TW201002766A - Cellulose ester film - Google Patents

Abstract

Disclosed is a cellulose ester film having excellent front contrast. Specifically disclosed is a cellulose ester film characterized by having a haze value of 0.02 or less when a solvent having a refractive index of plus or minus 0.05 of the refractive index of the film is used as a film interface in the haze measurement of the film on a haze meter.

Description

201002766 VI. Description of the Invention: [Technical Field] The present invention relates to a cellulose ester film for use in a liquid crystal display device, and in particular relates to a cellulose ester film which is excellent in frontal contrast. [Prior Art] Cellulose An ester film, a polycarbonate film, a polycycloolefin film, or the like is often used as a phase difference film for a liquid crystal display device. The phase difference film is required to have high optical transparency and low complex refractive index. In recent years, in particular, liquid crystal display devices have been developed toward large-scale and high-definition, and have been demanded more stringently than ever with the improvement of their frontal contrast. In order to improve the frontal contrast, the improvement in the transmittance of the components constituting the liquid crystal display device is continuing to be reviewed, and the phase difference film disposed beside the crystal cell of the polarizing plate continues without exception. Review the improvement in penetration rate. For example, Non-Patent Document 1 proposes a technique in which a polycarbonate film or a polycycloolefin film is formed into one piece. However, even with such a technique, an optical compensation film having a protective film for a polarizing plate is not completely compatible with a polyvinyl alcohol as a polarizer, and is protected by a polarizing plate made of a cellulose ester film. Films, even nowadays, are still recognized as optical films that are necessary for liquid crystal displays. Therefore, there is a review of the proposal: the polarizing plate protective film is attached to the excellent -5 - 201002766 cellulose ester film, giving it the function of a phase difference film. Originally, cellulose ester films have been used as a protective film for polarizing plates because of low birefringence, but the function is not easy to impart. Another proposal is to add a compound having a phase difference enthalpy effect to a cellulose ester film to obtain a desired phase difference, and then to extend the film (Patent Documents 1, 2, and 3). However, there is a problem that the transmittance of the film due to stretching is deteriorated. The transmittance of the film is deteriorated, which is caused by an increase in the estimated haze (the cause of the scattering), which causes a phenomenon in which the front surface of the liquid crystal display is deteriorated. Therefore, when the cellulose ester film is used as a phase difference film, it is desirably deeply desired to simultaneously impart a decrease in phase difference and haze. Patent Document 1: JP-A-2006-299171, JP-A-2006-265382, JP-A-2006-265382, JP-A-2006-265382, JP-A No. JP-A-2006-265382 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The object of the present invention is to provide a fiber excellent in visibility (light leakage, hue, front contrast). Aliester film. 201002766 Means for Solving the Problems The above problems of the present invention are achieved by the following constitutions. (1) A cellulose ester film characterized by a haze measurement of a film by a haze meter, such as a haze system of 0.02 or less when a solvent having a refractive index of a refractive index of ±0.05 of a film is formed into a film interface. . (2) The cellulose ester film according to the above (1), wherein the cellulose ester film contains at least one aromatic terminal polyester compound represented by the following general formula (I); and has one or more and 12 At least one of the following pyranose structure or furanose structure, and all or a part of the OH group of the structure is a cellulose ester film of the esterified ester compound.

General formula (I) B—(GA)n—G—B (wherein B is an aryl carboxylic acid residue, G is an alkanediol residue having 2 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms; a diol residue or an oxyalkylene glycol residue having 4 to 12 carbon atoms, and A is an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms or an aryl dicarboxylic acid residue having 6 to 12 carbon atoms. Further, η is an integer of 1 or more). EFFECT OF THE INVENTION According to the present invention, it is possible to provide a cellulose ester which is excellent in frontal contrast

BEST MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the invention will now be described in detail, but the invention is not limited thereto. 201002766 As described above, a liquid crystal display device generally has a viewing angle characteristic, and when viewed from an angular position of a normal direction of a liquid crystal cell, a contrast reduction occurs. In order to solve the problem of such viewing angle characteristics, it is known that a cellulose ester film having an appropriate phase difference is disposed between a liquid crystal cell and a polarizer, and has a considerable effect. The phase difference is generally better, and the phase difference in the in-plane direction is in the range of 20 to 200 nm, and the phase difference Rt in the thickness direction is in the range of 70 to 400 nm, and the phase difference film of the present invention. The cellulose ester film is also preferred in this range. In addition, Ro=(nx-ny)xd

Rt=((nx+ ny)/2— nz)xd (wherein nx represents the refractive index in the direction of the slow axis in the plane of the cellulose ester film, and ny represents the direction orthogonal to the slow axis in the plane. The refractive index 'nz is the refractive index in the thickness direction, d is the thickness (nm) of the cellulose ester film, and the refractive index is measured at 590 nm. For the above refractive index, for example, KOBRA-21 ADH (Prince Measurement Machine (Unit)) can be used at 23. (:, in the environment of 55% RH, which is obtained at a wavelength of 590 nm. <Haze measured by haze in the present invention> The cellulose ester film of the present invention is characterized in that even in order to obtain When the solvent is formed into a film interface by using a solvent having a refractive index of a refractive index of ± 0.0 5 as a film interface, the haze measured by a haze meter is within a certain range of -8 to 201002766. For the sake of frontal contrast, it is necessary to reduce the haze of the cellulose ester film. However, if the haze is divided into the inside of the film and the surface, the improvement effect is greater for the inside. "Haze" refers to the haze caused by the scattering factor inside the film, and the so-called "internal" refers to the portion of the film surface that is more than 5#m. The internal haze is the refraction of the film refractive index ± 0.0 5 The solvent of the rate drops to the film interface' and is measured by haze as much as possible regardless of the haze of the film surface. <Haze inside the film (hereinafter, simply referred to as internal haze) measuring device> Meter (turbidity meter) (type NDH2000, Nippon Denshoku Co., Ltd.) The light source uses a 5V9W halogen ball; the light receiving unit uses a xenon phototube (with a specific sensitivity filter). In the present invention, the refractive index of the film is ± 〇. When the solvent of the refractive index of 〇5 is used as a film interface, the haze of the film is measured, and the enthalpy is 0.02 or less. The measurement is measured based on jIS Κ-7136. The measurement of the internal haze is as follows. 1 to 4, 〇 first, 'measured by the blank haze 1 of the measuring instrument other than the film. -9- 201002766 1. Drop a drop of 〇 (〇 5 ml) of glycerin on a clean glass slide. It should be noted that there should be no air bubbles in the droplets. Since the glass may be dirty if it is visually judged to be dirty, it should be washed with a lotion. Refer to Figure 1. 2. Cover the coverslip on it. Glycerin will expand even if it is not pressed. 3. Install on the haze meter and measure the blank haze 1. Then, measure the haze of the sample 2. 2. Drop the glycerin on the slide (〇. 〇 5 ml ). Figure 1 is referenced. The sample film was measured. Refer to Figure 2. 6. Drop glycerin (〇.〇5ml) onto the sample film. Refer to Figure 3. 7. Place a cover slip on it. Figure 4 Reference. 8. Install the haze meter and The haze was measured. 9. (Haze 2) - (Haze 1) = (Internal haze of the present invention) It can be calculated. In the above measurement, the slides and glycerin used are as follows 〇

Slide: MICRO SLIDE GLASS S9213 MATSUNAMI Glycerol: Kanto Chemicals Deer Grade To achieve the internal haze of the present invention, the cellulose ester film of the present invention, preferably, the cellulose ester film of the present invention contains at least one of the following An aromatic terminal polyester compound represented by the general formula (I);

