TW200537167A - Liquid crystal display device - Google Patents

Abstract

To provide an IFS (In-Plane Switching) type liquid crystal display device which can be easily constructed and has improved display quality as well as viewing angle. A liquid crystal display device comprises a first polarizing film, a first phase difference region and a second phase difference region, a first substrate, a liquid crystal layer, a second substrate, and a second polarizing film disposed in this order, the liquid crystal molecule of the liquid crystal layer being aligned parallel to the surface of a pair of the above substrates during black display, wherein the in-plane retardation Re of the second phase difference region is 100 nm or less, the retardation Rth in thickness direction is 50 nm to 200 nm, the refractivity anisotropy of the first phase difference region is negative and the optical axis is substantially parallel to the layer face, and the slow axis of the first phase difference region is perpendicular to transmittance axis of the first polarizing film and the slow axis direction of the liquid crystal molecule during black display.

Description

200537167 IX. Description of the invention: [Technical area to which the invention belongs] The present invention relates to a liquid crystal display device using a cellulose that is useful for the liquid crystal display device. The present invention relates to an in-plane switching mode) a liquid crystal display device that performs display by applying a lateral electric field to a nematic liquid crystal aligned in a horizontal direction, a ferroelectric liquid crystal display device, an antiferroelectric liquid crystal display device, and the like. [Prior art] A TN mode is widely used as a liquid crystal display device in which a twisted nematic liquid crystal layer is sandwiched between two orthogonal polarizers and an electric field is applied in a direction perpendicular to the substrate. When this method is used for black display, liquid crystals stand up against the substrate, so when viewed obliquely, light leakage due to the birefringence of liquid crystal molecules occurs. In view of this problem, the liquid crystal cell is optically compensated by using a thin film of liquid crystal molecules mixed with alignment, and a method for preventing the light leakage is being put into practical use. However, even if liquid crystal molecules are used, it is very difficult to completely compensate the liquid crystal cell line in optical light without problems, and there is a problem that the gray-scale inversion cannot be completely suppressed in the direction below the screen. In order to solve such a problem, a proposal discloses a liquid crystal display device that applies a lateral electric field to the liquid crystal, that is, an In-Plane Switching (IPS) mode, and a vertical alignment (VA) mode. Protrusions or slit electrodes formed in the plate are used for the alignment and division of liquid crystals with negative dielectric constant anisotropy, and are being put into practical use. In recent years, these boards have been used not only for monitors, but also for TV applications, and the brightness of the screen has been greatly improved. Therefore, in the black display of these operation modes, a slight light leakage in the oblique incident direction in the diagonal position will cause the display quality to be lowered. 200537167 ::, · The reason has not been noticed. In the IPS mode, optical compensation materials are also arranged between the liquid crystal layer and the polarizing plate. As a means to improve the hue and the viewing angle, for example, there are references (see the patent document | a white display viewed from an oblique direction). Or a method for mid-tone display is formed by disposing a birefringent birefringent medium between the substrate and the polarizing plate so that the optical axes for increasing or decreasing the retardation of the liquid crystal layer when tilted are orthogonal to each other. The proposal discloses a method for making a φ compensation film (refer to Patent Documents 2, 3, and 4). The optical compensation is made up of a styrene polymer or a dish-like liquid with a negative intrinsic refraction, and a combined optical compensation is also disclosed. Patent Document 5 of the film) This optical compensation film is a combination of a film with positive birefringence and in-plane light film, and a film with positive birefringence and optical axis in the film direction. This method is a two-half-axis optical compensation sheet (refer to Patent Document 6), which uses a film with negative hysteresis as a protective film for a polarizing plate. In this method, an optical compensation layer with positive hysteresis (refer to the patent) Wen Ye, however, because of the multiple refraction anisotropy of the liquid crystals in the liquid crystal cell to improve the viewing angle and oblique viewing of the orthogonal polarizer, the light leakage due to the intersection of the polarization axes and the angle deviation, There are problems that cannot be fully solved. Moreover, even if it is considered that the light leakage can be compensated, it is very difficult to completely compensate the liquid crystal cell optically. The protective film of the main light plate is optically anisotropic. In order to include this, To compensate, it is necessary to extremely increase the directionality of the retardation film and have a multi-fold black display. K 1) Reveal the improved color medium. The optical compensation film is compensated by the crystalline compound method (refer to the method where the academic axis is located). It has been proposed that one of the wavelengths of the line make the surface set K 7) 〇 By eliminating, it is more necessary for the light to be deflected from the cause of orthogonal polarization 200537167 to add an optical anisotropic layer. A method for reducing the phase difference of a protective film 'There are references (refer to Patent Documents 8 and 9) that use a film containing norbornene, or a film containing a resin having an imine group and a resin having a phenyl group and a nitrile group. Comes as a protective film. However, these synthetic resins are generally hydrophobic, have problems with adhesion to polarizing films, and are easily peeled. Furthermore, in the step of laminating the protective films on both sides of the polarizing film, there is a problem in that it is impossible to expect that moisture penetrates from the polarizing film and there is a problem that the polarization performance is deteriorated due to the residual moisture inside. [Patent Document 1] JP 9-80424 [Patent Document 2] JP 10-54982 [Patent Document 3] JP 1 -202323 [Patent Document 4] JP 9-292522 [Patent Document 5] Japanese Patent Application Laid-Open No. 1 1-1 33408 [Patent Literature 6] Japanese Patent Application Laid-open No. 1 1 -3052 1 [Patent Literature 7] Japanese Patent Application Laid-Open No. 10_30729 [Japanese Patent Application No. 8] Japanese Patent Laid-Open No. 2004-464 [Patent Document 9] Japanese Unexamined Patent Publication No. 2004-4642 [Summary of the Invention] The object of the present invention is to provide an in-plane switching (IPS) type liquid crystal display device. With a simple structure, not only the display level And can significantly improve the viewing angle. The means to solve the aforementioned problems are as follows. That is, the present invention is (1) a liquid crystal display device in which a first polarizing film, a first retardation region and a second retardation region, a first substrate, a liquid crystal layer, a second substrate, and a first polarizer are arranged in the following order. The liquid crystal layer is made of 2 polarizing films in black display 200537167; / the alignment of the liquid crystal molecules is parallel to the surfaces of the aforementioned pair of substrates, wherein the retardation 値 Re in the plane of the 2nd retardation region is 100 nm or less, and The retardation 値 Rth in the thickness direction is 50 nm to 200 nm. The refractive index anisotropy of the first retardation region is negative and the optical axis is substantially parallel to the layer system. The retardation axis system of the first retardation region and the first polarized light The transmission axis of the film is orthogonal to the retardation axis direction of liquid crystal molecules during black display. (2) The liquid crystal display device according to (1), wherein Re of the first phase difference region is 50 nm to 400 nm. (3) The liquid crystal display device according to (1) or (2), wherein the second phase difference region is The late phase axis system is substantially orthogonal to the transmission axis of the first polarizing film. (4) The liquid crystal display device according to any one of (1) to (3), wherein at least one of the first phase difference region and the second phase difference region contains a discotic liquid crystal compound. (5) The liquid crystal display device according to any one of (1) to (4), further comprising a second polarizing film on the outer side of the second substrate. (6) The liquid crystal display device according to any one of (1) to (5), wherein a pair of protective films are disposed so as to sandwich the first polarizing film and / or the second polarizing film described above. In the protective film, the phase difference Rth in the thickness direction of the protective film near the liquid crystal layer side is 25 nm or less. (7) The liquid crystal display device according to any one of (1) to (6), wherein a pair of protective films are disposed to sandwich the first polarizing film and / or the second polarizing film, and the pair of protective films The protective film near the liquid crystal layer is a halogenated cellulose film or a norbornene-based film. (8) The liquid crystal display device according to (6), wherein a pair of protective films are disposed in such a manner as to sandwich the first polarizing film and / or the second polarizing film, and the pair protects 200537167: The protective film on the liquid crystal layer side is a halogenated cellulose film that satisfies the following (I) and (II). (I) 0SRe (630) S10, and | Rth (630) | $ 25 (II) I Re (400) —Re (700) | $ 10, and | Rth (400) -Rth (700) | $ 35 (Formula (I ), (II), Re (λ) represents the hysteresis (nm) in the plane of the wavelength λ nm, and Rth (λ) represents the wavelength; the hysteresis nm (nm) in the thickness direction of 1 nm 〇) ( 9) The liquid crystal display device according to (8), wherein the aforementioned tritiated cellulose film contains at least one of the following formulae (III) and (IV) to reduce the hysteresis of the tritiated cellulose film in the film thickness direction: Of compounds. (III) (Rth (A)-Rth (0)) / A ^-1.0 (IV) 0.01 SAS 30 (In the formulae (III) and (IV), Rth (A) means a compound containing A% to reduce Rth Rth (nm) of the tritiated cellulose film, Rth (0) means Rth (nm) of the tritiated cellulose film which does not contain the compound which reduces Rth (λ), and A is relative to the fiber Plain film raw material polymer, reducing the weight (%) of the compound (R) (again). (10) The liquid crystal display device according to (8) or (9), in which the aforementioned halogenated cellulose film has a degree of substitution at the fluorene group The tritiated cellulose having a concentration of 2.85 to 3.00 contains at least one compound capable of reducing Rth (λ), and the compound has a solid content of 0.001 to 30% by mass relative to the solid content of the tritiated cellulose. (11) The liquid crystal display device according to any one of (8) to (10), wherein the halogenated cellulose film contains at least one kind that can reduce the halogenated cellulose film | Rth (400) — Rth (700) A compound of 0.001 to 30% by mass based on the solid content of the tritiated cellulose. -10- 200537167 · (1 2) The liquid crystal display device according to any one of (8) to (1 1), wherein the thickness of the aforementioned cellulose cellulose film is 10 to 120 microns. (13) The liquid crystal display device according to any one of (8) to (12), wherein the halogenated cellulose film contains at least one kind of reduced Rth (λ) and an octanol-water partition coefficient (L 〇g Ρ 値) The compound is 0 to 7 and the compound has a solid content of 0.01 to 30% by mass based on the solid content of the tritiated cellulose. (14) The liquid crystal display device according to (13), which contains a compound that can reduce the aforementioned RthU) and an octanol-water partition coefficient (Log P 値) of 0 to 7, and φ is selected from the following general formula (13) Or it is at least one of the compounds represented by the following general formula (18). [Chemical Formula 1] General Formula (13)

(In the general formula (13), R11 represents an alkyl group or an aryl group, and R12 and R13 represent independent hydrogen atoms, alkyl groups, or aryl groups.) [Chemical Formula 2] Formula (18) OR16 R14—CN- R15 (In the general formula (18), R14 represents an alkyl group or an aryl group, and R15 and R16 represent each independently a hydrogen atom, an alkyl group, or an aryl group.) (15) As in any of (8) to (14) A liquid crystal display device according to one item, wherein the above-mentioned 醯 -11- 200537167 ^% ·-chemical cellulose film has a spectral transmittance of 45 to 95% at a wavelength of 380 η m and a spectral transmittance of a wavelength of 350 nm of 10% or less . (16) The liquid crystal display device according to any one of (8) to (15), wherein the aforementioned tritiated cellulose film is treated with an Rth (λ) of 240 small-odor tritiated cellulose film under an environment of 90% RH. The amount of change is 15 nm or less. (17) The liquid crystal display device according to any one of (8) to (16), wherein after the halogenated cellulose film is treated in the environment for 240 hours, the amount of change in Rth (λ) of the halogenated film is 15nm or less. p (1 8) The liquid crystal display device according to any one of (8) to (16), wherein the in-plane retardation system of the pre-cellulose cellulose film satisfies the following formula. Re (n)-Re (0) | / η ^ 1.0 (where Re (n) is the retardation (nm) on the surface of η (%) stretched film surface, and Re (0) is the unstretched film surface Internal surface hysteresis (nm). (19) The liquid crystal display device according to any one of (8) to (16), wherein the pre-cellulose cellulose film is in the film surface, and the film is opposed to the film-making machinery. The direction (MD direction) perpendicular to the direction (TD direction) has a late phase axis. (20) The liquid crystal display device according to any one of (8) to (16), wherein the pre-cellulose cellulose film is in the film surface, The hysteresis 値 becomes smaller when extending in the direction with the slow phase axis, and the hysteresis 値 becomes larger in the extending direction perpendicular to the direction with the slow phase axis. (21) If the liquid crystal of any one of (1) to (20) shows A device in which one of the liquid crystal cell pair substrates is located on the opposite side of the substrate closer to the observation side, and the first phase difference region and the second phase difference region (22) such as any of (1) to (21) are arranged The liquid crystal display device of the item 'wherein one of the pair of liquid crystal cells is located closer to the substrate on the observation side, and it is arranged at 60 ° C, and the fiber is described as hysteresis at 80 ° C) The time is the aforementioned bit field. The foregoing includes the first -12-200537167 / the first phase difference region and the second phase difference region. '' The first polarizing film, the first retardation region and the second retardation region, the first substrate, the liquid crystal layer, the second substrate, and the 苐 2 polarizing film are arranged in the following order, and the liquid crystal molecules of the liquid crystal layer are displayed in black In the liquid crystal display device whose alignment is parallel to the surfaces of the aforementioned pair of substrates, the retardation 値 Re in the plane of the second retardation region is 100 nm or less, and the retardation 厚度 Rth in the thickness direction is 50 nm to 200 nm. The refractive index anisotropy of the region is negative and the optical axis is substantially parallel to the layer system. The retardation axis system of the first phase φ difference region is related to the transmission axis of the first polarizing film and the retardation of liquid crystal molecules during black display. The arrangement of the orthogonal axis direction does not change the characteristics of the front direction at all, which can improve the reduction in contrast caused by the deviation of the absorption axis of the two polarizers from 90 degrees when viewed from the oblique azimuth angle, especially from 45 degrees. The contrast in the oblique direction decreases. In addition, by making the protection of the polarizing film • *. The Rth of the protective film be 25nm or less, the contrast can be further improved. [Embodiment] Hereinafter, an embodiment φ of a liquid crystal display of the present invention and its constituent elements will be described in order. In addition, the number 数 range indicated by "~" used in this specification means that the number 所述 described before and after "~" is included as the lower limit 値 and the upper limit 値 range. In this specification, Re and Rth each indicate a hysteresis 値 and a thickness 的 in a thickness direction at a wavelength of 5 to 50 nm. Re was measured at KOBRA 21 AD Η (manufactured by Toshiki Instruments Co., Ltd.) with a wavelength of 5 50 n m incident in the direction of the normal direction. Rth KOB 21 ADH is based on the aforementioned Re and uses the in-plane retardation axis (determined by KOBRA 21ADH) as the tilt axis (rotation axis) from the normal direction of the film +40 degrees to the direction of the incident light at a wavelength of 5 50 nm Measure -13- 200537167 / fixed hysteresis chirp, and use the in-plane retardation axis as the tilt axis (rotation axis) to measure the hysteresis chirp measured by incident light with a wavelength of 5 5 Onm in the direction of the film's normal direction—40 degrees tilt, Calculate the hysteresis 定 determined in three directions in total. Here, the assumption of the average refractive index 値 can be used in the polymer handbook (] WIL N WILEY & SONS, INC), 目录 of various optical film catalogs. When the average refractive index is not known, it can be measured using a refractometer. Examples of the average refractive index of the main optical film are as follows: halogenated cellulose (1.48), cycloolefin polymer (1.5 2), polycarbonate (1.59), polymethacrylate (1.49), polybenzene Ethylene (1.5 9). KOBRA 21 ADH can calculate nx, ny, and nz when these average refractive indices are assumed to be 値 and film thickness. In addition, the Rth symbol is a hysteresis 得到 obtained by measuring light incident at a wavelength of 50 nm to +20 degrees of the normal direction of the film with the in-plane retardation axis as the inclination axis (rotation axis). , Negative if less than Re. However, a sample with an I Rth / Re | of 9 or more is a polarizing microscope with a rotating free stand. The phase advance axis is used as the tilt axis (rotation axis) and the tilt is + 40 degrees to the film normal direction. In the state, it can be determined by using a test plate of a polarizing plate. When the retardation axis of the sample is parallel to the film plane, it is positive, and when the retardation axis is in the thickness direction of the film, it is negative. In this specification, "parallel" and "orthogonal" mean the precise angle range of 10 degrees. The error between this range and the precise angle is preferably ± 5 degrees or less, and more preferably ± 2 degrees or less. The "late axis" means the direction of the maximum refractive index. In addition, if the measurement wavelength of the refractive index and the phase difference is not specifically described, the visible light range is λ = 5 5 Onm. When the "polarizing plate" in this manual is not notified in advance, the meaning used includes cutting ("cutting" in this manual includes "through" -14-200537167 / and "cut off" etc.) to become a long polarizing plate, And can be assembled into a polarizer of the size of a liquid crystal device. In this specification, the polarizing film is divided into a “polarizing film” and a “polarizing plate”, and the “polarizing plate” means a laminated body having a transparent protective film for protecting the polarizing film on at least one side of the “polarizing film”. The constitution of the protective film may also serve as another film, and it means that, for example, the constitution of the protective film may also serve as a retardation region. Hereinafter, embodiments of the present invention will be described in detail using drawings. Fig. 1 is a schematic diagram showing an example of a pixel area of a liquid crystal display device of the present invention. Fig. 2 is a schematic diagram of an embodiment of a liquid crystal display device of the present invention. [Liquid crystal display device] The liquid crystal display device shown in FIG. 2 includes polarizing films 8, 20, and a first retardation region 10, and a second retardation region 1, 2, a substrate 1, 3, 17, and a liquid crystal layer 15. . The polarizing films 8, 20 are sandwiched between the respective protective films 7a and 7b, and 19a and 19b. In the liquid crystal display device of FIG. 2, the liquid crystal cell system is composed of substrates 13 and 17 and a liquid crystal layer 15 sandwiched therebetween. The product of the thickness d (micrometers) of the liquid crystal layer and the refractive index anisotropy Δ η Δ d is in the transmission mode. IPS type without a curved structure, preferably in the range of 0.2 to 0.4 microns value. In this range, a white display has a high luminance and a black display has a low luminance, so that a bright and high-contrast display device can be obtained. An alignment film (not shown) is formed on the surfaces of the substrates 1 3 and 17 that contact the liquid crystal layer 15 so that the alignment of the liquid crystal molecules is slightly parallel to the surface of the substrate. At the same time, the wiping treatment direction 1 applied to the alignment film 1 4 and 18 can control the alignment direction of the liquid crystal molecules in the state of no applied voltage or low applied state, and can determine the direction of the late phase axis 16. The second figure shows that the wiping direction is parallel, but it may be non-parallel. -15- 200537167 Or the film is widened to the supporting role of the light field. The orientation of the crystal in the direction of the liquid crystal system is controlled by the direction of the beam. The base of the beam is in the phase of the crystal or • 1 t / | \ The angle of the crystal liquid film can be displayed in the forming surface. 7 11 2 In the figure, the plate electrode is shown in Figure 13, and the voltage is charged. Add Jiashi as the sub-degree angle of the low-temperature liquid crystal to t). In Fig. 1, the alignment of liquid crystal molecules in the 15-pixel region of the liquid crystal layer is shown schematically. Figure 1 shows the alignment of liquid crystal molecules in a very small area equivalent to 1 pixel of the liquid crystal layer 15 at the same time, the wiping direction 4 of the alignment film formed on the inner surface of the substrate 1 3 φ and 17, and can be aligned on the substrate Schematic diagrams of electrodes 2 and 3 for applying voltage to liquid crystal molecules formed on the inner surfaces of 13 and 17. When nematic liquid crystals with positive dielectric anisotropy are used as electric field effect liquid crystals, the orientation of liquid crystal molecules is 5a and 5b when no voltage is applied or in a low applied state during active driving. At this time, a black display can be obtained. . When a voltage is applied between the electrodes 2 and 3, the liquid crystal molecules change their alignment directions in the directions of 6a and 6b according to the voltage. This state is usually used for clear display. φ In FIG. 2, the arrangement of the transmission axis 9 of the polarizing film 8 is orthogonal to the transmission axis 21 of the polarizing film 20. The retardation axis 11 of the first retardation region 10 is orthogonal to the retardation axis 15 of the liquid crystal molecules 14 in the liquid crystal layer 14 of the polarizing film 8 and the liquid crystal layer 14 during black display. In the liquid crystal display device shown in Fig. 2, the structure of the polarizing plate 8 is sandwiched between the protective films 7a and 7b, but the protective film 7b may not be provided. The polarizing film 20 is also sandwiched between the two protective films 19a and 19b, but the protective film on the liquid crystal layer 15 side may not be required. When the protective films 7b and 19a are arranged, the phase difference Rth in the thickness direction of the protective film is preferably 25 nm or less. -16- 200537167-It is preferable that the protective film 19a which is close to the protective film 7b and the liquid crystal layer 15 side will be described later. The hysteresis cellulose with a small optical anisotropy (Re, Rth) used in the protective film has a retardation within a plane of a wavelength of 63 0 nm. Re (63 0) is 10 nm or less (OS Re (6 3 0) S 10), and The hysteresis in the film thickness direction is absolute of Rth (630) and less than 25nm (丨 Rth 丨 S 25nm). 〇 $ Re (6 3 0) S 5 and | Rth | S20nm are more preferable, and 0 $ Re (630) S2 and I Rth | S15nm are more preferable. In addition, the protective film used in the present invention is a fiber φ-dimensional element film with a small wavelength dispersion, | Re (400) — Re (700) | S 10, and Rth (400) —

