JP2005179638A - Oriented film, cellulose composition, cellulose film, and benzoic acid phenyl ester compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cellulose composition, with which an oriented film having good optical characteristics and a film having good optical performance can be formed. <P>SOLUTION: The oriented film contains at least 1 type of compound represented by following general formula (1). The cellulose composition contains cellulose and at least 1 type of compound represented by following general formula (2). In general formula (1), R<SP>0</SP>to R<SP>10</SP>each independently denotes a hydrogen atom or a substituent and at least one of R<SP>1</SP>to R<SP>5</SP>denotes an electron-releasing group. In general formula (2), R<SP>1</SP>to R<SP>10</SP>are as defined in general formula (1). R<SP>8</SP>denotes a hydrogen atom or a substituent such as 1-4C alkyl group. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a novel benzoic acid phenyl ester compound, and a cellulose composition and a film containing them.

  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.

  As described above, in the technical field of optical materials, when a polymer film requires optical anisotropy (high retardation value), a synthetic polymer film is used and optical isotropy (low retardation value) is used. It is common to use a cellulose acetate film when required.

However, recently, a cellulose acetate film having a high retardation value that can be used for applications requiring optical anisotropy has been required, and a technique corresponding to the cellulose acetate film has been proposed (for example, Patent Document 1). 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 the birefringence. However, in Patent Document 1, birefringence is achieved by simultaneously orienting additives in the stretching process. The rate can be increased and a high retardation value is realized.

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. Therefore, the optical performance required for the optical compensation sheet is even higher than the optical anisotropy (Re retardation value, Rth retardation value) that can be realized by a compound having a 1,3,5-triazine ring. Re and lower Rth have been required.
However, as a result of intensive studies by the inventor using the method disclosed in Patent Document 1, it has been found that this method has a problem that the Re retardation value and the Rth retardation value cannot be arbitrarily combined. . Therefore, development of new optical performance control technology has become necessary.
On the other hand, benzoic acid phenyl ester is well known as a liquid crystal compound (for example, Non-Patent Document 1), but benzoic acid phenyl ester compound having an alkoxy group at both positions 2 and 4 of benzoic acid and its properties are known. It was not done.

European Patent Application 0911656A2 "Liquid Crystal Handbook" Liquid Crystal Handbook Editorial Committee, page 272 Maruzen Co., Ltd.

A first object of the present invention is to provide a cellulose composition that can form a film excellent in optical performance.
The second object of the present invention is to provide a novel benzoic acid phenyl ester compound excellent in stability.
The third object of the present invention is to provide a stretched film having excellent optical properties.

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

(In the formula, R ⁰ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represents a hydrogen atom or a substituent, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ each represents an electron donating group.)
[2] A stretched film comprising a cellulose body and at least one compound represented by the following general formula (2).
General formula (2)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ each represents an electron donating group, R ⁸ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkynyl group having 2 to 6 carbon atoms. Group, aryl group having 6 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, aryloxy group having 6 to 12 carbon atoms, alkoxycarbonyl group having 2 to 12 carbon atoms, acylamino group having 2 to 12 carbon atoms, carbonyl Represents a group, a cyano group or a halogen atom.)
[3] A cellulose composition comprising at least one compound represented by the general formula (2) and a cellulose body.
[4] The cellulose composition according to [3], wherein the electron donating group of the general formula (2) is an alkoxy group.
[5] The cellulose composition according to [3], wherein the compound represented by the general formula (2) is a compound represented by the following general formula (2-D).
General formula (2-D)

(Wherein R ² , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ represent a hydrogen atom or a substituent, R ¹¹ represents an alkyl group having 1 to 12 carbon atoms. R ¹² represents a hydrogen atom or Represents an alkyl group having 1 to 4 carbon atoms, R ¹⁴ represents an alkyl group having 1 to 4 carbon atoms, R ⁸ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, carbon C2-C12 alkynyl group, C6-C12 aryl group, C1-C12 alkoxy group, C6-C12 aryloxy group, C2-C12 alkoxycarbonyl group, C2-C2 12 represents an acylamino group, a carbonyl group, a cyano group or a halogen atom.)
[6] A cellulose body film formed from the cellulose body composition according to any one of [3] to [5].
[7] The cellulose body film according to [6], wherein the cellulose body is cellulose acylate.
[8] A stretched cellulose body film formed from the cellulose body composition according to any one of [3] to [5].
[9] The stretched cellulose body film according to [8], wherein the cellulose body is cellulose acylate.
[10] A compound represented by the above general formula (2-D).
[11] A compound represented by the following general formula (2-E).
Formula (2-E)

Wherein R ⁸ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, 12 alkoxy group, an aryloxy group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, acylamino group having 2 to 12 carbon atoms, a carbonyl group, a cyano group or a halogen atom ^{.R 11} the number of carbon atoms R 1 represents an alkyl group having 1 to ^12. R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms R ¹⁴ represents an alkyl group having 1 to 4 carbon atoms R ²⁰ represents a hydrogen atom or a substituent. .)
[12] A compound represented by the following general formula (3).
General formula (3)

(Wherein R ² , R ⁴ and R ⁵ represent a hydrogen atom or a substituent. R ¹¹ represents an alkyl group having 1 to 12 carbon atoms. R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X represents an alkynyl group having 2 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, an acylamino group having 2 to 7 carbon atoms, or a cyano group.

The cellulose composition of the present invention is useful for forming a film excellent in optical performance that satisfies both the Re retardation value and the Rth retardation value specified individually. Therefore, the cellulose acylate film obtained from this is excellent in optical performance.
In addition, the benzoic acid phenyl ester compound of the present invention is excellent in stability and handleability, and therefore can be used as a component of a film having excellent optical performance.

[Benzoic acid phenyl ester compound]
First, the compound represented by the general formula (1) used in the present invention will be described in detail.

(In the formula, R ⁰ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represents a hydrogen atom or a substituent, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ each represents an electron donating group.)

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

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

R ² is preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group or a hydroxyl group, more preferably a hydrogen atom, an alkyl group or an alkoxy group, still more preferably a hydrogen atom or an alkyl group (preferably a carbon number). 1 to 4, more preferably a methyl group), an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to carbon atoms). 4). Particularly preferred are a hydrogen atom, a methyl group and a methoxy group, and most preferred is a hydrogen atom.

R ³ is preferably a hydrogen atom or an electron donating group, more preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, or a hydroxyl group, still more preferably an alkyl group or an alkoxy group, particularly preferably. An alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms). Most preferred are n-propoxy group, ethoxy group and methoxy group.

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

R ⁵ is preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group or a hydroxyl group, more preferably a hydrogen atom, an alkyl group or an alkoxy group, still more preferably a hydrogen atom or an alkyl group (preferably having a carbon number). 1 to 4 is more preferably a methyl group), an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms). It is. Particularly preferred are a hydrogen atom, a methyl group, and a methoxy group. Most preferably, it is a hydrogen atom.

R ⁶ , R ⁷ , R ⁹ and R ¹⁰ are preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms and a halogen atom, more preferably a hydrogen atom and a halogen atom. More preferably a hydrogen atom.

R ⁰ represents a hydrogen atom or a substituent, and R ⁰ is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or 1 to carbon atoms. 12 alkoxy groups, aryloxy groups having 6 to 12 carbon atoms, alkoxycarbonyl groups having 2 to 12 carbon atoms, acylamino groups having 2 to 12 carbon atoms, cyano groups, carbonyl groups, or halogen atoms.
Of the general formula (1), the following general formula (2) is more preferable.

