JP4480602B2 - Cellulose acylate composition, cellulose acylate film, and alkoxybenzoic acid compound - Google Patents

Description

The present invention relates to a cellulose acylate composition and a cellulose acylate film comprising the cellulose acylate composition. The present invention further relates to a novel trialkoxy benzoic acid compound and novel dialkoxy benzoic acid compound.

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

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

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

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

European Patent Application No. 0911656A2 JP 2003-344655 A

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

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

(Wherein R ¹ represents a hydrogen atom or an alkoxy group, R ² and R ⁵ each independently represents a hydrogen atom, an alkyl group or an alkoxy group, and R ⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or Represents an alkoxy group having 1 to 12 carbon atoms , R ¹³ represents an alkyl group containing one or more heteroatoms, L represents a single bond or —O— , Ar represents an aryl group or an aromatic heterocyclic group; To express.)
[2] The cellulose acylate composition according to item [1], wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

(Wherein R ² and R ⁵ each independently represents a hydrogen atom , an alkyl group or an alkoxy group , R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹³ represents one or more heteroatoms. Represents an alkyl group to be contained, L represents a single bond or —O— , and Ar represents an aryl group or an aromatic heterocyclic group.
[3] The cellulose acylate composition as described in the item [1], wherein the compound represented by the general formula (1) is a compound represented by the following general formula (3).

(Wherein R ² and R ⁵ each independently represents a hydrogen atom alkyl group or an alkoxy group , R ¹¹ and R ¹⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹³ represents hetero An alkyl group containing one or more atoms is represented, L represents a single bond or —O— , and Ar represents an aryl group or an aromatic heterocyclic group.
[4] The cellulose acylate of any one of [1] to [3], wherein the compound represented by the general formula (1) is a compound represented by the following general formula (4): Composition.

(Wherein R ²¹ represents a hydrogen atom or an alkoxy group, R ²² and R ²⁵ each independently represents a hydrogen atom , an alkyl group or an alkoxy group , and R ²⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, R ⁴³ represents an alkyl group containing one or more hetero atoms, L ¹ represents a single bond or -O-, L ² is a single bond, -CONH -, - NHCO-, -COO-, -OCO- or an alkynylene group , Ar ¹ represents an arylene group or an aromatic heterocyclic group, Ar ² represents an aryl group or an aromatic heterocyclic group, and n is 1 or more The n L ^{2 s} may be the same or different, and the n Ar ^{1 s} may be the same or different.)
[5] In the general formula (4), R ²¹ represents —OR ⁴¹ (R ⁴¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), and R ²⁴ represents a hydrogen atom. The cellulose acylate composition according to item [4].
[6] In the general formula (4), R ²¹ represents —OR ⁴¹ and R ²⁴ represents —OR ⁴⁴ (R ⁴¹ and R ⁴⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). The cellulose acylate composition according to item [4], wherein
[7] The cellulose acylate composition according to any one of [4] to [6], wherein in the general formula (4), n is an integer of 3 or more.
[ 8 ] A cellulose acylate film comprising the cellulose derivative composition according to any one of [1] to [ 7 ].
[ 9 ] A compound represented by the following general formula (4-A).

( Wherein R ⁴³ represents an alkyl group containing one or more heteroatoms, R ⁴¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L ¹ represents a single bond or —O—, ² represents a single bond , —CONH—, —NHCO—, —COO—, —OCO— or an alkynylene group , Ar ¹ represents an arylene group or an aromatic heterocyclic group, and Ar ² represents an aryl group or an aromatic group. Represents a telocyclic group, n represents an integer of 1 or more, n L ^{2 s} may be the same or different, and n Ar ^{1 s} may be the same or different .)
[ 10 ] A compound represented by the following general formula (4-B).

(In the formula , R ⁴³ represents an alkyl group containing one or more hetero atoms, R ⁴¹ and R ⁴⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and L ¹ represents a single bond or — represents O- and, L ² represents a single bond, -CONH -, - NHCO -, - COO -, - OCO- or .Ar ¹ representing the alkynylene group represents a heterocyclic group an arylene group or an aromatic, Ar ² is An aryl group or an aromatic heterocyclic group, n represents an integer of 1 or more, n L ^{2 s} may be the same or different, and n Ar ^{1 s} are the same May be different.)
[ 11 ] A polarizing plate in which a protective film is bonded to both surfaces of a polarizer, wherein at least one of the protective films is the cellulose acylate film described in the item [ 8 ].
[ 12 ] The polarizing plate as described in the item [ 11 ], having an optically anisotropic layer on at least one surface of the protective film.
[ 13 ] A liquid crystal having a liquid crystal cell and two polarizing plates arranged on both sides thereof, wherein at least one of the polarizing plates is the polarizing plate described in the item [ 11 ] or [ 12 ]. Display device.
[ 14 ] The liquid crystal display device according to [ 13 ], wherein the liquid crystal display device is in a VA mode.
[ 15 ] The liquid crystal display device according to item [ 13 ], wherein the liquid crystal display device is in an OCB mode.

The cellulose acylate composition of the present invention is useful for forming a film excellent in optical performance that satisfies both individually specified Re value and Rth value. Therefore, the cellulose acylate film obtained from this is excellent in optical performance.
The cellulose acylate film of the present invention can be suitably used as an optical film for liquid crystal display devices, particularly as an optical compensation sheet.

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

The cellulose acylate composition of the present invention contains cellulose acylate as an essential component, and contains at least one compound represented by the following general formula (1).
[Benzoic acid compound]
First, the compound represented by the general formula (1) of the present invention will be described in detail.

(Wherein R ¹ represents a hydrogen atom or an alkoxy group, R ² and R ⁵ each independently represents a hydrogen atom, an alkyl group or an alkoxy group, and R ⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or Represents an alkoxy group having 1 to 12 carbon atoms , R ¹³ represents an alkyl group containing one or more heteroatoms, L represents a single bond or —O— , Ar represents an aryl group or an aromatic heterocyclic group; To express.)

In the general formula (1), R ¹ represents a hydrogen atom or an alkoxy group, R ² and R ⁵ each independently represent a hydrogen atom, an alkyl group or an alkoxy group, and R ⁴ represents a hydrogen atom, which has 1 to 4 carbon atoms. to display the alkyl or alkoxy group having 1 to 12 carbon atoms.

Preferably the R ¹ is a main butoxy group.

R ² is water atom, an alkyl group (preferably having from 1 to 4 carbon atoms, more preferably methyl group.), Or an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, More preferably, it is C1-C6, Most preferably, it is C1-C4. Particularly preferred are a hydrogen atom, a methyl group and a methoxy group, and most preferred is a hydrogen atom.

R ⁴ is, water atom, an alkyl group having 1 to 4 carbon atoms or alkoxy group having 1 to 12 carbon atoms (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, more preferably 1 carbon atoms To 6, particularly preferably 1 to 4 carbon atoms, particularly preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, most preferably a hydrogen atom or a methoxy group. is there.

R ⁵ is, water atom, an alkyl group (preferably having from 1 to 4 carbon atoms, more preferably methyl group.), Or an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, More preferably, it is C1-C6, Most preferably, it is C1-C4. Particularly preferred are a hydrogen atom, a methyl group and a methoxy group. Most preferably, it is a hydrogen atom.

R ¹³ represents an alkyl group containing one or more heteroatoms. A hetero atom represents an atom other than a hydrogen atom or a carbon atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, phosphorus, silicon, a halogen atom (F, Cl, Br, I), and boron. Among these, atoms preferably used are N, O, S, F, Cl, and Si, more preferably N, O, and S, and most preferably N and O.
If one or more heteroatoms are contained in R ¹³ , the present invention falls within the scope of the present invention, but two or more heteroatoms may be contained. In this case, even if it contains different heteroatoms, it may contain a plurality of one kind of heteroatoms, both of which are preferably used.

The alkyl group represented by R ¹³ may contain at least one hetero atom, preferably has 1 to 30 carbon atoms, more preferably has 1 to 20 carbon atoms, and 2 to 20 carbon atoms. Most preferably.

Although the preferable example of a substituent represented by R < ¹³ > below is shown, this invention is not limited to these. The substituent represented in the following example is linked to the oxygen atom at the # portion.

L represents a single bond or represents -O-.

  Ar represents an aryl group or an aromatic heterocyclic group. The aryl group represented by Ar is preferably an aryl group having 6 to 50 carbon atoms and may be a single ring or may form a condensed ring with another ring. Further, if possible, it may have a substituent, and the substituent T described later can be applied as the substituent. More preferably, the aryl group represented by Ar has 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

  In the general formula (1), the aromatic heterocyclic group represented by Ar may be an aromatic heterocyclic group containing at least one of an oxygen atom, a nitrogen atom or a sulfur atom, and preferably 5 to 6 An aromatic heterocyclic group containing at least one of a member ring oxygen atom, nitrogen atom or sulfur atom. Moreover, you may have a substituent further if possible. Substituent T described later can be applied as the substituent.

