TW201207012A - Cellulose ester film, production method therefor, polarizing plate equipped with same, and liquid crystal display device - Google Patents

Abstract

Disclosed are a cellulose ester film that has a suitable retardation value and high uniformity with a narrow range of variation and a production method therefor. Also disclosed are a polarizing plate equipped with said cellulose ester film and a liquid crystal display device having high display uniformity. The cellulose ester film includes a cellulose ester with a C2-4 acyl substituent in which the degree of acyl group substitution is in the range of 2.0 to 2.5, and is characterized in that the in-plane retardation value (Ro), the retardation value in the thickness direction Rt(590), the plane orientation (S), and the thickness thereof are each within a specific range.

Description

201207012 SUMMARY OF THE INVENTION [Technical Field] The present invention relates to a cellulose ester film, a method for producing the same, a polarizing plate comprising the cellulose ester film, and a liquid crystal display device. More specifically, it relates to a cellulose ester film having a small unevenness in retardation at a specific light wavelength, and a method for producing the same, and a polarizing plate having the cellulose ester film. And display a liquid crystal display device with high uniformity. [Prior Art] The optical film system for liquid crystal display devices has been increasing in size and popularity with liquid crystal display devices, and the production volume has increased year by year. Then, in order to cope with this, the increase in the production speed of the film or the expansion of the film width was investigated. With the increase in the productivity of such an optical film, the film forming process is demanding a high speed, and the winding length of the film tends to be long. In order to increase the speed, length, and width of the film production, the load for solvent removal becomes large at the time of the solution film forming method, and it is difficult to remove the residual solvent in the film. The drying step in the film forming process can be easily removed, and the residual solvent can be easily removed. However, if the time required for the drying step is increased, the productivity is increased in the opposite direction. If the temperature of the drying step is raised, the phase difference is hard to occur, and the planarity is changed. difference. Moreover, in addition to the development of a liquid crystal display device, thin film formation is desired, and high phase difference developability is imparted. In particular, when only one phase difference film is used, a higher phase difference developability is sought. However, it has been found that when an optical film of a film having a phase difference of -5 to 201207012 is produced, there is a problem that the phase difference is large. The inventors of the present invention considered that the unevenness of the phase difference 起 is caused by a poor solvent removal of the optical film due to a thin film and a high phase difference, and the like. Therefore, as a result of the investigation, the thickness of the thinned film should be easy to remove the residual solvent. However, if the surface orientation of the film becomes high, the method of removing the residual solvent in the film can not be removed as desired. A method of hitting a film containing a gas having a boiling point higher than a solvent contained in a film in a drying step is described. However, in the film, for example, if the water vapor is touched, the film after drying tends to be uneven. It is also possible to contain water in the doping, but if the water content is high, the planarity of the film is deteriorated, or the problem of white turbidity still exists (for example, refer to Patent Document 2). However, it can be seen that, by using the resin to be used, for example, even if the same cellulose ester is used, the degree of substitution may be different, and the water content in the suitable doping is different, and when the optical film of the cellulose ester having a low degree of substitution is used, (For example, refer to Patent Documents 3 and 4), even if the moisture content in the doping is high, the film is not turbid. It is clear that the prior art document Patent Document 1: JP-A-2009-137280 Patent Document 2: Special opening 2 0 Patent Document 3: Japanese Laid-Open Patent Publication No. 2009-265 No. PCT Publication No. JP-A No. 2009-249386. SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION In view of the above problems and circumstances, the problem is to provide a cellulose ester film having an appropriate retardation, a small unevenness, and a high uniformity, and a method for producing the same. Further, a polarizing plate comprising the cellulose ester film and a liquid crystal display device having high display uniformity are provided. Means for Solving the Problems The above problems of the present invention can be solved by the following means. A cellulose ester film which is a cellulose ester film of a cellulose ester having a mercapto substituent in the range of 2 to 4 and having a mercapto substitution degree of 2.0 to 2.5, which is characterized In the in-plane retardation 値R〇(590) of the measurement light wavelength of 590 mm, the retardation 値Rt(590) is in the range of 150 to 300 nm, and the surface alignment degree S (590) is in the range of 40 to 100 nm. ) is in the range of 0.001 to 0.01 and has a thickness in the range of 20 to 50 / / m. 2. The cellulose ester film according to the above item 1, wherein the uneven retardation width of the in-plane retardation 値Ro (590) is 5 nm or less, and the retardation width of the retardation 値Rt (590) in the thickness direction is i. 〇nrn below. 3. The cellulose ester film according to the above item 1 or 2, wherein the film has a length in the range of 5 〇 00 to 1 0000 m, and the film has a width of i. 9 to 2.5 m in the range of 201207012. A method for producing a cellulose ester film, which is characterized in that the cellulose ester film according to any one of items 1 to 3 above is characterized in that the water content is in a range of more than 2% and not more than 1% by weight. A type of polarizing plate comprising a cellulose ester film according to any one of items 1 to 3 above. A liquid crystal display device characterized by comprising the cellulose ester film according to any one of the above items. The liquid crystal display device according to the above aspect, wherein the liquid crystal cell has a cellulose ester film according to any one of the above items 1 to 3, and the liquid crystal cell is disposed on a side opposite to the surface. The retardation 値Rt ( 5 90 ) in the thickness direction of the optical film provided is a retardation 値Rt ( 590 ) smaller than the thickness direction of the cellulose ester film. EFFECT OF THE INVENTION According to the above-described means of the present invention, it is possible to provide a cellulose ester film having an appropriate retardation 且 and having a small unevenness and high uniformity and a method for producing the same. Further, a polarizing plate comprising the cellulose ester film and a liquid crystal display device having high display uniformity are provided. The cellulose ester film of the present invention has a fluorenyl substituent in the range of 2 to 4 carbon atoms, and has a thiol substitution degree of 2.0 to 2.5, a thickness of 20 to 50/zm, and a measurement light. The in-plane retardation 値R〇(590) of a wavelength of 590 mm is in the range of 40 to 100 nm, and the retardation 値Rt(590) in the thickness direction is in the range of 15 0 to 30,000 nm, and the phase difference is small. Ester thin 201207012 The manufacturing method of the film. The cellulose ester film of the present invention contains a cellulose ester having a mercapto group having a carbon number of 2 to 4 and a mercapto group substitution degree of 2.0 to 2.5. a cellulose ester film characterized by having a retardation 値Ro (590) of 40 to 100 nm in the in-plane retardation wavelength of 5 90 mm and a retardation 値Rt (590) of 150-300 nm in the thickness direction. The surface orientation S (590) is in the range of 0.001 to 0.01, and the thickness is in the range of 20 to 5 Å Aim. This feature is a technical feature common to the inventions of claims 1 to 7. In the embodiment of the present invention, it is preferable that the unevenness of the in-plane retardation 値R 〇 ( 590 ) is 5 nm or less, and the retardation 値Rt ( 5 90 ) in the thickness direction is different from the viewpoint of the effect of the present invention. The width of the misalignment is below lOnm. Further, the length of the film is preferably in the range of 5,000 to 10,000 m, and the width of the film is in the range of 1.9 to 2.5 m. The method for producing a cellulose ester film of the present invention is preferably a method for producing a dope having a water content of more than 2% and 10% or less. The cellulose ester film of the present invention is suitably used for Polarizer and liquid crystal display device. In this case, it is preferable that the liquid crystal display device of the present invention has a cellulose ester film of the present invention on one side of the liquid crystal cell, and has a retardation in the thickness direction of the optical film provided on the surface opposite to the surface of the liquid crystal cell.値Rt(590) is a retardation 値Rt (590) smaller than the thickness direction of the aforementioned cellulose ester film. 201207012 Further, in the present case, R〇(590), Rt(590), and surface orientation S (590) are defined by the following formulas (I) to (III), respectively. Formula (I) : Ro ( 590 ) = ( nx-ny ) xd Equation (II) : Rt ( 590 ) = ( (nx + ny) /2 -nz ) xd Equation (III) : S ( 590 ) = ( nx + ny) /2-nz In the above formula, Ro (590) represents the in-plane retardation 値 in the film at a wavelength of 59 Onm, and Rt( 590) represents the retardation in the thickness direction of the film at a wavelength of 590 nm. value. d is the thickness (nm) of the film, and nx is the maximum refractive index in the in-plane of the film having a light wavelength of 590 nm, which is also referred to as the refractive index in the direction of the slow axis. The ny system indicates the refractive index in the direction perpendicular to the slow axis in the plane of the film having a light wavelength of 590 nm, and the nz indicates the refractive index of the film in the thickness direction of the measuring wavelength of 590 nm. Hereinafter, the present invention and its constituent elements, and aspects and aspects for carrying out the invention will be described in detail. <Cellulose Ester> The cellulose ester film of the present invention is characterized in that it contains a cellulose ester having a fluorenyl substituent in the range of 2 to 4 and a thiol substitution degree of 2.0 to 2.5. The cellulose ester of the present invention preferably has a hydroxyl (hydroxyl) residual (DR) of from 0.5 to 1.0, but the hydroxyl (hydroxyl) residue (DR) is more preferably from 0.5 to 0.8. Here, the "hydroxyl (hydroxyl) residue (DR)" is one of the three hydroxyl groups (hydroxyl groups) of the anhydrous glucose which constitutes cellulose, and represents the hydroxyl group (hydroxyl group) which is not esterified by -10 to 201207012. The number of (average 値). That is, the degree of esterification (also referred to as degree of substitution) of cellulose is expressed as a hydroxyl group (hydroxyl group) residue (DR) = 3 degree of esterification. Further, the degree of substitution of the cellulose ester is expressed by the degree of acetification, and the average degree of acetification of the cellulose ester means the amount of bound acetic acid per unit mass of cellulose, according to ASTM: D-817-96C cellulose acetate, etc. Test method) The measurement can be calculated and determined. The cellulose ester is a carboxylate having a carbon number of from 2 to 4, and may be an ester of an aromatic carboxylic acid. In particular, a lower fatty acid ester having a carbon number of 2 or less is more preferably a lower fatty acid ester having a carbon number of 2 or less. The number average molecular weight (??) of the cellulose ester used in the present invention is in the range of 3,000 to 300,000, and the mechanical strength of the obtained film is very good. More suitable to use 50,000 ~ 200,000. The ratio of the weight average molecular weight (Mw) of the cellulose ester to the number average molecular weight (??) Mw / Mn is preferably 1.4 to 3.0. The weight average molecular weight (Mw) and the number average molecular weight (??) of the cellulose ester were measured by gel permeation chromatography (GPC). The measurement conditions are as follows. Solvent: Dichloromethane column: Shodex K806, K805, K803 G (used in connection with 3 of Showa Denko). Column temperature: 25 °C Sample concentration: 〇.1 mass% Detector: RI Model 504 ( GL Science Co., Ltd.) -11 - 201207012 Pump: L6000 (manufactured by Hitachi, Ltd.) Flow rate: 1.0 ml/min Calibration curve: Standard polystyrene STK Standard polystyrene (manufactured by Tosoh Co., Ltd.) Mw=1 000000~5 00 of 13 sample calibration curve. 13 samples were used at approximately equal intervals. The cellulose of the raw material of the cellulose ester of the present invention is not particularly limited, and examples thereof include cotton linters, wood pulp, and Kenaf. Further, the cellulose esters obtained from these can be used in combination at any ratio. The cellulose ester of the present invention can be produced by a known method. Specifically, it can be synthesized by referring to the method described in Japanese Laid-Open Patent Publication No. Hei No. Hei. Commercially available products include, for example, L20, L30 'L40 'L50 manufactured by Daicel Chemical Industry Co., Ltd., Ca 398-3, Ca 3 98-6, Ca 3 98-1 0, Ca 398-30 of Eastman Chemical Co., Ltd. Ca 394-60S. The total amount of calcium and magnesium (PPm) and the amount of acetic acid (ppm) contained in the cellulose ester film of the present invention are preferably in the following relationship (1) » Relationship (1) 1S (acetic acid amount (ppm)) / (Total amount of calcium and magnesium (ppm)) $30 Calcium and magnesium are cellulose esters contained in the raw material of the cellulose ester film, but neutralize the acid catalyst (especially sulfuric acid) added in the cellulose ester production process, Since it is stabilized, it can also be added by forming a metal oxide, a metal hydroxide, a metal salt (mineral acid salt, organic acid salt). Further, when a cellulose ester film is formed into a film, a metal oxide, a metal hydroxide, a metal salt (inorganic acid salt or an organic acid salt) may be added, and calcium and magnesium contained in the cellulose ester film of the present invention may be added. The total amount (ppm) refers to the total amount of them. -12- 201207012 Further, the cellulose ester film is used in the production process, and acetic anhydride or acetic acid can be used as the reaction solvent or the esterifying agent. The degree of substitution can be adjusted depending on the amount of the esterifying agent used or the reaction time. Further, after the esterification reaction is terminated, it may be hydrolyzed as needed, and the degree of substitution may be adjusted. The unreacted acetic anhydride can be hydrolyzed by a reaction stopping agent (water, alcohol, acetic acid, etc.) to produce acetic acid. The amount of acetic acid (ppm) contained in the cellulose ester film of the present invention means the total amount of residual acetic acid or free acetic acid. In the above relation (1), the total amount (ppm) of calcium and magnesium / the amount of acetic acid (ppm) is preferably 1 or more and 30 or less. When it is less than 1, the amount of acetic acid is small with respect to the amount of calcium and magnesium, but light scattering due to calcium and magnesium metal salts reduces the contrast and is not preferable. Further, when it is more than 30, acetic acid is excessively added to the amount of calcium and magnesium. However, when the cellulose ester is bonded to the polarizer, acetic acid promotes deterioration of the polarizer, which is not preferable. The total amount of calcium and magnesium contained in the cellulose ester film is preferably 5 to 13 Oppm, more preferably 5 to 80 ppm, most preferably 5 to 50 ppm. The amount of acetic acid contained in the cellulose ester film is preferably from 20 to 500 ppm, more preferably from 25 to 250 ppm, most preferably from 30 to 150 ppm. The amount of calcium and magnesium contained in the cellulose ester film can be determined by a known method. However, after the dried cellulose ester is completely burned, the ash is dissolved in hydrochloric acid before treatment, and it can be measured by atomic absorption. Determination of lanthanide The calcium and magnesium contents of the cellulose ester lg in an absolute dry state can be obtained in ppm. A known method can be used for the quantitative determination of the acetic acid contained in the cellulose ester film, but the following method can be used. The film was dissolved in dichloromethane, and the reaction was carried out by adding methanol to a step of -13-201207012. The supernatant was filtered, and the supernatant was measured by gas chromatography to obtain the amount of acetic acid. <Additives> The cellulose ester film of the present invention preferably contains a retardation developing agent for the purpose of exhibiting retardation, a retardation controlling agent for controlling retardation, a plasticizer for imparting workability to a film, and a film preventing film. An additive such as a degraded antioxidant, an ultraviolet absorber that imparts an ultraviolet absorbing function, a matting agent that imparts slip properties to a film, and a peeling resistance (peeling resistance) when the film is peeled off from the metal support is used as an additive. (Retardation-developing agent) In the present invention, a retardation-developing agent may also be contained. The retardation-developing agent can be contained, for example, in a ratio of 0.5 to 10% by mass, and more preferably in a ratio of 2 to 6% by mass. By using a retardation-developing agent, high Re-reproducibility can be obtained at a low stretching ratio. The type of the retardation-developing agent is not particularly limited, and examples thereof include a rod-shaped or disk-shaped compound. As the above-mentioned rod-like or disc-shaped compound, a compound having at least two aromatic rings is preferably used as the retardation-developing agent. The amount of the retardation-developing agent which is composed of the rod-like compound is preferably 0.5 to 10 parts by mass, more preferably 2 to 6 parts by mass, per part by mass of the polymer component containing the cellulose ester. The disc-shaped retardation-developing agent is preferably used in an amount of from 0.5 to 10 parts by mass, more preferably from 1 to 8 parts by mass, based on 100 parts by mass of the polymer component containing the cellulose ester, and most preferably 2 ~6 parts by mass range -14-201207012 Two or more types of retardation-developing agents can also be used. The retardation-developing agent preferably has a maximum absorption in a wavelength region of from 2, 50 to 400 nm, and preferably has substantially no absorption in the visible light region. Explain about discotic compounds. As the discotic compound, a compound having at least two aromatic rings can be used. In the present specification, the "aromatic ring" may contain an aromatic heterocyclic ring in addition to the aromatic hydrocarbon ring. The aromatic hydrocarbon ring is particularly preferably a 6-membered ring (i.e., a benzene ring). The aromatic heterocyclic ring is generally an unsaturated heterocyclic ring. The aromatic heterocyclic ring is preferably a 5-membered ring, a 6-membered ring or a 7-membered ring, and more preferably a 5-membered ring or a 6-membered ring. Aromatic Heterocycles generally have the most double bonds. The hetero atom is preferably a nitrogen atom, an oxygen atom or a sulfur atom, and particularly preferably a nitrogen atom. Examples of the aromatic heterocyclic ring include a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an amidine ring, a terpene ring, a furazan ring, A triterpene ring, a fluorene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a 1,3,5-triazine ring. The aromatic ring system is preferably a benzene ring, a condensed benzene ring or a biphenyl ring. It is especially preferred to use a 1,3,5-triazine ring. Specifically, a compound disclosed in, for example, JP-A-2001-166144 is preferably used. The retardation developing agent has an aromatic ring preferably having a carbon number of 2 to 20, more preferably 2 to 12, most preferably 2 to 8, most preferably 2 to 6. The relationship between the two aromatic rings can be classified into (a) the case where a condensed ring is formed' (b) the case where a single bond is directly bonded and (c) the case where the bond is bonded via a link -15-201207012 (because of the aroma旄&amp; _ ring 'snail key system cannot be formed). The binding relationship can be any of (a) ~ (c). Examples of the condensed ring (a condensed ring of two or more aromatic rings of 119 or more) include: an anthracene ring, a naphthalene ring, a gannet cat, a daisy ring, an anthracene ring, a phenanthrene ring, an onion ring, a terpene, Biphenyl ring, Ding ring, 'poor b ring, anthraquinone ring, isoindole ring, benzofuran ring, benzothiophene ring, D lead night brain mazine ring, benzoxazole ring, benzothiazole Ring, benzimidazole ring, benzo = _ _ ~ feed ring, anthracene ring, carbazole ring, chromene ring, porphyrin ring, iso- ring, porphyrin exposure ring, (tetra) porphyrin ring, increase Linn (cinn〇line) ring, 喔 quinoline ring, (four) ring, dish (four) 1 (four), (four) ring, phenanthrenequinone, oxy-ketone ring, pheno-cyclo ring, pheno-salt ring, phenoxy thiophene (Phenoxathin) ring, dysentery A phenazine xazine ring and a thianthrene ring. Preferably, the single bond of the naphthalene ring, the chamomile ring, the anthracene ring, the benzo D-oxime ring, the benzothiazepine ring, the benzimidazole ring, the benzotrioxane ring, and the porphyrin ring (b) should be two aromatic The bond between the carbon atoms of the family ring. The two aromatic rings may be bonded by two or more single bonds, and an aliphatic ring or a non-aromatic heterocyclic ring may be formed between the two aromatic rings. The linking group of (c) is also preferably bonded to the carbon atoms of the two aromatic rings. The linking group is preferably a combination of an alkyl group, an alkenyl group, an alkynyl group, -CO-, -0-, -NH-, -S- or the like. Examples of the linking group composed of the combinations are shown below. Further, the left-right relationship of the examples of the following linking groups may be reversed. Cl· -C0-0-c2 : -CO-NH-c3 : ·alkylene-0- -16· 201207012 c4 : -NH-CO-NH-c5 : -NH-CO-O-c6 : -O- CO-O-c7: -o-alkylene- θα : -CO-alkenyl-c9: -CO-alkenyl-NH-clO: -CO-alkenyl-O-cll:-alkylene -CO-O-alkylene-O-CO.alkyl-cl2:-alkylene-CO-O-alkylene- O-CO-alkylene-O- cl3 : -O-CO -Extension Alkyl-CO-O-cl4: -NH-CO-alkenyl-c 1 5 : - c 〇-alkenyl-aromatic ring and linking group may also have a substituent. Examples of the substituent include: Halogen atom (F, Cl, Br, I), hydroxyl group, carboxyl group, hydrogen group, amine group, nitro group, sulfo group, methylamino group, amisulpht group, ureido group, alkyl group, alkenyl group, alkynyl group, An aliphatic sulfhydryl group, an aliphatic decyloxy group, an alkoxy group, an alkoxycarbonyl group, an alkoxycarbonylamino group, an alkylthio group, an alkyl sulfo group, an aliphatic decylamino group, an aliphatic sulfonylamino group, An aliphatic substituted amine group, an aliphatic substituted methylamino group, an aliphatic substituted sulfonamide group, an aliphatic substituted ureido group, and a non-aromatic heterocyclic group. The alkyl group preferably has 1 to 8 carbon atoms. The chain-like alkyl group is preferred to the cyclic alkyl group, and is particularly preferably a linear alkyl group. The alkyl group may further have a substituent (e.g., a hydroxyl group, a carboxyl group, an alkoxy group, an alkyl-substituted amine group). Examples of the alkyl group (containing a substituted alkyl group) include a methyl group, an ethyl group, a n-butyl group, a n-hexyl group, a 2-hydroxyl-17-201207012 group, a 4-hydroxybutyl group, a 2-methoxyethyl group, and a 2- Each group of diethylaminoethyl. The number of carbon atoms of the alkenyl group is preferably from 2 to 8. The chain-like alkenyl group is preferred to the cyclic alkenyl group, and particularly preferably a linear alkenyl group-alkenyl group may further have a substituent. Examples of alkenyl groups include vinyl, allyl and 1-hexenyl. The alkynyl group preferably has 2 to 8 carbon atoms. The alkynyl group is preferably a cyclic alkynyl group, more preferably a linear alkynyl group. The alkynyl group may further have a substituent. Examples of the alkynyl group include an ethynyl group, a 1-butynyl group, and a 1-hexynyl group. The aliphatic sulfhydryl group preferably has 1 to 1 carbon atom. Examples of the aliphatic thiol group include an ethyl group, a propyl group and a butyl group. The aliphatic methoxy group preferably has 1 to 10 carbon atoms. An example of an aliphatic methoxy group contains an ethoxy group. The alkoxy group preferably has 1 to 8 carbon atoms. The alkoxy group may further have a substituent (e.g., an alkoxy group). The alkoxy group (containing a substituted alkoxy group) is exemplified by a methoxy group, an ethoxy group, a butoxy group and a methoxyethoxy group. The alkoxycarbonyl group preferably has 2 to 10 carbon atoms. The alkoxycarbonyl group contains a methoxycarbonyl group and an ethoxycarbonyl group. The alkoxycarbonylamino group preferably has 2 to 10 carbon atoms. Examples of the alkoxycarbonylamino group include a methoxycarbonylamino group and an ethoxycarbonylamino group. The alkylthio group preferably has 1 to 12 carbon atoms. Examples of the alkylthio group containing a methylthio group, an ethylthio group and an octylthio group of a β alkylsulfonyl group have preferably 1 to 8 carbon atoms. Examples of the alkylsulfonyl group include a methanesulfonyl group and an ethanesulfonyl group. The aliphatic guanamine group preferably has 1 to 1 carbon atom. The aliphatic guanamine group -18-201207012 case contains 'acetamide. The aliphatic sulfonamide group preferably has 1 to 8 carbon atoms. Examples of the aliphatic sulfonamide group include a methanesulfonamide group, a butanesulfonylamino group, and an n-octanesulfonylamino group. The aliphatic substituted amine group preferably has 1 to 10 carbon atoms. Examples of the aliphatic substituted amine group include a dimethylamino group, a diethylamino group and a 2-carboxyethylamino group. The aliphatic substituted methylamine group preferably has 2 to 10 carbon atoms. Examples of the aliphatic substituted methylamine group include methylmethicone and diethylmethylammonium. The aliphatic substituted amisulphtyl group preferably has 1 to 8 carbon atoms. Examples of aliphatic substituted amsulfoxans include methylsulfamoyl and diethylsulfonamide. The aliphatic substituted urea group preferably has 2 to 10 carbon atoms. Examples of the aliphatic substituted urea group contain a methylureido group. Examples of the non-aromatic heterocyclic group include a hexahydropyridyl group and a morpholinyl group. The molecular weight of the retardation-developing agent is preferably from 300 to 800. A triazine compound represented by the following formula (1) is preferably used as the discotic compound. General formula (I)

