TW201226452A - Cellulose ester film, and polarizing plate and liquid crystal display device using the same - Google Patents

Abstract

The present invention is to provide a cellulose ester film which has the substantially improved water resistance and polarizer protection ability, and a polarizing and a liquid crystal display device using the same. The cellulose ester film of the present invention contains a cellulose acetate having a degree of remaining hydroxyl groups (DR) of 0.5-1.0, a hydrolysis inhibitor (A), and a retardation adjusting agent (B), and satisfies the following formulae (1) and (2). Formula (1): 4 < (logP(A)) - (logP(B)) < 12 (logP(A) and logP(B) respectively represent octanol-water distribution coefficients of the hydrolysis inhibitor (A) and the retardation adjusting agent (B).) Formula (2): 2.5 < (W(A)/W(B))*(1/DR) < 8.5 (W(A) and W(B) respectively represent the masses of the hydrolysis inhibitor (A) and the retardation adjusting agent (B) contained in the cellulose ester film, and DR represents the degree of remaining hydroxyl groups of the cellulose acetate).

Description

201226452 VI. Description of the Invention: [Technical Field] The present invention relates to a cellulose ester film, a polarizing plate using the same, and a liquid crystal display device. [Prior Art] A liquid crystal display device is widely used for an image display device because of its low power consumption and space saving. Although the VA type liquid crystal display device has an advantage of being superior to other liquid crystal display types, it has a problem of large contrast and color tone change depending on the viewing angle. In order to solve this problem, an improved method of optically compensating films and combinations thereof is proposed. For example, a method in which two biaxial films are placed on both sides in a liquid crystal cell (Patent Document 1). Since the cellulose ester film is excellent in transparency and can produce a film having controlled refractive index anisotropy, it can be widely used for optical applications such as a protective film for a polarizing plate and an optical compensation film. Among the cellulose ester films, a cellulose ester having a low degree of substitution such as a diacetyl cellulose is excellent in the phase difference, and is conventionally used for an optical film such as a λ/4 plate (Patent Document 2). . In other words, when the optical compensation film is used in combination with the polarizing plate, it is expected that the improvement of the polarization unevenness or the retardation of the in-plane direction exhibits an effect of suppressing the viewing angle of the color tone or the like. However, cellulose esters having a low degree of substitution have low heat and humidity resistance, so the protection of the photon is low and the use range is limited. It is proposed to use a compound having an octanol-water partition coefficient (logP) of 0 to 12 -5 - 201226452 as a plasticizer for a cellulose ester (Patent Document 3). However, when this method is used for a cellulose ester having a low degree of substitution, the plasticizer may be bleed out or the heat and humidity resistance of the film may be improved, but there is a problem that white turbidity is generated, and further improvement is required. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. [Inventive Summary] [Problems to be Solved by the Invention] Therefore, the object of the present invention is to use a film of a cellulose ester which is excellent in phase difference exhibitability and which is expected to have a low degree of substitution with a high optical compensation effect. It is possible to suppress haze and improve moisture and heat resistance, and in particular, it is used for a v A type liquid crystal display device, and a cellulose ester film having high contrast and excellent viewing angle characteristics can be obtained. [Means for Solving the Problem] The above problems of the present invention are achieved by the following constitution. A cellulose ester film characterized by containing at least one cellulose cellulose acetate having a hydroxyl residue (DR) of 0.5 M.0, a hydrolysis preventing agent (A), and a phase difference adjustment of 201226452 (B) And satisfying the following relationship (1), (2) relationship (1) 4 &lt; (l〇gP(A)) - (logP(B)) &lt; 12 (but logP (A): hydrolysis preventing agent ( A) octanol-water partition coefficient, logP (B): phase difference adjuster (B) octanol-water partition coefficient) relation (2) 2.5 &lt; (W (A) / W (B)) x (l/DR) &lt; 8.5 (but W (A): the mass of the hydrolysis preventing agent (A) contained in the cellulose ester film, W (B): the phase difference adjusting agent (B) in the cellulose ester film 2. The cellulose ester film according to the above item 1, wherein the cellulose ester film has an internal haze of 0.05 or less. 3. The cellulose ester film according to the above item 1, wherein the total amount (ppm) of calcium and magnesium contained in the cellulose ester film and the amount of acetic acid (ppm) satisfy the following relationship (3), The cellulose ester film according to any one of the above items 1 to 3, wherein the foregoing is the above formula (3) 1 ((amount of acetic acid (ppm)) / (total amount of calcium and magnesium (ppm)) logP ( A ) is 7 or more and less than 11, and logP ( B ) is less than 7

The cellulose ester film according to any one of the items 1 to 4, wherein the hydrolysis preventing agent (A) is at least one of a pyranose structure or a furanose structure containing two or more or less than one or less. And one of the 0H groups of its structure is an esterified ester compound. 6. The cellulose ester film according to any one of items 1 to 5 above, wherein the phase difference adjusting agent (B) of the above-mentioned 201226452 is represented by the following general formula (1).

General formula (1) B-(GA)nGB (wherein B represents a hydroxyl group or a carboxylic acid residue, and G represents an alkanediol residue having 2 to 12 carbon atoms or an aryl glycol having 6 to 12 carbon atoms; a residue or a carbon number 4 to 12 oxyalkylene glycol residue, and the A system represents an alkyl 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, and the η system represents 1 The above integer). 7. A cellulose ester film characterized by a cellulose acetate having a hydroxyl residue (DR) of 0.5 to 1.0, and an octanol-water partition coefficient (logP(A)) of 7 or more and less than 1 1 Hydrolysis inhibitor (A) and an anionic surfactant. 8. The cellulose ester film according to the above item 7, wherein the anionic surfactant is a compound of the following general formula (I) or (II), and the general formula (I) [R10(A0)n]pP (= 0)(0M)q General formula (II)

R2-LQ (R1 and R2 are the bases of the carbon number 8 to 22 which may have a linear or branched substituent. 'A series shows a non-carbon number of 2 to 4, and η is 0 or 1 to 20 Integer, p and q represent an integer of p + q = 3' and ρ = 1 or 2, and μ represents any 'L-type divalent linking group of a hydrogen atom, an alkali metal atom, or an ammonium group, and q represents a carboxy group. An acid or a salt thereof, a sulfonic acid or a salt thereof, a sulfate or a salt thereof). 9. The cellulose ester film according to the above item 7 or 8, wherein the anionic surfactant is contained in an amount of 0.005 to 0.5 parts by mass based on 100 parts by mass of the cellulose acetate. The cellulose ester film according to any one of the items 7 to 9 above, which comprises the phase difference adjusting agent (B) represented by the above general formula (1). 11_ A polarizing plate' characterized in that the cellulose vinegar film of any of the above items is bonded to at least one side of a polarizer composed of polyvinyl alcohol. A liquid crystal display device characterized in that at least one side of a liquid crystal cell has the polarizing plate of the eleventh aspect. In other words, the inventors carefully reviewed the results and found that for the cellulose ester having a lower degree of substitution, a compound having an octanol-water partition coefficient (10 gP 値) in a specific range, and a hydroxyl group of cellulose acetate was used. The optimum combination of the residual amount and the respective addition amount, or the use of the above-mentioned l〇gP値 within a specific range of the hydrolysis preventing agent and the anionic surfactant can suppress the haze of the film, improve the moist heat resistance, and significantly improve the photon. The protection is achieved by the present invention. [Effect of the Invention] According to the present invention, it is possible to provide a cellulose ester having a low degree of substitution, a low haze, and excellent heat and humidity resistance, particularly for a VA liquid crystal display device, which has high contrast and excellent viewing angle. A cellulose ester film having characteristics and a polarizing plate used for a polarizing plate protective film, and a liquid crystal display device having the polarizing plate. [Mode for Carrying Out the Invention] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to this -9 - 201226452. Each element will be described below. &lt; Octanol-water partition coefficient (logP) &gt; The cellulose ester film of the present invention is characterized by the difference between the octanol-water partition coefficient (logP) of the hydrolysis preventing agent (A) and the phase difference adjusting agent (B) a compound within a certain range. The compound with higher logP値 can improve the water resistance of the cellulose ester film, but the compatibility with the cellulose ester is low, so it is easy to produce white turbidity and precipitation, and the compound with lower logP値 can maintain the transparency of the cellulose ester film. However, the improvement in water resistance is insufficient. In particular, the cellulose ester having a high hydroxyl residue in the present invention is only compatible with a compound having an extremely low log P?, and it is not possible to simultaneously improve the white turbidity and water resistance of the cellulose ester film. The cellulose ester film of the present invention can satisfy the following relationship (1) and relation (2) without causing white turbidity of the film and improving water resistance. Relationship (1) 4 &lt; (logP(A)) - (logP(B)) &lt; 12 (but logP (A): octanol-water partition coefficient of hydrolysis inhibitor (A), logP (B): phase The octanol-water partition coefficient of the difference adjuster (B))) (2) 2.5&lt;(W(A)/W(B))x(l/DR)&lt;8.5 (but W(A), W ( B ): the mass of the hydrolysis preventive agent (A), the phase difference adjuster (B) contained in the cellulose ester film, and the DR: the hydroxyl residue of the cellulose acetate.) The reason is as follows. When the compound having a high logP値 is not easily soluble in the cellulose ester having a higher hydroxyl residue -10- 201226452, when only the cellulose ester of the hydrolysis preventing agent (A) is added, it is presumed that the compound exists in an island form. The compound in the form of islands in the cellulose ester causes light scattering, which impairs the transparency of the cellulose ester film. Further, if the relationship (1) contains a phase difference adjuster (B) having a difference in logP値, it contributes to the compatibility of the cellulose ester with the hydrolysis preventing agent (A), and the hydrolysis preventing agent (A) is uniform. Present in cellulose esters. In the relation (1), when the difference between 'logP(A) and l〇gP(B) is less than 4, the water resistance cannot be improved. When the difference between logP (A) and logP (B) exceeds 12, the compatibility of the compound cannot be improved. . The relationship (2) indicates the relationship between the mass of the cellulose ester film of the hydrolysis preventing agent (A) and the phase difference adjusting agent (B) and the hydroxyl residue (DR) of the cellulose acetate, but is less than 2.5. It is not possible to improve the water resistance', and when it exceeds 8_5, the improvement of compatibility is insufficient, which is not preferable. The measurement of the octanol-water partition coefficient (logP値) was carried out by a flask impregnation method described in JIS Z-7260-107 (2000). The octanol-water partition coefficient (logP値) can also be estimated by computational chemistry or empirical methods. The calculation method is preferably Crippen's fragmentation method ("J. Chem. Inf. Comput. Sci.", 27, p21 (1987)),

Viswanadhan's fragmentation method (u J. Chem. Inf. Comput. Sci., vol. 29, pl 63 (1989)), Broto's fragmentation method ("Eur. J. Med. Chem. - Chim. Theor. 55, Volume 19, P7 1 (1 9 84)), CLogP method (Reference Leo, A·, J〇w, PYC·, Silipo, C·, -11 - 201226452

Hansch, C., J. Med. Chem., 18, 8 65 1 975), etc., better

Crippen's fragmentation method ("J. Chem. Inf. Comput. Sci.", Vol. 27, p. 21 (1987)). &lt;Cellulose ester&gt; The cellulose ester of the present invention is a cellulose acetate having a hydroxyl group residual (DR) of 0.5 to 1.0, but the hydroxyl residue (DR) is more preferably 0.5 to 0.8. Here, the hydroxyl residue (DR) indicates the number of unesterified hydroxyl groups (average enthalpy) among the three hydroxyl groups of the anhydrous glucose constituting cellulose. In other words, the degree of esterification (also referred to as degree of substitution) using cellulose is expressed by the degree of hydroxyl residue (DR) = 3 - degree of esterification. In addition, the degree of substitution of the cellulose ester is expressed by the degree of acetification, and the degree of substitution = degree of acetification xl 62 / (6006 - degree of acetylation X42), and the average degree of acetification of the cellulose ester indicates the combination of the unit mass of cellulose. The amount of acetic acid is measured and calculated according to the test method of ASTM: D-817-96C cellulose acetate. The film obtained by the number average molecular weight (??) of the cellulose ester of the present invention in a range of from 30,000 to 300,000 is preferred because it has a strong mechanical strength. More preferably used for 50000~20000. The ratio of the weight average molecular weight (Mw) to the number average molecular weight (?η) of the cellulose ester, Mw/Mn, is preferably from 1.4 to 3.0. The weight average molecular weight Mw and the number average molecular weight Μη of the cellulose ester were measured by gel permeation chromatography (GPC). The measurement conditions are as follows. -12- 201226452 Solvent: Dichloromethane Column: Shodex K806, K805, K803G (Showa Electric Co., Ltd.)

