TW200831962A - Polaring plate and liquid crystal device - Google Patents

Abstract

The invention provides a polarizing plate having small variation in transmission and polarizing degree caused by heat and humidity and having high endurance, as well as providing a liquid crystal display device without leading variation in colors but showing high display quality. A polarizing plate formed by laminating a first protection film, polarizer, and a second protection film in this order, which is characterized in that the first protection film has moisture permeability of 300 g/m2.day or less at 60 DEG C, 95%RH, and the second protection film is cellulose acylate film.

Description

200831962 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a polarizing plate and a liquid crystal display device. [Prior Art] The liquid crystal display device is an image display device that consumes less power and is space-saving, and thus its use is expanding year by year. In the past, although the dependence of the image on the viewing angle is a big disadvantage of the liquid crystal display device, since the high viewing angle liquid crystal mode such as the VA mode and the I PS mode has been put into practical use in recent years, even a high viewing angle for the television and the like is required. The market is also rapidly expanding the demand for liquid crystal display devices. Accordingly, for the polarizing plate used in the liquid crystal display device, a higher performance of a higher layer is also required. In particular, the improvement of durability against temperature and humidity has been a major issue for polarizers. In the case of a polarizing plate, it is generally a method of adsorbing iodine by a hydrophilic polymer film such as a polyvinyl alcohol-based film or a partially homopolymerized polyvinyl alcohol or an ethylene-vinyl acetate copolymer partially alkalized film. Then, it is made by stretching it. However, when such a polarizing plate is used for a long period of time, there is a problem that the transmittance of the entire screen under the black display increases, the color odor changes, and the edge-like light leakage occurs. The reason for the increase in the transmittance and the edge leakage is known to be due to the relaxation of the stretched hydrophilic polymer and the decomposition of iodine, and is greatly affected by the amount of moisture permeation from the outside through the protective film. Further, as a polarizing plate protective film used on the cell side of the liquid crystal, although a deuterated cellulose film can be generally used in 200831962, the deuterated cellulose film may have a change in optical characteristics due to a change in humidity, so that display performance is obtained. The problem of deterioration. On the other hand, a method of providing a polarizing plate having a small change in transmittance and polarization due to heat and humidity has been disclosed in Japanese Laid-Open Patent Publication No. 2005-266222. Japanese Laid-Open Patent Publication No. 2005-309394 discloses a method of bonding a protective film having a low moisture permeability and a polarizer to form a polarizing plate. However, according to these methods, it is not necessarily effective to improve the durability. SUMMARY OF THE INVENTION [Invention] The object of the present invention is to solve the aforementioned problems and to achieve the following objects. That is, an object of the present invention is to provide a polarizing plate which has a small transmittance due to heat and humidity, a small change in a polarizing plate, and high durability. Further, it is an object of the present invention to provide a liquid crystal display device having high quality of a display device which does not cause a significant change in color odor. In order to solve the above problems, the inventors of the present invention have conducted an intensive review and obtained cognitive findings as described below. In other words, it has been recognized that in order to improve the durability of the polarizing plate under high temperature and high humidity and to achieve high display quality, it is possible to use a deuterated cellulose film having a function as a phase difference film. The sealing of the liquid crystal cell to the side of the protective layer is such that the moisture permeability of the first protective film provided on the opposite side across the polarizer reaches a predetermined thickness or less, thereby achieving high display quality. 200831962 The present invention has been completed based on the above-mentioned cognitive findings of the present inventors, and the means for solving the above problems are as follows. The polarizing plate of the present invention is a polarizing plate in which the first protective film, the polarizer and the second protective film are laminated in this order, wherein the first protective film is at a relative humidity of 60 ° C. The moisture permeability at 95% is 300 g/m 2 /day or less, and the second protective film is a deuterated cellulose film. The liquid crystal display device of the present invention is a liquid crystal display device comprising a liquid crystal cell and two polarizing plates disposed on both sides thereof, wherein at least one of the polarizing plates is composed of a first protective film, a polarizer, and a polarizing plate in which the second protective film is laminated in this order, wherein the first protective film has a moisture permeability of 300 deg/m 2 曰 at 60 ° C and a relative humidity of 9.5 %. The second protective film is a deuterated cellulose film, and the second protective film of the polarizing plate is attached to the opposite side of the liquid crystal cell. [Embodiment] DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a polarizing plate and a liquid crystal display device according to the present invention will be described in detail. In the description of the present embodiment, the numerical range indicated by the use of "~" means that the numerical range described before and after "~" is used as the upper limit 値 and the lower limit 値. Further, "45 °", "parallel" or "straight" in the present embodiment means that the angle of the angled soil is less than 5 °. The difference between the angle and the tight angle is preferably less than 4 °, more preferably less than 3 °. Also, as far as the angle is concerned, "+ _ 200831962 means the clockwise direction of rotation, and "-" means the direction of the counterclockwise rotation. Further, the "late phase axis" means the direction in which the refractive index is the largest. Further, the "visible light region" means a range of 380 to 780 nm. Further, the measurement wavelength of the refractive index is 在 in the visible light region (λ = 550 nm) unless otherwise specified. In the description of the present embodiment, the "polarizing plate" is intended to include both a long-length polarizing plate and a polarizing plate of a size incorporated in a liquid crystal device, unless otherwise specified. use. In addition, the term "cutting" as used in this article includes "stamping" and "cutting". Further, in the description of the present embodiment, the "polarizing film" and the "polarizing plate" are used differently. However, the "polarizing plate" means that the polarizing film is protected on at least one side of the "polarizing film". The meaning of the laminate of the transparent protective film. Further, in the description of the present embodiment, the "molecular symmetry axis" refers to the axis of symmetry when it has a molecular axis of symmetry, but does not require the molecular rotational symmetry in a strict sense. In general, in a discotic liquid crystalline compound, the molecular symmetry axis is identical to the axis passing through the center of the disk surface and perpendicular to the disk surface; in the rod-like liquid crystal compound, the molecular symmetry axis and the long axis of the molecule Consistent. Further, in the present specification, Re(λ) and Rth(λ) each indicate hysteresis in the plane into which the wavelength is entered and hysteresis in the thickness direction. (Re) is such that in the KOBRA 2 1 AD Η or WR (Prince Measurement Machine Co., Ltd.), the light of the wavelength λ is incident on the 値 measured by the normal direction of the film. In the case where the film to be measured represents a one-axis or two-axis refractive index round body of 200831962, Rt h ( λ ) is calculated in accordance with the following method.

Rth ( Λ ) is used as the tilting axis (rotating axis) for the in-plane slow phase axis (determined according to K〇BRA 21 AD Η or WR) (in the case of no slow phase axis, any direction in the film plane) In the normal direction of the film as the rotation axis, the Re (λ) of the light of the wavelength λ nm incident from the oblique direction is measured at a step of every 10 degrees from the normal direction to 50 degrees on one side. ) 'A total of 6 points were measured, based on the measured hysteresis 値, the assumption of the average refractive index 及, and the input film thickness 値, calculated by KOBRA21ADH or WR f . In the above, in the case of a film having a direction in which the hysteresis at a certain inclination angle is zero from the normal direction, the in-plane hysteresis axis, and the hysteresis of the angle larger than the inclination angle After the sign is changed to negative, it is calculated by KOBRA21ADH or WR. In addition, the retardation axis (rotation axis) can be used as the axis of inclination (rotation axis in the case where there is no slow phase axis), and the hysteresis 测定 can be measured from any two inclination directions, based on the 値, The assumption of the average refractive index 値 (and the film thickness of the input 値, R th is calculated according to the following formulas (A) and (B).

Re(^)1 ny r\z (nysin(sin !)-) )}2 + (nz cos(sm )}a _d_ an i sin (-Θ) cos {sin (-)} nx (A) Further, R e ( 0 ) is a hysteresis 方向 which is inclined from the normal direction by an angle of 0. 200831962 Further, η x in the formula (A) represents the refractive index in the in-plane slow axis direction, and ny represents The refractive index perpendicular to the ηχ* direction in the in-plane, ηζ indicates the refractive index in the direction of ηχ and ny, and d represents the film thickness.

Rth = ((nx + ny)/2— nz)xd............. (B) When the measured film cannot be expressed in an elliptical body with a refractive index of 1 or 2 axes, it does not matter. In the case of a film of an optical axis (optic ax is), Rth (λ) is calculated in accordance with the following method.

Rth(A) is the in-plane slow axis (determined according to KOBRA 21ADH or WR) as the tilt axis (rotation axis), from -50 degrees to +50 degrees with respect to the film normal direction, at every 1 degree Steps, respectively, measuring the above-mentioned R e ( λ )' of the light incident on the wavelength λ nm from the oblique direction thereof, and measuring 11 points based on the measured hysteresis 値, the average refractive index, and the input film Thickness 値, calculated by KOBRA 21ADH or WR. Further, among the above-mentioned measurements, the assumption of the average refractive index can be obtained by using a polymer handbook (JOHN WILEY & SONS, INC) and a catalogue of various optical films. The fact that the average refractive index is unknown to others can be measured by an Abbe refractometer. The average refractive index of the main optical films is as follows: deuterated cellulose film (1·4 8 ), ring-fired tobacco polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49) Polystyrene (1 _ 59). By inputting the assumptions of the average refractive index and the film thickness, nx, ny, and πζ are calculated by KOBRA 21ADH or WR. Using this calculated nx, ny, and πζ' further calculate Νζ(ηχ - 10- 200831962 —η z) / ( η x — ny). (Polarizing Plate) The polarizing plate of the present invention is formed by laminating at least a first protective film, a polarizer and a second protective film. <Polar photon> The above-mentioned polarizer is preferably composed of polyvinyl alcohol (PVA) and a dichroic molecule, but it is also possible to use PVA and poly group as described in JP-A-1-248937. A polyethylene-based polarizer obtained by dehydration and dechlorination of vinyl chloride to form a polyene structure and aligning it. Although PVA is a polymer material obtained by alkalizing polyvinyl acetate, for example, it may contain a copolymerizable with vinyl acetate such as an unsaturated carboxylic acid, an unsaturated sulfonic acid, an olefin, or a vinyl ether. ingredient. Further, a modified PVA containing an ethyl acetyl group, a sulfonic acid group, a carbonyloxy group, an alkyloxy group or the like may also be used. The self-regulating degree of the PVA is not particularly limited and may be appropriately selected according to the purpose. For example, from the viewpoint of solubility, etc., it is preferably 80 to 1 〇〇 ί : mol %, more preferably 9 0 〜 1 0 0 mole %. Further, the degree of polymerization of the PVA is not particularly limited and may be appropriately selected according to the purpose, and is, for example, preferably 1, 〇〇〇 10,000 to 10,000, more preferably 1,500 〜 5, 0 0 0 〇 PVA tacticity (syndiotacticity) is not particularly limited and may be appropriately selected according to the purpose. For example, as described in Japanese Patent No. 2978219, it is preferably -11-200831962 55 % or more for the purpose of improving durability; However, as described in Japanese Patent No. 331 7494, it is also preferable to use 45 to 52.5%. After the PVA is thinned, it is preferred to introduce a colorimetric molecule to constitute a polarizer. The method for producing a PVA film is generally preferably a method of casting a film by using a stock solution in which a PVA resin is dissolved in water or an organic solvent. The concentration of the polyvinyl alcohol-based resin in the stock solution is usually 5 to 20% by mass, and the film is formed by casting the stock solution, whereby a PVA film having a film thickness of 10 to 200 μm can be produced. The production of the PVA film can be carried out by the method described in the Japanese Patent Publication No. 334251, the Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The degree of crystallization of the PVA film is not particularly limited and may be appropriately selected according to the purpose. For example, the average degree of crystallinity (Xc) described in Patent No. 3251 073 is 50 to 75 mass. /. For the purpose of reducing the hue variation in the surface, a PVA film having a degree of crystallization of 38% or less as described in JP-A No. 20-2-2362-14 can also be used. The birefringence (??) of the PVA film is preferably small, and a PVA film having a birefringence of 1.0% or less and less than or equal to 10, 10, and 3, which is described in Japanese Patent No. 334251, can be suitably used. However, as described in JP-A-2002-228835, in order to avoid the cutting of the PVA film during stretching and to obtain a high degree of polarization, the birefringence of the PVA film can be set to 0.02 or more. In the case of 〇1 or less, the enthalpy of 200831962 (nx + ny)/2-nz may be set to 0.0003 or more to 〇·〇1 or less as described in JP-A-2002-060505. The in-plane retardation Re of the PVA film is preferably from 0 nm to less than 100 nm, more preferably from about 10,000 nm to less than 50 nm. Further, the retardation Rth of the (film) thickness direction of the PVA film is preferably from 0 nm to 500 nm, more preferably from 0 nm to 300 nm. In addition, the polarizing plate of the present invention can also be suitably used in a PVA film having a 1,2-glycol bond amount of 1.5 mol% or less as described in Japanese Patent No. 3021494, and JP-A-2001-31 6492 The optical foreign matter of 5 micrometers or more described in the publication of the publication is a PVA film of 500 or less per 100 square centimeters, and the hot water cutting temperature spot of the film described in JP-A-2002-0301 63 is 1 in the TD direction. The PVA film of 5 ° C or less may be suitably used in the form of a polyvalent alcohol having a valence of 3 to 6 per liter by mass of glycerin or the like, and a polyvalent alcohol of 15% by mass or more. A PVA film formed by forming a film of a mixture of the plasticizers described. The thickness of the film before stretching of the PVA film is not particularly limited and may be appropriately selected according to the purpose. For example, from the viewpoint of stability of film storage and homogeneity of stretching, it is preferably 1 μm to 1 mm. More preferably 20 to 200 microns. In addition, a thin PVA film having a stress of 10 to 6 times in water when it is stretched 4 to 6 times in water can be used as described in JP-A-2002-23621. The dichroic molecule may suitably be a high-valent iodine ion or a dichroic dye such as | 3 - or I 5 -. Among them, high-priced iodide ions are particularly suitable for use in the present invention. The high-priced iodide ion can be used as described in "Application of Polarizing Plates" (edited by Nagata Aya-13-200831962, published by CMC Materials), or Industrial Materials, Vol. 28, No. 7, pp. 39-45. The solution is immersed in a liquid and/or a boric acid aqueous solution obtained by dissolving iodine in an aqueous solution of potassium iodide to form PVA in an adsorbed or aligned state. In the case where a dichroic dye is used as the dichroic molecule, it is preferably an azo dye. Among them, a disazo dye and a trisazo dye are more preferable. The dichroic dye is preferably a water-soluble substance, and therefore a hydrophilic substituent such as a sulfonic acid group, an amine group or a hydroxyl group is introduced into the dichroic molecule, and is suitably used as a free acid (or an alkali metal salt or an ammonium salt). A salt of an amine. Specific examples of such a dichroic dye are, for example, c·丨_正红37, Congo red (C.丨·正红28), CI Zheng violet 12, c _丨·正蓝90, C·I. Zhenglan 22, CI Zhenglan 1, CI Zhenglan 151, C·丨·正绿1, etc., benzidine, CI Zhenghuang 44, CI Zhenghong 23, C.二·正红79 and other diphenyl urea series, CI Zhenghuang 12, etc., CI Zhenghong 31, etc. dinaphthylamine series, CI Zhenghong 81, C·I. 正紫罗兰 9, C. I. J-acid system such as Zhenglan 78. In addition, for example, it may be C. I. Zhenghuang 8, C. 丨·Zhenghuang 28, C. 丨·Zhenghuang 86, CI Zhenghuang 87, CI Zhenghuang 142, C·丨_ 正橙26, C·I. 正橙39, C.I·正橙72, C·I·正橙106, c·I. 正橙107, C I·正红2, C.丨·正红39, CI Zhenghong 83, C·丨·正红89, C. I·正红240, C· ·正红242, C·I.正红247, C·I. 正紫罗48, C_I·正紫罗兰51, C_I·正紫罗兰98, c_I·正蓝15, C·I.正蓝67, CI Zhenglan 71, C_丨·正蓝98, -14- 200831962 CI Zhenglan 168, CI Zhenglan 202, CI Zhenglan 236, c. I. Zhenglan 249, CI Zhenglan 270, C·丨_正Green 59, CI Zheng Green 85, CI Zheng Brown 44, CI Zheng Brown 106, C. 丨 · Zheng Brown 195, C·I. Zheng Brown 210, CI Zheng Brown 223, C. Ι·正棕224, C. Ι・正黑1, C.丨·正黑17, C. Ι·正黑19, C·Ι·正黑54, etc., and can be used in JP-A-62-70802, JP-A-1-61 Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. And a dichroic dye described in Japanese Laid-Open Patent Publication No. Hei 7-261204. In order to produce dichroic molecules of various hue, it is also possible to blend two or more of these dichroic dyes. In the case of using a dichroic dye, such as special opening As described in 2002 - 0 822 22, the absorption thickness can be 4 micrometers or more. The content of the dichroic molecule in the film is such that when it is too low, the degree of polarization is lowered, and even if it is too large, the transmittance of the veneer is lowered, so that it is relative to the matrix constituting the film. In the case of a polyvinyl alcohol-based polymer, it is usually adjusted to be from 1% by mass to 5% by mass. /. The scope. The film thickness of the polarizer is preferably 5 to 40 μm, more preferably 10 to 30 μm. Further, as described in JP-A-2002-147727, the ratio of the thickness of the polarizer to the thickness of the protective film described later is preferably 〇·0 1 $ A (polarized photon thickness) / B (protective film film) Thickness) The range of $〇·8. <First Protective Film> The first protective film described above is characterized by a moisture permeability of 300 g/m 2 •day at 95 ° C and a relative humidity of -15-200831962 Hereinafter, it is preferably 50 g/m2/day or less, more preferably 1 g/m2/day. The first protective film is not particularly limited as long as it can satisfies the conditions of the moisture permeability, and the transmittance is 80% or more, and can be appropriately selected according to the purpose. For example, a cycloolefin resin or a polyester is suitably used. A transparent film having a coating layer having low moisture permeability is provided on at least one surface of at least one surface of a transparent base film made of deuterated cellulose. Among these, a cycloolefin type resin is particularly preferred from the viewpoint of moisture permeability. <<Trans-humidity>> Here, the measurement method of the moisture permeability can be suitably applied to the "physical properties of polymers" (Polymer Experiment Lecture 4, Kyoritsu Publishing), pages 285 to 294: Vapor Permeation The method described in the measurement of mass (mass method, thermometer method, vapor pressure method, adsorption amount method). However, in the present invention, in addition to changing the humidity control condition to 60 ° C and 95 % R Η, J丨S Z- 0 2 0 8 calculates the moisture permeability. At this time, in the constant temperature and humidity device, the moisture permeable cup is taken out at appropriate time intervals for weighing, and the operation is repeated, and the mass increase per unit time is determined by two consecutive weighings until it becomes within 5%. A certain amount, and then continue to evaluate. Further, in addition to eliminating the influence caused by moisture absorption of the sample, the moisture permeable cup to which the moisture absorbent is not placed is measured to correct the moisture permeability. In the case of measuring the moisture permeability of the polarizing plate protective film having the resin layer containing the vinyl alcohol polymer, the resin layer of the tree-16-200831962 disposed on the transparent substrate film is placed in contact with the measuring cup. For the sample, the moisture permeability of the transparent substrate film side was measured in the same manner as above. <<Coating layer>> The coating layer on the above-described deuterated cellulose substrate is not particularly limited, and may be appropriately selected according to the purpose, for example, a vinyl monomer having a self-containing chlorine can be suitably used. a coating layer of a polymer in which a repeating unit is derived, a coating layer made of a vinyl alcohol polymer, a compound obtained from an alkoxysilane, a compound having a functional group reactive with a hydroxyl group or an alkoxy group, or a decane At least one of the C' mixture is used as a coating layer composed of a main component, a coating layer containing a coating composition containing polysiloxane, a coating layer containing a hydrophobic compound, a coating layer containing a hydrophobic compound, and a sugar layer. A coating layer formed by laminating a resin composition composed of a mercapto group-containing compound, and a resin composition composed of an amine group-containing polymer compound and an amine-containing reactive functional group-containing decyl group-containing organodecane compound The coating layer and the coating layer containing the inorganic layered compound having a particle radius of 〇1 to 10 μm. Among these, a coating layer of a polymer of a repeating unit derived from a chlorine-containing vinyl monomer and a coating layer composed of a vinyl alcohol i-based polymer are preferably used. [Chlorine-containing vinyl monomer] A chlorine-containing vinyl monomer is generally 'exemplary', for example, it may be vinyl chloride or vinylidene chloride. The chlorine-containing polymer can be obtained by copolymerizing a vinyl chloride or vinylidene chloride monomer with a monomer copolymerizable therewith. [Monomer capable of copolymerizing with a chlorine-containing vinyl monomer] -17- 200831962 A monomer capable of copolymerizing with a chlorine-containing vinyl monomer, for example, it may be from an olefin, styrene Classes, acrylates, methacrylates, acrylamides, methacrylamides, itaconic acid diesters, maleates, fumaric acid diesters, N-alkyl mala A single selected from the group consisting of quinone imines, maleic anhydride, acrylonitrile, vinyl ethers, vinyl esters, ketenes, ethylene heterocyclic compounds, glycidyl esters, unsaturated nitriles, and unsaturated carboxylic acids body. Examples of the olefins may be, for example, dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, isoprene, chloropentadiene, butadiene, 2, for example. 3-dimethylbutadiene and the like. Styrenes, for example, may be styrene, methyl styrene, dimethyl ethylene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, Alkyl styrene, ethoxylated styrene, chlorostyrene, dichlorostyrene, bromostyrene, trifluoromethylstyrene, vinyl benzoic acid methyl ester, and the like. Specific examples of the acrylates and methacrylates may, for example, be methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, Octyl acrylate, t-octyl acrylate, 2-methoxyethyl acrylate, 2-butoxyethyl acrylate, 2-phenoxyethyl acrylate, chloroethyl acrylate, cyanoethyl acrylate, dimethyl acrylate Ethyl amyl ethyl ester, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate ,methacrylic acid-18- 200831962 butyl ester, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, benzyl methacrylate, cyanoacrylate Ethyloxyethyl ester, chlorobenzyl methacrylate, propyl propyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2-methoxyethyl methacrylate, A 2-(3-phenylpropoxy)ethyl acrylate, Dimethylpentylphenoxyethyl acrylate, furan methyl methacrylate, tetrahydrofuran methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, hydroxyethyl methacrylate Ester, hydroxypropyl acrylate, isopropyl hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, 2,2-dimethyl hydroxy acrylate Propyl ester, 5-hydroxypentyl acrylate, diethyl acrylate monoacrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, methyl 5-hydroxypropyl acrylate, diethylene glycol monomethacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, and the like. Further, specific examples of the vinyl ethers may, for example, be methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, mercapto vinyl ether, ethylhexyl vinyl ether, or Oxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl ether, dimethyl pentane Ethyl vinyl ether, diethyl amyl ethyl vinyl ether, butyl amyl ethyl vinyl ether, benzyl vinyl ether, tetrahydrofuran methyl vinyl ether, vinyl phenyl ether, vinyl tolyl ether, vinyl Chlorophenyl ether, ethylene-2,4-dichlorophenyl ether, ethyl 4-naphthyl ether, ethyl; alkenyl nonyl ether. Further, specific examples of the vinyl esters may, for example, be -19-200831962 vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl dimethyl propionate, Ethyl butyric acid vinyl ester, vinyl valerate, vinyl hexanoate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butyrate, vinyl phenyl acetate Ethyl vinyl acetate, vinyl lactate, vinyl -3-phenylbutyrate, vinyl cyclohexylcarboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorate, tetrachlorobenzoic acid Vinyl ester, vinyl naphthate, and the like. Acrylamides, for example, may be acrylamide, methacrylamide, ethyl acrylamide, propyl acrylamide, butyl acrylamide, t-butyl acrylamide , cyclohexyl acrylamide, benzyl acrylamide, hydroxymethyl acrylamide, methoxyethyl acrylamide, dimethylamine ethyl acrylamide, phenyl acrylamide, dimethyl methacrylate Amine, diethyl acrylamide, cold-cyanoethyl acrylamide, N-(2-acetamidoethoxyethyl) acrylamide, and the like. The methacrylamide amines, for example, may be methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methyl propyl, ene amide, butyl methyl Propylene decylamine, t-butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacrylamide, dimethyl Base amine ethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, cyanoethyl methacrylamide, N-(2- Ethyl ethoxylated ethyl) methacrylamide or the like. Further, an acrylamide having a hydroxyl group may also be used, and such an example may, for example, be N-hydroxymethyldimethyl-3--20-200831962 pendant oxy-butyl)propene. Indoleamine, N-methylol acrylamide, N-methylol methacrylamide, N-ethyl-N-hydroxymethyl acrylamide, N,N-dimethylol decylamine, N _ Ethanol acrylamide, N-propanol acrylamide, N-methylol acrylamide, and the like. The ikonic acid diesters may, for example, be dimethyl ikonate, diethyl itaconate, dibutyl itaconate or the like. The maleic acid diester, for example, may be diethyl maleate, dimethyl maleate, dibutyl maleate or the like. The fumaric acid diesters may, for example, be diethyl fumarate, dimethyl fumarate, dibutyl fumarate or the like. The ketenes may, for example, be methyl ketene, phenyl ketene, methoxyethyl ketene or the like. The ethylene heterocyclic compound may, for example, be vinyl pyridine, N-vinylimidazole, N-vinyl thioxanthone, N-ethylene triazole, N-vinylpyrrolidone or the like. The glycidyl ester may, for example, be glycidyl acrylate, glycidyl methacrylate or the like. The unsaturated nitrile, for example, may be acrylonitrile, methacrylonitrile or the like. The N-alkyl maleimide, for example, may be, for example, N-ethyl maleimide, N-butyl maleimide or the like. The unsaturated carboxylic acid, for example, may be acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, etc.; moreover, such as fumaric acid, itaconic acid, and Malay An anhydride such as an acid. Further, it is also possible to use two or more such copolymerizable monomers. In the case of the chlorinated polymer in the present invention, it is disclosed in Japanese Laid-Open Patent Publication No. SHO-A No. SHO-A No. Hei. Japanese Laid-Open Patent Publication No. Sho 57-1 39 1/36, JP-A-KOK-A-60- 2 3 5 8 8 8 , JP-A-6-101, No. 62-256871, JP-A-62-256871 JP-A-62-280207, JP-A-6-256665, and the like are described above. In the chlorine-containing polymer, the proportion of the chlorine-containing ethylene monomer is preferably 50 to 9.9 mass. /〇, more suitable is 6 0~9 8 quality. /. More ideally, 7 0 to 9 7 mass%. When the proportion of the chlorine-containing ethylene monomer is 50% or more, it is not suitable for the deterioration of moisture permeability, and if it is 99% or less, the solubility of each solvent can be obtained. So it is ideal. The chlorine-containing polymer system is commercially available from Asahi Kasei Chemicals Co., Ltd. and Wu Yu Chemical Company. For example, "Sharon Resin R24 1 C", "Sharon Resin F2 16", "Sharon Resin R2 04", "Sharon Latex L502" can be purchased from Asahi Kasei Chemicals Co., Ltd. "Sharon Latex L529B", "Sharon Latex L5 3 6B", "Sharon Latex L544D", "Sharon Latex L549B", "Sharon Latex L551B", "Sharon Latex L557", "Sharon Latex" L561A", "Sand C, Latex Latex L116A", "Sharon Latex L411A", "Sharon Latex L120", "Sharon Latex L123D", "Sharon Latex L106C", "Sharon Latex L131A", "Shalang Latex L111", "Sharon Latex L2 32A" and "Sharon Latex L321B". Since the above-mentioned coating layer has many examples of wet coating, the use of a solvent in the coating composition is a particularly important factor. The necessary conditions include, for example, sufficient dissolution of the above-mentioned solute, difficulty in coating unevenness during coating-drying, uneven drying, and the like. Further, the transparent substrate-22-200831962 does not have too high solubility of the film (preventing the deterioration of planarity and whitening, etc.), and conversely, the support is dissolved and expanded (the need for adhesion) ) is also a suitable feature. Although the solvent may be one type, it is particularly preferable to use two or more kinds of solvents to adjust the solubility and expandability of the support, the solubility of the material, the drying characteristics, the aggregability of the particles, and the like. By adding a small amount of solvent having a high expansion property to the main solvent having a low expansion property with respect to the transparent support, it is possible to prevent deterioration of other properties and surface properties, and to increase the density of the transparent support (transparent base film). Synergy. The coating liquid may contain an organic solvent such as a ketone system, an alcohol system, an ester system or an ether system. Preferred organic solvents are tetrahydrofuran, ketones (methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, etc.), ethyl acetate, and butyl acetate. It is also suitable to use BTX such as toluene. In the present invention, in the case where the chlorine-containing polymer is vinylidene chloride, the main solvent is preferably tetrahydrofuran. Further, by selecting a copolymer of vinylidene chloride, it can be dissolved in toluene or a ketone solvent; more preferably, toluene or a ketone solvent is used without using tetrahydrofuran. Further, it is also suitable to use a solvent in which the solvent is added in a range in which the solute is dissolved in tetrahydrofuran. Further, in the case where a chlorine-containing polymer is supplied as a latex dispersion, water is preferably used as a main solvent. In the case of a latex dispersion, it is preferred to use a surfactant or a tackifier. In the case where a coating layer containing a chlorine-containing polymer is applied to a transparent base film, in order to improve the blocking resistance, it is also preferable to use 相对·2 to 1 with respect to the chlorine-containing polymerization-23-200831962. · 0% of the Irisia (made by Fuji Silisia Co., Ltd.), a fine powder such as Kasuga (made by Mizusawa Chemical Industry Co., Ltd.), Neptune (made by Nippon Kasei Co., Ltd.), etc.; or add 0.2~5.0 A wax emulsion of a paraffin wax (manufactured by Nippon Seiko Co., Ltd.), behenic acid (manufactured by Nippon Oil Co., Ltd.), or stearic acid (manufactured by Sakamoto Oil Co., Ltd.). Further, the modified wax described in paragraphs [0012] to [0016] of JP-A-9-143419 is also suitably used. Since the chlorine-containing polymer is decomposed and colored by heat, light, or ultraviolet rays, it is preferably used together with stabilizers such as stearic acid, silver salts, and magnesium oxide such as lead, zinc, and barium. Further, an antioxidant as described in paragraphs [13] to [0020] of JP-A-2004-359819 may be used. Further, in order to improve the adhesion between the coating layer including the chlorine-containing polymer and the transparent base film, and other layers, it is also suitable to use 添加·1 to 1.0 parts relative to the chlorine-containing polymer. An isocyanate-based adhesive such as Klenet L (manufactured by Nippon Polyurethane Co., Ltd.) or Teknett Α3 (manufactured by Takeda Pharmaceutical Co., Ltd.). Although the coating method is not particularly limited, it may be by dip coating method, air knife coating method, curtain coating method, roll coating method, wire-rod coating method, gravure coating method, or extrusion coating method (die coating). A well-known method, such as the method of the U.S. Patent No. 2,668,242, and the micro gravure coating method, among these, from the viewpoint of high productivity and uniformity of the coating film, A micro gravure coating method or a die coating method is suitable. The drying condition is preferably such that the concentration of the organic solvent in the coating liquid film is 5% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less after drying in the dry-24-200831962. Although the drying conditions are affected by the heat strength and the conveying speed of the transparent base film, the length of the drying step, and the like, it is preferable to make the content ratio of the organic solvent as much as possible from the viewpoint of film hardness and adhesion prevention. The lower the better. In the case where the organic solvent is not contained, the drying step may be omitted, and ultraviolet irradiation may be performed immediately after the application. The thickness of the coating layer is preferably from 1 to 10 μm, more preferably from 2 to 9 μm, still more preferably from 3 to 8 μm. When the thickness is 1 μm or less, the moisture resistance is deteriorated; when the thickness is 1 μm or more, a brittle film is formed and it becomes easy to be colored, and thus it is not suitable as a polarizing plate protective film. The haze of the layer is preferably 5% or less, more preferably 3% or less, more preferably 1% or less, and the ratio of surface haze to internal haze is not particularly limited and may be appropriately selected according to the purpose, but the surface is The haze is preferably 1% or less. [Coated layer formed of a vinyl alcohol polymer] The vinyl alcohol polymer constituting the coating layer may be, for example, a single polymerization of polyvinyl alcohol (PVA) or the like. And ethylene-vinyl alcohol copolymer (EVOH), etc. Further, these vinyl alcohol-based polymers may be partially modified by carbonyl, decyl alcohol, epoxy modified, acetamidine. A copolymer of an ethylene group, an amine group or an ammonium compound may be used, and a copolymer containing a dipropanone ketone acrylamide unit or the like may be used in a part thereof. Further, various vinyl alcohol polymers Can be used alone, or can be -25- 200831962 It can be used in combination of two or more. The degree of gradation of the vinyl alcohol polymer can be selected from the range of 80 mol%, but it is preferably 96 mol% or more, more preferably 99 mol. The above polymerization degree of the vinyl alcohol polymer is preferably from 200 to 5,000 in terms of moisture permeability and coatability, and is preferably from 300 to 5,000, more preferably from 300 to 3,000. In the present invention, the inorganic layered compound is a structure in which a unitary crystal layer is laminated, and the interlayer is coordinated by the layer. Or an inorganic compound which exhibits swelling or cracking properties by absorbing a solvent. As an inorganic compound like this, it may be, for example, a swellable aqueous citrate, for example, a smectite clay mineral (montmorillonite, g stone, hectorite, etc.), brown garnet (pa丨mqurite) group of clay minerals, kaolin clay minerals, strontium silicate (mica, etc.). Also, it is suitable to use synthetic inorganic layered compounds as synthetic inorganic The layered compound, for example, may be synthetic smectite (montmorillonite, vermiculite, stilpnsaite, etc.), synthetic mica, etc.; preferably smectite, montmorillonite, mica; It is more preferably montmorillonite or mica; more preferably mica. Among them, from the viewpoint of reducing moisture permeability and suppressing the adhesion of color, it is particularly preferable to synthesize vermiculite. Further, such an inorganic layered compound is also It may be obtained by subjecting the inorganic layered compound to an organic treatment. The swellable inorganic layered compound has two properties such as gas barrier property and adhesion between the substrate and the gas barrier layer. The swellable inorganic layered compound which has been subjected to the granulation treatment is usually in the form of a flat or flat shape, and the planar shape is not particularly limited, and may be unequal. The flat diameter of the swellable inorganic layered compound (average particle diameter of the planar shape), for example, is preferably 〇·1 to 1 〇 micrometer is preferably 〇. 5 to 8 μm, more preferably 0.8 〜 6 microns. When the particle diameter is smaller than this, the effect of reducing the moisture permeability is not sufficient; when the particle diameter is larger than the range, the haze is increased, the surface roughness is increased, and the like, which is not preferable. The concentration of the inorganic compound is preferably from 3 to 60% by mass, more preferably 3% by mass, still more preferably from 3 to 40% by mass. When the concentration of the inorganic compound is 3% by mass, the effect of reducing the moisture permeability is insufficient. When the inorganic compound concentration is more than 60% by mass, the haze is increased, the brittleness is deteriorated, and the like, which is not preferable. In the present invention, it is possible to use a vinyl alcohol polymer and a layered inorganic

