KR101239544B1 - Composition of cellulose derivative, film of cellulose derivative and trialkoxybenzoic acid derivative - Google Patents

Abstract

(Problem) To provide the cellulose derivative composition which can form the film which has a preferable retardation value as an optical film, and the cellulose derivative film which has a preferable retardation value as an optical film.

(Solution means) A cellulose derivative composition comprising at least one compound represented by the general formula (1). A cellulose derivative film comprising the cellulose derivative composition. The compound represented by general formula (2).

In general formula (1)

In general formula (2)

Cellulose derivative composition, cellulose derivative film, trialkoxybenzoic acid derivative compound

Description

Cellulose derivative composition, cellulose derivative film, and trialkoxy benzoic acid derivative compound {COMPOSITION OF CELLULOSE DERIVATIVE, FILM OF CELLULOSE DERIVATIVE AND TRIALKOXYBENZOIC ACID DERIVATIVE}

[Patent Document 1] European Patent Publication EP0911656A2

[Patent Document 2] Japanese Unexamined Patent Publication No. 2003-344655

The present invention relates to a cellulose derivative composition and a cellulose derivative film composed of the cellulose derivative composition. The present invention also relates to novel trialkoxybenzoic acid derivative compounds.

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 calculated | required in optical compensation sheets (retardation film), such as a liquid crystal display device. Therefore, as an optical compensation sheet, it was common to use the synthetic polymer film with high retardation value like a polycarbonate film and a polysulfone film.

However, in recent years, the cellulose acetate film which has a high retardation value which can be used also for the use which requires optical anisotropy is proposed (for example, patent document 1, patent document 2). In the disclosed invention, in order to realize a high retardation value in 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 which is difficult to stretch, and it is known that it is difficult to increase the optical anisotropy. However, in Patent Documents 1 and 2, it is possible to increase the optical anisotropy by simultaneously aligning the additives by the stretching treatment, High retardation value is realized.

In recent years, in order to reduce the weight of a liquid crystal display device and to reduce manufacturing cost, the thinning of a liquid crystal cell becomes essential. Therefore, optical anisotropy which can be implement | achieved by the compound which has the 1,3,5-triazine ring of the said patent documents 1 and 2 in optical films including an optical compensation sheet (Re: retardation value in surface inside a film, Rth: film thickness) Retardation value in the direction), higher Re and lower Rth are required.

However, as a result of earnestly examining the method disclosed in Patent Literatures 1 and 2, the present inventors have found that there is a problem that the Re value and the Rth value described above cannot be controlled within the preferred ranges, respectively. Therefore, the development of new optical performance control technology is needed.

The 1st objective of this invention is providing the cellulose derivative composition which can form the film which has a preferable retardation value as an optical film.

The 2nd object of this invention is to provide the cellulose derivative film which has a preferable retardation value as an optical film.

(MEANS FOR SOLVING THE PROBLEMS)

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

[1] A cellulose derivative composition comprising at least one compound represented by the following General Formula (1).

In general formula (1)

(Wherein Ar ¹ and Ar ³ each independently represent an aryl group or an aromatic hetero ring, Ar ² represents an arylene group or an aromatic hetero ring, and L ¹ , L ² each independently represent a single bond or a divalent linking group. n represents an integer greater than or equal to 3, and Ar <^2> , L <^2> may be same or different, respectively. )

[2] The cellulose derivative composition according to [1], wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

In general formula (2)

(Wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom or a substituent. Ar ² represents an arylene group or An aromatic hetero ring, L ² and L ³ each independently represent a single bond or a divalent linking group, n represents an integer of 3 or more, and Ar ² and L ² may be the same or different.)

[3] The cellulose derivative composition according to [1] or [2], wherein the cellulose derivative contains cellulose acylate.

[4] A cellulose derivative film comprising the cellulose derivative composition according to any one of [1] to [3].

[5] A compound represented by the following General Formula (2).

In general formula (2)

(Wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom or a substituent. Ar ² represents an arylene group or An aromatic hetero ring, L ² and L ³ each independently represent a single bond or a divalent linking group, n represents an integer of 3 or more, and Ar ² and L ² may be the same or different.)

(Effects of the Invention)

The cellulose derivative composition of this invention is useful in order to form the film excellent in optical performance which satisfy | fills simultaneously the designated Re value and Rth value, respectively. Therefore, the cellulose derivative film obtained from this is excellent in optical performance.

(Best Mode for Carrying Out the Invention)

EMBODIMENT OF THE INVENTION Below, this invention is demonstrated in detail. Although description of the element | module described below may be made | formed based on the typical embodiment of this invention, this invention is not limited to such an embodiment. In addition, the numerical range displayed using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

The cellulose derivative composition of this invention is a composition containing a cellulose derivative, It is characterized by containing at least 1 sort (s) of the compound represented by General formula (1).

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

In General Formula (1), Ar ¹ and Ar ³ each independently represent an aryl group or an aromatic hetero ring, Ar ² represents an arylene group or an aromatic hetero ring, and L ¹ and L ² each independently represent a single bond, or A bivalent coupling group is shown. n represents an integer greater than or equal to 3, and Ar <^2> , L <^2> may be same or different, respectively.

Ar ¹ and Ar ³ each independently represent an aryl group or an aromatic hetero ring. Ar ¹ and Ar ³ may be different or may be the same. As an aryl group represented by Ar <^1> , Ar <^3> , Preferably it is a C6-C30 aryl group, You may be mono-cyclic and may form a condensed ring with another ring. Moreover, when possible, you may have a substituent and the substituent (T) mentioned later can be applied as a substituent.

In General Formula (1), as an aryl group represented by Ar <^1> , Ar <^3> , More preferably, it is C6-C20, Especially preferably, it is C6-C12, For example, a phenyl group, p-methylphenyl group, a naphthyl group, etc. Can be mentioned.

Ar ² represents an arylene group or an aromatic hetero ring, and Ar ² in the repeating unit may be all the same or different. The arylene group is preferably an arylene group having 6 to 30 carbon atoms, and may be monocyclic or may form a condensed ring with another ring. Moreover, when possible, you may have a substituent and the substituent (T) mentioned later can be applied as a substituent.

In general formula (1), as an arylene group represented by Ar <^2> , More preferably, it is C6-C20, Especially preferably, it is C6-C12, For example, a phenylene group, p-methylphenylene group, a naphthylene group, etc. Can be mentioned.

In General Formula (1), the aromatic hetero ring represented by Ar ¹ , Ar ² , Ar ³ may be an aromatic hetero ring including at least one of an oxygen atom, a nitrogen atom or a sulfur atom, and preferably 5 to It is an aromatic hetero ring containing at least 1 of an oxygen atom, a nitrogen atom, or a sulfur atom of a 6-membered ring. Moreover, if possible, you may further have a substituent. The substituent (T) mentioned later is applicable as a substituent.

As a specific example of the aromatic hetero ring represented by Ar <^1> , Ar <^2> , Ar <^3> in General formula (1), For example, furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyridine, pyri Chopped, triazole, triazine, indole, indazole, purine, thiazolin, thiazole, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoox Saline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzthiazole, benzotriazole, tetrazaindene, pyrrolotriazole And pyrazolotriazole. Preferable examples of the aromatic hetero ring are benzimidazole, benzoxazole, benzthiazole and benzotriazole.

In General Formula (1), L ¹ and L ² each independently represent a single bond or a divalent linking group. L ¹ and L ² may be the same or different. In addition, all L <^2> in a repeating unit may be same or different.