Rth (700) | S 35. Re (400) — Re (700) | S 5 and I Rth (400) — Rth (700) | $ 25 is better, and | Re (400) —

Re (700) | S3, and | Rth (400)-Rth (700) | $ 15 is even better. The protective film 7b and the protective film 19a are preferably 10 to 120 microns, and more preferably (30 to 90) microns. The first phase difference region and the second phase difference region are based on the position of the liquid crystal cell, and can be arranged between the liquid crystal cell and the polarizing film on the observation side, or φ can be placed between the liquid crystal cell and the polarizing film on the back side. In addition, FIG. 2 shows a state of a transmission mode display device including an upper polarizing plate and a lower polarizing plate. However, the present invention may also be a reflection mode with only one polarizing plate. In this case, because the liquid crystal cell The optical path of the lens is doubled, so the optimal value of Δ n · d becomes a value of about ½ of the above. The liquid crystal cell used in the present invention is not limited to the IPS mode, and any liquid crystal display device in which liquid crystal molecules are aligned substantially parallel to the surface of the pair of substrates in black display can be suitably used. This example includes a ferroelectric liquid crystal display device, an antiferroelectric liquid crystal display device, and an EC B-type liquid -17-200537167 / crystal display device. The liquid crystal display device of the present invention is not limited to the structure shown in Fig. 2, and may include other members. For example, a color filter may be disposed between the liquid crystal layer and the polarizing film. Further, the surface of the protective film of the polarizing film may be subjected to a reflection prevention treatment or a hard coat treatment. It is also possible to use a material that imparts conductivity to a component. When used as a transmissive type, a cold cathode or hot cathode fluorescent tube, or a light emitting diode, a field emission element, an electroluminescent element, and a backlight as a light source can be arranged on the back surface. At this time, the arrangement of the φ backlight plate may be on the upper side or the lower side in FIG. 2. Further, a reflective polarizing plate, a diffusion plate, a prism sheet, or a light guide plate may be disposed between the liquid crystal layer and the backlight plate. As described above, the liquid crystal display device of the present invention may be a reflective type. In this case, a polarizing plate may be arranged only on the observation side, and a reflective film may be arranged on the back surface of the liquid crystal cell or the inner surface of the lower substrate of the liquid crystal cell. Of course, a light plate before using the light source can also be provided on the liquid crystal cell observation side. The liquid crystal display device of the present invention includes a portrait direct-view type, a portrait projection φ type, and a light modulation type. Aspects of the present invention are particularly effective when applied to an active matrix liquid crystal display device using a 3-terminal or 2-terminal semiconductor element such as a TFT or MIM. Of course, the aspect applied to a passive matrix liquid crystal display device called time division driving is also effective. In the following, preferred optical characteristics of the various components that can be used for the liquid crystal display device of the present invention, materials used for the components, and a manufacturing method thereof are described in detail. [First phase difference region] The present invention is configured with a negative refractive index anisotropy, and the optical axis is true to the plane. 18- 200537167 • The first phase difference region that is substantially parallel is based on the first phase difference region. The retardation axis is arranged so as to be orthogonal to the transmission axis of the first polarizing film and the retardation axis direction of the liquid crystal molecules during black display. The first phase difference region is not particularly limited in material and form as long as it has front optical characteristics. For example, on a retardation film composed of a birefringent polymer film and a transparent support, a retardation film having a retardation layer formed by coating or transferring a low-molecular or high-molecular liquid crystal compound is applied. can use. Various types can also be used by stacking them. I The first retardation region is arranged such that the retardation axis thereof is orthogonal to the retardation axis direction of the liquid crystal molecules during black display. In order to effectively reduce light leakage in the oblique direction, the Re of the first retardation region is preferably 50 nm to 400 nm, more preferably 80 nm to 250 nm, and most preferably 110 nm to 210 nm. < First retardation region having a birefringent polymer film > A retardation film composed of a birefringent polymer having the above-mentioned optical characteristics can be easily formed by stretching a polymer film. It is preferable that the material of the polymer film has negative refractive index anisotropy. Examples of the polymer having a negative refractive index anisotropy include a styrene-based polymer. Styrene polymers can be roughly divided into: styrene or styrene derivatives alone; styrene or copolymers of styrene derivatives and other monomers; styrene or styrene derivatives and other monomers Graft copolymers; and mixtures of these polymers. Examples of individual polymers of styrene or its derivatives' include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, p-chlorostyrene, and o-nitrobenzene Separate polymerization of ethylene, p-aminostyrene, p-carboxystyrene, p-phenylstyrene, and 2,5-chlorophenethylbenzene. Examples of styrene or copolymers of styrene derivatives and other monomers include styrene / acrylonitrile copolymers, styrene / methacrylonitrile copolymers, and styrene / methyl methacrylate copolymers. Polymer, styrene / ethyl methacrylate copolymer, styrene / chloroacrylonitrile copolymer, styrene / methyl acrylate copolymer, styrene / ethyl acrylate copolymer, styrene / butyl acrylate copolymer, benzene Ethylene / acrylic acid copolymer, styrene / methacrylic acid copolymer, styrene / butadiene copolymer, styrene / isoprene copolymer, styrene / maleic anhydride copolymer, styrene / Itaconic Acid copolymer, styrene / vinylcarbazole copolymer, styrene / N-phenylacrylamide copolymer, styrene / vinylpyridine copolymer, styrene / vinylnaphthalene copolymer, α-methyl Styrene / acrylonitrile copolymer, methylstyrene / methacrylonitrile copolymer, methylstyrene / ethyl acetate copolymer, styrene / α-methylstyrene / acrylonitrile copolymer, styrene / α -Methylstyrene / methacrylonitrile copolymer, and benzene Ethylene / methyl styrene / methyl methacrylate copolymer, and styrene / styrene derivative copolymers. The styrene-based polymer is preferably a copolymer obtained by graft-polymerizing at least one of a styrene / butadiene copolymer with styrene, | acrylonitrile, and α-methylstyrene. Regarding styrenic polymers, Japanese Unexamined Patent Publication No. 4-97322 and Japanese Unexamined Patent Publication No. 6-67 1 69 are described. The retardation layer is uniaxially optically negative and has an optical axis parallel to the substrate. For example, the retardation layer can be obtained by uniaxially stretching a polymer having negative refractive index anisotropy such as the styrene polymer. < A first retardation region having a retardation layer formed of a liquid crystal compound > A retardation of -20-200537167 / layer formed of a liquid crystal compound having the above-mentioned optical characteristics can be used on a support or temporarily The support is coated with a dish-shaped liquid crystal compound containing negative birefringence or a composition containing the same, and the liquid crystal molecules are aligned vertically, and the optical axis of the liquid crystal is substantially horizontal with the substrate, and the support is formed. When it is formed on a temporary support, it can be produced by transferring the retardation layer to the support. Moreover, not only one retardation layer but also a plurality of retardation layers may be laminated to form a first retardation region capable of displaying the above-mentioned optical characteristics. In addition, the first retardation region may be configured such that the entire laminated body of the support and the retardation layer satisfies the optical characteristics described above. < Disc-shaped liquid crystalline compound > Various documents can be used in the present invention (C. Destirade et al., Mol. Crysr. Liq. Cryst., vol. 71, page 111 (1981); ed. General Chemistry, No. 22, Liquid Crystal Chemistry, Chapter 5, Chapter 10, Section 2 (1994); B. Kohne et al., Angew. Chem. Soc. Chem.

Comm., Page 1 794 (1 98 5); J. Zhang et al., J. Am. Chem. Soc ·, vo 1 · 1 1 6, page 2 6 5 5 (1 9 9 4)) Liquid crystal compound. Japanese Patent Application Laid-Open No. 8-272 84 describes the polymerization of a discotic liquid crystalline compound. p The dish-like liquid crystal compound preferably contains a polymerizable group in a form which can be fixed by polymerization. For example, the structure can be considered as a substituent in which a polymerizable group is bonded to the disc-shaped core of the discotic liquid crystalline compound. However, when directly bonded to the disc-shaped core, it is difficult to maintain the alignment state during the polymerization reaction. Therefore, the 'disc-shaped core' has a structure having a linking group with a polymerizable group. That is, the dish-like liquid crystalline compound having a polymerizable group is preferably a compound represented by the following formula. D (— L — P) η In the formula, D is a disc-shaped core, L is a divalent linking group, and P is a polymerization group; 21-200537167, and η is an integer from 4 to 12. Preferred specific examples of the disc-shaped core (D), the divalent linking group (L), and the polymerizable group (P) in the aforementioned formulas are (D1) to (D15) described in Japanese Patent Application Laid-Open No. 2001-4837. ), (L1) to (L25), (P1) to (P18), the content described in the bulletin can be used appropriately. The first retardation region has a retardation layer formed of a dish-shaped liquid crystal compound that is substantially vertically aligned. The retardation axis of the retardation layer is similar to that of the liquid crystal molecules during black display. Arranged so that the direction of the late phase axis is orthogonal. The adjustment of Re in the first retardation region is performed by controlling the thickness of the disc-shaped liquid crystal layer formed by coating. In addition, it is necessary to perform the alignment of the disc surface so that the dish-like liquid crystalline compound is substantially perpendicular to the film surface (average inclination angle in the range of 70 to 90 degrees). The dish-like liquid crystalline compound can also be tilted and aligned, or the tilt angle can be changed slowly (mixed alignment). When tilt alignment or hybrid alignment, the average tilt angle is preferably 70 degrees to 90 degrees, more preferably 75 degrees to 90 degrees, and most preferably 80 degrees to 90 degrees. When the average tilt angle is smaller than this, the light leakage distribution becomes asymmetric. $ < Formation method of first retardation region having retardation layer > A retardation layer formed of a discotic liquid crystalline compound can be coated with a discotic liquid crystal by coating a vertical alignment film formed on a support The compound is formed by performing vertical alignment and fixing the alignment state according to a desired coating liquid such as a polymerizable initiator, an air interface vertical alignment agent, and other additives. An organic solvent is preferably used as a solvent for preparing the liquid cloth. Examples of the organic solvent include amidine (for example, N, N-dimethylformamide), fluorene (for example, dimethylmethane), heterocyclic compounds (for example, pyridine), and hydrocarbons (Example-22- 200537167- (Such as benzene, hexane), halogenated alkyl (such as chloroform, dichloromethane), esters (such as methyl acetate, butyl acetate), ketones (such as acetone, methyl ethyl ketone), ethers (such as tetrahydrofuran, 1, 2. Dimethoxyethane). Among them, halogenated alkyls and ketones are preferred. Two or more kinds of organic solvents may be used in combination. The coating liquid can be applied by a known method (for example, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, or a die coating method). It is preferred that the liquid crystal compound undergoes vertical alignment to maintain and fix the alignment state. The immobilization is preferably performed by a polymerization reaction of a polymerized φ-based group (P) introduced into the liquid crystal compound. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator. Among them, photopolymerization is preferred. Examples of the photopolymerization initiator include α-carbonyl compounds (described in the specifications of U.S. Patent No. 2, 3,766, 1 and 2,67,670), diethyl ether (described in the specification of U.S. Patent No. 244 8 828), and α-hydrocarbon substituted aromatic Family marriage compounds (described in US Pat. No. 277225 1 2), polynuclear benzoquinone compounds (described in US Pat. Nos. 3046 1 27 and 295 1 75 8), triarylimidazole dimers, and o-aminobenzene Combinations of ketones φ (described in US Patent No. 3 5 49 3 67), acridine and phenanthrene compounds (Japanese Patent Publication No. 60-1 05667, described in US Patent No. 423 985 0 0), and Shu · Diazole compounds (Described in US Patent 42 1 2970). The amount of the photopolymerization initiator used is preferably from 0.01 to 20% by mass, and more preferably from 0.5 to 5% by mass. In order to irradiate the dish-shaped liquid crystal molecules with polymerization light, ultraviolet rays are preferably used. The irradiation energy is preferably 20mJ / cm2 to 50J / cm2, and more preferably 100mJ / cm2 to 800J / cm2. In order to promote the photopolymerization reaction, light irradiation may be performed under heating conditions. The thickness of the first retardation region containing the optically anisotropic layer is preferably -23-200537167 0.1 to 10 microns, more preferably 0.5 to 5 microns, and most preferably 1 to 5 microns. < Vertical alignment film > In order to vertically align the liquid crystal compound to the alignment film side, it is important to reduce the surface energy of the alignment film. Specifically, the functional group of the polymer is used to reduce the surface energy, thereby bringing the liquid crystal compound into an upright state. Functional groups that can reduce the surface energy of the alignment film are effective for fluorine and hydrocarbon groups with a carbon number of .10 or more. In order for a fluorine atom or a hydrocarbon group to exist on the surface of the alignment film, it is better to introduce a fluorine atom or a hydrocarbon group into the side chain than in the main chain of the polymer. The fluorine-containing polymer preferably contains a fluorine atom at a ratio of 0.05 to 80% by mass, more preferably at a ratio of 0.1 to 70% by mass, more preferably at a ratio of 0.5 to 65% by mass, and at a ratio of 1 to 60% by mass. For the best. The hydrocarbon group is an aliphatic group, an aromatic group, or a combination thereof. The aliphatic group may be cyclic, branched, or linear. The aliphatic group is preferably an alkyl group (or a cycloalkyl group) or an alkenyl group (or a cycloalkenyl group). The hydrocarbon group may contain a substituent such as a halogen atom which does not exhibit strong hydrophilicity. The carbon number of the hydrocarbon group is preferably 10 to 100, more preferably 10 to 60, and most preferably 10 to 40. The polymer main chain preferably has a polyfluorene imine structure or a polyvinyl alcohol structure. Polyfluorene imine is usually synthesized by a condensation reaction of a tetracarboxylic acid and a diamine. It is also possible to use two or more types of tetracarboxylic acids or two or more types of diamines to synthesize polyfluorene imide equivalent to a copolymer. The fluorine atom or the hydrocarbon group may exist in a repeating unit of tetracarboxylic acid origin, may exist in a repeating unit of diamine origin, or both. When a polyimide is introduced with a hydrocarbon group, it is particularly preferable to use a steroid structure formed on the main chain or side chain of the polyimide. The Kf group, which is equivalent to a hydrocarbon having 10 or more carbon atoms in a steroid structure such as a side chain, has a function of vertically aligning a liquid crystal compound. For the purposes of this specification *, a sterol structure refers to a cyclopentane hydrogenated phenanthrene ring structure or a ring structure in which a part of the ring bond forms a double bond in the range of an aliphatic ring (the range where no aromatic ring is formed). The method of vertically aligning the liquid crystalline compound can be suitably used a method of mixing an organic acid with a polymer of polyvinyl alcohol, modified polyvinyl alcohol, or polyimide. The mixed acid is preferably a carboxylic acid, a sulfonic acid, or an amino acid. _ Among the air surface compounding agents mentioned later, acidic substances can be used. In addition, it is also possible to use grade 4 ammonium salts. The blending amount is preferably 0.1% to 20% by mass, and more preferably 0.5% to 10% by mass relative to the polymer. The saponification degree of the polyvinyl alcohol is preferably 70 to 100%, and more preferably 80 to 100%. The degree of polymerization of polyvinyl alcohol is preferably from 100 to 5,000. When the discotic liquid crystalline compound is aligned, the alignment film is preferably composed of a polymer having a hydrophobic group in a side chain as a functional group. Specifically, the type of the functional group 0 is determined according to the type of the liquid crystal molecule and the necessary alignment state. For example, the modified group of modified polyvinyl alcohol can be introduced by copolymerization modification, chain shift modification, or block polymerization modification. Examples of the modifying group include a hydrophilic group (carboxylic acid group, sulfonic acid group, phosphonic acid group, amine group, ammonium group, amidine group, thiol group, etc.), and a hydrocarbon group having 10 to 100 carbon atoms. Fluorine-substituted hydrocarbon groups, thioether groups, polymerizable groups (unsaturated polymerizable groups, epoxy groups, acryl propane groups, etc.), alkoxysilyl groups (trialkoxy, dialkoxy, Alkoxy) and so on. Specific examples of such modified polyvinyl alcohol compounds include, for example, paragraph number-25-200537167 • 9 in the specification of Japanese Patent Laid-Open No. 2000-155255216 [0022] ~ [0145], the same Items described in paragraph numbers [0018] to [0022] in the specification of 2002-62426. The alignment film is formed using a polymer having a side chain in which a crosslinkable functional group is bonded to the main chain, or a polymer having a function of aligning liquid crystal molecules, and a polymer having a crosslinkable functional group in a side chain. When the composition of the polyfunctional monomer forms an optically anisotropic layer thereon, the polymer in the alignment film and the polyfunctional monomer in the optically anisotropic layer formed thereon can be copolymerized. As a result, covalent bonds are not only formed between the polyfunctional monomers, but also between the polymer of the alignment film and between the polyfunctional monomer and the alignment film monomer, and the alignment film and optical anisotropy are strongly combined. Floor. Therefore, by forming an alignment film using a polymer having a crosslinkable functional group, for example, the strength of a member including a first retardation region in an optical compensation sheet can be significantly improved. The crosslinkable functional group system and the polyfunctional monomer of the alignment film polymer preferably contain a polymerizable group. Specific examples include those described in paragraphs [0080] to [〇1〇〇] in the specification of JP 2000-1552552 16. 0 In addition to the above-mentioned crosslinkable functional group, the alignment film polymer may be crosslinked using a crosslinker. Cross-linking agents include aldehydes, N-methylol, derivatives of Erguayuan, compounds acting by activating carboxyl groups, active ethylene compounds, active halogen compounds, isoxazole and dialdehyde starch. It is also possible to use two or more types of crosslinking agents in combination. Specific examples include those described in paragraphs [0023] to [024] in the specification of Japanese Patent Laid-Open No. 2 00 2-6 24 26 and the like. Highly reactive aldehydes, especially glutaraldehyde, are preferred. The amount of the cross-linking agent to be added is from 0.1 to 20% by mass relative to the polymer, and more preferably from 0.5 to 15% by mass. Amount of residual unreacted cross-linking agent of the alignment film -26- 200537167-Preferably: L0% by mass or less, more preferably 0.5% by mass or less. With this adjustment, even if the alignment film is used for a long time in the liquid crystal display device, or if it is left in a high-temperature and high-humidity environment for a long time, it can have sufficient durability without wrinkles. The alignment film can basically be formed by coating a transparent support with a composition containing the above-mentioned polymer as an alignment film-forming material and a cross-linking agent, followed by heating and drying (cross-linking), followed by wiping treatment. The cross-linking reaction can be performed at any time after coating on the support as described above. When a water-soluble polymer of φ polyvinyl alcohol is used as the alignment film forming material, it is preferable to apply a miscible mixture of an organic solvent (such as methanol) and water with a defoaming effect. When the ratio is mass ratio, water: methanol is preferably 0: 1 00 to 99: 1, and 0 ·. 100 to 9 1: 9 is more preferable. Thereby, it is possible to suppress the occurrence of bubbles, significantly reduce the defects of the alignment film, and further the surface of the optically anisotropic layer. The coating method of the alignment film is a spin coating method, a dip coating method, a curtain coating method, a pressure coating method, a rod coating method, Alternatively, roll coating is preferred. Roll coating is particularly preferred. The film thickness after drying is preferably 0.1 to 10 microns. Heating and drying can be performed at I 20 ° C ~ 1 lOt. In order to form sufficient cross-linking, 60 ° C to 100 ° C is preferred, 80 ° C to 10 ° C (TC is particularly preferred. Drying time is 1 minute to 1 hour, and 1 minute to 30 minutes is preferred. The pH is preferably It is preferable to set the most suitable cross-linking used. When using pentanediol, the pH is preferably 4.5 to 5.5, and 5 is particularly preferred. The alignment film is preferably set on a transparent support. The alignment film is as described, The above-mentioned wiping treatment can be obtained by wiping the surface after the polymer layer is cross-linked. It can be applied to the processing method widely used in LCD liquid crystal alignment processing steps. That is, using paper, gauze, felt, rubber, or as usual, Permeate the liquid agent to reduce the extrusion. Above 36 agents, the resistance is -27- 200537167. Polyamide, polyester fiber, etc. Wipe the surface of the alignment film in a certain direction to obtain the alignment method. Generally, the length and thickness are used. The average flocked cloth is wiped for several times. The dish-like liquid crystal compound is uniformly aligned, and it is usually better to control the alignment direction by a vertical alignment film with wiping treatment. It is best not to wipe the vertical alignment of the composition. After the liquid crystal composition is aligned using an alignment film, the liquid crystal compound maintained in this alignment state can be fixed to form an optically anisotropic layer. An optically anisotropic layer is transferred onto a polymer film (or a transparent support). ≪ Air surface vertical alignment agent> In general, liquid crystal compounds have the property of oblique alignment on the air surface side. In the vertical alignment state, it is necessary to uniformly control the vertical alignment of the liquid crystalline compound on the air surface side. For this purpose, it is best to use a liquid crystal coating solution that contains liquids that tend to exist on the air surface side and occupy space or electrostatic effects. The compound that achieves the effect of vertical alignment of the liquid crystal compound is preferable to form a retardation film. The effect of the vertical alignment of the liquid crystal compound is equivalent to the reduction of the inclination angle of the guide plate when the liquid crystal compound is dish-like That is, the angle formed by the guide plate and the air-side surface of the coated liquid crystal can reduce the dish-like liquid crystal molecules. As the compound of the inclination angle of the guide plate, a polymer containing a rigid structural unit having a volume-occupying effect such as a cis-butenediamido group is preferably used. In addition, Japanese Patent Laid-Open No. 2002-203 63 can be used. The compound described in JP 2002- 1 29 1 62 is used as an air surface alignment agent. In addition, paragraph numbers [00〇72] to [0075], -28-200537167 in JP 2002-212100 specification Paragraph numbers [0037] to [0039] in the specification No. -262239, paragraph numbers [00〇71] to [007 8] in the specification No. 2003-9-9 7 52, paragraph numbers in the specification No. 2003-119959 [ 0052] ~ [0054], [0065] ~ [0066], [0092] ~ [0094], paragraph numbers [0028] ~ [0030] in the Japanese Patent Application No. 2003-330303, paragraphs in the Japanese Patent Application No. 2004-003804 The matters described by numbers [0087] to [0090] can also be suitably applied to the present invention. In addition, by blending these compounds, the coating properties can be improved, unevenness and shrinkage spots can be suppressed. p The use amount of the air surface alignment agent with respect to the liquid crystal coating liquid is preferably from 0.05 mass% to 5 mass%. When a fluorine-based air surface alignment agent is used, it is preferably 1% by mass or less. < Other materials in the retardation layer > The use of plasticizers, surfactants, and polymerizable monomers together with the above-mentioned liquid crystal compounds can improve the uniformity of the coating film, the strength of the film, and the alignment of the liquid crystal compounds, etc. . These materials are preferably compatible with liquid crystalline compounds and do not interfere with alignment. Examples of the φ polymerizable monomer include compounds having a radical polymerizable property or a cationic polymerizable property. It is preferable to use a polyfunctional radical polymerizable monomer, and it is preferable that the polymerizable group contains a polymerizable group with a liquid crystal compound. Examples thereof include those described in paragraphs [001 8] to [0020] in the specification of Japanese Patent Application Laid-Open No. 2002-296423. The amount of the compound to be added is usually in the range of 1 to 50% by mass, and preferably in the range of 5 to 30% by mass relative to the dish-like liquid crystalline molecules. Examples of the surfactant include conventionally known compounds, and particularly a fluorine-based compound is preferred. Specifically, there can be cited JP 200B 3 30725-29-200537167, the articles described in paragraph numbers [0 0 2 8] to [0 0 5 6] in the specification of the bulletin, and Japanese Patent Application No. 2003-295212 Paragraph numbers [0069] to [0126] in the description. The polymer used in combination with the liquid crystalline compound is preferably one capable of thickening the coating liquid. Examples of the polymer include cellulose esters. Preferable examples of the cellulose ester include those described in paragraph number [0 1 7 8] of the specification of JP 2000-1552552. In order not to hinder the compounding of the liquid crystal compound, the amount of the polymer added is preferably in the range of 0.1 to 10% by mass relative to the liquid crystal molecules, and more preferably in the range of 0.1 to 8% by mass. Liquid crystal properties The compound-disc nematic liquid crystal phase-solid phase transition temperature is preferably 70 to 300 ° C, and more preferably 70 to 170 ° C. < Support > In the present invention, a retardation layer made of a liquid crystal compound can be formed on a support. The support is preferably transparent, and the specific light transmittance is preferably 80% or more. The support preferably has a small wavelength dispersion, and specifically, the ratio of R e 4 0 0 / R e 7 0 0 is preferably less than 1.2. Among them, polymer films are preferred. The transparent support may also serve as a second retardation region or a protective film for a polarizing plate. In addition, the first phase difference region may be constituted by the transparent support and the entire phase difference layer $. The optical anisotropy of the support is preferably small, and the in-plane hysteresis (R e) is preferably 20 nm or less, more preferably 100 nm or less, and most preferably 5 nm or less. In the case of the second retardation region, the hysteresis 方向 Rth in the thickness direction is 50 nm to 200 nm, and the 箪 B circumference of 60 nm to 150 nm is more preferable. The fe circumference of 70 nm to 130 nm is most preferable. In addition, when used also as a polarizing protective film, the retardation 値 Rth in the thickness direction is 25 nm or less, more preferably 20 nm or less, and most preferably 10 nm or less. -30- 200537167 •-Examples of polymer films for the support include films of cellulose esters, polycarbonates, polyfluorenes, polyethers, polyacrylates, and polymethacrylates. A cellulose ester film is preferred, an ethyl acetate cellulose film is more preferred, and a triacetate cellulose film is most preferred. The polymer film is preferably formed by a solvent casting method. The thickness of the transparent support is preferably 20 to 500 microns, and more preferably 40 to 200 microns. In order to improve the adhesion between the transparent support and the layer (adhesive layer, vertical alignment film or retardation layer) provided on it, a surface treatment (such as a light-emitting discharge treatment, a corona discharge φ discharge) can also be performed on the transparent support. Treatment, ultraviolet (UV) treatment, flame treatment. An adhesive layer (base layer) can also be provided on the transparent support. In addition, the transparent support or long transparent support is used to impart slippage during the transport step or to prevent curling. After taking it, the inner surface is adhered to the surface to apply a polymer layer on one side of the support (mixed with inorganic particles with a solid content ratio of 5% to 40% and an average particle diameter of about 10 to 100nm) or by supporting [Second phase difference region] $ The optical characteristics of the second phase difference region. The hysteresis in the thickness direction is