  In the general formula (1), specific examples of the aromatic heterocyclic ring represented by Ar include, for example, furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, Indole, indazole, purine, thiazoline, thiazole, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, Examples include benzthiazole, benzotriazole, tetrazaindene, pyrrolotriazole, and pyrazolotriazole. For example, a hydrogen atom of these aromatic heterocyclic rings is removed to give the aromatic heterocyclic group described above. Preferred as the aromatic heterocycle are benzimidazole, benzoxazole, benzthiazole, and benzotriazole.

The compound represented by the general formula (1) is any of the following general formulas (2) to (5) or (4-A), (4-B), (5-A) or (5-B). It is more preferable that it is a compound represented by.
Next, the compound represented by the general formula (2) will be described.

(Wherein R ² and R ⁵ each independently represents a hydrogen atom , an alkyl group or an alkoxy group , R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹³ represents one or more heteroatoms. Represents an alkyl group to be contained, L represents a single bond or —O— , and Ar represents an aryl group or an aromatic heterocyclic group.

In general formula (2), R ² , R ⁵ , R ¹³ , L and Ar have the same meanings as those in general formula (1), and the preferred ranges are also the same.
R ¹¹ is also hydrogen atom is an alkyl group having a carbon number of 1 to 4, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably methyl group.
Next, the compound represented by the general formula (3) will be described.

(Wherein R ² and R ⁵ each independently represents a hydrogen atom alkyl group or an alkoxy group , R ¹¹ and R ¹⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹³ represents hetero An alkyl group containing one or more atoms is represented, L represents a single bond or —O— , and Ar represents an aryl group or an aromatic heterocyclic group.

In general formula (3), R ² , R ⁵ , R ¹³ , L and Ar have the same meanings as those in general formula (1), and the preferred ranges are also the same.
R ^11, R ¹⁴ each independently or hydrogen atom is an alkyl group having a carbon number of 1 to 4, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably methyl group. R ¹¹ and R ¹⁴ may be the same or different, but both are particularly preferably methyl groups.
Next, the compound represented by the general formula (4) will be described.

(Wherein R ²¹ represents a hydrogen atom or an alkoxy group, R ²² and R ²⁵ each independently represents a hydrogen atom , an alkyl group or an alkoxy group , and R ²⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a carbon number) represents from 1 to 12 alkoxy group, R ⁴³ represents an alkyl group containing one or more hetero atoms, L ¹ represents a single bond or -O-, L ² is a single bond, -CONH -, - NHCO- , —COO—, —OCO— or an alkynylene group , Ar ¹ represents an arylene group or an aromatic heterocyclic group, Ar ² represents an aryl group or an aromatic heterocyclic group, and n is an integer of 1 or more And n L ^{2 s} may be the same or different, and n Ar ^{1 s} may be the same or different.

R ²¹ represents a hydrogen atom or an alkoxy group, R ²² and R ²⁵ each independently represent a hydrogen atom, an alkyl group or an alkoxy group, and R ²⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 12 carbon atoms. Represents an alkoxy group.
Preferable examples of R ²¹ , R ²² , R ²⁴ and R ²⁵ are shown. R ²¹ is the same as that shown as a preferred example of R ^{1 in} the general formula (1). R ²² is the same as that shown as a preferred example of R ^{2 in} the general formula (1). R ²⁴ is the same as that shown as a preferred example of R ^{4 in} the general formula (1). R ²⁵ is the same as that shown as a preferred example of R ^{5 in} the general formula (1).

Ar ¹ represents a heterocyclic group an arylene group or an aromatic, (Ar ¹ -L ²⁾ Ar ¹ in the repeating unit represented by _n may all be different from each be the same. Ar ² represents an aryl group or an aromatic heterocyclic group.
In the general formula (4), the arylene group represented by Ar ¹ is preferably an arylene group having 6 to 30 carbon atoms, which may be a single ring or may form a condensed ring with another ring. Good. Further, if possible, it may have a substituent, and the substituent T described later can be applied as the substituent. More preferably, the arylene group represented by Ar ¹ has 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include a phenylene group, a p-methylphenylene group, and a naphthylene group.
In general formula (4), the aryl group represented by Ar ² is preferably an aryl group having 6 to 30 carbon atoms, which may be a single ring or may form a condensed ring with another ring. Good. Further, if possible, it may have a substituent, and the substituent T described later can be applied as the substituent. The aryl group represented by Ar ² has more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include a phenyl group, a p-methylphenyl group, and a naphthyl group.

In the general formula (4), the aromatic heterocyclic group represented by Ar ¹ or Ar ² may be an aromatic heterocyclic group containing at least one of an oxygen atom, a nitrogen atom or a sulfur atom, Is an aromatic heterocyclic group containing at least one of a 5- to 6-membered ring oxygen atom, nitrogen atom or sulfur atom. Moreover, you may have a substituent further if possible. Substituent T described later can be applied as the substituent. Specific examples of the aromatic heterocyclic group are the same as those shown as the example of Ar in the general formula (1).

In the general formula (4), L ¹ represents a single bond or -O-, L ² is a single bond, -CONH -, - NHCO -, - COO -, - OCO- or an alkynylene group. (Ar ¹ -L ²⁾ L ² in the repeating unit represented by _n, all be the same but it may also be different.

In the compound represented by the general formula (4) used in the present invention, Ar ¹ is bonded to L ¹ and L ^2, and when Ar ¹ is a phenylene group, -L ¹ -Ar ¹ -L ^2- , and -L ² -Ar ¹ -L ² - is most preferably in the relation of mutually para position (1,4-position).
In general formula (4), n represents an integer greater than or equal to 1, Preferably it is 1-7, More preferably, it is 2-7, More preferably, it is 3-6.
Among the compounds represented by the general formula (4), those in which n is 3 or more have a longer portion represented by (—Ar ¹ -L ² —) _n , compared with conventional compounds having the same structure. The cellulose acylate film has a higher retardation development ability. Further, it is possible to realize a high solubility of cellulose acylate composition by containing a hetero atom in R ^43.

  The compound represented by the general formula (4) is more preferably a compound represented by the following general formula (4-A) or general formula (4-B).

( Wherein R ⁴³ represents an alkyl group containing one or more heteroatoms, R ⁴¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L ¹ represents a single bond or —O—, ² represents a single bond , —CONH—, —NHCO—, —COO—, —OCO— or an alkynylene group , Ar ¹ represents an arylene group or an aromatic heterocyclic group, and Ar ² represents an aryl group or an aromatic group. Represents a telocyclic group, n represents an integer of 1 or more, n L ^{2 s} may be the same or different, and n Ar ^{1 s} may be the same or different .)

In general formula (4-A), R ²² , R ²⁵ , R ⁴³ , L ¹ , L ² , Ar ¹ , Ar ² and n have the same meanings as those in general formula (4), and the preferred ranges are also the same. is there.
R ⁴¹ is also hydrogen atom is an alkyl group having a carbon number of 1 to 4, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably methyl group.

(In the formula , R ⁴³ represents an alkyl group containing one or more hetero atoms, R ⁴¹ and R ⁴⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and L ¹ represents a single bond or — represents O- and, L ² represents a single bond, -CONH -, - NHCO -, - COO -, - OCO- or .Ar ¹ representing the alkynylene group represents a heterocyclic group an arylene group or an aromatic, Ar ² is An aryl group or an aromatic heterocyclic group, n represents an integer of 1 or more, n L ^{2 s} may be the same or different, and n Ar ^{1 s} are the same May be different.)

In general formula (4-B), R ²² , R ²⁵ , R ⁴³ , L ¹ , L ² , Ar ¹ , Ar ² and n have the same meanings as those in general formula (4), and the preferred ranges are also the same. is there.
R ^41, R ⁴⁴ each independently or hydrogen atom is an alkyl group having a carbon number of 1 to 4, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably methyl group.

  The compound represented by the general formula (4) is more preferably a compound represented by any of the following general formula (5), general formula (5-A), or general formula (5-B).

(Wherein R ²¹ represents a hydrogen atom or an alkoxy group, R ²² and R ²⁵ each independently represents a hydrogen atom , an alkyl group or an alkoxy group , and R ²⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a carbon number) 1 to 12 alkoxy groups , R ⁴³ represents an alkyl group containing one or more heteroatoms, and L ¹ represents a single bond, —O—, —CONH—, —NHCO—, —COO—, —OCO—. Or an alkynylene group, L ² represents a single bond, —O— or —NH— , Ar ¹ represents an arylene group or an aromatic heterocyclic group, n represents an integer of 1 or more, and n L ¹ may be the same or different, and n Ar ¹ may be the same or different.

In the general formula (5), R ²¹ , R ²² , R ²⁴ , R ²⁵ , R ⁴³ , A r ¹ and n have the same meanings as those in the general formula (4), and preferred ranges are also the same.

Wherein R ²² and R ²⁵ each independently represent a hydrogen atom , an alkyl group or an alkoxy group , R ⁴³ represents an alkyl group containing one or more heteroatoms, and R ⁴¹ represents a hydrogen atom or an alkyl group. , L ¹ is a single bond, -O -, - CONH -, - NHCO -, - COO -, - OCO- or an alkynylene group, L ² represents a single bond, .Ar ¹ representing -O- or -NH- Represents an arylene group or an aromatic heterocyclic group, n represents an integer of 1 or more, n L ^{1 s} may be the same or different, and n Ar ^{1 s} are the same. Or different.)

