200946989 九、發明說明 【發明所屬之技術領域】 本發明關於複合偏光板輥、複合偏光板組及液晶顯示 裝置。 【先前技術】 近年來，消耗電力低、以低電壓動作、輕量且薄型的 © 液晶顯示器係作爲攜帶型電話、攜帶型資訊終端、電腦用 的監視器、電視等的資訊用顯示裝置而迅速普及。隨著液 晶技術的發展，有提案各式各樣模式的液晶顯示器，正在 消除響應速度或對比、窄視野角等液晶顯示器的問題點。 然而依然地，與陰極線管（CRT )相比，窄的視野角係被 指摘，爲了視野角擴大，有進行各種嘗試。 如此的液晶顯示裝置之一個係使具有正或負的介電常 數各向異性的棒狀液晶分子對於基板呈垂直配向的垂直配 ® 向（VA )模式之液晶顯示裝置。此垂直配向模式在非驅 動狀態下，由於液晶分子對於基板係呈垂直配向，故光係 不隨著偏光的變化而通過液晶層。因此’藉由在液晶面板 的上下以吸收軸爲正交的方式配設直線偏光板’可在從正 面觀看時’得到幾乎完全的黑顯示，可得到高的對比。 然而，於如此的液晶胞僅具備偏光板的V A模式液晶 顯示裝置中，當傾斜地觀看它時’所配設的偏光板之軸角 度若與90。偏離，則晶胞內的棒狀液晶分子表現雙折射’ 而導致發生漏光，對比顯著降低，斜視時的色調係隨著角 -5- 200946989 度而大不相同。將斜視時的對比及色變化包括在內稱爲「 視野角特性」。 爲了消除此視野角特性的不良，必須在液晶胞與直線 偏光板之間配設光學補償薄膜，以往採用將二軸性的相位 差板在液晶胞與上下偏光板之間各配設1片的方式，或將 一軸性的相位差板與完全二軸性的相位差板各一片配置在 液晶胞的上下，或2片皆配設在液晶胞的一側之方式。例 如特開2001 -109009號公報（專利文獻1 )記載在垂直配 0 向模式的液晶顯示裝置中，於上下的偏光板與液晶胞之間 ，各配置a板（即正一軸性的相位差板）及c板（即完全 二軸性的相位差板）。 正一軸性的相位差板係Nz係數大約1 · 0的薄膜，而 完全二軸性的相位差板係面內的相位差値R〇大致0的薄 膜。此處，以薄膜的面內遲相軸方向之折射率當作nx，以 薄膜的面內進相軸方向之折射率當作ny，以薄膜的厚度方 向之折射率當作nz，以薄膜的厚度當作d時，面內的相位 〇 差値Rc、厚度方向的相位差値Rth及Nz係數分別係由下 式（1 )〜（3 )所定義。 R〇= ( nx-ny ) x d ( 1 )BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite polarizing plate roll, a composite polarizing plate group, and a liquid crystal display device. [Prior Art] In recent years, the liquid crystal display with low power consumption and low voltage operation, lightweight and thin is rapidly used as a display device for information such as a portable telephone, a portable information terminal, a monitor for a computer, and a television. popular. With the development of liquid crystal technology, there are proposals for various types of liquid crystal displays that are eliminating the problem of response speed or contrast, narrow viewing angle and other liquid crystal displays. However, in contrast to the cathode wire tube (CRT), a narrow viewing angle is referred to, and various attempts have been made for the expansion of the viewing angle. One of such liquid crystal display devices is a liquid crystal display device of a vertical alignment (VA) mode in which a rod-like liquid crystal molecule having a positive or negative dielectric constant anisotropy is vertically aligned with respect to a substrate. In the non-driving state, since the liquid crystal molecules are vertically aligned with respect to the substrate, the light system does not pass through the liquid crystal layer as the polarized light changes. Therefore, by arranging the linear polarizing plate ‘the absorption axis is orthogonal to the upper and lower sides of the liquid crystal panel, an almost complete black display can be obtained when viewed from the front side, and high contrast can be obtained. However, in such a V A mode liquid crystal display device in which the liquid crystal cell is provided only with a polarizing plate, the axial angle of the polarizing plate disposed when the liquid crystal cell is viewed obliquely is 90. Deviation, the rod-like liquid crystal molecules in the unit cell exhibit birefringence, which causes light leakage, and the contrast is remarkably lowered. The hue of the squint is greatly different with the angle -5 - 200946989 degrees. The contrast and color change when squinting is included is called "viewing angle characteristic". In order to eliminate the defect of the viewing angle characteristic, it is necessary to arrange an optical compensation film between the liquid crystal cell and the linear polarizing plate. In the related art, a biaxial phase difference plate is disposed between the liquid crystal cell and the upper and lower polarizing plates. Alternatively, one of the one-axis phase difference plate and the completely biaxial phase difference plate may be disposed on the upper and lower sides of the liquid crystal cell, or both of them may be disposed on one side of the liquid crystal cell. For example, JP-A No. 2001-109009 (Patent Document 1) discloses a liquid crystal display device in a vertical alignment mode in which a plate (ie, a positive-axis phase difference plate) is disposed between the upper and lower polarizing plates and the liquid crystal cell. ) and c board (that is, a completely biaxial phase difference plate). The positive-axis phase difference plate is a film having a Nz coefficient of about 1.0 mm, and a film having a phase difference 値R 〇 substantially 0 in the plane of the completely biaxial phase difference plate. Here, the refractive index in the in-plane slow axis direction of the film is taken as nx, the refractive index in the in-plane axis direction of the film is taken as ny, and the refractive index in the thickness direction of the film is taken as nz, as the film When the thickness is regarded as d, the phase difference 値Rc in the in-plane, the phase difference 値Rth and the Nz coefficient in the thickness direction are defined by the following formulas (1) to (3), respectively. R〇= ( nx-ny ) x d ( 1 )
Rth = [ ( nx + ny) /2-nz] χ d ( 2 ) Nz 係數=(nx-nz) / ( nx-ny ) 一軸性的薄膜，由於 nz与（幾乎等於）ny，故Nz係 -6 - 200946989 數与1.0。即使爲一軸性的薄膜，Nz係數也隨著拉伸條件 的變動，而在0.80〜1.50左右之間變化。完全二軸性的薄 膜，由於nx与ny，故R〇4〇。完全二軸性的薄膜，由於僅 厚度方向的折射率不同（小），而亦稱爲具有負一軸性， 光學軸在法線方向的薄膜，而且如上述地亦稱爲c板。 一軸性的相位差薄膜，例如一般多用經由自由端縱一 軸拉伸或固定端橫一軸拉伸等而拉伸的樹脂薄膜等。於固 © 定端橫一軸拉伸時，帶有1.1〇< Nz係數$1.50程度的若 干二軸性之情況係多。具有如此Nz係數的相位差薄膜， 雖然是一軸性，但不能說是完全一軸性。此處所言的完全 —軸性之相位差薄膜係指0.90 SNz係數$1.10的範圍者。 藉由使用如專利文獻1所揭示的各式各樣的相位差薄 膜，雖然VA模式的視野角相當地變廣，但據說尙有改良 的餘地。 本發明係爲了解決上述問題而完成者，其目的爲提供 W 可提高液晶顯示裝置（尤其VA模式的液晶顯示裝置）之 視野角特性的複合偏光板組以及使用其的液晶顯示裝置。 【發明內容】 發明所欲解決的問題 關於VA模式液晶顯示裝置，本發明者爲了更提高其 視野角特性，進行專心致力的檢討，結果發現於一軸性相 位差薄膜與完全二軸性相位差薄膜的組合中，使一軸性相 位差薄膜的光學特性成爲完全一軸性，則可得到視野角特 200946989 性更良好的液晶顯示裝置，而達成本發明。即，本發明係 如以下。 本發明之特徵爲具有在吸收軸方向與長度方向呈平行 配置的偏光板之長條輥上，層合第一相位差板的長條輥之 構造，第一相位差板的遲相軸方向與偏光板的吸收軸方向 以80〜100°的角度交叉方式配置的複合偏光板輥，第一 相位差板係將丙烯系樹脂拉伸所成，面內的相位差値R。 係在90〜200nm的範圍，而且以薄膜的面內遲相軸方向之 ❹ 折射率當作nx，以薄膜的面內進相軸方向之折射率當作 ny，以薄膜的厚度方向之折射率當作nz時，以下式所定 義的Nz係數爲在0.90〜1.10的範圍，Rth = [ ( nx + ny) /2-nz] χ d ( 2 ) Nz coefficient = (nx - nz) / ( nx - ny ) A linear film, since nz is (almost equal to) ny, the Nz system - 6 - 200946989 number and 1.0. Even in the case of a one-axis film, the Nz coefficient varies from 0.80 to 1.50 depending on the stretching conditions. A completely biaxial film, due to nx and ny, is R〇4〇. A completely biaxial film is also referred to as a film having a negative one-axis property, a negative optical axis in the normal direction, and a c-plate as described above, since the refractive index in the thickness direction is different (small). For the one-axis retardation film, for example, a resin film which is stretched by stretching through a free end longitudinal axis or a fixed end transverse axis stretching or the like is generally used. When the solid-set © fixed-end horizontal axis is stretched, there are many cases where there are 1.1 〇 < Nz coefficients of about $1.50. A retardation film having such an Nz coefficient, although it is monoaxial, cannot be said to be completely monoaxial. The fully-axial phase difference film referred to herein means a range of 0.90 SNz coefficient of $1.10. By using various retardation films disclosed in Patent Document 1, although the viewing angle of the VA mode is considerably larger, it is said that there is room for improvement. The present invention has been made to solve the above problems, and an object thereof is to provide a composite polarizing plate group which can improve the viewing angle characteristics of a liquid crystal display device (particularly, a VA mode liquid crystal display device) and a liquid crystal display device using the same. DISCLOSURE OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION In order to further improve the viewing angle characteristics of the VA mode liquid crystal display device, the inventors of the present invention conducted a review of the intrinsic effort, and found that the one-axis retardation film and the completely biaxial retardation film were found. In the combination, the optical characteristics of the one-axis retardation film are completely uniaxial, and a liquid crystal display device having a better viewing angle angle of 200946989 can be obtained, and the present invention has been achieved. That is, the present invention is as follows. The present invention is characterized in that a long roll having a first phase difference plate is laminated on a long roll of a polarizing plate disposed in parallel with the longitudinal direction of the absorption axis, and the slow phase axis of the first phase difference plate is The composite polarizing plate roll in which the absorption axis direction of the polarizing plate is arranged at an angle of 80 to 100°, and the first phase difference plate is formed by stretching a propylene-based resin, and the phase difference 値R in the plane. It is in the range of 90 to 200 nm, and the refractive index of the in-plane retardation axis direction of the film is regarded as nx, and the refractive index in the in-plane axis direction of the film is regarded as ny, and the refractive index in the thickness direction of the film When it is regarded as nz, the Nz coefficient defined by the following formula is in the range of 0.90 to 1.10.
Nz 係數=(nx-nz) / ( nx-ny) 本發明的複合偏光板輥之第一相位差板較佳係對丙烯 Ο 系樹脂進行固定端橫一軸拉伸而得之薄膜。 又，本發明亦提供複合偏光板組，其係用於液晶顯示 裝置的第一複合偏光板與第二複合偏光板之組，第一複合 偏光板具有依順序層合偏光板、第一相位差板及感壓性黏 著劑層之構造，第一相位差板係將丙烯樹脂拉伸而成之相 位差薄膜，面內的相位差値Ro係在90〜200nm的範圍， 且以薄膜的面內遲相軸方向之折射率當作nx，以薄膜的面 內進相軸方向之折射率當作ny，以薄膜的厚度方向之折射 -8- 200946989 率當作nz時，以下式所定義的Nz係數爲在0.90〜1.10的 範圍’而且其遲相軸方向與偏光板的吸收軸方向爲以80〜 100°的角度交叉方式配置，第二複合偏光板具有依順序 層合偏光板、第二相位差板及感壓性黏著劑層的構造，第 二相位差板含有有機修飾黏土複合體與黏結劑樹脂，面內 的相位差値R〇係在0〜3 Onm的範圍，厚度方向的相位差 値Rth係在30〜300nm的範圍， ❹Nz coefficient = (nx - nz) / (nx - ny) The first phase difference plate of the composite polarizing plate roll of the present invention is preferably a film obtained by stretching a propylene ray resin at a fixed end transversely. Moreover, the present invention also provides a composite polarizing plate set for a group of a first composite polarizing plate and a second composite polarizing plate of a liquid crystal display device, wherein the first composite polarizing plate has a laminated laminated polarizing plate and a first phase difference. The structure of the plate and the pressure-sensitive adhesive layer, the first phase difference plate is a phase difference film obtained by stretching an acrylic resin, and the in-plane phase difference 値Ro is in the range of 90 to 200 nm, and the film is in-plane. The refractive index in the direction of the slow axis is taken as nx, and the refractive index in the in-plane axis direction of the film is regarded as ny, and when the refractive index in the thickness direction of the film is -8-200946989 as nz, Nz defined by the following formula The coefficient is in the range of 0.90 to 1.10' and the slow axis direction is arranged at an angle of 80 to 100° with respect to the absorption axis direction of the polarizing plate, and the second composite polarizing plate has the laminated polarizing plate and the second phase in sequence. The structure of the difference plate and the pressure-sensitive adhesive layer, the second phase difference plate contains the organic modified clay composite and the binder resin, and the in-plane phase difference 値R〇 is in the range of 0 to 3 Onm, and the phase difference in the thickness direction値Rth is in the range of 30~300nm, ❹
Nz 係數=(nx-nz) / ( nx-ny) 本發明的複合偏光板組之第一相位差板較佳係對丙烯 系樹脂進行固定端橫一軸拉伸而得之薄膜。 本發明的複合偏光板組較佳係用於VA模式的液晶顯 示裝置。 又，本發明也提供液晶顯示裝置，其係具備上述本發 明的複合偏光板組及液晶胞的液晶顯示裝置，於液晶胞的 一側介於其感壓性黏著劑層貼合第一複合偏光板，而且於 液晶胞的另一側介於其感壓性黏著劑層貼合第二複合偏光 板所成。 【實施方式】 實施發明的最佳形態 Π ]複合偏光板組 -9- 200946989 本發明的複合偏光板組，爲了在液晶胞的一側配置第 一複合偏光板，在另一側配置第二複合偏光板，而製作液 晶顯示裝置，係當作第一複合偏光板及第二複合偏光板的 組合來供應。本發明中的第一複合偏光板及第二複合偏光 板係各自具有依順序層合有偏光板、相位差板（第一相位 差板或第二相位差板）及感壓性黏著劑層的構造。 [1-1]第一複合偏光板 〇 此處，第1圖以分離各層的狀態示意地顯示本發明的 複合偏光板組所用的較佳一例之第一複合偏光板1的斜視 圖，第2圖以分離各層的狀態示意地顯示本發明的複合偏 光板組所用的較佳其它例之第一複合偏光板1 1的斜視圖 。第1圖及第2圖所示的第一複合偏光板1、11，除了偏 光板2、12的構成爲一部分不同以外，係具有同樣的構造 ，由在偏光板2、12上層合第一相位差板3與感壓性黏著 劑層4所成。 © 本發明所用的第一相位差板3之特徵的1個爲將丙烯 樹脂拉伸而成的相位差薄膜，面內的相位差値R。係在90 〜2 OOnm的範圍。即，本發明所用的第一相位差板3係完 全一軸性的相位差薄膜（如上述地，0.90 SNz係數S 1.10 的範圍之一軸性薄膜）。爲了得到如此的正完全一軸性之 相位差薄膜，通常可將固有雙折射爲正的樹脂薄膜拉伸配 向，拉伸方法係可採用固定端一軸拉伸、自由端一軸拉伸 等。 -10- 200946989 此處’使用對於薄膜的長條輥，連續地進行自由端一 軸拉伸時，在其長度方向（流動方向）中拉伸薄膜的稱爲 縱拉伸的拉伸方法。以如此方法所得之相位差薄膜的遲相 軸方向係與薄膜的長度方向呈大致平行。又，偏光板通常 亦由對聚乙烯醇樹脂所成的薄膜之長條輥進行自由端縱一 軸拉伸而得，其吸收軸方向係與其長度方向呈大致平行。 以相位差薄膜的遲相軸方向與偏光板的吸收軸方向呈正交 © 的方式貼合此等時，將至少任一個長條輥以片狀切出某一 程度的大小，使其方向旋轉90度後，必須對另一方的薄 膜一片一片地貼合。相對於此，當用拉幅機等以固定端橫 一軸拉伸所得之相位差薄膜時，由於遲相軸方向與長條輥 的長度方向成爲正交方向（寬度方向），可藉由輥對輥來 連續貼合相位差薄膜的長條輥與偏光板的長條輥。然而， 於對通常的非晶質樹脂薄膜進行固定端橫一軸拉伸時，難 以得到完全一軸性的相位差薄膜，Nz係數> 1 · 1 0的情況 ❿係多。 於本發明中，由於使用即使施予固定端橫一軸拉伸時 ，以某一程度以上的高倍率進行拉伸，也可得到完全一軸 性的特性之丙烯樹脂，而使用第一相位差板3當作完全一 軸性的相位差薄膜。此處，所謂某一程度以上的高倍率， 通常就是2倍以上，較佳爲3倍以上，更佳爲3 · 5倍以上 〇 拉伸倍率的上限係沒有特別的限制，但由於若太過度 拉伸，則薄膜斷裂，故通常以1 〇倍以下拉伸，較佳以8 -11 - 200946989 倍以下拉伸，更佳以6倍以下拉伸。進行固定端橫一軸拉 伸所得的相位差薄膜’由於其遲相軸方向係大致平行與薄 膜的長度方向呈90度不同的方向（=寬度方向）’故藉 由以輥對輥將丙烯樹脂經固定端橫一軸拉伸所得之相位差 薄膜的長條輥與偏光板的長條輥貼合’可高效率且容易地 製作本發明的複合偏光板組所用的第一複合偏光板。此意 味如本發明地，在相位差薄膜可使用由丙烯樹脂所構成的 薄膜。 © 本發明的第一複合偏光板之第一相位差板所用的丙嫌 樹脂，主要係由丙烯單元所構成的樹脂，一般爲結晶性者 ，除了丙烯的均聚物，亦可爲丙烯及與其可共聚合的共聚 單體之共聚物。 作爲與丙嫌共聚合的共聚單體’例如可舉出乙@ 原子數4〜2〇 ( CM〜C20)的α-烯烴。作爲碳原子數4〜 20的a-烯烴，具體地可舉出1-丁烯、2_甲基_丨_丙嫌（以 上C4) ; 1-戊稀、2-甲基-1-丁靖、3-甲基丁烯（以上 ◎ C 5 ) ; 1 -己烯、2 -乙基-1 - 丁烯、2，3 -二甲基-〗_ 丁嫌、2-甲 基-1-戊烯、3-甲基-1-戊烯、4-甲基-K戊燦、3,3_二甲基· 1-丁稀（以上C6) ，1_庚嫌、2 -甲基-1-己嫌、23 —甲 基-1-戊烯、2-乙基-1-戊烯、2-甲基-3_乙烯_丨_丁烯（以上 C7) ; 1-辛烯、5-甲基-1-庚烯、2-乙基-丨_己嫌、3,3 —二 甲基-1-己烯、2-甲基-3-乙基-1-戊烯、2,3,4_三甲基_丨_戊 烯、2-丙基-1-戊烯、2,3-二乙基-1-丁烯（以上C8) . ι 壬烯（C9) ; 1-癸稀（CIO) ; 1-十一燦（C11)十二嫌 -12- 200946989 (C12 ) ; 1-十三烯（C13) ; 1-十四烯（C14) ; 1-十五 烯（C15) ; 1-十六烯（C16);丨_十七烯（C17) ; 1-十 八烯（C18) ;1-十九烯（C19)等。 於上述α-烯烴之中，較佳爲碳原子數4〜12的α-烯 烴’具體地可舉出卜丁烯、2 -甲基-1·丙烯；卜戊烯、2 -甲 基-1-丁烯、3-甲基-1-丁烯；卜己烯、2-乙基-卜丁烯、2,3-二甲基-1-丁烯、2-甲基-卜戊烯、3-甲基-丨_戊烯、4-甲基-® 1-戊烯、3，3-二甲基-1-丁烯；1-庚烯、2-甲基-1-己烯、 2,3-二甲基-1-戊烯、2-乙基-1-戊烯、2-甲基-3-乙基-1-丁 烯；1-辛烯、5-甲基-1-庚烯、2-乙基-丨_己烯、3,3-二甲 基-1-己烯、2-甲基-3-乙基-1-戊烯、2,3,4-三甲基-1-戊烯 、2-丙基-1-戊烯、2,3-二乙基-1-丁烯；1-壬烯；1-癸烯； 十一烯；1-十二烯等。從共聚合性的觀點來看，較佳爲 從1-丁烯、1-戊烯、1-己烯及1_辛烯所選出的至少任一者 ，特佳爲1-丁烯及/或1-己烯。 響 共聚物可爲無規共聚物’也可爲嵌段共聚物。 作爲較佳的共聚物，可舉出丙烯-乙烯共聚物或丙烯-1· 丁烯共聚物。丙烯-乙烯共聚物或丙烯-I-丁烯共聚物的 乙嫌單兀含量、1-丁稀單兀含量，例如可依照「筒分子分 析手冊」（ 1995年，紀伊國屋書店發行）的第616頁記載 的方法進行紅外線（IR )光譜測定而求得。 從提高透明度或加工性的觀點來看，較佳爲使用以丙 烯當作主體的與任意不飽和烴之無規共聚物。其中較佳爲 與乙烯的共聚物。 -13- 200946989 作爲共聚物時，丙烯以外的不飽和烴類之共聚合比例 爲1〜1 0重量％係有利，更佳的共聚合比例爲3〜7重量％ 。藉由使丙烯以外的不飽和烴類之單元成爲1重量％以上 ，有產生提高加工性或透明性的效果之傾向。但是，該比 例若超過1 0重量％，則樹脂的熔點下降，耐熱性有變差的 傾向，故不宜。再者，於使2種類以上的共聚單體與丙烯 共聚合時，所得到的共聚物中所含有全部共聚單體而來單 元之合計含量較佳爲在上述範圍內。 ❹ 丙烯樹脂係可藉由將丙烯均聚合的方法、將丙烯與其 它共聚合性共聚單體共聚合的方法等來製造。 於此等方法中，例如可合適地使用（1)以鎂、鈦及 鹵素當作必要成分的固體觸媒成分所成的鈦-鎂（Ti-Mg) 系觸媒，（2)以鎂、鈦及鹵素當作必要成分的固體觸媒 成，與有機鋁化合物及視需要的供電子性化合物等的第三 成分所組合成的觸媒系，（3)金屬茂系觸媒等眾所周知 的聚合用觸媒。 〇 於上述觸媒系之中，最一般使用以鎂、鈦及鹵素當作 必要成分的固體觸媒成分、與有機鋁化合物及供電子性化 合物的組合。更具體地，作爲有機鋁化合物，可舉出三乙 基鋁、三異丁基鋁、三乙基鋁及二乙基鋁氯化物的混合物 、四乙基二鋁氧烷等；作爲供電子性化合物，可舉出環己 基乙基二甲氧基矽烷、第三丁基丙基二甲氧基矽烷、第三 丁基乙基二甲氧基矽烷、二環戊基二甲氧基矽烷等。 另一方面，作爲以鎂、鈦及鹵素當作必要成分的固體 -14- 200946989 觸媒成分，例如可舉出特開昭61 -21 8606號公報、特開昭 61-28 7 904號公報、特開平7-216017號公報等記載的觸媒 系，而且作爲金屬茂系觸媒，例如可舉出日本發明專利第 258725 1號公報、日本發明專利第2627669號公報、日本 發明專利第2668732號公報等記載的觸媒系。 