被要求削減成本。其方法有減少偏光板損耗之方法。液晶顯示裝置需要與辨識側及背光側正交之兩片偏光板。顯示裝置尤其是電視或監視器等畫面之長寬之長度不同。因此，在自通常使用之長度方向具有吸收軸之長條偏光板切出偏光板時，一方面，其尺寸被限制於偏光板寬度之長度，而無法對應於大型化。另外，效率亦差。 Liquid crystal display devices are required to cut costs. The method has a method of reducing the loss of the polarizing plate. The liquid crystal display device requires two polarizing plates orthogonal to the identification side and the backlight side. The length of the screen, such as a television or a monitor, is different in length. Therefore, when the polarizing plate is cut out from the long polarizing plate having the absorption axis in the longitudinal direction of the usual use, on the one hand, the size is limited to the length of the width of the polarizing plate, and it is not suitable for the enlargement. In addition, the efficiency is also poor.

作為改善上述問題之方法，除通常於長度方向具有吸收軸之偏光板以外，也考慮製作另一片於寬度方向具有吸收軸之偏光板，且分別自其切出辨識側用與背光側用之正交偏光板之方法。於寬度方向具有吸收軸之偏光板之製作例有專利文獻1所揭示之技術。其中，已揭示有於製作在寬度方向具有吸收軸之偏光板時會成為問題之原材料寬度方向之兩端部中之偏光度偏差獲得改善，且使用於液晶面板時獲得優異之光學特性之光學薄膜。 As a method for improving the above problem, in addition to a polarizing plate having an absorption axis in the longitudinal direction, it is also considered to produce another polarizing plate having an absorption axis in the width direction, and the identification side and the backlight side are respectively cut out therefrom. The method of making a polarizing plate. A manufacturing example of the polarizing plate having an absorption axis in the width direction is disclosed in Patent Document 1. Among them, an optical film which has improved polarization deviation in both end portions in the width direction of the raw material which is a problem in the case of producing a polarizing plate having an absorption axis in the width direction, and which is excellent in optical characteristics when used in a liquid crystal panel has been disclosed. .

然而，上述專利文獻1中，雖評價作為偏光板之光學性能，但並關於實際在面板中使用時之評價並未提及。 However, in the above Patent Document 1, although the optical performance as a polarizing plate is evaluated, it is not mentioned about the evaluation when it is actually used in a panel.

另一方面，隨著近來之液晶面板之正面對比度提高， 迄今仍成為問題之小的黑色顯示時之亮度不均變得更明顯，即使以上述專利文獻1所揭示之技術亦無法改善而亮度不均仍成為問題。 On the other hand, with the recent contrast of the front panel of the liquid crystal panel, The unevenness in brightness at the time of black display which is still a problem so far becomes more conspicuous, and even the technique disclosed in the above Patent Document 1 cannot be improved, and unevenness in brightness is still a problem.

又，為了削減成本，在將偏光板對液晶胞之貼合失敗時，為了再利用液晶胞而有必要將偏光板自液晶胞剝離並進行重工(rework)，但當偏光板中使用之光學補償膜較薄時，亦會發生偏光板破裂斷裂而在單元上產生剝離殘留而難以重工之問題。 Further, in order to reduce the cost, when the bonding of the polarizing plate to the liquid crystal cell fails, it is necessary to peel the polarizing plate from the liquid crystal cell and perform rework in order to reuse the liquid crystal cell, but optical compensation is used in the polarizing plate. When the film is thin, cracking and rupture of the polarizing plate may occur, and peeling remains on the cell, which is difficult to rework.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]特開2010-26112號公報 [Patent Document 1] JP-A-2010-26112

本發明係鑑於上述問題．狀況而完成者，其解決課題為提供在寬度方向具有吸收軸，重工容易之長條狀偏光板。另外，本發明提供黑色顯示時之亮度不均經改善之液晶顯示裝置。 The present invention is in view of the above problems. In order to solve the problem, the problem is to provide a long-length polarizing plate which has an absorption axis in the width direction and is easy to rework. Further, the present invention provides a liquid crystal display device in which luminance unevenness is improved in black display.

本發明之上述課題係藉以下之手段予以解決。 The above problems of the present invention are solved by the following means.

1.一種長條狀偏光板，其為長條狀之至少依透明保護膜、偏光器及光學補償膜之順序層合而成之長條狀偏光板，其特徵為前述偏光器在寬度方向具有吸收軸，且該偏 光器之N_Z係數在1.05~1.20之範圍內，且前述光學補償膜之膜厚d在滿足下述式(1)之範圍內，式(1)：10μm<d<40μm。 1. A long strip-shaped polarizing plate which is an elongated strip-shaped polarizing plate in which at least a transparent protective film, a polarizer and an optical compensation film are laminated in order, wherein the polarizer has a width direction The absorption axis, and the N _Z coefficient of the polarizer is in the range of 1.05 to 1.20, and the film thickness d of the optical compensation film satisfies the following formula (1), and the formula (1): 10 μm < d < 40 μm .

2.一種液晶顯示裝置，其為至少具有背光、液晶胞、與該液晶胞之辨識側及背光側各具有一片偏光板之液晶顯示裝置，其特徵為具備將如前述1所記載之長條狀偏光板裁斷所得之偏光板，且滿足下述要件(a)~(c)，(a)作為前述液晶胞之背光側之偏光板(以下稱為「偏光板1」)，係以使如前述1所記載之長條狀偏光板裁斷所得之偏光板之光學補償膜(以下稱為「光學補償膜1」)位於前述液晶胞側之方式配置，(b)前述液晶胞之辨識側之偏光板(以下稱為「偏光板2」)係以透明保護膜、偏光器及光學補償膜(以下稱為「光學補償膜2」)之順序層合而成之偏光板，且以該光學補償膜2位於該液晶胞側之方式配置，(c)以使前述偏光板1與前述偏光板2之吸收軸正交之方式配置。 2. A liquid crystal display device comprising at least a backlight, a liquid crystal cell, and a liquid crystal display device having a polarizing plate on each of an identification side and a backlight side of the liquid crystal cell, characterized in that it has a strip shape as described in the above 1 The polarizing plate is cut by the polarizing plate, and the following requirements (a) to (c) are satisfied, and (a) the polarizing plate (hereinafter referred to as "polarizing plate 1") on the backlight side of the liquid crystal cell is as described above. The optical compensation film (hereinafter referred to as "optical compensation film 1") of the polarizing plate obtained by cutting the long polarizing plate described in the first embodiment is disposed on the liquid crystal cell side, and (b) the polarizing plate on the identification side of the liquid crystal cell. (hereinafter referred to as "polarizing plate 2") is a polarizing plate in which a transparent protective film, a polarizer, and an optical compensation film (hereinafter referred to as "optical compensation film 2") are laminated in this order, and the optical compensation film 2 is used. It is disposed on the liquid crystal cell side, and (c) is disposed such that the polarizing plate 1 and the absorption axis of the polarizing plate 2 are orthogonal to each other.

3.如前述2所記載之液晶顯示裝置，其中前述液晶胞為垂直配向型液晶胞，前述光學補償膜2含有平均醯基取代度在2.0~2.6之範圍內之纖維素酯，且滿足以下述式(2)~式(5)表示之關係，式(2)：Ro(1)≦5nm式(3)：-10nm≦Rt(1)<20nm式(4)：60nm≦Ro(2)≦80nm 式(5)：190nm≦Rt(2)≦260nm[但，前述光學補償膜1及前述光學補償膜2之在23℃、55%RH、測定波長589nm測定之面內相位差值Ro分別設為Ro(1)、Ro(2)，且厚度方向之相位差值Rt分別設為Rt(1)、Rt(2)，且，Ro及Rt係以下述式定義，式(I)：Ro=(n_x-n_y)×d(nm)式(II)：Rt={(n_x+n_y)/2-n_z}×d(nm)上述式中，Ro表示光學補償膜(亦稱為相位差膜)之面內相位差值，Rt表示膜內之厚度方向之相位差，且，d表示光學補償膜之厚度，n_x表示光學補償膜之面內最大(遲相軸方向)之折射率，n_y表示光學補償膜面內之與遲相軸呈直角之方向(進相軸方向)之折射率，n_z表示厚度方向中之光學補償膜之折射率，又，測定條件係與上述相同]。 3. The liquid crystal display device according to the above 2, wherein the liquid crystal cell is a vertical alignment type liquid crystal cell, and the optical compensation film 2 contains a cellulose ester having an average thiol substitution degree in the range of 2.0 to 2.6, and satisfies the following The relationship between the formula (2) and the formula (5), the formula (2): Ro(1) ≦ 5 nm (3): -10 nm ≦ Rt (1) < 20 nm (4): 60 nm ≦ Ro (2) ≦ 80 nm (5): 190 nm ≦ Rt (2) ≦ 260 nm [However, the in-plane retardation values Ro measured at 23 ° C, 55% RH, and measurement wavelength 589 nm of the optical compensation film 1 and the optical compensation film 2 are respectively set. Ro(1) and Ro(2), and the phase difference Rt in the thickness direction is set to Rt(1) and Rt(2), respectively, and Ro and Rt are defined by the following formula: (I): Ro= (n _x -n _y ) × d (nm) Formula (II): Rt = {(n _x + n _y ) / 2 - n _z } × d (nm) In the above formula, Ro represents an optical compensation film (also called The in-plane retardation value of the retardation film, Rt represents the phase difference in the thickness direction in the film, and d represents the thickness of the optical compensation film, and n _x represents the maximum in-plane of the optical compensation film (the direction of the slow phase axis) refractive index, n _y represents the optical compensation film plane at right angles to the direction of the (fast axis direction) of the refractive index of the slow axis was, n _z table The optical compensation film of the refractive index in the thickness direction, and measurement conditions were the same as above Department].

4.如前述2或3所記載之液晶顯示裝置，其中反射型亮度提高薄膜係具備於前述背光與前述偏光板1之間，且以該反射型亮度提高薄膜之透過軸與前述偏光板1之偏光器之吸收軸呈正交之方式配置。 4. The liquid crystal display device according to the above 2 or 3, wherein the reflective brightness enhancement film is provided between the backlight and the polarizing plate 1, and the transmission axis of the reflective brightness enhancement film and the polarizing plate 1 are The absorption axes of the polarizers are arranged in an orthogonal manner.

依據本發明之上述手段，可提供一種於寬度方向具有吸收軸，且容易重工之長條狀偏光板。而且，可提供黑色顯示時之亮度不均經改善之液晶顯示裝置。 According to the above means of the present invention, it is possible to provide a long-length polarizing plate which has an absorption axis in the width direction and is easy to rework. Further, it is possible to provide a liquid crystal display device in which luminance unevenness is improved in black display.

依據本發明之上述手段，將偏光器之吸收軸設為寬度方向時，藉由使偏光器之N_Z係數成為1.05~1.20之範圍內而維持偏光器中之聚合物之絡合，提高偏光器之膜強度，在層合之光學補償膜為薄膜時，在重工時不會使偏光板產生龜裂，且不會出現剝離殘留。 According to the above aspect of the present invention, when the absorption axis of the polarizer is set to the width direction, the polarization of the polymer in the polarizer is maintained by setting the N _Z coefficient of the polarizer to be in the range of 1.05 to 1.20, thereby improving the polarizer. When the laminated optical compensation film is a film, the film strength does not cause cracking of the polarizing plate during rework, and peeling does not occur.

另外，藉由使背光側偏光板之偏光器之N_Z係數落在1.05~1.20之範圍內，在組裝於垂直配向型液晶顯示裝置時可一方面使對比性處於實用範圍內，一方面改善亮度不均。 In addition, by setting the N _Z coefficient of the polarizer of the backlight-side polarizing plate to be in the range of 1.05 to 1.20, when assembled in the vertical alignment type liquid crystal display device, on the one hand, the contrast is in a practical range, and on the other hand, the brightness is improved. Uneven.

本發明之長條狀偏光板為長條狀之至少以透明保護膜、偏光器、及光學補償膜之順序層合而成之長條狀偏光板，其特徵為前述偏光器在寬度方向具有吸收軸，該偏光器之N_Z係數在1.05~1.20之範圍內，且前述光學補償膜之膜厚d滿足式(1)：10μm<d<40μm之範圍。該特徵為與申請專利範圍第1至4項之請求項相關之發明共通之技術特徵。 The strip-shaped polarizing plate of the present invention is an elongated strip-shaped polarizing plate in which at least a transparent protective film, a polarizer, and an optical compensation film are laminated in the order of the strip, and the polarizer has absorption in the width direction. The axis, the N _Z coefficient of the polarizer is in the range of 1.05 to 1.20, and the film thickness d of the optical compensation film satisfies the range of the formula (1): 10 μm < d < 40 μm. This feature is a technical feature common to the invention related to the claims of claims 1 to 4.

本發明之長條狀偏光板可較好地應用於液晶顯示裝置。尤其，可使用於至少具有背光、液晶胞、於該液晶胞之辨識側及背光側各具一片偏光板之液晶顯示裝置，為具備將本發明之長條狀偏光板裁斷所得之偏光板，且滿足前述要件(a)~(c)之樣態之液晶顯示裝置。該情況下，前述液晶胞為垂直配向型液晶胞，前述光學補償膜2含有 平均醯基取代度在2.0~2.6之範圍內之纖維素酯，且較好滿足以前述式(2)~式(5)表示之關係。另外，反射型亮度提高薄膜較好為具備於前述背光與偏光板1之間，且該反射型亮度提高薄膜之透過軸與前述偏光板1之偏光器之吸收軸以正交之方式配置之樣態之液晶顯示裝置(參照圖1)。 The strip-shaped polarizing plate of the present invention can be preferably applied to a liquid crystal display device. In particular, a liquid crystal display device having at least one backlight, a liquid crystal cell, and a polarizing plate on the side of the liquid crystal cell and the backlight side can be provided with a polarizing plate obtained by cutting the long polarizing plate of the present invention, and A liquid crystal display device that satisfies the above requirements (a) to (c). In this case, the liquid crystal cell is a vertical alignment type liquid crystal cell, and the optical compensation film 2 contains The cellulose ester having an average thiol substitution degree in the range of 2.0 to 2.6 preferably satisfies the relationship represented by the above formulas (2) to (5). Further, the reflective brightness enhancement film is preferably provided between the backlight and the polarizing plate 1, and the transmission axis of the reflective brightness enhancement film and the absorption axis of the polarizer of the polarizing plate 1 are arranged to be orthogonal to each other. Liquid crystal display device (refer to FIG. 1).

以下，針對本發明之構成要素，及實施本發明之形態．樣態加以詳細說明。又，本申請案中，「~」意味著包含其前後所記載之數值作為下限值及上限值而使用。 Hereinafter, the constituent elements of the present invention and the form of the present invention are implemented. The form is described in detail. In the present application, "~" means that the numerical values described before and after are included as the lower limit and the upper limit.

(本發明之長條狀偏光板之概要) (Summary of the long strip polarizing plate of the present invention)

本發明之長條狀偏光板為長條狀之至少以透明保護膜、偏光器、及光學補償膜之順序層合而成之長條狀偏光板，其特徵為前述偏光器在寬度方向具有吸收軸，該偏光器之N_Z係數在1.05~1.20之範圍內，且前述光學補償膜之膜厚d滿足下述式(1)之範圍內，式(1)：10μm<d<40μm之範圍。 The strip-shaped polarizing plate of the present invention is an elongated strip-shaped polarizing plate in which at least a transparent protective film, a polarizer, and an optical compensation film are laminated in the order of the strip, and the polarizer has absorption in the width direction. In the axis, the N _Z coefficient of the polarizer is in the range of 1.05 to 1.20, and the film thickness d of the optical compensation film satisfies the following formula (1), and the formula (1): 10 μm < d < 40 μm.

又，本申請案中，所謂「長條狀」意指具有500m以上長度之薄膜。另外，自該長條狀偏光板之輥切斷成特定尺寸之四角形者稱為「薄片狀偏光板」。 In the present application, the term "long strip" means a film having a length of 500 m or more. Further, a person who cuts a square of a specific size from a roller of the long polarizing plate is referred to as a "flaky polarizing plate".

[偏光器] [Polarizer]

本發明之長條狀偏光器較好以下述式(i)定義之N_Z係數為1.05<N_Z<1.20，更好為1.05<N_Z<1.15。為1.05 以下時重工性差，為1.20以上時在面板上使用時之黑色顯示之光漏太大而無法作為黑色進行顯示。 The strip-shaped polarizer of the present invention preferably has an N _Z coefficient defined by the following formula (i) of 1.05 < N _Z < 1.20, more preferably 1.05 < N _Z < 1.15. When the hardness is 1.05 or less, the reworkability is poor. When it is 1.20 or more, the black light displayed on the panel is too large to be displayed as black.

式(i)N_Z=(n_x-n_z)/(n_x-n_y) Equation (i)N _Z =(n _x -n _z )/(n _x -n _y )

(式中，n_x為薄膜面內之遲相軸方向之折射率，n_y為薄膜面內之進相軸方向之折射率，n_z為薄膜之厚度方向之折射率)。 (wherein n _x is the refractive index in the direction of the slow axis in the plane of the film, n _y is the refractive index in the direction of the phase axis in the plane of the film, and n _z is the refractive index in the thickness direction of the film).

又，本申請案中，所謂「偏光器(亦稱為「偏光膜」)」意指具有僅使具有特定振動方向之直線偏光透過之功能之膜(薄膜)。 In the present application, the term "polarizer (also referred to as "polarizing film") means a film (film) having a function of transmitting only linearly polarized light having a specific vibration direction.

偏光器之折射率n_x、n_y、n_z可使用自動雙折射率計測定。例如，使用KOBRA-WX100/IR(王子量測設備股份有限公司製造)，在溫度23℃、濕度55%RH之環境下，於波長為1000nm求得。 The refractive indices n _x , n _y , n _{z of the} polarizer can be measured using an automatic birefringence meter. For example, it is obtained by using KOBRA-WX100/IR (manufactured by Oji Scientific Equipment Co., Ltd.) at a temperature of 23 ° C and a humidity of 55% RH at a wavelength of 1000 nm.

至於偏光器可依據目標而採用任意適當之偏光器。列舉為例如，於聚乙烯醇(PVA)系薄膜、部分甲醛化之聚乙烯醇系薄膜、乙烯．乙酸乙烯酯共聚物系部分皂化薄膜等之親水性高分子薄膜中吸附碘或雙色性染料等之雙色性物質並延伸者，聚乙烯醇之脫水處理物或聚氯化乙烯之脫鹽酸處理物等多烯系配項薄膜等。該等中，於聚乙烯醇系薄膜中吸附碘等之雙色性物質並經延伸之偏光器之偏光雙色比較高故而最好。該等偏光器之厚度並無特別限制，但較好為5~80μm左右。 As for the polarizer, any suitable polarizer can be used depending on the target. For example, it is a polyvinyl alcohol (PVA) film, a partially formaldehydeized polyvinyl alcohol film, and ethylene. In the hydrophilic polymer film such as a partially saponified film of a vinyl acetate copolymer, a dichroic substance such as iodine or a dichroic dye is adsorbed and extended, and a dehydrated material of polyvinyl alcohol or a dehydrochlorinated product of polyvinyl chloride is treated. A polyene-based compound film or the like. Among these, it is preferable to adsorb a dichroic substance such as iodine in a polyvinyl alcohol-based film and to have a relatively high polarized two-color polarizer. The thickness of the polarizers is not particularly limited, but is preferably about 5 to 80 μm.

於聚乙烯醇系薄膜中吸附碘並經延伸之偏光器可藉由例如將聚乙烯醇浸漬於碘之水溶液中而染色，且延伸至原 長度之3~7倍而製作。亦可視需要浸漬於可含有硼酸或硫酸鋅、氯化鋅等之碘化鉀等之水溶液中。另亦可視需要在染色之前將前述聚乙烯醇系薄膜浸漬於水中進行水洗。 A polarizer that adsorbs iodine in a polyvinyl alcohol-based film and is extended can be dyed by, for example, immersing polyvinyl alcohol in an aqueous solution of iodine, and extending to the original Produced by 3 to 7 times the length. It may also be immersed in an aqueous solution of potassium iodide or the like which may contain boric acid or zinc sulfate, zinc chloride or the like as needed. Alternatively, the polyvinyl alcohol-based film may be immersed in water for washing with water before dyeing.

藉由水洗聚乙烯醇系薄膜，不僅可洗淨聚乙烯醇系薄膜表面之污物或抗黏連劑，亦具有藉由使聚乙烯醇系薄膜膨潤而防止染色不均之不均勻之效果。延伸亦可在以碘染色後進行，亦可邊染色邊延伸，且亦可經延伸後再以碘染色。亦可在硼酸或碘化鉀等水溶液中或水浴中進行延伸。 By washing the polyvinyl alcohol-based film with water, not only the stain or anti-blocking agent on the surface of the polyvinyl alcohol-based film can be washed, but also the effect of preventing unevenness in dyeing unevenness by swelling the polyvinyl alcohol-based film. The extension may also be carried out after dyeing with iodine, or may be extended while dyeing, and may also be dyed with iodine after stretching. It can also be extended in an aqueous solution such as boric acid or potassium iodide or in a water bath.

[偏光板] [Polarizer]

本申請案中，所謂「偏光板」意指以透明保護膜、偏光器及光學補償膜之順序層合而成之光學薄膜。又，視情況而定，亦使用包含長條狀(輥狀)偏光板或薄片狀偏光板之意思。 In the present application, the "polarizing plate" means an optical film in which a transparent protective film, a polarizer, and an optical compensation film are laminated in this order. Further, depending on the case, a long-length (roller-shaped) polarizing plate or a sheet-shaped polarizing plate is also used.

本發明之偏光板可藉一般方法製作。較好以透明保護膜及光學補償膜，夾持在碘溶液中經浸漬延伸而製作之偏光器之兩面並貼合。貼合用之接著劑可列舉為PVA系接著劑或胺基甲酸酯系接著劑、UV硬化性接著劑等。 The polarizing plate of the present invention can be produced by a general method. Preferably, the transparent protective film and the optical compensation film are sandwiched between both sides of the polarizer which is formed by immersion stretching in an iodine solution. The adhesive for bonding can be a PVA-based adhesive, a urethane-based adhesive, a UV curable adhesive, or the like.

