TWI448781B - Liquid crystal display device - Google Patents

Liquid crystal display device Download PDF

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TWI448781B
TWI448781B TW097122561A TW97122561A TWI448781B TW I448781 B TWI448781 B TW I448781B TW 097122561 A TW097122561 A TW 097122561A TW 97122561 A TW97122561 A TW 97122561A TW I448781 B TWI448781 B TW I448781B
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film
retardation layer
retardation
liquid crystal
layer
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TW200919020A (en
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Ayako Ouchi
Takashi Takebe
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Konica Minolta Opto Inc
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G02F1/133634—Birefringent elements, e.g. for optical compensation the refractive index Nz perpendicular to the element surface being different from in-plane refractive indices Nx and Ny, e.g. biaxial or with normal optical axis
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1343—Electrodes
    • G02F1/134309—Electrodes characterised by their geometrical arrangement
    • G02F1/134363—Electrodes characterised by their geometrical arrangement for applying an electric field parallel to the substrate, i.e. in-plane switching [IPS]
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/40—Materials having a particular birefringence, retardation
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2413/00—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates
    • G02F2413/02—Number of plates being 2

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)

Description

液晶顯示裝置Liquid crystal display device

本發明關於液晶顯示裝置，更詳細地，關於視野角經改善，從傾斜45度方向觀看時色移良好的橫電場切換模式型液晶顯示裝置(以下稱為IPS模式型液晶顯示裝置)。More specifically, the present invention relates to a horizontal electric field switching mode liquid crystal display device (hereinafter referred to as an IPS mode liquid crystal display device) in which the viewing angle is improved and the color shift is good when viewed from a direction inclined at 45 degrees.

橫電場切換模式型液晶顯示裝置，相對於其它液晶顯示裝置的液晶模式，例如TN模式而言，係色調、對比、視野角等優異，還有相對於垂直配向模式(VA、MVA、PVA等)而言，係視野角等的顯示性能優異，而且由於視角所致的亮度變化少、中間調的響應速度之下降少等優異的效果，故作為通稱的IPS(In Plane Switching)模式型液晶顯示裝置(IPS模式型TV等)被市場活躍地提供。作為IPS模式型液晶顯示裝置，除了所謂的IPS模式，還可舉出FFS(邊緣電場切換)模式、FLC(鐵電性液晶)模式。The horizontal electric field switching mode liquid crystal display device is excellent in hue, contrast, viewing angle, and the like with respect to the liquid crystal mode of other liquid crystal display devices, for example, the TN mode, and the vertical alignment mode (VA, MVA, PVA, etc.) The IPS (In Plane Switching) mode liquid crystal display device is excellent in display performance such as a viewing angle and the like, and has excellent effects such as a small change in luminance due to a viewing angle and a small decrease in the response speed of the intermediate tone. (IPS mode TV, etc.) is actively provided by the market. As the IPS mode liquid crystal display device, in addition to the so-called IPS mode, an FFS (Fringe Electric Field Switching) mode and an FLC (Ferroelectric Liquid Crystal) mode are also mentioned.

然而，IPS模式雖然具有垂直方向、水平方向的視野角寬之特徴，但是亦有傾斜方向的視野角窄之問題點。However, although the IPS mode has the characteristics of the viewing angle width in the vertical direction and the horizontal direction, there is also a problem that the viewing angle in the oblique direction is narrow.

因此，有提案使用2分之1波長板的方法當作視野角補償方法(例如參照專利文獻1)。Therefore, a method of using a one-half wavelength plate has been proposed as a viewing angle compensation method (for example, refer to Patent Document 1).

但是，為了製作2分之1波長板，必須有使經拉伸的薄膜進行熱收縮的繁雜操作，而且由於收縮片的貼合生產 ，不適合於輥對輥，還有因為經由黏著層或接著層來貼合複數的薄膜，而費工夫及成本，再者有發生透過率降低下或偏光板的厚膜化之問題。因此，此等方法係難以輥對輥來偏光板化，而且有由於熱收縮而發生不均，成為軸精度低等的相位差薄膜之問題。However, in order to produce a one-half wave plate, there must be a complicated operation of heat-shrinking the stretched film, and due to the bonding production of the shrink film. It is not suitable for the roll-to-roller, and it is laborious and costly to bond a plurality of films through the adhesive layer or the adhesive layer, and there is a problem that the transmittance is lowered or the polarizing plate is thickened. Therefore, in such a method, it is difficult to polarize the sheet by the roll, and unevenness occurs due to heat shrinkage, which causes a problem of a retardation film having low axial accuracy.

對如此的問題，亦想出藉由簡便的拉伸薄膜來補償(例如參照專利文獻2)。該專利提案負的1軸性光學薄膜與nx>ny>nz的光學薄膜之積層相位差薄膜。於此構成的情況中，nx>ny>nz的薄膜之面內相位差Ro係被視為愈小愈佳。Such a problem is also thought to be compensated by a simple stretched film (for example, refer to Patent Document 2). The patent proposes a laminated retardation film of a 1-axis optical film and an optical film of nx>ny>nz. In the case of this constitution, the in-plane phase difference Ro of the film of nx>ny>nz is considered to be smaller as possible.

又，有提案藉由折射率各向異性為負的Ro＝50~330nm、Rth＝0~－100nm的相位差層與Ro<50nm、Rth＝－10~100nm的相位差層之層合體來作光學補償。於此情況下，Ro係被視為愈小愈佳(例如參照專利文獻3)。Further, it has been proposed to use a laminate of a phase difference layer of Ro = 50 to 330 nm, Rth = 0 to -100 nm, and a phase difference layer of Ro < 50 nm and Rth = -10 to 100 nm, which are negative in refractive index anisotropy. Optical compensation. In this case, the Ro system is considered to be as small as possible (for example, refer to Patent Document 3).

再者，有提案Ro<100nm且Rth＝50~200nm的相位差層與折射率各向異性為負且面內具有光學軸的層之積層(例如參照專利文獻4)，藉由使兩層的遲相軸成一致，Ro的加算係可能，而且判斷能減少Ro。如此地，負的1軸性薄膜上所層合之正的薄膜之面內相位差無者為佳，或者僅止於負的1軸性薄膜之面內相位差的補助角色。In addition, there is a laminate in which a retardation layer of Ro<100 nm and Rth=50-200 nm and a layer having a refractive index anisotropy and an optical axis in the plane are provided (for example, refer to Patent Document 4), by making two layers The late phase axes are consistent, Ro's addition system is possible, and the judgment can reduce Ro. In this way, the in-plane phase difference of the positive film laminated on the negative 1-axis film is preferably no better, or only the auxiliary role of the in-plane phase difference of the negative 1-axis film.

然而，於此等的構成中，若與沒有相位差薄膜相比，雖然可見到某一程度的視野角改善，但是傾斜方向的視野角之改善係不充分，或黑顯示的色移亦大。此處理所言的黑顯示之色移係意味不從法線方向而從傾斜方向觀察黑顯 示時的液晶顯示裝置之情況，由於方位角而導致黑色調變化。However, in such a configuration, although a certain degree of viewing angle is improved as compared with the absence of the retardation film, the improvement of the viewing angle in the oblique direction is insufficient, or the color shift of the black display is large. The color shift of the black display in this process means that the black display is not observed from the normal direction from the oblique direction. In the case of the liquid crystal display device shown at the time, the black tone changes due to the azimuth angle.

專利文獻1：特開平11-305217號公報Patent Document 1: Japanese Patent Publication No. 11-305217

專利文獻2：特開2006-293108號公報Patent Document 2: JP-A-2006-293108

專利文獻3：特開2006-71964號公報Patent Document 3: JP-A-2006-71964

專利文獻4：特開2005-309382號公報Patent Document 4: JP-A-2005-309382

因此，本發明之目的為提供視野角經改善，而且從傾斜45度方向觀看時色移良好之IPS模式型液晶顯示裝置。Accordingly, an object of the present invention is to provide an IPS mode type liquid crystal display device in which the viewing angle is improved and the color shift is good when viewed from a direction inclined at 45 degrees.

本發明的上述課題係藉由以下的構成來達成。The above problems of the present invention are achieved by the following constitution.

1.一種液晶顯示裝置，係依順序配置有第1偏光鏡、第1基板、液晶層、第2基板及第2偏光鏡，在第1偏光鏡與第1基板之間配置有第1相位差層及第2相位差層，黑顯示時該液晶層的液晶分子係相對於一對基板的表面呈平行地配向，其特徵為：第1相位差層係負的一軸性，第2相位差層之由下述式所表示的面內的遲滯值Ro為5<Ro≦100nm，且第2相位差層的厚度方向之遲滯值Rth為100<Rth≦200nm， 第1偏光鏡的吸收軸與液晶層的摩擦方向係正交，第1相位差層及第2相位差層之中，靠近第1基板之側的相位差層之遲相軸係與液晶層的摩擦方向實質上呈平行，第1相位差層及第2相位差層之中，靠近第1偏光鏡之側的相位差層之遲相軸係與第1偏光鏡的吸收軸實質上呈平行，Ro＝(nx－ny)×d Rth＝{(nx＋ny)/2－nz}×d1. A liquid crystal display device in which a first polarizer, a first substrate, a liquid crystal layer, a second substrate, and a second polarizer are disposed in this order, and a first phase difference is disposed between the first polarizer and the first substrate In the layer and the second retardation layer, the liquid crystal molecules of the liquid crystal layer are aligned in parallel with respect to the surfaces of the pair of substrates in black display, and the first retardation layer is negatively uniaxial, and the second retardation layer is The in-plane hysteresis value Ro represented by the following formula is 5<Ro≦100 nm, and the hysteresis value Rth in the thickness direction of the second retardation layer is 100<Rth≦200 nm, The absorption axis of the first polarizer is orthogonal to the rubbing direction of the liquid crystal layer, and among the first retardation layer and the second retardation layer, the retardation axis of the retardation layer on the side close to the first substrate and the liquid crystal layer The rubbing direction is substantially parallel, and among the first retardation layer and the second retardation layer, the retardation axis of the retardation layer on the side close to the first polarizer is substantially parallel to the absorption axis of the first polarizer. Ro=(nx-ny)×d Rth={(nx+ny)/2-nz}×d

(式中，nx係相位差層面內的遲相軸方向之折射率，ny係相位差層面內的進相軸方向之折射率，nz係相位差層厚度方向之折射率，d係相位差層的厚度(nm))。(In the formula, the refractive index of the slow phase axis in the nx phase difference layer, the refractive index of the phase axis direction in the phase difference layer of the ny phase, the refractive index in the thickness direction of the nz phase retardation layer, and the d phase retardation layer Thickness (nm)).

2.如前述1記載的液晶顯示裝置，其中前述第1相位差層的Ro為50≦Ro≦300nm，下述式所示的Nz為－0.5≦Nz≦0，Nz＝(nx－nz)/(nx－ny)。2. The liquid crystal display device according to the above 1, wherein Ro of the first retardation layer is 50 ≦ Ro ≦ 300 nm, and Nz represented by the following formula is -0.5 ≦ Nz ≦ 0, and Nz = (nx - nz) / (nx-ny).

3.如前述1或2記載的液晶顯示裝置，其中於前述第2基板與第2偏光鏡之間配置有第3相位差層，該第3相位差層滿足0≦Ro≦5nm，且0≦| Rth |<40nm。3. The liquid crystal display device according to the above aspect 1 or 2, wherein a third retardation layer is disposed between the second substrate and the second polarizer, and the third retardation layer satisfies 0≦Ro≦5 nm and 0≦ | Rth |<40nm.

4.如前述1~3中任一項記載的液晶顯示裝置，其中前述第2相位差層含有纖維素酯系樹脂。4. The liquid crystal display device according to any one of the above aspects, wherein the second retardation layer contains a cellulose ester resin.

5.如前述1~4中任一項記載的液晶顯示裝置，其中前述第1相位差層含有苯乙烯系樹脂或茀系樹脂。In the liquid crystal display device according to any one of the above aspects, the first retardation layer contains a styrene resin or a lanthanum resin.

藉由本發明，可生產性佳地提供視野角經改善，從傾斜45度方向觀看時色移良好之IPS模式型液晶顯示裝置。According to the present invention, it is possible to provide an IPS mode type liquid crystal display device which is improved in viewing angle and has good color shift when viewed from a direction inclined at 45 degrees.

實施發明的最佳形態Best form for implementing the invention

以下詳細說明用於實施本發明的最佳形態，惟本發明不受此等所限定。The best mode for carrying out the invention is described in detail below, but the invention is not limited thereto.

最初，本發明所言的相位差層係定義為具有將背光的光等經由第1片的偏光板而一旦直線偏光化，但通過液晶層等則會橢圓偏光化者，再度轉換成直線偏光的所謂光學補償機能之機能層、基板或薄膜。因此，除了基板或薄膜本身具有光學補償機能的情況，亦包括在將具有相位差機能的層塗佈在基材上或蒸鍍而賦有光學補償機能的基板或薄膜之兩者。First, the phase difference layer according to the present invention is defined as a method in which light of a backlight or the like is linearly polarized by a polarizing plate of a first sheet, but is polarized by a liquid crystal layer or the like, and is converted into linear polarized light again. The functional layer, substrate or film of optical compensation function. Therefore, in addition to the case where the substrate or the film itself has an optical compensation function, it also includes both a substrate or a film in which a layer having a phase difference function is coated on a substrate or vapor-deposited to impart an optical compensation function.

本發明中的相位差層，從加工適合性、操作容易性之觀點來看，較佳為相位差薄膜，本說明書中的相位差層與相位差薄膜亦有視為同義處理的情況。The phase difference layer in the present invention is preferably a retardation film from the viewpoint of processing suitability and ease of handling, and the phase difference layer and the retardation film in the present specification are also treated as synonymous.

本發明人們鑒於上述問題，進行專心致力的檢討，結果發現在IPS模式型液晶顯示裝置中，藉由將具有負的1軸性之相位差層及具有面內相位差的相位差層，以打消各自的面內相位差方式使各個遲相軸正交的方式而重疊，從傾斜45度方向觀看時的色移變良好的新知識，終於完成 本發明。In view of the above problems, the inventors of the present invention conducted an intensive review and found that in an IPS mode liquid crystal display device, a phase difference layer having a negative one-axis property and a phase difference layer having an in-plane phase difference are eliminated. The respective in-plane phase difference modes overlap each other so that the respective slow-phase axes are orthogonal, and the new knowledge that the color shift becomes good when viewed from the oblique 45-degree direction is finally completed. this invention.

藉由層合具有不同光學特性的層，相位差層單層所無法的偏光狀態之轉換係變成可能。此時，若藉由層合不具有面內相位差的相位差層，則只有厚度方向成分的偏光變換才可能，但藉由特意地層合具有面內相位差的相位差層，則不僅在厚度方向而且在面內方向轉換偏光狀態係成為可能。By laminating layers having different optical characteristics, it is possible to convert a polarization state which is impossible for a single layer of the phase difference layer. At this time, by laminating the phase difference layer having no in-plane phase difference, only the polarization conversion of the thickness direction component is possible, but by intentionally laminating the phase difference layer having the in-plane phase difference, not only in the thickness It is possible to change the polarization state in the direction and in the in-plane direction.

茲推測從傾斜方向觀看時的色移，由於受到厚度方向與面內方向兩方的偏光狀態之影響，故藉由層合具有面內相位差的相位差層，而轉換面內、厚度兩方的偏光狀態，大幅改善從傾斜方向觀看時的色移。再者，為了不改變第1相位差層與第2相位差層所轉換的偏光狀態，後述的第3相位差層之相位差係愈小愈佳。It is presumed that the color shift when viewed from the oblique direction is affected by both the thickness direction and the in-plane direction, so that the in-plane and thickness are converted by laminating the phase difference layer having the in-plane phase difference. The polarized state greatly improves the color shift when viewed from the oblique direction. In addition, in order not to change the polarization state of the first retardation layer and the second retardation layer, the phase difference of the third retardation layer to be described later is preferably as small as possible.

即，本發明的液晶顯示裝置係依順序配置有第1偏光鏡、第1基板、液晶層、第2基板及第2偏光鏡，在第1偏光鏡與第1基板之間配置有第1相位差層及第2相位差層，黑顯示時該液晶層的液晶分子係相對於一對基板的表面呈平行地配向之液晶顯示裝置，其特徵為：第1相位差層係負的一軸性，第2相位差層之由下述式所表示的面內的遲滯值Ro為5<Ro≦100nm，較佳為20≦Ro≦100nm，且第2相位差層的厚度方向之遲滯值Rth為100<Rth≦200nm，第1偏光鏡的吸收軸與液晶層的摩擦方向係正交，第1相位差層及第2相位差層之中，靠近第1基板之 側的相位差層之遲相軸係與液晶層的摩擦方向實質上呈平行，第1相位差層及第2相位差層之中，靠近第1偏光鏡之側的相位差層之遲相軸係與第1偏光鏡的吸收軸實質上呈平行。In the liquid crystal display device of the present invention, the first polarizer, the first substrate, the liquid crystal layer, the second substrate, and the second polarizer are disposed in this order, and the first phase is disposed between the first polarizer and the first substrate. a liquid crystal display device in which the liquid crystal molecules of the liquid crystal layer are aligned in parallel with respect to the surface of the pair of substrates in the black layer display, wherein the first retardation layer is negatively uniaxial, The in-plane hysteresis value Ro of the second retardation layer represented by the following formula is 5 < Ro≦ 100 nm, preferably 20 ≦ Ro ≦ 100 nm, and the hysteresis value Rth of the thickness direction of the second retardation layer is 100. <Rth≦200 nm, the absorption axis of the first polarizer is orthogonal to the rubbing direction of the liquid crystal layer, and the first retardation layer and the second retardation layer are close to the first substrate. The retardation axis of the side retardation layer is substantially parallel to the rubbing direction of the liquid crystal layer, and the retardation axis of the retardation layer close to the side of the first polarizer is among the first retardation layer and the second retardation layer. It is substantially parallel to the absorption axis of the first polarizer.

於本發明中，所謂的上述第1相位差層具有負的一軸性，就是指下述式所定義的Nz滿足-0.5≦Nz≦0的範圍。In the present invention, the first retardation layer has a negative one-axis property, and means that Nz defined by the following formula satisfies a range of -0.5 ≦ Nz ≦ 0.

Ro=(nx-ny)×dRo=(nx-ny)×d

Rth={(nx+ny)/2-nz}×dRth={(nx+ny)/2-nz}×d

Nz=(nx-nz)/(nx-ny)Nz=(nx-nz)/(nx-ny)

(式中，nx係相位差層面內的遲相軸方向之折射率，ny係相位差層面內的進相軸方向之折射率，nz係相位差層厚度方向之折射率，d係相位差層的厚度(nm))。(In the formula, the refractive index of the slow phase axis in the nx phase difference layer, the refractive index of the phase axis direction in the phase difference layer of the ny phase, the refractive index in the thickness direction of the nz phase retardation layer, and the d phase retardation layer Thickness (nm)).

為了對前述第1相位差層賦予負的一軸性，例如較佳為藉由苯乙烯系樹脂或茀系樹脂等來形成該層，在最適合的方向中進行一軸或二軸拉伸。或者，亦較佳為將該樹脂塗佈在基材上及使乾燥、固定化，再者也較佳為以積層狀態來進行拉伸。In order to impart a negative one-axis property to the first retardation layer, for example, it is preferable to form the layer by a styrene resin or a fluorene-based resin, and to perform one-axis or two-axis stretching in an optimum direction. Alternatively, it is also preferred to apply the resin to a substrate, to dry and fix it, and it is also preferred to carry out stretching in a laminated state.

為了使前述第2相位差層的遲滯值成為上述數值範圍，較佳為將該第2相位差層在加熱處理的狀態下進行一軸或二軸拉伸處理。又，該相位差層含有纖維素酯的情況，於加熱處理而拉伸時，為了盡可能地減少殘留畸變，較佳為在纖維素酯的玻璃轉移點±10℃左右的範圍，以1.1倍 ~1.5倍左右，在與輸送方向正交的方向中拉伸，或將藉由溶液流延所製作的薄膜，在殘留溶劑量為2~100質量%左右的殘留狀態下，於與輸送方向正交的方向中，以1.1~1.7倍左右進行拉伸。In order to make the hysteresis value of the second retardation layer into the above numerical range, it is preferred that the second retardation layer is subjected to one-axis or two-axis stretching treatment in a state of heat treatment. Further, in the case where the retardation layer contains a cellulose ester, it is preferable to reduce the residual distortion as much as possible in the case of stretching by heat treatment, and it is preferably 1.1 times in the range of about ±10 ° C of the glass transition point of the cellulose ester. ~1.5 times or so, stretching in a direction orthogonal to the transport direction, or a film produced by solution casting, in a residual state in which the amount of residual solvent is about 2 to 100% by mass, in the direction of transport In the direction of intersection, the stretching is performed at about 1.1 to 1.7 times.

又，較佳為控制第2相位差層的面內不均。因此，較佳為精密地控制拉伸溫度與拉伸倍率的平衡，在該相位差層的兩側獨立地控制拉伸部分(拉幅機的夾具等)。此係可藉由相對於夾具位置及夾具的應力，調整拉伸溫度與拉伸倍率來達成。Further, it is preferable to control the in-plane unevenness of the second retardation layer. Therefore, it is preferable to precisely control the balance between the stretching temperature and the stretching ratio, and independently control the stretching portion (the holder of the tenter, etc.) on both sides of the phase difference layer. This can be achieved by adjusting the stretching temperature and the stretching ratio with respect to the position of the jig and the stress of the jig.

再者，本發明的液晶顯示裝置係於前述第2基板與第2偏光鏡之間配置有第3相位差層，該第3相位差層的遲滯值滿足0≦Ro≦5nm，且0≦| Rth |<40nm，此係為能進一步提高視野角的改善效果，改善從傾斜45度方向觀察時色移之較佳態樣。特佳為滿足0≦| Rth |<10nm。Further, in the liquid crystal display device of the present invention, the third retardation layer is disposed between the second substrate and the second polarizer, and the hysteresis value of the third retardation layer satisfies 0≦Ro≦5 nm and 0≦| Rth |<40 nm, which is an improvement effect of further improving the viewing angle, and improving the color shift when viewed from a direction of 45 degrees. Very good for satisfying 0≦| Rth |<10nm.

即，藉由將第1相位差層及第2相位差層的遲滯值控制在特定範圍，而且降低第3的相位差層之遲滯值Ro、Rth，則除了IPS模式型液晶顯示裝置的視野角擴大效果，亦可大幅抑制色移，雖然以往黑顯示時色調變化係顯著，但此可大幅地減低它。In other words, by controlling the hysteresis values of the first retardation layer and the second retardation layer to a specific range and reducing the hysteresis values Ro and Rth of the third retardation layer, the viewing angle of the IPS mode liquid crystal display device is removed. By expanding the effect, the color shift can be greatly suppressed. Although the color change in the black display is remarkable in the past, this can be greatly reduced.

為了使前述第3相位差層的遲滯值在上述數值範圍，若第3相位差層的主成分為纖維素酯，則較佳為藉由熔融製膜來製造，或藉由溶液製膜，在途中於玻璃轉移點以上的溫度保持15秒以上，或添加具有與纖維素酯相反的雙折射展現性之添加劑。又，若為環烯烴系薄膜，則較佳為 不對熔融或溶液流延所製造的薄膜進行拉伸處理而照原樣地使用。In order to make the hysteresis value of the third retardation layer in the above numerical range, if the main component of the third retardation layer is a cellulose ester, it is preferably produced by melt film formation or by film formation by solution. The temperature above the glass transition point is maintained for more than 15 seconds, or an additive having a birefringence exhibitivity opposite to that of the cellulose ester is added. Further, in the case of a cycloolefin film, it is preferably The film produced by melt or solution casting is not subjected to stretching treatment and used as it is.

以下詳細說明本發明的各要素。Hereinafter, each element of the present invention will be described in detail.

〈遲滯值的測定〉<Measurement of hysteresis value>

作為本發明中的遲滯值之測定的一例，係使用王子計測機器製KOBRA21ADH，對試料的10個地方，在23℃、55%RH的環境下，以590nm的波長進行3次元折射率測定，求得折射率nx、ny、nz。As an example of the measurement of the hysteresis value in the present invention, KOBRA21ADH manufactured by Oji Scientific Instruments Co., Ltd. was used to measure the decile index at a wavelength of 590 nm in 10 places of the sample at 23 ° C and 55% RH. The refractive indices nx, ny, nz are obtained.

本發明中相位差層的厚度方向之遲滯值成為負值的樣品，係於計算遲滯值時，以相位差層的面內進相軸當作傾斜軸，測定40度傾斜時的遲滯值，使用於計算。In the present invention, when the hysteresis value in the thickness direction of the phase difference layer is a negative value, when the hysteresis value is calculated, the in-plane phase axis of the phase difference layer is used as the tilt axis, and the hysteresis value at the 40-degree tilt is measured. For calculation.

〈偏光板及液晶顯示裝置的構成〉<Construction of polarizing plate and liquid crystal display device>

使用圖式來說明本發明的偏光板及液晶顯示裝置之構成。The configuration of the polarizing plate and the liquid crystal display device of the present invention will be described using a drawing.

第1圖係與申請專利範圍第1項有關的偏光板及液晶顯示裝置之構成。Fig. 1 is a view showing a configuration of a polarizing plate and a liquid crystal display device relating to the first item of the patent application.

第1偏光鏡1、第2相位差層3、第1相位差層2、第1基板4、液晶層5、第2基板6、第2偏光鏡8係依順序配置著。第1偏光鏡1的吸收軸11與第2相位差層3的遲相軸13係平行，第1相位差層2的遲相軸12與第1基板4的摩擦方向14係平行。即，第1相位差層2的遲相軸12與第2相位差層3的遲相軸13係正交。再者， 於第2基板6與第2偏光鏡8之間，配置與申請專利範圍第3項有關的第3相位差層7。第2偏光鏡8的吸收軸16係與第2基板6的摩擦方向15呈平行。背光(BL)的位置係可在第1偏光鏡側、第2偏光鏡側中任一側。The first polarizer 1, the second retardation layer 3, the first retardation layer 2, the first substrate 4, the liquid crystal layer 5, the second substrate 6, and the second polarizer 8 are arranged in this order. The absorption axis 11 of the first polarizer 1 is parallel to the slow axis 13 of the second retardation layer 3, and the slow axis 12 of the first retardation layer 2 is parallel to the rubbing direction 14 of the first substrate 4. That is, the slow axis 12 of the first retardation layer 2 and the slow axis 13 of the second retardation layer 3 are orthogonal to each other. Furthermore, The third retardation layer 7 related to the third item of the patent application is disposed between the second substrate 6 and the second polarizer 8. The absorption axis 16 of the second polarizer 8 is parallel to the rubbing direction 15 of the second substrate 6. The position of the backlight (BL) can be either one of the first polarizer side and the second polarizer side.

第2圖係與申請專利範圍第1項有關的偏光板及液晶顯示裝置的另一構成。Fig. 2 is another configuration of a polarizing plate and a liquid crystal display device relating to the first aspect of the patent application.

