KR101709419B1 - Optical film, method for producing optical film, polarizing plate and liquid crystal display device - Google Patents

Abstract

An object of the present invention is to provide an optical film which is less opaque, hard to generate heat wrinkles, and has little deterioration of the wound shape in a roll body, and thereby provides a liquid crystal display device with high luminance. The optical film of the present invention contains a cellulose ester in which the total degree of substitution of the acyl group is 2.0 to 3.0 and both of the acyl groups are acetyl groups and the stretching elongations in two mutually orthogonal directions in the film plane are all 1 to 10 %, And a thickness of 15 to 35 mu m.

Description

TECHNICAL FIELD [0001] The present invention relates to a polarizing plate and a liquid crystal display device, and more particularly to a polarizing plate and a liquid crystal display device using the polarizing plate and the polarizing plate.

The present invention relates to an optical film, a production method of the optical film, a polarizing plate and a liquid crystal display device.

Currently, portable liquid crystal display devices such as smart phones and tablets are widely spread. These portable liquid crystal display devices are required to be thin.

The liquid crystal display has a liquid crystal cell and a pair of polarizing plates for supporting the liquid crystal cell. The polarizing plate usually has a polarizer and a pair of protective films for supporting the polarizer. Therefore, along with the reduction in thickness of the portable liquid crystal display device, reduction of the thickness of the protective film as a component thereof is also required.

The protective film is usually produced by stretching a formed film material. In order to make the protective film thinner, it is also effective to make the thickness of the film material thinner; If the film fabric is thinned, wrinkles tend to occur. For this reason, it is desired to make the protective film thinner by increasing the stretching ratio, not by reducing the thickness of the film raw material.

On the other hand, after obtaining a film fabric containing cellulose acetate such as TAC or DAC by a solution casting method; There has been proposed an optical film obtained by stretching the film raw material in one direction at a high magnification (Patent Documents 1 to 3). Further, after obtaining a film material comprising a cellulose ester containing an acyl group having 3 or more carbon atoms such as CAP or CAB by a melt film-forming method; An optical film obtained by biaxially stretching the above-mentioned film raw material at a high magnification is also proposed (Patent Document 4). Further, an optical film obtained by biaxially stretching a film raw material comprising cellulose acetate and a phosphate ester plasticizer by a solution casting method has been proposed (Patent Document 5).

Japanese Patent Application Laid-Open No. 2009-288259 Japanese Patent Application Laid-Open No. 2002-127244 Japanese Patent Application Laid-Open No. 2007-264110 Japanese Patent No. 4834444 Japanese Patent Application Laid-Open No. 2008-3126

However, as shown in Patent Document 4, resins such as CAP and CAB to which the melt film forming method is applied have relatively high flexibility. For this reason, there is a problem that the film material containing these resins can be stretched at a high magnification, but the film after stretching easily becomes cloudy.

In addition, a film obtained by stretching a film fabric including such a highly flexible resin at a high magnification tends to have a high elongation at break and a low tensile elastic modulus. When the rolled body of the film having a low tensile modulus of elasticity is held for a long period of time so that the winding core is horizontal, there is a problem that when the film thickness is small, the central portion in the widthwise direction of the film is recessed as its own weight, there was.

In addition, a portable liquid crystal display device such as a smart phone or a tablet may have a higher temperature than a television or notebook. For this reason, when a film having a high elongation at break is used as a protective film of a portable liquid crystal display device, the film tends to expand and contract due to the influence of heat and humidity such as a backlight, thereby causing thermal wrinkle. In addition, there is a problem that heat wrinkles occur even in a film stretched in one direction at a high magnification (or in a film having only a low elongation in one direction in the film surface) as in Patent Documents 1 to 3.

In addition, the film fabric of Patent Document 5 obtained by the solution casting method has insufficient stretchability, and it is difficult to sufficiently increase the stretching magnification.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide an optical film having less white turbidity, less heat wrinkling, and less deterioration of the winding shape when stored in a roll. Another object of the present invention is to provide a liquid crystal display device including such an optical film and having high brightness.

[1] A cellulose acylate film, which comprises cellulose ester wherein the total degree of substitution of acyl groups is 2.0 to 3.0 and both of acyl groups are acetyl groups, And an elongation of 1 to 10%, and a thickness of 15 to 35 mu m.

[2] The optical film according to [1], wherein the haze measured according to JIS K-7136 is 0.5 or less.

[3] The optical film according to [1] or [2], wherein the optical film further contains an additive having a ring structure and having a molecular weight of 10,000 or less.

[4] The additive preferably has a polyester compound or styrene compound or a pyranose structure or a furanose structure in which the ring structure contained in the repeating unit is a non-aromatic ring structure or an aromatic ring structure, The optical film according to [3], wherein the structure or the furanose structure is a sugar ester compound having a substituent group including a non-aromatic ring structure or an aromatic ring structure.

[5] The optical film according to [3] or [4], wherein the ring structure is an aromatic ring.

[6] The optical film according to any one of [3] to [5], wherein the additive is a polyester compound having a molecular weight of 600 or more, or a styrene compound having a molecular weight of 600 or more, wherein the ring structure contained in the repeating unit is an aromatic ring structure.

[7] The optical film according to any one of [3] to [6], wherein the content of the additive is 5 to 30 mass% with respect to the cellulose ester.

[8] Any one of [1] to [7], wherein the tensile elastic modulus at 23 ° C and 55% RH is 5.0 to 8.0 적어도, at least one of the direction of the slow axis in the film plane and the direction perpendicular to the slow axis direction, ≪ / RTI >

[9] The optical film described in any one of [1] to [8], wherein the elongation at break at 25 ° C in the direction of the slow axis in the film plane and the direction perpendicular to the slow axis direction are all 1 to 5%.

[10] The optical film according to any one of [1] to [9], wherein the in-plane retardation R _o (590) at 23 ° C. and 55% RH at a measurement wavelength of 590 nm is 10 nm or less.

[11] A process for producing a dope comprising a cellulose ester in which the total substitution degree of an acyl group is 2.0 to 3.0, and all of the acyl groups are an acetyl group, and an additive having a ring structure and having a molecular weight of 10,000 or less,

A step of softening the dope liquid onto an endless metal support,

A step of peeling the filmy material obtained by drying the flexible dope liquid from the metal support,

A step of stretching the peeled film-like material at a stretching magnification ratio of 1.3 to 4.0 times in two mutually orthogonal directions in the plane of the film-like material to obtain an optical film having a thickness of 15 to 35 占 퐉; Way.

[12] The additive preferably has a polyester compound or a styrene compound or a pyranose structure or a furanose structure in which the ring structure contained in the repeating unit is a non-aromatic ring structure or an aromatic ring structure, Structure or the furanose structure is a sugar ester compound having a substituent group containing a non-aromatic ring structure or an aromatic ring structure.

[13] The method for producing an optical film according to [11] or [12], wherein the ring structure is a aromatic ring.

[14] The additive is an optical film according to any one of [10] to [13], wherein the additive is a polyester compound having a molecular weight of 600 or more, or a styrene compound having a molecular weight of 600 or more, Gt;

[15] The production method of an optical film according to any one of [10] to [14], wherein the content of the additive is 5 to 30 mass% with respect to the cellulose ester.

[16] The optical film according to any one of [10] to [15], wherein the retardation R _o (590) in the in-plane direction at 23 ° C. and 55% RH and at a measurement wavelength of 590 nm is 10 nm or less ≪ / RTI >

[17] A polarizing plate comprising the optical film according to any one of [1] to [10].

[18] A liquid crystal display device comprising the optical film according to any one of [1] to [10].

[19] A liquid crystal display comprising a liquid crystal cell, a first polarizer disposed on one side of the liquid crystal cell and having a first polarizer, and a second polarizer disposed on the other side of the liquid crystal cell and having a second polarizer , Wherein the first polarizing plate has the optical film according to any one of [1] to [10], which is disposed on the side of the first polarizer opposite to the liquid crystal cell, or the second polarizing plate has, The liquid crystal display device according to any one of [1] to [10], wherein the optical film is disposed on the side of the second polarizer opposite to the liquid crystal cell.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an optical film having less white turbidity, less occurrence of thermal wrinkles, and less deterioration of the wound shape when stored in a roll. Thereby, a liquid crystal display device having a high luminance can be provided.

1 is a schematic diagram showing an example of a basic configuration of a liquid crystal display device of the present invention.

Hereinafter, the present invention will be described in detail. In the present specification, " to " is used to mean that the numerical values described before and after the lower limit and the upper limit are included.

1. Optical film

The optical film of the present invention comprises a cellulose ester and an additive having a cyclic structure.

Cellulose ester

The glucose unit having? -1,4 bonding that constitutes cellulose has a hydroxyl group (hydroxyl group) of glass at the second, third and sixth positions. The cellulose ester is a polymer (polymer) obtained by acylating part or all of these hydroxyl groups (hydroxyl groups). The total degree of substitution of the acyl group means the ratio (acylation of 100%) of the hydroxyl groups (hydroxyl groups) of cellulose located at the second, third and sixth positions to acylation (substitution degree 3 of 100%).

The acyl group contained in the cellulose ester is preferably an acetyl group for reasons such as to reduce the whitening of the film after stretching as described later. That is, the cellulose ester is preferably cellulose acetate in which all the acyl groups are acetyl groups.

The total substitution degree of the acyl group of the cellulose ester is preferably 2.0 to 3.0, more preferably 2.5 to 2.95. The cellulose ester in which the total degree of substitution of the acyl group is not less than 2.5 and all the acyl groups are acetyl groups can not be formed by the melt softening method and in order to realize biaxial stretching at a high magnification, Is particularly effective. The total substitution degree of the acyl group can be measured in accordance with ASTM-D817-96. Biaxial stretching is preferably performed in both the carrying direction (MD direction) and the width direction (TD direction) of the film.

The weight average molecular weight of the cellulose ester is preferably 5.0 x 10 ⁴ to 5.0 x 10 ⁵ , more preferably 1.0 x 10 ⁵ to 3.0 x 10 ⁵ , and more preferably 1.5 x 10 ⁴ to obtain a film having a mechanical strength of a certain level or higher. More preferably 10 ⁵ to 2.5 10 ⁵ . The molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn) of the cellulose ester is preferably 1.0 to 4.5.

The weight average molecular weight and molecular weight distribution of the cellulose ester can be measured by gel permeation chromatography (GPC). The measurement conditions are as follows.

Solvent: methylene chloride

Column: Three shodex K806, K805 and K803G (manufactured by Showa Denko K.K.) are connected and used.

Column temperature: 25 ° C

Sample concentration: 0.1 mass%

Detector: RI Model 504 (manufactured by GL Science)

Pump: L6000 (manufactured by Hitachi Seisakusho Co., Ltd.)

Flow rate: 1.0 ml / min

Calibration curve: standard polystyrene STK standard A calibration curve of 13 samples with polystyrene (manufactured by TOSO CORPORATION) Mw = 1.0 × 10 ⁶ to 5.0 × 10 ² is used. 13 samples are preferably selected at substantially equal intervals.

The cellulose ester is generally synthesized by acylating the raw cellulose with a fatty acid corresponding to the acyl group (preferably acetic acid) or its acid anhydride. The cellulose ester can be synthesized, for example, by the method described in JP-A-10-45804.

The raw cellulose may be a wood pulp or a cotton linter. Wood pulp may be coniferous or hardwood. The cellulose esters obtained from the raw material cellulose may be mixed appropriately or used alone.

For example, the ratio of cellulose ester derived from cotton linter: cellulose ester derived from wood pulp (softwood) to cellulose ester derived from wood pulp (hardwood) is 100: 0: 0, 90: 10: 0, 85: 15: 50: 0, 20: 80: 0, 10: 90: 0, 0: 100: 0, 0: 0: 100, 80:10:10, 85: 0:15, 40:30:30.

As described above, the cellulose ester (cellulose acetate) in which all the acyl groups are acetyl groups has low flexibility as compared with the cellulose ester (cellulose mixed ester) in which a part of the acyl group is propionyl group and the like. Therefore, the film of cellulose acetate usually has poor stretchability, and it is difficult to biaxially stretch at a high magnification.

