JP2006083203A - Optical cellulose acylate film, method for producing the same, polarizing plate and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical cellulose acylate film having excellent properties of developing in-plane retardation and retardation in the thickness direction with slight dispersion of retardation value in the width direction and having a low coefficient of linear expansion and to provide a VA (vertically aligned) type liquid crystal display device with slight unevenness by black display and slight light leakage in corners. <P>SOLUTION: The optically biaxially stretched cellulose acylate film is characterized as follows. A film having <3% residual solvent content is delivered from a delivery apparatus, preheated at a lower temperature than the stretch temperature by 10-40°C and then stretched at 1.1-1.6 times in the width direction in a tenter apparatus heated at 140-180°C. The polarizing plate and the VA type liquid crystal display device are obtained by using the film. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an optical cellulose acylate film, a method for producing the same, a polarizing plate using the film, and a liquid crystal display device.

Liquid crystal display devices are widely used in monitors for personal computers and portable devices, and for television applications because of their various advantages, such as low voltage and low power consumption, enabling miniaturization and thinning. In such a liquid crystal display device, various modes have been proposed depending on the alignment state of the liquid crystal in the liquid crystal cell. Conventionally, the TN has an alignment state twisted by about 90 ° from the lower substrate to the upper substrate of the liquid crystal cell. The mode was mainstream.
In general, a liquid crystal display device includes a liquid crystal cell, an optical compensation sheet, and a polarizer. The optical compensation sheet is used for eliminating image coloring or expanding the viewing angle, and a stretched birefringent film or a film obtained by applying a liquid crystal to a transparent film is used. For example, Patent Document 1 discloses a technique of applying an optical compensation sheet in which a discotic liquid crystal is applied on a triacetyl cellulose film, aligned, and fixed to a TN mode liquid crystal cell to widen the viewing angle. However, a television-use liquid crystal display device that is expected to be viewed from various angles on a large screen has a strict requirement for viewing angle dependency, and even with the above-described method, the requirement cannot be satisfied. Therefore, liquid crystal display devices different from the TN mode, such as an IPS (In-Plane Switching) mode, an OCB (Optically Compensatory Bend) mode, and a VA (Vertically Aligned) mode, have been studied. In particular, the VA mode is attracting attention as a liquid crystal display device for TV because of its high contrast and relatively high production yield.

The cellulose acylate film is characterized by high optical isotropy (low retardation value) compared to other polymer films. Therefore, it is common to use a cellulose acetate film for an application requiring optical isotropy, for example, a polarizing plate.
On the other hand, the optical compensation sheet (retardation film) of the liquid crystal display device is required to have optical anisotropy (high retardation value). In particular, an optical compensation sheet for VA requires in-plane retardation (Re) of 30 to 200 nm and thickness direction retardation (Rth) of 70 to 400 nm. Therefore, it is common to use a synthetic polymer film having a high retardation value such as a polycarbonate film or a polysulfone film as the optical compensation sheet.
As described above, in the technical field of optical materials, when a polymer film requires optical anisotropy (high retardation value), a synthetic polymer film is used and optical isotropy (low retardation value) is used. It was a general principle to use cellulose acetate film when required.

Non-Patent Document 1 discloses a cellulose acetate film having a high retardation value that can be used for applications requiring optical anisotropy, overcoming the conventional general principle. On page 29 of Non-Patent Document 1, a method for producing a cellulose acylate phase difference plate that is stretched at 30 to 160 ° C. in a uniaxial direction or a biaxial direction at a temperature equal to or lower than the glass transition temperature is disclosed. It is preferable that the film process and the stretching process are performed sequentially or continuously, and the film is stretched in a state where the solvent remains in the film. In Patent Document 2, in order to achieve a high retardation value with cellulose triacetate, an aromatic compound having at least two aromatic rings, particularly a compound having a 1,3,5-triazine ring, is added and subjected to stretching treatment. . Cellulose triacetate is generally a polymer material that is difficult to stretch, and it is known that it is difficult to increase the birefringence. To achieve a high retardation value. Since this film can also serve as a protective film for the polarizing plate, there is an advantage that an inexpensive and thin liquid crystal display device can be provided.
Patent Document 3 discloses a cellulose ester optical biaxial film that is stretched 1.2 to 4.0 times in at least one direction at a temperature of 15 to 160 ° C. within a residual solvent amount of 10 to 100% by mass. Patent Document 4 discloses a cellulose mixed ester optical biaxial film that is stretched at a temperature of 140 to 200 ° C. under a condition that the residual solvent amount is 3 to 50 mass%.

As described above, in the conventional method for producing a cellulose acylate optical biaxial film, a method of heating and stretching in the presence of a residual solvent in a drying process after solvent casting, followed by drying and winding is performed. In other words, a method in which casting, stretching, and drying are consistently performed is common. This method has the advantage that it can be stretched at a relatively low temperature, but has many disadvantages. That is, the stretching process is rate-limiting and the production speed is slow. If trouble occurs somewhere in the process, the entire process is lost. Variations in the retardation value in the width direction are large, and unevenness in brightness and color tone of a liquid crystal display device using this film is likely to occur. Furthermore, the thermal expansion coefficient of the resulting film is increased, and the liquid crystal display device using the film has problems such as light leakage at the four sides and corners.
Invention Association Open Technique 2001-1745 European Patent Application No. 91656 JP 2002-187960 A JP 2003-14933 A

An object of the present invention is to provide a cellulose acylate film excellent in in-plane and thickness direction retardation, having little in-plane retardation variation, a low thermal expansion coefficient, and good production efficiency, and polarized light using the same. Is to provide a board.
Another object of the present invention is to provide a liquid crystal display device having excellent viewing angle characteristics and less unevenness.

These objects have been achieved by the following means.
(1) A roll film having a residual solvent amount of less than 3% is sent out from a delivery device, preheated at a temperature 10 to 40 ° C. lower than the stretching temperature, and then heated in a tenter device heated from 140 to 180 ° C. An optical biaxial cellulose acylate film that is stretched 1.1 to 1.6 times.
(2) The cellulose acylate film for optical use according to the above (1), wherein the in-plane retardation value Re and the retardation value Rth in the film thickness direction satisfy the following formulas (I) and (II).
(I) 30 ≦ Re ≦ 100
(II) 120 ≦ Rth ≦ 400
[Wherein, Re and Rth are values (unit: nm) at a wavelength of 590 nm. ]
(3) The cellulose acylate film for optical use according to (2), wherein 50 ≦ Re ≦ 100, Rth = a−5.9Re and 580 ≦ a ≦ 670.
(4) The optical cellulose acylate film as described in (2) above, wherein 30 ≦ Re ≦ 45 and 120 ≦ Rth ≦ 180.
(5) A difference ΔRe between a maximum Re value and a minimum Re value measured at 7 points in the width direction and an average Re value Rea measured at 7 points in the width direction satisfy the following formula (III): )-(4) The cellulose acylate film for optics in any one.
(III) ΔRe / Rea ≦ 0.025
(6) A difference ΔRth between a maximum Rth value measured at 7 points in the width direction and a minimum Rth value and an average Rth value Rtha measured at 7 points in the width direction satisfy the following formula (IV): The cellulose acylate film for optics according to any one of) to (5).
(IV) ΔRth / Rtha ≦ 0.02
(7) The thermal expansion coefficient in the casting direction (MD) is 75 ppm / ° C. or less and the thermal expansion coefficient in the width direction (TD) is 45 ppm / ° C. or less. An optical cellulose acylate film according to claim 1.
(8) A film comprising cellulose acylate obtained by substituting the hydroxyl group of cellulose with an acyl group having 2 or more carbon atoms, wherein the substitution degree of the acyl group at the 2-position is DS2 and the acyl group at the 3-position When the substitution degree is DS3 and the substitution degree of the acyl group at the 6-position is DS6, the following formulas (V) and (VI) are satisfied: Cellulose acylate film.
(V) 2.0 ≦ DS2 + DS3 + DS6 ≦ 3.0
(VI) DS6 / (DS2 + DS3 + DS6) ≧ 0.315
(9) The cellulose acylate film for optical use according to any one of (1) to (8), wherein the acyl group is an acetyl group.
(10) A roll-like film having a residual solvent amount of less than 3% is sent out from a delivery device, preheated at a temperature 10 to 40 ° C. lower than the stretching temperature, and then heated in a tenter device heated from 140 to 180 ° C. in the width direction A method for producing an optical biaxial cellulose acylate film, wherein the film is stretched 1.1 to 1.6 times.
(11) A polarizing plate using at least one optical cellulose acylate film according to any one of (1) to (9) as a protective film for a polarizer.
(12) The single plate transmittance TT, parallel transmittance PT, orthogonal transmittance CT, and polarization degree P at 25 ° C. and 60% RH of the polarizing plate satisfy at least one of the following formulas (a) to (d). The polarizing plate as described in (11) above, which is characterized.
(A) 40.0 ≦ TT ≦ 45.0
(B) 30.0 ≦ PT ≦ 40.0
(C) CT ≦ 2.0
(D) 95.0 ≦ P
(13) When the orthogonal transmittance at wavelength λ is CT ₍ λ ₎ , CT ₍₃₈₀₎ , CT ₍₄₁₀₎ , and CT ₍₇₀₀₎ satisfy at least one of the following formulas (e) to (g). The polarizing plate as described in (11) or (12) above.
(E) CT ₍₃₈₀₎ ≦ 2.0
(F) CT ₍₄₁₀₎ ≦ 0.1
(G) CT ₍₇₀₀₎ ≦ 0.5
(14) The orthogonal transmittance change amount ΔCT and the polarization degree change amount ΔP when left at 60 ° C. and 95% RH for 500 hours satisfy at least one of the following formulas (j) and (k): The polarizing plate according to any one of (11) to (13).
(J) −6.0 ≦ ΔCT ≦ 6.0
(K) -10.0 ≦ ΔP ≦ 0.0
(However, the amount of change is the value obtained by subtracting the pre-test measurement value from the post-test measurement value)
(15) A polarizing plate in which at least one layer of a hard coat layer, an antiglare layer and an antireflection layer is provided on the surface of the other protective film of the polarizing plate according to any one of (11) to (14).
(16) The polarizing plate packaged in a moisture-proof bag, wherein the humidity in the packaged state is 43% RH to 70% RH at 25 ° C. (11) The polarizing plate in any one of-(15).
(17) A polarizing plate packaged in a bag subjected to moisture-proofing treatment, wherein the humidity in the packaged state is within 15% RH with respect to the humidity when the polarizing plate is bonded to a liquid crystal panel. The polarizing plate (18) according to any one of the above (11) to (16), wherein the optical cellulose acylate film according to any one of (1) to (9) or the above (11) OCB mode liquid crystal display device using at least one polarizing plate according to any one of (1) to (17).
(19) The optical cellulose acylate film according to any one of (1) to (9) or the polarizing plate according to any one of (11) to (17) is used. VA mode liquid crystal display device.
(20) The optical cellulose acylate film according to any one of the above (1) to (3) and (5) to (9) or the polarizing plate according to any one of the above (11) to (17) A VA mode liquid crystal display device using only one sheet.
(21) The optical cellulose acylate film according to any one of (1), (2) and (4) to (9) above or the polarizing plate according to any one of (11) to (17) above as a liquid crystal A VA mode liquid crystal display device using one cell on each side of a cell.
(22) A cellulose acylate film comprising a mixed fatty acid ester of cellulose obtained by substituting a hydroxyl group of cellulose with an acetyl group and an acyl group having 3 or more carbon atoms, wherein the substitution degree of acetyl group is A and carbon atoms The optical cellulose acylate film according to any one of (1) to (9) above, wherein the substitution degree B of the acyl group having 3 or more satisfies the following formulas (VII) and (VIII):
(VII) 2.0 ≦ A + B ≦ 3.0
(VIII) 0.7 ≦ B
(23) The cellulose acylate film for optics according to the above (1) to (9), comprising at least one retardation developer composed of a rod-like or discotic compound.
(24) The optical cellulose acylate film according to any one of (1) to (9) above, which contains at least one of a plasticizer, an ultraviolet absorber, and a release agent.
(25) The optical cellulose acylate film according to any one of claims 1 to 9, wherein the film has a thickness of 40 to 160 µm.
(26) The above (1) and (B) are both satisfied between Re ₍ λ ₎ and Rth ₍ λ ₎ measured by changing the wavelength λ at 25 ° C. and 60% RH. The cellulose acylate film for optics of (9) to (9).
(A) 0.98 ≦ Re ₍₄₈₀₎ / Re ₍₆₃₀₎ ≦ 1.05
(B) 0.98 ≦ Rth ₍₄₈₀₎ / Rth ₍₆₃₀₎ ≦ 1.05

  The cellulose acylate film of the present invention is excellent in in-plane and thickness direction retardation, has little fluctuation in in-plane retardation, has a small thermal expansion coefficient, and is excellent in production efficiency. Further, since the liquid crystal display device of the present invention includes the cellulose acylate film, the liquid crystal display device is excellent in viewing angle characteristics and has little display unevenness.

  Hereinafter, the present invention will be described in detail. In the present specification, when a numerical value represents a physical property value, a characteristic value, etc., the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”. . In the present specification, the description “(meth) acrylate” means “at least one of acrylate and methacrylate”. The same applies to “(meth) acrylic acid” and the like.

(Cellulose acylate)
First, the cellulose acylate preferably used in the present invention will be described in detail. Glucose units having β-1,4 bonds constituting cellulose have free hydroxyl groups at the 2nd, 3rd and 6th positions. Cellulose acylate is a polymer obtained by esterifying some or all of these hydroxyl groups with acyl groups. The degree of acyl substitution DS2, DS3, DS6 means the ratio of esterification of the hydroxyl groups at the 2-position, 3-position and 6-position (100% esterification has a degree of substitution of 1). The total acyl substitution degree, that is, DS2 + DS3 + DS6 is preferably 2.00 to 3.00, more preferably 2.22 to 2.90, and particularly preferably 2.40 to 2.82. Further, DS6 / (DS2 + DS3 + DS6) is preferably 0.315 or more, more preferably 0.322 or more, and particularly preferably 0.324 to 0.340.
The acyl group used in the cellulose acylate of the present invention is most commonly an acetyl group. When the substitution degree of the acetyl group is A and the substitution degree of the acyl group having 3 or more carbon atoms is B, the sum of A and B is 2.0 or more, more preferably 2.22 to 2.90. And particularly preferably 2.40 to 2.82.
In addition, when B is 0.7 or more, a solution having a preferable solubility can be prepared. In particular, in a non-chlorine organic solvent, a favorable solution can be prepared. Furthermore, it becomes possible to produce a solution having a low viscosity and good filterability. The value of B is preferably 1.0 or more, and particularly preferably 1.7 or more.

  The acyl group having 3 or more carbon atoms of the cellulose acylate of the present invention may be an aliphatic group or an allyl group, and is not particularly limited. These are, for example, cellulose alkylcarbonyl esters, alkenylcarbonyl esters, aromatic carbonyl esters, aromatic alkylcarbonyl esters, and the like, each of which may further have a substituted group. These preferred B include propionyl, butanoyl, keptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, iso-butanoyl, t-butanoyl, cyclohexanecarbonyl, oleoyl, benzoyl , Naphthylcarbonyl, cinnamoyl group, and the like. Among these, propionyl, butanoyl, dodecanoyl, octadecanoyl, t-butanoyl, oleoyl, benzoyl, naphthylcarbonyl, cinnamoyl and the like. Particularly preferred are propionyl and butanoyl.

(Method for synthesizing cellulose acylate)
The basic principle of the method for synthesizing cellulose acylate is described in Mita et al., “Wood Chemistry”, pages 180-190 (Kyoritsu Shuppan, 1968). A typical synthesis method is a liquid phase esterification method using a carboxylic acid anhydride-acetic acid-sulfuric acid catalyst. Specifically, cellulose raw materials such as cotton linter and wood pulp are pretreated with an appropriate amount of acetic acid, and then put into a pre-cooled carboxylated mixed solution to be esterified to complete cellulose acylate (2nd, 3rd and 6th The total degree of acyl substitution at the position is approximately 3.00). The carboxylated mixed solution generally contains acetic acid as a solvent, carboxylic anhydride as an esterifying agent, and sulfuric acid as a catalyst. The carboxylic anhydride is usually used in a stoichiometric excess over the sum of the cellulose that reacts with it and the water present in the system. After completion of the acylation reaction, a neutralizing agent (for example, calcium, magnesium, iron, aluminum or zinc) is used for hydrolysis of excess carboxylic anhydride remaining in the system and neutralization of a part of the esterification catalyst. Of carbonate, acetate or oxide). Next, the obtained complete cellulose acylate is saponified and aged by maintaining it at 50 to 90 ° C. in the presence of a small amount of an acetylation reaction catalyst (generally, remaining sulfuric acid) to obtain the desired degree of acyl substitution and polymerization. The cellulose acylate having a degree is changed. When the desired cellulose acylate is obtained, the catalyst remaining in the system is completely neutralized with the neutralizing agent as described above, or in water or dilute sulfuric acid without neutralization. The cellulose acylate solution is added (or water or dilute sulfuric acid is added into the cellulose acylate solution) to separate the cellulose acylate, and the cellulose acylate is obtained by washing and stabilizing treatment.

The cellulose acylate film of the present invention is preferably composed of a cellulose acylate in which the polymer component constituting the film substantially has the above definition. “Substantially” means 55% by mass or more (preferably 70% by mass or more, more preferably 80% by mass or more) of the polymer component. Cellulose acylate particles are preferably used as a raw material for film production. 90% by mass or more of the particles to be used preferably have a particle diameter of 0.5 to 5 mm. Moreover, it is preferable that 50 mass% or more of the particle | grains to be used have a particle diameter of 1-4 mm. The cellulose acylate particles preferably have a shape as close to a sphere as possible.
The degree of polymerization of the cellulose acylate preferably used in the present invention is a viscosity average degree of polymerization of 200 to 700, preferably 250 to 550, more preferably 250 to 400, and particularly preferably a viscosity average degree of polymerization of 250 to 350. The average degree of polymerization can be measured by Uda et al.'S intrinsic viscosity method (Kazuo Uda, Hideo Saito, Journal of Textile Society, Vol. 18, No. 1, pages 105-120, 1962). Further details are described in JP-A-9-95538.

When the low molecular component is removed, the average molecular weight (degree of polymerization) increases, but the viscosity becomes lower than that of normal cellulose acylate, which is useful. Cellulose acylate having a small amount of low molecular components can be obtained by removing low molecular components from cellulose acylate synthesized by a usual method. The removal of the low molecular component can be carried out by washing the cellulose acylate with an appropriate organic solvent. In addition, when manufacturing a cellulose silicate with few low molecular components, it is preferable to adjust the sulfuric acid catalyst amount in an acetylation reaction to 0.5-25 mass parts with respect to 100 mass parts of cellulose. When the amount of the sulfuric acid catalyst is within the above range, cellulose acylate that is preferable in terms of molecular weight distribution (uniform molecular weight distribution) can be synthesized. When used in the production of the cellulose acylate of the present invention, its moisture content is preferably 2% by mass or less, more preferably 1% by mass or less, and particularly 0.7% by mass or less. It is a cellulose acylate having a rate. In general, cellulose acylate contains water and is known to be 2.5 to 5% by mass. In order to obtain the water content of the cellulose acylate in the present invention, it is necessary to dry it, and the method is not particularly limited as long as the desired water content is obtained.
These cellulose acylates of the present invention are described in detail on page 7 to page 12 of the raw material cotton and the synthesis method in the Japan Society of Invention and Innovation Technical Bulletin No. 2001-1745 (issued March 15, 2001, Japan Society of Invention and Innovation). It is described in.