丙烯樹脂例如可藉由使用以己烷、庚烷、辛烷、癸烷 、環己烷、甲基環己烷、苯、甲苯、二甲苯等的烴化合物 ® 所代表的惰性溶劑之溶液聚合法，使用液狀單體當作溶劑 的塊狀聚合法，使氣體單體照原樣地聚合之氣相聚合法等 來製造。此等方法的聚合係可以分批式來進行，也可以連 續式來進行。 丙烯樹脂的立體規則性係可爲同排、對排、雜排的任 一者。於本發明中，從耐熱性之點來看，較宜使用對排或 同排的丙烯樹脂。 本發明中所用的丙烯樹脂之依照JIS K7210在溫度 — 23〇°C、荷重21.18N所測定的熔體流動速率（MFR)較佳 爲在0.1〜200 g/10分鐘的範圍，特佳爲在0.5〜50g/10分 鐘的範圍。藉由使用MFR在此範圍的丙烯樹脂，可對擠 壓機不施加大負荷而得到均勻的薄膜狀物。 丙烯樹脂，於不妨礙本發明的效果之範圍內，亦可配 合眾所周知的添加物。作爲添加物，例如可舉出抗氧化劑 '紫外線吸收劑、抗靜電劑、滑劑、造核劑、防霧劑、防 黏連劑等。抗氧化劑例如有酚系抗氧化劑、磷系抗氧化劑 、硫系抗氧化劑、受阻胺系光安定劑等，而且亦可使用具 -15- 200946989 有1分子中例如兼具酚系抗氧化機構與磷系抗氧化機構的 單元之複合型抗氧化劑。作爲紫外線吸收劑，例如可舉出 2-羥基二苯甲酮系、羥基苯基苯并***系等的紫外線吸收 劑、苯甲酸酯系的紫外線遮斷劑等。抗靜電劑可爲聚合物 型、寡聚物型、單體型的任一種。作爲滑劑，可舉出芥醯 胺或油醯胺等的高級脂肪醯胺、硬脂酸等的高級脂肪酸及 其鹽等。作爲造核劑，例如可舉出山梨糖醇系造核劑、有 機磷酸鹽系造核劑、如聚乙烯環己烷的高分子系造核劑等 0 。作爲防黏連劑，球狀或接近其的形狀之微粒子，可使用 無機系或有機系。此等添加物可倂用複數種。 於本發明中，將如上述的丙烯樹脂製成薄膜，作爲相 位差薄膜用的捲筒來使用。例如，藉由熔融樹脂的擠壓成 形法，將溶解於有機溶劑中的樹脂流延在平板上，去除溶 劑以製膜的溶劑流延法等，可得到實質上沒有面內相位差 的丙烯系樹脂薄膜。 茲詳細說明藉由擠壓成形來製造薄膜的方法。丙烯樹 Ο 脂係藉由擠壓機中的螺桿之旋轉而熔融混煉，由T模頭擠 出成片狀。所擠出的熔融狀片之溫度係180〜30(TC。此時 的熔融狀片之溫度若低於1 80°C，則延展性不充分，所得 到的薄膜之厚度變不均勻，有成爲相位差不均的薄膜之可 能性。又，其溫度若超過300°C，則容易發生樹脂的劣化 或分解，在片中會產生氣泡，或含有碳化物。 擠壓機可爲單軸擠壓機或2軸擠壓機。例如於單軸擠 壓機時，螺桿的長度L與直徑D的比即L/D係24〜36左 -16- 200946989 右，樹脂供給部的螺紋溝之空間容積與樹脂計量部的螺紋 溝之空間容積的比（前者/後者）即壓縮比係1.5〜4左右 ，可使用具有全螺紋型、屏障型、馬多克（Madoc )型的 混煉部分之類型等的螺桿。從抑制丙烯樹脂的劣化或分解 ，均勻熔融混煉的觀點來看，較佳係使用L/D爲28〜36 、壓縮比爲2.5〜3.5的屏障型螺桿。又，爲了盡可能地抑 制丙烯樹脂的劣化或分解，擠壓機內較佳係爲氮氣環境或 © 真空。再者，爲了去除由於丙烯系樹脂的劣化或分解所產 生的揮發氣體，亦較佳爲在擠壓機的前端設置直徑1〜 5mm的孔，提高擠壓機前端部分的樹脂壓力。提高孔的擠 壓機前端部分之樹脂壓力，係意味提高前端的背壓，藉此 可提高擠出的安定性。所用的孔之直徑更佳爲直徑2〜 4mm 〇 擠出所使用的T模頭較佳爲在樹脂的流路表面沒有微 小的階梯差或損傷者，而且其唇部分較佳係經與熔融的丙 ® 烯系樹脂之摩擦係數小的材料所鍍敷或塗覆，且唇前端較 佳係經硏磨到直徑0.3mm以下的尖銳邊緣形狀者。作爲摩 擦係數小的材料，可舉出碳化鎢系或氟系的特殊鍍敷等。 藉由使用如此的T模頭，可抑制口模焦料的發生，同時可 抑制口模線，故可得到外觀均一性優異的樹脂薄膜。此T 模頭之歧管爲衣架形狀，而且較佳爲滿足以下的條件（1 )或（2 )，更佳爲滿足條件（3 )或（4 )。 •條件（1 ) T模頭的唇寬小於1 500mm時：T模頭的厚度方 -17- 200946989 向長度> 1 80mm •條件（2 ) T模頭的唇寬爲1 500mm以上時：T模頭的厚度 方向長度> 220mm •條件（3 ) T模頭的唇寬小於1 500mm時：T模頭的高度方 向長度> 250mm •條件（4 ) T模頭的唇寬爲1 500mm以上時：T模頭的高度 方向長度> 280 mm 藉由使用滿足如此條件的T模頭，可整頓T模頭內部 的熔融狀丙烯樹脂之流動，而且即使在唇部分也可邊抑制 厚度不均邊擠出，故可得到厚度精度更優異、相位差更均 一的保護薄膜。 從抑制丙烯樹脂的擠出變動之觀點來看，較佳在擠壓 機與T模頭之間經由接頭安裝齒輪泵。又，爲了去除丙烯 樹脂中的異物，較佳爲安裝葉盤過濾器。 由T模頭所擠出的熔融狀片，係在金屬製冷卻輥（亦 稱爲驟冷輥或鑄輥）與含有壓接於該金屬製冷卻輥的圍周 方向旋轉的含彈性體的接觸輥之間，被夾壓而冷卻固化， 而得到所欲的薄膜。於此情況下，接觸輥可以橡膠等的彈 性體照原樣地當作表面，也可以金屬套筒所成的外筒來被 覆彈性體輥的表面。 於使用彈性體輥的表面經金屬套筒所成的外筒被覆的 -18- 200946989 接觸輥時，通常在金屬製冷卻輥與接觸輥之間，直接夾持 丙烯樹脂的熔融狀片及進行冷卻。另一方面，於使用表面 爲彈性體的接觸輥時，亦可使熱塑性樹脂的二軸拉伸薄膜 存在於丙烯樹脂的熔融狀片與接觸輥之間而夾壓。 於丙烯樹脂的溶融狀片被上述冷卻輥與接觸輥夾持而 冷卻固化時，必須先降低冷卻輥與接觸輥之表面溫度，將 熔融狀片急冷。具體地，將兩輥的表面溫度調整到0〜 © 30°c的範圍。此等的表面溫度若超過30°c，則由於熔融狀 片的冷卻固化費時，丙烯樹脂中的結晶成分會成長，所得 到的薄膜有透明性變差之虞。另一方面，輥的表面溫度若 低於〇 °C，則金屬製冷卻輥的表面會結露而附著水滴，薄 膜的外觀有惡化的傾向。 所使用的金屬製冷卻輥，由於其表面狀態係轉印到丙 烯樹脂薄膜表面，故其表面具有凹凸時，有降低所得到的 丙烯樹脂薄膜之厚度精度的可能性。因此，金屬製冷卻輥 W 的表面盡可能較佳爲鏡面狀態。具體地，金屬製冷卻輥的 表面粗度以最大高度的標準數列表示較佳爲0.3S以下， 更佳爲0.1〜0.2S。 與金屬製冷卻輥形成輥隙部分的接觸輥之彈性體的表 面硬度，以JIS K 63 01所規定的彈簧式硬度試驗（A形） 所測定的値較佳爲65〜80，更佳爲70〜80。藉由使用如 此表面硬度的橡膠輥，可容易均勻地維持對熔融狀片所施 加的線壓，而且在金屬製冷卻輥與接觸輥之間不會形成熔 融狀片的堆積物（樹脂積留），可容易成形爲薄膜。 -19- 200946989 夾壓熔融狀片時的壓力（線壓）’係由對金屬製冷卻 輥推壓接觸輥的壓力來決定。線壓較佳爲50〜3 OON/cm， 更佳爲100〜25 ON/cm。藉由使線壓在前述範圍，不會形 成堆積物，可容易邊維持一定線壓邊邊製造丙烯樹脂薄膜 〇 於金屬製冷卻輥與接觸輥之間夾壓丙烯樹脂的熔融狀 片及熱塑性樹脂的二軸拉伸薄膜時，構成此二軸拉伸薄膜 的熱塑性樹脂，只要是不會與丙烯樹脂堅固地熱熔黏的樹 © 脂即可，具體地可舉出聚酯、聚醯胺、聚氯乙烯、聚乙烯 醇、乙烯-乙烯醇共聚物、聚丙烯腈等。於此等之中，最 佳爲濕度或熱等所致的尺寸變化少之聚酯。此情況下的二 軸拉伸薄膜之厚度通常爲5〜50 μιη左右，較佳爲10〜 3 0 μχη 〇 於此方法中，從Τ模頭的唇到金屬製冷卻輥與接觸輥 所夾壓爲止的距離（空氣隙）較佳爲200mm以下，更佳 爲160mm以下。由T模頭所擠出的熔融狀片，若在從唇 © 到輥爲止之間被拉伸，則容易發生配向。如上述地縮短空 氣隙，可得到配向更小的薄膜。空氣隙的下限値係由所使 用的金屬製冷卻輥之直徑、接觸輥之直徑及所使用的唇之 前端形狀來決定，通常爲5 0mm以上。 以此方法製造丙烯樹脂薄膜時的加工速度，係由用於 將熔融狀片冷卻固化所需要的時間來決定。所使用的金屬 製冷卻輥之直徑若變大，則由於熔融狀片與該冷卻輥的接 觸距離變長，故可更高速地製造。具體地，使用直徑 -20- 200946989 600mm的金屬製冷卻輥時，加工速度最大爲5〜20m/分鐘 左右。 金屬製冷卻輥與接觸輥之間所夾壓的熔融狀片，係藉 由與輥的接觸而冷卻固化。而且，按照需要切割端部後， 在捲繞機捲繞而成爲薄膜。於此情況下，爲了在使用薄膜 之前的期間保護其表面，亦可在其一面或兩面上貼合有由 其它熱塑性樹脂所成的表面保護薄膜之狀態下捲繞。於金 〇 屬製冷卻輥與接觸輥之間夾壓丙烯樹脂的熔融狀片及熱塑 性樹脂所成的二軸拉伸薄膜時，亦可將二軸拉伸薄膜當作 一側的表面保護薄膜。 本發明的第一複合偏光板所用的第一相位差板係如上 述地，面內的相位差値R〇在90〜200nm的範圍內。第一 相位差板之面內的相位差値Ro若在此範圍以外，則安裝 有其的液晶顯示裝置之視野角特性變差。再者，本發明的 第一相位差板之面內的相位差値R〇係指使用自動雙折射 ® 測定裝置KOBRA-21ADH (王子計測機器（股）製）所測 定之値。此自動雙折射測定裝置KOBRA-21 ADH係可同時 測定、顯示面內的相位差値Rc以及厚度方向的相位差値 Rth、Nz係數、面內遲相軸方向的折射率nx、面內進相軸 方向的折射率ny及厚度方向的折射率nz。 本發明的第一複合偏光板所用的第一相位差板亦更具 有一個特徵爲：以薄膜的面內遲相軸方向之折射率當作nx ，以薄膜的面內進相軸方向之折射率當作ny，以薄膜的厚 度方向之折射率當作nz時，以下式所定義的Nz係數爲在 -21 - 200946989 0.90〜1 .10的範圍，Nz coefficient = (nx - nz) / (nx - ny) The first phase difference plate of the composite polarizing plate group of the present invention is preferably a film obtained by stretching a propylene-based resin at a fixed end transversely. The composite polarizing plate group of the present invention is preferably used in a VA mode liquid crystal display device. Further, the present invention provides a liquid crystal display device comprising the composite polarizing plate group of the present invention and a liquid crystal display device of the liquid crystal cell, wherein the first composite polarized light is adhered to the pressure-sensitive adhesive layer on one side of the liquid crystal cell. The plate is formed on the other side of the liquid crystal cell with the pressure-sensitive adhesive layer attached to the second composite polarizing plate. [Embodiment] The best mode for carrying out the invention Π Composite polarizing plate group-9-200946989 The composite polarizing plate group of the present invention has a first composite polarizing plate disposed on one side of the liquid crystal cell and a second composite layer disposed on the other side. A polarizing plate is used to fabricate a liquid crystal display device, which is supplied as a combination of a first composite polarizing plate and a second composite polarizing plate. The first composite polarizing plate and the second composite polarizing plate of the present invention each have a polarizing plate, a phase difference plate (first phase difference plate or second phase difference plate), and a pressure-sensitive adhesive layer laminated in this order. structure. [1-1] First composite polarizing plate 〇 Here, FIG. 1 is a perspective view schematically showing a first composite polarizing plate 1 of a preferred example of the composite polarizing plate assembly of the present invention in a state in which the respective layers are separated, and second. The figure schematically shows a perspective view of a first composite polarizing plate 11 of a preferred other example used in the composite polarizing plate group of the present invention in a state in which the respective layers are separated. The first composite polarizing plates 1 and 11 shown in Figs. 1 and 2 have the same structure except that the polarizing plates 2 and 12 are partially different, and the first phase is laminated on the polarizing plates 2 and 12. The difference plate 3 and the pressure-sensitive adhesive layer 4 are formed. © One of the features of the first retardation film 3 used in the present invention is a retardation film obtained by stretching an acrylic resin, and has a phase difference 値R in the plane. It is in the range of 90 to 2 OOnm. That is, the first phase difference plate 3 used in the present invention is a completely one-axis phase difference film (as described above, an axial film of a range of 0.90 SNz coefficient S 1.10). In order to obtain such a positively-uniform retardation film, it is generally possible to stretch the resin film having a positive intrinsic birefringence, and the stretching method may be a fixed-end one-axis stretching, a free-end one-axis stretching, or the like. -10-200946989 Here, a stretching method called longitudinal stretching in which the film is stretched in the longitudinal direction (flow direction) when the free end is continuously stretched by a long roll for a film is used. The retardation axis direction of the retardation film obtained in this manner is substantially parallel to the longitudinal direction of the film. Further, the polarizing plate is usually obtained by stretching a free end of a long roll of a film made of a polyvinyl alcohol resin, and the absorption axis direction is substantially parallel to the longitudinal direction thereof. When the retardation axis direction of the retardation film is perpendicular to the absorption axis direction of the polarizing plate, at least one of the long rollers is cut into a sheet shape to a certain extent, and the direction is rotated. After 90 degrees, the other film must be attached one by one. On the other hand, when the phase difference film obtained by stretching the fixed end transversely by a tenter or the like is used, since the direction of the slow axis and the longitudinal direction of the long roll are orthogonal directions (width direction), the pair of rolls can be used. The roller is continuously attached to the long roller of the retardation film and the long roller of the polarizing plate. However, when the normal amorphous resin film is stretched by the one end of the fixed end, it is difficult to obtain a completely one-axis retardation film, and the Nz coefficient > 1 · 1 0 is more. In the present invention, the propylene resin having a completely one-axis property can be obtained by stretching at a high magnification of a certain degree or more even when the fixed end is applied to the horizontal axis, and the first phase difference plate 3 is used. It is regarded as a completely axial retardation film. Here, the high magnification of a certain degree or more is usually 2 times or more, preferably 3 times or more, more preferably 3 5 times or more, and the upper limit of the stretching ratio is not particularly limited, but if it is too excessive When the film is stretched, the film is broken, and it is usually stretched at a ratio of 1 Torr or less, preferably 8 -11 to 200946 989 times or less, more preferably 6 times or less. The retardation film obtained by stretching the fixed end transversely axially has a direction in which the slow axis direction is substantially parallel to the longitudinal direction of the film at a different angle of 90 degrees (=width direction), so the acrylic resin is passed through the roll to roll. The long roll of the retardation film obtained by stretching the fixed end transversely to the axis is bonded to the long roll of the polarizing plate', and the first composite polarizing plate used in the composite polarizing plate group of the present invention can be efficiently and easily produced. This means that, as in the present invention, a film composed of an acrylic resin can be used for the retardation film. The acrylic resin used in the first phase difference plate of the first composite polarizing plate of the present invention is mainly a resin composed of a propylene unit, generally crystalline, and may be propylene and a propylene homopolymer thereof. a copolymer of copolymerizable comonomers. The comonomer which is copolymerized with the propylene is exemplified by an α-olefin having an atomic number of 4 to 2 Å (CM to C20). Specific examples of the a-olefin having 4 to 20 carbon atoms include 1-butene and 2-methyl-hydrazine-propion (above C4); 1-pentene, 2-methyl-1-butylene , 3-methylbutene (above ◎ C 5 ); 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-〗 _ Ding, 2-methyl-1-pentyl Alkene, 3-methyl-1-pentene, 4-methyl-K-pentan, 3,3-dimethyl-1-butan (above C6), 1_g, 2 -methyl-1- Suspected, 23-methyl-1-pentene, 2-ethyl-1-pentene, 2-methyl-3_ethylene_丨-butene (above C7); 1-octene, 5-methyl 1-heptene, 2-ethyl-hydrazine-hexa-, 3,3-dimethyl-1-hexene, 2-methyl-3-ethyl-1-pentene, 2,3,4_ Trimethyl 丨 丨 pentene, 2-propyl-1-pentene, 2,3-diethyl-1-butene (above C8) . ι decene (C9) ; 1- 癸 (CIO) ; 1- eleven can (C11) twelve suspects-12- 200946989 (C12); 1-tridecene (C13); 1-tetradecene (C14); 1-pentadecene (C15); 1-ten Hexene (C16); oxime-heptadecene (C17); 1-octadecene (C18); 1-nonenylene (C19) and the like. Among the above α-olefins, an α-olefin having a carbon number of 4 to 12 is specifically exemplified by butene, 2-methyl-1·propene, pentene and 2-methyl-1. -butene, 3-methyl-1-butene; p-hexene, 2-ethyl-b-butene, 2,3-dimethyl-1-butene, 2-methyl-p-pentene, 3 -methyl-non-pentene, 4-methyl-® 1-pentene, 3,3-dimethyl-1-butene; 1-heptene, 2-methyl-1-hexene, 2, 3-dimethyl-1-pentene, 2-ethyl-1-pentene, 2-methyl-3-ethyl-1-butene; 1-octene, 5-methyl-1-heptene , 2-ethyl-non-hexene, 3,3-dimethyl-1-hexene, 2-methyl-3-ethyl-1-pentene, 2,3,4-trimethyl-1 -pentene, 2-propyl-1-pentene, 2,3-diethyl-1-butene; 1-decene; 1-decene; undecene; 1-dodecene and the like. From the viewpoint of copolymerizability, at least one selected from the group consisting of 1-butene, 1-pentene, 1-hexene and 1-octene is particularly preferably 1-butene and/or 1-hexene. The copolymer may be a random copolymer or a block copolymer. As a preferable copolymer, a propylene-ethylene copolymer or a propylene-1. butene copolymer is mentioned. The bismuth content and the 1-butadiene monoterpene content of the propylene-ethylene copolymer or the propylene-I-butene copolymer can be, for example, according to the "Handbook of Molecular Analysis" (1995, issued by Kiiiyaya Bookstore), page 616. The method described is determined by infrared (IR) spectrometry. From the viewpoint of improving transparency or processability, it is preferred to use a random copolymer of any unsaturated hydrocarbon having propylene as a main component. Among them, a copolymer with ethylene is preferred. In the case of the copolymer, the copolymerization ratio of the unsaturated hydrocarbon other than propylene is preferably from 1 to 10% by weight, and more preferably from 3 to 7% by weight. When the unit of the unsaturated hydrocarbon other than propylene is 1% by weight or more, there is a tendency that the workability or transparency is improved. However, if the ratio exceeds 10% by weight, the melting point of the resin is lowered, and the heat resistance tends to be deteriorated, which is not preferable. In addition, when two or more types of comonomers are copolymerized with propylene, the total content of all the comonomers contained in the obtained copolymer is preferably within the above range. The propylene resin can be produced by a method of homopolymerizing propylene, a method of copolymerizing propylene with another copolymerizable comonomer, or the like. Among these methods, for example, a titanium-magnesium (Ti-Mg) catalyst formed by a solid catalyst component containing magnesium, titanium, and halogen as essential components, and (2) magnesium, a catalyst system in which titanium and halogen are used as essential components, a catalyst system in combination with an organoaluminum compound and a third component such as an electron-donating compound, and (3) a well-known polymerization such as a metallocene catalyst. Use catalyst. Among the above catalyst systems, a solid catalyst component containing magnesium, titanium and halogen as essential components, and a combination of an organoaluminum compound and an electron-donating compound are most commonly used. More specifically, examples of the organoaluminum compound include triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride, tetraethyldialuminoxane, and