TW581885B - Optical compensator, polarizer and liquid crystal display - Google Patents

Abstract

The present invention relates to an optical compensator used in liquid crystal displays, which has a cellulose acetate film consisting of a cellulose acetate having a degree of acetylation of 59.0 to 61.5% and 0.01 to 20 mass% of an aromatic compound having at least two aromatic rings based on 100 mass% of the cellulose acetate. The cellulose acetate film has a Re retardation of 0 to 200 nm, a Rth retardation of 70 to 400 nm and a thickness of 10 to 70 mum.

Description

581885 V. Description of the invention (1) [Technical Field] The present invention relates to an optical compensation sheet, a polarizing plate and a liquid crystal display device using the same. [Prior art] Cellulose acetate film can be used for various photographic materials or optical materials in terms of its toughness and flame retardancy. Cellulose acetate film is a typical carrier of photographic photosensitive materials. The cellulose acetate film can also be used in liquid crystal display devices. Compared with other polymer films, cellulose acetate films are characterized by high optical isotropy (low hysteresis). Therefore, for applications requiring optical isotropy, such as protective films for polarizing plates, cellulose acetate films are generally used. In contrast, the optical compensation sheet (phase difference film) of the liquid crystal display device requires optical anisotropy (high hysteresis). Therefore, the optical compensation sheet generally uses a synthetic polymer film having a high retardation such as a polycarbonate film or a polyfluorene film (specifically, a stretched birefringent film obtained by stretching a synthetic polymer film). As mentioned above, in the technical field of optical materials, when polymer films are required to have optical anisotropy (quotient hysteresis), synthetic polymer films are used, and when optical isotropy (low hysteresis) is required, cellulose acetate film. It is disclosed in European Patent No. 0 9 1 1 6 5 6 A 2 that cellulose acetate films with high hysteresis can be used for applications requiring optical anisotropy based on conventional general principles. It is revealed that by inserting the cellulose acetate film into polarized light 581885 5. Description of the invention (2) Between the panel and the liquid crystal cell, a liquid crystal display device with high display quality can be obtained.

It is proposed to replace the stretched birefringent film with an optical compensation sheet containing an optically anisotropic layer containing a disc-shaped compound on a transparent support. The optically anisotropic layer is formed by aligning a disc-shaped compound and fixing the alignment state. The discoid compound generally has a large birefringence. Moreover, the disk-shaped compound has various alignment morphologies. Therefore, when a disc-shaped compound is used, an optical compensation sheet having optical properties not known in a conventional stretched birefringent film can be obtained. An optical compensation sheet using a disc-shaped compound is described in the specifications of Japanese Patent Application Laid-Open No. 6-214116, U.S. Patent No. 5,853,679, No. 5667703, and West German Patent Publication No. 39 1 1 620A1. Furthermore, the λ / 4 plate to which the optical compensation sheet is applied has various uses related to an antireflection film or a liquid crystal display device. However, even if it is called; I / 4 board, most of them are those who reach λ / 4 within a certain wavelength.

JP Laid-open Nos. 5-27118 and 5-27119 disclose λ / 4 plates in which the optical axis of a birefringent film with a large hysteresis and a birefringent film with a small hysteresis are orthogonally crossed. When the retardation of the two thin films is λ / 4 for all specific wavelengths, it theoretically functions as a λ / 4 plate for the entire visible light range. Japanese Patent Application Laid-Open No. 10-6 8 8 1 6 discloses that a polymer film having a specific wavelength of λ / 4 and a polymer film made of the same raw material and a polymer film having the same wavelength as λ / 2 are laminated at a wide range of wavelengths. Fan 圔 can get λ / 4 of λ / 4 plate. Japanese Patent Application Laid-Open No. 10-90521 also discloses that it can be achieved in a wide range of wavelengths by laminating two polymer films; ^ / 4 of a λ / 4 plate. The above poly 581885 V. Description of the invention (3) The composite film can be a stretched film of synthetic polymer such as polycarbonate. 0 Liquid crystal display (LCD) and <: RT (cathode) 1 inch wire tube) phase Ratio, has the advantage of being thin > light weight \ low power consumption. The liquid crystal display device is composed of a liquid crystal cell and a pair of polarizing plates arranged on both sides of the liquid crystal cell. A liquid crystal cell is formed by rod-shaped liquid crystal molecules, two substrates enclosed therein, and an electrode layer for applying voltage to the rod-shaped liquid crystal molecules. In order to align the enclosed rod-shaped liquid crystal molecules, an alignment film is provided on two substrates. The polarizing plate is formed by setting a transparent protective film on both sides of the polarizing film. When the coloring of the image displayed in the liquid crystal cell is removed, most of the time, an optical compensation plate (phase difference plate) is set between the liquid crystal cell and the polarizing plate. The laminated body of the polarizing plate (or polarizing film) and the optical compensation sheet has the function of an elliptical polarizer. 0 The optical compensation sheet also has the function of expanding the viewing angle of the liquid crystal cell. 0 The optical compensation sheet has been used since ancient times. Refractive index film 〇In the current mainstream TN (twisted nematic) TFT (thin film transistor) liquid crystal display device, as described in JP-A-8-50206, an optical compensation sheet is inserted between a polarizing plate and a liquid crystal cell, and the display is achieved. The quality bureau ’s liquid crystal display device 0 However, this method causes problems such as the liquid crystal display device becoming thicker. In Japanese Patent Application Laid-Open No. 1-68940, an optical compensation sheet is used on one surface of the polarizing film. An elliptical polarizing plate with a protective film on the other side prevents the liquid crystal display device from becoming thick and improves the front contrast. The optical compensation sheet of the invention is prone to phase differences due to distortion such as heat. 0 Second 5 Liquid crystal display device When the display is black, the transmittance of the frame edges in the display screen will increase (light leakage).

581885 V. Description of the invention (4) 〇 For the problem of phase difference caused by distortion, in Japanese Patent Application Laid-Open Publication No. 7-191217 and European Patent No. 09 1 1 656A2, the optical disc (round The optical compensation sheet of the optically anisotropic layer formed by the compound of a disk shape is directly used as a protective film of the polarizing plate, so that the liquid crystal display device does not become thick, and the problem of durability can be solved. In addition, U.S. Patent Nos. 458 3 825 and 54 1 0422 have disclosed the use of a curved alignment type liquid crystal cell in which rod-shaped liquid crystal molecules are aligned substantially in opposite directions (symmetrically) on the upper and lower portions of the liquid crystal cell. . Since the rod-shaped liquid crystal molecules are symmetrically aligned above and below the liquid crystal cell, the curved alignment type liquid crystal cell has its own optical compensation function. Therefore, this liquid crystal type is also referred to as an OCB (Optically Compensated Bending) liquid crystal type. The curved alignment type liquid crystal display device has the advantage of a fast response speed. Compared with the general liquid crystal type (TN type, STN type), the bending alignment type has the characteristics of wider viewing angle and faster response speed. However, an optical compensation sheet made of a conventional stretched birefringent film has insufficient optical compensation function for a bending alignment type liquid crystal display device. It is proposed to replace the stretched birefringent film with an optical compensation sheet having an optically anisotropic layer containing a disc-shaped compound and a transparent carrier as described above. The use of discs is disclosed in Japanese Patent Application Laid-Open No. 9-1 97 3 97 (US Patent No. 5 805 2 53) and International Patent No. W 096/3 7804 (European Patent No. 2007 3 3 28A). Bending alignment type liquid crystal display device for optical compensation sheet of compound in the form of a compound. Significant improvement can be achieved by using optical compensation plates containing disc-like compounds

581885 V. Description of the invention (5) Viewing angle of curved alignment type liquid crystal display device. In addition, in Japanese Unexamined Patent Publication No. 1 1-3 1 6 3 7 8 the use of optical compensation sheets containing disc-shaped compounds in curved alignment type liquid crystal display devices was reviewed. There may be light leakage at specific wavelengths, and color may be displayed on the display image. problem. The reason for this coloring is related to the wavelength of the transmittance of the elliptical polarizer (the laminated sheet of the polarizing element and the optical compensation sheet). Next, the optically anisotropic layer and the polarizing film are arranged at an angle of an average direction of the normal projection of the transparent carrier with the normal of the disc surface of the disc-shaped compound to the transparent carrier and the angle of the transmission axis in the plane of the polarizing film is substantially 45 °. , The maximum optical compensation effect can be obtained for the curved alignment type liquid crystal cell. [Disclosure of the invention] The present inventors use an optical compensation sheet (an optical compensation sheet made of cellulose acetate film or an optical anisotropic layer on a cellulose acetate film) mounted on a large display panel of 17 inches or more. When the resulting optical compensation sheet was used as a polarizing plate for a protective film, it was found that the frame-like transmittance did not increase at all due to thermal distortion. The optical compensation sheet must not only provide the liquid crystal cell with optical compensation function, but also must be excellent in durability due to changes in the use environment. The optical compensation sheet about the function of the λ / 4 plate can reach λ / 4 in a wide range of wavelengths by laminating two polymer films. However, the angles of the two polymer films must be closely adjusted and laminated. A λ / 4 plate made of a polymer film is also proposed. However, a thin film that can reach λ / 4 in a wide wavelength range is almost non-existent. In addition,

581885 V. Description of the invention (6) It can be seen that when using a λ / 4 plate made of a polymer film in a liquid crystal display device, it is impossible to expect an improvement in the viewing angle of the heterocrystalline display device. Therefore, although a reflection type liquid crystal display device using one film can obtain a comparison equal to or more than the above-mentioned two type λ / 4 films, a portable terminal device (especially an area) is used as the main application of the reflection type liquid crystal display device. Large displays) can cause durability issues due to thermal distortion. Specifically, due to the distortion caused by the heat generated by the backlight of the liquid crystal display device, there may be a problem in the film surface such as hysteresis streaks or changes in the direction of the slow axis, and the transmittance around the liquid crystal cell increases in a black display , "Frame-shaped transmittance rises (light leakage)" will occur. 'The polarizing plates used in liquid crystal display devices are provided with transparent protective films on both sides of the polarizing film. Then, when the optical compensation sheet and the polarizing film are laminated to form an (elliptical) polarizing plate, the optical compensation sheet can function as a transparent protective film on the polarizing film side. This polarizing plate has a sequential layer structure of a transparent protective film, a polarizing film, and an optical compensation sheet. The liquid crystal display device is characterized by being thin and light. When it is reduced by using one of the constituent elements (the protective film on the polarizing plate side), the device can be made thinner and lighter. In addition, when reducing the constituent elements of a liquid crystal display device, the bonding process of one constituent element is also reduced, which can reduce the failure situation when manufacturing the device. When a cellulose acetate film is used as a transparent protective film, there is a problem of compatibility with a polarizing film (usually a polyvinyl alcohol film). There is no appropriate adhesive capable of strongly bonding both the polyvinyl alcohol film and the cellulose acetate film. ^ Japanese Unexamined Patent Publication No. 8-94838 can be made by making the transparent protective film alkaline. 581885 5. Explanation of the invention (7) Solve the problem of affinity between polarizing film and transparent carrier. When the transparent protective film is alkalized, the ester bond of the cellulose acetate on the surface part is partially decomposed by water, and the cellulose is restored to the original hydroxyl group. Cellulose and polyvinyl alcohol use polyhydroxy polymer to improve affinity. Therefore, the alkali-treated transparent protective film and the polarizing film can be easily adhered. When observing the polarizing plate of an optical compensation sheet made of a transparent protective film, a polarizing film, and a cellulose acetate film produced by performing alkali treatment and lamination, it can be seen that the optical function of the optical compensation sheet is lower than that before the alkali treatment. In addition, the lye used in the alkalizing treatment causes yellowing problems after the treatment. In addition, there is still room for improvement in the adhesion between cellulose acetate films and polarizing films. As described above, the liquid crystal display device uses an optical compensation sheet made of a cellulose acetate film or an optical compensation sheet made of an optically anisotropic layer formed of a liquid crystal compound on the cellulose acetate film. However, when these optical compensation sheets are used, the frame-like transmittance may increase on the display screen of the liquid crystal display device, and in particular, the liquid crystal display device with a large screen size may have a significant increase in transmittance. Another problem is that the cellulose acetate film has poor adhesion with other materials (polarizing film, alignment film, etc.), and the optical compensation sheet has practical durability. An object of the present invention is to provide an optical compensation sheet made of a cellulose acetate film which can prevent a liquid crystal cell from having a light leakage problem, and which can be optically compensated, or an optically anisotropic layer provided on the cellulose acetate film. Optical compensation sheet.

581885 V. Description of the invention (8) Another object of the present invention is to provide an optical compensation sheet (λ / 4 plate) which has no light leakage problem and can reach λ / 4 in a wide wavelength range. Another object of the present invention is to provide an optical compensation sheet capable of optically compensating a liquid crystal cell and having excellent adhesion to a polarizing film. Another object of the present invention is to provide an optical compensation sheet having substantially no change in optical function before and after alkalization. Another object of the present invention is to provide an excellent (ellipsoidal) polarizing plate that integrates an optical compensation sheet and a polarizing film without causing light leakage problems or adhesion problems. Another object of the present invention is to provide a circularly polarizing plate that integrates a λ / 4 plate (optical compensation sheet) with a polarizing film without any problem of light leakage or adhesion, and can achieve circularly polarized light in a wide wavelength range. Another object of the present invention is to provide a liquid crystal display device (especially an OCB type liquid crystal cell) which is optically compensated by an optical compensation sheet and has no light leakage problem. In order to optically compensate a liquid crystal cell, an optical compensation sheet made of a cellulose acetate film or an optical compensation sheet made of a liquid crystal compound on a cellulose acetate film is used. As a result of repeated in-depth investigations by the present inventors, it has been found that when the thickness of the cellulose acetate film used in the optical compensation sheet is in a range of 10 to 70 // m, light leakage can be prevented from occurring in the liquid crystal display device. The light leakage and the thickness of the cellulose acetate film are as follows. The present invention provides an optical compensation sheet which is based on 100 mass parts of acetic acid degree of 59,0 to 6 1.5% cellulose acetate, and contains 0.0 1 to 20 mass parts of cellulose acetate with at least two aromatic Aromatic ring

-10- 581885 V. Description of the invention (9) In the optical compensation sheet of cellulose acetate film, it is characterized in that the 1 ^ retardation (1 ^ 5 5 ()) of cellulose acetate film measured at a wavelength of 5 50nm is 0 ~ 2 () () 11111, Rth hysteresis (Rth5 50) of cellulose acetate film measured at a wavelength of 550nm is 70 ~ 400_, thickness of cellulose acetate film is 10 ～ 70μΐΏ 〇 Re hysteresis of film and Rth hysteresis of film Each is defined by the following formulae (I) and (II). (I) Re == (nx—ny) Xd (II) Rth = {(η x + ny) / 2 — η z} X d In formulas (I) and (II), nx is in the plane of the film The refractive index in the direction of the late phase axis (the direction with the largest refractive index). In formulae (I) and (II), ny is the refractive index in the direction of the phase advance axis (the direction of the smallest refractive index) in the film plane. In the formula (I I), nz is the refractive index in the thickness direction of the film. In the formulae (I) and (11), d is a film thickness in nm. In addition, the present invention provides a polarizing plate, which is formed of a polarizing film and two transparent protective films arranged on both sides thereof. The transparent protective film is made of 59.0 to 61.5% cellulose acetate to 100 parts by mass of acetate And Re hysteresis (Re5 50) of cellulose acetate films made from cellulose acetate films containing 0.01 to 20 parts by mass of an aromatic compound having at least two aromatic rings and measured at a wavelength of 55 nm. ) Is 0 ~ 200nm and the Rth hysteresis (Rth5 50) of cellulose acetate film measured at a wavelength of 5 5 0ηπ is 70 -11- 581885 5. Description of the invention (1〇) ~ 400nm, the thickness of cellulose acetate film is 10 ~ 70μπι. In addition, the present invention provides a liquid crystal display device, which is formed by a liquid crystal cell and two polarizing plates arranged on two sides thereof, and the polarizing plate is a polarizing film and two plates arranged on both sides In a liquid crystal display device made of a transparent protective film, at least one of the two transparent protective films disposed between the liquid crystal cell and the polarizing film has 59.0 to 61.5% cellulose acetate and 100% cellulose acetate to 100 parts by mass. The Re hysteresis (Re550) of a cellulose acetate film formed from a cellulose acetate film containing 0.01 to 20 parts by mass of an aromatic compound having at least two aromatic rings and measured at a wavelength of 550 nm is 0 to 2 0 0 nm. The R th hysteresis (Rth550) of the cellulose acetate film measured at a wavelength of 50 nm is 70 to 400 nm, and the thickness of the cellulose acetate film is 10 to 70 μm. The present invention provides a circular polarizing plate, which is based on optical The compensation film and the linear polarizing film are substantially circular retarders laminated with the retardation axis and the linear polarizing film in the optical compensation plane. The angle of the transmission axis is 45 °. The optical compensation film is characterized by having 100 parts by mass. Degree of chemical conversion: 59.0 ~ 61.5% cellulose acetate and cellulose acetate: 0.01 ~ 20 mass parts of cellulose acetate film containing an aromatic compound having at least two aromatic rings; acetic acid measured at a wavelength of 550nm The Re hysteresis (Re550) of the cellulose film is 0 to 200 nm, the Rth hysteresis (Rth5 50) of the cellulose acetate film measured at a wavelength of 5 50 nm is 70 to 400 nm, and the thickness of the cellulose acetate film is 10 to 70 μΐΏ. The invention provides a reflective liquid crystal display device, which is based on sequential lamination.

-12- 581885 V. Description of the invention (11) In a reflective liquid crystal display device with a reflecting plate, a liquid crystal cell and a polarizing plate, it is characterized in that a pair of 100 parts by mass of acetic acid is 59.0 between the reflecting plate and the polarizing film. ~ 61.5% cellulose acetate and cellulose acetate 0.01 to 20 parts by mass containing an aromatic compound having at least two aromatic rings, a cellulose acetate film measured at a wavelength of 550 nm The Re hysteresis (Re550) of 0 to 200 nm, the Rth retardation (Rth550) of cellulose acetate films measured at a wavelength of 550 nm is 70 to 400 nm, and the Re hysteresis (Re590) of the cellulose acetate films measured at a wavelength of 450 nm is The Re hysteresis (Re590) of the cellulose acetate film at 100 to 125 nm and measured at a wavelength of 590 nm is 120 to 160 nm, which satisfies the relationship of Re590-Re450 ^ 2 nm, and the thickness of the cellulose acetate film is 10 to 70 μm. The invention provides a liquid crystal display device, which is a liquid crystal display device formed by a curved alignment type liquid crystal cell and a pair of polarizing plates arranged on both sides of the liquid crystal cell. At least one polarizing plate is composed of a disc-shaped compound as a mixed alignment. An optically anisotropic layer 1, an optically anisotropic layer formed with at least one cellulose acetate film 2, and a laminate formed with a polarizing film, and the polarizing film is arranged in the outermost elliptical polarizing plate, It is characterized in that the direction of the maximum refractive index in the plane of the optically anisotropic layer 1 and the transmission axis in the plane of the polarizing film are arranged in parallel or perpendicular to the optically anisotropic layer 1, the optically anisotropic layer 2 and the polarizing film. The cellulose film of the anisotropic layer 2 is an aromatic compound having 0.01 to 20 parts by mass of cellulose acetate having at least two aromatic rings for 100 parts by mass of 59.0 to 6 1.5% cellulose acetate and cellulose acetate. Re hysteresis (Re550) of cellulose acetate film measured at a wavelength of 50 nm

-13- 581885 V. Description of the invention (12) 1 ~ 20nm, Rth hysteresis (Rth550) of cellulose acetate film measured at a wavelength of 550nm is 150 ~ 300nm, and the thickness of the cellulose acetate film is 1 0 ~ 7 Ο μηι 0 The present invention provides a liquid crystal display device, which is a liquid crystal display device composed of a bend-aligned liquid crystal cell and a pair of polarizing plates arranged on both sides of the liquid crystal cell. At least one polarizing plate is a mixture of disc-shaped compounds. Aligned optically anisotropic layer 1, an optically anisotropic layer formed with at least one cellulose acetate film, and a laminate formed with a polarizing film, and the polarizing film is arranged in the outermost elliptical polarizing plate , Characterized in that the maximum refractive index direction in the plane of the optical anisotropic layer 1 and the in-plane transmission axis of the polarizing film are 45 °, and the maximum refractive index direction in the plane of the optical anisotropic layer 2 and the in-plane transmission of the polarizing film The optically anisotropic layer 1, the optically anisotropic layer 2 and the polarizing film are arranged substantially parallel or perpendicular to the axis. The cellulose film of the optically anisotropic layer 2 is cellulose acetate having a degree of acetic acid 59.0 to 61.5% of 100 parts by mass ,and In terms of acid cellulose, 0.01 to 20 parts by mass of an aromatic compound having at least two aromatic rings, and the Re hysteresis (1 ^ 5 50) of a cellulose acetate film measured at a wavelength of 55 nm is 20 to 10011111, The Rth hysteresis (Rth550) of the cellulose acetate film measured at a wavelength of 55〇11111 is 150 to 300 nm, and the thickness of the cellulose acetate film is 10 to 70 μm. The inventors adjusted the thickness of the cellulose acetate film used in the optical compensation sheet, the types and amounts of additives (specifically, aromatic compounds having two aromatic rings), or manufacturing conditions (such as film stretching) Condition), no light leakage problem will occur, and the liquid crystal cell will be optically compensated successfully. -14- 581885 V. Description of the invention (13) Furthermore, the inventors adjusted the thickness of cellulose acetate film used in the optical compensation sheet and additives (specifically, an aromatic compound having two aromatic rings). The type and amount, or manufacturing conditions (such as the stretching conditions of the film), can successfully provide an optical compensation sheet (λ / 4 plate) that does not have the problem of light leakage and can reach λ / 4 in a wide wavelength range. In addition, by using the phase difference plate in a liquid crystal display device, the viewing angle can be significantly improved. The use of a cellulose acetate film can obtain an optical compensation sheet (λ / 4 plate) that can reach λ / 4 in a wide range of wavelengths, and it is not necessary to carry out a process of laminating the angles of the conventional two polymer films to perform the lamination. In the invention, in order to optically compensate the liquid crystal cell, the hysteresis chirp (Re550) measured at a wavelength of 550 nm of the cellulose acetate film used in the optical compensation sheet was adjusted to 0 to 200 nm and the Rth hysteresis chirped at a wavelength of 5 50 nm ( Rth550) is 70 to 400 nm. In the present invention, in order to suppress the frame-like transmittance from increasing, the thickness of the cellulose acetate film used for the optical compensation sheet is adjusted to 10 to 70 // m. Generally, when the thickness of the cellulose acetate film becomes thin, the R t h hysteresis becomes smaller, and the liquid crystal cell cannot be optically compensated sufficiently. In the present invention, the liquid crystal cell is fully optically compensated by adding an additive to the cellulose acetate film so that the film thickness can prevent light leakage. By making the thickness of the cellulose acetate film in the range of 10 ~ 70 // m, the production process of the optical compensation sheet or the bonding process of the optical compensation sheet in the production process of the polarizing plate is rational, and the problem of light leakage can be solved. When the thickness of the optical compensation sheet of the present invention is reduced, the manufacturing cost of the liquid crystal display device can be suppressed, and the thickness of the liquid crystal display device can be reduced.

-15 · 581885 5. Description of the invention (14) Furthermore, the polarizing plate is made of a polarizing film and protective films arranged on both sides thereof. Therefore, the polarizing film is used to adsorb iodine or a dichroic pigment to a polyvinyl alcohol stretch alignment person, and the protective film is generally made of a cellulose acetate film. When the above optical compensation sheet is used as a protective film on one side of the polarizing plate, the number of constituent elements of the polarizing plate will not increase, and an optical compensation function can be added to the polarizing plate. At this time, when a surface treatment is applied to a cellulose acetate film, the surface energy of the film is 55 to 75 mN / m, and a polarizing plate having improved adhesion with polyvinyl alcohol (through an adhesive) can be obtained. . In addition, when the surface of the cellulose acetate film is alkalized, by adjusting the processing conditions, the optical characteristics will not substantially change before and after the alkalization treatment, and the coloring of the alkali treatment liquid used in the alkalization treatment can be changed. Small optical compensation plate. In addition, when cellulose acetate having a degree of acetation of less than 59.0 is used, although the above-mentioned optical anisotropy can be easily achieved, the physical properties as a cellulose acetate film are reduced. In the present invention, by using cellulose acetate having a degree of acetification of 59.0 to 61.5%, and by other methods (adjusting the above-mentioned additives or manufacturing conditions) to achieve the above-mentioned hysteresis, cellulose acetate films having excellent optical anisotropy and physical properties can be obtained. . The polarizing plate using the optical compensation sheet and the optical compensation sheet as a protective film can be advantageously used in a VA (vertical alignment) type, an OCB (optical compensation bending) type, a TN (twisted nematic) type liquid crystal display device, and Reflection type liquid crystal display device. The optical compensation sheet of the present invention is preferably a liquid crystal display device used in a curved alignment type (OCB type).

-16 · 581885 V. Description of the invention (15) In the past, optical compensation films containing a disc-shaped compound for forming an elliptical polarizing plate used in a curved alignment type liquid crystal display device have been proposed to have good birefringence in terms of optical characteristics Raw materials (polycarbonate, etc.). In the curved alignment type liquid crystal display device of the present invention, the polarizing plate is made of at least one optically anisotropic cellulose acetate film (hereinafter referred to as an optically anisotropic layer 2) which can impart optical characteristics to the cellulose acetate film, Formed with an optically anisotropic layer (hereinafter referred to as an optically anisotropic layer 1) made of a disc-shaped compound, and a polarizing film. Secondly, the optically anisotropic layer i and the optically anisotropic layer i and the angle of the normal projection average normal direction of the disc-shaped compound to the cellulose acetate film and the angle of the in-plane transmission axis of the polarizing film are substantially 45 °. The polarizing film and the optically anisotropic layer 2 and the polarizing film are disposed under an angle where the retardation axis of the optically anisotropic layer 2 and the transmission axis in the plane of the polarizing film are substantially parallel or substantially vertical. An OCB type liquid crystal cell that can be completely optically compensated and has no light leakage at the 4 corners of the display screen under lighting. In this specification, "substantially parallel" refers to a range of 5 ° or less at a relatively tight angle. The range is ± 4. The following is better and better is ± 3. Below, the best is ± 2 ° or less. In addition, in this specification, "slow axis (s 1 ow ax i s)" means the direction in which the refractive index is maximum, and "transmission axis" means the direction in which the transmittance is maximum. [Brief Description of the Drawings] FIG. 1 is a schematic diagram showing a basic configuration of a reflective liquid crystal display device. -17- 581885 V. Description of the invention (16) Figure 2 is a cross-sectional schematic diagram showing a typical type of a host-guest reflective liquid crystal display element. Fig. 3 is a schematic cross-sectional view showing another typical form of the subject-guest reflective liquid crystal display. Fig. 4 is a typical cross-sectional view showing the alignment of liquid crystal compounds in a curved alignment liquid crystal cell. Fig. 5 is a schematic diagram showing an elliptically polarizing plate of the present invention. Fig. 6 shows a curved alignment type liquid crystal display device of the present invention. Fig. 7 is a conceptual diagram showing an optical compensation relationship of a bend alignment type liquid crystal display device. Fig. 8 is a schematic diagram showing various types of elliptically polarizing plates. Fig. 9 is a schematic diagram showing another form of the elliptical polarizer. (Prevention of light leakage) As a result of intensive investigations by the present inventors, it has been found that the frame-shaped transmittance rise (light leakage) of the display screen of the liquid crystal display device is caused by the following two reasons. The first reason is the change in the humid and hot conditions in the environment in which the liquid crystal display device is used. When an optical compensation sheet is used in a liquid crystal display device, a bonding agent or an adhesive is generally used to fix the optical compensation sheet to a liquid crystal cell or the like. The cellulose acetate film used in the optical compensation sheet is expanded or contracted due to changes in the humidity and heat conditions. Since this expansion or contraction is suppressed by fixing the optical compensation sheet, internal stress is generated in the film. The internal stress causes birefringence in the film (photoelastic effect) to change the optical characteristics, and it can be seen that this is the cause of light leakage.

-18- 581885 V. Explanation of the invention (17) The second reason is that the temperature distribution in the optical compensation sheet is generated by the backlight of the liquid crystal display device. It can be seen that a thermal distortion occurs in the optical compensation sheet by the temperature distribution, and this distortion causes the same optical characteristics as described above to cause a light leakage. It is known that polymers having a hydroxyl group such as cellulose acetate are greatly affected by changes in environmental conditions. In order to prevent the occurrence of light leakage, the optical characteristics of the optical compensation sheet should be small, and the temperature distribution generated by the optical compensation should be uniform. The change in the optical characteristics is related to the change in the thickness of the optical compensation sheet, the photoelastic coefficient, and the environmental conditions, and it can be seen that there is a relationship between the virtual distortion and the elastic modulus. Therefore, the thinner the thickness of the optical compensation sheet, the lower the photoelastic coefficient, the smaller the distortion due to the change in environmental conditions, and the smaller the elastic modulus, the light leakage can be significantly reduced. Moreover, the temperature distribution generated by the optical compensation sheet can be reduced and reduced by reducing the thermal conductivity of the optical compensation sheet. Secondly, in order to solve the problem of light leakage, it is particularly effective to reduce the thickness of the cellulose acetate film. The transmittance is related to the product of the birefringence and the thickness of the cellulose acetate film (phase difference). The larger the phase difference, the greater the transmittance. Therefore, when the thickness of the cellulose acetate film is reduced, it is found that the frame-like transmittance rise can be reduced because the phase difference is small even at the same birefringence. However, when the thickness of the cellulose acetate film becomes too small, a problem of poor rationality of the film may occur. The thickness of the cellulose acetate film that prevents light leakage and maintains the balance with the handling properties when producing an optical compensation sheet is as follows.

-19- 581885 5. Description of the invention (18) In the present invention, the thickness of the cellulose acetate film used in the optical compensation sheet is adjusted within a range of 10 to 70 // m. The thickness of the cellulose acetate film is more preferably 20 to 60 // m, and the most preferable is 30 to 50 # m. The thermal conductivity of the cellulose acetate film is preferably 1 W / (m · K) or more. In order to make the imaginary distortion small, it is preferable to increase the surface orientation of the polymer molecules by biaxially stretching the cellulose acetate film, or to make the coefficient of hygroscopic expansion to 30 X 1 (Γ 5 /% RH or less. Acetate fiber The coefficient of hygroscopic expansion of the plain film is 15 X1 (T5 /% RH or lower is better, the best is i0xi0_5 /% rh or lower. The photoelastic coefficient of cellulose acetate film is 1.05-5 cm2 / Kg or less is preferred. The elasticity of the cellulose acetate film is preferably 3000 MPa or less, and more preferably 2500 MPa or less. (Hysteresis of the film) Re hysteresis and Rth hysteresis of the film are each represented by the following formula (I) and ( II) Definition 0 (I) Re = (nx — ny) Xd (II) Rth = {(nx + ny) X2 — nz} Xd In formulae (I) and (II), nx is the delay in the plane of the film The refractive index in the phase axis direction (the direction with the largest refractive index). In formulas (I) and (II), ny is the refractive index in the phase axis direction (the direction with the smallest refractive index) in the film plane. In 11), nz is the refractive index in the thickness direction of the film.

-20- 581885 V. Description of the invention (19) In formulae (I) and (11), d is the thickness of the film in nm. In the present invention, the Re hysteresis chirp (R e 5 5 0) measured at a wavelength of 550 nm of a cellulose acetate film is in the range of 0 to 2 0 nm, and the Rth hysteresis chirp (Rth 5 50) measured at a wavelength of 5 5 0 n id. The range is 70 to 400 nm. An optical compensation sheet made of a cellulose acetate film is preferably adjusted to have a Re hysteresis (Re550) measured at a wavelength of 5 to 50 nm of the cellulose acetate film of 20 to 70 nm. An optically-compensated sheet formed by disposing an optically anisotropic layer on a cellulose acetate sheet, preferably having a Re hysteresis (Re550) measured at a wavelength of 550 nm of the cellulose acetate film, is 0 to 20 nm. When an optical compensation sheet is used for a liquid crystal display device, the hysteresis (Rth550) measured at a wavelength of 5 to 50 nm of the cellulose acetate film is preferably 150 to 400 nm. When two optical compensation sheets are used for a liquid crystal display device, the Rth hysteresis (Rth 5 50) measured at a wavelength of 550 nm of the cellulose acetate film is preferably 70 to 250 nm, and more preferably 70 to 200 nm. The birefringence (Δ η ·· nx-ny) of the cellulose acetate film measured at a wavelength of 550 nm is preferably 0.00028 to 0.020, more preferably 0.00 1 96 to 0.01375, and even more preferably 0.00168 to 0.006875, and most preferably Those are 0.0027 5 to 0.004 58. In addition, the birefringence in the thickness direction of the cellulose acetate film measured at a wavelength of 550 nm (nx + ny) / 2-nz) was from 0.001 to 0.04. (λ / 4 plate)

-21-581885 5. Description of the invention (20) The optical compensation sheet made of cellulose acetate film is used as the hysteresis (Re 450) measured at a wavelength of 450ηΐΏ for the I / 4 board is 100 ~ 125nm. The hysteresis (Re 5 90) measured at a wavelength of 590 nm is 120 to I60 nm, and it is better to adjust to satisfy the relationship of Re590-Re450 g 2 nm. The better is Re590-Re450-5nn) and the best is Re590-Re4502 10nm. The hysteresis chirp (Re450) measured at a wavelength of 450 ηπ is 108 to 120 nm, and the hysteresis chirp (Re 5 50) measured at a wavelength of 5 50 nm is 125 to 142 nm. The relationship between Re590-Re 550-2ηη is better adjusted. The better is Re590-Re5502 5nm, and the best is Re590-Re550gl0nm. In addition, Re550-Re4502 10nm is preferred. In addition, it is preferable that one λ / 4 plate (optical compensation sheet) of the present invention satisfies the following formula. (nx ~ nz) // (nx—ny) (where η x is the refractive index of the retardation plate in the plane of the retardation plate; ny is the refractive index of the retardation plate in the plane of the retardation plate in the vertical direction ; Nz is the refractive index in the thickness direction) The above-mentioned cellulose acetate film with optical properties can be prepared from the following cellulose acetate film containing a hysteresis rising agent. The correlation between the hysteresis of cellulose acetate film and its wavelength can be adjusted by (1) the composition of cellulose acetate (especially the average degree of vinegarization), (2) the type and amount of the retardation rising agent, and (3) Film thickness control. In particular, by using the hysteresis rising agent of (2), the conventional optical isotropy can be used.