將本發明之透明保護膜及光學補償膜貼合於偏光器上時，較好之前先對該薄膜之表面施以易接著處理、親水化處理或電暈處理。親水化處理列舉為皂化處理、電漿處理、火焰處理、及紫外線照射處理。且，皂化處理包含酸皂化處理及鹼皂化處理，但本發明中較好使用鹼皂化處理。 When the transparent protective film and the optical compensation film of the present invention are bonded to a polarizer, it is preferred that the surface of the film is subjected to easy subsequent treatment, hydrophilization treatment or corona treatment. The hydrophilization treatment is exemplified by saponification treatment, plasma treatment, flame treatment, and ultraviolet irradiation treatment. Further, the saponification treatment includes an acid saponification treatment and an alkali saponification treatment, but in the present invention, an alkali saponification treatment is preferably used.

鹼皂化處理較好以將該薄膜直接浸漬於皂化液之槽中之方法，或將皂化液塗佈於纖維素醯化物薄膜上之方法進行。塗佈方法可列舉為浸漬塗佈法、簾流塗佈法、擠出塗佈法、棒塗佈法及E型塗佈法。鹼皂化處理塗佈液之溶劑較好選擇使皂化液對於透明支撐體塗佈之潤濕性良好，且不會因皂化液溶劑而在透明支撐體表面形成凹凸，保持良好之面形狀之溶劑。具體而言，較好為醇系溶劑，最好為異丙醇。另外，亦可使用界面活性劑之水溶液作為溶劑。鹼皂化塗佈液之鹼較好為溶解於上述溶劑中之鹼，更好為KOH、NaOH。皂化塗布液之pH較好為10以上，更好為12以上。鹼皂化時之反應條件較好為在室溫下1秒~5分鐘，更好為5秒~5分鐘，最好為20秒~3分鐘。鹼皂化反應後，較好進行以水洗或酸洗淨皂化液塗布面之水洗。 The alkali saponification treatment is preferably carried out by directly immersing the film in a tank of a saponification solution or by applying a saponification solution to a cellulose oxime film. The coating method may, for example, be a dip coating method, a curtain flow coating method, an extrusion coating method, a bar coating method, or an E-type coating method. The solvent of the alkali saponification treatment coating liquid is preferably a solvent which is excellent in wettability of the saponification liquid to the transparent support, and which does not form irregularities on the surface of the transparent support due to the saponification solution solvent, and maintains a good surface shape. Specifically, an alcohol solvent is preferred, and isopropyl alcohol is preferred. Alternatively, an aqueous solution of a surfactant may be used as a solvent. The base of the alkali saponification coating liquid is preferably a base dissolved in the above solvent, more preferably KOH or NaOH. The pH of the saponified coating liquid is preferably 10 or more, more preferably 12 or more. The reaction conditions for alkali saponification are preferably from 1 second to 5 minutes at room temperature, more preferably from 5 seconds to 5 minutes, and most preferably from 20 seconds to 3 minutes. After the alkali saponification reaction, it is preferred to carry out water washing with a water-washed or acid-washed saponification solution coated surface.

本發明中，可依據保護膜或光學補償膜之個別要求特性，在與偏光器貼合之前加工薄膜表面以提高性能。該表面處理列舉為例如防眩光處理、消炫光處理或抗反射處理作為防止表面反射而提高液晶面板之辨識性之處理；降低表面之污物附著用之抗靜電處理或防污處理；提高機械特性、提高表面硬度且提高耐溶劑性與耐化學藥品性之硬塗層處理；賦予所需色相用之著色處理等。該等處理可依據目的以習知方法進行。亦可重疊實施數種之表面處理。 In the present invention, the surface of the film can be processed to improve performance before being bonded to the polarizer depending on the individual required characteristics of the protective film or the optical compensation film. The surface treatment is exemplified by, for example, anti-glare treatment, glare treatment, or anti-reflection treatment as a treatment for preventing surface reflection from improving the visibility of the liquid crystal panel; reducing antistatic treatment or antifouling treatment for adhesion of dirt on the surface; A hard coat treatment for improving the surface hardness and improving solvent resistance and chemical resistance; coloring treatment for imparting a desired hue. These treatments can be carried out in a conventional manner depending on the purpose. Several surface treatments can also be performed in an overlapping manner.

[光學補償膜1] [Optical compensation film 1]

本發明之長條狀偏光板為長條狀之至少依透明保護 膜、偏光器及光學補償膜之順序層合而成之長條狀偏光板，其特徵為前述光學補償膜之膜厚d在滿足下述式(1)之範圍內，式(1)：10μm<d<40μm。 The strip-shaped polarizing plate of the present invention is long-shaped and at least transparently protected a strip-shaped polarizing plate in which a film, a polarizer, and an optical compensation film are laminated in this order, wherein the film thickness d of the optical compensation film satisfies the following formula (1), and the formula (1): 10 μm <d<40 μm.

該光學補償膜之在23℃、55%RH、測定波長589nm測定之面內相位差值Ro在0~10nm之範圍內，且厚度方向之相位差值Rt較好為-20~45nm之範圍內。 The in-plane retardation value Ro of the optical compensation film measured at 23 ° C, 55% RH, and the measurement wavelength of 589 nm is in the range of 0 to 10 nm, and the phase difference Rt in the thickness direction is preferably in the range of -20 to 45 nm. .

另外，該光學補償膜在使用於例如具有背光、液晶胞、在該液晶胞之辨識側及背光側上各具有一片偏光板之液晶顯示裝置中時，較好為使作為前述液晶胞之背光側之偏光板(以下稱為「偏光板1」)之將前述長條狀偏光板裁斷所得之偏光板的光學補償膜(以下稱為「光學補償膜1」)配置在前述液晶胞側之樣態。 In addition, when the optical compensation film is used in, for example, a liquid crystal display device having a backlight, a liquid crystal cell, and a polarizing plate on the side of the liquid crystal cell and the backlight side, it is preferable to use the backlight side as the liquid crystal cell. The optical compensation film (hereinafter referred to as "optical compensation film 1") of the polarizing plate obtained by cutting the long polarizing plate on the polarizing plate (hereinafter referred to as "polarizing plate 1") is disposed on the liquid crystal cell side. .

又，該光學補償膜1之在23℃、55%RH、測定波長589nm測定之面內相位差值Ro設為Ro(1)，且厚度方向之相位差值Rt設為Rt(1)時，較好滿足下述式(2)及(3)，式(2)：Ro(1)≦5nm When the in-plane retardation value Ro measured at 23 ° C, 55% RH, and measurement wavelength 589 nm is set to Ro (1), and the phase difference Rt in the thickness direction is Rt (1), It is preferable to satisfy the following formulas (2) and (3), and formula (2): Ro(1) ≦ 5 nm

式(3)：-10nm≦Rt(1)<20nm Formula (3): -10 nm ≦ Rt (1) < 20 nm

又，Ro及Rt下以下述式定義， Also, Ro and Rt are defined by the following formula,

式(I)：Ro=(n_x-n_y)×d(nm) Formula (I): Ro = (n _{x -} n _y ) × d (nm)

式(II)：Rt={(n_x+n_y)/2-n_z}×d(nm) Formula (II): Rt={(n _x +n _y )/2-n _z }×d(nm)

上述式中，Ro表示光學補償膜之面內相位差值，Rt表示膜內之厚度方向之相位差，且，d表示光學補償膜之 厚度，n_x表示光學補償膜之面內最大(遲相軸方向)之折射率，n_y表示光學補償膜面內之與遲相軸呈直角之方向(進相軸方向)之折射率，n_z表示厚度方向中之光學補償膜之折射率。又，測定條件係與上述相同。 In the above formula, Ro represents the in-plane retardation value of the optical compensation film, Rt represents the phase difference in the thickness direction in the film, and d represents the thickness of the optical compensation film, and n _x represents the in-plane maximum of the optical compensation film (lattic phase) The refractive index in the axial direction, n _y represents the refractive index in the direction of the optical compensation film in the direction perpendicular to the slow axis (the direction of the phase axis), and n _z represents the refractive index of the optical compensation film in the thickness direction. Further, the measurement conditions were the same as described above.

光學補償膜1中使用之樹脂列舉為纖維素酯樹脂、丙烯酸樹脂、環烯烴系樹脂等。其中，以含有丙烯酸樹脂者較佳。 The resin used in the optical compensation film 1 is exemplified by a cellulose ester resin, an acrylic resin, a cycloolefin resin, or the like. Among them, those containing an acrylic resin are preferred.

可使用於該光學補償膜之丙烯酸樹脂亦包含甲基丙烯酸樹脂。至於樹脂並無特別限制，但較好為由甲基丙烯酸甲酯單位50~99質量%，及可與其共聚合之其他單體單位1~50質量%所組成者。 The acrylic resin used in the optical compensation film may also contain a methacrylic resin. The resin is not particularly limited, but is preferably composed of 50 to 99% by mass of methyl methacrylate unit and 1 to 50% by mass of other monomer units copolymerizable therewith.

可共聚合之其他單體列舉為烷基數之碳數為2~18之甲基丙烯酸烷酯、烷基數之碳數為1~18之丙烯酸烷酯、丙烯酸、甲基丙烯酸等之α、β-不飽和酸、馬來酸、富馬酸、衣康酸等含不飽和基之二元羧酸，苯乙烯、α-甲基苯乙烯、核取代之苯乙烯等芳香族乙烯化合物，丙烯腈、甲基丙烯腈等之α、β-不飽和腈，馬來酸酐、馬來醯亞胺、N-取代之馬來醯亞胺、戊二酸酐等，該等可單獨使用，或併用兩種以上使用。 Other monomers which can be copolymerized are exemplified by alkyl methacrylate having an alkyl number of 2 to 18, alkyl acrylate having an alkyl number of 1 to 18, α, β- of acrylic acid, methacrylic acid or the like. An aromatic vinyl compound containing an unsaturated group such as an unsaturated acid, maleic acid, fumaric acid or itaconic acid, styrene, α-methylstyrene, or a phenol substituted by a nucleus, acrylonitrile, α,β-unsaturated nitrile such as methacrylonitrile, maleic anhydride, maleimide, N-substituted maleimide, glutaric anhydride, etc., which may be used alone or in combination of two or more. use.

該等中，以丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸正丁酯、丙烯酸第二丁酯、丙烯酸2-乙基己酯等較佳，最好使用丙烯酸甲酯或丙烯酸正丁酯。 Among these, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, second butyl acrylate, 2-ethylhexyl acrylate, etc. are preferred, and methyl acrylate or butyl acrylate is preferably used. ester.

丙烯酸樹脂可使用市售者。列舉為例如DELPET 60N、80N(旭化成化學(股)製造)、DIANAL BR52、 BR80、BR83、BR85、BR88(三菱縲縈(股)製造)、KT75(電氣化學工業(股)製造)等。 Acrylic resins can be used commercially. Listed as, for example, DELPET 60N, 80N (made by Asahi Kasei Chemicals Co., Ltd.), DIANAL BR52, BR80, BR83, BR85, BR88 (manufactured by Mitsubishi Electric Co., Ltd.), KT75 (manufactured by Electrochemical Industry Co., Ltd.), etc.

另外，本發明中，亦可使用具有內酯環構造之(甲基)丙烯酸樹脂作為丙烯酸樹脂。至於該具有內酯環構造之(甲基)丙烯酸樹脂列舉為特開2000-230016號公報、特開2001-151814號公報、特開2002-120326號公報、特開2002-254544號公報、特開2005-146084號公報等中所記載之具有內酯環構造之(甲基)丙烯酸樹脂。 Further, in the present invention, a (meth)acrylic resin having a lactone ring structure may be used as the acrylic resin. The (meth)acrylic resin having a lactone ring structure is disclosed in JP-A-2000-230016, JP-A-2001-151814, JP-A-2002-120326, and JP-A-2002-254544. A (meth)acrylic resin having a lactone ring structure described in JP-A-2005-146084.

又，丙烯酸樹脂亦可與其他樹脂摻合。其他樹脂就提高物性．耐熱性之觀點而言，較好併用纖維素酯樹脂。例如，較好以95：5~30：70之質量比含有丙烯酸樹脂與纖維素酯樹脂。較好丙烯酸樹脂(A)為50質量%以上。且，以該纖維素酯樹脂之平均醯基取代度為2.00~3.00，乙醯基取代度(ac)為0~1.89，乙醯基以外之醯基之碳數為3~7，重量平均分子量(Mw)為75000~280000之樣態較佳。 Further, the acrylic resin may be blended with other resins. Other resins improve physical properties. From the viewpoint of heat resistance, a cellulose ester resin is preferably used in combination. For example, it is preferred to contain an acrylic resin and a cellulose ester resin in a mass ratio of 95:5 to 30:70. The acrylic resin (A) is preferably 50% by mass or more. Moreover, the average thiol substitution degree of the cellulose ester resin is 2.00 to 3.00, the ethyl thiol substitution degree (ac) is 0 to 1.89, and the fluorenyl group other than the ethyl fluorenyl group has 3 to 7 carbon atoms, and the weight average molecular weight is 3 to 7. (Mw) is preferably 75,000 to 280000.

[光學補償膜2] [Optical compensation film 2]

液晶顯示裝置中使用將本發明之前述長條狀偏光板裁斷所得之偏光板時，例如使用於具有背光、液晶胞、於該液晶胞之辨識側及背光側上各具一片偏光板之樣態之液晶顯示裝置中使用時，前述液晶胞之辨識側之偏光板(以下稱為「偏光板2」)為依透明保護膜、偏光器、及光學補償膜(以下稱為「光學補償膜2」)之順序層合而成之偏 光板，該光學補償膜2較好配置於該液晶胞側。 In the liquid crystal display device, when the polarizing plate obtained by cutting the long polarizing plate of the present invention is used, for example, it is used in a state in which a backlight, a liquid crystal cell, and a polarizing plate are provided on the identification side and the backlight side of the liquid crystal cell. In the liquid crystal display device, the polarizing plate (hereinafter referred to as "polarizing plate 2") on the side of the liquid crystal cell is a transparent protective film, a polarizer, and an optical compensation film (hereinafter referred to as "optical compensation film 2"). The order of the layers The optical compensation film 2 is preferably disposed on the liquid crystal cell side.

又，前述光學補償膜2較好含有纖維素酯。該光學補償膜2中使用之纖維素酯，就相位差展示性、耐濕性等之觀點而言，平均醯基取代度較好為1.00~2.80，更好為2.0~2.6。 Further, the optical compensation film 2 preferably contains a cellulose ester. The cellulose ester used in the optical compensation film 2 preferably has an average thiol substitution degree of from 1.00 to 2.80, more preferably from 2.0 to 2.6, from the viewpoints of phase difference display property and moisture resistance.

又，本發明之纖維素酯為多數之β-葡萄糖分子以β-1,4-糖苷(glycoside)鍵而聚合成直鏈狀之樹脂。以該β-1,4-糖苷鍵構成纖維素之葡萄糖單位具有於2位、3位及6位游離之羥基(氫氧基)。因此，本發明之纖維素酯樹脂為以醯基酯化該等羥基(氫氧基)之一部分或全部之聚合物(樹脂)。 Further, the cellulose ester of the present invention is a resin in which a large number of β-glucose molecules are polymerized into a linear chain by a β-1,4-glycoside bond. The glucose unit which constitutes cellulose by the β-1,4-glycosidic bond has a hydroxyl group (hydroxyl group) which is free at the 2, 3 and 6 positions. Therefore, the cellulose ester resin of the present invention is a polymer (resin) which partially or whollys one of the hydroxyl groups (hydroxyl groups) with a mercapto group.

所謂「醯基取代度」係表示針對重複單位之葡萄糖之2位、3位及6位，羥基(氫氧基)經酯化之比例之合計。具體而言，以纖維素酯之2位、3位及6位之各羥基(氫氧基)為100%酯化時取代度分別為1。因此，纖維素酯之2位、3位及6位之全部經100%酯化時，取代度為最大的3。 The term "thiol substitution degree" means the total ratio of the hydroxyl group (hydroxyl group) esterified to the 2, 3, and 6 positions of the repeating unit of glucose. Specifically, the degree of substitution is 1 when the hydroxyl groups (hydroxyl groups) of the 2, 3, and 6 positions of the cellulose ester are 100% esterified. Therefore, when all of the 2, 3, and 6 positions of the cellulose ester are 100% esterified, the degree of substitution is the largest 3.

本申請案中，所謂「平均醯基取代度」意指以構成纖維素酯之複數種葡萄糖單位之醯基取代度以每單位之平均值表現之醯基取代度。又，本申請案中，特定之醯基，例如乙醯基、丙醯基等之取代度之平均值，於如「乙醯基取代度」、「丙醯基取代度」等，分別以「平均」概略表現。 In the present application, the "average thiol substitution degree" means the thiol substitution degree expressed by the average value per unit of the thiol substitution degree of a plurality of glucose units constituting the cellulose ester. Further, in the present application, the average value of the degree of substitution of a specific thiol group, such as an ethyl sulfonyl group, a propyl fluorenyl group, etc., is, for example, "the degree of substitution of the ethyl thiol group" and the degree of substitution of the propyl group, etc., respectively. Average "general performance.

醯基取代度之測定方法可依據ASTM-D817-96測定。 The method for determining the degree of substitution of thiol can be determined in accordance with ASTM-D817-96.

至於醯基可列舉為乙醯基、丙醯基、丁醯基、戊醯基、己醯基、辛醯基、癸醯基、十二烷醯基、十三烷醯基、十四烷醯基、十六烷醯基、十八烷醯基、異丁醯基、第三丁醯基、環己烷羰基、油醯基、苯甲醯基、萘羰基、桂皮醯基等。 As the fluorenyl group, it may be exemplified by an ethyl group, a propyl group, a butyl group, a butyl group, a pentyl group, a hexyl group, a octyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, and a hexadecane. An alkanoyl group, an octadecyl fluorenyl group, an isobutyl fluorenyl group, a tert-butyl fluorenyl group, a cyclohexanecarbonyl group, an oil fluorenyl group, a benzamyl group, a naphthalenecarbonyl group, a cinnamyl group, and the like.

該等中，更好為乙醯基、丙醯基、丁醯基、十二烷醯基、十八烷醯基、第三丁醯基、油醯基、苯甲醯基、萘羰基、桂皮醯基等，最好為乙醯基、丙醯基、丁醯基(醯基為碳原子數2~4之情況)，又最好為乙醯基。 Among these, it is more preferably an ethyl group, a propyl group, a butyl group, a dodecyl group, an octadecyl group, a tert-butyl group, an oil group, a benzepidine group, a naphthylcarbonyl group, a cinnamyl group, or the like. Preferably, it is an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group (the fluorenyl group is a carbon number of 2 to 4), and preferably an acetyl group.

又，脂肪族醯基之情況下，就纖維素酯合成之生產性、成本之觀點而言，碳數較好為2~6，更好為2~4。且，未以醯基取代之部分較好通常以羥基(氫氧基)存在。 Further, in the case of an aliphatic sulfhydryl group, the carbon number is preferably from 2 to 6, more preferably from 2 to 4, from the viewpoint of productivity and cost of cellulose ester synthesis. Further, a portion which is not substituted with a mercapto group is preferably present as a hydroxyl group (hydroxyl group).

本發明中，該光學補償膜2之相位差值Ro為60~80nm，Rt為190~260nm，就擴大垂直配向型液晶顯示裝置之視角而言較佳。亦即，較好滿足以下述式(4)及(5)表示之關係。 In the present invention, the phase difference Ro of the optical compensation film 2 is 60 to 80 nm, and Rt is 190 to 260 nm, which is preferable in terms of expanding the viewing angle of the vertical alignment type liquid crystal display device. That is, the relationship expressed by the following formulas (4) and (5) is preferably satisfied.

式(4)：60nm≦Ro(2)≦80nm Formula (4): 60nm≦Ro(2)≦80nm

式(5)：190nm≦Rt(2)≦260nm Formula (5): 190 nm ≦ Rt (2) ≦ 260 nm

但，前述光學補償膜2之在23℃、55%RH、測定波長589nm測定之面內相位差值Ro設為Ro(2)，且厚度方向之相位差值Rt設為Rt(2)。且，Ro及Rt係以前述式(I)及(II)定義。 However, the in-plane retardation value Ro measured at 23 ° C, 55% RH, and measurement wavelength 589 nm of the optical compensation film 2 is set to Ro (2), and the phase difference Rt in the thickness direction is set to Rt (2). Further, Ro and Rt are defined by the above formulae (I) and (II).

膜厚d並無特別限制，較好為50~80μm。 The film thickness d is not particularly limited, and is preferably 50 to 80 μm.

且，光學補償膜2較好含有後述之葡萄糖化合物。 Further, the optical compensation film 2 preferably contains a glucose compound described later.

為獲得本發明中之目標相位差值(遲滯值)Ro、Rt，較好光學補償膜係作成本發明之構成，進而藉由輸送張力之控制、延伸操作進行折射率控制。 In order to obtain the target phase difference values (hysteresis values) Ro and Rt in the present invention, a preferable optical compensation film is constructed by the present invention, and the refractive index control is performed by the control of the conveyance tension and the stretching operation.

例如，藉由降低或提高長度方向之張力可改變相位差值(遲滯值)。 For example, the phase difference value (hysteresis value) can be changed by lowering or increasing the tension in the length direction.

又，對於薄膜之長度方向(製膜方向)及與其在薄膜面內正交之方向，亦即寬度方向，可依序或同時進行雙軸延伸或單軸延伸。 Further, biaxial stretching or uniaxial stretching may be performed sequentially or simultaneously with respect to the longitudinal direction of the film (film forming direction) and the direction orthogonal to the film surface, that is, the width direction.

