KR101133474B1 - Oriented film, cellulose composition, cellulose film, and benzoic acid phenylester compound - Google Patents

Abstract

Provided is a cellulose-like composition capable of forming a stretched film having excellent optical properties and a film having excellent optical performance.

The stretched film containing at least 1 sort (s) of the compound represented by following General formula (1), and a cellulose body and the cellulose body composition containing at least 1 sort (s) of the compound represented by following General formula (2).

General formula (1)

(Wherein, R ⁰ to R ¹⁰ each independently represent a hydrogen atom or a substituent, and at least one of R ¹ to R ⁵ represents an electron donating group)

General formula (2)

(Wherein, R ¹ ~ R ¹⁰ is the same meaning as R ¹ ~ R ¹⁰ in the formula (1). R ⁸ represents a substituent such as hydrogen atom or an alkyl group having from 1 to 4 carbon atoms)

Stretched Film, Cellulose

Description

Stretched Film, Cellulose Composition, Cellulose Film and Benzoic Acid Phenol Ester Compound {ORIENTED FILM, CELLULOSE COMPOSITION, CELLULOSE FILM, AND BENZOIC ACID PHENYLESTER COMPOUND}

The present invention relates to a novel benzoic acid phenyl ester compound, a cellulose-like composition and a film containing the same.

Among the cellulose films, the 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 the use which requires optical isotropy, for example, a polarizing plate. On the other hand, optical anisotropy (high retardation value) is required for optical compensation sheets (retardation films) such as liquid crystal display devices. Therefore, as the optical compensation sheet, it was common to use a synthetic polymer film having a high retardation value such as a polycarbonate film or a polysulfone film.

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

In recent years, however, a cellulose acetate film having a high retardation value that can be used for applications requiring optical anisotropy is required, and a technology corresponding thereto has been proposed (for example, European Patent Application Publication No. 0911656A2). In the above-mentioned invention, in order to realize a high retardation value with cellulose triacetate, an aromatic compound having at least two aromatic rings, and especially a compound having a 1,3,5-triazine ring, is added and stretched.

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 the European Patent Application Publication No. 0911656A2, it is possible to increase the birefringence by simultaneously aligning the additives by stretching treatment. The retardation value is realized.

In recent years, in order to reduce the weight of the liquid crystal display device and reduce the manufacturing cost, thinning of the liquid crystal cell has become essential. Therefore, the optical performance required for the optical compensation sheet is higher than Re and lower with respect to the optical anisotropy (Re retardation value, Rth retardation value) that can be realized by the compound having 1,3,5-triazine ring. Rth has been required.

However, as a result of earnestly examining the present invention by the method disclosed in the specification of European Patent Application Publication No. 0911656A2, it has been found that there is a problem that the above-described method cannot arbitrarily combine the above-described Re retardation value and Rth retardation value. Therefore, the development of a new optical performance control technology is needed.

On the other hand, benzoic acid phenyl ester is well known as a liquid crystalline compound (for example, `` Liquid Crystal Handbook '' Liquid Crystal Handbook Editing Committee Editing Page 272 Maruzen Co., Ltd.). Its properties are not known.

It is a first object of the present invention to provide a cellulosic composition capable of forming a film having excellent optical performance.

A second object of the present invention is to provide a novel benzoic acid phenyl ester compound having excellent stability.

A third object of the present invention is to provide a stretched film having excellent optical characteristics.

The object of the present invention is achieved by the following means.

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

General formula (1)

[Formula 1]

(Wherein R ⁰ , 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 At least one of R ³ , R ⁴ and R ⁵ 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)

[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 , At least one of R ⁴ and R ⁵ represents an electron-donating group R ⁸ represents a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, an alkynyl group of 2 to 6 carbon atoms, or an aryl group of 6 to 12 carbon atoms , Alkoxyl 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 group, cyano group or halogen atom)

[3] A cellulosic composition comprising at least one compound represented by the cellulose body and the general formula (2).

[4] The cellulosic composition according to [3], wherein the electron donating group of the general formula (2) is an alkoxy group.

[5] The cellulose-based 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)

(In formula, R <^2> , R <^5> , R <^6> , R <^7> , R <^9> and R <^10> represent a hydrogen atom or a substituent, R <^11> represents a C1-C12 alkyl group. R <^12> is a hydrogen atom or C1-C12 An alkyl group of 4. R ¹⁴ represents an alkyl group having 1 to 4 carbon atoms, R ⁸ represents a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, an alkynyl group of 2 to 6 carbon atoms, and 6 to 6 carbon atoms 12 aryl group, a C1-C12 alkoxy group, a C6-C12 aryloxy group, a C2-C12 alkoxycarbonyl group, a C2-C12 acylamino group, a carbonyl group, a cyano group, or a halogen atom)

[6] A cellulose-like film formed from the cellulose-based 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 cellulose-based stretched film formed from the cellulose-based composition according to any one of [3] to [5].

[9] The cellulose-based stretched film according to [8], wherein the cellulose body is cellulose acylate.

[10] A compound represented by the general formula (2-D).

[11] A compound represented by the following General Formula (2-E).

General formula (2-E)

Wherein R ⁸ represents a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, an alkynyl group of 2 to 6 carbon atoms, an aryl group of 6 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, or carbon number 6-12 aryloxy group, a represents an alkoxycarbonyl group, an acylamino group, a carbonyl group, a cyano group or a halogen atom, having 2 to 12 carbon atoms of 2 to 12. R ¹¹ represents an alkyl group having a carbon number of 1 ~ ^12. R 12 is hydrogen An 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)

In the formula, 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 carbon number Alkynyl group having 2 to 7, aryl group having 6 to 12 carbon atoms, alkoxycarbonyl group having 2 to 6 carbon atoms, acylamino group having 2 to 7 carbon atoms, and cyano group)

Best Mode for Carrying Out the Invention

[Benzoic acid phenyl ester compound]

First, the compound represented by General formula (1) used for this invention is demonstrated in detail.                     

(Wherein R ⁰ , 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 , At least one of R ³ , R ⁴ and R ⁵ 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> respectively independently represent a hydrogen atom or a substituent, The substituent T mentioned later can be applied.

At least one of R ¹ , R ² , R ³ , R ^4, and R ⁵ represents an electron donating group. Preferably, one of R ¹ , R ^3, or R ⁵ is an electron donating group, and R ³ is an electron donating group. Do.

The electron donating group indicates that the σ _p value of Hammet is 0 or less, and Chem. Rev., 91, 165 (1991). It is possible to apply preferably that σ _p value of Hammet of the substrate is 0 or less, more preferably -0.85 to 0. For example, an alkyl group, an alkoxy group, an amino group, a hydroxyl group, etc. are mentioned.

As an electron-donating group, Preferably it is an alkyl group and an alkoxy group, More preferably, an alkoxy group (preferably C1-C12, More preferably, it is C1-C8, More preferably, it is C1-C6, Especially preferably, Carbon number 1-4).

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, still more preferably an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a hydroxyl group, Especially preferably, it is an alkoxy group (preferably C1-C12, More preferably, it is C1-C8, More preferably, it is C1-C6, Especially preferably, it is C1-C4), Most preferably, a methoxy group to be.

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 having 1 to 4 carbon atoms, Preferably it is a methyl group, and an alkoxy group (preferably C1-C12, More preferably, it is C1-C8, More preferably, it is C1-C6, Especially preferably, it is C1-C4). Especially preferably, they are a hydrogen atom, a methyl group, and a methoxy group, Most preferably, they are 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 Is C1-C12, More preferably, it is C1-C8, More preferably, it is C1-C6, Especially preferably, it is C1-C4). Most preferably, they are n-propoxy group, an ethoxy group, and a 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, more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a C 1 to 12 carbon group. Alkoxy group (preferably C1-C12, More preferably, it is C1-C8, More preferably, it is C1-C6, Especially preferably, it is C1-C4), Especially preferably, it is a hydrogen atom and C1-C4 It is an alkyl group of 4 and a C1-C4 alkoxy group, Most preferably, they are a hydrogen atom, a methyl group, and 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 1 to 4 carbon atoms) Preferably it is a methyl group, and an alkoxy group (preferably C1-C12, More preferably, it is C1-C8, More preferably, it is C1-C6, Especially preferably, it is C1-C4). Especially preferably, they 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, a halogen atom, more preferably a hydrogen atom or a halogen atom, and more preferably It is hydrogen atom.

R ⁰ represents a hydrogen atom or a substituent, and preferably R ⁰ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, It is a C6-C12 aryloxy group, a C2-C12 alkoxycarbonyl group, a C2-C12 acylamino group, a cyano group, a carbonyl group, or a halogen atom.

More preferably in General formula (1), it is following General formula (2).

Next, the compound represented by General formula (2) of this invention is demonstrated 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 represent a hydrogen atom or a substituent, and R ¹ , R ² , R ³ , R At least one of ⁴ and R ⁵ represents an electron-donating group, R ⁸ represents a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, an alkynyl group of 2 to 6 carbon atoms, an aryl group of 6 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, Aryloxy group having 6 to 12 carbon atoms, alkoxycarbonyl group having 2 to 12 carbon atoms, acylamino group having 2 to 12 carbon atoms, cyano group, carbonyl group or 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> respectively independently represent a hydrogen atom or a substituent, and General formula (1) The same meaning as in, and the preferred range is also the same.

R ⁸ is a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, an alkynyl group of 2 to 12 carbon atoms, an aryl group of 6 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, an aryloxy group of 6 to 12 carbon atoms, or 2 to 12 carbon atoms An alkoxycarbonyl group, 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, and the substituent T described below may be applied as the substituent. In addition, a substituent may substitute again.

R ⁸ is preferably an alkyl group of 1 to 4 carbon atoms, an alkynyl group of 2 to 12 carbon atoms, an aryl group of 6 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, an alkoxycarbonyl group of 2 to 12 carbon atoms, or a 2 to 12 carbon atoms. It is an acylamino group and a cyano group, More preferably, they are a C2-C12 alkynyl group, a C6-C12 aryl group, a C2-C12 alkoxycarbonyl group, a C2-C12 acylamino group, a cyano group, More preferably, Is 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, and particularly preferably a phenylethynyl group, a phenyl group, and p- Cyanophenyl group, p-methoxyphenyl group, benzoylamino group, n-propoxycarbonyl group, ethoxycarbonyl group, methoxycarbonyl group and cyano group.

More preferably in General formula (2), it is following General formula (2-A).

General formula (2-A)                     

(In formula, R <^1> , R <^2> , R <^4> , R <^5> , R <^6> , R <^7> , R <^9> and R <^10> represent a hydrogen atom or a substituent each independently. R <^8> is a hydrogen atom and C1-C4. Alkyl group, C2-C12 alkynyl group, C6-C12 aryl group, C1-C12 alkoxy group, C6-C12 aryloxy group, C2-C2 alkoxycarbonyl group, C2-C12 acylamino group , A cyano group, a carbonyl group or a halogen atom, R ¹¹ represents an alkyl group having 1 to 12 carbon atoms.)