Further, a cross-linking agent of a vinyl alcohol-based polymer is added as a component of the composition, whereby the water resistance of the adhesive layer can be improved. The above-mentioned crosslinking agent is not particularly limited and may be selected according to the purpose, and for example, it may be a phenol resin, a melamine resin, a polyamine polyurea, a dimethylol urea, a dihydroxyl group. A melamine, a polyvalent compound, a dialdehyde compound, a polyvalent isocyanate resin, an oxirane compound, a polyamidoamine alcohol compound, an activated vinyl compound, and a two-carbon micronizer are plate-shaped homogenized, more widely, Then ~50 is a small substance and thus the compound resin is appropriate, urea epoxide ester -27-200831962 compound, thiol-containing compound (polyvalent carboxylic acid polyvalent compound), colloidal vermiculite, chromium salt, polyvalent metal salt, boric acid a titanium compound such as phosphoric acid, polyacrylic acid, dicarboxylic acid, adipic anhydride, succinic anhydride, tetraisopropyl titanate or diisopropoxy bis(acetonitrile) titanate; A coupling agent such as 3-glycidylpropyl methoxy decane or a radical generator such as a peroxide can also be used. Further, a catalyst for promoting a crosslinking reaction and other additives may be added. The amount of the crosslinking agent to be added is preferably 0.5% by mass or more, and more preferably 1% by weight based on (crosslinking agent / (vinyl alcohol polymer + crosslinking agent)). /. The above is particularly preferably 2% by mass or more. The mass ratio of the crosslinking agent is less than 0.5 mass with respect to both the PVA-based polymer and the crosslinking agent. /. In the case of this, the effect of adding a crosslinking agent cannot be exhibited. The mass ratio of the crosslinking agent is preferably 50% by mass or less, more preferably 40% by mass, based on both the vinyl alcohol polymer and the crosslinking agent. /. Hereinafter, it is more desirable to be 30% by mass or less. Among the crosslinking agents such as the aldehyde compound, since there is a substance which turns yellow due to heat, it is necessary to reduce the amount of the crosslinking agent to reduce the discoloration to the allowable range. Inside. A method of forming a coating layer made of a vinyl alcohol polymer or a vinyl alcohol polymer and an inorganic layered compound may be a dip coating method, an air knife coating method, a curtain coating method, a roll coating method, or a line- Among the above-mentioned methods, such as a rod coating method, a gravure coating method, or an extrusion coating method (mold coating method) (refer to the specification of US Pat. No. 2,668,242), a micro gravure coating method, and the like, From the viewpoint of high productivity and uniformity of the coating film, it is suitable to use a micro-gravure -28-200831962 printing coating method or a die coating method. In this case, in order to optimize the liquid viscosity of the coating device at the time of film formation, a viscosity adjusting agent such as a tackifier may be added to the coating liquid to adjust the liquid viscosity of the coating liquid. Further, in order to further improve the moisture permeability and the water resistance of the coating layer, it is preferred to apply the coating layer on the deuterated cellulose-based substrate, and then carry out the coating at 90 ° C or more and 150 ° C or less for several minutes. The heat treatment is more preferably heated at 1 30 ° C or higher and 1 50 ° C or lower. The heat treatment time is preferably from 1 minute to 20 minutes, more preferably from 5 minutes to 15 minutes, from the viewpoint of productivity and water resistance. Further, from the viewpoint of the adhesion between the resin and the cellulose-deposited cellulose substrate, it is preferred to subject the deuterated cellulose to an alkalization treatment in advance. The thickness of the coating layer is preferably from 1 to 10 μm, more preferably from 2 to 9 μm, still more preferably from 3 to 8 μm. <<Polyester-based resin>> The polyester-based resin is not particularly limited and may be appropriately selected according to the purpose. For example, it may be polyethylene terephthalate or polynaphthalene. Ethylene dicarboxylate, polybutylene terephthalate, polybutylene naphthalate, and the like. Among these, it is particularly preferable to use polyethylene terephthalate from the viewpoint of cost and mechanical strength. Among them, a particularly desirable material is a resin obtained by subjecting an aromatic dicarboxylic acid and an aliphatic diol to polycondensation. As the aromatic diacid, in addition to terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, or the like may be used, and such lower alkyl esters (anhydrides, lower alkyl esters, etc.) may be used. An ester derivative can be formed). -29- 200831962 The aliphatic diols are ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,4-cyclohexanol, diethylene glycol, and P-dimethyl glycol. Among them, polyethylene terephthalate obtained by reacting terephthalic acid and ethylene glycol is preferably used as a main component. The main component is polyethylene terephthalate, which means that the repeating unit of polyethylene terephthalate accounts for 80% by mass or more of the copolymer, or in the case of blending, it contains 80% by mass or more of the pair. Ethylene phthalate. The polyester used in the protective film may be further copolymerized with other components or may be blended with other polymers within a range not impairing the effects of the present invention. The aforementioned polyester, for example, may be a monofunctional compound such as benzoic acid, benzalkonium benzoate, benzyloxybenzoic acid or methoxypolyalkylene glycol, which blocks the terminal hydroxyl group and Any one of the carboxyl groups, or, for example, a compound having a very small amount of a trifunctional or tetrafunctional ester such as glycerin or pentaerythritol, and a substantially linear copolymer can be obtained. Modified inside. Further, in order to enhance the heat resistance of the film, the polyester used in the present invention may be copolymerized with a bisphenol compound or a compound having a naphthalene ring or a cyclohexane ring. Further, the glass transition temperature (Tg) of the polyester used in the present invention is preferably 80 ° C or more, more preferably 90 ° C or more. When the film is less than 80 ° C, the dimensionality under high temperature and high humidity may be deteriorated. The T g is obtained from the peak of tan 5 measured by dynamic viscoelasticity. -30- 200831962 The polyester used in the present invention may also contain an antioxidant. In particular, in the case where the polyester is a compound having a polyoxyalkylene group, the effect is particularly remarkable. The antioxidant to be contained is not particularly limited, and various antioxidants can be used. For example, it may be an antioxidant such as a hindered phenol compound, a phosphite compound or a thioether compound. . Among them, from the viewpoint of transparency, it is preferably an antioxidant of a hindered phenol compound. The content of the antioxidant is usually from 0.01 to 2% by mass, more preferably from 0.1 to 0.5% by mass, based on the total amount of the polyester. In the above polyester film, slipperiness can be imparted as needed. The means for imparting the slipperiness is not particularly limited. However, it is generally a method of adding an external particle to which an inert inorganic particle is added to a polyester, a method of depositing an internal particle which precipitates a catalyst to be added when synthesizing a polyester, or A method of coating a surfactant on a surface of a film or the like. In the polyester film, in order to prevent deterioration of the polarizer and the liquid crystal, an ultraviolet absorber may be added as needed. From the viewpoint of excellent ultraviolet absorbing ability and good liquid crystal display property, as the ultraviolet absorbing agent, it is preferred that the polyester film to which the ultraviolet absorbing agent is added has a transmittance of 0 to 50 at a wavelength of 380 nm. %, more preferably 〇~ 30%, more ideally 〇~1 〇%. Further, the penetration rate at 600 nm is preferably 80 to 100%, more preferably 8 5 to 1 〇 〇 %, and more desirably 9 0 to 1 0 0 %. The polyester film is preferably a polyester film formed by biaxial stretching. In the case of the above polyester film, it can be carried out by a known method. In this case, the longitudinal direction means the film forming direction (long axis direction) of the film, and the horizontal direction 200831962 is the direction perpendicular to the film forming direction of the film. First, the raw material polyester is formed into a nine-grain shape, dried by hot air or vacuum dried, then melt-extruded, and extruded into a sheet shape by a τ mold, and adhered to a cooling roll by an electrostatic application method or the like to be solidified by cooling. An unstretched sheet is obtained. Next, the obtained unstretched sheet is heated to a glass transition temperature (Tg) of the polyester film to (Tg + 100) ° C by at least one of a plurality of roll groups and a heating device such as infrared heating. Within the range, one or more longitudinal stretching methods are performed. Next, the polyester film was stretched in the longitudinal direction obtained by the above-described method, and transversely stretched in a temperature range of Tg to Tm (melting point), followed by heat setting. The heat-fixed film is usually cooled to below Tg, and the jaw holding portions at both ends of the film are cut and taken up. In this case, it is preferable to carry out a relaxation treatment of 0.1 to 1 〇 % in at least one of the lateral direction and the longitudinal direction in a temperature range of not more than the final heat-fixing temperature or more than Tg. The means for cooling and relaxation treatment is not particularly limited, and it can be carried out by a conventionally known means. However, from the viewpoint of improving the dimensional stability of the film, it is particularly preferable to carry out the cooling while sequentially cooling the plurality of temperature regions. deal with. The conditions suitable for the heat setting conditions and the cooling relaxation treatment conditions are different depending on the polyester constituting the film, and the physical properties of the obtained stretched film may be measured and adjusted according to appropriate adjustment. The way the feature is decided. Further, in the production of the above film, a functional layer such as an antistatic layer, a slippery layer, an adhesive layer or a barrier layer may be applied at least one time before and after stretching from -32 to 200831962. At this time, various surface treatments such as corona discharge treatment, atmospheric piezoelectric slurry treatment, and chemical liquid treatment can be carried out as needed. The clamp holding portion at both ends of the cut film may be used as a film of the same type after being subjected to pulverization treatment or, if necessary, granulation treatment, depolymerization, repolymerization, or the like. Raw materials or raw materials for different types of film. The thickness of the polyester film is preferably 5 to 200 μm, more preferably 5 to 1 1 μm, and more desirably 40 to 100 μm. [Adhesion to polarizer] The adhesive surface between the polyester resin and the polarizer can be lifted as needed. Representative examples of such a treatment are, for example, a drying treatment and an easy adhesion treatment. Specific examples of the drying treatment are, for example, corona treatment, gas corona treatment, plasma treatment, low pressure UV treatment and the like. Examples of easy-to-adhere treatments, for example, coating easy-to-adhere materials. The adhesive material may be, for example, a fiber-based resin, a virgin resin, a sand compound coupler, a sand base, a PVA, a nylon, a styrene resin, or the like. Drying and easy adhesion treatment can also be used together. Alternatively, the adhesion can be improved by alkalizing with an aqueous solution of sodium hydroxide. The alkalization treatment can also be used together with the easy adhesion treatment. <<Polycarbonate-Based Resin>> The polycarbonate-based resin used in the present invention means a polyester between a carbonic acid and a diol or a valence phenol of 2 -33 - 200831962, of course, including carbonic acid and 2,2 '-bis(4-hydroxyphenyl)-propane (generally referred to as bisphenol A) is an aromatic polycarbonate of a structural unit, and is not unquestionably limited in the present invention, for example, it may Is from 1,1-bis(4-hydroxyphenyl)-alkylcycloalkane, 1,1-bis(3-substituted-4-hydroxyphenyl)-alkylcycloalkane, 1,1-di (3) , 5-substituted-4-hydroxyphenyl)-alkylcycloalkane, 9,9-bis(4-hydroxyphenyl) olefin, at least one selected from the group consisting of divalent phenols as a monomer component Or a copolymerized polycarbonate, a mixture of the above-mentioned bis- and bis-A as a monomer component, a copolymerized polycarbonate having the above-mentioned divalent hydrazine and bisphenol A as a monomer component ester. Specific examples of 1,1-bis(4-hydroxyphenyl)-alkylcycloalkane, for example, 1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane 1, 彳 bis(4-hydroxyphenyl)-3,3-dimethyl-5,5-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3- Dimethyl-5-methylcyclopentane and the like. It can be used as 1,1-bis(3-substituted-4-hydroxyphenyl)-alkylcycloalkane as 彳j-double (4_ substituted by an alkyl group having 1 to 12 carbon atoms and a halogen group. Hydroxyphenyl)-alkylcycloalkane; for example, it may be 1,1-bis(3-methyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1_bis(3-ethyl-4-hydroxyphenyl)·3,3-dimethyl-5,5-dimethylcyclohexane, 1,1-bis(3-chloro-4-hydroxyl Phenyl)-3,3-dimethyl-4-methylcyclopentanol, 1,1-bis(3-bromo-4-hydroxyphenyl)-3,3-dimethyl-5-methyl ring Pentane and the like. It can be used as a 1,1 -bis(3,5-substituted-4-hydroxyphenyl)-alkylcycloalkane which is substituted with an alkyl group having 1 to 12 carbon atoms and a halogen group, > - bis(4-hydroxyphenyl)-alkylcycloalkane; for example, it may be 1,1-bis(3-methyl-4-hydroxy-34-200831962phenyl)-3,3, 5-trimethylcyclohexane, 1,1-bis(3,5-dichloro-4-hydroxyphenyl)-3,3-dimethyl-5-methylcyclohexane, 1,1-double (3-ethyl-5-methyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-3,3-dimethyl-5-methylcyclohexane Alkane, etc. It can be used as a 9,9-bis(4-hydroxyphenyl) olefin, for example, it can be 9,9-bis(4-hydroxyphenyl)anthracene, 9,9-bis(3- Indole-4-hydroxyphenyl) anthracene, 9,9-bis(3-ethyl-4-hydroxyphenyl)anthracene, and the like. Further, other bisphenol components may be used; for example, it may be 2,2'-bis(4-hydroxyphenyl)propane (bisphenol A), 4,4'-(α-methyl group Benzylidene bisphenol, bis(4-hydroxyphenyl)methane, 2,2'-bis(4-hydroxyphenyl)butane, 3,3'-bis(4-hydroxyphenyl)pentane, 4 , 4'-bis(4-hydroxyphenyl)heptane, 4,4'-bis(4-hydroxyphenyl)2,5-dimethylheptane, bis(4-hydroxyphenyl)methylphenyl Methane, bis(4-hydroxyphenyl)diphenylmethane, 2,2'-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl) 4) fluorophenylmethane, 2,2'-bis(3-fluoro-4-hydroxyphenyl)propane, bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2'- Bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(3,5-dimethyl-4-hydroxyphenyl)phenylethane, bis(3-methyl-4-hydroxybenzene) Diphenylmethane or the like; these may be used singly or in combination of two or more. The above polycarbonate contains, in addition to the above-mentioned bisphenol, a polyester carbonate containing a conjugated monomer having a small amount of an aliphatic or aromatic diacid as an acid component. It can be used as an aromatic dicarboxylic acid, for example, for citric acid, iso-35-200831962 decanoic acid, p-xylene diol, bis(4-phenylene)-methyl, 1,1 '_Bis(4-phenyl)-ethane, 1,1 bis(4-hydroxyphenyl)-butane, 2,2 bis(4-hydroxyphenyl)-butyl or the like. Among these, it is more suitable for citric acid and isophthalic acid. The polycarbonate used has a viscosity average molecular weight of preferably from 2, 〇〇〇 100,000, more preferably from 5,000 to 70,000, more preferably from 7,000 to 50,000 °, in a dimethyl chloride solution having a concentration of 0.7 g/dL. The specific viscosity measured at 20 t; is preferably 0.07 to 2.70, more preferably 0.15 to 1.80, more preferably 0.20 to 1.30. Insofar as the average molecular weight of the viscosity is less than 2, it is not suitable because the obtained film becomes brittle; and in the case of 10 〇 or more, it is difficult to be difficult due to the processability of the film. . In the polycarbonate resin, an ultraviolet absorber may be added as needed in the same manner as the polyester resin. Further, in order to enhance the adhesion between the polarizers and the polarizers, drying treatment and easy adhesion treatment can be carried out. The method for producing a film from a polycarbonate resin may be, for example, a solution casting method, a melt extrusion method, or the like; however, it is preferably excellent in thickness uniformity, no gelation, bulging, fish eyes, A method of optical defects such as scratching. <<Cycloolefin-based resin> The term "cycloolefin-based resin" means, for example, a unit composed of a cyclic olefin (cycloolefin) such as a decene- or a polycyclic norbornene-based monomer. Thermoplastic resin. The cycloolefin-based resin may be a cyclic olefin and a chain, in addition to a ring-opening polymer of a cyclic olefin, 36-200831962 or a hydride of a ring-opening polymer obtained by using two or more kinds of cyclic olefins. An olefin or an aromatic addition copolymer having a vinyl group. The decene-based resin is one which has a decylene skeleton in the repeating unit, and is disclosed, for example, in Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei. Known resin. In the present invention, it may be suitably used in a conventionally known decene-based resin; for example, 'which may be a ring-opening polymer hydride of a reduced-flammable monomer, valerene f: Addition polymer between body addition polymer, norbornene monomer and olefin monomer such as ethylene or α-olefin; norbornene monomer and cyclopentene, cyclooctene, 5, 6 An addition polymer of a cyclic olefin monomer such as dihydrodicyclopentadiene or a modified product of the polymer. The above-mentioned tear-reducing monomer, for example, may be a norbornene, 5-methyl-2-northene, 5-ethyl-2-northene, 5-butyl-2 -Danfan_, 5-ethylidene-2-norbornene, 5-methoxycarbonyl-2-northene, 5,5-dimethylnordecene, 5-cyano-2 -nordecene , 5-methyl-5-methoxycarbonyl-2-northene, 5-phenyl-2-northene, 5-phenyl-5-methyl-2-northene, ethylene-tetracyclic Copolymer, 6-methyl-1,4: 5,8-dimethyl-1,4,43,5,6,7,8,83-octahydronaphthalene, 6-ethyl-1,4: 5,8-monomethyl-1,4,43,5,6,7,8,83-octahydronaphthalene, 6-methyl-1,4:5,8-ethylene-1,4,4a ,5,6,7,8,8a-octahydronaphthalene, 6-chloro-1,4: 5,8-dimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalene , 6 · cyano μ, 4: 5,8-dimethyl-1,4,43,5,6,7,8,83-octahydronaphthalene, 6-pyridyl-1,4:5,8- Monomethyl-1,4,43,5,6,7,8,83-octahydronaphthalene, 6-methoxyl base_1,4:5,8_-37- 200831962 1,4-dimethyl- 1,4,4a,4b —^A-1,4,43,5,6,7,8,83-octachloronaphthalene, 1,4- a, 5,8,8a-octahydro-2.3-