Preferred examples of the divalent linking group include a group represented by -NR ^7- (R ⁷ represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group), -SO _2- , -CO-, an alkylene group, a substituted alkyl. A ethylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, -O-, -S-, -SO- and a group obtained by combining two or more of these divalent groups, and among them, -O-, -CO- , -SO ₂ NR ^7- , -NR ⁷ SO _2- , -CONR ^7- , -NR ⁷ CO-, -COO-, and -OCO-, an alkynylene group, most preferably -CONR ⁷ -,- NR ⁷ CO-, -COO-, and -OCO-, an alkynylene group.

In the compound represented by the general formula (1) of the present invention, Ar ² is bonded to L ¹ and L ² , but when Ar ² is a phenylene group, L ¹ -Ar ² -L ² , and L ² -Ar ² Most preferably, -L ² is in a relationship between para positions (1,4-position) of each other.

In general formula (1), n represents the integer of 3 or more, Preferably it is 3-7, More preferably, it is 3-5.

Among the compounds represented by the general formula (1), preferred are compounds represented by the general formula (2).

Next, the compound represented by General formula (2) is demonstrated in detail.

In General Formula (2), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ^23, and R ²⁴ each independently represent a hydrogen atom or a substituent. Ar ² represents an arylene group or an aromatic hetero ring, and L ² and L ³ each independently represent a single bond or a divalent linking group. n represents an integer greater than or equal to 3, and Ar <^2> , L <^2> may be same or different, respectively.

Ar ² , L ² , and n are as described with respect to general formula (1), L ³ represents a single bond or a divalent linking group, and as an example of the divalent linking group, preferably, -NR ^7- (R ⁷ represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group), an alkylene group, a substituted alkylene group, -O-, and a group obtained by combining two or more of these divalent groups, among which- O-, -NR ^7- , -NR ⁷ SO _2- , and -NR ⁷ CO-.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a substituent, preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or carbon number 1 And an alkyl group having 4 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group, etc.), an aryl group having 6 to 12 carbon atoms (eg, phenyl group, naphthyl group), and more preferably an alkyl group having 1 to 4 carbon atoms. .

R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom or a substituent, preferably a hydrogen atom, an alkyl group, an alkoxy group or a hydroxyl group, and more preferably a hydrogen atom or an alkyl group (preferably An alkyl group having 1 to 4 carbon atoms, more preferably a methyl group).

The substituent (T) mentioned above is demonstrated below.

As a substituent (T), Preferably it is a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (preferably an alkyl group of 1-30 carbon atoms, for example, a methyl group, an ethyl group, n-propyl) Group, isopropyl group, t-butyl group, n-octyl group, 2-ethylhexyl group), cycloalkyl group (preferably, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example, cyclohexyl group, A hydrogen atom from a cyclopentyl group, a 4-n-dodecylcyclohexyl group, a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a bicycloalkane having 5 to 30 carbon atoms). It is a monovalent group removed one, for example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octan-3-yl), and an alkenyl group (preferably carbon number). A substituted or unsubstituted alkenyl group of 2 to 30, for example, a vinyl group and an allyl group, and a cycloalkenyl group (preferably Is a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms, for example, 2-cyclopenten-1-yl, 2 -Cyclohexen-1-yl), a bicyclo alkenyl group (substituted or unsubstituted bicyclo alkenyl group, preferably a substituted or unsubstituted bicyclo alkenyl group having 5 to 30 carbon atoms, that is, a bicyclo having one double bond) It is a monovalent group which removed one hydrogen atom of an alkene, for example, bicyclo [2,2,1] hepto-2-en-1-yl, bicyclo [2,2,2] octo-2-ene -4-yl), an alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, an ethynyl group, a propargyl group), an aryl group (preferably substituted to 6 to 30 carbon atoms, or Unsubstituted aryl groups such as phenyl groups, p-tolyl groups, naphthyl groups, heterocyclic groups (preferably substituted with 5 or 6 atoms or It is a monovalent group remove | excluding one hydrogen atom from an unsubstituted aromatic or non-aromatic heterocyclic compound, More preferably, it is a C3-C30 aromatic or heterocyclic group. For example, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably, C1-C1) A substituted or unsubstituted alkoxy group of 30, for example, methoxy group, ethoxy group, isopropoxy group, t-butoxy group, n-octyloxy group, 2-methoxyethoxy group), aryloxy group (preferably Is a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, a phenoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group ), Silyloxy group (preferably, a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy group, tert-butyldimethylsilyloxy group), heterocyclic oxy group (preferably 2 to 30 carbon atoms) Substituted or unsubstituted heterocyclic oxy group, 1-phenyltetrazol-5-oxy group, 2-tetrahydropyranyloxy group), acyloxy group ( Preferably, formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy group, acetyloxy group, p Valoyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group), carbamoyloxy group (preferably C1-C30 substituted or unsubstituted carbamoyloxy group, for example , N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyl jade Alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, methoxycarbonyloxy group, ethoxycarbonyloxy group, tert-butoxycarbon) Carbonyloxy group, n-octylcarbonyloxy group), aryloxycarbonyl jade (Preferably, a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, a phenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxyphenoxycarbo) Neyloxy group), an amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted alinino group having 6 to 30 carbon atoms, for example, an amino group, methylamino group, dimethylamino group, anyl) Lino group, N-methyl-anilino group, diphenylamino group, acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted carbon atoms to 6 to 30 Arylcarbonylamino group, for example, formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group, aminocarbonylamino group (preferably, carbon number 1) A substituted or unsubstituted aminocarbonylamino group of -30, for example, a carbamoylamino group, a N, N-dimethylaminocarbonylamino group, a N, N-diethylaminocarbonylamino group, a morpholinocarbonylamino group), Alkoxycarbonylamino group (preferably substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino group, ethoxycarbonylamino group, tert-butoxycarbonylamino group, n-octade Siloxycarbonylamino group, N-methyl-methoxycarbonylamino group, aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, methoxycarbonyl Amino group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxycarbonylamino group), sulfamoylamino group (preferably, substituted or unsubstituted sulfamo having 0 to 30 carbon atoms) Amino groups such as sulfamoylamino groups, N, N-dimethylaminosulfonylamino groups, Nn-octylaminosulfonylamino groups, alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulphyl having 1 to 30 carbon atoms) Phenylamino, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, for example, methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p -Methylphenylsulfonylamino group), mercapto group, alkylthio group (preferably substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, for example, methylthio group, ethylthio group, n-hexadecylthio group) , Arylthio group (preferably substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, for example, phenylthio group, p-chlorophenylthio group, m-methoxyphenylthio group), heterocyclic group ( Preferably a value of 2 to 30 carbon atoms Or an unsubstituted hetero cyclic group such as 2-benzothiazolylthio group, 1-phenyltetrazol-5-ylthio group, sulfamoyl group (preferably substituted or unsubstituted sulfamo having 0 to 30 carbon atoms) Diary, for example, N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N-benzoylsulfamoyl group, N- (N'phenylcarbamoyl) sulfamoyl group), sulfo group, alkyl and arylsulfinyl group (preferably, substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms) Sulfinyl groups such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl, alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, 6 Substituted or unsubstituted arylsulfonyl group of -30, for example, methylsulfonyl group, ethylsulfonyl group, phenylsulfonyl group, p- Ylphenylsulfonyl group), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, for example, acetyl group and pivaloyl) Benzoyl group), aryloxycarbonyl group (preferably substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, p-tert -Butylphenoxycarbonyl group), alkoxycarbonyl group (preferably substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, n-octadecyloxycarbonyl group) ), Carbamoyl group (preferably substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, for example, carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamo Group, N, N-di-n-octylcarbomoyl group, N- (methylsulfonyl) carbamoyl group), aryl and hetero gorazoxy group (preferably substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, 3 carbon atoms) Substituted or unsubstituted hetero cyclic group of -30, for example, a phenyl azo group, a p-chlorophenyl azo group, 5-ethylthio-1,3,4-thiadiazol-2-yl azo group, an imide group (preferably Is an N-succinimide group, an N-phthalimide group, or a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, a dimethylphosphino group and a diphenyl phosph) Pino group, methylphenoxyphosphino group), phosphinyl group (preferably, a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, for example, phosphinyl group, dioctyloxyphosphinyl group, diethoxy phosph) Pinyl group), phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, for example, Diphenoxyphosphinyloxy group, dioctyloxyphosphinyloxy group), phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino group, dimethylaminophosph) A pinylamino group) and a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, for example, trimethylsilyl group, tert-butyldimethylsilyl group, and phenyldimethylsilyl group).

