TW200835945A - Polarization plate and liquid crystal display device - Google Patents

Abstract

Provided is a polarization plate appropriate for an in-plane switching mode liquid crystal display device. The polarization plate can reduce a hue change when an angle-of-view is changed. A liquid display device using the polarization plate is also provided. The polarization plate includes at least: a first protection film, a first polarization film, a second protection film containing a particular cellulose ester as a main content, and a phase difference layer for fixing the orientation of the bar-shaped liquid crystal oriented substantially vertical to the surface of polarization film or the second protection film. These components are arranged in this order. Each retardation between the second protection film and the phase difference layer, retardation in the state that the second protection film and the phase difference layer are layered, and the wavelength dispersion characteristic are in a particular range. An absolute value of the angle defined by the transmittance axis of the polarization film and the in-plane delayed phase axis of the second protection film is in a range from 0 to 1 degree.

Description

200835945 IX. INSTRUCTIONS OF THE INVENTION [Technical Field] The present invention relates to a polarizing plate and a liquid crystal display device, and more particularly to a polarizing plate suitable for a horizontal electric field switching type liquid crystal display device, which can be changed in a viewing angle A polarizing plate with a reduced color change and a liquid crystal display device using the same. [Prior Art] The horizontal electric field switching type liquid crystal display device is superior to the liquid crystal mode of other liquid crystal display devices, for example, in terms of color, contrast, viewing angle, etc. with respect to the xenon mode, and is relative to the vertical alignment mode (VA, MVA). (PVA, etc.) is excellent in display performance such as the viewing angle, and the effect of the change in the brightness of the intermediate adjustment is small, and the effect of the decrease in the response speed (reSponse) is small. Effect, In Plane Switching) The liquid crystal display device of the mode type is extremely popular in the market. In addition to the IPS mode, the IPS mode liquid crystal display device has an FFS (fringe field switching) mode and an FLC (strong dielectric liquid crystal) mode. The IP S method of the prior art has a necessity that the liquid crystal cell itself is not compensated, and a wide viewing angle can be obtained even if it is a non-compensating film (see, for example, Patent Document 1). However, the polarizing plate itself used for the liquid crystal display device is in the crossed Nicols state at the absorption axis with 45. The direction in which the viewing angle is changed causes light leakage, which causes a decrease in the contrast of the periphery of the liquid crystal display device. -5-200835945 Therefore, a method in which an optical film such as Patent Document 2 or Patent Document 3 is laminated on a polarizing plate to suppress light leakage of the polarizing plate has been proposed. However, these methods are difficult to achieve by polarizing the roll to roll, and because the adhesive layer or the adhesive layer is bonded to a plurality of films, it takes a lot of labor and cost, and thus causes transmission. The problem is a decrease in the rate or a thick film of the polarizing plate. Further, as disclosed in Patent Document 4, a method in which a rod-like liquid crystal is vertically aligned and a cured layer is provided in a support in which a retardation-increasing agent is placed is proposed as disclosed in Patent Document 5, and the normal direction and the film surface of the discotic liquid crystal are aligned. A film that becomes a parallel way. These alignment layers are provided in the alignment treatment, and the alignment is achieved under the honing treatment to widen the contrast viewing angle. However, the films produced by these methods have problems in wavelength dispersion characteristics. As a result, in the case where the films are used in a liquid crystal display device, the color change is remarkable when the viewing angle of the front view is deviated, and the quality is improved. It will cause great problems for self-evident. [Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-13 1700 (Patent Document 2) Japanese Patent Application Laid-Open No. Hei 2 0 0 6 - 1 2 6 7 7 0 Patent Document 3 Japanese Patent Publication No. 2 005-31626 Patent Literature 4 JP-A-2005-265 379 PATENT DOCUMENT 5: JP-A-2005-309379 SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION -6 - 200835945 A polarizable film can be obtained in a liquid crystal angle of view, and is mainly composed of an ester. The surface will be substantially in the form of a difference layer; the environment is at Rt, and therefore, the object of the present invention is a polarizing plate suitable for a horizontal electric field mode switching crystal display device, the purpose of which is to provide a polarizing plate which is used to change the color change and to use it. Means for Solving the Problem of the Liquid Crystal Display Device The above problems of the present invention can be achieved by the following configuration.

[1] A polarizing plate in which at least a first protective film and a first and a laminated retardation layer are arranged in this order, and the laminated retardation layer is laminated to satisfy the following formula 1 a second protective film of cellulose, and a phase of the second protective film and 23° C of the phase difference layer, which are fixed to the alignment of the rod-shaped liquid crystal vertically aligned on the polarizing film or the second protective film, 55% RH j Wavelength 5 90 nm The retardation Ro shown by the following formula 3, 4 is: 2nd protective film: Ro: 30~115 nm

Rt: 100 ~ 250 nm

Rt/Ro: 1.6 to 4.4 retardation layer: R〇: 〇~i〇nm Rt: -100 ～-400 nm, the laminated retardation layer has an optical axis in the plane, at 23 ° C, 55% RH In the environment, the retardation at wavelength 590 nm is Ro: 30~105 nm, Rt = -300~25 nm, and the wavelength dispersion defined by the following formulas 5, 6, 7, 8 is special 200835945 D ( Ro ) 1 : 0·9 〜1 .〇D(Ro) 2· -9.5 〇nm D ( Rt ) 1 ·· 〇·3 ～0.9 D(Rt) 2: _100 __i 〇 nm, the transmission axis of the polarizing film and the second protection The absolute angle of the angle formed by the slow axis in the plane of the film is 0~1. In the range, Equation 1: 2·00$(Χ + Υ)^2·60 (wherein, as the degree of substitution of the thiol group of the cellulose ester, X represents the degree of substitution of the thiol group, and the degree of substitution of the fluorenyl group) Formula 3 ·· Ro = (nx-ny)xd Equation 4: Rt= [ (nx+ny)/2_nz] xd (wherein the second protective film or retardation layer, or the second protective film and the retardation layer The refractive index of the in-plane slow axis direction of the laminate is nx, and the refractive index in the direction orthogonal to the slow axis in the in-plane is ny, and the refractive index in the thickness direction is nz, and d is the thickness (nm) of each) Equation 5: D(R〇)1-R〇(6 3 0)/R〇(4 8 0) Equation 6: D(R〇)2 = R〇(630)-R〇(4 80) Equation 7: D(Rt)l= | Rt(630)/Rt(480) | Equation 8 ·· D(Rt)2 = Rt(480)-Rt(630) -8- 200835945 (where R〇(480), R〇(630) shows 480 nm at 23 °C and 5 5% RH, and the delays in 630 nm are R値, Rt(480) and Rt(6 3 0 ) at 480 nm and 630 nm. Delay Rt値). [2] The polarizing plate of item 1, wherein the cellulose ester satisfies the following formula 2, Formula 2: O.lOSYgl.OO. [3] The polarizing plate of the first aspect, wherein the first surface of the second protective film faces the polarizing film, and the second surface of the second protective film facing the first surface is disposed to face the phase difference The way of the layer. [4] The polarizing plate of the first aspect, wherein the retardation layer is disposed between the second protective film and the polarizing film. [5] A liquid crystal display device comprising: the polarizing plate of the first item, wherein the liquid crystal molecules are substantially aligned in a direction parallel to the glass base when the black color is displayed, and the alignment of the two glass base sides a liquid crystal cell having a substantially parallel direction and a polarizing plate comprising a third protective film, a second polarizing film, and a fourth protective film, the second protective film of the polarizing plate of the first aspect of the patent application The retardation phase axis is substantially parallel to the alignment direction of the liquid crystal cell, and the third protective film is Ro: 0 to 5 nm, Rt: -10 to 10 nm, and further the film thickness of the third protective film is 20~ 45 μιη. [6] A liquid crystal display device comprising the polarizing plate of the first item, wherein the liquid crystal molecules are substantially aligned in a direction parallel to the glass base and the alignment of the two glass base sides The direction is a substantially parallel liquid crystal cell, and a polarizing plate composed of a third protective film and a second polarizing film and a fourth protective film -9-200835945; the phase axis of the first term, and the liquid crystal cell The alignment film is Ro: 0 to 5 nm, and Rt: -10 to 1 is 20 to 45 μm. Advantageous Effects of Invention According to the present invention, it is possible to provide a polarizing plate suitable for a crystal display device, and it is possible to provide a polarizing plate and a liquid crystal display device using the same. BEST MODE FOR CARRYING OUT THE INVENTION The present invention is not limited to the above. The inventors of the present invention have found that the wavelength dispersion characteristics of the phase difference of the transverse electric field mode switching mode plate and the wavelength dispersion characteristic of the difference have a large influence on the above-mentioned problems, and the repeated force control means the color change means. The horizontal electric field mode switch light plate of the present invention is obtained by arranging a polarizing film in the following order, and a polarizing plate is provided in accordance with the following formula 1, a protective film, and a alignment of the polarizing film or the second aligned rod-shaped liquid crystal. The inward direction of the second protective film is substantially orthogonal, the third protection is 0 nm, and the color change of the third protective film is reduced when the horizontal electric field mode switching mode liquid crystal viewing angle is lowered. The good form is explained in detail, but this effort repeatedly repeats the review results. 'In the first type of liquid crystal display device, the phase difference, especially the phase of the film thickness direction, can be confirmed by changing the color of the viewing angle, in the perspective of the viewing angle. Can be clear. In the case of the mode liquid crystal display device, at least the first protective film and the surface of the second protective film containing the cellulose ester of the first film are substantially perpendicularized to the phase difference layer of the polarizing plate -10- In 200835945, the second protective film and the phase difference layer have a retardation Ro and Rt represented by the formula 3, 4 at a wavelength of 5 90 nm in an environment of 23 ° C and 55% RH, and the second protective film: R 各自: 30 to 115 nm R t : 1 0 0 to 2 5 0 nm Rt/Ro: 1.6 to 4.4 retardation layer: Ro: 0 to 10 nm Rt: -100 to -400 nm 'In laminating the second protective film with In the state of the phase difference layer, the retardation at the wavelength of 590 nm in the state of 23, 5 5% RH is R〇: 30~105 nm, Rt= _3 00~25 nm, and the laminated film is in the same plane. The wavelength dispersion characteristic having an optical axis and defined by the following formulas 5, 6, 7, and 8 is D(Ro) 1: 0·9 to 1.0 D (Ro) 2 : -9·5 〜 〇 nm D ( Rt) 1 : 〇·3 〇9 D ( Rt ) 2 : -ΐ00 〜 _1 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The scope is characterized by it. Formula 1 · 2 〇〇S(X + Y)S2.60 Formula 2 : 0.l〇gYSL〇〇 (wherein f乍 is the substitution of the cellulose ester _ group, X 醯 取代 取代 substitution degree, Y Showing the substitution degree of propyl thiol). -11 - 200835945 Equation 3: Ro=(nx-ny)xd Equation 4: Rt = ((nx + ny)/2_nz)xd (wherein the second protective film or retardation layer, or the second protective film and phase The refractive index of the retardation axis in the plane of the poor layer shows nx, the refractive index in the direction of the in-plane and the stagnation axis is ny, the refractive index in the thickness direction shows nz, and d shows the thickness (nm ))) Equation 5: D(R〇)1=R〇(630)/R〇(480) Equation 6: D(R〇)2 = R〇(63 0)-R〇(480) Equation 7: D (Rt)l= | Rt(630)/Rt(480) | Equation 8 _ D(Rt)2 = Rt(480)-Rt(630)