In general formula (5-A), R ²² , R ²⁵ , R ⁴³ , A r ¹ and n have the same meanings as those in general formula (4), and the preferred ranges are also the same.
R ⁴¹ each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, still more preferably. Is a methyl group.

(Wherein R ²² and R ²⁵ each independently represents a hydrogen atom , an alkyl group or an alkoxy group , R ⁴³ represents an alkyl group containing one or more heteroatoms, and R ⁴¹ and R ⁴⁴ each independently represents a hydrogen atom) L ¹ represents a single bond, —O—, —CONH—, —NHCO—, —COO—, —OCO— or an alkynylene group, and L ² represents a single bond, —O— or —NH. - .Ar ¹ representing a represents a heterocyclic group an arylene group or an aromatic, n represents an integer of 1 or more, n number of L ¹ may be the each be the same or different, n groups of Ar ¹ may be the same or different.

In general formula (5-B), R ²² , R ²⁵ , R ⁴³ , Ar ¹ and n have the same meanings as those in general formula (4), and the preferred ranges are also the same.
R ⁴¹ and R ⁴⁴ each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. More preferably, it is a methyl group.

The aforementioned substituent T will be described below.
The substituent T is preferably a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group. , Isopropyl group, t-butyl group, n-octyl group, 2-ethylhexyl group), cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group), a bicycloalkyl group (preferably, a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group in which one hydrogen atom is removed from a bicycloalkane having 5 to 30 carbon atoms. For example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octa 3-yl),

An alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as a vinyl group or an allyl group), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, That is, it 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), bicycloalkenyl group (substituted or unsubstituted). A substituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] oct-2-en-4-yl), alkyl Le group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl group, propargyl group),

An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, a p-tolyl group, a naphthyl group), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic group A monovalent group obtained by removing one hydrogen atom from an aromatic or non-aromatic heterocyclic compound, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably substituted or unsubstituted having 1 to 30 carbon atoms) Alkoxy groups such as methoxy group, ethoxy group, isopropoxy group, t-butoxy group, n-octyloxy group, 2-methoxyethoxy group), aryloxy group Preferably, it is a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy. Group),

A silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy group or tert-butyldimethylsilyloxy group), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocycle having 2 to 30 carbon atoms) Ring oxy group, 1-phenyltetrazole-5-oxy group, 2-tetrahydropyranyloxy group), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, carbon number 6-30 substituted or unsubstituted arylcarbonyloxy groups such as formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group), carbamoyloxy group (preferably Or substitution of 1 to 30 carbon atoms Is an unsubstituted carbamoyloxy group, for example, N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn -Octylcarbamoyloxy group), alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, methoxycarbonyloxy group, ethoxycarbonyloxy group, tert-butoxycarbonyloxy group, n- Octylcarbonyloxy group), aryloxycarbonyloxy group (preferably substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group) , P-n-hexadecyloxycarbonyl phenoxycarbonyl group),

An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as an amino group, a methylamino group, a dimethylamino group; , Anilino 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 6 to 30 carbon atoms, or Unsubstituted arylcarbonylamino group, for example, formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group), aminocarbonylamino group (preferably substituted or unsubstituted amino acid having 1 to 30 carbon atoms) Carbonylamino group, for example, carbamoylamino group, N, N-dimethylamino Sulfonylamino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group), alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino group, ethoxycarbonyl) Amino group, tert-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group), aryloxycarbonylamino group (preferably substituted or unsubstituted aryloxy having 7 to 30 carbon atoms) Carbonylamino group, for example, phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxycarbonylamino group),

Sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms such as sulfamoylamino group, N, N-dimethylaminosulfonylamino group, Nn-octylamino Sulfonylamino groups), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino groups having 6 to 30 carbon atoms, such as methylsulfonylamino) Group, butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group), mercapto group, alkylthio group (preferably substituted with 1 to 30 carbon atoms or Unsubstituted alkylthio groups such as meth Thio group, ethylthio group, n-hexadecylthio group), arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, such as phenylthio group, p-chlorophenylthio group, m-methoxyphenylthio group), A heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, for example, 2-benzothiazolylthio group, 1-phenyltetrazol-5-ylthio group),

Sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group N-acetylsulfamoyl group, N-benzoylsulfamoyl group, N- (N′-phenylcarbamoyl) sulfamoyl group), sulfo group, alkyl and arylsulfinyl group (preferably having 1 to 30 carbon atoms substituted or Unsubstituted alkylsulfinyl groups, 6-30 substituted or unsubstituted arylsulfinyl groups such as methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group, p-methylphenylsulfinyl group), alkyl and arylsulfonyl groups (preferably , A device having 1 to 30 carbon atoms Or unsubstituted alkylsulfonyl group, 6 to 30 or a substituted or unsubstituted arylsulfonyl group, for example, methylsulfonyl group, ethylsulfonyl group, phenylsulfonyl group, p- methylphenyl sulfonyl group),

An acyl group (preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, such as an acetyl group or a pivaloylbenzoyl group), Aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, p-tert-butylphenoxy Carbonyl group), alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, n-octadecyloxycarbonyl group), carbamoyl Base Preferably, the substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, for example, carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- (Methylsulfonyl) carbamoyl group),

Aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, such as phenylazo group, p-chlorophenylazo group, 5-ethylthio-1,3,4-thiadiazol-2-ylazo group), imide group (preferably N-succinimide group, N-phthalimide group), phosphino group (preferably substituted or non-substituted having 2 to 30 carbon atoms) Substituted phosphino groups such as dimethylphosphino group, diphenylphosphino group, methylphenoxyphosphino group), phosphinyl groups (preferably substituted or unsubstituted phosphinyl groups having 2 to 30 carbon atoms such as phosphinyl group, dioctyl Oxyphosphinyl group, diethoxyphosphinyl group), phosphinyloxy group (preferred Or a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as a diphenoxyphosphinyloxy group or a dioctyloxyphosphinyloxy group, or a phosphinylamino group (preferably having a carbon number) 2-30 substituted or unsubstituted phosphinylamino groups such as dimethoxyphosphinylamino group, dimethylaminophosphinylamino group, silyl groups (preferably substituted or unsubstituted groups having 3 to 30 carbon atoms) Silyl group, for example, trimethylsilyl group, tert-butyldimethylsilyl group, phenyldimethylsilyl group).

Among the above-mentioned substituents, those having a hydrogen atom may be substituted with the above-mentioned group after removing this. Examples of such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.
Moreover, when there are two or more substituents, they may be the same or different. If possible, they may be linked together to form a ring.

Preferred compounds represented by the general formula (5) are
R ²¹ is a methoxy group,
R ²² and R ²⁵ are both hydrogen atoms,
R ²⁴ is a hydrogen atom or a methoxy group,
R ⁴³ is an alkyl group containing one or more heteroatoms,
L ¹ is a single bond, —O—, —CONH—, —NHCO—, —COO—, —OCO— , and an alkynylene group ,
L ² is —O— or —N H— ;
Ar ¹ is an arylene group,
The thing whose n is 3-6 is mentioned.

  Specific examples of the compound represented by any one of the general formulas (1) to (5) or (4-A), (4-B), (5-A) or (5-B) are shown below. The present invention is not limited by the following specific examples.

The compound represented by the general formula (1) used in the present invention can be synthesized by first synthesizing a substituted benzoic acid and then performing a general ester reaction or amidation reaction of the substituted benzoic acid and a phenol derivative or aniline derivative. Any reaction can be used as long as it is an ester bond or amide bond forming reaction. For example, a method of converting a substituted benzoic acid to an acid halide and then condensing it with a phenol derivative or aniline derivative, a method of dehydrating and condensing a substituted benzoic acid with a phenol derivative or aniline derivative using a condensing agent or catalyst, etc. It is done.
In view of the production process and the like, a method in which a substituted benzoic acid is functionally converted to an acid halide and then condensed with a phenol derivative or aniline derivative is preferred.

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

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

（式中、Ａは水酸基、ハロゲン原子等の反応性基を表し、Ｒ²¹、Ｒ²²、Ｒ⁴³、Ｒ²⁴、およびＲ²⁵は先に記載した通りである。）
を有する原料化合物を、水酸基、アミノ基等の反応性部位を有する誘導体との反応に付して得られた中間体：

（式中、Ａ’はカルボキシル基等の反応性基を表し、Ｒ²¹、Ｒ²²、Ｒ⁴³、Ｒ²⁴、Ｒ²⁵、Ａｒ¹、およびＬ¹は先に記載した通りである。）
２分子を、

（式中、ＢおよびＢ’は水酸基、アミノ基等の反応性基を表し、Ａｒ²およびＬ²は先に記載したＡｒ¹、Ｌ¹と同義である。）
１分子により連結することによって得ることができる。ただし、本発明に用いられる化合物の合成法はこの例に限定されない。 The compound represented by the general formula (5) can be synthesized by a known method. For example, in the case of a compound where n = 4, the following structure:

(In the formula, A represents a reactive group such as a hydroxyl group or a halogen atom, and R ²¹ , R ²² , R ⁴³ , R ²⁴ , and R ²⁵ are as described above.)
An intermediate obtained by subjecting a raw material compound having a reaction with a derivative having a reactive site such as a hydroxyl group or an amino group:

(In the formula, A ′ represents a reactive group such as a carboxyl group, and R ²¹ , R ²² , R ⁴³ , R ²⁴ , R ²⁵ , Ar ¹ , and L ¹ are as described above.)
2 molecules

(In the formula, B and B ′ represent a reactive group such as a hydroxyl group and an amino group, and Ar ² and L ² have the same meanings as Ar ¹ and L ¹ described above.)
It can be obtained by linking by one molecule. However, the synthesis method of the compound used in the present invention is not limited to this example.

