JP2006096023A - Cellulose acylate film, its manufacturing method, optical compensation film, polarizing plate and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cellulose acylate film having a high retardation value and excellent in optical uniformity within a film plane, and also resistant to curling and excellent in processability, its manufacturing method, an optical compensation film and a polarizing plate which use the cellulose acylate film excellent in above characteristics as a support, and a liquid crystal display device using the polarizing plate. <P>SOLUTION: This cellulose acylate film contains ≥0.1 pts. mass and ≤30 pts. mass of additives, in which one kind at least has the ≥300 molecular weight, per 100 pts. mass of a cellulose acylate, and the cellulose acylate film such that the ratio of the existence quantity of respective additives satisfies the formula: 0.25 <existence quantity of additives on air side face/existence quantity of additives on support side face <4, wherein the support side face means the side of the cellulose acylate film which is in contact with the face of a band or a drum, and the air side face means the side which faces the air, is used. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

  In a liquid crystal display device, it is a well-known technique to use an optical compensation film for widening the viewing angle, improving image coloring, and improving contrast. Among them, a film in which a low molecular compound having a highly planar molecular structure is added to cellulose acylate is particularly useful because it allows retardation adjustment in a wide range. For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2000-1111914). ), Patent Document 2 (Japanese Patent Laid-Open No. 2000-166144), and the like. However, these compounds were used in the drying process when a cellulose acylate film was produced by the solvent cast method, and the film was bleed out on the film surface to make the film optically non-uniform, and an optical compensation film comprising this film was used. The liquid crystal display device has a problem that display quality is remarkably inferior.

An object of the present invention is to provide a cellulose acylate film having a high retardation value, excellent optical uniformity in the film plane, small curl and excellent processability, and a method for producing the same.
Another object of the present invention is to provide an optical compensation film and a polarizing plate using a cellulose acylate film having excellent properties as described above as a support.
A further object of the present invention is to provide a liquid crystal display device having good display quality using the polarizing plate.

As a result of intensive studies, the inventors bleeded out the additive in the drying step when producing a cellulose acylate film by the solvent cast method. As a result, it was concluded that re-diffusion into the cellulose acylate film was not sufficiently performed, and it was found that the problem can be solved by sufficiently slowing down the solvent volatilization rate during drying.
Further, the amount of additive present on the surface of the support surface (hereinafter simply referred to as “support surface”) and the air surface on the air side (hereinafter simply referred to as “air surface”) in contact with the band or drum surface of the film by the above method. It was found that the amount of additives present on the side surface could be balanced, and the film properties such as curling were remarkably improved, and a cellulose acylate film excellent in processability could be obtained.
That is, according to the present invention, a cellulose acylate film production method, a cellulose acylate film, an optical compensation film, a polarizing plate, and a liquid crystal display device having the following constitution are provided, and the object of the present invention is achieved.

1. A cellulose acylate film containing at least one additive having a molecular weight of 300 or more and 0.1 to 30 parts by mass with respect to 100 parts by mass of cellulose acylate,
For each additive, the abundance ratio of the cellulose acylate film on the side of the support surface that was in contact with the band or drum surface and the air surface that was on the air side satisfies the following formula: Cellulose acylate film.
0.25 <additive amount of additive on air surface / additive amount of additive on surface of support <4
2. A cellulose acylate film containing at least one additive having a molecular weight of 300 or more and 0.1 to 30 parts by mass with respect to 100 parts by mass of cellulose acylate,
The ratio of the total amount of additives present in the total amount of all additives present on the surface of the support surface that was in contact with the band or drum surface of the cellulose acylate film and the air surface that was on the air side was A cellulose acylate film satisfying the following formula:
0.5 <total additive abundance on air surface / total additive abundance on support surface <1.75
3. 3. The cellulose acylate film as described in 1 or 2 above, wherein at least one of the additives is a retardation increasing material.
4). 4. The cellulose acylate film as described in any one of 1 to 3 above, wherein at least one of the additives is a plasticizer.
5. The cellulose acylate film as described in any one of 1 to 4 above, wherein at least one of the additives is an ultraviolet absorber.
6). 6. The cellulose acylate film as described in any one of 1 to 5 above, wherein at least one of the additives is a hydrophobizing agent.
7). The cellulose acylate film as described in any one of 1 to 6 above, wherein at least one of the additives is a retardation reducing agent.
8). The cellulose acylate film as described in any one of 1 to 7 above, wherein at least one of the additives is a dye.
9. A method for producing a cellulose acylate film cast on a band by a solvent cast method,
A step of casting a cellulose acylate solution containing 0.01 to 20 parts by mass of phenyl benzoate as a retardation increasing agent having a molecular weight of 300 or more with respect to 100 parts by mass of cellulose acylate, and stripping A method for producing a cellulose acylate film, comprising the step of drying in the first half of the pre-drying for 10 seconds to 90 seconds in a substantially windless manner.
10. A method for producing a cellulose acylate film cast on a drum by a solvent cast method,
1 second in the first half of the step of casting a cellulose acylate solution containing 0.1 to 30 parts by mass of an additive having a molecular weight of 300 or more with respect to 100 parts by mass of cellulose acylate and drying before peeling The manufacturing method of the cellulose acylate film characterized by including the process of drying for 10 seconds or less substantially in a windless manner.
11. A method for producing a cellulose acylate film cast on a band by a solvent cast method,
A step of casting a cellulose acylate solution containing 0.1 to 30 parts by mass of an additive having a molecular weight of 300 or more with respect to 100 parts by mass of cellulose acylate, and 10 seconds in the first half of drying before peeling A method for producing a cellulose acylate film, comprising the step of drying in a substantially windless manner for a period of 90 seconds or less.
12 3. The cellulose acylate film as described in 1 or 2 above, which is produced by the method according to any one of 9 to 11 above.
13. The cellulose acylate film according to any one of 1 to 8 and 12, wherein the additive is represented by the following general formula (II).
Formula (II)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ each represents an electron donating group, R ⁸ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkynyl group having 2 to 6 carbon atoms. Group, aryl group having 6 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, aryloxy group having 6 to 12 carbon atoms, alkoxycarbonyl group having 2 to 12 carbon atoms, acylamino group having 2 to 12 carbon atoms, cyano Represents a group or a halogen atom.)
14 14. The cellulose acylate film as described in 13 above, wherein the electron donating group of the general formula (II) is an alkoxy group.
15. 14. The cellulose acylate film as described in 13 above, wherein the compound represented by the general formula (II) is a compound represented by the following general formula (II-D):

(In the formula, R ² , R ⁴ and R ⁵ each represent a hydrogen atom or a substituent. R ²¹ and R ²² are each independently an alkyl group having 1 to 4 carbon atoms. X ¹ has 6 to 6 carbon atoms. 12 aryl groups, C2-C12 alkoxycarbonyl groups, and cyano groups.)
16. The cellulose acylate film according to any one of 1 to 8 and 12, wherein the additive is a 1,3,5-triazine compound.
17. The cellulose acylate film as described in any one of 1 to 8 and 12 to 16, wherein the retardation value Rth in the thickness direction is in the range of 70 to 400 nm.
18. The retardation value Re in the in-plane direction is 20 nm or more and 200 nm or less, and the film is stretched at a draw ratio of 1.05 or more and 2.00 or less, according to any one of 1 to 8 and 12 to 17 above Cellulose acylate film.
19. 21. The cellulose acylate films of 1 to 8 and 12 to 16, which have an Rth retardation value of −20 nm to 20 nm and an Re retardation value of 5 nm or less. An optical compensation film comprising an optically anisotropic layer formed of liquid crystalline molecules on the cellulose acylate film according to any one of 1 to 8 and 12 to 19.
21. A polarizing plate in which an optically anisotropic layer formed from a transparent protective film, a polarizing film, a transparent support, and a liquid crystalline molecule is laminated in this order,
A polarizing plate, wherein the transparent support is the cellulose acylate film of any one of 1 to 8 and 12 to 19.
22. A polarizing plate comprising a liquid crystal cell and two polarizing plates disposed on both sides thereof,
22. A liquid crystal display device, wherein at least one of the two polarizing plates is the polarizing plate described in 21 above.
23. 23. The liquid crystal display device as described in 22 above, wherein the liquid crystal cell is a TN mode, bend alignment mode or vertical alignment mode liquid crystal cell.

  The cellulose acylate film obtained by the production method of the present invention has a high retardation value and excellent optical uniformity in the film plane. Furthermore, the cellulose acylate film of the present invention has small curl and excellent processability. A liquid crystal display device using an optical compensation film and a polarizing plate using the cellulose acylate film as a support is excellent in display quality.

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

First, the additive used for the cellulose acylate of the present invention will be described. The additive of the present invention is preferably a compound having a molecular weight of 300 or more, more preferably a low molecular compound having a molecular weight of 300 or more and 2000 or less, and further preferably 350 or more and 1500 or less.
By using a compound having a molecular weight within this range, it is possible to appropriately adjust the diffusion of the additive in the drying step, and to reduce the additive abundance ratio of the air surface and the support surface.

In addition, the additive of the present invention is used in an amount of 0.1 to 30 parts by mass, preferably 1 to 25 parts by mass with respect to 100 parts by mass of cellulose acylate. By using an additive in this range, its functions (retardation control, plasticization, hydrophobization, ultraviolet absorption, etc.) can be exhibited effectively. If the amount is less than 0.1 parts by mass, the effect is insufficient. If the amount exceeds 30 parts by mass, the additive is not compatible with cellulose acylate and crystallizes or phase separates in the film.
The retardation increasing agent for benzoic acid phenyl ester such as the compound represented by the general formula (II) is used in an amount of 0.01 to 20 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the cellulose ester. . By using the retardation increasing agent within this range, the retardation of the film can be appropriately controlled. When the amount is less than 0.01 parts by mass, the retardation is not increased and the retardation cannot be suppressed. If the amount exceeds 20 parts by mass, the retardation increasing agent is not compatible with the cellulose ester and crystallizes in the film.
Moreover, it is preferable that the film surface of the additive of the present invention is balanced as much as possible between the air surface side and the support surface side. When the drying on the band or drum proceeds uniformly, problems such as bleeding out are less likely to occur, and curling of the film is also reduced. The abundance on the film surface can be measured by a time-of-flight secondary ion mass spectrometer (TOF-SIMS). According to this method, it is possible to quantify the amount of additive present on the outermost surface of 1 nm or less from the gas-solid interface. Furthermore, by taking a relative ratio between the ionic strength caused by the additive and the ionic strength caused by the cellulose acylate, it is possible to correct and evaluate variations between measurements such as ionization efficiency.

In the cellulose acylate film of the present invention, the abundance ratio of each additive on the air surface surface and the support surface surface is preferably 0.25 <air surface abundance / support surface abundance <4.0, and 0.3 <air. Surface abundance / support surface abundance <3.0 is more preferred, and 0.5 <air surface abundance / support surface abundance <2.0 is most preferred.
In addition, the ratio of the total abundance (total additive abundance) obtained by adding the abundances of all additives on the air surface surface and the support surface of the cellulose acylate film of the present invention is 0.5 <total air surface existence. Amount / support surface total abundance <1.75 is preferred, and 0.75 <air surface total abundance / support surface total abundance <1.5 is more preferred.

Control of the ratio of the amount of additive on the air surface / the amount of additive on the surface of the support is effective for additives with various functions, such as plasticizers, UV absorbers, and hydrophobizing agents. It is particularly effective for a retardation increasing agent that has high properties and is relatively incompatible with cellulose acylate.
Next, the retardation increasing agent used in the present invention will be described.

[Retardation raising agent]
In the present invention, it is preferable to use a benzoic acid phenyl ester as a retardation increasing agent such as a compound represented by the following general formula (II). The compound represented by the general formula (II) is preferable because it has a rod-like structure and a large polarizability anisotropy, has high retardation, and can be produced at low cost. In the step of casting a cellulose acylate solution described later, the solution preferably contains 0.01 to 20 parts by mass of benzoic acid phenyl ester as a retardation increasing agent with respect to 100 parts by mass of cellulose acylate.
Formula (II)

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

In general formula (II), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent, and the substituent will be described later. The substituent T can be applied.
At least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ represents an electron donating group. Preferably, one of R ¹ , R ³ or R ⁵ is an electron donating group, and R ³ is more preferably an electron donating group.
The electron donating group is one having Hammet's σ _p value of 0 or less. Rev. 91, 165 (1991). Sigma _p value of Hammet described is 0 following can be preferably used, more preferably those -0.85～0 is used. Examples thereof include an alkyl group, an alkoxy group, an amino group, and a hydroxyl group.
The electron donating group is preferably an alkyl group or an alkoxy group, more preferably an alkoxy group (preferably having a carbon number of 1 to 12, more preferably a carbon number of 1 to 8, still more preferably a carbon number of 1 to 6, particularly preferably carbon. 1 to 4).

R ¹ 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 ² 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 ³ 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 ⁴ 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.

R ⁵ 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 having a carbon number). 1 to 4 is 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 4 carbon atoms). It is. Particularly preferred are a hydrogen atom, a methyl group and a methoxy group.

R ⁶ , R ⁷ , R ⁹ and R ¹⁰ 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 ⁸ is a hydrogen atom, 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, or an aryloxy having 6 to 12 carbon atoms. Group, 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, which may have a substituent if possible. The group T can be applied.
R ⁸ is preferably 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, or an aryloxy group having 2 to 12 carbon atoms. And more preferably an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an aryloxy group having 6 to 12 carbon atoms, more preferably an alkoxy group having 1 to 12 carbon atoms (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms), and particularly preferably a methoxy group, an ethoxy group, and n. -A propoxy group, an iso-propoxy group, and an n-butoxy group.

Of the general formula (II), the following general formula (II-A) is more preferable.
Formula (II-A)

(Wherein R ¹¹ represents an alkyl group. R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represents a hydrogen atom or a substituent. R ⁸ Is a hydrogen atom, 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, an aryloxy group having 6 to 12 carbon atoms, (Represents 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.)
In the general formula (II-A), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are respectively synonymous with those in the general formula (II), and The preferable range is also the same.

In General Formula (II-A), R ¹¹ represents an alkyl group having 1 to 12 carbon atoms, and the alkyl group represented by R ¹¹ may be linear or branched, and further has a substituent. However, it is preferably 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, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group and the like.

Of the general formula (II), the following general formula (II-B) is more preferable.
General formula (II-B)

(In the formula, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represents a hydrogen atom or a substituent. R ¹¹ is an alkyl having 1 to 12 carbon atoms. X represents 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, or an aryloxy group having 6 to 12 carbon atoms. A group, 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.)

In general formula (II-B), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ have the same meanings as those in general formula (II), and the preferred ranges are also the same. It is.
In General Formula (II-B), R ¹¹ has the same meaning as that in General Formula (II-A), and the preferred range is also the same.