-22- 581885 5. Description of the invention (21) Cellulose acetate film is used as a phase difference plate. The above-mentioned cellulose acetate film having optical properties can be manufactured by the following materials and methods. (Cellulose acetate) In the present invention, cellulose acetate having a degree of vinegarization of 59.0 to 6 1.5% is used. The degree of vinegarization is preferably 59.5 to 61.3%. The degree of vinegarization refers to the amount of combined acetic acid equivalent to a unit mass of cellulose. The degree of acetic acid was measured and calculated by the degree of acetylation of ASTM: D-817-91 (test method of cellulose acetate, etc.). The viscosity average degree of polymerization (DP) of cellulose acetate is preferably 2 50 or more, and more preferably 290 or more. In addition, the cellulose acetate used in the present invention preferably has a narrow molecular weight distribution of Mw / Mn (Mw is a mass average molecular weight and Mη is a number average molecular weight) measured by a gel permeation chromatography method. The specific Mw / Mn is preferably 1.0 to 1.7, more preferably 1.3 to 1.65, and most preferably 1.4 to 1.6. It is better that the cellulose acetate has a high degree of substitution at 6 positions, specifically 0.88 or more, and the ratio of the degree of substitution at 6 positions to the total degree of substitution of cellulose acetate at positions 2, 3, and 6. 32% or more is preferred, 33% or more is better, and 34% is better. A general method for synthesizing cellulose acetate is that the degree of substitution of the ethyl acetate at the 2- or 3-position is higher than that of the ethyl acetate at the 6-position. Therefore, in order to increase the degree of substitution at the 6th position to a value that is higher than 0.88 or more, or 3 to 2% of the total, the synthesis reaction must be specifically adjusted. • 23 · 581885 V. Description of the invention (22) Specific reaction conditions are to reduce the amount of sulfuric acid catalyst and increase the time for vinegarization reaction. The more sulfuric acid catalysts, the faster the vinegarization reaction, but depending on the amount of catalyst, sulfate esters are formed between cellulose acetate and cellulose at the end of the reaction, resulting in residual hydroxyl groups. Sulfuric acid esters are produced more frequently by the highly reactive 6-position. Therefore, the more the sulfuric acid catalyst, the smaller the degree of substitution at the 6-position. Therefore, in the synthesis of cellulose acetate having a high degree of substitution at the 6-position, it is necessary to extend the reaction time in order to reduce the amount of sulfuric acid catalyst as much as possible and to compensate for the reduced reaction speed. The degree of substitution of ethyl acetate at the 2-, 3-, and 6-positions of cellulose acetate can be determined by I3C-NMR measurement after the cellulose acetate is acrylized. The measurement method is described in detail in Tezuka (Carbohydr. Res. 273 (1 995) 83 -91). The cellulose acetate having a high substituent at the 6-position is described in Japanese Unexamined Patent Publication Nos. 1 1 to 5 85 (especially Synthesis Examples 1 to 3). (Hysterescensing agent) In order to adjust the retardation effect of the cellulose acetate film, an aromatic compound having at least two aromatic rings is used as a hysteresis increasing agent. The aromatic compound is 0.01 to 20 parts by mass for 100 parts by mass of cellulose acetate. The aromatic compound is preferably 0.05 to 15 parts by mass with respect to 100 parts by mass of cellulose acetate, and more preferably 0.1 to 10 parts by mass. It is also possible to use two or more aromatic compounds. The aromatic hydrocarbon ring is preferably a 6-carbon ring (ie, a benzene ring). Aromatic heterocycles are generally unsaturated heterocycles. Aromatic heterocyclic ring with 5 carbons

-24- 581885 V. Description of the invention (23) A ring, a 6-carbon ring or a 7-carbon ring is preferred, and a 5-carbon ring or a 6-carbon ring is more preferred. Aromatic heterocycles generally have at most double bonds. The hetero atom is preferably a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably a nitrogen atom. Examples of the aromatic heterocyclic ring include a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, a furan ring, a triazole ring, and a pyran ring. , Pyridine fixed ring, pyridine ring, pyridine fixed ring, pyridine ring, and 1, 3, 5 · triple ring. Aromatic rings are compared with benzene ring, furan ring, thiophene ring, pyrrole ring, oxazole ring, thiazole ring, imidazole ring, triazole ring, pyridine ring, pyrimidine ring, pyridine ring, and 1,3,5-tridentate ring. The better, the better is the benzene ring, that is, the 3,5 -three plough ring. The aromatic compound preferably has at least one 1,3,5-triplet ring. The number of aromatic rings in the aromatic compound is preferably 2 to 20, more preferably 2 to 12, more preferably 2 to 8, and most preferably 2 to 6. The bonding relationship of a fragrant ring can be divided into (a) when a condensed ring is formed, (b) when a single bond is directly connected, and (c) when it is bonded through a bonding group (because of an aromatic ring, a rotational bond cannot be formed) ). The bonding relationship may be any one of (a) to (c). (a) Condensed rings (condensed rings of two or more aromatic rings) include indene ring, naphthalene ring, ring, castor ring, fluorene ring, phenanthrene ring, anthracene ring, naphthalene ring, biphenyl ring, naphthalene Benzene ring, stilbene ring, indole ring, isoindole ring, benzofuran ring, benzothiophene ring, indole ring, benzoxazole ring, benzothiazole ring, benzimidyl ring, benzene Benzene tricyclic ring, purine ring, indine ring, chromocyclic ring, quinine ring, isoquinoline ring, quinone ring, thiazole ring, perylene ring, oxoxaline ring, silent well ring, pteridine ring, Carbazole ring, acridine ring, phenanthridine ring, glutathione ring, phenoxine ring, phenothion ring, phenothion ring, phenox ring and benzothiazole ring. Tsai

-25- 581885 5. Description of the invention (24) Rings, core rings, indole rings, benzoxazole rings, benzothiazole rings, benzimidazole rings, benzotriazole rings and quinoline rings are preferred. The single bond of (b) is preferably bonded between carbon atoms of two aromatic rings. Two aromatic rings are bonded with two or more single bonds to form an aliphatic ring or a non-aliphatic heterocyclic ring between the two aromatic rings. The bonding group of (c) is preferably bonded to a carbon atom of two aromatic rings. The bonding group is preferably an alkylene group, an alkenyl group, an alkynyl group, -C0-, -O-, -NH-, -S- or a combination thereof. An example of the bonding group formed by the combination is shown below. Furthermore, the left-right relationship of the following bonding examples may be the opposite relationship. cl: —C〇〇〇 一 c 2: -CO-NH-c 3: 〇 一 c 4: NH—C〇—NH — c 5: -NH ~ CO-〇-c 6 ·· —〇 一 C 〇〇〇—c 7: —〇 一 7> ^ b; y—〇 一 c 8: —C〇-7 /; i ^ r: p ^ — c 9: — C〇7> 々 * = p ^ — Nh — clO: —C〇〇〇 一 ell ·· c〇-〇 I have a teenager-c0-7 children ^^ a cl2 ·· -〇 一 -〇--cl3 ·· -〇 一 C〇- T ^ year — cl4 ·· —NH — C〇7_ ^ 二 二 ^^ c 15 · — 〇 一 c 〇々 瓜 々 二 方 曰 族 5¾ and the bonding group may also have a substituent. -26- V. Description of the invention (25) Substituents include, for example, halogen atoms (F, C 1, B r, I), hydroxyl, carboxyl, cyano, amino, nitro, sulfo, aminoformyl, Aminosulfonyl, ureido, alkyl, alkenyl, alkynyl, aliphatic fluorenyl, aliphatic fluorenyloxy, alkoxy, alkoxycarbonyl, alkoxycarbonylamino, alkylthio, alkyl Sulfosulfenyl, aliphatic sulfonyl, aliphatic sulfonyl, aliphatic substituted amine, aliphatic substituted amine methylsulfonyl, aliphatic substituted sulfanilino, aliphatic substituted urea, and non-aromatic heterocyclic Ring base. The number of carbon atoms of the group is preferably 1 to 8. For a cyclic alkyl group, a linear alkyl group is preferable, and a linear alkyl group is more preferable. The alkyl group has another substituent (for example, a hydroxyl group, a carboxyl group, an alkoxy group, and an alkyl-substituted amino group). Alkyl (including substituted alkyl) includes, for example, methyl, ethyl, n-butyl, n-hexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl, and 2-diethylamine Ethyl. The carbon number of the alkenyl group is preferably 2 to 8. For cyclic alkenyl, chain alkenyl is preferred, and linear alkenyl is more preferred. The alkenyl group may have another substituent. Examples of alkenyl are vinyl, allyl and 1-hexenyl. The number of carbon atoms of the alkynyl group is preferably 2 to 8. For a cyclic alkynyl group, a chain alkynyl group is preferred, and a linear alkynyl group is more preferred. An alkynyl group may have another substituent. Examples of alkynyl include ethynyl, 1-butynyl and 1-hexynyl. The number of carbon atoms of the aliphatic fluorenyl group is preferably 1 to .10. Examples of the aliphatic fluorenyl group include ethenyl, propionyl, and butyryl. The number of carbon atoms of the aliphatic fluorenyloxy group is preferably 1 to 10. The aliphatic fluorenyloxy group includes, for example, ethynyloxy. The number of carbon atoms of the alkoxy group is preferably 1 to 8. An alkoxy group may have another substituent (• 27- 581885 V. Description of the Invention (26) such as an alkoxy group). Examples of the alkoxy group (including a substituted epoxy group) include a methoxy group, an ethoxy group, a butoxy group, and a methoxyethoxy group. The carbon number of the alkoxycarbonyl group is preferably 2 to 10. The alkoxycarbonyl group includes, for example, a methoxycarbonyl group and an ethoxycarbonyl group. The carbon number of the alkoxycarbonylamino group is preferably 2 to 10. The alkoxycarbonylamino group includes, for example, a methoxycarbonylamino group and an ethoxycarbonylamino group. The number of carbon atoms in the alkylthio group is preferably 1 to 12. Alkylthio includes, for example, methylthio, ethylthio, and pentathio. The number of carbon atoms of the alkylsulfonyl group is preferably 1 to 8. The number of carbon atoms of the alkylsulfonyl group includes, for example, a methanesulfonyl group and an ethanesulfonyl group. The number of carbon atoms of the aliphatic amido group is preferably 1 to 10. An aliphatic amido group is, for example, an acetamido group. The number of carbon atoms of the aliphatic sulfa group is preferably 1 to 8. Examples of the aliphatic amine group include methanesulfonyl, butanesulfonyl and n-octanesulfonyl. The number of carbon atoms of the aliphatic substituted amine group is preferably 1 to 10. The aliphatic substituted amino group includes, for example, a dimethylamino group, a diethylamino group, and a 2-carboxydiethylamino group. Aliphatic substituted aminoformamyl and ethylaminoformamyl. The number of carbon atoms of the aliphatic substituted sulfamoyl group is preferably 1 to 8. Aliphatic substituted amine sulfonyl groups such as methyl amine sulfonyl and diethylamine sulfonyl. The aliphatic substituted ureido group includes, for example, a methylureido group. Non-aromatic heterocyclic groups include, for example, pyridyl and morpholinyl. The molecular weight of the hysteresis rising agent is preferably 300 to 800. The boiling point of the hysteresis rising agent is preferably 260 ° C or higher. The boiling point can be measured using a commercially available measuring device (for example, TG / DTA100, manufactured by Seiko Instruments Inc.). Hysteresis

-28- 581885 5. Details of the invention description (27) are described in JP 2000-1 1 1914, 2000-275434 and other publications and P <: ΤΠ00 / 026 1 9 specifications. (Infrared absorbing agent) In order to adjust the hysteresis of each wavelength, an infrared absorbing agent can be added to the cellulose acetate film. For 100 parts by weight of cellulose acetate, the infrared absorber is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 2 parts by weight, and most preferably 0.1 to 0.5 parts by weight. Can use more than two kinds of infrared absorbers. The infrared absorber preferably has a maximum absorption in a wavelength range of 750 to 1100 nm, and more preferably has a maximum absorption in a wavelength range of 800 to 100 nm. The infrared absorber is preferably one which does not substantially absorb in the visible range. The infrared absorbing agent is preferably an infrared absorbing dye or an infrared absorbing pigment, and more preferably an infrared absorbing dye. The infrared absorbing dye contains an organic compound and an inorganic compound. Infrared absorbing dyes using organic compounds are preferred. The organic infrared absorbing dye includes a quinoline compound, a metal chelate compound, an amine sulfonium salt compound, a diimmonium compound, a quinone compound, a squalene key salt compound, and a methylene compound. Infrared absorbing dyes such as color materials, 61 [4] 2 1 5-226 (1 988), and chemical industry, 43-53 (1 986, May) are described. When reviewing the type of dye in terms of infrared absorption function or absorption spectrum, infrared absorption dyes developed in the technical range of silver halide photographic photosensitive materials are excellent. Infrared developed in the technical scope of silver halide photographic photosensitive materials

-29- 581885 V. Description of the invention (28) The linear absorption dye contains dihydronaphthyl hydroxy meta-diazona squalene iron salt dye (US Patent No. 5 3 806 3 No. 5 and Japanese Patent Application No. 8-1 898 1 7 No. description in the manual), quinoline blue dye (Japanese Patent Publication No. 62 · 1 2345 No. 4, No. 3-1 38640, No. 3-211542, No. 3-226736, No. 5-3131305, No. 6-43 5 8 Publications No. 3, Japanese Patent Application No. 7-269 09, and European Patent Application No. 043 0 2 44), pyridinium dyes (Japanese Patent Application No. 3- 1 38640, same as Japanese Patent Application No. 3- 2 1 1 542 Documented in the Gazette), diimmonium dyes (documented in JP-A-3-1-38,640, as described in various publications No. 3-2 1 1 542), pyrazolinone dyes (documented in Japanese Patent Publication No. 2-282244), indoaniline dyes ( Japanese Unexamined Patent Publication No. 5-323500, as described in various publications No. 5-32 3 50), polymethine dyes (Japanese Unexamined Patent Publication No. 3-26765, published in various publications No. 4-1 90343, and European Patent 37796 specification 1) Oxanol dyes (as described in JP-A-3-9346), anthraquinone dyes (as described in JP-A-4-1654), phthalocyanine pigments (US Patent No. 5,009,989 describes the specification) and naphthalene lactone dye (described in European patent specification No. 568,267). (Production of cellulose acetate film) The cellulose acetate film is preferably produced by a solution casting method. Using an organic solvent as a casting solvent, it is more preferable to produce a cellulose acetate film by a solvent casting method. The solvent casting method uses a solution (dope) in which cellulose acetate is dissolved in an organic solvent to produce a thin film. The organic solvent is preferably a solvent containing an ether selected from 3 to 12 carbons, a ketone from 3 to 12 carbons, an ester from 3 to 12 carbons, or a halogenated hydrocarbon from 1 to 6 carbons. Ethers, ketones and esters may also have a cyclic structure. Has more than two ethers, ketones and esters

-30- 581885 5. The functional group of the description of the invention (29) (ie, any of the compounds of -0, -C0- and -coo-) can also be used as an organic solvent. The organic solvent may have other functional groups such as an alcoholic hydroxyl group. In the case of an organic solvent having two or more kinds of functional groups, the carbon number may be within a predetermined range of a compound having any one of the functional groups. Examples of ethers having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, tetrahydrofuran, anisole, and phenylethyl ether. Ketones having 3 to 12 carbon atoms include, for example, acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone, and methyl cyclohexanone. The esters having 3 to 12 carbon atoms include, for example, ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate, and amyl acetate. The organic solvent having two or more kinds of functional groups includes, for example, 2-ethoxyethyl acetate, 2-methoxyethanol, and 2-butoxyethanol. The number of carbon atoms of the halogenated hydrocarbon is preferably 1 or 2, and more preferably 1. The halogen of the halogenated hydrocarbon is preferably chlorine. The ratio of the halogen atom to the halogen atom of the halogenated hydrocarbon is preferably 25 to 75 mole%, more preferably 30 to 70 mole%, more preferably 35 to 65 mole%, and most preferably 40 to 60 mole%. Dichloromethane is a typical halogenated hydrocarbon. It can also be used by mixing two or more organic solvents. The cellulose acetate solution can be prepared by a general method. The general method refers to the treatment at a temperature above 0 ° C (normal temperature or high temperature). The preparation of the solution can be performed by a solution preparation method and a device using a general solvent casting method. Moreover, it is preferable to use a halogenated hydrocarbon (especially dichloromethane) as the organic solvent in a general method.

-31-581885 5. Description of the invention (30) The amount of cellulose acetate is adjusted to include 10 to 40% by mass in the obtained solution. The amount of cellulose acetate is more preferably 10 to 30% by mass. Any of the following additives may be added to the organic solvent (main solvent). The solution can be prepared by stirring cellulose acetate and an organic solvent at room temperature. High concentration solutions can be stirred under pressure or heat. Specifically, cellulose acetate and an organic solvent are added to a pressurized container and sealed, and the solvent is heated to a temperature in the range above the boiling point of normal temperature and the solvent does not boil under pressure and stirred. The heating temperature is usually above 40 ° C, preferably 60 to 200 ° C, and most preferably 80 to 110 ° C. The ingredients can be added to the container after rough mixing in advance. Moreover, they can be put into a container sequentially. The container must be agitable. It is also possible to increase the vapor pressure of the solvent by heating. Or, after the container is sealed, the components are added under pressure. The heating is preferably performed by external heating of the container. For example, a sleeve-type heating device can be used. Further, a plate heater is provided outside the container for piping, and the entire container is heated by circulating the liquid. It is better to use stirring wings inside the container. It is preferable that the stirring wings reach a length near the wall of the container. When the end of the stirring wing is to update the liquid film on the container wall, it is better to set the finning wing. In the container, gauges such as a pressure gauge and a thermometer can also be provided. Each component was dissolved in a solvent in a container. After cooling, remove the prepared solution from the container, or use a heat exchanger to cool it after taking out. The solution can also be prepared by a cooling dissolution method. The cooling and dissolving method

-32- 581885 V. Explanation of the invention (31) Dissolve cellulose acetate in an organic solvent that is not easily soluble. In addition, a solvent that can dissolve cellulose acetate by a general dissolving method also has the effect of obtaining a rapid and uniform solution by a cooling dissolving method. Cellulose acetate was slowly added by a cooling and dissolving method at room temperature, in an organic solvent, and with stirring. The amount of cellulose acetate is preferably adjusted to include 10 to 40% by mass in the mixture. The amount of cellulose acetate is more preferably 10 to 30% by mass. In addition, any of the following additives may be added to the mixture. Then, the mixture is cooled to -100 to -10 ° C (preferably -80 to -10 ° C, more preferably -50 to -20 ° C, and most preferably -50 to -30 ° C). Cooling can be performed, for example, in a dry ice • methanol bath (-7 5 ° C) or a cooled diethylene glycol solution (-30 to -20 ° C). After cooling in this way, the mixture of cellulose acetate and an organic solvent is hardened. The cooling rate is preferably 4 ° C / min or more, more preferably 8 ° C / min or more, and most preferably 12t / min. The faster the cooling rate, the better, but with a theoretical upper limit of 10,000 ° C / sec, a technical upper limit of 1000 ° C, and 10 (TC is a practical upper limit). Moreover, the cooling rate is the temperature at the beginning of cooling and the final cooling. The temperature difference at that time removes the time from the beginning to the final cooling temperature. In addition, it is heated to 0 ~ 200 ° C (preferably 0 ~ 150 ° C, more preferably 0 ~ 120t, the best When it is 0 ~ 50 ° C), cellulose acetate is dissolved in organic solvents. The temperature can be raised only at room temperature or in a warming bath. The heating rate is preferably 4 ° C / min or more. 8 ° C / min or more is better, -33- 581885 V. Invention description (32) 1 2 ° C / min or more is best. The faster the heating speed, the better, but the theoretical upper limit is 10,000 ° C / s値, 1 000 ° c is the technical upper limit 値, and loot is the practical upper limit 而且. Furthermore, the heating rate is the time difference between the temperature at the beginning of the heating and the temperature at the end of the heating, excluding the time from the start to the final heating temperature 値In this way, a uniform solution is prepared. In addition, if the dissolution is insufficient, the operation of cooling and heating can be repeated. Is it sufficiently dissolved? It can be judged only by visually observing the appearance of the solution. In the cooling and dissolving method, in order to avoid mixing of moisture due to dew condensation during cooling, it is better to use a closed container. In addition, in the cooling and heating operation, it can be pressurized during cooling, The pressure is reduced during heating to shorten the dissolution time. For pressure and pressure reduction, it is better to use a pressure-resistant container. Furthermore, cellulose acetate (degree of vinegarization: 60.9%, average degree of viscosity: 2 9 9) ) A 20% by mass solution was dissolved in methyl acetate by a cooling dissolution method, and a phase transition point suspected of a sol state or a gel state exists near 33 ° C by differential scanning calorimetry (DSC). Below the temperature, it becomes a non-uniform gel state. Therefore, the solution must be maintained at a temperature above the suspected phase transition temperature, preferably a temperature of the gel phase transition temperature + 10X. However, the suspected phase transition temperature is acetated by cellulose acetate. Degree, viscosity average degree of polymerization, solution concentration or the organic solvent used. The cellulose acetate solution (dope) is prepared from the cellulose acetate solution by a solvent casting method. The solution is cast on On the barrel or tube, the solvent is evaporated to form a thin film. The solution before casting is preferably adjusted to a concentration of solid content of 18 to 35%. The barrel or -34- 581885 V. Description of the invention (33) The surface of the tube is Mirror surface processing is preferred. For the casting and drying methods of solvent casting method, such as U.S. Patent No. 2 3 3 6 3 10, the same as 23 67 603, the same as 2492078, the same as 2492977, the same as 2492978, the same The specifications of 2607704, the same as 2739069, the same as 2739070, the British patent 64073 1 and the same as 7 3 68 92, JP 45-45 54. It is described in the same publications as 49-56 1 No. 4, Japanese Patent Application Laid-Open No. 60-1 76834, No. 60-203430, and No. 6 2-1 15 0 35. The solution is preferably cast on a bucket or tube with a surface temperature below 10 ° C. It is better to air-dry for 1 second after casting. Alternatively, the obtained solution may be stripped from a bucket or a tube, and then dried in a high-temperature air at a temperature ranging from 100 to 160 ° C in order to evaporate the residual solvent. The above method is described in Japanese Patent Publication No. 5-1 7844. This method can shorten the time from casting to stripping. To implement this method, the solution must be gelled at the surface temperature of the time-delay barrel or tube. The film can be formed by a co-casting method in which two or more layers are cast using the adjusted cellulose acetate solution (dope). In this case, it is preferable to produce a cellulose acetate film by a solvent casting method. The solution is cast on a barrel or tube, and the solvent is evaporated to form a thin film. The solution before casting is preferably adjusted to a concentration of 10 to 40% of the solid content. The surface of the barrel or tube is better processed into a mirror surface. Delaying the flow of several cellulose acetates with two or more layers can cast several cellulose acetate solutions, and several casting ports with intervals in the direction of the carrier are used to cast and laminate the solution containing cellulose acetate to produce film. For example, it is described in JP 6 1-1 584 1 No. 4, JP 1- 1 224 1 9 and JP-35- 581885 V. Description of the invention (34) JP 1 1-1 98285 method. In addition, the cellulose acetate solution can be cast into a thin film by casting from two casting ports. For example, use JP Sho 60-27 5 62, JP Sho 6 1-94724, JP Sho 61-94 6245, JP Sho 6 1-1 048 1 3, JP Sho 6 1-1 5841 No. 3, and JP-A-6-1 3493 The methods described in the respective manuals. Alternatively, a cast of a high-viscosity cellulose acetate solution as described in Japanese Patent Application Laid-Open No. Sho 56-1 626 1 7 may be used to pack the low-viscosity cellulose acetate solution to make the high- and low-viscosity cellulose acetate solution. Casting method of cellulose acetate film simultaneously extruded with an ester solution. In addition, a film can be produced by using two casting ports, peeling a film formed on the carrier through the first casting port, and performing a second casting on the surface side connected to the carrier. For example, the method described in Japanese Patent Publication No. 44-2023 5 is used. As the cast cellulose acetate solution, the same solution may be used, or different cellulose acetate solutions may be used. In order to make the several cellulose acetate layers function, depending on the functions, the cellulose acetate solution is cast out and cast out. In addition, the cellulose acetate solution of the present invention can be cast simultaneously with other functional layers (such as an adhesive layer, a dye layer, a tube prevention layer, an anti-halo layer, an ultraviolet absorbing layer, a polarizing layer, etc.). When the conventional single-liquid layer has a necessary thickness, a high-viscosity cellulose acetate solution must be extruded at a high concentration. At this time, the stability of the cellulose acetate solution is mostly degraded, solids are produced, and malfunctions and flat surfaces are formed. Bad type problem. By casting several cellulose acetate solutions from the casting mouth, the high viscosity solution can be pressed onto the carrier at the same time, which can not only produce good flatness, but also excellent

-36- 581885 V. Description of the invention (35) The film with different surfaces can reduce the drying load by using a thick cellulose acetate solution, and can increase the production speed of the film. To improve the mechanical properties of the cellulose acetate film or to increase the drying speed, a plasticizer may be added. As the plasticizer, a phosphate ester or a carboxylic acid ester is used. Examples of the phosphate ester include triphenyl phosphate (TPP) and tricresol phosphate (TCP). Examples of carboxylic acid esters include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), naphthyl phthalate (DOP), and diphenyl phthalate (DPP) and diethylhexylphthalate (DEHP). Examples of citric acid esters include 0-ethylammonium triethyl citrate (0ACTE) and 0-ethylammonium tributyl citrate (0ACTB). Other carboxylic acid esters include, for example, butyl oleate, methyl ethyl ricinoleate, dibutyl decanoate, and various trimelates. Phthalate plasticizers (DMP, DEP, DBP, DOP, DPP, DEHP) are preferred. DEP and DPP are better. The amount of the plasticizer to be added is preferably 0.1 to 25 mass%, more preferably 1 to 20 mass%, and most preferably 3 to 15 mass% of the cellulose acetate. Anti-deterioration agents (such as antioxidants, peroxide decomposers' radical inhibitors, metal inertizers, acid trapping agents, amines) can also be added to cellulose acetate films. Examples of anti-deterioration agents are described in JP-A-3-1,920,910, 5-1,90,707-3, 5-1,789,789, 5-27,47,1, and 6-1,078,54. The addition amount of the anti-deterioration agent is preferably 0.01 to 1% by mass of the prepared solution (dope), and more preferably 0.001 to 0.2% by mass. If the added amount is less than 0.01% by mass, the effect of the anti-deteriorating agent is almost completely eliminated. If the added amount is more than 1% by mass, the anti-deteriorating agent may bleed out to the surface of the film. Better anti-deterioration agents are, for example, butylated hydroxy-37-581885. V. Description of the Invention (36) Toluene (BHT), Tritylamine (TBA). [Polyester Polyurethane] When the mechanical properties of cellulose acetate film are improved, it is preferable to add polyester polyurethane. The polyester polyurethane is preferably a reactant of a polyester and a diisocyanate represented by the following general formula (1), and more preferably, it is soluble in dichloromethane. (1) Η- (-0- (CH2) q-00C- (CH2) m-C0) η-0- (CH2) q-0H (where q is an integer of 2 to 4 and m is 2 to 2 An integer of 4, and η represents an integer of 1 to 100) More specifically, the constituent polyester-based alcohol component is ethylene glycol, 1,3-propanediol, or 1,4-butanediol, and a dibasic acid component. It is a polyester with hydroxyl groups at both ends formed by succinic acid, glutaric acid, or adipic acid, and the degree of polymerization η thereof is 1 to 100. When the polymerization degree η is 1 to 100, the optimum polymerization degree varies depending on the type of alcohol and dibasic acid used, and the molecular weight of the polyester is more preferably in the range of 1,000 to 4,500. Dichloromethane-soluble polyester urethane resins can be prepared by reacting a polyester with a diisocyanate of formula (1). The general formula is a compound represented by the repeating unit of formula (2). (2) CONH-R-NHCO- (0- (CH2) cOOC- (CH2) cCO) nO- (CH2: U-0) _ (where q is an integer of 2 to 4 and m is 2 to 4 In the integer, η represents an integer of 1 to 100, and R represents a divalent radical group residue.) The divalent radical group residue is represented by the following formula, for example. -38- 581885 V. Description of the invention (π: (R1) — (CH2) p— (p = 2 ~ 8) (R2)

I ch3

(R4)

(R5)

The diisocyanate components used are, for example, typical polydiisocyanates such as ethyl diisocyanate, trimethyl diisocyanate, tetramethyl diisocyanate, and hexamethyl diisocyanate. Methyl ester (general formula: OCN (CH2) pNCO (p is an integer from 2 to 8)), p-phenylene diisocyanate, tolyl diisocyanate, P · P'-diisocyanate Aromatic diisocyanates such as phenylmethane ester, diisocyanate-1,5-naphthyl ester, and diisocyanate-m-xylyl ester are not limited thereto. Among these, toluene diisocyanate, diisocyanate-m-xylyl ester, and tetramethylene diisocyanate are preferred in terms of easy availability, stability, and ease of handling. In the case of a urethane, it is preferable because it has excellent compatibility with a cellulose acetate film. -39- 581885 V. Description of the invention (38) The molecular weight of the polyester polyurethane resin is preferably 2000 to 50000, and it is appropriate depending on the type and molecular weight of the diisocyanate component polyester or these bonded groups. Decide. The molecular weight of the polyester polyurethane resin is more preferably 5,000 to 15,000 in terms of improving the mechanical properties of the cellulose acetate film and the compatibility with cellulose acetate.

The synthesis of dichloromethane-soluble polyester polyurethane can be easily prepared by mixing the polyester diols and diisocyanates represented by formula (1) and heating under stirring. The polyesters represented by the formula (1) can be obtained by thermal melting condensation of equivalent dibasic acids or their alkyl esters, polyesterification reaction or transesterification reaction with alcohols, or Either of the methods of the interface condensation of acid chloride and alcohol, the terminal group is appropriately adjusted to a hydroxyl group, and it is easily synthesized.

