TWI345083B - Polarizing film and liquid crystal display - Google Patents

Description

F1345083 IX. Description of the Invention: [Technical Field] The present invention relates to a polarizing plate and a liquid crystal display device using the same. [Prior Art] A liquid crystal display device is an image display device which is low in power consumption and requires a small space and is increasingly used. In the past, although the dependence of the viewing angle of the image is large, it is a major drawback of the liquid crystal display device. However, in recent years, the high viewing angle liquid crystal mode such as the VA (Vertical Alignment) mode 'iPS (in-plane switching) mode has been put into practical use. Therefore, in the market where high-vision field angles such as televisions are required, the demand for liquid crystal display devices is rapidly expanding. Therefore, the retardation film used in the liquid crystal display device and the polarizing plate using the same are also required to further improve the performance. In particular, the durability of improved temperature and humidity is a major technical problem of polarizing plates. The polarizing plate system generally adsorbs iodine to a hydrophilic polymer film such as a polyvinyl alcohol film or a partially formalized polyvinyl alcohol or an ethylene/vinyl acetate copolymer partial saponified film, and then extends the iodine. be made of. However, when the polarizer of the 0 is used for a long period of time, there is a problem that the transmittance of the entire screen under the black display rises and the frame-like light leaks. The reason for the increase in the transmittance and the frame-like light leakage is the relaxation of the extended hydrophilic polymer and the decomposition of iodine, and it is known that it is greatly affected by the amount of water permeation from the outside through the protective film. To. In this regard, a method of manufacturing a polarizing plate by bonding a protective film having a low moisture permeability to a polarizing film has been disclosed in Patent Document 1 and Patent Document 2. However, according to these methods, although the 13405083 moisture from the outside after the polarizing plate is formed can be inhibited, in the polarizing plate manufacturing step, the moisture which is evaporated from the inside to the outside during drying is thus Obstruction, so that the moisture in the polarizing film is still retained at a high level, and the durability improvement effect is not sufficient. [Patent Document 1] Japanese Patent Laid-Open No. 2002-328223 [Invention Patent Document 2] Japan [Problem to be Solved] The object of the present invention is to provide a polarizing plate which has a small change in transmittance and a degree of polarization due to heat and humidity. Another object of the present invention is to provide a liquid crystal display device with a polarizing plate having different moisture permeability protective films disposed on both sides of the polarizing film for use in a liquid crystal display device to provide a liquid crystal display device which does not cause problems such as light leakage and the like. . [Technical method for solving the problem] The inventors of the present invention have focused on the result of the discussion. When the polarizing plate is bonded to the liquid crystal cell, the evaporation from the water in the polarizing film is mainly transmitted through the protection of the air interface side of the polarizing film. The film (hereinafter also referred to as "first protective film") was used to carry out the film, and it was found that the liquid crystal cell side protective film (hereinafter also referred to as "second protective film") was set to be sufficient for the polarizing film when manufacturing the polarizing plate. The high water permeability required for evaporation of the water, and the air interface side protective film are set so as not to cause the water from the outside to invade the low permeability of the bonded polarizing film, thereby solving the problem This technical problem. That is, the objective can be achieved by the following technical methods. (1) A polarizing plate is characterized in that a first protective film 'polarizing film and a second protective film -6-1345083 are laminated in this order, and the first protective film has a lower moisture permeability than the second protection. The moisture permeability of the membrane. (2) The polarizing plate of item (1), wherein the difference between the first protective film and the second protective film measured at 60 ° C and 95% RH is 200 to 2,000 g/m 2 · 24 Hr. (3) The polarizing plate of item (1) or (2), wherein the first and second protective film systems are polymer films mainly composed of the same polymer, and the first and second protective films The type and/or amount of additives contained are different. (4) The polarizing plate according to any one of (1) to (3), wherein the first and second protective films are deuterated cellulose films. C 5 ) The polarizing plate of item (1) or (2), wherein the first and second protective films are deuterated cellulose films, and the first and second protective films contain deuterated cellulose The types are different. (6) The polarizing plate according to any one of (1) to (5), wherein the first protective film has a moisture permeability of 250 〜1,0〇〇 measured at 60 ° C and 95% RH. g/m2· 24 hr. (7) The polarizing plate according to any one of (1) to (6), wherein the second protective film has a moisture permeability of 500 to 5 as measured under conditions of 6 ° C and 95% rh. 〇g/m2 · 24 hr. (0) The polarizing plate of any one of (1) to (9), wherein the first and second protective films have a thickness of 40 μm or more and 12 μm or less and the first protective film and the second protective layer The thickness ratio of the film is 0·5 or more and 2 or less. 1345083 (11) The polarizing plate of any one of (1) to (10) is provided with an adhesive layer. (12) The polarizing plate of any one of (1) to (11), wherein an anti-glare layer is provided on a surface opposite to a surface of the polarizing film with respect to the first protective film. (13) The polarizing plate of any one of (1) to (12), wherein a reflective layer or a semi-transmissive reflective layer is provided. (14) A polarizing plate according to any one of (1) to (13), wherein a retardation layer or a λ/4 layer is provided. (15) The polarizing plate of any one of (1) to (14), wherein a viewing angle compensation layer (16) is provided, wherein the polarizing plate of any one of (1) to (I5) is set Brightness enhancement layer. (17) A liquid crystal display device characterized by having a liquid crystal cell and two polarizing plates disposed on both sides thereof, and at least one of the polarizing plates is polarized light according to any one of items (1) to (16) The second protective film of the polarizing plate is located on the liquid crystal cell side. (18) The liquid crystal display device of (17), wherein the liquid crystal cell system is in a mode. (19) The liquid crystal display device of (17), wherein the liquid crystal cell is in an OCB mode. (2) The liquid crystal display device of (17), wherein the liquid crystal cell is in an IPS mode. (twenty one )

A liquid crystal display device according to (17), wherein the liquid crystal cell system V A 1345083 mode. [Effect of the Invention] The inventors succeeded in producing a polarizing plate having excellent durability against heat and humidity. The above polarizing plate is suitable for use in TN (Twisted Nematic) type, OCB (Optically Compensated Bend) type, ECB (Electrically Controlled Birefringence) type, VA (Vertical Alignment; Vertically Aligned) ), IPS (In-Plane Switching) type liquid crystal display device. [Best Mode for Carrying Out the Invention] 1. Configuration of Polarizing Plate First, a polarizing film and a protective film for constituting the polarizing plate of the present invention will be described below. (1) Polarizing film The polarizing film of the present invention is preferably composed of polyvinyl alcohol (PVA) and a dichroic molecule, but it can also be used as described in Japanese Patent Laid-Open No. Hei No. 1 _ 248 937. A polyethylene-based polarizing film which dehydrates and dechlorinates PVA or polyvinyl chloride to form a polyene structure and aligns it.