Next, the compound represented by the general formula (2) of the present invention will be described in detail.
General formula (2)

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

In general formula (2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent, and general formula (1 And the preferred range is also the same.

R ⁸ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryloxy having 6 to 12 carbon atoms. Group, an alkoxycarbonyl group having 2 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, a cyano group, a carbonyl group, or a halogen atom, and if possible, may have a substituent. Substituent T described below can be applied. Further, the substituent may be further substituted.
R ⁸ is preferably an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkoxycarbonyl group having 2 to 12 carbon atoms. , An acylamino group having 2 to 12 carbon atoms and a cyano group, more preferably an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, and 2 carbon atoms. An acylamino group having 12 to 12 carbon atoms, and more preferably an alkynyl group having 2 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, and an acylamino having 2 to 7 carbon atoms. Group, cyano group, particularly preferably phenylethynyl group, phenyl group, p-cyanophenyl group, p-methoxyphenyl group, benzoylamino group, n-propoxy group. A sicarbonyl group, an ethoxycarbonyl group, a methoxycarbonyl group, and a cyano group.

Of the general formula (2), the following general formula (2-A) is more preferable.
Formula (2-A)

(In the formula, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represents a hydrogen atom or a substituent. R ⁸ is a hydrogen atom, 4 alkyl group, C2-C12 alkynyl group, C6-C12 aryl group, C1-C12 alkoxy group, C6-C12 aryloxy group, C2-C12 alkoxycarbonyl A group, an acylamino group having 2 to 12 carbon atoms, a cyano group, a carbonyl group, or a halogen atom, and R ¹¹ represents an alkyl group having 1 to 12 carbon atoms.)
In general formula (2-A), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have the same meanings as those in general formula (2), and The preferable range is also the same.

In General Formula (2-A), R ¹¹ represents an alkyl group having 1 to 12 carbon atoms, and the alkyl group represented by R ¹¹ may be linear or branched, and further has a substituent. However, it is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms (for example, , Methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group and the like.

Of the general formula (2), the following general formula (2-B) is more preferable.
General formula (2-B)

(In the formula, R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represents a hydrogen atom or a substituent. R ⁸ is a hydrogen atom or an alkyl having 1 to 4 carbon atoms. Group, alkynyl group having 2 to 12 carbon atoms, aryl group having 6 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, aryloxy group having 6 to 12 carbon atoms, alkoxycarbonyl group having 2 to 12 carbon atoms, carbon R 2 represents an alkylamino group having 2 to 12 carbon atoms, a cyano group, a carbonyl group or a halogen atom, R ¹¹ represents an alkyl group having 1 to 12 carbon atoms, and R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. )

In general formula (2-B), R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ have the same meanings as in general formula (2-A), The preferred range is also the same.
In General Formula (2-B), R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or methyl. Group, an ethyl group, more preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.

Of the general formula (2-B), the following general formula (3) or (2-C) is preferable.
General formula (3)

(Wherein R ² , R ⁴ , R ⁵ , R ¹¹ and R ¹² have the same meanings as those in formula (2-B), and preferred ranges are also the same. X is alkynyl having 2 to 7 carbon atoms. Group, an aryl group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, an acylamino group having 2 to 7 carbon atoms, and a cyano group.)

  In general formula (3), X represents an alkynyl group having 2 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, an acylamino group having 2 to 7 carbon atoms, and a cyano group. Preferably a phenylenityl group, a phenyl group, a p-cyanophenyl group, a p-methoxyphenyl group, a benzoylamino group, an alkoxycarbonyl group having 2 to 4 carbon atoms, and a cyano group, more preferably a phenyl group, A p-cyanophenyl group, a p-methoxyphenyl group, an alkoxycarbonyl group having 2 to 4 carbon atoms, and a cyano group.

Hereinafter, the general formula (2-C) will be described.
Formula (2-C)

(In the formula, R ² , R ⁴ and R ⁵ have the same meanings as those in the general formula (2-B), and the preferred range is also the same, but one of them is a group represented by —OR ^13. (R ¹³ is an alkyl group having 1 to 4 carbon atoms.) R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ _, R ¹¹ and R ¹² have the same meanings as those in formula (2-B). And the preferred range is also the same.)

In general formula (2-C), R ² , R ⁴ and R ⁵ have the same meanings as those in general formula (2-B), and preferred ranges are also the same, but one of them is represented by —OR ^13. (R ¹³ is an alkyl group having 1 to 4 carbon atoms), preferably R ⁴ and R ⁵ are groups represented by —OR ¹³ , more preferably R ⁴ is —OR ¹³ . It is a group represented.
R ¹³ represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably an ethyl group or a methyl group, and still more preferably a methyl group.

Of the general formula (2-C), the general formula (2-D) is more preferable.
General formula (2-D)

(Wherein R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ _, R ¹¹ and R ¹² have the same meanings as those in formula (2-C), and preferred ranges are also the same) R ¹⁴ represents an alkyl group having 1 to 4 carbon atoms.)
R ¹⁴ represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably an ethyl group or a methyl group, and still more preferably a methyl group.

Of the general formula (2-D), the following general formula (2-E) is preferable.
Formula (2-E)

_{^{(Wherein, R 8, R 11, R}} 12 and ^{R 14} have the same meanings as those in formula (2-D), and their preferable examples are also the same ^{.R 20} represents a hydrogen atom or a substituent.)
R ²⁰ represents a hydrogen atom or a substituent, and the substituent T described later can be applied as the substituent. R ²⁰ may be substituted at any position of the directly connected benzene ring, but a plurality of R ²⁰ are not present. R ²⁰ is preferably a substituent having 4 or less constituent atoms obtained by removing hydrogen from the total number of hydrogen atoms or substituents, more preferably hydrogen is removed from the total number of hydrogen atoms or substituents A substituent having 3 or less constituent atoms, more preferably a hydrogen atom or a substituent having 2 or less constituent atoms obtained by removing hydrogen from all the atoms of the substituent, particularly preferably a hydrogen atom, methyl Group, methoxy group, halogen atom, formyl group, and cyano group, particularly preferably a hydrogen atom.