5,8,8a,9a-octahydronaphthalene, 5,8-methyl-i,2,3,4,4a cyclopentaphthalene, 4,9: -1H-phenylene terene, 4,11 : 5,10 : 9,9 a,1 0,1 0 a,1 1,1 1 a-dodecane-1 η-quinone. The method for polymerizing the above-described norbornene-based monomer may be a known method, and may be copolymerized with other copolymerizable monomers as needed, or may be hydrogenated to form a decene-based polymer hydride. . Further, it is also possible to use an α, an oxime-unsaturated carboxylic acid and a derivative thereof, a styrene-based hydrocarbon, an odorary unsaturated bond, and an organic ruthenium compound having a hydrolyzable group, and an unsaturated method by a known method. An epoxy monomer or the like is used to modify a polymer or a polymer hydride. The above polymerization system may be a hydrated salt of ", Os, Ru trichloride, MoC15, WC16, ReCI5, (C2H5) 3A (C2H5) 3AI / TiCI4, (π C4H7) 4Mo / TiCU, (ττ _C4H7) 4W/TiCI4, (7Γ-C3H5)3Cr/WCI6, etc. are used as a polymerization medium. As the above-mentioned decene-based resin, for example, the product name "ZEO NOR" manufactured by Japan's Liyang Co., Ltd., " ZEONEX", the product name "ARTON" manufactured by JSR Corporation, the product name "OPTOREZ" manufactured by Hitachi Chemical Co., Ltd., and the product name "APEL" manufactured by Mitsui Petrochemical Industries Co., Ltd., and other commercial products. Similarly to the polyester resin, the decene-based resin may be added with an ultraviolet absorber as needed. In addition, in order to enhance the adhesion to the polarizer, it is possible to carry out drying treatment and easy adhesion treatment at -38 to 200831962. [Method for Producing Phenol-Based Resin Film] The norbornene-based resin film can be formed by a melt molding method. The melt molding method includes a melt extrusion method such as a method using a T mold and an expansion method, an inexpensive power method, a hot press method, and an injection molding method. Among them, a melt extrusion method using a T mold which is small in thickness unevenness, easy to process to a thickness of about 50 to 500 μm, and hysteresis and a small variation thereof is preferable. The conditions for melt forming are the same as those used for the polycarbonate having the same degree of Tg. For example, in the melt extrusion method using a T-die, it is preferred to select a resin temperature of about 240 to 300 ° C, and the temperature of the collecting roller is set at a relatively high temperature of about 1 to 150 ° C, and the resin can be used. Slowly cool the conditions. Further, in order to reduce the surface defects of the mold line or the like, it is necessary to reduce the retention portion in the mold as much as possible. Therefore, it is preferable to use the inside of the mold and the rib without extremely damage. Moreover, such sheets can be further improved in surface accuracy by honing the surface as needed. <Second Protective Film> As the second protective film, from the viewpoint of productivity in processing of the polarizing plate, it is possible to use cellulose deuterated, and it is particularly preferable to use 25 ° C and a relative humidity of The absolute 値 of the difference between the retardation 値 (Re10) in the in-plane direction at 10% and the hysteresis Re (Re80) in the in-plane direction at 25t and relative humidity of 80%, divided by 25°C and relative humidity Hysteresis in the in-plane direction at 60% -39- 200831962 値(R e 6 0 ) 値gr is 0.0 6 or more. Hereinafter, cellulose deuterated is described in detail. The cellulose used as the raw material for deuterated cellulose in the present invention is cotton fluff, wood pulp or the like. However, deuterated cellulose obtained from any raw material cellulose may be used, or may be used in combination. Further, in the present invention, the cellulose deuterated cellulose is preferably a cellulose which has a degree of substitution with respect to the cellulose group and which satisfies the following formulas (I) and (π): 2.30^SA + SB< 2.80 ...........Formula (I) OS SBS 1_〇〇...............Formula (Π) Here, in Formula (I) and In (Π), SA and SB represent substituents of a mercapto group substituted by a hydroxyl group of cellulose, SA represents a degree of substitution of an ethyl group, and SB represents a degree of substitution of a mercapto group having 3 to 4 carbon atoms. . The glucose unit constituting the /3 -1,4 linkage of cellulose has a radical at the 2, 3 and 6 positions. The deuterated cellulose is a polymer (polymer) obtained by esterifying a part or all of the hydroxyl groups of the thiol group. The thiol substitution degree means the ratio of esterification to each of the celluloses at the 2, 3, and 6 positions (the degree of substitution of 100% esterification is 1). From the viewpoint of the discovery of optical anisotropy, in the present invention, the sum of substitution degrees of SA and SB of the hydroxyl group is preferably 2.30 S SA + SB < 2.80, more preferably 2.30 SSA + SB < 2.60. Further, the smaller the sum of the degrees of substitution, the less likely it is that the complex fold is found and the moisture permeability is also increased. Therefore, the present inventors have found that: -40-200831962, even when the moisture permeability of the first protective film is 300 g/m 2 · day or less, even if a cellulose oxide film of 2.30 SSA + SB < 2_80 is used In this case, it is also possible to suppress a change in hysteresis caused by a change in optical characteristics due to humidity. The basic principle of the synthesis method of cellulose derivative of cellulose derivative used in the present invention is described in Odita, Wood Chemistry, pp. 180-190 (Kyoritsu Publishing, 1 968). A representative synthesis method is a liquid phase hydration method using a carboxylic acid anhydride-monoacetic acid-sulfuric acid catalyst. The cellulose derivative film used in the present invention is preferably a polymer component constituting the film formed of a cellulose derivative substantially having the above definition. The term "substantially" means 55 mass% or more of the polymer component (preferably 70 mass% / 〇, more preferably 80 mass% or more). It is preferred to use cellulose derivative particles as a raw material for producing a film. It is preferable that 90% by mass or more of the particles to be used have a particle diameter of 0.5 to 5 mm. Further, it is preferable that 50% by mass or more of the particles to be used have a particle diameter of 1 to 4 mm. The cellulose derivative particles are preferably in a shape having a spherical shape as close as possible. The polymerization degree of the cellulose derivative which is more suitably used in the present invention is preferably a viscosity average polymerization degree of 200 to 700, more preferably 250 to 550, more preferably 250 to 400, and particularly preferably 250 to 350. . The average degree of polymerization can be measured by the limit viscosity method of Uda et al. (Uda Kazuo, Saito Hideo, Fiber Society, Vol. 18, No. 1, pp. 1, pp. In addition, it is also described in detail in JP-A-9-95538. 0-41-200831962 Further, the cellulose-deposited cellulose used in the present invention is preferably Mw/Mn (Mw is a mass average) measured by a gel dialysis chromatograph. The molecular weight distribution of the molecular weight, Μη is the number average molecular weight) is narrow. The range of Mw/Mn is preferably 1.Q to 1.7, more preferably 1.3 to 1.65, more preferably 1.4 to 1.6. <<Deuterated cellulose film having the largest refractive index in the film thickness direction>> From the viewpoint of optical compensation, a cellulose oxide film having a maximum refractive index in the film thickness direction can also be used. The driving mode of the liquid crystal cell is not particularly limited and may be appropriately selected according to the purpose. However, for example, an I P S mode, an E C B mode, or a VA mode may be used, and among them, the IPS mode is suitably used. The substituent which is bonded to the three hydroxyl groups on the /3-glucose ring of the constituent unit of the deuterated cellulose is preferably a substituent having a large difference in the polar ratio. An optical compensation film having a maximum refractive index in the film thickness direction can be obtained by introducing a substituent having a large difference in the polarization ratio into the deuterated cellulose and adjusting the other substituents and the degree of substitution. [Terminal spacing of the substituents and the polarization of the polarization ratio] The terminal spacing and the polarization of the substituents of the cellulose derivative having the largest refractive index in the film thickness direction are the high-intensity (version B.03, The software of the company is calculated. The end spacing is calculated by the calculation of the B3LYP/6-3 1 G* level and then calculated as the most separate atomic spacing. The polarization rate isotropically uses a configuration optimized by B3LYP/6-31 G* level, and the polarization ratio is calculated at 3LYP/6-31G**, and the resulting polarization is different from -42 to 200831962. After the tensor is diagonalized, it is calculated from the diagonal component. When calculating the terminal pitch of the substituent and the heteropolarity of the partiality, the substituent which is bonded to the hydroxyl group on the - glucose ring of the constituent unit of the cellulose derivative is calculated in a partial structure of the oxygen atom containing a hydroxyl group. Obtained. The polarization heterogeneity of the cellulose derivative having the largest refractive index in the film thickness direction is defined by the following formula (A). Further, in the following formula (A), ax, ay, and α are inherent flaws obtained by diagonally dividing the polarization tensor, a X - a y 2 a ζ. Δ a = αχ—(ay + a ζ) 12.........Formula (A) The fractional heterogeneity is related to the refractive index perpendicularity in the vertical direction of stretching of the film. . That is, in the case where the above-described partial polarization anisotropy is small, the slow phase axis can be found in the tensile direction, and in the case where the above-described partial polarization is different in directivity, the late phase can be found in the vertical direction of the stretching. axis.

In order to obtain an optical complementary film having a hysteresis in the film thickness direction, the above-mentioned partial polarity is more excellent, preferably 2.5 X 1 (T24 cm_3, more preferably 3.5×10_24 cm_3, particularly preferably 4.5×10). -24 cm-3. A preferred cellulose derivative having a maximum refractive index in the film thickness direction is preferably a fatty acid sulfhydryl group and a mixed acid ester having a substituted or unsubstituted aromatic fluorenyl group. The substituted or unsubstituted aromatic fluorenyl group, for example, may be a group represented by the following general formula (A): -43- 200831962

One-step formula (Α> First, the general formula (Α) is illustrated. In the general formula (Α), X is a substituent, and an example of the substituent, for example, 'for example, it may be a halogen atom, a cyano group, or an alkane Alkyl, alkoxy, aryl, aryloxy, fluorenyl, carboxylamido, sulfonylamino, ureidoarylalkyl, nitro, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, amine Mercapto, sulfonyl, decyloxy, alkenyl, alkynyl, alkylsulfonyl, arylsulfonyl, alkoxyalkyl, aryloxysulfonyl, alkylsulfonyloxy And arylsulfonyloxy, -S-R, -NH-CO-OR, -PH-R, -P(-R)2, -PH-〇-R, -P(-R)(- 0—R), —P(—〇一R)2, a PH(=〇)-R—P(=〇)(一R)2, a PH(=〇)—〇一R,一p (= 〇)(一R)(—〇一R), 一P(=〇)(—〇一R)2, 一〇一PH(=〇)-R, 一〇一P(=〇)(一R) 2 —〇—PH (=〇)—〇—r, 一〇—p(二〇)(一R)(—〇一R), 一〇一P(=〇)(—〇—R)2, one NH-PH (二〇)—R, — NH— p(=〇)(— R)(—〇-R), —NH—P(=〇)(一〇—R)2, —SiH2—R,—SiH(—R)2, —Si(— R 3, a mono-SiH2-R, a hydrazine-SiH (-R) 2, and a ^ Si (- R) 3 o The above R is an aliphatic group, an aromatic group or a heterocyclic group. Preferably, it is one to five, more preferably one to four, and more preferably one to three, particularly preferably one or two. -44- 200831962 The above substituent is preferably a halogen atom or a cyano group. , an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a decyl group, a carboxy oxime group, a sulfonylamino group and a ureido group; among these, a halogen atom, a cyano group, an alkyl group, an alkoxy group is more preferable a aryl group, an aryloxy group, a fluorenyl group and a carboxy oxime group; among these, a halogen atom, a cyano group, an alkyl group, an alkoxy group, and an aryloxy group are more preferable; among these, a halogen atom is particularly preferable. The alkyl group and the alkoxy group are particularly preferably a group. The above halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. f Further, the above-mentioned alkyl group is exemplified by Said, for example, it can be methyl, ethyl, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a hexyl group, a cyclohexyl group, an octyl group, and a 2-ethylhexyl group. Further, the above alkoxy group may have a cyclic structure or may have a branch. The number of carbon atoms of the oxy group is preferably from 1 to 20, more preferably from 1 to 12, still more preferably from 1 to 6, particularly preferably from 1 to 4. The above-mentioned oxy group may be further subjected to other oxy groups. The substituted alkoxy group, for example, may be, for example, a methoxy group, a ethoxy group, a 2-methoxyethoxy group, a 2-methoxy-2-ethoxy group, a butoxy group. Base, hexyloxy and octyloxy. The above aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. Examples of the aryl group, for example, it may be a phenyl group and a naphthyl group. Further, the above aryloxy group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. Examples of the aryloxy group' are exemplified by, for example, a phenoxy group and a naphthyloxy group. Further, the number of carbon atoms of the above mercapto group is preferably from 1 to 20, more preferably from 1 to 12. Examples of the fluorenyl group, for example, may be a fluorenyl group, an ethyl fluorenyl group, and a benzamidine group. Further, the above-mentioned carboguanamine group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms. Examples of the carboxylamido group, for example, may be an acetamino group and a benzylamino group. Further, the above sulfonamide group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms. Examples of the sulfonamide group include methanesulfonamide, benzenesulfonylamine and hydrazine-toluenesulfonamide. Further, the number of carbon atoms of the above urea group is preferably from 1 to 20, more preferably from 1 to 12. Examples of the ureido group are, for example, (unsubstituted) ureido groups. Further, the above alkyl group may have a cyclic structure or may have a branch. The above alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12, still more preferably 1 to 6, and particularly preferably 1 to 4. Further, the above aralkyl group preferably has 7 to 20' carbon atoms in an amount of 7 to 12'. Examples of the aralkyl group, for example, may be a benzyl group, a phenethyl group, and a naphthylmethyl group. Further, the above alkoxycarbonyl group has preferably 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. An example of the alkoxycarbonyl group, for example, it may be a methoxycarbonyl group. Further, the above aryloxy ore group preferably has 7 to 20 carbon atoms, more preferably 7 to 12 carbon atoms. An example of the aryloxycarbonyl group, for example, it may be a phenoxycarbonyl group. Further, the above-mentioned aralkoxycarbonyl group preferably has 8 to 20 carbon atoms, more preferably 8 to 12 carbon atoms. An example of the aralkyloxycarbonyl group, for example, it may be a present methoxy iron group. Further, the above mercaptoamine group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms. Examples of the formamidine group, for example, may be (unsubstituted) formamidine and N-methylformamido. Further, the number of carbon atoms of the above sulfonamide group is preferably 20 or less, more preferably 12 or less. Examples of the sulfonamide group are, for example, a gastric (unsubstituted) sulfonamide group and an N-methylsulfonylamino group. Further, the above-mentioned decyloxy group preferably has 1 to 20 carbon atoms, more preferably 2 $1 2 . Examples of the decyloxy group include an ethoxylated group and a benzamidineoxy group. The above alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. Examples of the above alkenyl group are, for example, a vinyl group, an allyl group and an isopropenyl group. Further, the above alkynyl group has a carbon number of 2 to 20, more preferably 2 to 12 °, and is exemplified by, for example, a thienyl group. Further, the above alkylsulfonyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms. Further, the above-mentioned arylsulfonyl group has preferably 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. Further, the above alkoxysulfonyl group has preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms. Further, the above-mentioned aryloxysulfonyl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. And, in the fatty acid ester residue in the cellulose mixed acid ester, for example, the aliphatic fluorenyl group has 2 to 20 carbon atoms, and specifically, for example, it may be an ethyl ketone group or a propylene group. Sulfhydryl, butyl sulfhydryl, isobutyl fluorenyl, pentamidine, trimethylethenyl, hexyl, octyl, laurel, stearyl and the like. Among these, it is preferably an ethyl group, a propyl group and a butyl group; among these, it is preferably an ethyl group. In the present invention, the aforementioned aliphatic thiol group also includes the meaning of having a further substituent; the substituent, for example, may be exemplified as the X of the above general formula (A) . Further, in the above general formula (A), the number (?) of the substituents replacing the aromatic ring is preferably α or 1 to 5, more preferably 1 to 3, more preferably 1 or 2. Further, when the number of substituents of the substituted aromatic ring is two or more, the above substituents may be the same or different from each other. Further, they may be linked to each other to form a condensed polycyclic compound (for example, naphthalene, anthracene, anthracene, phenanthrene, quinoline, isoquinoline, chromene, chroman, diazepine, acridine, anthracene, anthracene). Porphyrin, etc.). Next, a method of performing an aromatic thiol group substitution to a hydroxyl group of cellulose, for example, "for example, an aromatic carboxylic acid chloride, a symmetric acid anhydride derived from an aromatic carboxylic acid, and a method of mixing an acid anhydride can be generally used. A particularly preferred method 'for example' may be, for example, a method using an anhydride derived from an aromatic carboxylic acid - 48-200831962 (described in the Journal of Applied Polymer Science, Vol. 29, No. 3 9 8 1 3990 (1 984)) The method for producing the aforementioned cellulose mixed acid ester compound by the above method, for example, it may be (1) at the time of production of a cellulose fatty acid monoester or diester In the residual hydroxyl group, a method of introducing a mixed acid anhydride of the above aromatic sulfhydryl group represented by the general formula (A), and (2) reacting the cellulose directly with a mixed acid anhydride of an aliphatic carboxylic acid and an aromatic carboxylic acid Method etc. In the method of the above (1), although the method for producing the cellulose fatty acid ester or the diester itself is a conventional method, the reaction of the aromatic sulfhydryl group further introduces the type of the aromatic thiol group. Different, however, the reaction temperature is preferably 0 to 100 ° C, more preferably 20 to 50 ° C. Further, the reaction time is preferably 30 minutes or more, more preferably 30 to 300 minutes. Further, in the method of using the mixed acid anhydride in the above (2), the reaction conditions may vary depending on the type of the mixed acid anhydride, but the reaction temperature is preferably 〇 100 ° C, more preferably 20 to 50 ° C. Further, the reaction time is preferably from 30 to 300 minutes, more preferably from 60 to 200 minutes. The reaction in any of the above (1) to (2) may be carried out in the absence of a solvent or a solvent, but it is preferably carried out using a solvent. The solvent may, for example, be dichloromethane, chloroform, dioxane or the like. The degree of substitution is recorded as 3.0 when 100% of the hydroxyl groups of the cellulose are substituted. In addition, the degree of substitution can be determined from the peak intensity of the carbonyl carbon in the fluorenyl group of c13-nmr. The degree of substitution of the aromatic thiol group is preferably 2.0 or less, more preferably 0.1 to 2 · 0, more preferably 0.1 to 1 · 0, in the case of the cellulose fatty acid monoester, relative to the residual hydroxyl group. . Further, the degree of substitution of the cellulose fatty acid diester (cellulose diacetate) is preferably 1.0 or less, more preferably 0.1 to 1.0, based on the residual hydroxyl group. Further, the total substitution degree P A of the deuterated cellulose is preferably 2.4 to 3.

Further, in order to find a negative Rth, it is preferred to introduce a substituent having a large partial unipolarity in the 2-position and the 3-position of the Θ-glucose ring. The 2nd position and the 3rd position are presumed to be lower in the degree of freedom than the 6th position in which the substituent is introduced from the 0-glucose ring through the carbon atom, so that the introduced substituent is easily aligned in the film thickness direction, which is easy. The film is oriented in the film thickness direction by a stretching treatment. Specific examples of the aromatic fluorenyl group represented by the general formula (A) are exemplified below, but the present invention is not limited thereto. Further, in the present invention, the aromatic fluorenyl group represented by the general formula (A) is preferably the numbers 1, 3, 5, 6, 8, 13, 18 and 28 in the following specific examples; More preferably, the numbers 1, 3, 6, and 13.

-50 200831962

ο

-51- 200831962

32 H3CO\A〇~. -O"4— -52- 200831962

The refractive index of the meniscus in the thickness direction is the highest, and the average degree of polymerization is preferably from 350 to 800, and more preferably from 370 to 600. Further, the refractive index of the film thickness direction is the largest, and the average molecular weight of the cellulose is more than 70, 〇〇〇~230,000, and more preferably has a mass average of 75,000 -53 - 200831962 ~ 230,000 The molecular weight, more desirably, has an average molecular weight of from 78,000 to 120,000. A oximation agent which can use an acid anhydride or an acid chloride. In the case where the aforementioned hydrating agent is an acid anhydride, an organic acid (e.g., acetic acid) or dichloromethane may be used as the reaction solvent. The aforementioned catalyst can be a protonic catalyst such as sulfuric acid. In the case where the aforementioned deuterating agent is an acid chloride, a base blocking medium can be used as a catalyst. The most common synthetic method known in the industry is an organic acid (acetic acid, propionic acid, butyric acid) or an anhydride (acetic anhydride, propionic anhydride) containing an oxime group and other sulfhydryl groups. A method of synthesizing a cellulose ester by esterifying cellulose with a mixed organic acid component of butyric anhydride. In this method, most of the cases are: cellulose such as cotton and wood pulp is activated by an organic acid such as acetic acid, and then used in the presence of a sulfuric acid catalyst, as described above. A mixture of such organic acid components is described for esterification. ί· The organic acid anhydride component is generally used in excess of the amount of hydroxyl groups present in the cellulose. In the esterification treatment, in addition to the esterification reaction, the hydrolysis reaction (depolymerization reaction) of the cellulose main chain /3 1-> 4-glucose bond is carried out. When the main chain hydrolysis reaction is carried out, Then, the polymerization of the cellulose ester is lowered, and the physical properties of the produced cellulose ester are lowered. Therefore, the reaction conditions such as the reaction temperature are preferably determined in consideration of the degree of polymerization and molecular weight of the obtained cellulose-54-200831962 vitamin ester. In order to obtain a cellulose ester having a high degree of polymerization (large molecular weight), it is important to adjust the maximum temperature in the esterification reaction step to 50 ° C or lower. The aforementioned maximum temperature is preferably adjusted to 35 to 50 ° C, and more preferably to 37 to 47 ° C. When the reaction temperature is 35 ° C or more, the esterification reaction can be carried out smoothly, which is preferable. When the reaction temperature is at most 50 °C, the degree of polymerization of the cellulose ester is unfavorable, which is not preferable. When the reaction is stopped while suppressing the temperature rise after the esterification reaction, the decrease in the degree of polymerization can be further suppressed, and the cellulose ester having a high degree of polymerization can be synthesized. That is, when a reaction terminator (e.g., water or acetic acid) is added after the end of the reaction, the excess acid anhydride which is not related to the esterification reaction is hydrolyzed to form a corresponding organic acid. Such a hydrolysis reaction causes a temperature rise in the reaction apparatus with intense heat generation. (As long as the reaction rate of the reaction stop reaction is not excessively large, it does not occur: rapid heating occurs beyond the cooling capacity of the reaction apparatus, so that the hydrolysis reaction of the cellulose main chain proceeds remarkably, resulting in polymerization of the obtained cellulose ester. Further, a part of the catalyst in the esterification reaction is combined with cellulose, and most of them are dissociated from the cellulose in the stop of the addition reaction. At this time, if the reaction stopper is added at a high speed, If it is large, it can be -55-200831962 to ensure sufficient reaction time for dissociation of the catalyst, so that it is difficult to cause problems due to the binding of a part of the catalyst to the fiber. The cellulose ester has very poor stability and is easily decomposed due to heat or the like in the case of drying the product, so that the degree of polymerization is lowered. For these reasons, after the esterification reaction, it is preferred to spend 4 minutes or more, more preferably 4 ~30 minutes to add the reaction stop agent, in order to stop the reaction. In addition, if the addition time of the reaction stop agent is less than 30 minutes It is preferred because it does not cause problems such as a decrease in productivity, etc. (As a reaction-stopping agent, water or an alcohol which decomposes an acid anhydride can be generally used. However, in the present invention, in order to prevent precipitation In the case of a triester having a low solubility in an organic solvent, it is preferred to use a mixture of water and an organic acid as a reaction stopper. When the esterification reaction is carried out under the above conditions, the mass average degree of polymerization can be easily synthesized. It is a high molecular weight cellulose ester of 500 or more. <<> Manufacture of a cellulose-deposited film>> The above-described cellulose-deposited film is produced by a solvent casting method.

In the C method, a film (coating liquid) obtained by dissolving deuterated cellulose in an organic solvent is used to produce a film. Hereinafter, an organic solvent capable of dissolving a cellulose derivative will be described. First, a chlorine-based organic solvent which is suitably used in the production of a solution of a cellulose derivative is described. The chlorine-based organic solvent is not particularly limited as long as it can achieve its purpose within the range in which the cellulose derivative can be dissolved. -56- 200831962 These chlorine-based organic solvents are preferably dichloromethane or chloroform. Particularly preferred is methylene chloride. Further, organic solvents other than the mixed chlorine-based organic solvent are not particularly problematic. In this case, the chlorine-based organic solvent is preferably used in an amount of at least 50% by mass or more. The following describes the non-chlorinated organic solvents that can be used. That is, a preferred non-chlorine organic solvent is preferably a solvent selected from the group consisting of esters, ketones, ethers, alcohols, hydrocarbons, and the like having 3 to 12 carbon atoms. Esters, ketones, ethers and alcohols may also contain an f-ring structure. Further, the alcohol to be used in combination with the chlorine-based organic solvent may preferably be a straight chain, and may have a branch or a ring; and among them, a saturated aliphatic hydrocarbon is preferred. The basis of dropping out of school can be any of the first level to the third level. Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 2-methyl-2-butanol, and a ring. Hexanol. In addition, a fluorine-based alcohol can also be used as the alcohol. For example, it may be 2 fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol L: and the like. Further, the hydrocarbon may be linear, may have a branch, or may have a ring shape. Any of an aromatic hydrocarbon and an aliphatic hydrocarbon can be used. The aliphatic hydrocarbon may be saturated or unsaturated. Examples of hydrocarbons include cyclohexyl hydrocarbon, hexanyl, benzene, toluene, and xylene. Next, a non-chlorine-based organic solvent will be described. In the present invention, in the range in which the cellulose derivative can be cast, as long as it can achieve the object, the non-chlorinated organic solvent is not particularly limited. The non-chlorine organic solvent is preferably a solvent selected from the group consisting of esters, ketones and ethers having 3 to 12 carbon atoms. The ethers, ketones and ethers may also have a cyclic structure. Further, any two or more of the functional groups (g卩, Ο-, -C Ο, and one C Ο Ο) having an ether, a ketone, and an ether may be used as a main solvent. For example, It may have other functional groups such as an alcoholic hydroxyl group. In the case of a main solvent having two or more kinds of functional groups, the number of carbon atoms may be within a predetermined range of a compound having any functional group, that is, C1. Examples of the ester having 3 to 12 carbon atoms may, for example, be an ethyl formate, a propyl formate, a valerate, a methyl acetate or an ethyl acetate. And pentyl acetate. Examples of the ketone having 3 to 12 carbon atoms may, for example, be acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclopentanone, and methylcyclohexanone. . Examples of the ether having 3 to 12 carbon atoms may, for example, be diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1, 3-dioxolane, tetrahydrofuran, anisole, phenylethyl ether. Examples of the organic solvent having two or more kinds of functional groups may, for example, be 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol. With respect to the non-chlorine-based organic solvent used in the above cellulose derivative, although it can be selected in view of the above various viewpoints, it is preferably as described in -58-200831962. That is, a preferred solvent for the cellulose derivative is a mixed solvent containing three or more kinds different from each other, and the first solvent is derived from methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, and dioxane. At least one selected from the group consisting of pentane and dioxane or a mixture thereof; the second solvent is selected from a ketone or ethyl acetate having 3 to 7 carbon atoms, and the third solvent is from a carbon number The alcohol selected from the group consisting of 1 to 10 alcohols or hydrocarbons is more preferably an alcohol having 1 to 8 carbon atoms. Further, when the first solvent is a mixed solution of two or more kinds of solvents, the second solvent may not be used. The first solvent is more preferably methyl acetate, acetone, methyl formate, ethyl formate, f% % ' or a mixture of the same; the second solvent is preferably acetone, methyl ethyl ketone, cyclopentanone, cyclohexane Ketone, ethyl acetate, methyl acetate, may also be a mixture thereof. The cellulose derivative is preferably dissolved in an organic solvent to have an amount of from 1 to 30% by mass, more preferably from 3 to 27% by mass, particularly preferably an aqueous solution of a fiber derivative dissolved in 15 to 25% by mass. The method of producing the cellulose derivative of such a concentration may be carried out in such a manner as to achieve a predetermined concentration in the dissolution stage; or, after a low concentration solution (for example, 9 to 14% by mass) may be prepared in advance, Then adjust the concentration process to the specified high concentration solution. Further, it is also possible to add various additives to a predetermined low-concentration cellulose derivative after the high cellulose derivative in advance. [Additive] In the above-mentioned deuterated cellulose solution, various additives may be added along with the use in each preparation step (for example, a plasticizer, an ultraviolet preventive agent, an optical anisotropic control agent, a fine particle, a release agent, and an infrared ray). Absorbents, etc.); they may be solid or oily. That is, the melting point and boiling point -59 - 200831962 are not particularly limited. For example, a mixture of ultraviolet absorbing materials of 20 ° C or less and 20 ° C or more, and a mixture of a plasticizer and the like are described, for example, in JP-A No. 2001-51901. Further, an infrared absorbing dye is described, for example, in JP-A No. 2001-1 94522. Further, although the addition period may be added at any time in the coating liquid preparation step, it may be carried out by adding a preparation step of adding an additive in the final preparation step of the coating liquid preparation step. Further, the amount of each material added is only required to exhibit a function, and is not particularly limited. Further, when the deuterated cellulose film is formed of a plurality of layers, the types and addition amounts of the additives of the respective layers may be different. For example, it has been described on the Japanese Patent Laid-Open Publication No. 2001-51 902, and the like. These are known techniques. It has been possible to use materials which have been proposed by the prior art as a material for miniaturizing the moisture permeability. Further, a method of adding a highly molecularized plasticizer to deuterated cellulose has been disclosed in Japanese Laid-Open Patent Publication No. 2002-22956. Further, a method of using a rosin-based plasticizer has been disclosed in Japanese Laid-Open Patent Publication No. 2002-1 46044. Further, a method of using a hydrophobic plasticizer and a deterioration preventing agent for enamel has been disclosed in Japanese Laid-Open Patent Publication No. 2001-343528. Further, a method of using a compound containing two aromatic rings has been disclosed in Japanese Laid-Open Patent Publication No. 2002-14230. Further, in Japanese Laid-Open Patent Publication No. Hei 9-90101, a method of changing fluorinated cellulose to form a hydrophobic substance has been proposed. -60-200831962 A more specific material is exemplified as follows. However, the moisture permeability controlling agent which can be used in the present invention is not limited to the following.