In 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 in formula (2), and Preferred ranges are 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, branched, or may further have a substituent, but preferably Alkyl group of 1 to 12 carbon atoms, more preferably an alkyl group of 1 to 8 carbon atoms, still more preferably an alkyl group of 1 to 6 carbon atoms, particularly preferably an alkyl group of 1 to 4 carbon atoms (e.g., methyl group, ethyl group, n- Propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, etc. are mentioned.

More preferably in General formula (2), it is following General formula (2-B).

General formula (2-B)

(In formula, R <^2> , R <^4> , R <^5> , R <^6> , R <^7> , R <^9> and R <^10> represent a hydrogen atom or a substituent each independently. R <^8> is a hydrogen atom, a C1-C4 alkyl group, carbon number C2-C12 alkynyl group, C6-C12 aryl group, C1-C12 alkoxy group, C6-C12 aryloxy group, C2-C12 alkoxycarbonyl group, C2-C12 acylamino group, cyano group Or a carbonyl group or a halogen atom, 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)

In General Formula (2-B), R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ have the same meanings as in General Formula (2-A), and Preferred ranges are also the same.

In general formula (2-B), R <^12> represents a hydrogen atom or a C1-C4 alkyl group, Preferably it is a hydrogen atom or a C1-C3 alkyl group, More preferably, it is a hydrogen atom, a methyl group, and an ethyl group. More preferably, it is a hydrogen atom or a methyl group, Especially preferably, it is a methyl group.

In general formula (2-B), Preferably, it is the following general formula (3) or general formula (2-C).

General formula (3)

(In formula, R <^2> , R <^4> , R <^5> , R <^11> and R <^12> are synonymous with general formula (2-B), and its preferable range is also the same. X is a C2-C7 alkynyl group and carbon number 6-12 aryl group, C2-C6 alkoxycarbonyl group, C2-C7 acylamino group, cyano group)

In general formula (3), X represents a C2-C7 alkynyl group, a C6-C12 aryl group, a C2-C6 alkoxycarbonyl group, a C2-C7 acylamino group, and a cyano group, Preferably it is phenyl Ethynyl group, phenyl group, p-cyanophenyl group, p-methoxyphenyl group, benzoylamino group, alkoxycarbonyl group having 2 to 4 carbon atoms, cyano group, more preferably phenyl group, p-cyanophenyl group, p-methoxyphenyl group , Alkoxycarbonyl group and cyano group having 2 to 4 carbon atoms.

General formula (2-C) is demonstrated below.

General formula (2-C)                     

(In formula, R <^2> , R <^4> , R <^5> is synonymous with general formula (2-B), and although a preferable range is also the same, either is a group represented by -OR <^13> (R <^13> is carbon number 1 R <^6> , R <^7> , R <^8> , R <^9> , R <^10> , R <^11> and R <^12> are synonymous with general formula (2-B), and its preferable range is also the same).

In general formula (2-C), R <^2> , R <^4> and R <^5> are synonymous with general formula (2-B), and the preferable range is also the same, but either is a group represented by -OR <^13> ( R <^13> is a C1-C4 alkyl group), Preferably R <^4> , R <^5> is group represented by -OR <^13> , More preferably, R <^4> is group represented by -OR <^13> .

R <^13> represents a C1-C4 alkyl group, Preferably it is a C1-C3 alkyl group, More preferably, it is an ethyl group and a methyl group, More preferably, it is a methyl group.

In general formula (2-C), More preferably, it is general formula (2-D).

General formula (2-D)                     

(In formula, R <^2> , R <^5> , R <^6> , R <^7> , R <^8> , R <^9> , R <^10> , R <^11> and R <^12> have the same meaning as in general formula (2-C), and its preferable range is also the same. R ¹⁴ represents an alkyl group having 1 to 4 carbon atoms).

R <^14> represents a C1-C4 alkyl group, Preferably it is a C1-C3 alkyl group, More preferably, it is an ethyl group and a methyl group, More preferably, it is a methyl group.

In general formula (2-D), Preferably it is the following general formula (2-E).

General formula (2-E)

(Wherein R ⁸ , R ¹¹ , R ¹² and R ¹⁴ have the same meanings as in General Formula (2-D), and the preferred range is 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 mentioned later can be applied as a substituent. In addition, R ²⁰ is substituted on the benzene ring may be the one where a direct connection, there is no thing which R ²⁰ is a plurality exist. R ²⁰ is preferably a substituent having 4 or less members except hydrogen in all of the atoms of a hydrogen atom or a substituent, more preferably a substituent having 3 or less members except hydrogen in all atoms of a hydrogen atom or substituents, More preferably, it is a substituent having 2 or less members except hydrogen in all atoms of hydrogen atoms or substituents, particularly preferably hydrogen atoms, methyl groups, methoxy groups, halogen atoms, formyl groups, cyano groups, and particularly preferably It is a hydrogen atom.

The substituent T mentioned above is demonstrated below.

As the substituent T, for example, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms), for example, methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), alkenyl group (preferably C2-C20, more preferably C2-C12, especially preferable) Preferably it is C2-C8, and a vinyl, allyl, 2-butenyl, 3-pentenyl, etc. are mentioned, an alkynyl group (preferably C2-C20, More preferably, it is C2-C12) Especially preferably, they are C2-C8, For example, propargyl, 3-pentynyl, etc. are mentioned, An aryl group (preferably C6-C30, More preferably, C6-C20, Especially Preferably it is C6-C12, For example, phenyl, p-methylphenyl, naphthyl, etc. are mentioned), substitution Is an unsubstituted amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, for example, amino, methylamino, dimethylamino, diethylamino, dibenzyl) Amino, etc.), an alkoxy group (preferably C1-C20, More preferably, it is C1-C12, Especially preferably, it is C1-C8, For example, methoxy, ethoxy, butoxy etc. Aryloxy group (preferably C6-C20, More preferably, it is C6-C16, Especially preferably, it is C6-C12, For example, phenyloxy, 2-naphthyloxy, etc. are mentioned. Can be heard),

Acyl group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, acetyl, benzoyl, formyl, pivaloyl, etc. are mentioned), Alkoxycarbonyl group (preferably C2-C20, More preferably, it is C2-C16, Especially preferably, it is C2-C12, For example, methoxycarbonyl, ethoxycarbonyl, etc. are mentioned), Aryl Oxycarbonyl group (preferably C7-20, More preferably, C7-16, Especially preferably, C7-10, For example, phenyloxycarbonyl etc. are mentioned), Acyloxy group (preferably Is C2-C20, More preferably, it is C2-C16, Especially preferably, it is C2-C10, For example, acetoxy, benzoyloxy, etc. are mentioned, Acylamino group (Preferably C2-C20) More preferably 2 to 16 carbon atoms, Preferably it is C2-C10, for example, acetylamino, benzoylamino, etc., an alkoxycarbonylamino group (preferably C2-C20, More preferably, it is C2-C16, Especially preferably, Is C2-C12, For example, a methoxycarbonylamino etc. are mentioned, An aryloxycarbonylamino group (preferably C7-20, More preferably, C7-16, Especially preferably, carbon number 7-12, a phenyloxycarbonylamino etc. are mentioned, for example, a sulfonylamino group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12) Methanesulfonylamino, benzenesulfonylamino, etc.);

Sulfamoyl groups (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, and particularly preferably 0 to 12 carbon atoms, for example, sulfamoyl, methyl sulfamoyl, dimethyl sulfamoyl, phenyl sulfamoyl, etc. Carbamoyl group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, carbamoyl, methylcarbamoyl, diethyl Carbamoyl, phenylcarbamoyl, etc.) and an alkylthio group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, methyl Thio, ethylthio, etc.) and an arylthio group (preferably C6-C20, More preferably, it is C6-C16, Especially preferably, it is C6-C2, For example, phenylthio etc. are mentioned. Sulfonyl group (preferably 1 to 20 carbon atoms) Preferably it is C1-C16, Especially preferably, it is C1-C12, For example, mesyl, tosyl, etc., A sulfinyl group (preferably C1-C20, More preferably, C1-C16) Especially preferably, it is C1-C12, For example, methane sulfinyl, benzene sulfinyl, etc. are mentioned, A ureido group (preferably C1-C20, More preferably, it is C1-C16, Especially preferable Preferably it is C1-C12, for example, ureido, methylureido, phenylureido, etc.), phosphate amide group (preferably C1-C20, More preferably, C1-C16, Especially Preferably it is C1-C12, For example, a diethyl phosphate amide, a phenyl phosphate amide, etc. are mentioned, A hydroxy group, a mercapto group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) ), Cyano group, sulfo group, carboxyl group, Tro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably C1-C30, More preferably, it is 1-12, As a hetero atom, For example, a nitrogen atom, oxygen Atoms, sulfur atoms, and specific examples thereof include imidazolyl, pyridyl, quinolyl, furyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, and the like; Group (preferably C3-C40, More preferably, it is C3-C30, Especially preferably, it is C3-C24, For example, trimethylsilyl, a triphenylsilyl, etc. are mentioned). . These substituents may be substituted again.

In addition, when there are two or more substituents, they may be same or different. In addition, if possible, they may be connected to each other to form a ring.

Although the specific example is given and demonstrated in detail about the compound represented by General formula (1) below, this invention is not limited at all by the following specific examples.                     

The compound represented by General formula (1) of this invention can be synthesize | combined by the general ester reaction of substituted benzoic acid and a phenol derivative, and what kind of reaction may be used if it is ester bond formation reaction. For example, the method of condensation with a phenol after functional group conversion of substituted benzoic acid to an acid halide, the method of dehydrating condensed benzoic acid and a phenol derivative using a condensing agent or a catalyst, etc. are mentioned.

Considering the production process, a method of condensing with phenol after converting the substituted benzoic acid into an acid halide is preferable.

As the reaction solvent, a hydrocarbon solvent (preferably toluene, xylene), an ether solvent (preferably dimethyl ether, tetrahydrofuran, dioxane, etc.), a ketone solvent, an ester solvent , Acetonitrile, dimethylformamide, dimethylacetamide and the like can be used. These solvents may be used alone or in combination of various kinds thereof. Preferably, the reaction solvent is toluene, acetonitrile, dimethylformamide or dimethylacetamide.

As reaction temperature, Preferably it is 0-150 degreeC, More preferably, it is 0-100 degreeC, More preferably, it is 0-90 degreeC, Especially preferably, it is 20 degreeC-90 degreeC.

It is preferable not to use a base for this reaction, and when using a base, any of an organic base and an inorganic base may be sufficient, Preferably it is an organic base, Pyridine, tertiary alkylamine (preferably triethylamine, Ethyl diisopropylamine, etc.);

Although the synthesis method of the compound of this invention is described concretely below, this invention is not limited at all by the following specific examples.

Synthesis Example 1 Synthesis of Exemplary Compound A-1

24.6 g (0.116 mole) of 3,4,5-trimethoxybenzoic acid, 100 mL of toluene and 1 mL of NN-dimethylformamide were heated to 60 ° C, and then 15.2 g (0.127 mole) of thionyl chloride was slowly added dropwise to 60 ° C. Heated at 2 h. Then, the liquid which melt | dissolved 4-5.1 cyano phenol 15.1 g (0.127 mol) in 50 mL of acetonitrile was slowly dripped, and it stirred by heating and stirring at 60 degreeC for 3 hours after completion | finish of dripping. After the reaction solution was cooled to room temperature, liquid separation was carried out with ethyl acetate and water, and the obtained organic phase was removed with sodium sulfate, and then the solvent was distilled off under reduced pressure. Then, 100 mL of acetonitrile was added to the solid obtained to perform recrystallization. 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. In addition, the compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

Melting | fusing point of the obtained compound was 172-173 degreeC.

