TWI282013B - Long polarizing film, polarizing plate, production method thereof and liquid crystal display using the same - Google Patents

Abstract

The present invention can provide a polarizing plate excellent in the dimensional stability, particularly in the aging stability, a method for easily producing a polarizing plate, being capable of improving the yield in the step of punching the polarizing plate, and a liquid crystal display having excellent display grade at a low cost, and a polarizing plate of the present invention, comprising: a polarizing film; and a protective film attached to at least one surface of the polarizing film, wherein the angle made by the stretching axis of the protective film and the stretching axis of the polarizing film is no less than 10 DEG and less than 90 DEG.

Description

1282013 玖., invention instructions.

BRIEF DESCRIPTION OF THE DRAWINGS (Technical Field, Prior Art, Content, Embodiment, and Schematic Description of the Invention) (1) Field of the Invention: The present invention relates to a polarizing plate having excellent dimensional stability, Manufacturing method, and liquid crystal display using a polarizing plate. (•1) Prior art:

With the spread of liquid crystal display devices (hereinafter referred to as LCDs), the demand for polarizing plates has rapidly increased. Such a polarizing plate generally includes a polarizing film having a polarizing ability, and a protective film attached to both sides or one side of the polarizing plate via an adhesive layer.

The material used as the polarizing film is mainly polyvinyl alcohol (hereinafter referred to as PV A). The PVA film is uniaxially stretched and then dyed with iodine or a two-color dye' or is stretched after dyeing. This film system is further crosslinked with a boron compound to form a polarizing film. Usually, such a polarizing film is produced by stretching (longitudinally stretching) into a continuous film in the moving direction (longitudinal direction), and therefore, the absorption axis of the polarizing film is substantially parallel to the longitudinal direction. On the other hand, the protective film attached to at least one surface of the polarizing plate requires a low hysteresis, because if it has birefringence, the polarized state will change. However, the shortcomings of hysteresis increase with the temperature and humidity in the environment, and this problem has been solved by the attached protective film before, even if the retardation axis of the protective film moves and is perpendicular to the polarizing film. The axis (ie, the hysteresis axis of the protective film is parallel to the absorption axis of the polarizing film). However, in this case, since the retardation axis of the protective film and the absorption of the polarizing film 1282013 are parallel to each other, the dimensional stability is poor, and in particular, it is a problem of ripeness stability. On the other hand, in the conventional LCD, the polarizing plate is arranged such that its transmission axis is 45 with the longitudinal or lateral direction of the image plane. Tilt, therefore, if the polarizing film is formed by stretching in the longitudinal direction or the transverse direction as described above, the polarizing plate which is formed into a roll shape must be formed in the longitudinal direction with respect to the roll during the pressing process. Stamped in the 5 ° direction. In this case, the yield will be reduced, or the polarizing plate material will be difficult to reuse after lamination, with the result that the disadvantage of forming waste is increased. In order to solve such a problem, then (see JP-A - 2 0 0 0 - 9 9 1 2 (the term 4 PA used herein refers to a Japanese patent application published without review) and JP-A- 3 - 1 8270 1 ) A method of producing a polarizing plate by tilting the orientation axis of the polymer film at an appropriate angle with respect to the film transport direction has been proposed. a polarizing film having an absorption axis that is not parallel to the longitudinal direction; however, since the longitudinal or transverse stretching of the plastic film is performed at a different rate from each other on the left or right side in the stretching direction, the film is broken or formed. Wrinkles, so that it is difficult to produce a desired angle of inclination (45 ° in a polarizing plate). Therefore, this method is not feasible. As far as the protective film is concerned, most of the cellulose triacetate has been used because of this film system. It is light transmissive and has low birefringence. Generally, such a polarizing film is obtained by stretching (longitudinally stretching) into a continuous film along the moving direction (longitudinal direction), and thus, the absorption axis of the polarizing film is substantially Parallel to the longitudinal In addition, when other optical components, for example, attaching a λ / 4 plate, must be attached to each panel, this method is cumbersome. In addition, when the fabrication step of the laminate 1282013 stratified film is required, Strictly control the angle because the sliding of the angle will cause light leakage, causing the color display in the black portion to change to yellow or blue. Therefore, a roll-to-roll shape attachment is required.

In recent years, liquid crystal displays have been used not only indoors but also outdoors. Examples of outdoor use include large displays for street advertising, liquid crystal displays for vapor transportation fixed on vehicles, and liquid crystal display mobile media represented by mobile phones. At the same time, as these operating environments change, liquid crystal displays not only require color changes, but also require reduced transmission polarization, even under high temperature and high humidity conditions. Due to such changes, the polarizing plate also needs to meet the requirement of light transmittance, and the light transmission and color change of the image on the entire display are small, even in a high temperature and high humidity environment. In order to solve such problems, as described above, (JP-A-2000 - 9 9 1 2), several methods have been proposed in which the orientation axis of the polymer film is inclined at an appropriate angle with respect to the film transport direction.

JP-A- 3 - 1 8 2 70 1 proposes a method of mechanically producing a film having a stretching axis at any angle Θ to the direction of travel of the film, the method being included on both side edges of the continuous film, Providing a plurality of laterally paired support points formed at an angle Θ between the direction of travel of the film, each pair of points can stretch the film to the x-direction when the film is advanced. Moreover, in this method, since the rate of travel between the right edge and the left edge of the film is different, collapse and wrinkles are generated on the film. Therefore, in order to reduce this problem, the stretching stage must be extended, resulting in a significant increase in equipment costs. JP-A-2 - 1 1 3 9 2 0 proposes a method of producing a stretched film by advancing the film in a direction diagonal to the mechanical direction of the film while sandwiching the edges of the sides 1282013 to keep it The carriage track on which the two rows of chucks travel is '俾 such that the distances of the chucks in a particular travel segment are different from each other. Moreover, in this method, folds and wrinkles are generated in diagonally opposite corners, and this method is also disadvantageous for optical films. Moreover, these stretching methods have a fundamental problem mainly due to the bending of the stretching shaft caused by the bending of the film when it is separated from the tensioner clip. A polarizing plate whose absorption axis is inclined by a rubbing treatment is disclosed in Korean Unexamined Patent Publication No. P-200-005-84. However, as is well known, the use of friction to regularize orientation is only effective over the surface of the membrane, and for most nanoscale parts and polarizers such as iodine or dichroic dyes, the orientation is not met; There are disadvantages that are not conducive to polarized light performance. As for other conventional methods, IP-A-6-1 676 1 1 discloses a liquid crystal display using a polarizing plate to reduce the percentage of shrinkage under high temperature and high humidity conditions. JP-A-1 2 - 0 3 5 5 1 2 discloses a polarizing plate which reduces the amount of change in transmittance at a high temperature by controlling the amount of addition of zinc, the degree of polymerization of PVA, and the degree of soap of PVA. Further, I P - A - 1 3 - 0 8 3 3 2 9 discloses an iodinated polarizing film which utilizes an aqueous solution containing boric acid at a specific pH to reduce the polarization of the polarizing phenomenon under high temperature and high humidity conditions. However, these are not sufficient for the purpose of improving durability. (III) SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a polarizing plate which has excellent dimensional stability, particularly ripening stability. Another object of the present invention is to provide a long roll-shaped polarizing plate which has excellent dimensional stability and an improved yield of 1282013 in the polarizing plate stamping step. Another object of the present invention is to provide a long polarizing plate which reduces the dispersion of the stretching axis and which is inexpensive, and which comprises oblique stretching, which can be improved in the yielding step of the polarizing plate. Still another object of the present invention is to provide a polarizing plate which has high efficiency and which reduces attenuation of a polarizing effect under high temperature and high humidity conditions, and is inexpensive, that is, excellent durability; it includes oblique stretching An improved yield in the polarizing plate stamping step. Further, another object of the present invention is to provide a manufacturing method using an oblique stretching method which can easily produce a polarizing plate having dimensional stability as described above and provide a polarizing plate containing the above. LCD Monitor. These objects can be obtained by the following constitution. What is claimed is: 1. A polarizing plate comprising: a polarizing film; and a protective film attached to at least one surface of the polarizing film; wherein an angle formed between a stretching axis of the protective film and a stretching axis of the polarizing film Not less than 10 ° and less than 90 °. 2. The polarizing plate of item 1, which is a roll-shaped elongated polarizing plate; wherein a protective film having a stretching axis parallel to the longitudinal axis direction is attached to a film having neither parallel nor vertical At least one surface of the polarizing film of the stretching axis in the direction of the longitudinal axis. 3. A long polarizing film 'having: an absorption axis that is neither parallel nor perpendicular to the longitudinal axis; 90% or more of the 550 nm polarization; 1282013 at 550 nm The plate transmittance is 35 % or more; and when the angle is measured in the cross-sectional direction, the dispersion angle from the stretching axis to the longitudinal axis is within ± 0.5 °. 4. A long polarizing film having: an absorption axis that is neither parallel nor perpendicular to the longitudinal axis; a polarization of 90% or more at 550 nm; a single at 550 nm The plate transmittance is 35% or more;

The dispersion of the polarization angle in the plane is within ±0.5%; and the dispersion of the transmittance of the veneer is within ±〇·5%. 5. A long polarizing film having: an absorption axis that is neither parallel nor perpendicular to the longitudinal axis; a polarization of 550 nm is 80% or more; a single of 550 nm The plate transmittance is 35% or more; and the surface roughness: Ra is 10 μm or less. 6. The polarizing plate of item 2, wherein

(a) The polarizing film has an absorption axis that is neither parallel nor perpendicular to the longitudinal axis. When the degree of polarization is calculated by the following formula (1), the polarizing plate is transparent to a single plate of 550 nm. 40% or more; and 95% or more of the 550 nm polarization; and (b) when the polarizing plate is placed in an atmosphere of 60 ° and a humidity of 90% for 500 hours, The polarizing plate has: (b - 1 ) when compared with the starting enthalpy, its variation in transmittance at 550 nm is within ±10%; and -12-1282013 (b - 2) When the initial comparison is made, the variation of the polarization degree at 550 nm is within ±10%; formula (1) Ρ = [(Η0-Η1) / (Η0 + Η1)], /2χΐ〇0 , HO is the transmittance (%) when the two polarizing plates are stacked to make the absorption axis coincide, and Η 1 is the transmittance (%) 〇7 when the two polarizing plates are stacked to make the absorption axis orthogonal. The elongated polarizing film of item 5, wherein the number of color sliding stripes is 4 or less per 1 m 2 . 8. The polarizing plate of item 1, 2 or 6, wherein the protective film is a light transmissive film, and the retardation 偏 of the polarizing plate at 6 3 2 . 8 nm is 10 nm or less. 9. A method of manufacturing a polarizing plate, comprising: attaching a stretched roll-shaped protective film to at least one surface of a polarizing film; wherein the polarizing film is manufactured by a method for stretching a polymer film The method comprises: supporting both sides of the continuously fed polymer film with a supporting device; and stretching the film when the supporting device moves to the longitudinal axis of the film and applies tension to the film; , L 1 represents the trajectory between the support device from the substantial support starting point to the substantial support release point on one edge of the polymer film; L2 represents the support device from the substantial support starting point to the other edge of the polymer film The substantial support supports the trajectory between the points; and W represents the distance between the two substantial support release points; L 1 , L2 and W satisfy the relationship of 1282013 represented by the following formula (2), and the left and right film holdings The difference in the conveying speed in the longitudinal direction between the devices is less than 1%; Equation (2) | L2 - L1 | > 0.4W. The method of producing a polarizing plate according to Item 9, wherein the polymer film maintains the supporting property of the polymer film while being stretched, and allows a volatile content ratio of 5% or more to exist; The volatile content ratio is then reduced while the polymer film is shortened.

1 1 The method for producing a polarizing plate according to item 9, wherein the polymer film suitable for the polarizing film is a film mainly composed of polyvinyl alcohol. A method of producing a polarizing plate according to item 10, wherein the proportion of the volatile matter is reduced while the polymer film is shortened, and the ratio of the volatile content is reduced by 1% / min. The method of producing a polarizing plate according to any one of items 9 to 12, wherein an angle formed by a longitudinal direction and an absorption axis direction of the polarizing film is 20 to 70

The method of producing a polarizing plate according to Item 13, wherein the longitudinal axis direction and the absorption axis direction of the polarizing film form an angle of 40 ° to 50 °. A method of producing a polarizing plate according to any one of items 9 to 14, which comprises drying a stretched polymer film for a polarizing plate to shorten and reduce it. a ratio of volatile content; after drying or during drying, a protective film is attached to at least one surface of the polymer film; and 14-1282013 heat-treats the laminate of the protective film and the polymer film. A method of manufacturing a polarizing plate, comprising: attaching a stretched roll-shaped protective film to at least one surface of the polarizing film; the polarizing film having: a polarizing light at 550 nm 80% or more of the degree; 35% or more of the veneer transmittance of 550 nm; and surface roughness: Ra of 10 μm or less; wherein the polarizing film utilizes a film for stretching the polymer film The method is manufactured, and the system includes:

Supporting the support device for both sides of the continuously fed polymer film; and stretching the film when the support device is moved to the longitudinal axis of the film and the film is subjected to tension;

Here, L 1 represents the trajectory between the support device from the substantial support starting point to the substantial support release point on one edge of the polymer film; L2 represents the support device from the substantial support starting point to the other in the polymer film The substantial support on the edge releases the trajectory between the points; and W represents the distance between the two substantial support release points; LI, L2, and W systems satisfy the formula (2): | L2-L1 | >〇.4W; The elastic modulus of the polymer film used for the polarizing film is 0.1 to 500 MPa before stretching; and the polymer film can maintain the supporting property of the polymer film while being stretched. At the same time, a ratio of volatile content of 5% or more is allowed to exist; and then the ratio of the volatile content is reduced while the polymer film is shortened. The method of producing a polarizing plate according to item 16, wherein the polymer film for the polarizing film is a film of polyvinyl alcohol having an average degree of polymerization of from 2,000 to 5,000. 18. The method of producing a polarizing plate according to item 16, wherein the method for stretching the polymer film for the polarizing film comprises the step of adding a metal salt. The method of producing a polarizing plate according to item 18, wherein the step of adding the metal salt is a step of immersing the polymer film in an aqueous solution containing a metal salt. The method of producing a polarizing plate according to item 17, wherein the metal salt concentration in the solution containing the metal salt is from 0.01 to 1.0% by weight. The method of producing a polarizing plate according to any one of the items 9 to 15, wherein the content of the volatile component in the film for the polarizing film is 5% or less before stretching. The method of producing a polarizing plate according to Item 16, wherein after the stretched roll-shaped protective film is attached to at least one surface of the polarizing film, the laminated body of the polarizing film and the protective film is post-heated. deal with. A liquid crystal display comprising a liquid crystal cell and a polarizing plate disposed on both sides of the liquid crystal cell; wherein at least one of the polarizing plates is punched out by at least one selected from the group consisting of the following groups; The polarizing plate according to the first, second or sixth aspect; the polarizing plate having at least one of the polarizing films of the third, fourth, fifth and seventh aspects; and A polarizing plate manufactured by the method according to any one of items 9 to 22. -16- 1282013 That is to say, it has been found that when the stretched protection and the tension are combined, the angle of the stretching axis is greater than 1 〇. And less than 90. Improves dimensional stability and provides excellent ripening stability. The polarizing plate 90 shown in Fig. 1 is obtained by contacting at least one of the polarizing film 80 having the stretching axis 8 1 with the stretching axis 〇 7 ;; if necessary, through the adhesive layer 74, The stretching axis 7 1 of the extension shaft 8 1 and the protective film (that is, the broken line 7 1 ') is not less than 10 ° and less than 90 °. Within this range, qualitative can be obtained. In view of dimensional stability and polarizing performance, the angle between the protective film and the off-axis is preferably 20 to 80°, more preferably 40 to 50°. The polarizing plate used herein is not only a long roll but also a long one. The polarizing plate punches out a polarizing plate suitable for an LCD. Regarding the angle between the stretching axis and the stretching axis of the protective film, when the polarizing film and the protective sheet are peeled off, and the phase difference between the absorption axis of the polarizing film and the protective film is measured, the angle formed by the absorption axis and the phase retardation axis can be estimated. The stretching axis of the polarizing film is defined as: when the polarizing plate is superposed on the absorption axis, the axis of the stretching axis providing the maximum penetration density is defined as: when measured on the plane of the protective film In the case of a number, the axial direction of the maximum refractive index is provided. The angle between the stretching axes of the film of the polarizing film is determined by the axial direction of the film. In the present invention, the angle is not less than 1 〇 and is less than the penetration density of the film. The density index can be measured by penetrating the densitometer (for example, 'X Wright Μ filter 3 1 0TR ) to measure the refractive index symmetry of the protective film. Instrumental (for example, 'ΑΕΡ - 1 0, made by Komatsu). The stretched polarizing film will be significantly more special, on the surface of the protective film of U, and the angle between the stretched film of the polarizing film is increased to the stretched plate with excellent light film, and the film of the polarizing film is self-protected. When the polarization is delayed, it will have a known direction. The angle between the deflection of the protective film and the angle formed by the protection is 90°. The polarizing light may be an ellipse 1282013. Preferably, the stretching axis 7 1 of the protective film 70 is parallel to the traveling speed to the longitudinal polarizing plate 8 2 or the lateral direction 8 3 , and the stretching axis 8 1 of the polarizing film 80 is formed. An angle of 45° with respect to the longitudinal direction 82 or the lateral direction 83 of the polarizing plate. The use of the stretched protective film in the present invention includes not only an example of providing a stretching step for stretching a film but also an example of not providing an independent stretching step; and the film is protected by it. The additional tension applied in the longitudinal direction of the roll in the post-heating step after drying of the film is stretched.