The aforementioned substituent T will be described below.
Examples of the substituent T include an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms such as methyl, ethyl, iso-propyl, tert-butyl, and n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably carbon number). 2 to 8, for example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), an alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably carbon number). 2-8, for example, propargyl, 3-pentynyl, etc.), aryl groups (preferably having 6-30 carbon atoms) More preferably, it has 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, naphthyl and the like, and a substituted or unsubstituted amino group (preferably having 0 to 0 carbon atoms). 20, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino, etc.), an alkoxy group (preferably having a carbon number) 1 to 20, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as methoxy, ethoxy, butoxy, etc.), an aryloxy group (preferably 6 to 20 carbon atoms, more Preferably it has 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyloxy, 2-naphthyloxy and the like. Is.),

An acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include acetyl, benzoyl, formyl, pivaloyl and the like), an alkoxycarbonyl group ( Preferably it has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonyl, ethoxycarbonyl and the like, and an aryloxycarbonyl group (preferably having a carbon number). 7 to 20, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms, such as phenyloxycarbonyl, etc.), acyloxy group (preferably 2 to 20 carbon atoms, more preferably carbon 2 to 16, particularly preferably 2 to 10 carbon atoms. For example, acetoxy, benzoyloxy An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino). An alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino), aryloxycarbonylamino group (Preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, and particularly preferably having 7 to 12 carbon atoms, such as phenyloxycarbonylamino), a sulfonylamino group (preferably having 1 carbon atom) -20, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, Methanesulfonylamino, and the like benzenesulfonylamino is.),

Sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, and particularly preferably 0 to 12 carbon atoms. Examples thereof include sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, and phenylsulfamoyl. ), A carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc. An alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio and ethylthio), an arylthio group (preferably). Has 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, Preferably it has 6 to 12 carbon atoms, such as phenylthio, etc.), a sulfonyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, For example, mesyl, tosyl, etc.), sulfinyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc. Ureido group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include ureido, methylureido, and phenylureido). A phosphoramide group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 carbon atom) 12 such as diethyl phosphate amide, phenyl phosphate 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. Atoms, sulfur atoms, specifically imidazolyl, pyridyl, quinolyl, furyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, etc.), silyl groups (preferably having 3 to 40 carbon atoms, More preferably, it has 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms. For example, trimethylsilyl, triphenylsilyl, etc.). These substituents may be further substituted.

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

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

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

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

The reaction temperature is preferably 0 to 150 ° C, more preferably 0 to 100 ° C, still more preferably 0 to 90 ° C, and particularly preferably 20 ° C to 90 ° C.
In this reaction, it is preferable not to use a base. When a base is used, either an organic base or an inorganic base may be used, preferably an organic base such as pyridine, tertiary alkylamine (preferably triethylamine, ethyldiisopropyl). Pyramine and the like).

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

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

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

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

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

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

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

[Synthesis Example 4: Synthesis of Exemplary Compound A-4]
After heating 25.0 g (118 mmol) of 2,4,6-trimethoxybenzoic acid, 100 mL of toluene and 1 mL of dimethylformamide to 60 ° C., 15.4 g (129 mmol) of thionyl chloride was slowly added dropwise, Stir for hours. Thereafter, a solution prepared by previously dissolving 15.4 g (129 mmol) of 4-cyanophenol in 50 mL of acetonitrile was slowly added dropwise. After completion of the addition, the mixture was heated and stirred at 80 to 85 ° C. for 4.5 hours. After cooling the reaction solution to room temperature, liquid separation operation was performed with ethyl acetate and water. After removing water from the obtained organic phase with sodium sulfate, the solvent was distilled off under reduced pressure, and 500 mL of methanol and 100 mL of acetonitrile were added, Recrystallization operation was performed. The precipitated crystals were collected by filtration to obtain 10.0 g (yield 27%) of the target compound as white crystals. The compound was identified by mass spectrum.
Mass spectrum: m / z 314 (M + H) ⁺ ,
The melting point of the obtained compound was 172 to 173 ° C.

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

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

[Synthesis Example 6: Synthesis of Exemplified Compound A-6]
The synthesis was performed in the same manner except that 2,3-dimethoxybenzoic acid in Synthesis Example 5 was changed to 2,4-dimethoxybenzoic acid. The compound was identified by mass spectrum.
Mass spectrum: m / z 284 (M + H) ⁺ ,
The melting point of the obtained compound was 134 to 136 ° C.

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

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

[Synthesis Example 8: Synthesis of Exemplary Compound A-8]
The synthesis was performed in the same manner except that 2,3-dimethoxybenzoic acid in Synthesis Example 5 was changed to 2,6-dimethoxybenzoic acid. The compound was identified by mass spectrum.
Mass spectrum: m / z 284 (M + H) ⁺ ,
The melting point of the obtained compound was 130 to 131 ° C.

[Synthesis Example 9: Synthesis of Exemplary Compound A-11]
The target compound was obtained in the same manner except that 71.5 g of 4-cyanophenol in Synthesis Example 2 was changed to 76.9 g of 4-chlorophenol. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

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

[Synthesis Example 10: Synthesis of Exemplified Compound A-12]
After heating 45.0 g (212 mmol) of 2,4,5-trimethoxybenzoic acid, 180 mL of toluene and 1.8 mL of dimethylformamide to 60 ° C., 27.8 g (233 mmol) of thionyl chloride was slowly added dropwise to the mixture at 60 ° C. And stirred for 2.5 hours. Thereafter, a solution prepared by dissolving 35.4 g (233 mmol) of methyl 4-hydroxybenzoate in 27 mL of dimethylformamide was slowly added, and the mixture was heated and stirred at 80 ° C. for 3 hours. 270 mL was added, and the precipitated crystals were collected by filtration to obtain 64.5 g (yield 88%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

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

[Synthesis Example 11: Synthesis of Exemplary Compound A-13]
After heating 20.0 g (94.3 mmol) of 2,4,5-trimethoxybenzoic acid, 100 mL of toluene and 1 mL of dimethylformamide to 60 ° C., 12.3 g (104 mmol) of thionyl chloride was slowly added dropwise to the mixture at 60 ° C. And stirred for 3.5 hours. Thereafter, a solution in which 17.7 g (104 mmol) of 4-phenylphenol was dissolved in 150 mL of toluene was slowly added, and the mixture was heated and stirred at 80 ° C. for 3 hours. The reaction solution was then cooled to room temperature, and 250 mL of methanol was added. The precipitated crystals were collected by filtration to obtain 21.2 g (yield 62%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

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

[Synthesis Example 12: Synthesis of Exemplified Compound A-14]
After heating 12.9 g (61 mmol) of 2,4,5-trimethoxybenzoic acid, 50 mL of toluene, and 0.6 mL of dimethylformamide to 60 ° C., 8.0 g (67 mmol) of thionyl chloride was slowly added dropwise to the mixture at 60 ° C. And stirred for 3.5 hours. Thereafter, a solution prepared by previously dissolving 17.7 g (104 mmol) of 4-phenoxyphenol in 25 mL of acetonitrile was slowly added, and the mixture was heated and stirred at 80 ° C. for 3 hours. The reaction solution was then cooled to room temperature, and 100 mL of methanol was added. The precipitated crystals were collected by filtration to obtain 21.6 g (yield 93%) of the target compound as white crystals. The compound was identified by mass spectrum.
Mass spectrum: m / z 381 (M + H) ⁺ ,
The melting point of the obtained compound was 91-92 ° C.

[Synthesis Example 13: Synthesis of Exemplary Compound A-15]
The target compound was obtained in the same manner except that 71.5 g of 4-cyanophenol in Synthesis Example 2 was changed to 56.4 g of phenol. The compound was identified by ¹ H-NMR and mass spectrum.

¹ H-NMR (CDCl ₃ ) δ 3.91 (s, 3H), 3.93 (s, 3H), 3.99 (s, 3H), 6.58 (s, 1H), 7.19-7. 27 (m, 3H), 7.42 (m, 2H), 7.58 (s, 1H),
Mass spectrum: m / z 289 (M + H) ⁺ ,
The melting point of the obtained compound was 105 to 108 ° C.

[Synthesis Example 14: Synthesis of Exemplified Compound A-16]
The target compound can be obtained in the same manner except that 71.5 g of 4-cyanophenol in Synthesis Example 2 is changed to 74.4 g of 4-methoxyphenol. The compound was identified by ¹ H-NMR and mass spectrum.

