KR20050012158A - Cellulose composition, cellulose film and modifier for use therefor, and polarizing plate protecting film, liquid crystal display device and silver halide photographic photosensitive material employing the film - Google Patents

Abstract

PURPOSE: Provided are a cellulose composition, a cellulose film with lower moisture permeability and lower optical anisotropy using the same, a modifier for the cellulose film, and a polarizing plate protecting film, a liquid crystal display device and silver halide photographic photosensitive material using the cellulose film. CONSTITUTION: The cellulose composition comprises a cellulose and as a modifier for a cellulose film, at least one compound represented by the formula 1, or the formula 2, wherein each of R1, R2 and R3 independently represents a hydrogen atom or an alkyl group; X represents a divalent linking group formed by at least one group selected from the group 1 of a linking group consisting of a sing bond, -O-, -CO-, -NR4-(in which, R4 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group), an alkylene group and an arylene group; Y represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group; each of Q1, Q2 and Q3 independently represents a 5-membered or 6-membered ring; and X1 represents B, C-R(in which, R is a hydrogen atom or a substituent), N, P or P=O.

Description

Cellulose composition, cellulosic film and modifier used therefor, polarizing plate protective film, liquid crystal display device and silver halide photosensitive material having the film DEVICE AND SILVER HALIDE PHOTOGRAPHIC PHOTOSENSITIVE MATERIAL EMPLOYING THE FILM}

TECHNICAL FIELD The present invention relates to a cellulose body composition and a cellulose body film, and more particularly, to a cellulose body film modifier showing low moisture permeability, a cellulose body composition and a cellulose body film containing the modifier. Moreover, this invention relates to the manufacturing method of the said cellulose body film. Moreover, this invention relates to the polarizing plate protective film, the liquid crystal display device, and the silver halide photographic photosensitive material using this cellulose body film.

Conventionally, cellulose acylate films have been used for photographic supports and various optical materials because of their toughness and flame retardancy. In particular, recently, it has been used a lot as an optical transparent film for liquid crystal display devices. Cellulose acylate film has excellent optical transparency and optically isotropy, and is excellent as an optical material for polarizing devices such as liquid crystal display devices. It has been used as a support for an optical compensation film which can be done well (viewing angle compensation).

A polarizer protective film is formed on at least one side of a polarizer by adhesion to the polarizing plate which is one of the members for liquid crystal display devices. A general polarizer can be obtained by dyeing a stretched polyvinyl alcohol (PVA) -based film with iodine or a dichroic dye. In most cases, as a protective film of a polarizer, the cellulose acylate film which can be directly adhere | attached with respect to PVA, especially the triacetyl cellulose film is used. The optical characteristic of the protective film of this polarizer greatly influences the characteristic of a polarizing plate.

On the other hand, a cellulose acylate film generally has a significantly higher moisture permeability under high temperature and high humidity compared to other transparent supports, for example, polyethylene terephthalate films, so that the performance is deteriorated, so that a compound called a plasticizer is often added. As a plasticizer added to cellulose acylate, phosphoric acid triesters such as triphenyl phosphate and biphenyl diphenyl phosphate, phthalic acid esters and the like are known (for example, Japanese Patent Laid-Open No. 9-95557). In addition, sulfonamide compounds such as N-ethyltoluenesulfonamide are also known, and it is known that increasing the content of these plasticizers improves moisture permeability and improves film performance.

However, the glass transition point of a cellulose acylate film becomes low gradually by increasing a plasticizer, and there existed a problem that dimensional stability deteriorated by softening of a film. In addition, by simply increasing the amount of the plasticizer, the plasticizer is not compatible with the cellulose acylate film and the film becomes cloudy, or the optical anisotropy (for example, retardation value (Rth) in the thickness direction) of the film is increased. There is a problem.

When using a cellulose acylate film for an optical material, it is preferable to make the optical anisotropy of a film small depending on a use use. It is known that the compound called the plasticizer has an effect of lowering the optical anisotropy of the cellulose acylate film. For example, certain fatty acid esters are disclosed (for example, JP 2001-247717 A, Japanese Unexamined Patent Publication No. 2001-336179, Japanese Unexamined Patent Publication No. 2000-63560, and Japanese Unexamined Patent Publication No. Hei 11-246704), such plasticizers have a disadvantage of deteriorating moisture permeability under high temperature and high humidity.

Therefore, the development of the cellulose acylate film and its modifier which have small optical anisotropy and low moisture permeability under high temperature and high humidity is urgently desired.

The 1st object of this invention is to provide the cellulose body film which has low moisture permeability under high temperature, high humidity.

The 2nd object of this invention is to provide the cellulose body film with small optical anisotropy.

A third object of the present invention is to provide a polarizing plate protective film, a liquid crystal display device, and a support for a silver halide photographic photosensitive material produced using a cellulose-based film having low moisture permeability under high temperature and high humidity.

The object of the present invention has been achieved by the following means.

(1) A cellulose body composition characterized by containing at least one of a cellulose body and a compound represented by the following general formula (1):

General formula (1)

[Wherein, R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group. X represents a divalent linking group formed of at least one group selected from the following linking group group 1. Y represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group.

(Connection gigun 1) a single ^{bond, -O-, -CO-, -NR 4 -} , represents an alkylene group or arylene group. R ⁴ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.].

(2) A cellulose body composition characterized by containing at least one of a cellulose body and a compound represented by the following general formula (2):

General formula (2)

[Wherein, Q ¹ , Q ² and Q ³ each independently represent a 5 or 6 membered ring. X <^1> represents B, CR (R represents a hydrogen atom or a substituent), N, P, P = O.].

(3) The manufacturing method of the cellulose body composition characterized by including the process of containing at least one compound represented by the said General formula (1) or General formula (2) in a cellulose body.

(4) A cellulosic film comprising at least one compound represented by the general formula (1) or (2).

(5) Said general formula (2) is represented by following general formula (3), The cellulose body film as described in (4) characterized by the above-mentioned:

General formula (3)

[Wherein, X ² represents B, CR (wherein R represents a hydrogen atom or a substituent), N, P, or P═O. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are each independently a hydrogen atom Or a substituent.

One group selected from the group consisting of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ and one group selected from the group consisting of R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ You may bond through a coupling group (such as an alkylene group having 1 to 10 carbon atoms) to form a cyclic structure.].

(6) The cellulose body film according to (4) or (5), wherein the cellulose body is cellulose acylate.

(7) A cellulose acylate film containing cellulose acylate and at least one compound represented by the general formula (1) or (2) in an amount of 1 to 30% by mass of the cellulose acylate.

(8) The cellulose acylate film as described in (6) or (7) whose acyl substitution degree of cellulose acylate is 2.60-3.00.

(9) The cellulose acylate film according to (6) or (7), wherein the acyl substitution degree of the cellulose acylate is 2.80 to 2.95.

(10) The cellulose acylate film as described in (6) or (7) whose substitution degree substituted by the acetyl group of a cellulose acylate is 2.60-3.00.

(11) The cellulose acylate film as described in (6) or (7) whose substitution degree substituted by the acyl group of 3-22 carbon atoms of a cellulose acylate is 0.00-0.80.

(12) (6) wherein cellulose acylate is substituted with an acetyl group and an acyl group having 3 to 22 carbon atoms, and at least 30% of the acyl groups having 3 to 22 carbon atoms are present as substituents on the 6th-position hydroxyl group; The cellulose acylate film as described in (7).

(13) The cellulose acylate film according to (6) or (7), wherein the acyl substitution degree at the 6th position of the cellulose acylate is 0.80 to 1.00.

(14) The cellulose acylate film according to (6) or (7), wherein the acyl substitution degree at the 6th position of the cellulose acylate is 0.85 to 1.00.

(15) A modifier for cellulose-based film, which is represented by General Formula (1), General Formula (2) or General Formula (3).

(16) A polarizing plate protective film, comprising one or more layers of the cellulose-based film according to any one of the above (4) to (14).

(17) A liquid crystal display device comprising one or more layers of the cellulose-based film according to any one of (4) to (14).

(18) A silver halide photographic photosensitive material using the cellulose-based film according to any one of (4) to (14) as a support.

(The best mode for carrying out the invention)

In the present invention, at least one compound represented by the following general formula (1), (2) or (3) is used as a modifier for cellulose bodies.

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

General formula (1)

In the general formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (eg, methyl, ethyl, propyl, isopropyl, amyl, isoamyl). ), And particularly preferably at least one of R ¹ , R ² and R ³ is an alkyl group having 1 to 3 carbon atoms (eg methyl, ethyl, propyl, isopropyl). X is a single bond, -O-, -CO-, an alkylene group (preferably having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, for example, methylene, ethylene, propylene) or an arylene group (Preferably having 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms, for example, a divalent linking group formed of at least one group selected from phenylene, biphenylene, naphthylene). And it is especially preferable that it is a bivalent coupling group formed from 1 or more types chosen from -O-, an alkylene group, or an arylene group. Y is a hydrogen atom, an alkyl group (preferably 2 to 25 carbon atoms, more preferably 2 to 20 carbon atoms), for example, ethyl, isopropyl, t-butyl, hexyl, 2-ethylhexyl, t-octyl , Dodecyl, cyclohexyl, dicyclohexyl, adamantyl), aryl group (preferably having 6 to 24 carbon atoms, more preferably 6 to 18, for example, phenyl, biphenyl, terphenyl , Naphthyl) or an aralkyl group (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, for example benzyl, credyl, t-butylphenyl, diphenylmethyl, triphenylmethyl) It is preferable that it is and it is especially preferable that it is an alkyl group, an aryl group, or an aralkyl group. As a combination of -XY, it is preferable that the total carbon number of -XY is 0-40, It is more preferable that it is 1-30, It is most preferable that it is 1-25. Although the preferable example of the compound represented by these General formula (1) is shown below, this invention is not limited to these specific examples.

