TW200302361A - Polarizing plate comprising linearly polarizing film and phase retarder - Google Patents

Abstract

A polarizing plate comprises a linearly polarizing film and a phase retarder. The linearly polarizing film has a longitudinal direction and an absorption axis. The phase retarder has a longitudinal direction and a slow axis. The longitudinal direction of the linearly polarizing film is essentially parallel to the longitudinal direction of the phase retarder. One of the absorption axis and the slow axis is essentially parallel to the longitudinal direction. The other is essentially neither parallel nor perpendicular to the longitudinal direction.

Description

200302361 发明 Description of the invention (The description of the invention should state: the technical field to which the invention belongs, the prior art, the content, the embodiments and the drawings) (1) The technical field to which the invention belongs The invention relates to a linear polarizing film "(Ρ 〇1 arizingfi 1 m) and" phase retarder "polarizing plate, wherein the polarizing film and the retarder are arranged in the longitudinal direction and are substantially parallel to each other. The present invention also relates to a roll-shaped polarizing plate Wherein, the linear polarizing film and the λ / 4 plate are arranged so that the absorption axis of the film is located at an angle of 45 ° to the late phase axis of the λ / 4 plate. In addition, the present invention relates to an optical compensation film, a roll-shaped polarizing plate, and Liquid crystal cell π (1 iquidcrysta 1 ce 11), in which nematic liquid crystals capable of bending alignment or mixed alignment are sealed. The orientation vector of the liquid crystal changes its direction with the voltage applied to the liquid crystal cell. If the voltage changes, the orientation vector The angle between the substrate and the substrate will also change. (2) Compared with the prior art and the cathode ray tube (CRT), the advantage of the "liquid crystal display" (hereinafter referred to as LCD) is thinner Light weight and low power consumption. As a result, LCDs have been widely used in, for example, notebook personal computers, monitors, televisions, personal digital assistants (PDAs), mobile phones, car navigation systems, or cameras. The most common LCDs are "reverse nematics" (TN) type unit cell, which uses twisted nematic liquid crystal. However, TN type display will change color or contrast depending on the viewing direction. In addition, its response time is difficult to be completely satisfactory. US Patent 4, 5 8 3 Nos. 8 2 5 and 5, 4 1 0, 4 2 2 published LCDs with liquid crystal chips in curved alignment mode, with rod-shaped liquid crystal molecules on the upper side and a substantially reverse (symmetrical) arrangement on the lower side. Because The upper rod-shaped liquid crystal molecules are symmetrically arranged with the lower 200302361. This type of bending alignment mode of the liquid crystal sheet itself performs optical compensation. Therefore, this mode is called 0 c B (optically compensated bending) mode. The LCD in OCB mode must be installed The optical compensation film can avoid the development delay seen from the front and enlarge the viewing angle. The optical compensation film contains a transparent carrier and an optical anisotropic layer, please refer to Japanese Patent Application Publication Publication No. 6 (1996) -214116, US Patent Nos. 5,583,679 and 5,646,703, and West German Patent No. 3 1 1 6 2 0 A 1. In order to further improve the viewing angle of LCDs in OCB mode, some people have investigated the use of ordinary LCD Optical compensation films used in such applications as U.S. Patent Nos. 5,805,253, 6,064,457 and World Patent No. 96/37804 (equivalent to European Patent Application 0 7 8 3 1 28 A) Layer of optical compensation film. In these documents, the OC mode liquid crystal display of such a film is also published. Because of the compensation film with a different direction of the disc-shaped liquid crystal layer, the published LC has a wider viewing angle. In addition, at the 42nd Japanese Open Physics Association (Spring) Conference (29a-SZC-20, 1 9 9 5), a liquid crystal cell with a HAN (Hybrid Alignment-Nematic) mode was published, so the aforementioned ideas have been applied to reflective displays . In the liquid crystal cell of the HAN mode, the rod-shaped liquid crystal molecules above the liquid crystal cell in the bending alignment mode are aligned in the mixed alignment direction. Biaxially stretched films are suggested as optical compensation films for HAN mode liquid crystal cells. In order to further improve the viewing angle of the HAN mode LCD, Japanese Patent Application Laid-Open No. 9 (1 99 7) -2 1 9 1 4 and Japanese Patent Mu 97 have published optical compensation films having a disc-shaped liquid crystal optically anisotropic layer. In this patent, a HAN mode LCD with a compensation film is also issued. 200302361 Compared with the traditional LCD cell (TN mode, STN mode), the LCD panel of 〇CB mode or Η AN mode has a wider viewing angle and faster response, so it has been used in transmissive displays. In addition, it is also desirable to develop a reflective or transflective display with a liquid crystal cell of 0 c B or Η AN mode. Because reflective or semi-transmissive displays must use a λ / 4 plate, compared to transmissive displays, the system is more complex and yields are often lower. The complex refractive index (b i r e f I · i n g e n c e) effect of the liquid crystal in E C Β (electronically controlled complex refractive index) mode L C d can display colors, so the brightness and resolution of the image are excellent. Therefore, LCDs that are widely used in color TFTs (Thin Film Transistors) can be found in Japanese Patent Application Publication No. 7 (1995) -230087, and "EL, PDP, and LCD monitor. " In OCB, HAN, or ECB mode liquid crystal cells, the polarizing film must be placed at an angle of 20 ° to 70 ° between the transmission axis of the film and the liquid crystal wiping orientation clip. A polarizing plate usually includes a polarizing film (having a polarizing ability) and a protective film 'which includes an adhesive layer on a film or the entire film surface layer. The material of the polarizing film is mainly polyvinyl alcohol (hereinafter referred to as PVA). For example, after the PVA film is uniaxially stretched, it is colored with iodine or a two-color dye to obtain a polarizing film. Or after being colored, the thin film is stretched and then cross-linked with boride. The protective film is mainly a cellulose triacetate film because of its high light transmittance and low birefringence. The P V A film is usually uniaxially extended in the longitudinal direction, so the absorption axis of the produced polarizing film (plate) is almost parallel to the longitudinal direction. Therefore, when applied to L C D in 0CB 'HAN or E C B mode, the roll of polarizing plate must be clamped with the longitudinal oblique 20 to 70. Corner stamping. Due to this oblique punching, the entire board produced cannot be used, but in fact the edges of the polarizing plate in a roll cannot be used. Especially when manufacturing large-size polarizing plates, the yield is very low. In addition, because it is not easy to reuse the remaining polarizers (which have many punched holes), there will be a lot of waste. In order to solve the foregoing problems, there have been proposed methods including extending the orientation of the polymer at a desired angle in the moving direction of the membrane. Japanese Patent A Publication No. 200 0-9 9 1 2 and a method for manufacturing an orientation axis inclined in a uniaxial extension direction. In this method, the plastic film is stretched laterally or longitudinally, and each side of the film is stretched longitudinally or laterally at different speeds. However, if this method is performed using a tenter, each side of the film must be moved at a different rate. As a result, the resulting film is often embossed (streaks due to uneven tension ^ & uneven thickness of the stomach, so it is not easy to obtain the tilt angle obtained (for example, the film used for polarizing plates is 45.) If the difference in the movement rates between the two sides is too small, then the extension step must be extended, and the cost rises significantly. In the method published in Japanese Patent Application Laid-Open No. 3 (199.1)-1 8 2 7 0 1 The two sides of the continuous film are clamped by many pairs of clamps. With the clamp MM f, the extension direction and the moving direction are angled to an angle θ, so that the resulting film @ 丨 申 车 由 and the moving direction are angled to Θ. But even if this is used Method, the moving speed of the two sides of the film is different, which often causes the resulting film to have embossing and crepe. In order to solve the problem, the process must be greatly extended. If so, the cost will also be increased. 2 (1 9 9 0)-1 1 3 9 2 0 In the method issued, 'the film is fed into two rows of chucks. The chucks move along the tenter track' so that each row of chucks goes Different distances. When the film is moving, its two sides are clamped by the chuck The chuck stretching direction and moving longitudinal direction are inclined. However, even if the film is stretched by this method, there are often ridges and creases, which is not conducive to the application of light-9-200302361. (3) Summary of the invention The purpose of the present invention It is to improve the polarizing plate, which can be a mode LCD, or a reflective HAN mode LCD, a polarizing plate, and an improved transflective or reflective type. Another object of the present invention is to provide a polymer film tilt to improve the yield of the polarizing plate. Another object of the present invention is to provide a polarizing plate of the film obtained by the former method. The target polarizing plate has high performance. Another object of the present invention is to provide an LCD having the aforementioned polarized ECB mode. The present invention provides the following polarizing plates (1) to (4), and _ (1) a polarizing plate with a linear polarizing film, which includes a longitudinal polarizing film and a retarder with a longitudinal and a retardation axis, which are substantially parallel to the longitudinal direction of the retarder, and the linear nature Is parallel to the longitudinal direction of the linear polarizing film, and the late phase is not parallel or perpendicular to the longitudinal direction of the retarder. (2) A polarizing plate as defined in (1), wherein the retarder of the retarder is substantially delayed The phase of the phaser is 4 (3) lines The polarizing plate of the polarizing film includes a longitudinal optical film and a retarder with a longitudinal and a late phase axis, which are substantially parallel to the longitudinal direction of the retarder, and are not parallel in nature and perpendicular to the linear polarizing film The vertical axis is substantially parallel to the longitudinal direction of the retarder. It is in the semi-transmissive OCB and provides a yield rate that can simplify the process of LCD. The method of oblique extension is used in polymerization with oblique extension and can be produced at low cost. ΗAN or the following LCDs (5) to (8). The retardation axis of the absorption axis realizer of the longitudinal polarizing film of the linear polarizing film in the linearity of the absorption axis is substantially λ / 4 plate, and the retardation phase is 5 °. The angle between the linear polarization of the absorption axis and the absorption axis of the longitudinal polarizing film of the linear polarizer, the retardation of the retarder -10-200302361 (4) A polarizer as defined in (3), where the retarder is λ / 4 plate, and the absorption axis of the linear polarizing film is substantially at an angle of 45 ° with the longitudinal direction of the linear polarizing film. (5) LCD with a liquid crystal cell and at least one polarizing plate. The liquid crystal cell contains a pair of substrates, each of which has a transparent electrode, and its surface has an alignment layer, while nematic liquid crystals with a curved formula or mixed alignment are sealed on the two alignment layers of the substrate. Among them, the polarizing plate is selected from the polarizing plates defined by (1) to (4). (6) The LCD as defined in (5), wherein the optical compensation film is interposed between the liquid crystal cell and the polarizing plate, and the optical compensation film includes a transparent carrier and an optically anisotropic layer of a dish-shaped liquid crystal with a fixed orientation, wherein The anisotropy of this optical anisotropic layer is Re (0.) Hysteresis 値 is 10 to 60 nm (35 ± 25 nm) '

Re (40 °) hysteresis is 80 to 130 nm (105 ± 25 nm) and Re (-40 °) hysteresis is 10 to 60 nm (35 ± 25 nm).

Re (0.), Re (40.), And Re (-40.) Hysteresis 値 represent the optical anisotropy 値 of the optical compensation film. It is on the plane containing the thin film normal and the minimum hysteresis direction of the optically anisotropic layer, using 6 3 3 nanometers of light to move from the normal direction and deviate from the normal to the minimum hysteresis side clamp 40 ° The direction and normal and the direction that provides the least hysteresis are clamped 40. The direction measured by the direction. (7) The LCD as defined in (6), wherein the optically anisotropic layer of the transparent carrier of the optical compensation film is Re hysteresis 値 10 to 70 nm and Rth hysteresis 70 70 to 400 nm.