R1-X 丫N 丫 X-Ri N 丫N

X

I R1 In the above formula (I): R1 each independently represents an aromatic ring and a heterocyclic ring having a substituent of at least one of an ortho, meta and para. -19 - 201207012 X independently indicates a single button or NR2-. Here, R2 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group or a heterocyclic group. The aromatic ring represented by R1 is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aromatic ring represented by R1 may have at least one substituent at the substitution position of either. Examples of the aforementioned substituent include a halogen atom, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group, a mercaptooxy group, an alkoxy group. Carbonyl, alkenyloxycarbonyl, aryloxycarbonyl, sulfonyl, alkyl substituted amisulphtyl, alkenyl substituted amisulphtyl, aryl substituted amisulphtyl, sulfonylamino, methylamine An alkyl-substituted methylamino group, an alkenyl-substituted methylamino group, an aryl-substituted methylamino group, a decylamino group, an alkylthio group, an alkenylthio group, an arylthio group and an anthracenyl group. The heterocyclic group represented by R1 is preferably aromatic. The aromatic heterocyclic ring is generally an unsaturated heterocyclic ring, and is preferably a heterocyclic ring having the most double bonds. The heterocyclic ring should be a 5-member ring, a 6-member ring or a 7-member ring, and is preferably a 5-member ring or a 6-member ring, and is preferably a 6-member ring. The hetero atom of the hetero ring is preferably a nitrogen atom, a sulfur atom or an oxygen atom, and particularly preferably a nitrogen atom. The aromatic heterocyclic ring is particularly preferably a pyridine ring (heterocyclic group is 2-pyridyl group or 4-pyridyl group). The heterocyclic group may also have a substituent. Examples of the substituent of the heterocyclic group are the same as those of the substituent of the above aryl moiety. The heterocyclic group when X is a single bond is preferably a heterocyclic group having a free valence of a nitrogen atom. The heterocyclic group having a free valence of a nitrogen atom is preferably a 5-membered ring, a 6-membered ring or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and most preferably a 5-membered ring. The heterocyclic group may also have a plurality of nitrogen atoms. Further, the heterocyclic group may have a hetero atom other than a nitrogen atom (e.g., 0, S). The following is an example of a heterocyclic group having a free valence of -20 to 201207012 in a nitrogen atom. [Chemical 2]

COOC4H9(n) R2 represents an alkyl group which may be a cyclic alkyl group or a chain alkyl group, but is preferably a linear alkyl group having a branched chain alkyl group, more preferably a linear alkyl group. The number of carbon atoms of the alkyl group is preferably from 1 to 30, more preferably from 1 to 20, most preferably from 1 to 1 Torr, particularly preferably from 1 to 8, most preferably from 1 to 6. The alkyl group may also have a substituent. Examples of the substituent include a halogen atom, an alkoxy group (e.g., methoxy group, ethoxy group), and an anthracene group (e.g., propylene decyloxy group, methacryloxy group). R2 represents an alkenyl group which may be a cyclic alkenyl group or a chain alkenyl group, but is preferably a chain alkenyl group, and has a branched chain alkenyl group, and is more preferably a linear alkenyl group. The number of carbon atoms of the alkenyl group is preferably 2 to 30', more preferably 2 to 20', most preferably 2 to 10, particularly preferably 2 to 8, most preferably 2 to 6. The alkenyl group may also have a substituent. Examples of the substituent are the same as the substituent of the above alkyl group. R2 represents an aromatic ring group and a heterocyclic group, and R1 represents an aromatic ring and a heterocyclic ring, and the preferred range is also the same. The aromatic ring group and the heterocyclic group may have a substituent in the step -21 - 201207012, and the substituent is the same as the substituent of the aromatic ring and the hetero ring of R1. As the discotic compound, a triphenylene compound represented by the following formula (Π) is also preferably used. [Chemical 3] - General formula (II) R «〇 ORl

