JP2006124649A - Cellulose body composition, cellulose body film, cellulose film modifier, polarizing plate protective membrane, liquid crystal display device and silver halide sensitized material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cellulose body film having small optical isotropy and the like. <P>SOLUTION: A cellulose body composition comprises a cellulose body and at least one compound represented by formula (1) [wherein R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, and R<SP>4</SP>are each hydrogen, a substituted or nonsubstituted aliphatic group or a substituted or nonsubstituted aromatic group; X<SP>1</SP>, X<SP>2</SP>, X<SP>3</SP>, and X<SP>4</SP>are each at least one group selected from the group consisting of a single bond, -CO- and -NR<SP>5</SP>- (wherein R<SP>5</SP>is a substituted or nonsubstituted aliphatic group or a substituted or nonsubstituted aromatic group); a, b, c, and d are each an integer of ≥0 and a+b+c+d≥2; and Q<SP>1</SP>is an (a+b+c+d) valent organic group]. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a cellulose composition, a cellulose film, a cellulose film modifier, a polarizing plate protective film, a liquid crystal display device, and a silver halide photographic light-sensitive material. Specifically, the present invention relates to a cellulose film exhibiting low moisture permeability and a small optical anisotropy, a polarizing plate protective film using the cellulose film, a liquid crystal display device, a silver halide photographic light-sensitive material, and the like.

  Conventionally, cellulose acylate films have been used for photographic supports and various optical materials because of their toughness and flame retardancy. In particular, in recent years, it has been widely used as an optical transparent film for liquid crystal display devices. Cellulose acylate films are particularly excellent as optical materials for devices that handle polarized light, such as liquid crystal display devices, because of their high optical transparency and high optical isotropy. It has been used as a support for polarizer protective films and optical compensation films that can improve display (viewing angle compensation) when viewed from an oblique direction.

  A polarizer protective film is bonded to at least one side of a polarizer in a polarizing plate which is one of members for a liquid crystal display device. A general polarizer is obtained by dyeing a stretched polyvinyl alcohol (PVA) film with iodine or a dichroic dye. In many cases, a cellulose acylate film that can be directly bonded to PVA, especially a triacetyl cellulose film is used as a protective film for a polarizer. The optical properties of the polarizer protective film greatly influence the properties of the polarizing plate.

  On the other hand, the cellulose acylate film is a compound called a plasticizer because the moisture permeability under high temperature and high humidity is remarkably increased and the performance is deteriorated as compared with other supports such as polyethylene terephthalate film. Is often added. Known main plasticizers added to cellulose acylate include phosphate triesters such as triphenyl phosphate and biphenyl diphenyl phosphate, and phthalate esters (for example, Patent Document 1). In addition, sulfonamide compounds such as N-ethyltoluenesulfonamide are also known, and it is known that when the content of these plasticizers is increased, moisture permeability is lowered and film performance is improved. .

  However, there has been a problem in that the glass transition point of the cellulose acylate film is further lowered by increasing the amount of the plasticizer, and the dimensional stability is deteriorated by the softening of the film. Also, simply increasing the amount of plasticizer does not make the plasticizer compatible with the cellulose acylate film, causing the film to become cloudy, or increasing the optical anisotropy of the film (for example, the retardation value Rth in the thickness direction). There are problems such as enlargement. In addition, low molecular weight plasticizers have high heat volatility due to their low molecular weight and have a problem of volatilization in the drying process at the time of production, which has been regarded as a problem as a main cause of process contamination.

When a cellulose acylate film is used as an optical material, it is preferable to reduce the optical anisotropy of the film depending on the intended use. Among the compounds called plasticizers described above, those having an effect of reducing the optical anisotropy of the cellulose acylate film are known. For example, specific fatty acid esters are disclosed (for example, Patent Document 2, 3, 4, and 5). However, such a plasticizer has a problem that the moisture permeability under high temperature and high humidity deteriorates.
Therefore, development of a cellulose acylate film having a small optical anisotropy and a low moisture permeability under high temperature and high humidity, and a modifier thereof has been eagerly desired.

  In addition, in response to the above-mentioned problem of thermal volatility, by using a polymer compound such as rosin resin, epoxy resin, ketone resin and toluenesulfonamide resin, volatility is suppressed, and a cellulose acylate film having low moisture permeability is used. The technique to obtain is known (for example, patent document 6). However, since it is a polymer plasticizer, the compatibility is not sufficient, and the compatibility as low molecular plasticizer cannot be obtained.

  Therefore, the compatibility with cellulose acylate is good, and it gives low moisture permeability at high temperature and high humidity to the cellulose acylate film without volatilization and precipitation during casting drying, and has optical anisotropy. Development of a cellulose acylate modifier that can be reduced is eagerly desired.

JP-A-9-95557 JP 2001-247717 A JP 2001-336179 A JP 2000-63560 A Japanese Patent Laid-Open No. 11-246704 JP 2002-146044 A

  Therefore, the compatibility with cellulose acylate is good, and it gives low moisture permeability at high temperature and high humidity to the cellulose acylate film without volatilization and precipitation during casting drying, and has optical anisotropy. Development of a cellulose acylate modifier that can be reduced is eagerly desired.

The first object of the present invention is to provide a cellulose film having a small optical anisotropy.
A second object of the present invention is to provide a polarizing plate protective film, a liquid crystal display device, and a support for silver halide photographic light-sensitive material produced using a cellulose film having low moisture permeability under high temperature and high humidity. is there.

（一般式（１）中、Ｒ¹、Ｒ²、Ｒ³およびＲ⁴は、それぞれ、水素原子、置換若しくは無置換の脂肪族基または置換若しくは無置換の芳香族基を表す。Ｘ¹、Ｘ²、Ｘ³およびＸ⁴は、それぞれ、単結合、−ＣＯ−および−ＮＲ⁵−（Ｒ⁵は置換若しくは無置換の脂肪族基または置換若しくは無置換の芳香族基を表す）からなる群から選ばれる１種以上の基から形成される２価の連結基を表す。ａ、ｂ、ｃおよびｄは０以上の整数であり、ａ＋ｂ＋ｃ＋ｄは２以上である。Ｑ¹は（ａ＋ｂ＋ｃ＋ｄ）価の有機基を表す。）
（２）前記一般式（１）で表される化合物が下記一般式（２）で表される化合物であるセルロース体組成物。
一般式（２）

（一般式（２）中、Ｒ¹¹、Ｒ¹²、Ｒ¹³およびＲ¹⁴は、それぞれ、水素原子、置換若しくは無置換の脂肪族基または置換若しくは無置換の芳香族基を表す。Ｘ¹¹、Ｘ¹²、Ｘ¹³およびＸ¹⁴は、それぞれ、単結合、−ＣＯ−および−ＮＲ⁵−（Ｒ⁵は置換若しくは無置換の脂肪族基または置換若しくは無置換の芳香族基を表す）からなる群から選ばれる１種以上の基から形成される２価の連結基を表す。ｋ、ｌ、ｍおよびｎは０または１であり、ｋ＋ｌ＋ｍ＋ｎは２、３または４である。Ｑ²は２〜４価の有機基を表す。） The object of the present invention has been achieved by the following means.
(1) A cellulose body composition containing a cellulose body and at least one compound represented by the following general formula (1).
General formula (1)

(In the general formula (1), R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. X ¹ , X ² , X ³ and X ⁴ are each selected from the group consisting of a single bond, —CO— and —NR ⁵ — (R ⁵ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group). Represents a divalent linking group formed from one or more selected groups, a, b, c and d are integers of 0 or more, a + b + c + d is 2 or more, Q ¹ is an (a + b + c + d) -valent organic compound Represents a group.)
(2) A cellulose composition, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).
General formula (2)

(In the general formula (2), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each represent a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. X ¹¹ , X ¹² , X ¹³ and X ¹⁴ are each selected from the group consisting of a single bond, —CO— and —NR ⁵ — (R ⁵ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group). Represents a divalent linking group formed from one or more selected groups, k, l, m and n are 0 or 1, and k + 1 + m + n is 2, 3 or 4. Q ² is 2-4. Represents an organic group of

（一般式（１）中、Ｒ¹、Ｒ²、Ｒ³およびＲ⁴は、それぞれ、水素原子、置換若しくは無置換の脂肪族基または置換若しくは無置換の芳香族基を表す。Ｘ¹、Ｘ²、Ｘ³およびＸ⁴は、それぞれ、単結合、−ＣＯ−および−ＮＲ⁵−（Ｒ⁵は置換若しくは無置換の脂肪族基または置換若しくは無置換の芳香族基を表す）からなる群から選ばれる１種以上の基から形成される２価の連結基を表す。ａ、ｂ、ｃおよびｄは０以上の整数であり、ａ＋ｂ＋ｃ＋ｄは２以上である。Ｑ¹は（ａ＋ｂ＋ｃ＋ｄ）価の有機基を表す。）
（４）前記一般式（１）で表される化合物は、下記一般式（３）で表される化合物である（３）に記載のセルロース体フィルム。
一般式（３）

（一般式（３）中、Ｒ²¹およびＲ²²は、それぞれ、置換若しくは無置換の脂肪族基または置換若しくは無置換の芳香族基を表す。Ｙ¹およびＹ²は、それぞれ、−ＣＯＮＲ²³−または−ＮＲ²⁴ＣＯ−を表す（Ｒ²³およびＲ²⁴は置換若しくは無置換の脂肪族基または置換若しくは無置換の芳香族基を表す）。Ｌ¹は、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ₂−、−ＣＯ−、−ＮＲ²⁵−（Ｒ²⁵は水素原子、置換若しくは無置換の脂肪族基または置換若しくは無置換の芳香族基を表す。）、アルキレン基およびアリーレン基からなる群から選ばれる１種以上の基から形成される２価の有機基を表す。）
（５）前記一般式（１）で表される化合物は、下記一般式（４）で表される化合物である（３）に記載のセルロース体フィルム。
一般式（４）

（一般式（４）中、Ｒ³¹、Ｒ³²、Ｒ³³およびＲ³⁴はそれぞれ置換若しくは無置換の脂肪族基または置換若しくは無置換の芳香族基を表す。Ｌ²は−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ₂−、−ＣＯ−、−ＮＲ³⁵−（Ｒ³⁵は水素原子、置換若しくは無置換の脂肪族基または置換若しくは無置換の芳香族基を表す。）、アルキレン基およびアリーレン基からなる群から選ばれる１種以上の基から形成される２価の有機基を表す。）
（６）前記一般式（１）で表される化合物は、下記一般式（５）で表される化合物である（３）に記載のセルロース体フィルム。
一般式（５）

（一般式（５）中、Ｒ⁴¹、Ｒ⁴²、Ｒ⁴³およびＲ⁴⁴はそれぞれ置換若しくは無置換の脂肪族基または置換若しくは無置換の芳香族基を表す。Ｌ³は−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ₂−、−ＣＯ−、−ＮＲ⁴⁵−（Ｒ⁴⁵は水素原子、置換若しくは無置換の脂肪族基または置換若しくは無置換の芳香族基を表す。）、アルキレン基およびアリーレン基からなる群から選ばれる１種以上の基から形成される２価の有機基を表す。）
（７）前記一般式（１）で表される化合物は、下記一般式（６）で表される化合物である（３）に記載のセルロース体フィルム。
一般式（６）