The dichloromethane-soluble polyester polyurethane resin used in the present invention has excellent compatibility with cellulose acetate having a degree of vinegarization of more than 58%. The structure of the resin is slightly different. When the molecular weight of the polyester polyurethane is 10,000 or less, 100 parts by mass of cellulose acetate is compatible with 200 parts by mass of the polyester polyurethane. . Therefore, when the polyester polyurethane resin is mixed with cellulose acetate to improve the mechanical properties of the film, the content of the polyester polyurethane resin can be based on the type, molecular weight, and location of the polyurethane. The desired mechanical properties are appropriately determined. In order to maintain the characteristics of cellulose acetate and improve the mechanical properties, 100 parts by mass of cellulose acetate should contain 0.1 to 30 parts by mass of polyester polyaminomethyl-40-581885. 5. Description of the invention (3 £) Ester resin is preferred. Also, the polyester polyurethane resin is stable at least at 180 ° C without thermal decomposition. The dichloromethane-soluble polyester polyurethanes have a degree of acetic acidification. More than 58% cellulose acetate and TZm have good compatibility. Therefore, y is mixed to form a film: When: a very transparent film can be obtained. And because these polyester polyurethanes have an average molecular weight iRj, they are different from conventional low-molecular-weight plasticizers, and they hardly volatilize even at high temperatures. The plasticizer volatilization of conventional plasticizers rarely occurs in subsequent processing \ Disadvantages due to migration 〇 By adding polyester polyurethane to the cellulose acetate film, local temperature and low temperature will be caused The lower bending strength and crack initiation strength become larger, so the film may be broken. In the past, when the bending strength and crack initiation strength of the film were raised, a low molecular plasticizer was used. This method has a normal temperature and humidity. The effect to some extent is that the film becomes extremely soft at low temperature and local humidity, and the 4ττΓ- method obtains a satisfactory effect. 0 In addition, it is possible to improve the mechanical properties by low molecular plasticizers.5 The addition amount of the agent and mechanical properties such as tensile strength are significantly reduced. 0 When dichloromethane soluble polyester polyurethane resin is added to cellulose acetate) The resin is added JS. The tensile strength is slightly reduced. In this case, when compared with the addition of a low-molecular-weight plasticizer, it is apparent that a small reduction in strength is obtained, and a strong and tough film having approximately the same flexural strength as that without addition is obtained. In addition, by mixing the polyester polyurethane, it can prevent low temperature and local humidity.-41-

581885 V. Description of the invention (40) The migration of plasticizer. Therefore, a transparent and shiny film is obtained which does not adhere to the film, has a very soft, wrinkle-free condition. (High thermal conductivity particles) The thermal conductivity of the cellulose acetate film is preferably 1 W / (m_K) or more. The higher the thermal conductivity, the better, but it is generally less than 0W / (m · K) when adjusted by the following method. In order to control the thermal conductivity of the cellulose acetate film, it is preferable to add highly thermally conductive particles to the dope used in the production of the cellulose acetate film. In addition, in order to control the thermal conductivity, a heat conductive layer containing highly thermally conductive particles is additionally provided on one surface of the cellulose acetate film. The heat conductive layer can be provided by co-casting a polymer containing highly thermally conductive particles with cellulose acetate, or by coating a cellulose acetate film. The materials of the highly thermally conductive particles include aluminum nitride, silicon nitride, boron nitride, magnesium nitride, silicon carbide, aluminum oxide, silicon oxide, zinc oxide, magnesium oxide, carbon, diamond, and metals. In order not to impair the transparency of the film, it is preferable to use transparent particles. The blending amount of the highly thermally conductive particles to the cellulose acetate film is preferably 5 to 100 parts by mass for 100 parts by mass of the cellulose acetate. If the blending amount is less than 5 parts by mass, the effect of improving heat conduction is insufficient, and if it is greater than 50 parts by mass, it is difficult in terms of productivity and the cellulose acetate film becomes brittle. The average particle diameter of the highly thermally conductive particles is preferably from 0.05 to 80 // m, and more preferably from 0.1 to 10 μm. Either spherical particles or acicular particles can be used. -42- 581885 V. Description of the invention (41) In the present invention, the thermal conductivity of the cellulose acetate film is measured as follows.酉 S acid cellulose thin film fl is sandwiched in a TO-3 heating box and compressed to 10% of the film thickness. Then, 5 W of electricity was applied to the copper heating box and held for 4 minutes, and the temperature difference between the copper heating box and the copper plate was measured. The thermal conductivity can be calculated by the following formula. Thermal conductivity {W / (m · K)) = {electricity (w) x thickness (m)) / {temperature difference (κ) X measured area (m2)} (stretching treatment of cellulose acetate film) is a modulation hysteresis It is better to stretch the cellulose acetate film when it acts and reduces the virtual distortion. By stretching the film, imaginary distortion in the stretching direction can be reduced. Therefore, in order to reduce the distortion in all directions in the plane, it is better to make the film biaxially stretched. The cellulose acetate film is preferably stretched at a stretching ratio of 3 to 100%. Biaxial stretching includes simultaneous biaxial stretching and sequential biaxial stretching. For continuous manufacturing, a sequential biaxial stretching method is preferred. After the solution is cast in a biaxial stretching method, the film is peeled from the tube or barrel, stretched in the width direction, and then stretched in the length direction. This stretching is performed in the order of the longitudinal direction and the width direction. Methods of stretching in the width direction include, for example, JP-A-Sho 62-1 1 5035, JP-A-Hei 4-152125, the same as 4-2842 1 1, the same as 4- 2983 1 0, and the same as 1 1-4827 1 And other records. Stretching of the film is carried out under long temperature or heating conditions. The heating temperature is preferably below the glass transition temperature of the film. Film -43- 581885 V. Description of the invention (42) It can be stretched during processing in drying, especially when solvent remains. When the film is stretched in the longitudinal direction, for example, the speed of the film transfer roller is adjusted to stretch the film at a film winding speed faster than the film peeling speed. When the film is stretched in the width direction, the film is held and transported by a tenter, and the film is gradually expanded by the tenter to stretch the film. After the film is dried, it can be stretched with a stretcher (preferably, it is stretched uniaxially with a long stretcher). The stretch ratio of the film (by increasing the proportion of the original length stretch) is preferably 5 to 50%, more preferably 10 to 40%, and most preferably 15 to 35. The processes from casting to post-drying can be performed in an air atmosphere or an inert gas atmosphere such as a nitrogen gas. The coiler used in the production of the cellulose acetate film used in the present invention can be used by general users, and can be wound using a constant tension method, a fixed torque method, a taper tension method, an internal stress-programmed tension control method, and the like. Method to take it up. (Hygroscopic expansion coefficient) The hygroscopic expansion coefficient indicates the amount of change in the length of a sample when the relative humidity is changed at a certain temperature. In order to prevent the frame-like transmittance from rising, the hygroscopic expansion coefficient of cellulose acetate film is preferably 30 × 10 · 5 / MΗ or less, more preferably 15 × l (T5 /% RH or less, and the most preferable is 10M0 · 5 / MΗ Below, the smaller the coefficient of hygroscopic expansion, the better, usually 1.0 M0 · 5 /% RH or more. The method for measuring the coefficient of hygroscopic expansion is as follows. From the produced polymer film (phase difference plate) ) The width is 5 digits. Cut out a sample with a length of 20γτιιτι and fix the other end, and hang it at 25 ° C, 20MΗ (Κϋ) atmosphere. Another -44- 581885 V. Description of the invention (43) One end hangs 0.5 The load of g 'is left for 10 minutes and the length (L.) is measured. Next, the length (h) is measured at a temperature of 25 ° C and a humidity of 80% cents (1 ^). The coefficient of hygroscopic expansion is calculated by the following formula .Measurement is made on 10 identical samples, using average 値. Moisture expansion coefficient [/% RH] = {(1 ^ —L.) / L.} / (Ri —R.) The above dimensional changes due to moisture absorption It can be known from the small free volume of the polymer film. When the free volume is large, there will be residual solvent amount during film formation. The smaller the general method to reduce the residual solvent is drying at high temperature and for a long time, but the productivity will be reduced when the time is quite long. Therefore, the amount of residual solvent is 0.001 to 1 mass for cellulose acetate film. % Is better, more preferred is 0.02 to 0.07 mass%, and the most preferred is 0.03 to 0.055% by mass. By controlling the amount of the residual solvent, a polarizing plate having optical compensation energy can be made at a low price. Manufacture with high productivity. In addition, it is preferable to add a compound having a hydrophobic group as another method to reduce the dimensional change due to the moisture absorption. As long as the raw material having a hydrophobic group is a hydrophobic group having an alkyl group or a phenyl group in the molecule The raw materials are sufficient, and there is no particular limitation, and especially the plasticizers or anti-deterioration agents added to the above cellulose acetate film are better. Such preferable raw materials are, for example, triphenyl phosphate (TPP), triphenyl phosphate Benzylamine (TBA), etc. The amount of these compounds having a hydrophobic group is preferably from 0.1 to 10% by mass for the adjusted solution (dope), and more preferably from 0.1 to 5 Mass%, the best is 1 to 3 mass%. — -45- 581885 V. Description of the invention (44) The amount of residual solvent is that a certain amount of sample is dissolved in chloroform and measured by gas chromatography (GC1 8 A, manufactured by Shimadzu Corporation). Solution Casting The method is to use a solution (dope) in which a polymer material is dissolved in an organic solvent to make a film. The drying by the solution casting method is as follows when the barrel (or tube) is used to dry the film. (Or tube) When the surface is dry, it is better to dry slowly at a temperature not exceeding the boiling point of the solvent used (foaming above the boiling point). Moreover, the drying during film transport is to transfer the glass of the polymer material. It is better to perform at the point ± 30t, and the better is ± 20 ° C. (Surface treatment of cellulose acetate film) It is preferable to apply a surface treatment to the cellulose acetate film. The surface treatment includes, for example, saponification treatment, plasma treatment, flame treatment, and ultraviolet irradiation treatment. The saponification treatment includes an acid saponification treatment and an alkali saponification treatment. The plasma treatment includes a corona discharge treatment and a glow discharge treatment. In addition, as described in Japanese Patent Application Laid-Open No. 7-3 3 3 43 3, it is preferable to use an undercoat layer. The surface energy of the film after the surface treatment is preferably 55 mN / m or more, and more preferably 60 mN / m to 75 mN / m. By using the cellulose acetate film as a transparent protective film for a polarizing plate, the adhesion between the polarizing film and the cellulose acetate film can be improved. When an optically anisotropic layer is provided on the cellulose acetate film, in order to ensure the adhesion between the conventional cellulose acetate film and the alignment film, a gelatin undercoat layer must be provided between the two. By using a surface energy of 55 ~ 75mN / m cellulose acetate film can be used without gelatin undercoating. In terms of maintaining the flatness of the film, the temperature of the cellulose acetate film is -46- 581885 in these treatments. 5. Description of the invention (45) Tg (glass transition temperature) or less, specifically 150 ° C or less Better. When an optical compensation sheet is used as the transparent protection M of the polarizing plate, it is more preferable to apply an acid treatment or an alkali treatment, and an alkali treatment to the cellulose acetate film in terms of adhesion to the polarizing film. The surface energy of a solid can be obtained by the contact angle method, moist heat method, and adsorption method described in "The Foundation and Application of Wet" (published by Tria Rice, Inc., 1 989. 1 2.10). . In the case of the cellulose acetate film of the present invention, the contact angle method is preferably used. Specifically, two kinds of solutions having a known surface energy are dropped into a cellulose acetate film, and an angle formed by the wiring of the droplet and the surface of the film is drawn at the intersection of the surface of the droplet and the surface of the film. The angle is defined as the contact angle, and the surface energy of the film can be calculated by calculation. The alkalizing treatment is preferably performed by immersing the surface of the film in an alkali solution, and then neutralizing, washing, and drying with an acidic solution. The alkali solution includes, for example, a potassium hydroxide solution and a sodium hydroxide solution, and the prescribed concentration of the hydroxide ion is preferably 0.1 to 3.0N, and more preferably 0.5 to 2.0N. The temperature of the alkaline solution is preferably room temperature to 90 ° C, and more preferably 40 to 70 ° C. The alkali is preferably an alkali metal hydroxide of sodium hydroxide or potassium hydroxide. The pH of the aqueous solution is preferably 10 or more. The alkali treatment is preferably carried out by immersing at least the side surface of the polarizing film of the cellulose acetate film in an alkali aqueous solution, or both sides may be alkali treated. The dipping treatment is preferably 1 to 300 seconds, and more preferably 5 to 240 seconds. The processing temperature is 25 ~ 7 (TC is better, more preferably 35 ~ 60t. After the dipping is finished, it is better to wash the cellulose acetate film with water. When only one-sided alkali treatment is performed, water washing is performed after alkali coating. At this time, 581885 V. Description of the invention (46), it is better that the solvent of the alkali coating solution does not swell the cellulose acetate film. And 'to improve coating properties or alkali solubility, propylene glycol can be used. Or a mixed solvent of water. By performing this alkalizing treatment, the change of Re550 before and after the alkalizing treatment of the cellulose acetate film can be changed to 3 nm or less. In addition, the alkali solution used in the alkalizing treatment does not cause yellowing after the treatment. The corona discharge treatment is to apply a high voltage between the electrode connected to the high voltage generating device and the induction roller, and place a cellulose acetate film in the corona discharge generated between the electrode and the induction roller, or move it. In addition, in this specification, it is described that the frequency of applying a high voltage between the electrode and the electromotive roller is the discharge frequency. Corona discharge treatment is extremely simple in the atmosphere, and the treatment device is sealed or semi-closed as required. In the closed state, other gases can be filled or mixed with other gases such as nitrogen, oxygen, and oxygen. In corona discharge treatment, the discharge frequency is generally 50Hz ~ 5000kHz, and the frequency is 5kHz ~ 100kHz. If the discharge frequency is too low in the corona discharge treatment, the discharge is unstable and pinholes will be generated in the cellulose acetate film, so it is not desirable. In addition, if the discharge frequency is too high, a device must be added to adjust the impedance In addition, the device is extremely expensive, so it is not desirable. Generally, when the wettability is improved, the corona discharge treatment of the cellulose acetate film is preferably 0 · 00 1 ~ 5kV · A · min / m2, more preferably 0 · 01 to lkV · A · min / m2. The distance between the electrode and the electromotive roller is preferably 0.5 to 2.5 mm, and more preferably 1.0 to 2.0 mm.

-48- 581885 5. Description of the Invention (47) Glow discharge treatment is to apply a high voltage between a pair of electrodes in a low-pressure gas, place a cellulose acetate film in the glow discharge generated between the electrodes, or move it. The gas pressure in the glow discharge process is generally 0.005 to 20 Torr, and more preferably 0.02 to 2 Torr. If the pressure is too low, the surface treatment effect decreases. If excessive current flows when the pressure is too high, sparks may be easily generated and the cellulose acetate may be damaged. The discharge can be generated by applying a high voltage between metal plates or metal rods arranged in more than one space in a vacuum. This voltage can be obtained by the composition and pressure of the atmospheric gas, and usually causes a stable steady glow discharge within the above pressure range between 500 and 5000V. In order to improve the adhesion, the range of the applied voltage is preferably 2000 to 4000V. In addition, the discharge frequency is generally from DC to 1000 MHz, and more preferably from 50 Hz to 20 MHz. In order to obtain the desired bonding strength, the glow discharge treatment of the treated object is preferably 0 · 0 1 to 5 kV · A · min / m2, and more preferably 0.15 to 1 kV * A · min / m2. The ultraviolet irradiation treatment can be performed by irradiating the cellulose acetate film with ultraviolet rays. When the surface temperature of the film is increased to 1 50 ° C during the ultraviolet irradiation treatment, there will be performance problems. A high-pressure mercury lamp with a main wavelength of 3 65 nm can be used as the light source. When low temperature processing is required: ^ It is better to use a low-pressure X mercury lamp with a main wavelength of 254nm. Moreover, ozone-free high-pressure mercury lamps and low-pressure mercury lamps can also be used. Regarding the amount of processed light, although the more the amount of processed light, the adhesion between the thin film and the adhered layer can be increased, but with the increase of the amount of light, the film will be colored and the film will become brittle easily. Therefore, when using a high-pressure mercury lamp with a main wavelength of 3 6 5nm -49- 581885 V. Invention Description (4 8), the irradiation light quantity is preferably 20 to 10,000 (m) / cm2, and the more preferable is 50 to 2000 ( mJ / cm2). When a low-pressure mercury lamp with a main wavelength of 254 nm is used, the irradiation light amount is preferably 100 to 10,000 (mJ / cm2), and more preferably 300 to 150 (mJ / cm2). (Optical compensation sheet having an optically anisotropic layer) The optical compensation sheet having an optically anisotropic layer of the present invention can be produced by disposing an optically anisotropic layer formed of a liquid crystal compound on a cellulose acetate film. An alignment film is preferably provided between the cellulose acetate film and the optically anisotropic layer provided thereon. The alignment film allows the liquid crystalline compound used in the present invention to be aligned and operated in a certain direction. Therefore, the alignment film is an essential product when manufacturing the optical compensation sheet of the present invention. However, when the liquid crystal compound is aligned and its alignment state is fixed, the alignment film can achieve its effect, so it is an essential product as a constituent element of the optical compensation sheet. In other words, only the optically anisotropic layer on the alignment film whose alignment state is fixed can be copied on the cellulose acetate film to produce an optical compensation sheet. (Alignment film) The alignment film has a function of defining an alignment direction of a liquid crystal compound. The alignment film can be processed by lamination of organic compounds (preferably polymers), oblique evaporation of inorganic compounds, formation of layers with micro-groups, or accumulation of organic compounds (such as ω) -Method of behenic acid, octacosylmethylammonium chloride, methyl stearate). In addition, by applying an electric field, a magnetic field, or light irradiation, an alignment film having an alignment function can be obtained. The alignment film is preferably formed by laminating a polymer. -50- 581885 V. Description of the invention (49) It is better to form the alignment film by laminating polymer. Polyvinyl alcohol is preferably a polymer. The preferred polymer is more preferably a modified polyvinyl alcohol having a hydrophobic group bonded thereto. The alignment film may be formed of one kind of polymer, so that a layer made of two kinds of cross-linked polymers is preferably formed by lamination. As the at least one polymer, a polymer that can be crosslinked by itself or a polymer that is crosslinked by a cross-linking agent is preferably an alignment film. Heat, pH change, etc. are formed between polymers; or a cross-linking agent of a highly reactive compound is used to introduce a bond group derived from the cross-linking agent between the polymers to form a cross-link between the polymers. This cross-linking is performed by applying the above-mentioned polymer or an alignment coating solution containing a mixture of a polymer and a cross-linking agent to a cellulose acetate film, followed by heating or the like. In order to ensure the durability of the final product (optical compensation sheet), the cellulose acetate film may be coated with an alignment film and then subjected to a crosslinking treatment at any stage until the optical compensation sheet is obtained. In consideration of the orientation of a layer (optically anisotropic layer) made of a liquid crystal compound formed on the alignment film, it is preferable that the liquid crystal compound is fully crosslinked after being aligned. The cross-linking of the alignment film is generally performed by coating an alignment film coating liquid on a cellulose acetate film and heating and drying it. The heating temperature of the coating liquid is set to a low temperature, and it is preferable to perform sufficient cross-linking of the alignment film during the addition treatment stage when forming the optically anisotropic layer.

• 51-581885 5. Description of the invention (50) The polymer used for the alignment film may be a polymer crosslinked by itself or a polymer crosslinked by a crosslinking agent. Of course, it can also be a two-way polymer. Examples of the polymer include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleimide copolymer, polyvinyl alcohol and modified polyvinyl alcohol, and poly (N-hydroxymethacrylamide). ), Styrene / vinyl toluene copolymer, chlorinated polyethylene, nitrocellulose, polyvinyl chloride vinyl, chlorinated polyolefin, polyester, polyimide, vinyl acetate / chlorinated vinyl copolymer Polymers, polymers such as ethylene / vinyl acetate copolymers, carboxymethyl cellulose, polyethylene, polypropylene, and polycarbonate, and compounds such as silane coupling agents. Preferred polymers are, for example, water-soluble polymers such as poly (N-hydroxymethyl acrylamide), carboxymethyl cellulose, gelatin, polyvinyl alcohol, and modified polyvinyl alcohol. Gelatin, polyvinyl alcohol, and modified polyvinyl alcohol are preferred, and more preferred are polyvinyl alcohol and modified polyvinyl alcohol. Furthermore, it is most preferable to use two kinds of polyvinyl alcohols or modified polyvinyl alcohols having different polymerization degrees. Polyvinyl alcohol is, for example, polyvinyl alcohol having a degree of alkalinity of 70 to 100%. Generally, the degree of alkalinity is 80 to 100%, and more preferably 85 to 95%. In addition, the degree of polymerization of polyvinyl alcohol is preferably 100 to 3000. Examples of the modified polyvinyl alcohol include polyvinyl alcohol modified by copolymerization, modified by chain movement, or modified by block polymerization. Examples of the modification group during the copolymerization modification include COONa, Si (OX) 3, N (CH3) 3 · Cl, C9H | 9COO, S03, Na, C12H25, and the like. Examples of the modification group when modified by chain transfer include COONa, SH, C12H25, and the like. Moreover, when modified by block polymerization,

-52- 581885 V. Description of the invention (51) Modified groups include, for example, COOH, CONH2, COOR, C6H5. Among these, unmodified or modified polyvinyl alcohol having a degree of alkalinity of 80 to 100% is preferred. Moreover, unmodified polyvinyl alcohol and modified polyvinyl alcohol having a degree of alkalinity of 85 to 95% are more preferable. The modified polyvinyl alcohol is particularly preferably a polyvinyl alcohol modified product using a compound represented by the following general formula. The modified polyvinyl alcohol is described in the following specific modified polyethylene glycol.

(Wherein 'R1' represents an alkyl group, an acrylfluorenylalkyl group, a methacrylfluorenyl group group, or an epoxy alkyl group; W is a halogen atom, an alkyl group, or an alkoxy group; X is a formation activity Necessary atomic group of ester, acid anhydride, or acid halide; P is 0 or 1; η is an integer of 0 to 4) The specific modified polyvinyl alcohol described above is also a polyvinyl alcohol of a compound represented by the following general formula Modified materials are preferred.

(Wherein “X1” is an atomic group necessary to form an active ester, acid anhydride, or halide, and m is an integer of 2 to 24. Examples of the polyvinyl alcohol used for reacting with a compound represented by the general formula include: The above-mentioned unmodified polyvinyl alcohol and copolymerized modified products, namely, -53-581885 V. Description of the invention (52) Polyethylene modified by chain movement, modified by block polymerization, etc. Alcohol modification. Preferable details of the specific modified polyvinyl alcohol are described in detail in, for example, Japanese Patent Application Laid-Open No. 9: 52509. The methods for synthesizing these polymers, such as the measurement of visible absorption spectrum and the method for determining the rate of introduction of the modified group, are described in detail in Japanese Patent Application Laid-Open No. 8-3389 1. Examples of the crosslinking agent include aldehydes, N-methylol compounds, dioxane derivatives, compounds activated by carboxyl groups, activated ethylene compounds, activated halides, isoxazoles, and dialdehyde starches. Examples of the aldehydes include formaldehyde, acetaldehyde, and valeraldehyde. Examples of the N-hydroxymethyl compound include dimethylol urea and hydroxymethyl dimethylhein. Dioxane derivatives are, for example, 2,3-dihydroxydioxane. Examples of compounds that activate carboxyl groups include carbonyloxy key salts, 2-naphthalenesulfonates, 1,1-bispyrrolidinyl-1 -pyridinium chloride, and 丨 morpholinylcarbonyl-3-( Sulfoaminomethyl). Examples of activated ethylene compounds include 1,3,5-tripropenyl-hexahydro-second 2-trap, bis (vinyl maple) methane, and n, N, -methinebis [Θ-(vinylsulfonate Group) ammonium propionate]. The active halide is, for example, 2,4-dichloro-6-hydroxy-S-triple. These can be used alone or in combination. It is preferable to use the above-mentioned water-soluble polymer, especially polyvinyl alcohol and modified polyvinyl alcohol (including the specific modified product described above). In terms of productivity, it is preferable to use aldehydes having high reactivity, that is, valeraldehyde. There is no particular limitation on the amount of crosslinker added to the polymer. Moisture resistance When adding more cross-linking agents, it tends to be better. However, when the crosslinking agent is added to the polymer in an amount of 50% by mass or more, the alignment energy as an alignment film is reduced. -54- 581885 V. Description of the invention (53) Therefore, '¥ 1 [Polymer and eye parenter's additive house; with 0.1 to 2 0% by mass of chapter, better, 0.5 to 1 5 quality%. The alignment film still contains a certain amount of unreacted crosslinking agent even after the crosslinking reaction is completed, but the amount of the crosslinking agent in the alignment film is preferably 1.0% by mass or less, and more preferably 0.5. Mass% or less. When the alignment film contains an unreacted crosslinking agent of more than 1.0% by mass, sufficient durability cannot be obtained. In other words, when it is used in a liquid crystal display device, a strange phenomenon may occur when it is used for a long time or in a high temperature and high humidity atmosphere for a long time.

The alignment film is formed by applying a solution containing the above polymer or a solution containing the above polymer and a cross-linking agent onto a cellulose acetate film, followed by drying by heating (crosslinking), and lamination. The crosslinking reaction may be performed at any time after the coating liquid is applied to the cellulose acetate film. Next, when a water-soluble polymer such as polyvinyl alcohol is used as an alignment film forming material, it is preferable to use an organic solvent such as methanol having a defoaming effect or a mixed solvent of an organic solvent and water in order to prepare a solvent for the coating solution. When using methanol as an organic solvent, the ratio is based on the mass ratio of water: methanol is generally 0:

1 00 ~ 99: 1, preferably 0: 1 00 ~ 9 1: 9. This can suppress the generation of foam and significantly reduce the surface defects of the alignment film and the optically anisotropic layer. Examples of the coating method include a spin coating method, a dip coating method, a curtain coating method, an extrusion coating method, a rod coating method, and an E-type coating method. Of these, E-type coating is preferred. The thickness of the alignment film is preferably from 0 · 1 to 1 0 // Hi. Heating and drying can be performed at a heating temperature of 60 to 100 ° C, and more preferably 80 to 100 x. Drying time can be -55- 581885 V. Description of the invention (54) It is performed in 1 minute to 36 hours. It is preferably 5 to 30 minutes. PH 値 & is preferably set to the most suitable cross-linking agent to be used. When valeraldehyde is used, pH 値 is 4.5 ~ 5.5 is better, more preferably pH5. The alignment film is disposed on the cellulose acetate film or the undercoat layer. The alignment film is obtained by cross-linking the polymer layer and then by forming a surface area layer. The lamination process can use a processing method widely used in LCD liquid crystal alignment processing projects. In other words, it is a method of using paper or gauze, blanket 'rubber or nylon, polyester fiber, etc. on the surface of the alignment film to obtain the alignment by wiping in a certain direction. Generally, it is carried out by laminating several times by using a cloth with an average length of fibers and uniformly planted fibers. The alignment film has a predetermined function for aligning a liquid crystal compound provided thereon. (Optically Anisotropic Layer) In the present invention, the optically anisotropic layer formed of a liquid crystal compound is formed on an alignment film provided on a cellulose acetate film. The liquid crystal compound used in the optically anisotropic layer includes a rod-shaped liquid crystal compound and a disc-shaped liquid crystal compound. The rod-shaped liquid crystal compound and the disc-shaped liquid crystal compound may be polymer liquid crystals or low-molecular liquid crystals, and include liquid crystals having low-molecular liquid crystals which are not crosslinked. The optically anisotropic layer can be formed by applying a coating liquid containing a liquid crystal compound and a polymerizable initiator or an optional component as required on the alignment film. It is preferable to adjust the solvent used for the coating liquid to use an organic solvent. Organic solvents include, for example, amidines (for example, N, N-dimethylformamide), methylene (for example, dimethylmethylene), heterocyclic compounds (for example, pyridine), and hydrocarbons (for example, benzene, hexane).

-56- 581885 V. Description of the invention (55) Alkanes), halogenated alkyls (such as chloroform, dichloromethane, tetrachloroethane), esters (such as methyl acetate, butyl acetate), ketones (such as acetone, methyl Ethyl ketone), ethers (such as tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides and ketones are preferred. Two or more organic solvents can be used. The coating liquid can be applied by conventional methods (for example, a bar coating method, an extrusion coating method, a direct photogravure coating method, a reversible photogravure coating method, and a mold coating method).

The thickness of the optically anisotropic layer is preferably in the range of 0.1 to 20 # m, more preferably 0.5 to 1 and 10 to 10 // m. The liquid crystalline compound used in the present invention is preferably a discotic liquid crystalline compound. (Rod-shaped liquid crystalline compound)

As the rod-like liquid crystalline compound, azomethine, azooxy, cyanobiphenyl ', cyanophenyl, benzoate, cyclohexanecarboxylic acid benzoate, and cyanophenyl are used. Cyclohexanes, cyano-substituted phenylpyridines, and alkoxy-substituted Π are preferred over π-baseds, phenyldioxanes, diphenylacetylenes, and alkenylcyclohexylbenzonitrile. Furthermore, the metal compound is contained in the rod-like liquid crystalline compound. Alternatively, a liquid crystal polymer contained in a rod-shaped liquid crystal compound as a repeating unit may be used as the rod-shaped liquid crystal compound. In other words, the rod-like liquid crystalline compound may be bonded to a (liquid crystal) polymer. About the rod-like liquid crystalline compounds, such as quarterly chemistry, 22 volumes of liquid crystal chemistry (1 994) Chapter 4, Chapter 7 and Chapter 11 edited by the Japanese Chemical Society, and -57- 581885 5. Description of the invention (56) LCD Display Manual Chapter 14 of the Committee for the Promotion of the Japanese Academy of Sciences, Chapter 12 The birefringence of the rod-like liquid crystal compound is preferably in the range of 0.00 to 0.7. When the rod-like liquid crystalline compound has a fixed alignment state, it is preferable to have a polymerizable group. Examples of the polymerizable group (Q) are described below. Cut (Q2) (Q3) (Q4) —CH = QH2 —CH; CH-CH3 —CH: i: CH-C2H5. —CH two CH-n-C3H7 (Q5) (Q6) (Q7) (Q8) ( Q9) (Ql〇)

--C = CH2 --CH-C-CH3 --CECH 0 H --SH CH3 CH〇-CH ~ CHp N, -ch-ch2 (Qll) (Q12) (Q13) (Q14) (Q15) (Q16) (Q! 7)

—CHO —OH —C02H —N = C = 0 —NH2 —S03H —N = C = S Polymerizable group (Q) is unsaturated polymerizable group (q 1 ~ Q7), epoxy group (Q8) or triple well The group (Q9) is preferred, the unsaturated polymerizable group is more preferred, and the ethylenically unsaturated polymerizable group (Q1 to Q6) is most preferred. It is preferable that the rod-like liquid crystalline compound has an approximately symmetrical molecular structure in the minor axis direction. Therefore, it is preferable to have polymerizable groups at both ends of the rod-like molecular structure. -58 · 581885 V. Description of the invention (57 Examples of rod-shaped liquid crystalline compounds are shown in the following (N1)

c〇 一 ο -〇-cn (N2) P 'H2G DiC Η-〇〇〇〇〇〇71 ^ 4

CO (Ν3) CH2 = CH -C〇 -0-C7H14 (N4) P 'h2c -ch-c〇-〇-c7h14

(N5) / — \ ch2 = ch —c〇〇〇 一 c7h14— ^ / rCN -59- 581885

581885 V. Description of the invention (59 (N16)

CH ^ CH —C〇〇〇〇〇〇7 ^ 14 N = N General 〇C4H9 (N17) CH2 = CH -CO -〇_C7H140 -CH: N—C4H9 (N18) ch2 = ch ~ co -o-c5h10 ( N19)

Η2〇 / —b.H —C〇〇〇 一 C7H14— 三 C 一 ^ r " ^ > -〇C2H5 (N20) / -χ ch2 = ch-cq-o-c3h6—H ^ -ch = qh

. (N21) CH = CH 10010 107H14 -〇-c °-° -〇-v_, (N22) P 'H2C —CH —〇〇〇〇〇07H14

ch-co-o-c7h14o n = ch

N-ί: x / -〇5H ^ N = N

CH ^ (N24) O H ^ C-CH-CO -〇-C7H14-C〇〇〇

Credit (N25) CH2 = CH —C〇〇〇 一一 7H14 CO -0— < x N > -CN F F. OCsHn -61-581885 V. 'Explanation of invention (6〇

CH2 (N26) CH CO

CH II CH i · CO 2 0-C4H80 ~ H ^ >-CO -o general

〇_C〇 普, ch2. 〇C 丨 CH I .CO 〇C4H8 —〇

CH2 (N28) CH

N = CH

F

2 Η H〇crc--cl〇 0: He-

CH2 (N30) CH CO o—c7h14 ~ Qr CH = CH-CO-0 o.c4 2 Η H〇CM cl CIO I n8 (N31) ch2 = ch_c〇〇〇 一 c7h14 (N32) P, h2c-ch- co ~ o-c7h14 (N33). CH2 = CH — c〇〇〇 一 c7h14

〇C8H t 6 —〇 One C〇 One C H Two C H2

oc3h6 ~ o-hc-ch2 oc3h6-o-hAh2 -62- 581885 V. Description of the invention (61 (N34) GH2 = CH—C〇 一 〇_C7H14—η} — {Η) —〇C8H16—〇'-CO ~ CH ::: CH2 (N35)

CHp II. ^ CH C2H4

(N36) CH2 = CH -CO -O-C5H10 (N37) P, h2chdh -c〇-〇_c7h14

OC ^ H! 〇 -0 -CO -C H = C H2

.〇.C5H10-〇-C〇-hAh2

CH2 (N38) C ~ CH

CHo II ^ C-CHo 1 d CO -c ◦ 一 〇c5h10 — FREE

.CH2 (N39), CH 2

CH2 (N40) 9-ch3. CO 〇C7H14〇

CH 1 CO I CH2 ii ^ C-CH,

CO 〇〇5Η1〇 —〇-63- 581885 V. Description of the invention (62) (N41). CH2 = CH—C〇-〇〇 一一 7H14 — ^^ — 〇 一 C〇

(N42) CH2 = CH —C〇〇〇〇 一 c7h14-^^ > -〇 一 c〇 ch2 == ch-co ~ o-c7h14—V-o-co

Fe (N43)

oc7h14-o -64- 581885 V. Description of the invention (63)

-65- V. Description of the Invention (64) The optically anisotropic layer contains a rod-like liquid crystalline compound or a polymerizable initiator or any additive described below (for example, a plasticizer, a monomer, a surfactant, a cellulose ester, A liquid crystal composition (coating solution) of a 1,3,5-triple compound) is formed on the alignment film by coating. (Disc-shaped liquid crystal compound) Since the above-mentioned disc-shaped (liquid crystal) compound generally has a large negative refractive index and various alignment forms, a conventional stretched negative refractive index film can be produced by using a disc-shaped compound. Unobtainable optical compensation sheet with optical properties. An optical compensation sheet using a disc-shaped compound is disclosed in JP-A-H 6-2 1 4 1 16, US Patent 558 367 9, US 56 46 7 0 3, and West German Patent Gazette 39 1 1 620A1. Documented. The discotic (nematic) liquid crystalline compounds include, for example, the research report by C. Destrade, et al., M ο 1. C1 · yst. 71 Vol. 1, 11 (p. 181). Wu, C. Destrade et al.'S research report, Mol. Cryst. 122, 141 (1985), Physics lett, A, 78, 82 (1 990), the indene derivatives, B. Kohne et al. Research Report, Angew Chei Vol. 96, Cyclohexane Derivatives described in 70 pages (1984) and JM Lehn et al. Research Report, Chem. Co_um. '1 794 pages (1 9 1985), J. Zhang et al.'S research report,]. Am. Chem · Soc. Vol. 116, 265 p. 5 (1, 994) phenylacetylene-based microcirculation, etc. In addition, the discotic liquid crystalline compound generally includes a mother core having such a molecular center, and a structure in which a linear alkyl group or an alkoxy group, a substituted benzyloxy group, or the like is substituted in a radial manner as a linear chain. With liquid crystal-66- ————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————- (65) The invention is described It is only necessary that the molecules have a negative uniaxiality and have a certain orientation, and are not limited to these. In addition, in the present invention, the optically anisotropic layer formed of a discotic liquid crystalline compound does not necessarily have to be the above-mentioned compound, and also includes, for example, a low-molecular discotic liquid crystalline compound that reacts with heat, light, or the like. Groups, as a result of which they are polymerized or cross-linked by reactions such as heat and light, have a high molecular weight, and lose liquid crystallinity. A preferred discotic liquid crystalline compound is described in, for example, Japanese Patent Application Laid-Open No. 8-27284. In order to polymerize and fix the discotic liquid crystalline compound, a polymerizable group as a substituent must be bonded to the discotic core of the discotic liquid crystalline compound. However, when the discotic fibers are directly bonded to the polymerizable group, it is not easy to maintain the alignment state during the polymerization reaction. Therefore, a bonding group is introduced between the disc-shaped core and the polymerizable group. Therefore, the discotic liquid crystalline compound having a polymerizable group is preferably a compound represented by the following formula (111). * (III) D (-L — P) rx (where D is a disc-shaped core, L is a divalent bonding group, P is a polymerizable group, and η is an integer of 4 to 12) Examples of the disc-shaped core (D) are described below. In the following examples, 1 ^ < or PL) means a combination of a divalent bonding group (L) and a polymerizable group (ρ). .