延伸網片之方法並無特別限制。列舉為例如使複數之輥具有周速差，於其間利用輥之周速差於縱向延伸之方法，夾住或以針固定網片之兩端，於行進方向擴大夾具或針之間隔而於縱向方向延伸之方法，同樣地於橫向方向擴大並於橫向延伸之方法，或於縱橫同時擴大並朝縱橫兩方向延伸之方法。當然該等方法亦可組合使用。 The method of extending the mesh is not particularly limited. For example, the plurality of rolls have a peripheral speed difference, and the circumferential speed difference of the rolls is used to extend the longitudinal direction therebetween, and the ends of the mesh sheets are clamped or fixed by needles, and the distance between the clamps or the needles is enlarged in the traveling direction. The method of extending the direction is similarly a method of expanding in the lateral direction and extending in the lateral direction, or expanding in the vertical and horizontal directions and extending in both the longitudinal and lateral directions. Of course, these methods can also be used in combination.

且，所謂拉幅法之情況，由於以直線驅動方式驅動夾具部分時可順利進行延伸，而可減少破裂之危險性故較佳。 Further, in the case of the tenter method, since the clip portion can be smoothly extended when the grip portion is driven by the linear driving method, the risk of cracking can be reduced, which is preferable.

製膜步驟之該等寬度保持或橫向方向之延伸較好以拉幅機進行，可為針式拉幅機亦可為夾具拉幅機。 The width of the film forming step or the extension of the transverse direction is preferably carried out by a tenter, and may be a pin tenter or a clip tenter.

本發明之光學補償膜之遲相軸或進相軸存在於薄膜面內，且與製膜方向之角度設為θ1時，θ1較好為-1°以上+1°以下，更好為-0.5°以上+0.5°以下。 When the retardation axis or the phase axis of the optical compensation film of the present invention is present in the film surface, and the angle with the film formation direction is θ1, θ1 is preferably -1 or more and +1 or less, more preferably -0.5. °+0.5° or less.

該θ1作為配向角定義時，θ1之測定可使用自動雙折 射計KOBRA-21ADH(王子量測設備)進行。θ1滿足上述各關係，則可在顯示畫面中獲得高的亮度，有助於抑制或防止光漏，有助於在彩色液晶顯示裝置中獲得忠實之顏色再現。 When θ1 is defined as the alignment angle, the measurement of θ1 can use automatic bi-folding. The shot meter KOBRA-21ADH (Prince Measurement Equipment) was carried out. When θ1 satisfies the above relationships, high luminance can be obtained on the display screen, which contributes to suppressing or preventing light leakage, and contributes to obtaining faithful color reproduction in the color liquid crystal display device.

[透明保護膜1] [Transparent protective film 1]

本申請案中，所謂「透明保護膜」為偏光板之構成構件，意指擔任在貼合於偏光器時抑制偏光器之尺寸變化或物性變化之角色之薄膜。例如，一般使用三乙醯基纖維素(TAC)薄膜等之樹脂膜。本發明中可使用之樹脂基材之細節敘述於後。 In the present application, the "transparent protective film" is a constituent member of the polarizing plate, and means a film which suppresses the dimensional change or physical property change of the polarizer when it is bonded to the polarizer. For example, a resin film such as a triethylenesulfonated cellulose (TAC) film is generally used. Details of the resin substrate which can be used in the present invention are described later.

又，作為透明保護膜較好使用例如市售之光學薄膜(例如，KONICA MONITEX KC8UX、KC4UX、KC5UX、KC8UY、KC4UY、KC12UR、KC8UCR-3、KC8UCR-4、KC8UCR-5、KC8UE、KC4UE、KC4FR-3、KC4FR-4、KC4HR-1、KC8UY-HA、KC8UX-RHA，以上均為KONICA MONITA ADVANCE LAYER(股)製造)等。 Further, as the transparent protective film, for example, commercially available optical films (for example, KONICA MONITEX KC8UX, KC4UX, KC5UX, KC8UY, KC4UY, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC8UE, KC4UE, KC4FR- are preferably used. 3. KC4FR-4, KC4HR-1, KC8UY-HA, KC8UX-RHA, all of which are manufactured by KONICA MONITA ADVANCE LAYER (shares).

透明保護膜1中使用之纖維素酯樹脂，就即使溫度上升仍可抑制因薄膜收縮造成之不均發生之觀點而言，平均醯基取代度為2.70~3.00之纖維素酯樹脂之情況下之效果顯著。該推定係由於該範圍之醯基取代度之纖維素酯樹脂具有優異之耐濕性，故可見到顯著效果者。 The cellulose ester resin used in the transparent protective film 1 can suppress the occurrence of unevenness due to shrinkage of the film even if the temperature rises, and the cellulose ester resin having an average thiol substitution degree of 2.70 to 3.00 is used. The effect is remarkable. This presumption is that a cellulose ester resin having a thiol substitution degree in this range has excellent moisture resistance, so that a remarkable effect can be seen.

透明保護膜1之膜厚並無特別限制，但較好為10~40μm。 The film thickness of the transparent protective film 1 is not particularly limited, but is preferably 10 to 40 μm.

[透明保護膜2] [Transparent protective film 2]

透明保護膜2中使用之纖維素酯樹脂係如前述，為了具有保護功能，平均醯基取代度較好為2.70~3.00。 The cellulose ester resin used in the transparent protective film 2 is as described above, and the average thiol substitution degree is preferably from 2.70 to 3.00 in order to have a protective function.

透明保護膜之膜厚並無特別限制，較好為40~80μm。 The film thickness of the transparent protective film is not particularly limited, but is preferably 40 to 80 μm.

[纖維素酯] [Cellulose ester]

可使用於本發明之透明保護膜及光學補償膜中之纖維素酯可使用習知之光學薄膜中使用者，列舉為纖維素三乙酸酯、纖維素二乙酸酯、纖維素酯丙酸酯等。 The cellulose ester used in the transparent protective film and the optical compensation film of the present invention can be used by a user of a conventional optical film, which is exemplified by cellulose triacetate, cellulose diacetate, cellulose ester propionate. Wait.

纖維素酯之數平均分子量(Mn)在30000~300000之範圍獲得之薄膜之機械強度較強故較佳。更好為50000~200000者。 The mechanical strength of the film obtained by the number average molecular weight (Mn) of the cellulose ester in the range of 30,000 to 300,000 is relatively strong. Better for 50,000 to 200,000.

纖維素酯之重量平均分子量(Mw)與數平均分子量(Mn)之比Mw/Mn之值較好為1.4~3.0。 The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the cellulose ester Mw/Mn is preferably from 1.4 to 3.0.

纖維素酯之數平均分子量(Mn)、重量平均分子量(Mw)係使用凝膠滲透層析法(GPC)測定。 The number average molecular weight (Mn) and weight average molecular weight (Mw) of the cellulose ester were measured by gel permeation chromatography (GPC).

測定條件如下。 The measurement conditions are as follows.

溶劑：二氯甲烷 Solvent: dichloromethane

管柱：Shodex K806、K805、K803G(昭和電工(股)製造，三根串聯使用) Pipe column: Shodex K806, K805, K803G (made by Showa Denko (share), three in series)

管柱溫度：25℃ Column temperature: 25 ° C

試料濃度：0.1質量% Sample concentration: 0.1% by mass

檢測器：RI型號504(GL科技公司製造) Detector: RI model 504 (manufactured by GL Technology)

泵：L6000(日立製作所(股)製造) Pump: L6000 (manufactured by Hitachi, Ltd.)

流量：1.0ml/min Flow rate: 1.0ml/min

校正曲線：使用利用標準聚苯乙烯STK standard聚苯乙烯(TOSOH(股)製造)Mw=1000000~500之13種樣品獲得之校正曲線。13種樣品大致等間隔使用。 Calibration curve: A calibration curve obtained using 13 samples of standard polystyrene STK standard polystyrene (manufactured by TOSOH) Mw = 1000000 to 500 was used. Thirteen samples were used at approximately equal intervals.

纖維素酯之原料纖維素並無特別限制，可列舉為棉花棉籽絨、木材紙漿(來自針葉樹、來自闊葉樹)，洋麻(Kenaf)等。且由該等獲得之纖維素酯可以任意比例混合使用。 The cellulose raw material of the cellulose ester is not particularly limited, and examples thereof include cotton cotton linters, wood pulp (from conifers, from broadleaf trees), and kenaf (Kenaf). And the cellulose ester obtained from the above may be used in combination in any ratio.

本發明之纖維素酯可以習知方法製造。具體而言可參考特開平10-45804號公報、特開2009-161701號公報等所記載之方法合成。 The cellulose ester of the present invention can be produced by a known method. Specifically, it can be synthesized by the method described in JP-A-H05-45804, JP-A-2009-161701, and the like.

[葡萄糖化合物] [glucose compound]

本發明之光學補償膜，尤其是前述光學補償膜2，較好含有葡萄糖化合物。藉由於光學補償膜中添加葡萄糖化合物，該葡萄糖化合物發揮作為水分調整劑之作用，可使薄膜更容易收縮。 The optical compensation film of the present invention, particularly the optical compensation film 2 described above, preferably contains a glucose compound. By adding a glucose compound to the optical compensation film, the glucose compound functions as a moisture regulator, and the film can be more easily shrunk.

本發明中較好含有以下述通式(I)表示之化合物作為葡萄糖化合物。 In the present invention, a compound represented by the following formula (I) is preferably contained as a glucose compound.

(式中，R¹¹、R¹²各獨立表示碳原子數1~10之烷基，或碳原子數2~10之烯基，該等基中存在之一個CH₂基或不鄰接之兩個以上之CH₂基亦可經氧原子(O)取代，L¹表示-OCO-*、-OCH₂-*(在*側與B鍵結)、或單鍵，A、B各獨立表示可經取代之反式-1,4-伸環己基、或1,4-伸苯基，R¹³、R¹⁴各獨立表示氫原子或碳數1~10之醯基)。 (wherein R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and one CH ₂ group present in the group or two or more adjacent thereto The CH ₂ group may also be substituted by an oxygen atom (O), L ¹ represents -OCO-*, -OCH ₂ -* (bonded to the B side on the * side), or a single bond, and A and B each independently represent a substitutable The trans-1,4-cyclohexylene group or the 1,4-phenylene group, and each of R ¹³ and R ¹⁴ independently represents a hydrogen atom or a fluorenyl group having 1 to 10 carbon atoms.

至於R¹¹、R¹²較好各獨立為碳數1~10之烷基、烷氧基、烷氧基烷基或碳原子數2~10之烯基。更好為碳數1~6之烷基、烷氧基、烷氧基烷基或碳原子數2~5之烯基。又更好為乙基、正丙基、正丁基、正戊基、甲氧基、乙氧基、正丙氧基、正丁氧基或烯丙基，最好為甲氧基。該等R¹¹及R¹²可相同亦可不同。 R ¹¹ and R ^{12 are} each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alkoxyalkyl group or an alkenyl group having 2 to 10 carbon atoms. More preferably, it is an alkyl group having 1 to 6 carbon atoms, an alkoxy group, an alkoxyalkyl group or an alkenyl group having 2 to 5 carbon atoms. Further preferred is ethyl, n-propyl, n-butyl, n-pentyl, methoxy, ethoxy, n-propoxy, n-butoxy or allyl, preferably methoxy. These R ¹¹ and R ¹² may be the same or different.

L¹表示-OCO-*、-OCH₂-*(在*側與B鍵結)或單鍵，較好為-OCO-*或-OCH₂-*。 L ¹ represents -OCO-*, -OCH ₂ -* (bonded to the B side on the * side) or a single bond, preferably -OCO-* or -OCH ₂ -*.

A、B各獨立表示反式-1,4-伸環己基、或1,4-伸苯基。較好為1,4-伸苯基。A、B亦可經取代，此時之取代基舉例較好為甲基、乙基、甲氧基等，但更好為以甲基取代或未經取代。 A and B each independently represent a trans-1,4-cyclohexylene group or a 1,4-phenylene group. It is preferably 1,4-phenylene. A and B may be substituted, and the substituent at this time is preferably a methyl group, an ethyl group, a methoxy group or the like, but more preferably a methyl group or an unsubstituted group.

R¹³、R¹⁴各獨立為氫原子或碳數1~10之醯基，較好為氫原子、乙醯基、丙醯基、丁醯基、苯甲醯基，最好為氫原子或乙醯基。該等R¹³、R¹⁴各可相同亦可不同。 R ¹³ and R ^{14 are} each independently a hydrogen atom or a fluorenyl group having 1 to 10 carbon atoms, preferably a hydrogen atom, an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group or a benzamidine group, preferably a hydrogen atom or an ethyl fluorenyl group. . These R ¹³ and R ¹⁴ may be the same or different.

以上述通式(I)表示之化合物中，較好為以下述通式(II)表示之葡萄糖化合物。 Among the compounds represented by the above formula (I), a glucose compound represented by the following formula (II) is preferred.

(式中，R¹⁵、R¹⁶各獨立表示碳原子數1~6之烷基，或碳原子數2~5之烯基，該等基中存在之一個CH₂基或不鄰接之兩個以上之CH₂基亦可經O取代，L²表示-OCO-*、-OCH₂-*(在*側與伸苯基鍵結)，R¹⁷、R¹⁸各獨立表示氫原子或碳數1~10之醯基，R¹⁹、R²⁰各獨立表示氫原子、甲基或甲氧基)。 (wherein R ¹⁵ and R ¹⁶ each independently represent an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and one CH ₂ group present in the group or two or more adjacent thereto The CH ₂ group may also be substituted by O, L ² represents -OCO-*, -OCH ₂ -* (bonded to the phenyl group on the * side), and R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or a carbon number of 1~ The thiol group of 10, R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a methyl group or a methoxy group).

下述列示以通式(I)或(II)表示之化合物之具體例，但本發明絕不限定於以下具體例。又，本申請案中，Ac表示乙醯基。 Specific examples of the compound represented by the formula (I) or (II) are listed below, but the present invention is by no means limited to the following specific examples. Further, in the present application, Ac represents an ethyl group.

本發明之以通式(I)表示之化合物可依循下述反應流程圖，由(D)-葡萄糖合成。例如於J.Am.Chem. Soc.,2000,124(33),pp9756-9767中記載自(D)-葡萄糖經過乙縮醛交換、醯化、1位羥基之選擇性脫醯化而合成中間體B之方法。接著自中間體B衍生成葡萄糖化合物A之方法可使用任意之酯化反應。列舉為例如使用對應之醯鹵化物或縮合劑之方法等。獲得葡萄糖化合物B之方法係依據Carbohyd.Res.1985,135,203，或Angew.Chem.,Int.Ed.Engl.1986,25,212中所記載之方法，衍生成中間體C後，進行對應之醇與醣基化之方法等。但，本發明化合物之合成方法並不限於該例。 The compound represented by the formula (I) of the present invention can be synthesized from (D)-glucose according to the following reaction scheme. For example, at J.Am.Chem. Soc., 2000, 124 (33), pp9756-9767 describes a method for synthesizing intermediate B from (D)-glucose by acetal exchange, deuteration, and selective depurification of a hydroxyl group. The method of deriving the intermediate compound B into the glucose compound A can then use any esterification reaction. For example, a method of using a corresponding ruthenium halide or a condensing agent, or the like is exemplified. The method for obtaining the glucose compound B is carried out according to the method described in Carbohyd. Res. 1985, 135, 203, or Angew. Chem., Int. Ed. Engl. 1986, 25, 212, and after derivatization to the intermediate C, the corresponding alcohol and sugar are carried out. The method of basicization and so on. However, the method of synthesizing the compound of the present invention is not limited to this example.

本發明之纖維素組成物中，以通式(I)或(II)表示之化合物之含量相對於纖維素化合物較好為0.1~15質量%，更好為0.5~10質量%，又更好為1~5質量%。 In the cellulose composition of the present invention, the content of the compound represented by the formula (I) or (II) is preferably from 0.1 to 15% by mass, more preferably from 0.5 to 10% by mass, even more preferably the cellulose compound. It is 1 to 5 mass%.

前述之以通式(I)或(II)表示之化合物可使用作為光學薄膜用遲滯上升劑(控制劑)，尤其可適當地使用作為利用延伸獲得優異之遲滯展現性之薄膜用之遲滯上升劑。 The compound represented by the formula (I) or (II) can be used as a hysteresis-increasing agent (control agent) for an optical film, and in particular, a hysteresis-increasing agent for a film which exhibits excellent hysteresis exhibitability by extension can be suitably used. .

〈羧酸糖酯〉 <carboxylic acid sugar ester>

本發明之光學補償膜或透明保護膜較好視需要添加羧酸糖酯。 The optical compensation film or the transparent protective film of the present invention is preferably added with a carboxylic acid sugar ester as needed.

此處，所謂「羧酸糖酯」意指由糖類之羥基(OH基：亦稱為「氫氧基」)與羧酸之羧基衍生之具有酯鍵之化合物。但，本申請案中，纖維素酯不包含於該羧酸糖酯中。 Here, the "carboxylic acid saccharide ester" means a compound having an ester bond derived from a hydroxy group (OH group: also referred to as "hydroxyl group") of a saccharide and a carboxyl group of a carboxylic acid. However, in the present application, the cellulose ester is not included in the carboxylic acid sugar ester.

該羧酸糖酯可較好地使用例如具有1個以上12個以下之吡喃糖構造或呋喃糖構造之至少一種，且其構造之羥基之一部分經酯化之酯化合物。酯化之比例較好為70%以上。 As the carboxylic acid sugar ester, for example, an ester compound having at least one of a pyranose structure or a furanose structure of one or more and 12 or less, and a part of a hydroxyl group of the structure may be preferably esterified. The ratio of esterification is preferably 70% or more.

本發明中可較好地使用以下述通式(1)表示之化合物作為羧酸糖酯。 In the present invention, a compound represented by the following formula (1) can be preferably used as the carboxylic acid sugar ester.

本發明中，以下述通式(1)表示之化合物之所謂取代度係表示通式(1)所含之8個羥基(氫氧基)中，以氫以外之取代基取代之數，亦即，表示通式(1)之R₁~R₈中，含有氫以外之基之數。因此，R₁~R₈全部以氫以外之取代基取代時，取代度成為最大值之8.0，R₁~R₈全部為氫原子時取代度成為0.0。 In the present invention, the degree of substitution of the compound represented by the following formula (1) represents the number of substituents other than hydrogen in the eight hydroxyl groups (hydroxyl groups) contained in the formula (1), that is, Further, R ₁ to R ₈ in the formula (1) contain a number of groups other than hydrogen. Therefore, when all of R ₁ to R ₈ are substituted with a substituent other than hydrogen, the degree of substitution becomes 8.0 of the maximum value, and when all of R ₁ to R ₈ are a hydrogen atom, the degree of substitution becomes 0.0.

本發明中，以通式(1)表示之化合物之取代度，就遲滯、透過率、揮發性、機械強度等之觀點而言，較好為2.8~6.0。又，更好為2.8~5.2。 In the present invention, the degree of substitution of the compound represented by the formula (1) is preferably from 2.8 to 6.0 from the viewpoints of hysteresis, transmittance, volatility, mechanical strength and the like. Also, it is better to be 2.8~5.2.

以通式(1)表示之化合物之取代度以使用平均取代度較適當，可由以下述方法，利用高速液體層析儀之顯示取代度分布之圖表之面積比測定平均取代度。 The degree of substitution of the compound represented by the formula (1) is suitably determined by using the average degree of substitution, and the average degree of substitution can be determined by the area ratio of the graph showing the degree of substitution distribution of the high-speed liquid chromatograph by the following method.

超低取代度之纖維素酯由於殘留之羥基(氫氧基)較多，故相較於既存之取代度高之纖維素酯會有耐水性之顧慮。為改善此，只要添加可塑劑即可，但相溶性不合時會揮發。以該點為基礎，添加構造與纖維素酯類似，取代度低之羧酸糖酯可進一步增加本發明之效果。 Since the cellulose ester having an ultra-low degree of substitution has a large amount of residual hydroxyl groups (hydroxyl groups), there is a concern that the cellulose ester having a high degree of substitution has a water resistance. In order to improve this, it is only necessary to add a plasticizer, but it will volatilize when the compatibility is not good. Based on this point, the addition of a carboxylic acid sugar ester having a structure similar to that of a cellulose ester can further increase the effects of the present invention.

又，超低取代度之纖維素酯由於容易受到水分之影響，故於作為偏光板時之耐久時收縮會成為問題。因此， 藉由使羧酸糖酯之取代度更小，殘留較多羥基(氫氧基)，恰如低取代度之纖維素酯與羧酸酯之氫鍵而被良好地軟化，可減少偏光板中收縮之影響。 Further, since the cellulose ester having an ultra-low degree of substitution is easily affected by moisture, shrinkage at the time of durability as a polarizing plate becomes a problem. therefore, By making the degree of substitution of the carboxylic acid sugar ester smaller, more hydroxyl groups (hydroxyl groups) remain, just as the low-degree substitution of the cellulose ester and the carboxylate hydrogen bond are well softened, and the shrinkage in the polarizing plate can be reduced. The impact.

通式(1)中，R₁~R₈表示氫原子、經取代或未經取代之烷基羰基、或經取代或未經取代之芳基羰基，亦即醯基，且R₁~R₈可相同亦可不同(以下亦稱氫原子以外之R₁~R₈為醯基)。 In the formula (1), R ₁ to R ₈ represent a hydrogen atom, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group, that is, a fluorenyl group, and R ₁ to R ₈ They may be the same or different (hereinafter, R ₁ to R ₈ other than hydrogen atoms are sulfhydryl groups).

本發明之羧酸糖酯之合成原料糖之例可列舉為以下者，但本發明並不限於該等。 Examples of the synthetic raw material sugar of the carboxylic acid sugar ester of the present invention include the following, but the present invention is not limited thereto.

列舉為葡萄糖、半乳糖、甘露糖、果糖、木糖、或***糖、乳糖、蔗糖、蔗果四糖(nystose)、1F-蔗果五糖(fructosyl nystose)、水酥糖(stachyose)、麥芽糖醇、乳糖醇、乳果糖、纖維雙糖(cellobiose)、麥芽糖、纖維三糖、麥芽三糖、棉子糖或蔗果三糖(kestose)。 Listed as glucose, galactose, mannose, fructose, xylose, or arabinose, lactose, sucrose, nystose, 1F-fructosyl nystose, stachyose, maltose Alcohol, lactitol, lactulose, cellobiose, maltose, cellotriose, maltotriose, raffinose or kestose.

