KR20080088427A - Cellulose compound composition, cellulose compound film, optically compensatory sheet, polarizing plate and liquid crystal display device - Google Patents

Abstract

A cellulose compound composition, a cellulose compound film, an optically compensatory sheet, a polarizing plate, and an LCD(Liquid Crystal Display) device are provided to form a cellulose compound film, in which a change of in-plane retardation(Re) and retardation(Rth) in a thickness direction due to a change of humidity is reduced, and provide an excellent effect at the same time that the Re and Rth can be freely controlled in a wide range. A cellulose compound composition comprises a cellulose compound. The cellulose compound includes an aliphatic acyl group(A) having a carbon number of 5 to 30 and an acyl group containing an aromatic group(B). The cellulose compound additionally includes an aliphatic acyl group(C) having a carbon number of 2 to 4. The cellulose compound satisfies a following formula(I): 2.4<=DSA+DSB+DSC<=3.0. DSA, DSB and DSC indicate the substitution degrees of the acyl group(A), the acyl group(B) and the acyl group(C) respectively.

Description

Cellulose Compound Composition, Cellulose Compound Film, Optical Compensation Sheet, Polarizer and Liquid Crystal Display Device {CELLULOSE COMPOUND COMPOSITION, CELLULOSE COMPOUND FILM, OPTICALLY COMPENSATORY SHEET, POLARIZING PLATE AND LIQUID CRYSTAL DISPLAY DEVICE}

The present invention relates to a cellulose compound composition, a film, an optical compensatory sheet, a polarizing plate, and a liquid crystal display device. More specifically, the present invention provides a suitable glass having a large absolute value of in-plane retardation (Re) and a retardation in the thickness direction (Rth), small dependence on humidity of Re and Rth, and suitable glass. A cellulose compound film having a transition temperature and a mechanical property, and an optical compensation sheet, a polarizing plate, and a liquid crystal display device using the cellulose compound film, respectively.

With the recent spread of liquid crystal display devices, the demand for display performance and durability is higher, resulting in a higher response speed and more in order to satisfy the contrast, color balance, etc. of the displayed image when viewed from an oblique direction. Compensating the viewing angle over a wide range is a challenge. In order to solve these problems, display elements of vertical alignment (VA) mode, optical compensated bend (OCB) mode and in-plane switching (IPS) mode are developed, There is a need for optical film materials having various retardation developing properties, depending on the respective liquid crystal mode. In particular, the retardation film is required to control the values of the in-plane retardation Re and the thickness retardation Rth in accordance with various liquid crystal modes.

Cellulose acylate films are widely used as polarizing plate protective films for liquid crystal display devices because of their transparency and toughness. For example, optical films obtained by film-forming fatty acid cellulose esters such as cellulose acetate propionate and cellulose acetate butyrate have been proposed (JP-A-2000-352620 (terms used herein) "JP-A" means "Japanese Unexamined Patent Publication"). However, Re and Rth obtainable in such a film are limited, and this film is not sufficient as a retardation film. In addition, a high stretched film formed of cellulose mixed acylate containing linear carboxylic acid having 5 to 22 carbon atoms and acetic acid has recently been proposed (JP-A-2006-249221). However, this film is an optical film showing low birefringence. Furthermore, an optical film obtained by film-forming an aromatic carboxylic acid-mixed acylate has recently been proposed (JP-A-2006-328298).

However, such a film is not only able to obtain sufficient Re and Rth as a polarizing plate protective film further having a function as a retardation film, but still has a problem that the delay is changed by humidity fluctuations and causes white spot generation.

In view of these problems, an object of the present invention is a cellulose compound film having a small change in in-plane retardation (Re) and a retardation (Rth) in the thickness direction due to humidity variation, and having a high absolute value of Re and Rth, and respectively. An optical compensation film, a polarizing plate, and a liquid crystal display device using this cellulose compound film are provided.

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

[1] A cellulose compound composition comprising a cellulose compound containing an acyl group (B) containing an aliphatic acyl group (A) having 5 to 30 carbon atoms and an aromatic group.

[2] The cellulose compound composition according to [1], wherein the cellulose compound further comprises an aliphatic acyl group (C) having 2 to 4 carbon atoms.