In the above formula (II), R1, R2, R3, R4, R5 and R6 each independently represent a hydrogen atom or a substituent. The substituent represented by each of R1, R2, R3, R4, R5 and R6 may, for example, be an alkyl group (preferably having a carbon number of 1 to 40, more preferably a carbon number of 1 to 30, and particularly preferably a carbon number of 1 to 30). The alkyl group of 20, for example, methyl, ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.) And an alkenyl group (preferably a carbon number of 2 to 40, more preferably a carbon number of 2 to 30, and particularly preferably an alkenyl group having 2 to 20 carbon atoms), and examples thereof include a vinyl group, an allyl group, and a 2-butenyl group. 3-pentenyl or the like), alkynyl group (preferably a carbon number of 2 to 4 Å, more preferably a carbon number of 2 to 30, and particularly preferably an alkynyl group having 2 to 20 carbon atoms, and examples thereof include propynyl group, 3 _Pentynyl, etc.), aryl (preferably a carbon number of 6 to 30, more preferably a carbon number of 6 to 20, and particularly preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group and a p-methylbenzene group. a group, a naphthyl group, or the like, a substituted or unsubstituted amine group (preferably having a carbon number of 〇~4〇, more preferably a carbon number of 〇30, and particularly preferably a carbon number of 20-20), for example, Substituted amine group, methyl-22-201207012 amino group, dimethylamino group, diethylamino group, anilino group, etc.), alkoxy group (preferably carbon number) 1 to 40, more preferably a carbon number of 1 to 30, particularly preferably an alkoxy group having 1 to 20 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a butoxy group, and the like, and an aryloxy group (preferably, a carbon number of 6 to 40, more preferably a carbon number of 6 to 30, particularly preferably an aryloxy group having 6 to 20 carbon atoms, and examples thereof include a phenoxy group and a 2-naphthyloxy group, and a mercapto group (preferably carbon). The number of the thiol group is preferably from 1 to 40, more preferably from 1 to 30, and particularly preferably from 1 to 20, and examples thereof include an ethyl fluorenyl group, a benzamidine group, a methyl group, a trimethyl acetyl group, and the like. And an alkoxycarbonyl group (preferably a carbon number of 2 to 40, more preferably a carbon number of 2 to 30, and particularly preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, and examples thereof include a methoxycarbonyl group and an ethoxy group). a carbonyloxy group or the like, an aryloxycarbonyl group (preferably a carbon number of 7 to 40, more preferably a carbon number of 7 to 30, and particularly preferably an aryloxycarbonyl group having 7 to 20 carbon atoms, such as a phenoxycarbonyl group) And an anthraceneoxy group (preferably a carbon number of 2 to 40, more preferably a carbon number of 2 to 30, and particularly preferably a carbon number of 2 to 20), and examples thereof include an ethyl oxy group and a benzhydryloxy group. Further, a mercaptoamine group (preferably having a carbon number of 2 to 40' is preferably a carbon number of 2 to 30, and particularly preferably an amine group having 2 to 20 carbon atoms, and examples thereof include an ethyl group. Alkoxycarbonylamino group (preferably a carbon number of 2 to 40, more preferably a carbon number of 2 to 30, and particularly preferably an alkoxycarbonylamine having a carbon number of 2 to 20) The base may, for example, be a methoxycarbonylamino group, or an aryloxycarbonylamino group (preferably having a carbon number of 7 to 40, more preferably a carbon number of 7 to 30, and particularly preferably an aromatic oxygen having a carbon number of 7 to 20). The carbonylcarbonylamino group may, for example, be a phenoxycarbonylamino group or the like, or a sulfonylamino group (preferably having a carbon number of 1 to 40, more preferably a carbon number of 1 to 30, and particularly preferably a carbon number of 1 to 20). The sulfonylamino group may, for example, be a methanesulfonylamino group or a benzenesulfonylamino group, or a sulfonamide group (preferably having a carbon number of 〇40 to 40, more preferably a carbon number of 0 to 30). Aminosulfonyl group having a carbon number of 0 to 20, such as, for example, sulfonamide, methylsulfamoyl, dimethylsulfamoyl-23-201207012, phenylsulfamoyl, etc., An amidoxime group (preferably a methylamine group having a carbon number of 1 to 40, more preferably a carbon number of 1 to 30, and particularly preferably a carbon number of 1 to 20, and examples thereof include an unsubstituted methylamine thiol group and a methyl group. Amine thiol, diethylmethylamino hydrazino, phenylmethylamine hydrazino, etc.), alkoxythio group (preferably carbon number 1) ～40, more preferably, the carbon number is 1 to 3 〇, and the carbon number is 1 to 20, and examples thereof include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, and a hexylthio group, a heptylthio group, an octylthio group, etc., an arylthio group (preferably having a carbon number of 6 to 40, a more preferred carbon number of 6 to 30, and a particularly preferred carbon number of 1 to 20). For example, a phenylthio group or the like, a sulfonyl group (preferably having a carbon number of 1 to 40, more preferably a carbon number of 1 to 30 Å, and a sulfonyl group having a carbon number of 1 to 20) may be, for example, a methylsulfonyl group. , toluenesulfonyl group, etc., sulfinyl group (preferably having a carbon number of 1 to 40, more preferably a carbon number of 1 to 30, and particularly preferably a sulfinyl group having 1 to 20 carbon atoms, such as methane Sulfhydryl group, phenylsulfinyl group, etc., urea group (preferably having a carbon number of 1 to 40, more preferably a carbon number of 1 to 30, and particularly preferably a urea group having 1 to 20 carbon atoms) may be, for example, unsubstituted. Urinyl group, methylurea group, phenylureido group, etc.), guanidinium phosphate group (preferably having a carbon number of 1 to 40, more preferably a carbon number of 1 to 30, and particularly preferably having a carbon number of 1 to 20) Examples of the amine group include a diethylphosphonium amide group, a phenylphosphonium amide group, and the like, a hydroxyl group, a thiol group, and a halogen atom (for example, a fluorine atom). Chlorine atom, bromine atom, iodine atom) 'cyano group, sulfo group, carboxyl group, nitro group, hydroxylamine group, sulfinic acid group, hydrazine group, imido group, heterocyclic group (preferably, carbon number 1 to 3) 0, more preferably a heterocyclic group of 1 to 12, for example, a heterocyclic group having a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom, and examples thereof include an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, and a hexahydro group. Pyridyl, morpholinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, 1,3,5-triazinyl, etc., methoxyalkyl (preferably carbon number 3 to 40, more) Good carbon number 3~30, especially good carbon-24-201207012 number 3~24 of methacrylate, etc.). Replace. Also, it is different. Further, r| , R2, aryl, and substituted Q may be exemplified below. The alkyl group may, for example, be a substituent such as a trimethylmethane group or a triphenyl group. Further, the substituent may be the same or two or more substituents. Can be combined with each other to form a ring. R3, R4 'R5 and R6 are each a specific example of a compound represented by the formula (π) in which the substituent is an alkyl group or an unsubstituted amino group, an alkoxy group, an alkylthio group or a halogen atom, but not -25- V-2

201207012 [Chemical 4] V-1 V-3

RO OR V-4

OR

-26- 201207012 [化5]

V-7 Ο

RO OR

R

C3h7 -27- 201207012 [Chem. 6]

The compound represented by the formula (I) can be, for example, the method described in JP-A-2003-34465, and the compound represented by the formula (II) can be used, for example, in JP-A-2005-134384. The method described is synthesized by a known method. In the present invention, it is also preferred to use a rod-like compound having a linear structure in addition to the above-mentioned disc-shaped compound. The linear molecular structure means that the molecular structure of the rod-like compound in the thermodynamically most stable structure is linear. The thermodynamically most stable structure can be obtained by crystal structure analysis or molecular orbital calculation. For example, molecular orbital calculation software (for example, Win MOP AC 20 00, Fujitsu Co., Ltd.) is used for molecular orbital calculation, and a molecular structure in which the heat of formation of a compound is minimized can be sought. The linear structure of the molecular structure means that the thermodynamically most stable structure sought as described above is formed, and the angle of the molecular structure main chain is 140 degrees or more. The rod-like compound having at least two aromatic rings is preferably a compound represented by the following formula (ΠΙ). -28-201207012 Formula (III): Ari-Li-Ar2 In the above formula (III), human 1 and Ar 2 are each independently an aromatic group. In the present specification, the aromatic group contains an aryl group (aromatic). A trivalent hydrocarbon), a substituted aryl group, an aromatic heterocyclic group, and a substituted aromatic heterocyclic group. The aryl group and the substituted aryl group are more preferably an aromatic heterocyclic group or a substituted aromatic heterocyclic group. The heterocyclic ring of the aromatic heterocyclic group is generally unsaturated. The aromatic heterocyclic ring is preferably a 5-membered ring, a 6-membered ring or a 7-membered ring, and more preferably a 5-membered ring or a 6-membered ring. Aromatic heterocycles generally have the most double bonds. The hetero atom is preferably a nitrogen atom, an oxygen atom or a sulfur atom, more preferably a nitrogen atom or a sulfur atom. The aromatic ring of the aromatic group is preferably a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, a thiazole ring, an imidazole ring, a triazole ring, a pyridine ring, a pyrimidine ring or a pyrazine ring, and particularly preferably a benzene ring. . Examples of the substituent of the substituted aryl group and the substituted aromatic heterocyclic group include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxyl group, a cyano group, an amine group, an alkylamine group (for example, a methylamine). a base, an ethylamino group, a butylamino group, a dimethylamino group, a nitro group, a sulfo group, a methylamino group, an alkylmethylamino group (for example, N-methylmethylamino group, N-ethylmethylamine sulfhydryl, N,N-dimethylmethylamine thiol), sulfonamide, alkylsulfamoyl (eg N-methylsulfamoin, N-B Alkylsulfonyl, N,N_: methylsulfamoyl group), urea group, alkylurea group (eg N-methylureido, indole, indole-dimethylureido, anthracene, anthracene) , Ν'- each of the trimethylurea), alkyl (eg methyl, ethyl, propyl, butyl, pentyl, heptyl, octyl, isopropyl, t-butyl, third pentyl Alkenyl, cyclohexyl, cyclopentyl), alkenyl (eg vinyl, -29-201207012 allyl, hexenyl), alkynyl (eg ethynyl, butynyl), fluorenyl (eg, methyl group, ethyl group, butyl group, hexyl group, base of laurel base) Alkoxy (e.g., ethoxycarbonyl, butyloxy, hexyloxy, lauryloxy), alkoxy (e.g., methoxy, ethoxy, propoxy, butoxy) Each of pentyloxy, heptyloxy, octyloxy), aryloxy (eg phenoxy), alkoxycarbonyl (eg methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxy) a group of a carbonyl group, a pentyloxycarbonyl group, a heptyloxycarbonyl group, an aryloxycarbonyl group (for example, a phenoxycarbonyl group), an alkoxycarbonylamino group (for example, a butoxycarbonylamino group, a hexyloxycarbonylamino group) , alkylthio (such as methylthio, ethylthio, propylthio, butylthio, pentylthio, heptylthio, octylthio), arylthio (such as phenylthio), alkane Alkylsulfonyl (for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, pentylsulfonyl, heptylsulfonyl, octylsulfonyl) And a non-aromatic heterocyclic group (for example, morpholino group, pyrazinyl group) of an amidino group (for example, an acetamino group, a butylammonium group, a hexamethyleneamine group, or a lauric acid group). Among them, preferred substituents include, for example, a halogen atom, a cyano group, a carboxyl group, a hydroxyl group, an amine group, an alkylamino group, a decyl group, a decyloxy group, a decylamino group, an alkoxycarbonyl group, an alkoxy group, and an alkylthio group. Base, and alkyl. The alkyl moiety of the alkylamino group, the alkoxycarbonyl group, the alkoxy group and the alkylthio group may further have a substituent with the alkyl group. Examples of the substituent of the alkyl group and the alkyl group include a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, an amine group, an alkylamino group, a nitro group, a sulfo group, a methylamino group, an alkylamino group, an amsulfoxane. Base, alkylsulfonyl, ureido, alkylureido, alkenyl, alkynyl, decyl, decyloxy, -30-201207012 alkoxy, aryloxy, alkoxycarbonyl, aryloxy A carbonyl group, an alkoxycarbonylamino group, an alkylthio group, an arylthio group, an alkylsulfonyl group, a decylamino group, and a non-aromatic heterocyclic group. The substituent of the alkyl moiety and the alkyl group is preferably a halogen atom, a hydroxyl group, an amine group, an alkylamino group, a decyl group, a decyloxy group, a decylamino group, an alkoxycarbonyl group or an alkoxy group. In the formula (III), L is a divalent linking group selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, -0-, -CO-, and the like. The alkylene group may also have a cyclic structure. The cyclic alkyl group is preferably a cyclohexyl group, and particularly preferably a 1,4-cyclohexyl group. The chain alkyl group is more preferred than the linear alkyl group. The number of carbon atoms of the alkyl group is preferably from 1 to 20, more preferably from 1 to 15, most preferably from 1 to 10, particularly preferably from 1 to 8, most preferably from 1 to 6. The alkenyl group and the alkynylene group are not as suitable as the cyclic structure, and have a chain structure, and it is more preferred to have a linear structure than the branched chain structure. The number of carbon atoms of the alkenyl group and the alkynylene group is preferably from 2 to 10, more preferably from 2 to 8, most preferably from 2 to 6, particularly preferably from 2 to 4, most preferably 2 (ethylene or acetylene). base). The aryl group preferably has a carbon number of 6 to 2 0, more preferably 6 to 16, and most preferably 6 to 12 〇 in the molecular structure of the formula (III), the angle between the formation of L, An and Ar 2 is preferably It is 140 degrees or more. The rod-like compound is more preferably a compound represented by the following formula (IV) - 31 - 201207012 Formula (IV) · Ar 1 - L2 - X_L3-Ar2 In the above formula (IV), An and 八 1* 2 are independently aromatic groups. The definition and examples of the aromatic group are the same as those of An and Man of the formula (ΠΙ). In the formula (IV), 1 and L2 are each independently a divalent linking group selected from the group consisting of an alkyl group, a fluorene group, a -CO- group, and the like. The alkylene group does not have a chain structure and has a chain structure, and the chain structure having a branching is inferior to a linear structure. The alkyl group has preferably 1 to 10 carbon atoms, more preferably 1 to 8, more preferably 1 to 6, more preferably 1 to 4, most preferably 1 or 2 (methylene or ethylene). . L2 and l3 are especially -O-CO- or C0-0-. In the formula (IV), X is a 1,4-cyclohexyl group, a vinyl group or an ethynyl group. Specific examples of the compound represented by the formula (III) or (IV) include, for example, the compound described in JP-A-2004-109657, which is a compound of the formula [Chemical Formula 1] to [Chemical Formula 1]. A rod-like compound having a maximum absorption wavelength (Λ max) longer than 250 nm may be used in two or more types. The rod-like compound can be synthesized by referring to the method described in the literature. For literature, for example, Mol. Cryst. Liq. Cryst·, Vol. 53, 229 (1979), Vol. 89, p. 93 (1982), Vol. 145, 111 (1987), Vol. 170, 43 Page (1 9 9 9), J. Am. Chem. Soc., Vol. 113, p. 1349 (1991), Vol. 118, p. 5346 (1996), same as 92, 1 5 8 2 (1) 970), J. Org. Chem., 40, 420 (1 975), Tetrahedron, 48, 16 and 3,437 (1 992). Further, as the retardation-developing agent, a rod-shaped aromatic compound described in pages 11 to 14 of JP-A-2-4051-6 can also be used. Further, as the retardation-developing agent, one type of compound may be used alone or two or more types of compounds may be mixed and used. When the retardation-developing agent uses two or more kinds of compounds which are different from each other, the retardation can be adjusted to a wide range and can be easily adjusted to a desired range, which is preferable. The amount of the retardation-developing agent to be added is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass based on 100 parts by mass of the cellulose ester. Further, when the cellulose ester film is produced by a solvent casting method, the retardation developing agent may be added to the doping. The addition may be carried out at any timing, for example, after dissolving the retardation-developing agent in an organic solvent such as alcohol, dichloromethane, or dioxolane, or may be added to the cellulose ester solution (doping). Or it can be added directly to the doping composition. In particular, the ratio of the discotic compound is preferably from 10% to 90%, more preferably from 20% to 80%, based on the total mass of the discotic compound and the rod compound, and other rods other than those described in the above publications Specific examples of preferred compounds of the compound are shown below. -33- 201207012 [化7] C3H7 h15 CeHia _Η0^〇4-^)-Ι-〇^〇- Η17„3c^J-^&gt;Io^-chs ci—^~~y~〇-c—^ ~~co—^~~y~ci Hope y〇^〇』-〇^-〇-〇-Br ch3 ]C2H5 He )(n)C4H9-H^-0-C-^yC-0-QK C4Hg( n) h3c-ch ch-ch3 (2 (3 (5 (6 (7 (8 (9 (9))

