TW200301375A - Circularly polarizing plate and liquid crystal display device - Google Patents

Abstract

A circularly polarizing plate in a continuous length comprising: a polarizing film having an absorption axis neither parallel nor perpendicular to the lengthwise direction, at least one optical film provided at: at least one surface of the polarizing film; and an adhesive layer provided at an outside of at least one of the polarizing film and the optical film, wherein an angle between the absorption axis and the slow axis of at least one of the optical films is no less than 10 degrees and less than 90 degrees, and the formulation (1) and (II) defined in the specification are satisfied.

Description

200301375 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 are briefly explained.) (1) The technical field to which the invention belongs The technical scope of the invention The invention relates to a type with excellent durability The circular polarizing plate with high performance and productivity can obtain a circular polarized light for any incident light in the visible light range; and a liquid crystal display device using the same with high display quality. (II) Prior art I. Technical background With the popularity of liquid crystal display devices (hereinafter abbreviated as n LCD "), the demand for polarizing plates has increased significantly. Polarizing plates are usually laminated with a protective film, a protective surface film, a retardation plate (λ / 4 plate, λ / 2 plate) or similar optical film on the two or one side of a polarizing film (film) with polarizing ability. To make. Furthermore, an adhesive layer is usually provided on the outer side of at least one side of the optical film and the polarizing film, and the polarizing plate is adhered to other components such as a liquid crystal display device via the adhesive layer. As the material for the polarizing film, polyvinyl alcohol has been mainly used (hereinafter abbreviated " PVA "). The polarizing film can be formed by uniaxially stretching a PVA film, then dyeing it with iodine or a dichroic dye (or in addition, stretching after dyeing), and further, crosslinking with a boron compound. The polarizing film is generally manufactured by stretching in a direction in which the film is continuously moved (longitudinal (axial) direction) (longitudinal stretching), so the absorption axis of the polarizing film becomes almost parallel to the longitudinal direction. It is desirable to laminate a protective film with low hysteresis on at least one side of the polarizing film -6-200301375 'because in the case where the protective film has birefringence, this can change the polarization state. However, there is still a problem that the hysteresis increases depending on the ambient temperature and humidity. Therefore, 'the countermeasure for this problem is that the protective film has been laminated on the polarizing film'. Therefore, the low axis of the protective film becomes perpendicular to the transmission axis of the polarizing film (that is, the low axis of the protective film becomes absorption with the polarizing film. The axes are parallel). However, in this example, it has been found that because the low axis of the protective layer is parallel to the absorption axis of the polarizing film, the resulting laminated board has poor dimensional stability, especially including the problem of time stability. That is, on the conventional polarizing plate, it has been found that the protective film shrinks in the same direction when the polarizing film contracts. Although this force can be blocked by an adhesive layer, it cannot sufficiently reduce the shrinkage of the polarizing plate. Similarly, it has been found that the λ / 4 plate (quarter wave plate) has many applications related to anti-reflection films and liquid crystal display devices and has been laminated on the polarizing film, so the optical axis of the polarizing film will be different from λ / The optical axes of the 4 plates intersect. On the other hand, the polarizing plate has been arranged in the conventional LCDs, so the transmission axis of the polarizing plate will be inclined at 45 degrees with the vertical or horizontal direction of the screen. Therefore, in the example of manufacturing the polarizing film by using the longitudinal stretching or the transverse stretching as described above, a cutting step has been required to turn the manufactured film into a roller in a direction inclined at 45 degrees from the longitudinal direction of the roller. Individual polarizers are cut out of the polarizers of the form. In this example, 'includes a problem that the yield of the polarizing plate is low or it is difficult to reuse the polarizing plate after lamination, resulting in an increased amount of waste. To solve this problem, it has been suggested to tilt the orientation axis of the polymer to a desired degree (relative to the film transport direction) to obtain a polarizing film. For example, Japanese Patent Laid-Open Publication No. 9 9 2/2 0 0 0 proposes uniaxial stretching in the horizontal 200301375 or the longitudinal direction, and at the same time at different speeds in the lateral or longitudinal direction different from the stretching direction. Tension is used to stretch the left and right sides of the film in the stretching direction, so the orientation axis is inclined relative to the uniaxial stretching direction. However, in an example of a method using, for example, a stretching machine system in which the conveying speeds of the left and right sides must be made different from each other, it is difficult to obtain a desired tilt angle (45 degrees with respect to the polarizing plate), and wrinkles and Wiggle. In order to reduce the difference in conveying speed between the left and right sides, the stretching step needs to be extended, resulting in huge equipment costs. Similarly, Japanese Patent Laid-Open Publication No. 1 8 2 7 0 1/1 9 9 1 proposes a method for manufacturing a film having a stretched shaft having any angle θ (for the direction in which the film moves). The mechanism is On the two edges of the continuous film, a plurality of pairs of film gripping points with an orientation angle of Θ (for the direction of movement of the film) are provided. As the film moves, each pair of points can stretch the film in the direction θ. However, in this method, a film moving speed difference between the left and right sides of the film may occur, and the film may be distorted or wrinkled. In order to reduce this, extremely long stretching steps are required, which leads to huge equipment costs. > Furthermore, Japanese Patent Laid-Open Publication No. 113920/1990 proposes a production process in which the two edges of the film are gripped by two rows of chalks that can be moved on a track (which is configured within a predetermined range of movement). The moving distance between the two edges is different, so the film can be stretched in a direction that intersects with the longitudinal direction of the film. However, in this process, distortions or wrinkles are also formed after being skewed and stretched, so this process is not convenient for optical films. Similarly, Korean Patent Laid-Open Publication No. P200 1-005 1 84 proposes a polarizing plate in which the transmission axis is tilted by rubbing treatment. However, it is generally known that the orientation obtained by friction is effective only at the most nanometer series on the surface of the film, and this technique cannot sufficiently orient a polarizing element containing iodine or a dichroic dye. As a result, the disadvantage is that it has a low polarization ability. (3) Summary of the Invention The present invention therefore aims to solve various problems of the aforementioned techniques mentioned above. That is, the object of the present invention is to provide a skew-oriented circularly polarizing plate having a continuous length and excellent durability, which can obtain a circularly polarized light over a wide wavelength range and can improve the yield. Another object of the present invention is to provide a circular polarizing plate having a protective film, which has excellent durability and can obtain a circularly polarized light over a wide wavelength range. A further object of the present invention is to provide a process for manufacturing the circularly polarizing plate described above. A still further object of the present invention is to provide a reflective liquid crystal display device using a circularly polarizing plate, which can correct the deviation of the circular polarization at a shorter wavelength side to provide a high display quality without color deviation. It was found that the above-described object of the present invention can be obtained by the following configurations. 1) A circular polarizing plate having a continuous length, comprising a polarizing film whose absorption axes are not parallel or perpendicular to the longitudinal direction; at least one surface of the polarizing film is covered with at least one optical film, and at least one of the polarizing film and the optical film is An outer side is provided with an adhesive layer; wherein an angle between an absorption axis of the polarizing film and a low axis of the at least -9-200301375 piece of optical film is 10 degrees to less than 90 degrees; durability test of the circular polarizing plate Later, when the light of 450 nm is incident on the circular polarizing plate from the side of the polarizing film, the transmittance of the circular polarizing plate in a direction parallel to the transmission axis and its transmittance in a direction perpendicular to the transmission axis The ratio of light transmittance can satisfy the following formula (I); and after the endurance test of the circularly polarizing plate, when 5 90 nm light enters the circularly polarizing plate from the side of the polarizing film, the circularly polarizing plate is in contact with The ratio of the transmittance in a direction parallel to the transmission axis and the transmittance in a direction perpendicular to the transmission axis can satisfy the following formula (II): Formula (I) 0 · 95 < T // (4 5 0 ) / Τ 丄 (4 5 0) · 05 Formula (II) 0.95 < T // (590) / Τ 丄 (590) 21. 05 where T // (4 50) represents the light transmittance of a circular polarizer in a direction parallel to its transmission axis when 450 nm light is incident from the side of the polarizing film; T 丄 (450) represents when When the light of 450 nm is incident from the side of the polarizing film, the light transmittance of the circular polarizer in a direction perpendicular to its transmission axis; T // (590) represents when the light of 590 nm is incident from the side of the polarizing film , The light transmittance of the circular polarizing plate in a direction parallel to its transmission axis; and T (5 9 0) represents that when 590 nm light is incident from the side of the polarizing film, the circular polarizing plate is at its transmission axis Transmittance in the vertical direction 〇 2) —A circular polarizing plate comprising a polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction. At least one surface of the polarizing film is covered with at least one optical film. An adhesive layer is provided on the outer side of at least one of the film and the optical film; wherein the angle between the absorption axis of the polarizing film and the low axis of the at least one optical film is 10 degrees to less than 90 degrees; at the circularly polarized light After the durability test of the board, when 450 nanometers of light from the side of the polarizing film entered the circular polarization-1 0 _ 200301375 In the case of a light plate, the ratio of the light transmittance of the circularly polarizing plate in a direction parallel to the light transmission axis to the light transmittance in a direction perpendicular to the light transmission axis may satisfy the formula (I) described in the above description 1). ); And after the endurance test of the circularly polarizing plate, when light of 590 nm is incident from the side of the polarizing film into the circularly polarizing plate, the circularly polarizing plate transmits light in a direction parallel to the transmission axis The ratio of the transmittance to its transmittance in a direction perpendicular to the transmission axis may satisfy the formula (II) described in the above description 1). 3) A process for manufacturing a circularly polarizing plate as described in (1) or 2) above, which includes using a clamp to grip the two edges of the film to stretch a continuously fed polymer film, And move the device in the longitudinal direction of the film while granting tension there; the track L 1 of the jig starts from a point that essentially begins to grip one side of the polymer film, to the essence that the grip is on the same side To the point of release; the track L2 of the jig starts from a point where the other side of the polymer film is substantially gripped to a point where the grip is substantially released from the same side; and The distance W between the grip release points can satisfy the following formula (1), and the difference between the longitudinal conveying speed of the clamp between the two films is less than 1%:

(1) I LI-L2 | > 0.4W 4) A process for manufacturing a circular polarizing plate as described in 3) above, wherein at least one optical film sheet whose low axis is parallel to the longitudinal direction is continuously laminated on The polarizing film is on at least one side. 5) A liquid crystal display device that insists on using a circular polarizing plate cut from a continuous-length circular polarizing plate described in the above description 1) or a circular polarizing plate described in 2) as a configuration in the liquid crystal From the two sides of the unit up to _ 1 1-20030137ο One piece of circular polarizer is missing. It has been found in the circular polarizing plate of the present invention that due to the intersection of the absorption axis of the polarizing film and the low axis of the optical film, the shrinkage of the circular polarizing film in the direction along the absorption axis of the polarizing film can be caused by The presence of an optical film with intersecting optical axes effectively reduces · even an adhesive layer with a weak elastic force can sufficiently reduce shrinkage (due to the presence of the adhesive layer). Furthermore, because the absorption axis of the polarizing film in the continuous-length circular polarizer of the present invention is neither parallel nor perpendicular to the longitudinal direction (hereinafter, this continuous-length polarizer is sometimes referred to as "skew-oriented" Polarizing plate "), which can significantly improve the yield in the cutting step. The present invention further includes the following structure: 6) a circular polarizing plate comprising at least one polarizing film having polarizing ability; wherein one is cut from A polarizing plate with a continuous length of polarizing plate whose absorption axis is neither parallel nor perpendicular to the longitudinal direction, and a broadband λ / 4 plate (which will provide a λ / 4 plate with 1/4 wavelength retarded birefringent light and 1 / 2 wavelength phase retarded birefringent λ / 2 plates combined) laminated so that their optical axes intersect each other. 7) —A circularly polarizing plate containing at least one piece of polarized light with polarizing power and a protective film laminated on at least one side of it Film, wherein a polarizing plate having the protective layer and a polarizing film (the relationship between the low axis of the protective film and the absorption axis of the polarizing film is 10 degrees to less than 90 degrees) and a broadband λ / 4 plate ( It will be available 1/4 wavelength retarded birefringent λ / 4 plates are combined with λ / 2 plates that can provide 1/2 wavelength retarded birefringent light, so that their optical axes intersect each other. 8) — a kind of manufacturing circular polarizer The manufacturing process includes a polarizing plate cut from a polarizing plate with a continuous length of 200301375 degrees and a broadband λ / 4 plate (which will provide a 1/4 wavelength retarded birefringent light and a λ / 4 plate that can provide 1/4 2 wavelength phase retarded birefringent λ / 2 plates combined) so that their optical axes intersect each other; the polarizing plate can be prepared by stretching a continuously fed film, so the orbit L i of the fixture is removed from the film The starting point of the substantial grip of one edge starts to the releasing point of the substantial grip; the track L2 of the other clamp starts from the starting point of another substantial grip of the other edge of the polymer film and ends at the releasing point of the substantial grip. ; And the distance w between the two gripping release points can satisfy the following formula (丨); and in order to maintain the self-supporting properties of the polymer film, the volatile component is maintained at a level of 5% or more, and then Allowed when reducing volatile ingredients Shrinkage = Formula (1) | L2-L1 | > 0.4W. 9) A liquid crystal display device, wherein the at least one circular polarizing plate disposed on the liquid crystal cell is the circle described in 6) or 7) above. As described above, the circularly polarizing plate of the present invention is a circularly polarizing plate that cuts from a continuous length of polarizing plate having a polarizing plate whose absorption axis is neither parallel nor perpendicular to the longitudinal direction (hereafter, this Continuous-length polarizers are referred to as skewed polarizers in some cases and a broadband λ / 4 plate as mentioned above, and can improve the output in the step of cutting individual polarizers. In addition, the resulting circular polarizing plate has excellent polarizing ability. In the present invention, a semi-transmissive liquid crystal display device having the following structure is preferred. 10) a semi-transmissive liquid crystal display device, which has a backlight, a circular polarizer, and a liquid crystal display element that can be used for both reflective and transmissive display devices, of which: -13- 200301375 (a) A polarizing film in a circularly polarizing plate is disposed between a 1/4 wavelength plate and a protective film having an in-plane retardation 20 of 20 nm or less, so the angle between the absorption axis of the polarizing film and the low axis of the protective film and The angle between the absorption axis of the polarizing film and the low axis of the 1/4 wavelength plate is 20 degrees to less than 70 degrees; and (b) the thickness of the circular polarizing plate is 80 micrometers to 250 micrometers. 1 1) A process for manufacturing a circularly polarizing plate for a transflective liquid crystal display device as described in the above 10), which includes a polymer film (for a polarizing film) continuously fed by using a clamp, and Two edges, and tension is granted when the clamp is moved in the longitudinal direction of the film and stretched during this period, so: (i) the track L1 of the clamp starts from the substantial grip starting point of one edge of the film to the substantial grip Up to the release point; the track U of the other clamp starts from another substantial grip start point on the other edge of the polymer film and ends at the substantial grip release point; and the distance w between the two substantial grip release points may be Satisfy the following formulae (1) and (ii) in order to maintain the self-supporting properties of the polymer film, maintain the volatile component at a level of 5% or more; and then allow the film to shrink when the volatile component is reduced; and The resulting polarizing film is laminated with a protective film and / or a λ / 4 plate, while maintaining the water content of the polarizing film at a level of 5% or less, thus forming a circular polarizing plate. Formula (1) I L2-L1 | > 0.4W The present invention will be described in more detail below. The circular polarizing plate of the present invention includes a polarizing film having a polarizing ability, and at least one optical film is provided on two sides or one side of the polarizing film through an adhesive layer or an adhesive layer. Herein, the optical film of the present invention means a film which must have properties as a circular polarizing plate. It means in particular a surface protective film, a protective film or a phase retardation film. The phase retardation film can be any thin film that can provide circular polarizing properties when it is superimposed on a linear circular polarizer, and the number of the films is not particularly limited. Similarly, the surface protection film includes a hard coating layer, an AG layer, an AR layer, and a CV layer, and a combination of two or more thereof may be selectively used. It may be additionally satisfied that the low axis of at least one of the two or more optical films intersects the absorption axis of the polarizing film as mentioned above. A viable circularly polarizing plate is usually obtained by manufacturing a circularly polarizing plate of a continuous length (typically a roller shape) and cutting it according to the end use. The name '' circular polarizing plate 'as used in the present invention has the meaning of use unless it is otherwise specified in detail, and includes both a circular polarizing plate of continuous length and a circularly polarizing plate obtained by cutting out from each other. In the present invention, the angle between the longitudinal direction of the circularly polarizing plate of a continuous length and the absorption axis of the polarizing film can be freely set in a range of 10 degrees to less than 90 degrees, so it can be combined with other optical members according to the used And easily choose the right angle. ® As described above, the continuous-length circular polarizer of the present invention is characterized in that its absorption axis is neither parallel nor perpendicular to the longitudinal direction (that is, it is skew-oriented). Specifically, in the circular polarizing plate 85 shown in FIG. 1, an optical film 70 having a low axis 7 1 is laminated on at least one side of a polarizing film 80 having an absorption axis 8 1 via an adhesive layer 74 (if necessary). The circular polarizing plate is characterized in that the angle Θ between the absorption axis 81 of the polarizing film and the stretching axis of the optical film (that is, the dotted line 7) is in a range from 10 degrees to less than 90 degrees. In this range, -15- 200301375 excellent durability has been obtained. The angle between the longitudinal direction of the circularly polarizing plate of the continuous length and the absorption axis is preferably 20 degrees to 70 degrees, more preferably 40 degrees to 50 degrees, and particularly preferably 44 to 46 degrees. This feature can provide the circularly polarizing plate to be cut as shown in Fig. 2, and therefore the yield of the circularly polarizing plate in the cutting step can be significantly improved. Here, the angle between the absorption axis of the polarizing film and the low axis of the optical film can be estimated by separating the optical film and the polarizing film of the circular polarizing plate from each other, and measuring the absorption axis of the polarizing film and the low axis of the optical film. . Similarly, the absorption axis of a polarizing film is defined as the axial direction that provides the maximum transmission density when a polarizing plate is stacked on a polarizing plate whose absorption axis is known to be at the position of crossed Nicols. Similarly, the low axis of an optical film is defined as the axis that provides the maximum birefringence when birefringence is measured in the plane of the optical film. The angle between the absorption axis of the polarizing film and the low axis of the optical film means an angle between two axes, and is preferably 10 degrees to less than 90 degrees. The transmission density of the polarizing film can be measured by a transmission densitometer (for example, Xite (Rite.) 3 1 OTR) equipped with a Status M filter (Status M fi 1 ter); a protective film The refractive index can be measured by a polarizing analyzer (ρ ο 1 a 1. izati ο nana 1 yzer) (for example, a polarizing analyzer manufactured by Shimazu Seisakusho KK (ρ 〇1 arizati ο η ana 1 yzer) ) AEP-1 0) to measure. Furthermore, 'in the example of the optical film where the low axis intersects the absorption axis of the polarizing film', the low axis 71 of the protective film 70 in the above-mentioned FIG. 1 is parallel to the longitudinal direction 8 2 or transverse direction 8 3 of the polarizing plate, and The absorption axis 81 of the polarizing film 80 crosses the vertical direction 8 2 or the horizontal direction 8 3 at an angle of preferably 20 to 70 degrees (more preferably 40 to 50 degrees, particularly preferably 44 to 46 degrees). It is best to use a roller-shaped polarizing plate of the type-1 6-200301375, which has a protective film with a low axis parallel to the longitudinal direction laminated on at least one side of the polarizing film (its absorption axis 81 crosses the longitudinal direction 82 at an angle of about 45 degrees) on. This polarizing plate roller can obtain good polarizing plate yield. Similarly, the circular polarizing plate of the present invention preferably has a single-plate light transmittance of 35% or more at 550 nm or more, and the polarization degree at 550 nm is 80% or more many. The veneer light transmittance is preferably 40% or more, and the polarization degree is preferably 95.0% or more, more preferably 99% or more, and particularly preferably 99.9% or more. In the present invention, light transmittance additionally means veneer light transmittance, unless otherwise specified in detail. The circular polarizing plate of the present invention has excellent single-plate light transmittance and degree of polarization. In the case where it is used in a liquid crystal display device, it can improve its contrast and is therefore excellent. The circular polarizing plate structure of the present invention includes at least one optical film and a polarizing film, and they are arranged so that the angle between the low axis of the optical film and the absorption axis of the polarizing film becomes from 10 degrees to less than 90 degrees. When light of 450 nm is incident from the side of the polarizing film of the circular polarizing plate, the transmittance (T // (450)) of the circular polarizing plate of the present invention in a direction parallel to the transmission axis The ratio of the light transmittance (Τ 丄 (450)) in the direction in which the optical axis is perpendicular can satisfy the following formula '· Formula (1) 0.95ST // (450) / T 丄 (450) 51.05 Furthermore, formula 0 · 98 $ Τ // (450) / Τ 丄 (4 5 0) S1.02 is better. Similarly, when 5 90 nm light is incident from the polarizing film edge of the circular polarizing plate, the light transmittance (T // (590)) of the circular polarizing plate of the present invention in a direction parallel to the transmission axis is the same as The ratio of the light transmittance (Τ 丄 (5 9 0)) in the direction perpendicular to the light transmission axis can satisfy the following formula:-1 7-200301375 Formula (II) 0.95ST // (590) / T ± (590) S1.05 Furthermore, the formula 0.98 £ ding // (5 90) / 丄 丄 (5 90) $ 1.02 is better. In the case of using a single thin-film optical film as a λ / 4 plate, it is preferable that the hysteresis chirp (R e (4 50 0)) measured at a wavelength of 450 nm is 100 to 1 2 5 In the range of nanometers, the hysteresis (Re (590)) measured at a wavelength of 590 nanometers is in the range of 120 to 160 nanometers, and the relationship between Re (590) and Re (450) is So Re (590) -Re (45 0) 22nm. This relationship is more preferably such that Re (590) -Re (450) 25 nm, and most preferably Re (590) -Re (450) 2l0 nm. Preferably, the hysteresis chirp (Re (450)) measured at a wavelength of 450 nanometers is in the range of 108 to 120 nanometers, and the hysteresis chirp (Re (550)) In the range of 125 to 142 nanometers, the hysteresis (Re (59 0)) measured at a wavelength of 590 nanometers is in the range of 130 to 152 nanometers, and in the range of Re (5 9 0 ) And Re (5 50) are Re (5 90) -Re (550) 22 nm. This relationship is more preferably Re (590) -Re (550) 25 nm, and most preferably Re (5 90) -Re (5 50) 210 nm. It is also preferable that the relationship between Re (450) and Re (550) is Re (550) -Re (450) 210 nm. In the case of using a single thin-film optical film as a λ / 2 plate, it is preferable that the hysteresis (R e (4 50 0)) measured at a wavelength of 450 nm is between 2 0 and 2 5 0 In the range of nanometers, the hysteresis (Re (590)) measured at a wavelength of 590 nanometers is in the range of 240 to 320 nanometers, and between Re (590) and Re (450) The relationship is Re (5 90)-Re (450) ^ 4 nm. This relationship is more preferably Re (590) -Re (450R10 nm, most preferably Re (590)-200301375

Re (4 5 0) 220 nm. It is preferable that the hysteresis chirp (Re (450)) measured at a wavelength of 450 nm is in the range of 2 16 to 240 nanometers, and the hysteresis chirp measured at a wavelength of 500 nm (Re (550)) is in the range of 250 to 284 nm, and the hysteresis (Re (5 90)) measured at a wavelength of 590 nm is in the range of 2 60 to 30 04 nm, and in R The relationship between e (5 9 0) and Re (5 50 0) is R e (5 9 0 0 Re (5 5 0) 24 nm. This relationship is more preferably Re (590) -Re (5 5 0) 210 nm, most preferably Re (5 90) -Re (5 5 0) 220 nm. It is also preferable that the relationship between Re (4 5 0) and Re (5 5 0) is Re (5 5 0) -Re (450) 220 nm. Hysteresis 値 (Re) can be calculated according to the following formula: Hysteresis 値 (Re) = (nx-ny) xd where nx is the low axis in the plane of the phase difference plate The refractive index (maximum in-plane refractive index) in the direction, ny is the refractive index perpendicular to the low-axis direction in the plane of the phase retardation plate, and d is the thickness (nanometer) of the phase retardation plate. Satisfactorily satisfies the following formula: l < (nx-nz) / (nx-ny) < 2 where η X is the low-axis square in the plane of the phase difference plate Refractive index (maximum in-plane refractive index), ny is the refractive index ′ perpendicular to the low-axis direction in the retardation plate plane, and η Z is the refractive index in the thickness direction. ≪ Optical film > An optical film of a specific nature can be produced from a polymer produced by a process described below. (Phase retardation film) -19- 200301575 As for the phase retardation film to be used in the present invention, it has been clarified, for example, in this patent publication The retardation plates described in the bulletin case numbers 2 7 1 1 8/1 9 9 3 and 2 7 1 1 9/1 9 9 3, wherein a birefringent film having a large hysteresis and a birefringence having a small hysteresis The film is laminated so that the optical axes intersect at the correct angle. For this film, if the retardation between the two films is all λ / 4 in the visible light range, the retardation plate can theoretically be used in the entire visible light range. λ / 4 plate. Similarly, a phase retardation plate described in Japanese Patent Laid-Open Publication No. 6 88 1 6/1 998 can be used, which will act as a polymer film of λ / 4 plate at a specific wavelength and Acts as λ / at the same wavelength Polymer films of the same material of 2 plates are laminated to each other, which can be used as a λ / 4 plate in a wide wavelength range; and the phase difference described in Japanese Patent Laid-Open Publication No. 9 0 5 2 1/1 9 98 Plate which laminates two polymer films in order to obtain λ / 4 over a wide wavelength range. Furthermore, in the present invention, the retardation plates described in Japanese Patent Laid-Open Publications Nos. 1 3 7 1 1 6/2000 and WO 00/2670 5 show (as a single polymer film) that they are relatively short when measured. The wavelength has a small phase difference. This technique using a single-phase retardation film is better, so its production steps can be simplified ', but it has also been found that the circularly polarized light generated is insufficient. Therefore, in the present invention, in the case where the phase retardation film which is to be laminated on the two or one side of the polarizing film having polarizing ability through an adhesive layer or an adhesive layer, and which includes a single film, it is preferable that A retardation film is laminated on the polarizing film so that the angle between the low axis of the retardation film and the absorption axis of the polarizing film becomes a range of 10 degrees to less than 90 degrees, resulting in a circular shape at a shorter wavelength side. The deviation of the degree of polarization can be corrected by using a hysteresis increasing agent, so -20-200301375 can obtain a circular polarizing plate with a wide wavelength range. This is based on the insufficient contrast that has been found in reflective liquid crystal displays using a conventional retardation plate because the degree of circular polarization occurs at a shorter wavelength side after the incident light passes through the polarizer and the λ / 4 film. deviation. (Polymer film for phase retardation film) It is preferable to use a polymer film having a light transmittance of 80% or more. As the polymer film to be used in the present invention, those which are difficult to exhibit birefringence by external force are preferred, and examples thereof include cellulose-based polymers such as triethylfluorene-based cellulose and diethylfluorene-based fiber Pigments; norbornene-based polymers such as Artone and Ze on ex; and polymethyl methacrylate. In particular, cellulose esters are better, and lower fatty acid esters of cellulose are better. The name " lower fatty acids " means fatty acids containing 6 or fewer carbon atoms. The number of carbon atoms is preferably 2 (cellulose acetate), 3 (cellulose acrylate) or 4 (cellulose butyrate). Cellulose acetate is particularly preferred. It is also possible to use a mixed fatty acid ester, such as cellulose acetate propionate or cellulose acetate butyrate. Similarly, even conventionally well-known polymers that easily display birefringence, such as polycarbonate or poly (R), which exhibit birefringence reduction properties through molecular modification described in WO 00/26705, can be used. As for the polymer film for the phase retardation film, it is preferable to use cellulose acetate having a degree of acetylation of 57.0 to 61.5%. The degree of acetylation means the amount of acetic acid bound per unit weight of cellulose. The degree of acetylation can be measured and calculated according to ASTM: D-817-91 (Test method for cellulose acetate or its 200301375 analogue). The viscosity average degree of polymerization (DP) of the cellulose ester is preferably 250 or more, and more preferably 290 or more. Similarly, the cellulose ester to be used in the present invention has a narrow molecular weight distribution, as far as Mw / Mn is concerned (Mw; weight average molecular weight; Mη: number average molecular weight) according to gel permeation chromatography. As for the specific Mw / Mn, 値 is preferably 1.0 to 1.7, 1.3 to 1.6 is better, and 1.4 to 1.6 is still better. Provides adhesion between the upper layers (adhesive layer, alignment film, or optically anisotropic layer). The polymer film can be surface treated (eg, glow discharge treatment, corona discharge treatment, UV ray treatment, or flame treatment). These polymer films preferably contain a UV-ray absorbent and the like. Similarly, as described in Japanese Patent Laid-Open Publication No. 3 3 3 4 3 3/1 9 95, an adhesive layer (undercoat layer) may be provided on the polymer film. The thickness of the adhesive layer is preferably 0.1 μm to 2 μm, and more preferably 0.2 μm to 1 μm. (Control of Hysteresis) As for the hysteresis of a polymer film for a phase retardation film, a method of providing an external force (such as stretching) for adjustment is usually performed. An aromatic compound having at least two aromatic rings (as described in European Patent No. 9 1 1 6 5 6 A 2) can also be used as a retardation increasing agent. The aromatic compound is used in an amount of 0.01 to 20 parts by weight per 100 parts by weight of cellulose acetate. A preferred amount of the aromatic compound is 0.05 to 15 parts by weight per 100 parts by weight of cellulose acetate, and 0.1 to 10 parts by weight-22 to 200301375 are more preferable. A combination of two or more aromatic compounds can be used. Examples of the aromatic ring in the aromatic compound include an aromatic heterocyclic ring other than an aromatic hydrocarbon ring. Particularly preferably, the aromatic hydrocarbon ring is a 6-membered ring (ie, a benzene ring). The aromatic heterocyclic ring is usually an unsaturated heterocyclic ring. The aromatic heterocyclic ring is more preferably a 5-, 6-, or 7-membered ring, and more preferably a 5- or 6-membered ring. This aromatic heterocyclic ring usually contains the most double bonds. As for the hetero atom, nitrogen atom, oxygen atom and sulfur atom are preferred, and nitrogen atom is particularly preferred. Examples of the aromatic heterocyclic ring include a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, a furacyl ring, a triazole ring, a pyran Ring, orbital ring, pyridine ring, pyrimidine ring, pyridine ring, and 1, 3, 5 _ Sangeng ring. As for the aromatic ring, the benzene ring, furan ring, thiophene ring, pyridine ring, fluorene ring, thiazole ring, imidazole ring, triazole ring, pyridine ring, pyrimidine ring, pyridine ring, and 1, 3, 5- Three coaxes are better. The number of aromatic rings of the aromatic ring is preferably 2 to 20, more preferably 2 to 12'2 to 8 are still more preferable, and 3 to 6 are most preferable. Similarly, the aromatic compound preferably has at least one 1, 3, 5-triad ring as an aromatic ring. The relationship between two aromatic rings can be classified into three cases: (a) a case where two aromatic rings form a fused ring; (b) a case where two aromatic rings are directly bonded to each other through a single bond; and (c) two In the case where two aromatic rings are bonded to each other via a linking group (spiro bonds are not formed because they are aromatic rings). This relationship can be any one of (a) to (c). Examples of the case (a) in which a fused ring is formed (a fused ring composed of two or more aromatic rings) include a ® ring, a naphthalene ring, a fluorene ring, a fluorene ring, a phenanthrene ring, an anthracene ring, an scarene ring, a tetrahedral ring , Fluorene ring, probe ring, hydrazone ring, benzofuran ring, benzo one 23- 200301375 thiophene ring, indole ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzo Triazole ring, purine ring, indazole ring, ene ring, quinoline ring, isoquinoline ring, hydrazone ring, oxazoline ring, hydrazone ring, quinoxaline ring, hydrazone ring, pteridine ring , Carbazole ring, acridine ring, morphine ring, gluttonium ring, morphine ring, morphine ring, phenastine ring (ph e 1Ίox Hne) ring, morphine ring and thion ring. The naphthalene ring, fluorene ring, indole ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzotriazole ring and quinoline ring are preferred. The single bond in case (b) is preferably a bond between carbon atoms of two aromatic rings. It can also bond two aromatic rings via two or more single bonds to form an alicyclic ring or a non-aromatic heterocyclic ring. The linking group in case (c) is preferably bonded to a carbon atom of two aromatic rings. The linking group is preferably an alkylene group, an alkenylene group, an alkynylene group, < 0-, -0-, -NH-, -S-or a combination thereof. Conventional examples of linking groups composed of combinations are shown below. Additionally, the left-right relationship of the following linking groups may be reversed. cl: -C〇-〇-c2; -CO-NH-c3: alkylene-〇-c4: -NH-CO-NH-c5: -NH-C0-0-c6;-0 ~ C0- 0 -c 7:-0 -alkylene-〇-c8: -C0-alkenylene- c9: -C0-alkylene-NH- -24-2ι] 〇3〇ΐ37ύ el〇: ~ co-Asia Alkenyl-〇- ell: -alkylene-C0-0-alkylene-0-C0-alkylene- e 1 2 ·-0 -alkylene-C0-0 -alkylene-〇- C0 -伸 院 基 -〇-