In general formula (II-B), X 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, or 6 carbon atoms. Represents an aryloxy group having 12 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.
When R ¹ , R ² , R ⁴ and R ⁵ are all hydrogen atoms, X is preferably an alkyl group, alkynyl group, aryl group, alkoxy group or aryloxy group, more preferably an aryl group or alkoxy group. Group, aryloxy group, more preferably alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms). And particularly preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group or an n-butoxy group.

When at least one of R ¹ , R ² , R ⁴ and R ⁵ is a substituent, X is preferably an alkynyl group, an aryl group, an alkoxycarbonyl group, or a cyano group, more preferably an aryl group (preferably 6 to 12 carbon atoms), a cyano group, and an alkoxycarbonyl group (preferably 2 to 12 carbon atoms), more preferably an aryl group (preferably an aryl group having 6 to 12 carbon atoms, more preferably a phenyl group, p-cyanophenyl group and p-methoxyphenyl group), an alkoxycarbonyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms, particularly preferably methoxycarbonyl, Ethoxycarbonyl, n-propoxycarbonyl), cyano group, particularly preferably phenyl group, methoxy group. Group, an ethoxycarbonyl group, n- propoxycarbonyl group, a cyano group.

Of the general formula (II), the following general formula (1-C) is more preferable.
General formula (II-C)

(In the formula, R ¹ , R ² , R ⁴ , R ⁵ , R ¹¹ and X are synonymous with those in the general formula (II-B), and preferred ranges are also the same.)

Of the compounds represented by the general formula (II), compounds represented by the following general formula (II-D) are preferred.
General formula (II-D)

(Wherein R ² , R ⁴ and R ⁵ have the same meanings as those in formula (II-C), and preferred ranges thereof are also the same. R ²¹ and R ²² each independently has 1 to 4 carbon atoms. X ¹ is an aryl group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or a cyano group.

R ²¹ represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably an ethyl group or a methyl group.
R ²² 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.

X ¹ is an aryl group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or a cyano group, preferably an aryl group having 6 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, or a cyano group. More preferably a phenyl group, a p-cyanophenyl group, a p-methoxyphenyl group, a methoxycarbonyl, an ethoxycarbonyl, an n-propoxycarbonyl, a cyano group, and still more preferably a phenyl group, a methoxycarbonyl group, an ethoxycarbonyl group, n-propoxycarbonyl group and cyano group.

Of the general formula (II), the following general formula (II-E) is most preferred.
General formula (II-E)

(In the formula, R ² , R ⁴ and R ⁵ have the same meanings as those in formula (II-D), and the preferred range is also the same, but one of them is a group represented by —OR ¹³ ( R ¹³ is an alkyl group having 1 to 4 carbon atoms.) R ²¹ , R ²² and X ¹ have the same meanings as those in formula (II-D), and preferred ranges thereof are also the same.

In the general formula (II-E), R ² , R ⁴ and R ⁵ have the same meanings as those in the general formula (1-D), and preferred ranges are also the same, but any one of them is represented by —OR ^13. (R ¹³ is an alkyl group having 1 to 4 carbon atoms), preferably R ⁴ and R ⁵ are groups represented by —OR ¹³ , more preferably R ⁴ is —OR ¹³ . It is a group represented.
R ¹³ 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.

  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, and particularly preferably 1 to 8 carbon atoms such as methyl, ethyl, iso-propyl, tert-butyl, and 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, and particularly preferably carbon number). 2 to 8, 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, and particularly preferably carbon number). 2-8, for example, propargyl, 3-pentynyl, etc.), aryl groups (preferably having 6-30 carbon atoms) More preferably, it has 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, naphthyl and the like, and a substituted or unsubstituted amino group (preferably having 0 to 0 carbon atoms). 20, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino, etc.), an alkoxy group (preferably having a carbon number) 1 to 20, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as methoxy, ethoxy, butoxy, etc.), an aryloxy group (preferably 6 to 20 carbon atoms, more Preferably it has 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, and examples thereof include acetyl, benzoyl, formyl, and pivaloyl). An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, etc.), an aryloxycarbonyl group ( Preferably it has 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms, and examples include phenyloxycarbonyl, etc.), an acyloxy group (preferably 2 to 20 carbon atoms, More preferably, it has 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms. Nzoyloxy and the like. ), An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino), 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), aryloxycarbonylamino group (preferably having carbon number) 7 to 20, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino, and the like, and sulfonylamino groups (preferably 1 to 20 carbon atoms, more preferably Has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms. And sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, and particularly preferably 0 to 12 carbon atoms, such as sulfamoyl and methylsulfamoyl). , Dimethylsulfamoyl, phenylsulfamoyl, etc.), a carbamoyl group (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, phenylcarbamoyl, etc.), an alkylthio group (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 group (preferably Has 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, and a sulfonyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl, tosyl, etc.), sulfinyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably Has 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc.), ureido group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms). For example, ureido, methylureido, phenylureido, etc.), phosphoric acid amide group (preferably having 1 to 20 carbon atoms) More preferably, it is C1-C16, Most preferably, it is C1-C12, for example, diethyl phosphoric acid amide, phenylphosphoric acid amide etc. are mentioned. ), Hydroxy group, mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, Heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, piperidyl , Morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, etc.), silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms). For example, trimethylsilyl, triphenylsilyl, etc.) . 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 formula (II) 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 (II) of 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, a method of dehydrating the substituted benzoic acid and a phenol derivative using a condensing agent or a catalyst, and the like.
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.

  Reaction solvents include hydrocarbon solvents (preferably toluene and xylene), ether solvents (preferably dimethyl ether, tetrahydrofuran, dioxane, etc.), ketone solvents, ester solvents, acetonitrile, dimethylformamide, dimethyl Acetamide or the like can be used. These solvents may be used alone or in admixture of several kinds, and preferred reaction solvents are toluene, acetonitrile, dimethylformamide and 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 and the like).

  The method for synthesizing the compound of the present invention is specifically described below, but the present invention is not limited by the following specific examples.

[Synthesis Example 1: Synthesis of Exemplified Compound A-1]
After heating 24.6 g (0.116 mol) of 3,4,5-trimethoxybenzoic acid, 100 mL of toluene and 1 mL of NN-dimethylformamide to 60 ° C., 15.2 g (0.127 mol) of thionyl chloride was slowly added. And then 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 A-2]
After heating 106.1 g (0.5 mol) of 2,4,5-trimethoxybenzoic acid, 340 mL of toluene and 1 mL of dimethylformamide to 60 ° C., 65.4 g (0.55 mol) of thionyl chloride was slowly added dropwise, Heated at 65-70 ° 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 Exemplified Compound A-3]
After heating 10.1 g (47.5 mmol) of 2,3,4-trimethoxybenzoic acid, 40 mL of toluene and 0.5 mL of dimethylformamide 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 A-4]
After heating 25.0 g (118 mmol) of 2,4,6-trimethoxybenzoic acid, 100 mL of toluene and 1 mL of dimethylformamide to 60 ° C., 15.4 g (129 mmol) of thionyl chloride was slowly added dropwise, Stir for 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 Exemplary Compound A-5]
After heating 15.0 g (82.3 mmol) of 2,3-dimethoxybenzoic acid, 60 mL of toluene and 0.5 mL of dimethylformamide to 60 ° C., 10.7 (90.5 mmol) of thionyl chloride was slowly added dropwise. 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, and 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 A-6]
The synthesis was performed in the same manner except that 2,3-dimethoxybenzoic acid in A-5 was changed to 2,4-dimethoxybenzoic acid. 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 Exemplified Compound A-7]
After heating 25.0 g (137 mmol) of 2,5-dimethoxybenzoic acid, 100 mL of toluene and 1.0 mL of dimethylformamide to 60 ° C., 18.0 (151 mmol) of thionyl chloride was slowly added dropwise. Stir for 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 Exemplary Compound A-8]
The synthesis was performed in the same manner except that 2,3-dimethoxybenzoic acid in A-5 was changed to 2,6-dimethoxybenzoic acid. 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 Exemplary Compound A-11]
The target compound was obtained in the same manner except that 71.5 g of 4-cyanophenol in A-2 was changed to 76.9 g of 4-chlorophenol. 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 A-12]
After heating 45.0 g (212 mmol) of 2,4,5-trimethoxybenzoic acid, 180 mL of toluene and 1.8 mL of dimethylformamide to 60 ° C., 27.8 g (233 mmol) of thionyl chloride was slowly added dropwise to the mixture at 60 ° C. And stirred for 2.5 hours. Thereafter, a solution prepared by 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 A-13]
After heating 20.0 g (94.3 mmol) of 2,4,5-trimethoxybenzoic acid, 100 mL of toluene and 1 mL of dimethylformamide to 60 ° C., 12.3 g (104 mmol) of thionyl chloride was slowly added dropwise to the mixture at 60 ° C. And stirred 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 A-14]
After heating 12.9 g (61 mmol) of 2,4,5-trimethoxybenzoic acid, 50 mL of toluene, and 0.6 mL of dimethylformamide to 60 ° C., 8.0 g (67 mmol) of thionyl chloride was slowly added dropwise to the mixture at 60 ° C. And stirred for 3.5 hours. Thereafter, a solution prepared by dissolving 17.7 g (104 mmol) of 4-phenylphenol in 25 mL of acetonitrile was slowly added 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 Exemplary Compound A-15]
The target compound was obtained in the same manner except that 71.5 g of 4-cyanophenol in A-2 was changed to 56.4 g of phenol. 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)
The melting point of the obtained compound was 105 to 108 ° C.
Mass spectrum: m / z 289 (M + H) ⁺

[Synthesis Example 14: Synthesis of Exemplified Compound A-16]
The target compound can be obtained in the same manner except that 71.5 g of 4-cyanophenol in A-2 is changed to 74.4 g of 4-methoxyphenol. 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 A-17]
The target compound was obtained in the same manner except that 71.5 g of 4-cyanophenol in A-2 was changed to 73.3 g of 4-ethylphenol. The compound was identified by 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 Exemplary Compound A-24]
After heating 27.3 g (164 mmol) of 4-ethoxybenzoic acid, 108 mL of toluene, and 1 mL of dimethylformamide to 60 ° C., 21.5 g (181 mmol) of thionyl chloride was slowly added dropwise, and the mixture was heated and stirred 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 A-25]
After heating 24.7 g (149 mmol) of 4-ethoxybenzoic acid, 100 mL of toluene and 1 mL of dimethylformamide to 60 ° C., 19.5 g (164 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 dissolving 25.0 g (165 mmol) of 4-propoxyphenol 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, 100 mL of methanol was added to the obtained solid, and recrystallization was performed. The obtained crystals were collected by filtration to obtain 33.9 g (yield 76%) of the target compound as white crystals. It was. 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 Exemplified Compound A-27]
The compound was synthesized in the same manner except that 27.3 g of 4-ethoxybenzoic acid in the synthesis method of A-24 was changed to 29.5 g of 4-propoxybenzoic acid. 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 Exemplary Compound A-28]
The compound was synthesized in the same manner except that 24.7 g of 4-ethoxybenzoic acid in the synthesis method of A-25 was changed to 26.8 g of 4-propoxybenzoic acid. 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 Exemplified Compound A-40]
After heating 20.0 g (109 mmol) of 2,4-dimethoxybenzoic acid, 80 mL of toluene, and 0.8 mL of dimethylformamide to 60 ° C., 14.4 g (121 mmol) of thionyl chloride was slowly added dropwise, The mixture was heated and stirred for 5 hours. Thereafter, a solution prepared by previously dissolving 20.5 g (121 mmol) of 4-phenylphenol in 50 mL of dimethylformamide was slowly added and stirred at 80 ° C. for 6 hours. After cooling the reaction solution to room temperature, 100 mL of methanol was added. 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 Exemplified Compound A-42]
After heating 30.0 g (165 mmol) of 2,4-dimethoxybenzoic acid, 120 mL of toluene, and 1.2 mL of dimethylformamide to 60 ° C., 21.6 g (181 mmol) of thionyl chloride was slowly added dropwise. Stir for hours. Thereafter, a solution prepared by 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. Methanol (140 mL) 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.

  Further, a UV absorber may be used in combination with a benzoic acid phenyl ester retardation increasing agent such as a compound represented by the general formula (II). The use amount of the UV absorber is preferably 10% or less, more preferably 3% or less in terms of mass ratio with respect to the retardation increasing agent.

  In addition to the benzoic acid phenyl ester such as the compound represented by the general formula (II), a triazine compound represented by the following general formula (I) can also be used as a retardation increasing agent. When the triazine compound represented by the general formula (I) is used as the retardation increasing agent, the amount of the compound used is the same as that of the benzoic acid phenyl ester such as the compound represented by the general formula (II). It's okay.

The triazine compound that can be used as the retardation increasing agent in the cellulose acylate film having the above-mentioned ratio of the retardation increasing agent is a compound represented by the following general formula (I). Since this compound has a highly planar molecular structure, it exhibits high retardation and can be produced at low cost.
Formula (I)

In the above general formula (I):
R ¹² each independently represents an aromatic ring or a heterocyclic ring having a substituent in at least one of the ortho position, meta position and para position.
X ¹¹ each independently represents a single bond or —NR ¹³ —. Here, each R ¹³ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, or a heterocyclic group.

The aromatic ring represented by R ¹² is preferably phenyl or naphthyl, and particularly preferably phenyl. The aromatic ring represented by R ¹² may have 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 R ¹² 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 ¹¹ is 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. In addition, the heterocyclic group may have a hetero atom other than the nitrogen atom (eg, O, S). Examples of heterocyclic groups having free valences on nitrogen atoms are shown below.

In general formula (I), X ¹¹ represents a single bond or —NR ¹³ —. R ¹³ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, or a heterocyclic group.
The alkyl group represented by R ¹³ may be a cyclic alkyl group or a chain alkyl group, but a chain alkyl group is preferable, and a linear alkyl group is more preferable than a branched chain alkyl group. preferable. 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 R ¹³ may be a cyclic alkenyl group or a chain alkenyl group, but is preferably a chain alkenyl group, and is a straight chain alkenyl group rather than a branched chain alkenyl group. More preferably it represents a 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 ¹³ are the same as the aromatic ring and heterocyclic ring represented by R ¹² , and the preferred range is 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 ¹² .

The molecular weight of the retardation increasing agent represented by the general formula (I) is preferably 300 to 800.
Moreover, you may use a UV absorber together with the retardation increasing agent represented by general formula (I). The amount of the UV absorber used is preferably 10% or less, more preferably 3% or less in terms of mass ratio with respect to the retardation increasing agent represented by the general formula (I).

  Specific examples of the retardation increasing agent represented by the general formula (I) used in the present invention are shown below. Several R shown in each example means the same group. The definition of R is shown after the formula together with the specific example number.