HjC CHS -34- 201207012 =) 613⁄4 ΗΟ-£?ΗΟ—ΙΝο-οΛγο-οΛ丫? . People? *5-δι£?ΟΗ Ηο-^-^ο=\__/ο=\_^ Ηο-ΝΖ) —o=i—IN3—£3l=vol£ul*HOAvo=c!&gt;A丫=οιοΛ ^~£:ϊι£3ιοι=ϋι£3ιΙΝ:ϊι=νο— ο=ο=^―^ο=^―一〆y——^o=o= S-ο-=ο-=νι!5-ο- Ο-=ο-ο-=υ-ο^ο~£?£ϋ-ο-=ϋ-=ϋ-ο--5 2 0 0 ^^^ ο ο οoa ί.^.0ιΝχ01ο.0^ιοί ^0ότ£0.0^.0£ ί Qf οιοιο.^10τ^οιύτο.£οιο χ!ΟΙΟ^ότ^ϊοιο- ΗΟ-£ο-£ο-^ ^-0-0-^ 0-0-^ ^- ΝΗυ-£ο—ΟΗJrs ^L1 ^ Jcl I HO—x*o-^ro-3-^ vo-0-^ y£?ohJcl ^ JLl 巨丨— 0££3 0ό.ο^ό1^οότ?. χ^ ΟΙΟ,-ΛΤ^

£3⁄4 us!. -35- 201207012 [Chemistry 9]

(23) c8h„-^〇-2-〇Io-^c8h17 ho-ch2-ch2o ^Q^〇_il_^.^0-^-〇-CH2-CH2-〇H (25) (26) (27 ) (28) (29) (30) (31) (32) CH3-0-C-^~~^-0-C-^ yC-〇-^~^-C-〇-CH3 C2Hs-0-C -^~^-0-C-^~~〉一C_〇-^~y~C_0_C2Hs (n)C4H9-〇- C-^~y-〇-C-^ yC-〇-^~~^- C-〇-C4H9(n) 〇βΗ13-〇- C-^~yQC-^ yC-〇-^~^-CQ-C6H13CeH^^^^OH^-O-CHQK CSH&quot; ch3-^~~^- Co-^ ^-oc-^~~^-ch3 C2H5 C2Hs (n)C4H9 C4H9(n) -36- 201207012 [10] (33) ch3-o-^~~^-co-^ ^-oc- ^~^-o-ch3 (34) (〇)〇4«9-〇-〇^〇-〇-{^0^-〇- 〇-C4H9(n) (35) 0

w we-. · W (36) o (37) o c2h5 AJH0.C.CSC.C_0

C2Hs (38) (n)C4H9 -cc=cco—/&quot;&quot;^― C4H9(n) (39) CH,_〇分〇-c-cec-co o 0-CH3 (40&gt; oo 〇2„ 5_〇4^〇_0_1〇.〇4-〇^-?-〇-〇2»6 o (41)

CtH15 (42) C7H18-〇-C—^y~o-c-^ y-c-o-^~~^-c-o-cTH1s -37- 201207012 [化11] Ο (43)

CeH„-0 Ο ο ιι ιι C-CH=CH-C-0 o-c6h13 (44)

C7H1S ~Qr o o M II 0-C-CH=CH-C-0 c7h15 (45) 〇 C7H1S-o-c o o

Ιι II 0-C-CH=CH-C-0 o c-o-c7h16 -38- 201207012 [Chem. 12]

(H3C〇-^~~y-C-Q-^~^-CN ((n)H9C4〇-^~y-C-〇-^~^-CN

((n)H13C60-^y-C-0-^^-CN ^ (n)H17C,〇-^^-C-〇-^^-CN

O ((n)HiaCeO-^~^-C-〇-^~~^-〇CH3 ^ r^-^^-C_〇-^^-〇CeH13(r〇-^~~yoc-oc-ch2ch2 -co-&lt; (52) NC-

CN 〇(53) H6C2^_〇_ihq.i_〇^KC2„6 (n)H9C4 (n)H9C40 OC4H9(n) ^ (n)H15C7 —oc—co—C7his (55) C4H9(n) ( 57) c2h5 C2Hs H3C(H2C)3-CHCH2〇och26h-(ch2&gt;3ch3 (S8)~ψ H3C(H2C)3-CHCH2〇C COCH2CH-(CH2)sCH3 (8) h9c4o _hG^hC}^_o^~ 〇C4H9 (n)^-〇4^l〇-〇-(

&lt;59) _ J

O-I- (60) (61) (62) (63) H3C〇- H8C2〇-

o II COCH* -to

O 〇 C4H9(n) C2H5 OCHs - 〇c2h5 The above specific examples (1) to (34), (41) and (42) have two carbon atoms at the 1st and 4th positions of the cyclohexane ring. However, the specific examples (1), (4)-(34), (41), and (42) have a symmetry-type molecule-39-201207012 structure 'no optical anisotropy (optical activity), and only geometric anisotropy exists. Body (trans and cis type). The trans form (l-trans ) and the cis form (Ι-cis) of the specific example (1) are shown below. [Chem. 13]

As described above, the rod-like compound preferably has a linear molecular structure. Therefore, the trans type is better than the cis type. Specific examples (2) and (3) are optically anisotropic (in total of four heterogeneous bodies) in addition to geometric anisotropy. For the geometrically heterogeneous system, the same trans type is better than the cis type. There is no particular advantage to the optically heterogeneous system, and it may be any of D, L or racemate. In the specific examples (43) to (45), the ethylene bond at the center has a trans form and a cis form. For the same reason as described above, the trans type is better than the cis type (delay control agent). The retardation controlling agent used in the film of the present invention is a compound having a repeating unit in the compound -40 - 201207012, and the number average molecular weight is preferably It is 700 or more and 10000 or less. The retardation controlling agent is used in the solution casting method because it accelerates the volatilization rate of the solvent or reduces the amount of residual solvent. Further, even in the film formed by the melt film forming method, the retardation controlling agent is a material for preventing coloring or deterioration of film strength. Further, the addition of the retardation control agent to the film of the present invention shows a useful effect in terms of improvement in mechanical properties, imparting flexibility, imparting water absorption resistance, and reducing water permeability. The content of the additive is from 1 to 35% by mass, preferably from 4 to 30% by mass, more preferably from 1 to 35% by mass, from 1 to 35% by mass, more preferably from 1 to 3, from the viewpoints of temperature and humidity variability, prevention of whitening of the film, physical properties, and the like. 25 mass%. Here, the number average molecular weight of the retardation controlling agent of the present invention is more preferably a number average molecular weight of 7 〇〇 or more, less than 10,000, more preferably a number average molecular weight of 800 to 8,000, and most preferably a number average molecular weight of 800 to 5 〇〇. 〇, especially suitable for number average molecular weight 1 0 00~5 000. With such a range, the compatibility is better. The following description of the retardation controlling agent used in the present invention will be described in detail with reference to specific examples thereof. However, the retardation controlling agent used in the present invention is not limited thereto. The retardation controlling agent is preferably a polyester-based polymer, and particularly preferably an aliphatic polyester or an aromatic polyester. (Polyester-based polymer) The polyester-based polymer used in the present invention may be a mixture of an aliphatic dicarboxylic acid having 2 to 20 carbon atoms and an aromatic dicarboxylic acid having 8 to 20 carbon atoms. -41 - 201207012 At least one type of diol reaction selected from aliphatic diols having 2 to 12 carbon atoms, alkyl ether diols having 4 to 20 carbon atoms, and aromatic diols having 6 to 20 carbon atoms As a result, both ends of the reactant may be directly used as a reactant, but further, a monocarboxylic acid, a monool or a phenol may be reacted, and so-called terminal blocking may be performed. This terminal blocking system is particularly effective in the absence of free carboxylic acids, and is effective in terms of storage stability and the like. The dicarboxylic acid used in the polyester polymer of the present invention is preferably an aliphatic dicarboxylic acid residue having 4 to 20 carbon atoms or an aromatic dicarboxylic acid residue having 8 to 20 carbon atoms. The aliphatic dicarboxylic acid having 2 to 20 carbon atoms which is preferably used in the present invention may, for example, be oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid or octane. Diacid, azelaic acid, sebacic acid, dodecanedioic acid and 1,4-cyclohexanedicarboxylic acid. Further, the aromatic dicarboxylic acid having a carbon number of 8 to 20 is: citric acid, p-nonanoic acid, isophthalic acid, 1,5-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,8-naphthalene Dicarboxylic acid, 2,8-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, etc. The preferred aliphatic dicarboxylic acids among these are malonic acid, succinic acid, maleic acid, and fumaric acid. , glutaric acid, adipic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, aromatic dicarboxylic acid is citric acid, p-nonanoic acid, isophthalic acid, 1,5-naphthalene dicarboxylic acid, 1 , 4_naphthalenedicarboxylic acid. More preferably, the aliphatic dicarboxylic acid is succinic acid, glutaric acid or adipic acid, and the aromatic dicarboxylic acid is citric acid, p-nonanoic acid or isodecanoic acid. In the present invention, at least one of the aliphatic dicarboxylic acid and the aromatic dicarboxylic acid is used in combination, and the combination thereof is not particularly limited, and there is no problem even if the number of the respective components is combined. a diol or an aromatic cyclic diol-42-201207012 used for a high molecular weight additive, for example, an aliphatic diol having 2 to 20 carbon atoms, an alkyl ether diol having 4 to 20 carbon atoms, and a carbon number of 6~ The selected aromatic ring diol of 20 is selected. Examples of the aliphatic diol having 2 to 20 carbon atoms include an alkyl diol and an alicyclic diol, and examples thereof include ethylene glycol, 1,2-propylene glycol, iota, 3-propanediol, and 1,2-butylene. Alcohol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl-1,3-propanediol (3,3-dihydroxymethylpentane), 2-n-butyl-2-ethyl-1,3-propanediol ( 3,3·Dimethylol heptane), 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol , 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-nonanediol, 1,1 2-18 Carbon diol or the like, these glycols may be used in combination of one or more kinds. Preferred aliphatic diols are ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4 _cyclohexane dimethanol' is particularly preferably ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol. The alkyl ether diol having 4 to 20 carbon atoms is preferably, for example, polytetramethylene ether glycol, polyvinyl ether glycol, and polypropylene ether glycol, and combinations thereof. The average degree of polymerization is not particularly limited, but is preferably 2 to 20 Å, more preferably 2 to 10 Å, and 2 to 5, particularly preferably 2 to 4. Examples of the commercially available polyether glycols which are typically useful are, for example, Carbowax resin, Pluronics resin, and Niax resin-43-201207012. The aromatic diol having 6 to 20 carbon atoms is not particularly limited, but for example, Bisphenol A, 1,2-hydroxybenzene, 1,3-hydroxybenzene, 1,4 hydroxybenzene, 1,4-benzenedimethanol, preferably bisphenol A, I, 4-hydroxybenzene, I, 4- Diphenylmethanol. In the present invention, a high molecular weight additive having a terminal terminated with an alkyl group or an aromatic group is particularly preferred. By protecting the terminal with a hydrophobic functional group, it is effective for deterioration of high temperature and high humidity over time, and it is shown that the coloring which delays the hydrolysis of the ester group is an important factor. In the present invention, in order to prevent both ends of the polyester additive from becoming a carboxylic acid or an OH group, it is preferred to protect with a monool residue or a monocarboxylic acid residue. In this case, the monool is preferably a substituted or unsubstituted monool having 1 to 30 carbon atoms, and examples thereof include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, isoamyl alcohol, and Alcohol, isohexanol, cyclohexanol, octanol, isooctanol, 2-ethylhexanol, decyl alcohol, isodecyl alcohol, third sterol, decyl alcohol, dodecyl alcohol, hexadecanol, octadecyl alcohol An aliphatic alcohol such as an alcohol, allyl alcohol or oleyl alcohol, a substituted alcohol such as benzyl alcohol or 3-phenylpropanol, or the like. Preferred terminal blocking alcohols are methanol, ethanol, propanol, isopropanol, butanol, isobutanol, isoamyl alcohol, hexanol, isohexanol, cyclohexanol, isooctanol, 2-ethyl Hexanol, isodecyl alcohol, oleyl alcohol, benzyl alcohol, particularly preferably methanol, ethanol, propanol, isopropanol, cyclohexanol, 2-ethylhexanol, isodecyl alcohol, benzyl alcohol. Further, the monocarboxylic acid which is used as a monocarboxylic acid residue when the monocarboxylic acid residue is blocked is preferably a substituted or unsubstituted monocarboxylic acid having 1 to 30 carbon atoms. These may be aliphatic monocarboxylic acids or carboxylic acids containing aromatic rings. The aliphatic monocarboxylic acid which is preferably -44 to 201207012 is exemplified by acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, citric acid, dodecanoic acid, stearic acid, oleic acid, and aromatic. Monocarboxylic acids such as benzoic acid, p-tert-butylbenzoic acid, p-third amyl benzoic acid, o-xylene acid, m-xylene acid, p-xylene acid, dimethyl benzoic acid, ethyl benzoic acid , n-propyl benzoic acid, amino benzoic acid, ethoxylated benzoic acid, etc., these may be used alone or in combination of two or more. The synthesis of the high molecular weight additive of the present invention may also be carried out by a polyesterification reaction or a transesterification reaction of the above dicarboxylic acid with a diol and/or a terminally blocked monocarboxylic acid or a monool by a usual method. Any of the methods of the hot melt condensation method or the interface condensation method of the acid chloride and the glycol may be easily synthesized. For these polyester-based additives, Yuki Hiroshi's "The Theory and Application of Additives" (the company's fortunate study, the first edition of the first edition of the 1st edition of the Showa era on March 1, 48) is described in detail. In addition, it can also be used in JP-A-2005-155809, JP-A-2005-155810, JP-A-5-197073, JP-A-2006-259494, JP-A-2007-330670, JP-A-2006-342227, The materials described in each of the publications of 2007-003679 and the like are disclosed. The following is a specific example of the polyester-based polymer which can be used in the present invention, but the polyester-based polymer which can be used in the present invention is not limited thereto. -45- 201207012