General formula (I) B -(G-A)n-G-B (wherein, B is an aryl carboxylic acid residue, G is a carbon number 2 to 12 alkane di-10-201002766 alcohol residue or carbon a 6 to 12 aryl diol residue or a C 4 to 12 oxyalkylene glycol residue, and A is a C 4 to 12 alkyl dicarboxylic acid residue or a carbon number of 6 to 12 The base dicarboxylic acid residue, η is an integer of 1 or more). Further, at least one of a pyranose structure or a furanose structure having at least one of 12 or less, and all or a part of the thiol group of the structure is a cellulose ester film of an esterified ester compound. <Cellulose ester film> The cellulose ester film of the present invention is not particularly limited, and the cellulose ester is a carboxylate having a carbon number of from 2 to 22, which may be an ester of an aromatic carboxylic acid, and The lower fatty acid ester having a carbon number of 6 or less is preferred. The thiol group bonded to the hydroxyl group may be a straight chain or a branched chain, or may form a ring. It can be substituted with other substituents. In the case of the same degree of substitution, when the carbon number is large, the birefringence is lowered, and the carbon number is preferably selected from the group of 2 to 6 fluorenyl groups. The cellulose ester is preferably a carbon number of 2 to 4, and preferably has a carbon number of 2 to 3. Specifically, the cellulose ester may be combined with propionic acid in addition to an ethyl acetate such as cellulose acetate propionate, cellulose acetate butyrate or cellulose acetate propionate butyrate. A mixed fatty acid ester of cellulose of an ester group or a butyrate group. Further, a butylate group of butyrate is formed, which may be linear or branched. The cellulose ester preferably used in the present invention is cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate phthalate. -11 - 201002766 It is preferred that the cellulose esters other than the cellulose acetate phthalate which are preferred in the present invention satisfy the following formulas (1) and (2) at the same time. Formula (1) 2.0SX+YS3.0 Formula (2) 0 ^ Y ^ 1.5 wherein, the degree of substitution of the X-based acetyl group, the substitution degree of the Y-based propyl fluorenyl group or the butyl group, or a mixture thereof. Further, in order to obtain optical properties which can meet the purpose, it is also possible to use a resin having a different degree of substitution. The mixing ratio is preferably 1 0 : 9 0 to 9 0 : 1 0 (mass ratio). Among them, cellulose acetate propionate is preferred. In cellulose acetate propionate, it is preferred to use 1-0SXS2.5, 0.1SYS1.5, and 2.0 X X YS3.0. The method for determining the degree of substitution of the thiol group can be determined in accordance with ASTM-D817-96. The number average molecular weight of the cellulose ester used in the present invention is in the range of from 600 Å to 300,000, and the obtained film is more mechanically strong and preferable. Further, 70,000 to 200,000 are the best. The weight average molecular weight Mw and the number average molecular weight Μη of the cellulose vinegar were measured by gel permeation chromatography (GPC). The measurement conditions are as follows. Solvent: Dichloromethane Column: Shodex Κ806, Κ8 05, K8 03 G (Use 3 tubes connected by Showa Denko Co., Ltd.)

Column temperature: 25°C Sample concentration: 0_1 mass% -12- 201002766 Detector: RI Model 5 04 (manufactured by GL Scientific Co., Ltd.) Pump: L6000 (manufactured by Hitachi, Ltd.) Flow rate: 1.0 ml/min Calibration curve : A calibration curve prepared by using 13 samples of standard polystyrene STK standard polystyrene (manufactured by TOSHO Co., Ltd.) Mw = 1 00 0000 to 5.00. 1 3 samples, almost equally spaced. The raw material cellulose of the cellulose ester used in the present invention is not particularly limited, and examples thereof include cotton linters, wood pulp, kenaf and the like. Further, the cellulose ester obtained therefrom can be used in any ratio. The cellulose ester of cellulose acetate phthalate or the like of the present invention can be produced by a known method. Specifically, it can be synthesized by referring to the method of JP-A-10-50804. <Aromatic terminal polyester compound represented by the general formula (I)> In the present invention, the aromatic terminal polyester compound represented by the following general formula (I) is used.

General formula (I) B-(G-A)n-G-B (wherein B-based aryl carboxylic acid residue, G-based alkanediol residue having carbon number 2 to 12 or carbon number 6 to 12 An aryl diol residue or an oxyalkylene glycol residue having a carbon number of 4 to 12' A is an alkylene dicarboxylic acid residue having a carbon number of 4 to 12 or an aryl dicarboxylic acid residue having a carbon number of 6 to 12. Base, and n is an integer of 1 or more). In the general formula (I), an aryl carboxylic acid residue represented by hydrazine and an alkyl diol residue or an oxyalkyl diol residue or an aryl diol residue represented by G, and an alkylene represented by hydrazine. The dicarboxylic acid residue or the aryl dicarboxylic acid residue can be obtained by the same reaction as the general polyester compound from -13 to 201002766. The aryl carboxylic acid component of the aromatic terminal polyester compound used in the present invention is, for example, benzoic acid, p-tert-butylbenzoic acid, o-toluic acid, methyltoluic acid, p-toluic acid, dimethylbenzoic acid. Ethyl benzoic acid, n-propyl benzoic acid, amino benzoic acid, acetoxy benzoic acid, etc. may be used alone or in combination of two or more. The alkanediol component having 2 to 12 carbon atoms of the aromatic terminal polyester compound which can be used in the present invention includes ethylene glycol, u-propylene glycol, propylene glycol, 1,2-butanediol, and 1,3-butyl Alcohol, 1) 2-propane diol, 2-methyl-1, propane diol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propane Glycol (neopentyl glycol), 2,2-diethyl-1,3-propanediol (3,3-dihydroxymethylpentane), 2-11-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, ι, 10_癸The "diols" such as alkanediol and 1,12-octadecanediol may be used alone or in combination of two or more. Among them, an alkanediol having a carbon number of 2 to 12 is particularly preferred because it has excellent compatibility with a cellulose ester. Further, the oxyalkylene glycol component having 4 to 12 carbon atoms of the aromatic terminal polyester compound may, for example, be diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol or tripropylene glycol. The diol may be used alone or in combination of two or more. Aromatic terminal polyester compound having a carbon number of 4 to 12 alkyl dicarboxyl-14-201002766 acid component, for example, succinic acid, maleic acid, fumaric acid, glutaric acid, hexanoic acid, azelaic acid And azelaic acid, dodecanedicarboxylic acid, and the like, which may be used in the form of a work type or a mixture of two or more kinds. Examples of the aryldicarboxylic acid component having 6 to 12 carbon atoms include phthalic acid, p-benzoic acid, m-formic acid, 1,5 naphthalene diacid, 1,4 naphthalene diacid. The aromatic terminal polyester compound used in the present invention is preferably η of 1 or more and 100 or less, and preferably has a number average molecular weight of 1,500 to 1,500, more preferably 400 to 1,000. Further, the acid value is 0.5 mgKOH/g or less, and the hydroxyl value is 25 mgKOH/g or less; preferably, the acid value is 0.3 mgKOH/g or less, and the base price is 15 mgKOH/g or less. The aromatic terminal polyester compound represented by the general formula (I) of the present invention is preferably contained in an amount of 0.5 to 30% by mass based on the cellulose ester. The following are specific examples of the aromatic terminal polyester compound which can be used in the present invention, but the present invention is not limited to these ranges. -15- 201002766 r=\

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Χο- οοΟΗο*Ηο'·οοο· χο I -οοΟΗΟ£οοόο -ΟΟΟΗΟΙΟΟΟ. -Ι"ο -0,5 § < at least one of one or more 12 or less pyranose structures or furanose structures, and all or a part of the OH group of the structure is esterified ester compound > The cellulose ester film of the present invention is characterized in that it contains all or one of OH groups having at least one of 1 to 19-201002766 having at least one of 12 or less pyranose structures or furanose structures. The fraction is an esterified ester compound. The ratio of esterification is preferably 70% or more of the OH groups present in the pyranose structure or the furanose structure. In the present invention, it is collectively referred to as an ester compound, and is also referred to as a sugar ester compound. The ester compound of the present invention is exemplified by the following examples, but the present invention is not limited to these ranges. For example: glucose, galactose, mannose, fructose, xylose, or arabinose, lactose, sucrose, cane tetrasaccharide, 1F-fructose cane tetrasaccharide, stachyose, maltitol, lactitol, lactulose, Cellobiose, maltose, cellotriose, maltotriose, raffinose, or canetriose. In addition, 'gentiobiose, gentian triose, gentian tetraose, xylotriose, galactosyl sucrose, and the like. Among these compounds, a compound having both a smogose structure and a furanose structure is preferred. For example, sucrose, canetriose, cane tetrasaccharide, 1F-fructose-based canetetraose, stachyose, etc. are preferred, and sucrose is preferred. In the present invention, the monocarboxylic acid used in the esterification of the pyranose structure or the furanose structure is not particularly limited, and a conventional aliphatic monocarboxylic acid can be used. An alicyclic monocarboxylic acid, an aromatic monocarboxylic acid or the like. The carboxylic acid to be used may be one type or a mixture of two or more types. Preferred aliphatic monocapric acid 'for example: acetic acid, propionic acid, butyric acid, isobutyric acid, oxalic acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, 2_B-20-201002766-hexane-carboxylate Acid, undecanoic acid, lauric acid, tridecanoic acid, myristyl acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nineteen acid, arachidic acid, behenic acid, tetracosic acid, Saturated fatty acid, undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, peanut-impregnated with twenty-six acid, twenty-seven acid, octadecanoic acid, tridecanoic acid, and tridecanoic acid An unsaturated fatty acid such as an acid or an octenoic acid. Preferred alicyclic monocarboxylic acids are, for example, acetic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, or the like. Preferred aromatic monocarboxylic acids include, for example, benzoic acid, phenylacetic acid, etc., an alkyl group, an alkoxy group, an aromatic monocarboxylic acid, a cinnamic acid, a diphenyl glycolic acid, a biphenyl group introduced into a benzene ring of benzoic acid. An aromatic monocarboxylic acid having two or more benzene rings, such as a carboxylic acid, a naphthalenecarboxylic acid or a naphthyl carboxylic acid, or a derivative thereof, etc. More specifically, for example, dimethylbenzoic acid, dimethyl Benzoic acid, aspartic acid, trimethyl succinic acid, r-heodoic acid, ruthenic acid, keto acid, "-homoic acid, cumene, alpha-toluic acid, hydrogenated atropic acid, Atoric acid, hydrogenated cinnamic acid, salicylic acid, guanidine-anisic acid, m-anisic acid, ρ-anisic acid, phenolic acid, 〇-liter salicylic acid, m-liter salicylic acid, ρ-liter salicylic acid, hydrazine - pyrocatechin, hydroxydibenzoic acid, vanillic acid, isovaleric acid, leucovoric acid, 0-retinoic acid, gallic acid, asaric acid, mandelic acid, p-methoxyphenylacetic acid, levic acid, Rilic acid, 0-liter leucovoric acid, decanoic acid, ρ-coumaric acid, but benzoic acid is the best. The oligosaccharide ester compound is suitably used as a compound having at least one of 1 to 12 pyranose structures or furanose structures in the present invention. The oligosaccharide is produced by the enzyme such as amylase which acts on starch, sucrose-21 - 201002766, etc. It is suitable for the oligosaccharide of the present invention, for example, malto-oligosaccharide, isomalto-oligosaccharide, fruit Oligosaccharides, galactooligosaccharides, xylooligosaccharides. Further, the ester compound is a compound having at least one of a pyranose structure or a furanose structure of at least one of 12 or less represented by the following general formula (A). However, 'Rn~Ri5, R21 to R25 are an alkyl group having a carbon number of 2 to 22 or a hydrogen atom; m and n are each an integer of 〇12, and m+n is an integer of 1 to 12. - General (A) --- (-F-hr