(1) phenyl (2) 3-ethoxycarbonylphenyl (3) 3-butoxyphenyl (4) m-biphenylyl (5) 3-phenylthiophenyl (6) 3-chlorophenyl (7) 3-benzoylphenyl (8) 3 Acetoxyphenyl (9) 3-benzoyloxyphenyl (10) 3-phenoxycarbonylphenyl (11) 3-methoxyphenyl (12) 3-anilinophenyl (13) 3-isobutyrylaminophenyl (14) 3-phenoxy Carbonylaminophenyl (15) 3- (3-ethylureido) phenyl (16) 3- (3,3-diethylureido) phenyl (17) 3-methylphenyl (18) 3-phenoxyphenyl (19) 3-hydroxyphenyl

(20) 4-ethoxycarbonylphenyl (21) 4-butoxyphenyl (22) p-biphenylyl (23) 4-phenylthiophenyl (24) 4-chlorophenyl (25) 4-benzoylphenyl (26) 4-acetoxyphenyl ( 27) 4-Benzoyloxyphenyl (28) 4-phenoxycarbonylphenyl (29) 4-methoxyphenyl (30) 4-anilinophenyl (31) 4-isobutyrylaminophenyl (32) 4-phenoxycarbonylaminophenyl ( 33) 4- (3-Ethylureido) phenyl (34) 4- (3,3-diethylureido) phenyl (35) 4-methylphenyl (36) 4-phenoxyphenyl (37) 4-hydroxyphenyl

(38) 3,4-diethoxycarbonylphenyl (39) 3,4-dibutoxyphenyl (40) 3,4-diphenylphenyl (41) 3,4-diphenylthiophenyl (42) 3,4-dichlorophenyl (43 ) 3,4-dibenzoylphenyl (44) 3,4-diacetoxyphenyl (45) 3,4-dibenzoyloxyphenyl (46) 3,4-diphenoxycarbonylphenyl (47) 3,4-dimethoxyphenyl ( 48) 3,4-dianilinophenyl (49) 3,4-dimethylphenyl (50) 3,4-diphenoxyphenyl (51) 3,4-dihydroxyphenyl (52) 2-naphthyl

(53) 3,4,5-triethoxycarbonylphenyl (54) 3,4,5-tributoxyphenyl (55) 3,4,5-triphenylphenyl (56) 3,4,5-triphenylthiophenyl (57) 3,4,5-trichlorophenyl (58) 3,4,5-tribenzoylphenyl (59) 3,4,5-triacetoxyphenyl (60) 3,4,5-tribenzoyloxyphenyl (61 ) 3,4,5-triphenoxycarbonylphenyl (62) 3,4,5-trimethoxyphenyl (63) 3,4,5-trianilinophenyl (64) 3,4,5-trimethylphenyl (65) 3,4,5-triphenoxyphenyl (66) 3,4,5-trihydroxyphenyl

(67) Phenyl (68) 3-ethoxycarbonylphenyl (69) 3-butoxyphenyl (70) m-biphenylyl (71) 3-phenylthiophenyl (72) 3-chlorophenyl (73) 3-benzoylphenyl (74) 3 Acetoxyphenyl (75) 3-benzoyloxyphenyl (76) 3-phenoxycarbonylphenyl (77) 3-methoxyphenyl (78) 3-anilinophenyl (79) 3-isobutyrylaminophenyl (80) 3-phenoxy Carbonylaminophenyl (81) 3- (3-ethylureido) phenyl (82) 3- (3,3-diethylureido) phenyl (83) 3-methylphenyl (84) 3-phenoxyphenyl (85) 3-hydroxyphenyl

(86) 4-Ethoxycarbonylphenyl (87) 4-butoxyphenyl (88) p-biphenylyl (89) 4-phenylthiophenyl (90) 4-chlorophenyl (91) 4-benzoylphenyl (92) 4-acetoxyphenyl ( 93) 4-Benzoyloxyphenyl (94) 4-phenoxycarbonylphenyl (95) 4-methoxyphenyl (96) 4-anilinophenyl (97) 4-isobutyrylaminophenyl (98) 4-phenoxycarbonylaminophenyl ( 99) 4- (3-Ethylureido) phenyl (100) 4- (3,3-diethylureido) phenyl (101) 4-methylphenyl (102) 4-phenoxyphenyl (103) 4-hydroxyphenyl

(104) 3,4-diethoxycarbonylphenyl (105) 3,4-dibutoxyphenyl (106) 3,4-diphenylphenyl (107) 3,4-diphenylthiophenyl (108) 3,4-dichlorophenyl (109) ) 3,4-Dibenzoylphenyl (110) 3,4-diacetoxyphenyl (111) 3,4-dibenzoyloxyphenyl (112) 3,4-diphenoxycarbonylphenyl (113) 3,4-dimethoxyphenyl ( 114) 3,4-dianilinophenyl (115) 3,4-dimethylphenyl (116) 3,4-diphenoxyphenyl (117) 3,4-dihydroxyphenyl (118) 2-naphthyl

(119) 3,4,5-triethoxycarbonylphenyl (120) 3,4,5-tributoxyphenyl (121) 3,4,5-triphenylphenyl (122) 3,4,5-triphenylthiophenyl (123) 3,4,5-trichlorophenyl (124) 3,4,5-tribenzoylphenyl (125) 3,4,5-triacetoxyphenyl (126) 3,4,5-tribenzoyloxyphenyl (127 ) 3,4,5-triphenoxycarbonylphenyl (128) 3,4,5-trimethoxyphenyl (129) 3,4,5-trianilinophenyl (130) 3,4,5-trimethylphenyl (131) 3,4,5-triphenoxyphenyl (132) 3,4,5-trihydroxyphenyl

(133) phenyl (134) 4-butylphenyl (135) 4- (2-methoxy-2-ethoxyethyl) phenyl (136) 4- (5-nonenyl) phenyl (137) p-biphenylyl (138) 4-ethoxy Carbonylphenyl (139) 4-butoxyphenyl (140) 4-methylphenyl (141) 4-chlorophenyl (142) 4-phenylthiophenyl (143) 4-benzoylphenyl (144) 4-acetoxyphenyl (145) 4-benzoyl Oxyphenyl (146) 4-phenoxycarbonylphenyl (147) 4-methoxyphenyl (148) 4-anilinophenyl (149) 4-isobutyrylaminophenyl (150) 4-phenoxycarbonylaminophenyl (151) 4- ( 3-ethylureido) phenyl ( 52) 4- (3,3-diethyl-ureido) phenyl (153) 4-phenoxyphenyl (154) 4-hydroxyphenyl

(155) 3-Butylphenyl (156) 3- (2-methoxy-2-ethoxyethyl) phenyl (157) 3- (5-nonenyl) phenyl (158) m-biphenylyl (159) 3-ethoxycarbonylphenyl (160 ) 3-butoxyphenyl (161) 3-methylphenyl (162) 3-chlorophenyl (163) 3-phenylthiophenyl (164) 3-benzoylphenyl (165) 3-acetoxyphenyl (166) 3-benzoyloxyphenyl (167) ) 3-phenoxycarbonylphenyl (168) 3-methoxyphenyl (169) 3-anilinophenyl (170) 3-isobutyrylaminophenyl (171) 3-phenoxycarbonylaminophenyl (172) 3- (3-ethylureido) ) Phenyl (173) 3- (3 - diethyl ureido) phenyl (174) 3-phenoxyphenyl 175 3-hydroxyphenyl

(176) 2-Butylphenyl (177) 2- (2-methoxy-2-ethoxyethyl) phenyl (178) 2- (5-nonenyl) phenyl (179) o-biphenylyl (180) 2-ethoxycarbonylphenyl (181) ) 2-butoxyphenyl (182) 2-methylphenyl (183) 2-chlorophenyl (184) 2-phenylthiophenyl (185) 2-benzoylphenyl (186) 2-acetoxyphenyl (187) 2-benzoyloxyphenyl (188) ) 2-phenoxycarbonylphenyl (189) 2-methoxyphenyl (190) 2-anilinophenyl (191) 2-isobutyrylaminophenyl (192) 2-phenoxycarbonylaminophenyl (193) 2- (3-ethylureido ) Phenyl (194) 2- (3 - diethyl ureido) phenyl (195) 2-phenoxyphenyl (196) 2-hydroxyphenyl

(197) 3,4-dibutylphenyl (198) 3,4-di (2-methoxy-2-ethoxyethyl) phenyl (199) 3,4-diphenylphenyl (200) 3,4-diethoxycarbonylphenyl (201 ) 3,4-didodecyloxyphenyl (202) 3,4-dimethylphenyl (203) 3,4-dichlorophenyl (204) 3,4-dibenzoylphenyl (205) 3,4-diacetoxyphenyl (206) 3 , 4-Dimethoxyphenyl (207) 3,4-di-N-methylaminophenyl (208) 3,4-diisobutyrylaminophenyl (209) 3,4-diphenoxyphenyl (210) 3,4-dihydroxyphenyl

(211) 3,5-dibutylphenyl (212) 3,5-di (2-methoxy-2-ethoxyethyl) phenyl (213) 3,5-diphenylphenyl (214) 3,5-diethoxycarbonylphenyl (215 ) 3,5-didodecyloxyphenyl (216) 3,5-dimethylphenyl (217) 3,5-dichlorophenyl (218) 3,5-dibenzoylphenyl (219) 3,5-diacetoxyphenyl (220) 3 , 5-Dimethoxyphenyl (221) 3,5-di-N-methylaminophenyl (222) 3,5-diisobutyrylaminophenyl (223) 3,5-diphenoxyphenyl (224) 3,5-dihydroxyphenyl

(225) 2,4-dibutylphenyl (226) 2,4-di (2-methoxy-2-ethoxyethyl) phenyl (227) 2,4-diphenylphenyl (228) 2,4-diethoxycarbonylphenyl (229) ) 2,4-didodecyloxyphenyl (230) 2,4-dimethylphenyl (231) 2,4-dichlorophenyl (232) 2,4-dibenzoylphenyl (233) 2,4-diacetoxyphenyl (234) 2 , 4-Dimethoxyphenyl (235) 2,4-di-N-methylaminophenyl (236) 2,4-diisobutyrylaminophenyl (237) 2,4-diphenoxyphenyl (238) 2,4-dihydroxyphenyl

(239) 2,3-dibutylphenyl (240) 2,3-di (2-methoxy-2-ethoxyethyl) phenyl (241) 2,3-diphenylphenyl (242) 2,3-diethoxycarbonylphenyl (243 ) 2,3-didodecyloxyphenyl (244) 2,3-dimethylphenyl (245) 2,3-dichlorophenyl (246) 2,3-dibenzoylphenyl (247) 2,3-diacetoxyphenyl (248) 2 , 3-Dimethoxyphenyl (249) 2,3-di-N-methylaminophenyl (250) 2,3-diisobutyrylaminophenyl (251) 2,3-diphenoxyphenyl (252) 2,3-dihydroxyphenyl

(253) 2,6-dibutylphenyl (254) 2,6-di (2-methoxy-2-ethoxyethyl) phenyl (255) 2,6-diphenylphenyl (256) 2,6-diethoxycarbonylphenyl (257 ) 2,6-didodecyloxyphenyl (258) 2,6-dimethylphenyl (259) 2,6-dichlorophenyl (260) 2,6-dibenzoylphenyl (261) 2,6-diacetoxyphenyl (262) 2 , 6-Dimethoxyphenyl (263) 2,6-di-N-methylaminophenyl (264) 2,6-diisobutyrylaminophenyl (265) 2,6-diphenoxyphenyl (266) 2,6-dihydroxyphenyl

(267) 3,4,5-tributylphenyl (268) 3,4,5-tri (2-methoxy-2-ethoxyethyl) phenyl (269) 3,4,5-triphenylphenyl (270) 3,4 , 5-triethoxycarbonylphenyl (271) 3,4,5-tridodecyloxyphenyl (272) 3,4,5-trimethylphenyl (273) 3,4,5-trichlorophenyl (274) 3,4,5 -Tribenzoylphenyl (275) 3,4,5-triacetoxyphenyl (276) 3,4,5-trimethoxyphenyl (277) 3,4,5-tri-N-methylaminophenyl (278) 3,4 , 5-Triisobutyrylaminophenyl (279) 3,4,5-triphenoxyphenyl (280) 3,4,5-trihydroxyphenyl

(281) 2,4,6-tributylphenyl (282) 2,4,6-tri (2-methoxy-2-ethoxyethyl) phenyl (283) 2,4,6-triphenylphenyl (284) 2,4 , 6-triethoxycarbonylphenyl (285) 2,4,6-tridodecyloxyphenyl (286) 2,4,6-trimethylphenyl (287) 2,4,6-trichlorophenyl (288) 2,4,6 -Tribenzoylphenyl (289) 2,4,6-triacetoxyphenyl (290) 2,4,6-trimethoxyphenyl (291) 2,4,6-tri-N-methylaminophenyl (292) 2,4 , 6-Triisobutyrylaminophenyl (293) 2,4,6-triphenoxyphenyl (294) 2,4,6-trihydroxyphenyl

(295) pentafluorophenyl (296) pentachlorophenyl (297) pentamethoxyphenyl (298) 6-N-methylsulfamoyl-8-methoxy-2-naphthyl (299) 5-N-methylsulfamoyl-2- Naphthyl (300) 6-N-phenylsulfamoyl-2-naphthyl (301) 5-ethoxy-7-N-methylsulfamoyl-2-naphthyl (302) 3-methoxy-2-naphthyl (303) 1- Ethoxy-2-naphthyl (304) 6-N-phenylsulfamoyl-8-methoxy-2-naphthyl (305) 5-methoxy-7-N-phenylsulfamoyl-2-naphthyl (306) 1- (4 -Methylphenyl) -2-naphthyl (307) 6,8-di-N-methylsulfamoyl-2-naphthyl (308) 6-N 2-acetoxyethyl sulfamoyl-8-methoxy-2-naphthyl (309) 5-acetoxy -7-N-phenyl-sulfamoyl-2-naphthyl (310) 3-benzoyloxy-2-naphthyl

(311) 5-acetylamino-1-naphthyl (312) 2-methoxy-1-naphthyl (313) 4-phenoxy-1-naphthyl (314) 5-N-methylsulfamoyl-1-naphthyl (315) 3 -N-methylcarbamoyl-4-hydroxy-1-naphthyl (316) 5-methoxy-6-N-ethylsulfamoyl-1-naphthyl (317) 7-tetradecyloxy-1-naphthyl (318) 4- ( 4-methylphenoxy) -1-naphthyl (319) 6-N-methylsulfamoyl-1-naphthyl (320) 3-N, N-dimethylcarbamoyl-4-methoxy-1-naphthyl (321) 5-methoxy- 6-N-Benzylsulfamoyl-1-naphthyl (322) 3,6-di-N-phenylsulfamoyl-1-naphthyl

(323) methyl (324) ethyl (325) butyl (326) octyl (327) dodecyl (328) 2-butoxy-2-ethoxyethyl (329) benzyl (330) 4-methoxybenzyl

(331) Methyl (332) phenyl (333) butyl

As the retardation increasing agent of the present invention, a compound represented by the following general formula (IV) can also be preferably used.
When the compound represented by the general formula (IV) is used as the retardation increasing agent, the amount of the compound used is the same as that of the benzoic acid phenyl ester such as the compound represented by the general formula (II). Good.

