JP5183772B2 - Liquid crystal display - Google Patents

Description

  The present invention relates to a liquid crystal display device using a cellulose acylate film.

  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. Various modes have been proposed for such a liquid crystal display device depending on the alignment state of the liquid crystal molecules in the liquid crystal cell. Conventionally, the liquid crystal display device is in an alignment state twisted by about 90 ° from the lower substrate to the upper substrate of the liquid crystal cell. The TN mode was mainstream.

  In general, a liquid crystal display device includes a liquid crystal cell, an optical compensation sheet, and a polarizing film. 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 compound to a transparent film is used. For example, Patent Document 1 discloses a technique in which an optical compensation sheet in which a discotic liquid crystal compound is applied on a triacetyl cellulose film and aligned and fixed is applied 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. Particularly, the VA mode is attracting attention as a liquid crystal display device for television because it has a high contrast and a relatively high manufacturing yield.

  By the way, the cellulose acylate film is characterized by high optical isotropy (low retardation value) as compared with other polymer films. Therefore, it is common to use a cellulose acylate film for an application requiring optical isotropy, for example, a constituent member of 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). Particularly, in the optical compensation sheet for VA mode, a front retardation (Re) of 30 to 200 nm and a thickness direction retardation (Rth) of 70 to 400 nm are required. 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 rule to use cellulose acylate films when required.

  Patent Document 2 proposes a cellulose acetate film having a high retardation value that can be used for applications requiring optical anisotropy, overcoming the conventional general principle. In this proposal, in order to achieve a high retardation value with cellulose triacetate, an aromatic compound having at least two aromatic rings 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, but it is necessary to increase the birefringence by simultaneously orienting the additives in the stretching process. 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 has an acyl group having 2 to 4 carbon atoms as a substituent, where the substitution degree of acetyl group is A and the substitution degree of propionyl group or butyryl group is B, formula 2.0 ≦ A + B ≦ 3.0 and a cellulose ester satisfying the formula A <2.4 at the same time, and the refractive index Nx in the slow axis direction and the refractive index Ny in the fast axis direction at a wavelength of 590 nm An optical film characterized by satisfying 0005 ≦ Nx−Ny ≦ 0.0050 is disclosed.

In Patent Document 4, the degree of substitution of the hydroxyl group of the cellulose ester resin satisfies the following formulas (1) and (2) at the same time, and an ultraviolet absorbing monomer having a specific chemical structure with respect to 100 parts by mass of the cellulose ester resin. 1 to 20 parts by mass of an ultraviolet-absorbing polymer derived by containing at least, and stretched so that the in-plane direction retardation value R0 is 20 to 100 nm and the thickness direction retardation value Rt is 70 to 300 nm. A cellulose ester film is disclosed which is characterized in that
Formula (1) 2.4 <= A + B <= 2.8
Formula (2) 1.4 ≦ A ≦ 2.0
[Wherein, A represents the degree of substitution of the acetyl group, and B represents the degree of substitution of the acyl group having 3 or 4 carbon atoms. ]

  In Patent Document 5, a polarizing plate used in a VA mode liquid crystal display device, the polarizing plate has a polarizing film and an optically biaxial mixed fatty acid cellulose ester film, and is disposed between the liquid crystal cell and the polarizing film. A polarizing plate is disclosed in which the optically biaxial mixed fatty acid cellulose ester film is disposed.

Japanese Patent No. 2587398 European Patent Application 0911656A2 JP 2002-71957 A JP 2002-71957 A JP 2002-270442 A

  The use of a cellulose acylate film as in the method disclosed in the above-mentioned literature is effective in that an inexpensive and thin liquid crystal display device can be obtained. However, when the cellulose acylate film is made thinner, sagging, wrinkles, and bending of the film are likely to occur, and the problem that handling is difficult occurs. This problem has been particularly noticeable when processing into a polarizing plate and when bonding to a liquid crystal display device.

  An object of the present invention is to provide a cellulose acylate film that is excellent in expression of front and film thickness direction retardation, is thin, and is easy to handle during production and processing. The second object of the present invention is to provide a liquid crystal display device using the cellulose acylate film with little change in viewing angle characteristics and a polarizing plate used for the liquid crystal display device.

  As a result of diligent research, the present inventors can solve the above-mentioned problems associated with thinning by adjusting the elastic modulus of the cellulose acylate film to a specific range that is higher in elasticity than a conventionally used film. It was found that a cellulose acylate film which can be easily handled during manufacture and processing can be provided. At the same time, the present inventors have found a method for producing such a thin and high elastic cellulose acylate film without solving the above-mentioned problems and without causing breakage or haze.

  As the elastic modulus of the cellulose acylate film, a material having a viscosity of about 2 to 3.5 GPa has been widely used in the past, but the present inventors have made a thin film by setting the elastic modulus to 3.5 GPa or more. However, it has been found that sagging, wrinkling, and bending do not occur when processing into a polarizing plate or bonding to a liquid crystal display device. On the other hand, it has also been found that if the elastic modulus exceeds 10 GPa, chips may be generated when a slit of a film or a polarizing plate is punched. That is, by setting the elastic modulus to 3.5 to 10 GPa, the object of the present invention can be achieved, and the elastic modulus is preferably 4 to 7 GPa, and most preferably 4 to 6 GPa.

  The “elastic modulus” in the present specification is a value obtained by measuring the elastic modulus according to the method described in JIS K7127 after conditioning the sample for 24 hours in an environment of 25 ° C. and 60% RH. Tensilon manufactured by A & D Co., Ltd. was used as the tensile tester.

  In addition, the film thickness of the cellulose acylate film is preferably as thin as possible in order to realize an inexpensive and thin liquid crystal display device. However, if the film is too thin, it is bonded even if the elastic modulus is appropriately adjusted as described above. It has been found that handling is difficult due to problems such as wrinkles of time, and that these problems do not occur when the film thickness is 20 to 70 μm. Therefore, by setting the film thickness to 20 to 70 μm, the object of the present invention can be achieved, and the film thickness is preferably 30 to 60 μm, and most preferably 30 to 50 μm.

  Furthermore, as a result of earnest research on the method for producing a stretched film, the present inventors have stretched the above-mentioned book by stretching 1.2 to 4.0 times and 1.05 to 3.8 times in two orthogonal directions. It has been found that the object of the invention can be achieved. This is because, in such a biaxial stretching method, it has been found that if the stretching ratio is set too high, breakage during stretching may occur. By setting the draw ratio within a specific range, a thin cellulose acylate film having a high elastic modulus as described above can be realized.

  Further, the present inventors have further studied and found that using cellulose acylate having a substituent by a propionyl group, a butyryl group or a benzoyl group is more preferable for preventing the breakage as described above.

  Further, when the draw ratio is increased when producing the above-described thin film, conventionally, the haze of the film tends to increase. When the haze is increased, the resolution and contrast of the image are lowered when the film is used in a liquid crystal display device. Therefore, a film having the smallest possible haze is desired.

  Therefore, as a result of examining the temperature and stretching speed at the time of stretching, the present inventors have conducted biaxial stretching at a temperature of the glass transition temperature of the cellulose acylate film + 25 ° C. or more and the crystallization temperature or less, Alternatively, it has been found that by carrying out biaxial stretching at a stretching rate of 10% / min or less, the haze can be reduced even with a thin film produced by high-magnification stretching.

  In particular, the haze value of the cellulose acylate film is preferably as small as possible, but is preferably 1% or less, and more preferably 0.7% or less. The haze value is a value measured using a haze meter MODEL 1001DP (manufactured by Nippon Denshoku Industries Co., Ltd.).

  It supplements about the description of "stretch ratio" in this specification. The 2.0-fold stretching is a description that means that the length of the unstretched film is stretched to twice as long as 1.0, and is equivalent to a description of 100% stretching. The notation of 10% / min of the stretching speed is equivalent to the notation of 0.1 times / min. Specifically, 10% / min means that the film is stretched for a length of 0.1 per minute when the unstretched film is 1.