[3] The cellulose compound composition according to [2], wherein the cellulose compound satisfies the following formula (I):

Formula I

2.4 ≤ DSA + DSB + DSC ≤3.0

[Wherein, DSA, DSB and DSC each represent a degree of substitution of the acyl group (A), the acyl group (B) and the acyl group (C).].

[4] The cellulose compound composition according to [1], wherein the cellulose compound satisfies the following formula (II):

Formula II

0.1 <DSA <0.8

[In formula, DSA shows the substitution degree of the said acyl group (A).].

[5] The cellulose compound composition according to [1], wherein the cellulose compound satisfies the following formula (III):

Formula III

0.1 <DSB <0.8

[In formula, DSB shows substitution degree of the said acyl group (B).].

[6] The cellulose compound composition according to [1], wherein the cellulose compound satisfies the following formula (IV) or formula (IV-I):

Formula IV

0.7DSB ≤ DSB ₆

Formula IV-I

DSB ₆ ≤ 0.3DSB

[In the meal,

DSB represents the substitution degree of the said acyl group (B),

DSB ₆ represents the substitution degree of the acyl group (B) at the 6 position.

[7] The cellulose compound composition according to [1], wherein the acyl group (A) is selected from the group consisting of hexanoyl group, octanoyl group, 2-ethylhexanoyl group, dodecanoyl group, octadecanoyl group, and cyclohexanoyl group.

[8] The cellulose compound composition according to [1], wherein the acyl group (B) is selected from the group consisting of benzoyl group, phenylbenzoyl group and 4-heptylbenzoyl group.

[9] A cellulose compound film formed of the cellulose compound composition as described in [1].

[10] A retardation film containing a cellulose compound film as described in [9].

[11] an optical compensation film comprising:

Cellulose compound films as described in [9]; And

An optically anisotropic layer formed by orienting a liquid crystal compound.

[12] An antireflective film comprising:

Cellulose compound films as described in [9]; And

Antireflective layer.

[13]

Polarizing film; And

A polarizing plate comprising two protective films sandwiching a polarizing film, wherein at least one of the two protective films comprises a cellulose compound film as described in [9].

[14] An image display device comprising:

The cellulose compound film as described in [9].

The cellulose compound composition of the present invention can form a cellulose compound film in which the change of the in-plane retardation (Re) and the retardation (Rth) in the thickness direction due to humidity fluctuation is reduced, and at the same time freely controlling Re and Rth in a wide range. It provides an excellent effect. The cellulose compound film of the present invention can be suitably used in an optical compensation sheet, a polarizing plate, a liquid crystal display device, etc., and can exhibit excellent display performance.

The present invention is described in detail below.

[Cellulose Compound]

The cellulose compound contained in the cellulose compound composition of this invention contains the acyl group (B) containing a C5-C30 aliphatic acyl group (A) and an aromatic group.

(Aliphatic acyl group (A))