[Hysteric retardation rising agent] In the second protective film provided opposite to the liquid crystal cell, in order to increase the retardation, an aromatic compound having at least two aromatic rings can be used as the hysteresis rising agent. Such a hysteresis rising agent is an aromatic compound having at least two aromatic rings, for example, it may be a three-till (triphenyl-1,3,5-tri-trap), three-m- Tolyl-1,3,5-three-till, etc.), diester of cis-1,4-cyclohexanedicarboxylic acid (diester of pn-hexylphenol, diester of pn-aminophenol, etc.) . Other specific examples are described in JP-A-2000-1 1 1 91, JP-A-2000-275434, and PCT/JP00/02619. It is also possible to use two or more kinds of aromatic compounds. The aromatic aromatic ring of the aromatic compound includes, in addition to the aromatic hydrocarbon ring, an aromatic heterocyclic ring. -61- 200831962 The molecular weight of the hysteresis rising agent is preferably 300~800. In the case of using a deuterated cellulose as the unit cell side protective film, an aromatic compound in the range of 1 to 20 parts by mass based on 1 part by mass of the deuterated cellulose can be used. It is preferable to use an aromatic compound in the range of 0.05 to 15 parts by mass, more preferably in the range of 0.1 to 1 part by mass, based on 100 parts by mass of the deuterated cellulose. The second protective film disposed opposite to the liquid crystal cell can also be used to reduce hysteresis by an additive known in the art. In Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2000-63560, the disclosure of which is incorporated herein by reference. A method for reducing the refraction reproducibility. In more detail, it is preferably used in the Invention Association Open Technical Report (public technology 5 tiger code 2001-1745, March 15, 2001 issue, invention association) The materials described in detail on page 22. On the above air-side protective film, it is necessary to add an anti-UV agent. However, it is not necessary to add an anti-UV V--agent on the cell side protective film. Modulation] The deuterated cellulose solution can be prepared by a general method of treatment at a temperature of 0 ° C or higher (normal temperature or high temperature). The preparation of the solution can be prepared by using a coating liquid in a common solvent casting method. The method and the device are implemented. In addition, in the case of the general method, it is preferred to use a halogenated hydrocarbon (especially a dichlorocarbyl) as an organic solvent. The amount of the deuterated cellulose is obtained according to the obtained 62- In the solution of 200831962 The amount is adjusted to be 10 to 40 mass%. The amount of deuterated cellulose is preferably 10 to 30 mass%. In an organic solvent (main solvent), any additives described later may be added. The solution can be prepared by stirring the deuterated cellulose and the organic solvent at normal temperature (0 to 40 ° C). The high concentration solution can also be stirred under pressure and heating conditions. The deuterated cellulose and the organic solvent are placed in a pressurized container and sealed, and are heated while being heated to a temperature above the normal temperature boiling point of the solvent and at a temperature at which the solvent does not boil. The heating temperature is usually preferably 40 ° C. The above is more preferably 60 to 200 ° C or more, and more preferably 80 to 1 10 ° C or more. The components may be roughly mixed beforehand and then put into a container. Alternatively, they may be sequentially placed in a container. It is a structure that can be stirred. The container can be pressurized by injecting an inert gas such as nitrogen gas. Alternatively, the vapor pressure of the solvent heated by heating can be used. Alternatively, the container can be sealed and then pressurized. In the case of heating, it is preferred to heat the outside of the container. For example, a sleeve type heating device may be used, or a plate heater may be provided outside the container to perform piping. The liquid is circulated to heat the entire container. It is preferred to provide a stirring wing inside the container and use it for agitation. The stirring wing is preferably an item having a length near the wall of the container. At the end of the stirring wing, For the purpose of updating the liquid film on the wall of the container, it is preferable to set the wing to be set -63- 200831962. In the container, a gauge such as a pressure gauge or a thermometer may be provided. In the container, the components are dissolved in the solvent. The prepared coating liquid is taken out from the container after cooling, or taken out and then cooled using a heat exchanger or the like. The solution can also be adjusted by a cooling dissolution method. The cooling dissolution method is a method in which cellulose deuterated cellulose can be dissolved even in an organic solvent which is not easily dissolved by an ordinary dissolution method. Further, even if it is a conventional dissolution method capable of dissolving a deuterated cellulose solvent, when a cooling dissolution method is used, a so-called rapid uniform solution effect can be obtained. Therefore, when it is only dissolved in a non-chlorine solvent, it is preferred to use a cooling dissolution method. In the case of the cooling dissolution method, cellulose deuterated cellulose is initially added to an organic solvent at room temperature while stirring. The amount of deuterated cellulose is preferably adjusted so as to contain 1 〇 to 40% by mass in the mixture. The amount of deuterated cellulose is more preferably 1 〇 to 30% by mass. Further, any of the additives described later may be added to the mixture. 1. Secondly, it is preferred to cool the mixture to _ 1 〇〇~10 °c (more preferably - 80--10 ° C, more ideally - 50--20 ° C, especially preferably -50- -30 °C). The cooling ' can be carried out, for example, in a dry ice/methanol bath (75 ° C) or in a cooled diethylene glycol solution (3 〇 ° C - 20 ° C). The mixture of deuterated cellulose and an organic solvent is solidified by cooling. The cooling rate is preferably 4 ° C / min or more, more preferably 8 ° C / min or more, more preferably 12 ° C / min or more. -64- 200831962 Although the cooling rate is as fast as possible, the theoretical upper limit is 10,000 ° c / sec, while the technical upper limit is 1,000 ° c / sec, and the practical upper limit is 1 〇〇 ° c / second. In addition, the cooling rate is the difference between the temperature at which cooling starts and the final cooling temperature, divided by the time from the start of cooling to the time when the final cooling temperature is reached. Furthermore, when it is heated to 0 to 200 ° C (more preferably 0 to 150 ° C, more preferably 〇 ~ 1 2 0 °c, particularly preferably 0 to 50 ° C), bismuth fiber The compound is dissolved in an organic solvent. The temperature rise can be carried out not only at room temperature, but also by warm bathing. The heating rate is preferably 4 ° C / min or more, more preferably 8 ° C / min or more, more preferably 1 2 ° C / min or more. Although the heating speed is as fast as possible, the theoretical upper limit is 1 〇, 〇〇〇 ° C / sec, and the technical upper limit is 1, 〇〇〇 ° C / sec, and the practical upper limit is 1 0 0 °C / sec. In addition, the heating rate is the difference between the temperature at which the heating starts and the final heating temperature, divided by the time from the start of heating to the final heating temperature. According to the above, a uniform solution can be obtained. Further, in the case where the dissolution is insufficient, the operation of cooling and heating can be repeated. Whether or not the dissolution is sufficient can be judged only by visually observing the appearance of the solution. In the cooling and dissolving method, in order to avoid condensation due to condensation during cooling, it is desirable to use a closed container. Further, in the cooling and heating operation, when the pressure is increased by cooling and the pressure is reduced by heating, the dissolution time can be shortened. In order to carry out pressurization and decompression, it is expected to use a pressure-resistant container. -65- 200831962 In addition, a 20% by mass solution obtained by dissolving deuterated cellulose (degree of deuteration: 60.9%, viscosity average degree of polymerization: 299) in methyl acetate by a cooling dissolution method, when scanning by differential scanning When measured by a calorimeter (DSC), it has a suspected phase transition point between the sol state and the gel state at around 30 ° C, and at this temperature, it becomes a uniform gel state. Therefore, the solution needs to be maintained at a temperature above the suspected phase transition point, preferably at a temperature of about 1 〇 °C at the suspected phase transition point of the gel. However, the temperature of the suspected phase transition point varies depending on the degree of thiol substitution of the deuterated cellulose, the average degree of polymerization of the viscosity, the concentration of the solution, and the organic solvent used. [Casting] A deuterated cellulose film was produced by a solvent casting method from a prepared deuterated cellulose solution (coating liquid). It is preferable to add the aforementioned hysteresis sputum rising agent to the coating liquid. The coating liquid is cast on a roll or belt to evaporate the solvent to form a film. The coating liquid before casting is preferably adjusted so that the amount of solid matter becomes 18 to 35 %. The surface of the roll or belt is preferably pre-finished into a mirrored state. Preferably, the coating liquid is applied to a roll or belt having a surface temperature below 10 °C. In the present invention, in the case where the coating liquid (deuterated cellulose solution) is cast on the belt, it is preferred to carry out the first half of the drying before the stripping, and it is preferably carried out for 10 seconds or more and 90 seconds or less. A step of substantially no air drying of from 1 5 seconds to 90 seconds. Further, in the case of casting on a roll, it is preferable to carry out the first half of the drying before the stripping for 1 second or more to 10 seconds or less, and preferably for 2 seconds or more to 5 to 66 to 200831962 seconds or less. The drying step. The term "drying before stripping" as used in the present invention means drying from the application of a coating liquid onto a belt or a roll to peeling off as a film. Further, the "first half" refers to a step before half of the total time required from the application of the coating liquid to the stripping. Further, the term "substantially no wind" means that no wind speed of 〇 5 meters/second or more is detected in a distance from the surface of the belt or the surface of the roller to within 200 mm. (In the first half of the drying before stripping, although it is usually about 30 to 300 seconds in the case of belting, it is more than 1 sec. to less than 9 sec., more preferably more than 15 sec. Drying in the absence of wind for a period of 90 seconds or less. In the case of a roller, it is usually about 5 to 30 seconds, but it is preferably 1 second or more and 10 seconds or less, more preferably 2 seconds or more and 5 minutes or less. The time below seconds is 'drying under no wind. The temperature of the atmosphere is preferably 〇~1 80 0:, but more preferably 4 0~1 50 ° C. The operation without air drying, although it can be before stripping It is carried out in any stage of the first half of the drying process, but it is preferably carried out immediately after the casting 11 -. When the time of no air drying is less than 1 〇 second, the additive is difficult to be uniformly distributed in the film; When the temperature is 0 seconds, the surface of the film is deteriorated due to insufficient drying. The time other than the airless drying during the drying before stripping can be carried out by blowing air with an inert gas. The air temperature at this time is preferably 〇~1 8 〇 It is more preferably 40~150 ° C. About solvent casting The drying method is described in U.S. Patent No. -67-200831962, No. 23,363, 031, U.S. Patent No. 2, 367, 603, U.S. Patent No. 2, 492, 078, U.S. Patent No. 2,492, 977, U.S. Patent No. 2,492, 978, U.S. Patent No. 2,607, 704, U.S. Patent No. 2739069, U.S. Patent No. 2,739,070, British Patent No. 640,731, British Patent No. 736,892, Japanese Patent Publication No. Sho 45-4554, Japanese Patent Publication No. Sho 49-561, No. 60-1 76834 In JP-A-60-203430, JP-A-62-1 1 5035, drying on a belt or a roll can be carried out by blowing air through an inert gas such as air or nitrogen. The film is stripped from the roll or strip, and can be further dried by continuously changing the temperature of the high temperature wind from 100 to 160 ° C to evaporate the residual solvent. The above method is described in the special fair. In the case of this method, the time from casting to stripping can be shortened. In order to carry out this method, it is necessary to apply a gel to the surface temperature of the roll or belt which is delayed. Chemical. /... The prepared deuterated cellulose solution (coating liquid) is also thinned by casting two or more layers. In this case, it is preferred to prepare the deuterated cellulose by solvent casting. The coating liquid is cast on a roll or a belt, and the solvent is evaporated to form a film. The coating liquid before casting is preferably adjusted in such a manner that the amount of solid matter is in the range of 10 to 40%. The surface is preferably processed into a mirror-like state. In the case of a plurality of deuterated cellulose solutions cast over two layers, it is possible to cast a plurality of deuterated cellulose solutions at intervals of -68-200831962, or The casting opening in the direction in which the support is carried out is placed, and the solution containing the deuterated cellulose is separately cast, and a film is formed while laminating. For example, the method described in the publications of JP-A-61-158414, JP-A-1-122419, and JP-A-11-198285 can be used. Further, it is also possible to carry out thinning by casting a deuterated cellulose solution from two casting openings. For example, it can be used in Japanese Patent Publication No. 60-275, No. 61-94724, JP-A-61-947245, JP-A-61-104813, and JP-A-61-1 584 1 And the method described in each of the publications of JP-A-6-1-134933. Further, the flow of the high-viscosity deuterated cellulose solution described in JP-A-56-1 6261 7 may be mixed into a low-viscosity deuterated cellulose solution, and the high and low viscosity may be simultaneously applied. A casting method in which a cellulose solution is extruded to form a bismuth cellulose film. Further, the film formed by the first casting opening on the support may be peeled off by using two casting openings, and the second casting may be performed on the side contacting the support surface to form a film. For example, the method described in Japanese Patent Publication No. Sho 44-20235. The cast deuterated cellulose solution may use the same solution or a different deuterated cellulose solution. In order to impart a function to a plurality of deuterated cellulose layers, the deuterated cellulose solution can be squeezed out from the casting opening separately. Further, the aforementioned deuterated cellulose solution may be cast simultaneously with other functional layers (for example, an adhesive layer, a dye layer, an antistatic layer, an antireflection layer, an ultraviolet absorption layer - 69-200831962 layer, etc.). In the conventional single-layer liquid, in order to form a film of a desired thickness, it is necessary to carry out extrusion with a high-concentration, high-viscosity deuterated cellulose solution. In this case, the stability of the deuterated cellulose solution is often deteriorated to cause solid matter, object damage, poor planarity, and the like. The solution to this problem can be solved by casting a plurality of deuterated cellulose solutions from the casting opening and simultaneously pushing the high-viscosity solution onto the support, thereby improving the planarity. It is excellent in surface-thinness (film), and it is also possible to achieve a reduction in drying load by using a thick deuterated cellulose solution, and to increase the production speed of the film. In the deuterated cellulose film, in order to improve the machine For the physical properties, the following plasticizers can also be used. Phosphate esters or carbonates can be used as the plasticizer. Examples of the phosphate esters include triphenyl phosphate (TPP) and trishydroxymethylphenyl phosphate (TCP). It is represented by phthalic acid esters and citrate esters. Examples of phthalic acid esters include dimethyl phthalate (DM P), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl citrate. Ester (DOP), diphenyl phthalate (DPP) and diethylhexyl phthalate (DEHP). Examples of citrates include triethyl ethoxide (OACTE) and 〇-acetamidine. Tributyl citrate (OACTB). Examples of other carbonates Butyl oleate, methyl decyl ricinate, dibutyl sebacate, various trimellitic acid esters. Among them, it is preferred to use a phthalate plasticizer (DMP, DEP, DBP). , D〇P, DPP, DEHP); especially good for DEP and DPP. -70- 200831962 The amount of plasticizer added is preferably 0.1 to 25 mass% of the amount of deuterated cellulose, more preferably 1 to 20 mass. More preferably, it is 3 to 15% by mass. A deterioration preventing agent (for example, an antioxidant, a peroxide decomposing agent, a radical inhibitor, a metal inerting agent, or an acid compensating agent) may be added to the deuterated cellulose film. Agents and amines. The anti-deterioration agent is described in Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In the respective publications, the amount of the deterioration preventing agent added is preferably 〇1 to 1% by mass of the prepared solution (coating liquid), more preferably 〇. 〇1 to 〇. 2% by mass. When the amount added is less than When it is 0.0% by mass, the effect of the deterioration preventing agent is hardly observed. When the amount added exceeds 1% by mass, there is noticeable deterioration. The case where the stopper penetrates (bleeds out) into the film. Examples of the preferable deterioration preventing agent are, for example, butylated hydroxytoluene (BHT) and tritylamine (TBA). The step of stretching to the post-drying may be carried out under an air atmosphere, or may be carried out under an inert atmosphere such as nitrogen. 1/ Manufacturing of a cellulose-deposited film for use in the present invention The upper coiler may be generally used, or may be wound by a winding method such as a constant tension method, a fixed torque method, a τ division method, or a constant internal stress control method. [Surface Treatment of Deuterated Cellulose Film] The deuterated cellulose film is preferably subjected to surface treatment. Specific methods include, for example, corona treatment, glow discharge treatment, flame treatment, acid treatment, saponification treatment, or ultraviolet irradiation treatment. Further, it is preferable to provide the lower layer as described in Japanese Laid-Open Patent Publication No. Hei 7-33 34-33. From the viewpoint of maintaining the planarity of the film, it is preferable to set the temperature of the deuterated cellulose film to be lower than Tg (glass transition temperature) in these treatments; specifically, it is preferably set to 150 °C or lower. In the case of being used as a transparent protective film for a polarizing plate, it is particularly preferable to carry out an alkali treatment for the deuterated cellulose film from the viewpoint of adhesion to the polarizer. The surface energy is preferably 55 mN/m or more, more preferably 60 mN/m or more ("~75 mN/m or less. Hereinafter, an example of alkali saponification treatment is specifically described. Preferably, after immersing the surface of the film in an alkali solution, a cycle of neutralizing with an acidic solution, washing with water, and drying is performed. The alkali solution, for example, may be a potassium hydroxide solution or a sodium hydroxide solution; The equivalent concentration of the oxidizing ion is preferably in the range of 〇·1 to 3.0 N, more preferably in the range of 0.5 to 2.0 N. The temperature of the alkali solution is preferably in the range of room temperature to Q 90 ° C, more preferably 40 to 701. The surface energy of solids can be obtained by contact angle method, wet heat method and adsorption method as described in "Basic and Application of Wetting" (Reality Press, issued on December 10, 1989). In the case of the deuterated cellulose film of the present invention, it is preferred to use a contact angle method. Specifically, 'two kinds of solutions of known surface energy are dropped onto the deuterated cellulose film on the surface of the droplets and The intersection between the surface of the film, at the intersection of the droplets At the angle between the surface of the film and the surface of the film, the angle of the side containing the droplet is defined as the contact angle of -72-200831962. The surface energy of the film can be calculated by calculation. The retardation of the in-plane direction of the film can be achieved by film formation. The stretching in the transport direction and/or the width direction is performed to provide molecular chain alignment of the deuterated cellulose for adjustment. The stretching may be either uniaxial stretching or biaxial stretching. There are simultaneous biaxial stretching method and sequential biaxial stretching method. However, from the viewpoint of continuous production, it is preferred to use a sequential biaxial stretching method to remove the film from the belt or the roll after casting the coating liquid. After the stretching ζ'·\ in the width direction (long-axis direction), the stretching in the long-axis direction (width direction) is performed. The method of stretching in the width direction, for example, may be in the special opening 62-1 1 5035 No. 4, No. 4, No. 521, No. 4, No. 4, 521, No. 1, No. 4, No. 4, No. 4, No. 1, No. 4, No. 4, No. 4, 298, and No. 11 - 4, 8271, etc. The film is stretched at room temperature. Or under heating conditions. The heating temperature is preferably the temperature of the glass in the film. Hereinafter, the film can be stretched by a treatment in a dry state, especially in the case of a residual solvent. I In the case of stretching in the long axis direction, for example, adjusting the speed of the film conveying roller, when the film is rolled When the speed is accelerated to a faster rate than the stripping speed of the film, the film is stretched. In the case of stretching in the width direction, it can also be carried by holding the wide side of the film on the tenter. 'Slowly pull the wide side of the tenter to stretch the film. You can also use the stretching machine to stretch after the film is dried (it is better to use a long stretcher for uniaxial stretching) ° -73 - 200831962 The stretching ratio of the film (relative to the original length due to the ratio of the increased amount of stretching), preferably in the range of 5 to 50%, more preferably in the range of 10 to 40%, more preferably 1 5~ 3 5 % range. In the case of mainly stretching in the direction of the long axis, the elongation in the long axis direction should be set to 1 〇 to 40%, preferably 15 to 35%; the stretching ratio in the width direction should be set to - 20 to 20%, preferably - 1 0 to 1 0 %. Further, even if the crystallinity is increased by treating the cellulose-deposited film at a high temperature, the water permeability can be lowered. The above-mentioned treatment is required to be carried out at a temperature and time which is not caused by the volatilization of the low molecular compound and the thermal decomposition of the cellulose film itself. The treatment temperature is preferably more than 100 ° C to less than 260 ° C, more preferably from 140 ° C to less than 240 ° C. The treatment time is preferably 5 minutes or more and 2 hours or less, more preferably 10 minutes or more and 1 hour or less. [Moisture absorption coefficient] The coefficient of hygroscopic expansion indicates the amount of change in the length of the sample when the relative humidity is changed at a certain temperature. In order to prevent the increase in the penetration rate of the green amount, the hygroscopic expansion coefficient of the J cellulose film is preferably 30x1 CT5/%RH or less, more preferably 15x1 (T5/%RH, more preferably 10x10_5/%). RH. Further, the smaller the coefficient of hygroscopic expansion is, the better it is. However, it is usually 1.0x1 (T5/%RH or more. The method for measuring the coefficient of hygroscopic expansion is as follows. From the produced polymer film ( The phase difference plate was cut out to have a width of 5 mm and a length of 20 mm, and the end of one side was fixed and placed under an atmosphere of 25 ° C and 20% RH (R〇). The weight of 0.5 g was hanged, and then the length (LQ) was set for 1 。. Then the length (L1) at 80 ° RH (Ri) of wet 74-200831962 was directly measured at 25 °C. The coefficient of hygroscopic expansion is calculated by the following formula. The measurement of 10 samples for the same sample 'is average 値. Hygroscopic expansion coefficient [/% RH] = { ( L1 — L 0) 7 L 0 丨 7 ( R 1 — R 0) In order to reduce the above dimensional change due to moisture absorption, it is preferred to reduce the amount of residual solvent in the film formation and to shrink the polymer film. Free volume. The general method for reducing the residual solvent is to dry at a high temperature for a long time. However, when the time is long, the growth property is naturally lowered. Thus, the amount of residual solvent relative to the deuterated cellulose film is relatively small. It is preferably in the range of 0 · 0 1 to 1% by mass, (more preferably in the range of 0.02 to 0.07 mass. / 〇, more preferably in the range of 0.03 to 0.05 mass. /. by controlling the above residue The amount of solvent can be used to produce a polarizing plate having optical compensation ability at low cost and high productivity. The amount of residual solvent is obtained by dissolving a certain amount of the sample in chloroform, using a gas chromatograph (GC18A, Shimadzu Corporation) In the solution casting method, a film (coating liquid) formed by dissolving a polymer material in an organic solvent is used to produce a film. The drying system in the solution casting method can be roughly classified into, for example, Such a roll (or the drying of the (J-belt) surface and the drying of the film during the conveyance described later. When drying the roll (or belt) surface, it is preferably a temperature not exceeding the boiling point of the solvent used (more than The foam is slowly dried at the point of the film. Further, the drying of the film is preferably carried out at a glass transition temperature of the polymer material of ± 30 ° C, and more preferably at ± 2 0 (: proceeding below. [Thin film retardation] The in-plane retardation Re (Re) and the thickness direction retardation R (Rth) of the film are defined by the following formula (I) and formula (Π). -75- 200831962 • Formula (I) • Formula (Π)

Re = (nx- ny)xd......