The present invention has been made based on the points found by the present inventors described above, and specifically has the following configuration.
[1]
A liquid crystal display device having a polarizing plate having a polarizing film and a pair of protective films sandwiching the polarizing film,
Cellulose acylate in which at least one of the protective films is formed by solution casting with a film thickness of 20 to 70 μm having an elastic modulus of 3.5 to 10 GPa in at least one of the film casting direction and the width direction A film,
The front retardation Re of the cellulose acylate film is in the range of 30 to 70 nm, the retardation Rth in the film thickness direction is in the range of 120 to 180 nm,
A liquid crystal display device having a viewing angle of at least three polar directions of up, down, left, and right, and a polar angle of 80 ° or more, and a contrast in a front direction represented by white display brightness / black display brightness is 300 or more.
[2]
The liquid crystal display device according to [1], wherein the elastic modulus is 4 to 6 GPa .
[3]
The liquid crystal display device according to [1] or [2], wherein the haze of the cellulose acylate film is 1% or less.
[4]
The liquid crystal display device according to any one of [1] to [3], wherein the cellulose acylate film is substantially composed of cellulose acylate satisfying the following formulas (I) and (II).
Formula (I): 2.6 ≦ A + B ≦ 3.0
Formula (II): 0 <B
(In the formulas (I) and (II), A is the degree of substitution of the hydroxyl group in the glucose unit of the cellulose acylate with an acetyl group, and B is the propionyl group or butyryl group of the hydroxyl group in the glucose unit of the cellulose acylate. Or the degree of substitution with a benzoyl group)
[5]
The liquid crystal display device according to any one of [1] to [4], which is an OCB or VA mode liquid crystal display device.
[6]
A VA mode liquid crystal display device having a liquid crystal cell and a pair of polarizing plates disposed on both sides of the liquid crystal cell, wherein the cellulose acylate film is provided on a backlight side polarizing plate. Any one of [1] to [5] A liquid crystal display device according to claim 1.
Although this invention is invention which concerns on said [1]-[6], below, other matters are also described.
1) A cellulose acylate film having a film thickness of 20 to 70 μm and an elastic modulus of 3.5 to 10 GPa in at least one of a film casting direction and a width direction.
2) The cellulose acylate film according to 1), wherein the front retardation Re is in the range of 20 to 80 nm and the retardation Rth in the film thickness direction is in the range of 100 to 250 nm.
3) The cellulose acylate film according to 1) or 2), wherein the haze of the film is 1% or less.
4) The cellulose acylate film according to any one of 1) to 3), which is substantially composed of cellulose acylate satisfying the following formulas (I) and (II).
Formula (I): 2.6 ≦ A + B ≦ 3.0
Formula (II): 0 <B
(In the formulas (I) and (II), A is the degree of substitution of the hydroxyl group in the glucose unit of the cellulose acylate with an acetyl group, and B is the propionyl group or butyryl group of the hydroxyl group in the glucose unit of the cellulose acylate. Or the degree of substitution with a benzoyl group)
5) A method for producing a cellulose acylate film having a stretching step, wherein the stretching step has stretching ratios in biaxial directions orthogonal to each other of 1.2 to 4.0 times and 1.05 to 3.8, respectively. The film is stretched at a glass transition temperature of the film + 25 ° C. and below the crystallization temperature, and the film thickness of the film after the stretching process is 20 to 70 μm. A method for producing a cellulose acylate film.
6) It is a manufacturing method of the cellulose acylate film which has a extending process, Comprising: The extending process WHEREIN: The draw ratio of the biaxial direction orthogonal to each other is 1.2-4.0 times, 1.05-3.8, respectively. It is a step of stretching at a stretch rate of at least one of biaxial directions perpendicular to each other and a stretching speed of 10% / min or less, and the film thickness of the film after the stretching step is 20 to 70 μm. A method for producing a cellulose acylate film.
7) The cellulose acylate film according to any one of 1) to 4), which is produced by the production method according to 5) or 6).
8) A polarizing plate having a polarizing film and a pair of protective films sandwiching the polarizing film, wherein at least one of the protective films is a cellulose acylate according to any one of 1) to 4) and 7) A polarizing plate characterized by being a film.
9) A liquid crystal display device comprising the cellulose acylate film according to any one of 1) to 4) and 7) or the polarizing plate according to 8).
10) An OCB or VA mode liquid crystal display device having a liquid crystal cell and a pair of polarizing plates disposed on both sides of the liquid crystal cell, wherein at least one of the polarizing plates is a polarizing plate according to 8). There is a liquid crystal display device.
11) A VA mode liquid crystal display device having a liquid crystal cell and a pair of polarizing plates disposed on both sides of the liquid crystal cell, wherein the liquid crystal display has the polarizing plate described in 8) on the backlight side. apparatus.

  ADVANTAGE OF THE INVENTION According to this invention, the cellulose acylate film which is excellent in the expression property of a front direction and a film thickness direction retardation, is thin, and is easy to handle at the time of manufacture and processing is provided. Moreover, according to this invention, the polarizing plate used for a liquid crystal display device with little viewing angle characteristic change using the said cellulose acylate film, and a liquid crystal display device is provided.

It is sectional drawing for demonstrating typically the liquid crystal display device produced in the Example.

Hereinafter, the present invention will be described in more detail.
The cellulose acylate film of the present invention is characterized in that the film thickness is within a specific range, and the elastic modulus in at least one of the film casting direction and the width direction is within a specific range.
Hereinafter, first, the cellulose acylate film of the present invention will be described in detail in the order of the raw materials, the production method, and the film itself.

<Raw material of cellulose acylate film>
[Cellulose acylate]
First, the cellulose acylate used in the present invention is described in detail. In the present invention, two or more different cellulose acylates may be mixed and used.
As the cellulose acylate, when the substitution degree of the hydroxyl group in the glucose unit of cellulose acylate by A is A and the substitution degree by propionyl group, butyryl group or benzoyl group is B, A and B are represented by formula (I) And cellulose acylate satisfying (II) can be preferably used.

Formula (I): 2.6 ≦ A + B ≦ 3.0
Formula (II): 0 <B

  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 means the proportion of cellulose esterified at each of the 2-position, 3-position and 6-position (100% esterification has a degree of substitution of 1 at each position). The degree of acyl substitution can be measured according to ASTM-D817-96.

In the present invention, the total sum (A + B) of the substitution degree of hydroxyl groups A and B is preferably 2.6 to 3.0 as shown in the above formula (I). Further, the substitution degree of B is preferably greater than 0, more preferably 0.5 or more and 1.2 or less, still more preferably 0.6 or more and 0.8, as shown in the above formula (II). It is as follows.
When A + B is less than 2.6, the above range is preferable because it is easily affected by environmental humidity due to excessive hydrophilicity. In addition, it is preferable to use cellulose acylate having a B greater than 0, that is, a substituent having a propionyl group, a butyryl group, or a benzoyl group, as described above, which can prevent breakage of the film. The cellulose acylate may have one or more kinds of substituents having a substitution degree B, that is, a propionyl group, a butyryl group, or a benzoyl group.

{Synthesis Method of Cellulose Acylate}
The basic principle of the cellulose acylate synthesis method is described in Mita et al., Wood Chemistry pages 180-190 (Kyoritsu Shuppan, 1968). A typical synthesis method is a liquid phase acetylation method using a carboxylic acid anhydride-acetic acid-sulfuric acid catalyst.
In order to obtain the cellulose acylate, specifically, a cellulose raw material such as cotton linter or wood pulp is pretreated with an appropriate amount of acetic acid, and then esterified by introducing it into a pre-cooled carboxylated mixed solution. Synthesize the rate (total of acyl substitution at the 2nd, 3rd and 6th positions is approximately 3.00). The carboxylated mixed solution generally contains acetic acid as a solvent, carboxylic anhydride as an esterifying agent (for example, acetic anhydride and propionic anhydride, or butyric anhydride) 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 esterification 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 a 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 to the cellulose acylate solution), the cellulose acylate is separated, washed and stabilized, etc. Can be obtained.

The cellulose acylate film is preferably composed of cellulose acylate in which the polymer component constituting the film substantially satisfies the above formulas (I) and (II). “Substantially” means 55% by mass or more (preferably 70% by mass or more, more preferably 80% by mass or more) of the polymer component.
The cellulose acylate is also preferably used in the form of particles. 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, preferably 200 to 700, more preferably 250 to 550, still more preferably 250 to 400, and particularly preferably 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 (polymerization degree) is increased, but the viscosity is lower than that of ordinary cellulose acylate. Therefore, the cellulose acylate from which the low molecular component is removed 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 acylate 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 acylates. When the amount of the sulfuric acid catalyst is in 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 cellulose acylate, the water content is preferably 2% by mass or less, more preferably 1% by mass or less, and particularly 0.7% by mass or less. In general, cellulose acylate contains water and is known to have a water content of 2.5 to 5% by mass. In order to obtain the water content of the cellulose acylate in the present invention, it may be dried, and the method is not particularly limited as long as the desired water content is obtained.
The cellulose acylate raw material cotton and the synthesis method thereof are disclosed in JIII Journal of Technical Disclosure No. 2001-1745 (issued March 15, 2001, Invention Association) p. Raw material cotton and synthesis methods described in detail in 7-12 can be employed.

  The cellulose acylate film of the present invention can be obtained by forming a film using a solution prepared by dissolving the specific cellulose acylate and, if necessary, an additive in an organic solvent.

{Additive}
Examples of the additive that can be used in the cellulose acylate solution in the present invention include a plasticizer, an ultraviolet absorber, a deterioration preventing agent, a retardation (optical anisotropy) developing agent, fine particles, a peeling accelerator, and an infrared ray. An absorbent etc. can be mentioned. In the present invention, a retardation developer may be used. It is also preferable to use at least one of a plasticizer, an ultraviolet absorber and a peeling accelerator.

  They may be solid or oily. That is, the melting point and boiling point are not particularly limited. For example, ultraviolet absorbers of 20 ° C. or lower and 20 ° C. or higher can be mixed and used, and plasticizers can also be mixed and used, for example, as described in JP-A No. 2001-151901.

  As the ultraviolet absorber, any type can be selected according to the purpose, and a salicylic acid ester-based, benzophenone-based, benzotriazole-based, benzoate-based, cyanoacrylate-based, nickel complex-based absorber or the like is used. Preferred are benzophenone series, benzotriazole series, and salicylic acid ester series.

  Examples of benzophenone ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-acetoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-di-hydroxy-4-methoxybenzophenone, 2, 2′-di-hydroxy-4,4′-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4- (2-hydroxy-3- And methacryloxy) propoxybenzophenone.

  As a benzotriazole ultraviolet absorber, 2 (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2 (2′-hydroxy-5′-tert-butylphenyl) ) Benzotriazole, 2 (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) benzotriazole, 2 (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5 And chlorobenzotriazole, 2 (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, and the like.

  Examples of salicylic acid esters include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Among these exemplified ultraviolet absorbers, in particular, 2-hydroxy-4-methoxybenzophenone, 2,2′-di-hydroxy-4,4′-methoxybenzophenone, 2 (2′-hydroxy-3′-tert-butyl- 5'-methylphenyl) -5-chlorobenzotriazole, 2 (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2 (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) ) Benzotriazole, 2 (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole is particularly preferred.