另外，以列舉為龍膽二糖(gentiobiose)、龍膽三糖、龍膽四糖、木三糖(xylotriose)、半乳蔗糖(galactosylsucrose)等。 Further, it is exemplified by gentiobiose, gentiotriose, gentiantetraose, xylotriose, galactosylsucrose, and the like.

其中，就相溶性與揮發性之觀點而言以蔗糖較佳。 Among them, sucrose is preferred from the viewpoint of compatibility and volatility.

本發明之羧酸糖酯之合成時使用之單羧酸可使用習知之脂肪族單羧酸、脂環族單羧酸、芳香族單羧酸等。使用之羧酸可為一種或混合兩種以上。 As the monocarboxylic acid used in the synthesis of the carboxylic acid sugar ester of the present invention, a conventional aliphatic monocarboxylic acid, an alicyclic monocarboxylic acid, an aromatic monocarboxylic acid or the like can be used. The carboxylic acid to be used may be one type or a mixture of two or more types.

較佳之脂肪單羧酸之例可列舉為乙酸、丙酸、丁酸、異丁酸、戊酸、己酸、庚酸、辛酸、正壬酸(pelargonic acid)、癸酸、2-乙基己酸、十一烷酸、月桂酸、十三烷酸、肉荳蔻酸、十五烷酸、棕櫚酸、十七烷酸、硬脂酸、十九烷酸、花生酸、山萮酸、木蠟酸(lignoceric acid)、蟲蠟酸(cerotic acid)、二十七烷酸、褐煤酸(montanoic acid)、蜂花酸(melissic acid)、蟲漆蠟酸(Lacceric acid)等之飽和脂肪酸，十一碳烯酸、油酸、山梨酸、亞油酸、亞麻酸、花生油酸、辛烯酸等之不飽和脂肪酸等。 Preferred examples of the fatty monocarboxylic acid are acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid, and n-decanoic acid (pelargonic). Acid), citric acid, 2-ethylhexanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecane Acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, heptacosanoic acid, montanic acid, melissic acid, lacquer wax A saturated fatty acid such as Lacceric acid, an unsaturated fatty acid such as undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid or octenoic acid.

較佳之脂環族單羧酸之例可列舉為環戊烷羧酸、環己烷羧酸、環辛烷羧酸、或該等之衍生物。 Examples of preferred alicyclic monocarboxylic acids include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, or the like.

較佳之芳香族單羧酸之例可列舉為苯甲酸、甲苯酸等之於苯甲酸之苯環上導入1~5個烷基或烷氧基之芳香族單羧酸、桂皮酸、二苯基乙醇酸、聯苯羧酸、萘羧酸、四氫萘羧酸等之具有兩個以上苯環之芳香族單羧酸，或該等之衍生物，但最好為苯甲酸。 Examples of the preferred aromatic monocarboxylic acid include an aromatic monocarboxylic acid, cinnamic acid, and diphenyl group in which 1 to 5 alkyl groups or alkoxy groups are introduced into a benzene ring of benzoic acid such as benzoic acid or toluic acid. An aromatic monocarboxylic acid having two or more benzene rings, such as glycolic acid, a biphenylcarboxylic acid, a naphthalenecarboxylic acid or a tetrahydronaphthalenecarboxylic acid, or a derivative thereof, preferably benzoic acid.

本發明之以通式(1)表示之化合物之具體例之一部分示於下，但下表中之R係表示通式(1)中之以R₁~R₈表示之醯基之任一個。 One of the specific examples of the compound represented by the formula (1) of the present invention is shown below, but R in the following table represents any one of the fluorenyl groups represented by R ₁ to R ₈ in the formula (1).

本發明之羧酸糖酯可藉由使醯化劑(亦稱為酯化劑，例如乙醯氯之醯鹵化物，乙酸酐等酸酐)與糖酯進行反應而製造，酯化率之分布係以醯化劑之量、添加時機、酯化反應時間之調節而達成，但藉由酯化率不同之羧酸糖酯之混合，或純粹混合單離之酯化率不同之化合物，可製作目標之羧酸糖酯。 The carboxylic acid sugar ester of the present invention can be produced by reacting a oximation agent (also referred to as an esterifying agent such as an oxime halide of acetonitrile, an acid anhydride such as acetic anhydride) with a sugar ester, and the distribution of the esterification rate is It can be achieved by adjusting the amount of the oximation agent, the timing of addition, and the esterification reaction time. However, it is possible to produce a target by mixing a carboxylic acid sugar ester having a different esterification rate or by simply mixing a compound having a different esterification rate. Carboxy sugar ester.

[消光劑] [matting agent]

本發明之光學補償膜及透明保護膜在處理所製作之膜時，為了防止產生傷痕，防止輸送性變差，亦較好添加微粒子作為消光劑。 In the optical compensation film and the transparent protective film of the present invention, in order to prevent the occurrence of scratches and to prevent deterioration of transportability, it is preferable to add fine particles as a matting agent.

至於微粒子以無機化合物之例可列舉為二氧化矽、二氧化鈦、氧化鋁、氧化鋯、碳酸鈣、碳酸鈣、滑石、黏 土、燒成高嶺土、燒成矽酸鈣、水合矽酸鈣、矽酸鋁、矽酸鎂及磷酸鈣等。微粒子為含矽者，就降低濁度方面而言較佳，最好為二氧化矽。 Examples of the inorganic compound as the fine particles include cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, and viscous. Soil, calcined kaolin, calcined calcium citrate, hydrated calcium citrate, aluminum citrate, magnesium citrate and calcium phosphate. The microparticles are ruthenium-containing, and are preferred in terms of reducing turbidity, and are preferably cerium oxide.

微粒子之一次粒子之平均粒徑較好為5~400nm，更好為10~300nm。該等亦可作為主要為粒徑0.05~0.3μm之二次凝聚體而含有，若為平均粒徑80~400nm之粒子則亦較好可不凝聚而作為一次粒子含有。薄膜中之該等微粒子之含量較好為0.01~1質量%，最好為0.05~0.5質量%。以共澆鑄法獲得之多層構成之光學補償膜之情況下，以表面含有該添加量之微粒子較佳。 The average particle diameter of the primary particles of the fine particles is preferably from 5 to 400 nm, more preferably from 10 to 300 nm. These may be contained as a secondary aggregate mainly having a particle diameter of 0.05 to 0.3 μm, and if it is a particle having an average particle diameter of 80 to 400 nm, it is preferably contained as a primary particle without agglomeration. The content of the fine particles in the film is preferably from 0.01 to 1% by mass, preferably from 0.05 to 0.5% by mass. In the case of an optical compensation film having a multilayer structure obtained by a co-casting method, it is preferred to include the added amount of fine particles on the surface.

二氧化矽之微粒子可使用例如以Aerosil R972、R972V、R974、R812、200、200V、300、R202、OX50、TT600(以上均為日本Aerosil(股)製造)之商品名銷售者。 As the fine particles of cerium oxide, for example, those sold under the trade names of Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (all of which are manufactured by Japan Aerosil Co., Ltd.) can be used.

氧化鋯微粒子可使用例如以Aerosil R976及R811(以上均為日本Aerosil(股)製造)之商品名銷售者。 As the zirconia fine particles, for example, those sold under the trade names of Aerosil R976 and R811 (all of which are manufactured by Japan Aerosil Co., Ltd.) can be used.

樹脂之例可列舉為聚矽氧樹脂、氟樹脂及丙烯酸樹脂。以聚矽氧樹脂較佳，最好為具有三次元之網狀構造者，可使用例如TOSPEARL 103、TOSPEARL 105、TOSPEARL 108、TOSPEARL 120、TOSPEARL 145、TOSPEARL 3120及TOSPEARL 240(以上均為東芝聚矽氧(股)製造)之商品名銷售者。 Examples of the resin include polyoxyxylene resins, fluororesins, and acrylic resins. Preferably, the polyoxyxylene resin, preferably a three-dimensional network structure, can be used, for example, TOSPEARL 103, TOSPEARL 105, TOSPEARL 108, TOSPEARL 120, TOSPEARL 145, TOSPEARL 3120, and TOSPEARL 240 (all of which are Toshiba Poly Oxygen (stock) manufacturing) trade name seller.

該等中Aerosil 200V、Aerosil R972V由於可保持光學補償膜之低濁度，同時降低摩擦係數之效果較大故最適 用。本發明之光學補償膜中，以至少一面之動摩擦係數為0.2~1.0較佳。 These Aerosil 200V and Aerosil R972V are optimal because they can maintain the low turbidity of the optical compensation film and reduce the friction coefficient. use. In the optical compensation film of the present invention, the dynamic friction coefficient of at least one side is preferably 0.2 to 1.0.

又，消光劑可均勻地分散於薄膜整體中，亦可僅局部存在於表層中。 Further, the matting agent may be uniformly dispersed in the entire film, or may be locally present only in the surface layer.

(光學補償膜及透明保護膜之製造方法) (Method for producing optical compensation film and transparent protective film)

本發明之光學補償膜及透明保護膜之製造方法可使用通常之吹塑法、T-模嘴法、簾流法、切削法、澆鑄法、乳液法、加熱板法等製造法，但就抑制變色、抑制異物缺陷、抑制刀模線等之光學缺陷等之觀點而言，以澆鑄法進行之溶液澆鑄法、及熔融澆鑄法較佳。 The optical compensation film and the transparent protective film of the present invention can be produced by a usual blow molding method, a T-die method, a curtain flow method, a cutting method, a casting method, an emulsion method, a hot plate method, or the like, but are suppressed. The solution casting method and the melt casting method by a casting method are preferable from the viewpoints of discoloration, suppression of foreign matter defects, suppression of optical defects such as a die line, and the like.

以下針對製作本發明之光學補償膜時之製造方法加以詳述。又，本發明之透明保護膜可藉過去習知之一般方法製造，例如可藉依據下述之光學補償膜之製造方法之方法製造。 Hereinafter, a manufacturing method for producing the optical compensation film of the present invention will be described in detail. Further, the transparent protective film of the present invention can be produced by a conventional method known in the art, and can be produced, for example, by the method of producing an optical compensation film described below.

〈以溶液澆鑄法進行之光學補償膜之製造方法〉 <Method of Manufacturing Optical Compensation Film by Solution Casting Method> 《有機溶劑》 "Organic solvents"

以溶液澆鑄法製造本發明之光學補償膜時，於形成摻雜有用之有機溶劑只要為使纖維素酯樹脂等之熱可塑性樹脂溶解者即可無限制的使用。 When the optical compensation film of the present invention is produced by a solution casting method, the organic solvent used for forming the doping may be used without limitation in order to dissolve the thermoplastic resin such as a cellulose ester resin.

例如，氯系有機溶劑可列舉為二氯甲烷，非氯系有機溶劑可例舉為乙酸甲酯、乙酸乙酯、乙酸戊酯、丙酮、四氫呋喃、1,3-二氧雜環戊烷、1,4-二噁烷、環己酮、甲酸 乙酯、2,2,2-三氟乙醇、2,2,3,3-六氟-1-丙醇、1,3-二氟-2-丙醇、1,1,1,3,3,3-六氟-2-甲基-2-丙醇、1,1,1,3,3,3-六氟-2-丙醇、2,2,3,3,3-五氟-1-丙醇、硝基乙烷、乳酸乙酯、乳酸、二丙酮醇等，較好可使用二氯甲烷、乙酸甲酯、乙酸乙酯、丙酮、乳酸乙酯等。 For example, the chlorine-based organic solvent may be dichloromethane, and the non-chlorine organic solvent may, for example, be methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran or 1,3-dioxolane, , 4-dioxane, cyclohexanone, formic acid Ethyl ester, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3 ,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1 -propanol, nitroethane, ethyl lactate, lactic acid, diacetone alcohol or the like, preferably dichloromethane, methyl acetate, ethyl acetate, acetone, ethyl lactate or the like can be used.

摻雜劑中除上述有機溶劑以外，亦可含有1~40質量%之碳原子數1~4之直鏈或分支鏈狀之脂肪族醇。摻雜劑中之醇之比率高時網片會凝膠化，自金屬支撐體剝離變容易，另外，醇之比例少時，亦扮演促進非氯系有機溶劑系中之熱可塑性樹脂溶解之角色。 The dopant may contain, in addition to the above organic solvent, 1 to 40% by mass of a linear or branched aliphatic alcohol having 1 to 4 carbon atoms. When the ratio of the alcohol in the dopant is high, the mesh gels, and it is easy to peel off from the metal support. In addition, when the ratio of the alcohol is small, it also plays a role in promoting the dissolution of the thermoplastic resin in the non-chlorine organic solvent system. .

尤其，較好為於含有二氯甲烷及碳數1~4之直鏈或分支鏈狀之脂肪族醇之溶劑中，熱可塑性樹脂以至少合計溶解10~45質量%之摻雜劑組成物較佳。 In particular, it is preferred that the thermoplastic resin is dissolved in at least 10 to 45% by mass of the dopant composition in a solvent containing a linear or branched aliphatic alcohol having dichloromethane and a carbon number of 1 to 4. good.

碳原子數1~4之直鏈或分支鏈狀之脂肪族醇可列舉為甲醇、乙醇、正丙醇、異丙醇、正丁醇、第二丁醇、第三丁醇。該等中就摻雜劑之安定性、沸點亦較低、乾燥性亦良好等而言以乙醇較佳。 The linear or branched aliphatic alcohol having 1 to 4 carbon atoms may, for example, be methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol or tert-butanol. Among these, ethanol is preferred in terms of stability of the dopant, low boiling point, and good drying property.

以下，針對本發明之光學補償膜(以下亦簡稱為「薄膜」)之較佳製膜方法加以說明。 Hereinafter, a preferred film forming method of the optical compensation film (hereinafter also simply referred to as "thin film") of the present invention will be described.

1)溶解步驟 1) Dissolution step

以對熱可塑性樹脂為良溶劑為主之有機溶劑中，邊於溶解釜中攪拌熱可塑性樹脂、其他添加劑邊溶解形成摻雜劑之步驟。 In the organic solvent mainly containing a thermoplastic resin as a good solvent, a step of dissolving the thermoplastic resin and other additives while dissolving the thermoplastic resin and the other additives is performed.

熱可塑性樹脂之溶解可使用在常壓下進行之方法、在主溶劑之沸點以下進行之方法、在主溶劑之沸點以上加壓進行之方法、如特開平9-95544號公報、特開平9-95557號公報、或特開平9-95538號公報中所記載之以冷卻溶解法進行之方法、如特開平11-21379號公報中所記載之在高壓下進行之方法等各種溶解方法，但最好為在主溶劑之沸點以上經加壓進行之方法。 The dissolution of the thermoplastic resin can be carried out by a method carried out under normal pressure, a method carried out below the boiling point of the main solvent, or a method of pressurizing at a boiling point or higher of the main solvent, for example, JP-A-9-95544, JP-A-9- Various methods of dissolving, such as the method described in the method of the cooling and dissolving method, and the method described in JP-A-11-21379, which is carried out under high pressure, are described in JP-A-H05-95538, but it is preferable. It is a method of pressurizing above the boiling point of the main solvent.

所謂回收材為薄膜經細粉碎之物，意指在薄膜製膜時產生之切掉薄膜之兩側部分之物，或有擦傷等成為規格外之薄膜原料，均可再使用。 The recycled material is a finely pulverized material of the film, which means that the film is cut off at the time of film formation, and the film material on both sides of the film is cut off, or the film material other than the scratch is used.

2)澆鑄步驟 2) Casting step

使摻雜劑通過送液泵(例如，加壓型定量齒輪泵)送液到加壓模嘴中，使摻雜劑自加壓模嘴狹縫澆鑄於無限移送之環狀金屬輸送帶，例如不鏽鋼輸送帶、或者旋轉之金屬滾筒等金屬支撐體上之澆鑄位置上之步驟。 The dopant is sent to the pressurized die by a liquid feeding pump (for example, a pressurized quantitative gear pump), and the dopant is cast from the nozzle of the pressurized die to the infinitely transferred annular metal conveyor belt, for example The step of casting on a metal support such as a stainless steel conveyor belt or a rotating metal drum.

較好為可調整模嘴之金屬蓋部分之狹縫形狀，使膜厚容易均勻之加壓模嘴。加壓模嘴有衣架型模嘴或T模嘴等，均可較好地使用。金屬支撐體之表面為鏡面。將提高製膜速度用之加壓模嘴以二台以上設置於金屬支撐體上，亦可分割摻雜劑量並重疊。或者使複數種摻雜劑以同時澆鑄之共澆鑄法獲得層合構造之薄膜亦較佳。 It is preferable to adjust the slit shape of the metal lid portion of the nozzle to make the film thickness easy to be uniform and pressurize the nozzle. The pressurizing die mouth can be preferably used by a hanger type die mouth or a T die mouth. The surface of the metal support is mirrored. Two or more pressurizing nozzles for increasing the film forming speed are provided on the metal support, and the doping amount may be divided and overlapped. Alternatively, it is preferred to obtain a film of a laminated structure by co-casting a plurality of kinds of dopants by simultaneous casting.

3)溶劑蒸發步驟 3) Solvent evaporation step

在澆鑄用支撐體上加熱網片(將摻雜劑澆鑄於澆鑄用支撐體上，形成之摻雜劑膜稱為網片)，使溶劑蒸發之步驟。 A step of heating the web on the support for casting (casting the dopant onto the support for casting, forming a dopant film called a mesh) to evaporate the solvent.

使溶劑蒸發有自網片側吹風之方法及/或自支撐體之裏面以液體傳熱之方法、以輻射熱自表裏傳熱之方法，但以裏面液體傳熱方法之乾燥效率較佳。又，亦可較好地使用組合該等之方法。較好使澆鑄後之支撐體上之網片在40~100℃之環境下，在支撐體上乾燥。就維持在40~100℃之環境下而言，較好在藉由使嘎溫度之熱風碰觸織物上面或以紅外線等手段加熱。 The evaporation of the solvent has a method of blowing from the side of the web and/or a method of transferring heat from the inside of the support by means of liquid heat, and heat transfer from the surface by radiant heat, but the drying efficiency of the liquid heat transfer method is better. Further, a method of combining these methods can also be preferably used. Preferably, the mesh on the support after casting is dried on the support in an environment of 40 to 100 ° C. In the case of maintaining the temperature of 40 to 100 ° C, it is preferred to heat the surface by touching the hot air of the crucible temperature or by means of infrared rays or the like.

就面品質、透濕性、剝離性之觀點而言，較好在30~120秒以內自支撐體剝離該網片。 From the viewpoint of surface quality, moisture permeability, and peelability, it is preferred to peel the web from the support within 30 to 120 seconds.

4)剝離步驟 4) Stripping step

此係將於金屬支撐體上已蒸發溶劑之網片在剝離位置剝離之步驟。將經剝離之網片送到下一步驟。 This is the step of stripping the web of evaporated solvent on the metal support at the stripping position. The stripped web is sent to the next step.

金屬支撐體上之剝離位置之溫度較好為10~40℃，更好為11~30℃。 The temperature at the peeling position on the metal support is preferably from 10 to 40 ° C, more preferably from 11 to 30 ° C.

又，剝離時點之金屬支撐體上之網片之剝離時殘留溶劑量較好依據乾燥條件之強弱、金屬支撐體之長度等在50~120質量%之範圍剝離，但在殘留溶劑量更多之時點剝離時，網片太過柔軟時會損及剝離時之平面性，容易因剝離張力而出現皺摺或縱向皺摺，故需兼顧經濟速度與品質而決定剝離時之殘留溶劑量。 Moreover, the amount of residual solvent at the time of peeling of the mesh on the metal support at the time of peeling is preferably in the range of 50 to 120% by mass, depending on the strength of the drying conditions and the length of the metal support, but the amount of residual solvent is more When peeling at a time point, when the mesh is too soft, the flatness at the time of peeling is impaired, and wrinkles or longitudinal wrinkles are likely to occur due to the peeling tension. Therefore, the amount of residual solvent at the time of peeling is determined in consideration of economic speed and quality.

網片之殘留溶劑量係以下述式定義。 The residual solvent amount of the mesh is defined by the following formula.

殘留溶劑量(%)=(網片之加熱處理前質量-網片加熱處理後質量)/(網片加熱處理後質量)×100 Residual solvent amount (%) = (mass before heat treatment of mesh - mass after heat treatment of mesh) / (quality after heat treatment of mesh) × 100

又，測定殘留溶劑量時之加熱處理表示在115℃下進行1小時之加熱處理。 Further, the heat treatment at the time of measuring the amount of residual solvent showed heat treatment at 115 ° C for 1 hour.

剝離金屬支撐體與薄膜時之剝離張力通常為196~245N/m，但在剝離時容易產生皺摺之情況下，較好以190N/m以下之張力剝離，再者較好在可剝離之最低張力~166.6 N/m，其次在最低張力~137.2N/m下剝離，但最好在最低張力~100N/m下剝離。 When the metal support and the film are peeled off, the peeling tension is usually 196 to 245 N/m. However, when wrinkles are likely to occur at the time of peeling, it is preferably peeled at a tension of 190 N/m or less, and preferably at the lowest peelable. The tension is ~166.6 N/m, followed by peeling at a minimum tension of ~137.2 N/m, but it is best to peel off at a minimum tension of ~100 N/m.

本發明中，較好使該金屬支撐體上之剝離位置溫度成為-50~40℃，更好為10~40℃，最好為15~30℃。 In the present invention, the peeling position temperature on the metal support is preferably from -50 to 40 ° C, more preferably from 10 to 40 ° C, most preferably from 15 to 30 ° C.

5)乾燥及延伸步驟 5) Drying and stretching steps

剝離後，使用使網片交互通過複數個配置在乾燥裝置內之輥而輸送之乾燥裝置，及/或以夾具夾住網片之兩端而輸送之拉幅機延伸裝置，使網片乾燥。 After the stripping, the web is dried by using a drying device that transports the webs through a plurality of rolls disposed in the drying apparatus, and/or a tenter stretching device that is conveyed by gripping both ends of the web with a jig.

