JP2006235483A - Cellulose acylate film, manufacturing method thereof, polarizing plate using the same and liquid crystal display device using the polarizing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cellulose acylate film which has little thickness unevenness and hardly causes front retardation change, to provide a polarizing plate using the cellulose acylate film and to provide a liquid crystal display device which uses such a polarizing plate, causes no display irregularity and is high-quality. <P>SOLUTION: In the cellulose acylate film, an orientation degree P<SB>0</SB>of cellulose acylate molecular chain on the film surface and a mean orientation degree P<SB>t</SB>of cellulose acylate molecular chain over the whole thickness of the film satisfy the following relation; 2≤P<SB>0</SB>/P<SB>t</SB>≤5 (expression 1). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a cellulose acylate film, an elliptically polarizing plate, and a display device.

  In recent years, liquid crystal displays have become larger and have begun to be used in new applications such as televisions, and the demand for improved image quality has further increased. In particular, the viewing angle dependency of contrast and color is a problem peculiar to a liquid crystal display device, and is a high performance for obtaining the necessity for improvement.

  Therefore, new liquid crystal modes such as IPS, VA, and OCB have been proposed in addition to the conventional TN type. However, in any of these liquid crystal modes, it is difficult to obtain sufficient contrast and viewing angle dependency with the liquid crystal cell alone, and it is common to compensate for the birefringence of the liquid crystal cell with some retardation film.

The cellulose acylate film has been conventionally used as a polarizing plate protective film, but in recent years, a method of actively imparting a retardation to the cellulose acylate film and using it as an optical compensation film has been proposed. Patent Document 1 discloses a method of using a tenter-stretched cellulose acylate film as a VA liquid crystal mode retardation film.
JP 2003-170492 A

  However, since these stretched cellulose acylate films have large thickness unevenness that occurs during film formation, liquid crystal display devices that use this as a polarizing plate protective film and / or retardation film cause display unevenness. Therefore, improvement was strongly desired.

  An object of the present invention is to provide a cellulose acylate film and a polarizing plate with little thickness unevenness and small change in frontal retardation. Another object of the present invention is to provide a high-quality liquid crystal display device free from display unevenness.

  As a result of intensive studies, the present inventors have found that the thickness unevenness of the cellulose acylate film is mainly caused by drying on the band, and the thickness unevenness is the elasticity of the film surface in the soft film state after peeling. It has been found that the rate is reduced by making it higher than the elastic modulus inside the film, and that the thickness unevenness is further reduced by drying while balancing the stretching speed in the width direction and the conveying speed. The thickness of the high elastic modulus region on the film surface is preferably in the range of 0.1 μm to 20 μm, and it is preferable that the elastic modulus changes continuously from the film surface toward the inside. Furthermore, as a method of forming a region having a high elastic modulus on the film surface, cellulose acylate is mainly formed on the film surface rather than inside the film by stretching while controlling the I / O ratio of the residual solvent, the residual solvent content, and the stretching speed. The inventors have found that a method of forming a region having a high degree of chain orientation is effective, and have completed the present invention.

That is, the object of the present invention has been achieved by the following constitutions 1) to 8).
1) Cellulose characterized in that the orientation degree P _o of the cellulose acylate molecular chain on the film surface and the average orientation degree P _t of the cellulose acylate molecular chain over the entire thickness of the film satisfy the relationship of the following formula (1): Acylate film.
Formula (1): 2 ≦ P _o / P _t ≦ 5
2) The cellulose acylate film as described in 1) above, wherein Re and Rth at a wavelength of 590 nm satisfy the relationships of the following formulas (2) to (4).
Formula (2): 20 ≦ Re ≦ 200
Formula (3): 70 ≦ Rth ≦ 400
Formula (4): 1 ≦ Rth / Re ≦ 10

3) Step (1) of conveying a cellulose acylate film peeled after casting a cellulose acylate and a dope solution containing an organic solvent on a band or a drum, step (2) of gripping the edge of the width In the production of a cellulose acylate film having the step (3) of stretching in the width direction, the cellulose having a residual solvent content of 1% by mass to 100% by mass and an I / O ratio of the residual solvent of 0.65 to 6 A method for producing a cellulose acylate film, comprising: stretching an acylate film by 1% or more and 100% or less in a film transport direction and / or a direction perpendicular thereto under the condition of the following formula (5).
Formula (5): 1% / min ≦ stretching speed ≦ 50% / min 4) The method for producing a cellulose acylate film according to the above 3), which satisfies the condition of the following formula (6).
Formula (6): 5 ≦ conveying speed / stretching speed ≦ 300

5) The cellulose acylate film according to 1) or 2) produced by the method of 3) or 4).
6) The degree of substitution of cellulose acylate is 2.0 or more and 2.85 or less, and the additive content in the film is 12% by mass or more with respect to cellulose acylate, as described in 1), 2) or 5) above. Cellulose acylate film.

7) In the polarizing plate in which a protective film is bonded to both sides of a polarizer, at least one of the protective films is the cellulose acylate film described in 1), 2), 5) or 5) above. A polarizing plate.
8) The polarizing plate as described in 7) above, which has an optically anisotropic layer on at least one protective film.

9) A liquid crystal display device comprising a liquid crystal cell and two polarizing plates arranged on both sides thereof, at least one of the polarizing plates being the polarizing plate described in 7) or 8) above.

  According to the present invention, there are provided a cellulose acylate film and a polarizing plate with little thickness unevenness and a small change in front retardation, and a liquid crystal display device using the cellulose acylate film and the polarizing plate has no display unevenness and has high quality. It is.

Hereinafter, the present invention will be described in detail.
<Cellulose acylate film>
The cellulose acylate film of the present invention is characterized in that the degree of orientation of the film surface is higher than the degree of orientation inside. The relationship between the orientation degree P _o of the cellulose acylate molecular chain on the film surface and the average orientation degree P _t of the cellulose acylate molecular chain at the entire thickness of the film must satisfy the relationship of the following formula (1). It is preferable to satisfy | fill the relationship of following numerical formula (1-2).
Formula (1): 2 ≦ P _o / P _t ≦ 5
Formula (1-2): 2.5 ≦ P _o / P _t ≦ 4
P _o / P when the value of _t is too small thickness unevenness reduction effect becomes insufficient. Further, curling of the film is increased when the value of P _o / P _t is too large.

Orientation of the film surface (alignment order parameter) P _o is carrying film X-ray using an In-Plain method measurement, 2Shitakai detected by rotating the detector and the sample of X-ray at an angle of 2Shitakai and [Phi / [Phi = It can be calculated from the peak intensity of 6 to 11 ° by the following mathematical formula (7).
Formula (7): P _o = (3 cos ² β−1) / 2
here,

The average orientation degree P _t in the entire film thickness can be determined from the average value of the peak intensity of 2 [Theta] = 6 to 11 ° in the transmission two-dimensional X-ray measured by using the above equation.

  The internal / surface relative relationship of the main chain orientation degree of the cellulose acylate film of the present invention can be adjusted by appropriately controlling the stretching speed and the affinity of the residual solvent for cellulose acylate during stretching. The cellulose acylate film of the present invention will be described in detail below.

[Cellulose acylate]
First, the cellulose acylate used in the present invention will be described.
The degree of substitution of cellulose acylate means the ratio of acylation of three hydroxyl groups present in cellulose structural units (glucose having β1 → 4 glycosidic bonds). The degree of substitution can be calculated by measuring the amount of bound fatty acid per unit weight of cellulose. The measurement method is carried out according to ASTM-D817-91.

  The cellulose acylate used in the present invention is preferably cellulose acetate having an acetylation degree of 2.0 or more and 2.85 or less. The degree of acetylation is more preferably 2.5 or more and 2.83 or less.

Moreover, it is more preferable to use a cellulose acetate having a substitution ratio at the 6-position of 0.31 or more and a total substitution degree of 2.85 or less represented by the following formula (8).
Formula (8): 6-position substitution ratio = 6-position substitution degree / (2-position substitution degree + 3-position substitution degree + 6-position substitution degree)

  Furthermore, another preferable cellulose acylate that can be used in the present invention has an acylation degree of 2.0 or more and 2.85 or less, and has two or more kinds of acyl groups. The acyl group preferably has 2 to 6 carbon atoms, and more preferably an acetyl group, a propionyl group, or a butyryl group. When the cellulose acylate film of the present invention has an acetyl group and other acyl groups, the substitution degree of the acetyl group is preferably less than 2.5, more preferably less than 2.3.

  The cellulose acylate used in the present invention preferably has a weight average polymerization degree of 250 to 800, more preferably 300 to 600. The cellulose acylate used in the present invention preferably has a number average molecular weight (Mn) of 70,000 to 230,000, more preferably 75,000 to 230,000, and most preferably 78,000 to 120,000.

The cellulose acylate used in the present invention can be synthesized using an acid anhydride or acid chloride as an acylating agent. When the acylating agent is an acid anhydride, an organic acid (for example, acetic acid) or methylene chloride is used as a reaction solvent. As the catalyst, a protic catalyst such as sulfuric acid is used. When the acylating agent is an acid chloride, a basic compound is used as a catalyst.

  In the industrially most common synthesis method, cellulose is synthesized from organic acids corresponding to acetyl groups and other acyl groups (acetic acid, propionic acid, butyric acid, etc.) or acid anhydrides thereof (acetic anhydride, propionic anhydride, A cellulose ester is synthesized by esterification with a mixed organic acid component including butyric anhydride. In this method, cellulose such as cotton linter and wood pulp is activated with an organic acid such as acetic acid, and then esterified using a mixture of organic acid components as described above in the presence of a sulfuric acid catalyst. There are many cases to do. The organic acid anhydride component is generally used in an excess amount relative to the amount of hydroxyl groups present in the cellulose. In this esterification treatment, a hydrolysis reaction (depolymerization reaction) of the cellulose main chain β1 → 4 glycoside bond) proceeds in addition to the esterification reaction. When the hydrolysis reaction of the main chain proceeds, the degree of polymerization of the cellulose ester is lowered, and the physical properties of the cellulose ester film to be produced are lowered. Therefore, the reaction conditions such as the reaction temperature are preferably determined in consideration of the degree of polymerization and molecular weight of the resulting cellulose ester.

  In order to obtain a cellulose ester having a high degree of polymerization (high molecular weight), it is important to adjust the maximum temperature in the esterification reaction step to 50 ° C. or lower. The maximum temperature is preferably adjusted to 35 to 50 ° C, more preferably 37 to 47 ° C. A reaction temperature of 35 ° C. or higher is preferable because the esterification reaction proceeds smoothly. A reaction temperature of 50 ° C. or lower is preferred because problems such as a decrease in the degree of polymerization of the cellulose ester do not occur.

  After the esterification reaction, when the reaction is stopped while suppressing a temperature rise, a decrease in the degree of polymerization can be further suppressed, and a cellulose ester having a high degree of polymerization can be synthesized. That is, when a reaction terminator (for example, water, acetic acid, etc.) is added after completion of the reaction, the excess acid anhydride that did not participate in the esterification reaction is hydrolyzed to form the corresponding organic acid as a by-product. This hydrolysis reaction is accompanied by intense heat generation, and the temperature in the reactor rises. If the rate of addition of the reaction terminator is too large, it will generate heat rapidly exceeding the cooling capacity of the reaction apparatus, the hydrolysis reaction of the cellulose main chain will proceed significantly, and the degree of polymerization of the resulting cellulose ester will decrease. is there. In addition, a part of the catalyst is bonded to the cellulose during the esterification reaction, and most of the catalyst is dissociated from the cellulose during the addition of the reaction terminator. However, when the addition rate of the reaction terminator is too high, there is no sufficient reaction time for the catalyst to dissociate, and a part of the catalyst may remain in a state of being bound to cellulose. Cellulose esters in which a strong acid catalyst is partially bonded have very poor stability, and easily decompose by heat during drying of the product and cause a decrease in the degree of polymerization. For these reasons, after the esterification reaction, it is preferable to stop the reaction by adding a reaction terminator over a period of preferably 4 minutes or more, more preferably 4 to 30 minutes. In addition, if the addition time of the reaction terminator is 30 minutes or less, problems such as a decrease in industrial productivity do not occur.

  As the reaction terminator, water or alcohol that decomposes an acid anhydride is generally used. However, in the present invention, a mixture of water and an organic acid is preferably used as a reaction terminator in order not to precipitate triesters having low solubility in various organic solvents. When the esterification reaction is carried out under the above conditions, a high molecular weight cellulose ester having a weight average polymerization degree of 500 or more can be easily synthesized.

  The cellulose acylate film of the present invention is preferably composed of a cellulose acylate in which the polymer component constituting the film substantially has the above definition. Here, “substantially” means 55% by mass or more (preferably 70% by mass or more, more preferably 80% by mass or more) of the polymer component. Cellulose acylate particles are preferably used as a raw material for film production. 90% by mass or more of the particles to be used preferably have a particle size 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.

[Retardation raising agent]
The cellulose acylate film of the present invention preferably contains a retardation increasing agent.
As the retardation increasing agent used in the present invention, a compound represented by the following general formula (1) is particularly preferable. These compounds are described in detail below.
General formula (1):

In the general formula (1), R ^{11 to} R ¹⁷ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or a substituent, and the substituent T described later can be applied to the substituent.

R ¹⁸ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. Group, an aryloxy group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, a cyano group, or a halogen atom, and having a substituent if possible The substituent T described later can be applied as the substituent.

At least one of R ^{11 to} R ¹⁵ represents an electron donating group. One of R ¹¹ , R ¹³ or R ¹⁵ is preferably an electron donating group, and R ¹³ is more preferably an electron donating group.

The electron donating group refers to those having Hammet's σ _p value of 0 or less, “Chem. Rev.”, Vol. 91, p. 165 (1991). Those having a Hammett's σ _p value of 0 or less are preferably applicable, and those having −0.85 to 0 are more preferably used. Examples of such an electron donating group include an alkyl group, an alkoxy group, an amino group, and a hydroxyl group, preferably an alkyl group and an alkoxy group, more preferably an alkoxy group (preferably having a carbon number of 1 to 12). More preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms.

R ¹¹ is preferably a hydrogen atom or an electron donating group, more preferably an alkyl group, an alkoxy group, an amino group, or a hydroxyl group, and still more preferably an alkyl group having 1 to 4 carbon atoms or a carbon number 1 to 12 Particularly preferably an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms). Most preferred is a methoxy group.

R ¹² is preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group or a hydroxyl group, more preferably a hydrogen atom, an alkyl group or an alkoxy group, still more preferably a hydrogen atom or an alkyl group (preferably a carbon number). 1 to 4, more preferably a methyl group), an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to carbon atoms). 4). Particularly preferred are a hydrogen atom, a methyl group and a methoxy group.

R ¹³ is preferably a hydrogen atom or an electron donating group, more preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, or a hydroxyl group, still more preferably an alkyl group or an alkoxy group, particularly preferably. An alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms). Most preferred are n-propoxy group, ethoxy group, and methoxy group

R ¹⁴ is preferably a hydrogen atom or an electron donating group, more preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, or a hydroxyl group, and still more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. , An alkoxy group having 1 to 12 carbon atoms (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms), particularly preferably. Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and most preferably a hydrogen atom, a methyl group, or a methoxy group.

Preferred groups for R ¹⁵ are the same as those listed for R ¹² .
R ¹⁶ , R ¹⁷ , R ¹⁹ and R ²⁰ are preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom, more preferably a hydrogen atom or a halogen atom. More preferably a hydrogen atom.

R ¹⁸ is preferably an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkoxycarbonyl having 2 to 12 carbon atoms. Group, an acylamino group having 2 to 12 carbon atoms, and a cyano group, more preferably an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, and a carbon number An acylamino group having 2 to 12 carbon atoms, and a cyano group, and more preferably an alkynyl group having 2 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, and 2 to 7 carbon atoms. Acylamino group and cyano group, particularly preferably phenylethynyl group, phenyl group, p-cyanophenyl group, p-methoxyphenyl group, benzoylamino group, n-propo group. Aryloxycarbonyl group, an ethoxycarbonyl group, a methoxycarbonyl group, a cyano group.

Of the general formula (1), a compound represented by the following general formula (1-1) is more preferable.
General formula (1-1):

In the general formula (1-1), R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are respectively synonymous with those in the general formula (1). The preferred range is also the same.

In general formula (1-1), R ¹¹¹ represents an alkyl group, may be linear or branched, and may further have a substituent. Preferably it is a C1-C12 alkyl group, More preferably, it is a C1-C8 alkyl group, More preferably, it is a C1-C6 alkyl group, Most preferably, it is a C1-C4 alkyl group (for example, methyl) Group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group and the like).

Of the general formula (1), a compound represented by the following general formula (1-2) is more preferable.
General formula (1-2):

In general formula (1-2), R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁹ and R ²⁰ have the same meanings as those in general formula (1), and the preferred ranges are also the same. It is. R ¹¹¹ has the same meaning as that in formula (1-1), and the preferred range is also the same.

In general formula (1-2), ^R112 is an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and the number of carbon atoms. A 6-12 aryloxy group, a C2-C12 alkoxycarbonyl group, a C2-C12 acylamino group, a carbonyl group, a cyano group, or a halogen atom is represented.

When R ¹¹ , R ¹² , R ¹⁴ , and R ¹⁵ are all hydrogen atoms, R ¹¹² is preferably an alkyl group, an alkynyl group, an aryl group, an alkoxy group, or an aryloxy group, more preferably an aryl group. , An alkoxy group and an aryloxy group, more preferably an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms). And particularly preferably a methoxy group, a methoxy group, an n-propoxy group, an i-propoxy group, or an n-butoxy group.

When at least one of R ¹¹ , R ¹² , R ¹⁴ and R ¹⁵ is a substituent, R ¹¹² is preferably an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or 2 carbon atoms. An alkenyl group having 2 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, and a cyano group, more preferably an alkynyl group having 2 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an alkoxy group having 2 to 6 carbon atoms. A carbonyl group, an acylamino group having 2 to 7 carbon atoms, and a cyano group, particularly preferably a phenylethynyl group, a phenyl group, a p-cyanophenyl group, a p-methoxyphenyl group, a benzoylamino group, an n-propoxycarbonyl group, An ethoxycarbonyl group, a methoxycarbonyl group, and a cyano group;

  Of the general formula (1), a compound represented by the following general formula (1-3) is more preferable. General formula (1-3):

In general formula (1-3), R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹¹¹ and R ¹¹² have the same meanings as those in general formula (1-2), and the preferred ranges are also the same.

Among the compounds represented by the general formula (1), a compound represented by the following general formula (1-4) is particularly preferable.
General formula (1-4):

In General Formula (1-4), R ¹² , R ^14, and R ¹⁵ are synonymous with those in General Formula (1-3), and preferred ranges are also the same. More preferably, any one of R ¹² , R ^14, and R ¹⁵ is a group represented by —OR ¹¹³ , preferably R ¹⁴ , R ¹⁵ is a group represented by —OR ¹¹³ , More preferably, R ¹⁴ is a group represented by —OR ¹¹³ . R ¹²¹ and R ¹²² each independently represents an alkyl group having 1 to 4 carbon atoms. R ¹²³ represents an alkynyl group having 2 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, an acylamino group having 2 to 7 carbon atoms, or a cyano group. R ¹¹³ represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably an ethyl group or a methyl group, and still more preferably a methyl group.

R ¹²¹ is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an ethyl group or a methyl group. R ¹²² is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an ethyl group or a methyl group, and still more preferably a methyl group.
R ¹²³ is preferably a phenylethynyl group, a phenyl group, a p-cyanophenyl group, a p-methoxyphenyl group, a benzoylamino group, an n-propoxycarbonyl group, an ethoxycarbonyl group, a methoxycarbonyl group, or a cyano group.

The aforementioned substituent T will be described below.
Examples of the substituent T include an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as methyl, ethyl, i-propyl, and t-butyl. , N-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms). For example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), an alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, Propargyl, 3-pentynyl, etc.), an aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 6 carbon atoms). 2, for example, phenyl, p-methylphenyl, naphthyl, etc., a substituted or unsubstituted amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms). Yes, for example, amino, methylamino, dimethylamino, diethylamino, dibenzylamino, etc.), an alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, For example, methoxy, ethoxy, butoxy and the like), an aryloxy group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyloxy, 2-naphthyloxy and the like. ), An acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, Acetyl, benzoyl, formyl, pivaloyl, etc.), alkoxycarbonyl groups (preferably having 2-20 carbon atoms, more preferably 2-16 carbon atoms, particularly preferably 2-12 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, etc.) An aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms such as phenyloxycarbonyl), an acyloxy group (preferably having 2 to 2 carbon atoms). 20, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as acetoxy, benzoyloxy and the like, acylamino group (preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, Particularly preferably, it has 2 to 10 carbon atoms, such as acetylamino, benzoylamino, etc. ), An alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino), an aryloxycarbonylamino group (preferably 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino, etc., sulfonylamino group (preferably 1 to 20 carbon atoms, more preferably carbon 1 to 16, particularly preferably 1 to 12 carbon atoms, for example, methanesulfonylamino, benzenesulfonylamino, etc.), sulfamoyl groups (preferably 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, particularly preferably C 0-12, for example, sulfamoyl, methylsulfamoyl, dimethyls Famoyl, phenylsulfamoyl, etc.), carbamoyl groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenyl Carbamoyl etc.), alkylthio groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio, ethylthio, etc.), arylthio groups (preferably having 6 carbon atoms). To 20, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, etc., sulfonyl groups (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably Has 1 to 12 carbon atoms, such as mesyl, tosyl, etc. Has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms. For example, methanesulfinyl, benzenesulfinyl, etc.), ureido group (preferably 1 to 20 carbon atoms, more preferably C1-C16, Most preferably, it is C1-C12, for example, ureido, methylureido, phenylureido etc.), phosphoric acid amide groups (preferably C1-C20, more preferably C1-C16, Particularly preferred are those having 1 to 12 carbon atoms, such as diethyl phosphoric acid amide and phenyl phosphoric acid amide), hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom etc.), cyano group , Sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group ( Preferably it has 1 to 30 carbon atoms, more preferably 1 to 12, and the hetero atom includes, for example, a nitrogen atom, oxygen atom, sulfur atom, specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, piperidyl, morpholino, Benzoxazolyl, benzimidazolyl, benzthiazolyl, etc.), a silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms. Phenylsilyl and the like). These substituents may be further substituted.