The compound represented by any one of the general formulas (1) to (5) or (4-A), (4-B), (5-A) or (5-B) in the cellulose acylate composition of the present invention. Is preferably 0.1 to 20% by mass, more preferably 0.5 to 16% by mass, still more preferably 1 to 12% by mass, and particularly preferably 1 to 8% by mass with respect to cellulose acylate. %.

The compound represented by any one of the general formulas (1) to (5) or (4-A), (4-B), (5-A) or (5-B) is a retardation control for an optical film. In particular, it can be suitably used as a retardation control agent for obtaining a film having excellent Re developability by stretching. The compound represented by any one of the general formulas (1) to (5) or (4-A), (4-B), (5-A) or (5-B) is particularly a cellulose acylate film letter. Useful as a foundation control agent. Details of a method for producing a film containing these compounds will be described later.

[Cellulose acylate composition]
The cellulose acylate composition of the present invention comprises cellulose acylate (cellulose triacylate, cellulose acylate propionate, etc.) and the general formulas (1) to (5) or (4-A), (4- B), a composition containing at least one selected from compounds represented by any one of (5-A) and (5-B) . But it may also be used as a mixture two or more different cellulose acylate in the present invention.

Good Masui cellulose acylate mention may be made of the following materials. That is, the cellulose acylate is a cellulose acylate in which the degree of substitution of the hydroxyl group 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 in the formula represent a substituent of an acyl group substituted with a hydroxyl group of cellulose, SA is a substitution degree of an acetyl group, and SB is a substitution degree of an acyl group having 3 to 22 carbon atoms. . Glucose units having β-1,4 bonds constituting cellulose have free hydroxyl groups at the 2nd, 3rd and 6th positions. Cellulose acylate is a polymer obtained by esterifying some or all of these hydroxyl groups with acyl groups. The degree of acyl substitution means the proportion of cellulose esterified at each of the 2-position, 3-position and 6-position (100% esterification has a degree of substitution of 1). In the cellulose acylate used in the present invention, the total substitution degree of the hydroxyl groups SA and SB is more preferably 1.50 to 2.96, and particularly preferably 2.00 to 2.95. Further, the substitution degree of SB is 0 to 1.5, particularly 0 to 1.0. Further, SB is preferably 28% or more of the substituent group of the 6-position hydroxyl group, more preferably 30% or more is the substituent of the 6-position hydroxyl group, more preferably 35% or more, and particularly preferably 40% or more. It is also preferable that the substituent is a 6-position hydroxyl group. Furthermore, cellulose acylate having a total substitution degree of SA and SB at the 6-position of cellulose acylate of 0.8 or more, more preferably 0.85 or more, and particularly 0.90 or more may be used. it can.

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

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

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

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

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

  In addition, when manufacturing a cellulose acylate with few low molecular components, it is preferable to adjust the sulfuric acid catalyst amount in an acetylation reaction to 0.5-25 mass parts with respect to 100 mass of cellulose. When the amount of the sulfuric acid catalyst is in the above range, cellulose acylate that is preferable in terms of molecular weight distribution (uniform molecular weight distribution) can be synthesized. The water content of the cellulose acylate used in the present invention is preferably 2% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.7% by mass or less. In general, cellulose acylate contains water and is known to have a water content of 2.5 to 5% by mass. In the present invention, in order to obtain a cellulose acylate having a low moisture content, the cellulose acylate may be dried, and the method is not particularly limited as long as the desired moisture content (for example, 2% by mass or less) can be obtained.

  As for these cellulose acylates that can be used in the present invention, the raw material cotton and the synthesis method thereof are disclosed on the 7th to 12th pages of the Japan Society for Invention and Technology (Publication No. 2001-1745, published on March 15, 2001, Japan Society of Inventions). It is described in detail on the page.

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

Cellulose acylate composition of the present invention, cellulose acylate and the general formula (1) to (5) or (4-A), (4 -B), any one of (5-A) or (5-B) In addition to the compounds represented by the formula, various additives (for example, plasticizers, UV inhibitors, deterioration inhibitors, optical anisotropy control agents, fine particles, release agents, infrared absorptions) in each preparation step. Agents, etc.), which may be solid or oily. That is, the melting point and boiling point are not particularly limited. For example, mixing of ultraviolet absorbing material at 20 ° C. or lower and 20 ° C. or higher, and similarly, mixing of a plasticizer is described in, for example, JP-A-2001-151901. Furthermore, infrared absorbing dyes are described, for example, in JP-A No. 2001-194522. Moreover, the addition time may be added at any time in the dope preparation step, but may be added by adding an additive to the final preparation step of the dope preparation step.

Furthermore, the amount of each material added is not particularly limited as long as the function is manifested. Moreover, if the cellulose acylate film comprising a cellulose acylate composition of the present invention is formed of plural layers, the kind and amount of additives in the various layers may be different. For example, it is described in Japanese Patent Application Laid-Open No. 2001-151902, but these are conventionally known techniques.

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

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

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

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

The non-chlorine organic solvent used for dissolving the above cellulose acylate is selected from the various viewpoints described above, and is preferably as follows. That is, in the present invention, a preferable solvent used for dissolving cellulose acylate is a mixed solvent of three or more different from each other, and the first solvent is methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, dioxolane, It is at least one selected from dioxane or a mixture thereof, and the second solvent is selected from ketones having 4 to 7 carbon atoms or acetoacetate, and the third solvent has 1 to 10 carbon atoms. Selected from alcohols and hydrocarbons, more preferably alcohols having 1 to 8 carbon atoms.

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

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

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

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

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

-Methyl acetate / acetone / methanol / ethanol / butanol (75/10/5/5/5, parts by mass),
-Methyl acetate / acetone / methanol / ethanol / propanol (75/10/5/5/5, parts by mass),
Methyl acetate / acetone / methanol / butanol / cyclohexane (75/10/5/5/5, parts by mass),
・ Methyl acetate / acetone / ethanol / butanol (81/8/7/4, parts by mass)
・ Methyl acetate / acetone / ethanol / butanol (82/10/4/4, parts by mass)
・ Methyl acetate / acetone / ethanol / butanol (80/10/4/6, part by mass)
Methyl acetate / methyl ethyl ketone / methanol / butanol (80/10/5/5, parts by mass),

Methyl acetate / acetone / methyl ethyl ketone / ethanol / isopropanol (68/10/10/5/7, parts by mass),
Methyl acetate / cyclopentanone / methanol / isopropanol (77/10/5/8, parts by mass)
・ Methyl acetate / acetone / butanol (90/5/5, part by mass),
Methyl acetate / cyclopentanone / acetone / methanol / butanol (59/15/15/5/6, 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, parts by mass),
Methyl acetate / dioxane / acetone / methanol / ethanol (60/20/10/5/5, parts by mass),
Methyl acetate / acetone / cyclopentanone / ethanol / isobutanol / cyclohexane (65/10/10/5/5/5, parts by mass),
Methyl formate / methyl ethyl ketone / acetone / methanol / ethanol (50/20/20/5/5, parts by mass),
-Methyl formate / acetone / ethyl acetate / ethanol / butanol / hexane (65/10/10/5/5/5, parts by mass)

Acetone / methyl acetoacetate / methanol / ethanol (65/20/10/5, parts by mass)
Acetone / cyclopentanone / ethanol / butanol (65/20/10/5, parts by mass)
Acetone / 1,3-dioxolane / ethanol / butanol (65/20/10/5, parts by mass)
1,3-dioxolane / cyclohexanone / methyl ethyl ketone / methanol / butanol (60/20/10/5/5, parts by mass)
Etc.

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

In the practice of the present invention, in preparing the cellulose acylate solution (composition) of the present invention, a chlorinated organic solvent is sometimes used as a main solvent. In the present invention, the chlorinated organic solvent is not particularly limited as long as the object can be achieved as long as the cellulose acylate can be dissolved, cast, and formed into a film. These chlorinated organic solvents are preferably dichloromethane and chloroform. Particularly preferred is dichloromethane.