R11 to R15 and R2 1 to R25 are preferably a benzamidine group or a hydrogen atom. The benzoyl group may further have a substituent R-26 (p is 0 to 5), such as an alkyl group, an alkenyl group, an alkoxy group, a phenyl group, and further, the alkyl group, the alkenyl group, and the phenyl group may have Substituent. The oligosaccharide can also be produced by the same method as the ester compound of the present invention. Hereinafter, specific examples of the ester compound of the present invention are given, but the present invention is not limited to this range. -22- 201002766 [Chemical 6] Compound 1

Ο R1 == —C-CH3 Compound 2 OHjOCOCHg R20

H R2〇/CH2〇COCH3 OR2 OR2 Η Ο R2= — C-CHCH3 ch3 Compound 3

R3: Compound 4

R4 a C-C2H5 -23 201002766 [Chemistry 7]

Compound S

R5= —C-CH3

〇 R$= —C-CH3 Compound 6 Compound 7 CH, OR7

R7= —C-CH3 Compound 8

R8» —C-CH3 -24-

H OR9 H OR9 H OR9 201002766 [Chemical 8] Compound 9 Compound 10 CH2OR10 Ο R9= —C-CHa

R10=—C-CHj -25- 201002766 [Chemical 9] Compound 11

CH2〇R11 1〆〇,

Y° \H R110/ ., a _ R11 = \| |/CH2OR11 L· I I OR11 H och3

OOHS Compound 12 CH2〇R12 CH2OR12

CHzOR12 OR12 H R12= OCH3 Compound 13

R13=—C-CHa-^~^ Compound 14

Och3 26- 201002766 Compound 15 GHzOR15 I_〇 χ 4, vOR15 R15. , Η, 4 R15 H GR15 Compound 16 CH2〇R16 I 〇 4 , , OR16 R1SO, \f16 4 R16 H OR16 -C—CHg Compound 17

R17* -I-^ch3 -ο ο ιι -c-ch3

-27- 201002766 [Chem. 11] Compound 18

0- Compound 19 CH2OR19 OR19 •Ο. CH2OR18 *〇--CH2 OR19|_ OR18

Ο· OR18 η=2^-8 CH2〇Rl8 -Ο, OR18 OR18 OR18 Ο R18= —C-CH3 CH2OR19 OR19 OR19

OR19 Ο. OR19 OR19 OR19 〇 R19= —C-CH3 -28- 201002766 [Chemistry 12] Compound 20

〇 R20O

R20O 〇, R20〇/ CH9

R20O Ο

R20O 200^/ CH, R20 = O II c-ch3 R20O,

R20O Ο, «〇〇/ CH2 Ο

R20O/ R20O, 〇 R20O CH2 i

R20O 29- 201002766 [Chem. 13] Compound 21

II R21= —C-CH? Compound 22 CH,〇R22

In the cellulose ester film of the present invention, in order to suppress the phase difference, the display quality is stabilized, and the sugar esterification of the present invention is preferably 0.5 to 30% by mass of the cellulose ester film, and is preferably in an amount of For the best. The content of the aromatic terminal polymer and the sugar ester compound represented by the general formula (I) of the present invention may be varied in a mass ratio of 9 9 : 1 to 1, and the compound is a compound of 5 to 30 mass esters: 99 In the range of -30-201002766, the total amount of the two compounds is preferably from 1 to 40% by mass based on the cellulose ester. <Other Additives> (Plasticizer) The cellulose ester film of the present invention may contain a plasticizer as needed, in order to obtain the effects of the present invention. The plasticizer is not particularly limited, but preferably, it can be selected from the group consisting of a polycarboxylic acid ester plasticizer, a glycolate plasticizer, a phthalate plasticizer, a fatty acid ester plasticizer, and a plurality of An alcohol ester type plasticizer, a polyester type plasticizer, a propylene type plasticizer, or the like. Among them, when two or more kinds of plasticizers are used, at least one of them is preferably a polyol ester-based plasticizer. The polyol ester-based plasticizer is a plasticizer composed of an aliphatic polyol of 2 or more and an ester of a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule. The best one is a 2 to 20 member aliphatic polyol ester. The polyol which is preferably used in the present invention is as shown in the following general formula (a). General formula (a) R1 - (OH)n However, R1 is an organic group having an η valence, n is a positive integer of 2 or more, and an OH group is an alcoholic group and/or a phenolic hydroxyl group. Examples of preferred polyols are exemplified below, but the invention is not limited to the scope of the invention. Ribool, arabitol, ethylene glycol, diethylene glycol, triethylene glycol-31 - 201002766, tetraethylene glycol, 1,2-propylene glycol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1, 2-butanediol, 1,3-butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexyl Glycol, hexanetriol, galactitol, mannitol, 3-methylpenter-1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylol Ethane, xylitol, and the like. Among them, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferred. The monocarboxylic acid to be used as the polyol is not particularly limited, and a conventional aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid or the like can be used. However, when an alicyclic monocarboxylic acid or an aromatic monocarboxylic acid is used, it is preferable because it is improved in moisture permeability and retention. The preferred monocarboxylic acid is, for example, exemplified below, but the invention is not limited to the scope of the invention. As the aliphatic monocarboxylic acid, a fatty acid having a linear or side chain having a carbon number of 1 to 32 can be preferably used. The carbon number of 1 to 20 is better, and the 1 to 10 is the best. Since the compatibility with cellulose ester can be increased when acetic acid is contained, it is preferred, and it is preferred to use acetic acid in combination with other monocarboxylic acids. Preferred aliphatic monocarboxylic acids, for example, acetic acid, propionic acid, butyric acid, oxalic acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, 2-ethyl-hexane acid, undecanoic acid, lauric acid, Tridecanoic acid, myristate etheric acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nineteen acid, arachidic acid, behenic acid, tetracosic acid, hexacylic acid, twenty-seven acid , octadecanoic acid, tribasic acid, tridecanoic acid and other saturated fatty acids, ^--carbonic acid, oleic acid, sorbic acid, linoleic acid '-32- 201002766 linolenic acid, phenylmethane oxygen and the like. Its 1500 is a kind of unsaturated fatty acid such as acid or peanut-impregnated acid. Preferred alicyclic monocarboxylic acids are, for example, cyclopentanecarboxylic acid, cyclohexanecarboxycyclodecanoic acid, or derivatives thereof. A preferred aromatic monocarboxylic acid, for example, an aromatic monocarboxylic acid or a biphenyl group having a base of 1 to 3 alkyl groups, a methoxy group or an ethoxy group introduced into a benzene ring of an acid such as benzoic acid or phenylacetic acid. The carboxylic acid, the naphthalene carboxylic acid, the naphthalene carboxylic acid, the aromatic monocarboxylic acid having two or more benzene rings, or the like, is preferably benzoic acid. The molecular weight of the polyol ester is not particularly limited, but is preferably 300 Torr and preferably 350 to 750. It is preferred because it is difficult to produce a large molecular weight, and it is preferably a small one based on moisture permeability and compatibility with cellulose ester. The carboxylic acid which can be used for the polyol ester can be one type or can be a mixture of two or more. Further, the OH group in the 'polyol' may be all esters, or may be a part in which the 〇H group remains. Hereinafter, specific compounds of the polyol ester are exemplified. -33- 201002766 [Chem. 14] C4H9-C-〇-{CH2)2-〇-{CH2)2-〇-(CH2)2-〇-C-C4H9ο 〇τ ο ο-<CH2>2-O —tCHJa-O—(CH2)2—Ο-ς