The polarizing plate can be easily produced by designing each of the polarizing film and the protective film to have a stretching axis which provides the above-mentioned desired stretching axis angle, and combining the films. However, it is preferable to use a roll-shaped polarizing plate as shown in Fig. 2, in which a protective film having a stretching axis 71 parallel to the longitudinal direction is followed by a stretching shaft 8 having neither parallel nor perpendicular to the longitudinal direction 82. 1 on at least one surface of the polarizing film (ie, the obliquely stretched film). Thereby, when the polarizing plate is subjected to punching as shown in Fig. 2, the yield in the step of punching the polarizing plate can be improved. The oblique angle oriented polarizing film as shown in Fig. 2 can be obtained by the following

By the method of supporting the device to support the two edges of the continuously supplied polymer film, and applying tension to stretch the film while allowing the support device to advance in the longitudinal direction of the film; here, L 1 represents the support The trajectory between the point from the substantial support starting point to the substantial support release point on one edge of the polymer film; L2 represents the substantial support release point of the support device from the substantial support starting point to the other edge of the polymer film The trajectory between the two; and W represents the distance between the two substantial support release points; L 1 , L2 and W satisfy the relationship represented by the following formula (1) and the longitudinal axis direction between the left and right film holding devices The difference in conveying speed is less than 1% (hereinafter, this method is particularly referred to as a diagonal stretching method of a special angle). When at least -18-1282013 on a surface of the polarizing film obtained by oblique stretching, such as a roll-shaped protective film having a stretching axis in the longitudinal direction, it is thus more efficiently produced. A roll of polarizing plate.

Fig. 1 is an embodiment of a conventional polarizing plate for stamping. In the conventional polarizing plate, as shown in Fig. 11, the absorption axis 71 of the polarized light, that is, the stretching axis coincides with the longitudinal direction 7 2 . In contrast, in the polarizing plate of the present invention, as shown in Fig. 2, the absorption axis 8 1 of the polarized light, that is, the stretching axis is inclined by 45 ° with respect to the longitudinal direction 8 2 and is followed by the liquid crystal cell in the LCD. At this time, the angle is the same as the angle formed between the absorption axis of the polarizing plate and the opposite direction of the vertical or liquid crystal cell itself; therefore, oblique punching is not required in the punching step. Furthermore, as shown in FIG. 2, since the polarizing plate of the present invention is cut in a straight line in the longitudinal direction, a practical polarizing plate can be obtained by cutting along the longitudinal direction even without punching the elongated polarizing plate. From this result, a remarkable high yield can be obtained.

The polarizing plate of the present invention comprises a polarizing film having polarization stability, and a protective film is provided on both surfaces or a surface of the polarizing film, usually through an adhesive layer. In summary, a long polarizing plate (usually a roll shape) is produced and stamped according to the application, thereby obtaining a practical polarizing plate. Unless otherwise specified, the "polarizing plate" used in the present invention includes a long polarizing plate and a punched polarizing plate. A first preferred embodiment of the polarizing film of the present invention is characterized in that, in the long polarizing plate, the absorption axis is neither parallel nor perpendicular to the longitudinal axis direction (hereinafter, such an elongated shape) The polarizing plate is often referred to as "polarized plate oriented by oblique angle". The angle of inclination formed between the stretching axis of the protective film and the stretching axis of the polarizing film is preferably from 10 to less than 90, more preferably from 20 to 70, still more preferably from 40 to 50, and particularly preferably 44. To 46 degrees. Since such a tilt angle is -19-1282013 degrees, a single polarizing plate can be produced with high yield in the step of stamping it from the long polarizing plate. In the present invention, the inclination angle can be freely set. Thus, when the polarizing plate is combined with other optical elements, the most appropriate angle can be freely selected.

A first preferred embodiment of the polarizing film of the present invention is characterized in that: the transmittance of the veneer at 550 nm is 35% or more; and the degree of polarization at 50 50 nm is 90% or more. . The transmittance of the veneer is preferably 40% or more; and the degree of polarization is preferably 95.0% or more, more preferably 99. 0% or more, and particularly preferably 99.9% or more. Since the polarizing plate of the present invention has excellent veneer transmittance and polarization degree, and thus can be used as a liquid crystal display, the contrast can be effectively improved.

The obliquely oriented polarizing plate of the present invention can be easily produced by the following method. That is, the bevel orientation is obtained by stretching the polymer film while setting the proportion of the volatile content in the stretched film, the shrinkage percentage of the shrink film, and the elastic modulus before stretching. . Also, it is preferred to control the amount of foreign matter adhered before the stretched film. In a first preferred embodiment of the polarizing film of the present invention, the angle of dispersion of the stretching axis with respect to the longitudinal direction is small in the transverse direction, and the dispersion is within ±5 °, preferably ±3 °. As a result, the dispersion of the black zone density at the cross time can be accurately estimated and the level can be increased. The above-mentioned lateral width is effectively used as the width (effective width) of the polarizing film, and does not include the grip portions at both edges and the like in the preparation of the polarizing film. -20- 1282013 After stretching to the desired tilt angle, in order to reduce the dispersion of the stretch axis, the orientation state is offset. An effective method for this purpose is a method for controlling the ratio of the volatile content of the polymer film, the percentage of shrinkage in the shrink film, the drying point of the film, and the ratio of the volatile content.

In a second preferred embodiment of the polarizing film of the present invention, the dispersion of the degree of polarization and the transmittance (the difference between the maximum or the minimum of the degree of polarization and the transmittance) can be controlled by volatilization. The content ratio, the percentage of shrinkage in the shrink film, the amount of foreign matter adhered before stretching the film, the rate of decrease in the proportion of volatile matter, and the content of volatile components in the film before stretching are reduced.

A third preferred embodiment of the polarizing film of the present invention is characterized in that the surface roughness Ra of the polarizing film is 10 μm or less. The surface roughness Ra of such a polarizing film is preferably 5 μm or less, more preferably 1 μm or less. The surface roughness Ra used herein is a standard measurement enthalpy measured by the measurement methods described in JIS B060 1 and B0660. In practice, the surface roughness can be measured as a conventional device such as a roughness meter and an AFM. In the present invention, the surface roughness Ra of the obliquely oriented polarizing film is 10 μm or less, so that an excellent polarizing plate freely producing color sliding stripes can be obtained. That is, the present invention provides a polarizing film having a color sliding stripe of 1 or less per 1 meter. The color sliding stripe used herein is meant to be a stripe-like color change observed on a polarizing film, or a polarizing plate. The color sliding stripe is visually confirmed, especially in the range of 550 nm to the normal area, the length is 1 cm or more, and the width is 0.1 cm or more, and the difference in density is 0.2 or The above. The number of color sliding stripes -21 - 1282013 is preferably 4 or less per 1 m 2 , more preferably 2 or less per 1 m 2 , and most preferably 1 or less per 1 m 2 .

A third preferred embodiment of the polarizing film of the present invention is further characterized in that the transmittance of the veneer at 550 nm is 35 % or more; and the degree of polarization at 550 nm Up to 80% or more. The transmittance of the veneer is preferably 40% or more; and the degree of polarization is preferably 95.0% or more, more preferably 99.0 or more, and particularly preferably 99.9% or more. In the present invention, the transparency refers to the transmittance of the veneer unless otherwise specified. Since the polarizing plate of the present invention has excellent single-plate transmittance and polarization, and thus can be used as a liquid crystal display, the contrast can be effectively improved.

The obliquely oriented polarizing plate of the present invention can be easily produced by the following method. That is, the bevel orientation is obtained by stretching the polymer film while setting the proportion of the volatile content in the stretched film, the shrinkage percentage of the shrink film, and the elastic modulus before stretching. . Also, it is preferred to control the amount of foreign matter adhered before the stretched film. According to this, a polarizing film having a small surface roughness, excellent smoothness, and no wrinkles and patterns can be obtained, even in the warp direction. Since no wrinkles/patterns are produced, wrinkles do not occur and the tensile tension applied to the film is not reduced. The polarizing plate of the preferred embodiment of the present invention has excellent durability, that is, it can reduce variations in polarizing performance under high temperature and high humidity conditions. Further, a polarizing plate having a length of 10 m or more and having excellent durability can be manufactured in the present invention for the first time in the form of a roll. As a result, the polarizing plate will be able to be roll-to-roll adhered to other optical components, such as λ / 4 plates, and the yield is increased. Due to the substantial roll shape, this polarizing plate also has excellent package characteristics and storage properties of -22-1282013. Further, a polarizing plate for a liquid crystal display can be punched out from a roll-shaped polarizing plate in a yield. A preferred embodiment of the polarizing film of the present invention is characterized in that the transmittance of the veneer at 50 nm is 40% or more; and the calculation is performed at the formula (1) at 550 nm. And the degree of polarization is 95% or more. The veneer transmittance is preferably 40% or more, more preferably 43% or more; and the degree of polarization is preferably 9 9% or more, more preferably 99.9 or more. In the present invention, the transmittance refers to the transmittance of the veneer unless otherwise specified. Since the polarizing plate of the present invention has excellent single-plate transmittance and polarization, and thus can be used as a liquid crystal display, the contrast can be effectively improved.

Further, a preferred embodiment of the polarizing plate of the present invention is characterized in that, after the polarizing plate is placed in an atmosphere of a temperature of 60 ° C and a humidity of 90% for 500 hours, at 550 nm. The variation width of the transmittance is within ±10% with respect to the starting enthalpy, and the variation width of the polarization at 550 nm is within ±10% with respect to the starting enthalpy. Thus, the polarizing plate of the present invention can avoid deterioration of polarizing performance under high temperature and humidity conditions and exhibit excellent durability. The meaning of the initial enthalpy used herein refers to the enthalpy of the polarizing plate before it is exposed to a high temperature and high humidity environment. The obliquely oriented polarizing plate of the present invention can be easily produced by the following method. That is, the bevel orientation is obtained by stretching the polymer film while specifying the proportion of the volatile content in the stretched film, the amount of the metal salt added to the film, and the degree of polymerization of the polymer constituting the film. . Also, it is preferred to control the amount of foreign matter adhered before the stretched film. -23-1282013 <Durability> When the liquid crystal display is used outdoors for a long period of time, there is a problem of deterioration, for example, an increase or decrease in the transmittance of the display image plane, and a color change such as discoloration or non-production Color, and reduce the degree of polarization. When the polarizing plate is placed in an atmosphere of a temperature of 60 ° C and a humidity of 90%, there is a phenomenon that the heat shrinkage is supported, and the polarizing film and the protective film are deteriorated. This will be used as a test to improve the deterioration of the polarizer. In view of the heat resistance, the degree of resistance, and the resistance to heat, the polarizing plate of the present invention preferably has a small change in transmittance and polarization in the above-described deterioration-improvement test. Further, after the polarizing plate is placed in an atmosphere of a temperature of 60 ° C and a humidity of 90% for 500 hours, the variation of the transmittance is ±10% with respect to the starting lanthanum, preferably ± 5%; More preferably within ± 2%; and the variation in the degree of polarization is ± 10% relative to the starting lanthanum, more preferably ± 5%; more preferably within ± 2%. The polarizing plate obtained by the method of the present invention has such durability, wherein an average polymerization degree of from 1 Torr to 1 Torr, preferably from 2,000 to 5,000, is used. The film of the polymer is used as a polymer film and is doped with a metal salt in the polarizing film. However, the present invention is not particularly limited to this method. In the polarizing plate of the present invention, the protective film is adhered to at least one surface of the polarizing film such that the inclination angle between the stretching axis of the protective film and the stretching axis of the polarizing film is not less than 10 and less than 90. Such a bonding method is not particularly limited to such a combination as long as the length can be satisfied. The adhesiveness required to combine the polarizing film and the protective film is not particularly limited, and examples thereof include a PVA-based resin (containing modified PVA such as ethyl acetophenone, sulfate group, carboxyl group, 1282013, and oxygen extension). Alkyl)' and an aqueous solution of a boron compound. Among them, PVA-based resins are ideally used. After drying, the thickness of the adhesive layer is preferably from 0.01 to 10 μm, more preferably from 0.05 to 5 μm. The embodiment for the method of combining the films includes a method of stamping each of the ordinary longitudinally stretched polarizing film and the protective film, and combining the pressed films so that each The other stretching axis forms an angle of inclination as described above. Preferably, at least each of the polarizing film and the protective film has a stretching axis which is neither parallel nor perpendicular to the longitudinal direction, because the tilting angle formed by the stretching axis of the polarizing plate of the present invention, such as no polarizing plate and protection It is impossible for the film to be subjected to the aforementioned stamping system to be parallel, and only a protective film and a polarizing film which are both in the form of a roll are adhered. In particular, the polarizing film is preferably a stretching axis which is neither parallel nor perpendicular to the longitudinal direction. Further, the polarizing film used as the polarizing plate for the LCD is preferably a stretching shaft having an inclination angle of 40 to 50 with respect to the longitudinal direction, more preferably 44 to 46.

Preferably, a polarizing film having a stretching axis which is neither parallel nor perpendicular to the longitudinal direction is produced, as described above, by a diagonal stretching method. This is as follows. Each of Figures 3 and 4 is a schematic plan view showing a typical method of obliquely stretching a polymer film. The specific oblique stretching method comprises: (a) a step of introducing a raw material into a direction indicated by an arrow (1), (b) a step of stretching the film in an opposite direction, and (c) stretching the film. The film is transported to the subsequent step, in the direction indicated by arrow (ii). Hereinafter, the "stretching step" as used herein includes the steps of (a) -25-1282013 to (c), and represents the complete step of performing the oblique stretching method. The film system is continuously introduced in the direction indicated by (i), and is initially supported at the point B 1 by the support means viewed from the upstream side to the left. At this moment, the other edges of the film are unsupported, so no tension is generated in the width direction. Namely, the point B1 is not equal to the substantial support starting point of the present invention (hereinafter referred to as a substantial support starting point).

In the present invention, the substantial support starting point is defined as the point at which the two edges of the film are initially supported. The substantial support starting point is a substantial support starting point indicated by two points of the support starting point A 1 and the point C 1 on the downstream side, wherein the straight line is drawn perpendicularly from the point A 1 to the center line 1 of the film on the lead-in side 1 (Fig. 3) or 2 1 (Fig. 4), the line intersects the trajectory 13 (Fig. 3) or 2 3 of the support device (Fig. 4).

Starting from these points, when the support means on both edges move at substantially the same rate, A 1 moves to A 2, A 3 ... A η every unit time, and Cl moves to C2, C3 as well. ...Cn. That is to say, the straight line connecting the points An and Cn at this time is the stretching direction based on the passage of the supporting device at the same timing. In the specific oblique stretching method, as shown in Figs. 3 and 4, the An line gradually falls after Cn, and therefore, the stretching direction is gradually inclined from the perpendicular to the conveying direction. The substantial release point of the support (hereinafter referred to as the substantial support release point) is defined by two points, that is, the point Cx from the support device downstream of the film, defined by two points of the point Ay, the line drawn at the point Ay The line perpendicular to the film is transported from Cx to the centerline of the subsequent step 1 2 (Fig. 3) or 2 2 (Fig. 4) 'The line between the line and the support device on the other side 1 4 (Fig. 3) or 2 4 (Fig. 4-26-1282013) intersects.

The angle of the final stretching direction of the film is determined by the ratio of the difference Ay-Ax (i.e., IL1-L2 I ) between the paths, which is between the right and left support devices, and ends substantially at the stretching step. The distance W (the distance between Cx and Ay) between the point (substantial support release point) and the substantial support release point. Therefore, the inclination angle of the stretching direction with respect to the direction of conveyance to the subsequent step is an angle satisfying the following relationship: tan6=W/(Ay-Ax), that is, tan0=W/IL1—L2I although the third and the third The upper edge of the film in Figure 4 is supported up to 18 (Fig. 3) or 28 (Fig. 4), even after point Ay, however, because the other edge is unsupported. Therefore, no new stretching is formed in the lateral direction, so that 18 and 28 are not substantial support release points.