Rth is 50 nm to 200 nm, preferably 60 nm to 150 nm, and more preferably 70 nm to 130 nm. The arrangement of the second phase difference region in the direction of the late phase axis is not particularly limited as long as Re is 20 nm or less, and if it is greater than 20 nm, it is preferable that the direction is substantially orthogonal to the transmission axis of the first polarizing film. In such a configuration, for example, when the first retardation region contains a retardation layer formed of a liquid crystalline compound, the thickness of the retardation layer can be made thin. The material of the second retardation region is not particularly limited as long as it has the aforementioned optical characteristics. For example, a retardation film composed of a birefringent polymer film-31-200537167 ^ and a phase having a retardation layer formed by coating or transferring a low-molecular or barrel-molecule liquid crystal compound on a transparent support. Differential films can be used. Moreover, you may use each by stacking. < A second retardation region having a birefringent polymer film> A retardation film composed of a birefringent polymer film having the above-mentioned optical characteristics can be easily formed into a polymer film by uniaxial or biaxial stretching. (For example, Japanese Patent Laid-Open No. 2003-1 962 1 and Japanese Patent Laid-Open No. 2002-1 46045). In addition, the φ-dimensional fluorescein fibers which can only express optical characteristics by being cast but not stretched can be suitably used. In this way, the cellulose described in Japanese Patent Application Laid-Open No. 2000-275434, Japanese Patent Application No. 200 1 66 1 44, Japanese Patent Application No. 2002- 1 6 1 1 44 and Japanese Patent Application No. 2002-9054 can be used. . As the material of the polymer film, synthetic polymers (for example, polycarbonate, polyether, polyether, polyacrylate, polymethacrylate, norbornene resin, and tritiated cellulose) can be generally used. < A second retardation region having a retardation layer formed of a liquid crystal compound > ^ A retardation layer formed of a liquid crystal compound having the above-mentioned optical characteristics can be used on a support or a temporary support A rod-shaped cholesterol-type liquid crystal composition containing a palm-shaped structural unit is applied, and the spiral axis thereof is aligned substantially perpendicular to the substrate, and is formed by being fixed. When the temporary support is formed with the aforementioned retardation layer, it can be produced by transferring to the support. In addition, a dish-shaped liquid crystal compound having negative birefringence is horizontally aligned (the guide plate is perpendicular to the substrate), a retardation layer formed by immobilization, and a retardation layer formed by casting and fixing a polyimide polymer on a substrate. It can be used similarly. Furthermore, not only a retardation layer but also a plurality of retardation layers may be laminated to form a second retardation region capable of expressing the above-mentioned optical characteristics. In addition, the second retardation region may be constituted by a method in which the entire laminated body of the support and the retardation layer satisfies the aforementioned optical characteristics. < Method for forming a retardation layer formed by horizontally aligning a discotic liquid crystalline compound > A second retardation region containing a retardation layer formed of a discotic liquid crystalline compound can be formed on a support The horizontal alignment film is coated with a coating liquid containing a discotic liquid crystalline compound or the aforementioned polymerizable initiator or | air surface horizontal alignment agent (for example, as described in Japanese Patent Application No. 2003 -3 8 8 308) and other additives mentioned above. To form. As the alignment film for horizontally aligning the dish-like liquid crystal layer, a polymer alignment film such as polyvinyl alcohol, polyimide, polyimide, acrylic acid or the like having a solid content of 0.1% by mass or less as an organic acid or a salt can be used. After the alignment film is formed, it may or may not be wiped. In addition, examples of usable discotic liquid crystalline compounds, examples of solvents used in the preparation of coating liquids, examples of coating methods, other materials such as polymerizable initiators and polymerizable monomers, and those used to form retardation layers The support is the same as the material and the like exemplified in the description of the retardation layer constituting the first retardation region. < Protective film for polarizing film > Among the protective films for polarizing plates used in the liquid crystal display device of the present invention, it is preferable to use a halogenated cellulose film as the protective film near the liquid crystal layer side. That is, it is preferable to use a tritiated cellulose film that satisfies any one of the following conditions (1) and (2) as a protective film, and particularly a protective film disposed near the liquid crystal layer side. (1) A tritiated cellulose film satisfying the following formulae (I) and (II); -33- 200537167 Li, * (I) OS Re (630) S 10, and I Rth (630) | ^ 25 '( II) I Re (400) — Re (700) | S 10, and | Rth (400) — Rth (700) IS 35 (In the above formulae (I) and (II), Re (A) represents the wavelength λ Frontal hysteresis (nm) in nm, Rth (λ) is a hysteresis (nm) in the film thickness direction at a wavelength of λ nm. (2) A compound containing a compound that reduces Rth in the film thickness direction of the tritiated cellulose film Therefore, Rth satisfies the following tritiated cellulose membranes of formulae (III) and (IV); (III) (Rth (A) —Rth (0)) / AS— 1.0 _ (IV) 0.01 S AS30 (Formula ( In III) and (IV), Rth (A) represents the Rth (nm) of a tritiated cellulose film containing A% of compounds that reduce Rth, and Rth (O) represents the absence of Rth (also) compounds Rth (nm) of the halogenated cellulose film, A means the weight (%) of the compound that reduces Rth (again) relative to the raw material of the cellulose film °) The following is a detailed description of the preferred halogenated fibers used in the present invention素 膜。 Plain film. Examples of the cellulose of the tritiated cellulose raw material include cotton linters, wood φ pulp (Pinus sylvestris, coniferous pulp), and the like. The tritiated cellulose obtained from any kind of raw cellulose may be used, or it may be mixed and used according to circumstances. For details about these raw materials, cellulose, for example, can be used. (17) Cellulose resin (Kutazawa, Uda, Nikkan Kogyo Shimbun, published in 1970), Invention Association Publication Gazette 2001-1745 (7 The cellulose described in pages 8 to 8) is not particularly limited to the front cellulose film. Degree of substitution of tritiated cellulose The tritiated cellulose that can be used in the present invention includes, for example, cellulose having hydroxyl groups that are tritiated, and its substituent may be a triphenyl group having 2 to 22 carbon atoms. -34-

200537167 Any of the bases. The impregnated group of the cellulose which can be used in the present invention is not particularly limited, and the degree of binding of the hydroxyl group of the substituted cellulose and / or the fatty acid having 3 to 22 atoms can be determined by calculation. The measurement method can be performed according to AS TM D-8 1 7-9 1 as described above, and the cellulose hydroxyl group substitution is specifically determined, wherein the degree of substitution of the cellulose group to the cellulose hydroxyl group is 2,50, It is preferably 2.75 to 3.00, and more preferably 2.85 to 3.00. Among the hydroxy acetic acid and / or 3 to 22 carbon atoms substituted for cellulose, the fluorenyl group having 2 to 22 carbon atoms may be an aliphatic group or a radical group ', or may be a mixture of two or more kinds. For example, alkylcarbonyl esters, alkenylcarbonyl esters of cellulose, aromatic carbonyl aromatic alkylcarbonyl esters, and the like. These may also each have a more preferable substituent. Examples include ethyl, propyl, butyl, hexamyl, octyl, decyl, dodecyl, and thirteen. Base, hexadecyl, octadecyl, isobutylfluorenyl, tertiary 1 cyclohexanecarbonyl, oleyl, phenylfluorenyl, naphthylcarbonyl, ethanyl, propanyl, butylfluorenyl, decyl The fluorenyl, octyl, fluorenyl, oleyl, phenyl fluorenyl, naphthylcarbonyl, and cinnamon fluorenyl groups are preferably fluorenyl, propionyl, and butylfluorenyl. As a result of an intensive review by the present inventors, it was found that when the fluorene substituents which substituted the above-mentioned fibrous base were substantially composed of two types: ethyl fluorenyl, propyl fluorenyl, and butyl fluorene, the total degree of substitution was 2.50 to 3.00. Low optical anisotropy of cellulose. It is preferably 2.60 to 3.00 and 2.65 to 3.00. The degree of polymerization of the tritiated cellulose film is obtained from acetic acid and substituted with acetic acid. The fat is allyl cellulose ester and aromatic. Among these, heptyl, decadecyl, and tertiary butyl groups can be lowered by the hydroxyl group of ethyl group. -35- 200537167,-Polymerization of the better tritiated cellulose film used in the present invention Degree, the viscosity / average degree of polymerization is 180 ~ 700. In the case of acetocellulose, 180 to 5 50 is preferable, 180 to 400 is more preferable, and 180 to 350 is particularly preferable. By setting the degree of polymerization to be less than or equal to a certain value, it is possible to prevent the film from being difficult to be produced by casting because the viscosity of the coating solution of the tritiated cellulose is too high. By setting the degree of polymerization to a certain level or more, it is possible to have the effect of preventing a decrease in the strength of the produced film. The average degree of polymerization can be measured by, for example, the intrinsic viscosity method of Uda (Kazuo Uda, Hideo Saito, The Journal of the Textile Society, Vol. 18 No. 1, pp. 105-120, p 1962). This method is described in detail in paragraph numbers (14 to 15) of Japanese Patent Application Laid-Open No. 9-95 5 38. The molecular weight distribution of the tritiated cellulose of the present invention is preferably evaluated by gel permeation chromatography. The polydispersity index Mw / Mn (Mw-based mass average molecular weight, Mη coefficient average molecular weight) is small, and the molecular weight distribution is small. Smaller is better. Specifically, Mw / Mn 値 is preferably 1.0 to 3.0, more preferably 1.0 to 2.0, and most preferably 1.0 to 1.6. When the low-molecular component is removed, the average molecular weight (degree of polymerization) increases, but it is useful because I has a lower viscosity than ordinary tritiated cellulose. Tritiated cellulose 'having fewer low-molecular components can be obtained by removing low-molecular components from the synthetic tritiated cellulose by a common method. Removal of low-molecular components can be carried out by washing the tritiated cellulose with a suitable organic solvent. In addition, when producing tritiated cellulose with low low-molecular components, the amount of sulfuric acid catalyst in the tritiation reaction is preferably adjusted to 0.5 to 25 parts by mass relative to 100 parts by mass of cellulose. When the amount of the sulfuric acid catalyst is in the above range, a better (uniform molecular weight distribution) tritiated cellulose can be synthesized from the viewpoint of molecular weight distribution. When producing tritiated cellulose that can be used in the present invention, the moisture content that can be used for tritiated cellulose is preferably 2 mass% to 36-200537167 /% or less, more preferably 1 mass% or less, and 0.7 mass% or less. Better. Generally, the moisture content of tritiated cellulose is known to be 2.5 to 5% by mass. In order to make the moisture content of the tritiated cellulose into the above range, it is necessary to dry it. If the moisture content can be achieved, the method is not particularly limited. The raw cotton and synthetic methods of the cellulose of this invention are disclosed in the Technical Bulletin of the Invention Association (Public Technology No. 200, 1745, issued on March 15, 2001, Association of Inventions) on pages 7-12 Described. When the substituted cellulose, the degree of substitution, the degree of polymerization, the molecular weight distribution, and the like of the halogenated cellulose are within the aforementioned ranges, a single or a mixture of two or more different cellulose celluloses may be used. < Additives of tritiated cellulose > The tritiated cellulose solution that can be used in the present invention can be added with various additives (such as compounds that reduce optical anisotropy, wavelength dispersion modifiers, and ultraviolet inhibitors) in each preparation step according to the application. , Plasticizer, aging preventive agent, fine particles, optical property adjuster, etc.), which are described below. In addition, the addition period can be added in each coating liquid manufacturing step, or it can be performed by adding an additive adding adjusting step to the last preparing step of the coating liquid preparing step. The tritiated cellulose film which can be used in the present invention, it is preferable that the compound contains a compound that can reduce Rth so that Rth in the thickness direction of the film satisfies Rth of the following formulae (II) and (IV). (III) (Rth (A)-Rth (0)) / A ^-1.0 (IV) 0.01 ^ A ^ 30 (In the formulae (III) and (IV), Rth (A) means that Ath Rth (nm) of the protective film of the compound, Rth (O) means that the protective film does not contain a compound that reduces -37- 200537167-Rth (nm), and A means the weight of the polymer relative to the film material When it is 100, the weight (%) of the compound that reduces Rth. (III), (IV) is (IIM) (Rth (A) -Rth (0)) / A ^-2.0 (IV-I) 0 · 1 'A-20 is more preferable. The characteristics of the compound structure that reduces the optical anisotropy of the tritiated cellulose film are explained. The compound that reduces the optical anisotropy of the tritiated cellulose film. The inventors of the present invention, etc. As a result of the review, the use of a compound in which the tritiated cellulose in the inhibitor film is aligned in the plane and in the thickness direction can sufficiently reduce the optical anisotropy, so that Re is zero and Rth is close to zero. Here, near zero refers to, for example, ( 0 ± 25nm). For this purpose, the compounds that reduce the optical anisotropy are more compatible with cellulose tritiated, the compound itself does not have a rod-like structure or a planar structure In particular, when it has a plurality of planar functional groups such as aromatic groups, it is advantageous in structure to have other functional groups such as non-planar and non-planar structures. • 10 g P 値 can be used in the production of the present invention. In the case of the tritiated cellulose film, as described above, among compounds that inhibit tritiated cellulose in the film from aligning in-plane and film thickness to reduce optical anisotropy, the water partition coefficient (logP 値) of octanol is 0. A compound of ~ 7 is preferred. By using 10 g of a compound having a P 値 of 7 or less, it has better compatibility with tritiated cellulose, which can more effectively prevent white turbidity of the film and the emergence of powder. Also, by using Compounds with a logP 値 of 0 or higher, because of their high hydrophilicity, can effectively prevent deterioration of the water resistance of the tritiated cellulose film. 10 P 値 is more preferably in the range of 1 to 6, and 1 · 5 to 5 The range of the special-38-200537167 is good. The measurement of the octanol-water partition coefficient (logP 値) can be carried out according to the flask permeation method described in nS Japan Industrial Standard Z7 2 6 (M 07 (2000)). The octanol-water partition coefficient (logP 値) can also be determined by Computational chemistry method or empirical method instead of actual measurement to estimate. The calculation method is to use Cnppen's fragmentation method (J.Chem. Inf. Comput. Sci ·, 27, 21 (1987) ·), Viswanadhan's fragmentation method (J. Chem. Inf Comput. Sci., 29, 163 (1989). Among them, the Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 2 1 (1 987) ·) is preferred. When the logP of a compound is not the same because of the measurement method or calculation method, it is better to use the Crippen's fragmentation method to determine whether the compound is within the scope of the present invention. Physical properties of compounds that reduce optical anisotropy Compounds that reduce optical anisotropy may contain an aromatic group or may not contain them. In addition, the molecular weight of the compound that reduces optical anisotropy is preferably 150 to 3000, more preferably 170 to 2000, and even more preferably 200 to 1,000. In such a molecular weight range, a specific monomer structure may be used, and the monomer units may have an oligomer structure, a polymer structure, etc., which are plurally combined. The compound for reducing optical anisotropy is preferably a 25 t liquid and a solid having a melting point of 25 to 250 ° C, and a 25 ° C liquid and a solid having a melting point of 25 to 200 ° C is more preferable. In addition, it is preferable that the compound that reduces optical anisotropy does not cause volatilization during the casting and drying of the coating solution during the production of the cellulose film. To reduce the amount of the optically anisotropic compound, it is preferably 0.01 to 30% by mass of tritiated cellulose, more preferably 1 to 25% by mass, and particularly preferably 5 to 20% by mass -39-200537167%. The optical anisotropy-reducing compound may be used alone, or two or more compounds may be mixed in any proportion. The time for adding the optical anisotropy-reducing compound may be added at any step in each coating liquid manufacturing step, or may be performed at the end of the coating liquid preparation step. The average content of the compound that reduces the optical anisotropy from the surface of at least one side to the entire film thickness of 10% is preferably the compound present in the center of the tritiated cellulose film. The average content rate is preferably 80 to 99%. The amount of the compound which reduces the optical anisotropy can be obtained by measuring the amount of the compound on the surface and the center using, for example, the method of infrared absorption spectrum described in JP-A-8-57 87-9. The following are specific examples of compounds which are preferably used in the present invention to reduce the optical anisotropy of the tritiated cellulose film, but the present invention is not limited to these compounds. The first example of a compound for reducing optical anisotropy is the following general formula (1 3)