乾燥手段一般為對網片之兩面吹送熱風，但亦可以微波代替風進行加熱之手段。過度急速乾燥容易損及完成之薄膜之平面性。以高溫進行之乾燥宜在使殘留溶劑為8質量%以下後再進行。整體而言乾燥大概在40~250℃進行，最好在40~160℃乾燥。 The drying means generally blows hot air to both sides of the mesh, but it can also be heated by microwave instead of the wind. Excessive rapid drying tends to damage the planarity of the finished film. Drying at a high temperature is preferably carried out after the residual solvent is 8% by mass or less. Drying is generally carried out at 40 to 250 ° C, preferably at 40 to 160 ° C.

使用拉幅機延伸裝置時，較好使用利用拉幅機之左右 固定機構，可於左右獨立控制薄膜之固定長度(自固定開始至固定結束之距離)之裝置。又，拉幅機步驟中，為改善平面性較好亦刻意區分出具有不同溫度之區域。 When using a tenter extension device, it is better to use the left and right of the tenter The fixing mechanism can independently control the fixed length of the film (the distance from the start of fixing to the end of fixing). Moreover, in the tenter step, it is better to improve the planarity and to deliberately distinguish regions having different temperatures.

且，亦較好設置中間區域以使不同溫度區域間不會引起各別區域干涉。 Moreover, it is also preferable to set the intermediate portion so that different temperature regions do not cause interference between the respective regions.

又，延伸操作亦可分割成多階段進行，亦較好朝澆鑄方向、寬度方向進行雙軸延伸。且，進行雙軸延伸時可同時進行雙軸延伸，亦可階段性實施。 Further, the stretching operation may be divided into a plurality of stages, and it is also preferable to perform biaxial stretching in the casting direction and the width direction. Moreover, the biaxial stretching can be performed simultaneously at the time of biaxial stretching, or can be carried out in stages.

該情況下，所謂階段性為例如可依序進行延伸方向不同之延伸，亦可將同一方向之延伸分割成多階段，且亦可於其任一階段施加不同方向之延伸。亦即，亦可為例如如下之延伸步驟。 In this case, the gradation is, for example, an extension in which the extending directions are different, and the extension in the same direction may be divided into a plurality of stages, and extension in different directions may be applied at any of the stages. That is, it may be, for example, an extension step as follows.

． 朝澆鑄方向延伸-朝寬度方向延伸-朝澆鑄方向延伸-朝澆鑄方向延伸 . Extending in the casting direction - extending in the width direction - extending in the casting direction - extending in the casting direction

． 朝寬度方向延伸-朝寬度方向延伸-朝澆鑄方向延伸-朝澆鑄方向延伸 . Extending in the width direction - extending in the width direction - extending in the casting direction - extending in the casting direction

且，同時雙軸延伸亦包含於一方向延伸，於另一方向使張力緩和而收縮之情況。同時雙軸延伸之較佳延伸倍率可在寬度方向、長度方向均為×1.01倍~×1.5倍之範圍。 Moreover, the simultaneous biaxial stretching also includes the case where the tension is relaxed and contracted in the other direction. At the same time, the preferred stretching ratio of the biaxial stretching can be in the range of ×1.01 times to 1.5 times in the width direction and the length direction.

進行拉幅時之網片之殘留溶劑量較好於拉幅開始時為20~100質量%，且較好邊施加拉幅直至網片之殘留溶劑量成為10質量%以下邊進行乾燥，更好為5質量%以下。 The residual solvent amount of the mesh at the time of tentering is preferably from 20 to 100% by mass at the beginning of the tentering, and it is preferred to apply the tenter until the residual solvent amount of the mesh is 10% by mass or less, and it is better to dry. It is 5% by mass or less.

進行拉幅時之乾燥溫度較好為30~160℃，更好為50~150℃，最好為70~140℃。 The drying temperature at the time of tentering is preferably from 30 to 160 ° C, more preferably from 50 to 150 ° C, most preferably from 70 to 140 ° C.

拉幅步驟中，環境之寬度方向之溫度分佈少，就提高薄膜之均一性之觀點而言較佳，拉幅步驟中之寬度方向之溫度分佈較好為±5℃以內，更好為±2℃以內，最好為±1℃以內。 In the tentering step, the temperature distribution in the width direction of the environment is small, and it is preferable from the viewpoint of improving the uniformity of the film, and the temperature distribution in the width direction in the tentering step is preferably within ±5 ° C, more preferably ± 2 Within °C, preferably within ±1 °C.

6)捲取步驟 6) Winding step

網片中之殘留溶劑量成為2質量%以下以後，利用捲繞機以薄膜進行捲取之步驟，藉由使殘留溶劑量成為0.4質量%以下可獲得尺寸安定性良好之薄膜。最好於0.00~0.10質量%捲取。 In the case where the amount of the residual solvent in the mesh is 2% by mass or less, the film is wound by a film by a winder, and the film having a good dimensional stability can be obtained by setting the amount of the residual solvent to 0.4% by mass or less. It is preferably taken up at 0.00 to 0.10% by mass.

捲取方法只要使用一般使用者即可，有定扭力法、定張力法、張力漸增法、內部應力一定之程式張力控制法等，只要使用該等即可。 The winding method may be a general user, and a fixed torque method, a constant tension method, a tension increasing method, a program tension control method with a constant internal stress, and the like may be used.

本發明之薄膜較好為長條狀薄膜，具體而言為顯示100m~5000m左右者，通常為以輥狀提供之形態者。且，薄膜寬度較好為1.3~4m，更好為1.4~2m。 The film of the present invention is preferably a long film, and specifically, a film of about 100 m to 5,000 m is usually provided in the form of a roll. Further, the film width is preferably from 1.3 to 4 m, more preferably from 1.4 to 2 m.

本發明之薄膜膜厚並無特別限制，較好為20~200μm。 The film thickness of the film of the present invention is not particularly limited, but is preferably from 20 to 200 μm.

〈以熔融澆鑄製膜法之光學補償膜之製造方法〉 <Method of Manufacturing Optical Compensation Film by Melt Casting Film Formation Method>

針對以本發明之纖維素酯樹脂、丙烯酸樹脂等之熱可塑性樹脂薄膜基材作為光學補償膜，利用熔融澆鑄製膜法製造時之方法加以說明。 A method of producing a film of a thermoplastic resin film such as a cellulose ester resin or an acrylic resin of the present invention as an optical compensation film by a melt casting film forming method will be described.

〈熔融顆粒製造步驟〉 <Molten particle manufacturing step>

構成用於熔融擠出之熱可塑性樹脂薄膜之組成物通常較好經預先混練並顆粒化。 The composition constituting the thermoplastic resin film for melt extrusion is usually preferably pre-kneaded and granulated.

顆粒化經常以習知方法，例如以送料機將乾燥之熱可塑性樹脂與依據目的之添加劑供給於擠出機中，使用單軸或雙軸擠出機進行混練，自模嘴擠出呈線股狀，經水冷或空氣冷卻並切割而成。 Granulation is often carried out in a conventional manner by a conventional method, for example, feeding a dry thermoplastic resin with a purpose-dependent additive to an extruder, using a uniaxial or twin-screw extruder for kneading, and extruding from a nozzle into a strand. Shaped, cooled by water or air and cut.

原材料在擠出前預先乾燥對於防止原材料分解之方面相當重要。尤其纖維素酯由於容易吸濕，故預先以除濕熱風乾燥機或真空乾燥機在70~140℃乾燥3小時以上，使水分率成為200ppm以下，更好成為100ppm以下。 Pre-drying of raw materials prior to extrusion is important to prevent decomposition of raw materials. In particular, the cellulose ester is dried at 70 to 140 ° C for 3 hours or more in a dehumidifying hot air dryer or a vacuum dryer in advance, so that the water content is 200 ppm or less, more preferably 100 ppm or less.

添加劑亦可在供給於擠出機之前預先混合，亦可分別以各別之送料機供給。抗氧化劑等之少量添加劑為了均勻混合，較好在供給於擠出機之前預先混合。 The additives may also be pre-mixed before being supplied to the extruder, or may be supplied separately by respective feeders. A small amount of the additive such as an antioxidant is preferably mixed in advance before being supplied to the extruder for uniform mixing.

抗氧化劑之混合可使固體彼此混合，亦可視需要將抗氧化劑溶解於溶劑中，含浸於熱可塑性樹脂中予以混合，或者亦可經噴霧混合。 The mixing of the antioxidants may allow the solids to be mixed with each other, and the antioxidant may be dissolved in a solvent, impregnated with the thermoplastic resin, or may be mixed by spraying.

真空NAUTA混合機等由於可同時乾燥與混合故較佳。且，自送料機部或模嘴之出口等與空氣接觸時，較好在除濕空氣或除濕之N₂氣體等環境下。 Vacuum NAUTA mixers and the like are preferred because they can be dried and mixed at the same time. Further, in the case of contact with air from the feeder portion or the mouth of the nozzle, it is preferably in an environment such as dehumidified air or dehumidified N ₂ gas.

擠出機較好在以能夠抑制剪斷力、不使樹脂劣化(分子量下降、變色、生成凝膠等)之方式顆粒化之低溫下加工。例如，雙軸押出機時，較好使用深溝型之螺桿，以相同方向旋轉。基於混練之均勻性，較好為咬合類型。 The extruder is preferably processed at a low temperature which is capable of suppressing the shearing force and granulating the resin so as not to deteriorate the resin (molecular weight, discoloration, gel formation, etc.). For example, in the case of a two-axis extruder, it is preferable to use a deep groove type screw to rotate in the same direction. Based on the uniformity of the kneading, it is preferably a type of occlusion.

使用如上述獲得之顆粒進行薄膜製膜。亦可未經顆粒化，將原材料之粉末直接以送料機供給至擠出機，且直接進行薄膜製膜。 Film formation was carried out using the pellets obtained as described above. Alternatively, the powder of the raw material may be directly supplied to the extruder as a feeder without granulation, and the film may be directly formed into a film.

〈自模嘴朝冷卻輥擠出熔融混合物之步驟〉 <Step of extruding molten mixture from the die mouth toward the chill roll>

首先，製作之顆粒使用單軸或雙軸型擠出機，使擠出時之熔融溫度Tm成為200~300℃左右，以葉盤型之過濾器等過濾去除異物後，自T模嘴共擠出成薄膜狀，且在冷卻輥上固化，邊以彈性接觸輥按壓邊澆鑄。 First, the granules to be produced are uniaxially or biaxially extruded, so that the melting temperature Tm at the time of extrusion is about 200 to 300 ° C, and the foreign matter is filtered from the T die after being filtered by a leaf disc type filter or the like. The film was formed into a film and solidified on a cooling roll, and was cast while being pressed by an elastic contact roll.

自供給料斗朝擠出機導入時較好處於真空下或減壓下或惰性氣體環境下以防止氧化分解等。又，Tm為擠出機之模嘴出口部分之溫度。 When the feed hopper is introduced into the extruder, it is preferably under vacuum or under reduced pressure or in an inert gas atmosphere to prevent oxidative decomposition and the like. Further, Tm is the temperature at the exit portion of the nozzle of the extruder.

於模嘴上附著傷痕或可塑劑之凝聚物等異物時，會有發生條紋狀缺陷之情況。該缺陷亦稱為刀模線，但為了使刀模線等之表面缺陷變小，較好將自擠出機至模嘴之配管做成使樹脂之滯留部分極少之構造。較好使用模嘴之內部或唇部極度無紋理者。 When foreign matter such as a flaw or agglomerates of a plasticizer adheres to the nozzle, streaky defects may occur. This defect is also called a die line. However, in order to reduce the surface defects of the die line or the like, the pipe from the extruder to the die is preferably made to have a structure in which the resin retaining portion is extremely small. It is better to use the inside of the nozzle or the lip is extremely textureless.

擠出機或模嘴等之與熔融樹脂接觸之內面係使用表面粗糙度小，且表面能量低之材質等，且較好施予難以使熔融樹脂附著之表面加工。具體而言，列舉為使硬鉻電鍍或陶瓷熔射而成者以成為表面粗糙度0.2S以下之方式研磨而成者。 The inner surface of the extruder or the die which is in contact with the molten resin is a material having a small surface roughness and a low surface energy, and is preferably subjected to surface processing in which it is difficult to adhere the molten resin. Specifically, it is a case where the hard chrome plating or the ceramic is sprayed, and the surface roughness is 0.2 S or less.

本發明中之冷卻輥並無特別限制，但可為具備使溫度可控制之熱介質或冷介質流經高剛性之金屬輥內部而成之 構造之輥，大小並無限制，只要可使熔融擠出之薄膜充分冷卻之大小即可，通常冷卻輥之直徑為100mm至1m左右。 The chill roll in the present invention is not particularly limited, but may be formed by flowing a heat medium or a cold medium whose temperature can be controlled through a metal roller having high rigidity. The size of the roll to be constructed is not limited as long as the melt-extruded film can be sufficiently cooled. Usually, the diameter of the cooling roll is about 100 mm to 1 m.

冷卻輥之表面材質列舉為碳鋼、不鏽鋼、鋁、鈦等。為了進一步提高表面硬度，且改良與樹脂之剝離性，較好施予硬質鍍鉻、鍍鎳、非晶質鍍鉻等，或陶瓷熔射等表面處理。 The surface material of the cooling roll is exemplified by carbon steel, stainless steel, aluminum, titanium, and the like. In order to further increase the surface hardness and improve the releasability to the resin, it is preferred to apply a surface treatment such as hard chrome plating, nickel plating, amorphous chrome plating, or ceramic spraying.

冷卻輥表面之表面粗糙度以算術平均粗糙度Ra表示較好為0.1μm以下，更好為0.05μm以下。輥表面愈平滑，則所得薄膜之表面亦可愈平滑。當然較好經表面加工之表面進而研磨成上述之表面粗糙度。 The surface roughness of the surface of the cooling roll is preferably 0.1 μm or less, more preferably 0.05 μm or less, in terms of arithmetic mean roughness Ra. The smoother the surface of the roll, the smoother the surface of the resulting film. Of course, it is preferred that the surface-treated surface is further ground to the above-mentioned surface roughness.

本發明中，彈性接觸輥可使用如特開平03-124425號、特開平08-224772號、特開平07-100960號、特開平10-272676號、WO 97/028950、特開平11-235747號、特開2002-36332號、特開2005-172940號或特開2005-280217號公報中所記載之表面被覆薄膜金屬條之矽橡膠輥。 In the present invention, the elastic contact roller can be used, for example, in Japanese Patent Laid-Open No. Hei 03-124425, No. Hei 08-224772, No. Hei 07-100960, No. Hei 10-272676, WO 97/028950, and No. 11-235747. A rubber roll having a surface-coated metal strip as described in JP-A-2002-36332, JP-A-2005-172940, or JP-A-2005-280217.

自冷卻輥剝離薄膜時，較好控制張力以防止薄膜變形。 When the film is peeled off from the cooling roll, the tension is preferably controlled to prevent deformation of the film.

〈延伸步驟〉 <Extension step>

本發明中，如上述獲得之薄膜在通過接觸冷卻輥之步驟後，亦可進而於至少一方向進行1.01~3.0倍延伸。 In the present invention, the film obtained as described above may be further extended in at least one direction by 1.01 to 3.0 times after the step of contacting the cooling roll.

較好縱向(薄膜輸送方向)、橫向(寬度方向)二方 向分別延伸1.1~2.0倍。 Better longitudinal (film transport direction), lateral (width direction) The direction is extended by 1.1 to 2.0 times.

延伸方法可較好地使用習知之輥延伸機或拉幅機等。尤其光學補償膜兼作偏光器保護模時，由於可藉由以延伸方向作為寬方向而使與偏光薄膜之層合為輥形態故較佳。 The stretching method can preferably use a conventional roll stretcher or tenter or the like. In particular, when the optical compensation film also serves as a polarizer protective mold, it is preferable to laminate the polarizing film into a roll form by extending the direction as the width direction.

藉由朝寬度方向延伸而使光學補償膜之遲相軸成為寬度方向。 The retardation axis of the optical compensation film is made to extend in the width direction by extending in the width direction.

通常，延伸倍率為1.1~3.0倍，較好為1.2~2倍，延伸溫度通常在構成薄膜之樹脂之Tg~Tg+50℃，較好在Tg~Tg+50℃之溫度範圍進行。 Usually, the stretching ratio is 1.1 to 3.0 times, preferably 1.2 to 2 times, and the stretching temperature is usually carried out at a temperature of Tg to Tg + 50 ° C of the resin constituting the film, preferably in a temperature range of Tg to Tg + 50 ° C.

延伸較好在長度方向或寬度方向以經控制之均一溫度分佈下進行。較好為±2℃以內，更好為±1℃以內，最好為±0.5℃以內。 The extension is preferably carried out in the longitudinal direction or in the width direction with a controlled uniform temperature distribution. It is preferably within ± 2 ° C, more preferably within ± 1 ° C, and preferably within ± 0.5 ° C.

以上述方法製作之薄膜狀樹脂薄膜作為光學補償膜使用時，為減小該光學補償膜之相位差(遲滯)調整或尺寸變化率，亦可使薄膜於長度方向或寬度方向收縮。 When the film-form resin film produced by the above method is used as an optical compensation film, the film may be contracted in the longitudinal direction or the width direction in order to reduce the phase difference (hysteresis) adjustment or the dimensional change rate of the optical compensation film.

朝長度方向收縮有例如使寬度延伸夾具暫時放鬆於朝長度方向予以鬆弛，或藉由使橫向延伸機之相鄰之夾具之間隔緩緩變窄，使薄膜收縮之方法。 Shrinking in the longitudinal direction is, for example, a method in which the width extending jig is temporarily loosened to be relaxed in the longitudinal direction, or the film is shrunk by gradually narrowing the interval between adjacent jigs of the lateral stretching machine.

遲相軸方向之均勻性亦相當重要，相對於薄膜寬度方向，角度較好為-5~+5°，更好為-1~+1°之範圍，最好為-0.5~+0.5°之範圍，又最好為-0.1~+0.1°之範圍。該等偏離數值可藉由使延伸條件最適化而達成。 The uniformity of the direction of the slow phase axis is also very important. The angle is preferably -5 to +5 °, more preferably -1 to +1 °, and preferably -0.5 to +0.5 ° with respect to the width direction of the film. The range is preferably in the range of -0.1 to +0.1. These deviation values can be achieved by optimizing the extension conditions.

本發明之光學補償膜較好為長條狀薄膜，具體而言表示100m~10000m左右者，且通常為以輥狀提供之形態 者。另外，薄膜之寬度較好為1.3~4m，更好為1.4~2.5m。 The optical compensation film of the present invention is preferably a long film, specifically, it is about 100 m to 10,000 m, and is usually provided in the form of a roll. By. Further, the width of the film is preferably from 1.3 to 4 m, more preferably from 1.4 to 2.5 m.

本發明之光學補償膜之膜厚並無特別限制，較好依目的變化。例如，使用於偏光保護膜中時較好為20~200μm。 The film thickness of the optical compensation film of the present invention is not particularly limited, and it is preferably changed depending on the purpose. For example, it is preferably from 20 to 200 μm when used in a polarizing protective film.

(液晶顯示裝置) (liquid crystal display device)

藉由於液晶顯示裝置中使用本發明之偏光板，可製作各式各樣之辨識性優異之本發明之液晶顯示裝置。 By using the polarizing plate of the present invention in a liquid crystal display device, it is possible to produce a wide variety of liquid crystal display devices of the present invention having excellent visibility.

本發明之偏光板可使用於STN、TN、OCB、HAN、VA(MVA、PVA)、IPS、OCB等各種驅動方式之液晶顯示裝置中，較好為IPS(In-Plane-Switching，橫向切換)及VA(Vertical Alignment，垂直排列)型液晶顯示裝置。 The polarizing plate of the present invention can be used for liquid crystal display devices of various driving methods such as STN, TN, OCB, HAN, VA (MVA, PVA), IPS, OCB, etc., preferably IPS (In-Plane-Switching, horizontal switching) And a VA (Vertical Alignment) type liquid crystal display device.

本發明中，尤其為具有背光、液晶胞、及於該液晶胞之辨識側及背光側上各具有一片偏光板之液晶顯示裝置，且就亮度不均改善之觀點而言，較好特徵為具備將本發明之長條狀偏光板裁斷獲得之偏光板，且滿足下述要件(a)~(c)之液晶顯示裝置。 In the present invention, in particular, a liquid crystal display device having a backlight, a liquid crystal cell, and a polarizing plate on the identification side and the backlight side of the liquid crystal cell, and in view of improvement in luminance unevenness, is preferably characterized in that The long polarizing plate of the present invention cuts off the obtained polarizing plate, and satisfies the liquid crystal display devices of the following requirements (a) to (c).

(a)作為前述液晶胞之背光側之偏光板(以下稱為「偏光板1」)，係以使如申請專利範圍第1項所記載之長條狀偏光板裁斷所得之偏光板之光學補償膜(以下稱為「光學補償膜1」)位於前述液晶胞側之方式配置，(b)前述液晶胞之辨識側之偏光板(以下稱為「偏 光板2」)係以透明保護膜、偏光器及光學補償膜(以下稱為「光學補償膜2」)之順序層合而成之偏光板，且以該光學補償膜2位於該液晶胞側之方式配置，(c)以使前述偏光板1與前述偏光板2之吸收軸正交之方式配置。 (a) The polarizing plate as the backlight side of the liquid crystal cell (hereinafter referred to as "polarizing plate 1") is optically compensated for the polarizing plate obtained by cutting the long polarizing plate described in the first aspect of the patent application. The film (hereinafter referred to as "optical compensation film 1") is disposed on the liquid crystal cell side, and (b) the polarizing plate on the identification side of the liquid crystal cell (hereinafter referred to as "bias" The light plate 2") is a polarizing plate in which a transparent protective film, a polarizer, and an optical compensation film (hereinafter referred to as "optical compensation film 2") are laminated in this order, and the optical compensation film 2 is located on the liquid crystal cell side. In the mode arrangement, (c) is disposed such that the polarizing plate 1 is orthogonal to the absorption axis of the polarizing plate 2.