In contrast, the present inventors have found that the addition of a " additive having a cyclic structure " to cellulose acetate increases the film stretchability of cellulose acetate. This is presumably due to the fact that the ring structure of the " additive having a cyclic structure " has a high bulk density, so that it is introduced between the cellulose acetate molecular chains and extends the gap between the cellulose acetate molecular chains.

Unlike a film obtained by biaxially stretching a film of cellulose acetic acid ester such as cellulose acetate propionate or the like at a high magnification, the film obtained by biaxially stretching the film of such a cellulose acetate film at a high magnification has low white turbidity, All the elongation at break in the two stretching directions in the plane were low and the tensile elastic modulus was high. That is, since the film obtained is less cloudy, the brightness of the liquid crystal display device can be increased. In addition, since both the elongation at break in the two stretching directions of the obtained film are all low and the tensile elastic modulus is high, it is possible to suppress the wrinkling of the polarizing plate under high temperature and high humidity and the deterioration of the winding shape when it is stored in a roll form .

(Additive having a cyclic structure)

The additive having a cyclic structure includes a non-cyclic structure or an aromatic cyclic structure, preferably an aromatic cyclic structure, as a cyclic structure.

The non-aromatic ring structure is preferably a substituted or unsubstituted aliphatic hydrocarbon ring or aliphatic hetero ring having 5 to 22 carbon atoms. Examples of the non-aromatic ring structure include cyclopentyl, cyclohexyl, norbornyl, cycloheptyl, isobornyl, adamantyl, cyclodecyl, dicyclopentyl, and anhydride rings (for example, -CH -C (= O) OC (= O) -CH-) and the like.

The aromatic ring structure is preferably a substituted or unsubstituted aromatic hydrocarbon ring or aromatic hetero ring having 6 to 23 carbon atoms, more preferably a substituted or unsubstituted aromatic hydrocarbon ring. Examples of the aromatic ring structure include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring and the like.

Examples of the substituent which the aliphatic hydrocarbon ring, aliphatic heterocycle, aromatic hydrocarbon ring or aromatic heterocycle may have include an alkyl group having 1 to 3 carbon atoms, an alkoxy group, a cyano group, a hydroxyl group and the like.

The additive having a cyclic structure may be a polyester compound or a styrene compound or a pyranose structure or a furanose structure in which the cyclic structure contained in the repeating unit is a non-aromatic cyclic structure or an aromatic cyclic structure, Structure or furanose structure is a sugar ester compound having a substituent group including a non-aromatic ring structure or an aromatic ring structure.

Polyester compound

The polyester compound includes a repeating unit derived from a condensation product of a dicarboxylic acid and a diol. The repeating unit preferably includes a non-aromatic ring structure or an aromatic ring structure. That is, at least one of the dicarboxylic acid and the diol constituting the polyester compound preferably contains a non-aromatic cyclic structure or an aromatic cyclic structure, but it is preferable that the dicarboxylic acid includes a non-aromatic cyclic structure or an aromatic cyclic structure desirable.

The dicarboxylic acid may be an aliphatic dicarboxylic acid, an alicyclic dicarboxylic acid or an aromatic dicarboxylic acid. The carbon number of the aliphatic dicarboxylic acid is preferably 4 to 20, more preferably 4 to 12. Examples of aliphatic dicarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandicarboxylic acid, dodecanedicarboxylic acid and the like .

The number of carbon atoms of the aromatic dicarboxylic acid is preferably 8 to 20, more preferably 8 to 12. Examples of the aromatic dicarboxylic acid include 1,2-benzenedicarboxylic acid (phthalic acid), 1,3-benzenedicarboxylic acid (isophthalic acid), 1,4-benzenedicarboxylic acid (terephthalic acid), 1 , 5-naphthalene dicarboxylic acid, 1,4-xylylene dicarboxylic acid, and the like.

The carbon number of the alicyclic dicarboxylic acid is preferably 6 to 20, more preferably 6 to 12. Examples of the alicyclic dicarboxylic acid include 1,3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid Acetic acid and the like.

The dicarboxylic acid constituting the polyester compound may be one kind or two or more kinds. The dicarboxylic acid constituting the polyester compound preferably contains an aromatic dicarboxylic acid, and more preferably contains both an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid. As the aromatic dicarboxylic acid, 1,4-benzenedicarboxylic acid (terephthalic acid) is particularly preferable.

The diol may be an aliphatic diol, an alkyl ether diol, an alicyclic diol or an aromatic diol. The carbon number of the aliphatic diol is preferably 2 to 20, more preferably 2 to 12. Examples of aliphatic diols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, Propane diol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2- Ethyl-1,3-propanediol (3,3-dimethylolheptane), 3-methyl-1,5-pentanediol, 1,6-hexanediol , 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,9- Diol, 1,12-octadecanediol, and the like. The number of carbon atoms of the alkyl ether diol is preferably 4 to 20, more preferably 4 to 12. Examples of the alkyl ether diol include polytetramethylene ether glycol, polyethylene ether glycol, and polypropylene ether glycol.

The carbon number of the alicyclic diol is preferably 4 to 20, more preferably 4 to 12. Examples of the alicyclic diols include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like.

The carbon number of the aromatic diol is preferably 6 to 20, more preferably 6 to 12. Examples of the aromatic diol include 1,2-dihydroxybenzene (catechol), 1,3-dihydroxybenzene (resorcinol), 1,4-dihydroxybenzene (hydroquinone) and the like.

The diol constituting the polyester compound may be one type or two or more types. The diol constituting the polyester compound preferably contains an aliphatic diol.

Among these, a polyester compound containing a repeating unit derived from a condensation product of a dicarboxylic acid containing an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid with an aliphatic diol is preferable because the film containing the repeating unit is excellent in transparency .

The molecular end of the polyester compound may be sealed with a monocarboxylic acid or a monoalcohol if necessary.

The monocarboxylic acid may be an aliphatic monocarboxylic acid, an alicyclic monocarboxylic acid, or an aromatic monocarboxylic acid. The carbon number of the aliphatic monocarboxylic acid may preferably be 2 to 30, more preferably 2 to 4. Examples of the aliphatic carboxylic acid include acetic acid, propionic acid, butanoic acid, caprylic acid, caproic acid, decanoic acid, dodecanoic acid, stearic acid, oleic acid and the like. Examples of the alicyclic monocarboxylic acid include cyclohexyl monocarboxylic acid and the like. Examples of the aromatic monocarboxylic acid include benzoic acid, para-tert-butylbenzoic acid, orthotoluenic acid, metatoluic acid, paratoluic acid, dimethylbenzoic acid, ethylbenzoic acid, normal propylbenzoic acid, aminobenzoic acid, acetoxybenzoic acid, phenylacetic acid, 3 - phenylpropionic acid, and the like.

The monoalcohol may be an aliphatic monoalcohol, an alicyclic monoalcohol or an aromatic monoalcohol. The aliphatic monoalcohol has 1 to 30 carbon atoms, preferably 1 to 3 carbon atoms. Examples of aliphatic monoalcohols include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, isopentanol, hexanol, isohexanol, octanol, isooctanol, 2-ethylhexyl alcohol, Nonyl alcohol, tert-nonyl alcohol, decanol, dodecanol, dodecahexanol, dodeca-octanol, allyl alcohol, oleyl alcohol and the like. Examples of the alicyclic monoalcohols include cyclohexyl alcohol and the like. Examples of the aromatic monoalcohol include benzyl alcohol, 3-phenylpropanol, and the like.

Specific examples of the polyester compound having a cyclic structure include the following. TPA: terephthalic acid, PA: phthalic acid, SA: succinic acid, AA: adipic acid, SEA: sebacic acid are shown in Table 1 to be described later.

Styrene compound

The styrene-based compound may be a homopolymer of a styrene-based monomer, or a copolymer of a styrene-based monomer and other copolymerizable monomers. The content ratio of the constitutional unit derived from the styrene-based monomer in the styrene compound is preferably 30 to 100 mol%, more preferably 50 to 100 mol% in order for the molecular structure to have a bulk (high bulk density) %. ≪ / RTI >

The styrene-based monomer is preferably a compound represented by the following formula (1).

R ¹⁰¹ to R ¹⁰³ in the general formula (1) each independently represent a hydrogen atom or an alkyl group or an aryl group having 1 to 30 carbon atoms. R ¹⁰⁴ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group, an aryl group, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group, an alkyloxycarbonyl group having 2 to 30 carbon atoms, an aryloxycarbonyl group, An alkylcarbonyloxy group, an arylcarbonyloxy group, a hydroxyl group, a carboxyl group, a cyano group, an amino group, an amide group and a nitro group. Each of these groups may further have a substituent (for example, a hydroxyl group, a halogen atom, an alkyl group, etc.). R ¹⁰⁴ may be the same or different and may be bonded to each other to form a ring.

Examples of the styrene-based monomer include styrene; alkyl-substituted styrenes such as? -methylstyrene,? -methylstyrene and p-methylstyrene; Halogen-substituted styrenes such as 4-chlorostyrene and 4-bromostyrene; hydroxystyrenes such as p-hydroxystyrene,? -methyl-p-hydroxystyrene, 2-methyl-4-hydroxystyrene and 3,4-dihydroxystyrene; Vinylbenzyl alcohols; alkoxy-substituted styrenes such as p-methoxystyrene, p-tert-butoxystyrene and m-tert-butoxystyrene; Vinylbenzoic acids such as 3-vinylbenzoic acid and 4-vinylbenzoic acid; 4-vinylbenzyl acetate; 4-acetoxystyrene; Amide styrenes such as 2-butyl amide styrene, 4-methyl amide styrene and p-sulfonamide styrene; Aminostyrenes such as 3-aminostyrene, 4-aminostyrene, 2-isopropenyl aniline and vinyl benzyl dimethyl amine; Nitrostyrenes such as 3-nitrostyrene and 4-nitrostyrene; Cyanostyrenes such as 3-cyanostyrene and 4-cyanostyrene; Vinylphenylacetonitrile; Aryl styrenes such as phenylstyrene, and indenes. The styrene-based monomer may be used alone or in combination of two or more.

The copolymerizable monomer to be combined with the styrenic monomer may be a (meth) acrylic acid ester compound represented by the following formula (2), maleic anhydride, citraconic anhydride, cis-1-cyclohexene-1,2-anhydrous dicarboxylic acid, -Methyl-cis-1-cyclohexene-1,2-anhydro dicarboxylic acid, and 4-methyl-cis-1-cyclohexene-1,2-anhydrodicarboxylic acid, acrylonitrile, Nitrile group-containing radically polymerizable monomers such as acrylonitrile; Amide bond-containing radically polymerizable monomers such as acrylamide, methacrylamide, and trifluoromethanesulfonylaminoethyl (meth) acrylate; Fatty acid vils such as vinyl acetate; Chlorine-containing radically polymerizable monomers such as vinyl chloride and vinylidene chloride; Conjugated diolefins such as 1,3-butadiene, isoprene and 1,4-dimethylbutadiene, and the like. The (meth) acrylic acid ester compound represented by the following formula (2) or maleic anhydride is preferable.

R ¹⁰⁵ to R ¹⁰⁷ in the general formula (2) each independently represent a hydrogen atom or an alkyl group or an aryl group having 1 to 30 carbon atoms. R ¹⁰⁸ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group or an aryl group. Each of these groups may further have a substituent (for example, a hydroxyl group, a halogen atom, an alkyl group, etc.).

Examples of the (meth) acrylate compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n- (tert-), pentyl (meth) acrylate (n-, i-, s-), hexyl (meth) acrylate, n- (N-, i-), (meth) nonyl acrylate (n-, i-), myristyl (meth) acrylate (n-, i-), (meth) (Meth) acrylic acid (2-hydroxypropyl), (meth) acrylic acid (3-hydroxypropyl), (meth) acrylic acid (Meth) acrylic acid (2-methoxyethyl), (meth) acrylic acid (2-ethoxyethyl) acrylate, Acrylic acid (2 or 4-chlorophenyl), (meth) acrylic acid (2 or 3 or 4-ethoxycarbonylphenyl), (meth) (meth) acrylic acid (2-naphthyl), (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenethyl Hexyl), (meth) acrylic acid (4-ethylcyclohexyl), and the like.

Specific examples of the styrene-based compound include styrene / maleic anhydride copolymer, styrene / acrylic acid ester copolymer, styrene / hydroxystyrene polymer, styrene / acetoxystyrene polymer and the like. Among them, a styrene / maleic anhydride copolymer is preferable.