The compound represented by General formula (2) of this invention below is demonstrated in detail.

General formula (2)

Q ¹ , Q ² and Q ³ each independently represent a 5 or 6 membered ring, may be a hydrocarbon ring or a hetero ring, and these may be a single ring or may form a condensed ring with another ring.

As a hydrocarbon ring, Preferably, they are a substituted or unsubstituted cyclohexane ring, a substituted or unsubstituted cyclopentane ring, and an aromatic hydrocarbon ring, More preferably, they are an aromatic hydrocarbon ring.

As a hetero ring, it is a ring which preferably contains at least one of an oxygen atom, a nitrogen atom or a sulfur atom of a 5 or 6 membered ring. As a hetero ring, More preferably, it is an aromatic hetero ring containing one or more of an oxygen atom, a nitrogen atom, or a sulfur atom.

As Q ¹ , Q ² and Q ³ , they are preferably aromatic hydrocarbon rings or aromatic hetero rings.

As an aromatic hydrocarbon ring, Preferably it is a C6-C30 single ring or a double ring aromatic hydrocarbon ring (For example, a benzene ring, a naphthalene ring, etc. are mentioned.), More preferably, C6-C20 aromatic It is a hydrocarbon ring, More preferably, it is a C6-C12 aromatic hydrocarbon ring, Especially preferably, it is a benzene ring.

As an aromatic hetero ring, Preferably, it is an aromatic hetero ring containing an oxygen atom, a nitrogen atom, or a sulfur atom. As specific examples of the hetero ring, for example, furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazolin, thiazole , Thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cynoline, pteridine, acridine, phenanthroline, phenazine And tetrazole, benzimidazole, benzoxazole, benzthiazole, benzotriazole, tetrazaindene and the like. Particularly preferred as aromatic hetero rings are pyridine, triazine and quinoline.

As Q <^1> , Q <^2> and Q <^3> , More preferably, it is an aromatic hydrocarbon ring, Especially preferably, it is a benzene ring.

Moreover, Q <^1> , Q <^2> and Q <^3> may have a substituent and the substituent T mentioned later is mentioned as a substituent.

X ¹ represents B, CR (wherein R represents a hydrogen atom or a substituent), N, P, P = 0, and X ¹ preferably represents B, CR (R preferably an aryl group, substituted or Unsubstituted amino group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, hydroxy group, mercapto group, halogen An atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) and a carboxyl group, more preferably an aryl group, an alkoxy group, an aryloxy group, a hydroxy group or a halogen atom, and more preferably an alkoxy group or a hydroxy group and, particularly preferably a hydroxy group is.), N, is preferably CR, N than as X ^1, and particularly preferably CR.

As general formula (2), it is a compound preferably represented by the following general formula (3).

General formula (3)

X ² represents B, CR (wherein R represents a hydrogen atom or a substituent), N, P, and P = 0, and X ² preferably represents B, CR (R preferably an aryl group, substituted or Unsubstituted amino group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, hydroxy group, mercapto group, halogen Atoms (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) and a carboxyl group, More preferably, they are an aryl group, an alkoxy group, an aryloxy group, a hydroxyl group, and a halogen atom, More preferably, an alkoxy group and a hydroxyl group And, particularly preferably, a hydroxy group.), N, and P = O, more preferably CR and N, and particularly preferably CR.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ represent a hydrogen atom or a substituent The substituent T mentioned later can be applied as a substituent. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are preferably alkyl groups, Alkenyl, alkynyl, aryl, substituted or unsubstituted amino, alkoxy, aryloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, Sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, ureido group, phosphate amide group, hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine Atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having 1 to 30 carbon atoms) Preferably it is 1-12, As a hetero atom, For example, a nitrogen atom, An oxygen atom, a sulfur atom, specifically, imidazolyl, pyridyl, quinolyl, furyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, etc. are mentioned, for example. .), A silyl group, more preferably an alkyl group, an aryl group, a substituted or unsubstituted amino group, an alkoxy group, an aryloxy group, and more preferably an alkyl group, an aryl group, or an alkoxy group.

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

The substituent T mentioned above is demonstrated below. As the substituent T, for example, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms), for example, methyl, ethyl, iso-propyl, tert- Butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like.), Alkenyl group (preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms) , Particularly preferably 2 to 8 carbon atoms, for example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), an alkynyl group (preferably 2 to 20 carbon atoms), more preferably Is C2-C12, Especially preferably, it is C2-C8, For example, propargyl, 3-pentynyl, etc. are mentioned.), An aryl group (preferably C6-C30, More preferably, Is 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, for example, And a substituted or unsubstituted amino group (preferably 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms). For example, amino, methylamino, dimethylamino, diethylamino, dibenzylamino, etc.), an alkoxy group (preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably C1-C8, for example, methoxy, ethoxy, butoxy, etc.), an aryloxy group (preferably C6-C20, More preferably, C6-C16, Especially preferably, Has 6 to 12 carbon atoms, and examples thereof include phenyloxy, 2-naphthyloxy, and the like.), An acyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably Is 1 to 12 carbon atoms, for example, Acetyl, benzoyl, formyl, pivaloyl, etc.) and an alkoxy carbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms). For example, methoxycarbonyl, ethoxycarbonyl, etc.), an aryloxycarbonyl group (preferably C7-20, More preferably, C7-16, Especially preferably, it is C7-10, For example, phenyloxycarbonyl etc.) and an acyloxy group (preferably C2-C20, More preferably, it is C2-C16, Especially preferably, it is C2-C10, For example, , Acetoxy, benzoyloxy, etc.), acylamino group (preferably C2-C20, More preferably, it is C2-C16, Especially preferably, it is C2-C10, For example, acetylamino , And alkoxycarbonylamino group (preferably C2-C20, More preferably, it is C2-C16, Especially preferably, it is C2-C12, For example, methoxycarbonyl Amino, etc.) and an aryloxycarbonylamino group (preferably C7-20, More preferably, C7-16, Especially preferably, it is C7-12, For example, Phenyloxycarbonyl Amino, etc.), sulfonylamino group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, methanesulfonylamino, benzene Sulfonylamino, etc.), sulfamoyl group (preferably C0-20, More preferably, C0-16, Especially preferably, C0-12, For example, sulfamoyl, Methyl sulfamoyl, dimethyl sulfamoyl, phenyl sulfamoyl, etc.), carbamoyl group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, Examples include carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, and the like.), An alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 20 carbon atoms). 16, particularly preferably 1 to 12 carbon atoms, for example, methylthio, ethylthio, etc.), an arylthio group (preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms); Especially preferably, it is C6-C12, and a phenylthio etc. are mentioned, for example.) A sulfonyl group (preferably C1-C20, More preferably, C1-C16, Especially preferably, C1-C1) To 12, for example, Thread, tosyl, etc.), sulfinyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, methanesulfinyl, benzene Sulfinyl, etc.), a ureido group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, ureido, methylureido , Phenylureido, etc.), phosphate amide group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, diethyl phosphoric acid Amide, phenyl phosphate amide, etc.), hydroxy group, mercapto group, halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, Hydroxyl group, sulfino group, Dragino group, imino group, heterocyclic group (preferably C1-C30, More preferably, it is 1-12, As a hetero atom, For example, a nitrogen atom, an oxygen atom, a sulfur atom, For example, , Imidazolyl, pyridyl, quinolyl, furyl, piperidyl, morpholino, benzooxazolyl, benzimidazolyl, benzthiazolyl, etc.), silyl group (preferably having 3 to 3 carbon atoms) 40, More preferably, it is C3-C30, Especially preferably, it is C3-C24, For example, trimethylsilyl, triphenylsilyl, etc. are mentioned). These substituents may further be substituted. Moreover, when there are two or more substituents, they may be same or different. In addition, if possible, they may be connected to each other to form a ring.

Among the compounds represented by the general formula (3), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ³¹ , R ³² , R ³³ , R One group selected from the group consisting of ³⁴ and R ³⁵ and other compounds represented by general formula (3) R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ , One group selected from the group consisting of R ²⁵ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ is bonded by a single bond or a divalent group (such as an alkylene group having 1 to 10 carbon atoms), and in one molecule Compounds having two X ² can also be used in the present invention.

In General Formula (3), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ³¹ , R ³² , R ³³ , R ³⁴ And as a substituent of R <^35> , the structure represented by following General formula (4) can also be employ | adopted.

General formula (4)

[Wherein, X ² represents B, CR (wherein R represents a hydrogen atom or a substituent), N, P, or P═O. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom or a substituent.]

Moreover, it is preferable that the addition amount of the cellulose-type modifier of this invention is 0.1-20 mass% with respect to a cellulose body, It is more preferable that it is 0.5-16 mass%, It is further more preferable that it is 1-16 mass%, 2-15 It is especially preferable that it is mass%.

Next, although the preferable example of a compound represented by General formula (2) is shown below, this invention is not limited to these specific examples.

