JP2006096875A - Cellulose derivative composition, cellulose derivative film, and bis-type 1,3,5-triazine derivative compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cellulose derivative composition capable of forming a film having a preferable retardation value as an optical film, and to provide the cellulose derivative film having the preferable retardation value as the optical film. <P>SOLUTION: This cellulose derivative composition contains at least one kind of compound expressed by general formula (1). The cellulose derivative film is formed out of the cellulose derivative composition. Further, a compound expressed by general formula (2) is provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a cellulose derivative composition containing a bis-type 1,3,5-triazine derivative compound and a cellulose derivative film comprising the cellulose derivative composition. The present invention further relates to a novel bis-type 1,3,5-triazine derivative compound.

  Among cellulose films, cellulose acetate film is characterized by high optical isotropy (low retardation value) as compared with other polymer films. Therefore, it is common to use a cellulose acetate film for an application requiring optical isotropy, for example, a polarizing plate. On the other hand, optical anisotropy (high retardation value) is required for an optical compensation sheet (phase difference film) such as a liquid crystal display device. Therefore, it is common to use a synthetic polymer film having a high retardation value such as a polycarbonate film or a polysulfone film as the optical compensation sheet.

Recently, however, a cellulose acetate film having a high retardation value that can be used for applications requiring optical anisotropy has been proposed (for example, Patent Document 1 and Patent Document 2). In the disclosed invention, in order to achieve a high retardation value with cellulose triacetate, an aromatic compound having at least two aromatic rings, particularly a compound having a 1,3,5-triazine ring, is added and subjected to stretching treatment. .
In general, cellulose triacetate is a polymer material that is difficult to stretch, and it is known that it is difficult to increase optical anisotropy. However, in Patent Documents 1 and 2, the additives are simultaneously oriented by stretching treatment. Therefore, it is possible to increase the optical anisotropy and realize a high retardation value.

  In recent years, it has become essential to reduce the thickness of a liquid crystal cell in order to reduce the weight of the liquid crystal display device and reduce the manufacturing cost. For this purpose, optical anisotropy (Re: retardation in the film plane) that can be realized with the compound having a 1,3,5-triazine ring described in Patent Documents 1 and 2 is applied to an optical film such as an optical compensation sheet. With respect to the value, Rth: retardation value in the film thickness direction, higher Re and lower Rth have been demanded.

  However, as a result of intensive studies on the methods disclosed in Patent Documents 1 and 2, the inventor has a problem that the Re value and the Rth value described above cannot be controlled within a preferable range. found. Therefore, development of new optical performance control technology has become necessary.

European Patent Publication EP0911656A2 JP 2003-344655 A

The first object of the present invention is to provide a cellulose derivative composition capable of forming a film having a preferable retardation value as an optical film.
The second object of the present invention is to provide a cellulose derivative film having a preferable retardation value as an optical film.

The object of the present invention has been achieved by the following means.
[1] A cellulose derivative composition comprising at least one compound represented by the following general formula (1).

（式中、Ａｒ¹、Ａｒ²、Ａｒ³、Ａｒ⁴はそれぞれ独立にアリール基または芳香族ヘテロ環を表し、Ｒ⁵は２価の連結基を表す。Ｌ¹、Ｌ²、Ｌ³、Ｌ⁴、Ｌ⁵、Ｌ⁶はそれぞれ独立に−Ｏ−、または−ＮＲ−を表す。Ｒは水素原子、アルキル基、またはアリール基を表し、Ａｒ¹、Ａｒ²、Ａｒ³、Ａｒ⁴、またはＲ⁵と互いに結んで環を形成していても良い。）
［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［１］に記載のセルロース誘導体組成物。

（式中、Ａｒ¹、Ａｒ²、Ａｒ³、Ａｒ⁴はそれぞれ独立にアリール基または芳香族ヘテロ環を表す。Ｌ¹、Ｌ²、Ｌ³、Ｌ⁴、Ｌ⁵、Ｌ⁶はそれぞれ独立に−Ｏ−、または−ＮＲ−を表す。Ｒは水素原子、アルキル基、またはアリール基を表し、Ａｒ¹、Ａｒ²、Ａｒ³、Ａｒ⁴、またはＲ⁵と互いに結んで環を形成していても良い。Ｌ⁷は単結合、または２価の連結基を表す。Ｒ¹¹、Ｒ¹²はそれぞれ独立に置換基を表し、m、nはそれぞれ独立に１〜４の整数を表す。）
［３］前記セルロース誘導体としてセルロースアシレートを含有することを特徴とする[１]または[２]に記載のセルロース誘導体組成物。
［４］[１]〜[３]のいずれかに記載のセルロール誘導体組成物からなるセルロース誘導体フイルム。
［５］下記一般式（２）で表される化合物。

（式中、Ａｒ¹、Ａｒ²、Ａｒ³、Ａｒ⁴はそれぞれ独立にアリール基または芳香族ヘテロ環を表す。Ｌ¹、Ｌ²、Ｌ³、Ｌ⁴、Ｌ⁵、Ｌ⁶はそれぞれ独立に−Ｏ−、または−ＮＲ−を表す。Ｒは水素原子、アルキル基、またはアリール基を表し、Ａｒ¹、Ａｒ²、Ａｒ³、Ａｒ⁴、またはＲ⁵と互いに結んで環を形成していても良い。Ｌ⁷は単結合、または２価の連結基を表す。Ｒ¹¹、Ｒ¹²はそれぞれ独立に置換基を表し、m、nはそれぞれ独立に１〜４の整数を表す。）

(In the formula, Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represents an aryl group or an aromatic heterocycle, and R ⁵ represents a divalent linking group. L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ each independently represents —O— or —NR—, R represents a hydrogen atom, an alkyl group or an aryl group, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ or R ⁵ may be connected to each other to form a ring.)
[2] The cellulose derivative composition according to [1], wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

(In the formula, Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent an aryl group or an aromatic heterocycle. L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ are each independently —O— or —NR—, wherein R represents a hydrogen atom, an alkyl group, or an aryl group, and is bonded to Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , or R ⁵ to form a ring. L ⁷ represents a single bond or a divalent linking group, R ¹¹ and R ¹² each independently represents a substituent, and m and n each independently represents an integer of 1 to 4.)
[3] The cellulose derivative composition according to [1] or [2], wherein the cellulose derivative contains cellulose acylate.
[4] A cellulose derivative film comprising the cellulose derivative composition according to any one of [1] to [3].
[5] A compound represented by the following general formula (2).

(In the formula, Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent an aryl group or an aromatic heterocycle. L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ are each independently —O— or —NR—, wherein R represents a hydrogen atom, an alkyl group, or an aryl group, and is bonded to Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , or R ⁵ to form a ring. L ⁷ represents a single bond or a divalent linking group, R ¹¹ and R ¹² each independently represents a substituent, and m and n each independently represents an integer of 1 to 4.)

  The cellulose derivative composition of the present invention is useful for forming a film excellent in optical performance satisfying both individually designated Re value and Rth value. Therefore, the cellulose derivative film obtained from this is excellent in optical performance.

  Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

The cellulose derivative composition of the present invention is a composition containing a cellulose derivative and is characterized by containing at least one compound represented by the general formula (1).
First, the compound represented by the general formula (1) will be described in detail.

In general formula (1), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent an aryl group or an aromatic heterocycle, and R ⁵ represents a divalent linking group. L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ each independently represent —O— or —NR—. R represents a hydrogen atom, an alkyl group, or an aryl group, and may be bonded to Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , or R ⁵ to form a ring.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represents an aryl group or an aromatic heterocycle. Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ may be different from each other, any two or more of them may be the same, or all may be the same. Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are preferably all the same for controlling the retardation of the optical film. The aryl group represented by Ar ¹ , Ar ² , Ar ³ , Ar ⁴ is preferably an aryl group having 6 to 30 carbon atoms, and may be a single ring or may form a condensed ring with another ring. May be. Further, if possible, it may have a substituent, and the substituent T described later can be applied as the substituent.
In general formula (1), the aryl group represented by Ar ¹ , Ar ² , Ar ³ , Ar ⁴ is more preferably an aryl group having 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms. A phenyl group, a p-methylphenyl group, a naphthyl group, etc. are mentioned.