Ester ester compound

The sugar ester compound is a compound obtained by esterifying a hydroxyl group and a monocarboxylic acid contained in a sugar.

The sugar constituting the sugar ester compound is more preferably a compound having a structure in which at least one of the furanose structure and the pyranose structure is bound to 1 to 12 sugars.

Examples of the sugar constituting the sugar ester compound include monosaccharides such as glucose, galactose, mannose, fructose, xylose and arabinose; 2 sugars such as lactose, sucrose, maltitol, cellobiose, and maltose; And triploids such as celotriose and raffinose. Among them, sugars having both a pyranose structure and a furanose structure are preferable, and sucrose is particularly preferable.

The monocarboxylic acid constituting the sugar ester compound may be an aliphatic monocarboxylic acid, an alicyclic monocarboxylic acid, or an aromatic monocarboxylic acid. In order to obtain a sugar ester compound having a high bulk density, the monocarboxylic acid constituting the sugar ester compound preferably contains an alicyclic monocarboxylic acid or an aromatic monocarboxylic acid, and an aromatic monocarboxylic acid More preferable. The monocarboxylic acid may be a single kind or a combination of two or more kinds. For example, an aliphatic monocarboxylic acid and an aromatic monocarboxylic acid may be combined.

Examples of the aliphatic monocarboxylic acid include acetic acid, propionic acid, and the like. Examples of the alicyclic monocarboxylic acid include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, and the like. Examples of the aromatic monocarboxylic acid include benzoic acid, phenylacetic acid and the like.

The sugar ester compound is preferably a compound represented by the following formula (3).

R ₁ to R ₈ in Formula (3) represent a monovalent group derived from an aliphatic monocarboxylic acid, a monovalent group derived from an alicyclic monocarboxylic acid, or a monovalent group derived from an aromatic monocarboxylic acid; At least one of R ₁ to R ₈ is a monovalent group derived from an alicyclic monocarboxylic acid or a monovalent group derived from an aromatic monocarboxylic acid. R ₁ to R ₈ may be the same or different.

Examples of the monovalent group derived from an aliphatic monocarboxylic acid include a monovalent group derived from an aliphatic monocarboxylic acid having 2 or more carbon atoms such as a methylcarbonyl group (acetyl group). Examples of the monovalent group derived from an alicyclic monocarboxylic acid include a monovalent group derived from an alicyclic monocarboxylic acid having 5 or more carbon atoms of cyclopentylcarboxylic acid or cyclohexylcarboxylic acid. Examples of the monovalent group derived from an aromatic monocarboxylic acid include a monovalent group derived from an aromatic monocarboxylic acid having 7 or more carbon atoms such as a phenylcarbonyl group (benzoyl group) and a phenylmethylcarbonyl group. The aromatic ring in the monovalent group derived from the non-aromatic ring or aromatic monocarboxylic acid in the monovalent group derived from the alicyclic monocarboxylic acid may further have a substituent such as an alkyl group or an alkoxyl group.

Among them, R ₁ to R ₈ are preferably a monovalent group derived from an aromatic monocarboxylic acid.

Specific examples of the compound represented by the general formula (3) include the following. R in the following table represents R ₁ to R ₈ in the general formula (3).

The average degree of substitution of the sugar ester compound is preferably 3.0 to 8.0, and particularly preferably 5.0 to 8.0. When the substituent bonded to the carbon atom constituting the pyranose structure or the furanose structure includes a non-aromatic ring structure or an aromatic ring structure, when the average degree of substitution is within the above range, the bulk of the sugar ester compound It is easy to do.

The sugar ester compound having the cyclic structure may be used in combination with a sugar ester having no cyclic structure, if necessary. Examples of the sugar ester compound having no cyclic structure include the following. R in the following table represents R ₁ to R ₈ in the following formula (A).

(A)

Of these, a polyester compound, a styrene compound, and a sugar ester compound having an aromatic ring structure, in which the repeating unit has an aromatic ring structure, are preferable from the viewpoint of having a sufficient molecular structure and the molecular structure is preferably a relatively straight chain structure , And it is more preferable to use a polyester compound or a styrene compound having an aromatic ring structure as the repeating unit in the point that the stretching property of the film is easily increased (the plasticizing effect is easily obtained).

The additive having a cyclic structure is present between the cellulose ester molecules as described above, and the interval between the molecular chains of the cellulose ester can be widened. Thus, it is considered that the stretching property of the film can be enhanced. Therefore, the additive having a cyclic structure preferably has a sufficient bulk of its molecular structure, and preferably contains a large number of ring structures.

The bulk density (bulk) of the additive having a cyclic structure can be evaluated by a " bulk index " defined by the following formula.

Bulk index = total molecular weight of cyclic moiety / total molecular weight of additive having cyclic structure

The "ring structure moiety" in the above formula represents a non-aromatic ring structure or an aromatic ring structure itself. When a nonaromatic ring structure or aromatic ring structure has a substituent, the substituent is also considered to be part of the ring structure. For example, the "cyclic structure portion" of the exemplified compound 6 of the polyester in Table 1 is a phenylene group (-C ₆ H ₄ -) derived from terephthalic acid and a phenyl group derived from benzoic acid (-C ₆ H ₅ ). The "cyclic moiety" of the styrene / maleic anhydride copolymer is a phenyl group (-C ₆ H ₅ ) constituting styrene and -CHC (═O) OC (═O) CH- derived from maleic anhydride. The " cyclic structure portion " of the styrene / hydroxystyrene copolymer is a hydroxyphenyl group (-C ₆ H ₄ OH) constituting styrene and a phenyl group (-C ₆ H ₅ ) constituting hydroxystyrene. The " cyclic structure portion " of the sugar ester compound represented by the above formula (FA-1) is preferably a phenyl group contained in a substituent group other than the glucoside bond which is bonded to the carbon atom constituting the pyranose structure or furanose structure -C ₆ H ₅ ).

The bulk index of the additive having a cyclic structure is preferably 0.2 or more, and more preferably 0.6 or more. The upper limit of the " bulk index " can be, for example, about 0.9.

The weight average molecular weight of the additive having a cyclic structure is preferably 10,000 or less, and more preferably 5,000 or less, for reasons such as ensuring compatibility with the cellulose ester. The weight average molecular weight of the additive having a cyclic structure may be preferably 300 or more, and more preferably 400 or more, for reasons such as suppressing bleed-out or the like.

When the additive having a cyclic structure is a polyester compound or a styrene-based compound having a repeating unit having an aromatic ring structure, the weight average molecular weight of these compounds tends to increase the stretchability of the film and also increase the tensile modulus of the film after stretching Is preferably 600 or more, more preferably 1000 or more, and even more preferably 2000 or more.

The content of the additive having a cyclic structure is preferably 5 to 30 mass%, more preferably 5 to 20 mass%, based on the cellulose ester. If the content of the additive having a cyclic structure is less than 5% by mass, the interval between the molecular chains of cellulose ester may not be sufficiently extended. When the content of the additive having a cyclic structure is more than 30% by mass, not only is it easy to bleed out from the film, but also the elongation at break is increased.

Other additives

The optical film of the present invention may further contain various additives such as a plasticizer, an ultraviolet absorber, and a matting agent (fine particles), if necessary.

Plasticizer

Examples of the plasticizer include a polyester compound having no cyclic structure, a polyhydric alcohol ester compound, and the like among the above polyester compounds. Examples of the polyvalent alcohol ester compound include compounds described in paragraphs (0218 to 0170) of JP-A No. 2010-32655 and the like.

The content of the plasticizer is preferably 1 to 40% by mass, more preferably 5 to 20% by mass with respect to the cellulose ester.

Ultraviolet absorber

The optical film of the present invention may further contain an ultraviolet absorber. Examples of the ultraviolet absorber include a benzotriazole-based compound, a 2-hydroxybenzophenone-based compound, a salicylic acid phenyl ester-based compound, and the like.

Among them, an ultraviolet absorber having a molecular weight of 400 or more is difficult to sublimate or volatilize at a high boiling point, and is not easily scattered even when the film is dried at a high temperature. Therefore, from the viewpoint of effectively improving weatherability by the addition of a relatively small amount Do. Examples of the ultraviolet absorber having a molecular weight of not less than 400 include 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2-benzotriazole, 2,2- (1,1,3,3-tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol], bis (2,2,6,6-tetramethyl-4- Peridyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and the like, and further 2- (3,5-di- (1,2,2,6,6-pentamethyl-4-piperidyl), 1- [2- [3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5- 6,6-tetramethylpiperidine, and the like. These compounds may be used either singly or in combination of two or more. Among them, preferred are 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -Tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol] is particularly preferred.

The ultraviolet absorber may be a commercially available product. Examples of the ultraviolet absorber include tinuvin series such as Tinuvin 109, Tinuvin 171, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328 and Tinuvin 928 manufactured by BASF Japan; (1,1,3,3-tetramethylbutyl) phenol] (molecular weight: 659, commercially available product: ADEKA (trade name) manufactured by Kabushiki Kaisha, LA31) can be preferably used.

The content of the ultraviolet inhibitor is preferably 1 ppm to 1000 ppm, more preferably 10 ppm to 1000 ppm, in mass ratio in the optical film.

Matte

The optical film of the present invention may further contain a matting agent for imparting slidability. As the matting agent, an inorganic compound or an organic compound may be used provided that the transparency of the obtained film is not deteriorated and the heat resistance upon melting is not deteriorated. The matting agent may be used alone or in combination of two or more.

Among them, silicon dioxide having a refractive index close to that of the cellulose ester and excellent in transparency (haze) of the film is particularly preferably used. Specific examples of silicon dioxide include Aerosil 200V, Aerosil R972V, Aerosil R972, R974, R812, 200, 300, R202, OX50, TT600, NAX50 (manufactured by Nippon Aerosil Co., (Manufactured by Nippon Silica Industry Co., Ltd.), Admapine SO (manufactured by Nippon Silica Kagaku Kogyo Co., Ltd.), Sephosta KEP-30 Manufactured by Admatechs Co., Ltd.) and the like can be preferably used.

The shape of the particles is not particularly limited, such as irregular, needle-like, flat, spherical, or the like. When spherical particles are used, transparency of the obtained film is favorable, which is preferable.

The particle size is preferably smaller than the wavelength of the visible light and is preferably not more than 1/2 of the wavelength of the visible light, because the light is scattered when the wavelength is close to the wavelength of the visible light and the transparency deteriorates. If the particle size is too small, the slidability may not be improved. Therefore, it is preferable that the particle size is in the range of 80 nm to 180 nm. The particle size means the size of the aggregate when the particles are aggregates of primary particles. When the particle is not spherical, it means the diameter of the circle corresponding to the projected area.

The content of the mat agent may be about 0.05 to 1.0% by mass, preferably 0.1 to 0.8% by mass, based on the cellulose ester.

The thickness of the optical film of the present invention is preferably 15 to 35 占 퐉, and more preferably 15 to 30 占 퐉. If the thickness is less than 15 mu m, the strength of the film may not be sufficient. If the thickness is more than 35 mu m, for example, the optical film for a portable liquid crystal display may be too thick.

The optical film of the present invention can be obtained by biaxially stretching a film having a cellulose ester as a main component, which is an acetyl group as the acyl group, at a high magnification, as described later. Therefore, the optical film of the present invention has low whitishness (low haze), high tensile modulus in two stretching directions, and both elongation ratios in the two stretching directions are constant or less.

[Tensile modulus]

The tensile elastic modulus of the optical film of the present invention under 23 DEG C and 55RH in the direction of the slow axis and the direction perpendicular to the slow axis direction is preferably 3.0 to 8.5 mu m and more preferably 5.0 to 8.0 mu m desirable.

Particularly, in order to enhance the tensile elastic modulus in the TD / MD direction of the polarizing plate in a balanced manner when the polarizing plate is obtained by bonding the polarizer and the optical film by roll-to-roll bonding, And the tensile modulus in the direction (TD direction) orthogonal to the tensile modulus is preferably high. The tensile modulus of elasticity of the optical film in the direction (TD direction) perpendicular to the absorption axis direction (MD direction) of the polarizer is more preferably 5.0 to 8.0..