As mentioned above, the substantial support starting point on both edges of the film is not the point at which only the right and left sides of the support device engage. In order to describe the above two substantial support starting points more strictly, these points are defined as: a line connecting the right or left support points with other support points, which intersects the center line of the step of guiding the film to support the film almost vertically. Point, and is the support point at the most upstream position. Similarly, the two substantial support release points are defined as the line connecting the right or left support point with the other support points, the point at which the film is introduced into the center line of the step supporting the film, and is at the most downstream position. Support point. As used herein, the term "almost perpendicular to the intersection" means that the center line of the film is 90 ± 0.5 with the straight line connecting the right and left substantial support starting points or the substantial support release point. . -27- 1282013 If the stretching machine using the tensioning system causes a path difference between the right and left sides of the supporting device, the supporting points supported by the supporting device and the substantial support are supported due to mechanical constraints such as the length of the rail. There is a great difference between the starting point, or between the release point of the support device and the substantial support release point. However, as long as the path between the substantial support starting point and the substantial support release point defined above satisfies the relationship of equation (1), the oblique stretching can be effectively performed. The inclination angle of the orientation axis of the obtained stretched film can be controlled by the ratio of the exit width W at the step (c) and the substantial path difference 丨LI-L2丨 between the right and left sides of the support device. Adjustment. In the case of a polarizing plate and a retardation film, it is often required to orient the film at 45° with respect to the longitudinal direction. In this case, in order to obtain close to 45. The orientation angle preferably satisfies the following equation (2): 0.9W < IL1-L2I < 1.1W (2) More preferably, the following equation (3) is satisfied: 0.97W < IL1-L21 < 1.03W (3)

The specific embodiment of the stretching step is as shown in Figures 1 to 6, in which the polymer film is subjected to oblique stretching while satisfying the equation (1), and these can be freely set in consideration of equipment cost and productivity. The angle formed by the direction (i) of the film introduction stretching step and the direction (i i ) of the film transport to the subsequent step may be any number. From the standpoint of minimizing the total equipment mounting area before or after stretching, this angle is preferably as small as possible. The angle is preferably 3 ° or less, and more preferably 〇 · 5. Or below. For example, the structure shown in Figures 3 and 6 can achieve this. In the method as described above, the film traveling direction is substantially unchanged, and it is difficult to obtain a distance from the longitudinal direction by only -28-1282013 by amplifying the distance between the supporting means. The orientation angle which is suitable for the polarizing plate and the retardation film. Thus, the 丨LI-L2 I can be made larger by providing a step of shrinking the film after one stretching as shown in Fig. 3. The stretching ratio is preferably from 1 · 1 to 1 0 · 0 times, and more preferably from 2 to 10 times. The subsequent shrinkage percentage is preferably 10% or more. Further, as shown in Fig. 6, it is preferable to repeat the stretching-contraction a plurality of times because |L 1 - L2 I can be made large.

Further, from the viewpoint of minimizing the installation cost of the stretching step, the number of track cycles and the bending angle of the supporting device are preferably as small as possible. From this point of view, as shown in Figures 4, 5 and 7, the direction of travel of the film is preferably curved while maintaining the state of the edges of the support film so that the step of supporting the edges of the film exits The direction in which the film travels is inclined from the substantial stretching direction of the film to 20 to 70. .

A device suitable for stretching a film by applying tension while supporting both side edges, preferably as a bracing system as shown in Figures 3 to 7. In addition to the conventional two-dimensional draw frame, a spiral stretching step having a path difference between the two edges can also be used using the support device shown in Fig. 8. In many instances, the draw frame type stretching machine has a structure in which the chain to which the clip is attached moves in many cases along the track. However, when a vertical and non-uniform stretching method is used in the present invention, as shown in Figures 3 and 4, at the entrance and exit of this step, the end of one of the tracks may end from the other track. Deviate and engage or not engage at the same time on the left and right sides. In this case, the substantial path lengths L 1 and L2 are not simply the distance between the support point and the release point, but as explained above, the length of the path -29-1282013 is the film supported by the supporting device. The distance between the ends.

When there is a difference in the traveling speed between the right and left edges of the film at the exit of the stretching step, wrinkles and locally uneven film thickness are generated at the exit of the stretching step. Therefore, the right and left film support devices are substantially the same at the delivery rate. The difference in the conveying rate is preferably 1% or less, more preferably less than 0.5%, and most preferably less than 0.05%. The term "rate" as used herein means the length per minute of the trajectory formed by the movement of the right and left sides of the support device. In a conventional draw type stretching machine, the rate unevenness is less than a few seconds or less, and depending on the period of the chain drive chain and the frequency of the drive motor, a few percent unevenness is often generated. However, the unevenness of this rate is not below the rate difference described in the present invention.

Wrinkles and film slippage occur due to path differences between the right and left support devices. In order to solve this problem, the polymer film is preferably stretched while maintaining the support characteristics, and allows the presence of a volatile content of 5% or more, and then shrinks the film to reduce the volatile content. As used herein, the term "polymer film retains support characteristics" means that the film is supported on both sides without damaging the film properties. Furthermore, the term "stretching while allowing the presence of a volatile content of 5% or more" does not mean that the volatile content is maintained at 5% or more throughout the stretching step, but as long as the volatile content is 5 The stretching at % or more may exhibit the effects of the present invention, and in a part of the stretching step, the volatile content may be 5% or less. An example of a method involving volatile content, the form comprising: a cast film process containing a volatile such as water or a non-aqueous solvent; a method of immersing the film in a volatile such as water or a non-aqueous solvent, and using it -30 before stretching - 1282013

A method of coating a film or spraying it onto a film; and a method of coating a film with a volatile such as water or a non-aqueous solvent during stretching. a hydrophilic polymer such as polyvinyl alcohol containing water, placed in a high temperature or humidity atmosphere, and thus by stretching the humidity in a high humidity atmosphere, then stretching the film, or by stretching under high humidity conditions Make it contain volatiles. In addition to these methods, any other means may be used as long as the volatile content of the polymer film is 5% or more.

The preferred volatile content will vary with the type of polymeric film. The maximum amount of volatile matter can be any enthalpy as long as the supporting properties of the polymer film can be maintained. In the case of polyvinyl alcohol, the volatile matter content is preferably from 10% to 100%, and in the case of cellulose acylate, the volatile matter content is preferably from 10% to 200%. <% shrinkage: percentage of shrinkage during or after stretching>

The stretched film can be shrunk at any step during or after stretching. It suffices that shrinkage can be used to eliminate the wrinkles of the polymer film and the dispersion produced by the stretching axis in the oblique orientation. In the case of shrinking the film, the method of heating the film can be used to remove the volatile content, however, any method can be used as long as the film can be shrunk. Preferably, the film shrinks to 1 / s i η 0 or several times, where 0 is the orientation angle with respect to the longitudinal direction. The percentage of shrinkage is preferably 10% or more. <Distance from wrinkle generation to disappearance> The wrinkle of the polymer film produced in the orientation in the oblique direction may be sufficient as long as it disappears before reaching the substantial support release point of the present invention. However, if it takes a long time for the wrinkles to be produced to disappear, dispersion may occur in the stretching direction. Therefore, the wrinkles, from the point where the wrinkles are generated, are preferably released within a moving distance as short as possible. For this purpose, for example, a method in which the volatilization rate of the volatile matter is high can be used. <Distribution of volatile component content>

In the case of producing a long, in particular roll-shaped, polarizing plate in a complete step, it is necessary to have no uneven or undyed spots. If the volatile component in the film has a non-uniform distribution prior to stretching (the amount of volatile component varies depending on the position in the film), it will result in uneven or undyed spots. Accordingly, the smaller the distribution of the volatile component content in the film before stretching, the better, and it is preferably at least 5% or less. The ratio of the volatile content used in the present invention means the volume of the volatile component contained in the film per unit volume, and is obtained by dividing the volume of the volatile component by the volume of the film. The meaning of the above distribution is the variation width of the volatile matter content per 1 m 2 (a large difference from the maximum enthalpy of the volatile content ratio, or the difference between the minimum enthalpy and the average enthalpy) ratio). In order to reduce the distribution of the volatile content ratio, a method of uniformly blowing the front surface and the back surface of the film by means of uniform air, a method of uniformly pressing the film by means of a rolling roller, or a method of wiping off the volatile component by using a rubbing cloth may be used. . However, the distribution can be made uniform using the methods used so far. Figures 12 to 14 show examples of an air blowing device, a rolling device, and a doctor device, respectively. <Elastic Modulus> Regarding the physical properties of the polymer film before stretching, if the modulus of elasticity is too small, the percentage of shrinkage decreases during or after stretching, and the wrinkles are hard to disappear, on the contrary If it is too high, it is necessary to apply the tension of -32-1282013 when stretching. As a result, the portion of the side edges of the supporting film must be increased in strength, so that the mechanical load is increased. The modulus of elasticity of the film, in terms of Young's modulus, is preferably from 1 to 5000 MPa, more preferably from 0.1 to 500 MPa. <Drying: drying rate and drying point>

In order to produce a long, especially roll-shaped polarizing plate, it is necessary to adhere the protective film in a state where the volatile component is reduced. Preferably, the polarizing film adheres to the protective film prior to drying and preferably has a dry point prior to releasing the edges of the supported sides. It is better to adjust the drying point to a minimum moving distance after obtaining the desired orientation angle. Further, by setting the drying to a point at which the support of the both side edges is released, the dispersion of the stretching axis can be lowered. The drying point means that the surface temperature of the film becomes equal to the temperature of the atmosphere in the environment. For the reasons described above, the drying rate is also preferably as high as possible. <rate of volatile content ratio>

The ratio of the volatile content ratio used in the present invention means the reduction rate per unit volume of the volatile component contained per unit volume. If the volatile content is less than the reduction rate, the shrinkage is time consuming, and during this period, the stretched and oriented polymer film is believed to have undergone directional dispersion, and as a result, it is easy to be in polarizing performance, veneer transmittance. Dispersion occurs in aspects such as the like. Therefore, the ratio of the volatile matter content is preferably as high as possible, and the reduction rate is particularly preferably 1% / min or more. <Drying Temperature> The polymer film must be dried until it is combined with the protective film, and therefore, in the case of preparing a polarizing plate using a polyvinyl alcohol film, the drying temperature is preferably 40 to 90 ° C, more preferably 60 to 85 ° C. -33-1282013 <% expansion> In the present invention, when the polymer film is polyvinyl alcohol and a hardener is used, the percentage of water swelling before and after stretching is preferably different. Reverted to its original shape; however, it should be maintained in a state of being stretched at an oblique angle. More preferably, it is preferred to have a high percentage of expansion before stretching and a low percentage of expansion after stretching. Most preferably, the percentage by which the water expands before stretching is more than 3%, and the percentage of expansion after drying is 3% or less. <Description of curved portion>

In the present invention, it is usually necessary to have a large bending ratio to adjust the track of the trajectory of the supporting device. In order to avoid the other sudden bending of the film engaging device or to avoid the interference of the stress density at the place, the trajectory of the engaging device is preferably drawn in an arcuate shape at the bent position. <stretching speed>

In the present invention, the higher the speed of the stretched film, the better, and the stretching ratio per unit time is preferably 1.1 times/minute or more, more preferably 2 times/minute or more. <Exogenous substance> In the present invention, if the foreign substance adheres to the polymer film before stretching, the surface becomes rough. Therefore, it is preferred to remove foreign matter. It is assumed that there is foreign matter, especially when manufacturing a polarizing plate, which will result in color/optical unevenness. Further, it is also important that the foreign substance is not adhered to the polymer film until it is combined with the protective film. Therefore, it is preferred that the polarizing plate be fabricated in an environment where the floating dust particles are reduced as much as possible. The "amount of foreign matter" used in the present invention means the weight of the substance adhered to the surface of the film - 34 - 1282013 divided by the surface area, and expressed in grams per square meter. . The amount of the foreign substance is preferably 1 g/meter 2 or less, more preferably 0.5 g/meter 2 or less. The smaller the amount, the better. The method of removing the foreign matter is not particularly limited, and any method may be used as long as it can remove the foreign matter, but does not adversely affect the polymer film at the stretching. Examples thereof include a method of ejecting a water stream to scrape off a substance, a method of scraping a material by a jet, and a scraping knife made of cloth, rubber or the like to scrape a substance.

<Tension in the longitudinal direction> In the present invention, when both side edges of the film are supported by the supporting means, the film is preferably stretched to be supported. To this end, a specific embodiment thereof includes a method of applying tension in the longitudinal direction to cause the film to be stretched. This force varies depending on the state of the film before stretching, but is preferably applied to such an extent that the film is not released. <humidity during stretching>

In the case of stretching polyvinyl alcohol which is a film having a volatile matter of water, the film is preferably stretched under a humidity-adjusting atmosphere. In particular, when a hardener is added, if the water is reduced, the speed and stretching of the film hardening becomes difficult. Therefore, the humidity is preferably 50% or more, more preferably 80% or more, and particularly preferably 90% or more. <Transport speed in the longitudinal direction> In the case of stretching a polyvinyl alcohol film doped with a hardener, the hardening of the film proceeds as the stretching time passes. Therefore, the moving speed in the longitudinal direction is preferably 1 m/min or more. According to the productivity point of view, the better -35-1282013 is a higher speed. In any case, the upper limit depends on the stretched film and the stretching machine. <Polarizing Film> In the present invention, the film to be stretched is not particularly limited, and a polymer including a suitable thermoplastic may be used as the film. Examples of the polymer include PVA, polycarbonate, cellulose acylate, and polyfluorene.

The film thickness before stretching is not particularly limited, however, the thickness is preferably from 1 μm to 1 mm, more preferably from 20 to 200 μm, from the viewpoint of supporting film stability and uniformity of stretching. . In the case of using the present invention to produce a polarizing film, the polymer is preferably PVA. PVA is usually produced by saponification of polyvinyl alcohol, but may contain a copolymerization component with ethylene acetate, for example, an unsaturated carboxylic acid, an unsaturated sulfonic acid, an olefin, and a vinyl ether. Further, a modified PVA containing an ethyl hydrazine alkyl group, a sulfonic acid group, a carboxyl group, an oxygen alkyl group or the like can also be used.

The degree of saponification of PVA is not particularly limited, but is preferably from 80 to 100 mol%, more preferably from 90 to 100 mol%, from the viewpoint of solubility and the like. Further, the degree of polymerization of PVA is also not particularly limited, but is preferably from 1,000 to 1,000, more preferably from 1,500 to 5,000. <Staining Formulation/Method> The polarizing film is obtained by dyeing a polymer such as PVA suitable for a polarizing film, and the dyeing step is carried out by using a gas phase or a liquid phase. In the case of liquid phase dyeing, when iodine is used as the polarizing agent, the dyeing is carried out by immersing the polymer film suitable for the polarizing film in a liquid aqueous solution of iodine-potassium iodide. The iodine is preferably from 0.1 to 20 g/liter, and the potassium iodide is preferably from 1 to 200 to 36 to 128, 2013 g/liter, and the weight of iodine to potassium iodide is preferably from 1 to 200. The dyeing time is preferably from 10 to 5,000 seconds, and the liquid temperature is preferably from 5 to 60 tons. The dyeing is not particularly limited, and any method other than immersion may be used, such as coating, or spraying iodine or a dye solution. In the present invention, the dyeing step may be before or after stretching, however, the dyeing is preferably carried out in the liquid phase before stretching because the film is properly expanded and the stretching proceeds smoothly. <polarizing agent>

In addition to iodine, it is also preferred to use a two-color dye as a polarizing agent and to dye the film with a two-color dye. Specific examples of the dichroic dye include dye-type compounds such as azo dyes, anthraquinone dyes, pyrazolone dyes, triphenylmethane dyes, quinoline dyes, hydrazine dyes, thiline dyes, and hydrazines. Lanthanide dyes. It is preferably a water-soluble compound, but the present invention is not particularly limited thereto. Further, the hydrophilic component may be, for example, a sulfonic acid group, an amine group and a hydroxyl group are preferably introduced into a two-color molecule. Specific examples of bicolor molecules include CI·true jaundice 2, CI·true orange 39, CI true orange 7 2, C. I · true red 3 9 , C · I · true red 7 9 , C . I · true red 8 丨, c. ][ • True Red 8 3 , CI True Red 89, CI True Purple 48, CI True Blue 67, ci True Blue 90, CI True Green 59 and CI Acid Red 37, and more include jp_A-62_7〇802, JP-A -1-161202, JP-A-172906, JP-A-1-1 72907, JP-A-1-183602, JP-A-1-248105, JP-A-1-265205, and JP-A-7- Dye as described in 261024. These two-color molecules are used as free acid, alkali metal salts, ammonium salts or amine salts. A polarizing agent having a different color tone can be produced by mixing one or more of such dichroic molecules. The polarizing means or the polarizing plate is preferably blended with a compound (dye) which provides black when the polarizing axis intersects at a right angle, or a different type of two-color molecule of -37-1282013 is blended to provide black because it is excellent The transparency and polarizing rate of the veneer. The stretching method used in the present invention is preferably used to produce a so-called polyethylene-based polarizing film, where PVA is dehydrated, or polyvinyl chloride is dechlorinated to form a polyolefin structure, and The yoke double bond is used to obtain polarization. <Addition of Curing Agent (Crosslinking Agent) and Metal Salt> A curing agent (crosslinking agent) is described with reference to the following examples, in which a PVA film is used as a polymer film for a polarizing film. During the production of the polarizing film by stretching the PVA, it is preferred to use an additive for crosslinking the PVA. In particular, when the oblique stretching method of the present invention is used, if the PVA film is not sufficiently hardened at the exit of the drawing step, the orientation of the PV A film is deviated due to the tensile force given in the step. Therefore, in the step before stretching or in the stretching step, it is preferred to harden the PVA film by dipping it into a hardener (crosslinking agent) or by applying a solution of the hardener (crosslinking agent). The agent (crosslinking agent) is incorporated into the PVA film. The meaning of "incorporating a hardener (crosslinking agent) into a PVA film" is not particularly limited, and may be soaked, coated or sprayed using, for example, a hardener (crosslinking agent) or a hardener (crosslinking agent). Any method of the film, however, preferably using a soaking method and a coating method. The meaning of coating means that any generally known device can be used, for example, a roll coater, a die coater, a strip coater, a sheet coater, and an inexpensive coater. Further, a method of bringing the film into contact with a cloth impregnated with a solution, cotton, a porous material, or the like is preferred. As the hardener (crosslinking agent), the hardener (crosslinking agent) described in U.S. Patent No. 2 3 2 8 9 can be used. However, it is practical to use boric acid and borax. -38- 1282013 This hardener (crosslinking agent) can be incorporated before or after the film is placed on a stretching machine. This can be performed in any step 'until the end of step (b) in the embodiment shown in Figures 3 and 4, where the 'lateral stretch' is substantially completed. A rinse/water wash step can be provided after the addition of the hardener (crosslinker). The hardener described in the above is referred to as an example of using a PVA film as a polymer film for a polarizing film. However, those described herein are slightly changed depending on the kind of the polymer, and most of them are also It can be applied to the case of using other polymer films.