In the formula, Ar ¹ , Ar ² and Ar ³ represent an aryl group or an aromatic heterocycle, and L ¹ and L ² represent a simple bond or a divalent linking group. n represents an integer of 3 or more, and Ar ² and L ² may be the same or different.
The compound represented by the general formula (IV) is more preferably a compound represented by the following general formula (V).

In the formula, R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ represent a hydrogen atom or a substituent. Ar ² represents an aryl group or an aromatic heterocycle, and L ² and L ³ represent a simple bond or a divalent linking group. n represents an integer of 3 or more, and Ar ² and L ² may be the same or different.
First, the compound represented by formula (IV) of the present invention will be described in detail.

In general formula (IV), Ar ¹ , Ar ² , Ar ³ represent an aryl group or an aromatic heterocycle, and L ¹ , L ² represent a simple bond or a divalent linking group. n represents an integer of 3 or more, and Ar ² and L ² may be the same or different.

Ar ¹ , Ar ² , Ar ³ represent an aryl group or an aromatic heterocycle, and the aryl group represented by Ar ¹ , Ar ² , Ar ³ is preferably an aryl group having 6 to 30 carbon atoms, It may be present or may form a condensed ring with another ring. Further, if possible, it may have a substituent, and the substituent T described later can be applied as the substituent.
In general formula (IV), the aryl group represented by Ar ¹ , Ar ² , Ar ³ is more preferably 6-20 carbon atoms, particularly preferably 6-12 carbon atoms, such as phenyl, p-methylphenyl, And naphthyl.

In the general formula (IV), the aromatic heterocycle represented by Ar ¹ , Ar ² , or Ar ³ is any heterocycle as long as it is an aromatic heterocycle containing at least one of an oxygen atom, a nitrogen atom, or a sulfur atom. Although it may be a ring, it is preferably an aromatic heterocycle containing at least one of a 5- to 6-membered oxygen atom, nitrogen atom or sulfur atom. 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 ¹ , Ar ² , Ar ³ in the general formula (IV) 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, tetrazaindene, pyrrolotriazole, pyrazolotriazole and the like. Preferred examples of the aromatic heterocycle include benzimidazole, benzoxazole, benzthiazole, and benzotriazole.

In the general formula (1), L ¹ and L ^{2 each} represent a mere bond or a divalent linking group, preferably as an example of a divalent linking group, preferably —NR ⁴⁷ — (R ⁴⁷ represents a hydrogen atom, a substituent A group represented by -SO _2- , -CO-, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, -O-, —S—, —SO— and a group obtained by combining two or more of these divalent groups, and more preferred among them are —O—, —CO—, —SO ₂ NR ⁴⁷ —, —NR ⁴⁷ SO. _2- , —CONR ⁴⁷ —, —NR ⁴⁷ CO—, —COO—, and —OCO—, an alkynylene group, most preferably —CONR ⁴⁷ —, —NR ⁴⁷ CO—, —COO—, and —OCO— , An alkynylene group.

When the compound represented by the general formula (IV) of the present invention, Ar ² binds to L ¹ and L ² Ar ² is a phenylene group, L1 ^- Ar ² -L ^2, and L ^{2-Ar 2} -L ² are most preferably in the relation of mutually para position (1,4-position).

  n represents an integer of 3 or more, preferably 3 to 7, and more preferably 3 to 5.

  Of the general formula (IV), the general formula (V) is preferable, and the general formula (V) will be described in detail.

^R41 , ^R42 , ^R43 , ^R44 , ^R45 , ^R46 , ^R51 , ^R52 , ^R53 and ^R54 each independently represents a hydrogen atom or a substituent. Ar ² represents an aryl group or an aromatic heterocycle, and L ² and L ³ represent a simple bond or a divalent linking group. n represents an integer of 3 or more, and Ar ² and L ² may be the same or different.

Ar ² , L ² , and n are the same as in the example of the general formula (1), L ³ represents a mere bond or a divalent linking group, and preferably —NR ⁴⁷ as an example of a divalent linking group. A group represented by — (R ⁴⁷ represents a hydrogen atom, an alkyl group or an aryl group which may have a substituent), an alkylene group, a substituted alkylene group, —O—, and these divalent groups are represented by 2 a one or more combination obtained group, -O is preferred from them ^{-, - NR 47 -, -} NR 47 SO 2 -, and -NR ⁴⁷ is CO-.

R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represents a hydrogen atom or a substituent, preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or carbon. An alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, and an isopropyl group) and an aryl group having 6 to 12 carbon atoms (for example, a phenyl group and a naphthyl group), and more preferably 1 to 4 carbon atoms. It is an alkyl group.

R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom or a substituent, preferably a hydrogen atom, an alkyl group, an alkoxy group or a hydroxyl group, more preferably a hydrogen atom or an alkyl group (preferably Is a C1-C4, more preferably a methyl group.

The aforementioned substituent T will be described below.
The substituent T is preferably a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, t -Butyl, n-octyl, 2-ethylhexyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), bicycloalkyl Group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. For example, bicyclo [1, 2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl) ,

An alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as vinyl, allyl), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, A monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms, such as 2-cyclopenten-1-yl and 2-cyclohexen-1-yl, and a bicycloalkenyl group (substituted or unsubstituted). A bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group in which one hydrogen atom of a bicycloalkene having one double bond is removed. , 2,1] hept-2-en-1-yl, bicyclo [2,2,2] oct-2-en-4-yl An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl), an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl), a heterocyclic group (preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and Preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms (for example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl),

A cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2 -Tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably having 2 to 30 carbon atoms) Substituted or unsubstituted heterocyclic oxy group, 1- Phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted group having 6 to 30 carbon atoms) Arylcarbonyloxy groups such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), carbamoyloxy groups (preferably substituted or unsubstituted carbamoyloxy having 1 to 30 carbon atoms) Groups such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy) An alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxycarbonyloxy group (Preferably, a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy),

An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms) A group such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino), an aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms such as carbamoylamino, N, N -Dimethylaminocarboni Amino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxy Carbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino , P-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino), sulfamoylamino group (preferably substituted or unsubstituted having 0 to 30 carbon atoms) Sulfamoylamino groups such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino, alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted 1 to 30 carbon atoms) Substituted alkylsulfonylamino, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenyl Sulfonylamino), mercapto group, alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio), arylthio group (preferably carbon number) 6 to 30 substituted or unsubstituted arylthio, for example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, For example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio),

Sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N- Acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl and arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms) 6-30 substituted or unsubstituted arylsulfinyl groups such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl)
Alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p- Methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, such as acetyl, pivaloyl Benzoyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylpheno Cicarbonyl), an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably Substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl) Aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms such as phenylazo, p-chlorophenylazo, 5- Ethylthio- , 3,4-thiadiazol-2-ylazo), an imide group (preferably N-succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethyl Phosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), A phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), a phosphinylamino group (preferably Is substituted or unsubstituted having 2 to 30 carbon atoms Phosphinylamino group such as dimethoxyphosphinylamino, dimethylaminophosphinylamino), silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms such as trimethylsilyl, t-butyldimethyl Silyl, phenyldimethylsilyl).

  Among the above-mentioned substituents, those having a hydrogen atom may be substituted with the above-mentioned group after removing this. Examples of such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

  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 compounds represented by the general formula (1) and the general formula (2) will be described in detail with specific examples, but the present invention is not limited to the following specific examples.

  Another effective example of controlling the ratio of the amount of additive present on the air surface / the amount of additive present on the support surface is a retardation reducing agent represented by the following general formula (III).

In the general formula (III), R ³¹ represents an alkyl group or an aryl group, and R ³² and R ³³ each independently represent a hydrogen atom, an alkyl group, or an aryl group. Moreover, it is particularly preferable that the total number of carbon atoms of R ³¹ , R ³² and R ³³ is 10 or more. As the substituent, a fluorine atom, an alkyl group, an aryl group, an alkoxy group, a sulfone group, and a sulfonamide group are preferable, and an alkyl group, an aryl group, an alkoxy group, a sulfone group, and a sulfonamide group are particularly preferable. Further, the alkyl group may be linear, branched or cyclic, and preferably has 1 to 25 carbon atoms, more preferably 6 to 25, and more preferably 6 to 20 (E.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, cyclohexyl, heptyl, octyl, bicyclooctyl, nonyl, adamantyl, decyl, t-octyl, undecyl, Dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, didecyl) are particularly preferred. As the aryl group, those having 6 to 30 carbon atoms are preferable, and those having 6 to 24 carbon atoms (for example, phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, triphenylphenyl) are particularly preferable. Moreover, in this invention, it is preferable that the addition amount of the compound represented by general formula (III) is 0.1-30 mass% with respect to a cellulose acylate, and it is further 1-25 mass% Preferably, it is 2-20 mass%, and it is especially preferable. Although the preferable example of a compound represented by general formula (II) is shown below, this invention is not limited to these specific examples.

  Next, the cellulose acylate film which is an object of the present invention and used in the optical compensation film and the polarizing plate will be described in detail.

[Cellulose acylate]
The cellulose acylate used in the present invention is preferably a lower fatty acid ester of cellulose. Lower fatty acid means a fatty acid having 6 or less carbon atoms. The number of carbon atoms is preferably 2 (cellulose acetate), 3 (cellulose propionate), and 4 (cellulose butyrate).
Of these, cellulose acetate is particularly preferable. Moreover, you may use the cellulose acylate of mixed fatty acid that cellulose acetate propionate and cellulose acetate butyrate are mixed. Furthermore, a cellulose aromatic acid ester such as cellulose benzoate, or a cellulose acylate of a mixed acid of an aliphatic acid and an aromatic acid in which cellulose acetate benzoate and cellulose propionate benzoate are mixed may be used. .
Among these, it is particularly preferable to use cellulose acetate having an acetylation degree in the range of 59.0 to 61.5%. The degree of acetylation means the amount of bound acetic acid per unit mass of cellulose. The degree of acetylation follows the measurement and calculation of the degree of acetylation in ASTM D-817-91 (test method for cellulose acetate and the like). The viscosity average degree of polymerization (DP) of cellulose acylate is preferably 250 or more, and more preferably 290 or more.
The cellulose acylate used in the present invention preferably has a narrow molecular weight distribution represented by Mw / Mn (Mw is a mass average molecular weight, Mn is a number average molecular weight) by gel permeation chromatography. The specific value of Mw / Mn is preferably in the range of 1.0 to 1.7, more preferably in the range of 1.3 to 1.65, and in the range of 1.4 to 1.6. Most preferably.

[Production of cellulose acetate film]
The cellulose acetate 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 acetate 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 range of carbon atoms 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 halogenated hydrocarbon hydrogen atoms substituted with halogen is preferably 25 to 75 mol%, more preferably 30 to 70 mol%, and more preferably 35 to 65 mol%. More preferably, it is 40 to 60 mol%, and most preferably. Methylene chloride is a representative halogenated hydrocarbon.
Two or more organic solvents may be mixed and used.

A cellulose acetate solution can be prepared by a general method comprising treating 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 acetate is adjusted so that it is contained in an amount of 10 to 40% by mass in the resulting solution. The amount of cellulose acetate is more preferably 10 to 30% by mass. Arbitrary additives described later may be added to the organic solvent (main solvent).
The solution can be prepared by stirring cellulose acetate and an organic solvent at room temperature (0 to 40 ° C.). High concentration solutions may be stirred under pressure and heating conditions. Specifically, cellulose acetate 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., 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 the container. The prepared dope is taken out of the container after cooling, or 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 acetate 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 acetate 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 acetate is gradually added to an organic solvent with stirring at room temperature.
The amount of cellulose acetate is preferably adjusted so as to be contained in the mixture at 10 to 40% by mass. The amount of cellulose acetate 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.). Upon cooling, the mixture of cellulose acetate and organic solvent solidifies.
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 until the final cooling temperature is reached.

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 acetate is dissolved 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 a 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. .
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, the dissolution time can be shortened. In order to perform pressurization and decompression, it is desirable to use a pressure-resistant container.
In addition, according to the measurement by a differential scanning calorimeter (DSC), the 20 mass% solution which melt | dissolved cellulose acetate (acetylation degree: 60.9%, viscosity average polymerization degree: 299) in methyl acetate by the cooling dissolution method is. In the vicinity of 33 ° C., there exists a quasi-phase transition point between a sol state and a gel state, and a uniform gel state is obtained below this temperature. Therefore, this solution needs to be maintained at a temperature equal to or higher than the pseudo phase transition temperature, preferably about the gel phase transition temperature plus about 10 ° C. 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 acetate film is produced from the prepared cellulose acetate solution (dope) by a solvent cast method. It is preferable to add the above-mentioned retardation increasing agent to the dope.
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 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.

In the present invention, when the dope (cellulose acylate solution) is cast on the band, it is substantially 10 seconds to 90 seconds, preferably 15 seconds to 90 seconds in the first half of the drying before peeling, and substantially no wind. The process of drying is performed. In the case of casting on a drum, in the first half of drying before peeling, a step of drying in a substantially windless manner for 1 second to 10 seconds, preferably 2 seconds to 5 seconds is performed.
In the present invention, “drying before peeling” refers to drying from when a dope is applied on a band or drum to when it is peeled off as a film. In addition, the “first half” refers to a process before half of the total time required from dope application to stripping. “Substantially no wind” means that a wind speed of 0.5 m / s or more is not detected at a distance within 200 mm from the band surface or drum surface (the wind speed is less than 0.5 m / s).
The first half of the pre-peeling drying is usually about 30 to 300 seconds on the band, but is dried for 10 to 90 seconds, preferably 15 to 90 seconds, without wind. When it is on the drum, it is usually about 5 to 30 seconds, but it is dried without wind for 1 to 10 seconds, preferably 2 to 5 seconds. The ambient temperature is preferably 0 ° C to 180 ° C, more preferably 40 ° C to 150 ° C. The operation of drying without wind can be performed at any stage in the first half of the drying before peeling, but it is preferable to perform the operation immediately after casting. When the time for drying without wind is less than 10 seconds on the band (less than 1 second on the drum), it is difficult for the additive to be uniformly distributed in the film, and when it exceeds 90 seconds (drum In the above case, if it exceeds 10 seconds), the film will be peeled off due to insufficient drying, and the surface condition of the film will deteriorate.
Drying can be performed by blowing an inert gas for a time other than drying without wind in drying before peeling. The air temperature at this time is preferably 0 ° C to 180 ° C, more preferably 40 ° C to 150 ° C.