The compounds used in the present invention can all be prepared from known compounds. Generally, the compound of General formula (1) can be synthesize | combined by the following method. That is, it is obtained by condensation reaction of phosphorus oxychloride and the corresponding trimethylol derivative.

<Manufacture example 1>

Synthesis of A-1: Into a 500 ml three-necked flask equipped with a mechanical stirrer, thermometer, cooling tube, and dropping funnel, 26.8 g of trimethylolpropane was weighed, and 30.7 g of phosphorus oxychloride was added dropwise under ice cooling, followed by room temperature. The reaction was carried out for 6 hours at room temperature, and again for 3 hours at 70 ° C. After the reaction mixture was returned to room temperature, 100 mL of 1N sodium hydroxide aqueous solution was added thereto, followed by separating and extracting with 200 mL of methylene chloride. The obtained organic layer was washed twice with 150 ml of 1N aqueous sodium hydroxide solution and saturated brine, dehydrated with anhydrous magnesium sulfate, and concentrated to give 15 g of a white solid. The obtained white solid was recrystallized from 200 ml of water, and the crystals were filtered, and then dried overnight at 60 ° C. to obtain 8.9 g of the target compound A-1 (yield 25%). Melting point 140 ° C.

<Manufacture example 2>

Synthesis of A-2: A 1 L three-necked flask equipped with a thermometer, a cooling tube, and a dropping funnel weighed 35.5 g of n-octan, 152 g of aqueous formaldehyde solution (37%), 170 ml of ethanol, and 170 ml of water. Then, a potassium hydroxide solution (potassium hydroxide / ethanol / water = 14 g / 67 ml / 67 ml) was added dropwise at room temperature, followed by reaction at room temperature for 4 hours. After concentrating the reaction solution, 300 ml of ethyl acetate was added, washed three times with 200 ml of saturated brine, and the obtained organic layer was dehydrated with anhydrous magnesium sulfate and concentrated to give a colorless transparent oil. 27.3g of desired trimethylol derivatives (white crystals) were obtained by refine | purifying the obtained oily substance by the silica gel column (developing solvent: methylene chloride / methanol = 10/1) (yield 54%).

Next, 17.0 g of the trimethylol derivative was weighed into a 300 ml three-necked flask equipped with a mechanical stirrer, thermometer, cooling tube, and dropping funnel, 12.8 g of phosphorus oxychloride was added dropwise under ice cooling, and then returned to room temperature. The mixture was reacted for 2 hours at and further reacted at 50 ° C for 4 hours. After the reaction mixture was returned to room temperature, 100 mL of 1N sodium hydroxide aqueous solution was added thereto, followed by separating and extracting with 150 mL of methylene chloride. The obtained organic layer was washed twice with 150 ml of 1N aqueous sodium hydroxide solution and saturated brine, dehydrated with anhydrous magnesium sulfate, and concentrated to give a white solid. The obtained white solid was purified by a silica gel column (developing solvent: methylene chloride / methanol = 10/1), and then dried at 60 ° C. overnight to obtain 5.0 g of the target compound A-2 (yield 24%).

<Manufacture example 3>

Synthesis of A-19: 201.3 g of 3-phenylpropionaldehyde, 913 g of formaldehyde aqueous solution (37%), 900 ml of ethanol and 900 ml of water in a 5-liter three-necked flask equipped with a thermometer, a cooling tube, and a dropping funnel. Was measured, and potassium hydroxide solution (potassium hydroxide / ethanol / water = 84 g / 400 mL / 400 mL) was added dropwise at room temperature, and then reacted at room temperature for 4 hours, and then further reacted at 40 ° C for 6 hours. After concentrating the reaction solution, 1 L of ethyl acetate was added, washed three times with 500 ml of saturated brine, and the obtained organic layer was dehydrated with anhydrous magnesium sulfate and concentrated to give a colorless transparent oil. The obtained oily substance was refine | purified by the silica gel column (developing solvent: methylene chloride / methanol = 10/1), and 189.1g of desired trimethylol derivatives (white crystals) were obtained (yield 64%).

Next, 180 g of the trimethylol derivative and 500 ml of pyridine were weighed into a 2-liter three-necked flask equipped with a mechanical stirrer, a thermometer, a cooling tube, and a dropping funnel, and dropwise 140.7 g of phosphorus oxychloride was added at room temperature. The mixture was returned to react at room temperature for 2 hours and further reacted at 60 ° C for 4 hours. After returning the reaction mixture to room temperature, 500 ml of 1N sodium hydroxide aqueous solution was added, and it liquid-separated and extracted with 1 L of methylene chloride. The obtained organic layer was washed twice with 500 ml of 1N aqueous sodium hydroxide solution and saturated brine, dehydrated with anhydrous magnesium sulfate, and then concentrated to give a white solid. The obtained white solid was recrystallized from the mixed solvent of ethyl acetate / hexane, the crystal | crystallization was filtered, and 114.6g of target compound A-19 was obtained by drying overnight at 60 degreeC (yield 52%).

<Manufacture example 4>

Synthesis of A-43: 13.6 g of pentaerythritol and 500 ml of pyridine were weighed into a 1 L three-necked flask equipped with a thermometer, a cooling tube, and a dropping funnel, and 29.3 g of trityl chloride were added directly at room temperature. It was made to react at 100 degreeC for 4 hours. After concentrating the reaction solution, 400 ml of methylene chloride was added and washed three times with 300 ml of 1N hydrochloric acid and saturated brine, respectively. The obtained organic layer was dehydrated with anhydrous magnesium sulfate and concentrated to give a yellow transparent oil. 8.6g of the desired trimethylol derivatives (white crystals) were obtained by refine | purifying the obtained oily substance by the silica gel column (developing solvent: methylene chloride / methanol = 10/1) (yield 23%).

Next, 8.5 g of the trimethylol derivative and 50 ml of pyridine were weighed into a 300 ml three-necked flask equipped with a mechanical stirrer, thermometer, cooling tube, and dropping funnel, and 3.4 g of phosphorus oxychloride was added dropwise under ice cooling. It returned to room temperature and made it react at room temperature for 8 hours. After the reaction mixture was returned to room temperature, 150 mL of 1N sodium hydroxide aqueous solution was added thereto, followed by separating and extracting with 200 mL of methylene chloride. The obtained organic layer was further washed twice with 200 ml of 1N aqueous sodium hydroxide solution, 1N hydrochloric acid and saturated brine, dehydrated with anhydrous magnesium sulfate and concentrated to give a white solid. The obtained white solid was recrystallized from the mixed solvent of ethyl acetate / hexane, and the crystal | crystallization was filtered, and 3.0g of target compound A-43 was obtained by drying overnight at 60 degreeC (yield 32%).

As for the compound represented by the general formula (2) of the present invention, most of them are known compounds and can be obtained from Tokyo Kasei Kogyo Co., Ltd. and the like. Hereinafter, the manufacture example regarding a newly synthesized compound is given.

Production Example 5

Synthesis of B-13: A 200 ml three-necked flask equipped with a thermometer, cooling tube, and dropping funnel weighed 1.07 g of magnesium (sliced), 0.23 g of 4-bromobiphenyl, and 10 ml of dehydrated THF. Stir vigorously at 50 ° C. Subsequently, 10.26 g of 4-bromobiphenyl dissolved in 10 ml of THF was slowly added dropwise to reflux for 2 hours. 7.29 g of benzphenone dissolved in 10 mL of THF was slowly added dropwise to reflux for 3 hours. The reaction solution was poured into water / ammonium chloride / water = 75 g / 15 g / 30 g with vigorous stirring, and 300 mL of ethyl acetate was added to separate and extract. The obtained organic layer was washed three times with 200 ml of water, dehydrated with anhydrous magnesium sulfate and concentrated to give a colorless transparent oily substance. The obtained oily substance was purified by a silica gel column (developing solvent: ethyl acetate / hexane = 1/5), and then dried at 60 ° C. overnight to obtain 7.1 g of the target compound B-13 (yield 53%).

<Manufacture example 6>

Synthesis of B-14: A 200 ml three-necked flask equipped with a thermometer, cooling tube, and dropping funnel weighed 1.07 g of magnesium (sliced), 0.23 g of 4-bromobiphenyl and 10 ml of dehydrated THF. Stir vigorously at 50 ° C. Subsequently, 10.26 g of 4-bromobiphenyl dissolved in 10 ml of THF was slowly added dropwise to reflux for 2 hours. Further, 10.33 g of 4-phenylbenzophenone dissolved in 10 ml of THF was slowly added dropwise to reflux for 3 hours. The reaction solution was poured into ice / ammonium chloride / water = 75 g / 15 g / 30 g with vigorous stirring, and 300 ml of ethyl acetate was added thereto for separation and extraction. The obtained organic layer was washed three times with 200 ml of water, dehydrated with anhydrous magnesium sulfate and concentrated to give a colorless transparent oily substance. The obtained oily substance was purified by a silica gel column (developing solvent: methylene chloride / methanol = 10/1), and then dried at 60 ° C overnight to obtain 6.0 g of the target compound B-14 (yield 33%).

Next, the cellulose body used for this invention is demonstrated in detail. Any cellulose body used for this invention may be a compound which uses cellulose as a raw material. Preferably cellulose acylate. The cellulose acylate used in the present invention is not particularly limited as long as the effect of the present invention is expressed, and other two or more kinds of cellulose acylate may be mixed and used. Especially, the following are mentioned as a preferable cellulose acylate. That is, a cellulose acylate is a cellulose acylate which the substitution degree with respect to the hydroxyl group of cellulose satisfy | fills all following formula (I)-(III).