-67- 581885 V. Description of the Invention (66)

(D5) (D6)

PL LP

PL LP

(D7) PL LP

(D8) LP LP PL LP, Lp -68 ^ 581885 5. Description of the invention (67) (D9)

LP LP

(D10) LP

LP LP

(D11) .LP

-69 > 581885 V. Description of the invention (68 (D12)

LP

(D13) (D14)

PL LP

P.L LP

LP LP

PL LP

581885 V. Description of the invention (69) (In the formula (11 I), the divalent bonding group (L) is selected from the group consisting of an alkylene group, an alkylene group, an alkylene group, -CO-,--,-0 -, -S-and combinations thereof are preferably divalent bonding groups. The divalent bonding group (L) is selected from the group consisting of an alkylene group, an arylene group, _c〇 ... ~ NH-,-0- , -S-and the combination of divalent bonding groups are more preferable. The divalent bonding group (L) contains at least two selected from the group consisting of alkylene, aryl, -CCK, and -0-divalent. The two bonding groups are the best. The carbon number of the alkylene group is preferably 1 to 12. The carbon number of the alkylene group is preferably 2 to 12. The carbon number of the alkylene group is 6 ~ 1 0 is preferred) Examples of the divalent bonding group (L) are described below. The left side is bonded to the disc-shaped core (D), and the right side is bonded to the polymerizable group (P). AL means alkylene or alkenyl, AR means aryl. Furthermore, the alkylene, alkenyl, and arylene groups may have a substituent (e.g., an alkyl group). : One AL—C〇〇〇 一 AL—.; L 2: one AL ~ C〇—〇— AL ~ 〇— L 3: one AL — C〇〇〇 一 AL — 〇AL AL — ^ L 4: one AL_C 0_10_AL 10_C 0_L 5: 1 C 0_AR-0_AL-L 6: 1 C_0 AR-0_AL-0_L 7: 1 C_AR — 0 ~ AL—-〇— C〇— L 8: -C〇-NH ~ AL ~ L 9: -NH-AL —〇—L10: — NH — AL — 〇—C〇1

Lll: —〇— AL — L12: —〇—AL — 〇— L13: —〇 一 AL — O- C〇 一, L14: 〇AL— 〇 一 C〇-NH —.AL — -71-* 581885 V. Explanation of Ming (7〇) L15;-· 〇-AL-S-A TL-L * 16: ~ 〇-C0-AR-O-eight L ~ C〇-L17: 101-001 AR — Ο — AL — O — CO — L 18: —〇 — CO — AR — 〇 — AL — Ο — AL — 0 — CO — L19: — 〇 —CO * ~ AR — 0 ~ ~ AL — O — AL -— AL — Ο — C Ο — L20: -S-AL- · L21: -S-AL — 〇 • •. L22; —S-AL-O—CO—. L23: — S—A. L — S—AL—L24: ~ S—AR-AL—The polymerizable group (P) of formula (III) depends on the type of polymerization reaction. Examples of the polymerizable group (P) are described below. (P1)-(P2) (P3). —CH—CHg • —CmCH / —οη2 ^ ξοη (P4) (m .㈣ '—N H2 —s〇gH —ch2-ch-ch (P7) _ (P9 ) —C—CH2 ch3 —CH-CH-CHg —N = c = s' (P10) (Pll) _ —SH —CHO —OH · (P13) (P14) (P15) —0〇2 ^ * ~ CH = CHfc-C2H5 (P16) (? 17) (PI 8) —CH = CH-n ^ C3H7 —'— CH ^ CCH3 0 Λ V * CH3 ^ *. —Ch-ch2 581885 V. Description of the invention (71) Polymerization The unsaturated group (P) is preferably an unsaturated polymerizable group (PI, P2, P3, P7, P8, P15, P16, P17) or an epoxy group (P6, P18). The most preferred is an ethylenically unsaturated polymerizable group (P1, P7, P8, P15, P16, P17). In formula (III), η is an integer of 4 to 12. The specific number depends on the disc-shaped core. (D) depends on the type. Moreover, the combination of several L and P may be different or the same. The discotic liquid crystalline compound 'such as JP-A No. 7-28 1028, the same as 7-3063 1-7, the same Nos. 8-50206, 9-1 04656, 9-1 048 66, and 9-1 1 240 are described. When using a discotic liquid crystalline compound, optical anisotropy The layer is a layer having a negative refractive index, and the surface of the disc-shaped structural unit is inclined with respect to the surface of the cellulose acetate film, and the angle formed by the surface of the disc-shaped structural unit and the surface of the cellulose acetate film varies with the optical The depth direction of the anisotropic layer changes better. The angle (tilt angle) of the surface of the disc-shaped structural unit generally increases as the depth direction of the optical anisotropic layer and the distance from the bottom of the optical anisotropic layer increase or Decrease. It is better for the tilt angle to increase as the distance increases. In addition, changes in the tilt angle include, for example, continuous increase, continuous decrease, intermittent increase, intermittent decrease, changes including continuous increase and continuous decrease, and interruptions between increase and decrease. Change. Intermittent changes include the range where the tilt angle does not change during the thickness direction. The tilt angle also includes the range where the tilt angle does not change, and it is better to increase or decrease the whole. In addition, 'the tilt angle is better to increase the whole, especially to continuous changes. More preferably, the inclination angle of the disc-shaped unit on the carrier side can be determined by selecting the material of the disc-shaped liquid crystal compound or the alignment film, Or borrow

-73- 581885 V. Description of the invention (72) It is adjusted by selecting the layer processing method. The inclination angle of the I »discoid unit on the surface side (air side) is generally adjusted by the discotic liquid crystal compound or the discotic liquid crystal compound and the compound used. The discotic liquid crystal primary compound and the compound used include, for example, a plasticizer, a surfactant, a polymerizable monomer, and a polymer. In addition, the degree of change of the tilt angle can be adjusted by the same selection as described above.

The plasticizer, surfactant, and polymerizable single system used with the discotic liquid crystalline compound have compatibility with the discotic liquid crystalline compound, and have a function of changing the tilt angle of the discotic liquid crystalline compound. Or any compound that does not hinder the alignment. ‘Among these, a polymerizable monomer (for example, a compound having a vinyl group, a vinyloxy group, a propenyl group, and a methacryl group) is preferred. The amount of the compound to be added is generally 1 to 50% by mass, preferably 5 to 30% by mass, for the discotic liquid crystalline compound.

The polymer used with the discotic liquid crystalline compound may be any polymer having compatibility with the discotic liquid crystalline compound and having a function of changing the tilt angle of the discotic liquid crystalline compound. The polymer is, for example, cellulose ester. Preferred cellulose esters are, for example, cellulose acetate, cellulose acetate propionate, hydroxypropyl acetate, and cellulose acetate butyrate. The amount of the polymer added to the above-mentioned polymer without hindering the formulation of the discotic liquid crystalline compound is generally 0.1 to 1% by mass for the discotic liquid crystalline compound, and preferably 0.1 to 8 Mass%, more preferably 0.1 to 5 mass%. The optically anisotropic layer generally applies a solution in which a discotic liquid crystalline compound and other compounds are dissolved in a solvent is coated on the alignment film and dried. Then, -74 »581885 V. Description of the invention (73) Heating to a nematic phase It is obtained by maintaining the alignment state (nematic phase) and cooling. Or the optically anisotropic layer is a solution in which a discotic liquid crystalline compound and other compounds (such as a polymerizable monomer and a photopolymerization initiator) are dissolved in a solvent are applied to an alignment film, dried, and then heated to nematic Obtained after polymerization at the phase formation temperature (UV light irradiation, etc.) and cooling. The nematic liquid crystal phase-solid phase transfer temperature of the discotic liquid crystalline compound used in the present invention is preferably 70 to 30 CTC, and more preferably 70 to 170 ° C. (Fixing of the alignment state of the liquid crystal compound) The aligned liquid crystal compound can be fixed while maintaining the alignment state. The immobilization is preferably carried out by a polymerization reaction. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator. Photopolymerization is preferred. The photopolymerization initiator includes, for example, an α-carbonyl compound (described in US Pat. Nos. 23 6 7 66 1 and 23 67 6 70), an indole ether (described in US Pat. No. 2448828), and an α-hydrocarbon-substituted aromatic compound. Family marriage compounds (described in US Pat. No. 277225 12), polynuclear quinone compounds (US Pat. No. 3,046,27, and 295 1 7 5 8), triarylimidazoline dimers and p-amino groups Combinations of phenyl ketones (described in US Patent No. 3 5 4 9 3 6 7), pyridine and phenoxine compounds (Japanese Patent Publication No. 60-1 05 667, US Patent No. 423 98 50) and dioxin An azole compound (described in U.S. Patent No. 42 1 2970). The amount of the photopolymerization initiator used is preferably 0.001 to 20% by mass of the solid content of the coating liquid, and more preferably 0.5 to 5% by mass. -75- 581885 V. Description of the invention (74) In order to irradiate the liquid crystal compound with light, ultraviolet rays are preferably used. The irradiation energy is preferably 20 mJ / cm2 ~ 50 J / cm2, more preferably 20 J / cm2 ~ 5000 J / cm2, and most preferably 100 J / cm2 ~ 800 J / cm2. In order to promote the photopolymerization reaction, light irradiation may be performed under heating conditions. A protective layer may also be provided on the optically anisotropic layer. (Polarizing plate) The polarizing plate is made of a polarizing film and two transparent protective films arranged on its two sides. As one of the protective films, an optical compensation sheet made of the cellulose acetate film or an optical compensation sheet made of an optically anisotropic layer on the cellulose acetate film can be used. As the other protective film, a general cellulose acetate film can also be used. The polarizing film includes an iodine-based polarizing film, a dye-based polarizing film using a dichroic dye, or a polyolefin-based polarizing film. Iodine-based polarizing films and dye-based polarizing films are generally manufactured using polyvinyl alcohol-based films. The transmission axis of the polarizing film is equivalent to the direction perpendicular to the film stretching direction. It is preferred that the retardation axis of the cellulose acetate film and the transmission axis of the polarizing film be arranged substantially parallel or substantially vertically. Moreover, it turns out that the moisture permeability of a protective film is extremely important for the productivity of a polarizing plate. The polarizing film and the protective film are bonded with an aqueous adhesive, and the solvent of the adhesive is diffused in the protective film and dried. The higher the moisture permeability of the protective film, the faster the drying will improve the productivity, but when it is too high, the polarizing energy will be reduced due to the use of the liquid crystal display device (under high humidity) and moisture entering the polarizing film -76- 581885 Description of the invention (75) The moisture permeability of the optical compensation sheet is determined by the thickness, free volume, or hydrophobicity of the polymer film (and the polymerizable liquid crystal compound). When an optical compensation sheet is used as a protective film for a polarizing plate, the moisture permeability of the optical compensation sheet is preferably 100 to 1 000 (g / m2) / 24 hours, and more preferably 300 to 7 00 (g / m2) / 24 hour. The thickness of the optical compensation sheet can be adjusted by cutting flow rate and line speed, or stretching and compression when the cellulose acetate film is formed. Since the moisture permeability of the main materials used is different, the thickness can be adjusted to a better range. The free volume of the optical compensation sheet can be adjusted by drying temperature and time during film formation. At this time, since the moisture permeability of the main raw materials used is different, the free volume can be adjusted to a better range. The hydrophobicity of the optical compensation film can be adjusted by additives. When a hydrophilic additive is added to a free volume, moisture permeability can be improved, and when a hydrophobic additive is added, moisture permeability can be reduced. By adjusting the moisture permeability of the optical compensation sheet, a polarizing plate with optical compensation performance can be manufactured at low cost and high productivity. (Circular polarizing plate) The λ / 4 plate (optical compensation sheet made of cellulose acetate film) of the present invention and the polarizing film substantially form an angle between the retardation axis in the plane of the λ / 4 plate and the transmission axis of the polarizing film. Laminated at 45 ° to obtain a circular polarizer. Essentially 45. Means 40 ~ 50 °. The angle between the retardation axis in the λ / 4 plane and the transmission axis of the polarizing film is preferably 41 to 49 °, and more preferably 42 to 48. The best is 43 ~ 47. , Especially preferred is 44 ~ 46. . -ΊΊ-581885 V. Description of the invention (76) The λ / 4 of the polarizing film is preferably provided with a transparent protective film on the opposite side. The transparent protective film can also use a common cellulose acetate film. (Liquid crystal display device) The polarizing plate obtained by bonding the optical compensation sheet, or the optical compensation sheet and the polarizing film, is particularly useful for transmission type liquid crystal display devices and reflective Liquid crystal display device. Depending on the characteristics of the liquid crystal display device, the retardation of the optically anisotropic cellulose acetate film can be determined to be an appropriate one. (Transmissive liquid crystal display device)

A transmissive liquid crystal display device is composed of a liquid crystal cell and two polarizing plates disposed on both sides thereof. The polarizing plate is made of a polarizing film and two transparent protective films arranged on both sides thereof. The liquid crystal cell carries liquid crystal between two electrode substrates. When the optical compensation sheet of the present invention is used in a liquid crystal display device, one optical compensation sheet is arranged between the liquid crystal cell and one polarizing plate, or two optical compensation sheets are arranged between the liquid crystal cell and the polarizing plates on both sides.

When the polarizing plate of the present invention is used in a liquid crystal display device, the polarizing plate of the present invention may be used instead of one of the two polarizing plates. The polarizing plate of the present invention may be used in place of both polarizing plates. When the polarizing plate of the present invention is used in a liquid crystal display device, the polarizing plate is arranged on the liquid crystal cell side of the optical compensation sheet as a protective film. The liquid crystal cell is preferably an OCB type, a VA type, or a TN type. The VA type also includes the MVA type. OCB type liquid crystal cell uses liquid crystal display that uses rod-shaped liquid crystal molecules in the liquid crystal cell. -78- V. Description of the invention (77) The upper or lower part of the liquid crystal cell is aligned in a substantially opposite direction (symmetric). The device is disclosed in the specifications of U.S. Patent No. 4,585,825, and No. 54 1 0422. Since the rod-like liquid crystal molecules are symmetrically aligned above and below the liquid crystal cell, this liquid crystal type is called an OCB (Optically Compensated Bend) liquid crystal type. The curved alignment type liquid crystal display device has the advantage of fast response speed. In the case of a VA-type liquid crystal cell, when no voltage is applied, the rod-shaped liquid crystal molecules are substantially vertically aligned. The VA-type liquid crystal cell includes (1) a narrowly defined VA-type liquid crystal cell in which rod-shaped liquid crystal molecules are substantially vertically aligned when no voltage is applied and substantially horizontally aligned when a voltage is applied (Japanese Patent Application Laid-Open No. 2-1 76625 and Special Fair No. 7-6 9 5 3 6), (2) Because of the large viewing angle, it also contains VA type multi-range liquid crystal cell. Specifically, it includes MVA (SID97, Digest of tech. Paper s (pre-draft) 28 (1997) 845, SID 99, Digest of tech. Paper s (pre-draft) 30 (1999) 206 and JP 11-25 86 05)), SURVAIVAL (Monthly Monitor, Volume 6, No. 3 (1999) 14), PVA (Asia Display 98, Proc. Of the 18lh Inter. Display res · Conf. (Preliminary Collection) (1) 998) 383), Para-A (published by LCD / PDP International, 99), DDVA (SID 98, Digest of tech. Papers (pre-draft) 29 (1 998) 83 8), EOC (SID98, Digest of tech. Papei.s (Pre-Draft) 29 (1998) 319), PSHA (SID 98, Digest of tech. Papers (Pre-Draft) 29 (1998) 1081), RFFMH (Asia Display 98, Proc · 0 fthe 1 81 h I ntel · · D isp 1 ayres. C ο nf · (Pre-draft-79- 581885 V. Description of the Invention (78)) (1 99 8) 3 7 5), HMD (SID98, Disgest of tech Papers (pre-draft collection) 2 9 (1 9 9 8) 7 02). And (3) the rod-shaped liquid crystalline molecules are substantially vertically aligned when no voltage is applied, and the liquid crystal cell (I WD, 98 'Proc. Of the 5 "of the multi-range alignment type (η-ASM type) is twisted when voltage is applied. Inter. Display Workshop. (1998) (143). When no voltage is applied to the TN-type liquid crystal cell, the rod-shaped liquid crystal molecules are substantially horizontally aligned and twisted at 60 to 120 °. The TN type liquid crystal cell is mostly used in a color TFT liquid crystal display device, and has been described in most documents. (Reflective liquid crystal display device) FIG. 1 is a schematic diagram showing a basic configuration of a reflective liquid crystal display device. The reflective liquid crystal display device shown is from bottom to top (1) lower substrate, (2) reflective electrode, (3) lower alignment film, (4) liquid crystal layer, (5) upper alignment film, (6) transparent electrode, (7) The upper substrate, (8) λ / 4 plate, and (9) polarizing film. The lower substrate (1) and the reflective electrode (2) constitute a reflective plate. The lower alignment film (3) to the upper alignment film (5 ) Constitutes a liquid crystal cell. The λ / 4 plate (8) can be arranged between the reflective plate and the polarizing film (9) Any position. For color display, another color filter layer is provided. The color filter layer is provided between the reflective electrode (2) and the lower alignment film (3), or between the upper alignment film (5) and the transparent electrode (6). It is better to use a transparent electrode instead of the reflective electrode (2) shown in Fig. 1. Alternatively, a reflective plate may be provided outside the description of the invention (79). The reflective plate used in combination with the transparent electrode is preferably a metal plate. When the surface of the reflecting plate is smooth, only the specular reflection component reflects and the viewing angle is narrow. Therefore, it is better to introduce a concave-convex structure on the surface of the reflecting plate (Patent No. 2 7 5 6 20). When the surface of the reflecting plate is flat (replaces Concave-convex structure is introduced into the surface), and a light-scattering film is provided on one side (unit cell side or outside) of the polarizing film. The liquid crystal cell is of TN (twisted nematic) type, STN (super twisted nematic) type, or HAN (mixed arrangement). Nematic) type is preferred. The twist angle of the TN liquid crystal cell is preferably 40 to 100 °, more preferably 50 to 90 °, and most preferably 60 to 80 °. The refractive index anisotropy of the liquid crystal layer ( △ η) and the thickness (d) of the liquid crystal layer (△ nd): 0 · 1 ~ 0.5 // m The best and better is 0.2 ~ 0.4 // Π). The twist angle of STN type liquid crystal cell is preferably 180 ~ 3 60 °, and the more preferable is 2 20 ~ 2 70 °. The refractive index anisotropy of the liquid crystal layer The product of (△ η) and the thickness (d) of the liquid crystal layer (△ nd) is preferably 0 · 3 ~ 1 · 2 // m, and more preferably 0 · 5 ~ 1.0 μm 〇HAN type liquid crystal The unit cell is substantially vertically aligned on one substrate, and the pretilt angle on the other substrate is preferably 0 to 45 °. The product of the refractive index anisotropy (△ η) of the liquid crystal layer and the thickness (d) of the liquid crystal layer (△ nd) is preferably 0.1 to 1.0 μm, and more preferably 0.3 to 0.8 μm. The substrate on which the liquid crystal is vertically aligned can be a substrate on the reflective plate side or a substrate on the transparent electrode side. A reflective liquid crystal display device can be used in the original white type when the applied voltage is low and the display is dark , Or dark display when the applied voltage is low, -81-581885 V. Description of the invention (so) When the voltage is high, the original black type is bright display. The original white type is better. (Host-guest reflective liquid crystal display element) Fig. 2 is a schematic cross-sectional view showing a typical type of the host-guest reflective liquid crystal display element. The host-guest reflective liquid crystal display element shown in FIG. 2 includes (1 1) a lower substrate, (1 2) an organic layer insulating film, (1 3) a metal reflective plate, (1 4) λ / 4 plate, and ( 1 5) lower transparent electrode, (1 6) lower alignment film, (1 7) liquid crystal layer, (1 8) upper alignment film, (1 9) upper transparent electrode, (20) light diffusion plate, (2 1) upper A structure in which a substrate and (22) an antireflection layer are sequentially laminated. The lower substrate (1 1) and the upper substrate (2 1) are made of a glass plate or a plastic film. A TFT (23) is provided between the lower substrate (1 1) and the organic interlayer insulating film (12). The liquid crystal layer (17) is made of a mixture of liquid crystal and a dichroic dye. Liquid crystal. The layer can be obtained by injecting a mixture of liquid crystal and dichroic pigment into the cell gap formed by the pitch control plate (24). Instead of being provided on the light diffusing plate (20) ', unevenness is provided on the surface of the metal reflecting plate (1 3) so that the metal reflecting plate (1 3) has a light diffusing function. The anti-reflection layer (22) has an anti-glare function in addition to the anti-reflection function. Fig. 3 is a schematic cross-sectional view of another typical form of the host-guest reflective liquid crystal display element. The host-guest reflective liquid crystal display element shown in FIG. 3 includes a lower substrate (3)), (32) an organic interlayer insulating film, (33) a cholesterol-type color reflective plate, (34) input / 4 plates, and (3 5) Transparent electrode, (3 6) lower alignment film, (3 7) liquid crystal layer, -82- 581885 V. Description of the invention (81) (3 8) upper alignment film, (3 9) upper transparent electrode, upper substrate (4 1 ) And the anti-reflection layer 142) are sequentially laminated. The lower substrate (3 1) and the upper substrate (4 1) are made of a glass plate or a plastic film. A TFT (43) is provided between the lower substrate (31) and the organic interlayer insulating film (32). • The λ / 4 plate (34) also functions as a light diffusion plate. The liquid crystal layer (37) is made of a mixture of liquid crystal and a dichroic dye. The liquid crystal layer is obtained by injecting a mixture of liquid crystal and a dichroic pigment into a cell gap formed by a pitch control plate (44). A plastic substrate (4 5) is provided between the upper transparent electrode (3 9) and the upper substrate (4 1). In addition to the anti-reflection function, the anti-reflection layer (42) also has an anti-glare device tb. The λ / 4 plate of the present invention can be used as the λ / 4 plate of the reflective liquid crystal display device illustrated in FIG. 1, or the λ / 4 plate of the host-guest reflective liquid crystal display element described in FIGS. 2 and 3. (1 4) and (3 4). Host-guest reflective LCD devices with λ / 4 plates such as JP 6-222 3 50 0, the same 8-3 6 1 74, the same 10-2 68300, the same 10-292175, the same 10-293301 Nos., 10-311976, 10-319442, 10-325953, 10-333138, and 11-384 10. The λ / 4 plate of the present invention can also be used for the subject-guest reflective liquid crystal display elements described in the aforementioned publications. (Bending alignment type liquid crystal display device) The optical compensation sheet having an optically anisotropic layer of the present invention is particularly used.

-83-V. Description of the Invention (82) It is better for curved alignment type liquid crystal display device. The bending alignment type liquid crystal display device using the optical compensation sheet is described in detail below. FIG. 4 is a cross-sectional view of an alignment mode of a liquid crystal compound in a curved alignment liquid crystal cell. The curved alignment liquid crystal cell as shown in FIG. 4 has a structure in which a liquid crystal compound (1 1 1) is sealed between an upper substrate (1 1 4a) and (1 1 4b). The liquid crystal compound (1 1 1) used in the bending alignment liquid crystal cell generally has a positive anisotropy of the electromotive force. The upper substrate (1 1 4a) and the lower substrate (1 1 4b) of the liquid crystal cell each have an alignment film (1 12a, 1 12b) and an electrode layer (1 13a, 1 13b). The alignment film has a function of aligning rod-shaped liquid crystalline molecules (1 1 1 a to 1 1 1 j). RD is the lamination direction of the alignment film. The electrode layer has a function of applying a voltage to the rod-shaped liquid crystalline molecules (1 1 1 a to 1 1 1 j). When the applied voltage of the bend alignment liquid crystal cell is low, as shown in FIG. 4 ff, the rod-shaped liquid crystal molecules (1 1 la to 1 1 e) on the substrate (114a) side of the liquid crystal cell and the lower substrate The rod-shaped liquid crystalline molecules (1 1 1 f to 1 1 lj) on the (1 14b) side are aligned in the opposite direction (symmetrical up and down). In addition, the rod-shaped liquid crystal molecules (1 11 a, 1 1 1 b, 1 1 1 1, 1 1 1 j) near the substrate (114a, 114b) are aligned approximately horizontally, and the center of the liquid crystal cell The rod-shaped liquid crystalline molecules (1 1 1 d to 11 1 g) are aligned approximately in the vertical direction. As shown in on of FIG. 4, when the applied voltage is high, the rod-shaped liquid crystal molecules (1 1 a, 1 1 U) near the substrate (1 14 a, 1 14 b) are aligned approximately horizontally. In addition, the rod-shaped liquid crystal molecules (1 1 1 e, 1 1 1 f) in the center of the liquid crystal cell are arranged approximately in a vertical direction. By increasing the voltage change alignment, rod-shaped liquid crystal molecules (1 1 1 b, 1 1 1 C, 1 1 1 d) are provided between the substrate and the liquid crystal-84-581885 , 1 1 1 g, 1 1 1 h, 111 i), and these are also vertically aligned in the 0ff state. However, the rod-shaped liquid crystal molecules (1 1 1 a to 1 1 1 e) on the upper substrate (1 14a) side of the liquid crystal cell and the rod-shaped liquid crystal molecules (1 1] f on the lower substrate (1 1 4b) side ~ 1 1 1 ″) Reverse (vertical up and down) alignment, same as off state. Fig. 5 is a schematic diagram showing an elliptically polarizing plate of the present invention. The elliptically polarizing plate shown in FIG. 5 is an optically anisotropic layer 1 (1 3 1) containing a disc-shaped compound (1 3 1 a to 1 3 1 〇) and at least one cellulose acetate film. An anisotropic layer 2 (1 33) and a polarizing film (1 34) are laminated. The elliptically polarizing plate shown in Fig. 5 is formed between the optically anisotropic layer 1 (131) and the optically anisotropic layer 2 (1 33) There is an alignment film between them. The discoid compound (1 3 1 a to 1 3 1 e) of the optically anisotropic layer 1 (1 3 1) is a planar molecule. The discoid compound (131a to 131e) is in the molecule There is only one plane among them, that is, the disc surface. The disc is inclined toward the surface of the optical anisotropic layer 2 (133). The angle (tilt angle) between the disc surface and the optical anisotropic layer 2 surface As the distance between the disc-shaped compound and the alignment film increases, the average tilt angle is preferably 15 to 50 °. When the tilt angle shown in FIG. 5 is changed, the viewing angle expansion function of the elliptical polarizer is significantly improved. In addition, the elliptically polarizing plate with a changed inclination angle also has the function of displaying day image inversion and preventing the change of tone or coloring. The average 化合物 of the normal (NL) of the disc surface of the discoid compound (1 3 U ~ 1 3 1 e) to the direction (PL) of the orthographic projection of the optically anisotropic layer 2 (133) and the alignment film (132) The laminated direction (RD) has an anti-parallel relationship. -85- 581885 V. Description of the invention (84) The average direction of the normal projection of the normal of the disc surface of the disc-shaped compound to the transparent carrier, and the optical The angle of the in-plane late phase axis (SA) of the anisotropic layer 2 (1 3 3) is substantially 4 5. Therefore, 'the lamination direction (RD) of the alignment film (1 32) and The angle (0) of the retardation axis (SA) in the plane of the transparent carrier is substantially adjusted to 45 °. In addition, the present invention makes the retardation axis (SA) in the plane of the optically anisotropic layer 2 and the polarizing film (1 34) ) The in-plane transmission axis (TA) is arranged substantially parallel or substantially perpendicular to the transparent carrier and the polarizing film. The elliptical polarizing plate shown in Fig. 5 is a sheet of transparent carrier arranged in parallel. The surface of the transparent carrier (1 3 3) The internal late phase axis (SA) corresponds in principle to the stretching direction of the optically anisotropic layer 2. The in-plane transmission axis (TA) of the polarizing film (1 34) ) In principle, the direction is quite perpendicular to the stretching direction of the polarizing film. Fig. 6 is a schematic diagram of the curved alignment type liquid crystal display device of the present invention.丨 丨 0), a pair of elliptically polarizing plates (丨 3 丨 A ~ 丨 3 4 A, 131B ~ 134B) and backlight (BL) arranged on both sides of the liquid crystal cell. Bending alignment liquid crystal cell (1 10) is equivalent to the liquid crystal cell shown in FIG. The stacked directions (RD2, RD3) above and below the liquid crystal cell (110) are the same direction (parallel). The elliptical polarizer is sequentially laminated with an optically anisotropic layer 1 (1 3 1 A, 1 3 1 B), an optically anisotropic layer 2 (〖3 3 A, 3 3B), and a polarizing film (1 34A) from the liquid crystal cell side. , 1 34B). Optical Anisotropic Layer Disc-shaped ((31 A, 3 1B) -86-581885) V. Description of the Invention (85) Laminated direction of the compound (RD 1, RD 4) and the direction of the laminated liquid crystal cell (RD2, RD3) into an anti-parallel relationship. As described above, the lamination direction (RD1, RD4) of the disc-shaped compound makes the average direction of the normal projection of the normal of the disc surface to the transparent carrier surface anti-parallel. Optical anisotropic layer 2 (133A, 133B) in-plane retardation (SA1, SA2) and polarizing film (134A, 134B). Inner retardation (TA1, TA2) and disc-shaped compound The directions are in the same plane and at an angle of substantially 45 °. Then, the in-plane transmission axes (TA1, TA2) of the two polarizing films (134A, 1 34B) are arranged perpendicular to each other (cross-coil). FIG. 7 is a schematic diagram of the optical compensation relationship of the curved alignment type liquid crystal display device. The liquid crystal display device of the present invention shown in FIG. 7 is configured to coordinate a curved alignment liquid crystal cell (1 1 0) to coordinate the optical anisotropic layer 1 (1 3 1 A, 1 3 1 B) and the optical anisotropic layer 2 ( 1 3 3 A, 1 3 3B), to be optically compensated. By setting the lamination direction (RD1, RD4) of the discotic compound of the optically anisotropic layer 1 (1 3 1 A, 1 3 1 B) and the lamination direction (RD2, RD3) of the liquid crystal cell, an anti-parallel relationship is established. In order to make the liquid crystal molecules of the bend-aligned liquid crystal cell (1 10) correspond to the disc-shaped compounds of the optically anisotropic layer 1 (1 3 1 A, 1 3 1 B), optical compensation is performed. Then, the optically anisotropic layer 2 (133A, 133B) is designed to correspond to (d, h) in the liquid crystal molecules in which the central portion of the curved alignment liquid crystal cell (110) is substantially vertically aligned. The ellipse of the optically anisotropic layer 2 (133A, 133B) is a refractive index ellipse generated by the optical anisotropy. FIG. 8 is a schematic diagram of each form of the elliptically polarizing plate.