Cl3: -0-C0-alkylene- C0-0- el4: -NH-CO-alkylene-el5: -0-C0-alkylene- ^ aromatic group and linking group may have one Or more substituents. ^ Examples of substituents include halo atoms (F, Cl, Br, or I), warp, end, cyano, amine, nitro, sulfo, carbamoyl, sulfamoyl, and phosphono , Alkyl, alkenyl, alkynyl, aliphatic fluorenyl, aliphatic fluorenyl, alkoxy, oxocarbonyl, alkoxycarbonylamino, alkylthio, alkylsulfonyl, aliphatic amine Sulfonamido, aliphatic substituted amine, aliphatic substituted carbamoyl, aliphatic substituted sulfamoyl, aliphatic substituted urea and non-aromatic heterocyclic groups. The number of carbon atoms in the base is preferably 1 to 8. A chain alkyl group is better than a cycloalkyl group 'and a linear chain group is particularly preferred. The base may further have one or more substituents (for example, a hydroxyl group, a carboxyl group, an alkoxy group, or an alkyl-substituted amino group). Examples of the alkyl group (including substituted groups) include methyl, ethyl, n-butyl, n-hexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl, and 2-di Ethylaminoethyl. The number of carbon atoms of the alkenyl group is preferably 2 to 8. Alkenyl alkenyl groups are better than cyclic alkenyl groups, and linear alkenyl groups are particularly preferred. The alkenyl group may further have one or more substituents. Examples of the alkenyl include vinyl, allyl, and 1-hexenyl. The number of carbon atoms of the alkynyl group is preferably 2 to 8. Alkenyl alkenyl is better than cyclic alkynyl -25-200301375, and straight-chain alkynyl is especially good. The alkynyl group may further have one or more substituents. Examples of the alkenyl group include ethynyl, 1-butynyl and hexadecyl. The number of fe atoms of the lipase group is preferably from 1 to 10. Examples of the fatty acid group include ethenyl, propionyl and butylamyl. The number of carbon atoms of the aliphatic fluorenyloxy group is preferably 1 to 10. Examples of the aliphatic fluorenyl group include an acetate group. The number of carbon atoms of the alkoxy group is preferably 1 to 8. The alkoxy group may further have one or more substituents. Examples of the alkoxy group (including substituted alkoxy groups) include methoxy, ethoxy, butoxy, and methoxyethoxy. The number of carbon atoms of a cinnoxycarbonyl group is preferably 2 to 10. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. The number of carbon atoms of the hydroxenylamino group is preferably 2 to 10. Examples of the oxominylamino group include a methoxycarbamino group and an ethoxyfluorenylamino group. The number of carbon atoms of the alkylthio group is preferably 1 to 12. Examples of the alkylthio group include methylthio, ethylthio and octylthio. The number of carbon atoms of the alkyl maple group is preferably 1 to 8. Examples of the alkyl alkynyl group include methanesulfonyl and ethanesulfonyl. The number of carbon atoms of the aliphatic amido group is preferably from 1 to 10. Examples of the aliphatic amido group include an acetamido group. The number of carbon atoms of the aliphatic sulfonamide group is preferably 1 to 8. Examples of the aliphatic sulfonamido group include methanesulfonamido group, butanesulfonamido group, and n-octanesulfonamido group. The number of carbon atoms of the aliphatic-substituted amine group is preferably from 1 to 10. Examples of the aliphatic-substituted amino group include a dimethylamino group, a diethylamino group, and a 2-carboxyethylamino group. -26-200301375 The number of carbon atoms of the aliphatic substituted carbamate group is preferably from 2 to 10. Examples of the aliphatic substituted aminoformamyl include methylaminoformamyl and diethylaminoformamyl. The number of carbon atoms of the aliphatic-substituted sulfamoyl group is preferably 1 to 8. Examples of the aliphatic substituted aminesulfonyl group include methylaminesulfonyl and diethylaminesulfonyl. The number of carbon atoms of the aliphatic-substituted ureido group is preferably 2 to 10. Examples of the aliphatic substituted ureido group include methylureido. Examples of the non-aromatic heterocyclic group include N-hexahydropyridyl and morpholino. The molecular weight of the retardation increasing agent is preferably 300 to 800. As for the retardation enhancer, descriptions have also been provided in Japanese Patent Laid-Open Publications Nos. 1 1 9 1 4/2000 and 275434/2000, and those compounds described in these publications can be used. The phase retardation film of the present invention is preferably a phase retardation film, which comprises a λ / 4 plate (which is a birefringent film capable of providing 1/4 wavelength phase retardation birefringent light) and a λ / 2 plate (which is A birefringent film that provides retarded birefringent light with a 1/2 wavelength phase), so its optical axes intersect each other at a predesigned angle. In the present invention, this phase retardation film is specifically referred to as " broadband λ / 4 plate " in some examples. The broadband λ / 4 board which can be preferably used in the present invention is described in detail below. The coordinate axis is defined as shown in Figure 1 1 Α. The optical elements are arranged in the y z plane, and the light travels along the X axis. Similarly, the axis direction of the optical element is measured at an angle of-27-200301375 in the y-z plane (which is positive clockwise from the y-axis), as shown in Figure 11B. The same definitions apply equally to the following description. In Fig. 10A, 1 2 4 indicates a λ / 4 plate, 1 2 1 and 1 2 3 are adhesives, 122 indicates a λ / 2 plate, and 1 10 indicates a polarizing plate. As shown in Fig. 10B, the stretching axis of the λ / 4 plate 1 2 4 is arranged in the direction of 20 degrees; as shown in the figure 10C, the stretching axis of the λ / 2 plate 1 2 2 is arranged. In the direction of 75 degrees. The polarizing plate 1 1 0 is arranged so that the transmission axis is horizontal, as shown in FIG. 10D. The element is designed so that when light enters the element from the side of the λ / 4 plate, the circularly polarized light in the counterclockwise direction can be absorbed by the polarizer, and only the circularly polarized light in the clockwise direction can pass through. The circularly polarizing plate 100 of the practical form shown in Figs. 10A to 10D is configured so that the retardation wavelength dispersion characteristic of the λ / 4 plate is eliminated from the characteristics of the λ / 2 plate 1 2 2 When the circular polarizing plate is in the visible light range (400 nm to 70 nm), it can show almost fixed properties. Similarly, suitable characteristic properties can be selected by appropriately changing the angle between the λ / 2 plate and the λ / 4 plate according to a required specification (such as a desired wavelength range), and further, the wavelength diffusion property can be improved . As for the angle between the λ / 2 plate 1 2 2 and the λ / 4 plate 1 24, it is preferable to appropriately select this angle so that the retardation ratio of the wavelength of the incident light becomes fixed. Similarly, in the present invention, when at least one wavelength plate constituting a phase retardation film has a refractive index in the direction of the angular coordinate system axis in the plane of the wavelength plate and its refractive index in the direction of the film thickness, nx, ny and At ηζ, they preferably satisfy the relationship of nx > ny and (nx-ny) < 1. The retarded wavelength dispersion can be 200301575 using a predesigned λ / 4 plate (which can show a 1/4 retardation of the designed wavelength (λ0) (which can be defined as the refractive index difference (Δη) and thickness of birefringent light The product of (d) (And))) and the λ / 2 plate (which can show a ½ hysteresis) are controlled. In particular, the ratio (And / λ) of the retardation to the wavelength (λ) of the incident light can be caused to be almost constant, and the characteristic properties of the optical system using the phase retardation film can be improved. A wavelength plate having this property is characterized in that when light is not incident in a direction perpendicular to the wavelength plate but in a skewed direction, it will show less hysteresis. Therefore, when a wavelength plate with this property is used to prepare a phase retardation film (broadband λ / 4 plate), it can control the wavelength spreading properties over a wide range of incident angles, thus further improving the advantages of the present invention. The λ / 2 plate or λ / 4 plate of the present invention can usually be prepared by stretching a high polymer film. In the present invention, polycarbonate, triethylfluorene cellulose, polyolefin and the like are preferred, and they can be widely used as a material for a wavelength plate. The thickness is not particularly limited 'but a preferred range is from 1 micrometer to 1,000 micrometers. The lamination of the λ / 2 plate and the ν / 4 plate and the wideband λ / 4 plate and the polarizing plate can be performed using a well-known contact bonding type or a hot-melt type adhesive or adhesive. Thus, the laminated angle of the broadband λ / 4 plate and the polarizing plate is appropriately selected, so that the resulting laminated plate can have certain properties that can be used as a circular polarizing plate in the visible light range. (Protective film) The polarizing film of the present invention is preferably used as a polarizing plate by laminating a protective film on both or one side. The type of protective film is not particularly limited, and cellulose acetates (such as cellulose acetate and cellulose acetate butyrate) can be used here. -29- 200301375, polycarbonate, polyolefin, polystyrene, and poly ester. The protection that can be used for polarizing plates needs to have these physical properties, such as light transmittance, suitable water vapor permeability, low birefringence, and suitable hardness. From the overall point of view, cellulose acetates are preferred, and cellulose acetate is particularly preferred. The protective film is usually fed in the form of a roller, and is preferably continuously laminated on a circular polarizer of this continuous length, so that the longitudinal direction of the former corresponds to the latter. Herein, the orientation axis (low axis) of the protective film may be any direction, but from the viewpoint of convenience of operation, the orientation axis of the protective film is preferably parallel to the longitudinal direction. Similarly, the angle between the low axis (orientation axis) of the protective film and the absorption axis (stretch axis) of the polarizing film is not particularly limited, and may be appropriately selected depending on the end use. Because the absorption axis of the continuous-length circular polarizer of the present invention is not parallel to the longitudinal direction, hereby, a protective film parallel to the orientation axis and the longitudinal direction can be continuously laminated to the continuous-length circular polarizer of the present invention to obtain a A polarizing plate whose absorption axis of the polarizing film is not parallel to the orientation axis of the protective film. When the angle between the low axis of the protective film and the absorption axis of the polarizing film is in the range of 10 degrees to less than 90 degrees (more preferably 20 degrees to 80 degrees), an effective dimensional stability improvement effect can be exhibited. The physical properties of the protective film can be selected according to the end use, but the typical ones used for general transmissive LCDs shown below are preferred. In consideration of handling properties and durability, the thickness of the film is preferably 5 to 500 µm, more preferably 20 to 200 µm, and particularly preferably 20 to 100 µm. The hysteresis at 6 3 2 8 nm is preferably 0 to 150 nm, more preferably 0 to 20, and particularly preferably 0 to 5 nm. In consideration of preventing linearly polarized light from becoming elliptically polarized, it is preferable that the low axis of the protective film is substantially parallel or perpendicular to the absorption axis of the polarizing film. However,-3 0-200301375 is an example in which the protective film is given the function of changing the polarizing ability (phase retardation function). This does not apply. The angle between the low axes of the polarizing plate's absorbing film can be any number. The visible light transmittance of the protective film is preferably 60% or more, and 90% or more. The reduced ruler after treatment at 90 ° C for 120 hours is from 0.3 to 0.1%, particularly preferably from 0.1 to 0.01%. The tensile strength measured by this thin test is preferably 50 to 1,000 million, more preferably 100 to 300 million Pa. The film has a water vapor permeability of 800 g / m 2 · day, and particularly preferably 300 to 600] foot · day. Needless to say, the application of the present invention is not limited to the above description. The cellulose acetates of the preferred cellulose acetates as protective films will be described in detail below as those which satisfy all of the following formulas (I) to (I V) in relation to the hydroxyl groups of cellulose:

Formula (I) 2 · 6SA + BS3. 0 Formula (II) 2.0SAS3 · 0 Formula (III) 0SB Only 8 Formula (IV) 1.9 < AB In the above formula, A and B represent fluorenyl substituted cellulose The degree of hydroxyl group, and A represents the degree of substitution of ethenyl, and B represents the degree of substitution of fluorenyl having one carbon atom. Cellulose has three hydroxyl groups per cellulose, and the above-mentioned 値 represents the degree of substitution with the number of hydroxy groups of 3.0 ', so that the maximum 値 is 3.0. Cellulose triacetate has a degree of substitution A of 2.6 to 3.0. (In this example, the shaft and protection of the non-warp plate is particularly preferred. The tension is preferably a film, and the tensile strength is particularly preferred. The ratio of the preferred degree of substitution is 3 to 5 sugar units with a hydroxyl group of 200301375 which is usually substituted by the base ester. The ratio is 0.4) and the degree of substitution B is 0. As for the cellulose acetate used in the protective film for polarized light, all of the ethyl groups are cellulose triacetate of ethyl group and the ratio of ethyl acetate is 2.0 or more, having 3 to The degree of substitution of the fluorenyl group of 5 carbon atoms is 0.8 or less, and the degree of unsubstituted hydroxyl group is 0.4 or less is preferred. When a fluorenyl group having 3 to 5 carbon atoms is used, the degree of substitution is particularly preferably 0.3 or less from the viewpoint of physical properties. The degree of substitution can be additionally obtained by measuring the degree of bonding of the hydroxyacetic acid of the substituted cellulose and the fatty acid having 3 to 5 carbon atoms, followed by calculation. This measurement method can be performed in accordance with ASTM D-81 7-91. The fluorenyl and propenyl groups having 3 to 5 carbon atoms to be used are propionyl (C2H5CO-), butyl fluorenyl (C3H7CO-), (n-, iso-), and pentamyl (C4H9CO-) (n- , Iso-, secondary-, tertiary-). Among these, in consideration of the mechanical strength and ease of dissolution when forming a thin film, the positive type is preferred, and the n-propylfluorenyl group is particularly preferred. In the case where the degree of substitution of acetamyl is reduced, this results in a reduction in mechanical strength and resistance to moist heat. In the example where the degree of substitution of a fluorenyl group having 3 to 5 carbon atoms is increased, an improved solubility in an organic solvent is produced here. As long as the degree of substitution is within the range described above, good properties can be obtained. The degree of polymerization (average viscosity) of the cellulose acetate is preferably 200 to 700, and particularly preferably 2 50 to 5 50. This viscosity average degree of polymerization can be measured by an Oswald's (0 stwa 1 d's) viscometer, and calculated using the measured intrinsic viscosity [η] of cellulose phosphonate according to the following formula: DP Two [η] / Km -32-20030073d where DP represents the average degree of polymerization of viscosity and Km represents the constant 6χ 1 0_4. As the starting materials for cellulose acetate, cotton wool fibers and wood pulp have been clarified. Cellulose gallate obtained from any starting cellulose can be used, and mixtures thereof can be used as well. (Preparation of polymer film) The above-mentioned cellulose acetate is usually produced by a solvent casting method. The solvent casting method is a method in which cellulose acetate and various additives are dissolved in a solvent to prepare a concentrated solution (hereinafter referred to as " coating compound ") and wound into continuous On a carrier, such as a roller or belt, and the solvent is evaporated to form a thin film. The coating compound is preferably adjusted so that the solid amount becomes 10 to 40% by weight. The surface of the roller or belt is preferably polished to a mirror state. As for the casting method and the drying method in the solvent casting method, it is described in U.S. Pat. Instructions are provided in / 1970 and 5 6 1 4/1 974; Japanese Patent Laid-Open Publication No. 1 768 3 4/1 98 5, 203430/1985 and 115035/1987. It is also preferable to use a method of casting two or more coated rubber layers. In the case of casting a plurality of coating compounds, the film can be formed by providing a plurality of sections in a direction in which the carrier moves, and separately casting the solution containing the coating compound through the plurality of casting gaps, thereby forming A coated rubber layer. For example, those methods described in Japanese Patent Laid-Open Publication Nos. 1 5 84 1 4/1 9 86, 1 224 1 9/1 989 and 19828 5/1 9 99 can be applied. Similarly, the film can be formed by casting cellulose acetate solution-33- 200301375 through two casting gaps. This can be based on, for example, Japanese Patent Publication No. 27 5 62/1 9 8 5; 158413/1986 and 34933/1994. Likewise, a casting method in which a high-viscosity coating compound is surrounded by a low-density coating compound and a high- and low-viscosity coating compound is simultaneously extruded can be preferably used (also described in the Japanese Patent Publication No. 162617/1981). Examples of organic solvents that can be used to dissolve cellulose acetate include hydrocarbons (eg, benzene and toluene), halogenated hydrocarbons (eg, dichloromethane and chlorobenzene), alcohols (eg, ethanol and diethylene glycol) , Ketones (for example, acetone), esters (for example, ethyl acetate and propyl acetate), and ethers (for example, tetrahydrofuran and methyl glycol ether). It is preferred to use halogenated hydrocarbons having 1 to 7 carbon atoms, and most preferably dichloromethane is used. In consideration of physical properties (such as the dissolving properties of cellulose acetate, the properties of peeling from the carrier, the mechanical strength and optical properties of the resulting film), it is preferable to use one or several kinds of 1 to 5 carbon atoms. Alcohols and combined with dichloromethane. The content of the alcohol is preferably 2 to 25% by weight, and more preferably 5 to 20% by weight (based on the entire solvent). Specific examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, and n-butanol, and methanol, ethanol, n-butanol, or a mixture thereof is preferably used. As for components which become solid other than cellulose acetate after drying, plasticizers, UV absorbers, heat stabilizers such as salts of inorganic particles and alkaline earth metals (for example, calcium or magnesium) may be optionally included here. ), Antistatic agents, flame retardants, lubricants, oils, agents to accelerate stripping from the carrier, agents to prevent hydrolysis of cellulose acetate, and so on. As the plasticizer to be preferably added, a phosphate ester or a carboxylic acid ester -34-2,300,3,0 can be used. Examples of phosphates include triphenyl phosphate (TPP), tricresyl phosphate (TCP), tolylene phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, and tributyl phosphate . As for the carboxylic acid esters, there are typically phthalates and citrates. Examples of phthalates include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), diphenyl phthalate (DPP) ) And diethylhexyl phthalate (DEHP). Examples of citric acid esters include 0-ethylammonium triethyl citrate (OACTE), 0-ethylammonium tributyl citrate (0ACTB), ethylammonium citrate and ethyltributylammonium citrate. Examples of other carboxylic acid esters include butyl oleate, methyl ethyl ricinoleate, dibutyl sebacate, and trimellitates such as trimethyl trimelliate. Examples of glycolic acid esters include triacetin, tributyl essence, butyl phthalocyanobutyl glycolate, ethyl phthalocyanoethyl glycolate, methyl phthaloyl ethyl glycolate, and butyl phthalate Fluorenyl butyl ester. Among the plasticizers described above, triphenyl phosphate, diphenyl biphenyl phosphate, tricresyl phosphate, tolylene phosphate, tributyl phosphate, dimethyl phthalate, and diphthalate are preferably used. Ethyl acetate, dibutyl phthalate, dioctyl acetate, diethylhexyl phthalate, triacetin, ethyl phthaloacetate glycolate, and trimethyl trimellitate (trimethy 1 trima 1 1 itate). In particular, triphenyl phosphate, diphenyl biphenyl phosphate, diethyl phthalate, ethyl glycolate ethyl phthalate and trimethyl trimelliate are preferred. These plasticizers can be used alone or in combination of two or more. The plasticizing amount to be added is preferably 5 to 30% by weight, particularly preferably 8 to 16% by weight (based on cellulose acetate). These compounds may be added together with cellulose acetate and a solvent to prepare a cellulose acetate solution, or may be added during or after the preparation of the solution. -35-200301375 As for the UV ray absorbent, any one can be selected according to the end use. Here, salicylate type, benzophenone type, benzotriazole type, benzoate type, cyanoacrylate can be used. As the absorbent of the type and the nickel complex type, the benzophenone type, the benzotriazole type, and the salicylate type absorbent are preferable. Examples of benzophenone-type UV-ray absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-acetamidooxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2 , 2'-Di-hydroxy-4-methoxybenzophenone, 2,2, -di-hydroxy-4,4, -dimethoxybenzophenone, 2-hydroxy-4-n-octyloxydione Benzophenone, 2-hydroxy-4-dodecyloxybenzophenone and 2-hydroxy-4- (2-hydroxy-3-methacryloxy) propoxybenzophenone. Examples of benzotriazole-type UV ray absorbers include 2 (2'-hydroxy-3'-tertiary butyl-5, methylphenyl) -5-chlorobenzotriazole, 2 (2hydroxy-5 ' -Tertiary butylphenyl) benzotriazole, 2 (2 ^ hydroxy-3 ', 5, di-tertiary pentylphenyl) benzotriazole, 2 (2' · hydroxy-3,5, -Di-tertiary butylphenyl) -5 -chlorobenzotriazole and 2 (2f -hydroxy-5 ^ tertiary octylphenyl) benzotriazole. Examples of the salicylate type include phenyl salicylate and p-octylphenyl salicylate, p-tert-butylphenyl salicylate. Among these clarified UV-ray absorbers, 2-hydroxy-4-methoxybenzophenone, 2,2 1-di-hydroxy-4,4'-methoxybenzophenone, 2 (2 · -hydroxy -3, tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2 (2 ^ hydroxy-5'-tert-butylphenyl) benzotriazole, 2 (2 Hydroxy-3,5'-di-tertiary pentylphenyl) benzotriazole and 2 (2'-hydroxy-3 ', 5'-di-tertiary-butylphenyl) -5 -chloro- Benzotriazole is particularly preferred. It is particularly preferable to use several kinds of absorbers whose absorption wavelengths are different from each other in order to obtain a high potential accumulation effect in a wide wavelength range. The amount of the UV ray absorbing agent is preferably from 0.01 to 5% by weight, particularly preferably from 0.1 to 3% by weight (based on cellulose 20030137). The νν ray absorber can be added when the cellulose acetate is dissolved, or it can be added to the coating compound in which the cellulose acetate is dissolved. It is particularly preferred to use a static mixer to add the UV ray absorbent solution to the coating compound immediately before casting. As for the inorganic fine particles to be added to the cellulose phosphonate, silicon dioxide, kaolin, talc, diatomaceous earth, quartz, calcium carbonate, barium sulfate, titanium oxide, and aluminum oxide can be freely used according to the end use. Prior to being added to the coating compound, these particles can preferably be dispersed in the adhesive solution using any equipment, such as a high speed mixer, ball mill, grinder, or ultrasonic disperser. As for the adhesive, cellulose acetate is preferred. It is also preferably dispersed with other additives such as UV-ray absorbers. As the dispersing solvent, any solvent may be used, but a solvent having a composition similar to that used for coating the rubber compound is preferred. The number average particle size of the dispersed particles is preferably from 0.01 to 100 μm, and particularly preferably from 0.1 to 10 μm. The dispersant mentioned above may be added at the time of the cellulose acid vinegar step, or may be added to the coating compound in any step. However, as for the UV absorbing agent, the dispersant can be preferably added immediately using a static mixer or the like before casting. As for the agent which accelerates the peeling from the carrier, the surfactant has this effect and can be used. Any surfactant based on phosphate, surfactant based on expanded salt, surfactant based on carboxylate, nonionic surfactant, and cationic surfactant are not special limit. These have been described in, for example, Japanese Patent Laid-Open Publication No. 2 4 3 8 3 7/19 8 6. In the example-37-200301375 using the aforementioned cellulose acetate film as a protective film, it is preferable to impart hydrophilicity to the film surface by a method such as saponification, corona treatment, flame treatment, or glow discharge treatment. Sex. Similarly, a hydrophilic resin may be dispersed in a solvent having a certain affinity for cellulose acetate, and the dispersion may be coated on the film in a thin layer. Among the methods mentioned above, saponification is particularly preferable because it does not impair the planar and physical properties of the film. The saponification treatment can be performed, for example, by immersing the film in an aqueous solution of an alkali such as sodium hydroxide. After the treatment, it is preferably neutralized with a low concentration of acid to remove excess alkali, followed by washing with sufficient water. The following specifically describes the saponification treatment with an alkali (which can be preferably used as a surface treatment method for a cellulose acetate film). It is preferably treated in a cyclic manner in which the surface of the cellulose acetate film is immersed in an alkaline solution, neutralized with an acidic solution, then washed with water and dried. As for the alkaline solution, potassium hydroxide solution and sodium hydroxide solution have been clarified. The equivalent concentration of hydroxide ions is preferably from 0.1N to 3.0N, more preferably from 0.5N to 2.0N. The temperature of the alkaline solution is preferably room temperature to 90 ° C, and more preferably 40 ° C to 70 ° C. Subsequently, the film is usually washed with water, and after passing through an acidic aqueous solution, washed with water to obtain a surface-treated cellulose acid acid film. In this case, the acid may be hydrochloric acid, nitric acid, sulfuric acid, acetic acid, formic acid, chloroacetic acid, oxalic acid, or the like, and the concentration thereof is preferably from 0.00 · N to 3.0N, and more preferably 0.05N. To 2.0N. In the case where a cellulose acetate film is used as a transparent protective film for a polarizing plate, considering the adhesion to the polarizing film, it is particularly preferable to perform an acid treatment and an alkali treatment, that is, a saponification treatment of the cellulose acetate . The surface energy of the solid thus obtained can be measured by contact angle method, damp heat method-3 8-method or adsorption method, as described in " Nure No Kι so To Oyo " (Dec. 10, 1989 by Riarayi In (Riaraizu KK · Announcement), the contact angle method is better. In terms of contact angle, the surface energy may be 5 to 90 degrees, and more preferably 5 to 70 degrees. Any functional layer such as an optical anisotropic layer to compensate the viewing angle of the LCD can be provided on the surface of the protective film of the circular polarizer of the present invention (described in Japanese Patent Laid-Open Publications Nos. 229828/1992, 75115/1994, and 50206/1996) An anti-glare or anti-reflection layer used to improve the viewing properties of a display, a layer that has the function of separating PS waves by improving the luminous brightness by anisotropic scattering or anisotropic optical interference (for example, a dispersed high polymer liquid crystal layer or Cholesterol liquid crystal layer), a hard coating layer for improving the scratch resistance of a polarizing plate, a gas barrier layer for suppressing the diffusion of moisture or oxygen, a simple adhesive layer or an adhesive for improving the adhesion to a polarizing film or itself Adhesives, and layers used to impart distorted properties. These functional layers may be provided on the side of the polarizing film or on the side opposite to the polarizing film, and may be appropriately selected according to the end use. On the polarized light I of the present invention, a thin film with different functions can be laminated directly on one side or as a protective film. As far as the functional film itself is concerned, here will explain the phase retardation film (such as a λ / 4 plate or λ / 2 plate), a light scattering film, a plastic unit with a conductive layer on the opposite side of the polarizing plate, and an anisotropic scattering Or anisotropic optical interference function of the luminous brightness improvement film, reflecting plate and translucent reflecting plate. As the protective film for a polarizing plate, a single sheet of the preferable protective film described above or a multi-layer laminated film thereof can be used. The same protective film can be laminated on the two sides of the polarizing film, or a protective film having different functions and physical properties from each other can be laminated on each side. Similarly, the protective film may be laminated on only one side of the polarizing film and an adhesive layer may be directly provided on the other side for directly laminating a liquid crystal cell without laminating the protective film. In this example, a peelable separator film is preferably provided on the outer edge of the adhesive layer. (Surface protection film). As for the surface protective film, the hard coat layer, the AG layer, the AR layer, and the CV layer are explained here. These layers may be composed of a single layer or a plurality of layers, but from the viewpoint of the production steps, the film is preferably composed of a single film. The single layer can be formed by coating several times after coating and drying, as long as the layers have the same composition. On the other hand, the name " multilayer " means that the layers can be formed in the formulation separately from each other. As such, these layers can be used in combination. The hard coating layer preferably contains a hardenable composition, particularly preferably a compound containing an ethylenically unsaturated group-containing compound and a molecule containing three or more ring-opening polymerizable groups in the molecule. A hardenable composition of a compound. The contained components may preferably undergo a crosslinking reaction after the hardening reaction. This crosslinking reaction may be any of a radical polymerization reaction and a cationic polymerization reaction. In both examples, the polymerization can be performed by heat and / or light. The polymerization reaction generally allows the addition of a small amount of a free radical generator or an cation generator (or an acid generator) (referred to as a polymerization initiator) and is performed by thermal and / or photolysis to generate free radicals or cations. The radical polymerization reaction and the cationic polymerization reaction can be performed separately, but it is preferable to allow them to proceed simultaneously. As for the method of allowing the cross-linking reaction without the addition of a free radical generator, there is a method of heating only the system ', but it is preferable to use a 40-200301375 line (such as radiation, gamma rays, alpha rays, etc.) with actinic energy. , Electron beam and UV rays). If necessary, crosslinkable fine particles may be added to the hardenable composition. The addition of crosslinkable particles can provide improved adhesion to the substrate because it can reduce the hardening shrinkage of the hard coating layer and, in the case where the substrate is a plastic film, it is provided to reduce curling. As for the crosslinkable fine particles, inorganic fine particles, any organic fine particles, and organic-inorganic composite fine particles can be used without particular limitation. Examples of the inorganic fine particles include silicon dioxide particles, titanium dioxide particles, chromium oxide particles, and aluminum oxide particles. Inorganic particles are generally hard, and they can be added to the hard coating layer to provide reduced shrinkage after hardening and, in addition, can increase the hardness of the surface. In general, inorganic particles have low affinity for organic components such as the polymer of the present invention and polyfunctional vinyl monomers, so mixing them alone may cause the formation of aggregates or harden in some instances The hard coating layer was broken. Therefore, in order to increase the affinity between the inorganic fine particles and the organic component, the surface of the inorganic fine particles may be treated with a surface modifier of an organic part. As for the organic fine particles, there have been clarified those obtained by crosslinking a general-purpose resin , Such as polyethylene, polypropylene, polytetrafluoroethylene, nylon, polyethylene terephthalate, polystyrene, poly (meth) acrylic and ammonium, polyvinyl chloride, ethyl cellulose , Nitrocellulose and polydimethylsiloxane and crosslinked rubber particles (such as SBR and NBR). The thickness of the hard coating layer is also different from the hardness of the substrate to be coated; and the effect of increasing the hardness and forming a hard coating layer that is difficult to break and peel can be obtained by increasing the thickness of the hard coating layer -41- 200301375 Become obvious. This thickness may be from 1 to 200 microns, preferably from 20 to 200 microns, more preferably from 30 to 200 microns, still more preferably from 40 to 200 microns, and most preferably from 50 to 200 microns. The surface hardness of the hard coating layer formed from the hardenable composition is also different from the type of the substrate to be coated, but it is preferably higher. The surface hardness to be used herein in the present invention can be expressed by the pencil strength as defined by I S K 5 400, and can be evaluated by directly scratching the surface of the hard coating layer with a pencil. In terms of pencil hardness, the surface hardness of the hard coating layer is 3H to 9H, preferably 4H to 9H, and more preferably 5H to 9H. Similarly, for the purpose of improving the adhesion properties between the substrate and the hard coating layer, both or one side of the substrate may be subjected to a surface treatment (for example, by an oxidation method or a roughening method). As for the surface treatment method, for example, chemical treatment, mechanical treatment, corona discharge treatment, glow discharge treatment, chromic acid treatment (wet process), flame treatment, high frequency treatment, hot air treatment, ozone treatment , UV radiation treatment, activated plasma treatment and mixed acid treatment. Furthermore, one or more undercoat layers may be provided. As for the material for the undercoat layer, there have been clarified copolymers of vinyl chloride, vinylidene chloride, butadiene, (meth) acrylates, styrene, vinyl esters, etc., and their emulsions, polyesters, and polymers. Urethanes, and water-soluble polymers (such as gelatin). Furthermore, a functional layer having different functions may be provided on the hard coating layer, such as an anti-reflection layer, a UV ray and infrared absorption layer, a layer capable of absorbing light of a selected wavelength, an electromagnetic wave shielding layer or a dyed waterproof layer. These functional layers can be formed using conventionally well-known techniques. Similarly, in order to improve the adhesion between the functional layer and the hard coating layer, the hard coating layer may be subjected to a surface treatment, or an adhesive layer may be provided thereon. < Polarizing film > The skew-oriented polarizing plate of the present invention can be easily obtained by the method described below. That is, the skewed orientation can be 'inquired' by stretching the polymer film. The volatile ratio of the film after stretching, the shrinkage of the film after shrinking, and the film during stretching can be appropriately selected. The former elastic modulus. Furthermore, it is also preferable to adjust the amount of foreign substances adhered to the film before stretching. Therefore, the stretched film does not suffer from shrinkage even when it is stretched skewly, and a polarizing film having small surface roughness and excellent flatness can be obtained here. Similarly, since no shrinkage is formed, no skew is formed, and therefore, the tensile tension applied to the film is not reduced, and this large sheet can provide a conditional change without causing color. The following is a detailed description of the preferred stretching method for obtaining the polarizing plate of the present invention (hereinafter referred to as "the stretching method of the present invention" in some examples). (Stretching method) Figures 3 and 4 show skewed pull Schematic plan view of an example of stretching the polymer film. The stretching method of the present invention includes: a step indicated by (a), wherein the raw film is introduced from the direction shown by the arrow (丨); (B) the step indicated in which the film is stretched in the transverse direction; and a step indicated by (c) in which the stretched film is conveyed to the next step in the direction indicated by the arrow (2) After this, the name " drawing step " means all the steps used to carry out the drawing method of the present invention, including these steps (a) to (c) -43- 200301375 The film is continuously from the direction ( l) Introduced, first clamped by the clamp at point B 1 on the left (viewed from the upstream side). At this point, the other edge of the film was not clamped, so there was no tension in the transverse direction. That is, , B1 is not the starting point of the actual grip (here The back finger is "the starting point of the substantial grip". In the present invention, the starting point of the substantial grip is defined as the point of the two edges of the gripping film. The starting point of the substantial grip can be displayed by two points: one is at The gripping start point A1 on the further downstream side; and c 1 another point, which is pulled from A1 in a direction almost perpendicular to the film centerline 1 1 (Figure 3) or 2 3 (Figure 4) — Straight line, and the opposite side track 1 3 (picture 3) or 2 3 (picture 4) intersects. When the fixtures on the two edges start conveying at the substantially equal speed from the starting point of the substantial grip ' A1 will move to A2, A3 ~ An per unit time, and C1 will similarly move to the stretching direction of the connection time point passed by c2, C3 at the same time. • Cn. In other words, refer to the grip device