In the general formula (1), the aromatic heterocycle represented by Ar ¹ , Ar ² , Ar ³ , Ar ⁴ is an aromatic heterocycle containing at least one of an oxygen atom, a nitrogen atom or a sulfur atom. An aromatic heterocycle containing at least one of a 5- to 6-membered oxygen, nitrogen or sulfur atom is preferable. Moreover, you may have a substituent further if possible. Substituent T described later can be applied as the substituent.

In the general formula (1), specific examples of the aromatic heterocycle represented by Ar ¹ , Ar ² , Ar ³ , Ar ⁴ include, for example, furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, Triazole, triazine, indole, indazole, purine, thiazoline, thiazole, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole Benzoxazole, benzthiazole, benzotriazole, tetrazaindene, pyrrolotriazole, pyrazolotriazole and the like. Preferred as the aromatic heterocycle are benzimidazole, benzoxazole, benzthiazole, and benzotriazole.

R ⁵ represents a divalent linking group. Preferred examples of the divalent linking group include an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a group obtained by combining two or more of these divalent groups. When comprised by the combination of these, you may be further connected with another bivalent coupling group. As such a divalent linking group, a group represented by —NR ⁷ — (R ⁷ represents a hydrogen atom, an alkyl group or an aryl group which may have a substituent), —O—, — S -, - SO -, - SO 2 -, - CO -, - SO 2 NR 7 -, - NR 7 SO 2 -, - CONR 7 -, - NR 7 CO -, - COO-, and -OCO- the Can be mentioned. Here, the substituent T described later can be applied as the substituent.

In general formula (1), L ¹ , L ² , L ³ , L ⁴ , L ⁵ , and L ⁶ each independently represent —O— or —NR—. R represents a hydrogen atom, an alkyl group, or an aryl group, and may be bonded to Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , or R ⁵ to form a ring. Preferred examples of R include a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, and an isopropyl group), and an aryl group having 6 to 12 carbon atoms (for example, a phenyl group and a naphthyl group). And more preferably an alkyl group having 1 to 6 carbon atoms. Note that L ¹ , L ² , L ³ , L ⁴ , L ⁵ , and L ⁶ may be different from each other, any two or more of them may be the same, or all may be the same. In order to control the retardation of the optical film, it is preferable that L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ are all the same.

Next, the compound represented by the general formula (2) will be described.
In the formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , L ¹ , L ² , L ³ , L ⁴ , L ⁵ , and L ⁶ are the same as those described in the general formula (1), and L ⁷ is Represents a single bond or a divalent linking group. Preferred examples of the divalent linking group include an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, —NR ⁷ — (R ⁷ is a hydrogen atom, and an alkyl group which may have a substituent. Or an aryl group), —O—, —S—, —SO—, —SO ₂ —, —CO—, —SO ₂ NR ⁷ —, —NR ⁷ SO ₂ —, —CONR ^{7 -, - NR 7 CO -,} - COO-, and -OCO- can be mentioned. Here, the substituent T described later can be applied as the substituent.

Hereinafter, the substituent T will be described.
The substituent T is preferably a halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, Isopropyl group, t-butyl group, n-octyl group, 2-ethylhexyl group), cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms such as cyclohexyl group, cyclopentyl group, 4 -N-dodecylcyclohexyl group), a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. For example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octa -3-yl), an alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as a vinyl group or an allyl group), a cycloalkenyl group (preferably a substituted or unsubstituted group having 3 to 30 carbon atoms). Substituted cycloalkenyl groups, that is, monovalent groups in which one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms has been removed (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), bicyclo Alkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] oct-2-ene-4 Yl), an alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as an ethynyl group or a propargyl group), an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms) A phenyl group, a p-tolyl group, a naphthyl group, a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound with one hydrogen atom removed. A 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and 2-benzothiazolyl. Group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example For example, methoxy group, ethoxy group, isopropoxy group, t-butoxy group, n-octyloxy group, 2-methoxyethoxy group), aryloxy group (preferably substituted or unsubstituted aryloxy having 6 to 30 carbon atoms) Groups such as phenoxy, 2-methylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy, silyloxy (preferably silyloxy having 3 to 20 carbons) Group, for example, trimethylsilyloxy group, tert-butyldimethylsilyloxy group), heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, 1-phenyltetrazole-5-oxy group , 2-tetrahydropyranyloxy group), acyloxy group (preferably formyloxy group, charcoal) A substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 primes, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy Group, p-methoxyphenylcarbonyloxy group), carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyl group) Oxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group), alkoxycarbonyloxy group (preferably substituted or unsubstituted having 2 to 30 carbon atoms) Alkoxycarbonyloxy group For example, a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a tert-butoxycarbonyloxy group, an n-octylcarbonyloxy group), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy having 7 to 30 carbon atoms) Group, for example, phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxyphenoxycarbonyloxy group), amino group (preferably amino group, substituted or unsubstituted having 1 to 30 carbon atoms) Alkylamino group, substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as amino group, methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, diphenylamino group), acylamino group (preferably Is formylami Group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino group, acetylamino group, pivaloylamino group, lauroylamino group , Benzoylamino group), aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as carbamoylamino group, N, N-dimethylaminocarbonylamino group, N, N- Diethylaminocarbonylamino group, morpholinocarbonylamino group), alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino group, ethoxycarbonylamino group, tert-butoxy A rubonylamino group, an n-octadecyloxycarbonylamino group, an N-methyl-methoxycarbonylamino group), an aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, Phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxycarbonylamino group), sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms) , For example, sulfamoylamino group, N, N-dimethylaminosulfonylamino group, Nn-octylaminosulfonylamino group, alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted having 1 to 30 carbon atoms) Alkylsulfonyla Group, substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p- Methylphenylsulfonylamino group), mercapto group, alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio group, ethylthio group, n-hexadecylthio group), arylthio group (preferably carbon number) 6-30 substituted or unsubstituted arylthio groups such as phenylthio group, p-chlorophenylthio group, m-methoxyphenylthio group, heterocyclic thio group (preferably substituted or unsubstituted heterogeneous group having 2 to 30 carbon atoms) A ring thio group, for example, a 2-benzothiazolylthio group, 1-phenyltetrazol-5-ylthio group), sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl Group, N, N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N-benzoylsulfamoyl group, N- (N′-phenylcarbamoyl) sulfamoyl group), sulfo group, alkyl and arylsulfinyl group ( Preferably, it is a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group, p-methylphenylsulfinyl. Group), alkyl and aryls A sulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms such as a methylsulfonyl group, an ethylsulfonyl group, a phenylsulfonyl group, p- Methylphenylsulfonyl group), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, such as acetyl group, A valoylbenzoyl group), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as a phenoxycarbonyl group, an o-chlorophenoxycarbonyl group, an m-nitrophenoxycarbonyl group, p-tert-butylphenoxycarbonyl ), An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, an n-octadecyloxycarbonyl group), a carbamoyl group ( Preferably, the substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, for example, carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- (Methylsulfonyl) carbamoyl group), aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, such as phenylazo Group, p-chlorophenylazo group, 5-ethylthio 1,3,4-thiadiazol-2-ylazo group), imide group (preferably N-succinimide group, N-phthalimide group), phosphino group (preferably substituted or unsubstituted phosphino group having 2 to 30 carbon atoms) For example, dimethylphosphino group, diphenylphosphino group, methylphenoxyphosphino group), phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms such as phosphinyl group, dioctyloxyphosphinyl) Group, diethoxyphosphinyl group), phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy group, dioctyloxyphosphini Ruoxy group), a phosphinylamino group (preferably a C2-C30 substituent or Unsubstituted phosphinylamino group such as dimethoxyphosphinylamino group, dimethylaminophosphinylamino group, silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms such as trimethylsilyl Group, tert-butyldimethylsilyl group, phenyldimethylsilyl group).

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

  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.

R ¹¹ and R ¹² each independently represents a substituent, and examples of preferred substituents have the same meaning as the above-described substituent T. R ¹¹ and R ¹² are more preferably a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an acyloxy group, an acylamino group, an alkylthio group, an acyl group, an aryloxycarbonyl group, or an alkoxycarbonyl group. .
m and n each independently represents an integer of 1 to 4. When m and n are 2 or more, R ¹¹ and R ¹² may all be the same or different.