-87- V. Description of the Invention (86) The a1 form in Fig. 8 is the most basic elliptical polarizer not shown in Fig. 5. The elliptical polarizer in the form of a1 is sequentially laminated with an optically anisotropic layer 1 (131), an optically anisotropic layer 2 (133), and a polarizing film (134). The lamination direction (RD) of the discoid compound is substantially 45 ° from the retardation axis (SA) of the optically anisotropic layer 2 (133), and the retardation axis (SA) of the optically anisotropic layer 2 (133) ) Is substantially parallel to the transmission axis (TA) of the polarizing film (134). The form a2 in FIG. 8 is also a sequential laminated optically anisotropic layer 1 (1 3 1), an optically anisotropic layer 2 (1 33), and a polarizing film (134). The lamination direction (RD) of the discoid compound is substantially 45 ° with the late phase axis (SA) of the optically anisotropic layer 2 (133), and the late phase axis (SA) of the optically anisotropic layer 2 (133) ) Is substantially perpendicular to the transmission axis (TA) of the polarizing film (134). The a 3 morphology of FIG. 8 is formed by two optically anisotropic layers 2 (1 3 3 a, 133b). At least one of the two layers of the present invention (133b in the figure) can satisfy the above definition and be configured with an optically anisotropic layer 1 (1 3 1) and a polarizing film (1 34). In other words, the lamination direction (RD) of the disc-shaped compound and the angle of the slow phase axis (SA2) of an optically anisotropic layer 2 (133b) are substantially 45 °, and the optically anisotropic layer 2 (1 3 3b) The late phase axis (SA2) is substantially parallel to the transmission axis (TA) of the polarizing film (134). In the a3 form, another optically anisotropic layer 2 (133a) is also the same as the conventional technique, and the late phase axis (SA1) and the lamination direction (RD) of the disc-shaped compound are arranged substantially in parallel. The a4 morphology of FIG. 8 is formed by any one of the two optically anisotropic layers 2 (133a, 13 3b), which can satisfy the above definition and be configured with an optically anisotropic layer 1 (1 3 1) and a polarizing film (1 34). In other words, the discoid compound of -88- 581885 V. Description of the invention (87) The angle of the lamination direction (RD) and the late phase axes (SA1, SA2) of the two optically anisotropic layers 2 (133a, 133b) are substantially At 45 °, the retardation axes (SA1, SA2) of the two transparent carriers (133a, 133b) and the transmission axis (TA) of the polarizing film (134) are substantially parallel. The morphology of a5 in FIG. 8 is formed by any one of the two optically anisotropic layers 2 (133a, 133b), and the optically anisotropic layer 1 (131) and the polarizing film (134) can be configured to meet the above definition. In other words, the angle of the lamination direction (RD) of the discoid compound and the retardation axis (SA1, SA2) of the two optically anisotropic layers 2 (133a, 133b) is substantially 45 °, which is close to the optically anisotropic layer 1 The retardation axis (SA1) of the optically anisotropic layer 2 (133a) of (131) is substantially perpendicular to the transmission axis (TA) of the polarizing film (134) and is close to the optically anisotropic layer of the polarizing film (134). The retardation axis (SA2) of 2 (133b) is substantially parallel to the transmission axis (TA) of the polarizing film (134). FIG. 9 is a schematic diagram of another type of elliptical polarizer. Fig. 9b shows the elliptical polarizing plate of the type in which the optically anisotropic layer 2 (133), the optically anisotropic layer 1 (131), and the polarizing film (134) are sequentially laminated. The lamination direction (RD) of the discoid compound is substantially 45 ° from the late phase axis (SA) of the optically anisotropic layer 2 (1 33), and the late phase axis of the optically anisotropic layer 2 (133) ( SA) is substantially parallel to the transmission axis (TA) of the polarizing film (134). The shape of b2 in FIG. 9 is also a sequential laminated optical anisotropic layer 2 (133), an optical anisotropic layer 1 (1 3 1), and Polarizing film (1 34). The lamination direction (RD) of the discoid compound and the late phase axis (SA) of the optically anisotropic layer 2 (1 33)

-89- 581885 V. Description of the invention (88) The angle is substantially 45. The retardation axis (SA) of the optically anisotropic layer 2 (133) is substantially perpendicular to the transmission axis (TA) of the polarizing film (134). The b3 morphology of the stomach 9 has two optically anisotropic layers 2 (133a, 133b). At least one of the two layers of the present invention (133b in the figure) can satisfy the above definition and be configured with an optically anisotropic layer 1 (1 3 1) and a polarizing film (134). In other words, the lamination direction (rd) of the disc-shaped compound and the angle of the slow phase axis (SA2) of one optically anisotropic layer 2 (133b) are substantially 45. 'The late phase axis (SA2) of the optically anisotropic layer 2 (1 3 3b) is substantially parallel to the transmission axis (TA) of the polarizing film (134). The other optically anisotropic layer 2 (1 3 3 a) in the form of b3 is also the same as the conventional technique, and the late phase axis (s A 1) and the lamination direction (RD) of the disc-shaped compound are arranged substantially in parallel. The b4 morphology shown in FIG. 9 is formed of any one of the two optically anisotropic layers 2 (133a, 133b), which can satisfy the above definition and be configured with an optically anisotropic layer 1 (131) and a polarizing film (134). In other words, the angle of the lamination direction (RD) of the disc-shaped compound and the retardation axes (SA1, SA2) of the two optically anisotropic layers 2 (133a, 133b) are substantially 45. The retardation axis (SA1, SA2) of the optically anisotropic layer 2 (133a, 133b) and the transmission axis (TA) of the polarizing film (Π4) are substantially parallel. The form b5 in FIG. 9 is a configuration in which the optical anisotropic layer 1 (1 3 1) and the polarizing film U 3 4) are configured by the total of the two optical anisotropic layers 2 (133a, 133b) satisfying the above definition. In other words, the angles of the lamination direction (RD) of the disc-shaped compound and the retardation axes (SA1, SA2) of the two optically anisotropic layers 2 (133a, 133b) are substantially 45. The late phase of the optically anisotropic layer 2 (1 3 3 a) far from the polarizing film (1 3 4) of the invention description (89) 1 (1 3 1) from the optically anisotropic layer -90- 581885 The axis (SA 1) is substantially parallel to the transmission axis (TA) of the polarizing film (1 34). The elliptically polarizing plate is an optically anisotropic layer 2 composed of a disk-shaped compound as a mixed alignment 1 ′ and an optically anisotropic cellulose acetate 2 made of cellulose acetate having optical anisotropy 2 , Laminated with polarizing film. When an OCB type liquid crystal cell is used, it is preferable that the optically anisotropic layer 1 made of a disc-shaped compound does not have a direction (optical axis) where the hysteresis is zero. Moreover, it is preferable that the direction in which the absolute value of the hysteresis 中 is the smallest in the optically anisotropic layer. The optically anisotropic layer does not have a normal direction in the plane. The optical properties of the optically anisotropic layer 1 and the optically anisotropic layer 2 are the Re hysteresis 定义 defined by the following formula (9) and the R t h hysteresis 定义 defined by the following formula (10a) or (10b) are extremely important. (9) R e = (η X — ny) X d (10a) Rth = [(n2 + n3) / 2 —nl:] Xd (10 b) Rth = [(nx + ny) / 2 — nz] Xd (Where nx is the refractive index of the in-plane late phase axis of the optical anisotropic layer 1 or the optical anisotropic layer 2; ny is the in-plane late phase of the optical anisotropic layer 1 or the optical anisotropic layer 2 Refractive index of the axis; η 1 is the minimum value of the main refractive index of the optical anisotropic layer 1; η 2 and ι 3 are the other main refractive index of the optical anisotropic layer 1; η ζ is the optical anisotropy Refractive index in the thickness direction of layer 2; d is the thickness of optically anisotropic layer 1 or optically anisotropic layer 2) -91-581885 V. Description of the invention (90) Wavelength of optically anisotropic layer 1 5 50nm The measured Re hysteresis (Re5 50) is preferably 10 to 100 nm. The Rth hysteresis (Rth550) of the optically anisotropic layer 1 measured at a wavelength of 5 to 50 nm is preferably 40 to 200 nm. In addition, the direction (the smallest angle) of the major axis of the refractive index of the optically anisotropic layer 1 and the normal of the film (not shown) is 20 to 50. Better. The Rth hysteresis (Rth550) of the optically anisotropic layer 2 measured at a wavelength of 550 nm is preferably 150 to 300 nm, and more preferably 180 to 280 nm. Moreover, the Re hysteresis (R e 5 5 0) measured by the wavelength 550 nm of the 'optical anisotropic layer 2 depends on the configuration of the transmittance of the polarizing film, and its preferable range is also different. When the in-plane late phase axis of the optically anisotropic layer 2 is substantially parallel to the transmission axis, it is preferably 20 to 100 nm, and more preferably 30 to 60 nm. When the optically anisotropic layer 2 is composed of two layers, it is preferable to use two cellulose acetate films or to orient the liquid crystal compound on the cellulose acetate film. The liquid crystal display device of the present invention is characterized by optical compensation. The wavelength dependence of the action is low. When the wavelength dependence of the optical compensation effect is low, it is specifically used in a liquid crystal display device. The difference between the total Re hysteresis of the optical anisotropic layer 1 and the optical anisotropic layer 2 (the total of all the optical anisotropic layer 1 when two elliptical polarizers are used) and the difference between the Re hysteresis of the liquid crystal cell In the range of 400 to 7 0011111, it is 1011111 or less. According to the present invention, the optically anisotropic layer 1, the optically anisotropic layer 2 and the polarizing film are arranged in the elliptical polarizing plate, and this can be easily achieved. The optically anisotropic layer 1 is a circle of a disc-shaped compound as shown in FIG. 5 -92-581885 V. Description of the invention (91) The angle formed by the disk surface and the transparent carrier surface to change the optically anisotropic layer 1 The depth direction (hybrid alignment) is better. The optical axis of the discoid compound exists in the normal direction of the disc surface. The disk-shaped compound has a birefringence having a large refractive index in the disk surface direction with respect to the refractive index in the optical axis direction. The optically anisotropic layer 1 is preferably formed by aligning the discotic compound with the following alignment film, and fixing the discotic compound in the aligned state. The disk-shaped compound is preferably immobilized by a polymerization reaction. In addition, the direction in which the hysteresis 値 is zero does not exist in the optically anisotropic layer 1. In other words, the minimum hysteresis of the optically anisotropic layer 1 is larger than 0. The alignment film has the function of specifying the alignment direction of the disc-shaped compound of the optically anisotropic layer 1. The β-alignment film can be laminated with organic compounds (preferably polymers), oblique evaporation of inorganic compounds, and micro-groups. A layer is formed, or it is set by accumulating organic compounds (for example, omega-tricosanoic acid, octacosylmethylammonium chloride, and methyl stearate) by a Ramill adsorption method (LB film). In addition, by applying an electric field, a magnetic field, or light irradiation, an alignment film having an alignment function can be obtained. The alignment film is preferably formed by laminating a polymer. Polyvinyl alcohol is the preferred polymer. In particular, modified polyvinyl alcohols bonded with hydrophobic groups are more preferred. Since the hydrophobic group and the disc-shaped compound of the optically anisotropic layer 1 are hydrophilic, the disc-shaped compound can be uniformly aligned by introducing a hydrophobic group into polyvinyl alcohol. The hydrophobic group is bonded to the main chain end or side chain of the polyvinyl alcohol. The hydrophobic group is preferably an aliphatic group having 6 or more carbon atoms (preferably an alkane-93-581885). 5. The description of the invention (92) or an alkenyl group or an aromatic group is preferred. When a hydrophobic group is bonded to the end of the main chain of polyvinyl alcohol, a bonding group is preferably introduced between the hydrophobic group and the end of the main chain. Examples of bonding groups include -s-, -aCN)! ^-, -NR2-, -CS-, and combinations thereof. Each of Ri and R2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably an alkyl group having 1 to 6 carbon atoms). When a hydrophobic group is introduced into the side chain of polyvinyl alcohol, the ethyl acetate unit (-CO-CH3) of vinyl acetate unit of some polyvinyl alcohol can be replaced with an awake group (-CO-R3) having a carbon number of 7 or more. R3 is an aliphatic group or an aromatic group having 6 or more carbon atoms. In addition, commercially available modified polyvinyl alcohol (for example, MP 103, MP203, R1130, and Clare Co., Ltd.) can be used. The saponification degree of the (modified) polyvinyl alcohol used in the alignment film is preferably 80% or more. (Modification) The degree of polymerization of polyvinyl alcohol is preferably 200 or more. The lamination process is performed by making the surface of the alignment film several times in a certain direction with paper or cloth. It is preferable to use a uniformly planted fiber using uniform length and width fibers. Furthermore, after the disk-shaped compound of the optically anisotropic layer 1 is aligned using an alignment film, the alignment state of the disk-shaped compound can be maintained even if the alignment film is removed. In other words, since the alignment film aligns the disc-shaped compound, it is necessary in the manufacture of elliptical polarizers, but not necessary in the manufactured elliptical polarizers. When the alignment film is provided between the optically anisotropic layer 2 and the optically anisotropic layer 1, it is also preferable that an undercoat layer (adhesive layer) be provided between the optically anisotropic layer 2 and the alignment film. The optically anisotropic layer 2 is made of at least one cellulose acetate film. -94- V. Explanation of the Invention (93) The present invention can achieve the objective optical characteristics by using one cellulose acetate film, two cellulose acetate films, or a laminate of a cellulose acetate film and a polymerizable liquid crystal compound. What you want. When the optically anisotropic layer is formed of two layers (for example, two cellulose acetate films), there may be an intermediate layer (for example, an adhesive layer) between the two layers. When the optically anisotropic layer 2 is composed of two or more layers', the optical characteristics achieved by the two or more layers are achieved. Re retardation of cellulose acetate film can be made high by stretching cellulose acetate film. The R th hysteresis of cellulose acid film can be achieved by (1) using a hysteresis rising agent, (2) adjusting the average degree of acetification (degree of acetylation), or (3) manufacturing the film by the cooling and dissolving method. High. In addition, the above-mentioned cellulose acetate film may be used as a carrier and a polymerizable liquid crystal layer having a horizontal alignment may be coated. The polymerizable liquid crystal compound is preferably a rod-shaped liquid crystal or a nematic liquid crystal (the above-mentioned discotic compound), and it is more preferable to use a nematic liquid crystal in order to control the R t h hysteresis. The elliptically polarizing plate can be continuously manufactured as described below. First, adjust the retardation of Re and Rth to the desired cellulose acetate film (optical anisotropic layer 2) to form an alignment film, and make the direction of the cellulose acetate film transport (the direction of the late axis consistent). 45. The angle is implemented as a lamination process. Then, a disc-shaped compound layer (optically anisotropic layer 1) is formed on the alignment film and wound. Then, the cellulose acetate film surface was subjected to an alkali treatment, and the polarizing film was bonded via an adhesive (at this time, one of the commercially available triethylfluorene-based cellulose films was bonded via the adhesive). -95- 581885 V. Description of the Invention (94) When the optically anisotropic layer 2 is made of two cellulose acetate films, firstly, a disc-shaped compound is coated on a cellulose acetate film as described above and then wound up. In order to prevent damage to the optically anisotropic layer 1 and adhesion of garbage, 'the laminated film can be laminated on the disc-shaped compound side and re-rolled. The other cellulose acetate film can be alkalized and passed through The adhesive is bonded to the polarizing film (at this time, a commercially available triethylfluorene-based cellulose film is bonded to the other side via the adhesive). The cellulose acetate film surface of the roll film to which the laminated film is laminated is bonded to the cellulose acetate film surface of the above-mentioned polarizing film (the present invention) via an adhesive. Then, when the optically anisotropic layer 2 is made of a cellulose acetate film and a polymerizable liquid crystal, a discoid compound is first coated on a cellulose acetate film of the same type and rolled up. When the anisotropic layer 1 is damaged and the garbage is adhered, the laminated film can be pasted on the disc-shaped compound side and re-rolled. The other cellulose acetate film was subjected to an alkali treatment, and the polarizing film was bonded via an adhesive (at this time, a commercially available triethylfluorene-based cellulose film subjected to an alkali treatment was bonded via the adhesive on the other side). The cellulose acetate film surface of the roll film to which the laminated film is laminated is bonded to the cellulose acetate film surface of the above-mentioned polarizing film (the present invention) via an adhesive. The elliptical polarizing plate of the present invention is particularly effective for a liquid crystal display device that combines a curved alignment liquid crystal cell and a horizontal alignment liquid crystal cell. Bending alignment liquid crystal cell can also twist the liquid crystal molecules in the central part of the cell -96- 581885 V. Description of the invention (95) Alignment. The refractive index anisotropy △ η of the liquid crystal compound of the bend alignment liquid crystal cell system and the product of the thickness d of the liquid crystal layer of the liquid crystal cell (Δ η X d) are such that the luminance and the viewing angle are equal to each other, and 100 to 2000 nm It is better, more preferably 150 to 1 700 nin, and the best one is 500 to 1 500 ·. Both curved alignment liquid crystal cells can be used in the original white type (NW type) or the original black type (NB type). [Example 1] The following composition was charged into a mixing tank to prepare a cellulose acetate solution. , Heating and stirring, so that each component is dissolved in cellulose acetate solution to constitute 60.9% of cellulose acetate 100 parts by mass of triphenyl phosphate (plasticizer) 7.8 parts by mass of biphenyl diphenyl phosphate (plasticizer) 3 9 parts by mass of dichloromethane (first solvent) 300 parts by mass of methanol (second solvent) 54 parts by mass of 1-butanol (third solvent) 1 1 part by mass was placed in another mixing tank 16 parts by mass of the following A hysteresis rising agent, 80 parts by mass of dichloromethane and 20 parts by mass of methanol, and heating and stirring to prepare a hysteresis raising agent solution. 25 4 parts by mass of the lagging agent solution was mixed in 4 7 4 parts by mass of the cellulose acetate solution, and the solution was sufficiently stirred. The amount of the retardation rising agent is 5.5 parts by mass for 100 parts by mass of cellulose acetate. -97-581885 V. Description of the invention (96) Hysteresis rising agent

_ch3

The obtained solution was cast using a belt caster. A film with a residual solvent content of 15% by mass was laterally stretched under a condition of i3 (rc) at a draw ratio of 25% using a tenter to produce a cellulose acetate film. The produced cellulose acetate film (optical compensation Film: KH _ 〇i) is measured using a Yeriber cable (transliteration) (50, manufactured by JASCO Corporation), and measured the Re hysteresis (Re550) and Rth hysteresis (Rth550) at a wavelength of 550 nm. Results As shown in Table 1.

In addition, using a digital film thickness meter (K-40 2B, manufactured by Anritz Co., Ltd.), the produced cellulose acetate film was measured at an area of 100 square meters. The average thickness of the film thickness was 52. 0 // m, and the standard deviation was 1.5. [Example 2] Except that 474 parts by mass of cellulose acetate solution was mixed with 56 parts by mass of a hysteresis rising agent solution to prepare a solution (the The addition amount is 7.8 parts by mass based on 100 parts by mass of cellulose acetate), and the change in stretching ratio is 12% -98- 581885 5. Except for the description of the invention (97), it was produced in the same manner as in Example 1. Cellulose acetate film (optical compensation sheet: K Η * · 0 2) and evaluated. The results are shown in Table 1. In addition, the produced cellulose acetate film was immersed in a 1.5N potassium hydroxide solution (40 ° C) for 5 minutes, and then neutralized with sulfuric acid, washed with pure water, and dried. When the surface energy of the cellulose acetate film was determined by the contact angle method, it was 68 mN / m. In addition, a digital film thickness meter (K-402B, manufactured by Allitz) was used for the produced cellulose acetate film. 100 points were measured in an area of 1 square meter (l_Xlmm). The average 値 is 40.0 // m and the standard deviation is 1.8 / m. This cellulose acetate film was coated with a coating solution of the following composition 2 # 8 6 with an iron wire applicator # 16. Dry at 60 ° C for 60 seconds and at 90 ° C for 150 seconds. Then, a lamination process was performed on the film formed with the late phase axis (measured at a wavelength of 632.8 nm) of the cellulose acetate film and a direction of 45 °. Composition of alignment film coating liquid ~ The following modified polyvinyl alcohol ------- ~-10 parts by mass of water 371 parts by mass of methanol 11 9 parts by mass of valeraldehyde (crosslinking agent) 0.5 parts by mass -99- 581885 5 Description of the invention (98)

Modified polyvinyl alcohol — (CH2— (JH) 87.8— OH-(ch2—9H) 0.2

_ (CH2-(pH) 12 (r 〇I. C = 〇CH, 0 (CH2) 40C0CH = CH2 (formation of optically anisotropic layer) 102 g of an iron wire rod coated on an alignment film was dissolved 41.01 g of the optical disc (disc) liquid crystal compound used in Example 2, 4.06 g of ethylene oxide-modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemicals Co., Ltd.), 0.9 0g cellulose acetate butyrate (CAB55 1-0.2, manufactured by Eston Chemical Co., Ltd.), 0.23g cellulose acetate butyrate (CAB531-1, manufactured by Eston Chemical Co., Ltd.), 1.35g of photopolymerization initiator (Irukhaki (Transliteration) 907, manufactured by Chiba Machinery Co., Ltd.), 0.45g of sensitizer (Carradich (Transliteration), DETX, Nippon Kayaku Co., Ltd.) methyl ethyl A coating solution of ketone. Attach it to a metal frame, and heat it in a horizontal bath at 13 ° C for 2 minutes to align the disc-shaped compound. Then, use a 120W / Cm high-pressure mercury lamp at 130 ° C, The UV-ray was irradiated for 1 minute to polymerize the disc-shaped compound. Then, it was cooled to room temperature. Thus, an optically anisotropic layer was formed to prepare an optical compensation sheet (KH-12). The Re hysteresis of the optically anisotropic layer measured at a length of 550 nm is -100 to 581885. V. Description of the invention (99) 3 8ηη. Moreover, the angle (tilt angle) with the surface of the cellulose acetate film is 40 ° on average. Sex compounds

R

[Example 3] A cellulose acetate film (optical compensation sheet: KH) was produced in the same manner as in Example 1 except that 6.0 parts by mass of a hysteresis rising agent was used for 100 parts by mass of cellulose acetate and the stretching ratio was changed to 30%. -03) and evaluated. The results are shown in Table 1. In addition, the produced cellulose acetate film was immersed in a 2.0N potassium hydroxide solution (25 ° C) for 2 minutes, and then neutralized with sulfuric acid, washed with pure water, and dried. When the surface energy of the cellulose acetate film was determined by the contact angle method, it was 63 mN / m. In addition, the produced cellulose acetate film was measured using a digital film thickness meter (K-4 0 2B, manufactured by Allitz Corporation). ). Measure 100 points in an area of 1 square meter (Π_ x 丨). The mean 値 is 3 8 · 5 μ m and the standard deviation is 1 · 4 // m. [Comparative Example 1] A cellulose acetate film (optical) was produced in the same manner as in Example 1, except that the cellulose acetate solution was directly used as the solution and the stretching was not performed -101-581885. Compensation film: KH-Η 1) and evaluated. The results are shown in Table 1. In addition, a 100-point thickness was measured using a digital film thickness meter (K-402B, manufactured by Anritz Corporation) on the produced cellulose acetate film in an area of 1 square meter (lmm × lmm). The average 値 is 8 0. 5 // m and the standard deviation is 1. 7 // m. -102- 581885 V. Description of the invention (101) Stretching ratio of film hysteresis rising agent Re550 Rt550 Example 1 KH-01 5.5 parts by mass 25% 40nm 130nm Example 2 KH-02 7.8 parts by mass 12% 20nm 110nm Example 3 KH-03 6.0 parts by mass 30% 50nm 130nm Comparative Example 1 KH-H1 M / \ \\ Not stretched 4nm 48nm [Example 4] Adsorb iodine on a stretched polyvinyl alcohol film to make a polarizing film, Using a polyvinyl alcohol-based adhesive, the KH-01 (optical compensation sheet) produced in Example 1 was attached to one side of a polarizing film. A commercially available cellulose acetate film (Fujitak TD80UF, Fuji Photo Negative Film (stock)) was saponified, and a polyethylene-based adhesive was used and attached to the opposite side of the polarizing film. The transmission axis of the polarizing film is arranged parallel to the retardation axis of the KH-01 (optical compensation sheet) produced in Example 1. The transmission axis of the polarizing film and the late phase axis of a commercially available cellulose triacetate film are arranged orthogonally. Thus, a polarizing plate was produced. [Example 5] A polarizing film was prepared by adsorbing iodine on a stretched polyvinyl alcohol film, and using a polyvinyl alcohol-based adhesive, the KH-02 (optical compensation sheet) produced in Example 2 was attached to the polarizing film One side. Saponification of commercially available cellulose acetate film (Fujitak TD80UF, Fuji Photo Negative Film (stock)), using polyethylene adhesive, attaching -103- 581885 V. Description of the invention (102) in polarized light The opposite side of the membrane. In addition, the KH-12 (optical compensation sheet) produced in Example 2 was bonded in parallel with these slow-phase axes via an adhesive on the -02 (optical compensation sheet) side. Thus, a polarizing plate was produced. [Example 6] A polarizing plate was produced in the same manner as in Example 4 except that KH-0 (optical compensation sheet) produced in Example 3 was used. [Example 7] A pair of polarizing plates and a pair of optical compensation sheets provided on a liquid crystal display device (VL-1 530S, manufactured by Fujitsu Co., Ltd.) using a vertical alignment type liquid crystal cell were peeled, and Example 4 was peeled off. The produced polarizing plate was adhered to the liquid crystal cell side of the KH-01 (optical compensation sheet) produced in Example 1 through an adhesive, and attached to the observer side. In addition, a commercially available polarizer (HLC2-5618HCS, Selitz) is attached to the backlight side. The transmission axis of the polarizer on the viewer side faces up and down, and the transmission axis of the polarizer on the background light side crosses the coils to the left and right. As for the produced liquid crystal display device, the viewing angle was measured in eight stages from a black display (L1) to a white display (L8) using a measuring machine (redundant-Conti. Astl60D, manufactured by ELDIM Corporation) '. The measurement results are shown in Table 2. [Comparative Example 2] A liquid crystal display device (VL-1530S, manufactured by Fujitsu Co., Ltd.) using a vertical alignment type liquid crystal cell, and a measuring device (EZ-Con tr as t 1 60D, manufactured by ELDI M) was displayed in black. (L 1) to white display (L8) are measured in 8 angles. The results are shown in Table 2. -104- 581885 V. Description of the invention (1 〇3) Table 2 Viewing angle of liquid crystal display device (contrast range of 10 or more on the black side without range inversion) Transmission axis direction 45 ° from transmission axis Example 7 > 80 ° > 80. Comparative Example 2 > 80 ° 44 ° (Note) Inversion of tone on the black side: Inversion between L 1 and L2 (Evaluation of improvement in frame-shaped transmittance)

A pair of polarizing plates provided on a 15-inch liquid crystal display device (VL-1 5 3 0SW, manufactured by Fujitsu Co., Ltd.) using a vertical alignment type liquid crystal cell was peeled, and the polarizing plate prepared in Example 4 was passed through The adhesive is adhered to the liquid crystal cell side of the optical compensation sheet, and one sheet is attached to each of the observer side and the background light side. The transmission axis of the polarizer on the observer side and the transmission axis of the polarizer on the background side are arranged orthogonally.

Under ambient conditions of temperature 25 ° C and relative humidity 60%, continuously turn on the backlight for 5 hours continuously and visually observe the full black display state in a dark room to evaluate light leakage. As a result, the 15-inch liquid crystal display device using the polarizing plate produced in Example 4 did not have a frame-shaped transmittance increase (light leakage). [Example 18] (Fabrication of curved alignment liquid crystal cell) With ITO attached A polyimide film as an alignment film is provided on the glass substrate of the electrode, and a lamination process is performed on the alignment film. The two glass substrates obtained are -105- 581885. 5. Description of the invention (104) The combination is arranged parallel to the lamination direction, and the cell gap is set to 6 // m. A liquid crystal compound (ZL I 1 12 3, manufactured by Meluk Corporation) having a Δη of 0.113 was injected into the gap to produce a curved alignment liquid crystal cell. The two elliptical polarizing plates prepared in Example 5 were bonded to each other while sandwiching the bent alignment cell. The optically anisotropic layer of the elliptically polarizing plate is opposed to the cell substrate, and the lamination direction of the liquid crystal cell is arranged in antiparallel to the lamination direction of the opposite optical anisotropic layer. A rectangular wave voltage of 55 Hz was applied to the liquid crystal cell. 2V white display and 5V black original white display. The transmittance ratio (white display / black display) is used as a control ratio, and the angle of view is measured in eight stages from black display (L1) to white display (L8) using a measuring device (EZ-Contra ras t 1 60D, manufactured by ELDIM). . The measurement results are shown in Table 3. Table 3 Viewing angle of the liquid crystal display device (comparative to the range of 10 or more on the black side, there is no range of tone inversion). 80. 80 ° (Note) Inverted tone on the black side: Inversion between L1 and L2 (evaluation of frame-shaped transmittance improvement) Same as the above-mentioned curved alignment liquid crystal cell, using two sheets of Example 5 The elliptical polarizing plate is a 17-inch curved alignment liquid crystal cell. -106- 581885 V. Description of the invention (105) Under the environmental conditions of a temperature of 25 ° C and a relative humidity of 60%, the backlight of the produced liquid crystal display device is continuously turned on for 5 hours and visually inspected in a dark room. Observe the full black display state to evaluate the light leakage situation. As a result, the manufactured 17-inch liquid crystal panel has no frame-shaped transmittance increase (light leakage). [Example 9] A pair of polarizing plates provided on a liquid crystal display device (6E-A3, manufactured by Sharp) using a TN-type liquid crystal cell was peeled off, and the polarizing plate prepared in Example 6 was passed through an adhesive. Adhere one to the liquid crystal cell side of the KH-03 (optical compensation sheet) produced in Example 3 on the observer side and the backlight side. The transmission axis of the polarizer on the observer side and the transmission axis of the polarizer on the background side are arranged in a 0-type (orthogonal) configuration. The manufactured liquid crystal display device used a measuring machine "Red-Cont ras t 1 60D, manufactured by ELDIM Co., Ltd.", and the viewing angle was measured in 8 steps from black display (L1) to white display (L8). The results are shown in Table 4. [Comparative Example 3] A liquid crystal display device (6 E-A 3, sharp) made by a TN-type liquid crystal cell, using a measuring machine (EZ-Cpnt i.as t 160D, manufactured by ELDIM), self-black The display (L 1) to white display (L8) are measured in 8 steps. -107-581885 V. Description of the invention (106) Table 4 Viewing angle of the liquid crystal display device (the contrast is greater than 10 on the black side without step inversion) Rotated joints h Up, down, left and right Example 9 18 ° 23. 77 ° Comparative example 3 15. 25. 37 ° (Note) Black-side tone inversion: inversion between L 1 and L 2 (frame-edge transmission A flat estimate of the ratio) A pair of polarizing plates provided on a 20-inch liquid crystal display device (manufactured by LC-20V1, sharp) using a TN liquid crystal cell is peeled off, and the polarized light produced in Example 6 is removed. The plate is adhered to the liquid crystal cell side of the optical compensation sheet via an adhesive, and one sheet is attached to each of the observer side and the background light side. The polarized light on the observer side The transmission axis is arranged perpendicular to the transmission axis of the polarizing plate on the background light side. Under ambient conditions of temperature 25 ° C and relative humidity 60%, the backlight of the manufactured liquid crystal display device is continuously turned on for 5 hours in a dark room The overall black display state was visually observed to evaluate the light leakage situation. As a result, in the 20-inch liquid crystal display device using the polarizing plate produced in Example 6, no frame-shaped transmittance improvement (light leakage) occurred. [Example 1 0 ] The following composition was put into a mixing tank, heated and stirred to dissolve each component to prepare a cellulose acetate solution. The cellulose acetate solution was composed of 100 parts by mass of cellulose acetate having a degree of acetic acid of 60.9% -108- —- ^ '581885 V. Description of the invention (107) Triphenyl phosphate (plasticizer) 7. 8 parts by mass of biphenyl diphenyl phosphate (plasticizer) 3.9 parts by mass of dichloromethane (first Solvent) 300 parts by mass of methanol (second solvent) 5 4 parts by mass of 1-butanol (third solvent) 1 1 part by mass of 1 6 parts by mass of a hysteresis increasing agent used in Example 1, 80 parts by mass Parts by mass of dichloromethane and 20 parts by mass Methanol, heat and stir to prepare a hysteresis rising agent solution. In 46 8 parts by mass of cellulose acetate, mix 32 parts by mass of a hysteresis rising agent solution, and stir thoroughly to prepare a solution. The amount of hysteresis rising agent to 100 parts by mass For cellulose acetate, it is 4.5 parts by mass. The obtained solution was cast using a belt casting machine. After the film surface temperature on the tube was 40 ° C, it was dried for 1 minute and stripped. Under a dry wind of 0 ° C, it was stretched with a 25% tenter transverse axis. Then, it was stretched in the conveying direction by 10% of the longitudinal axis under a drying wind of 140 ° C, and dried under a drying wind of 130t for 15 minutes, and the residual solvent content was 0.3% by weight cellulose acetate film (thickness: 5 0 // m ) 〇 Regarding the produced cellulose acetate film (KH-04), the Re hysteresis (1 ^ 5 50) and 1 at a wavelength of 550 nm were measured using a Jerebsor tester (M-150, manufactured by JASCO Corporation). "" Hysteresis (1 ^ 115 50). The results are shown in Table 5. [Example 1M The solution obtained in Example 10 was cast using a tape casting machine. After the film surface temperature on the tube was 40 ° C , After drying for 1 minute and stripping, at 130t

-109- 581885 V. Description of the invention (108) Under the drying wind, 20% of the tenter cross-axis stretching is performed. Then, it was stretched in the conveying direction by 8% of the longitudinal axis under a Mot: t drying wind, and dried under a drying wind at 130 ° C for 15 minutes to produce a residual solvent amount of 0.3% by weight cellulose acetate thin moon (thickness) : 5 8 // m).