  Regarding the drying method in the solvent cast method, U.S. Pat. Nos. 45-4554, 49-5614, JP-A-60-176834, JP-A-60-203430, and JP-A-62-115035. Drying on the band or drum can be performed by blowing an inert gas such as air or nitrogen.

  The obtained film can be peeled off from the drum or band, and further dried by high-temperature air whose temperature is successively changed from 100 to 160 ° C. to evaporate the residual solvent. 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.

  It is also possible to form a film by casting two or more layers using the adjusted cellulose acetate solution (dope). In this case, it is preferable to produce a cellulose acetate 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 acetate liquids of two or more layers, it is possible to cast a plurality of cellulose acetate solutions, and cellulose acetate from a plurality of casting openings provided at intervals in the traveling direction of the support. A film may be produced while casting and laminating solutions each containing. 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 acetate 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 each publication can be used. Further, a cellulose acetate film casting method is disclosed in which a flow of a high-viscosity cellulose acetate solution described in JP-A-56-162617 is wrapped with a low-viscosity cellulose acetate solution, and the high- and low-viscosity cellulose acetate solution is simultaneously extruded. It can also be used.

Also, using two casting ports, the film formed on the support by the first casting port is peeled off, and the second casting is performed on the side that was in contact with the support surface to produce a film. You can also For example, the method described in Japanese Patent Publication No. 44-20235 can be mentioned.
As the cellulose acetate solution to be cast, the same solution may be used, or different cellulose acetate solutions may be used. In order to give a function to a plurality of cellulose acetate layers, a cellulose acetate solution corresponding to the function may be pushed out from each casting port. Furthermore, the cellulose acetate solution of 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 absorption layer, a polarizing layer, etc.).

  In the conventional single-layer liquid, it is necessary to extrude a cellulose acetate 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 acetate solution is poor and solid matter is generated, which often causes problems such as defects in the surface and poor flatness. As a solution to this problem, by casting a plurality of cellulose acetate solutions from the casting port, it is possible to extrude a highly viscous solution onto the support at the same time. Not only can it be produced, but also the use of a concentrated cellulose acetate solution can achieve a reduction in drying load and increase the production speed of the film.

In order to improve the mechanical properties of the cellulose acetate film, the following plasticizers can be used. 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, more preferably 1 to 20% by mass, and most preferably 3 to 15% by mass of the amount of cellulose acylate.

Degradation inhibitors (eg, antioxidants, peroxide decomposers, radical inhibitors, metal deactivators, acid scavengers, amines) may be added to the cellulose acetate 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 0.01 to 1% by mass of the solution (dope) to be prepared from the viewpoint of manifesting the effect and suppressing the bleeding out of the deterioration preventing agent to the film surface. Preferably, it is 0.01 to 0.2 mass%.
Examples of particularly preferred deterioration inhibitors include butylated hydroxytoluene (BHT) and tribenzylamine (TBA).

[Biaxial stretching]
The cellulose acetate film may be stretched to reduce virtual strain. Since stretching can reduce virtual strain in the stretching direction, biaxial stretching may be performed in order to reduce strain in all directions in the plane.
Biaxial stretching includes simultaneous biaxial stretching and sequential biaxial stretching, but sequential biaxial stretching is preferred from the viewpoint of continuous production, and after casting the dope, the film is peeled off from the band or drum, After stretching in the width direction (longitudinal method), the film is stretched in the longitudinal direction (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 not higher than the glass transition temperature of the film. The film can be stretched by a treatment during drying, and is particularly effective when the solvent remains. In the case of stretching in the longitudinal direction, for example, the film is stretched by adjusting the speed of the film transport roller so that the film winding speed is higher than the film peeling speed. 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 stretch ratio of the film (the ratio of the increase due to stretching relative to the original length) is preferably in the range of 5 to 50%, more preferably in the range of 10 to 40%, and in the range of 15 to 35%. Most preferably.

  These steps from casting to post-drying may be performed in an air atmosphere or an inert gas atmosphere such as nitrogen gas. The winder used for producing the cellulose acetate film used in the present invention may be a commonly used winder such as a constant tension method, a constant torque method, a taper tension method, a program tension control method with a constant internal stress, or the like. It can be wound up by the method.

[Surface treatment of cellulose acetate film]
The cellulose acetate film is preferably subjected to a surface treatment. Specific examples include corona discharge treatment, glow discharge treatment, flame treatment, acid treatment, alkali treatment, and ultraviolet irradiation treatment. It is also preferable to provide an undercoat layer as described in JP-A-7-333433.
From the viewpoint of maintaining the flatness of the film, the temperature of the cellulose acetate film in these treatments is preferably Tg (glass transition temperature) or less, specifically 150 ° C. or less.
When used as a transparent protective film of a polarizing plate, it is particularly preferable to carry out acid treatment or alkali treatment, that is, saponification treatment on cellulose acetate, from the viewpoint of adhesiveness with a polarizer.
The surface energy is preferably 55 mN / m or more, and more preferably 60 mN / m or more and 75 mN / m or less.

Hereinafter, the alkali saponification treatment will be specifically described as an example.
The alkali saponification treatment of the cellulose acetate film is preferably performed in a cycle in which the film surface is immersed in an alkaline solution, neutralized with an acidic solution, washed with water and dried.
Examples of the alkaline solution include a potassium hydroxide solution and a sodium hydroxide solution, and the hydroxide ion concentration is preferably in the range of 0.1 to 3.0 mol / liter, and preferably 0.5 to 2.0 mol / liter. More preferably, it is in the range of liters. The alkaline solution temperature is preferably in the range of room temperature to 90 ° C, and more preferably in the range of 40 to 70 ° C.

The surface energy of a solid can be determined by a contact angle method, a wet heat method, and an adsorption method as described in “Basics and Applications of Wetting” (issued by Realize 1989.12.10). In the case of the cellulose acetate film of the present invention, it is preferable to use a contact angle method.
Specifically, two types of solutions having known surface energies are dropped on a cellulose acetate film, and at the intersection between the surface of the droplet and the surface of the film, the angle formed by the tangent line drawn on the droplet and the film surface The surface angle of the film can be calculated by defining the angle containing the droplet as the contact angle.

[Film retardation]
In this specification, Re and Rth respectively represent in-plane retardation and retardation in the thickness direction at a wavelength λ. Re is measured with KOBRA 21ADH (manufactured by Oji Scientific Instruments Co., Ltd.) by making light of wavelength λ nm incident in the normal direction of the film. Rth was measured by making light having a wavelength λ nm incident from a direction inclined + 40 ° with respect to the normal direction of the film with the slow axis in the plane (determined by KOBRA 21ADH) as the tilt axis (rotation axis). A retardation value and a retardation value measured by making light having a wavelength λ nm incident from a direction inclined −40 ° with respect to the film normal direction with the in-plane slow axis as the tilt axis (rotation axis). KOBRA 21ADH is calculated based on the retardation value measured in the direction. Here, as the assumed value of the average refractive index, values in the polymer handbook (John Wiley & Sons, Inc.) and catalogs of various optical films can be used. Those whose average refractive index is not known can be measured with an Abbe refractometer. 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), and polystyrene (1.59). The KOBRA 21ADH calculates nx, ny, and nz by inputting the assumed value of the average refractive index and the film thickness. Nz = (nx−nz) / (nx−ny) is further calculated from the calculated nx, ny, and nz.

The cellulose acylate film of the present invention is used as a protective film for a polarizing plate, and can be particularly preferably used as a retardation film corresponding to various liquid crystal modes.
When the cellulose acylate film of the present invention is used as a retardation film, preferred optical properties of the cellulose acylate film vary depending on the liquid crystal mode.
For the OCB mode, Re is preferably 10 to 100, more preferably 20 to 70. Rth is preferably 50 to 300, more preferably 100 to 250.
For the VA mode, Re is preferably 20 to 150, more preferably 30 to 120. Rth is preferably from 50 to 300, more preferably from 120 to 250.
For TN, Re is preferably 0-50, more preferably 2-30. Rth is preferably 10-200, more preferably 30-150.
For IPS, Re is preferably 0 to 5, and more preferably 0 to 2. Rth is preferably -20 to 20, and more preferably -10 to 10.
In the OCB mode and the TN mode, an optically anisotropic layer can be applied on the cellulose acylate film having the retardation value and used as an optical compensation film.

  In addition, it is preferable that the birefringence ((DELTA) n: nx-ny) of a cellulose acylate film exists in the range of 0.00 thru | or -0.002 micrometer. The birefringence {(nx + ny) / 2-nz} in the thickness direction of the support film and the counter film is preferably in the range of 0.00 to 0.04.

[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 / N or less. 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.

Next, the polarizing plate of the present invention will be described in detail.
(Configuration of polarizing plate)
First, a protective film and a polarizer constituting the polarizing plate of the present invention will be described.
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, etc., and is a cellulose acylate film. Most preferred.

(2) Polarizer The polarizer of the present invention is preferably composed of polyvinyl alcohol (PVA) and a dichroic molecule. However, as described in JP-A-11-248937, PVA and polyvinyl chloride are dehydrated, A polyvinylene polarizer in which a polyene structure is generated by dechlorination and oriented is also usable.

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.
The syndiotacticity of PVA is preferably 55% or more for improving durability as described in Japanese Patent No. 2978219, but 45 to 52.5% described in Japanese Patent No. 3317494 is also preferably used. Can do.

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 in which a PVA resin is dissolved 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 No. 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 during stretching of the PVA film. Alternatively, as described in JP-A-2002-060505, the value of (nx + ny) / 2-nz may be set to 0.0003 or more and 0.01 or less. The retardation (in-plane) of the PVA film is preferably from 0 nm to 100 nm, and more preferably from 0 nm to 50 nm. Moreover, 0 nm or more and 500 nm or less are preferable, and, as for Rth (film thickness direction) of a PVA film, 0 nm or more and 300 nm or less are more preferable.

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 range in the TD direction of 1.5 ° C. or less of the film described in JP-A-2002-030163 Further, a film was formed from a solution in which 1 to 100 parts by mass of a tri- to hexavalent polyhydric alcohol such as glycerin or a plasticizer described in JP-A 06-289225 was mixed at least 15% by mass. A 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 may be used in which the stress generated when stretching 4 to 6 times in water is 10 N or less.

The dichroic molecules, I ₃ ^- and I ₅ ^- can be preferably used an 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 at least one of a solution obtained by dissolving iodine in a potassium iodide aqueous solution and 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, so that a free acid, an alkali metal salt, an ammonium salt or an amine is introduced. 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 such as Direct Red 79, C.I. I. Stilbene series such as Direct Yellow 12, C.I. I. Dinaphthylamine type such as Direct Red 31, C.I. I. Direct Red 81, C.I. I. Direct Violet 9, C.I. I. Mention may be made of J acid systems 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 in the film is usually from 0.01% by mass with respect to the polyvinyl alcohol polymer constituting the film matrix from the viewpoint of maintaining a high degree of polarization and single plate transmittance. It is adjusted in the range of 5% by mass.
A preferable film thickness of the polarizer is preferably 5 μm to 40 μm, 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 ≦ A (polarizer film thickness) / B (protective film film thickness) ≦ 0, as described in JP-A No. 2002-174727. A range of 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 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. Moreover, 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 to sequentially perform the swelling process, the dyeing process, the hardening process, the stretching process, the drying process, the protective film bonding process, and the drying process after bonding in the order described. An on-line surface inspection step may be provided during or after the above-described steps.

The swelling step is preferably performed only with water, but as described in JP-A-10-153709, for the purpose of stabilizing optical performance and avoiding wrinkling of the polarizing plate substrate in the production line. It is also possible to manage the degree of swelling of the polarizing plate substrate 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 step, the method described in JP-A-2002-86554 can be used. Further, as a dyeing method, not only immersion but any means such as application or spraying of iodine or a dye solution can be used. 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 preferably 0.05 to 20 g / l, potassium iodide is 3 to 200 g / l, and the mass ratio of iodine and potassium iodide is preferably 1 to 2000. The dyeing time is preferably 10 to 1200 seconds, and the liquid temperature is preferably 10 to 60 ° C. More preferably, iodine is 0.5 to 2 g / l, potassium iodide is 30 to 120 g / l, the mass ratio of iodine and potassium iodide is 30 to 120, dyeing time is 30 to 600 seconds, and liquid temperature is 20-50 degreeC is good.
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 step, it is preferable to immerse in the crosslinking agent solution or apply the solution to contain 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 a 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. However, as described in JP-A No. 2000-35512, zinc halide such as zinc iodide, zinc sulfate such as zinc acetate is 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 perform dura- tion by immersing the PVA film. Boric acid is preferably 1 to 100 g / l, potassium iodide is 1 to 120 g / l, zinc chloride is preferably 0.01 to 10 g / l, hardening time is preferably 10 to 1200 seconds, and liquid temperature is preferably 10 to 60 ° C. . More preferably, boric acid is 10 to 80 g / l, potassium iodide is 5 to 100 g / l, zinc chloride is 0.02 to 8 g / l, hardening time is 30 to 600 seconds, and liquid temperature is 20 to 50 ° C is preferable.

  For the stretching step, it is preferable to use a longitudinal uniaxial stretching method as described in US Pat. No. 2,454,515 or the like, or a tenter method as described in JP-A-2002-86554. it can. 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. In addition, the relationship between the draw ratio, the original fabric thickness, and the polarizer thickness is described in JP-A No. 2002-040256 (polarizer film thickness after protective film bonding / original fabric film thickness) × (total draw ratio) )> 0.17, or the relationship between the width of the polarizer when leaving the final bath and the width of the polarizer when bonding the protective film is 0.80 ≦ (protection) described in JP-A-2002-040247 It is also preferable to set the polarizer width at the time of film bonding / the width of the polarizer when leaving the final bath) ≦ 0.95.

  As the 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 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 performed.

  A protective film bonding process is a process of bonding the both surfaces of the above-mentioned polarizer which went out of the drying process 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% 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. PVA resin is preferable. 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 undercoat layer may be provided after the surface treatment. As described in JP-A-2002-267839, 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 the preferred temperature range is 30 ° C. to 100 ° C., and the preferred 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.

Element content in the polarizer, iodine 0.1 to 3.0 g / ^{m 2,} boron 0.1 to 5.0 g / ^{m 2,} potassium 0.1~2.00g / ^{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 mass%-0.5 mass%.

  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. It is also possible to use and contain at least one compound selected from organic titanium compounds and organic zirconium compounds. 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 is 42.5% or more and 49.5% or less, more preferably 42.8% or more and 49.0% or less. A preferable range of the degree of polarization defined by Formula 1 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. A preferable range of the dichroic ratio defined by Formula 2 is 48 or more and 1215 or less, and more preferably 53 or more and 525 or less.

  The above-described transmittance is defined by Equation 3 below based on JISZ8701.