Rth= { (nx + ny)/2 - nz } xd In the formula (I) and the formula (Π), nx is the direction of the phase axis in the plane of the film (the direction in which the refractive index becomes maximum). In the formula (I) and the formula (Π), ny is the direction of the phase in the film (the direction in which the refractive index becomes the smallest). In the formula (Π), 112 is the refractive index in the thickness direction of the film. In the formula (I) and the formula (Π), d is a film thickness in units of nm. The second protective film is not particularly limited and may be appropriately selected according to the purpose. For example, a protective film having a Re of 20 to 70 nm and an Rth of 30 to 400 nm is preferably used, as described later. A protective film having Re of 1 〇 or less and Rth of 25 nm or less is used. Further, in order to obtain the most appropriate hysteresis, a phase-sensitive film may be laminated on the second protective film. Further, the complex refractive index (?n: nx - ny) of the protective film is preferably in the range of 0.00 to 0.002 μm. Further, the complex refractive index ((nx+ny)/2-nz} in the thickness direction of the support film and the opposite film is preferably in the range of 0·00 to 0.04. Further, the thickness of the transparent protective film (dry thickness) Preferably, it is 120 microns or less, more preferably 20 to 110 microns, and more preferably 40 to 100 microns. The crossing angle of the retardation axis of the protective film and the absorption axis of the polarizer can be any 値', however, it is preferably parallel or 45. Azimuth angle of ±20 ° [Photoelasticity] -76- 200831962 The photoelastic coefficient of the protective film is preferably 60 x 1 cr8 cm 2 /N or less, more preferably 20x1 (T8cm2/N or less. Photoelastic coefficient It can be obtained by a circular polarizer. [Glass transfer temperature] The glass transition temperature of the protective film is preferably 1 20 ° C or higher, more preferably 1 40 ° C or higher. The glass transition temperature is determined by differential scanning. The calorimeter (DSC) is obtained by taking the average temperature of the temperature at which the glass transitions to the baseline and the temperature at which the baseline starts to change at the temperature increase rate of 10 ° C /min. Polarizing plate, in addition to the aforementioned polarizer and protective film, It is also possible to have a component of the pressure-sensitive adhesive layer, the separator film, and the protective film. <Production Procedure of Polarizing Plate> Hereinafter, the manufacturing process of the polarizing plate of the present invention will be described. The engineering is preferably composed of a swelling process, a dyeing process, a hard film process, a stretching process, a drying process, a protective film bonding process, and a post-bonding drying process. The dyeing process, the hard film process, and the stretching process can be arbitrarily changed. In the present invention, it is also possible to combine a plurality of processes and simultaneously perform the same. Further, as described in Japanese Patent No. 333 1 6 1 5, it is also suitable to perform water washing after the hard film process. It is specially carried out in the order of the swelling process, the dyeing process, the hard film process, the drawing process, the drying process, the protective film bonding process, and the post-bonding drying process. Also, in the above process or even after the design, even the design The above-mentioned step of the line does not matter. -77- 200831962 The swelling process is preferably carried out only with water, but it can also be recorded as No. 1 0-1 53709 In this way, in order to stabilize the optical performance and avoid wrinkles of the polarizing plate substrate on the manufacturing line, the polarizing plate substrate can be expanded by the boric acid aqueous solution to manage the degree of expansion of the polarizing plate substrate. The temperature and time can be arbitrarily set, but it is preferably 1 〇 ° C or more to 60 ° C or less, 5 seconds or more to 2, 0 0 0 seconds or less. The dyeing process can be used by the special opening 2002-86554 Further, the dyeing method may be not only impregnation, but also any means of applying or spraying 3 atomic iodine or a dye solution. Further, a method of dyeing the iodine concentration, the dye bath temperature, the stretching ratio in the solution, and the bath in the stirring bath, as described in JP-A No. 2001-290025, may be used. In the case where a high-priced iodide ion is used as the dichroic molecule, in order to obtain a highly contrasted polarizing plate, the dyeing process is preferably a liquid obtained by dissolving iodine in an aqueous solution of potassium iodide. In this case, the iodine in the aqueous solution of iodine-potassium iodide is preferably in the range of 0.05 to 20 g/liter, and the potassium iodide is preferably in the range of 3 to 200 g/liter, and the mass of iodine and potassium iodide is preferably in the range of 1 to 2,000. . The dyeing time is preferably 1 0 to 1,200 seconds, and the liquid temperature is preferably 1 〇~60 °C. More preferably, the iodine is 0.5 to 2 g/liter and the potassium iodide is 30 to 120 g/liter; the mass ratio of iodine to potassium iodide may be 3 0 to 1 2 0; the dyeing time may be 3 to 600 seconds, and the liquid temperature may be It is 20~50 °C. Further, a boron-based compound such as boric acid or borax may be added to the dyeing liquid as described in Japanese Patent No. 3145747. -78- 200831962 The hard coat process is preferably immersed in a crosslinking agent solution or a coating solution to contain a crosslinking agent. Further, the hard coat process may be carried out in fractions as described in JP-A No. 1 1-521-30. The cross-linking agent can be used as described in Japanese Laid-Open Patent Publication No. 232 897. As described in Japanese Patent No. 3357 1 09, a polyvalent aldehyde is used as a crosslinking agent for the purpose of improving dimensional stability. Suitable for the use of boric acid. In the case where boric acid is used as the crosslinking agent in the hard coat process, metal ions may be added to the boric acid-potassium iodide aqueous solution. The metal ion is preferably zinc chloride. However, zinc chloride such as zinc iodide, zinc sulfate or zinc acetate may be used instead of zinc chloride as described in JP-A-200-35512. . In the present invention, it is suitable to prepare a boric acid-potassium iodide aqueous solution to which zinc chloride is added, and to impregnate the PVA film to carry out a hard film. Boric acid is preferably 10~100g/L, potassium iodide is preferably 1~120g/L, zinc chloride is preferably 〇.〇1~1 〇g/L, and the dura time is preferably 1 〇~1. 200 seconds, the liquid temperature is preferably 10 to 60 ° C. More preferably, boric acid is 1 〇~80 g/L, potassium iodide is 5~100 g/L, zinc chloride is 0.02-8 g/L, hard film time can be 30~600 sec, liquid temperature can be 20~ 50 °C. The stretching process is preferably a longitudinal uniaxial stretching method as described above in U.S. Patent No. 2,451,451, or the like, or a tentering method as described in JP-A-2002-86554. The stretching ratio is preferably 2 times or more and 1 2 times or less. More preferably, it is 3 times or more and 10 times or less. Further, the relationship between the stretching ratio, the thickness of the original sheet, and the thickness of the polarizer can be made as described in JP-A-2002-0020 (the thickness of the polarizing film after the protective film is bonded/original) -79- 200831962 Film thickness) χ (total stretching ratio) &gt; 0.1 7, the relationship between the width of the polarizer when the final bath is taken out and the width of the polarizer when the protective film is bonded is JP-A-2002-040247 The 0.08 S (the width of the polarizing film when the protective film was bonded/the width of the polarizer when the film was taken out from the final bath) was 0.95. The drying process can be carried out by a known method of JP-A-2002-86554. However, a preferred temperature range is 30 to 100 ° C, and a preferred drying time is 30 seconds to 60 minutes. Further, it is also possible to carry out a heat treatment such as setting the fading temperature in water to 50 ° C or higher as described in Japanese Patent No. 3 1 8 8 5 1 3; or as in JP-A 07-325215 or As described in Japanese Laid-Open Patent Publication No. Hei 07-325218, etching is performed under an atmosphere controlled by temperature and humidity. The protective film bonding process is a step of bonding the both faces of the polarizer taken out from the drying system by two protective films. It is preferable to use a method in which an adhesive is supplied before bonding, and a pair of rolls are attached in such a manner that the polarizer and the protective film are superposed. In addition, as described in JP-A Nos. 2001-29 64 265 and JP-A-2002-86554, it is preferable to adjust the fit in order to suppress the unevenness of the recording groove due to the stretching of the polarizer. In the present invention, the moisture content of 0.1 to 30% is suitably used. The adhesion between the polarizer and the protective film is not particularly limited, but for example, it may be a PVA system. a resin (including a modified PVA such as an ethyl acetonitrile group, a sulfonic acid group, a carboxyl group or an alkyloxy group), an aqueous solution of a boron compound, etc. Among these, a PVA resin is preferred, and the thickness of the adhesive is After drying, it is preferably 〇. 〇1 -80- 200831962 〜5 μm, more preferably 0.05~3 μm. Also, in order to improve the adhesion between the polarizer and the protective film, it is suitable for surface treatment and hydrophilicity of the protective film. The surface treatment method is not particularly limited, but a method of alkalizing using an alkali solution, a corona treatment method, or the like can be employed. Also, after the surface treatment, Set white plastic primer, etc. The contact angle of the surface of the protective film and the water is preferably 50 ° or less as described in JP-A-2002-267839. The drying conditions after lamination are as described in JP-A-2002-86554. The method preferably has a temperature range of 30 to 10,000 ° C, and a preferred drying time is 30 seconds to 60 minutes. Further, it can be managed by temperature and humidity as described in JP-A 07-325220. The uranium engraving is carried out under the atmosphere. The content of elements in the photon is preferably 0.1~3·0 g/m2, boron is 0.1~5.0 g/m2, and potassium is 〇1~2.0 g/ In the square meter, the zinc content is 0 to 2.0 g/m 2 . Further, the potassium content may be 〇·2 mass as described in JP-A-2001-166143. The zinc content in the photon may be In the case of the polarizing plate, as described in Japanese Patent No. 3 3 2 3 2 5 5, as described in JP-A No. 2,035,512, Dimensional stability, it is also possible to add organotitanium compounds in any process of dyeing process, stretching process and hard film process. At least one of the organic chromium compounds may contain at least one compound selected from the group consisting of an organic titanium compound and an organic zirconium compound. Further, in order to adjust the color of the polarizing plate -81-200831962, dichroism may be added. &lt;Characteristics of polarizing plate&gt;&lt;&lt;Transmission rate and degree of polarization&gt;&gt; The transmittance of the polarizing plate of the polarizing plate is preferably 42.5 % or more and 49.5 % or less, more preferably 4 2 8 Further, the range of the degree of polarization defined by the following formula (1) is preferably 99.900% or more to 99_999% or less, more preferably 99.940 or more to 9 9.9 9 5 % or less. . Further, the range of the parallel transmittance is preferably 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. Further, the range of the dichroic ratio defined by the mathematical formula (2) of the following formula is preferably 48 or more and 1215 or less, more preferably 53 or more and 525 or less. Mathematical Formula (1) I Parallel Transmittance - Orthogonal Transmittance V Parallel Transmittance + Orthogonal Transmittance

Log dichromatic ratio (Rd) =

Log 穿透 plate penetration rate 100 II plate penetration rate 100

(1 + polarizing plate 100 polarizing plate 100)])] Mathematical formula (2) The iodine concentration and the veneer transmittance may be in the range described in JP-A-2002-258051. The parallel transmittance may be such a small wavelength dependency as that described in JP-A-2001-083328 and JP-A-2002-022950. The optical characteristics in the case where the polarizing-82-200831962 plate is disposed in the crossed Nicols can be the range described in JP-A-2001-09 1736; parallel transmittance and orthogonal transmittance. The relationship may be within the range described in JP-A 02 0 -1 7 4 7 2 8 . The standard deviation of the parallel transmittance per 10 nm between light wavelengths of 420 to 700 nm may be 3 or less, as described in JP-A-2002-22 1 61 8 and at the wavelength of light. The minimum enthalpy per square nanometer (parallel transmittance/straight penetration) between 420 and 700 nm may be 300 or more. f ^ Parallel transmittance and orthogonal transmittance at 440 nm wavelength for polarizing plates, parallel transmittance, wavelength at 550 nm and orthogonal transmittance, parallel transmittance at 610 nm wavelength, and orthogonal The penetration rate can also be suitably set in the range described in JP-A-2002-258-42 and JP-A-2002-258043. &lt;&lt;Durability&gt;&gt; [Damp heat durability] (When the temperature is 60 ° C, 90% RH is placed in a helium atmosphere at 60 ° C, as described in JP-A No. 200 1 -1 1 6922, The absolute 値 of the rate of change of the light transmittance and the degree of polarization before and after the yaw is preferably 3% or less. In particular, the rate of change of the light transmittance is preferably 2% or less, and the absolute rate of change of the degree of polarization is 0.5% or less, more preferably 0.2% or less. Further, as described in Japanese Patent Laid-Open No. 07-077608, the degree of polarization at 500 ° C and 90% RH for 500 hours is preferably 95% or more. The rate is also preferably 38% or more. (2-2) Dry Durability -83- 200831962 Placed in a dry atmosphere at 80 ° C for 500 hours, before and after the light transmittance and polarization The absolute value of the rate of change is preferably less than 3%. In particular, the rate of change of light transmittance is preferably less than 2%, and the absolute rate of change of the degree of polarization is preferably less than 0.5%, more preferably less than 0.2%. [Other durability] In addition, the shrinkage ratio after being placed at 80 ° C for 2 hours as described in JP-A 06-167611 is set to 〇·5 % or less; The polarizing plate laminated body in which the crossed Nicols are arranged on both sides of the glass plate is placed in an atmosphere of 69 ° C for 7 50 hours, and X 値 and y 値 are set as a special opening 10 -06881 No. 8; also suitable for placing in 80 ° C, 9 〇 % R Η atmosphere 2 Ο 0 hour after Raman spectroscopy, the spectral intensity ratio of 105 cm_1 and 157 cm_1 is set to The range described in JP-A 08-07 948 34 and Kaiping 09-1 971 27 is carried out as follows. &lt;&lt;Alignment degree &gt;&gt; The higher the degree of alignment of PVA, the better the polarizing performance is obtained. The order parameter calculated by means of polarized Raman scattering and polarized FT-IR is preferably in the range of 0.2 to 1.0. Further, as described in JP-A-59-1 33509, the photon is The difference between the alignment coefficient of the polymer segment of the total amorphous region and the alignment coefficient of the occupied molecule (0.7 5 or more) may be at least 1 1 5 ; it may also be suitable as described in JP-A 04-2 04 9 07 In this way, the alignment coefficient of the total amorphous region of the polarizer is set to 0.65 to 0.85, and the high iodine ion of 13_, 丨5' The degree of alignment of the sub-84-200831962 is set to 0.8 to 1.0. &lt;&lt;Othercharacteristics&gt;&gt; As described in JP-A-2002-006 1 33, about 30 °C at 80 °C The contraction force in the absorption axis direction of the average unit width at the minute is set to 4.0 N/cm or less, and it is also suitable to place the polarizing plate under heating at 70 ° C as described in JP-A-2002-23621-3. In the case of an hour, the ratio of the change in the absorption axis direction of the polarizing plate to the rate of change in the direction of the polarization axis is set to ±0.6% or less, and the moisture content of the polarizing plate such as f ^ % may be suitable for 2002- The description of No. 090546 is performed in such a manner that it is set to 3% by mass or less. Further, the surface roughness in the vertical direction of the stretching axis may be suitably set to 0.04 μm or less based on the center line average roughness as described in JP-A-2000-249832, and may be suitable for, for example, the special opening degree 1 0-268294. It is described that the refractive index n Q in the direction of the transmission axis is set to be greater than 1.6, and it is also suitable to set the relationship between the thickness of the polarizing plate and the thickness of the protective film, such as the special opening 1 0-1 1 1 4 1 The range described on the 1st is performed in this way. I; &lt;Functionalization of Polarizing Plate&gt; The polarizing plate described above is suitably used as a λ / 4 plate for an LCD having an enlarged viewing angle film, a reflective LC D, and a display for improving the visibility of the display. A functional polarizing plate in which an optical film of a functional layer such as a brightness enhancement film, a hard coating layer, a front scattering layer, and an antiglare layer is combined. A configuration example in which the former polarizing plate and the above-described functional optical film are combined is shown in Fig. 1. It is also possible to bond the optical film and the polarizer of the protective film on one side of the polarizing plate through an adhesive (refer to the first drawing), or to bond the functional optical film to the polarizing photo through the adhesive-85-200831962 agent. A polarizing plate provided with a protective film on both sides (see Fig. 1B). In the case of the former, any transparent protective film can be used on one of the protective films. The degree of peeling between the layers of the functional layer and the protective film is preferably 4.0 N/25 mm or more as described in JP-A-2002-31 1 238. Preferably, the functional optical film is disposed on the liquid crystal module side along with the function, and is preferably disposed on the opposite side of the liquid crystal module, that is, disposed on the display side or the backlight side. Furthermore, in FIGS. 1A and 1B, 1a and 1b are protective films, 2

C 1 is a polarizer, 3 is a functional optical film, and 4 is an adhesive layer. Hereinafter, a functional optical film used in combination with the polarizing plate of the present invention will be described. &lt;&lt;Expanding the viewing angle film&gt;&gt; The polarizing plate described above may be the same as the image TN (twisted nematic), IPS (in-plane switching type), OCB (optical compensation bending type), VA (vertical nematic type). The expanded viewing angle film proposed by the display mode such as ECB (Electrically Controlled Birefringence Type) is used together. In this case, the polarizing plate of the present invention is used in the VA mode and the | ps mode. It is possible to obtain a small change in color odor due to temperature and humidity and a higher display quality. [TN mode] The above-mentioned polarizing plate can be used in a TN mode liquid crystal display device by the following method so as not to cause light leakage. A display device with high display quality, such as a high display quality, and an extended viewing angle film for TN mode, which is preferably used in combination with the Japanese Society of Printing Society, Vol. 36 No. 3 (1 999), 40th to 44th - 86th - 200831962 Pages, monitors, August issue (2002), pages 20 to 24, special Kaiping 4-229828, special Kaiping 6-75115, special Kaiping 6-214116, special Kaiping 8-5 02 06, etc. WV film (made by Fujifilm Co., Ltd.), which is described in TN mode. The preferred structure of the large viewing angle film is that the alignment layer and the optically different direction layer are sequentially provided on the transparent support. The enlarged viewing angle film can be used by bonding with the polarizing plate through the adhesive, but from the viewpoint of thinning. In particular, it is one of the protective films of the above-mentioned polarizers, as described in SID 'OO Dig., page 551 (2000). The alignment layer may be provided with an organic compound (preferably an aggregate). The rubbing treatment of the material, the oblique vapor deposition of the inorganic compound, and the formation of a layer having micro-pits. Further, although an alignment layer for providing an alignment function by providing an electric field, providing a magnetic field, or light irradiation is also known. However, it is particularly preferable to form an alignment layer by performing a rubbing treatment of the polymer. The rubbing treatment is preferably carried out by rubbing the surface of the polymer several times by paper or cloth in a certain direction. The absorption axis direction of the polarizer and the rubbing direction Preferably, it is substantially parallel. The type I' of the polymer used for the alignment layer I': It is suitable to use polyimine or polyvinyl alcohol, as described in JP-A-9-152509 The polymer having a polymerizable group, etc. The thickness of the alignment layer is preferably 0.01 to 5 μm, more preferably 0.05 to 2 μm. The optically isotropic layer is preferably a liquid crystal compound. The liquid crystal used in the present invention. The compound is particularly preferably a discotic compound (disc liquid crystal). The discotic liquid crystal molecule has a disc-shaped core portion and has a benzophenanthrene derivative represented by the following general formula (D-1). Further, in order to provide stability over time, it is preferable to introduce a base which reacts with light, heat, etc., and a preferred example of the above-mentioned disc-shaped liquid crystal. This is described in Japanese Patent Publication No. 8-50206.

The tilt angle of the rubbing direction of the discotic liquid crystal molecules in the vicinity of the alignment layer is aligned almost parallel to the plane of the film, and on the opposite air side, the discotic liquid crystal molecules are aligned to an upright shape which is nearly perpendicular to the surface. The dish-like liquid crystal layer is mixed and aligned in the whole system, and the viewing angle of the TFT-LCD in the TN mode can be realized by this layer structure. The optically anisotropic layer is generally applied to an alignment layer by dissolving a dish-like compound and another compound (for example, a polymerizable monomer or a photopolymerization initiator) in a solvent. It is dried, and then heated to a dish-like nematic phase formation temperature, and then polymerized by irradiation of UV light or the like, and further cooled. The dish-like liquid crystal phase-solid phase transfer temperature of the discotic liquid crystal compound used in the present invention is preferably 70 to 300 ° C, more preferably 70 to 170 ° C. -88-200831962 Further, the compound other than the dish-like compound to be added to the optically anisotropic layer may have a compatibility with the disc compound, and may provide a preferable tilt angle change to the liquid crystal disc compound, or Do not hinder the alignment, any compound can be used. Among these, a polymerizable monomer (for example, a compound having a vinyl group, a vinyloxy group, a propylene fluorenyl group, and a methacryl fluorenyl group), an air-side-side alignment control additive such as a fluorine-containing tri-trap compound, For example, it may be a polymer of cellulose acetate, cellulose acetate propionate, hydroxypropyl cellulose, and cellulose acetate butyrate. The amount of such a compound to be added is generally 0.1 to 50% by mass, more preferably 0. 1 to 30% by mass based on the disc compound. /. . The thickness of the optically anisotropic layer is preferably from 0.1 to 10 μm, more preferably from 0.5 to 5 μm. Further, the Re of the optical anisotropic layer is preferably 10 to 100 nm, more preferably 20 to 70 nm, more preferably 3 0 to 50 nm. The front side retardation Re of the deuterated cellulose substrate used at this time is preferably in the range of 0 to 50 nm, more preferably 2 to 30 nm. Further, the retardation 値Rth in the film thickness direction is preferably in the range of 10 to 200 nm, more preferably 30 to 150 nm. A preferred aspect of the expanded viewing angle film is formed by using a deuterated cellulose film as a transparent substrate film, an alignment layer disposed thereon, and an optically anisotropic layer formed of a disk-like liquid crystal formed on the alignment layer. And the optically anisotropic layer is crosslinked by irradiation with UV light. In addition, in the case of combining the enlarged viewing angle film and the polarizing plate of the present invention, for example, it is also possible to suitably have a direction intersecting the board surface as described in Japanese Laid-Open Patent Publication No. Hei 07-1 98942. The optical axis is laminated with a phase difference plate which exhibits the directionality of the birefringence of -89-200831962, and the dimensional change rate of the protective film and the optical anisotropic layer can be substantially as described in JP-A-2002-258052. Equivalent. In addition, the moisture content of the polarizing plate bonded to the enlarged viewing angle film may be 2.4% or less as described in JP-A-2000-258632, and may be expanded as described in JP-A-2002-267839. The angle of contact of the viewing angle film with water is 70° or less. [OCB mode] The polarizing plate described above can provide a liquid crystal display device having high display quality without causing problems such as light leakage when applied to a liquid crystal display device of the CB mode, as described below. . The Ο C B mode is sometimes referred to as a bending mode or a τι cell mode from the alignment state of liquid crystal molecules. When an electric field is not applied and an electric field is applied by 〇 F F , the liquid crystal alignment state when 〇 N is applied with an electric field greatly changes. When an electric field is applied, the alignment state of the liquid crystal molecules in the liquid crystal cell exhibits a relationship of optical compensation to each other, and the viewing angle is broad. Moreover, compared with other display modes, it is characterized by a fast response speed. In order to perform the black display in the ΟN state, the optical compensation layer must be arranged. The CB mode liquid crystal cell expands the viewing angle film, which is used to perform liquid crystal layer on the liquid crystal layer which is vertically aligned to the central portion of the liquid crystal layer by the application of an electric field and obliquely aligned in the vicinity of the substrate interface, thereby improving the viewing angle characteristics in black display. . In the case where the above-mentioned polarizing plate is used for the 0 CB mode liquid crystal cell, -90-200831962 is suitable for a discotic liquid crystalline compound as described in U.S. Patent No. 5,805,525, and the like. The combined viewing angle film is used in combination. The front side retardation 値Re (unit: nanometer) of the deuterated cellulose substrate used at this time is preferably in the range of 1 〇 to 1 〇〇 nanometer, and more preferably 20 to 70 nm. Further, the retardation 値Rth (unit: nanometer) in the film thickness direction is preferably in the range of 50 to 300 nm, more preferably 100 to 250 nm. Further, the Re of the optically oriented layer having the second protective film is preferably 1 〇 1 〇〇 〇〇 奈 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ [ECB mode] The polarizing plate described above can provide a liquid crystal display device having high display quality without causing problems such as light leakage when applied to an ECB mode liquid crystal display device as described below. In the case of use in a transflective liquid crystal display device, it is suitable to use an optical compensation film which is circularly polarized. In this case, the optical compensation film is suitable for use in the in-plane hysteresis of 1 / 4 of the wavelength of light, the so-called λ / 4 plate. In the all visible light region, for the purpose of satisfying such conditions, for example, an optical compensation film having a hysteresis λ λ /4 and a retardation axis of the optical compensation film of λ /2 can be crossed (refer to Japanese Patent No. 3236304). . As the polarizing plate described above, a circular polarizing plate laminated with a λ / 4 plate can be used. The λ / 4 plate used in the present invention is preferably a retardation film having a hysteresis (Re) of about 1⁄4 of a wavelength in the visible light wavelength range in order to obtain almost complete circularly polarized light in the visible light wavelength range. The so-called "approximately 1 / 4 hysteresis in the visible wavelength range" refers to -91- 200831962. In the wavelength of 400 to 700 nm, the longer the long wavelength, the longer the hysteresis, and the wavelength is The hysteresis Re (Re4 50) measured at 450 nm is 80 to 125 nm and the retardation Re (Re590) measured at a wavelength of 590 nm is in the range of 120 to 160 nm. It is preferably Re590 - Re450^5 nm, more preferably Re590 - Re450g 10 nm. The λ /4 plate used in the present invention is not particularly limited as long as the above conditions are satisfied, however, for example, it can be used for the special opening λ /4 plate made up of a plurality of polymer films described in the publications 5 - 2 7 1 1 8 , JP-A-10-1 688 1 6 , and JP-A-10-0-9052 The λ /4 plate which is obtained by stretching one polymer film described in WO 00/65384, WO 00/26705, and can also be used in JP-A-2000-284126 A known λ /4 plate such as a λ /4 plate having at least one optical anisotropic layer on a polymer film as described in JP-A-2002-31717. Further, the retardation axis direction of the polymer film and the alignment direction of the optically different direction layer can be arranged in an arbitrary I direction suitable for the liquid crystal cell. In the circularly polarizing plate, the slow axis of the λ /4 plate and the transmission axis of the above polarizing plate may be crossed at an arbitrary angle, but it is preferable to cross within a range of 45 ° ± 20 °. However, the retardation axis of the λ /4 plate and the transmission axis of the above-mentioned polarizer do not depend on the range other than the above. In the case of the λ /4 plate and the λ / 2 plate layer, the λ /4 plate is preferably used as described in Japanese Patent No. 3,236,304 and JP-A-10-68816, in accordance with the λ /4 plate and The in-plane slow axis of the λ/2 plate and the angle of the transmission axis of the polarizing plate-92-200831962 are substantially 75° and 15°. In the case of a transmissive liquid crystal display device, it is preferred to use a combination of a discotic liquid crystal compound and a mixed viewing angle film. At this time, the Re of the cellulose substrate is preferably 0 to 300 nm, more preferably 0 to 200 nm. Rth is preferably 0 to 200 nm, more preferably 0 to 100 nm. The Re of the optically different directional layer is preferably 10 to 100 nm, more preferably 10 to 50 nm. [VA Mode] The polarizing plate described above can provide a liquid crystal display device having high display quality without causing problems such as light leakage when applied to a VA mode liquid crystal display device as described below. The VA mode liquid crystal cell optical compensation film system can improve the viewing angle characteristics of the black display state in which the liquid crystal molecules are vertically aligned with respect to the substrate surface in the absence of an applied electric field. Such an optical compensation film is suitably used as a sheet having a phase difference in the in-plane of 0 and a phase difference in the thickness direction (Japanese Patent No. 2866372). The rod-like and vertical alignment of the liquid crystal molecules is optically compensated, and it is preferred to arrange the disc-shaped compound parallel to the substrate. For example, in some cases, a stretched film having the same in-plane retardation , is laminated in such a manner that the slow axis is orthogonal, and some examples are formed by applying a disk-shaped liquid crystalline compound. Further, in order to prevent the deterioration of the orthogonal transmittance in the oblique direction of the polarizing plate, there is also an example in which a sheet composed of a rod-like compound of liquid crystal molecules is laminated. In the polarizing plate, the polarizing plate is formed by laminating the above-mentioned polarizing plate protective film on at least one side of the polarizing film. By arranging the polarizing plate obtained in this way on one surface side or both surface sides of a VA (vertical nematic) type liquid crystal cell, a VA type liquid crystal display device can be obtained. The second protective film used on the polarizing plate described above can be used as an optical anisotropic film. In this case, the front retardation 値Re (unit: nanometer) is preferably 20 to 100 nm. The range is more preferably 30~70 nm. $ Again, the retardation in the thickness direction 値Rth (unit: nanometer) is preferably in the range of 50 to 250 nm, more preferably 80 to 170 nm. When a polarizing plate having a retardation 値 (Rth値) in the thickness direction as a protective film of a polarizing plate in the above range is used, good viewing angle characteristics of the VA liquid crystal display device can be obtained. Further, in addition to the second protective film having the above-described optical anisotropy, any phase difference & film may be used between the above polarizing plate and the liquid crystal cell. Although it is not particularly limited, a stretched decene-based resin film and a polycarbonate-based resin film may be used, or a retardation film formed of a resin film such as polyamide or polyester may be used. Although not particularly limited to the above combination, in order to present a representative combination of good viewing angle characteristics when only the optical anisotropy of the second protective film is present, for example, a thickness of 40 to 100 μm may be used. A fluoridation film having a base substitution degree SA+SB of 2.30SSA+SB<2.80, 0SSBS1.00, which is stretched by 10 to 35% to have a desired optical property of -94-200831962 As the second polarizing plate protective film, a method of forming a polarizing plate formed therefrom and bonding it to the side surface of at least one end of the VA mode liquid crystal cell through an adhesive is prepared. Among them, a polarizing plate having a second polarizing plate protective film obtained by stretching a deuterated cellulose film having a thiol substitution degree SA+SB of 2.30SSA+SB<2_60 and 0.50SSBg0.80, is bonded to the crystal. On both sides of the cell, there is also a polarizing plate having a second polarizing plate protective film obtained by stretching a deuterated cellulose film having a thiol substitution degree SA+SB of 2.30SSA+SB<3.00 and SB=0. A method of using the backlight side of the unit cell for compensation. In addition to the second protective film, the method of using a phase difference plate is also known to provide a polyamine, a polyimine, a polyester poly(ether ketone), between a VA mode liquid crystal cell and a polarizing plate. A polymer of at least one selected from the group consisting of poly(amidoximine) and poly(esterimide), and the refractive index in the in-plane direction is denoted as nx and ny, and the thickness direction When the refractive index is nz, a method of compensating for a retardation film of η X &gt; ny &gt; η z can be satisfied. [IPS mode] The polarizing plate described above can provide a liquid crystal display device having high display quality without causing problems such as light leakage when applied to a liquid crystal display device of the I P S mode as described below. The optical compensation film for liquid crystal cells of the I PS mode is used to enhance the optical compensation thin of the liquid crystal molecules aligned on the parallel substrate surface and the viewing angle characteristics of the orthogonal transmittance of the polarizing plate when the black display is not applied. -95- 200831962 The I P S mode is black in the absence of an applied electric field, and the transmission axes of the upper and lower polarizing plates are orthogonal. However, in the case of observing from an oblique direction, the crossing angle of the transmission axis is not 90°, and light leakage occurs to reduce the contrast. In the case where the above-mentioned polarizing plate is used in the IPS mode, in order to reduce the light leakage, it is suitable to have a phase difference close to the in-plane and a phase difference in the thickness direction, as described in Japanese Laid-Open Patent Publication No. Hei No. Hei. The expanded viewing angle film is used in combination. For example, for example, a polarizing plate having a retinal film having a Re of 0 to 100 nm and an Rth of 0 to 200 nm as a second protective film is used, and Re is 50~ A phase difference plate of 300 nm and Rth of 0 to 200 nm is used in combination; in some cases, it is set on a smectin film having a Re of 0 to 100 nm and an Rth of 0 to 200 nm. A polarizing plate having an optically anisotropic layer is used in combination with a phase difference plate having a Re of 50 to 300 nm and an Rth of 0 to 200 nm. Further, the polarizing plate which can be used for optical compensation of the liquid crystal display device of the PS mode is not limited to the following. However, it may be suitably used by combining a retardation film having a maximum refractive index in the film thickness direction. By the means as described above, it is possible to use the bismuth hydride film as the second protective film of the polarizing plate by having the property that the refractive index in the film thickness direction is maximized. The preferable optical characteristics in which the refractive index in the film thickness direction is maximized as described above are the characteristics of the phase difference film to be combined. However, the following characteristics are suitable for use in the -96-200831962. For example, R e is preferably 〇~50 nm, and more preferably 〇~10 nm. On the other hand, Rth is preferably a 20-300 nm, more preferably an 80--160 nm. Further, the polarizing plate which can be used for optical compensation of the liquid crystal display device of the PS mode is not limited to the following. However, it is also possible to suitably use an additive having an optical anisotropy which reduces the thickness of the disintegrated film, and includes a positive electrode. The hysteresis is I Re| €10, the retardation in the thickness direction is I Rth| $25 of the second protective film of the polarizing plate, or has a substitution ratio of SA+SB of 2.30 SSA+SB&lt;3_00, 0$SB&lt;; 1_00, a polarizing plate of a second polarizing plate protective film composed of a deuterated cellulose film having a film thickness of 40 to 80 μm, or a second optical anisotropy stretched by the above-described deuterated film A polarizing plate or the like for protecting a film. Further, the polarizing plate may be used in combination with a phase difference film obtained by coating a liquid crystalline compound on a norbornene resin, a polycarbonate resin or the like. As a specific example, for example, a polarizing plate using Z-TAC (manufactured by Rich Films Co., Ltd.) as a second protective film may be attached to the backlight side of the unit cell, on the side of the viewer. A polarizing plate having a deuterated cellulose film having a film thickness of 40 μm of 2.30 SSA + SB &lt; 2.50, 0.80&lt; SB &lt; 1.00, and a film thickness of 40 μm as a second polarizing plate protective film, and the polarizing plate and the liquid crystal cell are used thereon An embodiment in which a stretched norbornene film or a polycarbonate film is stretched between them is provided. Further, on the backlight side of the unit cell, a deuterated cellulose film having 2.30 S SA + SB &lt; -97-200831962 2·50, 0.80&lt;SB&lt;1.00, and a film thickness of 40 μm is provided as the second polarizing plate Between the polarizing plate of the protective film and the liquid crystal cell, a decene-based film having a thickness of 80 to 100 μm is stretched, and has a phase difference of Re of 100 to 250 nm and Rth of 50 to 150 nm. The plate is provided with a bismuth cellulose film of 2 · 30 SSA + SB &lt; 2 · 5 0, 0.8 0 &lt; SB &lt; 1· 〇〇, film thickness 40 μm on the side of the viewer. The polarized plate of the two polarizing plate protective film and the liquid crystal cell are provided with a stretched poly-carbonate phase difference of 50 to 100 μm, Re of 200 to 300 nm, and Rth of 0 to 50 nm. Board compensation method, etc. &lt;&lt;Antireflection Film&gt;&gt; The polarizing plate described above can be used in combination with an antireflection film. As the antireflection film, a film having a reflectance of about 1.5% of a low refractive index material such as a fluorine-based polymer or a film having a reflectance of 1% or less by multilayer interference of a film can be used. One. In the present invention, a structure in which a low refractive index layer and at least one layer having a higher refractive index than the low refractive index layer (i.e., a high refractive index layer, a medium refractive index layer) are laminated on the transparent support are suitably used. Further, the antireflection film described in the Japanese Journal of Technology, Vol. 38, No. 1, May 2000, pages 26 to 28, and JP-A-2002-301783 may be suitably used. The refractive index of each layer satisfies the following relationship. 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 The transparent support system used for the antireflection film can be suitably used in the former-98- 200831962 A transparent polymer used for the protective film of the polarizing layer. The refractive index of the low refractive index layer is preferably 1.20 to 1.55, more preferably 1.30 to 1. 5 0 〇 The low refractive index layer is preferably used as the outermost layer having scratch resistance and antifouling properties. In order to improve the scratch resistance, it is also suitable to impart a smoothness to the surface by using a material containing fluorine. The fluorine-containing compound, for example, may be suitably used in the paragraphs [0018] to [0026] in the specification of Japanese Laid-Open Patent Publication No. Hei 9-222503, and the paragraph number [001 9] in the specification of the Japanese Patent Laid-Open Publication No. Hei No. Hei. ～ 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 The ruthenium-containing compound is preferably a compound having a polyoxo structure, however, reactive ruthenium (for example, Sayrapram (manufactured by Nitrogen Co., Ltd.)) or a polyoxyalkylene having a decyl group at both terminals may be used. (Japanese Unexamined Patent Publication No. 11-2584303), et al. It is also possible to carry out a condensation reaction by a condensation reaction of an organometallated 1' compound such as a decane coupling agent with a specific fluorinated hydrocarbon-containing decane coupling agent in the presence of a catalyst (JP-A-58-1 42958) Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. 2001-48590 and JP-A-2002-53804. On the low refractive index layer, an additive other than the above may be suitably used to contain a chelating agent (for example, cerium oxide ( vermiculite), fluorine-containing particles (magnesium fluoride, -99-200831962 藏化铭, fluorine) /Chemical lock) The refractive index inorganic compound of the low refractive index layer of the temple having an average particle diameter of 1 to 150 nm, and the paragraph number in the Japanese Patent Publication No. 1彳-3 8 2 0 [〇〇2 0] ~ [〇〇3 8] organic fine particles, etc.), a decane coupling agent, a smoothing agent, a surfactant, and the like. The low refractive index layer can be formed by a vapor phase method (vacuum evaporation method, sputtering method, ion plating method, plasma CV D method, etc.), but it is preferably from the viewpoint of being inexpensive to manufacture. It is formed by a coating method. The coating method is preferably a drop coating method, an air knife coating method, an air curtain coating method, a roll coating method, a wire coating method, a gravure coating method, or a micro gravure coating method. The film thickness of the low refractive index layer is preferably from 30 to 200 nm, more preferably from 50 to 150 nm, more preferably from 60 to 120 nm. The medium refractive index layer and the high refractive index layer are preferably composed of an inorganic compound ultrafine particle having a high refractive index layer having an average particle diameter of 1 〇 〇 or less dispersed in a material for a base material. The inorganic compound fine particles of the high refractive index layer are preferably an inorganic compound having a refractive index of 1.65 or more, for example, Ti, Zn, Sb, Sn, Zr, Ce,