The tensile modulus of elasticity of the optical film in the slow axis direction (for example, the MD direction) can be measured by the following method. First, the optical film is cut into a size of 100 mm (MD direction) x 10 mm (TD direction) to obtain a sample film. This sample film was stretched in the slow axis direction (for example, the MD direction) with a chuck distance of 50 mm by using Tensilon RTC-1225A manufactured by Orientech Co., Ltd. according to JIS K7127, The tensile modulus of elasticity in the MD direction is measured. The measurement can be performed at 23 ° C and 55% RH.

The tensile modulus of elasticity in the direction orthogonal to the slow axis of the optical film (for example, in the direction of TD) is the same as the tensile elastic modulus of the optical film in the direction perpendicular to the slow axis (for example, TD direction) Can be measured in the same manner as described above.

[Breaking Shunt]

The elongation at break of the optical film of the present invention in the direction of the slow axis and the direction perpendicular thereto is preferably 1 to 10% and more preferably 1 to 5% at 23 캜 and 55% RH.

The elongation at break of the optical film in the slow axis direction (for example, the MD direction) can be measured by the following method. First, the optical film is cut into a size of 100 mm (MD direction) x 10 mm (TD direction) to obtain a sample film. Subsequently, the sample film is stretched in the direction of the slow axis (for example, the MD direction) with a chuck distance of 50 mm by using Tensilon RTC-1225A manufactured by Orientech, and the elongation at break is obtained from the breaking point of the film . The measurement can be carried out under the conditions of 23 占 폚 and 55% RH at a tensile rate of 50 mm / min.

The elongation at break in the direction orthogonal to the slow axis of the optical film (for example, the direction TD) is obtained by changing the direction in which the sample film is stretched in the direction perpendicular to the slow axis (for example, the TD direction) Can be measured in the same manner as described above.

The elongation at break (or tensile elastic modulus) of the optical film can be adjusted by 0, for example, by the total degree of substitution of the acyl group of the cellulose ester (acetyl group degree of substitution of cellulose acetate), the type of additive, the stretching condition and the like. In order to lower the elongation at break of the optical film (or increase the tensile modulus of elasticity), for example, a cellulose ester having a high degree of substitution of an acyl group may be selected, a polyester compound or a styrene compound having a certain molecular weight may be selected, The stretching ratio may be increased.

[Hayes]

As described above, the optical film of the present invention has less white turbidity and less haze. The haze value of the optical film of the present invention is preferably 1.0% or less, more preferably 0.5% or less. When the optical film of the present invention is used as a scattering film, the haze value may exceed the above range. The haze can be measured with a haze meter (turbidity meter) (model: NDH 2000, manufactured by Nippon Denshoku Co., Ltd.) in accordance with JIS K-7136.

[Retardation]

In the optical film of the present invention, the retardation R _o in the in-plane direction, which is measured under conditions of a measurement wavelength of 590 nm and 23 ° C and 55% RH, preferably satisfies ₀ ≦ R _o ≦ 20 nm, It is more preferable that _{o? 10} nm is satisfied. The retardation Rth in the thickness direction of the optical film measured under conditions of a measurement wavelength of 590 nm and 23 占 폚 55% RH preferably satisfies 0 nm? Rth? 80 nm, satisfies 0 nm? Rth? . The optical film having such a retardation value is preferably used as a protective film (F1 / F4) of a liquid crystal display device as described later.

R _o and Rth can be adjusted by the total substitution degree of the acyl group of the cellulose ester, the stretching condition and the like. In order to obtain R _o , for example, the total substitution degree of the acyl group of the cellulose ester may be increased or the difference in the draw ratio in the TD / MD direction may be reduced.

The retardation R _o and Rth are respectively defined by the following equations.

(I): R _o = (nx-ny) × d (nm)

(II): Rth = {(nx + ny) / 2-nz} xd (nm)

(In the formulas (I) and (II)

nx represents the refractive index in the slow axis direction x at which the refractive index becomes the maximum in the in-plane direction of the optical film;

ny represents a refractive index in an in-plane direction of the optical film in a direction y perpendicular to the slow axis direction x;

nz represents the refractive index in the thickness direction z of the optical film;

d (nm) represents the thickness of the optical film)

The retardation R _o and Rth can be determined, for example, by the following methods.

1) Moisture the optical film at 23 ° C and 55% RH. The average refractive index of the optical compensation film after humidity control is measured by an Abbe refractometer or the like.

2) R _o when light having a measurement wavelength of 590 nm is incident on the optical film after the humidity control in parallel with the normal line of the film surface is measured by KOBRA21DH, Oji Keisuke Co., Ltd.

3) When the light in a wavelength of 590 nm was incident from an angle (incident angle (?)) With respect to the surface normal line of the optical film by using KOBRA21ADH as the inclined axis (rotation axis) (?) Is measured. The measurement of the retardation value R ([theta]) can be performed at six points every 10 degrees in the range of [theta] of 0 DEG to 50 DEG. The in-plane slow axis of the optical film can be confirmed by KOBRA21ADH.

4) From the measured R ₀ and R (θ) and the above-mentioned average refractive index and film thickness, nx, ny and nz are calculated by KOBRA 21ADH, and Rth at the measurement wavelength of 590 nm is calculated. The measurement of the retardation can be performed under conditions of 23 占 폚 and 55% RH.

The angle? 1 (orientation angle) formed by the in-plane slow axis of the optical film and the width direction of the film is preferably -1 to + 1, more preferably -0.5 to + 0.5. Measurement of the orientation angle? 1 of the optical film can be carried out using an automatic birefringence system KOBRA-WR (Oji-Keisoku Kikuchi).

The optical film of the present invention has a total light transmittance of preferably 90% or more, and more preferably 93% or more.

The optical film of the present invention may further include a functional layer such as a hard coating layer, an antistatic layer, a back coat layer, an antireflection layer, an inactive layer, an adhesive layer, an antiglare layer and a barrier layer.

[Hard Coating Layer]

The hard coat layer contains a cured product of the active ray curable compound. As the active ray curable compound, a component containing a monomer having an ethylenically unsaturated double bond is preferably used. Examples of the active ray curable compound include an ultraviolet ray curable compound and an electron ray curable compound, but a compound which is cured by ultraviolet ray irradiation is preferable from the viewpoint of excellent mechanical strength (scratch resistance, pencil hardness).

As the ultraviolet ray hardening compound, for example, an ultraviolet ray hardening type urethane acrylate resin, an ultraviolet ray hardening type polyester acrylate resin, an ultraviolet ray hardening type epoxy acrylate type resin, an ultraviolet ray hardening type polyol acrylate type resin or an ultraviolet ray hardening type epoxy resin, Is used. Among them, an ultraviolet curable acrylate resin is preferable.

The hard coating layer can be obtained by coating a coating liquid for a hard coating layer containing a chemical compound and a photopolymerization initiator on an optical film and curing the coating liquid by actinic ray irradiation.

Specific examples of the photopolymerization initiator include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone,? -Amyloxime ester, thioxanthone, and derivatives thereof, but are not limited thereto. The amount of the photopolymerization initiator in the coating liquid for the hard coating layer is preferably in the range of 20: 100 to 0.01: 100 in terms of the mass ratio of the photopolymerization initiator: the incompatible compound.

The coating liquid for the hard coating layer preferably further contains inorganic fine particles or organic fine particles as required. Examples of the inorganic fine particles include silicon oxide, titanium oxide, aluminum oxide, tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, Aluminum silicate, magnesium silicate and calcium phosphate, and preferably silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide and the like are used.

Examples of the organic fine particles include polymethacrylic acid methyl acrylate resin powder, acryl styrene resin powder, polymethyl methacrylate resin powder, and silicone resin powder.

The average particle diameter of the fine particles is not particularly limited, but is preferably in the range of 0.01 to 5 탆, more preferably in the range of 0.01 to 1.0 탆, from the viewpoint of forming the antiglare layer. It may contain two or more kinds of fine particles having different particle diameters. The average particle diameter of the fine particles can be measured by, for example, a laser diffraction particle size distribution measuring apparatus.

The content of the fine particles is preferably in the range of 10 to 400 parts by mass, more preferably in the range of 50 to 200 parts by mass with respect to 100 parts by mass of the ultraviolet curable compound.

These hard coat layers are coated with a coating composition for forming a hard coat layer by a known method such as gravure coater, dip coater, reverse coater, wire bar coater, die coater, ink jet method, And the like.

The dry film thickness of the hard coat layer is in the range of 0.1 to 30 mu m, preferably 1 to 20 mu m, particularly preferably 6 to 15 mu m, on the average film thickness.

As the light source for the UV curing treatment, any light source that generates ultraviolet rays can be used without limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp and the like can be used.

Irradiation conditions vary depending on the respective lamps, but the irradiation dose of the active rays is usually in the range of 5 to 500 mJ / cm 2, preferably in the range of 5 to 200 mJ / cm 2.

[Antireflection layer]

The optical film of the present invention may further include an antireflection layer on the upper layer of the hard coat layer. Thereby, the optical film of the present invention can be used as an antireflection film having an external light reflection preventing function.

It is preferable that the antireflection layer is laminated in consideration of the refractive index, the film thickness, the number of layers, the layer order, and the like so as to reduce the reflectance by optical interference. It is preferable that the antireflection layer is composed of a combination of a low refractive index layer having a lower refractive index than the support (the optical film described above), or a high refractive index layer and a low refractive index layer having a higher refractive index than the support. Particularly preferably, three antireflection layers composed of three or more refractive index layers and having different refractive indices from the support side are used as the intermediate refractive index layer (a layer having a higher refractive index than the support and a refractive index lower than that of the high refractive index layer) / a high refractive index layer / Low refractive index layer are preferably laminated in this order. Alternatively, an antireflection layer having a layer structure of four or more layers in which two or more high refractive index layers and two or more low refractive index layers are alternately laminated is also preferably used.

As the layer structure of the antireflection film, the following structure is conceivable, but the present invention is not limited thereto.

Optical film / hard coating layer / low refractive index layer

Optical film / hard coating layer / medium refractive index layer / low refractive index layer

Optical film / hard coating layer / medium refractive index layer / high refractive index layer / low refractive index layer

Optical film / hard coating layer / high refractive index layer (conductive layer) / low refractive index layer

Optical film / hard coating layer / antiglare layer / low refractive index layer

The low refractive index layer necessary for the antireflection film preferably contains silica-based fine particles. The refractive index of the silica-based fine particles is lower than the refractive index of the support (the optical film described above) and is preferably in the range of 1.30 to 1.45 at 23 DEG C and a wavelength of 550 nm. As the silica-based fine particles, it is particularly preferable to have at least one outer layer and at least one porous or hollow particle inside. Particularly, it is preferable that the particles having the outer layers and the inside of which is porous or hollow are hollow silica-based fine particles.

The film thickness of the low refractive index layer is preferably from 5 nm to 0.5 탆, more preferably from 10 nm to 0.3 탆, and most preferably from 30 nm to 0.2 탆.

The low refractive index layer can be obtained by applying and drying a coating liquid for a low refractive index layer, and then curing it. The coating liquid for a low refractive index layer may further contain an organic silicon compound represented by the following formula (4), a hydrolyzate thereof, or a polycondensate thereof, containing the above silica-based fine particles.

The organosilicon compound represented by the general formula (4): wherein R represents an alkyl group having 1 to 4 carbon atoms. Specifically, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane and the like are preferably used.

The coating liquid for the low refractive index layer may further contain a solvent, a silane coupling agent, a curing agent, a surfactant and the like, if necessary.

2. Manufacturing method of optical film

The optical film of the present invention can be produced by a solution casting method or a melt casting method from the viewpoints of suppressing coloration, suppressing foreign matter defects, suppressing optical defects such as die lines, and the like. Of these, the solution casting method is preferable in that the obtained film has good planarity, fault tolerance such as stripe and film thickness accuracy and the like.

The production of the optical film of the present invention by the solution softening method comprises the steps of 1) dissolving a cellulose ester, an additive having a molecular weight of 10,000 or less having a ring structure and, if necessary, other additives in a solvent to obtain a dope solution, 2) (3) a step of peeling the film obtained by drying the softened dope liquid from the metal support, (4) a step of stretching the film, (5) a step of stretching the film after stretching It is preferable that the step of winding is performed.