(wherein, Ro ( 480 ) and R 〇 ( 63 0 ) are 48 0 nm in the environment of 23 ° C, 55% RH, and the delay in 63 0 nm, Rt ( 480 ), • Rt ( 6 30) is a retardation Rt値 at 480 nm and 630 nm.) In order to make the second protective film in the above range, the second proof film is subjected to heat treatment. Stretching treatment is preferred. Further, in the case where the cellulose ester is heat-treated and stretched, in order to reduce the residual shape as much as possible, the glass transition temperature is about ± 1 〇 ° C, which is orthogonal to the transport direction. Stretching in a direction of about 1. 1 times to about 1⁄5 times, or a film produced by solution casting (f 1 〇wcasting), in a residual state in which the amount of residual solvent is about 2 to 100% by mass. It is preferable to perform stretching of about 1 · 1 to 1 · 7 times in the direction of the direction of the conveyance. Further, in order to make the retardation layer in the above range from -12 to 200835945, the film thickness control of the retardation layer is performed, the temperature at the time of ultraviolet curing, the tilt angle control, and the pre-heating of the support and the air interface. The control of the tilt angle is preferred. In particular, the film thickness control and the temperature at the time of hardening have a great influence on the phase difference control. Further, in the case of the alignment of the liquid crystal or the use of the vertical alignment film, since the pretilt angle of the liquid crystal material of the present invention and the air interface can reach the susceptor side, a special alignment film is not necessary. Further, in order to prevent the retardation of the laminated retardation layer in which the second protective film and the retardation layer are laminated within the range of the number, the R〇 of the second protective film is controlled by the above-described means, and 2 The phase difference when the protective film and the retardation layer are observed in the respective oblique directions is controlled to be achieved. The phase difference in the oblique direction of the second protective film is preferably controlled in the stretching condition at the time of producing the second protective film. When the phase difference is reduced by the in-plane axis of the second protective film, the stretching ratio can be increased or the stretching temperature can be lowered. The phase difference in the oblique direction of the retardation layer is preferably controlled by the film thickness of the retardation layer or the temperature at the time of hardening. In order to reduce the phase difference in the oblique direction, the film thickness can be made thinner or the temperature at the time of hardening can be increased. Rt can be calculated by the sum of the phase differences from the tilt direction and the in-plane phase difference based on the phase axes. Further, in terms of means for controlling the dispersion of the wavelength, D ( Ro ) 1, D (Ro) 2 is preferably a material and a production method suitable for selecting the second protective film. In the case of a material, the substituent can be achieved by changing the substituent (type/degree of substitution) with a cellulose ester-based material. In the case of only the ethyl hydrazide group, the lower the degree of substitution, the larger the enthalpy, and the more the fluorenyl group is increased, the smaller the enthalpy is -13-200835945. It can also be changed by additives. In the case of the retardation increasing agent or the like described in Patent Document 3 or the like, there is a tendency to become large. D ( Rt ) 1, D (Rt ) 2 can control the phase difference between the second protective film and the retardation layer to achieve the specific phase, and in particular, the phase difference of the second protective film becomes relatively large and becomes smaller. value. In the present invention, the absolute axis of the transmission axis of the first polarizing film and the retardation axis of the second protective film surface is 〇1. The range is characterized by the fact that the in-plane slow axis and the transport direction of the second protective film are in a straight direction and can be achieved by unevenness in the control surface. For this reason, the balance between the stretching temperature and the stretching ratio is precisely controlled so that the stretching portion (the jig of the stretcher or the like) can be independently controlled on both sides of the protective film. This is achieved by adjusting the stretching temperature and the stretching ratio with respect to the clamp position and the stress of the jig. Further, the liquid crystal display device of the present invention has the polarizing plate of the present invention and the black display of the characteristics of the IP S mode type liquid crystal cell, wherein the liquid crystal molecules are substantially aligned in a direction parallel to the glass base, both sides a polarizing plate comprising a liquid crystal cell substantially parallel to the glass substrate side and a third polarizing film and a fourth polarizing film, and the polarizing plate of the first protective film according to claim 1 The surface retardation axis of the second protective film is substantially parallel or orthogonal to the alignment direction of the liquid crystal cell, and the third protective film is Ro: 0 to 5 nm, Rt: -10 to 10 urn, and further 3 A horizontal electric field mode switching type liquid crystal display device in which the film thickness of the protective film is 20 to 45 μm. In other words, the retardation 値 of the second protective film and the retardation layer is controlled to a specific range of −14 to 200835945, and the delay of the third protective film 値R〇, Rt is reduced and thinned, and the transverse electric field mode switching mode can be improved. The viewing angle expansion effect of the liquid crystal display device can also greatly suppress the change in color, and it is known that the color change in the black display is remarkable, but it can be greatly reduced. When the third protective film has a retardation within the range of the number, the third protective film is a cellulose ester, and can be formed by melt film formation or film formation using a solution, and is maintained at a temperature higher than the glass transition temperature in the middle. It is preferred to add an additive having a birefringence developance opposite to that of the cellulose ester for more than 15 seconds. Further, in the case of a cycloolefin-based film, it is preferred to use a film produced by melt casting or solution casting without using a stretching treatment. Hereinafter, each element of the present invention will be described in detail. (Measurement of delayed enthalpy) An example of the delayed enthalpy measurement of the present invention was carried out using an environment of KOBRA21ADH manufactured by Oji Scientific Instruments at 23 ° C and 5 5 % R Η. Further, when calculating the retardation in the thickness direction, an Abbreviation is used and the refractive index 该 of the wavelength of each layer is measured. Further, in the case of the laminate, it is decided to use the average enthalpy of the refractive index of each layer. In the present invention, in the case where the retardation in the thickness direction of the laminate becomes a negative enthalpy, when the retardation enthalpy is calculated, the in-plane phase axis of the laminate is used as the tilt axis, and the retardation at the 40-degree tilt is measured and determined for calculation. . (Configuration of Polarizing Plate and Liquid Crystal Display Device) The configuration of the polarizing plate and the liquid crystal display device of the present invention is as shown in Fig. -15-200835945. Fig. 1(A) shows the configuration of a polarizing plate and a liquid crystal display device according to item 5 of the patent application. The phase difference layer 7 in which the first protective film 1, the first polarizing film 5, the second protective film 2, and the alignment of the rod-shaped liquid crystal are fixed to each other is visually recognized, and a polarizing plate on the visible side is formed. It is combined with the liquid crystal cell 8 held by the glass substrate 9,10. Further, on the surface opposite to the liquid crystal cell 8, a polarizing plate composed of the third protective film 3, the second polarizing film 6, and the fourth protective film 4 is disposed. The in-plane retardation axis b of the second protective film is parallel to the alignment direction c of the liquid crystal cell. The polarized light of the polarizing film passes through the axis a, and the honing axis d of the glass substrate is in the direction shown in the drawing. In the figure, the phase difference layer 7 can be disposed between the first polarizing film 5 and the second protective film 2. (B) of Fig. 1 is a configuration of a polarizing plate and a liquid crystal display device according to claim 6 of the patent application. The polarizing plate is formed by the fourth protective film 4, the second polarizing film 6, and the third protective film 3, and the polarizing plate is bonded to the liquid crystal cell 8 held by the glass substrate 9, 1 . Further, on the surface opposite to the liquid crystal cell 8, a retardation layer 7 for fixing the alignment of the rod-like liquid crystal, a second protective film 2, a first polarizing film 5, and a first protective film 1 are disposed. A polarizing plate is constructed. The retardation axis b in the plane of the second protective film and the alignment direction c of the liquid crystal cell are orthogonal. The polarized light of the polarizing film passes through the axis a, and the honing axis d of the glass substrate is in the direction shown in the drawing. In the figure, the phase difference layer 7 can be disposed between the first polarizing film 5 and the -16-200835945 second protective film 2. (Phase retardation layer) The liquid crystal alignment is performed by applying a liquid crystal (or a liquid crystal solution) to a substrate to perform drying and heat treatment (which may be referred to as alignment treatment) by ultraviolet ray or thermal polymerization. The immobilization is characterized by a retardation layer having a substantially vertical alignment of rod-like liquid crystal. The retardation layer ' is formed as a substrate on the second polarizing film or the second protective film, and is preferably formed on the second protective film. Φ This definition of S-directed orientation refers to the case where the optical phase difference of the obtained liquid crystal alignment layer is evaluated by using a polarizing microscope, and the liquid crystal alignment layer is held between the crossed Nicols polarizing elements. It can be seen that the black 'in the case of tilting the liquid crystal alignment layer between the crossed Nicols polarizing elements, the light is the vertical alignment of the transmissive. In the formation of the liquid crystal alignment layer, a so-called vertical alignment film may be preferably used, and the vertical alignment film is not particularly limited, and the liquid crystal material itself is vertically aligned at the air interface, and the alignment regulating force and the air interface are In the case of the opposite interface, the alignment film is not particularly necessary, and it is preferable from the viewpoint of simplification. In the case of using a vertical alignment film, an alignment film of a block polymer composition containing a (meth)acrylic block polymer described in JP-A-2005-148473 or the like can be used. It is better. The retardation layer of the present invention has a retardation 値R〇 of 0 to 10 nm, and Rt is a substantially vertically aligned rod-like liquid crystal in the range of -100 to -400 nm. -17 - 200835945 retardation layer. Further, R 〇 is preferably in the range of 0 to 5 nm. In order to make the phase difference layer have the above range, the film thickness control of the phase difference layer, the temperature at the time of ultraviolet curing, the inclination angle control, and the control of the pretilt angle of the support and the air interface are preferable. The phase difference layer is formed by hardening a liquid crystal material which has a set temperature and which is a liquid crystal phase and which has a predetermined liquid crystal regularity. The upper limit of the temperature of the liquid crystal phase is not particularly limited as long as the temperature of the transparent resin film of the substrate is not damaged. Specifically, from the viewpoint of easiness of control of the process temperature and maintenance of dimensional accuracy, it is preferably 120 or less, more preferably 100 ° C or lower, and the liquid crystal material of the liquid crystal phase can be suitably used. On the other hand, 'the lower temperature limit of the liquid crystal phase is displayed, and when it is used as a phase difference plate, the temperature at which the gastric liquid crystal material maintains the alignment state can be obtained. As the liquid crystal material used for the phase difference plate of the present invention, a polymerizable liquid crystal material is preferably used. The polymerizable liquid crystal material can be polymerized by irradiation with the active radiation to be irradiated, and the state of being polymerized is fixed in the alignment state. Therefore, when a polymerizable liquid crystal material is used, the lower limit of the temperature of the liquid crystal phase is not particularly limited. In the case of the polymerizable liquid crystal material, any of a polymerizable liquid crystal monomer, a polymerizable liquid crystal oligomer or a polymerizable liquid crystal polymer may be used, or may be used in combination with each other. Since the polymerizable liquid crystal material can be fixed in the alignment state, the alignment of the liquid crystal can be easily performed at a low temperature, and the alignment state can be fixed during use. Therefore, it can be used regardless of the use conditions such as temperature. In terms of the polymerizable liquid crystal material, in the above, a polymerizable liquid crystal -18-200835945 monomer can be suitably used. The polymerizable liquid crystal monomer can be aligned at a lower temperature than the polymerizable liquid crystal oligomer or the polymerizable liquid crystal polymer, and the sensitivity is high at the time of alignment, so that it is easy to align. Specific examples of the polymerizable liquid crystal monomer include the rod-like liquid crystal compound (I) represented by the following general formula (1) and the rod-like liquid crystal compound (II) represented by the following general formula (2). In the case of the rod-like liquid crystal compound (I), two or more kinds of the compounds of the general formula (1) may be used in combination, and similarly, the rod-like liquid crystal compound (II) may be mixed and contained in the general formula (2). Two or more kinds of compounds are used. In addition, one type or more of the rod-like liquid crystal compound (I) may be used, and one type or more of the rod-like liquid crystal compound (Π) may be used in combination. General formula (1) R1 Ο ch2c-co^ch2Vo—/^V-CO—