  Moreover, when there are two or more substituents, they may be the same or different. If possible, they may be linked together to form a ring.

  Hereinafter, the compound represented by the general formula (1) will be described in detail with specific examples, but the present invention is not limited to the following specific examples.

The compound represented by the general formula (1) used in the present invention can be synthesized by a general ester reaction of a substituted benzoic acid and a phenol derivative, and any reaction may be used as long as it is an ester bond forming reaction. Examples thereof include a method of converting a substituted benzoic acid to an acid halide and then condensing with phenol, and a method of dehydrating condensation of a substituted benzoic acid and a phenol derivative using a condensing agent or a catalyst.
In view of the production process and the like, a method in which the substituted benzoic acid is functionally converted to an acid halide and then condensed with phenol is preferable.

  A hydrocarbon solvent (preferably toluene, xylene, etc.), an ether solvent (preferably dimethyl ether, tetrahydrofuran, dioxane, etc.), a ketone solvent, an ester solvent, acetonitrile, dimethylformamide, dimethylacetamide, etc. may be used as the reaction solvent. it can. These solvents may be used alone or in admixture of several kinds, and the reaction solvent is preferably toluene, acetonitrile, dimethylformamide, or dimethylacetamide.

  The reaction temperature is preferably 0 to 150 ° C, more preferably 0 to 100 ° C, still more preferably 0 to 90 ° C, and particularly preferably 20 ° C to 90 ° C.

  In this reaction, it is preferable not to use a base. When a base is used, either an organic base or an inorganic base may be used, preferably an organic base such as pyridine, tertiary alkylamine (preferably triethylamine, ethyldiisopropyl). Pyramine, etc.).

In the cellulose acylate film of the present invention, a compound represented by the following general formula (2) can also be preferably used as a retardation increasing agent.
Formula ^{(2): Ar 21 -L 21} -X 21 -L 22 -Ar 22
In the formula, Ar ²¹ and Ar ²² represent an aryl group or an aromatic heterocycle. L ²¹ and L ²² are represented by -C (
═O) O— or —C (═O) NR ⁰² — (R ⁰² represents a hydrogen atom or an alkyl group). X ²¹ represents the following general formula (2a) or general formula (2b).

  General formula (2a):

In the general formula (2a), R ^21a , R ^22a , R ^23a , R ^24a , R ^25a , R ^26a , R ^27a and R ^28a represent a hydrogen atom or a substituent.

  General formula (2b):

In the general formula (2b), R ^21b , R ^22b , R ^23b , R ^24b , R ^25b , R ^26b , R ^27b and R ^28b represent a hydrogen atom or a substituent.

In the general formula (2), Ar ²¹ and Ar ²² represent an aryl group or an aromatic heterocycle as described above, preferably an aryl group having 6 to 30 carbon atoms, and may be a single ring, Furthermore, you may form a condensed ring with another ring. Further, if possible, it may have a substituent, and the substituent T can be applied as the substituent.

In the general formula (2), the aryl group represented by Ar ²¹ and Ar ²² is more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms. For example, phenyl, p-methylphenyl, naphthyl, etc. Can be mentioned.
The aromatic heterocycle represented by Ar ²¹ and Ar ²² may be any aromatic heterocycle containing at least one of an oxygen atom, a nitrogen atom or a sulfur atom, preferably an oxygen atom or a nitrogen atom. Alternatively, it is a 5- to 6-membered aromatic heterocycle containing at least one of sulfur atoms. Moreover, you may have a substituent further if possible. Substituent T described later can be applied as the substituent.

Specific examples of the aromatic heterocycle represented by Ar ²¹ and Ar ²² include, for example, furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazoline, Thiazole, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzthiazole, benzotriazole, tetrazain Den, pyrrolotriazole, pyrazolotriazole and the like. Preferred examples of the aromatic heterocycle include benzimidazole, benzoxazole, benzthiazole, and benzotriazole.

In the general formula (2), L ²¹ and L ²² represent —C (═O) O— or —C (═O) NR ⁰² — as described above, and both are similarly preferable. R ⁰² represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably a hydrogen atom. And a methyl group, particularly preferably a hydrogen atom.

In the above general formula (2a), R ^21a , R ^22a , R ^23a , R ^24a , R ^25a , R ^26a , R ^27a and R ^28a each independently represents a hydrogen atom or a substituent, As the group, the above-described substituent T can be applied. R ^21a , R ^22a , R ^23a , R ^24a , R ^25a , R ^26a , R ^27a and R ^28a are preferably a hydrogen atom, an alkyl group, an amino group, an alkoxy group, a hydroxy group or a halogen atom, more preferably Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, or a halogen atom, more preferably a hydrogen atom, a methyl group, a methoxy group, a hydroxy group, a chlorine atom, or fluorine. An atom, particularly preferably a hydrogen atom or a fluorine atom, and most preferably a hydrogen atom.

In the general formula (2b), R ^21b , R ^22b , R ^23b , R ^24b , R ^25b , R ^26b , R ^27b and R ^28b each independently represents a hydrogen atom or a substituent, As the group, the above-described substituent T can be applied. R ^21b , R ^22b , R ^23b , R ^24b , R ^25b , R ^26b , R ^27b and R ^28b are preferably a hydrogen atom, an alkyl group, an amino group, an alkoxy group, a hydroxy group or a halogen atom, more preferably Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, or a halogen atom, more preferably a hydrogen atom, a methyl group, a methoxy group, a hydroxy group, a chlorine atom, or fluorine. An atom, particularly preferably a hydrogen atom or a fluorine atom, and most preferably a hydrogen atom.

Of the compounds of the general formula (2), a compound represented by the general formula (2-2) is preferable.
General formula (2-1):

In the formula, R ²¹¹ , R ²¹² , R ²¹³ , R ²¹⁴ , R ²¹⁵ , R ²¹⁶ , R ²¹⁷ , R ²¹⁸ , R ²¹⁹ and R ²²⁰ each independently represents a hydrogen atom or a substituent. L ²¹ , L ²² and X ²¹ are synonymous with those in the general formula (2), and preferred ranges are also the same.

R ²¹¹ and R ²¹⁶ each independently represent a hydrogen atom or a substituent, preferably an alkyl group, an alkoxy group, an amino group, or a hydroxyl group, more preferably an alkyl group having 1 to 4 carbon atoms or 1 carbon atom. And preferably an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms). And particularly preferred is a methoxy group.

R ²¹² and R ²¹⁷ each independently represent a hydrogen atom or a substituent, preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, or a hydroxyl group, and more preferably a hydrogen atom, an alkyl group, or an alkoxy group. More preferably, a hydrogen atom, an alkyl group (preferably having 1 to 4 carbon atoms, more preferably a methyl group), an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably. It is C1-C6, Most preferably, it is C1-C4. Particularly preferred are a hydrogen atom, a methyl group and a methoxy group.

R ²¹³ and R ²¹⁸ each independently represents a hydrogen atom or a substituent, preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, or a hydroxyl group, more preferably an alkyl group or an alkoxy group, Preferably it is an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms). Most preferred are n-propoxy group, ethoxy group and methoxy group.

R ²¹⁴ and R ²¹⁹ each independently represent a hydrogen atom or a substituent, preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, or a hydroxyl group, more preferably a hydrogen atom or a C 1-4 carbon atom. An alkyl group, an alkoxy group having 1 to 12 carbon atoms (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms); Particularly preferred are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms, and most preferred are a hydrogen atom, a methyl group and a methoxy group.

R ²¹⁵ and R ²²⁰ each independently represents a hydrogen atom or a substituent, preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group or a hydroxyl group, more preferably a hydrogen atom, an alkyl group or an alkoxy group. And more preferably a hydrogen atom, an alkyl group (preferably having a carbon number of 1-4, more preferably a methyl group), an alkoxy group (preferably having a carbon number of 1-12, more preferably having a carbon number of 1-8, further Preferably it is C1-C6, Most preferably, it is C1-C4. Particularly preferred are a hydrogen atom, a methyl group and a methoxy group.

Of the compounds of the general formula (2), more preferred is a compound represented by the general formula (2-2).
General formula (2-2):

In the formula, R ²¹¹ , R ²¹² , R ²¹⁴ , R ²¹⁵ , R ²¹⁶ , R ²¹⁷ , R ²¹⁸ , R ²¹⁹ , R ²²⁰ , L ²¹ , L ²² and X ²¹ are those in the general formula (2-1). The preferred range is also the same.

In the general formula (2-2), R ²²¹ represents an alkyl group having 1 to 12 carbon atoms, and the alkyl group may be linear or branched, and may further have a substituent. Is an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group) Group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group and the like).

Of the compounds of general formula (2), more preferred are compounds represented by general formula (2-3).
General formula (2-3):

In the formula, R ²¹² , R ²¹⁴ , R ²¹⁵ , R ²¹⁶ , R ²¹⁷ , R ²¹⁸ , R ²¹⁹ , R ²²⁰ , R ²²¹ , L ²¹ , L ²² and X ²¹ are those in the general formula (2-2). The preferred range is also the same.

R ²²² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom, a methyl group, or an ethyl group, and still more preferably. Is a hydrogen atom or a methyl group, particularly preferably a methyl group.

Of the compounds represented by the general formula (2), a compound represented by the general formula (2-4) is particularly preferable.
General formula (2-4):

In the formula, R ²¹² , R ²¹⁵ , R ²¹⁶ , R ²¹⁷ , R ²¹⁸ , R ²¹⁹ , R ²²⁰ , R ²²¹ , R ²²² , L ²¹ , L ²² and X ²¹ are those in the above general formula (2-3). The preferred range is also the same.

R ²²³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.

  Hereinafter, the compound represented by the general formula (2) will be described in detail with specific examples, but the present invention is not limited to the following specific examples.

The compounds represented by the general formulas (1) to (1-4) can be synthesized by a general esterification reaction or amidation reaction of a substituted benzoic acid and phenol or an aniline derivative, and can be an ester bond forming reaction. Any reaction may be used. For example, a method in which a substituted benzoic acid is functionally converted to an acid halide and then condensed with a phenol or aniline derivative, or a method in which a substituted benzoic acid is condensed with a phenol or aniline derivative using a condensing agent or a catalyst, etc. It is done.
Considering the production process and the like, a method in which a substituted benzoic acid is functionally converted to an acid halide and then condensed with phenol or an aniline derivative is preferable.

  Reaction solvents include hydrocarbon solvents (preferably toluene, xylene, etc.), ether solvents (preferably dimethyl ether, tetrahydrofuran, dioxane, etc.), ketone solvents, ester solvents, acetonitrile, dimethylformamide, dimethylacetamide, etc. Can be used. These solvents may be used alone or in admixture of several kinds, and the reaction solvent is preferably toluene, acetonitrile, dimethylformamide, or dimethylacetamide.

  The reaction temperature is preferably 0 to 150 ° C, more preferably 0 to 100 ° C, still more preferably 0 to 90 ° C, and particularly preferably 20 ° C to 90 ° C.

  In this reaction, it is preferable not to use a base. However, when a base is used, either an organic base or an inorganic base may be used, preferably an organic base, such as pyridine, tertiary alkylamine (preferably triethylamine, ethyldiiso). Such as purpylamine).

Moreover, the compounds represented by the general formulas (3), (3-1) and (3-2) can also be preferably used as the retardation increasing agent in the present invention.
General formula (3):

  Formula (3-1)

In the general formula (3), R ³¹ , R ³² and R ³³ each independently represents an aromatic ring or a heterocyclic ring which may have a substituent, and each represents a different aromatic ring or heterocyclic ring. R ³¹ and R ³³ may be the same, and represents an aromatic ring or a heterocyclic ring having a substituent at the ortho position, meta position and / or para position, and R ³² is an aromatic ring having a substituent. Or you may represent a heterocyclic ring. However, when R ³¹ and R ³³ represent an aromatic ring having a substituent at the ortho-position, meta-position and / or para-position, and R ³² represents an aromatic ring having a substituent, R ³¹ and R ³³ and R ³² is never the same.

  The “different aromatic ring or heterocycle” means that the aromatic ring and the heterocycle including the substituent are not the same. For example, even if they are the same aromatic ring or heterocyclic ring, when the substituents are different, and when the substituents are the same even if they are the same, they are included in “different aromatic rings or heterocyclic rings”. Further, “not identical” means that they are not identical including a substituent, for example, when the substituent is different even in the same aromatic ring, and when the substitution position is different even if the substituent is identical. Is included when “not identical”.

X ³¹ represents a single bond or —NR ³³ —, X ³² represents a single bond or —NR ³⁴ —, and X ³³ represents a single bond or —NR ³⁵ —. R ³³ , R ³⁴ and R ³⁵ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group, aryl group or heterocyclic group.

More specifically, the aromatic ring represented by each of R ^{31 to} R ³³ is preferably phenyl or naphthyl, and particularly preferably phenyl. The aromatic ring represented by R ³¹ and R ³³ preferably has a substituent at least in the ortho-position, meta-position and / or para-position, and may have a substituent in other positions. Good. The aromatic ring represented by R ³² preferably has at least one substituent at any substitution position. Examples of the substituent include a halogen atom, hydroxyl, cyano, nitro, carboxyl, alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, acyloxy group, alkoxycarbonyl group, alkenyloxycarbonyl group , Aryloxycarbonyl group, sulfamoyl group, alkyl-substituted sulfamoyl group, alkenyl-substituted sulfamoyl group, aryl-substituted sulfamoyl group, sulfonamide group, carbamoyl, alkyl-substituted carbamoyl group, alkenyl-substituted carbamoyl group, aryl-substituted carbamoyl group, amide group, alkylthio group , An alkenylthio group, an arylthio group, and an acyl group.

The heterocyclic group represented by each of R ^{31 to} R ³³ preferably has aromaticity. The heterocycle having aromaticity is generally an unsaturated heterocycle, preferably a heterocycle having the largest number of double bonds. The heterocyclic ring is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and most preferably a 6-membered ring. The hetero atom of the heterocyclic ring is preferably a nitrogen atom, a sulfur atom or an oxygen atom, and particularly preferably a nitrogen atom. As the heterocyclic ring having aromaticity, a pyridine ring (2-pyridyl or 4-pyridyl as the heterocyclic group) is particularly preferable. The heterocyclic group may have a substituent. Examples of the substituent of the heterocyclic group are the same as the examples of the substituent of the aryl moiety.

When X ³¹ , X ³² and X ³³ are each a single bond, the heterocyclic group is preferably a heterocyclic group having a free valence on the nitrogen atom. The heterocyclic group having a free valence on the nitrogen atom is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and a 5-membered ring. Is most preferred. The heterocyclic group may have a plurality of nitrogen atoms. Further, the heterocyclic group may have a hetero atom other than a nitrogen atom (for example, an oxygen atom or a sulfur atom). Examples of heterocyclic groups having free valences on nitrogen atoms are shown below.

In the general formula (3), as described above, X ³¹ represents a single bond or —NR ³³ —, X ³² represents a single bond or —NR ³⁴ —, and X ³³ represents a single bond or —NR ³⁵ —. R ³³ , R ³⁴ and R ³⁵ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group, aryl group or heterocyclic group. The alkyl group represented by each of R ³³ , R ³⁴ and R ³⁵ may be a cyclic alkyl group or a chain alkyl group, preferably a chain alkyl group, and a branched chain alkyl group. It is more preferable to represent a linear alkyl group. The number of carbon atoms of the alkyl group is preferably 1-30, more preferably 1-20, further preferably 1-10, still more preferably 1-8, and 1-6. Most preferred. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group (for example, methoxy, ethoxy) and an acyloxy group (for example, acryloyloxy, methacryloyloxy).

The alkenyl group represented by each of R ³³ , R ³⁴ and R ³⁵ may be a cyclic alkenyl group or a chain alkenyl group, but preferably represents a chain alkenyl group, and has a branched chain alkenyl group. It is more preferable to represent a linear alkenyl group. The number of carbon atoms in the alkenyl group is preferably 2 to 30, more preferably 2 to 20, still more preferably 2 to 10, still more preferably 2 to 8, 6 is most preferred. The alkenyl group may have a substituent. Examples of the substituent are the same as those of the alkyl group described above.

The aromatic ring group and heterocyclic group represented by R ³³ , R ³⁴ and R ³⁵ are the same as the aromatic ring and heterocyclic ring represented by R ³¹ and R ³² , respectively, and the preferred ranges are also the same. The aromatic ring group and the heterocyclic group may further have a substituent, and examples of the substituent are the same as those of the aromatic ring and heterocyclic ring of R ³¹ and R ³² .

Next, the compound of the general formula (3-1) will be described in detail.
In General Formula (3-1), R ³¹² represents an aromatic ring or a heterocyclic ring having a substituent at the ortho position and / or the meta position. The aromatic ring and heterocyclic R ³¹² is represented by the general formula (3) R ³¹ and R ³² in is the same meaning as the aromatic ring and heterocyclic ring represented respectively, the preferred range is also the same. In addition, examples of the substituent include those exemplified as the substituents having the aromatic ring and the heterocyclic ring represented by R ³¹ and R ³² , respectively. The aromatic ring represented by R ³¹² has at least a substituent at the ortho position and / or the meta position, and may have a substituent at other positions.

X ³¹¹ represents a single bond or —NR ³¹³ —, X ³¹² represents a single bond or —NR ³¹⁴ —, and X ³¹³ represents a single bond or —NR ³¹⁵ —. R ³¹³ , R ³¹⁴ and R ³¹⁵ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group, aryl group or heterocyclic group. With respect to the substituted or unsubstituted alkyl group, alkenyl group, aryl group or heterocyclic group represented by R ³¹³ , R ³¹⁴ and R ³¹⁵ , R ³³ , R ³⁴ and R ^{35 in the} general formula (3) are respectively It is synonymous with each group to represent, and its preferable range is also the same.

  Specific examples of compounds having a 1,3,5-triazine ring, which are compounds represented by the general formulas (3) and (3-1), are shown below as retardation increasing agents preferably used in the present invention. However, the present invention is not limited by the following specific examples.

The molecular weight of the retardation increasing agent used in the present invention is preferably 200 or more and 1,000 or less, and more preferably 300 or more and 850 or less. If it is this range, the solubility to a solvent and the retentivity at the time of film forming can be made compatible.
The boiling point of the retardation increasing agent is preferably 260 ° C. or higher. The boiling point can be measured using a commercially available measuring device such as “TG / DTA100” {manufactured by Seiko Electronics Co., Ltd.}.

  The retardation increasing agent in the present invention can be used alone or in combination of two or more. The addition amount of the retardation increasing agent is preferably 2 to 30 parts by mass, more preferably 3 to 25 parts by mass with respect to 100 parts by mass of the cellulose acylate. By using the compound in this range, the retardation can be increased without causing bleed out.

  In the present invention, the retardation increasing agent may be added to the cellulose acylate solution (dope) after being dissolved in an organic solvent such as alcohol, methylene chloride or dioxolane, or may be added directly to the dope composition. .

[Manufacture of cellulose acylate film]
In the method for producing a cellulose acylate film of the present invention, a cellulose acylate and a dope solution containing an organic solvent are cast on a band or a drum, and then the peeled cellulose acylate film is conveyed (1), width. In the production of a cellulose acylate film having the step (2) of gripping the edge of the hand and the step (3) of stretching in the width direction, the residual solvent content is 1% by mass to 100% by mass, and the residual solvent I / O A cellulose acylate film having a ratio of 0.65 or more and 6 or less is stretched under the condition of the following mathematical formula (5).
Formula (5): 1% / min ≦ stretching speed ≦ 50% / min Hereinafter, the production method of the present invention will be described in detail.
The cellulose acylate film of the present invention is produced by a solvent cast method. In the solvent cast method, a film is produced using a solution (dope) in which cellulose acylate is dissolved in an organic solvent.

The organic solvent is a solvent selected from ethers having 3 to 12 carbon atoms, ketones having 3 to 12 carbon atoms, esters having 3 to 12 carbon atoms, and halogenated hydrocarbons having 1 to 6 carbon atoms. It is preferable to contain.
The ether, ketone and ester may have a cyclic structure. A compound having two or more functional groups of ether, ketone, and ester (that is, —O—, —CO—, and —COO—) can also be used as the organic solvent. The organic solvent may have another functional group such as an alcoholic hydroxyl group. In the case of an organic solvent having two or more types of functional groups, the number of carbon atoms is preferably within the above-described preferable number of carbon atoms range of the solvent having any functional group.

Examples of the ether having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, anisole and phenetole.
Examples of ketones having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexanone.
Examples of the esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate.

Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol.
The number of carbon atoms of the halogenated hydrocarbon is preferably 1 or 2, and most preferably 1. The halogen of the halogenated hydrocarbon is preferably chlorine. The proportion of halogen atoms substituted by halogen in the halogenated hydrocarbon is preferably 25 to 75 mol%, more preferably 30 to 70 mol%, and more preferably 35 to 65 mol%. More preferably, it is most preferable that it is 40-60 mol%. Methylene chloride is a representative halogenated hydrocarbon.

  In the present invention, the organic solvent is preferably used by mixing methylene chloride and alcohol, and the ratio of alcohol to methylene chloride is preferably 1% by mass to 50% by mass, preferably 10% by mass to 40% by mass, and 12% by mass. % To 30% by mass is most preferable. As the alcohol, methanol, ethanol, and n-butanol are preferable, and two or more kinds of alcohols may be mixed and used.

  A cellulose acylate solution can be prepared by a general method comprising treatment at a temperature of 0 ° C. or higher (ordinary temperature or high temperature). The solution can be prepared by using a dope preparation method and apparatus in a normal solvent cast method. In the case of a general method, it is preferable to use a halogenated hydrocarbon (particularly methylene chloride) as the organic solvent.