1) Dissolution Process

The organic solvent useful for preparing the dope may be any solvent as long as it dissolves a cellulose ester or an additive having a ring structure at the same time.

For example, as the chlorine-based organic solvent, methylene chloride may be mentioned. Examples of the non-chlorinated organic solvent include organic solvents such as methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2- Ethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-methyl 2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane and the like . Among them, methylene chloride, methyl acetate, ethyl acetate, acetone and the like are preferable.

The dope preferably contains a linear or branched aliphatic alcohol having 1 to 4 carbon atoms in an amount of 1 to 40 mass% in addition to the above-mentioned organic solvent. When the alcohol is contained in the dope liquid, the membrane becomes gelated, and separation from the metal support is facilitated.

Examples of the straight chain or branched aliphatic alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol and tert-butanol. Ethanol is preferable because the stability and the boiling point of the inner dope are relatively low and the drying property is also good.

In particular, it is preferable to dissolve the cellulose ester and the additive having a cyclic structure in at least 15 to 45 mass% of the system in a solvent containing methylene chloride and a linear or branched aliphatic alcohol having 1 to 4 carbon atoms.

The dissolution of the cellulose ester and the like can be carried out by a method of performing the reaction at normal pressure, a method of performing the reaction at the boiling point or lower of the main solvent, a method of performing the reaction by pressurization at a boiling point or more of the main solvent, There are various methods such as a method of carrying out by a cooling dissolution method as described in JP-A-9-95538, a method of carrying out at high pressure as disclosed in JP-A-11-21379, Or more is preferable.

The concentration of the cellulose ester or the like in the dope liquid may be in the range of 15 to 45 mass% in total.

The filtration is preferably performed using a filter material having a collection particle diameter of 0.5 to 5 mu m and a filtration time of 10 to 25 sec / 100 ml for a filtration time.

In this method, by using the aggregate remaining at the time of dispersing the particles or the aggregates generated at the time of adding the main dope into the filter medium within the range of the collection particle diameter of 0.5 to 5 μm and the filtration time within the range of the filtration time of 10 to 25 sec / 100 ml Can be removed. In the main dope, since the concentration of the particles is sufficiently thin as compared with the additive liquid, the aggregates do not adhere to each other at the time of filtration, and the filtration pressure does not increase suddenly.

2) Flexible process

The dope liquid is fed to the pressure die through a feed pump (for example, a pressurized metering gear pump). Then, the dope liquid is plied to a flexible position of an endless metal support body (for example, a stainless steel belt or a rotating metal drum) which is infinitely transferred from the slit of the pressure die.

It is preferable to use a press die which can adjust the slit shape of the crotch member portion of the die and make the film thickness uniform. The pressure die includes a coated hanger die and a T die, all of which are preferably used. The surface of the metal support is mirror-finished. In order to increase the film-forming speed, two or more pressure dies may be provided on the metal support and the flow rate of the dope liquid may be divided to form an intermediate layer (double layer). Or a laminated structure film may be obtained by a covalent bonding method in which a plurality of dope liquids are simultaneously flexible.

3) Solvent evaporation and peeling process

The softened dope liquid on the metal support is heated on the metal support to evaporate the solvent in the dope liquid to obtain a film.

In order to evaporate the solvent, there are a method of blowing air from the side of the dope liquid and / or a method of transferring heat from the back surface of the support by liquid, and a method of transferring heat from the front and rear sides by radiant heat. Good. Also, a method of combining them is also preferably used. It is preferable that the dope liquid on the metal support is dried on the support under an atmosphere in the range of 40 to 100 캜. In order to keep the temperature within the range of 40 to 100 DEG C, it is preferable to heat the hot air at this temperature to the surface of the dope on the metal support or to heat it by means of infrared rays or the like.

The film obtained by evaporating the solvent on the metal support is peeled off at the peeling position. From the viewpoint of the surface quality, moisture permeability and releasability of the film-like material obtained, it is preferable to peel the film-like material from the metal support within 30 to 120 seconds after the softening. The temperature at the peeling position on the metal support is preferably in the range of 10 to 40 占 폚, and more preferably in the range of 11 to 30 占 폚.

The amount of the residual solvent at the time of peeling the film on the metal support at the time of peeling is desirably peeled in the range of 50 to 120 mass% depending on the strength of the drying condition, the length of the metal support, and the like. However, when the amount of the residual solvent is peeled off at a point where the amount of the residual solvent is larger, if the film is too soft, the flatness is deteriorated in peeling, and tearing or vertical stripes are liable to occur due to the peeling tension. Therefore, the amount of the residual solvent at the time of peeling is determined by a balance between the economic speed and the quality.

The amount of residual solvent in the membrane is defined by the following formula.

Residual solvent amount (%) = (mass before heat treatment of membrane-mass after heat treatment of membrane) / (mass after heat treatment of membrane) 占 100

The heat treatment at the time of measuring the residual solvent amount means that heat treatment is performed at 140 占 폚 for 1 hour.

The peel tension at the time of peeling the metal support and the film is usually in the range of 196 to 245 N / m, but it is preferable to peel off with a tension of 190 N / m or less when wrinkles tend to occur at peeling.

4) Drying and drawing process

The peeled film-like material is dried while being conveyed by a plurality of rollers arranged in the drying apparatus. Then, both ends of the film-like material are collected while being clipped by a tenter stretching device, and the film-like material is stretched.

Drying is generally carried out by blowing hot air on both sides of the membrane, but it may be heated by microwaves instead of hot air. Too rapid drying tends to impair the finished film planarity. Drying at a high temperature is preferably carried out at a residual solvent of about 8 mass% or less. And the drying is carried out within a range of approximately 40 to 250 ° C. Particularly preferably in the range of 40 to 200 ° C.

In the case of drying with a tenter stretching apparatus, the drying temperature is preferably in the range of 30 to 160 ° C, more preferably in the range of 50 to 150 ° C. In the tenter stretching apparatus, it is preferable that the temperature distribution in the width direction of the atmosphere is small from the viewpoint of enhancing the uniformity of the film. Therefore, the temperature distribution in the width direction in the tenter process is preferably within ± 5 ° C, more preferably within ± 2 ° C, and most preferably within ± 1 ° C.

In order to obtain the optical film of the present invention, stretching is preferably performed in at least two directions (biaxial stretching). The biaxial stretching is preferably performed in the stretching direction (MD direction) and the width direction (TD direction). The biaxial stretching may be performed at the same time or stepwise.

By stepwise, for example, it is also possible to sequentially perform different stretching in the stretching direction, to divide the stretching in the same direction in multiple steps, and to stretch in different directions to any one of the steps. For example, the following stretching step is possible.

Stretching in the flexible direction Stretching in the width direction

Stretching in the width direction Stretching in the width direction

Stretching in the flexible direction? Stretching in the width direction? Stretching in the width direction

Stretching in the width direction Stretching in the width direction Stretching in the stretting direction

The simultaneous biaxial stretching may include stretching in one direction and shrinking the other by relaxing the tension.

The drawing magnification is set so that the sum of the drawing magnifications in the drawing direction (MD direction) and the width direction (TD direction) is in the range of 2.5 to 9 times, preferably 3 to 6 times, more preferably 3.2 to 6 times . Specifically, the draw magnifications in the softening direction (MD direction) and the width direction (TD direction) may be 1.3 to 4.0 times, preferably 1.5 to 3.0 times, respectively. For example, when the draw ratio in the cross direction (MD direction) is 2.0 times and the draw ratio in the width direction (TD direction) is 1.5 times, the sum of the draw ratio becomes 2.0 + 1.5 = 3.5.

As described above, the film-like material containing a cellulose ester in which both of the acyl groups are acetyl groups and an additive having a cyclic structure has high extensibility. Therefore, the optical film obtained by biaxially stretching the film-like material at a high magnification has difficulty in causing cloudiness, has high tensile modulus in both directions perpendicular to each other, and has a reduced elongation at break.

The amount of the residual solvent of the film-like material at the start of the stretching is preferably in the range of 20 to 100 mass%. It is preferable that the film obtained after the stretching is dried until the residual solvent amount becomes 5% by mass or less, preferably 1% by mass or less.

5) Winding Process

The optical film obtained after stretching and drying is wound into a roll by a winding machine. As the winding method, those generally used may be used, and there are a static torque method, a constant tension method, a taper tension method, a program tension control method with a constant internal stress, and the like.

The optical film of the present invention may be a long film. For example, a long film having a length of 100 m to 10000 m and a width of 1 to 4 m, preferably 1.4 to 3 m, can be used. The long film can be usually saved as a roll wound in a direction perpendicular to the width direction.

Prior to winding, knurling (embossing) may be further applied to both ends in the width direction in order to prevent the attachment of the inner surface of the winding and the scratching, after the width direction end portion of the optical film is slit and cut. The knurling process can be performed by heating or pressurizing a metal ring having a concavo-convex pattern on its side surface.

In the optical film of the present invention, as described above, the tensile modulus of elasticity is increased. Therefore, even when the film thickness is as thin as about 15 to 35 占 퐉, it is possible to suppress the deformation (change in the winding shape) such that the central portion in the widthwise direction of the film becomes concave or convex when the winding core is held horizontally .

3. Polarizer

The polarizing plate of the present invention has a polarizer and an optical film of the present invention disposed on at least one side thereof.

The polarizer is an element that allows only light of a polarization plane in a certain direction to pass, and examples thereof include a polyvinyl alcohol polarizing film. The polyvinyl alcohol polarizing film includes a polyvinyl alcohol film stained with iodine and a dichroic dye stained.

The polarizer may be obtained by uniaxially stretching and dyeing a polyvinyl alcohol film; Or by dyeing a polyvinyl alcohol film, followed by uniaxially stretching, preferably by further performing a durability treatment with a boron compound. The film thickness of the polarizer is preferably in the range of 5 to 30 mu m, more preferably in the range of 5 to 15 mu m.

Examples of the polyvinyl alcohol film include those having an ethylene unit content of 1 to 4% by mole, a degree of polymerization of 2000 to 4000, and a degree of saponification of 99.0 to 99.99% by mole as described in JP-A-2003-248123 and JP-A-2003-342322 Ethylene-modified polyvinyl alcohol is preferably used.

When the optical film of the present invention is disposed on one surface of the polarizer, a retardation film may be disposed on the other surface of the polarizer. The retardation of the retardation film can be set according to the type of the liquid crystal cell to be combined. For example, the in-plane retardation R _o (590) of the retardation film measured at 23 ° C RH 55% and at a wavelength of 590 nm is preferably in the range of 30 to 150 nm, and the retardation R th (590) Is preferably in the range of 70 to 300 nm. The retardation film having the retardation within the above range can be preferably used, for example, in a VA type liquid crystal cell.

The bonding between the optical film and the polarizer is not particularly limited, but can be performed using a fully saponified polyvinyl alcohol-based adhesive, an active energy ray-curable adhesive, or the like. It is preferable to use an active energy ray-curable adhesive because the elasticity of the obtained adhesive layer is high and deformation of the polarizing plate is easily suppressed.

Preferable examples of the active energy ray-curable adhesive include (a) a cationic polymerizable compound, (β) a photo cationic polymerization initiator, (γ) a A photosensitizer exhibiting maximum absorption, and a photo-curable adhesive composition containing each component of (?) Naphthalene-based photo-sensitization assistant. However, other photo-curable adhesives may be used.

Hereinafter, an example of a method for producing a polarizing plate using a photo-curing adhesive will be described. The polarizing plate is provided with: 1) a pretreatment step of 1) facilitating the adhesion of the surface of the optical film to which the polarizer is adhered, 2) an adhesive application step of applying the following photocurable adhesive to at least one of the surface of the polarizer and the optical film, ) A joining step of joining the polarizer and the optical film to each other via the obtained adhesive layer and 4) a curing step of curing the adhesive layer in a state where the polarizer and the optical film are bonded via the adhesive layer have. 1) may be carried out as needed.

(Pre-processing step)

In the preprocessing step, an adhesion facilitating treatment is performed on the adhesion surface of the optical film to the polarizer. When an optical film is adhered to both surfaces of a polarizer, adhesion facilitating treatment is performed on the surface of each optical film to be adhered to the polarizer. Examples of the adhesion facilitating treatment include corona treatment and plasma treatment.