Column temperature: 2 5 °C Sample temperature: 0.1% by mass Detector: RI Model 504 (produced by GL Scientific) Pump: L6000 (produced by Hitachi, Ltd.) Flow: 1.0ml/min Proofreading curve: Use Proofreading curve obtained from 13 samples of standard polystyrene STK standard polystyrene (made by Tosoh Co., Ltd.) Mw = 1 000000-5 00 "13 samples are used at almost 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 velvet, wood pulp, and ramie. Further, each of the cellulose esters obtained by them may 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 JP-A-10-4 5 804. Commercially available products are, for example, Daicel L20, L30, L40, L50, Eastman Chemical Co., Ca398-3, Ca398-6, C a3 9 8 - 1 0, Ca398-30, Ca394-60S. The total amount (ppm) of calcium and magnesium contained in the cellulose ester film of the present invention and the amount of acetic acid (ppm) preferably satisfy the following relationship (3). Relationship (3) 1 $ (Amount of acetic acid (ppm)) / (Total amount of calcium and magnesium (ppm)) ^30 Calcium and magnesium are contained in the cellulose ester of the raw material of the cellulose ester film, which is -13- 201226452 Neutralizes and stabilizes the acid catalyst (especially sulfuric acid) added in the cellulose ester production process, so it can be added in the form of metal oxides, metal hydroxides, metal salts (mineral acid salts, organic acid salts). . Further, in the case of forming a cellulose ester film, it may be added in the form of a metal oxide, a metal hydroxide or a metal salt (mineral acid salt, organic acid salt). The total amount (ppm) of calcium and magnesium contained in the cellulose ester film of the present invention means the total amount of them. Cellulose Ester In the manufacturing process, water-free acetic acid or acetic acid can be used as the reaction solvent or esterifying agent. The unreacted anhydrous acetic acid is hydrolyzed by a reaction stopper (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 (3), the total amount (ppm) of calcium and the amount of acetic acid (ppm) is preferably 1 or more and 30 or less. When less than 1, the amount of acetic acid is small relative to the amount of calcium and magnesium, due to calcium and Magnesium metal salts produce light scattering, which reduces the contrast and is therefore not good. Further, when it is more than 30, the amount of acetic acid is excessively large relative to the amount of calcium and magnesium. When the cellulose ester and the polarizer are bonded together, the photon deterioration is promoted by acetic acid, which is not preferable. The total amount of calcium and magnesium contained in the cellulose ester film is preferably from 5 to 130 ppm, more preferably from 5 to 80 ppm, still more preferably from 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, still more preferably from 30 to 150 ppm. The calcium and magnesium contained in the cellulose ester film can be determined by a known method. For example, after the dried cellulose ester is completely burned, the ash is dissolved in the -14 to 201226452 hydrochloric acid before treatment. Then, it can be determined by atomic absorption spectrometry. . The lanthanide is obtained in units of ppm of calcium and magnesium in the cellulose ester of the absolute dry state. A known method can be used for the amount of acetic acid contained in the cellulose ester film. For example, the following method can be used. The film was dissolved in dichloromethane and re-precipitated by the addition of methanol. The supernatant was filtered, and the supernatant was determined by gas chromatography to obtain the amount of acetic acid. &lt;Internal haze&gt; The internal haze of the cellulose ester film of the present invention is preferably 0.05 or less, more preferably 0.03 or less, still more preferably 0.01 or less. In order to improve the frontal contrast, it is necessary to lower the haze of the cellulose ester film, and when the haze is divided into the inside of the film and the surface, it is known that the improvement effect is large. The internal haze refers to the haze generated by the scattering factor inside the film, and the internal refers to the portion of 5 μm or more from the surface of the film. This internal haze is obtained by dropping a solvent having a refractive index of a refractive index of ±0.05 of the film to the interface of the film so that the haze of the film surface can be neglected as much as possible, as measured by a haze meter. &lt;Internal haze measuring device&gt; Haze meter (turbidity meter) (type: NDH 2000, Nippon Electric Co., Ltd.) The light source is a 5V9W halogen lamp, and the light receiving unit is silicone -15- 201226452 ph 〇t 〇ce 11 (approximate visual sensitivity filter). In the present invention, the haze of the film when the solvent having the refractive index of the film refractive index ± 〇 · 〇 5 is dropped onto the film is measured by the apparatus, and the enthalpy is 〇·〇5 or less. The measurement was carried out in accordance with Π S Κ - 7 1 3 6 . The internal haze measurement was carried out as follows. This will be described with reference to Figs. First, the blank haze 1 of the measuring instrument other than the film was measured. 1. Drop a drop (0.05 ml) of glycerin onto a clean slide glass. At this point, take care to avoid air bubbles in the droplets. Even if the glass is dry and sometimes it is polluter, it must be washed with a lotion. (Refer to Figure 1) 2. Place the cover glass. Even if the glass is not covered, the glycerin will diffuse. 3. Set in the haze meter and measure the blank haze1. Next, the haze 2 containing the sample was measured in the following order. 4. Drop the glycerin onto the slide. (0.05 ml) (refer to Fig. 1) 5 - The sample film to be measured was placed on the way to prevent the entry of air bubbles. (Refer to Figure 2) 6_ Drop glycerin onto the sample film. (0.05 ml) (refer to Fig. 3) 7. The cover glass was placed thereon. (Refer to Fig. 4) 8. The laminate prepared as described above (cover glass/glycerin/sample film/glycerin/slide from the top) was placed on a haze meter, and haze 2 was measured. 9. Calculation (haze 2) - (haze 1) = (internal haze of the cellulose ester film of the present invention). The cellulose vinegar film was prepared at 23 ° C, 5 5 % R Η, and the sample was prepared after conditioning for 5 hours or more -16-201226452 ', and the haze measurement was carried out at 23 ° C and 55 % RH. Further, the glass and glycerin used in the above measurement are as follows.

Glass: MICRO SLIDE GLASS S9213 MATSUNAMI Glycerin: Deer grade (purity &gt; 99.0%) manufactured by Kanto Chemical Co., Ltd. Refractive index 1.47 &lt; Hydrolysis preventing agent (A) &gt; The hydrolysis preventing agent (A) of the present invention is not particularly limited, and octanol- The water partition coefficient (logP (A)) is preferably 7 or more and less than 11. When logP (A) is less than 7, the hydrolysis prevention effect is small, and when logP (A) is 1 or more, compatibility with cellulose ester is low, and bleeding occurs due to moist heat, which is not preferable. The hydrolysis preventing agent (A) is preferably an ester compound containing at least one of a pyranose structure or a furanose structure containing one or more and 12 or less, and one of the OH groups of the structure is esterified. mixture. Preferably, at least one of a pyranose structure or a furanose structure containing at least one of 12 or less, and a ratio of esterification of all or a part of the esterified ester compound of the OH group of the structure is preferably present. More than 70% of the OH groups in the pyranose structure or the furanose structure. In the present invention, the above ester compounds are collectively referred to as a sugar ester compound. Examples of the ester compound used in the present invention include, for example, the following, but the present invention is not limited thereto. For example, glucose, galactose, mannose, fructose, xylose, or arabinose, lactose, sucrose, cane tetrasaccharide, 1F-fructose cane tetrasaccharide, stachyose, maltitol 'lactitol, lactulose, Cellobiose, maltose-17- 201226452, cellotriose, maltotriose, raffinose or canetriose. Further, for example, gentiobiose, gentian trisaccharide, gentiantetraose, xylotriose, galactosyl sucrose, and the like are mentioned. Among these compounds, a compound having a pyranose structure and a furanose structure is preferred. For example, sucrose, canetriose, canetetraose, 1F-fructose-based canetetraose, stachyose, etc. are preferred, and sucrose is more preferred. The monocarboxylic acid used for esterification of all or a part of the OH group in the pyranose structure or the furanose structure is not particularly limited, and a conventional aliphatic monocarboxylic acid 'alicyclic monocarboxylic acid, aroma can be used. Group of monocarboxylic acids and the like. The carboxylic acid which can be used may be one type or a mixture of two or more types. Preferred aliphatic monocarboxylic acids are, for example, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, 2-ethyl-hexanecarboxylic acid, ten Monoacid, lauric acid, tridecanoic acid, myristate etheric acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nineteen acid, arachidic acid, behenic acid, tetracosic acid, twenty-six Saturated fatty acid, undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, octyl acid, acid, notoginsic acid, octadecanoic acid, tridecanoic acid, tridecanoic acid An unsaturated fatty acid such as an enoic acid. Preferred alicyclic monocarboxylic acids are, for example, acetic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, or derivatives thereof. Preferred aromatic monocarboxylic acids, such as benzoic acid, toluic acid, etc., are introduced into the benzene ring of benzoic acid to introduce an alkyl group, an alkoxy aromatic monocarboxylic acid, cinnamic acid, diphenyl glycolic acid, biphenyl -18-201226452 of a carboxylic acid, a naphthalene carboxylic acid, a naphthalene carboxylic acid, etc., an aromatic monocarboxylic acid having two or more benzene rings, or a derivative thereof, and more specifically, for example, dimethylbenzoic acid, Dimethylphenyl acid, milinic acid, tricandylic acid, γ-heteroduic acid, lyric acid, ketonic acid, (X-isoduccinic acid, cumene, α-toluic acid, hydrogenated Butic acid, atropic 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, p-liter salicin Acid, strontium-pyroic acid, β-hydroxydibenzoic acid, vanillic acid, isovaleric acid, leucovoric acid riric acid, gallic acid, asaric acid, picramic acid, p-methoxyphenylacetic acid, liter Vanillic acid, ascorbic acid, strontium sulphonic acid, decanoic acid, decanoic acid, particularly preferably benzoic acid, naphthic acid. The oligosaccharide ester compound is suitable as the present invention having 1-1 A compound of at least one of a pyranose structure or a furanose structure is used. The oligosaccharide is produced by using an enzyme such as amylase and starch, sucrose or the like, and is suitable for use in the oligosaccharide of the present invention, for example, maltose. Further, the ester compound is one or more of 12 or less pyridose structures or furans represented by the following general formula (Α). At least one of the sugar structures is a compound obtained by condensation, but Rii to Ri5 and R21 to R25 represent a fluorenyl group or a hydrogen atom having 2 to 22 carbon atoms, and each of m and η is an integer of 〇~12, and m + n is An integer from 1 to 12. -19- 201226452 [Chemical 1] General formula {A} -fp-fc- -tFh-

CH2〇Rai CHjOR25

OR„ H

Rh~R15 and R2l~R25 are preferably a benzamidine group or a hydrogen atom. The benzylidene group may have a substituent r26, and may, for example, be an alkyl group, an alkenyl group, an alkoxy group or a phenyl group. Further, the alkyl group, the alkenyl group or the phenyl group may have a substituent. The oligosaccharide can also be produced in the same manner as the ester compound of the present invention. Specific examples of the ester compound of the present invention are given below, but the present invention is not limited thereto. -20- 201226452 [Chemical 2]

A-4

Average degree of substitution 7.0 R3* -21 - 201226452 [Chemical 3]

A-6

22- 201226452 [化4] A-8

R5= Ο ιι -c-ch3 Α-9 CH, OR6

R6: &quot;C-CH, A-10 CH, OR7

H/h r7== —C-CH, A-11

R8« 0 it •C~CH, -23- 201226452 [化5] A-12

R9= —C-CH3 A-13

o R10= —C-CH3 24- 201226452 [Chem. 6] A-14

〇CH, A-15

Ο II R12= — C Average degree of substitution 8.0 A to 16

R13 =

Ο u -C-CH -ο Α-17

OCH, -25- 201226452 [Chem. 7] A-18

ο R15= —C- A-19

O R16= —C —CHZ person A-20

R17= —C-CH,

-26 201226452 [化8] A-21

A one 22

R19=—C-CH3 -27- 201226452 [Chem. 9] A-23

Ο

ο Η c-ch3 -28 201226452 [Chem. 10] A-24 OR21 0R21^ 〇Ri1 L OR21 ”n OR21 R21= —C-CHa A A 25

H · OR22 R22 = -C~CHa The cellulose ester film of the present invention preferably contains 0.5 to 30% by mass of the cellulose ester film, more preferably 5 to 3 % by mass of the hydrolysis preventing agent (a). It is particularly preferably contained in an amount of 2 to 15% by mass. &lt;Phase Difference Adjusting Agent (B)&gt; The phase difference adjusting agent (B) of the present invention is not particularly limited, and the octanol-water partitioning coefficient (logP (B)) is preferably a compound having 0 or more and less than 7. The phase difference adjuster needs to be compatible with the moderate solubility of the resin. In the fiber -29-201226452 ester ester of the present invention, when the logP (B) is less than 〇, the water solubility of the compound is higher, thus causing disorder of alignment, in addition, logP ( When Β) is 7 or more, the alignment of the compound is low, so that the desired phase difference cannot be obtained, which is not preferable. The phase difference adjusting agent (B) is preferably an ester compound represented by the following general formula (1).