  As the ultraviolet absorber, it is preferable to use a combination of a plurality of absorbers having different absorption wavelengths because a high blocking effect can be obtained in a wide wavelength range. From the viewpoint of preventing deterioration of the liquid crystal, the ultraviolet absorbent for liquid crystal is preferably excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less, and from the viewpoint of liquid crystal display properties, the absorption of visible light having a wavelength of 400 nm or more is small. Particularly preferred ultraviolet absorbers are the benzotriazole compounds, benzophenone compounds, and salicylic acid ester compounds mentioned above. Among these, a benzotriazole-based compound is preferable because unnecessary coloring with respect to the cellulose ester is small.

  As for the UV absorber, JP-A-60-235852, JP-A-3-199201, JP-A-51907073, JP-A-5-194789, JP-A-5-271471, JP-A-6-107854, JP-A-6-107854. 118233, 6-148430, 7-11056, 7-11055, 7-11056, 8-29619, 8-239509, JP-A-2000-204173 These compounds can also be used.

  0.001-5 mass parts is preferable with respect to 100 mass parts of cellulose acylates, and, as for the addition amount of a ultraviolet absorber, 0.01-1 mass part is more preferable. If the addition amount is 0.001 part by mass or more, the effect of addition can be sufficiently exhibited, and if the addition amount is 5 parts by mass or less, the ultraviolet absorber does not bleed out to the film surface, which is preferable.

  Further, the ultraviolet absorber may be added simultaneously with the dissolution of cellulose acylate, or may be added to the dope after dissolution. In particular, a mode in which an ultraviolet absorbent solution is added to the dope immediately before casting using a static mixer or the like is preferable because the spectral absorption characteristics can be easily adjusted.

  The deterioration inhibitor can prevent cellulose triacetate and the like from deteriorating and decomposing. Examples of the deterioration preventing agent include butylamine, hindered amine compounds (JP-A-8-325537), guanidine compounds (JP-A-5-271471), benzotriazole-based UV absorbers (JP-A-6-235819), and benzophenone-based compounds. There are compounds such as UV absorbers (JP-A-6-118233).

  The plasticizer is preferably a phosphate ester or a carboxylic acid ester. The plasticizer is triphenyl phosphate (TPP), tricresyl phosphate (TCP), cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), diphenyl phthalate (DPP), diethyl hexyl phthalate (DEHP), triethyl O-acetylcitrate (OACTE), tributyl O-acetylcitrate (OACTB), Acetyl triethyl acid, acetyl tributyl citrate, butyl oleate, methyl acetyl ricinoleate, dibutyl sebacate, triacetin, tri Chirin, butyl phthalyl butyl glycolate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, and more preferably one selected from butyl phthalyl butyl glycolate. Furthermore, the plasticizer is preferably (di) pentaerythritol esters, glycerol esters, diglycerol esters.

Examples of the peeling accelerator include ethyl esters of citric acid.
Furthermore, infrared absorbers are described, for example, in JP-A No. 2001-194522.

  These additives may be added at any time in the dope preparation process, but may be added to the final preparation process of the dope preparation process by adding the preparation process. 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 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 the like, but these are conventionally known techniques. The glass transition point Tg measured with a dynamic viscoelasticity measuring device for cellulose acylate film (Vibron: DVA-225 (ITG Measurement Control Co., Ltd.)) is determined at 70 to 150 ° C. It is preferable to make it. More preferably, the glass transition point Tg is 80 to 135 ° C. That is, the cellulose acylate film of the present invention preferably has a glass transition point Tg in the above range from the viewpoint of process suitability for polarizing plate processing and liquid crystal display device assembly.

Furthermore, regarding the additive, the Japan Society of Invention and Innovation Technical Bulletin No. 2001-1745 (issued March 15, 2001, Japan Society of Invention) p. Those described in detail after 16 can be used as appropriate.
These additives can be added in an addition amount that does not impair the desired effects of the present invention.

{Retardation expression agent}
In the present invention, a retardation developer may be used in order to develop a preferable retardation value.
Examples of the retardation enhancer that can be used in the present invention include those composed of rod-shaped or discotic compounds.
As the rod-like or discotic compound, a compound having at least two aromatic rings can be used.
The addition amount of the retardation enhancer composed of the rod-shaped compound is preferably 0.1 to 30 parts by mass, and preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymer component containing cellulose acylate. Further preferred.
The disk-shaped retardation developer is preferably used in a range of 0.05 to 20 parts by mass, and in a range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer component containing the cellulose acylate. It is more preferable to use it, it is more preferable to use it in the range of 0.2-5 mass parts, and it is most preferable to use it in the range of 0.5-2 mass parts.
Since the discotic compound is superior to the rod-shaped compound in Rth expression, it is preferably used particularly when a large Rth is required.
Two or more retardation developing agents may be used in combination.
The retardation developer composed of a rod-like or discotic compound preferably has maximum absorption in the wavelength region of 250 to 400 nm, and preferably has substantially no absorption in the visible region.

The discotic compound will be described. As the discotic compound, a compound having at least two aromatic rings can be used.
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, a compound disclosed in JP 2001-166144 A is preferably used as the discotic compound.

The number of aromatic rings contained in the discotic compound is preferably 2 to 20, more preferably 2 to 12, still more preferably 2 to 8, and most preferably 2 to 6. preferable.
The bonding relationship between two aromatic rings can be classified into (a) when a condensed ring is formed, (b) when directly linked by a single bond, and (c) when linked via 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 substituents include halogen atoms (F, Cl, Br, I), hydroxyl groups, carboxyl groups, cyano groups, amino groups, nitro groups, sulfo groups, carbamoyl groups, sulfamoyl groups, ureido groups, alkyl groups, alkenyls. 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 An aliphatic substituted carbamoyl group, an aliphatic substituted sulfamoyl group, an aliphatic substituted ureido group, and a non-aromatic heterocyclic group.

It is preferable that the alkyl group 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 group, carboxy group, 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- A diethylaminoethyl group is included.
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 the alkenyl group include a vinyl group, an allyl group, and a 1-hexenyl group.
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 the alkynyl group include ethynyl group, 1-butynyl group and 1-hexynyl group.

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

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

In the present invention, in addition to the aforementioned discotic compound, a rod-shaped compound having a linear molecular structure can also be preferably used. 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 {for example, WinMOPAC2000, manufactured by Fujitsu Limited} to obtain a 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 specific examples of these discotic compounds and rod-shaped compounds, compounds listed in JP-A Nos. 2004-243628 and 2005-134863 can be used alone or in combination.

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 by a method described in the literature. As literature, Mol. Cryst. Liq. Cryst. 53, 229 pages (1979), 89, 93 pages (1982), 145, 111 pages (1987), 170 pages, 43 pages (1989), J. Am. Am. Chem. Soc. 113, p. 1349 (1991), p. 118, p. 5346 (1996), p. 92, p. 1582 (1970). Org. Chem. 40, 420 pages (1975), Tetrahedron, Vol. 48, No. 16, page 3437 (1992).

{Matte agent fine particles}
The cellulose acylate film of the present invention is preferably formed by adding fine particles as a matting agent as an additive. The fine particles used in the present invention include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, silica Mention may be made of magnesium and calcium phosphates. Fine particles containing silicon are preferable in terms of low turbidity, and silicon dioxide is particularly preferable. The silicon dioxide fine particles preferably have a primary average particle size of 20 nm or less and an apparent specific gravity of 70 g / liter or more. Those having an average primary particle size as small as 5 to 16 nm are more preferred because they can reduce the haze of the film. The apparent specific gravity is preferably 90 to 200 g / liter or more, and more preferably 100 to 200 g / liter or more. A larger apparent specific gravity is preferable because a high-concentration dispersion can be produced, and haze and aggregates are improved.
The amount of silicon dioxide fine particles used is preferably 0.01 to 0.3 parts by mass with respect to 100 parts by mass of the polymer component containing cellulose acylate.

These fine particles usually form secondary particles having an average particle diameter of 0.1 to 3.0 μm, and these fine particles are present as aggregates of primary particles in the film, and 0.1 to 0.1 μm on the film surface. An unevenness of 3.0 μm is formed. The secondary average particle size is preferably from 0.2 μm to 1.5 μm, more preferably from 0.4 μm to 1.2 μm, and most preferably from 0.6 μm to 1.1 μm. When it is larger than 1.5 μm, the haze becomes strong, and when it is smaller than 0.2 μm, the effect of preventing stain is reduced.
The primary and secondary particle diameters are determined by observing the particles in the film with a scanning electron microscope and using the diameter of a circle circumscribing the particles as the particle diameter. Also, 200 particles are observed at different locations, and the average value is taken as the average particle diameter.

  As fine particles of silicon dioxide, for example, commercially available products such as Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.) can be used. Zirconium oxide fine particles are commercially available, for example, under the trade names Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.), and can be used.

  Among these, Aerosil 200V and Aerosil R972V are fine particles of silicon dioxide having a primary average particle diameter of 20 nm or less and an apparent specific gravity of 70 g / liter or more, and the coefficient of friction is maintained while keeping the turbidity of the optical film low. It is particularly preferable because it has a great effect of reducing the effect.