第1偏光鏡1、第1相位差層2、第2相位差層3、第1基板4、液晶層5、第2基板6、第2偏光鏡8係依順序配置著。第1偏光鏡1的吸收軸11與第1相位差層2的遲相軸12係平行，第2相位差層3的遲相軸13與第1基板4的摩擦方向14係平行。即，第1相位差層2的遲相軸12與第2相位差層3的遲相軸13係正交。再者，於第2基板6與第2偏光鏡8之間，配置與申請專利範圍第3項有關的第3相位差層7。背光(BL)的位置係可在第1偏光鏡側或第2偏光鏡側中任一側。The first polarizer 1, the first retardation layer 2, the second retardation layer 3, the first substrate 4, the liquid crystal layer 5, the second substrate 6, and the second polarizer 8 are arranged in this order. The absorption axis 11 of the first polarizer 1 is parallel to the slow axis 12 of the first retardation layer 2, and the slow axis 13 of the second retardation layer 3 is parallel to the rubbing direction 14 of the first substrate 4. That is, the slow axis 12 of the first retardation layer 2 and the slow axis 13 of the second retardation layer 3 are orthogonal to each other. Further, a third retardation layer 7 related to the third item of the patent application is disposed between the second substrate 6 and the second polarizer 8. The position of the backlight (BL) may be either one of the first polarizer side or the second polarizer side.

於本說明書中，所謂實質地「平行」、「正交」就是意味嚴密角度±10°以內的範圍內。該範圍與嚴密角度的誤差較佳為小於±5°，較佳為小於±2°。In the present specification, the term "substantially parallel" or "orthogonal" means a range within a range of ±10° from a strict angle. The error between the range and the tight angle is preferably less than ± 5°, preferably less than ± 2°.

對於第1相位差層與第2相位差層的積層順序，例如於纖維素系樹脂所作成的第2相位差層接於第1偏光鏡時，與PVA偏光鏡的接著係變容易，由於可藉由現有的製程來貼合，故生產性高。When the second retardation layer formed of the cellulose resin is bonded to the first polarizer, for example, when the first retardation layer and the second retardation layer are laminated, the adhesion to the PVA polarizer becomes easy. It is highly productive because it is bonded by the existing process.

又，對於第1相位差層與第2相位差層的積層順序，例如於苯乙烯系樹脂所作成的第1相位差層接於第1偏光 鏡時，藉由使拉伸方向與長度方向成一致，可不導入拉幅機拉伸等的複雜拉伸製程，而僅藉由單純的輸送張力使展現相位差。Further, in the order of lamination of the first retardation layer and the second retardation layer, for example, the first retardation layer formed of the styrene resin is bonded to the first polarized light. In the case of the mirror, by conforming the stretching direction to the longitudinal direction, it is possible to exhibit a phase difference by simply conveying the tension without introducing a complicated stretching process such as tenter stretching.

上述第1偏光鏡、第2偏光鏡係可藉由一般的方法來製作。偏光鏡係僅使一定方向的偏波面之光通過的元件，作為現在已知的代表性偏光鏡，有聚乙烯醇系偏光薄膜，此有對聚乙烯醇系薄膜以碘染色者及以二色性染料染色者。偏光鏡係使用將聚乙烯醇水溶液製膜，將其一軸拉伸及染色，或染色後進行一軸拉伸，較佳為以硼化合物進行耐久性處理者。The first polarizer and the second polarizer can be produced by a general method. The polarizer is an element that passes only light of a polarized surface in a certain direction, and is a representative polarizer which is known now, and has a polyvinyl alcohol-based polarizing film, and the polyvinyl alcohol-based film is dyed with iodine and has two colors. Sex dye dyes. The polarizer is formed by forming a film of a polyvinyl alcohol aqueous solution, stretching and dyeing it in one axis, or performing one-axis stretching after dyeing, and it is preferred to carry out durability treatment with a boron compound.

通常偏光鏡之兩側係被作為保護層的TAC薄膜所挾持。對將TAC薄膜的背面側進行鹼皂化處理，在上述碘溶液中浸漬拉伸所製作的偏光鏡之至少一面，較佳為使用完全皂化型聚乙烯醇水溶液來貼合。另一方面，可使用該TAC薄膜，或使用其它的偏光板保護薄膜。亦較宜使用市售的纖維素酯薄膜(例如Konicaminoltatec KC8UX、KC4UX、KC5UX、KC8UCR3、KC8UCR4、KC8UCR5、KC8UY、KC4UY、KC12UR、KC4FR，以上Konica－Minolta Opto(股)製)。Usually, both sides of the polarizer are held by a TAC film as a protective layer. The back side of the TAC film is subjected to alkali saponification treatment, and at least one surface of the polarizing lens produced by immersing and stretching the iodine solution is preferably laminated using a completely saponified polyvinyl alcohol aqueous solution. Alternatively, the TAC film can be used, or other polarizing plates can be used to protect the film. It is also preferred to use a commercially available cellulose ester film (for example, Konicaminoltatec KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC12UR, KC4FR, manufactured by Konica-Minolta Opto Co., Ltd.).

於本發明的構成中，第1偏光鏡、第2偏光鏡皆係由2片TAC薄膜所挾持，第1相位差層、第2相位差層、第3相位差層係可經由接著劑層來貼合第1偏光鏡較佳為直接貼合第1相位差層或第2相位差層，較佳為第2偏光鏡係直接貼合第3相位差層，因為可薄膜化、減少構件。In the configuration of the present invention, both the first polarizer and the second polarizer are held by two TAC films, and the first retardation layer, the second retardation layer, and the third retardation layer can be via the adhesive layer. Preferably, the first polarizer is bonded to the first retardation layer or the second retardation layer. Preferably, the second polarizer directly bonds the third retardation layer, because the film can be thinned and the member can be reduced.

藉由將上述本發明的偏光板併入液晶顯示裝置中，可製作視覺辨識性優異的本發明之液晶顯示裝置。By incorporating the above-described polarizing plate of the present invention into a liquid crystal display device, it is possible to produce a liquid crystal display device of the present invention which is excellent in visibility.

本發明的偏光板係直接貼合於挾持著液晶層的第1基板、第2基板，從液晶胞的基板要求高度的平面性、平滑性來看，主要使用具有透光性的玻璃基板。為了滿足所欲的平面性、平滑性時，玻璃基板亦可為塑膠基板。使用塑膠基板時，基板的厚度係容易成為0.2mm以下的薄度，因此可使顯示元件極薄且輕量化。又，由於基板薄，故顯示不會成為雙重影像，可得到寬視角的顯示元件。第1基板、第2基板係可為相同材質或不同者。The polarizing plate of the present invention is directly bonded to the first substrate and the second substrate sandwiching the liquid crystal layer, and a glass substrate having light transmissivity is mainly used from the viewpoint of high planarity and smoothness of the substrate of the liquid crystal cell. In order to satisfy the desired planarity and smoothness, the glass substrate may be a plastic substrate. When a plastic substrate is used, since the thickness of the substrate is likely to be 0.2 mm or less, the display element can be made extremely thin and lightweight. Moreover, since the substrate is thin, the display does not become a double image, and a display element having a wide viewing angle can be obtained. The first substrate and the second substrate may be the same material or different.

本發明的偏光板係使用在IPS模式型液晶顯示裝置。IPS模式型液晶顯示裝置之特徵為黑顯示時液晶層的液晶分子相對於前述一對基板的表面呈平行地配向，除了IPS模式，亦可舉出FFS(邊緣電場切換)模式、FLC(鐵電性液晶)模式等。The polarizing plate of the present invention is used in an IPS mode liquid crystal display device. The IPS mode liquid crystal display device is characterized in that the liquid crystal molecules of the liquid crystal layer are aligned in parallel with respect to the surfaces of the pair of substrates in the black display, and the FFS (Fringe Electric Field Switching) mode and the FLC (ferroelectric) are also mentioned in addition to the IPS mode. Liquid crystal) mode, etc.

本發明的液晶顯示裝置係不限定於第1圖、第2圖所示的構成，亦可含有其它構件。例如，於液晶層與偏光鏡之間亦可配置彩色濾光片。於偏光鏡的保護膜之表面，亦可施予抗反射處理或硬塗層。又，亦可使用對構成構件賦有導電性者。還有，於作為透射型使用時，可為以冷陰極或熱陰極螢光管、或發光二極體、場發射元件、電致發光元件當作光源的背光配置在背面。於此情況下，背光的配置係可在第1圖及第2圖的上側或下側。又，於液晶層與背光之間，亦可配置反射型偏光板或擴散板、稜鏡片或導 光板。又，如上述地，本發明的液晶顯示裝置亦可為反射型，於該情況下，偏光板可為在觀察側僅配置1片，在液晶胞背面或液晶胞的下側基板之內面配置反射膜。當然，亦可將使用前述光源的正面光設置在液晶胞觀察側。The liquid crystal display device of the present invention is not limited to the configuration shown in Figs. 1 and 2, and may include other members. For example, a color filter may be disposed between the liquid crystal layer and the polarizer. An anti-reflection treatment or a hard coat layer may be applied to the surface of the protective film of the polarizer. Further, it is also possible to use a conductor that imparts conductivity to the constituent members. Further, when used as a transmissive type, a backlight having a cold cathode or a hot cathode fluorescent tube, or a light emitting diode, a field emission element, or an electroluminescence element as a light source may be disposed on the back surface. In this case, the arrangement of the backlights can be on the upper side or the lower side of the first and second figures. Further, between the liquid crystal layer and the backlight, a reflective polarizing plate or a diffusing plate, a cymbal or a guide may be disposed. Light board. Further, as described above, the liquid crystal display device of the present invention may be of a reflective type. In this case, the polarizing plate may be disposed only on the observation side, and may be disposed on the back surface of the liquid crystal cell or the inner surface of the lower substrate of the liquid crystal cell. Reflective film. Of course, the front light using the aforementioned light source can also be disposed on the liquid crystal cell observation side.

本發明的液晶顯示裝置，尤其在畫面為30型以上，特別是30型~54型的大畫面，也能對比高，尤其抑制視角所致的色調變化，有即使長時間觀賞，眼睛也不會疲勞的效果。In the liquid crystal display device of the present invention, in particular, a large screen having a screen size of 30 or more, particularly a 30-type to 54 type, can also be contrasted, and in particular, suppresses a change in color tone caused by a viewing angle, and even if it is viewed for a long time, the eyes are not The effect of fatigue.

(相位差層〉(phase difference layer)

(第1相位差層)(first phase difference layer)

本發明的第1相位差層之特徵為具有負的一軸性，第1相位差層的遲滯值Ro係在50≦Ro≦300nm的範圍，前述式所表示的Nz為-0.5≦Nz≦0，此在得到本發明的效果之方面係較宜。Ro特佳為在100≦Ro≦200nm的範圍。The first retardation layer of the present invention is characterized by having a negative one-axis property, and the hysteresis value Ro of the first retardation layer is in the range of 50 ≦Ro ≦ 300 nm, and the Nz represented by the above formula is -0.5 ≦ Nz ≦ 0. This is preferred in terms of obtaining the effects of the present invention. Ro Tejia is in the range of 100≦Ro≦200nm.

為了對本發明的第1相位差層賦予負的一軸性，較佳為使用苯乙烯系樹脂或茀系樹脂。In order to impart a negative primary axis to the first retardation layer of the present invention, a styrene resin or a fluorene-based resin is preferably used.

苯乙烯系樹脂可大區分為：苯乙烯或苯乙烯衍生物的均聚物；苯乙烯或苯乙烯衍生物與其它單體的共聚物；由苯乙烯或苯乙烯衍生物與其它單體所得之接枝共聚物；及此等的聚合物之混合物。The styrenic resin can be broadly distinguished as: a homopolymer of styrene or styrene derivatives; a copolymer of styrene or a styrene derivative with other monomers; and a styrene or styrene derivative and other monomers. a graft copolymer; and a mixture of such polymers.

作為苯乙烯或其衍生物的均聚物之例，可舉出苯乙烯、α-甲基苯乙烯、鄰甲基苯乙烯、對甲基苯乙烯、對氯苯乙烯、鄰硝基苯乙烯、對胺基苯乙烯、對羧基苯乙烯、對 苯基苯乙烯及2,5－二氯苯乙烯的均聚物。作為苯乙烯或苯乙烯衍生物與其它單體的共聚物之例，可舉出苯乙烯/丙烯腈共聚物、苯乙烯/甲基丙烯腈共聚物、苯乙烯/甲基丙烯酸甲酯共聚物、苯乙烯/甲基丙烯酸乙酯共聚物、苯乙烯/α－氯丙烯腈共聚物、苯乙烯/丙烯酸甲酯共聚物、苯乙烯/丙烯酸乙酯共聚物、苯乙烯/丙烯酸丁酯共聚物、苯乙烯/丙烯酸共聚物、苯乙烯/甲基丙烯酸共聚物、苯乙烯/丁二烯共聚物、苯乙烯/異戊二烯共聚物、苯乙烯/馬來酸酐共聚物、苯乙烯/伊康酸共聚物、苯乙烯/乙烯基咔唑共聚物、苯乙烯/N－苯基丙烯醯胺共聚物、苯乙烯/乙烯基吡啶共聚物、苯乙烯/乙烯基萘共聚物、α－甲基苯乙烯/丙烯腈共聚物、α－甲基苯乙烯/甲基丙烯腈共聚物、α－甲基苯乙烯/醋酸乙烯酯共聚物、苯乙烯/α－甲基苯乙烯/丙烯腈共聚物、苯乙烯/α－甲基苯乙烯/甲基丙烯酸甲酯共聚物、及苯乙烯/苯乙烯衍生物共聚物。Examples of the homopolymer of styrene or a derivative thereof include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, p-chlorostyrene, and o-nitrostyrene. Amino styrene, p-carboxystyrene, pair A homopolymer of phenylstyrene and 2,5-dichlorostyrene. Examples of the copolymer of styrene or a styrene derivative and another monomer include a styrene/acrylonitrile copolymer, a styrene/methacrylonitrile copolymer, and a styrene/methyl methacrylate copolymer. Styrene/ethyl methacrylate copolymer, styrene/α-chloroacrylonitrile copolymer, styrene/methyl acrylate copolymer, styrene/ethyl acrylate copolymer, styrene/butyl acrylate copolymer, benzene Ethylene/acrylic acid copolymer, styrene/methacrylic acid copolymer, styrene/butadiene copolymer, styrene/isoprene copolymer, styrene/maleic anhydride copolymer, styrene/iconic acid copolymer , styrene/vinyl carbazole copolymer, styrene/N-phenyl acrylamide copolymer, styrene/vinyl pyridine copolymer, styrene/vinyl naphthalene copolymer, α-methyl styrene/ Acrylonitrile copolymer, α-methylstyrene/methacrylonitrile copolymer, α-methylstyrene/vinyl acetate copolymer, styrene/α-methylstyrene/acrylonitrile copolymer, styrene/ Α-methylstyrene/methyl methacrylate copolymer, and phenylethyl / Styrene derivative copolymers.

作為接枝共聚物之例，可舉出下述的(p－1~p－17)。Examples of the graft copolymer include the following (p-1 to p-17).

但是，(A)表示主幹聚合物(亦可為嵌段共聚物)，(B)表示枝部分(接枝部分)。又，下述的量比表示質量比。However, (A) represents a trunk polymer (may also be a block copolymer), and (B) represents a branch portion (grafted portion). Further, the amount ratio described below indicates the mass ratio.

[p－1]：(A1)/(B1)＝10/90 (A1)苯乙烯/丁二烯共聚物(20/80)(B1)苯乙烯/丙烯腈/α－甲基苯乙烯(60/20/20)[p-1]: (A1)/(B1)=10/90 (A1) styrene/butadiene copolymer (20/80) (B1) styrene/acrylonitrile/α-methylstyrene (60/20/20)

[p－2]：(A1)/(B1)＝5/95[p-2]: (A1)/(B1)=5/95

[p－3]：(A1)/(B2)＝10/90 (B2)苯乙烯/丙烯腈(80/20)[p-3]: (A1) / (B2) = 10/90 (B2) styrene/acrylonitrile (80/20)

[p－4]：(A1)/(B2)＝7/93[p-4]: (A1)/(B2)=7/93

[p－5]：(A2)/(B3)＝12.5/87.5 (A2)苯乙烯/丁二烯共聚物(50/50)(B3)苯乙烯/丙烯腈(75/25)[p-5]:(A2)/(B3)=12.5/87.5 (A2) styrene/butadiene copolymer (50/50) (B3) styrene/acrylonitrile (75/25)

[p－6]：(A2)/(B4)＝15/85 (B4)苯乙烯/丙烯腈/α－甲基苯乙烯(60/30/10)[p-6]:(A2)/(B4)=15/85 (B4) styrene/acrylonitrile/α-methylstyrene (60/30/10)

[p－7]：(A2)/(B4)＝10/90[p-7]: (A2) / (B4) = 10/90

[p－8]：(A2)/(B3)＝10/90[p-8]: (A2) / (B3) = 10/90

[p－9]：(A3)/(B5)＝5/95 (A3)聚丁二烯(B5)苯乙烯/丙烯腈(70/30)[p-9]:(A3)/(B5)=5/95 (A3) Polybutadiene (B5) Styrene/Acrylonitrile (70/30)

[p－10]：(A3)/(B6)＝10/90 (B6)苯乙烯/丙烯腈/甲基丙烯腈(75/15/10)[p-10]:(A3)/(B6)=10/90 (B6) Styrene/Acrylonitrile/Methylacrylonitrile (75/15/10)

[p－11]：(A2)/(B7)＝12/88 (B7)苯乙烯[p-11]:(A2)/(B7)=12/88 (B7) styrene

[p－12]：(A4)/(B8)＝10/90 (A4)苯乙烯/丁二烯共聚物(23/77)(B8)苯乙烯/甲基甲基丙烯酸酯/丙烯腈(70/10/20)[p-12]:(A4)/(B8)=10/90 (A4) styrene/butadiene copolymer (23/77) (B8) styrene/methyl methacrylate/acrylonitrile (70/10/20)

[p－13]：(A5)/(B9)＝10/90 (A5)聚異戊二烯(B9)苯乙烯/第三丁基苯乙烯(70/30)[p-13]: (A5)/(B9)=10/90 (A5) Polyisoprene (B9) styrene / TBT (70/30)

[p－14]：(A6)/(B2)＝10/90 (A6)丙烯腈/丁二烯共聚物(50/50)[p-14]:(A6)/(B2)=10/90 (A6) Acrylonitrile/butadiene copolymer (50/50)

[p－15]：(A7)/(B1)＝12/88 (A7)丙烯腈/丁二烯共聚物(25/75)[p-15]:(A7)/(B1)=12/88 (A7) Acrylonitrile/butadiene copolymer (25/75)

[p－16]：(A8)/(B10)＝10/90 (A8)丙烯酸乙基/丁二烯共聚物(50/50)(B10)苯乙烯/甲基甲基丙烯酸酯(80/20)[p-16]:(A8)/(B10)=10/90 (A8) Acrylic Ethyl/Butadiene Copolymer (50/50) (B10) Styrene/Methyl Methacrylate (80/20)

[p－17]：(A9)/(B11)＝15/85 (A9)丙烯酸乙基/苯乙烯/丁二烯共聚物(40/30/30)(B11)苯乙烯/甲基丙烯腈(75/25)[p-17]:(A9)/(B11)=15/85 (A9) Acrylic Ethyl/Styrene/Butadiene Copolymer (40/30/30) (B11) Styrene/Methacrylonitrile (75/25)

關於苯乙烯系樹脂，在特開平4－97322號公報及特開平6－67169號公報中有記載。具有光學負的一軸性之相位差層，例如可藉由對上述苯乙烯系聚合物等的固有雙折射為負的聚合物進行一軸拉伸而得。又，亦較佳為藉由將上述聚合物塗佈在透明基材上之後，與基材一起拉伸而形成。The styrene-based resin is described in JP-A-4-97322 and JP-A-6-67169. The retardation layer having an optically negative monoaxial property can be obtained by, for example, monoaxially stretching a polymer having a negative intrinsic birefringence such as the above styrene polymer. Further, it is also preferably formed by stretching the above polymer onto a transparent substrate and then stretching it together with the substrate.

再者，第1相位差層亦可使用茀系樹脂。特別地，為了使具有茀骨架的鏈段能成為負的光學各向異性，較佳為具有茀骨架的聚碳酸酯、具有茀骨架的聚碳酸酯系共聚物、具有茀骨架的聚酯、具有茀骨架的聚酯系共聚物、具茀骨架的聚酯碳酸酯、具有茀骨架的聚酯碳酸酯系共聚物、具有茀骨架的聚芳酯、具有茀骨架的聚芳酯系共聚物等。Further, a lanthanoid resin may be used for the first retardation layer. In particular, in order to impart a negative optical anisotropy to a segment having an anthracene skeleton, a polycarbonate having an anthracene skeleton, a polycarbonate-based copolymer having an anthracene skeleton, a polyester having an anthracene skeleton, and A polyester-based copolymer of an anthracene skeleton, a polyester carbonate having an anthracene skeleton, a polyester carbonate-based copolymer having an anthracene skeleton, a polyarylate having an anthracene skeleton, a polyarylate-based copolymer having an anthracene skeleton, and the like.

與苯乙烯系樹脂同樣地，具有光學負的一軸性之相位 差層，例如可藉由將固有雙折射為負的上述茀系樹脂等之聚合物進行一軸拉伸，或塗佈在基材而形成。Like the styrene-based resin, it has an optically negative one-axis phase The poor layer can be formed, for example, by stretching a polymer such as the above-described fluorene-based resin having a negative intrinsic birefringence or by coating it on a substrate.

(相位差層的製造方法)(Method of manufacturing phase difference layer)

接著，關於本發明的第1、第2、第3相位差層之製造方法，以特佳形態的相位差薄膜當作例子來說明。Next, the method for producing the first, second, and third retardation layers of the present invention will be described by taking a particularly advantageous retardation film as an example.

本發明中所用的相位差層較佳為由溶液流延法或熔融流延法所製造的相位差薄膜。The retardation layer used in the present invention is preferably a retardation film produced by a solution casting method or a melt casting method.

本發明中所用的相位差薄膜之製造係藉由以下的步驟來進行：使上述樹脂或後述的纖維素酯及添加劑溶解於溶劑中以調製膠漿(dope)的步驟，將膠漿流延在無限移行的循環金屬支持體上之步驟。使所流延的膠漿乾燥成料片(web)之步驟，從金屬支持體剝離的步驟，拉伸或寬度保持步驟，再乾燥的步驟，將所完成的薄膜捲繞之步驟。The production of the retardation film used in the present invention is carried out by dissolving the above resin or a cellulose ester and an additive described later in a solvent to prepare a dope, and casting the paste at Steps on an infinitely moving cyclic metal support. The step of drying the cast paste into a web, the step of peeling from the metal support, the step of stretching or width maintaining, and the step of drying, the step of winding the finished film.

茲說明調製膠漿的步驟。就膠漿中的樹脂或纖維素酯之濃度而言，雖然濃者可減低在金屬支持體上流延後的乾燥負荷而較宜，但若樹脂或纖維素酯的濃度過濃，則過濾時的負荷增加，過濾精度變差。作為使此等並存的濃度，較佳為10~35質量%，更佳為15~25質量%。The step of preparing the glue is explained. In terms of the concentration of the resin or the cellulose ester in the dope, although it is preferable to reduce the drying load after casting on the metal support, if the concentration of the resin or the cellulose ester is too rich, the filtration is performed. The load increases and the filtration accuracy deteriorates. The concentration at which these are coexisted is preferably 10 to 35 mass%, more preferably 15 to 25 mass%.

膠漿所用的溶劑可單獨使用，也可併用2種以上，但從生產效率之點來看，較佳為混合使用樹脂或纖維素酯的強溶劑與弱溶劑，從樹脂或纖維素酯的溶解性之點來看，強溶劑多者為佳。The solvent used for the dope may be used singly or in combination of two or more kinds. However, from the viewpoint of production efficiency, it is preferred to use a strong solvent and a weak solvent in which a resin or a cellulose ester is used in combination, and to dissolve from a resin or a cellulose ester. From the point of view of sex, it is better to have more strong solvents.

強溶劑與弱溶劑的混合比率之較佳範圍係強溶劑為 70~98質量%，弱溶劑為2~30質量%。所謂的強溶劑、弱溶劑，就是將能單獨溶解所使用的樹脂或纖維素酯者定義為強溶劑，將單獨不能膨潤或溶解者定義為弱溶劑。The preferred range of the mixing ratio of the strong solvent to the weak solvent is that the strong solvent is 70 to 98% by mass, and the weak solvent is 2 to 30% by mass. The so-called strong solvent and weak solvent are those in which the resin or cellulose ester which can be used alone is defined as a strong solvent, and those which cannot be swollen or dissolved alone are defined as weak solvents.

因此，例如取決於纖維素酯的平均乙醯化度(乙醯基取代度)，強溶劑、弱溶劑會改變，例如於使用丙酮當作溶劑時，在纖維素酯的乙酸酯(乙醯基取代度2.4)、纖維素乙酸酯丙酸酯係成為強溶劑，在纖維素的乙酸酯(乙醯基取代度2.8)係成為弱溶劑。Therefore, for example, depending on the average degree of acetylation of the cellulose ester (degree of substitution of ethyl thiol), strong solvents and weak solvents may be changed, for example, when acetone is used as a solvent, acetate in cellulose ester (acetamidine) The degree of substitution of the base is 2.4), the cellulose acetate propionate is a strong solvent, and the cellulose acetate (the degree of substitution of acetyl group of 2.8) is a weak solvent.

本發明中所用的強溶劑係沒有特別的限定，可舉出二氯甲烷等的有機鹵化合物或二噁茂烷類、丙酮、醋酸甲酯、乙醯醋酸甲酯等。特佳可舉出二氯甲烷或醋酸甲酯。The strong solvent to be used in the present invention is not particularly limited, and examples thereof include an organic halogen compound such as dichloromethane or a dioxane, acetone, methyl acetate, methyl acetate or the like. Particularly preferred are dichloromethane or methyl acetate.

又，本發明中所用的弱溶劑係沒有特別的限定，例如較宜使用甲醇、乙醇、正丁醇、環己烷、環己酮等。又，於膠漿中較佳為含有0.01~2質量%的水。另外，樹脂或纖維素酯之溶解時所用的溶劑，係將薄膜製膜步驟之乾燥而從薄膜去除的溶劑進行回收，將其再利用而使用。Further, the weak solvent used in the present invention is not particularly limited, and for example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone or the like is preferably used. Further, it is preferred to contain 0.01 to 2% by mass of water in the dope. Further, the solvent used in the dissolution of the resin or the cellulose ester is obtained by drying the solvent removed from the film by drying the film forming step, and recycling it.

作為於調製上述記載的膠漿時之樹脂或纖維素酯的溶解方法，可使用一般的方法。若組合加熱與加壓，則可加熱到常壓的沸點以上。若於溶劑的常壓之沸點以上且在加壓下溶劑不沸騰的範圍之溫度，邊加熱邊攪拌溶解，則可防止稱為凝膠或疙瘩的塊狀未溶解物之發生而較宜。又，較宜使用在混合樹脂或纖維素酯與弱溶劑以使濕潤或膨潤後，更添加強溶劑而進行溶解之方法。As a method of dissolving the resin or the cellulose ester in the preparation of the above-described dope, a general method can be used. When combined with heating and pressurization, it can be heated to above the boiling point of normal pressure. When the temperature of the solvent is higher than the boiling point of the normal pressure and the solvent does not boil under pressure, stirring and dissolving while heating can prevent the occurrence of agglomerated undissolved matter called gel or mash. Further, it is preferred to use a method in which a resin or a cellulose ester and a weak solvent are mixed to wet or swell, and a strong solvent is further added to dissolve.