（一般式（６）中、Ｒ⁵¹、Ｒ⁵²、Ｒ⁵³およびＲ⁵⁴はそれぞれ置換若しくは無置換の脂肪族基または置換若しくは無置換の芳香族基を表す。Ｌ⁴は−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ₂−、−ＣＯ−、−ＮＲ⁵⁵−（Ｒ⁵⁵は水素原子、置換若しくは無置換の脂肪族基または置換若しくは無置換の芳香族基を表す。）、アルキレン基およびアリーレン基からなる群から選ばれる１種以上の基から形成される２価の有機基を表す。） (3) A cellulose film containing at least one compound represented by the following general formula (1).
General formula (1)

(In the general formula (1), R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. X ¹ , X ² , X ³ and X ⁴ are each selected from the group consisting of a single bond, —CO— and —NR ⁵ — (R ⁵ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group). Represents a divalent linking group formed from one or more selected groups, a, b, c and d are integers of 0 or more, a + b + c + d is 2 or more, Q ¹ is an (a + b + c + d) -valent organic compound Represents a group.)
(4) The cellulose body film according to (3), wherein the compound represented by the general formula (1) is a compound represented by the following general formula (3).
General formula (3)

(In General Formula (3), R ²¹ and R ²² each represent a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. Y ¹ and Y ² are each —CONR ²³ —. Or —NR ²⁴ CO— (wherein R ²³ and R ²⁴ represent a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group) L ¹ represents —O—, —S—, —SO —, —SO ₂ —, —CO—, —NR ²⁵ — (R ²⁵ represents a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group), an alkylene group and an arylene group. Represents a divalent organic group formed from one or more groups selected from the group consisting of
(5) The cellulose body film according to (3), wherein the compound represented by the general formula (1) is a compound represented by the following general formula (4).
General formula (4)

(In the general formula (4), R ³¹ , R ³² , R ³³ and R ³⁴ each represent a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. L ² represents —O— or —S. —, —SO—, —SO ₂ —, —CO—, —NR ³⁵ — (R ³⁵ represents a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group), an alkylene group. And a divalent organic group formed from one or more groups selected from the group consisting of an arylene group.)
(6) The cellulose body film according to (3), wherein the compound represented by the general formula (1) is a compound represented by the following general formula (5).
General formula (5)

(In the general formula (5), R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ each represent a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. L ³ represents —O— or —S. —, —SO—, —SO ₂ —, —CO—, —NR ⁴⁵ — (R ⁴⁵ represents a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group), an alkylene group. And a divalent organic group formed from one or more groups selected from the group consisting of an arylene group.)
(7) The cellulose body film according to (3), wherein the compound represented by the general formula (1) is a compound represented by the following general formula (6).
General formula (6)

(In the general formula (6), R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ each represent a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. L ⁴ represents —O— or —S. -, - SO -, - SO 2 -, - CO -, - NR 55 - (. R 55 is represents a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group), an alkylene group And a divalent organic group formed from one or more groups selected from the group consisting of an arylene group.)

(8) The cellulose body film according to any one of (3) to (7), wherein the cellulose body is cellulose acylate.
(9) The cellulose body film according to (8), wherein the cellulose acylate has an acyl substitution degree of 2.60 to 3.00.
(10) The cellulose body film according to (8), wherein the cellulose acylate has an acyl substitution degree of 2.80 to 2.95.
(11) The cellulose body film according to any one of (8) to (10), wherein the degree of substitution with the acetyl group in the cellulose acylate is 2.60 to 3.00.
(12) The degree of substitution of the cellulose acylate substituted with an acyl group having 3 to 22 carbon atoms is 0.00 to 0.80, according to any one of (8) to (11) Cellulosic film.
(13) The cellulose acylate is substituted with an acetyl group and an acyl group having 3 to 22 carbon atoms, and 30% or more of the acyl groups having 3 to 22 carbon atoms are substituted with a hydroxyl group at the 6-position The cellulosic film according to any one of (8) to (12), which exists as:
(14) The cellulose body film according to any one of (8) to (13), wherein the acyl substitution degree at the 6-position of the cellulose acylate is 0.80 to 1.00.
(15) The cellulose body film according to any one of (8) to (13), wherein the acyl substitution degree at the 6-position of the cellulose acylate is 0.85 to 1.00.
(16) The cellulosic body and any one of (8) to (15) including at least one compound represented by the general formula (1) in an amount of 2 to 30% by mass of the cellulosic body. Cellulosic film.
(17) The cellulose body film according to any one of (8) to (16), wherein the cellulose body has a viscosity average polymerization degree of 250 to 550.

（一般式（１）中、Ｒ¹、Ｒ²、Ｒ³およびＲ⁴は、それぞれ、水素原子、置換若しくは無置換の脂肪族基または置換若しくは無置換の芳香族基を表す。Ｘ¹、Ｘ²、Ｘ³およびＸ⁴は、それぞれ、単結合、−ＣＯ−および−ＮＲ⁵−（Ｒ⁵は置換若しくは無置換の脂肪族基または置換若しくは無置換の芳香族基を表す）からなる群から選ばれる１種以上の基から形成される２価の連結基を表す。ａ、ｂ、ｃおよびｄは０以上の整数であり、ａ＋ｂ＋ｃ＋ｄは２以上である。Ｑ¹は（ａ＋ｂ＋ｃ＋ｄ）価の有機基を表す。）
（１９）（３）〜（８）のいずれか１項に記載のセルロース体フィルムを有する偏光板保護膜。
（２０）（３）〜（８）のいずれか１項に記載のセルロース体フィルムを有する液晶表示装置。
（２１）（３）〜（８）のいずれか１項に記載のセルロース体フィルムを有するハロゲン化銀写真感光材料。 (18) A cellulose body film modifier containing at least one compound represented by the following general formula (1).
General formula (1)

(In the general formula (1), R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. X ¹ , X ² , X ³ and X ⁴ are each selected from the group consisting of a single bond, —CO— and —NR ⁵ — (R ⁵ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group). Represents a divalent linking group formed from one or more selected groups, a, b, c and d are integers of 0 or more, a + b + c + d is 2 or more, Q ¹ is an (a + b + c + d) -valent organic compound Represents a group.)
(19) A polarizing plate protective film having the cellulose film according to any one of (3) to (8).
(20) A liquid crystal display device having the cellulose film according to any one of (3) to (8).
(21) A silver halide photographic light-sensitive material having the cellulose film according to any one of (3) to (8).

  The cellulose body composition of the present invention can provide a cellulose body film having low moisture permeability under high temperature and high humidity. Therefore, the cellulosic film of the present invention also has an excellent effect that the optical anisotropy is small in addition to the above-described good moisture permeability. Moreover, the cellulose body film of this invention can be preferably used for a polarizing plate protective film, a liquid crystal display device, a silver halide photographic light-sensitive material, etc., for example.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

  The cellulose composition of the present invention is a composition containing a cellulose compound and a compound having a cellulose skeleton (cellulose body) obtained by introducing a functional group biologically or chemically using cellulose as a raw material. Among the cellulose bodies, cellulose esters are preferable, and cellulose acylate is more preferable.

In the present invention, at least one compound represented by the general formula (1) is used as a cellulose body modifier.
Hereinafter, the compound represented by the general formula (1) of the present invention will be described.
In the general formula (1), R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, and the aliphatic group is preferable. The aliphatic group may be linear, branched or cyclic. Examples of the substituent that the aliphatic group and the aromatic group may have include the substituent T described later, but an unsubstituted one is preferable. X ¹ , X ² , X ³ and X ⁴ are each a single bond, —CO—, —NR ⁵ (wherein —R ⁵ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group; An unsubstituted group and / or an aliphatic group is more preferable.) A divalent linking group formed from one or more groups selected from the group consisting of The combination of X ¹ , X ² , X ³ and X ⁴ is not particularly limited, but is more preferably selected from —CO—, —NR ⁵ — (. A, b, c and d are integers of 0 or more. A + b + c + d is 2 or more, a + b + c + d is preferably 2 to 8, more preferably 2 to 6, and further preferably 2 to 4. Q ¹ represents an (a + b + c + d) -valent organic group. The valence of ¹ is preferably 2-8, more preferably 2-6, and most preferably 2-4.
An organic group refers to a group composed of an organic compound. However, you may have a substituent in the range which does not deviate from the meaning of this invention.

The general formula (1) is preferably a compound represented by the general formula (2).
In the general formula (2), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each represent a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, and the aliphatic group is preferable. The aliphatic group may be linear, branched or cyclic. Examples of the substituent that the aliphatic group and the aromatic group may have include the substituent T described later, but an unsubstituted one is preferable. X ¹¹ , X ¹² , X ¹³ and X ¹⁴ are each independently a single bond, —CO—, —NR ¹⁵ — (R ¹⁵ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group; An unsubstituted group and / or an aliphatic group is more preferable.) A divalent linking group formed from one or more groups selected from The combination of X ¹¹ , X ¹² , X ¹³ and X ¹⁴ is not particularly limited, but is more preferably selected from —CO— and —NR ¹⁵ —. k, l, m and n are 0 or 1, and k + 1 + m + n = 2, 3 or 4. Q ¹ represents a divalent to tetravalent organic group. The valence of Q ¹ is more preferably 2 or 3.

The general formula (1) is preferably a compound represented by the general formula (3).
In the general formula (3), R ²¹ and R ²² each represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, and an aliphatic group is preferable. The aliphatic group may be linear, branched or cyclic. Examples of the substituent that the aliphatic group and the aromatic group may have include the substituent T described later, but an unsubstituted one is preferable. Y ¹ and Y ² each independently represent —CONR ²³ — or —NR ²⁴ CO—, wherein R ²³ and R ²⁴ represent a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, and are unsubstituted. And / or aliphatic groups are more preferred. L ¹ is a divalent organic group formed from one or more groups selected from —O—, —S—, —SO—, —SO ₂ —, —CO—, —NR ²⁵ —, an alkylene group and an arylene group. Represents a group. The combination of L ¹ is not particularly limited, but is preferably selected from —O—, —S—, —NR ²⁵ —, and an alkylene group, and more preferably selected from —O—, —S—, and an alkylene group. Most preferably, it is selected from, -O-, -S- and an alkylene group.

The general formula (1) is preferably a compound represented by the general formula (4).
In the general formula (4), R ³¹ , R ³² , R ³³ and R ³⁴ each represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, and an aliphatic group is preferred. The aliphatic group may be linear, branched or cyclic. Examples of the substituent that the aliphatic group and the aromatic group may have include the substituent T described later, but an unsubstituted one is preferable. L ² represents —O—, —S—, —SO—, —SO ₂ —, —CO—, —NR ³⁵ — (R ³⁵ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. And a divalent linking group formed from one or more groups selected from an alkylene group and an arylene group. The combination of L ² is not particularly limited, but is preferably selected from —O—, —S—, —NR ³⁵ —, and an alkylene group, more preferably selected from —O—, —S—, and an alkylene group. Most preferably, it is selected from, -O-, -S- and an alkylene group.