The aliphatic acyl group (A) used in the present invention is an acyl group having 5 to 30 carbon atoms, and may be linear or branched, or may include a cyclic structure or an unsaturated bond, and these are not particularly limited. The aliphatic acyl group is preferably an acyl group having 5 to 20 carbon atoms, more preferably 6 to 18 carbon atoms, and most preferably 8 to 18 carbon atoms. Specific examples thereof include pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, undecanoyl group, dodecanoyl group, tridecanoyl group, tetradecanoyl group, pentatetradecanoyl group, hexa Decanoyl group, heptadecanoyl group, octadecanoyl group, nonadecanoyl group, eicosanoyl group, henecosanoyl group (heneicosanoyl), docosanoyl group, tricosanoyl group, tetracosanoyl group, hexacosanoyl group, Heptacosanoyl group, octacosanoyl group, triacosanoyl group, trimethylacetyl group, 2-methylbutyryl group, isovaleryl group, 2-ethylbutyryl group, 2,2-dimethylbutyryl group, tert-butylacetyl group, 2 -Methyl valeryl group, 3-methyl valeryl group, 4-methyl valeryl group, 2-propylpentanoyl group, 2-methylhexanoyl group, 2-ethylhexanoyl group, 2-methyl-2-pentenoyl group, 2,2-dimethylpente Noil group, 2-octenoyl group, citroneryl group, undecylenoyl group, myristole , Palmitoleyl group, oleoyl group, erylidyl group, eicosenoyl group, erucyl group, nerbonyl group, 2,4-pentadienoyl group, 2,4-hexadienoyl group, 2,6-pentadienoyl group, geranyl group, Linoleyl group, 11,14-eicosadienoyl group, linoleyl group, 8,11,14-eicosartrienoyl group, arachidyl group, 5,8,11,14,17-eicosapentaenoyl group, 4 , 7,10,13,16,19-docosahexanoyl group, cyclobutylacetyl group, cyclopentanoyl group, cyclopentylacetyl group, cyclopentylpropionyl group, cyclohexanoyl group, cyclohexylacetyl group, cyclohexylpropionyl group , Cyclohexyl butyryl group, cyclohexyl pentanoyl group, dicyclohexylacetyl group, 1-methyl-1-cyclohexanecarbonyl group, 2-methyl-1-cyclohexanecarbonyl group, 3-methyl-1-cyclohexanecarbonyl group, 4-methyl -1-cyclohexanecarbonyl group, 4-tert-butyl-1-cyclohexanecarbonyl group, 4-pentyl-1-cyclohexanecarbonyl group, 4-methyl- Clohexaneacetyl group, cycloheptyl group, 2-norborneneacetyl group, 4-pentyl bicyclo [2,2,2] octane-1-carbonyl group, 3-oxotricyclo [2,2,1,0 (2,6)]-heptane-7-carbonyl group, 3-noradamantanecarbonyl group, 1-adamantanecarbonyl group, 1-adamantaneacetyl group, 1-cyclopentene-1-carbonyl group, 1-cyclopentene-1 -Acetyl group, 1-cyclohexene-1-carbonyl group and 1-methyl-2-cyclohexene-1-carbonyl group.

Among these, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, undecanoyl group, dodecanoyl group, tridecanoyl group, tetradecanoyl group, pentatetradecanoyl group, hexadecanoyl Diary, heptadecanoyl group, octadecanoyl group, nonadecanoyl group, eicosanoyl group, henecosanoyl group, docosanoyl group, trimethylacetyl group, 2-methylbutyryl group, isovaleryl group, 2-ethylbutyryl group , 2,2-dimethylbutyryl group, tert-butylacetyl group, 2-methyl valeryl group, 3-methyl valeryl group, 4-methyl valeryl group, 2-propylpentanoyl group, 2-ethylhexanoyl group, citroneryl group, undecylenate Silenoyl group, myristoyl group, palmitole group, oleoyl group, erylidyl group, eicosenoyl group, erucyl group, nerbonyl group, 2,4-pentadienoyl group, 2,4-hesadienoyl group, 2, 6-pentadienoyl group, geranyl group, linoleyl group, cyclohexanoyl group, cyclohexyl acetyl Group, cyclohexyl propionyl group, cyclohexyl butyryl group, cyclohexylpentanoyl group, dicyclohexylacetyl group, 1-methyl-1-cyclohexanecarbonyl group, 2-methyl-1-cyclohexanecarbonyl group, 3-methyl-1- A cyclohexanecarbonyl group, 4-methyl-1-cyclohexane carbonyl group, 4-tert-butyl-1-cyclohexanecarbonyl group, 4-pentyl-1-cyclohexanecarbonyl group and 4-methyl-cyclohexaneacetyl group are preferable.

More preferred are hexanoyl group, octanoyl group, nonanoyl group, decanoyl group, dodecanoyl group, hexadecanoyl group, octadecanoyl group, 2-ethylbutyryl group, 2,2-dimethylbutyryl group, tert-butylacetyl group , 2-methyl valeryl group, 3-methyl valeryl group, 4-methyl valeryl group, 2-ethylhexanoyl group, palmitoleyl group, oleoyl group, cyclohexanoyl group and cyclohexylacetyl group.

Most preferred are hexanoyl group, octanoyl group, 2-ethylhexanoyl group, dodecanoyl group, octadecanoyl group and cyclohexanoyl group.