the like; The compound may, for example, be cyclohexylethyldimethoxydecane, tert-butylpropyldimethoxydecane, tert-butylethyldimethoxydecane or dicyclopentyldimethoxydecane. On the other hand, as a solid component of the catalyst, which is a component of the catalyst, which is a component of the composition of the present invention, for example, JP-A-61-210,606, and JP-A-61-28-7904, Japanese Patent No. 258725, Japanese Patent No. 2,627,669, Japanese Patent No. 2,627, 669, and Japanese Patent No. 2,668,732, the disclosure of which is incorporated herein by reference. Such as the catalyst system described. The propylene resin can be, for example, a solution polymerization method using an inert solvent represented by a hydrocarbon compound® such as hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, benzene, toluene or xylene. In the bulk polymerization method using a liquid monomer as a solvent, a gas monomer is produced by a gas phase polymerization method in which a gas monomer is polymerized as it is. The polymerization of these methods can be carried out batchwise or continuously. The stereoregularity of the propylene resin may be any of the same row, the opposite row, and the miscellaneous row. In the present invention, it is preferred to use the propylene resin in the opposite row or in the same row from the viewpoint of heat resistance. The melt flow rate (MFR) of the propylene resin used in the present invention measured in accordance with JIS K7210 at a temperature of 23 ° C and a load of 21.18 N is preferably in the range of 0.1 to 200 g/10 min, particularly preferably A range of 0.5 to 50 g/10 minutes. By using an acrylic resin having an MFR in this range, a uniform film can be obtained without applying a large load to the extruder. The propylene resin may be blended with a well-known additive insofar as it does not impair the effects of the present invention. Examples of the additive include an antioxidant 'ultraviolet absorber, an antistatic agent, a lubricant, a nucleating agent, an antifogging agent, an anti-blocking agent, and the like. Examples of the antioxidant include a phenolic antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, a hindered amine-based light stabilizer, and the like, and it is also possible to use, for example, a phenolic antioxidant mechanism and phosphorus in one molecule of -15-200946989. A compound antioxidant that is a unit of an antioxidant mechanism. Examples of the ultraviolet absorber include a UV absorber such as a 2-hydroxybenzophenone type or a hydroxyphenylbenzotriazole type, and a benzoate type ultraviolet blocking agent. The antistatic agent may be any of a polymer type, an oligomer type, and a monomer type. The slip agent may, for example, be a higher fatty acid such as a crude fatty guanamine such as mustardamine or ceramide or a higher fatty acid such as stearic acid or a salt thereof. Examples of the nucleating agent include a sorbitol-based nucleating agent, an organic phosphate-based nucleating agent, and a polymer-based nucleating agent such as polyethylene cyclohexane. As the anti-blocking agent, a spherical or nearly fine particle shape can be used in an inorganic or organic system. These additives can be used in a plurality of types. In the present invention, a propylene resin as described above is formed into a film and used as a roll for a phase difference film. For example, by extrusion molding of a molten resin, a resin dissolved in an organic solvent is cast on a flat plate, a solvent is removed to form a film by a solvent casting method, or the like, and a propylene system having substantially no in-plane retardation can be obtained. Resin film. A method of manufacturing a film by extrusion molding will be described in detail. The propylene resin is melt-kneaded by the rotation of the screw in the extruder, and is extruded into a sheet shape by a T die. The temperature of the molten sheet to be extruded is 180 to 30 (TC. When the temperature of the molten sheet at this time is lower than 180 ° C, the ductility is insufficient, and the thickness of the obtained film becomes uneven. The possibility of a film having an uneven phase difference. Further, if the temperature exceeds 300 ° C, deterioration or decomposition of the resin is likely to occur, and bubbles may be generated in the sheet or carbide may be contained. The extruder may be uniaxially extruded. Machine or 2-axis extruder. For example, in a single-axis extruder, the ratio of the length L of the screw to the diameter D is L/D system 24~36 left-16-200946989 right, the space volume of the thread groove of the resin supply part The ratio of the space volume of the thread groove of the resin measuring unit (the former/the latter) is about 1.5 to 4, and the type of the kneading part having the full thread type, the barrier type, and the Madoc type can be used. From the viewpoint of suppressing deterioration or decomposition of the propylene resin and uniform melt-kneading, it is preferable to use a barrier type screw having an L/D of 28 to 36 and a compression ratio of 2.5 to 3.5. Inhibiting the deterioration or decomposition of the propylene resin, preferably in a nitrogen atmosphere or in the extruder © Vacuum. Further, in order to remove volatile gas generated by deterioration or decomposition of the propylene resin, it is preferable to provide a hole having a diameter of 1 to 5 mm at the tip end of the extruder to increase the resin pressure at the tip end portion of the extruder. Increasing the resin pressure at the front end portion of the extruder means increasing the back pressure of the front end, thereby improving the stability of the extrusion. The diameter of the hole used is preferably 2 to 4 mm in diameter. Preferably, the head is not slightly stepped or damaged on the surface of the flow path of the resin, and the lip portion is preferably plated or coated with a material having a small coefficient of friction with the molten propylene-based resin, and the lip The tip end is preferably honed to a sharp edge shape having a diameter of 0.3 mm or less. As a material having a small friction coefficient, a tungsten carbide-based or fluorine-based special plating may be used. By using such a T die, By suppressing the occurrence of the die cavities and suppressing the die line, a resin film excellent in uniformity of appearance can be obtained. The manifold of the T die is in the shape of a hanger, and preferably satisfies the following condition (1) or ( 2), better to meet Piece (3) or (4) • Condition (1) When the lip width of the T die is less than 1 500 mm: Thickness of the T die -17- 200946989 Direction length > 1 80 mm • Condition (2) T die When the lip width is 1 500 mm or more: Length of the thickness direction of the T die> 220 mm • Condition (3) When the lip width of the T die is less than 1 500 mm: Length of the height of the T die > 250 mm • Condition (4) T When the lip width of the die is 1 500 mm or more: the length of the T die is 280 mm. By using a T die that satisfies such conditions, the flow of the molten acrylic resin inside the T die can be rectified, and even in The lip portion can also be extruded while suppressing uneven thickness, so that a protective film having more excellent thickness precision and uniform phase difference can be obtained. From the viewpoint of suppressing the extrusion variation of the propylene resin, it is preferred to mount the gear pump via the joint between the extruder and the T die. Further, in order to remove foreign matter in the propylene resin, it is preferred to install a leaf disc filter. The molten sheet extruded from the T die is contacted by a metal cooling roll (also referred to as a chill roll or a casting roll) and an elastomer-containing body that is rotated in the circumferential direction of the metal chill roll. Between the rolls, they are pinched and cooled to solidify to obtain the desired film. In this case, the contact roller may be used as a surface as an elastic body such as rubber, or may be coated on the surface of the elastic roller by an outer cylinder formed of a metal sleeve. When the contact roller of the -18-200946989 coated with the outer cylinder formed by the metal sleeve is used, the molten sheet of the acrylic resin is directly sandwiched between the metal cooling roller and the contact roller and cooled. . On the other hand, when a contact roll having an elastic surface is used, a biaxially stretched film of a thermoplastic resin may be present between the molten sheet of the acrylic resin and the contact roll to be pinched. When the molten sheet of the propylene resin is held by the cooling roll and the contact roll and cooled and solidified, the surface temperature of the cooling roll and the contact roll must be lowered to rapidly cool the molten sheet. Specifically, the surface temperature of the two rolls was adjusted to a range of 0 to 30 °c. When the surface temperature exceeds 30 ° C, the cooling and solidification of the molten sheet takes time, the crystal component in the propylene resin grows, and the obtained film has poor transparency. On the other hand, when the surface temperature of the roll is lower than 〇 °C, the surface of the metal cooling roll will condense and adhere to water droplets, and the appearance of the film tends to deteriorate. The metal cooling roll to be used is transferred to the surface of the propylene resin film because of its surface state. Therefore, when the surface has irregularities, the thickness precision of the obtained propylene resin film may be lowered. Therefore, the surface of the metal cooling roll W is preferably mirror-like as much as possible. Specifically, the surface roughness of the metal cooling roll is preferably 0.3 S or less, more preferably 0.1 to 0.2 S, in a standard number of maximum heights. The surface hardness of the elastic body of the contact roll forming the nip portion with the metal cooling roll is preferably 65 to 80, more preferably 70, as measured by a spring type hardness test (A shape) prescribed in JIS K 63 01. ~80. By using the rubber roller having such a surface hardness, the line pressure applied to the molten sheet can be easily and uniformly maintained, and a deposit of the molten sheet (resin accumulation) is not formed between the metal cooling roll and the contact roll. It can be easily formed into a film. -19- 200946989 The pressure (linear pressure) when the molten sheet is pinched is determined by the pressure of the metal cooling roller to press the contact roller. The line pressure is preferably 50 to 3 OON/cm, more preferably 100 to 25 ON/cm. By pressing the wire in the above range, deposits are not formed, and it is easy to produce a propylene resin film while maintaining a certain line pressure, and a molten sheet and a thermoplastic resin which sandwich the acrylic resin between the metal chill roll and the contact roll. In the case of the biaxially stretched film, the thermoplastic resin constituting the biaxially stretched film may be any resin which does not strongly heat-adhere to the acrylic resin, and specifically, polyester, polyamide, and poly Vinyl chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacrylonitrile, and the like. Among these, polyester which is less in dimensional change due to humidity or heat is preferable. The thickness of the biaxially stretched film in this case is usually about 5 to 50 μηη, preferably 10 to 30 μχη. In this method, the lip of the tantalum die is pressed from the metal cooling roll and the contact roll. The distance (air gap) is preferably 200 mm or less, more preferably 160 mm or less. When the molten sheet extruded from the T die is stretched from the lip © to the roll, alignment tends to occur. By shortening the air gap as described above, a film having a smaller alignment can be obtained. The lower limit of the air gap is determined by the diameter of the metal cooling roller used, the diameter of the contact roller, and the shape of the tip end of the lip to be used, and is usually 50 mm or more. The processing speed at the time of producing the propylene resin film by this method is determined by the time required for cooling and solidifying the molten sheet. When the diameter of the metal cooling roll to be used is increased, the contact distance between the molten sheet and the cooling roll becomes long, so that it can be manufactured at a higher speed. Specifically, when a metal cooling roll having a diameter of -20 - 200946989 600 mm is used, the processing speed is at most about 5 to 20 m/min. The molten sheet sandwiched between the metal cooling roll and the contact roll is cooled and solidified by contact with the roll. Further, the end portion is cut as necessary, and then wound up in a winder to form a film. In this case, in order to protect the surface thereof before the film is used, it may be wound in a state in which a surface protective film made of another thermoplastic resin is bonded to one surface or both surfaces thereof. When a biaxially stretched film of a molten sheet of acrylic resin and a thermoplastic resin is sandwiched between a cooling roll and a contact roll of a metal enamel, the biaxially stretched film may be used as a surface protective film on one side. The first phase difference plate used in the first composite polarizing plate of the present invention is as described above, and the in-plane phase difference 値R 〇 is in the range of 90 to 200 nm. If the phase difference 値Ro in the plane of the first retardation film is outside this range, the viewing angle characteristics of the liquid crystal display device mounted thereon are deteriorated. In addition, the phase difference 値R〇 in the plane of the first retardation film of the present invention is measured by the automatic birefringence meter measuring device KOBRA-21ADH (manufactured by Oji Scientific Instruments Co., Ltd.). This automatic birefringence measuring device KOBRA-21 ADH can simultaneously measure and display the phase difference 値Rc in the plane, the phase difference 値Rth, Nz coefficient in the thickness direction, the refractive index nx in the in-plane slow axis direction, and the in-plane phase inversion. The refractive index ny in the axial direction and the refractive index nz in the thickness direction. The first phase difference plate used in the first composite polarizing plate of the present invention further has a feature that the refractive index in the in-plane slow axis direction of the film is regarded as nx, and the refractive index in the in-plane axis direction of the film As ny, when the refractive index in the thickness direction of the film is taken as nz, the Nz coefficient defined by the following formula is in the range of -21 - 200946989 0.90 to 1.10.