The general formula (1) is preferably a compound represented by the general formula (5).
In the general formula (5), R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ each represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, and an aliphatic group is preferred. The aliphatic group may be linear, branched or cyclic. Examples of the substituent that the aliphatic group and the aromatic group may have include the substituent T described later, but an unsubstituted one is preferable. L ³ represents —O—, —S—, —SO—, —SO ₂ —, —CO—, —NR ⁴⁵ — (R ⁴⁵ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. And a divalent linking group formed from one or more groups selected from an alkylene group and an arylene group. The combination of L ³ is not particularly limited, but is more preferably selected from —O—, —S—, —NR ⁴⁵ —, and an alkylene group, and more preferably selected from —O—, —S—, and an alkylene group. Preferably, it is most preferably selected from —O—, —S— and an alkylene group.

The general formula (1) is preferably a compound represented by the general formula (6).
In the general formula (6), R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ each represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, and an aliphatic group is preferred. The aliphatic group may be linear, branched or cyclic, and more preferably cyclic. Examples of the substituent that the aliphatic group and the aromatic group may have include the substituent T described later, but an unsubstituted one is preferable. L ⁴ represents —O—, —S—, —SO—, —SO ₂ —, —CO—, —NR ⁵⁵ — (R ⁵⁵ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. And a divalent linking group formed from one or more groups selected from an alkylene group and an arylene group. The combination of L ⁴ is not particularly limited, but is preferably selected from —O—, —S—, —NR ⁵⁵ —, and an alkylene group, and more preferably selected from —O—, —S—, and an alkylene group. Most preferably, it is selected from, -O-, -S- and an alkylene group.

  The above-described substituted or unsubstituted aliphatic group will be described below. The aliphatic 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 Particularly preferred. Specific examples of the aliphatic group include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, tert-butyl group, amyl group, isoamyl group, tert- Amyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, bicyclooctyl group, adamantyl group, n-decyl group, tert-octyl group, dodecyl group, hexadecyl group, octadecyl group, didecyl group, etc. Is mentioned.

  The above-mentioned aromatic group will be described below. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, and more preferably an aromatic hydrocarbon group. As the aromatic hydrocarbon group, those having 6 to 24 carbon atoms are preferable, and those having 6 to 12 carbon atoms are more preferable. Specific examples of the aromatic hydrocarbon group include benzene, naphthalene, anthracene, biphenyl, terphenyl, and the like. As the aromatic hydrocarbon group, benzene, naphthalene, and biphenyl are particularly preferable. As the aromatic heterocyclic group, those containing at least one of an oxygen atom, a nitrogen atom or a sulfur atom are preferable. Specific examples of the heterocyclic ring include, for example, furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazoline, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, Examples thereof include isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzthiazole, benzotriazole, tetrazaindene and the like. As the aromatic heterocyclic group, pyridine, triazine, and quinoline are particularly preferable.

Further, the above-described substituent T will be described in detail below.
Examples of the substituent T include an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12, particularly preferably 1 to 8, such as a methyl group, an ethyl group, an isopropyl group, and tert-butyl. Group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl, cyclohexyl group, etc.), alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms). In particular, it is 2 to 8, and examples thereof include a vinyl group, an allyl group, a 2-butenyl group, and a 3-pentenyl group.), An alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 2 carbon atoms). 12, particularly preferably 2 to 8, for example, propargyl group, 3-pentynyl group, etc.), aryl group (preferably carbon The number of children is 6 to 30, more preferably 6 to 20, particularly preferably 6 to 12, and examples thereof include a phenyl group, a biphenyl group, and a naphthyl group.), An amino group (preferably having 0 to 20 carbon atoms, More preferably, it is 0-10, Most preferably, it is 0-6, for example, an amino group, a methylamino group, a dimethylamino group, a diethylamino group, a dibenzylamino group etc.), an alkoxy group (preferably carbon atom number). 1-20, more preferably 1-12, particularly preferably 1-8, for example, a methoxy group, an ethoxy group, a butoxy group, etc.), an aryloxy group (preferably having 6-20 carbon atoms, more Preferably it is 6-16, Most preferably, it is 6-12, for example, a phenyloxy group, 2-naphthyloxy group etc. are mentioned), acyl (Preferably having 1 to 20 carbon atoms, more preferably 1 to 16, particularly preferably 1 to 12, and examples thereof include acetyl group, benzoyl group, formyl group, and pivaloyl group), alkoxycarbonyl group (preferably Has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as a methoxycarbonyl group and an ethoxycarbonyl group, and an aryloxycarbonyl group (preferably 7 carbon atoms). -20, more preferably 7-16, particularly preferably 7-10, for example, a phenyloxycarbonyl group, etc.), an acyloxy group (preferably having 2-20 carbon atoms, more preferably 2-16, Particularly preferred is 2 to 10, and examples thereof include an acetoxy group and a benzoyloxy group. An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms such as acetylamino group and benzoylamino group). ), An alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms such as a methoxycarbonylamino group), an aryloxycarbonylamino group ( Preferably it has 7 to 20 carbon atoms, more preferably 7 to 16 and particularly preferably 7 to 12, and examples thereof include a phenyloxycarbonylamino group, and a sulfonylamino group (preferably 1 to 20 carbon atoms). More preferably, it is 1-16, Most preferably, it is 1-12, for example, a methanesulfonylamino group, a benzenesulfonylamino group, etc.), a sulfamoyl group (preferably C0-20, more preferably 0). To 16, particularly preferably 0 to 12, such as sulfamoyl group, methyl Rufamoyl group, dimethylsulfamoyl group, phenylsulfamoyl group, etc.), carbamoyl group (preferably 1-20 carbon atoms, more preferably 1-16, particularly preferably 1-12, for example, Carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, phenylcarbamoyl group, etc.), alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, particularly preferably 1 to 12, Methylthio group, ethylthio group, etc.), arylthio group (preferably 6-20 carbon atoms, more preferably 6-16, particularly preferably 6-12, such as phenylthio group). A sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, Is preferably 1 to 12, for example, mesyl group, tosyl group, etc.), sulfinyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16, particularly preferably 1 to 12, For example, a methanesulfinyl group, a benzenesulfinyl group, etc.), a ureido group (preferably 1-20 carbon atoms, more preferably 1-16, particularly preferably 1-12, such as a ureido group, a methylureido group). , Phenylureido groups, etc.), phosphoric acid amide groups (preferably having 1-20 carbon atoms, more preferably 1-16, particularly preferably 1-12, such as diethylphosphoric acid amide, phenylphosphoric acid Amide, etc.), 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). A hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom, specifically an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a piperidyl group, a morpholino group, a benzoxazolyl group, a benzimidazolyl group, Examples thereof include a benzthiazolyl group. ), A silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include a trimethylsilyl group and a triphenylsilyl group). 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.

  Moreover, it is preferable that the addition amount of the compound represented by any one or more of General formula (1)-(6) is 1-30 mass% with respect to a cellulose body, and is 2-30 mass%. Is more preferable, it is more preferable that it is 2-25 mass%, and it is most preferable that it is 2-20 mass%.

  Although the preferable example of a compound represented by General formula (1) is shown below, this invention is not limited to these specific examples.

  Any of the compounds used in the present invention can be produced from known compounds. The compound represented by any one or more of the general formulas (1) to (6) is obtained, for example, by a condensation reaction of carbonyl chloride and an amine.

  The cellulose body used in the present invention will be described in detail. The cellulose body used in the present invention may be anything as long as it is a compound using cellulose as a raw material. Cellulose acylate is preferred.

[Cellulose acylate raw material cotton]
The cellulose of the cellulose acylate raw material used in the present invention is not particularly limited, and examples thereof include cotton linter and wood pulp (hardwood pulp, softwood pulp), and cellulose obtained from any raw material cellulose. An acylate can also be used, and in some cases, a mixture may be used. Detailed descriptions of these raw material celluloses can be found in, for example, “Plastic Materials Course (17) Fibrous Resin” (Marusawa, Uda, Nikkan Kogyo Shimbun, published in 1970), and the Japan Institute of Technical Disclosure (Public Technical Report). 2001-1745, pages 7-8, issued on March 15, 2001, Invention Association).

The specific cellulose acylate is a mixed fatty acid ester of cellulose obtained by substituting the hydroxyl group of cellulose with an acetyl group and an acyl group having 3 or more carbon atoms, and the degree of substitution of the cellulose with a hydroxyl group is as follows: It is preferable that the cellulose acylate satisfies the mathematical formulas (4) and (5).
Formula (4): 2.0 ≦ A + B ≦ 3.0
Formula (5): 0 <B
Here, A and B in the formula represent the substitution degree of the acyl group substituted with the hydroxyl group of cellulose, A is the substitution degree of the acetyl group, and B is the substitution degree of the acyl group having 3 or more carbon atoms.

  Glucose units having β-1,4 bonds constituting cellulose have free hydroxyl groups at the 2nd, 3rd and 6th positions. Cellulose acylate is a polymer obtained by esterifying some or all of these hydroxyl groups with acyl groups. The degree of acyl substitution means the proportion of cellulose esterified at each of the 2-position, 3-position and 6-position (100% esterification has a degree of substitution of 1).

[Degree of polymerization of cellulose acylate]
The degree of polymerization of the cellulose acylate used in the present invention is preferably 180 to 700 in terms of viscosity average polymerization degree, more preferably 180 to 550, still more preferably 180 to 400, and particularly preferably 180 to 350 in cellulose acetate. By setting the degree of polymerization to 700 or less, the viscosity of the dope solution of cellulose acylate does not become too high, and it becomes easy to produce a film by casting. By making the degree of polymerization 180 or more, the strength of the produced film can be made better. The average degree of polymerization can be measured by the intrinsic viscosity method of Uda et al. (Kazuo Uda, Hideo Saito, “Journal of the Textile Society”, Vol. This is described in detail in JP-A-9-95538.
The molecular weight distribution of cellulose acylate preferably used in the present invention is evaluated by gel permeation chromatography, and its polydispersity index Mw / Mn (Mw is a mass average molecular weight, Mn is a number average molecular weight) is small, and the molecular weight distribution. Is preferably narrow. The specific value of Mw / Mn is preferably 1.0 to 3.0, more preferably 1.0 to 2.0, and most preferably 1.0 to 1.6. preferable.

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

  The cellulose acylate of the present invention can be used by mixing two or more types of cellulose acylate within the range not departing from the gist of the present invention.

[Additive to cellulose acylate]
In the cellulose acylate solution of the present invention, various additives other than the compound that reduces the moisture permeability of the present invention in each preparation step (for example, an ultraviolet ray inhibitor, a plasticizer, a deterioration inhibitor, fine particles, An optical property adjusting agent or the like) can be added, and the addition timing thereof may be added at any time in the dope preparation process. Moreover, you may add and add the process of adding an additive to the last preparation process of dope preparation process.

  They may be solid or oily. That is, the melting point and boiling point are not particularly limited. For example, ultraviolet absorbers of 20 ° C. or lower and 20 ° C. or higher can be mixed and used, and plasticizers can also be mixed and used, for example, as described in JP-A-2001-151901.