Synthesis Example 2: Synthesis of Exemplary Compound A-2

106.1 g (0.5 mole) of 2,4,5-trimethoxybenzoic acid, 340 mL of toluene, and 1 mL of dimethylformamide were heated to 60 ° C, and then 65.4 g (0.55 mole) of thionyl chloride was slowly added dropwise to 65 to 70 hours. Heated at ° C. Then, the liquid which melt | dissolved 4-cyano phenol 71.5g (0.6 mol) in 150 mL of acetonitrile was slowly dripped, and after completion | finish of dripping, it heated and stirred at 80-85 degreeC for 2 hours. After cooling the reaction solution to room temperature, liquid separation operation was carried out with ethyl acetate (1 L) and water, and the obtained organic phase was dried with magnesium sulfate to remove water, and about 500 mL of the solvent was distilled off under reduced pressure, and then 1 L of methanol was added for recrystallization. Was carried out. The precipitated crystals were collected by filtration to obtain 125.4 g (yield 80%) of the title compound as white crystals. In addition, the compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

Melting | fusing point of the obtained compound was 116 degreeC.

Synthesis Example 3: Synthesis of Exemplary Compound A-3

10.1 g (47.5 mmol) of 2,3,4-trimethoxybenzoic acid, 40 mL of toluene and 0.5 mL of dimethylformamide were heated to 80 ° C, and then 6.22 g (52.3 mmol) of thionyl chloride was slowly added dropwise to 2 at 80 ° C. It was stirred by heating for a time. Then, the liquid which melt | dissolved 6.2 g (52.3 mmol) of 4-cyano phenols previously in 20 mL of acetonitrile was dripped slowly, and after completion | finish of dripping, it stirred by heating and stirring at 80-85 degreeC for 2 hours. The reaction solution was cooled to room temperature, followed by separating operation with ethyl acetate and water, and then removing the moisture from the obtained organic phase with sodium sulfate. The solvent was distilled off under reduced pressure and 50 mL of methanol was added to carry out recrystallization. The precipitated crystals were collected by filtration to obtain 11.9 g (yield 80%) of the target compound as white crystals. In addition, the compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

Melting | fusing point of the obtained compound was 102-103 degreeC.

Synthesis Example 4: Synthesis of Exemplary Compound A-4

25.0 g (118 mmol) of 2,4,6-trimethoxybenzoic acid, 100 mL of toluene and 1 mL of dimethylformamide were heated to 60 DEG C, and then 15.4 g (129 mmol) of thionyl chloride was slowly added dropwise thereto at 60 DEG C for 2 hours. It was heated and stirred. Then, the liquid which melt | dissolved the 4-cyano phenol 15.4g (129 mmol) previously in 50 mL of acetonitrile was dripped slowly, and after completion | finish of dripping, it stirred by heating and stirring at 80-85 degreeC for 4.5 hours. The reaction solution was cooled to room temperature, followed by separating operation with ethyl acetate and water, and then removing the moisture from the obtained organic phase with sodium sulfate. The solvent was distilled off under reduced pressure, 500 mL of methanol and 100 mL of acetonitrile were added to carry out recrystallization. The precipitated crystals were collected by filtration to obtain 10.0 g (yield 27%) of the title compound as white crystals. In addition, the identification of the compound was performed by the mass spectrum.

Mass spectrum: m / z 314 (M + H) ⁺ ,

Melting | fusing point of the obtained compound was 172-173 degreeC.

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 at 60 ° C, 10.7 g (90.5 mmol) of thionyl chloride was slowly added dropwise and heated at 60 ° C for 2 hours. Stirred. Then, the liquid which melt | dissolved 4-0.8 cyano phenol 10.8g (90.5 mmol) in 30 mL of acetonitrile was dripped slowly, and after completion | finish of dripping, it stirred by heating and stirring at 70-80 degreeC 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. In addition, the identification of the compound was performed by the mass spectrum.

Mass spectrum: m / z 284 (M + H) ⁺

Melting | fusing point of the obtained compound was 104 degreeC.

Synthesis Example 6 Synthesis of Exemplary Compound A-6

It synthesize | combined by the same method except changing 2, 3- dimethoxy benzoic acid in the synthesis example 5 into 2, 4- dimethoxy benzoic acid. In addition, the identification of the compound was performed by the mass spectrum.

Mass spectrum: m / z 284 (M + H) ⁺ ,

Melting | fusing point of the obtained compound was 134-136 degreeC.

Synthesis Example 7: Synthesis of Exemplary Compound A-7

25.0 g (137 mmol) of 2,5-dimethoxybenzoic acid, 100 mL of toluene and 1.0 mL of dimethylformamide were heated to 60 ° C, and then 18.Og (151 mmol) of thionyl chloride was slowly added dropwise thereto at 60 ° C for 2 hours. It was heated and stirred. Then, the liquid which melt | dissolved 4-8.0 cyano phenol 18.0g (151 mmol) previously in 50 mL of acetonitrile was dripped slowly, and it stirred by heating and stirring at 70-80 degreeC for 7.5 hours after completion | finish of dripping. After the reaction solution was cooled to room temperature, liquid separation was performed with ethyl acetate and saturated brine, and the obtained organic phase was removed with sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain silica gel column chromatography (hexane-ethyl acetate (9/1). , V / V)) to obtain 18.8 g (yield 48%) of the title compound as white crystals. In addition, the identification of the compound was performed by the mass spectrum.

Mass spectrum: m / z 284 (M + H) ⁺ ,

Melting | fusing point of the obtained compound was 79-80 degreeC.

Synthesis Example 8: Synthesis of Exemplary Compound A-8

It synthesize | combined by the same method except changing 2, 3- dimethoxy benzoic acid in the synthesis example 5 into 2, 6- dimethoxy benzoic acid. In addition, the identification of the compound was performed by the mass spectrum.

Mass spectrum: m / z 284 (M + H) ⁺ ,

Melting | fusing point of the obtained compound was 130-131 degreeC.

Synthesis Example 9: Synthesis of Exemplary Compound A-11

The target compound was obtained in the same manner except changing 71.5 g of 4-cyanophenol in Synthesis Example 2 to 76.9 g of 4-chlorophenol. In addition, the compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

Melting | fusing point of the obtained compound was 127-129 degreeC.

Synthesis Example 10 Synthesis of Exemplary Compound A-12                     

45.0 g (212 mmol) of 2,4,5-trimethoxybenzoic acid, 180 mL of toluene and 1.8 mL of dimethylformamide were heated to 60 ° C, and then 27.8 g (233 mmol) of thionyl chloride was slowly added dropwise to 2.5 at 60 ° C. Stirring was carried out for time. Thereafter, a solution obtained by dissolving methyl 4-hydroxybenzoate 35.4 g (233 mmol) in 27 mL of dimethylformamide was slowly added thereto, and the mixture was heated and stirred at 80 ° C. for 3 hours. The reaction solution was cooled to room temperature, and methanol 270 mL was added. The crystals added and precipitated were collected by filtration to obtain 64.5 g (yield 88%) of the title compound as white crystals. In addition, the compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

Melting | fusing point of the obtained compound was 121-123 degreeC.

Synthesis Example 11: Synthesis of Exemplary Compound A-13

20.0 g (94.3 mmol) of 2,4,5-trimethoxybenzoic acid, 100 mL of toluene and 1 mL of dimethylformamide were heated to 60 ° C, and then 12.3 g (104 mmol) of thionyl chloride was slowly added dropwise to 3.5 hours at 60 ° C. It was heated and stirred. Thereafter, a solution obtained by previously dissolving 17.7 g (104 mmol) of 4-phenylphenol in 150 mL of toluene was slowly added and stirred by heating at 80 ° C. for 3 hours. The reaction solution was cooled to room temperature, and 250 mL of methanol was added to precipitate crystals. The product was recovered by filtration to give 21.2 g (yield 62%) of the title compound as white crystals. In addition, the compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

Melting | fusing point of the obtained compound was 131-132 degreeC.

Synthesis Example 12 Synthesis of Exemplary Compound A-14

12.9 g (61 mmol) of 2,4,5-trimethoxybenzoic acid, 50 mL of toluene and 0.6 mL of dimethylformamide were heated to 60 ° C, and then 8.0 g (67 mmol) of thionyl chloride was slowly added dropwise to 3.5 at 60 ° C. The mixture was stirred for a while by heating. Thereafter, a solution obtained by dissolving 17.7 g (104 mmol) of 4-phenoxyphenol in 25 mL of acetonitrile was slowly added and stirred by heating at 80 ° C. for 3 hours, and then the reaction solution was cooled to room temperature and 100 mL of methanol was added to precipitate. One crystal was recovered by filtration to obtain 21.6 g (yield 93%) of the title compound as white crystals. In addition, the identification of the compound was performed by the mass spectrum.

Mass spectrum: m / z 381 (M + H) ⁺ ,

Melting | fusing point of the obtained compound was 91-92 degreeC.

Synthesis Example 13 Synthesis of Exemplary Compound A-15

The target compound was obtained by the same method except changing 71.5 g of 4-cyano phenols in Synthesis Example 2 to 56.4 g of phenols. In addition, identification of the compound was performed by ¹ H-NMR and mass spectrum.

Melting | fusing point of the obtained compound was 105-108 degreeC.

Synthesis Example 14 Synthesis of Exemplary Compound A-16

A target compound can be obtained by the same method except changing 71.5 g of 4-cyano phenols in the synthesis example 2 into 74.4 g of 4-methoxy phenols. In addition, identification of the compound was performed by ¹ H-NMR and mass spectrum.

Melting | fusing point of the obtained compound was 102-103 degreeC.

Synthesis Example 15 Synthesis of Exemplary Compound A-17

The target compound was obtained in the same manner except changing 71.5 g of 4-cyanophenol in Synthesis Example 2 to 73.3 g of 4-ethylphenol. In addition, the compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

Mass spectrum: m / z 317 (M + H) ⁺ ,

Melting | fusing point of the obtained compound was 70-71 degreeC.                     

Synthesis Example 16: Synthesis of Exemplary Compound A-24

27.3 g (164 mmol) of 4-ethoxybenzoic acid, 108 mL of toluene and 1 mL of dimethylformamide were heated to 60 ° C, and then 21.5 g (181 mmol) of thionyl chloride was slowly added dropwise and stirred at 60 ° C for 2 hours. Thereafter, a solution obtained by dissolving 2-5.0 g (181 mmol) of 4-ethoxyphenol in 50 mL of acetonitrile was slowly added and stirred at 80 ° C. for 4 hours. After cooling the reaction solution to room temperature, 100 mL of methanol was added thereto. The precipitated crystals were collected by filtration to obtain 30.6 g (yield 65%) of the target compound as white crystals. In addition, the compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

Melting | fusing point of the obtained compound was 113-114 degreeC.