  The amount of cellulose acylate is adjusted so as to be contained in the obtained solution in an amount of 10 to 40% by mass. The amount of cellulose acylate is more preferably 10 to 30% by mass. Arbitrary additives described later may be added to the organic solvent (main solvent).

The cellulose acylate solution can be prepared by stirring cellulose acylate and an organic solvent at room temperature (0 to 40 ° C.). The high concentration solution may be stirred under pressure and heating conditions. Specifically, cellulose acylate and an organic solvent are placed in a pressure vessel and sealed, and stirred while heating to a temperature not lower than the boiling point of the solvent at normal temperature and in a range where the solvent does not boil.
The heating temperature is usually 40 ° C. or higher, preferably 60 to 200 ° C., and more preferably 80 to 110 ° C.

  Each component may be coarsely mixed in advance and then placed in a container. Moreover, you may put into a container sequentially. The container needs to be configured so that it can be stirred. The container can be pressurized by injecting an inert gas such as nitrogen gas. Moreover, you may utilize the raise of the vapor pressure of the solvent by heating. Or after sealing a container, you may add each component under pressure.

  When heating, it is preferable to heat from the outside of the container. For example, a jacket type heating device can be used. The entire container can also be heated by providing a plate heater outside the container and piping to circulate the liquid.

  It is preferable to provide a stirring blade inside the container and stir using this. The stirring blade preferably has a length that reaches the vicinity of the wall of the container. A scraping blade is preferably provided at the end of the stirring blade in order to renew the liquid film on the vessel wall.

  Instruments such as a pressure gauge and a thermometer may be installed in the container. Each component is dissolved in a solvent in a container. The prepared dope is taken out of the container after cooling, or is taken out and then cooled using a heat exchanger or the like.

  A solution can also be prepared by a cooling dissolution method. In the cooling dissolution method, cellulose acylate can be dissolved in an organic solvent that is difficult to dissolve by a normal dissolution method. In addition, even if it is a solvent which can melt | dissolve a cellulose acylate with a normal melt | dissolution method, there exists an effect that a uniform solution can be obtained rapidly according to a cooling melt | dissolution method.

  In the cooling dissolution method, first, cellulose acylate is gradually added to an organic solvent at room temperature while stirring. The amount of cellulose acylate is preferably adjusted so as to be contained in the mixture in an amount of 10 to 40% by mass. The amount of cellulose acylate is more preferably 10 to 30% by mass. Furthermore, you may add the arbitrary additive mentioned later in a mixture.

  The mixture is then cooled to -100 to -10 ° C (preferably -80 to -10 ° C, more preferably -50 to -20 ° C, most preferably -50 to -30 ° C). The cooling can be performed, for example, in a dry ice / methanol bath (−75 ° C.) or a cooled diethylene glycol solution (−30 to −20 ° C.). The mixture of the cellulose acylate and the organic solvent is solidified by cooling.

  The cooling rate is preferably 4 ° C./min or more, more preferably 8 ° C./min or more, and most preferably 12 ° C./min or more. The faster the cooling rate, the better. However, 10,000 ° C./second is the theoretical upper limit, 1000 ° C./second is the technical upper limit, and 100 ° C./second is the practical upper limit. The cooling rate is a value obtained by dividing the difference between the temperature at the start of cooling and the final cooling temperature by the time from the start of cooling to the final cooling temperature.

  Furthermore, when this is heated to 0 to 200 ° C. (preferably 0 to 150 ° C., more preferably 0 to 120 ° C., most preferably 0 to 50 ° C.), cellulose acylate dissolves in the organic solvent. The temperature may be increased by simply leaving it at room temperature or in a warm bath.

  The heating rate is preferably 4 ° C./min or more, more preferably 8 ° C./min or more, and most preferably 12 ° C./min or more. The higher the heating rate, the better. However, 10,000 ° C./second is the theoretical upper limit, 1000 ° C./second is the technical upper limit, and 100 ° C./second is the practical upper limit. The heating rate is the value obtained by dividing the difference between the temperature at the start of heating and the final heating temperature by the time from the start of heating until the final heating temperature is reached. is there.

  A uniform solution is obtained as described above. If the dissolution is insufficient, the cooling and heating operations may be repeated. Whether or not the dissolution is sufficient can be determined by merely observing the appearance of the solution with the naked eye.

In the cooling dissolution method, it is desirable to use a sealed container in order to avoid moisture mixing due to condensation during cooling. In the cooling and heating operation, when the pressure is applied during cooling and the pressure is reduced during heating,
Dissolution time can be shortened. In order to perform pressurization and decompression, it is desirable to use a pressure-resistant container.

  For example, a 20% by mass solution of cellulose acetate (acetylation degree: 60.9%, viscosity average polymerization degree: 299) dissolved in methyl acetate by the cooling dissolution method is measured with a differential scanning calorimeter (DSC). According to this, there exists a quasi-phase transition point between a sol state and a gel state in the vicinity of 33 ° C., and a uniform gel state is obtained below this temperature. Therefore, it is necessary to keep this solution at a temperature equal to or higher than the pseudo phase transition temperature, preferably about 10 ° C. plus the gel phase transition temperature. However, this pseudo phase transition temperature varies depending on the degree of acetylation of cellulose acetate, the degree of viscosity average polymerization, the concentration of the solution, and the organic solvent used.

  A cellulose acylate film is produced from the prepared cellulose acylate solution (dope) by a solvent cast method. It is preferable to add a retardation increasing agent to the dope.

  The dope is cast on a drum or band and the solvent is evaporated to form a film. The concentration of the dope before casting is preferably adjusted so that the solid content is 18 to 35%. 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 10 ° C. or less.

  Regarding the drying method in the solvent casting method, U.S. Pat. Each specification, British Patent Nos. 640731 and 736892, and Japanese Patent Publication Nos. 45-4554, 49-5614, JP-A-60-176634, 60-203430, and 62- There is a description in each publication of No. 115035. Drying on the band or drum can be performed by blowing an inert gas such as air or nitrogen.

The obtained cellulose acylate film is preferably peeled off from the drum or band, conveyed to a tenter, and then stretched by gripping the end in the width direction. The residual solvent content at the time of stripping is preferably 20% to 150%, more preferably 30% to 100%. After stripping off, it can be further dried with hot air or the like before the tenter process.
Further, the residual solvent can be evaporated by drying with high-temperature air whose temperature is successively changed from 100 ° C. to 160 ° C. The above method is described in Japanese Patent Publication No. 5-17844. According to this method, it is possible to shorten the time from casting to stripping. In order to carry out this method, it is necessary for the dope to gel at the surface temperature of the drum or band during casting.

  A film can also be formed by casting two or more layers using the adjusted cellulose acylate solution (dope). In this case, it is preferable to produce a cellulose acylate film by a solvent cast method. The dope is cast on a drum or band and the solvent is evaporated to form a film. It is preferable to adjust the concentration of the dope before casting so that the solid content is in the range of 10 to 40%. The surface of the drum or band is preferably finished in a mirror state.

When casting a plurality of cellulose acylate solutions of two or more layers, it is possible to cast a plurality of cellulose acylate solutions, from a plurality of casting openings provided at intervals in the direction of travel of the support. You may produce a film, casting and laminating the solution containing a cellulose acylate, respectively. For example, the methods described in JP-A-61-158414, JP-A-1-122419, and JP-A-11-198285 can be used. It can also be formed into a film by casting a cellulose acylate solution from two casting ports. For example, JP-B-60-27562, JP-A-61-94724, JP-A-61-947245, JP-A-61-104413, JP-A-61-158413, and JP-A-6-134933. The method described in the publication can be used. Further, a cellulose acylate film described in JP-A-56-162617 is a cellulose acylate film in which a flow of a high-viscosity cellulose acylate solution is wrapped with a low-viscosity cellulose acylate solution and the high-low viscosity cellulose acylate solution is simultaneously extruded. A casting method can also be used.

  In addition, after peeling off the film formed on the support by the first casting port using the two casting ports, the second casting is performed on the side of the film that is in contact with the support surface. Thus, a film can also be produced. For example, the method described in Japanese Patent Publication No. 44-20235 can be mentioned.

  As the cellulose acylate solution to be cast, the same solution may be used, or different cellulose acylate solutions may be used. 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 used in the present invention can be cast simultaneously with other functional layers (for example, an adhesive layer, a dye layer, an antistatic layer, an antihalation layer, an ultraviolet absorbing layer, a polarizing layer, etc.).

  In the conventional single-layer solution, it is necessary to extrude a cellulose acylate solution having a high concentration and a high viscosity in order to obtain a necessary film thickness. In such a case, the stability of the cellulose acylate solution is poor and solid matter is generated, which often causes problems due to defects or poor flatness. As a solution to this problem, by casting a plurality of cellulose acylate solutions from the casting port, it is possible to extrude a highly viscous solution onto the support at the same time, improving the flatness and improving the planar film. Not only can be produced, but also the use of a concentrated cellulose acylate solution can reduce the drying load and increase the production speed of the film.

[Stretching treatment]
In the method for producing a cellulose acylate film of the present invention, the cellulose acylate film is stretched. By stretching, it is possible to impart a desired retardation to the cellulose acylate film, and it is possible to eliminate thickness unevenness that occurs during drying on the band. In the production method of the present invention, the stretching direction of the cellulose acylate film is the width direction.

  Methods for stretching in the width direction are described in, for example, JP-A-62-115035, JP-A-4-152125, JP-A-2842211, JP-A-298310, and JP-A-11-48271. Yes. The film is stretched at room temperature or under heating conditions. The heating temperature is preferably in the range of the glass transition temperature of the film ± 30 ° C. In the case of stretching in the width direction, the film can also be stretched by conveying while holding the width of the film with a tenter and gradually widening the width of the tenter. After the film is dried, it can be stretched using a stretching machine (preferably uniaxial stretching using a long stretching machine).

The cellulose acylate film of the present invention is preferably stretched at a constant stretching speed in a state containing a certain residual solvent. The residual solvent content at the start of stretching is 1% by mass to 100% by mass, preferably 5% by mass to 100% by mass, and more preferably 10% by mass to 50% by mass. The residual solvent content at the end of stretching is preferably from 0.1% by weight to 50% by weight, and more preferably from 1% by weight to 30% by weight.
By starting stretching in the above range, the amount of residual solvent at the time of stretching becomes film surface> inside the film, and further, Tg on the film surface> Tg inside the film, and the film surface has cellulose molecular chains rather than the inside of the film. Can be easily oriented.

Moreover, it is preferable that the residual solvent at the time of extending | stretching of the cellulose acylate film of this invention is the range of a fixed I / O ratio. The I / O ratio of the residual solvent is preferably 0.65 or more and 6 or less, and more preferably 0.75 or more and 5 or less. The I / O ratio can be calculated by the calculation method described in Sankyo Publishing, Yoshio Koda, organic conceptual diagram.
By extending | stretching in the said range, the Tg difference of the said film surface and an inside can be further amplified.

In the present invention, the I / O ratio of the mixed solvent containing M mass% of solvent A and (100-M) mass% of solvent B is Ra / I ratio of solvent A. Where Rb is calculated by the following mathematical formula (9).
Formula (9): Ra * M / 100 + Rb * (100-M) / 100

Moreover, in the manufacturing method of the cellulose acylate film of this invention, extending | stretching on the conditions of following numerical formula (5) is preferable, and extending | stretching on the conditions of following numerical formula (5-1) is further more preferable.
Formula (5): 1% / min ≦ stretching speed ≦ 50% / min Formula (5-1): 5% / min ≦ stretching speed ≦ 40% / min By setting the stretching speed within the above range, The difference in elastic modulus on the surface can be effectively used, and the effect of uniformizing the film thickness by stretching can be maximized.
By setting the stretching speed, residual solvent content, and residual solvent I / O ratio within the above ranges, it is possible to form a region with a higher degree of orientation of the main chain of cellulose acylate on the surface of the film than inside the film. It becomes.

Furthermore, the stretching speed and the film transport speed preferably satisfy the relationship represented by the following mathematical formula (6), and more preferably satisfy the relationship represented by the following mathematical formula (6-1).
Formula (6): 5 ≦ conveying speed / stretching speed ≦ 300
Formula (6-1): 10 ≦ conveying speed / stretching speed ≦ 200
When the stretching speed and the transport speed of the film satisfy the above ranges, it is possible to increase the effect of eliminating the thickness unevenness generated on the band. Thereby, the orientation degree difference between the surface and the inside of the film can be sufficiently generated, and the effect of eliminating thickness unevenness can be sufficiently exhibited.

  The atmospheric temperature during stretching is preferably 100 ° C. or higher and 160 ° C. or lower, and more preferably 120 ° C. or higher and 150 ° C. or lower.

The stretch ratio of the film is preferably 1% to 100%, more preferably 5% to 90%. In addition, in this invention, the draw ratio of a film shall point out the numerical value calculated | required by following numerical formula (10).
Formula (10): {(Dimension after stretching / Dimension before stretching) -1} × 100 (%)

[Additive]
The cellulose acylate film of the present invention preferably contains additives such as an ultraviolet absorber and a plasticizer in addition to the retardation increasing agent.

(UV absorber)
The cellulose acylate film of the present invention may contain an ultraviolet absorber.
Examples of ultraviolet absorbers include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like, but less benzotriazole compounds Compounds are preferred. Further, ultraviolet absorbers described in JP-A-10-182621 and JP-A-8-337574, and polymer ultraviolet absorbers described in JP-A-6-148430 are also preferably used. When the cellulose acylate film of the present invention is used as a protective film for a polarizing plate, the ultraviolet absorber is excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less, from the viewpoint of preventing deterioration of a polarizer and liquid crystal, and From the viewpoint of liquid crystal display properties, those that absorb less visible light having a wavelength of 400 nm or more are preferred.
The addition amount of the ultraviolet absorber is preferably 0.01% by mass or more and 20% by mass or less, and more preferably 0.1% by mass or more and 10% by mass or less of the amount of cellulose acylate.

  Specific examples of the benzotriazole ultraviolet absorber useful in the present invention include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t -Butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butyl Phenyl) -5-chlorobenzotriazole, 2- [2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazole, 2,2 -Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2'-hydroxy-3 ' t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methylphenol, octyl-3- [3-t-Butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-t-butyl-4-hydroxy-5- (5 -Chloro-2H-benzotriazol-2-yl) phenyl] propionate and the like can be mentioned, but not limited thereto.

  As commercial products, “TINUVIN 109”, “TINUVIN 171”, “TINUVIN 326”, “TINUVIN 328” {all manufactured by Ciba Specialty Chemicals Co., Ltd.} Can be preferably used.

(Plasticizer)
In order to improve mechanical properties, the following plasticizers can be used for the cellulose acylate film.
As the plasticizer, phosphoric acid ester or carboxylic acid ester is used. Examples of phosphate esters include triphenyl phosphate (TPP) and tricresyl phosphate (TCP). Representative examples of the carboxylic acid ester include phthalic acid esters and citric acid esters. Examples of phthalic acid esters include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), diphenyl phthalate (DPP) and diethylhexyl phthalate (DEHP). Examples of citrate esters include triethyl O-acetylcitrate (OACTE) and tributyl O-acetylcitrate (OACTB). Examples of other carboxylic acid esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters. Phthalate plasticizers (DMP, DEP, DBP, DOP, DPP, DEHP) are preferably used. DEP and DPP are particularly preferred.

The addition amount of the plasticizer is preferably 0.1 to 25% by mass of the amount of cellulose acylate, more preferably 1 to 20% by mass, and most preferably 3 to 15% by mass.

(Deterioration inhibitor)
In addition, a degradation inhibitor (eg, antioxidant, peroxide decomposer, radical inhibitor, metal deactivator, acid scavenger, amine) may be added to the cellulose acylate film. The deterioration preventing agents are described in JP-A-3-199201, JP-A-51907073, JP-A-5-194789, JP-A-5-271471, and JP-A-6-107854. The addition amount of the deterioration preventing agent is preferably 0.01 to 1% by mass of the solution (dope) to be prepared, and more preferably 0.01 to 0.2% by mass. An addition amount of 0.01% by mass or more is preferable because the effect of the deterioration preventing agent is exhibited. If the addition amount is 1% by mass or less, bleeding out (bleeding out) of the deterioration preventing agent to the film surface does not occur, which is preferable. Examples of particularly preferred deterioration inhibitors include butylated hydroxytoluene (BHT) and tribenzylamine (TBA).

  These steps from casting to post-drying may be performed in an air atmosphere or in an inert gas atmosphere such as nitrogen gas. The winder used in the production of the cellulose acylate film of the present invention may be one generally used, such as a constant tension method, a constant torque method, a taper tension method, a program tension control method with a constant internal stress, etc. It can be wound up by a winding method.

[Characteristics of cellulose acylate film]
(Thickness of cellulose acylate film)
The thickness of the cellulose acylate film of the present invention is preferably 10 μm to 200 μm, more preferably 20 μm to 150 μm, and most preferably 30 μm to 100 μm.

(curl)
The cellulose acylate film of the present invention preferably has a small curl change due to humidity. The curl degree can be measured by cutting the film into a width direction of 50 mm and a longitudinal direction of 2 mm, adjusting the humidity at a predetermined humidity for 24 hours, and measuring the curl value of the film using a curvature scale. . The curl value is represented by 1 / R, where R is a radius of curvature and the unit is m.
The curl value change per 1% RH of the cellulose acylate film of the present invention is preferably 0.02 or less, and more preferably 0.015 or less. By making the curl value change per humidity 1% RH within this range, deformation due to the change in the use environment humidity after the polarizing plate processing is reduced, and light leakage due to a change in the use environment of the liquid crystal display device can be prevented.

(Dimensional change under high temperature and high humidity)
The cellulose acylate film of the present invention preferably has a small dimensional change under high temperature and humidity. The dimensional change rate before and after treatment for 24 hours at 40 ° C. and 95% RH is preferably 0.20% or less, more preferably 0.15% or less. By making the dimensional change under high temperature and humidity within this range, deformation due to the change in the use environment humidity after the processing of the polarizing plate is reduced, and light leakage accompanying a change in the use environment of the liquid crystal display device can be prevented.

(Moisture permeability)
The moisture permeability is calculated as the amount of moisture (g) evaporated in 24 hours per 1 m ^{2 of} the area by measuring the moisture permeability of each sample in accordance with the method described in JIS Z-0208. The moisture permeability is a film property closely related to the durability of the polarizing plate, and the durability of the polarizing plate can be improved by reducing the moisture permeability. The cellulose acylate film of the present invention, 60 ° C., it is preferable moisture permeability 95% RH, 24 hours is 200 g / m ² or more 1700 g / m ² or less.
More preferably 500 g / m ² or more 1400 g / m ² or less.

(Moisture content)
The moisture content of the cellulose acylate film can be evaluated by measuring the equilibrium moisture content at a constant temperature and humidity. Equilibrium moisture content is calculated by measuring the moisture content of the sample that has reached equilibrium after being left at the above temperature and humidity for 24 hours, and dividing the moisture content (g) by the sample mass (g). is there.
The water content of the cellulose acylate film of the present invention at 25 ° C. and 80% RH is preferably 4.5% by mass or less, more preferably 4.0% by mass or less, and 3.5% by mass or less. Most preferably it is.

(Film retardation)
In the present specification, Re _λ and Rth _λ respectively represent the front retardation and the retardation in the thickness direction at the wavelength λ. Re _λ is measured using “KOBRA 21ADH” (manufactured by Oji Scientific Instruments) with light having a wavelength of λ nm incident in the normal direction of the film. Rth _λ is the Re _λ , and the in-plane slow axis (determined by “KOBRA 21ADH”) is the tilt axis (rotation axis), and light having a wavelength of λ nm from the direction inclined + 40 ° with respect to the film normal direction Retardation value measured by making it incident, and retardation measured by making light of wavelength λ nm incident from a direction inclined by −40 ° with respect to the film normal direction with the in-plane slow axis as the tilt axis (rotation axis) “KOBRA 21ADH” is calculated based on the retardation values measured in three directions.

Here, the assumed value of average refractive index is “Polymer Handbook” (John Wiley &
(SONS, INC), catalog values of various optical films can be used. If the average refractive index is not known, it can be measured with an Abbe refractometer. Examples of the average refractive index values of main optical films are given below:
Cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), polystyrene (1.59).
By inputting the assumed average refractive index values and thicknesses, "KOBRA 21ADH" calculates the _{n x, n y, n z} .

The Re ₅₉₀ of the cellulose acylate film of the present invention is preferably 20 to 200 nm, more preferably 30 to 150 nm, and most preferably 60 to 120 nm. Rth ₅₉₀ is preferably 70 to 400 nm, more preferably 50 to 400 nm, still more preferably 100 to 300 nm, and most preferably 150 to 250 nm.
The Rth ₅₉₀ / Re ₅₉₀ ratio is preferably 1 or more and 10 or less, and more preferably 2 or more and 8 or less.

  In the OCB mode and the TN mode, an optically anisotropic layer can be coated on a cellulose acylate film having the retardation value and used as an optical compensation film.

(Photoelasticity)
The photoelastic coefficient of the cellulose acylate of the present invention is preferably 60 × 10 ⁻⁸ cm ² / N or less, and more preferably 20 × 10 ⁻⁸ cm ² . The photoelastic coefficient can be obtained by an ellipsometer.

(Glass-transition temperature)
The glass transition temperature of the cellulose acylate of the present invention is preferably 120 ° C. or higher, more preferably 140 ° C. or higher. The glass transition temperature is a temperature at which the base line derived from the glass transition of the film starts to change and a temperature at which it returns to the base line again when measured at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC). Is obtained as an average value of.

[Saponification]
The cellulose acylate film of the present invention can be used as a polarizing plate protective film by imparting adhesion to polyvinyl alcohol by alkali saponification treatment.

  The alkali saponification treatment of the cellulose acylate film is preferably performed in a cycle in which the film surface is immersed in an alkali solution, neutralized with an acidic solution, washed with water and dried. Examples of the alkaline solution include an aqueous potassium hydroxide solution and an aqueous sodium hydroxide solution, and the prescribed concentration of hydroxide ions is preferably in the range of 0.1 to 5.0 mol / L, and preferably 0.5 to 4.0 mol / L. More preferably, it is in the range of L. The alkaline solution temperature is preferably in the range of room temperature to 90 ° C, more preferably in the range of 40 to 70 ° C.