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

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

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

  Examples of salicylic acid esters include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

  Among these exemplified ultraviolet absorbers, in particular, 2-hydroxy-4-methoxybenzophenone, 2,2′-di-hydroxy-4,4′-methoxybenzophenone, 2 (2′-hydroxy-3′-t-butyl- 5'-methylphenyl) -5-chlorobenzotriazole, 2 (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2 (2'-hydroxy-3 ', 5'-di-t-amylphenyl) ) Benzotriazole, 2 (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole is particularly preferred.

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

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

  0.001-5 mass% is preferable with respect to a cellulose acylate, and, as for the addition amount of a ultraviolet absorber, 0.01-1 mass% is more preferable. If the addition amount is 0.001% by mass or more, the effect of addition can be sufficiently exerted, and if the addition amount is 5% by mass or less, it is preferable because bleeding out of the ultraviolet absorber to the film surface can be suppressed.

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

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

[Plasticizer]
The plasticizer is preferably a phosphate ester or a carboxylic acid ester. Examples of the phosphate ester plasticizer include triphenyl phosphate (TPP), tricresyl phosphate (TCP), cresyl diphenyl phosphate, octyl diphenyl phosphate, biphenyl diphenyl phosphate (BDP), trioctyl phosphate, tributyl phosphate and the like; Examples of the acid ester plasticizer include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), diphenyl phthalate (DPP), diethyl hexyl phthalate (DEHP), O-acetyl citrate. Acid triethyl (OACTE), O-acetyl tributyl citrate (OACTB), acetyl triethyl citrate, acetyl tributyl citrate, oleic acid , Methyl ricinoleate, dibutyl sebacate, triacetin, tributyrin, butyl phthalyl butyl glycolate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, etc. The plasticizer used in the invention is more preferably selected from these exemplified plasticizers. Furthermore, the plasticizer is preferably (di) pentaerythritol esters, glycerol esters, diglycerol esters.

[Peeling accelerator]
Examples of the peeling accelerator include citric acid ethyl esters.
[Infrared absorber]
Furthermore, as an infrared absorber, it describes in Unexamined-Japanese-Patent No. 2001-194522, for example.

[dye]
In the present invention, a dye for adjusting the hue may be added. The content of the dye is preferably 10 to 1000 ppm, more preferably 50 to 500 ppm in terms of a mass ratio with respect to cellulose acylate. By containing the dye in this way, light piping of the cellulose acylate film can be reduced, and yellowness can be improved. These compounds may be added together with cellulose acylate and a solvent during the preparation of the cellulose acylate solution, or may be added during or after the solution preparation. Moreover, you may add to the ultraviolet absorber liquid added in-line. The dyes described in JP-A-5-34858 can be used.

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

  These fine particles usually form secondary particles having an average particle diameter of 0.1 to 3.0 μm, and these fine particles are present as aggregates of primary particles in the film, and 0.1 to 0.1 μm on the film surface. An unevenness of 3.0 μm is formed. The secondary average particle diameter is preferably 0.2 μm to 1.5 μm, more preferably 0.4 μm to 1.2 μm, and most preferably 0.6 μm to 1.1 μm. The primary and secondary particle sizes were determined by observing the particles in the film with a scanning electron microscope and determining the diameter of a circle circumscribing the particles as the particle size. In addition, 200 particles were observed at different locations, and the average value was taken as the average particle size.

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

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

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

  The solvent used is preferably lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol and the like. Although it does not specifically limit as solvents other than a lower alcohol, It is preferable to use the solvent used at the time of film forming of a cellulose ester.

[Rate of compound addition]
In the cellulose acylate film of the present invention, the total amount of compounds having a molecular weight of 3000 or less is preferably 5 to 45% based on the weight of the cellulose acylate. More preferably, it is 10-40%, More preferably, it is 15-30%. As described above, these compounds include compounds that reduce optical anisotropy, wavelength dispersion regulators, ultraviolet inhibitors, plasticizers, deterioration inhibitors, fine particles, release agents, infrared absorbers, etc. Is preferably 3000 or less, and more preferably 2000 or less. When the total amount of these compounds is 5% or less, the properties of cellulose acylate alone are likely to be obtained, and there are problems such as that the optical performance and physical strength are likely to vary with changes in temperature and humidity. Moreover, when the total amount of these compounds is 45% or more, problems such as exceeding the limit of compound compatibility in the cellulose acylate film and depositing on the film surface to cause the film to become cloudy (crying out of the film) occur. It becomes easy.

[Organic solvent for cellulose acylate solution]
In the present invention, it is preferable to produce a cellulose acylate film by a solvent cast method, and the film is produced using a solution (dope) in which cellulose acylate is dissolved in an organic solvent. The organic solvent preferably used as the main solvent of the present invention is preferably a solvent selected from esters, ketones, ethers having 3 to 12 carbon atoms, and halogenated hydrocarbons having 1 to 7 carbon atoms. Esters, ketones and ethers may have a cyclic structure. A compound having two or more functional groups of esters, ketones and ethers (that is, —O—, —CO— and —COO—) can also be used as a main solvent. It may have a functional group of In the case of the main solvent having two or more kinds of functional groups, the number of carbon atoms may be within the specified range of the compound having any functional group.

  As described above, for the cellulose acylate film of the present invention, a chlorinated halogenated hydrocarbon may be used as a main solvent, and the technical report of the Japan Society of Invention (Publication No. 2001-1745, pages 12-16, March 15, 2001). Non-chlorine solvents may be used as the main solvent, as described in Jissu, Japan Institute of Invention, and are not particularly limited to the cellulose acylate film of the present invention.

  In addition, the solvent for the cellulose acylate solution and film of the present invention is disclosed in the following patent documents including the dissolution method, and is a preferred embodiment. For example, JP-A-2000-95876, JP-A-12-95877, JP-A-10-324774, JP-A-8-152514, JP-A-10-330538, JP-A-9-95538, and JP-A-9 JP-A-95557, JP-A-10-235664, JP-A-12-63534, JP-A-11-21379, JP-A-10-182853, JP-A-10-278056, JP-A-10-279702, JP-A-10- 323853, JP-A-10-237186, JP-A-11-60807, JP-A-11-152342, JP-A-11-292988, JP-A-11-60752, JP-A-11-60752, and the like. Has been. According to these patent documents, not only the preferred solvent for the cellulose acylate of the present invention but also the physical properties of the solution and the coexisting substances to be coexisted are described, which is also a preferred embodiment in the present invention.

[Manufacturing process of cellulose acylate film]
(Dissolution process)
The method for dissolving the cellulose acylate solution (dope) of the present invention is not particularly limited, and it may be performed at room temperature or further by a cooling dissolution method or a high temperature dissolution method, or a combination thereof. Regarding the preparation of the cellulose acylate solution in the present invention, and further the steps of solution concentration and filtration accompanying the dissolution step, JIII Journal of Technical Disclosure (Technical No. 2001-1745, pages 22-25, March 2001) The manufacturing process described in detail in the Japanese publication, Invention Association) is preferably used.

  The dope transparency of the cellulose acylate solution of the present invention is preferably 85% or more. More preferably, it is 88% or more, More preferably, it is 90% or more. In the present invention, it was confirmed that various additives were sufficiently dissolved in the cellulose acylate dope solution. As a specific method for calculating the dope transparency, the dope solution is injected into a 1 cm square glass cell, and the absorbance at 550 nm is measured with a spectrophotometer (manufactured by Shimadzu Corporation, UV-3150). Only the solvent is measured in advance as a blank, and the transparency of the cellulose acylate solution is calculated from the ratio with the absorbance of the blank.

(Casting, drying, winding process)
Next, a method for producing a film using the cellulose acylate solution of the present invention will be described. As a method and equipment for producing the cellulose acylate film of the present invention, a solution casting film forming method and a solution casting film forming apparatus conventionally used for producing a cellulose triacetate film are used. The dope (cellulose acylate solution) prepared from the dissolving machine (kettle) is temporarily stored in a storage kettle, and the foam contained in the dope is defoamed for final preparation. The dope is sent from the dope discharge port to the pressure die through a pressure metering gear pump capable of delivering a constant amount of liquid with high accuracy, for example, by the number of rotations. The dry-dried dope film (also referred to as web) is peeled off from the metal support at a peeling point that is uniformly cast on the metal support and substantially rounds the metal support. The both ends of the obtained web are sandwiched between clips, transported by a tenter while holding the width and dried, and then the obtained film is mechanically transported by a roll group of a drying device, dried, and then rolled by a winder Wind up to a predetermined length. The combination of the tenter and the roll group dryer varies depending on the purpose. In the solution casting film forming method used for the functional protective film or the silver halide photographic light-sensitive material which is an optical member for electronic display, which is the main use of the cellulose acylate film of the present invention, a solution casting film forming apparatus In addition, a coating apparatus is often added for surface processing on films such as an undercoat layer, an antistatic layer, an antihalation layer, and a protective layer. These are described in detail in the Japan Institute of Invention Disclosure Technical Bulletin (Public Technical Number 2001-1745, pages 25-30, issued March 15, 2001, Japan Institute of Invention). Including), metal support, drying, peeling and the like, and can be preferably used in the present invention.
Moreover, 10-120 micrometers is preferable, as for the thickness of a cellulose acylate film, 20-100 micrometers is more preferable, and 30-90 micrometers is more preferable.

[Stretching treatment]
The cellulose acylate film preferably used in the present invention is preferably adjusted for retardation by stretching treatment. In particular, when the in-plane retardation value of the cellulose acylate film is set to a high value, a method of positively stretching in the width direction, for example, JP-A-62-115035, JP-A-4-152125, A method for stretching the produced film described in JP-A-4-284111, JP-A-4-298310, and JP-A-11-48271 can be used.

  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 stretching of the film may be uniaxial stretching only in the longitudinal or lateral direction, or may be simultaneous or sequential biaxial stretching. Usually, the stretching is performed at 1 to 200%, but the stretching is preferably performed at 1 to 100%, particularly preferably 1 to 50%.

  In order to suppress light leakage when the polarizing plate is viewed obliquely, it is necessary to arrange the transmission axis of the polarizer and the in-plane slow axis of the cellulose acylate film in parallel. Since the transmission axis of the roll film-like polarizer produced continuously is generally parallel to the width direction of the roll film, it is composed of the roll film-like polarizer and the roll film-like cellulose acylate film. In order to continuously bond the protective film, the in-plane slow axis of the roll film-shaped protective film needs to be parallel to the width direction of the film. Therefore, it is preferable to stretch more in the width direction. The stretching process may be performed in the middle of the film forming process, or the original fabric that has been formed and wound may be stretched. In the former case, stretching may be performed in a state containing a residual solvent, and the stretching can be preferably performed at a residual solvent amount of 2 to 30% by mass.

  The film thickness of the cellulose acylate film preferably used in the present invention obtained after drying varies depending on the purpose of use, but is usually preferably in the range of 5 to 500 μm, more preferably in the range of 20 to 300 μm, particularly 30. A range of ˜150 μm is preferred. Moreover, it is preferable that it is 40-110 micrometers for optical use, especially for VA liquid crystal display devices. The film thickness may be adjusted by adjusting the solid content concentration contained in the dope, the slit gap of the die base, the extrusion pressure from the die, the metal support speed, and the like so as to obtain a desired thickness.