- General formula (1) B-(GA)nGB (wherein, B is a hydroxyl group or a carboxylic acid residue, G is an alkylene glycol residue having a carbon number of 2 to 12 or an arylethylene group having a carbon number of 6 to 12 An alcohol residue or an alkylene oxide diol residue having a carbon number of 4 to 12, and A is an alkyl 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, η Indicates an integer greater than 1). In the general formula (1), the hydroxyl or carboxylic acid residue represented by hydrazine is represented by an alkylene glycol residue or an alkylene oxide diol residue or an aryl glycol residue represented by G, and hydrazine. The alkyl dicarboxylic acid residue or the aryl dicarboxylic acid residue can be obtained by the same reaction as a general ester compound. The carboxylic acid component of the ester compound represented by the general formula (1), for example, acetic acid, propionic acid, butyric acid, benzoic acid, p-tert-butylbenzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, and dimethyl The benzoic acid, ethyl benzoic acid, n-propyl benzoic acid, amino benzoic acid, acetoxybenzoic acid, aliphatic acid, and the like can be used in the form of a mixture of one type or two or more types. The alkylene glycol component of the ester compound represented by the formula (1) having 2 to 12 carbon atoms, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,2-propanediol, 2-methyl1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1, 3-propanediol (neopentyl glycol), 2,2-diethyl-1,3-propanediol (3,3-dihydroxymethylpentane), •30- 201226452 2-n-butyl-2 -ethyl-1,3 propanediol (3,3-dihydroxymethylheptane), 3-methyl-1,5-pentanediol 1,6-hexanediol, 2,2,4-trimethyl ι,3-pentanediol, 2-ethyl1,3-hexanol '2-methyl 1,8-octanediol, 19-nonanediol, hydrazine, 1 〇·decanediol, 1,12 - Ethylene glycol, such as alcohol, etc., may be used in combination of one or a mixture of two or more. Among them, the carbon dioxide number of 2 to 12 is excellent in compatibility with the cellulose ester, which is particularly preferable. Further, the 'oxyalkylene glycol component having a carbon number of 4 to 12 of the ester compound represented by the above general formula (1)' may be, for example, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol or tripropylene glycol. The ethylene glycol may be used in the form of a mixture of two or more kinds of the above-mentioned esters of the above-mentioned general formula (1). Maleic acid, fumaric acid 'glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, etc. may be used in combination of one type or two or more types. The exoaryl dicarboxylic acid component having a carbon number of 6 to 12 is, for example, phthalic acid, terephthalic acid, isophthalic acid, 1,5 naphthalene dicarboxylic acid or 1,4 naphthalene dicarboxylic acid. The average molecular weight of the vinegar-based compound coefficient of the general formula (1) is preferably in the range of 3 〇〇 to 1 50,000 Å or more preferably in the range of 400 to 1 0000. Further, the acid value is 〇.5 mgKOH/g or less, and the hydroxyl value is 25 mgKOH/g or less, more preferably the acid value is 〇.3 mgK〇H/g or less, and the hydroxyl value is 15 mgKOH/g or less. Specific compounds of the vinegar-based compound represented by the general formula (1) which can be used in the present invention are exemplified below, but the present invention is not limited thereto. -31 - 201226452 9S ; Ms "ooox^xooou . £0 &quot;5 广 ν-80Η°£υ08 « ^ΓΊ心 £-υ 〈丫 80h°£u08 cl l

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«ΧΟ -32- 201226452 κεΓ Ms

Sn: I SCI: Ms 9S : Ms zla [--] ^—^loool£o^xoo£o£oogo—^—^ I « o I ^—^loool£0£0o£0£0o^0^£ 0TO00£0^x0o£0£oo^ioo—^—^ 030£-H30£&quot;H30^03-80£&quot;5°-5£00t3-9-80£&quot;Ηυ0£ϋ£ϋ?- 8 »ιω «—a &quot;Ho "8~H~50 8i ^.00040^000 £0 , /rs?H0£88—/^«Χ0 -yT^ -5000ixo£oooo^" "ύ80ιηο"508λ" ΗεΓ Ms 93Zl· : Ms ο, xo 娜 80h0£3003 οτω 广~v-80LH3Hi?~03 "030 丨NHOHis IOO —^" «χυ —— 03o5“H008— 8?H~H308 cl £0 ό ZTm WTm -33 - 201226452 [Chemistry 13]

The cellulose ester film of the present invention preferably contains 0.1 to 30% by mass of the cellulose ester film, and particularly preferably contains 0.5 to 10% by mass of the phase difference adjusting agent (B). &lt;Anionic surfactant&gt; As described above, when only the cellulose ester of the hydrolysis preventing agent (A) having a high logP値 is added, it is inferred that the compound exists in an island form. The anionic surfactant can be used to help the cellulose ester to be compatible with the hydrolysis preventing agent (A), and the hydrolysis preventing agent (A) can be uniformly present in the cellulose ester at -34 to 201226452. Further, the cellulose ester film of the present invention contains a hydrolysis preventing agent (A)' which preferably contains a phase difference adjusting agent (B), but has a low degree of substitution and a high hydrophilicity, and has a high temperature at a high temperature. When placed in wet for a long time, it is sometimes found that their additives slightly ooze or are accompanied by a slight increase in haze. As a result of review by the inventors of the present invention, it has been found that an anionic surfactant can be used to avoid the bleeding or the increase in haze. This is because the anionic surfactant has a function as a dispersant of the additive and prevents aggregation of the additive. The cellulose ester film of the present invention contains the content of the hydrolysis preventing agent (A) and the phase difference adjusting agent (B), and preferably satisfies the above relation (2). The anionic surfactant of the present invention is not particularly limited, and examples thereof include fatty acid salts, rosin acid salts, hydroxyalkane sulfonates, alkane sulfonates, 'dialkyl sulfosuccinate salts, and α-. Olefin sulfonates, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl phenoxy polyoxyethylene propyl sulfonates, poly Oxyethylene alkyl sulfonate phenyl ether salt, Ν-methyl-Ν-oleyl taurate sodium salt, Ν-alkyl sulfosuccinate monoamine amine disodium salt, petroleum sulfonate, sulfuric acid Sulfate oil, sulfate ester of fatty acid alkyl ester, alkyl sulfate salt, polyoxyethylene alkyl ether sulfate salt, fatty acid monoglyceride sulfate salt, polyoxyethylene alkylphenyl ether sulfate salt , polyoxyethylene phenethyl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates - polyoxyethylene alkyl phenyl ether phosphates, styrene / maleic anhydride Part of the soap of the copolymer -35- 201226452 Part of the saponification of the compound, olefin/maleic anhydride copolymer, naphthalene sulfonate A Water condensates and the like. Among them, particularly preferred are compounds represented by the following general formula (I) or (II) 〇 General formula (I) [R10(A0)n]p-P(=0)(0M)q General formula (II)

R2-L-Q R1 and R2 represent a linear or branched alkyl group having 8 to 22 carbon atoms, particularly preferably an alkyl group having 1 to 18 carbon atoms. The alkyl group may have a substituent such as a halogen atom, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a decyl group, a hydroxyl group, a decyloxy group, an amine group, or an alkyl group. An oxycarbonyl group, a mercaptoamine group, an oxycarbonyl group, an aminomethylguanidinyl group, a sulfonyl group, an aminesulfonyl group, a sulfonyl group, a sulfo group, a carboxyl group or the like. The A system represents an alkylene group having 2 to 4 carbon atoms, and an η system of 0 or an integer of 1 to 20. p and q are p + q = 3 ' and an integer of P = 1 or 2. The lanthanide group represents a hydrogen atom, an alkali metal atom, and an ammonium group. L represents a divalent linking group, and Q represents a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a sulfate or a salt thereof. Specific examples of the anionic surfactant of the present invention are exemplified below, but the present invention is not limited thereto. RZ-1 c8 Hi7〇-P( = 〇)-(OH)2 RZ-2 C, 2Η25〇-Ρ( = 〇)·(〇Κ)2 RZ-3 C, 2H25〇CH2CH2〇-P( = 〇 )-(〇K)2 RZ-4 C, 5H31(OCH2CH2)5〇-P( = 〇)-(〇k)2 -36- 201226452 {C12H250(CH2CH20)5}2-P( = 0)-0H RZ'6 {C18H35(0CH2CH2)80}2-P( = 0)-0NH4 RZ'7 (t-C4H9)3-C6H2-OCH2CH20-P( = 〇)-(〇K)2 RZ'8 (iso- C9Hl9-C6H4-0-(CH2CH20)5-P( = 〇)-(〇K)(OH) RZ_9 C12H25S03Na RZ-!〇Ci2H25〇S〇3Na

RZ'1 1 C17H33COOH RZ-1 2 C17H33COOH · N(CH2CH2OH)3 RZ*1 3 iso-C8Hl7-C6H4-0-(CH2CH20)3-(CH2)2S03Na RZ*1 4 (iso-C9H 丨9)2- C6H3-0-(CH2CH2〇)3-(CH2)4S03Na RZ'15 sodium triisopropyl naphthalene sulfonate RZ-16 sodium tris-t-butylnaphthalene sulfonate C17H33C0N(CH3)CH2CH2S03Na RZ-1 8 C The amount of the 丨2H25-C6H4S03 · NH4 anionic surfactant is preferably 0.005 to 0.5 parts by mass based on 100 parts by mass of the cellulose acetate. More preferably, it is 0.01-0.2 parts by mass, more preferably 0.02 to 0.1 parts by mass. The method of addition is not particularly limited, and it is preferably added to the cellulose acetate solution in the form of a liquid or a solid or a solution dissolved in a solvent. &lt;Other Additives&gt; (Plasticizer) The cellulose ester film of the present invention may contain a plasticizer if necessary in order to obtain the effect of the present invention. -37- 201226452 The plasticizer is not particularly limited, but is preferably selected from the group consisting of a polybasic residual acid vinegar plasticizer, a glycolate plasticizer, a phthalate plasticizer, a fatty acid ester plasticizer, and a polyol ester. It is a plasticizer, a polyester plasticizer, a propylene plasticizer, and 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 a divalent or higher aliphatic polyol and a monocarboxylic acid ester, and preferably has an aromatic ring or a cycloalkyl ring in the molecule. Preferably, it is an aliphatic polyol ester of 2 to 20 members. The polyol which is preferably used in the present invention is represented by the following general formula (a): general formula (a) Rl-(〇H)n, but R1 is an organic group of η valence, η is a positive integer of 2 or more, OH group It is an alcoholic and/or phenolic hydroxyl group. Preferred polyols are, for example, those exemplified below, but the invention is not limited thereto. Ribool, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butyl Alcohol, 1,3-butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, Triol, galactitol, mannitol, 3-methyl-pentan-1,3,5-triol, pinacol, sorbitol, trimethylolpropane trimethylolethane, Xylitol and the like. Particularly preferred are diethyl alcohol, tetraethyl alcohol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, xylitol. -38-201226452 The monocarboxylic acid to be used for the polyol is not particularly limited, and a conventional aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid or the like can be used. When an alicyclic monocarboxylic acid or an aromatic monocarboxylic acid is used, moisture permeability and retention are improved, which is preferable. The preferred monocarboxylic acid is, for example, exemplified below, but the invention is not limited thereto. The aliphatic monocarboxylic acid is preferably a fatty acid having a linear or side chain having 1 to 3 carbon atoms. Carbon number 1~2 is better, and 1~10 is especially good. It is preferable because it can increase the compatibility with the cellulose ester when it contains acetic acid, and it can also be used by mixing acetic acid and other monocarboxylic acids. Preferred aliphatic monocarboxylic acids are, for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, 2-ethyl-hexanoic acid, acid, lauric acid, ten Triacid, myristate etheric acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nineteen acid, arachidic acid, behenic acid, tetracosic acid, hexacylic acid, twenty-seven acid, A saturated fatty acid such as octadecanoic acid, triacyl acid or tridecanoic acid, an unsaturated fatty acid such as undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid or arachidonic acid. Preferred alicyclic monocarboxylic acids are, for example, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, or derivatives thereof. A preferred aromatic mono-residual acid is an aromatic monocarboxylic acid having an alkoxy group of 1 to 3 alkyl groups, a methoxy group or an ethoxy group, and a benzene ring of benzoic acid such as benzoic acid or toluic acid. An aromatic mono-residual acid having two or more benzene rings, such as a phenylcarboxylic acid or a naphthalenecarboxylic acid 'naphthyl carboxylic acid, or a derivative thereof. Particularly preferred is benzoic acid. -39- 201226452 The molecular weight of the polyol ester is not particularly limited, but is preferably from 3 0 to 1,500, more preferably from 3 to 50 to 75. Since it is difficult to volatilize because it has a large molecular weight, it is preferable, and it is preferable in terms of moisture permeability and compatibility with a cellulose ester. The carboxylic acid to be used for the polyol ester may be one type or a mixture of two or more types. Further, the OH group in the polyol may be all esterified, or may be a part in which the OH group remains. Hereinafter, specific compounds of the polyol ester are exemplified. C-0-(CH2)2-0-(CH2)2-0-(CH2)2-0-C»C4He 〇'0-(CH2)2-0-(CH2)2-0- (CH2)j-0-C-/^ 〇-〇-(CH2)2-〇-(CH2)2-〇-(CH2)3-〇-C-/〉 0 X&quot;&quot;' O o-^ Ch2-ch2-o-^-c-c4h9 4 6 〇-^CH2-CH2-〇-^-C-CbH17 ύ 0 '~9 o c4h9-co-^ch2ch2ch2-o-^-c-c4h9 o * c «h9-Qrο-α-