(Additive)
In the cellulose acylate solution of the present invention, various additives (for example, plasticizers, UV inhibitors, deterioration inhibitors, retardation (optical anisotropy) modifiers, fine particles, peeling) according to the application in each preparation step. Agents, infrared absorbers, etc.), which may be solid or oily. That is, the melting point and boiling point are not particularly limited. For example, mixing of ultraviolet absorbing materials having melting points of 20 ° C. or less and 20 ° C. or more, and similarly, mixing of a plasticizer is described in, for example, JP-A-2001-151901. Examples of the release agent include ethyl esters of citric acid. Furthermore, infrared absorbing dyes are described, for example, in JP-A No. 2001-194522. Moreover, the addition time may be added at any time in the dope preparation step, but may be added by adding an additive to the final preparation step of the dope preparation step. Furthermore, the amount of each material added is not particularly limited as long as the function is manifested. Moreover, when a cellulose acylate film is formed from a multilayer, the kind and addition amount of the additive of each layer may differ. For example, it is described in Japanese Patent Application Laid-Open No. 2001-151902, and these are conventionally known techniques. It is preferable to set the glass transition point Tg of the cellulose acylate film to 70 to 145 ° C. and the elastic modulus measured with a tensile tester to 1500 to 5000 MPa depending on the selection of the types and addition amounts of these additives.
Further, for these details, materials described in detail on page 16 and after in the Invention Association Public Technical Bulletin No. 2001-1745 (issued on March 15, 2001, Invention Association) are preferably used.

(Retardation expression agent)
In the present invention, since a retardation value is expressed, a compound having at least two aromatic rings can be preferably used as a retardation developer. The retardation developer is preferably used in the range of 0.05 to 20 parts by mass, more preferably in the range of 0.1 to 10 parts by mass, with respect to 100 parts by mass of the polymer. It is more preferable to use in the range of 5 to 5 parts by mass, and most preferable to use in the range of 0.5 to 2 parts by mass. Two or more retardation developing agents may be used in combination. Moreover, when using together with the phosphate ester type plasticizer which has 3 or more aromatic rings, when the usage-amount of this plasticizer exceeds 8 mass%, the effect of a retardation enhancer may be diminished. In such a case, it is advantageous to reduce the amount of the plasticizer used to 8% by mass or less, preferably 6% by mass or less.
The retardation developer preferably has a maximum absorption in the wavelength region of 250 to 400 nm, and preferably has substantially no absorption in the visible region.

In the present specification, the “aromatic ring” includes an aromatic hetero ring in addition to an aromatic hydrocarbon ring.
The aromatic hydrocarbon ring is particularly preferably a 6-membered ring (that is, a benzene ring).
The aromatic heterocycle is generally an unsaturated heterocycle. The aromatic heterocycle is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring. Aromatic heterocycles generally have the most double bonds. As the hetero atom, a nitrogen atom, an oxygen atom and a sulfur atom are preferable, and a nitrogen atom is particularly preferable. Examples of aromatic heterocycles include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring, pyridine ring , Pyridazine ring, pyrimidine ring, pyrazine ring and 1,3,5-triazine ring.
As the aromatic ring, benzene ring, furan ring, thiophene ring, pyrrole ring, oxazole ring, thiazole ring, imidazole ring, triazole ring, pyridine ring, pyrimidine ring, pyrazine ring and 1,3,5-triazine ring are preferable, In particular, a 1,3,5-triazine ring is preferably used. Specifically, for example, compounds disclosed in JP-A No. 2001-166144 are preferably used.

The number of aromatic rings contained in the retardation enhancer is preferably 2 to 20, more preferably 2 to 12, still more preferably 2 to 8, and most preferably 2 to 6. preferable.
The bond relationship between two aromatic rings can be classified into (a) a condensed ring, (b) a direct bond with a single bond, and (c) a bond through a linking group (for aromatic rings). , Spiro bonds cannot be formed). The connection relationship may be any of (a) to (c).

  Examples of the condensed ring (a condensed ring of two or more aromatic rings) include an indene ring, a naphthalene ring, an azulene ring, a fluorene ring, a phenanthrene ring, an anthracene ring, an acenaphthylene ring, a biphenylene ring, a naphthacene ring, Pyrene ring, indole ring, isoindole ring, benzofuran ring, benzothiophene ring, indolizine ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzotriazole ring, purine ring, indazole ring, chromene ring, quinoline ring, isoquinoline Ring, quinolidine ring, quinazoline ring, cinnoline ring, quinoxaline ring, phthalazine ring, pteridine ring, carbazole ring, acridine ring, phenanthridine ring, xanthene ring, phenazine ring, phenothiazine ring, phenoxathiin ring, phenoxazine ring and thiant It includes emissions ring. Naphthalene ring, azulene ring, indole ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzotriazole ring and quinoline ring are preferred.

  The single bond (b) is preferably a bond between carbon atoms of two aromatic rings. Two aromatic rings may be bonded with two or more single bonds to form an aliphatic ring or a non-aromatic heterocyclic ring between the two aromatic rings.

The linking group in (c) is also preferably bonded to carbon atoms of two aromatic rings. The linking group is preferably an alkylene group, an alkenylene group, an alkynylene group, —CO—, —O—, —NH—, —S—, or a combination thereof. Examples of linking groups composed of combinations are shown below. In addition, the relationship between the left and right in the following examples of the linking group may be reversed.
c1: -CO-O-
c2: —CO—NH—
c3: -alkylene-O-
c4: —NH—CO—NH—
c5: —NH—CO—O—
c6: —O—CO—O—
c7: -O-alkylene-O-
c8: -CO-alkenylene-
c9: -CO-alkenylene-NH-
c10: -CO-alkenylene-O-
c11: -alkylene-CO-O-alkylene-O-CO-alkylene-
c12: -O-alkylene-CO-O-alkylene-O-CO-alkylene-O-
c13: -O-CO-alkylene-CO-O-
c14: -NH-CO-alkenylene-
c15: -O-CO-alkenylene-

The aromatic ring and the linking group may have a substituent.
Examples of the substituent include halogen atom (F, Cl, Br, I), hydroxyl, carboxyl, cyano, amino, nitro, sulfo, carbamoyl, sulfamoyl, ureido, alkyl group, alkenyl group, alkynyl group, aliphatic acyl group , Aliphatic acyloxy group, alkoxy group, alkoxycarbonyl group, alkoxycarbonylamino group, alkylthio group, alkylsulfonyl group, aliphatic amide group, aliphatic sulfonamido group, aliphatic substituted amino group, aliphatic substituted carbamoyl group, aliphatic Substituted sulfamoyl groups, aliphatic substituted ureido groups and non-aromatic heterocyclic groups are included.

The alkyl group preferably has 1 to 8 carbon atoms. A chain alkyl group is preferable to a cyclic alkyl group, and a linear alkyl group is particularly preferable. The alkyl group may further have a substituent (eg, hydroxy, carboxy, alkoxy group, alkyl-substituted amino group). Examples of alkyl groups (including substituted alkyl groups) include methyl, ethyl, n-butyl, n-hexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl and 2-diethylaminoethyl.
The alkenyl group preferably has 2 to 8 carbon atoms. A chain alkenyl group is preferable to a cyclic alkenyl group, and a linear alkenyl group is particularly preferable. The alkenyl group may further have a substituent. Examples of alkenyl groups include vinyl, allyl and 1-hexenyl.
The alkynyl group preferably has 2 to 8 carbon atoms. A chain alkynyl group is preferable to a cyclic alkynyl group, and a linear alkynyl group is particularly preferable. The alkynyl group may further have a substituent. Examples of alkynyl groups include ethynyl, 1-butynyl and 1-hexynyl.

The aliphatic acyl group preferably has 1 to 10 carbon atoms. Examples of the aliphatic acyl group include acetyl, propanoyl and butanoyl.
The aliphatic acyloxy group preferably has 1 to 10 carbon atoms. Examples of the aliphatic acyloxy group include acetoxy.
The number of carbon atoms of the alkoxy group is preferably 1 to 8. The alkoxy group may further have a substituent (eg, alkoxy group). Examples of alkoxy groups (including substituted alkoxy groups) include methoxy, ethoxy, butoxy and methoxyethoxy.
The alkoxycarbonyl group preferably has 2 to 10 carbon atoms. Examples of the alkoxycarbonyl group include methoxycarbonyl and ethoxycarbonyl.
The number of carbon atoms of the alkoxycarbonylamino group is preferably 2 to 10. Examples of the alkoxycarbonylamino group include methoxycarbonylamino and ethoxycarbonylamino.

The alkylthio group preferably has 1 to 12 carbon atoms. Examples of the alkylthio group include methylthio, ethylthio and octylthio.
The alkylsulfonyl group preferably has 1 to 8 carbon atoms. Examples of the alkylsulfonyl group include methanesulfonyl and ethanesulfonyl.
The aliphatic amide group preferably has 1 to 10 carbon atoms. Examples of the aliphatic amide group include acetamide.
The aliphatic sulfonamide group preferably has 1 to 8 carbon atoms. Examples of the aliphatic sulfonamido group include methanesulfonamido, butanesulfonamido and n-octanesulfonamido.
The number of carbon atoms of the aliphatic substituted amino group is preferably 1 to 10. Examples of the aliphatic substituted amino group include dimethylamino, diethylamino and 2-carboxyethylamino.
The aliphatic substituted carbamoyl group preferably has 2 to 10 carbon atoms. Examples of the aliphatic substituted carbamoyl group include methylcarbamoyl and diethylcarbamoyl.
The aliphatic substituted sulfamoyl group preferably has 1 to 8 carbon atoms. Examples of the aliphatic substituted sulfamoyl group include methylsulfamoyl and diethylsulfamoyl.
The number of carbon atoms in the aliphatic substituted ureido group is preferably 2 to 10. Examples of the aliphatic substituted ureido group include methylureido.
Examples of non-aromatic heterocyclic groups include piperidino and morpholino.
The molecular weight of the retardation developer is preferably 300 to 800.

  In the present invention, a rod-shaped compound having a linear molecular structure can be preferably used in addition to a compound using a 1,3,5-triazine ring. The linear molecular structure means that the molecular structure of the rod-like compound is linear in the most thermodynamically stable structure. The most thermodynamically stable structure can be obtained by crystal structure analysis or molecular orbital calculation. For example, molecular orbital calculation can be performed using molecular orbital calculation software (eg, WinMOPAC2000, manufactured by Fujitsu Limited) to determine the molecular structure that minimizes the heat of formation of the compound. The molecular structure being linear means that in the thermodynamically most stable structure obtained by calculation as described above, the angle of the main chain constituting the molecular structure is 140 degrees or more.

  As the rod-shaped compound having at least two aromatic rings, a compound represented by the following general formula (1) is preferable.

Formula (1): Ar ¹ -L ¹ -Ar ²

In the general formula (1), Ar ¹ and Ar ² are each independently an aromatic group.
In the present specification, the aromatic group includes an aryl group (aromatic hydrocarbon group), a substituted aryl group, an aromatic heterocyclic group, and a substituted aromatic heterocyclic group.
An aryl group and a substituted aryl group are more preferable than an aromatic heterocyclic group and a substituted aromatic heterocyclic group. The heterocycle of the aromatic heterocyclic group is generally unsaturated. The aromatic heterocycle is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring. Aromatic heterocycles generally have the most double bonds. As a hetero atom, a nitrogen atom, an oxygen atom or a sulfur atom is preferable, and a nitrogen atom or a sulfur atom is more preferable.
As the aromatic ring of the aromatic group, a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, a thiazole ring, an imidazole ring, a triazole ring, a pyridine ring, a pyrimidine ring and a pyrazine ring are preferable, and a benzene ring is particularly preferable. .

  Examples of the substituent of the substituted aryl group and the substituted aromatic heterocyclic group include halogen atom (F, Cl, Br, I), hydroxyl, carboxyl, cyano, amino, alkylamino group (eg, methylamino, ethylamino) , Butylamino, dimethylamino), nitro, sulfo, carbamoyl, alkylcarbamoyl groups (eg, N-methylcarbamoyl, N-ethylcarbamoyl, N, N-dimethylcarbamoyl), sulfamoyl, alkylsulfamoyl groups (eg, N- Methylsulfamoyl, N-ethylsulfamoyl, N, N-dimethylsulfamoyl), ureido, alkylureido groups (eg, N-methylureido, N, N-dimethylureido, N, N, N′-trimethyl) Ureido), alkyl groups (eg, methyl, ethyl, propyl, butyl, pentyl, Heptyl, octyl, isopropyl, s-butyl, t-amyl, cyclohexyl, cyclopentyl), alkenyl groups (eg, vinyl, allyl, hexenyl), alkynyl groups (eg, ethynyl, butynyl), acyl groups (eg, formyl, acetyl, Butyryl, hexanoyl, lauryl), acyloxy groups (eg, acetoxy, butyryloxy, hexanoyloxy, lauryloxy), alkoxy groups (eg, methoxy, ethoxy, propoxy, butoxy, pentyloxy, heptyloxy, octyloxy), aryloxy groups (Eg, phenoxy), alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, heptyloxycarbonyl), aryloxycarbo Group (eg, phenoxycarbonyl), alkoxycarbonylamino group (eg, butoxycarbonylamino, hexyloxycarbonylamino), alkylthio group (eg, methylthio, ethylthio, propylthio, butylthio, pentylthio, heptylthio, octylthio), arylthio group (eg, , Phenylthio), alkylsulfonyl groups (eg, methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, pentylsulfonyl, heptylsulfonyl, octylsulfonyl), amide groups (eg, acetamido, butyramide, hexylamide, laurylamide) and non- Aromatic heterocyclic groups (eg, morpholyl, pyrazinyl) are included.

Examples of the substituent for the substituted aryl group and the substituted aromatic heterocyclic group include a halogen atom, cyano, carboxyl, hydroxyl, amino, alkyl-substituted amino group, acyl group, acyloxy group, amide group, alkoxycarbonyl group, alkoxy group, alkylthio And groups and alkyl groups are preferred.
The alkyl part and the alkyl group of the alkylamino group, alkoxycarbonyl group, alkoxy group and alkylthio group may further have a substituent. Examples of alkyl moieties and substituents of alkyl groups include halogen atom, hydroxyl, carboxyl, cyano, amino, alkylamino group, nitro, sulfo, carbamoyl, alkylcarbamoyl group, sulfamoyl, alkylsulfamoyl group, ureido, alkylureido Group, alkenyl group, alkynyl group, acyl group, acyloxy group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxycarbonylamino group, alkylthio group, arylthio group, alkylsulfonyl group, amide group and non-aromatic An aromatic heterocyclic group is included. As the substituent for the alkyl moiety and the alkyl group, a halogen atom, hydroxyl, amino, alkylamino group, acyl group, acyloxy group, acylamino group, alkoxycarbonyl group and alkoxy group are preferable.

In the general formula (1), L ¹ is a divalent linking group selected from an alkylene group, an alkenylene group, an alkynylene group, —O—, —CO— and a combination thereof.
The alkylene group may have a cyclic structure. As the cyclic alkylene group, cyclohexylene is preferable, and 1,4-cyclohexylene is particularly preferable. As the chain alkylene group, a linear alkylene group is more preferable than a branched alkylene group.
The alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 15, more preferably 1 to 10, still more preferably 1 to 8, and most preferably 1 to 6 carbon atoms. It is.

The alkenylene group and alkynylene group preferably have a chain structure rather than a cyclic structure, and more preferably have a linear structure rather than a branched chain structure.
The number of carbon atoms of the alkenylene group and the alkynylene group is preferably 2 to 10, more preferably 2 to 8, further preferably 2 to 6, further preferably 2 to 4, and most preferably 2. (Vinylene or ethynylene).
The arylene group preferably has 6 to 20 carbon atoms, more preferably 6 to 16, and still more preferably 6 to 12.

In the molecular structure of the general formula (1), the angle formed by Ar ¹ and Ar ² across L ¹ is preferably 140 degrees or more.

  As the rod-like compound, a compound represented by the following formula (2) is more preferable.

Formula ^{(2): Ar 1 -L 2} -X-L 3 -Ar 2

In the general formula (2), Ar ¹ and Ar ² are each independently an aromatic group. The definition and examples of the aromatic group are the same as those of Ar ¹ and Ar ^{2 in} the general formula (1).
In the general formula (2), L ² and L ³ are each independently a divalent linking group selected from an alkylene group, —O—, —CO—, and a group consisting of a combination thereof.
The alkylene group preferably has a chain structure rather than a cyclic structure, and more preferably has a linear structure rather than a branched chain structure.
The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 8, more preferably 1 to 6, still more preferably 1 to 4, and 1 or 2 (methylene or Most preferred is ethylene).
L ² and L ³ are particularly preferably —O—CO— or —CO—O—.

In the general formula (2), X is 1,4-cyclohexylene, vinylene or ethynylene.
Specific examples of the compound represented by the general formula (1) are shown below. (The compound represented by the general formula (2) is also included.)

  Specific examples (1) to (34), (41), and (42) have two asymmetric carbon atoms at the 1-position and the 4-position of the cyclohexane ring. However, since the specific examples (1), (4) to (34), (41), and (42) have a symmetrical meso type molecular structure, there are no optical isomers (optical activity), and geometric isomers (trans Type and cis type). The trans type (1-trans) and cis type (1-cis) of specific example (1) are shown below.

As described above, the rod-like compound preferably has a linear molecular structure. Therefore, the trans type is preferable to the cis type.
Specific examples (2) and (3) have optical isomers (a total of four isomers) in addition to geometric isomers. As for geometric isomers, the trans type is similarly preferable to the cis type. The optical isomer is not particularly superior or inferior, and may be D, L, or a racemate.
In specific examples (43) to (45), the central vinylene bond includes a trans type and a cis type. For the same reason as above, the trans type is preferable to the cis type.
Other preferred compounds are shown below.

    A compound represented by the following general formula (3) is also preferable.

（式中、R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁹およびR¹⁰はそれぞれ独立に水素原子または置換基を表し、R¹、R²、R³、R⁴およびR⁵のうち少なくとも1つは電子供与性基を表す。Ｒ⁸は水素原子、炭素数１〜４のアルキル基、炭素数２〜６のアルケニル基、炭素数２〜６のアルキニル基、炭素数６〜１２のアリール基、炭素数1〜１２のアルコキシ基、炭素数６〜１２のアリールオキシ基、炭素数２〜１２のアルコキシカルボニル基、炭素数２〜１２のアシルアミノ基、シアノ基またはハロゲン原子を表す。）

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ each represents an electron donating group, wherein R ⁸ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkynyl group having 2 to 6 carbon atoms. Group, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, cyano Represents a group or a halogen atom.)

