TW200925672A - Long phase difference film, long elliptic polarization film, elliptic polarization plate and image display device - Google Patents

Abstract

Provided is a long elliptic polarization film having excellent productivity in manufacture and excellent view angle characteristics when used for an image display device and excellent color stability when stored in a high-temperature and high-humidity environment. A long phase difference film required for providing such long elliptical polarization film is also provided. Furthermore, an image display device using an elliptical polarization plate clipped from the elliptical polarization film is also provided. The long phase difference film is provided by arranging a vertically aligned liquid crystal layer on a long base material film composed of a transparent resin. The angle formed by the delayed phase axis within the surface of the base material film and the longitudinal direction of the film is 10-80 DEG .

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a strip-shaped retardation film, an elongated elliptical polarizing film, the elliptically polarizing plate, and a reflective liquid crystal display device using the same, and a touch An image display device such as a panel or an organic EL (organic electroluminescence) display device. [Prior Art] In the image display device such as a reflective or transflective liquid crystal display device, a touch panel, or an organic EL display device, a method of suppressing external light reflection and making bright room contrast is used. A circular polarizing plate which is a phase difference plate of a λ/4 plate (and a λ/2 plate) and a linear polarizing plate is known. In the production of the circular polarizing plate, conventionally, after the transparent resin film is formed, the object is extended in the longitudinal direction or the width direction of the film, and a slow phase axis appears in the surface of the optical film, and only a necessary area is cut out. A method in which the retardation axis 〇 and the transmission axis of the linear polarizing plate are inclined at a position of 45° and are bonded to the linear polarizing plate. Therefore, there is a problem that the loss of the phase difference plate is cut off and the procedure of the cutting operation itself, and the productivity cannot be improved, or the misalignment of the bonding axes from the phase difference plates and the linear polarizing plates is likely to occur. Problems such as performance changes. In this patent, Patent Literatures 1 to 3 disclose a retardation film in which the angle formed by the width direction of the roll-shaped film and the slow phase axis is a non-right angle and is non-parallel (ie, inclined). A linear polarizing film having an absorption axis in the longitudinal direction of the roll-shaped film, which is aligned in the longitudinal direction, laminated -4-200925672, a circular polarizing film produced, or a method for producing the same. By such a technique, a round polarizing film having better productivity can be produced. However, the viewing angle characteristics of the important characteristics of the circular polarizing plate disposed on the surface of the image display device by the technique of the present invention (that is, when viewed from various angles) cannot be achieved by the front view. Or contrast. Further, the action of various image display devices has been carried out until now, and the demand for displaying the same optical φ characteristics under various environmental changes is extremely high as the method of use thereof is diversified. In other words, the color tone stability under high temperature and high humidity is important, but the technique of the above Patent Documents 1 to 3 cannot be completely matched to this requirement. A method for improving the viewing angle characteristics, for example, a technique in which the liquid crystal layer disposed in the film thickness direction is disclosed in Patent Document 4, and the phase difference in the thickness direction caused by the extension of the substrate is almost completely disappeared is know. However, the improvement in the technique is only the viewing angle characteristic, and it is difficult to improve the color stability of the wide temperature cylinder under wet conditions.专利 Patent Document 1: Japanese Laid-Open Patent Publication No. 2003-94007 No. JP-A-2007-94007 Patent Document 3: JP-A-2007- 1 53926 Patent Document 4: Japanese Patent Laid-Open No. 20-42683 SUMMARY OF THE INVENTION The object of the present invention is to provide an elongated elliptically polarized light which is excellent in productivity at the time of manufacture, has a viewing angle characteristic when used in an image display device, and has excellent color tone stability when stored in a high-temperature and high-humidity environment. A film, and a strip-shaped retardation film which is necessary for the purpose of -5 to 200925672 is provided. Further, another object is to provide an image display apparatus using an elliptically polarizing plate cut out from the above elliptically polarizing film. The above problems of the present invention are achieved by the following constitution. 1. A long stripe retardation film characterized by being provided in a long retardation film formed by vertically aligning a liquid crystal layer on a long base film formed of a transparent resin, wherein the base film is in-plane The angle between the retardation axis and the length of the film © direction is 10° to 80°. 2. The elongated retardation film according to 1, wherein the transparent resin used on the base film is a cellulose ester. 3. The elongated retardation film according to the above 2, wherein the cellulose ester is cellulose acetate propionate. 4. A long strip-shaped elliptically polarizing film characterized in that at least one of the elongated retardation film according to any one of the above 1 to 3 and the long linear polarizing film are laminated in the longitudinal direction . </ RTI> A elliptically polarizing plate characterized in that it is cut out from the long ellipsic polarizing film described in the above 4. A type of image display device comprising the elliptical polarizing plate described in the above 5. [Effect of the Invention] According to the present invention, it is possible to provide an elongated elliptical polarizing film which is excellent in productivity at the time of production, has a viewing angle characteristic when used in an image display device, and has excellent color tone stability when stored in a high-temperature and high-humidity environment. A long stripe retardation film which is necessary for the purpose of -6-200925672 is provided. Further, an image display device using an elliptically polarizing plate cut out from the above elliptically polarizing film can be provided. BEST MODE FOR CARRYING OUT THE INVENTION In the following, the best mode for carrying out the invention will be described in detail, but the invention is not limited thereto. φ The retardation film of the present invention is characterized in that in the long retardation film formed by vertically aligning the liquid crystal layer on the elongated base film formed of a transparent resin, the retardation in the surface of the substrate film The angle between the shaft and the length direction of the film is 10° to 80°. By laminating at least one of the retardation film and the long linear polarizing film in the longitudinal direction, it is possible to obtain a viewing angle characteristic which is excellent in productivity at the time of manufacture and which is used in an image display device. An elliptical G polarizing film excellent in the effect of the present invention which is excellent in color tone stability when stored in a high-temperature and high-humidity environment. The inventors of the present invention have further studied the color tone stability under high temperature and high humidity which is one of the problems of the present invention. As a result, it has been found that even if a vertical alignment liquid crystal layer is provided on the base film of the film in the longitudinal direction or the width direction of the film, The effect of the present invention is still not obtained, and the effect of the present invention can be obtained when a vertical alignment liquid crystal layer is provided on a substrate film having a retardation axis of 10° to 80° in the longitudinal direction. Although this system is an unpredictable phenomenon, it may cause chaos in the molecular arrangement in the vertical alignment liquid crystal layer during high-temperature and high-humidity storage, which may affect the degree of wavelength dispersion of the in-plane retardation of the substrate film. 200925672 Confusion situation. Therefore, the disorder is not caused by the angle formed by the retardation axis of the base film and the longitudinal direction of the film, in other words, it is presumed that the longitudinal axis is 10 in the longitudinal direction. ~80. When a vertical alignment liquid crystal layer is disposed on the base film, a vertical alignment liquid crystal layer is disposed on the base film of the film in the longitudinal direction or the width direction of the film, and is stored in the vertical alignment liquid crystal layer at a high temperature and high humidity. The disorder of molecular alignment becomes smaller and more stable. @ The following describes the invention in detail. (Long stripe retardation film of the present invention) The retardation film referred to in the present invention refers to a film in which the phase difference in the plane shows λ/4 or λ/2 in a wide wavelength range. More specifically, when the phase difference 値R 〇 (5 50 ) measured at a wavelength of 50 50 nm is a so-called λ/4 plate, it is preferably 108 nm to 168 nm, more preferably 128 nm to 148 nm, and 1 3 8 ± 5 . The best is nm. Further, in the case of the λ / 2 plate, it is preferably 2 4 5 n m to 3 0 5 n m, more preferably 265 nm to 285 nm, and most preferably 275 ± 5 nm. Here, the in-plane phase difference 値R〇 is obtained based on the following equation.