The present invention is characterized in that a metal salt is present in the polarizing film, and thus a high single-plate transmittance can be obtained while maintaining the orientation of the polarizer. This is considered to be the result of the formation of salts by metal ions and polyiodide ions due to the presence of metal salts and ionic species of higher numbers.

The metal used in the present invention is preferably a metal element capable of forming a multivalent ion. In particular, a metal element belonging to a transition element is preferred. Specific examples of these include zinc, cobalt, chromium, iron, nickel and manganese. Among them, zinc is preferred. The addition of zinc is not particularly limited, but the addition may be carried out before the dyeing, after the dyeing, before the stretching, after the stretching, after the drying, or in the step of joining the polarizing film and the protective film. Such zinc may be added as zinc ions in a dry solution or a hardened solution, or may be added in other prepared zinc-containing aqueous solutions. The method of adding zinc is not particularly limited as long as zinc can be added, but the addition may include any one of a dipping method, a coating method, and a spraying method, before dyeing, after dyeing, before stretching, stretching. It is carried out after -39-1282013, after drying, or in the step of bonding the polarizing film and the protective film. For the purpose of adding zinc, for example, a method in which a zinc salt is dissolved in each aqueous solution is used. In the present invention, in view of ease of manufacturability, it is preferred to dissolve the zinc salt in the hardening solution and to incorporate zinc into the immersion hardening solution.

As the zinc salt, for example, a zinc halide including zinc chloride and zinc iodide, zinc sulfate, or zinc acetate is exemplified. The amount of the zinc salt used may be appropriately selected as long as the content of zinc in the polarizing plate or the polarizing film becomes a content defined in the present invention; for example, when zinc is added by immersion, the amount of the zinc salt may be used as the case may be. Need, depending on the concentration of zinc in the soaking solution, soaking time, and soaking temperature. When the soaking time is from 60 to 200 seconds, and the soaking temperature is 30 to 40 ° C, the amount of zinc chloride used is 0.5 to 15 parts by weight per 1 part by weight of the water, preferably It is 0.7 to 5 parts by weight.

The zinc content in the obtained polarizing plate or polarizing film is from 0.04 to 0.5% by weight. When the zinc content is less than 0. 04% by weight or more than 0.5% by weight, the resistance to high temperature and high humidity tends to deteriorate, and the degree of polarization and the transmittance of the veneer are also deteriorated. The zinc content in the polarizing plate or the polarizing film is a percentage 锌 of the weight of zinc in 100 parts by weight of the polarizing plate. The method for adding the metal salt to the film is not particularly limited, but may be a step of dyeing the film with a polarizing agent, a step of adding a hardener to the film, and a step of combining the polarizing film and the protective film. Add in any step. Among them, the metal ions are preferably added in the step of dyeing the film with a polarizing agent, and/or added when a curing agent is added to the film. In many embodiments, a 0. 0 1 to 0. 0 wt% metal salt is added to two liquid iodine/potassium iodide aqueous solutions as a polarizing agent solution, and -40-1282013 is a liquid boric acid/potassium iodide aqueous solution. As an aqueous solution of a liquid hardener, it is obtained to perform dyeing of a film and addition of a hardener to a film, and at the same time, addition of a metal salt. In many embodiments, only 0. 0 1 to 10.0% by weight of the metal salt is added to the liquid boric acid/potassium iodide aqueous solution as a liquid hardener aqueous solution, thereby obtaining a hardener to the film and The addition of metal salts.

The shrink-stretched polarizing film can be carried out at any time during or after stretching. The method for shrinking the film may be a method of heating a film and thereby removing volatiles, however, any method may be used as long as it can shrink the film. The volatile matter content after drying is preferably 3% or less, more preferably 2% or less, and particularly preferably 1.5% or less. As described above, in a preferred embodiment of the present invention, the stretching method comprises: (i) stretching the film at least 1.1 to 20.0 times in the width direction;

(ii) providing a difference in moving speed between the side edges of the supporting device in 1% or more; (iii) moving the curved film while supporting both edges of the film so that the two supporting films The angle of the film moving at the exit in the edge step is inclined to 20 to 70° with respect to the substantially advanced stretching direction of the film; (1 v ) stretching the film while maintaining the supporting properties of the polymer film, and allowing the presence of 5 The volatile content of % or more is then shrunk to reduce the volatile content. In the present invention, the track of the trajectory of the support device is usually adjusted to have a large -41 - 1282013 bend ratio. In order to avoid the other sudden bending of the film engaging device or to avoid the interference of the stress density at the place, the trajectory of the engaging device is preferably drawn in an arcuate shape at the bent position.

In order to adhere the protective film to the polarizing film and to produce the oblique stretching, for example, an adhesive may be used in the drying step described above to adhere the protective film to the polarizing film while the both edges are maintained. Then, the method of cutting the side edges is used, or a method of removing the polarizing film from the side edge support portions after drying and cutting both side edges of the film, and adhering thereto.

As shown in Fig. 2, an embodiment of a polarizing plate obtained by punching obliquely (example of 45 ° tilt) is released. As shown in Fig. 2, since the stretching axis 81 of the polarized light, that is, the absorption axis of the polarized light, is inclined by 45° with respect to the longitudinal direction 82, and the absorption axis 71 of the protective film is parallel to the longitudinal direction, the inclination therebetween The angle becomes 45 °. Moreover, when the liquid crystal cell in the LCD is followed, the angle of the polarizing axis 8 1 is the same as the angle formed between the absorption axis of the polarizing plate and the opposite direction of the vertical or liquid crystal cell itself; therefore, it is not required in the punching step. Tilt punching. Moreover, as shown in FIG. 2, since the polarizing plate of the present invention is cut in a straight line in the longitudinal direction, a practical polarizing can be obtained even if the elongated polarizing plate is not punched by cutting along the longitudinal direction. The plate, from which a significant high yield can be obtained. The polarizing plate of the present invention preferably has a high transmittance and a high degree of polarization from the viewpoint of increasing the contrast of the liquid crystal display device. The light transmittance at 5 50 nm is preferably 30% or more, more preferably 40% or more. The degree of polarization at 550 nm is preferably 95% or more, more preferably 99.0% or more, and particularly preferably 99.9% - 42 to 1282013 or more. Unless otherwise specified, "transparency" as used in the present invention means the transmittance of a veneer.

The polarizing plate of the present invention is preferably used for a liquid crystal display. The liquid crystal display usually includes a liquid crystal display element and a polarizing plate. The liquid crystal display element includes a liquid crystal display layer, a substrate supporting the liquid crystal display layer, and an electrode layer for applying a potential to the liquid crystal display. The substrate and the electrode layer are made of a transparent material for display. In the case of a transparent material, a glass sheet or a resin can be used. In the case where the liquid crystal display needs to have some flexibility, a resin film must be used. Further, for high transparency, a liquid crystal display is required to have low birefringence and thermal resistance. Generally, a phase difference plate is provided in a liquid crystal display. The phase difference plate is a birefringent film for removing color on a liquid crystal image element and analyzing black and white image. The phase difference plate is also produced using a resin film. The phase difference plate requires high birefringence. The polarizing plate includes a polarizing film and a protective film. The polarizing film is a resin film using iodine or a two-color dye as a polarizing element. The protective film is provided on one surface or both surfaces of the polarizing film for the purpose of protecting the polarizing film. In the case where a protective film is provided only on one surface of the polarizing film, the liquid crystal substrate as described above is usually used as a protective film on the other surface. The protective film of the polarizing plate is required to have transparency and low birefringence (low hysteresis ,), and the cellulose acetate film used in the present invention is particularly advantageous for such purposes. The protective film of the polarizing plate includes an iodine type polarizing film, a dye type polarizing film using a two-color dye, and a polyene type polarizing film. Any of these polarizing films obtained is usually a polyvinyl alcohol type film. The thickness of the protective film of the polarizing plate is preferably 25 to 350 μm, more preferably 50 to 200 μm. In the protective film, an ultraviolet absorber, a slip agent, a decolorizing inhibitor, and a plasticizing agent-43-1282013 can be added. A surface treatment film may be further provided on the protective film of the polarizing plate. The function of the surface treatment film includes hard coating and anti-cloud treatment. The polarizing plate and its protective film are described in: ί P - A - 4 · 2 1 9 7 0 3, P - A - 5 - 2 1 2 8 2 8 , and JP - A · 6 - 5 1 1 1 7 in. The thickness of the protective film of such a polarizing plate is preferably from 1 350 to 350 μm, more preferably from 25 to 200 μm.

In the surface of the protective film of the polarizing plate of the present invention, any functional layer may be provided, for example, an optical anisotropic layer for compensating for the viewing angle of the LCD, an anti-glare layer or an anti-reflection layer for improving the visibility of the display, or a record Improving the brightness of LCDs by separating PS waves due to anisotropic or anisotropic optical refraction in JP-A-4-229828, JP-A-6-75115, and JP-A-8-50206 a layer (for example, a polymer dispersed liquid crystal layer, a cholesteric liquid crystal layer), a hard coating layer for improving the scratch resistance of the polarizing plate, and an air barrier layer for eliminating moisture or oxygen diffusion, for improving adhesion to the polarizing film Sexual adhesion layer, adhesive, or pressure sensitive adhesive, or layer that imparts slidability.

The functional layer may be provided on the side of the polarizing film or on the opposite surface of the polarizing film. The side layer provided with the functional layer can be appropriately selected according to the purpose. On one surface or both surfaces of the polarizing film of the present invention, different functional films can be directly bonded. Examples of the functional film include a phase difference plate such as a λ / 4 plate and a λ /2 plate, a light scattering film, a plastic crystal element having a conductive layer provided on the opposite surface of the polarizing plate, and an anisotropic diffraction or a different The film is modified to a brightness of an optical refractive function, a refractive plate, and a refractive plate having a reverse refractive index. One of the above protective films may be attached to be used as a protective film for a polarizing plate, or a plurality of sheets may be attached. The same protective film can be attached to both surfaces of the polarizing film -44-1282013, or the protective film attached to both surfaces can have different functions and physical properties from the other. It is also possible to attach the above-mentioned protective film 'only on one surface and not to attach the protective film to the opposite surface, but directly to a pressure-sensitive adhesive layer directly attached to the liquid crystal cell. In this case, the release separation membrane is preferably provided on the outer side of the pressure-sensitive adhesive. <Combination angle of protective film and polarizing film> In the present invention, when the protective film and the polarizing film are combined such that the orientation axis of the protective film (phase retardation axis) and the stretching axis (absorption axis) of the polarizing film are not parallel At an angle, it is possible to provide an effect of giving excellent dimensional stability. In order to obtain such an effect, the angle is preferably from not less than 10° to less than 90°, more preferably from 20° to less than 70°. <Protective film> The protective film is attached to both surfaces or a surface of the polarizing film produced by the present invention, and this laminated system is used as a polarizing plate. The protective film of this type is not particularly limited, and for example, cellulose deuterated cellulose such as cellulose acetate and cellulose acetate butyrate, polycarbonate, polyolefin, polystyrene, and polyester can be used. The protective film of such a polarizing plate is required to have, for example, transparency, proper moisture permeability, low birefringence, and appropriate rigidity; and from this point of view, it is preferably cellulose deuterated, and more preferably cellulose acetate. . The protective film may have any physical property 依照 depending on the purpose of use, and in this case, a representative 値 of a protective film for a normal transfer type LCD. The description is as follows. In view of portability and durability, the film thickness is preferably from 5 to 500 μm, more preferably from 20 to 20 μm, and particularly preferably from 20 to 1 μm. The hysteresis of 632.8 nm is preferably 〇 to 150 nm, preferably 〇1282013 to 20 nm, more preferably 0 to 10 nm, and particularly preferably 0 to 5 nm. The phase retardation axis of the protective film is preferably substantially parallel or orthogonal to the absorption axis of the polarizing film from avoiding linear polarization of the elliptical form. However, these are not applicable to the case of a protective film having a function of changing the polarizing property, such as a phase difference plate; and the absorption axis of the polarized light can form any angle with the phase retardation axis of the protective film.

The visible light transmittance is preferably 60% or more, more preferably 90% or more. The amount of reduction in size after treatment at 90 ° C for 120 hours is preferably from 0.3 to 0.01%, more preferably from 0.15 to 0.11%. The tensile strength in the film test is preferably from 50 to 100 MPa, more preferably from 100 to 300 MPa. The moisture permeation force of the film is preferably from 100 to 800 g/meter 2 day, more preferably from 300 to 600 g/m 2 day. Of course, the invention is not limited to this. Preferred deuterated cellulose as a protective film is described in detail below. Preferably, the deuterated cellulose has a degree of substitution to the hydroxyl group of the cellulose satisfying all of the following equations (I) to (IV) · (I) 2.6 A + B ' 3.0 (π ) 2. 0 A ^ 3.0 (ΙΠ ) 0 B ^ 0.8 (IV ) 1 · 9 A - B where A and B are: the degree of substitution of the hydroxyl group of the thiol-substituted cellulose, respectively

The degree of substitution of the A group is an ethyl group, and the degree of substitution of the group B with a group of 3 to 5 carbon atoms. The cellulose has three hydroxyl groups in one glucose unit, and the above number indicates that the degree of substitution of the hydroxyl group is 3.0, and the maximum degree of substitution is 3.0. In cellulose triacetate, the degree of substitution A is usually 2.6 to 3 · 0 (in this case -4 6 - 1282013

Under the shape, the unsubstituted base has a maximum of 0.4), and the enthalpy is 〇. The cellulose used for the protective film of the polarizing plate is preferably cellulose triacetate, wherein the fluorenyl group is all ethyl ketone group; or the oxime group in the fluorinated cellulose is 2.0 or more. The acid group of 3 to 5 carbon atoms is 0.8 or less, and the unsubstituted hydroxy group is 0.4 or less. The fluorenyl group having 3 to 5 carbon atoms is preferably 0·3 or less in terms of physical properties. The degree of substitution can be calculated from the measured degree of bonding of the acetic acid replacing the hydroxyl group of cellulose with the fatty acid having 3 to 5 carbon atoms. This measurement can be carried out by a method based on ASTM D-8 1 7 - 9 1 .