-46- 201207012 1 Number of liver mass 1000 1000 1000 1000 1000 2000 2000 2000 2000 900 1000 2000 1000 3000 5500 1000 1000 1500 2000 1〇〇〇| 1000 1500 2000 1000 1500 1000 Terminal hydroxyl hydroxyhydroxy hydroxyethyl methacrylate residue Ethyl decyl ester residue ethyl decyl ester residue ethyl decyl ester residue m AM? m Avoid mm κι Acetyl ester residue Ethyl ester residue Ethyl ester residue Ethyl ester residue B Mercaptoester residue ethyl ester ester residue ethyl ester ester residue ethyl ester ester residue ethyl ester ester residue ethyl ester ester residue ethyl ester ester residue acetal acid ethyl ester ester residue Mercaptoester residue ethyl ester ester residue ethyl ester ester residue ethyl ester ester residue η diol ratio (mole %) 〇〇〇ο r*H 〇§ 〇〇rH 100 100 ο 100 100 100 100 100 〇100 〇〇〇! 1〇〇§ 100 〇〇 aliphatic diol fun II Κ) Chi 11 Κ 1 Interest 11 KI Ethylene glycol ethylene glycol propylene glycol butanediol hexanediol ethylene glycol ethylene Alcohol glycol ethylene glycol ethylene glycol glycol ethylene glycol ethylene glycol ethylene glycol ethylene glycol glycol Glycol glycol ethylene glycol II II K1 dicarboxylic acid dicarboxylic acid than the desert %) 15/35/20/30 20/30/20/30 10/50/30/10 5/45/30/20 〇pH 〇〇〇〇〇〇Ο *-Η 60/40 60/40 60/40 ο 〇〇〇〇50/50 50/50 50/50 40/30/30 ! 33/33/34 50/20/ 30 50/30/20 50/50 50/50 45/55 Aliphatic dicarboxylic acid SA/AA SA/AA SA/AA SA/AA · &lt;&lt; AA/SA AA/SA AA/SA 5 S5 SA/AA SA/AA SA/AA SA/AA 5 5 Aromatic dicarboxylic acid ΡΑ/ΤΡΑ ΡΑ/ΤΡΑ ΡΑ/ΤΡΑ ΡΑ/ΤΡΑ 1 1 1 1 1 1 1 1 1 1 1 1 &lt;&lt; £ 2 &lt;&lt; £ - &lt; 1 00 &lt;Ν 1 (3⁄4 σ&gt; CVJ 1 Ο. 1 CO 1 ca co 1 PU CO co 1 inch CQ 1 in co 1 &lt;D co 1 CO 1 00 co 1 CU σ&gt; CQ 1 cu § 1 CU 1 ft 1 〇4 CO 1 〇1 1 λ LO inch 1 CD 1 1 〇4 1 0, 1 Oi S 1 S3 1 CQ ΙΛ 1 0^ -47- 201207012 〇 〇 CSJ ο ο ο ο os 0 1 o § oooooooooo ο ο O o O 8 o CQ o § o CO oosmmmmmmmm paste mmm paste mm «1 mmm AM? forging m bullying AM? 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Another ο s Another II Another ssss \ \ \ \ \ Wear § § Guide s S \ \ \ \ \ \ 8 s Another s \ \ \ \ \ \ \ \ Another s another a LO CO s \ \ \ \ \ Guide through the guide to wear s in CO \ \ \ \ \ \ sudden S! 5 wear \ \ \ \ \ \ sss in \ \ \ \ \ S ss in in ο ίο in &lt; 3 5 55 5 5 Interest 11 搂 S5 \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ 搲 II S5 This is fun 搲 1 I 卜 - &lt; - &lt; « &lt; * &lt; ¢- g £ 2 S gg t. ss ss £ z £ ss s ss Fan Qu a* Q. \ \ \ \ \ \ \ 1 1 1 1 1 ss i 2 2 2 2 •—1 rH •-H CQ-like κ I s IKI s I This I ffi I s | s I (〇| S } SIS 1 | s I s I s I s I 0 1 r—1 I CU CU 0, OU 〇l Λ Ph CU CU CU CU Oi Table 3, PA stands for tannic acid, TPA stands for tannic acid, IPA stands for isonic acid, AA stands for adipic acid, SA stands for succinic acid, 2,6-NPA stands for 2,6-naphthalene Carboxylic acid, 2,8-NPA means 2,8-naphthalene dicarboxylic acid, 1,5-NPA means 1,5-naphthalene dicarboxylic acid, 1,4-NPA means 1,4-naphthalene dicarboxylic acid, 1 , 8-NPA-48-201207012 shows 1,8-naphthalene dicarboxylic acid. (Plasticizer) Plasticizer can use phosphate or carboxylate. Phosphate damage triphenyl phosphate (TPP) and tricresol Phosphate ester (TCP) is represented by phthalate ester and citrate ester. Examples of phthalate esters are phthalate ester (DMP), diethyl phthalate (DEP), dibutyl (DBP), Dioctyl phthalate (DOP), diphenyl decanoic acid I) and diethylhexyl decanoate (DEHP). Supply of citrate esters Ethyl citrate triacetate (OACTE) and o-ethenyl lemon® (OACTB). Examples of other carboxylic acid esters include butyl oleate, methyl acetoacetate, dibutyl sebacate, various trimellitates, and phthalate-based plasticizers (DMP, DEP 'DBP, DOP DEHP) ). Especially suitable for DEP and DPP. Additive amount of additives: The mass of the resin is 0.1 to 25% by mass, more preferably 20 to 15% by mass. (Antioxidant) In the present invention, a known β agent such as 2,6-di-t-butyl-4-methylphenol or 4,4'-thiobis-(6-yl-3) may be added to the cellulose ester solution. -methylphenol), 1,1'-bis(4-hydroxyphenyl)cyclohexane, methyl bis(4-ethyl-6-tert-butylphenol), 2,5-di-tertiary A phenolic or hydroquinone antioxidant such as pentaerythritol-tetrakis[3·(3,5-di-t-butyl-4-hydroxyphenyl). Further preferably, it is preferably a tris(4-system containing a carboxylate dimethyl phthalate (DPP comprises o-tributyl pomacein. DPP is preferred as fiber %, and the most J anti-oxidation-third cyan 2, 2'- sub ^hydroquinone, propionate] methoxy- -49- 201207012 3,5-diphenyl) phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-t-butyl Phenyl) phosphite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphoric acid a phosphorus-based antioxidant such as an ester. The amount of the antioxidant added is 0.05 to 5.0 parts by mass based on 100 parts by mass of the cellulose resin. (Ultraviolet absorber) In the present invention, a polarizing plate or a cellulose ester solution is used. From the viewpoint of preventing deterioration of the liquid crystal or the like, it is preferable to use an ultraviolet absorber. The ultraviolet absorber is excellent in absorption energy from ultraviolet rays having a wavelength of 370 nm or less, and from the viewpoint of good liquid crystal display properties, it is preferable to use absorption of visible light having a wavelength of 400 nm or more. Specific examples of the ultraviolet absorber to be preferably used in the present invention include, for example, a hindered phenol compound and a hydroxyl group. a benzophenone-based compound, a benzotriazole-based compound, a salicylate-based compound, a benzophenone-based compound, a cyanoacrylate-based compound, a nickel-salted salt-based compound, etc. Examples of the phenol-resistant compound can be exemplified. Such as 2,6-di-t-butyl-p-cresol, pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], Ν, Ν'- Methylene bis(3,5-di-t-butyl-4-hydroxy-hydroxy cinnamate), 1,3,5-trimethyl-2,4,6-tris (3,5-di third Butyl-4-hydroxybenzyl)benzene, tris-(3,5-di-t-butyl-4-hydroxybenzyl)trimeric isocyanate, etc. Examples of the benzotriazole-based compound include, for example, 2- (2,-Hydroxy-5'-methylphenyl)benzotriazole, 2,2-methylenebis(4-(1,1,3,3-tetramethylbutyl)-6-(211 -benzotriazol-2-yl)phenol), (2,4-bis-(n-octylsulfo)-6-(4-hydroxy-3,5-di--50-201207012 tributylanilinyl) -1,3,5-triazine, triethylene glycol-bis[3-(3-tributyl-5-methyl-4-hydroxyphenyl)propionate], N,N'-hexa Methyl bis(3,5-di-t-butyl-4-hydroxy-hydroxy cinnamate), 1,3 , 5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 2(2'-hydroxy-3', 5'-di- T-butylphenyl)-5-chlorobenzotriazole, 2(2'-hydroxy-3',5'-di-third-pentylphenyl)-5-chlorobenzotriazole, 2,6 - di-t-butyl-p-cresol, pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] and the like. The amount of the ultraviolet ray-imparting agent added is preferably from 1 ppm to 1.0% by mass in the entire cellulose ester film, and is more preferably from 10 Å to 1 〇〇〇 ppm. (matte agent) It is preferred to add fine particles as a matte agent to the cellulose ester film of the present invention. The fine particles used in the present invention may, for example, be cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, calcium carbonate, talc, earth, calcined kaolin, calcined calcium citrate, water and calcium citrate, aluminum citrate, citric acid. Magnesium and calcium phosphate. The micro-particles contain bismuth, and the turbidity becomes lower, preferably, especially cerium oxide. The fine particle system of cerium oxide has a primary particle size of 2 Å or less and an apparent specific gravity of 70 g/liter or more. The average diameter of the primary particles is as small as 5 to 16 nm, which lowers the haze of the film, and is more preferable. The apparent specific gravity is preferably 90 to 200 g/liter or more, more preferably 100 to 200 g/liter or more. The larger the apparent specific gravity, the higher the concentration of the dispersion can be produced, and the haze and agglomerate are good, so it is preferable. These fine particles generally form secondary particles having an average particle size of 0.1 to 3 ·0//πι. These fine particles are attached to the film to form aggregates of primary particles, and form 0.1 to 3.0 on the surface of the film. /zm bump. 2 times flat-51 - 201207012 The average particle size should be 0.2~1.5/zm, more preferably 0.4~1.2//m, most preferably 0.6~1 times, and the secondary particle size is observed in the film by scanning electron microscope. The particle has a diameter that is circumscribing the circle of the particle and is the particle size. Further, 200 particles were observed by changing the position, and the average enthalpy was used as the average particle size. As the fine particle system of cerium oxide, commercially available products such as Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, 0X50, TT600 (manufactured by Japan Aerosil Co., Ltd.) can be used. The fine particles of zirconia are sold under the trade names of, for example, Aerosil R9 76 and R81 1 (manufactured by Japan Aerosil Co., Ltd.), and can be used. Among them, Aerosil 200V and Aerosil R972V are fine particles of cerium oxide having an average particle diameter of 20 nm or less and an apparent specific gravity of 70 g/liter or more, which keeps the turbidity of the optical film low and reduces the friction coefficient. Big, so it is especially good. In the present invention, in order to obtain a film having particles having a small average particle diameter of 2, a method of preparing a dispersion of fine particles can be devised. For example, a fine particle dispersion in which a mixed solvent and fine particles are stirred is prepared in advance, and this fine particle dispersion is added to a separately prepared small amount of a cellulose ester solution to be stirred and dissolved, and further mixed with a main cellulose ester dope. This method is preferably a dispersion method of the cerium oxide microparticles, and is a preferred modulation method insofar as the cerium oxide microparticles are difficult to further agglomerate. In addition, a small amount of cellulose ester is added to the solvent, and after stirring and dissolving, fine particles are added and dispersed by a disperser, thereby using the microparticle addition liquid as a fine particle addition liquid, and the microparticle addition liquid is sufficiently mixed with the doping liquid by the in-line mixer. method. The present invention is not limited to the above method, but the concentration of the cerium oxide when the cerium oxide fine particles are mixed with a solvent or the like is preferably 5 to 30% by mass, more preferably 10 to 25% by mass. %, most preferably 15 to 20% by mass. When the dispersion concentration is high, the liquid turbidity of the added amount becomes low, and the haze and aggregates become good, which is preferable. Further, when a matte agent is added to the cellulose ester film of the present invention, the matte content of the film surface layer is 0.05 to 1.00 by mass based on 1 part by mass of the film surface layer, regardless of the spherical or amorphous particles. The fraction is preferably from 0.07 to 0.60 parts by mass, more preferably from 0.1 to 0.40 parts by mass. When the content of the fine particles in the surface layer is less than 0.05 parts by mass, it is difficult to ensure the smoothness and the anti-adhesion property of the surface of the cellulose ester film, and if it exceeds 1.00% by mass, the transparency is deteriorated. The solvent-based lower alcohol to be used is preferably, for example, methanol, ethanol, propanol, isopropanol or butanol. The solvent other than the lower alcohol is not particularly limited, but it is preferably used in the solvent used in the film formation of the cellulose ester. (Peel Promoter) A peeling accelerator may be added to the film of the present invention. The release accelerator may be contained, for example, in a ratio of 0.001 to 1% by mass. The peeling accelerator is preferably a compound described in Paragraph No. 0048 to 0069 of JP-A-2006-45497. (Physical properties of the cellulose ester film) The properties of the cellulose ester film of the present invention as physical properties of the optical film are described below. -53- 201207012 (delay and surface alignment s) retardation and surface alignment s from the produced optical film cut sample 35mmx35mm, humidity control at 25 ° C, 5 5 % RH for 2 hours, with automatic birefringence (KOBRA WR, prince measurement (strand)), the enthalpy measured from the vertical direction of 590 nm and the extrapolation of the retardation enthalpy measured while tilting the film surface, calculate R 〇 ( 590 ) and Rt (at each wavelength) 590 ) , S ( 590 )° The cellulose ester film of the present invention is characterized in that the in-plane retardation 値R 〇 ( 590 ) defined by the following formula (I) is 40 to 10 nm at a light wavelength of 5 90 nm. In the range, the retardation 値Rt ( 590 ) in the thickness direction defined by the following formula (II) is in the range of 150 to 300 nm, and the surface alignment degree S ( 590 ) defined by the following formula ( ΠΙ ) is 0.001 to 0.01. Within the range, and the thickness is in the range of 20 to 50 gm. Further, in the present invention, the enthalpy of Ro (590 nm) is 40 to 100 nm, but for the polarizer, the phase difference is adjusted by the retardation film of only one side, and it is more preferable to release 60 to 100 nm. Further, in the present invention, Rt (590) is 150 to 300 nm, but for the polarizer, the phase difference is adjusted by the retardation film on only one side, and more preferably 200 to 300 nm. The surface alignment degree S is more preferably in the range of 0.003 to 0.01. In the present case, R 〇 (590) ' Rt ( 590 ) and the surface orientation S (. 