Ro=(nx-ny)xd (wherein nx is the refractive index of the retardation axis in the plane of the retardation film (the maximum refractive index in the plane), and ny is the retardation perpendicular to the in-plane of the retardation film. The refractive index 'd in the axial direction is the thickness (nm) of the retardation film). The retardation film of the present invention is disposed on the -8-200925672 elongated substrate film formed of a transparent resin. The liquid crystal molecules aligned in the thickness direction of the film are coated and fixed, but the transparency of the transparent resin constituting the substrate film of the present invention means that the visible light transmittance is 60% or more. It is 80% or more, and more preferably 90% or more. Therefore, the transparent resin is a resin having the above transmittance for light of a desired wavelength, and is particularly preferably a thermoplastic resin. Further, the transparent tree used in the present invention is preferably formed of a resin having a positive complex refracting enthalpy. Examples of the transparent resin are cellulose ester, polyolefin, poly maple, polycarbonate, polymethyl methacrylate, polyester, polyvinyl alcohol and the like. In particular, a resin having a small photoelastic coefficient is used, and since a phase difference spot due to thermal deformation can be suppressed, it is preferred to use a cellulose ester or a polyolefin. The most preferred is cellulose ester. The base film before stretching can be formed by a solution casting method or a melt casting method, and the most suitable method is preferably used depending on the selected resin characteristics. The retardation film of the present invention is formed of a base film having the above-described phase difference in the plane and a vertical alignment liquid crystal layer on the base film. In this case, the vertical alignment liquid crystal layer is a layer obtained by applying liquid crystal molecules aligned in the thickness direction of the film to the base film and fixing them. It is characterized in that the retardation axis in the plane of the substrate film and the angle formed in the longitudinal direction of the film are 10° to 80°. When the vertical alignment liquid crystal layer is applied, the coating direction is preferably in conformity with the length direction of the substrate film. Thereby, an elongated linear polarizing film having an absorption axis in the longitudinal direction is laminated and aligned in the longitudinal direction of the retardation film, whereby a highly productive, elongated elliptical polarizing film can be obtained. The retardation axis in the surface of the base film constituting the retardation film and the longitudinal direction of the film are in the range of 20° to 70°, preferably 30° to 60° in the range of -9 to 200925672. The range is from 40° to 50°, and the best is substantially 45°. It is 45° in nature and refers to the range of 4542°. As a method of producing the long strip film of this feature, generally, the following oblique stretching method of the base film is used. &lt;Slanting device and oblique stretching method&gt; Hereinafter, a film using a thermoplastic resin will be described as an example of the phase difference film of the present invention. The oblique stretching device used in the present invention is a preheating zone, a heating extension zone, and a cooling zone, and any heating means used in the extension of a conventional thermoplastic resin film can be used. The thermoplastic resin film is obtained by preheating in a preheating zone, extending in a heating extension zone, and aligning in a cooling zone to obtain a stretched film. The holder for the oblique stretching device used in the present invention can be used as long as it can fix the end portion of the thermoplastic resin film, for example, a user of a conventional tenter stretching machine, a groove or The ridges are provided under the driving of mechanical elements that are arranged in a spiral shape. The mechanical element used in the present invention is such that the groove or the ridge is provided in a spiral shape, and a holder is set and driven on the groove or the ridge, such as a screw or a ball screw. The shape of the groove or the ridge is preferably such that the shape of the sine wave or the circular arc is continuous. In the present invention, the mechanical element is disposed at the left and right of the heating device, and the distance between the spirals of at least one of the mechanical elements is changed in the heating extension zone. In other words, by changing the pitch of the spiral, the distance between the pair of holders is varied by changing the speed of the holder, by which the thermoplastic resin film can be stretched. The material of the mechanical element is preferably a metal having excellent heat resistance for use in injection molding or extrusion molding, and is preferably subjected to surface treatment such as heat treatment or rubbing treatment on the surface thereof. Further, it is preferable that the driving source of the mechanical element is capable of controlling the moving speed of the fixed device with high precision, such as a servo motor, a classifying motor, an inverter motor or the like. The apparatus for manufacturing the stretched film of the present invention will be described with reference to the drawings. Fig. 1 is a typical plan view showing an example of a manufacturing apparatus of the stretched film of the present invention. In the figure, '1 is a thermoplastic resin film, and 5 is an extended film. The thermoplastic resin film 1 is fixed to both end portions by the holders 8, 81, and is conveyed in the direction of the arrow A to perform preheating in the preheating zone 2, to extend in the heating extension zone 3, and to perform alignment fixation in the cooling zone 4 to obtain The film 5 is stretched.温度 The temperature of the heating extension 3 may be approximately the same as the glass transition temperature of the stretched thermoplastic resin film, and may be appropriately determined depending on the desired properties of the optical film to be produced. The heating method of the heating extension zone 3 is not particularly limited as long as the thermoplastic resin film can be uniformly heated, for example, a heating device such as a hot air type, a plate heater, a halogen heater, or the like, and the heating extension zone 3 and the cooling zone are heated. Temperature control at the boundary of 4 'The hot air type with high precision is preferred. The temperature of the cooling zone 4 can be generally set to be lower than the glass transition temperature of the stretched thermoplastic -11 - 200925672 resin film by extending the temperature at which the thermoplastic resin film can be aligned. The cooling method of the cooling zone 4 is not particularly limited as long as it can be cooled in the direction in which the thermoplastic resin film is aligned in parallel, and is, for example, a heating device such as a hot air type, a flat heater or a halogen heater, or a heating medium. It is preferable to control the temperature of the boundary between the extension zone 3 and the cooling zone 4 by piping or the like through which the refrigerant passes, and to perform the hot air type with high precision. In addition, the heating extension zone 3 and the cooling zone 4 refer to a region in which the thermoplastic 0 resin film is substantially extended and a region in which the alignment cooling by the stretching is fixed, and does not mean a mechanically and structurally independent region, which means that it can be formed. A region above the temperature at which the thermoplastic resin film is stretched and a region formed by forming the temperature or lower. 6,7 is a spiral provided on the right and left sides of the heating device, and the spiral 6 is as shown in the second (1) diagram, and the squeegees 61 of the ridges are disposed at the same pitch. Further, the spiral 7 is as shown in Fig. 2(2), and the squeegee 71 of the ridge is provided at a varying pitch. In other words, in the preheating zone 2 and the cooling zone 4, the distance between the squeegees 71 is narrow, the pitch of the squeegee 6 1 of the spiral 6 is the same, and the distance between the extension zones 3 is gradually widened and narrowed again, and the cooling zone 4 is The spacing is the same. The above-mentioned spirals 6, 7 are capable of driving a plurality of holders 8, 81, and on the bottom of the spirals 6, 7 (preheating zone 2), the holder 8 provided on the spiral 6, and the fixing provided on the spiral 7. The unit 81 is set downward. Further, 9,91 is a belt for transporting the holders 8, 81 on the side of the front end (cooling zone 4) of the spiral 6, 7 to the bottom (preheating zone 2) side of the spirals 6, 7. Next, a method of extending the thermoplastic resin film will be described. -12-200925672 In the manufacturing apparatus of the above-mentioned stretched film, the end portion of the thermoplastic resin film 1 supplied is fixed by the holders 8 and 81, and is conveyed toward the direction in which the thermoplastic resin film 1 is carried out (in the direction A). 'The conveying speed of the thermoplastic resin film 1 is the same as the speed of the holder 81, and the thermoplastic resin film 1 is not extended in the progress direction. The thermoplastic resin film 1 to be supplied is preheated at its both ends by a preheating zone 2 fixed by a holder 8, 81, and conveyed to the heating extension zone 3. In the preheating Q zone 2, since the distance between the doctor blades 61 and 71 is the same, the moving speeds of the holders 8, 81 are the same, and the thermoplastic resin film 1 is not extended in any direction, and is transported to the heating extension zone 3. In the heating extension 3, the moving speed of the holder 81 is constant, but the moving speed of the holder 8 is gradually widened due to the distance between the blades 6, and becomes faster than the moving speed of the holder 81, and the fixing device 8 is fixed. The distance between the stoppers 81 is gradually widened, and the thermoplastic resin film 1 is extended only in a direction different from the direction in which the thermoplastic resin film 1 is moved. Q Next, the stretched thermoplastic resin film 1 is conveyed to the cooling zone 4, and is aligned and fixed. Since the pitch of the blade 7 1 of the cooling zone 4 is the same as the pitch of the blade 61, the stretched thermoplastic resin film is aligned and fixed in a direct state. The stretched film 5 which is stretched and aligned is discharged from the cooling zone 4 to obtain a stretched film 5 which is aligned in a direction different from the direction in which the thermoplastic resin film 1 is oriented. In other words, in the same manner as shown in Fig. 3, in the obtained stretched film 5, the alignment axis (optical axis) is oblique to the longitudinal direction of the stretched film. -13- 200925672 Therefore, as shown in Fig. 4, by directly laminating the obtained stretched film 2 1 (for example, a linear polarizing film) and the stretched film 24 (for example, a retardation film) obtained by extending the longitudinal axis, it is perpendicular to The direction of the direction is cut, 'the optical axis 23 of the stretched film 21 is different from the direction of the optical axis 25 of the stretched film 24'. A laminate 26 of a film having a different optical axis (for example, a circularly polarizing film) can be obtained. The holders 8, 81 are conveyed to the vicinity of the inlet of the preheating zone 2 by the tapes 9, 91 when the cooling zone 4 is taken out, and the subsequent thermoplastic resin film is fixed and prepared. Next, a method of extending the manufacturing apparatus of the other stretched film in a direction inclined by 45° will be described. In order to extend the thermoplastic resin film obliquely in the direction of substantially 45° in the longitudinal direction, it is preferable to use the tenter shown in Fig. 5. Figure 5 is a typical diagram of oblique extension by a tenter. As shown in Fig. 5, the thermoplastic resin film 101 is conveyed in a constant conveyance direction 1〇3, and is extended obliquely (45°) by the tenter 102. Fig. 5 is a diagram showing the change in the width of the Q film in the extending direction by a dotted line. The film which is latticed at one of the positions (104L and 104R) in Fig. 5 is moved toward the position (105R) away from the rapidity (106R) by moving the left side toward the position (105L) which is close to the slow speed (106L). , implement oblique extension processing. The stretching ratio is preferably 2 to 30 times, more preferably 3 to 10 times. When the glass transition temperature of the thermoplastic resin film is Tg during stretching, heating and stretching in the range of (Tg-30) to (Tg+100) °C is preferred, and (Tg-20)~(Tg+ 80) The range of °C is better. In particular, it is preferred to carry out stretching in a temperature range of (Tg-20) to (Tg + 20) °C and then heat-fixing. Moreover, after the extension step, the mitigation -14-200925672 treatment is preferred. The oblique extension process can also be implemented in several steps. Particularly in the case of high-magnification stretching, it is preferable to obtain a uniform stretching result in a plurality of steps. Further, in order to prevent shrinkage in the width direction, it is also possible to perform a plurality of stretching processes in the lateral direction or the longitudinal direction before the oblique stretching. The oblique extension can be carried out by different steps described above by extending the tenter used in the case where the general film is biaxially stretched. In order to extend Q at different speeds from left to right, the thickness of the film before stretching is adjusted to be different from left to right. When the polyvinyl alcohol solution is cast and formed into a film, the flow rate of the solution can be adjusted to be different from left to right. The adjustment of the flow rate can be easily carried out by attaching a cone to the mold. In addition, it is possible to use the first to fourth drawings of the Japanese Patent Publication No. 2004-20827 or the first to fourth drawings of the Japanese Patent Publication No. 2007-94007, or the first drawing of the Japanese Patent Publication No. 2007-2 03 5 5 6 The oblique extending device described in Fig. 4 and the like. Further, in producing the retardation film of the present invention, it is preferred to extend in the oblique direction before applying the vertical alignment liquid crystal layer described below. In the case of the above-described extension, when the purpose of improving the degree of freedom of control in the direction of the slow axis in the plane of the retardation film is to extend in the longitudinal direction of the film, the length direction is obliquely extended, or the length is After extending obliquely in the direction, it is preferred to extend in the longitudinal direction. In order to achieve a specific example of the object, the film stretching device described in JP-A-2007-3 0466 is preferably used. Preferred embodiments of the present invention will be described with reference to the drawings in the drawings. In the eleventh and twelfth drawings, the plane and the cross section of the film stretching device (expansion device) 4〇1 according to an embodiment of the present invention are shown. Film Stretch Pack -15- 200925672 401 is a longitudinal extension formed by a supply device 403 for supplying a film 402, a longitudinal stretching furnace 404 for heating the film, and an intermediate transfer device 405 for transporting the film 402 downstream (longitudinal extension) The expansion/contraction unit 406, the obliquely extending machine 407 that extends in the oblique direction with respect to the conveyance direction of the conveyance film 402, and the obliquely extending furnace that is provided under the central portion of the cover obliquely extending machine 407 to heat the film 402 The obliquely extending portion (obliquely stretched portion) 409 formed by the 408 is formed by the winding device 410 that winds the film 402. The φ supply device 403 is a device for winding the raw material reel 411 of the film 402, and the film 402 is sandwiched by the reference roller 412 and the nip roller 413, and is fed at a predetermined conveyance speed. The longitudinal stretching furnace 404 is a casing composed of a heat-dissipating material having a hot air duct (heating method) 4M which blows hot air different from each other on the film 402. In the intermediate transfer device 405, the film 402 is sandwiched and conveyed by the proportional roller 415 and the nip roller 416, and extends in the transport direction and the parallel E1 direction. The oblique stretching machine 407 transports the film 402 by the extension chain 417 disposed on both sides of the film 402, and extends only in the direction of the 角度 2 direction of the inclination angle α in the conveyance direction, as will be described in detail below. The obliquely extending furnace 408 is a casing composed of a heat-insulating material having a hot air duct 418 for blowing hot air from the lower surface of the film 420. The winding device 410 adjusts the tension by the tension roller 41 9 to wind the film 402 onto the product reel 420. Fig. 13 shows the configuration of the oblique stretching machine 407. The oblique stretching machine 407 is provided by two parallel extending chains 411, a plurality of bases 421 disposed at a certain interval on the extended chain 411, and slidably mounted on the respective bases 421 in a certain direction. The arm 422 is formed by a holder 423 provided at the front end of each arm 422. The holder 423 is formed by fixing the side edges of the film 402 to -16 - 200925672, and the extension chain 41 7 is formed by erecting a vertical sprocket 4 24 around the surface of the film 420. Figure 14 shows a more detailed configuration of the obliquely extending shaft 407. The extension chain 417 is spaced apart by 1 to fix the base 421. The base body 421 is provided with two slide shafts 425 which are inclined by 45 (the angle ? in Fig. 1) for each pair of extension chains 417, and slidable arms 422 are provided along the respective slide shafts 42 5 . A position determining member 426 formed of a bearing is disposed above the arm 42 2, and the member 426 is disposed by the wire 427 so that the arm 422 can be protruded or retracted. The holder 423 provided at the front end of the arm 422 is a conventional film fixing mechanism for switching switching (fixing or liberating the film 402) with the wire 4W. The oblique stretching machine 407 protrudes from the arm 422 formed by the base 421 of the extended chain 417, and both side edges of the film 402 are fixed by the holder 423, and the extended chain 41 7 is carried out to convey the film 402. In the meantime, the film 402 is retracted by the fixing member 423, and the arm 422 is retracted so that the film 402 extends and widens in the sliding direction of the arm 422 (the direction shown in Fig. 11 and Fig. 2). When the width is widened, the amount of backward movement between the arms 422 facing the sliding direction of the arm 422 becomes equal. After the film 402 is widened, the holder 423 opens the film 402. The arm 422 is then retracted to cause the retainer 423 to contact the film 402 when the extended chain 41 7 is folded back along the sprocket 424. Next, the extension processing of the film 402 of the film stretching device 401 formed by the above configuration will be described. In the longitudinally extending portion 406, the film 402 is fed at a predetermined speed by the reference roller 412, and when the proportional roller 415 is transported at a faster speed than the reference roller 41 2, the heated portion is heated in the longitudinally extending furnace 4〇4. In the transport direction (Ε1 direction -17-200925672), the transfer speed is extended by the ratio of the ratio roller 4 1 5 to the reference roller 4 1 2 . By the extension in the longitudinal direction, the alignment angle of the molecules of the film 402 in the transport direction and the longitudinal direction is imparted. Further, in the obliquely extending portion 409, the film 402 extends in the E2 direction only in the downward direction of the inclination angle α in the conveyance direction. By stretching in the oblique direction, the film 402 is stretched in the direction of the crucible 2 to cause stress on the deformation of the film 402, and when the molecules are arranged at an angle larger than the direction of the second direction in the direction of the second direction of the film 402, The extension force operates to impart an alignment angle to the oblique direction. As a result, the film 402 complements the alignment angle imparted in the longitudinally extending portion 406 with the alignment angle imparted in the obliquely extending portion 409 to the direction in which the combination is achievable, and the longitudinally extending portion 406 and the obliquely extending direction The extension strength (elongation ratio) of the portion 409 is given, and the phase difference 値 is given. When the film 402 is obliquely extended by the film stretching device 1 to produce an alignment film, the film 402 is actually stretched in the longitudinally extending portion 406 and the obliquely extending portion 409, and the alignment angle of the obtained film 402 is measured and available. At the desired alignment angle, the extension ratio of the longitudinal extension 406 is adjusted by increasing or decreasing the speed of the proportional roller 415. Moreover, by adjusting the extension ratio of the obliquely extending portion 409, the desired phase difference 値 can be obtained. For example, when the retardation film (alignment film) is produced by extending the polycarbonate film, the speeds of the reference roller 412 and the proportional roller 41 5 are set to the same speed (the elongation of the longitudinal extension 406 is 〇%). And in the oblique extension 409 is α = 45. When the lower 18% oblique extension is performed, the alignment angle of the film 402 is about 60 in the conveyance direction. Under the condition of 'not changing the oblique extension -18 - 200925672 extension condition 409, about 10% extension in the longitudinal extension 406 (the speed of the proportional roller 415 is about 10% faster than the speed of the reference roller 412) The alignment angle of the film 402 can be made 45°. In short, the film stretching device 40 1, by setting the angle α of the tilting extension 407 to the conveying direction of the extending direction E2, is set to an approximate value of the empirically desired alignment angle, actually by performing the film 402. Extend, adjust the speed of the proportional roller 4 1 5 to adjust the alignment angle. The proportional roller 4 1 5 can be changed while being operated by the 〇 inverter or the stepless transmission, and the desired alignment angle can be easily obtained. In the above embodiment, the film 402 is extended in the oblique direction, and the oblique stretching machine 407 is reversely disposed to perform reverse rotation. It is possible to use a shrinkage action in the direction of the Ε2 direction inside the obliquely extending furnace 408 which defines the heat-shrinkable film, and to heat-shrink the molecules in the direction of the tilt. Further, in the case of the present invention, the film may be stretched in the oblique direction or contracted, and the film may be extended or contracted in the longitudinal direction. ❹ &lt;Cellulose ester&gt; The transparent resin used for the base film constituting the retardation film of the present invention is preferably a cellulose ester. More specifically, it is preferred to use a cellulose ester as a main component and a mixture of a plasticizer, an ultraviolet absorber, or the like. The base film of the present invention contains 60 to 100% by mass of a cellulose ester. The degree of substitution of the total thiol group of the cellulose ester is preferably from 2.1 to 2.9. The cellulose ester used in the present invention is a carboxylate having a carbon number of about 2 to 22, an ester of an aromatic carboxylic acid, and particularly preferably a lower fatty acid having a carbon number of 6 or less. The thiol group bonded to the hydroxy group may be a straight chain, may be branched, or form a ring. Alternatively, other substituents may be substituted. In the case of the same degree of substitution, it is preferable to select a fluorenyl group having a carbon number of 2 to 6 because the above-mentioned carbon number is large and the 'refractive index is lowered. The cellulose ester preferably has a carbon number of 2 to 4 and a carbon number of 2 to 3. The specific cellulose ester can be bonded with an ethyl ketone group such as cellulose acetate propionate, cellulose sulphate butyrate, cellulose acetate propionate butyrate or cellulose acetate phthalate. A mixed fatty acid ester of cellulose propionate, butyrate or sulfhydryl. Further, the butyric acid group forming the butyric acid ester may be linear or branched. Preferred cellulose esters for use in the present invention are particularly preferably cellulose acetate, cellulose acetate butyrate or cellulose acetate propionate. Among them, cellulose acetate propionate is the best. In the cellulose acetate having an average degree of acetalization (degree of acetylation) of 45 to 62.5 %, for example, a film of a retardation agent described in JP-A-2002-22944 is used, and it is extremely useful in the present invention. It is effective, but cellulose acetate propionate is more preferable in the case where it is not caused to permeate on the surface of the film under high temperature and high humidity storage, resulting in a decrease in quality. The cellulose vinegar of the present invention is preferably one which satisfies the following formulas (1) and (2). Formula (1) 2.1 SX + YS2.9 Formula (2) 0 S YS 1 .5 -20- 200925672 wherein lanthanide is the degree of substitution of acetamidine, γ is propyl fluorenyl or butyl fluorenyl, or a mixture thereof Degree of substitution. Moreover, the degree of substitution of the thiol group with the substitution of other thiol groups can be determined by the method specified in ASTM-D817-96. Further, in order to obtain the objective optical characteristics, a resin having a different degree of substitution may be used. The mixing ratio is preferably 10:90 to 90:10 (mass ratio). Among them, it is more preferable to use cellulose acetate propionate. Cellulose acetate propionate, 1.0SXS2.5 '0.1SYS1.5, 2.1SX + YS2.9 more preferred. The number average molecular weight of the cellulose ester used in the present invention is in the range of 60,000 to 3 000 00, and the obtained The film is preferably mechanically strong. Further, it is more preferably from 70,000 to 200,000. The weight average molecular weight Mw and the number average molecular weight Μη' of the cellulose ester are measured by gel permeation chromatography (GPC). The measurement conditions are as follows. Solvent: Dichloromethane column · Shodex Κ 806, Κ 8 05, K8 03 G (connected to 3 Showa Denko (share) system) Column temperature: 2 5 °C Sample concentration: 〇. 1% by mass Detector: RI Model 504 (made by GL Science) Pump: L6 0 00 (manufactured by Hitachi, Ltd.) Flow: 1. Oml/min Calibration curve: using standard polystyrene STK standard polystyrene (Tosoh ( Stock)) Mw = 1 000000~500 of 13 samples corrected - 21 - 200925672 Curve. 1 3 samples were used at approximately equal intervals. Further, as the measurement method, a measurement method of another polymer of the present invention can also be used. The raw material cellulose of the cellulose ester of the present invention is not particularly limited. For example, cotton wool, wood pulp, kenaf or the like can be used. Further, the cellulose ester thus obtained can be used in any combination in any ratio. The cellulose ester of the present invention can be produced by a conventional method. Specifically, φ 言 can be synthesized by referring to the method described in JP-A-10-4 5804. In addition, cellulose esters are affected by trace amounts of metal components in cellulose esters. Such considerations are related to the water used in the manufacturing step, and it is preferred that the composition obtained by forming the insoluble core is small, and metal ions such as iron, calcium, magnesium, etc. are decomposed by polymerization with the possibility of having an organic acid group. When a substance or the like forms a salt and forms an insoluble matter, it is preferably less. The iron (Fe) component is preferably 1 ppm or less. An acidic component such as a calcium (Ca) component φ , a carboxylic acid or a sulfonic acid easily forms a complex compound (i.e., a complex) with a plurality of ligands, and forms a residue derived from insoluble calcium (insoluble precipitation, turbidity). The calcium (Ca) component is 60 ppm or less, preferably 〇3 to 3 ppm. Regarding the magnesium (Mg) component, since it is insoluble in excess, it is preferably 0 to 7 ppm, more preferably 0 to 20 ppm. The metal component such as the content of iron (Fe) component, the content of calcium (Ca) component, and the content of magnesium (Mg) component can be used to dry the cellulose ester in a micro-digester wet decomposition apparatus (sulfuric acid decomposition), alkali After pre-melting by melt, it was analyzed using IC P - -22-200925672 AES (Derivative Bonded Plasma Luminescence Spectroscopic Analysis Apparatus). &lt;Other Additives&gt; The base film constituting the retardation film of the present invention may contain a suitable additive as needed. &lt;Ester compound having at least one pyranose structure or furanose structure of one or more and 12 or less and having all or a part of OH group esterification of the structure&gt; A base film constituting the retardation film of the present invention It is preferable to use an ester compound having at least one pyranose structure or a furanose structure having one or more and 12 or less and having all or a part of the OH group of the structure esterified. In the present invention, it is collectively referred to as the above ester compound, and is also called a sugar ester compound. The ester compound used in the present invention is, for example, the one shown below, but the present invention is not limited thereto. For example, glucose, galactose, mannose, fructose, xylose, or arabinose, lactose, sucrose, butyrate, if, butadiene, stachyose, mannobiose, lactobiose, lactulose, cellobiose , maltose, cellotriose, mannotriose, honeydew trisaccharide or canetriose. Further, for example, gentiobiose, gentian trisaccharide, gentiantetraose, xylotriose, galactose and the like. Among the compounds of this # is particularly preferably a compound having both a ruthenium sugar structure and a furanose structure. For example, sucrose, canetriose, butyrate, 1F fructose, stachyose, etc. are preferred, and sucrose is more preferred. -23- 200925672 The monocarboxylic acid used in the pyranose structure or the furanose structure of the present invention in which all or a part of the OH group is esterified is not particularly limited, and a conventional aliphatic monocarboxylic acid or alicyclic ring can be used. A monocarboxylic acid, an aromatic monocarboxylic acid or the like. The carboxylic acid to be used may be one type or two or more types. Preferred aliphatic monocarboxylic acids, such as acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, 2-ethyl-hexanoic acid, &quot; 1 hospital acid, 12 yard acid, thirteen yard acid, meat citrate, fific acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanic acid, eicosanoic acid, behenic acid , saturated fatty acids such as palmitic acid, waxic acid, heptacosanoic acid, montanic acid, triacontanic acid, and tridecanoic acid, undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, An unsaturated fatty acid such as arachidonic acid or octenoic acid. Preferred are alicyclic monocarboxylic acids such as acetic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, or derivatives thereof. A preferred aromatic monocarboxylic acid, for example, an alkyl group, an alkoxy aromatic monocarboxylic acid, or a cinnamic acid, a benzoic acid or a biphenyl carboxylic acid, is introduced on a benzene ring of benzene φ formic acid such as benzoic acid or toluic acid. An aromatic monocarboxylic acid having two or more benzene rings, such as a naphthalenecarboxylic acid or a tetralincarboxylic acid, or a derivative thereof, more specifically, for example, xylene benzoic acid or 2,3-dimethylphenylene acid , 3,5-dimethylbenzoic acid, 2,3,4-trisuccinic acid, r-isobutyric acid, ruthenic acid, leucovoric acid, α-isobutyric acid, p-isophenylbenzoic acid , α-phenylacetic acid, α-methylphenylacetic acid, α-methyl propylene, hydrogenated cinnamic acid, salicylic acid, hydrazine-anisic acid, m-anisic acid, P-anisic acid, phenolic acid, hydrazine-water Salicylic acid, m-salicylic acid, P-salicylic acid, yttrium-pyroic acid, P-dihydroxybenzoic acid, vanillic acid 'isoxiang-24- 200925672 oxalic acid, 3,4-dimethylbenzoic acid , 〇-cured acid, gallic acid, asaric acid, mandelic acid, anisic acid, homovanillic acid, all 3,4-dimethylbenzoic acid, hydrazine-all 3,4-dimethylbenzoic acid , decanoic acid, ρ-coumaric acid, especially benzoic acid Preferably. An oligosaccharide ester compound can be used as the compound having at least one pyranose structure or furanose structure of 1 to 12. The oligosaccharide is an oligosaccharide which can be used in the present invention, such as malto-oligosaccharide, isomalto-oligosaccharide, and oligosaccharide, which are produced by the action of an enzyme such as a guanamine enzyme in starch or sucrose. 'Half-milk oligosaccharides, milk oligosaccharides. Further, the above ester compound is a compound obtained by condensing at least one of a pyranose structure or a furanose structure represented by the following general formula (Α) by at least one of 12 or less. Here, R11 to Rl5 and r21 to R25 are a carbon number of 2 to 22 or a hydrogen atom, m and n are each an integer of 〇12, and m + n is an integer of 1 to 12. General (A)