It is also a compound represented by general formula (18). [Chemical Formula 3] General Formula (13)

R13 N ~ R12 In the general formula (13), R11 represents an alkyl group or an aryl group. R12 and Ri3 represent each independently hydrogen, alkyl or aryl. The total number of carbon atoms in R11, R12, and R13 is particularly preferably 10 or more. Ru, RU, and R13 may also have a substituent of -40-200537167. The substituent is preferably a fluorine atom, an alkyl group, an aryl group, an alkoxysulfonamido group, or a cyano group. An alkyl group, an aryl group, or an alkoxy group is preferred. Amine groups are particularly preferred. The methyl group may be linear or cyclic. The number of carbon atoms is preferably 1 to 25, and 6 to 25 6 to 20 (for example, methyl, ethyl, propyl, isopropyl, Base, tertiary butyl, amine, isoamine, tertiary amine, hexylheptyl, octyl, bicyclooctyl, nonyl, adamantyl, decyl, undecyl, dodecyl, ten Three-, fourteen-, and fifteen-based φ seventeen-, eighteen-, nineteen-, and didecyl) are particularly preferred: 6 to 30 are preferred, and 6 to 24 (phenyl , Biphenyl, naphthyl, binaphthyl, triphenylphenyl) are particularly preferred. [Chemical Formula 4] General Formula (18) OR16 II I R1 ^ —C—Γν-R15 In General Formula (18), R14 represents an alkyl group or an aryl group, and R15 0 represents an independent hydrogen atom, an alkyl group, or Is aryl. R14 is preferably a phenyl group or a cyclic alkyl group. R15 and R16 are preferably an alkyl group. Alkyl is preferably a cyclic alkyl group or a linear alkyl group. These groups may have a substituent. The substituent is preferably a fluorine atom, an alkoxy group, a sulfo group, and a sulfonamido group, and particularly preferably an alkyl group, a group, a sulfo group, and a sulfonamido group. The compound represented by the general formula (18) is represented by the general formula (19): Preferred. Sulfo, sulfo, and sulfo and sulfo are branched, and are more preferably `` butyl, isobutyl :, cyclohexyl, aryl, tertiary octyl :, hexadecyl, aryl carbon, terphenyl, and The R16 series is based on the compound of any one of benzene, alkyl, arylaryl, and alkoxy as -41- 200537167 9 [Chemical Formula 5] General Formula (19) OR116

II I R11-C-N-R115 In the general formula (19), R114, R115, and R116 each represent an independent alkyl group or an aryl group. Either an alkyl-based cyclic alkyl group or a linear alkyl group is preferable, and an aryl-based group is preferably a phenyl group. Hereinafter, preferred examples of the compound represented by the general formula (13) are shown in the following p, but the present invention is not limited to these specific examples. In the compounds, Pri means isopropyl (the same applies hereinafter).

-42- 200537167

-43- 200537167 [Chemical Formula 7]

Α-3 Ο A-31

A-34

A-3 5

A-39 -44- 200537167

Hereinafter, preferred examples of the compound represented by the general formula (18) (and the general formula (19)) are shown below, but the present invention is not limited to these specific examples. In the compound, Bui means isobutyl.

-45- 200537167 [Chemical Formula 9]

[Chemical Formula 10] FA-1 CH,

FA-2 FA-3

〇--rP

C-N C:

FA-4 FA-5 FA ·?

CH ^ CHa -46-200537167

-47- 200537167 [Chemical Formula 12] FA-13 FA-19 FA-20

-48- 200537167 [Chemical Formula 13] FB-1 FB-2 FB-3

CH3

Ο C ~ N

FS-4

FB-S ra-6

ιϊΡ

Ο s ^ o cy

FB-7

FB-S

^ H, C O you 1® O

^ ViKD h3c o

FB-12

Ffi-U Οτ ^ Ο ^ ϊΚΙ) CHa [\ CHj CH3 CHj FB-13

QXO FB-I4

O FB-16

P

FB-1S

-49- 200537167 [Chemical Formula 14] FB-17

FB-18

-H3CO

FB-22 Momichi! T-wing

FB-23 FB-24

50- 200537167 [Chemical Formula 15] FC-I FC-2 FC-3

FC * 7 FC-S 〇lif > u〇 FC-9

Or o u C-N h3c y = \

H, C O

FC-1I FC 12

-51- 200537167 [Chemical Formula 16] PC-18

FC-19

Hac〇H〇 讧 FC‘23 FC-23

-52- 200537167 [Chemical Formula 17] FD ^ 3 FD-1 Fl > 2

FD-7

FD-IO

-53- 200537167 [Chemical Formula 18]

FD-14 FD-15

-54- 200537167. Wavelength Dispersion Adjuster '' Describes compounds that reduce the wavelength dispersion of tritiated cellulose films (hereinafter also referred to as wavelength dispersion adjusters). In order to improve the Rth wavelength dispersion of the tritiated cellulose of the present invention, a method of satisfying the ranges of the following formulae (V) and (VI) includes at least one type of wavelength dispersion ARth that reduces the Rth represented by the following (VII) ARth II | Rth (400) — Rth (700) | compounds are preferred. (VII) ARth = | Rth (400)-Rth (700) | (V) (ARth (B)-ARth (0)) / B ^-2.0 _ (VI) 0.01 SBS 30 Above (V), (VI) (V- I) (ARth (B)-ARth (0)) / B ^-3.0 (VI-I) 0.05 ^ B ^ 25 is preferred, and (V- II) (ARth (B)-ARth (0)) / B ^-4.0 (VI-II) O. 1 ^ B ^ 20 ^ is more preferable. The above requirements are compounds containing at least one compound that has absorption in the ultraviolet region of 200 to 400 nm, and can reduce the film. Re (400) — Re (700) | and I Rth (40 0) — Rth (7 00) | It is achieved by 0.01 to 30% by mass based on the solid content of the tritiated cellulose. The content is more preferably 0_1 to 20% by mass of tritiated cellulose, and particularly preferably 0.2 to 10% by mass. Re and Rth of the tritiated cellulose film generally have a wavelength dispersion characteristic that is larger on the long wavelength side than on the short wavelength side. Therefore, it is required to smooth the wavelength dispersion by increasing the relatively small Re and Rth on the short wavelength side. On the other hand, '-55- 200537167-The compound having absorption in the ultraviolet region of 200 to 400 nm has a wavelength dispersion characteristic in which the absorbance at the long wavelength side is larger than the absorbance at the short wavelength side. If the compound itself exists in the tritiated cellulose film isotropically, it is assumed that the compound's birefringence, and further, the wavelength dispersion system of Re and Rth and the wavelength dispersion of absorbance are similarly large on the short wavelength side. Therefore, as described above, 'by using a substance having an absorption in the ultraviolet region of 200 to 400 nm', the Re of the compound itself and the wavelength dispersion of Rth on the short-wavelength φ side can be adjusted to adjust the Re of the cellulose film. , Rth wavelength dispersion. Therefore, compounds requiring wavelength dispersion adjustment can be very uniformly compatible with tritiated cellulose. The absorption band of the compound in the ultraviolet region is preferably 200 to 400 nm, more preferably 220 to 395 nm, and even more preferably 240 to 390 nm. In addition, in recent years, in order to enable liquid crystal display devices such as televisions, notebook personal computers, and mobile terminal devices to use less power to increase brightness, the optical members used in the liquid crystal display devices are required to have excellent 0-transmittance. In this regard, it is required to have absorption in the ultraviolet region of 200 to 400 nm, which can reduce the film | Re (400) -Re (700) | and | Rth (400)-

The compound Rth (700) 丨 has excellent spectral transmittance when added to a tritiated cellulose film. In the tritiated cellulose film of the present invention, the spectral transmittance at a wavelength of 3 to 80 nm is 45% to 95%, and the spectral transmittance at a wavelength of 350 nm is preferably 10% or less. As mentioned above, the preferred wavelength dispersion adjusting agent used in the present invention has a molecular weight of preferably 250 to 1,000 from the viewpoint of volatility, more preferably 260 to 800, more preferably 270 to 800, and particularly 300 to 800. good. If the range of these molecular weights is -56- 200537167-the range may be a specific monomer structure, and the monomer unit may also be an oligomer structure, a polymer structure, etc. formed by a plurality of combinations. The wavelength dispersion adjusting agent is preferably such that the coating solution does not volatilize during the casting and drying processes when the tritiated cellulose film is manufactured. These wavelength dispersion adjusting agents may be used alone or as a mixture of two or more compounds in any ratio. The timing for adding such a wavelength dispersion adjusting agent may be performed in any one of the steps of manufacturing the coating liquid, or may be performed at the end of p in the step of preparing the coating liquid. Specific examples of the preferred wavelength dispersion adjusting agent used in the present invention include, for example, benzotriazole-based compounds, diphenylketones, cyano-containing compounds, hydroxydiphenylketone-based compounds, and salicylic acid. Ester compounds and nickel salt compounds, but the present invention is not limited to these compounds. As the benzotriazole-based compound, a substance represented by the following general formula (101) is preferably used as the wavelength dispersion adjusting agent of the present invention. General formula (101)

Q 丨 1-Q 丨 2-OH (In the general formula (101), Q11 represents a nitrogen-containing aromatic heterocyclic ring, and Q12 represents an aromatic ring.) Q11 represents a nitrogen-containing aromatic heterocyclic ring, with 5 to 7 Nitrogen-containing aromatic heterocyclic rings are more preferred, and nitrogen-containing aromatic heterocyclic rings having 5 or 6-membered rings are more preferred. Examples include an imidazole ring, a pyrazole ring, a triazole ring, a tetrazole ring, Thiazole ring, oxazole ring, selenazole ring, benzotriazole ring, benzothiazole ring, benzoxazole ring, benzoselazole ring, thiadiazole ring, oxadiazole ring, naphthothiazole ring, naphthalene Pyridoxazole ring, azebenzimidazole ring, purine ring, pyridine ring, pyridine ring, pyrimidine ring, -57- 200537167. Dagen ring, Sangen ring, triazindane ring, tetrazindene ring, etc. The fluorene-containing nitrogen-containing aromatic heterocyclic ring of the nodal ring is more preferable, and specifically, the 'imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiaπ ring, fluorene ring, benzotriazole ring, A benzothiazole ring, a benzoxazole ring, a thiadiazole ring, and an oxadiazole ring are preferred. A benzotriazole ring is particularly preferred. The nitrogen-containing aromatic heterocyclic ring represented by Q11 may further contain a substituent, and a substituent T described later may be suitably used as the substituent. In the case of a plurality of substituents, each may be cyclically contracted to form a ring. The nitrogen-containing aromatic ring represented by p Q12 may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. In addition, these may be a single ring, or may further form a condensed ring with other rings. The aromatic hydrocarbon ring is preferably a monocyclic or bicyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms, and a monocyclic or bicyclic aromatic hydrocarbon ring having 6 to 20 carbon atoms is preferred. 6 to 12 monocyclic or bicyclic aromatic hydrocarbon rings are more preferred. Q12 represents a nitrogen-containing aromatic ring. Specifically, a naphthalene ring and a benzene ring are preferable, and a benzene ring is more preferable. _ Aromatic heterocyclic ring is preferably an aromatic heterocyclic ring containing a nitrogen atom or a sulfur atom. Specific examples of the heterocyclic ring include a thiophene ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyritra ring, a datra ring, a triazole ring, a Sango ring, an indole ring, an indazole ring, and a purine ring. , Thiazoline ring, thiazole ring, thiadiazole ring, oxazoline ring, oxazoline ring, [azodiazole ring, quinoline ring, isoquinoline ring, phthalocyanine ring, D fixed ring, sialoline ring , Quinazoline ring, oxoline ring, pyrimidine ring, acridine ring, morpholine ring, morphine ring, four-ti seat ring, benzimidazole ring, benzopyridine ring, benzopyridine ring , Benzotriazole ring, tetrazindene ring and the like. The aromatic heterocyclic ring is preferably a pyridine ring, a Sango ring, or a quinoline ring. -58- 200537167 ·-Q12 may have a substituent, and the substituent τ, which will be described later, is preferred. * Examples of the substituent T include an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and most preferably 1 to 8 carbon atoms. , Ethyl, isopropyl, tertiary butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), alkenyl (with 2 to 20 carbons as Better, preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, for example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), alkyne Group (preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly 2 to 8 carbon atoms are particularly preferred, and examples thereof include propargyl, 3-propynyl, etc.), Aryl (preferably 6 to 30 carbons, more preferably 6 to 20 carbons, particularly 6 to 12 carbons), for example, phenyl, p-methylphenyl, naphthyl, etc. ), Substituted or unsubstituted amine groups (preferably 0 to 20 carbon atoms, more preferred 0 to 10 carbon atoms, particularly preferred 0 to 6 carbon atoms), for example, amine groups, methyl groups Amino group, dimethylamino group, diethylamino group, dibenzylamino group, etc.), alkoxy group (preferably carbon number 1-20) The carbon number is more preferably from 1 to 12, and the carbon number is particularly preferably from 1 to 8. Examples include methoxy, ethoxy, and butoxy.), Aryloxy (6 to 6 carbons) 20 is preferred, carbon number 6 to 16 is more preferred, carbon number 6 to 12 is particularly preferred. Examples include phenoxy, 2-naphthyloxy, etc., and fluorenyl (based on carbon number 1 to 20 is preferred, 1 to 16 carbons are more preferred, and 1 to 12 carbons are particularly preferred. Examples include ethenyl, benzamyl, formamyl, and trimethylacetamidine. Groups, etc.), alkoxycarbonyl groups (preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, for example, a methoxycarbonyl group , Ethoxycarbonyl, etc.), aryloxycarbonyl (preferably with 7 to 20 carbons, more preferably with 7 to 16 carbons, particularly preferably with 7 to 10 carbons, examples include For example, phenoxycarbonyl, etc.), fluorenyloxy (preferably with 2 to 20 carbons, more preferably 2 to 16 -59-200537167, particularly preferably 2 to 10 carbons, etc.) For example, ethoxyl 'group, benzamyloxy group, etc.), fluorenylamino group (preferably with 2 to 20 carbon atoms, and 2 with carbon atoms) ~ 16 is more preferable, and carbon number of 2 to 10 is particularly preferable. Examples include acetamido, benzamido, and the like.), Alkoxycarbonylamino (with 2 to 20 carbons) It is better to use 2 to 16 carbon atoms, particularly to 2 to 12 carbon atoms. Examples include methoxycarbonylamino groups.), Aryloxycarbonylamino groups (from 7 to carbon atoms) 20 is preferred, carbon number 7 to 16 is more preferred, carbon number 7 to 12 is particularly preferred. Examples include phenoxycarbonylamino groups, etc.), sulfonamido groups (with carbon | number 1 Preferably, it is -20, more preferably 1 to 16 carbons, and particularly preferably 1 to 12 carbons. Examples thereof include a methanesulfonamido group and a benzsulfonamido group. ), Sulfonyl (preferably 0 to 20 carbons, more preferably 0 to 16 carbons, particularly 0 to 12 carbons), for example, sulfamoyl, methylaminesulfonyl Fluorenyl, dimethylaminosulfonyl, phenylsulfonyl, etc.), aminomethylsulfonyl (preferably 1 to 20 carbons, more preferably 1 to 16 carbons, 1 to 1 carbons) 12 is particularly preferred, and examples thereof include aminomethylamido, methylaminomethylamido, diethylaminomethylamido, phenylaminomethylamido, etc.), alkylthio ( Carbon number is preferably 1 to 20, g carbon number is 1 to 16 is more preferable, carbon number is 1 to 12 is particularly preferable, and examples thereof include methylthio group and ethylthio group.), Aromatic Sulfhydryl (preferably 6 to 20 carbons, more preferably 6 to 16 carbons, and particularly preferably 6 to 12 carbons. Examples include phenylthio). (The carbon number is preferably 1 to 20, the carbon number is 1 to 16 is more preferable, and the carbon number is 1 to 12 is particularly preferable. Examples thereof include a methylsulfonyl group and a p-toluenesulfonyl group. ), Sulfenyl group (preferably with carbon number 1-20, more preferably with carbon number 1-16, particularly preferably with carbon number 1-12) Examples include, for example, methanesulfinyl sulfenyl, benzenesulfinyl sulfenyl and the like.), Ureido (preferably carbon number 1-20, more preferably carbon number 1-16, more preferably carbon number 1-12) Particularly preferred, 60-200537167 can be exemplified by ureido, methylureido, phenylureido, etc.), amine phosphate (preferably with carbon number 1-20, more preferably with carbon number 1-16) Carbon atoms are particularly preferred, and examples thereof include diethylphosphonium amino groups, phenylphosphonium amino groups, etc.), hydroxyl groups, hydrogen thio groups, halogen atoms (such as fluorine atoms, chlorine atoms, Bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, oxo group, sulfinyl group, hydrazine group, imino group, heterocyclic group (with carbon number 1-30, preferably carbon number 1 ~ 12 is more preferable. Heteroatoms such as nitrogen atom, oxygen atom, and sulfur atom may be specifically exemplified by imidazolyl, pyrazolyl, quinolinyl, furyl, piperidinyl, amidinyl, and benzoxazole Group, benzimidazolyl, benzozolyl, etc.), silyl (preferably 3 to 40 carbons, more preferably 3 to 30 carbons, particularly 3 to 24 carbons are particularly preferred. Trimethylalkyl, triphenyl Alkyl silicon, etc.), these substituents may also be further generations. When there are two or more substituents, they may be the same or different. If possible, they can be connected to each other to form a ring. The general formula (101) is preferably a compound represented by the following general formula (101-A). [Chemical Formula 1 9] General formula (101-A) 醯 12 acid ortho acid orthothione

(In the general formula (101-A), 'R1, R2, R3, R4, r5, r6, R7, and the like are independent hydrogen atoms or substituents.) R, R2' R3 'R4' R5 ' R6'R7, r8, and r9 each represent a hydrogen atom or a substituent of 1, and the aforementioned substituents can be substituted R8 mono-61-200537167 ... T. These substituents may be further substituted with other substituents. The substituents may be cyclically contracted to form a ring structure. R1 and R3 are each preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an amine group, an alkoxy group, an aryloxy group, a hydroxyl group, or a halogen atom, and a hydrogen atom, a fluorenyl group, an aryl group, or an alkane group. Oxygen, aryloxy, and halogen atoms are preferred, with hydrogen atoms and carbon 1-12 being more preferred, carbons 1-12 being particularly preferred (preferably 4-12 carbons) ). R2 and R4 are each preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an amine φ group, an alkoxy group, an aryloxy group, a hydroxyl group, or a halogen atom, and a hydrogen atom, an alkyl group, an aryl group, or an alkane group is preferred. An oxygen group, an aryloxy group, and a halogen atom are preferred, a hydrogen atom and an alkyl group of carbon 1 to 12 are more preferred, a hydrogen atom and a methyl group are particularly preferred, and a hydrogen atom is most preferred. R5 and R8 are each preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an amine group, an alkoxy group, an aryloxy group, a hydroxyl group, or a halogen atom, and a hydrogen atom, an alkyl group, an aryl group, or an alkoxy group A radical, an aryloxy group, and a halogen atom are preferred, a hydrogen atom and an alkyl group of carbon 1 to 12 are more preferred, a hydrogen atom and a methyl group are particularly preferred, and a hydrogen I atom is most preferred. R6 and R7 are each preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an amine group, an alkoxy group, an aryloxy group, a hydroxyl group, or a halogen atom, and a hydrogen atom, an alkyl group, an aryl group, or a halogen atom is preferred. A radical, an aryloxy group, and a halogen atom are more preferred, a hydrogen atom and a halogen atom are more preferred, and a hydrogen atom and a chlorine atom are particularly preferred. The general formula (101) is preferably a compound represented by the following general formula (1 (Η_B). [Chemical formula 20] General formula (101-B) -62- 200537167

In the general formula (101-B), R1, R3, R6, and R7 are equivalent to the general formula (1 (HA), and their preferred ranges are also the same. The general formula (1 0 1) is given below. Specific examples of the compounds shown, but the present invention is not limited at all by the following specific examples.