An and Cn lines can be displayed here

An is gradually delayed relative to Cn (such as

In the method of the present invention, the direction of An becomes inclined. Refers to the grip release point Cx of the "substantially grip release point"; draw a straight line in a direction perpendicular to the direction to be conveyed to the next figure 4), and the clamp (see figure 3) or 24 (picture 4) Intersection. -44-200301375 The angle of the final film stretching direction can be determined by the orbital difference Ay-Αχ (that is, | LI -L2) on the right and left sides of the fixture at the point where the stretching step is substantially completed (the substantial grip release point). ) And the distance W (distance between Cx and Ay) between the actual grip release point. Therefore, the inclination angle Θ between the stretching angle and the conveying direction in the next step is one that satisfies the following formula Angle: ta η Θ = W (A y-A x)

That is, t an0 = W / I LI-L2 I although it is shown above the film in Figures 3 and 4 the edge is still gripped until 18 (Figure 3) or 28 (Figure 4) after passing the point Ay, However, the other edge is not gripped, so any lateral stretching no longer occurs. Points 18 and 28 are not the actual grip release points of the present invention. As described above, in the present invention, the starting point of the substantial grip on the two edges of the film is not simply the points at which the film starts to grip the left and right sides of the film by the grips. In order to more strictly define the two gripping starting points of the present invention, the gripping starting point is a straight line connecting the gripping point on the left or right and the gripping point on the other side, which meets at an almost correct angle. To the center line of the film where the film gripping step is to be introduced, and the points located at the most upstream position. Similarly, in the present invention, the two substantial grip release points are defined as the line connecting the left or right grip point and the grip point on the other side at a nearly correct angle to the conveyance to the next step. The film centerline is located at those points at the most downstream position. Here, the name π almost at the correct angle π means that the centerline of the film is at an angle of 90 + -0.5 degrees (as the name used in this article π " means "plus or minus") ) Encountered the link between the start point of the left substantial grip and the right end of the right grip-45- 20030137ο the starting point of the grip or the line connecting the release point of the left substantial grip and the release point of the right substantial grip. To create a difference between the left and right tracks. 'Because of mechanical constraints (such as track length), it is often between the point at which the film begins to be gripped by the clamp and the point at which the substantial grip begins or at the beginning of the film A worrying gap occurs between the point and the substantial grip release point. However, 'As long as the step between the substantial grip start point and the substantial grip release point defined above satisfies the relationship of (1), it can be achieved OBJECTS OF THE INVENTION Φ In the above description, the orientation of the produced stretched film can be controlled by adjusting the ratio of the output width w of step (C) to the track difference IL 1-L2 I in the two substantial fixtures. Shaft Oblique angle. For polarizing plates and retardation films, it is often necessary to orient the film at an angle of 45 degrees from the longitudinal direction. In this example, it is preferable to satisfy the following formula (2) to obtain an orientation angle close to 45 degrees :