(Adhesive application step)

In the adhesive applying step, the photo-curing adhesive is applied to at least one of the bonding surfaces of the polarizer and the optical film. When the photo-curable adhesive is directly applied to the surface of the polarizer or optical film, the application method is not particularly limited. For example, various application methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater can be used. A method of softening the photo-curing adhesive between the polarizer and the optical film, then pressing the film with a roll or the like, and uniformly spreading the film can also be used.

(Bonding step)

After the photo-curable adhesive is applied in this way, it is supplied to the bonding step. In this bonding step, for example, when a photocurable adhesive is applied to the surface of the polarizer in the previous coating step, the optical films overlap with each other. When a photo-curing adhesive is applied to the surface of the optical film in the previous coating step, the polarizers overlap with each other. When the photo-curing adhesive is softened between the polarizer and the optical film, the polarizer and the optical film overlap with each other in this state. When an optical film is adhered to both sides of a polarizer, and when a photo-curing adhesive is used on both sides, the optical films overlap each other on both sides of the polarizer via a photo-curable adhesive. Normally, in this state, from both sides (on the side of the polarizer side and the optical film side when the optical films are overlapped with each other on the side of the polarizer, and on the side of the optical films on both sides thereof when the optical films are overlapped on both sides of the polarizer) And presses it. As the material of the roll, metal or rubber can be used. The rolls disposed on both sides may be the same material or different materials.

(Curing Process)

In the curing step, an uncured photocurable adhesive is irradiated with an active energy ray to cure the adhesive layer containing an epoxy compound or an oxetane compound. Thereby, the polarizer and the optical film superimposed on each other are bonded to each other via the photo-curable adhesive. When the optical film is bonded to one surface of the polarizer, the active energy ray may be irradiated from either the polarizer side or the optical film side. When an optical film is bonded to both surfaces of a polarizer, active energy rays are irradiated from either side of the optical film in a state where the optical films are superimposed on the both surfaces of the polarizer with a photo-curing adhesive interposed therebetween, It is advantageous to simultaneously cure the adhesive.

As the active energy ray, visible rays, ultraviolet rays, X rays, electron rays and the like can be used, and electron beams or ultraviolet rays are preferably used because they are easy to handle and have a sufficient curing speed.

Irradiation conditions of the electron beam may be any appropriate condition as long as the condition is such that the adhesive can be cured. For example, in the electron beam irradiation, the acceleration voltage is preferably in the range of 5 to 300 kV, more preferably in the range of 10 to 250 kV. When the accelerating voltage is less than 5 kV, the electron beam does not reach the adhesive and may be insufficiently cured. When the acceleration voltage exceeds 300 kV, the penetration force passing through the sample is too strong, There is a risk of causing damage. The irradiation dose is in the range of 5 to 100 kGy, more preferably in the range of 10 to 75 kGy. When the irradiation dose is less than 5 kGy, the adhesive becomes insufficient in curing. When the irradiation dose exceeds 100 kGy, the transparent optical film or the polarizer is damaged, resulting in a decrease in mechanical strength or yellowing, and desired optical characteristics can not be obtained.

The irradiation condition of the ultraviolet ray may be any appropriate condition as long as the adhesive can be cured. The amount of ultraviolet radiation is preferably in the range of 50 to 1500 mJ / cm2, more preferably in the range of 100 to 500 mJ / cm2 in terms of the accumulated light quantity.

In the polarizing plate thus obtained, the thickness of the adhesive layer is not particularly limited, but is usually within the range of 0.01 to 10, preferably within the range of 0.5 to 5 占 퐉.

In the optical film of the present invention, as described above, the elongation at break in the direction of the slow axis and the direction perpendicular to the slow axis direction are all reduced. Therefore, it is considered that the polarizing plate comprising the optical film of the present invention hardly causes heat wrinkling even under high temperature and high humidity.

4. Liquid crystal display

The liquid crystal display of the present invention includes a liquid crystal cell and a pair of polarizing plates for supporting the liquid crystal cell. At least one of the pair of polarizing plates may be a polarizing plate including the optical film of the present invention. At least one of the polarizing plates has a polarizer and an optical film of the present invention. The optical film of the present invention is preferably arranged on the side opposite to the liquid crystal cell of the polarizer (arranged as F1 or F4 described later).

1 is a schematic diagram showing an example of a basic configuration of a liquid crystal display device. 1, the liquid crystal display 10 of the present invention includes a liquid crystal cell 30, a first polarizing plate 50 and a second polarizing plate 70 for supporting the liquid crystal cell 30, a backlight 90 .

It is proposed that the liquid crystal cell 30 has various display modes such as STN, TN, OCB, HAN, VA (MVA, PVA), and IPS. In order to obtain a high contrast, a VA (MVA, PVA) mode is preferable.

The liquid crystal cell of the VA system has a pair of transparent substrates and a liquid crystal layer interposed between them.

On one of the pair of transparent substrates, a pixel electrode for applying a voltage to the liquid crystal molecules is disposed on one of the transparent substrates. The counter electrode may be disposed on the other transparent substrate (on which the pixel electrode is disposed) or may be disposed on the other transparent substrate. In order to increase the aperture ratio, the counter electrode may be disposed on the one transparent substrate .

The thickness of the transparent substrate is preferably in the range of 0.3 to 0.7 mm, and more preferably in the range of 0.3 to 0.5 mm.

The liquid crystal layer includes liquid crystal molecules having negative or positive dielectric anisotropy. It is preferable to use liquid crystal molecules having a negative dielectric constant anisotropy when the pixel electrodes are arranged on one transparent substrate and the opposing electrodes are arranged on the other transparent substrate. When both the pixel electrode and the counter electrode are disposed on one of the transparent substrates, it is preferable that the liquid crystal molecule has a positive dielectric constant anisotropy. The liquid crystal molecules are arranged such that the long axis of the liquid crystal molecules is parallel to the surface of the transparent substrate when the voltage is zero (no electric field is generated between the pixel electrode and the counter electrode) due to the alignment restraining force of the alignment film provided on the liquid crystal layer- And is oriented so as to be substantially perpendicular to the surface.

In the thus configured liquid crystal cell, an image signal (voltage) is applied to the pixel electrode to generate an electric field between the pixel electrode and the counter electrode. Thereby, the liquid crystal molecules which are initially aligned perpendicularly to the surface of the transparent substrate are oriented so that their long axes are in a horizontal direction with respect to the substrate surface. In this way, the liquid crystal layer is driven to change the transmissivity and reflectance of each sub-pixel to perform image display.

The first polarizing plate 50 includes a first polarizer 51, a protective film 53 (F1) disposed on the viewer-side surface of the first polarizer 51, And a protective film 55 (F2) disposed on the side of the protective film 55 (F2). The second polarizing plate 70 includes a second polarizer 71 and a protective film 73 (F3) disposed on the liquid crystal cell side surface of the second polarizer 71 and a backlight side And a protective film 75 (F4) disposed on the side of the protective film 75 (F4). One of the protective film 55 (F2) and the protective film 73 (F3) may be omitted if necessary.

At least one of the protective film 53 (F1) and the protective film 75 (F4); Preferably, both of them can be used as the optical film of the present invention.

As described above, the optical film of the present invention has less white turbidity and less haze. Therefore, the liquid crystal display device of the present invention having the optical film of the present invention as the protective film F1 / F4 can have a high luminance.

[Example]

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.

1. Material of optical film

1) Cellulose ester

Cellulose esters of the following table were used.

2) Additive

2-1) Additive having a cyclic structure

Polyester Compound 1: A terminal unsealed product of a condensate (weight average molecular weight 2000, bulk index 0.23) comprising succinic acid / terephthalic acid / ethylene glycol (50/50/100 molar ratio)

The bulk index of the polyester compound 1 was calculated as follows. That is, the polyester compound 1 contains a condensation unit of terephthalic acid / ethylene glycol- [C (═O) -C ₆ H ₄ -C (═O) -O-CH ₂ CH ₂ -O] - (molecular weight 192) (C = O) -CH ₂ CH ₂ -C (═O) -O-CH ₂ CH ₂ -O] - (molecular weight of 144) of the condensation unit of succinic acid / ethylene glycol. Therefore, the molecular weight of the polyester compound 1 is 192 x 50 + 144 x 50 + 18 = 16818. On the other hand, the total molecular weight of the aromatic ring structure (-C ₆ H ₄ -) in the polyester compound 1 is 76 (molecular weight of -C ₆ H ₄ -) × 50 (number) = 3800. Therefore, the bulk index of the polyester compound 1 becomes 3800/16818 = 0.23.

Polyester compound 2: A terminal unsealed product of a condensate (weight average molecular weight of 600) comprising succinic acid / terephthalic acid / ethylene glycol (50/50/100 molar ratio)

Polyester Compound 3: A terminal unsealed product of a condensate (weight average molecular weight: 3000) comprising succinic acid / terephthalic acid / ethylene glycol (50/50/100 molar ratio)

Polyester Compound 4: A terminal unsealed product of a condensate (weight average molecular weight 2000) comprising succinic acid / terephthalic acid / ethylene glycol (80/20/100 molar ratio)

Polyester Compound 5: A terminal unsealed product of a condensate (weight average molecular weight: 2000) consisting of succinic acid / terephthalic acid / ethylene glycol (75/25/100 molar ratio)

Polyester compound 6: A condensation product of a benzoic acid sealant (weight average molecular weight: 400) comprising adipic acid / phthalic acid / propylene glycol (50/50/100 molar ratio)

Polyester Compound 7: A benzoic acid sealant of a condensate (weight average molecular weight: 2000) consisting of succinic acid / terephthalic acid / ethylene glycol (75/25/100 molar ratio)

Polyester compound 8: A terminal unsealed product of a condensate (weight average molecular weight 1000) comprising adipic acid / terephthalic acid / propylene glycol (50/50/100 molar ratio)

Polyester Compound 9: A terminal unsealed product of a condensate (weight average molecular weight 1000) comprising sebacic acid / terephthalic acid / ethylene glycol (50/50/100 molar ratio)

(Styrene / maleic anhydride (67/33 mole ratio) copolymer, weight average molecular weight 9000, bulk index 0.82)

The bulk index of the styrene compound 1 was calculated as follows. That is, the styrene compound 1 contained 67 styrene units -CH (C ₆ H ₅ ) -CH ₂ - (molecular weight 104), maleic anhydride unit -C ₂ H ₂ (C ₂ O ₃ ) - (molecular weight 98) . Therefore, the molecular weight of the styrene compound 1 is 104 x 67 + 98 x 33 + 2 = 10204. On the other hand, the total molecular weight of the styrene-derived aromatic ring structure (-C ₆ H ₅ ) and the maleic anhydride derived non-aromatic ring structure (-CHC (═O) OC (═O) , 77 (molecular weight of -C ₆ H ₅ ) x 67 (number) +98 (molecular weight of -CHC (= O) OC (= O) CH-) x 33 (number) = 8393. Therefore, the bulk index of the styrene compound 1 is 8393/10204 = 0.82.

(Styrene / hydroxystyrene (50/50 mole ratio) copolymer having a weight average molecular weight of 2000, and a bulk index of 0.76) manufactured by Maruzen Kikuchi Kagaku Co., Ltd.,

The bulk index of the styrene compound 2 was calculated as follows. That is, the styrene-based compound 2 contains 50 styrene units -CH (C ₆ H ₅ ) -CH ₂ - (molecular weight 104), -hydroxystyrene unit -CH (C ₆ H ₅ OH) -CH ₂ - ) Are included, respectively. Therefore, the molecular weight of the styrene compound 2 is 120 x 50 + 104 x 50 + 2 = 11202. On the other hand, the total molecular weight of the aromatic ring structure -C ₆ H ₅ / -C ₆ H ₅ OH in styrene compound 2 is 77 (molecular weight of -C ₆ H ₅ ) × 50 (number) +93 (-C ₆ H ₅ OH molecular weight) x 50 (number) = 8500. Therefore, the bulk index of the styrene compound 2 is 8500/11202 = 0.76.