As a preferred embodiment of the compound represented by the general formula (2),
Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are each independently a substituted or unsubstituted aryl group, preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, more preferably a substituted or unsubstituted phenyl group. Or an aromatic heterocycle containing a nitrogen atom, preferably an aromatic heterocycle containing a 5- to 6-membered nitrogen atom or a condensed ring with another ring,
L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ are each independently —O— or —NR— (R represents a hydrogen atom, an alkyl group or an aryl group), preferably. R is a hydrogen atom, a methyl group or a phenyl group,
Examples of L ⁷ include a single bond, —COO—, —CO—, —SO ₂ —, a substituted or unsubstituted alkylene group, and a substituted or unsubstituted alkynylene group.

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

（式中、ＡおよびＡ’はアミノ基、水酸基等の反応性基を表し、Ｌ⁷は先に記載した通りである。）
を有する原料化合物を、シアヌル酸ハライドなどのシアヌル酸誘導体との反応に付し、その両末端に１，３，５−トリアジン環を導入して中間体を得た後、該中間体に所望の末端置換基を導入することによって得ることができる。また、先行して所望の末端置換基を２箇所に導入した１，３，５−トリアジンのハロゲン化物に前述の原料化合物を反応させることによっても得ることができる。一般式（１）で表される化合物も、同様の方法で合成することができる。ただし、本発明の化合物の合成法はこの例に限定されない。 The compound represented by the general formula (2) can be synthesized by a known method, for example, the following structure:

(In the formula, A and A ′ represent reactive groups such as amino group and hydroxyl group, and L ⁷ is as described above.)
Is subjected to a reaction with a cyanuric acid derivative such as cyanuric acid halide, and 1,3,5-triazine ring is introduced into both ends thereof to obtain an intermediate, and then the intermediate has a desired It can be obtained by introducing a terminal substituent. It can also be obtained by reacting the above-mentioned raw material compound with a halide of 1,3,5-triazine in which a desired terminal substituent is introduced at two positions in advance. The compound represented by the general formula (1) can also be synthesized by the same method. However, the synthesis method of the compound of the present invention is not limited to this example.

  In the cellulose derivative composition of the present invention, the content of the compound represented by the general formula (1) to the general formula (2) is preferably 0.1 to 20% by mass, more preferably based on the cellulose derivative. Is 0.5 to 16% by mass, more preferably 1 to 12% by mass, particularly preferably 1 to 8% by mass, and most preferably 1 to 5% by mass.

  The compound represented by the general formula (1) or the general formula (2) can be used as a retardation control agent for an optical film, and in particular, a retardation control agent for obtaining a film having excellent Re developability by stretching. Can be suitably used. The compounds represented by the general formulas (1) to (2) are particularly useful as retardation control agents for cellulose derivative films. Details of a method for producing a film containing these compounds will be described later.

[Cellulose derivative composition]
The cellulose derivative composition of the present invention is a composition comprising a cellulose derivative and at least one selected from the compounds represented by the general formulas (1) to (2). In the present invention, the “cellulose derivative” includes a cellulose compound and a compound having a cellulose skeleton obtained by introducing a functional group biologically or chemically using cellulose as a raw material. A preferable compound having a cellulose skeleton is a cellulose ester, and more preferable is a cellulose acylate (such as cellulose triacylate and cellulose acylate propionate). In the present invention, two or more different cellulose derivatives may be mixed and used.
Hereinafter, the present invention will be described using a case where cellulose acylate is used as the cellulose derivative as a representative example.

Among the cellulose derivatives, preferred cellulose acylates include the following materials. That is, the cellulose acylate is a cellulose acylate in which the degree of substitution of the cellulose with a hydroxyl group satisfies all of the following formulas (I) to (III).
(I) 1.0 ≦ SA + SB ≦ 3.0
(II) 0.5 ≦ SA ≦ 3.0
(III) 0 ≦ SB ≦ 1.5

  Here, SA and SB in the formula represent a substituent of an acyl group substituted with a hydroxyl group of cellulose, SA is a substitution degree of an acetyl group, and SB is a substitution degree of an acyl group having 3 to 22 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). In the cellulose acylate used in the present invention, the total substitution degree of the hydroxyl groups SA and SB is more preferably 1.50 to 2.96, and particularly preferably 2.00 to 2.95. Further, the substitution degree of SB is 0 to 1.5, particularly 0 to 1.0. Further, SB is preferably 28% or more of the substituent group of the 6-position hydroxyl group, more preferably 30% or more is the substituent of the 6-position hydroxyl group, more preferably 35% or more, and particularly preferably 40% or more. It is preferably a 6-position hydroxyl group substituent. Furthermore, the cellulose acylate having a total substitution degree of SA and SB at the 6-position of cellulose acylate of 0.8 or more, more preferably 0.85 or more, and particularly 0.90 or more can be used. .

  In the present invention, the acyl group having 3 to 22 carbon atoms representing the above-mentioned SB of cellulose acylate may be either an aliphatic acyl group or an aromatic acyl group, and is not particularly limited. These are, for example, cellulose alkylcarbonyl esters, alkenylcarbonyl esters, aromatic carbonyl esters, aromatic alkylcarbonyl esters, and the like, each of which may further have a substituted group. Examples of these preferred SB substituents include propionyl group, butanoyl group, heptanoyl group, hexanoyl group, octanoyl group, decanoyl group, dodecanoyl group, tridecanoyl group, tetradecanoyl group, hexadecanoyl group, octadecanoyl group, Examples include iso-butanoyl group, pivaloyl group, cyclohexanecarbonyl group, oleyl group, benzoyl group, naphthylcarbonyl group, cinnamoyl group and the like. Among these, a propionyl group, a butanoyl group, a dodecanoyl group, an octadecanoyl group, a pivaloyl group, an oleoyl group, a benzoyl group, a naphthylcarbonyl group, a cinnamoyl group, and the like can be given.

  The basic principle of the cellulose acylate synthesis method is described in Mita et al., Wood Chemistry pages 180-190 (Kyoritsu Shuppan, 1968). A typical synthesis method is a liquid phase acetylation method using a carboxylic acid anhydride-acetic acid-sulfuric acid catalyst. Specifically, cellulose raw materials such as cotton linter and wood pulp are pretreated with an appropriate amount of acetic acid, and then put into a pre-cooled carboxylic acid mixture to be esterified to complete cellulose acylate (2nd, 3rd and 6th). The total degree of acyl substitution at the position is approximately 3.00). The carboxylated mixed solution generally contains acetic acid as a solvent, carboxylic anhydride as an esterifying agent, and sulfuric acid as a catalyst.

  The carboxylic anhydride is usually used in a stoichiometric excess over the sum of the cellulose that reacts with it and the water present in the system. After completion of the acylation reaction, a neutralizing agent (for example, calcium, magnesium, iron, aluminum or zinc) is used for hydrolysis of excess carboxylic anhydride remaining in the system and neutralization of a part of the esterification catalyst. Of carbonate, acetate or oxide). Next, the obtained complete cellulose acylate is saponified and aged by maintaining it at 50 to 90 ° C. in the presence of a small amount of an acetylation reaction catalyst (generally, remaining sulfuric acid) to obtain the desired degree of acyl substitution and polymerization. The cellulose acylate having a degree is changed. When the desired cellulose acylate is obtained, the catalyst remaining in the system is completely neutralized with a neutralizing agent as described above, or in water or dilute sulfuric acid without neutralization. The cellulose acylate solution is added (or water or dilute sulfuric acid is added into the cellulose acylate solution) to separate the cellulose acylate, and the cellulose acylate is obtained by washing and stabilizing treatment.

  The degree of polymerization of the cellulose acylate preferably used in the present invention is a viscosity average degree of polymerization of 200 to 700, preferably 250 to 550, more preferably 250 to 400, and particularly preferably a viscosity average degree of polymerization of 250 to 350. The average degree of polymerization can be measured by Uda et al.'S intrinsic viscosity method (Kazuo Uda, Hideo Saito, Journal of Textile Society, Vol. 18, No. 1, pages 105-120, 1962). Further details are described in JP-A-9-95538.