  The width of the cellulose acylate film obtained as described above is preferably 0.5 to 3 m, more preferably 0.6 to 2.5 m, and still more preferably 0.8 to 2.2 m. The length is preferably 100 to 10,000 m per roll, more preferably 500 to 7000 m, and still more preferably 1000 to 6000 m. When winding, it is preferable to give knurling to at least one end, the knurling width is preferably 3 mm to 50 mm, more preferably 5 mm to 30 mm, and the height is preferably 0.5 to 500 μm, more preferably 1 to 200 μm. is there. This may be a single push or a double push.

The variation in Re ₅₉₀ value in the width direction of the film is preferably ± 5 nm, and more preferably ± 3 nm. Further, the variation in the Rth ₅₉₀ value in the width direction is preferably ± 10 nm, and more preferably ± 5 nm. Moreover, it is preferable that the variation in the Re value and the Rth value in the length direction is within the range of the variation in the width direction.

[Optical properties of cellulose acylate film]
In the present specification, Reλ and Rthλ represent in-plane retardation and retardation in the thickness direction at the wavelength λ, respectively. Reλ is measured by making light having a wavelength of λ nm incident in the normal direction of the film in “KOBRA 21ADH” (manufactured by Oji Scientific Instruments). Rthλ is light having a wavelength of λnm from the direction inclined by + 40 ° with respect to the normal direction of the film, using Reλ and the in-plane slow axis (determined by “KOBRA 21ADH”) as the tilt axis (rotation axis). The retardation value measured and the retardation measured by injecting light of wavelength λ nm from the direction inclined by -40 ° with respect to the film normal direction, with the in-plane slow axis as the tilt axis (rotation axis) “KOBRA 21ADH” is calculated based on the retardation value measured in a total of three directions, the assumed value of the average refractive index, and the input film thickness value.
Here, as the assumed value of the average refractive index, the values in the polymer handbook (JOHN WILEY & SONS, INC) and catalogs of various optical films can be used. Those whose average refractive index is not known can be measured with an Abbe refractometer. The average refractive index values of main optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), Polystyrene (1.59). The KOBRA 21ADH calculates nx, ny, and nz by inputting the assumed value of the average refractive index and the film thickness.

It is preferable that the Reλ retardation value and the Rthλ retardation value satisfy the following formulas (2) and (3), respectively, in order to widen the viewing angle of a liquid crystal display device, particularly a VA mode liquid crystal display device. In particular, a cellulose acylate film is preferable when used for a protective film on the liquid crystal cell side of the polarizing plate.
Formula (2): 0 nm ≦ Re ₅₉₀ ≦ 200 nm
Formula (3): 0 nm ≦ Rth ₅₉₀ ≦ 400 nm
[In the formula, Re ₅₉₀ and Rth ₅₉₀ are values at a wavelength λ = 590 nm (unit: nm). ]

When the cellulose acylate film preferably used in the present invention is used in the VA mode, a mode in which a total of two sheets are used on each side of the cell (two sheets type) and only one of the upper and lower sides of the cell are used. There are two types of forms (single sheet type).
In the case of the two-sheet type, Re ₅₉₀ is preferably 20 to 100 nm, and more preferably 30 to 70 nm. Rth ₅₉₀ is preferably 70 to 300 nm, and more preferably 100 to 200 nm.
In the case of a single sheet type, Re ₅₉₀ is preferably 30 to 150 nm, and more preferably 40 to 100 nm. Rth ₅₉₀ is preferably 100 to 300 nm, and more preferably 150 to 250 nm.

[Water permeability of film]
The moisture permeability of the cellulose acylate film used in the optical compensation sheet of the present invention is measured under conditions of a temperature of 60 ° C. and a humidity of 95% RH (relative humidity) based on JIS standard JISZ0208, and converted to a film thickness of 80 μm. It is preferable that it is 400-2000 g / m < ² > * 24h. More preferably 500~1800g / m ² · 24h, and particularly preferably 600~1600g / m ² · 24h. If it exceeds 2000 g / m ² · 24 h, the tendency of the absolute value of the humidity dependence of the Re value and Rth value of the film to exceed 0.5 nm /% RH becomes strong. Also, when an optically anisotropic film is formed by laminating an optically anisotropic layer on the cellulose acylate film of the present invention, the absolute value of the humidity dependence of the Re value and Rth value tends to exceed 0.5 nm /% RH. It becomes strong and is not preferable. When this optical compensation sheet or polarizing plate is incorporated in a liquid crystal display device, it causes a change in color and a decrease in viewing angle. In addition, when the moisture permeability of the cellulose acylate film is less than 400 g / m ² · 24 h, when the polarizing plate is prepared by being attached to both surfaces of the polarizing film, the cellulose acylate film prevents the drying of the adhesive, and adhesion Cause a defect.
If the film thickness of the cellulose acylate film is thick, the moisture permeability becomes small, and if the film thickness is thin, the moisture permeability becomes large. Therefore, it is necessary to convert the sample of any film thickness to a standard of 80 μm. Conversion of the film thickness is obtained as 80 μm-converted moisture permeability = actually measured moisture permeability × measured film thickness μm / 80 μm.
The measurement method for moisture permeability is “Polymer Physical Properties II” (Polymer Experiment Course 4, Kyoritsu Shuppan), pages 285 to 294: Measurement of vapor permeation (mass method, thermometer method, vapor pressure method, adsorption amount method) The cellulose acylate film sample 70 mmφ of the present invention was conditioned at 25 ° C., 90% RH, 60 ° C., and 95% RH for 24 hours, respectively, and a moisture permeation test apparatus (KK- 709007, trade name, Toyo Seiki Co., Ltd.) according to JIS Z-0208, calculate the amount of moisture per unit area (g / m ² ), and obtain moisture permeability = weight after humidity adjustment-weight before humidity adjustment. .

[Residual solvent amount of film]
It is preferable to dry on the conditions that the amount of residual solvents with respect to the cellulose acylate film of the present invention is in the range of 0.01 to 1.5% by mass. More preferably, it is 0.01-1.0 mass%. Curling can be suppressed by setting the residual solvent amount of the transparent support used in the present invention to 1.5% or less. More preferably, it is 1.0% or less. This is presumably because the main effect factor is that the free volume is reduced by reducing the amount of residual solvent during film formation by the solvent casting method described above.

[Hygroscopic expansion coefficient of film]
The hygroscopic expansion coefficient of the cellulose acylate film of the present invention is preferably 30 × 10 ⁻⁵ /% RH or less. The hygroscopic expansion coefficient is preferably 15 × 10 ⁻⁵ /% RH or less, and more preferably 10 × 10 ⁻⁵ /% RH or less. The hygroscopic expansion coefficient is preferably small, but usually it is 1.0 × 10 ⁻⁵ /% RH or more. The hygroscopic expansion coefficient indicates the amount of change in the length of the sample when the relative humidity is changed at a constant temperature. By adjusting this hygroscopic expansion coefficient, when the cellulose acylate film of the present invention is used as an optical compensation film support, the optical transmittance of the frame-shaped transmittance is increased while maintaining the optical compensation function of the optical compensation film. Leakage can be prevented.

[surface treatment]
The cellulose acylate film can achieve improved adhesion between the cellulose acylate film and each functional layer (for example, the undercoat layer and the back layer) by optionally performing a surface treatment. For example, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment can be used. The glow discharge treatment here may be low-temperature plasma that occurs in a low-pressure gas of 10 ^{−3 to} 20 Torr, and plasma treatment under atmospheric pressure is also preferable. A plasma-excitable gas is a gas that is plasma-excited under the above conditions, and includes chlorofluorocarbons such as argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, tetrafluoromethane, and mixtures thereof. It is done. The details of these are described in detail in the Japan Society for Invention and Innovation Technical Bulletin (Public Technical Number 2001-1745, pages 30 to 32, issued on March 15, 2001, Invention Association), and should be preferably used in the present invention. Can do.

[Alkaline saponification]
The alkali saponification treatment is preferably carried out by a method in which the cellulose acylate film is directly immersed in a saponification solution tank or a method in which the saponification solution is applied to the cellulose acylate film. Examples of the coating method include a dip coating method, a curtain coating method, an extrusion coating method, a bar coating method, and an E-type coating method.
The solvent of the alkali saponification coating solution has good wettability in order to apply the saponification solution to the cellulose acylate film, and the surface of the cellulose acylate film surface is not formed by the saponification solution solvent. It is preferred to select a solvent that remains good. Specifically, an alcohol solvent is preferable, and isopropyl alcohol is particularly preferable. An aqueous solution of a surfactant can also be used as a solvent. The alkali of the alkali saponification coating solution is preferably an alkali that dissolves in the above solvent, and more preferably KOH or NaOH. The pH of the saponification coating solution is preferably 10 or more, more preferably 12 or more. The reaction conditions during alkali saponification are preferably 1 second to 5 minutes at room temperature, more preferably 5 seconds to 5 minutes, and particularly preferably 20 seconds to 3 minutes. After the alkali saponification reaction, it is preferable to wash the surface on which the saponification solution is applied with water or with an acid and then with water.

[Functional layer]
The cellulose acylate film of the present invention is applied to optical uses and photographic light-sensitive materials as its uses. In particular, the optical application is preferably a liquid crystal display device, and the liquid crystal display device has a liquid crystal cell in which liquid crystal is supported between two electrode substrates, two polarizing elements disposed on both sides thereof, and the liquid crystal It is more preferable that at least one optical compensation sheet is disposed between the cell and the polarizing element. As these liquid crystal display devices, TN, IPS, FLC, AFLC, OCB, STN, ECB, VA and HAN are preferable.
In that case, when using the cellulose acylate film of this invention for the above-mentioned optical use, providing various functional layers is implemented. They are, for example, an antistatic layer, a cured resin layer (transparent hard coat layer), an antireflection layer, an easy adhesion layer, an antiglare layer, an optical compensation layer, an alignment layer, a liquid crystal layer, and the like. These functional layers and materials for which the cellulose acylate film of the present invention can be used include surfactants, slipping agents, matting agents, antistatic layers, hard coat layers, etc. No. 2001-1745, pages 32 to 45, published on March 15, 2001, Invention Association), and can be preferably used in the present invention.

[Application (Polarizing plate)]
The use of the cellulose acylate film of the present invention will be described.
The optical film of the present invention is particularly useful for a polarizing plate protective film. When using as a polarizing plate protective film, the manufacturing method of a polarizing plate is not specifically limited, It can manufacture by a general method. There is a method in which the obtained cellulose acylate film is treated with an alkali and bonded to both sides of a polarizer prepared by immersing and stretching a polyvinyl alcohol film in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. Instead of alkali treatment, easy adhesion processing as described in JP-A-6-94915 and JP-A-6-118232 may be performed.
Examples of the adhesive used for bonding the protective film treated surface and the polarizer include polyvinyl alcohol adhesives such as polyvinyl alcohol and polyvinyl butyral, vinyl latexes such as butyl acrylate, and the like.
The polarizing plate is composed of a polarizer and a protective film that protects both surfaces of the polarizer, and is further constructed by laminating a protective film on one surface of the polarizing plate and a separate film on the opposite surface. The protective film and the separate film are used for the purpose of protecting the polarizing plate at the time of shipping the polarizing plate and at the time of product inspection. In this case, the protect film is bonded for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the surface where the polarizing plate is bonded to the liquid crystal plate. Moreover, a separate film is used in order to cover the adhesive layer bonded to a liquid crystal plate, and is used for the surface side which bonds a polarizing plate to a liquid crystal plate.
In a liquid crystal display device, a substrate containing liquid crystal is usually disposed between two polarizing plates. However, a polarizing plate protective film to which the optical film of the present invention is applied can provide excellent display properties regardless of the location. . In particular, the polarizing plate protective film on the outermost surface of the display side of the liquid crystal display device is provided with a transparent hard coat layer, an antiglare layer, an antireflection layer, and the like.