-D

4 〇-r°-fCHi-CH2-°)r|^〇5 C4Hs—C —〇-^CH2**CH2—o^-c_c4h8 oo 6 CbH17-*C-〇-^CH2"CHz—Oj^— C-CeHn oo 7

-CH2CH2Cfl2-〇 2 9 C4He-poor one o-^ch2ch2ch2-o*^^-c4h9 o o 10 <νΗ17_α-. One ^ch2ch2CH2-o^-c-c8h17

〇 GH3 〇 o o 15 〇~r °-f CH^-°)r|-〇 -34- i?201002766 5] IX 6 1 a, one

17 ch2-oc-c4h9 οη,οη2-ο-οη2»ο·"〇-ο4η9I 〇ch2-oc-c4h9 I!o 18 i? CH 广0«·Η7 CHSCH2-C-CH2 a 0-C-CfHt7 I 〇20 qh2-〇«6h,7 ηoo

Ch2 CH3CH2-C-CH2-0-C-C«3o ch2-o-c-ch3 H o 22 o M gh2-o-c CH3CH2 — C-Cl CH2-0-C-CH3 llo

CH2 one OH -35- 201002766 [Chemistry 16

o o

*?CH

9 cso } 27 ΤΙό ?Li cloic = o ,ol~

o CIOICIC

Hi -36- 201002766 [Chem. 17]