Two or more rod-shaped compounds having a maximum absorption wavelength (λmax) shorter than 250 nm in the ultraviolet absorption spectrum of the solution may be used in combination.
The rod-like compound can be synthesized with reference to methods described in literature. References include Mol. Cryst. Liq. Cryst., 53, 229 (1979), 89, 93 (1982), 145, 111 (1987), 170, 43 Page (1989), J. Am. Chem. Soc., 113, 1349 (1991), 118, 5346 (1996), 92, 1582 (1970), J. Org Chem., 40, 420 (1975), Tetrahedron, 48, 16, 3437 (1992).

  The addition amount of the retardation enhancer is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, based on the amount of the polymer.

  The aromatic compound is used in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of cellulose acetate. The aromatic compound is preferably used in the range of 0.05 to 15 parts by mass, more preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of cellulose acetate. Two or more kinds of compounds may be used in combination.

Next, the organic solvent in which the cellulose acylate of the present invention is dissolved will be described.
(Chlorine solvent)
In preparing the cellulose acylate solution of the present invention, a chlorinated organic solvent is preferably used as the main solvent. In the present invention, the type of the chlorinated organic solvent is not particularly limited as long as the object can be achieved within a range where the cellulose acylate can be dissolved, cast and formed. These chlorinated organic solvents are preferably dichloromethane and chloroform. Particularly preferred is dichloromethane. In addition, there is no particular problem in mixing an organic solvent other than the chlorinated organic solvent. In that case, it is necessary to use at least 50% by mass of dichloromethane. The non-chlorine organic solvent used in combination with the chlorinated organic solvent in the present invention is described below. That is, as a preferable non-chlorine organic solvent, a solvent selected from esters, ketones, ethers, alcohols, hydrocarbons and the like having 3 to 12 carbon atoms is preferable. Esters, ketones, ethers and alcohols may have a cyclic structure. A compound having two or more functional groups of esters, ketones and ethers (that is, —O—, —CO— and —COO—) can also be used as a solvent. For example, other functional groups such as alcoholic hydroxyl groups can be used. You may have group simultaneously. In the case of a solvent having two or more types of functional groups, the number of carbon atoms may be within the specified range of the compound having any functional group. Examples of esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate. Examples of ketones having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and methylcyclohexanone. Examples of ethers having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, anisole and phenetole. Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol.

The alcohol used in combination with the chlorinated organic solvent may be linear, branched or cyclic, and among them, saturated aliphatic hydrocarbon is preferable. The hydroxyl group of the alcohol may be any of primary to tertiary. Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 2-methyl-2-butanol and cyclohexanol. As the alcohol, fluorine-based alcohol is also used. Examples thereof include 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol and the like. Furthermore, the hydrocarbon may be linear, branched or cyclic. Either aromatic hydrocarbons or aliphatic hydrocarbons can be used. The aliphatic hydrocarbon may be saturated or unsaturated. Examples of hydrocarbons include cyclohexane, hexane, benzene, toluene and xylene.
Although the following can be mentioned as a combination of the chlorinated organic solvent which is a preferable main solvent of this invention, It is not limited to these.

Dichloromethane / methanol / ethanol / butanol (75/10/5/5/5, parts by mass),
Dichloromethane / acetone / methanol / propanol (80/10/5/5, parts by mass),
Dichloromethane / methanol / butanol / cyclohexane (75/10/5/5/5, parts by mass),
Dichloromethane / methyl ethyl ketone / methanol / butanol (80/10/5/5, parts by mass),
Dichloromethane / acetone / methyl ethyl ketone / ethanol / isopropanol (75/8/5/5/7, parts by mass),
Dichloromethane / cyclopentanone / methanol / isopropanol (80/7/5/8, parts by mass),
Dichloromethane / methyl acetate / butanol (80/10/10, parts by mass),
Dichloromethane / cyclohexanone / methanol / hexane (70/20/5/5, parts by mass)
Dichloromethane / methyl ethyl ketone / acetone / methanol / ethanol (50/20/20/5/5, parts by mass),
Dichloromethane / 1, 3 dioxolane / methanol / ethanol (70/20/5/5, parts by mass),
Dichloromethane / dioxane / acetone / methanol / ethanol (60/20/10/5/5, parts by mass),
Dichloromethane / acetone / cyclopentanone / ethanol / isobutanol / cyclohexane (65/10/10/5/5/5, parts by mass)
Dichloromethane / methyl ethyl ketone / acetone / methanol / ethanol (70/10/10/5/5, parts by mass),
Dichloromethane / acetone / ethyl acetate / ethanol / butanol / hexane (65/10/10/5/5/5, parts by mass),
Dichloromethane / methyl acetoacetate / methanol / ethanol (65/20/10/5, parts by mass),
Dichloromethane / cyclopentanone / ethanol / butanol (65/20/10/5, parts by mass),
Etc.

(Non-chlorine solvent)
Next, a non-chlorine organic solvent that is preferably used in preparing the cellulose acylate solution of the present invention will be described. In the present invention, the non-chlorine organic solvent is not particularly limited as long as the object can be achieved as long as the cellulose acylate can be dissolved and cast and formed into a film. The non-chlorine organic solvent used in the present invention is preferably a solvent selected from esters, ketones and ethers having 3 to 12 carbon atoms. Esters, ketones and ethers may have a cyclic structure. A compound having two or more functional groups of esters, ketones and ethers (that is, —O—, —CO—, and —COO—) can also be used as a main solvent, such as an alcoholic hydroxyl group. It may have a functional group of In the case of the main solvent having two or more kinds of functional groups, the number of carbon atoms may be within the specified range of the compound having any functional group. Examples of esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate. Examples of ketones having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and methylcyclohexanone. Examples of ethers having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, anisole and phenetole. Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol.

  The non-chlorine organic solvent used in the above cellulose acylate is selected from the various viewpoints described above, and is preferably as follows. That is, a preferred solvent for the cellulose acylate of the present invention is a mixed solvent of three or more different from each other, and the first solvent is selected from methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, dioxolane, and dioxane. And at least one kind or a mixture thereof, the second solvent is selected from ketones having 4 to 7 carbon atoms or acetoacetate, and the third solvent is alcohol or hydrocarbon having 1 to 10 carbon atoms More preferably, it is a C1-C8 alcohol. Note that when the first solvent is a mixed liquid of two or more kinds of solvents, the second solvent may be omitted. The first solvent is more preferably methyl acetate, acetone, methyl formate, ethyl formate, or a mixture thereof, and the second solvent is preferably methyl ethyl ketone, cyclopentanone, cyclohexanone, or methyl acetyl acetate. It may be.

  The alcohol as the third solvent may be linear, branched or cyclic, and is preferably a saturated aliphatic hydrocarbon. The hydroxyl group of the alcohol may be any of primary to tertiary. Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 2-methyl-2-butanol and cyclohexanol. As the alcohol, fluorine-based alcohol is also used. Examples thereof include 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol and the like. Furthermore, the hydrocarbon may be linear, branched or cyclic. Either aromatic hydrocarbons or aliphatic hydrocarbons can be used. The aliphatic hydrocarbon may be saturated or unsaturated. Examples of hydrocarbons include cyclohexane, hexane, benzene, toluene and xylene. These alcohols and hydrocarbons as the third solvent may be used alone or in combination of two or more, and are not particularly limited. As the third solvent, preferred specific compounds include alcohol, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and cyclohexanol, cyclohexane, hexane, Are methanol, ethanol, 1-propanol, 2-propanol, 1-butanol.

  The above three types of mixed solvents preferably contain the first solvent in a proportion of 20 to 95% by mass, the second solvent in a proportion of 2 to 60% by mass, and the third solvent in a proportion of 2 to 30% by mass. The first solvent is preferably 30 to 90% by mass, the second solvent is preferably 3 to 50% by mass, and the alcohol as the third solvent is preferably 3 to 25% by mass. In particular, the first solvent is preferably 30 to 90% by mass, the second solvent is preferably 3 to 30% by mass, and the third solvent is preferably 3 to 15% by mass. In addition, when the first solvent is a mixed solution and the second solvent is not used, the first solvent is preferably contained in a ratio of 20 to 90% by mass and the third solvent in a ratio of 5 to 30% by mass, Furthermore, it is preferable that a 1st solvent is 30-86 mass%, and also a 3rd solvent is contained 7-25 mass%. The non-chlorine organic solvent used in the present invention is described in more detail in pages 12 to 16 of the Japan Society for Invention and Innovation Technical Report No. 2001-1745 (issued on March 15, 2001, Japan Society for Invention). It is described in detail. Preferred combinations of non-chlorine organic solvents of the present invention can include the following, but are not limited thereto.

-Methyl acetate / acetone / methanol / ethanol / butanol (75/10/5/5/5, parts by mass),
-Methyl acetate / acetone / methanol / ethanol / propanol (75/10/5/5/5, parts by mass),
Methyl acetate / acetone / methanol / butanol / cyclohexane (75/10/5/5/5, parts by mass),
・ Methyl acetate / acetone / ethanol / butanol (81/8/7/4, parts by mass)
・ Methyl acetate / acetone / ethanol / butanol (82/10/4/4, parts by mass)
・ Methyl acetate / acetone / ethanol / butanol (80/10/4/6, part by mass)
Methyl acetate / methyl ethyl ketone / methanol / butanol (80/10/5/5, parts by mass),
-Methyl acetate / acetone / methyl ethyl ketone / ethanol / isopropanol (75/8/5/5/7, parts by mass)
Methyl acetate / cyclopentanone / methanol / isopropanol (80/7/5/8, parts by mass),
Methyl acetate / acetone / butanol (85/10/5, parts by mass),
Methyl acetate / cyclopentanone / acetone / methanol / butanol (60/15/14/5/6, parts by mass),
-Methyl acetate / cyclohexanone / methanol / hexane (70/20/5/5, parts by mass)
Methyl acetate / methyl ethyl ketone / acetone / methanol / ethanol (50/20/20/5/5, parts by mass),
Methyl acetate / 1, 3 dioxolane / methanol / ethanol (70/20/5/5, parts by mass),
Methyl acetate / dioxane / acetone / methanol / ethanol (60/20/10/5/5, parts by mass),
Methyl acetate / acetone / cyclopentanone / ethanol / isobutanol / cyclohexane (65/10/10/5/5/5, parts by mass),

Methyl formate / methyl ethyl ketone / acetone / methanol / ethanol (50/20/20/5/5, parts by mass),
-Methyl formate / acetone / ethyl acetate / ethanol / butanol / hexane (65/10/10/5/5/5, parts by mass)
Acetone / methyl acetoacetate / methanol / ethanol (65/20/10/5, parts by mass)
Acetone / cyclopentanone / ethanol / butanol (65/20/10/5, parts by mass)
Acetone / 1,3 dioxolane / ethanol / butanol (65/20/10/5, part by mass),
1,3 dioxolane / cyclohexanone / methyl ethyl ketone / methanol / butanol (55/20/10/5/5/5, parts by mass)
Etc.
Furthermore, a cellulose acylate solution can also be used by the following method.
-Cellulose acylate solution is prepared with methyl acetate / acetone / ethanol / butanol (81/8/7/4, parts by mass), filtered and concentrated, and 2 parts by weight of butanol is added after addition.-Methyl acetate / acetone / ethanol / butanol (84/10/4/2, parts by mass) A cellulose acylate solution was prepared, and after filtration and concentration, 4 parts by weight of butanol was added. Methyl acetate / acetone / ethanol (84/10/6, parts by mass) Make a cellulose acylate solution, add 5 parts by weight of butanol after filtration and concentration

(Characteristics of cellulose acylate solution)
The cellulose acylate of the present invention is characterized in that it is a solution dissolved in an organic solvent in an amount of 10 to 30% by mass, more preferably 13 to 27% by mass, and particularly 15 to 25% by mass. The cellulose acylate solution is preferred. The method for carrying out the cellulose acylate at these concentrations may be carried out so as to obtain a predetermined concentration at the stage of dissolution, or it is prepared as a low-concentration solution (for example, 9 to 14% by mass) and then concentrated as described later You may adjust to a predetermined high concentration solution by a process. In addition, a cellulose acylate solution having a high concentration may be added to the cellulose acylate solution at a predetermined low concentration by adding various additives, and the cellulose acylate solution concentration of the present invention may be obtained by any method. There is no particular problem if it is implemented.

Next, in this invention, it is preferable that the aggregate molecular weight of the cellulose acylate of the diluted solution which made the cellulose acylate solution 0.1-5 mass% with the organic solvent of the same composition is 150,000-15 million. More preferably, the associated molecular weight is 180,000 to 9 million. This associated molecular weight can be determined by a static light scattering method. In that case, it is preferable to dissolve so that the inertial square radius required at the same time is 10 to 200 nm. A more preferable inertial square radius is 20 to 200 nm. Furthermore, it is preferable to dissolve so that the second virial coefficient is −2 × 10 ⁻⁴ to 4 × 10 ^−4, and more preferably, the second virial coefficient is −2 × 10 ⁻⁴ to 2 × 10 ^−4. It is. Here, the definition of the association molecular weight, the inertial square radius, and the second virial coefficient in the present invention will be described. These were measured using the static light scattering method according to the following method. Although the measurement was performed in a dilute region for the convenience of the apparatus, these measured values reflect the behavior of the dope in the high concentration region of the present invention. First, cellulose acylate was dissolved in a solvent used for the dope to prepare 0.1 mass%, 0.2 mass%, 0.3 mass%, and 0.4 mass% solutions. In order to prevent moisture absorption, the cellulose acylate was dried at 120 ° C. for 2 hours, and was measured at 25 ° C. and 10% RH. The dissolution method was carried out according to the method employed at the time of dope dissolution (room temperature dissolution method, cooling dissolution method, high temperature dissolution method). Subsequently, these solutions and the solvent were filtered through a 0.2 μm Teflon filter. The filtered solution was measured for static light scattering at intervals of 10 degrees from 30 degrees to 140 degrees at 25 ° C. using a light scattering measuring device (DLS-700 manufactured by Otsuka Electronics Co., Ltd.). The obtained data was analyzed by the BERRY plot method. In addition, the refractive index required for this analysis uses the value of the solvent calculated | required with the Abbe refraction system, and the refractive index concentration gradient (dn / dc) uses the differential refractometer (Otsuka Electronics Co., Ltd. product DRM-1021). The measurement was performed using the solvent and the solution used for the light scattering measurement.

(Dope preparation)
Next, with respect to the preparation of the cellulose acylate solution (dope) of the present invention, the dissolution method is not particularly limited, and may be room temperature, further a cooling dissolution method or a high temperature dissolution method, or a combination thereof. With respect to these, for example, JP-A-5-163301, JP-A-61-106628, JP-A-58-127737, JP-A-9-95544, JP-A-10-95854, JP-A-10-95854 -45950, JP-A-2000-53784, JP-A-11-322946, JP-A-11-322947, JP-A-2-276830, JP-A-2000-273239, JP-A-11-. No. 71463, JP-A No. 04-259511, JP-A No. 2000-273184, JP-A No. 11-323017, JP-A No. 11-302388, etc. describe methods for preparing cellulose acylate solutions. The above-described method for dissolving cellulose acylate in an organic solvent is applicable to the present invention as long as it is within the scope of the present invention. These details are described in detail on pages 22 to 25 in the non-chlorine-based solvent system, especially in the Japan Society for Invention and Innovation Technical Bulletin No. 2001-1745 (issued on March 15, 2001, Japan Society for Invention). Be implemented in a way that Further, the cellulose acylate dope solution of the present invention is usually subjected to solution concentration and filtration. Similarly, it is 25 according to the Japan Institute of Invention and Technology Publication No. 2001-1745 (issued on March 15, 2001, Invention Association). It is described in detail on the page. In addition, when it melt | dissolves at high temperature, it is the case where it is more than the boiling point of the organic solvent to be used, and in that case, it uses in a pressurized state.

The cellulose acylate solution of the present invention preferably has a viscosity and a dynamic storage modulus within the range. 1 mL of the sample solution was measured with a rheometer (CLS 500) using Steel Cone (both manufactured by TA Instruments) with a diameter of 4 cm / 2 °. Measurement conditions were measured by varying the range from 40 ° C. to −10 ° C. at 2 ° C./min with Oscillation Step / Temperature Ramp, and static non-Newtonian viscosity n ^* (Pa · s) at 40 ° C. and storage at −5 ° C. The elastic modulus G ′ (Pa) was determined. The sample solution was kept warm until the liquid temperature was kept constant at the measurement start temperature, and measurement was started. In the present invention, the viscosity at 40 ° C. is 1 to 400 Pa · s, the dynamic storage elastic modulus at 15 ° C. is preferably 500 Pa or more, more preferably the viscosity at 40 ° C. is 10 to 200 Pa · s, The dynamic storage elastic modulus at 15 ° C. is preferably 1 to 1,000,000. Furthermore, it is preferable that the dynamic storage elastic modulus at low temperature is larger. For example, when the casting support is −5 ° C., the dynamic storage elastic modulus is preferably 10,000 to 1,000,000 Pa at −5 ° C. When the body is at −50 ° C., the dynamic storage elastic modulus at −50 ° C. is preferably 10,000 to 5 million Pa.

  As described above, the concentration of the cellulose acylate solution is characterized in that a high-concentration dope can be obtained, and a cellulose acylate solution having a high concentration and excellent stability can be obtained without depending on the means of concentration. Furthermore, in order to make it easy to melt | dissolve, after making it melt | dissolve at a low density | concentration, you may concentrate using a concentration means. The concentration method is not particularly limited. For example, the low-concentration solution is guided between the cylindrical body and the rotation trajectory of the outer periphery of the rotating blade rotating in the circumferential direction, and the temperature between the solution and the solution. A method of obtaining a high-concentration solution while evaporating the solvent by giving a difference (for example, JP-A-4-259511), a heated low-concentration solution is blown into the container from the nozzle, and the solution is applied from the nozzle to the inner wall of the container In which the solvent is flash evaporated and the solvent vapor is withdrawn from the container and the concentrated solution is withdrawn from the bottom of the container (eg, US Pat. No. 2,541,012, US Pat. No. 2,858,229, US Pat. No. 4,414,341, US Pat. No. 4,504,355, etc.).

  Prior to casting, it is preferable to filter off foreign matters such as undissolved matter, dust, and impurities using a suitable filter medium such as a wire mesh or flannel. For the filtration of the cellulose acylate solution, a filter having an absolute filtration accuracy of 0.1 to 100 μm is used, and a filter having an absolute filtration accuracy of 0.5 to 25 μm is preferably used. The thickness of the filter is preferably 0.1 to 10 mm, and more preferably 0.2 to 2 mm. In that case, the filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, further 1.0 MPa or less, and particularly preferably 0.2 MPa or less. As the filter medium, conventionally known materials such as glass fibers, cellulose fibers, filter paper, fluororesins such as tetrafluoroethylene resin can be preferably used, and ceramics, metals and the like are particularly preferably used. The viscosity of the cellulose acylate solution immediately before film formation may be in a range that can be cast during film formation, and is usually prepared in a range of 10 Pa · s to 2000 Pa · s, preferably 30 Pa · s to 1000 Pa. · S is more preferable, and 40 Pa · s to 500 Pa · s is more preferable. In addition, although the temperature at this time will not be specifically limited if it is the temperature at the time of the casting, Preferably it is -5-70 degreeC, More preferably, it is -5-55 degreeC.