UV-7

UV-8

UV4 UV-9

UV-S

UV-10 200537167 [Chemical Formula 22]

UVA6 UV- Π

UV-J3 UV-18

UV.14 M9 UV-15 ^ 00¾ UV-20

UV-22

-64- 200537167 Among the benzotriazole-based compounds listed in the above examples, it was confirmed that when the tritiated cellulose film of the present invention is produced without containing a molecular weight of 3 to 20, from the standpoint of retention Is favorable. The diphenyl ketone compound is one of the wavelength dispersion adjusting agents used in the present invention. The diphenyl ketone compound is preferably one represented by the general formula (102). [Chemical Formula 23] General Formula (102)

(In the general formula (102), Q1 and Q2 each represent an aromatic ring. X represents NR (R represents a hydrogen atom or a substituent.), An oxygen atom, or a sulfur atom.) The aromatics represented by Q1 and Q2 The family ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. In addition, these may be single rings, or they may form fused rings with other rings. The aromatic hydrocarbon ring represented by Q1 and Q2 is preferably a monocyclic or bicyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms (for example, a benzene ring, a naphthalene ring, etc.), and preferably 6 to 30 carbon atoms. An aromatic hydrocarbon ring of 20 is more preferable, an aromatic hydrocarbon ring having 6 to 12 carbons is more preferable, and a benzene ring is more preferable. The aromatic heterocyclic ring represented by Q1 and Q2 is preferably an aromatic heterocyclic ring containing at least any one of an oxygen atom, a nitrogen atom, or a sulfur atom. Specific examples of the heterocyclic ring include, for example, a furan ring, a pyrrole ring, a thiophene ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrrole ring, a datra ring, a triazole ring, a sangen ring, an indole ring, Indazole ring, purine ring, thiazoline ring, thiazole ring, thiadiazole ring, -65- 200537167 »»-Supraline ring, oxazole ring, epidazole ring, quinoline ring, isoquinoline ring, Coaxing ring, pyridine ring, quinazoline ring, quinazoline ring, oxoline ring, disco ring, mouth ring, morpholine ring, morphine ring, tetrazole ring, benzimidazole ring, phenylhydrazone Shure ring, benzothiazole ring, benzotriazole ring, tetrazindene ring and the like. The aromatic heterocyclic ring is preferably a pyridine ring, a triple well ring, a quinoline ring, or the like. The aromatic heterocyclic ring represented by Q1 and Q2 is preferably an aromatic hydrocarbon ring, more preferably an aromatic hydrocarbon ring having 6 to 18 carbon atoms, and even more preferably a substituted or unsubstituted benzene ring. Q1 and Q2 may further have a substituent, and a substituent T described later is preferred, and the substituent does not include a carboxylic acid, a sulfonic acid, or a quaternary ammonium salt. If possible, the substituents may be linked to form a ring structure. X represents NR (R represents a hydrogen atom or a substituent. The substituent can use the above-mentioned substituent T.) 'oxygen or sulfur atom, preferably nr (r is fluorenyl or sulfo, These substituents may be further substituted) or an oxygen atom, particularly an oxygen atom. The general formula (102) is preferably a compound represented by the following general formula (102-A). _ [Chemical Formula 24] General Formula (102-A)

(In the general formula (102-A), R21, r ", r23, R25, r26, r27, R28, and R2 9 each represent an independent hydrogen atom or a substituent.) V ', R ^, R24 , R25, R26, R28, and each represent an independent hydrogen-66-200537167 atom or a substituent, and the aforementioned substituents can be used as the substituents. These substituents can be further substituted by other substituents Substitution: It is also possible to cyclically shrink to form a ring structure. R21, R23, R24, R25, r26, r28, and κ are gas atoms, alkyl groups, alkyl groups, fast groups, aryl groups, amino groups, and oxygen groups. , Aryloxy, hydroxyl, and halogen atoms are preferred, with hydrogen atoms, alkyl, aryl, alkoxy, and aryloxy halogen atoms being preferred. 'Hydrogen atoms, carbon 1 to 12 alkyl groups are more preferred Of these, chloro and methyl are particularly preferred, and hydrogen is preferred.

R22 is preferably a hydrogen atom, an alkyl group, an alkyl group, an alkynyl group, an aryl group, an amine group, an oxo group, an aryloxy group, a hydroxyl group, and a halogen atom, and is preferably a hydrogen atom, an alkyl group having a carbon number of i to 20, and a carbon atom. 0 to 20 amine groups, 1 to 12 carbon alkoxy groups, 6 to 12 carbon aryloxy groups, hydroxyl groups are preferred, 1 to 20 carbon alkoxy groups are more preferred, and carbon is An alkoxy group of 1 to 12 is particularly preferred. R27 is preferably a hydrogen atom, an alkyl group, a storage group, an alkynyl group, an aryl group, an amine group, an oxo group, an aryloxy group, a hydroxyl group, and a halogen atom, and a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon number. 〇 ~ 20 amine group, alkoxy group with 1 to 12 carbons, aryloxy group with 6 to 12 carbons, and hydroxyl group are preferred. Hydrogen atom, alkyl group with 1 to 20 carbon atoms (with 1 to 20 carbon atoms) 12 is preferable, carbon number 1 to 8 is more preferable, methyl group is more preferable), methyl group and hydrogen atom are particularly preferable. The compound represented by the general formula (102) is preferably a compound represented by the general formula (102-B). [Chemical Formula 25] -67- 200537167 General Formula (102-B)

(In the general formula (102-B), R1C) represents a hydrogen atom, an alkyl group, or an aryl group. )

R10 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group and has a substituent. As the substituent, the aforementioned substituent τ R1 can be used. An alkyl group is preferred, and an alkyl group having 5 to 20 carbon atoms is more preferred. An alkyl group (for example, n-hexyl, 2-ethylhexyl, n-octyl, n-dodecyl, benzyl, etc.) More preferably, it is particularly preferably an unsubstituted alkyl group (2-ethylhexyl, n-octyl, n-decyl, n-benzyl) having 6 to 12 carbon atoms. The compound represented by the formula (102) can be synthesized by a method known in Japanese Unexamined Patent Publication No. 11 · Gazette and known as 1. Examples of the compound represented by the general formula (^ a U 02) are given below, but the present invention does not limit the @ 1 夂 to the following specific examples. ;, Alkynyl,, and the like may be 0 to 5-12 groups, n-decyl is substituted or dodecyl, 12219 specific tl -68- 200537167 [Chemical formula 26] UV-101

Ο

VV ^ 〇3

O OH (/ τΧο [Chemical Formula 27] UV-J049 OH UV- 105 Λ

CflH17 (nJ υν-109 OH 〇 〇Η CeHsO ^ ^ OCsHs UV-130 0C «Hi7

UV406

υν ^ ιο »

UV-UI

Ο OH

° CaH17 (nJ 0¾ 69- 200537167 [Chemical Formula 28] W17 uv_m

qhh2-Q ^ 0¾ (rlCsHnO 〇CSHt1 (n)

/ -IIS 0 ΗΝ-ί s〇2-^-ch3

UV-121 (n) CeHi? I uv-ne

HsCOT ^ ^ 'OCiaUssCn) The cyano group-containing compound is one of the wavelength dispersion adjusting agents used in the present invention. The cyano group-containing compound is preferably one represented by the general formula (103). [Chemical Formula 29] General Formula (103)

X 31, χ 32

Q

3V

Q 32 -70- 200537167 (In the general formula (103), Q31 and Q32 are each independently X31 and X32 are each a gas atom or a substituent group 'to a cyano group, a carbonyl group, a sulfofluorenyl group, and an aromatic heterocyclic group. The aromatic ring represented by Q31 and Q32 may be aromatic or an aromatic heterocyclic ring. Also, these rings may be a monocyclic ring to form a condensed ring. The aromatic hydrocarbon ring is a monocyclic ring having 6 to 30 carbon atoms or 2 (For example, a benzene ring and a naphthalene ring are mentioned.) A carbon ring is more preferable, and an aromatic hydrocarbon ring having 6 to 12 carbons is more preferable. The aromatic heterocyclic ring preferably contains a nitrogen atom or a sulfur atom. Specific examples of the heterocyclic ring include a thiophene ring, a q-pyridine ring, a pyridine ring, a da trap ring, a tri-π seated ring, a trioxazole ring, a purine ring, a thiazoline ring, a thiazole ring, and thiadiazol. Oxazole ring, oxadiazole ring, quinoline ring, isoquinoline ring, quinoline fline ring, quinazoline ring, oxoline ring, pyrimidine ring, mouth, chlorin ring, tetrazole ring, benzene A benzimidazole ring, a benzoxazole ring, a benzotriazole ring, a tetrazindene ring, etc. The aromatic heterocyclic ring is preferably a quinolinol ring, etc. The aromatic rings represented by Q31 and Q32 are more preferably an aromatic ring. Q31 and Q32 may further have a substituent. In the above description, χ | and X2 are used to indicate a hydrogen atom or a substituent, to a non-cyano group, a carbonyl group, a sulfonyl group, and an aromatic heterocyclic ring. X! And a substituted group can be applied. The aforesaid substituents τ. And χ vertical aromatic rings. One of them is listed below.) Aromatic hydrocarbon rings, or aromatic hydrocarbon rings 5 to 20 with other aromatic hydrocarbon rings. The most aromatic ring is a long azole ring, a pyrazole ring, a ring, an indole ring, an indene ring, an oxazoline ring, a well ring, a pyridine ring, a 'pyridine ring, a morpholine ring,!, A benzothiazole ring, a: [: D fixed ring, a triad ring, and a hydrocarbon ring are preferred, and a benzene substituted group T is preferred. One of them is the formula represented by χ2 [The formula represented by X2 • 71-200537167 can be substituted by other substituents, and χ1 and χ2 can be cyclically contracted to form a ring structure. X1 and X2 are preferably a hydrogen atom, an alkyl group, an aryl group, a cyano group, a nitro group, a carbonyl group, a sulfofluorenyl group, and an aromatic heterocyclic ring, and more preferably a cyano group, a carbonyl group, a sulfonyl group, and an aromatic heterocyclic ring. Preferred are cyano and carbonyl, and cyano and alkoxycarbonyl (-C (= 〇) 〇R (R is: alkyl group with carbon number υο, aryl group with carbon number 6-12 and combinations thereof) ) Is particularly preferred. The general formula (103) is preferably a compound represented by the following general formula (103-A). [Chemical Formula 30] General formula (103-A)

R 32 3 5

R

R38, R39, and R3 ° represent each independently a hydrogen atom or a substituent. 31 and X32 have the same meaning as that of the general formula (103), and the preferred ranges are also the same. ) R ”, Rn, R34, R”, r36, R3 3 are each a separate hydrogen atom or a substituent, and the aforementioned substituent T may be used as the substituent. These substituents may be further substituted with other substituents. The substituents may be cyclically contracted to form a ring structure. K, factory, R'R ", r, R37, r3. Preferred are hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, amine group, alkoxy group, aryloxy group, hydroxyl group, and halogen atom. 'A hydrogen atom, alkyl group, aryl group, alkoxy group, and aryloxy group are preferred. A radical, -72-200537167 is more preferred, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms is more preferred, a hydrogen atom, a methyl group is particularly preferred, and a hydrogen atom is most preferred. R33 and R38 are preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an amine group, an alkoxy group, an aryloxy group, a hydroxyl group, and a halogen atom. A hydrogen atom, an alkyl group having 1 to 2q carbon atoms, Amino groups with 0 to 20 carbon atoms, Alkyl groups with 1 to 12 carbon atoms, Cryptoxy groups with 6 to 6 carbon atoms, and Warp groups are preferred. 'A nitrogen atom, 1 to 12 carbon atoms, and 1 to 12 carbon atoms An alkyl gas of ~ 12 is more preferred, and a hydrogen atom is particularly preferred. The general formula (103) is preferably a compound represented by the following general formula (io3-B). [Chemical Formula 31] General Formula (103-B) NC \ ^ X33

(In the general formula (103-B), R33 and R "are the same as the general formula (103-3), and the preferred range is also the same. X3 3 represents a hydrogen atom or a substituent.) X33 Represents a hydrogen atom or a substituent, and the substituent may be the aforementioned substituent T, and may be substituted by a substituent when possible. X33 is a hydrogen atom, an alkyl group, an aryl group, a cyano group, a nitro group, a carbonyl group, Sulfonyl and aromatic heterocycles are preferred'Cyanyl, carbonyl, sulfofluorenyl, and aromatic heterocycles are preferred, cyano and carbonyl are more preferred, and cyano and alkoxycarbonyl (-C (= 〇) 〇R3Q1 (R3.1 is: alkyl group with 1 to 20 carbons, aryl group with 6 to 12 carbons, and combinations thereof)) is particularly preferred. -73- 200537167 · General formula (103 ), A compound represented by the following general formula (103-C) is preferable. '[Chemical formula 32] General formula (103-C) 0

(In the general formula (103-C), R33 and R38 are equivalent to the general formula (103-A), and the preferred ranges are also the same. R3 ° 2 represents an alkyl group having 1 to 20 carbon atoms.) R3 ° 2 When both R33 and R38 are hydrogen atoms, alkyl groups with 2 to 12 carbon atoms are preferred. '4 to 12 carbon atoms are preferred, and 6 to 12 carbon atoms are more preferred. Preferably, n-octyl, tertiary octyl, 2-ethylhexyl, n-decyl, and n-dodecyl are particularly preferred, and 2-ethylhexyl is most preferred. R3 ° 2 When R33 and R38 are other than a hydrogen atom, the compound represented by the general formula (103-C) is preferably an alkyl group having a molecular weight of 300 or more and a carbon number of 20 or less. The compound represented by the general formula (103) of the present invention can be synthesized by the method described in Jouiial of American Chemical Society 63 Vol. 3452 (1941). Specific examples of the compound represented by the general formula (103) are given below, but the present invention is not limited at all by the following specific examples. -74- 200537167 [Chemical Formula 33]

-75 200537167 [Chemical Formula 34] UV-211

〇 UV-2I6 〇 h3c

Q UV-212

UV ^ 217

UV-21S Ο ^ Γ Οoxc UV-2L9 ο

UV-215 UV-220

76- 200537167

[Chemical Formula 35] UV-22I

UV ^ 226

UV-222

UV-231

PhWCN ^ HPI 〇Η-λ〇 Ph MC Ph -77- 200537167 κ *-Matting agent fine particles It is preferable to add fine particles as a matting agent for the tritiated cellulose film used in the present invention. Examples of the microparticles used in the present invention include silicon dioxide, titanium dioxide, aluminum oxide, chromium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, calcium silicate hydrate, aluminum silicate, magnesium silicate, and Calcium phosphate and so on. Microparticles are silicon-containing substances, which are preferred in terms of turbidity, and silicon dioxide is particularly preferred. Fine particles of silicon dioxide having a primary average particle size of 2 nm or less and an apparent specific gravity of 70 g / liter or more are preferred. One-time φ particles with an average diameter as small as 5 to 16 nm are preferred because they can reduce the haze of the film. The apparent specific gravity is preferably 90 to 200 g / liter or more, and more preferably 100 to 200 g / liter or more. The larger the apparent specific gravity, the more it can be used as a high-concentration dispersion, and it is preferable because it can improve haze and agglomerates. The average particle size of these fine particles is usually a secondary particle of 0.1 to 3.0 micrometers, and these fine particles exist as agglomerates of primary particles in the film. An unevenness of 0.1 to 3.0 microns is formed on the film surface. The secondary average particle size is preferably 0.2 μm to 1.5 μm, more preferably 0.4 μm to 1.2 μm, and most preferably 0.6 μm to 1.1 μm. The primary and secondary particle sizes are measured using a scanning electron microscope to observe the particles in the film, and the outer circle of the particles is used as the particle size. Furthermore, 200 particles were observed at different positions, and the average particle size was used as the average particle size. As the fine particles of silicon dioxide, commercially available products such as AEROSIL R972, R972V, R974, R812, 200, 200V, 300, R202, 0X50, and TT600 (the above are manufactured by Japan Ayelozilu (stock)) can be used. Europium oxide fine particles are commercially available such as AEROSIL R97 6, R81 1 (the above are manufactured by Ayelozilu (Japan)). -78- 200537167 蠡 ·. Of these, 'AEROSIL 200V, AEROSIL R972V Series 1' "fine particles with an average particle size of 20 nm or less and an apparent specific gravity of 70 g / L made of silicon dioxide, because the edges remain low The turbidity of the optical film is particularly good because it has the effect of reducing the coefficient of friction. In order to obtain a small-sized cellulose film with a secondary average particle size, the present invention considers several methods when preparing a dispersion of fine particles, and if it is prepared in advance, it is stirred A fine particle liquid made by mixing a solvent and fine particles. This fine particle dispersion is added to a small amount of tritiated fiber prepared separately. The solution is stirred and dissolved, and then the main tritiated cellulose coating solution. This method is a silica particle. The dispersibility is better, and it is a better preparation method because the silica particles are not easy to aggregate. In addition, a small amount of cellulose ester is added to the solvent, and after stirring and dissolving, the particles are added here and dispersed using a disperser. This is a method for sufficiently mixing the fine particle addition liquid and the coating liquid with an axial agitator as the fine particle addition liquid. This method is not limited to these methods, and the silicon dioxide is The concentration of silicon dioxide when the particles are mixed and dispersed is preferably 5 to 30% by mass | 10 to 25% by mass is more preferable, and 15 to 20% by mass is most preferable. The dispersion turbidity is relative to the amount of liquid turbidity added It is lower because it can improve haze and setting. Finally, it is better to add 0.01 ~ 1 g per square meter to the matting agent in the coating solution of tritiated cellulose, more preferably 0.03 ~ 0.3 g. ~ 0. 16g is the best. The solvents used are low carbon number alcohols, including methanol alcohol, propanol, isopropanol, butanol, etc. The solvents other than low carbon number alcohol are not limited, The solvent used in the film formation with cellulose ester is preferred. For example, a solvent selected from the group consisting of halogenated hydrocarbons having a carbon number of 1 to 7 can be used. There are micro-solvents, so that the solvent is added in the amount of high polymer, and the special solvent is -79- 200537167 ο *-. The solvent can be 1 type, or more than 2 types can be used in combination. '' Plastic Compounds, anti-aging agents, release agents compounds that reduce the aforementioned optical anisotropy, wavelength dispersion In addition to the bulking agent, the tritiated cellulose film of the present invention can be added with various additives (for example, plasticizer, UV preventive agent, aging preventive agent, release agent, infrared absorber, etc.) in each preparation step according to the purpose. These may be The solid may be an oily substance. That is, its melting point, boiling point, etc. are not particularly limited. For example, it is described in JP-A No. 200 1-15 1 90 1 and the like. For example, it absorbs ultraviolet rays at φ or lower at 20 ° C and 20 ° C. Mixing of materials, similarly mixing of plasticizers, and the like. In addition, infrared absorbing dyes are described in, for example, Japanese Patent Application Laid-Open No. 200 1-94522. In addition, the addition time may be added at any step in the manufacturing process of the coating liquid, or Addition of an additive addition preparation step to the final preparation step of the coating solution manufacturing step. In addition, the amount of each raw material added is not particularly limited as long as the function can be exhibited. In addition, when the tritiated cellulose film is formed of a plurality of layers, the types, addition amounts, and the like of the additives in each layer may be different. For example, Japanese Unexamined Patent Publication No. 200 1-1 5 1 902 and the like are conventionally known techniques. φ For details, it is better to use the raw materials detailed on pages 16 to 22 of the Invention Association's Public Technical Bulletin (public technical numbers 200 1-1 745, 200 issued March 15, 2001, Invention Association). Compound addition ratio In the tritiated cellulose film which can be used in the present invention, the total amount of compounds having a molecular weight of 3,000 or less is preferably 5 to 45% by weight based on the tritiated cellulose. 10 to 40% is more preferable, and 15 to 30% is more preferable. As mentioned above, there are compounds that reduce optical anisotropy, wavelength dispersion modifiers, ultraviolet inhibitors, plasticizers, aging inhibitors, fine particles, mold release agents, -80- 200537167 Λ · Infrared absorber, molecular weight is 3 0 0 0 or less is better, more preferably, 1 000 or less is more preferred. When these compounds are combined, the properties of tritiated cellulose monomers are more likely to occur, and changes in humidity are more likely to cause problems with optical properties and physical strength. In addition, if the total amount of these compounds is greater than 45%, the compatibility of the compounds in the tritiated cellulose film is greater than the organic solvent of the tritiated cellulose solution, such as precipitation on the surface of the film and making the film cloudy (emerging from the film). B The present invention uses a solvent casting method to produce tritiated fibers, which can be produced by dissolving a tritiated cellulose in an organic solvent (coating solution). The organic solvent that can be used as the main solvent of the present invention may be a solvent selected from the group consisting of an ester having 3 to 12 carbon atoms and a halogenated hydrocarbon having 1 to 7 carbon atoms, and the ether may have a cyclic structure. Any of two or more of 1-0, 1CO-, and 1CO1) containing an ester, ketone, and ether may be used as a main solvent, and may contain, for example, an alcoholic hydroxyl φ energy group. When the main solvent containing two or more kinds of functional groups is within a predetermined range of a compound containing any one of the functional groups, the halogenated cellulose film which can be used in the present invention is a chlorine-based halogenated hydrocarbon as the main solvent. As described in the invention agreement 200 1-1 745 (pages 12 to 16), a non-chlorine-based compound can also be used as the main solvent, and there is no particular limitation on the film that can be used in the present invention. In addition, the patents concerning the tritiated cellulose solution and thinner of the present invention are disclosed and also contain the dissolving method, but the amount is less than 5% if it is less than 2000. If there is a question about temperature change, it is more likely to exceed the limit. And the problem. A plain film is preferred, and the resulting solution is preferably a ketone or ether. The ester, _I energy group (that is, the other compounds of the compound also have a better carbon number. It can also make the technical report of the halogenated hydrocarbon-halogenated cellulose film solvent: a good appearance. -81- 200537167 • For example, Japanese Patent Laid-Open No. 2000 -9 5 87 No. 6, JP-A No. 1 2-95 877- *, JP-A No. 1 0-3 24774, JP-A No. 8-1 5 25 1 4 , Kaihei 1 0-3 3 05 3 8, kaihei 9-9 5 5 3 8, kaihei 9-9 5 5 5 7, kaihei 1 0- 23 5 664, kaihei 1 2- No. 63 5 No. 34, No. 11-21379, No. 1 Heping 1 0- 1 8285 No. 3, No. Heping 1 0-27 8056, No. 0-279702, No. 1 Heping 1 0-3 23 85 No. 3, JP-A-1 0-237 1 86, JP-A 1-60-60807, JP-A U-1 52342, JP-A 1-1-2929 88, JP-A 1 1 6075 2 and other publications. These patents describe not only the preferred solvents for the tritiated cellulose in the present invention, but also the physical properties of the solution and coexisting substances, etc., which are also preferred in the present invention. Manufacturing steps The method for preparing the tritiated cellulose solution (coating solution) of the present invention is not particularly limited, and it may be performed at room temperature, and further, by a cooling dissolution method or a high temperature dissolution method, and may be implemented in combination of these. The preparation of the tritiated cellulose solution is accompanied by further steps of solution concentration and filtration of the dissolution step, in order to use in the technical publication of the Invention Association (public technical number 2001-1745, issued on March 15, 2001, invention Association) The manufacturing steps detailed on pages 22 to 25 are preferred. Transparency of the coating solution The transparency of the coating solution of the tritiated cellulose solution used in the present invention is preferably 85% or more, 88% or more is preferable, and 90% or more More than% is more preferred. In the present invention, it has been confirmed that various additions can sufficiently dissolve tritiated cellulose in the coating solution. Specifically, to calculate the transparency of the coating liquid, the coating liquid can be poured into a 1 cm square glass container and used. Spectrophotometer • 82- 200537167 η-• (UV-3150, Shimadzu Corporation) Measure the absorbance at 550 nm. Pre-measurement " Only solvent as blank test The transparency of the tritiated cellulose solution was calculated from the absorbance ratio with the blank test. Casting, drying, and rolling steps Next, a method for manufacturing a tritiated cellulose film using the tritiated cellulose solution of the present invention will be described. In the present invention, As the method and equipment for producing a tritiated cellulose film, a solution casting film forming method and a solution casting film forming apparatus that were conventionally used to produce a tritiated cellulose film can be used. For example, temporarily store the coating solution prepared by a dissolver (pot) in a storage g pot, and defoam the bubbles contained in the coating solution to complete the final preparation. The coating liquid is sent from the coating liquid discharge port to the pressure die through a pressure type dosing pump capable of high precision quantitative liquid feeding by the number of rotations, so that the coating liquid is discharged from the nozzle of the pressure die (slit). Continuously and uniformly cast on the metal support of the casting portion, and at a peeling point of about one turn of the metal support, the semi-dry coating film (also referred to as a film) was peeled from the metal support. The two ends of the obtained film were clamped by clips, and the tenter was transported and dried while maintaining the width. Then, the obtained film was mechanically transported using a roller group of a drying device, and the coiler was used after drying. It is wound into a roll shape according to the specified length. The combination of the tenter and the drying device of the drum group is changed according to its purpose. Further, a coating device is most often added to the tritiated cellulose film used in the present invention for processing the surface of the polarizing film. These are described in detail in pages 25 to 30 of the Public Technical Bulletin of the Invention Association (public technology number 20 (H-1 745, 200 issued March 15, 2001, Invention Association), classified as cast (including co-cast), Metal supports, drying, peeling, etc., can be suitably used in the present invention. The thickness of the tritiated cellulose film is preferably 10 to 120 microns, and 20 to 100-83-200537167 is preferred. It is better to use 30 ~ 90 micron. •-Change of optical properties of tritiated cellulose film after high temperature treatment Tritiated cellulose film physical properties evaluation The tritiated cellulose film that can be used in the present invention is caused by environmental changes. The optical property #change 'is preferably a change in the Re and Rth of the halogenated cellulose film after being treated at 60 ° C, 90% R for 24 hours, preferably 15 nm or less, and preferably 12 nm or less. It is better to be less than 10 nm. Changes in optical properties of films after high temperature treatment • Re and Re of cellulose films treated at 80C and 240 hours