  When the low molecular component is removed, the average molecular weight (degree of polymerization) increases, but the viscosity becomes lower than that of normal cellulose acylate, which is useful. Cellulose acylate having a small amount of low molecular components can be obtained by removing low molecular components from cellulose acylate synthesized by a usual method. The removal of the low molecular component can be carried out by washing the cellulose acylate with an appropriate organic solvent.

  In addition, when manufacturing a cellulose 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 of cellulose. When the amount of the sulfuric acid catalyst is in the above range, cellulose acylate that is preferable in terms of molecular weight distribution (uniform molecular weight distribution) can be synthesized. The water content of the cellulose acylate used in the present invention is preferably 2% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.7% by mass or less. In general, cellulose acylate contains water and is known to have a water content of 2.5 to 5% by mass. In the present invention, in order to obtain a cellulose acylate having a low moisture content, the cellulose acylate may be dried, and the method is not particularly limited as long as the desired moisture content (for example, 2% by mass or less) can be obtained.

  As for these cellulose acylates that can be used in the present invention, the raw material cotton and the synthesis method thereof are disclosed in JIII Journal of Technical Disclosure (Technical No. 2001-1745, published on March 15, 2001, Invention Association), pages 7-12. It is described in detail on the page.

  The cellulose derivative content in the cellulose derivative composition of the present invention can be 55% by mass or more, preferably 70% by mass or more, and more preferably 80% by mass or more based on the total solid content. When preparing the cellulose derivative composition of the present invention as a raw material for film production, it is preferable to use cellulose acylate particles. 90% by mass or more of the particles to be used preferably have a particle size of 0.5 to 5 mm. Moreover, it is preferable that 50 mass% or more of the particle | grains to be used have a particle size of 1-4 mm. The cellulose acylate particles preferably have a shape as close to a sphere as possible.

  In addition to the cellulose derivative and the compound represented by the general formula (1) to the general formula (2), the cellulose derivative composition of the present invention includes various additives (for example, plastics) in each preparation step. Agents, ultraviolet inhibitors, deterioration inhibitors, optical anisotropy control agents, fine particles, release agents, infrared absorbers, etc.), which may be solid or oily. That is, the melting point and boiling point are not particularly limited. For example, mixing of ultraviolet absorbing material at 20 ° C. or lower and 20 ° C. or higher, and similarly, mixing of a plasticizer is described in, for example, JP-A-2001-151901. Furthermore, infrared absorbing dyes are described, for example, in JP-A No. 2001-194522. Moreover, the addition time may be added at any time in the dope preparation step, but may be added by adding an additive to the final preparation step of the dope preparation step.

  Furthermore, the amount of each material added is not particularly limited as long as the function is manifested. Moreover, when the cellulose derivative film which consists of a cellulose derivative composition of this invention is formed from a multilayer, the kind and addition amount of an additive of each layer may differ. For example, although it describes in Unexamined-Japanese-Patent No. 2001-151902 etc., these are techniques conventionally known.

  Further, as these materials, materials described in detail on pages 16 to 22 in the Japan Institute of Invention Disclosure Technical Report (Public Technical Number 2001-1745, published on March 15, 2001, Japan Institute of Invention) are preferably used. .

In the present invention, an organic solvent used for dissolving a cellulose derivative, preferably cellulose acylate is described.
First, in the present invention, a non-chlorine organic solvent that is preferably used in preparing a cellulose derivative solution will be described. In the present invention, the non-chlorine organic solvent is not particularly limited as long as the object can be achieved as long as the cellulose derivative can be dissolved, cast, and formed into a film. The non-chlorine organic solvent used in the present invention is preferably a solvent selected from esters, ketones and ethers having 3 to 12 carbon atoms.

  The ester, ketone and ether may have a cyclic structure. A compound having two or more functional groups of esters, ketones and ethers (that is, —O—, —CO— and —COO—) can also be used as a main solvent, such as an alcoholic hydroxyl group. It may have a functional group of In the case of the main solvent having two or more kinds of functional groups, the number of carbon atoms may be within the specified range of the compound having any functional group.

  Examples of esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate. Examples of ketones having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and methylcyclohexanone. Examples of ethers having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, anisole and phenetole. Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol.

  The non-chlorine organic solvent used in the above cellulose derivative is selected from the various viewpoints described above, and is preferably as follows. That is, in the present invention, a preferable solvent used for the cellulose derivative is a mixed solvent of three or more different from each other, and the first solvent is selected from methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, dioxolane, and dioxane. At least one selected from the above or a mixture thereof, and the second solvent is selected from ketones having 4 to 7 carbon atoms or acetoacetate, and alcohol having 1 to 10 carbon atoms as the third solvent. Or it is chosen from a hydrocarbon, More preferably, it is a C1-C8 alcohol.

  Note that when the first solvent is a mixed liquid of two or more kinds of solvents, the second solvent may be omitted. The first solvent is more preferably methyl acetate, acetone, methyl formate, ethyl formate, or a mixture thereof, and the second solvent is preferably methyl ethyl ketone, cyclopentanone, cyclohexanone, or methyl acetyl acetate. It may be.

  The alcohol as the third solvent may be linear, branched or cyclic, and is preferably a saturated aliphatic hydrocarbon. The hydroxyl group of the alcohol may be any of primary to tertiary. Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol and cyclohexanol. As the alcohol, fluorine-based alcohol is also used. Examples thereof include 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol and the like.

  Furthermore, the hydrocarbon may be linear, branched or cyclic. Either aromatic hydrocarbons or aliphatic hydrocarbons can be used. The aliphatic hydrocarbon may be saturated or unsaturated. Examples of hydrocarbons include cyclohexane, hexane, benzene, toluene and xylene. These alcohols and hydrocarbons as the third solvent may be used alone or in combination of two or more, and are not particularly limited. As the third solvent, preferred specific compounds include alcohol, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and cyclohexanol, cyclohexane, hexane, Are methanol, ethanol, 1-propanol, 2-propanol, 1-butanol.

  The above three types of mixed solvents preferably contain a first solvent in a proportion of 20 to 95% by mass, a second solvent in a proportion of 2 to 60% by mass, and a third solvent in a proportion of 2 to 30% by mass, Furthermore, it is preferable that a 1st solvent is 30-90 mass%, a 2nd solvent is 3-50 mass%, and also 3-25 mass% of 3rd alcohol is contained. In particular, it is preferable that the first solvent is 30 to 90% by mass, the second solvent is 3 to 30% by mass, and the third solvent is alcohol and 3 to 15% by mass.

  In addition, when the first solvent is a mixed solution and the second solvent is not used, the first solvent is preferably contained in a ratio of 20 to 90% by mass and the third solvent in a ratio of 5 to 30% by mass, Furthermore, it is preferable that a 1st solvent is 30-86 mass%, and also a 3rd solvent is contained 7-25 mass%. The non-chlorine organic solvent used in the present invention is described in more detail in pages 12 to 16 in the Japan Society for Invention and Technology (Public Technical Number 2001-1745, published on March 15, 2001, Japan Society for Invention). It is described in detail. Preferred combinations of non-chlorine organic solvents in the present invention can be listed below, but are not limited thereto.