The thing which has a hydrogen atom in the said substituent may remove this and may be substituted by the said group again. Examples of such functional groups include alkylcarbonylaminosulfonyl groups, arylcarbonylaminosulfonyl groups, alkylsulfonylaminocarbonyl groups, and arylsulfonylaminocarbonyl groups. Examples thereof include methylsulfonylaminocarbonyl group, p-methylphenylsulfonylaminocarbonyl group, acetylaminosulfonyl group, and benzoylaminosulfonyl group.

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.

As a preferable aspect of the compound represented by General formula (2),

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group:

R ²¹ , R ²² , R ²³ and R ²⁴ are all hydrogen atoms:

Ar ² is a substituted or unsubstituted arylene group, preferably a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, more preferably a substituted or unsubstituted phenylene group;

L ² is a single bond, -COO-, -OCO-, -CONR ^7- , -NR ⁷ CO-, -NR ^7- , -CONR ^7- (R ⁷ is a hydrogen atom, an alkyl group which may have a substituent or an aryl group. Preferably a hydrogen atom), -O-, or an alkynylene group;

And L ³ is —O— or —NR ⁷ — (R ⁷ represents a hydrogen atom, an alkyl group or an aryl group which may have a substituent.).

Although the specific example is given to the compound represented by General formula (1) and general formula (2) below, it demonstrates in detail, but this invention is not limited at all by the following specific examples.

The compound represented by General formula (2) can be synthesize | combined by a well-known method, For example, the following structure:

(In formula, A represents reactive groups, such as a hydroxyl group and a halogen atom, and R <^11> , R <^12> , R <^13> , R <^21> And R ²² is as described above. An intermediate obtained by reacting a raw material compound having a) with a derivative having a reactive site such as a hydroxyl group or an amino group:

(Wherein A ′ represents a reactive group such as a carboxyl group, and R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , Ar ² , and L ³ are as described above.)

2 molecules,

(In formula, B and B 'represent reactive groups, such as a hydroxyl group and an amino group, and Ar <^2> and L <^2> are as above-mentioned.)

It can obtain by connecting by 1 molecule. In addition, the compound represented by General formula (1) can also be synthesize | combined by the same method. However, the synthesis | combining method of the compound of this invention is not limited to this example.

It is preferable that content of the compound represented by General formula (1)-(2) in the cellulose derivative composition of this invention is 0.1-20 mass% with respect to a cellulose derivative, More preferably, it is 0.5-16. Mass%, More preferably, it is 1-12 mass%, Especially preferably, it is 1-8 mass%, Most preferably, it is 1-5 mass%.

The compounds represented by the general formulas (1) to (2) can be used as a retardation control agent for optical films, and particularly preferably as a retardation control agent for obtaining a film having excellent Re expressionability by stretching. Can be used. The compounds represented by the general formulas (1) to (2) are particularly useful as retardation control agents for cellulose derivative films. Details, such as a manufacturing method of the film containing these compounds, are mentioned later.

[Cellulose Derivative Composition]

The cellulose derivative composition of this invention is a composition containing a cellulose derivative and at least 1 sort (s) chosen from the compound represented by the said General formula (1)-(2). In this invention, a "cellulose derivative" shall include the cellulose compound and the compound which has a cellulose skeleton obtained by introduce | transducing a functional group biologically or chemically using a cellulose as a raw material. As a compound which has a cellulose skeleton, a cellulose ester is preferable, More preferably, it is a cellulose acylate (cellulose tricylate, a cellulose acylate propionate, etc.). In addition, in this invention, you may mix and use other 2 or more types of cellulose derivatives.

Hereinafter, the present invention will be described with a representative example of the case where cellulose acylate is used as the cellulose derivative.

Preferred cellulose acylates in the cellulose derivatives include the following materials. That is, a cellulose acylate is a cellulose acylate which the substitution degree to the hydroxyl group of cellulose satisfy | fills all of following formula (I)-(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 an acyl group of 3 to 22 carbon atoms. The glucose unit which binds (beta) -1,4 which comprises cellulose has free hydroxyl groups in 2nd, 3rd, and G 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 the cellulose acylate used by 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. In addition, SB is preferably at least 28% of the substituent portion of the 6-position hydroxyl group, more preferably at least 30% is the substituent of the 6-position hydroxyl group, 35% or more is particularly preferred, particularly 40% or more It is also preferable that it is a substituent of a hydroxyl group. Moreover, the cellulose acylate of the sum total of substitution degree of SA and SB of 6th position of a cellulose acylate is 0.8 or more, 0.85 or more, especially 0.90 or more can also be used.

In this invention, as a C3-C22 acyl group which shows said SB of a cellulose acylate, it may be an aliphatic acyl group, an aromatic acyl group, and is not specifically limited. They are alkylcarbonyl ester, alkenylcarbonyl ester or aromatic carbonyl ester, aromatic alkylcarbonyl ester, etc. of cellulose, for example, and may have group substituted further, respectively. As a substituent which shows these preferable SB, propionyl group, butanoyl group, heptanoyl group, hexanoyl group, octanoyl group, decanoyl group, dodecanoyl group, tridecanoyl group, tetradecanoyl group, hexadecanoyl group, octa Decanoyl group, isobutanoyl group, pivaloyl group, cyclohexanecarbonyl group, olein group, benzoyl group, naphthylcarbonyl group, cinnamoyl group and the like. Among these, propionyl group, butanoyl group, dodecanoyl group, octadecanoyl group, pivaloyl group, oleoyl group, benzoyl group, naphthylcarbonyl group, cinnamoyl group, etc. are mentioned.

The basic principle of the method for synthesizing cellulose acylate is described in Migita et al., Pages 180 to 190 (Kyoritsu Publication, 1968). A typical synthesis method is a liquid acetylation method using a carboxylic anhydride monoacetic 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 pre-cooled carboxylated mixture, followed by esterification and complete cellulose acylate (second, third and sixth acyl). The sum of substitution degree synthesizes almost 3.00). The said carboxylated 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 a 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 an oxide) is added. Next, saponified aging by maintaining the obtained complete cellulose acylate at 50 to 90 ° C. in the presence of a small amount of acetylation reaction catalyst (generally, sulfuric acid remaining), and a cellulose acyl having a desired acyl substitution degree and polymerization degree. Change up to rate. At the point when the desired cellulose acylate is obtained, the catalyst remaining in the system is neutralized completely with the neutralizing agent as described above, or the cellulose acylate solution is introduced into 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.

The polymerization degree of the cellulose acylate used preferably in the present invention is viscosity average polymerization degree 200 to 700, preferably 250 to 550, more preferably 250 to 400, and particularly preferably viscosity average polymerization degree 250 to 350. An average degree of polymerization can be measured by the intrinsic viscosity method (Uda Kazuo, Saito Hideo, Textile Society Journal, Vol. 18 No. 1, 105-120 pages, 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, which is useful. The cellulose acylate with few low molecular weight components can be obtained by removing a low molecular weight component from the cellulose acylate synthesize | combined by a conventional method. Removal of the low molecular weight component can be performed by washing a cellulose acylate with a suitable organic solvent.