(Film formation)
A method for producing a film using a cellulose acylate solution will be described. As a method and equipment for producing the cellulose acylate film of the present invention, a solution casting film forming method and a solution casting film forming apparatus conventionally used for producing a cellulose triacetate film are used. The dope (cellulose acylate solution) prepared from the dissolving machine (kettle) is temporarily stored in a storage kettle, and the foam contained in the dope is defoamed for final preparation. The dope is sent from the dope discharge port to the pressure die through a pressure metering gear pump capable of delivering a constant amount of liquid with high accuracy, for example, by the number of rotations. The dry-dried dope film (also referred to as web) is peeled off from the metal support at a peeling point that is uniformly cast on the metal support and substantially rounds the metal support. Both ends of the obtained web are sandwiched between clips, transported by a tenter while keeping the width, dried, then transported by a roll group of a drying device, dried, and wound up to a predetermined length by a winder. The combination of the tenter and the roll group dryer varies depending on the purpose. In the solution casting film forming method used for the functional protective film for electronic displays, in addition to the solution casting film forming apparatus, surface processing on films such as an undercoat layer, an antistatic layer, an antihalation layer, a protective layer, etc. Therefore, a coating device is often added. Although each manufacturing process is described briefly below, it is not limited to these.

  First, when the prepared cellulose acylate solution (dope) is produced by a solvent casting method, a dope is cast on a drum or a band, and the solvent is evaporated to form a film. It is preferable to adjust the concentration of the dope before casting so that the solid content is 5 to 40% by mass. The surface of the drum or band is preferably finished in a mirror state. The dope is preferably cast on a drum or band having a surface temperature of 30 ° C. or lower, and particularly preferably a metal support temperature of −10 to 20 ° C. Further, JP 2000-301555, JP 2000-301558, JP 07-032391, JP 03-193316, JP 05-086212, JP 62-037113, JP 02-276607. The techniques described in JP-A Nos. 55-014201, 02-111511, and 02-208650 can be applied in the present invention.

(Multilayer casting)
The cellulose acylate solution may be cast as a single layer liquid on a smooth band or drum as a metal support, or a plurality of cellulose acylate liquids of two or more layers may be cast. When casting a plurality of cellulose acylate solutions, produce a film while casting and laminating a solution containing cellulose acylate from a plurality of casting openings provided at intervals in the traveling direction of the metal support. For example, the methods described in JP-A-61-158414, JP-A-1-122419, and JP-A-11-198285 can be applied. Further, it may be formed into a film by casting a cellulose acylate solution from two casting ports. For example, JP-B-60-27562, JP-A-61-94724, JP-A-61-947245, It can be carried out by the methods described in JP-A Nos. 61-104813, 61-158413, and 6-134933. Further, a cellulose acylate film in which a flow of a high-viscosity cellulose acylate solution described in JP-A-56-162617 is wrapped with a low-viscosity cellulose acylate solution, and the high-low viscosity cellulose acylate solution is simultaneously extruded A casting method may be used. Furthermore, it is also a preferred embodiment that the outer solution described in JP-A-61-94724 and JP-A-61-94725 contains a larger amount of an alcohol component which is a poor solvent than the inner solution. Alternatively, by using two casting ports, peeling the film formed on the metal support by the first casting port, and performing the second casting on the side that was in contact with the metal support surface, A film may be produced, for example, a method described in Japanese Patent Publication No. 44-20235. The cellulose acylate solution to be cast may be the same solution or different cellulose acylate solutions, and is not particularly limited. In order to give a function to a plurality of cellulose acylate layers, a cellulose acylate solution corresponding to the function may be extruded from each casting port. Furthermore, the cellulose acylate solution can be cast by simultaneously casting other functional layers (for example, an adhesive layer, a dye layer, an antistatic layer, an antihalation layer, a UV absorbing layer, a polarizing layer).

  In the conventional single-layer liquid, it is necessary to extrude a high-concentration and high-viscosity cellulose acylate solution in order to obtain the required film thickness. In many cases, this causes a problem such as a fault or flatness. As a solution to this, by casting a plurality of cellulose acylate solutions from a casting port, a highly viscous solution can be extruded onto a metal support at the same time. Not only can it be produced, but also a concentrated cellulose acylate solution can be used to reduce the drying load and increase the film production speed. In the case of co-casting, the inner and outer thicknesses are not particularly limited, but preferably the outer side is preferably 1 to 50% of the total film thickness, and more preferably 2 to 30%. Here, in the case of co-casting with three or more layers, the total thickness of the layer in contact with the metal support and the layer in contact with the air side is defined as the outer thickness. In the case of co-casting, a cellulose acylate film having a laminated structure can be produced by co-casting cellulose acylate solutions having different additive concentrations such as the above-mentioned plasticizer, ultraviolet absorber and matting agent. For example, a cellulose acylate film having a structure of skin layer / core layer / skin layer can be produced. For example, the matting agent can be contained in the skin layer in a large amount or only in the skin layer. The plasticizer and the ultraviolet absorber can be contained in the core layer more than the skin layer, and may be contained only in the core layer. In addition, the kind of plasticizer and ultraviolet absorber can be changed between the core layer and the skin layer. For example, the skin layer contains a low-volatile plasticizer and / or an ultraviolet absorber, and the core layer has excellent plasticity. It is also possible to add a plasticizer or an ultraviolet absorber excellent in ultraviolet absorption. Moreover, it is also a preferable aspect that a release agent is contained only in the skin layer on the metal support side. It is also preferable to add more alcohol, which is a poor solvent, to the skin layer than the core layer in order to cool the metal support by the cooling drum method to gel the solution. The Tg of the skin layer and the core layer may be different, and the Tg of the core layer is preferably lower than the Tg of the skin layer. Further, the viscosity of the solution containing cellulose acylate during casting may be different between the skin layer and the core layer, and the viscosity of the skin layer is preferably smaller than the viscosity of the core layer. It may be smaller than the viscosity.

(Casting)
As a solution casting method, a method in which the prepared dope is uniformly extruded from a pressure die onto a metal support, and a method using a doctor blade in which the dope once cast on the metal support is adjusted with a blade is used. Alternatively, there is a method using a reverse roll coater that adjusts with a reverse rotating roll, and a method using a pressure die is preferable. The pressure die includes a coat hanger type and a T die type, and any of them can be preferably used. In addition to the methods listed here, it can be carried out by various methods of casting a cellulose triacetate solution known in the art, and by setting each condition in consideration of differences in the boiling point of the solvent used, etc. The same effects as those described in the above publication can be obtained. The endlessly running metal support used for producing the cellulose acylate film of the present invention includes a drum whose surface is mirror-finished by chrome plating and a stainless steel belt whose surface is mirror-finished by surface polishing (referred to as a band). May be used). One or two or more pressure dies used for producing the cellulose acylate film of the present invention may be installed above the metal support. Preferably 1 or 2 groups. When two or more units are installed, the amount of dope to be cast may be divided into various ratios for each die, or the dope may be fed to the dies from each of a plurality of precision quantitative gear pumps. The temperature of the cellulose acylate solution used for casting is preferably −10 to 55 ° C., more preferably 25 to 50 ° C. In that case, all of the steps may be the same or may be different at different points in the step. If they are different, it may be a desired temperature just before casting.

(Dry)
The drying of the dope on the metal support involved in the production of the cellulose acylate film is generally performed by applying hot air from the surface side of the metal support (drum or belt), that is, the surface of the web on the metal support, A method of applying hot air from the back of the drum or belt, contacting the temperature-controlled liquid from the back of the belt or drum opposite the dope casting surface, and heating the drum or belt by heat transfer to control the surface temperature Although there is a heat transfer method, the back surface liquid heat transfer method is preferable. The surface temperature of the metal support before casting may be any number as long as it is not higher than the boiling point of the solvent used for the dope. However, in order to promote drying and to lose fluidity on the metal support, the temperature should be set to 1 to 10 degrees lower than the boiling point of the lowest boiling solvent used. Is preferred. This is not the case when the cast dope is cooled and peeled off without drying.
The peeling step is a step of evaporating the organic solvent on the metal support and peeling the web before the metal support goes around. Thereafter, the web is sent to the post-drying step. The position at which the web is peeled from the metal support is called the peeling point, and the roll that helps the peeling is called the peeling roll. Although it depends on the thickness of the web, if the residual solvent amount of the web at the peeling point (the following formula) is too large, it will be difficult to peel, or conversely if it is peeled off after sufficiently drying on the support, May be peeled off. Usually, the web is peeled at a residual solvent amount of 20 to 150% by mass. In the present invention, the preferable amount of residual solvent for peeling is 20 to 40% by mass or 60 to 120% by mass, and particularly preferably 20 to 30% by mass or 70 to 115% by mass. As a method for increasing the film forming speed (the film forming speed can be increased because the film is peeled off while the residual solvent amount is as large as possible), there is a gel casting method (gel casting) that can be peeled even when the residual solvent amount is large. As the method, there are a method of adding a poor solvent for the cellulose ester into the dope and casting the dope and then gelling, a method of reducing the temperature of the support and gelling.
Here, the residual solvent amount refers to (amount of solvent in the film) × 100 / (amount of solid content in the film). The solid content in the film includes, in addition to cellulose acylate, non-volatile additives such as plasticizers, ultraviolet absorbers, and retardation enhancers.

In the post-drying step, a roll drying device in which the rolls are arranged in a staggered manner, and a method of drying while conveying the web with a tenter drying device that holds the both ends of the web with clips while maintaining the width or slightly extending in the width direction are adopted. In this invention, after peeling from a support body, it is preferable to make dimensional stability and planarity favorable by extending | stretching width direction with a tenter drying apparatus or 1.00 to 1.05 times. The means for drying the web is not particularly limited, and is generally performed by hot air, infrared rays, a heating roll, microwaves, or the like. Preferably, hot air drying is performed. The drying temperature is preferably increased stepwise in the range of 40 to 150 ° C, and more preferably in the range of 50 to 140 ° C in order to improve flatness. In this way, the film is dried until the residual solvent in the film is less than 3%. The residual solvent concentration is preferably less than 1%, more preferably 0.5% or less, and particularly preferably 0.2% or less.
The thickness of the finished cellulose acylate film of the present invention (after drying) is preferably in the range of 45 to 180 μm because it is easy to adjust the Re retardation and Rth retardation to appropriate values. Further, a range of 70 to 160 μm is preferable, and a range of 95 to 150 μm is particularly preferable. The final thickness is determined taking into account the thickness reduction due to the subsequent stretching step.

  The film thickness may be adjusted by adjusting the solid content concentration contained in the dope, the slit gap of the die base, the extrusion pressure from the die, the metal support speed, and the like so as to obtain a desired thickness. The width of the cellulose acylate film obtained as described above is preferably 0.5 to 3 m, more preferably 0.6 to 2.5 m, and still more preferably 0.8 to 2.2 m. The length is preferably 100 to 10000 m per roll, more preferably 500 to 7000 m, and still more preferably 1000 to 6000 m. When winding, knurling is preferably applied to at least one end, the width is 3 mm to 50 mm, more preferably 5 m to 30 mm, and the height is 0.5 to 500 μm, more preferably 1 to 200 μm. This may be a single push or a double push.

(Extension process)
In the present invention, the cellulose acylate film having a residual volatile content of less than 3% formed as described above is sent to a stretching apparatus and heated and stretched. The residual volatile content of the stretched film is preferably less than 1%, more preferably 0.5% or less, and particularly preferably 0.2% or less. Conventionally, the cellulose acylate film has been generally stretched when 3% or more of the solvent still remains in the film during the film forming process. A film in the course of drying in which the solvent remains in the film in an amount of 3% or more has a slightly different degree of progress in the width direction, and the elongation when pulled tends to change in the width direction. If the film is stretched under such conditions, the in-plane retardation Re in the width direction tends to be large at the center and small at both ends. Therefore, it is preferable to stretch in a sufficiently dried state as in the present invention. Further, as in the present invention, by forming the film and stretching separately, the machine can be stopped and repaired immediately even if a film cutting trouble that easily occurs during stretching occurs. If film formation and stretching are connected, it is impossible to stop the film-forming part when the film is cut in the stretching process. .
The stretching temperature is preferably 140 ° C. or higher and 180 ° C. or lower near the glass transition temperature of the film. At temperatures around 190 ° C., cellulose acylate crystallizes rapidly and must be avoided. More preferably, it is stretched at 145 to 165 ° C. The stretching of the film may be uniaxial stretching only in the longitudinal or lateral direction, or may be simultaneous or sequential biaxial stretching. Stretching of 1.1 to 2.0 times is performed. The stretching is preferably 1.15 to 1.5 times, particularly preferably 1.2 to 1.35 times. When used for a polarizing plate used in a VA liquid crystal display device or an OCB liquid crystal display device, it is preferable for the birefringence of the optical film that the refractive index in the width direction is larger than the refractive index in the length direction for the convenience of polarizing plate processing. . Therefore, in this case, it is preferable to stretch more in the width direction. A tenter device is usually used for stretching in the width direction. In order to stretch in the length direction, stretching is performed by a plurality of nip rolls that gradually increase in peripheral speed.

It is preferable to keep the temperature of the film at a temperature lower by 10 to 40 ° C. than the glass transition temperature immediately before stretching. If the film is stretched suddenly from a temperature lower than this, a temperature unevenness is generated in the film width direction, and a part that is easily stretched and a part that is not easily stretched are generated, resulting in unevenness in the optical characteristics of Re and Rth. On the other hand, if it is heated too much to the glass transition temperature, the film is softened and the flatness tends to be impaired. Therefore, it is preferable to keep the temperature 10 to 40 ° C. lower than the stretching temperature immediately before stretching of the cellulose acylate film. It is more preferable to keep the temperature 20 to 35 ° C lower.
After stretching, the mechanical strain generated in the film is maintained by maintaining the width and length of the stretched film at a temperature of 10 ° C. before and after the stretching temperature, or by holding the film while contracting 5 to 20% of the stretched amount in the stretching direction. Is preferably relaxed. Immediately after the relaxation step, the film temperature is lowered and wound up. Align the ears before winding, or in some cases cut the ears just before winding to align both sides of the winding.

The thickness of the finished cellulose acylate film of the present invention (after stretching) is preferably in the range of 40 to 160 μm because it is easy to adjust the Re retardation and Rth retardation to appropriate values. Furthermore, the range of 70-130 micrometers is preferable, and the range of 85-110 micrometers is especially preferable.
When a film having a residual volatile content of less than 3% was stretched as in the present invention, the linear expansion coefficient of the resulting stretched film was reduced. When an optical film having a large linear expansion coefficient is used in a liquid crystal display device such as a VA type or an OCB type, light leaks easily from the peripheral edge of the screen. However, it has been found that such light leakage is greatly reduced in the film of the present invention. Preferred linear expansion coefficients are 75 ppm or less in the MD direction and 45 ppm or less in the TD direction. More preferable linear expansion coefficients are 72 ppm or less in the MD direction and 38 ppm or less in the TD direction. The linear expansion coefficient tends to decrease in the stretching direction as the stretching ratio increases, but tends to increase in the direction perpendicular to the stretching direction, and can be controlled to some extent by adjusting the stretching ratio.
The variation range ΔRe of the in-plane retardation Re of the full width (difference between the maximum value and the minimum value of the Re measurement values at 7 points in the width direction) is preferably 1.7 nm or less, and more preferably 1.3 nm. Further, the value obtained by dividing ΔRe by the Re average value Rea at 7 points in the width direction is preferably 0.025 or less, and more preferably 0.020 or less. The larger this value, the easier it is to see the unevenness of light leakage in black display when the liquid crystal display device is assembled. The variation in the thickness direction retardation Rth of the entire width is preferably ± 10 nm, and more preferably ± 5 nm. Moreover, it is preferable that the variation in Re and Rth in the length direction is equal to the variation in the width direction.

(Optical properties of cellulose acylate film)
In the present invention, Re and Rth are measured using KOBRA 21ADH (manufactured by Oji Scientific Instruments) under the conditions of 25 ° C. and 60% RH. The measured values Re [60] and Rth [60] preferably satisfy the following expressions, respectively.
30 ≦ Re [60] ≦ 100, 120 ≦ Rth [60] ≦ 400
[Wherein, Re and Rth are values (unit: nm) at a wavelength of 590 nm. Further, nx is the refractive index in the slow axis direction in the film plane, ny is the refractive index in the fast axis direction in the film plane, nz is the refractive index in the thickness direction of the film, and d is the thickness of the film. That's it. ]
When the cellulose acylate film of the present invention is used on each side of the VA liquid crystal cell, preferable Re [60] and Rth [60] are 30 to 45 and 120 to 180, respectively.
On the other hand, when one cellulose acylate film of the present invention is used on only one side of the VA liquid crystal cell, preferable Re [60] and Rth [60] are 50 to 100 and 150 to 340, respectively. More preferably, it has an optical characteristic that satisfies the formula Rth [60] = a−5.9Re [60] and the formula 580 ≦ a ≦ 670 nm at the same time. The optimum calculated value of a is 625, and the black luminance value of the VA liquid crystal display device tends to increase as a shifts up and down from around 625. That is, light is leaked and it is not black. Re [60] and Rth [60] vary depending on the Δnd value of the VA liquid crystal cell to be used. For example, when the Δnd value of the VA liquid crystal cell is 350 nm, the most preferable Re [60] and Rth [60] are 55 to 60 and 270 to 290, respectively. When the Δnd value of the VA liquid crystal cell is 300 nm, the most preferable Re [60] and Rth [60] are 62 to 68 nm and 220 to 240 nm, respectively. When the Δnd value of the VA liquid crystal cell is 250 nm, the most preferable Re [60] and Rth [60] are 75 to 80 nm and 180 to 200 nm, respectively.

Further, it is preferable that the following relations hold between Re ₍ λ ₎ and Rth ₍ λ ₎ measured by changing the wavelength λ at 25 ° C. and 60% RH.
0.95 ≦ Re ₍₄₈₀₎ / Re ₍₆₃₀₎ ≦ 1.10 and 0.95 ≦ Rth ₍₄₈₀₎ / Rth ₍₆₃₀₎ ≦ 1.10.
More preferably, both of the following relationships hold:
0.98 ≦ Re ₍₄₈₀₎ / Re ₍₆₃₀₎ ≦ 1.05 and 0.98 ≦ Rth ₍₄₈₀₎ / Rth ₍₆₃₀₎ ≦ 1.05
If an optical film deviating from this range is used, color misregistration tends to occur in the display of the liquid crystal display device.
The optical characteristic values of Re and Rth tend to change with changes in environmental humidity. The smaller the change in Re and Rth, the less the color change of the liquid crystal display device. ΔRe / Re [60] ≦ 0.23 and ΔRth / Rth [60] ≦ 0, where ΔRe and ΔRth are the amounts of change in optical characteristics when the humidity at 25 ° C. is changed from 10% RH to 80% RH. .23 is preferable. By using cellulose acylate having a large substitution degree of 6-position acyl to reduce the change in optical properties due to humidity, or by using various hydrophobic additives (plasticizer, retardation developer, ultraviolet absorber, etc.) Reduce the moisture permeability and equilibrium moisture content of the film. The preferred moisture permeability is 400 to 2300 g per square meter at 60 ° C. and 95% RH for 24 hours. A preferable equilibrium water content is 3.4% or less at 25 ° C. and 80% RH. A preferred amount of hydrophobic additive is 10 to 30%, more preferably 12 to 25%, particularly preferably 14.5% to 20%, based on cellulose acylate.