-f-P-V H-f-V

-25- 200925672

R11 to Ris and R21 to R25 are particularly preferably a benzamidine group or a hydrogen atom. The benzinyl group may additionally have a substituent R26 (P is 0 to 5), for example, an alkyl group, an alkenyl group, an alkoxy group, or a phenyl group, and the alkyl group, the alkenyl group, and the phenyl group may have a substitution. base. The oligosaccharide can also be produced by the same method as the ester compound of the present invention. In the following, specific examples of the ester compound used in the present invention are φ, but the present invention is not limited thereto. Compound 2

Compound 2

Compound 3

-26- 200925672 Compound 4

R4 Ο ιι a C-C2H5 [Chemical 3] Compound 5

Compound 6

0 R6= —C-CH3 Compound 7

R7 —c-ch3 Compound 8

-27- ch2or$ CH2OR9 ch2ors R90

200925672 Compound 9 R9=—C-CHg Compound 10

CH2〇RtO

H R10〇/CH2OR10 OR10 OR10 H R10= O c-ch3 [Chemical 5] Compound 11 ❿

CH2OR11 R11〇\?r11 H

CH2OR11 OR11 OR11 H och3

Och3 och3 compound 12

o II R12= One C och3 -28- 200925672

Compound 13

ο R13= —C-CH2 Compound 14

R14= och3

OCHa och3 [Chemical 6] Compound 15

Compound 16

ο II —C—CH2

-29- 200925672 Compound 17

Ο

One C-CH3

[Chemical 7] Compound 18

R18=—C-CH3 Compound 19

η Ο il —C-CH3 R19 -30- 200925672 [Chemical 8] Compound 20

0

II R20= —C-CH3 [Chemistry 9] Compound 21

Η · OR21 -31 - 200925672

Compound 22

R22= —C-CH,

OR · OR22 constituting the base film of the phase difference of the present invention, in order to suppress the change of the phase difference 、 and to stabilize the display quality, it is preferable that the ester compound contains a phase difference film of 1 to 30% by mass, particularly It is preferably 5 to 30% by mass. When it is within this range, the excellent effects of the present invention can be exhibited without oozing out, which is preferable. &lt;Plasticizer&gt; The base film constituting the retardation film of the present invention can provide the effect of the present invention, and can also contain a plasticizer as needed. The plasticizer is not particularly limited, and may preferably be selected from the group consisting of polycarboxylic acid ester-32-200925672 plasticizer, glycolate plasticizer, phthalate plasticizer, fatty acid ester plasticizer, and polyol. An ester-based plasticizer, a polyester-based plasticizer, an acrylic plasticizer, and the like. Among them, when two or more kinds of plasticizers are used, it is preferred to use at least one type of polyol ester-based plasticizer. The polyol ester-based plasticizer is a plasticizer formed of a divalent or higher aliphatic polyol and a monocarboxylic acid ester, and preferably has an aromatic ring or a cycloalkane ring in the molecule. Preferred are aliphatic polyol esters having a 2 to 20 valence. Preferred polyols for use in the present invention are the following general formula (a) Table 7J\° General formula (a) Rl-(OH)n

Here, R1 is an η-valent organic group, and η is a positive integer of 2 or more. The 〇H group represents an alcoholic property and/or a phenolic hydroxyl group. © Preferred polyols, such as those shown below, except that the invention is not limited thereto. For example, ribitol, arabinol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 12-propylene glycol, 1,3-propanediol, dipropylene glycol, tripropanol, 1,2-butyl Alcohol, iota, butanediol, 1, butanediol, dibutylene glycol, 1,2,4-butanetriol, hydrazine, pentaerythritol, hydrazine, 6-hexanediol, hexa Alcohol, galactitol, mannitol, 3-methylpentane-1,3,5-triol, tetramethyl glycol, sorbitol, trimethoprim, Sanjing Methylamine , xylene oxime, etc. -33- 200925672 It is especially preferred to use triethylene glycol, tetraethylene glycol, dipropylene glycol, dipropanol, sorbitol, trimethylolpropane or xylenol. The monocarboxylic acid ' used in the polyol ester is not particularly limited, and a conventional aliphatic monocarboxylic acid, alicyclic monodecanoic acid, aromatic mono-residual acid or the like can be used. When an alicyclic monocarboxylic acid or an aromatic monocarboxylic acid is used, it is preferable in terms of improving moisture permeability and retention. Preferred monocarboxylic acids are, for example, those shown below, but the invention is not limited by these. The aliphatic monocarboxylic acid is preferably a fatty acid having a linear or side chain having a carbon number of 1 to 32. The carbon number is preferably from 1 to 20, preferably from 1 to 10. When acetic acid is contained, it is preferred to increase the compatibility with the cellulose ester. The use of mixed acetic acid and other monocarboxylic acids is also preferred. Preferred aliphatic monocarboxylic acids, such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, 2-ethyl-hexanoic acid, undecanoic acid, twelve Alkanoic acid, tridecanoic acid, meat citrate, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanic acid, eicosanoic acid, behenic acid, carnaubalic acid, wax Saturated fatty acid, undecylenic acid, oleic acid, sorbic acid, linoleic acid, linoleic acid, arachidonic acid, acid, heptacosanoic acid, montanic acid, triacontanic acid, tridecanoic acid, etc. Such as unsaturated fatty acids. Preferred are alicyclic monocarboxylic acids such as cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, or derivatives thereof. A preferred aromatic monocarboxylic acid, such as benzoic acid or toluic acid, is introduced into the benzene ring of benzoic acid, and an alkoxy group such as an alkyl group, a methoxy group or an ethoxy group is introduced into the benzene ring of benzoic acid. Further, an aromatic monocarboxylic acid having two benzene rings of -34 to 200925672, such as naphthalenecarboxylic acid or tetralincarboxylic acid, or the like is more preferably used. The molecular weight of the polyol ester is preferably not particularly limited, and is preferably from 350 to 750. The larger the molecular weight, the better, and the carboxylic acid used for the moisture permeability and the cellulose-compatible 〇 polyol ester can be used in combination of one kind of φ. Further, the OH group in the polyol may be partially retained as an anthracene group. In the following, a polyol ester-based plasticizer is exemplified. In particular, it is a specific compound which is benzophenone [[, 300 to 1500, which is less volatile, preferably 1 or 2 or more. -35- 200925672 1 C4H9-C-〇-(CH2)2-〇-(CH2)2-〇-(CH2)2-〇-C-C4H9 _ 0 〇_ 2 {7~i'〇 _(CHi)2_〇_(CHi)2_〇_(CH2,2~〇'u \ / 〇〇v=/ 3 {^&gt;-C-〇-(CH2)2-〇-(CH2) 2-〇-(CH2)2-〇-C-/ 〉 4 wide.)τ|-〇5 C4Hs_C_〇-^CH2_CH2—〇tc_C4H9 ο 4 ο ❹ 6 C8Hi7-C-〇^CH2-CH2-〇- ^--C-C8H17 ο ο 7 〇~r°-(CH^CH2-〇)ri^〇8 ^^-co-{-ch2ch2ch2-o^-c-^^ 9 C4H9&quot;C-〇-^CH2CH2CH2 -〇-^-C-C4H9 ο ο 1〇cbh"-co{ch2ch2ch2-o*^-c-c8h17 o 3 〇_ 11 cHiCH2CH2_o)r|-〇❹ 12 °-f cH^H-°)r- Ii-〇〇ch3 o13 c4h9-co-(-ch2ch-o^-c-c4h9 ch3 o 14 c8h17-co-(-ch2ch-o^-c-c8h17 〇CH^ 〇15〇-r°- ch3 -ch2ch - CHj -36- 200925672 [Chem. 11]

16 ΟΗ,-J CHjCH!—C-CH: CH3 °-l〇°Ί-〇17 ch2-oc-c4h9 CHaCH2- c - gh2 - 〇-e - c4h9 I 〇ch2-o a c-c4h9 iio 18 o Ch2-o-c-c8h17 19

ΟΗ,-0-C Ο ch3ch2-c-ch2-o-c-c8h17I 〇 CH2-〇*C-CbH17o

CH3CH wide C-CH2-0-C I II O % 20

o II CH2-〇&quot;C 21 ch2-oc-ch3 IIo O J_v ch2-oc-&lt;&gt; CH3〇H2-C-CH2-〇-C-CH3I ΰ ch2-oc-ch3 II 0 ch3ch2-c- Ci rb

Ch2-o-c-o23 ch2-o-c-(^) CH3CH2-C-CH2-0-C—/ 〉 ch2-oh ❹ -37- 200925672 [Chem. 12]

? ch2 — ch-ch_ch-ch2

〇=c o=c I I

0 o o 1 I I

-38- 200925672

[Chem. 13]