(I) 2.6 ≤ SA + SB ≤ 3.0

(II) 1.8 ≤ SA ≤ 3.0

(III) 0 ≤ SB ≤ 0.8

Here, SA and SB in the above formula means the substitution degree of the acyl group substituted with the hydroxyl group of cellulose, SA is the substitution degree of the acetyl group, and SB is the substitution degree of the acyl group having 3 to 22 carbon atoms. .

The glucose unit which comprises cellulose by (beta) -1, 4-glycosidic bond has a free hydroxyl group in 2nd, 3rd, and 6th positions. The cellulose acelate used for this invention is a polymer (polymer) which esterified some or all of these hydroxyl groups by the acyl group. In this specification, an acyl substitution degree means the ratio in which cellulose is esterified with respect to 2nd, 3rd, and 6th positions, and total acyl substitution degree represents the sum total of these. Specifically, the case where the hydroxyl groups of the 2nd, 3rd, and 6th positions of cellulose are each 100% esterified is referred to as substitution degree 1, respectively. Therefore, when all 2nd, 3rd, and 6th positions of the cellulose are 100% esterified, the total acyl substitution degree is at most 3.

In this invention, the sum total of substitution degree of SA and SB of a hydroxyl group becomes like this. More preferably, it is 2.7-2.96, Especially preferably, it is 2.80-2.95. The substitution degree of SB is preferably 0 to 0.80, particularly preferably 0 to 0.60. Moreover, it is preferable that 28% or more of SB is a substituent of 6-position hydroxyl group, More preferably, 30% or more is a substituent of 6-position hydroxyl group, 31% or more is more preferable, 32% or more is a substituent of 6-position hydroxyl group Is particularly preferred.

Moreover, the sum total of substitution degree of SA and SB of the 6th position of a cellulose acylate becomes like this. Preferably it is 0.8 or more, More preferably, it is 0.85 or more, Especially preferably, the cellulose acylate film is mentioned.

These cellulose acylates make it possible to produce a solution in which solubility is desirable, and in particular, a solution, preferably a film, in a non-chlorine-based organic solvent can be prepared.

As a C3-C22 acyl group (SB) of a cellulose acylate, it may be an aliphatic acyl group, an aromatic acyl group, and is not specifically limited. These are acyl groups in alkylcarbonyl ester, alkenylcarbonyl ester or aromatic carbonyl ester, aromatic alkylcarbonyl ester, etc. of cellulose, for example, and may have a group substituted further, respectively. Preferred specific examples thereof include propionyl, butanoyl, heptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl and hexadecanoyl. Octadecanoyl, iso-butanoyl, t-butanoyl, cyclohexanecarbonyl, oleoyl, benzoyl, naphthylcarbonyl, cinnamoyl group and the like. Among these, propionyl, butanol, dodecanoyl, octadecanoyl, t-butanol, oleyl, benzoyl, naphthylcarbonyl, cinnamoyl and the like.

The basic principle of the method for synthesizing cellulose acylate is described in Michi et al., Pp. 180-190 (Gyoritsu Publication, 1968). A typical synthesis method is liquid phase acetization with a carboxylic 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 charged into a pre-cooled carboxylated mixture, followed by esterification, followed by complete cellulose acylate (second, third and sixth place). The sum of the degree of acyl substitution synthesizes almost 3.00). The carboxylic acid mixed solution generally contains acetic acid as a solvent, anhydrous carboxylic acid as an esterifying agent and sulfuric acid as a catalyst. Anhydrous carboxylic acid is usually used in an excess amount stoichiometrically than the sum total of the cellulose which reacts with this, and the water which exists in a system. Neutralizing agents (e.g., carbonates, acetates or oxides of calcium, magnesium, iron, aluminum or zinc) for the hydrolysis of excess anhydrous carboxylic acid and partial neutralization of the esterification catalyst remaining in the system after completion of the acylation reaction An aqueous solution of is added. Next, the obtained complete cellulose acylate is saponified by maintaining at 50 to 90 ° C in the presence of a small amount of acelation reaction catalyst (usually remaining sulfuric acid), and changed to cellulose acylate having a desired acyl substitution degree and polymerization degree. Let's do it. At the time of obtaining the desired cellulose acylate, the cellulose acylate solution was added to water or dilute sulfuric acid (or water or diluted in cellulose acylate solution) without completely neutralizing or remaining neutralizing the catalyst remaining in the system using the neutralizing agent as described above. Sulfuric acid is added) to separate cellulose acylate, and cellulose acylate is obtained by washing and stabilizing treatment.

It is preferable that the cellulose acylate film of this invention consists of the cellulose acylate which the polymer component which comprises a film substantially has the said definition. "Substantially" means 55 mass% or more (preferably 70-100 mass%, More preferably, 80-100 mass%, More preferably, 90-100 mass%) of a polymer component. It is preferable to use cellulose acylate particles as a raw material for film production. It is preferable that 90 mass% or more of the particles to be used have a particle diameter of 0.5 to 5 mm. Moreover, it is preferable that 50 mass% or more of the particle to be used has a particle diameter of 1-4 mm. It is preferable that a cellulose acylate particle is a shape as close as spherical as possible.

The polymerization degree of the cellulose acylate preferably used in the present invention is a viscosity average polymerization degree of 200 to 700, preferably 250 to 550, more preferably 250 to 400, and particularly preferably 250 to 350 viscosity average polymerization degree. The average degree of polymerization can be measured by an intrinsic viscosity method such as Uda et al. (Kazuo Uda, Hideo Hideo, Textile Society, Vol. 18, No. 1, pp. 105-120, 1962). In addition, it is described in detail in Unexamined-Japanese-Patent No. 9-95538.

When the low molecular weight component is removed, the average molecular weight (polymerization degree) increases, but the viscosity is lower than that of ordinary cellulose acylate. The cellulose acylate with low low molecular weight component can be obtained by removing the low molecular weight component from the cellulose acylate synthesized by the usual method. Removal of the low molecular weight component can be performed by washing a cellulose acylate with a suitable organic solvent. Moreover, when manufacturing the cellulose acylate with few low molecular components, it is preferable to adjust the amount of sulfuric acid catalysts in an acetization reaction to 0.5-25 mass parts with respect to 100 mass parts of cellulose. When the amount of the sulfuric acid catalyst is in the above range, cellulose acylate which is preferable (even in molecular weight distribution) can be synthesized from the viewpoint of molecular weight distribution.

When used for the production of the cellulose body composition or the film of the present invention, for example, the water content of cellulose bodies such as cellulose acylate is preferably 2% by mass or less, more preferably 1% by mass or less, particularly preferably 0.7% by mass. % Or less Typical (eg commercially available) cellulose acylate contains 2.5 to 5 mass% of water. In this invention, in order to make it the moisture content of this cellulose acylate, it is necessary to dry, and the method will not be specifically limited if the target moisture content can be obtained.

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

Various additives (for example, a plasticizer, a sunscreen, a deterioration inhibitor, an optically anisotropic regulator, microparticles, a peeling agent, an infrared absorber, etc.) according to a use can be added to the cellulose body film of this invention in each manufacturing process. These may be solid or an oily substance may be sufficient as them. That is, the melting point or boiling point is not particularly limited. For example, it is mixing of the ultraviolet absorbing material below melting | fusing point 20 degreeC and melting | fusing point 20 degreeC or more, mixing of a plasticizer similarly, etc., for example, are described in Unexamined-Japanese-Patent No. 2001-151901. Moreover, as an infrared absorption dye, it is described in Unexamined-Japanese-Patent No. 2001-194522, for example. Moreover, the addition time may be added at any time in a dope preparation process, and you may add and implement the process of adding and manufacturing an additive to the last manufacturing process of a dope preparation process. In addition, the addition amount of each raw material is not specifically limited as long as a function is expressed. Moreover, when a cellulose acylate film is formed in multiple layers, the kind and addition amount of each layer additive may differ. For example, it is described in Unexamined-Japanese-Patent No. 2001-151902 etc. These are the techniques known conventionally.

As for these details, the materials described in detail on pages 16 to 22 of the Invention Association Publication (Publication No. 2001-1745, issued March 15, 2001, Invention Association) are preferably used.

Below, the organic solvent which melt | dissolves the cellulose body used for this invention is demonstrated.

First, the non-chlorine organic solvent used preferably when manufacturing the solution of a cellulose body is demonstrated. In the present invention, the non-chlorine-based organic solvent to be used is not particularly limited as long as the object can be achieved within the range in which the cellulose body is dissolved and can be cast or formed into a film. The non-chlorine organic solvent used in the present invention is preferably a solvent selected from esters, ketones and ethers having 3 to 12 carbon atoms. The ester, ketone and ether may have a cyclic structure. Compounds having two or more of functional groups of esters, ketones and ethers (ie, -O-, -CO- and -COO-) can also be used as the main solvent, and have other functional groups such as, for example, alcoholic hydroxyl groups. You may be. In the case of the main solvent which has two or more types of functional groups, the carbon atom number should just be in the defined range of the compound which has any one functional group.

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

Although the non-chlorine organic solvent used for the above-mentioned cellulose body is selected from the various viewpoints mentioned above, Preferably it is three or more types of mixed solvent different from each other.