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

[Synthesis Example 15: Synthesis of Exemplified Compound A-17]
The target compound was obtained in the same manner except that 71.5 g of 4-cyanophenol in Synthesis Example 2 was changed to 73.3 g of 4-ethylphenol. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.
Mass spectrum: m / z 317 (M + H) ⁺ ,
The melting point of the obtained compound was 70 to 71 ° C.

[Synthesis Example 16: Synthesis of Exemplary Compound A-24]
After heating 27.3 g (164 mmol) of 4-ethoxybenzoic acid, 108 mL of toluene, and 1 mL of dimethylformamide to 60 ° C., 21.5 g (181 mmol) of thionyl chloride was slowly added dropwise and stirred at 60 ° C. for 2 hours. . Thereafter, a solution in which 25.0 g (181 mmol) of 4-ethoxyphenol was previously dissolved in 50 mL of acetonitrile was slowly added, and the mixture was heated and stirred at 80 ° C. for 4 hours. After cooling the reaction solution to room temperature, 100 mL of methanol was added. The precipitated crystals were collected by filtration to obtain 30.6 g (yield 65%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

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

[Synthesis Example 17: Synthesis of Exemplified Compound A-25]
After heating 24.7 g (149 mmol) of 4-ethoxybenzoic acid, 100 mL of toluene and 1 mL of dimethylformamide to 60 ° C., 19.5 g (164 mmol) of thionyl chloride was slowly added dropwise, and the mixture was heated and stirred at 60 ° C. for 2 hours. . Thereafter, a solution prepared by dissolving 25.0 g (165 mmol) of 4-propoxyphenol in 50 mL of acetonitrile was slowly added, and the mixture was heated and stirred at 80 ° C. for 4 hours. After cooling the reaction solution to room temperature, 100 mL of methanol was added. The precipitated crystals were collected by filtration, 100 mL of methanol was added to the obtained solid, and recrystallization was performed. The obtained crystals were collected by filtration to obtain 33.9 g (yield 76%) of the target compound as white crystals. It was. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

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

[Synthesis Example 18: Synthesis of Exemplified Compound A-27]
The compound was synthesized in the same manner except that 27.3 g of 4-ethoxybenzoic acid in Synthesis Example 16 (synthesis of A-24) was changed to 29.5 g of 4-propoxybenzoic acid. The compound was identified by mass spectrum.
Mass spectrum: m / z 301 (M + H) ⁺ ,
The melting point of the obtained compound was 88-89 ° C.

[Synthesis Example 19: Synthesis of Exemplary Compound A-28]
The compound was synthesized in the same manner except that 24.7 g of 4-ethoxybenzoic acid in Synthesis Example 17 (synthesis of A-25) was changed to 26.8 g of 4-propoxybenzoic acid. The compound was identified by mass spectrum.
Mass spectrum: m / z 315 (M + H) ⁺ ,
The melting point of the obtained compound was 92 ° C.

[Synthesis Example 20: Synthesis of Exemplified Compound A-40]
After heating 20.0 g (109 mmol) of 2,4-dimethoxybenzoic acid, 80 mL of toluene and 0.8 mL of dimethylformamide to 60 ° C., 14.4 g (121 mmol) of thionyl chloride was slowly added dropwise, The mixture was heated and stirred for 5 hours. Thereafter, a solution prepared by previously dissolving 20.5 g (121 mmol) of 4-phenylphenol in 50 mL of dimethylformamide was slowly added and stirred at 80 ° C. for 6 hours. After cooling the reaction solution to room temperature, 100 mL of methanol was added. In addition, the precipitated crystals were collected by filtration to obtain 31.7 g (yield 86%) of the target compound as white crystals. The compound was identified by mass spectrum.
Mass spectrum: m / z 335 (M + H) ⁺ ,
The melting point of the obtained compound was 161-162 ° C.

[Synthesis Example 21: Synthesis of Exemplified Compound A-42]
After heating 30.0 g (165 mmol) of 2,4-dimethoxybenzoic acid, 120 mL of toluene and 1.2 mL of dimethylformamide to 60 ° C., 21.6 g (181 mmol) of thionyl chloride was slowly added dropwise. Stir for hours. Thereafter, a solution prepared by dissolving 27.6 g (181 mmol) of methyl 4-hydroxybenzoate in 40 mL of dimethylformamide was slowly added, and the mixture was heated and stirred at 80 ° C. for 6 hours. 140 mL was added, and the precipitated crystals were collected by filtration to obtain 24.4 g (yield 47%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.
¹ H-NMR (CDCl ₃ ) δ 3.92 (m, 9H), 6.56 (m, 2H), 7.27 (m, 2H), 8.09 (m, 3H),
Mass spectrum: m / z 317 (M + H) ⁺ ,
The melting point of the obtained compound was 122-123 ° C.

[Synthesis Example 22: Synthesis of Exemplified Compound A-51]
2,4,5-Trimethoxybenzoic acid 20.7 g (50 mmol) of 4-iodophenyl, 5.61 g (55 mmol) of ethynylbenzene, 27.8 mL (200 mmol) of triethylamine, and 40 mL of tetrahydrofuran were stirred at room temperature under a nitrogen atmosphere. Then, 114 mg (0.6 mmol) of cuprous chloride, 655 mg (2.5 mmol) of triphenylphosphine, and 351 mg (0.5 mmol) of bis (triphenylphosphine) palladium dichloride were added and heated at 60 ° C. for 6 hours. Stir. Thereafter, the reaction solution was cooled to room temperature, and 400 mL of water was added. The obtained crystals were filtered and recrystallized from 160 mL of methanol to obtain 17.2 g (yield 89%) of the target compound as yellowish white crystals.
The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.
¹ H-NMR (CDCl ₃ ) δ 3.92 (s, 3H), 3.95 (s, 3H) 4.00 (s, 3H) 6.58 (s, 1H), 7.22 (m, 2H) , 7.32 (m, 3H), 7.53-7.62 (m, 5H),
Mass spectrum: m / z 389 (M + H) ⁺ ,
The melting point of the obtained compound was 129 to 130 ° C.

[Synthesis Example 23: Synthesis of Exemplified Compound A-52]
2,4,5-trimethoxybenzoic acid 42.4 g (0.2 mol), 4-hydroxybenzaldehyde 26.8 g (0.22 mol), toluene 170 mL, N, N-dimethylformamide 1.7 mL at 80 ° C. After heating, 26.0 g (0.22 mol) of thionyl chloride was slowly added dropwise and heated at 80 ° C. for 6 hours. After cooling the reaction solution to room temperature, liquid separation operation was performed with ethyl acetate, water, and saturated saline, and after removing water with sodium sulfate, the solvent was distilled off under reduced pressure. To the product, 240 mL of isopropyl alcohol was added, and recrystallization was performed. The solution was cooled to room temperature, and the precipitated crystals were collected by filtration to obtain 40.8 g (yield 65%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.
¹ H-NMR (CDCl ₃ ) δ 3.92 (s, 3H), 3.95 (s, 3H) 4.00 (s, 3H), 6.58 (s, 1H), 7.34 (d, 2H ), 7.59 (s, 1H), 8.17 (d, 2H),
Mass spectrum: m / z 317 (M + H) ⁺ ,
The melting point of the obtained compound was 103 to 105 ° C.