Ch2^-o-cch2 b R2 [Chemical 2] General

R3 I CH2C—CO II

In the general formula (1) representing the rod-like liquid crystalline compound (I), R1 and R2 each represent a hydrogen atom or a methyl group, and R1 and R2 are both from the range of the temperature range of the liquid crystal phase -19 to 200835945. It is preferably a hydrogen atom. X is a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, a cyano group, or a nitro group, and a chlorine atom or a methyl group is preferred. Further, the (meth)acryloxy group at both ends of the molecular chain of the rod-like liquid crystalline compound (I) and the alkene chain length of the spacer which is a spacer are a and b, respectively. Any integer may be obtained in the range of 2 to 1 2, and preferably in the range of 4 to 10, and more preferably in the range of 6 to 9. The compound of the general formula (1) which is a = b = 0 lacks stability and is not only susceptible to hydrolysis, but also has high crystallinity of the compound itself. Further, a and b are compounds of the general formula (1) each of 13 or more, and the isotropic transfer temperature (ΤΙ) is low. From this reason, it is understood that the temperature range in which the liquid crystallinity is exhibited by any of the compounds is not preferable. The rod-like liquid crystalline compound (I) can be synthesized by any method. For example, a rod-like liquid crystalline compound (I) wherein X is a methyl group can be esterified with 1 equivalent of methylhydroquinone and 2 equivalents of 4-(m-(meth)acryloxypropoxy)benzoic acid. Got it. The esterification reaction is carried out by activating the above benzoic acid with mercapto chloride or pulverized acid anhydride or the like, and reacting it with methylhydroquinone. Further, by using a condensing agent such as DC C (dicyclohexylcarbodiimide), the carboxylic acid unit can be directly reacted with methylhydroquinone. In the other methods, first, one equivalent of methylhydroquinone is carried out, and esterification reaction with 2 equivalents of 4-(m-benzyloxyalkoxy)benzoic acid is carried out, followed by hydrogenation reaction or the like. After debenzylation, a rod-like liquid crystalline compound (I) can also be synthesized by a method in which a molecular end is acrylylated. In the esterification reaction of methylhydroquinone with 4-(m-benzyl-20-200835945 oxyalkoxy)benzoic acid, after introducing methylhydroquinone into diacetate, the above benzoic acid is It is also feasible to carry out the reaction in a molten state and directly obtain an ester body. In the general formula (where X is a non-methyl group, a rod-like liquid crystalline compound (〇, except that hydroquinone having a corresponding substituent is used, instead of methylhydroquinone, the same reaction is carried out to obtain the same. In the general formula (2) of the liquid crystalline compound (π), R3 represents a hydrogen atom or a methyl group, and R3 is preferably hydrogen in terms of the breadth of the temperature range in which the liquid crystal phase is displayed, and the chain length c of the alkylene group is shown. The rod-like liquid crystalline compound (II) having a rhodium of 2 to 12 does not exhibit liquid crystallinity. However, in consideration of compatibility with the rod-like liquid crystalline compound (I) having liquid crystallinity, c is 4 to 1 The range of 0 is preferably in the range of 6 to 9. The rod-like liquid crystalline compound (Π) can also be synthesized by any method, for example, by using 1 equivalent of 4-cyanophenol and 1 equivalent of 4-(positive (a) The rod-like liquid crystal compound (II) can be synthesized by esterification reaction of acryloxy alkoxy group and benzoic acid. The esterification reaction is the same as in the case of synthesizing the rod-like liquid crystal compound (I). Formic acid is activated by mercapto chloride or phthalic anhydride to react with 4-cyanophenol Further, a condensing agent such as DCC (dicyclohexylcarbodiimide) may be used to react the above benzoic acid with 4-cyanophenol. In addition to the above, a polymerizable liquid crystal oligomer or a polymerizable liquid crystal oligomer may be used in the present invention. In the case of such a polymerizable liquid crystal oligomer or a polymerizable liquid crystal polymer, a conventionally proposed product can be suitably used. In the present invention, a polymerizable liquid crystal material can be used as needed. Light-initiator. When a polymerizable liquid crystal material is polymerized by electron beam irradiation, a photopolymerization initiator may be unnecessary, and generally used - 21,359,945, for example, ultraviolet (uv) irradiation hardening In the case of the photopolymerization initiator, the photopolymerization initiator is usually used for the purpose of promoting the polymerization. In terms of the photopolymerization initiator, a benzyl group (also referred to as a bisphenyl fluorenyl group), a dibenzophenone butyl benzoate isopropyl ether can be exemplified. , diphenyl-, phenylhydrazinobenzoic acid, methyl benzoylbenzoate, 4-phenylhydrazinyl-4,-methyldiphenyl sulfide, benzylaminoketal, dimethylaminocarbamate Benzoate, 2_ n-butoxyethyl-4- Dimethylamino benzoate, p-amyl dimethylaminobenzoate ' 3,3'-dimethyl-4-methoxy diphenyl ketone, methylol benzyl fluorenyl Formate, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino] 丨(4 _ morpholino base)-butylidene-1-one, 1-(4-dodecylphenyl)-2-transmethyl-2-methylpropan-1-one' 1-yl ring Hexyl phenyl ketone, 2-bromo-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1 -keto' 2 -chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone , or ^ chloro-^ propoxy thioxanthone and the like. The amount of the photopolymerization initiator to be added is generally from 〇〇1% to 2%, more preferably from 1% to 1%, most preferably in the range of 5. 5 % to 5%. It is added to the polymerizable liquid crystal material of the present invention. Further, in addition to the photopolymerization initiator, a sensitizer may be added to the extent that the object of the present invention is not impaired. The film thickness of the liquid crystal layer in the present invention is preferably in the range of 0.1 μm to 20 μm, more preferably in the range of 0.2 to 10 μm. When the liquid crystal layer of the present invention is thicker than the above range, an unnecessary optical anisotropy is generated, and if it is thinner than the above range, the optical anisotropic property of the setting may not be obtained -22-200835945. Therefore, the film thickness of the liquid crystal layer can be determined in accordance with the necessary optical anisotropy. The polymerizable liquid crystal material can be used by mixing a photopolymerization initiator, a sensitizer, or the like to prepare a composition for forming a liquid crystal layer, and coating the substrate to form a layer for forming a liquid crystal layer. In the method of forming the layer for forming a liquid crystal layer, for example, a method in which a dry film or the like is previously formed to be laminated on a substrate as a layer for forming a liquid crystal layer, or a composition for forming a liquid crystal layer may be melted on a substrate. In the present invention, a solvent is added to the liquid crystal layer-forming composition, and a coating film composition in which other components are dissolved is coated on the alignment film, and a solvent is removed to form a liquid crystal layer. It is better to use layers. This is simpler in comparison with other methods. The solvent is a solvent which can dissolve the above-mentioned polymerizable liquid crystal material, and is not particularly limited as long as it does not lower the properties of the transparent resin film. Specifically, benzene, toluene, xylene, and the like are exemplified. a hydrocarbon such as butylbenzene 'diethylbenzene or tetrahydronaphthalene; an ether such as methoxybenzene, hydrazine, dimethoxybenzene or diethylene glycol dimethyl ether; acetone, methyl ethyl a ketone such as a ketone, methyl isobutyl ketone, cyclohexanone or 2,4-pentanedione; ethyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate , propylene glycol monoethyl ether acetate, or an ester of γ-butyrolactone; 2-pyrrolidone, Ν-methyl-2-pyrrolidone, dimethylformamide, or dimethyl Amidoxime solvent such as guanamine; chloroform, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloroethane, trichloroethylene, tetrachloroethylene, chlorobenzene, or halogen of o-dichlorobenzene Solvent; tertiary butyl alcohol, diacetone-23- 200835945 alcohol, glycerin, glycerin acetate, ethylene glycol, triethylene glycol, hexanediol, ethylene glycol monomethyl ether, Ethyl cellosolve, or an alcohol such as butyl cellosolve; or a phenol, a phenol such as p-chlorophenol, or the like, or a polymerizable liquid crystal material, etc., if only a single solvent is used. Solubility is insufficient 'as in the case of the above-mentioned uranium substrate. However, it is possible to avoid this by using a mixture of two or more solvents. Among the above-mentioned solvents, as a separate solvent, a hydrocarbon-based solvent and a glycol monoether acetate-based solvent are preferred as a mixed solvent, and are ethers or a mixture of ketones and ethylene glycols. . The concentration of the solution is determined according to the solubility of the polymerizable liquid crystal material or the thickness of the liquid crystal layer to be produced, and is usually not limited to 1% to 60%, more preferably 3% to 40%. % range adjustment. The liquid crystal layer-forming composition used in the present invention may contain a compound other than the above insofar as the object of the present invention is not impaired. The compound to be added may, for example, be a polyester prepolymer obtained by condensing a polyvalent alcohol with a basic acid or a polybasic acid, and reacting the (meth)acrylic acid to obtain a polyester (meth) acrylate; After reacting a polyhydric alcohol group with a compound having two isocyanate groups, a polyurethane (meth) acrylate obtained by reacting the reaction product with (meth)acrylic acid; a bisphenol A type epoxy resin' Bisphenol F type epoxy resin, novolak type epoxy resin, polycarboxylic acid polyepoxypropyl ester, polyalcohol polyepoxypropyl ether, aliphatic or alicyclic epoxy resin, amine epoxy An epoxy resin such as a base resin, a trisphenol methane type epoxy resin, a dihydroxybenzene type epoxy resin, or the like, and an epoxy group (meth) acrylate obtained by reacting (A-24-200835945-based) acrylic acid. The photopolymerizable compound or a liquid crystal compound having a propylene group or a photopolymerizable group having a methacryl group. The amount of the compound to be added to the composition for forming a liquid crystal layer of the present invention can be selected without departing from the scope of the object of the present invention. In general, the composition for forming a liquid crystal layer of the present invention is 40% or less. Better' is better than 20%. By the addition of these compounds, the hardenability of the liquid crystal material can be improved in the present invention, the mechanical strength of the resulting liquid crystal layer can be increased, and the stability can be improved. Further, a composition for forming a liquid crystal layer in a solvent is added, and a surfactant or the like may be added in order to facilitate the coating film. In the case where the surfactant to be added is exemplified, a cationic surfactant such as an imidazole, a fourth-order ammonium salt, an alkylamine oxide or a polyamine derivative; a polyoxyethylene-polyhydroxypropylene condensate; Grade or second alcohol hydroxyethyl ester, alkyl phenol hydroxyethyl ester, polyethylene glycol and its esters 'sodium lauryl sulfate, ammonium lauryl sulfate, ammonium lauryl sulfate 'alkyl substituted aromatic sulfonic acid An anionic surfactant such as a salt, an alkyl phosphate, an aliphatic or aromatic sulfonic acid formalin condensate; an amphoteric surfactant such as lauryl guanamine propyl betaine or lauryl amide acetate betaine; Non-ionic surfactants such as polyethylene glycol fatty acid esters, polyoxyethylene alkylamines, etc.; perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl ethylene oxide adducts , perfluoroalkyltrimethylammonium salt, perfluoroalkyl group, hydrophilic group-containing oligomer, perfluoroalkyl group, lipophilic group-containing oligomer, fluorine system containing perfluoroalkylamine formate, etc. Surfactant and the like. The amount of surfactant added is determined by the type of surfactant, the type of liquid crystal material, the type of solvent, and the type of alignment film of the solution coating film. Usually, it is an aqueous liquid crystal containing a solution of -25-200835945. The material i 〇ppm~〗 〇% is better, better! (10) ppm to 5%' is preferably in the range of 〇·ι to 1%. The method of coating the composition for forming a liquid BB layer may, for example, be a spin coating method, a roll coating method, a printing method, a immersion raising method, a die coating method, a casting method, a rod coating method, or a knife. A coating method, a spray coating method, a gravure coating method, an inverse coating method, or an extrusion coating method. The method of removing the solvent after coating the liquid 曰 θ layer forming composition, for example, may be air-dried, heated or removed, or removed under reduced pressure, and the like. A layer for forming a liquid crystal layer can be formed by removal of a solvent. In the step of curing the polymerizable liquid crystal material, energy for curing the polymerizable liquid crystal material can be imparted, and it can be heat energy, and it can usually be carried out by irradiation with ionizing radiation having a polymerization ability. If necessary, a polymerization initiator may be contained in the polymerizable liquid crystal material. In the case of the ionizing radiation, the radiation for polymerizing the polymerizable liquid crystal material is not particularly limited. Generally, ultraviolet light or visible light can be used from the viewpoint of easiness of the device, etc., and light having a wavelength of 150 to 500 nm is preferable. Preferably, it is 250 to 45 〇 nm, and the best is ultraviolet light at a wavelength of 3 0 0 to 4 0 nm. In the present invention, ultraviolet light (UV) is irradiated/irradiated as active radiation. It is preferred to carry out radical polymerization by ultraviolet radical self-polymerization initiator to carry out radical polymerization. The use of UV in the form of actinic radiation is a well-established technique, so that the polymerization initiator to be used can be applied to the present invention more easily. In terms of a light source that can illuminate the ultraviolet light, a low pressure mercury lamp (sterilization lamp 'fluorescent chemical lamp, black light lamp'), a high pressure discharge lamp (high pressure water -26-200835945 silver lamp 'metal halogen lamp), or a short arc discharge can be exemplified. Lights (ultra-high pressure mercury lamps, xenon lamps, mercury lamps). Among them, metal halide lamps, 氙 lamps, high-pressure mercury lamps, etc. can be recommended. The irradiation intensity can be suitably adjusted in accordance with the composition of the polymerizable liquid crystal material forming the liquid crystal layer or the photopolymerization initiator. In the step of forming the liquid crystal layer forming layer by the irradiation of the actinic radiation, the processing temperature, that is, the polymerizable liquid crystal material may be carried out under the temperature conditions of the liquid crystal phase, and the ratio may be liquid crystal phase. The temperature can be lowered at a lower temperature. When the polymerizable liquid crystal material of the liquid crystal phase is formed, even if the temperature is lowered later, the alignment state is not rapidly disturbed. (Substrate) In the present invention, the substrate to be used for the protective films of the first to fourth aspects is preferably one which is easy to manufacture, optically transparent, and the like, and particularly preferably a transparent resin film. % The transparency of the present invention means that the transmittance of visible light is 60% or more, preferably 80% or more, and particularly preferably 90% or more. The above properties are not particularly limited, and examples thereof include a cellulose diacetate film, a cellulose triacetate film, a cellulose acetate propionate film, a cellulose acetate butyrate film, and the like. Cellulose ester film, polyester film, polycarbonate film, polyarylate film, poly(polyether oxime) film, polyethylene terephthalate, polyethylene naphthalate Polyester film, polyethylene film, polypropylene film, cellophane, polyvinyl chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, heterogeneous -27-200835945 (syndiotactic) polystyrene film, Polycarbonate film, norbornene resin film, polymethylpentene film, polyether ketone film, polyether ketoximine film, polyamide film, fluororesin film, nylon film, poly A methyl methacrylate film, a propylene film or a glass plate. Among them, a primary alkenyl resin film and a cellulose ester film are preferred. The amorphous polyolefin film having a lower primary alkenyl structure, for example, APO manufactured by Mitsui Petrochemical Co., Ltd. or Zeonex manufactured by Zeon Corporation of Japan, manufactured by JSR Corporation, is used as the base resin-based resin film which can be suitably used in the present invention. ARTON and so on. In the protective film of the first to fourth aspects of the present invention, it is preferable to use a cellulose ester-based film, in particular, a substrate of the second protective film, and a cellulose ester having a specific cellulose ester as a main component described later. film. In terms of cellulose ester, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate phthalate, preferably cellulose acetate Ester, cellulose acetate propionate is preferred. Commercially available cellulose ester films include, for example, Konika Minolta Tac KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC12UR, KC4FR, KC8UY-HA, KC8UX-RHA (above, Konika Minoltaopt) Etc., it can be suitably used in terms of manufacturing, cost, transparency, adhesion, and the like. The film may be a film produced by melt casting, or a film produced by solution casting. -28-200835945 <Cellulose ester> The cellulose ester used in the second protective film of the present invention will be described in detail. The cellulose ester used in the second protective film of the present invention is preferably an aliphatic carboxylic acid ester or an aromatic carboxylic acid ester having a carbon number of from 2 to 22, or a mixed ester of an aliphatic carboxylic acid ester and an aromatic carboxylic acid ester. In particular, lower fatty acid esters of cellulose are preferred. The lower fatty acid ester of cellulose lower fatty acid means a fatty acid having 6 or less carbon atoms. Specifically, it is cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate phthalate, etc., or 曰本特开平1 0-45 804, the same as 8 A mixed fatty acid ester such as cellulose acetate propionate or cellulose acetate butyrate described in the specification of U.S. Patent No. 2,311,052, and the like. In the above description, in particular, the lower fatty acid ester of cellulose which can be suitably used is cellulose acetate propionate. The cellulose ester, which has a fluorenyl group having 2 to 22 carbon atoms as a substituent, has a degree of substitution of the ethyl ketone group of X, and when the degree of substitution of the fluorenyl group is Y, the following formulas 1 and 2 can be simultaneously satisfied. Cellulose ester. Equation 1 2.00SX + Y^2.60 Equation 2 0.10^ 1.00 where 2·30^Χ + Υ ‘2.55 is better, and 2.40SX + YS2.55 is better. Also, 〇.50$Υ^〇·90 is preferred, and 0.70SYS0.90 is preferred. -29- 200835945 The part that is not replaced by thiol 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-D 817-9. The cellulose ester is a cellulose ester synthesized from cotton linters, wood pulp, kenaf or the like as a raw material, and may be used singly or in combination. In particular, linter, it is preferred to use the cellulose ester synthesized from the wood pulp separately or in combination. Further, the cellulose esters obtained by the above may be used in combination at any ratio. In the case of the cellulose ester, when the cellulose raw material thiolating 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 can be used, and sulfuric acid is used. The protonic catalyst is obtained by reacting according to the conventional method. In the case of ethyl ketone cellulose, it is necessary to prolong the time of the oximation reaction in order to increase the acetylation rate. However, if the decomposition time is too long when the reaction time is too long, the polymer chain is cleaved or the acetamino group is decomposed, resulting in poor results. Therefore, in order to increase the degree of acetylation and suppress the decomposition to a certain extent, it is necessary to set the reaction time to a certain range. The reaction conditions are as specified in the reaction time, and the conditions of the reaction apparatus or equipment vary greatly, which is not appropriate. As the polymer is decomposed, the molecular weight distribution becomes wider, and even in the case of the cellulose ester, the degree of decomposition can be specified by the weight average molecular weight (Mw) / number average molecular weight (?n) which are usually used. That is, in the process of acetylation of cellulose triacetate, if it is too long, it does not undergo excessive decomposition, and in the case of acetamization, in order to carry out sufficient time, the oximation reaction is used as an index of the degree of reaction. - 200835945 Weight average molecular weight (Mw) / number average molecular weight (Μη). The ratio of the weight average fraction 3 of the cellulose ester used in the present invention to the number average molecular weight (??) Mw / Μη is preferably. Further, in the present invention, the cellulose ester film is a cellulose ester having a enthalpy of 1.4 to 3.0 as a material (preferably cellulose triacetate or cellulose acetate propionic acid M w / Μη).値 is preferably in the range of 1.4 to 3.0. It is difficult to form a cellulose ester having a uniform molecular weight by a gel filtration method, etc., but the cost of the method is remarkably low if it is 3.0 or less. Further, the amount of the cellulose ester used in the present invention, the number (??) is preferably from 80000 to 200000. The content of ΰ20000 is more preferably from 150,000 to 200,000. The average molecular weight and molecular weight distribution of the cellulose ester can be determined by a known method. The calculated amount and the weight average molecular weight can be calculated by the ratio (Mw / Μη) as follows. Solvent: dichloromethane Column: Shodex K806, K805, K803G (Use Showa Electric for 3 connections)

Column temperature: 2 5 °C Sample concentration: 〇. 1% by mass 値 can be made: amount (Mw) 1 · 4~3 · 0 is a cellulose ester ester which can contain Mw /) And can be improved. Further, it is more preferably an average molecular weight of 〇〇〇〇〇1 〇〇〇〇〇~ by a high-speed liquid number average molecular company. -31 - 200835945 Detector: RI Model 504 (made by GL Scientific) Pump: L6000 (Hitachi Manufacturing Co., Ltd. Flow rate: 1.0 ml/min Calibration curve: A calibration curve was obtained using 13 samples up to standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) Mw = 1 000000 to 500. 13 samples are preferably obtained at approximately equal intervals. A method for producing a cellulose ester can be obtained by the method of JP-A-10-50-804. Further, the cellulose ester is affected by a trace amount of a metal component in the cellulose ester. We believe that these are related to the water used in the manufacturing process, and the insoluble core is preferred as the lesser component, the metal ions such as iron, calcium, magnesium, etc., and the possibility of containing acidic groups. A polymer decomposition product or the like is formed by salt formation to form an insoluble matter, and preferably it is less. The iron (Fe) component is preferably 1 ppm or less. The punitive (Ca) component is contained in a large amount in the groundwater or river water. When it is used for a long time, it is hard water. It is not suitable as a beverage water, and an acidic component such as a carboxylic acid or a citric acid has a large amount of a ligand. It is easy to form a complex with a coordination compound, and forms a residue derived from a large amount of insoluble calcium (insoluble precipitate, turbidity).