C4H9-C C8H1V-C o°Or

CeH„· 11 o 12〇- 13 C«H,_

CbH17-

lsO -〇-^CH2CH2CH2-〇-^-C-CeH17 -ch2ch2ch2-o

-〇-fcH*?H-〇h-〇CH, 〇-O-^-CHjCH-O^-C-CtH, CH, O CH, 〇-40- 201226452 [化15] 16 ch3ch2-c-ch; Ch2-oc— oc—\ 17 o ch2-oc-c4h9 o ch2 - ch3ch2-c-ch2-oc-c4h9I 〇CH2-〇-C-C4Ha IIo 18

o II ch2-o-c-c8h17 ch3ch2-c-ch2-o-c-c8h17I 〇 ch2-o-c-c8h17 IIo

20

o M CHa-〇-C ch3ch2-c-ch2-o-c-ch3o ch2-o-c-ch, IIo

-41 - 201226452

2 5-0 Η clolc II ο Η C I Η clolc II t ο

Ηί C

Clo clolc = οHJ~ CIO • clo clolc II ο Ηί c -5 a ο ./ ^ ο-— έ=οό 26 Ηί C Η3Η CH_c-°-c ιι ο Η}Η CICIOIC Ι ο 28 29 {3~°= ?-L Η-Γ"ό ο~°=·ιΗίΊΗ ^.0.^.0 οτ^.ο—^ 〇τ27

Η2 C I Ηί OIC οτ o-r-lc-CH,

W2 C

Ηί •OIC Η ** cno 6

??αΗ,π^ο C 9 CUO ο -42- 201226452 [化17]