The amount of change in Rth is preferably 15 nm or less. The thickness is preferably 12 nm or less, and more preferably 10 nm or less. After the thin film heat treatment, the volatilization amount of the compound is in the halogenated cellulose film used in the present invention, the compound that reduces Rth and the compound that reduces ΔRth. Below 30% is preferred. 25% or less is preferable, and 20% or less is more preferable. φ In addition, from the volatility of the tritiated cellulose film, the tritiated cellulose film that has been treated at 80 ° C for 240 hours and the untreated tritiated cellulose film are each dissolved with a solvent, and the liquid is used at high speed. Chromatographic detection of the compound 'The peak area of the compound was taken as the remaining compound in the film, and it was calculated as follows. Volatile amount (%) = {(amount of residual compound in untreated product)-(amount of residual compound in processed product)} / (amount of residual compound in untreated product) X 100 × glass of cellulose film Transition temperature (Tg) The glass transition temperature Tg of the tritiated cellulose film that can be used in the present invention is -84-200537167-8 0 ~ 16 5 ° C. From the viewpoint of heat resistance, T g is more preferably from 100 to 160 ° C, and particularly preferably from 1 to 10 to 15 CTC. The measurement of the glass transition temperature (Tg) is to take 10 mg of the tritiated cellulose film sample that can be used in the present invention, and raise the temperature from normal temperature to 200 ° C, and the temperature increase rate is 5 ° C / min. (DSC2910, TAINSTRUMENT) By measuring the heat, the glass transition temperature (Tg) can be calculated. The haze of the tritiated cellulose film The haze of the tritiated cellulose film which can be used in the present invention is preferably 0.01 to 2.0% as φ. It is preferably from 0.05 to 1.5%, and more preferably from 0.1 to 1.0%. The haze can be measured on a 40mm X 80 mm sample of the tritiated cellulose film of the present invention at 25 ° C, 60% RH using a haze meter (HGM-2DP, Suga testing machine) in accordance with JIS K-6714 Determination. Humidity dependence of Re and Rth of tritiated cellulose film The phase difference (Re) and hysteresis (Rth) in the thickness direction of tritiated cellulose film that can be used in the present invention are both changed due to temperature. Smaller is better. Specifically, the difference between Rth at 25 ° C and 10% RH and Rth at 25 ° C and 80% RH Δ Rth (= Rth10% RH—Rth80% RH) is preferably 0 to 50 nm. 0 to 40 nm is preferable, and 0 to 35 nm is more preferable. Equilibrium moisture content of tritiated cellulose film The tritiated cellulose film that can be used in the present invention is not affected by the thickness of the film to a certain extent in order not to impair the adhesion with water-soluble polymers such as polyvinyl alcohol. The equilibrium moisture content of% 101 is preferably from 0 to 4%, more preferably from 0.1 to 3.5%, and particularly preferably from 1 to 3%. By making the equilibrium moisture content below 4%, the hysteresis can be further reduced. Dependence on changes in humidity is better. The moisture content of the present invention can be used for the 7-mm-35-200537167 cellulose film samples of the present invention using a sample drying device (CA-03, VA-05, Both are manufactured by Mitsubishi Chemical Corporation using the Carr-Fisher method, and calculated by dividing the moisture content (g) by the weight of the sample (g). Moisture permeability of tritiated cellulose membranes The present invention can be used The moisture permeability of the halogenated cellulose film was measured in accordance with the ns standard JISZ0208 at a temperature of 60 ° C and a humidity of 95% RH. The conversion film thickness was 80 microns and 400 to 2000 g / m2 for 24 hours. 500 to 1 800 g / m for 2.24 hours is more preferable, and 600 to 1 600 g / m2 · φ for 24 hours is particularly preferable. 2000 g / m2 · 24 hours or less, it is easier to keep the absolute temperature dependence of Re and Rth of the tritiated cellulose film 値 0.5 nm /% RH or less, and it can more effectively suppress the color development of liquid crystal displays Change, reduction of viewing angle, etc. Moreover, by making the moisture permeability of the tritiated cellulose film 400 g / m2 for more than 24 hours, the adhesive of the tritiated cellulose film can be dried more easily and the good adhesion can be changed. The thicker the membrane thickness of the tritiated cellulose membrane, the lower the moisture permeability. If the membrane thickness is thinner, the moisture permeability will increase. Therefore, no matter what the film thickness is, the sample can be converted by setting the benchmark at 80 microns. In the present invention, the film thickness is obtained as follows, and is converted to a moisture permeability of 80 micrometers = the measured moisture permeability X the measured film thickness micrometers / 80 micrometers.

The method of measuring the moisture permeability can be applied to "Polymer Properties II" (Polymer Experiment Lecture 4 Kyoritsu Publishing) pages 285 ~ 294: Measurement of vapor penetration (mass method, thermometer method, vapor pressure method, adsorption amount method) ) The method described in the above, "samples of tritiated cellulose films of 70 mmcD which can be used in the present invention" are subjected to humidity adjustment at 25 ° C, 90% RH and 60 ° C, 95% RH for 24 hours, and moisture permeability is used. Test device (KK_709007, Toyo Seiki Co., Ltd.) 'Calculate the water content per unit area (g / m2) based on JIS-86- 200537167 Z-0208, and use the moisture permeability: z weight after humidity adjustment-weight before humidity adjustment Find it. Dimensional change of film The dimensional stability of the tritiated cellulose film that can be used in the present invention, the dimensional change rate of standing for 24 hours (high humidity) under the conditions of 60 ° C and 90% RH, and at 90 ° C, 5 Any dimensional change rate of standing for 24 hours (high temperature) under% RH condition is preferably 0.5% or less. 0.3% or less is preferable, and 0.15% or less is more preferable. The dimensional change rate of the present invention can be obtained by the following method. That is, two 30mmxl20mm cellulose cellulose samples were prepared, humidity-controlled at 25 ° C and 60% RH for 24 hours, and an automatic needle gauge (Xindong Science Co., Ltd.) was used to open 6 μm holes at 100 mm at both ends as The original size of the perforation interval (L0). Measure the perforation interval size (L1) of one sample after treatment at 60 ° C and 90% RH for 24 hours, and measure the perforation interval size (L2) of another sample after treatment at 90 ° C and 5% RH for 24 hours . All intervals are measured until the minimum scale is 1 / 1000mm. 6 (TC, 90% RH (high humidity) dimensional change rate is obtained by the following formula, dimensional change rate = {| L0— Ll | / L0} xl00, 90 ° C, 5% RH (high temperature) dimensional change rate = {I L0 — L2 | / L0} xl00. Elasticity (elasticity) of the film The elasticity of the cellulose film to be used in the present invention is preferably 200 to 500 kgf / mm2. 240 to 470 kgf / mm2 It is better to use 270 ~ 4401 ^ [/ 1111112. The elasticity ratio of the present invention refers to the use of Toyo Borudin universal tensile testing machine STM T50BP, at 23 ° C, 70% environment, -87- 200537167 镛-得到 obtained by measuring the stress of 0.5% elongation at a tensile speed of 10% / min. ^ Photoelastic coefficient (photoelastic coefficient) of the film The elastic coefficient of the tritiated cellulose film that can be used in the present invention 50x10 13cm2 / dyne or lower is preferred. 30x 10 13cm2 / dyne or lower is preferred, and 20x1 (Γ " cm2 / dyne or lower is more preferred. The photoelastic coefficient is for 1 2 mm X 1 2 0 mm chemical fiber The tensile stress was applied to the long axis direction of the plain film sample, and the hysteresis 此时 at this time was measured using a polarizing ellipsometer (M150, Japan spectrometer (g)). Calculate the amount of change in the hysteresis 应力 of the stress before and after stretching, and prepare a 100x1 00mm sample for the detection of the hysteresis 正面 before and after stretching. Use a fixed uniaxial elongation machine at a temperature of 140 ° C. Extend in the conveying direction (MD direction) or vertical direction (TD direction). The frontal hysteresis of each sample before and after the extension is measured by an automatic refractometer KOBRA21 ADH. The detection of the retardation axis is performed when the hysteresis is measured. The orientation angle is determined. The change in Re due to elongation is preferably small. Specifically, Re (η) is the in-plane frontal hysteresis (nm) of the film extending n (%), and Re (0 When) is the in-plane frontal retardation nm (nm) of the unstretched film, it is preferable to have | Re (n)-Re (0) | / nS 1.0, and | Re (n) — Re (0) | / η ^ 0.3 is better. Orientation of the retarded cellulose film In order to make the polarizing film have an absorption axis in the mechanical conveying direction (MD direction), the retarded cellulose film can be used in the present invention. The vicinity of the MD direction or the vicinity of the TD is preferred. The leakage can be reduced by the retardation axis being parallel or orthogonal to the polarizing film. Light or hair color. Nearby means that, for example, the retardation axis and MD or TD directions are displayed at 0 to 10 degrees, and the range of 0 to 5 degrees is -88- 200537167 •-. Cellulose film The hysteresis cellulose film that can be used in the present invention has a large frontal hysteresis when the film is extended in the direction of the inner axis of the film, and a small frontal hysteresis when the film is extended in a direction with a retardation. This shows inherent folds, and extending in a direction perpendicular to the retardation axis is effective to eliminate the hysteresis system present on the cellulose membrane. This method, for example, when the film has a late phase axis in the mechanical transfer (MD direction), it can be considered that the use of a tenter stretch in a direction perpendicular to the MD (TD direction) can reduce the frontal hysteresis. For the film, when the film has a late phase axis in the TD direction, it can be considered that the positive chirp can be reduced when the film is stretched by the tension of the mechanical conveying roller in the if direction. Tritiated cellulose film with negative intrinsic birefringence The tritiated cellulose film that can be used in the present invention also has a negative hysteresis when the film is extended in the direction of the retardation axis, and a negative hysteresis when it is extended in the direction of the retardation.値 becomes larger. This shows that the intrinsic I is negative and extending in the same direction as the late phase axis is effective to eliminate the delayed actinide in the membrane. This method, for example, when the film has a slow axis in the direction of mechanical conveyance, can be considered to reduce the frontal hysteresis when stretched by increasing the tension of the machine roller in the MD direction. Phase, when the film has a late phase axis in the TD direction, it can be considered that the use of a tenter extension in a straight direction (TD direction) can reduce the frontal step of the cellulose film. The evaluation method of the cellulose film can be used in the present invention. The evaluation of the chemical cellulose film was measured in the following invention examples by performing the following method. An example where the vertical phase to the late phase axis is in the opposite direction of the direction of the apparent direction of transport. The strong md plane hysteresis in the plane shows the vertical birefringence to the axis. -200537167 (In-plane retardation 値 Re, film thickness direction retardation 値 Rth) A 30mm × 40mm sample was conditioned at 25 ° C and 60% RH for 2 hours. Re (λ) was in an autobirefringence meter K〇BRA21ADH ( Oji Measurement Equipment Co., Ltd.) measures light incident at a wavelength of A nm in the normal direction of the thin film. Rth (λ) uses the above-mentioned Re and the in-plane retardation axis as the tilt axis and the film The normal direction is regarded as 0 degrees, and the sample is tilted from 10 degrees to 50 degrees each time and measured with a wavelength of λ nm. The hysteresis chirp is used as the basis, and the assumption of the average refractive index is input.値 1.48 φ and film thickness are calculated. (Re and Rth wavelength dispersion measurement) A 30mm × 40mm sample is conditioned at 25 ° C and 60% RH for 2 hours, and is measured on a polarization ellipsometer M-150 (Manufactured by JASCO Corporation), and incident light with a wavelength of 7 80nm to 3 80nm in the direction of the film normal, Obtain Re, and measure the wavelength dispersion of Re. Regarding the wavelength dispersion of Rth, the above-mentioned Re is used, the in-plane retardation axis is used as the tilt axis, and the direction of the normal direction is +40 degrees. The incident wavelength is 7 8 0 nm. Hysteresis φ obtained by measuring light from 380 nm to φ, and using the in-plane retardation axis as the tilt axis and incident light with a wavelength of 780 nm to 3 80 nm in the direction of the normal direction of -40 degrees The hysteresis 得到 obtained by measurement is calculated based on the hysteresis 値 値 obtained by measuring in three directions in total, and the hypothesis of the average refractive index 値 1.48 and the film thickness are calculated. (Molecular alignment axis) 70 mmx100 mm For a sample, at 25t: 65% RH for 2 hours, using an automatic birefringence meter (KOBRA 21DH, Oji measurement (strand)), and changing the incident angle at normal incidence, the molecular alignment axis is calculated from the phase difference. -90- 200537167 (Axis deviation) In addition, an automatic birefringence meter (KOBRA-21 ADH, Oji measuring equipment (strand)) measures the angle of axis deviation. Measure 20 points at equal intervals, across the entire width in the width direction, and obtain Absolutely mean average. Again The lens of the late phase axis angle (axis deviation) is measured at 20 points at equal intervals, spans, and full width, and the average of the absolute largest deviation from the axis and the absolute deviation of the four points from the axis are smaller. (Transmittance) g For a 20 mm x 70 mm sample, measure the visible light (615 nm) at 25 ° C and 60% RH using an automatic birefringence meter (AKA Phototube Colorimeter, KOTAKI Co., Ltd.). Penetration. (Spectral characteristics) Using a spectrometer (U-3210, Hitachi, Ltd.) at a temperature of 25 ° C and 60% RH for a 13 mm x 40 mm sample, the transmittance at a wavelength of 300 to 450 nm was measured. The slope width is obtained at a wavelength of 72% to 5%. The limiting wavelength is expressed as a (tilt amplitude / 2) + 5% wavelength. The absorption end is expressed at a wavelength of 0.4% transmission. This was used to evaluate the transmittance of 380 nm and 350 nm. ® Properties of the surface of the tritiated cellulose film The surface of the tritiated cellulose film that can be used in the present invention is based on JISB060 1-1 994. The arithmetic average roughness (Ra) of the surface roughness of the film is 0.1 micron or less, and the maximum The height (Ry) is preferably 0.5 μm or less. It is preferable that the arithmetic mean thickness (Ra) is 0.05 micrometers or less and the maximum height (Ry) is 0.2 micrometers or less. The concave and convex shapes of the film surface can be evaluated using an atomic microscope (AFM). Hysteresis in-plane deviation of tritiated cellulose film -91- 200537167 • The tritiated cellulose film that can be used in the present invention preferably satisfies the following formula. Re (MAX)-Re (MIN) | S 3, and | Rth (MAX) — Rth (MIN) | S 5 In the formula, Re (MAX) and Rth (M AX) are randomly cut 1 meter square films The maximum hysteresis 値 値, Re (MIN), Rth (MIN) are the minimum 値. Retention of tritiated cellulose film The tritiated cellulose film that can be used in the present invention requires the retention of various compounds added to the film. Specifically, the mass change of the B film when the tritiated cellulose film usable in the present invention is left at 80 ° C and 90% RH for 48 hours is preferably 0 to 5%, and preferably 0 to 3%. For better, 0 ~ 2% is more preferable. (Evaluation method of retention) The sample was cut into a sample having a size of 10 cm × 10 cm, and the mass was measured after being left in an environment of 23 ° C and 55% RH for 24 hours. The conditions were measured at 80 ± 5 ° C and 90 ± 10% RH. Let stand for 48 hours. Wipe the treated surface lightly, and leave it for one day at 23 ° C, 55% RH to measure the mass, and then calculate the retention by the following method. φ Retention (mass%) = {(mass before placing-mass after placing) / mass before placing} χ100 (mechanical properties of the film) curling Curling of the width direction of the cellulose film which can be used in the present invention 値It is better to use -10 / m ~ + 10 / m. When the halogenated cellulose film usable in the present invention is bonded in a long size, etc., the curl of the width direction of the halogenated cellulose film usable in the present invention is in the foregoing range, and the film can be more effectively prevented. Obstacles in handling, film truncation • 92-200537167, etc. In addition, because the film is reliably in contact with the conveying roller at the edge and center of the film, it can effectively prevent the generation of dust, a lot of foreign matter on the film, point defects of the optical compensation film, and the frequency of the coated lines exceeding the allowance. . Furthermore, it is also preferable from the viewpoint that bubbles can be prevented from entering when bonded to a polarizing film. The curl 値 can be measured according to the method specified by the American National Standards Institute (ANSI / ASCPH 1.29-1 9 8 5). (Tear strength) According to the tear strength (Ermandorf tear method) of JISK 7 1 28-2: 1 988, the film thickness of the tritiated cellulose film that can be used in the present invention is The range of 20 to 80 microns is preferably 2 g or more. 5 to 25 g or more is preferable, and 6 to 25 g or more is more preferable. When converted to 60 micrometers, 8 grams or more is preferable, and 8 to 15 grams is more preferable. Specifically, a 50 mm x 64 mm test piece may be subjected to humidity conditioning at 25 ° C and 65% RH for 2 hours, and then measured using a light load tear strength tester. Amount of residual solvent of tritiated cellulose film The amount of residual solvent of tritiated cellulose film that can be used in the present invention is preferably dried under conditions ranging from 0.01 to 1.5% by mass, and more preferably from 0.01 to 1.0% by mass. good. The curl can be controlled by setting the residual solvent amount of the polarizing film used in the present invention to 1.5% or less. It is more preferably 1.0% or less. The main reason for this effect is considered to be that free deposition can be reduced when the amount of residual solvent is small when forming a film using the solvent casting method described above. Hygroscopic expansion coefficient of tritiated cellulose film The hygroscopic expansion coefficient of tritiated cellulose film which can be used in the present invention is preferably 30x10-5% RH or less. The hygroscopic expansion coefficient is 15xl0_ 5% RH or lower -93- 200537167. It is better, and 10x1 5% RH or lower is more preferable. It is preferable that the coefficient of hygroscopic expansion be smaller, but the normal system is 1 · 0χ1 (Γ 5% RH or more. The coefficient of hygroscopic expansion indicates the amount of change in length of the sample when the relative humidity is changed at a certain temperature. Surface treatment The tritiated cellulose film is subjected to surface treatment according to the situation, which can improve the adhesion to the tritiated cellulose film. For example, light-emitting discharge treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment can be used. The light-emitting discharge treatment referred to in this g can be low-temperature plasma generation by low-pressure gas of 10_3 ~ 20 Torr, and plasma treatment can also be performed at atmospheric pressure. Plasma-excited gas system refers to the plasma under the above conditions. Examples of the excited gas include argon, ammonia, neon, krypton, xenon, nitrogen, carbon dioxide, fluorine such as tetrafluoromethane, and mixtures thereof. These are disclosed in the Invention Association Technical Bulletin (Public Technical Number 200). 1-1 745, 200 Issued on March 15, 2001, Association of Inventions) Details on pages 30 ~ 3 2 are suitable for use in the present invention. Contact angle of saponified cellulose surface treated with alkali saponification alkali saponification It is one of the effective surface treatment methods for the cellulose fiber film that can be used in the present invention. At this time, the contact angle on the surface of the fiber cellulose film after the alkali saponification treatment is preferably 55 degrees or less. The temperature is preferably below 45 °, and more preferably below 45 °. The method of evaluating the contact angle can be a drop of 3 mm in diameter on the surface of the film after the alkali saponification treatment. The light resistance is an index of the light durability of the tritiated cellulose film that can be used in the present invention. -94- 200537167 The super-xenon light is used to irradiate the tritiated cellulose film for 240 hours. The color difference Δ E * ab is preferably 20 or less. It is more preferably 18 or less, and more preferably 15 or less. The color difference can be measured using, for example, UV 3 1 00 (manufactured by Shimadzu Corporation). The measurement method is tritiated cellulose The film was humidity-conditioned at 25 ° C and 60% RH for more than 2 hours, and the color of the tritiated cellulose film was measured before irradiating the xenon light to obtain the initial 値 (L0 *, a0 *, b0 *). Then, Using tritiated cellulose film as monomer, using super xenon light weathering test Machine SX-75 (made by Suga testing machine (stock)), irradiated with xenon light for 240 hours under i50W / m2, 6CTC 50% RH. After a specified time, the tritiated cellulose film was taken out from the thermostatic bath, After adjusting the humidity at 60% RH for 2 hours, the color is measured again, and the 値 (L 1 *, a 1 *, b 1 *) after the irradiation is obtained. From this, the color difference ΔE * can be obtained by ab = ((L0 *-L1 * Plant 2 + (a0 * — al *) • 2 + (b0 * — bl *) · Plant 2 0.5 for measurement. [Examples] Examples and comparative examples are given below. The features of the present invention will be described more specifically. The materials, usage amounts, proportions, processing contents, and processing procedures shown in the following examples can be appropriately changed without departing from the meaning of the present invention. Therefore, the scope of the present invention should not limit the explanation of the specific examples illustrated below. [Example 1] < Manufacturing of IPS-mode liquid crystal cell 1> On a substrate, as shown in Fig. 1, the electrodes were arranged so that the distance between adjacent electrodes was 20 micrometers (2 and 3 in Fig. 1). A polyimide film is provided thereon as an alignment film, and a wiping treatment is performed. Wipe processing is performed in the direction 4 shown in Fig. 1. A polyimide film was provided on one surface of a separately prepared glass substrate, and wiped as an alignment film. The alignment films of the two glass substrates were faced to each other, and the interval (gap; d) of the substrates was -95- 200537167-3.9 micrometers, and the two glass substrates were overlapped and pasted in parallel with each other in a wiping direction. Then, A nematic liquid crystal composition having a refractive index anisotropy (Δη) of 0.0769 and a dielectric constant anisotropy (Δε) of 4.5 was incorporated. The d · Δ η of the liquid crystal layer was 300 nm. < Production of the first retardation region 1 > 170 g of a styrene-based polymer prepared by graft polymerization of 10 parts by weight of the copolymer of the following (A) and 90 parts by weight of the following (B) monomer mixture was dissolved In 830 grams of dichloromethane. • (A) styrene / butadiene copolymer (mass ratio: 20/80) (B) styrene / acrylonitrile / α-methylstyrene (mass ratio: 60/20/20) to dry the solution The film was cast to a glass plate with a thickness of 105 μm. After being left at room temperature for 5 minutes, the film was dried at 45 ° C for 20 minutes, and the obtained film (film) was peeled from the glass plate. Up. This film was attached to a rectangular frame and dried at 70 ° C for 1 hour. After drying at 110 ° C for 15 hours, a uniaxial extension was performed at a rate of 1.9 times using a tensile tester (SUTOROGURAF R2, manufactured by Toyo Seiki Co., Ltd.) at 115 ° C. As described above, the hysteresis 薄 of a film obtained from a uniaxially stretched film of a styrene polymer was measured. Re was 185 nm and Rth was -92 nm. The film has a negative refractive index anisotropy, and the optical axis of the film is in a direction parallel to the film surface (that is, in the film surface). This thin film was used as a first retardation region. < Production of the second phase difference region 1 > The following composition was put into a stirrer, and each component was dissolved while being stirred while heating to prepare a cellulose acetate solution having the following composition. -96- 200537167 Composition of cellulose acetate solution 100% by mass of cellulose acetate having a degree of acetylation of 60.9% triphenyl phosphate (plasticizer) 7.8 parts by mass biphenyl diphenyl phosphate (plasticizer) 3.9 parts by mass Dichloromethane (the first solvent) 300 parts by mass of methanol (the second solvent) 54 parts by mass of 1-butanol (the third solvent) 1 1 part by mass, 80 parts were mixed in another stirrer, and the following 16 parts by mass of the hysteresis値 Ascending agent φ parts by mass of dichloromethane and 20 parts by mass of methanol, stir while heating to delay the ascending agent solution. In a 487 part by mass cellulose acetate solution, 1 1 part by mass of the delayed rhenium rising agent solution was stirred thoroughly to prepare a coating solution. [Chemical Formula 36] The delayed rhenium rising agent