The component (Ca) is 60 ppm or less, preferably 0 to 30 ppm. When the magnesium (Mg) component is too large, an insoluble component is generated, so that it is preferably 0 to 70 ppm, particularly preferably 〇20 ppm. The metal component such as iron (Fe) content, calcium (Ca) content, and magnesium (Mg) content is a micro-digested wet decomposition apparatus (sulfuric acid decomposition), alkali After the pretreatment by melting, it was obtained by analyzing using ICP-AES-32-200835945 (inductively coupled plasma luminescence spectroscopic analyzer). 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 for measuring the refractive index of the film was measured using an A-fold refractometer according to Japanese Industrial Standard JI S K 7 105. <Additive> The cellulose ester film may contain an additive such as a plasticizer or an ultraviolet absorber, an antioxidant, a matting agent or the like. The cellulose ester film used in the third protective film of the present invention preferably has a retardation 〇 R〇 of 〇 5 5 nm and a Rt of -10 to 10 nm. In order to achieve the above range, when the third protective film is a cellulose ester, it may be produced by melt film formation, or may be formed into a film by a solution, and maintained at a temperature equal to or higher than the glass transition temperature for 15 seconds or more, or by adding fibers. Preferably, the ester is an additive having reproducible refraction. Among them, in order to adjust the retardation within the above range, it is preferred to contain the following propylene-based polymer. <Propylene-based polymer> The cellulose ester film used in the third protective film of the present invention contains a propylene group having a weight-average molecular weight of 50 Å or more and 30,000 or less with respect to a negative direction of birefringence in the direction of stretching. Preferably, the propylene-based polymer is preferably a propylene-based polymer having an aromatic ring in a side chain or a propylene-based polymer having a cyclohexyl group in a side chain. The polymer has a weight average molecular weight of 500 or more and 30,000 or less. -33-200835945 The composition of the polymer can be controlled to have good compatibility with the polymer. In particular, a propylene-based polymer, a propylene-based polymer having an aromatic ring in a side chain or a propylene-based polymer having a cyclohexyl group in a side chain, and preferably having a weight average molecular weight of 500 or more and 10,000 or less, may be displayed in addition to the above. The cellulose ester film after film formation is excellent in transparency and extremely low in moisture permeability, and is excellent as a protective film for a polarizing plate. Since the polymer has a weight average molecular weight of 500 or more and 30,000 or less, it is considered to be from an oligomer to a low molecular weight polymer. In order to synthesize such a polymer, it is difficult to control the molecular weight of the usual polymerization, and it is desirable to use a method in which the molecular weight is made as uniform as possible without excessive molecular weight. In the case of such a polymerization method, a method of using a peroxide polymerization initiator such as cumene peroxide or a tertiary butyl hydroperoxide may be exemplified, and a polymerization initiator may be used in a usual amount of polymerization. A method of using a chain transfer agent such as a hydrosulfide compound or carbon tetrachloride in addition to a polymerization initiator, and a method of using a polymerization inhibitor such as phenylhydrazine or dinitrobenzene in addition to a polymerization initiator. Further, as in Japanese Patent Laid-Open No. 2000-128911 Or a compound having a thiol group and a second-order hydroxyl group as in the case of the publication No. 2000-344823, or a method of performing block polymerization using the compound and a polymerization catalyst for an organometallic compound, etc. It is suitably used in the invention, and the method of the publication is particularly preferred. The monomer constituting the monomer unit of the useful polymer of the present invention may, but is not limited to, the following. The ethylenic composition constituting the polymer obtained by polymerizing the ethylenically unsaturated monomer is not -34 - 200835945. Saturated monomer unit: the ethyl ester ester may, for example, be vinyl acetate, vinyl propionate, vinyl butyrate or vinyl valerate. Ester, trimethyl vinyl acetate, acetamyl hexanoate, vinyl decanoate, vinyl laurate, vinyl crotonate, vinyl palmitate, vinyl stearate, ethylene cyclohexanecarboxylate Ester, vinyl octanoate, vinyl methacrylate, ethyl crotonate, vinyl sorbate, vinyl benzoate, vinyl cinnamate, etc.; and acrylate, for example, methyl acrylate, propylene Ethyl acetate, propyl propyl acrylate (iso, positive), butyl acrylate (positive, iso, secondary, tertiary), amyl acrylate (positive, iso, secondary), hexyl acrylate (positive, different) , propylene hexanoate (positive, iso), octyl acrylate (positive, iso), decyl acrylate (positive, iso), glycerin oleic acid (positive, iso), propylene hexanoate, (2-ethylhexyl) acrylate, benzyl acrylate, phenylethyl acrylate, propylene (ε-caprolactone), (2-hydroxyethyl) acrylate, (2-hydroxypropyl) acrylate, (3-hydroxypropyl) acrylate, (4-butylidene) vinegar Record acid (2 · butyl butyl) vinegar, acrylic acid _ p-hydroxymethyl phenyl ester, acrylic acid - p- (2-hydroxyethyl) phenyl ester, etc.; methacrylate type, change the above acrylate to methacrylic acid An ester; an unsaturated acid system such as acrylic acid, methacrylic acid, maleic anhydride, crotonic acid, itaconic acid or the like. The polymer composed of the above monomers may be a copolymer, a homopolymer of a vinyl ester, a copolymer of a vinyl ester, a copolymer of a vinyl ester and an acrylic acid or a methacrylate. In the present invention, the propylene-based polymer means a homopolymer or a copolymer of an acrylic acid or an alkyl methacrylate having no aromatic ring or a cyclohexyl monomer unit. The propylene-based polymer having an aromatic ring in the side chain means a propylene-based polymer containing an acrylic or methacrylic acid monomer unit having an aromatic ring of -35 to 200835945. Further, the propylene-based polymer having a cyclohexyl group in the side chain means a propylene-based polymer containing a monomer unit of an acrylic acid or a methacrylate having a cyclohexyl group. The acrylate monomer having no aromatic ring or cyclohexyl group may, for example, be methyl acrylate 'ethyl acrylate' propyl acrylate (iso-, positive), butyl acrylate (positive, different, secondary, tertiary) Amyl acrylate (positive, iso, secondary), hexyl acrylate (positive, iso), heptyl acrylate (positive, iso), octyl acrylate (positive 'iso), decyl acrylate (positive, iso), acrylic meat Myristyl ester (positive, iso), (2-ethylhexyl) acrylate, acrylic acid (ε-caprolactone), (2-hydroxyethyl) acrylate, (2-hydroxypropyl) acrylate, acrylic acid (3 -hydroxypropyl)ester, (4-hydroxybutyl) acrylate, (2-hydroxybutyl) acrylate, (2-methoxyethyl) acrylate, (2-ethoxyethyl) acrylate Etc., or to change the above acrylate to methacrylate. The propylene-based polymer is a homopolymer or a copolymer of the above monomers, preferably having a methyl acrylate monomer unit of 30% by mass or more, and further having a methyl methacrylate monomer unit of 40% by mass or more. It is better. In particular, a homopolymer of methyl acrylate or methyl methacrylate is preferred. As the acrylic or methacrylic acid ester monomer having an aromatic ring, for example, phenyl acrylate, phenyl methacrylate, acrylic acid (2 or 4-chlorophenyl) ester, methacrylic acid (2 or 4-chloro) may be mentioned. Phenyl) ester, acrylic acid (2 or 3 or 4-ethoxycarbonylphenyl) ester, methacrylic acid (2 or 3 or -36 - 200835945 4 -ethoxycarbonylphenyl) ester, acrylic acid (neighbor or between Or p-tolyl), methacrylic acid (o- or m- or p-tolyl) 'benzyl acrylate, benzyl methacrylate, phenylethyl acrylate, phenylethyl propyl acrylate, acrylic acid (2-naphthalene) Ethyl ester, etc., and benzyl acrylate, benzyl methacrylate, phenethyl acrylate, phenethyl methacrylate can be suitably used. In the propylene-based polymer having an aromatic ring in the side chain, the acrylic or methacrylic acid monomer unit having an aromatic ring has 20 to 40% by mass, and has a mass ratio of 50 to 80 in an acrylic or methyl methacrylate monomer unit. % is better. In the polymer, the acrylic acid or methacrylic acid monomer unit having a hydroxyl group is preferably 2 to 20% by mass. In the case of the cyanate ester monomer having a cyclohexyl group, for example, cyclohexyl acrylate, cyclohexyl methacrylate, (4-methylcyclohexyl) acrylate, and methacrylic acid (4-methyl group) may be mentioned. Cyclohexyl)ester, (4-ethylcyclohexyl)propionate, (4-ethylcyclohexyl) methacrylate, etc., may be suitably used as cyclohexyl acrylate and cyclohexyl methacrylate. In the propylene-based polymer having a cyclohexyl group in the side chain, the monomer unit of the acrylic acid or methacrylate having a cyclohexyl group is 20 to 40% by mass, and preferably 50 to 80% by mass. Further, in the polymer, the unit of the acrylic acid or methacrylic acid ester having a hydroxyl group is preferably 2 to 20% by mass. The polymer obtained by polymerizing the above ethylenically unsaturated monomer, a propylene-based polymer, a propylene-based polymer having an aromatic ring in a side chain, and a propylene-based polymer having a cyclohexyl group in a side chain are excellent in compatibility with a cellulose resin. In the case of an acrylic or methacrylic ester monomer having such a hydroxyl group, it is not a homopolymer but a constituent unit of the copolymer. In this case, it is preferred that the acrylic acid or methacrylic acid monomer unit having a hydroxyl group of -37 to 200835945 is contained in the propylene-based polymer in an amount of 2 to 20% by mass. In the present invention, a polymer having a hydroxyl group in a side chain can also be suitably used. The monomer unit having a hydroxyl group is the same as the monomer, and acrylic acid or methacrylate is preferred, and for example, (2-hydroxyethyl) acrylate or (2-hydroxypropyl) acrylate is exemplified. , (3-hydroxypropyl) acrylate, (4-hydroxybutyl) acrylate, (2-hydroxybutyl) acrylate, p-hydroxymethylphenyl acrylate, acrylic acid-p-(2-hydroxyethyl) The phenyl ester, or the acrylic acid substituted with methacrylic acid, is preferably 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. The acrylate or methacrylate monomer unit having a hydroxyl group in the polymer is preferably 2 to 20% by mass, more preferably 2 to 10% by mass in the polymer. The polymer is such that the monomer unit having the above hydroxyl group is contained in an amount of 2 to 20% by mass, and of course, compatibility with cellulose ester, retention, dimensional stability, moisture permeability is not only small, and is protected as a polarizing plate. The polarizing element of the film is excellent in adhesion, and has an effect of improving the durability of the polarizing plate. The method of having a hydroxyl group at at least one terminal of the main chain of the acrylic polymer, especially the method of having a hydroxyl group at the terminal of the main chain, is not limited, and azobis(2-hydroxyethylbutyrate) can be used. A method of a radical polymerization initiator having a hydroxyl group, using a method of a chain transfer agent having a hydroxyl group like 2-hydrothioethanol, 'using a polymerization stopper having a radical, by ionization ion polymerization A method having a hydroxyl group at the terminal, a compound having a thiol group and a hydroxyl group of 2, or a compound of the formula 2 and 2000-344823, or a compound of the compound and the organic gold-38-200835945 The polymerization catalyst of the compound can be obtained by a method of bulk polymerization, etc., and the method of the publication is particularly preferable. The polymer produced by the method related to the description of this publication is sold in the market under the Actflow series manufactured by Soybean Chemical Co., Ltd., and can be used just right. 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 of the polymer and improving the transparency. Further, in the case of the ethylenically unsaturated monomer which exhibits a negative alignment birefringence with respect to the stretching direction, it is preferred that a polymer having a styrene type exhibits negative refractive properties. Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethylstyrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, and methoxybenzene. Ethylene, ethoxylated styrene, chlorostyrene, dichlorostyrene, bromostyrene, methyl benzoate, etc., but is not limited thereto. The monomer may be copolymerized by the exemplified examples of the unsaturated ethylenic monomer, and two or more kinds of the above polymers may be used as the phase-soluble cellulose ester for the purpose of controlling the birefringence. Further, the cellulose ester film used in the present invention contains an ethylenically unsaturated monomer Xa having no aromatic ring and a hydrophilic group in the molecule, and an aromatic ring having no hydrophilic group, and having a hydrophilic group. A polymer X having a weight average molecular weight of 5,000 or more and 30,000 or less obtained by copolymerization of a saturated monomer Xb, and a polymer having a weight average molecular weight of 500 or more and 3000 or less, which is more preferably an ethylenically unsaturated monomer Ya having no aromatic ring. Y is better. -39 - 200835945 (Polymer X, polymer Y) The polymer X used in the present invention is an ethylenically unsaturated monomer Xa having no aromatic ring and hydrophilic group in the molecule, and has no aromatic ring in the molecule. A polymer having a weight average molecular weight of 5,000 or more and 30,000 or less obtained by copolymerization of a hydrophilic group-containing ethylenically unsaturated monomer Xb. It is preferably a propylene group or a methacryl monomer which does not have an aromatic ring and a hydrophilic group in the molecule, and a propylene group or a methacryl monomer which has a hydrophilic group in the Xb molecule. The polymer X used in the present invention is represented by the following general formula (X): 0. General formula (X) - (Xa) m - (Xb) n. (Xc) p-

Further, a polymer represented by the following general formula (X-1) is preferred. General formula (X-1) -[CH2-C(-Rl)(-C02R2)]m-[CH2-C(-R3)(-C02R4-0H)-]n-[Xc]p- (wherein R1, R3, R5 are hydrazine or CH3. R2 represents an alkyl group having a carbon number of 1 to 12, a cycloalkyl group. R4, R6 represents -CH2-, -C2H4- or -C3H6-. Xc is polymerizable in Xa, Xb The monomer units, m, η and p, show the molar composition ratio, but m is 0, η is 0, k妾0, m + n + p=100). -40- 200835945 The following is a list of constituents of the polymer conjugate used in the present invention, but is not limited thereto. In X, the hydrophilic group means a hydroxyl group and has an epoxy group: ethylene Xa which does not have an aromatic ring and a hydrophilic group in the molecule, and may, for example, be methyl acrylate, ethyl acrylate (iso-, n-), butyl acrylate (positive, different, secondary, acid amyl ester (positive, different, secondary), hexyl acrylate (heptyl orthoester (positive, iso), octyl acrylate (positive, different) (positive, different), acrylic meat Myristyl ester (positive, iso), hexyl) ester, acrylic acid (ε-caprolactone), acrylate, etc., or the above acrylate in methacrylic acid with methyl acrylate, ethyl acrylate, methacrylic acid Ethyl enoate, propyl methacrylate (iso, positive) is a monomer having no hydrophilic ring in the molecule, and a monomer having a hydrophilic group is preferably a acrylate having a hydroxyl group. For example, acrylic acid (2-hydroxy hydroxy acid) (2-hydroxypropyl) ester, acrylic acid (3-hydroxybutyl acid) (4-hydroxybutyl) ester, acrylic acid (2-hydroxybutyl group and the like substituted with methacrylic acid) Preferred as propethyl ester and methacrylic acid (2-hydroxyl) Yl) ester, propyl) acrylate, (3 - hydroxypropyl) ester.

In the Xc aspect, the content other than xa and Xb and the copolymerizable monomer are not particularly limited, and the unsaturated monomer having a monomeric ethane chain having no aromatic ring unit is propyl acrylate. ), propylene, iso), propylene, decyl acrylate acrylate (2-ethyl (2-ethoxyethyl ester substituted. Its methyl ester, methyl propyl oxime ethylenically unsaturated acrylic acid or methyl ethyl) ester, C Ester, propylene) ester, or the 'enoic acid (2-hydroxy acrylate (2-hydroxyindole) is not sufficient. -41 - 200835945

The molar composition ratio (m : n ) of Xa, Xb and Xc is preferably in the range of 99: i to 65: 35, more preferably in the range of 95: 5 to 75: 25. The p of xc is 0~10. Xc can be a plurality of monomer units.

When the molar composition ratio of Xa is large, the compatibility with cellulose vinegar can be improved, and the retardation 値Rt of the film thickness direction becomes large. When the molar composition ratio of Xb is large, the above compatibility is deteriorated, and the effect of reducing Rt is high. Further, when the composition ratio of the Mob of Xb exceeds the above range, the haze tends to occur at the time of film formation, and it is preferable to optimize the Xa and Xb composition ratios. The molecular weight of the polymer X is preferably 5,000 or more and 30,000 or less by weight average molecular weight, more preferably 8,000 or more and 25,000 or less. When the weight average molecular weight is 5,000 or more, the cellulose ester film can be reduced in size under high temperature and high humidity, and it is preferable that the polarizing plate protective film can have a small curl. The weight average molecular weight is less than 30,000, and the compatibility with the cellulose ester can be further improved. The flow under high temperature and high humidity can further suppress the occurrence of haze after film formation. The weight average molecular weight of the polymer X used in the present invention can be adjusted by a known molecular weight adjusting method. In the 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 usually from room temperature to 130 ° C, preferably from 50 ° C to 1 Torr. (: The temperature or the polymerization time may be adjusted. The method for measuring the weight average molecular weight can be achieved by the following method. (Method for measuring weight average molecular weight) -42- 200835945 Weight average molecular weight M w is a gel permeation chromatography The measurement conditions are as follows. Solvent: Dichloromethane column: Shodex K806, K805, K803G (manufactured by Showa Denko Co., Ltd., 3 connections) Column temperature: 25 ° C Sample concentration: 〇. 1 mass % Detector : RI Model 504 (manufactured by GL Scientific Co., Ltd.) Pump: L6000 (manufactured by Hitachi, Ltd.) Flow rate: 1.0 ml/min Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) Mw=10〇〇〇〇 The calibration curve is obtained for 13 samples up to 500500. The 13 samples are used at approximately equal intervals. The polymer Y used in the present invention has a weight average molecular weight obtained by polymerizing the ethylenically unsaturated monomer Ya having no aromatic ring. a polymer of 500 or more and 3000 or less. It is preferable to reduce the residual monomer of the polymer at a weight average molecular weight of 500 or more. Further, in the case of 300 or less, Zhi retardation Rt degrade performance so good.