34 &lt;〇Κ〇-ο^οη2-οη-ο^ο-ο-/Λ χ=/ ο ch3 ο λ~r 35

The glycolate-based plasticizer is not particularly limited, and it is preferred to use a hospital-based oxime alkyl glycolate. Alkyl decyl glycolic acid esters such as methyl hydrazine methyl glycolate, ethyl hydrazine ethyl glycolate, propyl hydrazide glycolate, butyl butyl butyl Glycolate, octyloctyl glycolate, methyl hydrazine ethyl glycolate, ethyl hydrazine methyl glycolate, ethyl propyl propyl glycolate, Methyl butyl butyl glycolate, ethyl butyl butyl glycolate, butyl hydrazine methyl glycolate, butyl hydrazine ethyl glycolate, propyl butyl butyl Glycolate, butyl 酞-43- 201226452 醯 propyl glycolate, methyl octyl glycolate, ethyl octyl glycolate, octyl methoxy glycolic acid Ester, octyl hydrazine ethyl glycolate and the like. The phthalate-based plasticizers are, for example, diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2- Ethylhexyl phthalate, dioctyl phthalate 'dicyclohexyl decanoate, dicyclohexyl phthalate, and the like. The citrate type plasticizer may, for example, be acetoxytrimethyl citrate, acetoxytriethyl citrate or butyl tributyl citrate. The fatty acid ester-based plasticizers are, for example, butyl oleate, methyl decyl phthalate, dibutyl sebacate and the like. Phosphate-based plasticizers are, for example, triphenyl phosphate, tricresol phosphate, cresol 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(OH)n (except that R2 represents an organic group of (m + n) valence 'm is a positive integer of 2 or more, 11 is an integer of 〇 or more, and a COOH group is a carboxyl group, The OH group is an alcoholic or phenolic hydroxyl group. Preferred polycarboxylic acids are exemplified below, but the present invention is not limited to -44 - 201226452. It is preferred to use a trimenic acid, trimesic acid, pyromellitic acid or higher aromatic polycarboxylic acid or a derivative thereof, succinic acid, adipicolinic acid, sebacic acid, oxalic acid, fumaric acid An oxopolycarboxylic acid such as maleic acid, an aliphatic polybasic carboxylic acid of tetrahydrofuran, tartaric acid, hydroxyphthalic acid, malic acid or acid. Among them, the use of an oxypolycarboxylic acid is particularly preferable in terms of retention retention and the like. The alcohol to be used in the polyvalent carboxylate compound which can be used in the present invention is particularly limited, and conventional alcohols and phenols can be used. For example, it is preferred to use a linear or pendant aliphatic saturated alcohol or an aliphatic unsaturated alcohol having a carbon number of 3 2 . In addition, it is more preferably a carbon number, particularly preferably a carbon number of 1 to 1 〇. Further, it is preferred to use an alicyclic alcohol derivative such as cyclopentanol or cyclohexanol, a polyvalent carboxylic acid such as an aromatic alcohol such as benzyl alcohol or cinnamyl alcohol or a derivative thereof, such as an oxypolycarboxylic acid. The alcoholic or phenolic hydroxyl group of the oxypolyacid can also be esterified using a monocarboxylic acid. Preferred carboxylic acids are exemplified below, but the invention is not limited thereto. The aliphatic monocarboxylic acid preferably has a linear or fatty acid having 1 to 32 carbon atoms. Further, more preferably, the carbon number is from 1 to 20, particularly preferably from 1 to 10 carbon atoms. Preferred aliphatic monocarboxylic acids are, for example, acetic acid, propionic acid, butyric acid, caproic acid, heptanoic acid, caprylic acid, capric acid: capric acid. , 2-ethyl-hexanecarboxylic acid monoacid, lauric acid, tridecanoic acid, myristate acid, pentadecanoic acid, palmitic acid, stearic acid, nonadecanic acid, arachidic acid, behenic acid, Twenty-two, twenty-six acid, twenty-seven acid, octadecanoic acid, thirty acid, thirty-two, three acid, acid, etc. lemon, /INN chain 1~20 or its &gt; Side chain valeric acid, deca-acid, tetra-acid, etc. -45- 201226452 saturated fatty acids, undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, etc. . Preferred alicyclic monocarboxylic acids are, for example, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, or derivatives thereof. The aromatic monocarboxylic acid having a benzene ring such as benzoic acid or toluic acid is preferably an alkyl group, a biphenyl carboxylic acid, a naphthalene carboxylic acid or a naphthyl carboxylic acid having two or more benzene rings. Aromatic monocarboxylic acids or derivatives thereof. Among them, particularly preferred are acetic acid, propionic acid, and benzoic acid. The molecular weight of the polyvalent carboxylate compound is not particularly limited, and is preferably in the range of from 3 to 00 to 1,000, more preferably from 3 to 50. From the viewpoint of improving retention, it is preferable that the larger one is preferable, and the smaller one is preferable from the viewpoints of moisture permeability and compatibility with cellulose ester. The alcohol to be used in the polycarboxylic acid ester to be used in the invention may be one type or a mixture of two or more types. The acid value of the polyvalent carboxylate compound which can be used in the present invention is preferably 1 mgKOH/g or less, more preferably 0.2 mgKOH/g or less. It is preferable to control the acid value in the above range to suppress environmental changes in retardation. Further, the acid value means the number of milligrams of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample (the carboxyl group present in the sample). The acid value is determined in accordance with JIS K0070. The particularly preferred polycarboxylic acid ester compound is exemplified below, but the present invention is not limited thereto. For example, there are triethyl citrate, tributyl citrate, acetyl sulfonate 3-46-201226452 ethyl citrate (ATEC), acetyl tributyl citrate (ATBC), benzamidine III Butyl citrate, acetaminotriphenyl citrate, acetyltribenzyl citrate, dibutyl tartrate, dibutyl butyl tartrate, tributyl trimellitate, homo benzene Tetrabutyl tetracarboxylate and the like. (Ultraviolet absorber) The cellulose ester film of the present invention may contain an ultraviolet absorber. The ultraviolet absorber is intended to enhance durability by absorbing ultraviolet rays of 400 nm or less, and particularly preferably a transmittance of 370 nm or less at a wavelength of 370 nm or less, more preferably 5% or less, more preferably 2% or less. The ultraviolet absorber used in the present invention is not particularly limited, and examples thereof include an oxybenzophenone-based compound, a benzotriazole-based compound, a salicylate-based compound, a benzophenone-based compound, and a cyanoacrylate-based compound. A compound, a triazine-based compound, a nickel-salted salt-based compound, an inorganic powder or the like. For example, 5-chloro-2-(3,5-di-sec-butyl-2-hydroxyphenyl)-2H-benzotriazole, (2-2H-benzotriazol-2-yl)-6 - (straight chain and side chain dodecyl) _4·methyl phenol, 2-hydroxy-4-benzyloxy benzophenone, 2,4-benzyloxybenzophenone, etc. There are TINUVIN classes such as TINUVIN 109, TINUVIN 171, TINUVIN 2 3 4, TINUVIN 326, TINUVIN 3 27, TINUVIN 3 2 8, etc., all of which are commercially available from Ciba Specialty. The ultraviolet absorber which is suitable for use in the present invention is a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a triazine-based ultraviolet absorber, and particularly preferably a benzotriazole-based ultraviolet absorber and a diphenyl group. Ketone UV absorption -47- 201226452 Recipient. Further, a discotic compound having a compound such as a 1,3,5-triazine ring or the like can also be suitably used as an ultraviolet absorber. The cellulose ester film of the present invention preferably contains two or more kinds of ultraviolet-wound absorbers. Further, as the ultraviolet absorber, it is preferred to use a polymer ultraviolet absorber, and in particular, a polymer type ultraviolet absorber described in Japanese Patent Laid-Open No. Hei 6-1 48430 is preferred. The ultraviolet absorber is added as a UV absorber. It is dissolved 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, or added to the paste, or may be directly added thereto. The composition of the glue. Inorganic powders such as inorganic powders which are insoluble in organic solvents are used in organic solvents and cellulose esters using a dissolver or a sand mill, and are added to the dope after dispersion. The amount of the ultraviolet absorber to be used varies depending on the type of the ultraviolet absorber, the use conditions, and the like. However, when the thickness of the dried film of the polarizing plate protective film is 30 to 200 μm, it is preferably relative to the protective film of the polarizing plate. 〇. 5 to 10% by mass, more preferably 0.6 to 4% by mass. (Antioxidant) An antioxidant is also called a deterioration preventive agent. When the liquid crystal display device or the like is placed in a state of high humidity and high temperature, the cellulose ester film may be deteriorated. The antioxidant is, for example, a halogen ester-48-201226452 or a phosphate of a phosphate-based plasticizer in a cellulose ester film, which delays or prevents decomposition of the cellulose ester film, so that the cellulose ester film contains an antioxidant. good. Such an antioxidant is preferably a hindered phenol-based compound such as 2,6-di-t-butyl-P-cresol or pentaerythritol-tetrakis[3-(3,5-di-t-butyl- 4-hydroxyphenyl)propionate], triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexane Alcohol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(η-octylthio)-6- (4- Hydroxy-3,5-di-1-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, Ν1-hexamethylene bis (3.5 - Di-t-butyl-4-hydroxy-hydrocinnamylamine), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxyl Benzyl)benzene, tris-(3,5-di-t-butyl-4-hydroxybenzyl)-trimeric isocyanate, and the like. Particularly preferred is 2,6-di-t-butyl-P-cresol, pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], triethyl Glycol-bis[3-(3-t-butyl_5-methyl-4-hydroxyphenyl)propionate]. Further, for example, a metal inert agent such as &gt;1, ^['-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propenyl]fluorene or the like may be used. A phosphorus-based processing stabilizer such as tris(2,4-di-1 -butylphenyl) phosphate. The addition amount of these compounds is expressed by mass ratio with respect to the cellulose derivative, preferably '1?? 111~1.〇%' is more than 1〇~1〇〇〇??111. (Microparticles) In order to provide slipperiness to the cellulose vinegar film of the present invention, it is preferred that -49 to 201226452 contain fine particles. The primary particle diameter of the primary particles is preferably 20 nm or less, more preferably 5 to 16 nm, and particularly preferably 5 to 12 nm. These fine particles are preferably formed into a retardation film after forming secondary particles having a particle diameter of 0.1 to 5 μm, and preferably have an average particle diameter of 0.1 to 2 μm, more preferably 0.2 to 0_6 4〇1. Thereby, the unevenness of the surface of the film is formed to a height of 0.1 to 1.0^1, and the surface of the film can be appropriately smoothed. The average particle diameter of the fine particles used in the present invention is measured by a transmission electron microscope (magnification 50). 10,000 to 2 million times) The particles are observed, and one particle is observed, and the average particle diameter is measured as the primary average particle diameter. The apparent specific gravity of the fine particles is preferably 70 g/L or more, more preferably 90%. 2 00g / L, particularly preferably 100 ~ 200g / L. The larger the apparent specific gravity, the higher concentration of the dispersion can be made, so that the haze, agglomerate is better, as in the present invention, the viscosity of the solid concentration is higher The slurry is particularly suitable. The dispersing machine which does not use a medium is, for example, an ultrasonic type, a centrifugal type, a high pressure type, etc., but in the present invention, a high pressure dispersing device is preferred. The high pressure dispersing device is a composition in which fine particles and a solvent are mixed. The high-pressure passage of the thin tube allows the production of special conditions such as high shear or high pressure. When the high pressure dispersing device is used, for example, in a thin tube having a diameter of 1 to 2000 μm, the maximum pressure inside the device is preferably 9.807 MPa or more. good It is 19.613 MPa or more. At this time, if the maximum arrival speed is 100 m/sec or more, the heat transfer rate is preferably 420 kJ/hr or more. For example, the above-mentioned local pressure dispersion device, for example, Micro fluidics (:0^(^3) "011" ultra-high pressure homogenizer (trade name 11^(;1&quot;〇111^丨261&gt;) or -50-201226452 nanomizer company-made high-speed disperser, other Manton_Gaulin type high-pressure dispersing device, for example, izumif0〇d UHN-01 made by homogenizer, Sanhe Machinery Co., Ltd., etc. In addition, 'casting the slurry containing fine particles directly in contact with the casting support' can obtain a film with high slipperiness and low haze. After casting, after peeling, drying, and winding into a roll, a functional film such as a hard coat layer or an anti-reflective layer may be provided. During processing or shipment, the protective article is protected from contamination or static electricity. The packaging material is usually packaged and processed. The packaging material is not particularly limited as long as it achieves the above object, and is preferably one which does not interfere with the volatilization of the residual solvent of the film. Specifically, for example, polyethylene, polyester, polypropylene, Ni Polystyrene, paper, various non-woven fabrics, etc. It is more suitable for the mesh to be cross-linked. <Method for Producing Cellulose Ester Film> Hereinafter, a method for producing the cellulose ester film of the present invention will be described. The ester film may be a film produced by a solution casting method, or a film produced by a melt casting method. In the solution casting method, the cellulose ester film of the present invention is produced by the following steps: a step of dissolving a cellulose ester and an additive in a solvent to prepare a dope; a step of casting the dope to an infinitely extended endless metal support; a step of drying the casted dope into a net; and supporting by a metal Step of stripping; step of extending or maintaining width; step of further drying; step of winding up the film after completion. The step of preparing the glue is explained. The concentration of the cellulose ester in the glue is better than that of -51 - 201226452. The concentration of the cellulose ester is lower than that of the metal support. Therefore, when the concentration of the cellulose ester is too rich, the load during filtration increases. The filtering accuracy will be worse. The concentration of both of them is preferably from 1 3 to 35 % by mass, more preferably from 15 to 25 % by mass. The solvent used for the dope may be used singly or in combination of two or more kinds, but a good solvent of the cellulose ester is used in combination with a poor solvent, and it is preferably from the viewpoint of production efficiency, and when the solvent is large, the cellulose ester is used. The viewpoint of solubility is preferred. 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" and "lean solvent" means that the cellulose ester used alone is a good solvent, and those which are swollen or insoluble in a single state are defined as a poor solvent. Therefore, depending on the average degree of acetification of the cellulose ester (degree of substitution of ethyl thiol), the good solvent and the poor solvent may change. The good solvent to be used in the present invention is not particularly limited, and examples thereof include an organic halogen compound such as dichloromethane or dioxapentane, acetone, methyl acetate, methyl acetate methyl acetate and the like. More preferably, for example, dichloromethane or methyl acetate. Further, the poor solvent to be used in the present invention is not particularly limited, and for example, methanol, ethanol, η-butanol, cyclohexane, cyclohexanone or the like can be used. Further, it is preferred that the binder contains 0.01 to 2% by mass of water. The solvent used for dissolving the cellulose ester is dried by the film forming step, and the solvent removed by the film is recovered and reused. In the recovery solvent, a small amount of an additive added to a cellulose ester, such as a plasticizer, an ultraviolet absorber, a polymer, a monomer component, etc., may be contained in the case of -52 to 201226452, and even if such a component is contained, it may be reused. It can be purified and reused. A general method can be used for the method of dissolving the cellulose ester in the preparation of the above-mentioned dope. When combined heating and pressurization, it can be prevented by heating under normal pressure to a boiling point or higher, at a boiling point of a normal pressure of a solvent or higher, and at a temperature within a range in which the solvent does not boil under pressure, while stirring and dissolving while heating, it can be prevented. It is preferred to produce agglomerated undissolved matter called a gel or agglomerate. Further, a method in which a cellulose ester is mixed with a poor solvent and wet or swelled, and then a good solvent is further added for dissolution can also be used. The pressurization can be carried out by a method of pressurizing an inert gas such as nitrogen or by increasing the vapor pressure of the solvent by heating. The heating is preferably carried out from the outside, and for example, it is preferable that the jacket is easy to control the temperature. The heating temperature at which the solvent is added is preferably from a viewpoint of solubility of the cellulose ester, but when the heating temperature is too high, the pressure required is increased, and the productivity is deteriorated. The preferred heating temperature is 45 to 120 ° C, more preferably 60 to uot, and most preferably 70 to 105 ° 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. In order to remove insoluble matter, etc., it is preferable that the absolute filtration accuracy is small, but the absolute filtration accuracy is too small, and the filter material is likely to be clogged. -53 - 201226452. Therefore, the filter material with an absolute filtration accuracy of 0.008 mm or less is preferable, the filter material of 0.00 1 -0.008 mm is more preferable, and the filter material of 0.003 to 0.006 mm is more preferable. The material of the filter material is not particularly limited, and a general filter material, preferably polypropylene, can be used. A plastic filter material such as Teflon (registered trademark) or a metal filter material such as stainless steel is preferred because it does not cause fiber detachment or the like. It is preferred to remove and reduce impurities contained in the cellulose ester of the raw material by filtration, especially bright foreign matter. The term "bright spot foreign matter" refers to a state in which two polarizing plates are arranged in a state of orthogonal polarizers, and an optical film or the like is provided therebetween, and light is irradiated from one side of the polarizing plate and viewed from the other side of the polarizing plate. A point (foreign matter) that is visible when light is leaking, and the number of bright points having a diameter of 0.01 mm or more is preferably 200 or less. More preferably, it is 100 pieces/cm2 or less, more preferably 50 pieces/cm2 or less, more preferably 0~10 pieces/cm2 or less. In addition, the highlights below 0.01 mm are also preferred. The filtration of the glue can be carried out according to the usual method, at a temperature above the boiling point of the solvent, and under the temperature range in which the solvent does not boil under pressure, the method of filtering while heating, and the difference of the filtration pressure before and after the filtration ( It is preferable that the rise of the differential pressure is small. The preferred temperature is 45 to 120 ° C, more preferably 45 to 70 ° C, and even more preferably 4 5 to 5 5 ° C. It is better to have a smaller filtration pressure. The filtration pressure is preferably 1.6 MPa or less, preferably 1.2-54 to 201226452 MPa or less, and more preferably 1.0 MPa or less. Here, the casting of the dope is explained. The metal support in the Cast step, preferably the surface is mirror-finished, and the metal support may use a stainless steel strip or cast, and the surface is plated. The width of the casting can be 1~4 m. The surface temperature of the metal support in the casting step is from -50 ° C to the temperature of the boiling point of the solvent. The higher temperature can increase the drying speed of the web, so it is better, but the mesh is too high. It will foam, or the flatness may deteriorate. The preferred support temperature is 0 to 55 ° C, more preferably 25 to 50 ° C. Alternatively, it is also preferable to use a method in which the web is gelled by cooling and the separator is peeled off 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, 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 efficiently transferred by using warm water, the time until the temperature of the metal support reaches a certain value is short, which is preferable. When using warm air, sometimes winds with a higher temperature than the target temperature are used. In order to show good planarity of the cellulose ester film, the residual solvent amount when the metal support peels off the mesh is preferably from 10 to 150% by mass, more preferably from 20 to 40% by mass or from 60 to 130% by mass. %, particularly preferably 20 to 30% by mass or 70 to 1% by mass. In the present invention, the amount of residual solvent is defined by the following formula. Residual solvent amount (% by mass) = {(1^-&gt;4)/:^丨\100 In addition, the lanthanide is a sample taken at the time of manufacture or after manufacture - any -55-201226452 Mass, N is the mass after heating at 1 1 5 °C for 1 hour. Further, in the drying step of the cellulose ester film, the mesh is peeled off from the metal support and dried, and the amount of the residual solvent is preferably 1% by mass or less, more preferably 0.1% by mass or less. Preferably, it is less than 0.01% by mass. In the film drying step, generally, a roll drying method (a plurality of rolls arranged in the upper and lower sides is used to alternately pass the web through drying) or a web in which the web is conveyed while drying is used. When the cellulose ester film of the present invention is produced, it is particularly preferred to extend in the width direction (lateral direction) by a tenter method of holding both ends of the mesh by a jig or the like. The peeling tension is preferably 300 N/m or less. The means for drying the web is not particularly limited. Generally, hot air, infrared rays, heating rolls, microwaves, and the like can be used, but the hot air is preferred in the mesh based on the simple viewpoint. The drying temperature in the drying step is preferably in a stepwise rise at 40 to 200 °C. The film thickness of the cellulose ester film is not particularly limited, and 10 to 200 μm can be used. The film thickness is particularly preferably 10 to ΙΟΟμιη, more preferably 20 to 60 μm. The cellulose ester film of the present invention is a film having a width of 4 m, particularly preferably 1.4 to 4 m, particularly preferably 1.6 to 3 m. If it is more than 4 m, it is difficult to transport. In order to impart the retardation 値R〇 and Rt to the cellulose ester film as described below, the cellulose ester film is constituted by the present invention, and it is preferable to control the refractive index by controlling the stretching tension and extending the operation. For example, by reducing or increasing the tension in the length direction, the -56-201226452 delay 値 can be changed. Further, it is preferable to perform the two-axis extension or the one-axis extension successively or simultaneously with respect to the longitudinal direction of the film (film formation direction) and the direction orthogonal thereto in the film plane, that is, for the width direction. The stretching ratios of the mutually orthogonal two-axis directions are preferably in the range of 〇·8 to 1.5 times in the casting direction and the range of 1.1 to 2.5 times in the width direction, preferably in the casting direction of 〇.8~ 1.0 times, the width direction is in the range of 1.2 to 2.0 times. The extension temperature is preferably from 1 2 0 ° C to 2 0 0 ° C, more preferably from 150 ° C to 2 0 0 t, more preferably more than 150 ° C and below 19 ° C. Perform the extension. The residual solvent in the film is preferably from 20 to 0%, more preferably from 1 to 5 %. Specifically, it is preferred to carry out the stretching at a temperature of 1 5 5 ° C at a residual solvent of 11%, or at a residual solvent of 2% at 155 t. Further, it is preferred to carry out the stretching at a residual solvent of 110% at 160 ° C, or at 160 ° C, at a residual solvent of less than 1%. The method of extending the mesh is not particularly limited. For example, there is a method of imparting a peripheral speed difference to a plurality of rolls, and in the longitudinal direction by using a difference in the circumferential speed of the rolls, the ends of the mesh are fixed by a jig or a needle, and the distance between the jig or the needle is extended. The method of extending in the longitudinal direction is similarly a method of extending in the lateral direction, extending in the lateral direction, or expanding in the longitudinal and lateral directions and extending in both the longitudinal and lateral directions. Of course, these methods can also be used in combination. Further, in the case of the so-called tenter method, when the portion of the jig can be driven by linear driving, smooth extension can be performed, and the risk of breakage or the like can be reduced, which is preferable. -57- 201226452 These width-maintaining or lateral extensions in the film forming step are preferably carried out by a tenter, and may also be a pin tenter or a clamp tenter. When the retardation axis or the phase axis of the cellulose ester film of the present invention exists in the film surface and the angle formed by the film formation direction is Θ1, it is preferable that Θ1 is -1° or more and +1° or less. 0.5° or more and +0.5° or less are more preferable, and those of -0.1% or more and +0.1° or less are more preferable. This Θ 1 is defined by the alignment angle, and the measurement of el can be measured using an automatic birefringence meter KOBRA-2 1 ADH (Prince Measurement Machine). When Θ1 satisfies the above various relationships, respectively, high brightness can be obtained in the display image, which helps to suppress or prevent light leakage, and faithful color reproduction can be obtained in the color liquid crystal display device. &lt;Physical properties of the cellulose ester film&gt; The moisture permeability of the ester film is 40 ° C, 90% RH, preferably 300 to 1 800 g / m 2 · 24 h, more preferably 4 0 0 ~ 1 500 g / m 2 · 24 h, Very good for 40~1 3 00 g/m2 · 24h. The moisture permeability is measured in accordance with the method described in JIS Z 0208. The cellulose ester film of the present invention preferably has an elongation at break of from 5 to 80%, more preferably from 10 to 50%. The visible light transmittance of the cellulose ester film of the present invention is preferably 90% or more, more preferably 93% or more. The haze of the cellulose ester film of the present invention is preferably less than 1%', more preferably 0 to 0.1%. Further, the cellulose ester film of the present invention can be further subjected to a coating layer of -58 to 201226452 to obtain a wider range of delayed enthalpy. &lt;Phase Difference 値&gt; The in-plane retardation Ro(Ro) and the retardation in the thickness direction of the cellulose ester film of the present invention (when RO is used as a polarizer protective film, 0SRO and Rt$70 nm are preferable. It is 0SR〇S30nm and 0SRtS50nm, more preferably 0SR〇'10nm and 0$Rt$30nm. The cellulose ester film of the present invention is preferably used as a retardation film, in which case 30 $ Ro $ 1 00 nm and 70 S Rt S 400 nm More preferably, it is 35 S Ro $ 65 nm and 90$RtS 180 nm. In addition, the variation or distribution of Rt is less than ±50%, preferably less than ±30%, and less than ±20%. 15% is better, less than ± 10% is better, less than ± 5% is better, and particularly preferably less than ± 1%. The best is no change of Rt. In addition, the delay 'Ro ' Rt can be obtained by the following formula .