Gh2 33 ch2-o- r〇

9 CHO ^^-Ο-Ο-ί^-ΟΗ,-ΟΗ,-Ο^Ο-Ο-ζ^) 34 -rr\ ηύ_ λ &gt;-f 35 c=o ό glycolate plasticizer, and There is no particular limitation, but alkyl sulfonyl glycolate esters are preferably used. Alkyl hydroxyalkyl glycolates, for example, methyl hydrazine methyl glycolate, ethyl hydrazine ethyl glycolate, propyl propyl glycol glycolate, butyl hydrazine Butyl glycolate, octyloctyl glycolate, methyl hydrazine ethyl glycolate, ethyl hydrazine methyl glycolate, ethyl propyl propyl glycolate , methyl butyl butyl glycolate, -37- 201002766 ethyl butyl butyl glycolate 'butyl butyl methyl glycolate 'butyl butyl ethyl glycolate, C Base butyl glycolate, butyl propyl glycol vinegar, methyl octyl glycolate, ethyl octyl glycolate, octyl hydrazine methyl alcohol Acid esters, octyl hydrazine ethyl glycolate, and the like. The phthalate-based plasticizers are, for example, diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, two-2 Ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, dicyclohexyl terephthalate, and the like. The citrate type plasticizer may, for example, be acetaminophen citrate, triethyl citrate, butyl tributyl citrate or the like. The fatty acid ester-based plasticizers are, for example, butyl oleate, methyl decyl ricinolate, dibutyl sebacate and the like. Phosphate-based plasticizers, for example, triphenyl phosphate, tricresol phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl Phosphate and the like. The polyvalent carboxylate compound is composed of a polyvalent carboxylic acid having 2 or more, preferably 2 to 20, and an ester of an alcohol. Further, the aliphatic polycarboxylic acid is preferably 2 to 20, and the aromatic polycarboxylic acid or alicyclic polycarboxylic acid is preferably 3 to 20. The polyvalent carboxylic acid can be represented by the following general formula (b). General formula (b) R2(COOH)m(〇H)n (except that R2 is an organic group of (m + n) valence, !!! is a positive integer of 2 or more, 11 is an integer of 〇 or more, and the COOH group is Carboxyl, fluorenyl is alcoholic or benzene-38 - 201002766 phenolic hydroxyl). Examples of preferred polycarboxylic acids are exemplified below, but the invention is not limited to the scope of the invention. Preferably, an aromatic polycarboxylic acid or a derivative thereof, such as trimellitic acid, trimesic acid, or pyromellitic acid, or the like, azelaic acid, sebacic acid, sebacic acid An aliphatic polycarboxylic acid such as oxalic acid, fumaric acid, maleic acid or tetrahydronaphthalene dicarboxylic acid; an oxypolycarboxylic acid such as tartaric acid, hydroxybenzenedioic acid, mineral acid or citric acid; and the like. Wherein the oxypolycarboxylic acid is used in particular, which is optimal based on the viewpoint of the improvement of the retention property. The alcohol which can be used in the polycarboxylic acid ester compound used in the present invention is not particularly limited and can be used. Known alcohols, phenols. For example, an aliphatic saturated alcohol or an aliphatic unsaturated alcohol having a linear or side chain having a carbon number of 1 to 32 can be preferably used. Further, a carbon number of 1 to 20 is more preferable, and a carbon number of 1 to 10 is most preferable. Further, an alicyclic alcohol such as cyclopentanol or cyclohexanol or a derivative thereof, an aromatic alcohol such as benzyl alcohol or cinnamyl alcohol or a derivative thereof is preferably a user. When a polyvalent carboxylic acid is used, for example, an alcoholic or phenolic hydroxyl group of an oxypolycarboxylic acid can be used for esterification using a monocarboxylic acid. The preferred monocarboxylic acid' is exemplified below, but the invention is not limited to the scope of the invention. As the aliphatic monocarboxylic acid, a fatty acid having a linear or side chain having a carbon number of 1 to 32 can be preferably used. Further, a carbon number of 1 to 20 is more preferable, and a carbon number of 1 to 10 is most preferable. -39- 201002766 Preferred aliphatic monocarboxylic acids 'for example: acetic acid, propionic acid, butyric acid, oxalic acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid '2-ethyl-hexanecarboxylic acid, ten Monoacid, lauric acid, tridecanoic acid 'myristate ether acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nineteen acid, arachidic acid, behenic acid, tetracosic acid, twenty-six a saturated fatty acid such as acid, notogenoic acid, octadecanoic acid, tridecanoic acid or tridecanoic acid, undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, etc. Unsaturated fatty acids, etc. Preferred alicyclic monocarboxylic acids are, for example, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, or the like. The aromatic monocarboxylic acid is preferably one having two or more of an alkyl group introduced into a benzene ring of benzoic acid, a biphenyl carboxylic acid, a naphthalene carboxylic acid, or a naphthyl carboxylic acid, such as benzoic acid or phenylacetic acid. An aromatic monocarboxylic acid of a benzene ring, or a derivative thereof. Among them, acetic acid, propionic acid and benzoic acid are the best. The molecular weight of the polyvalent carboxylate compound is not particularly limited, but is preferably in the range of 300 to 1,000 in terms of molecular weight, and is preferably in the range of 35 to 750. The preference based on the improvement of retention is preferred, and it is preferred from the viewpoint of moisture permeability and compatibility with cellulose esters. The alcohol which can be used in the polycarboxylic acid ester used in the present invention may be one type or a mixture of two or more types. The polyvalent carboxylate compound which can be used in the present invention has an acid value of preferably 1 mgKOH/g or less, and preferably 0.2 mgKOH/g or less. Controlling the acid price in the above range is preferable because the environmental variation of the phase difference is also suppressed. -40- 201002766 In addition, the acid value refers to the number of milligrams of potassium hydroxide necessary to neutralize the acid contained in 1 g of the sample (the sulfhydryl group present in the sample). The acid value is determined according to Jis K0070. The most preferred polycarboxylic acid ester compound is exemplified below, but the present invention is not limited to these ranges. For example, 'there are triethyl citrate, tributyl citrate, acetyl triethyl citrate (ATEC), acetyl tributyl citrate (ATBC), benzamidine tributyl citrate Ester, acetyl triphenyl citrate, acetyl tribenzyl citrate, dibutyl tartrate, dibutyl butyl tartrate, tributyl trimellitate, tetrabutyl trimellitate, and the like. (Ultraviolet absorber) The cellulose ester film B of the present invention may further contain an ultraviolet absorber. The ultraviolet absorber is based on the absorption of ultraviolet rays of 400 nm or less and can improve the durability. The transmittance of the wavelength of 370 nm is preferably 10% or less, and the case of 5% or less is more preferable. The ultraviolet absorber used in the present invention is preferably 2% or less, and is not particularly limited, and examples thereof include an oxybenzophenone compound, a benzotriazole compound, and a salicylate compound. a benzophenone-based compound, a cyanoacrylate-based compound, a diazine-based compound, a nickel-salted salt-based compound, an inorganic powder or the like. For example, θ ' has 5-chloro-2-(3,5·di-sec-butyl-2-hydroxyphenyl)-2H-benzotriazole, (2_2H•benzotriazole_2_yl)· 6_ (straight and side chain undecyl)-4-methylphenol, 2-hydroxy-4-indolyl benzophenone-41 - 201002766, 2,4-benzyloxybenzophenone In addition, there are also TINUVINs such as TINUVIN 109, TINUVIN 171, TINUVIN 23 4, TINUVIN 3 26, TINUVIN 327, TINUVIN 328, etc., all of which are commercially available from Ciba Specialty Chemicals. The ultraviolet absorber preferably used in the present invention is a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, and a triazine-based ultraviolet absorber, and the most preferable one is a benzotriazole-based ultraviolet absorber. , benzophenone-based UV absorber. Further, a disk-shaped compound having a compound such as a 1,3,5-triazine ring or the like is preferably used as a UV absorber. The polarizing plate protective film of the present invention preferably contains two or more kinds of ultraviolet absorbers. Further, as the ultraviolet absorber, it is preferable to use a polymer ultraviolet absorber, and in particular, a polymer type ultraviolet absorber of JP-A-6-148 4 3 0 is preferable. The method of adding a UV absorber can dissolve an ultraviolet absorber in an alcohol such as methanol, ethanol or butanol or an organic solvent such as dichloromethane, methyl acetate, acetone or dioxolane or a mixed solvent thereof. In addition, add rubber paddles, or add directly to the composition of the glue. If it is insoluble in an organic solvent such as an inorganic powder, it can be added to the dope after dispersing using a dissolver or a sand mill in an organic solvent and a cellulose ester. The amount of the ultraviolet absorber used may vary depending on the type of the ultraviolet absorber, the conditions of use, etc. 'When the dry film of the polarizing plate protective film is -42-201002766, the thickness is 30 to 200 μm, and the polarizing plate is protected. The film is preferably 0.5 to 10% by mass, and more preferably 〇6 to 4% by mass. (Antioxidant) An antioxidant is also called a deterioration preventive agent. When a liquid crystal display device or the like is provided under conditions of high humidity and high temperature, the cellulose ester film may be deteriorated. The antioxidant can, for example, delay the decomposition of the cellulose ester film caused by the amount of solvent remaining in the cellulose ester film or the phosphoric acid of the phosphate-based plasticizer, and has a function of preventing decomposition thereof. It is preferred that the cellulose ester film contains an antioxidant. Such an antioxidant, for example, a hindered phenol-based compound is preferable, for example, 2,6-di-t-butyl-p-formamidine, pentaerythritol-tetrakis[3-(3,5·di-t-butyl) 4-hydroxyphenyl)propionate], triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], ι,6- Hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(η-octylthio)-6-( 4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,2-sulfan-diethylidene bis[3-(3,5-di-t- Butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, hydrazine, Ν'-hexa-extension Methyl bis(3,5-mono-t-butyl-4-yl-hydrocinnamoguanamine), 1,3,5-trimethyl-2,4,6-tris(3,5-di- T-butyl-4-hydroxybenzyl)benzene, tris-(3,5-di-t-butyl-4-hydroxybenzyl)-trimeric isocyanate, and the like. Among them, especially 2,6-di-t-butyl-P-cresol, pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], three Ethylene glycol-bis[3-(3--43-201002766 t-butyl-5-methyl-4-hydroxyphenyl)propionate] is preferred. Further, for example, 'N,N'-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanyl]anthracene may be used as the metal inactive of the lanthanide series. A phosphorus-based processing stabilizer such as tris(2,4-di-t-butylphenyl) phosphate. The amount of such a compound to be added is preferably from 1 ppm to 1.0% by mass based on the cellulose derivative, and preferably from 10 to 1,000 ppm. (Microparticles) The cellulose ester film of the present invention preferably contains fine particles. Examples of the inorganic compound used in the present invention include cerium oxide, titanium oxide, aluminum oxide, oxidized pin calcium carbonate, talc, white clay, calcined kaolin, calcined calcium citrate, water and calcium citrate, and strontium. Aluminum acid, magnesium citrate, and calcium phosphate. Further, it is preferable to use fine particles of an organic compound. Examples of organic compounds include polytetrafluoroethylene, cellulose acetate, polystyrene, polymethyl methacrylate, polypropyl methacrylate, polymethacrylate, polyvinyl carbonate, and propylene benzene. Ethylene resin, polyketone resin, polycarbonate resin, benzoguanamine resin, melamine resin, polyolefin powder, polyester resin, polyamine resin, polyimide resin, Or a pulverized fraction of an organic polymer compound such as a polyvinyl fluoride resin or a starch. Further, a polymer compound synthesized by a suspension polymerization method, a polymer compound obtained by a spray drying method or a dispersion method, or an inorganic compound may be used. The microparticles, which contain bismuth, are preferred because they have a low turbidity -44-201002766, and sand dioxide is preferred. The average particle diameter of the primary particles of the microparticles is preferably 5 to 400 nm, and preferably 10 to 300 nm. These may be those which mainly contain secondary aggregates having a particle diameter of 〇.〇5~0.3&quot;m, and if they are particles having an average particle diameter of 100 to 400 nm, they do not aggregate, and thus are contained in primary particles. Also good. The content of such fine particles in the protective film of the polarizing plate is preferably 0.01 to 1% by mass, particularly preferably 0.05 to 0.5% by mass. In the case of a polarizing plate protective film composed of a plurality of layers formed by a co-casting method, it is preferred that the particles have such an added amount on the surface. As the particle size of cerium oxide, for example, AEROSIL R972, R972V, R974, R812, 200, 200V, 300, R202, 0X50, TT600 (all of which are manufactured by Japan AEROSIL Co., Ltd.) are commercially available. use. As the zirconia fine particles, for example, commercially available AEROSIL R976 and R81 1 (all of which are manufactured by Japan AEROSIL Co., Ltd.) can be used. Examples of the polymer include polyketone resin, fluororesin, and acrylic resin. It is preferably a polyfluorene ketone resin, and is preferably a three-dimensional network structure, such as TO S PEARL 103, the same 105, the same 108, the same 120, the same 145, the same 3120 and the same 240 (above) The product names of Toshiba Polydecyl Ester (shares) can be used. Among them, AEROSIL 200V and AEROSIL R972V can maintain the polarizing plate protective film in a low turbidity state, and the friction-45-201002766 coefficient is very effective, so it is most suitable for use. In the polarizing plate protective film used in the present invention, it is preferred that the dynamic friction coefficient of at least one side is 〇2 to 10. Various additives may be added in batches to the cement containing the cellulose ester solution before film formation. Alternatively, an additive solution may be separately prepared and then added on the line. Among them, in order to reduce the load of the microparticles on the over-rubber material, it is preferable to carry out the addition of a part or the whole amount on the line. When the additive solution is added in a line, it is preferred to dissolve a small amount of the cellulose ester in order to improve the compatibility with the dope. The amount of the preferred cellulose ester is relative to the solvent: 〇 〇 by mass, and is 1 to 1 〇 by mass, preferably 3 to 5 parts by mass. In order to perform on-line addition and mixing in the present invention, for example, an in-line mixer such as a Stitch Mixer (TORAY Engineering) or a SWJ (TORAY Static In-Tube Mixer Hi-Mixer) can be preferably used. <Method for Producing Cellulose Ester Film> The following describes the method for producing the cellulose ester film of the present invention. The cellulose ester film of the present invention may preferably be a film produced by a solution casting method or a film produced by a melt casting method. The cellulose ester film of the present invention is produced by the steps of: dissolving a cellulose ester and an additive in a solvent to prepare a dope; and casting