(Acyl group (B) containing an aromatic group)

The acyl group (B) containing an aromatic group used in the present invention can be bonded directly or via a linking group to the ester linkage portion. As used herein, the linking group represents an alkylene group, an alkenylene group or an alkynylene group, and the linking group may have a substituent. The linking group is preferably an alkylene, alkenylene or alkynylene group having 1 to 10 carbon atoms, more preferably an alkylene or alkenylene group having 1 to 6 carbon atoms, most preferably alkylene or alkenyl having 1 to 4 carbon atoms. It's Rengi.

The aromatic group may have a substituent, and examples of the substituent substituted in the aromatic group and the substituent substituted in the linking group include an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 8 carbon atoms). Methyl, ethyl, propyl, isopropyl, tert-butyl, n-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl), alkenyl groups (preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 8 carbon atoms, for example, vinyl, allyl, 2-butenyl, and 3-pentenyl groups, and an alkynyl group (preferably 2 carbon atoms). 20 to 20, more preferably 2 to 12, even more preferably 2 to 8, for example propargyl, 3-pentynyl, an aryl group (preferably 6 to 30 carbon atoms, more preferably 6 to 20, even more preferably 6 to 12, for example, phenyl, biphenyl, naphthyl), an amino group (preferably 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, even more preferably 0 to 6 carbon atoms, for example Amino, methylamino, dimethylamino, diethylamino, dibenzylamino), an alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 8 carbon atoms, for example Methoxy, ethoxy, butoxy), an aryloxy group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, even more preferably 6 to 12 carbon atoms, for example, phenyloxy, 2-naph; Yloxy), an acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, for example acetyl, benzoyl, formyl, pivaloyl), alkoxy Carbonyl groups (preferably It is a minority 2-20, More preferably, it is 2-16, More preferably, it is 2-12, For example, methoxycarbonyl, ethoxycarbonyl), An aryloxycarbonyl group (preferably C7-20, More preferably 7 to 16, even more preferably 7 to 10, for example phenyloxycarbonyl), acyloxy group (preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms) Preferably it is 2-10, for example, acetoxy, benzoyloxy, an acylamino group (preferably C2-C20, More preferably, it is 2-16, More preferably, it is 2-10, acetyl Amino group, benzoylamino), alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, still more preferably 2 to 12 carbon atoms, for example, Carbonylamino), an aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16, even more preferably 7 to 12 carbon atoms, for example phenyloxycarbonylamino), sulfonyl Amino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, even more preferably 1 to 12 carbon atoms, for example methanesulfonylamino, benzenesulfonylamino), sulfamoyl group (preferably Having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, and even more preferably 0 to 12 carbon atoms, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, and phenylsulfamoyl) and carbamoyl groups (preferably Having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, for example carbamoyl, methylcarbamoyl, diethylcarbamoyl, or phenylcarbamoyl); Alkylthio groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, for example methylthio and ethylthio), and arylthio groups (preferably 6 carbon atoms) 20 to 20, more preferably 6 to 16, and even more preferably 6 to 12, for example, phenylthio) and a sulfonyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms). Preferably it is 1 to 12, for example mesyl, tosyl), sulfinyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16, even more preferably 1 to 12, for example Methanesulfinyl, benzenesulfinyl), ureido groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, for example, ureido, methylureido, phenyl Ouray Fig.), Phosphate amide groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, for example diethyl phosphate amide, phenyl phosphate amide), hydroxy group , Mercapto group, halogen atom (e.g. fluorine, chlorine, bromine, iodine), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic Groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, heteroatoms are for example nitrogen atoms, oxygen atoms or sulfur atoms, specifically for example imidazolyl, pyridyl, quinine Nolyl, furyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzothiazolyl), silyl group (preferably 3 to 40 carbon atoms, more preferably 3 to 30, even more preferably Is 3 to 24, for example Trimethylsilyl, triphenylsilyl). Each of these substituents may be further substituted. When two or more substituents are present, these substituents may be the same or different. Further, where possible, substituents may be combined with each other to form a ring.

"Aromatics" is described in Rikagaku Jiten (Physics and Chemistry Dictionary) , 4th ed., Page 1208 (Iwanami Shoten)], and the aromatic groups used in the present invention may be aromatic hydrocarbon groups or aromatic heterocyclic groups, preferably aromatic It is a hydrocarbon group.