-Methyl acetate / acetone / methanol / ethanol / butanol (75/10/5/5/5, parts by mass),
-Methyl acetate / acetone / methanol / ethanol / propanol (75/10/5/5/5, parts by mass),
Methyl acetate / acetone / methanol / butanol / cyclohexane (75/10/5/5/5, parts by mass),
・ Methyl acetate / acetone / ethanol / butanol (81/8/7/4, parts by mass)
・ Methyl acetate / acetone / ethanol / butanol (82/10/4/4, parts by mass)
・ Methyl acetate / acetone / ethanol / butanol (80/10/4/6, part by mass)
Methyl acetate / methyl ethyl ketone / methanol / butanol (80/10/5/5, parts by mass),
-Methyl acetate / acetone / methyl ethyl ketone / ethanol / isopropanol (75/10/10/5/7, parts by mass)
Methyl acetate / cyclopentanone / methanol / isopropanol (80/10/5/8, parts by mass),
・ Methyl acetate / acetone / butanol (85/5/5, part by mass),
Methyl acetate / cyclopentanone / acetone / methanol / butanol (60/15/15/5/6, parts by mass),
-Methyl acetate / cyclohexanone / methanol / hexane (70/20/5/5, parts by mass)
・ Methyl acetate / methyl ethyl ketone / acetone / methanol / ethanol (50/20/20/5/5, part by mass),
・ Methyl acetate / 1, 3 dioxolane / methanol / ethanol (70/20/5/5, part by mass),
-Methyl acetate / dioxane / acetone / methanol / ethanol (60/20/10/5/5, parts by mass),
Methyl acetate / acetone / cyclopentanone / ethanol / isobutanol / cyclohexane (65/10/10/5/5/5, parts by mass),
・ Methyl formate / methyl ethyl ketone / acetone / methanol / ethanol (50/20/20/5/5, part by mass),
-Methyl formate / acetone / ethyl acetate / ethanol / butanol / hexane (65/10/10/5/5/5, parts by mass)
Acetone / methyl acetoacetate / methanol / ethanol (65/20/10/5, parts by mass),
Acetone / cyclopentanone / ethanol / butanol (65/20/10/5, parts by mass),
Acetone / 1,3 dioxolane / ethanol / butanol (65/20/10/5, part by mass),
1,3 dioxolane / cyclohexanone / methyl ethyl ketone / methanol / butanol (55/20/10/5/5, parts by mass)
Etc.

  In addition to the non-chlorine organic solvent, the cellulose derivative solution may contain dichloromethane in an amount of 10% by mass or less of the total organic solvent amount.

  In the present invention, when preparing a cellulose derivative solution (composition liquid), a chlorine-based organic solvent may be used as a main solvent in some cases. In the present invention, the chlorinated organic solvent is not particularly limited as long as the object can be achieved as long as the cellulose derivative can be dissolved, cast and film-formed. These chlorinated organic solvents are preferably dichloromethane and chloroform. Particularly preferred is dichloromethane.

  In addition, when a chlorinated organic solvent is used as the main solvent, it is not particularly problematic to mix an organic solvent other than the chlorinated organic solvent. In that case, it is preferable to use at least 50% by mass of dichloromethane. In the present invention, a non-chlorine organic solvent that can be used in combination with a chlorinated organic solvent as a main solvent is described below. That is, as a preferable non-chlorine organic solvent used in combination, a solvent selected from esters, ketones, ethers, alcohols, hydrocarbons and the like having 3 to 12 carbon atoms is preferable. Esters, ketones, ethers and alcohols may have a cyclic structure. A compound having two or more functional groups of esters, ketones and ethers (that is, —O—, —CO— and —COO—) can also be used as a solvent. For example, other functional groups such as alcoholic hydroxyl groups can be used. You may have group simultaneously. In the case of a solvent having two or more types of functional groups, the number of carbon atoms may be within the specified range of the compound having any functional group. Examples of esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate.

  Examples of ketones having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and methylcyclohexanone. Examples of ethers having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, anisole and phenetole. Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol.

  The alcohol used in combination with the chlorinated organic solvent may be linear, branched or cyclic, and among them, saturated aliphatic hydrocarbon is preferable. The hydroxyl group of the alcohol may be any of primary to tertiary. Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol and cyclohexanol. As the alcohol, fluorine-based alcohol is also used. Examples thereof include 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol and the like.

  Furthermore, the hydrocarbon may be linear, branched or cyclic. Either aromatic hydrocarbons or aliphatic hydrocarbons can be used. The aliphatic hydrocarbon may be saturated or unsaturated. Examples of hydrocarbons include cyclohexane, hexane, benzene, toluene and xylene.

  The non-chlorine organic solvent used in combination with the chlorine-based organic solvent that is the main solvent used for the above cellulose derivatives is not particularly limited, but is methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, dioxolane, dioxane. It is preferably selected from ketones or acetoacetates having 4 to 7 carbon atoms, alcohols or hydrocarbons having 1 to 10 carbon atoms. Preferred non-chlorine organic solvents used in combination include methyl acetate, acetone, methyl formate, ethyl formate, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl acetyl acetate, methanol, ethanol, 1-propanol, 2-propanol, 1- Mention may be made of butanol, 2-butanol, and cyclohexanol, cyclohexane, hexane. In the present invention, examples of a combination of a chlorinated organic solvent and a non-chlorinated organic solvent, which are preferable main solvents, include the following, but are not limited thereto.

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

In this invention, it is preferable that the aggregate molecular weight of the cellulose acylate of the diluted solution which made dope containing a cellulose acylate 0.1-5 mass% with the organic solvent of the same composition is 150,000-15 million. More preferably, the associated molecular weight is 180,000 to 9 million. This associated molecular weight can be determined by a static light scattering method. In that case, it is preferable to dissolve so that the inertial square radius required at the same time is 10 to 200 nm. A more preferable inertial square radius is 20 to 200 nm. Furthermore, it is preferable to dissolve so that the second virial coefficient is −2 × 10 ⁻⁴ to 4 × 10 ^−4, and more preferably, the second virial coefficient is −2 × 10 ⁻⁴ to 2 × 10 ^−4. It is. Here, the definition of the association molecular weight, the inertial square radius, and the second virial coefficient in the present invention will be described.

  These were measured using the static light scattering method according to the following method. Although the measurement was performed in a dilute region for the convenience of the apparatus, these measured values reflect the behavior of the dope in the high concentration region in the present invention. First, cellulose acylate was dissolved in a solvent used for the dope to prepare 0.1 mass%, 0.2 mass%, 0.3 mass%, and 0.4 mass% solutions. In order to prevent moisture absorption, the cellulose acylate was dried at 120 ° C. for 2 hours, and was measured at 25 ° C. and 10% RH. The dissolution method was carried out in accordance with the method (room temperature dissolution method, cooling dissolution method, high temperature dissolution method) employed during dope dissolution.

  Subsequently, these solutions and the solvent were filtered through a 0.2 μm Teflon filter. The filtered solution was measured for static light scattering at intervals of 10 degrees from 30 degrees to 140 degrees at 25 ° C. using a light scattering measuring device (DLS-700 manufactured by Otsuka Electronics Co., Ltd.). The obtained data was analyzed by the BERRY plot method. The refractive index necessary for this analysis is the value of the solvent determined by the Abbe refractive system, and the refractive index concentration gradient (dn / dc) is a differential refractometer (DRM-1021 manufactured by Otsuka Electronics Co., Ltd.). The measurement was performed using the solvent and the solution used for the light scattering measurement.

  Regarding the preparation of a dope containing a cellulose derivative in the present invention, the dissolution method is not particularly limited, and it may be performed at room temperature, further by a cooling dissolution method or a high temperature dissolution method, and further by a combination thereof. Regarding these, for example, JP-A-5-163301, JP-A-61-106628, JP-A-58-127737, JP-A-9-95544, JP-A-10-95854, JP-A-10-45950, JP 2000-53784, JP 11-322946, JP 11-322947, JP 2-276830, JP 2000-273239, JP 11-71463, JP 04-259511, Special JP-A 2000-273184, JP-A No. 11-323017, JP-A No. 11-302388 and the like disclose preparation methods of cellulose derivative solutions. The above-described method for dissolving these cellulose derivatives in an organic solvent can be applied to the present invention as long as it is within the scope of the present invention.

  These details are described in detail on pages 22 to 25 in the Japan Society for Invention and Technology (Publication No. 2001-1745, published on March 15, 2001, Japan Society for Inventions), especially for non-chlorine solvent systems. Yes. Furthermore, in the present invention, solution concentration and filtration are usually carried out for a dope containing a cellulose derivative, and the method is also disclosed in the JIII Journal of Technical Disclosure (Publication No. 2001-1745, published on March 15, 2001). , Invention Association), page 25. In addition, when it melt | dissolves at high temperature, it is the case where it is more than the boiling point of the organic solvent to be used, and in that case, it uses in a pressurized state.