Moreover, when manufacturing the cellulose acylate with few low molecular 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, a cellulose acylate (uniform in molecular weight distribution) can also be synthesized in terms of molecular weight distribution. It is preferable that the moisture content of the cellulose acylate used by this invention is 2 mass% or less, More preferably, it is 1 mass% or less, Especially preferably, it is 0.7 mass% or less. Generally, cellulose acylate contains water, and it is known that the water content is 2.5-5 mass%. In the present invention, in order to obtain a cellulose acylate having a low water content, the cellulose acylate may be dried, and the method is not particularly limited as long as the target water content (for example, 2% by mass or less) is possible.

These cellulose acylates which can be used in the present invention are described in detail on pages 7 to 12 in the raw material side and the synthesis method thereof in Korean Patent Publication (Publication No. 2001-1745, published March 15, 2001, Invention Association). It is described.

Content of the cellulose derivative in the cellulose derivative composition of this invention may be 55 mass% or more with respect to solid content whole quantity, Preferably it is 70 mass% or more, More preferably, it is 80 mass% or more. As a raw material for film production, when preparing the cellulose derivative composition of the present invention, it is preferable to use particles of cellulose acylate. It is preferable that 90 mass% or more of the particle | grains used have a particle size of 0.5-5 mm. Moreover, it is preferable that 50 mass% or more of the particle to use has a particle size of 1-4 mm. It is preferable that the cellulose acylate particles have a shape as close to a sphere as possible.

In the cellulose derivative composition of the present invention, in addition to the cellulose derivative and the compounds represented by the above general formulas (1) to (2), various additives according to the use in each preparation step (for example, plasticizers, sunscreens, anti-degradants) Optically anisotropic control agent, fine particles, release agent, infrared absorber and the like) can 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 mixing of the ultraviolet absorbing material of 20 degrees C or less and 20 degrees C or more, a plasticizer mixing, etc., and are described, for example in Unexamined-Japanese-Patent No. 2001-151901. Moreover, as an infrared absorbing dye, it is described, for example in Unexamined-Japanese-Patent No. 2001-194522. In addition, although the time to add may be added in a dope preparation process, you may 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. Moreover, when the cellulose derivative film which consists of a cellulose derivative composition of this invention is formed from a multilayer, the kind and addition amount of 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 these materials, the materials described in detail on pages 16 to 22 in the Publication of the Invention Association (Publication No. 2001-1745, issued March 15, 2001, Invention Association) are preferably used.

In the present invention, an organic solvent used for dissolving a cellulose derivative, preferably cellulose acylate, is described.

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

The ester, ketone and ether may have a cyclic structure. Compounds having two or more functional groups of esters, ketones and ethers (ie, -O-, -CO- and -CO0-) can also be used as the main solvent, and other functional groups such as, for example, alcoholic hydroxyl groups. You may have it. 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. 2-ethoxyethyl acetate, 2-methoxyethanol, and 2-butoxyethanol are mentioned as an example of the organic solvent which has two or more types of functional groups.

The non-chlorine organic solvents used in the above cellulose derivatives are selected from various viewpoints described above, but are preferably as follows. That is, in the present invention, preferred solvents used for the cellulose derivatives are three or more kinds of mixed solvents, wherein the first solvent is methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, dioxolane or dioxane. At least one selected or a mixture thereof, the second solvent is selected from ketones or acetoacetic acid esters having 4 to 7 carbon atoms, and selected from alcohols or hydrocarbons having 1 to 10 carbon atoms as the third solvent, and more preferably. Preferably an alcohol having 1 to 8 carbon atoms.

Moreover, when a 1st solvent is a liquid mixture of 2 or more types of solvent, there may be no 2nd solvent. More preferably, the first solvent is methyl acetate, acetone, methyl formate, ethyl formate or a mixture thereof, and the second solvent is preferably methyl ethyl ketone, cyclopentanone, cyclohexanone, or methyl acetyl acetate. It may be a mixed liquid of.

The alcohol which is a third solvent may be linear, may have a branch, or may be cyclic, and it is preferable that it is a saturated aliphatic hydrocarbon especially. 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, tert-butanol, 1-pentanol, 2-methyl-2-butanol and cyclohexanol. Moreover, 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. Any of aromatic hydrocarbons and aliphatic hydrocarbons can be used. The aliphatic hydrocarbon 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, or may be a mixture of 2 or more types, and is not specifically limited. As the third solvent, preferred specific compounds include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and cyclohexanol, cyclohexane, hexane, and especially methanol. , Ethanol, 1-propanol, 2-propanol, 1-butanol.

It is preferable that the above three types of mixed solvents contain 20-95 mass% of 1st solvents, 2-6 O mass% of 2nd solvents, and 2-30 mass% of 3rd solvents, and are 1st It is preferable that a solvent is 30-90 mass%, 3-50 mass% of a 2nd solvent, and 3-25 mass% of a 3rd alcohol are contained. Moreover, it is preferable that especially the 1st solvent is 30-90 mass%, the 2nd solvent is 3-30 mass%, and the 3rd solvent is alcohol, and 3-15 mass% is contained.

Moreover, when a 1st solvent does not use a 2nd solvent as a liquid mixture, it is preferable to contain 20-90 mass% of 1st solvents, and 5-30 mass% of 3rd solvents, and also 1st solvent It is preferable that it is 30-86 mass%, and 7-25 mass% of 3rd solvents are contained. The non-chlorine-based organic solvents used in the present invention described above are also described in detail on pages 12 to 16 in the Invention Association Publication (Publication No. 2001-1745, published March 15, 2001, Invention Association). Although the combination of the preferable non-chlorine organic solvent in this invention is mentioned below, it is not limited to these.

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

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

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

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

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

Methyl acetate / acetone / ethanol / butanol (80/10/4/6 parts by mass)

Methyl acetate / methyl ethyl ketone / methanol / butanol (80/10/5/5 mass parts);

Methyl acetate / acetone / methylethyl ketone / ethanol / isopropanol (75/10/10/5/7, parts by mass)

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

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

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

Methyl acetate / cyclohexanone / methanol / hexane (70/20/5/5, parts by mass),

Methyl acetate / methyl ethyl ketone / acetone / methanol / ethanol (50/20/20/5/5, parts by mass);

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

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

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

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

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

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

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

Acetone / 1,3-dioxolane / ethanol / butanol (65/20/10/5, parts by mass),

1,3 dioxolane / cyclohexanone / methylethylketone / methanol / butanol (55/20/10/5/5, parts by mass);

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

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

In addition, mixing of organic solvents other than chlorine-based organic solvents is not particularly a problem. In that case, it is preferable to use at least 50 mass% of dichloromethane. In this invention, the non-chlorine organic solvent used together with the chlorine organic solvent as a main solvent is described below. That is, as a preferable non-chlorine organic solvent used together, 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 functional groups of esters, ketones and ethers (ie, -0-, -CO- and -CO0-) can also be used as the solvent, and have simultaneously other functional groups such as, for example, alcoholic hydroxyl groups. You 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 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. 2-ethoxyethyl acetate, 2-methoxyethanol, and 2-butoxyethanol are mentioned as an example of the organic solvent which has two or more types of functional groups.

Moreover, as alcohol used together with a chlorine type 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 the alcohol may be any of the first to third classes. Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol and cyclohexanol. Moreover, 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, or may be cyclic. Any of aromatic hydrocarbons and aliphatic hydrocarbons can be used. The aliphatic hydrocarbon may be saturated or unsaturated. Examples of hydrocarbons include cyclohexane, hexane, benzene, toluene and xylene.