The obtained coating liquid was cast using a tape-type cast. After the belt temperature reached 40 ° C, it was dried with warm air at 60 ° C for 1 minute to peel off the thin band I. Next, the film was dried at 140 ° C for 10 minutes, and the film was about 80 microns thick. The optical characteristics of this film were obtained using an automatic complex refractive index (KOBRA-21ADH, manufactured by Oji Instruments Co., Ltd.), and determined by 湏 [J 定 Re ^ incidence angle dependency '. Re = 15nm, Rth = 120nm. This thin film serves as a second retardation region. < Production of the first polarizing plate with a retardation film > The surface-converted light will be -97- 200537167-so that the commercially available polarizing plate (HLC2-5618, Shanglizi (shares)) 's transmission axis and the first The first phase difference region 1 is bonded to the first phase difference region 1 such that the late phase axes thereof are orthogonal to each other. Then, a commercially available adhesive is applied to the first retardation region 1 at a thickness of 20 μm, and the second retardation region 1 is pasted so that the retardation axis is orthogonal to the transmission axis of the polarizing plate to form a retardation film. Of the first polarizing plate i. < Manufacturing liquid crystal display device 1 > On one side of the IPS mode liquid crystal cell 1 prepared as described above, a first polarizing plate 1 having a retardation film was attached. At this time, the late phase φ axis system of the first phase difference region 1 is orthogonal to the wiping direction of the liquid crystal cell (that is, the late phase axis of the first phase difference region 1 is a liquid crystal molecule that is related to the liquid crystal cell during black display. (The way the late axes are orthogonal). Next, a commercially available polarizing plate (HLC2-5618, manufactured by Shanglizi Co., Ltd.) was attached to the other side of the IPS mode liquid crystal cell 1 by orthogonal polarization to manufacture a liquid crystal display device. The light leakage of the thus produced liquid crystal display was measured. The measurement was started by placing the liquid crystal cell 1 without a polarizing plate on a diaphragm observer installed in a dark room, using an orientation of 45 ° in the left direction based on the wiping direction of the liquid crystal cell, and using the liquid crystal cell method. A luminance meter set at a distance of 60 meters in the direction of the line at a distance of 1 meter measures the luminance 1. Next, the liquid crystal display panel of Example 1 was placed on the same diaphragm observer as described above, and the luminance 2 was measured in the same manner in a dark display state. This is expressed as a ratio of 100 to the luminance 1 The light leakage was 0.0 9%. [Example 2] < Production of first retardation region 2 and retardation film 1 > The surface of a commercially available cellulose acetate film (FUJITAK TD 80UF, Fuji Photo-98-200537167 film (strand)) was cured. After gelatinization, the film was coated with 20 ml / m2 using a wire coating bar. The film was formed by drying at 60 ° C. for 60 seconds and 100 ° C. for 120 seconds. Next, a rubbing treatment is applied to the formed film in a direction parallel to the direction of the retardation axis of the film to form an alignment film. Composition of alignment film coating liquid The following modified polyvinyl alcohol 10 0 parts by mass of water 371 parts by mass methanol 1 1 9 parts by mass

Glutaraldehyde 0. 5 parts by mass Tetramethylammonium fluoride 0.3 part by mass [Chemical Formula 37] Modified polyvinyl alcohol

—F-CH2-CH —)-. _ F CH2-CH—V, I /86.3 V 2 I J12 \ 2 I Λ1β7 ch3 OH OCOCH3 OCONHCH2CH2OCOC «CH2 Next, 1.8 g of the following discotic liquid crystalline compound and 0.2 g Ethylene oxide modified tri (hydroxymethyl) propane triacrylate (V # 3 60, manufactured by Osaka Organic Chemicals Co., Ltd.), 0.06 g of photopolymerization initiator (IRUGAKYUA-907, manufactured by Ciba Cap Technology Co., Ltd.), 0.02 Kemin Huaqi! UKAYAKYUA-DETX, manufactured by Yoshimoto Kagaku Co., Ltd., a solution in which 0.01 g of an air surface side vertical alignment agent (exemplified compound P-6) is dissolved in 3.9 g of methyl ethyl ketone, and # 5 is used. A wire coating rod is coated on the alignment film. Place this on a metal frame and heat in a constant temperature bath at 1 25 ° C for 3 minutes to align the dish-like liquid crystal compound. Next, the dish-like liquid crystal compound was crosslinked by irradiating UV at a temperature of 100 ° C for 120 seconds using a high-pressure mercury lamp of 120 W / cm. It was then left to cool to room temperature. In this manner, a retardation film 1 having a retardation layer formed of a disc-like liquid crystal compound -99-200537167-was produced on a support serving as a protective film for a polarizing plate. '[Chemical Formula 38] Dish liquid crystal compound

The auto-refractive index meter (KOBRA-21ADH, manufactured by Oji measuring equipment φ (strand)) was used to measure the light incident angle dependency of Re of the polarizer protective film 1 by subtracting the contribution of the cellulose acetate film measured in advance. The optical characteristics when only the disc-shaped liquid crystal retardation layer manufactured above were calculated. As a result, it was confirmed that Re was 185 nm, Rth was 93 nm, the average tilt angle of the liquid crystal was 89.9 degrees, and the disc-shaped liquid crystal system was vertically aligned to the film surface. It is known that the refractive index anisotropy of this retardation layer is negative, and the optical axis is substantially parallel to the layers. The method of the late phase of the retardation layer is parallel to the wiping direction of the alignment film. This bit retardation layer is referred to as a first retardation region 2. ^ < Production of the first polarizing plate 2 having a retardation film > A polarizing film was produced by adsorbing iodine on the stretched polyvinyl alcohol film. The obtained retardation film 1 was attached to one side of the polarizing film so that the cellulose acetate film was on the side of the polarizing film using a polyvinyl-based adhesive. The polarizing film is arranged such that the transmission axis of the polarizing film and the retardation film of the retardation film 1 (the retardation axis of the first retardation region 2 also agrees with this) are orthogonal to each other. A commercially available cellulose acetate film (FUJITAK TD 80UF, manufactured by Fuji Photographic Film Co., Ltd.) was saponified, and a polyvinyl alcohol-based adhesive was applied to the opposite side of the polarizing film. In addition, the second phase difference region 1 composed of the acetate fiber -100- 200537167-plain film obtained in Example 1 is such that its late phase axis system is orthogonal to the transmission axis of the aforementioned "light film" The first polarizing plate 2 having a retardation film is attached to the retardation film 1 side. < Manufacturing of liquid crystal display device 2 > The first polarizing plate 2 having a retardation film manufactured as described above is attached to one side of the IPS mode liquid crystal cell 1 manufactured as described above. At this time, the manner in which the retardation axis of the first retardation region 2 of the aforementioned polarizing plate 2 is orthogonal to the wiping direction of the liquid crystal cell (that is, when the retardation axis of the first retardation region 2 is shown in black φ (The method is orthogonal to the late phase axis of the liquid crystal molecules of the liquid crystal cell), and the second phase difference region 1 is attached on the liquid crystal cell side. Next, a commercially available polarizing plate (HLC2-5618, manufactured by Shanglizi Co., Ltd.) was attached to the other side of the IPS mode liquid crystal cell 1 by orthogonal polarization to manufacture a liquid crystal display device. The light leakage of the thus-produced liquid crystal display device was 0.09%. [Example 3] < Production of the first polarizing plate 3 having a retardation film > A dish φ-shaped liquid crystal coating liquid of the same composition used in the production of the retardation film 1 of Example 2 was performed with # 4 · 1. The retardation film 2 was applied in the same manner as in Example 2. After subtracting the contribution of the triacetate cellulose support of this retardation film 2, Re was 130 nm and Rth was -65 nm. In the retardation film 2, the dish-like liquid crystalline compound in the retardation layer is aligned vertically as in the retardation film 1. The retardation layer formed of a discotic liquid crystalline compound has negative refractive index anisotropy, and the optical axis is substantially parallel to the plane. This phase difference layer is referred to as a first phase difference region 3. The extended polyvinyl alcohol film was made to adsorb iodine to produce a polarizing film. Using the adhesive, the retardation film 2 was pasted on the side of the polarizing film with the dish-like liquid crystal layer on the polarizing film side. The polarizing film is arranged so that the transmission axis of the polarizing film and the retardation film of the retardation film 2 are orthogonal to each other. A commercially available cellulose acetate film (FIHITAK TD 80UF, made by Fuji Photo Photo Film (stock)) was saponified, and a polyvinyl alcohol-based adhesive was used to stick to the opposite side of the polarizing film. Then, a commercially available cellulose acetate film was stuck on the retardation film 2 side to produce a first polarizing plate 3 having a retardation film. At this time, the tertiary ethyl acetate cellulose support of the retardation film 2 and the aforementioned cellulose acetate film system adjoining it as the second retardation region 3 function. Rth of the second B phase difference region 3 is 110 nm, and Re is 2 nm. < Manufacturing of the liquid crystal display device 3 > On the side of the IPS mode liquid crystal cell 1 manufactured as described above, the late phase axis system of the second phase difference region 3 of the first polarizing plate 3 having a retardation film and the liquid crystal cell The wiping direction is orthogonal (that is, the retardation axis of the first retardation region 3 is orthogonal to the retardation axis of the liquid crystal molecules of the liquid crystal cell during black display), and the retardation film 2 side is The LCD side is attached. Next, a commercially available polarizing plate (HLC2-5618, manufactured by Shanglizi Co., Ltd.) was attached to the other side of the IPS-mode liquid crystal cell 1 with orthogonal φ polarization to manufacture a liquid crystal display device. The light leakage of the thus-produced liquid crystal display device was 0.88%. [Example 4] < Production of support 1 > Cellulose acetate A was prepared by putting the following composition into a mixing tank, stirring and dissolving each component while heating. -102- 200537167 < Composition of cellulose acetate solution A > 100 parts by mass of triphenyl phosphate (plasticizer) with a degree of substitution of 2.86 7.8 parts by mass of biphenyl diphenyl phosphate (plasticizer) 3.9 parts by mass Dichloromethane (the first solvent) 300 parts by mass of methanol (the second solvent) 54 parts by mass of 1-butanol Π parts by mass was put into another stirring tank to dissolve each component to prepare an additive solution B. < Composition of additive solution B > and stirring while heating 80 parts by mass of methylene chloride 20 parts by mass of methanol 20 parts by mass The following optical anisotropy reducing agent [Chemical Formula 39] 40 parts by mass