  The cellulose derivative composition of the present invention comprises a solution obtained by dissolving the compound represented by the general formula (1) to the general formula (2) in an appropriate solvent and a cellulose derivative in an appropriate solvent. It can be prepared by mixing the obtained cellulose derivative solution. The mixing method of both solutions is not specifically limited, The solution obtained by mixing both solutions can be used as dope for film formation. However, in the present invention, the order of addition of the cellulose derivative and the compound represented by the general formula (1) to the general formula (2) is not limited, and both may be added simultaneously. The concentration of the cellulose derivative in the dope is preferably 10 to 30% by mass, more preferably 13 to 27% by mass, and particularly preferably 15 to 25% by mass. The method for dissolving the cellulose derivative at these concentrations may be carried out so that the cellulose derivative has a predetermined concentration at the stage of dissolution, or a concentration step which will be described later after being prepared in advance as a low concentration solution (for example, 9 to 14% by mass). May be adjusted to a predetermined high concentration solution. Furthermore, after preparing a high concentration cellulose derivative solution in advance, various additives may be added to obtain a predetermined low concentration cellulose derivative solution, and any method can be used as long as a dope having the above concentration can be obtained. .

  In addition, in order to dissolve the compounds represented by the general formula (1) or the general formula (2), the same solvents as those for the cellulose derivative described above can be used. The density | concentration of the compound represented by General formula (1) thru | or General formula (2) in dope can be 0.1-30 mass%, for example, Preferably it can be 1-15 mass%.

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

[Cellulose derivative film]
The cellulose derivative film of the present invention comprises the cellulose derivative composition of the present invention.
Next, the manufacturing method of the cellulose derivative film of this invention is described.

  As a method and equipment for producing the cellulose derivative film of the present invention, a solution casting film forming method and a solution casting film forming apparatus conventionally used for producing cellulose triacetate film can be used. A specific example will be described below. The dope (cellulose derivative composition solution) prepared from the dissolving machine (kettle) is once stored in a storage kettle, and the foam contained in the dope is defoamed for final preparation. The dope is sent from the dope discharge port to the pressure die through a pressure metering gear pump capable of delivering a constant amount of liquid with high accuracy, for example, by the number of rotations, and the dope is run endlessly from the die (slit) of the pressure die. The dry-dried dope film (also referred to as web) is peeled off from the metal support at a peeling point that is uniformly cast on the metal support and substantially rounds the metal support.

  Both ends of the obtained web are sandwiched between clips, transported by a tenter while keeping the width, dried, then transported by a roll group of a drying device, dried, and wound up to a predetermined length by a winder. The combination of the tenter and the roll group dryer varies depending on the purpose. In the solution casting film forming method used for silver halide photographic light-sensitive materials and functional protective films for electronic displays, in addition to the solution casting film forming apparatus, an undercoat layer, an antistatic layer, an antihalation layer, a protective layer, etc. In many cases, a coating apparatus is added to the surface processing of the film. Each of these manufacturing processes is described in detail on pages 25 to 30 in the Japan Institute of Invention Disclosure Technical Report (Public Technical Number 2001-1745, published on March 15, 2001, Japan Institute of Invention). (Including rolling), metal support, drying, peeling, stretching and the like.

  Here, although the space temperature of a casting part is not specifically limited in this invention, It is preferable that it is -50-50 degreeC. Furthermore, it is preferable that it is -30-40 degreeC, and it is especially preferable that it is -20-30 degreeC. In particular, the dope cast by the space temperature at a low temperature can be cooled on the support instantly to increase the gel strength, thereby holding the film containing the organic solvent. Thereby, without evaporating the organic solvent from the cellulose derivative, it can be peeled off from the support in a short time, and high-speed casting can be achieved. The means for cooling the space may be normal air, nitrogen, argon, helium or the like, and is not particularly limited. The humidity in that case is preferably 0 to 70% RH, and more preferably 0 to 50% RH. Moreover, in this invention, the temperature of the support body of the casting part which casts dope is -50-130 degreeC normally, Preferably it is -30-25 degreeC, More preferably, it is -20-15 degreeC. In order to keep the casting part at a desired temperature, it may be achieved by introducing a cooled gas into the casting part, or a cooling device may be arranged in the casting part to cool the space. At this time, it is important to take care not to attach water, and it can be carried out by a method such as using dry gas.

  In the present invention, the following configurations are particularly preferred for the contents and casting of each layer. That is, the dope is a dope containing 0.1 to 20% by mass of at least one liquid or solid plasticizer with respect to the cellulose derivative at 25 ° C. and / or at least one liquid or solid. And a fine particle powder having an average particle size of 5 to 3000 nm and at least one solid. Dope containing 0.001 to 5% by mass with respect to the derivative, and / or dope containing 0.001 to 2% by mass of at least one fluorosurfactant with respect to the cellulose derivative And / or a coating containing 0.0001 to 2% by mass of at least one release agent with respect to the cellulose derivative. And / or a dope containing 0.0001 to 2% by mass of at least one degradation inhibitor with respect to the cellulose derivative, and / or at least one optical anisotropy control agent. Is a dope containing 0.1 to 15% by mass of the cellulose derivative and / or 0.1 to 5% by mass of at least one infrared absorber based on the cellulose derivative. And a cellulose derivative film (preferably a cellulose acylate film) produced from the dope.

  In the casting step, one kind of dope may be cast as a single layer, or two or more kinds of dopes may be cast simultaneously and / or sequentially. In the case of having a casting process comprising two or more layers, in the dope and cellulose derivative film to be produced, the composition of the chlorinated solvent in each layer is either the same or different, and the additive in each layer It is either one type or a mixture of two or more types, the addition position of the additive to each layer is either the same layer or a different layer, the concentration of the additive in the solution Each layer has the same or different concentration, the molecular weight of the aggregates in each layer is the same or the molecular weight of the different aggregates, and the temperature of the solution in each layer is the same. Either one of the different or different temperatures, the application amount of each layer is the same or different application amount, whether the viscosity of each layer is the same or different The thickness of each layer after drying is either the same or different, and the materials present in each layer are in the same state or distribution or in different states or distributions, Made from a dope and its dope characterized in that the physical properties of each layer are either the same or different physical properties, the physical properties of each layer are either uniform or a distribution of different physical properties A cellulose derivative film (preferably a cellulose acylate film) is also preferable.

Here, the physical properties include physical properties described in detail on pages 6 to 7 of the Japan Society for Invention and Innovation Technical Report (Public Technical Number 2001-1745, issued on March 15, 2001, Japan Institute of Invention). For example, haze, transmittance, spectral characteristics, retardation Re, Rth, molecular orientation axis, axial misalignment, tear strength, folding strength, tensile strength, roll-in / out Rt difference, creaking, dynamic friction, alkaline hydrolysis, curl value, water content Rate, residual solvent amount, heat shrinkage rate, high humidity dimensional evaluation, moisture permeability, base flatness, dimensional stability, heat shrinkage starting temperature, elastic modulus, and measurement of bright spot foreign matter, etc. Impedance and surface shape used for evaluation are also included.
In addition, the Yellow Index, Transparency, Thermophysical Properties (Tg) of Cellulose Acylate described in detail on page 11 in the Japan Society for Invention and Innovation Technical Report (Public Technical Number 2001-1745, published on March 15, 2001, Invention Association) , Heat of crystallization) and the like.

  The cellulose derivative film of the present invention may be stretched. In order to develop optical anisotropy, the film is particularly preferably stretched at an arbitrary magnification.

  For the stretching, a known method can be used, for example, a roll uniaxial stretching method, a tenter uniaxial stretching method, a simultaneous biaxial stretching method at a temperature between 10 ° C. and 50 ° C. higher than the glass transition temperature (Tg) of the cellulose derivative film. The film can be stretched by an axial stretching method, a sequential biaxial stretching method, or an inflation method. Further, in the case of film production by the solution pouring method, the film can be stretched within the range of 1% to 30%, more preferably within the range of 5% to 20%. The draw ratio is preferably 1.1 to 3.5 times.

The cellulose derivative film can achieve improved adhesion between the cellulose derivative film and each functional layer (for example, an undercoat layer and a back layer) by optionally performing a surface treatment. For example, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment can be used. The glow discharge treatment here may be low-temperature plasma that occurs in a low-pressure gas of 10 ^{−3 to} 20 Torr, and plasma treatment under atmospheric pressure is also preferable.