590 ) are defined by the following formulas (I) to (III), respectively. Formula (I) : Ro ( 590 ) = ( nx-ny ) xd Formula (II) : Rt ( 590 ) = ( (nx + ny) / 2-nz) xd Formula (III) : S ( 5 9 0 ) = (nx + ny) / 2-nz -54- 201207012 In the above formula, R 〇 ( 590 ) indicates the in-plane retardation 値 in the film of the measurement wavelength of 590 nm, and Rt ( 590 ) indicates the wavelength 5 of the measurement light. 9 Onm film has a retardation in the thickness direction of the film. Further, d represents the thickness (nm) of the film, and nx represents the maximum refractive index in the plane of the film at a wavelength of 590 nm, which is also referred to as the refractive index in the direction of the slow axis. The ny system indicates the refractive index in the direction perpendicular to the slow axis in the plane of the film at a wavelength of 590 nm, and the refractive index in the thickness direction of the film at a wavelength of 5 90 nm. In the present invention, a cellulose ester, a retardation developing agent, and a retardation controlling agent are contained in an appropriate amount in the range of a thiol substituent having a carbon number of 2 to 4 and a thiol substitution degree of 2.0 to 2.5. In order to make the retardation 所 the desired enthalpy, and to adjust and control the temperature of the extension (the combination of the temperatures separately distinguished), the magnification, the speed of the extension, the order of the extension, the residual solvent amount of the film during the extension, and the like. Delay can be reduced to the desired defect. By adjusting the retardation to such a range, the viewing angle of the liquid crystal display device using the film of the present invention can be expanded, and the front contrast can be improved. Front contrast = (luminance of white display measured from the normal direction of the display device) / (luminance of black display measured from the normal direction of the display device) The viewing angle is such that the viewing direction of the liquid crystal display device is tilted from the normal direction A certain degree of contrast angle can be maintained. (The water content of the doping) The method for producing the cellulose ester film of the present invention is preferably a method of producing a doping having a water content of more than 2% and not more than 1% by weight. -55-201207012 In the present invention, the water content of the doping is preferably in the range of more than 2% and 10% or less, more preferably more than 2%, from the viewpoint of removal of residual solvent in the film, prevention of white turbidity, and the like. 5% or less, particularly preferably more than 2% and less than 3%. In addition, the "doping" is a raw material solution or a dispersion obtained by dissolving a film forming material such as a cellulose ester resin in a solvent or dispersing the dispersing agent. The "doped moisture content" of the present invention means the mass calculated by the mass of the water contained in the doping/(the mass of the doping containing water) xl 〇〇. In the present case, the moisture content of the doping is measured by a Karl Fischer method using a moisture analyzer (CA-03: manufactured by Mitsubishi Chemical Corporation) and a sample drying device (VA-05: Mitsubishi Chemical Corporation). Miscellaneous lcm3. The method for adjusting the moisture content of the doping is a change in the drying temperature at the time of production of the cellulose ester resin, a change in the moisture content of the cellulose ester resin itself, a change in temperature or humidity after the doping liquid is adjusted, The blowing of the dry gas or the water vapor of the doping liquid or the like is adjusted. <Method for Producing Cellulose Ester Film> The cellulose ester film of the present invention is produced by a solution casting method in which a cellulose ester and an additive are dissolved in a solvent to prepare a doping step; a step of doping on a metal support such as a conveyor belt or a drum; a step of casting the dope to form a braid; drying the step of peeling from the metal support; extending or maintaining a wide step; further drying Step; the step of taking up the finished film. -56- 201207012 "Steps on Modulation Doping" The concentration of the cellulose ester in the doping is preferably such that the dry load after casting on the metal support can be reduced, but if the concentration of the cellulose ester is too concentrated When the load increases, the filtration accuracy deteriorates. The concentration of such enthalpy is preferably from 10 to 35% by mass, more preferably from 15 to 25% by mass. The organic solvent preferably contains a solvent selected from the group consisting of an ether having 3 to 12 carbon atoms, a ketone having 3 to 12 carbon atoms, an ester having 3 to 12 carbon atoms, and a halogenated hydrocarbon having 1 to 6 carbon atoms. The ethers, ketones and esters may also have a cyclic structure. Any one or more of a functional group having an ether, a ketone or an ester (i.e., -〇-, -CO-, and -COO-) may be used as an organic solvent. The organic solvent may also have other functional groups such as an alcoholic hydroxyl group (hydroxyl group). In the case of an organic solvent having two or more kinds of functional groups, the number of carbon atoms may be an ether having 3 to 12 carbon atoms as long as it is within a predetermined range of a compound having a functional group of any one of them. Isopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolan, tetrahydrofuran, anisole and naphthol. Examples of the ketone having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone, and methylcyclohexanone. Examples of esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, amyl carboxate, methyl acetate, ethyl acetate, and pentyl acetate. . Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol, and 2-butoxyethanol. -57- 201207012 The halogenated hydrocarbon preferably has 1 or 2 carbon atoms, and most preferably 1. The halogenated halogen halide is preferably chlorine. The ratio of the hydrogen atom of the halogenated hydrocarbon to halogen is preferably from 25 to 75 mol%, more preferably from 30 to 70 mol%, most preferably from 35 to 65 mol%, particularly preferably from 40 to 60 mol%. A halogenated hydrocarbon represented by methylene chloride. These are called good solvents. In addition to the above organic solvent, the doping is preferably carried out in an amount of 1 to 4% by mass of an alcohol having 1 to 4 carbon atoms. After the doping is carried on the metal support, the solvent starts to evaporate and the ratio of the alcohol increases, so that the braided material (the doped film after doping the cellulose derivative on the support is called "knit") "Gelification" can be used as a gelling solvent which is easily peeled off from a metal support, or when the ratio is small, the role of dissolution of a cellulose derivative which promotes a non-chlorinated organic solvent is also suppressed. The role of gelation, precipitation, and viscosity increase of the reactive metal compound. The alcohol having 1 to 4 carbon atoms may, for example, be methanol, ethanol, n-propanol, isopropanol 'n-butanol, second butanol, third butanol or propylene glycol monomethyl ether. Among them, doping has excellent stability, low boiling point, and good drying property, and is preferably methanol. These are called weak solvents. Further, the solvent which can be used for the dissolution of the cellulose ester can be recovered by the solvent which is removed from the film by the film forming step, and used. In the recovery solvent, a small amount of the additive added to the cellulose ester may be contained, but it may be reused even if it is contained, and if necessary, it may be re-refined and reused. The method of dissolution can be carried out using a general method. When combined with heating and pressurization, it can be heated to the boiling point of normal pressure or higher -58-201207012. It is heated and stirred at a temperature above the boiling point of the solvent at normal pressure and under the pressure and the solvent is not boiling. It is preferred that the block or undissolved matter of the gel or the block occurs. Further, a method in which a cellulose ester is mixed with a weak solvent to wet or swell, and a good solvent is further added and dissolved is also preferably used. The pressurization system may be a method in which the vapor pressure of the solvent is raised by a method of injecting an inert gas such as nitrogen or by heating. The heating system should be carried out from the outside, for example, the jacket type is easy to control the temperature, preferably. The heating temperature at which the solvent is added is preferably from the viewpoint of the solubility of the cellulose ester. However, if the heating temperature is too high, the required pressure becomes large and the productivity is deteriorated. Preferably, the heating temperature is 45 to 12 (TC, more preferably 60 to 11 (TC, most preferably 70 to 105 t. Further, the pressure is adjusted to a temperature at which the solvent does not boil. In the present invention, the cooling dissolution method is also compared. The cellulose ester is dissolved in a solvent such as methyl acetate. The cellulose ester solution is filtered by using a suitable filter material such as filter paper. The filter material is an insoluble matter, and is preferably an absolute filter. The accuracy is small, but if the absolute filtration precision is too small, there is a problem that the filter material is easily clogged. Therefore, the absolute filtration precision should be 滤.〇〇8mm or less, more preferably 0_001~0.008mm filter, optimum It is a filter material of 0.003 to 0.006 mm. The material of the filter material is not particularly limited, and a general filter material can be used, but a filter material made of plastic such as polypropylene or Teflon (registered trademark) or a filter material made of metal such as stainless steel, -59- 201207012 It is advisable to use filtration to remove and reduce the quality of the cellulose ester of the raw material, especially the bright foreign matter. The bright spot foreign matter makes the two polarizing plates form a cross-Nicol state. In between In the case of an optical film or the like, when the side of the polarizing plate is viewed from the side of the other polarizing plate, the foreign matter is seen when the light leaks from the opposite side, and the number of bright dots having a diameter of 0.01 mm or more is 200/cm 2 . It is better to use 1〇〇/cm2 or less, preferably 50/cm2 or less, and 0~10/cm2 or less. Also, it should be less than 0.01mm. The method is carried out, but at a temperature above the normal boiling point of the solvent, and at the same time as the temperature at which the solvent does not boil under pressure, and the method of filtering and filtering, the difference in filtration pressure before and after the filtration (referred to as a difference in differential pressure is small, preferably. The temperature is preferably 45 to 120 ° C, more preferably 45 to 70 ° C, especially 4 5 to 55 ° C. The filtration pressure should be small. The filtration pressure should be 1.6 MPa or less, more preferably 1. It is below 1.0 MPa. "Casting step about doping" The metal supporting system in the casting (casting) step should be a mirror surface. The metal support should be a stainless steel conveyor belt or a drum for electroforming the surface of the casting. The width of the casting can be 1~4m. The temperature of the metal support in the casting step is -50 °C ~ the boiling point of the solvent is not reached. Degree, the temperature is higher, the speed of the fabric can be accelerated to 'definitely good' but if it is too high, the fabric will foam, sometimes 'mixed with:: from the point (C 0; should be the heat of rolling,) It is preferably 2MPa fine-grained surface dry surface -60- 201207012 deterioration. The preferred support temperature is 0~55 ° C, more preferably 25~50. (: or, by cooling to make the gel It is also preferable to peel off from the drum body in a state in which a large amount of residual solvent is contained. The method of controlling the temperature of the metal support is not particularly limited, but there is a method of blowing warm air or cold air, or contacting warm water with A method of the back side of a metal support. The heat transfer by the warm water is carried out efficiently, so that the temperature of the metal support is short, which is preferable. When using warm air, sometimes the wind is used at a temperature higher than the target temperature. In order to show that the cellulose ester film has good planarity, the residual solvent amount when the knitted fabric is peeled off from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or 60 to 130% by mass, particularly preferably It is 20 to 30% by mass or 70 to 120% by mass. In the present invention, the amount of residual solvent is defined by the following formula. Residual solvent amount (% by mass) = { ( MN ) /N } X 1 00 In addition, the quality of the sample of the braid or film is taken at any point during or after manufacture, and the twist is 1 1 5 ° C. Quality after heating for 1 hour "Related drying step" In the drying step of the cellulose ester film, the knitted fabric is peeled off from the metal support and further dried, preferably so that the residual solvent amount is 1% by mass or less, more preferably 〇. 1% by mass or less, particularly preferably 0 to 0.01% by mass or less. The film drying step is carried out by means of a general roll drying method (many rolls arranged in the upper and lower sides of -61 - 201207012 are alternately passed through the knitting and drying) or a stretcher to carry the knitted fabric while drying. In order to produce the cellulose ester film of the present invention, it is preferable to extend the width of the stretcher (the horizontal direction) so that the both ends of the knitted fabric are held by a jig or the like. The peeling