Regarding the produced cellulose acetate film (KH-05), the Re hysteresis (1 ^ 5 5 0) and 1 at a wavelength of 5 50 nm were measured using a Yerbuso tester (M-150, manufactured by JASCO Corporation). ^ 11 Hysteresis (1 ^ 115 50). The results are shown in Table 5. In addition, the prepared cellulose acetate was immersed in a 2.0N potassium hydroxide solution (25 ° C) for 2 minutes, and then neutralized with sulfuric acid, washed with pure water, and dried. Then, this cellulose acetate film is subjected to an alkali treatment. When the surface energy of the saponified cellulose acetate film was determined by the contact angle method, it was 63 mN / m. On the cellulose acetate film, a wire rod coater of # 1 6 was applied to 2 8m Ι. / m2 The alignment film used in Example 2. Dry at 60 ° C for 60 seconds and 90 ° C at 150 seconds. Then, a lamination process was performed on the film formed in the length direction of the cellulose acetate film and the 45 ° direction. (Formation of optically anisotropic layer) 102 g of an optical disk (disc-shaped) liquid crystal compound used in Example 2 was dissolved in 102 g of an iron wire rod of # 3.6 on the alignment film, and 4,06 g was dissolved. Ethylene oxide modified trimethylolpropane triacrylate (V # 3 60, manufactured by Osaka Organic Chemicals Co., Ltd.), 0.90 g of cellulose acetate butyrate (CAB551-0.2, Yi Shi Dun Ma ( (Transliteration) manufactured by Chemical Co., Ltd., 0.23 g of cellulose acetate butyrate (CAB531-1 -110- V. Description of the invention (109), manufactured by Eston Chemical Co., Ltd.), 1.3 g Polymerization initiator (Iruqakia (transliteration) 907, manufactured by Chiba Machinery Co., Ltd.), 0.45g of sensitizer (carthage (transliteration) DETX, manufactured by Nippon Kayaku Co., Ltd.) methyl ethyl ketone Overlay. It was heated for 2 minutes in the temperature range of 1 ° C to align the disc-shaped compound. Then, the disc-shaped compound was polymerized by using a 120W / crri high-pressure mercury lamp and UV irradiation at 60t for 1 minute. , And cooled to room temperature. The optically anisotropic layer was thus formed to prepare an optical compensation sheet (KH-1 5). The Re hysteresis of the optically anisotropic layer measured at a wavelength of 550 nm was 43 nm. Further, it was on the surface of the cellulose acetate film The average angle (tilt angle) was 42 °. [Example 12] The following composition was put into a mixing tank, heated and stirred to dissolve each component to prepare a cellulose acetate solution. The degree of vinegarization of the cellulose acetate solution composition 60,7% of cellulose acetate 100 parts by mass of polyester carbamate 16 parts by mass (B-3 26, Sumitomo Bayer Carbamate (stock), Dismokro 176) methylene chloride ( 1st solvent) 300 parts by mass of methanol (second solvent) 5 4 parts by mass of i-butanol (third solvent) 1 1 part by mass of 16 parts by mass of a hysteresis rising agent used in Example 1 , 80 parts by mass of dichloromethane and 20 parts by mass of methanol, heat and stir -111- V. Description of the invention (1 1 0) Mix 4 to 6 parts by mass of the cellulose acetate solution with 2 to 6 parts by mass of the hysteresis rising agent solution, and stir thoroughly to prepare the solution. Addition of the hysteresis rising agent The amount was 3.5 parts by mass for 100 parts by mass of cellulose acetate. The obtained solution was cast using a belt casting machine. After the film surface temperature on the tube was 40 ° C, it was dried for 1 minute and peeled. After taking it, it is stretched with a tenter in a width direction of 40% in a state where the residual granules are 5%, and drawn in a lengthwise direction with a residual solvent of 5% by weight under a dry wind of 130 ° C. It stretched 28%, and was dried at 1 40 ° C to produce a residual solvent of 0.3% by weight cellulose acetate film (thickness: 40 / zm). Regarding the produced cellulose acetate film (ΚΗ-0 6), The Rehysteresis (Re 5 5 0) and Rth Hysteresis (Rth 550) at a wavelength of 550 μm were measured using a Yerbeso tester (M-150, manufactured by JASCO Corporation). The results are shown in Table 5. Example 11: Alkaliization treatment and alignment film formation were performed on the produced cellulose acetate film in the same manner. Then, an optically anisotropic layer was formed to prepare an optical compensation sheet (KH-16). [Example 13] The following composition was put into a mixing tank, heated and stirred, and the components were dissolved to prepare a cellulose acetate solution. 100 parts by mass 3 0 0 parts by mass 5 4 parts by mass 1 1 part by mass of cellulose acetate solution composition cellulose acetate dichloromethane (first solvent) 60. 7% methanol (second solvent) 1 _ butanol (Third solvent) -112 581885 V. Description of the invention (1 1 1) Boron nitride powder (highly thermally conductive particles) 3 0 parts by mass was put into another mixing tank 16 parts by mass was used for the hysteresis rise of Example 1 Agent, 80 parts by mass of dichloromethane, and 20 parts by mass of methanol, and heating and stirring to prepare a hysteresis rising agent solution. To 474 parts by mass of the cellulose acetate solution, 25 parts by mass of the lagging agent solution was mixed, and the solution was sufficiently stirred. The amount of the retardation rising agent is 3.5 parts by mass for 100 parts by mass of cellulose acetate.

The obtained solution was cast using a belt caster. After the film surface temperature on the tube is 40 ° C, dry it for 1 minute and peel it off, and then at 140 ° C, make the film surface temperature on the tube 4 (after drying for 1 minute after TC and peel it off) Using a tenter under a drying wind at 140 ° C, 38% horizontal axis stretching was performed. Then, it was dried under a drying wind at 135 t for about 20 minutes to produce a residual solvent amount of 0.3% by weight cellulose acetate film ( Thickness: 65 // m).

When the thermal conductivity of the obtained cellulose acetate film was measured, it was 1.2 W / (ni · K). The thermal conductivity is that the sheet is sandwiched between the TO-3 heating box and the copper plate, the thickness of the sheet is compressed to 10%, the power is applied to the copper heating box for 5W, and the temperature is maintained for 4 minutes. The difference is calculated by the following formula. Thermal conductivity {W / (m · K)} = 丨 Power (W) X Thickness (m)} / {Temperature difference (K) X Measurement area (m2)} About the produced cellulose acetate film (KH-07) The Re hysteresis chirp (Re 5 50) and Rth hysteresis chirp (Rth 5 50) at a wavelength of 550 nm were measured using a Yerbeso tester (M-150, manufactured by JASCO Corporation). The results are shown in Table 5.

In addition, the produced cellulose acetate film (KH-07) was immersed in 1.5N -113- 581885 5. Potassium hydroxide solution (40 ° C) of the invention description (112) for 5 minutes. Wash and dry with pure water. When the surface energy of the cellulose acetate film (KH-0 7) was determined by the contact angle method, it was 68 mN / m. (Production of Alignment Film) On this cellulose acetate film, an alignment film of 28 m 1 / m 2 used in Example 2 was coated with a wire rod applicator of # 16. It was dried with warm air at 60 π for 60 seconds, and dried with warm air at 90 ° C for 150 seconds.

Then, a lamination process was performed on the film formed with the late phase axis (measured at a wavelength of 6 32 · 8 nm) of the cellulose acetate film and a direction of 45 °. (Production of liquid crystal compounds)

First, confirm the synthesis of the liquid crystalline polymer and the homeoti_opic alignment on the substrate without alignment processing. 10 millimoles 4-n-butylbenzoic acid, 95 millimoles p-benzoic acid, 50 millimoles methylhydroquinone diacetate, 50 millimoles catechol diacetate, and i OOmg of sodium acetate was polymerized under a nitrogen atmosphere at 270 ° C for 12 hours. Then, the obtained reaction product was dissolved in tetrachloroethane, and then reprecipitation treatment was performed with methanol to obtain 22.0 g of a liquid crystalline polyester. The liquid crystalline polyester had a logarithmic viscosity of 0.15, a twisted phase with a liquid crystal phase, an isotropic phase-liquid crystal phase transition temperature of 240 ° C, and a glass transition temperature of 75 ° C. This liquid crystalline polyester was used to prepare a 10 wt% benzene / tetrachloroethane mixed solvent (6/4 mass ratio) solution. The solution was applied on a soda glass plate by a rod coating method and the solvent was removed. Then, it was heat-treated at 1 90 ° C for 30 minutes, and then cooled and fixed at room temperature. As a result, -114- 581885 with uniform film thickness of 1 5 // m was prepared. 5. Description of the invention (113) Liquid crystal film. When observed with a cone lens, it was found that the polymer liquid crystal had a positive uniaxial structure, and the polymer had a torsional alignment in the same direction. (Formation of Optically Anisotropic Layer) An 8 wt% tetrachloroethane solution of the liquid crystalline polyester obtained above was prepared. Then, the alignment film is coated by a spin coating method. After removing the solvent, it was heat-treated at 190 ° C for 20 minutes. After heat treatment, it is air-cooled and fixed. The obtained optical compensation sheet (KH-17) was transparent, had no alignment defects, and had a uniform film thickness (1.55 // m). [Comparative Example 4] A cellulose acetate film (KH-H2) with a residual solvent of 3.0% by weight was produced and evaluated in the same manner as in Example 10, except that the cellulose acetate solution was directly used as the solution and subjected to a stretching treatment. The thickness of the produced cellulose acetate is 80 // m. The optical characteristics of the obtained film were measured. The results are shown in Table 5 -115- 581885. 5. Description of the invention (114) KH-06 3.5 parts by mass 25nm 120nm Example 13 KH-07 3.5 parts by mass 50nm 90nm Comparative Example 4 KH-H2 Niu \ w 4nm 48nm [Example 1 4] Adsorb iodine on a stretched polyvinyl alcohol film to A polarizing film was produced, and a polyvinyl alcohol-based adhesive was used, and the optical compensation sheet (KH-04) produced in Example 10 was attached to one side of the polarizing film. A commercially available cellulose acetate film (Fujitak TD80UF, Fuji Photo Negative Film (stock)) was saponified, and a polyethylene-based adhesive was used and attached to the opposite side of the polarizing film. The transmission axis of the polarizing film is arranged parallel to the retardation axis of the optical compensation sheet (KH-04). Thus, a polarizing plate was produced. [Example 15] An iodine was adsorbed on a stretched polyvinyl alcohol film to make a polarizing film, and a polyvinyl alcohol-based adhesive was used to make the optical compensation sheet (KH-15) prepared in Example 11 and the carrier The cellulose acetate film (KH-05) is on the polarizing film side, and its late phase axis and the transmission axis of the polarizing film are attached to one side in parallel. For commercially available cellulose acetate film (Fujitak TD80UF, Fuji Photo

-116- 581885 V. Description of the invention (115) Negative film (made from stock) is saponified, and it is attached to the opposite side of the polarizing film with a polyethylene adhesive. Thus, a polarizing plate was produced. [Sinus Example 16] An iodine was adsorbed on a stretched polyvinyl alcohol film to make a polarizing film, and a polyvinyl alcohol-based adhesive was used to make the optical compensation sheet (KH-16) produced in Example 12 and its The cellulose acetate film (KH-06) of the carrier is on the side of the polarizing film, and its late phase axis and the transmission axis of the polarizing film are attached to one side in parallel. A commercially available cellulose acetate film (Fujitak TD80UF, Fuji Photo Negative Film (stock)) was saponified, and a polyethylene-based adhesive was used and attached to the opposite side of the polarizing film. Thus, a polarizing plate was produced. [Example 17] An iodine was adsorbed on a stretched polyvinyl alcohol film to make a polarizing film, and a polyvinyl alcohol-based adhesive was used to make the optical compensation sheet (KH-17) prepared in Example 13 and the carrier The cellulose acetate film (KH-07) is on the polarizing film side, and its late phase axis and the transmission axis of the polarizing film are attached to one side in parallel. A commercially available cellulose acetate film (Fujitak TD80UF, Fuji Photo Negative Film (stock)) was saponified, and a polyethylene-based adhesive was used and attached to the opposite side of the polarizing film. Thus, a polarizing plate was produced. [Comparative Example 5] An iodine was adsorbed on a stretched polyvinyl alcohol film to produce a polarizing film, and an optical compensation sheet (kh -2) produced in Comparative Example 4 was attached to the polarizing film using a polyvinyl alcohol-based adhesive. One side. Saponification treatment of commercially available cellulose triacetate film (Fujitak TD80UF, Fuji-117- 581885 V. Description of the invention (116) Photo negative (stock)), using a polyethylene-based adhesive, attached to Opposite side of polarizing film. Thus, a polarizing plate was produced. [Example 1 8] A pair of polarizing plates and a pair of optical compensation sheets provided on a liquid crystal display device (VL-1 5 30S, manufactured by Fujitsu Co., Ltd.) using a vertical alignment type liquid crystal cell were peeled off and implemented. The polarizing plate produced in Example 14 was adhered to the liquid crystal cell side of the optical compensation sheet (KH-04) through an adhesive, and attached to the observer side. In addition, a commercially available polarizing plate (HLC2-5618HCS, (shares) Cyrels) is attached to the backlight side. The transmission axis of the polarizer on the viewer side faces up and down, and the transmission axis of the polarizer on the background side faces the left and right coils. Regarding the produced liquid crystal display device, the viewing angle was measured in eight steps from a black display (L1) to a white display (L8) using a measuring machine (Ultra-Contras 160D, manufactured by ELDIM). The measurement results are shown in Table 6. [Comparative Example 6] A pair of polarizing plates provided on a liquid crystal display device (VL-1 5 30S, manufactured by Fujitsu Co., Ltd.) using a vertically aligned liquid crystal cell was peeled, and the polarizing plate produced in Comparative Example 5 was peeled off. Adhere to the liquid crystal cell side of the optical compensation sheet (KH-H2) through the adhesive, and stick to the observer side. Furthermore, a commercially available polarizer (HLC2-5618HCS, (Srlitz)) is attached to the backlight side. The transmission axis of the polarizer on the viewer side faces up and down, and the transmission axis of the polarizer on the background side crosses the line along the left and right direction. Regarding the produced liquid crystal display device, a measuring machine "Redundant-Contrastl60D, manufactured by ELDI M. Co., Ltd." was used to measure the viewing angle in eight stages from black display (L1) to white display (L8).

-118- 581885 V. Description of the invention (117) Table 6 Viewing angle of the liquid crystal display device (contrast is more than 10 black; there is no range of tone inversion on the side) Transmission axis direction 45 ° from the transmission axis Example 18 > 80 ° __ > 80 ° Comparative Example 6 > 80 ° 44 ° (Note) Black-side tone inversion: inversion between L 1 and L2 (evaluation of frame-like transmittance improvement) When using vertical A pair of polarizing plates provided on a 15-inch liquid crystal display device (VL-1 5 30SW, manufactured by Fujitsu Co., Ltd.) of an alignment type liquid crystal cell is peeled off, and the polarizing plates prepared in Example 14 are adhered through an adhesive. Attach one to the liquid crystal cell side of the optical compensation sheet, one to the observer side and one to the background light side. The transmission axis of the polarizer on the observer side and the transmission axis of the polarizer on the background side are arranged orthogonally. Similarly, the polarizing plate produced in Comparative Example 5 was mounted on a liquid crystal display device. Under ambient conditions of temperature 25 ° C and relative humidity 60%, continuously turn on the backlight for 5 hours continuously and visually observe the full black display state in a dark room to evaluate light leakage. As a result, in a case where a peripheral edge of the display panel of the liquid crystal display device using the polarizing plate of Comparative Example 5 caused frame-shaped light leakage (increased transmittance), the 15-inch liquid crystal of the polarizing plate produced in Example 14 The display device does not have a frame-shaped transmittance increase (light leakage). [Example 19] (Production of curved alignment liquid crystal cell) -119- 581885 V. Description of the invention (118) A polyimide film as an alignment film was provided on a glass substrate with an ITO electrode, and was performed on the alignment film. Multilayer processing. The two glass substrates obtained were arranged in parallel in a lamination direction and combined, and the cell gap was set to 6 V m. Into the gap, a liquid crystal compound (ZLI 1 1 32, manufactured by Meluk Corporation) with a Δη of 0.1396 was injected to make a 17-inch curved alignment liquid crystal cell. (Manufacturing of a liquid crystal display device) Two polarizing plates prepared in Example 15 were bonded to each other under a bendable alignment cell that could be sandwiched. The optically anisotropic layer of the elliptically polarizing plate is opposed to the cell substrate, and the lamination direction of the liquid crystal cell is arranged in antiparallel to the lamination direction of the optical anisotropic layer on the opposite side. A rectangular wave voltage of 55 Hz was applied to the liquid crystal cell. 2V white display and 5V black original white display. The transmittance ratio (white display / black display) is used as a control ratio, and the field of view is measured in 8 stages from black display (L 1) to white display (L8) using a measuring device (EZ-Contras t 160D, manufactured by ELDIM). angle. The measurement results are shown in Table 7. [Example 20] (Production of curved alignment liquid crystal cell) A polyimide film as an alignment film was provided on a glass substrate with an IT0 electrode, and a lamination process was performed on the alignment film. The two glass substrates thus obtained were arranged in parallel in a stacking direction, and the cell gap was set to 6 / z m. A liquid crystal compound (ZLI 1132, manufactured by Meluk Corporation) having a Δη of 0.1 3 96 was injected into the gap to make a 17-inch curved alignment liquid crystal cell.

-120- 581885 V. Description of the invention (119) (manufacturing of liquid crystal display device) The two polarizing plates produced in Example 16 are bonded together under the bendable alignment cell that can be made. The optically anisotropic layer of the elliptically polarizing plate is opposed to the cell substrate, and the lamination direction of the liquid crystal cell is arranged in antiparallel to the lamination direction of the optical anisotropic layer on the opposite side.

A rectangular wave voltage of 55 Hz was applied to the liquid crystal cell. 2V white display and 5V black original white display. The transmittance ratio (white display / black display) was used as a control ratio, and the viewing angle was measured in eight stages from black display (L1) to white display (L8) using a measuring device (EZ-Contras t 160D, manufactured by ELDIM). The measurement results are shown in Table 7.

Table 7 Viewing angle of the liquid crystal display device (the contrast is black with 10 or more! PJ has no range of tone inversion) Up Down Left Right Example 19 80. 80 ° 80 ° Example 20 80 ° 80 ° 80. (Note) Inversion of black tone: Inversion between L1 and L2 (assessment of frame-shaped transmittance improvement) Under the environmental conditions of temperature 25 ° C and relative humidity 60%, in Example 19 and The manufactured LCD panel was equipped with a backlight, and after continuously lighting for 5 hours, the overall black display state was visually observed in a dark room to evaluate light leakage. As a result, in the liquid crystal display device using the polarizing plate of Comparative Example 5, -121-581885 V. Description of the Invention (12) There is no frame-like shape in the 17-inch liquid crystal panel manufactured using Examples 19 and 20 Increased transmittance (light leakage) occurs. [Example 2 1] A pair of polarizing plates provided on a liquid crystal display device (6E-A3, made by Sharp) using a TN-type liquid crystal cell was peeled off, and the polarizing plates prepared in Example 17 were bonded together. The agent is stuck to the liquid crystal cell side of KH-07, and one sheet is attached to each of the observer side and the backlight side. The transmission axis of the polarizer on the observer side and the transmission axis of the polarizer on the background side are arranged orthogonally. For the produced liquid crystal display device, a measuring machine "Red-Contras tl60D, manufactured by ELDIM Co., Ltd." was used, and the viewing angle was measured in 8 steps from the black display (L1) to the white display (L8). The results are shown in Table 8. Table 8 8 Viewing angle of liquid crystal display device (contrast range of 10 or more without black level inversion) Example 21 35. 60 ° 80. (Note) Black level inversion: between L1 and L2 Inversion (Evaluation of improvement of frame-shaped transmittance) A pair of polarizing plates provided on a 20-inch liquid crystal display device (manufactured by LC-20V1, made by Sharp) using a TN liquid crystal cell was peeled off, and Examples were made. 17 The produced polarizing plate is adhered to the liquid crystal cell side of the optical compensation sheet through an adhesive, and one sheet is attached to the observer side and the background light side. The polarizing plate on the observer side -122-581885 V. Description of the invention (121 ), The transmission axis is orthogonal to the transmission axis of the polarizer on the background light side. Under ambient conditions of temperature 25 ° C and relative humidity 60%, continuously turn on the backlight for 5 hours and visually observe the full black display in a dark room. The state is g to evaluate light leakage. As a result, the liquid crystal There is no light leakage on the display surface without the device. As a result, there is no frame-like transmittance improvement (light leakage) in the 20-inch liquid crystal display device using the polarizing plate manufactured in Example 17. [Implementation Example 22] The following composition was put into a mixing tank, and the components were heated and stirred to dissolve each component to prepare a cellulose acetate solution. The cellulose acetate solution composed of 100 parts by mass of triphenyl phosphate cellulose acetate having a degree of acetic acidity of 60.9%. (Plasticizer) 7.8 parts by mass of biphenyl diphenyl phosphate (plasticizer) 3.9 parts by mass of dichloromethane (first solvent) 300 parts by mass of methanol (second solvent) 54 parts by mass of 1-butanol ( Third solvent) 1 1 part by mass Put 16 parts by mass of the hysteresis rising agent used in Example 1, 80 parts by mass of dichloromethane, and 20 parts by mass of methanol in another mixing tank, and heat and stir to prepare a hysteresis raising agent solution. 25 mass parts of the stagnation rising agent solution was mixed in 474 parts by mass of the cellulose acetate solution, and the solution was thoroughly stirred to prepare a solution. The amount of the hysteresis rising agent was 3.5 parts by mass for 100 parts by mass of cellulose acetate. The solution was cast using a belt casting machine. The residual solvent amount was 1 5 -123- 581885. V. Description of the invention (122) The film of mass% was stretched at 25% using a tenter under the condition of 1 30 ° C. Stretched horizontally to obtain a cellulose acetate film (thickness: 70 V m). In addition, the prepared cellulose acetate was immersed in a 1.5 N potassium hydroxide solution (50 ° C) for 2 minutes, and then sulfuric acid was added. Neutralize. Then, take out the cellulose acetate film from the solution, wash it with pure water, and dry it. The surface energy of the saponified cellulose acetate film obtained by the contact angle method is 60mN / in. The produced cellulose acetate film (optical compensation sheet) was measured for a 5 ^ retardation chirp (1 ^ 5 50) and ^^ "at a wavelength of 550 nm using a Yelibuso tester (M-150, manufactured by JASCO Corporation). Hysteresis (1 ^ "5 50). The results are shown in Table 9. [Example 23] A solution was prepared by mixing 56 parts by mass of a hysteresis rising agent solution in 474 parts by mass of a cellulose acetate solution (the addition amount of the hysteresis rising agent was 7.8 parts by mass for 1,000 parts by mass of cellulose acetate. ), Except that the stretching ratio was changed to 14%, a cellulose acetate film (optical compensation sheet) was produced in the same manner as in Example 22. 〇 Furthermore, the produced cellulose acetate was immersed in a 1.5N potassium hydroxide solution (40 ° C) After 5 minutes, neutralize with sulfuric acid. The cellulose acetate film was taken out of the solution, washed with pure water, and then dried. The surface energy of the saponified cellulose acetate film obtained by the contact angle method was 68 mN / m. Regarding the produced cellulose acetate film (optical compensation sheet), a Yelibuso tester (M_150, manufactured by JASCO Corporation) was used to measure the wavelength of 550 nm -124- 581885. 5. Description of the invention (123) 1 ^ Hysteresis (1 ^ 5 50) and 1 ^} 1 hysteresis (1 ^} 15 50). The results are shown in Table 9. [Example 24] A cellulose acetate film was produced in the same manner as in Example 23 except that the stretching ratio was changed to 8%. In addition, the produced cellulose acetate film was immersed in a 2. ON potassium hydroxide solution (25 ° C) for 2 minutes, and then neutralized with sulfuric acid. The cellulose acetate film was taken out of the solution, washed with pure water, and then dried. When the surface energy of the saponified cellulose acetate film was determined by the contact angle method, it was 63 mN / m. On the cellulose acetate film, coating was performed with an iron wire coater of # 1 6 2 8 m I / m 2 and implemented. The alignment film used in Example 2. Dry at 60 ° C for 60 seconds and 90 ° C for 150 seconds. Then, a lamination process was performed on the film formed by the late phase axis (measured at a wavelength of 632.8 nm) of the cellulose acetate film and a direction of 45 °. (Formation of Optically Anisotropic Layer) On the alignment film, 102 g of an iron wire rod of # 3 was applied to dissolve 41.0 lg of a disc (disk-shaped) liquid crystal compound used in Example 2 and 4.06 g of ethylene oxide. Modified trimethylolpropane triacrylate (V # 3 60, manufactured by Osaka Organic Chemicals Co., Ltd.), 0.90 g of cellulose acetate butyrate (CAB551-0.2, manufactured by Eston Chemical Co., Ltd.), 0.02 g of cellulose acetate butyrate (CAB53, 1, manufactured by Eston Chemical Co., Ltd.), 1.5 g of a photopolymerization initiator (Erukhaya 907, manufactured by Chiba Machinery Co., Ltd.), 0.45 g of a methyl ethyl ketone coating solution of a sensitizer (Kayakiya DETX, manufactured by Nippon Kayaku Co., Ltd.). -125- 581885 V. Description of the invention (124) It is attached to a metal frame and heated in a horizontal temperature tank at 130 ° C for 2 minutes to align the disc-shaped compound. Then, the disc-shaped compound was polymerized by using a 120 W / Cm high-pressure mercury lamp and UV irradiation at 130 ° C. for 1 minute. Then 'is cooled to room temperature. Thus, an optically anisotropic layer was formed. Regarding the produced cellulose acetate film (optical compensation sheet), "Hysteresis (1 ^ 550) and 1?" "Hysteresis (1?" 550) were measured in the same manner as in Example 22. The results are shown in Table 9. [ Example 25] A solution was prepared by mixing 56 parts by mass of a hysteresis rising agent solution in 474 parts by mass of a cellulose acetate solution (the addition amount of the hysteresis rising agent was 7.8 parts by mass for 1,000 parts by mass of cellulose acetate) The stretching ratio was changed to 3 5% except that a cellulose acetate film (optical compensation sheet) was produced in the same manner as in Example 22. In addition, a corona discharge treatment with a discharge frequency of 100 kHz was performed on the surface of the produced cellulose acetate film. When the surface energy of the corona discharge-treated cellulose acetate film was determined by the contact angle method, it was 60 niN / m. Regarding the produced cellulose acetate film (optical compensation sheet), a wavelength of 550 was measured in the same manner as in Example 22. Dragon's 1 ^ retardation (1 ^ 550) and 1 ^ 11 retardation (Rth5 50). The results are shown in Table 9. [Comparative Example 7] A cellulose acetate solution was directly used as a solution, and a stretching treatment and Except for saponification treatment, it is the same as in Example 2. 2A cellulose acetate film (optical compensation sheet) was produced and evaluated in the same manner. The results are shown in Table 9. -126- 581885 V. Description of the invention (125) Table 9 Stretching ratio of retardation rising agent Re550 Rt550 Example 22 3.5 parts by mass 25% 40nm 130nm Example 23 7.8 parts by mass 14% 50nm 240nm Example 24 7.8 parts by mass 8% 20nm 220nm Example 25 7.8 parts by mass 35% 120nm 250nm Comparative Example 7 te / \ \\ Not stretched_ 4nm 48nm [Example 26] Adsorbed on a stretched polyvinyl alcohol film to make a polarizing film, and using a polyvinyl alcohol-based adhesive, the cellulose acetate film produced in Example 22 was attached to one side of the polarizing film . Then 'saponify a commercially available cellulose acetate film (Fujitak TD80UF, Fuji Photo Negative Film (stock)), and use a polyethylene-based adhesive to attach it to the opposite side of the polarizing film. Transmission axis of the polarizing film It is disposed orthogonally to a late phase axis of a commercially available cellulose triacetate film. In this way, a polarizing plate was produced. [Example 27] The same procedure as in Examples 2 to 6 was performed except that the cellulose acetate film produced in Example 23 was used. Polarizer [Example 28] A polarizing plate was produced in the same manner as in Example 2 except that the cellulose acetate film prepared in Example 24 was used. -127- 581885 V. Description of the invention (126) [Example 29] When using vertical A pair of polarizing plates and a pair of optical compensation sheets provided on an alignment type liquid crystal cell liquid crystal display device (VL-1530 S, manufactured by Fujitsu Co., Ltd.), and the polarizing plate produced in Example 26 was peeled off. The cellulose acetate film produced in Example 26 was adhered to the liquid crystal cell side through an adhesive, and one sheet was attached to each of the observer side and the backlight side. The transmission axis of the polarizer on the viewer side faces up and down, and the transmission axis of the polarizer on the background side faces the left and right cross coils. For the produced liquid crystal display device, a measuring machine "Red-Cont Ras 160D, manufactured by ELDIM Co., Ltd." was used, and the viewing angle was measured in 8 steps from the black display (L1) to the white display (L8). The results are shown in Table 10. [Example 30] A pair of polarizing plates and a pair of optical compensation sheets provided on a liquid crystal display device (VL- 1530S, manufactured by Fujitsu Co., Ltd.) using a vertical alignment type liquid crystal cell were peeled off, and Instead of the cellulose acetate film produced in Example 23, the polarizing plate produced in Example 27 was adhered to the liquid crystal cell side through an adhesive, and one sheet was attached to each of the observer side and the backlight side. Attach a commercially available polarizer (HLC2-5618HCS, made by Selitz). · The transmission axis of the polarizer on the viewer side is up and down, and the transmission axis of the polarizer on the background side is left and right Directional cross-coil arrangement. The produced liquid crystal display device was measured in 8 steps from a black display (L1) to a white display (L8) using a measuring machine "Red-Cont Ras 160D, manufactured by ELDIM". The results are shown in Table 10. -128- 581885 V. Description of the Invention (127) [Comparative Example 8] For a liquid crystal display device (VL-1530S, manufactured by Fujitsu Co., Ltd.) for a vertically aligned liquid crystal cell, a measuring machine (EZ-ConU'as t 160D) was used. (Manufactured by ELDIM), and the viewing angle is measured in 8 steps from black display (L1) to white display (L8). The results are shown in Table 10. Table 10 Viewing angle of the liquid crystal display device (contrast is a range with no tone reversal on the black side of 10 or more) Transmission axis direction 45 ° direction from the transmission axis Example 29 80 ° 80. Examples 30 80. 80. Comparative Example 8 80. 44 ° (Note) Inversion of tone on the black side: inversion between L 1 and L2 [Example 3 1] (Production of curved alignment liquid crystal cell) Provided as an alignment film on a glass substrate with ITO electrode A polyimide film is laminated on the alignment film. The two glass substrates obtained were arranged in parallel in the direction of lamination, and the cell gap was set to 6 // m. A liquid crystal compound (ZLI 1 1 32, manufactured by Meluk Corporation) having a Δη of 0.1396 was injected into the gap to produce a curved alignment liquid crystal cell. The two polarizing plates prepared in Example 28 were bonded to each other while sandwiching the produced bending alignment cell. The optically anisotropic layer of the polarizing plate is opposed to the cell substrate, and the stacked direction of the liquid crystal cell is opposite to the stacked direction of the optical anisotropic layer on the opposite side. -129- 581885 5. Description of the invention (128) Anti-parallel configuration. A rectangular wave voltage of 55 Hz was applied to the liquid crystal cell. 2V white display and 5V black original white display. The transmittance ratio (white display / black display) was used as a control ratio, and the viewing angle was measured in a δ stage from black display (L1) to white display (L8) using a measuring device (EZ-Contras t 160D, manufactured by ELDIM). The measurement results are shown in Table 11. Table 1 1 Viewing angle of a liquid crystal display device (contrast is a range with no tone inversion on the black side of 10 or more). 80. 80. (Note) Black-side tone inversion: Inversion between L1 and L2 [Example 32] A liquid crystal display device using a TN-type liquid crystal cell (6E-A3, sha 1 · ρ (share)) A pair of polarizing plates provided above, and the polarizing plate prepared in Example 26 was adhered to the liquid crystal cell side of the cellulose acetate film prepared in Example 2 through an adhesive, on the observer side and the backlight side Attach one to each. The transmission axis of the polarizer on the observer side and the transmission axis of the polarizer on the background side are arranged orthogonally. Regarding the manufactured liquid crystal display device, a measuring machine was used. ”-Contras 160D, manufactured by ELDIM Co., Ltd.) The viewing angle was measured in 8 steps from black display (L1) to white display (L8). The results are shown in Table 12 • 130- 581885 V. Description of the invention (129) [Comparative Example 9] A liquid crystal display device (6E_A3, sharp) made using a TN-type liquid crystal cell is a measuring device (EZ-Cntrast 1 6 0D, ELD (Made by IM company), and the viewing angle was measured in 8 stages from black to white (L 1) to white (L 8). The results are shown in Table 12. 2. Table 12 Viewing angle of liquid crystal display device (compared to 10 or more) The range on the black side does not have the tone inversion range) Example 32.18. 23. 77 ° Comparative Example 9 15. 25. 37. (Note) The tone inversion on the black side: between L1 and L2 [Example 33] (Production of cellulose acetate film) The following composition was put into a mixing tank and heated and stirred to dissolve each component to prepare a cellulose acetate solution. The cellulose acetate solution composition was 100 parts by mass of 7.8 3.9 parts by mass, 300 parts by mass, 54 parts by mass, 54 parts by mass, acetic acid degree of cellulose 69.0% Triphenyl Phosphate (Plasticizer) Biphenyl Diphenyl Phosphate (Plasticizer) Dichloromethane (first solvent) Methanol (second solvent) -131 V. Description of the invention (1 3 Ο) 1-Butanol (No. 3 solvents) 1 1 part by mass Put 16 parts by mass of the hysteresis rising agent, 80 parts by mass of dichloromethane, and 20 parts by mass of methanol in another mixing tank, and heat and stir to prepare a hysteresis raising agent solution. In 474 parts by mass of a cellulose acetate solution, 25 parts by mass of a hysteresis rising agent solution was mixed, and the solution was sufficiently stirred to prepare a solution. The amount of the hysteresis rising agent was 100 parts by mass of 3.5 parts by mass of cellulose acetate. The solution was cast using a belt caster. After the film surface temperature of the tube was 40 ° C, the film was dried with warm air at 70 ° C for 1 minute and the film was peeled from the tube. The film was dried in a drying wind at 140 ° C In 10 minutes, a cellulose acetate film (thickness: 50 // m) with a residual solvent content of 3% by mass was produced. The optical properties of the produced cellulose acetate film (CAF-0 1) were measured. The results are shown in Table 1 It is shown in 3. Moreover, the optical characteristics were measured using Yeriberso (M_150, manufactured by JASCO Corporation), and measured the retardation wavelengths of 55,101,101, and ^ 65 50) and! ^} 1, the retardation (Rth550). The produced cellulose acetate film was immersed in 2 After 2 minutes of ON potassium hydroxide solution (2 5 ° C), neutralized with sulfuric acid, washed with pure water, and dried. The surface energy of the cellulose acetate film was determined by the contact angle method to be 63 mN / m. (Formation of alignment film) The prepared cellulose acetate film was coated with an alignment film coating solution of 28 ml / m2 used in Example 2 with a # 16 iron wire bar coater. Dry at 60 ° C for 60 seconds and 9 ° C for 150 seconds. -132- 581885 V. Description of the Invention (131) Then, in a direction parallel to the length direction of the cellulose acetate film, The formed film was laminated. (Formation of an optically anisotropic layer) The alignment film was coated with 102 g of an iron wire rod of # 3.6 to dissolve 41.01 g of the optical disc (disc) used in Example 2 Liquid crystal compound, 4.06 g of ethylene oxide modified trimethylolpropane triacrylate (V # 3 60, manufactured by Osaka Organic Chemicals Co., Ltd.), 0.90 g of cellulose acetate butyrate (CAB551-0.2, Eston Chemical Co., Ltd.), 0.23g of cellulose acetate butyrate (CAB531-1, Eston Chemical Co., Ltd.), 1.35g of photopolymerization initiator (Elucia ( (Transliteration) 907, manufactured by Chiba Machinery Co., Ltd., 0.45 g of sensitizer (Carbachia DETX, Nippon Kayaku Co., Ltd.) methyl ethyl ketone coating solution. At 1 30 ° C Heat in the horizontal temperature zone for 2 minutes to align the disc-shaped compound. Then, use a 120 W / cm high-pressure mercury lamp and UV light at 60 ° C. The disk-shaped compound was polymerized for 1 minute. Then, it was cooled to room temperature. An optically anisotropic layer was formed in this manner to produce an optical compensation sheet (K Η-A 1) ο optical anisotropy measured at a wavelength of 5 50 nm The Re hysteresis of the anisotropic layer was 43 nm. The angle (inclination angle) between the disc surface and the first transparent carrier surface was 42 ° on average. [Example 34] (Production of cellulose acetate film) The following composition was prepared. Put into the mixing tank and heat and stir to dissolve each component to prepare a cellulose acetate solution. -133- 581885 V. Description of the invention (132) The cellulose acetate solution has a vinegarization degree of 60.7% and 100 parts by mass of cellulose acetate. 7.8 parts by mass of ether carbamate (B-326, Sumitomo Bayer carbamate (transliteration) (stock), Dismoklu (transliteration) 176) dichloromethane (first solvent) 300 Part by mass of methanol (second solvent) 54 parts by mass of 1-butanol (third solvent) 1 1 part by mass of 16 parts by mass of a hysteresis rising agent used in Example 1 and 80 parts by mass of dichloride in another mixing tank Methane and 20 parts by mass of methanol, heat and stir to adjust the hysteresis rise Solution. 15 parts by mass of a lagging riser solution was mixed in 484 parts by mass of a cellulose acetate solution, and the solution was thoroughly stirred to prepare a solution. The amount of the lagging riser was 2.0 parts by mass for 100 parts by mass of cellulose acetate. The resulting solution was cast using a belt caster. After the film surface temperature on the tube was 40 ° C, it was dried at 65 ° C for 1 minute and the film with a residual solvent of 15% was stripped from the tube. Then, The film was stretched by 20% in the width direction in this state with a tenter, and dried in a drying wind at 130 ° C. for 5 minutes to produce a residual solvent amount of 5% by mass. In this state, the film was stretched 18% in the longitudinal direction and dried at 140 ° C. for 10 minutes to produce a cellulose acetate film (thickness: 4 〇 // hi) with a residual solvent of 0.3% by mass. . About the produced cellulose acetate film (CAF-02), the optical characteristics were measured. The results are shown in Table 13.