[Synthesis Example 24: Synthesis of Exemplary Compound A-53]
After dropwise addition of 40 g (126 mmol) of 2,4,5-trimethoxybenzoic acid and 3.93 g (25.2 mmol) of sodium dihydrogen phosphate dissolved in 400 mL of acetonitrile in 5 mL of water, After 18.3 g of 35% hydrogen peroxide solution was added dropwise over 20 minutes, a solution prepared by dissolving 14.1 g (126 mmol) of 80% sodium chlorite in Wako Pure Chemical Industries, Ltd. in 43 mL of water was added dropwise over 20 minutes. For 4.5 hours at room temperature. Thereafter, 100 mL of water was added and cooled to 10 ° C. The obtained crystals were filtered off and recrystallized with 500 mL of methanol to obtain 25.4 g (yield 60%) of the target compound as white crystals.
¹ H-NMR (CDCl ₃ ) δ 3.92 (s, 3H), 3.95 (s, 3H) 4.00 (s, 3H), 6.59 (s, 1H), 7.40 (d, 2H ), 7.57 (s, 1H), 7.96 (d, 2H), 10.0 (s, 1H),
Mass spectrum: m / z 333 (M + H) ⁺ ,
The melting point of the obtained compound was 188 to 189 ° C.

[Synthesis Example 25: Synthesis of Exemplified Compound A-54]
5.00 g (23.5 mmol) of 2,4,5-trimethoxybenzoic acid, 5.52 g (23.5 mmol) of benzoic acid (4-hydroxy) anilide, 50 mL of acetonitrile, and 1.0 mL of N, N-dimethylformamide After heating to 70 ° C., 3.4 g (28.5 mmol) of thionyl chloride was slowly added dropwise and heated at 70 ° C. for 3 hours. After cooling the reaction solution to room temperature, 50 mL of methanol was added, and the precipitated crystals were collected by filtration to obtain 8.1 g (yield 84%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.
¹ H-NMR (CDCl ₃ ) δ 3.92 (s, 3H), 3.95 (s, 3H) 4.00 (s, 3H), 6.60 (s, 1H), 7.12-8.10 (M, 10H),
Mass spectrum: m / z 408 (M + H) ⁺ ,
The melting point of the obtained compound was 189 to 190 ° C.

[Synthesis Example 26: Synthesis of Exemplary Compound A-56]
2-hydroxy-4,5-dimethoxybenzoic acid 8.50 g (42.8 mmol), 4-cyanophenol 5.62 g (42.8 mmol) 45 mL toluene, 0.5 mL N, N-dimethylformamide at 70 ° C. After heating, 5.6 g (47.1 mmol) of thionyl chloride was slowly added dropwise and heated at 80 ° C. for 3 hours. After cooling the reaction solution to room temperature, 50 mL of methanol was added, and the precipitated crystals were collected by filtration to obtain 5.8 g (yield 45%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz).
¹ H-NMR (CDCl ₃ ) δ 3.92 (s, 3H), 3.97 (s, 3H), 6.67 (s, 1H), 7.38 (m, 3H), 7.77 (d, 2H), 10.28 (s, 1H),
The melting point of the obtained compound was 145 to 146 ° C.

[Synthesis Example 27: Synthesis of Exemplary Compound A-57]
2-hydroxy-4,5-dimethoxybenzoic acid 8.50 g (42.8 mmol), methyl 4-hydroxybenzoate 7.17 g (42.8 mmol) toluene 45 mL, N, N-dimethylformamide 0.5 mL 70 After heating to ° C., 6.1 g (51.2 mmol) of thionyl chloride was slowly added dropwise and heated at 80 ° C. for 3 hours. After cooling the reaction solution to room temperature, 50 mL of methanol was added, and the precipitated crystals were collected by filtration to obtain 6.9 g (yield 49%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz).
¹ H-NMR (CDCl ₃ ) δ 3.92 (s, 3H), 3.97 (s, 6H), 6.55 (s, 1H), 7.31 (d, 2H), 7.41 (s, 1H), 8.16 (d, 2H), 10.41 (s, 1H),
The melting point of the obtained compound was 128 ° C.

[Synthesis Example 28: Synthesis of Exemplified Compound A-58]
The synthesis was performed in the same manner as in Synthesis Example 2 by using vanillic acid instead of cyanophenol.
The melting point of the obtained compound was 201 to 203 ° C.

[Synthesis Example 29: Synthesis of Exemplified Compound A-62]
Synthesis was performed in the same manner as in Synthesis Example 10 except that 4-ethoxy-2-methoxybenzoic acid was used instead of 2,4,5-trimethoxybenzoic acid.
The melting point of the obtained compound was 88-89 ° C.
[Synthesis Example 30: Synthesis of Exemplified Compound A-63]
Synthesis was performed in the same manner as in Synthesis Example 10 except that 4-hydroxy-2-methoxybenzoic acid was used instead of 2,4,5-trimethoxybenzoic acid.
The melting point of the obtained compound was 108 to 113 ° C.
[Synthesis Example 31: Synthesis of Exemplified Compound A-65]
The compound was synthesized in the same manner as in Synthesis Example 2 by using 4-hydroxy-2-methoxybenzoic acid instead of 2,4-dimethoxybenzoic acid.
The melting point of the obtained compound was 142-144 ° C.

  Any one of the compounds represented by the general formulas (1), (2), (2-A) to (2-E) and (3) of the present invention is 0.1 to 20 mass based on cellulose. %, Preferably 0.5 to 16% by mass, more preferably 1 to 12% by mass, and particularly preferably 2 to 8% by mass. Most preferably, it is 3-7 mass%.

[Stretched film]
As long as the stretched film of the present invention is a film in which the film surface of the film is stretched by 5% or more immediately after film formation, any film material can be used, but preferably a polymer having a molecular weight of 5000 or more. For example, it is selected from polyester, polycarbonate, cycloolefin polymer, cellulose and the like, more preferably cellulose, further cellulose ester is preferable, and cellulose acylate is particularly preferable. The draw ratio is preferably 5 to 500%, more preferably 5 to 300%, still more preferably 5 to 100%, and particularly preferably 10 to 40%.

[Cellulose composition]
The cellulose composition of the present invention is a cellulose compound, or a compound having a cellulose skeleton obtained by biologically or chemically introducing a functional group using cellulose as a raw material (these are referred to as cellulose bodies) and the general formula (1), (2) A composition containing at least one selected from the compounds represented by (2-A) to (2-E) and (3). The compound having a cellulose skeleton is preferably a cellulose ester, and more preferably cellulose acylate (including cellulose triacylate and cellulose acylate propionate). In the present invention, two or more different cellulose acylates may be mixed and used.
Hereinafter, the present invention will be described using a case where cellulose acylate is used as the cellulose compound as a representative example.

Among the cellulose compounds, 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 present invention, the total substitution degree of SA and SB of the hydroxyl group 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 also preferable that the substituent is a 6-position hydroxyl group. Furthermore, a cellulose acylate film in which the total substitution degree of SA and SB at the 6-position of cellulose acylate is 0.8 or more, further 0.85 or more, particularly 0.90 or more can be mentioned. it can.