tension is preferably performed at 300 N/m or less. The means for drying the knitted fabric is not particularly limited, and generally can be carried out by hot air, infrared rays, heating rolls, microwaves, etc., but the point of simplicity is preferably carried out by hot air. The drying temperature in the drying step of the knitted fabric is preferably 40 to 200 ° C. Sexual improvement. The thickness (film thickness) of the cellulose ester film is not particularly limited, but may be 10 to 200 μm. In particular, the thickness is 10 to 100 μm. Most preferably 20 to 50/zm» The cellulose ester film of the present invention can be used in a width of 1 to 4 m. It is particularly preferable to use a width of 1.4 to 4 m, particularly preferably 1.9 to 2.5 m. By being in this range, efficient polarizing plates can be cut and operationally stored. Further, the cellulose ester film of the present invention preferably has a length of from 100 m to 1 0000 m per roll, more preferably from 1 000 m to 1 0000 m, and particularly preferably from 500 00 to 10 00 m. In this range, the treatment in the form of the rolls is easy, and further suitable for the continuous process of the polarizing plate has the effect of improving the yield. The cellulose ester film is provided with the desired retardation 値R〇, Rt, and the cellulose ester film has the constitution of the present invention. Further, it is preferable to control the refractive index by the control of the stretching force and the stretching operation. For example, to reduce or increase the tension in the long direction, the retardation 値 can be changed. Further, in the longitudinal direction of the film (film forming direction) and the direction orthogonal to the film surface, that is, the width direction, the biaxial stretching or the uniaxial stretching is performed successively or simultaneously. The extending ratios of the mutually orthogonal biaxial directions are respectively preferably 0.8 to 1.5 times in the casting direction, 1.1 to 2.5 times in the width direction, and 0.8 to 1.0 times in the casting direction, and the width direction is The range of 1.2 to 2.0 times is extended. The extension temperature is preferably 120 to 200 t: more preferably 120 to 180 ° C, and most preferably extended to more than 120 ° C and below 160 ° C. The residual solvent in the film is preferably from 20 to 0%, more preferably from 15 to 0%. The method of extending the braid is not particularly limited. For example, a method in which a plurality of rolls are provided with a circumferential speed difference and a longitudinal direction is extended by a roll circumferential speed difference is used; and both ends of the knitted fabric are fixed by a jig or a pin, and the interval between the jig or the pin is expanded in the direction of progress. A method of extending in the longitudinal direction; a method of expanding in the lateral direction and extending in the lateral direction; or a method of extending in both the vertical and horizontal directions while expanding in the vertical and horizontal directions. Of course, these methods can be used in combination. Further, in the case of the tensioner method, if the clamp portion is driven by the linear driving method, the smooth extension can be performed, and the risk of cracking or the like is reduced. Therefore, it is preferable to extend the width or the lateral direction of the film forming step. The tensioner is carried out, and can be a pin puller or a clamp puller. The late phase axis or the phase advancing axis of the cellulose ester film of the present invention exists in the film surface, and if the angle with the film forming direction is 01, 0 1 is preferably -1° or more + Γ or less, more preferably -or or more +0.5° or less, most preferably -0.1° or more + 〇.r -63- 201207012 or less. This 01 series can be defined as the alignment angle. The measurement of 01 can be performed by using the automatic birefringence meter KOBRA-21ADH (Om...) to satisfy the above relationship, which can help to obtain high brightness in the displayed image. Helps suppress or prevent light leakage, helping to achieve faithful color reproduction in color liquid crystal display devices. <Polarizing Plate> The cellulose ester film of the present invention can be used for a polarizing plate in the case of a polarizing plate protective film, and can also be used for a liquid crystal display device using the polarizing plate. The cellulose ester film is used as a polarizing plate protective film and is bonded to a polarizing plate of at least one surface of the polarizer. The liquid crystal display device of the present invention is preferably a liquid crystal cell surface of at least one of them, and the polarizing plate of the present invention is bonded via an adhesive layer. The polarizing plate of the present invention can be produced by a general method. The polarizer side of the cellulose ester film of the present invention is alkalized, and immersed in at least one surface of the polarizer produced by stretching in an iodine solution, and bonded together using a fully alkalized polyvinyl alcohol aqueous solution. The cellulose ester film can also be used on the other side, and other polarizing plate protective films can be attached. For example, commercially available cellulose ester films (eg, Konica Minolta KC8UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC4UE, KC8UE, KC8UY--64-201207012 HA, KC8UX-RHA, KC8UXW-RHA) should also be used. -C, KC8UXW-RHA-NC, KC4UXW-RHA-NC, above Konica Minolta Opto (share) system) &lt; The polarizing plate protective film used on the surface side of the liquid crystal display device is an anti-glare layer or a transparent hard coat layer, and preferably has an anti-reflection layer, an antistatic layer, an anti-staining layer, and a back coat. The polarizer of the constituent elements is a light element that passes only a polarizing surface in a certain direction. A representative polarizer is known as a polyvinyl alcohol-based polarizing film, which dyes iodine to a polyvinyl alcohol-based film and dyed two-color film. Sex dyes. The polarizer may be formed by using a film-forming polyvinyl alcohol aqueous solution, and then uniaxially stretching and dyeing, or uniaxially stretching after dyeing, preferably after treatment with a boron compound. The film thickness of the polarizer is preferably 5 to 30 / zm, particularly preferably 10 to 20 / z m. Further, ethylene having a content of 1 to 4 mol%, a polymerization degree of 2,000 to 4 000, and a degree of alkalinity of 99.0 to 99.99 mol% described in JP-A-2003-342132, JP-A-2003-342322, and the like. The modified polyvinyl alcohol is also preferably used in the form of an ethylene-modified polyvinyl alcohol film having a hot water cutting temperature of 6 6 to 73 ° C. The polarizer using this ethylene-modified polyvinyl alcohol film is excellent in polarizing performance and durability, and has few color spots, and is particularly preferably used in a large liquid crystal display device. The polarizer obtained as described above is generally used as a polarizing plate by bonding a protective film to both sides or one side thereof. The adhesive to be used for bonding, -65 to 201207012, for example, a PVA-based adhesive or a urethane-based adhesive, etc., is preferably used. However, a PVA-based adhesive is preferably used. <Liquid Crystal Display Device> By using the polarizing plate of the present invention in a liquid crystal display device, various liquid crystal display devices of the present invention having excellent visibility can be produced. The cellulose ester film of the present invention and the polarizing plate can be used for liquid crystal display devices of various driving methods such as STN, TN, OCB, HAN, VA (MVA, PVA), IPS, and OCB. It is preferably a VA (MVA, PVA) type liquid crystal display device. In particular, a liquid crystal display device having a large screen of 30 or more screens, and a liquid crystal display device having less environmental variation, light leakage, uneven color perception, and front contrast can be obtained. [Embodiment] The present invention will be specifically described below by way of examples, but the present invention is not limited thereto. Example 1 (Doping Modulation) <1 -1> Cellulose Ester Solution The following composition was placed in a mixing tank to 'stir and dissolve each component'. Further, after heating at about 90 ° C for about 10 minutes, the average pore diameter was 34. // m filter -66- 201207012 Paper and a sintered metal filter membrane with an average pore size of l〇ym for filtration. The cellulose ester resin described in Table 1 is 1 part by mass of methylene chloride, 406 parts by mass of methanol, 6 parts by mass of <1-2> matte agent dispersion, which is adjusted to be added to a dispersing machine by the above method to adjust the matte average. A dispersion of the following composition of a cellulose ester solution of a methanolic cellulose ester solution of methylene chloride in a volume of 16 nm. Sand particles (aerosil R972 Japan 2.0 parts by mass, 72.4 parts by mass, 10.8 parts by mass, 10.3 parts by mass, <1-3>; a retardation developing agent solution, the following composition containing the cellulose ester solution prepared by the above method is put into a mixing tank, The mixture was stirred and dissolved while heating to prepare a retardation-developing agent solution. The retardation-developing agent shown in Table 1 2 parts by mass of the retardation controlling agent shown in Table 1 〇 parts by mass of dichloromethane 5 8.3 parts by mass of methanol 8.7 parts by mass 2.8 parts by mass of the cellulose ester solution, 100 parts by mass of the cellulose ester solution, 1.35 -67 to 201207012 parts by mass of the matte agent dispersion, and citric acid half ester as a release accelerator are mixed with the cellulose ester resin to 300 ppm. In addition, the cellulose ester resin used as a raw material for doping and various additives are used at a temperature of 120 ° C using a silo manufactured by Nara Machinery Co., Ltd. in advance. The addition ratio of the retardation-developing agent is a mass fraction when the amount of the cellulose ester is 100 parts by mass. Further, the solid content concentration at this time is 19% by mass. The above doping is carried out by using a conveyor belt casting machine. After the feed gas temperature on the conveyor belt is 80 to 130 ° C (exhaust gas temperature is 75 to 120 ° C), the residual solvent amount is 25~ 3 5 mass% of the film stripped from the conveyor belt, the stretcher region of the feed gas temperature of 130 ° C (exhaust gas temperature of 90 to 125 ° C), extending in the width direction at a stretching ratio of 30%, manufactured In this case, the film thickness after stretching was 40 μm, and the film thickness was adjusted. The film having the composition shown in Table 4 was prepared, and the purpose of manufacturing the film was judged to have a roll width of 1.96 m and a film length of 5000 m. The film was used as the film of Example 1. The residual solvent amount of the obtained film was 0.01% by mass. Further, the residual solvent amount of the film was a film piece of 7 mm x 35 mm, which was used as a sample for measurement, and a residual solvent gasification device was used. (Measured by Teledyne Tekmar Co., Ltd.) and gas chromatography (manufactured by JL Science Co., Ltd.) [Examples and Comparative Examples 2 to 3 1] The resin, doping composition, and -68 used in the following Table 4 were changed. - 201207012 Additives, film thickness, moisture content, roll length, film The films of the respective examples and comparative examples were obtained in the same manner as in Example 1. Proud S: Micro sm 锊m Excited m 柃 micro 锊镞锊 锊镞锊 m 琅S: plagiarism! 饀饀镒a镟锊a 镒镒a 镒镞14 栩w 镞恃镟14 it 3 § § § § wear s Μ s § 5 § § § § wear § wear ο 8 s in inch s § § § wear § called ^ ca ο ς〇ο CO ΙΟ CO ο CO in (Μ in in CQ ο CO CO CSJ in CQ 03 in cq CD eg ?Η CSJ tn oo ο in CO (N LO CQ rH Μ ο Ο ιΗ lO o in rH 00 ο in o O in rH in CsJ in CO y—S i 〇) exhibition mm ii m _ 13⁄4 ¢1 o ο ο ο ο Ο ID o ο o ο Ο in 〇Ο oo ο o 〇Ο ο 00 00 σ&gt CO 00 ooo Ο o jun drni1 郷CD 1 OU 1 1 1 1 1 0U CO 1 a, R 1 ou 益 1 CU inch 1 〇U η 1 Ou S 1 cu 1 OU co 1 CU CO 1 〇4 CO 1 &amp; CO 1 a, ¢0 1 % CO 1 Oh CD 1 a, C0 1 PU CD 1 β. s 1 a. inch tc 1 a, 1 03 Om m \ a« 0u CO 1 Oh CO 1 Oh CO 1 CU CO 1 (X &lt;0 1 Oh g leaven different load η i1 _ &lt;N inch inch inch inch 04 inch (N Cvl (Ν CQ (N inch 05 CSJ 6ϊ 0*3 ¢^) &lt;Ν CSJ inch inch Tt ca CM &lt;NJ &lt;N) IN m ilmil m (M CO ^τΗ inch τΗ 1 (Μ 1 inch 1 rH inch f-H 1 1-H inch 1 rH &lt;Μ 1 f— &lt; Μ 1 &lt;M 1 »-H w (Μ W 1 CSJ f-H W 1 &lt;M 1 τ—ί &lt;M 1 »-H Ν 1 ι-Η W 1 ιΗ inch 1 rH inch 1 CO 1 iH inch ▼H oa 1 iH (MI w 1 03 1 (N 1 tH ss m 魈 thief shovel ^s. ifi \ b Φ 〇〇Ο ο 2 ο ο 00 ο ο οο Ο ο 00 Ο ο ooo 00 〇o 00 Ο 8 s Ο 8 Ο 8 § Ο 8 § o 8 § o 8 Ο Ο ΙΛ CO 1 ooo 2 ο 8 S 0 1 o 8 Ο Ο 00 00 Ο 00 00 oo 00 oo 〇o § 〇o 00 〇o 00 〇ooo 琶〇o 00 oo €〇4-» inch &lt;N inch CSJ inch CVJ inch CM inch (inch inch CV1 inch CVJ inch inch C &lt;3 inches (Ν inch &lt;Ν inch eg inch Οί inch Μ inch &lt;N 00 OJ (N 03 ΙΟ 卜 Μ CNJ &lt;NJ CO CQ CO inch CM &lt;N inch &lt;N inch CSJ CNi eg inch CS3 •2 〇Ο ο ο Ο ο oo Ο 〇Ο ο o Ο oo oo Ο 〇o Ο Ο ooo rH 〇oooo 〇〇ο ο ο ο ο ο oo Ο 〇Ο ο o ο ο Oo ο oo οο ο oooooooooa &lt;d inch inch CSJ inch &lt;Ν inch &lt;Ν inch &lt;Ν inch &lt;Ν &lt;N inch CNJ inch CQ (Μ 03 inch &lt;Ν 吋 CV| «Ν inch inch &lt;N 00 rH CSJ CQ m (Ν Μ •H (N CO N co eg iH «Η inch inch CsJ inch &lt;S) Inch CSJ vs. τΗ 1 ο r—( 1 ο »Η 1 Ο τ—1 1 α 1 Ο 1 υ tH 1 a tH 1 〇1 ο rH 1 υ 1 ο τΗ 1 ο rH 1 a Ύ—i 1 ο ΟΙ 1 Ο 03 1 0 + fH 1 o CO 1 a inch 1 ο LO 1 a CO 1 〇卜1 Ο *— &lt; 1 Ο 00 1 〇05 1 O o T 〇rH 1 a 1 〇1 oia •Η 1 o fH 1 υ 1-Η CO C0 inch ΙΟ C0 卜 σ σ) ο •-Η CO 3 1C CD 00 S eg CV3 ca inch CQ in CSJ &lt;〇 &lt;N 〇5 00 cq Oi &lt;N co -69 - 201207012 [Chemical 14] Delayed dominant agent 1_1