(Polarizer)
The polarizing plate is composed of a polarizer and two transparent protective films disposed on both sides thereof. As one protective film, the cellulose acylate film of the present invention can be used. The other protective film may be a normal cellulose acetate film. Examples of the polarizer include an iodine polarizer, a dye polarizer using a dichroic dye, and a polyene polarizer. The iodine polarizer and the dye polarizer are generally produced using a polyvinyl alcohol film. When the cellulose acylate film of the present invention is used as a polarizing plate protective film, the method for producing the polarizing plate is not particularly limited, and can be produced by a general method. There is a method in which the obtained cellulose acylate film is treated with an alkali and bonded to both sides of a polarizer prepared by immersing and stretching a polyvinyl alcohol film in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. Instead of alkali treatment, easy adhesion processing as described in JP-A-6-94915 and JP-A-6-118232 may be performed. Examples of the adhesive used to bond the protective film-treated surface and the polarizer include polyvinyl alcohol adhesives such as polyvinyl alcohol and polyvinyl butyral, vinyl latexes such as butyl acrylate, and the like. The polarizing plate is composed of a polarizer and a protective film that protects both surfaces of the polarizer. Further, a protective film is bonded to one surface of the polarizing plate, and a separate film is bonded to the opposite surface. The protective film and the separate film are used for the purpose of protecting the polarizing plate at the time of shipping the polarizing plate and at the time of product inspection. In this case, the protect film is bonded for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the surface where the polarizing plate is bonded to the liquid crystal plate. Moreover, a separate film is used in order to cover the contact bonding layer bonded to a liquid crystal plate, and is used for the surface side which bonds a polarizing plate to a liquid crystal plate.

  The cellulosic acylate film of the present invention is preferably bonded to the polarizer so that the transmission axis of the polarizer coincides with the slow axis of the cellulose acylate film of the present invention. In addition, when the polarizing plate produced under polarizing plate crossed Nicols was evaluated, the orthogonality accuracy between the slow axis of the cellulose acylate film of the present invention and the absorption axis of the polarizer (axis orthogonal to the transmission axis) was 1. It was found that when it was larger than 0 °, the polarization degree performance under the polarizing plate crossed Nicols was lowered and light leakage occurred. In this case, when combined with a liquid crystal cell, sufficient black level and contrast cannot be obtained. Therefore, the deviation between the direction of the main refractive index nx of the cellulose acylate film of the present invention and the direction of the transmission axis of the polarizing plate is preferably within 1 °, and preferably within 0.5 °.

In the polarizing plate of the present invention, the single plate transmittance TT, parallel transmittance PT, orthogonal transmittance CT, and polarization degree P at 25 ° C. and 60% RH satisfy at least one of the following formulas (a) to (d). Is preferred.
(A) 40.0 ≦ TT ≦ 45.0
(B) 30.0 ≦ PT ≦ 40.0
(C) CT ≦ 2.0
(D) 95.0 ≧ P
In the polarizing plate of the present invention, CT ₍₃₈₀₎ , CT ₍₄₁₀₎ , and CT ₍₇₀₀₎ are at least one of the following formulas (e) to (g) when the orthogonal transmittance at wavelength λ is CT ₍ λ ₎ It is preferable to satisfy one or more.
(E) CT ₍₃₈₀₎ ≦ 2.0
(F) CT ₍₄₁₀₎ ≦ 1.0
(G) CT ₍₇₀₀₎ ≦ 0.5
More preferably, CT ₍₃₈₀₎ ≤1.95, CT ₍₄₁₀₎ ≤0.9, CT ₍₇₀₀₎ ≤0.49, and further preferably CT ₍₃₈₀₎ ≤1.90, CT ₍₄₁₀₎ ≤0. .8, CT ₍₇₀₀₎ ≦ 0.48.
The polarizing plate of the present invention has an orthogonal transmittance change ΔCT and a polarization degree change ΔP of at least one of the following formulas (j) and (k) when left at 60 ° C. and 95% RH for 500 hours. It is preferable to satisfy the above.
(J) −6.0 ≦ ΔCT ≦ 6.0
(K) -10.0 ≦ ΔP ≦ 0.0
(However, the amount of change is the value obtained by subtracting the pre-test measurement value from the post-test measurement value)
More preferably, −5.8 ≦ ΔCT ≦ 5.8, −9.5 ≦ ΔP ≦ 0.0, and still more preferably, −5.6 ≦ ΔCT ≦ 5.6, −9.0 ≦ ΔP ≦ 0.0. It is.
The polarizing plate of the present invention has at least one of the following formulas (h) and (i) having an orthogonal transmittance change ΔCT and a polarization degree change ΔP when left at 60 ° C. and 90% RH for 500 hours. It is preferable to satisfy the above.
(H) −3.0 ≦ ΔCT ≦ 3.0
(I) −5.0 ≦ ΔP ≦ 0.0
In the polarizing plate of the present invention, the change amount ΔCT of the orthogonal transmittance and the change amount ΔP of the polarization degree satisfy at least one of the following formulas (l) and (m) when left at 80 ° C. for 500 hours. It is preferable.
(L) −3.0 ≦ ΔCT ≦ 3.0
(M) −2.0 ≦ ΔP ≦ 0.0
The single plate transmittance TT, the parallel transmittance PT, and the orthogonal transmittance CT of the polarizing plate were measured in the range of 380 nm to 780 nm using UV3100PC (manufactured by Shimadzu Corporation), and both TT, PT, and CT were measured 10 times. An average value (average value between 400 nm and 700 nm) is used. The degree of polarization P can be determined by the degree of polarization (%) = 100 × [(parallel transmittance−orthogonal transmittance) / (parallel transmittance + orthogonal transmittance)] ^1/2 . The polarizing plate durability test is carried out as follows in two forms of (1) only the polarizing plate and (2) the polarizing plate attached to glass with an adhesive. For the measurement of only the polarizing plate, two orthogonal and identical ones are prepared and measured so that the cellulose acylate film of the present invention is sandwiched between two polarizers. Two samples (approx. 5 cm × 5 cm) are prepared by attaching a polarizing plate on glass so that the cellulose acylate film of the present invention is on the glass side. In single-plate transmittance measurement, the sample is set with the film side facing the light source. Each of the two samples is measured, and the average value is taken as the transmittance of the single plate.

(Dampproof bag)
In the present invention, the “moisture-proof bag” is defined by the moisture permeability measured based on the cup method (JIS-Z208). In consideration of the environmental humidity outside the bag, it is preferable to use a material having a moisture permeability of 30 g / (m ² · Day) or less at 40 ° C. and 90% RH. When it is 30 g / (m ² · Day) or more, it becomes impossible to prevent the influence of environmental humidity outside the bag. More preferably, it is 10 g / (m ² · Day) or less, and most preferably 5 g / (m ² · Day) or less.
The material of the moisture-proof bag is not particularly limited as long as the material satisfies the moisture permeability described above, and a known material can be used (see the following documents 1 to 3).
[Non-Patent Document 1] "Handbook of packaging materials", Japan Packaging Technology Association (1995)
[Non-Patent Document 2] “Basic knowledge of packaging materials”, Japan Packaging Technology Association (November 2001)
[Non-Patent Document 3] “Introduction to Functional Packaging”, 21st Century Packaging Research Boundary (February 28, 2002, first edition, first print)

In the present invention, a material that has low moisture permeability and is light and easy to handle is desirable, and a composite material such as a film obtained by vapor-depositing silica, alumina, ceramics material, etc. on a plastic film or a laminated film of a plastic film and an aluminum foil is particularly preferably used. Can do. The thickness of the aluminum foil is not particularly limited as long as the humidity in the bag does not change in the environmental humidity, but it is preferably several μm to several 100 μm, and preferably 10 μm to 500 μm. Further preferred. It is preferable that the humidity in the bag subjected to the moisture-proofing treatment used in the present invention satisfies either of the following (A) and (B).
(B) It must be 43% RH to 70% RH at 25 ° C. with the polarizing plate packaged, and further 45% to 65%.
(B) The humidity in the bag with the polarizing plate packaged is within 15% RH with respect to the humidity when the polarizing plate is bonded to the liquid crystal panel.

(surface treatment)
The cellulose acylate film of the present invention can achieve improved adhesion between the cellulose acylate film and each functional layer (for example, the undercoat layer and the back layer) by optionally performing a surface treatment. For example, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment can be used. The glow discharge treatment here may be low-temperature plasma that occurs in a low-pressure gas of 10 ^{−3 to} 20 Torr, and plasma treatment under atmospheric pressure is also preferable. A plasma-excitable gas is a gas that is plasma-excited under the above conditions, and includes chlorofluorocarbons such as argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, tetrafluoromethane, and mixtures thereof. It is done. Details of these are described in detail on pages 30 to 32 in the Invention Association Public Technical Bulletin No. 2001-1745 (issued March 15, 2001, Invention Association). Note that, in the plasma treatment at atmospheric pressure which has been attracting attention in recent years, for example, irradiation energy of 20 to 500 Kgy is used under 10 to 1000 Kev, and more preferably irradiation energy of 20 to 300 Kgy is used under 30 to 500 Kev. Among these, an alkali saponification treatment is particularly preferable, and it is extremely effective as a surface treatment of a cellulose acylate film.

  The alkali saponification treatment is preferably carried out by a method in which the cellulose acylate film is directly immersed in a saponification solution tank or a method in which the saponification solution is applied to the cellulose acylate film. Examples of the coating method include a dip coating method, a curtain coating method, an extrusion coating method, a bar coating method, and an E-type coating method. The solvent of the alkali saponification coating solution has good wettability because it is applied to the transparent support of the saponification solution, and the surface state remains good without forming irregularities on the surface of the transparent support by the saponification solution solvent. It is preferred to select a solvent to keep. Specifically, an alcohol solvent is preferable, and isopropyl alcohol is particularly preferable. An aqueous solution of a surfactant can also be used as a solvent. The alkali of the alkali saponification coating solution is preferably an alkali that dissolves in the above solvent, and more preferably KOH or NaOH. The pH of the saponification coating solution is preferably 10 or more, more preferably 12 or more. The reaction conditions during alkali saponification are preferably 1 second to 5 minutes at room temperature, more preferably 5 seconds to 5 minutes, and particularly preferably 20 seconds to 3 minutes. After the alkali saponification reaction, it is preferable to wash the surface on which the saponification solution is applied with water or with an acid and then with water.

(Antireflection layer)
It is preferable to provide a functional film such as an antireflection layer on the transparent protective film disposed on the opposite side of the polarizing plate from the liquid crystal cell. In particular, in the present invention, at least a light scattering layer and a low refractive index layer are laminated in this order on the transparent protective film, or a medium refractive index layer, a high refractive index layer, and a low refractive index layer are formed on the transparent protective film. An antireflection layer laminated in order is preferably used. Preferred examples thereof are described below.

A preferred example of an antireflection layer in which a light scattering layer and a low refractive index layer are provided on a transparent protective film will be described.
In the light scattering layer of the present invention, mat particles are dispersed, and the refractive index of the material other than the mat particles in the light scattering layer is preferably in the range of 1.50 to 2.00. The refractive index of the layer is preferably in the range of 1.35 to 1.49. In the present invention, the light scattering layer has both antiglare properties and hard coat properties, and may be a single layer or a plurality of layers, for example, 2 to 4 layers.

The antireflection layer has an uneven surface shape with a center line average roughness Ra of 0.08 to 0.40 μm, a 10-point average roughness Rz of 10 times or less of Ra, an average mountain valley distance Sm of 1 to 100 μm, and an uneven depth. Designed so that the standard deviation of the height of the convex part from the part is 0.5 μm or less, the standard deviation of the average mountain valley distance Sm with respect to the center line is 20 μm or less, and the surface with the inclination angle of 0 to 5 degrees is 10% or more. By doing so, sufficient anti-glare properties and a visually uniform matte feeling are achieved, which is preferable. Further, the ratio of the minimum value and the maximum value of the reflectance within the range of a ^* value −2 to 2, b ^* value −3 to 3, and 380 nm to 780 nm under the light source C is 0.5. By being -0.99, the color of reflected light becomes neutral, which is preferable. Moreover, it is preferable that the b ^* value of the transmitted light under the C light source is 0 to 3 because the yellow color of white display when applied to a display device is reduced. In addition, when a 120 μm × 40 μm grid is inserted between the surface light source and the antireflection film of the present invention and the luminance distribution is measured on the film, the standard deviation of the luminance distribution is 20 or less. The glare when applying the film of the present invention is reduced, which is preferable.

  The optical properties of the antireflection layer of the present invention are such that the specular reflectance is 2.5% or less, the transmittance is 90% or more, and the 60 ° glossiness is 70% or less. Is preferable. In particular, the specular reflectance is more preferably 1% or less, and most preferably 0.5% or less. Haze 20% to 50%, internal haze / total haze value 0.3 to 1, haze value after formation of low refractive index layer from haze value to light scattering layer within 15%, comb width at 0.5 mm Transmission image clarity 20% to 50%, vertical transmission light / transmittance ratio of 2 degrees from vertical to 1.5 to 5.0 prevents glare on high-definition LCD panels, characters, etc. Reduction of blur is achieved, which is preferable.

(Low refractive index layer)
The refractive index of the low refractive index layer of the antireflection film of the present invention is 1.20 to 1.49, preferably 1.30 to 1.44. Further, the low refractive index layer preferably satisfies the following formula (1) from the viewpoint of reducing the reflectance.
Formula (1): (m / 4) × 0.7 <n1d1 <(m / 4) × 1.3
In the formula, m is a positive odd number, n1 is the refractive index of the low refractive index layer, and d1 is the film thickness (nm) of the low refractive index layer. Further, λ is a wavelength, which is a value in the range of 500 to 550 nm.

The material for forming the low refractive index layer of the present invention will be described below.
The low refractive index layer of the present invention contains a fluorine-containing polymer as a low refractive index binder. The fluorine polymer is preferably a fluorine-containing polymer that is crosslinked by heat or ionizing radiation having a coefficient of dynamic friction of 0.03 to 0.20, a contact angle with water of 90 to 120 °, and a sliding angle of pure water of 70 ° or less. When the antireflection film of the present invention is mounted on an image display device, the lower the peel strength from a commercially available adhesive tape, the easier it is to peel off after sticking a seal or memo, preferably 5N or less, more preferably 3N or less, Most preferred is 1N or less. Further, the higher the surface hardness measured with a microhardness meter, the harder it is to scratch, preferably 0.3 GPa or more, more preferably 0.5 GPa or more.

  Examples of the fluorine-containing polymer used in the low refractive index layer include hydrolysis and dehydration condensate of perfluoroalkyl group-containing silane compounds (for example, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane). And a fluorine-containing copolymer having a fluorine-containing monomer unit and a structural unit for imparting crosslinking reactivity as structural components.

  Specific examples of the fluorine-containing monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, perfluorooctylethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole. Etc.), partially (meth) acrylic acid or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (manufactured by Osaka Organic Chemical), M-2020 (manufactured by Daikin), etc.), fully or partially fluorinated vinyl ethers, etc. However, perfluoroolefins are preferred, and hexafluoropropylene is particularly preferred from the viewpoints of refractive index, solubility, transparency, availability, and the like.

  As structural units for imparting crosslinking reactivity, structural units obtained by polymerization of monomers having a self-crosslinkable functional group in the molecule in advance such as glycidyl (meth) acrylate and glycidyl vinyl ether, carboxyl groups, hydroxy groups, amino acids Polymerization of monomers having a group, a sulfo group, etc. (eg (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid, crotonic acid, etc.) The resulting structural unit, a structural unit in which a crosslinking reactive group such as a (meth) acryloyl group is introduced into these structural units by a polymer reaction (for example, an acrylic acid chloride is allowed to act on a hydroxy group). And the like.

  In addition to the above-mentioned fluorine-containing monomer units and structural units for imparting crosslinking reactivity, monomers not containing fluorine atoms can be copolymerized as appropriate from the viewpoints of solubility in solvents and film transparency. There are no particular limitations on the monomer units that can be used in combination. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid 2) -Ethylhexyl), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers (methyl) Vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate etc.), acrylamides (N-tert-butylacrylamide, N- Black hexyl acrylamide), methacrylamides, and acrylonitrile derivatives.

  As described in JP-A-10-25388 and JP-A-10-147739, a curing agent may be appropriately used in combination with the above polymer.

(Light scattering layer)
The light scattering layer is formed for the purpose of contributing to the film light diffusibility due to surface scattering and / or internal scattering, and hard coat properties for improving the scratch resistance of the film. Therefore, it is formed to contain a binder for imparting hard coat properties, matte particles for imparting light diffusibility, and inorganic fillers for increasing the refractive index, preventing cross-linking shrinkage, and increasing the strength as necessary. The

  The thickness of the light scattering layer is preferably 1 to 10 μm and more preferably 1.2 to 6 μm for the purpose of imparting hard coat properties. If it is too thin, the hard property will be insufficient, and if it is too thick, curling and brittleness will deteriorate and the workability will be insufficient.

  The binder of the scattering layer is preferably a polymer having a saturated hydrocarbon chain or a polyether chain as the main chain, and more preferably a polymer having a saturated hydrocarbon chain as the main chain. The binder polymer preferably has a crosslinked structure. As the binder polymer having a saturated hydrocarbon chain as a main chain, a polymer of an ethylenically unsaturated monomer is preferable. As the binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure, a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferable. In order to make the binder polymer have a high refractive index, the monomer structure contains an aromatic ring, at least one atom selected from halogen atoms other than fluorine, sulfur atoms, phosphorus atoms, and nitrogen atoms. You can also choose.

  Examples of the monomer having two or more ethylenically unsaturated groups include esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di ( (Meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-si Rhohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate), modified ethylene oxide, vinylbenzene and derivatives thereof (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1, 4-divinylcyclohexanone), vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylenebisacrylamide) and methacrylamide. Two or more of these monomers may be used in combination.

  Specific examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, and the like. Two or more of these monomers may be used in combination.

Polymerization of the monomer having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.
Accordingly, a coating liquid containing a monomer having an ethylenically unsaturated group, a photo radical initiator or a thermal radical initiator, mat particles, and an inorganic filler is prepared, and the coating liquid is applied on a transparent support and then ionizing radiation or heat is applied. The antireflection film can be formed by curing by the polymerization reaction. As these photo radical initiators, known ones can be used.

The polymer having a polyether as the main chain is preferably a ring-opening polymer of a polyfunctional epoxy compound. The ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with ionizing radiation or heating in the presence of a photoacid generator or a thermal acid generator.
Accordingly, a coating liquid containing a polyfunctional epoxy compound, a photoacid generator or a thermal acid generator, matte particles and an inorganic filler is prepared, and the coating liquid is applied onto a transparent support and then subjected to a polymerization reaction by ionizing radiation or heat. Curing can form an antireflection film.