The first solvent is at least one selected from methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, dioxolane and dioxane, or a mixture thereof, preferably methyl acetate, acetone, methyl formate, ethyl formate or these Is a mixture of.

The second solvent is at least one selected from ketones or acetoacetic acid esters having 4 to 7 carbon atoms or a mixture thereof, preferably methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl acetyl acetate or a mixture thereof. to be.

Moreover, when a 1st solvent is a liquid mixture of 2 or more types of solvents, you may not need a 2nd solvent.

The third solvent is selected from alcohols or hydrocarbons having 1 to 10 carbon atoms, preferably alcohols having 1 to 8 carbon atoms.

Portions other than the hydroxyl group of alcohol which is a 3rd solvent may be linear, may have a branch, or may be cyclic, and it is especially preferable that it is a saturated aliphatic hydrocarbon. Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 2-methyl-2-butanol and cyclohexanol. Moreover, fluorine-type alcohol can also be used as alcohol. For example, 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3- tetrafluoro-1-propanol, etc. are mentioned.

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

The alcohol and hydrocarbon which are these 3rd solvents may be individual, or may be a mixture of two or more types, and is not specifically limited. As the third solvent, preferred specific compounds include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol and cyclohexanol, cyclohexane, hexane, and in particular methanol, ethanol, 1-propanol, 2-propanol, 1-butanol.

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

Moreover, when a 1st solvent does not use a 2nd solvent in a liquid mixture, it is preferable to contain 20 to 90 mass% of a 1st solvent, and 5 to 30 mass% of a 3rd solvent, and a 1st solvent Is 30 to 86% by mass, and further preferably 7 to 25% by mass of the third solvent.

The non-chlorine-based organic solvent used in the present invention described above is described in more detail on pages 12 to 16 of the Invention Association Publication (Publication No. 2001-1745, issued March 15, 2001, Invention Association). Preferred combinations of non-chlorine organic solvents of the present invention include, but are not limited to these.

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 by mass),

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

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

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

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

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

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

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

Methyl acetate / cyclohexanone / methanol / hexane (70/20/5/5 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 / acetoacetic acid methyl / methanol / ethanol (65/20/10/5, parts by mass),

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

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

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

Etc. can be mentioned.

It is also possible to use a cellulose acylate solution in the following method.

In the dope used for this invention, 10 mass% or less of dichloromethane may be contained in addition to the said non-chlorine type organic solvent of the total amount of organic solvents.

Moreover, when manufacturing the solution of the cellulose acylate of this invention, a chlorine organic solvent is also used as a main solvent in some cases. In this invention, the chlorine organic solvent is not specifically limited in the range which cellulose acylate melt | dissolves, and can cast and film | membrane. These chlorine organic solvents are preferably dichloromethane and chloroform. Dichloromethane is particularly preferred. In addition, there is no problem in particular in mixing organic solvents other than a chlorine organic solvent. In that case, it is preferable to use 50 mass% or more of dichloromethanes.

As a non-chlorine organic solvent used together, the solvent chosen from ester of 3-12 carbon atoms, ketone, ether, alcohol, hydrocarbon, etc. is preferable. Esters, ketones, ethers and alcohols may have a cyclic structure. Compounds having at least two of functional groups of esters, ketones and ethers (ie, -O-, -CO- and -COO-) can also be used as the solvent, and have simultaneously other functional groups such as, for example, alcoholic hydroxyl groups. You may be. In the case of the solvent which has two or more types of functional groups, the carbon atom number should just be in the prescribed range of the compound which has any one functional group.

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

Moreover, as alcohol used together with a chlorine type organic solvent, Preferably, it may be linear, may have a branch, or may be cyclic, and it is especially preferable that it is a saturated aliphatic hydrocarbon. The hydroxyl group of the alcohol may be any of the first to third classes. Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2--butanol, t-butanol, 1-pentanol, 2-methyl-2-butanol and cyclohexanol. Fluorine alcohol is also used as the alcohol. For example, 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3- tetrafluoro-1-propanol, etc. are mentioned. In addition, a hydrocarbon may be linear, may have a branch, or may be cyclic. Both aromatic and aliphatic hydrocarbons can be used. The aliphatic hydrocarbon may be saturated or unsaturated. Examples of hydrocarbons include cyclohexane, hexane, benzene, toluene and xylene.

Although it does not specifically limit about the non-chlorine organic solvent used together with the chlorine organic solvent which is a main solvent used for the above-mentioned cellulose acylate, Methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, dioxolane, dioxane, and carbon atom number 4-7 ketones or acetoacetic acid esters, C1-C10 alcohols or hydrocarbons. Further preferred non-chlorine organic solvents used together are methyl acetate, acetone, methyl formate, ethyl formate, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl acetyl acetate, methanol, ethanol, 1-propanol, 2-propanol, 1 -Butanol, 2-butanol and cyclohexanol, cyclohexane and hexane. Although the following is mentioned as a combination with the chlorine type organic solvent which is a preferable main solvent of this invention, It is not limited to these.

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

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

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

ㆍ dichloromethane / methylethylketone / methanol / butanol (80/10/5/5, parts by mass)

Dichloromethane / acetone / methylethylketone / ethanol / isopropanol (75/10/10/5/7, parts by mass)

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

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

ㆍ dichloromethane / cyclohexanol / methanol / hexane (70/20/5/5, parts by mass)

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

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

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

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

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

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

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

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

Etc. can be mentioned.

The cellulose acylate of the present invention is preferably a solution in which 10 to 30% by mass is dissolved in an organic solvent, more preferably 13 to 27% by mass, and particularly, a cellulose acylate solution in which 15 to 25% by mass is dissolved. Is preferably. The method for producing cellulose acylate at these concentrations may be prepared so as to have a predetermined concentration in the dissolving step, and may be prepared in a low concentration solution (for example, 9 to 14 mass%) in advance and then prescribed in the concentration step described later. You may adjust with a high concentration solution of. Moreover, it is good also as a predetermined | prescribed low concentration cellulose acylate solution by adding various additives after making it into a high concentration cellulose acylate solution beforehand, and if it is implemented so that it may become the said preferable cellulose acylate solution concentration in any way, there will be no problem in particular.

Next, in this invention, it is preferable that the aggregate molecular weight of the cellulose acylate of the dilute solution which made the cellulose acylate solution the 0.1-5 mass% with the organic solvent of the same composition is 150,000-15 million. More preferably, the association molecular weight is 180,000 to 9 million. This association molecular weight can be calculated | required by the static light scattering method. It is preferable to melt | dissolve so that the inertia square radius calculated | required at that time may be 10-200 nm. More preferred inertia square radius is 20 to 200 nm. In addition, the second virial coefficient of -2 × 10 ^-4 ~4 × 10 ^-4 to be preferred, and more preferred to dissolve so that the second is -2 × 10 ^-4 ~2 × 10 ^-4 virial coefficient to be. Here, the definition of the association molecular weight and the inertia square radius and the second vial coefficient in the present invention will be described. These were measured using the static light scattering method according to the following method. Measurements were made in the lean region due to device circumstances, but these measurements reflect the dope behavior in the high concentration region of the present invention.

First, cellulose acylate was dissolved in a solvent used for dope to prepare a solution of 0.1% by mass, 0.2% by mass, 0.3% by mass, and 0.4% by mass. In addition, in order to prevent moisture absorption, the cellulose acylate was dried at 120 ° C. for 2 hours, and was used at 25 ° C. and 10% RH. The dissolution method was carried out according to the method adopted at the time of dope dissolution (normal temperature dissolution method, cooling dissolution method, high temperature dissolution method). Subsequently, these solutions and solvents were filtered with a filter made of 0.2 µm polytetrafluoroethylene (Teflon, trade name). And static light scattering of the filtered solution was measured at 10 degreeC from 25 degreeC to 30 degreeC at 25 degreeC using the light-scattering measuring apparatus (Otsuka Electronics Co., Ltd. product DLS-700, brand name). The obtained data were interpreted by the BERRY plot method. In addition, the refractive index required for this analysis uses the value of the solvent calculated | required with the Abbe refractometer, and the concentration gradient (dn / dc) of refractive index uses a differential refractometer (DRM-1021, brand name from Otsuka Electronics Co., Ltd.), and measures light scattering It measured using the solvent and solution which were used for.

Next, about manufacture of the cellulose acylate solution (dope) of this invention, the dissolution method is not specifically limited, Room temperature may be sufficient, and it is performed by a cooling dissolution method or a high temperature dissolution method, and a combination thereof. About these, for example, Unexamined-Japanese-Patent No. 5-163301, 61-106628, 58-127737, 9-95544, 10-95854, 10-45950, 2000 -53784, 11-322946, 11-322947, 2-2-276830, 2000-273239, 11-71463, 4-259511, 2000-273184, 11-323017 JP-A 11-302388 discloses a method for producing a cellulose acylate solution. The method of dissolving these cellulose acylates described above in an organic solvent can apply these techniques as long as it is a range of this invention suitably also in this invention. Specifically, the non-chlorine solvent system is carried out by the method described in detail on pages 22 to 25 of the Korean Patent Publication (Publication No. 2001-1745, issued March 15, 2001, Invention Association). Further, the dope solution of cellulose acylate of the present invention is usually concentrated in solution and filtered, and likewise described in detail on page 25 of the Korean Society of Publications (Publication No. 2001-1745, published March 15, 2001, Invention Association). have. Moreover, when it melt | dissolves at high temperature, it is most cases more than the boiling point of the organic solvent to be used, and in that case, it can use in a pressurized state.