加壓係可藉由將氮氣等的惰性氣體壓入之方法，或藉 由加熱使溶劑的蒸氣壓上升之方法進行。加熱較佳係從外部來進行，例如較佳為夾套型者，因為溫度控制容易。The pressurization system can be carried out by injecting an inert gas such as nitrogen or It is carried out by a method in which the vapor pressure of the solvent is raised by heating. The heating is preferably carried out from the outside, for example, preferably a jacket type, because temperature control is easy.

添加溶劑時的加熱溫度，從樹脂或纖維素酯的溶解性之觀點看，較佳為高溫，但若加熱溫度過高，則所需要的壓力變大，生產性變差。較佳的加熱溫度為45~120℃，尤佳為60~110℃，更佳為70℃~105℃。又，壓力係調整到在設定溫度溶劑不沸騰者。The heating temperature at the time of adding a solvent is preferably a high temperature from the viewpoint of solubility of the resin or the cellulose ester. However, if the heating temperature is too high, the required pressure is increased, and productivity is deteriorated. The preferred heating temperature is 45 to 120 ° C, preferably 60 to 110 ° C, more preferably 70 to 105 ° C. Also, the pressure is adjusted so that the solvent does not boil at the set temperature.

或者，亦較宜使用冷卻溶解法，藉此可使樹脂或纖維素酯溶解在醋酸甲酯等的溶劑中。Alternatively, it is preferred to use a cooling dissolution method whereby the resin or cellulose ester can be dissolved in a solvent such as methyl acetate.

接著，使用濾紙等適當的過濾材過濾該樹脂或纖維素酯溶液。作為過濾材，較佳為用於去除不溶物等的絕對過濾精度小者，若絕對過濾精度過小，則有過濾材容易發生堵塞的問題。因此，較佳為絕對過濾精度0.008mm以下的濾材，尤佳為0.001~0.008mm的濾材，更佳為0.003~0.006mm的濾材。Next, the resin or cellulose ester solution is filtered using a suitable filter material such as filter paper. As the filter material, it is preferable that the absolute filtration accuracy for removing insoluble matter or the like is small, and if the absolute filtration accuracy is too small, there is a problem that the filter material is likely to be clogged. Therefore, a filter material having an absolute filtration accuracy of 0.008 mm or less is preferable, and a filter material of 0.001 to 0.008 mm is preferable, and a filter material of 0.003 to 0.006 mm is more preferable.

濾材的材質係沒有特別的限制，可使用通常的濾材，聚丙烯、鐵弗龍(註冊商標)等的塑膠製濾材、或不銹鋼等的金屬製濾材係不會脫落纖維等而較宜。藉由過濾，可去除、減低原料的樹脂或纖維素酯中所含有的雜質尤其亮點異物而較宜。The material of the filter material is not particularly limited, and a general filter medium can be used. A plastic filter material such as polypropylene or Teflon (registered trademark) or a metal filter material such as stainless steel is preferably used without dropping fibers. By filtration, it is preferable to remove and reduce impurities contained in the resin or cellulose ester of the raw material, particularly bright foreign matter.

所謂的亮點異物就是指將2片偏光板以正交尼科耳狀態配置，於其間配置輥狀纖維素酯，從一方的偏光板之側照射光線，而從另一方的偏光板之側觀察時，看到來自相反側的漏光之點(異物)，較佳為直徑0.01mm以上的亮 點數係200個/cm2 以下，尤佳為100個/cm2 以下，更佳為50個/m2 以下，特佳為0~10個/cm2 以下。又，較佳為0.01mm以下的亮點亦少者。The term "bright spot foreign matter" means that two polarizing plates are arranged in a crossed Nicols state, and a roll of cellulose ester is disposed therebetween, and light is irradiated from one side of one polarizing plate to the side of the other polarizing plate. When the point of light leakage from the opposite side (foreign matter) is seen, it is preferable that the number of bright dots having a diameter of 0.01 mm or more is 200 pieces/cm 2 or less, particularly preferably 100 pieces/cm 2 or less, more preferably 50 pieces/m 2 . Hereinafter, it is particularly preferably 0 to 10 pieces/cm 2 or less. Further, it is preferable that the number of bright spots of 0.01 mm or less is also small.

膠漿的過濾係可藉由通常的方法來進行，較佳為在溶劑的常壓之沸點以上且在加壓下溶劑不沸騰的範圍之溫度邊加熱邊過濾的方法，其過濾前後的液壓之差(稱為差壓)的上升小。較佳的溫度為45~120℃，尤佳為45~70℃，更佳為45~55℃。The filtration system of the dope can be carried out by a usual method, and is preferably a method of filtering while heating at a temperature above the boiling point of the solvent at a pressure above the boiling point of the solvent under a pressure, and the hydraulic pressure before and after the filtration. The rise (called differential pressure) is small. The preferred temperature is 45 to 120 ° C, preferably 45 to 70 ° C, more preferably 45 to 55 ° C.

濾壓係愈小愈佳。濾壓較佳為1.6MPa以下，尤佳為1.2MPa以下，更佳為1.0MPa以下。The smaller the filter system, the better. The filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, still more preferably 1.0 MPa or less.

此處說明膠漿的流延。The casting of the glue is described here.

流延(cast)步驟中的金屬支持體較佳為表面經鏡面修飾者，作為金屬支持體，較宜使用不銹鋼帶或鑄物的表面經鍍層拋光的滾筒。流延的寬度可為1~4m。流延步驟的金屬支持體之表面溫度為－50℃~低於溶劑的沸點之溫度，溫度高則可加快料片的乾燥速度而較宜，但若太高則料片會發泡，平面性會變差。較佳的支持體溫度為0~40℃，更佳為5~30℃。The metal support in the casting step is preferably a mirror-finished surface. As the metal support, it is preferable to use a stainless steel strip or a surface of the cast which is polished by a plating. The width of the casting can be 1~4m. The surface temperature of the metal support in the casting step is -50 ° C ~ lower than the boiling point of the solvent, and the high temperature can accelerate the drying speed of the web, but if it is too high, the sheet will foam, flatness Will get worse. The preferred support temperature is from 0 to 40 ° C, more preferably from 5 to 30 ° C.

或者，亦較佳為藉由冷卻以使料片膠化，在含有許多殘留溶劑的狀態下從滾筒剝離的方法。Alternatively, it is also preferably a method of peeling from the drum in a state containing a plurality of residual solvents by cooling to gel the web.

金屬支持體的溫度之控制方法係沒有特別的限制，有噴吹溫風或冷風的方法，或使溫水接觸金屬支持體的內側之方法。用溫水者由於有效率地進行熱的傳導，可縮短金屬支持體的溫度到達一定為止的時間而較宜。用溫風的情 況係有使用比目的之溫度還高的溫度之風的情況。The method of controlling the temperature of the metal support is not particularly limited, and there is a method of blowing warm air or cold air, or a method of bringing warm water into contact with the inner side of the metal support. Since the warm water is efficiently conducted by the warm water, it is preferable to shorten the time until the temperature of the metal support reaches a certain level. With warmth In the case, there is a case where a wind having a temperature higher than the target temperature is used.

相位差薄膜為了顯示良好的平面性，於從金屬支持體剝離料片時，殘留溶劑量較佳為10~150質量%，更佳為20~40質量%或60~130質量%，特佳為20~30質量%或70~120質量%。In order to exhibit good planarity, the retardation film preferably has a residual solvent amount of 10 to 150% by mass, more preferably 20 to 40% by mass or 60 to 130% by mass, when it is peeled off from the metal support. 20 to 30% by mass or 70 to 120% by mass.

又，於輥狀相位差薄膜的乾燥步驟中，從金屬支持體剝離料片，再進行乾燥，較佳為使殘留溶劑量成為1質量%以下，更佳為0.1質量%以下，特佳為0~0.01質量%以下。Moreover, in the drying step of the roll-shaped retardation film, the web is peeled from the metal support and dried, and the amount of the residual solvent is preferably 1% by mass or less, more preferably 0.1% by mass or less, and particularly preferably 0%. ~0.01% by mass or less.

於薄膜乾燥步驟中，一般採用輥乾燥方式(使料片交互通過上下配置的多數輥而乾燥的方式)或拉幅機方式的邊輸送料片邊進行乾燥的方式。In the film drying step, a method of drying by a roll drying method (a method in which a web is alternately dried by a plurality of rolls arranged one above the other) or a side of a tenter type conveying sheet is generally used.

為了製作本發明的相位差薄膜中，較佳係在從金屬支持體剝離後立即的料片之殘留溶劑量多時，於輸送方向(＝長度方向)中拉伸，再藉由以夾具等抓住料片的兩端之拉幅機方式，於寬度方向中進行拉伸。In order to produce the retardation film of the present invention, it is preferred to stretch in the transport direction (=length direction) when the amount of residual solvent of the tablet immediately after peeling from the metal support is large, and then grasp by a jig or the like. The tenter method of the two ends of the web is stretched in the width direction.

拉伸操作係可分割成多階段來實施，可在輸送方向或寬度方向實施一軸拉伸，或在輸送方向及寬度方向中實施二軸拉伸。又，進行拉伸時係可同時地進行拉伸，也可階段地實施。於此情況下，所謂的階段，例如亦可能依順序進行不同拉伸方向的拉伸，也可能將同一方向的拉伸分割成多階段，且將不同方向的拉伸施加於其任一個階段。The stretching operation can be carried out in a plurality of stages, and one-axis stretching can be performed in the conveying direction or the width direction, or biaxial stretching can be performed in the conveying direction and the width direction. Further, when stretching is carried out, stretching may be carried out simultaneously or in stages. In this case, the so-called stage may, for example, be stretched in different stretching directions in order, or may be divided into a plurality of stages in the same direction, and stretching in different directions may be applied to any one of the stages.

較佳的拉伸倍率為1.05~2倍，更佳為1.1~1.5倍。拉伸時可在輸送方向或寬度方向中使收縮，收縮時係可進 行到0.8~0.99，較佳進行到0.9~0.99。較佳為輸送方向的拉伸及寬度方向的拉伸或收縮係使面積成為1.12倍~1.44倍，更佳係成為1.15倍~1.32倍。此係可藉由輸送方向的拉伸倍率×寬度方向的拉伸倍率來求得。The preferred draw ratio is 1.05 to 2 times, more preferably 1.1 to 1.5 times. When stretching, it can be contracted in the conveying direction or the width direction. The line is from 0.8 to 0.99, preferably from 0.9 to 0.99. It is preferable that the stretching in the conveying direction and the stretching or shrinking in the width direction make the area 1.12 times to 1.44 times, more preferably 1.15 times to 1.32 times. This can be obtained by the stretching ratio in the conveying direction × the stretching ratio in the width direction.

又，本發明中的所謂的「拉伸方向」，通常使用進行拉伸操作時直接施加拉伸應力的方向之意思，但於多階段地二軸拉伸時，亦使用最終的拉伸倍率成為大者(即通常為遲相軸的方向)之意思。In the "stretching direction" in the present invention, the direction in which the tensile stress is directly applied during the stretching operation is generally used. However, in the case of biaxial stretching in a plurality of stages, the final stretching ratio is also used. The meaning of the larger one (that is, the direction of the axis of the late phase).

拉伸係特別在基材的玻璃轉移點±10℃左右的範圍，以1.1倍~1.5倍左右在輸送方向或順方向中拉伸，或者將由溶液流延所製作的薄膜，於殘留溶劑量為2~100質量%左右殘留的狀態下，在輸送方向或寬度方向拉伸1.1~1.7倍左右，而可進行所欲的遲滯值範圍。The stretching system is particularly stretched in the transport direction or the forward direction in a range of about 0.1 to 1.5 times in the range of about ±10 ° C of the glass transition point of the substrate, or the film produced by casting the solution is in a residual solvent amount. When it is left in the range of about 2 to 100% by mass, it is stretched by about 1.1 to 1.7 times in the transport direction or the width direction, and the desired hysteresis value range can be performed.

(第2相位差層)(2nd phase difference layer)

作為本發明的第2相位差層所用的基材材料，較佳為製造容易且光學透明等，特佳為透明樹脂薄膜。The base material used for the second retardation layer of the present invention is preferably easy to manufacture and optically transparent, and is particularly preferably a transparent resin film.

本發明中所言的透明係指可見光的透過率60%以上，較佳為80%以上，特佳為90%以上。The term "transparent" as used in the present invention means that the transmittance of visible light is 60% or more, preferably 80% or more, and particularly preferably 90% or more.

只要具有上述性質則沒有特別的限定，例如可舉出纖維素二乙酸酯、纖維素三乙酸酯、纖維素乙酸酯丙酸酯、纖維素乙酸酯丁酸酯等的纖維素酯系樹脂、聚酯系樹脂、聚碳酸酯系樹脂、聚芳酯系樹脂、聚碸(亦包含聚醚碸)系樹脂、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等的聚 酯樹脂、聚乙烯樹脂、聚丙烯樹脂、賽珞玢、聚偏二氯乙烯樹脂、聚乙烯醇樹脂、乙烯－乙烯醇樹脂、間規聚苯乙烯系樹脂、原冰片烯系樹脂、聚甲基戊烯樹脂、聚醚酮樹脂、聚醚酮醯亞胺樹脂、聚醯胺樹脂、氟樹脂、耐隆填充聚甲基丙烯酸甲酯樹脂、丙烯酸樹脂等。其中，較佳為使用原冰片烯系樹脂及纖維素酯系樹脂。The above properties are not particularly limited, and examples thereof include cellulose esters such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, and cellulose acetate butyrate. Resin, polyester resin, polycarbonate resin, polyarylate resin, polyfluorene (also including polyether oxime) resin, polyethylene terephthalate, polyethylene naphthalate, etc. Gather Ester resin, polyethylene resin, polypropylene resin, cellophane, polyvinylidene chloride resin, polyvinyl alcohol resin, ethylene-vinyl alcohol resin, syndiotactic polystyrene resin, raw borneol resin, polymethyl A pentene resin, a polyether ketone resin, a polyether ketone imine resin, a polyamide resin, a fluororesin, a nylon-filled polymethyl methacrylate resin, an acrylic resin, or the like. Among them, it is preferred to use a norbornene-based resin and a cellulose ester-based resin.

本發明所較佳使用的原冰片烯系樹脂，係具有原冰片烯構造的非晶性聚聚烯烴，例如三石油化學(股)製的APO或日本ZEON(股)製的ZEONEX、JSR(股)製的ARTON等。The norbornene-based resin preferably used in the present invention is an amorphous polyolefin having a structure of a norbornene, for example, three APO manufactured by Petrochemical Co., Ltd., ZEONEX manufactured by Japan ZEON Co., Ltd., ARTON manufactured by JSR Co., Ltd., etc.

作為本發明的相位差層之較佳的纖維素酯系樹脂，較佳為纖維素酯的纖維素乙酸酯、纖維素乙酸酯丁酸酯、纖維素乙酸酯丙酸酯、纖維素乙酸酯丁酸酯，其中較宜使用纖維素乙酸酯、纖維素乙酸酯丙酸酯。此等樹脂較佳為藉由熔融流延製膜或溶液流延製膜使薄膜化。Preferred cellulose ester-based resins as the retardation layer of the present invention are preferably cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cellulose. Acetate butyrate, of which cellulose acetate, cellulose acetate propionate is preferably used. These resins are preferably formed into a film by melt casting film formation or solution casting film formation.

〈纖維素酯〉Cellulose ester

詳細說明本發明的第2相位差層所適用的纖維素酯。The cellulose ester to which the second retardation layer of the present invention is applied will be described in detail.

本發明的第2相位差層所用的纖維素酯，較宜使用碳數2~22左右的脂肪族羧酸酯或芳香族羧酸酯或脂肪族羧酸酯與芳香族羧酸酯的混合酯，特佳為纖維素的低級脂肪酸酯。纖維素的低級脂肪酸酯中之低級脂肪酸係意味碳原子數6以下的脂肪酸。具體地，纖維素乙酸酯、纖維素丙酸酯、纖維素丁酸酯、纖維素乙酸酯苯二甲酸酯等，或如 特開平10－45804號公報、同8－231761號公報、美國專利第2,319,052號等中記載的纖維素乙酸酯丙酸酯、纖維素乙酸酯丁酸酯等的混合脂肪酸酯。於上述記載之中，特佳使用的纖維素之低級脂肪酸酯係纖維素乙酸酯丙酸酯。The cellulose ester used in the second retardation layer of the present invention is preferably an aliphatic carboxylic acid ester or an aromatic carboxylic acid ester having a carbon number of 2 to 22 or a mixed ester of an aliphatic carboxylic acid ester and an aromatic carboxylic acid ester. Particularly preferred is a lower fatty acid ester of cellulose. The lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms. Specifically, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate phthalate, etc., or as A mixed fatty acid ester such as cellulose acetate propionate or cellulose acetate butyrate described in Japanese Patent No. 2,319,052, and the like. Among the above descriptions, a cellulose lower fatty acid ester which is particularly preferably used is cellulose acetate propionate.

該纖維素酯係具有碳原子數2~22的醯基當作取代基，以乙醯基的取代度當作X，以丙醯基的取代度當作Y時，為同時滿足下述式1及2的纖維素酯。The cellulose ester has a fluorenyl group having 2 to 22 carbon atoms as a substituent, and the degree of substitution of the acetyl group is regarded as X, and when the degree of substitution of the fluorenyl group is regarded as Y, the following formula 1 is satisfied. And 2 cellulose esters.

式1 2.00≦X＋Y≦2.60 式2 0.10≦Y≦1.00Equation 1 2.00≦X+Y≦2.60 Equation 2 0.10≦Y≦1.00

其中，較佳為2.30≦X＋Y≦2.55，更佳為2.40≦X＋Y≦2.55。又，較佳為050≦Y≦0.90，更佳為0.70≦Y≦0.90。Among them, it is preferably 2.30 ≦ X + Y ≦ 2.55, more preferably 2.40 ≦ X + Y ≦ 2.55. Further, it is preferably 050 ≦ Y ≦ 0.90, more preferably 0.70 ≦ Y ≦ 0.90.

醯基所不取代的部分通常係當作羥基存在著。此等可藉由眾所周知的方法來合成。又，此等醯基取代度係可依據ASTM－D817－96規定的方法來測定。The unsubstituted portion of the thiol group is usually present as a hydroxyl group. These can be synthesized by well-known methods. Further, the degree of substitution of the thiol groups can be determined in accordance with the method specified in ASTM-D817-96.

纖維素酯係可單獨或混合使用以棉籽絨、木材漿粕、洋麻等當作原料所合成的纖維素酯。特佳為單獨或混合使用由棉籽絨(以下亦僅稱棉絨)、木材漿粕所合成的纖維素酯。The cellulose ester can be used alone or in combination as a cellulose ester synthesized from cotton linters, wood pulp, kenaf or the like as a raw material. It is particularly preferred to use a cellulose ester synthesized from cotton linter (hereinafter also referred to as lint) and wood pulp alone or in combination.

又，由此等所得之纖維素酯係可各自以任意比例混合使用。此等纖維素酯，當醯化劑為酸酐(醋酸酐、丙酸酐、丁酸酐)時，係使用如醋酸的有機酸或二氯甲烷等的有機溶劑，使用如硫酸的質子性觸媒，藉由常用方法使纖維素原料反應而得。Further, the cellulose esters obtained by the above may be used in combination at any ratio. When the oxime agent is an acid anhydride (acetic anhydride, propionic anhydride, butyric anhydride), an organic solvent such as acetic acid or an organic solvent such as dichloromethane is used, and a protonic catalyst such as sulfuric acid is used. It is obtained by reacting a cellulose raw material by a usual method.

於乙醯纖維素時，若要提高乙醯化率，則必須延長乙醯化反應的時間。但是，反應時間若太長，則分解係同時進行，發生聚合物鏈的斷裂或乙醯基的分解等，招致不宜的結果。因此，為了提高乙醯化度，將分解抑制在某一程度，必須將反應時間設定在某一範圍。反應條件為各式各樣，因反應裝置或設備等的條件而有大幅變化，故不能適切地以反應時間來規定。隨著聚合物的分解之進展，分子量分布漸漸變廣，故於纖維素酯的情況中，分解的程度係可藉由通常所用的重量平均分子量(Mw)/數量平均分子量(Mn)之值來規定。即，於纖維素三乙酸酯的乙醯化之過程，為了不會太長而過度進行分解，且在乙醯化中為了進行充分時間的乙醯化反應，作為反應程度的一個指標可以使用重量平均分子量(Mw)/數量平均分子量(Mn)之值。In the case of acetaminophen cellulose, in order to increase the acetamidine rate, it is necessary to prolong the time of the acetamidine reaction. However, if the reaction time is too long, the decomposition system proceeds at the same time, and the polymer chain is broken or the acetamino group is decomposed, resulting in unfavorable results. Therefore, in order to increase the degree of acetylation, the decomposition is suppressed to a certain extent, and the reaction time must be set to a certain range. The reaction conditions are various and vary greatly depending on the conditions of the reaction apparatus or equipment, and therefore cannot be appropriately determined by the reaction time. As the decomposition of the polymer progresses, the molecular weight distribution gradually becomes wider, so in the case of the cellulose ester, the degree of decomposition can be obtained by the value of the weight average molecular weight (Mw) / number average molecular weight (Mn) which is usually used. Provisions. That is, in the process of acetylation of cellulose triacetate, it is excessively decomposed in order to prevent it from being too long, and in order to carry out a sufficient time of acetylation reaction in acetamidine, it can be used as an indicator of the degree of reaction. The value of the weight average molecular weight (Mw) / number average molecular weight (Mn).

本發明中所用的纖維素酯之重量平均分子量(Mw)與數量平均分子量(Mn)的比Mw/Mn之值較佳為1.4~3.0。再者，於本發明中，纖維素酯薄膜可含有Mw/Mn的值為1.4~3.0的纖維素酯當作材料，薄膜中所含有的纖維素酯(較佳為纖維素三乙酸酯或纖維素乙酸酯丙酸酯)全體之Mw/Mn的值更佳為在1.4~3.0的範圍。於纖維素酯的合成過程中，低於1.4係困難，藉由凝膠過濾等來分級，可得到分子量一致的纖維素酯。然而該方法係顯著花費成本。又，若為3.0以下，則容易維持平面性而較宜。再者，更佳為1.7~2.2。The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the cellulose ester used in the present invention Mw/Mn is preferably from 1.4 to 3.0. Furthermore, in the present invention, the cellulose ester film may contain a cellulose ester having a Mw/Mn value of 1.4 to 3.0 as a material, and a cellulose ester (preferably cellulose triacetate or The value of Mw/Mn of the cellulose acetate propionate is preferably in the range of 1.4 to 3.0. In the synthesis of cellulose esters, it is difficult to classify by lower than 1.4, and it is classified by gel filtration or the like to obtain a cellulose ester having a uniform molecular weight. However, this method is a significant cost. Moreover, when it is 3.0 or less, it is easy to maintain planarity, and it is preferable. Furthermore, it is preferably 1.7 to 2.2.

本發明中所用的纖維素酯之分子量以數量平均分子量(Mn)計較佳為使用80000~200000者，更佳為100000~200000者，特佳為150000~200000。The molecular weight of the cellulose ester used in the present invention is preferably from 80,000 to 200,000, more preferably from 100,000 to 200,000, and particularly preferably from 150,000 to 200,000, in terms of the number average molecular weight (Mn).

纖維素酯的平均分子量及分子量分布係可藉由使用高速液體層析術的眾所周知之方法來測定。使用它可算出數量平均分子量、重量平均分子量，計算其比(Mw/Mn)。The average molecular weight and molecular weight distribution of the cellulose ester can be determined by a well-known method using high speed liquid chromatography. Using this, the number average molecular weight and the weight average molecular weight were calculated, and the ratio (Mw/Mn) was calculated.

測定條件係如以下。The measurement conditions are as follows.

溶劑：二氯甲烷管柱：Shodex K806、K805、K803G(連接3支昭和電工(股)製的來使用)管柱溫度：25℃試料濃度：0.1質量%偵檢器：RI Model 504(GL科學公司製)泵：L6000(日立製作所(股)製)流量：1.0ml/min 校正曲線：使用標準聚苯乙烯STK standard聚苯乙烯(東曹(股)製)Mw＝1000000~500為止的13樣品之校正曲線。13個樣品較佳為以大致等間隔而得。Solvent: Dichloromethane column: Shodex K806, K805, K803G (connected to 3 Showa Denko (shares) for use) Column temperature: 25 °C Sample concentration: 0.1% by mass Detector: RI Model 504 (GL Science Company system) Pump: L6000 (Hitachi Manufacturing Co., Ltd. system) Flow: 1.0ml/min Calibration curve: A calibration curve of 13 samples up to standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) Mw = 1000000 to 500. The 13 samples are preferably obtained at substantially equal intervals.

纖維素酯的製造法係可藉由特開平10－45804號公報記載的方法來獲得。The method for producing a cellulose ester can be obtained by the method described in JP-A-10-45804.

又，纖維素酯係受到纖維素酯中的微量金屬成分所影響。茲認為此等係與製程中所使用的水有關係，可成為不溶性核的成分係愈少愈佳，鐵、鈣、鎂等的金屬離子藉由與具有含著有機酸性基之可能性的聚合物分解物等形成鹽 ，會形成不溶物，故其愈少愈佳。鐵(Fe)成分較佳為1ppm以下。鈣(Ca)成分多含於地下水或河川的水等中，其若多則成為硬水，作為飲用水亦不適當，與羧酸或磺酸等的酸性成分和許多的配位子容易形成配位化合物，即錯合物，形成許多之來自不溶鈣的浮渣(不溶性的沈澱、混濁)。Further, the cellulose ester is affected by a trace amount of a metal component in the cellulose ester. It is considered that these systems are related to the water used in the process, and the fewer the components that can become insoluble cores, the better the metal ions of iron, calcium, magnesium, etc., and the polymerization with the possibility of containing organic acidic groups. Decomposition product, etc. form salt , will form insoluble matter, so the less it is better. The iron (Fe) component is preferably 1 ppm or less. Calcium (Ca) is contained in groundwater, river water, etc., and if it is many, it is hard water, and it is not suitable as drinking water. It is easy to form a coordination with acidic components such as carboxylic acid or sulfonic acid and many ligands. The compound, a complex, forms a number of scum (insoluble precipitates, turbidity) from insoluble calcium.