In order to obtain a cellulose acylate film having particles having a small secondary average particle size in the present invention, several methods are conceivable when preparing a fine particle dispersion. For example, a method of preparing a fine particle dispersion in which a solvent and fine particles are mixed with stirring in advance, adding this fine particle dispersion to a small amount of a separately prepared cellulose acylate solution, stirring and dissolving, and further mixing with the main cellulose acylate dope solution There is. This method is a preferred preparation method in that the dispersibility of the silicon dioxide fine particles is good and the silicon dioxide fine particles are more difficult to reaggregate. In addition, after adding a small amount of cellulose ester to the solvent and dissolving with stirring, add the fine particles to this and disperse with a disperser to make this fine particle additive solution, and mix this fine particle additive solution with the dope solution using an in-line mixer. There is also a way to do it. The present invention is not limited to these methods, but the concentration of silicon dioxide when the silicon dioxide fine particles are mixed and dispersed with a solvent or the like is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, and 15 to 20%. Mass% is most preferred. A higher dispersion concentration is preferable because the liquid turbidity with respect to the added amount is lowered, and haze and aggregates are improved. The addition amount of the matting agent in the final cellulose acylate dope solution is preferably 0.01 to 1.0 g, more preferably 0.03 to 0.3 g, and 0.08 to 0.16 g per 1 m ^2. Most preferred.

  The solvent used is preferably lower alcohols such as methanol, ethanol, propanol, isopropanol, butanol and the like. Although it does not specifically limit as solvents other than a lower alcohol, It is preferable to use the solvent used at the time of film formation of a cellulose acylate film.

{Organic solvent}
Next, an organic solvent for dissolving the cellulose acylate when producing the cellulose acylate film of the present invention will be described.
In the present invention, any of a chlorinated solvent containing a chlorinated organic solvent as a main solvent and a non-chlorinated solvent not containing a chlorinated organic solvent can be used as the organic solvent.

(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 kind 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 in the total amount of the organic solvent. Other organic solvents used in combination with the chlorinated organic solvent in the present invention will be described below. That is, as another preferable 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.
Examples of combinations of chlorinated organic solvents and other organic solvents include the following compositions, but are not limited thereto.

Dichloromethane / methanol / ethanol / butanol (80/10/5/5, parts by mass),
Dichloromethane / acetone / methanol / propanol (80/10/5/5, parts by mass),
Dichloromethane / methanol / butanol / cyclohexane (80/10/5/5, 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, part 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).

(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, 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. The ester, ketone and ether 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, the non-chlorine solvent is preferably a mixed solvent containing the non-chlorine organic solvent as a main solvent, and is a mixed solvent of three or more different solvents, wherein the first solvent is methyl acetate, ethyl acetate, At least one selected from methyl formate, ethyl formate, acetone, dioxolane, and dioxane, or a mixture thereof; the second solvent is selected from ketones having 4 to 7 carbon atoms or acetoacetate; The solvent is a mixed solvent selected from alcohols or hydrocarbons having 1 to 10 carbon atoms, more preferably alcohols having 1 to 8 carbon atoms. 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, methyl acetyl acetate, or a mixed solvent thereof. 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 mixing ratio of the above three types of mixed solvents is 20 to 95% by mass for the first solvent, 2 to 60% by mass for the second solvent, and 2 to 30% by mass for the third solvent in the total amount of the mixed solvent. The first solvent is preferably 30 to 90% by mass, the second solvent is 3 to 50% by mass, and the third alcohol is preferably 3 to 25% by mass. . In particular, it is preferable that the first solvent is 30 to 90% by mass, the second solvent is 3 to 30% by mass, and the third solvent is alcohol and 3 to 15% by mass. The non-chlorine-based organic solvent used in the present invention described above is more specifically described in JIII Journal of Technical Disclosure No. 2001-1745 (issued March 15, 2001, Invention Association) p. 12-16. 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, parts 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, part 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, parts by mass)
1,3-dioxolane / cyclohexanone / methyl ethyl ketone / methanol / butanol (55/20/10/5/5, parts by mass).

Further, a cellulose acylate solution prepared by the following method can also be used.
A method of adding a cellulose acylate solution with methyl acetate / acetone / ethanol / butanol (81/8/7/4, parts by mass), adding 2 parts by weight of butanol after filtration and concentration,
A method of adding a cellulose acylate solution with methyl acetate / acetone / ethanol / butanol (84/10/4/2, parts by mass), adding 4 parts by weight of butanol after filtration and concentration,
A method in which a cellulose acylate solution is prepared with methyl acetate / acetone / ethanol (84/10/6, parts by mass), and 5 parts by weight of butanol is added after filtration and concentration.
In addition to the non-chlorine organic solvent of the present invention, the dope used in the present invention may contain dichloromethane in an amount of 10% by mass or less based on the total amount of the organic solvent of the present invention.

{Characteristics of cellulose acylate solution}
The cellulose acylate solution is preferably a solution in which cellulose acylate is dissolved in the organic solvent at a concentration of 10 to 30% by mass from the viewpoint of film forming casting suitability, and more preferably 13 to 27% by mass. It is particularly preferably 15 to 25% by mass. In order to adjust the cellulose acylate to these concentrations, the cellulose acylate may be adjusted to a predetermined concentration at the stage of dissolution, or may be prepared in advance as a low-concentration solution (for example, 9 to 14% by mass) and then concentrated later. You may adjust to a predetermined high concentration solution by a process. Furthermore, after preparing a high concentration cellulose acylate solution in advance, a predetermined low concentration cellulose acylate solution may be obtained by adding various additives, and the cellulose acylate solution concentration of the present invention is obtained by either method. If implemented, there is no particular problem.

Next, in this invention, it is preferable that the aggregate molecular weight of the cellulose acylate in 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 this 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 associated molecular weight, the inertial square radius and the second virial coefficient in the present invention will be described. These are measured using the static light scattering method according to the following method. Although the measurement is 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 is 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 is dried at 120 ° C. for 2 hours, and is measured at 25 ° C. and 10% RH. The dissolution method is 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, the solution and the solvent are filtered through a 0.2 μm Teflon (registered trademark) filter. The filtered solution is 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 is 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 refractive system, and the refractive index gradient (dn / dc) uses the differential refractometer (Otsuka Electronics Co., Ltd. product DRM-1021). Measure using the solvent and solution used for light scattering measurement.

Next, the manufacturing method of the cellulose acylate film of the present invention will be described.
The method for producing a cellulose acylate film of the present invention has a stretching step, and the stretching step is performed by stretching a biaxial stretching ratio orthogonal to each other within a specific range and a stretching temperature as a specific range. The film thickness of the film after the stretching process is in a specific range.
The production method of the present invention can be used in the production of the cellulose acylate film of the present invention, and can also be used in the production of other cellulose acylate films. In the following description, it demonstrates along manufacture of the cellulose acylate film of this invention.
The cellulose acylate film of the present invention is preferably produced by performing each step including the steps of dope adjustment and stretching treatment.

{Preparation of dope}
Preparation of a cellulose acylate solution (dope) will be described. The method for dissolving the cellulose acylate is not particularly limited, and may be room temperature, or a cooling dissolution method or a high-temperature dissolution method, or a combination thereof. Regarding 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-10-45950, JP-A-2000-53784, Kaihei 11-322946, JP-A-11-322947, JP-A-2-276830, JP-A-2000-273239, JP-A-11-71463, JP-A-04-259511, JP-A-2000-273184, JP-A-11-323017, JP-A-11-323017 No. 11-302388 describes a method for preparing a cellulose acylate solution. 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. For details of these, particularly for non-chlorine-based solvent systems, the Japan Society of Invention and Innovation Technical Bulletin No. 2001-1745 (issued March 15, 2001, Invention Association) p. It is carried out in the manner described in detail in 22-25. Furthermore, the cellulose acylate dope solution of the present invention is usually subjected to solution concentration and filtration. Similarly, the Japan Society of Invention and Innovation Technical Bulletin No. 2001-1745 (issued March 15, 2001, Invention Association) p. 25 in detail. 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.

  It is preferable that the cellulose acylate solution has a viscosity and a dynamic storage elastic modulus within the ranges described below because it is easy to cast. 1 mL of the sample solution is measured with a rheometer (CLS 500) using a Steel Cone (both manufactured by TA Instruments) having a diameter of 4 cm / 2 °. Measurement conditions were measured using Oscillation Step / Temperature Ramp with a range of 40 ° C. to −10 ° C. being changed at 2 ° C./min, static non-Newtonian viscosity at 40 ° C. n * (Pa · S) and storage at −5 ° C. The elastic modulus G ′ (Pa) is obtained. The sample solution is preliminarily kept at the measurement start temperature until the liquid temperature becomes constant, and then the measurement is 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, and more preferably the viscosity at 40 ° C. is 10 to 200 Pa · s. And the dynamic storage elastic modulus in 15 degreeC is 100-1 million Pa. Furthermore, it is preferable that the dynamic storage elastic modulus at a low temperature is large. For example, when the metal support of the casting part is −5 ° C., the dynamic storage elastic modulus is −5 ° C. and 10,000 to 1,000,000 Pa. Preferably, when the metal support of the casting part is −50 ° C., the dynamic storage elastic modulus at −50 ° C. is preferably 10,000 to 5 million Pa.

  In the present invention, when the above-described cellulose acylate is used, a high concentration dope can be obtained, so that 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, it is preferable to use a filter having an absolute filtration accuracy of 0.1 to 100 μm, and it is more preferable to use a filter having an absolute filtration accuracy of 0.5 to 25 μm. 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. The temperature at this time is not particularly limited as long as it is a temperature at the time of casting, but is preferably −5 to + 70 ° C., more preferably −5 to + 55 ° C.