<Polarizing plate>
Next, the polarizing plate of the present invention will be described in detail.

[Configuration of polarizing plate]
The polarizing plate of this invention may have an adhesive layer, a separate film, and a protective film as a component other than a polarizer and a protective film.

(1) Protective film The polarizing plate of the present invention has a total of two protective films, one on each side of the polarizer, and at least one is the cellulose acylate film of the present invention. Moreover, it is preferable that at least one of the two protective films has a function as a retardation film. When using the polarizing plate of this invention for a liquid crystal display device, it is preferable that at least one of the two polarizing plates arrange | positioned at the both sides of a liquid crystal cell is a polarizing plate of this invention.

  The protective film used in the present invention is preferably a polymer film produced from norbornene resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyarylate, polysulfone, cellulose acylate, and the like. Most preferably it is.

(2) Polarizer The polarizer used in the present invention is preferably composed of polyvinyl alcohol (PVA) and a dichroic molecule, but as described in JP-A-11-248937, A polyvinylene-based polarizer in which a polyene structure is produced by dehydrating or dechlorinating vinyl chloride and then oriented can also be used.

  PVA is a polymer material obtained by saponifying polyvinyl acetate, but may contain components copolymerizable with vinyl acetate such as unsaturated carboxylic acids, unsaturated sulfonic acids, olefins, and vinyl ethers. . In addition, modified PVA containing an acetoacetyl group, a sulfonic acid group, a carboxyl group, an oxyalkylene group, or the like can also be used.

  The saponification degree of PVA is not particularly limited, but is preferably 80 to 100 mol%, particularly preferably 90 to 100 mol% from the viewpoint of solubility and the like. The degree of polymerization of PVA is not particularly limited, but is preferably 1000 to 10,000, and particularly preferably 1500 to 5000.

As described in Japanese Patent No. 2978219, the syndiotacticity of PVA is preferably 55% or more in order to improve durability, but Japanese Patent No. 3317494.
45 to 52.5% described in the publication can be preferably used.

  After PVA is formed into a film, it is preferable to introduce a dichroic molecule to constitute a polarizer. As a method for producing a PVA film, a method of forming a film by casting a stock solution obtained by dissolving a PVA resin in water or an organic solvent is generally preferably used. The concentration of the polyvinyl alcohol-based resin in the stock solution is usually 5 to 20% by mass, and a PVA film having a thickness of 10 to 200 μm can be produced by forming this stock solution by casting. The PVA film can be produced with reference to Japanese Patent No. 3342516, Japanese Patent Application Laid-Open No. 09-328593, Japanese Patent Application Laid-Open No. 2001-302817, and Japanese Patent Application Laid-Open No. 2002-144401.

  The degree of crystallinity of the PVA film is not particularly limited. However, in order to reduce the average crystallinity (Xc) of 50 to 75% by mass and the in-plane hue variation described in Japanese Patent No. 3251073, JP-A-2002 A PVA film having a crystallinity of 38% or less described in JP-A-236214 can be used.

The birefringence (Δn) of the PVA film is preferably small, and a PVA film having a birefringence of 1.0 × 10 ⁻³ or less described in Japanese Patent No. 3342516 can be preferably used. However, as described in JP-A-2002-228835, the birefringence of the PVA film is set to 0.02 or more and 0.01 or less in order to obtain a high degree of polarization while avoiding cutting at the time of stretching the PVA film. may be, as described in JP 2002-060505 value of _{(n x + n y) /} 2-n z may be 0.0003 or 0.01 or less.

  The retardation Re (front) of the PVA film is preferably from 0 nm to 100 nm, and more preferably from 0 nm to 50 nm. The retardation Rth (film thickness direction) of the PVA film is preferably 0 nm or more and 500 nm or less, and more preferably 0 nm or more and 300 nm or less.

In addition, the polarizing plate of the present invention has a PVA film having a 1,2-glycol bond amount of 1.5 mol% or less described in Japanese Patent No. 3021494, and Japanese Patent Application Laid-Open No. 2001-316492. A PVA film having 500 or less optical foreign matters of 5 μm or more per 100 cm ² , and a PVA film having a hot water cutting temperature spot in the TD direction of 1.5 ° C. or less of the film described in JP-A-2002-030163 Further, from a solution in which 1 to 100 parts by mass of a tri- to hexavalent polyhydric alcohol such as glycerin is mixed, or a plasticizer described in JP-A 06-289225 is mixed in an amount of 15% by mass or more. A formed PVA film can be preferably used.

  Although the film thickness before extending | stretching of a PVA film is not specifically limited, 1 micrometer-1 mm are preferable and 20-200 micrometers is especially preferable from a viewpoint of stability of film holding | maintenance and the uniformity of extending | stretching. As described in JP-A-2002-236212, a thin PVA film in which the stress generated when stretching 4 to 6 times in water is 10 N or less may be used.

The dichroic molecules, I ₃ ^- and I ₅ ^- can be preferably used iodine ion or a dichroic dye higher such. In the present invention, higher-order iodine ions are particularly preferably used. Higher-order iodine ions are described in “Applications of Polarizing Plates” by Nagata Ryo, CMC Publishing and “Industrial Materials”, Vol. 28, No. 7, p. 39-p. 45, PVA can be produced by immersing PVA in a solution obtained by dissolving iodine in a potassium iodide aqueous solution and / or a boric acid aqueous solution and adsorbing and orienting the PVA.

  When a dichroic dye is used as the dichroic molecule, an azo dye is preferable, and a bisazo dye and a trisazo dye are particularly preferable. The dichroic dye is preferably a water-soluble dye. For this reason, a hydrophilic substituent such as a sulfonic acid group, an amino group or a hydroxyl group is introduced into the dichroic molecule, and as a free acid or as an alkali metal salt, ammonium salt or amine. It is preferably used as a salt.

  Specific examples of such dichroic dyes include C.I. I. Direct Red 37, Congo Red (C.I. Direct Red 28), C.I. I. Direct Violet 12, C.I. I. Direct Blue 90, C.I. I. Direct Blue 22, C.I. I. Direct Blue 1, C.I. I. Direct Blue 151, C.I. I. Benzidines such as Direct Green 1; C.I. I. Direct Yellow 44, C.I. I. Direct Red 23, C.I. I. Diphenylurea series such as Direct Red 79; I. Stilbene series such as Direct Yellow 12; I. Dinaphthylamine type such as Direct Red 31; I. Direct Red 81, C.I. I. Direct Violet 9, C.I. I. Examples thereof include a J acid type such as Direct Blue 78.

In addition, C.I. I. Direct Yellow 8, C.I. I. Direct Yellow 28, C.I. I. Direct Yellow 86, C.I. I. Direct
Yellow 87, C.I. I. Direct Yellow 142, C.I. I. Direct Orange 26, C.I. I. Direct Orange 39, C.I. I. Direct Orange 72, C.I. I. Direct Orange 106, C.I. I. Direct Orange 107, C.I. I. Direct Red 2, C.I. I. Direct Red 39, C.I. I. Direct Red 83, C.I. I. Direct Red 89, C.I. I. Direct Red 240, C.I. I. Direct
Red 242, C.I. I. Direct Red 247, C.I. I. Direct Violet 48, C.I. I. Direct Violet 51, C.I. I. Direct
Violet 98, C.I. I. Direct Blue 15, C.I. I. Direct
Blue 67, C.I. I. Direct Blue 71, C.I. I. Direct Blue 98, C.I. I. Direct Blue 168, C.I. I. Direct Blue 202, C.I. I. Direct Blue 236, C.I. I. Direct Blue 249, C.I. I. Direct Blue 270, C.I. I. Direct Green 59, C.I. I. Direct Green 85, C.I. I. Direct Brown 44, C.I. I. Direct Brown 106, C.I. I. Direct Brown 195, C.I. I. Direct Brown 210, C.I. I. Direct
Brown 223, C.I. I. Direct Brown 224, C.I. I. Direct Black 1, C.I. I. Direct Black 17, C.I. I. Direct Black 19, C.I. I. Direct Black 54 and the like are further disclosed in JP-A-62-70802, JP-A-1-161202, JP-A-1-172906, JP-A-1-172907, JP-A-1-183602, JP-A-1-248105, The dichroic dyes described in JP-A-1-265205 and JP-A-7-261024 can also be preferably used. In order to produce dichroic molecules having various hues, two or more of these dichroic dyes may be blended. When a dichroic dye is used, the adsorption thickness may be 4 μm or more as described in JP-A No. 2002-082222.

  The content of the dichroic molecule relative to the polyvinyl alcohol polymer constituting the matrix of the film is generally adjusted in the range of 0.01% by mass to 5% by mass. If the content of the dichroic molecule is equal to or higher than the lower limit value, a favorable degree of polarization is exhibited, and if the content is equal to or lower than the upper limit value, problems such as a decrease in single plate transmittance do not occur.

A preferable film thickness of the polarizer is preferably 5 μm to 40 μm, and more preferably 10 μm to 30 μm. The ratio of the thickness of the polarizer to the thickness of the protective film described later is 0.01 ≦ D _A (polarizer film thickness) / D _B (protective film thickness) ≦ described in JP-A-2002-174727. A range of 0.16 is also preferable.

  The crossing angle between the slow axis of the protective film and the absorption axis of the polarizer may be any value, but is preferably parallel or an azimuth angle of 45 ± 20 °.

[Polarizing plate manufacturing process]
Next, the manufacturing process of the polarizing plate of this invention is demonstrated.
The production process of the polarizing plate in the present invention is preferably composed of a PVA film swelling process, a dyeing process, a hardening process, a stretching process, a drying process, a protective film bonding process, and a post-bonding drying process. The order of the dyeing step, the hardening step, and the stretching step may be arbitrarily changed, or several steps may be combined and performed simultaneously. Further, as described in Japanese Patent No. 3331615, washing with water after the hardening step can be preferably performed.

  In the present invention, it is particularly preferable that the PVA film swelling step, the dyeing step, the hardening step, the stretching step, the drying step, the protective film bonding step, and the post-bonding drying step are sequentially performed in the order described. Further, an on-line surface inspection process may be provided during or after the above process.

The swelling process of the PVA film is preferably performed only with water, but as described in JP-A-10-153709, stabilization of optical performance and avoiding wrinkle generation of the polarizing plate substrate in the production line Therefore, the degree of swelling of the polarizing plate substrate can be managed by swelling the polarizing plate substrate with an aqueous boric acid solution.
Moreover, although the temperature and time of a swelling process can be defined arbitrarily, 10 to 60 degreeC and 5 to 2000 second are preferable.

  For the dyeing process of the PVA film, the method described in JP-A-2002-86554 can be used. Moreover, as a dyeing | staining method, not only immersion but arbitrary means, such as application | coating or spraying of an iodine or dye solution, are possible. Further, as described in JP-A-2002-290025, a method of dyeing while stirring the iodine concentration, the dyeing bath temperature, the draw ratio in the bath, and the bath liquid in the bath may be used.

  When higher-order iodine ions are used as the dichroic molecule, in order to obtain a high-contrast polarizing plate, it is preferable to use a solution obtained by dissolving iodine in an aqueous potassium iodide solution in the dyeing step. In this case, iodine in the iodine-potassium iodide aqueous solution is 0.05 to 20 g / L, further 0.5 to 2 g / L; potassium iodide is 3 to 200 g / L, and further 30 to 120 g / L; iodine. : The mass ratio of potassium iodide is 1: 1 to 2000, and more preferably 1:30 to 120. The dyeing time is preferably 10 to 1200 seconds, more preferably 30 to 600 seconds, and the liquid temperature is preferably 10 to 60 ° C, more preferably 20 to 50 ° C.

  Further, as described in Japanese Patent No. 3145747, boron compounds such as boric acid and borax may be added to the dyeing solution.

  In the hardening process of the PVA film, it is preferable to immerse the PVA film in a crosslinking agent solution, or apply the crosslinking agent solution to the film to include the crosslinking agent. Further, as described in JP-A-11-52130, the hardening process can be performed in several steps.

As the cross-linking agent, the one described in US Reissue Patent No. 232897 can be used, and as described in Japanese Patent No. 3357109, a polyvalent aldehyde is used as the cross-linking agent in order to improve dimensional stability. However, boric acids are most preferably used. When boric acid is used as the crosslinking agent used in the hardening step, metal ions may be added to the boric acid-potassium iodide aqueous solution. Zinc chloride is preferable as the metal ion, but as described in JP-A-2000-35512, zinc halide such as zinc iodide, zinc sulfate such as zinc acetate, and zinc acetate are used instead of zinc chloride. It can also be used.

  In the present invention, it is preferable to prepare a boric acid-potassium iodide aqueous solution to which zinc chloride has been added, and to perform the hardening by immersing the PVA film. Boric acid is 1 to 100 g / L, more preferably 10 to 80 g / L; potassium iodide is 1 to 120 g / L, further 5 to 100 g / L; zinc chloride is 0.01 to 10 g / L, and more preferably 0. 02-8 g / L; Hardening time is 10 to 1200 seconds, more preferably 30 to 600 seconds; liquid temperature is preferably 10 to 60 ° C., more preferably 20 to 50 ° C.

For the stretching process of the PVA film, a longitudinal uniaxial stretching method as described in US Pat. No. 2,454,515 or a tenter method as described in JP-A-2002-86554 can be preferably used. . A preferable draw ratio is 2 times or more and 12 times or less, and more preferably 3 times or more and 10 times or less. The relationship between the draw ratio, the thickness of the original fabric and the thickness of the polarizer is described in JP-A-2002-040256:
(Polarizer film thickness / raw film thickness after protective film bonding) × (total stretching ratio)> 0.17
JP, 2002-040247, A describes the relation between the width of the polarizer when leaving the final bath and the width of the polarizer when bonding the protective film:
0.80 ≦ (polarizer width at the time of protective film bonding / polarizer width when leaving the final bath) ≦ 0.95
It can also be preferably performed.

  As the PVA film drying step, a method known in JP-A-2002-86554 can be used, but a preferable temperature range is 30 ° C. to 100 ° C., and a preferable drying time is 30 seconds to 60 minutes. Further, as described in Japanese Patent No. 3148513, a heat treatment is performed so that the fading temperature in water is 50 ° C. or higher, or it is described in Japanese Patent Laid-Open Nos. 07-325215 and 07-325218. As described above, aging in an atmosphere in which the temperature and humidity are controlled can be preferably employed.

  The protective film laminating step is a step of laminating both surfaces of the above-described polarizer that has gone through the drying step with two protective films. A method of bonding with a pair of rolls is preferably used so that the adhesive liquid is supplied immediately before bonding and the polarizer and the protective film are overlapped. Further, as described in JP-A-2001-296426 and JP-A-2002-86554, in order to suppress the groove-like unevenness of the record due to the stretching of the polarizer, It is preferable to adjust the moisture content. In the present invention, a moisture content of 0.1 to 30% by mass is preferably used.

  The adhesive between the polarizer and the protective film is not particularly limited, and examples thereof include PVA resin (including modified PVA such as acetoacetyl group, sulfonic acid group, carboxyl group, oxyalkylene group) and boron compound aqueous solution, Of these, PVA resins are preferred. The thickness of the adhesive layer is preferably 0.01 to 5 μm, and particularly preferably 0.05 to 3 μm after drying.

Moreover, in order to improve the adhesive force of a polarizer and a protective film, it is preferable to perform adhesion after surface-treating the protective film to make it hydrophilic. The surface treatment method is not particularly limited, and a known method such as a saponification method using an alkaline solution or a corona treatment method can be used. Further, an easy adhesion layer such as a gelatin subbing layer may be provided after the surface treatment. JP200
As described in JP-A-2-267839, the contact angle of the protective film surface with water is preferably 50 ° or less.

  The drying conditions after bonding are in accordance with the method described in JP-A-2002-86554, but a preferable temperature range is 30 ° C. to 100 ° C., and a preferable drying time is 30 seconds to 60 minutes. It is also preferable to perform aging in an atmosphere with temperature and humidity control as described in JP-A-07-325220.

The element content in the polarizer is as follows: iodine 0.1-3.0 g / m ² , boron 0.1-5.0 g / m ² , potassium 0.1-2.00 g / m ² , zinc 0-2. It is preferably 00 g / m ² . Further, the potassium content may be 0.2% by mass or less as described in JP-A No. 2001-166143, and the zinc content in the polarizer is described in JP-A No. 2000-035512. It is good also as 0.04-0.5 mass% currently being carried out.

  As described in Japanese Patent No. 3323255, in order to increase the dimensional stability of the polarizing plate, an organic titanium compound and / or an organic zirconium compound is added in any of the dyeing process, the stretching process, and the hardening process. In addition, it can also contain at least one compound selected from organic titanium compounds and organic zirconium compounds. Further, a dichroic dye may be added to adjust the hue of the polarizing plate.

[Characteristics of polarizing plate]
(1) Transmittance and degree of polarization The preferred single plate transmittance of the polarizing plate of the present invention defined by the following formula (10) is 42.5% or more and 49.5% or less, more preferably 42. It is 8% or more and 49.0% or less. A preferable range of the degree of polarization defined by the following formula (11) is 99.900% or more and 99.999% or less, and more preferably 99.940% or more and 99.995% or less. A preferable range of the parallel transmittance is 36% or more and 42% or less, and a preferable range of the orthogonal transmittance is 0.001% or more and 0.05% or less. The preferable range of the dichroic ratio defined by the following formula (12) is 48 or more and 1215 or less, and more preferably 53 or more and 525 or less.

The transmittance is defined by the following formula (10) based on JIS Z-8701.
Formula (10):

  Here, K, S (λ), y (λ), and τ (λ) are as follows.

S (λ): spectral distribution of standard light used for color display y (λ): color matching function in XYZ color system (CIE1931 color system) τ (λ): spectral transmittance

  Formula (11):

  Formula (12):

  The iodine concentration and the single plate transmittance may be within the ranges described in JP-A-2002-258051.

  The parallel transmittance may be small in wavelength dependency as described in Japanese Patent Application Laid-Open No. 2001-083328 and Japanese Patent Application Laid-Open No. 2002-022950. The optical characteristics when the polarizing plates are arranged in crossed Nicols may be in the range described in Japanese Patent Application Laid-Open No. 2001-091736, and the relationship between parallel transmittance and orthogonal transmittance is disclosed in Japanese Patent Application Laid-Open No. 2002-174728. It may be within the range described in the publication.

  As described in Japanese Patent Application Laid-Open No. 2002-221618, the standard deviation of parallel transmittance every 10 nm is 3 or less and the light wavelength is 420 to 700 nm when the light wavelength is 420 to 700 nm. The minimum value of (parallel transmittance / orthogonal transmittance) every 10 nm may be 300 or more.

  The parallel transmittance and orthogonal transmittance at a wavelength of 440 nm, the parallel transmittance, the parallel transmittance and the orthogonal transmittance at a wavelength of 550 nm, and the parallel transmittance and the orthogonal transmittance at a wavelength of 610 nm of the polarizing plate are disclosed in JP-A-2002-258042. The range described in JP 2002-258043 A can also be preferably performed.

(2) Hue The hue of the polarizing plate of the present invention is preferably determined using the lightness index L ^* and the chromaticness index a ^* and b ^* in the L ^* a ^* b ^* color system recommended as the CIE uniform perceptual space. Be evaluated.
L ^* , a ^* , and b ^* are defined by Equation (13) using X, Y, and Z in the table XYZ color system.
Formula (13):

Here, X ₀ , Y ₀ , and Z ₀ represent tristimulus values of the illumination light source. In the case of standard light C, X ₀ = 98.072, Y ₀ = 100, Z ₀ = 118.225, and standard light D _In the case of ₆₅ , X ₀ = 95.045, Y ₀ = 100, Z ₀ = 108.892.

The preferable range of a ^* for a single polarizing plate is −2.5 or more and 0.2 or less, and more preferably −2.0 or more and 0 or less. A preferable range of b ^* of the single polarizing plate is 1.5 or more and 5 or less, and more preferably 2 or more and 4.5 or less. The preferable range of a ^* of the parallel transmitted light of the two polarizing plates is −4.0 to 0, and more preferably −3.5 to −0.5. The preferred range of b ^* of the parallel transmitted light of the two polarizing plates is 2.0 or more and 8 or less, more preferably 2.5 or more and 7 or less. The preferable range of a ^* of the orthogonally transmitted light of the two polarizing plates is −0.5 or more and 1.0 or less, and more preferably 0 or more and 2 or less. The preferable range of b ^* of the orthogonally transmitted light of the two polarizing plates is −2.0 or more and 2 or less, and more preferably −1.5 or more and 0.5 or less.

The hue may be evaluated by chromaticity coordinates (x, y) calculated from the X, Y, and Z. For example, the chromaticity (x _p , y _p ) of parallel transmitted light of two polarizing plates and The chromaticity (x _c , y _c ) of the orthogonal transmitted light is set to a range described in JP 2002-214436 A, JP 2001-166136 A, and JP 2002-169024 A, or hue and absorbance. The relationship between
It can also be preferably performed within the range described in 1-311827.

(3) Viewing angle characteristics When a polarizing plate is placed in crossed Nicols and light with a wavelength of 550 nm is incident, when normal light is incident, the angle from 45 ° to the polarization axis is 40 ° to the normal. It is also preferable that the transmittance ratio and the xy chromaticity difference when incident at an angle are within the ranges described in Japanese Patent Laid-Open Nos. 2001-166135 and 2001-166137. Further, as described in JP-A-10-068817, the light transmittance (T ₀ ) in the vertical direction and the light in the direction inclined by 60 ° from the normal line of the laminated body of the polarizing plate laminated body arranged in crossed Nicols. The ratio (T ₆₀ / T ₀ ) with the transmittance (T ₆₀ ) is set to 10000 or less, or as described in JP-A-2002-139625, the polarizing plate has an arbitrary angle from the normal to an elevation angle of 80 °. When natural light is incident at an angle, the transmittance difference of transmitted light within a wavelength range of 20 nm is set to 6% or less in the wavelength range of 520 to 640 nm of the transmission spectrum, or described in JP-A-08-248201. It is also preferable that the difference in luminance of transmitted light at an arbitrary 1 cm distance on the film is within 30%.