the dope to an infinitely moving endless metal support; casting The step of making the mortar -46 - 201002766 and drying it; the step of peeling off the metal support; the step of extending or maintaining the width; the step of further drying; and the step of winding the film after completion. The procedure for preparing the glue is explained. The concentration of the cellulose ester in the dope is preferably such that the drying load after casting on the metal support is reduced, but if the concentration of the cellulose ester is too rich, the load during filtration will be Increase, so the filtering accuracy will be worse. In order to achieve such a concentration, it is preferably 10 to 35 mass%, and more preferably 15 to 25 mass%. The solvent used in the dope may be used alone or in combination of two or more. However, if a good solvent of the cellulose ester is mixed with a poor solvent, it is preferred from the viewpoint of production efficiency; More often, it is preferable from the viewpoint of solubility of a cellulose ester. A preferred range of the mixing ratio of the good solvent to the poor solvent is 70 to 98% by mass of the good solvent and 2 to 30% by mass of the poor solvent. The term "good solvent, poor solvent" means that the cellulose ester used alone is dissolved as a good solvent, and those which are swollen or insoluble are defined as a poor solvent. Therefore, according to the average degree of acetification of the cellulose ester (the degree of substitution of ethyl ketone) 'the good solvent, the poor solvent will change 'for example, when acetone is used as a solvent', the acetate in the cellulose ester (the degree of substitution of ethyl ketone 2.4 ), cellulose acetate propionate is a good solvent; and cellulose acetate (acetylation degree 2.8), it becomes a poor solvent. The good solvent which can be used in the present invention is not particularly limited, and examples thereof include an organic halogen compound such as chloroformamidine or dioxolane, acetone, methyl acetate, methyl acetate methyl acetate and the like. The best ones are, for example, dichlorocarbazone or -47- 201002766 methyl acetate. Further, the poor solvent which can be used in the present invention is not particularly limited, and for example, methanol, ethanol, η-butanol, cyclohexane, cyclohexanone or the like can be preferably used. Further, it is preferable that the glue contains 1 to 2% by mass of water of 〇·〇. Further, the solvent used in the dissolution of the cellulose vinegar can be recovered by drying in a film forming step and then removed by a solvent removed from the film, and then reused. In the recovery solvent, there may be a trace amount of additives added to the cellulose ester, such as a plasticizer, a UV absorber, a polymer, a monomer component, etc., but even if such a component is contained, it is preferable to reuse it. It can also be purified and reused as necessary. In the preparation of the above-mentioned dope, a method of dissolving the cellulose ester can be carried out by a usual method. When heating and pressurization are combined, heating can be carried out above the boiling point in the normal pressure. For example, when the solvent is at a temperature above the boiling point of the normal pressure and the solvent does not boil under pressure, the mixture is stirred and dissolved while being heated, 'because the block-like undissolved matter called gel or agglomerate can be prevented. It happens better. Further, after the cellulose ester is mixed with a poor solvent and moisturized or swollen, a method of further adding a good solvent for dissolution is also preferred. The pressurization can be carried out by a method of injecting an inert gas such as nitrogen or a method of increasing the vapor pressure of the solvent by heating. It is preferred that the heating is controlled by an external person, e.g., in the form of a jacket, and the temperature is preferably controlled. -48- 201002766 Adding the heating temperature of the solvent, the solubility of the cellulose ester is good because of the high temperature, but if the heating temperature is too high, the required pressure becomes large, resulting in poor productivity. The preferred heating temperature is 4 5 to 1 2 0 ° C, more preferably 6 0 to 1 10 ° C, and the optimum is 70 to 1 05 ° C. In addition, the pressure is adjusted so that the solvent does not boil at the set temperature. Alternatively, it is preferred to use a cooling solvent method, whereby the cellulose ester can be dissolved in a solvent such as methyl acetate. Next, the cellulose ester solution is filtered using a suitable filter material such as filter paper. The filter material is preferably one in which the absolute filtration accuracy is small in order to remove insoluble matter, and if the absolute filtration accuracy is too small, the filter material is liable to cause clogging. Therefore, the absolute filtration accuracy is preferably a filter material of 0.008 mm or less, a filter material of 0.001 to 0.008 mm is more preferable, and a filter material of 0.003 to 0.006 mm is most preferable. The material of the filter material is not particularly limited, and a general filter material can be used, but a plastic filter material such as polypropylene or Teflon (registered trademark) or a metal filter material such as stainless steel is used, and the fiber does not fall off. The situation is better. By filtration, impurities contained in the cellulose ester of the raw material, particularly bright foreign matter, can be removed and reduced. The term "bright spot foreign matter" refers to a state in which two polarizing plates are arranged in a state of orthogonal polarizers. In the meantime, an optical film or the like is provided, and when one polarizing plate is irradiated and then viewed from the other side of the polarizing plate, the opposite is observed. The direction of light leakage (foreign matter) from -49 to 201002766 is preferably such that the number of bright points having a diameter of 0 _ 0 1 mm or more is 200 / cm 2 or less. More preferably, it is 100 pieces/cm2 or less, and the best one is 50 pieces/cm2 or less. ‘Excellent one is 0 to 10 pieces/cm2 or less. In addition, it is preferable that the number of bright spots below 〇 1 mm is small. The filtration of the glue can be carried out according to the usual method, except that the solvent is above the boiling point of the normal pressure and the temperature does not boil under the pressure, the method of filtering on the surface heating side, the filtration pressure before and after the filtration The difference in the difference (referred to as differential pressure) is small and preferable. Preferably, the temperature is 4 5 to 1 2 ° C, more preferably 4 5 to 7 0 ° C, and the optimum is 4 5 to 5 5 〇C. The filter system is preferably smaller. The filtration pressure is preferably 1. 6 MPa or less, more preferably 1.2 MPa or less, and most preferably 1 〇 MPa or less. Here, the casting of the glue will be described. The metal support in the Casting step is preferably such that the surface is processed into a mirror surface, and the metal support is a stainless steel belt or a drum which is surface-plated by a casting. Preferably. The width of the casting can be 1 to 4 m. The surface temperature of the metal support in the casting step is a temperature of -5 0 ° C to the boiling point of the solvent, and the drying speed of the mesh is high and the temperature is high, preferably, if the temperature is too high The material will foam and its planarity may deteriorate. The preferred support temperature is 0 to 5 5 ° C, and is preferably 2 5 to 50 ° C. Alternatively, it is also preferred to gel the web by cooling and to peel off the drum in a state rich in residual solvent. -50- 201002766 The method of controlling the temperature of the metal support is not particularly limited, and is, for example, a method of blowing warm air or cold air, or a method of bringing warm water into contact with the inside of the metal support. Since the heat can be transferred efficiently when using warm water, the temperature of the metal support is short and preferred before reaching a certain temperature. If warm air is used, winds with a higher temperature than the target temperature can also be used. In order to make the cellulose vinegar film have poor planarity, the amount of residual solvent when the mesh is peeled off from the metal support is preferably 10 to 150% by mass and is 20 to 40% by mass. % or 6 0 to 1 3 0% by mass is more preferable, and 20 to 30% by mass or 70 to 120% by mass is most preferable. In the present invention, the amount of residual solvent is defined by the following formula. Residual solvent amount (% by mass) = {(Μ - Ν) / Ν} χ 100 In addition, the lanthanide system will take the sample quality at the time of manufacture or at any time after manufacture, and the lanthanide will be used in 1 1 Heat at 1 °C for 1 hour. Further, in the drying step of the cellulose ester film, the mesh is peeled off from the metal support, dried, and the amount of the residual solvent is preferably 1% by mass or less, and further preferably 0.1% by mass or less. For better, it is preferably 0 to 0.01% by mass or less. In the film drying step, generally, a method in which the web is moved and dried by a roll drying method (a plurality of rolls arranged up and down, the web is alternately passed through to dry it) or a tenter method is used. For the production of the cellulose ester film of the present invention, it is preferred that the both ends of the web are stretched in the width direction (horizontal -51 - 201002766) by a tenter such as a clip. It is preferable that the peeling tension is 300 Å/m or less. The means for drying the web is not particularly limited, and general hot air, infrared rays, heated rolls, microwaves, and the like can be used, but hot air is preferred because of the simple viewpoint. The drying temperature in the drying step of the web is preferably 40 to 200 t. The film thickness of the cellulose ester film is not particularly limited, but it can be used in the range of 10 to 200 //m. Especially, the film thickness is preferably 10 to 100/zm, and the film thickness is preferably 20 to 60/zm. The cellulose ester film of the present invention is used in a width of 1 to 4 m. Especially preferably 1.4 to 4 m in width, and preferably 1.6 to 3 m in width. If it exceeds 4 m, there will be difficulties in moving. In order to obtain the phase difference 〇R〇, Rt' cellulose ester film of the present invention, it is preferred to use the constitution of the present invention, and to control the refractive index by the control of the transport tension and the stretching operation. For example, by reducing or increasing the tension in the long direction, the phase difference 値 can be changed. Further, the longitudinal direction (film formation direction) of the film and the direction orthogonal to the film surface, that is, the width direction, may be extended in two or seven axes one by one or simultaneously. The stretching ratios in the two-axis directions orthogonal to each other are preferably in the range of from 0.8 to 1.5 times in the casting direction and in the range of from 1 to 2.5 times in the width direction, and are preferably 〇·8 in the casting direction. The range of i.0 times and the width direction of 1.2 to 2.0 times is optimal. -52- 201002766 The extension temperature is preferably from 1 2 0 °C to 2 0 0 °C, and is 1 50. (: ~ 2 〇〇 ° C is better, and it is better to extend at more than 150 ° C and below 19 ° C. The residual solvent in the film is 20~0% Preferably, the extension is 15~ 〇%. Specifically, the residual solvent at 1 5 5 °c is 11% extension, or the residual solvent at 1 5 5 °c is 2% extension. Preferably, it is preferred that the residual solvent at 110 ° C is 11% extended, or the residual solvent at 1 60 ° C is less than 1%. The method is not particularly limited. For example, there is a method of imparting a peripheral speed difference on a plurality of rolls and extending in the longitudinal direction by using a circumferential speed difference of the rolls; Or a method in which the needle is fixed and the clip or the needle is extended in the direction of the direction to extend in the longitudinal direction; the method of expanding in the lateral direction and extending in the lateral direction; or simultaneously expanding in the longitudinal direction and the horizontal direction Method, etc. Of course, these methods can also be used in combination. In addition, in the case of the so-called tenter method, When the clip portion can be driven in a linear driving manner, a smooth extension occurs, so that the risk of breakage or the like can be reduced, and it is preferable that the width of the clip is maintained or extended in the lateral direction. Preferably, it is carried out by a tenter, which may be a pin tenter or a clip tenter. The cellulose ester film of the present invention has a slow phase or a phase axis which exists on the inner surface of the film and The angle 01 formed with the film forming direction is preferably 0 -1 to -201002766 or more and +1 or less, and is preferably -0.5 or more + 〇.5. The following is the best. It is defined as the alignment angle, and the measurement of 01 can be performed by the automatic complex refractometer KOBRA-21ADH (Prince Measurement Machine). When θ 1 satisfies the above various relationships, high brightness can be obtained in the display screen and it can be suppressed or prevented. The function of light leakage makes it possible to obtain faithful reproduction of color in a color liquid crystal display device. &lt;Physical properties of cellulose ester film&gt; The moisture permeability of the cellulose ester film of the present invention is 40 ° C and 90% RH. 300 ~ 1800g / m2, 24h is better, and 400 ~ 150 0g/m2·24h is more preferable, and 40~I 3 00g/m2 · 24h is preferable. The moisture permeability can be measured according to the method described in JIS Z 0208. The cellulose ester film of the present invention has elongation at break Preferably, it is preferably 10 to 80%, and preferably 20 to 50%. The cellulose ester film of the present invention preferably has a visible light transmittance of 90% or more and more than 93%. Preferably, the cellulose ester film of the present invention has a haze of less than 1% and is preferably 0 to 0.1%. Further, the cellulose ester film of the present invention is further borrowed. A larger range of phase differences can be further obtained by coating the liquid crystal layer '. &lt;Polarizing Plate&gt; The cellulose ester film of the phase difference film of the present invention can be used as a polarizing plate as a protective film for a polarizing plate of -54-201002766, and a liquid crystal display device of the present invention using the same. The polarizing plate of the present invention is characterized in that the cellulose ester film of the present invention is used as a polarizing plate protective film and is attached to a polarizing plate on at least one side of a polarizer. In the liquid crystal display device of the present invention, the polarizing plate of the present invention is bonded to the polarizing layer via at least one surface of the liquid crystal cell. The polarizing plate of the present invention can be produced by a general method. Preferably, the polarizing side of the cellulose ester film of the present invention is alkalized, and immersed in at least one side of the polarizing element prepared by stretching in an iodine solution, using a fully alkalized polyvinyl alcohol aqueous solution. fit. It is also preferred to use the cellulose ester film on the other side or to laminate the other polarizing plate protective film.