且，前述液晶胞為垂直配向型液晶胞，前述光學補償膜2較好含有醯基取代度在2.0~2.6之範圍內之纖維素酯，且滿足以前述式(2)~式(5)表示之關係。 Further, the liquid crystal cell is a vertical alignment type liquid crystal cell, and the optical compensation film 2 preferably contains a cellulose ester having a thiol substitution degree in the range of 2.0 to 2.6, and satisfies the above formula (2) to formula (5). Relationship.

再者，反射型亮度提高薄膜為具備在前述背光與偏光板1之間，且該反射型亮度提高薄膜之透過軸與前述偏光板2之偏光器之吸收軸成正交之方式配置之樣態之液晶顯示裝置，就維持黑色顯示性能之觀點而言係較佳。 Further, the reflective brightness enhancement film is disposed between the backlight and the polarizing plate 1 and the transmission axis of the reflective brightness enhancement film is orthogonal to the absorption axis of the polarizer of the polarizing plate 2. The liquid crystal display device is preferable from the viewpoint of maintaining black display performance.

[垂直配向型液晶胞] [vertical alignment type liquid crystal cell]

本發明之液晶顯示裝置較好具有垂直配向型液晶胞，但本發明之液晶胞可使用過去習知之各種液晶胞例如VA(MVA、PVA)型或VA-IPS、TBA型等。以兩片透明基板夾持之液晶之介電率向異性可為正亦可為負。 The liquid crystal display device of the present invention preferably has a vertical alignment type liquid crystal cell. However, the liquid crystal cell of the present invention can use various liquid crystal cells known in the art such as VA (MVA, PVA) type or VA-IPS, TBA type or the like. The dielectric anisotropy of the liquid crystal sandwiched between the two transparent substrates may be positive or negative.

且，本發明亦適用於COA方式，該COA方式係以例如特開2011-28207號公報等中所記載之方式，使彩色濾波器直接形成於液晶胞之驅動側基板上之彩色濾光器一體型驅動基板，與具備對向電極(導電層)之對向基板介隔隔離材而對向配置，且於其間隙部封入液晶材料而成之構成者，可在反射電極上形成彩色濾光器，且可使在高精密 時貼合之餘裕度變寬並提高良率或開口率。 Furthermore, the present invention is also applicable to a COA system in which a color filter is directly formed on a driving side substrate of a liquid crystal cell by a method described in, for example, JP-A-2011-28207. The bulk drive substrate can be disposed opposite to the counter substrate having the counter electrode (conductive layer), and the liquid crystal material can be sealed in the gap portion, and the color filter can be formed on the reflective electrode. And can be made in high precision The margin of fit is widened and the yield or aperture ratio is increased.

本發明中，該液晶胞之一例可在上下基板間使用介電向異性為負，△n=0.0815，△ε=-4.5左右之向列型(nematic)液晶材料等。 In the present invention, in one example of the liquid crystal cell, a nematic liquid crystal material having a negative dielectric anisotropy, Δn = 0.0815, Δε = -4.5 or so may be used between the upper and lower substrates.

液晶層之厚度d並無特別限制，但使用前述範圍特性之液晶時，可例如設定成3.5μm左右。 The thickness d of the liquid crystal layer is not particularly limited. However, when a liquid crystal having the above range characteristics is used, it can be set, for example, to about 3.5 μm.

又，垂直配向型(VA型)液晶顯示裝置中，添加TN模式之顯示裝置中常用之對掌性材料由於使動態應答特性變差故較少使用，但亦有為了降低配向不良而添加之情況。 Further, in the vertical alignment type (VA type) liquid crystal display device, the palm-shaped material commonly used in the display device in which the TN mode is added is less used because the dynamic response characteristics are deteriorated, but it is also added in order to reduce the misalignment. .

又，成為多區域構造時，就調整各區域間之邊界區域之液晶分子之配向亦為有利。 Further, in the case of a multi-region structure, it is also advantageous to adjust the alignment of the liquid crystal molecules in the boundary region between the regions.

又，所謂「多區域構造」意指將液晶顯示裝置之一像素分割成複數個區域之構造。例如，垂直配向型(VA)型液晶顯示裝置中，由於白色顯示時液晶分子傾斜，故於與傾斜方向相反之方向自斜向觀察時之液晶分子之雙折射大小不同，亮度或色調產生差異，但成為多區域構造時，由於亮度或色調之視角特性受到改善故較佳。 In addition, the "multi-region structure" means a structure in which one pixel of a liquid crystal display device is divided into a plurality of regions. For example, in a vertical alignment type (VA) type liquid crystal display device, since the liquid crystal molecules are inclined at the time of white display, the liquid crystal molecules have different birefringence sizes when viewed from an oblique direction in a direction opposite to the oblique direction, and the brightness or the hue is different. However, when it is a multi-region structure, it is preferable since the viewing angle characteristics of brightness or hue are improved.

具體而言，藉由使像素之各者以使液晶分子之初期配向狀態相互不同之兩個以上之區域構成而平均化，可減低依存於視角之亮度或色調之失衡。且，使各像素由在電壓施加狀態下液晶分子之配向方向連續變化之互不相同之兩個以上之區域構成亦可獲得同樣之效果。 Specifically, by averaging the pixels in each of two or more regions in which the initial alignment states of the liquid crystal molecules are different from each other, the imbalance between the brightness and the hue depending on the viewing angle can be reduced. Further, the same effect can be obtained by constituting each pixel by two or more regions which are different from each other in the direction in which the alignment of the liquid crystal molecules is continuously changed in the voltage application state.

就在全部方向獲得均等之視角而言，只要增多該分割 數即可，但藉由成為四分割以上即可獲得大致均等之視角。 As far as equal direction is obtained in all directions, as long as the segmentation is increased The number is sufficient, but a substantially equal angle of view can be obtained by being divided into four or more.

本發明在應用於畫面為30吋型以上之大畫面之垂直配向型液晶顯示裝置時，尤其可獲得黑色顯示時之亮度不均優異之液晶顯示裝置。 When the present invention is applied to a vertical alignment type liquid crystal display device having a large screen size of 30 Å or more, a liquid crystal display device excellent in luminance unevenness in black display can be obtained.

於液晶胞上貼合偏光板時，亦可不預先自長條狀偏光板切出片狀之偏光板，而係以輥狀直接貼合之輥對面板(roll to panel)之方式進行。 When the polarizing plate is bonded to the liquid crystal cell, the sheet-shaped polarizing plate may be cut out from the long-length polarizing plate in advance, and the roll-to-panel may be directly bonded in a roll shape.

[實施例] [Examples]

以下，列舉實施例具體說明本發明，但本發明並不限於該等。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

〈實施例1〉 <Example 1> [偏光器A1之製作] [Production of Polarizer A1]

以35℃之水使膜厚75μm之聚乙烯醇薄膜膨潤，將其浸漬在由碘0.075g、碘化鉀5g、水100g所組成之水溶液中60秒，接著浸漬在由碘化鉀3g、硼酸7.5g、水100g所組成之45℃水溶液中，隨後，在55℃下以拉幅機，以延伸倍率4.5倍進行橫向延伸。將其經水洗、乾燥，進行捲取，獲得捲繞長度1000m之長條狀偏光器A1。 The polyvinyl alcohol film having a thickness of 75 μm was swollen with water at 35 ° C, and immersed in an aqueous solution composed of 0.075 g of iodine, 5 g of potassium iodide, and 100 g of water, followed by immersion in 3 g of potassium iodide, 7.5 g of boric acid, and water. 100 g of a 45 ° C aqueous solution was formed, followed by lateral stretching at a stretching machine at a stretching ratio of 4.5 times at 55 ° C. This was washed with water, dried, and wound up to obtain a long strip-shaped polarizer A1 having a winding length of 1000 m.

[偏光器A2之製作] [Production of Polarizer A2]

藉由具有下述步驟之方法，製作偏光器A2。 The polarizer A2 was fabricated by the method having the following steps.

(1)膨潤步驟及延伸步驟 (1) swelling step and extension step

準備聚合度2400、皂化度99.9%之膜厚75μm之聚乙烯醇(PVA)薄膜(薄膜寬度：300mm)。將前述PVA薄膜之單面浸漬在30℃之溫水(膨潤浴)中60秒，經膨潤，且以相對於膨潤前之薄膜寬度成為2倍長之方式朝寬度方向進行拉幅機延伸(橫向延伸)。 A polyvinyl alcohol (PVA) film (film width: 300 mm) having a polymerization degree of 2400 and a saponification degree of 99.9% and a film thickness of 75 μm was prepared. The single surface of the PVA film was immersed in a warm water (swell bath) at 30 ° C for 60 seconds, swollen, and stretched in the width direction so as to be twice as long as the film width before swelling (horizontal extend).

(2)染色步驟及延伸步驟 (2) Dyeing step and extension step

自前述膨潤浴中拉出前述PVA薄膜，浸漬在以質量比1：7之比例包含碘與碘化鉀之濃度3.2質量%之30℃水溶液(染色浴)中60秒，且以相對於前述膨潤步驟前之PVA薄膜之寬度成為3.5倍長之方式，朝寬度方向進行拉幅機延伸(橫向延伸)。 The PVA film was pulled out from the swelling bath and immersed in a 30 ° C aqueous solution (dye bath) containing a concentration of iodine and potassium iodide at a mass ratio of 1:7 for 60 seconds, and before the swelling step. The width of the PVA film is 3.5 times longer, and the tenter stretches (laterally extends) in the width direction.

(3)交聯步驟及延伸步驟 (3) Cross-linking step and extension step

自前述染色浴拉出前述PVA薄膜，浸漬在含有3質量%之硼酸與3質量%之碘化鉀之30℃水溶液(交聯浴)中20秒後，以相對於前述膨潤步驟前之PVA薄膜之寬度成為3.6倍長之方式，朝寬度方向進行拉幅機延伸(橫向延伸)。 The PVA film was pulled out from the dyeing bath, and immersed in a 30 ° C aqueous solution (cross-linking bath) containing 3% by mass of boric acid and 3% by mass of potassium iodide for 20 seconds, relative to the width of the PVA film before the swelling step. In a manner of 3.6 times longer, the tenter is extended in the width direction (lateral extension).

(4)延伸步驟 (4) Extension step

自前述交聯浴拉出前述PVA薄膜，浸漬在含有4質 量%之硼酸與5質量%之碘化鉀之60℃水溶液(延伸浴)中60秒後，以相對於前述膨潤步驟前之PVA薄膜之寬度成為5.9倍長之方式，朝寬度方向進行拉幅機延伸(橫向延伸)。 Pulling out the aforementioned PVA film from the aforementioned cross-linking bath, immersed in a substance containing 4 60 seconds after the amount of boric acid and 5% by mass of potassium iodide in a 60 ° C aqueous solution (extension bath), the tenter stretching was performed in the width direction so as to be 5.9 times longer than the width of the PVA film before the swelling step. (lateral extension).

(5)調整(碘離子含浸處理)．乾燥步驟 (5) Adjustment (iodine ion impregnation treatment). Drying step

自前述延伸浴拉出前述PVA薄膜，浸漬在含3質量%之碘化鉀之30℃水溶液(調整浴)中20秒。接著，在60℃對該PVA薄膜施以乾燥處理4分鐘，獲得本實施例之偏光器A2。 The PVA film was pulled out from the above stretching bath, and immersed in a 30 ° C aqueous solution (adjustment bath) containing 3 mass% of potassium iodide for 20 seconds. Next, the PVA film was subjected to a drying treatment at 60 ° C for 4 minutes to obtain a polarizer A2 of the present example.

所得偏光器之吸收軸之寬度方向軸角度以原材料中心設為0°(TD方向)時，原材料之右端為-3°，左端為+3°，在兩端部軸錯開，產生彎曲變形現象(bowing Phenomenon)。 When the width direction of the absorption axis of the obtained polarizer is 0° (TD direction), the right end of the material is -3°, and the left end is +3°, and the shaft is staggered at both ends to cause bending deformation ( Bowing Phenomenon).

[偏光器A3之製作] [Production of Polarizer A3]

以35℃之水使膜厚75μm之聚乙烯醇薄膜膨潤，使其浸漬在由碘0.075g、碘化鉀5g、水100g所組成之水溶液中60秒，接著浸漬在由碘化鉀3g、硼酸7.5g、水100g所組成之45℃水溶液中並經單軸延伸(溫度55℃，延伸倍率5倍)。將其經水洗、乾燥，獲得偏光器A3。 The polyvinyl alcohol film having a thickness of 75 μm was swollen with water at 35 ° C, and immersed in an aqueous solution composed of 0.075 g of iodine, 5 g of potassium iodide, and 100 g of water, followed by immersion in 3 g of potassium iodide, 7.5 g of boric acid, and water. 100 g of a 45 ° C aqueous solution was formed and uniaxially stretched (temperature 55 ° C, stretching ratio 5 times). This was washed with water and dried to obtain a polarizer A3.

[偏光器A4之製作] [Production of Polarizer A4]

除延伸倍率設為3倍以外，餘以與偏光器A1之製作 相同，製作偏光器A4。 In addition to the extension ratio set to 3 times, the remainder is made with the polarizer A1 In the same manner, the polarizer A4 was fabricated.

[偏光器之N_Z係數之評價] [Evaluation of N _Z Coefficient of Polarizer]

使用KOBRA-WX100/IR(王子量測設備股份有限公司製造)，在溫度23℃、濕度55%RH之環境下，求得波長1000nm之n_x、n_y、n_z，且具算出N_Z。平均折射率係使用1.60。示於表1。 Using KOBRA-WX100/IR (manufactured by Oji Scientific Instruments Co., Ltd.), n _x , n _y , and n _{z having a} wavelength of 1000 nm were obtained in an environment of a temperature of 23 ° C and a humidity of 55% RH, and N _{Z was} calculated. The average refractive index was 1.60. Shown in Table 1.

[光學補償膜C1之製作] [Production of Optical Compensation Film C1] (微粒子分散液1) (Microparticle Dispersion 1)

微粒子(Aerosil R812日本AEROSIL(股)製造) Microparticles (Aerosil R812, manufactured by AEROSIL, Japan)

11質量份    11 parts by mass

乙醇 89質量份 Ethanol 89 parts by mass

以溶解器將上述成分攪拌混合50分鐘後，以均質機進行分散。 The above components were stirred and mixed for 50 minutes in a dissolver, and then dispersed by a homogenizer.

〈微粒子添加液1〉 <Microparticle Addition Liquid 1>

於投入有二氯甲烷之溶解槽中，邊充分攪拌邊緩慢添加微粒子分散液1。接著，以使二次粒子之粒徑成為特定大小之方式，以攪動機(attritor)進行分散。以日本精線(股)製造之FINEMET NF過濾，調製微粒子添加液1。 The fine particle dispersion 1 was slowly added while thoroughly stirring in a dissolution tank to which methylene chloride was charged. Next, the particles are dispersed at an attritor so that the particle diameter of the secondary particles becomes a specific size. The fine particle addition liquid 1 was prepared by filtration using FINEMET NF manufactured by Nippon Seisaku Co., Ltd.

二氯甲烷 99質量份 Methylene chloride 99 parts by mass

微粒子分散液1 5質量份 Microparticle dispersion 15 parts by mass

調製下述組成之主要摻雜劑。首先將二氯甲烷與乙醇添加於加壓溶解槽中。邊攪拌邊將乙醯基取代度2.45之纖維素酯投入該裝有溶劑之加壓溶解槽中。將其加熱，邊攪拌邊完全溶解。使用安積濾紙(股)製造之安積濾紙No.244將其過濾，調製主要摻雜劑。 The main dopant of the following composition was prepared. First, dichloromethane and ethanol were added to the pressurized dissolution tank. The cellulose ester having an ethylidene substitution degree of 2.45 was placed in the pressurized dissolution tank containing the solvent while stirring. It was heated and completely dissolved while stirring. The filter paper No. 244, manufactured by using an ampoule filter (strand), was filtered to prepare a main dopant.

(主要摻雜劑之組成) (composition of main dopants)

二氯甲烷 340質量份 Dichloromethane 340 parts by mass

乙醇 64質量份 Ethanol 64 parts by mass

纖維素酯(乙醯基取代度2.45,Mn=6000) 100質量份 Cellulose ester (acetamyl substitution degree 2.45, Mn=6000) 100 parts by mass

糖酯化合物M 12質量份 Sugar ester compound M 12 parts by mass

微粒子添加液1 1質量份 Microparticle addition solution 1 part by mass

將上述投入密閉之主溶解釜中，邊攪拌邊溶解而調製摻雜劑。 The above-mentioned main dissolution vessel was placed in a sealed state, and dissolved while stirring to prepare a dopant.

〈羧酸糖酯化合物M之合成〉 <Synthesis of Carboxylic Acid Glycol Compound M>

於具備攪拌裝置、回流冷卻器、溫度計及氮氣導入管之四頸燒瓶中饋入蔗糖34.2g(0.1莫耳)、苯甲酸酐135.6g(0.6莫耳)、吡啶284.8g(3.6莫耳)，在攪拌下邊自氮氣導入管吹拂氮氣邊升溫，且在70℃進行酯化反應5小時。 34.2 sucrose (0.1 mol), 135.6 g (0.6 mol) of benzoic anhydride The temperature was raised while blowing nitrogen gas from a nitrogen introduction tube while stirring, and the esterification reaction was carried out at 70 ° C for 5 hours.

接著，將燒瓶內部減壓至4×10²Pa以下，在60℃餾除 過量吡啶後，將燒瓶內部減壓至1.3×10Pa以下，升溫至120℃，餾除苯甲酸酐及生成之苯甲酸之大部分。接著，再添加甲苯1L、0.5質量%之碳酸鈉水溶液300g，在50℃攪拌30分鐘後，靜置，分取甲苯層。最後，將水100g添加於分取之甲苯層中，在常溫水洗30分鐘後，分取甲苯層，在減壓下(4×10² Pa以下)、於60℃餾除甲苯、獲得化合物A-1、A-2、A-3、A-4及A-5等之混合物之糖酯化合物M。 Next, the inside of the flask was depressurized to 4 × 10 ² Pa or less, and after the excess pyridine was distilled off at 60 ° C, the inside of the flask was depressurized to 1.3 × 10 Pa or less, and the temperature was raised to 120 ° C to distill off the benzoic anhydride and the benzoic acid formed. Most of it. Then, 300 g of a sodium carbonate aqueous solution of 1 L of toluene and 0.5% by mass was further added, and the mixture was stirred at 50 ° C for 30 minutes, and then allowed to stand, and the toluene layer was separated. Finally, 100 g of water was added to the separated toluene layer, and after washing at room temperature for 30 minutes, the toluene layer was separated, and toluene was distilled off under reduced pressure (4×10 ² Pa or less) at 60° C. to obtain a compound A- A sugar ester compound M of a mixture of A-2, A-3, A-4 and A-5.

以高速液體層析-質量分析(HPLC-MS)解析所得混合物後，A-1為1.2質量%，A-2為13.2質量%，A-3為14.2質量%，A-4為35.4質量%，A-5為40.0質量%。平均取代度為5.2。 After analyzing the obtained mixture by high-speed liquid chromatography-mass spectrometry (HPLC-MS), A-1 was 1.2% by mass, A-2 was 13.2% by mass, A-3 was 14.2% by mass, and A-4 was 35.4% by mass. A-5 was 40.0% by mass. The average degree of substitution is 5.2.

於不鏽鋼帶支撐體上進行澆鑄(Cast)並蒸發溶劑直到薄膜中之殘留溶劑量成為75%為止。接著，以剝離張力 130N/m自不鏽鋼帶支撐體剝離。剝離之光學補償膜邊施加170℃之熱邊使用拉幅機朝寬度方向延伸35%，延伸開始時之殘留溶劑為15%。 Casting was performed on a stainless steel belt support and the solvent was evaporated until the amount of residual solvent in the film became 75%. Next, take off the tension 130 N/m was peeled off from the stainless steel belt support. The peeling optical compensation film was stretched by 35% in the width direction by a tenter while applying a hot edge of 170 ° C, and the residual solvent at the start of the elongation was 15%.

接著，於乾燥區邊以多數輥邊輸送邊結束乾燥。乾燥溫度設為130℃，輸送張力設為100N/m。如上述，獲得乾燥膜厚38μm之光學補償膜C1。光學補償膜C1之面內相位差值Ro為52nm，厚度方向之相位差值Rt為125nm。 Next, the drying was completed while conveying at a plurality of rolls at the side of the drying zone. The drying temperature was set to 130 ° C, and the conveying tension was set to 100 N/m. As described above, an optical compensation film C1 having a dried film thickness of 38 μm was obtained. The in-plane retardation value Ro of the optical compensation film C1 was 52 nm, and the phase difference Rt in the thickness direction was 125 nm.

[光學補償膜C2之製作] [Production of Optical Compensation Film C2] 〈二氧化矽分散液〉 <cerium oxide dispersion>

Aerosil R812(日本AEROSIL(股)製造) 10質量份 Aerosil R812 (manufactured by AEROSIL Co., Ltd.) 10 parts by mass

(一次粒子之平均粒徑7nm) (average particle size of primary particles is 7 nm)

乙醇 90質量份 90 parts by weight of ethanol

以溶解器將上述成分攪拌混合30分鐘後，以均質機進行分散。邊攪拌邊將88質量分之二氯甲烷投入二氧化矽分散液中，以溶解器攪拌混合30分鐘，製作二氧化矽分散稀釋液。以微粒子分散稀釋液過濾器(Advantec東洋(股)：聚丙烯捲繞匣過濾器TCW-PPS-1N)過濾。 The above components were stirred and mixed for 30 minutes in a dissolver, and then dispersed by a homogenizer. 88 parts by mass of dichloromethane was introduced into the cerium oxide dispersion while stirring, and the mixture was stirred and mixed for 30 minutes with a dissolver to prepare a cerium oxide dispersion diluent. Filtration was carried out using a fine particle dispersion diluent filter (Advantec Toyo: polypropylene winding enthalpy filter TCW-PPS-1N).