(4) Durability (4-1) Damp heat durability The light transmittance and the rate of change of the degree of polarization before and after leaving in an atmosphere of 60 ° C. and 90% RH for 500 hours are 3% based on absolute values. The following is preferable. In particular, the change rate of the light transmittance is 2% or less, and the change rate of the polarization degree is preferably 1.0% or less, more preferably 0.1% or less based on the absolute value. Further, as described in JP-A-07-0777608, it is also preferred that the degree of polarization after standing for 500 hours at 80 ° C. and 90% RH is 95% or more and the single transmittance is 38% or more.

(4-2) Dry durability It is also preferable that the light transmittance and the change rate of the polarization degree before and after being left in a dry atmosphere at 80 ° C. for 500 hours are 3% or less based on absolute values. . In particular, the change rate of the light transmittance is preferably 2% or less, and the change rate of the polarization degree is preferably 1.0% or less, more preferably 0.1% or less based on the absolute value.

(4-3) Other durability Further, as described in JP-A-06-167611, the shrinkage after standing at 80 ° C. for 2 hours is 0.5% or less, or both surfaces of the glass plate The x and y values after leaving the polarizing plate laminate arranged in crossed Nicols in an atmosphere of 69 ° C. for 750 hours within the range described in JP-A-10-068818, after 200 hours standing process in an atmosphere of RH 90%, the change in spectral intensity ratio of the 105 cm ^-1 and 157cm ^-1 due to Raman spectroscopy, described in JP-a-08-094834 and JP 09-197127 It is also preferable to set the range.

(5) Orientation degree The higher the degree of orientation of PVA, the better the polarization performance, but the range of 0.2 to 1.0 is preferable as the order parameter value calculated by means such as polarization Raman scattering or polarization FT-IR. It is. Further, as described in JP-A-59-133509, the difference between the orientation coefficient of the polymer segment in the entire amorphous region of the polarizer and the orientation coefficient of the occupied molecule (0.75 or more) is at least 0. .15, or as described in JP 04-204907 A, the orientation coefficient of the amorphous region of the polarizer is 0.65 to 0.85, or a higher order of I ₃ ⁻ or I ₅ ⁻ . It is also preferable to adjust the degree of orientation of iodine ions to 0.8 to 1.0 as an order parameter value.

(6) Other characteristics As described in JP-A-2002-006133, the contraction force in the absorption axis direction per unit width when heated at 80 ° C. for 30 minutes is 4.0 N / cm or less. As described in JP-A No. 2002-236213, when the polarizing plate is placed under heating at 70 ° C. for 120 hours, the dimensional change rate in the absorption axis direction and the dimensional change in the polarizing axis direction of the polarizing plate It is also preferable to make the ratios both within ± 0.6%, or to set the moisture content of the polarizing plate to 3% by mass or less as described in JP-A-2002-090546. Further, as described in Japanese Patent Application Laid-Open No. 2000-249832, the surface roughness in the direction perpendicular to the stretching axis is 0.04 μm or less based on the center line average roughness, or Japanese Patent Application Laid-Open No. 10-268294. As described in JP-A-10-111411, the refractive index n ₀ in the transmission axis direction is made larger than 1.6, or the relationship between the thickness of the polarizing plate and the thickness of the protective film is It can also be preferably performed.

[Functionalization of polarizing plate]
The polarizing plate of the present invention includes an LCD viewing angle widening film, a retardation film such as a λ / 4 plate for application to a reflective LCD, an antireflection film for improving display visibility, a brightness enhancement film, It is preferably used as a functionalized polarizing plate combined with an optical film having functional layers such as a coat layer, a forward scattering layer, and an antiglare (antiglare) layer.

A configuration example in which the polarizing plate of the present invention is combined with the above functional optical film is shown in FIG.
As a protective film on one side of the polarizing plate 5, the functional optical film 3 may be adhered to the polarizer 2 through an adhesive layer {FIG. 1 (A)}, or the protective films 1 a and 1 b on both surfaces of the polarizer 2. The functional optical film 3 may be bonded to the polarizing plate 5 provided with the adhesive layer 4 through the adhesive layer 4 {FIG. 1 (B)}. In the former case, an arbitrary transparent protective film may be used for the other protective film 1. Moreover, in the polarizing plate of this invention, it is also preferable to stick an optical functional layer to a protective film through an adhesion layer, and to set it as the structure of FIG. The peel strength between layers such as a functional layer and a protective film is preferably 4.0 N / 25 mm or more described in JP-A-2002-311238. The functional optical film can be preferably disposed on the liquid crystal module side or on the opposite side of the liquid crystal module, that is, on the display side or the backlight side, depending on the intended function.

  The functional optical film used in combination with the polarizing plate of the present invention will be described below.

(1) Viewing Angle Enlargement Film The polarizing plate of the present invention includes TN (Twisted Nematic), IPS (In-Plane Switching), OCB (Optically Compensatory).
Bend), VA (Vertically Aligned), and ECB (Electrically Controlled Birefringence) can be used in combination with a viewing angle widening film proposed for display modes.

  As a viewing angle widening film for the TN mode, “Journal of the Japan Printing Society” Vol. 36, No. 3 (1999) p. 40-44, “Monthly Display” August issue (2002) p. “WV film” {Fuji Photo Film Co., Ltd. )} Are preferably used in combination.

A preferable configuration of the viewing angle widening film for the TN mode has an alignment layer and an optically anisotropic layer in this order on the cellulose acylate film of the present invention. Although a viewing angle expansion film may be used by being bonded to a polarizing plate via an adhesive, “SID'00 Dig.
", P. 551 (2000), it is particularly preferable from the viewpoint of thinning that the film is used also as one of the protective films of the polarizer.

  The alignment layer can be provided by means such as a rubbing treatment of an organic compound (preferably a polymer), oblique deposition of an inorganic compound, or formation of a layer having a microgroup. Furthermore, an alignment layer in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation is also known. The rubbing treatment is preferably performed by rubbing the surface of the polymer layer several times in a certain direction with paper or cloth. It is preferable that the absorption axis direction and the rubbing direction of the polarizer are substantially parallel. As the polymer used for the alignment layer, polyimide, polyvinyl alcohol, a polymer having a polymerizable group described in JP-A-9-152509, and the like can be preferably used. The thickness of the alignment layer is preferably 0.01 to 5 μm, and more preferably 0.05 to 2 μm.

The optically anisotropic layer preferably contains a liquid crystalline compound. The liquid crystalline compound used in the present invention particularly preferably has a discotic compound (discotic liquid crystal). The discotic liquid crystal molecule has a disk-like core portion like a triphenylene derivative, and has a structure in which side chains extend radially therefrom. In order to impart stability over time, it is also preferable to further introduce a group that reacts with heat, light or the like. Preferred examples of the discotic liquid crystal are described in JP-A-8-50206.
Examples of discotic liquid crystal molecules are shown below.

  The discotic liquid crystal molecules are aligned almost parallel to the film plane with a pretilt angle in the rubbing direction in the vicinity of the alignment layer, and the discotic liquid crystal molecules are oriented so that they are perpendicular to the plane on the opposite air side. is doing. The discotic liquid crystal layer as a whole has a hybrid alignment, and this layer structure can realize a wide viewing angle of a TN mode TFT-LCD.

  The optically anisotropic layer is generally formed by applying a solution of a discotic compound and other compounds (for example, a polymerizable monomer, a photopolymerization initiator, etc.) dissolved in a solvent onto the alignment layer, drying it, After heating to the temperature at which the tick nematic phase is formed, polymerization is performed by irradiation with UV light or the like, followed by cooling. The discotic nematic liquid crystal phase-solid phase transition temperature of the discotic liquid crystalline compound used in the present invention is preferably 70 to 300 ° C, particularly preferably 70 to 170 ° C.

  In addition to the discotic compound added to the optically anisotropic layer, the compound has compatibility with the discotic compound and can give a preferable change in tilt angle to the liquid crystalline discotic compound or inhibit the alignment. Any compound can be used as long as it is not. Among these, polymerizable monomers (for example, compounds having a vinyl group, vinyloxy group, acryloyl group and methacryloyl group), additives for controlling the orientation on the air interface side such as fluorine-containing triazine compounds, cellulose acetate, cellulose acetate propio And polymers such as nates, hydroxypropylcellulose and cellulose acetate butyrate. These compounds are generally used in an amount of 0.1 to 50% by mass, preferably 0.1 to 30% by mass, based on the discotic compound.

  The thickness of the optically anisotropic layer is preferably 0.1 to 10 μm, and more preferably 0.5 to 5 μm.

A preferred embodiment of the viewing angle widening film comprises a cellulose acylate film as a transparent substrate film, an alignment layer provided thereon, and an optically anisotropic layer comprising a discotic liquid crystal formed on the alignment layer. In addition, the optically anisotropic layer is crosslinked by UV light irradiation.

  In addition to the above, when the viewing angle widening film and the polarizing plate of the present invention are combined, for example, as described in Japanese Patent Application Laid-Open No. 07-198942, it has an optical axis in a direction intersecting the plate surface. Laminating with a retardation plate exhibiting birefringence anisotropy, or as described in JP-A-2002-258052, the dimensional change rate of the protective film and the optically anisotropic layer is substantially the same. It can also be preferably performed. Further, as described in JP-A-12-258632, the polarizing plate to be bonded to the viewing angle widening film has a moisture content of 2.4% or less, or described in JP-A-2002-267839. As can be seen, the contact angle of the viewing angle widening film surface with water can be preferably set to 70 ° or less.

  The viewing angle widening film for an IPS mode liquid crystal cell is used for optical compensation of liquid crystal molecules aligned in parallel to the substrate surface and improvement of viewing angle characteristics of the orthogonal transmittance of the polarizing plate during black display in the absence of an electric field. In the IPS mode, black is displayed when no electric field is applied, and the transmission axes of the pair of upper and lower polarizing plates are orthogonal. However, when observed from an oblique direction, the crossing angle of the transmission axes is not 90 °, and leakage light is generated, resulting in a decrease in contrast. When the polarizing plate of the present invention is used in an IPS mode liquid crystal cell, the in-plane retardation is close to 0 and the thickness direction is reduced as described in JP-A-10-54982 to reduce leakage light. Are preferably used in combination with a viewing angle widening film having a phase difference.

  The OCB mode viewing angle widening film for liquid crystal cells is intended to improve the viewing angle characteristics of black display by optically compensating the liquid crystal layer that is vertically aligned at the center of the liquid crystal layer by applying an electric field and tilted near the substrate interface. used. When the polarizing plate of the present invention is used in an OCB mode liquid crystal cell, a discotic liquid crystalline compound as described in US Pat. No. 5,805,253 is preferably used in combination with a viewing angle widening film that is hybrid-aligned.

  The viewing angle widening film for liquid crystal cells in the VA mode improves the viewing angle characteristics of black display in a state where liquid crystal molecules are vertically aligned with respect to the substrate surface in the absence of an electric field. As such a viewing angle widening film, a film having an in-plane retardation close to 0 and having a retardation in the thickness direction as described in Japanese Patent No. 2866372, or a discotic compound Is a film arranged in parallel to the substrate, a stretched film having the same front retardation value, a film in which the slow axes are laminated so as to be orthogonal, and prevention of deterioration of orthogonal transmittance in the oblique direction of the polarizing plate, It is preferably used in combination with a laminate of films made of rod-like compounds such as liquid crystal molecules.

(2) Retardation film The polarizing plate of the present invention preferably has a retardation layer. The retardation layer in the present invention is preferably a λ / 4 plate, and can be used as a circularly polarizing plate by laminating the polarizing plate of the present invention and the λ / 4 plate. The circularly polarizing plate has a function of converting incident light into circularly polarized light, and is preferably used for a reflective liquid crystal display device, a transflective liquid crystal display device such as an ECB mode, or an organic EL element.

The λ / 4 plate used in the present invention is a retardation film having a retardation (Re) of approximately ¼ of the wavelength in the visible light wavelength range in order to obtain almost perfect circularly polarized light in the visible light wavelength range. It is preferable that “Retardation of approximately ¼ in the wavelength range of visible light” means that the longer the wavelength, the larger the retardation is from 400 to 700 nm, and the retardation value (Re ₄₅₀ ) measured at a wavelength of 450 nm is 80 to 125 nm.
And the retardation value (Re ₅₉₀ ) measured at a wavelength of 590 nm is in a range satisfying the relationship of 120 to 160 nm. Still more preferably Re ₅₉₀ -Re ₄₅₀ ≧ 5nm, particularly preferably Re ₅₉₀ -Re ₄₅₀ ≧ 10nm.

  The λ / 4 plate used in the present invention is not particularly limited as long as it satisfies the above-mentioned conditions. For example, it is described in JP-A-5-27118, JP-A-10-68816, and JP-A-10-90521. A λ / 4 plate obtained by laminating a plurality of polymer films, a λ / 4 plate obtained by stretching one polymer film described in WO00 / 65384 pamphlet, WO00 / 26705 pamphlet, A known λ / 4 plate such as a λ / 4 plate described in JP 2000-284126 A and JP 2002-31717 A, in which at least one optically anisotropic layer is provided on a polymer film, is used. be able to. Moreover, the direction of the slow axis of the polymer film and the orientation direction of the optically anisotropic layer can be arranged in any direction according to the liquid crystal cell.

  In the circularly polarizing plate, the slow axis of the λ / 4 plate and the transmission axis of the polarizer can intersect at an arbitrary angle, but preferably intersect within a range of 45 ° ± 20 °. However, the slow axis of the λ / 4 plate and the transmission axis of the polarizer may intersect within a range other than the above.

When the λ / 4 plate is formed by laminating the λ / 4 plate and the λ / 2 plate, as described in Japanese Patent No. 3236304 and Japanese Patent Laid-Open No. 10-68816, the λ / 4 plate and the λ / 4 plate are used. / 2 It is preferable to bond so that the angle formed by the slow axis in the plane of the plate and the transmission axis of the polarizing plate is substantially 75 ° and 15 °.
When the λ / 4 plate is configured by laminating the λ / 4 plate and the λ / 2 plate, as described in Japanese Patent No. 3236304 and Japanese Patent Laid-Open No. 10-68816, the λ / 4 plate and Bonding is preferably performed so that the angle formed by the slow axis in the plane of the λ / 2 plate and the transmission axis of the polarizing plate is substantially 75 ° and 15 °.

(3) Antireflection film The polarizing plate of the present invention can be used in combination with an antireflection film. As the antireflection film, either a film having a reflectivity of about 1.5% only by applying a single layer of a low refractive index material such as a fluoropolymer, or a film having a reflectivity of 1% or less using multilayer interference of a thin film is used it can.

  In the present invention, a structure in which a low refractive index layer and at least one layer having a higher refractive index than that of the low refractive index layer (that is, a high refractive index layer and a medium refractive index layer) is laminated on the transparent support is preferably used. Is done. Further, an antireflection film described in “Nitto Technical Report” Vol. 38, No. 1 (May) (2000), pages 26 to 28, JP-A No. 2002-301783 and the like can also be preferably used.

The refractive index of each layer satisfies the following relationship.
Refractive index of high refractive index layer> refractive index of medium refractive index layer> refractive index of transparent support> refractive index of low refractive index layer

  As the transparent support used for the antireflection film, a transparent polymer film used for the protective film of the polarizer can be preferably used.

(Low refractive index layer)
The refractive index of the low refractive index layer is 1.20 to 1.55, preferably 1.30 to 1.50. The low refractive index layer is preferably used as an outermost layer having scratch resistance and antifouling properties. In order to improve the scratch resistance, it is also preferable to impart slipperiness to the surface using a material containing a silicone group or fluorine.

  Examples of the fluorine-containing compound include paragraph numbers [0018] to [0026] of JP-A-9-222503, paragraph numbers [0019] to [0030] of JP-A-11-38202, and paragraph numbers of JP-A-2001-40284. [0027] to [0028], compounds described in JP-A No. 2000-284102 and the like can be preferably used.

  The silicone-containing compound is preferably a compound having a polysiloxane structure, but reactive silicone [for example, “Silaplane” {manufactured by Chisso Corporation]] or polysiloxane having silanol groups at both ends (Japanese Patent Laid-Open No. 11-258403) ) Etc. can also be used. An organometallic compound such as a silane coupling agent and a specific fluorine-containing hydrocarbon group-containing silane coupling agent may be cured by a condensation reaction in the presence of a catalyst (Japanese Patent Laid-Open No. 58-142958, the same as above). 58-147483, 58-147484, JP-A-9-157582, 11-106704, JP-A-2000-117902, 2001-48590, 2002-53804 And the like).

  In the low refractive index layer, as an additive other than the above, the average primary particle diameter of fillers (for example, silicon dioxide (silica), fluorine-containing particles (magnesium fluoride, calcium fluoride, barium fluoride)) is 1 -150 nm low refractive index inorganic compound (organic fine particles described in paragraph Nos. [0020] to [0038] of JP-A No. 11-3820), silane coupling agent, slip agent, surfactant, etc. Can also be preferably performed.

  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.), but is preferably formed by a coating method because it can be manufactured at low cost. . As the coating method, dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, and micro gravure can be preferably used.

  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.

(Medium refractive index layer and high refractive index layer)
The medium refractive index layer and the high refractive index layer preferably have a structure in which ultrafine particles of high refractive index having an average particle diameter of 100 nm or less are dispersed in a matrix material. Inorganic compound fine particles having a high refractive index include inorganic compounds having a refractive index of 1.65 or more, for example, oxides such as Ti, Zn, Sb, Sn, Zr, Ce, Ta, La, and In, and metal atoms thereof. A composite oxide or the like can be preferably used.

  Such ultrafine particles may be obtained by treating the particle surface with a surface treatment agent (silane coupling agent, etc .: JP-A Nos. 11-295503, 11-153703, 2000-9908, anionic compounds) Or, an organic metal coupling agent: JP 2001-310432 A, a core-shell structure with high refractive index particles as a core (JP 2001-166104 A, etc.), or a specific dispersant is used in combination ( For example, it can be used in the form of JP-A No. 11-153703, US Pat. No. 6,210,858, JP-A No. 2002-27776069, and the like.

  As the matrix material, conventionally known thermoplastic resins, curable resin films, and the like can be used, but JP-A-2000-47004, 2001-315242, 2001-31871, and 2001-296401. It is also possible to use a curable film obtained from a polyfunctional material described in a gazette or the like or a metal alkoxide composition described in JP-A-2001-293818 or the like.

  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 haze of the antireflection film is preferably 5% or less, more preferably 3% or less. Further, the hardness 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 K-5400.

(4) Brightness improving film The polarizing plate of this invention can be used in combination with a brightness improving film. The brightness enhancement film has a function of separating circularly polarized light or linearly polarized light, and is disposed between the polarizing plate and the backlight, and reflects or backscatters one circularly polarized light or linearly polarized light to the backlight side. The re-reflected light from the backlight part partially changes the polarization state and partially transmits when it re-enters the brightness enhancement film and the polarizing plate. By repeating this process, the light utilization rate is improved. The front luminance is improved to about 1.4 times. As the brightness enhancement film, an anisotropic reflection method and an anisotropic scattering method are known, and both can be combined with the polarizing plate of the present invention.

  In the anisotropic reflection method, a brightness enhancement film having anisotropy in reflectance and transmittance is known by laminating a uniaxially stretched film and an unstretched film in multiple layers to increase the refractive index difference in the stretching direction. Multi-layer systems using the principle of dielectric mirrors (described in pamphlets of International Publication Nos. 95/17691, 95/17692, 95/17699) and cholesteric liquid crystal systems (European Patent No. No. 606940A2 and JP-A-8-271731) are known. Multi-layer brightness enhancement films that use the principle of dielectric mirrors include “DBEF-E”, “DBEF-D”, “DBEF-M” (all manufactured by 3M), and cholesteric liquid crystal brightness enhancement films. "NIPOCS" {manufactured by Nitto Denko Corporation} is preferably used in the present invention. Regarding “NIPOCS”, “Nitto Technical Report”, Vol. 38, No. 1 (May), 2000, pages 19 to 21, etc. can be referred to.

  In the present invention, the pamphlets of International Publication Nos. 97/32223, 97/32224, 97/32225, 97/32226, and JP-A-9-274108 and 11-174231 are used. It is also preferable to use in combination with a brightness enhancement film of an anisotropic scattering method, which is described in each publication and blended with a positive intrinsic birefringent polymer and a negative intrinsic birefringent polymer and uniaxially stretched. As the anisotropic scattering system brightness enhancement film, “DRPF-H” (manufactured by 3M) is preferable.

  The polarizing plate and the brightness enhancement film of the present invention are preferably used as an integrated type in which one of the polarizing film and the protective film of the polarizing plate is bonded via an adhesive.

(5) Other functional optical films The polarizing plate of the present invention further includes a hard coat layer, a forward scattering layer, an antiglare (antiglare) layer, a gas barrier layer, a sliding layer, an antistatic layer, an undercoat layer, a protective layer, and the like. It is also preferred to use it in combination with a functional optical film provided with These functional layers are preferably used in combination with each other in the same layer as the antireflection layer in the antireflection film or the optically anisotropic layer in the viewing angle compensation film. These functional layers can be used by providing them on one side or both sides of the anti-reflective film or viewing angle compensation film on the side of the polarizer or the side opposite to the polarizer (the side on the air side).

(5-1) Hard Coat Layer The polarizing plate of the present invention is preferably combined with a functional optical film provided with a hard coat layer on the surface of the transparent support in order to impart mechanical strength such as scratch resistance. Is called. When the hard coat layer is applied to the antireflection film, it is particularly preferable to provide it between the transparent support and the high refractive index layer.