Is not an fluorenyl group having 3 to 5 carbon atoms, including propyl ketone (CKO - ), butyl sulfonyl (C3H7CO -) (positive-, iso-) and pentamidine (C4H9CO -) (positive-, hetero- -,the second, the third-). From among the mechanical strength of the formed film, among them, n-propyl group is preferred. If the degree of substitution of the ethyl group is low, the mechanical strength and resistance to humidity and heat will be lowered. When the degree of substitution of a mercapto group having 3 to 5 carbon atoms is high, the dissociation characteristics in an optical solvent are increased, but when the degree of individual substitution falls within the above range, good physical properties can be obtained. The degree of polymerization (average viscosity) of the deuterated cellulose is preferably from 200 to 700, more preferably from 2 50 to 550. The average viscosity of the polymerization reaction can be measured using an Oswald viscosity meter. The degree of polymerization can be calculated from the measured inherent viscosity of the fiber ruthenium [7?] according to the following equation: DP = [77] / Km (where DP is the average viscosity of the polymerization reaction 値, The Κιώ system is 6x1 (constant of T4). -47· 1282013 The cellulosic system used as the raw material for deuterated cellulose includes cotton wool and pulp, but the deuterated cellulose can be used as raw material cellulose from any of them. Or it can be used as a user of its mixture. Deuterated cellulose is usually produced by a solvent casting method. In the solvent casting method, deuterated cellulose and different additives are dissolved in The solvent is prepared to form a concentrated solution (hereinafter referred to as a coating liquid), and is cast on an endless support such as a drum or a belt, and the solvent is evaporated to form a film into the gas. The coating liquid is preferably prepared to have 10 to 40% by weight solids concentration. The drum or belt is preferably finished to have a mirror surface. This method of casting and drying in the solvent casting method is described in U.S. Patent 23 3 3 3 1 0, 2 3 6760 3,2492078, 2492977, 2492978 , 2607704, 273069 and 2739070; British Patent 640731 and 73 6892; Japanese Patent; iP-B-45-4554, JP-B-49-5614, JP-A-60-176834, JP-A-60-203430 and JP -A-62-115035

A casting method of two or more coating liquids is also a preferred method of use. In the case of casting a plurality of coating liquids, the film can be produced by a casting solution containing a coating liquid supplied from a plurality of casting portions supported in a moving direction stacked on the other, respectively. Further, for example, the methods described in JP-A-61-158414, JP-A-1-122419, and JP-H-198285 can be used. The film may also be formed using a cast deuterated cellulose solution from two casting sites, and one may be used, for example, in JP-B-60-27562, JP-A-61-94724, JP-A-61-947245 , JP-A-61-104813, JP-A-6 1 - 1 5 8 4 1 3 and JP - A - 6 - 1 3 4 9 3 3. Further, it is also preferred to use the casting method described in JP-A-5 6 - 1 626 1 7 in which the -48-1282013 high-viscosity coating liquid flows together with the low-viscosity coating liquid and simultaneously squeezes Press out the high viscosity and low viscosity coating solution.

Examples of organic solvents in which deuterated cellulose is dissolved include hydrocarbons (e.g., 'benzene, toluene), halogen hydrocarbons (e.g., dichloromethane, chlorinated benzene), alcohols (e.g., methanol, ethanol, diethylene glycol). And ketones (for example, acetone), esters (for example, ethyl acetate, propyl acetate), and ethers (for example, tetrahydrofuran, methyl cellosolve). Among them, a halogen hydrocarbon having 1 to 7 carbon atoms is preferred, and more preferably dichloromethane. Depending on the solubility of the deuterated cellulose, the support slidability, and the properties of the film such as mechanical strength and optical properties, it is preferred to additionally add one or more alcohols having 1 to 5 carbon atoms to the methylene chloride. in. The content of the alcohol is preferably from 2 to 25% by weight, more preferably from 5 to 20% by weight, based on the total of the solvent. Specific examples of alcohols include methanol, ethanol, n-propanol, isopropanol, and n-butanol. Among them, methanol, ethanol, and n-butanol and mixtures thereof are preferred.

In addition to deuterated cellulose, when the component becomes a solid component after drying, the coating liquid may optionally contain a plasticizer, an ultraviolet absorber, an inorganic fine particle, a thermal stabilizer such as an alkaline earth metal salt (calcium; magnesium), Antistatic agents, fire retardants, lubricants, oils, support release accelerators, hydrolysis inhibitors for cellulose halides, and the like. The plasticizer added is preferably a phosphate or a carboxylate. Examples of phosphates include triphenyl phosphate (TPP), tricresyl phosphate (TCP), cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, Trioctyl phosphate, and tributyl phosphate. Representative examples of carboxylic acid esters include phthalic acid esters, and citric acid esters. Examples of phthalic acid esters include dimethyl decanoic acid-49.1282013 ester (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (D0P). ), diphenyl phthalate (DPP), and diethylhexyl phthalate (DEHP). Examples of citrate esters include triethyl 0-ethenyl citrate (0ACTE), tributyl sulfonium-ethenyl citrate (0ACTB), acetyltriethyl citrate, and B. Mercapto tributyl citrate.

Examples of other carboxylic acid esters include butyl oleate, methyl acetyl ricinoleate, dibutyl sebacate, and trimellitate such as trimethyl trimellitate. Examples of glycolic esters include triacetin, tributyrin, butyl decyl butyl hydroxyacetate, ethyl decyl ethyl hydroxyacetate, and methyl thioethyl hydroxy Acetate.

Among these plasticizers, it is preferred to use triphenyl phosphate, diphenyl biphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, tributyl phosphate, dimethyl decanoic acid. Ester, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diethyl hexyl phthalate, triacetin, ethyl decyl ethyl hydroxy acetate, and top three More preferred are trimellitates; more preferably triphenyl phosphate, diphenyl biphenyl phosphate, diethyl phthalate, ethyl decyl ethyl hydroxyacetate, and trimethyl trimellitate Acid ester. These plasticizers may be used singly or in combination of two or more kinds thereof. The amount of the plasticizer added is preferably from 5 to 30% by weight, more preferably from 8 to 16% by weight, based on the deuterated cellulose. These compounds may be combined with deuterated cellulose or a solvent for preparing a cellulose solution, or may be added together during or after the preparation of the solution. The ultraviolet absorber can be freely selected according to the purpose thereof. For example, for example, a salicylate type, a benzophenone type, a benzotriphenyl group, a benzoate type, or a cyanoacrylate type can be used. And nickel complex salt-based absorbent. At -50- 1282013

Among them, benzophenone-based, benzotriazole-based, and salicylate-based absorbents are preferred. Examples of benzophenone-based anti-ultraviolet absorbers include 2,C dihydroxybenzophenone, 2-hydroxy-4-acetoxybenzophenone, 2-hydroxy-4-methoxydiphenyl Methyl ketone, 2,2'-dihydroxy-4 methoxybenzophenone, 2, 2, dihydroxy-4, 4'-methoxybenzophenone, 2-dihydroxy-4-n-octyl Oxybenzophenone, 2-hydroxy-4-ylideoxybenzophenone, and 2-hydroxy-4-(2»hydroxy-3-methylpropenyloxy)propoxybenzophenone. Examples of the benzotriazole-based anti-ultraviolet absorber include 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-benzotriazole, 2-(2) '-Hydroxy-5'-t-butylphenyl)-benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butyl-pentylphenyl)-benzotriene Oxazole, 2-(2'-hydroxy-3',5'-di-t-butyl-butylphenyl)-5-chlorobenzotriazole, and 2 - ( 2 '-hydroxy-5 ' - Trioctyl-phenyl)benzotriazole. Examples of salicylate-based anti-UV absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-t-butylphenyl salicylate. Among these ultraviolet absorbers, 2-hydroxy-4-methoxybenzophenone, 2,2,-dihydroxy-4,4,-methoxybenzophenone, 2-(2) are preferably used. ,-hydroxy-3, tert-butyl-5,-methylphenyl)-5-chlorobenzotriazole, 2-(2,-hydroxy-5,-tert-butylphenyl)-benzotriene Azole, 2-(2,-hydroxy-3,5,-di-t-butyl-pentylphenyl)-benzotriazole, 2-(2,-hydroxy-3,5,-di- Third butyl-butylphenyl)-5-chlorobenzotriazole. It is preferred to use a combination of a plurality of absorbents having different absorption wavelengths because a high shielding effect over a wide range of wavelengths can be obtained. The amount of the ultraviolet absorber is preferably from 0. 01 to 5% by weight, more preferably from 1 to 3% by weight, based on the deuterated cellulose. The ultraviolet absorber may be added to the dissociated solution of deuterated cellulose in the same manner as -51 - 1282013, or the coating liquid may be added after the dissociation liquid. In particular, the form in which the ultraviolet absorber solution is added to the coating liquid may be a static stirrer or the like; it is preferably added immediately before casting.

Examples of the inorganic fine particles added to the deuterated cellulose are vermiculite, kaolin, talc, diatomaceous earth, quartz, carbonic acid, barium sulfate, oxidized chin and alumina, and can be freely selected according to the purpose. It is preferred to use fine particles such as a high speed mixer, a honing machine, an attritor, or an ultrasonic disperser to immediately disperse the solution in the binder solution before adding the coating liquid. Further, the fine particles are preferably dispersed and mixed together with other additives such as ultraviolet absorbers. Any dispersing solvent can be used, but it is preferably a dispersing solvent having a composition close to that of the coating liquid solvent. The average particle diameter of the dispersed particles is preferably from 0.01 to 100 μm, more preferably from 0.1 to 10 μm. The dispersion solution may be added simultaneously in the step of dissociating the deuterated cellulose, or the coating liquid may be added in any step. However, it is preferred to use a static mixer equal to the form of the dispersion solution immediately before casting, and the same applies to ultraviolet rays. Absorbent.

The surfactant is effective from supporting the release accelerator, and the surfactant is not particularly limited, but examples thereof include a phosphate system, a sulfonic acid system, a carboxylic acid system, a nonionic system, and a cationic surfactant. . For example, as described in JP-A-6 1 - 24 3 8 3 7 . In the case of using a deuterated cellulose film suitable for a protective film, it is preferred to impart hydrophilicity to the surface of the film by saponification, corona treatment, flame treatment, electric discharge treatment or the like to enhance adhesion of the PVA type resin. Sex. It is also possible to disperse the hydrophilic resin in the solution forming the thin layer. Among these means, it is preferred to be a saponification treatment because the planarity and physical properties of the film are not impaired. -52- 1282013 The saponification treatment is carried out by immersing the film in an alkaline aqueous solution such as caustic soda. After treatment, the film is preferably neutralized with a low concentration of acid and completely washed with water to remove excess base.

The alkali saponification treatment is preferably used as a surface treatment of deuterated cellulose, and is specifically described below. This treatment is preferably carried out by immersing the deuterated cellulose film in an alkaline solution, washing with water, and then drying the film. Examples of the alkaline solution include a potassium hydroxide solution and a sodium hydroxide solution. The equivalent concentration of hydroxide ions is preferably from 0.1 to 3.0 N, more preferably from 0.5 to 2.0 N. The temperature of the alkaline solution is preferably from room temperature to 90 ° C, more preferably from 40 to 70 ° C. Then, the film is usually washed with water, and then washed with an acidic aqueous solution and then with water to obtain a surface-treated cellulose film. Examples of the acid used herein include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, formic acid, chloroacetic acid, and oxalic acid. The concentration of the acid is preferably from 0.01 to 3.0 N, more preferably from 0.05 to 2.0 N. In the case of using a deuterated cellulose film as a transparent protective film for a polarizing plate, it is preferred to carry out an acid treatment and an alkali treatment, that is, a saponification treatment, from the viewpoint of adhesion of the polarizing film. The surface energy of the obtained individual can be obtained by the method described in the basis and application of the wet (Lilitz, December 10, 1989), that is, by the contact angle method, the humid heat method or the adsorption method. Decide. Among these, the contact angle method is preferred, and the contact angle of water is preferably 5 to 90 °, more preferably 5 to 70. . On the surface of the protective film of the polarizing plate of the present invention, any functional layer may be provided, for example, an optical anisotropic layer for compensating for the viewing angle of the LCD, an anti-glare layer or an anti-reflection layer for improving the visibility of the display, or It is described in JP-A-4-229828, JP-A-6-75115, and JP-A-8-50206, which have a PS wave separated by anisotropic or anisotropic optical refraction. a layer for improving the brightness of the LCD (for example, a polymer dispersed liquid crystal layer, a cholesteric liquid crystal layer), a hard coating layer for improving the scratch resistance of the polarizing plate, and an air barrier layer for eliminating moisture or oxygen diffusion for improving An adhesive layer that adheres to a polarizing film, a binder, or a pressure-sensitive adhesive, or a layer that imparts slidability. The functional layer may be provided on the side of the polarizing film or on the opposite surface of the polarizing film. The side layer provided with the functional layer can be appropriately selected according to the purpose.

On one surface or both surfaces of the polarizing film of the present invention, different functional films can be directly bonded. Examples of the functional film include a phase difference plate such as a λ / 4 plate and a λ /2 plate, a light scattering film, a plastic crystal element having a conductive layer provided on the opposite surface of the polarizing plate, and an anisotropic diffraction or a different The film is modified to a brightness of an optical refractive function, a refractive plate, and a refractive plate having a reverse refractive index.

One of the above protective films may be attached to be used as a protective film for a polarizing plate, or a plurality of sheets may be attached. The same protective film can be attached to both surfaces of the polarizing film, or the protective film attached to both surfaces can have different functions and physical properties from the other. It is also possible to attach the above-mentioned protective film only to one surface, and not to attach the protective film to the opposite surface, but directly to a pressure-sensitive adhesive layer directly attached to the liquid crystal cell. In this case, the release separation membrane is preferably provided on the outer side of the pressure-sensitive adhesive. The protective film is usually fed in a roll shape 'and is preferably continuously attached to the long polarizing plate so that the longitudinal direction can be uniform. Here, the orientation axis (phase delay axis) of the protective film may be in any direction, but the orientation axis of the protective film is preferably parallel to the longitudinal direction as viewed from the viewpoint of ease of operation and easiness.

The angle between the phase retardation axis (orientation axis) of the protective film and the absorption axis (tensile axis) of the polarizing film is not particularly limited, and may be appropriately set in accordance with the purpose of the polarizing plate. In the present invention, the absorption axis of the polarizing film is not parallel to the longitudinal direction; moreover, therefore, when a protective film having an orientation axis parallel to the longitudinal direction is continuously attached to the long polarizing plate of the present invention, absorption of a polarizing film can be obtained. A polarizing plate in which the axis and the orientation axis of the protective film are not parallel. Such a protective film and a polarizing film are combined to form a polarizing plate which makes the absorption axis of the polarizing film and the orientation axis of the protective film non-parallel, and provides an effect of imparting excellent dimensional stability. This property is particularly beneficial for polarizers suitable for use on liquid crystal displays. The inclination angle between the phase retardation axis of the protective film and the absorption axis of the polarizing film is preferably not less than 10° to less than 90°, more preferably 20° to less than 80°. <Adhesive>

The adhesive for combining the polarizing film and the protective film is not particularly limited, and the examples thereof include a PVA resin (containing an alkylene group, a sulfonic acid group, a carboxyl group, an oxygen alkyl group or the like). Modified PVA), and an aqueous solution of a boron compound. Among them, PVA resin is preferred. A boron compound, an aqueous potassium iodide solution or the like may be added to the PVA resin. The thickness of the adhesive layer after drying is preferably from 0.01 to 10 μm, more preferably from 0.05 to 5 μm. <Pressure-sensitive adhesive layer> The polarizing plate of the present invention can provide a pressure-sensitive adhesive layer for adhering other liquid crystal display elements. Preferably, a peeling film is provided on the surface of the pressure-sensitive adhesive layer. This pressure-sensitive adhesive layer is of course optically transparent and presents the appropriate -55- 1282013

Viscous and pressure sensitive. The pressure-sensitive adhesive layer used in the present invention can be obtained by, for example, forming and hardening a film using a polymer of an adhesive or a pressure-sensitive adhesive, or by a drying method, a chemical hardening method, or heating. It is obtained by a hardening method, a hot melting method or a photohardening method. The pressure-sensitive adhesive is a propylene-based copolymer, an epoxy resin, a polyurethane, a polyoxymethylene polymer, a polyether, a butyral resin, a polyamide resin, or a polyvinyl alcohol resin. Or synthetic rubber. Among these, the propylene-based copolymer is preferable because the pressure-sensitive adhesiveness can be easily controlled, and it is excellent in transparency, weather resistance and durability. <complete step>

In the present invention, it is preferred to provide a drying step of stretching the stretched film to reduce the volatile content ratio, and then attaching the protective film to at least one surface of the film after or during drying, and is preferably It is a step of providing a post-heating film. A specific embodiment of the method of bonding a protective film includes a method of attaching to a polarizing film using an adhesive while maintaining a state of supporting both side edges of the polarizing film during a drying step, and then cutting both side edges; The support film is released from both side edges during drying, and the side edges are cut and a protective film is attached thereto. In order to cut the edges, it is possible to use a conventional technique such as a method of cutting an edge using a cutter such as a cutting tool, or a method using a laser. Preferably, the composite film is heated to dry the adhesive and enhance the properties of the polarizing film. The daily heat condition depends on the adhesive, but in the case of an aqueous adhesive, the heating temperature is preferably 30 ° C or more, more preferably 40 to 100 ° C, and even more preferably 50 to 8 (TC). According to the performance and the yield benefit, 'these production steps are preferably carried out in one line. -56-1282013 <Uses, etc.> The polarizing plate of the present invention can be used for different purposes, and is characterized in that The orientation axis is inclined in the longitudinal direction. In particular, it is preferable to use a polarizing film having an inclination angle of 40 to 50 between the orientation axis and the longitudinal axis as an LCD (for example, such as TN, STN, OCB, ROCB, ECB). , CPA, IPS, and VA) polarizers for all liquid crystal modules, recycled polarizers for anti-reflection of organic EL displays, and the like.