An oxide of Ta, La, In or the like, a composite oxide containing such a metal atom, or the like. For the ultrafine particle system, a surface treatment agent can be used as a surface treatment agent (a decane coupling agent, etc., and an anionic compound, JP-A No. 1-295503, JP-A No. Hei 01-153703, JP-A-2000-9908, an anionic compound) Or an organic metal coupling agent; a core-shell structure having a high refractive index particle as a core, which has been treated, and the like, (specifically, 2001-166104-100-200831962, etc.) In the case of a material for use as a base material, a public plastic resin, a curable resin film, or the like can be used, for example, in the case of a material for use as a base material, for example, JP-A No. 1 1 -1 53 703. However, it is also possible to make a polyfunctional material such as No. 2000-47004, JP-A-2001-31 5242, No. 2001-319781, and JP-A-2001-296401, or The refractive index of the curable vine high refractive index layer obtained by the metal alkoxide composition described in No. 2938 1 8 is preferably 1.70 to 2.20. The height is preferably 5 nm to 10 μm, more preferably Is the refraction of 10 nm ~ medium refractive index layer It is adjusted to be between the low refractive index and the refractive index of the high refractive index layer. The refractive index of the medium refractive index layer is 1 _50 〜 1.70. The haze of the antireflection film is preferably 5% or less, more preferably In addition, the strength of the film is preferably 2 Η or more, more preferably 3 Η or more, in accordance with JIS Κ 5400 pencil hardness test 。. &lt;&lt; Lifting Θ度ΘΘ> The aforementioned polarizing plate system can In combination with the enhanced brightness film, the J-degree film system has a circularly polarized or linear polarizing function, and is disposed between the backlights, and reflects one side of the circular or linear polarized light on the backlight side or backscatters. Re-reflection from the backlight The light, which is known as the heat in the special section, the bulletin, etc., can be used in the 〇 refractive index layer / 1 micron. The refractive index of the layer is preferably less than 3%. It is more suitable. Enhance the brightness: polarizing plate and: rear, polarized state -101- 200831962 and then incident on the brightness-enhancing film and polarizing plate to form partial transmission, by repeating this process to enhance the use of light, the front brightness is raised to about 1 . As a film for improving brightness, it is known that there is an omnidirectional reflection mode directional scattering method, and any of them can be polarized with the present invention. In the case of the unidirectional reflection method, it has been known that a multi-layered one-stretch film and an unstretched film increase the refractive index difference in the stretching direction, and the directionality-increasing brightness film having a rate and a transmittance is used. Multilayer film method of dielectric body (WO 95/1 7691, WO 95/1 7692, No. 95/1 7699), and cholesteric liquid crystal (European Patent No. 606940A2, special Kaiping 8-- 271 731 public records). The present invention is suitable for the brightness film of the multilayer film of the dielectric Miller principle, DBEF-E, DBEF-D, and DBEF-M (all of which are NIPOCS (made by Nitto Electric Co., Ltd.) of the brightness enhancement film of the 3M company cholesteric liquid crystal system) For the NIPOCS system, refer to the Nitto Technical Daily No. 1.38 test number, May 2000, pages 19 to 21, etc. Further, in the present invention, it is preferable to use, as in WO 97/32223, No. 97/32224, WO 97/32225, WO 97/32226, and the special intrinsic birefringent polymers described in the Korean Patent Publication No. 9-274 1 08 and JP-A No. 1 1 -1 74231 The intrinsic complex-folding compound is blended, and it is uniaxially stretched by the unidirectional stretching method, and thus 4 times and the heterogeneous plate axis is pulled back, and the WO method is reported to improve the system): (share) B No. 1, w〇• Description i is a combination of poly-[Liang-102-200831962 degree film together. The brightness-increasing film of the isotropic scattering method is preferably DRPF-H (manufactured by 3M Company). The polarizing plate and the brightness-enhancing film of the present invention are preferably one which is bonded by an adhesive or an integrated type in which one side of the protective film of the polarizing film is used as a brightness-increasing film. &lt;&lt;Other functional optical film&gt;&gt; In the above polarizing plate, it is preferable to provide a hard coat layer, a front scattering layer, an antiglare layer, a gas barrier layer, and a smooth layer. A functional optical film such as an antistatic layer, an undercoat layer or a protective layer is used in combination. Further, it is preferable that these functional layers are used by combining the above-mentioned antireflection layer or optically anisotropic layer in the same layer. [Hard Coating Layer] The above-mentioned polarizing plate is preferably used in combination with a functional optical film provided on the surface of a transparent support for the purpose of imparting mechanical strength such as scratch resistance. In the case where a hard coat layer is used for the aforementioned antireflection film to be applied, it is particularly preferably provided between the transparent support and the high refractive index layer. The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of a curable compound by at least any one of light and heat. The organometallic compound having a curable functional group which is preferably a photopolymerizable functional group and a hydrolyzable functional group is preferably an organic compound oxide sand compound. For the specific constituents of the hard coat layer, for example, those described in JP-A-2002-144913, JP-A-2000-9908, WOOO/4 6617, and the like can be used. -103- 200831962 The film thickness of the hard coat layer is preferably 0.2 to 100 μm. The strength of the hard coat layer is preferably in accordance with the pencil hardness test of J I S K54 0 0 or more, more preferably 2H or more, more preferably 3H or more. Moreover, according to the abrasion test of JIS K5400, the less the amount of friction of the test piece before and after the test, the better. As the material for forming the hard coat layer, a compound containing an ethylenically unsaturated group or a compound containing a ring-opening polymerizable group can be used, and these compounds can be used singly or in combination. A preferred example of the compound containing an ethylenically unsaturated group, for example, f may be, for example, ethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tetraacrylate, pentaerythritol Polyacrylates of polyhydric alcohols such as acrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, etc.; diacrylate of bisphenol A diglycidyl ether, hexanediol diglycidyl ether An epoxy acrylate such as a diacrylate; a preferred compound such as an urethane acrylate obtained by a reaction of a hydroxyl group-containing acrylate such as polyisocyanate or hydroxyethyl acrylate. Further, commercially available compounds, for example, may be EB-600, EB-40, EB-140, EB-1150, EB-1290K, IRR214, EB-2220, TMPTA, TMPTMA (above is Daisy UCB) (Stock) company), UV-6300, UV-1700B (above is manufactured by Sakamoto Synthetic Chemical Industry Co., Ltd.). Further, preferred examples of the compound containing a ring-opening polymerizable group may, for example, be ethylene glycol diglycidyl ether of glycidyl ether, bis-104-200831962 phenol A diglycidyl ether, trishydroxyl Methyl ethane triglycidyl ether, trimethylolpropane triglycidyl ether, glyceryl triglycidyl ether, triglycidyl hydroxyethyl trimeric isocyanate, sorbitol tetraglycidyl ether, pentaerythritol tolyl tetra Glycidyl ether, polyglycidyl ether of cresol novolac resin, polyglycidyl ether of phenol novolac resin, etc.; erro oxide 2021 P of alicyclic epoxy resin, Cerro 2081, Eplide GT- 301, Optimus GT-401, EHPE3150CE (hereinafter referred to as Daisy Chemical Industry Co., Ltd.), phenol novolac resin polycyclohexyl epoxy methyl ether, etc., oxetane OXT-121 OXT-221, 〇X-SQ, PNOX-1009 (above is East Asia Synthetic Co., Ltd.). In addition to this, a polymer of glycidyl (meth) acrylate or a copolymer of a glycidyl (meth) acrylate and a monomer copolymerizable may be used for the hard coat layer. On the hard coat layer, in order to reduce the hardening shrinkage of the hard coat layer, the adhesion between the substrate and the adhesion between the substrates, and the purpose of reducing the curl of the hard coat treated article of the present invention, it is also suitable for adding bismuth, titanium, pin, aluminum. Crosslinked fine particles such as oxide fine particles or crosslinked particles such as polyethylene, poly(meth)acrylate or polydimethylcyclohexane, and organic fine particles such as crosslinked rubber fine particles such as SBR and NBR . The average particle size of such crosslinked microparticles is preferably from 1 to 20,000 nm. Further, the shape of the crosslinked fine particles may be a spherical shape, a rod shape, a needle shape, a plate shape or the like without particular limitation. The amount of the fine particles added is preferably 60% by volume or less, more preferably 40% by volume of the hard coat layer after hardening. /. the following. -105- 200831962 The hard coat layer is preferably hardened by using heat or active energy rays, and it is more preferable to use active energy rays such as radiation, r-line, α-line, electron beam, ultraviolet light, etc. from the viewpoint of safety and productivity. It is especially good to use electronic wires and ultraviolet rays. In the case of hardening by heat, when considering the heat resistance of the plastic itself, the heating temperature is preferably 1 40 °c or less, more preferably 1 〇 〇 °c or less. [Front Scattering Layer] The front scattering layer is used to improve the viewing angle characteristics (hue and brightness distribution) in the upper, lower, left and right directions when the polarizing plate of the present invention is applied to a liquid crystal display device. In the present invention, it is preferred that the fine particles having different refractive indices are dispersed in the binder. For example, the forward scattering coefficient can be used to specify the relative refractive index of the transparent resin and the fine particles. JP-A-2000-99809, and the configuration in which the haze is limited to 40% or more, and the like. Further, in order to control the viewing angle characteristics of the haze of the polarizing plate of the present invention, it is also suitable to be used in combination with the "Romez Emperor" described in Sumitomo Chemical Technical Report "Optical Functional Film" on pages 31 to 39. . [Anti-glare layer] An antiglare layer is used to scatter reflected light to prevent reflection. The anti-glare function can be obtained by forming irregularities on the outermost surface 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%, still more preferably from 7 to 20%. In the method of forming the concavities and convexities on the surface of the film, for example, a method of adding fine particles to the surface of the film by adding -106 to 200831962 (for example, JP-A-2000-271878, etc.), and adding a small amount (〇·1~) can be suitably used. 50% by mass of a larger particle (having a particle diameter of 5 to 2 μm) to form a surface unevenness film (for example, JP-A-2000-281 41 0, JP-A-2000-95893, JP-A-2007-95893 In the method of physically transferring the uneven shape on the surface of the film (for example, JP-A-63-278839, JP-A No. Hei 01-178371, JP-A No. 2001-28, No. 407, and the like) In the case of the inlaid processing method described in, for example, Japanese Laid-Open Patent Publication No. Hei. Preferably, the functional layers are provided on either one or both sides of the polarizer side and the opposite side of the polarizer. (Liquid Crystal Display Device) Next, a liquid crystal display device using the polarizing plate of the present invention will be described. 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 of the present invention has liquid crystal cells (15 to 19) and liquid crystal cells (15 to 19), and is disposed on the upper polarizing plate 11 and the lower polarizing plate 2 2 . Although the polarizing plate is held by the polarizing film and the pair of transparent protective films, in the second drawing, the integrated polarizing plate is shown, and the detailed structure is omitted. The liquid crystal cell is composed of a liquid crystal layer formed by the upper substrate 15 and the lower substrate 18, and the liquid crystal molecules 17 held thereby. The liquid crystal cells are classified into, for example, ΤΝ (twisted nematic), IPS (in-plane switching), OCB (optical compensation bending -107- 200831962), depending on the alignment state of the liquid crystal molecules when Ο 〇 〇 FF is displayed. The display mode of the type), VA (vertical nematic type), and EC B (electrically controlled birefringence type), however, the polarizing plate of the present invention can be used in any of the display modes, whether it is a transmissive type or a reflective type. An alignment film (not shown) is formed on the surface of the substrate 15 and 18 contacting the liquid crystal molecules 17 (hereinafter, referred to as "inner surface"), and rubbing treatment is performed on the alignment film. The alignment of the liquid crystal molecules 17 in the absence of an applied electric field or a low applied state is controlled. Further, on the inner surfaces of the substrates 15 and 18, a transparent electrode (not shown) capable of applying an electric field is formed on the liquid crystal layer composed of the liquid crystal molecules 17. The rubbing direction of the TN mode is performed in a direction in which the upper and lower substrates are orthogonal to each other, and the magnitude of the tilt angle is controlled by the strength and the number of rubbing times. The alignment film is formed by baking after coating polyimide. The magnitude of the twist angle (twist angle) of the liquid crystal layer is determined by the intersection angle of the rubbing direction of the upper and lower substrates and the optically active agent added to the liquid crystal material. In order to make the twist angle here 90°, an optically active agent having a pitch of about 60 μm is added. In addition, in the case of a notebook computer or a personal computer screen or a liquid crystal display device for a television, the twist angle is set at around 90° (85 to 95°), and is used as a reflective display device such as a mobile phone. In the case of use, it is set at 0 to 70 °. Also, in the IPS mode and the ECB mode, the twist angle is 0°. Further, in the 丨P S mode, the electrodes are disposed only on the lower substrate 18, and an electric field parallel to the substrate surface is applied. Further, in the OCB mode, there is no twist angle and the tilt angle becomes large; and in the VA mode, the liquid crystal molecules 17 are aligned perpendicular to the upper and lower substrates. -108- 200831962 Here, the thickness Δ n d of the thickness d of the liquid crystal layer and the refractive index anisotropy Δ η can change the brightness at the time of white display. Therefore, in order to obtain the maximum brightness, it is set within the range of each display mode. Generally, a high contrast is obtained by slightly orthogonally crossing the intersection angles of the absorption axis 1 2 of the upper polarizing plate 1 1 and the absorption axis 2 3 of the lower polarizing plate 2 2 . Although the crossing angle of the rubbing direction of the absorption axis 1 2 of the liquid crystal cell upper polarizing plate 1 and the upper substrate 15 is in accordance with the liquid crystal display mode, the TN and IPS modes are generally set to be parallel or vertical. In the OCB and ECB modes, it is mostly set to 45°. However, since the optimum color of each display mode is different by adjusting the color tone and the viewing angle of the display color, it should not be limited to this range. The liquid crystal display device using the polarizing plate is not limited to the configuration of Fig. 2, and may include other members. For example, a color filter may be disposed between the liquid crystal cell and the polarizer. Further, between the liquid crystal cell and the polarizing plate, the above-described viewing angle films 13 and 20 may be additionally provided. The polarizing plates 1 1 and 22 and the enlarged viewing angle films 13 and 20 may be disposed in a laminated form in which an adhesive is attached, or one of the liquid crystal cell side protective films may be used on the enlarged viewing angle film, that is, as a so-called integrated type.楕 Round polarizer for configuration. Further, in the case of use as a penetrating type, a cold cathode or a hot cathode fluorescent tube, or a light emitting diode, a field effect emitting element, or an electroluminescence element may be disposed on the back surface as a light source. Further, the liquid crystal display-109-200831962 apparatus using the polarizing plate of the present invention may be of a reflective type. In this case, only one polarizing plate may be disposed on the observation side, but on the back surface of the liquid crystal cell or under the liquid crystal cell. A reflective film is provided on the inner surface of the side substrate. Of course, the front light using the above-described light source may be provided on the liquid crystal cell observation side. According to the present invention, it is possible to provide a polarizing plate which has a small change in transmittance, a change in polarizing rate, and high durability with heat and humidity. Further, according to the present invention, it is possible to provide a liquid crystal display device which does not cause a significant change in color odor and which has high display quality. [Examples] Hereinafter, the present invention will be specifically described by way of examples, but the embodiments of the present invention are not limited thereto. &lt;Production of Cycloolefin-Based Resin Film A-1&gt; ZE〇N〇R 1 4 2 0 (Hydrogen of a ring-opening polymer of a decene-based product, manufactured by Nippon Co., Ltd., Tg: 140 ° C) Nine. Using the uniaxial extrusion molding machine (manufactured by Nippon Steel Co., Ltd.) having a cavity inner diameter of 50 nm and a spiral L/D of 28, the above-mentioned nine particles were melt-extruded at a barrel temperature of 260 °C. The mold temperature is 260. The coated die is extruded with a sheet-like molten resin having a width of 650 mm, so as to be in close contact with the first cooling drum (diameter: 200 mm, temperature T1: 135 ° C, peripheral speed R1: 12.50 m / s), directly transferred to the first cooling roller and then the second cooling cooling drum by a knife coater (diameter: 350 mm, temperature D: 2: 125. Weekly speed 82: 14.46 meters / sec), then the third cooling drum (diameter: 350 mm, temperature T3: 80 ° C, weekly speed R3 · · 14_40 m / s), -110- 200831962 successive cooling and borrowing Smoothing by transfer of the cooling drum surface to obtain a thermoplastic resin film having a width of 550 mm (retracted to 50 mm on the left and right sides); after adjusting the drum, it is cut off from both ends by a cutter 3 0 mm, a cylindrical drum is wound into a cylindrical shape to obtain a cylindrical optical film. At this time, the first cooling is performed. The contact time 11 of the sheet-shaped thermoplastic resin of the wheel is 3.1 (sec), and the resin temperature T1 when leaving the first cooling drum is 1 32 (° C.), then t1 X (T 1 - T g ) is a 1 2 (Unit: second • degree). In this way, a film of a terpene-based resin having a thickness of 80 μm is formed by extrusion. (Production of polyester resin film A-2) A small piece of polyester material is used in Henschel The mixer is dried in a paddle dryer to have a water content of 50 ppm or less, and then melted in an extruder having a heater temperature of 280 to 300 ° C. The molten polyester resin is molded by a die. The part is spit out onto a roller to which static electricity is applied to obtain a non-crystalline billet. The non-crystalline billet is stretched in the direction in which the billet flows, so that the draw ratio is 3.3 times, and then in the width direction of the billet. The polyester resin film A-2 having a thickness of 1 μm was produced by stretching at a draw ratio of 3.9 times. &lt;Production of polycarbonate resin film A-3&gt; 100 parts of polycarbonate Resin (viscosity average molecular weight 40,000, bisphenol A type), 1. 2-particulate 2-(2'-hydroxy-3',5'-di-t-butylbenzene - benzotriazole, 430 parts of dichloromethane, and 90 parts of methanol were placed in a sealed container, and kept at 80 ° C under pressure, and completely dissolved while stirring to obtain a coating liquid composition. 111- 200831962 Next, the coating liquid composition was filtered, cooled, kept at 33 ° C, uniformly cast on a stainless steel belt, and dried at 33 ° C for 5 minutes. The support roller was conveyed while drying to obtain a polycarbonate film having a film thickness of 100 μm. &lt;Preparation of vinylidene chloride-based resin film A-4&gt;&lt;&lt;&gt; Preparation of coating layer 1 to be coated&gt;&gt;&gt; [Composition of coating layer of coating layer 1] _ • Chlorine-containing polymer: R204. ............12g' (Asahi Kasei Life & Minsheng (share) company "Sharon Randy R204"} • Tetrahydrofuran.............. ....63 g &lt;&lt;Coated with layer 1&gt;&gt; On a cellulose triacetate film (TAC-TD80U, manufactured by Fujifilm Co., Ltd.) having a thickness of 80 μm, The coating machine for the slit die was applied with the coating liquid for the layer 1 so as to have a thickness of 3 μm after drying. The coating was applied at a conveying speed of 30 m/min to 60 ° C and 100 ° C. The film was dried for 5 minutes and wound up. <Production of vinyl alcohol-based resin layer-coated film A-5 and A-6> &lt;&lt;&gt;&gt; Preparation of layer 2 formed of vinyl alcohol-based polymer &gt; [Composition of the coating liquid of the layer 2] _ • Vinyl alcohol polymer HR-3010 (manufactured by Kuraray Co., Ltd.) · 5 parts by mass • Vermiculite ME-100 (solid matter) Ingredient ratio of 5% by mass, Kepu Chemical Company system).........10 parts by mass •water....................〇〇质量份-112- 200831962 ME-100 with The water was mixed according to the desired concentration, and then subjected to high-pressure dispersion treatment for 3 times at 30 ° C using a high-pressure disperser to disperse it in water. HR-3010 was stirred by water at 95 ° C for 2 hours. Dissolved &lt;&lt;Coated with Layer 2&gt;&gt; The side of the layered layer of cellulose triacetate (TAC-TD80U, manufactured by Fujifilm Co., Ltd.) was set at 1 m/liter. The alkali solution was subjected to alkalization treatment at 50 ° C. Then, on the alkalized surface of the cellulose triacetate film, a coater having a slit die was used in such a manner that the film thickness after drying was 5 μm. The coating liquid for coating layer 2 was applied, and then applied at a conveying speed of 30 m/min, and dried at 1 3 (TC for 5 minutes, and wound up. &lt;Production of First Protective Film&gt;&lt;&lt;Production of First Protective Film B-1&gt;&gt; Treatment of Object II - Using a high frequency transmitter (corona) on both sides of the above-mentioned cyclic olefin-based stem film A-1 HV05-2, manufactured by Tom Technology Co., Ltd.), with output voltage of 100%, output power of 250W, wire electrode with diameter of 1.2 mm, electrode length of 240 mm, working electrode spacing [5 mm The corona discharge treatment was carried out for 3 seconds, and the surface tension was surface-modified to become 0.072 Å/meter. &lt;Coating of the undercoat layer&gt; -113-200831962 The following is applied to both sides of the cycloolefin-based resin film A-1 which has been subjected to the pretreatment, so that the thickness of the dried film is 90 nm. The coating liquid for coating is shown below. [Composition of coating liquid for undercoating] ___ • Styrene butadiene latex (solid content: 43%)..... 300 g• 2,4-dichloro-6-hydroxy-s-three-pill sodium salt (8%).........49g•distilled water..................1,6 0 0g 200831962