  The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of the curable compound by light and / or heat. The curable functional group is preferably a photopolymerizable functional group, and the hydrolyzable functional group-containing organometallic compound is preferably an organic alkoxysilyl compound. As a specific constituent composition of the hard coat layer, for example, those described in JP-A-2002-144913, JP-A-2000-9908, WO 00/46617, etc. can be preferably used.

The film thickness of the hard coat layer is preferably 0.2 to 100 μm.
The hardness of the hard coat layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test according to JIS K-5400. Further, in the Taber test according to JIS K-5400, the smaller the wear amount of the test piece before and after the test, the better.

  As the material for forming the hard coat layer, a compound containing an ethylenically unsaturated group or a compound containing a ring-opening polymerizable group can be used, and these compounds can be used alone or in combination. Preferred examples of the compound containing an ethylenically unsaturated group include ethylene glycol diacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol. Polyacrylates of polyols such as hexaacrylate; epoxy acrylates such as diacrylate of bisphenol A diglycidyl ether, diacrylate of hexanediol diglycidyl ether; obtained by reaction of polyisocyanate and hydroxyl group-containing acrylate such as hydroxyethyl acrylate Examples of preferred compounds include urethane acrylates.

  Commercially available compounds include “EB-600”, “EB-40”, “EB-140”, “EB-1150”, “EB-1290K”, “IRR214”, “EB-2220”, “TMPTA”. , “TMPTMA” {above, manufactured by Daicel UCB Co., Ltd.}, “UV-6300”, “UV-1700B” {above, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.}, and the like.

Preferred examples of the compound containing a ring-opening polymerizable group include ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, trimethylol ethane triglycidyl ether, trimethylol propane triglycidyl ether, glycerol triglycidyl ether as glycidyl ethers. , Triglycidyl trishydroxyethyl isocyanurate, sorbitol tetraglycidyl ether, pentaerythritol tetraglycyl ether, polyglycidyl ether of cresol novolac resin, polyglycidyl ether of phenol novolac resin, etc .; "Celoxide 2081", "Epolide GT-301", "Epolide GT-401", "EHPE 150CE "{manufactured by Daicel Chemical Industries, Ltd.}, phenol novolak resin polycyclohexyl epoxy methyl ether, etc .; as oxetanes," OXT-121 "," OXT-221 "," OX-SQ "," PNOX- 1009 "{above, manufactured by Toagosei Co., Ltd.} and the like. In addition, a polymer of glycidyl (meth) acrylate or a copolymer of glycidyl (meth) acrylate and a monomer copolymerizable therewith can be used for the hard coat layer.

  For the hard coat layer, fine particles of oxide such as silicon, titanium, zirconium, and aluminum, and polyethylene are used to reduce curing shrinkage of the hard coat layer, improve adhesion to the substrate, and reduce curling of the polarizing plate of the present invention. It is also preferable to add crosslinked fine particles such as crosslinked fine particles such as polystyrene, poly (meth) acrylic acid esters and polydimethylsiloxane, and fine organic particles such as fine crosslinked rubber fine particles such as SBR and NBR. The average particle size of these crosslinked fine particles is preferably 1 nm to 20000 nm. Further, the shape of the crosslinked fine particles can be used without particular limitation, such as a spherical shape, a rod shape, a needle shape, or a plate shape. The addition amount of the fine particles is preferably 60% by volume or less, more preferably 40% by volume or less of the hard coat layer after curing.

  When the inorganic fine particles described above are added, these inorganic fine particles generally have poor affinity with the binder polymer. Therefore, these inorganic fine particles contain a metal such as silicon, aluminum, titanium, and the alkoxide group, carboxyl Surface treatment using a surface treatment agent having a functional group such as an acid group, a sulfonic acid group, or a phosphonic acid group is also preferably performed.

  The hard coat layer is preferably cured using heat or active energy rays. Among them, active energy rays such as radiation, gamma rays, alpha rays, electron rays, and ultraviolet rays are more preferred, and safety and productivity are improved. In view of the above, it is particularly preferable to use an electron beam or an ultraviolet ray. In the case of curing with heat, in consideration of the heat resistance of the plastic itself, the heating temperature is preferably 140 ° C. or lower, more preferably 100 ° C. or lower.

(5-2) Forward scattering layer The forward scattering layer is used to improve viewing angle characteristics (hue and luminance distribution) in the vertical and horizontal directions when the polarizing plate of the present invention is applied to a liquid crystal display device. In the present invention, a configuration in which fine particles having different refractive indexes are dispersed in a binder is preferable. The construction of JP-A No. 199809, JP-A No. 2002-107512 or the like which defines the haze value as 40% or more can be used. In addition, in order to control the viewing angle characteristics of haze, the polarizing plate of the present invention is also preferably used in combination with “Lumisty” described in Sumitomo Chemical's technical report “Photofunctional Films” on pages 31-39. be able to.

(5-3) Anti-glare layer The anti-glare (anti-glare) layer is used to scatter reflected light and prevent reflection. The antiglare function is obtained by forming irregularities on the outermost surface (display side) of the liquid crystal display device. The haze of the optical film having an antiglare function is preferably 3 to 30%, more preferably 5 to 20%, and most preferably 7 to 20%.

The method for forming irregularities on the film surface is, for example, a method of forming irregularities on the film surface by adding fine particles (for example, JP-A No. 2000-271878), relatively large particles (particle size 0.05-2 μm). ) Is added in a small amount (0.1 to 50% by mass) (for example, Japanese Patent Application Laid-Open Nos. 2000-281410, 2000-95893, 2001-100004, and 2001). No. 281407, etc.), a method of physically transferring the uneven shape onto the film surface (for example, as an embossing method, JP-A-63-278839, JP-A-11-183710, JP-A-2000-275401) Etc.)
Etc. can be preferably used.

[Liquid crystal display device using polarizing plate]
Next, a liquid crystal display device in which the polarizing plate of the present invention is used will be described.
FIG. 2 is an example of a liquid crystal display device in which the polarizing plate of the present invention is used.

  The liquid crystal display device of the present invention shown in FIG. 2 includes a liquid crystal cell (10-13), and an upper polarizing plate 6 and a lower polarizing plate 17 that are disposed with the liquid crystal cell (10-13) interposed therebetween. The polarizing plate is sandwiched between a polarizer and a pair of transparent protective films, but is shown as an integrated polarizing plate in FIG. The liquid crystal cell includes a liquid crystal layer formed of an upper electrode substrate 10 and a lower electrode substrate 13 and liquid crystal molecules 12 sandwiched therebetween. The liquid crystal cell is different in the alignment state of liquid crystal molecules that perform ON / OFF display. However, the polarizing plate of the present invention can be used in any display mode regardless of the transmissive and reflective types.

  An alignment film (not shown) is formed on the surface of the electrode substrates 10 and 13 in contact with the liquid crystal molecules 12 (hereinafter sometimes referred to as “inner surface”), and a rubbing process or the like applied on the alignment film is performed. Thus, the alignment of the liquid crystal molecules 12 in a state where no electric field is applied or a state where a low voltage is applied is controlled. Further, on the inner surfaces of the substrates 10 and 13, a transparent electrode (not shown) capable of applying an electric field to the liquid crystal layer made of the liquid crystal molecules 12 is formed.

  The rubbing direction of the TN mode is applied in directions perpendicular to each other on the upper and lower substrates, and the magnitude of the tilt angle can be controlled by the strength and the number of rubbing times. The alignment film is formed by applying and baking a polyimide film. The magnitude of the twist angle (twist angle) of the liquid crystal layer is determined by the crossing angle of the upper and lower substrates in the rubbing direction and the chiral agent added to the liquid crystal material. Here, a chiral agent having a pitch of about 60 μm is added so that the twist angle becomes 90 °.

  The twist angle is in the vicinity of 90 ° (85 to 95 °) in the case of a notebook computer, a personal computer monitor, and a liquid crystal display device for a television, and is 0 to 70 ° in the case of use as a reflective display device such as a mobile phone. Set. In the IPS mode and the ECB mode, the twist angle is 0 °. In the IPS mode, electrodes are disposed only on the lower substrate 8 and an electric field parallel to the substrate surface is applied. In the OCB mode, there is no twist angle and the tilt angle is increased, and in the VA mode, the liquid crystal molecules 12 are aligned perpendicular to the upper and lower substrates.

  Here, the magnitude of the product Δnd of the thickness d of the liquid crystal layer and the refractive index anisotropy Δn changes the brightness during white display. Therefore, in order to obtain the maximum brightness, the range is set for each display mode.

  High contrast can be obtained by laminating so that the crossing angle of the absorption axis 7 of the upper polarizing plate 6 and the absorption axis 18 of the lower polarizing plate 17 is generally orthogonal. The crossing angle between the absorption axis 7 of the upper polarizing plate 6 of the liquid crystal cell and the rubbing direction of the upper substrate 10 varies depending on the liquid crystal display mode, but is generally set to be parallel or vertical in the TN and IPS modes. In OCB and ECB modes, it is often set to 45 °. However, the optimum value differs in each display mode for adjusting the color tone and viewing angle of the display color, and the present invention is not limited to this range.

The liquid crystal display device in which the polarizing plate of the present invention is used is not limited to the configuration of FIG. 2, and may include other members. For example, a color filter may be disposed between the liquid crystal cell and the polarizer. Moreover, the viewing angle widening film mentioned above can also be separately arranged between the liquid crystal cell and the polarizing plate. The polarizing plates 6 and 17 and the optically anisotropic layers (viewing angle widening films) 8 and 15 may be arranged in a laminated form bonded with an adhesive, and one of the liquid crystal cell side protective films is used for widening the viewing angle. It may be arranged as a so-called integrated elliptical polarizing plate.

  When the liquid crystal display device using the polarizing plate of the present invention is used as a transmission type, a backlight using a cold cathode or a hot cathode fluorescent tube, or a light emitting diode, a field emission element, or an electroluminescent element as a light source. Can be placed on the back. Further, the liquid crystal display device in which the polarizing plate of the present invention is used may be of a reflective type. In such a case, only one polarizing plate may be disposed on the observation side, and the back of the liquid crystal cell or under the liquid crystal cell. A reflective film is installed on the inner surface of the side substrate. Of course, a front light using the light source may be provided on the liquid crystal cell observation side.

  EXAMPLES Hereinafter, although this invention is described concretely based on an Example and a synthesis example, this invention is not limited at all by these specific examples.

[Synthesis of retardation increasing agent]
Synthesis Example 1: Synthesis of Exemplified Compound (101) In a reaction vessel equipped with a stirrer, raw material addition apparatus, reflux condenser and thermometer, 24.6 g (0.116 mol) of 3,4,5-trimethoxybenzoic acid, toluene After charging 100 mL and 1 mL of N, N-dimethylformamide and heating to 60 ° C., 15.2 g (0.127 mol) of thionyl chloride was slowly added dropwise and heated at 60 ° C. for 2 hours. Thereafter, a solution prepared by previously dissolving 15.1 g (0.127 mol) of 4-cyanophenol in 50 mL of acetonitrile was slowly added dropwise, and after completion of the addition, the mixture was heated and stirred at 60 ° C. for 3 hours. After cooling the reaction solution to room temperature, liquid separation operation was performed with ethyl acetate and water. After removing water from the obtained organic phase with sodium sulfate, the solvent was distilled off under reduced pressure. 100 mL was added and recrystallization operation was performed. The acetonitrile solution was cooled to room temperature, and the precipitated crystals were collected by filtration to obtain 11.0 g (yield 11%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

¹ H-NMR (CDCl ₃ ): δ 3.50 (br, 9H), 7.37 (d, 2H), 7.45 (s, 2H), 7.77 (s, 2H)
Mass spectrum: m / z 314 (M + H) ⁺
The melting point of the obtained compound was 172 to 173 ° C.

Synthesis Example 2: Synthesis of Exemplified Compound (102) A reaction vessel similar to that used in Synthesis Example 1 was charged with 106.1 g (0.5 mol) of 2,4,5-trimethoxybenzoic acid, 340 mL of toluene, and 1 mL of dimethylformamide. After heating to 60 ° C., 65.4 g (0.55 mol) of thionyl chloride was slowly added dropwise and heated at 65 to 70 ° C. for 2 hours. Thereafter, a solution prepared by previously dissolving 71.5 g (0.6 mol) of 4-cyanophenol in 150 mL of acetonitrile was slowly added dropwise. After completion of the addition, the mixture was heated and stirred at 80 to 85 ° C. for 2 hours. After cooling the reaction solution to room temperature, liquid separation operation was performed with ethyl acetate (1 L) and water. After removing water from the obtained organic phase with magnesium sulfate, about 500 mL of the solvent was distilled off under reduced pressure, and 1 L of methanol was added. And recrystallization operation was performed. The precipitated crystals were collected by filtration to obtain 125.4 g (yield 80%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

¹ H-NMR (CDCl ₃ ): δ 3.91 (s, 3H), 3.93 (s, 3H), 3.98 (s, 3H), 6.59 (s, 1H), 7.35 (d , 2H), 7.58 (s, 1H), 7.74 (d, 2H)
Mass spectrum: m / z 314 (M + H) ⁺
The melting point of the obtained compound was 116 ° C.

Synthesis Example 3: Synthesis of Exemplary Compound (103) In a reaction vessel similar to that used in Synthesis Example 1, 10.1 g (47.5 mmol) of 2,3,4-trimethoxybenzoic acid, 40 mL of toluene and 0.5 mL of dimethylformamide And heated to 80 ° C., 6.22 g (52.3 mmol) of thionyl chloride was slowly added dropwise and stirred at 80 ° C. for 2 hours. Thereafter, a solution prepared by previously dissolving 6.2 g (52.3 mmol) of 4-cyanophenol in 20 mL of acetonitrile was slowly added dropwise. After completion of the addition, the mixture was heated and stirred at 80 to 85 ° C. for 2 hours. After cooling the reaction solution to room temperature, liquid separation operation was performed with ethyl acetate and water. After removing water from the obtained organic phase with sodium sulfate, the solvent was distilled off under reduced pressure, 50 mL of methanol was added, and recrystallization operation was performed. Went. The precipitated crystals were collected by filtration to obtain 11.9 g (yield 80%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

¹ H-NMR (CDCl ₃ ): δ 3.50 (br, 9H), 7.37 (d, 2H), 7.45 (s, 2H), 7.77 (s, 2H)
Mass spectrum: m / z 314 (M + H) ⁺
The melting point of the obtained compound was 102 to 103 ° C.

Synthesis Example 4: Synthesis of Exemplary Compound (104) A reaction vessel similar to that used in Synthesis Example 1 was charged with 25.0 g (118 mmol) of 2,4,6-trimethoxybenzoic acid, 100 mL of toluene, and 1 mL of dimethylformamide. After heating to 60 ° C., 15.4 g (129 mmol) of thionyl chloride was slowly added dropwise and stirred at 60 ° C. for 2 hours. Thereafter, a solution prepared by previously dissolving 15.4 g (129 mmol) of 4-cyanophenol in 50 mL of acetonitrile was slowly added dropwise. After completion of the addition, the mixture was heated and stirred at 80 to 85 ° C. for 4.5 hours. After cooling the reaction solution to room temperature, liquid separation operation was performed with ethyl acetate and water. After removing water from the obtained organic phase with sodium sulfate, the solvent was distilled off under reduced pressure, and 500 mL of methanol and 100 mL of acetonitrile were added, Recrystallization operation was performed. The precipitated crystals were collected by filtration to obtain 10.0 g (yield 27%) of the target compound as white crystals. The compound was identified by mass spectrum.

Mass spectrum: m / z 314 (M + H) ⁺
The melting point of the obtained compound was 172 to 173 ° C.

Synthesis Example 5: Synthesis of Exemplified Compound (105) A reaction vessel similar to that used in Synthesis Example 1 was charged with 15.0 g (82.3 mmol) of 2,3-dimethoxybenzoic acid, 60 mL of toluene and 0.5 mL of dimethylformamide. Then, after heating to 60 ° C., 10.7 (90.5 mmol) of thionyl chloride was slowly added dropwise, and the mixture was heated and stirred at 60 ° C. for 2 hours. Thereafter, a solution prepared by previously dissolving 10.8 g (90.5 mmol) of 4-cyanophenol in 30 mL of acetonitrile was slowly added dropwise. After completion of the addition, the mixture was heated and stirred at 70 to 80 ° C. for 7 hours. After cooling the reaction solution to room temperature, 90 mL of isopropyl alcohol was added, and the precipitated crystals were collected by filtration to obtain 12.3 g (yield 53%) of the target compound as white crystals. The compound was identified by mass spectrum.

Mass spectrum: m / z 284 (M + H) ⁺
The melting point of the obtained compound was 104 ° C.

Synthesis Example 6: Synthesis of Exemplified Compound (106) Exemplified Compound in Synthesis Example 5 in the same manner as in Synthetic Example 5 except that 2,4-dimethoxybenzoic acid was used instead of 2,3-dimethoxybenzoic acid. (106) was synthesized.
The compound was identified by mass spectrum.
Mass spectrum: m / z 284 (M + H) ⁺
The melting point of the obtained compound was 134 to 136 ° C.

Synthesis Example 7: Synthesis of Example Compound (107) A reaction vessel similar to that used in Synthesis Example 1 was charged with 25.0 g (137 mmol) of 2,5-dimethoxybenzoic acid, 100 mL of toluene, and 1.0 mL of dimethylformamide. After heating to 60 ° C., 18.0 (151 mmol) of thionyl chloride was slowly added dropwise, and the mixture was heated and stirred at 60 ° C. for 2 hours. Thereafter, a solution prepared by previously dissolving 18.0 g (151 mmol) of 4-cyanophenol in 50 mL of acetonitrile was slowly added dropwise. After completion of the addition, the mixture was heated and stirred at 70 to 80 ° C. for 7.5 hours. After cooling the reaction solution to room temperature, liquid separation operation was performed with ethyl acetate and saturated brine, and water was removed from the obtained organic phase with sodium sulfate. Then, the solvent was distilled off under reduced pressure, and silica gel column chromatography (hexane -Purification operation with ethyl acetate (9/1, V / V)) yielded 18.8 g (yield 48%) of the target compound as white crystals. The compound was identified by mass spectrum.

Mass spectrum: m / z 284 (M + H) ⁺
The melting point of the obtained compound was 79-80 ° C.

Synthesis Example 8: Synthesis of Exemplified Compound (108) Exemplified Compound in Synthesis Example 5 in the same manner as in Synthetic Example 5 except that 2,6-dimethoxybenzoic acid was used instead of 2,3-dimethoxybenzoic acid. (108) was synthesized. The compound was identified by mass spectrum.
Mass spectrum: m / z 284 (M + H) ⁺
The melting point of the obtained compound was 130 to 131 ° C.

Synthesis Example 9: Synthesis of Exemplified Compound (111) In Synthetic Example 2, instead of using 71.5 g of 4-cyanophenol, Exemplified Compound was prepared in the same manner as in Synthetic Example 2 except that 76.9 g of 4-chlorophenol was used. (111) was obtained. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

¹ H-NMR (CDCl ₃ ): δ 3.90 (s, 3H), 3.94 (s, 3H), 3.99 (s, 3H), 6.58 (s, 1H), 7.15 (d , 2H), 7.37 (d, 2H), 7.56 (s, 1H)
Mass spectrum: m / z 323 (M + H) ⁺
The melting point of the obtained compound was 127 to 129 ° C.

Synthesis Example 10: Synthesis of Exemplified Compound (112) The same reaction vessel as used in Synthesis Example 1 was charged with 45.0 g (212 mmol) of 2,4,5-trimethoxybenzoic acid, 180 mL of toluene and 1.8 mL of dimethylformamide. After heating to 60 ° C., 27.8 g (233 mmol) of thionyl chloride was slowly added dropwise, and the mixture was heated and stirred at 60 ° C. for 2.5 hours. Thereafter, a solution prepared by previously dissolving 35.4 g (233 mmol) of methyl 4-hydroxybenzoate in 27 mL of dimethylformamide was slowly added, and the mixture was heated and stirred at 80 ° C. for 3 hours. 270 mL was added, and the precipitated crystals were collected by filtration to obtain 64.5 g (yield 88%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

¹ H-NMR (CDCl ₃ ): δ 3.95 (m, 9H), 3.99 (s, 3H), 6.57 (s, 1H), 7.28 (d, 2H), 7.57 (s , 1H) 8.11 (d, 2H)
Mass spectrum: m / z 347 (M + H) ⁺
The melting point of the obtained compound was 121 to 123 ° C.

Synthesis Example 11 Synthesis of Exemplary Compound (113) A reaction vessel similar to that used in Synthesis Example 1 was charged with 20.0 g (94.3 mmol) of 2,4,5-trimethoxybenzoic acid, 100 mL of toluene and 1 mL of dimethylformamide. After heating to 60 ° C., 12.3 g (104 mmol) of thionyl chloride was slowly added dropwise and stirred at 60 ° C. for 3.5 hours. Thereafter, a solution in which 17.7 g (104 mmol) of 4-phenylphenol was dissolved in 150 mL of toluene was slowly added, and the mixture was heated and stirred at 80 ° C. for 3 hours. The reaction solution was then cooled to room temperature, and 250 mL of methanol was added. The precipitated crystals were collected by filtration to obtain 21.2 g (yield 62%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

¹ H-NMR (CDCl ₃ ): δ 3.93 (s, 3H), 3.96 (s, 3H), 3.99 (s, 3H), 6.59 (s, 1H), 7.26-7 .75 (m, 10H)
Mass spectrum: m / z 365 (M + H) ⁺
The melting point of the obtained compound was 131-132 ° C.

Synthesis Example 12: Synthesis of Exemplified Compound (114) A reaction vessel similar to that used in Synthesis Example 1 was charged with 12.9 g (61 mmol) of 2,4,5-trimethoxybenzoic acid, 50 mL of toluene and 0.6 mL of dimethylformamide. Then, after heating to 60 ° C., 8.0 g (67 mmol) of thionyl chloride was slowly added dropwise and stirred at 60 ° C. for 3.5 hours. Thereafter, a solution prepared by previously dissolving 17.7 g (104 mmol) of 4-phenylphenol in 25 mL of acetonitrile was slowly added, and the mixture was heated and stirred at 80 ° C. for 3 hours. The reaction solution was then cooled to room temperature, and 100 mL of methanol was added. The precipitated crystals were collected by filtration to obtain 21.6 g (yield 93%) of the target compound as white crystals. The compound was identified by mass spectrum.