{Film formation}
The cellulose acylate film of the present invention can be obtained by forming a film using the cellulose acylate solution. As the film forming method and equipment, 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, and the dope is run endlessly from the die (slit) of the pressure die. 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 cellulose acylate solution (dope) prepared is produced by a solvent casting method, a dope is cast on a drum or a band, and a 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 methods described in JP-A Nos. 55-014201, 02-111511, and 02-208650 can be used 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. A film may also be formed by casting a cellulose acylate solution from two casting ports. For example, Japanese Patent Publication Nos. 60-27562, 61-94724, 61-947245, 61-947245, This 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- and low-viscosity cellulose acylate solutions are simultaneously extruded. A casting method may be used. Furthermore, it is also a preferable aspect 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 prepared, for example, a method described in Japanese Patent Publication No. 44-20235. The cellulose acylate solutions to be cast may be the same solution or different cellulose acylate solutions, and are 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 type 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 to contain a peeling accelerator 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, but 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 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 processes may be the same, or may be different at various points in the process. If they are different, the temperature 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 ° C. lower than the boiling point of the lowest boiling solvent. Is preferred. This is not the case when the casting dope is cooled and peeled off without drying.

{Stretching treatment}
In the stretching step, as described above, the stretching ratios in the biaxial directions perpendicular to each other are set in a specific range, and the stretching temperature is set in a specific range.
The biaxial stretching ratios orthogonal to each other are the MD direction (casting direction) and the TD direction (direction perpendicular to the MD direction).
In the cellulose acylate film of the present invention, the retardation can be adjusted by a stretching treatment. Furthermore, there is also a method of positively stretching in the width direction. -48271, and the like. This stretches the produced film in order to increase the front retardation value of the cellulose acylate film.

  Furthermore, in Japanese Patent Application Laid-Open No. 2003-014933, as a method of stretching, a transverse stretching machine called a tenter that stretches in the lateral direction by fixing both ends of the web with clips and pins and widening the interval between the clips and pins in the lateral direction. It is described that can be preferably used. It is also disclosed that stretching or shrinking in the longitudinal direction can be performed by widening or shrinking the interval in the transport direction of the clip or pin in the transport direction (longitudinal direction) using a simultaneous biaxial stretching machine. . In addition, driving the clip portion by the linear drive method is preferable because it can be smoothly stretched and the risk of breakage can be reduced, and as a method of stretching in the longitudinal direction, a difference in peripheral speed is applied to a plurality of rolls. In the meantime, it is suggested that a method of stretching in the longitudinal direction by utilizing the difference in the circumferential speed of the roll can be used. These stretching methods may be used in combination, and the stretching process may be performed in two or more stages, such as (longitudinal stretching, lateral stretching, longitudinal stretching) or (longitudinal stretching, longitudinal stretching). It is described that it is good.

The temperature of the film stretching treatment is not less than 25 ° C. higher than the glass transition temperature (Tg) of the film and not more than the crystallization temperature. The temperature of the stretching treatment means the surface temperature of the film itself during stretching.
By setting the temperature within this range, the haze can be reduced in the case of a thin film produced by high magnification stretching.

  The draw ratio is 1.2 to 4.0 times and 1.05 to 3.8 times in the biaxial direction MD and TD direction orthogonal to each other. Preferred stretching ratios are 1.2 to 3.0 times and 1.2 to 2.8 times, respectively, and particularly preferably 1.2 to 2.0 times and 1.2 to 1.8 times, respectively. By making the draw ratio within the above specified range, it is possible to realize a thin and high elastic cellulose acylate film, which has excellent front and thickness direction retardation, and can be handled during production and processing. An easy film can be obtained. Furthermore, when the draw ratio is less than 1.2 times or 1.05 times, it becomes difficult to satisfy desired optical characteristics. If it exceeds 4.0 times or 3.8 times, breakage during stretching may occur.

  Further, at least one of the stretching speeds in the biaxial directions perpendicular to each other is preferably 10% / min or less, and more preferably 10 to 3% / min. By setting it within this range, the haze can be reduced even for a thin film produced by high-stretch stretching. Specifically, one of the MD direction and the TD direction needs to have a stretching speed of 10% / min or less. If either one is within the range of the stretching speed, the other stretching speed is There is no particular limitation. More preferably, both of the stretching speeds are within this range.

  The birefringence of the film is preferably such that the refractive index in the width direction is larger than the refractive index in the length direction. Therefore, it is preferable to stretch more in the width direction. In addition, the stretching process may be performed in the middle of the film forming process, or the raw film that has been formed and wound may be stretched. In the former case, the stretching may be performed in a state including the residual solvent amount, and the stretching can be preferably performed at a residual solvent amount of 2 to 30%.

  Control of the surface temperature of the film during drying and stretching is a useful means for obtaining a cellulose acylate film having the desired effects of the present invention. In general, as the cellulose acylate film is dried and the amount of solvent (volatile content) in the film is lowered, the glass transition temperature (Tg) of the film tends to increase. The surface temperature of the film is glass in any one of the initial drying process (time when the volatile content is around 70% (dry mass basis)), the stretching process, and the final drying process (time when the volatile content is approximately 0% by mass). It is effective to set the heating temperature during drying or stretching so as to exceed the transition temperature.

  In particular, it is effective to set the film surface temperature to a specific value in the stretching step. That is, in the stretching step, the surface temperature of the film is set to a temperature that is 25 ° C. higher than the Tg of the film and not higher than the crystallization temperature. It is preferable to control the temperature so as to be higher by 25 ° C. to 200 ° C., more preferably to control the temperature so as to be 40 to 150 ° C. higher than the Tg of the film, and to be 60 ° C. to 100 ° C. higher than the Tg of the film. It is particularly preferable to control the temperature.

  In addition, said glass transition temperature (Tg) is the temperature of the inflection point on the low temperature side of the endothermic (exothermic) curve measured under the following conditions using a differential scanning calorimeter (DSC) from the intersection of the tangent lines of the curve. This is the calculated value. The crystallization temperature (Tc) is a value obtained by reading the temperature at the apex of the exothermic peak appearing on the high temperature side of Tg.

Container Stainless steel sealed container 70μl
Measurement mode Modulated DSC
Scanning temperature range -50 ~ 200 ℃
Temperature rising rate 2 ℃ / min Temperature decreasing rate 20 ℃ / min Temperature rising amplitude ± 1 ℃
Amplitude period 80 seconds

  The film surface temperature is the film surface temperature measured with a non-contact infrared thermometer. In general, the surface temperature of the film tends to be lower than the air supply temperature of the drying zone, and this tendency increases due to the effect of latent heat of vaporization, especially at the time when the volatile matter is high. is important.

  As described above, the thickness of the cellulose acylate film of the present invention is 20 to 70 μm. Also in the case where the cellulose acylate film of the present invention is manufactured in the manufacturing method of the present invention, the film thickness of the cellulose acylate film obtained after the stretching step is 20 to 70 μm. The film thickness is more preferably 30 to 60 μm, and most preferably 30 to 50 μm. When the film thickness is less than 20 μm, even if the elastic modulus is appropriately adjusted within the range specified in the present invention, handling becomes difficult due to problems such as wrinkling at the time of bonding.

  Further, as described above, the elastic modulus of the cellulose acylate film of the present invention is 3.5 to 10 GPa, more preferably 4 to 7 GPa, and most preferably 4 to 6 GPa. When it is less than 3.5 GPa, when it is made into a thin film, slack, wrinkle, or bending occurs when it is processed into a polarizing plate or bonded to a liquid crystal display device. Chips may be generated when a board is punched. By setting the draw ratio within a specific range, it is possible to realize a cellulose acylate film that is thin as described above and that has a specific high elastic modulus as described above.

Further, the haze of the cellulose acylate film of the present invention is preferably 1% or less, and more preferably 0.7% or less.
A haze of 1% or less is preferable because the resolution and contrast of the image do not decrease when the film is used in a liquid crystal display device. The haze is obtained by carrying out biaxial stretching at a glass transition temperature of the cellulose acylate film + 25 ° C. or more and a temperature below the crystallization temperature, or by carrying out biaxial stretching at a stretching speed of 10% / min or less. It can be a range.

  On the other hand, the front retardation Re at a wavelength of 589 nm of the film is preferably in the range of 20 to 80 nm, more preferably in the range of 25 to 75 nm, and still more preferably in the range of 30 to 70 nm. The retardation Rth in the film thickness direction is preferably in the range of 100 to 250 nm, more preferably in the range of 110 to 190 nm, and still more preferably in the range of 120 to 180 nm.

In this specification, Re (λ) and Rth (λ) respectively represent front retardation and retardation in the film thickness direction at wavelength λ. Re (λ) is measured by making light having a wavelength of λ nm incident in the normal direction of the film in KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments). Rth (λ) is Re (λ), with the in-plane slow axis (determined by KOBRA 21ADH or WR) as the tilt axis (rotation axis) (in the absence of the slow axis, any in-plane value) The light is incident at a wavelength of λ nm from the inclined direction in steps of 10 degrees from the normal direction to 50 degrees on one side with respect to the film normal direction of the rotation axis of KOBRA 21ADH or WR calculates based on the measured retardation value, the assumed value of the average refractive index, and the input film thickness value. The retardation value is measured from any two directions with the slow axis as the tilt axis (rotary axis) (in the case where there is no slow axis, the arbitrary direction in the film plane is the rotational axis), Rth can also be calculated from the following formulas (1) and (2) based on the assumed average refractive index and the input film thickness value. Here, as the assumed value of the average refractive index, 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 the main optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), Polystyrene (1.59). By inputting these assumed values of average refractive index and film thickness, KOBRA 21ADH or WR calculates nx, ny, and nz. Nz = (nx−nz) / (nx−ny) is further calculated from the calculated nx, ny, and nz.
Formula (1)

Re (θ) in the equation (1) represents a retardation value in a direction inclined by an angle θ from the normal direction.
Formula (2)
Rth = ((nx + ny) / 2−nz) x d

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 preferably 3 mm to 50 mm, more preferably 5 mm to 30 mm, and the height is preferably 0.5 to 500 μm, more preferably 1 to 200 μm. This may be a single push or a double push.
The variation in the Re value over the entire width is preferably ± 5 nm, and more preferably ± 3 nm. Further, the variation of the Rth value is preferably ± 10 nm, and more preferably ± 5 nm. Moreover, it is preferable that the variation in the Re value and the Rth value in the length direction is also within the range of the variation in the width direction.