Instead of or in addition to a monomer having two or more ethylenically unsaturated groups, a monomer having a crosslinkable functional group is used to introduce a crosslinkable functional group into the polymer, and by reaction of this crosslinkable functional group, A crosslinked structure may be introduced into the binder polymer.
Examples of the crosslinkable functional group include isocyanate group, epoxy group, aziridine group, oxazoline group, aldehyde group, carbonyl group, hydrazine group, carboxyl group, methylol group and active methylene group. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition.
These binder polymers having a crosslinkable functional group can form a crosslinked structure by heating after coating.

For the purpose of imparting antiglare properties, the light scattering layer contains matte particles having an average particle size of 1 to 10 μm, preferably 1.5 to 7.0 μm, such as inorganic compound particles or resin particles, for the purpose of imparting antiglare properties. Is done.
As specific examples of the mat particles, inorganic particles such as silica particles and TiO ₂ particles; resin particles such as acrylic particles, cross-linked acrylic particles, polystyrene particles, cross-linked styrene particles, melamine resin particles, and benzoguanamine resin particles are preferable. Can be mentioned. Of these, crosslinked styrene particles, crosslinked acrylic particles, crosslinked acrylic styrene particles, and silica particles are preferable. The shape of the mat particles can be either spherical or irregular.

  Two or more kinds of mat particles having different particle diameters may be used in combination. It is possible to impart anti-glare properties with mat particles having a larger particle size and to impart other optical characteristics with mat particles having a smaller particle size.

  Furthermore, the particle size distribution of the mat particles is most preferably monodisperse, and the particle sizes of the particles are preferably closer to each other. For example, when a particle having a particle size of 20% or more than the average particle size is defined as a coarse particle, the proportion of the coarse particle is preferably 1% or less, more preferably 0.1% of the total number of particles. Or less, more preferably 0.01% or less. Matt particles having such a particle size distribution are obtained by classification after a normal synthesis reaction, and a matting agent having a more preferable distribution can be obtained by increasing the number of classifications or increasing the degree of classification.

The mat particles are contained in the light scattering layer so that the amount of mat particles in the formed light scattering layer is preferably 10 to 1000 mg / m ² , more preferably 100 to 700 mg / m ² .
The particle size distribution of the mat particles is measured by a Coulter counter method, and the measured distribution is converted into a particle number distribution.

The light scattering layer is made of an oxide of at least one metal selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony, in addition to the above mat particles, in order to increase the refractive index of the layer. Thus, it is preferable that an inorganic filler having an average particle size of 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.06 μm or less is contained.
Conversely, in order to increase the refractive index difference from the mat particles, it is also preferable to use a silicon oxide in order to keep the refractive index of the layer low in the light scattering layer using the high refractive index mat particles. The preferred particle size is the same as that of the aforementioned inorganic filler.
Specific examples of the inorganic filler to be used in the light scattering _{layer, TiO 2, ZrO 2, Al} 2 O 3, In 2 O 3, ZnO, SnO 2, Sb 2 O 3, ITO and SiO ₂ and the like. TiO ₂ and ZrO ₂ are particularly preferable from the viewpoint of increasing the refractive index. The surface of the inorganic filler is preferably subjected to a silane coupling treatment or a titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder species on the filler surface is preferably used.
The amount of these inorganic fillers added is preferably 10 to 90% of the total mass of the light scattering layer, more preferably 20 to 80%, and particularly preferably 30 to 75%.
In addition, since such a filler has a particle size sufficiently smaller than the wavelength of light, scattering does not occur, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.

  The bulk refractive index of the mixture of binder and inorganic filler in the light scattering layer is preferably 1.48 to 2.00, more preferably 1.50 to 1.80. In order to make the refractive index within the above range, the kind and amount ratio of the binder and the inorganic filler may be appropriately selected. How to select can be easily known experimentally in advance.

  In order to ensure surface uniformity such as coating unevenness, drying unevenness, point defects, etc., the light scattering layer should be coated with either a fluorine-based surfactant or a silicone-based surfactant, or both for forming an antiglare layer. Contained in the composition. In particular, a fluorine-based surfactant is preferably used because an effect of improving surface defects such as coating unevenness, drying unevenness, and point defects of the antireflection film of the present invention appears in a smaller addition amount. The purpose is to increase productivity by giving high-speed coating suitability while improving surface uniformity.

Next, an antireflection layer in which a middle refractive index layer, a high refractive index layer, and a low refractive index layer are laminated in this order on the transparent protective film will be described.
An antireflection film having a layer structure of at least a medium refractive index layer, a high refractive index layer, and a low refractive index layer (outermost layer) on the substrate is designed to have a refractive index satisfying the following relationship.
The refractive index of the high refractive index layer> The refractive index of the medium refractive index layer> The refractive index of the transparent support> The refractive index of the low refractive index layer Further, a hard coat layer is provided between the transparent support and the medium refractive index layer. Also good. Further, it may comprise a medium refractive index hard coat layer, a high refractive index layer and a low refractive index layer.
Examples thereof include JP-A Nos. 8-122504, 8-110401, 10-300902, JP-A 2002-243906, JP-A 2000-11706, and the like.
Other functions may be imparted to each layer, for example, an antifouling low refractive index layer or an antistatic high refractive index layer (eg, JP-A-10-206603, JP-A-2002). -243906 publication etc.) etc. are mentioned.
The haze of the antireflection film is preferably 5% or less, more preferably 3% or less. The strength of the film is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test according to JIS K5400.

(High refractive index layer and medium refractive index layer)
The layer having a high refractive index of the antireflection film is composed of a curable film containing at least an inorganic compound ultrafine particle having a high refractive index having an average particle diameter of 100 nm or less and a matrix binder.
Examples of the high refractive index inorganic compound fine particles include inorganic compounds having a refractive index of 1.65 or more, preferably those having a refractive index of 1.9 or more. Examples thereof include oxides such as Ti, Zn, Sb, Sn, Zr, Ce, Ta, La, and In, and composite oxides containing these metal atoms.
In order to obtain such ultrafine particles, the surface of the particles is treated with a surface treating agent (for example, silane coupling agents, etc .: JP-A Nos. 1-295503, 11-153703, 2000-9908). No., anionic compound or organometallic coupling agent: Japanese Patent Laid-Open No. 2001-310432, etc. (For example, JP-A-11-153703, US Pat. No. 6,210,858, JP-A-2002-27776069, etc.) and the like.
Examples of the material forming the matrix include conventionally known thermoplastic resins and curable resin films.
Further, it is selected from a polyfunctional compound-containing composition containing at least two radically polymerizable and / or cationically polymerizable groups, an organometallic compound containing a hydrolyzable group, and a partial condensate composition thereof. At least one composition is preferred. For example, the composition as described in Unexamined-Japanese-Patent No. 2000-47004, 2001-315242, 2001-31871, 2001-296401 etc. is mentioned.
A curable film obtained from a colloidal metal oxide obtained from a hydrolyzed condensate of metal alkoxide and a metal alkoxide composition is also preferred. For example, it describes in Unexamined-Japanese-Patent No. 2001-293818.
The refractive index of the high refractive index layer is generally 1.70 to 2.20. The thickness of the high refractive index layer is preferably 5 nm to 10 μm, and more preferably 10 nm to 1 μm.
The refractive index of the middle refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.50 to 1.70. The thickness is preferably 5 nm to 10 mμ, more preferably 10 nm to 1 μm.

(Low refractive index layer)
The low refractive index layer is formed by sequentially laminating on the high refractive index layer. The refractive index of the low refractive index layer is 1.20 to 1.55. Preferably it is 1.30-1.50.
It is preferable to construct as the outermost layer having scratch resistance and antifouling property. As means for greatly improving the scratch resistance, it is effective to impart slipperiness to the surface, and conventionally known thin film layer means such as introduction of silicone or introduction of fluorine can be applied.
The refractive index of the fluorine-containing compound is preferably 1.35 to 1.50. More preferably, it is 1.36-1.47. The fluorine-containing compound is preferably a compound containing a crosslinkable or polymerizable functional group containing fluorine atoms in the range of 35 to 80% by mass.
For example, paragraph numbers [0018] to [0026] of Japanese Patent Application Laid-Open No. 9-222503, paragraph numbers [0019] to [0030] of Japanese Patent Application Laid-Open No. 11-38202, and paragraph numbers of Japanese Patent Application Laid-Open No. 2001-40284. [0027] to [0028], compounds described in JP-A No. 2000-284102, and the like.
The silicone compound is a compound having a polysiloxane structure, preferably containing a curable functional group or a polymerizable functional group in the polymer chain and having a crosslinked structure in the film. For example, reactive silicone (eg, Silaplane (manufactured by Chisso Corporation), silanol group-containing polysiloxane (Japanese Patent Laid-Open No. 11-258403, etc.) and the like can be mentioned.
The crosslinking or polymerization reaction of the fluorine-containing and / or siloxane polymer having a crosslinking or polymerizable group is performed simultaneously with or after the application of the coating composition for forming the outermost layer containing a polymerization initiator, a sensitizer and the like. It is preferable to carry out by light irradiation or heating.

Also preferred is a sol-gel cured film in which an organometallic compound such as a silane coupling agent and a specific fluorine-containing hydrocarbon group-containing silane coupling agent are cured by a condensation reaction in the presence of a catalyst.
For example, a polyfluoroalkyl group-containing silane compound or a partially hydrolyzed condensate thereof (Japanese Patent Laid-Open Nos. 58-142958, 58-147483, 58-147484, Japanese Patent Laid-Open Nos. 9-157582, 11) -106704 and the like), silyl compounds containing a poly "perfluoroalkyl ether" group which is a fluorine-containing long chain group (Japanese Patent Application Laid-Open Nos. 2000-117902, 2001-48590, 2002-53804). Etc.) and the like.
The low refractive index layer has an average primary particle diameter of 1 to 150 nm such as a filler (for example, silicon dioxide (silica), fluorine-containing particles (magnesium fluoride, calcium fluoride, barium fluoride)) as an additive other than the above. A low refractive index inorganic compound, organic fine particles described in paragraphs [0020] to [0038] of JP-A-11-3820), silane coupling agents, slip agents, surfactants, and the like.
When the low refractive index layer is located below the outermost layer, the low refractive index layer may be formed by a vapor phase method (vacuum deposition method, sputtering method, ion plating method, plasma CVD method, etc.). The coating method is preferable because it can be manufactured at a low cost.
The film thickness of the low refractive index layer is preferably 30 to 200 nm, more preferably 50 to 150 nm, and most preferably 60 to 120 nm.

(Other layers of antireflection layer)
Further, a hard coat layer, a forward scattering layer, a primer layer, an antistatic layer, an undercoat layer, a protective layer, and the like may be provided.

(Hard coat layer)
The hard coat layer is provided on the surface of the transparent support in order to impart physical strength to the transparent protective film provided with the antireflection layer. In particular, it is preferably provided between the transparent support and the high refractive index layer. The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of a light and / or heat curable compound. As the curable functional group, a photopolymerizable functional group is preferable, and an organic metal compound containing a hydrolyzable functional group, particularly an organic alkoxysilyl compound is preferable.
Specific examples of these compounds are the same as those exemplified for the high refractive index layer. Specific examples of the constituent composition of the hard coat layer include those described in JP-A Nos. 2002-144913, 2000-9908, and WO 00/46617.
The high refractive index layer can also serve as a hard coat layer. In such a case, it is preferable to form fine particles dispersed in the hard coat layer using the method described for the high refractive index layer.
A hard-coat layer can also serve as the glare-proof layer (after-mentioned) which contained the particle | grains with an average particle diameter of 0.2-10 micrometers and provided the glare-proof function (anti-glare function).
The film thickness of the hard coat layer can be appropriately designed depending on the application. The film thickness of the hard coat layer is preferably 0.2 to 10 μm, more preferably 0.5 to 7 μm.
The strength of the hard coat layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test according to JIS K5400. Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

(Antistatic layer)
In the case of providing an antistatic layer, it is preferable to impart conductivity with a volume resistivity of 10 ⁻⁸ (Ωcm ⁻³ ) or less. The use of hygroscopic substances, water-soluble inorganic salts, certain surfactants, cationic polymers, anionic polymers, colloidal silica, etc. can give a volume resistivity of 10 ⁻⁸ (Ωcm ⁻³ ). There is a problem that dependency is large, and sufficient conductivity cannot be secured at low humidity. Therefore, a metal oxide is preferable as the conductive layer material. Some metal oxides are colored, but using these metal oxides as the conductive layer material is not preferable because the entire film is colored. Zn, Ti, Sn, Al, In, Si, Mg, Ba, Mo, W, or V can be given as the metal that forms the metal oxide without coloring, and a metal oxide containing this as a main component is used. It is preferable. Specific examples include ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ , WO ₃ , V ₂ O ₅ , or complex oxides thereof. In particular, ZnO, TiO ₂ and SnO ₂ are preferable. Examples of containing different atoms include, for example, additives such as Al and In for ZnO, addition of Sb, Nb and halogen elements for SnO ₂ , and Nb and Ta for TiO ₂ . Addition is effective. Furthermore, as described in Japanese Examined Patent Publication No. 59-6235, a material in which the above metal oxide is attached to other crystalline metal particles or fibrous materials (for example, titanium oxide) may be used. The volume resistance value and the surface resistance value are different physical properties and cannot be simply compared. However, in order to secure a conductivity of 10 ⁻⁸ (Ωcm ⁻³ ) or less in volume resistance, It is sufficient that the layer has a surface resistance value of approximately 10 ⁻¹⁰ (Ω / □) or less, and more preferably 10 ⁻⁸ (Ω / □). The surface resistance value of the conductive layer needs to be measured as a value when the antistatic layer is the outermost layer, and can be measured in the middle of forming the laminated film described in this patent.

(Liquid crystal display device)
The optical compensation sheet comprising the cellulose acylate film of the present invention or the polarizing plate using the cellulose acylate film of the present invention is advantageously used for a liquid crystal display device. The cellulose acylate film of the present invention can be used for liquid crystal cells in various display modes. TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal, AFLC) Various display modes such as HAN (Hybrid Aligned Nematic) have been proposed. Of these, the OCB mode or the VA mode can be preferably used.

  The OCB mode liquid crystal cell is a liquid crystal display device using a bend alignment mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned in a substantially opposite direction (symmetrically) between an upper portion and a lower portion of the liquid crystal cell. OCB mode liquid crystal cells are disclosed in US Pat. Nos. 4,583,825 and 5,410,422. Since the rod-like liquid crystal molecules are aligned symmetrically between the upper part and the lower part of the liquid crystal cell, the bend alignment mode liquid crystal cell has a self-optical compensation function. For this reason, this liquid crystal mode is also called an OCB (Optically Compensatory Bend) liquid crystal mode. The bend alignment mode liquid crystal display device has an advantage of high response speed.

In a VA mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied.
The VA mode liquid crystal cell includes (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). 176625) (2) Liquid crystal cell (SID97, Digest of tech. Papers (Preliminary Proceed) 28 (1997) 845 in which the VA mode is made into a multi-domain (MVA mode) for widening the viewing angle ), (3) Liquid crystal cell in a mode (n-ASM mode) in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied (Preliminary collections 58-59 of the Japanese Liquid Crystal Society) (1998)) and (4) SURVAVAL mode liquid crystal cells (announced at LCD International 98).
The VA mode liquid crystal display device includes a liquid crystal cell and two polarizing plates disposed on both sides thereof. The liquid crystal cell carries a liquid crystal between two electrode substrates. In one aspect of the transmissive liquid crystal display device of the present invention, the optical compensation sheet of the present invention is disposed between the liquid crystal cell and one polarizing plate, or between the liquid crystal cell and both polarizing plates. Place two in between.
In another aspect of the transmissive liquid crystal display device of the present invention, an optical compensation sheet made of the cellulose acylate film of the present invention is used as the transparent protective film of the polarizing plate disposed between the liquid crystal cell and the polarizer. The above optical compensation sheet may be used only for the transparent protective film (between the liquid crystal cell and the polarizer) of one polarizing plate, or between the polarizing plates (between the liquid crystal cell and the polarizer). The above optical compensation sheet may be used for the two transparent protective films. The cellulose acylate film of the present invention is preferably bonded to the liquid crystal cell on the VA cell side. The protective film may be a normal cellulose acylate film, and is preferably thinner than the cellulose acylate film of the present invention. For example, 40 to 80 μm is preferable, and commercially available KC4UX2M (40 μm manufactured by Konica Capto Co., Ltd.), KC5UX (60 μm manufactured by Konica Caputo Co., Ltd.), Fujitac TD80UF (80 μm manufactured by Fuji Photo Film Co., Ltd.) and the like can be mentioned. It is not limited to these.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to an Example.
[Measurement method]
Various characteristics of the cellulose acylate film were measured by the following methods.
(Retardation Re, Rth)
Re is measured by adjusting the cellulose acylate film at 25 ° C. and 60% RH for 24 hours, and then applying light of wavelength λ nm in the film normal direction in KOBRA 21ADH (manufactured by Oji Scientific Instruments). Rth was measured by making light having a wavelength λ nm incident from a direction inclined + 40 ° with respect to the film normal direction with the Re, in-plane slow axis (determined by KOBRA 21ADH) as the tilt axis (rotation axis). The retardation value and the retardation value measured by making light of wavelength λ nm incident from a direction inclined −40 ° with respect to the film normal direction with the in-plane slow axis as the tilt axis (rotation axis). KOBRA 21ADH is calculated based on the retardation value measured in the direction. Here, as the assumed value of the average refractive index, the values in the polymer handbook (JOHN WILEY & SONS, INC) and catalogs of various optical films can be used. Those whose average refractive index is not known can be measured with an Abbe refractometer. The average refractive index values of main optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), Polystyrene (1.59). The KOBRA 21ADH calculates nx, ny, and nz by inputting these assumed values of average refractive index and film thickness.
(Moisture content)
A 7 mm × 35 mm sample was measured by a Karl Fischer method using a moisture measuring device and a sample drying apparatus (CA-03, VA-05, both Mitsubishi Chemical Corporation). The moisture content (g) was calculated by dividing by the sample mass (g).

(Linear expansion coefficient)
Measurement was performed using a TA analyzer Thermo Analyzer TMA2940. The sample (effective sample length 3 cm) was heated from room temperature to 80 ° C., then measured for dimensional change when returning from 80 ° C. to room temperature, and the dimensional change rate per 1 ° C. was calculated. The MD direction and TD direction of the film were measured.
(Heat shrinkage)
Sample 30 mm x 120 mm was aged at 90 ° C, 5% RH for 24, 120 hours, and automatic pin gauge (Shinto Kagaku Co., Ltd.) was used to drill 6mmφ holes at both ends at 100mm intervals, and the original size of the interval (L1) Was measured to a minimum scale of 1/1000 mm. Furthermore, it was left to stand at 60 ° C., 95% RH or 90 ° C., 5% RH for 24 hours, and the dimension (L2) of the punch interval was measured. And the thermal contraction rate was calculated | required by {(L1-L2) / L1} * 100.
(Glass transition point Tg)
Grasp a film sample (unstretched) 5 mm x 30 mm with a dynamic viscoelasticity measuring device (Vibron: DVA-225 (manufactured by IT Measurement Control Co., Ltd.)) after conditioning at 25 ° C and 60% RH for 2 hours or more. Measured at a distance of 20 mm, a temperature increase rate of 2 ° C./min, a measurement temperature range of 30 ° C. to 200 ° C. and a frequency of 1 Hz, the logarithmic axis is the storage elastic modulus, and the horizontal axis is the temperature (° C.) on the linear axis. The straight line 1 and the straight line when the straight line 1 is drawn in the solid region and the straight line 2 is drawn in the glass transition region, when the storage elastic modulus sometimes shifts from the solid region to the glass transition region. The intersection of 2 is the temperature at which the storage elastic modulus suddenly decreases and the film begins to soften when the temperature rises, and is the temperature at which the film begins to move to the glass transition region, and is thus defined as the glass transition temperature Tg (dynamic viscoelasticity).