Ro=(nx-ny)xd

Rt=((nx+ny)/2-nz)xd where the thickness (nm) of the d-type film and the refractive index nx (the maximum refractive index in the plane of the film, also referred to as the refractive index in the direction of the slow axis), Ny (in the film plane, the refractive index in the direction perpendicular to the slow axis), nz (the refractive index of the film in the thickness direction). The delays Ro(Ro ) and (Rt) can be measured using an automatic complex refractometer. For example, KOBRA-21ADH (Prince Measurement Machine (share)) is obtained at a wavelength of 5 90 nm in an environment of 23T:, 55% RH. -59-201226452 &lt;Surface activation treatment&gt; The cellulose ester film of the present invention can be subjected to surface activation treatment, and the surface activation treatment means that the base can be applied to the side of the cellulose ester film where at least the photon is present. Saponification treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, bright discharge treatment, active plasma treatment, laser treatment, ozone oxidation treatment, and the like. Thereby, the surface free energy of the cellulose ester film is improved, and the contact angle with respect to pure water can be lowered. Further, a method of adjusting the surface free energy, for example, a method of applying a hydrophilic layer on the side where the photon is present. In the surface activation treatment of the cellulose ester film of the present invention, the alkali saponification treatment is easy to control the surface free energy, and therefore it is preferred to use a sodium hydroxide or potassium hydroxide solution for the alkali saponification treatment. &lt;Contact angle&gt; The method of measuring the contact angle is, for example, a method in which the contact angle measurement liquid is pure water, and a pure water is placed in a clean room at 23 ° C and 5 5% RH by a syringe. On the surface, the angle after dropping for 3 seconds was measured using a contact angle measuring instrument (manufactured by FIB LO Co., Ltd.) as a contact angle. &lt;Polarizing Plate&gt; The cellulose ester film of the present invention can be used as a polarizing plate protective film for a polarizing plate, and can be used for a liquid crystal display device using the polarizing plate. The polarizing plate of the present invention is preferably a polarizing plate in which the cellulose ester film of the present invention is used as a polarizing plate protective film and adhered to at least one side of a polarizer. The liquid crystal display device of the present invention is preferably bonded to the polarizing plate of the present invention via an adhesive layer on at least one of the liquid crystal cell surfaces -60 to 201226452. 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 subjected to alkali saponification treatment, and at least one surface of the polarizing film prepared by immersing and stretching in an iodine solution is adhered to each other using a completely saponified polyvinyl alcohol aqueous solution. Further, it is preferred that the other protective film of the polarizing plate can be bonded even if the cellulose ester film is used on the other surface. For example, commercially available cellulose ester films (eg, Konica Minolta KC8UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC4UE, KC8UE, KC8UY-HA, KC8UX-RHA, KC8UXW-RHA-C, KC8UXW) can be used. -RHA-NC, KC4UXW-RHA-NC, and the above is manufactured by Konica Minoltaopto Co., Ltd.) 0 In the polarizing plate protective film used on the surface side of the liquid crystal display device, it is preferable to use an anti-glare layer or a transparent hard coat layer. It has an anti-reflection layer, an antistatic layer, an antifouling layer, and a back coat layer. The polarizer of the main constituent elements of the polarizing plate refers to an element which passes only the light of the deflecting surface in a certain direction. A representative polarizer-based polyvinyl alcohol-based polarizing film which is known now, is a polyvinyl alcohol-based polarizing film. Iodine dyers and dichroic dyes. The polarizer is formed by forming a film of a polyvinyl alcohol aqueous solution, stretching it by one axis, and dyeing it or after performing one-axis stretching after dyeing, preferably after durability treatment with a boron compound. The film thickness of the polarizer is preferably 5 to 3 〇μιη, and particularly preferably 10 to 20 μm. In addition, the content of the ethylene unit described in JP-A-2003-248123, JP-A-2003-342 3 22, etc., 1 to 4 mol%, polymerization degree 2000 to 4000, and degree of saponification can also be used. 99.0 to 99.99 mol% of ethylene-denatured polyvinyl alcohol. Among them, an ethylene-modified polyvinyl alcohol film having a hot water cutting temperature of 66 to 73 ° C is preferably used. The polarizer of the ethylene-modified polyvinyl alcohol film is excellent in color performance and durability in addition to excellent polarizing performance and durability, and is particularly suitable for a large liquid crystal display device. The polarizer obtained as described above is generally provided with a protective film as a polarizing plate on both sides or one side thereof, and an adhesive used for bonding, for example, a PVA-based adhesive or a urethane-based adhesive. Agents and the like, among which PVA-based adhesives are preferably used. &lt;Liquid Crystal Display Device&gt; 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 and polarizing plate of the present invention can be used for liquid crystal display devices of various driving methods such as STN, TN, OCB, HAN, VA (MVA, PVA) 'IPS, OCB, and the like. A VA (MVA, PVA) type liquid crystal display device is preferred. 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 has less environmental variation, and which is excellent in visibility such as color unevenness of light leakage and front contrast. [Embodiment] Embodiments Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. Example 1 &lt;Production of Cellulose Ester CE-1&gt; 16 parts by mass of sulfuric acid, 260 parts by mass of anhydrous acetic acid, and 420 parts by mass of acetic acid were added to 100 parts by mass of cellulose, and the mixture was stirred and heated at room temperature for 60 minutes. The acetation reaction was carried out at 60 ° C and maintained at this temperature for 15 minutes. Next, after neutralizing sulfuric acid by adding an acetic acid-water mixed solution of magnesium acetate and calcium acetate, water vapor was introduced into the reaction system, and maintained at 60 ° C for 120 minutes to carry out saponification and ripening treatment. Then, it was washed with a large amount of water and dried to obtain a cellulose ester CE-1. The obtained cellulose ester CE-1 had a hydroxyl residue (DR) of 0.20, and when the number average molecular weight was Μη and the weight average molecular weight was Mw, Mn = 80000 and Mw/Mn = 2.4. The hydroxyl residue (DR), the amount of calcium, the amount of magnesium, the amount of acetic acid, and the molecular weight were obtained according to the methods described above. &lt;Production of Cellulose Ester CE-2-CE-18&gt; The cellulose ester CE was appropriately changed except that the hydroxyl residue (DR), the amount of calcium, the amount of magnesium, and the amount of acetic acid of the cellulose ester were as shown in Table 1. In addition to the production conditions of -1, cellulose esters CE-2 to CE-18 were produced in the same manner. -63- 201226452 [Table 1] Cellulose ester No. Substitution degree hydroxyl residue (DR) Number average molecular weight (Hn) Μι»/Μη CE- 1 2.80 0.20 80000 2.4 CE- 2 2'60 0.40 72000 2.8 CE-3 1.90 1.10 45000 2.1 CE — 4 2.10 0.90 43000 2.5 CE- 5 2.41 0.59 48000 2.8 CE- 6 2.41 0.59 35000 1.9 CE — 7 2.41 0.59 40000 1.9 CE-8 2.41 0.59 65000 2.8 CE-9 2.41 0.59 62000 3.1 CE —10 2.43 0.57 37000 2.1 CE —11 2.43 0.57 43000 2.7 CE—,2 2.43 0.57 53000 2,9 CE-13 2.43 0.57 48000 3.1 CE —14 2.43 0,57 61000 2.7 CE-15 1,95 1.05 78000 3.1 CE-16 2.42 0.58 54000 3.0 CE-17 2.45 0.55 37000 2.6 CE-I8 2.45 0.55 66000 2.6 &lt;Production of cellulose ester film 101 to 137&gt; (Production of cellulose ester film 1 0 1) &lt;Microparticle dispersion liquid&gt; Microparticle (AEROSIL) R812 Japan AEROSIL Co., Ltd.) 1 part by mass of ethanol 89 parts by mass The above was stirred and mixed for 50 minutes in a dissolver, and then dispersed by a Manton-Gaulin homogenizer. &lt;Microparticle-added liquid&gt; After the cellulose ester CE-1 was added to a dissolution tank containing methylene chloride, and the mixture was completely dissolved by heating, the filter paper made of the filter paper (stock) was used -64-201226452

No. 244 filtration. The filtered cellulose ester solution was thoroughly stirred while the fine particle dispersion was slowly added. Further, the particles are dispersed by an attritor to have a particle size of the secondary particles of a predetermined size. Further, it was filtered with FINEMETNF manufactured by Nippon Seisaku Co., Ltd. to prepare a fine particle addition liquid. Methylene chloride 99 parts by mass Cellulose ester CE-1 4 parts by mass Microparticle dispersion 1 1 part by mass The main gum of the following composition was prepared using cellulose ester CE-1. First, dichloromethane and ethanol are added to a pressurized dissolution tank. The cellulose ester CE-1 was placed in a pressurized dissolution tank containing a solvent while stirring. This was heated, stirred and completely dissolved, and then added with a hydrolysis inhibitor (A) (Compound No. 3) 'phase difference adjuster (B) to dissolve. The main filter slurry was prepared by using the filter paper No. 244 made of the filter paper (stock). 2 parts by mass of the fine particle addition liquid was added to 100 parts by mass of the main dope, and the mixture was thoroughly mixed using an inline mixer (IN-LINE MIXER) (Toray static in-line mixer Hi-Mixer, SWJ), and then the belt was used. The casting device was cast onto a stainless steel belt support having a width of 2 m. On the stainless steel belt support, the solvent was evaporated until the amount of residual solvent became 1 1 〇%, and it was peeled off from the stainless steel belt support. At the time of peeling, the tension was applied to extend the MD (MD) stretching ratio by 1.02 times, and then the both ends of the fiber web were held by a tenter, and the stretching ratio in the width (TD) direction was 1.25 times. The amount of residual solvent at the beginning was 30%. After the extension, the width was maintained for a few seconds, and the tension of the width -65 - 201226452 was relieved. Then, the width was kept 'drying at the first minute set at 125 ° C, and the width was 1.5 m, and the end portion was made. The cellulose of the present invention having a film thickness of 40 μm η of 8 μπι embossed &lt;composition of the main gum liquid&gt; dichloromethane cellulose ethanol ester CE-1 hydrolysis preventing agent (A) (compound Ν 〇. 3 ) phase difference adjusting agent (B) (Production of Cellulose Ester Films 102 to 137) The cellulose ester film 102 shown in Table 2 and Table 3 was changed to the cellulose ester film 102 as shown in Table 2 except that the cellulose ester and the hydrolysis prevention difference adjusting agent (B) shown in Table 1 were changed. ~137. 3 Drying zone transfer 30 There is a 1 cm wide, high ester film 101. 300 parts by mass 30 parts by mass 100 parts by mass 7 parts by mass 6 parts by mass of the agent (A), phase The same as the above -66-201226452 [s]