Sugar ester compound 1: a sugar ester compound represented by the following formula 3

(3)

R ₁ to R ₈ : benzoyl group (average degree of substitution: 5.5), and the remainder are hydrogen atoms

Sugar ester compound 2: a sugar ester compound obtained by changing the average substitution degree of the benzoyl group of R ₁ to R ₈ to 6.5 in the above formula (3)

Diester ester compound 3: A sugar ester compound obtained by changing the average substitution degree of the benzoyl group of R ₁ to R ₈ to 7.2 in the above formula (3)

Sugar ester compound 4: a sugar ester compound obtained by changing the average substitution degree of the benzoyl group of R ₁ to R ₈ to 8.0 in the above formula (3)

2-2) Other additives

Polyester Compound A: A terminal unsealed product of a condensate (weight average molecular weight: 1700) comprising adipic acid / ethylene glycol

TPP: Triphenylphosphate

BDP: Biphenyl diphenyl phosphate

2. Fabrication of optical film

[Example 1]

The following components were sufficiently dissolved while stirring and heating to prepare a dope solution.

(Composition of Dope Solution)

Cellulose ester A1: 100 parts by mass

Polyester compound 1: 10 parts by mass

Ultraviolet absorber: Ti928: 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) Nubin 928, manufactured by BASF Japan): 3.0 parts by mass

Matting agent: R972V (Nippon Aerosil Co., silica particles, average particle diameter = 16 nm): 0.30 parts by mass

Removal aid: Electronic Cut S412 (manufactured by Takemoto Yushi): 0.50 parts by mass

Methylene chloride: 300 parts by mass

Ethanol: 40 parts by mass

The obtained dope liquid was uniformly plied to the stainless steel band support at a temperature of 22 DEG C and a width of 2 m by using a belt softener. On the stainless steel band support, the solvent in the dope liquid was evaporated until the residual solvent amount became 100%. The obtained film was peeled off from the stainless steel band support at a peel tension of 162 N / m.

Subsequently, the peeled film was further dried at 35 DEG C, and then slit with a width of 1 m. The obtained film was stretched 2.0 times at 200 占 폚 in a conveying direction (MD direction) between rolls and stretched 1.5 times at 200 占 폚 in the transverse direction (TD direction) by a tenter. The amount of the residual solvent at the start of the stretching by the tenter was 8%.

After stretching in a tenter, relaxation treatment was performed at 130 캜 for 5 minutes, and the obtained film was dried while conveying a drying zone at 120 캜 and 140 캜 by a plurality of rollers. The resulting film was slit at a width of 1.5 m and knurled at both ends in the width direction of the film by a width of 10 mm and a height of 5 m and wound around the core. Thus, a roll of the optical film 101 was obtained. The film thickness of the optical film 101 was 25 탆, and the winding length was 4000 m.

[Examples 2 to 36, Comparative Examples 1 to 6 and 8 to 11]

Optical films 102 to 142 and 144 to 147 were obtained in the same manner as in Example 1 except that at least one of the cellulose ester, the additive and its content, the stretching condition and the film thickness were changed as shown in Table 3 or Table 4, ≪ / RTI >

[Comparative Example 7]

Production of pellets

The cellulose ester C (cellulose acetate propionate) shown in Table 1 was dried at 90 占 폚 for 6 hours or more with a dehumidifying hot air dryer to make the water content 80 ppm or less. The resulting cellulose ester C and the following additives were mixed with a hopper to prepare a resin composition.

(Composition of resin composition)

Cellulose ester C: 100 parts by mass

Polyester compound 1: 10 parts by mass

GSY-P101 (manufactured by Sakai Chemical Industry Co., Ltd.): 0.25 parts by mass

Irganox 1010 (manufactured by BASF Japan Ltd.): 0.5 parts by mass

Sumilizer GS (manufactured by Sumitomo Chemical Co., Ltd.): 0.24 parts by mass

R972V (Aerosil): 0.15 parts by mass

The resin composition was put in a twin-screw extruder and melted and kneaded. The molten resin was filtered with a metal mesh (filter portion) having a scale of 100 mu m installed immediately before the die, and then extruded at 240 DEG C from a circular bore of the die into a strand shape. After the extruded molten resin was water-cooled, it was cut into a cylindrical shape having a long diameter of 5 mm and a cross-sectional diameter of 2.5 mm by a strand cutter to obtain a pellet.

Production of film

The obtained pellets were dried under reduced pressure at 90 DEG C for 6 hours and then poured into a single screw extruder. Then, the mixture was melted and kneaded at 240 캜 in a nitrogen atmosphere, and then extruded from a die onto a cooling roll having a surface temperature of 90 캜. The extruded resin was cooled and solidified by a plurality of cooling rolls and then peeled off with a peeling roll to obtain a film. The resulting film-like product was slit at both ends and stretched 2.0 times at 200 占 폚 in a film-conveying direction (MD direction) by a roll stretching device and stretched 1.5 times at 200 占 폚 in the transverse direction (TD direction) . An optical film 143 having a thickness of 25 탆 was obtained in the same manner as in Example 1 except for the above.

The composition and elongation conditions of the optical films of Examples 1 to 19 and Comparative Examples 1 to 3 are shown in Table 3; Table 4 shows the composition of the optical films of Examples 20 to 36 and Comparative Examples 4 to 11 and the stretching conditions.

The tensile modulus, elongation at break, haze, R _o and Rth of the obtained optical film, and the wound shape were measured by the following methods.

[Tensile modulus and elongation at break]

First, the optical film was cut into a size of 10 mm (MD direction) x 100 mm (TD direction), and a sample film was obtained. This sample film was humidity-conditioned at 25 캜 and 55% RH for 24 hours. The tensile modulus of elasticity and the elongation at break of the sample film after the humidity control were measured in the MD direction using a tensile sheath RTC-1225A manufactured by Orientech Co., Ltd., in accordance with JIS K7127, with a chuck distance of 50 mm. The tensile modulus and the elongation at break in the TD direction were measured in the same manner except that the tensile direction of the sample film was changed to the TD direction. The tensile modulus and the elongation at break were measured at 23 DEG C under 55% RH at a tensile rate of 50 mm / min.

[Hayes]

The obtained optical film was humidity-conditioned at 23 占 폚 and 55% RH for 5 hours or more. Subsequently, the haze of the obtained optical film was measured with a haze meter (turbidity meter) (model: NDH 2000, manufactured by Nippon Denshoku Co., Ltd.) under the conditions of 23 占 폚 and 55% RH in accordance with JIS K-7136.

[R _o and Rth]

The in-plane retardation R _o and the thickness-direction retardation Rth of the optical film were measured by the following methods.

1) Humidify the optical film at 23 ° C and 55% RH. The average refractive index of the optical film after the humidity control was measured with an Abbe refractometer.

2) R _o when light with a measurement wavelength of 590 nm was incident on the optical film after humidity control in parallel with the normal line of the film surface was measured by KOBRA 21DH, Oji Keisuke Co., Ltd.

3) When the light in a wavelength of 590 nm was incident from an angle (incident angle (?)) With respect to the surface normal line of the optical film by using KOBRA21ADH as the inclined axis (rotation axis) (?) Was measured. The retardation value R ([theta]) was measured at 6 points every 10 degrees in the range of 0 DEG to 50 DEG. The in-plane slow axis of the optical film was confirmed by KOBRA21ADH.

4) From the measured R _o and R (θ) and the above-described average refractive index and film thickness, nx, ny and nz were calculated by KOBRA 21ADH to calculate Rth at a measurement wavelength of 590 nm.

[Change in winding shape]

A roll (winding length: 4000 m, width: 1330 m) obtained by winding the optical film in the direction perpendicular to the width direction was prepared. This roll was covered with a polyethylene sheet for preventing dust adhesion and stored for one month in a warehouse of 30 to 40 DEG C and 65% RH to 85% RH so that the lengthwise direction of the core (winding core) was horizontal. The wound state of the roll after one month was visually observed and evaluated as follows.

?: No change in wrinkles or deformation on the surface of the roll was observed.

?: A slight wrinkle was observed on the surface of the roll, but no deformation was confirmed.

?: Weak wrinkles were observed on the surface of the roll, and deformation was also confirmed on a part thereof.

X: Strong wrinkles on the surface or inside of the roll, strong deformation on the surface, and deformation to the inside.

The evaluation results of the optical films of Examples 1 to 19 and Comparative Examples 1 to 3 are shown in Table 5; The evaluation results of the optical films of Examples 20 to 36 and Comparative Examples 4 to 11 are shown in Table 6.

As shown in Tables 5 and 6, in the films of Examples 1 to 36, all of the elongation at break in the MD direction / TD direction was in the range of 1 to 10%, the haze was as low as 1% or less, It can be seen that the change is small. On the other hand, in the films of Comparative Examples 1 to 9, at least one of the MD direction and the TD direction has a high elongation at break of more than 10%, and the change in the winding shape is large.

Specifically, since the film of Comparative Example 1 contains CAP having a comparatively high flexibility, it is found that it produces cloudy appearance and has high fracture elongation. The film of Comparative Example 2 shows that the elongation at break is too high, so that the elongation at break is too low. The film of Comparative Example 4 is unstretched, the film of Comparative Example 5 is stretched only in the TD direction, and the film of Comparative Example 6 is stretched at a low magnification in both the MD / TD directions, . It can be seen that the film of Comparative Example 7 is not only cloudy but also has a high elongation at break because it is a melt-formed film using CAP. The TPP / BDP contained in the films of Comparative Examples 9 and 11 was found to be easy to bleed out, and the content in the film in the film forming process was reduced, so that the stretchability was low and the film elongation after stretching was high have. In Comparative Examples 8 and 10, the stretchability of the film was low, and it was found that the film was broken under the stretching condition shown in Table 4.

3. Fabrication of phase difference film

1) retardation film a

The following components were sufficiently dissolved while stirring and heating to prepare Dope Liquid 1.

(Composition of Dope Liquid 1)

Cellulose ester (diacetyl cellulose having an acetyl group substitution degree of 2.3 and a weight average molecular weight Mw of 18.5 million): 100 parts by weight

The following compound A-022 (retardation increasing agent): 4 parts by mass

A sugar ester compound represented by the following general formula (5): 10 parts by mass

R972V (manufactured by Nippon Aerosil Co., silica particles, average particle diameter = 16 nm, manufactured by Mat): 0.30 parts by mass

Methylene chloride: 300 parts by mass

Ethanol: 40 parts by mass

R ₁ to R ₈ : methylcarbonyl group (CH ₃ CO-), average degree of substitution: 5.5,

The dope liquid 1 prepared above was uniformly plied to a stainless steel band support at a temperature of 22 캜 and a width of 2 m using a belt pouring apparatus. The solvent in the dope liquid 1 of the stainless steel band support was evaporated until the amount of the residual solvent became 100%, and then peeled off from the stainless band support with a peeling tension of 162 N / m to obtain a film. Subsequently, the solvent in the obtained membrane was further evaporated at 35 DEG C, and then slit to a width of 1 m. The obtained membrane product was dried at 135 占 폚 while being stretched by 1.1 times in the conveying direction (MD direction) and 1.5 times in the transverse direction (TD direction) by stretching by tenter. The amount of the residual solvent at the start of the stretching by the tenter was 8%. After stretching in a tenter, relaxation treatment was performed at 130 캜 for 5 minutes.

The obtained film was dried while conveying a drying zone of 120 占 폚 and 140 占 폚 by a plurality of rollers. Thereafter, the film was slit at a width of 1.5 m and knurled at both ends in the width direction of the film by a width of 10 mm and a height of 5 탆 to obtain a retardation film a having a film thickness of 30 탆.

2) retardation film b

Preparation of Dope

The following components were mixed to prepare Dope Solutions A and B, respectively.