Ya is preferably a propylene or methacryl monomer having no aromatic ring. The polymer γ used in the present invention is represented by the following general formula (γ). -43- 200835945 The general formula (γ) - (Ya) k - (Yb) q - is further preferably a polymer represented by the following general formula (Y-1). General formula (Y-1) . [CH2-C(.R5)(-C02R6)]k-[Yb]q- (wherein R5 represents hydrazine or CH3. R6 represents an alkyl group or a ring having a carbon number of 1 to 12 Alkyl. Yb shows the monomer unit copolymerizable with Ya. k and q show the molar composition t匕. But k is 0, k + q = 1 0 0 ° )

Yb is not particularly limited as long as it is an ethylenically unsaturated monomer copolymerizable with Ya. Yb can be plural. k + q = 100, q is preferably 0 to 30. The ethylenically unsaturated monomer Ya constituting the polymer Y obtained by polymerizing an ethylenically unsaturated monomer having no aromatic ring may be exemplified by methyl acrylate, ethyl acrylate or propyl acrylate. ), butyl acrylate (positive, iso, secondary, tertiary), amyl succinate (positive, iso, secondary), hexyl acrylate (positive, iso), heptyl acrylate (positive, iso), acrylic Octyl ester (positive, iso), decyl acrylate (positive, iso), myristyl acrylate (positive, iso), cyclohexyl acrylate, (2-ethylhexyl) acrylate, acrylic acid (ε-caprolactone) , (2-hydroxyethyl) acrylate, (2-hydroxypropyl) acrylate, (3-hydroxypropyl) acrylate, (4-hydroxybutyl) acrylate, (2-hydroxybutyl) acrylate In the case of methacrylate, the above acrylate is substituted with methyl-44-200835945 acrylate; and the unsaturated acid may, for example, be acrylic acid, methacrylic acid, maleic anhydride, crotonic acid or itaconic acid. Wait.

Yb is not particularly limited as long as it is copolymerizable with Ya. The vinyl ester may, for example, be vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate or trimethyl vinyl acetate. Ester, vinyl hexanoate, vinyl decanoate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, vinyl octanoate, methacrylic acid Vinyl ester, vinyl crotonate, vinyl sorbate, vinyl cinnamate, etc. are preferred. Yb can be plural. In the synthetic polymer X, Y, it is difficult to control the molecular weight in usual polymerization, and it is desirable to use a method in which the molecular weight is as uniform as possible in the method of not excessively increasing the molecular weight. In the aspect of the polymerization method, there is a method of using a peroxide polymerization initiator such as cumene peroxide or a tertiary butyl hydroperoxide, and a polymerization initiator is polymerized in a larger amount than usual, and the polymerization is used in addition to polymerization. A method of using a chain transfer agent such as a hydrosulfide compound or carbon tetrachloride other than the agent, a method using a polymerization stopper such as phenylhydrazine or dinitrobenzene other than a polymerization initiator, and further, such as JP-A-2000- 1 289 1 1 or a compound having a thiol group and a hydroxy group as in the case of 2000-3 44823, or a method of bulk polymerization using a polymerization catalyst of the compound and an organometallic compound, It can be suitably used in the present invention, and in particular, a polymerization method in which a compound having a thiol group and a 2-stage hydroxyl group is used as a chain transfer agent in a molecule is preferred. In this case, at the end of the polymer X and the polymer Y, there are those having a hydroxyl group or a sulfide derived from a polymerization catalyst and a chain transfer agent. The compatibility of the polymer X, Y with the cellulose ester can be adjusted by the end -45·200835945 residue. The valence of the hydroxyl groups of the polymer X and hydrazine is preferably from 30 to 150 [mgKOH/g]. (Measurement method based on base price) This measurement is based on JIS K 0 0 7 0 (1 9 9 2). The valence of the hydroxy group is defined as the number of mg of potassium hydroxide necessary for neutralization of the acetic acid bonded to the hydroxy group when 1 g of the sample is acetylated. Specifically, the sample Xg (about lg) was placed in a flask, and 20 ml of an acetamylation reagent (in the case of 20 ml of acetic anhydride to 400 ml) was added correctly. An air cooling tube was installed at the mouth of the flask and heated in a glycerin bath at 95 to 100 °C. 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 to make the bending point of the obtained titration curve an end point. Further, in the empty test system, the sample was subjected to titration to determine the bending point of the titration curve (i n f 1 e X i ο η ρ 〇 i n t ). The hydroxyl value can be calculated from the following formula.

Hydroxyl value = {(BC)xfx28.05/X}+D (in the formula, B is used in the blank test. The amount of 5 mol/L potassium hydroxide ethanol solution (ml), C is 0·5 mol for titration. / L of potassium hydroxide ethanol solution (ml), f is 0.5 mo 1 / L potassium hydroxide ethanol solution factor, D is acid bismuth, and, another, 8.05 shows potassium hydroxide 1 mol amount 56.11 of 1 / 2) -46 - 200835945 The polymer χ, polymer γ is excellent in compatibility with cellulose ester, and has no evaporation or volatilization for excellent productivity. It has good retention as a protective film for polarizing plates, low moisture permeability and dimensional stability. Excellent sex. The content of the polymer X and the cellulose ester film of the polymer oxime is preferably in the range of the following formula (ί) and formula (ii). When the content of the polymer X is Xg (% by mass = mass of the polymer X / mass of the cellulose ester X 100), and the content of the polymer Y is Yg (% by mass), the formula (i) 5SXg + Yg$35 (mass %) Formula (ii) 0.05S Yg / (Xg + Yg) $0.4 The appropriate range of the formula (i) is from 10 to 25% by mass. When the total amount of the polymer X and the polymer Y is 5% by mass or more, the retardation 値Rt is sufficiently reduced. Further, when the total amount is 35 mass% or less, the adhesion to the polarizing element PVA is good. The polymer X and the polymer γ can be directly added to the material constituting the doping liquid described later, dissolved, or added to the doping liquid after being dissolved in advance in an organic solvent in which the cellulose ester is dissolved. <Other Additives> The cellulose ester film of the first to fourth protective films of the present invention may contain an additive added to a usual cellulose ester film. As such additives, plasticizers, ultraviolet absorbers, microparticles and the like can be exemplified. In the present invention, a plasticizer containing the following is preferred. For the plasticizer, for example, a phosphate ester plasticizer, a phthalate plasticizer, -47-200835945 1,2,4-benzenetricarboxylate plasticizer, pyromellitic acid plasticizer, glycolic acid can be suitably used. The ester-based plasticizer is a citric acid ester plasticizer, a polyester plasticizer, a polyvalent alcohol ester plasticizer, and the like. In the phosphate ester plasticizer, there are triphenyl phosphate, tricresol phosphate 'cresol diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate 'trioctyl phosphate , tributyl phosphate, etc., in the phthalate plasticizer, diethyl phthalate, dimethoxy ethyl phthalate, dimethyl phthalate, dioctyl Benzoate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, diphenyl phthalate, dicyclohexyl benzene Diacid ester, etc., in 1,2,4-benzenetricarboxylic acid plasticizer, tributyl trimellitate, triphenyl trimellitate, triethyl trimellitate, etc. Tetraester-based plasticizer, tetrabutyl pyrophorite, tetraphenylpyramine, tetraethylpyramine, etc., in glycolic acid plasticizer, triglyceride Acid ester, glyceryl tributyrate, ethyl phthalyl ethyl hydroxyacetate, methyl phthalic acid ethyl hydroxyacetate, butyl phthalyl butyl hydroxyacetate Etc., in citrate-based plasticizers, Triethyl citrate, tri-n-butyl citrate, ethyl triethyl citrate, ethyl tri-n-butyl citrate, ethyl tri-n-(2-ethylhexyl) citric acid Esters and the like can be suitably used. Examples of other carboxylic acid esters may include butyl oleate, methyl phthalate of ricinoleic acid, dibutyl sebacate, and various I,2,4-benzenetricarboxylates. As the polyester-based plasticizer, a copolymerized polymer of a dibasic acid such as an aliphatic dibasic acid, an alicyclic dibasic acid or an aromatic dibasic acid and ethylene glycol can be used. The aliphatic dibasic acid is not particularly limited, and adipic acid, -48-200835945 azelaic acid, citric acid, terephthalic acid, 1,4-cyclohexyldicarboxylic acid or the like can be used. For the ethyl alcohol, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propylene glycol, 1,4-butenyl glycol, 1,3·butenyl glycol, 1 can be used. , 2-butenyl glycol, and the like. These dibasic acids and ethylene glycol may be used singly or in combination of two or more. The polyvalent alcohol ester-based plasticizer may be formed from an ester of a divalent or higher aliphatic polyvalent alcohol and a monocarboxylic acid. Examples of preferred polyvalent alcohols include, for example, the following, but the present invention is not limited thereto. Ribonitol (adonito 1 ), arabitol (arabitol), ethylene glycol, diethyl alcohol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol , tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, dibutenyl glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, 2-n-butyl-2-ethyl-1,3-propanediol, galactitol, Mannitol, 3-methylpentane-1,3,5-triol, tetramethyl glycol, sorbitol, trimethylolpropane, trimethylolethane, xylitol ,Wait. In particular, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol (Xylit®) are preferred. The monocarboxylic acid to be used for the polyvalent alcohol ester is not particularly limited, and a 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, the moisture permeability is improved, and the retention is preferred. The following examples of the preferred monocarboxylic acid are exemplified, and 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 suitably used. It is better to have a carbon number of 1 to 20, and a carbon number of 1 to 1 0 -49-200835945. When acetic acid is contained, the compatibility with cellulose ester is preferably increased, and acetic acid may be used in combination 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, n-decanoic acid, 2-ethyl-hexanecarboxylic acid, and undecylic acid. , lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanic acid, icosonic acid, behenic acid, tetracosic acid, twenty-six Acid, thirty-seven acid, octadecanoic acid, tridecanoic acid, tridecanoic acid, etc., saturated fatty acid, undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid Such as unsaturated fatty acids. As an example of a suitable alicyclic monocarboxylic acid, a cyclopentanecarboxylic acid, a cyclohexanecarboxylic acid, a cyclooctanecarboxylic acid, or the like can be exemplified. Examples of a suitable aromatic monocarboxylic acid include benzoic acid, an alkyl group introduced into a benzene ring of benzoic acid such as tolylmethyl carboxylic acid, a biphenyl carboxylic acid, a naphthalene carboxylic acid, a tetrahydronaphthalene carboxylic acid, or the like. There are two or more aromatic monocarboxylic acids having a benzene ring, or such derivatives. Especially benzoic acid is preferred. The molecular weight of the polyvalent alcohol ester is not particularly limited, and is preferably in the range of from 30,000 to 1,500 Å, more preferably in the range of from 3 to 50 750. The larger one is preferable in terms of the improvement of the retention property, and the smaller one is preferable to the compatibility with the moisture permeability and the cellulose ester. The carboxylic acid used in the polyvalent alcohol ester used in the present invention may be one type or a mixture of two or more types. Further, the OH group in the polyvalent alcohol may be completely esterified with a carboxylic acid, or a part may be left as an OH group. These plasticizers are preferably used singly or in combination. The amount of the plasticizer to be used is preferably from 1 to 20% by mass, particularly preferably from 3 to 13 to 50 to 200835945% by mass, based on the film properties and workability. The ultraviolet absorber used in the present invention can be used for the purpose of improving durability by absorbing ultraviolet rays of 400 nm or less, and particularly preferably having a transmittance of 10% or less at a wavelength of 3 70 nm, more preferably 5% or less, more preferably 5% or less. It is 2% or less. The ultraviolet absorber to be used in the present invention is not particularly limited, and examples thereof include a hydroxydiphenyl ketone compound, a benzotriazole compound, a salicylate compound, a diphenyl ketone compound, and a cyanoacrylate system. A compound, a three well system compound, a nickel salt fault compound, an inorganic powder, and the like. It can also be used as a polymeric UV absorber. The cellulose ester film used in the present invention is preferably a microparticle. The fine particles may be an inorganic compound or an organic compound and may be used arbitrarily. Examples of the inorganic compound may, for example, be cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium citrate, water and calcium citrate, aluminum citrate , magnesium citrate and calcium phosphate. It is preferable that the microparticles have a turbidity lower by containing the ruthenium, and in particular, ruthenium dioxide is preferred. The average particle diameter of the primary particles of the microparticles is preferably 5 to 50 nm, more preferably 7 to 20 nm. It is preferable that the main component contains a condensate of 2 times as the particle size 〇·〇5~0·3μιη2. The content of the 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 a multi-layered cellulose ester film resulting from the co-flow casting method, it is preferred that the surface contains such an added amount of microparticles. The fine particles of cerium oxide are, for example, commercially available under the trade names of Aerosil R972, R972V, -51 - 200835945 R974, R812, 200, 200V, 300, R202, 0X50, TT600 (above 'Nippon Aero Si 1 Co., Ltd.), The fine particles of the cerium oxide can be used, for example, under the trade names of Aerosil R976 and R811 (above, manufactured by Nippon Aero Sil Co., Ltd.). The polymer may, for example, be a polyoxyn resin, a fluororesin or a propylene resin. Polyoxymethylene resin is preferred, especially those having a three-dimensional network structure, for example, Tospear 103, the same 1〇5, the same 108, the same 120, the same 145, the same 3120 and the same 240 (above, Toshiba Poly The trade name of Oxygen Co., Ltd. is commercially available and can be used. Among them, Aerosil 200V and Aerosil R972V can keep the turbidity of the cellulose ester film low, and the effect of lowering the friction coefficient is particularly suitable. <Method for Producing Cellulose Ester Film> Next, a method for producing a cellulose ester film used in the present invention will be described. The cellulose ester film used in the present invention is preferably a solution prepared by solution casting or melt casting. The cellulose ester film used in the present invention is a step of dissolving a cellulose ester and an additive in a solvent to prepare a doping step, and performing a casting process on the endless metal support in which the doping is infinitely transferred, and the flow is carried out. The step of casting the doping with a mesh, the step of peeling from the metal support, the step of stretching or wide-width maintaining, and then the step of drying, the step of winding the final processed thin-52-200835945 film get on. The steps of modulation doping are described below. The concentration of cellulose in the doping may be preferably a dry load after casting in a metal support, and an increase in load during filtration when the concentration of the cellulose ester is too high. The concentration of the coexistence is preferably 10 to 3 % by weight, more preferably 15 to 2 5 % by mass. The solvent used for doping may be used singly or in combination of two or more kinds of good solvents and weak solvents for mixing cellulose esters, and the solubility of the cellulose ester is preferably good. . The proper range of the mixing ratio of the good solvent to the weak solvent is 98% by mass of the good solvent and 2 to 30% by mass of the weak solvent. Good solvent, weak solvent The cellulose ester to be used can be dissolved as a good solvent, and it can be dissolved as a weak solvent. Therefore, due to the average degree of acetylation of cellulose esters (ethylidene degree), good solvents and weak solvents are changed. For example, when acetone is used, the cellulose ester of cellulose ester (acetamyl substitution degree) 2.4), the cellulose acetate propionate becomes a good solvent, and the cellulose acetate (degree of substitution 2 8 ) becomes a weak solvent. The good solvent to be used in the present invention is not particularly limited, and examples thereof include an organic halogen compound such as dioxane or a dioxolane ketone, methyl acetate or methyl acetacetate. Particularly preferred is dichloromethane or methyl ester. Further, the weak solvent used in the present invention is not particularly limited, and is preferably, for example, methanol, ethanol, n-butanol, cyclohexane or cyclohexanone. Further, the reduction of the ester makes the 5 mass, and the point 70~ is the swelling or substitution of the lyophilized fluorenyl chloride, and the propionic acid is used. In the -53-200835945, the water is preferably 0. 01~2 mass%. The solvent used for the solution is recovered by a solvent in the film forming step, and is reused for use in the preparation of the doping described above, and a general method can be used for the fiber surface. If heating and heating are above the boiling point. The boiling of the solvent at normal pressure may be heated at a temperature which does not cause boiling. It is preferred to prevent the formation of a gel or a block of undissolved material called an flour. After the solvent is mixed and wetted or expanded, the addition method can also be suitably used. The pressurization is preferably carried out by heating an inert gas such as a nitrogen gas to increase the vapor pressure of the solvent, for example, a jacket type. The heating temperature at which the solvent is added is preferably from a high viewpoint, and the productivity is deteriorated when the heating temperature is too high. The proper heating temperature is 45 to 120 ° C, and 70 ° C to 105 ° C is more preferable. Also, the pressure can be adjusted to the way it boils. Alternatively, the cooling dissolution method may be suitably used, and the solvent may dissolve the cellulose ester. Next, this cellulose ester solution was treated with hydrazine. Further, the dissolution of the cellulose ester is carried out by a method of dissolving the oxime ester which is dried and removed from the film. When the pressure is combined, it may be above the normal pressure and stirred and dissolved under pressure, because the fiber can be undissolved lump of The method of injecting the ester with a weakly added solvent or by adding it may be carried out. It is preferable to heat the external pressure due to the temperature control which is easily necessary for the solubility of the cellulose ester to make 4 60 to U0 ° C, so that the solvent does not cause the methyl acetate or the like at the set temperature: paper, etc. Appropriate filter material is filtered from -54 to 200835945. In terms of filtration and material, it is preferable to remove insoluble matter or the like, and it is preferable that the absolute filtration accuracy is small, and when the absolute filtration accuracy is too small, there is a problem that the mesh of the filter material is likely to be clogged. Therefore, it is preferable to use a filter material having an absolute filtration accuracy of 0.08 m m or less, a filter material of 0.001 to 0.008 mm, and a filter material of 0.003 to 0.006 mm. The material of the filter material is not particularly limited, and a usual filter medium can be used, and a filter material made of plastic such as polypropylene, Teflon (registered trademark), or a filter material made of metal such as stainless steel is preferably not detached from fibers. By filtration, it is preferred to reduce the impurities of the cellulose ester contained in the raw material, especially to remove the foreign matter at the bright spot. The bright spot foreign matter means that two polarizing plates are arranged in a crossed Nicols state, and a roll of cellulose ester is placed therebetween, and light is irradiated from the side of one of the polarizing plates, and is visible when viewed from the side of the other polarizing plate. When the light from the opposite side leaks (foreign matter), the number of bright dots having a diameter of 0.01 mm or more is preferably 200/cm2 or less. More preferably, it is 100 pieces/cm2 or less, more preferably 50 pieces/m2 or less, and even more preferably 〇~1〇/cm2 or less. Further, the highlights below 0.01 mm are preferably less. The doping filtration can be carried out by a usual method, and is carried out by heating at a temperature higher than the boiling point of the solvent under a normal pressure and under a pressure of a solvent at a temperature at which the solvent does not boil, because of a difference in filtration pressure before and after filtration (referred to as difference) It is better to increase the pressure). The proper temperature is 45 to 120 ° C, preferably 45 to 70 ° C, and more preferably 45 to 55 ° C. The filter pressure is preferably small. The filtration pressure is preferably 1.6 MPa or less, and 1.2-55-