-134- 581885 V. Description of the invention (133) Furthermore, the optical characteristics are measured using a Yelibuso tester (M -1 50, manufactured by JASCO Corporation), and the R e hysteresis (R e 5 5 0) and R th hysteresis (R th 5 5 0). Surface treatment was performed on the cellulose acetate film in the same manner as in Example 33 to form an alignment film and an optically anisotropic layer to produce an optical compensation sheet (KH-A2) ° [Example 3 5] (of the cellulose acetate film Production) The following composition was put into a mixing tank and heated and stirred to prepare a cellulose acetate solution. Cellulose acetate solution composition 60.7% cellulose acetate dichloromethane (first solvent) methanol (second solvent) 1-butanol (third solvent) boron nitride powder to dissolve 100% by mass of each component 300 parts by mass 5 4 parts by mass 1 1 part by mass 30 parts by mass Put 16 parts by mass of the hysteresis rising agent used in Example 1, 80 parts by mass of dichloromethane and 20 parts by mass of methanol in another mixing tank, heat and Stir to prepare a hysteresis solution. To 474 parts by mass of the cellulose acetate solution, 25 parts by mass of the lagging agent solution was mixed, and the solution was sufficiently stirred. The amount of the retardation rising agent is 3.5 parts by mass for 100 parts by mass of cellulose acetate. The obtained solution was cast using a belt caster. The film surface temperature of the tube is 40 -135- 581885 V. Description of the invention After (134) ° C, it is dried at 70 ° C for 1 minute and the film is peeled from the tube. It was dried at 14 ° C. for 10 minutes to produce a cellulose acetate film (thickness: 50 μm) with a residual solvent of 0.3% by mass. When the thermal conductivity of the obtained cellulose acetate film was measured, it was 1.2 W / (m · K). The optical characteristics of the produced cellulose acetate film (CAF-03) were measured. The results are shown in Table 13. In addition, the prepared cellulose acetate (CAF-03) was immersed in a 1.5N potassium hydroxide solution (40 ° C) for 5 minutes, and then neutralized with sulfuric acid, washed with pure water, and dried. When the surface energy of the cellulose acetate film (CAF-03) was determined by the contact angle method, it was 68 mN / m. (Formation of Alignment Film) The prepared cellulose acetate film was coated with a # 1 6 wire rod applicator and applied with 2 8 ml / m2 of the alignment film coating liquid used in Example 2. Dry at 60 ° C for 60 seconds and 90 ° C for 150 seconds. Then, the formed film is laminated in a direction parallel to the longitudinal direction of the cellulose acetate film. (Production of liquid crystalline compound) First, the synthesis of the liquid crystalline polymer and the alignment in the same direction on the non-aligned substrate were confirmed. 10 mmole 4-n-butylbenzoic acid, 95 mmole p-benzoic acid, 50 mmole methyl hydroquinone diacetate, 50 mmole catechin diacetate, and lO. 0mg of sodium acetate 'was polymerized in a nitrogen atmosphere at 270 ° C for 12 hours -136- 5. Description of the invention (1 35). Then, the obtained reaction product was dissolved in tetrachloroethane, followed by reprecipitation treatment with methanol, and purified to obtain 22.0 g of liquid crystalline polyester. The liquid crystalline polyester has a logarithmic viscosity of 0.15, a twisted phase with a liquid crystal phase, an isotropic phase-liquid crystal phase transition temperature of 240 ° C, and a glass transition temperature of 75 ° C. A 10 wt% benzene / tetrachloroethane mixed solvent (6/4 mass ratio) solution was prepared using the liquid crystalline polyester. The solution was applied on a soda glass plate by a rod coating method and the solvent was removed. After heat treatment at 1 90 ° C for 30 minutes, it was cooled and fixed at room temperature. As a result, a liquid crystal film having a uniform thickness of 15 # π was aligned. When observed with a cone lens, it was found that the polymer liquid crystal had a positive uniaxial structure, and the polymer had a torsional alignment in the same direction. (Formation of optically anisotropic layer) An 8wt% tetrachloroethane solution of the liquid crystalline polyester obtained above was prepared. Then, the solution is coated on the alignment film by a spin coating method. After removing the solvent, it was heat-treated at 190 ° C for 20 minutes. After the heat treatment, the alignment state of the liquid crystal compound is fixed by air cooling. The obtained optical compensation sheet (KH-A3) is transparent, has no alignment defects, and has a uniform film thickness (1.55 // m). [Comparative Example 10] The cellulose acetate solution used in Example 33 was directly used as a solution, and cast using a belt caster. After the film surface temperature on the tube is 40 ° C, it is dried in a warm air at 40 ° C for 1 minute, and the film is peeled from the tube. Then, the film was dried in a drying wind at 100 t: 10 minutes, and a cellulose acetate film (thickness: 80 // π〇) with a residual solvent amount of 3.0% by mass was produced. -137- 581885 V. Description of the invention (136) The optical properties of the produced cellulose acetate film (CAF-H1) were measured. The results are shown in Table 1 to 3. Table 13 Film retarder Re550 Rt550 Example 33 CAF-01 3.5 parts by mass 8nm 80nm Example 34 CAF-02 2.5 parts by mass 4nm 90nm Example 35 CAF-03 3.5 parts by mass 9nm 82nm Comparative Example 10 CAF-H1 jw \ 4nm 48nm [Example 36] An iodine was adsorbed on a stretched polyvinyl alcohol film to make a polarizing film, and a polymer was used The vinyl alcohol-based adhesive was used to attach the optical compensation sheet (kH-A 1) produced in Example 33 to one side of the cellulose acetate film (C AF-0 1) such as the polarizing film side. The transmission axis of the polarizing film Arranged parallel to the retardation axis of the optical compensation sheet (kH-A 1). Saponification treatment of commercially available cellulose triacetate film (Fujitak TD80UF, Fuji Photo Negative Film (stock)), using polyethylene It is an adhesive and is attached to the opposite side of the polarizing film. [Example 37] An polarizing film was prepared by adsorbing iodine on the stretched polyvinyl alcohol film, and using a polyvinyl alcohol-based adhesive, the optical compensation sheet (kH-A2) produced in Example 34 was used. Attached to the cellulose acetate film (CAF-Q2) as the polarizing film side -138- 581885 5. Invention description (137) side. The transmission axis of the polarizing film and the retardation axis of the optical compensation sheet (kH-A2) Dispose in parallel. Saponify a commercially available cellulose triacetate film (Fujitak TD80UF, Fuji Photo Negative Film) and use a polyethylene-based adhesive to attach it to the opposite side of the polarizing film. [Example 38] A polarizing film was produced by adsorbing iodine on a stretched polyvinyl alcohol film, and using the polyvinyl alcohol-based adhesive, the optical compensation sheet (kH-A3) produced in Examples 3 and 5 was used. It is attached to one side of the cellulose acetate film (CAF-03) such as a polarizing film side. The transmission axis of the polarizing film is arranged parallel to the retardation axis of the optical compensation sheet (kH-A3). Acetate film (Fujitak TD80UF, Fuji Photo Negative Film) ) Saponification treatment was carried out, and a polyethylene-based adhesive was used and attached to the opposite side of the polarizing film. In this way, a polarizing plate was produced. [Comparative Example 1 1] An iodine was adsorbed on a stretched polyvinyl alcohol film to make a polarizing film. The polyvinyl alcohol-based adhesive was such that the cellulose acetate film produced in Comparative Example 10 was attached to one side of the polarizing film. The transmission axis of the polarizing film was arranged parallel to the slow axis of the cellulose acetate film (CAF-H1). A commercially available cellulose triacetate film (Fujitak TD80UF, Fuji Photo Negative Film) is subjected to saponification treatment, and is attached to the opposite side of the polarizing film using a polyethylene-based adhesive. Thus, a polarizing plate was produced.

-139- 581885-~-^ V. Description of the invention (138) [Example 39] A pair of polarized lights provided on a liquid crystal display device (6E-A3, made of sharp) using a TN-type liquid crystal cell The plate was peeled off, and the polarizing plate prepared in Example 36 was adhered to the liquid crystal cell side of the optical compensation sheet (KH-A1) through the adhesive through the adhesive, each on the observer side and the backlight side. A polarizing plate prepared in Example 36 was attached. For the produced liquid crystal display device, a measuring machine "Red-Contrastl60D, manufactured by ELDIM Corporation" was used, and the viewing angle was measured in 8 steps from the black display (L1) to the white display (L8). The results are shown in Table 丨 4. Example 40]. A pair of polarizing plates provided on a liquid crystal display device (6E-A3, sharp (manufactured by Sharp)) using a TN-type liquid crystal cell was peeled off, and the polarizing plate prepared in Example 36 was passed through an adhesive The polarizing plate produced in Example 36 was adhered to the liquid crystal cell side of the optical compensation sheet (KH-A1), and one polarizing plate produced in Example 36 was attached to the observer side and the background light side. The liquid crystal display device used a measuring machine (£ Red-Contrastl60D, manufactured by ELDIM), and measured the viewing angle in 8 steps from the black display (L1) to the white display (L8). The results are shown in Table 14. [Example 41] A pair of polarizing plates provided on a liquid crystal display device (manufactured by 6E-A3 'sharp) using a TN-type liquid crystal cell was peeled off, and the polarizing plates prepared in Examples 38 were passed through the adhesive through Examples 38 The polarizing plate produced is stuck to the liquid crystal cell side of the optical compensation sheet (KH-A 1) 'On the viewer's side and the background light -140- 581885 V. Description of the invention (139) Each of the polarizing plates produced in Example 38 is attached. For the produced liquid crystal display device, a measuring machine (Ez_ Contrastl60D, ELDIM) is used. (Manufactured by the company), the viewing angle was measured in 8 steps from black display (li) to white display (L8). The results are shown in Table 14. [Comparative Example 12] A liquid crystal display device (6E-A3) related to a TN-type liquid crystal cell (Sharp, stock), using a measuring machine (EZ-Contras t 160D, manufactured by ELDIM), measuring the viewing angle in 8 steps from black display (L1) to white display (L8). The results are shown in Table 1 4 Table 14 Viewing angle of liquid crystal display device (contrast range of 10 or more on the black side without range inversion) Example 39 70. 45. 160 ° Example 40 75. 45. 160 ° Example 41 30. 55. 120 ° Comparative Example 12 15. 25. 37 ° (Note) Inversion of tone on the black side: Inversion between L1 and L2 [Example 4 2] In a 20-inch liquid crystal display device using a TN liquid crystal cell A pair of polarizing plates provided on (LC-20V1, sharp) was peeled off, and Example 36 was used. The produced polarizing plate is attached to the -141-581885 of the optical compensation sheet (KH-A 1) through an adhesive. 5. Description of the invention (14) On the liquid crystal cell side, one sheet is attached to the observer side and the backlight side. The transmission axis of the polarizer on the observer side and the transmission axis of the polarizer on the background side are arranged. Under ambient conditions of temperature and relative humidity of 60%, continuously turn on the backlight for 5 hours and visually observe the full black display state in a dark room to evaluate light leakage. As a result, there is no light leakage in the display screen of the liquid crystal display device. [Example 43] A polarizing plate was mounted on a liquid crystal display device in the same manner as in Example 42 except that the polarizing plate prepared in Example 37 was used. The light leakage situation was evaluated in the same manner as in Example 42. As a result, there is no light leakage in the display screen of the liquid crystal display device. [Example 44] A polarizing plate was mounted on a liquid crystal display device in the same manner as in Example 42 except that the polarizing plate prepared in Example 38 was used. The light leakage situation was evaluated in the same manner as in Example 42. As a result, there is no light leakage in the display screen of the liquid crystal display device. [Comparative Example 13] A polarizing plate was mounted on a liquid crystal display device in the same manner as in Example 42 except that the polarizing plate produced in Comparative Example 11 was used. The light leakage situation was evaluated in the same manner as in Example 42. As a result, a frame-shaped light leakage situation occurs on the display screen of the liquid crystal display device. ——— -142- 581885 V. Description of the invention (141) [Example 45] (Production of optical compensation sheet) The following composition was put into a mixing tank, heated and stirred to dissolve each component to prepare a cellulose acetate solution. . The cellulose acetate solution composition has a acetic acid degree of 60.9% of cellulose acetate 100 parts by mass of triphenyl phosphate (plasticizer) 7.8 parts by mass of biphenyldiphenyl phosphate (plasticizer) 3.9 parts by mass of two Methyl chloride (the first solvent) 300 parts by mass of methanol (the second solvent) 54 parts by mass of 1-butanol (the third solvent) Π parts by mass Put 16 parts by mass of the hysteresis used in Example 1 into another mixing tank The rising agent, 80 parts by mass of dichloromethane, and 20 parts by mass of methanol were heated and stirred to prepare a delayed rising agent solution. To 474 parts by mass of the cellulose acetate solution, 25 parts by mass of the lagging agent solution was mixed, and the solution was sufficiently stirred. The amount of the retardation rising agent is 3.5 parts by mass for 100 parts by mass of cellulose acetate. The obtained solution was cast using a belt caster. The film with a residual solvent amount of 15% by mass was horizontally stretched at a stretching rate of 25% using a tenter at a temperature of 130 ° C, and the width after stretching was directly held at 50 ° C for 30 seconds and then clamped. To manufacture cellulose acetate film (optical compensation sheet). The film thickness of the obtained film was 7 0 // ιώ. Regarding the produced optical compensation sheet (TAC-1), the measurement of the hysteresis of the wavelength of 550nm was performed using a Yerbuso measurement-143-581885. 5. Description of the invention (142) (M-150, manufactured by JASCO Corporation) , Re hysteresis (Re550) is 40ηίπ, Rth hysteresis (Rth 5 5 0) is 1 3 0 η m 〇 (Alkaliization treatment) Make the optical compensation sheet (TAC-1) at a liquid temperature of 5 5 ° C to a specified concentration It was immersed in a 1.5N aqueous sodium hydroxide solution (pH 1 3) for 2 minutes, and subjected to an alkali treatment, washed with running water, and dried. Regarding the produced optical compensation sheet, the change in Re hysteresis (Re5 50) before and after alkalization treatment (Re550 after alkalization-Re550 before alkalization), and the concentration of the dissolution hysteresis riser (for the original content and Word dissolution ratio). The results are shown in Table 15. [Comparative Example 1 4] (Production of transparent carrier) The following components were charged into a mixing tank, and heated and stirred to prepare a cellulose acetate solution. Cellulose acetate solution composition 69.0% cellulose acetate 100 parts by mass triphenyl phosphate 7.8 parts by mass biphenyldiphenyl phosphate 3.9 parts by mass dichloromethane (first solvent) 3 00 parts by mass of methanol (second solvent) 54 parts by mass of 1-butanol (third solvent) 1 1 part by mass of the following ingredients are placed in another mixing tank, and the mixture is heated and stirred to adjust the hysteresis -144- 581885 V. Description of the invention (143) liter solution. Hysteresis rising agent solution composition 2-hydroxy-4-benzyloxybenzophenone 12 parts by mass 2,4-benzyloxybenzophenone_ 4 parts by mass dichloromethane 80 parts by mass methanol 20 parts by mass 4 7 4 mass parts of cellulose acetate solution was mixed with 2 mass parts of the hysteresis rising agent solution, and the solution was sufficiently stirred. The amount of the stagnation-rising agent was 1,000 parts by mass with respect to cellulose acetate. The solution was cast from a casting orifice in a bath cooled to 0 ° C. When the solvent content of the film is 70% by mass, the film is peeled from the groove, and the two ends in the width direction of the film are fixed with a pin tenter, and the width direction is maintained within the range of 3 to 5 mass% of the solvent content. The stretch (direction perpendicular to the machine direction) is stretched at 3% intervals and dried. Then, by transporting it between the rollers of the heat treatment device and drying it, and the glass transition temperature is in the range of more than 120 ° C, the elongation in the mechanical direction is substantially 0%, (the mechanical direction is 4% when considering stripping) In terms of stretching), the ratio of the stretching ratio in the width direction to the stretching ratio in the mechanical direction is adjusted to 0.75 to produce a cellulose acetate film having a thickness of 107 // πm. Regarding the produced optical compensation sheet (TAC-3), a Yerbeso tester (M-150, manufactured by JASCO Corporation) was used to measure the hysteresis chirp at a wavelength of 5 to 50 nm. The Re hysteresis chirp (Re 5 50) was llnm, Rth hysteresis (Rth550) is 80nm 〇-145- 581885 V. Description of the invention (1 44) (Alkaline treatment) The optical compensation sheet (TAC-3) was subjected to alkali treatment in the same manner as in Example 45. Regarding the produced optical compensation sheet, the change in Re hysteresis (R e 5 5 0) before and after alkalization was measured Δ re (R e 5 5 0 after alkalization-R e 5 5 0 before alkalization), and Dissolved hysteresis riser concentration (ratio of dissolution to original content). The results are shown in Table 15. Table 15 Thin film ΔRe (Re after alkalinization-Re before alkalization) Dissolution amount of retardation rising agent Example 45 TAC-1 -2nm 0.1% Comparative Example 14 TAC-3 -4nm 0.7% [Example 46] (Polarizer (Production) Adsorb iodine on the stretched polyvinyl alcohol film to make a polarizing film. The alkali-treated optical compensation sheet TAC-1 prepared in Example 45 was bonded to one side of a polarizing film using a polyvinyl alcohol-based adhesive. Attach the average direction of the retardation axis of TAC-1 parallel to the length direction of the polarizing film. The average direction of the retardation axis of the optical compensation sheet TAC-1 is 0 ° with the transmission axis of the polarizing film. Saponification of commercially available cellulose triacetate film (Fujitaco TD80UF, manufactured by Fuji Photo Co., Ltd.), use of polyvinyl alcohol-based adhesive, and attaching -146- 581885 5. Description of the invention (145) On the opposite side of the polarizing film. Thus, a polarizing plate was produced. [Comparative Example 15] The polarizing plates produced in Examples 46 and 15 were attached to a glass plate using an acrylic adhesive, and after being etched under high temperature and pressure, they were added to a horizontal temperature bath at 90 ° C. Leave for 1000 hours. Then, visually observe whether the cellulose acetate film (optical compensation sheet) and the polarizing film are peeled off, and the occurrence of air bubbles. The results are shown in Table 16. Table 1 6 Polarization plate with or without peeling and no bubbles Example 46 Μ j \ w & E / \ y \ Comparative Example 1 5 Yes Yes (Evaluation of the viewing angle by installing a vertically aligned liquid crystal cell) Use vertical alignment for peeling A pair of polarizing plates and a pair of optical compensation plates provided on a liquid crystal display device (VL-1530S, manufactured by Fujitsu Co., Ltd.) of a liquid crystal cell, and replaced with the polarizing plate produced in Example 46 and produced in Example 45 A cellulose acetate film is adhered to the liquid crystal cell side through an adhesive, and one sheet is attached to each of the observer side and the backlight side. The transmission axis crossing coils of the polarizing plate on the observer side are arranged in the vertical direction, and the transmission axis crossing coils of the polarizing plate on the background side are arranged in the left and right direction. Regarding the produced liquid crystal display device, the viewing angle characteristic was measured using a measuring machine (redundant-Contras t 160D, manufactured by ELDIM). Contrast ratio -147- 581885 V. Description of the invention (146) The viewing angle range of 10 is more than 60 ° in the above direction and more than 160 ° in the left-right direction. (Evaluation of the viewing angle by installing a TN-type liquid crystal cell) One of the pair of polarizing plates provided on a liquid crystal display device (6E-A3, made by Sharp) using a TN-type liquid crystal cell was peeled off, and the The adhesive made the polarizing plate prepared in Example 46 adhere to the liquid crystal cell side instead of the cellulose acetate film produced in Example 45, and one sheet was attached to each of the observer side and the background light side. The transmission axis cross coil of the polarizer on the observer side is doubled in the up-down direction, and the transmission axis cross coil of the polarizer on the background side is arranged in the left and right directions. Regarding the produced liquid crystal display device, the viewing angle characteristics were measured using a measuring machine "Red-Contras 160D, manufactured by ELDIM Corporation." The viewing angle range of the contrast ratio 10 was 45 ° or more in the above direction and 160 ° or more in the left and right directions. [Example 47] (Production of phase difference plate) At room temperature, 120 parts by mass of cellulose acetate having an average degree of acetic acidity of 59.2%, 9.36 parts by mass of triphenyl phosphate, and 4.68 parts by mass of biphenyl diphenyl Phenyl phosphate, 1.50 parts by mass of a hysteresis rising agent used in Example 1, 2.000 parts by mass of tribenzylamine, 5 34.14 parts by mass of dichloromethane, 99.35 parts by mass of methanol, and 19.87 parts by mass The parts by mass of n-butanol were mixed to prepare a solution (dope). The obtained solution was cast on a film-forming tube and dried at room temperature for 丨 minutes, and then dried at 45 ° C for 5 minutes. The residual solvent amount after drying was 30% by mass. The cellulose acetate film was peeled from the tube and dried at 120 ° C for 10 minutes.

-148- 581885 5. After the description of the invention (147), it is stretched in the direction parallel to the casting direction at 1 3 (TC. It can be stretched and contracted freely in the direction perpendicular to the stretching direction. After stretching at 20% stretching ratio After drying at 120t for 30 minutes, the stretched film was taken out. The residual amount of the solvent residue after stretching was 0.1% by mass. _ The thickness of the obtained cellulose acetate film (phase difference plate) was 54 // m, Jerebasso (transliteration) measuring device (M-150, using Japan spectrophotometer), hysteresis chirps (Re450, Re550, Re590) at the wavelengths of 450nm, 5 50nm and 590nm, respectively 118.3nm '137.2nm and 140.7nm. Therefore, the cellulose acetate film can reach λ / 4 in a wide range of wavelengths. In this way, a λ / 4 plate is obtained. In addition, the refractive index is set by an Abbe refractometer, and the angle dependence of the hysteresis effect is measured. The refractive index nx in the plane of the retardation axis in the plane of the wavelength of 550nm, the refractive index ny in the perpendicular direction of the retardation axis in the plane, and the refractive index nz in the thickness direction can be measured, and calculated (nx-nz) / (nx-ny) The time is 1.58. [Example 48] (Production of phase difference) The solution obtained in Example 47 was used Cast with a belt caster. A film having a residual solvent content of 15% by mass was laterally stretched at 150 ° C using a tenter at a 45% stretching ratio to produce a cellulose acetate film. The obtained cellulose acetate was produced. The thickness of the thin film (phase difference plate) is 40 // m, the Yeriboso (transliteration) measuring device (M-150, using the Japanese spectrophotometer), the retardation wavelengths of the wavelengths 450nm, 5 50nm, and 590nm (Re450, Re550, Re 5 90), each is 118.3nm, 137.2nm, and 140.7nm. Therefore, this

-149- V. Description of the Invention (148) The cellulose acetate film can reach λ / 4 in a wide range of wavelengths. In this way, a λ / 4 plate was produced. In addition, since the refractive index is set by an Abbe refractometer and the angle correlation with the measurement of the hysteresis is measured, the refractive index nx in the plane of the retardation axis in the plane of the wavelength of 550 nm and the refractive index in the plane of the retardation axis in the perpendicular direction can be obtained. The refractive index 112 in the ny and thickness directions is 1.70 when the time between (1 ^ -1 ^) / (-1 ^) is calculated. [Example 50] (Production of phase difference plate) At room temperature, 120 parts by mass of cellulose acetate having an average degree of acetic acidification of 59.0%, 2.0 parts of the retardation rising agent used in Example 1, and 9. 36 'parts by mass of triphenyl phosphate, 4.68 parts by mass of biphenyl diphenyl phosphate, 2.00 parts by mass of triphenylmethylamine, 534.14 parts by mass of dichloromethane, 99.35 parts by mass of methanol, and 19.87 parts by mass of n-butanol were mixed, and Prepare a solution (dope). The obtained solution was cast on a film forming tube and dried at room temperature for 1 minute, and then dried at 45 ° C for 5 minutes. The residual amount of the solvent after drying was 30% by mass. After the cellulose acetate film was peeled from the tube and dried at 120 ° C for 5 minutes, it was stretched by about 50% in a direction of 45 ° to the casting direction at 130t. After stretching, after drying at 130 ° C for 20 minutes, the stretched film was taken out. The residual amount of the solvent after stretching was 0.1% by mass. The thickness of the obtained cellulose acetate film (phase difference plate) was 63 // rii, a Yeriberso measuring device (M-150, manufactured by JASCO Corporation), and a wavelength of 450 nin, 5 50 nm, and 590 nm. When the hysteresis (Re45 0, Re550, Re590) is 115.7nm, 137.4nm and 141.4nn ^ Therefore, the -150-581885 V. Description of the invention (149) Cellulose acetate film can reach λ in a wide range of wavelengths / 4. In this way, a λ / 4 plate was produced. The Rth hysteresis (Rth5 50) is 137.5nm. In addition, since the refractive index is set by an Abbe refractometer and the angle correlation with the measurement of the hysteresis is measured, the refractive index nx in the plane of the retardation axis direction at the wavelength of 550 ηm and the refractive index in the plane of the retardation axis in the vertical direction can be obtained. The refractive index nz in ny and the thickness direction and the time when (nx-nz) / (nx-ny) is calculated are 1.50. [Example 50] (Production of a circular polarizing plate) A cellulose acetate film obtained in Example 47 and a commercially available polarizing plate (produced by Selitz) were made with a slow axis of the cellulose acetate film and The transmission axis of the polarizing plate is arranged at 45 degrees, and the circular polarizing plate is produced by bonding with an adhesive. When observing the optical characteristics of the obtained circularly polarizing plate, almost completely circularly polarized light can be achieved in a wide wavelength range (450 nm to 590 nm). [Example 51] (Production of polarizing film) PVA having an average polymerization degree of 4000 and a saponification degree of 99.8 mol% was dissolved in water to obtain a 4.0% aqueous solution. This solution was cast and dried by a belt, stripped off by itself, stretched in a drier in the direction of casting, and directly immersed in a 50 g / l potassium iodide aqueous solution (liquid temperature 30 ° C) for 1 minute. Then, it was immersed in an aqueous solution of 100 g / l boric acid and 60 g / l potassium iodide (liquid temperature 70 ° C) for 5 minutes, and then washed with water (water temperature 20 ° C) for 10 minutes. The water-washed film was dried at 80 ° C for another 5 minutes to obtain a long-length polarizing film. The width of the film is 1 290mm and the thickness is 20 / z m. -151-581885 V. Description of the invention (15〇) (Production of circular polarizing plate) The cellulose acetate film produced in Example 4 9 was laminated in roll t0 roll order, the polarizing film produced, and commercially available acetic acid. Cellulose film (Fujitaq, Fuji Photographic Film (stock)) to make a circular polarizer. When observing the optical characteristics of the obtained circularly polarizing plate, almost complete circularly polarized light can be achieved in a wide wavelength range (450 to 59 Onm). [Example 52] (Production of TN-type reflective liquid crystal display device) A glass substrate provided with a transparent electrode of IT0 and a glass substrate provided with an aluminum reflective electrode forming a fine concave-convex projection were used. Polyimide alignment films (SE-7992, manufactured by Nissan Chemical Co., Ltd.) were formed on the electrode sides of the two glass substrates, respectively, and they were laminated. Via the distance adjustment plate of 3.4 // m, the two substrates are overlapped toward the alignment film. The two laminated films are crossed at an angle of 110 ° to adjust the substrate direction. Liquid crystal (MLC-62 52, manufactured by Meruk) is injected into the gap between the substrates to form a liquid crystal layer. Thus, a TN-type liquid crystal cell having a twist angle of 70 ° and a Δnd of 269 nm was produced. The? / 4 plate produced in Example 47 was attached to a glass substrate provided with an IT0 transparent electrode via an adhesive. A polarizing plate (a polarizing film with an AR-protective film on the surface layer) is attached to it. A rectangular wave voltage of 1 kHz was applied to the produced reflective liquid crystal display device. When visually evaluating white display 1 · 5V and black display 4 · 5V, there is no color odor in white display and black display, and a new black and gray display can be confirmed. Then, using a measuring machine (EZ con t ras t 1 60D, manufactured by El Dim) -152- 581885 V. Description of the invention (151) When measuring the contrast ratio of reflection luminance, the contrast ratio from the front is 25, and the contrast ratio is 3 The viewing angle is 120 ° above and below, and 120 ° from left to right. In addition, the endurance test at a temperature of 60 ° C, a relative humidity of 90%, and 500 hours did not cause any problems on the display. [Example 53] (Production of STN-type reflective liquid crystal display device) A glass substrate provided with an ITO transparent electrode and a glass substrate provided with a flat aluminum reflective electrode were used. Polyimide alignment films (SE-150, manufactured by Nissan Chemical Co., Ltd.) were formed on the electrode sides of the two glass substrates, and laminated processing was performed. Via the distance adjusting plate of 6 · 0 // m, the two substrates are overlapped toward the alignment film. The lamination direction of the two alignment films is crossed at an angle of 60 ° to adjust the substrate direction. Liquid crystal (ZL1-2977, manufactured by Meruk) is injected into the gap between the substrates to form a liquid crystal layer. In this way, an STN type liquid crystal cell having a twist angle of 240 ° and a Δnd of 791 nm was fabricated. An internal diffusion sheet (IDS, manufactured by Dainippon Printing Co., Ltd.) and a circularly polarizing plate produced in Example 51 were sequentially attached to the glass substrate side provided with the I TO transparent electrode through an adhesive, and the polarizing plate was made. Is the outermost layer. A rectangular wave voltage of 55 Hz was applied to the produced reflective liquid crystal display device. Visual evaluation of the black display at 2.0 · 0V and the white display at 2.5 V showed no color and odor in the white display and black display, and a new black and gray display was confirmed. Then, when the contrast ratio of the reflection luminance was measured using a measuring machine (E Z contrast 16D, manufactured by Eldim), the contrast ratio from the front is 8, the viewing angle of the contrast ratio 3 is 90 ° or more, and 105 ° or so. 4