31 32 -CH2—C-CHj-O-C-/ 〉'-b

U /~λ ii y \v ch2-o-g-f J ch3-gh2-c- ch2-o-c- ch:-〇i~〇-b ch2-o-c* 33

35 c-o-(ch2-ch-ch2-o)^—c—

The glycolate-based plasticizer is not particularly limited, and an alkylalkylalkyl glycolate is preferably used. Alkyl mercaptoalkyl glycolate such as methyl mercapto methyl glycolate, ethyl mercapto ethyl glycolate, propyl mercapto glycolate, butyl decyl butyl glycolate Ester, octyldecyl octyl glycolate, methyl decyl ethyl glycolate, ethyl decyl methyl glycolate, ethyl decyl propyl glycolate, methyl decyl butyl glycolate Ester, ethyl decyl butyl glycolate-39- 200925672 , butyl decyl methyl glycolate, butyl decyl ethyl glycolate, propyl butyl glycolate, butyl thiopropyl Glycolate, methyl mercapto glycolate, ethyl mercaptooctyl glycolic acid, octyldecyl methyl glycolate, octyldecyl ethyl glycolate, and the like. Phthalate-based plasticizers such as diethyl phthalate, dioxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl Phthalic acid 'di-2-hexyl phthalate decyl octyl phthalate, dicyclohexyl phthalate, dicyclohexyl p-dicarboxylate, and the like. A citrate-based plasticizer' such as acetoxytrimethyl citrate, acetoxytriethyl citrate, butyltributyl citrate or the like. A fatty acid ester-based plasticizer such as butyl oleate, methyl linoleic acid, dibutyl phthalate or the like. Phosphate vinegar-based plasticizers, such as triphenyl phosphate, tri-tolyl ester, hydroxytolyl diphenyl phosphate, octyl diphenyl phosphate, bis-phenyl phosphate, trioctyl phosphate , tributyl phosphate vinegar, and the like. The polyvalent phthalate compound ' is formed of an ester of a polyvalent carboxylic acid having a divalent or higher value, preferably a divalent to a valence, and an alcohol. Further, the aliphatic polycarboxylic acid preferably has a price of 2 to 20, and is preferably an aromatic polybasic acid or an alicyclic polybasic acid at a valence of from 3 to 20 carbon atoms. The polybasic acid is represented by the following general formula (b). General formula (b) R2(C〇〇H)m(〇H)n octyl octanoate, phenylphosphonium benzene 20 to 40-200925672 (where 'R2 is the (m + n) valence organic group 'm is a positive integer of 2 or more' π is an integer above 〇, a CO OH group is a carboxyl group, and an OH group is an alcoholic or phenolic hydroxyl group.) Examples of preferred polycarboxylic acids are as follows, but the present invention is not This is limited. For example, trimellitic acid, trimesic acid, pyromellitic acid, trivalent or higher aromatic polyphthalic acid or a derivative thereof, such as acesulfonic acid, adipic acid, strontium sebacate, sebacic acid, oxalic acid, rich An aliphatic polybasic carboxylic acid such as tartaric acid, maleic acid or tetrahydrophthalic acid, an oxidized polycarboxylic acid such as tartaric acid, hydroxymalonic acid, malic acid or citric acid is preferred. In particular, the use of an oxidized polycarboxylic acid is preferred in terms of improving retention and the like. The alcohol to be used in the polyvalent carboxylate compound which can be used in the invention is not particularly limited, and for example, a conventional alcohol or phenol can be used. For example, an aliphatic saturated alcohol or an aliphatic unsaturated alcohol having a linear or side chain having a carbon number of 1 to 32 is preferably used. Preferably, the carbon number is 1 to 20, and the carbon number is preferably 1 to 1 0. Further, an alicyclic alcohol such as cyclopentanol or cyclohexanol or a derivative thereof, an aromatic alcohol such as benzyl alcohol or cinnamyl alcohol or a derivative thereof is preferably used. When a polyvalent carboxylic acid is used as the oxidized polycarboxylic acid, the alcoholic or phenolic hydroxyl group of the oxidized polycarboxylic acid can be esterified with a monocarboxylic acid. Examples of preferred monocarboxylic acids are as described below, but the invention is not limited thereto. As the aliphatic monocarboxylic acid, a fatty acid having a linear or side chain having 1 to 32 carbon atoms can be preferably used. The carbon number is preferably 1 to 20, and the carbon number is preferably 1 to 10. Preferred aliphatic monocarboxylic acids, such as acetic acid, propionic acid, butyric acid, valeric acid-41 - 200925672, caproic acid, heptanoic acid 'octanoic acid, capric acid, capric acid, 2-ethyl-hexanecarboxylic acid, ten Alkanoic acid, dodecanoic acid, tridecanoic acid, meat sulphonic acid, fifteen acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanic acid, hexanilic acid, sylvestre, Saturated fatty acid, undecylenic acid, oleic acid, sorbic acid, linoleic acid, linoleic acid, such as palmitic acid, waxic acid, heptacosanoic acid, montanic acid, triacontanic acid, or tridecanoic acid An unsaturated fatty acid such as arachidonic acid, etc., preferably an example of an alicyclic monocarboxylic acid such as cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctane residual acid, or a derivative thereof . Examples of the preferred aromatic monocarboxylic acid, such as benzoic acid, toluic acid, etc., are introduced into the benzene ring of benzoic acid, and the alkyl group, the biphenyl carboxylic acid, the naphthalene carboxylic acid, the tetrahydronaphthalene carboxylic acid, etc. have two or more. An aromatic monocarboxylic acid of a benzene ring, or a derivative thereof. In particular, acetic acid, propionic acid, and benzoic acid are preferred. The molecular weight of the polyvalent carboxylate compound is not particularly limited, and is preferably in the range of 300 to 1 000, more preferably in the range of 350 to 750.愈 The greater the improvement in retention, the better the moisture permeability and the compatibility with cellulose esters. The alcohol to be used in the polyvalent carboxylic acid ester to be used in the invention may be one type or a mixture of two or more types. The acid hydrazine of the polyvalent phthalate compound which can be used in the invention is preferably 1 mgKOH/g or less, more preferably 〇2 mgKOH/g or less. By setting the acid strontium in the above range, it is preferable because it can suppress the environmental change of the enthalpy. Further, 'acid oxime refers to the number of mg of potassium hydroxide required to neutralize the acid contained in the Ig sample (the carboxyl group of -42-200925672 is present in the sample). The acid bismuth is measured based on JIS K0070. An example of a more preferred polycarboxylate compound is as follows, but the invention is not limited thereto. For example, triethyl cresate, tributyl cresate, ethyltriethyl cresate (ATEC), ethoxylated tributyl cresate (ATBC), benzamidine tributyl toluene Acid ester, acetyltriphenyl toluate, ethyltrityltoluate, dibutyl tartrate, dibutyl butyl tartrate, tributyl trimellitate, homo benzene Tetrabutyl tetracarboxylate and the like. The polyester-based plasticizer is not particularly limited, and a polyester-based plasticizer having an aromatic ring or a cycloalkane ring can be used in the molecule. The polyester-based plasticizer is not particularly limited, and for example, an aromatic terminal ester-based plasticizer represented by the following general formula (c) can be used.

General formula (c) B-(G-A)n-G-B

(wherein B is a benzene monocarboxylic acid residue, and G is an alkylene glycol residue having 2 to 12 carbon atoms or an aromatic alcohol residue having 6 to 12 carbon atoms or an alkylene oxide having 4 to 12 carbon atoms; Residue, A is an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms or an aryl dicarboxylic acid residue having 6 to 12 carbon atoms, and η is an integer of 1 or more). In the general formula (c), the benzene monocarboxylic acid residue represented by Β and the alkylene glycol residue or the oxyalkylene glycol residue or the aryl glycol residue represented by G are The alkylene dicarboxylic acid residue or the aryl dicarboxylic acid residue represented by Α is obtained by the same reaction as a general polyester plasticizer. -43- 200925672 The benzene monocarboxylic acid component of the polyester-based plasticizer used in the present invention, such as benzoic acid, p-tert-butylbenzoic acid, o-toluic acid, meta-toluic acid, p-toluic acid, two Methylbenzoic acid, ethyl benzoic acid, n-propyl benzoic acid, aminobenzoic acid, ethoxylated benzoic acid, etc. may be used alone or in combination of two or more. The alkanediol component having a carbon number of 2 to 12, such as ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1, which is a polyester-based plasticizer which can be used in the present invention. 3-butanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3 -propylene glycol (neopentyl alcohol), 2,2-diethyl-1,3-propanediol (3,3-dihydroxymethylpentane), 2-n-butyl-2-ethyl-1,3- Propylene glycol (3,3-dimethylolbutane), 3-methyl-1,5-pentanediol 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentane Alcohol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-nonanediol, 1,1 2-ten As the octanediol or the like, one type or a mixture of two or more types may be used as the ethylene glycol. Φ It is more preferable that the alkanediol having a carbon number of 2 to 12 is excellent in compatibility with a cellulose ester. Further, 'the above-mentioned aromatic terminal ester has an alkylene glycol component having a carbon number of 4 to 12', such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, etc. The diol may be used alone or in combination of two or more. An aromatic terminal ester having an alkylene dicarboxylic acid component having 4 to 12 carbon atoms, such as succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, sebacic acid, sebacic acid, dodecane As the dicarboxylic acid or the like, one or a mixture of two or more kinds of -44 to 200925672 can be used. An arylene dicarboxylic acid component having 6 to 12 carbon atoms, having phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, I,4-naphthalenedicarboxylic acid, etc. The polyester-based plasticizer used has a number average molecular weight of preferably from 3 Å to 15 Å, more preferably from 400 to 1,000. Further, the acid hydrazine is 0.5 mgKOH/g or less, the hydroxy hydrazine is 25 mgK, the hydrazine H/ or less, the preferred acid hydrazine is 0.3 mgKOH/g or less, and the hydroxy hydrazine is 15 nlgK 〇H/g or less. The following is a specific compound of the aromatic terminal ester-based plasticizer which can be used in the present invention, but the present invention is not limited thereto. ❹ 200925672 § - 52 o

OS VI S9 : 1 o

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"y-8o£0£0o-^-8 ε5-^^ - ^—^loooxo£oooo £—0 —oooxo£oooo *Ho- 8o_hunh0o 中 8 —o (£ οϋοιχο£οοοο· ”S-ζ pan) ^~^-ΟΟΟΙΝΗΟ5-?Α8 « 广οο?£ϋΗϋ-ΟΓ8—^ \yh Jc s «[ο (UV absorber) The substrate film of the present invention may also contain a UV absorber. When the ultraviolet ray of 400 nm or less is absorbed for the purpose of improving the durability, the transmittance of the wavelength of 370 nm is preferably 1% or less, preferably 5% or less, and most preferably 2% or less. The external absorbent according to the invention is not particularly limited. Examples - 47 - 200925672 For example, benzophenone-based compound, benzotriazole-based compound, salicylate-based compound, benzophenone-based compound, cyanide The acryl-based compound, the triterpenoid compound, the nickel complex-based compound, the inorganic powder, etc. (Microparticles) The base film of the present invention preferably contains fine particles. The fine particles used in the present invention, an inorganic compound such as cerium oxide , 0 titanium dioxide, alumina, zirconia, calcium carbonate, calcium carbonate, slippery , clay, calcined kaolin, calcined calcium citrate, hydrated calcium citrate, aluminum citrate, magnesium citrate and calcium phosphate. Microparticles are preferred, and turbidity is lower, especially in the case of oxidization. The average particle diameter of the primary particles of the preferred microparticles is preferably from 5 to 40 nm, more preferably from 10 to 300 nm. These may also contain two secondary aggregates having a particle diameter of 0.05 to 0.3 μm, as long as it is an average particle. When the diameter of the granules is 100 to 400 nm, the content of the fine particles in the protective film of the polarizing plate is preferably in the absence of agglomeration. The content of the fine particles in the protective film of the polarizing plate is preferably 〜1 〜1% by mass, preferably 0.05. More preferably, it is preferably 0.5% by mass. When the polarizing plate protective film having a multilayer structure is formed by the co-casting method, it is preferable to contain the added amount of fine particles on the surface. For the fine particles of cerium oxide, for example, commercially available Aerosil R972 can be used. , R972V, R974, R812, 200, 200V, 300, R202, 0X50, TT600 (the above are made by Japan Aerosil Co., Ltd.). For zirconia fine particles, for example, commercially available Aerosil R976 and -48- 200925672 can be used. 811 (above is Aerosil ( The product name is a polymer such as a polyoxyalkylene resin, a fluorine resin, and an acrylic resin. Preferably, the polyoxyalkylene resin is preferably a three-dimensional network structure, and for example, a commercially available Tospearl can be used. 103. Trade names of the same 105, the same 108, the same 120, the same 145, the same 3120 and the same 24 0 (above the Toshiba polyoxane (stock) system). Among them, when Aerosil 200V or Aerosil R972V is used, it is preferable because the turbidity of the polarizing plate protective film can be kept low and the friction coefficient is lowered. In the polarizing plate protective film used in the present invention, the dynamic friction coefficient of at least one side is preferably 0.2 to 1.0. Various additives may be added in portions to the slurry of the cellulose ester-containing solution before film formation, or may be additionally added to the line using an additive solution. In particular, since the fine particles can reduce the load on the filter material, it is possible to add part or the whole amount to the line. When the additive solution is added to the working line, the mixing with the slurry is good, so that a small amount of the cellulose ester is preferably dissolved. The amount of the cellulose ester is preferably from 1 to 10 parts by mass, more preferably from 3 to 5 parts by mass, per 100 parts by mass of the solvent. In the present invention, in order to add and mix the line, for example, an in-line mixer such as a static mixer (manufactured by Toray Engeering Engine) or SWJ (Toray Static In-Tube Mixer Hi-Mixer) is preferably used. . &lt;Production method of retardation film&gt; Next, a method of producing the retardation film of the present invention will be described. -49- 200925672 A substrate film constituting the retardation film of the present invention is preferably a cellulose ester film produced by a solution casting method or a melt casting method. When the substrate film constituting the retardation film of the present invention is produced, the step of casting the slurry onto the infinitely moving endless metal support by dissolving the cellulose ester and the additive in a solvent and preparing the slurry is performed. The step of subjecting the cast slurry to a web, drying, the step of peeling from the metal support, the step of stretching or maintaining the width, and the step of drying, the step of winding the warp-processed film. Describe the steps involved in modulating the slurry. The concentration of the cellulose ester in the slurry is preferably such that the drying load after casting on the metal support is reduced. However, when the concentration of the cellulose ester is too rich, the load during filtration is increased, and the filtration accuracy is deteriorated. The concentration of these two standings is preferably 10 to 35 mass%, more preferably 15 to 25 mass%. The solvent used for the slurry may be used singly or in combination of two or more kinds, and a good solvent of the cellulose ester may be used in combination with a poor solvent, which is preferable in terms of production efficiency, and a good solvent is a cellulose ester. It is preferred in terms of solubility. A preferred range of the mixing ratio of the good solvent to the poor solvent is 70 to 98% by mass of the good solvent and 2 to 30% by mass of the poor solvent. The good solvent and the poor solvent are those in which the cellulose ester to be used is dissolved as a good solvent, and those which are separately expanded or insoluble are defined as a poor solvent. Therefore, depending on the average degree of acetification of the cellulose ester (degree of substitution of ethyl ketone), when a good solvent or a poor solvent is changed, for example, when acetone is used as a solvent, the cellulose ester of the cellulose ester (the degree of substitution of acetyl group is 2.4), Cellulose acetate propionate is a good solvent of -50-200925672, and cellulose acetate (degree of ethylene-based substitution 2.8) is a poor solvent. The good solvent to be used in the present invention is not particularly limited, and examples thereof include an organic halide such as dimethane or dioxin, acetone, methyl acetate, methyl n-methyl acetate and the like. In particular, for example, dichloromethane or methyl acetate is preferred. Further, the poor solvent to be used in the present invention is not particularly limited, and examples thereof include methanol, ethanol, n-butanol, cyclohexane, cyclohexane and the like. Further, it is preferred that the slurry contains 0.01 to 2% by mass of water. Further, the solvent used for dissolving the cellulose oxime ester is a solvent which is removed from the film by drying in the film forming step, and the material is reused. A general method can be used for the method of dissolving the cellulose ester in the preparation of the slurry described above. When heated or pressurized in combination, it can be heated at normal pressure or above. When the solvent is heated at a temperature not higher than the boiling point under normal pressure and does not boil under pressure, it is preferred to prevent the formation of agglomerated undissolved matter called gel or undissolved matter when heated and stirred and dissolved. Further, it is preferred to mix the fiber, the vitamin ester, and the poor solvent to wet or swell, and then add a good solvent to dissolve. The pressurization can be carried out by a method of pressurizing by an inert gas such as nitrogen gas or by a method of increasing the vapor pressure of the solvent by heating. Heating is preferably carried out from the outside, and it is preferred that the sleeve type is easy to control the temperature. The heating temperature of the solvent to be added is preferably higher in terms of the solubility of the cellulose ester. However, when the heating temperature is too high, the necessary pressure is increased and the productivity is deteriorated. The heating temperature is preferably 45 to 120 ° C, more preferably 60 to 11 ° C, and more preferably 70 to 105 ° C. Moreover, the pressure is adjusted at the set temperature and the solvent will not boil in the range of -51 - 200925672. Further, it is preferred to use a cooling dissolution method, whereby the cellulose ester can be dissolved in a solvent such as methyl acetate. Next, the cellulose ester solution is filtered using an appropriate filter material such as filter paper. When the filter material is insoluble or the like, it is preferable that the absolute filtration precision is small, and the absolute filtration accuracy is too small, and the filter material is liable to cause clogging. Therefore, it is preferable to use a filter material having an absolute filtration accuracy of 〇. 〇〇 8 mm 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 general filter medium, a plastic filter material such as polypropylene or Teflon (registered trademark), or a metal filter material such as stainless steel can be used, and it is preferable that the fiber does not fall off. It is preferred to remove impurities such as bright foreign matter contained in the cellulose ester of the raw material by filtration.亮 Highlighting the foreign matter so that the two polarizing plates are placed in a cross-coil state, and a roll of cellulose ester is placed therebetween, and light is irradiated from one side of the polarizing plate, and light from the opposite side is generated when viewed from the other side of the polarizing plate. If there is a leak, there will be a visible point (foreign matter), and a number of bright dots having a diameter of 0.01 mm or more is preferably 200 or less. Preferably, it is 100 pieces/cm2 or less, more preferably 50 pieces/cm2 or less, and the most preferable one is 0~10 pieces/cm2 or less. In addition, the fewer the bright spots below 0.01 mm, the better. The filtration method of the slurry can be carried out by a general method, and the solvent is heated at a temperature higher than the boiling point of -52-200925672 and at a temperature at which the solvent does not boil under pressure, and the filtration method is performed before and after filtration. The rise in pressure difference (referred to as differential pressure) is small, so it is preferable. The preferred temperature is 45 to 120 ° C, preferably 45 to 70 ° C, more preferably 45 to 55 ° C. The smaller the filter pressure, the better. The filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and most preferably 1.0 MPa or less. 〇 Here, the casting step for the slurry is explained. The metal support of the casting (casting) step is preferred to make the surface mirror-finished, and the metal support may have a casting width of 1 to 4 m by using a stainless steel strip or casting to surface-treat the barrel. . The surface temperature of the metal support in the casting step is -50 ° C ~ the boiling temperature of the solvent is not reached, and the temperature is high, because the drying speed of the web can be made fast, it is better, but when it is too high, the web is too high. Foaming and deteriorating planarity. The preferred support temperature is 0 to 40 ° C, and more preferably 5 to 30 ° C. Further, by cooling, the web is gelated, and in a state where a large amount of residual solvent is contained, it is preferable to peel off from the tub. The method of controlling the temperature of the metal support is not particularly limited, and is a method of blowing warm air or cold air, and a method of bringing warm water into contact with the inside of the metal support. In the case of using warm water, since the heat can be efficiently transmitted, the temperature of the metal support body is short for a certain period of time, which is preferable. When using warm air, use a wind with a higher temperature than the destination temperature. -53- 200925672 When the roll-shaped cellulose ester has good planarity, the amount of solvent remaining when the web is peeled off from the metal support is preferably 10 to 150% by mass, preferably 20 to 40% by mass or 60 to 130% by mass. % is better, preferably 20 to 30% by mass or 7 to 1 to 2% by mass. In the present invention, the amount of residual solvent is defined by the following formula.