〈摻雜劑組成物〉 <Dopant Composition>

纖維素三乙酸酯 90質量份 Cellulose triacetate 90 parts by mass

(由亞麻棉合成之纖維素三乙酸酯，乙醯基取代度2.88，Mn=140000) (Cellulose triacetate synthesized from linen cotton, the substitution degree of ethyl ketone is 2.88, Mn = 140000)

丙烯酸化合物 10質量份 Acrylic compound 10 parts by mass

二氧化矽分散稀釋液 4質量份 Ceria dispersing diluent 4 parts by mass

二氯甲烷 432質量份 Dichloromethane 432 parts by mass

乙醇 38質量份 Ethanol 38 parts by mass

將上述投入密閉容器中，邊加熱、攪拌使完全溶解，且使用安積濾紙(股)製造之安積濾紙No.24過濾，調製摻雜劑。 The mixture was placed in a sealed container, and the mixture was heated and stirred to be completely dissolved, and filtered using an Augmentation filter paper No. 24, which was produced by using a filter paper (strand), to prepare a dopant.

接著，使用帶澆鑄裝置，均勻澆鑄於不鏽鋼帶支撐體上。在不鏽鋼帶支撐體上蒸發溶劑至殘留溶劑量成為100%為止，且自不鏽鋼帶支撐體剝離。使纖維素酯薄膜之網片在35℃下蒸發溶劑，切割成1.65m之寬度，以拉幅機保持寬度且以160℃之乾燥溫度(亦稱為熱處理溫度、延伸溫度)乾燥。乾燥開始時之殘留溶劑量為20%。隨後，在120℃之乾燥裝置內邊以多數輥輸送邊乾燥15分鐘後，對薄膜兩端施以寬度15mm、高度5μm之襯裡加工，且捲繞至捲芯上，獲得膜厚20μm之光學補償膜C2。該光學補償膜C2之面內相位差值Ro為0nm，厚度方向之相位差值Rt為5nm。光學補償膜C2之殘留溶劑量為0.2%，捲繞數為6000m。 Next, it was uniformly cast on a stainless steel belt support using a belt casting apparatus. The solvent was evaporated on the stainless steel belt support until the amount of residual solvent became 100%, and the stainless steel belt support was peeled off. The web of the cellulose ester film was evaporated at 35 ° C, cut into a width of 1.65 m, held in a tenter width, and dried at a drying temperature of 160 ° C (also referred to as heat treatment temperature, elongation temperature). The amount of residual solvent at the start of drying was 20%. Subsequently, after drying for 15 minutes in a drying apparatus at 120 ° C with a plurality of rolls, a lining of a width of 15 mm and a height of 5 μm was applied to both ends of the film, and wound onto a core to obtain an optical compensation of a film thickness of 20 μm. Film C2. The in-plane phase difference value Ro of the optical compensation film C2 was 0 nm, and the phase difference Rt in the thickness direction was 5 nm. The amount of residual solvent of the optical compensation film C2 was 0.2%, and the number of windings was 6000 m.

〈丙烯酸化合物之合成〉 <Synthesis of Acrylic Compounds>

於安裝攪拌機、兩個滴加漏斗、氣體導入管及溫度計之玻璃燒瓶中，饋入以MMA(甲基丙烯酸甲酯)為80、HEA(丙烯酸β-羥基乙酯)為20之比率混合之單體混合液40g、鏈轉移劑之巰基丙酸3.0g及甲苯30g，升溫至 90℃。隨後，在3小時內自其一滴加漏斗滴加與上述相同之單體混合液60g，同時自另一漏斗於3小時內滴加溶解於甲苯14g中之偶氮雙異丁腈0.6g。隨後再於2小時內滴加溶解於甲苯56g中之偶氮雙異丁腈0.6g後，再持續反應2小時，獲得丙烯酸化合物。 In a glass flask equipped with a stirrer, two dropping funnels, a gas introduction tube, and a thermometer, a single sample mixed with MMA (methyl methacrylate) of 80 and HEA (β-hydroxyethyl acrylate) of 20 was fed. 40 g of the body mixture, 3.0 g of mercaptopropionic acid as a chain transfer agent, and 30 g of toluene, and the temperature was raised to 90 ° C. Subsequently, 60 g of the same monomer mixture as above was added dropwise from a dropping funnel over 3 hours, while 0.6 g of azobisisobutyronitrile dissolved in 14 g of toluene was added dropwise from another funnel over 3 hours. Subsequently, 0.6 g of azobisisobutyronitrile dissolved in 56 g of toluene was added dropwise thereto over 2 hours, and the reaction was continued for 2 hours to obtain an acrylic compound.

〈分子量測定〉 <Molecular weight determination>

重量平均分子量之測定係使用高速液體層析儀測定。測定條件如下。 The measurement of the weight average molecular weight is carried out using a high speed liquid chromatograph. The measurement conditions are as follows.

溶劑：二氯甲烷 Solvent: dichloromethane

管柱：Shodex K806、K805、K803G(昭和電工(股)製造，三根串聯使用) Pipe column: Shodex K806, K805, K803G (made by Showa Denko (share), three in series)

管柱溫度：25℃ Column temperature: 25 ° C

試料濃度：0.1質量% Sample concentration: 0.1% by mass

檢測器：RI型號504(GL科技公司製造) Detector: RI model 504 (manufactured by GL Technology)

泵：L6000(日立製作所(股)製造) Pump: L6000 (manufactured by Hitachi, Ltd.)

流量：1.0ml/min Flow rate: 1.0ml/min

校正曲線：使用利用標準聚苯乙烯STK standard聚苯乙烯(TOSOH(股)製造)Mw=1000000~500之13種樣品獲得之校正曲線。13種樣品幾乎等間隔使用。 Calibration curve: A calibration curve obtained using 13 samples of standard polystyrene STK standard polystyrene (manufactured by TOSOH) Mw = 1000000 to 500 was used. Thirteen samples were used at almost equal intervals.

[光學補償膜C3及C5之製作] [Production of optical compensation film C3 and C5]

將下述通式中，R¹為氫原子，R²及R³為甲基之具有 內酯環構造之(甲基)丙烯酸樹脂{共聚合單體質量比=甲基丙烯酸甲酯/2-(羥基甲基)丙烯酸甲酯=8/2，內酯環化率約100%，內酯環構造之含有比例19.4%，重量平均分子量133000，熔融流動速率6.5g/10分鐘(240℃，98N(10kgf)，Tg 131℃)90質量份，與丙烯腈-苯乙烯(AS)樹脂{TOYO AS AS20，東洋苯乙烯公司製造}10質量分之混合物；Tg 127℃)之顆粒供給於雙軸擠出機中，在約280℃熔融擠出成薄片狀，獲得膜厚43μm之具有內酯環構造之(甲基)丙烯酸樹脂薄片。使該未延伸之薄片在160℃之溫度條件下延伸成縱向2.0倍、橫向2.4倍，獲得膜厚15μm之(甲基)丙烯酸樹脂薄膜C3。該光學補償膜C3之面內相位差值Ro為0nm，厚度方向之相位差值Rt為0nm。 A (meth)acrylic resin having a lactone ring structure in which R ¹ is a hydrogen atom and R ² and R ³ are a methyl group in the following formula: {Copolymerization monomer mass ratio = methyl methacrylate/2- Methyl (hydroxymethyl) acrylate = 8/2, cyclization rate of lactone is about 100%, content of lactone ring structure is 19.4%, weight average molecular weight is 133,000, and melt flow rate is 6.5 g/10 min (240 ° C, 98 N) (10 kgf), Tg 131 ° C) 90 parts by mass, and a mixture of acrylonitrile-styrene (AS) resin {TOYO AS AS20, manufactured by Toyo Styrene Co., Ltd., 10 parts by mass; Tg 127 ° C), for biaxial extrusion In the machine, it was melt-extruded into a sheet shape at about 280 ° C to obtain a (meth)acrylic resin sheet having a lactone ring structure having a film thickness of 43 μm. The unstretched sheet was stretched 2.0 times in the longitudinal direction and 2.4 times in the transverse direction at a temperature of 160 ° C to obtain a (meth)acrylic resin film C3 having a film thickness of 15 μm. The in-plane phase difference value Ro of the optical compensation film C3 was 0 nm, and the phase difference Rt in the thickness direction was 0 nm.

對(甲基)丙烯酸樹脂薄膜之單面施加電暈放電處理(電暈放電電子照射量：77W/m²/min)。混合聚酯胺基甲酸酯(第一工業至要製造，商品名：SUPERFLEX 210，固體成分33%)16.8g、交聯劑(含有噁唑啉之聚合物，日本觸媒製造，商品名：EPOCROS WS-700，固成分： 25%)4.2g、1質量%之氨水2.0g、膠體二氧化矽(扶桑化學工業製造，科特隆(COTLON)PL-3，固體成分：20質量%)0.42g及純水76.6g，獲得易接著劑組成物。 A corona discharge treatment (corona discharge electron irradiation amount: 77 W/m ² /min) was applied to one side of the (meth)acrylic resin film. Mixed polyester urethane (first industry to be manufactured, trade name: SUPERFLEX 210, solid content 33%) 16.8 g, cross-linking agent (polymer containing oxazoline, manufactured by Nippon Shokubai, trade name: EPOCROS WS-700, solid content: 25%) 4.2 g, 1% by mass aqueous ammonia 2.0 g, colloidal cerium oxide (manufactured by Fuso Chemical Industry, COTLON PL-3, solid content: 20% by mass) 0.42 g and pure water 76.6 g obtained an easy-adhesive composition.

以使乾燥後之厚度成為350nm之方式，以棒塗佈器(#6)將所得之易接著劑組成物塗佈於施以電暈放電處理之(甲基)丙烯酸樹脂膜之電暈放電處理面上。隨後，將(甲基)丙烯酸樹脂薄膜投入熱風乾燥機(140℃)中，使易接著劑組成物乾燥約5分鐘，形成易接著層(0.3~0.5μm)，獲得光學補償膜C3。 The resulting easy-to-adhere composition was applied to a corona discharge treatment of a (meth)acrylic resin film subjected to corona discharge treatment by a bar coater (#6) so that the thickness after drying became 350 nm. On the surface. Subsequently, the (meth)acrylic resin film was placed in a hot air dryer (140 ° C), and the easy-adhesive composition was dried for about 5 minutes to form an easy-adhesion layer (0.3 to 0.5 μm) to obtain an optical compensation film C3.

除熔融擠出時之膜厚成為25μm以外餘相同，獲得膜厚8μm之光學補償膜C5。該光學補償膜C5之面內相位差值Ro為0nm，厚度方向之相位差值Rt為0nm。 The optical compensation film C5 having a film thickness of 8 μm was obtained in the same manner except that the film thickness at the time of melt extrusion was 25 μm. The in-plane retardation value Ro of the optical compensation film C5 was 0 nm, and the phase difference Rt in the thickness direction was 0 nm.

[光學補償膜C4之製作] [Production of Optical Compensation Film C4]

含有降冰片烯系樹脂之高分子薄膜(日本ZEON(股)製造，商品名「ZEONOR」，膜厚：100μm，薄膜寬度：700mm)，使用拉幅延伸機，在143℃進行3倍之橫向單軸延伸，獲得膜厚35μm之光學補償膜C4。所得光學補償膜C4之面內相位差值Ro為270nm，厚度方向之相位差值Rt為197nm。 Polymer film containing norbornene-based resin (manufactured by ZEON Co., Ltd., trade name "ZEONOR", film thickness: 100 μm, film width: 700 mm), using a tenter stretching machine, three times horizontally at 143 ° C The shaft was extended to obtain an optical compensation film C4 having a film thickness of 35 μm. The in-plane retardation value Ro of the obtained optical compensation film C4 was 270 nm, and the phase difference Rt in the thickness direction was 197 nm.

[薄膜之相位差測定] [Measurement of phase difference of film]

所製作之光學補償膜在23℃、55%RH調濕後，使用Axometrcs公司製造之Axoscan，在測定波長590nm測定 相位差。Rt計算用之平均折射率係以Abbe折射計測定三方向之折射率，且使用將其平均而得之值。 The prepared optical compensation film was conditioned at 23 ° C and 55% RH, and then measured at a measuring wavelength of 590 nm using Axoscan manufactured by Axometrcs. Phase difference. The average refractive index for Rt calculation is measured by the Abbe refractometer in three directions, and the average value is used.

測定結果示於表2。 The measurement results are shown in Table 2.

[透明保護膜] [Transparent protective film]

分別使用市售之KONICA MONITA ADVANCE LAYER(股)製造之KC4UA-SW及KC6UA-SW作為透明保護膜B1、B2。 KC4UA-SW and KC6UA-SW manufactured by KONICA MONITA ADVANCE LAYER (commercial), which are commercially available, were used as the transparent protective films B1 and B2, respectively.

[偏光板P1、2之製作] [Production of polarizing plates P1 and 2]

使用50℃之2N KOH水溶液對透明保護膜B1及製作之光學補償膜進行鹼皂化處理，經水洗、乾燥，且如下述般進行偏光板加工。 The transparent protective film B1 and the produced optical compensation film were subjected to alkali saponification treatment using a 2N KOH aqueous solution at 50 ° C, washed with water, dried, and subjected to polarizing plate processing as follows.

使用水糊膠，以兩薄膜夾住偏光板之形態，以壓力20~30 N/cm²，輸送速度約10m/分鐘將前述已皂化之薄膜貼合於製作之偏光器A1之兩側，進行在70℃下約2分鐘，接著在60℃下約2分鐘之乾燥處理，經捲取而製作偏光板輥。將黏著層設置於經剝離加工之聚對苯二甲酸乙二酯薄膜上，且於所得偏光板之光學補償膜側貼合黏著層之面，製作黏著偏光板輥。作為透明保護膜．光學補償膜使 用之薄膜與偏光板之對應關係示於表3。 Using a water paste, the film is sandwiched between the two films, and the saponified film is attached to both sides of the polarizer A1 at a pressure of 20 to 30 N/cm ² at a transport speed of about 10 m/min. The polarizing plate roll was produced by coiling at 70 ° C for about 2 minutes, followed by drying at 60 ° C for about 2 minutes. The adhesive layer was placed on the peeled polyethylene terephthalate film, and the surface of the adhesive layer was bonded to the side of the optical compensation film of the obtained polarizing plate to prepare an adhesive polarizing plate roll. As a transparent protective film. The correspondence between the film used for the optical compensation film and the polarizing plate is shown in Table 3.

[偏光板P3、P5之製作] [Production of polarizing plates P3 and P5]

使用50℃之2N KOH水溶液進行透明保護膜B1之鹼皂化處理，並經水洗、乾燥。 The alkali saponification treatment of the transparent protective film B1 was carried out using a 2N KOH aqueous solution at 50 ° C, washed with water, and dried.

(接著劑組成物之調製) (modulation of the composition of the adhesive)

對於含有乙醯乙醯基之聚乙烯醇系樹脂(平均聚合度：1200，皂化度：98.5莫耳%，乙醯乙醯基變性度：5莫耳%)100質量份，在30℃之溫度條件下將羥甲基三聚氰胺20質量份添加於純水中，獲得固體成分濃度0.5%之水溶液。以所得水溶液作為接著劑組成物，在30℃之溫度條件下使用。 For a polyvinyl alcohol-based resin containing an ethyl acetonitrile group (average degree of polymerization: 1200, degree of saponification: 98.5 mol%, degree of denaturation of acetamidine: 5 mol%), 100 parts by mass, at a temperature of 30 ° C Under the conditions, 20 parts by mass of methylol melamine was added to pure water to obtain an aqueous solution having a solid concentration of 0.5%. The obtained aqueous solution was used as an adhesive composition, and it was used at a temperature of 30 °C.

(偏光板之製作) (production of polarizing plate)

調製上述接著劑組成物後30分鐘後，以乾燥後之厚度成為50nm之方式將接著劑組成物塗佈於光學補償膜C3或C5之易接著層側。同樣的，於如上述之已完成鹼皂化處理之透明保護膜B1之單面塗佈接著劑組成物。隨後，透過接著劑組成物，使用層合機將透明保護膜B1及光學補償膜C3或C5分別層合於偏光器A1之兩面上，放入熱風乾燥機(70℃)中乾燥5分鐘，獲得偏光板P3、P5。作為透明保護膜．光學補償膜使用之薄膜與偏光板之對應關係示於表3。 30 minutes after the preparation of the above-mentioned adhesive composition, the adhesive composition was applied to the easy-adhesion layer side of the optical compensation film C3 or C5 so that the thickness after drying became 50 nm. Similarly, the adhesive composition was applied to one side of the transparent protective film B1 which had been subjected to alkali saponification as described above. Subsequently, through the adhesive composition, the transparent protective film B1 and the optical compensation film C3 or C5 were laminated on both sides of the polarizer A1 using a laminator, and dried in a hot air dryer (70 ° C) for 5 minutes to obtain Polarizers P3, P5. As a transparent protective film. The correspondence between the film used for the optical compensation film and the polarizing plate is shown in Table 3.

[偏光板P4之製作] [Production of polarizing plate P4]

以光學補償膜C4及透明保護膜B1夾持偏光器A2之方式，以接著劑貼合上述偏光器A2、上述光學補償膜C4及透明保護膜B1。接著劑係使用對於含有乙醯乙醯基之聚乙烯醇系樹脂(平均聚合度：1200，皂化度：98.5莫耳%，乙醯乙醯化度：5莫耳%)100質量份，為20質量份之羥甲基三聚氰胺在30℃之條件下溶解於純水中而調製成固體成分濃度3.2質量%之水溶液。使用該接著劑，在30℃之溫度條件下，以輥壓機將前述光學補償膜C4與前述透明保護膜B1貼合於前述偏光器之兩面上後，在60℃乾燥4分鐘，製作偏光板P4。 The polarizer A2, the optical compensation film C4, and the transparent protective film B1 are bonded together with an adhesive so that the optical compensation film C4 and the transparent protective film B1 sandwich the polarizer A2. The following agent was used for 100 parts by mass of a polyvinyl alcohol-based resin (average degree of polymerization: 1200, degree of saponification: 98.5 mol%, degree of acetonitrile: 5 mol%) containing an ethyl acetonitrile group. A part by mass of methylol melamine was dissolved in pure water at 30 ° C to prepare an aqueous solution having a solid concentration of 3.2% by mass. Using the adhesive, the optical compensation film C4 and the transparent protective film B1 were bonded to both surfaces of the polarizer by a roll press at a temperature of 30 ° C, and then dried at 60 ° C for 4 minutes to prepare a polarizing plate. P4.

[重工性之評價] [Evaluation of heavy work]

將所得偏光板P1~P5沖壓成100×100mm尺寸，貼合於玻璃基盤上。自四角之一處自玻璃基盤少許的剝離偏光板，捏住剝離之偏光板邊壓住剝離基盤邊朝對角方向剝離。以合計10片之樣品進行同樣操作，依循以下基準進行評價。 The obtained polarizing plates P1 to P5 were punched into a size of 100 × 100 mm and attached to a glass substrate. A strip of polarizing plate was slightly peeled from one of the four corners from the glass substrate, and the peeling polarizing plate was pinched against the peeling base and peeled off in a diagonal direction. The same operation was performed on a total of 10 samples, and the evaluation was performed according to the following criteria.

○：0~5片產生剝離殘留 ○: 0~5 pieces produced peeling residue

×：6片以上產生剝離殘留 ×: 6 or more peeling residues were generated

上述評價之結果示於表3。 The results of the above evaluation are shown in Table 3.

由表3所示之評價結果可知，本發明之偏光板之重工性獲得改良。 As is apparent from the evaluation results shown in Table 3, the workability of the polarizing plate of the present invention was improved.

〈實施例2〉 <Example 2> [光學補償膜C6之製作] [Production of Optical Compensation Film C6] [摻雜劑組成物1] [Doping composition 1]

DIANALBR85(三菱縲縈(股)製造) 70質量份 DIANALBR85 (manufactured by Mitsubishi Electric Co., Ltd.) 70 parts by mass

纖維素酯(纖維素乙酸酯丙酸酯；平均醯基取代度2.75，乙醯基取代度0.19，丙醯基取代度2.56,Mw=200000) 30質量份 Cellulose ester (cellulose acetate propionate; average thiol substitution degree 2.75, ethyl sulfhydryl substitution degree 0.19, propyl ketone substitution degree 2.56, Mw = 200000)    30 parts by mass

二氯甲烷 300質量份 Dichloromethane 300 parts by mass

乙醇 40質量份 40 parts by weight of ethanol

邊加熱邊使上述組成物充分溶解，製作摻雜劑。 The composition was sufficiently dissolved while heating to prepare a dopant.

(薄膜之製膜) (film formation of film)

使用帶澆鑄裝置，將上述製作之摻雜劑均一澆鑄於溫度22℃、2m寬之不鏽鋼帶支撐體上。於不鏽鋼帶支撐體 上蒸發溶劑至殘留溶劑量為100%為止，以剝離張力162N/m自不鏽鋼帶支撐體上剝離。 The dopant prepared above was uniformly cast on a stainless steel belt support having a temperature of 22 ° C and a width of 2 m using a casting apparatus. Stainless steel belt support The solvent was evaporated to a residual solvent amount of 100%, and peeled off from the stainless steel belt support at a peeling tension of 162 N/m.

剝離之丙烯酸樹脂之網片在35℃下蒸發溶劑，切割成1.6m寬，隨後，以拉幅機邊朝寬度方向延伸1.1倍，邊在135℃之乾燥溫度下乾燥。此時以拉幅機開始延伸時之殘留溶劑量為10%。 The exfoliated acrylic resin web was evaporated at 35 ° C, cut into a width of 1.6 m, and then dried 1.1 times in the width direction with a tenter, and dried at a drying temperature of 135 ° C. At this time, the amount of residual solvent when the tenter was stretched was 10%.

拉幅機延伸後，在130℃進行緩和5分鐘後，邊以多數之輥輸送通過120℃、140℃之乾燥區邊結束乾燥，切割成1.5m寬，且對薄膜之兩端施以寬度10mm、高度5μm之襯裡加工，以初期張力220N/m、最終張力110N/m捲取至內徑15.24 cm捲芯上，獲得丙烯酸樹脂薄膜。 After the tenter was extended, after being relaxed at 130 ° C for 5 minutes, it was conveyed by a plurality of rolls through a drying zone of 120 ° C and 140 ° C to finish drying, cut into a width of 1.5 m, and a width of 10 mm was applied to both ends of the film. The lining of a height of 5 μm was wound up to an inner diameter of 15.24 cm by an initial tension of 220 N/m and a final tension of 110 N/m to obtain an acrylic resin film.