The definitions of Re and Rth hysteresis are shown in the following formulas (I) and (Π): (I) Re = (nx-ny) xd (II) Rth = {(nx + ny) / 2-nx} xd 200302361 ny is the refractive index of the transparent carrier along the moving axis, nz is the refractive index at the depth of the transparent carrier, and D is the thickness of the transparent carrier in nanometers. (8) LCD with polarizing film, its manufacturing method is to continuously provide optical polymer film in the bending path, in which both sides of the polymer film are sandwiched and extended according to the following conditions: (i) the longitudinal extension ratio is 1.2 to 2 10, (ii) the extension ratio in the transverse direction is 1.1 to 2 0.0, (iii) the difference in the longitudinal movement rate of the clamps on both sides is 1 ° /. Or below, (i v) there is a state where the volatile component content is 5% or more, (v) the moving direction and the substantially extending direction are clamped at the process exit by 20 ° to 70. Angle; its characteristic is that the LCD operates in OCB, HAN or ECB mode. In this specification, "substantially parallel to π," substantially perpendicular "or" substantially at an angle of 45 ° "means that there may be a deviation of an angle of ± 5 °. Therefore," substantially not parallel or perpendicular " It means that the included angle is between 5 ° and 85 ° (the included angle on the small side is not greater than 90 °). According to the present invention, the linear polarizing film and the retarder can be laminated in a roll-to-roll manner to form a polarizing plate. In order to manufacture polarizers for OCB, Η AN or ECB mode LCDs, or roll-shaped polarizers, polarizing films and retarders (λ / 4 plates in the case of roll-shaped polarizers) must be laminated so that the film Its absorption axis is neither parallel nor perpendicular to the retardation axis of the retarder (λ / 4 plate). In fact, in order to prepare a roll-shaped polarizing plate, the absorption axis of the polarizing film must be clamped by 45 ° with the retardation axis of the λ / 4 plate. The absorption axis of the linearly polarizing film in the form of a film roll obtained by a conventional method is parallel or perpendicular to the longitudinal direction. Therefore, in the roll-to-roll lamination operation, the absorption axis of the thin film cannot be made parallel or perpendicular to the retardation axis of the retarder. Thus, according to the conventional process, a sheet punched from a linear polarizing film and a sheet punched from a retarder are laminated. According to the present invention, a linear polarizer having a retarder which is neither parallel nor perpendicular to the longitudinal direction or a linear polarizing film whose absorption axis is not parallel or perpendicular to the longitudinal direction can be made into a film roll form. Therefore, the present invention can roll-to-roll laminated polarizing film and retarder, so that the absorption axis of the film is not parallel and perpendicular to the retarder of the retarder. Therefore, a polarizing plate (such as a circular polarizing plate) whose absorption axis is not parallel or perpendicular to the late-phase axis can be prepared by a roll-to-roll method. Due to the simple manufacturing method and the low cost and high speed production, curling is very advantageous compared to the coiled layer method and the traditional diaphragm and retarder layer method. L C D in bending alignment mode or Η AN mode is a reflective LCD with wide viewing angle and fast response. Therefore, if a roll-shaped polarizing plate necessary in a display can be produced in a simple manner with low cost and local productivity, the display of the bending alignment mode or the HAN mode can be more widely used. (Liquid crystal cell) The liquid crystal cell of the bending alignment mode or the Η AN mode is described in detail in Japanese Patent No. 03, 118, 197. A liquid crystal cell containing a bendable alignment liquid crystal (ie, a bend-aligned liquid crystal cell) is a symmetrical liquid crystal cell, and a liquid crystal display having the liquid crystal cell substantially has a wide viewing angle. Reflective liquid crystal displays with liquid crystals that can be aligned by HAN also have a wide viewing angle. The liquid crystal cell usually contains a pair of substrates' with a nematic liquid crystal in between. There are transparent electrodes on the surface of each substrate. In the bend alignment liquid crystal cell, a nematic liquid crystal which is oriented in the bend alignment by applying a voltage is used. -13- 200302361 crystals used to bend alignment liquid crystal cells usually have positive dielectric anisotropy. The orientation vector of a nematic liquid crystal changes its direction depending on the voltage applied to the liquid crystal cell. If the voltage is changed, the angle between the orientation vector and the substrate will change. Usually the voltage rises, the angle spreads, and the birefringence decreases to display the image. In this specification, "a liquid crystal with a bend orientation" means that the orientation vector (indicating axis or optical axis) of the liquid crystal molecules in the liquid crystal layer is symmetrical (linearly symmetric) to the center line of the layer, and at the same time at least near the substrate there is a Bend. "Bend π — The word refers to the line formed by the axis of the indicator near the bend of the substrate. In other words, if a voltage is applied to the liquid crystal cell in the bending alignment mode, the indicating axis of the liquid crystal molecules approaching the lower substrate will be almost parallel to the substrate. As the distance from the lower substrate increases, the angle between the indicator axis and the substrate becomes larger, and the indicator axis of molecules located in the central area (the distance from the lower substrate is almost the same as the distance from the upper substrate) is perpendicular or almost perpendicular to the substrate. As the distance from the lower substrate increases, the angle between the indicating shaft and the substrate becomes larger. Finally, the axes of the molecules near the upper substrate are almost parallel to the substrate. The indicator axis in the central area is a twisted alignment. In addition, the indicator axis approaching or touching the upper or lower substrate will be inclined along the surface of the substrate (that is, with an inclination angle). In a bend-aligned liquid crystal cell, the product of the refraction anisotropy (Δη) of the liquid crystal and the thickness (d) of the liquid crystal layer (Δηχ (1) is preferably 100 to 2,000 nm, particularly preferably 150 to 1,700 nm , Preferably 500 to 1,500 nanometers. If the product is within the aforementioned range, both high brightness and wide viewing angle can be achieved. In LCD, Η AN mode is well known. In ΗΑΝ alignment cell, below The substrate is placed on the center line of the corresponding curved alignment unit cell. The alignment layer of the lower substrate allows the nematic liquid crystal to follow the homeotropic alignment. When a voltage is applied to the cell, -14-200302361 is used for the nematic liquid crystal of the HAN alignment cell In the HAN alignment unit cell, it is preferred that the liquid crystal molecules on one substrate are substantially vertically aligned, and on the other substrate, there is a pretilt angle of 0 to 45 °. The refractive index of the liquid crystal is different The product of the directivity (Δη) and the thickness (d) of the liquid crystal layer (Anxci) is preferably 100 to 1,000 nm, particularly preferably 300 to 800 nm. The molecules of the vertical alignment substrate may be on the side of the reflective plate or On the transparent electrode side, the liquid crystal cell with bending alignment or HAN alignment has its own optical compensation Indicating axis. However, even if the display contains a self-optically compensated unit cell, when viewed obliquely (especially upwards and downwards), the transmittance through the black area of the displayed image will increase ® to reduce contrast. Attached to the unit cell, it can improve the contrast of the oblique viewing image before it is reduced without reducing the forward-looking function. (Linear polarizing film) To prepare a roll-shaped polarizing plate, the linear polarizing film is laminated on a λ / 4 plate. So that the absorption axis of the film and the late phase axis of the plate are clamped by 45 °. In order to use a roll-to-roller layer method to prepare a roll-shaped polarizing plate, it is preferable to use a rectangular linear shape with an absorption axis and a longitudinal clamp of 45 ° Rectangular retarder with polarizing film and late phase axis parallel to the longitudinal direction | or a rectangular retarder with absorption axis parallel to the longitudinal axis and a retarder with a retardation axis and longitudinal clamp of 45 °. Some methods have been suggested A desired angle is formed between the orientation axis of the polymer and the film moving direction. Japanese Patent No. 2000-9 9 1 2 discloses a method of forming an orientation axis with an angle between the uniaxial extension direction. In this method, the middle edge of the plastic film Horizontal or vertical extension, thin Each side of the film extends at different rates in the longitudinal or transverse direction, respectively. In the method -15-200302361 published in Japanese Patent Application Laid-Open No. 3 (199.1)-1 8 2 7 0, the continuous film is fed into Both sides of the film are clamped by the multi-clamp operation area. The film clamped by the clamp is extended along the direction of the desired θ angle with the moving direction to obtain the film with the angle θ of the extension axis and the moving direction. Japanese Patent Application Publication In the method published by 2 (199 0)-1 1 3 9 2 0, the film is fed into two rows of clamps. The clamps are moved on the tenter track so that each line of clamps can travel different distances. Under the condition that both sides are clamped by the clamp, the film is moved, so the extending direction and the longitudinal direction of the movement have an inclination angle. In addition, the polarizing plate can be subjected to wiping alignment processing to tilt the moving axis. Moreover, the polymer film can be obliquely extended to obtain a rectangular film rolled into a cylindrical form, which is preferably used to prepare a linear polarizing film. The linear polarizing film material is mainly polyvinyl alcohol (slightly P V A). For example, after uniaxial stretching, the P V A film is colored with iodine or a dichroic dye to obtain a polarizing film. Or the film is stretched after being colored and cross-linked with boride. Polyolefin films can also be used. For example, after stretching, a polyolefin film is dyed to obtain a polarizing film. A linear polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction can be produced, for example, by the following method. A polymer (usually PVA) film is continuously fed into the extension zone, with both sides of the film being clamped by clamps. When moving in the longitudinal direction, the film is stretched. The extension complies with the following formula (1): | L2-L1 | > 0.4W. In formula (1), L1 is the distance traveled from the starting position to the release position by one side of the film being clamped, L2 is the distance traveled by the other side of the film from the starting position to the release position, and W is the essence of the film after extension On the width. During the stretching of the film, the film is maintained in a state where the volatile component content is 5% or more. After stretching, the film is shrunk to reduce the volatile component content. The resulting film was finally wound on a roll. -1 6- 200302361 Figures 1 and 2 are plan views showing a typical example of the oblique stretching method of a polymer film. The stretching method includes: (a) introducing the raw material film in the direction of arrow (A), (b) extending in the width direction, and (c) sending the stretched film in the direction shown by arrow (b) to the next step . The following "extension step" means an extension step including (a) to (c). The film is continuously introduced in the direction shown in (A), and it is clamped at the left point B 1 with a clamp as the upstream side. At this time, the other side is not clamped, so there is no tension in the width direction. That is, the point B 1 is not the starting point of the substantial clamping. The starting point of substantial clamping according to the present invention is the point where both sides of the film are clamped. There are two gripping points for the starting point of the substantial clamping: A 1 and C 1, A 1 is a vertical line to the center line 11 (picture 1) of the leading edge, and 21 (picture 2) and the track 13 (picture 1) of the fixture running Picture) or 23 (picture 2) is C1. The clamps on both sides move at substantially the same speed, one side moves from A1 to A2, A3 ... An, and similarly C1 moves to C2, C3, " _Cn. The extending direction is indicated by the connecting line of An and C η, and An and Cn are the pinch points moved by the standard fixture at the same time. According to the method of the present invention, as shown in Figs. 1 and 2, An gradually lags behind Cn, so the extension axis becomes vertically deviated from the moving direction. The essential downstream release point according to the present invention is the points CX and AX at which the film is released by the fixture; and CX plots the centerline (Figure 1 12 or Figure 2 2 2), and trajectory 1 4 (No. 1) or 24 (2) to Ay. The final extension angle of the film is determined by the distance between Ay-Ax [ie, | L1-L2 |, that is, the difference between the left and right sides of the fixture at the substantial end point of the extension step 200302361 (the substantial release point of the fixture)], and the distance between the two points where the fixture is substantially released w (the distance between CX and Ay) determines it. The inclination angle Θ between the extending direction and the moving direction is defined by the following formula: tan6 = W / (Ay-Αχ), that is, tan0 = W / | Ll-L2 | Caught to point 1 8 (picture 1) or 2 8 (picture 2) (that is, after point Ay), and the other side was already released. Therefore, points 18 and 28 do not widen their width again, and thus are not the essential release points of the present invention. As mentioned above, the actual starting grips on the left and right sides are not the separate grips of the fixture. If the foregoing definition is more strictly described, the essential starting pinch point of the present invention is the point at which both sides begin to clamp at the same time, and its continuity and the film centerline are approximately at right angles (ie, A1 and C1). Similarly, the two substantial release points refer to the point where the left side has reached the most downstream point (Cx), and the angle of inclination of the vertical line clip Θ drawn by the CX point to the centerline of the film when the fixture is released at this point, and the intersection of the right side (AX). As used herein, '' is approximately at right angle π, which means that the angle between the line connecting the left and right substantial initial pinch points and the center line of the film is 90 ± 0.5 °. With the extension machine of the tenter system of the present invention, the distance traveled by the left and right clamps is different. The large gap between the clamp point of the clamp and the substantial starting clamp point, or between the clamp release point and the substantial release point is sometimes due to The limitation of the machine (such as the length of the track. However, as long as the substantial starting pinch and the substantial release point satisfy Equation (1), the purpose of the present invention can be achieved. The inclination angle of the orientation axis of the obtained stretched film can also be controlled. That is, the distance difference | L1-L2 | determined by the left and right clamps and the width of the exit (C) in step (C) are controlled by 200302361. In polarizing plates and birefringent films, films oriented at 45 ° with the longitudinal direction are often the In this case, in order to make the orientation angle close to 45 °, it is better to meet the following equation (2): 0.9W < | L1-L2 | < 1.1 W Equation (2) is more preferably to meet the following Equation (3): 0.97W < | L1-L2 | < 1.03 W Formula (3) In the specific example of the extended structure shown in Figs. 1 to 6, the obliquely stretched polymer film conforms to the equation (1 ), And can be arbitrarily designed taking into account the installation cost and yield. The angle between the direction (A) and the direction (B) of the film moving to the next step can be any number. In terms of minimizing the full area of the device including the steps before and after the extension, the smaller the angle, the better. This angle It is preferably within 3 °, and particularly preferably within 0.5 °. This can be achieved by the structure shown in Figures 1 and 4. In the method in which the film movement direction is substantially unchanged, if only the size of the fixture is enlarged The distance is not easy to obtain a suitable 45 ° orientation angle (for the vertical axis) of the polarizing plate and the birefringent film. Therefore, after extending the film as shown in Figure 1, and then shrinking the film, it can increase | L1-L2 In addition, in order to minimize the cost of installing the extension unit, it is preferable to make the fixture track bending period less and the bending angle smaller. From this point of view, the direction of film movement is preferably curved on both sides of the film The angle of 40 to 50 ° between the moving direction of the film at the exit of the two sides of the film and the extension direction of the film is clamped at an angle of 40 to 50 °, as shown in Figs. 2, 3, and 5. -19- 200302361 The extension device is preferably a tenter as shown in any one of Figures 1 to 5. In addition to the traditional two-degree space tenter, it is also possible to use the extension method in which the clamp trajectory shown in Figure 6 spirals to make the two sides different. In the tenter type extension machine, in many cases, due to the installation of fixtures The chain moves along the track. Like the laterally uneven stretching method of the present invention, deviations at the end of the track at the entrance and exit of the step can sometimes occur. As shown in Figures 1 and 2, the left and right sides of the film cannot be clamped and released simultaneously. In this case, the actual running distance is not simply the distance between the pinch point and the release point, but the length of the part where the two sides of the film are clamped and run as described above. If the left and right sides of the film move at different rates during the extension step, Then the film at the exit of the stretching step will be wrinkled and locally uneven in thickness. Therefore, the left and right film holder movement rates must be substantially the same. The difference in the movement rate is preferably 1% or less, more preferably less than 0.5%, and most preferably less than 0.05 ° /. . As used herein, the term '' rate '' refers to the distance that the left and right clamps can move per minute. In general tenter-type extension machines, the difference in speed is calculated in terms of time in seconds or less. It depends on the period of the sprocket teeth that drive the chain and the frequency of the drive motor. Uneven percentage points are generated. However, this rate unevenness has a limited effect on the rate described in the present invention. Due to the difference in the running speed of the left and right clamps, uneven film thickness and wrinkles can be caused. To solve this problem, the present invention includes maintaining the support quality of the film, stretching the film in the presence of a volatile component content of 5% or more, and then reducing the volatile component when shrinking the film. The term "maintaining the support quality of a polymer film" means that the film is clamped on both sides before it can impair its properties. -20- 200302361, "The stretch film in the presence of 5% or more volatile components" means that it is not necessary to maintain the volatile content of 5% throughout the stretching process or to have volatile components in one stomach 5 The state of% or above exerts the effect of the present invention, and it is mentioned that the volatile component in the part of the extension process can be less than $%. The method for maintaining the volatile component in this state includes: winding the film, and making water Or the volatile component of the anhydrous solvent is contained in its φ; before the extension, 'e.g. the volatiles of water or anhydrous solvents, or coating or spraying with volatiles. When stretching, for example, water or The volatiles of the anhydrous solvent are coated or cleared on the thin spleen μ ^ Bo Yi HL. For example, the hydrophilic polymer film of polyvinyl alcohol will absorb the moisture in the atmosphere of the door, so it can first absorb moisture in a high-humidity atmosphere. In addition to these methods, any other method that can make the polymer film contain 5% or more volatile components can be used. The preferred volatile component depends on the type of polymer film. As long as the support of the polymer film can be maintained, the maximum content of volatile components is not limited. In the case of Shuiyican, the content of volatile components is preferably 丨 0% to 100% ′, and tritiated cellulose is 0-1% to 2000%. The stretch film can be contracted during and after stretching. The shrinkage of the film involves increasing the temperature to remove volatile constituents. However, as long as the film can be shrunk, any method can be used. The content of volatile components after drying is preferably 3% or less, more preferably 2% or less, and most preferably 1.5% or less. In the present invention, the track that restricts the trajectory of the fixture often has a large bending curve. In order to prevent the thin film clamps from interfering with each other due to sharp turns or local application concentration, it is preferable that the trajectory of the clamps is changed along an arc. The polymer film to be stretched in the present invention is not particularly limited. -21- 200302361 can be used suitable polymer film soluble in volatile solvents. The polymers can be PVA, polycarbonate, tritiated cellulose and polymill. The thickness of the film before stretching is not particularly limited. In terms of the stability of the film and the uniformity of stretching, the preferred thickness is 1 micrometer to 1 millimeter, and more preferably 20 micrometers to 200 micrometers. Although the stretched film of the present invention has various applications, it is particularly suitable as a polarizing film or a birefringent film because of its orientation axis and longitudinal tilt angle; specifically, when used as an LCD polarizing plate, the tilt angle is 40 to 50 ° , Particularly preferably from 44 to 46 °. When the present invention is used to make a polarizing film, the preferred polymer is P V A. P V A is usually obtained by saponification of polyvinyl acetate. However, it may contain ingredients copolymerizable with vinyl acetate, such as unsaturated carboxylic acids, unsaturated sulfonic acids, alkenes, and vinyl ethers. It is also possible to modify the PVA by using acetamidine, sulfonyl, carbonyl and / or oxyalkylene groups. Although the degree of saponification of P V A is not particularly limited, in terms of solubility, it is preferably 80 to 100 mol%, and particularly preferably 90 to 100 mol%. In addition, although the polymerization degree of P V A is not particularly limited, it is preferably 100 to 10, 0 0, and particularly preferably 1, 500 to 5,000. P V A can be dyed to obtain a polarizing film. The dyeing method is adsorption in the gas or liquid phase. If iodine is used for liquid phase adsorption, the PVA film is immersed in an iodine-potassium iodide aqueous solution. The amount of iodine is preferably 0.1 to 20 g / L, the amount of potassium iodide is preferably 1 to 100 g / L, and the weight of iodine to potassium iodide is preferably 1 to 100. The dyeing time is preferably from 30 to 5,000 seconds, and the temperature of the solution is preferably from 5 to 50 ° C. There are many dyeing methods, not only dipping, but also coating or spraying with iodine or dye solution. The dyeing step may be before or after the extension step of the present invention. However, it is particularly preferred that the film is dyed in the liquid phase before the film -22- 200302361 is stretched, so that the film can be easily expanded after being properly expanded. It is also preferable to use a dichroic dye and iodine. Specific examples of the dichroic dye include an azo dye, a stilbene dye, a pyrazolinone dye, a triphenylmethane dye, a quinoline dye, an oxazine dye, a triazine dye, and an anthraquinone dye. This dye is preferably water-soluble, but is not limited to water-soluble. In addition, it is preferred that these dichroic molecules include a sulfonic acid group, an amine group, and a hydroxyl group. Specific examples of dichromatic dye molecules are CI · (Dye Index) Direct Yellow 12, CI · Direct Orange 39, CI Direct Orange 7 2, C · I · Direct Red 3 9, C · I · Direct Red 7 9, C · I · Direct Red 8 1, C. I · Direct Red 8 3, C · I. Direct Red 8 9, C. I · Direct Purple 4 8, C · I · Direct Blue 6 7, C · I. Direct Blue 9 0, C. I. Direct Green 5 9 and C. I. Direct Red 3 7 and Japanese Patent Application Publication i (1 9 8 9)-1 6 1 2 0 2, 1 (1 9 8 9)-1 7 2 9 0 6, 1 (1989) -172907, 1 (1989) -183602, 1 (1989) -248105, 1 (1989) -265205 and 7 (1995) -261024 dye. These dichroic molecules may be in the form of free acids, alkali metal salts, ammonium salts or amine salts. Polarizing plates with various shades can be obtained by blending two or more of these two-color molecules. Polarizing elements or polarizers containing black dyes when the polarization axes intersect perpendicularly, or those containing various dichroic molecules that can show black are excellent in terms of veneer transmission and polarization. When a polarizing film is produced by extending P VA, a cross-linking agent of P V A is preferably used. Specifically, when the oblique stretching of the present invention is used, the insufficiently hardened PVA at the exit of the stretching step may cause the orientation axis of the PVA film to shift due to the tension in the step. Therefore, it is preferable that the film is immersed or coated with a crosslinking agent solution before or during stretching so that the crosslinking agent is contained in the film. Suitable crosslinkers are described in -23-200302361 U.S. Re-published Patent No. 2 3 2 8 97, preferably boric acid compounds. The extension method of the present invention is also preferably used to make a so-called polyethylene photo film, in which the polyolefin structure is derived from conjugated double bonds of PVA dehydration or polyvinyl chloride dehydration which can cause polarizing performance. The linear polarizing film may be a cellulose triacetate film. Cellulose triacetate has light transmittance and low birefringence, so it can be used as a protective film for optical compensation film, late-phase summer plate) or normal polarizing plate. The polarizing film made according to the present invention has a protective film and a polarizing plate bonded on one or both sides. The type of the protective film is not particularly limited. Film materials which can be used in the present invention include cellulose esters such as cellulose acetate, cellulose butyrate, polycarbonate, polyolefin, polystyrene, and polyester. Essential characteristics of the protective film such as high light transmission, proper moisture permeability, low radiation, and proper stiffness. From this point of view, it is known that cellulose acetate is preferred, and cellulose acetate is preferred. The nature of the protective film depends on the intended application. The film for the transmissive LCD preferably has the following properties: in terms of operation and durability, the thickness is more than 5 to 500 microns, particularly preferably 20 to 200 microns, and particularly good. The hysteresis at 632.8 nm is preferably 0 to 150 nm, 0 to 20 nm, and most preferably 0 to 4 nm. The late phase axis of the protective film is substantially parallel or perpendicular to the absorption axis of the polarizing plate, so the linear film will not be circularly polarized. However, if the protective film is designed to change the polarizing element (such as a retarder), the retardation axis of the protective film can absorb the polarizing film at any angle. The light transmittance of visible light is preferably 60% or more, particularly good is 90% or the system is < and the high light ^ (1/4 is obtained, and the best protection of the light-reflection panel is 1 00, especially better Preferential polarized shaft clamp (top. -24- 200302361) After processing the film for 120 hours at 90 ° C, its shrinkage in one degree space is preferably 0.3 to 0.0 1%, particularly preferably 0.1 5 To 0.0 1%. The tensile strength measured by the tensile test is preferably 50 to 1,0 0 0 X 1 0 6 bar, particularly preferably 100 to 3 0 0 x 10 6 bar. Better moisture permeability 100 to 800 g / m2_day, particularly preferably 300 to 600 g / m2 · day. However, the present invention is not limited to the foregoing range and range. Tritonated cellulose which is preferably used for a protective film The details will be described below. In the preferred tritiated cellulose, the degree of substitution of hydroxyl groups in cellulose can satisfy the following formulae (I) to (IV): Formula (I) 2.6SA + BS3 · 0