The amount of residual solvent (% by mass) = {(MN) / N} xlOO 〇 Moreover, the lanthanum is the mass of the sample taken at any time during or after the manufacture of the web or film, and the lanthanum is at 1 1 5 The mass after heating at ° C for 1 hour. Further, in the drying step of the roll-shaped cellulose ester, the web is peeled off from the metal support and dried, and the amount of the residual solvent is preferably 1% by mass or less, more preferably 0.1% by mass or less, and most preferably It is 〇~0.01% by mass or less.薄膜 The film drying step is generally carried out by means of roll drying (the way in which several rolls arranged in the upper and lower rolls are alternately passed through the web and dried) or by means of a tenter to convey the web and dry it. In order to produce a base film constituting the retardation film of the present invention, when the amount of residual solvent in the web is large after peeling from the metal support, it is extended in the conveyance direction (=length direction), and the ends of the web are fixed. A fixed tenter method such as a device is preferably extended in the width direction. Further, when the angle formed by the in-plane retardation axis of the base film and the coating direction when the layer formed of the liquid crystal molecules is formed is adjusted to 〜8 〇°, the -54-200925672 is obliquely extended as described above. The device is preferably extended. &lt;Vertically Aligned Liquid Crystal Layer&gt; The retardation film of the present invention is characterized in that the base film has a vertical alignment liquid crystal layer (a layer in which liquid crystal molecules aligned in the thickness direction of the film are coated and fixed). The vertical alignment liquid crystal layer of the present invention is applied to a substrate film of the present invention by applying a liquid crystal material or a liquid crystal solution to the substrate film of the present invention, followed by drying and heat treatment (also referred to as alignment treatment), by ultraviolet curing or thermal polymerization. In the immobilization treatment of the liquid crystal alignment, it is preferable to form the phase difference plate by the rod-like liquid crystal aligned in the vertical direction. Here, the alignment in the vertical direction means that the rod-like liquid crystal molecules are aligned in the range of 70 to 90 (the vertical direction is 90) to the film surface. The rod-shaped liquid crystal can be diagonally aligned, and the alignment angle can be changed slowly. Preferably, it is in the range of 80 to 90°. G The vertical alignment liquid crystal layer of the present invention has a phase difference 値Ro of 0 to 10 nm in the in-plane direction, a phase difference 値Rth in the thickness direction of -50 to -40 nm, and a rod shape aligned in the vertical direction. The phase difference plate of the liquid crystal is preferred. It is more preferable that Ro is in the range of 0 to 5 nm. Here, Rth is defined by the following formula.

Rth={(nx + ny)/2 — nz}xd (wherein nx is the refractive index in the direction of the retardation axis in the plane of the phase difference film (the maximum refractive index in the surface -55-200925672), and the ny is vertical The refractive index in the retardation axis direction in the plane of the retardation film, nz is the refractive index in the thickness direction of the film, and d is the thickness (nm) of the retardation film. For the measurement of the phase difference KO, an automatic birefringence meter KOBRA-21ADH (manufactured by Oji Scientific Instruments Co., Ltd.) or the like can be used. The Rth of the vertical alignment liquid crystal layer is set under the offset of the Rth of the base film, and the viewing angle characteristic of the circularly polarizing film is good. Therefore, depending on the Rth of the base film, the vertical alignment liquid crystal layer is appropriately selected. The coating conditions (the type of liquid crystal molecules, the concentration of liquid crystal molecules in the coating liquid, the film thickness after drying, and the like) are important. For example, when the Rth of the base film is different from each other', when the vertical alignment liquid crystal layer is formed under the same liquid crystal molecule and under the same coating conditions, the substrate film can be imparted with excellent viewing angle characteristics as a circularly polarizing film. The Rth can be achieved by changing the thickness of the vertical alignment liquid crystal layer. When the rod-like liquid crystal is aligned to form a rod-like liquid crystal layer, an alignment film coated with a vertical alignment agent in which the liquid crystal material is arranged in the vertical direction is used, and the liquid crystal material is vertically aligned and then fixed. When the liquid crystal material itself is aligned in the vertical direction at the air interface until the alignment of the predetermined force with the air interface, and the alignment film is not particularly necessary, the composition can be simplified. For the specific method of aligning the liquid crystal material in the vertical direction, an alignment film formed of a crosslinked product containing a block polymer composition of a (meth)acrylic block polymer described in JP-A-2005-148473 or the like is used. The method is the same as the method of the vertical alignment film described in the publication No. 2005-265889, the method of using the air interface vertical alignment agent from -56 to 200925672, and the like. When the rod-like liquid crystal layer is in the above range, it is preferable to control the alignment of the rod-like liquid crystal layer, the control of the film thickness, the temperature at the time of ultraviolet curing, the control of the tilt angle, and the pretilt angle of the support and the air interface. The liquid crystal layer is a liquid crystal material having a liquid crystal phase at a predetermined temperature, and has a predetermined liquid crystal regularity and is formed by hardening. The upper limit 温度 of the temperature of the liquid crystal phase is displayed, for example, a temperature at which the cellulose ester film of the substrate is not damaged by hydrazine, and is not particularly limited. Specifically, it is preferable to use a liquid crystal material which forms a liquid crystal phase at a temperature of 1 20 ° C or less (preferably at a temperature of 100 ° C or less) in terms of ease of control of the step temperature and maintenance of dimensional accuracy. Further, the lower limit 显示 of the temperature at which the liquid crystal phase is displayed is a temperature at which the liquid crystal material is kept in alignment when used as a polarizing plate. The liquid crystal material used in the rod-like liquid crystal layer of the present invention is preferably a polymerizable liquid crystal material. The polymerizable liquid crystal material can be polymerized and used by irradiation with a predetermined active radiation, and the vertical alignment state is fixed in a polymerized state. The polymerizable liquid crystal material may be any of a polymerizable liquid crystal monomer, a polymerizable liquid crystal oligomer, or a polymerizable liquid crystal polymer, or may be used in combination with each other. In the above, the polymerizable liquid crystal monomer can be used as the polymerizable liquid crystal material because of the high sensitivity and the ease of vertical alignment. Specific polymerizable liquid crystal monomer, for example, a rod-like liquid crystal compound (1) represented by the following general formula (MV1), and a -57-200925672 rod-like liquid crystal compound (II) represented by the following general formula (MV2) ). The compound (I) can be used by mixing two or more compounds of the general formula (MV1), and similarly, the compound (II) can be used by mixing two or more compounds of the general formula (MV2). Further, one or more compounds (1) and one or more compounds (Π) may be used in combination. [Chem. 16] MV1 R1