  In the present invention, the acyl group having 3 to 22 carbon atoms representing the above-mentioned SB of cellulose acylate may be 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. These preferred substituents representing SB include propionyl, butanoyl, heptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, iso-butanoyl, pivaloyl, cyclohexanecarbonyl, oleyl, Examples include benzoyl, naphthylcarbonyl, cinnamoyl groups and the like. Among these, propionyl, butanoyl, dodecanoyl, octadecanoyl, pivaloyl, oleoyl, benzoyl, naphthylcarbonyl, cinnamoyl and the like.

  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 cellulose acylate film of the present invention is preferably composed of cellulose acylate in which the polymer component constituting the film substantially has the above definition. “Substantially” means 55% by mass or more (preferably 70% by mass or more, more preferably 80% by mass or more) of the polymer component. The balance is a plasticizer, an ultraviolet absorber and the like. When preparing a cellulose composition 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 diameter of 0.5 to 5 mm. Moreover, it is preferable that 50 mass% or more of the particle | grains to be used have a particle diameter of 1-4 mm. The cellulose acylate particles preferably have a shape as close to a sphere as possible.

  The degree of polymerization of the cellulose acylate preferably used in the present invention is a viscosity average degree of polymerization 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) is increased, but the viscosity is lower than that of ordinary 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. 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 reduce the moisture content of cellulose acylate in the present invention, drying is necessary, and the method is not particularly limited as long as the desired moisture content (for example, 2% by mass or less) can be achieved.

  These cellulose acylates of the present invention are described in detail on pages 7 to 12 of the raw material cotton and the synthesis method 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.

  In the cellulose acylate film of the present invention, various additives (for example, plasticizers, ultraviolet inhibitors, deterioration inhibitors, optical anisotropy control agents, fine particles, release agents, infrared rays) according to the use in each preparation step. Absorbents, etc.) can be added and they can be solid or oily. That is, the melting point and boiling point are not particularly limited. For example, mixing of ultraviolet absorbing materials at 20 ° C. or lower and 20 ° C. or higher, and similarly mixing of a plasticizer is described in, for example, Japanese Patent Application Laid-Open No. 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 a cellulose acylate film is formed from a multilayer, the kind and addition amount of the additive of each layer may differ. For example, they are described in JP-A No. 2001-151902, and these are conventionally known techniques.

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

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

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

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

  The non-chlorine organic solvent used in the above cellulose acylate is selected from the various viewpoints described above, and is preferably as follows. That is, a preferred solvent for the cellulose acylate of the present invention 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. And at least one kind or a mixture thereof, the second solvent is selected from ketones having 4 to 7 carbon atoms or acetoacetate, and the third solvent is alcohol or hydrocarbon having 1 to 10 carbon atoms 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 is preferably linear, branched or cyclic, and is preferably a saturated aliphatic hydrocarbon. The hydroxyl group of the alcohol may be any of primary to tertiary. Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 2-methyl-2-butanol and cyclohexanol. As the alcohol, fluorine-based alcohol is also used. Examples thereof include 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol and the like.

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

  The 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 of the present invention can include the following, but are not limited thereto.

-Methyl acetate / acetone / methanol / ethanol / butanol (75/10/5/5/5, parts by mass),
-Methyl acetate / acetone / methanol / ethanol / propanol (75/10/5/5/5, parts by mass),
Methyl acetate / acetone / methanol / butanol / cyclohexane (75/10/5/5/5, parts by mass),
・ Methyl acetate / acetone / ethanol / butanol (81/8/7/4, parts by mass)
・ Methyl acetate / acetone / ethanol / butanol (82/10/4/4, parts by mass)
・ Methyl acetate / acetone / ethanol / butanol (80/10/4/6, 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 (55/20/10/5/5/5, parts by mass)
Etc.

Furthermore, a cellulose acylate solution can also be used by the following method.
In addition to the non-chlorine organic solvent of the present technology, the dope used in the present technology may contain dichloromethane in an amount of 10% by mass or less based on the total amount of the organic solvent.

  In preparing the cellulose acylate solution (composition liquid) of the present invention, a chlorine-based organic solvent is sometimes used as a main solvent in some cases, and is described below. In the present invention, the chlorinated organic solvent is not particularly limited as long as the object can be achieved within a range in which cellulose acylate can be dissolved and cast and formed. These chlorinated organic solvents are preferably dichloromethane and chloroform. Particularly preferred is dichloromethane.

  In addition, there is no particular problem in mixing an organic solvent other than the chlorinated organic solvent. In that case, it is necessary to use at least 50% by mass of dichloromethane. The non-chlorine organic solvent used in combination with the present invention is described below. That is, as a preferable non-chlorine organic solvent, a solvent selected from esters, ketones, ethers, alcohols, hydrocarbons and the like having 3 to 12 carbon atoms is preferable. Esters, ketones, ethers and alcohols may have a cyclic structure. A compound having two or more functional groups of esters, ketones and ethers (that is, —O—, —CO— and —COO—) can also be used as a solvent. For example, other functional groups such as alcoholic hydroxyl groups can be used. You may have group simultaneously. In the case of a solvent having two or more types of functional groups, the number of carbon atoms may be within the specified range of the compound having any functional group. Examples of esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate.

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

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

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

  The non-chlorine organic solvent used in combination with the chlorine-based organic solvent that is the main solvent used for the cellulose acylate is not particularly limited, but methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, dioxolane , Dioxane, ketones having 4 to 7 carbon atoms or acetoacetate, alcohols having 1 to 10 carbon atoms or hydrocarbons. Preferred non-chlorine organic solvents used in combination are methyl acetate, acetone, methyl formate, ethyl formate, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl acetyl acetate, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol. , 2-butanol, and cyclohexanol, cyclohexane, and hexane. Although the following can be mentioned as a combination of the chlorinated organic solvent which is a preferable main solvent of this invention, It is not limited to these.

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, 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.

  The cellulose acylate of the present invention is preferably dissolved in an organic solvent at a concentration of 10 to 30% by mass, more preferably a concentration of 13 to 27% by mass, and particularly a concentration of 15 to 25% by mass. A cellulose acylate solution is preferred. The method for carrying out the cellulose acylate at these concentrations may be carried out so as to obtain a predetermined concentration at the stage of dissolution, or it is prepared as a low-concentration solution (for example, 9 to 14% by mass) and then concentrated as described later. You may adjust to a predetermined high concentration solution by a process. In addition, a cellulose acylate solution having a high concentration may be added to the cellulose acylate solution at a predetermined low concentration by adding various additives, and the cellulose acylate solution concentration of the present invention may be obtained by any method. There is no particular problem if it is implemented.

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

  These 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 of 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 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 (registered trademark) 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. In addition, the refractive index required for this analysis uses the value of the solvent calculated | required with the Abbe refractive system, and the refractive index gradient (dn / dc) uses the differential refractometer (Otsuka Electronics Co., Ltd. product DRM-1021). The measurement was performed using the solvent and the solution used for the light scattering measurement.

  Next, with respect to the preparation of the cellulose acylate solution (dope) of the present invention, the dissolution method is not particularly limited, and may be room temperature, further a cooling dissolution method or a high temperature dissolution method, or a combination thereof. Regarding these, for example, JP-A-5-163301, JP-A-61-106628, JP-A-58-127737, JP-A-9-95544, JP-A-10-95854, JP-A-10-45950, JP-A-2000-53784, Kaihei 11-322946, JP-A-11-322947, JP-A-2-276830, JP-A-2000-273239, JP-A-11-71463, JP-A-04-259511, JP-A-2000-273184, JP-A-11-323017, JP-A-11-323017 A method for preparing a cellulose acylate solution is described in each publication such as 11-302388. The above-described method for dissolving cellulose acylate in an organic solvent is applicable to the present invention as long as it is within the scope of the present invention.