Nz 係數=(nx-nz) / ( nx-ny) 本發明所用的第一相位差板，由於目標爲如上述的完 全一軸性，故其Nz係數必須在0.90〜1.10的範圍內。藉 由拉伸來製作Nz係數低於0.90的薄膜係困難。另一方面 ，於Nz係數超過1 . 1 0時，安裝有其的液晶顯示裝置之對 比視野角會降低。再者，本發明的第一相位差板之薄膜的 面內遲相軸方向之折射率nx、面內進相軸方向的折射率 ny、厚度方向的折射率nz及Nz係數係如上述，指例如使 用自動雙折射測定裝置KOBRA-21ADH (王子計測機器（ 股）製）所測定之値。 又，作爲本發明的第一複合偏光板所用的偏光板，可 爲該領域中所一般使用者，例如一般使用於聚乙烯醇樹脂 上吸附配向有二色性色素（碘、二色性有機染料等）的直 線偏光薄膜之兩面或一面上，層合有由三乙醯纖維素樹脂 、環狀環烯烴樹脂、鏈狀環烯烴樹脂等的樹脂薄膜所成的 保護層之構造。第1圖中顯示使用直線偏光薄膜5的兩面 上設有保護層6、7的偏·光板2之情況，而且第2圖中顯 示使用直線偏光薄膜5的一面（層合有第一相位差板3的 側之相反側的面）上設有保護層6的偏光板12之情況。 本發明中的第一複合偏光板，係於第一相位差板的遲 -22- 200946989 相軸方向與偏光板的吸收軸方向以80〜100°的角度交叉 方式配置的狀態下，層合第一相位差板與偏光板。第一相 位差板的遲相軸方向與偏光板的吸收軸方向所成的角度若 在此範圍外，則安裝有其的液晶顯示裝置在黑顯示時會發 生漏光而使對比降低，而且容易發生色不均。從更高對比 或色不均的減低之觀點來看，第一相位差板的遲相軸方向 與偏光板的吸收軸方向所成的角度較佳爲在85〜95°的 〇 範圍內，更佳爲在89〜91°的範圍內。 作爲第一複合偏光板1、11中的第一相位差板3之與 偏光板2、1 2鄰接側的相反側上所形成的感壓性黏著劑（ 黏著劑）層4，可使用以往的液晶顯示裝置用所用的各種 感壓性黏著劑，例如丙烯酸、橡膠、胺甲酸乙酯、聚矽氧 、聚乙烯醚等的感壓性黏著劑，其中以透明性、耐候性、 耐熱性等優異的丙烯酸樹脂當作基礎聚合物的黏著劑係較 合適。 ^ 丙烯酸系感壓性黏著劑係沒有特別的限制，可合適地 使用（甲基）丙烯酸丁酯、（甲基）丙烯酸乙酯、（甲基 )丙烯酸異辛酯、（甲基）丙烯酸2-乙基己酯般的（甲基 )丙烯酸酯基礎聚合物，或用2種類以上的此等（甲基） 丙儲酸酯等之共聚合基礎聚合物。再者，於此等基礎聚合 物中’極性單體係共聚合著。作爲極性單體，例如可舉出 (甲基）丙烯酸、（甲基）丙烯酸2-羥丙酯、（甲基）丙 嫌酸羥乙醋、（甲基）丙烯醯胺、N，N-二甲基胺基乙基（ 甲基）丙烯酸酯、基（甲基）丙烯酸縮水甘油酯般的具有 -23- 200946989 羧基、羥基、醯胺基、胺基、環氧基等的官能基之單體。 此等丙烯酸感壓性黏著劑當然可單獨使用，但通常倂 用交聯劑。作爲交聯劑，可例示2價或多價金屬鹽的在與 羧基之間形成羧酸金屬鹽者、多胺化合物的在與羧基之間 形成醯胺鍵者、聚環氧化合物或多元醇化合物的在與羧基 之間形成酯鍵者、聚異氰酸酯化合物的在與羧基之間形成 醯胺鍵者等。其中，廣泛使用聚異氰酸酯化合物當作有機 系交聯劑。 0 於感壓性黏著劑組成物中，除了上述基礎聚合物及交 聯劑’按照需要，爲了調整感壓性黏著劑的黏著力、內聚 力、黏性、彈性模數、玻璃轉移溫度等，例如亦可摻合天 然物或合成物的樹脂類、增黏樹脂、抗氧化劑、紫外線吸 收劑、染料、顏料、消泡劑、腐蝕抑制劑、光聚合引發劑 等的適宜添加劑。再者，也可含有微粒子當作顯示光散射 性的感壓性黏著劑層。 感壓性黏著劑層的厚度較佳爲1〜30μιη，更佳爲5〜 Ο 25μηι。感壓性黏著劑層若過薄，貝IJ黏著性降低，而若過厚 ，則感壓性黏著劑容易發生滲出等的不良狀況。 再者，於第一相位差板3上形成感壓性黏著劑層的方 法係沒有特別的限制，可在第一相位差板3之應形成感壓 性黏著劑層的面上，塗佈含有以上述基礎聚合物爲首的各 成分之溶液，進行乾燥而形成感壓性黏著劑層後，層合施 有聚矽氧等的脫模處理之分離片而得，於分離片上形成感 壓性黏著劑層後，亦可第一相位差板3轉印及層合。又， -24- 200946989 於偏光薄膜上形成感壓性黏著劑層之際，按照需要可對第 一相位差板及感壓性黏著劑層的至少一方施予密接處理， 例如電暈處理等。再者，所形成的感壓性黏著劑層之表面 通常係被施有脫模處理的分離膜所保護，分離膜係如後述 地在將本發明的複合偏光板組貼合於液晶胞之前被剝離。 於本發明的第一複合偏光板中，爲了貼合偏光薄膜與 保護層，或貼合偏光薄膜或保護層與第一相位差板，例如 ❹ 可使用以環氧樹脂、胺甲酸乙酯樹脂、氰基丙烯酸酯樹脂 、丙烯醯胺樹脂等當作成分的黏著劑。從減薄黏著劑層的 觀點來看，較佳的黏著劑例如是水系黏著劑，即黏著劑成 分溶解在水中者或分散在水中者。又，作爲其它較佳的黏 著劑’可舉出無溶劑型的黏著劑，具體地爲藉由加熱或活 性能量線的照射使單體或寡聚物反應硬化而形成黏著劑層 者。 作爲可成爲水系黏著劑的黏著劑成分，例如可舉出水 w 溶性的交聯性環氧樹脂、胺甲酸乙酯樹脂等。作爲水溶性 交聯性環氧樹脂，例如可舉出使二伸乙基三胺、三伸乙基 四胺等的多伸烷基多胺與己二酸等的二羧酸之反應所得之 聚醯胺多胺'與環氧氯丙烷反應而得之聚醯胺環氧樹脂。 作爲如此的聚醯胺環氧樹脂之市售品，具體地可舉出 Sumirez 650 (住化 CHEMTEX (股）製）、Sumirez 675 ( 住化CHEMTEX (股）製）等。 使用水溶性環氧樹脂當作黏著劑成分時，爲了進一步 提高塗佈性及黏著性，較佳爲混合聚乙烯醇樹脂等其它的 -25- 200946989 水溶性樹脂。聚乙烯醇樹脂，除了部分皂化聚乙烯醇、完 全皂化聚乙烯醇’亦可爲羧基改性聚乙烯醇、乙醯乙醯基 改性聚乙烯醇、羥甲基改性聚乙烯醇、胺基改性聚乙烯醇 般的改性聚乙烯醇系樹脂。其中’較佳爲使用醋酸乙烯酯 及不飽和羧酸或其鹽的共聚物之皂化物，即羧基改性聚乙 烯醇。再者，此處所言的「羧基」係包括-COOH及其鹽的 槪念。作爲羧基改性聚乙烯醇的市售品，具體地可舉出 Kur ar ay P 〇 v al KL- 5 0 6 ((股）KU R AR A Y 製）、Kur ar ay Poval KL-318 ((股）KURARAY 製）、Kuraray Poval KL-118 ((股）KURARAY 製）、Gohsenol T-3 3 0 (日本 合成化學工業（股）製）、Gohsenol T-3 5 0 (日本合成化 學工業（股）製）、DR-0415(電氣化學工業（股）製） 、AF-17 (日本 VAM-POVAL (股）製）、AT-17 (日本 VAM-POVAL (股）製）、AP-17 (曰本 VAM-POVAL (股 )製）等。 作爲含有水溶性環氧樹脂的黏著劑時，使該環氧樹脂 〇 及視需要添加的聚乙烯醇樹脂等其它水溶性樹脂溶解在水 中’以構成黏著劑溶液。於此情況下，水溶性環氧樹脂較 佳每100重量份的水有0.2〜2重量份的範圍之濃度。又 ’於摻合聚乙烯醇系樹脂時，其量較佳爲每1〇〇重量份的 水有1〜10重量份，更佳爲丨〜5重量份。 另一方面’於使用含胺甲酸乙酯樹脂的水系黏著劑時 ’作爲適當的胺甲酸乙酯樹脂之例，可舉出離子鍵聚合物 型的胺甲酸乙酯樹脂，尤其聚酯離子鍵聚合物型胺甲酸乙 -26- 200946989 酯樹脂。此處，所謂的離子鍵聚合物型’就是在構成骨架 的胺甲酸乙酯樹脂中導入有少量的離子性成分（親水成分 )者。又，所謂的聚酯離子鍵聚合物型胺甲酸乙酯樹脂， 就是具有聚酯骨架的胺甲酸乙酯樹脂，其中導入有少量的 離子性成分（親水成分）者。由於該離子鍵聚合物型胺甲 酸乙酯樹脂係不使用乳化劑而直接在水中乳化成爲乳液， 故適合作爲水系黏著劑。作爲聚酯離子鍵聚合物型胺甲酸 © 乙酯樹脂的市售品，具體地可舉出皆爲乳液形態的Hydran AP-20 (大日本油墨化學工業（股）製）、Hydran APX-101H(大日本油墨化學工業（股）製）等。 以離子鍵聚合物型的胺甲酸乙酯樹脂當作黏著劑成分 時，通常較佳爲更摻合異氰酸酯等的交聯劑。異氰酸酯交 聯劑係分子內具有至少2個異氰酸基（-NCO )的化合物 ，其例子有2,4-伸甲苯二異氰酸酯、伸苯二異氰酸酯、 4,4’-二苯基甲烷二異氰酸酯、1，6_六亞甲基二異氰酸酯、 ® 異佛爾酮二異氰酸酯般的聚異氰酸酯單體，以及彼等複數 分子附加於如三羥甲基丙烷的多元醇而成的加成物，二異 氰酸酯3分子在各自一末端異氰酸基的部分形成有異氰尿 酸酯環的3官能異氰尿酸酯體，二異氰酸酯3分子在各自 一末端異氰酸基的部分進行水合•脫碳酸而形成的縮二脲 體般之聚異氰酸酯改性體等。作爲異氰酸酯系交聯劑的市 售品，具體地可舉出Hydran Assist ar C-1 (大日本油墨化 學工業（股）製）等。 使用含離子鍵聚合物型的胺甲酸乙酯樹脂之系黏著劑 -27- 200946989 時’從黏度與黏著性的觀點來看，較佳爲以該胺甲酸乙酯 樹脂的濃度成爲10〜70重量％，尤其20〜50重量％的方 式，使分散有水中。於摻合異氰酸酯交聯劑時，對於100 重量份的胺甲酸乙酯樹脂而言，適宜選擇地摻合量，以使 異氰酸酯交聯劑成爲5〜100重量份。 將如以上的水系黏著劑塗佈在保護層、第一相位差板 、偏光薄膜的至少任一者上，貼合兩者而可成爲偏光板。 貼合偏光薄膜與保護層的方法係沒有特別的限定，例如在 ® 聚乙烯醇偏光薄膜或保護層之表面上均勻塗佈黏著劑，在 塗佈面上重疊另一方的薄膜，藉由輥等來貼合、乾燥的方 法等。乾燥例如係在60〜100°c左右的溫度進行。從更提 高黏著力的觀點來看，乾燥後較佳爲在比室溫稍高的溫度 ’例如30〜50°C左右的溫度熟化1〜10日左右。 又，於使用無溶劑型的黏著劑時，從反應性的觀點來 看，較佳使用經由加熱或活性能量線的照射，進行陽離子 聚合而硬化者。此處，所謂的無溶劑型的黏著劑，係指不 〇 含有有意義量的溶劑之形態的黏著劑，一般係包含經由加 熱或活性能量線的照射而聚合的硬化性化合物及聚合引發 劑所構成。 特別地，從耐候性或折射率等的觀點來看，較佳爲使 用分子內不含有芳香環的環氧化合物當作硬化性化合物。 作爲使用分子內不含有芳香環的環氧化合物之黏著劑，例 如可舉出特開2004-245925號公報中記載者。作爲如此不 含有芳香環的環氧化合物，可例示芳香族環氧化合物的氫 -28- 200946989 化物、脂環式環氧化合物、脂肪族環氧化合物等°黏著劑 所用的硬化性環氧化合物通常在分子中具有2個&±0^環 氧基。 芳香族環氧化合物的氫化物，係可藉由在觸媒的存在 下、加壓下，對芳香族環氧化合物的芳香環進行選擇地氫 化反應而得。作爲芳香族環氧化合物’例如可舉出雙酌A 的二縮水甘油醚、雙酚F的二縮水甘油醚、雙酚s的二縮 ® 水甘油醚等的雙酚型環氧化合物；苯酚酚酵清漆環氧樹脂 、甲酚酚醛清漆環氧樹脂、羥基苯甲醛苯酚酚醛清漆環氧 樹脂等的酚醛清漆型的環氧樹脂；四羥基二苯基甲烷的縮 水甘油醚、四羥基二苯甲酮的縮水甘油醚、環氧化聚乙烯 苯酚等的多官能型環氧化合物等。於此等芳香族環氧化合 物的氫化物之中，較佳者例如是經氫化的雙酚A之二縮水 甘油醚。 又，脂環式環氧化合物係指分子內具有至少1個如下 ® 式所示之鍵結於脂環式環的環氧基之化合物（式中，m表 示2〜5的整數）。Nz coefficient = (nx - nz) / (nx - ny) The first phase difference plate used in the present invention has a Nz coefficient in the range of 0.90 to 1.10 since the target is completely monoaxial as described above. It is difficult to form a film having an Nz coefficient of less than 0.90 by stretching. On the other hand, when the Nz coefficient exceeds 1.10, the contrast viewing angle of the liquid crystal display device mounted thereon is lowered. Further, the refractive index nx of the in-plane slow axis direction of the film of the first retardation film of the present invention, the refractive index ny of the in-plane axial direction, the refractive index nz of the thickness direction, and the Nz coefficient are as described above. For example, the enthalpy measured by the automatic birefringence measuring device KOBRA-21ADH (manufactured by Oji Scientific Instruments Co., Ltd.) is used. Further, the polarizing plate used in the first composite polarizing plate of the present invention may be a general user in the field, for example, generally used for adsorbing and aligning a dichroic dye (iodine, dichroic organic dye) on a polyvinyl alcohol resin. A structure of a protective layer made of a resin film such as a triacetyl cellulose resin, a cyclic cycloolefin resin or a chain cycloolefin resin is laminated on both surfaces or one surface of the linear polarizing film. Fig. 1 shows a case where the polarizing plate 2 having the protective layers 6 and 7 on both sides of the linear polarizing film 5 is used, and Fig. 2 shows the side on which the linear polarizing film 5 is used (the first phase difference plate is laminated) The case where the polarizing plate 12 of the protective layer 6 is provided on the surface on the opposite side of the side of 3 is provided. In the first composite polarizing plate of the present invention, in the state in which the phase axis direction of the first phase difference plate is delayed from the absorption axis direction of the polarizing plate at an angle of 80 to 100 degrees, the lamination is performed. A phase difference plate and a polarizing plate. If the angle between the slow axis direction of the first phase difference plate and the absorption axis direction of the polarizing plate is outside this range, the liquid crystal display device mounted thereon may leak light during black display to lower the contrast and easily occur. Uneven color. From the viewpoint of lowering the contrast of the higher contrast or the color unevenness, the angle between the direction of the slow axis of the first phase difference plate and the absorption axis direction of the polarizing plate is preferably in the range of 85 to 95°, and Good is in the range of 89~91°. As the pressure-sensitive adhesive (adhesive) layer 4 formed on the side opposite to the side opposite to the polarizing plates 2 and 1-2 of the first phase difference plate 3 in the first composite polarizing plates 1 and 11, the conventional pressure-sensitive adhesive (adhesive) layer 4 can be used. Various pressure-sensitive adhesives for liquid crystal display devices, such as pressure sensitive adhesives such as acrylic, rubber, urethane, polyoxymethylene, and polyvinyl ether, among which are excellent in transparency, weather resistance, heat resistance, and the like. The acrylic resin is suitable as an adhesive for the base polymer. ^ The acrylic pressure-sensitive adhesive is not particularly limited, and butyl (meth)acrylate, ethyl (meth)acrylate, isooctyl (meth)acrylate, or (meth)acrylic acid 2- can be suitably used. An ethyl acrylate-based (meth) acrylate base polymer or a copolymerized base polymer of two or more types of such (meth) acrylate. Further, in the base polymer, the "polar single system" is copolymerized. Examples of the polar monomer include (meth)acrylic acid, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid hydroxyethyl vinegar, (meth)acrylamide, and N,N-di a monomer having a functional group of a carboxyl group, a hydroxyl group, a decylamino group, an amine group, an epoxy group or the like of -23-200946989, such as methylaminoethyl (meth) acrylate or glycidyl (meth) acrylate. . These acrylic pressure-sensitive adhesives can of course be used singly, but usually a crosslinking agent is used. The crosslinking agent may, for example, be a divalent or polyvalent metal salt which forms a metal carboxylate with a carboxyl group, a polyamine compound which forms a guanamine bond with a carboxyl group, a polyepoxide compound or a polyol compound. Any one that forms an ester bond with a carboxyl group, a polyisocyanate compound that forms a guanamine bond with a carboxyl group, or the like. Among them, a polyisocyanate compound is widely used as an organic crosslinking agent. 0 In the pressure-sensitive adhesive composition, in addition to the above-mentioned base polymer and crosslinking agent, in order to adjust the adhesion, cohesion, viscosity, modulus of elasticity, glass transition temperature, etc. of the pressure-sensitive adhesive as needed, for example Suitable additives for blending natural materials or synthetic resins, tackifying resins, antioxidants, ultraviolet absorbers, dyes, pigments, antifoaming agents, corrosion inhibitors, photopolymerization initiators, and the like. Further, fine particles may be contained as a pressure-sensitive adhesive layer for exhibiting light scattering properties. The thickness of the pressure-sensitive adhesive layer is preferably from 1 to 30 μm, more preferably from 5 to 25 μm. If the pressure-sensitive adhesive layer is too thin, the adhesion of the shell IJ is lowered, and if it is too thick, the pressure-sensitive adhesive is liable to cause bleeding or the like. In addition, the method of forming the pressure-sensitive adhesive layer on the first retardation film 3 is not particularly limited, and may be applied to the surface of the first phase difference plate 3 where the pressure-sensitive adhesive layer is to be formed. The solution of each component including the above-mentioned base polymer is dried to form a pressure-sensitive adhesive layer, and then a release sheet obtained by releasing a mold such as polyfluorene or the like is laminated to form a pressure-sensitive property on the separator. After the adhesive layer, the first phase difference plate 3 can also be transferred and laminated. Further, when the pressure-sensitive adhesive layer is formed on the polarizing film, at least one of the first retardation film and the pressure-sensitive adhesive layer may be subjected to a close contact treatment such as corona treatment or the like as needed. Further, the surface of the pressure-sensitive adhesive layer to be formed is usually protected by a separation membrane subjected to a release treatment, and the separation membrane is as described later before the composite polarizing plate group of the present invention is attached to the liquid crystal cell. Stripped. In the first composite polarizing plate of the present invention, in order to bond the polarizing film and the protective layer, or to bond the polarizing film or the protective layer to the first phase difference plate, for example, an epoxy resin, a urethane resin, or the like may be used. An adhesive as a component such as a cyanoacrylate resin or a acrylamide resin. From the standpoint of thinning the adhesive layer, a preferred adhesive is, for example, a water-based adhesive, i.e., one in which the adhesive component is dissolved in water or dispersed in water. Further, as another preferred adhesive, a solventless type of adhesive is exemplified, and specifically, a monomer or an oligomer is reacted and hardened by irradiation with heating or an active amount line to form an adhesive layer. Examples of the adhesive component which can be a water-based adhesive include a water-soluble crosslinkable epoxy resin and an urethane resin. The water-soluble crosslinkable epoxy resin is, for example, a polyfluorene obtained by reacting a polyalkylene polyamine such as di-ethyltriamine or tri-extended ethyltetraamine with a dicarboxylic acid such as adipic acid. A polyamine epoxy resin obtained by reacting an amine polyamine with epichlorohydrin. Specific examples of the commercially available polyamine epoxy resin include Sumirez 650 (manufactured by CHEMTEX Co., Ltd.) and Sumirez 675 (manufactured by Sumitomo CHEMTEX Co., Ltd.). When a water-soluble epoxy resin is used as the adhesive component, in order to further improve coatability and adhesion, it is preferred to mix another -25-200946989 water-soluble resin such as a polyvinyl alcohol resin. Polyvinyl alcohol resin, in addition to partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol' can also be carboxyl modified polyvinyl alcohol, ethyl acetylated modified polyvinyl alcohol, hydroxymethyl modified polyvinyl alcohol, amine Modified polyvinyl alcohol-based modified polyvinyl alcohol-based resin. Among them, it is preferred to use a saponified product of a copolymer of vinyl acetate and an unsaturated carboxylic acid or a salt thereof, that is, a carboxyl group-modified polyvinyl alcohol. Further, the "carboxy group" as used herein includes the concept of -COOH and its salt. As a commercial item of a carboxyl group-modified polyvinyl alcohol, Kurar ay P 〇v al KL- 5 0 6 (manufactured by KU R AR AY), Kur ay Poval KL-318 (( ) Kuraray Poval KL-118 (manufactured by KURARAY), Gohsenol T-3 3 0 (made by Nippon Synthetic Chemical Industry Co., Ltd.), Gohsenol T-3 5 0 (Japan Synthetic Chemical Industry Co., Ltd.) ), DR-0415 (Electrical Chemical Industry Co., Ltd.), AF-17 (Japan VAM-POVAL (share) system), AT-17 (Japan VAM-POVAL (share) system), AP-17 (曰本VAM) -POVAL (share) system, etc. When an adhesive