CH2C-C〇^CH2^〇-^J^-C〇—5S

X cch2 I R2 [Chem. 17] MV2 R3 CHjC-CO- 士士. In the general formula (MV1) which represents the compound (I), R1 and R2 each represent hydrogen or a methyl group. When the temperature range in which the liquid crystal phase is displayed is wide, it is preferred that both R1 and R2 are hydrogen. X may be any of hydrogen, chlorine, bromine, iodine, an alkyl group having 1 to 4 carbon atoms, a methoxy group, a cyano group, or a nitro group, with chlorine or a methyl group being preferred. Further, the (meth)acryloxy group at both ends of the molecular chain of the compound (I) and the alkylene chain length of the distance from the aromatic ring are a and b, and may be any integer in the range of 2 to 12, respectively. It is preferably in the range of 4 to 10, and more preferably in the range of 6 to 9. Compound (I) can be synthesized by any method. For example, when X is a methyl group, -58 to 200925672, the compound (I) can be obtained by using 1 equivalent of methylhydroquinone and 2 equivalents of 4-(m-(methyl)propenyloxyalkoxy)benzoic acid. The esterification reaction is prepared. Esterification reaction The above-mentioned benzoic acid is activated by an acid chloride or a sulfonic acid anhydride or the like to cause a reaction with methylhydroquinone. Further, a condensing agent such as DCC (dicyclohexylcarbonyldiimide) can be used to directly react a carboxylic acid unit with methylhydroquinone. In addition to these methods, the ester can be first obtained by esterification of 1 equivalent of methylhydroquinone with 2 equivalents of 4-(m-benzyloxyalkoxy)benzoic acid, followed by © The compound (I) can be synthesized by debenzylation by a hydrogenation reaction or the like, followed by propylene thiolation of the molecular terminal. When an esterification reaction of methylhydroquinone with 4-(m-benzyloxyalkoxy)benzoic acid is carried out, methylhydroquinone is introduced into the diacetate, and then reacted with the above benzoic acid in a molten state, directly The ester body is obtained. The compound (I) wherein X of the general formula (MV1) is not a methyl group can also be obtained by the same reaction as described above by substituting methylhydroquinone with a hydroquinone having a corresponding substituent. In the general formula (MV2) representing the compound (?), when R3 is hydrogen or methyl hydrazine, when the temperature range of the liquid crystal phase is broad, it is preferred that R3 is hydrogen. Regarding c having an alkylene chain length, the compound (II) having a fluorene of 2 to 12 does not exhibit liquid crystallinity. However, in consideration of compatibility with the liquid crystal compound (I), c is preferably in the range of 4 to 10, more preferably in the range of 6 to 9. Compound (II) can also be synthesized by any method, for example, by esterification of 1 equivalent of 4-cyanophenol with 1 equivalent of 4-(η-(methyl)propenyloxyalkoxy)benzoic acid. , synthesis of compounds (Π). In general, the esterification reaction is carried out in the same manner as in the case of a synthetic compound (the above-mentioned benzoic acid is activated by an acid chloride or a sulfonic acid anhydride) to react with 4-cyanophenol. 200925672 The above benzoic acid is reacted with 4-cyanophenol using a condensing agent such as DCC (dicyclohexylcarbonyldiimide). In addition, a polymerizable liquid crystal oligomer or polymerization can be used in the present invention. The liquid crystal polymer or the like. The polymerizable liquid crystal oligomer or the polymerizable liquid crystal polymer can be appropriately selected and used. The layer thickness of the liquid crystal layer of the present invention is preferably in the range of 0.1 μm to 20 μm. It is more preferably in the range of 0.2 to ΙΟμηι. 〇 Direct inspection of the liquid crystal alignment level in the vertical alignment liquid crystal layer provided on the substrate film having the in-plane phase difference 非常 is very difficult, and one focus is made to make azo A sample in which the benzene-based liquid crystal is applied and fixed in an amount of about 1% by mass to 2% by mass in the vertical alignment liquid crystal, and the sample exhibits the same liquid crystal molecules as the sample containing no actual azobenzene liquid crystal. The absorbance in the vicinity of 5 5 Onm to 6 5 Onm is measured by a spectrophotometer, and the degree of alignment is known. In other words, when the absorbance is relatively low, it is possible to determine that substantially all of the liquid crystal molecules are vertically aligned and fixed. Conversely, the absorbance is relatively high. High time' can explain that the liquid crystal molecules of the original vertical alignment do not necessarily have to be vertically aligned. The light absorption area of the azobenzene liquid crystal in the buried gap becomes wider. &lt;Manufacturing method of liquid crystal layer&gt; Polymeric liquid crystal material, The photopolymerization initiator and the sensitizer are required to be used to prepare a composition for forming a liquid crystal layer, and are applied onto a substrate to form a layer for forming a liquid crystal layer. In the present invention, the photo-alignment layer is provided to remove the solvent. Further, it is preferred to use a coating composition in which other components are dissolved as a liquid crystal composition, and apply a layer of -60 to 200925672 on a substrate to remove a solvent to form a liquid crystal alignment layer. This method is preferable to other methods. In the case of a solvent which dissolves the polymerizable liquid crystal material or the like, and does not lower the properties of the transparent resin film, it is not necessary. There are a specific limitation 'specifically', for example, one or two or more kinds of hydrocarbons such as benzene, toluene, xylene, n-butylbenzene, diethylbenzene, tetralin, etc.; methoxybenzene, 1 may be used. An ether such as 2-dimethoxybenzene or diethylene glycol dimethyl ether; a ketone such as acetone, hydrazine methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone or 2,4-pentanedione Class: esters of ethyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate or γ-butyrolactone; 2_pyrrolidone, Ν-methyl- a guanamine solvent such as 2-pyrrolidone, dimethylformamide or dimethylacetamide; chloroform, dichloromethane, carbon tetrachloride, dichloroethane 'tetrachloroethane, trichloroethylene, a halogen-based solvent such as tetrachloroethylene, chlorobenzene or o-dichlorobenzene; 1,3-butanol, diacetone alcohol, glycerin, monoacetin, ethylene glycol, triethylene glycol, hexanediol, Alcohols such as ethylene glycol monomethyl ether, Ethyl acetate, or butyl cellosolve; phenols such as phenol and p-chlorophenol. When only a single solvent is used, the solubility of the polymerizable liquid crystal material or the like is insufficient, and the above-mentioned substrate is eroded. Further, by mixing two or more kinds of solvents, the problem can be avoided. Among the above solvents, a solvent of a hydrocarbon solvent and a solvent mixture of ethylene glycol monoether acetate solvent are preferable, and a mixture of an acid or a ketone and an ethylene glycol is preferable. The concentration of the solution 'is not related to the solubility of the polymerizable liquid crystal material or the film thickness of the liquid crystal layer at the time of the manufacture of the liquid crystal layer, and is usually 1% by mass to 60% by mass, preferably 3 The range of the mass % to 40% by mass is more preferable. In the liquid crystal layer-forming composition used in the present invention, a compound other than the above may be added to the extent that the object of the present invention is not impaired. a compound which can be added, for example, a polyester prepolymer obtained by condensing a polyol with a monobasic acid or a polybasic acid, and a polyester (meth) acrylate obtained by reacting with (meth)acrylic acid; having a polyol group and After the two isocyanate group-containing compounds are reacted with each other, the reaction product is reacted with (meth)acrylic acid to obtain a polyurethane urethane (bis) bisphenol A epoxy resin bisphenol F ring Oxygen resin, novolak type epoxy resin, polycarboxylate polyglycidyl ester, polyol polyglycidyl ether, aliphatic or alicyclic epoxy resin, amine epoxy resin, trisphenol methane epoxy resin, An epoxy resin such as a dihydroxybenzene type epoxy resin, a photopolymerizable compound such as an epoxy group (meth) acrylate obtained by reacting with (meth)acrylic acid, or a light having a propylene group or a methyl propylene group In the liquid crystal layer-forming composition of the present invention, the amount of such a compound to be added is selected within a range that does not impair the object of the present invention, and is generally used for forming a liquid crystal layer of the present invention. 40% by mass to less preferred composition, more preferably 20 mass% or less. In the present invention, a photopolymerization initiator can be used in addition to the polymerizable liquid crystal material as needed. When the polymerizable liquid crystal material is polymerized by electron beam irradiation, when a photopolymerization initiator is not required, when it is generally used, for example, by ultraviolet (UV) irradiation, the photopolymerization initiator is usually used to promote polymerization. 200925672 used. Photopolymerization initiators such as benzyl (also known as benzoyl), benzoin isobutyl ether, benzoin isopropyl ether, benzophenone, benzhydryl benzoic acid, benzoyl benzene Methyl formate, 4-benzylidene-4'-methyldiphenylsulfate, benzylmethylacetal, dimethylaminobenzoate, 2-n-butoxyethyl_4- Dimethylamino benzoate, P-dimethylaminobenzoic acid isotonic furnace, 3,3'-dimethyl-4 methoxybenzophenone, hydroxymethylbenzyl alkenyl acid Oxime ester, 2-methyl-1-(4-methylsulfonyl)phenyl)-2- morpholinylpropan-1-e, » benzyl-2-dimethylamino-1-(4) -morpholinylphenyl)-butan-1-one, κ\-dodecyl)-2-yl-cyano-2-methylpropan-1-one, hydrazine-cyclohexylbenzenephthalene 2 - Hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl')0-yl-2-methylpropan-1-one, 2-chlorothioxanthone , 2,4-diethyl-mouth, 2,4-diisopropylthioxanthone, 2,4-dimethylthioxanthone, isopropylpyrone, or 1-chloro-4-propanol Oxythioxanthone and the like. The amount of the photopolymerization initiator to be added is generally 〇.〇1 鼍% Ο 20% by mass, preferably 0.1% by mass to 1% by mass, more preferably 〇5 ·· ^ ^ % 〜5% by mass The optimum range is added to the polymerizable liquid crystal material of the present invention, and the addition of such a compound can improve the hardenability of the liquid crystal material of the present invention and increase the mechanical strength of the obtained liquid crystal layer and improve the stability thereof. Sex. Further, in the composition for forming a liquid crystal layer to which a solvent is blended, a surfactant or the like may be added in order to facilitate application. When a surfactant which can be added is exemplified, such as an imidazoline, a quaternary ammonium salt, a cationic surfactant such as -63-200925672 alkylammonium oxide or a polyamine derivative; a polyoxyethylene-polyoxypropylene condensate, a primary or Secondary alcohol hydroxyethyl ester, alkyl phenol hydroxyethyl ester, polyethylene glycol and its ester, sodium lauryl sulfate, lauryl sulfate, ammonium lauryl sulfate, hospital-based substituted aromatic sulfonate, hospital Anionic surfactant such as phosphatide, aliphatic or aromatic sulfonic acid morpholine condensate; amphoteric surfactant such as lauryl guanamine propyl betaine, laurylamine acetyl acetate betaine; Nonionic surfactants such as diol fatty acid esters, polyoxyalkylene ethylene alkylamines; perfluorinated alkyl sulfonates, perfluorinated alkyl carboxylates, perfluorinated alkyl oxyethylene adducts , a perfluorinated trimethylammonium salt, a perfluoroalkyl group-hydrophilic group-containing oligomer, a perfluorinated alkyl group/lipophilic group-containing oligomer, a perfluorinated alkyl group-containing amine A fluorine-based surfactant such as a carbamic acid ester or the like. The amount of the surfactant to be added depends on the kind of the surfactant, the kind of the liquid crystal material, the kind of the solvent, and the type of the alignment film of the coating solution, which is usually a polymer liquid crystal material contained in the solution. The ppm to 1 oxime® amount % is preferably, more preferably from 100 ppm to 5% by mass, and most preferably from 0.1 to 1% by mass. A method of applying a composition for forming a liquid crystal layer, for example, a spin coating method, a roll coating method, a printing method, a immersion pull-up method, a mold coating method, a casting method, a bar coating method, a knife coating method, a spray A coating method, a gravure coating method, a reversible coating method, or an extrusion coating method. The method of removing the solvent after applying the composition for forming a liquid crystal layer is carried out, for example, by air drying, heating removal, or removal under reduced pressure, and a method of combining these. By removing the solvent, a liquid crystal alignment fixed layer is formed. -64- 200925672 The step of curing the polymerizable liquid crystal material can be carried out by imparting energy to the polymerizable liquid crystal material, or heat energy, usually by irradiation with ionizing radiation having polymerization ability. The polymerization initiator may be contained in the polymerizable liquid crystal material as it is. The ionizing radiation is not particularly limited as long as it is a radiation that can polymerize the polymerizable liquid crystal material. In general, ultraviolet light or visible light is used for light having a wavelength of 150 to 500 nm. Preferably, Ο 250 to 450 nm is more preferable to ultraviolet light having a wavelength of from 3 〇〇 to 400 nm. In the present invention, a method of performing radical polymerization by irradiating ultraviolet rays (U V) as active radiation and generating radicals from a polymerization initiator by ultraviolet rays is preferred. The method of using UV as the actinic radiation is an established technique and thus contains a polymerization initiator to be used, and is easily applied to the present invention. A light source for illuminating the ultraviolet ray, such as a low pressure mercury lamp (sterilization lamp, fluorescent chemical lamp, black light lamp), a high pressure discharge lamp (high pressure mercury lamp, a metal halide lamp), or an arc discharge lamp (ultra high pressure mercury lamp, xenon lamp, mercury) G gas lamp) and so on. Among them, metal halide lamps, xenon lamps, high-pressure mercury lamps, and the like are recommended. The irradiation intensity is appropriately adjusted by the composition of the polymerizable liquid crystal material or the amount of the photopolymerization initiator used when the liquid crystal is aligned to the fixed layer. By the irradiation of the active radiation, the alignment fixing step 'can be performed at the processing temperature of the step of forming the above-mentioned liquid crystal layer forming layer, that is, under the temperature condition in which the polymerizable liquid crystal material forms a liquid crystal phase' can also be formed in the liquid crystal phase. Perform at low temperatures. -65-200925672 &lt;Linear polarizing film&gt; The linearly polarizing film ’ is not limited to these as long as it is an absorbing linear polarizing film, and various conventional forms can be used. In general, in addition to a film formed by a hydrophilic polymer such as polyvinyl alcohol, treated with a dichroic dye such as iodine, or a plastic film such as polyvinyl chloride to align the polydiene In addition to the polarizing film formed by the above, a polarizing film can be used as a protective film to protect the polarizing film. &lt;Configuration of Elliptical Polarizing Film&gt; The cross-sectional configuration of the elliptically polarizing film of the present invention is shown in the figure. 6 to 8 are diagrams showing an embodiment of the present invention, but the present invention is not limited thereto. Here, the term "elliptical polarizing film" means that the absorption axis of the linear polarizing film and the in-plane slow axis of the retardation film of the present invention form an angle of 0 to 90, wherein, in particular, 45. A range of ±2° is called a circularly polarized thin film. Fig. 6 is a view showing a conventional polarizing plate (having a composition of TAC (cellulose triacetate) / polarizer/TAC), which is used for the side of the phase difference film having the vertical alignment liquid crystal layer of the present invention, using an adhesive or bonding. A circular polarizing film to which the agent is applied. At this time, the polarizing plate can be directly used as a commercially available polarizing plate. Figure 7 is a phase difference film (λ/4) containing a vertical alignment liquid crystal layer of the present invention, and a conventional retardation film (λ/2) formed by obliquely extending only, and a general straight line. A polarizing plate is a circularly polarizing film that is attached to the axial angle of the drawing. -66- 200925672 Fig. 8 is a laminate and a laminate in which a retardation film of the present invention is used as a polarizing plate protective film on one side and another polarizing plate protective film is sandwiched between linear polarizing films. Circular polarizing film. In this case, the bonding surface of the retardation film of the present invention is a surface opposite to the surface on which the vertical alignment liquid crystal layer is provided. &lt;Reflective liquid crystal display device&gt; 层 A layer configuration example of a reflective liquid crystal display device having an elliptically polarizing plate cut out from the ellipsic polarizing film of the present invention is shown in Fig. 9. In the reflective liquid crystal display device shown in Fig. 9, the lower substrate 201, the reflective electrode 202, the lower alignment film 203, the liquid crystal layer 204, the upper alignment film 205, the transparent electrode 206, the upper substrate 207, and the transparent layer are laminated in this order from bottom to top. The conductive film 208 and the elliptically polarizing plate 209 of the present invention are formed. The lower substrate 201 and the reflective electrode 202 are each formed of a reflective plate, and each of the lower alignment film 203 and the upper alignment film 205 is composed of a liquid crystal cell. © When the color is displayed, the color filter layer is additionally set. The illustration of the color filter layer is omitted in Fig. 9, but the color filter layer is preferably provided between the reflective electrode 202 and the lower alignment film 203 or between the upper alignment film 205 and the transparent electrode 206. Further, in the reflective liquid crystal display device shown in Fig. 9, a transparent electrode may be used instead of the reflective electrode 202, and a reflector may be additionally provided. The reflecting plate used for the combination of the transparent electrodes is preferably a metal plate. When the surface of the reflecting plate is smooth, only the specular reflection component is reflected, and the viewing angle is narrowed. Therefore, it is preferable to introduce a concavo-convex structure on the surface of the reflecting plate (described in Japanese Patent No. 275 620). When the surface of the reflecting plate is flat (instead of the surface-concave-concave structure -67-200925672), a light-diffusing film can be provided on one side (cell side or outer side) of the polarizing element. Further, the liquid crystal type to be used is not particularly limited. The liquid crystal type is, for example, TN (Twisted Nematic) type, STN type (Super Twisted Nematic) type, HAN (Hybrid Aligned Nematic) type or the like. The reflective liquid crystal display device of the present invention can be used for a normal white display when the applied voltage is low and a dark display when the voltage is high, and a dark display when the applied voltage is low, and a normal black when the high voltage is high. (normally black) type. Further, a semi-transmissive liquid crystal display device can also be used for the elliptically polarizing plate of the present invention. &lt;Touch Panel&gt; The elliptically polarizing plate of the present invention is used as the anti-reflection layer of the touch panel, for example, the elliptically polarizing plate / the upper conductive film / the spacer / the lower side are electrically conductive from the input operation surface side of the touch panel. The membrane is constructed. The upper conductive film layer can be formed on a substrate such as an optically isotropic polymer film, either directly or as desired via a protective layer of an adhesive layer or a substrate. The touch panel of the present invention may be any one of the touch panels, and a touch panel having a transparent conductive film and a slit interface, for example, a resistive touch panel. The resistive touch panel is formed by arranging two transparent electrode substrates 'having a transparent conductive film on at least one surface and arranging the transparent conductive films against each other and bonding them together' by pressing the upper transparent electrode substrate to make 2 The conductive substrate is in contact with a touch panel of a detectable position. In the touch panel of the present invention, for example, an elliptically polarizing plate/upper conductive film/pitcher/lower conductive film may be sequentially formed from the input operation surface side of the touch panel. The upper conductive film can be formed directly on the substrate such as an optically isotropic polymer film or a protective layer or the like through the adhesive layer or the substrate. The touch panel of the present invention can be used in combination with various display devices. For example, a cathode ray tube (CRT) 'plasma display device (PDP), field emission/display device (FED), inorganic EL device 'organic EL device, liquid crystal display device, and the like. (Embodiment of EL Element) Fig. 10 is a schematic view showing a preferred embodiment of the elliptical polarizing element of the present invention used in an EL (electroluminescence) element. As shown in Fig. 10, the EL element 300 of the present embodiment includes the elliptically polarizing plate 3 of the present invention cut out from the circularly polarizing film of the present invention having the self-absorbing linear polarizer 301 and the laminate of the phase difference 302 of the present invention. 03.直线 The linearly polarized light transmitted through the absorption type linear polarizer 301 is formed by converting the phase difference film 302 into elliptically polarized light. Further, the EL element 300 includes a transparent substrate 340 disposed opposite to the elliptically polarizing plate 303, an anode 305 formed on the transparent substrate 304, a cathode 306 disposed opposite the anode 305, and an anode 305. A light-emitting layer 307 disposed between the cathodes 306. In the EL element 300 having this configuration, by injecting electrons from the cathode 306, a hole is injected from the anode 305, and the two are recombined with the light-emitting layer 307 to generate a visible light corresponding to the light-emitting characteristics of the light-emitting layer 307. . The light generated by the light-emitting layer 307 of -69-200925672 is directly or after being reflected by the cathode 306, and is formed by taking out the outside through the anode 305, the transparent substrate 304, and the elliptically polarizing plate 3 03' of the present invention. Further, the external light 11 incident from the outside of the EL element 300 (outer light incident from the direction perpendicular to the surface of the absorption type linear polarizer 3 〇1) by the indoor illumination or the like is absorbed by the absorption type linear polarizer 301 The remaining half is transmitted as linear polarized light and incident on the retardation film 302.光 The light incident on the retardation film 302 is disposed such that the optical axis of the absorption-type linear polarizer 301 and the retardation film 302 intersect at 45 degrees or 135 degrees as described above, and is transmitted through the elliptically polarizing plate 303 to be converted into The elliptical polarized light elliptically polarized light emitted from the elliptically polarizing plate 303, and when the cathode 306 is specularly reflected, the phase is reversed by 180 degrees, and the circularly polarized light which is inversely inverted is reflected. The reflected light R1 is re-incident on the circular polarizing plate 303, and is converted into parallel linear polarization when the absorption axis of the absorption type linear polarizer 301 (the axis perpendicular to the optical axis) is converted into parallel linear polarization. Sub-301 absorbs and does not exit the outside. The elliptically polarizing plate of the present invention can be used not only in the bottom emission mode but also in the top emission mode. [Embodiment] The present invention will be specifically described by way of Examples, but the invention is not limited thereto. -70-200925672 [Examples] Example 1 The preparation method of the long-length stretched film (A) of Example 1 in JP-A-2007-94007 is based on the preparation of a film of a raw spinel-based resin. The strip-shaped retardation film RF1 was obtained by the same method except that the film width was 300 mm. The RF1 coil is taken into a roll shape. The film was sent out from the RF1 roll, and the coating liquid A described below was applied by an applicator on one side, and the warm air was blown to © to dry, and then UV irradiation was performed to harden the entire layer to obtain a liquid crystal layer provided with a vertical alignment. Long strip retardation film RFl-a. After adjusting the hardening, the thickness of the vertically aligned liquid crystal layer was 1.77 μm. At this time, the direction of application of the vertical alignment liquid crystal coating liquid coincides with the direction of the length of RF 1 . As a result, the retardation 値Rth of the retardation film RF1-a in the film thickness direction was -3 nm. (Coating liquid A) 〇 Vertical alignment liquid crystal compound: UCL-018 manufactured by Dainippon Ink and Chemicals Co., Ltd. 16 parts by mass of methyl ethyl ketone 16.8 parts by mass of propylene glycol monomethyl ether 67.2 parts by mass, and then, as shown in Fig. 7, An elongated polarizing plate having a transmission axis parallel to the film width direction (manufactured by Sanritz Co., Ltd., HLC 2-5618S, thickness: 18 Ομηη) and an in-plane retardation axis in a direction inclined by 15° from the longitudinal direction of the film The long strip-shaped stretched film RFl-b having an internal retardation 値R〇 of 270 nm is bonded to the above-mentioned RF 1 -a in the order of a roll and a roll to obtain a long strip-shaped split-71 - 200925672 light film PF1. At this time, the angle between the in-plane slow axis of the stretched film RF1-b and the in-plane retardation axis of the stretched film RF1-a was 6 〇. The surface of RFl-a bonded to RFl-b and the surface on the opposite side to the surface on which the vertical alignment liquid crystal layer is provided are bonded. The measurement of the above-mentioned retardation ' is performed using an automatic complex refractometer KOBRA-2 1 ADH (manufactured by Oji Scientific Instruments Co., Ltd.) at a temperature of 2 5 ° C and 5 5 % RH at a wavelength of 550 nm. In the width direction, the 3 〇-dimensional complex refractive index measurement is performed at intervals of 1 cin, and the measurement is performed in the sub-type. Block 値R〇= (nx-ny)xd Block 値Rth={(nx + ny)/2-nz}xd (wherein η X is the refractive index of the retardation axis in the plane of the phase difference film) (maximum rate of attack in the plane), ny is the refractive index perpendicular to the retardation axis in the plane of the retardation film, the refractive index in the thickness direction of the nz film, and d is the thickness (nm) of the retardation film) ©Example 2 A base film RF2 made of a polycarbonate-polystyrene copolymer was produced in accordance with the method of Example 1 in JP-A-2003-294942. The elongation treatment was carried out by using the apparatus described in Example 1 at a temperature of 1 75 ° C and a magnification of 3.0, and in a direction in which the retardation axis and the film width direction were inclined at 45°. The coating liquid A was applied onto the RF 2, dried by blowing with a warm air, and then subjected to UV irradiation to cure the entire layer to obtain a long retardation film RF2-a provided with a vertically aligned liquid crystal layer. Adjust the hardened vertical alignment liquid crystal -72- 200925672 The thickness of the layer is 0.44 μηι. At this time, the application direction of the vertical alignment liquid crystal coating liquid coincides with the longitudinal direction of RF2. The long polarizing plate (manufactured by Sanritz Co., Ltd., HLC 2-5618S, thickness: 180 μm) used in Example 1 was inclined at 45 from the longitudinal direction of the film. The direction in-plane retardation axis in-plane retardation 値Ro is 140 nm long. The retardation film RF2-a is sequentially laminated with a roll and a roll to produce a long circular polarizing film PF2. Example 3 The following extended cellulose ester film was produced. The materials used are as follows. [Table 1]