For example, it is preferred to use a commercially available cellulose ester film (for example, Konica Minolta KC8UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC4UE, KC8UE, KC8UY-HA, KC8UX-RHA, KC8UXW-RHA-C, KC8UXW-RHA-NC, KC4UXW-RHA-NC, all of which are manufactured by Konica Minolta Co., Ltd.) 偏In the polarizing plate protective film used on the surface side of the display device, In addition to the glare layer or the transparent hard coat layer, it is preferred to have an antireflection layer, an antistatic layer, an antifouling layer, and a back coat layer. The polarizer of the main component of the polarizing plate refers to a component that allows only light of a polarized surface in a certain direction to pass through. A representative polarizer is known as -55-201002766, which is a polyvinyl alcohol-based polarizing film which can make iodine. Dyeing on polyvinyl alcohol-based films and dyes of dichroic dyes. In the case of a polarizer, a polyvinyl alcohol aqueous solution is formed into a film and stretched by one-axis stretching, or after dyeing and after one-axis stretching, it is preferred to carry out durability treatment with a boron compound. The film thickness of the polarizer is preferably 5 to 30 #m, preferably 10 to 20 // m. In addition, the content of the ethylene unit described in JP-A-2003-2481-23, JP-A-2003-342322, and the like is 1 to 4% by mole, the degree of polymerization is 2000 to 4000, and the degree of alkalinity is 99.0 to 99.99% by mole. The ethylene-modified polyvinyl alcohol is also preferably a user. Among them, an ethylene-denatured polyvinyl alcohol film having a hot water cut-off temperature of 66 to 73 ° C is preferably used. In addition, the difference between the hot water cut-off temperature between the two points at a distance of 5 cm in the TD direction of the film, such as below 1 °C, can reduce the color spots and better 'further, as in the film TD The difference between the hot water cut-off temperature between the two points in the direction of lcm is 0.5 °C or less, and the color spot is reduced to be optimal. In addition to excellent polarizing performance and durability, the polarizer of such an ethylene-denatured polyvinyl alcohol film exhibits less color unevenness and is particularly suitable for use in a large liquid crystal display device. The polarizer obtained as described above is generally used as a polarizing plate by attaching a protective film to both sides or one side thereof. The adhesive to be used for bonding is, for example, a P V A-based adhesive or a urethane-based adhesive, etc., but a PVA-based adhesive is preferred. -56-201002766 &lt;Liquid Crystal Display Device&gt; By using the polarizing plate of the present invention on a liquid crystal display device, it is possible to produce a liquid crystal display device of the present invention which is excellent in various visibility. The cellulose ester film of the present invention can be used in liquid crystal display devices of various driving methods such as STN, TN, OCB, HAN 'VA (MVA 'PVA), IPS, OCB, and the like. Preferably, it is a VA (MVA, PVA) type liquid crystal display device. In particular, even in a liquid crystal display device having a large screen of 30 吋 or more, it is possible to obtain a liquid crystal display device which is less environmentally variable, has a reduced light leakage, and is excellent in visibility such as hue and face ratio. [Embodiment] Hereinafter, the present invention will be described by way of examples, but the invention is not limited thereto. Example 1 &lt;Production of Cellulose Ester Film 101&gt;&lt;Microparticle Dispersion Liquid 1&gt; Microparticles (AEROSIL R972V, manufactured by Japan AEROSIL Co., Ltd.) 11 parts by mass of ethanol 89 parts by mass. The above was stirred and mixed for 50 minutes with a dissolver. 'Disperse with a homogenizer. -57-201002766 &lt;Microparticle-added liquid ι&gt; The mixture was sufficiently stirred in a dichloromethane dissolution vessel, and the microparticle-added liquid 1 was slowly added. Further, it is dispersed by an attritor to make the particle size of the secondary particles a predetermined size. Further, it was filtered with FINEMET NF manufactured by Nippon Seisaku Co., Ltd. to prepare a fine particle addition liquid 1. Methylene chloride 99 parts by mass Microparticle addition liquid 15 parts by mass The main dope of the following composition was prepared. First, dichloromethane and ethanol were added to the pressurized dissolution vessel. In the pressurized dissolution vessel to which the solvent was added, the cellulose esters A and B were placed while stirring. Heat it and stir it to dissolve completely. The main gel slurry was prepared by filtration using Angstrom filter paper No. 244 made of filter paper (strand). &lt;Composition of main dope&gt; 340 parts by mass 64 parts by mass 1 〇〇 parts by mass 6.5 parts by mass 6.0 parts by mass of 1 part by mass are stirred and dissolved to prepare a gel ethanol. The cellulose ester A of the present invention Polyester-based compound 1 4 The sugar ester compound 3 of the present invention The microparticle-adding liquid 1 The above-mentioned slurry is put into a sealed container. Then, the glue slurry was used at a temperature of 3 3 using an endless belt casting device. &lt;:, it is uniformly cast on the stainless steel belt support at a width of 1500 mm. The temperature of the stainless steel belt is controlled at 3 〇 °C. On the stainless steel belt support, the amount of residual solvent in the film which evaporates the solvent until casting (Cast) -58-201002766 becomes 75% 'then' and the peeling tension is 1 30 N/m, and the stripping is performed on the stainless steel belt support. . The peeled cellulose ester film was subjected to heat of 150 ° C while being stretched by 36% in the width direction using a tenter. The residual solvent at the beginning of the extension was 15%. Next, the drying zone is conveyed while the majority of the rolls are being conveyed, and the drying is completed. The drying temperature was 130 °C and the conveying tension was 100 N/m. As described above, a cellulose ester film 1 having a dry film thickness of 40/m was obtained (Π. The following '1 0 9 and 1 1 1 systems were further added with a plasticizer, and the solvent type, film thickness, and extension ratio were changed as shown in the table. The other ones were operated in the same manner as in 2, and a cellulose ester film 1〇2 to 115 was produced. Plasticizer A: triphenyl phosphate plasticizer B: ethyl hydrazine ethyl glycolate plasticizer C: three Hydroxymethylpropane benzoate was additionally used as a comparative sample 20 1 to 207. [Table 1]