[Application (Optical compensation film)]
The cellulose acylate film of the present invention can be used in various applications, and is particularly effective when used as an optical compensation film for liquid crystal display devices. The optical compensation film is generally used for a liquid crystal display device, refers to an optical material that compensates for a phase difference, and is synonymous with a phase difference plate, an optical compensation sheet, and the like. The optical compensation film has birefringence and is used for the purpose of removing the color of the display screen of the liquid crystal display device or improving the viewing angle characteristics.

(General liquid crystal display device configuration)
When the cellulose acylate film is used as an optical compensation film, the transmission axis of the polarizing element and the slow axis of the optical compensation film made of the cellulose acylate film may be arranged at any angle. The liquid crystal display device includes a liquid crystal cell having a liquid crystal supported between two electrode substrates, two polarizing elements disposed on both sides thereof, and at least one sheet between the liquid crystal cell and the polarizing element. The optical compensation film is arranged.
The liquid crystal layer of the liquid crystal cell is usually formed by sealing liquid crystal in a space formed by sandwiching a spacer between two substrates. The transparent electrode layer is formed on the substrate as a transparent film containing a conductive substance. The liquid crystal cell may further be provided with a gas barrier layer, a hard coat layer, or an undercoat layer (undercoat layer) (used for adhesion of the transparent electrode layer). These layers are usually provided on the substrate. The substrate of the liquid crystal cell generally has a thickness of 50 μm to 2 mm.

(Types of liquid crystal display devices)
The cellulose acylate film of the present invention can be used for liquid crystal cells in various display modes. TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), AFLC (Anti-Ferroly Liquid Liquid Crystal), OCB (Optically Liquid BTS). Various display modes such as ECB (Electrically Controlled Birefringence) and HAN (Hybrid Aligned Nematic) have been proposed. In addition, a display mode in which the above display mode is oriented and divided has been proposed. The cellulose acylate film of the present invention is effective in any display mode liquid crystal display device. Further, it is effective in any of a transmissive type, a reflective type, and a transflective liquid crystal display device.

(TN type liquid crystal display device)
The cellulose acylate film of the present invention may be used as a support for an optical compensation sheet of a TN type liquid crystal display device having a TN mode liquid crystal cell. TN mode liquid crystal cells and TN type liquid crystal display devices have been well known for a long time. The optical compensation sheet used in the TN type liquid crystal display device is described in JP-A-3-9325, JP-A-6-148429, JP-A-8-50206, and JP-A-9-26572. Moreover, it is described in Mori et al. (Jpn. J. Appl. Phys. Vol. 36 (1997) p. 143 and Jpn. J. Appl. Phys. Vol. 36 (1997) p. 1068). is there.

(STN type liquid crystal display device)
The cellulose acylate film of the present invention may be used as a support for an optical compensation sheet of an STN type liquid crystal display device having an STN mode liquid crystal cell. In general, in a STN type liquid crystal display device, rod-like liquid crystalline molecules in a liquid crystal cell are twisted in the range of 90 to 360 degrees, and the refractive index anisotropy (Δn) and cell gap (d) of the rod-like liquid crystalline molecules. Product (Δnd) is in the range of 300 to 1500 nm. The optical compensation sheet used in the STN type liquid crystal display device is described in JP-A-2000-105316.

(VA type liquid crystal display device)
The cellulose acylate film of the present invention is particularly advantageously used as a support for an optical compensation sheet of a VA liquid crystal display device having a VA mode liquid crystal cell. It is preferable that the Re retardation value of the optical compensation sheet used in the VA liquid crystal display device is 0 to 150 nm and the Rth retardation value is 70 to 400 nm. The Re retardation value is more preferably 20 to 70 nm. When two optically anisotropic polymer films are used in the VA liquid crystal display device, the Rth retardation value of the film is preferably 70 to 250 nm. When one optically anisotropic polymer film is used for the VA liquid crystal display device, the Rth retardation value of the film is preferably 150 to 400 nm. The VA-type liquid crystal display device may be an alignment-divided system as described in, for example, JP-A-10-123576.

(IPS liquid crystal display device and ECB liquid crystal display device)
The cellulose acylate film of the present invention is particularly advantageously used as a support for an optical compensation sheet of an IPS liquid crystal display device and an ECB liquid crystal display device having IPS mode and ECB mode liquid crystal cells, or as a protective film for a polarizing plate. It is done. In these modes, the liquid crystal material is aligned substantially in parallel during black display, and black is displayed by aligning liquid crystal molecules in parallel with the substrate surface in the absence of applied voltage. In these embodiments, the polarizing plate using the cellulose acylate film of the present invention contributes to improving the color tone, widening the viewing angle, and improving the contrast. In this aspect, the cellulose acylate film of the present invention is used for the protective film (the protective film on the cell side) disposed between the liquid crystal cell and the polarizing plate among the protective films of the polarizing plates above and below the liquid crystal cell. It is preferable to use the polarizing plate at least on one side. More preferably, an optically anisotropic layer is disposed between the protective film of the polarizing plate and the liquid crystal cell, and the retardation value of the disposed optically anisotropic layer is twice the value of Δn · d of the liquid crystal layer. It is preferable to set as follows.

(OCB type liquid crystal display device and HAN type liquid crystal display device)
The cellulose acylate film of the present invention is also advantageously used as a support for an optical compensation sheet of an OCB type liquid crystal display device having an OCB mode liquid crystal cell or a HAN type liquid crystal display device having a HAN mode liquid crystal cell. In the optical compensation sheet used for the OCB type liquid crystal display device or the HAN type liquid crystal display device, it is preferable that the direction in which the absolute value of retardation is minimum does not exist in the plane of the optical compensation sheet or in the normal direction. The optical properties of the optical compensation sheet used in the OCB type liquid crystal display device or the HAN type liquid crystal display device are also the optical properties of the optical anisotropic layer, the optical properties of the support, and the optical anisotropic layer and the support. Is determined by the arrangement of An optical compensation sheet used for an OCB type liquid crystal display device or a HAN type liquid crystal display device is described in JP-A-9-197397. Further, it is described in a paper by Mori et al. (Jpn. J. Appl. Phys. Vol. 38 (1999) p. 2837).

(Reflective liquid crystal display)
The cellulose acylate film of the present invention is also advantageously used as an optical compensation sheet for TN-type, STN-type, HAN-type, and GH (Guest-Host) type reflective liquid crystal display devices. These display modes have been well known since ancient times. The TN type reflection type liquid crystal display device is described in JP-A-10-123478, WO98848320, and Japanese Patent No. 3022477. The optical compensation sheet used in the reflective liquid crystal display device is described in WO00-65384.

(Other liquid crystal display devices)
The cellulose acylate film of the present invention is also advantageously used as a support for an optical compensation sheet of an ASM type liquid crystal display device having a liquid crystal cell in an ASM (axially aligned microcell) mode. The ASM mode liquid crystal cell is characterized in that the thickness of the cell is maintained by a resin spacer whose position can be adjusted. Other properties are the same as those of the TN mode liquid crystal cell. The ASM mode liquid crystal cell and the ASM type liquid crystal display device are described in Kume et al. (Kume et al., SID 98 Digest 1089 (1998)).

(Hard coat film, antiglare film, antireflection film)
The cellulose acylate film of the present invention can be preferably applied to a hard coat film, an antiglare film and an antireflection film. For the purpose of improving the visibility of flat panel displays such as LCD, PDP, CRT, EL, etc., any or all of a hard coat layer, an antiglare layer and an antireflection layer are provided on one or both sides of the cellulose acylate film of the present invention. Can be granted. A desirable embodiment of such an antiglare film and antireflection film is described in detail in JIII Journal of Technical Disclosure (Publication Technical Report 2001-1745, pages 54 to 57, published on March 15, 2001, Japan Society of Invention and Innovation). The cellulose acylate film of the present invention can be preferably used.

(Photo film support)
Furthermore, the cellulose acylate film of the present invention can be applied as a support for silver halide photographic light-sensitive materials, and various materials, formulations and processing methods described in the patent literature can be applied. Regarding these techniques, JP-A-2000-105445 describes in detail the color negative, and the cellulose acylate film of the present invention is preferably used. Further, application as a support for a color reversal silver halide photographic light-sensitive material is also preferable, and various materials, formulations and processing methods described in JP-A No. 11-282119 can be applied.

(Transparent substrate)
Since the cellulose acylate film of the present invention has an optical anisotropy close to zero and excellent transparency, it is an alternative to the liquid crystal cell glass substrate of a liquid crystal display device, that is, as a transparent substrate that encloses driving liquid crystals. Can also be used.
Since the transparent substrate enclosing the liquid crystal needs to be excellent in gas barrier properties, a gas barrier layer may be provided on the surface of the cellulose acylate film of the present invention as necessary. The form and material of the gas barrier layer are not particularly limited, but SiO ₂ or the like is vapor-deposited on at least one surface of the cellulose acylate film of the present invention, or a relatively gas barrier property such as vinylidene chloride polymer or vinyl alcohol polymer. A method of providing a high polymer coat layer can be considered, and these can be used as appropriate.
In order to use as a transparent substrate for enclosing liquid crystal, a transparent electrode for driving the liquid crystal by applying a voltage may be provided. Although it does not specifically limit as a transparent electrode, A transparent electrode can be provided by laminating | stacking a metal film, a metal oxide film, etc. on the at least single side | surface of the cellulose acylate film of this invention. Among these, a metal oxide film is preferable from the viewpoint of transparency, conductivity, and mechanical properties, and an indium oxide thin film mainly containing 2 to 15% of zinc oxide can be preferably used. Details of these techniques are disclosed in, for example, Japanese Patent Application Laid-Open Nos. 2001-125079 and 2000-227603.

  As for various materials and apparatuses used for the silver halide photographic light-sensitive material of the present invention, for example, the Japan Institute of Invention Disclosure Bulletin (Public Technical No. 2001-1745, page 59, issued on March 15, 2001, Invention Association) The thing described in can be adopted.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Synthesis Example 1>
Synthesis of A-1 After weighing 14.6 g of adipic acid into a 200 ml three-necked flask equipped with a mechanical stirrer, thermometer, condenser, and dropping funnel, 47.6 g of thionyl chloride was slowly added dropwise at 80 ° C. The reaction was carried out for 1 hour. After confirming that the reaction solution became uniform, the reaction system was concentrated as it was using an aspirator, and an excess amount of thionyl chloride was distilled off to obtain an oily product. Weigh out 24.9 g of N-methylcyclohexylamine, 22.3 g of triethylamine, and 200 ml of tetrahydrofuran (THF) in a 500 ml three-necked flask equipped with a new mechanical stirrer, thermometer, condenser, and dropping funnel. The oily substance obtained by the above reaction was slowly added dropwise. After completion of the dropping, the temperature was returned to room temperature, and the reaction was further continued for 4.5 hours. When the obtained reaction mixture was poured into 1 L of water with vigorous stirring, white crystals were precipitated. The crystals were filtered off and dried at 50 ° C. overnight to obtain 15.1 g of the target compound A-1 (yield 45%).