Formula (II) 2. 0 < A < 3. 0 Formula (III) 0SB50 · 8 Formula (IV) 1 · 9 &AB; where A is the degree of substitution of hydroxy groups in cellulose with A ethyl acetate, B is C 3 _ 5 Degree of substitution of amidino. Cellulose usually has three hydroxyl groups in one glucose unit, so the degree of substitution mentioned above is based on 3.0. That is, the maximum degree of substitution is 3.0. In cellulose triacetate, the degree of substitution is usually 2.6 to 3.0 (i.e., the most unsubstituted hydroxyl group is 0.4) and B is 0. The tritiated cellulose as the protective film of the polarizing plate is preferably cellulose triacetate, in which all the fluorenyl groups are acetamidine; or acetamidine containing 2.0 or more, 0.8 or more (considering the properties of the film, especially Preferably, it is 0.3 or less) fluorenyl groups and 0.4 or less unsubstituted hydroxyl groups. In order to determine the degree of substitution, the C 3 _ 5 free acid content of the hydroxyl groups in acetic acid and substituted cellulose was measured according to the American Standard Material Test Method A S T M D-8 1 7-9 1. Examples of C 3 _ 5 fluorenyl groups other than acetamidine are propylammonium (C 2 Η 5 C Ο-), butylammonium (n--25- 200302361, iso-C3H7CO-), and pentamidine (n-iso-, another-, Third-c4h9co-). In terms of the mechanical strength and solubility of the obtained film, among them, a n-substituent is preferable, and n-propanthion is particularly preferable. If the degree of substitution of ethenyl is low, the mechanical strength, heat resistance and humidity of the obtained film are poor. If c 3 _ 5 is highly substituted, the solubility of tritiated cellulose in organic solvents can be improved. The tritiated cellulose having a degree of substitution within the aforementioned range has better properties. The degree of polymerization (average viscosity) of the tritiated cellulose is preferably from 200 to 700, and even more preferably from 250 to 55. In order to determine the viscosity average polymerization degree, the viscosity was measured using an "Osto Huelt Viscometer" (0 s t w a 1 d v i s c 0 m e t er r). From the obtained specific viscosity [η], calculate the viscosity average polymerization degree DP according to the following formula: ΌΡ = [η] / Κηι where Km is a constant 6 × 10_4. Cellulose, the raw material for making tritiated cellulose, is obtained from cotton wool or wood pulp. Raw pulp can also be used. The tritiated cellulose protective film is usually prepared by a solution casting method, which includes dissolving tritiated cellulose and additives with a solvent to obtain a viscous solution (the so-called "dope"). This solution is cast on A continuous support, such as a drum or belt, evaporates the solvent to form a thin film. The thick liquid preferably has a solid content of 10 to 40% by weight. The surface of the drum or belt is preferably polished to a mirror surface. The casting and drying of the solvent casting method are described in U.S. Patent Nos. 2,3 3,6,3 10, 2,3 6,7,60 3, 2,492,078, 2,492,977, 2,492,998, 2,607,704, 2,7 3 9 , 0 6 9, 2, 7 3 9, 0 7 0, British patent 6 4 0, 7 3 1, 7 3 6, 8 9 2, Japanese patent 45 (1970)-4554, 49 (1974 ) -5614, Japanese Patent Application Laid-open Nos. 6 0 (1 9 8 5)-1 7 6 8 3 4, 6 0 (1 9 8 5)-2 0 3 4 3 0 -26- 200302361 and 62 ( 1987) -115035. Two or more kinds of tritiated cellulose can be co-casted into two or more layers. For example, two or more outlets along the moving direction of the carrier can be cast respectively. See Japanese Patent Application Laid-Open Nos. 6 1 (1 9 8 6)-1 5 8 4 1 4 and 1 (1 9 8 9) · 1 2 2 4 1 9 and 1 1 (1 9 9 9)-1 9 8 2 8 5 Or the tritiated cellulose solution can be cast into a film from two outlets, see Japanese Patent Nos. 60 (19 8 5)-2 7 5 6 2, 61 (1986) -947245, 61 (1986) -104813, 61 (1986) -158413 and 6 (1 9 9 4)-1 3 4 9 3 3. In addition, the high-viscosity tritiated cellulose solution stream can be enveloped by the low-viscosity solution stream to form a laminar stream, and the high- and low-viscosity solutions in the laminar stream can be simultaneously extruded into a film. See, Japanese Patent Application Publication No. 56 ( 1981) -162617. Solvents capable of dissolving tritiated cellulose are, for example, hydrocarbons (such as benzene, toluene), halogenated hydrocarbons (such as dichloromethane, chlorobenzene), alcohols (such as methanol, ethanol, diethylene glycol), ketones (such as acetone), and esters ( (Such as ethyl acetate, propyl acetate) and ethers (such as tetrahydrofuran, methyl cellosolve). Ci_7 halogenated hydrocarbons are preferred, and dichloromethane is most preferred. In terms of solubility, carrier peelability, mechanical and optical properties of the formed film, 'is preferably a mixed solvent of dichloromethane and one or more Ci-5 alcohols. The amount of the alcohol used is preferably 2 to 25% by weight, more preferably 5 to 20% by weight, based on the weight of the entire solvent. Alcohols such as methanol, ethanol, n-propanol, isopropanol, and n-butanol. Preference is given to using methanol, ethanol, n-propanol and mixtures thereof. In addition to tritiated cellulose, dope solution can contain additives such as plasticizers, UV absorbers, inorganic fine particles, and alkaline earth metals (such as calcium and magnesium) as heat stabilizers. Salts, antistatic agents, flame retardants, lubricants, oils, release agents and hydrolysis inhibitors of tritiated cellulose. -27- 200302361 Plasticizers include phosphate esters and carboxylic acid esters. Phosphate esters include, for example, triphenyl phosphate (TPP), tricresyl phosphate (TCP), toluene diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, and tributyl phosphate. Typical examples of carboxylic acid esters are phthalates and citrates. Phthalates include, for example, dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate, diphenyl phthalate (DPP), and diphthalate Ethylhexyl ester (DEHP). Citric citrates include, for example, triethyl orthoacetate citrate (0 AC T E) and tributyl orthoacetate citrate (OACTB), ethyl triethyl citrate, or ethyl tributyl citrate. You can also use other carboxylic acid esters such as butyl oleate, methyl ethyl ricinoleate, dibutyl sebacate and various trimellitic acid esters, such as trimethyl trimellitic acid. Glycol esters are, for example, triacetin, tributin, butyl glycol butyl phthalate, ethyl glycol ethyl phthalate, ethyl glycol methyl phthalate, and butyl glycol butyl Phthalate. Preference is given to using triphenyl ortho acid, biphenyl diphenyl phosphate, tricresyl phosphate, toluene diphenyl phosphate, tributyl phosphate, dimethyl phosphate, diethyl phthalate, dibutyl phthalate, Dioctyl phthalate, diethylhexyl phthalate, triacetin, glyceryl ethyl phthalate and trimethyl trimellitate. Particularly preferred are triphenyl phosphate, biphenyl diphenyl phosphate, diethyl phthalate, ethyl glycol ethyl acetate and trimethyl trimellitate. They can be used individually or in combination. The amount of the plasticizer is preferably 5 to 30% by weight of the tritiated cellulose, and particularly preferably 8 to 16% by weight. When preparing the blending solution, it can be added together with the tritiated cellulose and the solvent, or it can be added before preparing the blending solution. Depending on the target, UV absorbers can be used. The ultraviolet absorbent includes a salicylate-based absorbent, a benzophenone-based absorbent, a benzotriazole-based absorbent, a benzoic acid-28 · 200302361 ester-based absorbent, a cyanoacrylate-based absorbent, and a nickel complex salt-based absorbent. Absorbent. Preferred are benzophenone-based absorbent, benzotriazole-based absorbent, and salicylate-based absorbent. The benzophenone-based absorbent is, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-ethylacetophenone, 2-hydroxy-4-methoxybenzophenone, 2,2-dihydroxy- 4-methoxybenzylbenzene, 2,2'-di-hydroxy-4,4'-benzyloxybenzylbenzene, 2-hydroxy-4-n-octyloxybenzylbenzene, 2-hydroxy-4-dodecane Oxyphenazine and 2-hydroxy-4- (2-hydroxy-3-methacrylic acid) propoxyphenazine. A benzotriazole-based absorbent is, for example, 2-(2 1 -hydroxy-3 1 -third butyl-5'_toluene) -5_chlorobenzotriazole 2- (2hydroxy-5 '-third butyl Group) benzotriazole, di-"'-hydroxyl' ^ '-di-third pentylbenzene benzotriazole,:-^^!-〗' ^ '-: Third butylbenzene) -5-chloro Benzotriazole and 2- (2'-hydroxy-5'-third octylbenzo) benzotriazole. Salicylate-based absorbents are phenyl salicylate, p-octylphenyl salicylate, and Para-tert-butylphenyl salicylate. Especially preferred are 2-hydroxy-4-methoxybenzibenzyl, 2,2'-bishydroxy-4,4'-methoxybenzibenzyl, 2- (2 '· Hydroxy-3 · -Third-Butyl-5'-Toluene) -5-Chlorobenzotriazole, 2- (2'-Hydroxy-5'-Third-Butylbenzene) benzotriazole, 2- ( 2'-Hydroxy-3 ', 5'-bis-tertiary butyl benzene) -5 -chlorobenzotriazole. Particularly preferred is the use of two or more ultraviolet absorbers that absorb light of different wavelengths, so that the polarizing plate can be shielded widely. Ultraviolet light in the wavelength range. The amount of the ultraviolet absorber is preferably from 0.01 to 5% by weight, and more preferably from 0.1 to 3% by weight. The absorber can be added to the solvent and the cellulose to be absorbed, Or add the prepared blending solution It is preferable to mix the ultraviolet absorber solution into the blending liquid by using, for example, a static mixer immediately before coating. Inorganic fine particles such as silica, kaolin, talc, diatomaceous earth, quartz powder, calcium carbonate, barium sulfate, titanium dioxide And alumina. Before adding the blending liquid, it is preferred to disperse the fine particles in the binder solution using a high-speed mixer, ball mill, honing machine or ultrasonic disperser-29-200302361. The fine particles of the binder are preferably And any solvent such as an ultraviolet absorbent can be used to disperse the fine particles, but a solution is preferred. The average size of the number of particles is preferably from 0.1 to 10 microns. A dispersant may be added to dissolve the tritiated fibers, However, it is preferably incorporated in the blending solution just before the membrane mixer. The release agent is preferably a surfactant. The surfactant is a surfactant, a sulfonate surfactant, a nonionic surfactant, and Other surfactants in the cationic world. Japanese Patent Application 6: Documented release agents. If a cellulose acetate film is used as a protective film, chemical treatment, corona discharge treatment, flame treatment, or hydrophilic It can enhance the adhesion of PVA resin or the surface is coated with a hydrophilic resin solution, in which the esters are compatible. In order to make the film surface hydrophilic, it does not hinder the flatness and properties of the film. Soap is immersed in an aqueous solution such as sodium hydroxide . The warp and film, and fully washed with water. On the protective film of the polarizing plate, there are various optical layers with different functional layers for the viewing angle of the LCD (see Japanese Patent No. 4 (1992) -229828, No. 6 (1994) -75115, To improve the display, the polymer-dispersed liquid crystal layer is preferably tritium cellulose. Other additives are dispersed together. The same as the dope (dope) is 0.01 to 100 microns, before the stage of Eusep or other stages, such as static mixing. The surfactant is, for example, a phosphate-based carbonate-based surfactant or a surfactant. It is also possible to use [(1986) -243837, preferably a soap glow discharge treatment on its surface to make it more stable. The solvent can be used with saponified acetic acid. Saponification treatment is preferably used. For example, the film is treated with a low concentration of acid. The functional layer is, for example, a compensation of this patent application publication: and 8 (1996) -50206 or spiral nematic liquid crystal layer-30- 200302361 discriminative anti-flash layer or anti-reflection layer (which can use anisotropic scattering or Anisotropic optical interference separates PS waves to improve the brightness of LCD), hard coatings to improve the scratch resistance of polarizers, gas barriers to suppress the diffusion of moisture or oxygen, adhesive layers or adhesives to improve the adhesion of polarizing films and slip Floor. The functional layer can be on the polarizing film side or the other side; depending on the application, which side can be added with the functional layer. In the case of a protective film, the functional layer may be laminated on one or both sides thereof. The functional layer is, for example, a λ / 4 plate or a λ / 2 plate, a light diffusion film, a plastic cell with a conductive layer on the other side of the polarizing plate, a ® brightening film with different directions of scattering or optical interference from different directions, and a reflecting plate Or a transflective reflector. The aforementioned preferred protective film can be used as a protective film for polarizing plates. In addition, two or more kinds may be used in combination. The same protective film may be laminated on each surface of each polarizing film. Or use polarizing film with impossibility and properties on both surfaces. In addition, a protective film may be laminated on one surface of the polarizing film, and an adhesive layer may be added on the other surface to directly laminate the liquid crystal cell; in this case, it is preferable to laminate a release film on the outside of the adhesive layer. There is no particular limitation on the adhesive used for laminating the protective film on the polarizing film. The adhesive includes, for example, ρ v Α-based resin (including modified PVA having an ethyl acetamidine group, a sulfonic acid group, a carboxyl group, and / or an oxyalkylene group), and an aqueous boride solution. Among them, P VA-based resin is preferred. An aqueous solution of boride or potassium iodide can be added to the P VA resin. The thickness of the adhesive layer after drying is preferably from 0.01 to 10 μm, and particularly preferably from 0.05 to 5 μm. Fig. 7 is a conventional polarizing film obtained by punching, and Fig. 8 is a polarizing film of the present invention obtained by punching. As shown in FIG. 7, the direction of the polarizing light absorption axis of the conventional polarizing film -3 1- 200302361 is the same as the longitudinal direction, and the polarizing film of the present invention has a polarizing light absorption axis 8 i (that is, an extension axis) and a longitudinal 82 clip 45. , As shown in Figure 8. This angle is equal to the angle between the absorption axis of the polarizing plate laminated to the liquid crystal cell in the LCD and the vertical or horizontal direction of the liquid crystal cell itself, so no diagonal punching is necessary in the stamping stage. In addition, as shown in FIG. 8, the polarizing film of the present invention is cut straight in the longitudinal direction, so it can be cut in the longitudinal direction without punching. Therefore, the polarizing plate of the present invention has excellent yield. In the polarizing plate of the present invention, an adhesive layer may be added for lamination with other elements in the LCD. On the adhesive layer, a laminated adhesive separation film is preferred. The adhesive layer is not only required to have optical transparency, but also to have appropriate viscoelasticity and adhesive properties. Examples of the adhesive layer material include acrylic copolymers, epoxy resins, polyurethanes, ketone polymers, polyethers, butyral resins, polyamides, polyvinyl alcohol resins, and synthetic rubbers. From these materials, a layer is formed and can be hardened by a drying method, a chemical hardening method, a thermal hardening method, a melting method, and a light hardening method. The preferred material is a propionic acid copolymer, because its adhesion can be easily controlled, and the formed layer has excellent transparency, weather resistance and durability. In terms of improving the contrast of L C D, it is preferred that the polarizing plate of the present invention has higher light transmission and higher polarization. The light transmittance at a wavelength of 55 nm is preferably 30% or more, particularly preferably 40% or more. At 5500 nm, the degree of polarization is preferably 95.0% or more, particularly preferably 99.0% or more, and particularly preferably 99.9% or more. The LCD of the present invention preferably contains a liquid crystal cell and a polarizing film (or a pair of polarizing films). In the liquid crystal cell, the liquid crystal is enclosed in a pair of substrates, each of which has an alignment layer. The transmission axis of the polarizing film is preferably between 20 and 70 in the longitudinal direction. , Especially -32- 200302361 is preferably 40 to 50. It is particularly preferred that the longitudinal direction of the film is 44 to 46 °, and the alignment direction is preferably parallel to align the liquid crystal. If the LCD contains a pair of polarizing films, the two absorption axes of the film are preferably vertical parent forks. (Optical compensation film) The optical compensation film is preferably an optically anisotropic layer containing at least one transparent carrier and a dish-shaped liquid crystal having a fixed alignment. The optical anisotropy of the optical anisotropic layer 値 Re (〇.), Re (40.), And Re (-40.) Are preferably 35 ± 2 nm, 105 ± 25 nm, and 35 ± 25, respectively. Nanometer range. The preceding Re (0.), Re (40 °), and Re (-4 °) represent the hysteresis of the optically anisotropic thin film. On the plane containing the normal of the thin film and the direction that provides the smallest direction of the optical anisotropic layer, the opposite sides of the light with a normal retardation of 6 3 3 nanometers and a minimum hysteresis are provided, and the opposite side deviation is 40 °, And measured from the normal direction to provide the minimum hysteresis in the direction of 40 ° measurement. (Transparent carrier) The transparent carrier of the optical compensation film is preferably a polymer film having a light transmittance of 80% or more. It is preferred that the polymer film has no birefringence even when an external force is applied. The polymer film is, for example, a cellulose-based polymer, an orbornene-based polymer [such as Artone® of JSR (Nippon Synthetic Rubber Co., Ltd.) and Zeoiiez® of NipponZeon Corporation] 'and polymethyl methacrylate. The cellulose polymer is more preferably a cellulose ester, and more preferably a cellulose ester of a lower fatty acid. Here, "lower fatty acids" means fatty acids of q or less. The carbon number is preferably 2 (cellulose acetate), 3 (cellulose propionate), or 4 (cellulose butyrate). Preferable fiber is 酉Examples of cellulose acetate include diacetyl cellulose and triethyl cellulose. Mixed fatty acid cellulose esters such as propionate acetate-33-200302361 cellulose and cellulose acetate butyrate can also be used. Generally speaking , The hydroxyl groups at the 2-, 3-and 6-positions of the tritiated cellulose are not identically substituted (that is, the degree of substitution at each position is not equal to 1/3 of the total degree of substitution), and the 6-position substitution The degree is usually small. In the tritiated cellulose used in the present invention, the degree of substitution at the 6-position is preferably greater than 2 _ and 3 _ positions. The substitution rate of the 6-position hydroxyl group by the fluorenyl group is preferably all The degree of substitution is 30% to 40%, particularly preferably 31% or more, more preferably 32% or more. In addition, the degree of substitution of the fluorenyl group at the 6-position is preferably 0.88 or more. 6-position of The meridian group may be substituted by a non-ethyl fluorene group of C 3 or more. The fluorene group of c 3 # or more is, for example, propane, butyl, pentyl, phenyl, and propylene. The degree of substitution at each position can be measured by nuclear magnetic resonance spectroscopy. The tritiated cellulose produced in Japanese Patent Application No. 1 (丨 9 9 9)-5 8 5 1 can be used in the present invention. (Hysteresis of polymer film) The hysteresis of a polymer film can be defined by the following formulae (I) and (11): Formula (I) Re = (nx-ny) xd · Formula (II) Rtli = {(nx + ny) / 2-nz} xd In formulas (I) and (Π), nx is the refractive index along the retardation axis (that is, along the direction of the maximum refractive index) on the film plane; ny is along the moving axis (that is, along the direction of the minimum refractive index) on the film plane. ); Η z is the refractive index along the thickness direction of the film; d is the thickness of the layer film in nanometers. In the present invention, Re and Rth 値 are preferably up to 70 mm and 70 to 4 respectively. 00 nm. The complex refractive index 値 (Δη = ηχ-η) of the polymer film is from 0.0 0 0 2 5 to 0. 〇〇〇〇 08, and the transparent carrier preferably has a multiple in the thickness direction -34- 200302361 Emissivity 値 is 0.00088 to 0.005. (Angle of the late phase axis in the polymer film) The extension direction of the polymer film is the standard line (0 °), and the The angle is the angle between the late phase axis and the standard line. If the roll-shaped film is extended horizontally, the horizontal direction is the standard line. If the film is extended longitudinally, the vertical direction is the standard line. The average angle of the late phase axis is preferably 3 ° or below, particularly preferably 2 ° or below, preferably 1 ° or below. The direction providing the average angle of the late phase axis is the average direction of the late phase. The angle of the late phase axis has a standard deviation, preferably 1. 5 ° or less, particularly preferably 0.8 ° or less, and most preferably 0.4 ° or less. After a period of electric shock, a transmissive LCD with an optical compensation film often displays an image screen with leaked light (the so-called `` uneven screen ''. This is due to the increased transmission around the screen, especially when displaying a black image. In addition, in a transflective LCD, the backlight will generate heat and the heat will be unevenly dispersed in the liquid crystal cell. The uneven thermal dispersion will change the optical properties of the optical compensation film (hysteresis, angle of the retardation axis). ), Which will cause "uneven picture". When the temperature rises, the optical compensation film will expand or contract. However, the expansion or contraction is limited because the film is fixed on the liquid crystal cell or linear polarizing film, so the film is elastically deformed. And change the optical properties. In order to avoid "uneven picture", it is better to use a polymer film with high thermal conductivity as the optical compensation film. The polymer with high thermal conductivity includes cellulose acetate [0.22 W / m.QC] , Low-density polyethylene [0 · 34 W / m · T:], ABS [0.36 W / m · ° C] and polycarbonate [0 · 19 W / m]. Cyclic olefin-35- 200302361 can also be used for polymerization , Such as Zeonez ^ O.20 W / m · C by Nippon Zeo η, Zeonor® [0.20 W / m. ° C], and Artone® [0.20 W / m- ° C] by JSR. Consider optics and For thermal properties, cellulose acetate with an acetic acid content of 5 9.0 to 6 1.5% is preferred. The term "acetic acid content" refers to all acetic acid per unit weight of cellulose. For the measurement of acetic acid content, see American Standard Material Test Method ASTMD-8 1 7-9 1 (Test Method of Cellulose Acetate). The film of the present invention has a viscosity average polymerization degree (DP) of preferably 2 50 or more, particularly preferably 2 9 0 Or above. In addition, the preferred polymer is a narrow molecular weight distribution Mw / Mn (Mw and Mη are the weight average molecular weight and number average molecular weight measured by the Colloidal Penetration Layer® analysis method, respectively). Mw / M η is preferably 1.0 to 1.7, particularly preferably 1.3 to 1.6, and most preferably 1.4 to 1.6. (Hysterescensing agent) In order to adjust the hysteresis of the polymer film, An aromatic compound having at least two aromatic rings is used as a hysteresis rising agent. A preferred hysteresis rising agent is preferably triphenyltriazine. Examples are Contained in Japanese Patent Nos. 2000-111,914 and 2000-275,434, and PCT / JP 0 0/0 2 6 1 9. ^ Two or more aromatic compounds may be mixed. The aromatic ring may be an aromatic hydrocarbon ring Or an aromatic heterocyclic ring. The retardation rising agent preferably has a molecular weight of 300 to 800. If the cellulose acetate film is a polymer film, it is preferably used per 100 parts by weight of cellulose acetate. 〇1 to 20 parts, particularly preferably 0.05 to 15 parts, and most preferably 0.1 to 10 parts of the aromatic compound. (Production of polymer film) The cellulose acetate film, which is a preferred polymer film, can be prepared by the method described in Japanese Technology -36- 200302361 Publication No. 2001-1745, March 15, 2001. Other polymer films can be made in the same way (extension of polymer film). The obtained polymer film can be stretched to control hysteresis. A better extension is 3 to 100%. The thickness of the polymer film is preferably 40 to 140 microns, and more preferably 70 to 120 microns. The extension conditions can be adjusted to reduce the standard deviation of the late phase axis angle. There is no special restriction on the extension method. For example, the film can be stretched with a tenter. In this case, immediately after the thin film is formed by the solvent coating method, the tenter is used to stretch in the lateral direction, and the film conditions are controlled so that the late axis angle has only a small standard deviation. In detail, immediately after stretching with a tenter, the film is kept close to the glass transition temperature and the tension is maintained to reduce the standard deviation of the late phase axis angle. If the film is kept below the glass transition temperature, the standard deviation will increase. Or use roller-to-roller mode to extend longitudinally, and increase the distance between the two rollers to reduce the standard deviation. (Surface treatment of polymer film) The polymer film used as the transparent protective film of the polarizing plate is preferably used for surface treatment. Surface treatment includes corona discharge treatment, glow discharge treatment, flame treatment, acid or alkali treatment, and ultraviolet (UV) treatment. An acid or alkali treatment (i.e., saponification treatment) is preferred. (Alignment layer) The function of the alignment layer is to enable alignment of the dish-shaped liquid crystal of the optically anisotropic layer. -37- 200302361 A preferred alignment layer includes an organic compound (preferably a polymer layer), an obliquely deposited layer of an inorganic compound, and a layer with micro grooves. In addition, an accumulation film formed of ω-glyceric acid, dioctadecyl dimethylammonium chloride, or methyl stearate according to the Langmuir-Blodgett technique can be used as an alignment layer. To prepare the alignment layer, the polymer film is preferably formulated. A preferred film polymer is polyvinyl alcohol. Particularly preferred is polyvinyl alcohol having a hydrophobic group. Due to the affinity of the hydrophobic group and the dish-shaped liquid crystal, the modified polyvinyl alcohol introduced with the hydrophobic group can evenly align the dish-shaped liquid crystal molecules. Hydrophobic groups can be placed at the ends or side chains of the polyvinyl alcohol backbone. The hydrophobic group is preferably a C6 or higher fatty group (especially an alkyl group or an alkenyl group) or an aryl group. The right hydrophobic group is placed at the terminal end of the main chain, and preferably a linker is provided between the terminal and the hydrophobic group. The linking group includes, for example, _s_, -C (CN) Ri-, -CS-, and combinations thereof. In the aforementioned groups, R and R2 are each independently a hydrogen or C1-6 alkyl group. If a hydrophobic group is placed on the side chain, the ethyl acetate (-CO-CH3) in the vinyl acetate unit of polyvinyl alcohol is replaced with a fluorenyl group (-co-R3) having c? Or more. In the foregoing formula, 'R3 has an aliphatic or aryl group of C6 or more. Denatured polyethylene glycol is described in Japanese Patent Application Laid-Open No. 9 (1 997) -1 5 2 509. Commercially available denatured polyvinyl alcohol (such as MP 1 03, MP 203, Ri i 3 0 by uraray company) can be used. The saponification degree of the (denatured) polyvinyl alcohol used in the present invention is preferably 80% or more, The degree of polymerization is preferably 200 or more. The wiping process uses paper or cloth to wipe the surface of the film layer in a certain direction and has the function of orientation -3 8- 200302361. It is preferable to wipe the film layer several times with a fiber cloth of the same length and thickness. Once the dish-shaped liquid crystal molecules in the optically anisotropic layer are aligned, they can maintain the alignment even after the orientation layer is removed. Therefore, although it is necessary to prepare an optical compensation film using an alignment layer, the finished optical compensation film need not include an alignment layer. If there is an alignment layer between the transparent support and the optically anisotropic layer, it is preferable to provide a bottom layer (adhesive layer) between the transparent support and the alignment layer. (Optical anisotropic layer) An optical anisotropy is prepared from a dish-shaped liquid crystal. Dish-shaped liquid crystal molecules are usually optically uniaxial. In the optical compensation film of the present invention, the angle between the dish-shaped plane and the transparent support in each liquid crystal molecule changes with the thickness (that is, the molecules are preferably oriented in the mixed alignment). In one direction of the optically anisotropic layer, the hysteresis is zero, that is, this layer has no optical axis. In order to form the optically anisotropic layer, the dish-shaped liquid crystal molecules are preferably aligned along the aforementioned alignment layer and maintain a fixed alignment. The thickness of the optically anisotropic layer is preferably 0.5 to 100 μm, and more preferably 0.5 to 30 μm. Dish-shaped liquid crystal molecules are described in various documents: C. Destrade et al., Π-molecular crystalline liquid crystals ", Vol. 71, 111, 1981; Japanese Chemical Society, Quarterly Chemistry Review (Japanese), Chapter 5, 10, Paragraph 2, 1994; B. Kohne et al., Angew. Chem. Soc. Chem. Comm., P. 1794, 1985; and J. Zhang et al., Journal of the American Chemical Society, Volumes 1 1 6 2 6 5 5 pages, 194 years. The polymerization reaction of dish-shaped liquid crystal molecules is described in Japanese Patent Application No. 8 (199.6)-2 7 2 8 4. -39- 200302361 The polymerizable group is preferably a disk-shaped nucleus bound to a disk-shaped liquid crystal molecule to cause a polymerization reaction of the compound. However, if the polymerizable group is directly bonded to the dish-shaped nucleus, it is difficult to maintain the alignment during the polymerization reaction. Therefore, the linking group is preferably introduced between the dish-shaped nucleus and the polymerizable group. To fix the alignment of the dish-shaped liquid crystal molecules, a photopolymerization initiator is used. Photopolymerization initiators are, for example, a-carbonyl compounds (described in U.S. Patent Nos. 2,36,7,66 1 and 2,3 6,7,670), acryl ethers (U.S. Patent 2,4,4,8, 8 2 8), α-hydrocarbon substituted acrolein compounds (U.S. Patent 2,7 2 2,5 1 2), polycyclic quinone compounds (U.S. Patent 2,9 5 1,7 5 8 and 3,0 4 6, 1 2 7), a mixture of triarylimidazole and p-aminophenone (US Patent 3 5 5 4 9, 3 6 7), acridine or phenazine compound Japanese Patent Application Publication 6 0 (1 9 8 5 )-1 0 5 6 6 7 and US Patent No. 4,2 3 9,8 50 0], and oxadiazole compounds (US Patent No. 4,21 2,9 7 0). The photopolymerization initiator is preferably used in an amount of from 0.01 to 20%, more preferably from 0.5 to 5%, based on the solid weight of the coating solution. The light irradiation of the photopolymerization reaction preferably uses ultraviolet rays. The irradiation energy is preferably 20 to 5000 mJ / cm2, and particularly preferably 1,000 to 800 mJ / cm2. The coating can be heated during light irradiation to accelerate the photopolymerization reaction. A protective film may be added on the optically anisotropic layer. (Delayer) The retarder is preferably used as a λ / 4 plate. The λ / 4 plate must have a hysteresis (measured at 590 nm) (Re 590) of 120 to 160 nm, which can include single or multiple films. This plate is preferably a single film which can provide a wide wavelength range of λ / 4, and is preferably a film roll. 200302361 λ / 4 must be laminated on a linear polarizing film so that the retardation axis of the plate and the absorption axis of the film are clamped at a 45 ° angle to form a circular polarizing plate. To enable roller-to-roller lamination, it is preferred to use an absorption shaft and a longitudinal clamp 45. The linear polarizing film and the retardation axis are parallel to the longitudinal λ / 4 plate. It is also preferable to use a rectangular linear polarizing film having an absorption axis parallel to the longitudinal direction, and a retardation axis and a longitudinal clamp 45. Rectangular λ / 4 plate. The retarders published in Japanese Patent Application Laid-Open Nos. 5 (1 9 9 3)-2 7 1 1 8 and 5 (1 9 9 3)-2 7 1 1 9 include a birefringent film with high hysteresis and low Hysteresis birefringent film. Laminating these birefringent films allows their optical axes to cross vertically. If the retardation difference between the two films is a λ / 4 plate in the entire visible light wavelength range, the retarder can theoretically be used as a λ / 4 plate in the entire visible light wavelength range. The retarder published in Japanese Patent Application Laid-Open Nos. 10 (9998) to 68881 16 contains two laminated polymer films made of the same material. At a certain wavelength, each film provides λ / 2, thus providing λ / 4 over a wide wavelength range. Japanese Patent Application Laid-Open Nos. 10 (19 9 8)-9 0 5 2 1 also disclose that two polymer films are laminated to form a retarder. This retarder also provides λ / 4 over a wide wavelength range. The λ / 4 plate preferably contains a single polymer film. In particular, the single-film λ / 4 plate described in the USP 20000-1 37 1 16 and the world patent 00/2 675 is preferred. The shorter the wavelength during measurement, the smaller the "phase" difference of the λ / 4 plate. The λ / 4 plate preferably has a hysteresis chirp (Re 4 50) measured at 450 nm of 100 to 125 nanometers, and a hysteresis chirp (Re590) measured at 590 nanometers of 120 to 16 〇nm. These Re hysteresis preferably meets the conditions of Re590-Re45022 nm, particularly preferably Re590-Re49025 nm ', and most preferably Re590-Re4502l0 nm. -4 1-200302361 The hysteresis 测 (Re 4 50) measured at 4 50 nm is preferably g 125 nm, and the hysteresis 测 measured at 5 50 nm is preferably 1 2 5 to 1 4 2 nm's hysteresis measured at 590 nm is preferably 130 to 152 nm; Re 5 50 and Re590 are preferably to meet Re590-Re55022 nm, especially Re590- Re55025 nanometers, preferably Re590-Re5520 nanometers. In addition, Re 5 50 and Re 4 50 are preferably to satisfy the conditions of Re 5 50-Re 4502 nm. Hysteresis (Re) is calculated from:

Re = (nx-ny) xd where η X is the refractive index along the retardation axis (that is, the direction providing the largest refractive index) on the plane of the λ / 4 plate; ny is the perpendicular to the retardation axis direction on the plane Refractive index; d is the thickness of the λ / 4 plate 'early position is nanometer. The λ / 4 plate is preferably a single polymer film that satisfies the following conditions: 1 < (nx-nz) / (nx-ny) < 2 where nx is the refractive index along the retardation axis on the plane of the λ / 4 plate, ny is the refractive index of the slow phase axis perpendicular to the plane of the λ / 4 plate, and ηζ is the refractive index in the thickness direction of the λ / 4 plate. To prepare a preferred λ / 4 plate with the aforementioned optical properties, the polymer film may be stretched. Alternatively, after the rod-shaped liquid crystal is coated, the polymer film is wiped to align the rod-shaped liquid crystal molecules. Then, for example, photo-polymerization is used to fix the alignment of the molecules to form an optically anisotropic layer. The polymer film thickness thus treated can form a λM plate. This λM plate can be extended obliquely or wiped to control the direction of the late phase axis. -42- 200302361 (λ / 4 plate with a single film) The thickness of a single film constituting a λ / 4 plate is preferably 5 to 1,000 micrometers, particularly preferably 10 to 500 micrometers, more preferably 40 to 200 micrometers. It is preferably 70 to 120 microns. (Polymer film) The polymer from which the polymer film is prepared is the transparent support material previously used to prepare an optical compensation film. The polymer is preferably a cellulose ester, particularly preferably a cellulose ester of a lower fatty acid. "Lower fatty acid π means fatty acids of C 6 or below. The carbon number is preferably 2 (cellulose acetate), 3 (cellulose propionate) or 4 (cellulose butyrate). Particularly preferred is cellulose acetate. Use cellulose esters of mixed fatty acids, such as cellulose acetate propionate and cellulose acetate butyrate. The average acetic acid content (degree of acetylation) of cellulose acetate is preferably 4 5 · 0 to 6 2 · 5%, especially It is preferably 5 5 · 0 to 6 1 · 0%, and most preferably 5 9 · 0 to 6 0 · 0%. (Hysteresis rising agent) A hysteresis rising agent may be added to the polymer (preferably cellulose acetate) film. In order to control the hysteresis, the hysteresis rising agent is, for example, a triphenyltriazine compound (which can be used in an optical compensation film). However, the hysteresis rising agent is preferably a rod-shaped compound having at least one aromatic ring, such as 1,4-cyclohexyl Alkyl dicarboxylic acid p-n-heptyl diester. The amount of the retardation rising agent is preferably from 0.05 to 20 parts per 1,000 parts by weight of the polymer, more preferably from 0.1 to 10 parts, more preferably It is 0.2 to 5 parts, preferably 0.5 to 2 parts. Two or more kinds of hysteresis rising agents can be used. The hysteresis rising agent is preferably the largest The take-up wavelength range is from 250 to 400 nm, and it is also preferred that there is substantially no absorption band in the visible wavelength range. -43- 200302361 In addition, it is preferable to extend the polymer film to control the refractive index (in the film The refractive index nx, ny, and nz along the slow axis, moving axis, and thickness direction of the surface). This film can be extended obliquely like the aforementioned PVA film, so that the slow axis and longitudinal direction are clamped by 45 °. (Coated type λ / 4 plates) The λ / 4 plate can be a coated λ / 4 plate as described in Japanese Patent No. 2001-21720. The coated λ / 4 plate includes two optically anisotropic layers sandwiching a twisted structure over a wide wavelength range It has significantly improved properties. The two optically anisotropic layers are preferably birefringent films or liquid crystal-containing layers. It is particularly preferred that at least one optically anisotropic layer is a liquid crystal layer, and it is preferred that both layers are liquid crystals. The optical properties of the liquid crystal layer are easier to control than the birefringent film. In the liquid crystal-containing anisotropic layer, the wiping direction of the liquid crystal molecules can be used to orient the late phase axis. If the amount and type of liquid crystal are appropriately controlled, The hysteresis can be tightly adjusted. The thickness and orientation of the optically anisotropic layer can be adjusted. Emission is measured in the range of 550 nm (also in the middle of the wavelength range of light), and the range is 1500 to 3500 nm. In a twisted structure, the twist angle is 3 to 45 °. If there is no distortion structure 0, then the product of thickness and orientation birefringence 乃 is retarded ((birefringent film) Other optically anisotropic layers are preferably in the range of 550 nm (also the middle of the light wavelength range). A birefringent film having a "phase" difference of 60 to 170 nanometers. The polymer of the birefringent film is, for example, a polyolefin (such as polyethylene, polypropylene, orbornene-based polymer), polyvinyl chloride, poly Styrene, polyacrylonitrile, polymill, polyarylate, polyvinyl alcohol, polymethacrylate, polyacrylic polymer and cellulose ester. Copolymers or mixtures can also be used. -44- 200302361 The optical anisotropy of the film is preferably derived from elongation. The film is preferably uniaxially stretched. For uniaxial stretching, it is preferred to use two or more rollers with different rotation speeds for longitudinal stretching, or two sides of the tenter to hold the film for transverse stretching. Two or more thin films are laminated so that the obtained laminated film satisfies the aforementioned conditions. The polymer film is preferably manufactured by a solvent coating method to reduce the unevenness of the film. The thickness of the film is preferably 20 to 500 nm, more preferably 50 to 200 nm, and most preferably 50 to 100 nm. (Reel-shaped polarizing plate) A λ / 4 plate and a linear polarizing film are laminated so that the retardation axis of the skin and the absorption axis of the film are substantially sandwiched by 45 ° to obtain a roll-shaped polarizing plate. If the absorption axis of the film and the longitudinal direction are substantially 45 °, the late phase axis of the plate is preferably substantially parallel to the longitudinal direction. If the absorption axis of the film is substantially parallel to the longitudinal direction, the late phase axis of the plate is preferably substantially 45 ° from the longitudinal direction. The retardation axis of the plate and the absorption axis of the film are preferably 41 to 49 °, more preferably 42 to 48 °, more preferably 43 to 47 °, and most preferably 44 to 46 °. Thus, the λ / 4 plate and the linear polarizing film were laminated to obtain a laminated composition. A protective film is preferably added to the back surface of the composition. The protective film is preferably made of a transparent polymer (light transmittance of 80% or more). Transparent polymers are, for example, polyolefins (e.g. Artone®, Zeonex®, Zeonor®), cellulose acetate, polycarbonate, polyarylate, polyether, and polyether maple. Commercially available transparent polymers and films can also be used. The retardation axis of the protective film is preferably substantially parallel to the absorption axis of the linear polarizing film. The linear polarizing film and the λ / 4 plate, or the linear polarizing film and the protective film are laminated with an adhesive -45- 200302361 adhesive. The adhesive is preferably an aqueous solution of a polyvinyl alcohol-based resin or a boride, and more preferably an aqueous solution of a polyvinyl alcohol-based resin. The polyvinyl alcohol-based resin is, for example, a denatured polyvinyl alcohol having a non-alcohol functional group such as an ethyl acetofluorenyl group, a sulfo group, a carboxyl group, or a hydrocarbyloxy group. The thickness of Nile has been preferably from 0.01 to 10 microns, particularly preferably from 0.05 to 5 microns. (Liquid crystal display "LCD ") The LCD of the present invention can be designed in a normal white mode (low or high voltage will show bright or dark images, respectively), or a normal black mode (low or high voltage will show dark or bright images, respectively) Image). If the present invention is applied to a reflective or transflective LCD, the active matrix is better than the simple matrix mode. It is particularly preferred to use TFT (thin film transistor), TFD (thin film diode) or MTM (metal insulation Metal mode). In the case of TFT mode, it is better to use cold polysilicon or grain boundary silicon. LCD is detailed in various documents or publications, such as "Liquid Crystal Device Handbook" (Japanese, Japan Science Promotion Association, Chapter 142th Committee, Nikkan Industry Press; `` Liquid Crystal Application '' (Japanese), oka η 〇, Baifuka η Press; `` Color LCD '' (Japanese, Kobayashi, Sangyo Shuppan Press; '' LCD monitors of the next generation π (Japanese, Uchida, Kogyou Chosakai Publishing House; n latest LCD monitors (Japanese), young liquid crystal scholars group, Sigma Publishing House; "Liquid Crystal: Original and New Applications of LCD" (Japanese), Young LCD Scholar Group, Sigma Press. (4) Embodiment F Sin Example 1 1: Preparation of Η AN mode liquid crystal cells On the glass substrate of the tin oxide) electrode, a polyimide 200302361 layer is added, and the layer is wiped to form an alignment layer. In addition, silicon oxide is deposited on another glass substrate having an iτ〇 electrode to form an alignment layer. Two glass substrates were placed face to face so that the gap between the two plates was 4.8 microns. Nematic liquid crystals (ZLI 1 1 2 3, A η = 0 · 1 3 9 6) from Mock were inserted into the gap to obtain Η AN The liquid crystal cell of the mode. The hysteresis of the obtained liquid crystal cell is 6 7 1 nm. (Preparation of roll type λ / 4 plate) At room temperature, 120 parts by weight of cellulose acetate (average acetic acid content: 5 9.5%), 9.36 parts by weight of triphenyl phosphate, 4.68 parts by weight of biphenyl diphenyl phosphate, and 1.000 parts by weight of a hysteresis rising agent (trans-1,4-cyclohexanedicarboxyl-4 -N-φheptyl diester), 543.14 parts by weight of dichloromethane, 99.35 parts by weight of methanol and 1 9.87 parts by weight, and Dissolve into a solution (blended solution). Pour this (viscous dope) solution on a moving stainless steel strip, send it to a drying area to dry at 25 ° C for 1 minute, and 4 5 ° C for 5 minutes. The film thus formed尙 Contains 30% by weight of solvent. After being stripped from the steel strip, it is wound at a faster speed than the moving speed of the steel strip and extended at 130 ° C. During this longitudinal stretching, the film is contracted laterally. After stretching, it was dried in a drying area of 12 ° C. for 30 minutes | minutes, and then rolled up. The formed film contained 0.1% by weight of a solvent. The thickness of the obtained roll-shaped film was 101 μm, The hysteresis 値 R e measured at 450 nm, 550 nm, and 590 nm using an ellipsometer (M-150 of Japan Spectrum Corporation) was 1 19.3 nm, 1 3 7.2 nm, and 1 4 2 · 7nm. The retardation axis of the film is parallel to the direction of movement (extension) (longitudinal direction). In addition, the refractive index is measured using an Abbe refractometer, and the effect of the angle on the hysteresis is also measured. Refractive index of the retardation axis), ny (refractive index of the vertical retardation axis) and nz (refractive index in the depth direction) are 1.60. -47- 200302361 (method of forming a linear polarizing film in the form of a roll) The PVA film was immersed in an aqueous solution containing 2.0 g / liter of iodine and 4.0 g / liter of potassium iodide at 25 ° C for 240 seconds, and then immersed in an aqueous solution of 10 g / liter of boric acid at 25 ° C for 60 seconds. The dipped film was stretched at a stretch ratio of 5.3 times, and then dried at 8 ° C to shrink under the condition that the width remained unchanged. Then it was taken by a tenter. And take up the film. The water content of the film before and after drying were 31% and 1.5%, respectively. The difference in the speed of movement between the left and right sides was less than 0.05%, and the angle between the introduction and departure of the film from the two centerlines of the tenter. It is 4 6 °. At the exit, no wrinkles and deformation can be seen in the film. The retardation axis and the moving direction (longitudinal) of the obtained linear polarizing film are at an angle of 4 5 °. At 5 500 nm, The light transmittance and polarized light are 43.7% and 99.97%, respectively. (Production method of roll-shaped polarizing plate) Triethyl cellulose film (Fuji tac TD80 of Fujifilm Corporation) and the aforementioned λ / 4 plates were immersed in a 0.1N sodium hydroxide aqueous solution at 55t for 1 minute to saponify the film and the two surfaces of the plate. One surface of the plate film was coated with a 30 micron thick polyvinyl alcohol-based adhesive layer, and the aforementioned linear polarizing film Laminated between triethyl cellulose film and λ / 4 plate in a roller-to-roller manner. The laminated composition thus obtained was dried at 8 ° C to obtain a roll-shaped polarizing plate having a thickness of about 2 4 1 micron (method of making optical compensation film) Pour the following ingredients into a mixing tank, stir and heat to dissolve each component Cellulose triacetate solution. Cellulose triacetate solution: -48-200302361 1 000 parts by weight of cellulose acetate (acetic acid content 60 · 9%) 8.1 parts by weight of triphenyl phosphate (plasticizer) 3.6 parts by weight of diphenyl diphenyl phosphate (plasticizer) 3 3 8 parts by weight of dichloromethane (first solvent) 2 7 parts by weight of methanol (second solvent) Pour 15 weight in another mixing tank Part of the following hysteresis rising agent, 80 parts by weight of dichloromethane and 20 parts by weight of methanol were stirred and heated to obtain a hysteresis rising agent solution. (Hysteresis)