  A plasma-excitable gas is a gas that is plasma-excited under the above conditions, and includes chlorofluorocarbons such as argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, tetrafluoromethane, and mixtures thereof. It is done. Details of these are described in detail on pages 30 to 32 in the Journal of the Invention Association (Technology No. 2001-1745, issued on March 15, 2001, Invention Association). Note that, in the plasma treatment at atmospheric pressure which has been attracting attention in recent years, for example, irradiation energy of 20 to 500 Kgy is used under 10 to 1000 Kev, and more preferably irradiation energy of 20 to 300 Kgy is used under 30 to 500 Kev. Among these, an alkali saponification treatment is particularly preferable, and it is extremely effective as a surface treatment of cellulose acylate film.

  The alkali saponification treatment is performed by applying a saponification solution. Examples of the coating method include a dip coating method, a curtain coating method, an extrusion coating method, a bar coating method, and an E-type coating method. The solvent of the alkali saponification coating solution has good wettability because it is applied to the transparent support of the saponification solution, and the surface state remains good without forming irregularities on the surface of the transparent support by the saponification solution solvent. It is preferred to select a solvent to keep. Specifically, an alcohol solvent is preferable, and isopropyl alcohol is particularly preferable.

An aqueous solution of a surfactant can also be used as a solvent. The alkali of the alkali saponification coating solution is preferably an alkali that dissolves in the above solvent, and more preferably KOH or NaOH. The pH of the saponification coating solution is preferably 10 or more, more preferably 12 or more. The reaction conditions during the 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.
Further, the coating-type saponification treatment and the alignment film uncoating described later can be performed continuously, and the number of steps can be reduced.

  In order to achieve adhesion between the film and the emulsion layer, after surface activation treatment, a functional layer is applied directly on the cellulose derivative film to obtain adhesion, and after some surface treatment Alternatively, there is a method in which an undercoat layer (adhesive layer) is provided and a functional layer is applied thereon without surface treatment. Details of these subbing layers are described on page 32 in the Japan Society for Invention and Innovation (Technical Number 2001-1745, published on March 15, 2001, Japan Institute of Invention). In addition, various functional layers of the cellulose derivative film of the present invention are also disclosed in pages 32 to 45 in the Japan Society of Invention and Innovation Technical Report (Public Technical Number 2001-1745, published on March 15, 2001, Japan Society of Invention and Innovation). It is described in detail.

  In order to control the Re value and the Rth value of the cellulose derivative film of the present invention within preferable ranges, the types of the compounds (retardation control agents) represented by the general formula (1) to the general formula (2) to be used and It is preferable to appropriately adjust the addition amount and the draw ratio of the film. In particular, in the present invention, a retardation control agent capable of achieving a desired Rth value is selected, and the addition amount of the retardation control agent and the stretching ratio of the film are appropriately set so as to obtain a desired Re value. By doing so, a cellulose derivative film having a desired Re value and Rth value can be obtained.

  In this specification, Re (λ) and Rth (λ) represent in-plane retardation and retardation in the thickness direction at a wavelength λ, respectively. Re (λ) 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). Rth (λ) is the light of wavelength λnm from the direction inclined by + 40 ° with respect to the film normal direction, with Re (λ) and the in-plane slow axis (determined by KOBRA 21ADH) as the tilt axis (rotation axis). And a retardation value measured by making light of wavelength λ nm incident from a direction inclined by −40 ° with respect to the film normal direction with the in-plane slow axis as the tilt axis (rotation axis). KOBRA 21ADH calculates based on the retardation value measured in 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 the main optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), Polystyrene (1.59).

The use of the cellulose derivative film of the present invention will be briefly described first.
The cellulose derivative film of the present invention is an optical film, particularly for a polarizing plate protective film, an optical compensation sheet for a liquid crystal display device (also referred to as a retardation film), an optical compensation sheet for a reflective liquid crystal display device, and a silver halide photographic light-sensitive material. Useful as a support.
Accordingly, the thickness of the film of the present invention is determined by these uses and is not particularly limited, but is preferably 30 μm or more, more preferably 30 to 200 μm.

  When using as a polarizing plate protective film, the production method of a polarizing plate is not specifically limited, It can produce by a general method. There is a method in which the obtained cellulose derivative film is subjected to alkali treatment, and a polarizer prepared by immersing and stretching the polyvinyl alcohol film in an iodine solution is bonded to both surfaces 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 sides 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 other 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 or at the time of product inspection.

  In this case, the protective 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. The separate film is used for the purpose of covering the adhesive layer to be bonded to the liquid crystal plate, and is used on the side of the surface for bonding the polarizing plate to the 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 film of the present invention is applied can provide excellent display properties regardless of where it is placed. In particular, the polarizing plate protective film on the outermost surface on the display side of the liquid crystal display device is provided with a transparent hard coat layer, an antiglare layer, an antireflective layer, and the like. Therefore, it is particularly preferable to use the polarizing plate protective film in this portion.

  The cellulose derivative film of the present invention can be used in various applications, and is particularly effective when used as an optical compensation sheet for liquid crystal display devices. The cellulose derivative 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-ferroelectric Liquid Crystal), OCB (Optically Compensatory Bend), STN (Supper Twisted Nematic), VA (Vertically Aligned) and Various display modes such as 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 derivative film is effective in the liquid crystal display device of any display mode. Further, it is effective in any of a transmissive type, a reflective type, and a transflective liquid crystal display device. The cellulose derivative 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. The cellulose derivative 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 STN mode liquid crystal cells.

  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 product of the refractive index anisotropy of the rod-like liquid crystalline molecules and the cell gap is 300 to It is in the range of 1500 nm. The optical compensation sheet used in the STN type liquid crystal display device is described in JP-A-2000-105316. 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. The cellulose derivative 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.

  The cellulose derivative film of the present invention is also advantageously used as an optical compensation sheet for TN, STN, HAN, and GH (Guest-Host) type reflective liquid crystal display devices. These display modes have been well known since ancient times. The TN-type reflective liquid crystal display device is described in JP-A-10-123478, International Publication WO98 / 48320, and Japanese Patent No. 3022477. The optical compensation sheet used in the reflective liquid crystal display device is described in International Publication No. WO00 / 65384. The cellulose derivative 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 an ASM (Axially Symmetric Aligned Microcell) mode liquid crystal cell. 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 a paper by Kume et al. (Kume et al., SID 98 Digest 1089 (1998)). The use of these detailed cellulose derivative films described above is described in detail on pages 45 to 59 in the Japan Society for Invention and Technology (Publication No. 2001-1745, published on March 15, 2001, Japan Society for Invention). ing.

  The features of the present invention will be described more specifically with reference to examples and comparative 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 should not be construed as being limited by the specific examples shown below.

Synthesis of Compound Represented by General Formula (1) [Synthesis Example 1: Synthesis of Exemplary Compound (15)]
Exemplified compound (15) was synthesized according to the following scheme.

［中間体（Ｃ）の合成］
氷冷下、シアヌル酸クロライド１８．４４ｇ、炭酸ナトリウム１２．７２ｇ、テトラヒドロフラン（以下ＴＨＦと略す）１００ｍｌの混合物に、化合物（Ａ）１２．２１ｇのＴＨＦ５０ｍｌ溶液を内温が１０℃を越えないようにゆっくりと滴下し、滴下後室温下で１時間攪拌した。反応後、無機塩をろ別し、ろ液を減圧留去した。こうしてガラス状紛体として中間体（Ｃ）を２５．８２ｇ（粗収率９５．６％）得た。

[Synthesis of Intermediate (C)]
Under ice cooling, a mixture of 18.44 g of cyanuric chloride, 12.72 g of sodium carbonate and 100 ml of tetrahydrofuran (hereinafter abbreviated as THF) is mixed with a solution of 12.21 g of compound (A) in 50 ml of THF so that the internal temperature does not exceed 10 ° C. The solution was slowly added dropwise, and stirred at room temperature for 1 hour after the addition. After the reaction, inorganic salts were removed by filtration, and the filtrate was distilled off under reduced pressure. In this way, 25.82 g (crude yield 95.6%) of intermediate (C) was obtained as a glassy powder.