<Polarizing plate>
Next, the polarizing plate of the present invention will be described.
The polarizing plate of the present invention uses at least one cellulose acylate film of the present invention as a protective film for the polarizing film.

The polarizing plate is usually composed of a polarizing film and a pair of protective films that sandwich the polarizing films disposed on both sides thereof. In the present invention, the cellulose acylate film of the present invention is used as at least one protective film. The other protective film may be the cellulose acylate film of the present invention or a normal cellulose acetate film.
Examples of the polarizing film include an iodine polarizing film, a dye polarizing film using a dichroic dye, and a polyene polarizing film. The iodine polarizing film and the dye polarizing film 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. For example, there is a method in which the obtained cellulose acylate film is treated with an alkali and bonded to both surfaces of a polarizing film 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 polarizing film 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 polarizing film and protective films for protecting both surfaces of the polarizing film. Further, a protective film may be bonded to one surface of the polarizing plate and a separate film may be 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 adhesive 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 cellulose acylate film of the present invention is preferably bonded to the polarizing film so that the transmission axis of the polarizing film coincides with the slow axis of the cellulose acylate film of the present invention.
In addition, the polarizing plate produced under polarizing plate crossed Nicol, when the orthogonal accuracy between the slow axis of the cellulose acylate film of the present invention and the absorption axis of the polarizing film (axis orthogonal to the transmission axis) is greater than 1 °, Polarization degree performance under a polarizing plate crossed Nicole decreases, light leakage occurs, and when combined with a liquid crystal cell, a sufficient black level and contrast cannot be obtained, so the main refractive index of the cellulose acylate film of the present invention The deviation between the direction of nx and the direction of the transmission axis of the polarizing plate is preferably within 1 °, 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
The single plate transmittance TT, the parallel transmittance PT, and the orthogonal transmittance CT are more preferably 40.5 ≦ TT ≦ 45, 32 ≦ PT ≦ 39.5, and CT ≦ 1.5, respectively, in this order. Preferably, 41.0 ≦ TT ≦ 44.5, 34 ≦ PT ≦ 39.0, and CT ≦ 1.3. The degree of polarization P is preferably 95.0% or more, more preferably 96.0% or more, and further preferably 97.0% or more.

In the polarizing plate of the present invention, T (380), T (410), and T (700) are at least one of the following formulas (e) to (g), where T (λ) is an orthogonal transmittance at a wavelength λ. It is preferable to satisfy one or more.
(E) T (380) ≦ 2.0
(F) T (410) ≦ 1.0
(G) T (700) ≦ 0.5
More preferably, T (380) ≦ 1.95, T (410) ≦ 0.9, T (700) ≦ 0.49, and even more preferably T (380) ≦ 1.90, T (410) ≦ 0. .8, T (700) ≦ 0.48.

The polarizing plate of the present invention has an orthogonal single plate transmittance change ΔCT and a polarization degree change ΔP of at least the following formulas (j) and (k) when left at 60 ° C. and 95% RH for 500 hours. It is preferable to satisfy one or more.
(J) −6.0 ≦ ΔCT ≦ 6.0
(K) -10.0 ≦ ΔP ≦ 0.0
(However, the amount of change indicates the value obtained by subtracting the measured value before the test from the measured value after the test.)
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 an orthogonal single plate transmittance change ΔCT and a polarization degree change ΔP of at least the following formulas (h) and (i) when left at 60 ° C. and 90% RH for 500 hours. It is preferable to satisfy one or more.
(H) −3.0 ≦ ΔCT ≦ 3.0
(I) −5.0 ≦ ΔP ≦ 0.0

In the polarizing plate of the present invention, the amount of change ΔCT and the degree of polarization change ΔP of the orthogonal single plate when left standing at 80 ° C. for 500 hours have at least one of the following formulas (l) and (m): It is preferable to satisfy.
(L) −3.0 ≦ ΔCT ≦ 3.0
(M) −2.0 ≦ ΔP ≦ 0.0

  Single plate transmittance TT, parallel transmittance PT, and 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 the average of 10 measurements for TT, PT, and CT. The value (average value from 400 nm to 700 nm) is used. 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 films are prepared and measured so that the cellulose acylate film of the present invention is sandwiched between the two polarizing films. 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.

{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. As the 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 under a low pressure gas of 10 ^{−3 to} 20 Torr (0.133 Pa to 2.66 kPa), 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. Regarding these, the details are disclosed in the Invention Association Public Technical Bulletin No. 2001-1745 (issued March 15, 2001, Invention Association) p. 30-32. 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 in order to apply the saponification solution to the cellulose acylate film, and the surface of the cellulose acylate film surface is not formed by the saponification solution solvent. It is preferred to select a solvent that remains good. 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.

  In the polarizing plate of the present invention, it is preferable that at least one layer of a hard coat layer, an antiglare layer and an antireflection layer is provided on the surface of the protective film on the other side of the polarizing plate. That is, when the polarizing plate is used for a liquid crystal display device, it is preferable to provide a functional film such as an antireflection layer on the protective film disposed on the side opposite to the liquid crystal cell. It is preferable to provide at least one layer of a glare layer and an antireflection layer. Each layer does not need to be provided as a separate layer. For example, the antiglare layer may be used as an antireflection layer or an antiglare layer by providing the antireflection layer or the hard coat layer with the function.

(Antireflection layer)
In the present invention, at least a light scattering layer and a low refractive index layer are laminated in this order on the protective film, or a medium refractive index layer, a high refractive index layer, and a low refractive index layer are arranged in this order on the protective film. A laminated antireflection layer is preferably used. Preferred examples thereof are described below.

{Antireflection layer with a light scattering layer and a low refractive index layer on the protective film}
A preferred example of an antireflection layer in which a light scattering layer and a low refractive index layer are provided on a protective film will be described.
In the light scattering layer, mat particles are preferably 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, and the low refractive index The refractive index of the layer is preferably in the range of 1.20 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 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. Glare when applying the film of the present invention is reduced, which is preferable.

  The antireflective layer that can be used in the present invention suppresses reflection of external light by setting its optical characteristics to a specular reflectance of 2.5% or less, a transmittance of 90% or more, and a 60 degree gloss of 70% or less. This is preferable because visibility is improved. 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 that can be used in the present invention is preferably 1.20 to 1.49, more preferably 1.30 to 1.44. Furthermore, the low refractive index layer preferably satisfies the following formula (VIII) from the viewpoint of reducing the reflectance.

Formula (VIII)
(Mλ / 4) × 0.7 <n1d1 <(mλ / 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. Λ is a wavelength and is in the range of 500 to 550 nm.

The material for forming the low refractive index layer will be described below.
The low refractive index layer preferably contains a fluorine-containing polymer as a low refractive index binder.
The fluorine-containing 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 polarizing plate 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 sticker or memo, and 500 gf (4. 90 N) or less, more preferably 300 gf (2.94 N) or less, and most preferably 100 gf (0.98 N) or less. Further, the higher the surface hardness measured with a micro hardness tester, 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 advance in the molecule such as glycidyl (meth) acrylate and glycidyl vinyl ether, carboxyl groups, hydroxy groups, amino groups Obtained by polymerization of a monomer having a sulfo group or the like (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid, crotonic acid, etc.) And a structural unit obtained by introducing a crosslinking reactive group such as a (meth) acryloyl group into these structural units by a polymer reaction (for example, it can be introduced by a technique such as allowing acrylic acid chloride 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 including a binder for imparting hard coat properties, matte particles for imparting light diffusibility, and inorganic fillers for increasing the refractive index, preventing crosslinking shrinkage, and increasing the strength as necessary. The In addition, by providing such a light scattering layer, the light scattering layer also functions as an antiglare layer, and the polarizing plate has an antiglare layer.

  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 light 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 or 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.
Therefore, 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 onto a protective film and then ionizing radiation or heat. It can be cured by a polymerization reaction to form a light scattering layer. 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.
Therefore, 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 on a protective film and then cured by ionizing radiation or heat polymerization reaction. Thus, a light scattering layer can be formed.

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 diameter 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, particles of inorganic compounds such as silica particles and TiO ₂ particles; resin particles such as acrylic particles, crosslinked acrylic particles, polystyrene particles, crosslinked 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 mat particles 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 matte 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 matte particles, in order to increase the refractive index of the layer. Thus, it is preferable that an inorganic filler having an average particle diameter 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 difference in refractive index from the mat particles, it is also preferable to use a silicon oxide in order to keep the refractive index of the light scattering layer using the high refractive index mat particles low. The preferred particle size is the same as that of the aforementioned inorganic filler.
Specific examples of the inorganic filler used for the light scattering layer include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO and SiO ₂ . 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%.
Such a filler does not scatter because the particle size is sufficiently smaller than the wavelength of light, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.

  The refractive index of the bulk of the mixture of binder and inorganic filler in the light scattering layer (that is, the portion other than the matting particles in the light scattering layer) is preferably 1.50 to 2.00, more preferably 1.51 to 1. .80. In order to make the refractive index within the above range, the type 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 uneven coating, uneven drying, 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 the light scattering 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.

{Antireflection layer in which a medium refractive index layer, a high refractive index layer, and a low refractive index layer are provided on a protective film}
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 protective film will be described.
The antireflection layer comprising at least a middle refractive index layer, a high refractive index layer, and a low refractive index layer (outermost layer) in order on the protective film is designed to have a refractive index that satisfies the following relationship. .