CHa H3C〇";i,.7f-A'0 female(10) 〇CH3 och3 8 0 : 2 0 molar ratio general formula (1) In addition, the condensation ratio α measured by 29Si-NMR is 〇·56. As a result, it can be understood that most of the decane coupling agent sol is a linear structural part. Moreover, the residual rate of the raw material propylene oxypropyl trimethoxide sands is analyzed by gas chromatography. < 5% or less. &lt;&lt;Preparation of coating liquid for hard coating layer&gt;&gt; [Composition of coating liquid for hard coating layer] 40.0 g I 0.0 g • 2.0 g. 2.0 g 13.0 g 0.06 g II · gram 38.5 grams • ΡΕΤ-30........... • DPHA ............ • I rg aq u re 184......... • SX- 350 (30%)........ • Crosslinked acrylate-styrene particles (30%) • FP-1 3............ • Sol solution.... ........ • Ψ ............. -115- 200831962 A filter made of polypropylene with a pore size of 30 μm is filtered to prepare a hard coating. The coating liquid for the layer. The various compounds used are as follows: • PET-3 0: pentaerythritol triacrylate, pentaerythritol tetraacrylate Mixture (manufactured by Nippon Kayaku Co., Ltd.) • Irgaqure 184: polymerization initiator (made by Ciba Specialty Chemicals Co., Ltd.) • SX-350: crosslinked polystyrene particles with an average particle diameter of 3.5 μm (refraction) The rate is 1.7, 30% toluene dispersion made by the company, used in a polytron dispersion machine at 10, rpm for 20 minutes.) • Crosslinked acrylate-styrene Particles: an average particle diameter of 3.5 μm (refractive index of 1.55, a 30% toluene dispersion manufactured by Nippon Chemical Co., Ltd., and dispersed by a polytron disperser at 10,000 rpm for 20 minutes) The produced cycloolefin-based resin film A-1 is wound into a cylindrical form, and the coating liquid for a hard coating layer is directly extruded and applied to a polarizing plate protective film on an auxiliary roll using a coater having a slit die. At the end of the coating layer, the coating was carried out at a conveying speed of 30 m/min, dried at 30 ° C for 15 seconds, dried at 90 ° C for 20 seconds, and further dried with nitrogen. Under the quality, use a 1 60 W/cm air to cool the methyl halide lamp ( Irradiated by ultraviolet light of 90 mJ/cm2, the coating layer is cured to form an anti-glare layer having an anti-glare property of 6 μm thick, and is wound up in a cycloolefin resin. A hard coating layer is provided on the film A-1. &lt;Coating of Low Refractive Index Layer&gt; -116- 200831962 &lt;&lt;Synthesis of Perfluoroolefin Copolymer (1)&gt;&gt; In an autoclave equipped with a stirrer made of stainless steel having a content of 100 ml 40 ml of ethyl acetate, 14.7 g of hydroxyethyl vinyl ether, and 0.55 g of dilauryl peroxide were charged and degassed into nitrogen in the system. Further, in an autoclave, 25 g of hexafluoropropane (HFP) was introduced and the temperature was raised to 65 °C. The pressure at the point where the temperature in the autoclave reached 65 ° C was 0.53 M Pa (5.4 kg/cm 2 ). # Maintain the reaction at this temperature for 8 hours, turn off the heat when the pressure reaches 0.3 1 MPa (3.2 kg/cm 2 ), and let it cool. When the internal temperature dropped to room temperature, the unreacted polymer was driven out, and the autoclave was opened to take out the reaction liquid. The obtained reaction liquid was poured into a large excess of hexane, and the solvent was removed by dehydration, and the precipitated polymer was taken out. Further, this polymer was dissolved in a small amount of ethyl acetate, and the remaining monomer was completely removed by reprecipitation twice with hexane. After drying, it was obtained to 28 g of polymer. Then, 20 g of the polymer was dissolved in 100 ml of N,N-dimethylacetamide, and 11.4 g of chlorinated acrylic acid was added dropwise under ice cooling, and the mixture was stirred at room temperature for 1 hour. . Ethyl acetate was added to the reaction mixture, and the organic layer was extracted with water and then concentrated, and the obtained polymer was re-precipitated with hexane to obtain 19 g of perfluoro group represented by the following general formula (2). Olefin copolymer (1). The resulting polymer had a refractive index of 1.421. Perfluoroolefin copolymer (υ -117- 200831962 CF2 - CF-.I cf3 50 十 H2 CH--V / 50 Otl OCHaCHaOCCH^CHg 50 : 50 means Mobi ratio general formula (2) &lt;&lt;Sol 2 Modulation &gt;&gt; In a reactor equipped with a stirrer and a reflux condenser, 120 parts of methyl ethyl ketone and 100 parts of acrylonitrile oxypropyl trimethoxy decane (KBM-5103, Shin-Etsu Chemical) were added. Industrial Co., Ltd.), 3 parts of diisopropoxy aluminum ethyl acetoacetate, after mixing, add 30 parts of ion-exchanged water, react at 60 ° C for 4 hours, and cool to The sol solution 2 was obtained at room temperature. The mass average molecular weight was 1,600; among the components having an oligomer component or more, the component having a molecular weight of 1,000 to 20,000 was 100%. Further, by gas chromatography, the raw material was analyzed. Acryloxypropyltrimethoxysilane does not remain at all. &lt;&lt;Preparation of coating liquid for low refractive index layer&gt;&gt; 13 g of thermal crosslinkability of polysiloxane and hydroxyl group having a refractive index of 1 to 44 is added Fluoropolymer (JTA11 3, solid content concentration: 6%, manufactured by JSR Co., Ltd.), 1 3 Colloidal vermiculite dispersion MEK-ST-L (trade name, average particle diameter of 45 nm, solid content concentration of 30%, manufactured by Nissan Chemical Co., Ltd.), 0.65 g of the aforementioned sol solution, And 4.4 g of methyl ethyl ketone and 1.2 g of cyclohexanone, and after stirring, the mixture was filtered with a polypropylene-118-200831962 filter having a pore size of 1 μm to prepare a low refractive index layer coating liquid 1. The refractive index of the layer formed by the coating liquid is 1.45. The cycloolefin-based resin film A-1 having the above-described hard coating layer is wound into a cylindrical form, and a low refractive index is used using a coater having a slit die. The coating layer for the rate layer is directly pressed onto the surface of the polarizing plate protective film coated with the auxiliary roller and coated with the hard coating layer. After drying at 150 ° C for 150 seconds, further to 1 Dry at 40 °C for 8 minutes, then purge with nitrogen, under an atmosphere of oxygen concentration of 0.1%, ^ use 240W/cm air-cooled methyl basified material (made by Agrafkus Co., Ltd.) ), irradiating ultraviolet rays of an irradiation amount of 300 mJ/cm 2 to form a low fold of a thickness of 100 nm The luminosity layer is wound up and formed on the cycloolefin resin film A-1 having the hard coating layer formed thereon, and the first protective film B-1 having a low refractive index is further formed. [Measurement of moisture permeability] As described above, in addition to changing the humidity control condition to 60 ° C and 95% RH, moisture permeability was calculated in accordance with JIS Z- 0 0 0 8. At this time, the thermostatically humidified device was taken out at appropriate time intervals. In the cup, the weighing operation is repeated, and the average mass increase per unit time is obtained by two consecutive weighings, and the evaluation is continued until they become 5% or less. Further, in order to eliminate the influence of the moisture absorption of the sample, the empty cup to which the moisture absorbent is not added is measured to correct the moisture permeability. The first protective film B-1 thus obtained has a moisture permeability of 5 g/m2. -119- 200831962 &lt;&lt;Production of First Protective Films B-2 to B-13&gt;&gt; In the same manner as the first protective film B·1, each of the first protective films B-1 was prepared. Humidity B-2 ~ B-13. In addition, the first *protected 5 蒦 film B-2 ~ (g / m ^ 2 • day) is shown in Table 1. Further, in the measurement of moisture permeability, in the case of measuring the moisture permeability of the polarizing plate protective film containing the resin layer of the vinyl alcohol polymer, the resin layer provided on the transparent substrate film is brought into contact with the measuring cup. In the manner of setting the sample, the moisture permeability on the transparent substrate film side was measured in the same manner as described above. Table 1 First protective film film layer pretreatment undercoat hard coating low-refractive-index layer moisture permeability (g/m2·day) B-1 A-1 (cycloolefin resin film) Corona has 5 B - 2 A-2 (Polyester-based resin film) Corona has 49 B-3 A-3 (polycarbonate-based resin film) Corona has 230 B-4 A-4 (vinyl chloride-coated film) ) 川川, Μ There are 140 B-5 A-5 (vinyl alcohol resin coated film) Μ j\\\ and j\\\ There are 219 B-6 TAC-TD80U (Fuji film (stock) system) Black Μ j\\\ has 900 B-7 A-1 (cycloolefin resin film) inL· black Μ J \ \Ν & EJ\ \\ no 5 B-8 A-2 (polyester resin film ) Μ Μ j\\\ and j\\\ No 50 B-9 A-3 (Polycarbonate resin film) Μ 4επι None 250 B-1 0 A-4 (vinylidene chloride coating film) Μ y \ 4jtji m Charm j\ \\ chick 150 B-1 1 A-5 (vinyl alcohol resin coated film) sister j\\\ Μ j\w Μ j\\\ Μ 224 -120- 200831962 B-1 2 TAC-TD80U (Fuji film (stock) system) &gt;fnr nil y \ nn No 4rrr. nrl j\\\ 1,200 B-1 3 A-5 (vinyl alcohol resin coated film &gt;fnr lilt: no te j\\\ 4τγτ lilt j\\\ 450 &lt;Production of second protective film&gt;&lt;&lt;Production of optical compensation film CF-1&gt;&gt; The composition was placed in a mixing tank and stirred while being heated to 30 ° C to dissolve the components to prepare cellulose hydride. The deuterated cellulose was obtained by using a total thiol substitution degree of 2.8 3 , a total oxime substitution degree of 2.8 3 , and a 6-position substitution degree of 0 · 90 . Table 2 Cellulose acetate solvent composition Inner layer (parts by mass) Outer layer (parts by mass) Deuterated cellulose 100 100 Triphenylphosphine (plasticizer) 7.8 7.8 Biphenyl diphenylphosphine (plasticizer) 3.9 3.9 Methylene chloride (1st solvent) 293 314 Methanol (2nd solvent) 71 76 1-butanol (3rd solvent) 1. 5 1.6 矽石microparticles (AEROSIL R972, Japan 0 0.8 Airo Dilu Co., Ltd.) Hysteresis 値 lifter shown in general formula (3) 0.5 0 -121- 200831962

The obtained coating liquid for coating for the inner layer was cast on a drum cooled to 0 °C using a three-layer co-casting die. The film having a residual solvent amount of 70% by mass was peeled off from the drum and fixed on a pin tenter dryer. The load in the transport direction was 1 1 1 5 %, and the solution was dried at 80 ° C while being transported. At 10%, dry at 1 1 〇 °c. Then, it was dried at a temperature of 150 ° C for 20 minutes to prepare a cellulose acetate film (outer layer: 3 μ: 74 μm, outer layer: 3 μm) having a solvent amount of 〇 3 mass %. The cellulose acetate film produced was used as a polymer substrate to determine optical properties. The polymer substrate C-1 has a width of 1,340 mm and a thickness of 630 nm retardation Re (Re) using an ellipsometer (Μ-150, manufactured by JASCO Corporation). The phase axis is in the direction of the carrier, and the 値 is 8 nm. Further, when the hysteresis 値 (Rt h ) in the wavelength of 630 nm was measured, the enthalpy was 9 〇 nanometer. For the liquid and the outer layer, set both ends: 匕 to the dose to cause residual long, inner layer: and measure 75 microns. The wavelength is the thickness of the orthogonal rice -122- 200831962. When the retardation R(Rth) in the thickness direction of the wavelength of 630 nm, the enthalpy is 90 nm. The polymer substrate C-1 was immersed in a 2.0 N potassium hydroxide solution (25 ° C) for 2 minutes, neutralized with sulfuric acid, washed with pure water, and dried. The surface energy of the polymer substrate C_1 was determined by the contact angle method to be 63 m N/m. &lt;Formation of optical anisotropic layer&gt; On the polymer substrate C-1 produced above, a coating of the following composition was applied at a coating amount of 28 ml/m 2 using a #16 line coater. Film coating solution. It was dried at 60 ° C for 60 seconds, and further dried at 90 ° C for 150 seconds. [Composition of alignment film coating liquid] ___ • Modified polyvinyl alcohol represented by the following general formula (4)···· 1 〇 parts by mass • water.............. ..... 371 parts by mass • Methanol................... 1 9 parts by mass • Glutaraldehyde (crosslinking agent)........ ...... 5 parts by weight - 4ch2 &quot; * ch4 - Bu ch2-ch }:. Shiyan &quot;2 - v z I f 87.2 x \ χ | 12 OH 0 〇C〇CH3 bo - n(ch2)ooc-c=ch2 ch3 General formula (4) Then, the alignment film is subjected to rubbing treatment. The rubbing direction was in the direction of 45° with respect to the late phase axis (measured at a wavelength of 632.8 nm) of the polymer substrate -1 to -12331. [Formation of Liquid Crystal Layer] 41.01 parts by mass of the cholesteryl liquid crystal compound represented by the following general formula (5) and 4.06 parts by mass of ethylene oxide-modified trimethylolpropane triacrylate (V#360, Osaka) Organic compound (manufactured by the company), 0.35 parts by mass of cellulose acetate butyrate (CAB531-1, manufactured by Eastman Chemical Co., Ltd.), and 1.35 parts by mass of photopolymerization initiator (lrgaqure 907, Ciba Geiger公司·45 parts by mass of sensitizer (Kacker DETX, manufactured by Nippon Kayaku Co., Ltd.), (and 0.1 parts by mass of the following fluorinated surfactant, dissolved in 102 parts by mass) A coating liquid was prepared as a coating liquid in the ethyl ketone, and the coating liquid was applied onto the above-mentioned alignment film by a #3.6 line coater, and heated at 1 30 ° C for 2 minutes to form a discotic liquid crystalline compound. The liquid crystal compound was polymerized by UV irradiation for 1 minute using a high-pressure mercury lamp of 1 ° C and 120 W / cm for 1 minute, and then left to cool to room temperature. / In this way, an optically different direction was formed. Optical compensation film for the layer It is the second protective film CF-1. In addition, the in-plane retardation 値Re of the optically anisotropic layer measured at a wavelength of 546 nm is 38 nm. Further, at 25 ° C and a relative humidity of 10% The difference between in-plane retardation Re (Re10) and in-plane hysteresis Re (Re80) at 25 ° C and relative humidity of 80% is 12.1 nm, which is divided by 25 ° C and relative humidity of 60%. The in-plane hysteresis (Re60) has a Gr of 0.40. -124- 200831962

R R

R= —〇-C II o

General Formula (5) &lt;&lt;Production of Deuterated Cellulose Films C-2 to C-10&gt;&gt; In addition to forming an optically anisotropic layer in the production of the second protective film CF_1, In the same manner as the film C F-1, a cellulose film C-2 to C-10 was produced. Further, in the production of the deuterated cellulose film C-2 to C-1, the deuterated cellulose CTA-1 to CTA-10 having the characteristics shown in Table 3 and the solvent S-1 shown in Table 4 were used. S-3, coating liquids D-1 to D-1 0 shown in Table 5 were produced. Further, the preparation of each coating liquid was classified into a solvent S-1, a solvent S-2, and a solvent S-3, and the preparation was carried out in accordance with the following procedure. [In the case of the solvent S-1] In a dissolution tank made of stainless steel having a stirring paddle and having 400 liters of cooling water circulating on the outer circumference, the solvent of the composition 1 was mixed, and then an additive other than the cellulose-degraded cellulose was dissolved. Next, the cellulose powder was slowly added while stirring, so that the total input amount was 300 kg. In addition, all of the solvent solutions of the dichlorocarbyl, butanol, and methanol systems have a water content of 〇 _ 2 by mass. /. The following things. The tank was closed, and the cooling water outside the tank was changed to 60 °C. While dissolving, the solution was dissolved for 2 hours to prepare a deuterated cellulose solution. Next, 'filter paper with absolute filtration accuracy of 〇.〇1 mm (made by Toyo Filter Co., Ltd., #63) -125- 200831962, and further filter paper with absolute filtration accuracy of 2.5 μm (made by Bolu Co., Ltd.) , F Η 0 2 5 ) for filtering. The second solution composition described below was prepared in another mixing tank, and 474 parts by mass of the above first solution and 25 parts by mass of the second solution were mixed. [Composition of the second solution] _ • Fine particles (cerium oxide (particle size: 20 nm), Mohs hardness of about 7).....0.5 parts by mass • dichloromethane... .......87 parts by mass • methanol..................13 parts by mass [in the case of solvents S-2 and S-3] with stirring paddle Wings, a 400 liter stainless steel dissolution tank having a cooling water circulation in the periphery, were mixed with a solvent to have a composition as shown in Table 2, and further, a plasticizer, a release agent, and an additive as shown in Table 3 were added and dissolved. The deuterated cellulose powder was slowly added while stirring, so that the total input amount was 200 kg. Further, all of the solvents of dichloromethane, butanol, and methanol are those having a water content of 0.2% by mass or less. First, the powder of deuterated cellulose is decompressed to 1,300 Pa in the tank into which the powder has been placed in the dispersion tank, at an initial agitation shear rate of 15 m/sec (shear stress 5\1041 &lt;9&quot; The dissolving rod type eccentric stirring shaft that is stirred at a peripheral speed of /36 () 2) and the peripheral speed of the anchoring wing on the central shaft is 1 m/sec (shear stress 1 x 1 〇 4 kgf / m / sec 2 The dispersion was carried out for 30 minutes under stirring. The starting temperature of the dispersion was 25 ° C, and the final temperature was 35 ° C by the flow of cooling water. -126- 200831962 After the end of the dispersion, stop the high-speed stirring, set the peripheral speed of the anchoring wing to 〇. 5 m / s and further stir for 1 〇 〇 minutes to swell the cellulose sulphide. When the swelling was completed, the inside of the tank was pressurized with nitrogen to make 0.12 MPa. At this time, the oxygen concentration in the tank was kept less than 2% by volume, and there was no problem in the explosion. Further, the amount of water in the coating liquid was confirmed to be 0.2 mass. /. the following. 470 parts by mass of this solution and 25 parts by mass of the additionally prepared second solution composition liquid were mixed. [Composition of the second solution] _ • Fine particles (cerium oxide (particle size: 20 nm), Mohs hardness of about 7).....0.5 parts by mass • decyl acetate... .......8 5 parts by mass • Acetone...................7 parts by mass • Ethanol............. 8 parts by mass of the obtained uneven sol-like solution, which was conveyed by a screw pump which was heated to 3 CTC on the central axis, and cooled from the outer peripheral portion of the spiral to a 75° in 3 minutes. The way C passes through the cooling section. The cooling was carried out using a refrigerant cooled to -80 ° C in a freezer. Then, the obtained solution was cooled by a screw pump to a temperature of 35 ° C by a screw pump and transferred to a container made of stainless steel. After uniformly stirring at 50 ° C for 2 hours, the filter was filtered with an absolute filtration accuracy of 〇 0 1 mm (made by Toyo Filter Co., Ltd., #6 3), and further with an absolute filtration accuracy of 2.5 μm. The filter paper (made by Bolu Co., Ltd., FH025) was filtered. -127- 200831962 The obtained cellulose derivative solution is heated to a temperature of 1 1 〇 ° C, 1 Μ P a by the heating portion of the liquid feeding tube, and released to atmospheric pressure (about 1 M Pa ). The organic solvent was volatilized and cooled to obtain a solution having a solid concentration of about 24% at a temperature of 40 °C. Table 3 Raw material 醯 total thiol substitution degree acetamyl substitution degree propyl thiol substitution degree 6 degree substitution degree CTA-1 ---- 2.87 2.87 0.00 0.90 CTA-2 2.30 2.30 0.00 0.90 CTA-3 2.83 2.83 0.00 0.91 CTA- 4 2.84 2.84 0.00 0.92 CTA-5 2.57 1.89 0.68 0.91 CTA-6 -------- 2.82 2.82 0.00 0.91 CTA-7 — 2.38 1.54 0.84 0.88 cTA-8 2.94 2.94 0.00 0.91 CTA-9 2.88 2.88 0.00 0.90 CTA -10 --- 2.87 2.87 0.00 0.91 袠4 Dichloromethane methyl acetate acetone methanol ethanol 1-butanol solvent S-1 87 — — 12 — 1 Solvent S-2 ----- — 8 1 7 — 8 4 Solvent S-3 1---- — 75 7 5 10 3 -128- 200831962 Table 5 Coating deuterated f Davis solvent plasticizer stripping agent additive (1) Additives (2) Addition amount of liquid name (parts by mass) Adding amount (parts by mass) Adding amount of the amount) Adding a scent (mass 纛) Type of addition (parts by mass) Type of addition (parts by mass) D-1 CTA-1 18 S-1 80 2.0 0.1 M-3 0.32 I—D-2 CTA-2 18 S-2 80 2.0 M-3 0.32 — — D-3 CTA-3 18 S-1 80 2.0 0.1 M-1 0.1 M-2 0.005 D-4 CTA-4 18 S- 1 80 2.6 0.1 M-3 0.1 M-2 0.005 D -5 CTA-5 18 S-3 80 2.4 0.1 M-3 0.32 — One D-6 CTA-6 18 S-1 80 2.4 ------ 0.1 M-1 0.1 M-2 0.005 D-7 CTA- 7 18 S-1 80 2.4 0.1 M-3 0.32 — — D-8 CTA-8 18 S-3 80 2.4 0.1 M-4 12 — A D-9 CTA-9 18 S-1 80 2.0 --S__. 0.1 — — — — D-10 CTA-10 18 S-1 80 2.0 0.1 M-4 5 — — In addition, all the plasticizers shown in Table 5 were used in an amount of 2 parts by mass of phenylphosphine and 1 part by mass. Mixed with biphenyl diphenyl phosphine. Further, as the release agent, ethyl citrate (a mixture of ethyl substitution degrees of 0 to 3) was used. In addition, the coating liquid additives Μ 1 to Μ 4 shown in Table 5 are not described.

Ch3 structural formula...a 1) -129- 200831962 f

Structural formula (Μ-2)