[Synthesis of Exemplary Compound (15)]
Intermediate (C) 5.40 g, metaanisidine 6.16 g, potassium carbonate 13.82 g, and metadichlorobenzene 100 ml were heated and stirred at 130 ° C. for 1 hour. Thereafter, the reaction solution was cooled to room temperature, extracted with chloroform, and the organic layer was concentrated under reduced pressure. The residue was recrystallized from methanol to obtain 5.22 g (yield 58.9%) of Exemplary Compound (15) as white crystals. The compound was identified by ¹ H-NMR (400 MHz).
¹ H-NMR (CDCl ₃ ) δ 3.55 (s, 6H), 3.70 (br. S, 12H), 6.57 (d, 4H), 6.80 (dd, 2H), 6.89 ( d, 2H), 7.00 to 7.20 (m, 14H), 7.40 to 7.60 (br.m, 6H)

[Synthesis Example 1: Synthesis of Exemplified Compound (17)]
Exemplified compound (17) was synthesized according to the following scheme.

［中間体（Ｇ）の合成］
氷冷下、シアヌル酸クロライド１８．４４ｇ、炭酸ナトリウム１２．７２ｇ、テトラヒドロフラン（以下ＴＨＦと略す）１００ｍｌの混合物に、化合物（Ｅ）１４．２６ｇのＴＨＦ５０ｍｌ溶液を内温が１０℃を越えないようにゆっくりと滴下し、滴下後室温下で１時間攪拌した。反応後、無機塩をろ別し、ろ液を減圧留去した。こうしてガラス状紛体として中間体（Ｇ）を２３．５５ｇ（粗収率９２．７％）得た。

[Synthesis of Intermediate (G)]
Under ice-cooling, a mixture of 18.44 g of cyanuric chloride, 12.72 g of sodium carbonate and 100 ml of tetrahydrofuran (hereinafter abbreviated as THF) is mixed with a solution of 14.26 g of compound (E) in 50 ml of THF so that the internal temperature does not exceed 10 ° C. The solution was slowly added dropwise, and stirred at room temperature for 1 hour after the addition. After the reaction, inorganic salts were removed by filtration, and the filtrate was distilled off under reduced pressure. In this manner, 23.55 g (crude yield 92.7%) of intermediate (G) was obtained as a glassy powder.

[Synthesis of Exemplary Compound (17)]
Intermediate (G) 5.08 g, metaanisidine 6.16 g, potassium carbonate 13.82 g, and metadichlorobenzene 100 ml were heated and stirred at 130 ° C. for 1 hour. Thereafter, the reaction solution was cooled to room temperature, extracted with chloroform, and the organic layer was concentrated under reduced pressure. The residue was recrystallized from methanol to obtain 6.48 g (yield 75.8%) of Exemplary Compound (17) as white crystals. The compound was identified by ¹ H-NMR (400 MHz).
¹ H-NMR (CDCl ₃ ) δ 1.96 (s, 6H), 3.70 (br. S, 12H), 6.57 (d, 4H), 6.94 (d, 2H), 7.05 7.25 (m, 16H), 7.40-7.60 (br.m, 6H)

Preparation of Cellulose Acetate Film Each component of the following cellulose acetate solution composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acetate solution.

(Cellulose acetate solution composition)
Cellulose acetate having an acetylation degree of 60.9% 100 parts by weight Triphenyl phosphate (plasticizer) 7.8 parts by weight Biphenyl diphenyl phosphate (plasticizer) 3.9 parts by weight Methylene chloride (first solvent) 318 parts by weight Methanol (No. 2 solvents) 47 parts by mass

In another mixing tank, exemplary compound (2), (7), (15), (17), (20) or (23), or 16 parts by mass of comparative compound, 87 parts by mass of methylene chloride and 13 parts by mass of methanol were added. The solution was stirred and stirred while heating to prepare a retardation control agent solution. Exemplified compounds (2), (7), (20) and (23) were synthesized according to the synthesis method of the exemplified compounds (15) and (17) described above.
A dope was prepared by mixing 36 parts by mass of a retardation control (raising) agent solution with 474 parts by mass of the cellulose acetate solution and stirring sufficiently. The retardation control agent was added in parts by mass as shown in Table 1 with respect to 100 parts by mass of cellulose acetate.

  The obtained dope was cast using a band casting machine. A cellulose acetate film (thickness: 92 μm) was produced by transversely stretching a film having a residual solvent amount of 15% by mass at a stretching ratio of 20% using a tenter at 130 ° C. About the produced cellulose acetate film (optical compensation sheet), Re and Rth at a wavelength of 590 nm were measured. The results are shown in Table 1.

<Measurement of Re and Rth>
Re was measured by making light having a wavelength of 590 nm incident in the normal direction of the film in KOBRA 21ADH (manufactured by Oji Scientific Instruments). Rth was measured by making light having a wavelength of 590 nm incident from a direction inclined + 40 ° with respect to the film normal direction, with the Re, in-plane slow axis (determined by KOBRA 21ADH) as the tilt axis (rotation axis). The retardation value and the retardation value measured by injecting light having a wavelength of 590 nm from a direction inclined by −40 ° with respect to the film normal direction with the in-plane slow axis as the tilt axis (rotation axis). It was calculated based on the retardation value measured in the direction, the assumed value of the average refractive index, and the input film thickness value.

Comparative compound (compound described in Patent Document 2)

From Table 1, the film containing no comparative compound, the film containing 2 parts by weight of the comparative compound, and the film containing 5 parts by weight of the comparative compound are all
Rth = Re × 3.6 + 43 (Formula 1)
It can be seen that Re and Rth are expressed according to the amount of the compound added. It is estimated that the same formula can be derived even when other known comparative compounds are used.
It is known that a film containing a comparative compound expresses Re by changing the draw ratio, but Rth does not change much. Therefore, a film prepared at a draw ratio smaller than the draw ratio (20%) of this example is obtained by adding a comparative compound,
Rth ≧ Re × 3.6 + 43 (Formula 2)
It can be seen that the film satisfies the optical characteristics of this region.
on the other hand,
Rth <Re × 3.6 + 43 (Formula 3)
In order to obtain a film satisfying the optical characteristics of the above region, it is necessary to increase the stretch ratio to a ratio higher than 20%. However, in general, it is difficult to increase the stretch ratio of cellulose acylate film. Satisfying this area with compounds is not easy.
On the other hand, by adding the compound represented by the general formula (1), it is possible to produce a novel cellulose derivative film having a greater Re developability (region of formula 3) that could not be realized by the film to which the comparative compound was added. I understand.

  As can be seen from the results in Table 1, by adding the compound of the general formula (1), a novel cellulose having optical characteristics in a region having a higher Re developability that could not be realized by a known discotic compound (comparative compound). Derivative films can be produced.

  The cellulose derivative film of the present invention can be suitably used as an optical film for liquid crystal display devices, particularly as an optical compensation sheet.

Claims (5)

A cellulose derivative composition comprising at least one compound represented by the following general formula (1).

(In the formula, Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represents an aryl group or an aromatic heterocycle, and R ⁵ represents a divalent linking group. L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ each independently represents —O— or —NR—, R represents a hydrogen atom, an alkyl group or an aryl group, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ or R ⁵ may be connected to each other to form a ring.) The cellulose derivative composition according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

(In the formula, Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent an aryl group or an aromatic heterocycle. L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ are each independently —O— or —NR—, wherein R represents a hydrogen atom, an alkyl group, or an aryl group, and is bonded to Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , or R ⁵ to form a ring. L ⁷ represents a single bond or a divalent linking group, R ¹¹ and R ¹² each independently represents a substituent, and m and n each independently represents an integer of 1 to 4.)   Cellulose acylate is contained as said cellulose derivative, The cellulose derivative composition of Claim 1 or 2 characterized by the above-mentioned.   The cellulose derivative film which consists of a cellulose derivative composition of any one of Claims 1-3. A compound represented by the following general formula (2).

(In the formula, Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent an aryl group or an aromatic heterocycle. L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ are each independently —O— or —NR—, wherein R represents a hydrogen atom, an alkyl group, or an aryl group, and is bonded to Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , or R ⁵ to form a ring. L ⁷ represents a single bond or a divalent linking group, R ¹¹ and R ¹² each independently represents a substituent, and m and n each independently represents an integer of 1 to 4.)