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

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

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

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

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

Dichloromethane / methanol / ethanol / butanol (80/10/5/5, parts by mass),
Dichloromethane / acetone / methanol / propanol (80/10/5/5, parts by mass),
Dichloromethane / methanol / butanol / cyclohexane (80/10/5/5, parts by mass),
Dichloromethane / methyl ethyl ketone / methanol / butanol (80/10/5/5, parts by mass),
Dichloromethane / acetone / methyl ethyl ketone / ethanol / isopropanol (67/10/10/5/7, parts by mass),
Dichloromethane / cyclopentanone / methanol / isopropanol (77/10/5/8, parts by mass),
Dichloromethane / methyl acetate / butanol (80/10/10, parts by mass),
Dichloromethane / cyclohexanone / methanol / hexane (70/20/5/5, parts by mass)
Dichloromethane / methyl ethyl ketone / acetone / methanol / ethanol (50/20/20/5/5, parts by mass),
Dichloromethane / 1,3-dioxolane / methanol / ethanol (70/20/5/5, 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 / methyl ethyl ketone / acetone / methanol / ethanol (70/10/10/5/5, parts by mass),
Dichloromethane / acetone / ethyl acetate / ethanol / butanol / hexane (65/10/10/5/5/5, parts by mass),
Dichloromethane / methyl acetoacetate / methanol / ethanol (65/20/10/5, parts by mass),
Dichloromethane / cyclopentanone / ethanol / butanol (65/20/10/5, parts by mass),
Etc.

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

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

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

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

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

The cellulose acylate composition of the present invention is represented by any one of the general formulas (1) to (5) or (4-A), (4-B), (5-A), or (5-B). a solution obtained by dissolving the compound in a suitable solvent, can be prepared by mixing the cellulose acylate solution obtained by dissolving cellulose acylate in a suitable solvent. The mixing method of both solutions is not specifically limited, The solution obtained by mixing both solutions can be used as dope for film formation. However, in the present invention, cellulose acylate and a compound represented by any one of general formulas (1) to (5) or (4-A), (4-B), (5-A) or (5-B) The order of addition is not limited, and both may be added simultaneously. The concentration of cellulose acylate in the dope is preferably 10 to 30% by mass, more preferably 13 to 27% by mass, and particularly preferably 15 to 25% by mass. The method for dissolving cellulose acylate in these concentrations may be carried out so that the cellulose acylate has a predetermined concentration at the stage of dissolution, or a concentration step which will be described later after it is prepared in advance as a low concentration solution (for example, 9 to 14% by mass). May be adjusted to a predetermined high concentration solution. Further, a high-concentration cellulose acylate solution may be added in advance and then various additives may be added to obtain a predetermined low-concentration cellulose acylate solution. Any method can be used as long as the dope having the above-mentioned concentration can be obtained. .

In order to dissolve the compound represented by any one of the general formulas (1) to (5) or (4-A), (4-B), (5-A) or (5-B) The same solvent as the solvent for cellulose acylate described above can be used. The concentration of the compound represented by any one of the general formulas (1) to (5) or (4-A), (4-B), (5-A), or (5-B) in the dope is, for example, 0. 0.1 to 30% by mass, preferably 1 to 15% by mass.

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

[Cellulose acylate film]
The cellulose acylate film of the present invention comprises the cellulose acylate composition of the present invention.
Next, a method for producing the cellulose acylate film of the present invention will be described.

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

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

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

In the present invention, the following configurations are particularly preferred for the contents and casting of each layer. That is, the dope is a dope containing 0.1 to 20% by mass of at least one liquid or solid plasticizer with respect to cellulose acylate at 25 ° C. and / or at least one liquid or solid. A dope containing 0.001 to 5% by mass of an ultraviolet absorber of cellulose based on cellulose acylate and / or fine particle powder having an average particle size of 5 to 3000 nm and at least one solid. Dope containing 0.001 to 5% by mass with respect to acylate and / or dope containing 0.001 to 2% by mass of at least one fluorosurfactant with respect to cellulose acylate it is, and / or at least one release agent relative to the cellulose acylate 0.0001 It is doped to contain amounts%, and / or at least one antidegradant which is doped to contain 0.0001 to 2 mass% of cellulose acylate, and / or at least one The optical anisotropy control agent is contained in an amount of 0.1 to 15% by mass with respect to the cellulose acylate , and / or at least one infrared absorber is contained in an amount of 0.1 to 5% by mass with respect to the cellulose acylate. it is to have doped, doped and made therefrom Rousset cellulose acylate fill-arm, characterized in are preferred.

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

Here, the physical properties include physical properties described in detail on pages 6 to 7 of the Japan Society for Invention and Innovation Technical Report (Public Technical Number 2001-1745, issued on March 15, 2001, Japan Society of Inventions). For example, haze, transmittance, spectral characteristics, retardation Re, same Rth, molecular orientation axis, axial misalignment, tear strength, folding strength, tensile strength, inside / outside Rt difference, creaking, dynamic friction, alkaline hydrolysis, curl value, water content Rate, residual solvent amount, heat shrinkage rate, high humidity dimensional evaluation, moisture permeability, base flatness, dimensional stability, heat shrinkage starting temperature, elastic modulus, and measurement of bright spot foreign matter, etc. Impedance and surface shape used for evaluation are also included.
In addition, the Yellow Index, Transparency, Thermophysical Properties (Tg) of Cellulose Acylate described in detail on page 11 in the Japan Society of Invention Disclosure Technical Report (Public Technical No. 2001-1745, issued on March 15, 2001, Invention Association) , Heat of crystallization) and the like.

The cellulose acylate film of the present invention may be stretched. It is particularly preferable that the film is stretched at an arbitrary magnification in order to exhibit optical anisotropy.

For the stretching, a known method can be used. For example, a tenter uniaxial stretching method, a simultaneous biaxial stretching method, a sequential method at a temperature between 10 ° C. and 50 ° C. higher than the glass transition temperature (Tg) of the cellulose acylate film. The film can be stretched by a biaxial stretching method or an inflation method. Moreover, in the case of film production by the solution pouring method, the residual solvent can be stretched within a range of 1 to 30%, more preferably within a range of 5 to 20%. The draw ratio is preferably 1.01-2.

The cellulose acylate film can achieve an improved adhesion between the cellulose acylate film and each functional layer (for example, the undercoat layer and the back layer) by optionally performing a surface treatment. For example, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment can be used. The glow discharge treatment here may be low-temperature plasma that occurs in a low pressure gas of 10 ^{−3 to} 20 Torr (0.133 Pa to 2.67 kPa), and plasma treatment under atmospheric pressure is also preferable.

  A plasma-excitable gas is a gas that is plasma-excited under the above conditions, and includes chlorofluorocarbons such as argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, tetrafluoromethane, and mixtures thereof. It is done. Details of these are described in detail on pages 30 to 32 in the technical report of the Invention Association (Public Technical Number 2001-1745, published on March 15, 2001, Invention Association). In the plasma treatment at atmospheric pressure, which has been attracting attention in recent years, for example, irradiation energy of 20 to 500 kGy is used under 10 to 1000 keV, and more preferably irradiation energy of 20 to 300 kGy is used under 30 to 500 keV. Among these, an alkali saponification treatment is particularly preferable, and it is extremely effective as a surface treatment of cellulose acylate film.

  The alkali saponification treatment is preferably performed in a cycle in which the film surface is immersed in an alkali solution, neutralized with an acidic solution, washed with water and dried. Examples of the alkaline solution include potassium hydroxide solution and sodium hydroxide solution, and the concentration of hydroxide ions is preferably in the range of 0.1 to 5.0 mol / L, and preferably 0.5 to 4.0 mol / L. More preferably, it is in the range. The alkaline solution temperature is preferably in the range of room temperature to 90 ° C, more preferably in the range of 40 to 70 ° C.

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

An aqueous solution of a surfactant can also be used as a solvent. The alkali of the alkali saponification coating solution is preferably an alkali that dissolves in the above solvent, and more preferably KOH or NaOH. The pH of the saponification coating solution is preferably 10 or more, more preferably 12 or more. The reaction conditions during alkali saponification are preferably 1 second to 5 minutes at room temperature, more preferably 5 seconds to 5 minutes, and particularly preferably 20 seconds to 3 minutes. After the alkali saponification reaction, it is preferable to wash the surface on which the saponification solution is applied with water or with an acid and then with water.
Further, the coating-type saponification treatment and the alignment film uncoating described later can be performed continuously, and the number of steps can be reduced.

In order to achieve adhesion between the film and the functional layer, after surface activation treatment, directly apply the functional layer on the cellulose acylate film to obtain adhesive force, and after some surface treatment Alternatively, there is a method in which an undercoat layer (adhesive layer) is provided and a functional layer is applied thereon without surface treatment. Details of these subbing layers are described on page 32 of the Japan Society for Invention and Innovation (Public Technical Number 2001-1745, published on March 15, 2001, Japan Society of Inventions). Various functional layers of the cellulose acylate film of the present invention are also disclosed on pages 32 to 45 in the Japan Society for Invention and Technology (Publication No. 2001-1745, published on March 15, 2001, Invention Association). It is described in detail.