The non-chlorine organic solvent used in combination with the chlorine-based organic solvent which is the main solvent used for the above-described cellulose derivative is not particularly limited, but methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, dioxolane, dioxane, It is preferable to select from ketones or acetoacetic acid esters of 4 to 7 carbon atoms, alcohols or hydrocarbons of 1 to 10 carbon atoms. Moreover, as a preferable non-chlorine organic solvent used together, 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. In this invention, although the following is mentioned as a combination of the chlorine type organic solvent and non-chlorine type organic solvent which are preferable main solvents, it is not limited to these.

ㆍ dichloromethane / methanol / ethanol / butanol (75/10/5/5, parts by mass),

Dichloromethane / acetone / methanol / propanol (80/10/5/5, parts by mass),

ㆍ dichloromethane / methanol / butanol / cyclohexane (75/10/5/5/5, parts by mass)

ㆍ 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 mass parts),

Dichloromethane / methyl acetate / butanol (80/10/10 mass parts),

Dichloromethane / cyclohexanone / methanol / hexane (70/20/5/5, parts by mass),

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

ㆍ dichloromethane / 1,3 dioxolane / methanol / ethanol (70/20/5/5, parts by mass),

ㆍ dichloromethane / dioxane / acetone / methanol / ethanol (60/20/10/5/5, parts by mass),

ㆍ dichloromethane / acetone / cyclopentanone / ethanol / isobutanol / cyclohexane (65/1 0/10/5/5/5, parts by mass)

ㆍ dichloromethane / methylethylketone / acetone / methanol / ethanol (70/10/10/5/5, parts by mass)

ㆍ dichloromethane / acetone / ethyl acetate / ethanol / butanol / hexane (65/10/10/5/5/5, parts by mass)

ㆍ dichloromethane / acetoacetic acid methyl / methanol / ethanol (65/20/10/5, parts by mass),

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

And the like.

In this invention, it is preferable that the aggregate molecular weight of the cellulose acylate of the dilute solution which made dope containing cellulose acylate into 0.1-5 mass% in 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 calculated | required by the static light scattering method. It is preferable to melt | dissolve so that the square moment of inertia calculated | required at the time may be 10-200 nm. More preferred square radius of inertia is 20 to 200 nm. The second factor is seen irregularities -2 × 10 ^-4 ~4 × 10 ^-4 to be preferred, and more preferred to dissolve so that the second coefficient has irregularities Al ^{-2 × 10 -4 ~2 × 10 -} 4 to be. Here, the definition of the association molecular weight in the present invention, and also the inertia square radius and the second virial coefficient is described.

These were measured using the static light scattering method according to the following method. Measurements were made in the lean region due to the circumstances of the apparatus, but these 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 balance amount was performed at 25 degreeC and 10% RH, using what dried the cellulose acylate for 2 hours at 120 degreeC in order to prevent moisture absorption. The dissolution method was performed in accordance with the method (normal temperature dissolution method, cooling dissolution method, high temperature dissolution method) employed at the time of dope dissolution.

Subsequently, these solutions and the solvent were filtered through a 0.2 µm Teflon filter. And the static light scattering of the filtered solution was measured at 30 degreeC from 30 degree | times to 140 degree | times at 25 degreeC using the light-scattering measuring apparatus (DLS-700 by Otsuka Electronics Co., Ltd.). The obtained data were interpreted by the BERRY plot method. In addition, the refractive index required for this analysis uses the value of the solvent calculated | required by the Abbe refractometer, and the density | concentration gradient (dn / dc) of the refractive index uses a differential refractometer (DRM-1021 by Otsuka Electronics Co., Ltd.) for light scattering measurement. It measured using the used solvent and solution.

Regarding the preparation of the dope containing the cellulose derivative in the present invention, the dissolution method is not particularly limited, and the dissolution method is also at room temperature, and can be carried out by a cooling dissolution method or a high temperature dissolution method or a combination thereof. About these, Unexamined-Japanese-Patent No. 5-163301, Unexamined-Japanese-Patent No. 61-106628, Unexamined-Japanese-Patent No. 58-127737, Unexamined-Japanese-Patent No. 9-95544, Unexamined-Japanese-Patent No. Japanese Patent Application Laid-Open No. Hei 10-95854, Japanese Patent Application Laid-open No. Hei 10-45950, Japanese Patent Application Laid-Open No. 2000-53784, Japanese Patent Application Laid-Open No. 11-322946, and Japanese Patent Application Laid-Open No. 11-322947 Japanese Patent Application Laid-Open No. 2-276830, Japanese Unexamined Patent Publication No. 2000-273239, Japanese Unexamined Patent Publication No. 11-71463, Japanese Unexamined Patent Publication No. 04-259511, Japanese Unexamined Patent Publication No. 2000-273184 The preparation method of a cellulose derivative solution is described by each publication 11-1123017 and Unexamined-Japanese-Patent No. 11-302388. The method of dissolving these cellulose derivatives in the organic solvent described above can be applied as long as it is the scope of the present invention as appropriate in the present invention.

These details are described in detail on pages 22 to 25, especially in the non-chlorine solvent system, published by the Society of the Invention (Publication No. 2001-1745, published March 15, 2001, Invention Association). In the present invention, the dope containing the cellulose derivative is usually concentrated in solution and filtered, and the method is similarly disclosed in the Invention Association Publication (Publication No. 2001-1745, issued March 15, 2001, Invention Association). ), Which is described in detail on page 25. Moreover, when melt | dissolving at high temperature, the case more than the boiling point of the organic solvent to be used is mostly, and in that case, it is used in a pressurized state.

The cellulose derivative composition of this invention is prepared by mixing the solution obtained by melt | dissolving the compound represented by the said General formula (1)-(2) in a suitable solvent, and the cellulose derivative solution obtained by melt | dissolving a cellulose derivative in a suitable solvent. can do. The mixing method of both solutions is not specifically limited, The solution obtained by mixing both solutions can be used as dope for film formation. In the present invention, however, the order of addition of the cellulose derivative and the compounds represented by the general formulas (1) to (2) may be added simultaneously. It is preferable that the density | concentration of the cellulose derivative in dope is 10-30 mass%, More preferably, it is 13-27 mass%, It is preferable that it is 15-25 mass% especially. The method of dissolving a cellulose derivative in these concentrations may be performed so that it may become a predetermined | prescribed density | concentration in the dissolving | staining step, and also it produced previously as a low concentration solution (for example, 9-14 mass%), and then predetermined | prescribed high concentration in the below-mentioned concentration process You may adjust with a solution. In addition, it is good also as a cellulose derivative solution of a high density | concentration beforehand, and it is good also as a predetermined | prescribed low concentration cellulose derivative solution by adding various additives, and as long as the dope of the said density | concentration is obtained, any method may be sufficient.

In addition, in order to melt | dissolve the compound represented by the said General formula (1)-(2), the same thing as the solvent for cellulose derivatives mentioned above can be used. The density | concentration of the compound represented by General formula (1)-(2) in dope can be 0.1-30 mass%, for example, Preferably it can be 1-15 mass%.

In this invention, it is preferable that the dope containing a cellulose derivative is a range with the viscosity and the dynamic storage elastic modulus of this solution. 1 mL of the sample solution was measured on a rheometer (CLS 500) using Steel Cone (all manufactured by TA Instruments) having a diameter of 4 cm / 2 °. The measurement conditions were measured by varying the range from 40 ° C to -10 ° C at 2 ° C / min in Oscillation Step / Temperature Ramp, and the static non-Newtonian viscosity of 40 ° C n * (Pa · s) and storage modulus G of -5 ° C. (Pa) was obtained. In addition, the sample solution was measured until the solution temperature was kept constant at the measurement start temperature in advance. In this invention, it is preferable that the viscosity in 40 degreeC is 1-400 Pa.s, and the dynamic storage elastic modulus in 15 degreeC is 500 Pa or more, and the viscosity in 40 degreeC is 10-200 Pa.s, and dynamic storage in 15 degreeC It is more preferable that the elastic modulus is 1 to 1 million. In addition, the larger 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 ℃, and the support is -50 ℃ As for the dynamic storage elastic modulus in -50 degreeC, 10,000-5 million Pa are preferable.