PVA is a polymer material obtained by alkalizing polyvinyl acetate, but may contain, for example, a component in which an unsaturated carboxylic acid 'unsaturated sulfonic acid, an olefin, or an ethylene ether can be copolymerized with vinyl acetate. Further, although the degree of saponification of the modified pVA 1345083 PVA containing an acetamidine group, an acid extension group, a carboxyl group alkylene oxide or the like may be used, it is preferably not particularly limited, but it is preferably from the viewpoint of solubility and the like. It is 80% to 100% by mole, and the best is 90% to 00%. Further, although the degree of polymerization of the PVA is not particularly limited, it is preferably from 1,000 to 10,000, particularly preferably from 1,500 to 5,000. The alignment of the PVA (stereo) is as described in the invention patent No. 2,978,919, and is preferably 55% or more for improving the durability, but is described in the invention patent No. 3, 3, 494. 45 ~ 52.5 % can also be used. After the PVA is thinned, it is preferred to introduce a dichroic molecule to form a polarizing film. The method for producing a PVA film is generally a method in which a PVA-based resin is dissolved in a water or an organic solvent to cast a film to form a film. The concentration of the polyvinyl alcohol-based resin in the stock solution is usually 5 to 20% by mass, and the raw material is formed into a film by a casting method to obtain a PVA film having a film thickness of 10 to 200 μm. For the production of the PVA film, the method described in the invention patents Nos. 3,342, 516, and JP-A-09-328593, JP-A-2001-302817, and JP-A-2002-144401 can be referred to. The degree of crystallization of the PVA film is not particularly limited, but the average degree of crystallinity (Xc) described in Patent No. 3,251,073 can be 50 to 75 mass%, or the variability of the in-plane hue can be reduced. A PVA film having a crystallinity of 38% or less is described in JP-A No. 2,002-23,621. The birefringence (?n) of the PVA film is preferably small, and the PVA film having a birefringence of 1.00 or less as described in Japanese Patent No. 3,342,516 is suitable for use. However, as described in Japanese Laid-Open Patent Publication No. 14-22-8835, in order to avoid the high degree of polarization when the PVA film is cut during stretching, the birefringence of the PVA film can be set to 〇·〇〇2. In the case of 0.01 or less, the value of {(nx + ny) /2 - nz } as described in JP-A-2002-060505 may be set to 0.0003 or more and 0.01 or less. The retardation 値 (in-plane) of the PVA film is preferably 〇N or more and 100 nm or less, and more preferably 0 nm or more and 50 nm or less. Further, the Rth (film thickness direction) of the 'PVA. film is preferably 〇N or more and 5 Å or less, more preferably 〇N or more and 300 nm or less. In addition, the polarizing plate of the present invention is also suitable for use in a PVA film having a 1,2-ethyl alcohol-bonding amount of 1.5 mol% or less as described in Japanese Patent No. 3,021,494. The optical foreign matter of 5 μm or more per 100 cm 2 described in No. 1-316492 is a PVA film of 500 or less, and the hot water in the TD direction of the film described in JP-A No. 2〇〇2-3〇163 A PVA film having a temperature change of 1.5 ° C or less is cut off, and a polyol of 3 to 6 yuan by mixing 1 to 1 part by mass of glycerin or the like, or a mixture of 15% by mass or more of No. 06-289225 A PVA film formed by the solution of the plasticizer described. The film thickness of the PVA film before stretching is not particularly limited, but it is preferably from 1 micrometer to 1 millimeter, particularly preferably from 20 to 200, from the viewpoint of maintaining the stability of the film and the homogeneity of the elongation. Micron. It is also possible to use a thin PVA film having a stress of 10 N or less when a 4 to 6 times extension is applied to water as described in Japanese Patent Laid-Open Publication No. 2002-236212. High-grade iodide or dichroic dyes such as ruthenium or osmium. In the present invention, the use of higher-order iodide ions is particularly suitable for the use of 1,345,083 ^ high-order iodide ions can be as described in "Application of Polarizing Plates", Yong Tianliang, CMC Publishing, or Industrial Materials, Volume 28, No. 7 As described in the pages 39 to 45, the PVA is immersed in a solution in which iodine is dissolved in a potassium iodide aqueous solution and/or a boric acid aqueous solution, and is adsorbed and aligned to PVA. When a dichroic dye is used as the dichroic dye, it is preferably an azo dye. In particular, a disazo type and a azo dye are preferable. The dichroic dye is preferably a water-soluble one. Therefore, a hydrophilic substituent such as a sulfonic acid group, an amine group or a hydroxyl group is introduced into the dichroic molecule to be used as a free acid or an alkali metal salt, an ammonium salt or an amine. salt. Specific examples of the dichroic dye as described above include: CI Direct Red 3 7 , Congo Red (C. I · Direct Red 2 8 ), C · I. Direct Violet 12, C. I· Direct Blue 90 , CI Direct Blue 22, CI Direct Blue 1, CI Direct Blue 151, C. I. Direct Green 1 and other benzidines; C. l Direct Yellow 44, CI Direct Red 23, C·I. Direct Red 79, etc. Diphenylurea; CI direct yellow 12 and other distyrene; CI direct red 31 and other dinaphthylamine; CI direct red 81, CI direct violet 9, CI direct blue 78 and other J acid system. In addition, it can also be used: CI Direct Yellow 8' CI Direct Yellow 28, CI Direct Yellow 86, CI Direct Yellow 87, CI Direct Yellow 142, C. I. Direct Orange 26, CI Direct Orange 39, CI Direct Orange 72, CI direct orange l〇6'CI direct orange 107, C_I. direct red 2, (: _1. direct red 39, (:.1. direct red 83, (:.1. direct red 89, (: · I. direct Red 240, CI Direct Red 242, CI Direct Red 247, C·I· Direct Violet 48, CI Direct Violet 51, CI Direct Violet 98'CI 1345083 Direct Blue 15, C_I. Direct Blue 67' CI Direct Blue 71, CI Direct Blue 98, CI Direct Blue 168, CI Direct Blue 202, CI Direct Blue 23 6, CI Direct Blue 249, C. I_ Direct Blue 270 'CI Direct Green 59, C. I· Direct Green 85, CI Direct Brown 44, CI Direct Brown 106, CI Direct Brown 195, CI Direct Brown 210, CI Direct Brown 223, C_I. Direct Brown 224, C_I_ Direct Black l'c· I. Direct Black 17 'σι. Direct Black 19, c. I. Direct black 54; etc.; and Japanese Patent Laid-Open No. 62-70802, Special Kaiping No. 1-161202, Special Kaiping No. 1-1 72906, Special Kaiping No. 1-172907, Special Kaiping A dichroic dye described in each of the publications of Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The dichroic dye may be used in combination of two or more kinds. The dichroic dye may have a sorption thickness of 4 μm or more as described in JP-A-2002-082222. When the content of the coloring molecule is too small, the degree of polarization becomes low. If the content of the coloring element is too small, the transmittance of the veneer is lowered. Therefore, the polyvinyl alcohol polymer is usually adjusted to 0.01 mass with respect to the matrix of the film. The range of % to 5% by mass. The preferred film thickness of the polarizing film is from 5 μm to 40 μm, more preferably from 10 μm to 30 μm. The ratio of the thickness of the polarizing film to the thickness of the protective film described later can also be set to Japan. Patent Document No. 2002-1 74727 discloses a range of $1$ person (polarized film thickness) /: 8 (protective film thickness) $〇.16. (2) Protective film The protective film of the present invention Preferably, by reducing a terpene resin, polyethylene terephthalate 1345083 acid ethylene glycol (PET), polynaphthalene A polymer film made of ethylene glycol diester, polycarbonate, polystyrene, polyaryl vinegar, polythene cellulose, etc. Further, the protective film of the present invention is preferably the first and second Both sides of the protective film are substantially the same resin. The term "substantially identical" means that the main component is the same resin, and the additives other than the main component may be the same or different. Among them, a cellulose acetate film is preferably used, and it is preferred to use deuterated cellulose on both sides. The cellulose film to be used in the present invention is explained below. [Production of Deuterated Cellulose and Deuterated Cellulose Film] Although the mercapto group of the deuterated cellulose film is not particularly limited, it is preferably an ethylene group, a propenyl group or a butyl group, and particularly preferably a醯基. The degree of substitution of the total thiol group is preferably from 2.7 to 3.0, more preferably from 2.8 to 2.95. When a cellulose acetate having a fluorenyl group is used, the degree of substitution of the ethane group is preferably from 2.7 to 2.95, more preferably from 2.8 to 2.95, and most preferably from 2.84 to 2.89. In addition, it is described in the above-mentioned Japanese Patent Laid-Open No. 13-356214, which is 2.5 〇 or more and 2. S6 or less, or the acetonitrile substitution degree of 2.75 or more and 2.86 or less which is described in the above-mentioned Japanese Patent Laid-Open No. 1 3-226495. Also suitable for use. If it is too low, Re is likely to be larger than what is desired due to the tension in the flow delay, and there is also a problem that surface unevenness is likely to occur. Further, the degree of substitution of the thiol group of 6 is suitably 0.9 or more. When the degree of substitution is 0.9 or less, the unevenness of Re and Rth is likely to occur. Further, the degree of substitution in the sulfhydryl group of the present invention is 値 from -14 to 1345083 calculated in accordance with ASTM D817. In the present invention, cellulose acetate having a degree of acetylation of from 59.0 to 61.5% is preferably used. "Ethylation degree" means the amount of combined acetic acid per unit mass of cellulose. The degree of acetylation is determined according to ASTM: D-817-91 (test method for cellulose acetate, etc.) And the cellulose acetate of the present invention is measured by the calculation method, and the synthesis example 1 and the paragraph number 0048 to 0049 described in Paragraph No. 0043 to 0044 of Japanese Patent Laid-Open Publication No. Hei No. Hei. The cellulose acetate obtained by the synthesis method of Synthesis Example 3 described in the synthesis example 2 and the paragraph number 0 0 5 1 - 0 0 5 2 described above. Further, in the present invention, it is also suitable to use a celluloseized cellulose having two or more sulfhydryl groups as described in JP-A-H08-231761 and JP-A-2003-170492. The viscosity average polymerization degree (DP) of the deuterated cellulose is preferably 250 or more, and more preferably 290 or more. Further, in the cellulose deuterated film used in the present invention, the molecular weight distribution of Mw/Mn (Mw is a mass average molecular weight, Μη is a number average molecular weight) according to gel permeation chromatography is preferably narrow. The specific Mw/Mn ratio is preferably in the range of 1.0 to 1.7, more preferably in the range of 1.3 to 1.65, and most preferably in the range of 1.4 to 1.6. Cellulose acetate prepared by a synthetic method can be used. [Production of Deuterated Cellulose Film] The deuterated cellulose film of the present invention is preferably produced by a solvent casting method. 1345083 In the solvent casting method, a film is produced by using a solution (coating liquid: dope) in which deuterated cellulose is dissolved in an organic solvent. The organic solvent preferably contains an ether selected from the group consisting of 3 to 12 carbon atoms, a ketone having 3 to 12 carbon atoms, an ester having 3 to 12 carbon atoms, and a halogenated carbon having 1 to 6 carbon atoms. A solvent in a group of hydrogen compound solvents. The ether, ketone and ester systems may also have a cyclic structure. Any of two or more of the functional groups of the ether, ketone and ester (i.e., -0-'-CO- and -C00-) can also be used as the organic solvent. The organic solvent may also have other functional groups like an alcoholic hydroxyl group. In the case of an organic solvent having two or more functional groups, it is preferred that the number of carbon atoms is a solvent having any of the above-mentioned preferred carbon atom numbers. Examples of the ether having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, and 1,3-pentanepentane. , tetrahydrofuran, methoxybenzene, and phenylethyl ether. Examples of the ketone having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclohexyl-1, and methylcyclohexanone. Examples of the ester having 3 to 12 carbon atoms include ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate, and amyl acetate. Examples of the organic solvent having two or more functional groups include 2-ethoxyethyl acetate '2-methoxyethanol, and 2-butoxyethanol. Halogenated hydrocarbons preferably have a carbon number It is 1 or 2, and the best is 1. The halogen of the halogenated hydrocarbon is preferably chlorine. The ratio of the hydrogen atom of the halogenated hydrocarbon to halogen is preferably from 25 to 75 mol%, more preferably from 16 to 1345083, more preferably from 30 to 70 mol%, still more preferably from 35 to 65 mol%, and further preferably The best is 4〇 to 60mol%. Dichloromethane is a representative halogenated hydrocarbon. It is also possible to mix two or more organic solvents. The deuterated cellulose solution can be prepared by a general method comprising treatment at a temperature above 〇 °C (normal temperature or high temperature). The preparation of the solution can be carried out by a method and apparatus for preparing a coating liquid by a usual solvent casting method. Further, when a general method is used, it is preferred to use a halogenated hydrocarbon (particularly dichloromethane) for the organic solvent. The amount of deuterated cellulose should be adjusted to be 10 to 40% by mass in the resulting solution. The amount of deuterated cellulose is preferably from 1 to 30% by mass. Any additives described later may also be added to the organic solvent (main solvent). The solution can be prepared by stirring the deuterated cellulose with an organic solvent at a normal temperature (〇 to 40 ° C). The high concentration solution can be stirred under pressure and heating. Specifically, the deuterated cellulose and the organic solvent are placed in a pressurized container and sealed, and then heated under pressure to a temperature above the boiling point of the solvent at a normal temperature, and the solvent is not boiled while stirring. . The heating temperature is usually 40 ° C or higher, preferably 60 to 200 ° C, more preferably 80 to 110 ° C. The components may also be coarsely mixed beforehand and then placed in a container. Moreover, it can be loaded gradually. The container must have a structure that can be agitated. An inert gas such as nitrogen may be injected to pressurize the container. In addition, the increase in solvent vapor pressure caused by heating -17-1345083 can also be utilized. Or after sealing the container, add the ingredients under pressure. When heating, it should be heated from the outside of the container. For example, a jacket type heating device can be used. Further, it is also possible to adopt a method in which a plate heater is provided outside the container and piping is provided to circulate the liquid to heat the entire container. It is preferred to provide a stirring wing inside the container and use it for agitation. The agitating wings preferably have a length that is accessible to the vicinity of the wall of the container. Preferably, a scraper wing is provided at the end of the agitating wing to renew the liquid film of the container wall. A gauge such as a pressure gauge or a thermometer can be provided in the container. Dissolve the ingredients in a solvent in the container ® . The coating liquid prepared by the preparation is cooled and taken out from the container, or taken out, and then cooled by using a heat exchanger or the like. The solution can also be prepared by a cooling dissolution method. The cooling dissolution method allows the deuterated cellulose to be dissolved in an organic solvent which is not easily dissolved according to a usual dissolution method. Further, even if it is a solvent capable of dissolving deuterated cellulose according to a usual dissolution method, when a cooling dissolution method is employed, it has an effect of rapidly obtaining a uniform solution. The cooling dissolution method was initially carried out by slowly adding deuterated cellulose at room temperature in an organic solvent while stirring. The amount of deuterated cellulose is preferably adjusted to be 10 to 40% by mass in the mixture. The amount of deuterated cellulose is more preferably 3% by mass. Further, any of the additives described later may be added in advance to the mixture. Next, 'cool the mixture to -100 to -10 ° C (preferably -80 to -10 ° C, more preferably -50 to -2 ° C, and most preferably -5 to - 18 - 1345083) 3 0 ° C). The cooling system can be carried out, for example, in a dry ice methanol bath (-75 ° C) or a cooled diethylene glycol solution (-30 to -20 t). The mixture of cooled deuterated cellulose and an organic solvent will harden. The cooling rate is preferably 4 t/min or more, more preferably 8 ° C/min or more, and most preferably 12 ° C / min or more. The faster the cooling rate, the better, but 10,000 ° C / sec is the theoretical upper limit, 1,000 ° C / sec is the technical upper limit, and l 〇〇 ° C / sec is the practical upper limit. Further, the cooling rate is obtained by dividing the difference between the temperature at which cooling starts and the last cooling temperature by the time required from the start of cooling to the time of reaching the final cooling temperature. Then, when it is heated to 200 ° C (preferably 0 to 150 ° C, more preferably 〇 to 120 ° C, and most preferably 0 to 5 ° ° C), the cellulose is about to dissolve. In organic solvents. The temperature rise can be placed only at room temperature or in a warm bath. The heating rate is preferably 4 ° C / min or more, more preferably 8 t / min or more, and most preferably 12 ° C / min or more. Although the heating speed is as fast as possible, 10,000 ° C / sec is the theoretical upper limit, 1,000 ° C / sec is the technical upper limit, and l 〇〇 ° C / sec is practical. The upper limit "heating rate" is the difference between the temperature at which the heating starts and the final heating temperature are divided by the time required from the start of heating to the time of reaching the final heating temperature. A homogeneous solution can be obtained in the manner described above. If the dissolution is not sufficient, the cooling and heating operations may be repeated. Whether the dissolution is sufficient or not can be judged only by visually observing the appearance of the solution. In the cooling dissolution method, in order to avoid condensation due to condensation (condensation) upon cooling, it is preferred to use a closed container. In addition, in the operation of cooling and heating -19 - 1345083, it is pressurized when cooling is performed, and when it is decompressed when heating is performed, the dissolution time can be shortened. When pressure and pressure are reduced, it is preferred to use a pressure resistant container. In addition, cellulose acetate (degree of acetylation: 60.9 %, viscosity average degree of polymerization: 2 99) was dissolved in a solution of 20% by mass in methyl acetate by a cooling dissolution method, and was determined according to differential scanning heat. In the measurement of the method (DSC), there is a pseudo phase transition point in the sol state and the gel state in the vicinity of 3 3 t, and a uniform gel state is below this temperature. Therefore, the solution must be stored at a temperature above the pseudo phase transition temperature, preferably at a gel phase transfer temperature plus about 1 〇 ° C. However, the pseudo phase transfer temperature differs depending on the degree of acetylation of cellulose acetate, the average degree of polymerization of the viscosity, the concentration of the solution, or the organic solvent used. A deuterated cellulose film was produced by a solvent casting method from a prepared deuterated cellulose solution (coating liquid). It is preferred to add the above-mentioned retardation agent and retardation reducing agent to the coating liquid. The coating liquid is cast on a drum or belt, and the solvent is evaporated to form a film. The coating liquid before casting is preferably adjusted to have a solid content of 18 to 35 % by weight. The surface of the drum or belt is preferably pre-finished into a mirrored state. The coating liquid is preferably cast on a drum or belt having a surface temperature of 1 〇 ° C or less. The method of drying in the solvent casting method is disclosed in U.S. Patent Nos. 2, 3, 36, 301, 2, 367, 603, 2, 492, 078, 2, 492, 977, 2, 492, 978, and 2, 607, 704. , with the 2nd, 739, 〇69, the same as the 2nd, 739, 〇7〇, the British invention patent -20- 1345083 64〇, 731, the same as the 736, 892 manual, Japanese Patent Special Public Show No. 45-4554 It is described in the bulletins No. 49-5614, Special Open No. 60-176834, the same as No. 60'2〇3430, and the same as No. 62-115〇35. The drying on the belt or the drum can be carried out by blowing an inert gas such as nitrogen gas. The obtained film may also be stripped from a drum or a belt and dried by a hot air which gradually changes temperature from 100 to 160 ° C to evaporate the residual solvent. The above method is described in Japanese Patent Laid-Open Publication No. Hei 5-7-1844. According to this method, the time required from the self-flow to the stripping can be shortened. To carry out the process, the coating liquid must be gelled at the surface temperature of the rotating drum or belt. It is also possible to carry out casting of two or more layers to form a film by using the prepared deuterated cellulose solution (coating liquid). In this case, it is preferred to produce a deuterated cellulose film by a solvent casting method. The coating liquid is cast on a drum or belt, and then the solvent is evaporated to form a film. The coating liquid before casting is preferably adjusted to have a solid content of from 10 to 4% by weight. The surface of the drum or belt is preferably pre-finished into a mirrored state. When casting a plurality of layers of deuterated cellulose liquid, it is also possible to cast several kinds of deuterated cellulose solutions, or to take several casting openings which are arranged at intervals from the direction of the support body. A method of casting a solution containing deuterated cellulose to form a film on one surface layer. For example, the method described in each of the publications of Japanese Laid-Open Patent Publication No. 61-158414, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei. Further, the deuterated cellulose solution can be thinned by casting the two casting openings. For example, -21 - 1345083, can be used in Japanese Patent Special Publication No. 60-27562, Tongtekai Show No. 6 1 -94724, Tongte Zhaozhao No. 6 1 -947245, and Tongkai Zhaoxian No. 61-1 048 The method described in each of the publications of the Japanese Unexamined-Japanese-Patent No. 6-1 3 493 3 In addition, in the state in which the fluid of the high-viscosity deuterated cellulose solution is coated with a low-viscosity deuterated cellulose solution as described in the Japanese Patent Publication No. 56-1 626 1 7 A casting method of a tantalum cellulose film extruded simultaneously with a high- and low-viscosity deuterated cellulose solution. In addition, it is also possible to use two casting openings, peeling off the film formed on the support by the first casting opening, and then applying a second casting on the side contacting one side of the supporting body to manufacture a film. . For example, the method described in Japanese Patent Publication No. 44-2 02 35 can be used. The same solution may be used for the cast deuterated cellulose solution, or a different deuterated cellulose solution may also be used. In order for the deuterated cellulose layer to have several functions, it is preferred to extrude the deuterated cellulose solution according to its function from each of the casting openings. Further, the deuterated cellulose solution of the present invention may be cast simultaneously with other functional layers (e.g., an adhesive layer, a dye layer, an antistatic agent, an anti-corona layer, an ultraviolet absorbing layer, a polarizing layer, etc.). In the previous single layer liquid, in order to obtain the desired film thickness, it is necessary to extrude a high viscosity deuterated cellulose solution at a high concentration. At this time, the stability of the deuterated cellulose solution is not good, and a solid matter is formed to constitute a defect of the unevenness, or the planarity is deteriorated, and most of them become a problem. To solve this problem, if several kinds of deuterated cellulose solution are delayed from the casting mouth, the high viscosity solution can be simultaneously extruded on the support, so that -22- 1345083 can not only make the plane The film is also obtained in a favorable and excellent surface, and the drying load can be reduced by using the concentrated deuterated cellulose solution, thereby achieving an increase in the production rate of the film. The following plasticizer can be used for the deuterated cellulose film to improve its mechanical properties. Examples of the "plasticizer" which can be used as a phosphate or a carboxylate "phosphate" include triphenyl phosphate (TPP) and tricresyl phosphate (TCP). The "carboxylic acid esters" are represented by phthalic acid esters and citrate esters. Examples of phthalates include: dimethyl phthalate (DMP) 'diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate Ester (DOP), diphenyl phthalate (DPP), and diethylhexyl phthalate (DEHP). Examples of citrates include: o-ethenyl triethyl citrate (〇ACTE), and o-ethinyl tributyl citrate (OACTB). Examples of other carboxylic acid esters include: butyl oleate, methyl decyl ricinolate, dibutyl sebacate, and various 1,2,4-benzenetricarboxylates. Phthalate plasticizers (DMP, DEP, DBP, DOP, DPP, DEHP) are suitable for use, among which DEP and DPP are particularly preferred. The amount of the plasticizer added is preferably from 0.1 to 25 mass%', more preferably from 1 to 20 mass%, and most preferably from 3 to 15 mass%, based on the amount of the deuterated cellulose. An anti-deterioration agent (for example, an antioxidant, a peroxide decomposing agent, a radical inhibitor, a metal inerting agent, an acid trapping agent, or an amine agent) may be added to the deuterated cellulose film. Regarding the anti-deterioration agent, Japanese Patent Laid-Open No. 3 - 1 9920 1 'same as No. 5-1 97073, No. 5-1 94789, No. 5-271471, and No. 6-1〇7854 In each of the publications, the amount of the anti-inferiority -23-1345083 agent is preferably 0.01 to 1% by mass, and more preferably 〇.〇1 to the target solution (coating solution) to be prepared. 〇·2% by mass. When the amount added is less than 0.01% by mass, the effect of the deterioration preventing agent is hardly observed. If the amount added is more than 1% by mass, there is a possibility that the deterioration of the surface of the film by the deterioration preventing agent occurs. Examples of particularly desirable anti-deterioration agents are butylated hydroxytoluene (BHT) and tritylamine (TBA). The steps from the self-flow to the post-drying may be carried out under an air atmosphere or under an inert gas atmosphere such as nitrogen. The coiler which can be used in the manufacture of the cellulose-deposited film of the present invention can also be used by a general user, that is, a constant tension method, a constant torque method, a cone torque method, and an internal stress constant. The method of volume control such as the program tension control method is used for winding. [Surface Treatment of Deuterated Cellulose Film] The deuterated cellulose film is preferably subjected to surface treatment. The specific method can be treated by corona discharge treatment, glow discharge treatment, flame treatment, acid treatment, inspection treatment, or ultraviolet irradiation treatment. Further, a base coat layer may be provided as described in Japanese Laid-Open Patent Publication No. Hei 7-333433. From the viewpoint of maintaining the planarity of the film, at the time of the treatment, the temperature of the bismuth cellulose film is set to be lower than T g (glass transition temperature), and specifically, it is preferably set at 15 〇. Below C. When it is used as a transparent protective film for a polarizing plate, it is considered to be subjected to acid treatment or alkali burying from the viewpoint of adhesion to a polarizing film, that is, it is particularly preferable to carry out saponification treatment on deuterated cellulose. The surface energy is preferably 55 mN/m or more or more preferably mN/m or more and -24 to 1345083 7 5 mN /m or less. The basic alkalization treatment is taken as an example, and the details are as follows. The alkaline alkalization treatment of the deuterated cellulose film is preferably carried out by immersing the surface of the film in an alkali solution, neutralizing it with an acidic solution, then washing with water and drying it. The alkaline solution includes a potassium hydroxide solution and a sodium hydroxide solution, and the equivalent concentration of the hydroxide ions is preferably in the range of 0.1 to 3.0 N, and more preferably in the range of 0.5 to 2.0 N. The temperature of the alkaline solution is preferably in the range of room temperature to 9 (rc, more preferably in the range of 40 to 70 ° C. φ The surface energy of the solid is such as "basis and application of wetting" (Realize, 1 98) It can be obtained by contact angle method, wet heat method, and adsorption method as described in the first book on December 10, 1999. In the case of the cellulose-deposited film of the present invention, it is preferred to use the contact angle method. Specifically, the surface energy is a known solution of two kinds of drops on the deuterated cellulose film, at the intersection of the surface of the droplet and the surface of the film, to draw at the corner formed by the wiring of the droplet and the surface of the film, and includes The angle of the dropper is defined as the contact angle, and the surface energy of the film can be calculated by calculation. ® [Transistence Humidity] For the protective film used in the polarizing plate of the present invention, it is also possible to use any resin as long as the moisture permeability is different. Preferably, however, the first and second protective films are the same type of polymer substrate film, and more preferably, the difference in moisture permeability between the first and second protective films is caused by the type and/or amount of the additive. Permeability is based on JIS According to the method described in Z0208, the moisture permeability of each sample is measured from -2545345, and the amount of water (g) evaporated per 24 m area in 24 hours is calculated. The moisture permeability of the protective film can be adjusted by various methods. The addition of a hydrophobic compound to the deuterated cellulose film reduces the water absorption of the deuterated cellulose film, thereby reducing the moisture permeability. In this case, it is particularly preferable to use a low compatibility with the deuterated cellulose. An additive having a small plasticizing effect. A compound represented by the following general formulae (I) to (III) is particularly suitable for use. Next, the compound represented by the general formula (I) used in the present invention is explained in detail. As follows: General formula (I) [Chemical 1]