-153- 581885 V. Description of the invention (152) [Example 54] (Production of HAN reflective liquid crystal display device) A glass substrate provided with a transparent electrode of ITO and a glass substrate provided with a flat aluminum reflective electrode were used. A polyimide alignment film (SE-6 10, manufactured by Nissan Chemical Co., Ltd.) was formed on the electrode side of a glass substrate provided with a transparent TO electrode, and laminated processing was performed. A vertical alignment film (SE-1 2 1 1., manufactured by Nissan Chemical Co., Ltd.) was formed on the electrode side of a glass substrate provided with an aluminum reflective electrode. The phase matching film on the aluminum reflective electrode is not laminated. The two substrates were stacked toward the alignment film. Liquid crystal (ZLI-155, manufactured by Meruk) is injected into the gap between the substrates to form a liquid crystal layer. In this way, a HAN-type liquid crystal cell having a diameter of Δnd of 5 1 9 nm was produced. The λ / 4 plate produced in Example 47 was attached to a glass substrate provided with an IT0 transparent electrode via an adhesive. A polarizing plate (NPF-G 1 22 5DU, manufactured by Nitto Denko Corporation) was attached thereto, and a light diffusing film (Rumisto (transliteration), manufactured by Sumitomo Chemical Co., Ltd.) was attached thereto. A rectangular wave voltage of 55 Hz was applied to the produced reflective liquid crystal display device. When visually evaluating 0.8V for black display and 2.0V for white display, there is no color odor in white display and black display, and a new black and gray display can be confirmed. Then, when the contrast ratio of the reflection luminance was measured using a measuring machine (E Z contras 1160D, manufactured by Eldim), the contrast ratio from the front was 8, the viewing angle of the contrast ratio 3 was 120 ° or more, and 120 ° from the left and right. [Example 55] (Production of G / Η type liquid crystal display element) -154- 581885 V. Description of the invention (153) A glass substrate provided with a transparent electrode of I TO was coated with a vertical alignment film to form a polymer (LQ-1 800 , Hitachi Chemical Co., Ltd. (made by DuPont Microsystems) and dried, and then laminated. On the glass substrate on which aluminum was vapor-deposited as a reflecting plate, a λ / 4 plate prepared in Example 48 was attached with an adhesive, and an SI0 layer was provided by a sputtering method. An ITO transparent electrode is provided thereon. The transparent electrode was coated with a solution of a vertical alignment film-forming polymer (LQ-1 800, manufactured by Hitachi Chemical Co., Ltd., DuPont Microsystems), dried, and then laminated from the 45 ° direction of the retardation axis direction of the λ / 4 plate. . The two glass substrates are overlapped toward the alignment film via a distance adjusting plate of 7.6 // m. The substrate direction is adjusted in anti-parallel to the laminated layer direction of the alignment film. A mixture of 2.0% by mass liquid crystal dichroic dye (NKX-1 366, manufactured by Nippon Photographic Pigment Co., Ltd.) and 98 · 0% by mass liquid crystal (ZLI-2806, manufactured by Meruk Corporation) was injected into the gap between the substrates. 1. A liquid crystal layer is formed by vacuum injection, and a rectangular wave voltage of 1 kHz is applied between the ITO electrodes of the host-guest reflective liquid crystal display element. The transmittances of white display iv and black display 10V are 6 5% and 6%, respectively. The transmittance ratio (control ratio) of the white display and the black display is 1 1: 1. When the viewing angle of the contrast ratio of 2: 1 is obtained by measuring the vertical direction, the vertical and horizontal directions are 120 ° or more. The transmittance was measured by increasing and decreasing the voltage, and the transmittance-voltage curve was completely free from irregularities. [Comparative Example 16] (Production of λ / 4 plate)

-155- V. Description of the Invention (154) A polycarbonate having a mass average molecular weight of 100,000 was dissolved in dichloromethane to obtain a polycarbonate solution having a concentration of 17% by mass. This solution was cast on a glass substrate at a dry film thickness of 80 / zm, dried at room temperature for 30 minutes, and then dried at 70 ° C for minutes. The polycarbonate film (volatile component: about 1% by mass) was peeled from the glass plate and cut into a size of 5 cm × 10 cm. Stretched biaxially at 1 58 ° C to obtain a stretched birefringent film of polycarbonate. The obtained polycarbonate film (λ / 4 plate) was measured using a Yerbeso tester (M-150, manufactured by JASCO Corporation), and measured hysteresis 波长 at wavelengths of 450 nm, 5 50 nm, and 5 9011111 (1 ^ 450, 1 ^ 550, 1 ^ 590), respectively 147.8 ·, 13 7.5nm, and 134.9nmo (production of λ / 2 plate) Except the use of polycarbonate solution used for making λ / 4 plate, dry film thickness A cast of 100 / im was performed, and a λ / 2 plate was produced in the same manner as λ / 4. The obtained polycarbonate film (λ / 2 plate) was measured using a Yelibuso tester (M-150, manufactured by JASCO Corporation), and measured hysteresis (Re450, Re 5) at 450 nm, 5 50 nm, and 590 nm. 50, Re590), respectively 29.5.0nm, 275.0nm, and 269.8nmo (production of TN reflective liquid crystal display device) On the glass substrate side of the ITO transparent electrode provided with the TN liquid crystal cell prepared in Example 52 Laminated λ / 4 plate, λ / 2 plate, and polarizing plate (a polarizing film laminated with a protective film with AR treatment on the surface) in order through the adhesive. For example, the transmission axis of the polarizing film and the retardation axis of the L / 2 plate are 20 °, and the retardation axis of the λ / 2 plate and the retardation angle of the λ / 4 plate are 55 °. -156- 581885 V. Description of the Invention (155) A rectangular wave voltage of 丨 kHz is applied to the produced reflective liquid crystal display device. When visually evaluating 1.5 V for white display and 4.5 V for black display, it can be seen that the white display is slightly yellow and the black display is slightly blue. Then, when measuring the contrast ratio of the reflection luminance using a measuring machine (EZ cont ras t 160D, manufactured by Eldim), the contrast ratio from the front is 10, the viewing angle of the contrast ratio 3 is 100 ° or more above and below, and about 80 is around. . . Furthermore, the temperature 6 was performed (at the endurance test of TC, relative humidity of 90%, and 500 hours, light leakage occurred around the display (frame-like display streaks)) [Example 5 6] (Production of cellulose acetate film SE5) In a greenhouse, 45 parts by mass of an average degree of vinegarization of 60.9% cellulose acetate, 3.12 parts by mass of the following hysteresis rising agent (4), 232.7 parts by mass of methylene chloride, 42.57 parts by mass of methanol, and 8.50 parts by mass of n-butanol Mix and prepare a solution (dope).

The obtained solution was subjected to a belt casting machine having an effective length of 6 m, and the film was cast and dried to a thickness of 60 / z η and dried. Regarding the obtained cellulose acetate film SE5, a Yelibuso tester (M -1 50, manufactured by JASCO Corporation) and a hysteresis chirp at a wavelength of 5 50 nm, Re-157-581885 V. Description of the invention (156) The hysteresis (1 ^ 5 50) is 511111, and the 1? "Hysteresis (1 ^} 15 50) is 12〇11111. A gelatin base coat with a thickness of 0.1 // m is set in the cellulose acetate film SE5. On the gelatin base On the coating layer, an alignment coating liquid used in Example 2 of 28 ml / m2 was coated with a wire rod applicator of # 16. Drying was performed at 60 ° C for 60 seconds and 90 ° C. 150 seconds. Then, the film was formed in a direction of 45 ° with the retardation axis (measured at a wavelength of 6 3 2.8 nm) of the cellulose acetate film SE5, and the laminated film was subjected to a lamination treatment. 102 g of the alignment film was dissolved with 4 1 · 0 1 g of the liquid crystal (disc-shaped) liquid crystal compound used in Example 2 and 4.06 g of ethylene oxide-modified trimethylolpropane tripropionate (V # 360, Osaka Organic (Made by Chemical Co., Ltd.), 0.90 g of cellulose acetate butyrate (CAB 5 5 1-0 · 2, manufactured by Eston Chemical Co., Ltd.), 0.23 g of cellulose acetate butyrate (CAB53 1-1, manufactured by Eston Chemical Co., Ltd.), 1. 35 g of photopolymerization initiator (Eruca Kaya (Translated) 907, manufactured by Chiba Machinery Co., Ltd.), 0.45 g sensitizer (California Yeqiya (transliteration) DETX (Nippon Kayaku Co., Ltd.) methyl ethyl ketone coating solution, coated with # 3 iron wire rod. Attach it to a metal frame at 130 ° C Using a 120 W / cm high-pressure mercury lamp, UV irradiation was performed for 4 seconds to polymerize the disc-shaped compound. Then, it was cooled to room temperature. Thus, the optically anisotropic layer 1 E was formed. Re of the optically anisotropic layer 1E measured at a wavelength of 550 nm The hysteresis (Re 5 50) is 40 nm. In addition, the average angle (tilt angle) between the disc surface and the SE1 surface is 42 ° on average. (Production of elliptical polarizing plate E) Manufactured by alkali treatment in an alkaline bath Cellulose acetate film SE5, -158- V. Explanation of the invention (157) The cellulose acetate film surface of the optically anisotropic layer 1E and the SE5 surface of the polarizing plate are bonded with an adhesive to produce an elliptical polarizing plate. Polarizing film The transmission axis is orthogonal to the slow axis of the cellulose acetate film of the optically anisotropic layer 1 B (also with S The delay axis of E5 is orthogonal to each other.] [Example 57] (Production of cellulose acetate film SE6) At room temperature, the average acetate degree of 4 5 parts by mass was 60.9% of cellulose acetate and 3.62 parts by mass. The hysteresis rising agent (1), 232.72 parts by mass of dichloromethane, 42.57 parts by mass of methanol, and 8.50 parts by mass of n-butanol were mixed to prepare a solution (dope). (1) ·

The resulting solution was stretched to form a film using a belt caster and tenter having an effective length of 6 m, and cast and dried with a dry film thickness of 40 # m. Regarding the obtained cellulose acetate film (SE6), an in-plane hysteresis (Re550) was used at a Yelibuso tester (M-150, manufactured by JASCO Corporation) at a wavelength of 50 nm. The time is 18 nm, and the Rth hysteresis (Rth550) is 100 nm. The surface of SE6 is saponified with 2N sodium hydroxide aqueous solution and washed with water. The contact angle of pure water on the surface of saponified SE6 was 30 degrees. On this surface, an alignment coating liquid used in Example 2 of 28 ml / m2 was applied with a wire rod applicator of # 16. Dry at 60 ° C for 60 seconds, and at 90 ° C -159- V. Description of the Invention (1 58) Dry at 150 ° C for 50 seconds. Then, the late phase axis (measured at a wavelength of 632.8 nm) with the SE6 becomes 45. The film formed in the direction 'is laminated. On the formed alignment film, 1.02 g of 4 1. 0 1 g of the optical disc (disk-shaped) liquid crystal compound used in Example 2 and 4.06 g of ethylene oxide-modified trimethylolpropane triacrylic acid were dissolved. Ester (V # 360, manufactured by Osaka Organic Chemicals Co., Ltd.), 0.90 g of cellulose acetate butyrate (CAB5 51-0.2, manufactured by Eston Chemical Co., Ltd.), 0. 23 g of cellulose acetate butyrate ( CAB53 1-1. Yiston Chemical (manufactured by Transsound) Chemical Co., Ltd., 1.35g of photopolymerization initiator (Irukhaki (Transliteration) 907, manufactured by Chiba Machinery Co., Ltd.), 0.45g sensitizer (Carya The coating solution of methyl ethyl ketone of Asia (trans) DETX and Nippon Kayaku Co., Ltd. is coated with a wire rod of # 3. It was affixed to a metal frame and heated in a horizontal temperature bath at 130 ° C for 2 minutes to align the disc-shaped compound. The disc-shaped compound was polymerized by using a 120 W / cm high-pressure mercury lamp and UV irradiation at 130 ° C for 4 seconds. Then, it was cooled to room temperature. In this way, the optically anisotropic layer 1 F is formed. The Re hysteresis (Re 5 50) of the optically anisotropic layer 1F measured at a wavelength of 550 nm was 40 nm. The average angle (inclination angle) between the disc surface and the transparent carrier surface is 42 ° on average. (Production of elliptical polarizing plate F) SE6 produced by alkali treatment in an alkaline bath, and PVA and a polarized photon made of iodine were bonded to SE6 via an adhesive. In addition, the cellulose acetate film surface of the optically anisotropic layer 1 F and the SE6 of the polarizing plate were bonded via an adhesive to prepare an elliptical polarizing plate. The transmission axis of the polarizing film and the optically anisotropic layer 1F -1 6 0-581885 V. The retardation axis of the cellulose acetate film of the invention description (159) is parallel (also parallel to the SE6 retardation axis) [Comparative Example 1 7 ] (Production of Cellulose Acetate Film SE7) A gelatin primer with a thickness of 0.1 / m is set on a 100 # m triacetyl cellulose film (Fujitak, Fuji Photographic Film (stock)). Layer to make a cellulose acetate film SE7. The Re hysteresis (Re 5 50) measured at a wavelength of 550 nm was 0.6 nm, and the Rth hysteresis (Rth550) was 35 nm. On a gelatin base coat layer of Se7, an alignment coating liquid used in Example 2 of 28 m 1 / m 2 was applied with a wire rod applicator of # 16. Dry at 60 ° C for 60 seconds and at 90 ° C for 150 seconds. Then, the film was formed in a direction of 45 ° with the late phase axis (measured at a wavelength of 6 32. 8 nm) of the cellulose acetate film, and the formed film was laminated. On this alignment film, 102 g of the optical disc (disk-shaped) liquid crystal compound used in Example 4.0 was dissolved, and 4.06 g of ethylene oxide-modified trimethylolpropane triacrylate (V # 360, (Made by Osaka Organic Chemical Co., Ltd.), 0.90 g of cellulose acetate butyrate (CAB5 5 1-0.2, manufactured by Eston Chemical Co., Ltd.), 0.23 g of cellulose acetate butyrate (CAB531-1, clothing history) Tonma (produced by Chemical Co., Ltd.), 1.35g of photopolymerization initiator (Irukhaki (Transliteration) 907, Chiba Machinery Co., Ltd.), 0.45g of sensitizer (Carafia (Transliteration) DETX, A coating solution of methyl ethyl ketone of Nippon Kayaku Co., Ltd. was coated with a wire rod of # 3. Attach it to a metal frame and heat it in a horizontal temperature bath at 13 ° C for 2

-161-581885 5. Description of the invention (160) minutes to align the disc-shaped compound. The disc-shaped compound was polymerized by using a 120 W / cm high-pressure mercury lamp and UV irradiation at 130 ° C. for 1 minute. Then, cool to room temperature. Thus, the optically anisotropic layer 1 G was formed. The Re hysteresis (Re5 50) of the optically anisotropic layer 1G measured at a wavelength of 5 50 nm was 40 nm. Moreover, the angle (tilt angle) between the disc surface and the SE7 is 42 ° on average. An 2,2'-bis (4-hydroxyphenyl) propane polycarbonate resin (viscosity average molecular weight: 28000) was dissolved in dichloromethane to prepare an 18% by mass solution. The solution was degassed in vacuo to make a solution. The solution was cast on a tube, dried at 50 ° C for 10 minutes, and then stripped, and dried at 100 ° C for 10 minutes. The obtained film was stretched 3.3% in longitudinal direction and 4.7% in transverse direction at 170 ° C to obtain a biaxially stretched roll film having a thickness of 80 // m. The longitudinal stretching is controlled by the speed difference between the two check rolls, and the transverse stretching is controlled by the width of the tenter. The Re hysteresis (Re 5 50) measured at a wavelength of 5 50 nm of the obtained polycarbonate film was 4 nm, and the Rth hysteresis (Rth 5 5 0) was 205 nm. (Formation of the elliptical polarizing plate G) PVA, a polarizer made of iodine, and a polycarbonate film were bonded via an adhesive. In addition, a polycarbonate surface was bonded to the SE7 surface of the optically anisotropic layer 1 G through an adhesive to prepare an elliptically polarizing plate. The transmission axis of the polarizing film is orthogonal to the retardation axis of the cellulose acetate film of the optically anisotropic layer 1G (also orthogonal to the retardation axis of the polycarbonate film).

• 162 · 581885 V. Description of the invention (16〇 Table 17 one by one ___ Elliptical polarizer optical anisotropic layer 1 Optical anisotropic layer 2 Re550 β Re550 Rth550 Example 56 40 42 12.0 250 Example 57 40 42 40.0 210 Comparative Example 17 40 42 3.6 235 (Note): Re 5 50: Re hysteresis chirp (nm) measured at a wavelength of 550 nm Rth 5 50: Rth hysteresis chirp (nm) measured at a wavelength of 550 nm Cold: average inclination of the disc surface (°) [Example 58] (Production of curved alignment liquid crystal cell) A polyimide film was set as an alignment film on a glass substrate with an ITO electrode, and a lamination process was performed on the alignment film. Two sheets were obtained. The glass substrate is arranged and combined in parallel with the lamination direction, and a 6 # π unit cell gap is set. A liquid crystal compound having a Δ η of 0.1 3 9 6 is injected into the gap (ZL I 1 1 2 2. Meruk Corporation) Manufacture) to produce a curved alignment liquid crystal cell. In a curved alignment liquid crystal cell, a 55 Hz rectangular wave, a voltage of 5 or 5.5 V, and a wavelength of 436 nm, 546 nm, and 61 1.5 nm were used to measure the Re hysteresis (the liquid crystal display device). (Made by) can be made by clamping the bend Under the unit cell, paste the elliptically polarizing plate E made in Example 56-163- 581885 in Example 56 (162). Make the optical anisotropy layer of the elliptically polarizing plate face the unit cell substrate, and make the liquid crystal unit The lamination direction is arranged antiparallel to the oblique direction of the optically anisotropic layer opposite to the lamination direction. [Example 59] (Manufacturing of a liquid crystal display device)

The elliptically polarizing plate F produced in Example 57 was stuck under the bendable alignment cell produced in Example 58. The optically anisotropic layer of the elliptically polarizing plate is faced to the cell substrate, and the lamination direction of the liquid crystal cell is arranged in anti-parallel to the lamination direction of the optical anisotropic layer on the opposite side. [Comparative Example 18] (Manufacturing of a liquid crystal display device) The elliptic polarizing plate G prepared in Comparative Example 17 was pasted under a bendable alignment unit cell prepared in Example 58 and sandwiched therebetween. The optically anisotropic layer of the elliptically polarizing plate is faced to the cell substrate, and the lamination direction of the liquid crystal cell is arranged in anti-parallel to the lamination direction of the optical anisotropic layer on the opposite side. (Evaluation of liquid crystal display device)

A rectangular wave voltage of 5 to 5 Hz was applied to the liquid crystal cell of the liquid crystal display device manufactured in Example 58, Example 59, and Comparative Example 18. Original white type with 2 V in white and 5 V in black. The transmittance ratio was used as a control ratio, and a viewing angle of 10 with a contrast ratio of up, down, left, and right was obtained. In addition, the backlight was lit for 2 hours, and speckles displayed in black were evaluated visually. The above results are shown in Table 18. -164- 581885 V. Description of the invention (163) Table 18 Liquid crystal display viewing angle, left and right black display speckles Example 58, ...) 73 59 57 The best embodiment '' '1 80 75 78 78 best II, Φ; N 18 80 58 56 55 Observe the increase in transmittance at the 4 ends. Uli): Comparison table of main components with a viewing angle of 80 ° or more (1) Lower substrate (2) Reflective electrode (3) Lower alignment film (4) Liquid crystal layer (5 ) Upper alignment film (6) Transparent electrode (7) Upper substrate (8) λ / 4 plate (9) Polarizing film (11) Lower substrate (12) Organic layer insulation film (13) Metal reflection plate (14) λ / 4 Plate (15) Under transparent electrode (16) Under alignment film_ 1 65-581885 V. Description of the invention (164) (17) (18) (19) (20) (21) (22) (23) (24) ( 31) (32) (33) (34) (35) (36) (37) (38) (39) (41) (42) (110) (111) (Ilia ~ lllj) (112a, 112b) Liquid crystal layer Alignment film on the transparent electrode on the upper alignment film. Anti-reflective layer on the substrate. TFT Adjuster. Lower substrate. Organic layer. Insulation film. Cholesterol type λ / 4. Under transparent electrode. Unit cell liquid crystalline compound Rod-shaped liquid crystal molecular alignment film ~ 166- 581885 V. Description of the invention (165) (113a, 113b) Electrode layer (114a) Upper substrate (114b) Lower substrate (131, 131A, 131B) Optical anisotropic layer 1 (131a ~ 131 e) Disc compound (132) Alignment film (1 33, 1 33A, 133B, 133a, 133b) Optical anisotropic layer 2 (134, 1 34A, 134B) Polarizing film RD5RD1, RD2, RD3, RD4 Direction TA Transmission axis SA, SA1, SA2 Late phase axis NL Normal PL Direction of normal projection Θ Angle -167-

Claims (1)

581885 Patent case No. 90 1 1 1 6 3 5 "Optical compensation sheet, polarizing plate and liquid crystal display device" (Amended on July 14, 1992) 6. Scope of patent application: An optical compensation sheet comprising a cellulose acetate film comprising cellulose acetate having a degree of acetic acid of 59.0 to 61.5% and 0.01 to 20 parts by mass (relative to 100 parts by mass of cellulose acetate). An aromatic compound having at least two aromatic rings, wherein the Re hysteresis (Re 5 50) of the cellulose acetate film measured at a wavelength of 5 50 nm is 0 to 200 nm, and the cellulose acetate film measured at a wavelength of 5 50 nm The Rth hysteresis (Rth550) is 70 to 400 nm, and the thickness of the cellulose acetate film is in the range of 10 to 70 μm. 2. If the optical compensation sheet according to item 1 of the patent application range, where Re 5 50 is 20 to 70 nm 〇 3 If the optical compensation sheet according to item 1 of the patent application range, it can meet the wavelength The Re hysteresis (Re450) of the cellulose acetate film measured at 450 nm is 100 to 125 μm, the Re hysteresis (Re590) of the cellulose acetate film measured at a wavelength of 590 nm is 120 to 160 nm, and Re590-Re450 2 2 nm Relationship. 4 · The optical compensation sheet according to item 丨 of the patent application scope, wherein the change of Re550 before and after the alkali cellulose film undergoes alkalizing treatment, the change of Re550 is less than 3nm. 5. The optical compensation sheet according to item 1 of the scope of patent application, wherein the surface energy of at least one side of the plain film on the acetate fiber 581885 is 55 to 75 mN / m. 6. The optical compensation sheet according to item 1 of the patent application, wherein at least one side of the cellulose acetate film is treated with a corona discharge having a discharge frequency of 50 Hz to 5000 kHz. 7. The optical compensation sheet according to item 1 of the patent application scope, wherein at least one side of the cellulose acetate film is subjected to alkali saponification treatment with an alkali solution of a specified concentration of 0.1 to 3.0N. 8. The optical compensation sheet according to item 1 of the patent application scope, wherein the cellulose acetate film is stretched. 9 · The optical compensation sheet according to item 8 of the patent application scope, wherein the stretching magnification is 3 to 100%. 10 · The optical compensation sheet according to item 8 of the patent application scope, wherein the stretching treatment is biaxial stretching. 11. The optical compensation sheet according to item 1 of the patent application, wherein Re 5 50 is 0 to 20 nm 〇1 2 · The optical compensation sheet according to item 11 of the patent application, wherein a liquid crystal film is provided on the fiber acetate film An optically anisotropic layer formed by a reactive compound. 1 3. The optical compensation sheet according to item 1 of the patent application range, wherein the liquid crystal compound is a disc-shaped compound. 14. The optical compensation sheet according to item 1 of the scope of patent application, wherein the aromatic compound has at least one 1,3,5-three plough ring. 15. —A polarizing plate comprising a polarizing film and a transparent 581885, patent-pending protective film disposed on both sides thereof, one of which is a transparent protective film containing acetate fiber having a degree of acetic acid of 59.0 to 61.5% And 0.01 to 20 parts by mass (relative to 100 parts by mass of cellulose acetate) of an aromatic compound having at least two aromatic rings, in which 1 ^ hysteresis of a cellulose acetate film measured at a wavelength of 550 nm (86 5 50) is 0 to 20011111, the Rth hysteresis (Rth550) of the cellulose acetate film measured at a wavelength of 55011111 is 70 to 400 nm, the thickness of the cellulose acetate film is in the range of 10 to 70 μηι, and the cellulose acetate film Stretched. 16. A liquid crystal display device, which is composed of a liquid crystal cell and two polarizing plates arranged on both sides thereof, and the polarizing plate is a polarizing film and two transparent plates arranged on both sides Made of a protective film, at least one of the two transparent protective films arranged between the liquid crystal cell and the polarizing film contains cellulose acetate having a degree of acetic acid of 59.0 to 61.5% and 0.01 to 20 parts by mass (relative to 100 parts) A mass fraction of cellulose acetate) An aromatic compound having at least two aromatic rings, wherein the Re hysteresis (Re 5 50) of the cellulose acetate film measured at a wavelength of 550 nm is 0 to 200 nm, and The measured Rth hysteresis (Rth550) of the cellulose acetate film was 70 to 40 nm, the thickness of the cellulose acetate film was in the range of 10 to 70 μm, and the cellulose acetate film was stretched. 17. The liquid crystal display device according to item 16 of the patent application scope, wherein the liquid crystal cell system is a TN type, a VA type, an MVA type, an n-ASM type, or an OCB type liquid crystal cell. 18. A circular polarizing plate, which is a laminated layer of an optical compensation sheet and a linear polarizing film. The scope of the patent application is that the retardation axis of the optical compensation sheet and the transmission axis of the linear polarizing film are 45 ° laminated. A circularly polarizing plate in which the optical compensation sheet is cellulose acetate having a degree of acetic acid of 59.0 to 61.5% and 0.01 to 20 parts by mass (relative to 100 parts by mass of cellulose acetate) having at least two aromatic rings Aromatic compounds in which the Re hysteresis (Re 5 50) of cellulose acetate films measured at a wavelength of 550 nm is 0 to 200 nm, and the Rth hysteresis (Rth550) of cellulose acetate films measured at a wavelength of 550 nm is 70 to 400 nm The Re hysteresis (Re450) of the cellulose acetate film measured at a wavelength of 450 nm is 100 to 125 nm, and the Re hysteresis (Re 590) of the cellulose acetate film measured at a wavelength of 590 nm is 120 to 160 nm, and satisfies Re59. The relationship between 0-Re45 0 $ 2nm, the thickness of the cellulose acetate film is in the range of 10 to 70 μm, and the cellulose acetate film is stretched. 19. A reflective liquid crystal display device, which is a crystal liquid crystal display device in which a reflective liquid is sequentially laminated with a reflective plate, a liquid crystal cell, and a polarizing plate, wherein a cellulose acetate film is disposed between the reflective plate and the polarizing film, including acetic acid Cellulose acetate having a degree of 59.0 to 61.5% and 0.01 to 20 parts by mass (relative to 100 parts by mass of cellulose acetate) of an aromatic compound having at least two aromatic rings, of which cellulose acetate is measured at a wavelength of 550 nm The Re hysteresis (Re 5 50) of a plain film is 0 to 200 nm, and the Rth hysteresis (Rth550) of a cellulose acetate film measured at a wavelength of 5 50 nm is 70 to 400 nm. The Re hysteresis chirp (Re450) is 100 to 125nm, and the wavelength 590nm is 581885. 6. The Re hysteresis chirp (Re 5 9 0) of the cellulose acetate film measured from the patent application range is 120 to 160nm, and meets Re5 90- Re45 0 S 2nra has a relationship 'the thickness of the cellulose acetate film is in the range of 10 to 70 μm' and the cellulose acetate film is stretched. 20. A liquid crystal display device, which is a liquid crystal display device formed by a bend-aligned liquid crystal cell and a pair of polarizing plates disposed on both sides of the liquid crystal cell. At least one of the polarizing plates is a mixture of disc-shaped compounds. Aligned optically anisotropic layer 1, an optically anisotropic layer formed with at least one cellulose acetate film 2, and a laminated body formed with a polarizing film, and the polarizing film is arranged in an outermost elliptical polarizing plate , Characterized in that the maximum refractive index direction in the plane of the optical anisotropic layer and the in-plane transmission axis of the polarizing film are 45 °, and the maximum refractive index direction in the plane of the optical anisotropic layer and the in-plane transmission of the polarizing film The optical anisotropic layer 1, the optical anisotropic layer 2 and the polarizing film are arranged in parallel or perpendicular to the axis. The cellulose film of the optical anisotropic layer 2 is cellulose acetate containing 59.0 to 61.5% acetic acid and 0.01 to 20 parts by mass (relative to 100 parts by mass of cellulose acetate) of an aromatic compound having at least two aromatic rings, wherein the Re hysteresis (Re550) of the cellulose acetate film measured at a wavelength of 550 nm is 1 to 20nm to Long 550nm Rth measured retardation of a cellulose acetate film Zhi (Rth550) of 150 to 300 nm, the thickness of the cellulose acetate film is in the range of 10 to 70μιη, and a cellulose acetate film by a stretching treatment. 21. A liquid crystal display device, which is a liquid crystal display device formed by a pair of polarizing plates arranged on both sides of a liquid crystal cell on a bend-aligned liquid crystal cell and 581885 6. At least one of the polarizing plates is made of The disc-like compound is an optically anisotropic layer with a mixed alignment 1, an optically anisotropic layer with at least one cellulose acetate film 2, a laminated body with a polarizing film, and the polarizing film is disposed on The outermost elliptically polarizing plate is characterized by the maximum refractive index direction in the plane of the optically anisotropic layer 1 and the transmission axis in the plane of the polarizing film at 45 °, and the maximum refractive index direction in the plane of the optical anisotropic layer 2 The optically anisotropic layer 1, the optically anisotropic layer 2 and the polarizing film are arranged substantially parallel or perpendicular to the in-plane transmission axis of the polarizing film. The cellulose film of the optically anisotropic layer 2 contains a degree of acetic acid of 59.0 to 61.5% cellulose acetate and 0.01 to 20 parts by mass (relative to 100 parts by mass of cellulose acetate) of an aromatic compound having at least two aromatic rings, wherein the cellulose acetate film is measured at a wavelength of 550 nm The 1 ^ retardation chirp (1 ^ 5 50) is 20 to 10011111, and the Rth retardation chirp (Rth550) of the cellulose acetate film measured at a wavelength of 5501111 is 150 to 300nm. The thickness of the cellulose acetate film is between In the range of 10 to 70 μm, the cellulose acetate film is stretched.