  Refractive index of high refractive index layer> refractive index of medium refractive index layer> refractive index of protective film> refractive index of low refractive index layer

A hard coat layer may be provided between the protective film and the middle refractive index layer. Furthermore, the constitution may be a medium refractive index hard coat layer, a high refractive index layer and a low refractive index layer.
Examples thereof include antireflection layers described in JP-A-8-122504, JP-A-8-110401, JP-A-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 layer is preferably 5% or less, more preferably 3% or less. Further, 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 layer is composed of a curable film containing at least an inorganic compound fine 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 fine particles, the surface of the particles is treated with a surface treatment agent (for example, silane coupling agents, etc .: JP-A Nos. 11-295503, 11-153703, 2000-9908, Anionic compounds or organometallic coupling agents: JP 2001-310432 A, etc., core-shell structure with high refractive index particles as a core (JP 2001-166104 A, etc.), specific dispersant combination (example) JP-A-11-153703, Patent No. US62010858B1, JP-A-2002-27776069, etc.).

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. Examples thereof include compounds described in JP-A Nos. 2000-47004, 2001-315242, 2001-31871, and 2001-296401.
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 preferably 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 μm, and 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 preferably 1.20 to 1.55. More 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, imparting slipperiness to the surface is effective, and conventionally known thin film layer means such as introduction of silicone or introduction of fluorine can be applied.
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], JP-A 2000-284102, and the like.
The refractive index of the fluorine-containing compound is preferably 1.35 to 1.50. More preferably, it is 1.36-1.47.

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 coating composition for forming the outermost layer containing a polymerization initiator, a sensitizer and the like is applied. The low refractive index layer is preferably formed 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), 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), 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. Low refractive index inorganic compounds, organic fine particles described in paragraphs [0020] to [0038] of JP-A-11-3820, etc.), silane coupling agents, slip agents, surfactants, and the like can be contained.

When the low refractive index layer is positioned 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.

(Hard coat layer)
The hard coat layer is preferably provided on the surface of the protective film in order to impart physical strength to the protective film provided with the antireflection layer. In particular, it is preferably provided between the protective film 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. The curable functional group in the curable compound is preferably a photopolymerizable functional group. Also, hydrolyzable functional group-containing organometallic compounds and organoalkoxysilyl compounds are preferred.
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 hard coat layer can also serve as a high refractive index 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.
The hard coat layer can also serve as an antiglare layer containing particles having an average particle size of 0.2 to 10 μm and imparted with an antiglare function (antiglare 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.

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

(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. Although it is possible to give a volume resistivity of 10 ⁻⁸ (Ωcm ⁻³ ) by using a hygroscopic substance, a water-soluble inorganic salt, a certain surfactant, a cationic polymer, an anionic polymer, colloidal silica or the like, 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 antistatic layer material. Some metal oxides are colored, but if these metal oxides are used as an antistatic layer material, the entire film is colored, which is not preferable. Zn, Ti, AL, In, Si, Mg, Ba, Mo, W or V can be cited as the metal forming the metal oxide without coloring, and at least one selected from these metals is the main component. It is preferable to use a metal oxide. Specific examples include ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ , V ₂ O ₅ , or a composite oxide thereof. In particular, ZnO, TiO ₂ and SnO ₂ are preferable. Further, it may contain different atoms, for example, an additive such as Al or In for ZnO, an addition of Sb, Nb, or a halogen element for SnO ₂ , or Nb or Ta for TiO ₂ 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 ensure conductivity of 10 ⁻⁸ (Ωcm ⁻³ ) or less in volume resistance, the charging The prevention layer only ^needs to have a surface resistance value of approximately 10 ⁻¹⁰ (Ω / □) or less, and more preferably 10 ⁻⁸ (Ω / □). The surface resistance value of the antistatic 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.

<Liquid crystal display device>
The liquid crystal display device of the present invention has a liquid crystal display device (first embodiment) using either the above-described cellulose acylate film of the present invention or the polarizing plate of the present invention, and a pair of polarizing plates above and below the liquid crystal cell. An OCB or VA mode liquid crystal display device (second embodiment) in which at least one of the polarizing plates is the polarizing plate of the present invention, and a pair of polarizing plates above and below the liquid crystal cell. It is the VA mode liquid crystal display device (3rd form) used for the backlight side.
That is, the cellulose acylate film of the present invention can be advantageously used as an optical compensation sheet when used in a liquid crystal display device. Moreover, the polarizing plate using the cellulose acylate film of the present invention is advantageously used in 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, and the cellulose acylate film of the present invention and a polarizing plate using the same can be used for any of them, VA mode or It can be preferably used in the OCB mode.

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 (in Japanese Patent Publication No. 176625), and (2) a liquid crystal cell (SID97, Digest of tech. Papers (Proceedings) 28 (1997) 845 in which the VA mode is converted into a multi-domain (for MVA mode) in order to enlarge the viewing angle. ), (3) A 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 Japan Liquid Crystal Society) (1998)) and (4) SURVAVAL mode liquid crystal cells (announced at LCD International 98).
Examples of the VA mode liquid crystal display device include a liquid crystal cell (VA mode cell) and two polarizing plates arranged 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 cellulose acylate film of the present invention is used as an optical compensation sheet, and one sheet is disposed between the liquid crystal cell and one polarizing plate, or the liquid crystal cell Two sheets are arranged between both polarizing plates.
In another aspect of the transmissive liquid crystal display device of the present invention, the cellulose acylate film of the present invention is used as a protective film for a polarizing plate disposed between the liquid crystal cell and the polarizing film. The cellulose acylate film may be used only for the protective film between the liquid crystal cell and the polarizing film in one polarizing plate, or two sheets of protective film between the liquid crystal cell and the polarizing film in both polarizing plates. You may use said cellulose acylate film for a film | membrane. For the lamination to the liquid crystal cell, the cellulose acylate film of the present invention is preferably on the VA cell side. When the above cellulose acylate film is used only for the protective film between the liquid crystal cell and the polarizing film in one polarizing plate, this is the upper polarizing plate (observer side), the lower polarizing plate (light source side: backlight) Both sides may be functional and there is no functional problem. However, since it is necessary to provide a functional film on the observer side (upper side) when used as an upper polarizing plate, the production yield may decrease, so it is considered that the use of the functional film as a lower polarizing plate is high. It is considered a preferred embodiment.
When a film other than the cellulose acylate film of the present invention is used as the protective film, it may be a normal cellulose acylate film and is preferably thinner than the cellulose acylate film of the present invention. For example, 40-80 μm is preferable, and commercially available KC4UX2M
(40 μm manufactured by Konica Capto Corporation), KC5UX (60 μm manufactured by Konica Corporation), TD80 (80 μm manufactured by Fuji Photo Film Co., Ltd.), etc.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not restrict | limited to the following example.
Hereinafter, Examples 3, 4, and 8 to 10 shall be read as Reference Examples 3, 4, and 8 to 10, respectively.

[Example 1]
(Cellulose acylate)
Cellulose acylate was prepared by adding sulfuric acid as a catalyst to cellulose as a raw material, adding carboxylic anhydride as a raw material for acyl substituents to carry out an acylation reaction, followed by neutralization and saponification aging. .
At this time, by adjusting the amount of catalyst, the type and amount of carboxylic anhydride, the amount of neutralizing agent added, the amount of water added, the reaction temperature and the aging temperature, the type of acyl group, the degree of substitution, the bulk specific gravity, the degree of polymerization Different cellulose acylates were prepared. Further, the low molecular weight component of the cellulose acylate was removed by washing with acetone.

(Dope adjustment and preparation of cellulose acylate film)
Among the cellulose acylates prepared as described above, the substitution degree of acetyl group (A in formula (I)) 2.00, the substitution degree of propionyl group (B in formula (I)) 0.60, viscosity average polymerization Using a cellulose acylate having a degree of 350, 100 parts by weight of cellulose acylate, 5 parts by weight of ethylphthalylethyl glycolate, 3 parts by weight of triphenyl phosphate, 290 parts by weight of methylene chloride, and 60 parts by weight of ethanol are placed in a sealed container. The mixture was gradually warmed up with slow stirring and dissolved up to 80 ° C. over 60 minutes. The inside of the container was 1.5 atm. This dope was added to Azumi Filter Paper No. After filtering using 244, it left still for 24 hours and the bubble in dope was removed.

  Separately, 5 parts by mass of the above cellulose acylate, 5 parts by mass of TINUVIN 109 (manufactured by Ciba Specialty Chemicals), 15 parts by mass of TINUVIN 326 (manufactured by Ciba Specialty Chemicals), AEROSIL A UV absorber solution was prepared by mixing 0.5 parts by mass of R972V (manufactured by Nippon Aerosil Co., Ltd.) with 94 parts by mass of methylene chloride and 8 parts by mass of ethanol, stirring and dissolving. R972V was previously dispersed in ethanol and added.

The ultraviolet absorbent solution was added at a ratio of 6 parts by mass with respect to 100 parts by mass of the dope and sufficiently mixed by a static mixer.
The above-mentioned dope was cast using a glass plate casting apparatus. The film was dried for 6 minutes with warm air at a supply air temperature of 70 ° C., and the film peeled off from the glass plate was fixed to the frame. It dried and manufactured the cellulose acylate film as a precursor of the final product with a film thickness of 100 micrometers. The cellulose acylate film had a glass transition temperature of 140 ° C. and a crystallization temperature of 180 ° C.
This film was gripped on four sides with a biaxial stretching test apparatus (manufactured by Toyo Seiki Seisakusho Co., Ltd.) and subjected to a simultaneous biaxial stretching process under the conditions shown in Table 1. As common conditions, preheating for 3 minutes was performed at the specified supply air temperature in each example before stretching, and after cooling, air cooling was performed for 5 minutes while holding the clip to obtain a cellulose acylate film as a final product. . Table 1 shows the film thickness and elastic modulus of the obtained cellulose acylate film. In addition, MD in a table | surface points out the casting direction at the time of glass plate casting, and TD points out the width direction orthogonal to it.