In the above formula (I), 'R21, R22 and R23 are preferably each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group). , butyl, pentyl, isopentyl); particularly preferably at least one of R21, R22 and R23 is an alkyl group having 1 to 3 carbon atoms (for example: methyl, ethyl, propyl, isopropyl) The base 〇X21 is preferably selected from the group consisting of: a single bond, a 0-, a CO-, a stretching base (preferably a carbon number of 1 to 6, more preferably 1 to 3, for example: a a base of "extended ethyl, propyl", 1345083 or an aryl group (preferably having a carbon number of 6 to 24, more preferably 6 to 12). For example, stretching phenyl, stretching phenyl, stretching A divalent linking group formed by one or more groups of the naphthyl group; particularly preferably a divalent linking group formed of one or more selected from the group consisting of: an anthracene, an alkylene group or an extended aryl group. Y21 is a hydrogen atom or an alkyl group (preferably, the number of carbon atoms is from 2 to 25, more preferably from 2 to 20), for example, ethyl, isopropyl, tert-butyl, hexyl, 2-ethyl Hexyl, tertiary-octyl, dodecyl, cyclohexyl, dicyclohexyl, adamantyl), aryl (preferably having a carbon number of 6 to 24, more preferably 6 to 18). For example, benzene a base of 'biphenyl, terphenyl, naphthyl) or aralkyl (preferably having a carbon number of 7 to 30, more preferably 7 to 20), for example, a benzyl group or a cresol group. 'Tris-butylphenyl, diphenylmethyl, triphenylmethyl): particularly preferably an alkyl group, an aryl group or an aralkyl group. The combination of _X21-Y21' preferably has a total carbon number of from 0 to 40, more preferably from 1 to 3, and particularly preferably from 1 to 25. Preferred examples of the compounds represented by the above formula (I) are shown below, but the invention is not limited to the specific examples. -27- 1345083

28- 1345083

Next, the compound represented by the formula (II) will be specifically described below. -29- 1345083 Formula (π )

S—N—

II o In the above formula (II), R1 represents an alkyl group or an aryl group, and R2 and R3 each independently represent a hydrogen atom, an alkyl group, or an aryl group. Further, it is particularly preferable that the total number of carbon atoms of Ri, R2 and R3 is 1 〇 or more. The substituent is preferably a fluorine (the atomic group, the aryl group, the oxy group, the acid group, and the amine group: particularly preferably an alkyl group, an aryl group, an alkoxy group, a sulfonic acid group, and a sulfonamide). Further, the 'hospital base system may be straight chain, branched, or ring-shaped, and the number of carbon atoms is preferably from 1 to 25', more preferably from 6 to 25, and particularly preferably from 6 to 20 (for example, methyl group). ,ethyl 'propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, tertiary-pentyl, hexyl, cyclohexyl, heptyl, octyl, bicyclooctyl Base, fluorenyl, adamantyl, fluorenyl, tert-octyl, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen , a 19-based 'diindenyl group. The aryl group is preferably a carbon number of 6 to 30, particularly preferably 6 to 24 (for example, phenyl, biphenyl 'biphenyl, naphthyl, hydrazine Naphthyl, triphenylphenyl). Preferred examples of the compound represented by the formula (II) are as follows, but the present invention is not limited to the specific examples. -30- 1345083 [Chemical 5]

1345083

A- 3 Ο Next, the compound represented by the formula (III) used in the present invention will be described in detail as follows: -32-1345083 Formula (III) [Chem. 7]

In the above formula (III), X2 represents B, C - R (R represents a hydrogen atom or a substituent), N'P or P = OdR11, ^12,! ^13'!^4' R15 ' R21, R22, R23, R24, R25, R31, R32, R33, R34 and R35 each independently represent a hydrogen atom or a substituent. X represents B, c-R (R represents a hydrogen atom or a substituent.), N, P, P = 0; X is preferably B, C_R (R is preferably: aryl, substituted φ or not Substituted amine, alkoxy, aryloxy, decyl, alkoxycarbonyl, aryloxycarbonyl, decyloxy, decylamino, alkoxycarbonylamino, aryloxycarbonyl, sulfonylamino , a thiol group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a carboxyl group; more preferably an aryl 'alkoxy group, an aryloxy group, a hydroxyl group or a halogen atom; further preferably It is an alkoxy group, a hydroxyl group, particularly preferably a hydroxyl group.), Ν, Ρ = 0; further preferably C-R, N; and particularly preferably C-R. R12, R13, R14, r15, R21, R22, R23, R24, R25, -33-1345083 R31, R32, R33, R34 and R35 represent a hydrogen atom or a substituent, and the substituent T can be applied to the substituent. R", R12' R]3' R14' R15' Rn, R22, R23, r24, r25, r31, r32, r33, r34 and R35 are preferably: alkyl, alkenyl, alkynyl, aryl, substituted Or unsubstituted amino, alkoxy ' aryloxy 'fluorenyl 'alkoxycarbonyl, aryloxycarbonyl, decyloxy, decylamino 'alkoxycarbonylamino, aryloxycarbonyl, sulfonate Amidino, amine sulfonyl, amine methyl sulfonyl, alkylthio, arylthio, sulfonyl, sulfinyl, ureido 'phosphonium amide, hydroxyl, thiol' halogen atom (eg fluorine Atom, chlorine, bromine, iodine), cyano, sulfonate, carboxyl, nitro, isophthalic acid, sub-acid, hydrazino 'imine, heterocyclic (preferably, the number of carbon atoms is from 1 to 30, more preferably from 1 to 12, and the hetero atom includes, for example, a nitrogen atom, an oxygen atom, a sulfur atom, and specifically includes, for example, an imidazolyl group, a pyridyl group, a quinoline. a base, a furyl group, a piperidinyl group, a benzoxazolyl group, an N-morpholino group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazole group, etc., a decyl group; more preferably an alkyl group or an aryl group Substituted or The substituted amino group, an alkoxy group, an aryloxy group; further more preferably an alkyl group, an aryl group, an alkoxy group. These substituents may also be further substituted. Further, when there are two or more substituents, they may be different. If possible, they can also be joined to each other to form a ring. The above substituent T is explained below. The "substituent T" includes, for example, "alkyl group" (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms). Examples include: methyl, ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.); Alkenyl" (preferably 1345083 is a carbon number of 2 to 20, more preferably a carbon number of 2 to 12, particularly preferably a carbon number of 2 to 8', for example, including: an ethyl group, an aryl group 2, butenyl, 3-pentenyl, etc.); "alkynyl" (preferably having 2 to 20 carbon atoms) more preferably 2 to 12 carbon atoms, particularly preferably a carbon atom The number is 2 to 8, and includes, for example, propargyl group, 3-pentenyl group, etc.; "aryl group" (preferably, the number of carbon atoms is 6 to 30', and more preferably the number of carbon atoms is 6 to 20 ' Particularly preferred is a carbon atom number of 6 to 12, for example, including a phenyl group, a p-methylphenyl group, a naphthyl group, etc.); a "substituted or unsubstituted amine group" (preferably a carbon atom) The number is 〇~2〇, and more preferably the number of carbon atoms is 〇~ particularly good is the carbon atom. For example, 〇~6' includes: an amine group, a methylamino group, a dimethylamino group 'diethylamino group', a benzhydryl group, etc.): an "alkoxy group" (preferably a carbon atom) The number is 1 to 20, more preferably the number of carbon atoms is 1 to 12, and particularly preferably the number of carbon atoms is 1 to 8, including, for example, methoxy, ethoxy, butoxy, etc.); Oxyl group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, including, for example, phenoxy group, 2-naphthalene) Oxyl group, etc.); "fluorenyl group" (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms), for example, including: Ethylene, benzylidene, methionyl, trimethylethenyl, etc.); "alkoxycarbonyl" (preferably having 2 to 20 carbon atoms, more preferably having a carbon number of 2 to 16, particularly preferably having 2 to 12 carbon atoms, and includes, for example, a methoxycarbonyl group, an ethoxycarbonyl group, etc.; ""oxycarbonyl group" (preferably having a carbon number of 7 to 20) 'More preferably, the number of carbon atoms is 7 to 16, and the best is carbon. The sub-number is 7 to 10, and includes, for example, a phenoxycarbonyl group or the like.); "oximeoxy group" (better than -35-1345083, preferably having 2 to 20 carbon atoms, more preferably 2 to 20 carbon atoms) 16, particularly preferred is a carbon number of 2 to 10, for example, including: ethoxycarbonyl, benzhydryl, etc.); "nonylamine" (preferably having 2 to 20 carbon atoms, more preferably The number of carbon atoms is 2 to 16, particularly preferably 2 to 10 carbon atoms, and includes, for example, acetamino group, benzylamino group, etc.; "alkoxycarbonylamino group" (preferably) The number of carbon atoms is from 2 to 20, more preferably from 2 to 16, particularly preferably from 2 to 12, and includes, for example, a methoxycarbonylamine group. "Alkoxycarbonylamino group" (preferably having a carbon number of 7 to 20', more preferably a carbon number of 7 to 16, particularly preferably a carbon number of 7 to 12', including, for example, a phenoxy group a carbonylamino group, etc.; "sulfonamide group" (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms), for example, including: Methanesulfonamide, benzenesulfonylamine, etc.; "aminesulfonyl" (preferably having a carbon number of 0 to 20' is more preferably a carbon number of 〇~16, particularly preferably a carbon number For example, 12 includes, for example, an amine sulfonyl group, a methylamine sulfonyl group, a dimethylamine sulfonyl group, a phenyl amidino group, etc.); an "aminomethyl group" (preferably a carbon atom) Preferably, the number is from 1 to 20', and the number of carbon atoms is from 1 to 16', and the number of carbon atoms is from 1 to 12', for example, including: amine-mercapto-methylamine-mercapto-diethylamine-methyl fluorenyl , phenylamine carbhydryl group, etc.); "alkylthio" (preferably having 1 to 20 carbon atoms) more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms For example, it includes: methylthio 'ethylthio group, etc.); "arylthio" ( Preferably, the number of carbon atoms is 6 to 20, more preferably the number of carbon atoms is 6 to 16', and the number of carbon atoms is 6 to 12', for example, including: phenylthio group, etc.); Preferably, the number of carbon atoms is from 1 to 20, more preferably from 1 to 16 to 36 to 1345,083, and particularly preferably from 1 to 12, and includes, for example, methylsulfonyl, toluenesulfonyl and the like. "Sulfosyl" (preferably having 1 to 2 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, including, for example, sulfinamide) Base, phenylsulfinyl group, etc.); "ureido group" (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms), particularly preferably 1 to 12 carbon atoms, for example Including urea group, methylurea group, phenylurea group, etc.; "phosphoric acid amide group" (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably carbon) The number of atoms is 1 to 12, and includes, for example, diethylphosphonium amide, phenylphosphonium amide, hydroxyl group, hydrogenthio group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyanide. Base, sulfonic acid group, carboxyl group, nitrate , a hydroxamic acid group, a sulfinic acid group, a fluorenyl group, an imido group; a "heterocyclic group" (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 2), and the hetero atom system includes, for example, The nitrogen atom and the oxygen atom 'sulfur atom, specifically, include, for example, an imidazolyl group, a pyridyl group, a quinolyl 'furanyl group, a piperidinyl group, a fluorenyl group, a benzoxazolyl group, a benzimidazolyl group, Benzothiazolyl, etc.); "decylalkyl" (preferably having a carbon number of from 3 to 40' is more preferably a carbon atom of from 3 to 30, particularly preferably a carbon number of from 3 to 24, for example: three Methyl decyl group, triphenyl decyl group, etc.), etc. These substituents may be further substituted. Further, if there are two or more substituents, they may be the same or different. If possible, they may be bonded to each other to form a ring. The specific examples of the compound represented by the formula (III) will be described in detail below, but the present invention is not limited to the specific examples. 1345083 〔化8〕 F- 1 F-