Synthesis Example 17 Synthesis of Exemplary 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 degreeC, 19.5 g (164 mmol) of thionyl chlorides were dripped slowly, and it stirred and heated at 60 degreeC for 2 hours. Thereafter, a solution obtained by previously dissolving 2-5.0 g (165 mmol) of 4-propoxyphenol in 50 mL of acetonitrile was slowly added and stirred at 80 ° C. for 4 hours. After cooling the reaction solution to room temperature, 100 mL of methanol was added thereto. Precipitated crystals were recovered by filtration, 100 mL of methanol was added to the obtained solid to recrystallize, and the obtained crystals were recovered by filtration to obtain 33.9 g (yield 76%) of the title compound as white crystals. On the other hand, the compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

Melting | fusing point of the obtained compound was 107 degreeC.

Synthesis Example 18 Synthesis of Exemplary Compound A-27

Synthesis was carried out 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. In addition, the identification of the compound was performed by the mass spectrum.

Mass spectrum: m / z 301 (M + H) ⁺ ,

Melting | fusing point of the obtained compound was 88-89 degreeC.

Synthesis Example 19 Synthesis of Exemplary Compound A-28

Synthesis was carried out 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. In addition, the identification of the compound was performed by the mass spectrum.

Mass spectrum: m / z 315 (M + H) ⁺ ,

Melting | fusing point of the obtained compound was 92 degreeC.

Synthesis Example 20 Synthesis of Exemplary Compound A-40

20.0 g (109 mmol) of 2,4-dimethoxybenzoic acid, 80 mL of toluene and 0.8 mL of dimethylformamide were heated to 60 ° C, and then 14.4 g (121 mmol) of thionyl chloride was slowly added dropwise and stirred at 60 ° C for 3.5 hours. It was. Thereafter, a solution in which 20.5 g (121 mmol) of 4-phenylphenol was previously dissolved in 50 mL of dimethylformamide was slowly added and stirred by heating at 80 ° C. for 6 hours. After cooling the reaction solution to room temperature, 100 mL of methanol was added thereto. The precipitated crystals were collected by filtration to obtain 31.7 g (yield 86%) of the target compound as white crystals. In addition, the identification of the compound was performed by the mass spectrum.

Mass spectrum: m / z 335 (M + H) ⁺ ,

Melting | fusing point of the obtained compound was 161-162 degreeC.

Synthesis Example 21 Synthesis of Exemplary Compound A-42

30.0 g (165 mmol) of 2,4-dimethoxybenzoic acid, 120 mL of toluene and 1.2 mL of dimethylformamide were heated to 60 ° C, and then 21.6 g (181 mmol) of thionyl chloride was slowly added dropwise and stirred at 60 ° C for 2 hours. It was. Thereafter, a solution of 27.6 g (181 mmol) of methyl 4-hydroxybenzoate previously dissolved in 40 mL of dimethylformamide was slowly added thereto, and stirred at 80 ° C. for 6 hours. After cooling the reaction solution to room temperature, 140 mL of methanol was added. Was added and the precipitated crystals were collected by filtration to obtain 24.4 g (yield 47%) of the target compound as white crystals. In addition, the compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

Melting | fusing point of the obtained compound was 122-123 degreeC.                     

Synthesis Example 22 Synthesis of Exemplary Compound A-51

20.7 g (50 mmol) of 2,4,5-trimethoxybenzoic acid 4-iodinephenyl, 5.61 g (55 mmol) of ethynylbenzene, 27.8 mL (200 mmol) of triethylamine, and 40 mL of tetrahydrofuran under a nitrogen atmosphere, After stirring at room temperature, 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 thereto, followed by heating at 60 ° C for 6 hours. Stirred. The reaction solution was then 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 an off-white crystal.

In addition, the compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

Melting | fusing point of the obtained compound was 129-130 degreeC.

Synthesis Example 23 Synthesis of Exemplary Compound A-52

42.4 g (0.2 mol) of 2,4,5-trimethoxybenzoic acid, 26.8 g (0.22 mol) of 4-hydroxybenzaldehyde, 170 mL of toluene and 1.7 mL of N, N-dimethylformamide were heated to 80 ° C., followed by Thionyl 26.0 g (0.22 mol) was slowly added dropwise and heated at 80 ° C for 6 hours. After cooling the reaction solution to room temperature, liquid separation was carried out with ethyl acetate, water and saturated brine, and the obtained oil phase was removed with sodium sulfate to remove water, and the solvent was distilled off under reduced pressure to add 240 mL of isopropyl alcohol to the obtained solid to recrystallize. The operation 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. In addition, identification of the compound was performed by ¹ H-NMR (400 MHz) and mass spectrum.

Melting | fusing point of the obtained compound was 103-105 degreeC.

Synthesis Example 24 Synthesis of Exemplary Compound A-53

40 g (126 mmol) of 2-, 4,5-trimethoxybenzoic acid 4-formylphenyl and a solution of 3.93 g (25.2 mmol) of sodium dihydrogen phosphate dissolved in 5 mL of water were added dropwise into 400 mL of acetonitrile, followed by 35% hydrogen peroxide. After 18.3 g of water was added dropwise for 20 minutes, a solution obtained by dissolving 14.1 g (126 mmol) of 80% pure sodium chlorite made by Wako Pure Chemical Industries, in 43 mL of water was added dropwise for 20 minutes, followed by stirring at room temperature for 4.5 hours. Thereafter, 100 mL of water was added and cooled to 10 ° C. The obtained crystals were separated by filtration and recrystallized from 500 mL of methanol to obtain 25.4 g of a target compound (yield 60%) as white crystals.

Melting | fusing point of the obtained compound was 188-189 degreeC. ?

Synthesis Example 25 Synthesis of Exemplary 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, 1.0 mL of N, N-dimethylformamide were heated to 70 ° C. Then, 3.4 g (28.5 mmol) of thionyl chlorides were dripped slowly, and it heated at 70 degreeC for 3 hours. After cooling the reaction solution to room temperature, 50 mL of methanol was added thereto, and the precipitated crystals were collected by filtration to obtain 8.1 g (yield 84%) of the target compound as white crystals. In addition, the compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

Melting | fusing point of the obtained compound was 189-190 degreeC.

Synthesis Example 26 Synthesis of Exemplary Compound A-56

8.50 g (42.8 mmol) of 2-hydroxy-4,5-dimethoxybenzoic acid, 5.62 g (42.8 mmol) of 4-cyanophenol, 45 mL of toluene and 0.5 mL of N, N-dimethylformamide were heated to 70 ° C., followed by Thionyl 5.6g (47.1 mmol) was dripped slowly, and it heated at 80 degreeC for 3 hours. After cooling the reaction solution to room temperature, 50 mL of methanol was added thereto, and the precipitated crystals were collected by filtration to obtain 5.8 g (yield 45%) of the target compound as white crystals. On the other hand, the compound was identified by ¹ H-NMR (400 MHz).

Melting | fusing point of the obtained compound was 145-146 degreeC.

Synthesis Example 27 Synthesis of Exemplary Compound A-57

8.50 g (42.8 mmol) of 2-hydroxy-4,5-dimethoxybenzoic acid, 7.17 g (42.8 mmol) of methyl 4-hydroxybenzoate, and 45 mL of toluene and 0.5 mL of N, N-dimethylformamide were heated to 70 ° C. And 6.1 g (51.2 mmol) of thionyl chlorides were dripped slowly, and it heated at 80 degreeC for 3 hours. After cooling the reaction solution to room temperature, 50 mL of methanol was added thereto, and the precipitated crystals were collected by filtration to obtain 6.9 g (yield 49%) of the target compound as white crystals. In addition, the compound was identified by ¹ H-NMR (400 MHz).

Melting | fusing point of the obtained compound was 128 degreeC.

Synthesis Example 28 Synthesis of Exemplary Compound A-58

It synthesize | combined by using vanillic acid instead of cyanophenol by the method similar to the synthesis example 2.

Melting | fusing point of the obtained compound was 201-203 degreeC.

Synthesis Example 29 Synthesis of Exemplary Compound A-62                     

It synthesize | combined by using 4-ethoxy-2-methoxybenzoic acid instead of 2,4,5-trimethoxybenzoic acid by the method similar to the synthesis example 10.

Melting | fusing point of the obtained compound was 88-89 degreeC.

Synthesis Example 30 Synthesis of Exemplary Compound A-63

It synthesize | combined by using 4-hydroxy-2- methoxy benzoic acid instead of 2,4, 5- trimethoxy benzoic acid by the method similar to the synthesis example 10.

Melting | fusing point of the obtained compound was 108-113 degreeC.

Synthesis Example 31 Synthesis of Exemplary Compound A-65

It synthesize | combined by using 4-hydroxy-2- methoxy benzoic acid instead of 2, 4- dimethoxy benzoic acid by the method similar to the synthesis example 2.

Melting | fusing point of the obtained compound was 142-144 degreeC.

As for any one compound represented by general formula (1), (2), (2-A)-(2-E), and (3) of this invention, 0.1-20 mass% of at least 1 sort (s) is added with respect to cellulose. Preferably, More preferably, it is 0.5-16 mass%, More preferably, it is 1-12 mass%, Especially preferably, it is 2-8 mass%. Most preferably, it is 3-7 mass%.

[Stretched film]

If the stretched film of this invention is a film in which the film surface of a film is extended | stretched 5% or more by the extending | stretching means immediately after film forming, what kind of material of a film may be sufficient, Preferably it is a polymer of molecular weight 5000 or more, For example, polyester, poly It is selected from a carbonate, a cycloolefin polymer, a cellulose, etc., More preferably, it is a cellulose, Furthermore, a cellulose ester is preferable and especially a cellulose acylate is preferable. As a draw ratio, Preferably it is 5 to 500%, More preferably, it is 5 to 300%, More preferably, it is 5 to 100%, Especially preferably, it is 10 to 40%.

[Cellulose Body Composition]

The cellulose body composition of the present invention is a cellulose compound or a compound having a cellulose skeleton obtained by introducing a functional group biologically or chemically from cellulose as a raw material (these are called cellulose bodies) and the general formulas (1), (2) and (2 It is a composition containing at least 1 sort (s) chosen from the compound represented by -A)-(2-E), (3). As a compound which has a cellulose skeleton, Preferably it is a cellulose ester, More preferably, it is a cellulose acylate (cellulose triacrylate, cellulose acylate propionate, etc.) are mentioned. In the present invention, two or more different cellulose acylates may be mixed and used.

Hereinafter, this invention is demonstrated to the representative example which uses the cellulose acylate as a cellulose compound.