5 2 parts by weight of the obtained lagging agent solution and 4 7 7 parts by weight of cellulose acetate were mixed and stirred to obtain a viscous dope solution. The obtained dope liquid was applied to a film by a band-shaped film-coating machine. When the amount of solvent remaining in the formed film reaches 50% by weight, the film is peeled from the transmission belt. Extend the film laterally at 17% at 130 ° C and leave it at 130 ° C for 30 seconds while maintaining the width. Then, the film was taken out from the jig to obtain a cellulose triacetate film. Re and Rth 値 were obtained by measuring cellulose acetate using an ellipsometry (M-150 from Japan Spectrum Co., Ltd.) at a wavelength of 500 nm. The angle of the late phase axis is measured using a light-49-200302361 sciplex analyzer (KOBTA-21 ADH from Qji Scientific Instruments) at a horizontal equidistance of 10 points. The standard deviation of the late phase axis is also calculated. The results are shown in Table 1. Table 1 Standard deviation of the retardation angle of the transparent carrier Re 値 Rth 値 Example 1 40nm 220nm 1.4 ° Example 2 40nm 220nm 1.3 ° On the aforementioned cellulose acetate film, use # 3 line coating A 0.1 N potassium hydroxide solution (isopropanol / propylene glycol / water in the solvent = 75/13/12 weight ° / 〇) was applied to the rod. After heating at 60 ° C for 10 seconds, the rod was washed with # 1.6 wire and the nozzle was sprayed with water at 40 ° C at 500 ml / m2. After that, the film was blown three times with a jet blade. It was then dried with hot air at 10 ° C to obtain saponified cellulose triacetate. On the saponified surface of cellulose triacetate, the following modified polyvinyl alcohol / 36 grams of water solution was coated with a #M wire coating bar ( It contains 12 g of methanol and 0.1 g of glutaraldehyde as the cross-linking agent), dried with 6 (TC hot air for 60 seconds, and 90 t: dried for 160 seconds, making the roll of triacetic acid An orientation layer is formed on the cellulose film. Then the orientation layer is wiped in the moving direction (longitudinal direction). (Denatured polyvinyl alcohol) — (CH2—CH) 〇2— — (ch2—ch) 12.〇—? CO CO φ άΗ3 _ (CH2—CH) 87.8—