Further, the polarizing plate of the present invention is suitable for use in combination with different optical elements, for example, phase difference modes such as λ / 4 and λ / 2 plates, viewing angle magnifying film, anti-glare film and hard coated film. The invention will be explained in more detail with reference to the examples, however, the invention is not limited thereto. (4) Implementation: [Example 1]

On the surface of one of the longitudinally uniaxially stretched polyvinyl alcohol (PVA) films (a polarizing film having an absorption axis in the longitudinal direction), a liquid 3% PVA (PVA-117H, Kura 芮) was used. A solution made by Co., Ltd. is used as an adhesive, and a saponified Fuji film (cellulose triacetate, hysteresis: 3.0 nm) made by Fuji Photo Film Co., Ltd. is attached to prepare a first 〇 The five patterns shown in the figure (number 1 to number 5). Each of the obtained polarizing plates was evaluated as follows, that is, the dimensional stability and warpage which were matured in a dry constant humidity oven (D63) manufactured by Yamato Chemical Co., Ltd. were evaluated. (Size stability) -57- 1282013 Measure the percentage of shrinkage after 1 hour of treatment at 40 ° C and 30 % relative humidity. 〇: Within 2% △ : 2 ～ 5% X : More than 5 % {warping}

The polarizing plate was treated under an atmosphere of 40 ° C and 30% relative humidity for 100 hours, and then placed on a smooth surface. Visually observe the presence or absence of warpage and evaluate it in the following three stages. Warpage: Numbering of polarizing plate Stability Stabilization Remarks No. 1 〇〇 Inventive No. 2 〇〇 Inventive No. 3 〇〇 Inventive No. 4 XX Comparative Example No. 5 XX Comparative Example [Example 2] 〇: almost cocked △: warp X: severe warpage [Table 1]_

The PVA film was immersed in an aqueous solution containing 1 · gram / liter of iodine and 60 gram / liter of potassium iodide at 25 ° C for 90 seconds, and further immersed in 4 gram / liter of boric acid and 30 at 25 ° C 0 g / liter of potassium iodide in an aqueous solution for 120 seconds. Next, at -58-1282013, the film is introduced into a draw-type stretching machine having the form shown in Fig. 3, and after one stretching to 7.0 times, in an environment of 60 ° C and 90% RH. , the film will be shrunk to 5.3 times. Thereafter, it was dried at 70 ° C while maintaining a constant width, and the film was taken out by a draw frame. The PVA film had a volatile content of 31% before the start of stretching and 1.5% after drying. The difference in conveyance rate between the right and left puller clips is less than 0.05%, and the angle between the center line of the introduced film and the center line of the film fed to the subsequent step is 〇°. Here, 丨L1-L2I is 0.7 m, W is 0.7 m, and satisfies the relationship of 丨L1-L2 I =W. No wrinkles or film slips were seen at the exit of the ram. The obtained polarizing film had a stretching axis with an inclination angle of 45 ° with respect to the longitudinal direction. Then, 3% PVA (PVA-1 17H, manufactured by Kura, Inc.) containing an aqueous solution of potassium iodide as described above was used as an adhesive, and the saponified roll was stretched parallel to the longitudinal direction of Fuji Photo Film Co., Ltd. The Fuji film (cellulose triacetate, hysteresis 3: 3.0 nm) is continuously bonded to a long polarizing film while allowing the Fuji film to travel in the longitudinal direction, and at 8 (TC drying to obtain an effective one) a polarizing plate having a width of 650 mm. Then, the polarizing plate was cut into a size of 3 1 0 X 2 3 3 mm as shown in Fig. 2. As a result, an area efficiency of 91.5% was obtained, and a polarizing plate having an absorption axis inclined at 45° to the side. The transmittance of the polarizing plate is 43.3% at 550 nm, and the degree of polarization is 991.8%. It was carried out at 63 2.8 nm using KOBRA21DH manufactured by Ogi Test Instruments Co., Ltd. [Example 3] -59-1282013 The iodine type polarizing plates 9 1 and 9 2 prepared in Example 2 were used as two a polarizing plate with a liquid crystal cell 7 for LCD placed therebetween. As shown in Fig. 9, it will be biased. The board 9 1 is placed on the side of the display and attached to the liquid crystal cells 97 by an adhesive to prepare an LCD. The LCD thus prepared exhibits excellent brightness, viewing angle characteristics and visibility, and even at 40 After 100 hours in the atmosphere of °C and 30% RH, the polarizing plate was not separated from the liquid crystal display, indicating that the LCD has no problem in display characteristics.

[Embodiment 4]

The PVA film was immersed in an aqueous solution containing 1 g / liter of iodine and 60.0 g / liter of potassium iodide at 30 ° C for 90 seconds, and further immersed in a solution containing 40 g / liter of boric acid and 30 g at 30 ° C / liter of potassium iodide in an aqueous solution for 120 seconds. Next, the film is introduced into a stretcher type stretcher having the form shown in Fig. 3, and after stretching once to 6.4 times, the film is shrunk in an environment of 50 ° C and 95% RH. To 4.5 times. Thereafter, the film was dried at a constant width of 7 ° C and the film was taken out by a draw frame. The edge of 3 cm in the lateral direction was cut by a cutter, and then the PVA film was attached to the saponified using an aqueous solution of 3% PVA (PVA-1 17H manufactured by Kura) and 4% potassium iodide as an adhesive. Fujifilm (sodium triacetate, hysteresis: 3.0 nm) manufactured by Fuji Photo Film Co., Ltd., and further dried at 60 ° C for 30 minutes' to produce a polarized light with an effective width of 650 mm board. The moisture content of the PVA film was 30%' before the start of stretching and 1.5% after drying. The moisture content reduction rate during shrinkage was 5% / min' and the dry point was in the middle of the (c) zone. -60- 1282013 The difference in conveying rate between the right and left bracing machine clamps is less than 0.05% and the angle between the centerline of the introduced film and the centerline of the film fed to the subsequent step is 0. . . Here, 丨Ll-L2丨 is 〇·7 meters′... is 〇·7 meters and satisfies the relationship of 丨LI-L2丨=W. No wrinkles or deformation of the film were observed at the exit of the ram.

The obtained polarizing film had a stretching axis with an inclination angle of 45 ° with respect to the longitudinal direction. The inclination angle of the absorption axis of the polarizing plate was examined every 50 mm intervals in the lateral direction, and as a result, the average inclination angle of the stretching axis with respect to the longitudinal direction was 45°, and the dispersion 値 was ±0.5°. On a plane of 1 m 2 , the transmittance and the degree of polarization of the polarizing plate at 550 mm were examined every 50 mm intervals, and the average transmittance was 40.2%, and the average degree of polarization was 9 9 . . 5 6%. Further, the polarizing plate was cut into a size of 3 1 0 X 2 3 3 mm as shown in Fig. 2. As a result, a polarizing plate having an area efficiency of 91.5% and an absorption axis inclined at 45 with respect to the side was obtained. [Embodiment 5]

The PVA film was immersed in an aqueous solution containing 1.0 g/L of iodine and 10.0 g/L of potassium iodide at 40 ° C for 90 seconds, and further immersed in 40 g / liter of boric acid and 30 g at 40 ° C / liter of potassium iodide in an aqueous solution for 60 seconds. Thereafter, the film was introduced into a stretcher type stretcher having the form shown in Fig. 4, and stretched to 4.5 times at 65 ° C and 95 %. Next, the stretching direction of the film was bent as shown in Fig. 4, after which the film was kept at a fixed width while drying the film in an atmosphere of 8 〇 ° C, and the film was taken out by a zipper. The edge of 3 cm in the lateral direction was cut by a cutter, and then a PVA-61 - 1282013 film was attached by using an aqueous solution of 3% PVA (PVA-117H manufactured by Kura) and 4% potassium iodide as an adhesive. It was made into a Fuji film (cellulose triacetate, hysteresis 3: 3.0 nm) made by saponified Fuji Photo Film Co., Ltd., and further dried at 60 ° C for 30 minutes to make an effective width of 6 50 Millimeter polarizer. The moisture content of the PVA film was 3 0.5% before the start of stretching, and 1.5% after drying. The moisture content reduction rate during shrinkage was 10%/min, and the drying point was at the point of 1/3 of the (c) zone.

The difference in transport rate between the right and left draw frame clamps is less than 〇0.55%, and the angle between the centerline of the introduced film and the centerline of the film fed to the subsequent step is 46°. Here, 丨L1-L 2丨 is 0.7 meters, W is 0.7 meters, and satisfies the relationship of 丨Ll-L2 I =W. The solid drawing direction Ax - Cx at the exit of the ram is inclined at an angle of 45 ° with respect to the center line 22 of the film to be delivered to the subsequent step. At the exit of the ram, no wrinkles and deformation of the film were observed.

The absorption axis direction of the obtained polarizing plate was inclined at 45 ° with respect to the longitudinal direction. The inclination angle of the absorption axis of the polarizing plate was examined every 50 mm intervals in the lateral direction, and as a result, the average inclination angle of the stretching axis with respect to the longitudinal direction was 45°, and the dispersion 値 was ±0.25°. On a plane of 1 m 2 , the transmittance and the degree of polarization of the polarizing plate at 550 mm were examined every 50 mm intervals, and the average transmittance was 42. 2%, and the average degree of polarization was 99. 97% In addition, the polarizing plate was cut to a size of 3 10 0 23 3 mm as shown in Fig. 2. As a result, a polarizing plate having an area efficiency of 91.5% and an absorption axis inclined at 45° with respect to the side was obtained. -62-1282013 [Comparative Example 2] The PVA film was immersed in an aqueous solution containing 1.0 g/L of iodine and 120.0 g/L of potassium iodide at 40 ° C for 90 seconds, and further immersed in 40 g at 40 ° C. / liter of boric acid and 30 g / liter of potassium iodide in an aqueous solution for 60 seconds. Thereafter, the film was introduced into a stretcher type stretcher having the form shown in Fig. 4 and stretched to 4.5 times. Next, the stretching direction of the film was bent as shown in Fig. 4, after which the film was dried at a constant temperature while drying the film in an atmosphere of 40 ° C, and the film was taken out by a draw machine. The edge of 3 cm in the lateral direction was cut by a cutter, and then the PVA film was attached to the saponified Fuji using an aqueous solution of 3% PVA (PVA-117H manufactured by Kura) and 4% potassium iodide as an adhesive. Fuji Film (cellulose triacetate, hysteresis 3: 3.0 nm) manufactured by Photographic Film Co., Ltd., and further dried at 60 ° C for 30 minutes to prepare a polarized light having an effective width of 650 mm. board. The direction of the absorption axis of the obtained polarizing plate was 45 ° with respect to the longitudinal direction. The inclination angle of the absorption axis of the polarizing plate was examined every 50 mm in the lateral direction, and as a result, the average inclination angle of the stretching axis with respect to the longitudinal direction was 45 °, and the dispersion 値 was ±3%. On a plane of 1 m 2 , the transmittance and the degree of polarization of the polarizing plate at 550 nm were examined every 50 mm intervals, and the average transmittance was 41.1%, and the average degree of polarization was 9 9 . 7 8%. [Example 6] The iodine type polarizing plates 9 1 and 92 prepared in Example 5 were used as two polarizing plates with a liquid crystal cell 9 for LCD placed therebetween. As shown in Fig. 9, a polarizing plate 9 1 was placed on the side of the display, and attached to the liquid crystal cell 9 through an adhesive to prepare an LCD. -63-1282013 The LCD thus prepared exhibits excellent brightness, viewing angle characteristics, and visibility, and the display level is not attenuated even if it is used for one month in an atmosphere of 40 ° C and 30% RH. (Measurement of transmittance and polarization at 550 nm)

The transmittance was measured with a Shimadzu automatic recording spectrophotometer UV2100. Furthermore, when the two polarizing plates overlap each other and the absorption axes coincide with each other, the measured transmittance is H0 (%), and when the two polarizing plates overlap each other and the absorption axes intersect at right angles, the measured transmittance is Η 1 (%), the degree of polarization P (%) can be determined by the following equation, ie Ρ[[Η0-Η1) / (Η0 + Η1)] 1/2 xl 00 (measurement of hysteresis )) at 6 3 2 The hysteresis of 8ηπι was measured by using KOBRA 2 1DH manufactured by Ogilvy Test Instruments. [Embodiment 7]

The surface of the PVA film is washed with ion-exchanged water at a water flow rate of 2 liters/min, and the air is blown to drain the moisture on the surface, so that the substance adhering to the surface is reduced to 0. 5% Or below. This PVA film was immersed in an aqueous solution containing 1.0 g/liter of iodine and 60.0 g/liter of potassium iodide at 30 ° C for 90 seconds, and further immersed in a solution containing 40 g / liter of boric acid and 30 g / liter of potassium iodide at 30 ° C The aqueous solution has a history of 120 seconds. Then, the blowing air removes excess moisture on the surface so that the moisture content distribution in the film becomes 2% or less. In this state, the film is introduced into a stretcher type stretcher having the form shown in Fig. 3, and after one stretching to 6.4 times, in an environment of 45 ° C and 9 5% RH. The film will be shrunk to -64-1282013 4 · 5 times. After that, it was dried at 80 °C while maintaining the width fixed, and the thin 0 was taken out by the bracing machine. The edge of 3 cm in the lateral direction was cut by a cutter, and then the PVA film was attached to the saponified Fuji using an aqueous solution of 3% PVA (PVA-117H manufactured by Kura) and 4% potassium iodide as an adhesive. Fuji Film (cellulose triacetate, hysteresis 3: 3.0 nm) manufactured by Photographic Film Co., Ltd., and further dried at 60 ° C for 30 minutes to prepare a polarized light having an effective width of 650 mm. board. The moisture content of the PVA film was 30% before the start of stretching, and was 1.5% after drying. The moisture content reduction rate during shrinkage was 5% / min. The difference in conveying rate between the right and left bracing machine clamps is less than 0.05%, and the angle between the center line of the introduced film and the center line of the film fed to the subsequent step is 0°. Here, 丨L1-L 21 is 0.7 meters, W is 0.7 meters, and the relationship of IL1_L2 l=W is satisfied. At the exit of the ram, no wrinkles or deformation of the film were observed. The absorption axis direction of the obtained polarizing plate was 45 ° with respect to the longitudinal direction, and the inclination angle with respect to the phase retardation axis of the Fuji film as a protective film was also 45 °. In the plane of 1 m 2 , the transmittance and the degree of polarization of the polarizing plate at 550 nm were examined every 50 mm intervals, and the average transmittance was 40.8%, and the average degree of polarization was measured. It is 99.55%, and the maximum 値 and the minimum 値 of the two transmittances and the degree of polarization are ± 0.5%. Further, the polarizing plate was cut into a size of 3 1 0 X 2 3 3 mm as shown in Fig. 2. As a result, a polarizing plate having an area efficiency of 91.5% and an absorption axis inclined at 45 ° with respect to the side was obtained. -65-1282013 [Embodiment 8]

The surface of the PVA film is washed with ion-exchanged water at a water flow rate of 2 liters/min, and the air is blown to drain the moisture on the surface, so that the substance adhering to the surface is reduced to 0. 5% Or below. The PVA film was immersed in an aqueous solution containing K 0 g / liter of iodine and 10.0 g / liter of potassium iodide at 40 ° C for 90 seconds, and further immersed in 4 (TC immersed with 40 g / liter of boric acid and 30 g / liter of potassium iodide in an aqueous solution for 60 seconds. Then, the blowing air will remove excess moisture on the surface, so that the moisture content distribution in the film becomes 2% or less. In this state, the film is introduced into one The stretch-type stretching machine of the form shown in Fig. 4 is stretched to 4.5 times in an environment of 65 ° C and 9 5% RH. Then, the stretching direction of the film is bent as the fourth As shown in the figure, after that, the film was kept at a fixed width while drying the film in an atmosphere of 80 ° C, and the film was taken out by a bracing machine. The edge was cut at a distance of 3 cm in the lateral direction by a cutter, and then 3% PVA (library) was used. Lava company's PVA-1 17H) aqueous solution and 4% potassium iodide were used as adhesives. The PVA film was attached to a saponified Fuji Photo Film Co., Ltd. Fuji film (cellulose triacetate, hysteresis: 3 . 0 nm), and further dried at 60 ° C for 30 minutes, and made a A polarizing plate having an effective width of 65 mm. The moisture content of the PVA film is 32% before the start of stretching, and is 5% after drying. The moisture content reduction rate during shrinkage is 10%/ The difference in the transport rate between the right and left puller clips is less than 0.05%, and the angle between the centerline of the introduced film and the centerline of the film fed to the subsequent step is 46°. Where, 丨L1-L2I is 0.7 meters, W is 0.7 meters, and satisfies the relationship of I L1-L2 。. The substantial stretch at the exit of the broaching machine -66- 1282013 to Αχ - Cx relative to The inclination angle of the center line 22 of the film fed to the subsequent step is 45°. At the exit of the ram, no deformation of the wrinkles and the film is observed. The absorption axis direction of the obtained polarizing plate is relative to the longitudinal direction. The angle of inclination is 45 °. On a plane of 1 m 2 , the transmittance and polarization of the polarizing plate at 550 nm are examined every 50 mm intervals, and the average transmittance is 4 2.9%. And the average degree of polarization is 9 9.9 7%, and the maximum 値 and the minimum 値 of the two transmittances and the degree of polarization are ±0 . 25%.