鈣(Ca)成分為60ppm以下，較佳為0~30ppm。鎂(Mg)成分同樣地若過多則生成不溶分，故較佳為0~70ppm，特佳為0~20ppm。鐵(Fe)分的含量、鈣(Ca)分含量、鎂(Mg)分含量等的金屬成分，係可藉由與絕對乾燥的纖維素酯，以微蒸煮濕式分解裝置(硫硝酸分解)、鹼熔融進行前處理後，使用ICP－AES(感應耦合電漿發光分光分析裝置)進行分析而求得。The calcium (Ca) component is 60 ppm or less, preferably 0 to 30 ppm. When the magnesium (Mg) component is too large, an insoluble component is formed, so that it is preferably 0 to 70 ppm, particularly preferably 0 to 20 ppm. The metal component such as the content of iron (Fe), the content of calcium (Ca), and the content of magnesium (Mg) can be micro-cooked by a wet decomposition apparatus (sulfuric acid decomposition) with an absolutely dried cellulose ester. The alkali fusion was pretreated, and then analyzed by ICP-AES (inductively coupled plasma luminescence spectroscopic analyzer).

本發明所用的纖維素酯薄膜之折射率較宜使用550nm為1.45~1.60者。薄膜的折射率之測定方法係使用阿貝折射率計，根據日本工業規格JIS K 7105來測定。The refractive index of the cellulose ester film used in the present invention is preferably from 1.45 to 1.60 at 550 nm. The method of measuring the refractive index of the film was measured using an Abbe refractometer according to Japanese Industrial Standard JIS K 7105.

(添加劑)(additive)

可於纖維素酯薄膜中含有可塑劑或紫外線吸收劑、抗氧化劑、消光劑等的添加劑。An additive such as a plasticizer or an ultraviolet absorber, an antioxidant, a matting agent, or the like may be contained in the cellulose ester film.

如前述地，本發明的第2相位差層之面內遲滯值Ro為5<Ro≦100nm，且厚度方向的遲滯值Rth為100<Rth≦200nm。As described above, the in-plane hysteresis value Ro of the second retardation layer of the present invention is 5 < Ro≦ 100 nm, and the hysteresis value Rth in the thickness direction is 100 < Rth ≦ 200 nm.

為了成為上述數值範圍，第2相位差層若為纖維素酯 薄膜，則較佳為在熔融製膜之後進行二軸拉伸，或在溶液製膜之後進行一軸或二軸拉伸。於與輸送方向正交的方向進行拉伸時，較佳為精密控制拉伸溫度與拉伸倍率的平衡，在該相位差層的兩側獨立地控制拉伸部分(拉幅機的夾具等)。此等係可藉由相對於夾具位置和夾具的應力，調整拉伸溫度和拉伸倍率來達成。In order to be in the above numerical range, the second retardation layer is a cellulose ester. The film is preferably subjected to biaxial stretching after melt film formation or one-axis or two-axis stretching after solution film formation. When stretching in a direction orthogonal to the conveying direction, it is preferable to precisely control the balance between the stretching temperature and the stretching ratio, and independently control the stretching portion on both sides of the retardation layer (clamp of the tenter, etc.) . These can be achieved by adjusting the stretching temperature and the stretching ratio with respect to the clamp position and the stress of the jig.

〈其它添加劑〉<Other Additives>

本發明的第1~第3相位差層係可含有下述所列的可塑劑、紫外線吸收劑、微粒子等的添加劑。The first to third retardation layers of the present invention may contain additives such as a plasticizer, an ultraviolet absorber, and fine particles listed below.

本發明的相位差層較佳為含有如下述的可塑劑。作為可塑劑，例如可較佳地使用磷酸酯系可塑劑、苯二甲酸酯系可塑劑、偏苯三酸酯系可塑劑、均苯四酸系可塑劑、乙醇酸酯系可塑劑、檸檬酸酯系可塑劑、聚酯系可塑劑、多元醇酯系可塑劑等。The retardation layer of the present invention preferably contains a plasticizer as described below. As the plasticizer, for example, a phosphate-based plasticizer, a phthalate-based plasticizer, a trimellitate-based plasticizer, a pyromellitic acid-based plasticizer, a glycolate-based plasticizer, or a lemon can be preferably used. An acid ester type plasticizer, a polyester type plasticizer, a polyol ester type plasticizer, and the like.

於磷酸酯系可塑劑中，可較佳地使用磷酸三苯酯、磷酸三甲苯酯、磷酸甲苯基二苯基酯、磷酸辛基二苯基酯、磷酸二苯基聯苯酯、磷酸三辛酯、磷酸三丁酯等；於苯二甲酸酯系可塑劑中，可較佳地使用苯二甲酸二乙酯、苯二甲酸二甲氧基乙基酯、苯二甲酸二甲酯、苯二甲酸二辛酯、苯二甲酸二丁酯、苯二甲酸二－2－乙基己酯、苯二甲酸丁基苄酯、苯二甲酸二苯酯、苯二甲酸二環己酯等；於偏苯三酸系可塑劑中，可較佳地使用偏苯三酸三丁酯、偏苯三酸三苯酯、偏苯三酸三乙酯等；於均苯四酸酯系可塑劑 中，可較佳地使用均苯四酸四丁酯、均苯四酸四苯酯、均苯四酸四乙酯等；於乙醇酸酯系可塑劑中，可較佳地使用甘油三乙酸酯、甘油三丁酯、乙基苯二甲醯基乙基乙醇酸酯、甲基苯二甲醯基乙基乙醇酸酯、丁基苯二甲醯基丁基乙醇酸酯等；於檸檬酸酯系可塑劑中，可較佳地使用檸檬酸三乙酯、檸檬酸三正丁酯、檸檬酸乙醯基三乙酯、檸檬酸乙醯基三正丁酯、檸檬酸乙醯基三正(2－乙基己基)酯等。於其它的羧酸酯之例中，包含油酸丁酯、蓖麻酸甲基乙醯酯、癸二酸二丁酯、各種的偏苯三酸酯。Among the phosphate ester plasticizers, triphenyl phosphate, tricresyl phosphate, tolyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate can be preferably used. Ester, tributyl phosphate, etc.; in the phthalate plasticizer, diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, benzene can be preferably used. Dioctyl dicarboxylate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, diphenyl phthalate, dicyclohexyl phthalate, etc.; Among the trimellitic acid-based plasticizers, tributyl trimellitate, triphenyl trimellitate, triethyl trimellitate, and the like; and pyromellitate plasticizers can be preferably used. Among them, tetrabutyl pyromelliate, tetraphenyl pyromelliate, tetraethyl pyromelliate and the like can be preferably used; in the glycolate plasticizer, triacetin can be preferably used. Ester, tributyl glyceride, ethyl phthalic acid ethyl glycolate, methyl phthalic acid ethyl glycolate, butyl phthalic acid butyl glycolate, etc.; Among the ester-based plasticizers, triethyl citrate, tri-n-butyl citrate, ethyl citrate triethyl citrate, acetyl citrate tri-n-butyl acrylate, citrate-based tri-n-butyl acrylate can be preferably used. (2-ethylhexyl) ester and the like. Examples of other carboxylic acid esters include butyl oleate, methyl decyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters.

作為聚酯系可塑劑，可使用脂肪族二元酸、脂環式二元酸、芳香族二元酸等的二元酸與二醇共聚合聚合物。作為脂肪族二元酸，並沒有特別的限定，可使用己二酸、癸二酸、苯二甲酸、對苯二甲酸、1,4－環己基二羧酸等。作為二醇，可使用乙二醇、二乙二醇、1,3－丙二醇、1,2－丙二醇、1,4－丁二醇、1,3－丁二醇、1,2－丁二醇等。此等二元酸及二醇可各自單獨使用，也可2種以上混合使用。As the polyester-based plasticizer, a dibasic acid such as an aliphatic dibasic acid, an alicyclic dibasic acid or an aromatic dibasic acid and a diol copolymerized polymer can be used. The aliphatic dibasic acid is not particularly limited, and adipic acid, sebacic acid, phthalic acid, terephthalic acid, 1,4-cyclohexyl dicarboxylic acid or the like can be used. As the diol, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol can be used. Wait. These dibasic acids and diols may be used alone or in combination of two or more.

多元醇酯系可塑劑係由2價以上的脂肪族多元醇與單羧酸的酯所構成。作為較佳的多元醇之例，例如可舉出如以下者，但本發明不受此等所限定。可舉出核糖醇、***糖醇、乙二醇、二乙二醇、三乙二醇、四乙二醇、1,2－丙二醇、1,3－丙二醇、二丙二醇、三丙二醇、1,2－丁二醇、1,3－丁二醇、1,4－丁二醇、二丁二醇、1,2,4－丁三醇、1,5－戊二醇、1,6－己二醇、己三醇、2－正丁基－2－乙基－1,3－丙二醇、半乳糖醇、甘露糖醇、3－甲基戊烷－1,3,5－三醇、 頻哪醇、山梨糖醇、三羥甲基丙烷、三羥甲基乙烷、木糖醇等。特別地，較佳為三乙二醇、四乙二醇、二丙二醇、三丙二醇、山梨糖醇、三羥甲基丙烷、木糖醇。多元醇酯所用的單羧酸係沒有特別的限制，可使用眾所周知的脂肪族單羧酸、脂環族單羧酸、芳香族單羧酸等。若使用脂環族單羧酸、芳香族單羧酸，從提高透濕性、保留性之點來看係較宜。作為較佳的單羧酸之例，可舉出如以下者，但本發明不受此等所限定。作為脂肪族單羧酸，可較佳地使用具有碳數1~32的直鏈或側鏈之脂肪酸，更佳為碳數1~20，特佳為碳數1~10。若含有醋酸，由於與纖維素酯的相溶性增大而較宜，亦較佳為混合使用醋酸與其它單羧酸。作為較佳的脂肪族單羧酸，可舉出醋酸、丙酸、丁酸、戊酸、己酸、庚酸、辛酸、壬酸、癸酸、2－乙基－己烷羧酸、十一酸、月桂酸、十三酸、肉豆蔻酸、十五酸、棕櫚酸、十七酸、硬脂酸、十九酸、花生酸、山萮酸、廿四酸、蠟酸、廿七酸、褐煤酸、三十酸、三十二酸等的飽和脂肪酸，十一烯酸、油酸、山梨酸、亞油酸、亞麻酸、花生酸等的不飽和脂肪酸等。作為較佳的脂環族單羧酸之例，可舉出環戊烷羧酸、環己烷羧酸、環辛烷羧酸、或此等的衍生物。作為較佳的芳香族單羧酸之例，可舉出在苯甲酸、甲苯酸等的苯甲酸之苯環導入有烷基者、聯苯基羧酸、萘羧酸、萘滿羧酸等之具有2個以上苯環的芳香族單羧酸、或此等的衍生物。特佳為苯甲酸。多元醇酯的分子量係沒有特別的限制，分子量較佳為在300~1500的範圍， 更佳為在350~750的範圍。從保留性提高之點來看，大者為佳，從透濕性、與纖維素酯的相溶性之點來看，小者為佳。The polyol ester-based plasticizer is composed of an ester of a divalent or higher aliphatic polyol and a monocarboxylic acid. Examples of preferred polyhydric alcohols include, for example, the following, but the present invention is not limited thereto. Examples thereof include ribitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2 -butanediol, 1,3-butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexane Alcohol, hexanetriol, 2-n-butyl-2-ethyl-1,3-propanediol, galactitol, mannitol, 3-methylpentane-1,3,5-triol, Pinacol, sorbitol, trimethylolpropane, trimethylolethane, xylitol, and the like. Particularly, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferred. The monocarboxylic acid to be used for the polyol ester is not particularly limited, and a well-known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid or the like can be used. When an alicyclic monocarboxylic acid or an aromatic monocarboxylic acid is used, it is preferable from the viewpoint of improving moisture permeability and retention. Examples of preferred monocarboxylic acids include the following, but the present invention is not limited thereto. As the aliphatic monocarboxylic acid, a fatty acid having a linear or side chain having 1 to 32 carbon atoms can be preferably used, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms. If acetic acid is contained, it is preferred to increase the compatibility with the cellulose ester, and it is preferred to use acetic acid together with other monocarboxylic acids. Preferred examples of the aliphatic monocarboxylic acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, 2-ethyl-hexanecarboxylic acid, and eleven. Acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nineteen acid, arachidic acid, behenic acid, amaronic acid, wax acid, succinic acid, A saturated fatty acid such as montanic acid, triacyl acid or tridecanoic acid, or an unsaturated fatty acid such as undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid or arachidic acid. Examples of preferred alicyclic monocarboxylic acids include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and the like. Examples of the preferred aromatic monocarboxylic acid include an alkyl group, a biphenyl carboxylic acid, a naphthalene carboxylic acid, a naphthyl carboxylic acid, and the like, which are introduced into a benzene ring of benzoic acid such as benzoic acid or toluic acid. An aromatic monocarboxylic acid having two or more benzene rings or a derivative thereof. Particularly preferred is benzoic acid. The molecular weight of the polyol ester is not particularly limited, and the molecular weight is preferably in the range of 300 to 1,500. More preferably in the range of 350 to 750. From the point of view of improvement in retention, the larger one is preferable, and the small one is preferable from the viewpoint of moisture permeability and compatibility with cellulose ester.

本發明所用的多元醇酯所用的羧酸可為一種類，也可為2種以上的混合。又，多元醇中的OH基可皆被羧酸所酯化，也可一部分照OH基原樣地殘留。The carboxylic acid used in the polyol ester used in the present invention may be one type or a mixture of two or more types. Further, the OH group in the polyol may be esterified with a carboxylic acid, or a part of the OH group may remain as it is.

此等可塑劑係單獨或併用為佳。These plasticizers are preferably used singly or in combination.

此等可塑劑的使用量，從薄膜性能、加工性等之點來看，對於纖維素酯而言較佳為1~20質量%，特佳為3~13質量%。The amount of the plasticizer to be used is preferably from 1 to 20% by mass, particularly preferably from 3 to 13% by mass, based on the properties of the film, the processability, and the like.

本發明中所可使用的紫外線吸收劑係以吸收400nm以下的紫外線，提高耐久性為目的，特別地波長370nm的透過率為10%以下，較佳為5%以下，更佳為2%以下。The ultraviolet absorber which can be used in the present invention is intended to absorb ultraviolet rays of 400 nm or less and to improve durability. Specifically, the transmittance at a wavelength of 370 nm is 10% or less, preferably 5% or less, more preferably 2% or less.

本發明所用的紫外線吸收劑係沒有特別的限定，例如可舉出氧基二苯基酮系化合物、苯并***系化合物、水楊酸酯系化合物、二苯基酮系化合物、氰基丙烯酸酯系化合物、三系化合物、鎳錯鹽系化合物、無機粉體等。亦可為高分子型的紫外線吸收劑。The ultraviolet absorber to be used in the present invention is not particularly limited, and examples thereof include an oxydiphenyl ketone compound, a benzotriazole compound, a salicylate compound, a diphenyl ketone compound, and a cyanoacrylate. Ester compound, three A compound, a nickel salt-salt compound, an inorganic powder, or the like. It can also be a polymeric UV absorber.

於本發明所用的相位差層中，較佳為使用微粒子。微粒子可使用無機化合物或有機化合物中任一者。作為無機化合物之例，可舉出二氧化矽、二氧化鈦、氧化鋁、氧化鋯、碳酸鈣、碳酸鈣、滑石、黏土、煅燒高嶺土、煅燒矽酸鈣、水合矽酸鈣、矽酸鋁、矽酸鎂及磷酸鈣。從濁度變低之點來看，微粒子較佳為含矽者，特佳為二氧化矽。In the phase difference layer used in the present invention, fine particles are preferably used. As the fine particles, either an inorganic compound or an organic compound can be used. Examples of the inorganic compound include cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium citrate, calcium citrate hydrate, aluminum citrate, and citric acid. Magnesium and calcium phosphate. From the point of view that the turbidity is low, the fine particles are preferably bismuth-containing, and particularly preferably cerium oxide.

微粒子的一次粒子之平均粒徑較佳為5~50nm，更佳為7~20nm。此等較佳為主要當作粒徑0.05~0.3μm的2次凝聚物被含有。纖維素酯薄膜中的此等微粒子之含量較佳為0.05~1質量%，特佳為0.1~0.5質量%。於共流延法的多層構成之纖維素酯薄膜的情況，較佳為表面含有該添加量的微粒子。The average particle diameter of the primary particles of the fine particles is preferably 5 to 50 nm, more preferably 7 to 20 nm. These are preferably mainly contained as secondary aggregates having a particle diameter of 0.05 to 0.3 μm. The content of such fine particles in the cellulose ester film is preferably from 0.05 to 1% by mass, particularly preferably from 0.1 to 0.5% by mass. In the case of the cellulose ester film having a multilayer structure of the co-casting method, it is preferred that the surface contains the added amount of fine particles.

二氧化矽的微粒子例如可使用以Aerosil R972、R972V、R974、R812、200、200V、300、R202、OX50、TT600(以上為日本Aerosil(股)製)的商品名所市售者。As the fine particles of cerium oxide, for example, those commercially available under the trade names of Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, and TT600 (all manufactured by Japan Aerosil Co., Ltd.) can be used.

氧化鋯的微粒子例如可使用以Aerosil R976及R811(以上為日本Aerosil(股)製)的商品名所市售者。As the fine particles of zirconia, for example, those commercially available under the trade names of Aerosil R976 and R811 (all manufactured by Japan Aerosil Co., Ltd.) can be used.

作為聚合物之例，可舉出聚矽氧樹脂、氟樹脂及丙烯酸樹脂。較佳為聚矽氧樹脂，特佳為具有三次元的網狀構造者，例如可使用以Tosperal 103、同105、同108、同120、同145、同3120及同240(以上為東芝聚矽氧(股)製)的商品名所市售者。Examples of the polymer include a polyfluorene oxide resin, a fluororesin, and an acrylic resin. Preferably, it is a polyoxyxylene resin, particularly preferably a three-dimensional network structure, for example, Tosperal 103, the same 105, the same 108, the same 120, the same 145, the same 3120, and the same 240 (the above is Toshiba Poly The trade name of the product name of the oxygen (stock) system.

於此等之中，特佳為使用Aerosil 200V、Aerosil R972V，因為將纖維素酯薄膜的濁度保持低，同時降低摩擦係數的效果大。Among them, it is particularly preferable to use Aerosil 200V and Aerosil R972V because the turbidity of the cellulose ester film is kept low and the effect of lowering the friction coefficient is large.

(第3相位差層)(3rd phase difference layer)

本發明中的第3相位差層係面內及厚度方向的遲滯值為0≦Ro≦5nm、且0≦| Rth |<40nm的範圍之相位差薄膜 ，較佳為當作IPS模式型液晶顯示裝置中所用的相位差薄膜。0≦| Rth |<10nm的範圍為特佳。In the third phase difference layer of the present invention, the retardation value in the in-plane and thickness direction is 0 ≦ Ro ≦ 5 nm, and the retardation film in the range of 0 ≦ | Rth | < 40 nm Preferably, it is used as a retardation film used in an IPS mode liquid crystal display device. 0≦| Rth |<10nm is particularly good.

第3相位差層較佳為纖維素酯薄膜，其含有當作偏光板保護薄膜的皂化適合性等加工性優異之纖維素酯、及對於拉伸方向顯示負的配向雙折射性之重量平均分子量為500以上30000以下的丙烯酸聚合物。該纖維素酯薄膜可較佳地使用與前述第2相位差層所用的纖維素酯薄膜同樣的材料、同樣的製造方法。The third retardation layer is preferably a cellulose ester film containing a cellulose ester excellent in workability such as saponification suitability as a protective film for a polarizing plate, and a weight average molecular weight exhibiting negative birefringence in the direction of stretching. It is an acrylic polymer of 500 or more and 30,000 or less. As the cellulose ester film, the same material and the same production method as those of the cellulose ester film used in the second retardation layer can be preferably used.

又，該丙烯酸聚合物較佳為側鏈具有芳香環的丙烯酸聚合物或側鏈具有環己基的丙烯酸聚合物。Further, the acrylic polymer is preferably an acrylic polymer having an aromatic ring in a side chain or an acrylic polymer having a cyclohexyl group in a side chain.

〈丙烯酸聚合物〉<Acrylic Polymer>

該聚合物的重量平均分子量為500以上30000以下，藉由控制該聚合物的組成，可使纖維素酯與該聚合物的相溶性成為良好。The polymer has a weight average molecular weight of 500 or more and 30,000 or less, and by controlling the composition of the polymer, the compatibility of the cellulose ester with the polymer can be improved.

特別地，於丙烯酸聚合物、側鏈具有芳香環的丙烯酸聚合物或側鏈具有環己基的丙烯酸聚合物中，較佳係重量平均分子量為500以上10000以下者，除了上述，還顯示製膜後的纖維素酯薄膜之透明性優異、透濕度亦極低的作為偏光板用保護薄膜之優異性能。In particular, in the acrylic polymer, an acrylic polymer having an aromatic ring in a side chain, or an acrylic polymer having a cyclohexyl group in a side chain, the weight average molecular weight is preferably 500 or more and 10,000 or less, and in addition to the above, it is also shown after film formation. The cellulose ester film is excellent in transparency as a protective film for a polarizing plate, which is excellent in transparency and extremely low in moisture permeability.

該聚合物由於重量平均分子量為500以上30000以下，故被認為係在寡聚物至低分子量聚合物之間。要合成如此的聚合物，通常的聚合中分子量之控制係困難，希望使用不使分子量太大的方法，可使分子量盡可能一致的方法 。Since the polymer has a weight average molecular weight of 500 or more and 30,000 or less, it is considered to be between the oligomer and the low molecular weight polymer. In order to synthesize such a polymer, it is difficult to control the molecular weight in the usual polymerization, and it is desirable to use a method which does not make the molecular weight too large, and the molecular weight can be made as uniform as possible. .

作為該聚合方法，可舉出使用如過氧化枯烯或第三丁基過氧化氫的過氧化物聚合引發劑之方法，比一般聚合更大量使用聚合引發劑之方法，除了聚合引發劑亦使用巰基化合物或四氯化碳等的鏈轉移劑之方法，除了聚合引發劑亦使用如苯醌或二硝基苯的聚合停止劑之方法，以及使用如特開2000－128911號或同2000－344823號公報中的具有一個硫醇基及2級羥基的化合物、或併用該化合物與有機金屬化合物的聚合觸媒的塊狀聚合之方法等，皆可在本發明中被較佳地用，特佳為該公報中記載的方法。As the polymerization method, a method of using a peroxide polymerization initiator such as cumene peroxide or t-butyl hydroperoxide, a method of using a polymerization initiator in a larger amount than usual polymerization, and a polymerization initiator are also used. A method of using a chain transfer agent such as a mercapto compound or carbon tetrachloride, in addition to a polymerization initiator, a method of using a polymerization stopper such as benzoquinone or dinitrobenzene, and a method such as JP-A-2000-128911 or 2000-344823 The method of blocking polymerization of a compound having one thiol group and a second-order hydroxyl group, or a polymerization catalyst using the compound and an organometallic compound, etc., can be preferably used in the present invention. It is the method described in this publication.

下述舉出作為構成本發明可用的聚合物之單體單位的單體，惟不受其所限定。The monomers constituting the monomer unit of the polymer usable in the present invention are exemplified below, but are not limited thereto.

作為構成將乙烯性不飽和單體聚合而得之聚合物的乙烯性不飽和單體單位：有乙烯酯，例如可舉出醋酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、戊酸乙烯酯、三甲基乙酸乙烯酯、己酸乙烯酯、癸酸乙烯酯、月桂酸乙烯酯、肉豆蔻酸乙烯酯、棕櫚酸乙烯酯、硬脂酸乙烯酯、環己烷接酸乙烯酯、辛基酸乙烯酯、甲基丙烯酸乙烯酯、巴豆酸乙烯酯、山梨酸乙烯酯、苯甲酸乙烯酯、肉桂酸乙烯酯等；丙烯酸酯，例如可舉出丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙基(i－、n－)酯、丙烯酸丁基(n－、i－、s－、t－)酯、丙烯酸戊基(n－、i－、s－)酯、丙烯酸己基(n－、i－)酯、丙烯酸庚基(n－、i－)酯、丙烯酸辛基(n－、i－)酯、丙烯酸壬基(n－、i－)酯、丙烯酸肉豆蔻基(n－、i－)酯、丙烯酸 環己酯、丙烯酸(2－乙基己基)酯、丙烯酸苄酯、丙烯酸苯乙酯、丙烯酸(ε－己內酯)、丙烯酸(2－羥乙基)酯、丙烯酸(2－羥丙基)酯、丙烯酸(3－羥丙基)酯、丙烯酸(4－羥丁基)酯、丙烯酸(2－羥丁基)酯、丙烯酸對羥甲基苯酯、丙烯酸對(2－羥乙基)苯酯等；甲基丙烯酸酯，例如可舉出將上述丙烯酸酯變成甲基丙烯酸酯者；不飽和酸，例如可舉出丙烯酸、甲基丙烯酸、馬來酸酐、巴豆酸、伊康酸等。上述單體所構成的聚合物係可為共聚物或均聚物，較佳為乙烯酯的均聚物、乙烯酯的共聚物、乙烯酯與丙烯酸或甲基丙烯酸酯的共聚物。The ethylenically unsaturated monomer unit constituting the polymer obtained by polymerizing the ethylenically unsaturated monomer: a vinyl ester, and examples thereof include vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl valerate. , trimethyl vinyl acetate, vinyl hexanoate, vinyl decanoate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexane, octyl Acid vinyl ester, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl benzoate, vinyl cinnamate, etc.; acrylate, for example, methyl acrylate, ethyl acrylate, propyl acrylate ( I-, n-) ester, butyl acrylate (n-, i-, s-, t-) ester, pentyl acrylate (n-, i-, s-) ester, hexyl acrylate (n-, i-) Ester, heptyl (n-, i-) acrylate, octyl (n-, i-) acrylate, fluorenyl (n-, i-) acrylate, myristyl (n-, i-) acrylate ,acrylic acid Cyclohexyl ester, (2-ethylhexyl) acrylate, benzyl acrylate, phenylethyl acrylate, acrylic acid (ε-caprolactone), (2-hydroxyethyl) acrylate, acrylic acid (2-hydroxypropyl) Ester, (3-hydroxypropyl) acrylate, (4-hydroxybutyl) acrylate, (2-hydroxybutyl) acrylate, p-hydroxymethyl phenyl acrylate, (2-hydroxyethyl) benzene acrylate Examples of the methacrylate include those obtained by changing the above acrylate to methacrylate; and examples of the unsaturated acid include acrylic acid, methacrylic acid, maleic anhydride, crotonic acid, and itaconic acid. The polymer composed of the above monomers may be a copolymer or a homopolymer, and is preferably a homopolymer of a vinyl ester, a copolymer of a vinyl ester, or a copolymer of a vinyl ester and an acrylic acid or a methacrylate.

於本發明中，所謂的丙烯酸聚合物(僅稱丙烯酸聚合物)，就是指不具有含芳香環或環己基的單體單位之丙烯酸或甲基丙烯酸烷基酯的均聚物或共聚物。所謂的側鏈具有芳香環的丙烯酸聚合物，就是含有必定具有芳香環的丙烯酸或甲基丙烯酸酯單體單位之丙烯酸聚合物。In the present invention, the so-called acrylic polymer (hereinafter referred to as acrylic polymer) means a homopolymer or a copolymer of acrylic acid or alkyl methacrylate which does not have a monomer unit containing an aromatic ring or a cyclohexyl group. The so-called acrylic polymer having an aromatic ring in the side chain is an acrylic polymer containing an acrylic or methacrylic monomer unit which must have an aromatic ring.