OH 〇 一 (ch2) 4—〇-〇〇 一 ch = ch2 -50- 200302361 In order to prepare a coating solution, 38.4 g of the following dish-shaped liquid crystal compound was dissolved in 102 g of methyl alcohol, 4.1 g Ethylene oxide denatured trimethylolpropane triacrylate (V # 3 6 0 of Osaka Organic Chemical Co., Ltd.), 0.8 g of cellulose acetate butyrate (C ΑΒ-55 1-0.2 of Eastman Corporation), 0.2 g Cellulose acetate butyrate (CAB-531-1 from Eastman Corporation), 1.5 g of photopolymerization initiator (Irgacure® 907 from Ciba Corporation) and 0.5 g of sensitizer (Kayacure £ D £ TX from Kayaku, Japan). Then use The wire coating rod applies the solution to the alignment layer (wipe in a direction of 5 ° with the longitudinal clamp). The thus-treated film was fixed on a metal frame, and heated at 13 CTC for 2 minutes to orient the dish-shaped compound molecules in the single-zone ® block-shaped nematic phase. Ultraviolet rays were emitted from a high-pressure mercury lamp (120 W / cm), and the film was irradiated at 130 ° C for 1 minute to polymerize the disc-shaped liquid crystal molecules. It was then cooled to room temperature, so that the formed optically anisotropic layer was used to prepare an optical compensation film. (Dish-shaped liquid crystal compound)