Further, the polarizing plate was cut into a size of 3 1 0 X 2 3 3 mm as shown in Fig. 2. As a result, a polarizing plate having an area efficiency of 91.5% and an absorption axis inclined at 45 with respect to the side was obtained. [Comparative Example 3]

The ion exchange water with a water flow rate of 0.1 liter/min is used to wash both surfaces of the PVA film, and the air is blown to drain the moisture on the surface, so that the foreign matter adhered to the surface is reduced to 2%. Or below. The PVA film was immersed in an aqueous solution containing 1.0 g/liter of iodine and 10.0 g/liter of potassium iodide at 40 ° C for 90 seconds, and further immersed in 40 g / liter of boric acid at 40 ° C. And 60 g / liter of potassium iodide in an aqueous solution for 60 seconds. Then, without blowing air onto both surfaces of the film, the moisture content distribution in the film became 10%. In this state, the film was introduced into a draw-type stretching machine of the form shown in Fig. 4 and stretched to 4.5 times. This tying machine was bent in the stretching direction as shown in Fig. 4, after which it was kept at a fixed width and contracted while being dried in an atmosphere of 40 ° C, and the film was taken out by a zipper. Using a cutter to cut the edge at a distance of 3 cm, and then use a 3% PVA (Kura Co., Ltd. -67-1282013)

PVA - 1 17H) aqueous solution and 4% potassium iodide as an adhesive, this PVA film was attached to a saponified Fuji Photo Film Co., Ltd. Fuji film (cellulose triacetate, hysteresis: 3.0 nm) The film was further dried at 60 ° C for 30 minutes to prepare a polarizing plate having an effective width of 650 mm. Dyeing unevenness is generated and spread over the entire surface of the film. On a plane of 1 m 2 , the transmittance and the degree of polarization of the polarizing plate at 550 nm were examined every 50 mm intervals, and the average transmittance was 40.1%, and the average degree of polarization was measured. It is 99.46%, and the maximum enthalpy and minimum enthalpy of the two transmittances and the degree of polarization are ±3%. [Example 9] The iodine type polarizing plates 9 1 and 9 2 prepared in Example 8 were used as two polarizing plates with a liquid crystal cell 9 for LCD placed therebetween. As shown in Fig. 9, a polarizing plate 9 1 was placed on the side of the display, and attached to the liquid crystal cell 9 through an adhesive to prepare an LCD.

The LCD thus prepared exhibits excellent brightness, viewing angle characteristics, and visibility, and the display level is not attenuated even if it is used for one month in an atmosphere of 40 ° C and 30% RH. (Measurement of Transmittance and Polarization at 550 nm) The transmittance was measured with a Shimadzu automatic recording spectrophotometer UV2 100. Furthermore, when the two polarizing plates overlap each other and the absorption axes coincide with each other, the measured transmittance is Η 0 (%), and when the two polarizing plates overlap each other and the absorption axis intersects at right angles, the measured transmittance is obtained. For Η 1 ( % ), the degree of polarization Ρ ( % ) can be determined by the following equation, ie

Ρ=[ (Η0-Η1 ) / (Η0 + Η1 ) ] 1/2 xlOO -68- 1282013 (Measurement of hysteresis )) The hysteresis at 6 3 2 . 8 nm is achieved by using Ogi Test Instruments Manufactured KOBRA 21DH to measure. [Example 1 0]

The surface of the PVA film is washed with ion-exchanged water at a water flow rate of 2 liters/min, and the air is blown to drain the moisture on the surface, so that the foreign matter adhered to the surface is reduced to 0·5%. Or below. The PVA film was immersed in an aqueous solution containing 1.0 g/liter of iodine and 605 g/liter of potassium iodide at 25 ° C for 90 seconds, and further immersed in a solution containing 40 g / liter of boric acid at 25 ° C. And in an aqueous solution of 30 g / liter of potassium iodide for 1 20 seconds. Next, the film is introduced into a stretcher type stretcher having the form shown in Fig. 3, and after stretching once to 7.0 times, the film is applied in an environment of 40 ° C and 95% RH. Shrink to 5.3 times. Thereafter, it was dried at 60 ° C while maintaining the width fixed, and the film was taken out by a draw machine. The VVA film had a volatile content of 30% before the start of stretching and 1.5% after drying. The PVA film had an elastic modulus of 35 MPa before stretching in an atmosphere of 40 ° C and 9 5%. The difference in conveyance rate between the right and left puller clips is less than 0.05%, and the angle between the center line of the introduced film and the center line of the film fed to the subsequent step is 0°. Here, IL1-L2I is 0.7 m, W is 0.7 m, and satisfies the relationship of 丨L1-L2丨=W. No wrinkles or film slips were seen at the exit of the ram. At this time, the surface roughness Ra of the polarizing plate was measured by a surface roughness tester (manufactured by Sakaka Laboratory Co., Ltd.), and the enthalpy was 1.0 μm. Then, this PVA film is attached to the saponified, Fuji Photo Film Co., Ltd. -69- 1282013

Fujifilm (cellulose triacetate, hysteresis 値: 3.0 nm; saponification of cellulose triacetate film is carried out as follows: the cellulose triacetate film is immersed in a 1.5 Ν sodium hydroxide solution, Washed at 55 ° C for 2 minutes, at room temperature in a water bath, neutralized with 0.1 °N sulfuric acid at 30 ° C, then washed in a water bath at room temperature, and then at 100 ° On the air-dried C, an aqueous solution of 3% PVA (PVA-117H manufactured by Kura) and 4% potassium iodide were used as an adhesive, and further dried at 60 ° C for 3.0 minutes to prepare an effective width. It is a 6 50 mm polarizer. Such a film adheres to other films in a good state, that is, a substantially smooth surface. The absorption axis direction of the obtained polarizing plate was 45 ° with respect to the longitudinal direction, and the inclination angle with respect to the phase retardation axis of the Fuji film (protective film) was also 45°. The polarizing plate has a transmittance of 41.3% at 550 nm and a polarization degree of 99.60%.

In addition, the polarizing plate was cut to a size of 31 Ο X 2 3 3 mm as shown in Fig. 2. As a result, a polarizing plate having an area efficiency of 91.5% and an absorption axis inclined at 45 with respect to the side was obtained. No color sliding streaks were visually observed. [Example 1 1] The two surfaces of the pva film were washed with ion-exchanged water having a water flow rate of 2 liters/min, and the air was blown to drain the moisture on the surface to adhere the surface to the foreign matter. Reduced to 0. 5 % or less. The PVA film was immersed in an aqueous solution containing 1.0 g/liter of iodine and 12.0 g/liter of cesium iodide at 40 ° C for 90 seconds, and further immersed in 40 ° C at 40 ° C. / liter of boric acid and 30 g / liter of potassium iodide in an aqueous solution for 60 seconds. Next, the film will be guided -70- 1282013

The film was stretched to 4.5 times in a draw type stretching machine having the form shown in Fig. 4. The film was bent in the direction of stretching as shown in Fig. 4, and then kept at a fixed width and shrunk while drying the film in an atmosphere of 80 ° C and the film was taken out by a stretcher. The edge of 3 cm in the lateral direction was cut by a cutter, and then the PVA film was attached to the saponified using an aqueous solution of 3% PVA (PVA-1 17H manufactured by Kura) and 4% potassium iodide as an adhesive. Fuji Film Co., Ltd. made Fuji film (cellulose triacetate, hysteresis 3: 3.0 nm), and further dried at 60 ° C for 30 minutes to make an effective width of 650 mm. Polarizer. The moisture content of the PVA film was 32% before the start of stretching, and was 1.5% after drying. The PVA film had an elastic modulus of 2 5 M p a before stretching in an atmosphere of 40 ° C and 9 5%. The surface roughness Ra of the polarizing plate after drying was measured using the tester of Example 1 and found to be 0.05 μm.

The difference in transport rate between the right and left draw frame clamps is less than 〇 〇 5%, and the angle between the centerline of the introduced film and the centerline of the film fed to the subsequent step is 46°. Here, IL1-L 21 is 0.7 m, W is 0.7 m, and satisfies the relationship of 丨L1-L2丨=W. The solid drawing direction Ax - Cx at the exit of the ram is inclined at an angle of 45 ° with respect to the center line 22 of the film to be delivered to the subsequent step. At the exit of the ram, no wrinkles and deformation of the film were observed. The direction of the absorption axis of the obtained polarizing plate was 45° with respect to the longitudinal direction. The polarizing plate has a transmittance of 42.3% at 5 50 nm and a degree of polarization of 99.9.7%. Further, the polarizing plate was cut into a size of 3 10 0 2 3 3 mm as shown in Fig. 8. As a result, a polarizing plate having an area efficiency of 91.5% and an absorption axis of -71 - 1282013 and inclined at 45 ° with respect to the side was obtained. No color sliding streaks were visually observed. [Comparative Example 4]

The water is sprayed at a water flow rate of 2 liters/min. The two surfaces of the pva film are washed, and the air is blown to drain the water on the surface, so that the foreign matter adhered to the surface is reduced to 0.5%. Or below. The PVA film was immersed in an aqueous solution containing 1.0 g/liter of iodine and 12.0 g/liter of potassium iodide at 40 ° C for 90 seconds, and further immersed in 40 g / liter of boric acid at 40 ° C and An aqueous solution of 30 g/liter of potassium iodide was used for 60 seconds. The PVA film had a moisture content of 1%, and in this state, the modulus of elasticity was 8 MPa. Then, the PVA film is introduced into a stretcher type stretching machine of the form shown in Fig. 4 and stretched to 4.5 times 'after' to maintain a fixed width and shrink, while drying in an atmosphere of 8 Torr, and pulling Take out the film. The wrinkles are spread over the entire surface of the film, and the surface roughness Ra is 2 cm. Since the roughness is large, the protective film cannot be attached, and thus the polarizing plate cannot be obtained. A large number of color sliding stripes exist on the entire surface. [Example 1 2] The iodine type polarizing plates 9 1 and 9 2 prepared in Example 11 were used as two polarizing plates with a liquid crystal cell 7 for LCD placed therebetween. As shown in Fig. 9, a polarizing plate 9 1 was placed on the side of the display, and attached to the liquid crystal cell 7 through an adhesive to prepare an LCD. The LCD thus prepared exhibits excellent brightness, viewing angle characteristics, and visibility, and the display level is not attenuated even if it is used for one month in an atmosphere of 40 ° C and 30% RH. -72-1282013 (Measurement of Transmittance and Polarization at 5 50 nm) The transmittance was measured with a Shimadzu automatic recording spectrophotometer UV2 100. Furthermore, when the two polarizing plates overlap each other and the absorption axes coincide with each other, the measured transmittance is H0 (%), and when the two polarizing plates overlap each other and the absorption axes intersect at right angles, the measured transmittance is Η 1 (%), the degree of polarization P (%) can be determined by the following equation, ie

Ρ=[(Η0-HI )/(Η0 + Η1 )]丨/2 xlOO (Measurement of hysteresis値)

The hysteresis at 6 8 8 nm was measured by using KOBRA 2 1DH manufactured by Ogilvy & Mather. [Example 1 3] <Preparation of polarizing plate>

The PVA film having an average degree of polymerization of 1 700 was immersed in an aqueous solution containing 1 g / liter of iodine and 60 g / liter of potassium iodide at 40 ° C for 90 seconds, and further immersed in 40 ° C An aqueous solution containing 40 g/L of boric acid and 30.0 g/L of potassium iodide and added with a concentration of 1.0% by weight of ferric chloride was used for 1 20 seconds. Next, the film was introduced into a stretcher type stretcher having the form shown in Fig. 3, and after stretching once to 7.0 times, the film was shrunk to 5.3 times. Thereafter, it was dried at 60 ° C while maintaining a constant width, and the film was taken out by a draw frame. The moisture content (volatile content) of the PVA film was 3 1% before the start of stretching, and was 丨.5% after drying. The difference in transport rate between the right and left puller clips is less than 〇 〇 5%, and the angle between the centerline of the introduced film and the centerline of the film fed to the subsequent step is zero. . Here, 丨L1-L2I is 0.7 meters, W is 〇·7 meters -73-1282013, and the relationship of IL1-L2 l=W is satisfied. The angle of inclination of the substantial stretch direction Ax - Cx at the exit of the ram at the center line 22 of the film to be delivered to the subsequent step is 45 °. No wrinkles and deformation of the film were observed at the exit of the broaching machine. Then, a 3% PVA (PVA-1 17H made by Kura) company was used as an adhesive, and this PVA film was photographed with saponified Fuji. A Fuji film (cellulose triacetate, hysteresis 値: 3.0 nm) manufactured by Soft Film Co., Ltd. was attached, and dried at 80 ° C to obtain a polarizing plate having an effective width of 650 mm. The absorption axis direction of the obtained polarizing plate is 45 ° with respect to the longitudinal direction, and the inclination angle with respect to the phase retardation axis of the Fuji film is also 45 °. The transmittance of the polarizing plate is 550 nm at 42 nm. 9%, and the degree of polarization is 99.89%.

Further, the polarizing plate was cut into a size of 3 10 0 2 3 3 mm as shown in Fig. 2. As a result, a polarizing plate having an area efficiency of 91.5% and an absorption axis inclined at 45 with respect to the side was obtained. The obtained polarizing plate was subjected to a heat resistance test, and a humidity resistance and a heat test. As a result, the width of variation of the transmittance of the veneer was 9.2%, and the variation width of the degree of polarization was 8.3%. <Evaluation of Humidity Resistance and Heat Resistance> (Exposure to High Humidity and High Temperature) The polarizing plate was placed in an atmosphere of 60 ° C and a humidity of 90% for 500 hours at a fixed temperature and a fixed humidity. It is used as a sample in the oven (G-42M, Shandu Chemical Co., Ltd. - 74-1282013). (Variation width of transmittance) The transmittance at 550 nm was measured with a Shimadzu automatic recording spectrophotometer UV 2100, and the variation width was calculated according to the following equation: Variation width of transmittance = (I Ti-Tol /T.)xlOO where T! is the transmittance of the sample exposed to high humidity and high temperature, and enthalpy. It is the transmittance before exposure. (variation width of polarization)

The transmittance at 550 nm was measured with a Shimadzu automatic recording spectrophotometer UV2 100, and the degree of polarization Ρ (%) was obtained according to the equation (1), and then the variation width was calculated by the following equation (1): The variation width of the transmittance = (I Pi - P. I / Ρ.) xlOO where Pi is the transmittance of the sample exposed to high humidity and high temperature, and the transmittance of P ◦ before exposure. <Evaluation of heat resistance>

(Exposure to high temperature) The polarizing plate was placed in an atmosphere of 80 ° C and a humidity of 30% for 500 hours in a Shimadzu dry fixed temperature oven (D6 3 ), and used as a sample. (Variation width of the transmittance and width of the polarization degree) The width of variation of the transmittance and the variation width of the degree of polarization were evaluated in the same manner as described in <Evaluation of Humidity Resistance and Heat Resistance>. [Example 1 4] <Preparation of polarizing plate> -75-1282013 A PVA film having an average degree of polymerization of 17,000 was immersed in a mixture containing 1. gram per liter of iodine and 60 Å at 0 °C at 40 °C. / liter of potassium iodide in an aqueous solution for 90 seconds, and further immersed in 40 ° C / 40 ° / liter of boric acid and 30 · 0 g / liter of potassium iodide, and added a concentration of 1.0% by weight of zinc chloride aqueous solution The middle calendar is 1 2 0 seconds. Next, the film was introduced into a stretcher type stretcher having the form shown in Fig. 3, and after stretching once to 7.0 times, the film was shrunk to 5.3 times. Thereafter, it was dried at 60 ° C while maintaining a constant width, and the film was taken out by a draw frame. The moisture content (volatile content) of the PVA film was 31% before the start of stretching, and was 1.5% after drying. The difference in conveyance rate between the right and left puller clips is less than 0.05%, and the angle between the center line of the introduced film and the center line of the film fed to the subsequent step is 0°. Here, 丨L1-L2I is 0.7 meters, W is 0.7 meters, and satisfies the relationship of 丨L 1 -L2 I =W. No wrinkles or deformation of the film were observed at the exit of the ram. Then, using a 3% PVA (PVA-1 17H manufactured by Kuraaki Co., Ltd.) aqueous solution as an adhesive, the PVA film and the saponified Fuji Photo Film Co., Ltd. Fuji film (cellulose triacetate, hysteresis) : 3.0 nm), and dried at 80 ° C to obtain a polarizing plate having an effective width of 650 mm. The absorption axis direction of the obtained polarizing plate was 45 ° with respect to the longitudinal direction, and the inclination angle with respect to the phase retardation axis of the Fuji film was also 45 °. The transmittance of the polarizing plate was 43 at 550 nm. 0%, and the degree of polarization is 99.95%. -76- 1282013 The obtained polarizing plate was subjected to a heat resistance test, and humidity resistance and heat test. As a result, the variation width of the transmittance of the veneer was 2.4%, and the degree of polarization was measured. The variation width is 1.2%. [Example 1 5] <Preparation of polarizing plate>

The PVA film having an average degree of polymerization of 2400 was immersed in an aqueous solution containing 1.0 g/L of iodine and 60 g/l of potassium iodide for 90 seconds at 40 ° C, and further immersed in 40 ° C An aqueous solution containing 40 g/L of boric acid and 30.0 g/L of potassium iodide and added with 1.0% by weight of zinc chloride for 1 20 seconds. Next, the film was introduced into a stretcher type stretcher having the form shown in Fig. 3, and after stretching once to 7.5 times, the film was further shrunk to 5.3 times. Thereafter, it was dried at 60 ° C while maintaining a constant width, and the film was taken out by a draw frame. The moisture content (volatile content) of the PVA film was 31% before the start of stretching, and was 1.5% after drying.