<Synthesis Example 2>
Synthesis of A-2 Weigh 71.3 g of 3,3′-thiodipropionic acid into a 300 ml three-necked flask equipped with a mechanical stirrer, thermometer, condenser, and dropping funnel, and slowly add 104.7 g of thionyl chloride. After dripping, it was made to react at 80 degreeC for 2 hours. After confirming that the reaction solution became uniform, the reaction system was concentrated as it was using an aspirator, and an excess amount of thionyl chloride was distilled off to obtain an oily product. Weighed 92.1 g of N-methylcyclohexylamine, 82.3 g of triethylamine, and 500 ml of THF in a 1 L three-necked flask equipped with a new mechanical stirrer, thermometer, condenser, and dropping funnel. The oil obtained in was dropped slowly. After completion of the dropwise addition, the temperature was returned to room temperature, and the reaction was further continued for 4 hours. To the resulting reaction mixture, 500 ml of water was added, and liquid separation and extraction were performed with 500 ml of ethyl acetate. The obtained organic layer was washed twice with 500 ml of 1N hydrochloric acid, 500 ml of saturated aqueous sodium hydrogen carbonate and 500 ml of water, dehydrated over anhydrous magnesium sulfate, and concentrated to give a yellow oil. The obtained oil was vacuum-dried at room temperature to obtain 120.1 g of the target compound A-2 (yield 81%).

<Synthesis Example 3>
Synthesis of A-3 In a 500 ml three-necked flask equipped with a mechanical stirrer, thermometer, condenser, and dropping funnel, 40.4 g of dicyclohexylamine, 22.6 g of triethylamine and 150 ml of THF were weighed. 4 g of adipic acid chloride was slowly added dropwise, followed by reaction at room temperature for 2 hours. To the resulting reaction mixture, 300 ml of water was added, followed by separation and extraction with 300 ml of ethyl acetate. The obtained organic layer was washed twice with 300 ml of 1N hydrochloric acid, 300 ml of saturated sodium bicarbonate water and 300 ml of water, dehydrated with anhydrous magnesium sulfate, and then concentrated to obtain a transparent oil. The obtained oil was vacuum-dried at room temperature to obtain 30.0 g of the target compound A-3 (yield 60%).

<Synthesis Example 4>
Synthesis of A-4 After weighing 25.0 g of 3-methyladipic acid into a 300 ml three-necked flask equipped with a mechanical stirrer, thermometer, condenser, and dropping funnel, 40.9 g of thionyl chloride was slowly added dropwise. The reaction was carried out at 80 ° C. for 2 hours. After confirming that the reaction solution became uniform, the reaction system was concentrated as it was using an aspirator, and an excess amount of thionyl chloride was distilled off to obtain an oily product. Weighed 27.3 g of N-methylcyclohexylamine, 24.3 g of triethylamine and 100 ml of THF into a 500 ml three-necked flask equipped with a new mechanical stirrer, thermometer, condenser and dropping funnel, and the above reaction under ice cooling. The oil obtained in was dropped slowly. After completion of the dropwise addition, the temperature was returned to room temperature, and the reaction was further continued for 4 hours. To the resulting reaction mixture, 300 ml of water was added, followed by separation and extraction with 300 ml of ethyl acetate. The obtained organic layer was washed twice with 300 ml of 1N hydrochloric acid, 300 ml of saturated sodium bicarbonate water and 300 ml of water, dehydrated with anhydrous magnesium sulfate, and then concentrated to obtain a transparent oil. The obtained oil was vacuum-dried at room temperature to obtain 25.3 g of the target compound A-4 (yield 47%).

<Synthesis Example 5>
Synthesis of A-5 After weighing 20.2 g of sebacic acid into a 300 ml three-necked flask equipped with a mechanical stirrer, thermometer, condenser, and dropping funnel, 47.6 g of thionyl chloride was slowly added dropwise at 80 ° C. The reaction was performed for 2 hours. After confirming that the reaction solution became uniform, the reaction system was concentrated as it was using an aspirator, and an excess amount of thionyl chloride was distilled off to obtain an oily product. Weigh out 24.9 g of N-methylcyclohexylamine, 22.3 g of triethylamine, and 200 ml of THF in a 300 ml three-necked flask equipped with a new mechanical stirrer, thermometer, condenser, and dropping funnel. The oil obtained in was dripped slowly. After completion of the dropwise addition, the temperature was returned to room temperature, and the reaction was further continued for 4 hours. When the obtained reaction mixture was poured into 1 L of water, white crystals were precipitated. The crystals were filtered off and dried at 50 ° C. overnight to obtain 19.9 g of the target compound A-5 (yield 84%).

<Synthesis Example 6>
Synthesis of A-8 After weighing 20.2 g of sebacic acid into a 300 ml three-necked flask equipped with a mechanical stirrer, thermometer, condenser, and dropping funnel, 47.6 g of thionyl chloride was slowly added dropwise at 80 ° C. The reaction was performed for 2 hours. After confirming that the reaction solution became uniform, the reaction system was concentrated as it was using an aspirator, and an excess amount of thionyl chloride was distilled off to obtain an oily product. 39.9 g of dicyclohexylamine, 22.3 g of triethylamine and 200 ml of THF were weighed into a 300 ml three-necked flask equipped with a new mechanical stirrer, thermometer, condenser, and dropping funnel. The oil was slowly added dropwise. After completion of the dropwise addition, the temperature was returned to room temperature, and the reaction was further continued for 4 hours. When the obtained reaction mixture was poured into 1 L of water, white crystals were precipitated. The crystals were separated by filtration and dried at 50 ° C. overnight to obtain 25.4 g of the target compound A-8 (yield 48%).

<Synthesis Example 7>
Synthesis of A-13 Weighed 28.4 g of di-sec-butylamine, 22.6 g of triethylamine and 150 ml of THF into a 500 ml three-necked flask equipped with a mechanical stirrer, thermometer, condenser, and dropping funnel, and cooled on ice. 18.3 g of adipic acid chloride was slowly added dropwise, followed by reaction at room temperature for 2 hours. To the resulting reaction mixture, 300 ml of water was added, followed by separation and extraction with 300 ml of ethyl acetate. The obtained organic layer was washed twice with 300 ml of 1N hydrochloric acid, 300 ml of saturated sodium bicarbonate water and 300 ml of water, dehydrated with anhydrous magnesium sulfate, and then concentrated to obtain a transparent oil. The obtained oil was vacuum-dried at room temperature to obtain 22.1 g of the target compound A-13 (yield 60%).

<Synthesis Example 8>
Synthesis of A-16 In a 500 ml three-necked flask equipped with a mechanical stirrer, thermometer, condenser, and dropping funnel, weigh 16.1 g of diethylamine, 22.6 g of triethylamine and 150 ml of THF, and 23.9 g under ice cooling. Of sebacic acid chloride was slowly added dropwise, followed by reaction at room temperature for 2 hours. To the resulting reaction mixture, 300 ml of water was added, followed by separation and extraction with 300 ml of ethyl acetate. The obtained organic layer was washed twice with 300 ml of 1N hydrochloric acid, 300 ml of saturated sodium bicarbonate water and 300 ml of water, dehydrated with anhydrous magnesium sulfate, and then concentrated to obtain a transparent oil. The obtained oil was vacuum-dried at room temperature to obtain 19.9 g of the intended compound A-16 (yield 64%).

<Synthesis Example 9>
Synthesis of A-20 Weighed 28.4 g of di-sec-butylamine, 22.6 g of triethylamine, and 150 ml of THF into a 500 ml three-necked flask equipped with a mechanical stirrer, thermometer, condenser, and dropping funnel. 23.9 g of sebacic acid chloride was slowly added dropwise, followed by reaction at room temperature for 2 hours. To the resulting reaction mixture, 300 ml of water was added, followed by separation and extraction with 300 ml of ethyl acetate. The obtained organic layer was washed twice with 300 ml of 1N hydrochloric acid, 300 ml of saturated sodium bicarbonate water and 300 ml of water, dehydrated with anhydrous magnesium sulfate, and then concentrated to obtain a transparent oil. The obtained oil was vacuum-dried at room temperature to obtain 29.7 g of the intended compound A-20 (yield 70%).

<Synthesis Example 10>
Synthesis of A-22 After weighing 20.2 g of sebacic acid into a 300 ml three-necked flask equipped with a mechanical stirrer, thermometer, condenser, and dropping funnel, 47.6 g of thionyl chloride was slowly added dropwise at 80 ° C. The reaction was performed for 2 hours. After confirming that the reaction solution became uniform, the reaction system was concentrated as it was using an aspirator, and an excess amount of thionyl chloride was distilled off to obtain an oily product. Weighed 22.3 g of diisopropylamine, 22.3 g of triethylamine and 200 ml of THF into a 300 ml three-necked flask equipped with a new mechanical stirrer, thermometer, condenser, and dropping funnel. The oil was slowly added dropwise. After completion of the dropwise addition, the temperature was returned to room temperature, and the reaction was further continued for 4 hours. When the obtained reaction mixture was poured into 1 L of water, white crystals were precipitated. The crystals were separated by filtration and dried at 50 ° C. overnight to obtain 29.9 g of the target compound A-22 (yield 81%).

<Synthesis Example 11>
Synthesis of B-1 In a 300 ml three-necked flask equipped with a mechanical stirrer, thermometer, condenser, and dropping funnel, 10.0 g N, N′-dimethyl-1,3-diaminopropane, 20.8 g triethylamine and After THF was weighed out and 29.6 g of cyclohexanecarbonyl chloride was slowly added dropwise under ice cooling, the mixture was returned to room temperature and further reacted at room temperature for 2 hours. To the obtained reaction mixture, 200 ml of water was added, and liquid separation and extraction were performed with 300 ml of ethyl acetate. The obtained organic layer was washed twice with 300 ml of 1N hydrochloric acid, 300 ml of saturated sodium bicarbonate water and 300 ml of water, dehydrated with anhydrous magnesium sulfate, and then concentrated to obtain a transparent oil. The obtained oil was vacuum-dried at room temperature to obtain 27.7 g of the target compound B-1 (yield 47%).