Re (°) and Re (40 °) are measured on the plane containing the rubbing direction and the normal from the direction of the normal and the angle between the normal 40 ° and the direction -40 °. (-4 0 °). The results are shown in Table 2. 2 200302361

Optical compensation film ReTO0) Re (-40 °) Re (40 °) Example 1 38nm 42nm 83nm Example 2 40nm 44nm 87nm (manufacturing method of reflective HAN mode LCD)

An AN mode liquid crystal cell is laminated on a reflecting plate used in a commercially available reflective LCD. The optical compensation film was laminated on the unit cell with an acrylic adhesive, and the cellulose acetate side of the film was brought into contact with the unit cell. The unit cell wiping direction is parallel to the film wiping direction but opposite. In addition, an acrylic adhesive is used to laminate a roll-shaped polarizing plate on the laminated film so that the λ / 4 plate of the polarizing plate and the film are in contact with each other, and the retardation axis of the λ / 4 plate is parallel to the wiping direction of the unit cell. In this way, a reflective ΗAN mode LCD can be obtained. The produced LCD has the following components: Roll-shaped polarizing plate protective film (TD 8 0U) linear polarizing film (P va / i2) retarder (λ / 4 plate) optical compensation film transparent carrier (triacetyl cellulose film) optical Anisotropic layer (dish-shaped liquid crystal layer) Η AN mode liquid crystal cell reflector