[Cellulose Derivative Film]

The cellulose derivative film of this invention consists of the cellulose derivative composition of this invention.

Next, the manufacturing method of the cellulose derivative film of this invention is said.

As the method and equipment for producing the cellulose derivative film of the present invention, a solution casting film forming method and a solution casting film forming apparatus conventionally provided for cellulose triacetate film production can be used. Below, the specific example is demonstrated. The dope (cellulose derivative composition solution) prepared in the dissolver (pot) is once stored in a storage pot, and the final result is obtained by defoaming the foam contained in the dope. The dope is sent from the dope outlet to a pressurized die through a pressurized metering gear pump capable of metering fluid with high precision, for example, by rotational speed, and the dope is running endlessly from the slit of the pressurized die. The less dry dope film (also called a web) is peeled from the metal support at a peeling point that is uniformly cast on the metal support of the flexible part and the metal support is almost round.

Both ends of the web to be obtained are sandwiched with a clip, conveyed by a tenter and dried while maintaining the width, then conveyed by a roll group of the drying apparatus, terminated by drying, and wound up to a predetermined length by a winder. The combination of a tenter and the drying apparatus of a roll group changes with the objective. In the solution casting film forming method used for a silver halide photosensitive material and the functional protective film for electronic displays, in addition to a solution casting film forming apparatus, the surface to films, such as a lower layer, an antistatic layer, an antihalation layer, a protective layer, etc. For processing, an application device is often added. Each of these manufacturing processes is described in detail on pages 25 to 30 by the Korean Society of Publications (Publication No. 2001-1745, published March 15, 2001, Invention Association), and is flexible (including covalent 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. It is more preferable that it is -30-40 degreeC, and it is especially preferable that it is -20-30 degreeC. In particular, the dope cast by the space temperature at low temperature can be temporarily cooled on the support to increase the gel strength, so that the film containing the organic solvent can be maintained. Thereby, it becomes possible to peel from a support body in a short time, without evaporating an organic solvent from a cellulose derivative, and high speed casting can be achieved. The means for cooling the space may be ordinary air, nitrogen, argon, helium or the like, and is not particularly limited. Moreover, in that case, 0-70% RH is preferable and 0-50% RH is more preferable. Moreover, in this invention, the temperature of the support body of the flexible part which casts dope is normally -50-130 degreeC, Preferably it is -30-25 degreeC, More preferably, it is -20-15 degreeC. In order to maintain a flexible part at a desired temperature, you may achieve by introducing the gas cooled to the flexible part, or you may arrange | position a cooling apparatus to the flexible part, and cool a space. At this time, it is important to be careful not to adhere water, and it can be carried out by a method such as 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 dope is a dope which contains 0.1-20 mass% of at least 1 sort (s) of liquid or solid plasticizer with respect to a cellulose derivative at 25 degreeC, and / or at least 1 sort (s) of liquid or solid ultraviolet absorber It is dope containing 0.001-5 mass% with respect to a derivative, and / or It is dope containing 0.001-5 mass% with respect to a cellulose derivative, At least 1 sort (s) of solid particle whose average particle size is 5-3000 nm with respect to a cellulose derivative. A dope containing 0.001 to 2% by mass of the cellulose derivative and / or at least one fluorine-based surfactant in the cellulose derivative, and / or 0.0001 to 2% by mass of the cellulose derivative in the cellulose derivative. Dope and / or dope containing 0.0001-2 mass% of at least 1 sort (s) of deterioration inhibitor with respect to a cellulose derivative, and / or at least 1 Dope containing 0.1-15 mass% of optically anisotropic control agents with respect to a cellulose derivative, and / or 0.1-5 mass% of at least 1 type of infrared absorbers with respect to a cellulose derivative, and The cellulose derivative film (preferably a cellulose acylate film) produced from it is preferable.

In the casting step, one type of dope may be single layered, or two or more types of dope may be simultaneously and / or sequentially shared. In the case of having a casting process consisting of two or more layers, in the dope and cellulose derivative film to be produced, the composition of the chlorine-based solvent of each layer is one of the same or different composition, the additive of each layer is one kind, or two Any one of a mixture of more than one kind, the position at which the additives are added to each layer is the same or any of the different layers, the concentration in the solution of the additives is the same or all of the different concentrations in each layer, Any one of the same or different aggregate molecular weights of each layer, one of the same or different temperatures of the solution of each layer, and any of the same or different coating amounts of each layer Of which the viscosity of each layer is the same or different, the film thickness after drying of each layer is the same One of different or different thicknesses, the material present in each layer being in the same state or distribution or in a different state or distribution, the physical properties of each layer being one of the same or different properties, the physical properties of each layer It is also preferable that it is a dope and cellulose derivative film (preferably a cellulose acylate film) produced from the dope which is characterized by any one of uniform or different distribution of a physical property.

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, Spectral Characteristics, Retardation Re, Copper Rth, Molecular Orientation Axis, Axis Offset, Tear Strength, Breaking Strength, Tensile Strength, Winding In / Out Rt, Squeak, Copper Friction, Alkaline Hydrolysis, Curing Value, Water Content, Residual Solvent Amount, Heat Shrinkage rate, high-humidity numerical evaluation, water vapor transmission rate, the planarity of a base, numerical stability, heat shrinkage start temperature, elasticity modulus, a measurement of a bright point foreign material, etc., and also the impedance and surface shape used for evaluation of a base are included.

In addition, the yellow index, transparency, thermal properties (Tg, heat of crystallization) of cellulose acylate described in detail on page 11 of the Invention Association publication (air number 2001-1745, issued March 15, 2001, Invention Association). Can be mentioned.

The cellulose derivative film of this invention may be extended | stretched. Particular preference is given to stretching at any magnification in order to express optical anisotropy.

Stretching can use a well-known method, for example, from the temperature of 10 degreeC higher than the glass transition temperature (Tg) of a cellulose derivative film to the temperature between 50 degreeC high, roll-axis stretching method, tenter-axis stretching It can extend | stretch by the method, simultaneous biaxial stretching method, the successive biaxial stretching method, and the inflation method. Moreover, in the case of film manufacture by the solution casting method, it can extend | stretch within the range which is 1%-30% of residual solvent, More preferably, it is within the range of 5%-20%. As for draw ratio, 1.1-3.5 times are used preferably.

The cellulose derivative film can be surface-treated in some cases, and the improvement of the adhesion of a cellulose derivative film and each functional layer (for example, the undercoat layer and a white layer) can be achieved. 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 conditions described above, and may include argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, prolons 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). Moreover, the irradiation energy of 20-500 Kgy is used, for example under 10-1000 Kev, and the irradiation energy of 20-300 Kgy is used more preferably under 30-500 Kev for the plasma processing which is attracting attention recently. Among these, especially preferably, it is an alkali saponification process and is very effective as a surface treatment of a cellulose acylate film.

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 treatment coating liquid has good wettability in order to apply it to the transparent support of the saponification liquid, and selects a solvent which maintains a good shape without forming irregularities on the transparent support surface by the saponification liquid solvent. 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. The alkali which the alkali saponification coating liquid dissolves in the said solvent is preferable, and KOH and NaOH are more preferable. 10 or more are preferable and, as for pH of saponification coating liquid, 12 or more are more preferable. 1 second or more and 5 minutes or less are preferable at room temperature, as for reaction conditions at the time of alkali saponification, 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 alkali saponification reaction, it is preferable to wash the saponified solution coated surface with water or acid and then wash with water.