Preferred cellulose acylates in the cellulose compound include the following materials. That is, cellulose acylate is a cellulose acylate in which the degree of substitution of cellulose 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 represent a substituent of the acyl group substituted by the hydroxyl group of a cellulose, SA is a substitution degree of an acetyl group, and SB is a substitution degree of the acyl group of 3 to 22 carbon atoms. The β-1 and 4-bonded glucose units constituting cellulose have free hydroxyl groups in 2nd, 3rd and 6th positions. A cellulose acylate is a polymer (polymer) which esterified some or all of these hydroxyl groups by the acyl group. Acyl substitution degree means the ratio (100% esterification is substitution degree 1) which cellulose is esterifying about 2nd, 3rd, and 6th positions, respectively. In this invention, the sum total of substitution degree of SA and SB of a hydroxyl group becomes like this. More preferably, it is 1.50-2.96, Especially preferably, it is 2.00-2.95. Moreover, substitution degree of SB is 0-1.5, and is 0-1.0 especially. Further, SB is preferably at least 28% of the substituent portion of the 6-position hydroxyl group, more preferably at least 30% is the substituent at the 6-position hydroxyl group, 35% or more is particularly preferred, particularly 40% or more is 6-position It is also preferable that it is a substituent of a hydroxyl group. Moreover, the sum total of substitution degree of SA and SB of the 6th position of a cellulose acylate is 0.8 or more, Furthermore, the cellulose acylate film of 0.85 or more and especially 0.90 or more is mentioned.

In this invention, as a C3-C22 acyl group which shows said SB of a cellulose acylate, an aliphatic acyl group, an aromatic acyl group may be sufficient, and it is not specifically limited. These are, for example, alkylcarbonyl esters, alkenylcarbonyl esters or aromatic carbonyl esters of cellulose, aromatic alkylcarbonyl esters, and the like, and may each further have a substituted group. Substituents which represent these preferable SB include propionyl, butanoyl, heptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, iso- Butanoyl, pivaloyl, cyclohexanecarbonyl, oleyl, benzoyl, naphthylcarbonyl, cinnamoyl group and the like. Among these, propionyl, butanoyl, dodecanoyl, octadecanoyl, pivaloyl, oleyl, benzoyl, naphthylcarbonyl, cinnamoyl and the like.

The basic principle of the method for synthesizing cellulose acylate is described in Migita et al., Pages 180-190 of wood chemistry (Kyoritsu Publication, 1968). A typical synthesis method is a liquid 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 introduced into a cooled carboxylic acid mixture and esterified to complete cellulose acylate (acyl substitution of 2nd, 3rd and 6th positions). The sum of the figures synthesizes almost 3.00). The said carboxylic acid liquid mixture generally contains acetic acid as a solvent, carboxylic anhydride as an esterifying agent, and sulfuric acid as a catalyst.

Carboxylic anhydride is usually used in an excess amount stoichiometrically than the sum total of the cellulose which reacts with this, and the moisture which exists in the system. After completion of the acylation reaction, neutralizing agents (e.g., carbonates, acetates or salts of calcium, magnesium, iron, aluminum or zinc) for the hydrolysis of excess anhydrous carboxylic acid remaining in the system and for the neutralization of part of the esterification catalyst An aqueous solution of oxide) is added. Next, the obtained cellulose acylate is saponified by maintaining at 50 to 90 ° C in the presence of a small amount of an acetylation reaction catalyst (usually, sulfuric acid remaining), and a cellulose acylate having a desired acyl substitution degree and a degree of polymerization. Change to At the point when the desired cellulose acylate is obtained, the catalyst remaining in the system is neutralized completely using the neutralizing agent as described above, or the cellulose acylate solution is added to water or dilute sulfuric acid (or the cellulose acylate solution). Water or dilute sulfuric acid is added) to separate cellulose acylate, and cellulose acylate is obtained by washing and stabilizing treatment.

It is preferable that the cellulose acylate film of this invention consists of the cellulose acylate which the polymer component which comprises a film substantially has said definition. "Substantially" means 55 mass% or more (preferably 70 mass% or more, more preferably 80 mass% or more) of a polymer component. Remainder is a plasticizer, a ultraviolet absorber, etc. When preparing a cellulose composition etc. as a raw material of film manufacture, it is preferable to use the particle | grains of a cellulose acylate. It is preferable that 90 mass% or more of the particle | grains used have a particle diameter of 0.5-5 mm. Moreover, it is preferable that 50 mass% or more of the particle to use has a particle diameter of 1-4 mm. It is preferable that the cellulose acylate particles have a shape as close to a sphere as possible.

The polymerization degree of the cellulose acylate used preferably in this invention is 200-700 of viscosity average polymerization degree, Preferably it is 250-550, More preferably, it is 250-400, Especially preferably, it is 250-350. The average degree of polymerization can be measured by the intrinsic viscosity method (Uda Kazuo, Hideo Hideo, Textile Society, Vol. 18 No. 1, 105-120, 1962). It is also described in detail in Japanese Patent Laid-Open No. 9-95538.                     

When the low molecular weight component is removed, the average molecular weight (polymerization degree) increases, but the viscosity is lower than that of the usual cellulose acylate. The cellulose acylate with few low molecular weight components can be obtained by removing the low molecular weight component from the cellulose acylate synthesized by a conventional method. Removal of the low molecular weight component can be carried out by washing the cellulose acylate with a suitable organic solvent.

On the other hand, when manufacturing the cellulose acylate with few low molecular weight components, it is preferable to adjust the amount of sulfuric acid catalysts 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 which is preferable in terms of molecular weight distribution (molecular weight distribution is uniform) can be synthesized. When used at the time of production of the cellulose acylate of the present invention, the water content is preferably 2% by mass or less, more preferably 1% by mass or less, particularly cellulose acylate having a water content of 0.7% by mass or less. Generally, cellulose acylate contains water and 2.5-5 mass% is known. In order to make water content of cellulose acylate small in this invention, drying is needed and the method will not be specifically limited if it can be made into the target water content (for example, 2 mass% or less).

These cellulose acylates of the present invention are described in detail on pages 7 to 12 in the invention association publication (Publication No. 2001-1745, issued March 15, 2001, Invention Association). .

To the cellulose acylate film of the present invention, various additives (e.g., plasticizer, ultraviolet light inhibitor, deterioration inhibitor, optically anisotropic control agent, fine particles, peeling agent, infrared absorber, etc.) according to the use in each preparation step may be added. And they may be solid or oily. That is, it is not specifically limited in the melting point or boiling point. For example, it is described in Unexamined-Japanese-Patent No. 2001-151901 etc. by mixing a 20 degreeC or less and 20 degreeC or more ultraviolet absorbing material, similarly a plasticizer, etc. Moreover, as an infrared absorption dye, it is described in Unexamined-Japanese-Patent No. 2001-194522, for example. Moreover, although the time to add can be added in a dope preparation process, you may further perform the process of adding and preparing an additive to the last preparation process of a dope preparation process.

In addition, the addition amount of each raw material is not specifically limited as long as a function expresses. In addition, when a cellulose acylate film is formed in multiple layers, the kind and addition amount of the additive of each layer may differ. For example, although it is described in Unexamined-Japanese-Patent No. 2001-151902 etc., these are the techniques known conventionally.

In addition, as for these details, the material described in detail on pages 16-22 by the invention association publication publication (air number 2001-1745, issued March 15, 2001, invention association) is used preferably.

The organic solvent in which the cellulose acylate of the present invention is dissolved is described.

First, the non-chlorine organic solvent which is preferably used in producing the solution of the cellulose acylate of the present invention will be described. In the present invention, within the range in which cellulose acylate can be dissolved, cast and film forming, the non-chlorine organic solvent is not particularly limited as long as the object can be achieved. 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.

Ester, ketone, and ether may have a cyclic structure. Compounds having two or more of functional groups of esters, ketones and ethers (i.e., -0-, -CO- and -CO0-) can also be used as the main solvent and have other functional groups such as, for example, alcoholic hydroxyl groups. There may be. In the case of the main solvent which has two or more types of functional groups, the carbon atom number should just be in the defined range of the compound which has any one 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 phentol Can be mentioned. Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol.

Although the non-chlorine organic solvent used for the above cellulose acylate is selected from the various viewpoints mentioned above, Preferably it is as follows. That is, the preferable solvent of the cellulose acylate of the present invention is at least three kinds of mixed solvents different from each other, wherein the first solvent is at least one selected from methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, dioxolane and dioxane. One kind or a mixture thereof, and the second solvent is selected from ketones or acetoacetic acid esters having 4 to 7 carbon atoms, and is selected from alcohols or hydrocarbons having 1 to 10 carbon atoms as the third solvent, and more preferably carbon number. It is 1-8 alcohols.

On the other hand, when the first solvent is a mixed liquid of two or more solvents, the second solvent may not be present. More preferably, the first solvent is methyl acetate, acetone, methyl formate, ethyl formate or a mixture thereof, and the second solvent is methyl ethyl ketone, cyclopentanone, cyclohexanone and methyl acetyl acetate. It may be a mixed liquid.

The alcohol which is the third solvent is preferably linear, may have a branch, or may be cyclic, and among them, saturated aliphatic hydrocarbon is preferable. The hydroxyl group of alcohol may be any of the 1st class-3rd class. Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 2-methyl-2-butanol and cyclohexanol. In addition, a fluorine-type alcohol is also used as alcohol. For example, 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3- tetrafluoro-1-propanol, etc. are mentioned.

In addition, a hydrocarbon may be linear, may have a branch, and may be cyclic. Both aromatic hydrocarbons and aliphatic hydrocarbons can be used. Aliphatic hydrocarbons may be saturated or unsaturated. Examples of hydrocarbons include cyclohexane, hexane, benzene, toluene and xylene. The alcohol and hydrocarbon which are these 3rd solvents may be individual, 2 or more types of mixtures are not specifically limited. Specific examples of the third solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol and cyclohexanol, cyclohexane and hexane as alcohols. In particular, methanol, ethanol , 1-propanol, 2-propanol, 1-butanol.

It is preferable that the above three types of mixed solvents contain 20 to 95 mass% of the first solvent, 2 to 60 mass% of the second solvent, and 2 to 30 mass% of the third solvent. It is preferable that 30-90 mass% of solvents, 3-50 mass% of 2nd solvents, and 3-25 mass% of 3rd alcohols are contained. Moreover, it is preferable that especially 1-30 mass% of 1st solvents, 3-30 mass% of 2nd solvents, and 3-15 mass% of 3rd solvents are contained as alcohol.

On the other hand, when a 1st solvent does not use a 2nd solvent as a mixed liquid, it is preferable that a 1st solvent is contained in the ratio of 20-30 mass%, and a 3rd solvent 5-30 mass%, and also the 1st solvent It is preferable that it is 30-86 mass%, and 7-25 mass% of 3rd solvents are contained. The non-chlorine organic solvent used in the present invention described above is described in detail in pages 12 to 16 of the Invention Association Publication (Publication No. 2001-1745, issued March 15, 2001, Invention Association). . Although the combination of the preferable non-chlorine organic solvent of this invention is mentioned below, it is not limited to these.