F-2

CHj

F- 3 F- 8

OCH3 F- 4

F

OH

F-10 F- 5

-38- 1345083

39- 1345083 〔化1 〇〕 F -21 F_23

-40- 1345083

B - 7 OCH,

B - 8

OCH

OCH3 O

-41 - 1345083 [Chem. 1 2] B -11

H3CO 〇ch3 B ~ 16 CHc

Ch3 B -12 巳一17

日一18 巳一13

Ν' code, CH3 B -14

B -19

H U

B - 15

B -20 CH.

N -42- 1345083 [Chemical 1 3] 巳 _ 21 D — 1

-43 - 1345083 [Chem. 1 4]

The compound represented by the formula (I) to (ΠΙ) is used in an amount of from 0.01 to 20 parts by mass, more preferably from 0.5 to 10 parts by mass, based on 100 parts by mass of the cellulose ester. The above compounds are used in this range, whereby the retardation and water permeability of the film can be appropriately controlled. If the amount used is less than 质量·〇 1 part by mass, the control of delayed enthalpy and water permeability will be insufficient. If the amount used is more than 20 parts by mass, the additive will not be compatible with the cellulose ester and may crystallize in the film. Further, the discotic compound disclosed in Japanese Patent Laid-Open Publication No. 2001-661-44 is also particularly suitable for use. The amount of the compound having such a hydrophobic group is preferably in the range of 0.01 to 30% by mass, more preferably 0.1 to 20% by mass based on the solution (coating liquid) to be prepared. Further, the moisture permeability system can be reduced by extending the alignment of the deuterated cellulose molecular chains in the direction of transport and/or the width direction during film formation. The -44- 1345083 extension can be implemented in either the uniaxial extension method or the biaxial extension method. Although the biaxial stretching method includes both the simultaneous biaxial stretching method and the sequential biaxial stretching method, but from the viewpoint of continuous manufacturing, it is preferably a sequential biaxial stretching method, which is cast coated. After the liquid, the film is peeled off from the belt or the drum to extend in the width direction (longitudinal direction) and then in the longitudinal direction (width direction). The method of extending in the width direction is described in, for example, Japanese Patent Laid-Open No. 62-1105035, JP-A-4-41 1 25, the same as No. 4-28421, the same as 4-2983. No. 1 0, in the same bulletin as No. 1 1 -4827 No. 1. The extension of the film is carried out under normal temperature or heating conditions. The heating temperature is preferably below the glass transition temperature of the film. The film can be stretched by treatment in a dry state, and is particularly effective when a solvent remains. When extending in the longitudinal direction, for example, the film conveyance roller speed is adjusted so that the film winding speed is faster than the film peeling speed, and the film can be stretched. When extending in the width direction, the film can be stretched by a method in which the width of the film is held by the tenter while being conveyed, and the width of the tenter is gradually enlarged. It is also possible to extend the film after it has been dried (preferably using a uniaxial extension of a long stretcher). The stretching ratio of the film (ratio of the amount of increase in the original length extension) is preferably in the range of 5 to 50%, more preferably in the range of 10 to 40%, and most preferably in the range of 15 to 35%. . Further, the cellulose film is treated at a high temperature to increase the degree of crystallization, whereby the water permeability can be lowered. The above treatment must be carried out at a temperature and time at which the volatilization of the low molecular compound and the thermal cracking of the cellulose film itself do not cause the problem -45 - l345 〇 83. The treatment temperature is preferably 160 ° C or more and 260 ° C or less, more preferably 180 ° C or more and 240 ° C or less. The treatment time is preferably 5 minutes or more and 2 hours or less, and more preferably 1 minute or more and 1 hour or less. In the present invention, the moisture permeability measured by the first protective film at 60 ° C and 95% RH is preferably 250 g/m 2 · 24 hr or more and 1,000 g / m 2 · 24 hr or less, more preferably 400 or less. g/m2 · 24 hr or more and 1,000 g/m2 · 24 hr or less. The moisture permeability of the second protective film measured under conditions of 60 ° C and 95 % RH is preferably 500 g/m 2 · 24 hr or more and 5,000 g/m 2 · 24 hr or less, more preferably 700 g/m 2 . Above hr and below 3,000 g/m2 · 24 hr. Further, the difference in the moisture permeability measured by the first protective film and the second protective film at 60 ° C '95% RH is preferably 200 to 2,000 g/m 2 · 24 hr, and more preferably 300 to 1 , 500 g/m2 · 24 hr. If the difference is too large, the curl of the polarizing plate becomes large, so that a problem arises when the polarizing plate is attached to the liquid crystal cell. [Delay of film] Re retardation 値 (nano) and Rth retardation 奈 (nano) of the film can be defined by the following formulas (I) and (II). (I) Re = ( nx - ny) xd (II) Rth = { ( nx + ny ) /2 - nz } χ d In the formulas (I) and (II), nx is the direction of the slow phase in the plane of the film The refractive index (the refractive index will become the largest direction). In the formulae (I) and (II), ny is a refractive index in the direction of the phase in the plane of the film (the refractive index will become the smallest direction). _ 46 _ 1345083 In the formula (π), nz is the refractive index in the thickness direction of the film. In the formulae (I) and (II), d is the thickness of the film in nanometers. 〇 In the present invention, the air interface side protective film can be used with any retardation. In contrast, the liquid crystal cell side protective film can be used in various delays depending on its use. The liquid crystal cell side protective film itself can also be used as an optically anisotropic film. In this case, the OCB mode user preferably has a Re of 10 to 100, more preferably 20 to 70. Rth is preferably 50 to 300, more preferably 100 to 25 0. For the VA mode user, the shell [J Re is preferably 20 to 100, more preferably 30 to 70. Rth is preferably 50 to 250, more preferably 80 to 180. In addition, in the case of the TN mode, Re is preferably 〇~50, more preferably 2~30. Rth is preferably from 10 to 200, more preferably from 30 to 150. Alternatively, an optically anisotropic layer may be coated on the liquid crystal cell side protective film to serve as an optical compensation film. In this case, the optical characteristics of the liquid crystal cell side protective film alone are those in the IPS/VA mode, and Re is preferably 〇1 to 1, preferably more preferably 0 to 5. Rth is preferably 0 to 20, more preferably 〇~1. In the OCB mode and the TN mode, the optically anisotropic layer can be applied to the liquid crystal cell side protective film having the above retardation. Used as an optical compensation film. Among them, in the OCB mode and the TN mode, an optically anisotropic layer may be coated on the deuterated cellulose film having the above retardation to use 彳乍 as a light-47-I345〇83 compensation film. Further, the birefringence (? η : nx - ny ) of the protective film is in the range of 0.002 μm. Further, the birefringence { ( nx + ny) /2 - nz } of the support film and the opposite direction of the thin direction is preferably in the range of 0·. The thickness (dry film thickness) of the deuterated cellulose film is preferably from 20 to 110 μm, more preferably from 40 to 100 μ, and the intersection angle of the retardation axis of the protective film and the absorption axis of the polarizing film, any値, but preferably parallel or 45 degrees 20° azimuth. [Delaying Increasing Agent] In the liquid crystal cell side protective film, in order to increase the retardation, it is preferred that the aromatic compound to be an aromatic ring is used as a retardation rising agent, and the aromatic compound includes at least two aromatic rings. Such as triazine traps (triphenyl-1,3,5-triazine trap, tris-inter-tris-triazine, etc.); di-1,4-cyclohexanedicarboxylic acid diesters I a diester of phenol, a diester of p-n-pentylphenol, and the like. Other specific examples are described in Japanese Patent Laid-Open No. 111914, the specification of the Japanese Patent Publication No. 2000-275434, No. 00/02619, and the like. It is also possible to use two or more aromatic compounds. The aromatic hydrocarbon ring is added to the aromatic hydrocarbon ring to contain an aromatic hydrazine. The molecular weight of the retardation increasing agent is preferably from 300 to 800. When the deuterated cellulose film is used as the liquid crystal cell side protective film, it is preferably 0.00: the film thickness is 〇 0 to 0 _ 0 4 120 μm several meters. Although it can be used for the lesser. The retardation compound, for example, i - 1, 3, 5 [p-positive-hexanthene 2000-, PCT/JP compound family heterocyclic ring, then the aromatic-48-1345083 family compound should be relative to 100 parts by mass. The use of the aromatic cellulose in the range of 0.01 to 20 parts by mass is preferably used in the range of 0.05 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the deuterated cellulose. Used under the scope. [Delay Decrease Agent] The liquid crystal cell side protective film system can also be used as an additive to reduce the retardation enthalpy. The compound of the above formula (I) to (III) for this purpose can also be suitably used. In the liquid crystal cell side protective film, when a cellulose oxide film is used, the compound of the above formula (I) to (ΠΙ) is used in an amount of from 0.01 to 20 parts by mass based on 100 parts by mass of the deuterated cellulose. The aromatic compound is preferably used in an amount of from 0.05 to 15 parts by mass, more preferably from 0.1 to 10 parts by mass, per 100 parts by mass of the deuterated cellulose. [Photoelasticity] The photoelastic coefficient of the protective film of the present invention is preferably 6 〇χ 1 cm 2 /N or less 'more preferably 2 〇 x 1 (T8 cm 2 /N or less. The photoelastic coefficient can be obtained by an ellipsometer). [Glass transfer temperature] The protective film glass transition temperature of the present invention is preferably 120 ° C or higher, more preferably 140 ° C or higher. The glass transition temperature is measured by differential scanning calorimetry (DSC) ' at a temperature increase rate of 1 In the measurement of 〇°c/min, the average temperature of the temperature at which the baseline of the glass transition originating from the film will start to change and the temperature returned to the baseline again is determined. The polarizing plate of the present invention is other than the polarizing film or the protective film. It is also possible to have a binder layer, a separator film, and a protective film as constituent elements. -49-1345083 2. Manufacturing Procedure of Polarizing Plate Next, the manufacturing steps of the polarizing plate of the present invention will be described below. The manufacturing step is preferably a polarizing film swelling step, a polarizing film dyeing step, a polarizing film solid film step, a polarizing film stretching step, a polarizing film drying step, a protective film bonding step, and a drying step after bonding. The order of the dyeing step, the solid film step, and the stretching step may be arbitrarily changed, or a plurality of steps may be combined to be simultaneously performed. Alternatively, it may be as described in the invention patents 3, 3 3 1, 6 15 after the solid film step. In the present invention, it is preferred that the swelling step, the dyeing step, the solid film step, the stretching step, the drying step, the protective film bonding step, and the drying step after bonding are sequentially performed in the order described. In the above-described steps or after, a planar inspection step on the line may be provided. The swelling step is preferably carried out only using water, but as described in Japanese Patent Laid-Open No. Hei No. 1 5 3 709, The optical performance tends to be stabilized and the wrinkles of the polarizing plate substrate are prevented from being generated in the production line, and the polarizing plate substrate may be swollen by the boric acid aqueous solution to manage the swelling degree of the polarizing plate substrate. The temperature and time of the swelling step may be Arbitrarily set, but preferably l〇°C or more and 60°C or less, 5 seconds or more and 2,000 seconds or less. The dyeing step can be carried out according to Japanese Patent Laid-Open No. 2002-865 54 In addition, the dyeing method is not limited to the dipping method, and any method such as coating or spraying iodine or a dye solution may be used, and it may be used as described in Japanese Patent Laid-Open No. Hei No. Hei. Adjusting the concentration of iodine, the temperature of the dye bath, the stretching ratio in the bath, and the bath in the stirring bath, and simultaneously dyeing. 1345083 The dichroic molecule uses a high-order iodide ion to prepare a high contrast polarizing plate. Preferably, the dyeing step is to use a solution in which iodine is dissolved in an aqueous solution of potassium iodide. In this case, the preferred range of the iodine-potassium iodide aqueous solution is iodine of 0.05 to 2 g / liter 'potassium iodide is 3 to 200 g / liter, The mass ratio of iodine to potassium iodide is from 1 to 2,000. The dyeing time is preferably from 1 〇 to 1 μm, and the liquid temperature is preferably from 10 to 6 〇t. Further preferably, the iodine is 0.5 to 2 g/liter, the potassium iodide is 30 to 120 g/liter, the mass ratio of iodine to potassium iodide is 30 to 120, the dyeing time is 30 to 600 seconds, and the liquid temperature is 20 to 50 °C. . Further, as described in Japanese Patent No. 3,145,747, an anthraquinone compound such as boric acid or borax may be added to the dyeing liquid. The solid filming step is preferably carried out by immersing in a crosslinking agent solution or by subjecting a crosslinking agent to a coating solution. The solid filming step can also be carried out by dividing the solid filming step into several times as described in Japanese Patent Laid-Open No. Hei No. 1-5.2130. The cross-linking agent can be used as described in U.S. Republished Patent No. 2 3 2,8,9, or as described in the invention patent No. 3357 1-9, which is used as a cross-linking agent for improving dimensional stability. Aldehyde, but it is best to use boric acid. For the crosslinking agent used in the solid film step, when boric acid is used, metal ions may be added to the boric acid/potassium iodide aqueous solution. The metal ion is preferably zinc chloride. However, as described in Japanese Patent Laid-Open No. 2000-3551-2, zinc halide such as zinc iodide, zinc sulfate, zinc acetate or the like may be used instead of zinc chloride. Zinc salt. In the present invention, it is preferred to employ a method of first preparing a boric acid-potassium iodide aqueous solution to which zinc chloride is added, and then immersing the PVA film therein to solidify the film. -51 - 1345083 Preferably, the boric acid is 1 to 100 g / liter, the potassium iodide is 1 to 12 g / liter, the zinc chloride is 0.01 to 10 g / liter, and the solid film time is 10 to 1, 200 seconds. The liquid temperature is 10 to 60 ° C. More preferably, the boric acid is 10 to 80 g / liter, the potassium iodide is 5 to 100 g / liter, the zinc chloride is 〇 · 02 to 8 g / liter 'the solid film time is 30 to 600 seconds, and the liquid temperature is 20 ~ 5 0 ° C. The stretching step is suitable for the longitudinal single axial stretching method described in U.S. Patent No. 2,454,515, or the like, or the tenter method described in Japanese Patent Laid-Open No. 2002-8 6 5 4 . The stretching ratio is preferably 2 times or more and 12 times or less, more preferably 3 times or more and 10 times or less. In addition, the relationship between the stretching ratio and the thickness of the original package and the thickness of the polarizing film is also set as described in Japanese Patent Laid-Open No. Hei 14-040256 (the thickness of the polarizing film after the protective film is laminated/original roll) Film thickness) x (full extension ratio) 〇 _17, the relationship between the width of the polarizing film when the last bath comes out and the width of the polarizing film when the protective film is bonded is also suitable for use in the same general opening No. 1 4-040247 The 0.80% (the width of the polarizing film when the protective film is bonded/the width of the polarizing film when the last bath comes out) is S 0.95. The drying step can be carried out by the method described in Japanese Patent Laid-Open Publication No. 2002-86554, but the preferred temperature range is from 30 ° C to 10 ° C, and the drying time is from 30 seconds to 60 minutes. Further, as described in Japanese Patent No. 3,148,513, it is also suitable to apply a heat treatment for setting the fading temperature in water to 50 ° C or higher, or as in Japanese Patent Laid-Open No. 07-3252 15 or JP-A-7-3252. The aging treatment is applied in an atmosphere subjected to temperature and humidity management as described in No. 18. The protective film bonding step is a step of bonding two protective films to both sides of the above polarizing film subjected to a drying step of -52 to 1345083. It is a method of applying a bonding liquid immediately before bonding, and then preferably laminating the roller by laminating a polarizing film and a protective film. In addition, it is preferable to adjust the moisture ratio of the polarizing film to suppress the groove shape of the album produced by the extension of the polarizing film, as described in Japanese Patent Laid-Open No. 200-296426 and JP-A-2002-86 554. Bump. In the present invention, it is suitable to use a moisture content of 0.1 to 30%. The binder of the polarizing film and the protective film is preferably a PVA-based resin (modified PVA including acetamidine, sulfonate, carboxyl, oxyalkylene, etc.) or a boron compound, although it is not particularly limited. An aqueous solution or the like is preferably a PVA-based resin. The thickness of the adhesive layer is preferably from 〇1 to 5 μm after drying, more preferably from 5 to 3 μm. Further, it is also suitable to adopt a method in which the protective film is surface-treated to be hydrophilized and then bonded to improve the adhesion between the polarizing film and the protective film. The method of surface treatment is not particularly limited, and any method such as saponification using an alkali solution, corona treatment, or the like can be employed. Further, an easy-adhesion layer such as a base coat layer may be provided after the surface treatment. The contact angle of the surface of the protective film with water is preferably 50 or less as described in Japanese Patent Laid-Open Publication No. 2002-267839. The drying conditions after the lamination can be carried out according to the method described in JP-A-2002-86554, but the preferred temperature range is from 30 ° C to 100 ° C, and the preferred drying time is from 30 seconds to 60 minutes. In addition, as described in the Japanese Patent Laid-Open No. Hei 07-325220, the content of the element in the β-polarized film is preferably aged under the temperature and humidity management atmosphere. Preferably, the iodine is 0.1 to 3.0 g/ M2, boron 1345085 is 0.1 ~ 5.0 g / m2, potassium is 0 · 1 ~ 2.0 g / m2 'zinc is 0 ~ 2.0 g / m2. In addition, the potassium content can be set to 〇·2 mass% or less as described in Japanese Patent Laid-Open Publication No. 2001-166143. The zinc content in the polarizing film can also be set as described in JP-A-2000-0355. 0.04% by mass to 〇·5 mass%. In order to improve the dimensional stability of the polarizing plate, an organic titanium compound and/or an organic zirconium compound may be added to the dyeing step, the stretching step, and the solid film step, as described in Japanese Patent No. 3,323,255. At least one compound selected from the group consisting of an organic titanium compound and an organic chromium compound. Further, in order to adjust the hue of the polarizing plate, a dichroic dye may be added. 3. Characteristics of polarizing plate (1) Transmittance and degree of polarization The preferred single-plate transmittance of the polarizing plate of the present invention is 42.5 % or more and 49.5% or less, and more preferably 42.8 % or more and 49.0 % or less. The preferred range of the degree of polarization defined by the formula 4 is 99.900% or more and 99.999% or less, more preferably 99.940% or more and 99.995% or less. The parallel transmittance is preferably in the range of 36% or more and 42% or less, and the range of the orthogonal transmittance is preferably 0.001% or more and 0.05% or less. The preferred range of the dichroic ratio defined by the formula 5 is 48 or more and 1,2 15 or less, and more preferably 53 or more and 5 2 5 or less. The above transmittance can be defined by the following formula by JIS ZS 701: [Number 1]