  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 system τ (λ): spectral transmittance

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 Laid-Open No. 2002-221618, the standard deviation of the parallel transmittance every 10 nm when the light wavelength is 420 to 700 nm is 3 or less, and 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 the orthogonal transmittance at a wavelength of 440 nm of the polarizing plate, the parallel transmittance, the parallel transmittance and the orthogonal transmittance at a wavelength of 550 nm, the parallel transmittance and the orthogonal transmittance at a wavelength of 610 nm are disclosed in JP-A-2002-258042. It is also preferable to set the range described in Japanese Unexamined Patent Publication No. 2002-258043.

(2) Hue The hue of the polarizing plate of the present invention is preferably evaluated 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. Is done.
L ^* , a ^* , and b ^* are defined by Equation 5 using X, Y, and Z described above.

Here, X ₀ , Y ₀ , and Z ₀ represent tristimulus values of the illumination light source. In the case of the standard light C, X ₀ = 98.072, Y ₀ = 100, Z ₀ = 118.225, and the standard light In the case of D 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. The 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. A preferable range of b ^* of parallel transmitted light of the two polarizing plates is 2.0 or more and 8 or less, and 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 the chromaticity coordinates (x, y) calculated from the aforementioned X, Y, and Z. For example, the chromaticity (x _p , y _p ) of the parallel transmitted light of the two polarizing plates. And the chromaticity (x _c , y _c ) of the orthogonal transmitted light are within the ranges described in JP 2002-214436 A, JP 2001-166136 A, JP 2002-169024 A, It is also preferable to make the absorbance relationship within the range described in JP-A-2001-311827.

(3) Viewing angle characteristics When a polarizing plate is arranged in crossed Nicol and light with a wavelength of 550 nm is incident, when vertical light is incident, from a azimuth of 45 degrees with respect to the polarization axis, 40 degrees with respect to the normal line It is also preferable to set the transmittance ratio and the xy chromaticity difference in the range described in Japanese Patent Laid-Open Nos. 2001-166135 and 2001-166137 when the light is incident at an angle of. Further, as described in JP-A-10-068817, the light transmittance (T ₀ ) in the vertical direction of the polarizing plate laminated body arranged in crossed Nicols and the light in the direction inclined by 60 ° from the normal line of the laminated body 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 range from the normal to an elevation angle of 80 degrees. When natural light is incident at an angle, the transmittance difference of transmitted light within a wavelength range of 20 nm within the wavelength range of 520 to 640 nm of the transmission spectrum is set to 6% or less, 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) Wet heat durability When the light transmittance and the degree of polarization change before and after leaving in an atmosphere of 60 ° C. and 95% RH for 500 hours are 3% or less based on absolute values Preferably there is. 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 based on the absolute value. Further, as described in JP-A-07-0777608, it is also preferable that the degree of polarization after standing at 80 ° C., 90% RH and 500 hours is 95% or more and the single transmittance is 38% or more.

(4-2) Dry durability It is preferable that the light transmittance and the rate of change of the degree of polarization before and after standing in a dry atmosphere at 80 ° C. for 500 hours are also 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 No. 06-167611, the shrinkage rate after leaving at 80 ° C. for 2 hours is 0.5% or less, or on both surfaces of the glass plate. The x- and y-values after leaving the crossed Nicol-arranged polarizing plate laminate in an atmosphere of 69 ° C. for 750 hours are within the range described in JP-A-10-068818, or 80 ° C. and 90% RH. the change in spectral intensity ratio of the 105 cm ^-1 and 157cm ^-1 by Raman spectroscopy after 200 hours standing process in an atmosphere of a range described in JP-a-08-094834 and JP 09-197127 It can also be preferably performed.

(5) Orientation degree The higher the degree of orientation of PVA, the better the polarization performance, but the order parameter value calculated by means such as polarization Raman scattering or polarization FT-IR is preferably 0.2 to 1.0. It is a range. Also, 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 dye molecule (0.75 or more) is at least 0. .15, or the orientation coefficient of the amorphous region of the polarizer is 0.65 to 0.85 as described in JP-A No. 04-204907, or higher iodine of I ₃ ⁻ or I ₅ ⁻ The degree of orientation of ions can also be preferably set to 0.8 to 1.0 and 1.0 as order parameter values.

(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 Japanese Unexamined Patent Publication 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 rate in the polarizing axis direction of the polarizing plate are In addition, it can be preferably carried out within the range of ± 0.6%, or the moisture content of the polarizing plate can be 3% by mass or less as described in JP-A-2002-090546. Further, as described in JP 2000-249832 A, 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 in JP 10-268294 A As described, the refractive index n _{0 in the} direction of the transmission axis is made larger than 1.6, or the relationship between the thickness of the polarizing plate and the thickness of the protective film is within the range described in JP-A-10-111411. 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 and the above-described functional optical film are combined is shown in FIG. The functional optical film 3 and the polarizer 2 may be bonded via a pressure-sensitive adhesive layer as a protective film on one side of the polarizing plate 5 (FIG. 1A), and the protective films 1a and 1b are attached to both surfaces of the polarizer 2, respectively. The functional optical film 3 may be bonded to the provided polarizing plate 5 through the adhesive layer 4 (FIG. 1B). 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 as described in JP-A-2002-311238. The functional optical film is preferably disposed on the liquid crystal module side according to the intended function, or on the side opposite to the liquid crystal module, that is, on the display side or the backlight side.

The functional optical film used in combination with the polarizing plate of the present invention will be described below.
(1) Viewing angle expansion film The polarizing plate of the present invention includes TN (Twisted Nematic), IPS (In-Plane Switching), OCB (Optically Compensated Bend), VA (Vertically Aligned), and ECB (Electrically Bold). It can be used in combination with a viewing angle widening film proposed for the display mode.

As a viewing angle widening film for the TN mode, the Japan Printing Society Vol. 36, No. 3 (1999) p. 40-44, monthly display August issue (2002) p. No. 20-24, JP-A-4-229828, JP-A-6-75115, JP-A-6-214116, JP-A-8-50206, etc. are preferably used in combination. The
A preferred 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 transparent polymer film. Although a viewing angle expansion film may be used by being bonded to a polarizing plate via an adhesive, SID'00 Dig. , P. As described in 551 (2000), it is particularly preferable from the viewpoint of thinning that one of the protective films of the polarizer is also used.

  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, but an alignment layer formed by a rubbing treatment of a polymer is particularly preferable. 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 crystal 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 the triphenylene derivative of D-1, 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.

  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 a discotic compound and another compound (for example, a polymerizable monomer, a photopolymerization initiator) dissolved in a solvent, coated on the alignment layer, dried, and then discotic nematic. After heating to the phase formation temperature, it is obtained by polymerization by irradiation with UV light or the like and further 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, additives for controlling the orientation on the air interface side such as polymerizable monomers (eg, compounds having vinyl group, vinyloxy group, acryloyl group and methacryloyl group), fluorine-containing triazine compounds, cellulose acetate, cellulose acetate Mention may be made of polymers such as pionate, 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, more preferably 0.5 to 5 μm.

  A preferred embodiment of the viewing angle widening film is composed of 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 And 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 JP-A-07-198942, it has an optical axis in a direction intersecting the plate surface. It is laminated with a retardation plate exhibiting anisotropy in birefringence, or the dimensional change rate of the protective film and the optically anisotropic layer is substantially equal as described in JP-A No. 2002-258052. Can also be preferably performed. Further, as described in JP-A-12-258632, the moisture content of the polarizing plate bonded to the viewing angle widening film is set to 2.4% or less, or described in JP-A-2002-267839. It is also preferable to make the contact angle with water on the surface of the viewing angle widening film 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 for improving the viewing angle characteristics of the orthogonal transmittance of the polarizing plate during black display without 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 as described in JP-A-10-54982 is close to 0 and the thickness direction is reduced in order to reduce leakage light. It is 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, it is preferably used in combination with a viewing angle widening film in which a discotic liquid crystalline compound as described in US Pat. No. 5,805,253 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, and a discotic compound are used. Films arranged in parallel to the substrate, stretched films with the same in-plane retardation value laminated so that the slow axes are orthogonal, and liquid crystals to prevent the 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 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 is from 400 to 700 nm, the larger the retardation, and the retardation value (Re450) measured at a wavelength of 450 nm is 80 to 125 nm. And the range which satisfies the relationship whose retardation value (Re590) measured at wavelength 590nm is 120 thru | or -160nm is shown. It is more preferable that Re590-Re450 ≧ 5 nm, and it is particularly preferable that Re590-Re450 ≧ 10 nm.

  The λ / 4 plate used in the present invention is not particularly limited as long as the above conditions are satisfied, but for example, 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 a single polymer film described in WO00 / 65384, WO00 / 26705, JP 2000-284126 A, A known λ / 4 plate such as a λ / 4 plate in which at least one optically anisotropic layer is provided on a polymer film described in JP-A-2002-31717 can be used. 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 / 2 plate is preferably bonded so that the angle formed between 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% obtained by applying a single layer of a low refractive index material such as a fluorine polymer, or a film having a reflectivity of 1% or less using multilayer interference of thin films 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 middle refractive index layer) is laminated on a transparent support is preferably used. The In addition, Nitto Technical Report, vol. 38, no. 1, may, 2000, pages 26 to 28, JP-A-2002-301783, and the like can also be preferably used.
The refractive index of each layer satisfies the following relationship.

The refractive index of the high refractive index layer> The refractive index of the medium refractive index layer> The refractive index of the transparent support> The refractive index of the low refractive index layer. The transparent support used for the antireflection film is used for the protective film for the polarizer described above. A transparent polymer film can be preferably used.

  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 JP-A-2001-40284. The compounds described in paragraph Nos. [0027] to [0028] and JP-A No. 2000-284102 can be preferably used.

The silicone-containing compound is preferably a compound having a polysiloxane structure, but reactive silicone (eg, Silaplane (manufactured by Chisso Corporation), silanol group-containing polysiloxane at both ends (Japanese Patent Laid-Open No. 11-258403), etc. 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). Gazettes, 58-147483, 58-147484, JP-A-9-157582, 11-106704, JP-A-2000-117902, 2001-48590, 2002-2002. 53804).
The low refractive index layer has an average primary particle diameter of 1 to 150 nm such as fillers (for example, silicon dioxide (silica), fluorine-containing particles (magnesium fluoride, calcium fluoride, barium fluoride)) as additives other than the above. And a low refractive index inorganic compound, organic fine particles described in paragraphs [0020] to [0038] of JP-A-11-3820), silane coupling agents, slip agents, surfactants, and the like are also preferably included. be able to.

The low refractive index layer may be formed by a vapor phase method (vacuum vapor 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.

The medium refractive index layer and the high refractive index layer preferably have a constitution in which ultrafine particles of high refractive index having an average particle size 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-A No. 2001-310432 or the like, a core-shell structure having a high refractive index particle as a core (JP-A No. 2001-166104, etc.), or a specific dispersant (for example, Japanese Patent Application Laid-Open No. 11-153703, Japanese Patent No. US6110858B1, Japanese Patent Application Laid-Open No. 2002-276069, etc.).

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 strength of the film is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test according to JIS K5400.

(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 scatters one circularly polarized light or linearly polarized light back to the backlight side. Re-reflected light from the backlight part partially changes the polarization state and partially transmits when re-entering the brightness enhancement film and the polarizing plate, so the light utilization rate is improved by repeating this process. The front luminance is improved to about 1.4 times. As the brightness enhancement film, an anisotropic reflection system and an anisotropic scattering system are known, and both can be combined with the polarizing plate of the present invention.

  In the anisotropic reflection system, 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 and increasing the refractive index difference in the stretching direction. Multilayer film systems using the principle of dielectric mirrors (described in the specifications of WO95 / 17691, WO95 / 17692, WO95 / 17699) and cholesteric liquid crystal systems (European Patent No. 606940A2, Japanese Patent Laid-Open No. Hei 8- No. 271731) is known. DBEF-E, DBEF-D, and DBEF-M (all manufactured by 3M) are used as multi-layer brightness enhancement films using the principle of dielectric mirrors, and NIPOCS (Nitto Denko Corporation) as a cholesteric liquid crystal brightness enhancement film. )) Is preferably used in the present invention. For NIPOCS, see Nitto Giho, vol. 38, no. 1, may, 2000, pages 19 to 21 and the like.

Further, in the present invention, positive numbers described in the specifications of WO97 / 32223, WO97 / 32224, WO97 / 32225, WO97 / 32226 and JP-A-9-274108 and 11-174231 It is also preferable to use a combination of an anisotropic scattering type brightness enhancement film uniaxially stretched by blending an intrinsic birefringent polymer and a negative intrinsic birefringent polymer. 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 comprises 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 preferable to use in combination with the provided functional optical film. These functional layers are also preferably used in combination with each other in the same layer as the antireflection layer in the above-mentioned antireflection film or the optically anisotropic layer in the viewing angle compensation film. These functional layers can be used by providing either one side or both sides of the polarizer side and the surface opposite to the polarizer (more air side surface).

(5-1) Hard coat layer The polarizing plate of the present invention is preferably combined with a functional optical film having a hard coat layer provided on the surface of the transparent support in order to impart mechanical strength such as scratch resistance. . When the hard coat layer is applied to the above-described 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 a curable compound by at least one of light and heat. As specific constituent compositions of the hard coat layer, for example, those described in JP-A Nos. 2002-144913, 2000-9908 and WO00 / 46617 can be preferably used.
The film thickness of the hard coat layer is preferably 0.2 to 100 μm.
The strength of the hard coat layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test according to JIS K5400. Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

  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. Moreover, as a commercially available compound, EB-600, EB-40, EB-140, EB-1150, EB-1290K, IRR214, EB-2220, TMPTA, TMPTMA (above, Daicel UCB Co., Ltd. product), UV -6300, UV-1700B (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 2021P, Celoxide 2081 GT-301, Epolide GT-401, EHPE3150CE (above, Oxetane, OXT-121, OXT-221, OX-SQ, PNOX-1009 (above, manufactured by Toagosei Co., Ltd.), etc. Can be mentioned. In addition, a polymer of glycidyl (meth) acrylate or a copolymer of a monomer that can be copolymerized with glycidyl (meth) acrylate may be used for the hard coat layer.

  In the hard coat layer, fine particles of oxide such as silicon, titanium, zirconium, and aluminum are used to reduce curing shrinkage of the hard coat layer, improve adhesion to the substrate, and reduce curling of the hard coat treated article of the present invention. It is also preferable to add crosslinked fine particles such as crosslinked fine particles such as polyethylene, polystyrene, poly (meth) acrylic acid esters, polydimethylsiloxane, etc., and fine organic particles such as fine crosslinked rubber particles such as SBR and NBR. These crosslinked fine particles preferably have an average particle size of 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.