containing a water-soluble epoxy resin is used, the epoxy resin and other water-soluble resin such as a polyvinyl alcohol resin to be added as needed are dissolved in water to constitute an adhesive solution. In this case, the water-soluble epoxy resin preferably has a concentration in the range of 0.2 to 2 parts by weight per 100 parts by weight of water. Further, when the polyvinyl alcohol-based resin is blended, the amount thereof is preferably from 1 to 10 parts by weight, more preferably from 5% to 5 parts by weight, per 1 part by weight of water. On the other hand, when using an aqueous adhesive containing an urethane resin, as an example of a suitable urethane resin, an ionomer type urethane resin, particularly polyester ionomerization, may be mentioned. The form of urethane formic acid B-26-200946989 ester resin. Here, the ionomer type is a type in which a small amount of an ionic component (hydrophilic component) is introduced into the urethane resin constituting the skeleton. Further, the polyester ionomer type urethane resin is an urethane resin having a polyester skeleton in which a small amount of an ionic component (hydrophilic component) is introduced. Since the ionomer type urethane resin is emulsified directly into water as an emulsion without using an emulsifier, it is suitable as a water-based adhesive. As a commercial item of the polyester ionomer type urethane methacrylate resin, specifically, Hydran AP-20 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) and Hydran APX-101H (both manufactured by Dainippon Ink Chemicals Co., Ltd.) are used. Dainippon Ink Chemical Industry Co., Ltd.). When an urethane polymer type urethane resin is used as the adhesive component, it is usually preferred to further blend a crosslinking agent such as isocyanate. The isocyanate crosslinking agent is a compound having at least two isocyanato groups (-NCO) in the molecule, and examples thereof are 2,4-toluene diisocyanate, phenylene diisocyanate, and 4,4'-diphenylmethane diisocyanate. , 1,6_hexamethylene diisocyanate, ® isophorone diisocyanate-like polyisocyanate monomer, and an adduct of a plurality of molecules added to a polyol such as trimethylolpropane, The isocyanate 3 molecule forms a trifunctional isocyanurate body having an isocyanurate ring at a portion of the isocyanate group at each terminal, and the diisocyanate 3 molecules are hydrated and decarbonated at a portion of the isocyanate group at each terminal. The formed biuret-like polyisocyanate modified body or the like. Specific examples of the commercially available product of the isocyanate-based crosslinking agent include Hydran Assist ar C-1 (manufactured by Dainippon Ink Chemicals Co., Ltd.). When using an urethane-containing urethane resin-based adhesive -27-200946989, it is preferable that the concentration of the urethane resin is 10 to 70 by weight from the viewpoint of viscosity and adhesion. %, especially 20 to 50% by weight, in such a way that it is dispersed in water. When the isocyanate crosslinking agent is blended, the amount of the urethane resin is suitably blended in an amount of from 5 to 100 parts by weight based on 100 parts by weight of the urethane resin. The water-based adhesive as described above is applied to at least one of the protective layer, the first retardation film, and the polarizing film, and is bonded to each other to form a polarizing plate. The method of bonding the polarizing film and the protective layer is not particularly limited. For example, the adhesive is uniformly applied to the surface of the polyvinyl alcohol polarizing film or the protective layer, and the other film is superposed on the coated surface by a roller or the like. The method of bonding, drying, etc. Drying is carried out, for example, at a temperature of about 60 to 100 ° C. From the viewpoint of higher adhesion, it is preferred to be aged at a temperature slightly higher than room temperature, for example, at a temperature of about 30 to 50 ° C for about 1 to 10 days after drying. Further, when a solventless type of adhesive is used, from the viewpoint of reactivity, it is preferred to use a polymerization by heating or an active energy ray to carry out cationic polymerization and hardening. Here, the solvent-free type of adhesive refers to an adhesive which does not contain a significant amount of a solvent, and generally comprises a curable compound and a polymerization initiator which are polymerized by irradiation with heating or active energy rays. . In particular, from the viewpoint of weather resistance, refractive index, etc., it is preferred to use an epoxy compound which does not contain an aromatic ring in the molecule as a curable compound. An adhesive of an epoxy compound which does not contain an aromatic ring in the molecule is exemplified by JP-A-2004-245925. The epoxy compound which does not contain an aromatic ring is exemplified by a hardening epoxy compound which is used for an adhesive such as a hydrogen -28-200946989 compound, an alicyclic epoxy compound or an aliphatic epoxy compound of an aromatic epoxy compound. There are 2 & ± 0 ^ epoxy groups in the molecule. The hydride of the aromatic epoxy compound can be obtained by selectively hydrogenating an aromatic ring of an aromatic epoxy compound under pressure in the presence of a catalyst. Examples of the aromatic epoxy compound include bisphenol-type epoxy compounds such as diglycidyl ether of A, diglycidyl ether of bisphenol F, and di-glycidyl ether of bisphenol s; phenol phenol; Resin varnish epoxy resin, cresol novolac epoxy resin, hydroxybenzaldehyde phenol novolac epoxy resin and other novolac type epoxy resin; tetrahydroxydiphenylmethane glycidyl ether, tetrahydroxybenzophenone A polyfunctional epoxy compound such as glycidyl ether or epoxidized polyethylene phenol. Among these hydrides of the aromatic epoxide, for example, a hydrogenated bisphenol A diglycidyl ether is preferred. Further, the alicyclic epoxy compound means a compound having at least one epoxy group bonded to an alicyclic ring represented by the following formula (wherein m represents an integer of 2 to 5).
(CH^T^O 上述式中的（CH2) m中之氫原子經去掉1個或複數 個後的形式之基與其它化學構造所鍵結成的化合物，係能 成脂環式環氧化合物。又，形成脂環式環的氫亦可被如甲 基或乙基的直鏈狀烷基所適宜取代。其中，較佳爲使用具 有環氧基環戊烷環（上式中m = 3者）或環氧基環己烷環（ -29- 200946989 上式中m = 4者）的化合物。作爲脂環式環氧化合物的具體 例，可舉出3，4-環氧基環己基甲基、3，4_環氧基環己院竣 酸酯、3,4-環氧基-6-甲基環己基甲基、3,4·環氧基甲基 環己烷羧酸酯、伸乙基雙（3,4-環氧基環己烷羧酸醋）、 雙（3,4-環氧基環己基甲基）己二酸酯、雙（3,4-環氧基_ 6-甲基環己基甲基）己二酸酯、二乙二醇雙（3,4-環氧基 環己基甲基醚）、乙二醇雙（3,4_環氧基環己基甲基酸） 、2,3，14，15-二環氧基-7,11,18,21-四氧雜三螺- © [5_2.2.5.2.2]廿一烷（3,4-環氧基環己烷螺-2，，6’-二噁烷 螺-3，，5’’ -二噁烷螺- 3’’’，4’’’-環氧基環己烷）、4- ( 3,4- 環氧基環己基）-2,6-二氧雜-8,9-環氧基螺[5.5]~(--院、4- 乙烯基環己烯二氧化物、雙-2,3-環氧基環戊基醚、二環戊 二烯二氧化物等。 又，作爲脂肪族環氧化合物，脂肪族多元醇或其環氧 烷加成物的聚縮水甘油醚係相當於此。作爲如此的脂肪族 環氧化合物’例如可舉出i，4· 丁二醇的二縮水甘油醚、 ◎ 1,6 -己二醇的二縮水甘油醚、甘油的三縮水甘油醚、三羥 甲基丙烷的三縮水甘油醚、聚乙二醇的二縮水甘油醚、丙 二醇的二縮水甘油醚、在乙二醇或丙二醇、甘油般的脂肪 族多元醇附加1種或2種以上的環氧烷（環氧乙垸或環氧 丙烷）而得之聚醚多元醇的聚縮水甘油醚等。 此處所例示的環氧化合物係可各自單獨使用’且亦可 混合複數的環氧化合物來使用。 無溶劑型黏著劑所使用的環氧化合物之環氧當量通常 -30- 200946989 爲30〜3000g/當量，較佳爲50〜 1500g/當量的範圍。環氧 當量若低於30g/當量，則有硬化後的保護薄膜之可撓性降 低或黏著強度降低下的可能性。另一方面，若超過3 000g/ 當量，則有與其它成分的相溶性降低之可能性。 爲了藉由陽離子聚合使環氧化合物硬化，而摻合陽離 子聚合引發劑。陽離子聚合引發劑係藉由可見光線、紫外 線、X線、電子線等的活性能量線之照射或加熱，而產生 ® 陽離子種或路易士酸，引發環氧基的聚合反應。從操作性 的觀點來看，較佳爲所有類型的陽離子聚合引發劑皆賦予 潛在性。 又，使用光陽離子聚合引發劑時，係可在常溫硬化， 具有減少考慮偏光薄膜的耐熱性或膨脹所致的變形之需要 ，可良好地黏著保護薄膜的優點。又，光陽離子聚合引發 劑由於以光來催化作用，即使混合於環氧化合物中，保存 安定性或操作性也優異。作爲藉由活性能量線的照射產生 ® 陽離子種或路易士酸的化合物，例如可舉出如芳香族重氮 鑰鹽、芳香族碘鑰鹽或芳香族毓鹽的鑰鹽、鐵-丙二烯錯 合物等。於此等之中，特別佳爲使用芳香族鏑鹽，因爲在 3 0 Onm以上的波長區域亦具有紫外線吸收特性，故硬化性 優異，可給予具有良好的機械強度或黏著強度的硬化物。 此等光陽離子聚合引發劑係可由市售品容易取得，具 體地可舉出 Kayarad PCI-220 (日本化藥（股）製）、 Kayarad PCI-620 (日本化藥（股）製）、UVI-6990 ( Union Carbide 公司製.）'Adekaoptomer SP-150((股） -31 - 200946989 ADEKA 製）、Adekaoptomer SP-170 ((股）ADEKA 製） 、CI-5102 (曰本曹達（股）製）、CIT- 1370 (日本曹達 (股）製）、CIT- 1 682 (日本曹達（股）製）、CIP-18 66 8(日本曹達（股）製）、（：1?-204 88(日本曹達（股 )製）、CIP-2064S (日本曹達（股）製）、DPI-101 (綠 化學（股）製）、DPI-102 (綠化學（股）製）、DPI-103 (綠化學（股）製）、DPI-105 (綠化學（股）製）、 MPI-103 (綠化學（股）製）、MPI-105 (綠化學（股）製 )、BBI-101(綠化學（股）製）、BBI-102(綠化學（股 )製）、BBI-103(綠化學（股）製）、BBI-105(綠化學 (股）製）、TPS-101 (綠化學（股）製）、TPS-102 (綠 化學（股）製）、TPS-103 (綠化學（股）製）、TPS-105 (綠化學（股）製）、：MDS-103 (綠化學（股）製）、 MDS-105(綠化學（股）製）、DTS-102C綠化學（股） 製）、DTS-103 (綠化學（股）製）、PI-2074 ( Rhodia 公 司製）等。其中，尤其CI-51 02 (日本曹達（股）製）係 較佳的光陽離子聚合引發劑之一。光陽離子聚合引發劑的 摻合量，對於100重量份的環氧化合物而言，通常爲0.5 〜20重量份，較佳爲1〜15重量份。 再者，視需要可倂用光增感劑。藉由使用光增感劑， 可提高反應性，提高硬化物的機械強度或黏著強度。作爲 光增感劑，例如可舉出羰基化合物、有機硫化合物、過硫 化物、氧化還原系化合物、偶氮及重氮化合物、鹵素化合 物、光還原性色素等。當摻合光增感劑時，對於100重量 -32- 200946989 份的環氧化合物而言，其摻合量通常爲0.1〜20重量份。 又，熱陽離子聚合引發劑係經由加熱而產生陽離子種 或路易士酸的化合物，作爲如此的熱陽離子聚合引發劑’ 苄基锍鹽、噻吩鑰鹽、四氫噻吩鑰鹽、苄基銨、吡啶鎗鹽 、肼鑰鹽、羧酸酯、磺酸酯、胺醯亞胺等。熱陽離子聚合 引發劑亦可容易由市售品取得，例如可舉出Adekaopton CP77 ((股）ADEKA 製）、Adekaopton CP 66 ((股） © ADEKA 製）、CI-2639(日本曹達（股）製）、（:1-2624 ( 日本曹達（股）製）、Saneido SI-60LC三新化學工業（ 股）製）、Saneido SI-8 0L (三新化學工業（股）製）、 Saneido SI-100L(三新化學工業（股）製）等。 再者，於本發明中，亦可倂用上述光陽離子聚合與熱 陽離子聚合。 又，環氧基系黏著劑亦可更含有氧雜環丁烷類、多元 醇類等促進陽離子聚合的化合物。 於使用無溶劑型黏著劑時，作爲在偏光薄膜、保護層 及第一相位差板的至少任一者上塗佈的方法，並沒有特別 的限制’例如可利用刮刀、線桿、口模式塗佈機、凸輪塗 佈機、凹槽輥塗佈機等種種方式。於上述各方式中，由於 各自有最合適的黏度範圍，故可使用少量的溶劑來調整黏 度。作爲其所用的溶劑，例如可使用以甲苯所代表的烴類 、以醋酸乙酯所代表的酯類等之有機溶劑。再者，用無溶 劑型黏著劑的黏著劑層之厚度，通常爲5〇μιη以下，更佳 爲20μιη以下，更佳爲10pm以下，而且通常爲1μιη以上 -33- 200946989 於如上述地塗佈後 能量線或加熱，而使黏 護層、偏光薄膜或保護 量線的照射使硬化時， 外線光源，可舉出低壓 、黑光燈、金屬鹵化物 紫外線的照射強度或照 化，且對硬化後的黏著 薄膜沒有不利影響。又 般已知的方法來加熱， ’以使聚合引發劑充分 偏光薄膜、保護薄膜沒 再者，對保護層或 側，較佳預先施予電暈 ’可提高偏光薄膜與保 位差板之間的黏著力。 壓而放電，將電極間所 暈放電處理的效果雖然 壓、濕度、所使用的樹 較佳爲將電極間隔設定 〜20m/分鐘左右。 ，無溶劑型黏著劑係經由照射活性 著劑層硬化，以固著偏光薄膜與保 層與第一相位差板。於藉由活性能 較佳爲使用紫外線。作爲具體的紫 水銀燈、中壓水銀燈、高壓水銀燈 燈等。可適宜地選擇活性能量線或 射量，以便使聚合引發劑充分活性 劑層或偏光薄膜、保護層、相位差 ，於藉由加熱使硬化時，可藉由一 亦可適宜地選擇此時的溫度或時間 活性化，且對硬化後的黏著劑層或 有不利影響。 第一相位差板之與偏光薄膜貼合的 放電處理。藉由施予電暈放電處理 護層、偏光薄膜或保護層與第一相 電暈放電處理係在電極間施加高電 配置的樹脂薄膜活性化之處理。電 亦隨著電極的種類、電極間隔、電 脂薄膜之種類等而不同，但是例如 在1〜5mm，將移動速度設定在3 [2-2]第二複合偏光板 200946989 於此，第3圖係以分離各層的狀態示意地顯示本發明 的複合偏光板組所用的較佳一例之第二複合偏光板21的 斜視圖，第4圖係以分離各層的狀態示意地顯示本發明的 複合偏光板組所用的較佳其它例之第二複合偏光板31的 斜視圖。第3圖及第4圖中所示的第二複合偏光板21、31 ，除了偏光板22、32的構成係一部分不同以外，係具有 同樣的構造，在偏光板22、32上層合第二相位差板23與 ® 感壓性黏著劑層24而成。 本發明中所用的第二相位差板23之特徵爲面內的相 位差値R〇係在0〜30nm (較佳爲0〜10nm )的範圍，厚 度方向的相位差値Rth係在3 0〜3 OOnm (較佳爲 5 0〜 3 OOnm )的範圍。於第二相位差板23之面內的相位差値 R〇超過30nm時，發現伴隨正面相位差的偏光解消，對比 會降低。另一方面，於第二相位差板23之厚度方向的相 位差値Rth低於30nm時，無法充分抵銷液晶胞的液晶雙 ® 折射，視野角變窄，而若超過300nm，則反而過度補償液 晶胞的液晶雙折射，視野角變窄。再者，第二相位差板23 之面內的相位差値Rd及厚度方向的相位差値Rth，係指與 上述第一相位差板之面內的相位差値R〇同樣地使用自動 雙折射測定裝置KOBRA-21ADHC王子計測機器（股）製 )所測定之値。如此的相位差特性係可藉由使用有機修飾 黏土複合體與黏結劑樹脂來形成第二相位差板23而實現 〇 此處的有機修飾黏土複合體，係有機化合物與具有層 -35- 200946989 狀構造的黏土礦物之複合化者，可分散於有機溶劑中。本 發明中的第二相位差板23係可藉由使如此的有機修飾黏 土複合體與黏結劑樹脂一起含於有機溶劑中而調製塗佈液 ，將該塗佈液塗佈成層狀後，去除溶劑而形成。 作爲具有層狀構造的黏土礦物，可舉出綠土族、膨潤 性雲母等。其中，較佳爲使用綠土族，因爲透明性亦優異 。作爲屬於綠土族者，可例示鋰蒙脫石、蒙脫石、膨土等 。於此等之中，從雜質少、透明性優異等之點來看，較佳 〇 爲化學合成者。特別地，較佳爲使用粒徑被控制在小而合 成鋰蒙脫石丨i，因爲可抑制可見光線的散射。 作爲與黏土礦物複合化的有機化合物，可舉出能與黏 土礦物的氧原子或羥基反應或相互作用的化合物，或是能 與交換性陽離子交換的離子性化合物等，但只要有機修飾 黏土複合體可在有機溶劑中膨潤或分散即可，並沒有特別 的限制。作爲能與黏土礦物的氧原子或羥基相互作用的化 合物之具體例，可舉出矽烷偶合劑、鈦偶合劑等的表面修 Ο 飾劑，在系中可藉由聚合來進行修飾的ε-己內醯胺，以及 聚乙烯基耻咯烷酮、烷基取代吡咯烷酮等。又，作爲能與 交換性陽離子交換的離子性化合物物之具體例，可舉出含 氮化合物、含磷化合物等’例如1級、2級或3級胺、4 級銨化合物、4級鐃化合物等。其中，從陽離子交換容易 等來看，較佳爲使用4級銨化合物、4級錢化合物，例如 可舉出具有長鏈烷基者、具有烷基醚鏈者等。特別地，具 有碳數6〜30尤其碳數6〜10的長鏈烷基者，或具有η=1 -36- 200946989 〜50、尤其 n=5 〜30 的- (CH2CH(CH3) Ο) nH 基或-( CH2CH2CH20 ) nH 基者。 於有機修飾黏土複合體中，超因於其製造時所用的各 種副原料，混入含氯的化合物當作雜質者係多。如此的氯 化物之量若多，則在形成第二相位差板23時，有由薄膜 滲出的可能性。於該情況下，當經由感壓性黏著劑將該第 二相位差板23貼合於液晶胞玻璃時，黏著力係經時地大 © 幅降低。因此，較佳爲藉由洗淨來預先從有機修飾黏土複 合體去除氯化物，其中所含有的氯量若以2000ppm以下的 狀態含於有機溶劑中，則可抑制黏著力的降低。氯化物的 去除係可藉由水洗有機修飾黏土複合體的方法來進行。 有機修飾黏土複合體亦可組合2種類以上來使用。於 適當的有機修飾黏土複合體之市售品中，可舉出合成鋰蒙 脫石與4級銨化合物的複合體之Lucentite STN(CO-OP 化學（股）製）、：Lucentite SPN ( CO-OP 化學（股）製） ©等。 如此可分散於有機溶劑中的有機修飾黏土複合體，從 對基材等的塗佈容易性、光學特性的表現性或力學特性等 之點來看，係與黏結劑樹脂組合使用。與有機修飾黏土複 合體倂用的黏結劑樹脂，較佳爲使用溶解在甲苯、二甲苯 、丙酮、醋酸乙酯等的有機溶劑者，特佳爲使用玻璃轉移 溫度在室溫以下（約20。(：以下）者。又，於採用在液晶顯 示裝置時，爲了得到所必要的良好耐濕熱性及處理性，希 望具有疏水性者。作爲如此較佳的黏結劑樹脂，可舉出聚 -37- 200946989 乙烯縮丁醛、聚乙烯縮甲醛等的聚乙烯縮醛樹 酸纖維素等的纖維素樹脂，丙烯酸丁酯等的丙 胺甲酸乙酯樹脂、甲基丙烯酸樹脂、環氧樹脂 等。其中，從有機修飾黏土複合體的分散性良 佳爲胺甲酸乙酯樹脂。 作爲黏結劑樹脂的市售品，具體地的可舉 的醛改性樹脂之Denkabutyral # 3000-Κ (電 (股）製）、丙烯酸樹脂的Aron S1601 (東亞 製）、以異佛爾酮二異氰酸酯爲基礎的胺甲酸 SBU漆-0866 (住化拜耳胺甲酸乙酯（股））等 第二相位差板23中的有機修飾黏土複合 樹脂之含有率，從第二相位差板23的防破裂 提高的觀點來看，較佳爲前者：後者的重量比^ ·· 1的範圍，尤其在1: 1〜2: 1的範圍。 有機修飾黏土複合體及黏結劑樹脂，係如 散在有機溶劑中調製成塗佈液的狀態而塗佈在 此情況下，一般地將黏結劑樹脂溶解在有機溶 使有機修飾黏土複合體分散在有機溶劑中。此 體成分濃度，只要調製後的塗佈液在實用上沒 圍而不會膠化或白濁即可，並沒有限制，通常 黏土複合體與黏結劑樹脂的合計固體成分濃度 重量％左右的範圍來使用。最合適的固體成分 係隨著有機修飾黏土複合體與黏結劑樹脂的各 者的組成比而不同，故按各組成設定。又，亦 脂，乙酸丁 烯酸樹脂’ 、聚酯樹脂 好來看，較 出聚乙烯醇 氣化學工業 合成（股） 乙酯樹脂之 〇 體與黏結劑 等力學特性 生1 : 2〜1 〇 上述地以分 基材上。於 劑中，然後 塗佈液的固 有問題的範 以有機修飾 成爲3〜1 5 濃度，由於 自種類或兩 可添加用於 -38- 200946989 提高製膜時的塗佈性之黏度調整劑，或用於更提高疏水性 及/或耐久性的硬化劑等各種添加劑。 又’此塗佈液以卡爾費雪水分計所測定的含水率較佳 爲在0.15〜0_35重量％的範圍內。於該含水率超過0.35重 量％時’在非水溶性有機溶劑中發生相分離，塗佈液有分 離成2層的傾向。另一方面，於含水率低於〇_15重量％時 ’所形成的第二相位差板的霧度値有變高之虞。 使塗佈液的含水率成爲上述範圍內的方法係沒有特別 的限制’可藉由在塗佈液中添加水而簡便地調整含水率。 僅以通常的方法來混合如上述的有機溶劑、有機修飾黏土 複合體及，係幾乎無法顯示0.15重量％以上的含水率。因 此’較佳爲藉由在混有有機溶劑、有機修飾黏土複合體及 黏結劑樹脂的塗佈液中添加少量的水，以將含水率調整到 上述範圍內。水的添加時間點係沒有特別的限制，在調製 塗佈液而經過一定時間後，進行取樣測定含水率後，添加 指定量的水，係可高再現性及精度地控制含水率而較宜。 塗佈液的塗佈方式係沒有特別的限制，可使用直接凹 槽輥法、逆凹槽輥法、口模式塗佈法、凸輪塗佈法、桿塗 法等眾所周知的各種方式。 塗佈上述塗佈液的基材若爲面內的相位差値R〇大致 零的材料，則沒有特別的限定，較佳爲由鏈狀烯烴樹脂所 成的未拉伸薄膜、由環烯烴樹脂所成的未拉伸薄膜、由醯 化纖維素樹脂所成的未拉伸薄膜等。 又，於形成如第3圖所示的第二複合偏光板時，此基 -39- 200946989 材亦可兼任偏光板22的保護層27。於此情況下，可在保 護層27上塗佈上述塗佈液以形成第二相位差板23後，使 附有第二相位差板23的保護層27與偏光薄膜25貼合， 也可在預先貼合有保護層27而成的偏光薄膜25之保護層 27側，塗佈上述塗佈液以形成第二相位差板23。再者， 於此情況下，亦可在第二相位差板23與保護層27之間形 成底漆層。 又，本發明中的第二複合偏光板所用的偏光板，亦可 © 與第一複合偏光板所用的偏光板同樣地爲該領域中所一般 使用者，例如一般使用於聚乙烯醇樹脂上吸附配向有二色 性色素（碘、二色性有機染料等）的直線偏光薄膜之兩面 或一面上，層合有由三乙醯纖維素樹脂、環狀環烯烴樹脂 、鏈狀環烯烴樹脂等的樹脂薄膜所成的保護層之構造。第 3圖中顯示使用直線偏光薄膜25的兩面上設有保護層26 、27的偏光板22之情況，而且第4圖顯示使用直線偏光 薄膜25的一面（層合有第二相位差板23的側之相反側的 © 面）上設有保護層26的偏光板32之情況。 於本發明的第二複合偏光板21、31中，第二相位差 板23之與偏光板22、32的鄰接側之相反側上所形成的感 壓性黏著劑層24，係與第一複合偏光板1、11中的感壓性 黏著劑層4之上述者同樣地，可使用以往液晶顯示裝置用 所用的各種感壓性黏著劑來形成。又，於第二複合偏光板 中，爲了保護層與偏光薄膜、保護層或偏光薄膜與第二相 位差板之間的黏著，可同樣合適地使用第一複合偏光板中 -40- 200946989 的保護層與偏光薄膜、保護層或偏光薄膜與第一相位差板 之間的黏著所適用的上述黏著劑。 第5(a)圖係示意地顯示使用本發明的複合偏光板組 所製造的液晶顯示裝置之一例的樣子之截面圖，第5(b) 圖係以互相錯開各層的狀態顯示之上視圖。再者，於第5 圖中，以分離各層的狀態示意地顯示以第1圖所示例之第 一複合偏光板1與第3圖所示例之第二複合偏光板21組 β 合成的複合偏光板組，第一複合偏光板1係黏貼在液晶胞 50的一側，第二複合偏光板2 1係黏貼在液晶胞50的另一 側（省略感壓性黏著劑層的圖示）。 本發明的複合偏光板組係適用於垂直配向（VA )模 式的液晶顯示裝置。使用於垂直配向模式的液晶顯示裝置 時，如第5 ( b )圖所示地，第一複合偏光板1，係以在液 晶胞的視覺辨識側（正面側），偏光板2的吸收軸方向2a 與液晶胞的水平方向（長度方向）呈平行地配置，而且偏 ^ 光板2的吸收軸方向2a與第一相位差板3的遲相軸方向 3a呈大致垂直而交叉配置，而被黏貼。又，第二複合偏光 板2 1，係以在液晶胞的視覺辨識之相反側（背面側），偏 光板22的吸收軸方向22a與液晶胞的垂直方向（短邊方 向）呈平行地配置，而且偏光板22的吸收軸方向22 a與 第一複合偏光板1中的偏光板2之吸收軸方向2a大致垂 直而交叉配置，被黏貼。於此情況下’液晶胞若爲VA模 式的液晶胞，.則其種類係沒有特別的限制。 -41 - 200946989 [2] 液晶顯示裝置 於本發明中，提供具備如上述本發明的複合偏光板組 與液晶胞的液晶顯示裝置，亦提俣在液晶胞的一側配置第 一複合偏光板，同時在液晶胞的另一側配置第二複合偏光 板而成的液晶顯示裝置。關於此液晶顯示裝置，第一複合 偏光板係介於感壓性黏著劑層而貼合在液晶胞，第二複合 偏光板亦介於感壓性黏著劑層而貼合在液晶胞。如上述地 ，本發明的複合偏光板組，即使於觀看角度改變時，也不 易發生色調的變化，可得到良好的視野角特性。因此，本 發明的液晶顯示裝置係特別適合實現VA模式的液晶顯示 裝置。 [3] 複合偏光板輥 又，本發明亦提供複合偏光板輥，其係具有在吸收軸 方向與長度方向呈平行配置的偏光板之長條輥上，層合第 一相位差板的長條輥之構造，第一相位差板的遲相軸方向 與偏光板的吸收軸方向以80〜100°的角度交叉方式配置 的複合偏光板輥，第一相位差板係將丙烯系樹脂拉伸所成 ，面內的相位差値R〇係在90〜200nm的範圍，而且以薄 膜的面內遲相軸方向之折射率當作nx，以薄膜的面內進相 軸方向之折射率當作ny，以薄膜的厚度方向之折射率當作 nz時，Nz係數爲在0.90〜1.10的範圍，如此的本發明之 複合偏光板輥係可適用於製造上述本發明的複合偏光板組 中的第一複合偏光板。 -42- 200946989 本發明的複合偏光板輕中之第一相位差板的長條輕， 由於如本發明中的第一複合偏光板之第一相位差板的上述 者，使用丙烯樹脂，故即使施以固定端橫一軸拉伸時，也 可以某一程度以上的高倍率進行拉伸，得到完全一軸性的 特性。因此，本發明的複合偏光板輥中的第一相位差板， 較佳係由對丙烯樹脂進行固定端橫一軸拉伸而得之薄膜， 因此本發明的複合偏光板輥中的第一相位差板之遲相軸方 ® 向係與薄膜的長度方向不同90度的方向（=寬度方向）呈 大致平行，故可容易地以輥對輥與偏光板的長條輥貼合而 容易製造。藉由將如此所製造的本發明之複合偏光板輥裁 切成適宜的大小，可容易製造上述本發明的複合偏光板組 所用的第一複合偏光板。 以下舉出實施例來更詳細說明本發明，惟本發明不受 此等實施例所限定。例子中，只要沒特別記述，則表示使 用量或含量的「份」及「％」係以重量爲基準。又’面內 ® 的相位差値R〇、厚度方向的相位差値Rth及Nz係數皆係 使用自動雙折射測定裝置KOBRA-21ADH (王子計測機器 (股）製）所測定之値。 <實施例1 > (第一複合偏光板的樣品1之製作） 製造聚丙烯樹脂薄膜（住友N〇Prene W151，住友化 學（股）製）而得到4 0 μιη厚的薄膜後’進行固定端橫一 軸拉伸，得到完全一軸性的相位差薄膜’亦即第一相位差 -43- 200946989 板。於此第一相位差板的一側面，經由黏著劑貼合具有三 乙醯纖維素當作保護層的偏光板，而使偏光薄膜露出側鄰 接於第一相位差板，偏光板的吸收軸方向與第一相位差板 的遲相軸方向呈交叉方式配置的狀態。再者，在第一相位 差板之與偏光板鄰接側的相反側之面上，轉印分離膜上所 形成的感壓性黏著劑層（P-3 1 32, Lintec (股）製），以製 作第一複合偏光板的樣品1。第一相位差板之面內的相位 差値R。爲140nm，Nz係數爲1.00。 ❹ (第二複合偏光板的樣品1之製作） 作爲有機修飾黏土複合體，使用合成鋰蒙脫石與三辛 基甲基銨離子的複合體之 Lucentite STN(CO-OP化學（ 股）製），而且作爲黏結劑樹脂，使用以異佛爾酮二異氰 酸酯爲基礎之聚胺甲酸乙酯樹脂的固體成分濃度30%之樹 脂清漆，亦即SBU漆0866 (住化拜耳胺甲酸乙酯（股） 製），由以下組成來調製第二相位差模製作用之塗佈液。 Ο .胺甲酸乙酯樹脂清漆（SBU漆0866) 16.0份 •有機修飾黏土複合體（Lucentite STN) 7.2份 •甲苯 76.8份 •水 〇.3份 此處所用的有機修飾黏土複合體係由製造商以在有機 修飾前的合成鋰蒙脫石製造後，進行酸洗淨，將其有機修 飾，再成爲水洗的狀態取得。其所含有的氯量爲HHPPm 。又，此塗佈液係以上述組成混合，攪拌後’經由孔徑 -44 - 200946989 1 μιη的過濾器過濾而調製者，以卡爾費雪水分計所測定的 含水率爲0.25%。此塗佈液中的有機修飾黏土複合體/黏結 劑樹脂之固體成分重量比爲6/4。 以乾燥後的厚度成爲6.3 μηι的方式，藉由桌上型間隙 塗佈機，將如上述所調製的塗佈液直接塗佈在三乙醯纖維 素薄膜（KC8UX2MW，Konica-Minolta (股）製）上，在 8 〇°C乾燥2分鐘而形成塗佈的相位差層，得到第二相位差 β 板。所得到的第二相位差板之面內的相位差値R〇爲〇.2nm ，厚度方向的相位差値Rth爲170nm。 經由黏著劑將第二相位差板的三乙醯纖維素面側貼合 於在一側面具有三乙醯纖維素當作保護層的偏光板之偏光 薄膜的露出側，再於第二相位差板上，轉印分離膜上所形 成的感壓性黏著劑層（P-3132, Lintec (股）製），而得到 第二複合偏光板的樣品1。 ❹ （液晶顯示裝置） 拆解市售的液晶電視（BRAVIA KDL40V2500，Sony ( 股）製），將液晶胞上所黏貼的薄膜完全剝離後，在視覺 辨識側（正面側），以偏光板的吸收軸方向與液晶電視的 水平方向（長度方向）呈平行的方式，經由感壓性黏著劑 層黏貼第一複合偏光板的樣品1。再者，在液晶胞之與視 覺辨識側的相反側（背面側），以吸收軸方向與液晶電視 的垂直方向（短邊方向）呈平行的方式，經由感壓性黏著 劑層，黏貼第二複合偏光板的樣品1當作偏光板，而得到 -45- 200946989 液晶顯示裝置。 <比較例1〜4 > 除了對環烯烴系樹脂的原冰片烯樹脂薄膜（ZEONOR， (股）Optes製）進行固定端橫一軸拉伸，製作分別具有 如表1所示之面內的相位差値R。及Nz係數之第一相位差 板，分別使用此等以外，與實施例1同樣地，製作第一複 合偏光板的樣品2〜5。又，除了製作分別具有如表2所示 〇 之面內的相位差値R〇及厚度方向的相位差値Rth之第二 相位差板，分別使用此等以外，與實施例1同樣地，製作 第二複合偏光板的樣品2〜5。除了如表3所示地組合此等 第一複合偏光板的樣品與第二複合偏光板的樣品以外’與 實施例1同樣地，製作比較例1〜4的液晶顯示裝置。 -46- 200946989 —^_ 相 位 差 薄 膜 R〇(nm) Nz係數 第- -複 偏 光 板 樣 品 1 兀 全 — 軸 性 140 1.00 第- -複 △ 偏 光 板 樣 品 2 --- 軸 性 100 1.32 第- -複 合 偏 光 板 樣 品 3 一 軸 性 133 1.44 第- -複 a α 偏 光 板 樣 品 4 一 軸 性 95 1.47 第- -複 合 偏 光 板 樣 品 5 —' 軸 性 148 1.78 -----_ 相位差薄膜 R〇(nm ) Rth ( nm ) 第二複合偏光板樣品1 完全二軸性 0.2 170 第二複合偏光板樣品2 完全二軸性 0.1 125 第二複合偏光板樣品3 完全二軸性 0.1 130 第二複合偏光板樣品4 完全二軸性 0.1 130 第二複合偏光板樣品5 完全二軸性 0.1 130 X 第一複合偏光板 第二複合偏光板 CR視野角 (°) 實施例1 樣品1 樣品1 1 10 比較例1 樣品2 樣品2 105 比較例2 樣品3 樣品3 99 比鮫例3 樣品4 樣品4 98 比較例4 樣品5 樣品5 8 1(CH^T^O The compound in which the hydrogen atom in (CH2) m in the above formula is bonded to another chemical structure by removing one or more of the forms is capable of forming an alicyclic epoxy compound. The hydrogen forming the alicyclic ring may be suitably substituted by a linear alkyl group such as a methyl group or an ethyl group. Among them, it is preferred to use an epoxy group having a cyclopentane ring (m = 3 in the above formula) Or a compound of an epoxycyclohexane ring (m = 4 in the above formula: -29-200946989). Specific examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl group. 3,4_epoxycyclohexanyl phthalate, 3,4-epoxy-6-methylcyclohexylmethyl, 3,4·epoxymethylcyclohexanecarboxylate, ethyl Bis(3,4-epoxycyclohexanecarboxylic acid vinegar), bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methyl Cyclohexylmethyl) adipate, diethylene glycol bis(3,4-epoxycyclohexylmethyl ether), ethylene glycol bis(3,4-epoxycyclohexylmethyl acid), 2 ,3,14,15-diepoxy-7,11,18,21-tetraoxaspiro--[5_2.2.5.2.2]nonane (3,4-epoxy) Cyclohexane spiro-2,6'-dioxane spiro-3,,5''-dioxane spiro-3''',4'''-epoxycyclohexane), 4-(3 , 4-epoxycyclohexyl)-2,6-dioxa-8,9-epoxyspiro[5.5]~(--院, 4-vinylcyclohexene dioxide, bis-2, 3-epoxycyclopentyl ether, dicyclopentadiene dioxide, etc. Further, as the aliphatic epoxy compound, the polyglycidyl ether of the aliphatic polyol or the alkylene oxide adduct thereof corresponds to this. Examples of such an aliphatic epoxy compound include diglycidyl ether of i,4·butylene glycol, diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerin, and trishydroxyl. Triglycidyl ether of methyl propane, diglycidyl ether of polyethylene glycol, diglycidyl ether of propylene glycol, one or more epoxy resins added to ethylene glycol or propylene glycol, glycerol-like aliphatic polyol A polyglycidyl ether of a polyether polyol obtained by using an alkoxide (epoxyacetam or propylene oxide), etc. The epoxy compounds exemplified herein may be used singly or in combination with a plurality of epoxy compounds. no The epoxy equivalent of the epoxy compound used in the solvent-based adhesive is usually from 30 to 3000 g/equivalent, preferably from 50 to 1500 g/equivalent, and the epoxy equivalent is less than 30 g/equivalent. The flexibility of the latter protective film is lowered or the adhesive strength is lowered. On the other hand, if it exceeds 3 000 g/eq, there is a possibility that the compatibility with other components is lowered. The compound is hardened and blended with a cationic polymerization initiator. The cationic polymerization initiator is irradiated or heated by active energy rays such as visible light, ultraviolet rays, X-rays, electron beams, etc. to generate a cation species or a Lewis acid, and an initiation ring. Polymerization of an oxy group. From the standpoint of operability, it is preferred that all types of cationic polymerization initiators impart potential. Further, when a photocationic polymerization initiator is used, it can be cured at room temperature, and it is required to reduce the deformation resistance due to heat resistance or expansion of the polarizing film, and the advantage of the protective film can be favorably adhered. Further, since the photocationic polymerization initiator is catalyzed by light, it is excellent in storage stability and workability even when it is mixed in an epoxy compound. Examples of the compound which generates a cationic species or a Lewis acid by irradiation with an active energy ray include, for example, an aromatic diazo salt, an aromatic ioyl salt or an aromatic sulfonium salt, and an iron-propadiene. Complex and so on. Among these, it is particularly preferable to use an aromatic sulfonium salt because it has ultraviolet absorbing properties in a wavelength region of 30 Å or more, so that it has excellent curability and can give a cured product having good mechanical strength or adhesive strength. Such a photocationic polymerization initiator can be easily obtained from a commercially available product, and specifically, Kayarad PCI-220 (manufactured by Nippon Kayaku Co., Ltd.), Kayarad PCI-620 (manufactured by Nippon Kayaku Co., Ltd.), UVI- 6990 (manufactured by Union Carbide Co., Ltd.) 'Adekaoptomer SP-150 ((share) -31 - 200946989 ADEKA), Adekaoptomer SP-170 (made by Adeka), CI-5102 (曰本曹达(股)), CIT-1370 (Japan Soda (share) system), CIT-1682 (Japan Soda (share) system), CIP-18 66 8 (Japan Soda (share) system), (:1?-204 88 (Japan Soda ( Stocks), CIP-2064S (Japan Soda (share) system), DPI-101 (Green Chemical (share) system), DPI-102 (Green Chemical (share) system), DPI-103 (Green Chemistry (shares) System, DPI-105 (Green Chemical Co., Ltd.), MPI-103 (Green Chemical Co., Ltd.), MPI-105 (Green Chemical Co., Ltd.), BBI-101 (Green Chemical Co., Ltd.) , BBI-102 (Green Chemical Co., Ltd.), BBI-103 (Green Chemical Co., Ltd.), BBI-105 (Green Chemical Co., Ltd.), TPS-101 (Green Chemical Co., Ltd.), TPS -102 (Green Chemicals Co., Ltd.), TPS-103 (Green Chemical Co., Ltd.), TPS-105 (Green Chemical Co., Ltd.), MDS-103 (Green Chemical Co., Ltd.), MDS-105 (Green Chemical Co., Ltd.), DTS -102C Green Chemical Co., Ltd., DTS-103 (Green Chemical Co., Ltd.), PI-2074 (manufactured by Rhodia Co., Ltd.), etc. Among them, CI-51 02 (manufactured by Nippon Soda Co., Ltd.) is one of preferred photocationic polymerization initiators. The blending amount of the photocationic polymerization initiator is usually 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, per 100 parts by weight of the epoxy compound. Further, a light sensitizer can be used as needed. By using a photosensitizer, the reactivity can be improved and the mechanical strength or adhesion strength of the cured product can be improved. Examples of the photosensitizer include a carbonyl compound, an organic sulfur compound, a persulfide compound, a redox compound, an azo and a diazo compound, a halogen compound, and a photoreductive dye. When the photo sensitizer is blended, the blending amount is usually 0.1 to 20 parts by weight for 100 parts by weight to 32 to 200946989 parts of the epoxy compound. Further, the thermal cationic polymerization initiator is a compound which generates a cationic species or a Lewis acid by heating, and is a thermal cationic polymerization initiator such as a benzyl sulfonium salt, a thiophene key salt, a tetrahydrothiophene key salt, a benzyl ammonium salt, or a pyridine. Gun salt, hydrazine salt, carboxylate, sulfonate, amidoxime and the like. The thermal cationic polymerization initiator can be easily obtained from a commercially available product, and examples thereof include Adekaopton CP77 (manufactured by Adeka), Adekaopton CP 66 (manufactured by ADEKA), and CI-2639 (made by Japan Soda Co., Ltd.). ), (: 1-2624 (Japan Soda Co., Ltd.), Saneido SI-60LC Sanshin Chemical Industry Co., Ltd.), Saneido SI-8 0L (Sanshin Chemical Industry Co., Ltd.), Saneido SI-100L (Sanxin Chemical Industry Co., Ltd.) and so on. Further, in the present invention, the above photocationic polymerization and thermal cationic polymerization may also be employed. Further, the epoxy-based adhesive may further contain a compound which promotes cationic polymerization such as oxetane or polyol. When a solventless adhesive is used, the method of coating on at least one of the polarizing film, the protective layer, and the first retardation film is not particularly limited. For example, a doctor blade, a wire rod, or a mouth pattern can be used. Various methods such as cloth machine, cam coater and gravure coating machine. In each of the above modes, since each has the most suitable viscosity range, a small amount of solvent can be used to adjust the viscosity. As the solvent to be used, for example, an organic solvent such as a hydrocarbon represented by toluene or an ester represented by ethyl acetate can be used. Further, the thickness of the adhesive layer using the solventless adhesive is usually 5 μm or less, more preferably 20 μm or less, still more preferably 10 μm or less, and usually 1 μm or more -33 to 200946989. After the energy line or heating, and the curing of the adhesive layer, the polarizing film or the protective amount line is hardened, the external light source may be irradiated with low-voltage, black light, metal halide ultraviolet light or illuminate, and after hardening The adhesive film has no adverse effects. Further known methods are used for heating, 'so that the polymerization initiator is sufficiently polarized, the protective film is no longer, and the protective layer or the side is preferably pre-applied with a corona" to improve the relationship between the polarizing film and the retention plate. Adhesion. The effect of the discharge and discharge between the electrodes is that the pressure, the humidity, and the tree used are preferably set to about 20 m/min. The solvent-free adhesive is cured by irradiating the active agent layer to fix the polarizing film and the protective layer and the first phase difference plate. It is preferred to use ultraviolet rays by the active energy. As a specific purple mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, and the like. The active energy ray or the amount of radiation can be appropriately selected so that the polymerization initiator can sufficiently suffice the active agent layer or the polarizing film, the protective layer, and the phase difference. When hardening by heating, one can also be appropriately selected at this time. The temperature or time is activated and has an adverse effect on the hardened adhesive layer. The discharge treatment of the first phase difference plate to which the polarizing film is bonded. The resin film is activated by applying a corona discharge treatment layer, a polarizing film or a protective layer and a first phase corona discharge treatment system to apply a high-powered resin film between the electrodes. The electric power varies depending on the type of the electrode, the electrode interval, the type of the electric grease film, etc., but for example, at 1 to 5 mm, the moving speed is set to 3 [2-2] second composite polarizing plate 200946989, here, Fig. 3 A perspective view schematically showing a second composite polarizing plate 21 of a preferred example of the composite polarizing plate assembly of the present invention in a state in which the respective layers are separated, and a fourth embodiment schematically showing the composite polarizing plate of the present invention in a state in which the respective layers are separated. A perspective view of a second composite polarizing plate 31 of a preferred other example used in the group. The second composite polarizing plates 21 and 31 shown in Figs. 3 and 4 have the same configuration except that the configuration of the polarizing plates 22 and 32 is partially different, and the second phase is laminated on the polarizing plates 22 and 32. The difference plate 23 and the pressure-sensitive adhesive layer 24 are formed. The second phase difference plate 23 used in the present invention is characterized in that the in-plane phase difference 値R〇 is in the range of 0 to 30 nm (preferably 0 to 10 nm), and the phase difference 値Rth in the thickness direction is 30 to 30. A range of 3 OOnm (preferably 5 0 to 3 OOnm). When the phase difference 値 R 于 in the plane of the second phase difference plate 23 exceeds 30 nm, it is found that the polarization cancellation with the front phase difference is lowered. On the other hand, when the phase difference 値Rth in the thickness direction of the second phase difference plate 23 is less than 30 nm, the liquid crystal double refracting of the liquid crystal cell cannot be sufficiently offset, and the viewing angle is narrowed, and if it exceeds 300 nm, the compensation is excessively compensated. The liquid crystal