It is preferable that the cellulose acylate solution of this invention is a range with the viscosity and the dynamic storage elastic modulus of this solution. The viscosity and dynamic storage modulus of the solution can be measured by the following method. 1 ml of the sample solution is measured on a rheometer (TA Instruments Co., Ltd. make, brand name: CLS 500) using the Steel Cone (made by TA Instrumennts) of diameter 4cm / 2 degrees. The measurement conditions were measured by varying the range of 40 ° C to -10 ° C by 2 ° C / min with an Oscillation Step / Temperature Ramp, and the static non-Newtonian viscosity of 40 ° C n ^* (Pa · s) and storage modulus G 'of -5 ° C. Find (Pa). In addition, the sample solution is preliminarily kept warm until the liquid temperature is constant at the measurement start temperature, and then starts the measurement.

In this invention, the viscosity in 40 degreeC is 1-400 Pa.s, the dynamic storage elastic modulus in 15 degreeC is 500 Pa or more, More preferably, the viscosity in 40 degreeC is 10-200 Pa.s, 15 degreeC It is preferable that the dynamic storage elastic modulus at. Moreover, the larger the dynamic storage modulus at low temperature is preferable, for example, when the flexible support is -5 ° C, the dynamic storage modulus is preferably 10,000 to 1 million Pa at -5 ° C, and the support is -50 ° C. In this case, the dynamic storage modulus at −50 ° C. is preferably 10,000 to 5 million Pa.

Next, a method for producing a film using a cellulose-based solution will be described. The method and equipment for manufacturing the cellulose-based film according to the present invention include a solution-flexible film-forming method and a solution-flexible film-forming apparatus conventionally used for producing a cellulose acetate film. Used. The dope (cellulose acylate solution) prepared in the dissolver (pot) is once stored in a storage pot and finally prepared by degassing the bubbles contained in the dope. The dope is sent from the dope outlet to a pressurized die through a pressurized metering gear pump capable of metering and feeding with high precision at a rotational speed, for example, and the dope is running endlessly from the detention (slit) of the pressurized die. It is uniformly pliable on the metal support of the flexible part, so that a less dry dope film (also called a web) is peeled from the metal support at the peeling point at which the metal support is almost round. Both ends of the web to be obtained are clipped and dried in a tenter while maintaining their width, then conveyed by a roll group of a drying apparatus to finish drying and wound to a predetermined length with a winder. The combination of the tenter and the drying apparatus of the roll group depends on the purpose. In the solution casting film forming method used for a silver halide photosensitive material or the functional protective film for electronic displays, in addition to a solution casting film forming apparatus, the surface of films, such as a lower layer, an antistatic layer, an anti-halation layer, a protective layer, etc. A coating device is often added for processing. Each of these manufacturing processes is described in detail on pages 25 to 30 of the Invention Association Publication (Publication No. 2001-1745, published March 15, 2001, Invention Association), and is flexible (including covalent lead). ), Metal supports, drying, peeling, stretching and the like.

Here, although the space temperature of a flexible part is not specifically limited in this invention, It is preferable that it is -50-50 degreeC. Moreover, it is preferable that it is -30-40 degreeC, and it is especially preferable that it is -20-30 degreeC. In particular, the cellulose acylate solution softened by the space temperature at low temperature can be instantaneously cooled on the support to increase the gel strength to maintain a 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 general air, nitrogen, argon, helium or the like, and is not particularly limited. In this case, the humidity is preferably 0 to 70% RH, and more preferably 0 to 50% RH. Moreover, in this invention, the support body temperature of the casting | flow_spread part which casts a cellulose acylate solution is -50-130 degreeC, Preferably it is -30-25 degreeC, More preferably, it is -20-15 degreeC. In order to maintain a flexible part at the temperature of this invention, you may achieve by introducing the gas cooled to the flexible part, or you may arrange | position a cooling apparatus to the flexible part, and cool the space. At this time, it is important to be careful not to get water, and can be carried out by a method such as using a dried gas.

In the present invention, the following structures are particularly preferable for the contents and the softness of the respective layers. That is, the cellulose acylate solution is a cellulose acylate solution containing 0.1 to 20% by mass of at least one liquid or solid plasticizer relative to the cellulose acylate at 25 ° C., and / or ultraviolet rays of at least one liquid or solid. A cellulose acylate solution containing 0.001 to 5 mass% of an absorbent based on cellulose acylate, and / or one or more types of solid particles having an average particle diameter of 5 to 3000 nm from 0.001 to 5 relative to cellulose acylate. It is a cellulose acylate solution which contains mass%, and / or is a cellulose acylate solution which contains 0.001-2 mass% of cellulose acylate with respect to cellulose acylate, and / or 1 or more peeling agent Cellulose acyle containing 0.0001-2 mass% with respect to cellulose acylate Yit solution, and / or a cellulose acylate solution containing 0.0001 to 2% by mass of one or more deterioration inhibitors relative to cellulose acylate, and / or 0.1 or more optically anisotropic regulators to cellulose acylate It is a cellulose acylate solution which contains -15 mass%, and / or 0.1-5 mass% of 1 or more types of infrared absorbers with respect to a cellulose acylate, and the cellulose manufactured from it Acylate films are preferred.

In a casting | flow_spread process, one type of cellulose acylate solution may be single-layered, and two or more types of cellulose acylate solutions may be simultaneously and / or sequentially covalently flamed. Covalent lead can be implemented, for example in the aspect of Unexamined-Japanese-Patent No. 56-162617, 2002-316387. The number of layers in the case of producing the cellulose acylate film of the present invention by covalent lead is preferably 2 to 5 layers, more preferably 2 to 4 layers, particularly preferably 2 to 3 layers.

In the case of having a casting process consisting of two or more layers, the composition of the cellulose acylate solution and the cellulose acylate film to be produced should be one of the same or different compositions of the chlorine-based solvents in each layer. Any mixture of more than one kind, the position of addition of additives to each layer is the same layer or any one of the other layers, the concentration of the additive solution in each layer is the same concentration or one of different concentrations, each layer Either one of the same or different aggregate molecular weight, the solution temperature of each layer is the same or different temperature, the application amount of each layer is the same or different application amount, the viscosity of each layer Either the same or different viscosity, two films with the same or different thickness after drying of each layer Either the material present in each layer is in the same state or distribution or in a different state or distribution, the physical properties of each layer are the same or different physical properties, the physical properties of each layer are uniform or different distribution It is also preferable that it is any one of the cellulose acylate solution and the cellulose acylate film manufactured from this solution.

Here, the physical properties include the physical properties described in detail on pages 6 to 7 of the Invention Association Publication (Publication No. 2001-1745, issued March 15, 2001, Invention Association), for example, haze, Transmittance, Spectral Characteristics, Retardation Re, Retardation Rth, Molecular Orientation Axis, Axial Shift, Tear Strength, Cut-Out Strength, Tensile Strength, Cold-Round Difference, Grating, Dynamic Friction, Alkali Hydrolysis, Curl Value, moisture content, residual solvent amount, heat shrinkage rate, high humidity level evaluation, moisture permeability, base planarity, dimensional stability, heat shrinkage start temperature, modulus of elasticity and point foreign matter, and also include impedance and face shape used for base evaluation. will be. In addition, the yellow index, transparency, and thermal properties (Tg, heat of crystallization) of cellulose acylate, which are described in detail on page 11 of the Invention Association Publication No. 2001-1745, issued March 15, 2001, Invention Association). Can be mentioned.

In addition, the cellulose acylate film of the present invention may be stretched in any direction after casting and drying for the purpose of adjusting optical performance.

A cellulose acylate film can improve the adhesion of a cellulose acylate film and each functional layer (for example, an undercoat layer and a white layer) by performing surface treatment as needed. For example, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment can be used. The glow discharge treatment herein is a so-called low temperature plasma generated under a low pressure gas of 10 ⁻³ to 20 Torr (0.1 Pa to 2.7 kPa). And plasma treatment under atmospheric pressure is also preferable.

The plasma excited gas refers to a gas which is plasma excited under the above conditions, and examples thereof include argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, and freons such as tetrafluoromethane and mixtures thereof. These are described in detail on pages 30 to 32 of the Published Journal of the Invention Association (Publication No. 2001-1745, issued March 15, 2001, Invention Association). Moreover, the plasma treatment at atmospheric pressure which is attracting attention recently can use 20-500 Kgy of irradiation energy under 10-1000 Kev, More preferably, 20-300 Kgy of irradiation energy can be used under 30-500 Kev. . Among these, especially preferably, it is an alkali saponification process and is very effective as a surface treatment of a cellulose acylate film.

An alkali saponification process is performed by apply | coating a saponification liquid. Examples of the coating method include a dip coating method, curtain coating method, extrusion coating method, bar coating method and E type coating method. The solvent of the alkali saponification treatment coating liquid has good wettability in order to apply the transparent support to the saponification liquid. Moreover, it is preferable to select a solvent which keeps a cotton shape in a favorable state, without forming unevenness | corrugation on the surface of a transparent support body by a saponification liquid solvent. Specifically, an alcohol solvent is preferable and isopropyl alcohol is especially preferable. Moreover, the aqueous solution of surfactant can also be used as a solvent. Alkali which melt | dissolves in the said solvent as alkali of the alkali saponification coating liquid is preferable, and KOH and NaOH are more preferable. 10 or more are preferable and, as for pH of a saponification coating liquid, 12 or more are more preferable. 1 second or more and 5 minutes or less are preferable at room temperature, as for reaction conditions at the time of alkali saponification, 5 seconds or more and 5 minutes or less are more preferable, 20 seconds or more and 3 minutes or less are especially preferable. After the alkali saponification reaction, it is preferable to wash the saponified solution coated surface with water or acid, followed by water washing.