  In the case of adding the inorganic fine particles described above, since the affinity with the binder polymer is generally poor, it contains a metal such as silicon, aluminum, titanium, and the alkoxide group, carboxylic acid group, sulfonic acid group, phosphonic acid group, etc. It is also preferable to perform a surface treatment using a surface treatment agent having a functional group of

  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 the 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 that 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) Antiglare layer The antiglare (antiglare) 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.) can be preferably used.

5. (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 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 substrate 10 and a lower 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, and includes TN (Twisted Nematic), IPS (In-Plane Switching), OCB (Optically Compensatory Bend), VA (Vertical Aligned Electron), ECB (Etc. 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 substrates 10 and 13 in contact with the liquid crystal molecules 12 (hereinafter sometimes referred to as “inner surface”), and by a rubbing process or the like applied on the alignment film, 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.
In general, the crossing angle of the absorption axis 7 of the upper polarizing plate 6 and the absorption axis 18 of the plate 17 of the lower polarizing plate 17 is generally orthogonally laminated to obtain a high contrast. 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 depends 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. In addition, the aforementioned viewing angle widening films 8 and 15 can be separately disposed between the liquid crystal cell and the polarizing plate. The polarizing plates 6 and 17 and the viewing angle widening films 8 and 15 may be arranged in a laminated form bonded with an adhesive, or a so-called integrated elliptical polarization using one of the liquid crystal cell side protective films for widening the viewing angle. It may be arranged as a 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.

Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited to the examples.
<Measurement of retardation>
Re and Rth were measured at 25 ° C. and 60% RH by the following method.
In-plane retardation Re (0) was measured using an automatic birefringence meter (KOBRA-21ADH, manufactured by Oji Scientific Instruments). Retardation Re (40) and Re (-40) were measured with the in-plane slow axis as the tilt axis at 40 ° and -40 °. Using the film thickness and the refractive index nx in the slow axis direction as parameters, the refractive index ny and the thickness direction in the fast axis direction are fitted to these measured values Re (0), Re (40), and Re (−40). The refractive index nz was determined by calculation to determine the Rth retardation value. The measurement wavelength was 590 nm.

Example 1
(Preparation of cellulose acetate solution)
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acetate solution A.
<Composition of cellulose acetate solution A>
Cellulose acetate with 60.9% acetylation produced from lintercellulose
80.0 parts by weight Cellulose acetate produced from lintercellulose and having an acetylation degree of 61.2%
20.0 parts by mass Triphenyl phosphate (plasticizer) 7.0 parts by mass Biphenyl diphenyl phosphate (plasticizer) 4.0 parts by mass Methylene chloride (first solvent) 402.0 parts by mass Methanol (second solvent) 60.0 Parts by mass

(Preparation of matting agent solution)
The following composition was charged into a disperser and stirred to dissolve each component to prepare a matting agent solution.
<Matting agent solution composition>
Silica particles having an average particle diameter of 16 nm 2.0 parts by mass (AEROSIL R972, Methylene chloride (first solvent) 76.3 parts by mass Methanol (second solvent) 11.4 parts by mass Cellulose acetate solution A 10 manufactured by Nippon Aerosil Co., Ltd. .3 parts by mass The secondary particle size after preparation of the silica particles was 0.3 μm.

(Preparation of retardation increasing agent solution)
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a retardation increasing agent solution.
<Retardation raising agent solution composition>
Retardation increasing agent (Ex. No. 144) 19.8 parts by mass The following UV absorber (A) 0.07 parts by mass The following UV absorber (B) 0.13 parts by mass Methylene chloride (first solvent) 58.4 parts by mass Methanol (second solvent) 8.7 parts by mass Cellulose acetate solution A 12.8 parts by mass

(Production of cellulose acetate film)
94.6 parts by mass of the cellulose acetate solution A, 1.3 parts by mass of the matting agent solution, and 4.1 parts by mass of the retardation increasing agent solution were mixed after filtration, and 10 m / min using a band casting machine. Cast at speed. The mass ratio of the retardation increasing agent to cellulose acetate was 4.6%. The film was peeled from the band after drying to a residual solvent amount of 30% with a wind at a dew point of −10 ° C. Further, under the condition of 130 ° C., a film having a residual solvent amount of 13% by mass was horizontally stretched at a stretch ratio of 28% using a tenter, and held at 140 ° C. for 30 seconds with the stretched width. Thereafter, the clip was removed and dried at 140 ° C. for 40 minutes to produce a cellulose acetate film. The resulting cellulose acetate film had a residual solvent amount of 0.2% and a film thickness of 92 μm.
In the present invention, the amount of residual solvent in the film formed on the support is represented by the following formula.
Residual solvent amount = (mass of residual volatile matter / film mass after heat treatment) × 100%
The residual volatile matter mass is a value obtained by subtracting the film mass after the heat treatment from the film mass before the overheat treatment when the film is heat treated at 115 ° C. for 1 hour.
Cellulose acetate films 102 to 122 were produced in the same manner except that the time when the windless drying was performed immediately after casting and the retardation increasing agent were changed to those shown in Table 1 below.
The amount of the retardation increasing agent on the film surface was measured by a time-of-flight secondary ion mass spectrometer (TOF-SIMS). By taking the intensity ratio of the peak of the molecule + H ⁺ ion of the M retardation increasing agent to the positive ion peak m / Z = 109 (C ₆ H ₅ O ₂ ⁺ ) derived from the decomposition product of cellulose acylate, the air surface Each of the support surfaces was measured at N = 3, and the ratio of average air surface abundance / support surface abundance was determined. The results are shown in Table 1.

  Bleed-out was evaluated by visually observing the film surface and the presence or absence of foreign matter on the surface. In addition, the curl was evaluated by the deviation of the film edge from the horizontal plane when the film was cut into 20 cm × 20 cm and left on a flat table.

  From the results shown in Table 1, it can be seen that the cellulose acylate film of the present invention has no bleed-out and curl is small, which is preferable.

Example 2
(Saponification treatment)
On the cellulose acylate film 101 produced in Example 1, 5.2 ml / m ^{2 of the following} composition was applied 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 solution composition>
Isopropyl alcohol 818 parts by weight Water 167 parts by weight Propylene glycol 187 parts by weight Potassium hydroxide 80 parts by weight

(Formation of alignment film)
On the band surface side of the saponified cellulose acylate film (101), a coating solution having the following composition was applied at 24 ml / m ² with a # 14 wire bar coater. An alignment film was formed by drying with warm air of 60 ° C. for 60 seconds and further with warm air of 90 ° C. for 150 seconds.
Next, a rubbing treatment was performed on the alignment film formed in a direction of 45 ° with the stretching direction (same as the slow axis) of the cellulose acylate film (101).
<Alignment film coating solution composition>
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 and production of optical compensation film)
On the alignment film, 91 parts by mass of the following discotic compound, 9 parts by mass of ethylene oxide-modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.), cellulose acetate butyrate (CAB531-1, Eastman) Chemical Co., Ltd.) 1.5 parts by mass, Photopolymerization initiator (Irgacure 907, Ciba Geigy Co., Ltd.) 3 parts by mass, Sensitizer (Kayacure DETX, Nippon Kayaku Co., Ltd.) 1 part by mass A coating solution dissolved in parts by mass of methyl ethyl ketone was applied with 5.2 ml / m ² using 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 a hybrid optical compensation film (101) was produced.

(Preparation of polarizing plate)
A polarizing film was prepared by adsorbing iodine to a stretched polyvinyl alcohol film.
Next, the transparent support side of the produced optical compensation film (101) was attached to one side of the polarizing film using a polyvinyl alcohol-based adhesive. The slow axis of the transparent support and the transmission axis of the polarizing film 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 described above, and the other side of the polarizing film (the optical compensation film was not attached) using a polyvinyl alcohol-based adhesive. Affixed to the side).
In this manner, an elliptically polarizing plate (101) was produced.

(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 faced to each other so that the rubbing directions were parallel to each other, and the cell gap was set to 5.7 μm. A bend-aligned liquid crystal cell was prepared by injecting a liquid crystal compound (ZLI1132, manufactured by Merck & Co., Inc.) having a Δn of 0.1396 into the cell gap.

(Production of liquid crystal display device)
Two produced elliptical polarizing plates (101) were attached so as to sandwich the produced bend alignment cell. The optically anisotropic layer of the elliptically polarizing plate was arranged so as to face the cell substrate, and the rubbing direction of the liquid crystal cell and the rubbing direction of the alignment film facing it were antiparallel.
Similarly, for the cellulose acylate films (102) to (116), a liquid crystal display device on which an elliptically polarizing plate with an optical compensation film using the same is attached is produced, and display of point defects, spots, etc. in black display is performed. Checked for failure.
It was found that the liquid crystal display device using the cellulose acylate film of the present invention has few display defects and a good image can be obtained.

Example 3
The following cellulose acetate solution B composition was put into a mixing tank, stirred while heating to dissolve each component, and a cellulose acetate solution B was prepared.
<Cellulose acetate solution B composition>
Cellulose acetate produced from lintercellulose and having an acetylation degree of 60.7%
50.0 parts by weight Cellulose acetate with 61.3% acetylation produced from lintercellulose
50.0 parts by mass Triphenyl phosphate (plasticizer) 7.0 parts by mass Biphenyl diphenyl phosphate (plasticizer) 4.0 parts by mass Methylene chloride (first solvent) 402.0 parts by mass Methanol (second solvent) 60.0 Parts by mass

In another mixing tank, 16 parts by mass of retardation increasing agent (144), 80 parts by mass of methylene chloride and 20 parts by mass of methanol were added and stirred while heating to prepare retardation increasing agent solution D.
11 parts by mass of retardation increasing agent solution D was mixed with 474 parts by mass of cellulose acetate solution B, and the dope was prepared by sufficiently stirring. The addition amount of the retardation increasing agent was 1.6 parts by mass with respect to 100 parts by mass of cellulose acetate.
The obtained dope was cast using a band casting machine at a casting speed of 45 m / min, dried to a residual solvent amount of 30% with a wind at a dew point of −20 ° C., and then the film was peeled off from the band. Next, the film was dried with a drying air of 140 ° C. for 10 minutes to produce a cellulose acetate film 201 having a residual solvent amount of 0.3 mass% and a thickness of 58 μm.
Cellulose acetate films 202 to 211 were prepared in the same manner as the cellulose acetate film 201 except that the time for performing windless drying immediately after casting and the type of retardation increasing agent were changed to those shown in Table 2.
It turned out that the cellulose acetate films 201-204 of this invention do not have a bleed-out, and are excellent in surface shape.
In Comparative Examples 205 to 208, bleeding out was observed.

Example 4

(Saponification treatment)
On the cellulose acetate films 201 to 206 produced in Example 3, 5.2 ml / m ^{2 of the following} composition was applied 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 solution composition>
Isopropyl alcohol 818 parts by weight Water 167 parts by weight Potassium hydroxide 777 parts by weight

(Formation of alignment film)
On the saponified cellulose acetate film, a coating solution having the following composition was applied at 28 ml / m ² with a # 16 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 a direction parallel to the longitudinal direction of the cellulose acetate film.

(Orientation film coating solution composition)
Polyvinyl alcohol used for forming the alignment film in Example 2 10 parts by mass Water 371 parts by mass Methanol 119 parts by mass Glutaraldehyde (crosslinking agent) 0.5 parts by mass

(Formation of optically anisotropic layer)
On the alignment film, 41.01 g of the discotic liquid crystalline compound used in Example 2, 4.06 g of ethylene oxide-modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.), cellulose acetate butyrate ( CAB551-0.2, manufactured by Eastman Chemical Co.) 0.90 g, cellulose acetate butyrate (CAB531-1, manufactured by Eastman Chemical Co.) 0.23 g, photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy Co.) A coating solution in which 35 g and 0.45 g of a sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) were dissolved in 102 g of methyl ethyl ketone was applied with a wire bar of # 3.6. This was heated in a constant temperature zone of 130 ° C. for 2 minutes to orient the discotic compound. Next, UV irradiation was performed for 1 minute using a 120 W / cm high pressure mercury lamp in an atmosphere of 60 ° C. to polymerize the discotic compound. Then, it stood to cool to room temperature. Thus, an optically anisotropic layer was formed, and an optical compensation film (D-1) was produced.
The Re retardation value of the optically anisotropic layer measured at a wavelength of 546 nm was 43 nm. Further, the angle (inclination angle) between the disk surface and the first transparent support surface increased stepwise from the support surface, and averaged 42 °.

Iodine was adsorbed on the stretched polyvinyl alcohol film to prepare a polarizer, and was attached to one side of the polarizer using a polyvinyl alcohol adhesive so that the cellulose acetate film of the present invention was on the polarizing film side. The transmission axis of the polarizer and the slow axis of the optically anisotropic layer were arranged in parallel.
Further, a commercially available cellulose triacetate film (Fujitac TD80UF, manufactured by Fuji Photo Film Co., Ltd.) was saponified in the same manner as described above, and was attached to the opposite side of the polarizer using a polyvinyl alcohol adhesive.

(Production of liquid crystal display device)
A pair of polarizing plates provided in a 20-inch liquid crystal display device (LC-20V1, manufactured by Sharp Corporation) using a TN type liquid crystal cell is peeled off, and instead of the polarizing plate prepared above, an optical compensation film is used. One sheet was attached to the observer side and the backlight side through an adhesive so as to be on the liquid crystal cell side. The transmission axis of the polarizing plate on the observer side and the transmission axis of the polarizing plate on the backlight side were arranged so as to be orthogonal.
It was found that the liquid crystal display device using the cellulose acetate film of the present invention has few display defects and can provide a good image.

Example 5
(Preparation of cellulose acylate film)
The following composition was put into a mixing tank, stirred while heating to dissolve each component, and a cellulose acylate solution E was prepared.
(Cellulose acylate solution E composition)
Cellulose acetate produced from wood pulp and having an acetylation degree of 60.0%
10 parts by weight Cellulose acetate produced from wood pulp and having an acetylation degree of 61.1%
90 parts by weight Triphenyl phosphate (plasticizer) 7.8 parts by weight Biphenyl diphenyl phosphate (plasticizer) 3.9 parts by weight Methylene chloride (first solvent) 300 parts by weight Methanol (second solvent) 54 parts by weight 1-butanol 11 Parts by mass

The following composition was charged into another mixing tank, stirred while heating to dissolve each component, and a retardation increasing agent solution F was prepared.
<Retardation raising agent solution F composition>
Retardation raising agent (161) 3 parts by mass Methylene chloride 80 parts by mass Methanol 20 parts by mass

15 parts by mass of the retardation increasing agent solution F was added to 474 parts by mass of the cellulose acylate solution E, and the dope was prepared by sufficiently stirring. The addition amount of the retardation increasing agent is 2 parts by mass with respect to 100 parts by mass of cellulose acetate.
The dope was cast from a casting port onto a drum cooled to 0 ° C. After drying for 3 seconds from immediately after casting, the film is peeled off at a solvent content of 70% by mass, and both ends in the width direction of the film are fixed with a pin tenter (a pin tenter described in FIG. 3 of JP-A-4-1009). In a state where the solvent content was 3 to 5% by mass, the film was dried while maintaining an interval at which the stretching ratio in the transverse direction (direction perpendicular to the machine direction) was 3%. Then, it was further dried by conveying between rolls of a heat treatment apparatus to produce a cellulose acetate film having a thickness of 75 im, Rth of 82 nm, and Re of 8 nm.
The abundance ratio of the retardation increasing agent (161) on the air surface / support surface was 1.2.
Using this cellulose acetate film, in the same manner as in Example 2, saponification treatment, formation of an alignment film, formation of an optically anisotropic layer, and production of a polarizing plate were carried out to produce a TN type liquid crystal display device. It has been found that the liquid crystal display device of the invention has few display defects and a good image can be obtained.