In order to control the Re value and the Rth value of the cellulose acylate film of the present invention within preferable ranges, the general formulas (1) to (5) or (4-A), (4-B), (5- It is preferable to appropriately adjust the type and addition amount of the compound (retardation control agent) represented by either A) or (5-B), and the stretching ratio of the film. In particular, in the present invention, a retardation control agent capable of achieving a desired Rth value is selected, and the addition amount of the retardation control agent and the stretching ratio of the film are appropriately set so as to obtain a desired Re value. By doing so, a cellulose acylate film having a desired Re value and Rth value can be obtained.

  In this specification, Re (λ) and Rth (λ) represent in-plane retardation and retardation in the thickness direction at a wavelength λ, respectively. Re (λ) is measured by making light having a wavelength of λ nm incident in the normal direction of the film in KOBRA 21ADH (trade name, manufactured by Oji Scientific Instruments). Rth (λ) is the light of wavelength λnm from the direction inclined by + 40 ° with respect to the normal direction of the film, with Re (λ) and the in-plane slow axis (determined by KOBRA 21ADH) as the tilt axis (rotation axis) And a retardation value measured by making light of wavelength λ nm incident from a direction inclined by −40 ° with respect to the film normal direction with the in-plane slow axis as the tilt axis (rotation axis). KOBRA 21ADH calculates based on the retardation value measured in three directions, the assumed value of the average refractive index, and the input film thickness value. Here, as the assumed value of the average refractive index, “Polymer Handbook” (JOHN WILEY & SONS, INC), catalog values of various optical films can be used. Those whose average refractive index is not known can be measured with an Abbe refractometer. The average refractive index values of main optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), Polystyrene (1.59).

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

When using as a polarizing plate protective film, the production method of a polarizing plate is not specifically limited, It can produce by a general method. There is a method in which the obtained cellulose acylate film is treated with an alkali and bonded to both sides of a polarizer prepared by immersing and stretching a polyvinyl alcohol film in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. Instead of alkali treatment, easy adhesion processing as described in JP-A-6-94915 and JP-A-6-118232 may be performed. Examples of the adhesive used for bonding the protective film-treated surface and the polarizer include polyvinyl alcohol adhesives such as polyvinyl alcohol and polyvinyl butyral, vinyl latexes such as butyl acrylate, and the like. The polarizing plate is composed of a polarizer and a protective film that protects both sides of the polarizer, and is further constructed by laminating a protective film on one surface of the polarizing plate and a separate film on the other surface. The protective film and the separate film are used for the purpose of protecting the polarizing plate at the time of shipping the polarizing plate or at the time of product inspection.

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

The cellulose acylate film of the present invention can be used in various applications, and is particularly effective when used as an optical compensation sheet for liquid crystal display devices. The cellulose acylate film of the present invention can be used for liquid crystal cells in various display modes. TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), AFLC (Anti-ferroelectric Liquid Crystal), OCB (Optically Compensatory Bend), STN (Supper Twisted Nematic), VA (Vertically Aligned) and Various display modes such as HAN (Hybrid Aligned Nematic) have been proposed. In addition, a display mode in which the above display mode is oriented and divided has been proposed.

The cellulose acylate film is effective in the liquid crystal display device in any display mode. Further, it is effective in any of a transmissive, reflective, and transflective liquid crystal display device. The cellulose acylate film of the present invention may be used as a support for an optical compensation sheet of a TN type liquid crystal display device having a TN mode liquid crystal cell. The cellulose acylate film of the present invention may be used as a support for an optical compensation sheet of an STN type liquid crystal display device having an STN mode liquid crystal cell.

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

The cellulose acylate film of the present invention is also advantageously used as an optical compensation sheet for TN-type, STN-type, HAN-type, and GH (Guest-Host) type reflective liquid crystal display devices. These display modes have been well known since ancient times. The TN-type reflective liquid crystal display device is described in JP-A-10-123478, International Publication WO98 / 48320, and Japanese Patent No. 3022477. The optical compensation sheet used for the reflection type liquid crystal display device is described in WO00-65384. The cellulose acylate film of the present invention is also advantageously used as a support for an optical compensation sheet of an ASM type liquid crystal display device having an ASM (Axially Symmetric Aligned Microcell) mode liquid crystal cell. The ASM mode liquid crystal cell is characterized in that the thickness of the cell is maintained by a resin spacer whose position can be adjusted.

Other properties are the same as those of the TN mode liquid crystal cell. The ASM mode liquid crystal cell and the ASM type liquid crystal display device are described in a paper by Kume et al. (Kume et al., SID 98 Digest 1089 (1998)). The detailed uses of the cellulose acylate films described above are described in detail in pages 45 to 59 of the Japan Society for Invention and Technology (public technical number 2001-1745, published on March 15, 2001, Japan Society for Invention). ing.

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

Synthesis of compounds represented by any one of general formulas (1) to (5) or (4-A), (4-B), (5-A) or (5-B) [Example 1: Exemplary compounds Synthesis of (A-2)]
Exemplified compound (A-2) was synthesized according to the following scheme.

[Synthesis of Intermediate (S3)]
Methyl 2,4-dihydroxybenzoate (S1) (134.4 g), intermediate (S2) (263 g) and potassium carbonate (221 g) were added to MEK (1000 ml), and the mixture was heated and stirred on an 80 ° C. hot water bath for 6 hours. After completion of the reaction, the inorganic salt was filtered off under reduced pressure, and then the solvent was concentrated under reduced pressure. When the remaining amount reached about 700 g, 1000 ml of ethyl acetate and water were added to extract the organic layer. The organic layer was washed successively with 1N aqueous hydrochloric acid, water and saturated brine, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent, ethyl acetate / n-hexane = 1/2 to 2/3) to obtain an intermediate (S3) as an oily substance (100 g).
[Synthesis of Intermediate (S4)]
Intermediate (S3) (100 g), dimethyl sulfate (52.5 ml), and potassium carbonate (102 g) were added to dimethylformamide (DMF) (300 ml), and the mixture was heated and stirred on a 90 ° C. hot water bath for 6 hours. After completion of the reaction, ethyl acetate was added and the inorganic salt was filtered off under reduced pressure, and then water was added to the filtrate to extract the organic layer. The organic layer was washed successively with 1N aqueous hydrochloric acid, water and saturated brine, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The resulting oil was not purified and used in the next step.
This methyl ester compound was dissolved in 200 ml of methanol and 222 ml of 5N aqueous potassium hydroxide solution, and the mixture was heated and stirred at 40 ° C. for 2 hours. Thereafter, the mixture was added to a mixture of 500 ml of water and 92 ml of 12N hydrochloric acid, and then 500 ml of ethyl acetate was added to separate the organic layer. The organic layer was washed successively with water and saturated brine, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. In this way, 77 g of intermediate (S4) was obtained as an oil.

[Synthesis of Exemplary Compound (A-2)]
After the intermediate (S4) 15.3g, toluene 100ml, dimethylformamide 0.1ml was heated at 70 degreeC, the thionyl chloride 4.55ml was dripped slowly, and it heated and stirred at 70 degreeC after dripping for 1 hour. Thereafter, a solution prepared by dissolving 9.62 g of 4-phenylphenol (S5) in 20 ml of dimethylformamide was added to the reaction solution, and further reacted at 70 ° C. for 2 hours. After the reaction, after cooling to room temperature, the reaction solution was added to a mixed solution of 250 ml of water and 250 ml of methanol and stirred. The exemplified compound (A-2) was obtained as a white solid by filtration under reduced pressure (yield 60%).
The compound was identified by ¹ H-NMR (400 MHz).
¹ H-NMR (CDCl ₃ ) 3.41 (s, 3H), 3.60 (m, 2H), 3.75 (m, 2H), 3.92 (m, 5H), 4.26 (m, 2H), 6.58 (m, 2H), 7.29 (d, 2H), 7.36 (m, 1H), 7.44 (t, 2H), 7.60 (m, 4H), 8. 10 (d, 1H).

[Example 2: Synthesis of exemplified compound (A-27)]
Exemplified compound (A-27) was synthesized according to the following scheme.

[Synthesis of Intermediate (S7)]
77 g of intermediate (S4), 500 ml of toluene, and 0.6 ml of dimethylformamide were heated to 70 ° C., 29.5 ml of thionyl chloride was slowly added dropwise, and the mixture was heated and stirred at 70 ° C. for 1 hour. Thereafter, a solution prepared by dissolving 50.8 g of 4-hydroxybenzoic acid (S6) in 100 ml of dimethylformamide was added to the reaction solution, and further reacted at 70 ° C. for 2 hours. After the reaction, after cooling to room temperature, the reaction solution was added to a mixed solution of 1500 ml of water and 500 ml of methanol and stirred to precipitate the intermediate (S7) as a crude product. The crystals were separated by filtration under reduced pressure, then dispersed again in water / methanol, washed, and filtered under reduced pressure to obtain 100 g of intermediate (S7) as a white solid.