  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. Be implemented in a way that Further, the cellulose acylate dope solution of the present invention is usually subjected to solution concentration and filtration. Similarly, the dope solution of the invention is published in the technical report of the Invention Association (public technical number 2001-1745, published on March 15, 2001, Invention Association). It is described in detail on the page. 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 acylate solution of the present invention preferably has a viscosity and dynamic storage modulus within the range. 1 mL of the sample solution was measured with a rheometer (CLS 500) using Steel Cone (both manufactured by TA Instruments) having a diameter of 4 cm / 2 °. Measurement conditions were measured by varying at 2 ° C. / min range of 40 ℃ ~-10 ℃ in Oscillation Step / Temperature Ramp, static non-Newtonian viscosity of ^{40 ℃ n * (Pa · s} ) and storage of -5 ° C. The elastic modulus G ′ (Pa) was determined. The measurement was started after the sample solution was kept warm at the measurement start temperature until the liquid temperature became constant. 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, more preferably the viscosity at 40 ° C. is 10 to 200 Pa · s, The dynamic storage elastic modulus at 15 ° C. is preferably 1 to 1,000,000. Furthermore, it is preferable that the dynamic storage elastic modulus at a low temperature is large. 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.

[Film / Cellulose Film]
Next, the compound of general formula (2) or (2-A) to (2-E) of the present invention will be described with respect to a film containing at least one kind. The material of the film may be anything as long as it is a compound capable of producing a film, but is preferably a polymer having a molecular weight of 5000 or more, such as polyester, polycarbonate, cycloolefin polymer, cellulose, etc., more preferably cellulose. Furthermore, cellulose ester is preferable, and cellulose acylate is particularly preferable.

  Next, the production method will be described taking as an example a film using a cellulose acylate solution as the film / cellulose film of the present invention.

  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 cellulose triacetate film production are used. The dope (cellulose acylate solution) prepared from the dissolving machine (kettle) is temporarily stored in a storage kettle, and the foam contained in the dope is defoamed for final preparation. The dope is sent from the dope discharge port to the pressure die through a pressure metering gear pump capable of delivering a constant amount of liquid with high accuracy, for example, by the number of rotations, and the dope is run endlessly from the die (slit) of the pressure die. The dry-dried dope film (also referred to as web) is peeled off from the metal support at a peeling point that is uniformly cast on the metal support and substantially rounds the metal support.

  Both ends of the obtained web are sandwiched between clips, transported by a tenter while keeping the width, dried, then transported by a roll group of a drying device, dried, and wound up to a predetermined length by a winder. The combination of the tenter and the roll group dryer varies depending on the purpose. In the solution casting film forming method used for 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, etc.

  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 cellulose acylate solution cast at a low space 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 acylate, 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 a cellulose acylate solution is -50-130 degreeC, Preferably it is -30-25 degreeC, Furthermore, it is -20-15 degreeC. In order to keep the casting part at the temperature of the present invention, 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 cellulose acylate solution is a cellulose acylate solution containing 0.1 to 20% by mass of at least one liquid or solid plasticizer with respect to cellulose acylate at 25 ° C. and / or at least It is a cellulose acylate solution containing 0.001 to 5% by mass of one kind of liquid or solid UV absorber with respect to cellulose acylate, and / or an average particle size of 5 to 5 of at least one kind of solid. It is a cellulose acylate solution containing 0.001 to 5% by mass of fine particle powder of 3000 nm with respect to cellulose acylate, and / or at least one fluorosurfactant with respect to cellulose acylate A cellulose acylate solution containing 0.001 to 2% by mass and / or a small amount Both are cellulose acylate solutions containing 0.0001 to 2% by mass of one type of release agent with respect to cellulose acylate, and / or at least one type of deterioration inhibitor is 0.0001 with respect to cellulose acylate. A cellulose acylate solution containing ˜2 mass%, and / or containing 0.1-15 mass% of at least one optical anisotropy control agent with respect to cellulose acylate, and / or Or a cellulose acylate solution containing 0.1 to 5% by mass of at least one infrared absorber with respect to the cellulose acylate, and a cellulose acylate produced therefrom. A film is preferred.

  In the casting step, one type of cellulose acylate solution may be cast as a single layer, or two or more types of cellulose acylate solutions may be cast simultaneously and / or sequentially. In the case of having a casting process consisting of two or more layers, the composition of the chlorinated solvent in each layer is either the same or different in the cellulose acylate solution and the cellulose acylate film to be produced. The additive is one kind or a mixture of two or more kinds, the addition position of the additive to each layer is either the same layer or a different layer, The concentration in the solution is either the same or different in each layer, the aggregate molecular weight of each layer is either the same or a different aggregate molecular weight, Either the temperature is the same or a different temperature, the coating amount of each layer is the same or different, and the viscosity of each layer is the same Either one of the different viscosities, the film thickness after drying of each layer is the same or different, and the material present in each layer is the same or distribution or different or A cellulose acylate that is characterized by the distribution, the physical properties of each layer being the same or different, and the physical properties of each layer being either uniform or different. A cellulose acylate film prepared from the rate solution and the solution 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).

The cellulose acylate film can achieve an 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. 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 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 was directly applied onto the cellulose acylate film to obtain adhesive force, and some surface treatment was performed once. There is a method in which an undercoat layer (adhesive layer) is provided or a functional layer is applied thereon after or without surface treatment. Details of these subbing layers are described on page 32 of the Japan Society for Invention and Innovation (Public Technical Number 2001-1745, published on March 15, 2001, Japan Institute of Invention). Various functional layers of the cellulose acylate film of the present invention are also disclosed on pages 32 to 45 in the Japan Institute of Technology (Technical Number 2001-1745, published on March 15, 2001, Japan Society of Inventions). Are described in detail.

The optical performance of the cellulosic film of the present invention will be described. Using an ellipsometer (AEP-100, manufactured by Shimadzu Corporation), the value obtained by multiplying the longitudinal and lateral refractive index difference measured at a wavelength of 632.8 nm by the film thickness is obtained according to the following formula.
Re = (nx−ny) × d
Rth = {(nx + ny) / 2−nz} × d
nx: refractive index in the slow axis direction (direction in which the refractive index is maximum) ny: refractive index in the direction perpendicular to the slow axis nz: refractive index in the thickness direction d: film thickness (unit: nm)

The use of the cellulose acylate produced in the present invention will be briefly described first. The optical film of the present invention is particularly useful as a polarizing plate protective film, an optical compensation sheet for a liquid crystal display device, an optical compensation sheet for a reflective liquid crystal display device, and a support for a silver halide photographic light-sensitive material.
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 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 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 and 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 optical film of the present invention is applied can provide an excellent display property regardless of the position. . 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 acylate 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 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 Crystals), AFLC (Anti-Ferroelectric Liquid Crystals), OCB (Optically Charged TNS). 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 acylate film is effective in the liquid crystal display device in any display mode. Further, it is effective in any of a transmissive, reflective, and transflective 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. 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 ) 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. 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 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.