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

In order to achieve adhesion of the functional layer such as an emulsion layer and the film, a method of applying the functional layer directly on the cellulose acylate film after the surface activation treatment to obtain adhesive force, and after either surface treatment or surface treatment Instead, there is a method of forming an undercoat (adhesive layer) and applying a functional layer thereon. Details of these undercoats are described on page 32 of the Published Publication of the Society of the Invention (Publication No. 2001-1745, issued March 15, 2001, Invention Association). The functional layers of the cellulose acylate film of the present invention are also described in detail on pages 32 to 45 of the Korean Society of Publications (Publication No. 2001-1745, issued March 15, 2001, Invention Association). .

The water vapor transmission rate of the cellulose acylate of the present invention is preferably 200 to 1500 g / (m 2 · day), more preferably 400 to 1500 g / (m 2 · day), and 400 to 1400 g / (m 2 · day) Most preferred.

In the present invention, the moisture permeability is the amount of water that the film transmits per unit time under high temperature and high humidity conditions. The moisture permeability is specifically the mass change (g / (m 2 · day)) before and after leaving the cup containing calcium chloride sealed for 24 hours under the condition of 60 ° C. and 95% RH using each film sample as a lid. From the moisture permeability of the cellulose triacetate film based on the hygroscopicity of calcium chloride.

The optical performance of a cellulose acylate film is demonstrated below.

The in-plane retardation (Re) which is the optical performance of the cellulose acylate film of this invention, and the retardation (henceforth, Rth) of the film thickness direction use ellipsometer (AEP-100, a brand name, Shimadzu Corporation make). It is measured by.

Specifically, Re is a value obtained by multiplying the film thickness by an in-plane longitudinal transverse refractive index difference measured at a wavelength of 632.8 nm, and can be obtained according to the following formula.

Re = (nx-ny) × d

In the formula, nx is a refractive index in the slow axis direction (the direction in which the refractive index becomes maximum); ny is a refractive index in the direction orthogonal to the slow axis; and d is the thickness (unit: nm) of the film.

As in-plane retardation Re of a cellulose ester film, it is preferable that it is 50 nm or less, It is more preferable that it is 40 nm or less, It is further more preferable that it is 30 nm or less, It is most preferable that it is 20 nm or less.

Retardation (Rth) of the thickness direction of a film is the value which multiplied the film thickness by the birefringence of the thickness direction specifically measured at the wavelength of 632.8 nm, and can be calculated | required according to the following formula.

Rth = {(nx + ny) / 2-nz} × d

Where nx is the refractive index in the slow axis direction (the direction in which the refractive index is maximum); ny is the refractive index in the direction orthogonal to the slow axis; nz is the refractive index in the thickness direction; and d is the thickness of the film (unit: Nm).

As retardation (Rth) of the thickness direction of a cellulose ester film, it is preferable that it is 100 nm or less, It is more preferable that it is 50 nm or less, It is further more preferable that it is 40 nm or less, It is most preferable that it is 30 nm or less. The birefringence {(nx + ny) / 2-nz} in the thickness direction is preferably 0.0005 or less, more preferably 0.0002 or less, and most preferably 0.0001 or less.

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

When using as a polarizing plate protective film, the manufacturing method of a polarizing plate is not specifically limited, It can manufacture by a general method. There exists a method of alkali-processing the obtained cellulose acylate film and sticking to both surfaces of the polarizer produced by immersing and extending a polyvinyl alcohol film in an iodine solution using the fully saponified polyvinyl alcohol aqueous solution. Instead of the alkali treatment, simple adhesive processing such as those described in each of Japanese Unexamined Patent Publication Nos. Hei 6-94915 and 6-118232 may be performed. As an adhesive agent used for bonding a protective film process surface and a polarizer, polyvinyl alcohol adhesives, such as polyvinyl alcohol and polyvinyl butyral, vinyl latexes, such as butylacrylate, etc. are mentioned, for example. A polarizing plate consists of a polarizer and a protective film which protects both surfaces, and also consists of attaching a protective film to one side of the polarizing plate, and attaching a separate film to the opposite side. A protective film and a separation film can be used for the purpose of protecting a polarizing plate at the time of a polarizing plate shipment, a product inspection, etc. In this case, the protective film is adhered for the purpose of protecting the surface of the polarizing plate and is used on the side opposite to the surface on which the polarizing plate is adhered to the liquid crystal plate. In addition, a separation film is used for the purpose of covering the adhesive layer adhering to a liquid crystal plate, and is used for the surface side which adhere | attaches a polarizing plate to a liquid crystal plate. In a liquid crystal display device, although the board | substrate containing a liquid crystal is normally arrange | positioned between two polarizing plates, the polarizing plate protective film to which the optical film of this invention is applied can obtain the outstanding display property in what site | part. In particular, since a transparent hard coat layer, an antiglare layer, an antireflection layer, etc. are formed in the polarizing plate protective film of the display side outermost surface of a liquid crystal display device, it is especially preferable to use this polarizing plate protective film for this part.

The cellulosic film of this invention can be used for various uses, and when used as an optical compensation sheet of a liquid crystal display device, it is especially effective. The cellulose body film of this invention can be used for the liquid crystal cell of various display modes. Twisted Nematic (TN), In-Plane Switching (IPS), Ferroelectric Liquid Crystal (FLC), Anti-ferroelectric Liquid Crystal (AFLC), Optimal Compensatory Bend (OCB), Super Twisted Nematic (STN), Vertically Aligned (VA) and HAN Various display modes such as (Hybrid Aligned Nematic) have been proposed. Moreover, the display mode which orientation-divided the said display mode is also proposed. The cellulose-based film is effective in any liquid crystal display device of any display mode. It is also effective in any type of transmissive, reflective or transflective liquid crystal display device. You may use the cellulose body film of this invention as a support body of the optical compensation sheet of a TN type liquid crystal display device which has a liquid crystal cell of TN mode. You may use the cellulose body film of this invention as a support body of the optical compensation sheet of STN type liquid crystal display device which has a liquid crystal cell of STN mode. Generally, in STN type liquid crystal display devices, the bar liquid crystal molecules in the liquid crystal cell are twisted in the range of 90 to 360 degrees, and the product of the refractive index anisotropy (Δn) and the cell gap (d) of the bar liquid crystal molecules (Δnd) ) Is in the range of 300 to 1500 nm. The optical compensation sheet used for STN type liquid crystal display device is described in Unexamined-Japanese-Patent No. 2000-105316. The cellulose body film of this invention can be used especially advantageously as a support body of the optical compensation sheet of VA type | mold liquid crystal display device which has a liquid crystal cell of VA mode. The cellulose body film of this invention can be advantageously used also as a support body of the optical compensation sheet of the OCB type liquid crystal display device which has a liquid crystal cell of OCB mode, or the HAN type liquid crystal display device which has a liquid crystal cell of HAN mode.

The cellulose body film of this invention can be advantageously used also as an optical compensation sheet of a TN type, STN type, HAN type, and GH (Guest-Host) reflection type liquid crystal display device. These display modes are well known from the example. TN type reflective liquid crystal display devices are described in Japanese Patent Application Laid-open No. Hei 10-123478, International Publication No. WO98 / 48320, and Japanese Patent No. 3022477. The optical compensatory sheet used for a reflective liquid crystal display device is described in pamphlet of international publication WO00 / 65384.

The cellulose body film of this invention can be advantageously used also as a support body of the optical compensation sheet of an ASM type liquid crystal display device which has a liquid crystal cell of ASM (Axially Symmetric Aligned Microcell) mode. The liquid crystal cell of ASM mode has the characteristic that the thickness of the cell is hold | maintained by the resin spacer which can be adjusted. The other property is the same as that of the liquid crystal cell of TN mode. The liquid crystal cell of the ASM mode and the ASM type liquid crystal display are described in Kume et al. (Sume 98 Digest 1089 (1998)).

The use of these detailed cellulosic films described above is described in detail on pages 45 to 59 of the Published Publication of the Invention Association (Air No. 2001-1745, issued March 15, 2001, Invention Association).

(Example)

Next, although this invention is demonstrated in detail based on an Example, this invention is not limited at all by the following Example.

Example 1 Modifiers for Cellulose Films and Cellulose Films

(1-1) Preparation of Cellulose Acylate Solution

The cellulose triacetate powder A (flake) described below was gradually added to the 5 L glass container with a stirring blade, stirring well and disperse | distributing to the following solvent mixed solution, and it prepared so that the whole might be 2 kg. As the solvent, methyl acetate, acetone, and ethanol were used, all of which had a water content of 0.2% by mass or less. First, the powder of cellulose triacetate was put into the dispersion tank, the nitrogen gas was enclosed, and it disperse | distributed for 30 minutes by the stirrer with anchor blades in the eccentric stirring shaft and center axis | shaft of a dissolver form. The onset temperature of dispersion was 30 degreeC. After the dispersion was completed, the high speed stirring was stopped, and the circumferential speed of the anchor blade was set at 0.5 m / sec, followed by stirring for 100 minutes to swell the cellulose triacetate flake. Until the end of the swelling, the inside of the tank was pressurized to 0.12 MPa with nitrogen gas. At this time, the oxygen concentration in the tank was less than 2% by volume and remained in a trouble-free state on explosion-proof. Moreover, it was confirmed that the moisture content in dope is 0.2 mass% or less. The composition of the cellulose acylate solution is as follows.