[Synthesis of Exemplary Compound (A-27)]
14.7 g of the intermediate (S7) was dissolved in 150 ml of tetrahydrofuran (THF) and cooled to 0 ° C. with ice / methanol. Subsequently, 2.9 ml of mesyl chloride and 6.53 ml of N, N-diisopropylethylamine were slowly added dropwise while maintaining the internal temperature at 0 ° C. or lower, and stirring was continued at 0 ° C. or lower for 2 hours. Subsequently, a solution obtained by dissolving 3.0 g of intermediate (S8) in 20 ml of THF, 6.53 ml of N, N-diisopropylethylamine and 0.23 g of N, N-dimethylaminopyridine were added slowly and gradually to the room temperature. Stirring was continued while returning. After leaving overnight, 100 ml of methanol was added, and the precipitated white solid was separated by filtration. The obtained crude crystals were purified by recrystallization from ethyl acetate / methanol to obtain 8 g of Exemplified Compound (A-27) as a white solid (yield 56%).
The compound was identified by ¹ H-NMR (400 MHz).
¹ H-NMR (CDCl ₃ ) 3.41 (s, 6H), 3.60 (m, 4H), 3.75 (m, 4H), 3.92 (m, 10H), 4.26 (m, 4H), 6.58 (m, 4H), 7.32 (d, 4H), 7.40 (d, 4H), 7.65 (m, 4H), 8.10 (d, 2H), 8. 30 (d, 4H)
The melting point of the obtained compound was 115 ° C.

[Example 3: Synthesis of exemplified compound (B-26)]
Exemplified compound (B-26) was synthesized according to the following scheme.

[Synthesis of Intermediate (T3)]
After heating 17 g of intermediate (T1), 100 ml of toluene, and 0.25 ml of dimethylformamide to 70 ° C., 4.55 ml of thionyl chloride was slowly added dropwise, and the mixture was heated and stirred at 70 ° C. for 2 hours. Thereafter, a solution prepared by dissolving 7.82 g of 4-hydroxybenzoic acid (T2) in 20 ml of dimethylformamide was added to the reaction solution, and further reacted at 70 ° C. for 2 hours. After the reaction, the reaction mixture was cooled to room temperature, ethyl acetate and water were added, and the organic layer was separated. The organic layer was washed successively with 1N aqueous hydrochloric acid, water and saturated brine, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. Methylene chloride was added to the residue, and the precipitated white solid was collected by filtration to obtain 14.7 g of intermediate (T3) (yield 62%).

[Synthesis of Exemplified Compound (B-26)]
14.7 g of intermediate (T3) was dissolved in 100 ml of THF and cooled to 0 ° C. with ice / methanol. Subsequently, 2.71 ml of mesyl chloride and 6.10 ml of N, N-diisopropylethylamine were slowly added dropwise while maintaining the internal temperature at 0 ° C. or lower, and then stirring was continued at 0 ° C. or lower for 2 hours. Subsequently, a solution obtained by dissolving 2.17 g of 4,4′-biphenol in 20 ml of THF, 6.10 ml of N, N-diisopropylethylamine, and 0.214 g of N, N-dimethylaminopyridine were slowly added in this order, and the reaction solution was allowed to cool to room temperature. The stirring was continued while returning to the initial state. After leaving overnight, 100 ml of methanol was added, and the precipitated white solid was separated by filtration. The obtained crude crystals were purified by recrystallizing sequentially with ethyl acetate and methylene chloride / methanol to obtain 6.5 g of Exemplified Compound (B-26) as a white solid (yield 56%).
The compound was identified by ¹ H-NMR (400 MHz).
¹ H-NMR (CDCl ₃ ) δ 3.40 (s, 6H), 3.60 (m, 4H), 3.76 (m, 4H), 3.90 (s, 6H), 3.94 (s, 6H), 3.95 (m, 4H), 4.32 (m, 4H), 6.69 (s, 2H), 7.30 (d, 4H), 7.38 (d, 4H), 7. 60 (s, 2H), 7.65 (d, 4H), 8.28 (d, 4H)
The melting point of the obtained compound was 138 ° C.

[Example 4]
Preparation of Cellulose Acetate Film Each component of the following cellulose acetate solution composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acetate solution.
(Cellulose acetate solution composition)
Cellulose acetate having an acetylation degree of 60.9% 100 parts by weight Triphenyl phosphate (plasticizer) 7.8 parts by weight Biphenyl diphenyl phosphate (plasticizer) 3.9 parts by weight Methylene chloride (first solvent) 318 parts by weight Methanol (No. 2 solvents) 47 parts by mass

In another mixing tank, exemplary compounds (B-2), (B-17), (A-26), (B-26), (A-27), (B-31), (A-36), (B-36), (A-41), or (A-48), or 16 parts by mass of a comparative compound, 87 parts by mass of methylene chloride, and 13 parts by mass of methanol are added and stirred while heating to control retardation. An agent solution was prepared.
A dope was prepared by mixing 36 parts by mass of a retardation control (raising) agent solution with 474 parts by mass of the cellulose acetate solution and stirring sufficiently. Retardation control agents were added in parts by mass shown in Table 1 with respect to 100 parts by mass of cellulose acetate.

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

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

Comparative compound (compound described in JP-A-2003-344655)

Thus, by adding the compound of the present invention, it has optical characteristics with a Re / Rth ratio of 0.22 or higher, which cannot be realized with a known discotic compound (comparative compound), that is, has a higher Re expression. It has been found that a novel cellulose acylate film having a range of optical properties can be produced.

[Example 5] Production of polarizing plate [Saponification treatment of cellulose acylate film]
Cellulose acylate film No. 1 prepared in Example 4 was used. 6 was immersed in a 1.3 mol / L aqueous sodium hydroxide solution at 55 ° C. for 2 minutes, then washed in a water bath at room temperature, and neutralized with 0.05 mol / L sulfuric acid at 30 ° C. Again, it was washed in a water bath at room temperature and further dried with hot air at 100 ° C. In this way, the surface of the cellulose acylate film 6 was saponified.

  Further, a commercially available cellulose triacetate film “Fujitac TD80UF” (manufactured by Fuji Photo Film Co., Ltd., trade name) was saponified under the same conditions and used for the following polarizing plate sample preparation.

[Production of polarizer]
A stretched PVA film was made to adsorb iodine to produce a polarizer, and a cellulose acylate film No. saponified as described above using a polyvinyl alcohol-based adhesive. 6 was affixed to one side of the polarizer. The transmission axis of the polarizer and the slow axis of the cellulose acylate film were arranged in parallel.

  Further, “Fujitac TD80UF” saponified as described above was attached to the opposite side of the polarizer using a polyvinyl alcohol-based adhesive. In this way, a polarizing plate (A) was produced.

[Example 6] Production and evaluation of VA liquid crystal display device [Production of liquid crystal cell]
1 part by weight of octadecyldimethylammonium chloride (coupling agent) was added to 100 parts by weight of a 3% by weight aqueous solution of polyvinyl alcohol. This was spin-coated on a glass substrate with an ITO electrode, heat-treated at 160 ° C., and then rubbed to form a vertical alignment film. The rubbing treatment was performed in opposite directions on the two glass substrates. Two glass substrates were opposed to each other so that the cell gap (d) was 5 μm. A liquid crystal compound (Δn: 0.08) mainly composed of ester and ethane was injected into the cell gap to produce a vertically aligned liquid crystal cell. The product of Δn and d was 400 nm.

The polarizing plate (A) produced in Example 5 above was conditioned in advance under the temperature and humidity conditions of 25 ° C. and 60% RH, and then packaged in a moisture-proof bag and left for 3 days. The bag was a packaging material having a laminated structure of polyethylene terephthalate / aluminum / polyethylene, and the moisture permeability was 1 × 10 ⁻⁵ g / m ² · day or less.

  When the polarizing plate (A) was taken out in an environment of 25 ° C. and 60% RH, and adhered to both surfaces of the produced vertical alignment liquid crystal cell using an adhesive sheet, a liquid crystal display device was produced. It was found that a liquid crystal display screen using a polarizing plate including a cellulose acylate film has a wide color viewing angle and is preferable.

[Example 7] Cellulose acylate film no. 16 [Preparation of cellulose acylate solution]
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acylate solution.

(Composition of cellulose acylate solution)
Cellulose acetate having an acetylation degree of 2.87 100.0 parts by mass Plasticizer: Triphenyl phosphate 6.0 parts by mass Plasticizer: Biphenyl phosphate 3.0 parts by mass Methylene chloride (first solvent) 402.0 parts by mass Methanol (No. 2 solvent) 60.0 parts by mass

[Preparation of matting agent solution]
The following composition was charged into a disperser and stirred to dissolve each component to prepare a matting agent solution.

(Matting agent solution composition)
2.0 parts by mass of silica particles having an average particle size of 20 nm (AEROSIL R972, trade name, manufactured by Nippon Aerosil Co., Ltd.)
Methylene chloride (first solvent) 75.0 parts by mass Methanol (second solvent) 12.7 parts by mass Cellulose acylate solution 10.3 parts by mass

[Preparation of retardation increasing agent solution]
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a retardation increasing agent solution.