(Elastic modulus)
Sample 10mm x 200mm is conditioned for 2 hours at 25 ° C, 60% RH, and elastic modulus is measured with tensile tester (Strograph-R2 (manufactured by Toyo Seiki)) at initial sample length of 100mm and tensile speed of 100mm / min It was calculated from the stress and elongation at the initial stage of tension.
(Photoelastic coefficient)
A tensile stress was applied to the long axis direction of a 10 mm × 100 mm film sample, and the Re retardation at that time was measured with an ellipsometer (M150, JASCO Corporation), and the photoelastic coefficient was calculated from the amount of change in retardation with respect to the stress. Was calculated.
(Haze)
A sample of 40 mm × 80 mm was measured according to JIS K6714 with a haze meter (HGM-2DP, Suga Test Instruments) at 25 ° C. and 60% RH.

[Example 1]
1. Film formation of cellulose acylate film (1) Cellulose acylate Linter cellulose, catalytic sulfuric acid (7.8 parts by mass with respect to 100 parts by mass of cellulose) and carboxylic acid were added and an acylation reaction was carried out at 40 ° C. Thereafter, the total substitution degree and the 6-position substitution degree were adjusted by adjusting the amount of sulfuric acid catalyst, the amount of water, and the aging time. The aging temperature was 40 ° C. Further, the low molecular weight component of the cellulose acylate was removed by washing with acetone.
(2) Dope preparation A dope was prepared by mixing, stirring and dissolving cellulose acylate, a plasticizer (a 2-to-1 mixture of triphenyl phosphate and biphenyl diphenyl phosphate), and a solvent. When the solvent used was dichloromethane / methanol (87/13 parts by mass), it was heated and dissolved at 70 to 90 ° C. in a pressure-resistant sealed container and then filtered.
When the solvent used was methyl acetate / acetone / ethanol / butanol (81/8/7/4 parts by mass), the liquid swollen at room temperature was once cooled to −70 ° C. and then heated to 40 ° C. to dissolve. . After filtration of the resulting dope, flash concentration was performed at a temperature of 120 ° C., and the solid content concentration in the dope was adjusted to about 22%.
The properties of the cellulose acylate used are listed in Table 1.

(3) Preparation of Matting Agent Dispersion Next, the following composition containing the cellulose acylate solution prepared by the above method was charged into a dispersing machine to prepare each matting agent dispersion.

(Matting agent dispersion)
Silica particles having an average particle diameter of 16 nm (Aerosil R972 manufactured by Nippon Aerosil Co., Ltd. 2.0 parts by mass methylene chloride 72.4 parts by mass methanol 10.8 parts by mass cellulose acylate solution 10.3 parts by mass

  A matting agent dispersion containing methyl acetate as a main solvent was prepared using methyl acetate instead of the above solvents methylene chloride and methanol.

(4) Retardation developer solution Next, the following composition containing the cellulose acylate solution prepared by the above method was put into a mixing tank, and dissolved by stirring to prepare each retardation developer solution.

(Retardation developer solution)
Retardation developer 20.0 parts by mass Methylene chloride 58.3 parts by mass Methanol 8.7 parts by mass Cellulose acylate solution 12.8 parts by mass

  A matting agent dispersion containing methyl acetate as a main solvent was prepared using methyl acetate instead of the above solvents methylene chloride and methanol.

(5) Ultraviolet (UV) absorber solution Next, the following composition containing the cellulose acylate solution prepared by the above method was put into a mixing tank, dissolved by stirring to prepare a UV absorber solution.

(UV absorber solution)
Sumisorb 165F 20.0 parts by mass Methyl acetate 67.0 parts by mass Cellulose acylate solution 12.8 parts by mass

(6) Film formation The dope prepared in (1) is sent out with a gear pump, and a predetermined amount of matting agent dispersion, retardation developer solution and UV absorber solution are injected in the middle, and mixed uniformly with a static mixer. Cast using a casting machine. The composition of the casting dope is shown in Table 1. Next, the residual solvent amount is 25 to 35% by mass, and the film peeled off from the band is dried by applying hot air while holding the tenter while suppressing shrinkage in the width direction, and then the tenter conveyance is shifted to the roll conveyance. It dried, knurled, and wound up by 1440 mm width, and produced unstretched film R1 to R4. The residual solvent was all 0.2% or less. Table 1 shows the glass transition temperature (Tg) and thickness of this film.

(7) Stretching Unstretched films R1 to R3 were sent to a preheating zone and preheated. Thereafter, the film was stretched by 21 to 35% in the width direction (TD) by a tenter device, contracted by 5%, then exited from the tenter zone, cut off the ear after cooling, wound up with a width of 1440 mm with knurling. The optical biaxial cellulose acylate films F1 to F7 and Comparative Example F8 of Examples were prepared by changing the preheating temperature, the stretching temperature, and the stretching ratio. Table 2 shows the unstretched film, preheating temperature, stretching temperature, and stretching ratio used for each. The draw ratio in Table 2 is expressed as the ratio of the tenter outlet film width to the tenter inlet film width.

[Comparative Example 1]
The same dope, matting agent dispersion and retardation adjusting agent solution as in the production of the unstretched film R2 of Example 1 were used and cast in the same manner as R2. After peeling the film from the band, the residual solvent amount was 15 to 30%, held in a tenter clip, and stretched in the width direction by 25 to 30%. Thereafter, the film was shrunk by 5% while being held by a clip, and was taken out of the tenter zone. The ears were cut and further dried and wound up with the residual solvent amount being 0.2% or less to prepare optical biaxial cellulose acylate films of Comparative Examples F9 and F10. The stretching temperature and the stretching ratio are shown in Table 2. The draw ratio in Table 2 is expressed as the ratio of the tenter outlet film width to the tenter inlet film width.

The optical biaxial films of Examples and Comparative Examples thus prepared were measured for optical characteristics (Re, Rth) at 7 points in the width direction, and the average Rea, Rth and Re width ΔRe are listed in Table 2. The linear expansion coefficients in the casting direction (MD) and the width direction (TD) were measured and listed in Table 2. The moisture content after conditioning at 25 ° C. and 80% RH is all 2.3 to 3.0%, and the moisture permeability for 24 hours at 60 ° C. and 95% RH is all 800 to 1250 g / m ² / day. Is 0.1 to 0.9, the secondary average particle size of the matting agent is 1.0 μm or less, the tensile elastic modulus is 4 GPa or more, and when left standing at 80 ° C. and 90% RH for 48 hours. Mass change was 0-3%. Moreover, the dimensional change when it left still for 24 hours on the conditions of 60 degreeC95% RH and 90 degreeC5% RH was 0 to 4.5%. Furthermore, the photoelastic coefficient of all samples was 50 × 10 ⁻¹³ cm ² / dyne or less.

[Example 2]
<2-1-1>
(Preparation of polarizing plate-1)
A polarizer was produced by adsorbing iodine to a stretched polyvinyl alcohol film.
The cellulose acylate films (F1 to F10: corresponding to TAC1 in FIGS. 1 to 3) prepared in Example 1 and Comparative Example 1 were attached to one side of the polarizer using a polyvinyl alcohol-based adhesive. The saponification treatment was performed under the following conditions.
A 1.5N aqueous sodium hydroxide solution was prepared and kept at 55 ° C. A 0.01 N dilute sulfuric acid aqueous solution was prepared and kept at 35 ° C. The produced cellulose acylate film was immersed in the aqueous sodium hydroxide solution for 2 minutes, and then immersed in water to sufficiently wash away the aqueous sodium hydroxide solution. Subsequently, after being immersed in the above-mentioned dilute sulfuric acid aqueous solution for 1 minute, it was immersed in water to sufficiently wash away the dilute sulfuric acid aqueous solution. Finally, the sample was thoroughly dried at 120 ° C.
Commercially available cellulose triacylate film (Fujitac TD80UF, manufactured by Fuji Photo Film Co., Ltd .: functional film TAC2 in FIG. 2, equivalent to TAC2-1 or 2-2 in FIG. 3) is subjected to saponification treatment to obtain a polyvinyl alcohol type Using an adhesive, it was attached to the opposite side of the polarizer and dried at 70 ° C. for 10 minutes or more.
The transmission axis of the polarizer and the slow axis of the cellulose acylate film produced in Example 1 were arranged in parallel (FIG. 1). It arrange | positioned so that the transmission axis of a polarizer and the slow axis of a commercially available cellulose triacylate film might orthogonally cross.
Using a spectrophotometer (UV3100PC), the cellulose acylate films prepared in Example 1 and Comparative Example 1 are combined inside the polarizer so that the polarizing plate of 380 nm to 780 nm at 25 ° C. and 60% RH is single. The plate transmittance TT, the parallel transmittance PT, and the orthogonal transmittance CT were measured, and the average value of 400 to 700 nm and the degree of polarization P were determined. The TT was 40.8 to 44.7, and the PT was 34 to 38. 8, CT was 1.0 or less, and P was 99.98-99.99. Further, the orthogonal transmittances CT ₍₃₈₀₎ , CT ₍₄₁₀₎ and CT _{(700) at} wavelengths of 380 nm, 410 nm and 700 nm were 1.0 or less, 0.5 or less and 0.3 or less, respectively. Further, in the polarizing plate durability test at 60 ° C. and 95% RH for 500 hours, both fall within the range of −0.1 ≦ ΔCT ≦ 0.2 and −2.0 ≦ ΔP ≦ 0, and at −60 ° C. and 90% RH, −0.05 ≦ ΔCT ≦ 0.15 and −1.5 ≦ ΔP ≦ 0.
The thus-prepared polarizing plates A1 to A10 (the optical compensation film-integrated polarizing plate having no functional film in FIG. 2) are partly stored in a moisture-proof bag and the other part is 25. After humidity conditioning at 60 ° C. and 60% RH, it was stored in a moisture-proof bag. The moisture-proof bag was a packaging material having a laminated structure of polyethylene terephthalate / aluminum / polyethylene, and the moisture permeability was 0.01 mg / m ² (24 hours) or less.

<2-2-1>
(Preparation of coating solution for light scattering layer)
50 g of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (PETA, Nippon Kayaku Co., Ltd.) was diluted with 38.5 g of toluene. Further, 2 g of a polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) was added and mixed and stirred. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.51.
Further, a 30% toluene dispersion of crosslinked polystyrene particles having an average particle size of 3.5 μm (refractive index: 1.60, SX-350, manufactured by Soken Chemical Co., Ltd.) dispersed in this solution for 20 minutes at 10,000 rpm with a Polytron disperser. Add 13.3 g of 30% toluene dispersion of 1.7 g and crosslinked acrylic-styrene particles having an average particle size of 3.5 μm (refractive index 1.55, manufactured by Soken Chemical Co., Ltd.), and finally, fluorine-based surface modification 0.75 g of agent (FP-1) and 10 g of silane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) were added to obtain a finished solution.
The liquid mixture was filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating solution for the light scattering layer.

<2-2-2>
(Preparation of coating solution for low refractive index layer)
First, sol solution a was prepared as follows. A stirrer, a reactor equipped with a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyltrimethoxysilane (KBM5103, manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts of diisopropoxyaluminum ethyl acetoacetate were added and mixed. After adding 30 parts of ion-exchanged water and reacting at 60 ° C. for 4 hours, it was cooled to room temperature to obtain a sol solution a. The mass average molecular weight was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.
Thermally crosslinkable fluorine-containing polymer having a refractive index of 1.42 (JN-7228, solid content concentration 6%, manufactured by JSR Corporation) 13 g, silica sol (silica, MEK-ST particle size difference, average particle size 45 nm, solid content 30% concentration, manufactured by Nissan Chemical Co., Ltd.) 1.3 g, the above sol a0.6 g, methyl ethyl ketone 5 g, and cyclohexanone 0.6 g were added. A layer coating solution was prepared.

<2-2-3>
(Preparation of transparent protective film 01 with light scattering layer)
An 80 μm-thick triacetyl cellulose film (Fujitac TD80UF, manufactured by Fuji Photo Film Co., Ltd.) is unwound in a roll form, and the coating liquid for the functional layer (light scattering layer) is 180 lines / inch, depth Using a microgravure roll with a diameter of 50 mm and a doctor blade having a gravure pattern of 40 μm, coating was performed under the conditions of a gravure roll rotation speed of 30 rpm and a conveyance speed of 30 m / min, drying at 60 ° C. for 150 seconds, and further under nitrogen purge Using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.), the coating layer is cured by irradiating ultraviolet rays with an illuminance of 400 mW / cm ² and an irradiation amount of 250 mJ / cm ² , and a functional layer having a thickness of 6 μm And wound up.
The triacetyl cellulose film coated with the functional layer (light scattering layer) is unwound again, and the prepared coating liquid for the low refractive index layer is gravure with a line number of 180 lines / inch and a depth of 40 μm on the light scattering layer side. Using a micro gravure roll with a diameter of 50 mm and a doctor blade having a pattern, it was applied under conditions of a gravure roll rotation speed of 30 rpm and a conveyance speed of 15 m / min, dried at 120 ° C. for 150 seconds, and further dried at 140 ° C. for 8 minutes. Then, using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) under a nitrogen purge, ultraviolet rays with an illuminance of 400 mW / cm ² and an irradiation amount of 900 mJ / cm ² were irradiated, and a low refraction with a thickness of 100 nm The rate layer was formed and wound up (corresponding to the functional film TAC2 in FIG. 2 or TAC2-1 in FIG. 3).

<2-3-1>
(Preparation of polarizing plate-2)
A polarizer was produced by adsorbing iodine to a stretched polyvinyl alcohol film.
The prepared transparent protective film 01 with a light scattering layer is subjected to the same saponification treatment as described in <2-1-1>, and a side without a functional film and one side of a polarizer are pasted using a polyvinyl alcohol-based adhesive. I attached.
The same saponification treatment was performed on the cellulose acylate films (F1 to F10: corresponding to TAC1 in FIG. 1) prepared in Example 1 and Comparative Example 1, and on the opposite side of the polarizer using a polyvinyl alcohol-based adhesive. The film was pasted and dried at 70 ° C. for 10 minutes or more (the configuration in FIG. 2 was completed).
The transmission axis of the polarizer and the slow axis of the cellulose acylate film produced in Example 1 and Comparative Example 1 were arranged in parallel (FIG. 1). The transmission axis of the polarizer and the slow axis of the transparent protective film 01 with the light scattering layer were arranged so as to be orthogonal to each other. In this way, polarizing plates (B1 to B10: functional film and optical compensation film integrated polarizing plate (FIG. 2)) were produced. In the same manner as in <2-1-1> Production of Polarizing Plate, one was put in a moisture-proof bag after conditioning for 2 hours at 25 ° C. and 60% RH, and another was put in a moisture-proof bag without conditioning.
A polarizer was produced by adsorbing iodine to a stretched polyvinyl alcohol film. The transparent protective film 01 with the light scattering layer prepared in <2-2-3> and the triacetylcellulose film (Fujitac TD80UF, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm without applying the functional layer are described above. The saponification treatment was performed in the same manner as that described above, and was bonded to a polarizer in the same manner as described above using a polyvinyl alcohol-based adhesive. In this way, a polarizing plate (B0: functional film, optical compensation film integrated polarizing plate (FIG. 2)) was prepared. In the same manner as the production <2-1-1> of the polarizing plate, a product put in a moisture-proof bag after humidity control and a product put in a moisture-proof bag without conditioning were prepared.
Using a spectrophotometer (manufactured by JASCO Corporation), in the wavelength region of 380 to 780 nm, the spectral reflectance at an incident angle of 5 ° is measured from the functional film side, and the integrating sphere average reflectance of 450 to 650 nm is obtained. When determined, it was 2.3%.

<2-4-1>
(Preparation of coating solution for hard coat layer)
750.0 parts by mass of trimethylolpropane triacrylate (TMPTA, Nippon Kayaku Co., Ltd.), 270.0 parts by mass of poly (glycidyl methacrylate) having a mass average molecular weight of 3000, 730.0 g of methyl ethyl ketone, 500.0 g of cyclohexanone and light A polymerization initiator (Irgacure 184, manufactured by Nippon Ciba-Geigy Co., Ltd.) 50.0 g was added and stirred. The solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a hard coat layer.

<2-4-2>
(Preparation of titanium dioxide fine particle dispersion)
As the titanium dioxide fine particles, titanium dioxide fine particles (MPT-129, manufactured by Ishihara Sangyo Co., Ltd.) containing cobalt and surface-treated with aluminum hydroxide and zirconium hydroxide were used.
The following dispersant (38.6 g) and cyclohexanone (704.3 g) were added to 257.1 g of the particles and dispersed by dynomill to prepare a titanium dioxide dispersion having a mass average diameter of 70 nm.

<2-4-3>
(Preparation of coating solution for medium refractive index layer)
To 88.9 g of the above titanium dioxide dispersion, 58.4 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA), 3.1 g of a photopolymerization initiator (Irgacure 907), a photosensitizer (Kayacure DETX) 1.1 g of Nippon Kayaku Co., Ltd.), 482.4 g of methyl ethyl ketone and 1869.8 g of cyclohexanone were added and stirred. After sufficiently stirring, the solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for a medium refractive index layer.

<2-4-4>
(Preparation of coating solution for high refractive index layer)
To 56.8 g of the above titanium dioxide dispersion, 47.9 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), photopolymerization initiator (Irgacure 907, Nippon Ciba Geigy ( Co., Ltd.) 4.0 g, photosensitizer (Kayacure-DETX, Nippon Kayaku Co., Ltd.) 1.3 g, methyl ethyl ketone 455.8 g, and cyclohexanone 1427.8 g were added and stirred. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for a high refractive index layer.

<2-4-5>
(Preparation of coating solution for low refractive index layer)
A copolymer represented by the following formula was dissolved in methyl isobutyl ketone so as to have a concentration of 7% by mass, and a terminal methacrylate group-containing silicone resin X-22-164C (manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the solid content. 3% of the photoradical generator Irgacure 907 (trade name) was added in an amount of 5% by mass based on the solid content to prepare a coating solution for a low refractive index layer.

<2-4-6>
(Preparation of transparent protective film 02 with antireflection layer)
A hard coat layer coating solution was applied onto a triacetylcellulose film (Fujitac TD80UF, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm using a gravure coater. After drying at 100 ° C., an irradiance of 400 mW / cm using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm while purging with nitrogen so that the oxygen concentration becomes 1.0 vol% or less. ^{2. The} coating layer was cured by irradiating ultraviolet rays with an irradiation amount of 300 mJ / cm ² to form a hard coat layer having a thickness of 8 μm.
On the hard coat layer, a medium refractive index layer coating solution, a high refractive index layer coating solution, and a low refractive index layer coating solution were successively applied using a gravure coater having three coating stations.