又，所謂的側鏈具有環己基的丙烯酸聚合物，就是含有具環己基的丙烯酸或甲基丙烯酸酯單體單位之丙烯酸聚合物。Further, the so-called acrylic polymer having a cyclohexyl group in the side chain is an acrylic polymer containing a monomer unit of an acrylic acid or a methacrylate having a cyclohexyl group.

作為不具有芳香環及環己基的丙烯酸酯單體，例如可舉出丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙基(i－、n－)酯、丙烯酸丁基(n－、i－、s－、t－)酯、丙烯酸戊基(n－、i－、s－)酯、丙烯酸己基(n－、i－)酯、丙烯酸庚基(n－、i－)酯、丙烯酸辛基(n－、i－)酯、丙烯酸壬基(n－、i－)酯、丙烯酸肉豆蔻基(n－、i－)酯、丙烯酸(2－乙基己基 )酯、丙烯酸(ε－己內酯)、丙烯酸(2－羥乙基)酯、丙烯酸(2－羥丙基)酯、丙烯酸(3－羥丙基)酯、丙烯酸(4－羥丁基)酯、丙烯酸(2－羥丁基)酯、丙烯酸(2－甲氧基乙基)酯、丙烯酸(2－乙氧基乙基)酯等、或將上述丙烯酸酯改變成甲基丙烯酸酯者。Examples of the acrylate monomer having no aromatic ring or cyclohexyl group include methyl acrylate, ethyl acrylate, propyl (i-, n-) acrylate, and butyl acrylate (n-, i-, s-). , t-) ester, pentyl acrylate (n-, i-, s-) ester, hexyl (n-, i-) acrylate, heptyl (n-, i-) acrylate, octyl acrylate (n- , i-) ester, decyl acrylate (n-, i-) ester, acrylonitrile myristyl (n-, i-) ester, acrylic acid (2-ethylhexyl) Ester, acrylic acid (ε-caprolactone), (2-hydroxyethyl) acrylate, (2-hydroxypropyl) acrylate, (3-hydroxypropyl) acrylate, 4-hydroxybutyl acrylate Ester, (2-hydroxybutyl) acrylate, (2-methoxyethyl) acrylate, (2-ethoxyethyl) acrylate, etc., or the above acrylate is changed to methacrylate.

丙烯酸聚合物係上述單體的均聚物或共聚物，較佳為具有30質量%以上的丙烯酸甲酯單體單位，且較佳為具有40質量%以上的甲基丙烯酸甲酯之酯單體單位。特佳為丙烯酸甲酯或甲基丙烯酸甲酯的均聚物。The acrylic polymer is a homopolymer or a copolymer of the above monomer, preferably having a methyl acrylate monomer unit of 30% by mass or more, and preferably an ester monomer having 40% by mass or more of methyl methacrylate. unit. Particularly preferred is a homopolymer of methyl acrylate or methyl methacrylate.

作為具有芳香環的丙烯酸或甲基丙烯酸酯單體，例如可舉出丙烯酸苯酯、甲基丙烯酸苯酯、丙烯酸(2或4－氯苯基)酯、甲基丙烯酸(2或4－氯苯基)酯、丙烯酸(2或3或4－乙氧羰基苯基)、甲基丙烯酸(2或3或4－乙氧羰基苯基)酯、丙烯酸(o或m或p－甲苯基)酯、甲基丙烯酸(o或m或p－甲苯基)酯、丙烯酸苄酯、甲基丙烯酸苄酯、丙烯酸苯乙酯、甲基丙烯酸苯乙酯、丙烯酸(2－萘基)酯等，可較佳地使用丙烯酸苄酯、甲基丙烯酸苄酯、丙烯酸苯乙酯、甲基丙烯酸苯乙酯。Examples of the acrylic or methacrylic ester monomer having an aromatic ring include phenyl acrylate, phenyl methacrylate, acrylic acid (2 or 4-chlorophenyl) ester, and methacrylic acid (2 or 4-chlorobenzene). Ester, acrylic acid (2 or 3 or 4-ethoxycarbonylphenyl), methacrylic acid (2 or 3 or 4-ethoxycarbonylphenyl) ester, acrylic acid (o or m or p-tolyl) ester, Methacrylic acid (o or m or p-tolyl) ester, benzyl acrylate, benzyl methacrylate, phenylethyl acrylate, phenylethyl methacrylate, (2-naphthyl) acrylate, etc., preferably Benzyl acrylate, benzyl methacrylate, phenylethyl acrylate, phenylethyl methacrylate are used.

於側鏈具有芳香環的丙烯酸聚合物之中，較佳為含有20~40質量%的具有芳香環的丙烯酸或甲基丙烯酸酯單體單位，且較佳為具有50~80質量%的丙烯酸或甲基丙烯酸甲酯單體單位。該聚合物中較佳為含有2~20質量%的具有羥基的丙烯酸或甲基丙烯酸酯單體單位。Among the acrylic polymers having an aromatic ring in the side chain, it is preferred to contain 20 to 40% by mass of an acrylic or methacrylic ester monomer unit having an aromatic ring, and preferably 50 to 80% by mass of acrylic acid or Methyl methacrylate monomer unit. The polymer preferably contains 2 to 20% by mass of an acrylic or methacrylic monomer unit having a hydroxyl group.

作為具有環己基的丙烯酸酯單體，例如可舉出丙烯酸 環己酯、甲基丙烯酸環己酯、丙烯酸(4－甲基環己基)酯、甲基丙烯酸(4－甲基環己基)、丙烯酸(4－乙基環己基)酯、甲基丙烯酸(4－乙基環己基)酯等，可較佳地使用丙烯酸環己酯及甲基丙烯酸環己酯。As the acrylate monomer having a cyclohexyl group, for example, acrylic acid is exemplified. Cyclohexyl ester, cyclohexyl methacrylate, (4-methylcyclohexyl) acrylate, (4-methylcyclohexyl) methacrylate, (4-ethylcyclohexyl) acrylate, methacrylic acid (4 As the ethylcyclohexyl) ester, cyclohexyl acrylate and cyclohexyl methacrylate can be preferably used.

側鏈具有環己基的丙烯酸聚合物中係含有20~40質量%的具有環己基的丙烯酸或甲基丙烯酸酯單體單位，且較佳為含有50~80質量%。又，該聚合物中較佳為含有2~20質量%的具有羥基的丙烯酸或甲基丙烯酸酯單體單位。The acrylic polymer having a cyclohexyl group in the side chain contains 20 to 40% by mass of an acrylic acid or methacrylic acid ester monomer unit having a cyclohexyl group, and preferably contains 50 to 80% by mass. Further, the polymer preferably contains 2 to 20% by mass of an acrylic acid or methacrylic acid ester monomer unit having a hydroxyl group.

將上述乙烯性不飽和單體聚合而得之聚合物、丙烯酸聚合物、側鏈具有芳香環的丙烯酸聚合物及側鏈具有環己基的丙烯酸聚合物係皆與纖維素樹脂的相溶性優異。The polymer obtained by polymerizing the above ethylenically unsaturated monomer, an acrylic polymer, an acrylic polymer having an aromatic ring in a side chain, and an acrylic polymer having a cyclohexyl group in a side chain are excellent in compatibility with a cellulose resin.

此等具有羥基的丙烯酸或甲基丙烯酸酯單體之情況係不是均聚物而是共聚物的構成單位。於此情況下，較佳為在丙烯酸聚合物中含有2~20質量%的具有羥基的丙烯酸或甲基丙烯酸酯單體單位。The case of such a hydroxyl group-containing acrylic acid or methacrylate monomer is not a homopolymer but a constituent unit of the copolymer. In this case, it is preferred to contain 2 to 20% by mass of an acrylic acid or methacrylic acid ester monomer unit having a hydroxyl group in the acrylic polymer.

於本發明中，可亦較佳地使用側鏈具有羥基的聚合物。作為具有羥基的單體單位，係與前述單體同樣，較佳為丙烯酸或甲基丙烯酸酯，例如可舉出丙烯酸(2－羥乙基)酯、丙烯酸(2－羥丙基)酯、丙烯酸(3－羥丙基)酯、丙烯酸(4－羥丁基)酯、丙烯酸(2－羥丁基)酯、丙烯酸對羥基甲基苯基酯、丙烯酸對(2－羥乙基)苯酯、或將此等丙烯酸替換成甲基丙烯酸者，較佳為丙烯酸－2－羥乙酯及甲基丙烯酸－2－羥乙酯。聚合物中的具有羥基的丙烯酸酯 或甲基丙烯酸酯單體單位較佳係在聚合物中含有2~20質量%，更佳為2~10質量%。In the present invention, a polymer having a hydroxyl group in a side chain can also be preferably used. The monomer unit having a hydroxyl group is preferably an acrylic acid or a methacrylic acid ester, and examples thereof include acrylic acid (2-hydroxyethyl) ester, acrylic acid (2-hydroxypropyl) ester, and acrylic acid. (3-hydroxypropyl) ester, (4-hydroxybutyl) acrylate, (2-hydroxybutyl) acrylate, p-hydroxymethyl phenyl acrylate, (2-hydroxyethyl) phenyl acrylate, Alternatively, the acrylic acid may be replaced by methacrylic acid, preferably 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. Acrylate having a hydroxyl group in a polymer The methacrylate monomer unit is preferably contained in the polymer in an amount of 2 to 20% by mass, more preferably 2 to 10% by mass.

如前述的聚合物含有2~20質量%的上述具有羥基的單體單位者，當然與纖維素酯的相溶性、保留性、尺寸安定性優異，不僅透濕度小，而且與作為偏光板保護薄膜的偏光鏡之接著性特優，具有提高偏光板的耐久性之效果。When the polymer contains 2 to 20% by mass of the above monomer unit having a hydroxyl group, it is of course excellent in compatibility, retention, and dimensional stability with a cellulose ester, and is not only low in moisture permeability but also as a protective film for a polarizing plate. The polarizer has excellent adhesion and has an effect of improving the durability of the polarizing plate.

作為使丙烯酸聚合物的主鏈之至少一末端具有羥基的方法，只要是使主鏈的末端具有羥基的方法即可，並沒有特別的限定，可藉由使用偶氮雙(2－羥乙基丁酸酯)般之具有羥基的自由基聚合引發劑之方法，使用2－巰基乙醇般之具有羥基的鏈轉移劑之方法，使用具有羥基的聚合停止劑之方法，藉由活性離子聚合而使在末端具有羥基之方法，使用如特開2000－128911號或2000－344823號公報中的具有一個硫醇基及2級羥基的化合物、或併用該化合物與有機金屬化合物的聚合觸媒之塊狀聚合的方法等而得，特佳為該公報中記載的方法。The method of providing a hydroxyl group at at least one terminal of the main chain of the acrylic polymer is not particularly limited as long as it has a hydroxyl group at the terminal of the main chain, and azobis(2-hydroxyethyl) can be used. A method of a radical polymerization initiator having a hydroxyl group as in the case of a butyric acid ester, which is a method of using a chain transfer agent having a hydroxyl group like 2-mercaptoethanol, using a polymerization stopper having a hydroxyl group, by living ion polymerization In the method of having a hydroxyl group at the terminal, a compound having a thiol group and a hydroxy group in a thiol group and a hydroxy group as in the case of JP-A-2000-128911 or 2000-344823, or a polymerization catalyst of the compound and the organometallic compound may be used. The method of polymerization or the like is obtained, and the method described in the publication is particularly preferable.

以該公報記載所關聯的方法所製作的聚合物，係當作綜研化學公司製的Actflow系列所市售，可較佳地使用。上述末端具有羥基的聚合物及/或側鏈具有羥基的聚合物，於本發明中係具有顯著提高聚合物的相溶性、透明性之效果。The polymer produced by the method described in the above publication is commercially available as an Actflow series manufactured by Amika Chemical Co., Ltd., and can be preferably used. The polymer having a hydroxyl group at the terminal end and/or a polymer having a hydroxyl group in a side chain has an effect of remarkably improving the compatibility and transparency of the polymer in the present invention.

再者，較佳為使用苯乙烯類當作對拉伸方向顯示負的配向雙折射性之乙烯性不飽和單體之聚合物，因為使展現負的折射性。作為苯乙烯類，例如可舉出苯乙烯、甲基苯 乙烯、二甲基苯乙烯、三甲基苯乙烯、乙基苯乙烯、異丙基苯乙烯、氯甲基苯乙烯、甲氧基苯乙烯、乙醯氧基苯乙烯、氯苯乙烯、二氯苯乙烯、溴苯乙烯、乙烯基苯甲酸甲酯等，惟不受此等所限定。Further, it is preferred to use a styrene as a polymer of an ethylenically unsaturated monomer having a negative birefringence which exhibits a negative direction of stretching because it exhibits a negative refractive index. Examples of the styrenes include styrene and methylbenzene. Ethylene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, ethoxylated styrene, chlorostyrene, dichloro Styrene, bromostyrene, methyl benzoate, etc., are not limited by these.

亦可與作為前述不飽和乙烯性單體所舉例的單體進行共聚合，或以控制雙折射性為目的，也可使具有2種以上的上述聚合物之纖維素酯相溶而使用。Further, it may be copolymerized with a monomer exemplified as the unsaturated ethylenic monomer, or may be used by mixing two or more kinds of cellulose esters of the above polymer for the purpose of controlling birefringence.

再者，本發明的第3相位差層較佳為含有由分子內不具有芳香環和親水性基的乙烯性不飽和單體Xa與分子內不具有芳香環而具有親水性基的乙烯性不飽和單體Xb之共聚合而得的重量平均分子量5000以上30000以下之聚合物X、及更佳含有聚合不具有芳香環的乙烯性不飽和單體Ya而得之重量平均分子量500以上3000以下的聚合物Y。Further, the third retardation layer of the present invention preferably contains an ethylenically unsaturated monomer Xa having no aromatic ring and a hydrophilic group in the molecule, and an ethylenic group having no hydrophilic ring in the molecule and having a hydrophilic group. The polymer X having a weight average molecular weight of 5,000 or more and 30,000 or less obtained by copolymerization of the saturated monomer Xb, and more preferably having a weight average molecular weight of 500 or more and 3,000 or less by containing an ethylenically unsaturated monomer Ya having no aromatic ring. Polymer Y.

(聚合物X、聚合物Y)(Polymer X, Polymer Y)

本發明中所用的聚合物X係由分子內不具有芳香環和親水性基的乙烯性不飽和單體Xa與分子內不具有芳香環而具有親水性基的乙烯性不飽和單體Xb之共聚合而得之重量平均分子量5000以上30000以下的聚合物。較佳為Xa係分子內不具有芳香環和親水性基的丙烯酸或甲基丙烯酸單體，Xb係分子內不具有芳香環而具有親水性基的丙烯酸或甲基丙烯酸單體。The polymer X used in the present invention is a mixture of an ethylenically unsaturated monomer Xa having no aromatic ring and a hydrophilic group in the molecule and an ethylenically unsaturated monomer Xb having a hydrophilic group in the molecule and having a hydrophilic group. A polymer obtained by polymerization and having a weight average molecular weight of 5,000 or more and 30,000 or less. An acrylic or methacrylic monomer having no aromatic ring and a hydrophilic group in the Xa-based molecule, and an acrylic or methacrylic monomer having a hydrophilic group in the Xb-based molecule and having a hydrophilic group are preferable.

本發明中所用的聚合物X係由下述通式(X)所表示 。The polymer X used in the present invention is represented by the following general formula (X) .

通式(X) －(Xa)m－(Xb)n－(Xc)p－General formula (X) -(Xa)m-(Xb)n-(Xc)p-

更佳為下述通式(X－1)所示的聚合物。More preferably, it is a polymer represented by the following formula (X-1).

通式(X－1) －[CH2 －C(－R1)(－CO2 R2)]m－[CH2 －C(－R3)(－CO2 R4－OH)－]n－[Xc]p－(式中，R1、R3表示H或CH3 。R2表示碳數1~12的烷基、環烷基。R4表示－CH2 －、－C2 H4 －或－C3 H6 －。Xc表示對Xa、Xb可聚合的單體單位。m、n及p表示莫耳組成比。但是m≠0、n≠0、m＋n＋p＝100)。General formula (X-1) -[CH 2 -C(-R1)(-CO 2 R2)]m-[CH 2 -C(-R3)(-CO 2 R4-OH)-]n-[Xc] P- (wherein R1 and R3 represent H or CH 3 . R 2 represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group. R 4 represents -CH 2 -, -C 2 H 4 - or -C 3 H 6 - Xc represents a monomer unit which is polymerizable to Xa and Xb. m, n and p represent a molar composition ratio, but m≠0, n≠0, m+n+p=100).

下述舉出當作構成本發明中所用的聚合物X之單體單位的單體，惟不受其所限定。The monomer constituting the monomer unit of the polymer X used in the present invention is exemplified below, but is not limited thereto.

X中的親水性基係指具有羥基、環氧乙烷鏈的基。The hydrophilic group in X means a group having a hydroxyl group or an ethylene oxide chain.

分子內不具有芳香環和親水性基的乙烯性不飽和單體Xa，例如可舉出丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙基(i－、n－)酯、丙烯酸丁基(n－、i－、s－、t－)酯、丙烯酸戊基(n－、i－、s－)酯、丙烯酸己基(n－、i－)酯、丙烯酸庚基(n－、i－)酯、丙烯酸辛基(n－、i－)酯、丙烯酸壬基(n－、i－)酯、丙烯酸肉豆蔻基(n－、i－)酯、丙烯酸(2－乙基己基)酯、丙烯酸(ε－己內酯)、丙烯酸(2－乙氧基乙基)酯等、或將上述丙烯酸酯改變成甲基丙烯酸酯者。其中，較佳為丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙基(i－、n－)酯。Examples of the ethylenically unsaturated monomer Xa having no aromatic ring and hydrophilic group in the molecule include methyl acrylate, ethyl acrylate, propyl (i-, n-) acrylate, and butyl acrylate (n-, I-, s-, t-) ester, pentyl acrylate (n-, i-, s-) ester, hexyl (n-, i-) acrylate, heptyl (n-, i-) acrylate, acrylic acid Octyl (n-, i-) ester, fluorenyl (n-, i-) acrylate, n-, i-) acrylate (n-, i-) ester, (2-ethylhexyl) acrylate, acrylic acid (ε- Caprolactone), (2-ethoxyethyl) acrylate or the like, or the above acrylate is changed to methacrylate. Among them, preferred are methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and propyl (i-, n-) methacrylate.

作為分子內不具有芳香環而具有親水性基的乙烯性不 飽和單體Xb，具有羥基的單體單位較佳為丙烯酸或甲基丙烯酸酯，例如可舉出丙烯酸(2－羥乙基)酯、丙烯酸(2－羥丙基)酯、丙烯酸(3－羥丙基)酯、丙烯酸(4－羥丁基)酯、丙烯酸(2－羥丁基)酯、或將此等丙烯酸換成甲基丙烯酸者，較佳為丙烯酸(2－羥乙基)酯及甲基丙烯酸(2－羥乙基)酯、丙烯酸(2－羥丙基)酯、丙烯酸(3－羥丙基)酯。Ethylene which does not have an aromatic ring in the molecule and has a hydrophilic group The saturated monomer Xb, the monomer unit having a hydroxyl group is preferably acrylic acid or methacrylic acid ester, and examples thereof include (2-hydroxyethyl) acrylate, (2-hydroxypropyl) acrylate, and acrylic acid (3-hydroxyl). a propyl) ester, a (4-hydroxybutyl) acrylate, a (2-hydroxybutyl) acrylate, or a methacrylic acid, preferably a 2-(hydroxyethyl) acrylate and (2-Hydroxyethyl) methacrylate, (2-hydroxypropyl) acrylate, (3-hydroxypropyl) acrylate.

作為Xc，只要是Xa、Xb以外者且可共聚合的乙烯性不飽和單體即可，並沒有特別的限制，較佳為不具有芳香環者。The Xc is not particularly limited as long as it is a copolymerizable ethylenic unsaturated monomer other than Xa or Xb, and preferably has no aromatic ring.

Xa、Xb的莫耳組成比m：n較佳為99：1~65：35的範圍，更佳為95：5~75：25的範圍。Xc的莫耳組成比p為0~10。Xc亦可為複數的單體單位。The molar composition ratio m:n of Xa and Xb is preferably in the range of 99:1 to 65:35, more preferably in the range of 95:5 to 75:25. The molar composition ratio of Xc is 0-10. Xc can also be a plurality of monomer units.

Xa的莫耳組成比若大，雖然與纖維素酯相溶性變優良，但薄膜厚度方向的遲滯值Rth變大。Xb的莫耳組成比若大，雖然上述相溶性變差，但減低Rth的效果高。又，Xb的莫耳組成比若超過上述範圍，製膜時有出現霧濁的傾向，較佳為謀求此等的最佳化，決定Xa、Xb的莫耳組成比。When the molar composition ratio of Xa is large, the compatibility with cellulose ester becomes excellent, but the hysteresis value Rth in the thickness direction of the film becomes large. Although the molar composition ratio of Xb is large, although the above compatibility is deteriorated, the effect of reducing Rth is high. Further, when the molar composition ratio of Xb exceeds the above range, fogging tends to occur during film formation, and it is preferable to optimize these and determine the molar composition ratio of Xa and Xb.

聚合物X的分子量係重量平均分子量為5000以上30000以下，更佳為8000以上25000以下。The molecular weight of the polymer X is a weight average molecular weight of 5,000 or more and 30,000 or less, more preferably 8,000 or more and 25,000 or less.

藉由使重量平均分子量成為5000以上，纖維素酯薄膜在高溫高濕下的尺寸變化少，作為偏光板保護薄膜可得到捲曲少等的優點而較宜。於重量平均分子量為30000以 內時，可更提高與纖維素酯的相溶性，可抑制高溫高濕下的滲出以及製膜後立即的霧濁之發生。When the weight average molecular weight is 5,000 or more, the dimensional change of the cellulose ester film under high temperature and high humidity is small, and it is preferable to obtain the advantage of being less curled as the polarizing plate protective film. The weight average molecular weight is 30,000 In the meantime, the compatibility with the cellulose ester can be further improved, and the bleeding under high temperature and high humidity and the occurrence of haze immediately after film formation can be suppressed.

本發明中所用的聚合物X之重量平均分子量係可藉由眾所周知的分子量調節方法來調整。作為如此的分子量調節方法，例如可舉出添加四氯化碳、月桂基硫醇、巰基乙酸辛酯等的鏈轉移劑之方法等。又，聚合溫度係在通常室溫至130℃進行，較佳在50℃至100℃進行，可調整該溫度或聚合反應時間。The weight average molecular weight of the polymer X used in the present invention can be adjusted by a well-known molecular weight adjustment method. As such a method of adjusting the molecular weight, for example, a method of adding a chain transfer agent such as carbon tetrachloride, lauryl mercaptan or octyl thioglycolate may be mentioned. Further, the polymerization temperature is carried out usually at room temperature to 130 ° C, preferably at 50 ° C to 100 ° C, and the temperature or polymerization reaction time can be adjusted.

重量平均分子量的測定方法係可藉由下述方法。The method for measuring the weight average molecular weight can be carried out by the following method.

(重量平均分子量測定方法)(Method for measuring weight average molecular weight)

重量平均分子量Mw係使用凝膠滲透層析術來測定。The weight average molecular weight Mw was determined using gel permeation chromatography.

測定條件係如以下。The measurement conditions are as follows.

溶劑：二氯甲烷管柱：Shodex K806、K805、K803G(連接3支昭和電工(股)製的來使用)管柱溫度：25℃試料濃度：0.1質量%偵檢器：RI Model 504(GL科學公司製)泵：L6000(日立製作所(股)製)流量：1.0ml/min 校正曲線：使用標準聚苯乙烯STK standard聚苯乙烯(東曹(股)製)Mw＝1000000~500為止的13樣品之校正曲線。13個樣品係大致等間隔地使用。Solvent: Dichloromethane column: Shodex K806, K805, K803G (connected to 3 Showa Denko (shares) for use) Column temperature: 25 °C Sample concentration: 0.1% by mass Detector: RI Model 504 (GL Science Company system) Pump: L6000 (Hitachi Manufacturing Co., Ltd. system) Flow: 1.0ml/min Calibration curve: A calibration curve of 13 samples up to standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) Mw = 1000000 to 500. Thirteen samples were used at approximately equal intervals.

本發明中所用的聚合物Y係將不具有芳香環的乙烯性不飽和單體Ya聚合而得之重量平均分子量500以上3000以下的聚合物。The polymer Y used in the present invention is a polymer obtained by polymerizing an ethylenically unsaturated monomer Ya having no aromatic ring and having a weight average molecular weight of 500 or more and 3,000 or less.

重量平均分子量500以上係能減少聚合物的殘留單體而較宜。又，3000以下由於能維持遲滯值Rth下降性能而較宜。A weight average molecular weight of 500 or more is preferred to reduce residual monomers of the polymer. Further, 3000 or less is preferable because the hysteresis value Rth can be maintained.

Ya較佳為不具有芳香環的丙烯酸或甲基丙烯酸單體。Ya is preferably an acrylic or methacrylic monomer having no aromatic ring.

本發明中所用的聚合物Y係由下述通式(Y)所表示。The polymer Y used in the present invention is represented by the following formula (Y).

通式(Y) －(Ya)k－(Yb)q－General formula (Y) -(Ya)k-(Yb)q-

更佳為下述通式(Y－1)所示的聚合物。More preferably, it is a polymer represented by the following formula (Y-1).

通式(Y－1) －[CH2 －C(－R5)(－CO2 R6)]k－[Yb]q－General formula (Y-1) -[CH 2 -C(-R5)(-CO 2 R6)]k-[Yb]q-

(式中，R5表示H或CH3 。R6表示碳數1~12的烷基或環烷基。Yb表示可與Ya共聚合的單體單位。k及q表示莫耳組成比。但是，k≠0、k＋q＝100)。(Wherein, R5 represents H or CH 3 .R6 represents an alkyl group having 1 to 12 carbon atoms, or represents cycloalkyl .Yb copolymerizable with Ya and q monomeric units .k molar ratio. However, k ≠0, k+q=100).

Yb只要是可與Ya共聚合的乙烯性不飽和單體即可，並沒有特別的限制。Yb亦可為複數。k＋q＝100，q較佳為0~30。Yb is not particularly limited as long as it is an ethylenically unsaturated monomer copolymerizable with Ya. Yb can also be plural. k+q=100, q is preferably 0~30.