200835945 is preferably MPa or less, more preferably 1.0 MPa or less. Here, the doping casting is explained. In the casting (casting) step, the metal support is preferred, and the final surface of the surface is preferred. In terms of the metal support, it is preferred that the surface is subjected to electroplating for final processing. ~4m. The surface temperature of the metal support of the casting step is the temperature at which the boiling point of the solvent is high, so that the mesh of the high temperature is preferred, and when it is too high, the mesh is foamed and shaped. A suitable support temperature is 〇~40 °C, and it is also an appropriate method to peel the mesh from the drum by cooling the mesh to a residual state by cooling. The method of controlling the temperature of the metal support does not have a special method of warm air or cold air, or a method of supporting warm water and metal. It is preferable that the temperature at which the temperature of the support can be efficiently performed by using warm water is short. The film-like cellulose ester which uses a wind having a temperature higher than the target temperature is a flat body which exhibits goodness. The amount of the residual solvent at the time of peeling off the mesh is preferably 1 or more, more preferably 20 to 40% by mass or 60 to 130% by mass or 3 to 1200% by mass. Further, in the drying step 1 of the film-form cellulose ester, the ruthenium support is peeled off and further dried, preferably in the amount of residual solvent, more preferably 0.1% by mass or less. In order to make the surface mirror stainless steel belt or the width of the casting can be 1 degree at -5 0 °c ~ undrying speed can be fast flatness deterioration 30 ° C is better. The amount of solvent remaining contains a limit, and there is a conduction of the inner side of the blown body, so that the metal: In the case of using warm wind. :, from the metal support 0~1 5 0% by mass is: %, especially preferably 20~, so that the mesh becomes 1% by mass from gold to 0~0.01% by mass to -56-200835945 in the film drying step generally The method of roll drying (which is configured such that a plurality of rolls are arranged to allow the web to alternately pass through drying) or the web is conveyed by a stretcher while drying. When the cellulose ester film used in the second protective film of the present invention is produced, the mesh is removed by the metal support, and the mesh is stretched in the transport direction (=longitudinal direction) with a large amount of residual solvent. Further, it is preferable to stretch the both ends of the mesh by a stretcher held by a jig or the like in a wide direction. The stretching operation can be carried out in a plurality of stages, and in the casting direction, the biaxial stretching is preferably carried out in the wide side direction. Further, even if biaxial stretching is performed simultaneously with biaxial stretching, it may be carried out stepwise. In this case, the staged means that it is also feasible to perform stretching in different stretching directions, for example, and the stretching in the same direction can be divided into multiple stages, and the stretching in different directions is increased at any stage. Also OK. 5倍倍。 Preferably, the stretching ratio is preferably 1. 5~2 times, preferably 1. 1~1. 5 times. At the same time, it can be contracted in the longitudinal direction at the time of the 2-axis stretching, and is shrunk in a manner of 0.8 to 0.99, preferably 0.9 to 0.99. Preferably, the area is 1.12 times to 1.44 times by stretching or shrinking in the transverse direction and in the longitudinal direction, and it is preferably 1.15 times to 1.32 times. This can be obtained by the stretching ratio in the longitudinal direction of the stretching ratio X. In the present invention, the "stretching direction" refers to a case where the stretching operation is performed in the sense of directly increasing the direction of the tensile stress, and in the case of performing biaxial stretching in multiple stages, There is a case in which the final stretching ratio is large (i.e., the direction usually becomes the direction of the slow axis) -57-200835945. In the cellulose ester film used in the second protective film of the present invention, the retardation 所示 represented by the following formulas 3 and 4, Ro is 30 to 115 nm, Rt is in the range of 100 to 250 nm, and Rt/Ro is 1.6 to 15 The scope of 4.4. Further, Ro is 45 to 95 nm, Rt is in the range of 110 to 200 nm, and Rt/Ro is preferably in the range of 2.0 to 3.5. In addition, the retardation enthalpy is measured at a wavelength of 590 nm in an environment of 23 ° C and 5 5% RH. In particular, in the range of about ±10 ° C of the glass transition temperature, the stretching is performed in a direction orthogonal to the conveying direction by about 1.1 times to about 1.5 times, or a film produced by solution casting is used in a residual solvent. The amount of the residue is about 2 to 10,000% by mass, and can be accommodated in the range of the above-mentioned retardation when the stretching is about 1.1 to 1.7 times in the direction of the conveyance direction. Further, in the state of laminating the state of the second protective film of the present invention and the retardation layer, R 〇 is 30 to 105 nm, and Rt is in the range of -3 00 to 25 nm. Further, Ro is 45 to 95 nm, Rt is -100 to 25 nm, and particularly preferably Rt is in the range of -6 0 to 2 0 n m. Further, in the state in which the second protective film of the present invention and the retardation layer are laminated, the laminated film has an optical axis in the same plane and is dispersed by wavelengths defined by the following formulas 5, 6, 7, and 8. Characteristic system D ( R 〇 ) 1 : 0 · 9 〜 1 . 0 D ( Ro ) 2: -9.5 ~ Onm D ( Rt) 1: 0.3~0.9 D ( Rt) 2 : -100~-10 nm , the first The absolute axis of the transmission axis of the polarizing film and the surface retardation axis of the second protective film -58-200835945 is characterized by the range of 〇~Γ. In particular, D (Ro) 1 is in the range of 0.93 to 0.98, preferably 〇·4 to 0.8, and preferably in the range of 0.45 to 0.65. The absolute angle of the transmission axis of the first polarizing film and the second protective slow axis is in the range of 〇 Γ Γ, so that the first surface retardation axis and the conveying direction are in the straight direction, and Can be reached. Therefore, the stretching temperature and the stretching ratio are precisely controlled so that the both sides of the stretched portion (the jig of the stretcher, etc.) are independently controlled. This is achieved by adjusting the stretching temperature and the stretching ratio with respect to the stress at the clamp position. Formula 3 ·· Ro = (nx-ny)xd Equation 4: Rt = ((nx + ny)/2-nz)xd (wherein the second protective film or retardation layer, or the layer of the second protective layer The refractive index in the direction of the phase axis in the plane of the compound is nx, the refractive index in the direction orthogonal to the phase axis is ny, and the thickness in the thickness direction is nz, and d is the thickness (nm). Equation 5: D(R〇)1=R〇(63 0)/R〇(480) Equation 6: D(R〇)2 = R〇(630)-R〇(480) Equation 7: D(Rt) l= | Rt(630)/Rt(480) | Equation 8: D(Rt)2 = Rt(480)-Rt(63 0) D ( Rt) 1 In-plane in-plane 2 protective film in-plane unbalance Applying the protection to the fixture film and the phase plane and the hysteresis index is -59- 200835945

(wherein, Ro ( 480 ) and Ro ( 63 0 ) are delayed at 480 nm and 63 0 nm in the environment of 23 ° C, 55% RH, respectively, R ( (480), Rt (630) Each shows a delay at 480 nm, 630 nm

Rt 値). In terms of means for controlling the dispersion of the wavelength, D ( Ro ) 1, D ( Ro ) 2 can be suitably selected by selecting the material and manufacturing method of the second protective film. It is preferable that the material is changed by a cellulose ester-based material to change a substituent (type/substitution degree). In the case of only the acetamidine group, the lower the degree of substitution, the larger the enthalpy, and the more the propyl sulfhydryl group is, the smaller the tendency is. It also changes due to additives. Generally, in the case of delaying the riser or the like, there is a tendency to become large. D (Rt ) 1, D ( Rt ) 2 controls the phase difference between the second protective film and the retardation layer to be preferable. Specifically, when the phase difference of the second protective film is relatively large, it becomes a small flaw. The first protective film used in the polarizing plate of the present invention is not particularly limited as long as the retardation of the fourth protective film, and the retardation 値Ro in the in-plane direction is preferably in the range of 30 nm to 100 nm, and more preferably It is preferably in the range of 30 nm to 500 nm, particularly preferably in the range of 30 nm to 15 0 nm, and most preferably in the range of 30 nm to 7 5 nm. Further, the retardation 値Rt in the thickness direction is preferably in the range of 30 nm to 1000 nm, more preferably in the range of 30 nm to 500 nm, and particularly preferably in the range of ～250 nm. The cellulose ester film used in the first to fourth protective films of the present invention preferably has a film thickness of 20 to 200 μm, more preferably 20 to 100 μm, and more preferably 20 to 80 μm. In particular, the cellulose ester-60-200835945 film used in the third protective film is preferably from 20 to 45 μm in obtaining the effects of the present invention. (Polarizing Plate) The polarizing plate can be produced by a general method. The inner surface side of the cellulose ester film used in the first to fourth protective films of the present invention is subjected to alkali saponification treatment, and immersed and stretched in at least one surface of the produced polarizing film in an iodine solution, and completely saponified polyvinyl alcohol is used. It is preferred that the aqueous solution is attached. On the other hand, even if the film is used, other polarizing plates can be used to protect the film. Commercially available cellulose ester films (for example, Konika Minolta Tac KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC12UR, KC4FR (above Konika Minoltaopt)) can also be used as appropriate. The polarizing film which is a main component of a polarizing plate is an element which passes only the light of a polarizing surface in a certain direction, and a typical polarizing film currently known is a polyvinyl alcohol type polarizing film, and this is a polyvinyl alcohol type. The film causes the iodine dye to be dyed with the dichroic dye. The polarizing film is formed by forming a film of a polyvinyl alcohol aqueous solution to be subjected to one-axis stretching for dyeing or after one-axis stretching after dyeing, and it is preferred to use a boron compound for durability treatment. (Display device) The liquid crystal display device of the present invention having excellent visibility can be produced by assembling the polarizing plate of the present invention to a liquid crystal display device. The polarizing plate of the present invention can be suitably used in an IP S mode type LCD, and in particular, the IPS mode-61 - 200835945 type liquid crystal display device which is constituted by the application of the scope of claim 5 or the scope of claim 6 can be used. Use it properly. In particular, the screen type 3 0 or above 'especially the 30-type to 54-type large-screen liquid crystal display device, the contrast is a bureau, especially the color change caused by the viewing angle can be suppressed, even if the viewing is long, the eyes will not be fatigued. . [Embodiment] The present invention will be more specifically described by way of examples, but the invention is not limited thereto. Example 1 "Delayed enthalpy, and measurement of wavelength dispersion" In the examples, delayed enthalpy measurement was carried out in an environment of 23 ° C and 55% RH using K0BRA21ADH manufactured by Oji Scientific Instruments. Further, in calculating the retardation in the thickness direction, an abbreviated refractometer is used to measure the refractive index of the wavelength of each layer. In the case of a laminate, the refractive index average 値 of each layer is used. For the calculation of the delay 値, Equation 3 below, Equation 4 can be used. In the present invention, the retardation 厚度 in the thickness direction of the laminate becomes a sample of negative enthalpy, and when the retardation enthalpy is calculated, the in-plane axis of the laminate is made to be an inclined axis, and the retardation at the time of 40-degree tilt is measured for calculation. . Formula 3: Ro = (nx-ny)xd Equation 4: Rt = ((nx + iiy)/2-nz)xd (wherein the second protective film or retardation layer, or the second protective film and phase -62 - 200835945 The refractive index of the retardation axis in the plane of the layer of the difference layer is ηχ'. The refractive index in the direction perpendicular to the axis of the slow axis is ny, and the refractive index in the thickness direction is 1^, 4 Thickness (11111)). Further, the wavelength dispersion characteristics can be obtained in accordance with Equations 5 to 8. Equation 5: D(Ro) 1 = R〇(6 3 0)/R〇(48 0) Equation 6: D(R〇)2 = R〇(630)-R〇(480) Equation 7: D(Rt )l= | Rt(63 0)/Rt(480) | ® Equation 8 ·· D(Rt)2 = Rt(4 80)-Rt(630) (wherein, Ro ( 480 ) , Ro ( 63 0 ) The temperature is 480 nm at 23 ° C, 55% RH, and the retardation in 630 nm, Rt (480), Rt (63 0 ) at 480 nm, 630 nm means retardation Rt値). "Preparation of protective film A to L with phase difference layer" (cerium oxide dispersion)

Aerosil 972V (manufactured by Nippon Aerosil Co., Ltd.) 12 parts by volume (average diameter of primary particles is 16 nm, apparent specific gravity: 90 g/liter) Ethanol 8 8 parts by mass - The above is stirred and mixed in a dissolver for 3 minutes, then Manton

The Gaulin disperser was dispersed. The turbidity of the dispersed liquid was 2 〇〇 ppm. The silica dioxide dispersion was stirred while stirring 8 8 parts by mass of the dichlorohydrin, and stirred and mixed for 30 minutes with a dissolver to prepare a dilute dispersion of the silica sand. -63- 200835945 (grab liquid) cellulose ester (acetamyl substitution degree 2.50, propyl ketone substitution degree 0 · 10, total 醯 10 parts by mass 5 parts by mass 5 parts by mass 1 〇 parts by mass 1.2 parts by mass · 8 parts by mass of 430 parts by mass, 40 parts by mass, degree of substitution 2 · 6 0 ) trimethylolpropane tribenzoate ethyl phthalate ethyl hydroxyacetate cerium oxide dispersion diluent

Tinuvin 109 (made by Chiba Special Chemicals Co., Ltd.)