Mass spectrum: m / z 381 (M + H) ⁺
The melting point of the obtained compound was 91-92 ° C.

Synthesis Example 13: Synthesis of Exemplified Compound (115) In Synthetic Example 2, Exemplified Compound (115) was prepared in the same manner as in Synthetic Example 2, except that 56.4 g of phenol was used instead of 71.5 g of 4-cyanophenol. Obtained. The compound was identified by ¹ H-NMR and mass spectrum.

¹ H-NMR (CDCl ₃ ): δ 3.91 (s, 3H), 3.93 (s, 3H), 3.99 (s, 3H), 6.58 (s, 1H), 7.19-7 .27 (m, 3H), 7.42 (m, 2H), 7.58 (s, 1H)
Mass spectrum: m / z 365 (M + H) ⁺
The melting point of the obtained compound was 105 to 108 ° C.

Synthesis Example 14: Synthesis of Exemplified Compound (116) In Synthetic Example 2, instead of using 71.5 g of 4-cyanophenol, Exemplified Compound (S) was prepared in the same manner as in Synthetic Example 2 except that 74.4 g of 4-methoxyphenol was used. 116) could be obtained. The compound was identified by ¹ H-NMR and mass spectrum.

¹ H-NMR (CDCl ₃ ): δ 3.84 (s, 3H), 3.92 (s, 3H), 3.93 (s, 3H), 3.99 (s, 3H), 6.58 (s , 1H), 6.92 (d, 2H), 7.12 (d, 2H), 7.42 (m, 2H), 7.58 (s, 1H)
Mass spectrum: m / z 319 (M + H) ⁺
The melting point of the obtained compound was 102 to 103 ° C.

Synthesis Example 15: Synthesis of Exemplified Compound (117) In Synthetic Example 2, instead of using 71.5 g of 4-cyanophenol, Exemplified Compound (S) was prepared in the same manner as in Synthetic Example 2 except that 73.3 g of 4-ethylphenol was used. 117) was obtained. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.
Mass spectrum: m / z 317 (M + H) ⁺
The melting point of the obtained compound was 70 to 71 ° C.

Synthesis Example 16: Synthesis of Exemplified Compound (124) A reaction vessel similar to that used in Synthesis Example 1 was charged with 27.3 g (164 mmol) of 4-ethoxybenzoic acid, 108 mL of toluene and 1 mL of dimethylformamide and heated to 60 ° C. Then, 21.5 g (181 mmol) of thionyl chloride was slowly added dropwise, and the mixture was stirred with heating at 60 ° C. for 2 hours. Thereafter, a solution in which 25.0 g (181 mmol) of 4-ethoxyphenol was previously dissolved in 50 mL of acetonitrile was slowly added, and the mixture was heated and stirred at 80 ° C. for 4 hours. After cooling the reaction solution to room temperature, 100 mL of methanol was added. The precipitated crystals were collected by filtration to obtain 30.6 g (yield 65%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

¹ H-NMR (CDCl ₃ ): δ 1.48-1.59 (m, 6H), 4.05 (q, 2H), 4.10 (q, 2H), 6.89-7.00 (m, 4H), 7.10 (d, 2H), 8.12 (d, 2H)
Mass spectrum: m / z 287 (M + H) ⁺
The melting point of the obtained compound was 113 to 114 ° C.

Synthesis Example 17: Synthesis of Exemplified Compound (125) A reaction vessel similar to that used in Synthesis Example 1 was charged with 24.7 g (149 mmol) of 4-ethoxybenzoic acid, 100 mL of toluene and 1 mL of dimethylformamide and heated to 60 ° C. After that, 19.5 g (164 mmol) of thionyl chloride was slowly added dropwise, and the mixture was stirred with heating at 60 ° C. for 2 hours. Thereafter, a solution prepared by previously dissolving 25.0 g (165 mmol) of 4-propoxyphenol in 50 mL of acetonitrile was slowly added and stirred at 80 ° C. for 4 hours. After cooling the reaction solution to room temperature, 100 mL of methanol was added. The precipitated crystals were collected by filtration, 100 mL of methanol was added to the resulting solid, and recrystallization was performed. The obtained crystals were collected by filtration to obtain 33.9 g of the target compound as white crystals (yield 76%). Obtained. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

¹ H-NMR (CDCl ₃ ): δ 1.04 (t, 3H), 1.45 (t, 3H), 1.82 (q, 2H), 3.93 (q, 2H), 4.04 (q , 2H), 6.89-7.00 (m, 4H), 7.10 (d, 2H), 8.12 (d, 2H)
Mass spectrum: m / z 301 (M + H) ⁺
The melting point of the obtained compound was 107 ° C.

Synthesis Example 18: Synthesis of Exemplary Compound (127) Synthesis was performed in the same manner as in Synthesis Example 16 except that 29.5 g of 4-propoxybenzoic acid was used instead of 27.3 g of 4-ethoxybenzoic acid in Synthesis Example 16. did. The compound was identified by mass spectrum.
Mass spectrum: m / z 301 (M + H) ⁺
The melting point of the obtained compound was 88-89 ° C.

Synthesis Example 19: Synthesis of Exemplified Compound (128) Synthesis was performed in the same manner as in Synthesis Example 17 except that, in Synthesis Example 17, instead of using 24.7 g of 4-ethoxybenzoic acid, 26.8 g of 4-propoxybenzoic acid was used. did. The compound was identified by mass spectrum.
Mass spectrum: m / z 315 (M + H) ⁺
The melting point of the obtained compound was 92 ° C.

Synthesis Example 20: Synthesis of Exemplary Compound (140) A reaction vessel similar to that used in Synthesis Example 1 was charged with 20.0 g (109 mmol) of 2,4-dimethoxybenzoic acid, 80 mL of toluene, and 0.8 mL of dimethylformamide. After heating to 60 ° C., 14.4 g (121 mmol) of thionyl chloride was slowly added dropwise and stirred at 60 ° C. for 3.5 hours. Thereafter, a solution in which 20.5 g (121 mmol) of 4-phenylphenol was previously dissolved in 50 mL of dimethylformamide was slowly added, and the mixture was stirred with heating at 80 ° C. for 6 hours. In addition, the precipitated crystals were collected by filtration to obtain 31.7 g (yield 86%) of the target compound as white crystals. The compound was identified by mass spectrum.
Mass spectrum: m / z 335 (M + H) ⁺
The melting point of the obtained compound was 161-162 ° C.

Synthesis Example 21: Synthesis of Exemplary Compound (142) A reaction vessel similar to that used in Synthesis Example 1 was charged with 30.0 g (165 mmol) of 2,4-dimethoxybenzoic acid, 120 mL of toluene and 1.2 mL of dimethylformamide. After heating to 60 ° C., 21.6 g (181 mmol) of thionyl chloride was slowly added dropwise and stirred at 60 ° C. for 2 hours. Thereafter, a solution prepared by previously dissolving 27.6 g (181 mmol) of methyl 4-hydroxyhydroxybenzoate in 40 mL of dimethylformamide was slowly added, and the mixture was heated and stirred at 80 ° C. for 6 hours. After cooling the reaction solution to room temperature, 140 mL of methanol was added, and the precipitated crystals were collected by filtration to obtain 24.4 g (yield 47%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

¹ H-NMR (CDCl ₃ ): δ 3.92 (m, 9H), 6.56 (m, 2H), 7.27 (m, 2H), 8.09 (m, 3H)
Mass spectrum: m / z 317 (M + H) ⁺
The melting point of the obtained compound was 122-123 ° C.

Synthesis Example 22: Synthesis of Exemplary Compound (201) In a reaction vessel similar to that used in Synthesis Example 1, 40.1 g (189 mmol) of 2,4,5-trimethoxybenzoic acid, 16.75 g of 4,4′-dihydroxybiphenyl (90 mmol), 200 mL of toluene and 2 mL of dimethylformamide were charged and heated to 70 ° C., 23.6 g (198 mmol) of thionyl chloride was slowly added dropwise, and the mixture was heated and stirred at 70 ° C. for 2.5 hours. Thereafter, the reaction solution was cooled to room temperature, 300 mL of methanol was added, and the precipitated crystals were collected by filtration to obtain 48.4 g (yield 94%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz).

¹ H-NMR (CDCl ₃ ): δ 3.93 (s, 6H), 3.95 (s, 6H), 3.99 (s, 6H), 6.58 (s, 2H), 7.28 (d , 4H), 7.62 (m, 6H) The melting point of the obtained compound was 227 to 229 ° C.

Synthesis Example 23: Synthesis of Exemplary Compound (202) In a reaction vessel similar to that used in Synthesis Example 1, 34 g (160 mmol) of 2,4,5-trimethoxybenzoic acid, 15 g of 4,4′-dihydroxy-3-fluorobiphenyl (73 mmol), 110 mL of toluene and 1.6 mL of dimethylformamide were charged and heated to 70 ° C., 20.9 g (176 mmol) of thionyl chloride was slowly added dropwise, and the mixture was heated and stirred at 70 ° C. for 2.5 hours. Thereafter, the reaction solution was cooled to room temperature, 300 mL of methanol was added, and the precipitated crystals were collected by filtration to obtain 37 g (yield 86%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz).

¹ H-NMR (CDCl ₃ ): δ 3.93 (s, 6H), 3.95 (s, 6H), 4.00 (s, 6H), 6.59 (s, 2H), 7.26-7 .45 (m, 5H), 7.63 (m, 4H)
The melting point of the obtained compound was 197 to 199 ° C.

Synthesis Example 24 Synthesis of Exemplary Compound (203) In a reaction vessel similar to that used in Synthesis Example 1, 23.3 g (110 mmol) of 2,4,5-trimethoxybenzoic acid, 4,4′-dihydroxy-3-chloro After charging 15 g (50 mmol) of biphenyl, 75 mL of toluene and 1.1 mL of dimethylformamide and heating to 70 ° C., 14.4 g (121 mmol) of thionyl chloride was slowly added dropwise and stirred at 80 ° C. for 2.5 hours. did. Thereafter, the reaction solution was cooled to room temperature, 250 mL of methanol was added, and the precipitated crystals were collected by filtration to obtain 26 g (yield 85%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz).

¹ H-NMR (CDCl ₃ ): δ 3.90-4.00 (m, 18H), 6.59 (s, 2H), 7.26-7.70 (m, 9H)
The melting point of the obtained compound was 168-170 ° C.

Synthesis Example 25: Synthesis of Exemplary Compound (204) In a reaction vessel similar to that used in Synthesis Example 1, 30.3 g (143 mmol) of 4,4,5-trimethoxybenzoic acid and 4,4′-dihydroxy-3-methyl After charging 15 g (65 mmol) of biphenyl, 100 mL of toluene and 1.4 mL of dimethylformamide and heating to 70 ° C., 18.7 g (157 mmol) of thionyl chloride was slowly added dropwise and stirred at 70 ° C. for 2.5 hours. did. Thereafter, the reaction solution was cooled to room temperature, 300 mL of methanol was added, and the precipitated crystals were collected by filtration to obtain 27.4 g (yield 72%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

¹ H-NMR (CDCl ₃ ): δ 2.31 (s, 3H), 3.95 (s, 6H), 4.00 (s, 6H), 6.60 (s, 2H), 7.10 (m , 2H), 7.27 (m, 3H), 7.40 (m, 2H), 7.63 (d, 2H)
Mass spectrum: m / z 589 (M + H) ⁺
The melting point of the obtained compound was 188 to 189 ° C.

Synthesis Example 26: Synthesis of Exemplified Compound (205) In a reaction vessel similar to that used in Synthesis Example 1, 5,72 g (26.9 mmol) of 2,4,5-trimethoxybenzoic acid and 3.5 g (27 mmol) of diisopropylethylamine were added. ) And 20 mL of tetrahydrofuran, and cooled with ice water, 3.1 g (27 mmol) of methanesulfonyl chloride was slowly added dropwise, and the mixture was stirred at room temperature for 2 hours. After cooling to ice water, a solution prepared by dissolving 2.9 g (13.7 mmol) of bis (4-hydroxyphenyl) acetylene and 3.5 g (27 mmol) of diisopropylethylamine in 40 mL of tetrahydrofuran was slowly added. The mixture was stirred at room temperature for 3 hours and at 50 ° C. for 1 hour. Thereafter, 160 mL of water was added, and the resulting crystals were collected by filtration, 100 mL of methanol was added, recrystallization was performed, and the precipitated crystals were collected by filtration to obtain 3.0 g of the target compound as white crystals (yield 19%). )Obtained. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

¹ H-NMR (CDCl ₃ ): δ 3.93 (s, 6H), 3.95 (s, 6H), 3.99 (s, 6H), 6.57 (s, 2H), 7.24 (m , 4H), 7.58 (m, 6H)
Mass spectrum: m / z 599 (M + H) ⁺
The melting point of the obtained compound was 201 to 203 ° C.

Synthesis Example 27 Synthesis of Exemplary Compound (206) (1) Synthesis of 2,4,5-trimethoxybenzoic acid-4-ethynylanilide In a reaction vessel similar to that used in Synthesis Example 1, 2,4,5-trimethoxybenzoic acid was added. After charging 21.2 g (100 mmol) of acid, 12.9 g (100 mmol) of diisopropylethylamine and 126 mL of tetrahydrofuran and cooling with ice water, 11.4 g (100 mmol) of methanesulfonyl chloride was slowly added dropwise. Stir for hours at room temperature. Thereafter, the mixture was cooled to ice water, and a solution prepared by previously dissolving 11.7 g (100 mmol) of 4-ethylaniline and 12.9 g (100 mmol) of diisopropylethylamine in 42 mL of tetrahydrofuran was slowly added, followed by stirring at room temperature for 6 hours. did. Thereafter, 200 mL of ethyl acetate was added, and the organic phase was washed in this order with water, a saturated aqueous sodium hydrogen carbonate solution, 0.5 mol / L aqueous hydrochloric acid, and saturated brine. Sodium sulfate was added to the organic phase, dehydration was performed, sodium sulfate was removed by filtration, and the organic solvent was distilled off under reduced pressure. Next, 350 mL of methanol was added thereto and recrystallization was performed, and the precipitated crystals were collected by filtration to obtain 15.0 g (yield 48%) of the target compound as white crystals.

(2) Synthesis of Exemplified Compound (206) In the same reaction vessel as that used in Synthesis Example 1, 3.1 g (10 mmol) of 2,4,5-trimethoxybenzoic acid-4-ethynylanilide obtained above was obtained. , 4,5-trimethoxybenzoic acid-4-iodophenyl (4.1 g, 10 mmol), triethylamine (5.56 mL, 40 mmol) and tetrahydrofuran (15 mL) were charged, and the mixture was stirred at room temperature under a nitrogen atmosphere. 22.8 mg (0.12 mmol), triphenylphosphine 131 mg (0.5 mmol), and bis (triphenylphosphine) palladium dichloride 70 mg (0.1 mmol) were added, and the mixture was heated and stirred at 60 ° C. for 3 hours. Thereafter, the reaction solution was cooled to room temperature, and 200 mL of water was added. The obtained crystals were filtered and recrystallized with 100 mL of methanol to obtain 5.6 g (yield 94%) of the target compound as yellowish white crystals.
The compound was identified by ¹ H-NMR (400 MHz).

¹ H-NMR (DMSO-d6): δ 3.92 (s, 3H), 3.93 (s, 3H), 4.05 (m, 9H) 4.15 (s, 3H) 6.96 (br, 2H), 7.46 (d, 2H), 7.55 (s, 1H), 7.62 (s, 1H), 7.69 (d, 2H), 7.76 (d, 2H), 7. 98 (d, 2H), 10.30 (s, 1H)
The melting point of the obtained compound was 216 to 218 ° C.

Synthesis Example 28: Synthesis of exemplary compound (223) Exemplary compound (223) was synthesized according to the following scheme.

(1) Synthesis of Intermediate (C) After heating 300 g of 2,4,5-trimethoxybenzoic acid, 1200 ml of toluene and 12 ml of dimethylformamide to 80 ° C., 112.1 ml of thionyl chloride was slowly added dropwise over 45 minutes, After the dropping, the mixture was heated and stirred at 80 ° C. for 1 hour. Thereafter, a solution in which 214.8 g of 4-hydroxybenzoic acid was dissolved in 800 ml of dimethylformamide was added to the reaction solution, and further reacted at 80 ° C. for 2 hours. After the reaction, toluene was distilled off and then cooled to room temperature. Subsequently, 2500 ml of methanol was added, and the precipitated crystals were collected by filtration to obtain 263.8 g (yield 56.3%) of intermediate (C) as white crystals.

(2) Synthesis of Exemplified Compound (223) After heating and refluxing 108.4 g of Intermediate (C), 7.24 g of dimethylaminopyridine, 32.67 g of Compound (D) and 500 ml of methylene chloride, 67.31 g of dicyclohexylcarbodiimide A 200 ml solution of methylene chloride was slowly added dropwise over 30 minutes, and the mixture was further refluxed for 2 hours. Thereafter, the reaction solution was cooled to room temperature, the precipitated crystals (dicyclohexylurea) were filtered off, and the filtrate was concentrated under reduced pressure. The residue was recrystallized three times with methanol to obtain 91.42 g (yield 75.8%) of Exemplary Compound (1) as white crystals. The compound was identified by ¹ H-NMR (400 MHz).

¹ H-NMR (CDCl ₃ ) δ 3.93 (s, 6H), 3.95 (s, 6H), 4.00 (s, 6H), 6.61 (s, 2H), 7.32 (d, 4H), 7.38 (d, 4H), 7.61 (s, 2H), 7.68 (d, 4H), 8.29 (d, 4H)
The melting point of the obtained compound was 199 to 200 ° C.

[Preparation of cellulose acylate film]
Example 1-1 Production of Cellulose Acylate Film (CAF1) [Preparation of Cellulose Acylate Stock Solution (CAL-1)]
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acetate stock solution (CAL-1).

{Composition of cellulose acylate stock solution (CAL-1)}
Cellulose acylate 100.0 parts by mass Acetylation degree 2.79
Triphenyl phosphate (plasticizer) 8.0 parts by weight Biphenyl phosphate (plasticizer) 4.0 parts by weight Methylene chloride (first solvent) 402.0 parts by weight Methanol (second solvent) 60.0 parts by weight

[Preparation of matting agent solution (Ma-1)]
The following composition was charged into a disperser and stirred to dissolve each component to prepare a matting agent solution (Ma-1).

{Matting agent solution (Ma-1) composition}
Silica particles having an average particle diameter of 20 nm 2.0 parts by mass “AEROSIL R972” manufactured by Nippon Aerosil Co., Ltd. Methylene chloride (first solvent) 75.0 parts by mass Methanol (second solvent) 12.7 parts by mass Cellulose acylate stock solution ( CAL-1) 10.3 parts by mass

[Preparation of Retardation Raising Agent Solution (Re-1)]
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a retardation increasing agent solution (Re-1).

{Composition of retardation increasing agent solution (Re-1)}
Retardation raising agent (302) 20.0 parts by mass Methylene chloride (first solvent) 58.4 parts by mass Methanol (second solvent) 8.7 parts by mass Cellulose acylate solution stock solution (CAL-1) 12.8 parts by mass

[Production of Cellulose Acylate Film (CAF1)]
After filtering 94.5 parts by mass of the cellulose acylate stock solution (CAL-1), 1.3 parts by mass of the matting agent solution (Ma-1) and 4.2 parts by mass of the retardation increasing agent solution (Re-1), respectively. Mix and cast using a band caster. The film obtained with a residual solvent content of 43% by mass was peeled from the band, and the film was transported at a speed of 30 m / min at an atmospheric temperature of 140 ° C., using a tenter, and at a stretching speed of 48% / min, 120% And then held at 140 ° C. for 30 seconds. The residual solvent content at the start of stretching was 25% by mass, and the I / O ratio of the residual solvent was 0.9. Thereafter, the clip was removed and dried at 130 ° C. for 40 minutes to produce a cellulose acylate film (CAF1). The residual solvent amount of the completed cellulose acylate film was 0.2% by mass.

Examples 1-2 and 1-3: Preparation of cellulose acylate films (CAF2) and (CAF3) [Preparation of cellulose acylate stock solutions (CAL-2) and (CAL-3)]
In the preparation of cellulose acylate stock solution (CAL-1), instead of using cellulose acylate having an acetylation degree of 2.79, cellulose acylate having an acetylation degree of 2.75 or an acetylation degree of 2.83 was used. Similarly, cellulose acylate stock solutions (CAL-2) and (CAL-3) were prepared.

[Preparation of matting agent solutions (Ma-2) and (Ma-3)]
In the preparation of the matting agent solution (Ma-1), instead of using the cellulose acylate stock solution (CAL-1), except that the cellulose acylate stock solution (CAL-2) or (CAL-2) is used, respectively, Matting agent solutions (Ma-2) and (Ma-3) were prepared.

[Preparation of Retardation Raising Agent Solution (Re-2)]
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a retardation increasing agent solution (Re-2).

{Composition of Retardation Raising Agent Solution (Re-2)}
Retardation increasing agent (112) 14.9 parts by mass Retardation increasing agent (302) 2.0 parts by mass Methylene chloride (first solvent) 58.4 parts by mass Methanol (second solvent) 8.7 parts by mass Cellulose acylate Solution stock solution (CAL-1) 12.8 parts by mass

[Preparation of Retardation Raising Agent Solution (Re-3)]
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a retardation increasing agent solution (Re-3).