[Examples 2-7 and Comparative Examples 1-8]
Hereinafter, Examples 2 to 7 and Comparative Examples 1 to 8 were produced in the same manner as Example 1 except that the stretching temperature and the stretching ratio were changed to the values shown in Table 1.
The Re, Rth, elastic modulus, haze, and viewing angle characteristics of the cellulose acylate films obtained in Examples 1 to 7 and Comparative Examples 1 to 8 were examined. The results are shown in Table 1.

[Measurement method]
The measuring method and definition of Re and Rth are as described above.
The haze was measured using a haze meter MODEL 1001DP (manufactured by Nippon Denshoku Industries Co., Ltd.).
As for the elastic modulus, a sample cut in the TD direction was conditioned for 24 hours in an environment of 25 ° C. and 60% RH, and the elastic modulus was measured according to the method described in JIS K7127. Tensilon manufactured by A & D Co., Ltd. was used as the tensile tester.

Viewing angle:
Using the cellulose acylate films of Examples 1 to 7 to Comparative Examples 1 to 8, polarizing plates and liquid crystal display devices were produced and evaluated as follows.

(Saponification treatment of cellulose acylate film)
First, the cellulose acylate films of Examples 1 to 7 to Comparative Examples 1 to 8 were immersed in a 1.3 mol / L sodium hydroxide aqueous solution at 55 ° C. for 2 minutes, and then washed in a water bath at room temperature. The mixture was neutralized with 0.05 mol / L sulfuric acid at 30 ° C., washed again in a water bath at room temperature, and further dried with hot air at 100 ° C. Thus, the surface of the cellulose acylate film was saponified and used for the following polarizing plate sample preparation.
In addition, a commercially available cellulose triacetate film (Fujitac TD80UF, manufactured by Fuji Photo Film Co., Ltd.) was saponified under the same conditions and used for the following polarizing plate sample preparation.

(Preparation of polarizing plate)
A polarizing film was prepared by adsorbing iodine to the stretched polyvinyl alcohol film, and the saponified cellulose acylate film was attached to one side of the polarizing film using a polyvinyl alcohol-based adhesive. The transmission axis of the polarizing film and the slow axis of the cellulose acylate film were arranged in parallel.
Furthermore, the commercially available cellulose triacetate film saponified as described above was attached to the opposite side of the polarizing film using a polyvinyl alcohol-based adhesive. In this way, a polarizing plate was produced.

At this time, the presence or absence of wrinkles when the cellulose acylate films of Examples and Comparative Examples were attached was evaluated.
○ No wrinkles ○ △ Wrinkles occurred on a part of the film during pasting, but it was resolved in the later process. Wrinkles occurred in the area of 1/3 or more of

(Production of liquid crystal cell)
The liquid crystal cell has a cell gap between the substrates of 3.6 μm, and a liquid crystal material having a negative dielectric anisotropy (MLC6608, manufactured by Merck & Co., Inc.) is dropped and sealed between the substrates, and a liquid crystal layer is interposed between the substrates. Formed. 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.

(Production of liquid crystal display device)
A liquid crystal display device as shown in FIG. 1 was produced.
That is, the liquid crystal display device shown in FIG. 1 uses the above-described vertical alignment type liquid crystal cell 31 and has a protective film 33, 35 on both sides of the polarizing film 34 as the upper (observer side) polarizing plate 30. A super high contrast product (HLC2-5618, manufactured by Sanlitz Co., Ltd.) was used as the lower (backlight side) polarizing plate 32, and the polarizing plates 32 produced as described above were used in Examples 1 to 7 to Comparative Examples. The cellulose acylate films 1 to 8 are each prepared by being attached via an adhesive so that the cellulose acylate film 36 is on the liquid crystal cell 31 side. Reference numeral 37 denotes a polarizing film, and reference numeral 38 denotes a commercially available cellulose triacetate film. The crossed Nicols were arranged so that the transmission axis of the polarizing plate on the viewer side was in the vertical direction and the transmission axis of the polarizing plate on the backlight side was in the horizontal direction.

In addition, using a measuring instrument (EZ-Contrast 160D, manufactured by ELDIM), the viewing angle (contrast ratio is 10 or more and black-side gradation inversion is displayed in eight stages from black display (L1) to white display (L8). No polar angle range) was measured and evaluated as follows.
◎ Viewing angle Up / down / left / right polar angle 80 ° or more ○ Viewing angle Up / down / left / right, 3 directions polar angle 80 ° or more △ Viewing angle Up / down / left / right 2 directions polar angle 80 ° or more × Viewing angle Up / down / left / right inside , Polar angle 80 ° or more in 0-1 direction

Further, as the front contrast, the contrast in the front direction in the same measurement (L8 luminance / L1 luminance) was evaluated.
◎ 500 or more ○ 500-300
△ 300-100
× Less than 100

As shown in Table 1, according to the present invention, the film thickness is 20 to 70 μm, and the elastic modulus in at least one direction of the film casting direction or the width direction is 3.5 to 10 GPa. It can be seen that the cellulose acylate films of Examples 1 to 7 are free from wrinkles when a polarizing plate is attached. Although the comparative example 3 does not generate wrinkles, since it is a thick cellulose acylate film, the polarizing plate becomes thick even when the polarizing plate is prepared. From a comparison between Comparative Example 3 and Examples 1 to 7, it can be confirmed that a good viewing angle as a liquid crystal display device can be provided by adjusting Re to a range of 20 to 80 nm and Rth to a range of 100 to 250 nm. It was. Furthermore, from the comparison between Examples 3 and 4 and Examples 1, 2, and 5-7, it was confirmed that when the haze was suppressed to 1% or less, higher front contrast was obtained as a liquid crystal display device.
Further, from Table 1, as a method for producing a thin cellulose acylate film having a high modulus as described above while suppressing haze, the biaxial stretching ratios orthogonal to each other are 1.2 to 4.0, respectively. It was confirmed that it was effective to adjust the temperature of the stretching treatment to the glass transition temperature of the film + 25 ° C. or more and the crystallization temperature or less, and the range of 1.05 to 3.8 times. It was also confirmed that setting at least one stretching speed in biaxial directions perpendicular to each other to 10% / min or less is effective in suppressing haze.

[Examples 8 to 10, Comparative Example 9]
Next, cellulose was obtained in the same manner as in Example 1 except that the substitution degree of the acetyl group (abbreviation Ac), the substitution degree of the propionyl group (abbreviation Pr), and the substitution degree of the butyryl group (abbreviation Bt) were changed to the values shown in Table 2. An acylate film was produced. The cellulose acylate film had a glass transition temperature of 140 ° C. and a crystallization temperature of 180 ° C. The measuring method is also the same as that in the first embodiment.

[Comparative Example 10]
A cellulose acylate film was produced in the same manner as in Comparative Example 9, except that the draw ratios in the TD direction and MD direction were changed to 1.25 times and 1.05 times, respectively. The measuring method is the same as that in Comparative Example 9.

  As shown in Table 2, in the cellulose acylate film of the present invention in which the substitution degree B by the propionyl group, butyryl group, or benzoyl group according to the present invention is larger than 0, the cellulose acylate of the comparative example in which the substitution degree B is 0 It can be seen that the desired Re and Rth values can be secured and a high elastic modulus can be achieved even with a thin film thickness as compared with the rate film. As a result, it was also confirmed that there was no generation of wrinkles when a polarizing plate was attached, and that a good viewing angle as a liquid crystal display device was provided.

30, 32 Polarizing plate 31 Liquid crystal cell 34, 37 Polarizing film 33, 35 Protective film 36 Cellulose acylate film 38 Commercially available cellulose acylate film

Claims (6)

A liquid crystal display device having a polarizing plate having a polarizing film and a pair of protective films sandwiching the polarizing film,
Cellulose acylate in which at least one of the protective films is formed by solution casting with a film thickness of 20 to 70 μm having an elastic modulus of 3.5 to 10 GPa in at least one of the film casting direction and the width direction A film,
The front retardation Re of the cellulose acylate film is in the range of 30 to 70 nm, the retardation Rth in the film thickness direction is in the range of 120 to 180 nm,
A liquid crystal display device having a viewing angle of at least three polar directions of up, down, left, and right, and a polar angle of 80 ° or more, and a contrast in a front direction represented by white display brightness / black display brightness is 300 or more.   The liquid crystal display device according to claim 1, wherein the elastic modulus is 4 to 6 GPa.   The liquid crystal display device according to claim 1, wherein the cellulose acylate film has a haze of 1% or less. The liquid crystal display device according to claim 1, wherein the cellulose acylate film is substantially composed of cellulose acylate satisfying the following formulas (I) and (II).
Formula (I): 2.6 ≦ A + B ≦ 3.0
Formula (II): 0 <B
(In the formulas (I) and (II), A is the degree of substitution of the hydroxyl group in the glucose unit of the cellulose acylate with an acetyl group, and B is the propionyl group or butyryl group of the hydroxyl group in the glucose unit of the cellulose acylate. Or the degree of substitution with a benzoyl group)   The liquid crystal display device according to claim 1, which is an OCB or VA mode liquid crystal display device.   A VA mode liquid crystal display device comprising a liquid crystal cell and a pair of polarizing plates disposed on both sides of the liquid crystal cell, wherein the cellulose acylate film is provided on a backlight side polarizing plate. The liquid crystal display device described.

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