C2h5 [Chemical 15] delayed dominant agent 1-2

C2hs [化16] delayed dominant agent 1 - 3

CH GHNyVNH·^ ΝΗ

l,C ΝγΝ delayed dominant agent 1-4

OCHj ch3 A part of the retardation controlling agent in Table 4 is the compound -70-201207012 described in Tables 1 to 3. Further, the retardation controlling agent 2-1 is a condensate (number average molecular weight: 2,500) composed of succinic acid/capric acid/ethylene glycol (2/3/5 molar ratio). TPP/BDP means triphenyl phosphate/biphenyl diphenyl phosphate. In Table 4, the doping moisture content is expressed by % by mass of the doping, and the addition amount of the retardation developing agent and the retardation controlling agent is the amount (% by mass) added to the cellulose ester resin. (Measurement of water content in doping) The water content in the doping is a moisture analyzer (CA-03: manufactured by Mitsubishi Chemical Corporation) and a sample drying device (VA-05: manufactured by Mitsubishi Chemical Corporation). 1 ml (lcm3) was determined by the Karl Fischer method. Further, the amount of water was divided by the mass (g) of the sample. Next, the unevenness of the retardation and retardation of the films of the respective examples and the comparative examples obtained above were evaluated by the following methods. The water content in the doping is carried out by changing the heating and humidifying conditions of the doping liquid. (Delayability) The surface alignment degree S (590), the retardation 値R〇(590), and Rt(590) are obtained based on the above definition formula. In addition, the surface matching degree S ( 5 90 ), the retardation 値Ro ( 590 ), and the Rt ( 590 ) system are at 23 ° C, 55% using an automatic birefringence meter KOBRA-21 ADH (Prince Measurement Machine (share)). In the RH environment, the measurement light wavelength was 5 90 nm. -71 - 201207012 (delayed jagged width) The measurement method for the delayed jagged width is KOBRA-21ADH (Oji Scientific Instruments), and the measurement method is performed in the following order. (a) The film is included in the extended film. When the tensioner extends, the ear of the clamp is cut from the end to the position of 200 mm. (b) The width direction is 20 points from both ends, and Ro and Rt are measured. (c) At this time, the maximum of Ro値 is Romax, the minimum 値 is Romin, the maximum 値 of Rt is Rtmax, and the minimum 値 is Rtmin. (d) Ro unevenness width = R〇max-Romin, Rt jagged width = Rtmax-Rtmin The above evaluation results are expressed in Table 5. -72- 201207012 [*5] Thickness (jum) Roll length (m) Film width 0) Surface alignment S Delayed surface unevenness Ready Ro (nn) Rt(nm) Ro(nin) Rt(nm) 1 40 5000 1.96 0.0055 70 220 1.0 3.0 The invention 2 40 5000 2.30 0.0068 80 270 4.0 8.0 The invention 3 40 5000 2.30 0.0068 70 270 1.0 4.0 The invention 4 40 5000 1.96 0.0063 80 250 4.0 7.0 The invention 5 40 5000 1.96 0.0055 70 220 2.0 3.0 The invention 6 40 5000 2.30 0.0055 70 220 2.0 3.0 The invention 7 20 8000 2.5 0 0.0100 60 200 1.0 3.0 The present invention 8 30 8000 2,30 0.0090 80 270 2.0 4.0 The present invention 9 50 4500 1.96 0.0060 90 300 3.0 6.0 The present invention 10 40 5000 2.30 0.0050 70 200 2.0 4.0 The present invention 11 40 4500 2.30 0.0068 80 270 3.0 6.0 The present invention 12 40 5000 2.50 0.0055 70 220 3.0 5.0 The present invention 13 40 5000 2.50 0.0050 60 200 2.0 4.0 The present invention 14 40 5000 2.50 0.0050 70 200 2.0 4.0 The present invention 15 40 5000 2.30 0.0068 80 270 1.0 3.0 The present invention 16 40 5000 2.30 0.0055 70 220 1.0 3.0 The present invention 17 40 5000 1.96 0.0075 100 300 8.0 15.0 Comparative Example 18 40 5000 2.50 0.0063 80 250 5.0 10.0 The present invention 19 40 5000 2.30 0.0055 80 220 1.0 3.0 The present invention 20 40 5000 2.50 0.0038 50 150 5.0 10.0 The present invention 21 40 5000 1.96 0.0033 40 130 2.0 3.0 Comparative Example 22 10 10000 2.50 0.0090 30 90 2.0 3.0 Comparative Example 23 60 3900 1.44 0.0030 80 180 6.0 13.0 Comparative Example 24 60 3900 1.44 0.0028 72 165 5.0 10.0 Comparative Example 25 45 3900 1.88 0.0027 50 120 6.0 12.0 Comparative Example 26 80 3900 1.48 0.0025 60 200 6.0 12.0 Comparative Example 27 40 5000 1.96 0.0055 70 22 0 4.0 8.0 The invention 28 40 5000 1.96 0.0055 70 220 3.0 6.2 The invention 29 40 5000 1.96 0.0055 70 220 2.1 5.2 The invention 30 40 5000 1.96 0.0055 70 220 1.1 3.0 The invention 31 40 5000 1.96 0.0055 70 220 4·2 7.3 The invention is apparent from the results shown in Table 5, and the cellulose ester film of the present invention has an appropriate retardation enthalpy, and has a small unevenness and high uniformity. <Preparation of polarizing plate> Using the obtained cellulose ester film 1 to 3 1, a polarizing plate was produced in the following manner. -73- 201207012 A 120/z m thick polyvinyl alcohol film was uniaxially stretched (temperature no ° C, stretching ratio 5 times). The mixture was further immersed in an aqueous solution of 75 g of iodine, 75 g of potassium iodide, and 100 g of water, and then immersed in a 68 ° C aqueous solution of 6 g of potassium iodide, 7.5 g of boric acid, and 1 g of water. It was washed with water and dried to obtain a polarizer. Then, the polarizer and the cellulose ester films 1 to 31 and the commercially available cellulose ester film (KC4UY, Konica Minolta Opto Co., Ltd.) were used as polarized light in the following steps 1 to 5; The plate protects the film to produce a polarizing plate. Step 1: The cellulose ester film 1 to 31 was immersed in a 2 mol/liter potassium hydroxide solution at 50 °C for 30 seconds, and then washed with water and dried to obtain a cellulose film having an alkalized surface. Step 2: The polarizer was immersed in a solid content 2% by mass of a polyvinyl alcohol adhesive bath for 1 to 2 seconds. Step 3: In step 2, the excess adhering agent attached to the polarizer is gently wiped, placed on the cellulose ester film treated in the step 1, and further placed on the back side cellulose ester film to be disposed. Step 4: The cellulose ester film 1 to 31 laminated in the step 3 was bonded to the polarizer and the cellulose ester film on the back side at a pressure of 20 to 30 N/cm 2 and a conveying speed of about 2 m/min. Step 5: The polarizer prepared by the step of preparing the polarizer prepared in the step 4 and the cellulose ester film 1 to 31 and the back side cellulose ester film was dried in a dryer at 80 ° C for 2 minutes to prepare a polarizing plate. -74-201207012 <Production of Liquid Crystal Display Device> A liquid crystal panel for measuring the viewing angle was produced as follows, and the characteristics of the liquid crystal display device were evaluated. The double-sided polarizing plate which was previously bonded to the VA mode liquid crystal display device (BRAVIAV 1 and 40 inch type manufactured by Sony) was peeled off, and the polarizing plate prepared as described above was used as the glass surface of the liquid crystal cell on the side of the cellulose ester film 1 to 31. The way it fits on both sides. At this time, the liquid crystal display device was produced in the same direction as the absorption axis of the polarizing plate to be bonded in advance. The results of evaluation of display uniformity for this liquid crystal display device are shown in Table 6. "Evaluation of Liquid Crystal Display Device" The backlight is continuously lit for 12 hours in an environment of 23 ° C and 5 5 % RH. The full black display state is visually observed in the dark room, and the evaluation shows uniformity. 6 in. [Display uniformity] Visually evaluate the display uniformity in black display according to the following criteria. 〇: Completely no speckles △: Partial or slightly weak speckles can be seen X: If strong speckles are seen, △ or more, No problem with use. -75-201207012 [Table 6] Display uniformity of liquid crystal display device 1 〇 The present invention 2 Δ The present invention 3 〇 The present invention 4 Δ The present invention 5 〇 The present invention 6 〇 The present invention 7 〇 The present invention 8 〇 The present invention 9 〇 The present invention 10 〇 the present invention 11 〇 the present invention 12 〇 the present invention 13 〇 the present invention 14 〇 the present invention 15 〇 the present invention 16 〇 the present invention 17 X comparative example 18 Δ the present invention 19 〇 the present invention 20 Δ the present invention 21 X comparative example 22 X Comparative Example 23 X Comparative Example 24 X Comparative Example 25 X Comparative Example 26 X Comparative Example 27 Δ The present invention 28 Δ The present invention 29 〇 The present invention 30 〇 The present invention 31 Δ According to the present invention, from Table 6, it is understood that the fiber of the present invention is used. The polarizing plate of the polyester film and the liquid crystal display device have excellent display uniformity. -76-

Claims (1)

201207012 VII. Patent application scope: 1. A cellulose ester film containing cellulose ester having a mercapto substituent in the range of 2 to 4 carbon atoms and having a mercapto substitution degree of 2.0 to 2.5. The cellulose ester film is characterized in that the retardation 値R 〇 (590) is in the range of 40 to 100 nm in the plane of the light wavelength of 5 90 mm, and the retardation 値Rt (590) in the thickness direction is in the range of 150 to 300 nm. The surface alignment degree S (590 ) is in the range of 0.001 to 0.01 and the thickness is in the range of 20 to 50 / zm. 2. The cellulose ester film according to claim 1, wherein the uneven retardation width of the in-plane retardation 値R〇(590) is 5 nm or less, and the retardation 値Rt(590) of the thickness direction is jagged. The width is 10 nm or less. 3. The cellulose ester film according to claim 1 or 2, wherein the film has a length in the range of 5,000 to 10,000 m, and the film has a width in the range of 1.9 to 2.5 m. A method for producing a cellulose ester film, which is a cellulose ester film according to any one of claims 1 to 3, which is characterized in that a water content of more than 2% and 10% or less is used. Dopant. A polarizing plate characterized by comprising the cellulose ester film according to any one of claims 1 to 3. A liquid crystal display device comprising the cellulose ester film according to any one of claims 1 to 3. 7. The liquid crystal display device of claim 6, wherein one of the liquid crystal cells has a cellulose ester film as described in any one of claims 1 to 3, which is opposite to the above-mentioned surface. The retardation 値Rt ( 5 90 ) in the thickness direction of the optical film of -77-201207012 on the side surface is a retardation 値Rt (590) smaller than the thickness direction of the cellulose ester film. -78- 201207012 IV. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the representative figure is simple: No 201207012 If there is a chemical formula in the case, please disclose the chemical formula that best shows the characteristics of the invention. :no