{Composition of retardation increasing agent solution (Re-3)}
Retardation raising agent (223) 11.0 parts by mass Methylene chloride (first solvent) 58.4 parts by mass Methanol (second solvent) 8.7 parts by mass Cellulose acylate solution stock solution (CAL-1) 12.8 parts by mass

[Production of Cellulose Acylate Films (CAF2) and (CAF3)]
In the production of the cellulose acylate film (CAF1), instead of using the cellulose acylate stock solution (CAL-1), the matting agent solution (Ma-1) and the retardation increasing agent solution (Re-1), the cellulose acylate stock solution ( CAL-2), matting agent solution (Ma-2) and retardation increasing agent solution (Re-2), or cellulose acylate stock solution (CAL-3), matting agent solution (Ma-3) and retardation increasing agent solution Example 1 except that (Re-3) was used, and the film was produced at the same time except that the conveyance speed, the draw ratio, the draw speed, the residual solvent content at the start of drawing and the I / O ratio were changed to those shown in Table 2. -1, cellulose acylate films (CAF2) and (CAF3) were produced.
Table 1 shows the types of cellulose acylate used for the production of the cellulose acylate films (CAF2) and (CAF3), the types of retardation increasing agents, and their addition amounts.

Example 1-4: Production of cellulose acylate film (CAF4) [Preparation of cellulose acylate stock solution (CAL-4)]
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acetate stock solution (CAL-4).

{Composition of cellulose acylate stock solution (CAL-4)}
Cellulose acylate 100.0 parts by mass Acetylation degree 1.80, propionylation degree 0.90
Triphenyl phosphate (plasticizer) 9.0 parts by weight Ethylphthalylethyl glycolate (plasticizer) 3.5 parts by weight Methylene chloride (first solvent) 362.0 parts by weight Ethanol (second solvent) 100.0 parts by weight

[Preparation of matting agent solution (Ma-4)]
The following composition was charged into a disperser and stirred to dissolve each component to prepare a matting agent solution (Ma-4).

{Composition of matting agent solution (Ma-4)}
Silica particles having an average particle size of 20 nm 2.0 parts by mass “AEROSIL R972” manufactured by Nippon Aerosil Co., Ltd. Methylene chloride (first solvent) 75.0 parts by mass Ethanol (second solvent) 12.7 parts by mass Cellulose acylate stock solution ( CAL-4) 10.3 parts by mass

[Preparation of Retardation Raising Agent Solution (Re-4)]
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a retardation increasing agent solution (Re-4).

{Composition of retardation increasing agent solution (Re-4)}
Retardation increasing agent (302) 20.0 parts by mass Methylene chloride (first solvent) 58.4 parts by mass Ethanol (second solvent) 8.7 parts by mass Cellulose acylate solution stock solution (CAL-4) 12.8 parts by mass

[Production of Cellulose Acylate Film (CAF4)]
94.5 parts by mass of the cellulose acylate stock solution (CAL-4), matting agent solution (Ma-
4) 1.3 parts by mass and 3.4 parts by mass of the retardation increasing agent solution (Re-4) were filtered, mixed, and cast using a band casting machine. The film obtained with a residual solvent content of 45% by mass was peeled off from the band, and the film was transported at a rate of 10 m / min at an ambient temperature of 140 ° C., using a tenter and 130% at a stretching rate of 36% / min. And then held at 140 ° C. for 30 seconds. The residual solvent content at the start of stretching was 27% by mass, and the I / O ratio of the residual solvent was 2.2. Thereafter, the clip was removed and dried at 130 ° C. for 40 minutes to produce a cellulose acylate film (CAF4). The residual solvent amount of the completed cellulose acylate film was 0.2% by mass.

Examples 1-5 and 1-6: Preparation of cellulose acylate films (CAF5) and (CAF6) [Preparation of cellulose acylate stock solutions (CAL-5) and (CAL-6)]
Instead of using cellulose acylate having a degree of acetylation of 1.80 and a degree of propionylation of 0.90 in the preparation of a cellulose acylate stock solution (CAL-4), cellulose having a degree of acetylation of 1.70 and a degree of propionylation of 0.95 Cellulose acylate stock solutions (CAL-5) and (CAL-6) were prepared in the same manner except for using acylate or cellulose acylate having an acetylation degree of 1.83 and a propionylation degree of 0.91.

[Preparation of matting agent solutions (Ma-5) and (Ma-6)]
In the preparation of the matting agent solution (Ma-4), instead of using the cellulose acylate stock solution (CAL-4), except that the cellulose acylate stock solution (CAL-5) or (CAL-6) is used, respectively, Matting agent solutions (Ma-5) and (Ma-6) were prepared.

[Preparation of Retardation Raising Agent Solution (Re-5)]
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a retardation increasing agent solution (Re-5).

{Composition of Retardation Raising Agent Solution (Re-5)}
Retardation increasing agent (112) 26.0 parts by mass Methylene chloride (first solvent) 53.2 parts by mass Ethanol (second solvent) 7.9 parts by mass Cellulose acylate solution stock solution (CAL-4) 12.8 parts by mass

[Preparation of Retardation Raising Agent Solution (Re-6)]
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a retardation increasing agent solution (Re-6).

{Composition of retardation increasing agent solution (Re-6)}
Retardation increasing agent (223) 11.2 parts by mass Retardation increasing agent (206) 17.6 parts by mass Methylene chloride (first solvent) 50.8 parts by mass Ethanol (second solvent) 7.6 parts by mass Cellulose acylate Solution stock solution (CAL-4) 12.8 parts by mass

[Production of Cellulose Acylate Films (CAF5) and (CAF6)]
In the production of the cellulose acylate film (CAF4), instead of using the cellulose acylate stock solution (CAL-4), the matting agent solution (Ma-4) and the retardation increasing agent solution (Re-4), the cellulose acylate stock solution ( CAL-5), matting agent solution (Ma-5) and retardation increasing agent solution (Re-5), or cellulose acylate stock solution (CAL-6), matting agent solution (Ma-6) and retardation increasing agent solution (Re-6)
In the production of a film, the same as Example 1-4, except that the conveying speed, stretching ratio, stretching speed, residual solvent content at the start of stretching, and I / O ratio were changed to the contents shown in Table 2. Thus, cellulose acylate films (CAF5) and (CAF6) were produced.
Table 1 shows the types of cellulose acylate used for the production of cellulose acylate films (CAF5) and (CAF6), the types of retardation increasing agents, and the amounts added.

Example 1-7: Production of Cellulose Acylate Film (CAF7) In Example 1-4, the conveyance speed, the draw ratio, the draw speed, the residual solvent content at the start of drawing, and the I / O ratio are shown. A cellulose acylate film (CAF7) was produced in the same manner as in Example 1-4 except that the content was changed to 2.

Comparative Example 1-1: Production of Cellulose Acylate Film (CALF8) [Preparation of Cellulose Acylate Stock Solution (CAL-7)]
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acetate stock solution (CAL-7).

{Composition of cellulose acylate stock solution (CAL-7)}
Cellulose acylate 100.0 parts by mass Acetylation degree 2.79
Triphenyl phosphate (plasticizer) 8.0 parts by weight Biphenyl phosphate (plasticizer) 4.0 parts by weight Methylene chloride (first solvent) 457.0 parts by weight Methanol (second solvent) 5.0 parts by weight

[Preparation of matting agent solution (Ma-7)]
The following composition was charged into a disperser and stirred to dissolve each component to prepare a matting agent solution (Ma-7).

{Matting agent solution (Ma-7) composition}
Silica particles having an average particle diameter of 20 nm 2.0 parts by mass “AEROSIL R972” manufactured by Nippon Aerosil Co., Ltd. Methylene chloride (first solvent) 82.0 parts by mass Methanol (second solvent) 5.7 parts by mass Cellulose acylate stock solution ( CAL-7) 10.3 parts by mass

[Preparation of Retardation Raising Agent Solution (Re-7)]
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a retardation increasing agent solution (Re-7).

{Composition of retardation increasing agent solution (Re-7)}
Retardation increasing agent (302) 20.0 parts by mass Methylene chloride (first solvent) 63.4 parts by mass Methanol (second solvent) 3.7 parts by mass Cellulose acylate solution (CAL-7) 12.8 parts by mass

[Production of Cellulose Acylate Film (CAF8)]
After filtering 94.5 parts by mass of the cellulose acylate stock solution (CAL-7), 1.3 parts by mass of the matting agent solution (Ma-7) and 4.2 parts by mass of the retardation increasing agent solution (Re-7), respectively. Mix and cast using a band caster. The film obtained with a residual solvent content of 15% by mass was peeled off from the band, and the film was conveyed at a rate of 20 m / min at an ambient temperature of 170 ° C., using a tenter, and at a stretching rate of 48% / min, 120% And then held at 140 ° C. for 30 seconds. The residual solvent content at the start of stretching was 5% by mass, and the I / O ratio of the residual solvent was 0.21. Thereafter, the clip was removed and dried at 130 ° C. for 40 minutes to produce a cellulose acylate film (CAF8). The residual solvent amount of the completed cellulose acylate film was 0.1% by mass.

Comparative Example 1-2: Preparation of Cellulose Acylate Film (CAF9) In Example 1-4, the conveyance speed, the draw ratio, the draw speed, the residual solvent content at the start of drawing, and the I / O ratio are shown. A cellulose acylate film (CAF9) was produced in the same manner as in Example 1-4 except that the content was changed to 2.

[Measurement of film characteristic values]
[Measurement of thickness distribution and Re distribution]
For the cellulose acylate films (CAF1) to (CAF9), the film thickness and Re ₅₉₀ and Rth ₅₉₀ were measured at a total of 100 locations in the longitudinal direction of 1 m and the width direction of 1 m every 10 cm, and the average value and the standard deviation were obtained.
Re and Rth were measured with an automatic birefringence meter “KOBRA 21ADH” (manufactured by Oji Scientific Instruments) at 25 ° C. and 60% RH.

[X-ray measurement]
Using “RINT RAPID” manufactured by Rigaku Denki Co., Ltd., X-rays were generated at 40 kV-36 mA using a Cu tube as the X-ray source. The collimator was 0.8 mmφ, and the film sample was fixed using a transmission sample stage. The exposure time was 600 seconds. In this way, the degree of orientation (orientation order parameter) P _o on the film surface and the average degree of orientation P _t at the total thickness of the film were measured, and P _o / P _t was determined.
The results are shown in Table 3.

  From the results shown in Table 3, it can be seen that the cellulose acylate film of the present invention has thickness unevenness eliminated as compared with the comparative sample.

[Preparation of polarizing plate]
Examples 11-1 to 11-7 and Comparative Examples 11-1 to 11-2
[Saponification treatment of cellulose acylate film]
Cellulose acylate films (CAF1) to (CAF9) prepared in Examples 1-1 to 1-7 and Comparative Examples 1-1 to 1-2 were respectively added to 1.4 mol / L sodium hydroxide aqueous solution. It was immersed for 2 minutes at 55 ° C., then washed in a water bath at room temperature, and neutralized with 0.05 mol / L sulfuric acid at 30 ° C. Next, it was washed again in a room temperature water bath and further dried with hot air at 110 ° C. In this way, the surfaces of the cellulose acylate films (CAF1) to (CAF9) were each saponified.

  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.

[Production of polarizer]
A polarizer was produced by adsorbing iodine to the stretched PVA film, and the cellulose acylate film (CAF1) produced in Example 1-1 was attached to one side of the polarizer using a PVA adhesive. The transmission axis of the polarizer and the slow axis of the cellulose acylate film were arranged in parallel.

  Further, “Fujitac TD80UF” saponified as described above was attached to the opposite side of the polarizer using a PVA adhesive. In this way, a polarizing plate (P1-1) was produced.

  For the cellulose acylate films (CAF 2 to 9), polarizing plates (P1-2) to (P1-7) and (PR1-1) to (PR1-2) were produced in the same manner. Table 4 shows the structure of the obtained polarizing plate.

Example 21-1 and Comparative Example 21-1
[Production and Evaluation of VA Mode Liquid Crystal Display Device 1]
A liquid crystal display device shown in FIG. 3 was produced.
That is, from the observation direction (upper), an upper polarizing plate, a VA mode liquid crystal cell (upper substrate, liquid crystal layer, lower substrate) and a lower polarizing plate were stacked, and a backlight light source was further arranged.
In the following example, a commercially available polarizing plate “HLC2-5618” {manufactured by Sanritz Co., Ltd.} is used for the upper polarizing plate, and the polarizing plate of the present invention is used for the lower polarizing plate.

[Production of liquid crystal cell]
The liquid crystal cell has a cell gap between substrates of 3.6 μm and a liquid crystal material having negative dielectric anisotropy (“MLC6608” manufactured by Merck & Co., Inc.) is dropped and sealed between the substrates. Was 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 300 nm. The liquid crystal material was aligned so as to be vertically aligned.

  The above-mentioned super high contrast product “HLC2-5618” is used for the upper polarizing plate of the liquid crystal display device (FIG. 3) using the vertical alignment type liquid crystal cell obtained above, and the embodiment is used for the lower polarizing plate. The polarizing plate (P1-3) produced in 11-3 is put on the liquid crystal cell via an adhesive so that the cellulose acylate film (CAF3) of the present invention which is one protective film is on the liquid crystal cell side. Pasted. 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.

  Next, the cellulose acylate film (CAF9) produced in Comparative Example 2 was used, and the polarizing plate (PR1-2) produced in Comparative Example 12 was also used for the lower polarizing plate in the same manner as described above. A device was made.

  It was found that the liquid crystal display device using the polarizing plate (P1-3) of the present invention was preferable because there was no display unevenness as compared with the liquid crystal display device using the polarizing plate (PR1-2) of the comparative example.

Example 31-1
[Production and Evaluation of VA Mode Liquid Crystal Display Device 2]
[Production of liquid crystal cell]
1 part by mass of octadecyldimethylammonium chloride (coupling agent) was added to 100 parts by mass of a 3% by mass aqueous solution of PVA. This was spin-coated on a glass substrate with an ITO electrode, heat-treated at 160 ° C., and then rubbed to form a vertical alignment film. The rubbing treatment was performed in opposite directions on the two glass substrates. Two glass substrates were opposed to each other so that the cell gap (d) was 5 μm. A liquid crystal compound (Δn: 0.08) mainly composed of ester and ethane was injected into the cell gap to produce a vertically aligned liquid crystal cell. The product of Δn and d (that is, retardation of the liquid crystal layer) was 400 nm.

The polarizing plate (P1-2) produced in Example 11-2 was preconditioned in a temperature and humidity condition of 25 ° C. and 60% RH, and then wrapped in a moisture-proof bag and left for 3 days. The bag was a packaging material having a laminated structure of polyethylene terephthalate / aluminum / polyethylene, and the moisture permeability was 1 × 10 ⁻⁵ g / m ² · day or less.

  Under an environment of 25 ° C. and 60% RH, the polarizing plate (P1-2) was taken out and attached to both surfaces of the vertically aligned liquid crystal cell prepared above by using an adhesive sheet to prepare a liquid crystal display device.

  It was found that the liquid crystal display device using the polarizing plate of the present invention is preferable since there is no display unevenness.

Example 12
[Preparation of polarizing plate]
[Preparation of optical compensation sheet]
(Saponification treatment of cellulose acylate film)
On the cellulose acylate film (CAF1) produced in Example 1-1, a solution having the following composition was applied at 6.0 mL / m ^{2 and} dried at 60 ° C. for 10 seconds. The surface of the film was washed with running water for 10 seconds, and air at 25 ° C. was blown to dry the film surface.

(Saponification composition)
Isopropyl alcohol 818 parts by weight Water 167 parts by weight Propylene glycol 187 parts by weight “EMALEX” manufactured by Nippon Emulsion Co., Ltd. 12 parts by weight Potassium hydroxide 67 parts by weight

(Formation of alignment film)
On the saponified cellulose acylate (CAF1), a coating solution having the following composition was applied at 24 mL / m ² with a # 14 wire bar coater. Drying was performed with warm air of 60 ° C. for 60 seconds, and further with warm air of 90 ° C. for 150 seconds.
Next, the formed film was rubbed in the direction of 45 ° on the stretching direction (substantially coincident with the slow axis) on the cellulose acylate (CAF1) (transparent support).

(Composition of alignment film coating solution)
Modified polyvinyl alcohol having the following structure 20 parts by mass Water 360 parts by mass Methanol 120 parts by mass Glutaraldehyde (crosslinking agent) 1.0 part by mass

(Formation of optically anisotropic layer)
On the alignment layer, 91 parts by mass of a discotic compound having the following structure, 9 parts by mass of ethylene oxide-modified trimethylolpropane triacrylate “V # 360” (manufactured by Osaka Organic Chemical Co., Ltd.), cellulose acetate butyrate “CAB531-1” ( 1.5 parts by mass of Eastman Chemical Co., Ltd., 3 parts by mass of photopolymerization initiator “Irgacure 907” (Ciba Geigy), 1 part by mass of sensitizer “Kayacure DETX” {manufactured by Nippon Kayaku Co., Ltd.} Then, 5.2 mL / m ^{2 of} the coating solution dissolved in 214.2 parts by mass of methyl ethyl ketone was applied with a # 3 wire bar coater. This was affixed to a metal frame and heated in a thermostatic bath at 130 ° C. for 2 minutes to orient the discotic compound. Next, using a 120 W / cm high-pressure mercury lamp at 90 ° C., UV irradiation was performed for 1 minute to polymerize the discotic compound. Then, it stood to cool to room temperature. Thus, an optically anisotropic layer was formed, and an optical compensation sheet (WV-1) was obtained.

(Saponification treatment of optical compensation sheet)
The optical compensation sheet (WV-1) was saponified in the same manner as in Example 11-1.

[Preparation of polarizing plate]
A polarizer was prepared by adsorbing iodine to a stretched polyvinyl alcohol film.
Next, the transparent support side of the optical compensation sheet (WV-1) saponified as described above was attached to one side of the obtained polarizer using a PVA adhesive. The slow axis of the transparent support and the transmission axis of the polarizer were arranged in parallel.

  A commercially available cellulose triacetate film “Fujitac TD80UF” (manufactured by Fuji Photo Film Co., Ltd.) was saponified in the same manner as in Example 11-1, and the other side of the polarizer (with an optical compensation sheet was used) using a polyvinyl alcohol adhesive. It was pasted on the side that was not pasted). In this way, an elliptically polarizing plate (P2-1) was produced.

Example 22
[Production of liquid crystal display device]
[Preparation of bend alignment liquid crystal cell]
A polyimide film was provided as an alignment film on a glass substrate with an ITO electrode, and the alignment film was rubbed. The obtained two glass substrates were opposed to each other so that the rubbing directions were parallel to each other, and the cell gap was set to 5.7 μm. A liquid crystal compound “ZLI1132” (manufactured by Merck & Co., Inc.) having Δn of 0.1396 was injected into the cell gap to produce a bend alignment liquid crystal cell.

[Production of liquid crystal display devices]
Two elliptically polarizing plates (P2-1) were attached so as to sandwich the produced bend alignment cell. The optically anisotropic layer of the polarizing plate faced the cell substrate, and the rubbing direction of the liquid crystal cell and the rubbing direction of the optically anisotropic layer facing it were antiparallel.

  Using the obtained liquid crystal display device, when light leakage was observed in black display when continuously lit for 1000 hours in an environment of 25 ° C. and 80% RH, the polarizing plate (P2-1) of the present invention was observed. The liquid crystal display device used was found to be preferable without display unevenness.

FIG. 1 is an example of a configuration in which the polarizing plate of the present invention and a functional optical film are combined. FIG. 2 is an example of a liquid crystal display device using the polarizing plate of the present invention. FIG. 3 shows an example of a VA mode liquid crystal display device using the polarizing plate of the present invention.

Explanation of symbols

1, 1a, 1b: Protective film 2: Polarizer 3: Functional optical film 4: Adhesive layer 5: Polarizing plate

6: Upper polarizing plate 7: Upper polarizing plate absorption axis 8: Upper optical anisotropic layer 9: Upper optical anisotropic layer alignment control direction 10: Upper electrode substrate of liquid crystal cell 11: Upper substrate alignment control direction 12: Liquid crystal molecule 13 : Lower electrode substrate of liquid crystal cell 14: Lower substrate orientation control direction 15: Lower optical anisotropic layer 16: Lower optical anisotropic layer orientation control direction 17: Lower polarizing plate 18: Lower polarizing plate absorption axis

30: Upper polarizing plate 31: VA mode liquid crystal cell 32: Lower polarizing plate 33: Cellulose acylate film 34: Polarizer

Claims (8)

Cellulose acylate characterized in that the orientation degree P _o of the cellulose acylate molecular chain on the film surface and the average orientation degree P _t of the cellulose acylate molecular chain at the entire film thickness satisfy the relationship of the following formula (1): the film.
Formula (1): 2 ≦ P _o / P _t ≦ 5 The cellulose acylate film according to claim 1, wherein Re and Rth at a wavelength of 590 nm satisfy a relationship of the following formulas (2) to (4).
Formula (2): 20 ≦ Re ≦ 200
Formula (3): 70 ≦ Rth ≦ 400
Formula (4): 1 ≦ Rth / Re ≦ 10 A step (1) of transporting a cellulose acylate film peeled after a dope solution containing cellulose acylate and an organic solvent is cast on a band or a drum, a step (2) of gripping the edge of the width, and a width In the production of a cellulose acylate film having the step (3) of stretching in the hand direction, a cellulose acylate having a residual solvent content of 1% by mass to 100% by mass and an I / O ratio of the residual solvent of 0.65 to 6 A method for producing a cellulose acylate film, wherein the film is stretched by 1% or more and 100% or less in a film transport direction and / or a direction perpendicular thereto under the condition of the following formula (5).
Formula (5): 1% / min ≦ stretching speed ≦ 50% / min The manufacturing method of the cellulose acylate film of Claim 3 which satisfy | fills the conditions of following Numerical formula (6).
Formula (6): 5 ≦ conveying speed / stretching speed ≦ 300   The cellulose acylate film according to claim 1 or 2 produced by the method according to claim 3 or 4.   A polarizing plate in which a protective film is bonded to both sides of a polarizer, wherein at least one of the protective films is the cellulose acylate film according to claim 1, 2 or 5.   The polarizing plate of Claim 6 which has an optically anisotropic layer on at least one protective film. A liquid crystal display device comprising a liquid crystal cell and two polarizing plates disposed on both sides thereof, at least one of the polarizing plates being the polarizing plate according to claim 6 or 7.

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