[2] 0 · 9W < | L1-L2 丨 &1; 1 · 1W The following formula (3) is more preferable: * Formula (3) 0. 97W < | LI -L2 | < 1. 03W. As long as the relationship of formula (1) is satisfied, a specific stretching step structure can be freely designed in consideration of equipment cost and productivity (as illustrated in Figs. 3 to 8). The angle between direction (1) (which introduces the film to the stretching step) and direction (2) (which conveys the film to the next step) can be any degree, but considering the reduction of equipment (including before stretching and The total area of the subsequent steps) is preferably made smaller. The angle is preferably within 3 degrees, and more preferably within 0.5 -46- 200301375 degrees. This frame can be obtained, for example, in the structures shown in Figures 3 and 4. In a method in which the direction of travel of the film is not substantially changed, it is difficult to obtain an orientation angle of 45 degrees in the longitudinal direction (this angle is preferable for a polarizing plate or a phase retardation film) only by increasing the width between the clamps. Therefore, as shown in Fig. 3, | | L · 1 -L2 | can be increased by providing a shrinking step after stretching the film once. The desired stretching ratio is from 1.1 to 10.0, more preferably from 2 to 10 ', and the subsequent shrinkage ratio is desired to be 10% or more. Similarly, as shown in Figure 6, repeated stretching and shrinking are better, as they can provide increased I L1-L2 |. Also, in consideration of reducing the equipment cost of the stretching step, the number of times and the bending angle of the track of the jig are preferably made smaller. From this point of view, it is preferable that the direction of the film is curved, so when the two edges of the film are gripped, the direction between the progress of the film at the output step of gripping the two edges of the film and the direction of the film's substantial stretching The angle is 20 to 70 degrees, as shown in Figures 4, 5 and 7. In the present invention, as for a device (so-called stretcher device) for stretching a film by gripping its two edges and granting tension, as shown in Figs. 3 to 7 is preferable. Similarly, in addition to the conventional two-dimensional stretching machine equipment, a stretching step can be used here, in which the edge clamp provides two spiral-shaped sides to generate a trajectory difference between the two equipment, as shown in FIG. 8 Displayed. For stretching type stretching machines, a clamping-fixing chain structure that moves along the track is often used, but in the case of using an unbalanced stretching method such as the present invention, the ends will eventually Alternate at the input and output steps as shown in Figures 3 and 4, in some instances, the start grip -47-200301575 grip and grip grip release do not occur simultaneously. In this example, the substantial step lengths L1 and L2 are not only the distance between the start of gripping and gripping release, but also the moving length of the film grip to grip the edge portion of the film as already described. In the case where there is a moving speed difference between the left and right sides of the film at the output of the stretching step, wrinkles or misalignment will occur during the output stretching step, so the conveying speed of the film holder on the left and the film The conveying speed of the jig on the right is substantially the same. The difference in conveying speed is preferably 1% or less, more preferably less than 0.5%, and most preferably less than 0.55%. Speed as used herein means the length of the track of the fixture on each of the right and left sides per minute. In the ordinary stretcher stretching machine or the like, the speed of the chain or the chain driven blade chain, the frequency of the drive motor, etc. will produce speed unevenness of seconds or less, often several% Unevenness. However, this unevenness does not correspond to the speed difference described in the present invention. (Shrinkage) The shrinkage of the stretched polymer film may be performed during or after stretching. Sufficient shrinkage can be performed to remove the wrinkles generated in the skewed polymer film after stretching. As for an apparatus for shrinking a film, a method of applying heat to thereby remove volatile components and the like have been elucidated. However, any device can be used as long as it can shrink the film. As for the preferable film shrinkage ratio, shrinkage of 1 / s i η Θ or more (orientation angle Θ used in the longitudinal direction), or 値 of 10% or more is preferable. (Volatile components) Similarly, wrinkles and distortions are formed when there is a difference in movement between the left and right sides of the film. In the present invention, in order to solve this problem and maintain the supporting properties of the polymer film, the polymer film retains 5% or more volatile components when stretched, and then reduces the volatile components to shrink. The volatile component in the present invention means the volume of the volatile component contained in a unit volume of the film, and its volume can be obtained by dividing the volume of the volatile component by the volume of the film. As for the method of incorporating volatile components, there have been clarified a method of casting the film to incorporate a solvent or water, a soaking method, applying or spraying a solvent, water or the like before stretching, and stretching A method in which a solvent or water is applied to a film. Films of hydrophilic polymers (such as polyvinyl alcohol, which contains water in a high temperature and high humidity environment) can be incorporated by stretching after the humidity has been adjusted to a high humidity environment or by stretching under high humidity conditions Volatile components. Any other equipment capable of incorporating 5% or more volatile components into the polymer film may be used. The preferred volatile component can vary depending on the type of polymer film. It can be increased to the maximum volatile content as long as the self-supporting properties of the polymer film are maintained. For polyvinyl alcohol, the volatile component is preferably 10% to 100%. For cellulose acetate, the volatile component is preferably 10% to 2000% (elastic modulus). Regarding the physical properties of the unstretched polymer film, too low an elastic modulus will be in tension. Reduction in shrinkage during and after stretching makes it difficult to remove wrinkles. Similarly, too high elastic modulus requires a large tension to be stretched 'and the strength of the two edges of the gripping film must be increased, which will cause a larger load on the machine. Therefore, the elastic film of the polymer film of the present invention before stretching is -49- 200301375 and the elastic modulus is from 0 · 1 million Pascals to 5 0 0 million Pascals, preferably from 0 · 丨 Mpa to 500 Papas. (In terms of Young's modulus). (The distance between the generation and removal of wrinkles) What needs to be satisfied is to remove the wrinkles generated in the skewed direction when the polymer film is oriented up to the substantial grip release point of the present invention. However, in the case where it takes time to remove the wrinkles it generates, since unevenness occurs in the stretching direction ', it is preferable to remove the wrinkles as short as possible from the point where the wrinkles occur. To achieve this, there have been methods for increasing the volatilization rate of volatile components. (Foreign matter) In the present invention, when a foreign matter adheres to an unstretched polymer film, the surface of the stretched film becomes rough, so it is preferable to remove the foreign matter. In addition, the presence of foreign substances can cause color unevenness and optical unevenness especially after the preparation of the polarizing plate. It is also important that no foreign matter adhere to the protective film before laminating it. It is preferred to operate in an environment that reduces floating dust. In the present invention, the foreign substance mass means a 値 '0 which can be obtained by dividing the weight of the foreign substance adhered to the film surface by the surface area, and the unit is grams per square meter. The amount of the foreign substance is preferably 1 g / m 2 or less, more preferably 0.5 g / m 2 or less, and a smaller amount is more preferable. The method for removing the foreign substance is not particularly limited, and any method that can remove the foreign substance without harmfully affecting the unstretched polymer film can be used. For example, a method for removing foreign substances by spraying a water stream, a method for removing foreign substances by spraying a gas, and removal by wiping -50-200301375 with cloth or a piece of corn (for example, rubber) have been explained. Excluding material methods. (Drying) Any drying conditions can be used to remove the wrinkles. However, it is preferred that the film be adjusted to reach the drying point in as short a travel distance as possible after being oriented to the desired angle. The drying point is a point where the surface temperature of the film becomes the same as the surrounding temperature. From this viewpoint, the drying speed is preferably as large as possible. (Drying temperature) Any drying temperature capable of removing the wrinkles generated may be used, however, it may vary depending on the type of film to be stretched. In the example of the polarizing plate prepared by the present invention using a polyvinyl alcohol film, the drying temperature is preferably 20 V to 100 ° C, and more preferably 4 (TC to 90 ° C. (Swelling ratio). In the present invention, when When polyvinyl alcohol is used as a polymer film and a hardener is used, the swelling ratio of the film in water is preferably different before and after stretching. In particular, the swelling ratio before stretching is preferably higher than that during stretching. Swelling ratio after stretching and drying. More preferably, the film has a swelling ratio in water of more than 3% before stretching and a swelling ratio of less than 3% after stretching. (Definition of curved part) Used to define the fixture The track of the track often needs to have a large bending ratio. In order to avoid the interference or local stress concentration between the thin film clamps due to sudden bending, it is desirable to pull the track of the clamp into an arc (stretch rate)- 51- 2ϋϋ30137υ As far as the stretching rate is concerned, the film stretching rate in the present invention is 1.1 times / minute or more, preferably 2 times / minute or more, and the larger the rate, the better. Similarly, in Movement speed in longitudinal direction is 0 1 m / min, preferably 1 m / min. Considering the productivity, the faster the better. In each example, the upper limit may vary depending on the film and the stretcher to be stretched. (In the longitudinal direction In the present invention, after the two edges of the film are gripped by a clamp, the film is preferably in a pulled state so as to facilitate gripping operation. In particular, a method for applying tension in the longitudinal direction and A similar method. As for the tension 41, the degree of tension that does not relax the film is better, depending on the state of the film before stretching. (Temperature after stretching) In the present invention, the environment after the film is stretched The temperature may be at least the curing point or higher of the volatile components contained in the film. In the case where the film is a polyvinyl alcohol film, the temperature is preferably 25 t or higher. Similarly, in the case of stretching doping In the case where a polyvinyl alcohol film of iodine and boric acid is used to prepare a polarizing film, the temperature is preferably 25 ° C to 90 ° C. (Humidity after stretching) Film (such as polyvinyl alcohol film or cellulose acetate film) In an example, the stretching may be performed in an environment with adjusted humidity. For polyvinyl alcohol, the humidity is preferably 50% or more, more preferably 80% or more, and still more preferably 90%. % Or greater. (Polymer film for polarizing film) The polymer film to be stretched in the present invention is not limited, and a film composed of a suitable thermoplastic polymer of -52-20030137ο can be used. The polymer Examples include PVA, polycarbonate, cellulose acetate, and polymill. The thickness of the unstretched film is not particularly limited, but considering film grip stability and stretch uniformity, the thickness is preferably 1 micron To 1 mm, particularly preferably 20 to 200 microns. As the polymer film for polarizing films, PVA is preferably used. PVA is usually a saponified product of polyvinyl acetate, and may contain a polymer that can be copolymerized with vinyl acetate. Components such as unsaturated carboxylic acids, unsaturated sulfonic acids, olefins or vinyl ethers. Similarly, a modified PVA containing an acetamidine group, a sulfonic acid group, a 4C carboxylic acid group, or an oxyalkylene group can be used. The degree of saponification of PVA is not particularly limited, but from the viewpoint of solubility or the like, it is preferably 80 to 100 mol%, particularly preferably 90 to 100 mol%. The degree of polymerization of PVA is not particularly limited, but it is preferably from 1,000 to 1 0 0 0, particularly preferably from 1 500 to 5 0 0. (Formulation and dyeing method) The polarizing film can be obtained by dyeing PVA, and the dyeing step can be performed by gas phase 丄 / or liquid phase adsorption. In a specific embodiment of the liquid phase method using iodine, the dyeing can be performed by immersing a PVA film in an iodine-potassium iodide aqueous solution. The iodine component in the solution is preferably 0.1 to 20 g / liter, the potassium iodide component is preferably 1 to 200 g / liter, and the ratio of iodine to potassium iodide is preferably 1 to 200. The dyeing time is preferably from 10 to 5000 seconds, and the temperature of the solution is preferably from 5 to 60 ° C. As for the dyeing method, any method such as a method of applying or spraying an iodine or a dye solution and a soaking method can be used. This dyeing step may be provided before or after the stretching step of the present invention, but because the film is suitably swelled to make stretching easier by -53- 200301375 ', it is particularly preferable to dye in the gas phase before the stretching step. (A hardening agent (crosslinking agent or metal salt) In the step of manufacturing a polarizing film by stretching PVA, it is preferable to use an additive capable of crosslinking PV A. In particular, the skew drawing of the present invention In the example of the stretching method, in the case where the PVA is not sufficiently hardened in the output stretching step, the orientation direction of the PVA may deviate in some examples due to the tension during the step. Therefore, it is preferable to immerse the film in The solution is applied in the cross-linking agent solution or before or during the stretching step to thereby incorporate the cross-linking agent into the film. The method of granting the cross-linking agent to the PVA film is not particularly limited, and any method such as applying The method of immersing a film in a solution, the method of coating or spraying a solution on or over a film, etc. The immersion method and the coating method are particularly preferable. As for the coating equipment, any generally known equipment such as a roll coater can be used , Die coater, rod coater, slide coater or curtain coater. Similarly, the method of contacting the film with the cloth, cotton or porous material impregnated with the solution is preferred. As for the crosslinking agent Those described in U.S. Patent No. 2 3 28 97 are actually better with boric acid or borax. Similarly, salts of metals such as zinc, cobalt, zirconium, iron, nickel, and manganese can be used and crosslinked Agent combination. A washing or water washing step can be provided after the hardener is added. The crosslinking agent can be applied before or after gripping by the stretcher, and is shown in the specific examples in Figures 3 or 4 Medium (where the stretching in the width direction is substantially completed) can be performed in any step up to the end of step (b). (Polarizing element) It is preferably dyed with a dichroic dye and iodine. Specific examples of this dichroic dye -54- 200301375 Includes dye compounds such as azo dyes, Sty 1 bene dyes, pyrazolone dyes, triphenylmethane dyes, quinoline dyes, hydrazone dyes, thiazine dyes, and quinone dyes. Water-soluble dyes are preferred, but are not limited thereto. It is also preferred to introduce hydrophilic groups (such as sulfonic acid groups, amine groups, and hydroxyl groups) into these two-color molecules. Examples of specific two-color molecules include CK Derrickt (D irect) Yellow 1 2, C. I. Drexit Orange 3 9, C. I. D. Derekt Orange 7 2, C. I. Drexit Red 3 9, C. I. Drexit Red 7 9, C. I. Derekte Red 8 1, C. I. Derekte 83, C. I. Derekte 89, C. I. Derekte 48, CI De Rickert Blue 67, CI Derekert Blue 90, CI Druckett Green 5 9 and C.I. Acid Red 37, and further include those described in Japanese Patent Publication No. 70802/1987, 161202 / 1989, 172906/1989, 172907/1989, 183602/1989, 248105/1989, 265205/1989 and 26 1 024/1 99 5. These dichroic molecules are used in the form of free acid or alkali metal salt, ammonium salt or amine salt. Polarizing elements having different colors can be manufactured by mixing two or more of these two-color molecules. Therefore, those compounds (dyestuffs) are preferably black when the polarization axis of the polarizing element or polarizing plate containing it is made at the right angle intersection, or the element may contain a combination of two dichromatic molecules to make them appear Black, so that the device can display both excellent veneer light transmittance and excellent polarization. The stretching method of the present invention can also be preferably applied to manufacture a so-called polyethylene-based polarizing film. Its polyolefin structure can be formed by removing water or chlorine from PVA or polyvinyl chloride to provide polarized light. Conjugated double bond. < Adhesive> There is no particular limitation on the adhesive between the polarizing film and the protective film, and it has been clarified. A modified alkylene alkylene group (PVA) and an aqueous solution of a boron compound are particularly preferred for resins based on PVA. A boron compound or an aqueous potassium iodide solution can be added to a PVA-based resin and used. The dry thickness of the adhesive layer is preferably from 0.01 to 10 m, particularly preferably from 0.05 to 5 m. < Integration step > In the present invention, the method preferably includes a drying step for shrinking the stretched film after stretching the film and reducing its volatile component; and a step of laminating the protective film to After at least one side of the film, a post-heating step after drying or during. As for the specific lamination method, it has been clarified that a method of laminating a protective film on the film using an adhesive under the state of being gripped on both edges of the film during drying, and then trimming the two edges; and After drying, the two sides have been released from the clamp, and a protective layer is laminated on the film after trimming. As for the trimming method, general techniques can be used here, such as a method of cutting by a cutter (such as a trimming tool) and a method of using a laser. After lamination, heating is preferably performed to dry the adhesive and improve the polarizing ability. As for the heating conditions, a heating temperature of 30 ° C or higher is preferred (for a water system), but it may depend on the type of additive, 40 ° C to 100 ° C is better, and 50 ° C to 80 ° C is still more good. Considering performance and yield, it is better to perform these steps on the integration line. < Cut > Fig. 2 shows an example of cutting the polarizing plate of the present invention. When the absorption axis 7 1 (that is, the stretching axis of the conventional polarizing plate) of the polarizing plate coincides with the longitudinal direction 7 2, the absorption axis 8 1 (that is, the stretching axis of the polarizing plate of the present invention) and -56- 200301375 Tilt 8 2 at 45 degrees, as shown in Figure 2. Since this angle is in accordance with the angle between the vertical or horizontal direction of the absorption axis of the polarizing plate and the liquid crystal cell after the film is laminated on the liquid crystal cell in the LCD, skew cutting is not required in the cutting step. In addition, as can be seen from Fig. 2, the polarizing plates of the present invention can be cut in a straight line along the longitudinal direction. Therefore, they can be manufactured by cutting along the longitudinal direction without using cutting, and thus their yield is remarkably excellent. < Adhesive layer > In the circular polarizing plate of the present invention, an adhesive layer for laminating on other liquid crystal display members is provided to at least one side of the above-mentioned polarizing film or optical film. A release film is preferably provided on the surface of the adhesive layer. The adhesive layer is optically transmissive and exhibits suitable viscoelasticity and adhesive properties. As for the adhesive layer in the present invention, an adhesive or a self-adhesive polymer (such as an acrylic copolymer, an epoxy-based resin, a polyurethane, a silicone-based Polymer, polyether, butyral-based resin, polyamidamine-based resin, polyvinyl alcohol-based resin or synthetic rubber) to form a thin film, and then chemically hardened according to the drying method Hardening method, thermosetting method, heat melting method or light hardening method. Among the above, the acrylic copolymer is the easiest to control the adhesive properties, and has excellent transparency, weather resistance and durability, so it can be preferably used. Similarly, the adhesive layer of the present invention can be subjected to a crosslinking treatment. In this example, the crosslinking treatment using the intermolecular crosslinking agent may be performed according to a method of mixing the adhesive solution and the intermolecular crosslinking agent. As for the intermolecular cross-linking agent, any suitable cross-linking agent can be used without limitation depending on the kind of functional groups related to the intermolecular cross-linking of the adhesive polymer. Therefore, any well-known cross-linking agent can be used. In the present invention, it is preferable to adjust the elastic modulus under relaxation to a suitable range, thereby avoiding the curling of the polarizing plate (when the liquid crystal display device is exposed to high temperature and high humidity conditions for a long time (Due to the shrinkage of the polarizing film) and the trouble of optical changes such as white unevenness. In particular, after a relaxation time of 105 seconds at a standard temperature of 23 ° C, the elastic modulus at relaxation is preferably 1 5 X 1 0 5 dyne / cm 2 or less, more preferably 13 × 105 dyne / Cm², particularly preferably ιοχίο 5 dyne / cm² or less. In the case where the elastic modulus is too small at the time of relaxation, the contact surface of the adhesive layer is bonded and destroyed; in the case where the elastic modulus is too large at the time of relaxation, the polarizing film cannot sufficiently relax and shrink, resulting in a warped liquid crystal display device. Qu or similar problems. A specific method for measuring the elastic modulus at relaxation is described below. Storage modulus of 1 mm thick adhesive layer (5 mm x 1.1 mm) at _ 100 to 200 ° C (Γ can use dynamic viscoelasticity measuring equipment (by Se i ko Denshi) KK (Manufactured) is measured at a frequency of 1 Hz. The data obtained in this way can be converted into diffusion data G '(ω) using the following WLF-type time-temperature conversion rule at a standard temperature of 23 ° C according to the frequency ω, and then at The elastic modulus Gk and relaxation time tk at the time of relaxation can be estimated according to the summarized Maxwell model. Therefore, the elastic modulus at the time of relaxation is measured at a standard temperature of 23 ° C and a relaxation time of 105 seconds. LogaT = Cl (T-Ts) / (C2 + T-Ts) g '(co) = Gk [co · τ] 〇2 / {1 + (α) · τ] 〇2}] In the above formula , 丨 〇gTa represents the offset factor, τ represents the temperature 'coefficient -58-2ύ〇3〇ΐ375 CU8.86, the coefficient C2 = lOl.6, the characteristic temperature Ts = glass transition temperature Tg + 4 5 ° C, and η k represents the relaxed viscosity. < Liquid crystal display device and the like > The polarizing plate of the present invention has been found to have a variety of applications, but because of its characteristic that the orientation axis is inclined to the longitudinal direction The polarizing film with a tilt angle of 40 to 50 degrees between the orientation axis and the longitudinal direction can be used particularly well for polarizing plates and LCDs (for example, all liquid crystal modes, including TN, STN, OCB, ROCB, ECB, CPA, IPS And VA) and circular polarizers used in organic EL displays to prevent reflections. They can also be used appropriately with different components (such as phase retardation films (for example, λ / 4 plates and λ / 2 plates), and wide viewing angles. Film, anti-glare film, or hard-coated film). The basic structure of a reflective liquid crystal display device is described below. For example, a reflective liquid crystal display device may include (from the bottom) a lower substrate, a reflective electrode, and a lower orientation. Film, liquid crystal layer, upper alignment layer, transparent electrode, upper substrate, λ / 4 plate and polarizing film. The lower substrate and reflective electrode can form a reflective plate. The lower alignment film to the upper alignment film can constitute a liquid unit. The λ / 4 plate can be configured Any position between the reflective plate and the polarizing film. In the example of a color display, a color filter layer is further provided. The color filter layer is preferably provided between the reflective electrode and the lower alignment film or between Between the orientation film and the transparent electrode. It is also possible to use a transparent electrode instead of a reflective electrode to provide a reflective plate separately. As for a reflective plate to be used in combination with a transparent electrode, a metal plate is preferred. The surface of the reflective plate is flat and In the smooth example, only -59- 20030137α can reflect the directional reflective component in some examples, so the viewing angle is narrow. Therefore, it is preferable to use an uneven structure on the surface of the reflective plate (described in Japanese Patent Case No. 2 7 5 6 2 0). For reflectors with flat surfaces, a light-scattering film can be provided on one side of the polarizing film (on the cell edge or on the outside) (instead of introducing uneven structures onto the surface). The liquid crystal cell is preferably a TN (Twisted Nematic) mode, a STN (Super Twisted Nematic) mode, or a ΗΑΝ (hybrid array nematic) mode. The torsional angle in the TN mode liquid crystal cell is preferably 40 to 100 degrees, more preferably 50 to 90 degrees, and most preferably 60 to 80 degrees. The product (And) 获得 obtained by multiplying the refractive anisotropy (Δη) of the liquid crystal layer by the thickness (d) of the liquid crystal layer is preferably 0.1 to 0.5 μm, and more preferably 0.2 to 0.4 μm. The twist angle in the STN mode liquid crystal cell is preferably 180 to 360 degrees, and more preferably 220 to 270 degrees. The product (And) 获得 obtained by multiplying the refractive anisotropy (Δn) of the liquid crystal layer by the thickness (d) of the liquid crystal layer is preferably 0.3 to 1.2 microns, and more preferably 0.5 to 1.0 microns. For the HAN mode liquid crystal cell, it is preferable that the liquid crystal molecules are substantially vertically aligned on one substrate, and the pretilt angle on the other substrate is 0 to 45 degrees. The product (And) 获得 obtained by multiplying the refractive anisotropy (Δn) of the liquid crystal layer by the thickness (d) of the liquid crystal layer is preferably from 0.1 to 1.0 μm, more preferably from 0.3 to 0.8 μm. The substrate in which the liquid crystal molecules are vertically aligned may be a substrate on the side of a reflective plate or a substrate on the side of a transparent electrode. The reflective liquid crystal display device can be in a normal white mode (where a portion to which a low voltage is applied appears bright and a portion to which a high voltage is applied appears dark) or in a normal black mode (where a portion where a low voltage is applied appears dark and a high voltage is applied) — 60- 200301375 part of the display is bright) use, normal white mode is better. A typical configuration example of the transflective liquid crystal display device is shown in FIG. 13 as a schematic sectional view. Of course, those skilled in the art can understand that the transflective liquid crystal display device of the present invention is not limited to this example, but can have various variations. The transflective liquid crystal display device 1 shown in FIG. 13 includes a front end. Substrate 1 0 3, a rear substrate 1 〇4, a liquid crystal portion 1 〇5, a plurality of front electrodes 1 〇6, a rear electrode 1 〇7 matching the front electrode 106, a front circular polarizer 1 〇8 A circular polarizing plate 1110 at the rear end and two or more color filters having mutually different wavelengths of transmitted light. The structure and manufacturing process of the transflective liquid crystal display device 141 are described in detail below. A substrate including a glass material is used as the front substrate 103 and the rear substrate 104. A thin film of a conductive material composed of molybdenum (Ta) or the like (according to the sputtering method) is formed on one side of the back substrate 104, and the thin film is patterned into a provided shape. Therefore, the signal electrode 125 can be formed in the two terminal elements 1 13 and the signal wiring connected to the signal electrode 125. Subsequently, in order to form the insulating layer 1 124 in the two terminal elements, the surface of the signal electrode 125 and the surface of the signal wiring are anodized in an electrolyte of tartrate or the like. Then, in order to form the upper electrode 1 1 2 2 in the two terminal elements, a thin film of a conductive material (such as titanium (T i)) may be formed on one side surface of the back-end substrate 104, and then the film is patterned into the provided shape. Next, in order to form a rear electrode 10 7 as a pixel electrode, the surface of the back substrate 10 04 (two terminal elements 1 1 3 have been formed on this surface) is shaped into a 201301375 semi-transparent aluminum (A 1) film. According to the vacuum deposition method or the sputtering method using a photomask. Therefore, the rectangular portions of the many translucent films remain as the back-end electrode 107, and the rectangular back-end electrode 107 is arranged in a row, and is in contact with the upper electrodes 1 2 5 of the respective two terminal elements. . The thickness of the rear electrode 10 is about 50 nanometers, and it can reflect the external light that has passed through the liquid crystal layer in the reflection mode, and can partially penetrate the light from the backlight 1 12 in the transmission mode. For each color, a color filter 142 composed of a resin material that can penetrate only a light component of a predetermined wavelength range is printed on one side of the front substrate 103. Then, a transparent ITO film is formed on one side of the front-end substrate 103, and then patterned so that a strip-shaped portion arranged in the stripe remains on the front electrode 106. Then the end substrate 103 and the back substrate 104 are registered (one side surface of each * part is formed), so the front electrode 106 faces the rear electrode 107, and the signal wiring and formation on the back substrate 104 The longitudinal direction of the front electrode 106 of the bar is at a right angle (viewed along the vertical direction of the substrate). Furthermore, the two substrates are laminated with a predetermined interval left around them. A liquid crystal material (for example, a TN liquid crystal having a refractive index anisotropy Δη of 0.065) used to form the liquid crystal portion 105 is sealed inside the interval of the liquid crystal cell thus obtained. After the liquid crystal portion 105 is formed, a circular polarizing plate is laminated on both surfaces of the liquid crystal cell. The transflective liquid crystal display device 141 includes a combination of a panel thus prepared and a backlight 1 12. The display of the image can be achieved by using two types of circular polarizers (in the example of reflection mode, the state of the light is polarized by the circular polarizer) and by applying a voltage to the liquid crystal layer-62- 200301375 The orientation state is changed. The light transmission axis of the polarizing film of the circular polarizing plate laminated on the front substrate 103, the light transmission axis of the polarizing film of the circular polarizing plate laminated on the rear substrate 104, and the closest to the substrate in the liquid crystal portion 105 The alignment of the liquid crystal molecules of 103 and 104 is usually registered, so the monochrome liquid crystal display panel becomes normally white (displays white when no voltage is applied to the liquid crystal portion 105), but it is not limited to this configuration. (IV) Embodiment Examples The present invention will be described in detail with reference to examples, but the present invention is not limited in any way. Example 1 Preparation of Π U / 4 plate 100 g of 8-methyl-8-methoxycarbonyl tetracyclo [4.4.0.12, 5.17, 10] dodec-3-ene, 60 g of 1,2-diene Methoxyethane, 240 g of cyclohexane and 3.4 ml of a solution of 0.96 mol / l of diethylaluminum chloride in toluene were added to a 1-liter autoclave with an internal volume. In a separate flask, 20 ml of a 0.5-mole / liter solution of tungsten hexachloride in 1,2-dimethoxyethane and 10 ml of a mole / liter of paraldehyde were mixed.丨, 2_ Dimethoxyethane solution. 4.9 ml of this mixed solution was added to the mixture described above in a pressure cooker. After tightly closing the pressure cooker, the mixture was heated to 80 ° C with stirring for 3 hours. A mixed solvent of 1,2-dimethoxyethane and cyclohexane (2/8 by weight ratio) was added to the polymer solution thus obtained to adjust the polymer / solvent ratio to 1 / 丨. (By weight ratio) 'Then 20 g of triethanolamine was added thereto and stirred for 10 minutes. -63- 0301375 Add 500 grams of methanol to this polymer solution, and stir for 30 minutes and then stand. The upper layer of the two separated layers was discarded, and methanol was added again, followed by stirring and standing, and the upper layer was discarded. Further, the same procedure was repeated twice, and the resulting lower layer was appropriately diluted with cyclohexane and 1,2-diethane to obtain a 10% cyclohexane-1,2-dimethoxyl solution (polymerization concentration). To this solution was added 20 g of palladium / magnesium dioxide (manufactured by Nikki Kagaku KK; made of palladium, and hydrogenated in a pressure cooker under a hydrogen pressure of 40 kg / cm2, 4 Hours, followed by removal of the hydrogenation catalyst-hydrogenated (co) polymer solution by filtration. Similarly, pentaerythritol-tetrakis [3-(3,5-di-tert-butyl-phenyl) propionic acid Ester] antioxidant was added to this copolymer solution in an amount of 0.1% (based on the (co) polymer), and then the solvent was removed under reduced pressure at ° C. Subsequently, the extruder was used to melt the pellets under a nitrogen atmosphere to obtain a thermal grease A containing a basic skeleton of tricyclodecane. From the nine particles of Resin A using a solution-casting method using dichloromethane as a solvent, a film having a thickness of 100 m and a retardation of 15 nm was obtained. The resulting base film was uniaxially stretched at a stretch ratio of 125% to obtain a λ / 4 plate A having a thickness of 90 m and a retardation of 値 135 nm. (Film thickness) The thickness can be measured by a laser focus shift meter (LT-8010, manufactured by (K i e n c e) KK · KK ·). In addition, the measurement of hysteresis can be measured using a 64-minute clock given by Ogi to Socorgi, and then there is repeated phase methoxysilane silane oxygen content = 5%) E 165 ° C to obtain 4-hydroxyl ^ (380 resin and plastic tree thermoplastic base thin to obtain Keynesi (Oj i 200301375