作為構成將不具有芳香環的乙烯性不飽和單體聚合而得之聚合物Y的乙烯性不飽和單體Ya，有丙烯酸酯，例如可舉出丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙基(i－、n－ )酯、丙烯酸丁基(n－、i－、s－、t－)酯、丙烯酸戊基(n－、i－、s－)酯、丙烯酸己基(n－、i－)酯、丙烯酸庚基(n－、i－)酯、丙烯酸辛基(n－、i－)酯、丙烯酸壬基(n－、i－)酯、丙烯酸肉豆蔻基(n－、i－)酯、丙烯酸環己酯、丙烯酸(2－乙基己基)酯、丙烯酸(ε－己內酯)、丙烯酸(2－羥乙基)酯、丙烯酸(2－羥丙基)酯、丙烯酸(3－羥丙基)酯、丙烯酸(4－羥丁基)酯、丙烯酸(2－羥丁基)酯；甲基丙烯酸酯，可舉出將上述丙烯酸酯改變成甲基丙烯酸酯者；不飽和酸，例如可舉出丙烯酸、甲基丙烯酸、馬來酸酐、巴豆酸、伊康酸等。The ethylenically unsaturated monomer Ya constituting the polymer Y obtained by polymerizing an ethylenically unsaturated monomer having no aromatic ring may be an acrylate, and examples thereof include methyl acrylate, ethyl acrylate, and acryl propyl ( I-, n- Ester, butyl acrylate (n-, i-, s-, t-) ester, pentyl (n-, i-, s-) acrylate, hexyl (n-, i-) acrylate, heptyl acrylate (n-, i-) ester, octyl (n-, i-) acrylate, fluorenyl (n-, i-) acrylate, myristyl (n-, i-) acrylate, cyclohexyl acrylate , (2-ethylhexyl) acrylate, ε (caprolactone), (2-hydroxyethyl) acrylate, (2-hydroxypropyl) acrylate, (3-hydroxypropyl) acrylate, (4-hydroxybutyl) acrylate, (2-hydroxybutyl) acrylate; methacrylate, which is exemplified by changing the above acrylate to methacrylate; and unsaturated acid, for example, acrylic acid, Methacrylic acid, maleic anhydride, crotonic acid, itaconic acid, and the like.

Yb只要是可與Ya共聚合的乙烯性不飽和單體即可，並沒有特別的限制，作為乙烯酯，例如較佳為醋酸乙烯酯、丙酸乙烯醋、丁酸乙烯酯、戊酸乙烯酯、三甲基乙酸乙烯酯、己酸乙烯酯、癸酸乙烯酯、月桂酸乙烯酯、肉豆蔻酸乙烯酯、棕櫚酸乙烯酯、硬脂酸乙烯酯、環己烷羧酸乙烯酯、辛基酸乙烯酯、甲基丙烯酸乙烯酯、巴豆酸乙烯酯、山梨酸乙烯酯、肉桂酸乙烯酯等。Yb亦可為複數。Yb is not particularly limited as long as it is an ethylenically unsaturated monomer copolymerizable with Ya. As the vinyl ester, for example, vinyl acetate, vinyl vine acetate, vinyl butyrate, vinyl valerate is preferred. , trimethyl vinyl acetate, vinyl hexanoate, vinyl decanoate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, octyl Vinyl acetate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl cinnamate, and the like. Yb can also be plural.

於合成聚合物X、Y中，通常的聚合係難以控制分子量，希望盡可能使用不使分子量太大的方法，可使分子量一致的方法。作為該聚合方法，可舉出使用如過氧化枯烯或第三丁基過氧化氫的過氧化物聚合引發劑之方法，比一般聚合更大量使用聚合引發劑之方法，除了聚合引發劑亦使用巰基化合物或四氯化碳等的鏈轉移劑之方法，除了聚合引發劑亦使用如苯醌或二硝基苯的聚合停止劑之方法， 以及使用如特開2000－128911號或同2000－344823號公報中的具有一個硫醇基及2級羥基的化合物、或併用該化合物與有機金屬化合物的聚合觸媒的塊狀聚合之方法等，皆可在本發明中被較佳地用。特佳為使用分子中具有硫醇基及2級羥基的化合物當作鏈轉移劑之聚合方法。In the synthetic polymers X and Y, it is difficult to control the molecular weight in a usual polymerization system, and it is desirable to use a method in which the molecular weight is uniform without using a method in which the molecular weight is too large. As the polymerization method, a method of using a peroxide polymerization initiator such as cumene peroxide or t-butyl hydroperoxide, a method of using a polymerization initiator in a larger amount than usual polymerization, and a polymerization initiator are also used. a method of using a chain transfer agent such as a mercapto compound or carbon tetrachloride, in addition to a polymerization initiator, a method of using a polymerization stopper such as benzoquinone or dinitrobenzene, And a method of bulk polymerization using a compound having one thiol group and a second-order hydroxyl group, or a polymerization catalyst of the compound and an organometallic compound in combination with JP-A-2000-128911 or JP-A-2000-344823, Both of them can be preferably used in the present invention. Particularly preferred is a polymerization method using a compound having a thiol group and a hydroxy group in the molecule as a chain transfer agent.

於此情況下，在聚合物X及聚合物Y的末端，變成具有起因於聚合觸媒及鏈轉移劑的羥基、硫醚。藉由此末端殘基，可調整聚合物X、Y與纖維素酯的相溶性。In this case, at the end of the polymer X and the polymer Y, a hydroxyl group or a thioether which is caused by a polymerization catalyst and a chain transfer agent is obtained. By virtue of this terminal residue, the compatibility of the polymers X, Y with the cellulose ester can be adjusted.

聚合物X及Y的羥值較佳為30~150[mgKOH/g]。The hydroxyl value of the polymers X and Y is preferably from 30 to 150 [mgKOH/g].

(羥值的測定方法)(Method for measuring hydroxyl value)

此測定係依照JIS K0070(1992)。此羥值係定義為將1克試料乙醯化時，用於中和與羥基所鍵結的醋酸所需要的氫氧化鉀之毫克數。具體地，於燒瓶中精秤Xg(約1克)試料，於其中正確地添加20ml的乙醯化試藥(於20ml的醋酸酐中添加吡啶而成為400ml者)。於燒瓶口安裝空氣冷卻管，在95~100℃的甘油浴中加熱。This measurement is in accordance with JIS K0070 (1992). This hydroxyl value is defined as the number of milligrams of potassium hydroxide required to neutralize the acetic acid bonded to the hydroxyl group when one gram of the sample is oxime. Specifically, a sample of Xg (about 1 g) was weighed in a flask, and 20 ml of an acetamidine reagent (a pyridine was added to 20 ml of acetic anhydride to become 400 ml) was correctly added thereto. An air cooling tube was installed at the mouth of the flask and heated in a glycerin bath at 95 to 100 °C.

1小時30分鐘後，進行冷卻，從空氣冷卻管添加1毫升的精製水，將醋酸酐分解成醋酸。接著，使用電位差滴定裝置，以0.5mol/L氫氧化鉀乙醇溶液來進行滴定，以所得到的滴定曲線之反曲點當作終點。再者，作為空白試驗，不加入試料而進行滴定，求得滴定曲線的反曲點。After 1 hour and 30 minutes, cooling was carried out, and 1 ml of purified water was added from an air cooling tube to decompose acetic anhydride into acetic acid. Next, titration was carried out using a potentiometric titration apparatus in a 0.5 mol/L potassium hydroxide ethanol solution, and the inflection point of the obtained titration curve was taken as an end point. Further, as a blank test, titration was carried out without adding a sample, and the inflection point of the titration curve was obtained.

羥值係由下式來算出。The hydroxyl value is calculated by the following formula.

羥值＝{(B－C)×f×28.05/X}＋DHydroxyl value = {(B-C) × f × 28.05 / X} + D

(式中，B係空白試驗中所用的0.5mol/L之氫氧化鉀乙醇溶液的量(ml)，C係滴定中所用的0.5mol/L之氫氧化鉀乙醇溶液的量(ml)，f係0.5mol/L氫氧化鉀乙醇溶液之因數，D係酸價，而且28.05表示氫氧化鉀的1莫耳量56.11之1/2)。(In the formula, the amount (ml) of a 0.5 mol/L potassium hydroxide ethanol solution used in the B-series blank test, and the amount (ml) of a 0.5 mol/L potassium hydroxide ethanol solution used in the C-system titration, f It is a factor of 0.5 mol/L potassium hydroxide ethanol solution, D is the acid value, and 28.05 represents 1 mol of potassium hydroxide, 1/2 of 56.11).

上述聚合物X、聚合物Y皆係與纖維素酯的相溶性優異，亦不會蒸發或揮發，生產性優異，作為偏光板用保護薄膜的保留性良好，透濕度小，尺寸安定性優異。Both the polymer X and the polymer Y are excellent in compatibility with the cellulose ester, do not evaporate or volatilize, and are excellent in productivity, and have good retention properties as a protective film for a polarizing plate, small moisture permeability, and excellent dimensional stability.

聚合物X及聚合物Y在纖維素酯薄膜中的含量，較佳為滿足下述式(i)、式(ii)的範圍。以聚合物X的含量當作Xg(質量%＝(聚合物X的質量/纖維素酯的質量)×100)，以聚合物Y的含量當作Yg(質量%)時，式(i)5≦Xg＋Yg≦35(質量%) 式(ii)0.05≦Yg/(Xg＋Yg)≦0.4The content of the polymer X and the polymer Y in the cellulose ester film preferably satisfies the following formulas (i) and (ii). The content of the polymer X is taken as Xg (% by mass = (mass of polymer X / mass of cellulose ester) × 100), and when the content of polymer Y is taken as Yg (% by mass), formula (i) 5 ≦Xg+Yg≦35 (% by mass) Formula (ii) 0.05≦Yg/(Xg+Yg)≦0.4

式(i)的較佳範圍係10~25質量%。A preferred range of the formula (i) is 10 to 25% by mass.

聚合物X與聚合物Y的總量若為5質量%以上，則對遲滯值Rth的減低有充分作用。又，總量若為35質量%以下，則與偏光鏡PVA的接著性良好。When the total amount of the polymer X and the polymer Y is 5% by mass or more, the hysteresis value Rth is sufficiently reduced. In addition, when the total amount is 35% by mass or less, the adhesion to the polarizer PVA is good.

聚合物X與聚合物Y係可當作構成後述膠漿液的材料而直接添加、溶解，或預先溶解在溶解纖維素酯的有機溶劑中後，加於膠漿液中。The polymer X and the polymer Y may be directly added or dissolved as a material constituting a slurry to be described later, or may be dissolved in an organic solvent in which a cellulose ester is dissolved, and then added to the dope.

〈其它〉<other>

於前述纖維素酯或丙烯酸聚合物以外，亦可藉由將環狀烯烴樹脂、聚酯、聚碳酸酯等熔融製膜，不施予拉伸處理，而製作0≦Ro≦5nm且0≦| Rth |<40nm之範圍的相位差薄膜。In addition to the cellulose ester or the acrylic polymer, a cyclic olefin resin, a polyester, a polycarbonate or the like may be melt-formed, and a stretching treatment may be performed without causing a stretching treatment to produce 0≦Ro≦5 nm and 0≦| A phase difference film of Rth |<40 nm.

實施例Example

以下舉出實施例來具體說明本發明，惟本發明不受此等所限定。The invention is specifically illustrated by the following examples, but the invention is not limited thereto.

(遲滯值Ro、Rth、Nz的測定)(Measurement of hysteresis values Ro, Rth, Nz)

用自動雙折射計(王子計測機器(股)製的KOBRA－21ADH)來測定相位差薄膜的遲滯值。對相位差薄膜，在23℃、55%RH的環境下，以590nm的波長在10個地方測定，進行3次元折射率測定，求得折射率nx、ny、nz。依照公式算出面內方向的遲滯值Ro及厚度方向的遲滯值Rth。各自測定10個地方，以其平均值表示。The hysteresis value of the retardation film was measured by an automatic birefringence meter (KOBRA-21ADH manufactured by Oji Scientific Instruments Co., Ltd.). The retardation film was measured at 10 wavelengths at a wavelength of 590 nm in an environment of 23 ° C and 55% RH, and a three-dimensional refractive index measurement was performed to obtain refractive indices nx, ny, and nz. The hysteresis value Ro in the in-plane direction and the hysteresis value Rth in the thickness direction are calculated according to the formula. Each of the 10 places was measured and expressed as an average value.

Ro＝(nx－ny)×d Rth＝((nx＋ny)/2－nz)×d Nz＝(nx－nz)/(nx－ny)Ro=(nx-ny)×d Rth=((nx+ny)/2-nz)×d Nz=(nx-nz)/(nx-ny)

(式中，Ro表示薄膜面內遲滯值，Rth表示薄膜厚度方向遲滯值，nx表示薄膜面內的遲相軸方向之折射率，ny表示薄膜面內的進相軸方向之折射率，nz表示薄膜的厚度方向之折射率，d表示薄膜的厚度(nm))。(wherein, Ro represents the in-plane hysteresis value of the film, Rth represents the retardation value in the thickness direction of the film, nx represents the refractive index in the direction of the slow axis in the plane of the film, ny represents the refractive index in the direction of the phase axis in the plane of the film, and nz represents The refractive index of the film in the thickness direction, and d represents the thickness (nm) of the film.

〈相位差薄膜1的製作〉<Preparation of retardation film 1>

(膠漿液1的調製)(modulation of glue 1)

將以上投入密閉容器內，進行加熱，邊攪拌邊使完全溶解，使用安積濾紙(股)製的安積濾紙No.24來過濾，調製混合物1。在製膜生產線中藉由日本精線(股)製的Finemet NF來過濾膠漿1。The above was placed in a sealed container, heated, and completely dissolved while stirring, and filtered using an filter paper No. 24 made of a filter paper (package) to prepare a mixture 1. The dope 1 was filtered by Finemet NF manufactured by Nippon Seisaku Co., Ltd. in a film production line.

(二氧化矽分散液)(cerium oxide dispersion)

將以上在溶解器中攪拌混合30分鐘後，以蒙頓高林(Manton Gaulin)進行分散。分散後的液濁度為200ppm 。於二氧化矽分散液中邊攪拌邊投入80質量份的二氯甲烷，在溶解器中攪拌混合30分鐘，製作二氧化矽分散稀釋液。然後，對於100質量份的上述纖維素的混合物，添加10質量份的二氧化矽分散稀釋液，充分攪拌以成為膠漿液1。The mixture was stirred and mixed for 30 minutes in the dissolver, and then dispersed in Manton Gaulin. The turbidity of the liquid after dispersion is 200ppm . 80 parts by mass of dichloromethane was added to the cerium oxide dispersion while stirring, and the mixture was stirred and mixed for 30 minutes in a dissolver to prepare a cerium oxide dispersion diluent. Then, 10 parts by mass of a cerium oxide dispersion diluent was added to 100 parts by mass of the mixture of the above cellulose, and the mixture was sufficiently stirred to obtain a dope 1.

使用帶式流延裝置，在溫度35℃，以1800mm的寬度將膠漿液1均勻地流延在不銹鋼帶支持體上。藉由不銹鋼帶支持體使溶劑蒸發，直到殘留溶劑量成為100%為止，從不銹鋼帶支持體上剝離。將所剝離的纖維素酯之料片，在55℃蒸發溶劑，切割成1650mm寬，然後藉由拉幅機邊保持1.0倍的寬度，邊施加輸送張力而在MD方向(與薄膜的輸送方向並行)中於160℃拉伸1.3倍。此時拉幅機開始拉伸時的殘留溶劑量為18%。然後，在160℃、110℃的乾燥區中邊以多數的輥來輸送邊完成乾燥，切割成1500mm寬，對薄膜兩端施予寬度15mm、平均高度10μm的滾花加工，以捲繞初期張力220N/m、終點張力110N/m，捲繞在內徑6吋的芯上，得到相位差薄膜1。相位差薄膜1的殘留溶劑量為0.1%，平均膜厚為60μm，捲數為4000m。此相位差薄膜1的Ro60nm、Rth125nm，遲相軸係在MD方向。The dope 1 was uniformly cast on the stainless steel belt support at a temperature of 35 ° C and a width of 1800 mm using a belt casting apparatus. The solvent was evaporated by a stainless steel belt support until the residual solvent amount became 100%, and it was peeled off from the stainless steel belt support. The exfoliated cellulose ester tablet was evaporating the solvent at 55 ° C, cut into a width of 1650 mm, and then maintained at a width of 1.0 times by a tenter while applying a conveying tension in the MD direction (in parallel with the conveying direction of the film) It was stretched 1.3 times at 160 °C. At this time, the amount of residual solvent at the time when the tenter was stretched was 18%. Then, in a drying zone of 160 ° C and 110 ° C, the drying was carried out by a plurality of rolls, and the film was cut into a width of 1500 mm, and a knurling process of a width of 15 mm and an average height of 10 μm was applied to both ends of the film to wind the initial tension. 220 N/m and an end point tension of 110 N/m were wound around a core having an inner diameter of 6 Å to obtain a retardation film 1. The amount of residual solvent of the retardation film 1 was 0.1%, the average film thickness was 60 μm, and the number of rolls was 4000 m. Ro60nm and Rth125nm of the retardation film 1 are in the MD direction.

〈相位差薄膜2的製作〉<Preparation of retardation film 2>

與相位差薄膜1同樣地製作膠漿液1，同樣地進行直到對帶上流延．剝離．切割為止，然後藉由拉幅機在TD 方向(與薄膜的輸送方向正交的方向)中於160℃拉伸1.35倍。此時拉幅機開始拉伸時的殘留溶劑量為18%。然後，除了在160℃、110℃的乾燥區中邊以多數的輥來輸送邊使乾燥以外，與相位差薄膜1同樣地進行，得到相位差薄膜2。相位差薄膜2的殘留溶劑量為0.1%，平均膜厚為60μm，捲數為4000m，Ro60nm、Rth125nm，遲相軸係在TD方向。The dope 1 was produced in the same manner as the retardation film 1, and was similarly carried out until the tape was cast. Stripping. Cut it, then use the tenter in TD The direction (direction orthogonal to the conveying direction of the film) was 1.35 times stretched at 160 °C. At this time, the amount of residual solvent at the time when the tenter was stretched was 18%. Then, the retardation film 2 was obtained in the same manner as in the retardation film 1 except that it was conveyed by a plurality of rolls while drying in a drying zone of 160 ° C and 110 ° C. The amount of residual solvent of the retardation film 2 was 0.1%, the average film thickness was 60 μm, the number of turns was 4000 m, Ro60 nm and Rth were 125 nm, and the slow phase axis was in the TD direction.

〈相位差薄膜3的製作〉<Preparation of retardation film 3>

與相位差薄膜1同樣地製作膠漿液1，同樣地進行直到對帶上流延．剝離．切割為止，然後藉由拉幅機邊在TD方向中拉伸1.1倍，邊施加輸送張力而在MD方向(與薄膜的輸送方向並行)中於160℃拉伸1.2倍。此時拉幅機開始拉伸時的殘留溶劑量為18%。然後，除了在120℃、110℃進行乾燥以外，與相位差薄膜1同樣地進行，得到相位差薄膜3。相位差薄膜3的殘留溶劑量為0.1%，平均膜厚為48μm，捲數為4000m，Ro30nm、Rth125nm，遲相軸係在MD方向。The dope 1 was produced in the same manner as the retardation film 1, and was similarly carried out until the tape was cast. Stripping. After cutting, the film was stretched by 1.1 times in the TD direction by a tenter, and the transport tension was applied and stretched by 1.2 times at 160 ° C in the MD direction (in parallel with the film transport direction). At this time, the amount of residual solvent at the time when the tenter was stretched was 18%. Then, the retardation film 3 was obtained in the same manner as in the retardation film 1 except that the film was dried at 120 ° C and 110 ° C. The amount of residual solvent of the retardation film 3 was 0.1%, the average film thickness was 48 μm, the number of turns was 4000 m, Ro30 nm and Rth were 125 nm, and the slow phase axis was in the MD direction.

〈相位差薄膜4的製作〉<Preparation of retardation film 4>

除了與相位差薄膜1同樣地製作膠漿液1，同樣地進行直到對帶上流延．剝離．切割為止，藉由拉幅機在TD方向(與薄膜的輸送方向正交的方向)中於160℃拉伸1.3倍以外，與相位差薄膜2同樣地進行，得到相位差薄 膜4。拉幅機開始拉伸時的殘留溶劑量為18%。相位差薄膜4的殘留溶劑量為0.1%，平均膜厚為40μm，捲數為4000m，Ro45nm、Rth125nm，遲相軸係在TD方向。The dope 1 was produced in the same manner as the retardation film 1, and was similarly carried out until the tape was cast. Stripping. Before the dicing, the tenter was stretched by 1.3 times at 160 ° C in the TD direction (the direction orthogonal to the transport direction of the film), and the phase difference film 2 was obtained in the same manner as the retardation film 2 was obtained. Membrane 4. The amount of residual solvent at the start of stretching of the tenter was 18%. The retardation film 4 had a residual solvent amount of 0.1%, an average film thickness of 40 μm, a number of turns of 4000 m, a Ro45 nm and a Rth of 125 nm, and a slow phase axis in the TD direction.

〈相位差薄膜5的製作〉<Preparation of retardation film 5>

與相位差薄膜1同樣地製作膠漿液1，同樣地進行直到對帶上流延．剝離．切割為止，藉由拉幅機邊保持1.0倍的寬度，邊施加輸送張力而在MD方向(與薄膜的輸送方向並行)中於160℃拉伸1.3倍。此時拉幅機開始拉伸時的殘留溶劑量為18%。然後，除了在160℃、150℃進行乾燥以外，與相位差薄膜1同樣地進行，得到相位差薄膜5。相位差薄膜5的殘留溶劑量為0.1%，平均膜厚為80μm，捲數為4000m，Ro90nm、Rth125nm，遲相軸係在MD方向。The dope 1 was produced in the same manner as the retardation film 1, and was similarly carried out until the tape was cast. Stripping. The film was stretched by 1.3 times at 160 ° C in the MD direction (in parallel with the film transport direction) by applying a transport tension while being cut by a tenter. At this time, the amount of residual solvent at the time when the tenter was stretched was 18%. Then, the retardation film 5 was obtained in the same manner as the retardation film 1 except that it was dried at 160 ° C and 150 ° C. The amount of residual solvent of the retardation film 5 was 0.1%, the average film thickness was 80 μm, the number of turns was 4000 m, Ro90 nm and Rth were 125 nm, and the slow phase axis was in the MD direction.

〈相位差薄膜6的製作〉<Preparation of retardation film 6>

與相位差薄膜1同樣地製作膠漿液1，同樣地進行直到對帶上流延．剝離．切割為止，藉由拉幅機在TD方向邊拉伸1.0倍，邊施加輸送張力而在MD方向(與薄膜的輸送方向並行)中於160℃拉伸1.05倍。此時拉幅機開始拉伸時的殘留溶劑量為18%。然後，除了在120℃、110℃進行乾燥以外，與相位差薄膜1同樣地進行，得到相位差薄膜6。相位差薄膜6的殘留溶劑量為0.1%，平均膜厚為40μm，捲數為4000m，Ro0.2nm、Rth60nm，遲相軸係在 MD方向。The dope 1 was produced in the same manner as the retardation film 1, and was similarly carried out until the tape was cast. Stripping. Before cutting, the film was stretched 1.0 times in the TD direction by a tenter, and while applying a transport tension, it was stretched 1.05 times at 160 ° C in the MD direction (in parallel with the film transport direction). At this time, the amount of residual solvent at the time when the tenter was stretched was 18%. Then, the retardation film 6 was obtained in the same manner as in the retardation film 1 except that the film was dried at 120 ° C and 110 ° C. The retardation film 6 has a residual solvent amount of 0.1%, an average film thickness of 40 μm, a number of windings of 4000 m, a Ro0.2 nm, and a Rth of 60 nm, and a slow phase axis system. MD direction.

〈相位差薄膜7的製作〉<Preparation of retardation film 7>

(膠漿液3的調製)(modulation of glue 3)

將以上投入密閉容器內，進行加熱，邊攪拌邊使完全溶解，使用安積濾紙(股)製的安積濾紙No.24來過濾，接著以日本精線(股)製的Finemet NF來過濾，製作膠漿液3。The above-mentioned liquid was placed in a sealed container, heated, and completely dissolved by stirring. The filter paper No. 24 made of Azure filter paper was used for filtration, and then filtered by Finemet NF manufactured by Nippon Seiki Co., Ltd. to prepare a gel. Slurry 3.

〈聚合物UV劑P－1的合成〉<Synthesis of Polymer UV Agent P-1>

依照下述記載的方法來合成2(2’－羥基－5’－第三丁基－苯基)－5－羧酸－(2－甲基丙烯醯氧基)乙基酯－2H－苯并***(聚合物UV劑P－1)。Synthesis of 2(2'-hydroxy-5'-tert-butyl-phenyl)-5-carboxylic acid-(2-methylpropenyloxy)ethyl ester-2H-benzene according to the method described below Triazole (polymer UV agent P-1).

將20.0克3－硝基－4－胺基－苯甲酸溶解在160ml的水中，添加43ml的濃鹽酸。於0℃添加溶解在20ml的水中之8.0克亞硝酸鈉後，同樣在0℃攪拌2小時。於此溶液中，邊以碳酸鉀將液性保持鹼性邊於0℃滴下由17.3克4－第三丁基酚溶解在50ml的水與100ml的乙醇中而成的溶液。邊將該溶液保持在0℃邊攪拌1小時，再於室溫攪拌1小時。以鹽酸使反應液成為酸性，過濾所生成的沈澱物後，充分水洗。20.0 g of 3-nitro-4-amino-benzoic acid was dissolved in 160 ml of water, and 43 ml of concentrated hydrochloric acid was added. After adding 8.0 g of sodium nitrite dissolved in 20 ml of water at 0 ° C, the mixture was stirred at 0 ° C for 2 hours. In this solution, a solution obtained by dissolving 17.3 g of 4-tert-butylphenol in 50 ml of water and 100 ml of ethanol was dropped at 0 ° C while maintaining the liquidity with potassium carbonate. The solution was stirred at 0 ° C for 1 hour while stirring at room temperature for 1 hour. The reaction solution was made acidic with hydrochloric acid, and the resulting precipitate was filtered, and washed thoroughly with water.

使所過濾的沈澱物溶解在500ml的1莫耳/升之NaOH水溶液中，添加35克鋅粉末後，滴下110克40%NaOH水溶液。滴下後，攪拌約2小時，進行過濾、水洗，以鹽酸中和濾液使成為中性。過濾所析出的沈澱物，進行水洗、乾燥後，以醋酸乙酯與丙酮的混合溶劑進行再結晶，而得到2(2’－羥基－5’－第三丁基－苯基)－5－羧酸－2H－苯并***。The filtered precipitate was dissolved in 500 ml of a 1 mol/L aqueous NaOH solution, and after adding 35 g of zinc powder, 110 g of a 40% aqueous NaOH solution was dropped. After the dropwise addition, the mixture was stirred for about 2 hours, filtered, washed with water, and the filtrate was neutralized with hydrochloric acid to be neutral. The deposited precipitate was filtered, washed with water, dried, and recrystallized from a mixed solvent of ethyl acetate and acetone to obtain 2(2'-hydroxy-5'-t-butyl-phenyl)-5-carboxylate. Acid-2H-benzotriazole.

其次，將10.0克2(2’－羥基－5’－第三丁基－苯基)－5－羧酸－2H－苯并***、0.1克氫醌、4.6克甲基丙烯酸2－羥乙酯及0.5克對甲苯磺酸加到100ml的甲苯中，藉由具備酯管的反應容器進行10小時加熱回流。將反應溶液注入水中，過濾所析出的結晶，進行水洗、乾燥，以醋酸乙酯進行再結晶，而得到2(2’－羥基－5’－第三丁基－苯基)－5－羧酸－(2－甲基丙烯醯氧基)乙基酯－2H－苯并***。Next, 10.0 g of 2(2'-hydroxy-5'-tert-butyl-phenyl)-5-carboxylic acid-2H-benzotriazole, 0.1 g of hydroquinone, 4.6 g of 2-hydroxyethyl methacrylate The ester and 0.5 g of p-toluenesulfonic acid were added to 100 ml of toluene, and heated under reflux for 10 hours through a reaction vessel equipped with an ester tube. The reaction solution was poured into water, and the precipitated crystals were filtered, washed with water, dried, and recrystallized with ethyl acetate to obtain 2(2'-hydroxy-5'-t-butyl-phenyl)-5-carboxylic acid. -(2-Methylacryloxy)ethyl ester-2H-benzotriazole.