Resin cellulose ester substitution degree Μη Mw/Mn A Ethyl decyl 1,6-propyl aryl group: 0.9 40000 2.5 B Ethyl decyl 1,8-propyl fluorenyl group: 1.1 80000 2.4 C Ethyl decyl 1,2-propionate Base: 1.1 50000 2.4 Plasticizer A 丨· . . a _ aromatic terminal ester exemplified compound No. 1 B aromatic terminal ester exemplified compound No. 3 C aromatic terminal ester exemplified compound No. 13 D trimethylolpropane three Benzoate-73- 200925672 Microparticles AEROSILR972V (made by Yayarojiru, Japan) UV absorber A Gilubin (transliteration) 326 (Chiba Special Chemical System) B Gilubin 109 (Chiba Special Chemical System) C Gibbin 171 (manufactured by Chiba Specialty Chemicals Co., Ltd.) (fine particle dispersion) Ο 10 parts by mass of fine particles of 89 parts by mass of ethanol, and the mixture was stirred and mixed for 50 minutes in a dissolver, and then subjected to dispersion treatment by a homogenizer. &lt;Microparticle-added liquid&gt; The cellulose ester A was added to a dissolution tank to which methylene chloride was added, and after heating and completely dissolved, the product was subjected to An® filter paper No. 244 manufactured by Azure filter paper. filter. The filtered cellulose ester solution was sufficiently stirred, and the fine particle dispersion was slowly added thereto. Further, the particle diameter of the secondary particles is dispersed in a bead mill at a predetermined size. This product was filtered with finemet NF manufactured by Finemet Co., Ltd., manufactured by Nippon Seisaku Co., Ltd. to prepare a fine particle addition liquid. Methylene chloride 99 parts by mass Cellulose ester A 4 parts by mass Microparticle dispersion 11 parts by mass A main slurry of the following composition was prepared. First add two -74-200925672 methyl chloride and ethanol to the pressurized dissolution tank. The cellulose ester A was stirred and charged in a pressurized dissolution tank to which a solvent was added. The material is heated, stirred and completely dissolved, and a plasticizer and an ultraviolet absorber are added to dissolve. This product was filtered using an filter paper No. 244 made of a filter paper (strand) to prepare a main slurry. 1 part by mass of the main slurry liquid and 2 parts by mass of the microparticle-added liquid are added, and the mixture is thoroughly mixed by an in-line mixer (Toray static in-line mixer Hi-Mixer, SWJ), and then a belt casting device is used. Uniformly cast on a stainless steel belt support with a width of 〇2m. On the stainless steel belt support until the residual solvent amount was 110%, the solvent was evaporated and peeled off from the stainless steel belt support. Then, using the apparatus described in Example 1 of the present invention, the substrate film RF3 was obtained by drying at a temperature of 17 (TC, a magnification of 2.0, and a direction in which the slow axis was inclined by 45° in the film width direction). Composition of main slurry liquid> 300 parts by mass of dichloromethane, 57 parts by mass of ethanol, cellulose vinegar A, 100 parts by mass of plasticizers (A), (B), (C), and a ratio of 1:1:1 to 5.5 parts by mass. Agent (D) 5.5 parts by mass of ultraviolet absorber (A) 0.4 parts by mass of ultraviolet absorber (B) 0.7 part by mass of ultraviolet absorber (C) 0.6 parts by mass