40 parts by mass of the additive solution B was added to 477 parts by mass of the cellulose acetate solution A, and the coating solution was prepared by sufficiently stirring. The coating solution was cast from a casting nozzle onto a roller cooled to 0 ° C. Both ends in the width direction of the film peeled from the field and the solvent content rate was 70% by mass were fixed to a needle plate tenter (the needle plate tenter described in JP-A-Heisei 4- 1 009 as shown in FIG. 3). In a state where the content rate is 3 to 5% by mass, drying is performed while maintaining an interval of 3% in the lateral direction (the direction perpendicular to the mechanical direction). Subsequently, it was further dried by being transported between the rollers of the heat-103-200537167-processing device to obtain a support body 1 having a thickness of 80 * micron. Using an automatic birefringence meter (KOBRA-21ADH Measuring Instruments Co., Ltd.), the dependence of the incident angle of Re light was measured, and the optical characteristics were calculated. As a result, it was confirmed that Re was 1 nm and Rth was 6 nm. < Production of the first polarizing plate 4 having a phase film > A retardation film 1 was manufactured in the same manner as in Example 2 except that the above-mentioned support 1 was used as the support and a # 4.2 rod was used to coat the dish-shaped liquid crystal coating liquid, φ A retardation layer is formed on the support 1. The retardation layer formed had a Re of 140 nm and a Rth of -70 nm. The discotic liquid crystalline compound in the formed retardation layer is vertically aligned like the retardation film 1. The refractive index anisotropy of the retardation layer formed of a discotic liquid crystalline compound is negative, and the optical axis is substantially parallel to the plane. This phase difference layer is referred to as a first phase difference region 4. A cellulose acetate film was produced in the same manner as in the production of the second retardation region 1 of Example 1 except that the retarded rhenium raising agent solution was 9.2 parts by mass. Rth of the obtained cellulose acetate film was 110 nm, and Re was 7 nm. This cellulose acetate film was adhered to the first retardation region 4 as the second retardation region 4 by the same method as in Example 2 except that the adhesive was coated and sold at a thickness of 20 µm. Using a polyvinyl alcohol-based adhesive, the laminated body of the first retardation region 4 and the second retardation region 4 was affixed to the side of the polarizing film obtained in Example 2 with the support 1 being on the side of the polarizing film. . The polarizing film is arranged so that the transmission axis of the polarizing film is orthogonal to the late phase axis of the first retardation region 4 (the late phase agent of the first retardation region 2 coincides with this). The commercially available cellulose acetate film was subjected to a saponification treatment -104- 200537167-and attached to the opposite side of the polarizing film to produce a first polarizing plate 4 having a retardation film. < Manufacturing of liquid crystal display device 4 > On the side of the IPS mode liquid crystal cell 1 manufactured as described above, the late phase axis system of the first phase difference region 4 of the first polarizing plate 4 having a retardation film and the liquid crystal cell The wiping direction is orthogonal, and the second retardation film region 4 side is attached to the liquid crystal cell side. Next, a commercially available polarizing plate (HLC2-5618, manufactured by Shangliz Co., Ltd.) was attached to the other side of the IPS-mode φ-type liquid crystal cell 1 by orthogonal polarization to manufacture a liquid crystal display device. The light leakage of the liquid crystal display device thus obtained was 0.09%. [Example 5] < Production of the first polarizing plate 5 having a retardation film> A cellulose acetate film was produced in the same manner as in the second retardation region 2 of Example 2 except that the hysteresis rising solution was 7 parts by mass. The Rth of this film was 80 nm and the Re was 9 nm. This thin film is referred to as a second retardation region 5. Next, except that the prepared second phase retardation region 5 composed of cellulose acetate was used as a support, and a # 4.3 rod was used to coat the dish-shaped liquid crystal coating liquid, the retardation film 1 of Example 2 was used. The same manufacturing method is used to form the layer. The prepared layer had Re of 145 nm and Rth of 73 nm. In the layer, the dish-like liquid crystalline compound is fixed in a vertical alignment state. The refractive index of this layer is negative, and the optical axis is substantially parallel to the layer. This phase difference layer is referred to as a first phase difference region 5. On the other hand, the polarizing film produced in Example 2 was laminated with a polyvinyl alcohol-based adhesive so as to be sandwiched between the support 1 and a commercially available cellulose acetate film subjected to saponification treatment to produce a polarizing plate A. Apply the adhesive on the support-105-200537167 ^ body 1 side of this polarizing plate, and attach the round ^ coating side of the first retardation area 5 to manufacture the first polarizing plate 5 with retardation film < liquid crystal display Manufacture of device 5> On one side of the IPS mode liquid crystal cell 1 manufactured as described above, the wiping direction of the late-phase liquid crystal cell of the first phase difference region 5 of the first polarizing plate 5 of the parallax film is orthogonal, The second retardation region is affixed on the liquid crystal cell side. Next, on the cell-side of the IPS-mode liquid crystal, the support 1 of the polarizing plate A is used as the cell-side, and it is stuck in a positive g manner to manufacture a liquid crystal display device. The light leakage of the liquid crystal device thus prepared was 0.03%. [Example 6] < Production of the first polarizing plate 6 having a retardation film > Except for a state where the retardation rhenium raising agent solution was 6 parts by mass and the solvent contained 3 to 5% by mass, the horizontal direction was maintained (machine The acetic acid ^ film was produced by the same method as that of the production of the second phase difference region 2 except that the elongation in the vertical direction was stretched at intervals of 25%. The Rth of this film was 75 nm and the Re was 30 nm. This film 2 has a retardation region 6. Next, the phase is the same as that of Example 2 except that the second retardation region 6 made of cellulose acetate is used as a support and a # 4.1 rod-shaped liquid crystal coating liquid is used. The difference film 1 is formed by the same method. The Re of the thin film obtained is 135 nm, -67 nm. In the layer, the dish-like liquid crystalline compound is fixed in a vertical alignment. The refractive index anisotropy of the layer is Negative, the optical axis is parallel to the plane. This retardation layer is used as the first retardation region 6. On the other hand, the support plate-shaped liquid of the polarizing plate A obtained in Example 5 has an axis system and a 5-side system. 1) The other cross-polarized light shows that the loading rate is Ϊ direction) Example 2 Cellulose as the second film The coated Rth is coated in a state of being substantially supported. 1 -106- 200537167 Fei-The side is coated with an adhesive, and the disc-shaped side of the first retardation region 6 is pasted to produce the first polarized light having a retardation film. Plate 6. < Manufacturing of the liquid crystal display device 6 > In a manner in which the wiping direction of the liquid crystal cell in the first retardation region 6 of the first polarizing plate 6 of the side retardation film of the IPS mode liquid crystal cell 1 manufactured as described above is orthogonal, The second phase difference is affixed to the liquid crystal cell. Next, on the liquid side of the IPS mode, the support 1 of the polarizing plate A is used as a cell side, and a positive φ type is attached to manufacture a liquid crystal display device. The light leakage of the liquid crystal thus obtained was 0.04%. [Example 7] < Production of ferroelectric liquid crystal cell 1 > A polyimide film was provided on a glass substrate having an ITO electrode, and a wiping treatment was performed. Make two pieces of this substrate, make the alignment film so that the distance between the substrates (gap; d) is 1.9 microns, and overlap and attach the two glass-wipe directions in parallel, and then set the refractive index ^ (△ η) to 0.15 and spontaneous polarization (Ps) is an iron product of 12nCcm_2. The d · Δ η of the liquid crystal layer is 280 nm. A first polarizing plate 2 having a retardation film was obtained on one of the two sides of the obtained ferroelectric liquid crystal cell 1. Example 2 The retardation axis system of the first retardation region 2 of this polarizing plate 2 is pasted such that the retardation axis 2 of the liquid crystal molecules orthogonal to each other when the DC voltage is applied at 10V is on the liquid crystal cell side. The other side of the electric liquid crystal cell 1 is an orthogonally polarized light plate (HLC2_5618, manufactured by Shangliz Co., Ltd.) to manufacture a liquid crystal liquid crystal coating surface to have a late phase axis system and a region 6 side system cell The film of a cross-polarized square display device of 1 is used as the alignment [the opposite direction, the rubbing rate of the glass substrate is different from the direction of the electric liquid crystal group, and when it is pasted and implemented, the foregoing is applied in the liquid crystal cell mode, and then, in iron. Commercially available bias display devices. -107- 200537167 The light leakage of the liquid crystal display thus manufactured was 0.10%. [Example 8] < Production of support 2 > (Preparation of cellulose acetate solution) The following composition was put into a stirring tank, and stirred to dissolve cellulose acetate solution A. (Composition of cellulose acetate solution A) Cellulose acetate with a degree of acetylation of 2.86 φ methylene chloride (first solvent) methanol (second solvent) (preparation of matting agent solution) 20 parts by mass average particle size 16nm (AEROSIL R972, made by Ayloziru (share), stir well and mix for 30 minutes to make the silica particle dispersion into the disperser with the following composition, and then dissolve each component to prepare a matting agent. (Composition of Matting Solution) Dispersion of Dioxide Dioxide Particles with an Average Particle Size of 16 n m Dichloromethane (first solvent) Methanol (second solvent)

Cellulose acetate solution A (preparation of additive solution) The following composition was put in a stirrer and heated to prepare a cellulose acetate solution. (Additive composition) Each component was decomposed to prepare 100.0 parts by mass, 402.0 parts by mass, 6 0.0 parts by mass of silica particles, and 80 parts by mass of methanol 'sub-dispersion. This: Stir for 30 minutes to 1 0.0 parts by mass 7 6.3 parts by mass 3.4 parts by mass 10.3 parts by mass Dissolve each component while stirring -108- 200537167

Compound (A _ 丨 9) for reducing optical anisotropy Wavelength dispersion adjusting agent (UV-102) Dichloromethane (first solvent) Methanol (second solvent) Cellulose acetate solution A 49.3 parts by mass 7.6 parts by mass 5 8.4 parts by mass 8.7 parts by mass, 1 2.8 parts by mass, and Log P 値 of A-19 and UV-102 were 2.9 and 5.6, respectively. (Production of cellulose acetate film) 94. 6 parts by mass of the above cellulose acetate solution A, 1.3 parts by mass of matting agent φ4.1, and 4.1 parts by mass of additive solution were filtered and mixed, respectively, and cast using a belt-type casting machine. . The mass ratio of the compound having the above-mentioned composition to reduce optical anisotropy and the wavelength dispersion modifier to cellulose acetate were 12% and 1.8%, respectively. A film having a residual solvent content of 30% was peeled from the tape, and dried at 140 ° C for 40 minutes to produce cellulose ethyl ester. The residual cellulose content of the obtained cellulose acetate film was 0.2%, and the film thickness was 40 m. The Re (630) of this film was 0.3 nm, Rth (630) was 3.2 nm, | Re (400) —Re (700) I was 1.2 nm, and I Rth (400) —Rth (700) I was 7.5 nm. The Tg of the φ thin film was 134.3t, the haze of the thin film was 0.34%, and the Δΐαΐι (10% KΗ—80% RH) was 24.9nm. This thin film was used as the protective film 1. < Production of polarizing plate B > Next, the extended polyvinyl alcohol was used to adsorb iodine to produce a polarizing film. Commercially available cellulose acetate film (FUJflTAK TD 80UF, Fuji Photographic Film (Stock), Re = 2nm, Rth = 48 nm), and then apply a polyethylene glycol-based adhesive to one side of the polarizing film. Then, the support 2 is attached to the other side of the polarizing film so that the cellulose acetate film side is on the polarizing film side, and a polarizing plate B is manufactured. -109- 200537167 [Example 8] 'Adhesive was applied to the support 2 side of the polarizing plate B of the second retardation region 5 and the first retardation region 5 formed in the same manner as in Example 5, and the first retardation region was formed. The first plate-shaped polarizing plate 8 having a retardation film was produced by sticking the dish-shaped liquid crystal application surface side of the fifth plate. < Manufacturing of the liquid crystal display device 8 > On the side of the IPS mode liquid crystal cell 1 manufactured as described above, the late phase axis system of the first retardation region 5 of the first polarizing plate 8 having a retardation film and the φ liquid crystal A method in which the wiping directions of the cells are orthogonal, and the side of the second retardation region 5 is attached to the side of the liquid crystal cell. Next, on the other side of the IPS-mode liquid crystal cell 1, the support 1 of the polarizing plate A is used as the cell side, and a liquid crystal display device is manufactured by applying orthogonal polarization. The light leakage of the thus-produced liquid crystal display device was 0.02%. [Comparative Example 1] A polarizing plate (HLC2-5618, manufactured by Shanglizi) was attached to both sides of the IPS mode liquid crystal cell 1 manufactured as described above by orthogonal polarization to produce a liquid crystal φ display device. No optical compensation film is used. The protective film of this commercially available polarizing plate was peeled off in hot water and the optical properties were measured. Re (6 3 0) was 4.7 nm, Rth (630) was 48.5 nm, and Re (400) — Re (700 ) | Is l0.1 nm, I Rth (400)-Rth (700) I is 23.4 nm. The liquid crystal display device described above is attached to the polarizing plate so that the penetrating axis of the polarizing plate on the upper side is parallel to the wiping direction of the liquid crystal cell as in Example 1. The light leakage of the liquid crystal display device thus obtained was 0.55%. [Comparative Example 2] < Production of the first polarizing plate 9 having a retardation film > -110- 200537167 A polarizing film was produced by adsorbing iodine on the stretched polyvinyl alcohol film. Using a polyvinyl alcohol-based adhesive, the retardation film 1 obtained in Example 2 was attached to one side of the polarizing film so that the cellulose ester film was on the side of the polarizing film. The polarizing film is arranged so that its transmission axis is parallel to the retardation axis of the retardation film 1. A commercially available cellulose acetate film (FIHITAK TD 80UF, manufactured by Fuji Photographic Film Co., Ltd.) was saponified, and a polyvinyl alcohol-based adhesive was applied to the opposite side of the polarizing film. Then, the second retardation region 1 obtained in Example 1 was pasted on the phase φ difference film 1 side so that its late phase axis system was orthogonal to the transmission axis of the polarizing plate, and a phase difference film 1 was manufactured. First polarizing plate 9. < Manufacturing of the liquid crystal display device 9 > On the side of the IPS mode liquid crystal cell 1 manufactured as described above, the late phase axis system of the first phase difference region 1 of the first polarizing plate 1 having a retardation film and the liquid crystal cell The rubbing direction is parallel, and the second retardation region 1 side is attached to the liquid crystal cell side. Next, a commercially available polarizing plate (HLC2-5618, manufactured by Shanglizi Co., Ltd.) was attached with a cross polarized configuration to manufacture a liquid crystal display device. The light leakage of the thus-produced liquid crystal display device was 0.48%. [Comparative Example 3] A first polarizing plate 3 having a retardation film was manufactured in the same manner as the first polarizing plate 2 having a retardation in Example 2 except that the second retardation region was not bonded. On the side of the IPS mode liquid crystal cell 1 manufactured in Example 1, the retardation axis system of the first retardation region 2 of the first polarizing plate 3 having the retardation film is orthogonal to the wiping direction of the liquid crystal cell. The dish-shaped liquid crystal application surface side is attached to the liquid crystal cell side. Next, on the other side of the IPS-mode liquid crystal cell 1, a commercially available polarizing plate (HLC2-5618, manufactured by Sunlinks Co., Ltd.-111-200537167) was pasted in an orthogonally polarized configuration to manufacture a liquid crystal display device. The light leakage of the liquid crystal display device thus obtained was 1.5%. The evaluation results of Examples 1 to 8 and Comparative Examples 1 to 3 are summarized below. [Table 1] The first crystal moon 'polarizer's liquid-bag-side protective film 1st retardation region 2nd retardation region 2nd polarizing film liquid crystal cell-side protective film Light leakage material Rth (nm) Material Re (nm) Material Re (nm) Rth (nm) Material Rth (nm) Example 1 TAC 45 Polystyrene film 185 TAC 15 120 TAC 45 0.09% Example 2 TAC 45 DLC 185 TAC 15 120 TAC 45 0.09% Example 3--DLC 130 TAC (2 pieces) 2 110-48 0.08% Example 4 TAC 6 DLC 140 TAC 7 110 TAC 48 0.09% Example 5 TAC 6 DLC 145 TAC 9 80 TAC 5 0.03% Example 6 TAC 6 DLC 135 2-axis TAC 30 75 TAC 5 0.04% Example 7 TAC 45 DLC 185 TAC 15 120 TAC 45 0.10% Example 8 TAC 2 DLC 145 TAC 9 80 TAC 2 0.02% Comparative Example 1 TAC 45 4ΐΐΤ-4π3ΐ ιιΓ if 11 J \\\ ^ \\\ TAC 45 0.55% Comparative Example 2 TAC 45 DLC 185 TAC 15 120 TAC 45 0.48% Comparative Example 3 TAC 45 TAC 15 120 | TAC 45 1.5% In the table, TAC represents the meaning of triethylfluorene cellulose film. In the table, DLC means the meaning of dish-shaped liquid crystal. In the table, the late phase axis of the first retardation region is parallel to the transmission axis of the first polarizing film. [Brief description of the drawings] FIG. 1 is a schematic diagram showing an example of a pixel area of a liquid crystal display device of the present invention. Fig. 2 is a schematic diagram showing an example of a liquid crystal display device of the present invention. [Description of Symbols of Main Components] 1 Pixel area of liquid crystal element 2 Pixel electrode 3 Display electrode 4 Wipe direction -112- 200537167 " 5 a, 5 b Orientation direction of liquid crystal compound during black display 6a, 6b Liquid crystal compound during white display Alignment directions 7a, 7b, 19a, 19b Protective film for polarizing film 8, 20 Polarizing film 9, 21 Polarizing light transmission axis of polarizing film 10 First phase difference area 11 First phase difference area Late phase axis 12 Second phase difference area 13, 17 Cell substrate 14, 18 Wipe direction of the cell substrate 15 Liquid crystal layer 16 Late phase direction of the liquid crystal layer

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Claims (1)

200537167 X. Scope of patent application: 1 · A liquid crystal display device in which a first polarizing film, a first retardation region and a second retardation region, a first substrate, a liquid crystal layer, a second substrate, and a second polarizer are arranged in the following order. It is made of a polarizing film. The alignment of liquid crystal molecules of the liquid crystal layer is parallel to the surfaces of the pair of substrates during black display. The retardation in the second retardation region 差 Re is 100 nm or less, and the retardation in the thickness direction 値 Rth 50nm to 200nm, the refractive index anisotropy of the first retardation region is negative and the optical axis is substantially parallel to the layer system. • The late axis system of the first retardation region and the transmission axis of the first polarizing film. The direction of the retardation axis of the liquid crystal molecules is orthogonal to the black display. 2. The liquid crystal display device according to item 1 of the patent application range, wherein Re of the first phase difference region is 50 nm to 400 nm. 3. The liquid crystal display device according to item 1 or 2 of the patent application scope, wherein the late phase axis system of the second phase difference region is substantially orthogonal to the transmission axis of the first polarizing film. 4. The liquid crystal display device according to any one of claims 1 to 3, wherein at least one of the first retardation region and the second retardation region contains a discotic liquid crystal compound. 5. The liquid crystal display device according to any one of claims 1 to 4, wherein a second polarizing film is provided on the outer side of the second substrate. 6. The liquid crystal display device according to any one of claims 1 to 5 in the scope of application for a patent, wherein a pair of protective films are arranged to sandwich the first polarizing film and / or the second polarizing film, and the pair of protections The phase difference Rth in the thickness direction of the protective film in the film near the liquid crystal layer side is 25 nm or less. 7 · If the liquid crystal display device of any one of items 1 to 6 of the scope of patent application, -114- 200537167 ·-which is arranged to sandwich the first polarizing film and / or the second polarizing film " There are a pair A protective film, the protective film of the pair of protective films near the liquid crystal layer side is a halogenated cellulose film or a norbornene-based film. 8. The liquid crystal display device according to item 6 of the scope of patent application, wherein a pair of protective films are arranged to sandwich the first polarizing film and / or the second polarizing film, and the pair of protective films is close to the liquid crystal layer side. The protective film is a tritiated cellulose film that satisfies the following (I) and (II), (I) OS Re (630) S 10, and | Rth (630) | S 25 (II) | Re (400)- Re (700) IS 10, and | Rth (400)-Rth (700) | S 35 (In the formulae (I) and (II), Re (A) represents the hysteresis (nm) 'in the plane of the wavelength Anm) Rth (A) is a hysteresis (nm) that is not in the film thickness direction at a wavelength of λ nm. 〇9. The liquid crystal display device according to item 8 of the patent application scope, wherein the tritiated cellulose film satisfies the following formula (III The range of) and (IV) contains at least one compound that reduces the hysteresis of the tritiated cellulose film in the film thickness direction, (III) (Rth (A) — Rth (0)) / AS — 1.0 • (IV) 0.01 ^ A ^ 30 (In the formulae (III) and (IV), Rth (A) represents the Rth (nm) of a tritiated cellulose film containing a compound that reduces Rth by A%, and Rth (0) represents the tritiated Rth (nm) of tritiated cellulose membranes containing cellulose compounds not containing compounds that reduce Rth (λ) The A series represents the weight (%) of a compound that reduces Rth (again) relative to the cellulose film base polymer). 1 · The liquid crystal display device as claimed in claim 8% or 9 of the patent scope, wherein the tritiated cellulose 0 Wu 'contains at least one kind of tritiated cellulose in the substitution degree of 2.85 ~ 3.00. A compound for reducing Rth (λ), the compound-115-200537167 has a solid content of 0.01 to 30% by mass relative to tritiated cellulose ° 1 1 · As a liquid crystal display of any one of claims 8 to 10 in the scope of patent application Device, wherein the tritiated cellulose film contains at least one compound that can reduce the Rth (400)-Rth (700) I of the tritiated cellulose film 'The solid content of the compound relative to the tritiated cellulose is 0.01 ~ 30% by mass. 1 2. The liquid crystal display device according to any one of claims 8 to 11 in the scope of patent application, wherein the thickness of the halogenated cellulose film is 10 to 120 microns. 1 3. The liquid crystal display device according to any one of claims 8 to 12, wherein the tritiated cellulose film contains at least one kind of reduced Rth (λ) and an octanol-water partition coefficient (Log P) A compound of 0 to 7 having a solid content of 0.01 to 30% by mass based on the solid content of the tritiated cellulose. 1 4 · The liquid crystal display device according to item 13 of the patent application scope, which contains a compound that can reduce the Rth (λ) and the octanol-water partition coefficient (Log ρ 値) is 0 ~ 7, which is selected from the following formula General formula (13) or at least one of the compounds represented by the following general formula (18), [Chemical Formula 1] General formula (13) 2 (In the general formula (13), R11 represents an alkyl group or an aryl group, and R12 and ru represent a separate hydrogen atom, an alkyl group, or an aryl group) [Chemical Formula 2] -116- 200537167 ·-General Formula (1 8) · — O R16 I! I ^ R14—C—N-R15 (In the general formula (18), R14 is an alkyl group or an aryl group, and R15 and R16 are each independently a hydrogen atom, a radical or an aromatic group. base). 1 5. The liquid crystal display device according to any one of claims 8 to 14 in the scope of patent application, wherein the tritiated cellulose film has a spectral transmittance of 45 to 95% at a wavelength of 3 to 80 nm, and a wavelength of 350 nm. The spectral transmittance is 10% or less. g 1 6. The liquid crystal display device according to any one of items 8 to 15 of the patent application, wherein the halogenated cellulose film is treated for 240 hours under an environment of 60 ° C and 90% RH, and then cured. The amount of change in Rth (λ) of the cellulose film is 15 nm or less. 1 7. The liquid crystal display device according to any one of claims 8 to 16 in the scope of patent application, wherein after treating the tritiated cellulose film in an environment of 80 ° C for 240 hours, the Rth ( λ) is 15 nm or less. 1 8 · The liquid crystal display device according to any one of claims 8 to 17 in the scope of patent application, wherein the frontal retardation in the film surface of the tritiated cellulose film is full ^ S The following formula, I Re (n )-Re (0) | / η ^ 1.0 (where Re (n) is the in-plane frontal hysteresis (nm) of η (%) stretched film, and Re (0) is the in-plane frontal hysteresis of unstretched film値 (nm)). 19. The liquid crystal display device according to any one of claims 8 to 18, wherein the tritiated cellulose film is in the film surface and is perpendicular to the film conveying direction (MD direction) of a machine for manufacturing the film The direction (TD direction) has a late phase axis. -117- 200537167 ^ 2 (K as in the liquid crystal display device of any of claims 1 to 19 in the scope of application for patents, wherein the tritiated cellulose film extends in the direction of the film with a slow axis When the frontal hysteresis becomes smaller, the frontal hysteresis becomes larger when extending in a direction perpendicular to the direction having the retardation axis. 2 1 · As for any of the liquid crystal display devices of the first to the 20th of the scope of patent application, the device is installed therein. The first retardation region and the second retardation region are arranged at a position of one of the pair of substrates of the liquid crystal cell which is closer to the substrate on the opposite side to the observation side. Φ 22. As in any of the items 1 to 21 of the scope of patent application The liquid crystal display device of one item, wherein the first phase difference region and the second phase difference region are arranged at a position closer to the observation-side substrate among the pair of substrates of the liquid crystal cell. -118