birefringence of the liquid crystal cell narrows the viewing angle. In addition, the phase difference 値Rd in the plane of the second phase difference plate 23 and the phase difference 値Rth in the thickness direction mean that the automatic birefringence is used similarly to the phase difference 値R〇 in the plane of the first phase difference plate. The measurement device KOBRA-21ADHC prince measuring machine (manufactured by the company) was measured. Such a phase difference characteristic can be achieved by forming an organic second modified phase difference plate 23 by using an organically modified clay composite and a binder resin to realize an organic modified clay composite, which is an organic compound having a layer of -35-200946989. The composite of the constructed clay minerals can be dispersed in an organic solvent. In the second phase difference plate 23 of the present invention, the coating liquid can be prepared by disposing such an organically modified clay composite together with a binder resin in an organic solvent, and the coating liquid is applied in a layered form. Formed by removing the solvent. Examples of the clay mineral having a layered structure include a green earth group and a swelling mica. Among them, it is preferable to use a smectite group because transparency is also excellent. As a smectite, hectorite, montmorillonite, and bentonite can be exemplified. Among these, it is preferable that it is a chemical synthesizer from the viewpoint of having less impurities and excellent transparency. In particular, it is preferred to use a particle size controlled to be small to synthesize hectorite, because scattering of visible light rays can be suppressed. Examples of the organic compound compounded with the clay mineral include a compound that reacts or interacts with an oxygen atom or a hydroxyl group of a clay mineral, or an ionic compound that can exchange with an exchangeable cation, but only an organically modified clay composite. It may be swelled or dispersed in an organic solvent, and is not particularly limited. Specific examples of the compound which can interact with the oxygen atom or the hydroxyl group of the clay mineral include a surface-repairing agent such as a decane coupling agent or a titanium coupling agent, and ε-hexyl which can be modified by polymerization in the system. Indoleamine, as well as polyvinylpyrrolidone, alkyl substituted pyrrolidone, and the like. Further, specific examples of the ionic compound which can be exchanged with the exchangeable cation include a nitrogen-containing compound, a phosphorus-containing compound, and the like, for example, a primary, secondary or tertiary amine, a tertiary ammonium compound, and a tertiary sulfonium compound. Wait. In particular, a quaternary ammonium compound or a quaternary compound is preferably used, and examples thereof include those having a long-chain alkyl group and those having an alkyl ether chain. In particular, a long-chain alkyl group having a carbon number of 6 to 30, particularly a carbon number of 6 to 10, or -(CH2CH(CH3) Ο) nH having η = 1 - 36 to 200946989 to 50, especially n = 5 to 30 Base or -(CH2CH2CH20) nH base. In the organically modified clay composite, many of the auxiliary materials used in the production of the composite are mixed with chlorine-containing compounds as impurities. When the amount of such a chloride is large, there is a possibility that the second phase difference plate 23 is oozing out of the film. In this case, when the second retardation film 23 is bonded to the liquid crystal cell glass via the pressure-sensitive adhesive, the adhesion is greatly reduced over time. Therefore, it is preferable to remove the chloride from the organically modified clay composite in advance by washing, and if the amount of chlorine contained in the organic solvent is 2,000 ppm or less, the decrease in the adhesive strength can be suppressed. The removal of the chloride can be carried out by washing the organically modified clay composite. The organically modified clay composite may be used in combination of two or more types. Among the commercially available products of a suitable organically modified clay composite, Lucentite STN (manufactured by CO-OP Chemical Co., Ltd.), which is a composite of a synthetic hectorite and a 4-grade ammonium compound, and a Lucentite SPN (CO-) are mentioned. OP Chemical (share) system) ©etc. The organically modified clay composite which can be dispersed in an organic solvent is used in combination with a binder resin from the viewpoints of ease of application to a substrate or the like, expression of optical properties, and mechanical properties. The binder resin used for the organically modified clay composite is preferably an organic solvent dissolved in toluene, xylene, acetone, ethyl acetate or the like, and particularly preferably has a glass transition temperature of not more than room temperature (about 20. In the case of using a liquid crystal display device, in order to obtain good moist heat resistance and handleability, it is desirable to have hydrophobicity. As such a preferable binder resin, poly-37 is exemplified. - 200946989 A cellulose resin such as polyvinyl acetal cellulose such as vinyl butyral or polyvinyl formal, an urethane resin such as butyl acrylate, a methacrylic resin or an epoxy resin. The dispersibility of the organically modified clay composite is preferably an urethane resin. As a commercial product of a binder resin, specifically, an aldehyde-modified resin of Denkabutyral #3000-Κ (manufactured by Electric Co., Ltd.), Acrylic resin Aron S1601 (made in East Asia), isophorone diisocyanate-based urethane formic acid SBU lacquer -0866 (sodium sulphate) The content ratio of the machine-modified clay composite resin is preferably from the viewpoint of the improvement of the rupture prevention of the second phase difference plate 23, the former: the weight ratio of the latter is in the range of +1, especially 1:1 to 2:1 The organic modified clay composite and the binder resin are coated in a state in which a coating liquid is prepared in an organic solvent, and in this case, the binder resin is generally dissolved in an organic solvent to dissolve the organically modified clay composite. It is dispersed in an organic solvent. The concentration of the body component is not limited as long as it is practically not gelled or turbid, and is not limited. Usually, the total solid concentration of the clay composite and the binder resin is It is used in the range of about % by weight. The most suitable solid content differs depending on the composition ratio of each of the organically modified clay composite and the binder resin, so it is set for each composition. Also, it is also a fat, acetic acid butenoic acid resin. ', polyester resin is good, compared with the mechanical properties of the polyvinyl alcohol gas chemical industrial synthesis (stock) ethyl ester resin, such as carcass and binder 1 : 2 ~ 1 〇 the above ground to sub-substrate In the agent, then the inherent problem of the coating liquid is organically modified to a concentration of 3 to 15 5, due to the addition of the viscosity modifier for the coating property at the time of film formation from -38 to 200946989 Or various additives such as a hardener for further improving hydrophobicity and/or durability. Further, the water content of the coating liquid measured by Karl Fischer moisture meter is preferably in the range of 0.15 to 0-35 wt%. When the water content exceeds 0.35% by weight, the phase separation occurs in the water-insoluble organic solvent, and the coating liquid tends to separate into two layers. On the other hand, when the water content is less than 〇15% by weight, it is formed. The haze of the second retardation film is increased. The method of setting the water content of the coating liquid to the above range is not particularly limited. The water content can be easily adjusted by adding water to the coating liquid. rate. The organic solvent and the organically modified clay composite as described above are merely mixed by a usual method, and the water content of 0.15% by weight or more is hardly exhibited. Therefore, it is preferable to adjust the water content to the above range by adding a small amount of water to the coating liquid in which the organic solvent, the organically modified clay composite, and the binder resin are mixed. The addition time of the water is not particularly limited. After a predetermined period of time has elapsed after the preparation of the coating liquid, sampling and measuring the water content, and adding a specified amount of water, it is preferable to control the water content with high reproducibility and precision. The coating method of the coating liquid is not particularly limited, and various known methods such as a direct groove roll method, a reverse groove roll method, a die coating method, a cam coating method, and a rod coating method can be used. The substrate to which the coating liquid is applied is not particularly limited as long as the phase difference 値R〇 is substantially zero, and is preferably an unstretched film made of a chain olefin resin or a cycloolefin resin. A formed unstretched film, an unstretched film made of a deuterated cellulose resin, or the like. Further, when the second composite polarizing plate shown in Fig. 3 is formed, the base-39-200946989 material can also serve as the protective layer 27 of the polarizing plate 22. In this case, after the coating liquid is applied onto the protective layer 27 to form the second retardation film 23, the protective layer 27 with the second retardation film 23 and the polarizing film 25 may be bonded to each other. The protective layer 27 on the polarizing film 25 in which the protective layer 27 is bonded in advance is applied to the protective layer 27 side, and the coating liquid is applied to form the second retardation film 23. Further, in this case, a primer layer may be formed between the second phase difference plate 23 and the protective layer 27. Further, the polarizing plate used in the second composite polarizing plate of the present invention may be used by a general user in the field, similarly to the polarizing plate used for the first composite polarizing plate, for example, generally used for adsorption on polyvinyl alcohol resin. a double-sided or one surface of a linear polarizing film having a dichroic dye (iodine, a dichroic organic dye, etc.), and a layer of a triacetyl cellulose resin, a cyclic cycloolefin resin, a chain cycloolefin resin, or the like The structure of the protective layer formed by the resin film. Fig. 3 shows a case where the polarizing plates 22 provided with the protective layers 26 and 27 on both sides of the linear polarizing film 25 are used, and Fig. 4 shows one side of the linear polarizing film 25 (the second phase difference plate 23 is laminated). The polarizing plate 32 of the protective layer 26 is provided on the side opposite to the side. In the second composite polarizing plates 21 and 31 of the present invention, the pressure-sensitive adhesive layer 24 formed on the side opposite to the adjacent side of the polarizing plates 22 and 32 of the second phase difference plate 23 is combined with the first composite. The above-described pressure-sensitive adhesive layer 4 in the polarizing plates 1 and 11 can be formed by using various pressure-sensitive adhesives used in conventional liquid crystal display devices. Further, in the second composite polarizing plate, for the adhesion between the protective layer and the polarizing film, the protective layer or the polarizing film and the second phase difference plate, the protection of the first composite polarizing plate -40-200946989 can be suitably used. The above-mentioned adhesive suitable for adhesion between the layer and the polarizing film, the protective layer or the polarizing film and the first phase difference plate. Fig. 5(a) is a cross-sectional view showing an example of a liquid crystal display device manufactured by using the composite polarizing plate assembly of the present invention, and Fig. 5(b) is a top view showing a state in which the layers are shifted from each other. Further, in the fifth drawing, the composite polarizing plate of the first composite polarizing plate 1 shown in Fig. 1 and the second composite polarizing plate 21 shown in Fig. 3 is schematically shown in the state in which the respective layers are separated. In the group, the first composite polarizing plate 1 is adhered to one side of the liquid crystal cell 50, and the second composite polarizing plate 21 is adhered to the other side of the liquid crystal cell 50 (the illustration of the pressure-sensitive adhesive layer is omitted). The composite polarizing plate set of the present invention is suitable for a liquid crystal display device of a vertical alignment (VA) mode. When used in a liquid crystal display device of a vertical alignment mode, as shown in Fig. 5(b), the first composite polarizing plate 1 is on the visual recognition side (front side) of the liquid crystal cell, and the absorption axis direction of the polarizing plate 2 2a is arranged in parallel with the horizontal direction (longitudinal direction) of the liquid crystal cell, and the absorption axis direction 2a of the polarizing plate 2 is arranged to be substantially perpendicular to the slow axis direction 3a of the first phase difference plate 3, and is adhered to each other. Further, the second composite polarizing plate 21 is disposed on the side opposite to the visual recognition of the liquid crystal cell (back side), and the absorption axis direction 22a of the polarizing plate 22 is arranged in parallel with the vertical direction (short side direction) of the liquid crystal cell. Further, the absorption axis direction 22a of the polarizing plate 22 is disposed so as to be substantially perpendicular to the absorption axis direction 2a of the polarizing plate 2 in the first composite polarizing plate 1, and is adhered. In this case, the liquid crystal cell is a liquid crystal cell of the VA mode, and the kind thereof is not particularly limited. -41 - 200946989 [2] Liquid crystal display device In the present invention, a liquid crystal display device including the composite polarizing plate group and the liquid crystal cell of the present invention described above is provided, and a first composite polarizing