The coating liquids D -1 to D -10 obtained in this manner were cast on a mirror stainless steel drum support. After peeling the film from the drum while stretching about 5% in the longitudinal direction, the film is dried in the width direction by a tenter, and further dried while being transported between the plurality of rolls, and then -130- Rolled up in 200831962. The thickness, thickness direction retardation R (Rth) and in-plane retardation Re (Re) of the deuterated cellulose films c-1 to C-1 0 obtained in this manner were measured. The results and the stretch ratio in the width direction are shown in Table 6. Further, the stretch ratio in the width direction shown in Table 6 is expressed as a percentage from the width dimension of the film before stretching to the dimension increased by stretching and the width dimension of the film before stretching. &lt;&lt;Production of Deuterated Cellulose Films C-11 to C-12&gt;&gt; 40 g of Daysill in a three-liter flask equipped with a mechanical stirrer, a thermometer, a cooling, and a dropping funnel The company made cellulose (ethyl ketone substitution degree of 2.41), 46.0 ml of pyridine, and 300 ml of dichloromethane, and stirred at room temperature. Thereto, 62.4 ml of benzamidine chloride was slowly dropped, and after the addition, stirring was further carried out at room temperature. After the reaction, when the reaction solution was poured into 4 liters of methanol while vigorously stirring, a white solid precipitated. The white solid described above was separated by suction filtration, and washed with a large amount of methanol three times. The obtained white solid was dried overnight at 60 ° C, and dried under vacuum at 90 ° C to give the title compound (deuterated cellulose) CTA-11 as a white powder. The total substitution degree of the fluorenyl group of the compound CTA-11 was 3.0, and the degree of substitution of the aromatic fluorenyl group was 0.58. [Deuterated cellulose film C-11] The above-described deuterated cellulose film CTA-1 1 was dried at 2 to 20 ° C for 2 hours - 131 to 200831962, and then the composition described below was put into a mixing tank. The mixture was stirred and dissolved to prepare a deuterated cellulose solution. [Composition of deuterated cellulose solution] • Dichloromethane................2 91 parts by mass • Methanol............... ...44 parts by mass • Deuterated cellulose (CTA-11)..........100 parts by mass • cerium oxide microparticles.............0.25 mass The above-mentioned deuterated cellulose solution was heated at 30 ° C and cast on a mirror stainless steel support through a casting machine having a width of 800 mm. Further, the casting point was set on a casting roll set to 22 ° C, and the temperature of the other roll of the support belt was 30 ° C. Further, the space temperature of the entire casting portion was set at 7 °C. The casting speed was 3 m/sec and the coating width was 80 cm. At a distance of 50 cm from the casting portion, the cast cellulose film which was cast and rotated was peeled off from the belt, and both ends of the film were held by a tenter. The tenter unit of 1 1 〇 °C is transported while keeping the width of the film constant. Then, after the tenter is removed from the tenter, the portions of the nip marks on both ends of the film are cut off, and then the film is passed through a drying portion of 135 ° C to 145 ° C composed of a plurality of transition rolls to dry the residual solvent amount to 0.1% or less. After drying, the roll was attached to a core to obtain a long-sized film of deuterated cellulose film C-11 having a film thickness of 80 μm, and for the obtained cellulose-deposited film C-1 1, an automatic complex refractive index was used ( KOBRA-21 ADH, manufactured by Oji Scientific Instruments Co., Ltd., measured the dependence of light incident angle on hysteresis 132-132-200831962, and calculated the optical characteristics as 'Re = 4.5 nm' Rth = - 141 nm. The deuterated cellulose film C-11 is at 25. (:, the absolute 値 of the difference between the in-plane hysteresis Re (Re 10) at a relative humidity of 10% and the in-plane hysteresis Re (Re80) at 25 ° C and a relative humidity of 80%, divided by 25° C. The in-plane retardation 値 (Re60) under the relative humidity of 60% is Gr. 0.16. The elongation ratio, thickness, in-plane retardation Re (Re), thickness direction retardation of the bismuth cellulose film C-11 R (Rth) and Gr 値 are shown in Table 6. [Production of Deuterated Cellulose Film C-12] The same as the production of the cellulose-deposited film C 1 1 except that the completed thickness was set to 50 μm. In the same manner, a long-length deuterated cellulose film C1 2 was obtained. For the obtained deuterated cellulose film C 1 2, an automatic complex refractive index (KOBRA-2 1 ADH, manufactured by Oji Scientific Instruments Co., Ltd.) was used. The incident angle dependence of the light of the hysteresis was measured, and the optical characteristics were calculated. Re = 2 nm, Rth = -190 nm. The cellulose film C12 was in the plane at 25 ° C and a relative humidity of 10%. The absolute 値 of the difference between the retardation Re (Re 1 0) and the in-plane hysteresis Re (Re 80) at 25 ° C and a relative humidity of 80%, divided by 25 ° C The in-plane retardation 値 (Re60) at a relative humidity of 60% is Gr 0.2. The elongation ratio, thickness, in-plane retardation Re (Re), and thickness retardation of the bismuth cellulose film C-12 (Rth) and Gr値 are shown in Table 6. Table 6 - 133 - 200831962 Film name using coating liquid in the width direction stretch ratio (%) Film thickness Re (nm) Rth (nm) Gr C-1 D - 1 5 80 9.6 80 1.26 C-2 D-2 5 80 12.5 96 1.68 C-3 D — 3 18 80 35 180 0.34 C-4 D-4 28 80 2 50 4.60 C-5 D-5 22 80 50 130 0.24 C-6 D — 6 16 70 55 200 0.09 C-7 D — 7 30 40 45 118 0.16 C-8 D-8 5 70 2 4 0.90 C-9 D — 9 5 80 6.8 44 1.59 C-10 D-10 20 80 11 18 0.05 C-11 D —11 0 80 4.5 -141 0.16 C-12 D-12 0 50 2 -90 0.2 Then, the produced deuterated cellulose films C-1 to C-12 were at 50 ° C After immersing in a sodium hydroxide aqueous solution for 2 minutes, it was washed with water and dried. &lt;&lt;&lt;&gt; Preparation of optical film CF-2&gt;&gt; [Application of optical anisotropic layer] The same method as the optical compensation film CF-1 described above on the cellulose film C-2 The optically oriented layer was formed into an optical compensation film CF-2. The optical compensation film CF-2 produced had a Re of 28 nm and an Rth of 170 nm; an in-plane retardation (8610) at 25 ° C and a relative humidity of 10% and a relative humidity of 80% at 251. The absolute 値 of the difference between the lower surface hysteresis ([^80) -134- 200831962, divided by the in-plane retardation R(R e 6 0 ) at 25 ° C and 60% relative humidity 値G r System 0.7 0. &lt;&lt;Production of optical compensation film CF-3&gt;&gt; [Application of optical anisotropic layer] The same as the optical compensation film CF-1 described above on the cellulose-deposited film C-3 produced The method is to apply an alignment film, transport the film at a speed of 20 m/min, and set a rubbing roller (300 mm in diameter) by rubbing with respect to a longitudinal direction of 45° to make it 650. The rpm was rotated, and the surface provided with the alignment film was subjected to a rubbing treatment. Then, on the rubbed-treated alignment film, a trimethylolpropane triacrylate (V#360, Osaka) was modified from 41.0 kg of a discotic liquid crystal compound and 4.06 kg of ethylene oxide. Organic compound (manufactured by the company), 0.35 kg of cellulose acetate butyrate (CAB531-1, manufactured by Eastman Chemical Co., Ltd.), 1.35 kg of photopolymerization initiator (Irgaqure 907, manufactured by Ciba Geiger Co., Ltd.) ), 0.45 kg of sensitizer (Kacker DETX, manufactured by Nippon Kayaku Co., Ltd.), 0.45 kg of citrate (Sansei Chemical Co., Ltd., AS3) dissolved in 1 〇 2 kg of methyl ethyl ketone 1·1 kg of fluoroaliphatic-based copolymer (Megafacu F7 80, manufactured by Dainippon Ink Co., Ltd.) was added to the resulting coating solution, so that the #3.2 line coater was in the same direction as the film. The direction was rotated at 3 9 1 rpm and continuously applied to the alignment film surface of C-3 transported at 20 meters/min. The film surface air velocity is set to be parallel to the film by drying the solvent by continuously heating from room temperature to 1 〇〇 ° C, and then drying the film at a temperature of 130 ° C in a dry region at 130 ° C. The transport direction is 2 · 5 meters / sec, and the heating is about 90 seconds to align the discotic liquid crystal compound. Next, it is transported to a dry area of 80 ° C, and the surface temperature of the film is about 1 〇〇 ° C, by means of an ultraviolet irradiation device (ultraviolet lamp: output power is 160 W / cm, and the luminous length is 1 _ 6 m). The ultraviolet ray having an illuminance of 60 0 mW is subjected to a crosslinking reaction to fix the discotic liquid crystal compound in the alignment direction. Then, it was left to cool to room temperature, and it was rolled into a cylindrical shape to have a cylindrical shape. In this way, a cylindrical optical compensation film (C F - 3) was produced. The optical anisotropic layer produced had a Re of 30 nm and an Rth of 90 nm; an in-plane retardation (Re10) at 25 ° C and a relative humidity of 10% and a relative humidity of 8 at 25 ° C. The absolute 値 of the difference between the in-plane hysteresis R(R e 8 0 ) at 0 %, divided by the in-plane hysteresis (Re60) at 25 ° C and 60% relative humidity, Gr system 0 · 80 〇 &lt;&lt;Production of optical compensation film CF-4&gt;&gt; [Application of optical anisotropic layer] on the fluorinated cellulose film C-4 produced above, and the optical compensation film CF-1 In the same manner, an alignment film was applied, and an optically anisotropic layer such as Re of 30 nm and Rth of 80 nm was provided to prepare an optical compensation film (CF-4). The optical compensation film CF-4 produced had a Re of 28 nm and an Rth of 1 30 nm; in-plane retardation Re (Re1 0) at 25 ° C and a relative humidity of 10%, and at 25 ° C, The absolute enthalpy of the in-plane hysteresis Re (Re80) at a relative humidity of 80% is -136-200831962, divided by the in-plane retardation Re (Re60) at 25t and a relative humidity of 60%, and the Gr system is 0.6. (Example 1) (Production of polarizing plate) &lt;Production of polarizer&gt; A polyvinyl alcohol film having a thickness of 120 μm was immersed in 1 part by mass of iodine, 2 parts by mass of potassium iodide, and 4 parts by mass of boric acid. In the aqueous solution, it was stretched 4 times at 50 ° C to prepare a polarizer. 2 parts by mass of a maleic anhydride modified ethylene butadiene styrene block copolymer hydrogenated product (melt flow index 値, at 2000 ° C, 5 kg load is 1 · gram / 10 minutes, the styrene acid content is 30 mass%, the hydrogenation rate is 80% or more, the maleic anhydride addition amount is 2%), and it is dissolved in 8 parts by mass of xylene and 40 parts by mass of methyl group. In a mixed solvent of butyl ketone, a filter made of polytetrafluoroethylene having a pore size of 1 μm was filtered to obtain a primer solution. Then, by not providing the hard coating layer of the first protective film Β-1, on the surface of the corona-treated surface and the uncoated optical anisotropic layer of the alkalized WV film, The prepared primer solution is used as a polarizer adhesive, and the first protective film and the polarizer are attached, and the completely alkalized polyvinyl alcohol 5% aqueous solution is used as an adhesive, and the second protective film and polarized light are used. The sheets are attached to each other to form an upper polarizing plate. In the same manner, the first protective film Β-7, the polarizer and the second protective film CF-) are bonded in this order to form a lower polarizing plate. &lt;Evaluation of durability of polarizing plate&gt; -137- 200831962 The polarizing plate obtained by the above method was placed in an environment of 60 ° C and 9 5 % R 1 for 1 hour, and the degree of polarization was measured. Based on the following evaluation criteria. The results are shown in Table 6. Further, the degree of polarization is as described above. The degree of polarization at a wavelength of 550 nm is obtained by the above formula (1). As a result of evaluating the durability of the polarizing plate of Example 1 in this manner, the degree of polarization was 99.5 %, which was a problem-free grade. [Evaluation Criteria] 〇: The degree of polarization is 99% or more, and there is no practical problem; △: The degree of polarization is 98% or more and 99% or less, and there is no practical problem; X: The degree of polarization is less than 98%, and it is practical. problem. (Production of Liquid Crystal Display Device) A pair of polarizing plates (upper polarizing plate and lower polarizing plate) provided on a 20-inch liquid crystal display device (LC-20V1, manufactured by Sharp Co., Ltd.) using a ΤΝ-type liquid crystal cell In the same manner as in the polarizing plate produced in the first embodiment, the second protective film was passed through the adhesive, and one of the viewer side and the backlight side was attached so as to be on the liquid crystal cell side. The polarizing plate is disposed such that the transmission axis of the polarizing plate (upper polarizing plate) on the observer side and the transmission axis of the polarizing plate (lower polarizing plate) on the backlight side are orthogonal to each other. At this time, a polarizing plate having a first protective film of a hard coating layer is disposed on a polarizing plate (upper polarizing plate) on the observer side, and a polarizing plate (lower polarizing plate) on the backlight side is disposed without a hard coating. Layer of polarizing plate. &lt;Evaluation of Liquid Crystal Display Device&gt; Next, using a measuring machine (ΕΖ-Comp. 160D, manufactured by ELDIM Co., Ltd.), measuring -138-200831962 is set at an azimuth angle of 45 ° which is a reference in the lateral direction of the liquid crystal display screen. The normal direction of the reference is the color of the black display when the polar angle of the reference is 60°. Next, this liquid crystal display device was placed in a house at normal temperature and normal humidity (25 ° C, 60% RH, no humidity control) for one week, and the color odor at the time of black display was measured again. Further, this liquid crystal display device was allowed to stand at 25 ° C under 1 〇 % R 1 for one week, and then the color odor at the time of black display was measured. Further, the same liquid crystal display device was allowed to stand at 25 ° C and 80 % RH for one week, and then the color tone at the time of black display was measured. With respect to the color odor measurement obtained above, the evaluation of the color change was performed based on the following evaluation criteria. ◎: black taste change (Δ E*) is less than 0.1, and there is no practical problem; 〇: black taste change (ΔΕ*) is 0.1 or more to 〇·3 or less, and there is no practical problem; Δ: black taste change ( ΔΕ*) is 〇·3 or more and 0·5 or less, and there is a practical problem; X: Black taste change (ΔΕ*) is 〇·5 or more, and there are practical problems. Further, as a result of observing the liquid crystal display device, it is possible to realize a black display in which both the front direction and the viewing angle are uniformly adjusted (n u t r a 丨). (Production of Polarizing Plates of Examples 2 to 15 and Comparative Examples 彳1 to 13) The same procedure as in the above-described Example 1 was carried out using the first protective films B-2 to B-1 3 and the above-described first protective film. The second protective film cF-彳~CF-4, C-5~-139- 200831962 C _ 1 0 'The combination shown in Table 7 is made into a polarizing plate. At this time, b 4~B-6, B10~B13 and the second protective film are subjected to neutralization, water washing and alkalization after being immersed in 15 mol/liter of 55 NaOH aqueous solution for 2 minutes, and then A fully alkalized polyvinyl alcohol 5% aqueous solution is used as an adhesive and adheres to a polarizer. Further, the protective films of B2, B3 and B7 to B9 were bonded to the polarizers in the same manner as in Example 1 after the corona treatment. &lt;Evaluation of polarizing plates of Examples 2 to 5, Examples 1 to 3 and Comparative Example 1&gt;(&lt;&lt;TN mode liquid crystal cell evaluation&gt;&gt; In addition to the polarizing plate used, Table 7 In the same manner as in the first embodiment, the polarizing plates of Examples 2 to 5, Examples 1 to 3, and Comparative Example 1 were placed in a liquid crystal display device in the same manner as in Example 1. The evaluation of the color change was carried out. The evaluation results are shown in Table 7. <Evaluation of the polarizing plate of Example 6 and Comparative Example> &lt;&lt; OCB mode liquid crystal cell production &gt;&gt; A polyimide film having an alignment film is provided on the glass substrate having the I TO electrode, and rubbing treatment is performed. The rubbing treatment is performed in such a manner that the two glass substrates are opposed to each other, so that the cell gap (d) becomes In a mode of 8 micrometers, two glass substrates were bonded to each other, and a liquid crystal compound (ZLI1132, manufactured by Meruku) having a Δη of 0.1 396 was injected into the cell gap to prepare an OCB mode liquid crystal cell. On the liquid crystal cell, in the manner of holding the liquid crystal cell, making -140- 200831962 The polarizing plate prepared as described above is disposed so that the optically oriented layer of the optical compensation film and the glass of the liquid crystal cell face each other. The rubbing direction of the alignment film of the liquid crystal cell of the 〇CB mode and the optical compensation film are used. The rubbing direction of the alignment film was reversed and arranged. On both sides, the polarizing element was placed by a crossed Nicols method. In this case, the polarizing plates of Example 6 and Comparative Example 4 were used. The color change was evaluated in the same manner as in Example 1 on the produced 〇CB mode liquid crystal display device. The evaluation results are shown in Table 7. <Polarization of Example 7 and Comparative Example 5 Evaluation of the board &lt;&lt;&lt;Evaluation of ECB mode liquid crystal cells&gt;&gt; The liquid crystal cell system has a cell gap of 3.5 μm, which is dropped by injecting a nematic liquid crystal material having a positive dielectric constant direction layer It is sealed between the substrates, and the Δη·d of the liquid crystal layer is set to 300 nm. The liquid crystal material is positive in dielectric anisotropy and refractive index isotropic, Δ n = 0.0854 (589 nm, 20 °C), △ ε = + 8 a nematic liquid crystal of about _5 (for example, MLC-9100 of Meruku). Further, the intersection angle of each of the alignment axes (friction axes) of the upper substrate and the lower substrate is 〇°, and then, the upper and lower polarizing plates are attached. Then, the rubbing axis direction (alignment control direction) of the upper and lower substrates of the liquid crystal cell is bonded to the retardation axis of the support of the optically anisotropic layer at 45°. Further, the absorption axis of the polarizing film The alignment direction (friction direction) of the liquid crystal cells is approximately 45°, and the intersection angle of the absorption axes of the upper and lower polarizing films is approximately 90° crossed Nicols. The polarizing plates of Example 7 and Comparative Example 5 were evaluated for color change when used in the produced -141-200831962 ECB mode liquid crystal display device. The evaluation results of these are shown in Table 7. &lt;Evaluation of Polarizing Plates of Examples 8 to 9 and Comparative Examples 6 to 7&gt; The polarizing plate and the retardation film provided on a VA liquid crystal display device (LC-26GD3, manufactured by Sharp Co., Ltd.) were peeled off. The polarizing plates of Examples 8 to 9 and Comparative Examples 6 to 7 were replaced so that the transmission axis was aligned with the polarizing plate attached to the product. Then, the evaluation of the color change was carried out in the same manner as in Example 1. The evaluation results are shown in Table 7. &lt;Evaluation of polarizing plate of Example 1 0, 15 and Comparative Example &gt;&lt;&lt;Production of first retardation film&gt;&gt;&gt; 2,2'-bis(3,4-dicarboxyphenyl) Polyheximide synthesized from hexafluoropropane and 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, prepared using cyclohexanone as a solvent A 5 mass% solution was applied to a 50 μm thick triethylenesulfonated cellulose film. Then, by drying at 1 °C °C for 10 minutes, a film having a residual solvent amount of 7% and a thickness of 6 μm was obtained. Then, the film formed on the triethylenesulfonated cellulose film, each substrate (triethylenesulfonated cellulose film) was subjected to 5% longitudinal uniaxial stretching at a temperature of 160 ° C, from the foregoing three The acetonitrile-based cellulose film was peeled off to obtain a first retardation film. The first retardation film has characteristics of Δ n d = 60 nm, Rth = 250 nm, d = 5.5 μm, ΔηΙηχ-ηζ^Ο.ΟΜδ, nx&gt;ny &gt; η z. The polarizing plate and the retardation film provided on the VA liquid crystal display device (LC-26GD3, manufactured by Sharp Co., Ltd.) were peeled off, and the polarized light of Example 10, 1-5-142-200831962 and Comparative Example 8 was changed. The plate is attached in such a manner that the penetration axis coincides with the polarizing plate attached to the article. Further, on the liquid crystal cell side (second protective film side) of the polarizing plate (lower polarizing plate) on the backlight side, the η X direction and the absorption axis of the polarizing plate are orthogonal to each other, and the above-mentioned adhesive is applied thereto. The first retardation film. Further, the polarizing plate (upper polarizing plate) on the observer side is attached to the liquid crystal cell through the adhesive so that the absorption axis of the polarizing plate is orthogonal to each other without interposing the first retardation film. / Then, the evaluation of the color change was carried out in the same manner as in Example 1. Γ The evaluation results are shown in Table 7. &lt;Evaluation of polarizing plate of Example 1 and Comparative Example&gt;&lt;&lt;&gt; Evaluation of second retardation film&gt;&gt; A terpene-based resin film having a thickness of 135 μm (made by JSR Corporation) Twisting, stretching treatment at 175 °C, to produce a refractive index characteristic of η X &gt; ny &gt; nz, Re is 40 nm and Rth is 200 nm. film. Then, the polarizing plate and the retardation film provided on the IPS type liquid crystal display device (Th-26LX300, manufactured by Matsushika Electric Industrial Co., Ltd.) are peeled off, and the polarizing plate of the present invention is changed to pass through. The shaft is attached in a manner consistent with the polarizing plate attached to the product. Further, on the liquid crystal cell side (second protective film side) of the polarizer (upper polarizing plate) on the observer side, the second retardation film described above is attached via an adhesive. Further, the polarizing plate (lower polarizing plate) on the backlight side is bonded to the liquid crystal cell through the adhesive without interposing the second retardation film described above. Then, the evaluation of the color change was carried out in the same manner as in Example 1. -143- 200831962 The evaluation results are shown in Table 7. &lt;Evaluation of polarizing plate of Example 1 2 and Comparative Example 1&gt;&lt;&lt;3rd retardation film&gt;&gt;&gt; 17% dichloromethane solution of polycarbonate having a mass average molecular weight of 80,000 After extending the stainless steel strip to make the residual volatiles 3%, the film was subjected to a longitudinal uniaxial stretching of 1 5% at a temperature of 158 ° C to obtain hysteresis (with a light of 5 90 nm). A third retardation film formed of polycarbonate having Re = 15 nm and Rth = 270 nm was measured. &lt;&lt;Production of Fourth Disparity Film&gt;&gt; ί A ruthenium-based resin film (trade name "Ou Noah 1 420R", manufactured by Sakamoto Co., Ltd.) in a tenter type stretching machine The stretching treatment was carried out to prepare a second retardation film having a refractive index characteristic of nx &gt; ny &gt; nz, a Re of 213 nm and an Rth of 106 nm. Then, the polarizing plate and the retardation film provided on the 丨PS type liquid crystal display device (Th-26LX300, manufactured by Matsushita Electric Industrial Co., Ltd.) were peeled off, and the polarizing plate of the present invention shown in Table 7 was changed. The attachment is performed in such a manner that the penetration axis coincides with the polarizing plate attached to the article.

C Further, the third retardation film described above is attached to the liquid crystal cell side (second protective film side) of the polarizer (upper polarizing plate) on the observer side through an adhesive. Further, the polarizing plate (lower polarizing plate) on the backlight side is bonded to the fourth retardation film through an adhesive. Then, the evaluation of the color change was carried out in the same manner as in Example 1. The evaluation results are shown in Table 7. &lt;Evaluation of the polarizing plate of Example 1 and Comparative Example 1&gt; In the case of Example J1, in addition to the use of the third retardation film in place of the first-144-200831962 retardation film, Example 1 In the same manner as in Example 1, a liquid crystal display device of Example 13 was produced. In the same manner as in Example 11, a 丨ps liquid crystal display device was used and color odor evaluation was performed. The results are shown in Table 7. In Comparative Example 9, except that the third retardation film was used instead of the first retardation film, the liquid crystal display device of Comparative Example] was produced in the same manner as in Comparative Example 9 in the same manner as in Comparative Example 9. Using 丨ps liquid crystal display device and performing color taste evaluation. The results are shown in Table 7. &lt;Evaluation of Polarizing Plate of Example 1&gt; In the first embodiment, the first protective film b_彳2 was used instead of the first protective layer used in the polarizing plate (lower polarizing plate) on the backlight side. A liquid crystal display device of Example 14 was produced in the same manner as in Example 13 except for the film B_7. In the same manner as in Example 13, a liquid crystal display device was used to evaluate the color tone. The results are shown in Table 7. (Production of Polarizing Plate of Comparative Example 13) In the first embodiment, the first protective film of the polarizing plate (upper polarizing plate) on the observer side and the polarizing plate (lower polarizing plate) on the backlight side are separately provided. The liquid crystal of Comparative Example 13 was produced in the same manner as in Example 1 except that the second protective film was changed to the first protective film B-7 (the cycloolefin-based resin film A-1 produced in Example 1 r). Display device. Further, the first protective film B-7 (the cycloolefin-based resin film A-1 produced in Example 1) had an in-plane retardation (Re10) at 25 ° C and a relative humidity of 10% and at 25 ° C. The absolute 値 of the difference between the in-plane retardation Re (Re 80) at a relative humidity of 80%, divided by the in-plane retardation Re (Re60) at 25 ° C and a relative humidity of 60%, Gr system 0 · 04. In this Comparative Example 13, productivity was remarkably lowered. &lt;Example 1 Production and evaluation of polarizing plate of 6 to 17&gt;&lt;&lt;Production of fifth retardation film&gt;&gt;&gt; -145- 200831962 Dissolving polycarbonate-polystyrene copolymer in two The coating liquid solution prepared by methyl chloride was cast into a cast film, and a retardation film of Re = 140 nm and Rth = 70 nm was obtained by performing free uniaxial stretching at a temperature of 175 t. Then, the polarizing plate and the retardation film provided on the IPS liquid crystal display device (Th-26LX300, manufactured by Matsushita Electric Industrial Co., Ltd.) were peeled off, and the polarizing plate of the present invention as shown in Table 7 was changed. The penetration axis is attached in such a manner as to conform to the polarizing plate attached to the article. Further, on the liquid crystal cell side (second protective film side) of the polarizing plate (upper polarizing plate) on the observer side, the adhesive is applied so as to be parallel to the absorption axis of the observer-side polarizing plate. The fifth retardation film described above is combined. The polarizing plate produced as described above was evaluated in the same manner as in Example 1 using a 丨P S liquid crystal display device'. The results are shown in Table 7 〇-146- 200831962 Table 7 Upper polarizing plate polarizing plate phase difference liquid crystal cell phase film difference lower side polarizing plate color change color change first protective film second protective film durability film first protective film Second protective film (25., 60% - 25 °C '60% RH) (25〇C '60% -25, 60% RH) Example 1 B-1 CF-1 ◎ 4rrr Depending on the TN mode Μ J\\\ B-7 CF-1 〇〇Example 2 B-7 CF-1 ◎ No TN mode Ατντ ΠΙΓ B-7 CF-1 〇〇Example 3 B-2 CF-1 〇4τττ Young TN mode drrr J \ w B-8 CF-1 〇〇 Example 4 B-4 CF-1 〇 no TN mode irrr Λ\\ B-10 CF-1 〇〇. Example 5 B-1 CF-2 〇TN mode B -7 CF-2 ◎ ◎ Example 6 B-3 CF-3 〇 No OCB mode No B-9 CF-3 〇〇 Example 7 B-5 CF-4 〇 No ECB mode B-11 CF-4 〇〇 Example 8 B-1 C-5 ◎ No VA mode No B-7 C-5 ◎ ◎ Example 9 B-1 C-6 ◎ No VA mode No B-7 C-9 ◎ 〇 Example B-1 C -9 ◎ No VA mode first retardation film B-7 C-9 ◎ 〇 Example 11 B-1 C-7 ◎ Second phase Differential film VA mode without B-7 C-8 ◎ ◎ Example 12 B-1 C-7 ◎ Third retardation film IPS mode Fourth retardation film B-7 C-7 ◎ ◎ Example 13 B-1 C -7 ◎ Third retardation film IPS mode B-7 C-9 ◎ ◎ Example 14 B-1 C-7 ◎ Third retardation film IPS mode without B-12 C-9 〇〇 Example 15 B-1 C-10 ◎ No VA mode First retardation film B-7 C-10 〇〇 Example 16 B-1 C-11 ◎ Fifth retardation film IPS mode No B-7 C-8 ◎ ◎ Example 17 B -1 C-12 ◎ Fifth retardation film IPS mode without B-7 C-8 ◎ ◎ -147- 200831962

Comparative Example 1 B-6 CF-1 X No TN mode B-12 CF-1 Δ X Comparative Example 2 B-12 CF-1 X No TN mode No B-12 CF-1 Δ X Comparative Example 3 B-6 CF -2 X No TN mode No B-12 CF-2 XX Comparative Example 4 B-6 CF-3 X No OCB mode ΛττΤ. B-12 CF-3 XX Comparative Example 5 B-6 CF-4 X No ECB mode None B-12 CF-4 XX Comparative Example 6 B-6 C-5 X No VA mode No B-12 C-5 XX Comparative Example 7 B-6 C-6 X No VA mode int Μ B-12 C-9 Δ Δ Comparative Example 8 B-6 C-9 X No VA mode First retardation film B-12 C-9 Δ Δ Comparative Example 9 B-6 C-7 X Second retardation film IPS mode dot Hot B-12 C -8 XX Comparative Example 10 B-6 C-7 X Third phase difference film ips mode Fourth phase difference film B-12 C-7 XX Comparative Example 11 B-6 C-7 X Third phase difference film ips mode B-12 C-9 XX Comparative Example 12 B-13 CF-1 Δ No TN mode No B-13 CM Δ X As shown in Table 7, it was confirmed that the polarizing plates of Examples 1 to 17 have Comparative Example 1 ~1 2 polarizers also have high durability. Further, it was confirmed that the liquid crystal display devices of Examples 1 to 17 have superior productivity with respect to the liquid crystal display devices of Comparative Examples 1 to 12, and the stability of the color odor is high. In particular, it has been confirmed that the effects of the liquid crystal cells of the VA mode and the IPS mode are particularly clear; in the above, the degree of substitution of the second protective film is in the range specified by the present invention. The effects of Example 8 and Example 1 2 were most remarkable. Further, in Comparative Example 13 having a polarizing plate using a film having a low moisture permeability on both sides of the polarizer, since moisture does not escape from the polarizer after bonding, the drying time required thereafter is required. It is necessary to spend several times of the times of Examples 1 to -148-200831962 1 7 and Comparative Examples 1 to 1 1 so that both manufacturing and practical use are not applicable, resulting in poor productivity. The polarizing plate of the present invention has excellent productivity, has no display unevenness, and has a stable color stability over time (high durability), and thus can be suitably used for a liquid crystal display device. The liquid crystal display device of the present invention has excellent productivity, no display unevenness, and color stability over time (high durability), and thus can be suitably used for mobile phones, computer monitors, televisions, liquid crystal projectors, and the like. . BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1A is a cross-sectional view showing the configuration of a polarizing plate of the present invention. Fig. 1B is a cross-sectional view showing the structure of a polarizing plate of the present invention. Fig. 2 is a perspective view showing the configuration of a liquid crystal display device of the present invention. [Main component symbol description] I a Protective film 1b Protective film 1 Protective film 2 Polarized photo 3 Functional optical film 4 Adhesive layer 11 Upper polarizing plate 12 Absorption axis 13 Expanded viewing angle film 15 Upper substrate -149- 200831962 17 Liquid crystal molecule 18 Side substrate 20 enlarged viewing angle film 22 lower polarizing plate 23 absorption axis

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Claims (1)

200831962 X. Patent Application Range 1. A polarizing plate characterized in that the first protective film, the polarizer and the second protective film are laminated in this order, wherein the first protective film is formed. The moisture permeability at 60 ° C and a relative humidity of 95% is 30 g / m ^ 2 · day, and the second protective film is a deuterated cellulose film. 2. For the polarizing plate of claim 1, wherein the first protective film has a moisture permeability of 50 g/m 2 •day. f 3 as in the polarizing plate of claim 1 of the patent, wherein the second protective film has a retardation Re (Re 1 0) in the in-plane direction at 25 ° C and a relative humidity of 10%, and at 25 ° C, relative The absolute 値 of the difference between the retardation 値 (Re80) in the in-plane direction at a humidity of 80%, divided by the retardation Re (Re60) in the in-plane direction at 25 ° C and a relative humidity of 60 %, Gr 0.06 the above. 4. The polarizing plate of claim 1, wherein the second protective film satisfies the following formulas (I) and (Π): 2.30 S SA + SB &lt; 2.80... (I) 0SSBS1.00.............Formula (Π) In the above formulas (I) and (Π), SA and SB represent 醯 substituted by the hydroxyl group of cellulose. The substituent of the group, the SA represents the degree of substitution of the ethyl group, and the SB represents the degree of substitution of the fluorenyl group having 3 to 4 carbon atoms. 5. The polarizing plate of claim 1, wherein the second protective film is stretched, and the retardation in the in-plane direction defined by the following formula (melon) is 20 to 70 nm. The range, and the retardation 値Rth in the thickness direction defined by the following formula (IV) is in the range of 30 to 400 nm, -151 - 200831962 Re- (nx- ny) xd... ·••式(El) Rth 二((nx+ny)/2— nz}xd· · · · · · (IV) In the above formulas (IE) and (IV), the nx film is in-plane The refractive index in the direction of the slow axis, the refractive index in the direction of the phase axis in the plane of the ny-type film, the refractive index in the thickness direction of the η z-based film, and the thickness of the d-type film. 6. Polarization as in the first item of the patent application The plate, wherein the second protective films Re and Rth are deuterated cellulose films satisfying the following formulas (V) and (Vi), | Rth | ........... .. (VI) 7 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ At least a hard cover is placed on the protective film At least one of a coating layer and an anti-reflection layer. A liquid crystal display device having a liquid crystal cell and two liquid crystal display devices disposed on both sides thereof, at least one of which The polarizing plate is a polarizing plate as described in claim 1, and the second protective film of the polarizing plate is attached to the opposite side of the liquid crystal cell. 1 液晶 · The liquid crystal display of claim 9 The device, wherein at least one of a liquid crystal cell VA mode and an IPS mode. -152-