Cellulose triacetate A (SA + SB is 2.78, SA is 2.78, SB is 0, cellulose acylate flake having a viscosity-average degree of polymerization of 303 and a water content of 1% by mass or less. (100 parts by mass), methyl acetate (522.0 parts by mass), acetone (48.0 parts by mass), ethanol (30.0 parts by mass), and triphenylphosphate (TPP) (12.0 parts by mass). Sample 2 was prepared.

The sample 1 was prepared without adding the TPP used in the sample 2. In addition, regarding Samples 3 to 13, TPP used in Sample 2 was substituted with a comparative compound and the modifier of the present invention, respectively, to prepare 12.0 parts by mass or 18.0 parts by mass.

(1-2) Cellulose Triacetate Film Solution

The obtained non-uniform gel-like solution was sent to the screw pump, and the cooling part was passed through for 3 minutes at -70 degreeC. Cooling was performed using a -80 ° C refrigerant cooled in a refrigerator. And the solution obtained by cooling was transferred to the container made from stainless steel, stirred at 50 degreeC for 2 hours, it was made into a homogeneous solution, and the filter paper of 0.01 mm of absolute filtration accuracy (made by Toyoji Co., Ltd., # 63 (brand name)). The filtrate was further filtered through a filter paper (FH025, trade name) manufactured by Pole Corporation with an absolute filtration accuracy of 2.5 µm.

(1-3) Preparation of Cellulose Triacetate Film

The filtered cellulose triacetate solution at 50 ° C. was cast on a mirror stainless steel support through a casting dye. The temperature of the support was 5 ° C, the casting speed was 3 m / min, and the coating width thereof was 30 cm. It left to stand at room temperature for 1 minute, and after that, the drying air of 55 degreeC was blown for drying. 5 minutes later, it removed from the mirror stainless steel support body, and after that, it dried for 27 minutes at 133 degreeC, and obtained the cellulose triacetate film with a film thickness of 80 micrometers.

(1-4) Measurement of moisture permeability and Rth of cellulose triacetate film

The water vapor transmission rate and Rth were measured about the obtained cellulose triacetate (TAC) film. In the present Example, the water vapor transmission rate and Rth of the cellulose triacetate film were measured as follows.

(Measurement of moisture permeability)

From the change in mass (g / (m 2 · day)) before and after leaving the cup with calcium chloride sealed for each film sample for 24 hours at 60 ° C and 95% RH, the hygroscopicity of calcium chloride was determined. The water vapor transmission rate of the cellulose triacetate film on which it was based was evaluated. The results are shown in Table 1.

(Measurement of Rth)

(1) In-plane retardation (Re) as a value obtained by multiplying the film thickness by the difference in longitudinal and horizontal refractive indexes measured at a wavelength of 632.8 nm using an ellipsometer (AEP-100 (trade name), manufactured by Shimadzu Corporation). ) Was further obtained by multiplying the birefringence in the thickness direction by the film thickness, and the retardation (Rth) in the film thickness direction was calculated according to the following formula, respectively.

Re = (nx-ny) × d

Rth = {(nx + ny) / 2-nz} × d

nx: refractive index in ground axis direction (direction in which refractive index becomes maximum)

ny: Refractive index of direction orthogonal to ground axis

nz: refractive index in the thickness direction

d ： Thickness of film (unit: nm)

sample Remarks Modifier Addition amount (mass%) Moisture permeability (g / ㎡ ・ day) Rth (nm) Sample 1 Sample 2 Sample 3 Sample 4 Comparative Comparison -TPPTEPH-1 -121212 2500180027001850 831034055 Sample 5 Samples 6 Samples 7 Samples 8 Samples 9 Samples 10 Samples 11 Samples 12 Samples 13 Inventive Invention Invention Invention Invention Invention Invention Invention Invention Invention Invention A-1A-1A-19A-43B-7C-1C-1D-2E-1 121812121212181212 170017001400150011001700160017001600 262039455558487060 (Note) The addition amount is the mass% with respect to the mass of a cellulose acylate.

The results shown in Table 1 show that by adding the compound of the present invention, a cellulose acetate film having a smaller optical anisotropy (lower retardation) and lower moisture permeability than a widely used TPP can be produced. In particular, by adding the modifier of the present invention, the optical anisotropy can be significantly reduced with respect to TPP.

According to the inventors' estimation, for example, compounds having three or more rings directly linked to one atom, such as B-7, C-1, D-2, and E-1 of the present invention, Since each ring is hardly oriented isotropically due to the steric hindrance of, optical anisotropy can be reduced. However, it has been clarified by Comparative Examples 1 and 2 that the optical anisotropy is increased rather than the optical anisotropy in a compound such as TPP which has three or more rings and is not directly linked to a ring from one atom. .

<Example 2>

A cellulose acylate film was produced in the same manner as in Example 1 using the following composition.

Cellulose triacetate (acetization degree 60.9%) (100 parts by mass)

Methylene chloride (300 parts by mass)

Methanol (45 parts by mass)

Modifier (11.7 parts by mass) used in Samples 2 to 10 described in Example 1

Also in this case, the favorable result was obtained with the cellulose-type film of this invention similarly to Example 1.

Example 3 Polarizing Plate Protective Film

About the samples 2-13 of Example 1, the polarizing plate protective film of Samples 302-313 was produced and evaluated by the method of Example 1 of Unexamined-Japanese-Patent No. 11-316378. The optical characteristic of the elliptical polarizing plate obtained by the cellulose-based film of the present invention was excellent. In addition, the durability with time also did not have a problem compared with the protective film obtained in Comparative Sample 2.

Example 4 Liquid Crystal Display

Regarding Samples 2 to 13 of Example 1, the liquid crystal display device according to Example 1 of JP-A-10-48420, and the discotic liquid crystal molecule according to Example 1 of JP-A 9-26572 are contained. Optically anisotropic layer, alignment film coated with polyvinyl alcohol, VA type liquid crystal display device shown in FIGS. 2-9 of JP 2000-154261, OCB type liquid crystal display of FIG. 10-15 of JP 2000-154261 Each device was produced and evaluated. In the apparatus obtained using the cellulose body film of this invention, favorable performance was obtained in any case.

Example 5 Silver Halide Photosensitive Material

With respect to Samples 2 to 13 of Example 1, Samples 502 to 513 were produced in the same manner as in Example 1 except that the film thickness was 120 μm. One side of the obtained film was provided with the 1st layer and 2nd layer of Example 1 of Unexamined-Japanese-Patent No. 4-73736, and the back layer which made the cationic polymer an electroconductive layer was created. And each layer which has the composition similar to the sample 105 of Example 1 of Unexamined-Japanese-Patent No. 11-38568 to the opposite surface of the film base which provided the obtained white layer was apply | coated, and the silver halide photographic photosensitive material was produced. The silver halide photographic photosensitive material obtained by using the cellulose-based film of the present invention had all excellent images and no problem in handling thereof.

The cellulosic film to which the compound represented by the said General formula (1), General formula (2), or General formula (3) was added has the outstanding effect that optical anisotropy is small and it has low moisture permeability under high temperature, high humidity. Thereby, the said cellulose film can be used also for a polarizing plate protective film, a liquid crystal display device, a silver halide photographic photosensitive material, etc., for example.

Claims (10)

A cellulose body composition characterized by containing at least one of a cellulose body and a compound represented by the following general formula (1): General formula (1) [Wherein, R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group; X represents a divalent linking group formed of at least one group selected from the following linking group group 1; Y represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group: (Linking group group 1) represents a single bond, -O-, -CO-, -NR ^4- , an alkylene group or an arylene group; R ⁴ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. A cellulose body composition characterized by containing at least one of a cellulose body and a compound represented by the following general formula (2): General formula (2) [Wherein, Q ¹ , Q ² and Q ³ each independently represent a 5 or 6 membered ring; X ¹ represents B, CR (wherein R represents a hydrogen atom or a substituent), N, P, and P = 0. A method for producing a cellulose body composition, comprising the step of containing at least one compound represented by the general formula (1) or the general formula (2) in a cellulose body. A cellulosic film comprising at least one compound represented by the general formula (1) or (2). The cellulose-based film of claim 4, wherein the general formula (2) is represented by the following general formula (3): General formula (3) [Wherein, X ² represents B, CR (wherein R represents a hydrogen atom or a substituent), N, P, or P═O; R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are each independently a hydrogen atom Or a substituent; One group selected from the group consisting of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ and one group selected from the group consisting of R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ May be coupled with a connector]. The cellulose body film according to claim 4, wherein the cellulose body is cellulose acylate. The modifier for cellulose body films represented by General formula (1), General formula (2), or General formula (3) of Claim 1, 2 or 5. At least one layer of the cellulose body film of Claim 4 is included, The polarizing plate protective film characterized by the above-mentioned. A liquid crystal display device comprising at least one layer of the cellulose-based film according to claim 4. A silver halide photographic photosensitive material using the cellulose-based film according to claim 4 as a support.