Methyl acetate / acetone / methanol / ethanol / butanol (75/10/5/5/5, mass part),

Methyl acetate / acetone / methanol / ethanol / propanol (75/10/5/5/5, mass part),

Methyl acetate / acetone / methanol / butanol / cyclohexane (75/10/5/5/5, mass part),

Methyl acetate / acetone / ethanol / butanol (81/8/7/4, parts by mass)

Methyl acetate / acetone / ethanol / butanol (82/10/4/4, mass part)                     

Methyl acetate / acetone / ethanol / butanol (80/10/4/6, mass part)

Methyl acetate / methyl ethyl ketone / methanol / butanol (80/10/5/5, mass part),

Methyl acetate / acetone / methyl ethyl ketone / ethanol / isopropanol (75/10/10/5/7, mass part),

 Methyl acetate / cyclopentanone / methanol / isopropanol (80/10/5/8, parts by mass),

Methyl acetate / acetone / butanol (85/5/5, parts by mass),

Methyl acetate / cyclopentanone / acetone / methanol / butanol (60/15/15/5/6, mass part),

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, mass part),

Methyl acetate / 1,3-dioxolane / methanol / ethanol (70/20/5/5, parts by mass),

Methyl acetate / dioxane / acetone / methanol / ethanol (60/20/10/5/5, mass part),

Methyl acetate / acetone / cyclopentanone / ethanol / isobutanol / cyclohexane (65/10/10/5/5/5, mass part),

Methyl formate / methyl ethyl ketone / acetone / methanol / ethanol (50/20/20/5/5, mass part),

Methyl formate / acetone / ethyl acetate / ethanol / butanol / hexane (65/10/10/5/5/5, mass part),

Acetone / acetoacetic acid methyl / methanol / ethanol (65/20/10/5, mass part),

Acetone / cyclopentanone / ethanol / butanol (65/20/10/5, parts by mass)

Acetone / 1,3 dioxolane / ethanol / butanol (65/20/10/5, mass part),

1,3 dioxolane / cyclohexanone / methylethylketone / methanol / butanol (55/20/10/5/5/5, parts by mass) may be mentioned.

Moreover, a cellulose acylate solution can also be used by the following method.

In the dope used for this technique, in addition to the non-chlorine organic solvent of the said technique, you may contain dichloromethane in 10 mass% or less of the total organic solvent amount.

In addition, in preparing the solution (composition liquid) of the cellulose acylate of this invention, a chlorine-type organic solvent is also used as a main solvent in some cases, and is described below. In this invention, the chlorine organic solvent is not specifically limited as long as the objective can be achieved in the range which cellulose acylate melt | dissolves, and can cast and film forming. These chlorine organic solvents are preferably dichloromethane and chloroform. Dichloromethane is particularly preferred.

In addition, there is no particular problem in mixing organic solvents other than the chlorine organic solvent. In that case, it is necessary to use at least 50 mass% of dichloromethane. The non-chlorine organic solvent used together of this invention is described below. That is, as a preferable non-chlorine organic solvent, the solvent chosen from ester of 3-12 carbon atoms, ketone, ether, alcohol, hydrocarbon, etc. is preferable. The ester, ketone, ether and alcohol may have a cyclic structure. Compounds having two or more of functional groups of esters, ketones and ethers (i.e., -0-, -CO- and -COO-) can also be used as solvents, having simultaneously different functional groups such as, for example, alcoholic hydroxyl groups. There may be. In the case of the solvent which has two or more types of functional groups, the carbon atom number should just be in the prescribed range of the compound which has any one 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 phentol Can be mentioned. Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol.

Moreover, as alcohol used together with a chlorine organic solvent, Preferably, it may be linear, may have a branch, may be cyclic, and it is especially preferable that it is a saturated aliphatic hydrocarbon. The hydroxyl group of alcohol may be any of the 1st class-3rd class. Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 2-methyl-2-butanol and cyclohexanol. In addition, a fluorine-type alcohol is also used as alcohol. For example, 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3- tetrafluoro-1-propanol, etc. are mentioned.

In addition, a hydrocarbon may be linear, may have a branch, and may be cyclic. Both aromatic hydrocarbons and aliphatic hydrocarbons can be used. Aliphatic hydrocarbons may be saturated or unsaturated. Examples of hydrocarbons include cyclohexane, hexane, benzene, toluene and xylene.                     

Although it does not specifically limit about the non-chlorine organic solvent used together with the chlorine organic solvent which is a main solvent used with respect to the above-mentioned cellulose acylate, Methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, dioxolane, dioxane And ketones or acetoacetic acid esters having 4 to 7 carbon atoms, alcohols or hydrocarbons having 1 to 10 carbon atoms. On the other hand, the preferred non-chlorine organic solvent used together is 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, hexane are mentioned. Although the following is mentioned as a combination of the chlorine type 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 / methylethylketone / methanol / butanol (80/10/5/5, parts by mass),

Dichloromethane / acetone / methylethylketone / 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 / methylethylketone / acetone / methanol / ethanol (50/20/20/5/5, parts by mass),                     

Dichloromethane / 1,3 dioxolane / methanol / ethanol (70/20/5/5, parts 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 / methylethylketone / 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 / acetoacetic acid / methanol / ethanol (65/20/10/5, parts by mass),

And dichloromethane / cyclopentanone / ethanol / butanol (65/20/10/5, parts by mass).

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 at a concentration of 13 to 27% by mass, and particularly at a concentration of 15 to 25% by mass. It is preferable that it is a rate solution. The method of performing cellulose acylate at these concentrations may be carried out so as to have a predetermined concentration in the dissolving step, and further produced in a low concentration solution (for example, 9-14 mass%) in advance, and then prescribed in the concentration step described later. It may be adjusted to a high concentration solution. Moreover, after making it into the high concentration cellulose acylate solution previously, you may make it the predetermined | prescribed low concentration cellulose acylate solution by adding various additives, and if it is performed so that the cellulose acylate solution concentration of this invention may be carried out by either method. There is no problem in particular.                     

In this invention, it is preferable that the aggregate molecular weight of the cellulose acylate of the dilution solution which made the cellulose acylate solution the 0.1-5 mass% with the organic solvent of the same composition is 150,000-15 million. More preferably, the association molecular weight is 180,000 to 9 million. This association molecular weight can be obtained by static light scattering. It is preferable to melt | dissolve so that the required square moment of inertia at the time may be 10-200 nm. Moreover, the preferable inertia square radius is 20-200 nm. In addition, the second virial coefficient of -2 × 10 ^-4 ~ 4 × 10 is to be dissolved, and more preferably ^-4 such that the second virial coefficient of ^{-2 × 1O -4 ~ 2 × 1O} -4 to be. Here, the definition of the association molecular weight in the present invention, furthermore, the inertia square radius and the second virtual coefficient will be described.

These were measured using the static light scattering method according to the following method. Measurements were made in the lean region on account of the apparatus, but their measurements reflect the dope behavior in the high concentration region of the present invention. First, cellulose acylate was dissolved in the solvent used for dope, and 0.1 mass%, 0.2 mass%, 0.3 mass%, and 0.4 mass% solution were prepared. In addition, the weighing was performed at 25 degreeC and 10% RH using what dried the cellulose acylate at 120 degreeC for 2 hours, in order to prevent moisture absorption. The dissolution method was carried out according to the method adopted at the time of dope dissolution (normal temperature dissolution method, cooling dissolution method, high temperature dissolution method).

Subsequently, these solutions and solvents were filtered through a 0.2 µm Teflon® filter. And the filtered solution was measured by the light scattering measuring device (DLS-700 by Otsuka Electronics Co., Ltd.) at 10 degree intervals from 30 degreeC to 140 degreeC at 25 degreeC. The obtained data were interpreted by the BERRY plot method. On the other hand, the refractive index required for this analysis is the value of the solvent obtained from the Abe refractometer, the concentration gradient (dn / dc) of the refractive index is used for the light scattering measurement using a differential refractometer (Otsuka Electronics Co., Ltd. DRM-1021) It measured using a solvent and a solution.

Next, about the preparation of the cellulose acylate solution (dope) of this invention, the dissolution method is not specifically limited, Room temperature may be sufficient, Furthermore, it is performed by a cooling dissolution method, a high temperature dissolution method, or a combination thereof. As for these, for example, JP-A-5-163301, JP-A-61-106628, JP-A-58-127737, JP-A-9-95544, JP-A-10. -95854, Japanese Patent Laid-Open No. 10-45950, Japanese Patent Laid-Open No. 2000-53784, Japanese Patent Laid-Open No. 11-322946, Japanese Patent Laid-Open No. 11-322947, Japanese Patent Laid-Open No. 2-276830, Japanese Laid Open Patent Publication No. 2000-273239, Japanese Patent Application Laid-Open No. Hei 11-71463, Japanese Patent Application Laid-Open No. 04-259511, Japanese Patent Application Laid-Open No. 2000-273184, Japanese Patent Application Laid-Open No. Hei 11-323017, Japanese Patent Application Laid-Open No. Hei 11-302388, etc. In each of the Japanese publications, a method for preparing a cellulose acylate solution is described. The dissolution method of these cellulose acylates in the organic solvent described above can apply these techniques as long as it is the range of this invention suitable also in this invention.

These details are carried out by the method described in detail on pages 22-25 in the invention association publication (Publication No. 2001-1745, issued March 15, 2001, and the Society of Inventions), particularly regarding non-chlorine solvent systems. . In addition, the dope solution of the cellulose acylate of the present invention is usually concentrated in solution and filtered, and is likewise described in detail on page 25 in the Invention Association Publication (Publication No. 2001-1745, issued March 15, 2001, Invention Association). It is described. On the other hand, when melt | dissolved at high temperature, it is most the case above the boiling point of the organic solvent to be used, and in that case, it is used in a pressurized state.

It is preferable that the cellulose acylate solution of this invention is a range with the viscosity and dynamic storage modulus of this solution. 1 mL of the sample solution was measured on a rheometer (CLS 500) using a Steel Cone (both manufactured by TA Instrumennts) having a diameter of 4 cm / 2 °. The measurement conditions were measured by varying the range from 40 ° C to -10 ° C to 2 ° C / min in the Oscillation Step / Temperature Ramp, and the static non-Newtonian viscosity at 40 ° C n ^* (Pa? '(Pa) was obtained. On the other hand, the sample solution was insulated until the liquid temperature became constant as the measurement start temperature in advance, and then the measurement was started. In the present invention, the viscosity at 40 ° C. is 1 to 400 Pa · s, the dynamic storage modulus at 15 ° C. is preferably 500 Pa or more, and more preferably the viscosity at 40 ° C. is 10 to 200 Pa · s, 15 ° C. The dynamic storage modulus at is preferably between 1 and 1 million. In addition, the higher the dynamic storage modulus at low temperature is preferable, for example, when the flexible support is -5 ℃, the dynamic storage modulus is preferably from 10,000 to 1 million Pa at -5 ℃, the support is -50 ℃ It is preferable that the dynamic storage modulus at −50 ° C. is 10,000 to 5 million Pa.

[Film? Cellulose Film]                     

Next, the film containing at least 1 sort (s) of any compound of General formula (2) or (2-A)-(2-E) of this invention is demonstrated. The material of the film may be any compound 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, for example, selected from polyester, polycarbonate, cycloolefin polymer, cellulose, and the like, more preferably cellulose, and A cellulose ester is preferable and especially a cellulose acylate is preferable.

Next, the manufacturing method is demonstrated to an example using the film which used the cellulose acylate solution as a film and a cellulose film of this invention.