The aromatic hydrocarbon group is preferably 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms, still more preferably 6 to 10 aromatic hydrocarbon groups. Specific examples of the aromatic hydrocarbon group include a phenyl group, naphthyl group, anthryl group, biphenyl group and terphenyl group. As an aromatic hydrocarbon group, a phenyl group, a naphthyl group, or a biphenyl group is preferable. As an aromatic heterocyclic group, the aromatic heterocyclic group containing at least 1 atom of an oxygen atom, a nitrogen atom, and a sulfur atom is preferable. Specific examples of the hetero ring include furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazolin, thiadiazole, oxazoline , Oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimi Dazoles, benzoxazoles, benzothiazoles, benzotriazoles and tetrazaindenes. Aromatic heterocyclic groups are preferably pyridyl groups, triazinyl groups or quinolyl groups.

Preferable examples of the acyl group (B) containing an aromatic group include phenylacetyl group, hydrocinnamoyl group, diphenylacetyl group, phenoxyacetyl group, benzyloxyacetyl group, O-acetylmandelyl group, 3-methoxyphenylacetyl Group, 4-methoxyphenylacetyl group, 2,5-dimethoxyphenylacetyl group, 3,4-dimethoxyphenylacetyl group, 9-fluorenylmethylacetyl group, cinnamoyl group, 4-methoxy-cinnamo Diary, benzoyl group, ortho-toluoyl group, meta-toluoyl group, para-toluoyl group, m-anisoyl group, p-anisoyl group, phenylbenzoyl group, 4-ethylbenzoyl group, 4-propylbenzoyl group , 4-tert-butylbenzoyl group, 4-butylbenzoyl group, 4-pentylbenzoyl group, 4-hexylbenzoyl group, 4-heptylbenzoyl group, 4-octylbenzoyl group, 4-vinylbenzoyl group, 4-ethoxybenzo Diary, 4-butoxybenzoyl group, 4-hexyloxybenzoyl group, 4-heptyloxybenzoyl group, 4-pentyloxybenzoyl group, 4-octyloxybenzoyl group, 4-nonyloxybenzoyl group, 4-decyloxybenzoyl group , 4-undecyloxybenzoyl group, 4-dodecyloxybenzoyl group, 4-isopropoxyoxybenzoyl group, 2,3-dimethoxybenzoyl group, 2,5-dimethoxybenzoyl group, 3,4-dimethoxybenzoyl group , 2,6-dimethoxybenzoyl group, 2,4-dimethoxybenzoyl group, 3,5-dimethoxy cybenzoyl group, 3,4,5-trimethoxybenzoyl group, 2,4,5-trimethoxy Benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 2-biphenylcarbonyl group, 4-biphenylcarbonyl group, 4'-ethyl-4-biphenylcarbonyl group, 4'-octyloxy-4-biphenylcarbonyl group, Piperonilloyl group, diphenylacetyl group, triphenylacetyl group, phenylpropionyl group, hydrocinnamoyl group, α-methylhydrocinnamoyl group, 2,2-diphenylpropionyl group, 3,3-diphenyl Propionyl group, 3,3,3-triphenylpropionyl group, 2-phenylbutyryl group, 3-phenylbutyryl group, 4-phenylbutyryl group, 5-phenylvaleryl group, 3-methyl-2-phenylvaleryl group, 6-phenylhexanoyl group, α-methoxyphenylacetyl group, phenoxyacetyl group, 3-phenoxy Propionyl group, 2-phenoxypropionyl group, 11-phenoxydecanoyl group, 2-phenoxybutyryl group, 2-methoxyacetyl group, 3- (2-methoxyphenyl) propionyl group, 3- (p -Toluyl) propionyl group, (4-methylphenoxy) acetyl group, 4-isobutyl-α-methylphenylacetyl group, 4- (4-methoxyphenyl) butyryl group, (2,4-di-tert- Pentylphenoxy) -acetyl group, 4- (2,4-di-tert-pentylphenoxy) -butyryl group, (3,4-dimethoxyphenyl) acetyl group, 3,4- (methylenedioxy) phenylacetyl Group, 3- (3,4-dimethoxyphenyl) propionyl group, 4- (3,4-dimethoxyphenyl) butyryl group, (2,5-dimethoxyphenyl) acetyl group, (3,5-dimethoxy Phenyl) acetyl group, 3,4,5-trimethoxyphenylacetyl group, 3- (3,4,5-trimethoxyphenyl) -propionyl group, acetyl group, 1-naphthylacetyl group, 2-naph Acetylacetyl group, α-trityl-2-naphthalene-propionyl group, (1-naphthoxy) acetyl group, (2-naphthoxy) acetyl group, 6-methoxy-α-methyl-2-naphthaleneacetyl group, 9-fluoreneacetyl group, 1 -Pyreneacetyl group, 1-pyrenebutyryl group, γ-oxo-pyrenebutyryl group, styreneacetyl group, α-methylcinnamoyl group, α-phenylcinnamoyl group, 2-methylcinnamoyl group, 2-methoxycinnamoyl group , 3-methoxy cinnamoyl group, 2,3-dimethoxy cinnamoyl group, 2,4-dimethoxy cinnamoyl group, 2,5-dimethoxy cinnamoyl group, 3,4-dimethoxy cinnamoyl group, 3, 5-dimethoxycinnamoyl group, 3,4- (methylenedioxy) cinnamoyl group, 3,4,5-trimethoxycinnamoyl group, 2,4,5-trimethoxycinnamoyl group, 3-methylidene- 2-carbonyl group, 4- (2-cyclohexyloxy) benzoyl group, 2,3-dimethylbenzoyl group, 2,6-dimethylbenzoyl group, 2,4-dimethylbenzoyl group, 2,5-dimethylbenzoyl group, 3 -Methoxy-4-methylbenzoyl group, 3,4-diethoxybenzoyl group, α-phenyl-0-toluyl group, 2-phenoxybenzoyl group, 2-benzoylbenzoyl group, 3-benzoylbenzoyl group, 4-benzoyl Benzoyl group, 2-ethoxy-1-naphthoyl group, 9-fluorene carbonyl group, 1-fluorene carbonyl group, 4-fluorene carbon Group, a 9-anthracene group, and include 1-pyrene group.