Moreover, a coating saponification process and the orientation film islands-state drawing mentioned later can be performed 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, a method of directly applying a functional layer on the cellulose derivative film to obtain adhesion, and after some surface treatment, or without surface treatment, There is a method of forming an undercoat (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 derivative film of the present invention are also described in detail on pages 32 to 45 in the Publication of the Invention Association (Publication No. 2001-1745, issued March 15, 2001, Invention Association).

In order to control Re value and Rth value of the cellulose derivative film of this invention in a preferable range, respectively, the kind and addition amount of the compound (retardation control agent) represented by General formula (1)-(2) to be used, and It is preferable to adjust the draw ratio of a film suitably. In particular, in the present invention, a desired Re is selected by selecting a retardation control agent capable of achieving a desired Rth value and appropriately setting the addition amount of the retardation control agent and the draw ratio of the film so as to obtain a desired Re value. A cellulose derivative film having a value and a Rth value can be obtained.

In this specification, Re ((lambda)) and Rth ((lambda)) represent the in-plane retardation in wavelength (lambda), and the retardation of the thickness direction, respectively. Re ((lambda)) is measured by making light of wavelength ((lambda) nm) into a film normal line direction in KOBRA 21ADH (made by Oclock side apparatus Co., Ltd.). Rth (λ) is a light having a wavelength (λnm) in a direction inclined at + 40 ° with respect to the film normal direction using Re (λ) and the in-plane slow axis (determined by KOBRA 21ADH) as the inclination axis (rotation axis). The sum of the retardation values measured by incidence and the retardation values measured by injecting light having a wavelength (λ nm) in a direction inclined at -40 ° with respect to the film normal direction using the in-plane slow axis as the inclination axis (rotation axis). KOBRA 21ADH is calculated based on the retardation value measured in the direction, the assumption of the average refractive index and the input film thickness value. Here, the hypothetical value of the average refractive index can be a polymer handbook (JOHN WILEY & SONS, INC) and values of catalogs of various optical films. The thing with which an average refractive index value is not already known can be measured with an Abbe refractometer. The value of the average refractive index of the main optical film is illustrated below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethylmethacrylate (1.49), polystyrene (1.59).

First, the use of the cellulose derivative film of the present invention will be briefly described.

The cellulose derivative film of this invention is useful as an optical film, especially a polarizing plate protective film, the optical compensation sheet (also called phase difference film) of a liquid crystal display device, the optical compensation sheet of a reflective liquid crystal display device, and the support for silver halide photosensitive materials. Do.

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 is a method in which the obtained cellulose derivative film is subjected to an alkali treatment and adhered to both surfaces of a polarizer produced by dipping and stretching the polyvinyl alcohol film in an oxo solution using a fully saponified polyvinyl alcohol aqueous solution. Instead of alkali treatment, the easy adhesion process described in each of Unexamined-Japanese-Patent No. 6-94915 and Unexamined-Japanese-Patent No. 6-118232 may be performed. As an adhesive agent used in order to attach a protective film process surface and a polarizer, polyvinyl alcohol adhesives, such as polyvinyl alcohol and polyvinyl butyral, vinyl latexes, such as butylacrylate, etc. are mentioned, for example. . A polarizing plate is comprised from the polarizer and the protective film which protects both surfaces, Moreover, a protective film is bonded to one surface of this polarizing plate, and it is comprised by bonding a separate film to the opposite surface. A protective film and a separate film are used for the purpose of protecting a polarizing plate at the time of a polarizing plate shipment, a product inspection, etc.

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 to a liquid crystal plate. In addition, a separator film is used for the purpose of covering the contact bonding layer bonded to a liquid crystal plate, and is used for the surface side which bonds a polarizing plate to a liquid crystal plate. Although the board | substrate containing a liquid crystal is normally arrange | positioned between two polarizing plates in a liquid crystal display device, the outstanding display property is obtained even if it arrange | positions in what site | part the polarizing plate protective film which applied the film of this invention. In particular, since a transparent hard coat layer, an antiglare layer, an antireflection layer, etc. are formed in the polarizing plate protective film of the display side outermost surface of a liquid crystal display device, it is especially preferable to use this polarizing plate protective film for this part.

The cellulose derivative film of this invention can be used for various uses, and it is especially effective when used as an optical compensation sheet of a liquid crystal display device. 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 Liquld Crystal (AFLC), 0ptically 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 derivative film is effective also in the liquid crystal display device of any display mode. Moreover, it is effective also in any liquid crystal display device of a transmissive type, a reflective type, and a transflective type. You may use the cellulose derivative film of this invention as a support body of the optical compensation sheet of the TN type liquid crystal display device which has the liquid crystal cell of TN mode. You may use the cellulose derivative film of this invention 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 STN type liquid crystal display devices, the rod-like liquid crystalline molecules in the liquid crystal cell are warped in the range of 90 to 360 degrees, and the refractive index anisotropy of the rod-like liquid crystalline molecules and the cell gap are in the range of 300 to 1500 nm. As for the optical compensation sheet used for STN type liquid crystal display device, it describes in Unexamined-Japanese-Patent No. 2000-105316. The cellulose acylate film of this invention is used especially advantageously as a support body of the optical compensation sheet of VA type liquid crystal display device which has a liquid crystal cell of VA mode. The cellulose derivative film of this invention is advantageously used also as a support body of the optical compensation sheet of the OCB type liquid crystal display device which has a liquid crystal cell of OCB mode, or the HAN type liquid crystal display device which has a liquid crystal cell of HAN mode.

The cellulose derivative film of this invention is advantageously used also as an optical compensation sheet of the reflection type liquid crystal display device of TN type, STN type, HAN type, and GH (Guest-Host) type | mold. These display modes have long been well known. Regarding the TN type reflective liquid crystal display device, there is a description in Japanese Unexamined Patent Application Publication Nos. Hei 10-123478, WO 98/48320, and Japanese Patent No. 3024277. As for the optical compensation sheet used for the reflective liquid crystal display device, there is a description in WO00-65384. The cellulose derivative 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 ASM mode has the characteristic that the thickness of the cell is hold | maintained by the resin spacer which can be adjusted.

The other property is the same as that of the TN mode liquid crystal cell. 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 derivative films described above is described in detail on pages 45 to 59 in the Society of the Invention (Publication No. 2001-1745, published March 15, 2001, Invention Association).

(Example)

The features of the present invention will be described in more detail with reference to Examples and Comparative Examples. The materials, the amounts used, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not interpreted limitedly by the specific example shown below.

Synthesis of Compounds Represented by General Formulas (1) to (2)

Synthesis Example 1 Synthesis of Exemplary Compound (1)

Exemplary compound (1) was synthesized according to the following scheme.

[Synthesis of Intermediate (C)]

300 g of 2,4,5-trimethoxybenzoic acid, 1200 ml of toluene, and 12 ml of dimethylformamide were heated to 80 ° C, and 112.1 ml of thionyl chloride was slowly added dropwise for 45 minutes, followed by heating at 80 ° C for 1 hour. Stirred. Then, the solution which melt | dissolved 214.8 g of 4-hydroxybenzoic acid in 800 ml of dimethylformamide was added to the reaction liquid, and also it was made to react at 80 degreeC for 2 hours. After reaction, toluene was distilled off and it cooled to room temperature. Subsequently, 2500 ml of methanol was added and the precipitated crystals were collected by filtration to obtain 263.8 g of an intermediate (C) as a white crystal (yield 56.3%).