Phase, a &gt; KK This /κ β difference, haze, scattered light intensity. The results are shown in Table 2 -59 - 201002766

(Is Meng Liu Jk § ν (S3 (sea ς inch · one (sv ι·ςι 0.9 0.9 0.9 ΟΟΟΊ 0.9 0·9 0.001 0·9 0·9 0·9 σοοι 0.9 o.lr) (S3 one ~ ΓΓ ( Sdlη一οΓ i«l

I 1 £ inch ιι 5.9 —s.9 15.9 15.9 15.9 IS9 ς·9 UM 5.9 5.9 S·inch 5.9 —S-9 — S.9 S·inch s.9

I 5 —91 ~ΤΓ d—inch one ~VT ΤΓ d,

V I

101 .02 一 i «1 [(N^J SI ΤΓ ΤΓ 0.9 01 ιι·ς οι Τ^Γ τ CQ called d- v v called 叫叫Η~ν 1^1 ν Id-1^,

β 90 二ςο(ΝΙ inch QltNI sz _ slz 9U s inch II eii s IU — ou § 901 SOI SI SI &lt;NIOI -60- 201002766 "Measurement of phase difference 、Ro, Rt" Cut the sample from the obtained film 35mmx35mm, humidity-adjusted for 2 hours at 25 ° C, 5 5% RH, and then with an automatic birefringence meter (KOBRA21DH '(Prince Measurement), according to the vertical direction measured at 590 nm and tilting the film surface The phase difference measured in the same manner was calculated by the intercalation of the two. The cellulose ester film of the present invention I 01 to 1 1 6 was found to be superior to the comparative films 201 to 207. Example 2 &lt;Production of Polarizing Plate&gt; A polyvinyl alcohol film having a thickness of 120/zm was stretched in one axis (temperature: 10 ° C, 5 times extension). It was immersed in iodine 〇 75 g, After immersing in an aqueous solution of 5 g of potassium iodide and 100 g of water for 60 seconds, it was immersed in an aqueous solution of 6 g of potassium iodide, 7.5 g of boric acid, and 100 g of water, and washed with water to obtain a polarizer. Then, according to the following steps 1 to 5', the polarizer and the aforementioned cellulose ester film 101 to 207, On the side, a Konica Minolta film KC4UY (Konica Minolta film) is used to make a polarizing plate. Step 1: 2 Mohr/L Hydroxide at 60 °C The sodium solution is immersed for 90 seconds, then washed with water and dried to obtain a cellulose ester film which is alkalized on one side of the polarizer. Step 2: The above-mentioned polarizer is immersed in a solid component of 2% by mass of poly-61 - 201002766 1 to 2 seconds in the vinyl alcohol solvent tank. Step 3: Gently wipe and remove the excess adhesive attached to the polarizer in step 2, and dispose it in the cellulose ester film treated in step 1. Step 4: The cellulose ester film 1〇1~207 and the polarizer and the inner cellulose ester film laminated in step 3 are conveyed at a pressure of 20 to 30 N/cm2 at a pressure of about 2 m/min. The bonding was carried out. Step 5: The photoposited material prepared in the step 4 was adhered to the cellulose ester film 101 to 207 and the Konica Minolta film KC4UY for 2 minutes in a dryer at 80 °C. Drying and making polarizing plates 1 0 1~1 1 6 , 201 ~ 207 〇 &lt;Production of liquid crystal display device&gt; The liquid crystal panel whose viewing angle was measured was produced as follows, and evaluated as a characteristic of the liquid crystal display device. The two-sided polarizing plate of the 40-inch display KLV-40J3000 of SONY was peeled off, and the polarizing plate prepared above was peeled off. 1 0 1 to 1 1 6 are attached to both faces of the glass surface of the liquid crystal cell. At this time, the bonding direction of the polarizing plate is such that the cellulose ester film surface of the present invention faces the liquid crystal cell side, and the absorption axis is oriented in the same direction as the previously attached polarizing plate, and the liquid crystal display device 101 is fabricated. 116, 201 to 207 〇 Regarding this liquid crystal display device, the color tone variation and the front contrast were evaluated. The results are shown in Table 3. -62-201002766 "Evaluation of the change in hue" The liquid crystal display device of the above-described production was measured for the change in color tone using a measuring machine (£2_Contrastl 060D, manufactured by ELDIM Co., Ltd.). In the CIE1976 and UCS coordinates, the maximum color tone variation range Δυ'ν' in the vertical direction (80° to 80° in the normal direction) is compared. <<Evaluation of Positive Contrast>> The backlight of each liquid crystal display device was continuously lit for one week in an environment of 23 ° C and 55% RH, and then measured. For the measurement, EZ_ContraStl60D manufactured by ELDIM Co., Ltd. was used, and the brightness of the liquid crystal display device and the normal direction of the display screen of the black display were measured, and the comparison was made as a frontal comparison. Front contrast = (luminance of white display measured by the normal direction of the display device) / (luminance of black display measured by the normal direction of the display device) -63- 201002766 [Table 3] Liquid crystal display device No. (Δ U, V' ) Front contrast Note 10 1 0.06 1170 The present invention 102 0.08 1150 The present invention 103 0.07 1120 The present invention 104 0.08 1120 The present invention 105 0.07 1130 The present invention 106 0.05 1170 The present invention 107 0.05 1140 The present invention 108 0.06 1120 Invention 109 0.06 1110 Invention 110 0.06 1150 Invention 111 0.06 1150 Invention 112 0.07 115 0 Invention 113 0.08 1150 Invention 114 0.07 1120 Invention 115 0.07 1170 Invention 116 0.06 1150 Invention 20 1 0.16 950 Comparative Example 202 0.18 950 Comparative Example 203 0.18 930 Comparative Example 204 0.15 970 Comparative Example 205 0.17 980 Comparative Example 206 0.16 950 Comparative Example 207 0.11 1050 Comparative Example From the results of Table 3, the liquid crystal display device 1 0 1 to 1 of the present invention can be clearly known. 1 6, which is a liquid crystal display device which is excellent in color tone change and front contrast. -64- 201002766 [Simple description of the diagram] ® 1 : Schematic diagram of the state of dropping glycerin on a glass slide. ® 2: Schematic diagram of the state in which the sample film is placed on glycerin. * 3: Schematic diagram of the state in which glycerin is dropped on the sample film. Fig. 4: Schematic diagram of the state in which the glace is placed on the cover glass -65-

Claims (1)

201002766 VII. Patent application scope: 1. A cellulose ester film is characterized by the haze measurement of a film by a haze meter, such as when a solvent having a refractive index of a refractive index of ±0.05 is used as a film interface. The haze is 0.02 or less. 2. The cellulose ester film according to claim 1, wherein the cellulose ester film contains at least one aromatic terminal polyester compound represented by the following general formula (I), and one or more 1 or less of at least one of a pyranose structure or a furanose structure, and all or a part of the OH group of the structure is a cellulose ester film of the esterified ester compound, and the general formula (I) B- (G-A)n - G-B (wherein B is an aryl decanoic acid residue, G is an alkylene glycol residue having a carbon number of 2 to 12 or an aryl group having a carbon number of 6 to 12 An alcohol residue or an oxy-an alcohol residue having a carbon number of 4 to 12' A is a dicarboxylic acid residue having a carbon number of 4 to 12 or an aryl dicarboxylic acid residue having a carbon number of 6 to 12, ^ is an integer greater than 1). -66 -