The difference in conveyance rate between the right and left draw frame clamps is less than 0.05%, and the angle between the center line of the introduced film and the center line of the film fed to the subsequent step is 〇°. Here, IL1-L2I is 0.7 meters, W is 0.7 meters, and the relationship of IL1-L2 l=W is satisfied. No wrinkles or deformation of the film were observed at the exit of the ram. Then, using a 3% PVA (PVA-117H manufactured by Kura) Co., Ltd. as an adhesive, the PVA film and the saponified Fuji Photo Film Co., Ltd. Fuji film (cellulose triacetate, hysteresis: 3 · 0 nm) was bonded and dried at 80 ° C to obtain a polarizing plate having an effective width of 65 mm. -77- 1282013 The absorption axis direction of the polarizing plate obtained is 45 ° with respect to the longitudinal direction, and the inclination angle with respect to the phase retardation axis of the Fuji film is also 45 °. The transmittance of the polarizing plate is 5 5 0 The nanometer was 43.2% and the degree of polarization was 99.74%. The obtained polarizing plate was subjected to heat resistance, humidity resistance and heat resistance test, and as a result, the variation width of the transmittance of the veneer was 0.8%, and the variation width of the degree of polarization was 0.3%.

[Example 1 6] <Preparation of liquid crystal display> The iodine type polarizing plates 9 1 and 9 prepared in Example 14 were used as two polarizing plates with a liquid crystal cell for LCD placed therebetween. 9 3. As shown in Fig. 9, a polarizing plate 91 is placed on the side of the display and attached to the liquid crystal cells 93 through an adhesive to prepare an LCD.

The LCD thus prepared exhibits excellent brightness, viewing angle characteristics, and visibility, and the display level is not attenuated even if it is used for one month in an atmosphere of 40 ° C and 30% RH. [Comparative Example 5] <Preparation of polarizing plate> A PVA film having an average degree of polymerization of 1,700 was immersed in an aqueous solution containing 1.0 g/liter of iodine and 60 g/l of potassium iodide at 40 °C. It was immersed in an aqueous solution containing 40 g / liter of boric acid and 30 · 0 g / liter of potassium iodide for 90 seconds at 90 ° C for 10 seconds. Next, the film was introduced into a stretcher type stretching machine having the form shown in Fig. 3, and subjected to one stretching to 7. 〇 times, and then -78-1282013 was used to shrink the film to 5.3 times. Thereafter, it was dried at 60 ° C while maintaining the width fixed, and the film was taken out by a draw frame. The moisture content (volatile content) of the PVA film was 31% before the start of stretching, and was 1.5% after drying. The difference in transport rate between the right and left puller clips is less than 〇 5% 5% ' and the angle between the centerline of the introduced film and the centerline of the film fed to the subsequent step is 0°. Here, 丨LI-L2I is 0.7 meters, W is 0.7 meters, and satisfies the relationship of 丨Ll-L2 l=W. No wrinkles or deformation of the film were observed at the exit of the ram. Then, using a 3% PVA (PVA-117H manufactured by Kura) Co., Ltd. as an adhesive, the PVA film and the saponified Fuji Photo Film Co., Ltd. Fuji film (cellulose triacetate, hysteresis) · 3.0 nm) bonded and dried at 80 ° C to obtain a polarizing plate having an effective width of 65 mm. The absorption axis direction of the obtained polarizing plate is 45 ° with respect to the longitudinal direction, and the inclination angle with respect to the phase retardation axis of the Fuji film is also 45 °.

The polarizing plate has a transmittance of 43.3% at 5 50 nm and a polarization degree of 99.98%. The obtained polarizing plate was subjected to heat resistance, humidity resistance and heat resistance test, and as a result, the variation width of the transmittance of the veneer was 13.5%, and the variation width of the degree of polarization was 12.7%. When comparing Comparative Example 5, Example 13 and 15 5, it is apparent that after performing the heat resistance test and the humidity resistance and heat test, using PVA having a high degree of polarization or a metal salt, the transmittance and polarization can be reduced. The degree of change in width, but not -79-1282013 leads to discoloration or color dissociation. Further, from the comparison between Examples 1 and 3, it is apparent that the use of the metal salt of zinc after the heat resistance test and the humidity resistance and heat test can reduce the variation width of the transparency and the degree of polarization. Further, from the comparison between Examples 14 and 16, after performing the heat resistance test and the humidity resistance and heat test, it was found that by using a PVA having a high degree of polymerization and a combination of metal salts, transparency and polarization can be made. The width of the change is minimized. INDUSTRIAL APPLICABILITY The present invention can provide a polarizing plate having excellent dimensional stability, particularly ripening stability; a method for easily manufacturing a polarizing plate, which can improve the yield in the step of punching a polarizing plate, and has an excellent A low-level LCD display with a low number of stages. (5) Brief Description of Drawings: Fig. 1 is a schematic perspective view showing a polarizing plate of the present invention. Fig. 2 is a schematic plan view showing the polarizing plate of the present invention in a pressed state. Figure 3 is a schematic plan view showing one embodiment of a method of obliquely stretching a polymer film of the present invention. Figure 4 is a schematic plan view showing another embodiment of the method of obliquely stretching a polymer film of the present invention. Figure 5 is a schematic plan view showing still another embodiment of the method of obliquely stretching a polymer film of the present invention. Figure 6 is a schematic plan view showing still another embodiment of the method of obliquely stretching a polymer film of the present invention. Figure 7 is a schematic plan view of an embodiment of the method of presenting an obliquely stretched polymer film of the present invention. Figure 8 is a schematic plan view showing still another embodiment of the method of obliquely stretching a polymer film of the present invention. Fig. 9 is a schematic plan view showing an embodiment of a layer structure of a liquid crystal display. Fig. 10 is a view showing the relationship between the stretching axis of the protective film and the stretching axis of the polarizing film in the embodiment.

Fig. 1 is a schematic plan view showing a conventional polarizing plate in a stamped state. Figure 12 shows a schematic view of the air blowing device. Fig. 13 is a schematic view showing the embossing device. Figure 14 shows a schematic view of the doctor apparatus. The reference numbers in the figure are as follows:

(i): direction in which the film is introduced (ii): direction in which the film is transported to the subsequent step (a): film introduction step (b): film stretching step (c): step A in conveying the stretched film to the subsequent step 1 : the position at which the supporting device engages the film, and the position at which the film is initially stretched (substantial support starting point: right side) β 1 : position at which the supporting device engages the film (left side) C 1 : position of the initial stretched film (essential Support starting point: left side): position of the release film and terminal reference position of the stretched film (substantial support release point: left side)

Ay : Terminal reference position of the stretched film (substantial support release point: right) • 81 - 1282013 IL 1 -L2 I : Path difference between the left and right film support devices W: The substantial width of the film at the end of the stretching step Θ : angle between the stretching direction of the film and the direction of travel 1 1 : center line of the film on the introduction side 1 2 : center line of the film fed to the subsequent step 1 3 : track of the film supporting device (left) 1 4 : film Trajectory of the support device (right)

1 5 : film on the lead-in side 16 : film fed to the subsequent step 1 7 , 1 7 ' : the left side and the right side of the starting support (engagement) film 18, 18': the left side of the film is released from the support device and Right point 2 1 : Center line 22 of the film on the introduction side: Center line of the film sent to the subsequent step 2 3 : Track of the film supporting device (left) 24 : Track of the film supporting device (right)

25: film on the introduction side 2 6 : film 27, 27' which is sent to the subsequent step: the left and right points of the initial support (engagement) film 2 8 , 2 8 ' : the left and right points of the film are released from the support device 3 3, 4 3, 5 3, 6 3 : Trajectory of the film supporting device (left) 34, 44, 54, 64: Trajectory of the film supporting device (right) 3 5, 4 5, 5 5, 6 5 : introduction side Film 36, 46, 56, 66: film 70 sent to the subsequent step: protective film - 82 - 1282013 7 1 , 7 Γ : stretching axis of the protective film (phase retardation axis) 7 4 : adhesive layer 80: polarizing film 8 1 : Stretching axis of polarizing film (absorption axis) 7 2, 8 2 : Longitudinal 83 : Horizontal 9 0 : Polarizing plate 9 1 , 9 2 : Iodine-type polarizing plate 9 7 : Liquid crystal cell 9 8 : Backlight 1 0 1 : Air blowing device 1 1 1 : rolling device 1 2 1 : doctor device -83-

Claims (1)

1282013 ♦Year of the year (more) original ~-».......___ ·.·~★~.,,,~,---------------- ------------- ---------- .·· 9D 1 1 3 2 6 5 6 "Long polarizing film, polarizing plate, its preparation method and use it "Liquid crystal display" patent case (amended on March 6, 2006) Pickup, patent application scope 1. A polarizing plate comprising: a polarizing film; and a protective film attached to at least one surface of the polarizing film Wherein the angle formed between the stretching axis of the protective film and the stretching axis of the polarizing film is not less than 10 ° and less than 90 °; and (a) the polarizing film has neither parallel nor perpendicular to the longitudinal axis direction Absorption axis When the degree of polarization is calculated by the following formula (1), the polarizing plate has a transmittance of 40% or more in a board of 550 nm, and a degree of polarization of 95 in a nanometer of 500 nm. % or more; and (b) when the polarizing plate is placed in an atmosphere having a temperature of 60 ° and a humidity of 90% for 500 hours, the polarizing plate has: (b - 1 ) when compared with the starting enthalpy The change in transmittance at 550 nm is within ±10%; and (b - 2) When compared with the starting enthalpy, the variation of the polarization degree at 550 nm is within ±10%; Formula (1) P=[ (H0-H1 ) / (H0 + H1 ) ] 1/ 2 xl 00 where H0 is the transmittance (%) when the two polarizers are stacked to make the absorption axes coincide, and Η 1 is the transmittance of the absorption axis when the two polarizers are stacked (%) ). 2. The polarizing plate of claim 1 which is a roll-shaped elongated polarizing plate; wherein a protective film having a stretching axis parallel to the longitudinal axis is attached! 282〇l3 is attached At least one surface of the polarizing film of the stretching axis which is neither parallel nor perpendicular to the longitudinal axis direction. 3·~ a long polarizing film having: an absorption axis that is neither parallel nor perpendicular to the longitudinal axis; a polarization degree of 90% or more at 5 50 nm; a veneer at 550 nm The luminosity system is 3 5% or more; and when the angle is measured in the cross-sectional direction, the dispersion angle from the stretching axis to the longitudinal axis is within ±0.5 °. 4 · ~ long polarizing film, the system has: An absorption axis that is neither parallel nor perpendicular to the longitudinal axis; 90% or more of the polarization at 550 nm; 35% or more of the veneer transmission at 550 nm; The dispersion of the polarizing angle is within ±0.5%; and the dispersion of the transmittance of the veneer is within ±0.5%. 5 · a long polarizing film having: an absorption axis that is neither parallel nor perpendicular to the longitudinal axis; a polarization of 80% or more at 550 nm; at 550 nm The veneer transmittance is 35% or more; and the surface roughness: Ra is 10 μm or less. 6. The elongated polarizing film of claim 5, wherein the number of color sliding stripes is 4 or less per 1 m 2 . 7. The polarizing plate of claim 1 or 2, wherein the protective film is a light transmitting film, and the retardation 偏 of the polarizing plate at 6 3 2 . 8 nm is 10 nm or less. 8. A method of manufacturing a polarizing plate, comprising: attaching a stretched roll-shaped protective film to at least one surface of a polarizing film; wherein the polarizing film is manufactured by a method for stretching a polymer film And the method comprises: 1282013 supporting the two sides of the continuously fed polymer film with the supporting device; and stretching the film when the supporting device moves to the longitudinal axis direction of the film and applies tension to the film; Here, L 1 represents the trajectory between the support device from the substantial support starting point to the substantial support release point on one edge of the polymer film; L2 represents the support device from the substantial support starting point to the other in the polymer film The substantial support on the edge releases the trajectory between the points; and W represents the distance between the two substantially supported release points; L 1 , L2 and W satisfy the relationship represented by the following formula (2), and are left and right The difference in the conveying speed in the direction of the longitudinal axis between the film holding devices is less than 1%; and the method of manufacturing the polarizing plate according to the eighth aspect of the patent application, wherein polymer The film maintains the support characteristics of the polymer film while being stretched, and allows a ratio of volatile content of 5% or more to exist; and then reduces the ratio of the volatile content while the polymer film is shortened; The angle formed by the longitudinal axis direction and the absorption axis direction of the polarizing film is 2 0 ° to 70 °. 10. The method of manufacturing a polarizing plate according to claim 8, wherein the polymer film suitable for the polarizing film is a film mainly composed of polyvinyl alcohol. 1 1 The method of producing a polarizing plate according to claim 9, wherein the ratio of the volatile matter content is reduced while the polymer film is shortened, and the rate of reduction of the volatile content is 1%/min. The method of manufacturing a polarizing plate according to the first aspect of the invention, wherein the longitudinal axis direction and the absorption axis direction of the polarizing film form an angle of 40. To 50. . 1 3 - a polarizing plate 1282013 manufactured according to any one of claims 8 to 2, wherein the stretched polymer film for a polarizing plate is dried to shorten and reduce the volatile content thereof a ratio; after drying or during drying, a protective film is attached to at least one surface of the polymer film; and the laminate of the protective film and the polymer film is heat-treated. 1 4 . A method of manufacturing a polarizing plate, comprising: attaching a stretched roll-shaped protective film to at least one surface of the polarizing film; the polarizing film having: a polarizing system at 5 50 nm 80% or more; veneer transmittance at 550 nm is 35% or more; Surface roughness: Ra is 10 micrometers or less; wherein the polarizing film is produced by a method for stretching a polymer film, which comprises: supporting both sides of the continuously fed polymer film with a supporting device; And stretching the film when the support device moves to the longitudinal axis of the film and the tension is applied to the film; Here, L 1 represents the trajectory between the support device from the substantial support starting point to the substantial support release point on one edge of the polymer film; L2 represents the support device from the substantial support starting point to the other in the polymer film The edge on the edge substantially supports the trajectory between the release points; and W represents the distance between the two substantial support release points; LI, L2, and W systems satisfy the formula (2): | L2-L1 I > 〇. 4W relationship; The elastic modulus of the polymer film for the polarizing film is 0.1 to 500 MPa before stretching; and the polymer film can maintain the supporting property of the polymer film while being stretched. And at the same time allowing a proportion of volatile content of 5% or more to exist; and then reducing the proportion of the volatile content while the polymer film is shortened. 1282013 1 5 A method for producing a polarizing plate according to claim 14 wherein the polymer film for the polarizing film is a film of polyvinyl alcohol having an average degree of polymerization of 2,000 to 5,000. The method of producing a polarizing plate according to the fourth aspect of the invention, wherein the method for stretching the polymer film for the polarizing film comprises the step of adding a metal salt. i 7 • A method of producing a polarizing plate according to claim 6 of the patent application, wherein the step of adding a metal salt is a step of immersing the polymer film in an aqueous solution containing a metal salt. The method for producing a polarizing plate according to the seventh aspect of the invention, wherein the metal salt concentration in the solution containing the metal salt is from 〇 1 to 1 〇 . The method of producing a polarizing plate according to any one of claims 8 to 13, wherein the content of the volatile component in the film for the polarizing film is 5% or less before stretching. 20. The method of producing a polarizing plate according to claim 14, wherein the laminated film of the polarizing film and the protective film is attached after the stretched roll-shaped protective film is attached to at least one surface of the polarizing film. Post-heat treatment is performed. 21 . A liquid crystal display comprising a liquid crystal cell and a polarizing plate disposed on both sides of the liquid crystal cell; wherein at least one of the polarizing plates is stamped by at least one selected from the group consisting of the following groups; And the composition of the group is: a polarizing plate as described in claim 1 or 2; and at least one of the polarizing films described in claims 3, 4, 5 and 7 of the patent application. A polarizing plate; and a polarizing plate manufactured by the method as described in any one of claims 8 to 20.