The drying condition of the medium refractive index layer is 100 ° C. for 2 minutes, and the ultraviolet curing condition is a 180 W / cm air-cooled metal halide lamp (I graphics ), And the irradiation amount was 400 mW / cm ² and the irradiation amount was 400 mJ / cm ² . The medium refractive index layer after curing had a refractive index of 1.630 and a film thickness of 67 nm.

The drying conditions of the high refractive index layer and the low refractive index layer are both 90 ° C., 1 minute, 100 ° C., 1 minute, and the ultraviolet curing condition is nitrogen so that the atmosphere has an oxygen concentration of 1.0% by volume or less. While purging, a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) was used to obtain an irradiation dose of 600 mW / cm ² and an irradiation dose of 600 mJ / cm ² .
The cured high refractive index layer had a refractive index of 1.905 and a film thickness of 107 nm, and the low refractive index layer had a refractive index of 1.440 and a film thickness of 85 nm. In this way, a transparent protective film 02 with an antireflection layer was produced (corresponding to the functional film TAC2 in FIG. 2 or TAC2-1 in FIG. 3).

<2-5-1>
(Preparation of polarizing plate-3)
A polarizing plate (C1 to C10: functional film, optical compensation film) is the same as <2-3-1> except that the transparent protective film 02 with an antireflection layer is used instead of the transparent protective film 01 with a light scattering layer. A body-type polarizing plate (FIG. 2) was produced. In the same manner, a polarizing film comprising a transparent protective film 02 with an antireflection layer, a triacetylcellulose film (Fujitac TD80UF, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm without applying a polarizer and a functional layer. A plate (C0) was produced.
Using a spectrophotometer (manufactured by JASCO Corporation), in the wavelength region of 380 to 780 nm, the spectral reflectance at an incident angle of 5 ° is measured from the functional film side, and the integrating sphere average reflectance of 450 to 650 nm is obtained. When determined, it was 0.4%.

[Example 3]
(Mounting on the panel)

[Example 3-1]
(Mounting on VA panel) (Single sheet type)
The liquid crystal display device of FIG. 3 was produced. That is, from the observation direction (top), the upper polarizing plate (TAC2-1 (with / without functional film), polarizer, TAC1-1), VA mode liquid crystal cell, lower polarizing plate (TAC1-2, polarizer, TAC2) -2) were laminated, and a backlight light source was further arranged. In the following example, a commercially available polarizing plate (HLC2-5618) is used for the upper polarizing plate, and a polarizing plate integrated with an optical compensation film is used for the lower polarizing plate. But there is no problem functionally. However, as an integrated polarizing plate, it is often used as a lower polarizing plate (if it is used as an upper polarizing plate, it is necessary to provide a functional film on the observation side (upper side) and the production yield may be lowered. Therefore, it is considered to be a more preferable embodiment.

<Production of liquid crystal cell>
The liquid crystal cell has a cell gap between substrates of 3.6 μm, and a liquid crystal material having negative dielectric anisotropy (“MLC6608”, manufactured by Merck & Co., Inc.) is dropped and sealed between the substrates. Prepared by forming a layer. The retardation of the liquid crystal layer (that is, the product Δn · d of the thickness d (μm) of the liquid crystal layer and the refractive index anisotropy Δn) was set to 300 nm. The liquid crystal material was aligned so as to be vertically aligned.

A commercially available super high contrast product (for example, HLC2-5618 manufactured by Sanlitz Co., Ltd.) is used for the upper polarizing plate (observer side) of the liquid crystal display device (FIG. 3) using the vertical alignment type liquid crystal cell. It was. A polarizing plate (A4) prepared in <2-1-1> of Example 2 using the optical compensation sheet prepared in Example 1 and Comparative Example 1 (F4 to F9) for the lower polarizing plate (backlight side) -A9) were placed so that the cellulose acylate film (corresponding to TAC1-2 in FIG. 3) produced in Example 1 was on the liquid crystal cell side. The upper polarizing plate and the lower polarizing plate were attached to the liquid crystal cell via an adhesive. The crossed Nicols were arranged so that the transmission axis of the upper polarizing plate was in the vertical direction and the transmission axis of the lower polarizing plate was in the left-right direction. The polarizing plate to be used is a liquid crystal that uses both a pre-packed and stored in a moisture-proof and moisture-proof bag for 2 hours under a temperature and humidity condition of 25 ° C. and 60% RH, and a polarizing plate that is stored in a bag without humidity control. A display device was created.
Here, a commercial product is used for the upper polarizing plate and the integrated polarizing plate of the present invention is used for the lower polarizing plate. As a result of observing the produced liquid crystal display device, the front direction and the viewing angle direction are also neutral. Black display was realized. However, in the samples using the polarizing plates of Comparative Examples A8 and A9, unevenness in blackness due to weak light leakage was observed depending on the location.
Using a measuring instrument (EZ-Contrast 160D, manufactured by ELDIM), viewing angles in 8 stages from black display (L1) to white display (L8) (contrast ratio is 10 or more and there is no gradation inversion on the black side) Was measured. Both the present example and the comparative example had a wide viewing angle.
Next, a measuring instrument (EZ-Contrast160D, manufactured by ELDIM) measuring the color at the time of black display with an azimuth angle of 45 ° based on the horizontal direction of the liquid crystal display screen and a polar angle of 60 ° based on the normal direction of the screen surface Was used as an initial value. Next, this panel was left in a room at room temperature and normal humidity (no humidity control at about 25 ° C. and 60% RH) for one week, and the color at the time of black display was measured again. As a result of observation, the color change of the polarizing plate before the assembly of the liquid crystal display device was particularly small in color change.
Finally, the liquid crystal display device was placed in an oven at 60 ° C. for 6 hours, taken out, left for 1 hour, and then observed with black display. Only the polarizing plate A9 of Comparative Example was clearly seen from the four corners. Light leakage was observed.

[Example 3-2]
The liquid crystal display device using the above vertical alignment type liquid crystal cell (FIG. 3) uses the optical compensation sheet prepared in Example 1 and Comparative Example 1 (F4 to F9) in the lower polarizing plate of Example 2 < The polarizing plate (A4 to A9) prepared in 2-1-1> is attached to the upper polarizing plate, and the polarizing plate (B0) prepared in <2-3-1> of Example 2 is attached via an adhesive. It was. The crossed nicols were arranged so that the transmission axis of the polarizing plate on the observer side was in the vertical direction and the transmission axis of the polarizing plate on the backlight side was in the horizontal direction. At this time, the air-conditioning was performed so that the temperature of the workplace was 20 to 25 ° C. and the humidity was 50 to 70% RH. The polarizing plates to be used are both those stored in a moisture-proof and moisture-proof bag for 2 hours under the temperature and humidity conditions of 25 ° C. and 60% RH, and those stored in a bag without humidity control. A liquid crystal display device was created.
Here, a commercial product is used for the upper polarizing plate and the integrated polarizing plate of the present invention is used for the lower polarizing plate. As a result of observing the produced liquid crystal display device, the front direction and the viewing angle direction are also neutral. Black display was realized. However, in the samples using the polarizing plates of Comparative Examples A8 and A9, unevenness in blackness due to weak light leakage was observed depending on the location.
Using a measuring instrument (EZ-Contrast 160D, manufactured by ELDIM), viewing angles in 8 stages from black display (L1) to white display (L8) (contrast ratio is 10 or more and there is no gradation inversion on the black side) Was measured. Both the present example and the comparative example had a wide viewing angle.
Next, a measuring instrument (EZ-Contrast160D, manufactured by ELDIM) measuring the color at the time of black display with an azimuth angle of 45 ° based on the horizontal direction of the liquid crystal display screen and a polar angle of 60 ° based on the normal direction of the screen surface Was used as an initial value. Next, this panel was left in a room at room temperature and normal humidity (no humidity control at about 25 ° C. and 60% RH) for one week, and the color at the time of black display was measured again. As a result of observation, the color change of the polarizing plate before the assembly of the liquid crystal display device was particularly small in color change.
Finally, the liquid crystal display device was placed in an oven at 60 ° C. for 6 hours, taken out, left for 1 hour, and then observed with black display. Only the polarizing plate A9 of Comparative Example was clearly seen from the four corners. Light leakage was observed.

[Example 3-3]
The liquid crystal display device using the above vertical alignment type liquid crystal cell (FIG. 3) uses the optical compensation sheet prepared in Example 1 and Comparative Example 1 (F4 to F9) in the lower polarizing plate of Example 2 < The polarizing plate (C0) prepared in <2-5-1> of Example 2 was attached to the upper polarizing plate via the adhesive, with the polarizing plate (A4 to A9) prepared in 2-1-1>. . The crossed nicols were arranged so that the transmission axis of the polarizing plate on the observer side was in the vertical direction and the transmission axis of the polarizing plate on the backlight side was in the horizontal direction. At this time, the air-conditioning was performed so that the temperature of the workplace was 20 to 25 ° C. and the humidity was 50 to 70% RH. The polarizing plates to be used are both those stored in a moisture-proof and moisture-proof bag for 2 hours under the temperature and humidity conditions of 25 ° C. and 60% RH, and those stored in a bag without humidity control. A liquid crystal display device was created.
Here, a commercial product is used for the upper polarizing plate and the integrated polarizing plate of the present invention is used for the lower polarizing plate. As a result of observing the produced liquid crystal display device, the front direction and the viewing angle direction are also neutral. Black display was realized. However, in the samples using the polarizing plates of Comparative Examples A8 and A9, unevenness in blackness due to weak light leakage was observed depending on the location.
Using a measuring instrument (EZ-Contrast 160D, manufactured by ELDIM), viewing angles in 8 stages from black display (L1) to white display (L8) (contrast ratio is 10 or more and there is no gradation inversion on the black side) Was measured. Both the present example and the comparative example had a wide viewing angle.
Next, a measuring instrument (EZ-Contrast160D, manufactured by ELDIM) measuring the color at the time of black display with an azimuth angle of 45 ° based on the horizontal direction of the liquid crystal display screen and a polar angle of 60 ° based on the normal direction of the screen surface Was used as an initial value. Next, this panel was left in a room at room temperature and normal humidity (no humidity control at about 25 ° C. and 60% RH) for one week, and the color at the time of black display was measured again. As a result of observation, the color change of the polarizing plate before the assembly of the liquid crystal display device was particularly small in color change.
Finally, the liquid crystal display device was placed in an oven at 60 ° C. for 6 hours, taken out and left for 1 hour, and then observed with black display. Only the polarizing plate A9 of Comparative Example was clearly seen from the four corners. Light leakage was observed.

[Example 3-4]
(Mounting on VA panel) (2 sheets)
The liquid crystal display device of FIG. 3 was produced. That is, from the observation direction (top), the upper polarizing plate (TAC2-1 (no functional film), polarizer, TAC1-1), VA mode liquid crystal cell, lower polarizing plate (TAC1-2, polarizer, TAC2-2) ) And a backlight light source.

<Production of liquid crystal cell>
The liquid crystal cell has a cell gap between substrates of 3.6 μm, and a liquid crystal material having negative dielectric anisotropy (“MLC6608”, manufactured by Merck & Co., Inc.) is dropped and sealed between the substrates. Prepared by forming a layer. The retardation of the liquid crystal layer (that is, the product Δn · d of the thickness d (μm) of the liquid crystal layer and the refractive index anisotropy Δn) was set to 300 nm. The liquid crystal material was aligned so as to be vertically aligned.

<2-1- of Example 2 which uses the optical compensation sheet produced in Example 1 (F1) for the upper and lower polarizing plates of the liquid crystal display device (FIG. 3) using the vertical alignment type liquid crystal cell described above. The polarizing plate (A1) produced in 1> was observed through an adhesive so that the cellulose acylate film (TAC1-1 and TAC1-2 in FIG. 3) produced in Example 1 was on the liquid crystal cell side. One sheet was attached to each side and backlight side. The crossed nicols were arranged so that the transmission axis of the polarizing plate on the observer side was in the vertical direction and the transmission axis of the polarizing plate on the backlight side was in the horizontal direction. At this time, the air-conditioning was performed so that the temperature of the workplace was 20 to 25 ° C. and the humidity was 50 to 70% RH. The polarizing plates to be used are both those stored in a moisture-proof and moisture-proof bag for 2 hours under the temperature and humidity conditions of 25 ° C. and 60% RH, and those stored in a bag without humidity control. A liquid crystal display device was created.
As a result of observing the manufactured liquid crystal display device, neutral black display was realized in the front direction and the viewing angle direction, and unevenness was hardly observed. In addition, using a measuring instrument (EZ-Contrast 160D, manufactured by ELDIM), the viewing angle (contrast ratio is 10 or more and there is no black-side gradation inversion) in eight stages from black display (L1) to white display (L8). Range).
Next, a measuring instrument (EZ-Contrast160D, manufactured by ELDIM) measuring the color at the time of black display with an azimuth angle of 45 ° based on the horizontal direction of the liquid crystal display screen and a polar angle of 60 ° based on the normal direction of the screen surface Was used as an initial value. Next, this panel was left in a room at room temperature and normal humidity (no humidity control at about 25 ° C. and 65% RH) for one week, and the color during black display was measured again.
This example had a wide viewing angle and almost no change in color. In the case where the humidity of the polarizing plate was adjusted before assembling the liquid crystal display device, the color change was particularly small.
Finally, the liquid crystal display device was placed in an oven at 60 ° C. for 6 hours, taken out and left for 1 hour, and then observed with a black display. No light leakage was observed at the corners.

It is a schematic diagram which shows the bonding method of the cellulose acylate film at the time of manufacture of the polarizing plate of this invention. It is sectional drawing which shows typically the cross-section of the polarizing plate of this invention. It is sectional drawing which shows typically the cross-section of the liquid crystal display device of this invention.

Claims (21)

  A roll-like film having a residual solvent amount of less than 3% is fed from a feeding device, preheated at a temperature 10 ° C. to 40 ° C. lower than the stretching temperature, and then 1. An optical cellulose acylate film which is stretched 1 to 1.6 times. The optical cellulose acylate film according to claim 1, wherein the in-plane retardation value Re and the retardation value Rth in the film thickness direction satisfy the following formulas (I) and (II).
(I) 30 ≦ Re ≦ 100
(II) 120 ≦ Rth ≦ 400
[Wherein, Re and Rth are values (unit: nm) at a wavelength of 590 nm. ]   The optical cellulose acylate film according to claim 2, wherein 50 ≦ Re ≦ 100, Rth = a−5.9Re and 580 ≦ a ≦ 670.   The optical cellulose acylate film according to claim 2, wherein 30 ≦ Re ≦ 45 and 120 ≦ Rth ≦ 180. The difference ΔRe between the maximum Re value and the minimum Re value measured at 7 points in the width direction and the average Re value Rea measured at 7 points in the width direction satisfy the following formula (III): Optical cellulose acylate film.
(III) ΔRe / Rea ≦ 0.025 6. The optical device according to claim 5, wherein a difference ΔRth between a maximum Rth value measured at 7 points in the width direction and a minimum Rth value and an average Rth value Rtha measured at 7 points in the width direction satisfy the following formula (IV): Cellulose acylate film.
(IV) ΔRth / Rtha ≦ 0.02   The optical cellulose acylate film according to any one of claims 1 to 6, wherein the thermal expansion coefficient in the casting direction (MD) is 75 ppm / ° C or less and the thermal expansion coefficient in the width direction (TD) is 45 ppm / ° C or less. A cellulose acylate film obtained by substituting the hydroxyl group of cellulose with an acyl group having 2 or more carbon atoms, wherein the substitution degree of the acyl group at the 2-position is DS2 and the substitution degree of the acyl group at the 3-position is 8. The optical cellulose acylate film according to claim 1, wherein the following formulas (V) and (VI) are satisfied when DS3 has a substitution degree of the acyl group at the 6-position of DS6.
(V) 2.0 ≦ DS2 + DS3 + DS6 ≦ 3.0
(VI) DS6 / (DS2 + DS3 + DS6) ≧ 0.315   9. The optical cellulose acylate film according to claim 1, wherein the acyl group is an acetyl group.   A roll-like film having a residual solvent amount of less than 3% is fed from a feeding device, preheated at a temperature 10 ° C. to 40 ° C. lower than the stretching temperature, and then 1. A method for producing an optical biaxial cellulose acylate film, wherein the film is stretched 1 to 1.6 times.   A polarizing plate using at least one optical cellulose acylate film according to claim 1 as a protective film for a polarizer. The single plate transmittance TT, parallel transmittance PT, orthogonal transmittance CT, and polarization degree P at 25 ° C. and 60% RH of the polarizing plate satisfy at least one of the following formulas (a) to (d). The polarizing plate according to claim 11.
(A) 40.0 ≦ TT ≦ 45.0
(B) 30.0 ≦ PT ≦ 40.0
(C) CT ≦ 2.0
(D) 95.0 ≦ P CT ₍₃₈₀₎ , CT ₍₄₁₀₎ and CT ₍₇₀₀₎ satisfy at least one of the following formulas (e) to (g), where CT ₍ λ ₎ is the orthogonal transmittance at wavelength λ. The polarizing plate according to claim 10 or 12.
(E) CT ₍₃₈₀₎ ≦ 2.0
(F) CT ₍₄₁₀₎ ≦ 0.1
(G) CT ₍₇₀₀₎ ≦ 0.5 The orthogonal transmittance change ΔCT and polarization degree change ΔP when left at 60 ° C. and 95% RH for 500 hours satisfy at least one of the following formulas (j) and (k): Item 14. The polarizing plate according to any one of Items 11 to 13.
(J) −6.0 ≦ ΔCT ≦ 6.0
(K) -10.0 ≦ ΔP ≦ 0.0
(However, the amount of change is the value obtained by subtracting the pre-test measurement value from the post-test measurement value)   The polarizing plate which provided at least one layer of the hard-coat layer, the glare-proof layer, and the antireflection layer in the surface of the other side protective film of the polarizing plate in any one of Claims 11-14.   The polarizing plate packaged in a bag subjected to moisture-proofing treatment, wherein the humidity in the packaged state is 43% RH to 70% RH at 25 ° C. The polarizing plate of crab.   The polarizing plate is packaged in a moisture-proof bag, and the humidity in the packaged state is within 15% RH of the humidity when the polarizing plate is bonded to the liquid crystal panel. The polarizing plate according to claim 11, wherein:   An OCB mode liquid crystal display device comprising at least one optical cellulose acylate film according to any one of claims 1 to 9 or a polarizing plate according to any one of claims 11 to 17.   A VA mode liquid crystal display device comprising at least one optical cellulose acylate film according to claim 1 or at least one polarizing plate according to claim 11. A VA mode liquid crystal display comprising only one optical cellulose acylate film according to any one of claims 1 to 3 and 5 to 9 or a polarizing plate according to any one of claims 11 to 17. apparatus.   An optical cellulose acylate film according to any one of claims 1, 2, and 4-9 or a polarizing plate according to any one of claims 11 to 17 is used on each side of a liquid crystal cell. VA mode liquid crystal display device.

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