  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 for the reflection type liquid crystal display device is described in WO00-65384. 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 (Axial Symmetrical 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 a paper by Kume et al. (Kume et al., SID 98 Digest 1089 (1998)). The use of these detailed cellulose acylate films described above is described in detail on pages 45-59 in the Japan Society for Invention and Technology (Publication No. 2001-1745, published on March 15, 2001, Japan Society for Invention). Has been.

EXAMPLES Next, although this invention is demonstrated further in detail based on an Example, this invention is not limited at all by the following Example.
[Example 1]
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. 1) 2 solvents) 47 parts by mass

In another mixing tank, 16 parts by mass of the compound of the present invention or comparative compound, 87 parts by mass of methylene chloride and 13 parts by mass of methanol were added and stirred while heating to prepare a retardation control agent solution.
A dope was prepared by mixing 36 parts by mass of the retardation control (raising) agent solution with 474 parts by mass of the cellulose acetate solution and stirring sufficiently. The addition amount of the retardation adjusting agent was 5.0 parts by mass (4.8% by mass) with respect to 100 parts by mass of cellulose acetate.

  The obtained dope was cast using a band casting machine. A film having a residual solvent amount of 15% by mass was laterally stretched at a stretch ratio of 26% using a tenter under the conditions of 130 ° C. to produce a cellulose acetate film (thickness: 80 μm). About the produced cellulose acetate film (optical compensation sheet), the Re retardation value and the Rth retardation value at a wavelength of 633 nm were measured using an ellipsometer (M-150, manufactured by JASCO Corporation). The results are shown in Table 1.

<Measurement of Rth and Re>
Using an ellipsometer (AEP-100, manufactured by Shimadzu Corporation), the value obtained by multiplying the longitudinal and lateral refractive index difference measured at a wavelength of 632.8 nm by the film thickness was determined according to the following formula.
Re = (nx−ny) × d
Rth = {(nx + ny) / 2−nz} × d
nx: refractive index in the slow axis direction (direction in which the refractive index is maximum) ny: refractive index in the direction perpendicular to the slow axis nz: refractive index in the thickness direction d: film thickness (unit: nm)

In Table 1, in additive 1), No. 6 and No. 12 adjust the amount of the retardation adjuster solution. 7 and No11 and samples with different addition amounts were prepared.
In addition, each symbol in optical performance evaluation 2) indicates that ◯ indicates that the optical performance is good (Re / Rth 0.30 to 0.35), and Δ indicates that an optical performance improvement effect is observed (Re / Rth0). .25 to 0.29), x indicates insufficient optical performance (Re / Rth 0.20 to 0.24).

Comparative compound 1

  As can be seen from the results in Table 1, the addition of the compound of the present invention makes it possible to produce a novel cellulose film having a large Re / Rth ratio that could not be realized with a known discotic compound (Comparative Compound 1). became. In addition, the combined use of the compound of the present invention, the compound and the comparative compound 1 makes it possible to produce a cellulose film having an arbitrary Re / Rth ratio.

[Example 2]
The stability of the compounds of the present invention was evaluated. In the stability test, a 5 mmol / L methanol solution of the compound of the present invention was prepared, the methanol solution was tightly sealed and allowed to stand at 50 ° C. for 3 days, and then the residual ratio of the compound of the present invention was quantified by HPLC (detection wavelength 254 nm). did. The results are shown in Table 2.

In Table 2, the symbols “Δ”, “◯”, and “◎” in the column of stability evaluation have the following meanings.
Remaining rate 80% or less △ Care must be taken when preparing solutions Remaining rate 80% to 90% ○ No problem Remaining rate 90% to 100% ◎ No problem at all

As shown in Table 2, it can be seen that the compounds represented by the general formulas (2-D) and (3) of the present invention are particularly excellent in stability in methanol as compared with the known compound A-1.

Claims (12)

A stretched film comprising at least one compound represented by the following general formula (1).
General formula (1)

(In the formula, R ⁰ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represents a hydrogen atom or a substituent, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ each represents an electron donating group.) A stretched film comprising a cellulose body and at least one compound represented by the following general formula (2).
General formula (2)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ each represents an electron donating group, R ⁸ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkynyl group having 2 to 6 carbon atoms. Group, aryl group having 6 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, aryloxy group having 6 to 12 carbon atoms, alkoxycarbonyl group having 2 to 12 carbon atoms, acylamino group having 2 to 12 carbon atoms, carbonyl Represents a group, a cyano group or a halogen atom.) A cellulose body composition comprising a cellulose body and at least one compound represented by the following general formula (2).
General formula (2)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ each represents an electron donating group, R ⁸ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkynyl group having 2 to 6 carbon atoms. Group, aryl group having 6 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, aryloxy group having 6 to 12 carbon atoms, alkoxycarbonyl group having 2 to 12 carbon atoms, acylamino group having 2 to 12 carbon atoms, carbonyl Represents a group, a cyano group or a halogen atom.)   4. The cellulose composition according to claim 3, wherein the electron donating group of the general formula (2) is an alkoxy group. The cellulose body composition according to claim 3, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (2-D).
General formula (2-D)

(Wherein R ² , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ represent a hydrogen atom or a substituent, R ¹¹ represents an alkyl group having 1 to 12 carbon atoms. R ¹² represents a hydrogen atom or Represents an alkyl group having 1 to 4 carbon atoms, R ¹⁴ represents an alkyl group having 1 to 4 carbon atoms, R ⁸ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, carbon C2-C12 alkynyl group, C6-C12 aryl group, C1-C12 alkoxy group, C6-C12 aryloxy group, C2-C12 alkoxycarbonyl group, C2-C2 12 represents an acylamino group, a carbonyl group, a cyano group or a halogen atom.)   A cellulose body film formed from the cellulose body composition according to any one of claims 3 to 5.   The cellulose body film according to claim 6, wherein the cellulose body is cellulose acylate.   A stretched cellulose body film formed from the cellulose body composition according to any one of claims 3 to 5.   The stretched cellulose body film according to claim 8, wherein the cellulose body is cellulose acylate. The compound represented by the following general formula (2-D).
General formula (2-D)

(Wherein R ² , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ represent a hydrogen atom or a substituent, R ¹¹ represents an alkyl group having 1 to 12 carbon atoms. R ⁸ represents a hydrogen atom, C1-C4 alkyl group, C2-C6 alkenyl group, C2-C6 alkynyl group, C6-C12 aryl group, C1-C12 alkoxy group, C6-C12 An aryloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, a carbonyl group, a cyano group, or a halogen atom, and R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ¹⁴ represents an alkyl group having 1 to 4 carbon atoms.) The compound represented by the following general formula (2-E).
Formula (2-E)

Wherein R ⁸ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or 1 to R ¹² represents an alkoxy group having 12 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, a carbonyl group, a cyano group, or a halogen atom. R 1 represents an alkyl group having 1 to ^12. R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹⁴ represents an alkyl group having 1 to 4 carbon atoms, R ²⁰ represents a hydrogen atom or a substituent. .) A compound represented by the following general formula (3).
General formula (3)

(Wherein R ² , R ⁴ and R ⁵ represent a hydrogen atom or a substituent. R ¹¹ represents an alkyl group having 1 to 12 carbon atoms. R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X represents an alkynyl group having 2 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, an acylamino group having 2 to 7 carbon atoms, or a cyano group.