As the method and equipment for producing the cellulose acylate film of the present invention, a conventional solution flexible film forming method and a solution flexible film forming apparatus used for producing a cellulose triacetate film are used. The dope (cellulose acylate solution) prepared in the dissolver (kiln) is once stored in a storage kiln, and the bubble contained in the dope is removed and finally prepared. The dope is sent from the dope outlet to the pressurized die through a pressurized metering gear pump capable of metering fluid with high precision according to the rotational speed, for example, and the dope is run endlessly from the detention (slit) of the pressurized die. It is uniformly pliable on the negative metal support, and the less dry dope film (also called a web) is peeled from the metal support at the peeling point at which the metal support is almost round.

Both ends of the web obtained are clipped and conveyed by a tenter while maintaining the width, and are dried. Then, they are conveyed by the roll group of a drying apparatus, complete drying, and are wound up to a predetermined length with a winder. The combination of the tenter and the drying apparatus of the roll group is changed depending on the purpose. In the solution flexible film forming method used for a silver halide photosensitive material or a functional protective film for an electronic display, in addition to a solution flexible film forming apparatus, it is applied for surface processing of films, such as a base layer, an antistatic layer, an antihalation layer, and a protective layer. Many devices are added. Each of these manufacturing processes is described in detail in pages 25 to 30 of the Invention Association Publication (Publication No. 2001-1745, published March 15, 2001, Invention Association), and flexible (including shared lead). , Metal supports, drying, peeling, stretching and the like.

Here, although the space temperature of a flexible part is not specifically limited in this invention, It is preferable that it is -50-50 degreeC. Moreover, 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 softened by the space temperature at low temperature can be instantly cooled on the support to increase the gel strength, thereby maintaining the film containing the organic solvent. As a result, the organic solvent can be peeled off from the support in a short time without evaporating the organic solvent from the cellulose acylate, thereby achieving high-speed flexibility. On the other hand, as a means for cooling a space, normal air may be sufficient, nitrogen, argon, helium, etc. may be sufficient and it is not specifically limited. In addition, 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 flexible part which casts a cellulose acylate solution is -50-130 degreeC, Preferably it is -30-25 degreeC, and is -20-15 degreeC. In order to maintain a flexible part at the temperature of this invention, you may achieve by introducing the gas cooled to a flexible part, or you may arrange | position a cooling apparatus to a flexible part, and cool a space. At this time, it is important to be careful not to adhere to the water, it can be carried out by using a dried gas.

In the present invention, the following configurations are particularly preferable regarding the contents and the softness of the respective layers. 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 relative to the cellulose acylate at 25 ° C, and / or at least one liquid or solid It is a cellulose acylate solution containing 0.001-5 mass% of ultraviolet absorbers with respect to a cellulose acylate, and / or 0.001-5 mass with respect to a cellulose acylate fine particle powder whose average particle diameter is 5-3000 nm with at least 1 sort (s) of solid. A cellulose acylate solution containing% and / or a cellulose acylate solution containing 0.001 to 2% by mass of at least one fluorine-based surfactant with respect to cellulose acylate, and / or at least one release agent It is a cellulose acylate solution containing 0.0001-2 mass% with respect to a rate, and / or at least 1 It is a cellulose acylate solution containing 0.0001-2 mass% of species deterioration inhibitors with respect to a cellulose acylate, and / or contains 0.1-15 mass% of at least 1 optically anisotropic control agent with respect to a cellulose acylate, And / or the cellulose acylate solution containing 0.1-5 mass% of at least 1 type of infrared absorbers with respect to a cellulose acylate, and the cellulose acylate film produced from it is preferable.

In the casting step, one kind of cellulose acylate solution may be single layered, or two or more kinds of cellulose acylate solutions may be simultaneously or gradually covalently smoked. When it has a casting | flow_spread process which consists of two or more layers, in the cellulose acylate solution and cellulose acylate film produced, the composition of the chlorine solvent of each layer should be the same or different composition, and the additive of each layer is 1 Of any kind, or of a mixture of two or more kinds, of which the addition position of the additive to each layer is the same or of different layers, the concentration of the additive in the solution of each layer is the same concentration, or any of the different concentrations One of the same or different aggregate molecular weight of each layer, one of the same or different temperature of solution of each layer, and the amount of coating of each layer is the same or different Either of which the viscosity of each layer is the same or different viscosity, after drying of each layer The thickness is either the same or different thickness, the material present in each layer is the same state or distribution or different state or distribution, the physical properties of each layer is one of the same or different physical properties, each layer It is also preferred that the cellulose acylate solution and the cellulose acylate film produced from the solution be characterized in that the physical property of the film is either one of a uniform or different physical property distribution.

Here, the physical properties include the physical properties described in detail on pages 6 to 7 of the Invention Association Publication (Publication No. 2001-1745, issued March 15, 2001, Invention Association), for example, haze, Transmittance, Spectroscopic Characteristics, Retardation Re, Retardation Rth, Molecular Orientation Axis, Axial Shift, Tear Strength, Cut Strength, Tensile Strength, Rolling In / Out Rt Difference, Squeak, Copper Friction, Alkali Hydrolysis, Curl Value, Water Content, Residual solvent amount, heat shrinkage rate, high humidity accuracy evaluation, permeability, baseness of the base, dimensional stability, heat shrinkage start temperature, elastic modulus and measurement of bright point foreign matter, and also includes impedance and plane used for base evaluation.

In addition, the yellow index, transparency and thermal properties (Tg, heat of crystallization) of cellulose acylate described in detail on page 11 in the Invention Association Publication (Publication No. 2001-1745, published March 15, 2001, Invention Association). And the like.

A cellulose acylate film can achieve the adhesion improvement of a cellulose acylate film and each functional layer (for example, a base coating layer and a back layer) by surface-treating in some cases. For example, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment can be used. The glow discharge treatment herein may be a low temperature plasma generated under a low pressure gas of 10 ⁻³ to 20 Torr, and also preferably a plasma treatment under atmospheric pressure.

The plasma-excited gas refers to a gas that is plasma-excited under the above conditions, and examples thereof include argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, freons such as tetrafluoromethane, and mixtures thereof. These are described in detail in pages 30 to 32 of the Invention Association Publication (Publication No. 2001-1745, issued March 15, 2001, Invention Association). On the other hand, the plasma treatment at atmospheric pressure, which has recently attracted attention, is used, for example, irradiation energy of 20 to 500 Kgy under 10 to 1000 Kev, and more preferably 20 to 300 Kgy of irradiation energy under 30 to 500 Kev. Among these, especially preferably, it is very effective as surface treatment of a cellulose acylate film as alkali soaping treatment.

An alkali saponification process is performed by apply | coating a saponification liquid. Examples of the coating method include a dip coating method, curtain coating method, extrusion coating method, bar coating method, and E type coating method. The solvent of the alkali saponification coating liquid has good wettability in order to apply it to the transparent support of the saponification liquid, and does not form unevenness on the surface of the transparent support by the saponification liquid solvent, and selects a solvent which keeps the surface in a good state. It is preferable. Specifically, an alcoholic solvent is preferable and isopropyl alcohol is especially preferable.

Moreover, the aqueous solution of surfactant can also be used as a solvent. Alkali which melt | dissolves in the said solvent is preferable, and, as for the alkali of an alkali saponification coating liquid, KOH and NaOH are more preferable. The pH of the saponified coating liquid is preferably 10 or more, more preferably 12 or more. 1 second or more and 5 minutes or less are preferable at room temperature, as for reaction conditions at the time of alkali soap, 5 seconds or more and 5 minutes or less are more preferable, 20 seconds or more and 3 minutes or less are especially preferable. After the alkaline soaping reaction, the saponified liquid coated surface is preferably washed with water or acid and then washed with water.

Moreover, a coating saponification process and the orientation film islands and islands drawing mentioned later can be used continuously, and the number of processes can be reduced.

In order to achieve adhesion between the film and the emulsion layer, after the surface activation treatment, the functional layer is directly applied onto the cellulose acylate film to obtain adhesive strength, and after the surface treatment of something, or without the surface treatment layer There is a method of forming (adhesive layer) and applying a functional layer thereon. Details of these undercoats are described on page 32 in the Published Journal of the Invention Association (Publication No. 2001-1745, published March 15, 2001, Invention Association). The functional layers of the cellulose acylate film of the present invention are also described in detail in pages 32 to 45 of the Korean Association Publication (Publication No. 2001-1745, issued March 15, 2001, Invention Association). have.

The optical performance of the cellulose body film of this invention is demonstrated. It is a value obtained by multiplying the film film thickness by an in-plane longitudinal and horizontal refractive index difference measured at an wavelength of 632.8 nm using an ellipsometer (AEP-100, manufactured by Shimadzu Corporation).

Re = (nx-ny) × d

Rth = {(nx + ny) / 2-nz} × d

nx: refractive index in the slow axis direction (the direction where the refractive index becomes maximum)

ny: refractive index in the direction orthogonal to the slow axis

nz: refractive index in the thickness direction

d: thickness of film (unit: nm)

The use of the cellulose acylate produced in the present invention will first be briefly described. The optical film of the present invention is particularly useful as a polarizing plate protective film, an optical compensation sheet of a liquid crystal display device, an optical compensation sheet of a reflective liquid crystal display device, and a support for a silver halide photosensitive material.

Therefore, the thickness of the film of this invention is decided according to these uses, and there is no restriction | limiting in particular, Preferably it is 30 micrometers or more, More preferably, it is 30-200 micrometers.                     

When using as a polarizing plate protective film, the manufacturing method of a polarizing plate is not specifically limited, It can manufacture by a general method. There exists a method of alkali-processing the obtained cellulose acylate film and bonding together the fully saponified polyvinyl alcohol aqueous solution to both surfaces of the polarizer produced by immersing and extending a polyvinyl alcohol film in the iodine solution. Instead of alkali treatment, reverse adhesion processing as described in Unexamined-Japanese-Patent No. 6-94915 and Unexamined-Japanese-Patent No. 6-118232 can also be performed. As an adhesive agent used for bonding a protective film process surface and a polarizer, polyvinyl alcohol adhesives, such as polyvinyl alcohol and polyvinyl butyral, vinyl latexes, such as butyl acrylate, etc. are mentioned, for example. . A polarizing plate is comprised by the polarizer and the protective film which protects both surfaces, Moreover, it is comprised by attaching a protective film to one side of this polarizing plate, and a separate film to the opposite side. The protective film and the separate film are used for the purpose of protecting the polarizing plate at the time of shipment of the polarizing plate and the inspection of the product.

In this case, a protective film is bonded in order to protect the surface of a polarizing plate, and is used for the opposite surface side of the surface which bonds a polarizing plate with a liquid crystal plate. In addition, a separator film is used for the purpose of covering the contact bonding layer bonded by a liquid crystal plate, and is used for the surface side which bonds a polarizing plate to a liquid crystal plate. In a liquid crystal display device, although the board | substrate containing a liquid crystal is normally arrange | positioned between two polarizing plates, the outstanding display property is obtained even if it arrange | positions in any site | part, the polarizing plate protective film which applied the optical film of this invention. In particular, since the transparent hard coat layer, the anti-glare layer, the anti-reflective layer, etc. are formed in the polarizing plate protective film on the outermost surface of the liquid crystal display device, it is particularly preferable to use the polarizing plate protective film in this portion.