-54- 1345083 where K, S(A), y(A), τ(λ) are as follows: [Number 2] (Equation 3) Κ 100ρ{λ) γ{λ) άλ S( λ): used The color distribution of the standard light of the display color; y(A) · the color parameter in the lanthanide system; τ ( λ ): the spectral transmittance; [number 3] (Formula 4) The degree of polarization (%) = 100 平行 Parallel transmission Rate-orthogonal transmittance χ·\(parallel transmittance + orthogonal transmittance (Equation 5) dichroic ratio _ = log 'single plate transmittance 100 Λ polarization, · 1 100 ) log , veneer transmittance Λ The degree of polarization, 1 100 (100 Jj iodine concentration and veneer transmittance can also be within the range described in Japanese Patent Laid-Open No. 20-25-2581. Parallel transmittance is as disclosed in Japanese Patent Laid-Open No. The wavelength dependence can also be small as described in No. 2001-083328 or JP-A-2002-22250. The optical characteristics of the polarizing plate when arranged in crossed Nicols can also be the same as the special opening 200 1 In the range described in No. 091,736, the relationship between the parallel transmittance and the orthogonal transmittance may also be within the range described in JP-A-2002- 1 74728-55- 1345083, for example, Japanese Patent Laid-Open No. 2002-221618 Number of light, wavelength Between 42〇~700nm, the standard deviation of parallel transmittance per 10nm can be 3 or less, and the wavelength of light is between 42 0~700 nm, every 10 nm (parallel transmittance / The minimum 値 of the orthogonal transmittance can be more than 300 〇. It can also make the polarizing plate parallel transmittance and orthogonal transmittance at 440 nm wavelength, parallel transmittance, parallel transmittance and orthogonality at 550 nm wavelength. The transmittance, and the parallel transmittance and the orthogonal transmittance at a wavelength of 610 nm are set as described in Japanese Patent Laid-Open No. 2002-258042 or the same as JP-A-2002-25804. (2) Hue The hue of the polarizing plate of the present invention can be evaluated using the brightness index and the chromaticity index a* and b* in the L*a*b* chromaticity system which is derived from the CIE equal sensible space. L*, a* The b* system can use the above X, Y, Z and is defined as (Formula 6). [Number 4] i* = H6(y/y0)i -16 (Formula 6) α- = 500^Χ/Χ0) Ϊ-{Υ/Υ〇)^ ^ = 2〇o[(y/y0)i-(z/z0)il where Xc, Yc, Ζο represents the three stimuli of the illumination source, in the case of standard light c The following is Χ〇 = 98.072, Υ〇 = 100, Ζ〇 = 118.2 25, in the case of the standard 1345083 quasi-optical 〇65, X〇 = 95.045, Y〇 = 1〇〇, = i〇84892

The preferred a* range of the O polarizing plate monolith is -2.5 or more and 0.2 or less, more preferably -2.0 or more and less than 〇. The preferred b* of the polarizing plate monolith is in the range of 1.5 or more and 5 or less, and more preferably 2 or more and 4.5 or less. The preferred range of a* of the parallel transmitted light of the two polarizing plates is -4.0 or more and 〇 or less, more preferably -3.5 or more and -0.5 or less. The preferred range of b* of the parallel transmitted light of the two polarizing plates is 2.0 or more and 8 or less, more preferably 2.5 or more and 7 or less. The preferred range of a* of the orthogonally transmitted light of the two polarizing plates is -5. or more and 2 or less, more preferably 0 or more and ί or less. The preferred range of b* of the orthogonally transmitted light of the two polarizing plates is -2.0 or more and 2 or less, more preferably -1 · 5 or more and 0.5 or less. The hue system can also be evaluated by the chromaticity coordinates (X, y) calculated by X, Y, and Z above, such as the chromaticity (Xp, yp) of the parallel transmitted light of two polarizing plates and the chromaticity of the orthogonal transmitted light. (Xe'ye), can be set to the range described in Japanese Patent Laid-Open No. 2002-2 14436, JP-A-2001-166136, or JP-A-2002-169024, or the hue and absorbance. The relationship is set within the range described in JP-A-2001-311827. (3) Viewing angle characteristics When the polarizing plate is arranged in crossed Nicols and the light of 550 nm wavelength is incident, it can also make the vertical light incident, and the orientation of the polarizing axis is 45 degrees. The transmittance ratio or the xy chromaticity difference when the normal is incident at an angle of 40 degrees is set as described in Japanese Patent Laid-Open No. 2001-166135 or the same as JP-A No. 2001-166. The scope. In addition, as described in JP-A No. 1345085, No. 1 0-0688 No. 7 ', the vertical light transmittance (T〇) of the polarizing plate laminate disposed as crossed Nicols can be compared with the laminated body $ The ratio (Teo/To) of the light transmittance (T6〇) in the direction of the normal inclination of 60° is set to 10,000 or less, or as described in JP-A No. I4-139625, for the polarizing plate to be 80 degrees from the normal line to the elevation angle. When natural light is incident at any angle, the transmission spectrum of the transmission light is in the wavelength range of 520 to 64 nanometers, and the transmittance difference of the transmitted light within the wavelength range of 2 nanometers is set to 6% or less, or The difference in luminance of transmitted light at any distance of 1 cm from the film described in Kaiping No. 08-248201 is set to be within 30%. (4) Durability (4-1) Damp heat durability, as described in Japanese Patent Laid-Open No. 2001-1-1646, placed in an atmosphere of 60 ° C, 90% RH for 500 hours, before and after The rate of change in light transmittance and degree of polarization is preferably 3% or less in absolute enthalpy. In particular, the rate of change of the light transmittance is 2% or less, or the rate of change of the degree of polarization is preferably 1.0% or less in terms of absolute enthalpy, and more preferably 〇·1% or less. Further, as described in JP-A No. 0 7-07 7 608, it is preferred that the polarizing degree after 95 hours at 80 ° C and 90% RH is 95% or more and the monomer transmittance is 38% or more. (4-2) Dry durability at 80. (: When the film is left in a dry atmosphere for 500 hours, the rate of change of the light transmittance and the degree of polarization before and after it is preferably 3% or less in absolute enthalpy. In particular, the rate of change of light transmittance is 2% or less. 'The rate of change of the other degree of polarization is preferably 1.0% or less, more preferably 0.1% or less in absolute terms. 1345083 (4 -3) Other durability, such as Japanese Patent Special Open As shown in No. 1 of 06-16761, the shrinkage ratio after standing at 80 ° C for 2 hours is set to 0.5% or less, or a polarizing plate laminate having crossed Nicols on both sides of the glass plate is placed and placed at 69 X75 and y値 after 75 hours in the atmosphere of °C are set within the range described in JP-A-H10-068818, or after being placed in an atmosphere of 80 T:, 90% RH for 200 hours, The change in the spectral intensity ratio of 105 cnT1 and 157 cnT1 by Raman spectroscopy is set as described in JP-A-2008-94884 or JP-A-09-197127. (5) Alignment Although the degree of alignment of the PVA is higher, the better polarization performance can be obtained, but by polarized Raman scattering or polarized FT-IR. The order parameter calculated by the method is preferably 0.2 to 1 · 0. Alternatively, the polymer portion of the entire amorphous domain of the polarizing film may be as described in Japanese Patent Laid-Open No. 59-133-509. The difference between the alignment coefficient and the occupational molecular alignment coefficient (0.75 or more) is set to be at least 0.15, or the amorphous domain alignment coefficient of the polarizing film is set to 0.65 to 0.85, or 13_ or as described in JP-A- 04-204907.配5· The orientation of the high-order iodide ion is set to 0.8 to 1.0. (6) Other characteristics can also be as described in Japanese Patent Laid-Open No. 2002-006 1 33, which will be at 80 ° C. The absorption axis direction contraction force per unit width at the time of heating for 30 minutes is set to 4.0 N/cm or less, or the polarizing plate is allowed to stand under heating at 70 ° C for 120 hours as described in JP-A No. 20 02-236213. Then, the dimensional change rate of the absorption axis direction of the polarizing plate and the dimensional change rate of the polarization axis direction, -59-1345083 are set to within ±0.6%, or the moisture ratio of the polarizing plate is set to be the same as 2002-09. 3 masses listed in No. 546. /. below. And 'can be further as special The surface roughness perpendicular to the direction of the extension axis is set to be 0. 04 μm or less in terms of the center line average roughness, as described in JP-A-2000-249832, or as described in JP-A No. 1,268,294. The refractive index no in the transmission axis direction is set to be larger than 1_6', or the relationship between the thickness of the polarizing plate and the thickness of the protective film is set to be in the range described in Japanese Laid-Open Patent Publication No. 10-111411. 4. Functionalization of Polarizing Plate The polarizing plate of the present invention is suitably used as a phase difference plate or λ which is required for a reflective or semi-transmissive LCD having a viewing angle expansion film (viewing angle compensation layer) having an LCD. a functional layer of a seesaw, a reflective layer or a semi-transmissive layer, an antireflection film reflective film, a brightness enhancement film (brightness enhancement layer) or a hard coat layer 'front scattering layer, an antiglare layer, etc. required to improve display visibility Optical film composite functionalized polarizer. A cross-sectional schematic view showing an example in which a polarizing plate of the present invention is combined with the above functional optical film is shown in Fig. 1. As shown in Fig. 1, the functional optical film 3 and the polarizing film 2 (Fig. 1(A)) may be bonded by a binder as a protective film 1 on one side of the polarizing plate, or may be bonded by the adhesive layer 4. The functional optical film 3 is bonded to a polarizing plate in which protective films ia and lb are provided on both surfaces of the polarizing film 2 (Fig. 1(B)). In the case of the former, any transparent protective film can be used on the other protective film. The peeling strength between the respective layers of the functional layer or the protective film may be set to 4.0 N/25 mm or more as described in Japanese Patent Laid-Open No. 22-32-338. Functional light -60-1345083 The film is preferably disposed on the side of the liquid crystal module according to the intended function, or on the opposite side to the liquid crystal phase group, that is, on the display side or the backlight side. The functional optical film to be used in combination with the polarizing plate of the present invention will be described below. (1) Viewing angle expansion film The polarizing plate of the present invention can be used in combination with, for example, TN (Twisted Nematic type), IPS (In-Plane Switching type), OCB. (optical compensation bending type:

Optically Compensatory Bend type), VA (vertical alignment type: Vertically Aligned type), ECB (electric field control birefringence type:

Electrically Controlled Birefringence type) The viewing angle expansion film of the display mode. The viewing angle expansion film for the TN mode can be printed by the Japan Printing Society, Vol. 36, No. 3 (1999), pages 40 to 44, the monthly display of the August issue (2002), pages 20 to 24, and the Japanese patent. WV film (Fuji Photo Film Co., Ltd.) described in Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. Used in combination. The preferred structure of the viewing angle expansion film for the TN mode is to laminate the alignment layer and the optically anisotropic layer on the above transparent polymer film in this order. The viewing angle expansion film can be used as a bonding agent to bond with a polarizing plate, but as described in SID' 00 Dig., p. 551 (2000), from the viewpoint of thinning, Jia is also one of the protective films for the above polarizing film. The -61 - 1345083 alignment layer can be provided by a rubbing treatment of an organic compound (preferably a polymer), an oblique vapor deposition of an inorganic compound, or a method of forming a layer having microgrooves. Further, it is known that an alignment layer which imparts an alignment function by imparting an electric field, imparting a magnetic field or by light irradiation is particularly preferable as an alignment layer formed by rubbing treatment of a polymer. The rubbing treatment is carried out by rubbing the surface of the polymer layer in a certain direction with paper or cloth several times. The absorption axis direction of the polarizing film and the rubbing direction are preferably substantially parallel. For the type of the polymer to be used as the aligning layer, a polymer having a polymerizable group described in JP-A-H09-52509, and the like can be used. The thickness of the alignment layer is preferably from 0.01 to 5 μm, more preferably from 〇 5 to 2 μm. The optically anisotropic layer preferably contains a liquid crystalline compound. The liquid crystalline compound to be used in the present invention is particularly preferably a discotic compound (disc liquid crystal). The discotic liquid crystal molecule has a disc-shaped core as the triphenylene derivative, and the side chain is a structure in which it radially extends. Further, in order to impart stability over time, it is also possible to introduce a group which can react with heat or the like. A preferred example of the above-mentioned dish-shaped liquid crystal is disclosed in Japanese Laid-Open Patent Publication No. 8-50206. In the vicinity of the alignment layer, the discotic liquid crystal molecules are aligned substantially parallel to the film plane at a pretilt angle to the rubbing direction, and the opposite air surface side discotic liquid crystal molecules are aligned perpendicularly to the surface. The dish-like liquid crystal layer forms a mixed alignment, and the layer structure can realize the viewing angle expansion effect of the TN mode TFT-LCD. The optically anisotropic layer is generally prepared by dissolving a dish-like compound and another compound -62-1345083 (and further a polymerizable monomer, a photopolymerization initiator) in a solvent, and coating the solution on the alignment layer. After drying, it is heated to a dish-like nematic phase to form a temperature, and then irradiated with uv (ultraviolet) light or the like to be polymerized, followed by cooling. The dish-like liquid crystal phase-solid phase transfer temperature for the dish-like liquid crystal compound used in the present invention is preferably 70 to 300 ° C, and particularly preferably 70 to 170 ° C. Further, a compound other than the discotic compound to be added to the optically anisotropic layer may have a compatibility with a discotic compound and impart a change in the inclination angle of the front surface of the liquid crystal disc compound or may not hinder For compounding, any compound can be used. Among these, an air interface of a polymerizable monomer (for example, a compound having a vinyl group, a vinyloxy group, an acryloyl group, and a methyl propyl group), or a triazine compound containing a fluorocarbon can be used. The additive for the alignment control of the side, a polymer such as cellulose acetate, cellulose acetate propionate, hydroxypropyl cellulose, and cellulose acetate butyrate. The amount of the compound to be added to the disc compound is usually 0.1 to 50% by mass, preferably 1 to 30% by mass. The thickness of the optically anisotropic layer is preferably from 0.1 to 10 μm, and more preferably from 0.5 to 5 μm. A preferred embodiment of the viewing angle expansion film is an optically exclusive direction composed of a deuterated cellulose film as a transparent substrate film, an alignment layer disposed thereon, and a discotic liquid crystal formed on the alignment layer. The layer is composed of a layer, and the optically anisotropic layer is crosslinked by irradiation of UV light. Further, in addition to the above, when the viewing angle expansion film is combined with the polarizing plate of the present invention, it is also possible to take a crossover with respect to the board surface as described in Japanese Patent Laid-Open No. Hei 07-63-1345083 1 98942. The direction in which the direction of the protective film and the optically anisotropic layer are set to be substantially the same as the optical axis and the phase difference plate in which the birefringence is different in the direction of the birefringence, or as described in JP-A-H14-258052 The same way. In addition, as described in JP-A No. 2-258632, the moisture content of the polarizing plate to be bonded to the viewing angle expansion film may be set to 2.4% or less, or may be taken as the special opening 2002- As described in No. 267,839, the contact angle with the water of the viewing angle expansion film surface is set to 70 or less. The IPS mode liquid crystal cell viewing angle expansion film is used to improve the optical compensation of the liquid crystal molecules aligned parallel to the substrate surface and the viewing angle characteristics of the orthogonal transmittance of the polarizing plate in the black display without the applied electric field state. The IPS mode is black in the absence of an applied electric field, and the transmission axes of the upper and lower polarizers are orthogonal. However, when viewed obliquely, the intersection angle of the transmission axis is no longer 90°, so that light leakage is caused to cause a decrease in contrast. When the polarizing plate of the present invention is used in an IP S mode liquid crystal cell, the phase difference in the in-plane of the Japanese Patent Laid-Open Publication No. 10-54982 is reduced to 0, and is in the thickness direction. A combination of viewing angle expansion film having a phase difference. The OCB mode liquid crystal cell viewing angle expansion film is used to optically compensate a liquid crystal layer which becomes a vertical alignment in the central portion of the liquid crystal layer due to an applied electric field and which is inclined in the vicinity of the substrate interface, thereby improving the viewing angle at the time of black display. characteristic. When the polarizing plate of the present invention is used in an OCB mode liquid crystal cell, it can be suitably used as a viewing angle expansion film group which is blended with a discotic liquid crystalline compound as described in U.S. Patent No. 5,805,253 - 64-1345083 Used together. The VA mode liquid crystal cell viewing angle expansion film is used to improve the viewing angle characteristic when the liquid crystal molecules are vertically aligned with respect to the substrate surface in the state where no electric field is applied. Such a viewing angle expansion film can be arranged in parallel with the substrate in a phase difference of 〇 in the in-plane phase described in Japanese Patent Publication No. 2,866,372, and having a phase difference in the thickness direction, or a disk-shaped compound. a thin film, or an extension film having the same in-plane retardation 积 laminated to form a film in which the slow phase axes are orthogonal, or to prevent deterioration of the orthogonal transmittance in the oblique direction of the polarizing plate, and to be made of a liquid crystal molecule® A film composed of a rod-like compound is used in combination with a laminate. (2) λ /4 plate The polarizing plate of the present invention can be used as a circularly polarizing plate laminated with a λ /4 plate. The circular polarizing plate has a function of converting incident light into circularly polarized light, and is suitable for use in a transflective liquid crystal display device such as a reflective liquid crystal display device or an ECB mode, or an organic EL (electroluminescence element) device. The λ /4 plate used in the present invention is capable of obtaining substantially complete circularly polarized light in the visible light wavelength range, preferably having a retardation (Re ) of substantially 1/4 of the wavelength in the range of the visible light wavelength. Phase difference film. The so-called "approximately 1/4 delay in the range of visible light wavelengths" means that from the wavelength of 400 to 700 nm, the longer the wavelength, the greater the delay and can meet the wavelength of 450 nm. The measured retardation Re (Re45Q) is 80 to 125 nm, and the retardation Re (Re59 〇) measured at a wavelength of 590 nm is in the range of 120 to 160 nm, and more preferably Re59. - Re45() g5 nm, especially good for Re59D - Re45〇2 1〇 nano. -65- 1345083 The λ /4 plate used in the present invention is not particularly limited as long as it can satisfy the above conditions, but it can be used, for example, in Japanese Patent Laid-Open No. 5-27310, and the same Japanese Patent Laid-Open No. 1 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 10-90521, the entire disclosure of which is incorporated herein by reference. A λ /4 plate in which a polymer film is stretched as described in the publication No. 26705 is provided on the polymer film as described in JP-A-2000-284126 and JP-A-2002-31717. An optically anisotropic layer above the layer; any Λ/4 plate of t / 4 plates, etc. Further, the retardation axis direction of the polymer film or the alignment direction of the optically anisotropic layer is coordinated to the liquid crystal cell and arranged in either direction. In the circularly polarizing plate, the retardation axis of the λ/4 plate and the transmission axis of the polarizing film may be crossed at any angle, but it is preferably 45. ±20. The range makes it cross. However, the retardation axis of the Λ/4 plate and the transmission axis of the polarizing film may be crossed in a range other than the above. When the λ Μ plate is composed of a laminated λ /4 plate and a λ /2 plate, it is described in Japanese Patent Laid-Open No. Hei. No. 3,236,304, or Japanese Patent Laid-Open No. Hei. Preferably, it is bonded so that the angle formed by the in-plane slow axis of the /2-plate and the transmission axis of the polarizing plate is substantially 75 and 15. (3) anti-reflection Film The polarizing plate of the present invention can be used in combination with an antireflection film. The antireflection film can be a film having a reflectance of about 1.5% of a low refractive index material such as a fluorine-based polymer imparted to a single layer, or a film. The multilayer interference has a reflectance of -66 to 1345083 1% or less. In the present invention, it is preferred to use a low refractive index layer on the transparent support and a high refractive index on the lower refractive index layer. The layer of at least one of the layers (that is, the high refractive index layer and the medium refractive index layer) is laminated, and is also suitable for use in the Nitto Technology News No. 38, No. 1, May 2000, 26 to 28 pages, or an antireflection film described in Japanese Patent Laid-Open Publication No. 2002-30 1 783, etc. The refractive index conforms to the following conditions: Refractive index of high refractive index layer &gt; Refractive index of medium refractive index layer &gt; Refractive index of transparent support&gt; Refractive index of low refractive index layer can be used as transparent support for antireflection film A transparent polymer film for the protective film of the above polarizing layer can be used. The refractive index of the low refractive index layer is 1.20 to 1.55, preferably 1.30 to 1.50. The low refractive index layer is preferably It is used as the outermost layer having scratch resistance and antifouling properties. In order to improve the scratch resistance, a material containing a polydecyloxy group or a fluorine-containing material may be used to impart slidability to the surface. In Japanese Patent Laid-Open No. 9-2225 03, the specification paragraph number [0018] to [0026], the same as paragraph No. 11-38202, paragraph number [0019] to [0030], and Tongkai No. 2001-40284 The compound described in the specification paragraph number [0027] to [0028], and the like, and the compound containing polyfluorene oxide, preferably a compound having a polysiloxane structure, But it can also Reactive polyazaite (for example, Sairaplein (manufactured by Nitrogen Co., Ltd An organometallic compound such as a coupling agent, such as -67- 1345083, and a specific fluorinated hydrocarbon-containing decane coupling agent are condensed by a condensation reaction in the presence of a catalyst (Japanese Unexamined Patent Publication No. Hei No. 58-142958, No. Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The compound described in the publication No. 2002-538〇4, etc.). The low refractive index layer may contain, in addition to the above additives, an average of primary particles such as silica, fluorine-containing particles (magnesium fluoride, calcium fluoride, barium fluoride). A low-refractive-index inorganic compound having a diameter of 1 to 150 nm, and an organic fine particle described in paragraph number [〇〇20] to [0038] of Japanese Patent Laid-Open No. Hei 1 - 3 8 2 0) , decane coupling agent, slip agent, surfactant, etc. The low refractive index layer may be formed by a vapor phase method (vacuum steaming method, sputtering method, ion plating method, plasma CVD method, etc.), but it is preferably coated from the viewpoint of being able to be manufactured at a low cost. Cloth formation. As the coating method, a dipping method, an air knife coating method, a curtain coating method, a roll coating method, a bar coating method, a photogravure coating method, or a micro gravure coating method can be used. The film thickness of the low refractive index layer is preferably from 30 to 200 nm, more preferably from 50 to 150 nm, and most preferably from 60 to 120 nm. The medium refractive index layer and the high refractive index layer are preferably one having a high refractive index inorganic compound ultrafine particle having an average particle diameter of 100 nm or less dispersed in a matrix material. As the inorganic compound fine particles having a high refractive index, an inorganic compound having a refractive index of 1.65 or more, for example, an oxide of Ti, Zn, Sb, Sn, Zr, Ce, Ta, La, In or the like, containing the complex oxidation of the metal atoms can be used. -68- 1345083 and so on. Such ultrafine particles can be treated with a surface treatment agent for the surface of the particles (a decane coupling agent, etc.: Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Compound or organometallic coupling agent: JP-A-2001 - 3 1 〇 432, etc.), a core-sheath structure having a high refractive index particle as a core (Japanese Patent Laid-Open No. 2001-166104, etc.), and a specific dispersing agent ( For example, it is used in a mode such as Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2002-2776069. For the material for the substrate, any thermoplastic resin, (thermosetting) resin film, or the like may be used, but it is also possible to use JP-A-2000-47004, the same as JP-A No. 200 1 - 3 15242, and the same. The polyfunctional material described in the above-mentioned Japanese Patent Publication No. 2001-296401, or the hardening of the metal alkoxide composition described in JP-A No. 2,001 -2, 9.38 18, and the like. Sex film. The refractive index of the high refractive index layer is preferably from 1.70 to 2.20. The thickness of the high refractive index layer is preferably from 5 nm to 10 μm, more preferably from 10 nm to 1 μm. The refractive index of the medium refractive index layer should be adjusted to be between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the medium refractive index layer is preferably from 1.50 to 1.70. The haze of the antireflection film is preferably 5% or less, more preferably 3% or less. Further, the strength of the film is preferably Η or more, more preferably 2H or more, and most preferably 3H or more, according to the pencil hardness test of FIS K5400. (4) Brightness improving film - 69 - 1345083 The polarizing plate of the present invention can be used in combination with a brightness improving film. Brightness Enhancement The separation function of the film with circular or linear polarization is used to arrange between the polarizing plate and the backlight module so that one of the circular or linear polarized light is reflected rearward or backscattered toward the backlight side. The re-reflected light from the backlight portion can locally change the polarization state, and when incident on the brightness enhancement film and the polarizing plate, it can be partially transmitted, and the process can be repeated to improve the light utilization efficiency. The front brightness is increased by about 1.4 times. Brightness improvement The film is known to have an omnidirectional reflection mode and an isotropic scatter mode, and the like can be used in combination with the polarizing plate of the present invention. In the aspect of the anisotropic reflection method, a brightness-enhancing film in which a uniaxially stretched film