Applying a coating liquid A to the base film RF3 and drying it with a warm air, and performing UV irradiation to harden the entire layer, a long retardation film provided with a vertical-75-200925672 alignment liquid crystal layer is prepared. RF3-a. After hardening, the thickness of the vertical alignment liquid crystal layer was adjusted to 0.60 μm. At this time, the application direction of the vertical alignment liquid crystal coating liquid coincides with the longitudinal direction of RF3. The long-length polarizing plate (manufactured by Sacn Corporation, HLC 2-5618S, thickness: 180 μm) used in Example 1 was inclined at 45 from the width direction of the film. The direction in which the in-plane retardation axis of the in-plane retardation axis 値Ro is 1 38 nm long stretch film RF3 -a is sequentially laminated with a roll and a roll to obtain a long strip-shaped circular light film PF3. Example 4 &lt;&lt;Preparation of polarizing plate&gt;&gt; An elongated film of polyvinyl alcohol having a thickness of 120 μm was stretched in one direction toward the MD (temperature 1 1 〇 ° C, stretching ratio 5 times) . This product was immersed in an aqueous solution of 0.075 g of iodine, 5 g of potassium iodide, and 100 g of water for 60 seconds, and then immersed in an aqueous solution of 68 ° C © which was formed by 6 g of potassium iodide, 7.5 g of boric acid, and 100 g of water. The material was washed with water and dried to obtain a polarizing film. Then, based on the following steps 1 to 5, the polarizing film film and the retardation film RF3-a described in the third embodiment and the following cellulose ester film as a polarizing plate protective film on the back side are used. The roller is bonded to the roller to form a circular polarizing film PF4. Step 1: immersed in a 2 mol/L sodium hydroxide solution at 60 ° C for 90 seconds, and then washed with water and dried to obtain a side to which the polarizer is attached (the surface of the liquid crystal layer not coated with the vertical alignment) Saponified retardation film. Step 2: The polarizing film was immersed in a polyvinyl alcohol adhesive-76-200925672 mixture tank having a solid content of 2% by mass for 1 to 2 seconds. Step 3: The excess adhesive to which the polarizing film was attached in the step 2 was gently removed, and the material was placed and placed on the cellulose ester film treated in the step 1. Step 4: The phase difference RF3-a laminated in the step 3 and the polarizing film and the back side cellulose ester film were bonded at a pressure of 20 to 30 N/cm 2 and a conveying speed of about 2 m/min. Step 5: Drying a sample in which the polarizing film formed in the step 4 and the cellulose ester film RF 3-a and the back side cellulose ester film are bonded in a dryer at 80 ° C for 2 minutes to prepare a sample Circular polarizing film PF4. (Production of the inside side cellulose ester film) &lt;Microparticle dispersion liquid&gt; Microparticles 1 1 part by mass Ethanol 8 9 parts by mass 上述 The above was stirred and mixed for 50 minutes in a dissolver, and dispersed by a homogenizer. &lt;Microparticle-added liquid&gt; The cellulose ester B was added to a dissolution vessel to which methylene chloride was added, and after heating and completely dissolved, the product was filtered using a filter paper No. 244 made of a filter paper. The filtered cellulose ester solution was sufficiently stirred, and the above fine particle dispersion was slowly added thereto. Further, the particle diameter of the secondary particles is dispersed in a bead mill at a predetermined size. The -77-200925672 was passed through a finemet NF made by Nippon Seisakusho Co., Ltd. to prepare a fine particle addition liquid. Methylene chloride 99 parts by mass Cellulose ester B 4 parts by mass Microparticle dispersion 11 parts by mass A main slurry of the following composition was prepared. First, methylene chloride and ethanol were added to the pressurized dissolution tank. The mixture was stirred in a pressure-containing dissolution vessel to which a solvent was added, and the cellulose ester ester (ethyl ketone group substitution degree 2.9, Mn 80000, Mw/Mn 2.4) was added. The material is heated, stirred and completely dissolved, and a plasticizer and an ultraviolet absorber are added to dissolve. This product was filtered using a filter paper No. 244 made of a filter paper (strand) to prepare a main slurry. 1 〇〇 mass of the main slurry liquid and 5 parts by mass of the microparticle-added liquid are added, and the mixture is thoroughly mixed by an in-line mixer (Toray static in-line mixer Hi-Mixer, SWJ), and then a belt casting device is used. Uniformly cast on a stainless steel belt support with a width of 2 m. The solvent was evaporated from the stainless steel belt support until the residual solvent dose was 110% on the stainless steel belt support. The tension was applied at the time of peeling, and the stretching was performed at a stretching ratio of 1.1 times in the longitudinal direction (MD). Then, both ends of the web were fixed by a tenter, and the stretching ratio in the width (TD) direction was 1.1 times. After the extension, the width was maintained for a few seconds, and the tension in the width direction was buffered, and the width was maintained. Further, the film was conveyed for 30 minutes in the third drying zone set to 125 ° C, and dried to have a width of 300 mm. A 40 μm thick cellulose ester film. &lt;Composition of main slurry liquid&gt; -78- 200925672 Methylene chloride 450 parts by mass of ethanol 30 parts by mass of cellulose ester (acetamyl substitution degree 2.9, Mn80000, Mw/Mn2.4) 100 parts by mass of plasticizer (A) 2.2 parts by mass of plasticizer (D) 9.5 parts by mass of ultraviolet absorber (A) 0.4 parts by mass of ultraviolet absorber (B) 0_7 parts by mass of 〇 ultraviolet absorber (C) 0.6 parts by mass of Example 5 used in Example 4 In the method of producing RF3-a, the retardation film RF5-a was produced in the same manner except that the device used for the oblique stretching was the oblique stretching device described in Fig. 1. This object was placed under the same back side cellulose film and polarizing film as in Example 4, and a circular polarizing film PF5 was produced by a roll and a roll.实施 Example 6 In the production method of RF5 used in Example 5, RF6' was produced in the same manner as in Example 5 except that the composition of the main slurry liquid was changed as follows, and then coated in the same manner. The liquid crystal layer is vertically aligned to produce RF6_a. In the subsequent method of producing a circularly polarizing film, a circularly polarizing film PF6 was obtained in the same manner as in Example 5. &lt;Composition of main slurry liquid&gt; -79- 200925672 Dichloromethane 3 80 parts by mass of ethanol 70 parts by mass of cellulose ester C 100 parts by mass of polymethacrylate (Mwl 000) 3 parts by mass of sugar ester compound 1 0 0 Among the parts by mass, the sugar ester compound is a mixture of sucrose octabenzoate, sucrose heptabenzoate, and sucrose hexabenzoate in a mass ratio of 1: 1:1. ❹ Comparative Example 1 For Example 2, except that the vertical alignment liquid crystal layer was not provided, the elongated retardation film RF7 was produced by the same fabrication method so that the object and the transmission axis were parallel to the film width direction. A long-length polarizing plate (manufactured by Sanritz Co., Ltd., HLC 2-5618S, thickness: 180 μm) was bonded to form a long circular polarizing film, and a circular polarizing plate PF 7 was cut out from the film. ΟComparative Example 2 In the RF3-a of Example 3, a strip of a vertically aligned liquid crystal layer was prepared in exactly the same manner except that the substrate film was obliquely extended by extension of the longitudinal stretching device in the longitudinal direction. Shape retardation film RF8-a. Then, the retardation axis of the phase difference plate and the polarizing plate (manufactured by Sanritz Co., Ltd., HLC 2-5618S, thickness: 180 μm) were cut at 45° from the RF8-a to obtain a circularly polarizing film PF8. Comparative Example 3 -80-200925672 In Comparative Example 2, a vertical alignment liquid crystal was prepared in the same manner except that the extension in the width direction (transverse extension) was carried out by the tenter in place of the extension in the longitudinal direction (longitudinal extension). Layer long strip retardation film RF9-a. Then, the retardation axis of the phase difference plate cut out from the RF8-a was bonded to the absorption axis of a polarizing plate (manufactured by Sanritz, HLC 2-5618S, thickness: 180 μm) at 45° to obtain a circularly polarizing film PF9. (Example 7) In the fourth embodiment, the in-plane retardation axis of the base film constituting the retardation film RF3-a was extended by 40° in the longitudinal direction of the film, and the phase difference film RF was obtained in the same manner. 1 Ο-a, using the same material as in Example 4, a circularly polarizing film PF10 was obtained. [Embodiment 8] In the fourth embodiment, the in-plane retardation axis of the base film © which constitutes the retardation film RF3-a is extended by 50° in the longitudinal direction of the film, and the phase difference film RF is obtained in the same manner. 1 1 -a, a circularly polarizing film PF11 was obtained in the same manner as in Example 4 using this. [Embodiment 9] In the fourth embodiment, the in-plane retardation axis of the base film constituting the retardation film RF3-a was extended by 10° in the longitudinal direction of the film, and the retardation film RF 1 was obtained in the same manner. 2-a, using the same material as in Example 4, an elliptically polarizing film PF12 was obtained. -81 - 200925672 EMBODIMENT 1 In the fourth embodiment, the in-plane retardation axis of the base film constituting the retardation film RF3-a is 80° in the longitudinal direction of the film, and all of them are obtained in the same manner. The retardation film RF13-a' was used in the same manner as in Example 4 to obtain an elliptically polarizing film PF13. [Example 11] (Evaluation of the performance of the circularly polarizing plate) (Production of the EL device) An organic EL device was produced based on the method described in JP-A-2003-3 3 2068. On one surface of the glass substrate, an anode formed of an ITO transparent film having a thickness of 120 nm was formed by a DC sputtering method from an ITO ceramic target (In2〇3: 811〇2 = 90% by mass: 10% by mass). Then, after ultrasonic cleaning, it is washed by ultraviolet ozone. © Next, on the ITO surface, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1] disposed on a molybdenum boat in a resistance-heated vacuum evaporation apparatus , 1'-biphenyl]-4,4'-diamine (TPD), and ginseng (8-quinolinol) aluminum (Alq) disposed on another molybdenum processing boat, so that the vacuum chamber is lxl ( In the decompressed state of T4pa, the TPD was heated at 220 ° C to form a hole transport layer formed of a TPD film having a thickness of 60 nm, on which Alq was heated at 275 ° C to form an Alq film having a thickness of 60 nm. On the other hand, through the magnesium disposed on the molybdenum boat and the silver disposed on the molybdenum processing boat, the vacuum chamber is formed by 2x-82-200925672 simultaneous evaporation to form 2xl (T4Pa). In the reduced pressure state, a cathode having a thickness i〇〇nrn formed by a Mg·Ag alloy (Mg/Ag = 9/1) was formed, and an organic EL element 1 which emits light in green (main wavelength: 513 nm) was produced. The light-emitting area of the member is 2 cm x 3 cm. Further, when the voltage of 6 V DC is applied to the organic EL element, the front luminance is 1200 cd/m 2 ° on the glass substrate of the organic EL element. The circularly polarizing plates PF1 to P6 to P6 to C13 to 10, and the circular polarizing plates P7 to P9 cut out from the comparative circularly polarizing films PF7 to 9 are bonded via acrylic. Further, the circular polarizing plate is bonded to the position of the phase difference plate between the absorption type linear polarizer of the circular polarizing plate and the glass substrate. &lt;The relationship between the color change of the external light reflection and the high temperature is high. Evaluation of the wetness resistance> After the organic EL device to which the circularly polarizing plate was bonded was stored in a room at 23 ° C and 55% RH for 48 hours (state 1), no voltage was applied, no light was emitted, and the illuminance was about 100 lx. The environment is placed in a direction of 45 degrees from the front to evaluate the black level of the reflected color, and the difference is compared. In addition, the evaluation of the black level of the front is stored in a room of 80 ° C, 90% RH. After 200 hours (state 2), the evaluation was performed in the same manner. The results are shown in Table 2. Moreover, the comparison results were evaluated by the following four states: &lt;&lt;Evaluation criteria of the angle change correlation of color tone&gt;&gt;; -83- 200925672 ◎: Complete with front and squint See the change in hue of external light reflection 〇: only the slight change of the external light reflection in front and squint, but not to the extent of influence △: the difference in hue of external light reflection in front and squint X: The difference in hue of external light reflection on the front and the squint is extremely large &lt;&lt;Evaluation criteria for high temperature and high humidity resistance&gt;&gt; ◎ ◎: Before and after storage, there is no change in hue of external light reflection 〇: before and after storage, only slightly outside The color tone of the light reflection changes, but the degree of influence is not affected Δ: before and after the preservation, there is a state of hue difference X: before and after the preservation, the state of the hue difference is extremely large. Example 1 2 In the method of manufacturing RF6-a used in Example 6 The retardation film RF 1 4-a was produced in the same manner except that the device used for the oblique slanting extension was the oblique stretching device described in the above-described 11th to 14th. This object was placed under the same back side cellulose film and polarizing film as in Example 4, and a circularly polarizing film PF14 was produced by a roll and a roll. [Example 1] In the production method of RF14-a used in Example 12, RF15-a was produced by changing the composition of the main slurry liquid to the same as in the above Example 1 except for the following. The subsequent method of producing a circularly polarizing film was carried out in the same manner as in Example 12, from -84 to 200925672, to obtain a circularly polarizing film PF15.

[Chem. 18]

&lt;Composition of main slurry liquid&gt; Methylene chloride 543 parts by mass of methanol 99 parts by mass of n-butanol 2 parts by mass of cellulose acetate having an average degree of clarification of 59.0% of cellulose oxide 1 2 parts by mass of triphenyl phosphate 9 5 parts by mass of the biphenyl diphenyl phosphate, 5 parts by mass of the following retardation sputum rising agent, 1 part by mass, Example 14 (Evaluation of the performance of a circularly polarizing plate) Using the circularly polarizing film PF14, 15 obtained from Examples 12 and 13, The circular polarizing plate was subjected to the same performance evaluation as in Example 11. The results are shown in Table 2. -85-200925672 οο (Ν^ Remarks Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 CN 镒J_3 JX Comparative Example 3 Example 7 Example 8 Example 9 Example 10 Implementation Example 12 Example 13 ΙΦ翻雄鼷岖固岖·Ν 〇〇◎ ◎ ◎ ◎ XXX ◎ ◎ &lt;] ◎ 色调 Front and squint color change 〇〇 ◎ ◎ ◎ ◎ X 〇〇〇〇〇〇 ◎ ◎ Ν 'Em «Κ 鲣 N N Nen 1? S ^ 0 0 V» No coated LCD 0 § 〇0 ο g 0 U | ffi S ^ t rm 0ί -Kr rn CN T-^ 〇oor 〇Ο Ο ο Oo 1- phase difference film Ro (550nm) Ο 〇00 m 00 cn 00 ro 00 m 1—^ Ο 00 ΓΛ 1—^ 00 m 00 m — H 00 m oo ΓΛ oo m 1—^ oo 00 m Differential film RFl-a 'RFl-b RF2-a 1 RF3-a RF3-a RF5-a RF6-a RF8-a RF9-a RF10-a RFll-a RF12-a RF13-a RF14-a RF15-a Use circular polarizing film Oh (N Oh C^i Uh cu 2 Oh 1/^ tlx 0- VO C1h pu 00 PU ON (X cu PF10 PF11 PF12 PF13 PF14 PF15 circular polarizer No. &lt;N ΓΛ inch κη vo Oo On o &lt;Ν m inch in -86- 200925672 As can be seen from Table 2, the EL elements using the circular polarizing plates PF1 to 6 and 10 to 15 of the present invention have no hue change angle dependence of external light reflection, particularly the black level of the front side even under high temperature and high humidity preservation. In addition, it is known that a cellulose ester is used as a base film, and in particular, the color change of the front side and the squint is small and excellent. Moreover, the circular polarizing plate of the present invention is known as a touch panel or a reflective 〇 liquid crystal display device. The same effect was obtained. Example 1 5 &lt;Performance Evaluation of Phase Difference Plates&gt; Phase difference plates cut out from the retardation films RF-14a and RF-15a obtained in Examples 12 and 13 at 8 ° C, 90 After 400 hours of storage under %RH, the appearance of precipitates on the surface of the film was visually evaluated by the following criteria. The results are shown in Table 3. © «Evaluation criteria for precipitates> ◎: No appearance before and after storage Change 〇: There is only a slight difference in appearance before and after storage, but the possibility of causing a problem is low △: There is a difference in appearance before and after storage. 'The possibility of causing a problem is high. X: There is a significant difference in appearance before and after storage. State of the problem-87-200925672 [Table 3] Phase difference plate No. Film surface precipitates after storage using a retardation film at 80 ° C and 90% RH-400 hours RF14-a ◎ 2 RF15-a Δ In addition, As is clear from Table 3, when RF14-a and RF15-a were compared, the precipitation resistance of RF14-a was extremely excellent. [Fig. 1] A typical plan view showing an example of a manufacturing apparatus of the stretched film of the present invention. [Fig. 2] is a plan view showing an example of a spiral provided on the right and left sides of the manufacturing apparatus of the stretched film of the present invention, and (1) the squeegee blade is a spiral '(2) squeegee blade provided at the same pitch. The spiral set under the change of the pitch. Q [Fig. 3] is a plan view showing an example of an extended film obtained by the apparatus for producing an stretched film of the present invention. [Fig. 4] is a plan view showing an example of a method of laminating and cutting the stretched film obtained by the apparatus for producing an stretched film of the present invention. [Fig. 5] is a typical plan view showing another example of the manufacturing apparatus of the stretched film of the present invention. [Fig. 6] Fig. 6 is a cross-sectional structural view showing a circular polarizing film of the present invention. Fig. 7 is a cross-sectional structural view showing a circular polarizing film of the present invention. -88-200925672 [Fig. 8] shows the present invention. Cross-sectional configuration of the circular polarizing film [Fig. 9] is a layer configuration diagram showing an example of the reflective liquid crystal display device of the present invention. [Fig. 10] Fig. 10 is a schematic view showing an embodiment of an organic EL device of the present invention. [Fig. 11] A film stretching device (expansion device) according to an embodiment of the present invention. [Fig. 12] A film stretching device (expansion device) according to an embodiment of the present invention. [Fig. 13] is a view showing the configuration of a diagonal stretcher. [Fig. 14] is a more detailed structural view showing a diagonal stretcher. [Description of main component symbols] φ 1 : thermoplastic resin film 2 : preheating zone 3 : heating extension zone 4 : cooling zone 5 : extension film 6.7 : spiral 6 1 , 7 1 : squeegee 8.8 1 : holder 9, 91 : Belt-89- 200925672 1 01 : Thermoplastic resin film 102 : tenter 103 : conveyance direction 104L : left lattice position 104R : right lattice position 105L : film left movement position 105R : film right movement position 〇 106L : left movement speed 106R: right moving speed 2 0 1 : lower substrate 202 : reflective electrode 203 : lower alignment film 2 〇 4 : liquid crystal layer 205 : upper alignment film 206 : transparent electrode 207 207 : upper substrate 2 〇 8 : transparent conductive film 209 : ellipse Polarizing plate 300: EL element 3 0 1 : Absorbing linear polarizer 3 02 : Phase difference film of the present invention 3 03 : Elliptical polarizing plate 304 of the present invention: Transparent substrate 3 0 5 : Anode-90 200925672 3 0 6 : Cathode 3 07 : luminescent layer 11 : normal incidence of external light 12 : obliquely incident external light 401 __ film stretching device (expansion device) 402 : film 403 : supply device 〇 4 04 : longitudinal stretching furnace 405 : intermediate conveying device 406 : vertical Extension 407: oblique extension machine 4 0 8 : obliquely extending furnace 4 0 9 : oblique extending portion 41 0 : winding device 4 1 1 : raw material reel © 4 1 2 : reference roller 4 1 3 : nip roller 414 : hot air duct 4 1 5 : proportional roller 4 1 6 : nip roller 4 1 7 : Extension chain 418 : hot air duct 4 1 9 : tension roller 420 : product reel - 91 - 200925672 421 : base 422 : arm 423 : holder 424 : sprocket 4 2 5 : sliding shaft 426 : position determining member 4 2 7: wire 〇 428: wire

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Claims (1)

200925672 X. Patent Application No. 1 A long stripe retardation film characterized in that a long retardation film formed by vertically aligning a liquid crystal layer is formed on a long base film formed of a transparent resin, the base The angle between the slow phase axis in the plane of the film and the length direction of the film is 10. ~80. . 2. The elongated retardation film of claim 1, wherein the transparent resin used on the substrate film is a cellulose ester. 3. The elongated retardation film of claim 2, wherein the cellulose ester is cellulose acetate propionate ο 4 · an elongated ellipsoidal film characterized by The long-length retardation film of any one of the first to third aspects of the patent application, and the long linear polarizing film are laminated and aligned in the longitudinal direction. 5. An elliptical polarizing plate characterized by cutting out a long strip-shaped elliptically polarizing film of the fourth item of the patent application. Ο 6. An image display device characterized by using an elliptically polarizing plate of claim 5 of the patent application. -93-