Keisoku Kiki) KOBRA-2 1 ADH manufactured by K.K. After that, the same procedure is applied. (2) Preparation of λ / 4 plate According to Example 3 of WO 00/2670 5, a film obtained by stretching a polycarbonate copolymer (λ / 4 plate B) was prepared. The in-plane hysteresis of the film at a wavelength of 450 nm is 148.5 nm, the in-plane hysteresis at a wavelength of 550 nm is 161.1 nm, and the in-plane hysteresis at a wavelength of 650 nm is 162.9 nm. . (3) Preparation of λ / 4 plate C calls for 100 parts by weight of cellulose acetate having an average degree of acetylation of 59.5%, 7.8 parts by weight of triphenyl phosphate, and 3.9 parts by weight of phosphoric acid Diphenyl biphenyl ester, 1.32 parts by weight of a retardation control agent (4 1 -trans), 5 8 7.6.9 parts by weight of dichloromethane, and 50.85 parts by weight of methanol are mixed at room temperature, To prepare a solution (coated rubber). C7H15 ^ 0 ^ 〇C〇..0 ^ C〇〇 __ ^^ C7Hi5 ❿ .. *. Ί-; · '·..: ..: 4 1-trans-coating compound thus obtained Cast onto a film strip, dried at room temperature for 1 minute, and dried at 14 5 ° C for 5 minutes. The residual amount of the solvent after drying was 30% by weight. The cellulose acetate film was removed from the tape, dried at 120 ° C for 10 minutes, and then stretched at 130 ° C in a direction parallel to the casting direction by 1 · 3 4 times. Extension ratio). The film shrinks freely in a direction perpendicular to the stretching direction. After stretching, the thin -65- 200301375 film was dried at 120 ° C for 30 minutes, and the resulting film was used as a λ / 4 plate C. The residual amount of the solvent after stretching was 0.1% by weight. The thickness of the generated λ / 4 plate C was 112.7 microns, measured by a polarized light ellipsimeter (M-50; manufactured by NihonBunko KK) at a wavelength of 450 nm, 550 nm, and 590 nm The hysteresis ratios are 125.2 nm, 137.8 nm, and 141.1 nm. Furthermore, Abbe can be used for the refractive index nx in the in-plane low-axis direction at a wavelength of 50 nm, the refractive index ny in the direction perpendicular to the in-plane low axis, and the refractive index nz in the thickness direction. The (Abbe) refractometer was used to measure the refractive index, and the angular dependence of the hysteresis was measured, and (η X-nz) / (η X-ny) 値 was calculated to be 1,48. Additionally, the (nx-az) / (nx-ny) 値 can be called the NZ parameter, and the larger this 値, the smaller the change in display contrast (due to the viewing angle). Therefore, the 値 is preferably larger. (4) Preparation of λ / 4 plate D in 6-methyl-1,4,5,8-dimethylalkyl-1,4,4 &, 5,6,7,8,8 & -octahydronaphthalene Add 10 parts of 15% triethylaluminum catalyst in cyclohexane solution, 5 parts of triethylamine and 10 parts of 20% titanium tetrachloride in cyclohexane solution, followed by ring opening in cyclohexane Polymerization. The resulting ring-opening polymerization product was assisted in hydrogenation with a nickel catalyst to obtain a polymer solution. This polymer solution can be coagulated in isopropanol and dried to obtain a powdery resin. This resin has a number average molecular weight of 40,000, a hydrogenation ratio of 99.8%, and a Tg of 142 ° C. The powdered resin mentioned above is melted at 250 ° C and then pelletized. These nine tablets were melted and extruded through a 300 mm wide T-die using a uniaxial extruder with 40-mm screw 200301575 pattern screws. A three-roller cooling roller with a diameter of 300 mm was used to wind the Obtain a slice. In these procedures, the resin temperature in the die section was 27 5 ° C, and the temperatures of the three cooling rollers were 12 (TC, 100 ° C, and 100 ° C (sequentially the first roller, the second roller, and the third Roller). Because the thickness of this unstretched sheet is uneven at the edges, trim the edge part with a width of 20 cm from the edge, and observe the surface visually and with an optical microscope. No foaming, Streaks and blemishes. Tg of film is 139 ° C, average film thickness is 75 microns, thickness non-uniformity is + -2 microns or less. Light transmittance is 91.5%, average hysteresis is 11 nm, surface The internal variability is +-5 nm. This unstretched sheet is controlled at 1 40 +-2 ° C and uniaxially stretched at a stretch ratio of 1.2 5 times to obtain a λ / 4 plate D The average thickness of the λ / 4 plate D is 50 micrometers, the thickness non-uniformity is + -1.2 micrometers and the average hysteresis is 140 nanometers, and the in-plane variability is + -7 nanometers. The λ / 4 plate D is maintained at 2 hours at 80 ° C, then cooled to room temperature, and then measured the hysteresis to an average of 136 nm. (5) Preparation of λ / 2 plate was made in the same manner as λ / 4 plate B λ / 2 plate. The average in-plane hysteresis is 272 nm. "I Π Preparation of circular polarizing plate (1) Preparation of circular polarizing plate A The average degree of polymerization was washed with ion exchange water at a temperature of 17 ° C and the thickness was The second surface of the 75 micron PVA film was 60 seconds. Then, the water on the surface of the PVA film was scraped off with a blade made of stainless steel 200301375. Then, the PVA film was immersed in 4CTC 0.77 g / L iodine and 60.0 g / Liter of potassium iodide in water solution for 5 5 seconds, while correcting the concentration to keep the concentration of the aqueous solution fixed. Then, immerse the PVA film in 40 ° C 42.5 g / liter of boric acid and 30 g / liter of potassium iodide solution in 90 Second, while correcting the concentration to keep the concentration of the aqueous solution fixed. Then, the excess water on the surface of the PVA film was scraped off with a blade made of stainless steel to reduce the water content distribution of the film to 2% or less. The introduction of the PVA film is shown in the stretcher of the stretcher shown in Figure 1. The film was fed at a rate of 100 meters at a conveying speed of 5 meters / minute, and then at 50 ° C and 9 5%. Stretching at a factor of 5.5. Then, dry at 70 ° C. The film was simultaneously flexed and contracted with a stretcher in the direction of stretching (as shown in Figure 2). The film was released from the stretcher, and then the two edges were trimmed by 3 cm with a knife. The film was on one side The λ / 4 board prepared above and the saponified Fu ji Tack (cellulose triacetate with in-plane retardation 値 3.0 nm and 80 micron thickness were prepared by Fuji Optical Film Co., Ltd. (Manufactured by Fuj i Photo Film Co., Ltd.), using a 3% PVA aqueous solution (PVA-1 17H; manufactured by Kuraray Co., Ltd.), and then heated to 70 ° C10 Minutes to obtain a polarizing plate A with an effective width of 650 mm and a length of 10-meters (in the form of a roller). Because the polarizing plate is used in the form of a roller, the usable area of the polarizing plate is as high as 91.5% (calculated by the area efficiency shown in Figure 2). The drying point was set in the middle of the region (c), and the water content of the PVA film before drying was 40% and the water content after stretching was 6.5%. 200301375 The difference in conveying speed between the tensioner on the left and the tensioner on the right is less than 0.55%, and the angle between the centerline of the introduced film and the centerline of the film to be fed to the next step is 0 degree. Here, | LI-L2 | is 0.7 meters and W is 0.7 meters, and the relationship is | L1-L2 | = W. No wrinkles or deformation of the film was observed at the output of the stretcher. The direction of the absorption axis of the resulting continuous-length circular polarizing plate A is inclined at 45 degrees with the low axis of the protective film (Fuji Adhesive) and the low axis of the λ / 4 plate. The degree of polarized light measured at 550 nm was 99.8%, and the light transmittance of the single polarizer was 41%. Similarly, the circular polarizing plate A has a thickness of 200 μm. (2) Preparation of circularly polarizing plates B, C, D, and E. Circularly polarizing plates B, C, and D were prepared in the same manner as mentioned above, except that λ / 4 plate B was used separately in the aforementioned process. , C, and D replace the λ / 4 plate A to prepare a circularly polarizing plate. Furthermore, a polarizing plate was prepared in the same manner as mentioned above, except that Fuji Adhesive cloth (cellulose triacetate with an in-plane retardation of 3.0 nm and a thickness of 80 micrometers) was manufactured by Fuji Photo Film Co., Ltd. ) Replace λ / 4 plate A. The polarizing plate was laminated with an acrylic adhesive layer (20 microns) having an elastic relaxation modulus of 12x1 04 dyne / cm and a λ / 4 plate B laminated therebetween, and then subjected to aging treatment at a temperature of 50 ° C to prepare a circle Polarizing plate E. Because the polarizing plate is used in the form of a roller, the usable area of the polarizing plate is as high as 91.5%. Calculate the area efficiency shown in Figure 2. (3) The preparation of the circular polarizing plate F is as shown in Figure 10. Happen 'insert λ / 2 plate 122 and λ / 4 plate B124 between them. Acrylic 20030137a adhesive layer (20 microns) with an elastic relaxation modulus of 1 2χ 1 04 dyne / cm is laminated. The orientations are 75 degrees and 20 degrees, respectively. The polarizing plate thus prepared was designed as a λ / 4 plate, which has an improved wavelength dispersion when it is irradiated with linear polarized light in a direction perpendicular to the λ / 2 plate edge (zero degree direction), so that it can be seen This linearly polarized light is converted into substantially circularly polarized light (regardless of wavelength) in the light range. Then, this wide-band λ / 4 plate was cut in a vertical direction to a size of 3 1 0 X 2 3 3 nm. The circularly polarizing plate F was prepared in the same process as that of the circularly polarizing plate A, except that the polarizing plate having a protective layer on one side thereof was made into a λ / 4-free plate A, and then the polarizing plate thus prepared was subjected to the same method. The unprotected layer is laminated with the broadband λ / 4 plate, and the longitudinal direction of the polarizing plate and the vertical direction of the broadband λ / 4 plate correspond to each other. For the lamination of the two plates, the broadband λ / 4 plate was coated with gelatin to a thickness of 0.5 micron, and the two plates were laminated with a 3% PVA aqueous solution (PVA-124Η) as an adhesive. Because the polarizing plate is used in the form of a roller, the usable area of the polarizing plate is as high as 9 1 · 5%-calculated based on the area efficiency shown in Figure 2. (4) Preparation of the circular polarizer G for comparison The commercially available polarizer with a base of iodine (HLC2-5618; width: 6 50 mm) can be used for comparison. Co., Ltd. (manufactured by Sanritz Corporation) to replace the polarizing plate, and cut the polarizing plate into a sheet-shaped polarizing plate with a size of 310x233 nanometers in a direction inclined at 45 degrees from the longitudinal direction, and then the strip and λ / 4 plates B laminated. Because the polarizer is cut in a 45-degree direction, the usable area of the polarizer is as high as 64.7% (calculated based on the area efficiency shown in Figure 12) 200301375 < Property evaluation > The following table lists the different polarizers Degree of polarization measured at 5 50 nm and veneer transmittance at 550 nm and Τ | | (450) / Τ 丄 (450) and Τ | | (590) / Τ 丄 before and after durability test (590). The usable area of these polarizing plates and the visual evaporation of these polarizing plates. < Visual evaluation method > For visual evaporation, the circularly polarizing plate was manufactured from Zaurus MI · L1 (manufactured by Sharp Corporation (Sharp) Co., Ltd.) ) Move _ Divide. Each of the previously mentioned circular polarizers was then mounted on the element. The hue of the element was then evaluated visually. < Durable evaporation method > The durable evaporation method was performed at a temperature of 60 ° C for 100 hours.