and an unstretched film are laminated into a plurality of layers to increase the refractive index difference in the extending direction to have an anisotropic property of reflectance and transmittance is known. And a multilayer film method using the principle of a dielectric mirror (described in the World Invention Patent No. WO 95/1 769 No. 1, the same as WO 95/1 7692, the same as WO 95/1 7699) Or a cholesteric liquid crystal method (described in the specification of the European Patent No. 606940 A2, Japanese Patent Laid-Open No. Hei 8-2 7 1 73 1). In the multi-layer brightness enhancement film using the principle of a dielectric mirror, DBEF-E, DBEF-D, and DBEF-M (all manufactured by 3M Company) are suitable for use in the present invention, and a brightness-enhancing film of a cholesteric liquid crystal type is used. NIP OCS (made by Nitto Denko Co., Ltd.) is suitable for use in the present invention. For NIPOCS, please refer to the Nitto Technology Newsletter No. 38 'No. 1, May 2000, 19~21, etc. Further, in the present invention, the specification of the inventions of the World Patent No. WO 97/32223, the same as WO 97/32224, the same as WO 97/32225, and the same as the specification of the Japanese Patent Publication No. 70- 1345083 WO 97/32226 can also be used. And the intrinsic birefringent polymer described in each of the publications of Japanese Patent Laid-Open Publication No. 9- 2:74 1 08 and the same as H- 1 7423 1 is blended with a negative intrinsic birefringent polymer, and A brightness enhancement film that is uniaxially extended by an isotropic scattering method is used in combination. The isotropic scattering type brightness enhancement film is preferably DRPF-H (manufactured by 3M Co., Ltd.). The polarizing plate and the brightness improving film of the present invention are preferably used in the form of being bonded by an adhesive or by forming one of the protective films of the polarizing plate as an integral type of a brightness improving film. (5) Other functional optical films The polarizing plate of the present invention may also be combined with a hard coat layer, a front scattering layer, an antiglare layer, a gas barrier layer, a slip layer, an antistatic layer, a base coat layer or a protective layer. The functional optical film is used in combination. Further, the functional layers may be used in combination in the same layer as each other or in the same layer as the above-mentioned antireflection layer or optically anisotropic layer. (5-1) Hard coat layer The polarizing plate of the present invention is a mechanical strength which imparts scratch resistance and the like, and is preferably a method in which a "hard coat layer" and a functional optical film provided on the surface of a transparent support are combined with each other. . When the hard coat layer is applied to the above antireflection film, it is preferably provided between the transparent support and the high refractive index layer. The hard coat layer is preferably formed by a crosslinking reaction using a light and/or heat curable compound or by a polymerization reaction. The curable functional group is preferably a photopolymerizable functional group. Further, the organometallic compound -71 - 1345083 containing a hydrolyzable functional group is preferably an organoalkoxyalkylene group compound. The specific structural composition of the hard coat layer can be, for example, those described in Japanese Laid-Open Patent Publication No. 2002-14493, the same as No. 2000-9908, and the World Patent No. WO 0/46617. The strength of the hard coat layer is preferably Η or more according to the pencil hardness test of ns K5400, more preferably 2H or more, and most preferably 3H or more. Further, in the results of the Taber abrasion test according to JIS Κ 54〇0, the amount of abrasion of the test piece before and after the test is preferably as small as possible. As the material for forming the hard coat layer, a compound containing an ethylenically unsaturated group β and a compound containing a ring-opening polymerizable group may be used, and these compounds may be used singly or in combination. Preferred examples of the compound containing an ethylenically unsaturated group include: ethylene glycol diacrylate, trimethylolpropane triacrylate, di-trimethylolpropane tetraacrylate, neopentyl glycol triacrylate, Polyacrylates of polyols such as neopentyl glycol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate; bisphenol bis diglycidyl ether diacrylate, hexanediol An epoxy acrylate such as a diacrylate of a glycidyl ether; an urethane acrylate such as a urethane obtained by reacting a polyisocyanate with a hydroxyethyl acrylate or the like; and a commercially available product The grades of the compounds include: ΕΒ-600, ΕΒ-40, ΕΒ-140, ΕΒ-1150, ΕΒ-1 290 Κ, IRR214, ΕΒ-2220, ΤΜΡΤΑ, ΤΜΡΤΜΑ (all of them are DAICEL. UCB (share)), UV -63 00, UV-1700B (all of them are made by Japan Synthetic Chemical Industry Co., Ltd. (all are trade names)). Further, preferred examples of the compound containing a ring-opening polymerizable group include: -72-1345083 Glycidyl ethers are: ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, trishydroxyl Ethylene triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, triglycidyl trihydroxy ether iso-cyanurate sorbitol tetraglycidyl ether , neopentyl alcohol tetraglycidyl ether, polyglycidyl ether of cresol novolac resin; polyglycidyl ether of phenol novolac resin; alicyclic epoxy type: Seloxide 202 IP, Seloxide 208 1. Epolead GT-301, Epolead GT - 4 0 1, HP E 3 1 5 0 CE (all of which are manufactured by DAICEL Chemical Industry Co., Ltd. (all are trade names)); Φ polycyclohexyl ring of phenol novolac resin Oxymethyl ether and the like; oxetane are: OXT-121, OXT-22 1, 0X-SQ, PNOX-1 009 (all of which are East Asian Synthetic (shares) (all are trade names)) Wait. Alternatively, a polymer of glycidyl (meth)acrylate or a copolymer of a monomer copolymerizable with glycidyl acrylate may be used as the hard coat layer. For the hard coat layer, in order to reduce the hardening shrinkage of the hard coat layer, improve the adhesion to the substrate, and reduce the curl of the hard coat treated article of the present invention, it is also suitable to add bismuth, titanium, zirconium, aluminum, or the like. Oxide particles, or crosslinked particles of poly(ethylene), polystyrene, poly(meth)acrylates, polydimethylsiloxane, SBR (styrene-butadiene rubber), NBR (butyronitrile) A method of crosslinking crosslinked fine particles such as organic fine particles such as rubber particles or the like. The average particle diameter of the crosslinked particles is preferably from 1 nm to 2,00.0 nm. Further, the shape of the crosslinked particles is not limited to the use of a spherical shape, a rod shape, a needle-like shape or the like. The amount of the fine particles added is preferably 60% by volume or less, more preferably 40% by volume or less, of the hard coating layer after hardening. -73- 1345083 When the inorganic fine particles described above are added, generally, since the affinity with the binder polymer is not good, it is also suitable to use a metal containing cerium, aluminum, titanium, or the like, and have an alkoxide group. A surface treatment agent having a functional group such as a carboxylic acid group, a sulfonic acid group or a phosphonic acid group is subjected to a surface treatment. The hard coat layer is preferably hardened by using heat or active energy rays. Among them, active energy rays such as radiation, gamma rays, α-rays, electron rays, ultraviolet rays, and the like are preferably used, but safety and productivity are considered. It is especially good to use electron rays and ultraviolet rays. When it is hardened by heat, the heating temperature is preferably 140 ° C or less, more preferably 1 Torr or less, from the viewpoint of heat resistance of the plastic itself. (5-2) Front Scattering Layer The "forward scattering layer" is used to improve the viewing angle characteristics (hue and luminance distribution) in the up, down, left, and right directions when the liquid crystal display device is applied to the polarizing plate of the present invention. In the present invention, a structure in which fine particles having different refractive indices are dispersed as a binder is used, for example, Japanese Patent Laid-Open No. II-3 82-8, which uses a forward scattering coefficient, can be used, and transparent resin and fine particles are used. The relative refractive index is defined as a structure of the Japanese Patent Laid-Open No. 2000-199809, and the Japanese Patent Laid-Open Publication No. 2002-1〇75 No. 2, which has a haze of 4 or more. In addition, the polarizing plate of the present invention can be used in combination with "Lumisuty" described on pages 31 to 39 of the technical report "Photofunctional Film" of Sumitomo Chemical Industries Co., Ltd. in order to control the viewing angle characteristics of the haze. (5-3) Anti-glare layer The "anti-glare layer" is used to scatter reflected light to prevent image reflection. Anti-glare -74- 1345083 The function is obtained by forming irregularities on the outermost surface (display side) of the liquid crystal display device. The haze of the optical film having an anti-glare function is preferably from 3 to 30%, more preferably from 5 to 20%, and most preferably from 7 to 20%. In the method of forming the unevenness on the surface of the film, for example, a method of adding fine particles to form irregularities on the surface of the film (for example, Japanese Patent Laid-Open Publication No. 2000-271878, etc.) and a small amount (0.1 to 50% by mass) are relatively large. A method of forming a surface unevenness film (particle size: 0.05 to 2 μm) (for example, Japanese Patent Laid-Open No. 2000-28 1 41 0, the same as No. 2000-95 893, the same as No. 2001-1 00004 Japanese Laid-Open Patent Publication No. 2001-28 1 407, etc., and a method of physically transferring a concavo-convex shape on a surface of a film (for example, Japanese Patent Laid-Open No. 63-278839, No. 1 1 - 1 837) Japanese Unexamined Patent Publication No. 2000-275401, etc., etc.). The functional layers may be provided on one side or both sides of either the polarizing film side and the reverse side of the polarizing film. 5. Liquid crystal display device using a polarizing plate Next, a liquid crystal display device using the polarizing plate of the present invention will be described below. Fig. 2 is an example of a liquid crystal display device using the polarizing plate of the present invention. As shown in Fig. 2, the liquid crystal display device has liquid crystal cells (15 to 19), and an upper polarizing plate 11 and a lower polarizing plate 22 are disposed via liquid crystal cells (15 to 19). The polarizing plate holds the polarizing film and the pair of transparent protective films, but in Fig. 2, it is shown as an integrated polarizing plate, and the detailed structure thereof is omitted. The "liquid crystal cell" includes an upper substrate 15 and a lower substrate 18, and a liquid crystal layer formed of the liquid crystal molecules 17 sandwiched therebetween. The liquid crystal cell system can be classified into TN (Twisted Nematic; Twisted Nematic) and IPS (In-Plane Switching) depending on the alignment state of liquid crystal molecules displayed by ON/OFF (on/off). In-plane switching))·'O.CB (Optically Compensatory Bend), VA (Vertically Aligned), ECB (Electrically Controlled Birefringence) display mode, but the polarizing plate of the present invention However, any display mode can be used regardless of the transmissive type and the reflective type. An alignment film (not shown) is formed on the surface of the liquid crystal® molecules 17 contacting the substrates 15 and 18 (hereinafter also referred to as "inner surface"), and liquid crystal molecules are not applied in an electric field or in a low applied state. The alignment is controlled by a rubbing treatment or the like applied to the alignment film. Further, on the inner surfaces of the substrates 15 and 18, a transparent electrode (not shown) capable of applying an electric field to the liquid crystal layer composed of the liquid crystal molecules 17 is formed. The rubbing direction of the TN mode is applied in a direction in which the upper and lower substrates are orthogonal to each other, and the magnitude of the tilt angle can be controlled by the strength and the number of rubbing times. The alignment film is formed by coating a polyimide film and baking it. The twist angle of the liquid W layer depends on the intersection angle of the rubbing direction of the upper and lower substrates and the chiral agent added to the liquid crystal material. In this example, when the twist angle is 90° and the pitch is about 60 μm, the palm powder β is added. When the twist angle is applied to a liquid crystal display device for a notebook computer, a personal computer monitor, or a television set, Then set to 90. Near (85 ~ 95°), when used as a reflective display device such as a portable telephone, 'set to 〇~7〇°»In IPS mode or ECB mode, the twist angle will be -76-1345083 0° . In the IPS mode, the electrodes are disposed only on the lower substrate 18 to apply an electric field parallel to the substrate surface. As for the OCB mode, there is no twist angle, and the tilt angle is set to be larger, and in the V A mode, the liquid crystal molecules 17 are aligned perpendicular to the upper and lower substrates. However, the thickness Δ nd due to the thickness d of the liquid crystal layer and the refractive index anisotropy Δ n causes the luminance to change in white display. Therefore, in order to obtain the maximum brightness, the range is set for each display mode. The intersection angle of the absorption axis 1 2 of the upper polarizing plate 1 1 and the absorption axis 23 of the lower polarizing plate 22 is generally so as to be substantially orthogonal, whereby high contrast can be obtained. The angle of intersection of the absorption axis 12 of the upper polarizing plate 11 of the liquid ® cell and the rubbing direction of the upper substrate 15 differs depending on the liquid crystal display mode, but in the TN and IPS modes, it is generally set to be parallel or perpendicular. In the OCB and ECB modes, it is mostly set at 45°. However, in order to adjust the color tone or the viewing angle of the display color, the optimum mode is different in each display mode, and thus it is not limited to these ranges. The liquid crystal display device to which the polarizing plate of the present invention can be used is not limited to the structure of Fig. 2, and may include other members. For example, a color filter may be disposed between the liquid crystal cell and the polarizing film. Further, the viewing angle expansion film 13 and 20 may be disposed between the liquid crystal cell and the polarizing plate ® . The polarizing plates 11 and 22 and the viewing angle expansion film 13 and 20 may be arranged in a laminated form in which the adhesive is bonded, or may be used as one of the liquid crystal cell side protective films for expanding the viewing angle. Integral ellipsometer configuration" In addition, when used as a transmissive type, the backlight can be configured with a cold cathode or a hot cathode fluorescent tube, or a light emitting diode, a field emission element, and an electroluminescent element as a light source. at the back. Further, the liquid-77-1345083 crystal display device for using the polarizing plate of the present invention may also be of a reflective type "in this case, the polarizing plate system may be disposed only on the observation side" and on the back surface of the liquid crystal cell or the liquid crystal cell. A reflective film is disposed on the inner surface of the lower side substrate. It is of course also possible to arrange the optical mode group on the liquid crystal cell observation side before using the above-mentioned light source. [Embodiment] [Examples] [Example 1] (Production of deuterated cellulose film (1, 3, 4, 6, 8, 10' 11, 13, 15)) The following composition was charged into a mixing tank. The mixture was heated while stirring to dissolve the components to prepare a bismuth cellulose solution A. <Composition of deuterated cellulose solution A> Cellulose acetate having a degree of acetylation of 60.9 % 100 parts by mass of triphenyl phosphate (plasticizer) 7.8 parts by mass of biphenyl diphenyl phosphate (plasticizer) 3.9 parts by mass Methylene chloride (first solvent) 300 parts by mass of methanol (second solvent) 54 parts by mass of 1-butanol 11 parts by mass. The following composition was placed in another mixing tank, and the ingredients were dissolved by heating while stirring to prepare Additive solution B - 1 to B - 6 » <Additive liquid B-1~; Composition of β-6> -78-1345083 Table 1 Coating liquid dichloromethane (parts by mass) 'Methanol (parts by mass) UV absorber (A) (mass) UV absorber (B) (parts by mass) Compound (F-7) (parts by mass) Compound (A-4) (parts by mass) B-1 80 20 2 4 No B-2 80 20 2 4 10 Μ B-3 80 20 2 4 Μ 10 B-4 80 20 2 4 10 10 B-5 80 20 2 4 15 15 B-6 80 20 2 4 15 20 [Chemical 1 5] Manufacture of the film (1)> In 474 parts by mass of the deuterated cellulose solution A, 20 parts by mass of the additive solution B-1 was added and stirred sufficiently to prepare a coating liquid. The coating liquid was cast from the casting port on a drum cooled to 〇 °C. The solvent is contained in a state in which the solvent content is 70% by mass, and the needle-clamping type is described in the third embodiment of the Japanese Patent Laid-Open No. 4-1009. The tenter was fixed, and in a state where the solvent content was 3 to 5 mass%, the elongation in the transverse direction (direction perpendicular to the machine direction) was maintained at an interval of 3%, and it was dried at the same time. Thereafter, it was re-dried by transfer between rolls of a heat treatment apparatus to obtain a cellulose-fibrin film (1) having a thickness of 80 μm. <Manufacture of bismuth cellulose film (3), (4), (6) > Addition of additive solution and thickness in the production of bismuth cellulose film (1)