(Composition of retardation increasing agent solution)
Retardation increasing agent (A-26) 10.0 parts by mass Retardation increasing agent (A-36) 10.0 parts by mass Methylene chloride (first solvent) 58.4 parts by mass Methanol (second solvent) 8.7 parts by mass Part 12.8 parts by weight of cellulose acylate solution

  93.3 parts by mass of the cellulose acylate solution, 1.3 parts by mass of the matting agent solution, and 5.4 parts by mass of the retardation increasing agent solution were filtered and mixed, and cast using a band casting machine. The web obtained with a residual solvent content of 35% by weight was peeled from the band, and stretched at a stretching rate of 30% / min up to a stretching ratio of 15% using a tenter at 140 ° C., and then stretched at 10%. The magnification was maintained at 140 ° C. for 30 seconds. Thereafter, the clip was removed and dried at 140 ° C. for 40 minutes. 16 was produced. The resulting cellulose acylate film had a residual solvent amount of 0.2% by mass, a film thickness of 80 μm, Re (590) of 38 nm, and Rth (590) of 175 nm.

[Example 8] Production of polarizing plate [Production of optical compensation sheet]
(Saponification treatment of cellulose acylate film)
Cellulose acylate film No. 1 prepared in Example 7 The liquid of the following composition was apply | coated 5.2 ml / m < ² > on 16, and it dried at 60 degreeC for 10 second. The surface of the film was washed with running water for 10 seconds, and air at 25 ° C. was blown to dry the film surface.

(Saponification composition)
Isopropyl alcohol 818 parts by weight Water 167 parts by weight Propylene glycol 187 parts by weight “EMALEX” (trade name) manufactured by Nippon Emulsion Co., Ltd. 10 parts by weight Potassium hydroxide 67 parts by weight

(Formation of alignment film)
Saponified cellulose acylate film no. A coating solution having the following composition was applied onto 16 by 24 mL / m ² using a # 14 wire bar coater. Drying was performed with warm air of 60 ° C. for 60 seconds, and further with warm air of 90 ° C. for 150 seconds.
Next, cellulose acylate film no. The formed film was rubbed in a direction of 45 ° with 16 stretching directions (almost coincident with the slow axis).

(Composition of alignment film coating solution)
Modified polyvinyl alcohol having the following structure 20 parts by mass Water 360 parts by mass Methanol 120 parts by mass Glutaraldehyde (crosslinking agent) 1.0 part by mass

(Formation of optically anisotropic layer)
On the alignment film, 91 parts by mass of a discotic compound having the following structure, 9 parts by mass of ethylene oxide-modified trimethylolpropane triacrylate (V # 360, trade name, manufactured by Osaka Organic Chemical Co., Ltd.), cellulose acetate butyrate (CAB531-1) , Trade name, manufactured by Eastman Chemical Co., Ltd.) 1.5 parts by mass, photopolymerization initiator (Irgacure 907, trade name, manufactured by Ciba Geigy) 3 parts by mass, sensitizer (Kayacure DETX, trade name, Nippon Kayaku ( A coating solution prepared by dissolving 1 part by mass in 214.2 parts by mass of methyl ethyl ketone was applied with 5.2 mL / m ² using a # 3 wire bar coater. This was affixed to a metal frame and heated in a thermostatic bath at 130 ° C. for 2 minutes to orient the discotic compound. Next, using a 120 W / cm high-pressure mercury lamp at 90 ° C., UV irradiation was performed for 1 minute to polymerize the discotic compound. Then, it stood to cool to room temperature. Thus, an optically anisotropic layer was formed, and an optical compensation sheet (B) was obtained.

(Saponification treatment of optical compensation sheet)
Saponification was performed in the same manner as in Example 5.

[Preparation of polarizing plate]
(Production of polarizer)
A polarizer was prepared by adsorbing iodine to a stretched polyvinyl alcohol film. Next, cellulose acylate film No. of the produced optical compensation sheet (B). The 16 side was affixed to one side of the polarizer using a polyvinyl alcohol-based adhesive. The slow axis of the cellulose acylate film (16) and the transmission axis of the polarizer were arranged in parallel.

  A commercially available cellulose triacetate film “Fujitac TD80UF” (trade name, manufactured by Fuji Photo Film Co., Ltd.) was saponified in the same manner as in Example 3, and the other side of the polarizer (optical compensation sheet) using a polyvinyl alcohol adhesive. Was pasted on the side that was not pasted). Thus, the elliptically polarizing plate (B) was produced.

[Example 9] Production of liquid crystal display device [Production of bend alignment liquid crystal cell]
A polyimide film was provided as an alignment film on a glass substrate with an ITO electrode, and the alignment film was rubbed. The obtained two glass substrates were opposed to each other so that the rubbing directions were parallel to each other, and the cell gap was set to 5.7 μm. A bend-aligned liquid crystal cell was produced by injecting a liquid crystal compound “ZLI1132” (trade name, manufactured by Merck & Co., Inc.) having Δn of 0.1396 into the cell gap.

[Production of liquid crystal display]
Two polarizing plates (B) were attached so as to sandwich the prepared bend alignment cell. The optically anisotropic layer of the polarizing plate faced the cell substrate, and the rubbing direction of the liquid crystal cell and the rubbing direction of the optically anisotropic layer facing it were antiparallel.

It was found that the liquid crystal display device using the polarizing plate of the present invention has a preferable image with a wide contrast viewing angle.

Claims (15)

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

(Wherein R ¹ represents a hydrogen atom or an alkoxy group , R ² and R ⁵ each independently represents a hydrogen atom, an alkyl group or an alkoxy group, and R ⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or Represents an alkoxy group having 1 to 12 carbon atoms , R ¹³ represents an alkyl group containing one or more heteroatoms, L represents a single bond or —O— , Ar represents an aryl group or an aromatic heterocyclic group; To express.) The cellulose acylate composition according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

(Wherein R ² and R ⁵ each independently represents a hydrogen atom , an alkyl group or an alkoxy group , R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹³ represents one or more heteroatoms. Represents an alkyl group to be contained, L represents a single bond or —O— , and Ar represents an aryl group or an aromatic heterocyclic group. The cellulose acylate composition according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (3).

(Wherein R ² and R ⁵ each independently represents a hydrogen atom alkyl group or an alkoxy group , R ¹¹ and R ¹⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹³ represents hetero An alkyl group containing one or more atoms is represented, L represents a single bond or —O— , and Ar represents an aryl group or an aromatic heterocyclic group. The cellulose acylate composition according to any one of claims 1 to 3, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (4).

(Wherein R ²¹ represents a hydrogen atom or an alkoxy group, R ²² and R ²⁵ each independently represents a hydrogen atom , an alkyl group or an alkoxy group , and R ²⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, R ⁴³ represents an alkyl group containing one or more hetero atoms, L ¹ represents a single bond or -O-, L ² is a single bond, -CONH -, - NHCO-, -COO-, -OCO- or an alkynylene group , Ar ¹ represents an arylene group or an aromatic heterocyclic group, Ar ² represents an aryl group or an aromatic heterocyclic group, and n is 1 or more The n L ^{2 s} may be the same or different, and the n Ar ^{1 s} may be the same or different.) 5. In the general formula (4), R ²¹ represents —OR ⁴¹ (R ⁴¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), and R ²⁴ represents a hydrogen atom. The cellulose acylate composition described in 1. In the general formula (4), R ²¹ represents —OR ⁴¹ and R ²⁴ represents —OR ⁴⁴ (R ⁴¹ and R ⁴⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). The cellulose acylate composition according to claim 4. In the said General formula (4), n is an integer greater than or equal to 3, The cellulose acylate composition of any one of Claims 4-6 characterized by the above-mentioned. Cellulose acylate film characterized by comprising a cellulose acylate composition according to any one of claims 1-7. The compound represented by the following general formula (4-A).

( Wherein R ⁴³ represents an alkyl group containing one or more heteroatoms, R ⁴¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L ¹ represents a single bond or —O—, ² represents a single bond , —CONH—, —NHCO—, —COO—, —OCO— or an alkynylene group , Ar ¹ represents an arylene group or an aromatic heterocyclic group, and Ar ² represents an aryl group or an aromatic group. Represents a telocyclic group, n represents an integer of 1 or more, n L ^{2 s} may be the same or different, and n Ar ^{1 s} may be the same or different .) The compound represented by the following general formula (4-B).

(In the formula , R ⁴³ represents an alkyl group containing one or more hetero atoms, R ⁴¹ and R ⁴⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and L ¹ represents a single bond or — represents O- and, L ² represents a single bond, -CONH -, - NHCO -, - COO -, - OCO- or .Ar ¹ representing the alkynylene group represents a heterocyclic group an arylene group or an aromatic, Ar ² is An aryl group or an aromatic heterocyclic group, n represents an integer of 1 or more, n L ^{2 s} may be the same or different, and n Ar ^{1 s} are the same May be different.) The polarizing plate in which a protective film is bonded to both surfaces of a polarizer, wherein at least one of the protective films is the cellulose acylate film according to claim 8 . The polarizing plate according to claim 11 , further comprising an optically anisotropic layer on at least one surface of the protective film. 13. A liquid crystal display device comprising a liquid crystal cell and two polarizing plates disposed on both sides thereof, wherein at least one polarizing plate is the polarizing plate according to claim 11 or 12 . The liquid crystal display device according to claim 13, wherein the liquid crystal display device is in a VA mode. The liquid crystal display device according to claim 13, wherein the liquid crystal display device is in an OCB mode.