Among these, more preferred are phenylacetyl group, hydrocinnamoyl group, diphenylacetyl group, phenoxyacetyl group, benzyloxyacetyl group, O-acetylmandelyl group, 3-methoxyphenylacetyl group, 4-methoxyphenyl Acetyl group, 2,5-dimethoxyphenylacetyl group, 3,4-dimethoxyphenylacetyl group, 9-fluorenylmethylacetyl group, cinnamoyl group, 4-methoxy-cinnamoyl group, benzoyl group, ortho- Toluoyl group, meta-toluoyl group, para-toluoyl group, m-anisoyl group, p-anisoyl group, phenylbenzoyl group, 4-ethylbenzoyl group, 4-propylbenzoyl group, 4-tert-butylbenzo Diary, 4-butylbenzoyl group, 4-pentylbenzoyl group, 4-hexylbenzoyl group, 4-heptylbenzoyl group, 4-octylbenzoyl group, 4-vinylbenzoyl group, 4-ethoxybenzoyl group, 4-butoxybenzo Diary, 4-hexyloxybenzoyl group, 4-heptyloxybenzoyl group, 4-pentyloxybenzoyl group, 4-octyloxybenzoyl group, 4-nonyloxybenzoyl group, 4-decyloxybenzoyl group, 4-undecyloxybenzo Group, 4-dodecyloxybenzoyl group, 4-isopropoxyoxybenzoyl group, 2,3-dimethoxybenzoyl group, 2,5-dimethoxybenzoyl group, 3,4-dimethoxybenzoyl group, 2,6-dimeth Methoxybenzoyl group, 2,4-dimethoxybenzoyl group, 3,5-dimethoxybenzoyl group, 2,4,5-trimethoxybenzoyl group, 3,4,5-trimethoxybenzoyl group, 1-naphtho Diary, 2-naphthoyl group, 2-biphenylcarbonyl group, 4-biphenylcarbonyl group, 4'-ethyl-4-biphenylcarbonyl group, and 4'-octyloxy-4-biphenylcarbonyl group.