[Synthesis of Example Compound (1)]

108.4 g of intermediate (C), 7.24 g of dimethylaminopyridine, 32.67 g of compound (D), and 500 ml of methylene chloride were heated to reflux, and a 200 ml solution of dicyclohexylcarbodiimide 67.31 g of methylene chloride was slowly added dropwise for 30 minutes. And refluxed for 2 hours. Thereafter, the reaction solution was cooled to room temperature, and the precipitated crystals (dicyclohexylurea) were filtered, and the filtrate was concentrated under reduced pressure. The residue was recrystallized three times with methanol to obtain 91.42 g (yield 75.8%) of Exemplary Compound (1) as white crystals. In addition, identification of the compound was performed by ¹ H-NMR (400 MHz).

Synthesis Example 2: Synthesis of Exemplary Compound (31)

Exemplary compound (31) was synthesized according to the following scheme.

[Synthesis of Intermediate (G)]

To a solution of 21.2 g of benzoic acid derivative (E), 11.7 g of ethynylaniline, and 100 ml of methylene chloride, a 50 ml solution of methylene chloride of dicyclohexylcarbodiimide 22.7 g was slowly added dropwise to the solution at room temperature for 2 hours, and further stirred at room temperature for 2 hours. The reaction was carried out under. Then, the precipitated crystal | crystallization (dicyclohexyl urea) was filtered and the filtrate was concentrated under reduced pressure. The residue was recrystallized three times with methanol to obtain 29.79 g (crude yield 95.8%) of the intermediate (G) as white crystals.

[Synthesis of Example Compound (31)]

A solution of 7.0 g of intermediate (G), 9.25 g of compound (H), 0.16 g of PdCl ₂ (PPh ₃ ) ₂ , 0.05 g of copper chloride, 0.3 g of triphenylphosphine, 9.38 g of triethylamine, and 50 ml of tetrahydrofuran The reaction was carried out at room temperature for 2 hours. After the reaction, the mixture was extracted with ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was put into a silica gel column chromatograph to obtain 8.35 g (crude yield 62.3%) of Exemplary Compound (31) as white crystals from ethyl acetate / n-hexane = 2/1. In addition, the compound was identified by ¹ H-NMR (400 MHz).

Preparation of Cellulose Acetate Film

Each component of the following cellulose acetate solution composition was thrown into the mixing tank, it stirred while heating, each component was melt | dissolved, and the cellulose acetate solution was prepared.

(Cellulose acetate solution composition)

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

Triphenyl phosphate (plasticizer) 7.8 parts by mass

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)

In another mixing tank, 16 mass parts of exemplary compound (1), (4), (18), (21), (27), or (31), or a comparative compound, 87 mass parts of methylene chloride, and 13 mass parts of methanol It injected | thrown-in, stirring while heating, and prepared the retardation control agent solution. Moreover, exemplary compound (4), (18), (21), and (27) were synthesize | combined according to the synthesis method of exemplary compound (1) and (31) mentioned above.

36 mass parts of retardation control (elevation) solutions were mixed with 474 mass parts of cellulose acetate solutions, and it fully stirred, and dope was prepared. The retardation control agent added the mass part of Table 1 with respect to 100 mass parts of cellulose acetates.

The obtained dope was cast using a band softener. The film of 15 mass% of residual solvents was lateral stretched at the draw ratio of 20% using the tenter on 130 degreeC conditions, and the cellulose acetate film (thickness: 92 micrometers) was produced. Re and Rth in wavelength 590nm were measured about the produced cellulose acetate film (optical compensation sheet). The results are shown in Table 1.

<Measurement of Re, Rth>

Re was measured by injecting light having a wavelength of 590 nm in the direction of the film normal in KOBRA 21ADH (manufactured by OH Clock Co., Ltd.). Rth is the retardation value measured by injecting the light of wavelength 590nm from the direction inclined +40 degree with respect to the film normal direction using said Re, the in-plane slow axis (determined by KOBRA 21ADH) as a tilt axis (rotation axis), And a retardation value and an average refractive index measured in a total of three retardation values measured by injecting light having a wavelength of 590 nm from a direction inclined at -40 ° to the film normal direction using the in-plane slow axis as the inclination axis (rotation axis). It was calculated based on the hypothesis value and the input film thickness value.

No additive Addition mass part Re (nm) Rth (nm) Remarks One none 0 2 50 Comparative example 2 Comparative compound 2 20 115 Comparative example 3 Comparative compound 5 38 180 Invention 4 Exemplary Compound (1) 2 39 140 Invention 5 Exemplary Compound (1) 5 85 254 Invention 6 Exemplary Compound (4) 2 40 142 Invention 7 Exemplary Compounds (18) 2 43 155 Invention 8 Exemplary Compounds (21) 2 43 152 Invention 9 Exemplary Compounds (27) 2 33 154 Invention 10 Exemplary Compounds (31) 2 35 152 Invention 11 Exemplary Compounds (31) 3.5 56 216 Invention

Comparative compound (compound described in Patent Document 2)

From Table 1, the film which does not contain a comparative compound, the film containing 2 mass parts of comparative compounds, and the film containing 5 mass parts of comparative compounds are all

Rth = Re × 3.6 + 43 (Equation 1)

It can be seen that Re and Rth are expressed depending on the amount of the compound added. It is assumed that the same formula is derived even when other known comparative compounds are used.

Although the film containing a comparative compound expresses Re by changing draw ratio, it is known that Rth does not change very much. Therefore, the film produced at the draw ratio smaller than the draw ratio (20%) of this example is obtained by adding a comparative compound,

Rth≥Re × 3.6 + 43 (Equation 2)

It can be seen that the film satisfies the optical characteristics of the region of.

Meanwhile,

Rth <Re × 3.6 + 43 (Equation 3)

In order to obtain a film that satisfies the optical properties of the region, it is necessary to increase the draw ratio to a magnification higher than 20%. In general, the cellulose acylate film is difficult to increase the draw ratio, and the comparative compound satisfy this region. Is not easy.

On the other hand, it can be seen that by adding the compound represented by the general formula (1), a novel cellulose derivative film (region of formula 3) having a larger Re expressionability that was not realized in the film to which the comparative compound was added can be produced. have.

As can be seen from the results in Table 1, by adding the compounds represented by the general formulas (1) to (2), the higher Re expressionability, which was not realized in the known disk-shaped compound (comparative compound), was higher. The production of a novel cellulose derivative film having optical properties of the region was made possible.

The cellulose derivative film of this invention can be used suitably as an optical film for liquid crystal display devices especially as an optical compensation sheet.

Claims (6)

It contains at least 1 type of compound represented by following General formula (1), The cellulose derivative composition characterized by the above-mentioned. In general formula (1)

(Wherein Ar ¹ and Ar ³ each independently represent an aryl group or an aromatic hetero ring, Ar ² represents an arylene group or an aromatic hetero ring, and L ¹ , L ² each independently represent a single bond or a divalent linking group) N represents an integer of 3 or more, and Ar ² and L ² may be the same or different, respectively.) The cellulose derivative composition according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2). In general formula (2)

(Wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom or a substituent. Ar ² represents an arylene group or An aromatic hetero ring, L ² and L ³ each independently represent a single bond or a divalent linking group, n represents an integer of 3 or more, and Ar ² and L ² may be the same or different.) The cellulose derivative composition according to claim 1 or 2, wherein cellulose acylate is contained as the cellulose derivative. The cellulose derivative film which consists of a cellulose derivative composition of Claim 1 or 2. The compound represented by following General formula (2). In general formula (2)

(Wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom or a substituent. Ar ² represents an arylene group or An aromatic hetero ring, L ² and L ³ each independently represent a single bond or a divalent linking group, n represents an integer of 3 or more, and Ar ² and L ² may be the same or different.) The cellulose derivative film which consists of a cellulose derivative composition of Claim 3.