接著，依照下述記載的方法來合成2(2’－羥基－5’－第三丁基－苯基)－5－羧酸－(2－甲基丙烯醯氧基)乙基酯－2H－ 苯并***與甲基丙烯酸甲酯的共聚物(聚合物UV劑P－1)。Next, 2(2'-hydroxy-5'-t-butyl-phenyl)-5-carboxylic acid-(2-methylpropenyloxy)ethyl ester-2H- was synthesized according to the method described below. Copolymer of benzotriazole with methyl methacrylate (Polymer UV Agent P-1).

於80ml的四氫呋喃中，添加上述所合成的4.0克2(2’－羥基－5’－第三丁基－苯基)－5－羧酸－(2－甲基丙烯醯氧基)乙基酯－2H－苯并***及6.0克甲基丙烯酸甲酯，接著添加1.14克偶氮異丁腈。於氮氣環境下加熱回流9小時。減壓餾去四氫呋喃後，再溶解於20ml的四氫呋喃中，滴到大量過剩的甲醇中。過濾取得所析出的沈澱物，在40℃進行真空乾燥，得到9.1克灰白色粉狀聚合物的高分子UV劑P－1。藉由以標準聚苯乙烯當作基準的GPC分析，確認該共聚物的數量平均分子量為4500。又，根據NMR光譜及UV光譜，確認上述共聚物為2(2’－羥基－5’－第三丁基－苯基)－5－羧酸－(2－甲基丙烯醯氧基)乙基酯－2H－苯并***與甲基丙烯酸甲酯的共聚物。上述聚合物的組成大略為2(2’－羥基－5’－第三丁基－苯基)－5－羧酸－(2－甲基丙烯醯氧基)乙基酯－2H－苯并***：甲基丙烯酸甲酯＝40：60。In 80 ml of tetrahydrofuran, 4.0 g of 2(2'-hydroxy-5'-tert-butyl-phenyl)-5-carboxylic acid-(2-methylpropenyloxy)ethyl ester synthesized above was added. -2H-benzotriazole and 6.0 g of methyl methacrylate followed by 1.14 g of azoisobutyronitrile. The mixture was heated under reflux for 9 hours under a nitrogen atmosphere. After distilling off tetrahydrofuran under reduced pressure, it was dissolved in 20 ml of tetrahydrofuran and dropped into a large excess of methanol. The precipitate which precipitated was collected by filtration, and vacuum-dried at 40 ° C to obtain 9.1 g of a gray UV-like polymer polymer UV P-1. The number average molecular weight of the copolymer was confirmed to be 4,500 by GPC analysis using standard polystyrene as a reference. Further, it was confirmed from the NMR spectrum and the UV spectrum that the above copolymer was 2(2'-hydroxy-5'-tert-butyl-phenyl)-5-carboxylic acid-(2-methylpropenyloxy)ethyl Copolymer of ester-2H-benzotriazole with methyl methacrylate. The composition of the above polymer is roughly 2 (2'-hydroxy-5'-tert-butyl-phenyl)-5-carboxylic acid-(2-methylpropenyloxy)ethyl ester-2H-benzotriene Azole: methyl methacrylate = 40:60.

其次，使用帶式流延裝置，在溫度22℃，以2m的寬度將膠漿液3均勻地流延在不銹鋼帶支持體上。藉由不銹鋼帶支持體使溶劑蒸發，直到殘留溶劑量成為100%為止，以162N/m的剝離張力從不銹鋼帶支持體上剝離。將所剝離的纖維素酯之料片，在35℃蒸發溶劑，切割成1.6m寬，然後藉由拉幅機邊在TD方向拉伸1.1倍，邊在135℃的乾燥溫度使乾燥。此時拉幅機開始拉伸時的殘留 溶劑量為10%。以拉幅機拉伸後，進行下述的加熱處理、環境氣體置換率、加壓處理，完成乾燥，切割成1.5m寬，對薄膜兩端施予寬度10mm、高度5μm的滾花加工，以初期張力220N/m、終點張力110N/m，捲繞在內徑6吋的芯上，得到相位差薄膜7。由不銹鋼帶支持體的旋轉速度及拉幅機的運轉速度所算出的MD方向之拉伸倍率為1.1倍。相位差薄膜7的殘留溶劑量為0.1%，膜厚為65μm，捲數為4000m。此相位差薄膜7為Ro0.1nm、Rth15nm。Next, using a belt casting apparatus, the dope 3 was uniformly cast on the stainless steel belt support at a temperature of 22 ° C with a width of 2 m. The solvent was evaporated by a stainless steel belt support until the residual solvent amount became 100%, and peeled off from the stainless steel belt support at a peeling force of 162 N/m. The exfoliated cellulose ester tablet was evaporated at 35 ° C, cut into 1.6 m width, and then stretched 1.1 times in the TD direction by a tenter, and dried at a drying temperature of 135 ° C. At this time, the tenter starts to stretch when it is stretched. The amount of solvent is 10%. After stretching by a tenter, the following heat treatment, ambient gas replacement rate, and pressure treatment were carried out, and the drying was completed, and the film was cut into a width of 1.5 m, and a knurling process having a width of 10 mm and a height of 5 μm was applied to both ends of the film to The initial tension of 220 N/m and the end point tension of 110 N/m were wound around a core having an inner diameter of 6 Torr to obtain a retardation film 7. The draw ratio in the MD direction calculated from the rotation speed of the stainless steel belt support and the operation speed of the tenter was 1.1 times. The amount of residual solvent of the retardation film 7 was 0.1%, the film thickness was 65 μm, and the number of rolls was 4000 m. This retardation film 7 was Ro 0.1 nm and Rth 15 nm.

〈相位差薄膜8的製作〉<Preparation of retardation film 8>

(聚合物X的合成)(Synthesis of Polymer X)

於附有攪拌機、2個滴液漏斗、氣體導入管及溫度計的玻璃燒瓶內，投入表1記載之種類及比率(莫耳組成比)的40克單體Xa、Xb混合液、2克鏈轉移劑的巰基丙酸及30克甲苯，升溫到90℃。然後，從一個滴液漏斗費3小時滴下表1記載之種類及比率(莫耳組成比)的60克單體Xa、Xb混合液，同時從另一個漏斗費3小時滴下溶解在14克甲苯中的0.4克偶氮雙異丁腈。然後再費2小時滴下溶解在56克甲苯中的0.6克偶氮雙異丁腈後，更繼續反應2小時，得到聚合物X。所得到的聚合物X在常溫為固體。表1中顯示藉由下述測定法所得之聚合物X的重量平均分子量。In a glass flask equipped with a stirrer, two dropping funnels, a gas introduction tube, and a thermometer, 40 g of a mixture of monomers Xa and Xb and 2 g of chain transfer were introduced into the types and ratios (molar composition ratio) shown in Table 1. The mercaptopropionic acid and 30 g of toluene were heated to 90 °C. Then, a mixture of 60 g of the monomers Xa and Xb of the type and ratio (molar composition ratio) described in the following Table 1 was dropped from a dropping funnel for 3 hours while being dissolved in 14 g of toluene by dropping from another funnel for 3 hours. 0.4 g of azobisisobutyronitrile. Then, after 0.6 g of azobisisobutyronitrile dissolved in 56 g of toluene was added dropwise for 2 hours, the reaction was further continued for 2 hours to obtain a polymer X. The obtained polymer X was a solid at normal temperature. The weight average molecular weight of the polymer X obtained by the following measurement is shown in Table 1.

又，表1記載的MMA、HEA分別為以下化合物的簡稱。Further, each of MMA and HEA described in Table 1 is an abbreviation of the following compounds.

MMA：甲基丙烯酸甲酯 HEA：丙烯酸2－羥乙酯MMA: Methyl methacrylate HEA: 2-hydroxyethyl acrylate

(重量平均分子量測定)(weight average molecular weight determination)

重量平均分子量的測定係使用凝膠滲透層析術來測定。The determination of the weight average molecular weight was determined using gel permeation chromatography.

測定條件係如以下。The measurement conditions are as follows.

溶劑：二氯甲烷管柱：Shodex K806、K805、K803G(連接3支昭和電工(股)製的來使用)管柱溫度：25℃試料濃度：0.1質量%偵檢器：RI Model 504(GL科學公司製)泵：L6000(日立製作所(股)製)流量：1.0ml/min 校正曲線：使用標準聚苯乙烯STK standard聚苯乙烯(東曹(股)製)Mw＝1000000~500為止的13樣品之校正曲線。13個樣品係大致等間隔地使用。Solvent: Dichloromethane column: Shodex K806, K805, K803G (connected to 3 Showa Denko (shares) for use) Column temperature: 25 °C Sample concentration: 0.1% by mass Detector: RI Model 504 (GL Science Company system) Pump: L6000 (Hitachi Manufacturing Co., Ltd. system) Flow: 1.0ml/min Calibration curve: A calibration curve of 13 samples up to standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) Mw = 1000000 to 500. Thirteen samples were used at approximately equal intervals.

(聚合物Y的合成)(Synthesis of Polymer Y)

藉由特開2000－128911號公報記載的聚合方法進行塊狀聚合。即，於具備攪拌機、氮氣導入管、溫度計、投入口及回流冷卻管的燒瓶內，投入當作單體Ya的下述丙烯酸甲酯(MA)，導入氮氣，以氮氣置換燒瓶內，在攪拌 下添加下述硫甘油。添加硫甘油後，使內容物的溫度適當地變化，進行4小時的聚合，使內容物回到室溫，於其中添加20質量份的苯醌5質量%四氫呋喃溶液，以停止聚合。將內容物移到蒸發器，於80℃在減壓下，去除四氫呋喃、殘留的單體及殘留的硫甘油，得到表1記載的聚合物Y。所得到的聚合物Y在常溫為液體。表1中顯示藉由上述測定法所得之該聚合物Y的重量平均分子量。The bulk polymerization is carried out by the polymerization method described in JP-A-2000-128911. Specifically, in the flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer, an inlet, and a reflux cooling tube, the following methyl acrylate (MA) as a monomer Ya was introduced, nitrogen gas was introduced, and the inside of the flask was replaced with nitrogen. The following thioglycerol was added. After the addition of thioglycerol, the temperature of the content was appropriately changed, polymerization was carried out for 4 hours, the content was returned to room temperature, and 20 parts by mass of a benzoquinone 5 mass% tetrahydrofuran solution was added thereto to stop the polymerization. The contents were transferred to an evaporator, and tetrahydrofuran, residual monomers, and residual sulfur glycerin were removed under reduced pressure at 80 ° C to obtain a polymer Y shown in Table 1. The obtained polymer Y was a liquid at normal temperature. The weight average molecular weight of the polymer Y obtained by the above measurement is shown in Table 1.

<膠漿的組成><Composition of glue>

(二氧化矽分散液)(cerium oxide dispersion)

將以上在溶解器中攪拌混合30分鐘後，以蒙頓高林(Manton Gaulin)進行分散。分散後的液濁度為200ppm。於二氧化矽分散液中邊攪拌邊投入88質量份的二氯甲 烷，在溶解器中攪拌混合30分鐘，製作二氧化矽分散稀釋液。The mixture was stirred and mixed for 30 minutes in the dissolver, and then dispersed in Manton Gaulin. The liquid turbidity after dispersion was 200 ppm. 88 parts by mass of dichloromethane was added to the cerium oxide dispersion while stirring The alkane was stirred and mixed in a dissolver for 30 minutes to prepare a cerium oxide dispersion diluent.

(膠漿添加液)(glue addition liquid)

關於以上，在邊攪拌邊使二氯甲烷與聚合物X和聚合物Y完全溶解後，添加二氧化矽分散液，進行攪拌混合以調製膠漿添加液。In the above, the dichloromethane and the polymer X and the polymer Y were completely dissolved while stirring, and then the cerium oxide dispersion was added and stirred and mixed to prepare a dope addition liquid.

(主膠漿液的調製)(modulation of the main glue)

將以上投入密閉容器內，進行加熱，邊攪拌邊使完全溶解，使用安積濾紙(股)製的安積濾紙No.24來過濾，調製主膠漿液。The above was put into a sealed container, heated, and completely dissolved while stirring, and filtered using an Augmentation filter paper No. 24 made of an Anion filter paper to prepare a main dope.

以日本精線(股)製的Finemet NF來過濾上述主膠 漿液，使用帶式流延裝置，在溫度22℃，以2m的寬度均勻地流延在不銹鋼帶支持體上。藉由不銹鋼帶支持體使溶劑蒸發，直到殘留溶劑量成為105%為止，以162N/m的剝離張力從不銹鋼帶支持體上剝離。將所剝離的纖維素酯之料片，在35℃蒸發溶劑，切割成1.6m寬，然後藉由拉幅機邊在寬度方向中拉伸1.1倍，邊在135℃的乾燥溫度使乾燥。此時拉幅機開始拉伸時的殘留溶劑量為10%。以拉幅機拉伸後，在130℃將寬度張力緩和而開放寬度保持後，在120℃、130℃的乾燥區中邊以多數的輥來輸送邊完成乾燥，切割成1.5m寬，對薄膜兩端施予寬度10mm、高度7μm的滾花加工，以初期張力220N/m、終點張力110N/m，捲繞在內徑6吋的芯上，得到纖維素酯薄膜1。由不銹鋼帶支持體的旋轉速度及拉幅機的運轉速度所算出的MD方向之拉伸倍率為1.1倍。纖維素酯薄膜1的殘留溶劑量為少於0.1%，膜厚為40μm，Ro0nm、Rth9nm。Filter the above main glue with Finemet NF made by Nippon Seiki Co., Ltd. The slurry was uniformly cast on the stainless steel belt support at a temperature of 22 ° C at a temperature of 2 m using a belt casting apparatus. The solvent was evaporated by a stainless steel belt support until the residual solvent amount became 105%, and peeled off from the stainless steel belt support at a peeling force of 162 N/m. The exfoliated cellulose ester tablet was evaporated at 35 ° C, cut into 1.6 m width, and then stretched 1.1 times in the width direction by a tenter, and dried at a drying temperature of 135 ° C. At this time, the amount of residual solvent at the time when the tenter was stretched was 10%. After stretching by a tenter, the width tension was relaxed at 130 ° C and the open width was maintained. After drying in a drying zone of 120 ° C and 130 ° C with a plurality of rolls, the drying was completed, and the film was cut into a width of 1.5 m. The both ends were knurled with a width of 10 mm and a height of 7 μm, and were wound around a core having an inner diameter of 6 以 at an initial tension of 220 N/m and an end tension of 110 N/m to obtain a cellulose ester film 1. The draw ratio in the MD direction calculated from the rotation speed of the stainless steel belt support and the operation speed of the tenter was 1.1 times. The cellulose ester film 1 had a residual solvent amount of less than 0.1%, a film thickness of 40 μm, and Ro0 nm and Rth of 9 nm.

〈相位差薄膜9~17、20~27的製作〉<Production of retardation film 9~17, 20~27>

與相位差薄膜1同樣地，適當地變更膜厚、拉伸倍率，製作各自具有表2記載的Ro、Rth之相位差薄膜9~17、20~27。In the same manner as the retardation film 1, the film thickness and the stretching ratio were appropriately changed, and the retardation films 9 to 17, 20 to 27 each having Ro and Rth described in Table 2 were produced.

〈相位差薄膜18、19的製作〉<Preparation of retardation films 18 and 19>

使三乙醯纖維素溶解在二氯甲烷溶劑中，以其當作膠漿溶液，藉由溶液流延來製作薄膜。然後，藉由調整拉伸 倍率，製作Ro5nm、Rth40nm的相位差薄膜18、Ro15nm、Rth60nm的相位差薄膜19。The triacetonitrile cellulose was dissolved in a dichloromethane solvent to prepare a film as a dope solution by solution casting. Then, by adjusting the stretch At a magnification, a retardation film 18 of Ro5nm and Rth 40 nm, a retardation film 19 of Ro15 nm and Rth of 60 nm were produced.

〈纖維素酯薄膜1的製作〉<Production of Cellulose Ester Film 1>

使用帶式流延裝置，在溫度32℃，以1800mm的寬度將膠漿1均勻地流延在不銹鋼帶支持體上。藉由不銹鋼帶支持體使溶劑蒸發，直到殘留溶劑量成為100%為止，從不銹鋼帶支持體上剝離。將所剝離的纖維素酯之料片，在35℃蒸發溶劑，切割成1650mm寬，然後藉由拉幅機邊在TD方向(與薄膜的輸送方向正交的方向)拉伸1.05倍，邊在135℃的乾燥溫度使乾燥。此時拉幅機開始拉伸時的殘留溶劑量為20%。Using a belt casting apparatus, the dope 1 was uniformly cast on the stainless steel belt support at a temperature of 32 ° C at a width of 1800 mm. The solvent was evaporated by a stainless steel belt support until the residual solvent amount became 100%, and it was peeled off from the stainless steel belt support. The exfoliated cellulose ester tablet was evaporated at 35 ° C, cut into a width of 1650 mm, and then stretched by 1.05 times in the TD direction (direction orthogonal to the film transport direction) by a tenter. Drying at 135 ° C allows drying. At this time, the amount of residual solvent at the time when the tenter was stretched was 20%.

然後，在120℃、110℃的乾燥區中邊以多數的輥來輸送邊完成乾燥，切割成1500mm寬，對薄膜兩端施予寬度15mm、平均高度10μm的滾花加工，以捲繞初期張力220N/m、終點張力110N/m，捲繞在內徑6吋的芯上，得到纖維素酯薄膜1。由不銹鋼帶支持體的旋轉速度及拉幅機的運轉速度所算出的剝離後立即的MD方向(與薄膜的輸送方向成同一方向)之拉伸倍率為1.07倍。纖維素酯薄膜1的殘留溶劑量為0.02%，平均膜厚為60μm，捲數為4000m。Then, in a drying zone of 120 ° C and 110 ° C, the drying was carried out by a plurality of rolls, and the film was cut into a width of 1500 mm, and a knurling process of a width of 15 mm and an average height of 10 μm was applied to both ends of the film to wind the initial tension. 220 N/m and an end point tension of 110 N/m were wound around a core having an inner diameter of 6 Torr to obtain a cellulose ester film 1. The stretching ratio in the MD direction (the same direction as the film conveying direction) immediately after the peeling calculated from the rotation speed of the stainless steel belt support and the running speed of the tenter was 1.07 times. The cellulose ester film 1 had a residual solvent amount of 0.02%, an average film thickness of 60 μm, and a number of rolls of 4000 m.

〈相位差薄膜A的製作〉<Preparation of retardation film A>

(膠漿液2的調製)(modulation of glue 2)

將以上投入密閉容器內，進行加熱，邊攪拌邊使完全溶解以成為膠漿液2。The above was put into a sealed container, heated, and completely dissolved to become a dope 2 with stirring.

使用帶式流延裝置，在溫度35℃，以1800mm的寬度將膠漿液2均勻地流延在不銹鋼帶支持體上。藉由不銹鋼帶支持體使溶劑蒸發，直到殘留溶劑量成為100%為止，從不銹鋼帶支持體上剝離。將所剝離的纖維素酯之料片，在90℃、140℃蒸發溶劑，切割成1750mm，然後施加輸送張力，在MD方向(與薄膜的輸送方向並行)中於100℃進行1.2倍的自由端一軸拉伸。開始拉伸時的殘留溶劑量為3%。然後，在100℃的乾燥區中邊以多數的輥來輸送邊完成乾燥，切割成1500mm寬，對薄膜兩端施予寬度15mm、平均高度10μm的滾花加工，以捲繞初期張力220N/m、終張力110N/m，在內徑6吋的芯上捲繞，得到相位差薄膜A。相位差薄膜A的殘留溶劑量為0.1%，平均膜厚為80μm，捲數為4000m。此相位差薄膜A係Ro150nm、Rth－75nm、Nz0，遲相軸係在TD方向。The dope 2 was uniformly cast on the stainless steel belt support at a temperature of 35 ° C and a width of 1800 mm using a belt casting apparatus. The solvent was evaporated by a stainless steel belt support until the residual solvent amount became 100%, and it was peeled off from the stainless steel belt support. The exfoliated cellulose ester tablet was evaporated at 90 ° C and 140 ° C, cut into 1750 mm, and then subjected to a transport tension, and 1.2 times of the free end was carried out at 100 ° C in the MD direction (in parallel with the film transport direction). One-axis stretching. The amount of residual solvent at the start of stretching was 3%. Then, in a drying zone of 100 ° C, the drying was carried out by a plurality of rolls, and the film was cut into a width of 1500 mm, and a knurling process of a width of 15 mm and an average height of 10 μm was applied to both ends of the film to obtain an initial tension of 220 N/m. The final tension was 110 N/m, and it was wound on a core having an inner diameter of 6 Torr to obtain a retardation film A. The amount of residual solvent of the retardation film A was 0.1%, the average film thickness was 80 μm, and the number of rolls was 4000 m. The retardation film A is Ro150nm, Rth-75nm, and Nz0, and the slow phase axis is in the TD direction.

〈相位差薄膜B的製作〉<Preparation of retardation film B>

除了在使用膠漿液2進行帶式流延．剝離．乾燥，切割成1650mm寬之後，藉由拉幅機在TD方向(與薄膜的 輸送方向正交的方向)中於100℃拉伸1.15倍以外，進行與相位差薄膜A同樣的操作，得到相位差薄膜B。相位差薄膜B的殘留溶劑量為0.1%，平均膜厚為80μm，捲數為4000m，Ro100nm、Rth－100nm、Nz－0.5，遲相軸係在MD方向。In addition to the use of the glue 2 for tape casting. Stripping. Dry, cut into 1650mm width, by tenter in the TD direction (with film The retardation film B was obtained in the same manner as the retardation film A except that the film was stretched by 1.15 times at 100 ° C in the direction in which the conveyance direction was orthogonal. The amount of residual solvent of the retardation film B was 0.1%, the average film thickness was 80 μm, the number of turns was 4000 m, Ro100 nm, Rth-100 nm, and Nz-0.5, and the slow phase axis was in the MD direction.

〈相位差薄膜C的製作〉<Preparation of retardation film C>

使用膠漿液2進行帶式流延．剝離．乾燥，切割成1650mm寬後，藉由拉幅機在TD方向(與薄膜的輸送方向正交的方向)中於100℃拉伸1.3倍。然後，除了在120℃、100℃乾燥的以外，進行與相位差薄膜A同樣的操作，得到相位差薄膜C。相位差薄膜C的殘留溶劑量為0.1%，平均膜厚為80μm，捲數為4000m，Ro150nm、Rth－90nm、Nz－0.1，遲相軸係在MD方向。Tape casting 2 is used for tape casting. Stripping. After drying and cutting into a width of 1,650 mm, it was stretched by 1.3 times at 100 ° C in a TD direction (a direction orthogonal to the conveying direction of the film) by a tenter. Then, the same operation as in the retardation film A was carried out except that the film was dried at 120 ° C and 100 ° C to obtain a retardation film C. The amount of residual solvent of the retardation film C was 0.1%, the average film thickness was 80 μm, the number of turns was 4000 m, Ro 150 nm, Rth-90 nm, and Nz-0.1, and the slow phase axis was in the MD direction.

〈相位差薄膜D的製作〉<Preparation of retardation film D>

使用膠漿液2進行帶式流延．剝離．乾燥，切割成1650mm寬後，藉由拉幅機邊在TD方向(與薄膜的輸送方向正交的方向)中於100℃拉伸1.25倍，邊施加輸送張力而在MD方向中拉伸1.05倍以外，進行與相位差薄膜A同樣的操作，得到相位差薄膜D。相位差薄膜D的殘留溶劑量為0.1%，平均膜厚為80μm，捲數為4000m，Ro150nm、Rth－120nm、Nz－0.3，遲相軸係在MD方向。Tape casting 2 is used for tape casting. Stripping. After drying and cutting into a width of 1,650 mm, the film was stretched by 1.25 times at 100 ° C in the TD direction (direction orthogonal to the film transport direction) by a tenter, and stretched 1.05 times in the MD direction while applying a transport tension. The same operation as in the retardation film A was carried out to obtain a retardation film D. The amount of residual solvent of the retardation film D was 0.1%, the average film thickness was 80 μm, the number of windings was 4000 m, Ro 150 nm, Rth-120 nm, and Nz-0.3, and the slow phase axis was in the MD direction.

〈位差薄膜E~I、L~N的製作〉<Production of Dislocation Films E~I, L~N>

與相位差薄膜A的製作同樣地使用膠漿液2，適當地調整膜厚、拉伸倍率，製作各自具有表2記載的Ro、Rth、Nz值之相位差薄膜E~I、L~N。In the same manner as in the production of the retardation film A, the film thickness 2 and the stretching ratio were appropriately adjusted, and the retardation films E to I and L to N each having the values of Ro, Rth, and Nz shown in Table 2 were produced.

(相位差薄膜J、K：具有茀骨架的聚碳酸酯薄膜之製作)(Retardation film J, K: production of polycarbonate film having an anthracene skeleton)

聚碳酸酯的聚合係藉由眾所周知的用光氣之界面聚縮合法來進行。於具備攪拌機、溫度計及回流冷卻器的反應槽內，投入氫氧化鈉水溶液及離子交換水，於其中使具有下述構造的單體[A]與[B]以86對14之莫耳比溶解，添加少量的亞硫酸氫鹽。接著，添加二氯甲烷，在20℃費約60分鐘吹入光氣。再者，添加對第三丁基酚以使乳化後，添加三乙胺，在30℃攪拌約3小時間而結束反應。反應結束後，分離取得有機相，使二氯甲烷蒸發而得到聚碳酸酯共聚物。所得到的共聚物之組成比係與投入量比大致同樣。The polymerization of the polycarbonate is carried out by a well-known interfacial polycondensation method using phosgene. A sodium hydroxide aqueous solution and ion-exchanged water were placed in a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, and the monomers [A] and [B] having the following structure were dissolved at 86 to 14 molar ratio. Add a small amount of bisulfite. Next, dichloromethane was added, and phosgene was blown at 20 ° C for about 60 minutes. Further, after adding p-tert-butylphenol so as to emulsify, triethylamine was added, and the mixture was stirred at 30 ° C for about 3 hours to complete the reaction. After completion of the reaction, the organic phase was separated and evaporated to give a polycarbonate copolymer. The composition ratio of the obtained copolymer was substantially the same as the ratio of the input amount.