Even more preferred are phenylacetyl group, diphenylacetyl group, phenoxyacetyl group, cinnamoyl group, 4-methoxy-cinnamoyl group, benzoyl group, phenylbenzoyl group, 4-ethylbenzoyl group, 4-propylbenzoyl group, 4-tert-butylbenzoyl group, 4-butylbenzoyl group, 4-pentylbenzoyl group, 4-hexylbenzoyl group, 4-heptylbenzoyl group, 3,4-dimethoxybenzoyl group, 2,6-dimethoxybenzoyl group, 2,4-dimethoxybenzoyl group, 3,5-dimethoxybenzoyl group, 3,4,5-trimethoxybenzoyl group, 2,4,5-trimethoxybenzoyl group, 1-naphthoyl group, 2- Naphthoyl group, 2-biphenylcarbonyl group, and 4-biphenylcarbonyl group.

Most preferred are benzoyl group, phenylbenzoyl group and 4-heptylbenzoyl group.

In addition to acyl group (A) and acyl group (B), it is preferable that the cellulose compound used by this invention further contains the C2-C4 aliphatic acyl group (C). Specific examples of the aliphatic acyl group (C) having 2 to 4 carbon atoms include an acetyl group, propionyl group, butyryl group, and isobutyryl group. Among these, an acetyl group, propionyl group and butyryl group are preferable, and an acetyl group is more preferable.

It is preferred that the cellulose compound for use in the present invention satisfy the following formula (I):

Formula (I)

2.4 ≤ DSA + DSB + DSC ≤ 3.0

[Wherein, DSA, DSB and DSC each represent a degree of substitution of the acyl group (A), the acyl group (B) and the acyl group (C).]. The β-1,4-linked glucose units making up cellulose have free hydroxyl groups in the 2-, 3- and 6-positions. In the present invention, the degree of substitution refers to the rate at which any one of the hydroxyl groups at the 2-, 3- and 6-positions is substituted with a specific substituent. When all of the hydroxyl groups at the 2-, 3- and 6-positions are substituted with substituents, the degree of substitution is 3.0. Furthermore, in the present invention, DSA + DSB + DSC represents the total degree of substitution and the degree of substitution of all substituents substituted with hydroxyl groups at the 2-, 3- and 6-positions. In the present invention, the degree of substitution and the degree of substitution of the substituents are determined using ¹ H-NMR using the method described in Cellulose Communication 6, 73-79 (1999) and Chrality 12 (9), 670-674. Or ^l3 C-NMR.

The cellulose compound used in the present invention preferably satisfies the following formula (Ia), and most preferably satisfies the following formula (Ib):

Formula Ia

2.6 ≤ DSA + DSB + DSC ≤ 3.0

Formula Ib

2.7 ≤ DSA + DSB + DSC ≤ 3.0

By setting the total substitution degree DSA + DSB + DSC of the cellulose compound to the above range, the humidity dependence of Re and Rth of the cellulose acylate film obtained from the composition containing the cellulose compound can be enhanced.

It is preferable that the cellulose compound used for this invention satisfy | fills following formula (II):

Formula (II)

0.1 <DSA <0.8

[In formula, DSA shows the substitution degree of the said acyl group (A). "

The cellulose compound used in the present invention preferably satisfies the following formula (IIa), and most preferably satisfies the following formula (IIb):

Formula (IIa)

0.15 <DSA <0.8

Formula (IIb)

0.2 <DSA <0.7

By setting the DSA to the above range, the humidity dependency of Re and Rth can be reduced, which is preferable.

It is preferable that the cellulose compound used for this invention satisfy | fills following formula (III):

Formula (III)

0.1 <DSB <0.8

[In formula, DSB shows substitution degree of the said acyl group (B).].

The cellulose compound used in the present invention preferably satisfies the following formula (IIIa), and most preferably satisfies the following formula (IIIb):

Formula (IIIa)

0.2 <DSB <0.8

Formula (IIIb)

0.25 <DSB <0.5.

By setting the DSB in the above range, a delay having a large absolute value can be expressed, which is preferable.

It is preferable that the cellulose compound used for this invention satisfy | fills following formula (IV) or (IV-I):

Formula (IV)

0.7DSB ≤ DSB ₆

Formula (IV-I)

DSB ₆ ≤ 0.3DSB

[In formula, DSB shows substitution degree of the said acyl group (B), DSB ₆ shows substitution degree in the 6-position of the said acyl group (B).