Comparative Example I 1 Comparative Example I 1 The present invention | 丨 The present invention 丨 1 The present invention II The present invention 1 The present invention 1 1 The present invention I 丨 The present invention 1 I The present invention I The present invention 1 The present invention 丨Invention I Comparative Example The present invention The present invention|The present invention| Relational formula (2) 16.00" 110.00 | CO CO | 4.89 I &lt;〇r* s Bub | 6.78 I | 4.36 I CNJ o 卜&lt;r- 5-.85) CM 〇r- LO 卜*—· CO 6.90 卜 | 3.64 | CO &lt;〇&lt;75 CO Relationship (1) I '4.69 I | 4.69 I 1 4-69.1 1 4·69 I &lt ;n ιύ 甘to in 06 5 Ο) | 4.69 | | 4.69 j cr&gt; | 6.40 j to in 00 [8.49 V- σ&gt; 1 4_69 1 I 4,69 1 —4·69_— | 4.69 I | 2.65 I 00 Ir&gt; CO CO 蘅m content W(8) 1〇CM iD C4 o inch to Cvi 1/) CM o CJ 〇Γ0; ιή CM in CO in M tn ▼ o cn ΙΛ ip CO o CO in &lt;〇in in 畤CO CM o &lt;N 1 U&gt; in in ΙΛ in in in U&gt; ID 卜卜 in to in in in 卜• *-· ΙΛ in m in in m in in tn IO 卜 in in 例 to exemplify compound IB —16 I ID 丁丁丁CD %Ω T CO CO T cn 卜丁ω 00 Τ C0 ID T ω &quot; or T m iO CQ j——B-.19 | r- T (Ώ o T cn 00 T CQ u> T CO butyl ω CO butyl CQ NT butyl CO Tinuvin 328 tn I ca hydrolysis inhibitor &lt; A ) iW 仞菖 &lt;0 o * - bis σ &gt; Γ 0 〇 σ &gt; o CO 〇o 2 o 々〇 05 O Oi CL g&gt; ca o CM 〇o »&quot;· CM 〇CV4 〇CVI ο CM 〇ra o 〇*—» CM 〇CM 〇〇C\J o CSJ 〇CM p fr~ (Μ CM CM o &quot;»—· ra ◦ CVJ oo cn exemplified compound l〇I &lt; in 1 &lt; in 1 &lt; in 1 &lt; A — 5 ιη 1 &lt; in 1 &lt; in 1 &lt; IO I &lt; in &lt; tn I &lt; in &lt; in 1 &lt; in &lt; to 1 &lt; in 1 &lt ; in I &lt; in &lt; in I &lt; In I &lt; In relation (3) Ratio i〇σ&gt; LO »-· 5 O CO 00 o CM CM T-1 30.50 I cn CM in csj 00 CO &lt;5 f 〇CO CM 00 CO CM isJ CO 24.00 s ΓΟ CSJ ΓΟ CM acetic acid amount ppm or» 〇CO tn iO g 卜 S U&gt;σ&gt; 00 00 CM cn CO 00 in in tn cn o «—* s &lt;M 00 ( OK CM CO cvi CO 1 i£&gt; in s O) un 〇0 CM σ&gt; CO σ&gt; in CM to CO r- 卜m 5 卜O) CO in tr&gt; Ro CM IO IO gt&gt; CM CO 00 CM OJ in mo CM IO in */) Ca amount ppm Irt m jn in CM ο 卜 g CO ΙΛ 兮mr* C4 o CO CM in CO 00 o ·- 〇鼹1 0.20 0.40 o •r— 0.90 0.59 0.59 o in p | 0.59 I 丨0.59 | C; o K o In 〇| 0.57 I | 0.57 j ·—· 0.58 0.55 0.55 0.57 K o Cellulose Ester No. 1 Ui CM 1 UJ CO i ui inch I UJ in 1 UJ ¢0 1 UJ 卜 1 UJ o 00 1 UJ σ&gt; ! UJ 0 ¥-· 1 UJ »—· ·— 1 Ui CM r*~ ! ω CO T tu o 1 LU in 1 LU CE-16 卜 i UJ o co '*-· I UJ xr t— I Ui sr I UJ o mm - 芸 it芸 魉 5 ss «r·* S g V&quot;· &lt;〇ο sggr- o — w^· CM CO r*· «« m IF — o »» · r* 00 CTi S &lt;as.)x((s\(s) : si s : _bh({a)dB0l)l(( v)dc»03 : (1) 静雄汇§ &quot; s -67- 201226452 [8] Killing Comparative Example 1 1 Comparative Example 1 I Present Invention II Comparative Example I 1 Comparative Example 1 [Comparative Example 1 I Comparative Example II The present invention I Translated Invention 1 [Invention 1 丨 Inventive 1 1 Invention 1 1 Invention 1 1 Invention 1 1 Invention 1 1 Invention 1 I Invention I Relationship (2) $ CO 1 4.09 1 00 in 1 7·02 1 〇c&gt; i n &lt;N4 σ&gt; 1 7·72 1 in in in | 5.85 j «·» i〇in 卜.97.....1 | 5.85 1 | 6.50 | | 7.63 | 丨Relationship (1) ST [0.84| I 5.32丨2.20| 1 10.2l| 丨4.69丨| 4.69| | 4;69| | 6.4〇| 1' 8.56| '5 ·· O} | 4.69| | 4-.38j .4.05 5+·79| o 00 in I 7.85| GQ mm W1 Remaining S $1 » in 兮o CO &lt;N in to in CM CM CM o to o (O in CM in C0 \n CO o to in CM ο cn o ro 卜 ·Μ· CO · CL σ&gt; ο ΙΛ 1〇in m O) in in xr in ΙΛ in in in XT r&gt; 卜 in in in uo i£&gt; c〇ro ca 鼷m exemplified compound &lt;〇1 CQ [B- 16 | I compound aj to ···» 1 GO &lt;7i ·- 1 CO 1 B-1.6 I | B —16 I B-16 1 B—9 i Bu op op ω 7 CO *·〇I ω | b 1 |Compound c | TinuvinP L EPEG Hydrolysis inhibitor (A) Content W(A) 1〇GO 卜o 〇oo ID ow^· w^· ο w*» ψ^· o O 00 m GO ooo | in 00 CM rr r* o CM o CNi d 04 〇CSI d »·· CM d 10.2. CM o 03⁄4 a; CO 〇CM 〇CM d exemplified compound α. ο. a. s u&gt;&lt; CM 1 &lt;&lt; in &lt; in &lt; in &lt; If) 1 &lt; i n I &lt; in &lt; to &lt; CD tz 〇L Tinuvin405 in 1 &lt; in &lt; in 1 &lt; relation (3) ratio CO CM &lt;n CNJ Γ0 CM r〇CM fO &lt;Ni CO CM ro CNi 00 CSI ro CM Γ0 ro CSJ CO CM ro CSI CO CM cr&gt; Γ4 ro ca CO cJ acetic acid ΡΡΠ CM CO &lt;Si CO CM CO CM CO CM m (SI CO CM ro ΓΜ CO CM CO OJ 00 CM ro CM CO &lt;NJ CO CNi Γ0 N ro CM CO CM CO fc 1 in in *·&quot;· ur&gt;v*&quot;· in m in in m in in iO ·*·- in in r — xn « MB ug ppm ir&gt; m in in LO in in in l〇in ur&gt; \n in IX) L〇xn Ca amount PPffl, ioooooo ό oo 〇〇〇ooooo off 1 5 〇vn o tn o in 〇in o 0.57 | 0.57 j K o K o A5ll in 〇i 0.57 | K o u&gt; o K o 0.57 K o Cellulose Ester No. 1 UJ Inch UJ 々T uj •&lt;r T LU -«r T UJ rr UJ «*·» I UJ 丁LU o } UJ o '«j· 1 UJ «Τ» 1 UJ *« 1 UJ ·-» 1 LiU 〇XT UJ 1 o •r— 1 UJ 1 UJ cellulose ester film No. 5 CM CO (SJ &lt;5 m &lt; N4 IT—i〇&lt;M CO CSJ O) CJ 沄r— CM CO 00 CO Ψ—in CO (O CO CO w-· (if \ox((s/) SM ) : s^_醒_娜:_βΗ { (g)a.cl&gt;01)l((v)l'a-'601) : (0 wipe awake __竑:_|&lt;83 -68- 201226452 Further, the details of each compound described in the table by abbreviations are as follows. TPP: triphenyl phosphate BDP: biphenyl diphenyl phosphate PET B: pentaerythritol tetrabenzoate EPEG: ethyl decyl ethyl glycolate [Chemical 18] Compound a Compound b

Tinuvin405 (made by diba iapan)

UnuvinP (manufactured by Ciba Japan)

HO

<<Evaluation item, evaluation method>> The following evaluation was performed using the obtained cellulose ester film. -69- 201226452 (Delayed) The delay 値R ο, R t is obtained by the following equation.

Ro=(nx-ny)xd

Rt = ((nx + ny)/2-nz)xd where the thickness of the d-type film (ηηι), the refractive index nx (the maximum refractive index in the plane of the film, also referred to as the refractive index in the direction of the slow axis), Ny (in the film plane, the refractive index in the direction perpendicular to the slow axis), nz (the refractive index of the film in the thickness direction). The delays R(R 〇 ) and ( R t ) can be measured using an automatic complex refractometer. For example, using KOBRA-21 ADH (Prince Measurement Machine (share)), it is obtained at a wavelength of 590 nm in an environment of 23 ° C and 55% RH. (Internal haze 値) After the produced cellulose ester film was conditioned for 5 hours or more in an environment of 23 ° C and 55% RH, the internal haze 评价 was evaluated by the following method. First, the blank haze 1 of the measuring instrument other than the film was measured. 1. Drop a drop (0.05 ml) of glycerin onto the cleaned slide. At this time, take care to avoid air bubbles in the droplets. If the glass is visually judged to be clean, it may be a polluter, so it must be washed with a lotion (refer to Figure 1). 2. Cover the cover with a cover slip. Even if the coverslip is not pressed, the glycerin will expand. 3. Set on the haze meter and measure the blank haze1. -70- 201226452 Receiver, according to the following steps to determine the haze 2 of the sample. 4. Drop glycerin onto the slide (0.05 ml) (see Figure 1). 5. The sample film of the measurement is placed on the state in which the bubble is prevented from entering (see Fig. 2). 6. Drop glycerin onto the sample film (0_05 ml) (see Figure 3). 7. Place a coverslip on it (see Figure 4). 8. The laminate prepared as described above (cover glass/glycerin/sample film/glycerin/carrier glass from above) was placed on a haze meter, and haze 2 was measured. 9. Calculation (haze 2) - (haze 1) = (internal haze of the cellulose ester film of the present invention).