(Composition of Dope Solution A)

Cellulose ester CE-1 (acetyl group substitution degree 2.81, acyl group total substitution degree 2.81): 100 parts by weight

Additive A-5: Acetic acid endblock (number average molecular weight 800) of terephthalic acid / succinic acid (55 mol% / 45 mol%) / ethylene glycol / propylene glycol (45 mol% / 55 mol%

The following compound A: 4 parts by mass

Matting agent dispersion (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd., secondary average particle size: 1.0 占 퐉 or less): 0.13 parts by mass of solid content relative to 100 parts by mass of cellulose ester

Dichloromethane: 406 parts by mass

Methanol: 61 parts by mass

Compound A

(Composition of Dope Liquid B)

Cellulose ester CE-2 (acetyl group degree of substitution: 2.43, total substitution degree of acyl group: 2.43): 100 parts by weight

Additive A-5: Acetic acid endblock (number average molecular weight 800) of terephthalic acid / succinic acid (55 mol% / 45 mol%) / ethylene glycol / propylene glycol (45 mol% / 55 mol%

Matting agent dispersion (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd., secondary average particle size: 1.0 占 퐉 or less): 0.13 parts by mass of solid content relative to 100 parts by mass of cellulose ester

Dichloromethane: 406 parts by mass

Methanol: 61 parts by mass

(Co-flexible film)

Simultaneous multilayer fusing was performed so that the obtained dope liquids A and B were laminated on the running flexible band in the order of the dope liquid A, the dope liquid B and the dope liquid A from the flexible die. The softness of each dope was adjusted so that the core layer (the layer of the dope liquid B) became thickest. The film peeled off from the flexible band at a residual solvent amount of about 30 mass% was stretched by 30% in the width direction while blowing hot air at 140 캜 by a tenter. Thereafter, the film was transferred from the tenter conveying to the roll conveying path and again dried at 120 ° C to 150 ° C to obtain a retardation film b. The film thickness of the resulting retardation film b was 2.5 占 퐉 / 55 占 퐉 / 2.5 占 퐉 in the skin layer (the layer of the dope liquid A) / the core layer (layer of the dope liquid B) / the skin layer (layer of the dope liquid A).

3) retardation film c

The pellets of ZEONOR1420 (manufactured by Nippon Zeon Co., Ltd.), a norbornene resin, were dried at 100 DEG C for 5 hours. Thereafter, the pellets were supplied to an extruder by a conventional method, melted at 250 DEG C, and discharged from the die onto a cooling drum to obtain an unstretched film having a thickness of 150 mu m.

Subsequently, the above-mentioned unstretched film was stretched 1.2 times in the machine direction (MD direction) at a temperature of 143 캜 by a vertical stretching machine using a float system between rolls. This was fed to a transverse stretching machine using a tenter method and further stretched 1.8 times in the transverse direction (TD direction) at a temperature of 150 DEG C while adjusting the drawing tension and the tenter chain tension. Thereby, a retardation film c was obtained.

The in-plane retardation R _o and retardation R _th in the thickness direction of the obtained retardation films a to c at a wavelength of 590 nm were measured in the same manner as described above. The evaluation results are shown in Table 7.

4. Production of Polarizer

[Example 37]

1) Preparation of Polarizer

A polyvinyl alcohol film having a thickness of 30 占 퐉 was swelled in water at 35 占 폚. The obtained film was immersed in an aqueous solution containing 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds and further immersed in an aqueous solution at 45 캜 comprising 3 g of potassium iodide, 7.5 g of boric acid and 100 g of water. The resulting film was uniaxially stretched under the conditions of a stretching temperature of 55 캜 and a draw ratio of 5. The uniaxially stretched film was washed with water and then dried to obtain a polarizer having a thickness of 10 mu m.

2) Preparation of photocurable adhesive

The following components were mixed and defoamed to prepare a photocurable adhesive. Further, triarylsulfonium hexafluorophosphate was compounded as a 50% propylene carbonate solution, and the solid content of triarylsulfonium hexafluorophosphate was shown below.

(Composition of photo-curable adhesive)

3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate: 45 parts by weight

Polyd GT-301 (alicyclic epoxy resin manufactured by Daicel Chemical Industries, Ltd.): 40 parts by mass

1,4-butanediol diglycidyl ether: 15 parts by mass

Triarylsulfonium hexafluorophosphate: 2.3 parts by mass

9,10-dibutoxyanthracene: 0.1 part by weight

1.4-Diethoxynaphthalene: 2.0 parts by mass

Production of Polarizer

On the prepared retardation film a, the photo-curable adhesive prepared above was applied using a micro gravure coater so as to have a dry thickness of 5 mu m to form a photo-curable adhesive layer. The application was performed under conditions of a gravure roller # 300 and a rotation speed of 140% / line speed.

Similarly, the photo-curable adhesive prepared above was applied on the optical film 101 so as to have a dry thickness of 5 占 퐉 to form a photo-curable adhesive layer.

The optical film (101) having the photo-curable adhesive layer formed thereon was disposed on the other side of the retarder film (a) having the photo-curable adhesive layer formed on one side of the polarizer, and the retardation film a / / Polarizer / photo-curable adhesive layer / optical film (101). The resulting laminate was joined by a roller. The bonding was performed such that the slow axis of the optical film 101 and the absorption axis of the polarizer were orthogonal to each other.

The polarizing plate 201 was obtained by irradiating electron beams from both sides of the bonded laminate to cure the photo-curable adhesive layer. The line speed was 20 m / min, the acceleration voltage was 250 kV, and the irradiation dose was 20 kGy.

[Examples 38 to 72 and Comparative Examples 12 to 22]

Polarizers 202 to 247 were obtained in the same manner as in Example 37 except that the kinds of the optical film and the retardation film were changed as shown in Table 8 or Table 9. [

The heat wrinkles of the obtained polarizing plate were evaluated by the following methods.

[Heat wrinkles]

The polarizing plate 201 thus obtained was stored under the condition of 85 캜 and 95% for 168 hours, and the presence or absence of heat wrinkling was visually observed.

◎: Wrinkles of heat are not confirmed.

○: A slight wrinkle of heat was generated, but it was practically no problem level.

X: Wrinkles of heat occurred to a large extent.

The evaluation results of the polarizers of Examples 37 to 55 and Comparative Examples 12 to 14 are shown in Table 8; The evaluation results of the polarizing plates of Examples 56 to 72 and Comparative Examples 15 to 22 are shown in Table 9.

As shown in Tables 8 and 9, the polarizing plates of Comparative Examples 10 to 16 and 18 were in a level at which the polarizing plates of Examples 37 to 72 had practically no problem even when heat wrinkling did not occur or wrinkles were generated, , And heat wrinkles occur. It is considered that the tensile elastic moduli of the films constituting the polarizing plates of Examples 37 to 72 at least in the TD direction (preferably both the TD direction and MD direction) are high. It can be seen from the comparison between Examples 51 and 52 and other examples that it is possible to make the polarizing plate less prone to thermal wrinkling by making the tensile elastic modulus in the TD direction of the optical film higher than the tensile elastic modulus in the MD direction .

5. Fabrication of Liquid Crystal Display

[Example 73]

A pair of polarizers joined to both surfaces of a liquid crystal cell of a commercially available VA type liquid crystal display device (SONY type 40 display KLV-40J3000) were peeled off, and the polarizer plate 201 was placed on both surfaces of the liquid crystal cell And the liquid crystal display device 301 was obtained. The polarizing plate 201 was bonded so that the above-mentioned retardation film a became the liquid crystal cell side.

[Examples 74 to 108, Comparative Examples 23 to 33]

Liquid crystal display devices 302 to 347 were obtained in the same manner as in Example 73 except that the polarizing plate 201 bonded to both surfaces of the liquid crystal cell was changed as shown in Table 10 or Table 11. [

The luminance of the obtained liquid crystal display device was measured by the following method.

[Front Contrast (Brightness)]

The luminance from the normal direction of the display screen in the white display of the liquid crystal display device and the luminance from the normal direction of the display screen in the black display were measured using EZ-Contrast 160D manufactured by ELDIM. The obtained value was applied to the following equation and calculated as the front contrast. The luminance was measured in an environment of 23 占 폚 and 55% RH.

Front contrast = (luminance of white display measured from the normal direction of the display device) / (luminance of black display measured from the normal direction of the display)

Then, the brightness of the liquid crystal display device was evaluated based on the following criteria.

?: Front contrast of 1200 or more

○: Front contrast is more than 1000 and less than 1200

X: Front contrast less than 1000

The evaluation results of the liquid crystal display devices of Examples 73 to 91 and Comparative Examples 23 to 25 are shown in Table 10; Table 11 shows the evaluation results of the liquid crystal display devices of Examples 92 to 108 and Comparative Examples 26 to 33.

As shown in Tables 10 and 11, it can be seen that the liquid crystal display devices of Examples 73 to 108 have higher luminance than the liquid crystal display devices of Comparative Examples 23 to 25, 29, 31 and 33. It is considered that the film of F1 / F4 constituting the liquid crystal display devices of Examples 73 to 108 is less turbid and has low haze.

The present application claims priority based on Japanese Patent Application No. 2012-242742 filed on November 2, The contents of the above specification and drawings are all incorporated herein by reference.

The optical film of the present invention is less opaque and hardly causes heat wrinkles, and deterioration of the wound shape when it is stored in a roll can be reduced. A liquid crystal display device including such an optical film can have a high luminance.

10 Liquid crystal display
30 liquid crystal cell
50 first polarizer plate
51 first polarizer
53 Protective film (F1)
55 Protective film (F2)
70 second polarizer plate
71 Second polarizer
73 Protective film (F3)
75 Protective film (F4)
90 backlight

Claims (19)

A biaxially oriented film which is stretched in two orthogonal directions and which contains a cellulose ester in which the total substitution degree of an acyl group is 2.0 to 3.0 and in which all of the acyl groups are acetyl groups and an additive having a molecular weight of from 600 to 10,000, Lt;
The additive having the above-mentioned ring structure and having a molecular weight of 600 or more and 10,000 or less is a polyester compound or styrene compound having an aromatic ring structure in the ring structure contained in the repeating unit,
The elongation at break at 25 deg. C in the direction of the slow axis in the film plane and the direction perpendicular to the slow axis direction are all 1 to 10%
And a thickness of 15 to 35 mu m. The method according to claim 1,
And the haze measured according to JIS K-7136 is 0.5 or less. The method according to claim 1,
Wherein the ring structure is an aromatic ring. The method according to claim 1,
The content of the additive is 5 to 30 mass% with respect to the cellulose ester. The method according to claim 1,
Wherein the film has a tensile modulus of 5.0 to 8.0 하 under at 23 캜 and 55% RH in at least one of the direction of the slow axis in the film plane and the direction perpendicular to the direction of the slow axis. The method according to claim 1,
Wherein the elongation at break at 25 deg. C in the direction of the slow axis in the film plane and the direction perpendicular to the slow axis direction are all 1 to 5%. The method according to claim 1,
The retardation R _o (590) in the in-plane direction at 23 占 폚 and 55% RH and at the measurement wavelength of 590 nm is 0 nm or more and 10 nm or less. A cellulose ester in which the total substitution degree of an acyl group is 2.0 to 3.0 and both of the acyl groups are acetyl groups and an additive having a molecular weight of 600 or more and 10,000 or less,
A step of softening the dope liquid onto an endless metal support,
A step of peeling the filmy material obtained by drying the flexible dope liquid from the metal support,
A step of stretching the peeled film-like material at a draw magnification ratio of 1.3 to 4.0 times in two mutually orthogonal directions in the plane of the film-like material to obtain an optical film having a thickness of 15 to 35 탆
Wherein the optical film has a refractive index that is different from that of the optical film. 9. The method of claim 8,
The additive has a polyester compound or styrene compound or a pyranose structure or a furanose structure in which the cyclic structure contained in the repeating unit is a non-aromatic cyclic structure or an aromatic cyclic structure, Wherein the nitrous structure is a sugar ester compound having a substituent including a non-aromatic ring structure or an aromatic ring structure. 9. The method of claim 8,
Wherein the ring structure is an aromatic ring. 9. The method of claim 8,
Wherein the additive is a polyester compound or styrene compound having an aromatic ring structure in the cyclic structure contained in the repeating unit. 9. The method of claim 8,
The content of the additive is 5 to 30 mass% with respect to the cellulose ester. 9. The method of claim 8,
The retardation R _o (590) in the in-plane direction of the optical film at 23 ° C and 55% RH at a measurement wavelength of 590 nm is 0 nm or more and 10 nm or less. A polarizing plate comprising the optical film according to claim 1. A liquid crystal display device comprising the optical film according to claim 1. A liquid crystal display device comprising a liquid crystal cell, a first polarizer disposed on one side of the liquid crystal cell, the first polarizer having a first polarizer, and a second polarizer disposed on the other side of the liquid crystal cell and having a second polarizer,
The first polarizing plate has the optical film according to claim 1 disposed on the side of the first polarizer opposite to the liquid crystal cell,
The liquid crystal display device according to claim 1, wherein the second polarizer is disposed on a side of the second polarizer opposite to the liquid crystal cell. delete delete delete

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