TinuVinl71 (manufactured by Chiba Specialty Chemicals Co., Ltd.) Dichloromethane Ethanol The above doped composition was placed in a sealed container, heated to 70 ° C, and the cellulose ester was completely dissolved while stirring to obtain a dope. Next, after the doping liquid was filtered, the doping liquid whose temperature was adjusted to 33 ° C was sent to the mold, and the mold was poured from the die gap to the stainless steel strip to a first-class casting with a width of 2.5 m. The casting section of the stainless steel belt is heated from the inner surface by warm water of 37 °C. After the casting, the doped film on the metal support (referred to as a mesh after the flow of the stainless steel strip) is blown by a warm air of 44 ° C to dry the strip, and the amount of the residual solvent is peeled off at 120% by mass. The tension at the time of peeling is stretched to 1.1 times the longitudinal stretching ratio, and then the residual solvent amount is 24%, and the end portion of the mesh is held at the 135 ° C at the use temperature, and the width direction is stretched. 1.2 times the draw ratio. After stretching, after maintaining the width for a few seconds, the tension in the width direction was alleviated, and after drying, the film was dried at 120 °C. A cellulose ester film having a film thickness of 30 μm, a width of 2.65 m, and a length of 7500 m, which was produced in the above manner, was wound into a core. The phase difference of the cellulose ester film was 30 nm, Rt was 130 nm, and Rt/Ro was 4 · 3 〇 Next, the following retardation layer was provided on the obtained cellulose ester film. Modulating 45% by mass of the compound of the following formula (a)

(a) CH2=6HCOO(CH2)3p -〇-cb0-〇A.om^_ O(0H2)3〇COCH=GH2 The compound of the following formula (b) is 45 mass% [Chem.4] ( b) -Or Jew 1 body 0{CH2) 60G0GH=eH2 GH2=CHG0G(CH2)60 hQhc. . ^ The mass of the compound of the following formula (d) is 10%. (d) CH2=GHC〇〇(CH2)e〇-^r^~~_ The polymerizable liquid crystal composition (H) is formed. The nematic-isotropic liquid phase transition temperature of this polymerizable liquid crystal composition (?) was 73 °C. Modification of poly-65-200835945 conjugate liquid crystal composition (Η) 99.7% of photopolymerization initiator Rushirin TPO (made by Basf Corporation) 0. 2%, hindered amine LS-765 (manufactured by Sankyo Life Tech Co., Ltd.) 0.1% polymerization Liquid crystal composition (HI). Then, a xylene solution containing a polymerizable liquid crystal composition (Η 1 ) 3 3 % was prepared. This xylene solution was applied to a cellulose ester film by a die coater at a thickness of 5 μm. The coated film was irradiated with an ultraviolet concentration of 0.2%, and an ultraviolet ray of 25 〇mJ/mm was irradiated at 80 ° C for 80 seconds to cure the polymerizable liquid crystal composition (Η 1 ) to obtain a protective film with a retardation layer. A. When measuring the phase difference of the cured film, R 〇 is 0.5 nm, Rt is -28 8 nm, and the laminated phase of the retardation layer protective film A is 30.5 nm, and Rt is · 1 0 5 nm. D(Ro) 1 is 0.9, D(Ro) 2 is - 3.09 nm, D(Rt) 1 is 0.70, and D(Rt) 2 is -36 nm. Next, as the second protective film, the cellulose ester of the type described in Table 1 and Table 2, the stretching conditions and film thicknesses shown in Table 3, and the compounds represented by the formulae (a), (b) and (d) were used. The composition ratio is changed to change the retardation 値 in Table 1 and the phase difference layer described in Table 2, and the phase difference layer protective film B to L is produced in the same manner as in the production of the phase difference layer protective film A described above. "Preparation of phase difference protective film Μ, N" In addition to cellulose ester, cellulose acetate propionate (acetate substitution degree 1.9, propyl ketone substitution degree 0.75), and other phase difference The protective film of the layer is similarly formed to have a phase difference layer protective film, Ν. -66 - 200835945 "Preparation of phase difference protective film 〇, p" The cellulose ester film of the second protective film was produced in the following manner. (Preparation of doping liquid B) Cellulose ester (cellulose triacetate synthesized from cotton wool) 100 parts by mass (Mn = 148000, Mw = 310000? Mw / Mn = 2.1) Triphenyl phosphate 9.5 Part by mass of ethyl phthalate ethyl hydroxyacetate 2.2 parts by mass of dichloromethane 440 parts by mass of ethanol 40 parts by mass. The above is put into a sealed container, heated, stirred, and completely dissolved. The filter paper NO.24 is filtered to modulate the dopant B. The dope B was filtered in a film line by Finemet NF manufactured by Nippon Seisen Co., Ltd. (One part of the doping liquid B is also used in the production of the online additive B described below). (Silica dioxide dispersion B)

Aerosil 200V (manufactured by Nippon Aerosil Co., Ltd.) 2 parts by mass (average diameter of primary particles 12 nm, apparent specific gravity 1 〇〇 g / liter) Ethanol 18 parts by mass or more, stirred and mixed in a dissolver for 30 minutes, dispersed by Manton Gaulin The machine is dispersed. The turbidity of the dispersed liquid was 100 ppm. In the -67-200835945 cerium oxide dispersion, the mixture was stirred while stirring 18 parts by mass of methylene chloride, and the mixture was stirred and mixed for 30 minutes in a dissolver to prepare a cerium oxide dispersion diluent B. (Production of on-line addition liquid B) 100 parts by mass 3 4 parts by mass 5 parts by mass 5 parts by mass 3 parts by mass At the same time, completely dissolved,

Dichloromethane doping solution B

Tinuvinl09 (manufactured by Chiba Specialty Chemicals Co., Ltd.) Tinuvinl 7 1 (manufactured by Chiba Specialty Chemicals Co., Ltd.) Tinuvin 3 26 (manufactured by Chiba Specialty Chemicals Co., Ltd.) The above is put into a closed container, heated, and stirred for filtration. Here, 20 parts by mass of the cerium oxide dispersion diluent B was added while stirring, and after stirring for 60 minutes, the polypropylene cartridge of the Advantic Toyo Co., Ltd. was wound by a wind cartridge filter. -1 N filter, modulation line (i η 1 ine ) addition liquid B. In the line of the liquid addition liquid, the liquid addition liquid B was added by FinemetNF manufactured by Nippon Seisen Co., Ltd. The filtered doping solution B was added to 2.5 parts by mass of the filtered on-line addition liquid B by 2.5 parts by mass, and thoroughly mixed with an in-line mixer (To ray static in-line mixer Hi-Mixer, SWJ), and then It was cast into a stainless steel belt support at a temperature of 35 C ' 2·5 ιη uniformly using a belt casting apparatus. The solvent was evaporated in the stainless steel belt support to allow the amount of residual solvent to reach 100%, and peeled off from the stainless steel belt support. The web of the exfoliated cellulose ester was subjected to solvent evaporation at -68-200835945 3 5 ° C, and thereafter, the stretcher was stretched by 1-2 times in the width direction while being at 130 ° C. Dry at dry temperature. At this time, the amount of residual solvent when the stretcher starts to stretch is 11%. Thereafter, the drying zone at 120 ° C and 11 ° C was conveyed by a plurality of rolls while drying, the slit was 2.6 m wide, and the width of the film was 15 mm wide, and the average height was 10 μηι knurling. The initial tension of 220 N/m was wound, and the final tension of 110 N/m was wound into a 6-inch inner diameter to prepare a cellulose ester film of a second protective film having a thickness of 80 μm and a length of 75 00 m. Similarly, the cellulose ester film P of the second protective film having a film thickness of 40 μm and a length of 750 mm was produced without stretching in the above-mentioned width direction. Next, a phase difference layer protective film Ο, P, was produced in the same manner as the phase difference layer protective film A, using the produced cellulose ester film 〇, P. "Preparation of phase difference protective film Q (and third protective film Q, V to Z)" <Synthesis of polymer> (Synthesis of polymer X) Refer to Japanese Laid-Open Patent Publication No. 2003-1285-9 The method described is used to synthesize polymer X. That is, in a glass flask equipped with a stirrer, two dropping funnels, a gas introduction tube and a thermometer, and charged with methyl methacrylate (MMA): 2·hydroxyethyl methacrylate (HEMA) to 80 40 g of a monomer mixture mixed at a ratio of 20, a chain transfer agent of thiophosphoric acid 3. 〇g and 30 g of toluene, and the temperature was raised to 90 °C. Thereafter, the funnel was dropped from one of the above, and the monomer mixture was dropped to 60 g over 3 hours while the azobisisobutyronitrile ruthenium 6 g dissolved in 14 g of toluene was dissolved in the other -69-200835945 funnel for 3 hours. dropping. Thereafter, azobisisobutyronitrile 〇·6 g dissolved in toluene (5 6 g) was further dropped over 2 hours, and further reacted for 2 hours to obtain a polymer X. The weight average molecular weight is 8,000. (Synthesis of Polymer Y) Block polymerization was carried out by the polymerization method of JP-A-2000-344823. Namely, a flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer, an inlet and a circulation cooling tube was heated to 70 ° C while introducing the following methyl methacrylate and rethenocene. Then, one of the following β-hydrothiopropionic acid, which was sufficiently substituted with a nitrogen gas, was added to the flask under stirring. After the addition of ?-hydrothiopropionic acid, the contents of the flask under stirring were maintained at 70 ° C for 2 hours of polymerization. Further, after the addition of half of the β-hydrothiopropionic acid substituted with nitrogen gas, the temperature of the content during stirring was maintained at 70 ° C for 4 hours. The temperature of the reactant was returned to room temperature, and 20 parts by mass of a 5% by mass solution of benzoquinone in tetrahydrofuran was added to the reactant to terminate the polymerization. The polymer was slowly heated to 8 (TC) under reduced pressure in an evaporator to remove tetrahydrofuran, residual monomers and residual thiol compound to obtain polymer Y. The weight average molecular weight was 1 000. Methyl methacrylate 1 〇〇 mass part of hafnocene (metal catalyst) 0. 05 parts by mass / 3 - mercaptopropionic acid 12 parts by mass weight average molecular weight measurement method is as follows. - 70- 200835945 (weight average molecular weight measurement method The weight average molecular weight Mw is determined by gel permeation chromatography. The measurement conditions are as follows. Solvent: dichloromethane column: Shodex K8 06, K8 0 5, K8 03 G (Showa Electric Co., Ltd. made 3 connections for use) Column temperature: 25°C Sample concentration: 〇. 1 mass% Detector: RI Model 504 (manufactured by GL Scientific Co., Ltd.) Pump·· L6 000 (manufactured by Hitachi, Ltd.) Flow rate: 1.0 ml/min Calibration curve: Standard polymerization Calibration curve for 13 samples up to styrene STK standard polystyrene (manufactured by Tosoh Corporation) Mw = 1 000000 to 500. The sample is used at approximately equal intervals. The above polymer X, Y is used as shown below. A third protective film Q with a retardation layer and a third protective film Q, V to Z without a retardation layer are formed. (Doping liquid) Cellulose triacetate (acetylation degree Μη = 2·0) Polymer X Polymer Υ Dichlorohydrin Ethanol: 61 · 5%, Μη : 1 1 0000' Mw / 1 0 0 parts by mass 1 〇 parts by mass 5 parts by mass 430 parts by mass 40 parts by mass - 71 - 200835945 The above doping composition The mixture was placed in a sealed container and heated to 70 ° C, and the cellulose triacetate (TAC) was completely dissolved to obtain doping while stirring. The time required for dissolution was 4 hours. Then, after the doping composition was filtered, The cellulose ester solution adjusted to a temperature of 33 ° C was sent to the mold, and was uniformly cast by a die slit on a stainless steel belt at a width of 2.5 m. The cast portion of the stainless steel strip was internally 3 Heating at 7 °C in warm water. After casting, the doped film on the metal support (called a mesh after the stainless steel strip is casted) is blown with a warm air of 44 °C to dry it, leaving the residue The amount of the solvent was peeled off at 120% by mass, and the tensile force at the time of peeling was applied to stretch the longitudinal stretching ratio, and then adjusted. The amount of solvent remaining was 4% by mass, and the temperature was 1 23 ° C. The end of the mesh was held by a stretcher and stretched in a wide hand direction to a draw ratio of 1.1 times. After stretching, the width was maintained. In the case of holding for a few seconds, the tension in the width direction is relaxed, and the width is kept at 120 ° C to be dried. The film thickness of the film is 41 μm, width 2.65 m, and length 750 0 m is the second protective film. The cellulose ester film is wound into a core. Next, a phase difference layer protective film Q having a retardation layer is formed in the same manner as the phase difference layer protective film A. Further, the cellulose ester film is used as the third protective film Q without providing a retardation layer. The retardation 第 of the third protective film Q is 0.8 nm and the Rt is 1 nm. Further, the ratio of the polymer X and the polymer Y is changed to prepare the delayed ruthenium and the film described in Table 1 and Table 2. Thick 3rd protective film V~ Ζ ° -72- 200835945

<<Preparation of the phase difference layer protective film R to U>> In addition to the change in the degree of substitution of the cellulose ester as described in Table 1, the phase difference layer protection is produced in the same manner as the production of the phase difference layer protective film A. Film R~U. -73- 200835945