The cellulose acylate film of this invention can be used for various uses, and when used as an optical compensation sheet of a liquid crystal display device, it is especially effective. The cellulose acylate film of this invention can be used for the liquid crystal cell of various display modes. Twisted Nematic (TN), In-Plane Switching (IPS), Ferroelectric Liquid Crystal (FLC), Anti-ferroelectric Liquid Crystal (AFLC), Optimally Compensatory Bend (OCB), Super Twisted Nematic (STN), Vertically Aligned (VA), and Various display modes such as HAN (Hybrid Aligned Nematic) have been proposed. Moreover, the display mode which orientation-divided the said display mode is also proposed.

A cellulose acylate film is effective also in the liquid crystal display device of any display mode. Also, it is effective in any liquid crystal display device of transmissive, reflective or transflective type. The cellulose acylate film of this invention can also be used as a support body of the optical compensation sheet of a TN type liquid crystal display device which has a liquid crystal cell of TN mode. The cellulose acylate film of this invention can also be used as a support body of the optical compensation sheet of STN type liquid crystal display device which has a liquid crystal cell of STN mode.

Generally, in the STN type liquid crystal display device, the rod-like liquid crystal component in the liquid crystal cell is twisted in the range of 90 to 360 degrees, and the product of the refractive index anisotropy (Δn) and the cell gap (d) of the rod-shaped liquid crystal component is (Δnd). It is in the range of 300-1500 nm. As for the optical compensation sheet used for an STN type liquid crystal display device, it describes in Unexamined-Japanese-Patent No. 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 advantageously used as a support for an optical compensation sheet of an OCB type liquid crystal display device having a liquid crystal cell of OCB mode or an HAN type liquid crystal display device having a liquid crystal cell of HAN mode.

The cellulose acylate film of the present invention is advantageously used as an optical compensation sheet of a reflective liquid crystal display device of TN type, STN type, HAN type, and GH (Guest-Host) type. These display modes are well known from before. Regarding the TN type reflective liquid crystal display device, there is a description in Japanese Patent Laid-Open Nos. 10-123478, WO9848320, and Patent No. 3022477. As for the optical compensation sheet used for the reflective liquid crystal display device, there is a description in WO00-65384. The cellulose acylate film of this invention is advantageously used also as a support body of the optical compensation sheet of an ASM type liquid crystal display device which has a liquid crystal cell of ASM (Axially Symmetric Aligned Microcell) mode. The liquid crystal cell of the ASM mode is characterized in that the thickness of the cell is maintained by the positionable resin spacer.

The other property is the same as that of the liquid crystal cell of TN mode. A liquid crystal cell of the ASM mode and an ASM type liquid crystal display device are described in Kume et al. (Sume 98 Digest 1089 (1998)). The use of these detailed cellulose acylate films described above is described in detail on pages 45 to 59 in the Invention Association Publication (Publication No. 2001-1745, issued March 15, 2001, Invention Association).

[Example]                     

Next, although this invention is demonstrated 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, stirred while heating, and each component was dissolved to prepare a cellulose acetate solution.

(Cellulose acetate solution composition)

100 parts by mass of cellulose acetate having an acetylation degree of 60.9%

7.8 parts by mass of triphenyl phosphate (plasticizer)

3.9 parts by mass of biphenyldiphenyl phosphate (plasticizer)

318 parts by mass of methylene chloride (first solvent)

47 parts by mass of methanol (second solvent)

16 mass parts of the compound of this invention or the comparative compound, 87 mass parts of methylene chlorides, and 13 mass parts of methanol were thrown into another mixing tank, and it stirred while heating, and prepared the retardation control agent solution.

36 mass parts of retardation control (rising) agent solutions were mixed with 474 mass parts of cellulose acetate solutions, and it fully stirred, and dope was prepared. The addition amount of the retardation regulator was 5.0 mass parts with respect to 100 mass parts of cellulose acetate (4.8 mass%).

The obtained dope was cast using a band softener. The film with 15 mass% of residual solvents was transversely stretched in the draw ratio of 26% using the tenter on 130 degreeC conditions, and the cellulose acetate film (thickness: 80 micrometers) was produced. About the produced cellulose acetate film (optical compensation sheet), the Re-retardation value and Rth retardation value in wavelength 633nm were measured using the ellipsometer (M-150, Nippon Bunco Co., Ltd. product). The results are shown in Table 1.

<Measurement of Rth, Re>

It was calculated | required according to the following formula using the ellipsomometer (AEP-100, the Shimadzu Corporation make) multiplied by the film thickness and the refractive index difference of the in-plane vertical and horizontal measured at the wavelength of 632.8 nm.

Re = (nx-ny) × d

Rth = {(nx + ny) / 2-nz} × d

nx: refractive index in the slow axis direction (the direction where the refractive index becomes maximum)

ny: refractive index in the direction orthogonal to the slow axis

nz: refractive index in the thickness direction

d: thickness of the film in nm                     

 In Table 1, in the additive 1), No. 6 and No. 12 adjusted the amounts of the retardation adjusting agent liquid and adjusted samples having different amounts of additions to No. 7 and No. 11, respectively.

In addition, each symbol in the optical performance evaluation 2) indicates that the optical performance is good (Re / Rth 0.30 to 0.35), and A represents the optical performance improvement effect (Re / Rth 0.25 to 0.39). ), × indicates the lack of optical performance (Re / Rth 0.20 ~ 0.24).

Comparative Compound 1                     

As can be seen from the results in Table 1, by adding the compound of the present invention, it was possible to produce a novel cellulose film having a large Re / Rth ratio that could not be realized in the known disk compound (Comparative Compound 1). Moreover, preparation of the cellulose film which has arbitrary Re / Rth ratio by using the compound of this invention and the comparative compound 1 is attained.

[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, and the methanol solution was sealed and left 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). The results are shown in Table 2.

In addition, in Table 2, each symbol of (triangle | delta), (circle), and (◎) in a stability evaluation column shows the following meaning.

Survival rate 80% or less

Retention rate 80% ～ 90% ○ No problem                     

Residual 90% ~ 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 compared with the known compound A-1.

The cellulose body composition of this invention is useful for forming the film excellent in the optical performance which satisfy | fills simultaneously the Re retardation value and Rth retardation value which were individually specified. Therefore, the cellulose acylate film obtained therefrom is excellent in optical performance.

Moreover, since the benzoic acid phenyl ester compound of this invention is excellent in stability and handleability, it can be used as a component of the film excellent in the said optical performance.

Claims (15)

The stretched film containing at least 1 sort (s) of the compound represented by following General formula (1). [General Formula (1)]

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an amino group or a hydroxyl group, and R ¹ , R ² , R ³ , R At least one of ⁴ and R ⁵ represents an alkoxy group, an alkylthio group or an amino group as an electron-donating group, R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a cyano group or a halogen atom, R ⁰ is a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, an alkynyl group of 2 to 6 carbon atoms, an aryl group of 6 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, a 6 to 12 carbon atoms Aryloxy group, alkoxycarbonyl group of 2 to 12 carbon atoms, acylamino group of 2 to 12 carbon atoms, acyloxy group of 2 to 10 carbon atoms, acyl group of 1 to 12 carbon atoms, carboxyl group, cyano group or halogen atom) At least 1 sort (s) of a cellulose body and the compound represented by following General formula (2), The stretched film characterized by the above-mentioned. [General Formula (2)]

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an amino group or a hydroxyl group, and R ¹ , R ² , R ³ , R At least one of ⁴ and R ⁵ represents an alkoxy group, an alkylthio group or an amino group as an electron-donating group, R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom, R ⁸ is a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, an alkynyl group of 2 to 6 carbon atoms, an aryl group of 6 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, a 6 to 12 carbon atoms An aryloxy group, a C2-C12 alkoxycarbonyl group, a C2-C12 acylamino group, a C1-C12 acyl group, a carboxyl group, a cyano group, or a halogen atom) A cellulose body composition and the cellulose body composition characterized by containing at least 1 sort (s) of the compound represented by following General formula (2). [General Formula (2)]

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an amino group or a hydroxyl group, and R ¹ , R ² , R ³ , R At least one of ⁴ and R ⁵ represents an alkoxy group, an alkylthio group or an amino group as an electron-donating group, R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom, R ⁸ is a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, an alkynyl group of 2 to 6 carbon atoms, an aryl group of 6 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, a 6 to 12 carbon atoms An aryloxy group, a C2-C12 alkoxycarbonyl group, a C2-C12 acylamino group, a C1-C12 acyl group, a carboxyl group, a cyano group, or a halogen atom) 4. The cellulose-based composition according to claim 3, wherein the electron donating group of the general formula (2) is an alkoxy group. 4. The cellulose-based 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 and R ⁵ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an amino group or a hydroxyl group, R ¹¹ represents an alkyl group having 1 to 12 carbon atoms, R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom, R ⁸ is a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, an alkynyl group of 2 to 6 carbon atoms, an aryl group of 6 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, a 6 to 12 carbon atoms An aryloxy group, a C2-C12 alkoxycarbonyl group, a C2-C12 acylamino group, a C1-C12 acyl group, a carboxyl group, a cyano group, or a halogen atom, 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) It formed from the cellulose body composition of any one of Claims 3-5, The cellulose body film characterized by the above-mentioned. The cellulose body film according to claim 6, wherein the cellulose body is cellulose acylate. It formed from the cellulose body composition of any one of Claims 3-5, The cellulose body stretched film characterized by the above-mentioned. The cellulose-based stretched film according to claim 8, wherein the cellulose is cellulose acylate. The compound represented by the following general formula (2-D). [General Formula (2-D)]

(Wherein R ² and R ⁵ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an amino group or a hydroxyl group, R ¹¹ represents an alkyl group having 1 to 12 carbon atoms, R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom, R ⁸ is a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, an alkynyl group of 2 to 6 carbon atoms, an aryl group of 6 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, a 6 to 12 carbon atoms An aryloxy group, a C2-C12 alkoxycarbonyl group, a C2-C12 acylamino group, a C1-C12 acyl group, a carboxyl group, a cyano group, or a halogen atom, 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). [General Formula (2-E)]

(In formula, R <^8> is a hydrogen atom, a C1-C4 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C6-C12 aryl group, a C1-C12 alkoxy group, a carbon number 6-12 aryloxy group, a C2-C12 alkoxycarbonyl group, a C2-C12 acylamino group, a C1-C12 acyl group, a carboxyl group, a cyano group, or a halogen atom, 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, R ¹⁴ represents an alkyl group having 1 to 4 carbon atoms, R ²⁰ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom) The compound represented by following General formula (3). [General Formula (3)]

(Wherein R ² , R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an amino group or a hydroxyl group, 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 is a C2-C7 alkynyl group, a C6-C12 aryl group, a C1-C12 alkoxy group, a C6-C12 aryloxy group, a C2-C6 alkoxycarbonyl group, a C2-C7 acylamino group Or cyano group) The stretched film according to claim 1, wherein at least two of R ¹ , R ² , R ³ , R ^4, and R ⁵ of the general formula (1) represent an electron donating group. The stretched film of claim 2, wherein at least two of R ¹ , R ² , R ³ , R ^4, and R ⁵ of the general formula (2) represent an electron-donating group. 4. The cellulosic composition of claim 3, wherein at least two of R ¹ , R ² , R ³ , R ^4, and R ⁵ of the general formula (2) represent an electron donating group.