使此共聚物溶解在二氯甲烷中，製作固體成分濃度18質量%的膠漿溶液。由於膠漿溶液製作流延薄膜，得到未拉伸薄膜。此未拉伸薄膜的殘留溶劑量為0.9質量%。藉由在拉伸溫度225℃，適當地調節拉伸倍率，對薄膜進行1軸拉伸，以製作Ro138nm、Rth－83nm的相位差薄膜J、及Ro83nm、Rth－50nm的相位差薄膜K。This copolymer was dissolved in dichloromethane to prepare a dope solution having a solid concentration of 18% by mass. An unstretched film was obtained by casting a cast film from the dope solution. The amount of residual solvent of this unstretched film was 0.9% by mass. The film was subjected to one-axis stretching at a stretching temperature of 225 ° C and the stretching ratio was appropriately adjusted to prepare a retardation film J of Ro 138 nm and Rth - 83 nm, and a retardation film K of Ro 83 nm and Rth - 50 nm.

《偏光板1、3、5~10的製作》"Production of polarizing plates 1, 3, 5~10"

將厚度120μm的聚乙烯醇薄膜浸漬在100kg含有1kg碘、4kg硼酸的水溶液中，於50℃拉伸6倍以製作膜厚25μm的偏光鏡。以完全皂化型聚乙烯醇5%水溶液當作黏著劑，藉由輥對輥，在該偏光鏡的一面上貼合已進行鹼皂化處理的市售之纖維素酯薄膜KC8UX(Konica－Minolta Opto(股)製)，在另一面上貼合同樣已進行鹼皂化處理的相位差薄膜1、3、5~7，而成為偏光板1、3、5~7。鹼皂化處理的條件係如以下。A polyvinyl alcohol film having a thickness of 120 μm was immersed in 100 kg of an aqueous solution containing 1 kg of iodine and 4 kg of boric acid, and stretched 6 times at 50° C. to prepare a polarizer having a film thickness of 25 μm. A fully saponified polyvinyl alcohol 5% aqueous solution was used as an adhesive, and a commercially available cellulose ester film KC8UX (Konica-Minolta Opto (s) was subjected to alkali saponification treatment on one side of the polarizer by a roll-to-roll method. In the film), the retardation films 1, 3, and 5 to 7 which have been subjected to alkali saponification treatment are bonded to the other surface to form polarizing plates 1, 3, and 5 to 7. The conditions of the alkali saponification treatment are as follows.

〈鹼皂化處理〉<alkali saponification treatment>

於上述條件下，對薄膜試料依順序進行皂化、水洗、中和、水洗，接著在80℃進行乾燥。Under the above conditions, the film samples were sequentially subjected to saponification, water washing, neutralization, and water washing, followed by drying at 80 °C.

除了代替市售的纖維素酯薄膜KC8UX，使用KC4UY (Konica－Minolta Opto(股)製)，代替相位差薄膜1、3、5~7，使用市售的纖維素酯薄膜KC4UE(Konica－Minolta Opto(股)製)以外，同樣地製作偏光板8。In addition to replacing the commercially available cellulose ester film KC8UX, use KC4UY (Konica-Minolta Opto Co., Ltd.), in place of the retardation films 1, 3, and 5 to 7, a polarizing plate 8 was produced in the same manner as in the case of a commercially available cellulose ester film KC4UE (manufactured by Konica-Minolta Opto Co., Ltd.). .

同樣地在偏光鏡的兩側貼合市售的纖維素酯薄膜KC4UY，以製作偏光板9。Similarly, a commercially available cellulose ester film KC4UY was bonded to both sides of the polarizer to prepare a polarizing plate 9.

同樣地，製作僅在偏光鏡的一側貼有市售的纖維素酯薄膜KC8UX之偏光板10。Similarly, a polarizing plate 10 in which a commercially available cellulose ester film KC8UX was attached only to one side of the polarizer was produced.

《液晶顯示裝置1~31的製作》"Production of Liquid Crystal Display Devices 1 to 31"

〈實施例〉<Example>

(實施例1)(Example 1)

於所製作的偏光板1之第2相位差層的相位差薄膜1側，使用丙烯酸系黏著劑，以輥對輥貼合第1相位差層的相位差薄膜A，以製作附相位差層的偏光板1。從IPS模式型液晶顯示裝置的日立製液晶電視Wooo W32L－H90剝離預先貼合的偏光板，於背光側的液晶胞之玻璃面上，以接於上述相位差薄膜側之方式，貼合附相位差層的偏光板1。此時，第1偏光鏡的吸收軸與液晶胞的摩擦方向係呈正交地配置。又，於視覺辨識側的液晶胞之玻璃面上，以接於KC4UE的方式且第2偏光鏡的吸收軸方向與液晶胞的摩擦方向成為平行的方式，貼合偏光板8，以製作液晶顯示裝置1。第1圖顯示偏光板、液晶胞的構成、配置。On the retardation film 1 side of the second retardation layer of the polarizing plate 1 to be produced, the retardation film A of the first retardation layer was bonded to the roller by a roll-to-roll using an acrylic adhesive to form a phase difference layer. Polarizing plate 1. The pre-bonded polarizing plate is peeled off from the Hitachi LCD TV Wooo W32L-H90 of the IPS mode liquid crystal display device, and is attached to the phase of the retardation film on the glass surface of the liquid crystal cell on the backlight side. The polarizing plate 1 of the difference layer. At this time, the absorption axis of the first polarizer and the rubbing direction of the liquid crystal cells are arranged orthogonally. Further, the polarizing plate 8 is bonded to the glass surface of the liquid crystal cell on the visual recognition side so that the absorption axis direction of the second polarizer and the rubbing direction of the liquid crystal cell are parallel to the KC4UE, thereby producing a liquid crystal display. Device 1. Fig. 1 shows the configuration and arrangement of a polarizing plate and a liquid crystal cell.

(實施例2)(Example 2)

對當作第1相位差層的相位差薄膜B之一面進行電暈處理，將所處理面與偏光板10之不貼合纖維素酯薄膜的側，使用完全皂化型聚乙烯醇5%水溶液當作黏著劑，以輥對輥貼合，再於相位差薄膜B之上，使用丙烯酸系黏著劑，以輥對輥貼合當作第2相位差層的相位差薄膜2，以製作附相位差層的偏光板2。除了代替實施例1之附相位差層的偏光板1，使用附相位差層的偏光板2以外，同樣地製作液晶顯示裝置2。偏光板、液晶胞的構成、配置係第2圖所示的構成、配置。One side of the retardation film B serving as the first retardation layer was subjected to corona treatment, and the side of the treated surface and the polarizing plate 10 not bonded to the cellulose ester film was used, and a completely saponified polyvinyl alcohol 5% aqueous solution was used. As an adhesive, the roll is applied to the roll, and the acrylic adhesive is applied to the retardation film B, and the retardation film 2 serving as the second retardation layer is bonded to the roll to form a phase difference. Layer of polarizing plate 2. The liquid crystal display device 2 was produced in the same manner as the polarizing plate 1 with the retardation layer of the first embodiment except that the polarizing plate 2 with the retardation layer was used. The configuration and arrangement of the polarizing plate and the liquid crystal cell are the configuration and arrangement shown in FIG.

(實施例3)(Example 3)

除了於實施例1中，用偏光板3代替偏光板1，該偏光板3係在第2相位差層使用相位差薄膜3以外，同樣地製作表2記載的液晶顯示裝置3。In the first embodiment, the polarizing plate 3 was used instead of the polarizing plate 3, and the liquid crystal display device 3 described in Table 2 was produced in the same manner as in the case of using the retardation film 3 in the second retardation layer.

(實施例4)(Example 4)

除了於實施例2中，用相位差薄膜C代替相位差薄膜B，使用相位差薄膜4代替相位差薄膜2以外，同樣地製作液晶顯示裝置4。In the second embodiment, the liquid crystal display device 4 was produced in the same manner except that the retardation film C was used instead of the retardation film B, and the retardation film 4 was used instead of the retardation film 2.

(實施例5)(Example 5)

[塗佈液1的調製][Modulation of Coating Liquid 1]

將以上投入密閉容器內，邊攪拌邊使完全溶解而成為塗佈液1。The above was put into a sealed container, and it was completely dissolved by stirring, and it became the coating liquid 1.

[積層相位差層5的製作][Production of laminated retardation layer 5]

於纖維素酯薄膜1上，使用擠壓塗佈機來塗佈塗佈液1，邊輸送邊在50℃進行乾燥，形成MS層。接著，邊加熱到100℃邊施加輸送張力，進行1.25倍的自由端一軸拉伸。然後，在80℃的乾燥區中邊以多數的輥來輸送邊完成乾燥，切割成1500mn寬，對薄膜兩端施予寬度15mm、平均高度10μm的滾花加工，以捲繞初期張力220N/m、終點張力110N/m，捲繞在內徑6吋的芯上，得到積層相位差層5。積層相位差層的平均膜厚為58μm，捲數為4000m。於此相位差層之中，纖維素層的Ro為45nm，Rth為100nm，遲相軸係在MD方向，MS層的Ro為145nm，Rth為－102nm，遲相軸係在TD方向。The coating liquid 1 was applied onto the cellulose ester film 1 by using an extrusion coater, and dried at 50 ° C while being conveyed to form an MS layer. Next, the conveying tension was applied while heating to 100 ° C, and 1.25 times of the free end one-axis stretching was performed. Then, in a drying zone of 80 ° C, the drying was carried out by a plurality of rolls, and the film was cut into a width of 1500 nm, and a knurling process of a width of 15 mm and an average height of 10 μm was applied to both ends of the film to obtain an initial tension of 220 N/m. The end point tension was 110 N/m, and it was wound around a core having an inner diameter of 6 Å to obtain a laminated retardation layer 5. The laminated retardation layer had an average film thickness of 58 μm and a number of turns of 4000 m. Among the retardation layers, the cellulose layer has a Ro of 45 nm, an Rth of 100 nm, a slow phase axis in the MD direction, a MS layer of Ro of 145 nm, an Rth of -102 nm, and a slow phase axis in the TD direction.

對所製作的積層相位差層5進行鹼皂化處理，在偏光板10的不貼合纖維素酯薄膜之側，以纖維素酯層與偏光鏡接觸的方式進行貼合。此時，使用完全皂化型聚乙烯醇5%水溶液當作黏著劑，以輥對輥使貼合，而成為附相位差層的偏光板5。除了於實施例1中用附相位差層的偏光板5代替附相位差層的偏光板1以外，同樣地製作液晶顯示裝置5。The produced retardation layer 5 is subjected to an alkali saponification treatment, and the cellulose ester layer is bonded to the polarizer on the side of the polarizing plate 10 to which the cellulose ester film is not bonded. At this time, a completely saponified polyvinyl alcohol 5% aqueous solution was used as an adhesive, and the roll was applied to the roll to form a polarizing plate 5 with a retardation layer. The liquid crystal display device 5 was produced in the same manner as in the first embodiment except that the polarizing plate 5 with the retardation layer was used instead of the polarizing plate 1 with the retardation layer.

(實施例6)(Example 6)

於纖維素酯薄膜1上，使用擠壓塗佈機來塗佈上述塗佈液1，邊輸送邊在50℃進行乾燥，接著藉由拉幅機在TD方向(與薄膜的輸送方向正交的方向)中在100℃拉伸1.3倍。然後，在80℃的乾燥區中以多數的輥邊輸送邊完成乾燥，切割成1500mm寬，對薄膜兩端施予寬度15mm、平均高度10μm的滾花加工，以捲繞初期張力220N/m、終點張力110N/m，捲繞在內徑6吋的芯上，得到積層相位差層6。積層相位差層的平均膜厚為60μm，捲數為4000m。於此相位差層之中，纖維素層的Ro為45nm，Rth為125nm，遲相軸係在TD方向，MS層的Ro為150nm，Rth為－135nm，遲相軸係在MD方向。The coating liquid 1 was applied onto the cellulose ester film 1 by using an extrusion coater, and dried at 50 ° C while being conveyed, followed by a tenter in the TD direction (orthogonal to the film transport direction). In the direction), it was stretched 1.3 times at 100 °C. Then, drying was carried out in a drying zone of 80 ° C with a plurality of rolls while being conveyed, and cut into a width of 1500 mm, and knurling processing of a width of 15 mm and an average height of 10 μm was applied to both ends of the film to obtain an initial tension of 220 N/m. The end point tension of 110 N/m was wound around a core having an inner diameter of 6 Å to obtain a laminated retardation layer 6. The laminated retardation layer had an average film thickness of 60 μm and a number of turns of 4000 m. Among the retardation layers, the cellulose layer has a Ro of 45 nm, an Rth of 125 nm, a slow phase axis in the TD direction, a MS layer of Ro of 150 nm, an Rth of -135 nm, and a slow phase axis in the MD direction.

對所製作的積層相位差層6之MS層側進行電暈處理，使用水系丙烯酸黏著劑，貼合偏光板10的不貼合纖維素酯薄膜之側，以成為附相位差層的偏光板6。除了於實施例2中，用附相位差層的偏光板6代替附相位差層的偏光板2以外，同樣地製作液晶顯示裝置6。The MS layer side of the produced laminated retardation layer 6 is subjected to corona treatment, and the side of the polarizing plate 10 to which the cellulose ester film is not bonded is bonded to the polarizing plate 6 having the retardation layer by using a water-based acrylic adhesive. . The liquid crystal display device 6 was produced in the same manner as in the second embodiment except that the polarizing plate 6 with the retardation layer was used instead of the polarizing plate 2 with the retardation layer.

(實施例7)(Example 7)

除了於實施例1中，用相位差薄膜5代替相位差薄膜1以外，同樣地製作偏光板，製作液晶顯示裝置7。In the same manner as in the first embodiment, a retardation film 5 was used instead of the retardation film 1, and a polarizing plate was produced in the same manner to fabricate a liquid crystal display device 7.

(實施例8)(Example 8)

除了於實施例1中，用相位差薄膜D代替相位差薄 膜A以外，同樣地製作液晶顯示裝置8。In addition to the first embodiment, the phase difference film D is used instead of the phase difference film. The liquid crystal display device 8 was produced in the same manner as the film A.

(實施例9)(Example 9)

除了於實施例1中，用偏光板9代替視覺辨識側的偏光板8以外，同樣地製作液晶顯示裝置9。The liquid crystal display device 9 was produced in the same manner as in the first embodiment except that the polarizing plate 9 was used instead of the polarizing plate 8 on the visual recognition side.

(實施例10)(Embodiment 10)

除了於實施例1中，用偏光板7代替視覺辨識側的偏光板8，相位差薄膜7係以接於視覺辨識側的液晶胞之玻璃面方式作配置以外，同樣地製作液晶顯示裝置10。In the first embodiment, the polarizing plate 7 was used instead of the polarizing plate 8 on the visual recognition side, and the retardation film 7 was placed on the glass surface of the liquid crystal cell on the visual recognition side, and the liquid crystal display device 10 was produced in the same manner.

(實施例11)(Example 11)

除了於實施例1中，用偏光板6代替視覺辨識側的偏光板8，相位差薄膜6係以接於視覺辨識側的液晶胞之玻璃面的方式作配置以外，同樣地製作液晶顯示裝置11。In the first embodiment, the polarizing plate 6 was used instead of the polarizing plate 8 on the visual recognition side, and the retardation film 6 was placed so as to be attached to the glass surface of the liquid crystal cell on the visual recognition side, and the liquid crystal display device 11 was produced in the same manner. .

(實施例12)(Embodiment 12)

除了於實施例1中，用相位差薄膜E代替相位差薄膜A，用相位差薄膜9代替相位差薄膜1，以及用下述偏光板11代替視覺辨識側偏光板8以外，同樣地製作液晶顯示裝置12。In the first embodiment, the retardation film A was replaced with the retardation film E, the retardation film 9 was replaced with the retardation film 9, and the liquid crystal display was produced in the same manner except that the polarizing plate 11 described below was used instead of the visibility side polarizing plate 8. Device 12.

偏光板11係藉由對所製作的相位差薄膜8進行鹼皂化處理，在偏光板10之不貼合纖維素酯薄膜的側，以纖維素酯層與偏光鏡接觸的方式進行貼合而製作。The polarizing plate 11 is formed by subjecting the produced retardation film 8 to alkali saponification, and bonding the cellulose ester layer to the side of the polarizing plate 10 without contacting the cellulose ester film. .

(實施例13~20)(Examples 13 to 20)

除了代替實施例1的偏光板1，使用一用表2記載的第1相位差層、第2相位差層之附相位差層的偏光板以外，同樣地製作液晶顯示裝置13~20。In place of the polarizing plate 1 of the first embodiment, liquid crystal display devices 13 to 20 were produced in the same manner as in the case of using the first retardation layer described in Table 2 and the polarizing plate with the retardation layer of the second retardation layer.

〈比較例〉<Comparative example>

(比較例1、4~11)(Comparative Example 1, 4~11)

除了代替實施例1所用的偏光板1，使用一用表2記載的第1相位差層、第2相位差層之附相位差層的偏光板以外，同樣地製作液晶顯示裝置21、24~31。In place of the polarizing plate 1 used in the first embodiment, a liquid crystal display device 21, 24 to 31 was produced in the same manner as in the case of using the first retardation layer described in Table 2 and the polarizing plate with the retardation layer of the second retardation layer. .

(比較例2)(Comparative Example 2)

代替實施例1所用的偏光板1，使用一用相位差薄膜J當作第1相位差層、用相位差薄膜18當作第2相位差層之附相位差層的偏光板，及在偏光板10之不貼合纖維素酯薄膜的面上，貼合相位差薄膜18當作第3相位差層，該貼合係以該相位差薄膜成為晶胞側，而製作液晶顯示裝置22。In place of the polarizing plate 1 used in the first embodiment, a polarizing plate using the retardation film J as the first retardation layer, the retardation film 18 as the retardation layer of the second retardation layer, and the polarizing plate are used. On the surface of the 10 which is not bonded to the cellulose ester film, the laminated retardation film 18 is used as the third retardation layer, and the bonding is performed on the cell side by the retardation film to produce the liquid crystal display device 22.

(比較例3)(Comparative Example 3)

代替實施例1所用的偏光板1，使用一用相位差薄膜K當作第1相位差層、用相位差薄膜19當作第2相位差層之附相位差層的偏光板，及作為視覺辨識側偏光板，在 偏光板10之不貼合纖維素酯薄膜的面上，貼合相位差薄膜19當作第3相位差層，該貼合係以該相位差薄膜成為晶胞側，而製作液晶顯示裝置23。In place of the polarizing plate 1 used in the first embodiment, a polarizing plate using the retardation film K as the first retardation layer and the retardation film 19 as the retardation layer of the second retardation layer, and as a visual recognition are used. Side polarizer, at On the surface of the polarizing plate 10 to which the cellulose ester film is not bonded, the laminated retardation film 19 is used as the third retardation layer, and the bonding is performed on the cell side, whereby the liquid crystal display device 23 is produced.

使用以上所製作的液晶顯示裝置1~31，進行以下的評價。The following evaluations were performed using the liquid crystal display devices 1 to 31 produced above.

《評價》"Evaluation"

(色移的評價)(evaluation of color shift)

使用EZ Contrast(ELDIM公司製)，對黑顯示時的色調變化進行評價。於傾斜45度(時鐘的1點30分之方向)中，測定自法線方向起到傾斜0~80度為止的色調變化，使用人類的視感度與數值的絕對值之變動更接近的CIELUV表色系之色空間，算出|△u’ |2 ＋|△v’ |2 ，藉由以下評價基準來評價。The change in color tone at the time of black display was evaluated using EZ Contrast (manufactured by ELDIM Co., Ltd.). In the case of tilting 45 degrees (1:30 in the direction of the clock), the color change from the normal direction to the tilt of 0 to 80 degrees is measured, and the CIELUV table in which the human visual sensitivity is changed to the absolute value of the numerical value is used. In the color space of the color system, |Δu' | 2 +|Δv' | 2 was calculated and evaluated by the following evaluation criteria.

5：0.0<|△u’ |2 ＋|△v’ |2 ≦1.0 4：1.0<|△u’ |2 ＋|△v’ |2 ≦2.0 3：2.0<|△u’ |2 ＋|△v’ |2 ≦3.0 2：3.0<|△u’ |2 ＋|△v’ |2 ≦4.0 1：4.0<|△u’ |2 ＋|△v’ |2 5:0.0<|Δu' | 2 +|△v' | 2 ≦1.0 4:1.0<|△u' | 2 +|△v' | 2 ≦2.0 3:2.0<|△u' | 2 +| △v' | 2 ≦3.0 2:3.0<|△u' | 2 +|△v' | 2 ≦4.0 1:4.0<|△u' | 2 +|△v' | 2

表2中顯示結果。The results are shown in Table 2.

對實施例1~20之構成的液晶顯示裝置1~20、比較例1~11之構成的液晶顯示裝置21~31，於23℃、55%RH的環境下，使用ELDIM公司製EZ－Contrast160D進行視野角測定，結果可知液晶顯示裝置1~20係具有優異的視野角特性。The liquid crystal display devices 21 to 31 of the liquid crystal display devices 1 to 20 and the comparative examples 1 to 11 having the constitutions of the first to the ninth embodiments were subjected to an EZ-Contrast 160D manufactured by ELDIM Co., Ltd. in an environment of 23 ° C and 55% RH. As a result of measuring the viewing angle, it was found that the liquid crystal display devices 1 to 20 have excellent viewing angle characteristics.

又，如表2中所示，相對於比較例1~11之構成的液晶顯示裝置21~31，可知實施例1~20之構成的液晶顯示裝置1~20係從傾斜45度方向觀看時色移良好，視野角、色移經改善的液晶顯示裝置。Further, as shown in Table 2, it is understood that the liquid crystal display devices 1 to 20 having the configurations of the first to tenth embodiments are viewed from the oblique 45-degree direction with respect to the liquid crystal display devices 21 to 31 having the configurations of the first to the eleventh embodiments. A liquid crystal display device with improved movement, improved viewing angle and color shift.

1‧‧‧第1偏光鏡1‧‧‧1st polarizer

2‧‧‧第1相位差層2‧‧‧1st phase difference layer

3‧‧‧第2相位差層3‧‧‧2nd phase difference layer

4‧‧‧第1基板4‧‧‧1st substrate

5‧‧‧液晶層5‧‧‧Liquid layer

6‧‧‧第2基板6‧‧‧2nd substrate

7‧‧‧第3相位差層7‧‧‧3rd phase difference layer

8‧‧‧第2偏光鏡8‧‧‧2nd polarizer

11‧‧‧第1偏光鏡1的吸收軸11‧‧‧Absorption axis of the first polarizer 1

12‧‧‧第1相位差層2的遲相軸12‧‧‧The phase axis of the first phase difference layer 2

13‧‧‧第2相位差層3的遲相軸13‧‧‧The retardation axis of the second phase difference layer 3

14‧‧‧第1基板4的摩擦方向14‧‧‧The rubbing direction of the first substrate 4

15‧‧‧第2基板6的摩擦方向15‧‧‧The rubbing direction of the second substrate 6

16‧‧‧第2偏光鏡8的吸收軸16‧‧‧ absorption axis of the second polarizer 8

第1圖係與本發明有關的偏光板及液晶顯示裝置之構成。Fig. 1 is a view showing the configuration of a polarizing plate and a liquid crystal display device according to the present invention.

第2圖係與本發明有關的偏光板及液晶顯示裝置之另一構成。Fig. 2 is a view showing another configuration of a polarizing plate and a liquid crystal display device according to the present invention.

Claims (5)

一種液晶顯示裝置，係依順序配置有第1偏光鏡、第1基板、液晶層、第2基板及第2偏光鏡，在第1偏光鏡與第1基板之間配置有第1相位差層及第2相位差層，黑顯示時該液晶層的液晶分子係相對於一對基板的表面呈平行地配向，其特徵為：第1相位差層之由下述式(1)所示的折射率各向異性Nz係於-0.5≦Nz≦0的範圍，且第1相位差層為一軸性，第2相位差層之由下述式(2)所表示的面內的遲滯值Ro為5<Ro≦100nm，且第2相位差層之由下述式(3)所表示的厚度方向之遲滯值Rth為100<Rth≦200nm，第1偏光鏡的吸收軸與液晶層的摩擦方向係正交，第1相位差層及第2相位差層之中，靠近第1基板之側的相位差層之遲相軸係與液晶層的摩擦方向實質上呈平行，第1相位差層及第2相位差層之中，靠近第1偏光鏡之側的相位差層之遲相軸係與第1偏光鏡的吸收軸實質上呈平行，Nz=(nx-nz)/(nx-ny)………(1) Ro=(nx-ny)×d………(2) Rth={(nx+ny)/2-nz}×d………(3)(式中，nx係相位差層面內的遲相軸方向之折射率，ny係相位差層面內的進相軸方向之折射率，nz係相位差層厚度方向之折射率，d係相位差層的厚度 (nm))。 In a liquid crystal display device, a first polarizer, a first substrate, a liquid crystal layer, a second substrate, and a second polarizer are disposed in this order, and a first retardation layer and a first retardation layer are disposed between the first polarizer and the first substrate. In the second retardation layer, the liquid crystal molecules of the liquid crystal layer are aligned in parallel with respect to the surfaces of the pair of substrates in the black display, and the first retardation layer has a refractive index represented by the following formula (1). The anisotropic Nz is in the range of -0.5 ≦Nz ≦ 0, and the first retardation layer is monoaxial, and the in-plane hysteresis value Ro of the second retardation layer represented by the following formula (2) is 5< Ro ≦ 100 nm, and the hysteresis value Rth of the second retardation layer in the thickness direction represented by the following formula (3) is 100 < Rth ≦ 200 nm, and the absorption axis of the first polarizer is orthogonal to the rubbing direction of the liquid crystal layer. Among the first retardation layer and the second retardation layer, the retardation axis of the retardation layer on the side close to the first substrate is substantially parallel to the rubbing direction of the liquid crystal layer, and the first retardation layer and the second phase Among the difference layers, the retardation axis of the phase difference layer close to the side of the first polarizer is substantially parallel to the absorption axis of the first polarizer, and Nz = (nx - nz) / (nx - ny)... (1) Ro=(nx-ny)×d... (2) Rth={(nx+ny)/2-nz}×d... (3) (where nx is within the phase difference plane The refractive index in the direction of the slow axis, the refractive index in the direction of the phase axis in the phase difference layer of ny, the refractive index in the thickness direction of the nz phase retardation layer, and the thickness of the retardation layer in the d system (nm)). 如申請專利範圍第1項之液晶顯示裝置，其中該第1相位差層的Ro為50≦Ro≦300nm。 The liquid crystal display device of claim 1, wherein Ro of the first retardation layer is 50 ≦Ro ≦ 300 nm. 如申請專利範圍第1或2項之液晶顯示裝置，其中於該第2基板與第2偏光鏡之間配置有第3相位差層，該第3相位差層滿足0≦Ro≦5nm，且0≦| Rth |<40nm。 The liquid crystal display device of claim 1 or 2, wherein a third retardation layer is disposed between the second substrate and the second polarizer, and the third retardation layer satisfies 0≦Ro≦5 nm, and 0 ≦ | Rth |<40nm. 如申請專利範圍第1項之液晶顯示裝置，其中該第2相位差層含有纖維素酯系樹脂。 The liquid crystal display device of claim 1, wherein the second retardation layer contains a cellulose ester resin. 如申請專利範圍第1項之液晶顯示裝置，其中該第1相位差層含有苯乙烯系樹脂或茀系樹脂。The liquid crystal display device of claim 1, wherein the first retardation layer contains a styrene resin or a lanthanum resin.
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