A voltage was applied to the liquid crystal cell (white: 2 volts, black: 6 volts) to display the image, and the front contrast was measured with a front-view measurement using an instrument (EZ-Comparer 1 60D from ELDIM). The field of view with a contrast ratio of 5 or more is left-to-right (and the wiping side -52- 200302361 is vertical). The results are shown in Table 3. Table 3 LCD front contrast 値 Viewing angle Example 1 15 120 ° Example 2 12 100. "Example 21: Preparation of curved alignment mode liquid crystal cells On a glass substrate with an Iτο electrode, aluminum was deposited, but a part of the window was reserved for secondary transmission to form a diffuse refractive plate. The polyimide layer and layer on the plate were wiped Process to form an alignment layer. In addition, a polyimide film is provided on another glass substrate with an ITO electrode to form an alignment layer. The two glasses are placed facing each other with a gap of 10 microns. In this gap A nematic liquid crystal (MLI's ZLI 1132, Aη = 0.1396) was inserted to obtain a liquid crystal cell having a bending alignment mode. The hysteresis of the obtained liquid crystal layer was 698 nm. The following components were mixed to obtain a solution and therein Add cellulose triacetate powder (average particle size 2 mm) gradually with stirring. Cellulose triacetate solution ▲ 1 00 parts by weight of cellulose diacetate (acetic acid content 60 · 5%) 8 · 9 parts by weight of triphenyl phosphate (aid Plasticizer) 4.9 parts by weight of diphenyl diphenyl phosphate (plasticizer) 240 parts by weight of methyl acetate (first solvent) 10 0 parts by weight of bad hexanone (second solvent) 2 5 parts by weight Alcohol (third solvent) 2 5 parts by weight of ethanol (fourth solvent) 0.5 parts by weight of silica particles (average size 20 nm) 6 · 7 parts by weight of the hysteresis-rising agent used in Example 1 -53- 200302361 Place the mixture at room temperature (2 5 ° C) for 3 hours. Cool the phase colloid at -7 0 ° C for 6 hours, then heat to 50 ° C to obtain the blending solution. From this viscous dope solution, imitate Example 1 A cellulose triacetate film was prepared. The optical properties and thermal conductivity of the cellulose acetate film are listed in Table 1. The cellulose acetate film was immersed in a 5 5 ° C 1 · 5 N sodium hydroxide aqueous solution. Neutralize it with 0 · 1 N sulfuric acid at 0 ° C. Wash with warm water and dry in hot air at 100 ° C. So the surface of the cellulose acetate membrane is saponified. Example 1 is on the surface of saponified membrane Form an alignment layer and wipe it. To prepare a coating solution, dissolve 4 1.0 g in 102 g of methyl ethyl ketone: the dish-shaped liquid crystal compound used, 4.0 g of ethylene oxide-modified trihydroxypropane triacrylic acid Ester (V # 360 of Osaka Organic Chemical Co., Ltd.), cellulose oxobutyrate (C of Eastman Co., Ltd. AB-5 5-0 · 2), 0.2 3 g 酉 j cellulose cellulose (Eastman's CAB-5 3 1-1), 1. 3 5 g photopolymerization agent (Ciba Corporation's Irgacure 907) and 0.45 Gram sensitizer (Kayacure® DETX from Kayaku, Japan). Use # 3 wire coating bar to dissolve the cloth in the alignment layer. The film thus treated was fixed with a metal frame, heated in a 130 ° C bath for 2 minutes, and the dish was oriented in a single block dish nematic phase. Ultraviolet light from a high-pressure mercury lamp (120 W / cm) irradiated the film for 1 minute to polymerize the disc-shaped liquid crystal molecules. Cool the film to. The optically anisotropic layer thus formed can be used to prepare an optical compensation measurement on a plane including the wiping direction and the normal, along the normal, and the clamp 40. And -40. Lag in direction. The results are listed in Table 2 above, and the membrane is in the ventricle for 1 minute. Example 1 Methyl gram vinegar 7 butyl acid initiation liquid coating ° c constant compound 130 ° c room temperature film. Normal line-54- 200302361 (Preparation of linear polarizing film) Immerse P VA film in an aqueous solution containing 2 g / L of iodine and 4.0 g / L of potassium iodide at 25 ° C for 2 40 seconds, and then at 2 5 t Immerse in an aqueous solution containing 10 g / L of boric acid for 60 seconds. The immersed film was stretched by a tenter according to the stretch ratio of 7.4, and then dried and shrunk at 80 ° C while keeping the width constant, and wound up. The water content before and after drying was 30% and 1.3%, respectively. The retardation axis of the obtained linear polarizing film is parallel to the moving direction (longitudinal direction). The transmittance and polarization of the film at 550 nm are 43.9% and 99.96%, respectively. (Production method of λ / 4 plate) Following the production method of the optical compensation film of Example 1, the following coating solution was applied to cellulose triacetate with a wire coating rod, and dried at 130 ° C for 3 minutes to form a thickness of 0.3 micrometers. Vertical alignment layer. Solution for vertical alignment layer 5.0% by weight Steroid-denatured polyamino acid 25.0% by weight N-methyl-2-pyrrolidone 25.0% by weight ethylene glycol monobutyl ether ^ 45.0% by weight % Methyl ethyl ketone rolls the film with the vertical alignment layer into a tube, and clamps it at 45 ° according to the moving direction (longitudinal direction) for wiping alignment treatment. The following coating solution was applied on the vertical alignment layer and irradiated with ultraviolet rays emitted from a high-pressure mercury lamp (500 watts / cm 2) for 1 second. The resulting λ / 4 plate λ / 4 plate hysteresis was 138 nm. And the retardation axis and longitudinal clamp on the film surface are 45 °. Solution for optical anisotropic layer 3 2.6 wt% Dish-shaped liquid crystal used in Example 1 -55- 200302361 0.2 wt% cellulose acetate butyrate 3.2 wt% trimethylolpropane triacrylate 0.4 wt% Irgacure® 907 (steam Barco) 1.1% by weight Kayacure® DETX (Kayaku, Japan) 0.35% by weight The following π para palmitate compound n (C-2) 6 2.5% by weight methyl ethyl ketone paracompound (C-2)

(Manufacturing method of roll-shaped polarizing plate) The method of Example 1 was followed by islanding a commercially available cellulose triacetate film (Fujitac TD80 of Fujifilm Corporation) and the surface of the aforementioned λ / 4 plate. The three cellulose acetate surfaces of each plate film are coated with a polyethylene-based adhesive layer of about 30 microns thick, and the aforementioned linear polarizing film is roll-to-roll, and the triethyl cellulose film and λ / 4 are used. Plates and sandwiches. The resultant composite layer composition was dried at 8 Ot to obtain a roll-shaped polarizing plate having a thickness of about 2 41 m. (Manufacturing method of semi-transmissive OCB alignment mode LCD) Each side of the liquid crystal cell in curved alignment mode is laminated with an acrylic adhesive to make the optical compensation film, so that the cellulose acetate of the thin film can contact the cell. The orientation of the cell is parallel to the orientation of the film. On the film, a roll-shaped polarizing plate was laminated with an acrylic adhesive so that the λ / 4 plate in the polarizing plate was in contact with the film. -56- 200302361 The retardation axis of the λ / 4 plate and the orientation of the unit cell are antiparallel. A cymbal and a diffuser are laminated on the reflective plate side in order to obtain a backlight unit. Thus, a semi-transmissive LCD was manufactured. The obtained LCD has the following components: Roll-shaped polarizing plate protective film (TD 80 U), linear polarizing film (pva / i2) retarder (λ / 4 plate), optical compensation film, transparent carrier (triacetyl cellulose film), optical Anisotropic layer (dish-shaped liquid crystal layer) Liquid crystal cell in curved alignment mode (CB mode) Optical compensation film Optical anisotropic layer (dish-shaped liquid crystal layer) Transparent carrier (cellulose acetate) Roll-shaped polarizer late phase (Λ / 4 plate) Linear polarizing film (pva / i2) Protective film (TD 80 U) The diaphragm diffuser backlight plate applies a voltage to the liquid crystal cell (white: 2 volts, black: 6 volts), showing the image, And the instrument (EZDI EZ-contrast instrument 160D) was used to measure the forward-looking contrast 値. The contrast ratio of the viewing angle measured from left to right (vertical alignment) is 5 -57- 200302361 or above. Result (five) The diagram is simple. Figure 1 is No. 2 is No. No. 3 is No. No. 4 is No. No. 5 is No. No. 6 is No. No. 7 is No. No. No. 8 is the main part of No. 8. Generation 11,21 13,23 A 1… A η C 1… C η 12,22 A χ, C χ L 1, L2 18,28 7 1,81 72,82 are listed in Table 3 above. A plan view illustrating an example in which the composite film extends diagonally. Another example of a plan view compound film extending diagonally. Another example of a plan view film extending diagonally. Another example of a plan view film extending diagonally. Another example of a plan view film extending diagonally. Another example is a plan view of a conventional polarizing plate formed by punching a compound film extending diagonally. A plan view of a polarizing plate of the present invention formed by punching. Explanation of Table Symbols Centerline Trajectory Grip Grip Middle; L ·, Line Release Point Distance on Both Sides Last Grip Absorption Axis Longitudinal -58-

Claims (1)

200302361 Patent application scope 1. A polarizing plate comprising a linear polarizing film with a longitudinal axis and an absorption axis, and a retarder with a longitudinal and retarding axis, wherein the longitudinal direction of the linear polarizing film is substantially parallel to the longitudinal direction of the retarder The absorption axis of the linear polarizing film is substantially parallel to the longitudinal direction of the linear polarizing film, and the retardation axis of the retarder is not substantially parallel or perpendicular to the longitudinal direction of the retarder. 2. If the polarizing plate of item 1 of the patent application scope, wherein the retarder is a λ / 4 plate, and the retarder of the retarder is substantially 45 ° from the longitudinal direction of the retarder. 3. A type of polarizing plate comprising a linear polarizing film with a longitudinal and absorption axis and a retarder with a longitudinal and late phase axis, wherein the longitudinal direction of the linear polarizing film is substantially parallel to the longitudinal direction of the retarder, and the linear polarizing film The absorption axis is not substantially parallel or perpendicular to the longitudinal direction of the linear polarizing film, and the retardation axis of the retarder is substantially parallel to the longitudinal direction of the retarder. 4. If the polarizing plate of item 3 of the patent application scope, wherein the retarder is a λ / 4 plate, and the absorption axis of the linear polarizing film is substantially at an angle of 45 ° with the longitudinal direction of the linear polarizing film. 5. A liquid crystal display comprising a liquid crystal cell and at least one polarizing plate. The liquid crystal cell includes a pair of substrates, each of which includes a transparent electrode with an alignment layer on the surface, and nematic liquid crystals with curved or mixed alignment are sealed on the two substrates. Between layers, and wherein the polarizing plate is selected from the polarizing plate of any one of claims 1 to 4. 6. The liquid crystal display according to item 5 of the patent application, wherein an optical compensation film is provided between the liquid crystal cell and the polarizing plate, and the optical compensation film contains a transparent carrier and an optically anisotropic layer of a dish-shaped liquid crystal with a fixed alignment. The anisotropy-59-200302361 layer has an optical anisotropy of Re (0 °) hysteresis, and Re (40 °) hysteresis, which is 80 to 130 nm, and 10 to 60 nm. 7. The optical anisotropy of the transparent carrier of the liquid crystal display according to item 6 of the patent application is Re hysteresis, and the hysteresis of Rth is 70 to 400 nm. 8. A type of liquid crystal display, in which the film of the polarizing film is continuously sent to the curved path. When the polymer is thin, the film is stretched according to the following conditions: (i) The longitudinal stretch ratio is in the range of 1 · 2 to 10 P ( ii) The range of lateral extension ratio is 1.1 to 20.0 p (iii) The difference in the longitudinal movement rate of the clamps on both sides is (iv) Keep the volatile content of 5% or more (v) at the exit of the path, Movement direction and angle in the range of 20 to 70 °; It is characterized in that the liquid crystal display is operated in OCB (optical 祎 H AV (hybrid-alignment-nematic) mode or ECB (electric mode). 10 to 60 nm, R e (-4 0 °) Hysteresis, where the optical compensation film 补偿 is 10 to 70 nanometers, which makes the clamps on both sides of the optical polymer film 1, within the figure, 1% or less, the state, the extension of the quality Direction clip ^ compensated bending) mode, sub-controlling complex refractive index)