<Example 1> Cellulose body film and cellulose body film modifier (1-1) Preparation of cellulose acylate solution In a 5 L glass container having a stirring blade, while being well stirred and dispersed in the following solvent mixed solution, The cellulose triacetate powder A (flakes) described below was gradually added, and the whole was charged to 2 kg. The solvents methyl acetate, acetone, and ethanol were all those having a water content of 0.2% by mass or less. First, the powder of cellulose triacetate was charged in a dispersion tank, filled with nitrogen gas, and dispersed with a stirrer having a dissolver type eccentric stirring shaft and an anchor blade on the central shaft for 30 minutes. The starting temperature of dispersion was 30 ° C. After completion of the dispersion, the high-speed stirring was stopped, and the peripheral speed of the anchor blade was set to 0.5 m / sec and further stirred for 100 minutes to swell the cellulose triacetate flakes. Until the end of swelling, the inside of the tank was pressurized to 0.12 MPa with nitrogen gas. At this time, the oxygen concentration in the tank was less than 2% by volume, so that no problem was found in terms of explosion protection. Further, it was confirmed that the water content in the dope was 0.2% by mass or less. The composition of the cellulose acylate solution is as follows.

  Cellulose triacetate A (cellulose acylate flakes having SA + SB of 2.78, SA of 2.78, SB of 0, viscosity average polymerization degree of 303 and water content of 1% by mass or less, and substitution at the 6-position of cellulose acylate (100 parts by mass), dichloromethane (300.0 parts by mass), methanol (45.0 parts by mass), TPP / BDP (2/1 part by mass) shown below ( The sample 102 shown in Table 1 was manufactured using 12.0 parts by mass).

  Sample 101 was prepared without adding the TPP / BDP used in sample 102. For samples 103 to 121, as shown in Table 1, the TPP / BDP used in sample 102 was replaced with the comparative compound and the modifier of the present invention, and 8.0 parts by mass or 12.0 parts by mass was used. Produced.

(1-2) Cellulose triacetate film solution The obtained non-uniform gel solution was fed with a screw pump and allowed to pass through a cooling part at -70 ° C for 3 minutes. Cooling was performed using a -80 ° C refrigerant cooled by a refrigerator. The solution obtained by cooling is transferred to a stainless steel container and stirred at 50 ° C. for 2 hours to obtain a uniform solution. The solution was filtered, and further filtered through a filter paper (FH025, manufactured by Pall) having an absolute filtration accuracy of 2.5 μm.

(1-3) Production of Cellulose Triacetate Film A filtered cellulose triacetate solution at 50 ° C. was cast on a mirror-surface stainless steel support through a casting Giesser. The temperature of the support was 5 ° C., the casting speed was 3 m / min, and the coating width was 30 cm. The mixture was left at room temperature for 1 minute, and then a drying air of 55 ° C. was blown for drying. After 5 minutes, the film was peeled off from the mirror surface stainless steel support and dried at 133 ° C. for 27 minutes to obtain a cellulose triacetate film having a thickness of 80 μm.

(1-4) Test of moisture permeability, heat volatility and Rth of cellulose triacetate film The obtained cellulose triacetate film was subjected to moisture permeability, heat volatility and Rth test. In this example, the moisture permeability, thermal volatility, and Rth test of the cellulose triacetate film were performed as follows.

(Measurement of moisture permeability)
The cup containing calcium chloride was covered with each film sample, and the sealed one was subjected to a change in weight (g / (m ² ) before and after standing for 24 hours at 60 ° C. and 95% RH. From day)), the moisture permeability of the cellulose triacetate film based on the hygroscopicity of calcium chloride was evaluated. The results are shown in Table 1.

(Measurement of heat volatility)
Using a TG / DTA simultaneous measurement device (TG / DTA6200, trade name) manufactured by Seiko Instruments Inc., the weight loss of the film when held at 133 ° C. for 1 hour is measured, and a plasticizer and a low molecular component The thermal volatility of the inventive modifier was evaluated. The weight loss value was calculated by rounding off the second decimal place. The results are shown in Table 1.

(Measurement of Rth)
A sample 30 mm × 40 mm was conditioned at 25 ° C. and 60% RH for 2 hours. Measured. Rth is the retardation measured by injecting light of wavelength λ nm with the slow axis in the plane as the tilt axis and the normal direction of the film as 0 °, tilting the sample up to 50 ° every 10 °. Based on the values, the assumed average refractive index of 1.48 and the film thickness were input and calculated.

  The structures of the comparative compounds TPP, BDP, D-1 and D-2 in Table 1 are shown below.

Comparative compound

  From Table 1, compound A-1, A-2, A-3, A-4, A-5, A-8, A-13, A-16, A-20, A-22, B- of this invention. By adding 1 and C-1, DPP having a skeleton similar to that of the modifier of the present invention (but outside the scope of the present invention) of TPP / BDP used for general purposes It was found that a cellulose triacetate film having lower moisture permeability than D-2 can be produced. Moreover, although the modifier of this invention of Table 1 is a low molecular compound, all the heat volatility is as low as about 0.1%, and the modifier of this invention is compared with the conventional plasticizer. I found it excellent. In addition to the low moisture permeability and low volatility, the cellulose triacetate film to which the compound of the present invention was added also exhibited the effect of exhibiting extremely small optical anisotropy (Rth).

<Example 2>
A cellulose acylate film was produced in the same manner as in Example 1 using the following composition.
Cellulose triacetate (acetylation degree 60.9%) (100 parts by mass)
Methyl acetate (522.0 parts by mass)
Acetone (48.0 parts by mass)
Ethanol (30.0 parts by mass)
The modifier (11.7 parts by mass) used in the samples 102 to 116 described in Example 1
Also in this case, as in Example 1, good results were obtained in the cellulose body film of the present invention.

<Example 3> Polarizing plate protective film By using the samples 102 to 116 of Example 1 and the samples 202 to 216 of Example 2, an ellipse was obtained by the method described in Example 1 of JP-A-11-316378. Polarizer samples 3102 to 3116 and samples 3202 to 3216 were prepared and evaluated. The optical properties of the elliptically polarizing plate obtained from the cellulose film of the present invention were excellent. Further, regarding the samples 3104 to 3116, durability over time was not particularly problematic as compared with the protective film obtained from the comparative sample 3102.

<Example 4> Liquid crystal display device Using the samples 102 to 116 of Example 1 and the samples 202 to 216 of Example 2, the liquid crystal display device described in Example 1 of JP-A-10-48420, An optically anisotropic layer containing discotic liquid crystal molecules described in Example 1 of Kaihei 9-26572, an alignment film coated with polyvinyl alcohol, and a VA type described in FIGS. 2 to 9 of JP-A-2000-154261 A liquid crystal display device, an OCB type liquid crystal display device described in FIGS. 10 to 15 of JP-A No. 2000-154261 was prepared and evaluated. In the device obtained using the cellulose body film of the present invention, good performance was obtained in any case.

<Example 5> Silver halide photographic light-sensitive material Example 1 or Example except that samples 102 to 116 of Example 1 and samples 202 to 216 of Example 2 were used and the film thickness was changed to 120 μm. In the same manner as in Example 3, Samples 5102 to 5116 and Samples 5202 to 5216 were produced. A first layer and a second layer described in Example 1 of JP-A-4-73736 were applied to one surface of the obtained film to form a back layer having a cationic polymer as a conductive layer. Furthermore, each layer having the same composition as that of Sample 105 described in Example 1 of JP-A No. 11-38568 is applied to the opposite side of the obtained film base to which the back layer is applied, and a silver halide photographic light-sensitive material is obtained. Produced. The silver halide photographic light-sensitive materials obtained using the cellulose film of the present invention were all excellent in images and had no problem in handling.

Claims (12)

The cellulose body composition containing a cellulose body and at least 1 sort (s) of the compound represented by following General formula (1).
General formula (1)

(In the general formula (1), R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. X ¹ , X ² , X ³ and X ⁴ are each selected from the group consisting of a single bond, —CO— and —NR ⁵ — (R ⁵ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group). Represents a divalent linking group formed from one or more selected groups, a, b, c and d are integers of 0 or more, a + b + c + d is 2 or more, Q ¹ is an (a + b + c + d) -valent organic compound Represents a group.) A cellulose composition, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).
General formula (2)

(In the general formula (2), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each represent a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. X ¹¹ , X ¹² , X ¹³ and X ¹⁴ are each selected from the group consisting of a single bond, —CO— and —NR ⁵ — (R ⁵ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group). Represents a divalent linking group formed from one or more selected groups, k, l, m and n are 0 or 1, and k + 1 + m + n is 2, 3 or 4. Q ² is 2-4. Represents an organic group of The cellulose body film containing at least 1 sort (s) of the compound represented by following General formula (1).
General formula (1)

(In the general formula (1), R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. X ¹ , X ² , X ³ and X ⁴ are each selected from the group consisting of a single bond, —CO— and —NR ⁵ — (R ⁵ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group). Represents a divalent linking group formed from one or more selected groups, a, b, c and d are integers of 0 or more, a + b + c + d is 2 or more, Q ¹ is an (a + b + c + d) -valent organic compound Represents a group.) The cellulose body film according to claim 3, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (3).
General formula (3)

(In General Formula (3), R ²¹ and R ²² each represent a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. Y ¹ and Y ² are each —CONR ²³ —. Or —NR ²⁴ CO— (wherein R ²³ and R ²⁴ represent a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group) L ¹ represents —O—, —S—, —SO —, —SO ₂ —, —CO—, —NR ²⁵ — (R ²⁵ represents a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group), an alkylene group and an arylene group. Represents a divalent organic group formed from one or more groups selected from the group consisting of The cellulose body film according to claim 3, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (4).
General formula (4)

(In the general formula (4), R ³¹ , R ³² , R ³³ and R ³⁴ each represent a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. L ² represents —O— or —S. —, —SO—, —SO ₂ —, —CO—, —NR ³⁵ — (R ³⁵ represents a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group), an alkylene group. And a divalent organic group formed from one or more groups selected from the group consisting of an arylene group.) The cellulose body film according to claim 3, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (5).
General formula (5)

(In the general formula (5), R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ each represent a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. L ³ represents —O— or —S. —, —SO—, —SO ₂ —, —CO—, —NR ⁴⁵ — (R ⁴⁵ represents a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group), an alkylene group. And a divalent organic group formed from one or more groups selected from the group consisting of an arylene group.) The cellulose body film according to claim 3, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (6).
General formula (6)

(In the general formula (6), R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ each represent a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. L ⁴ represents —O— or —S. -, - SO -, - SO 2 -, - CO -, - NR 55 - (. R 55 is represents a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group), an alkylene group And a divalent organic group formed from one or more groups selected from the group consisting of an arylene group.)   The cellulose body film according to any one of claims 3 to 7, wherein the cellulose body is cellulose acylate. The cellulose body film modifier containing at least 1 sort (s) of the compound represented by following General formula (1).
General formula (1)

(In the general formula (1), R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. X ¹ , X ² , X ³ and X ⁴ are each selected from the group consisting of a single bond, —CO— and —NR ⁵ — (R ⁵ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group). Represents a divalent linking group formed from one or more selected groups, a, b, c and d are integers of 0 or more, a + b + c + d is 2 or more, Q ¹ is an (a + b + c + d) -valent organic compound Represents a group.)   The polarizing plate protective film which has a cellulose body film of any one of Claims 3-8.   The liquid crystal display device which has a cellulose body film of any one of Claims 3-8.   A silver halide photographic light-sensitive material having the cellulose body film according to any one of claims 3 to 8.