The slides and glycerin used in the above measurement are as follows. Glass: MICRO SLIDE GLASS S9213 MATSUNAMI Glycerin: Kanto Chemical Deer Grade (Purity > 99.0%) Refractive Index 1.47 (Erosion Evaluation) Place the cellulose ester film in a high-temperature, high-humidity atmosphere at 80 °C and 90 % RH. After 000 hours, the surface of the film was evaluated for exudation. ◎: The surface of the film is completely oozing. There is a slight exudation on the surface of the film, but there is no problem in use. △: The surface of the film is completely exuded. X: The surface of the film is completely exuded. -71 - 201226452 (Haze for temperature and humidity changes) Change) The cellulose ester film to be produced is stored in a high-temperature and high-humidity atmosphere of 60t and 90% RH for 1 to 20 hours, and the haze change is evaluated. One film sample is measured, and NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd. is used. Measured in accordance with JIS-K7136. ◎: The haze change is less than 10% 〇: The haze change is 10% or more and less than 30% △: The haze change is 30% or more and less than 50% X: The haze change is 50% or more ( The phase difference 温 change in temperature and humidity change) The phase difference between the prepared cellulose ester film and the environment under the conditions of 23 ° C, 55% RH and 5 (TC 20% RH, humidity control for 5 hours or more) (Rt) ratio, the phase difference 値 is evaluated. ◎: The phase difference 値 does not change by 5% 〇: The phase difference 値 varies by 5% or more and does not reach 1 5%. △: The phase difference 値 varies by more than 1 5%. 24% X : phase difference 値 fluctuation was 25% or more &lt;Production of polarizing plate&gt; Using the obtained cellulose ester film 1〇1 to 137, a polarizing plate was produced by the following method. A polyvinyl alcohol film having a thickness of 120 μm was used. One-axis extension (temperature 1 10 ° C, extension magnification 5 times) was immersed in an aqueous solution of iodine 0.075 g, potassium iodide 5 g, -72-201226452 water 100 g, and then immersed in It was made into an aqueous solution of 6 g of potassium iodide, 7.5 g of boric acid, and 100 g of water, and washed with water and dried to obtain a polarizer. Then, according to the following steps 1 to 1 5, a polarizing plate can be prepared by using a polarizer and the cellulose ester film 101-137, and a konicaminoltatac KC8UY made of konicaminoltaopto as a polarizing plate protective film. Step 1: The cellulose ester film 101 to 137 is at 50 °. Immersed in a 2 mol/L sodium hydroxide solution for 30 seconds, then washed with water and dried to obtain a surface-saponified cellulose ester film. Step 2: The above-mentioned polarizer was solid content of 2% by mass of polyvinyl alcohol. Then immersing in the agent tank for 1~2 seconds. Step 3: Gently wipe and remove the excess adhesive attached to the polarizer in step 2, and load it onto the cellulose ester film treated in step 1, and then on the inner side. The cellulose ester film is disposed. Step 4: The cellulose ester film laminated in step 3 is 1 11~1 3 7 and the polarizer and the inner surface side cellulose ester film are conveyed at a pressure of 20 to 30 N/cm 2 . The bonding is carried out at about 2 m/min. Step 5: The sample prepared in step 4 is bonded to a sample of the cellulose ester film 101 to 137 and the inner surface side cellulose ester film in a dryer at 80 ° C, and dried. 2 minutes to make a polarizing plate. "Evaluation of polarizing plate" (No Evaluation) -73- 201226452 The polarizing plate obtained by the above method is cut into 5 〇〇 mm square, and after 1 2 〇 hours in 60 ° (:, 90% R Η high temperature and high humidity atmosphere) 'The orthogonality was formed on the light box, and the degree of polarization unevenness was visually evaluated. ◎: The unevenness of the polarization was not observed. 偏 The unevenness of the polarization was not observed with the naked eye. △: Although the polarization is uneven, the use is not used. No problem on X: There is a problem with the quality of the display as shown in Table 4 below. • 74- 201226452 [Table 4] Cellulose Ester Film No. Film Evaluation Polarizing Plate Evaluation Liquid Crystal Display Device Evaluation Remarks Ro (nm) Rt (nm) Internal Haze Phase Difference 値 Variable Haze Variation Permeation Uneven Viewing Angle 101 12 48 0.12 XX Δ Δ X Comparative Example 102 32 69 0.06 Δ X Δ Δ Δ Comparative Example 103 68 158 0.06 XXXXX Comparative Example 104 60 146 0.01 ◎ ◎ ◎ ◎ ◎ The present invention 105 55 137 0.05 〇〇 ◎ 〇〇 The present invention 106 51 139 0.02 ◎ 〇〇〇 ◎ The present invention 107 53 135 0.04 ◎ 〇〇〇 ◎ The present invention 108 55 132 0.03 〇 ◎ 〇〇〇 The present invention 109 58 133 0.01 ◎ ◎ © ◎ ◎ The present invention 110 55 135 0.01 〇 ◎ ◎ 〇〇 Invention 53 1 53 120 0.03 〇〇〇 ◎ 〇 Π 55 55 55 55 55 55 55 55 55 55 55 55 55 55 55 55 55 55 55 55 113 113 113 113 113 113 113 113 113 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 115 115 115 115 115 115 115 115 115 115 115 Δ XXX Comparative Example 116 55 137 0.03 〇 ◎ 〇〇〇 The present invention 117 50 137 0.04 〇〇 ◎ 〇〇 The present invention 118 55 133 0.01 〇 ◎ 〇〇〇 119 43 128 0.02 〇〇〇〇〇 The present invention 120 56 137 0.02 ◎ 〇〇〇 ◎ The present invention 121 38 125 0.07 XXXXX Comparative Example 122 42 no 0.06 XXXXX Comparative Example 123 45 143 0.01 ◎ ◎ ◎ ◎ ◎ The present invention 124 55 137 0.22 X Δ XXX Comparative Example 125 43 Ί33 0.19 XX Δ Δ X Comparative Example 126 55 137 0.32 Δ X Δ Δ Δ Comparative Example 127 57 141 0.10 X Δ XXX Comparative Example 128 55 136 0.01 ◎ ◎ ◎ ◎ ◎ The present invention 129 49 125 0.02 ◎ ◎ 〇 ◎ ◎ 51 130 51 130 130 130 130 131 131 131 131 131 131 131 131 131 131 131 131 131 131 131 131 131 131 132 132 132 132 132 132 132 132 132 132 132 132 132 132 132 132 132 132 132 132 132 132 132 132 132 132 132 132 132 132 132 132 132 132 132 132 〇The present invention 134 50 133 0.05 〇〇〇〇〇 The present invention 135 50 135 0.03 〇〇 ◎ 〇〇 the present invention 136 47 138 0.04 〇〇〇〇〇 the present invention 137 48 122 0.04 〇 ◎ 〇〇〇 The present invention from Table 4 As a result, it was found that the cellulose ester film of the present invention has sufficient phase difference 値, and the internal haze is low, the phase difference 値 varies, the haze fluctuation, and the bleed out property. It is excellent, and the polarizing plate of the present invention is also excellent in the degree of polarization unevenness. -75-201226452 &lt;Production of Liquid Crystal Display Device&gt; The liquid crystal panel in which the viewing angle was measured was produced in the following manner, and the characteristics of the liquid crystal display device were evaluated. The polarizing plate on both sides of the VA type liquid crystal display device (BRAVIAV1, 40吋 type manufactured by SONY) is peeled off, and the cellulose ester film 1 11 to 1 3 7 side is in a state of being a glass surface of the liquid crystal cell. The polarizing plate produced above is attached to both sides. At this time, the liquid crystal display device was produced by making the absorption axis oriented in the same direction as the polarizing plate to be bonded in advance. The liquid crystal display device was evaluated for the viewing angle, and the results are shown in Table 4. <<Evaluation of Liquid Crystal Display Device>> (Evaluation of viewing angle) 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. In the measurement, the EZ-Contrast 160D manufactured by ELDIM Co., Ltd. was used to measure the brightness in the direction in which the white line was tilted by 60 degrees from the normal direction of the display screen of the black display, and the ratio (60° contrast) was used as the angle of view. [Evaluation criteria of viewing angle] ◎ : 60° contrast is 100 or more 〇: 60° contrast is 90 or more and less than 100 △ : 60° contrast is 80 or more and less than 90 X : 60° contrast is less than 80 -76- 201226452 4 It is understood that the polarizing plate and the liquid crystal display device using the cellulose ester film of the present invention have an excellent viewing angle. Example 2 &lt;Production of Cellulose Ester Films 105A to 107A, 106B, and 133A to 136A&gt; (Production of Cellulose Ester Film 105A) In the production of the cellulose ester film 105, the main glue was changed to the following main glue. A cellulose ester film 105 A was also produced in the same manner as in the slurry A. &lt;Composition of main dope A&gt; Dichloromethane 300 parts by mass of ethanol 30 parts by mass of cellulose ester CE-5 100 parts by mass of hydrolysis preventing agent (A) (Compound No. 3) 7 parts by mass of phase difference adjusting agent ( B) 6 parts by mass of anionic surfactant RZ-1 〇. 〇 5 parts by mass (manufactured by cellulose ester film 1〇6Α~1〇7Α, 106B, 133A~136A) cellulose ester film 1〇6~107, In the production of 133 to 136, except that the anionic surfactant shown in Table 5 was added, and the main gel slurry was prepared, the cellulose ester film 1〇6Α~107A, 106B, 133A was produced in the same manner as in the production of the cellulose ester film 105A. 136A. The cellulose ester films 105A to 107A, 106B, and 133A to 1 3 6 A after the production were evaluated in the same manner as in Example 1. The results are shown in Table 6. -77- 201226452 [s] The present invention The present invention The present invention The relationship (2) of the present invention (ΓΟ) (〇 Bu 1 Bu 5. U&gt; 4.97 U) 00 m 6.50 I Ή S3 S b 2 w | 4.69 | 1 δ.56 1 1 σ\ 00 Γ0 V a&gt; \n 5.89 Anionic surfactant content (parts by mass) | 0.05 | ο ο I 0.02 I | 0.005 I csi CM 〇j 0.03 m 上上&lt;〇1 m OC CO ls CO 1 2 σ&gt; 1 T 2 T phase difference adjuster (B) content W(B) m CVJ ο CM 1 or〇in CM oc〇o C0 卜 csi logP tA in 卜卜 5.5 to i〇example Compound ΚΩ τ ω Τ m B-18 B-14 Compound b I Compound c Tinuvin P Hydrolysis inhibitor (4) Content W(A) «—· σ> cn 00 CO oo logP 10.2 h〇-2 • · Ο MO) 〇&gt 10.6 hM 10.2 exemplified compound ιη I &lt; ΙΟ 1 &lt; ιη &lt; in &lt; I PETB I Tinuvin 405 in &lt; LO 1 &lt; Relational formula (3) Ratio I 0.91 1 2.61 2.61 L2.04 2.13 2.13 2.13 &lt;;*&gt; CM grinding surface ppn 卜 (Ο S 2〇6 &lt;〇σ&gt; CsJ tn Csl CO (M cr&gt; cn 00 CM σ% σ&gt; ιό σ% in tn iin m Ug amount ppn iO σ&gt;&lt; Λ CM In U) in in Ca ΡΡπ &lt;Μ Μ ο ο 5 〇o O o hydroxy residue (DR) σ&gt; in Ο σ&gt; ιη ο 1 0.59 1 σ&gt; in 〇0.57 K d 0.57 κ o No. ιη UJ ΙΟ UJ ο i〇0J CE — 7 rt D UJ o D UJ T UJ o T Ui Alizarin film No. 1 105Α 1 1 106Α 1 106Β 107A 1 133A I 134A | 135A I 136A I\l) x§M\3*) ·· (§_ :_ΒΗ ((a )o.BOI)—((y&gt;dBOI) : (1)3⁄4雄醒_s : WIM3 -78- 201226452 [Table 6] Cellulose Ester film evaluation. Evaluation of film evaluation of liquid crystal display device Remarks Ro (ηπι) Rt (ηιη) Internal haze phase difference 値 fluctuating haze variation oozing unevenness viewing angle 105A 55 135 〇 ◎ ◎ 〇〇 发明 发明 106A 50 137 0.01 ◎ ◎ ◎ ◎ ◎ ◎ 66 66 66 66 66 66 66 66 66 66 107 107 107 107 107 107 107 107 107 107 107 107 107 107 107 107 本 本 本 本 本 本 本 本 本 本 本 本 本 133 本 本 本 本 134 134 134 134 134 134 134 134 134 134 134 134 134 134 134 134 134 134 134 134 134 134 134 134 〇The present invention 135A 49 135 ο.όι 〇◎ ◎ 〇〇 the present invention 136A 48 140 0.03 〇 ◎ ◎ 〇〇 The present invention is obtained from Table 6 It is known that when an anionic surfactant is used, the haze is lowered, and haze fluctuation and bleeding can be further improved. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] is a schematic view showing a state in which glycerin is dropped onto a glass slide. [Fig. 2] A schematic view showing a state in which a sample film is placed on glycerin. Fig. 3 is a schematic view showing a state in which glycerin is dropped onto a sample film. Fig. 4 is a schematic view showing a state in which a cover glass is placed on glycerin. -79-

Claims (1)

201226452 VII. Patent application scope: 1. A cellulose ester film characterized by cellulose acetate and hydrolysis inhibitor (A) with a hydroxyl residue (DR) of 0.5 to 1.0, and a phase difference adjuster (B) At least one of each '' and satisfying the following relationship (1), (2) relation (1) 4 &lt; (logP(A)) - (logP(B)) &lt;l 2 (but logP (A): hydrolysis The octanol-water partition coefficient of the preventive agent (a).logP (B): the octanol-water partition coefficient of the phase difference adjuster (B)) Relationship (2) 2.5 &lt; (W(A)/W(B ))x(l/DR)&lt;8.5 (but W(A): the quality of the hydrolysis preventive agent (A) contained in the cellulose ester film, W(B): phase difference adjuster (B) in cellulose The mass contained in the ester film, DR: hydroxyl residue of cellulose acetate). 2. The cellulose ester film according to claim 1, wherein the cellulose ester film has an internal haze of 〇. 3. The cellulose ester film according to claim 1 or 2, wherein the total amount (ppm) of calcium and magnesium contained in the cellulose ester film and the amount of acetic acid (ppm) satisfy the following relationship (3) , relationship (3) 1 $ (acetic acid amount (ppm)) / (total amount of calcium and magnesium (ppm)) ^ 3 0. 4. The cellulose ester film of any one of claims 1 to 3 wherein the aforementioned logP (A) is 7 or more and less than 1, and the logP (B) is 0 or less. 5. The cellulose ester film according to any one of the above-mentioned claims, wherein the hydrolysis preventing agent (A) is one or more than 12 or less pyridene-80-201226452 orphanose or furanose. At least one of the structures, and an ester compound in which one of the H groups of the structure is esterified. 6. The cellulose ester film according to any one of claims 1 to 5, wherein the phase difference adjusting agent (B) is represented by the following general formula (1), and the general formula (1) B-(GA) nGB (wherein B represents a hydroxyl group or a carboxylic acid residue, and G represents a carbon number&gt;; 2 a hospital alcohol residue or an aryl alcohol residue having a carbon number of 6 to 12 or a carbon number of 4~ The oxime diol residue of '12' represents an alkyl dicarboxylic acid residue having 4 to 12 carbon atoms or an aryl dicarboxylic acid residue having 6 to 12 carbon atoms, and η represents an integer of 1 or more). 7. A cellulose ester film characterized by having a hydroxyl residue (DR) of 〇·5~1 · 纤维素 cellulose acetate and an octanol-water partition coefficient (logP ( A ) ) of 7 or more A hydrolysis inhibitor (A) of up to 11 and an anionic surfactant. 8. The cellulose ester film of claim 7, wherein the anionic surfactant is a compound of the following general formula (I) or (II) &gt; general formula (I) [RlO(A0)n] pP( = 0)(0M)q General formula (II) R2-LQ (R1 and R2 represent a group of carbon atoms 8 to 2 2 which may have a linear or branched substituent. 'A series means carbon number 2 ～ alkyl group, η system 0 or an integer of 1 to 20, p and q represent p + q = 3, and ρ = 1 or 2 integer, lanthanide represents a hydrogen atom, test -81 - 201226452 metal atom Any one of the ammonium groups, L is a divalent linking group, and Q is a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a sulfate or a salt thereof. 9. The cellulose ester film according to claim 7 or 8, wherein the anionic surfactant is contained in an amount of 0.005 to 0.5 parts by mass based on 100 parts by mass of the cellulose acetate. 10. The cellulose ester film of any one of claims 7 to 9 which contains the phase difference adjusting agent (B) represented by the above general formula (1). A polarizing plate characterized in that the cellulose ester film according to any one of claims 1 to 1 is bonded to at least one side of a polarizer composed of polyvinyl alcohol. A liquid crystal display device is characterized in that at least one side of a liquid crystal cell has a polarizing plate of claim 11 of the patent application. -82-