[Is 3rd protective film thickness (μιη) τγ·^1 inch τ-Η inch rH inch f-H inch inch inch τ-Η inch inch t-H inch (N (N (N (N inch) 5 r-Η τ -Η Τ-Η 〇1 〇rH 1 H c§ 00 ο 00 ο oo o oo o oo 〇00 ο 00 ο οο ο oo ο 00 o CNI (N 00 o Film No. Ο Ο oa 〇Ο ο aa 〇&gt ; &gt; a (N ※ parallel parallel parallel) parallel parallel parallel parallel parallel parallel parallel parallel parallel parallel Η ※ rH 〇\ ο o 〇〇ο Ο ο τ-Η ο 〇τ-Η o 1-H o τ-Η o Lamination of the second protective film/phase difference layer D(Rt)2 rn 1 a\r-H 1 rH \ i 1 00 &lt;N -17.3 r - i &lt; cn cn VO (N TH rH 1 rH 1 ( ND(Rt)l 0.70 0.67 0.82 0.82 0.60 0.63 0.68 0.56 0.55 0.49 0.89 0.90 0.46 D(Ro)2 -3.09 -3.09 -3.98 -4.16 -4.16 -4.10 -4.29 -4.29 -3.67 -3.67 -4.06 -4.06 -3.84 D (Ro)l 0\ ο 〇\ ο 0.91 0.91 0.91 0.92 0.93 0.93 0.94 0.94 0.95 0.95 0.95 S r·—Η i -260 oo in ο cn 瞧ο cn i 〇cn oo as sr—H 1 cQ 30.5 34.0 43.3 45.3 45.3 51.5 60.2 60.2 60.2 60.2 80.5 80.5 97.2 phase difference layer -288 cn -314 -223 g (N -321 -320 -258 -244 oo 1 § rn -362 -265 ^Τ) Ο inch mom 〇m d&gt; ι-H (Ν Ο (Ν Ο &lt;N 〇( N 〇»r&gt; 〇o &lt;N (N 2nd protective film S c§ m — m cn rn oo (N oo Os (O 〇 (N ( (N m (N CO (N On 〇 τ—H ... τ-Η (N rH 220 Τ—Η Η 宕r—H rrH 00 rH 00 i—H oo Ο ΓΛ 9m 9 jrj ο § § § ON Cellulose Ester X+Y 2.60 2.60 2.60 2.55 2.55 2.46 2.50 2.50 2.43 2.43 2.40 2.40 2.30 0.10 0.49 0.50 0.68 0.68 0.70 0.80 0.80 0.90 0.90 0.82 0.82 0.50 X 2.50 2.11 2.10 1.87 1.87 1.76 1.70 1.70 L53 1.53 1.58 1.58 1.80 Film No. &lt; PQ u QQ PQ ΙΧι 〇 〇Liquid crystal display device No. τ—ί &lt;N m inch 00 ON o H t-H r-H CN m side ^ light lake _ system: Α + Χ ^ ms_sKI: x (. )]] s^?lIΠIψ3⁄4^M Hall 3⁄4CN moved 3⁄4w^鳏朱摩^M Song bang I※ -74- 200835945

Cnm 3rd protective film thickness (μηι) $ $ 00 H 00 i—H 00 tH ο 1 oo O rH oo face or—( Brewing (N r—f (N rH (N 1—H (NT—HI &lt; N 1 (NI vn v〇v〇vo v〇VO film No. XXXXNNN (N ※ Parallel parallel parallel parallel parallel 1 parallel parallel parallel parallel parallel parallel parallel parallel ※ CN Ο lH 〇m 〇cs rH H m 〇CN (N i —HH rH 1—H rH &lt;N 〇(N 〇 2nd protective film / phase difference layer lamination D(Rt) 2 m (N 1 H rH Q\ S 1 (N rH rH 1 § 1 VO S r -^ 1 cn rp rn D(Rt)l (Ν ^Τ) Ο VO to 〇rH oo o Ό —T—H o cn m 〇O Ό 〇匕ooso O o S tH 1 ON (N 〇D(Ro) 2 -8.90 -8.90 o § rn -2.97 j -4.42 卜1—(1—H 1 (N rH 〇VO 1—H rH -10.59 -12.95 (N oo 1 in oo tH 1 D(Ro)l τ—ί 〇\ ο ON 〇〇\ oo ov〇OO 〇v〇v〇〇v〇o 00 00 o O rH (N Os 〇ON 〇\〇Q\ 〇oo ON 〇2 ο o 1 Os VO Sun sy—&lt; 1 os (N o rH H 1 (N CN 1 卜mmo CN 1 100.0 100.5 100.5 o rH mo vd (N oo 00 129.0 131.0 1 127.0 oc Nw 〇Os C\ ΟΝ rn 00 ON cn 〇\ cn 1—H Ό &lt;N t—1 瞧oo 00 r—H 1 VO cn rH rH cn r—HK 1 s 1 oo rH 1 m cn cn cn v 〇 VO in · inch rH rH v〇&lt;N oo m (N 濉t&gt; (Ν l&gt; (N (N (N ON CO 〇〇in 卜: TH 〇H (N (NH &lt;N rH (N ( N (N 1-H Pan-CN 沄 (N 沄 (N 〇H § CO rH s (N § (N 8 (N oo G\ irv cn t-H ON ON tn H oo &lt;N 〇rH (NH OO rH T—((N ^r\ (N l-H cellulose ester X+Y 00 (N (N 00 CN oi o (N iH Ό oi CN oo 5 m 00 (N Qin (N t-H (N &lt; N oo Os r—H 00 C\ t—H &lt;NH inch&lt;N 5 oo o 〇CN rH oo osso 〇〇o S os oo 〇X § r—H g rH o H oo 1-—1 m oo t—H jn &lt;N (N 卜 rH inch T—H inch r—r rH 00 U^i H r~H film No. 〇CU σ Xfl CZ) H-port liquid crystal display device No. inch rH r-1 H 卜rH oo On 1—&lt; (N (N &lt;N (NV〇&lt;N &lt;N &lt;N side ill: Λ+Χ«^谨κ: Λ ms议κ]: χ 筚鼷忉侄枳俚囵wsIngInsm Wipe MS to _ν«ι·®(ν鹕^※Γ - - §^1 - —SMI- ^ —ffiliM—- - ^ -75 - 200835945 [Table 3]

2nd protective film Να stretching condition film thickness temperature 残留 residual solvent (%) (/zm) A 135 24 30 B 150 24 30 C 140 26 43 D 155 30 45 E 140 33 50 F 145 39 60 G 155 42 60 H 142 33 60 I 145 42 57 J 155 44 55 K 155 43 50 L 158 48 46 M 131 22 80 N 138 17 81 0 120 11 80 P 122 7 40 Q 123 4 41 R 155 48 49 S 151 51 46 T 151 51 78 U 159 47 61 As in the above manner, the protective films A to U with the retardation layer are formed, and the third protective films Q, V to Z of the retardation layer are not provided. <<Preparation of Polarizing Plate>> The phase difference protective film A to U prepared as described above is not provided with the third protective film Q of the retardation layer, V to Z is 2.5 mol/L sodium hydroxide-76 at 40 °C. 200835945 The aqueous solution was subjected to alkali treatment for 60 seconds, and subjected to saponification treatment with water washing for 3 minutes to obtain an alkali-treated film. Next, a polyvinyl alcohol film having a thickness of 120 μm was subjected to one-axis stretching (temperature ll 〇 ° C, stretching ratio 5 times). The solution was immersed in an aqueous solution of iodine 〇 75 g, 5 g of potassium iodide and 100 g of water for 60 seconds, followed by immersion in 6 g of potassium iodide, 7.5 g of boric acid, and 100 g of water to form a temperature of 68 ° C. Aqueous solution. It was washed with water and dried to obtain a polarizing film. Then, the polarizing film prepared above, and Konika Minolta Tac, KC4UY (manufactured by Konika Minoltaopt Co., Ltd.), which is a commercially available polarizing plate protective film, were saponified by the above method to make a completely saponified polyvinyl alcohol 5% aqueous solution as an adhesive. The protective film A to U with a retardation layer, a polarizing film, and KC4UY (first protective film) were laminated in this order to produce a polarizing plate on the visual side. In the same manner, the third protective film Q, V to Z, the polarizing film, and the KC4UY (fourth protective film) which are not provided with the retardation layer are laminated in this order to form a polarizing plate on the backlight side (BL side). <<Production of Liquid Crystal Display Device>> A liquid crystal panel in which the viewing angle was measured was produced in the following manner to evaluate the characteristics of the liquid crystal display device. The pre-bonded polarizing plate of the Hitachi LCD TV Wooo W17-LC50 of the IPS mode liquid crystal display device is peeled off, and the polarizing plate of the visible side and the BL side prepared as described above is constituted by the first A. The IP S mode liquid crystal display devices 1 to 26 were fabricated by bonding them to the glass surface of the liquid crystal cell. The in-plane retardation axis of the second protective film of the polarizing plate is substantially parallel to the alignment direction of the liquid crystal crystal -77-200835945. "Evaluation of Liquid Crystal Display Mounting" (Viewing Angle) The viewing angle was measured using the EZ-contrast manufactured by ELDIM Co., Ltd. on the liquid crystal display device produced above. The viewing angle is calculated by comparing the white display of the liquid crystal cell with the black display, and the angle of the tilt is 1 〇〇 as the viewing angle. (Colored) The color measurement in black display was performed using Topcon SR-3A. The color measurement of the inclination of the front side and the inclined surface (azimuth angle of 45 degrees) of 60 (front reference) was carried out, and ((x-x,) 2 + (y-y,) 2) 1/2 was evaluated. * In the formula, the front side: (x, y), the slope: (x, y,). The results obtained are shown in Table 4. -78- 200835945 [Table 4]

Liquid crystal display device Να viewing angle (degrees) color change test 1 55 0.078 invention 2 55 0.075 invention 3 60 0.067 invention 4 75 0.035 invention 5 75 0.030 invention 6 75 0.035 invention 7 80 0.008 invention 8 80 0.013 invention 9 80 0.008 invention 10 80 0.011 invention 11 60 0.061 invention 12 50 0.077 invention 13 65 0.043 invention 14 55 0.073 invention 15 55 0.072 invention 16 60 0.066 invention 17 35 0.093 comparative example 18 25 0.097 Comparative Example 19 20 0.101 Comparative Example 20 20 0.101 Comparative Example 21 20 0.105 Comparative Example 22 25 0.098 Comparative Example 23 30 0.097 Comparative Example 24 20 0.116 Comparative Example 25 30 0.095 Comparative Example 26 40 0.091 Comparative Example From the results of Table 4, In the liquid crystal display devices 1 to 16 of the present invention, the viewing angle (100 or more in comparison) exceeds 50 degrees, and the color change ratio is smaller than 0.09, which is superior to the comparative example. -79 - 200835945 Example 2 Using the retardation layer protective films A to u produced in Example 1, the polarizing plates were produced in the same manner as in Example 1 except that the third protective films Q, v to Z of the retardation layer were not provided. An IPS mode liquid crystal display device was fabricated as shown in Fig. 1(B). In this case, the in-plane retardation axis of the second protective film of the polarizing plate is substantially orthogonal to the alignment direction of the liquid crystal cell. When the viewing angle and coloring were evaluated in the same manner as in the first embodiment, the IPS mode liquid crystal display device was used, and the first embodiment was reproduced. Therefore, the liquid crystal display device of the present invention has excellent contrast and color. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] is a schematic view showing the configuration of a polarizing plate and a liquid crystal display device as claimed in the patent application. [Description of main component symbols] 1 : First protective film 2 : Second protective film 3 : Third protective film 4 : Fourth protective film 5 : First polarizing film 6 : Second protective film 7 : Phase difference layer 8 : Liquid crystal Cell-80-200835945 9,1 0 : Glass substrate a: Polarization transmission axis of polarizing film b: Phase axis of second protective film c = alignment direction of liquid crystal cell d: honing axis of glass substrate

-81

Claims (1)

200835945 X. Patent Application No. 1 A polarizing plate in which at least a first protective film and a first polarizing film and a laminated retardation layer are arranged in this order, characterized in that the laminated phase is The difference layer has a second protective film which satisfies the cellulose 'ester of the following formula 1 as a main component, and a rod-shaped liquid crystal which is substantially vertically aligned on the surface of the polarizing film or the second protective film a retardation layer to which the alignment is fixed; a retardation Ro, which is represented by the following formulas 3 and 4 at a wavelength of 5 90 nm in an environment of 23 ° C and 5 5% RH of the retardation layer; Rt 'each is, 2nd protective film ·· Ro : 30~1 15 nm Rt: 100~250 nm Rt/Ro : 1.6 〜4·4 Phase difference layer: R〇: 〇~l〇nm Rt: -10 0 ~-40 0 nm, the laminated phase difference layer has an optical axis in the plane, and the retardation at a wavelength of 5 90 nm in the environment of 23 ° C and 5 5% RH 0 is Ro: 30 to 105 nm, Rt = -3 00 to 25 nm, and the wavelength dispersion characteristic defined by the following formulas 5, 6, 7, and 8, D ( Ro ) 1 ···0·9 〜1 ·0 ' D(Ro) 2: -9.5 〜Onm D ( Rt) 1 : 0·3 ~ 0.9 D ( Rt ) 2 : -100 ~ -10 nm, the transmission axis of the polarizing film and the in-plane phase axis of the second protective film: the absolute angle of the angle is 〇~1 °, -82- 200835945 Equation 1 ·· 2.00S (X + Y)S2.60 (wherein, as the degree of substitution of the thiol group of the cellulose ester, x is the degree of substitution of ethyl hydrazide, Y is the degree of substitution of propyl thiol) Formula 3: Ro = (nx - ny) xd Formula 4: Rt=[(nx + ny)/2-nz]xd (wherein the second protective film or the retardation layer, or the refractive index of the retardation axis direction of the laminate of the second protective film and the retardation layer is Nx 'the refractive index in the plane perpendicular to the slow axis is ny, the refractive index in the thickness direction is nz, and d is the thickness (nm). Equation 5: D(R〇)1=R〇(63 0) / R〇 (480) Equation 6 ·· D(R〇)2 = R〇(630)-R〇(480) Equation 7: D(Rt)l= | Rt(63 0)/Rt(480) | Equation 8 ·· D(Rt ) 2 = Rt(48 0)-Rt(63 0) (wherein, Ro ( 480 ) and Ro ( 63 0 ) each show a delay of 480 nm and 630 nm in an environment of 2 3 ° C and 55% RH. Ro値, Rt(480) and Rt (630) each show a retardation Rt値 at 480 nm and 630 nm. 2. The polarizing plate of claim 1, wherein the cellulose ester can satisfy the following formula 2, -83-200835945, formula 2: 〇.l〇g ΐ·〇〇〇3. In the polarizing plate of the present invention, the first surface of the second protective film faces the polarizing film, and the second surface of the second protective film faces the first surface so as to face the retardation layer. 4. The polarizing plate of claim 1, wherein the phase difference layer is disposed between the second protective film and the polarizing film. A liquid crystal display device comprising: a polarizing plate according to claim 1 of the patent application, wherein the liquid crystal molecules are substantially aligned in a direction parallel to the glass base when the black display is present, and the two glass base sides are a polarizing plate comprising a third liquid crystal cell and a second polarizing film and a fourth protective film, wherein the alignment direction is a substantially parallel liquid crystal cell, and the second protective film of the polarizing plate of claim 1 The in-plane slow axis is substantially parallel to the alignment direction of the liquid crystal cell, and the third protective film is R〇: 0 to 5 nm, Rt: -10 to 10 nm, and the film thickness of the third protective film is 20~45 μιη. 6. A liquid crystal display device characterized by having a polarizing plate according to claim 1 of the patent application, wherein the liquid crystal molecules are substantially aligned in a direction parallel to the glass base when the black display is present, and the two glass base sides are a polarizing plate composed of a third liquid crystal cell and a second polarizing film and a fourth protective film; and the second protective film of the polarizing plate of claim 1 The in-plane slow axis A is substantially orthogonal to the alignment direction of the liquid crystal cell, and the third protective film is Ro: 0 to 5 nm, Rt: -10 to 10 nm, and the film thickness of the third protective film is 20 ~45 μιη. -84-