UV absorber A UV absorber B-79-1345083 was changed to the same as shown in Table 2, and the same was obtained in the same manner as the cellulose-deposited film (1) (3), (4), (6). [Example 2] The following composition was placed in a mixing tank, and the components were dissolved by heating while stirring to prepare a cellulose-deposited solution C. <Composition of deuterated cellulose solution C> Cellulose acetate having a degree of acetylation of 60.9 %, 100.0 parts by mass of triphenyl phosphate (plasticizer) 7.0 parts by mass of diphenyl diphenyl phosphate (plasticizer) 4.0 parts by mass Methylene chloride (first solvent) 402.0 parts by mass of methanol (second solvent) 60.0 parts by mass <Production of deuterated cellulose film (8) > 5 73 parts by mass of deuterated cellulose solution C, 24 parts by mass of additives Solution B-1 was thoroughly stirred to prepare a coating liquid. The resulting coating liquid was cast using a belt casting machine. After the film surface temperature reached 40t:, it was dried by 〇°C warm air for 1 minute, and then the film was peeled off by the tape. Next, the film was dried by drying at 14 ° C for 1 minute to obtain a deuterated cellulose film (8) having a residual solvent amount of 0.3% by mass and a thickness of 80 μm. <Production of Deuterated Cellulose Films (10), (11), and (13)> Except that the additive solution and the thickness are changed to those shown in Table 2 in the production of the deuterated cellulose film (8), Deuterated cellulose films (i), (H), and (13) were obtained in the same manner as the deuterated cellulose film (8). <Production of Deuterated Cellulose Film (15)> In addition to the production of the deuterated cellulose film (10), the cellulose acetate of the deuterated cellulose solution -80-1345083 C was changed to an acetylation degree of 1.8, A cellulose-deposited cellulose film (15) was obtained in the same manner except for cellulose acetate butyrate having a degree of hexadecanolization of 0.9. Table 2 Xie number additive solution thickness (min m) Additive amount (% by mass relative to deuterated cellulose) Moisture permeability (g/m2 · 24 hr) Finishing (F-7) Compound (A-4) (1) B-1 80 0 0 1,350 (2) B-2 80 4 0 1,000 (4) B-3 80 0 4 1,110 (6) B-5 80 8 0 520 (8) B-1 80 0 0 1,500 (10) B-2 80 4 0 1,220 (11) B-3 80 0 4 1,350 (13) B-5 80 8 0 810 (15) B-1 80 4 0 1,450 [Example 3] (alkali treatment) The cellulose film was immersed in a 1.5 equivalent sodium hydroxide aqueous solution at 55 ° C for 2 minutes. Then, it was washed in a water bath at room temperature, and neutralized using 30 ° C '0.1 equivalent of sulfuric acid. It was again washed in a water bath at room temperature and then dried at a temperature of 100 °C. The surface of the deuterated cellulose film is saponified in this manner. [Example 4] The iodine was adsorbed on the stretched polyvinyl alcohol film to obtain a polarizing film, and the deuterated cellulose film (6) obtained in Example 1 was attached to the polyvinyl alcohol-based adhesive. One side of the polarizing film. Further, the transmission axis of the polarizing film and the late phase axis of the bismuth cellulose film are arranged in parallel. Further, the deuterated cellulose film (8) obtained in Example 3 was attached to the opposite side of the polarizing film using a polyvinyl alcohol-based adhesive. In this way, 1345083 is obtained to obtain a polarizing plate (1). [Example 5] A polarizing plate (1) to (13) was produced in combination with a fluorinated cellulose film shown in Table 3, and a polarizing plate air interface ϊϋ~~ a cellulose film (first) Protective film) ------ π liquid crystal side deuterated cellulose film (second protective film) moisture permeability difference (first protective film - second protective film) (g/m2 · 24 hr) Remarks (1) ( 6) (15) 930 The present invention (2) (6) ___〇0) 700 The present invention (3) (6) _〇1) 830 The present invention (4) (6) Wide a, --- - (13) 290. The present invention_(5) / - a, (1) 830 The present invention (6) (13) (1) 540 The present invention (7) (13) (3) 290 The present invention (8) (13) (4) 300 The present invention ( 9) (13) (8) 690 The present invention (10) (6) _ (8) 980 The present invention (11) (1) (8) 500 The present invention 02) (1) (12) - 370 Comparative Example (13) (2) Γ ( 13) -1,050 Comparative Example

[Example 6] The polarizing plate obtained in the above manner was attached to a glass plate so that the liquid crystal side deuterated cellulose film was on the glass side, and was allowed to be made at 60 ° C and 90% RH φ. After 15,000 hours, the parallel transmittance and the orthogonal transmittance were measured with a Shimadzu UV 2200 spectrophotometer, and then the degree of polarization was calculated by the above (Formula 4). In addition, the amplitude of the curl of the polarizing plate was visually determined. The results are shown in Table 4. -82- 1345083 Table 4 Polarizing plate polarizing degree (%) Curl remark (1) 98.1 〇 The present invention (2) 98.4 〇 The present invention (3) 98.7 〇 The present invention (4) 99.9 〇 The present invention (5) 98.6 〇 The present invention (6) 99.5 〇 the present invention (7) 99.8 〇 the present invention (8) 99.7 〇 the present invention (9) 98.8 〇 the present invention (10) 98.1 〇 the present invention (11) 99.6 〇 the present invention (12) 95.2 Δ Comparative Example (13) 93.7 Δ Comparative Example It is known from the results that the polarizing plate of the present invention has a small change in the degree of polarization of heat and humidity, and according to the result, it is found that the change in the polarization degree of heat and humidity of the polarizing plate of the present invention is small, and The curl is small and therefore has superior durability. [Example 7] A polarizing plate was peeled off from one of a 20-inch liquid crystal display device (LC-20V1, manufactured by Sharp) using a TN type liquid crystal cell, and replaced with a binder. The polarizing plate obtained in Example 1 was attached to each of the viewer side and the backlight side in such a manner that the optical compensation sheet was positioned on the liquid crystal cell side. Further, the transmission axis of the polarizing plate on the observer side and the transmission axis of the polarizing plate on the backlight side are arranged to be orthogonal. Then, under the environmental conditions of a temperature of 25 ° C and a relative humidity of 60 %, the backlight module was continuously lit for 400 hours, and the overall black display state was visually observed in the dark room to evaluate the light leakage. As a result, in the polarizing plate of the comparative example, the frame-like light leakage was observed on the display image side of the liquid crystal display device, whereas the liquid crystal display device using the polarizing plate 1345083 of the present invention did not observe such a situation. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an example of a structure of a polarizing plate and a functional optical film of the present invention, respectively showing a functional one for bonding a functional optical film and a polarizing film by a binder to be used as a one-side protective film for a polarizing plate. Example (A), and an example (B) of bonding a functional optical film to a polarizing plate provided with a protective film on both sides of a polarizing film by a binder. Fig. 2 is a view showing an example of a liquid crystal display device for use in the polarizing plate of the present invention. [Main component symbol description] 1 , la, lb protective film 2 polarizing film 3 functional optical film 4 adhesive layer 11 upper polarizing plate 12 upper polarizing plate absorption axis 13 optical anisotropic layer (viewing angle expansion film) 14 optical Orthotropic layer alignment control direction 15 Liquid crystal cell upper electrode substrate 16 Upper substrate alignment control direction 17 Liquid crystal layer 18 Liquid crystal cell electrode substrate 19 Lower substrate alignment control direction 1345083 2 1 Optical anisotropic layer alignment control direction 22 Lower polarizer 23 lower polarizer absorption axis

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Claims (1)

1345083 Patent No. 93 1 2925 6 "Polarizing Plate and Liquid Crystal Display Device Using It" (Revised on January 12, 2011) X. Patent Application Range: 1. A polarizing plate, which is a first protective film, a polarizing film, The second protective film is formed by laminating in this order, and is characterized in that the moisture permeability of the first protective film is lower than the moisture permeability of the second protective film. 2. For the polarizing plate of claim 1, the difference between the first and second protective films measured at 60 ° C, 95 %, and RH is 200 ° ~ 2,000 g/m2 · 24 hr ° , 3. For the polarizing plate of claim 1, wherein the first and second protective films are polymer films containing the same polymer as the main component, and The types and/or amounts of additives contained in the first and second protective films are different. 4. The polarizing plate of claim 1, wherein the first and second protective films are deuterated cellulose films, and the first and second protective films contain different types of deuterated cellulose. 5. For the polarizing plate of claim 1, the first protective film has a moisture permeability of 250 to 1,000 g/m2 • 2 4 hr 〇6 at 60 ° C and 95 % RH. For example, in the polarizing plate of claim 1, wherein the second protective film has a moisture permeability of 500 to 5,000 g/m2 measured at 60 ° C and 95% RH. 7 · The polarizing plate of claim 1 is provided with an adhesive layer. 8. The polarizing plate of claim 1, wherein an anti-glare layer is provided on a surface opposite to a surface of the polarizing film with respect to the first protective film. 9. The polarizing plate of claim 1, wherein a reflective layer or a semi-transmissive reflective layer is provided. 10. For the polarizing plate of claim 1, the phase difference layer or the λ / 4 layer is provided. 1 1. A polarizing plate according to item 1 of the patent application/where a viewing angle compensation layer is provided. 12. The polarizing plate of claim 1, wherein a brightness enhancement layer is provided. The liquid crystal display device is characterized in that it has a liquid crystal cell and two polarizing plates disposed on both sides thereof, and at least one piece of polarized light A polarizing plate according to any one of claims 1 to 12, wherein the second protective film of the polarizing plate is located on the liquid crystal cell side. 1345083 Amendment page VII. Designated representative map (1) The representative representative of the case is: Figure 1 (A), (B). (2) The symbol of the representative figure of this representative figure is simple: 1 '1 a, lb protective film 2 polarizing film 3 functional optical film 4 adhesive layer 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: 〇 «Μ, -4-