plate is disposed on one side of the liquid crystal cell. At the same time, a liquid crystal display device in which a second composite polarizing plate is disposed on the other side of the liquid crystal cell is provided. In the liquid crystal display device, the first composite polarizing plate is bonded to the liquid crystal cell by the pressure-sensitive adhesive layer, and the second composite polarizing plate is also bonded to the liquid crystal cell by the pressure-sensitive adhesive layer. As described above, in the composite polarizing plate assembly of the present invention, even when the viewing angle is changed, the change in color tone is less likely to occur, and good viewing angle characteristics can be obtained. Therefore, the liquid crystal display device of the present invention is particularly suitable for realizing a VA mode liquid crystal display device. [3] Composite polarizing plate roll Further, the present invention also provides a composite polarizing plate roll having a long strip of a polarizing plate disposed in parallel with the longitudinal direction of the absorption axis, and a strip of the first phase difference plate laminated The structure of the roller, the composite polarizing plate roller in which the slow axis direction of the first retardation plate and the absorption axis direction of the polarizing plate are arranged at an angle of 80 to 100°, and the first phase difference plate is a propylene resin stretching device. The in-plane phase difference 値R〇 is in the range of 90 to 200 nm, and the refractive index in the in-plane slow axis direction of the film is regarded as nx, and the refractive index in the in-plane axis direction of the film is regarded as ny. When the refractive index in the thickness direction of the film is taken as nz, the Nz coefficient is in the range of 0.90 to 1.10, and the composite polarizing plate roll of the present invention can be suitably used in the manufacture of the above-mentioned composite polarizing plate group of the present invention. Composite polarizer. -42- 200946989 The length of the first phase difference plate of the composite polarizing plate of the present invention is light, and since the above-mentioned one of the first phase difference plates of the first composite polarizing plate of the present invention uses acrylic resin, even When the fixed end is stretched in one axial direction, it may be stretched at a high magnification of a certain degree or more to obtain a completely one-axis property. Therefore, the first phase difference plate in the composite polarizing plate roll of the present invention is preferably a film obtained by stretching the fixed end of the acrylic resin by a single axis, and thus the first phase difference in the composite polarizing plate roll of the present invention. The retardation axis of the plate is substantially parallel to the direction in which the longitudinal direction of the film is 90 degrees (=width direction), so that the roll-to-roll and the long roll of the polarizing plate can be easily bonded to each other and easily manufactured. The first composite polarizing plate used in the above composite polarizing plate group of the present invention can be easily produced by cutting the composite polarizing plate roll of the present invention thus produced into a suitable size. The invention is illustrated in more detail below by the examples, but the invention is not limited by the examples. In the examples, unless otherwise stated, the "parts" and "%" of the amount or content are based on the weight. Further, the phase difference 値R〇 of the in-plane ® and the phase difference 値Rth and the Nz coefficient in the thickness direction are measured by an automatic birefringence measuring device KOBRA-21ADH (manufactured by Oji Scientific Instruments Co., Ltd.). <Example 1 > (Production of Sample 1 of First Composite Polarizing Plate) A polypropylene resin film (Sumitomo N〇Prene W151, manufactured by Sumitomo Chemical Co., Ltd.) was obtained to obtain a film having a thickness of 40 μm, and then fixed. The end is stretched one axially to obtain a completely one-axis retardation film, that is, the first phase difference -43-200946989. On one side of the first phase difference plate, a polarizing plate having triacetyl cellulose as a protective layer is bonded via an adhesive, and the exposed side of the polarizing film is adjacent to the first phase difference plate, and the absorption axis direction of the polarizing plate A state in which the direction of the slow axis of the first phase difference plate is arranged in an intersecting manner. Further, a pressure-sensitive adhesive layer (P-3 1 32, manufactured by Lintec Co., Ltd.) formed on the separation film is transferred onto the surface of the first retardation film opposite to the side adjacent to the polarizing plate. To prepare Sample 1 of the first composite polarizing plate. The phase difference 値R in the plane of the first phase difference plate. It is 140 nm and the Nz coefficient is 1.00. ❹ (Production of Sample 1 of Second Composite Polarizing Plate) As an organically modified clay composite, Lucentite STN (CO-OP Chemical Co., Ltd.) which is a composite of synthetic hectorite and trioctylmethylammonium ion is used. And as a binder resin, a resin varnish having a solid concentration of 30% of a polyurethane resin based on isophorone diisocyanate, that is, SBU lacquer 0866 (sodium sulphate) The coating liquid for producing a second phase difference mode is prepared by the following composition. Ο . Ethyl urethane resin varnish (SBU lacquer 0866) 16.0 parts • Organic modified clay complex (Lucentite STN) 7.2 parts • Toluene 76.8 parts • Leech. 3 parts of the organic modified clay composite system used here by the manufacturer After the synthetic hectorite before the organic modification, it was acid-washed, organically modified, and washed in a state of being washed. The amount of chlorine contained therein is HHPPm. Further, the coating liquid was mixed with the above composition, and after being stirred and filtered through a filter having a pore diameter of -44 - 200946989 1 μηη, the water content measured by Karl Fischer moisture meter was 0.25%. The organic modified clay composite/adhesive resin in the coating liquid had a solid content weight ratio of 6/4. The coating liquid prepared as described above was directly coated on a triacetyl cellulose film (KC8UX2MW, manufactured by Konica-Minolta Co., Ltd.) by a table gap coater so that the thickness after drying became 6.3 μm. The coating was dried at 8 ° C for 2 minutes to form a coated retardation layer, and a second phase difference β plate was obtained. The phase difference 値R 面 in the plane of the obtained second phase difference plate was 〇.2 nm, and the phase difference 値Rth in the thickness direction was 170 nm. The surface of the triacetyl cellulose of the second phase difference plate is bonded to the exposed side of the polarizing film of the polarizing plate having triethyl cellulose as a protective layer on one side via an adhesive, and then on the second phase difference plate. The pressure-sensitive adhesive layer (P-3132, manufactured by Lintec Co., Ltd.) formed on the separation membrane was transferred to obtain a sample 1 of the second composite polarizing plate. ❹ (Liquid crystal display device) Disassemble a commercially available LCD TV (BRAVIA KDL40V2500, manufactured by Sony), and completely peel off the film adhered to the liquid crystal cell, and then absorb it by the polarizing plate on the visual identification side (front side). The axial direction is parallel to the horizontal direction (longitudinal direction) of the liquid crystal television, and the sample 1 of the first composite polarizing plate is adhered via the pressure-sensitive adhesive layer. Further, on the opposite side (back side) of the liquid crystal cell from the visual recognition side, the absorption axis direction is parallel to the vertical direction (short side direction) of the liquid crystal television, and the second is adhered via the pressure-sensitive adhesive layer. The sample 1 of the composite polarizing plate was used as a polarizing plate to obtain a liquid crystal display device of -45-200946989. <Comparative Examples 1 to 4 > In addition, the original borneol resin film (manufactured by ZEONOR Co., Ltd.) of the cycloolefin resin was subjected to a fixed-end transverse-axial stretching, and the in-planes as shown in Table 1 were produced. Phase difference 値R. Samples 2 to 5 of the first composite polarizing plate were produced in the same manner as in Example 1 except that the first phase difference plate of the Nz coefficient was used. In addition, a second retardation plate having a phase difference 値R〇 in the plane of the 〇 shown in Table 2 and a phase difference 値Rth in the thickness direction was produced, and the same procedure as in Example 1 was used. Samples 2 to 5 of the second composite polarizing plate. The liquid crystal display devices of Comparative Examples 1 to 4 were produced in the same manner as in Example 1 except that the samples of the first composite polarizing plates and the samples of the second composite polarizing plates were combined as shown in Table 3. -46- 200946989 —^_ Phase difference film R〇(nm) Nz coefficient first - complex polarizer sample 1 兀 full - axial 140 1.00 first - complex △ polarizing plate sample 2 --- axial 100 1.32 - - Composite polarizing plate sample 3 Axiality 133 1.44 First - complex a α Polarizing plate sample 4 Axial 95 1.47 First - composite polarizing plate sample 5 - 'Axis 148 1.78 -----_ Phase difference film R 〇 ( Nm ) Rth ( nm ) Second composite polarizer sample 1 Complete biaxiality 0.2 170 Second composite polarizer sample 2 Complete biaxiality 0.1 125 Second composite polarizer sample 3 Complete biaxiality 0.1 130 Second composite polarizer Sample 4 Complete biaxiality 0.1 130 Second composite polarizing plate sample 5 Complete biaxiality 0.1 130 X First composite polarizing plate Second composite polarizing plate CR viewing angle (°) Example 1 Sample 1 Sample 1 1 10 Comparative Example 1 Sample 2 Sample 2 105 Comparative Example 2 Sample 3 Sample 3 99 Comparative Example 3 Sample 4 Sample 4 98 Comparative Example 4 Sample 5 Sample 5 8 1
<評價試驗><Evaluation test>
作爲實施例1、比較例1〜4所得之液晶顯示裝置的評 價試驗，使用視野角測定裝置（EZ-contrast 88XL, ELDIM 公司製），測定CR (對比）視野角當作白、黑顯示時的 對比（=白顯示時的亮度/黑顯示時的亮度）在方位角45 度方向中100以上的仰角之角度範圍。表3中—倂顯示此 CR視野角的測定結果。 -47- 200946989 又，第6圖係顯示實施例1、比較例1〜4所得之液晶 顯示裝置的第一相位差板之Nz係數與CR視野角的關係 之曲線圖。由第6圖可知，使用完全一軸性的相位差薄膜 當作第一相位差板時，可得到良好的視野角特性。相對於 此，可知即使爲一軸性的相位差薄膜，但由於稍微帶有二 軸性，而視野角特性變差。 產業上的利用可能性 本發明的複合偏光板組，即使改變観看角度時，也不 易發生色調的變化，可得到良好的視野角特性，特別適用 作爲垂直配向模式的液晶顯示裝置用。 【圖式簡單說明】 第1圖係以分離各層的狀態示意地顯示本發明的複合 偏光板組所用的較佳一例之第一複合偏光板1的斜視圖。 第2圖係以分離各層的狀態示意地顯示本發明的複合 偏光板組所用的較佳其它例之第一複合偏光板1 1的斜視 圖。 第3圖係以分離各層的狀態示意地顯示本發明的複合 偏光板組所用的較佳一例之第二複合偏光板21的斜視圖 〇 第4圖係本發明的複合偏光板組所用的較佳其它例之 第二複合偏光板3 1的斜視圖。 第5圖、第5(a)圖係示意地顯示使用本發明的複合 -48- 200946989 偏光板組所製造的液晶顯示裝置之一例的截面圖，第5(b )圖係以互相錯開各層的狀態顯示之上視圖。 第6圖係顯示實施例1、比較例1〜4所得之液晶顯示 裝置的第一相位差板之Nz係數與對比視野角的關係之曲 線圖。 【主要元件符號說明】In the evaluation test of the liquid crystal display device of the first embodiment and the comparative examples 1 to 4, a viewing angle measuring device (EZ-contrast 88XL, manufactured by ELDIM Co., Ltd.) was used to measure the CR (comparative) viewing angle as white or black. Contrast (=luminance in white display/brightness in black display) An angular range of elevation angle of 100 or more in the azimuth angle of 45 degrees. In Table 3, 倂 shows the measurement result of this CR viewing angle. Further, Fig. 6 is a graph showing the relationship between the Nz coefficient of the first phase difference plate of the liquid crystal display device of Example 1 and Comparative Examples 1 to 4 and the CR viewing angle. As is apparent from Fig. 6, when a completely one-axis retardation film is used as the first retardation film, good viewing angle characteristics can be obtained. On the other hand, it is understood that even if it is a one-axis retardation film, it has a biaxial property and the viewing angle characteristics are deteriorated. Industrial Applicability The composite polarizing plate assembly of the present invention does not easily change the color tone even when the viewing angle is changed, and can obtain a good viewing angle characteristic, and is particularly suitable for use as a liquid crystal display device in a vertical alignment mode. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a perspective view schematically showing a first composite polarizing plate 1 of a preferred example used in the composite polarizing plate assembly of the present invention in a state in which the respective layers are separated. Fig. 2 is a perspective view schematically showing the first composite polarizing plate 1 1 of a preferred other example of the composite polarizing plate group of the present invention in a state in which the respective layers are separated. Fig. 3 is a perspective view schematically showing a second composite polarizing plate 21 of a preferred example of the composite polarizing plate assembly of the present invention in a state in which the respective layers are separated. Fig. 4 is a preferred embodiment of the composite polarizing plate assembly of the present invention. A perspective view of a second composite polarizing plate 3 1 of another example. Fig. 5 and Fig. 5(a) are schematic cross-sectional views showing an example of a liquid crystal display device manufactured by using the composite-48-200946989 polarizing plate group of the present invention, and Fig. 5(b) is a diagram in which the layers are shifted from each other. The status shows the top view. Fig. 6 is a graph showing the relationship between the Nz coefficient of the first phase difference plate of the liquid crystal display device of Example 1 and Comparative Examples 1 to 4 and the contrast viewing angle. [Main component symbol description]
1、 11 :第一複合偏光板 2、 12 :偏光板 3 :第一相位差板 4:感壓性黏著劑層 5、 25 :直線偏光薄膜 6、 7、26、27 :保護層 21、31 :第二複合偏光板 2 2、3 2 :偏光板 23 :第二相位差板 24 :感壓性黏著劑層 50 :液晶胞 -49-1, 11 : First composite polarizing plate 2, 12: Polarizing plate 3: First phase difference plate 4: Pressure-sensitive adhesive layer 5, 25: Linear polarizing film 6, 7, 26, 27: Protective layers 21, 31 : second composite polarizing plate 2 2, 3 2 : polarizing plate 23: second phase difference plate 24: pressure-sensitive adhesive layer 50: liquid crystal cell - 49-