Example 6
(Preparation of cellulose acylate film)
In the cellulose acylate film (103) of Example 1, a cellulose acylate film (301) was produced in the same manner as in Example 1 except that the addition amount of the retardation increasing agent was changed to 4%.
Re was 34 nm and Rth was 140 nm.
(Saponification treatment)
The produced cellulose acylate film 301 was immersed in an aqueous 1.4 mol / liter potassium hydroxide solution at 55 ° C. for 2 minutes. It was washed in a room temperature water bath and neutralized with 0.1 mol / liter sulfuric acid at 30 ° C. Again, it was washed in a water bath at room temperature and further dried with hot air at 110 ° C. In this way, the surface of the cellulose acylate film was saponified.
Further, 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 sample preparation.
(Preparation of polarizing plate)
A polarizer was prepared by adsorbing iodine to the stretched polyvinyl alcohol film, and a saponified cellulose acylate film 101 was attached to one side of the polarizer using a polyvinyl alcohol-based adhesive. The transmission axis of the polarizer and the slow axis of the cellulose acylate film were arranged in parallel.
Further, Fujitac TD80UF saponified in Example 2 was attached to the opposite side of the polarizer using a polyvinyl alcohol-based adhesive. In this way, a polarizing plate (301) was produced.
[Production and evaluation of VA liquid crystal display device 1]
1% by weight of octadecyldimethylammonium chloride (coupling agent) was added to a 3% by weight aqueous solution of polyvinyl alcohol. 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 prepare a vertically aligned liquid crystal cell. The product of Δn and d was 400 nm.

The polarizing plate (301) produced in Example 3 was conditioned in advance at 25 ° C. and 60% temperature and humidity, then packaged in a moisture-proof bag and allowed to stand 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%, the polarizing plate 202 was taken out and pasted to both surfaces of the prepared vertical alignment liquid crystal cell using an adhesive sheet, to produce a liquid crystal display device.
It was found that the liquid crystal display device using the polarizing plate of the present invention has high display quality with few point defects.

Example 7
(Preparation of cellulose acylate film)
In the cellulose acylate film (105) of Example 1, cellulose acylate was produced from linter pulp, except that the cellulose acetate was changed to cellulose acetate having a total acetylation degree of 2.72, a 6-position acetylation degree of 0.90, and a polymerization degree of 320. Similarly, a cellulose acylate film (401) was produced.
Re was 78 nm and Rth was 210 nm.
(Preparation of polarizing plate)
In the same manner as in Example 6, a polarizing plate (401) having a cellulose acylate film (401) on one side of a polarizer was produced.
[Production and evaluation of VA liquid crystal display device 2]
The liquid crystal display device of FIG. 3 was produced. That is, the upper polarizing plate 30, the VA mode liquid crystal cell 31 (upper substrate, liquid crystal layer, lower substrate) and the lower polarizing plate 32 were laminated from the observation direction (upper), and a backlight light source was further arranged. In the following example, a commercially available polarizing plate (HLC2-5618) is used for the upper polarizing plate, and 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. Prepared by forming a layer. The retardation of the liquid crystal layer (that is, the product Δn · d of the thickness d (μm) of the liquid crystal layer and the refractive index anisotropy Δn) was set to 300 nm. The liquid crystal material was aligned so as to be vertically aligned.

A commercially available super high contrast product (HLC2-5618 manufactured by Sanlitz Co., Ltd.) is used for the upper polarizing plate of the liquid crystal display device (FIG. 3) using the vertical alignment type liquid crystal cell, and Example 3 is used for the lower polarizing plate. The polarizing plate (401) produced in (1) was attached to the observer side and the backlight side one by one through an adhesive so that the cellulose acylate film (401) of the present invention was on the liquid crystal cell side. The crossed nicols were arranged so that the transmission axis of the polarizing plate on the observer side was in the vertical direction and the transmission axis of the polarizing plate on the backlight side was in the horizontal direction.
It has been found that the liquid crystal display device of the present invention has no point defects and has a small display of light leakage even when continuously lit, and has excellent display quality.

Example 8
The following composition was put into a mixing tank, stirred while heating to dissolve each component, and a cellulose acetate solution D was prepared.
<Cellulose acetate solution D composition>
Cellulose acetate produced from lintercellulose and having 62.0% acetylation
100.0 parts by mass Retardation reducing agent (A-106) 11.0 parts by mass Methylene chloride (first solvent) 402.0 parts by mass Methanol (second solvent) 60.0 parts by mass

In another mixing tank, 16 parts by mass of the ultraviolet absorber (D), 80 parts by mass of methylene chloride and 20 parts by mass of methanol were added and stirred while heating to prepare a retardation increasing agent solution D.
11 parts by mass of the ultraviolet absorbent solution D was mixed with 474 parts by mass of the cellulose acetate solution B, and the dope was prepared by sufficiently stirring. The addition amount of the retardation increasing agent was 1.6 parts by mass with respect to 100 parts by mass of cellulose acetate.
The obtained dope was cast using a band casting machine at a casting speed of 45 m / min, dried to a residual solvent amount of 30% with a wind at a dew point of −20 ° C., and then the film was peeled off from the band. Next, the film was dried with a drying air of 130 ° C. for 10 minutes to produce a cellulose acetate film 501 having a residual solvent amount of 0.3 mass% and a thickness of 80 μm.

The abundance ratio of the air surface / support surface of the retardation reducing agent (A) was 0.85, and the abundance ratio of air surface / support surface of the ultraviolet absorber (D) was 1.2.
Re was 1 nm and Rth was 1 nm.
It was found that the cellulose acetate film 501 of the present invention has no bleed out and is excellent in surface shape.
Further, a polarizing plate (501) was produced in the same manner as in Example 7.

(Evaluation of mounting on IPS liquid crystal display)
An optical compensation film obtained by uniaxially stretching polycarbonate was bonded to the polarizing plate (501) of the present invention produced above to have an optical compensation function. At this time, by making the slow axis of the in-plane retardation of the optical compensation film orthogonal to the transmission axis of the polarizing plate, the visual characteristics can be improved without changing the front characteristics at all. The in-plane retardation Re of the optical compensation film was 270 nm, and the retardation Rth in the thickness direction was 135 nm.
A laminated body of the polarizing plate (501) of the present invention and an optical compensation film, an IPS type liquid crystal cell, and a polarizing plate (501) of the present invention were assembled in a stacked manner from the top to produce a liquid crystal display device. At this time, the transmission axes of the upper and lower polarizing plates are orthogonal to each other, and the transmission axis of the upper polarizing plate is parallel to the molecular long axis direction of the liquid crystal cell (that is, the slow axis of the optical compensation layer and the molecular long axis direction of the liquid crystal cell are orthogonal). ). As the liquid crystal cell, electrode and substrate, those conventionally used as IPS can be used as they are. The alignment of the liquid crystal cell is horizontal alignment, and the liquid crystal has positive dielectric anisotropy, and those developed and marketed for IPS liquid crystals can be used. The physical properties of the liquid crystal cell were as follows: Δn of liquid crystal: 0.099, cell gap of liquid crystal layer: 3.0 im, pretilt angle: 5 degrees, rubbing direction: 75 degrees on both upper and lower sides of the substrate.
It was found that the liquid crystal display device manufactured as described above is preferable with few point defects during black display.

It is a schematic sectional drawing which shows an example of the structure which combined the polarizing plate of this invention and the functional optical film. It is a sketch which shows typically an example of the liquid crystal display device in which the polarizing plate of this invention is used. 6 is a schematic cross-sectional view of a VA liquid crystal display device manufactured in Example 7. FIG.

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 orientation control direction 10 Liquid crystal Cell upper electrode substrate 11 Upper substrate alignment control direction 12 Liquid crystal molecule 13 Liquid crystal cell lower electrode substrate 14 Lower substrate alignment control direction 15 Lower optical anisotropic layer 16 Lower optical anisotropic layer alignment 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 (17)

A cellulose acylate film containing at least one additive having a molecular weight of 300 or more and 0.1 to 30 parts by mass with respect to 100 parts by mass of cellulose acylate,
For each additive, the abundance ratio of the cellulose acylate film on the side of the support surface that was in contact with the band or drum surface and the air surface that was on the air side satisfies the following formula: Cellulose acylate film.
0.25 <additive amount of additive on air surface / additive amount of additive on surface of support <4 A cellulose acylate film containing at least one additive having a molecular weight of 300 or more and 0.1 to 30 parts by mass with respect to 100 parts by mass of cellulose acylate,
The ratio of the total amount of additives present in the total amount of all additives present on the surface of the support surface that was in contact with the band or drum surface of the cellulose acylate film and the air surface that was on the air side was A cellulose acylate film satisfying the following formula:
0.5 <total additive abundance on air surface / total additive abundance on support surface <1.75 A method for producing a cellulose acylate film cast on a band by a solvent cast method,
A step of casting a cellulose acylate solution containing 0.01 to 20 parts by mass of phenyl benzoate as a retardation increasing agent having a molecular weight of 300 or more with respect to 100 parts by mass of cellulose acylate, and stripping A method for producing a cellulose acylate film, comprising the step of drying in the first half of the pre-drying for 10 seconds to 90 seconds in a substantially windless manner. A cellulose acylate film produced by the production method according to claim 3,
About the retardation increasing agent, the ratio of the abundance between the surface of the support surface that is in contact with the band surface of the cellulose acylate film and the surface of the air surface that is the air side satisfies the following formula: Cellulose acylate film.
0.25 <the amount of retardation increasing agent present on the air surface / the amount of the retardation increasing agent present on the surface of the support <4 A cellulose acylate film produced by the production method according to claim 3,
The cellulose acylate film contains at least one additive having a molecular weight of 300 or more in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of the cellulose acylate,
For each additive, the ratio of the abundance between the surface of the support surface that was in contact with the band surface of the cellulose acylate film and the air surface that was on the air side satisfies the following formula: Cellulose acylate film.
0.25 <additive amount of additive on air surface / additive amount of additive on surface of support <4 A cellulose acylate film produced by the production method according to claim 3,
The cellulose acylate film contains at least one additive having a molecular weight of 300 or more in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of the cellulose acylate,
The ratio of the total amount of additives present in the total amount of all additives present on the surface of the support surface that was in contact with the band surface of the cellulose acylate film and the air surface that was on the air side was expressed by the following formula: A cellulose acylate film characterized by satisfying
0.5 <total additive abundance on air surface / total additive abundance on support surface <1.75 A method for producing a cellulose acylate film cast on a drum by a solvent cast method,
1 second in the first half of the step of casting a cellulose acylate solution containing 0.1 to 30 parts by mass of an additive having a molecular weight of 300 or more with respect to 100 parts by mass of cellulose acylate and drying before peeling The manufacturing method of the cellulose acylate film characterized by including the process of drying for 10 seconds or less substantially in a windless manner. A cellulose acylate film produced by the production method according to claim 7,
The cellulose acylate film contains at least one additive having a molecular weight of 300 or more in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of the cellulose acylate,
For each additive, the abundance ratio of the cellulose acylate film on the side of the support surface that is in contact with the drum surface and the air surface that is on the air side satisfies the following formula: Cellulose acylate film.
0.25 <additive amount of additive on air surface / additive amount of additive on surface of support <4 A cellulose acylate film produced by the production method according to claim 7,
The cellulose acylate film contains at least one additive having a molecular weight of 300 or more in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of the cellulose acylate,
The ratio of the total amount of additives present in the total amount of all additives present on the surface of the support surface that was in contact with the drum surface of the cellulose acylate film and the air surface that was on the air side was expressed by the following formula: A cellulose acylate film characterized by satisfying
0.5 <total additive abundance on air surface / total additive abundance on support surface <1.75 A method for producing a cellulose acylate film cast on a band by a solvent cast method,
A step of casting a cellulose acylate solution containing 0.1 to 30 parts by mass of an additive having a molecular weight of 300 or more with respect to 100 parts by mass of cellulose acylate, and 10 seconds in the first half of drying before peeling A method for producing a cellulose acylate film, comprising the step of drying in a substantially windless manner for a period of 90 seconds or less. A cellulose acylate film produced by the production method according to claim 10,
The cellulose acylate film contains at least one additive having a molecular weight of 300 or more in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of the cellulose acylate,
For each additive, the abundance ratio of the cellulose acylate film on the side of the support surface that is in contact with the drum surface and the air surface that is on the air side satisfies the following formula: Cellulose acylate film.
0.25 <additive amount of additive on air surface / additive amount of additive on surface of support <4 A cellulose acylate film produced by the production method according to claim 10,
The cellulose acylate film contains at least one additive having a molecular weight of 300 or more in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of the cellulose acylate,
The ratio of the total amount of additives present in the total amount of all additives present on the surface of the support surface that was in contact with the drum surface of the cellulose acylate film and the air surface that was on the air side was expressed by the following formula: A cellulose acylate film characterized by satisfying
0.5 <total additive abundance on air surface / total additive abundance on support surface <1.75   The cellulose acylate film according to any one of claims 1, 2, 8, 9, 11 and 12, wherein at least one of the additives is a retardation reducing agent.   An optically anisotropic layer formed of liquid crystalline molecules is provided on the cellulose acylate film according to any one of claims 1, 2, 4, 5, 6, 8, 9, 11, and 12. An optical compensation film characterized by the above. A transparent protective film, a polarizing film, a transparent support, and an optically anisotropic layer formed from liquid crystalline molecules are polarizing plates laminated in this order,
A polarizing plate, wherein the transparent support is the cellulose acylate film according to any one of claims 1, 2, 4, 5, 6, 8, 9, 11, and 12. A liquid crystal display device comprising a liquid crystal cell and two polarizing plates disposed on both sides thereof,
The liquid crystal display device, wherein at least one of the two polarizing plates is the polarizing plate according to claim 15.   The liquid crystal display device according to claim 16, wherein the liquid crystal cell is a liquid crystal cell of a TN mode, a bend alignment mode or a vertical alignment mode.

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