-71- 200301375 invention invention invention invention invention invention comparison circular polarizer A circular polarizer B circular polarizer C circular polarizer D circular polarizer E circular polarizer F circular polarizer G single plate light transmittance 41% 39% 38% 40% 37% 41% 39% Degree of polarization 99.6% 99.8% 99.8% 99.8% 99.5% 99.7% 99.8% Τ | | (450) / Τ 丄 (450) before durability test 0.98 0.98 0.97 0.98 0.98 0.97 0.97 Τ | | (450) / Τ 丄 (450) after durability test 0.97 0.98 0.96 0.97 0.97 0.96 0.96 Τ | | (590) / Τ 丄 (590) before durability test 0.99 0.99 0.99 0.99 0.99 0.98 0.98 0.98 τ | 1 ( 590) / Τ 丄 (590) 0.98 0.98 0.98 0.98 0.98 0.97 0.97 Polarizable plate usable area after durability test 91.5% 91.5% 91.5% 91.5% 91.5% 91.5% 91.5% 64.7% Visual evaluation is good

"III 1 Preparation elements A to E of the transflective liquid crystal display The circularly polarizing plates A to E were used to prepare the transflective liquid crystal display devices A to E shown in FIG. 13 according to the previously mentioned procedure. In addition, the The semi-transmissive liquid crystal display device E is for comparison. "IV 1 Evaluation of the liquid crystal display device The semi-transmissive liquid crystal display devices A to E thus prepared are subjected to the following evaluations (Π Display Quality in Reflection Mode-72- 200301375 per The reflectivity of a liquid crystal display device in a white display portion and its reflectance in a black display portion can be determined by using a spectral colorimeter (CM-2 0 2, manufactured by Mi Norut a KK · KK.) Measure and calculate the contrast ratio. The results are shown in Table 3-1. (2) Display quality in transmission mode The brightness of each liquid crystal display device in the white display portion after the backlight is turned on and its brightness in the black display portion can be measured. It was measured using a brightness meter (BM-5A, manufactured by TOPCOM KK ·), and the contrast ratio was calculated. The results are shown in Table 3-1. Table 3-1 ABCDE Translucent Liquid Crystal Display Device Invention Invention invention Compare the contrast ratio in reflection mode 9: 1 9: 1 12: 1 8: 1 8: 1 The contrast ratio in transmission mode 100: 1 105: 1 110 · · 1 90: 1 100: 1 Thickness (microns) 1500 1500 1523 1460 1600 From the results shown in Table 3-1, it is clear that compared with the comparative liquid crystal display device E, the liquid crystal panels of the liquid crystal display devices A to E are thinner by about 100 microns, but not reduced. Contrast ratio between reflection mode and transmission mode.

This application is based on Japanese Patent Application JP claimed on December 25, 2001

2001-391780; Japanese Patent Application JP 2002-2477 claimed on January 9, 2002; and Japanese Patent Application JP 2002-3778 claimed on January 10, 2002, the entire contents of those articles are incorporated herein by reference. (Same as detailed). -73- 20030137a (V) Brief description of the drawings Fig. 1 is a perspective view showing the relationship between the optical film and the polarizing film in the circular polarizing plate of the present invention. Fig. 2 is a plan view of the cutting state of the circular polarizing plate of the present invention. Fig. 3 is a plan view of an example of a method for skew-stretching a polymer film of the present invention. Fig. 4 is a plan view of an example of a method for skew-stretching a polymer film of the present invention. Fig. 5 is a plan view showing an example of a method for skew-stretching a polymer film of the present invention. Fig. 6 is a plan view of an example of a method for skew-stretching a polymer film of the present invention. Fig. 7 is a plan view of an example of a method for skew-stretching a polymer film of the present invention. Fig. 8 is a plan view of an example of a method for skew-stretching a polymer film of the present invention. FIG. 9 is a plan view of a structure layer of a liquid crystal display device of Example 3. FIG. Figures 10 (10A to 10D) are cross-sectional views of a specific embodiment of the circular polarizing plate of the present invention. Figure 11 (1 1 A and 1 1 B) illustrates the definition of the coordinate axis. Fig. 12 is a plan view of a conventional cutting method of a polarizing plate. Figure 13 is a diagram of a semi-transmissive liquid crystal display device of the present invention. "Description of reference characters and numbers 1 (1) Direction of film introduction; 200301375 (2) Direction of conveying film to the next step; (a) Film introduction step; (b) Film stretching step; (c) Applying The stretched film is conveyed to the next step; A 1 where the clamp starts to grip the film, and the film is stretched from this point (the substantial grip starting point; right); B1 where the clamp begins to grip the film (left) C 1 The position at which the film begins to stretch (the point at which the substantial grip begins; left);

Standard position for Cx film release, where film stretching is done (grass grip release point; left);

Ay completes the standard position for film stretching (substantially grip release point; right) 9 IL1-L2 | the difference in movement between the left side of the film holder and the right side of the film holder 9 w the substantial width of the film at the end of the stretching step The angle between the stretching direction and the film moving direction; 11 the film centerline of the film introduction edge; 1 2 the film centerline to be transported to the next step; 1 3 the track of the film holder (left); 1 4 the track of the film holder (right) ); 15 film introduction side of the film; 16 films to be transported to the next step; 17, 17 'left and right points of the film to start gripping; 18, 18' film release point of gripping;- 75- 200301375 2 1 film centerline of the film introduction edge; 2 2 film centerline of the film to be conveyed to the next step; 23 track of the film holder (left); 24 track of the film holder (right); 25 film of the film introduction side ; 26 the film to be transported to the next step; 27, 27 'left and right points to start gripping the film; 28, grip release point of the film; 33, 43, 53, 63 track of the film clamp (left); Lu 34,44,54,64 Road (right) 35, 45, 55, 65 film introduction side of the film 3 6, 46, 5 6, 6 6 film to be transported to the next step; 70 optical film * 7 1, 7 1 'low axis of optical film 74 adhesive layer or self-adhesive layer; 80 polarizing film; 0 8 1 polarizing film absorption axis; 82 longitudinal direction; 8 3 transverse direction; 90 circular polarizing plate; 9 1 iodine-containing polarizing plate; 92 adhesive layer; 97 liquid unit; 9 8 backlight; -76- 200301375 7 2 longitudinal direction; 100 circular polarizing plate; 1 1 0 polarizing plate; 1 2 1 adhesive layer; 1 2 2 λ / 2 plate; 1 2 3 adhesive layer; 1 2 4 λ / 4 plate ; 103 mesh 1 [end substrate; 104 rear substrate; Yu 105 liquid crystal part; 1 06 front electrode; 107 rear electrode; 108 front circular polarizing plate; 1 1 10 rear circular polarizing electrode ; 1 1 2 backlight; 1 1 3 2 terminal elements; 0 1 122 signal electrodes; 1 1 2 4 insulation layer; 1 2 5 electrodes on top of the 2 terminal elements; 1 4 1 transflective liquid crystal display device; 142 filters Color-77-

Claims (1)

20030137ο: Application: U1. A circular polarizing plate of continuous length, comprising: a polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction; at least one optical film provided on the polarizing film. At least one side surface; and an adhesive layer provided on at least one side of the polarizing film and the optical film; wherein the angle between the absorption axis and the low axis of the at least one optical film is not less than 10 degrees and less than 90 degrees; After the circular polarizing plate's durability test, when 450 nanometers of light was incident from the side of the polarizing film into the circular polarizing plate, the light transmittance of the circular polarizing plate in a direction parallel to the transmission axis The ratio of the light transmittance in the direction where the optical axis is perpendicular can satisfy the following formula (I); and after the endurance test of the circularly polarizing plate, when the light of 590 nm enters the circularly polarizing plate from the side of the polarizing film, The ratio of the light transmittance of the circular polarizing plate in a direction parallel to the transmission axis and the light transmittance in a direction perpendicular to the transmission axis can satisfy the following formula (II): Formula (I) 0 · 95 < Τ // (450) / Τ 丄 (45 0) £ 1 · 05 Formula (11) 0.95 < Τ // (590) / Τ 丄 (590) 51.05 where Τ // (450) represents the transmittance of the circularly polarizing plate in a direction parallel to the transmission axis when 450 nm light is incident from the side of the polarizing film Τ 丄 (450) represents the light transmittance of the circular polarizer in the direction perpendicular to the transmission axis when light of 450 nm is incident from the side of the polarizing film; T // (590) represents 590 nm The light transmittance of the circularly polarizing plate in a direction parallel to the transmission axis when light is incident from the side of the polarizing film; and T 丄 (590) represents when the 590 nm light is incident from the side of the polarizing film of -78- 200301375. The light transmittance of the circularly polarizing plate in a direction perpendicular to the transmission axis. 2. A circular polarizing plate comprising: a polarizing film; at least one protective film provided on at least one surface of the polarizing film; and an adhesive layer provided on at least one of the polarizing film and the protective film Outside; wherein the angle between the absorption axis of the polarizing film and the low axis of the protective film is not less than 10 degrees and less than 90 degrees; after the endurance test of the circular polarizing plate, when the light of 45 nm When the polarizing film is incident on the circular polarizing plate, the ratio of the light transmittance of the circular polarizing plate in a direction parallel to the transmission axis and the light transmittance in a direction perpendicular to the transmission axis can satisfy the following formula (I ); And after the endurance test of the circularly polarizing plate, when the light of 590 nm enters the circularly polarizing plate from the side of the polarizing film, the transmittance of the circularly polarizing plate in a direction parallel to the transmission axis is The ratio of the light transmittance in the direction perpendicular to the transmission axis can satisfy the following formula (II): Formula (I) 0.95 < T // (450) / Τ 丄 (450) 51.05 Formula (11) 0.95 < T // (590) / Τ 丄 (590) 51.05 where T // (45 0) represents the circle when light of 45 0 nm is incident from the side of the polarizing film The light transmittance of the light plate in a direction parallel to the light transmission axis; T 丄 (450) represents the light transmission of the circular polarizing plate in a direction perpendicular to the light transmission axis when light of 450 nm is incident from the side of the polarizing film. T // (590) represents the transmittance of the circularly polarizing plate in the direction of -79- 200301375 parallel to the transmission axis when light of 590 nm is incident from the side of the polarizing film; and T 丄 (5 9 0 ) Represents the light transmittance of the circularly polarizing plate in a direction perpendicular to the transmission axis when light of 5 to 90 nm is incident from the side of the polarizing film. 3. The circular polarizing plate according to item 1 of the patent application scope, further comprising a broadband λ / 4 plate, which includes a λ / 4 plate that provides birefringent light with a 1/4 wavelength phase retardation and a 1/2 wavelength phase The retarded birefringent λ / 2 plates' have their optical axes intersected with each other. 4. The circularly polarizing plate according to item 2 of the patent application scope, further comprising a broadband λ / 4 plate, which includes a λ / 4 plate that provides birefringent light with a retardation of 1/4 wavelength phase and a phase of 1/4 wavelength The retarded birefringent λ / 2 plates' have their optical axes intersected with each other. 5. A liquid crystal display device comprising a liquid crystal cell, a polarizing plate disposed on at least one side of the liquid crystal cell, and a circularly polarizing plate obtained by cutting a circularly polarizing plate such as the item 1 in the scope of patent application . 6. A liquid crystal display device comprising a liquid crystal cell, a polarizing plate disposed on at least one side of the liquid crystal unit, and a circularly polarizing plate obtained by cutting a circularly polarizing plate such as the second item in the scope of patent application. 7. A liquid crystal display device comprising a liquid crystal cell, a polarizing plate disposed on at least one side of the liquid crystal unit, and a circularly polarizing plate obtained by cutting a circularly polarizing plate such as the third item in the patent application. 8. A liquid crystal display device comprising a liquid crystal cell, a polarizing plate disposed on at least one side of the liquid crystal unit, and a circularly polarizing plate obtained by cutting a circularly polarizing plate such as item 4 of the scope of patent application. 9 · A process for manufacturing a circular polarizing plate, comprising:-80- 200301375 preparing a polarizing plate with a continuous length by stretching a continuously fed film, so the track 11 of the jig is on an edge of the film The start of the substantial grip start point 'until the release point of the substantial grip; the track L2 of the other clamp starts from another start point of the substantial grip on the other edge of the polymer film, until the release point of the substantial grip; And the distance W between the two gripping release points can satisfy the following formula (1); in order to maintain the self-supporting property of the polymer film, the volatile component is maintained at a level of 5% or more, and then allowed to be reduced The volatile component shrinks; a polarizing plate is cut from the polarizing plate having a continuous length; a broadband λ / 4 plate is prepared, which can be combined with a λ / 4 plate that provides birefringent light with a phase retardation of 1/4 wavelength It is prepared with a λ / 2 plate that provides birefringent light with a retardation of 1/2 wavelength, and the optical axes thereof intersect each other; and, the cut polarizing plate and the wideband 1/4 plate are laminated: (1 ) | L2-L1 | > 0 .4W