自不鏽鋼帶支撐體之旋轉速度與拉幅機之運轉速度算出之MD方向之延伸倍率為1.1倍，已完成之薄膜殘留溶劑量為0.1%，膜厚為20μm，面內相位差值Ro為0nm，厚度方向之相位差值Rt為0nm，捲繞長為4000m。 The stretching ratio in the MD direction calculated from the rotation speed of the stainless steel belt support and the running speed of the tenter is 1.1 times, the residual film residual solvent amount is 0.1%, the film thickness is 20 μm, and the in-plane retardation value Ro is 0 nm. The phase difference Rt in the thickness direction is 0 nm, and the winding length is 4000 m.

(易接著層之形成) (Easy to form the layer)

以使網片膜厚(wd)成為20μm之方式將下述組成之塗佈液(1a)塗佈於上述製作之薄膜之一面上，接著在100℃乾燥5分鐘，製作塗佈有易接著層之光學補償膜C6。 The coating liquid (1a) having the following composition was applied to one surface of the above-prepared film so that the mesh film thickness (wd) was 20 μm, and then dried at 100 ° C for 5 minutes to prepare an easy-adhesion layer. Optical compensation film C6.

〈塗佈液1a之調製〉 <Modulation of Coating Liquid 1a>

纖維素二乙酸酯(Daicel化學工業(股)製造，商品 名：L-50) 0.8質量份 Cellulose diacetate (Daicel Chemical Industry Co., Ltd., commodity Name: L-50) 0.8 parts by mass

丙酮 7質量份 Acetone 7 parts by mass

甲基乙基酮 7質量份 Methyl ethyl ketone 7 parts by mass

甲醇 6質量份 Methanol 6 parts by mass

[偏光板P11~P14之製作] [Production of polarizing plate P11~P14]

偏光板P11係如P1且P13係如P3般製作。但，關於光學補償膜C6係以使進行易接著處理之面成為聚乙烯醇側之方式貼合。作為透明保護膜．光學補償膜．偏光器使用之薄膜與偏光板之對應關係示於表4。 The polarizing plate P11 is made of P1 and P13 is made of P3. However, the optical compensation film C6 is bonded so that the surface subjected to the easy-to-treat treatment becomes the polyvinyl alcohol side. As a transparent protective film. Optical compensation film. The correspondence between the film used for the polarizer and the polarizing plate is shown in Table 4.

[液晶顯示裝置之製作] [Production of Liquid Crystal Display Device]

剝離IPS模式之東芝公司製造之REGZA42ZS1之偏光板，以表5中記載組合上述製作之偏光板並貼合於面板上，製作液晶顯示裝置(1-1~1-4)，且進行下述評價。 The polarizing plate of REGZA42ZS1 manufactured by Toshiba Co., Ltd. of the IPS mode was peeled off, and the polarizing plate produced as described above was combined and attached to the panel to produce a liquid crystal display device (1-1 to 1-4), and the following evaluation was performed. .

[不均評價] [Uneven evaluation]

在使背光點亮之狀態下，以畫面顯示黑色顯示，且依據以下基準以目視評價亮度不均。 In a state where the backlight is turned on, black display is displayed on the screen, and luminance unevenness is visually evaluated based on the following criteria.

◎：10人中有0~2人可確認出不均 ◎: 0 to 2 out of 10 people can confirm unevenness

○：10人中有3~5人可確認出不均 ○: 3 to 5 out of 10 people can confirm unevenness

×：除了10人中有6~10人可確認出不均以外，且為清楚的不均 ×: In addition to 6 to 10 out of 10 people, it is possible to identify unevenness and clear unevenness.

上述評價結果示於表5。 The above evaluation results are shown in Table 5.

由表5之評價結果可了解，使用本發明之偏光板之液晶顯示裝置幾乎無法確認出亮度不均可知為優異者。 As is apparent from the evaluation results of Table 5, the liquid crystal display device using the polarizing plate of the present invention hardly recognizes that the brightness is not known to be excellent.

〈實施例3〉 <Example 3> [光學補償膜C11之製作] [Production of Optical Compensation Film C11]

除使延伸倍率成為40%，且改變膜厚以外，於與前述薄膜C1同樣，獲得乾燥膜厚70μm之光學補償膜C11。該光學補償膜C11之面內相位差值Ro為70nm，厚度方向之相位差值Rt為240nm。 An optical compensation film C11 having a dried film thickness of 70 μm was obtained in the same manner as the above-described film C1 except that the stretching ratio was changed to 40% and the film thickness was changed. The in-plane retardation value Ro of the optical compensation film C11 was 70 nm, and the phase difference Rt in the thickness direction was 240 nm.

[光學補償膜C12之製作] [Production of Optical Compensation Film C12]

〈微粒子分散液之製作〉 <Production of Microparticle Dispersion>

微粒子(Aerosil R972V(日本AEROSIL股份有限公司製造) 11質量份 Microparticles (Aerosil R972V (manufactured by Japan AEROSIL Co., Ltd.) 11 parts by mass

(一次粒子之平均粒徑16nm，表觀比重90g/升) (The average particle size of primary particles is 16 nm, and the apparent specific gravity is 90 g/liter)

乙醇 89質量份 Ethanol 89 parts by mass

以溶解器攪拌混合以上50分鐘後，以均質機進行分散，獲得微粒子分散液。 The mixture was stirred and mixed for 50 minutes with a dissolver, and then dispersed by a homogenizer to obtain a fine particle dispersion.

〈微粒子添加液〉 <Microparticle Addition Liquid>

於饋入有二氯甲烷之溶解槽中添加纖維素酯(平均乙醯基取代度2.23，Mn=140000)，經加熱完全溶解後，使用安積濾紙(股)製造之安積濾紙No.244將其過濾。邊充分攪拌過濾後之纖維素乙酸酯溶液，邊於其中緩慢添加上述微粒子分散液。接著，以使二次微粒子之粒徑成為特定大小之方式，以攪動機進行分散。以日本精線(股)製造之FINEMET NF將其過濾，調製微粒子添加液。 Adding cellulose ester (average ethyl sulfhydryl substitution degree 2.23, Mn = 140,000) to a dissolution tank fed with methylene chloride, and completely dissolving it by heating, using the filter paper No. 244 manufactured by the filter paper (stock) filter. While the filtered cellulose acetate solution was sufficiently stirred, the above fine particle dispersion was slowly added thereto. Next, the particle size of the secondary fine particles is dispersed so as to have a specific size. It was filtered by FINEMET NF manufactured by Nippon Seisaku Co., Ltd. to prepare a microparticle-added liquid.

(微粒子添加液之組成) (composition of microparticle addition liquid)

二氯甲烷 99質量份 Methylene chloride 99 parts by mass

纖維素酯(上述) 4質量份 Cellulose ester (above) 4 parts by mass

微粒子分散液 11質量份 Microparticle dispersion 11 parts by mass

調製下述組成之主摻雜劑。首先於加壓溶解槽中添加二氯甲烷與乙醇。邊攪拌邊將纖維素酯投入加入有溶劑之 加壓溶解槽中。對其加熱，且邊攪拌邊完全溶解，再添加可塑劑，並經溶解。使用安積濾紙(股)製造之安積濾紙No.244將其過濾，調製主摻雜劑。 A main dopant of the following composition is prepared. First, dichloromethane and ethanol were added to the pressure dissolution tank. Adding cellulose ester to solvent with stirring Pressurize the dissolution tank. It is heated and completely dissolved while stirring, and then a plasticizer is added and dissolved. The prepreg was prepared by filtering the filter paper No. 244 manufactured by the filter paper (strand).

(主摻雜劑組成) (main dopant composition)

二氯甲烷 390質量份 Methylene chloride 390 parts by mass

乙醇 80質量份 80 parts by weight of ethanol

纖維素酯(平均醯基取代度2.48，乙醯基取代度1.58，丙醯基取代度0.90，Mn=160000) 100質量份 Cellulose ester (average thiol substitution degree 2.48, acetonitrile substitution degree 1.58, propyl ketone substitution degree 0.90, Mn=160000) 100 parts by mass

糖化合物([化3]之(A-2)) 4質量份 Sugar compound ((A-2) of [Chemical 3]) 4 parts by mass

以成為主摻雜劑100質量份與微粒子添加液 5質量份之方式添加，且以線上混合機(Toray靜止型管內混合機Hi-Mixer，SWJ)充分混合，接著使用帶澆鑄裝置，均一澆鑄於寬度2m之不鏽鋼帶支撐體上。在不鏽鋼帶支撐體上蒸發溶劑至殘留溶劑量成為110%為止，自不鏽鋼帶支撐體剝離。接著，以拉幅機固定網片之兩端，在185℃於寬度方向延伸42%，延伸結束後維持寬度且保持4秒鐘，寬度方向之張力緩和後釋放寬之固定，接著於設定成125℃之第三乾燥區中輸送30分鐘進行乾燥，且以捲繞長度4000m製作寬度1.49m且於端部具有寬1cm之襯裡之光學補償膜C12。該光學補償膜C12之膜厚為68μm。該光學補償膜C11之面內相位差值Ro為70nm，厚度方向之相位差值Rt為240nm。 It is added so as to be 100 parts by mass of the main dopant and 5 parts by mass of the fine particle addition liquid, and is sufficiently mixed by an in-line mixer (Toray static in-line mixer Hi-Mixer, SWJ), and then uniformly cast using a belt casting device. On a stainless steel belt support with a width of 2m. The solvent was evaporated on the stainless steel belt support until the amount of residual solvent became 110%, and the stainless steel belt support was peeled off. Next, the ends of the mesh are fixed by a tenter, and the width is extended by 42% at 185 ° C. After the extension is completed, the width is maintained for 4 seconds, the tension in the width direction is relaxed, and the width is released, and then set to 125. The third drying zone of °C was conveyed for 30 minutes for drying, and an optical compensation film C12 having a width of 1.49 m and a lining having a width of 1 cm at the end was produced at a winding length of 4000 m. The film thickness of this optical compensation film C12 was 68 μm. The in-plane retardation value Ro of the optical compensation film C11 was 70 nm, and the phase difference Rt in the thickness direction was 240 nm.

[光學補償膜C13之製作] [Production of Optical Compensation Film C13]

以擠出機使熱可塑性樹脂(商品名「ZEONOR1420」，日本ZEON(股)製造，降冰片烯樹脂)之顆粒熔融，供給於擠出用模嘴，形成原材料薄膜。 The pellet of the thermoplastic resin (trade name "ZEONOR 1420", manufactured by Japan ZEON Co., Ltd., norbornene resin) was melted by an extruder and supplied to an extrusion die to form a raw material film.

接著，以拉幅機延伸機使原材料薄膜在延伸溫度170℃，延伸倍率1.01倍下進行延伸，獲得膜厚20μm之長條之光學補償膜C13。該光學補償膜C11之面內相位差值Ro為2nm，厚度方向之相位差值Rt為10nm。 Next, the raw material film was stretched at a stretching temperature of 170 ° C and a stretching magnification of 1.01 by a tenter stretching machine to obtain a long optical compensation film C13 having a film thickness of 20 μm. The in-plane retardation value Ro of the optical compensation film C11 was 2 nm, and the phase difference Rt in the thickness direction was 10 nm.

[偏光板P21~27之製作] [Production of polarizing plate P21~27]

偏光板P21~25係如P1般且P26及27係如P3般製作。但，關於光學補償膜C6係以使進行易接著處理之面成為聚乙烯醇側之方式貼合。作為保護膜．光學補償膜．偏光器使用之薄膜與偏光板之對應關係示於表6。 The polarizing plates P21 to 25 are made like P1, and the P26 and 27 are made like P3. However, the optical compensation film C6 is bonded so that the surface subjected to the easy-to-treat treatment becomes the polyvinyl alcohol side. As a protective film. Optical compensation film. The correspondence between the film used for the polarizer and the polarizing plate is shown in Table 6.

[液晶顯示裝置之製作] [Production of Liquid Crystal Display Device]

剝離VA模式之SONY公司製造之BRAVIA KDL-46HX800之偏光板，以成為圖1之構成之方式，以表7中之記載組合上述製作之偏光板，且貼合於面板上，製作液晶顯示裝置(2-1~2-9)，進行下述評價。該液晶顯示裝 置之液晶胞為使彩色濾波器與驅動用薄膜電晶體配置於透明基板之一面之COA型液晶顯示裝置之液晶胞，背光單元中***於與偏光器1之吸收軸正交之方向具有透過軸之反射型亮度提高薄膜。 The polarizing plate of BRAVIA KDL-46HX800 manufactured by SONY Co., Ltd. in the VA mode was peeled off, and the polarizing plate produced as described above was combined as shown in Table 7, and bonded to the panel to fabricate a liquid crystal display device ( 2-1~2-9), the following evaluation was performed. The liquid crystal display device The liquid crystal cell is a liquid crystal cell of a COA liquid crystal display device in which a color filter and a driving thin film transistor are disposed on one surface of a transparent substrate, and a backlight unit is inserted in a direction perpendicular to an absorption axis of the polarizer 1 to have a transmission axis. Reflective brightness enhancement film.

[不均評價] [Uneven evaluation]

在使背光點亮之狀態下，以畫面顯示黑色顯示，且依據以下基準以目視評價亮度不均。 In a state where the backlight is turned on, black display is displayed on the screen, and luminance unevenness is visually evaluated based on the following criteria.

◎：10人中有0~2人可確認出不均 ◎: 0 to 2 out of 10 people can confirm unevenness

￮：10人中有3~5人可確認出不均 ○: 3 to 5 out of 10 people can confirm unevenness

×：除了10人中有6~10人可確認出不均以外，且為清楚的不均 ×: In addition to 6 to 10 out of 10 people, it is possible to identify unevenness and clear unevenness.

上述評價結果示於表7。 The above evaluation results are shown in Table 7.

由表7所示之評價結果可了解，使用本發明之偏光板 之液晶顯示裝置幾乎無法確認亮度不均可知為優異者。 It can be understood from the evaluation results shown in Table 7 that the polarizing plate of the present invention is used. In the liquid crystal display device, it is almost impossible to confirm that the brightness is not excellent.

又，比較例之液晶顯示裝置2-9在實施不均評價之前，黑色顯示時之正面光漏太大，無法作為顯示裝置之功能。 Further, before the evaluation of the unevenness of the liquid crystal display device 2-9 of the comparative example, the front light leakage at the time of black display was too large to function as a display device.

[產業上之可能利用性] [Industry possible use]

本發明之長條狀偏光板可用於電視及監視器等大型液晶顯示裝置用之偏光板及使用該長條狀偏光板之液晶顯示裝置之製造中。 The long-length polarizing plate of the present invention can be used in the production of a polarizing plate for a large-sized liquid crystal display device such as a television or a monitor, and a liquid crystal display device using the long polarizing plate.

1‧‧‧反射型亮度提高薄膜1 1‧‧‧Reflective brightness enhancement film 1

2‧‧‧透明保護膜1 2‧‧‧Transparent protective film 1

3‧‧‧偏光器1 3‧‧‧Polarizer 1

4‧‧‧光學補償膜1 4‧‧‧Optical compensation film 1

5‧‧‧液晶胞 5‧‧‧ liquid crystal cell

6‧‧‧光學補償膜2 6‧‧‧Optical compensation film 2

7‧‧‧偏光器2 7‧‧‧Polarizer 2

8‧‧‧透明保護膜2 8‧‧‧Transparent protective film 2

a‧‧‧透過軸 a‧‧‧Transmission axis

b‧‧‧吸收軸 b‧‧‧Absorption axis

c‧‧‧遲相軸 C‧‧‧late phase axis

F‧‧‧前面(辨識側) F‧‧‧ front (identification side)

R‧‧‧背面(背光側) R‧‧‧Back (backlit side)

圖1為顯示本發明之液晶顯示裝置之一例之概念圖。 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a conceptual view showing an example of a liquid crystal display device of the present invention.

Claims (4)

一種長條狀偏光板，其為長條狀之至少依透明保護膜、偏光器及光學補償膜之順序層合而成之長條狀偏光板，其特徵為前述偏光器在寬度方向具有吸收軸，且該偏光器之N_Z係數在1.05~1.20之範圍內，且前述光學補償膜之膜厚d在滿足下述式(1)之範圍內，式(1)：10μm<d<40μm。 A long strip-shaped polarizing plate which is an elongated strip-shaped polarizing plate in which at least a transparent protective film, a polarizer and an optical compensation film are laminated in a row, wherein the polarizer has an absorption axis in a width direction And the N _Z coefficient of the polarizer is in the range of 1.05 to 1.20, and the film thickness d of the optical compensation film satisfies the following formula (1), and the formula (1): 10 μm < d < 40 μm. 一種液晶顯示裝置，其為至少具有背光、液晶胞、與該液晶胞之辨識側及背光側各具有一片偏光板之液晶顯示裝置，其特徵為具備將如申請專利範圍第1項之長條狀偏光板裁斷所得之偏光板，且滿足下述要件(a)~(c)，(a)作為前述液晶胞之背光側之偏光板(以下稱為「偏光板1」)，係以使如申請專利範圍第1項之長條狀偏光板裁斷所得之偏光板之光學補償膜(以下稱為「光學補償膜1」)位於前述液晶胞側之方式配置，(b)前述液晶胞之辨識側之偏光板(以下稱為「偏光板2」)係以透明保護膜、偏光器及光學補償膜(以下稱為「光學補償膜2」)之順序層合而成之偏光板，且以該光學補償膜2位於該液晶胞側之方式配置，(c)以使前述偏光板1與前述偏光板2之吸收軸正交之方式配置。 A liquid crystal display device having at least a backlight, a liquid crystal cell, and a liquid crystal display device having a polarizing plate on each of the identification side and the backlight side of the liquid crystal cell, and is characterized in that it has a strip shape as in the first item of the patent application scope. The polarizing plate is cut by the polarizing plate, and the following requirements (a) to (c) are satisfied, and (a) the polarizing plate (hereinafter referred to as "polarizing plate 1") on the backlight side of the liquid crystal cell is used as The optical compensation film (hereinafter referred to as "optical compensation film 1") of the polarizing plate obtained by cutting the long polarizing plate of the first aspect of the patent range is disposed on the liquid crystal cell side, and (b) the identification side of the liquid crystal cell The polarizing plate (hereinafter referred to as "polarizing plate 2") is a polarizing plate in which a transparent protective film, a polarizer, and an optical compensation film (hereinafter referred to as "optical compensation film 2") are laminated in this order, and the optical compensation is performed. The film 2 is disposed on the liquid crystal cell side, and (c) is disposed such that the polarizing plate 1 and the absorption axis of the polarizing plate 2 are orthogonal to each other. 如申請專利範圍第2項之液晶顯示裝置，其中前述液晶胞為垂直配向型液晶胞，前述光學補償膜2含有平均 醯基取代度在2.0~2.6之範圍內之纖維素酯，且滿足以下述式(2)~式(5)表示之關係，式(2)：Ro(1)≦5nm式(3)：-10nm≦Rt(1)<20nm式(4)：60nm≦Ro(2)≦80nm式(5)：190nm≦Rt(2)≦260nm[但，前述光學補償膜1及前述光學補償膜2之在23℃、55%RH、測定波長589nm測定之面內相位差值Ro分別設為Ro(1)、Ro(2)，且厚度方向之相位差值Rt分別設為Rt(1)、Rt(2)，且，Ro及Rt係以下述式定義，式(I)：Ro=(n_x-n_y)×d(nm)式(II)：Rt={(n_x+n_y)/2-n_z}×d(nm)上述式中，Ro表示光學補償膜內之面內相位差值，Rt表示膜內之厚度方向之相位差，且，d表示光學補償膜之厚度，n_x表示光學補償膜之面內最大(遲相軸方向)之折射率，n_y表示光學補償膜面內之與遲相軸呈直角之方向(進相軸方向)之折射率，n_z表示厚度方向之光學補償膜之折射率，又，測定條件係與上述相同]。 The liquid crystal display device of claim 2, wherein the liquid crystal cell is a vertical alignment type liquid crystal cell, and the optical compensation film 2 contains a cellulose ester having an average thiol substitution degree in the range of 2.0 to 2.6, and satisfies the following The relationship between the formula (2) and the formula (5), the formula (2): Ro(1) ≦ 5 nm (3): -10 nm ≦ Rt (1) < 20 nm (4): 60 nm ≦ Ro (2) ≦ 80 nm (5): 190 nm ≦ Rt (2) ≦ 260 nm [However, the in-plane retardation values Ro measured at 23 ° C, 55% RH, and measurement wavelength 589 nm of the optical compensation film 1 and the optical compensation film 2 are respectively set. Ro(1) and Ro(2), and the phase difference Rt in the thickness direction is set to Rt(1) and Rt(2), respectively, and Ro and Rt are defined by the following formula: (I): Ro= (n _x -n _y ) × d (nm) Formula (II): Rt = {(n _x + n _y ) / 2 - n _z } × d (nm) In the above formula, Ro represents the surface in the optical compensation film The internal phase difference value, Rt represents the phase difference in the thickness direction in the film, and d represents the thickness of the optical compensation film, n _x represents the maximum in-plane refractive index of the optical compensation film (slow phase axis direction), and n _y represents optical the inner surface of the right angle of the compensation film direction (fast axis direction) and the slow axis of refractive index was, n _z represents a thickness direction, The refractive index of the optical compensation film, and measurement conditions were the same as above Department]. 如申請專利範圍第2或3項之液晶顯示裝置，其中反射型亮度提高薄膜係具備於前述背光與前述偏光板1之間，且以該反射型亮度提高薄膜之透過軸與前述偏光板1之偏光器之吸收軸呈正交之方式配置。 The liquid crystal display device of claim 2, wherein the reflective brightness enhancement film is provided between the backlight and the polarizing plate 1, and the transmission axis of the reflective brightness enhancement film and the polarizing plate 1 are The absorption axes of the polarizers are arranged in an orthogonal manner.