When the formula (IV) is satisfied, Rth represents a positive value, and when the formula (IV-I) is satisfied, Rth represents a negative value.

The cellulose compound used in the present invention preferably satisfies the following formula (IVa) or (IVa-I), and most preferably satisfies the following formula (IVb) or (IVb-I):

Formula (IVa)

0.75 DSB ≤ DSB ₆

Formula (IVa-I)

0.8 DSB ≤ DSB ₆

Formula (IVb)

DSB ₆ ≤ 0.25 DSB

Formula (IVb-I)

DSB ₆ ≦ 0.2DSB.

By setting DSB ₆ to the above range, the absolute values of Re and Rth can be increased, which is preferable.

Although the especially preferable example of the cellulose compound used for this invention is shown in Table 1, this invention is not limited to these specific examples. In Table 1, DSB ₆ shows the substitution degree of the substituent substituted at the 6-position in the substitution degree of the acyl group B containing an aromatic group.

In this invention, although a cellulose compound uses the cellulose as a raw material and shows the compound which has the cellulose skeleton obtained by introduce | transducing a functional group biologically or chemically, cellulose acylate is preferable.

In the raw cotton of the cellulose acylate used in the present invention, natural cellulose such as cotton linter and wood pulp (for example, hardwood pulp, softwood pulp), as well as wood such as microcrystalline cellulose Cellulose having a low degree of polymerization (polymerization degree 100 to 300) obtained by acid-hydrolysis of the pulp may also be used, and a mixture thereof may be used in some cases. These raw celluloses are described, for example, in Marusawa and Uda, Plastic Zairyo Koza (17), Seniso - kei Jushi (Lecture on Plastic Material (17), Fiber-Based Resin) , Nikkan Kogyo Shinbun Sha (1970)], JIII Journal of Technical Disclosure , No. 2001-1745, pp. 7-8, and Edited by The Cellulose Society of Japan, Cellulose no Jiten (Encyclopedia of Cellulose ), page 523, Asakura-Shoten (2000), and the cellulose described in the literature can be used. The cellulose is not particularly limited.

140-700 are preferable, as for the viscosity average polymerization degree of a cellulose acylate, 150-500 are more preferable, and 180-500 are the most preferable. When the average degree of polymerization is 500 or less, the viscosity of the dope solution of the cellulose compound does not become excessively high, and the film production by casting tends to be easy. Moreover, when the degree of polymerization is 140 or more, the strength of the produced film tends to be further improved, which is preferable. The average degree of polymerization is measured according to the intrinsic viscosity method proposed by Uda et al. (Kazuo Uda and Hideo Saito, Journal of the Society of Fiber Science and Technology, Japan , Vol. 18, No. 1, pp. 105-120 (1962)). can do. Specifically, it can measure in accordance with the method as described in JP-A-9-95538.

Cellulose compounds used in the present invention can be prepared by Aldrich cellulose acetate (acetyl substitution degree: 2.45) or Daicel Chemical Industries, Ltd. Cellulose acetate (acetyl substitution degree: 2.41 (trade name: L-70), 2.15 (trade name: FL-70), 1.70 (trade name) LL-10)) prepared as a starting material and used as a starting material It can be obtained by reaction.

The position of the acyl group is, for example, in the presence of a predetermined amount of base in an acetone solvent, after reacting the cellulose acetate with a predetermined amount of the acid chloride to be introduced at the 6-position, followed by the acid to be introduced at the 2 and 3-positions. Controlled by reaction with chloride.

[Cellulose Compound Composition]

The cellulose compound composition of this invention is demonstrated below.

The cellulose compound composition of this invention contains the cellulose compound containing the C5-C30 aliphatic acyl group (A) and the acyl group (B) containing an aromatic group.

The cellulose compound composition of the present invention preferably contains the cellulose compound in an amount of 70% by weight or more based on the entire composition, more preferably 80% by weight or more, and most preferably 90% by weight or more.

The cellulose compound composition of the present invention can take various forms such as granules, powders, fibers, lumps, solutions, melts and films.

As a raw material of film manufacture, it is preferable that a shape is granule or powder. Thus, the cellulose acylate composition after drying may be ground or sieved to uniformize particle size or improve handleability.

In the present invention, only one kind of cellulose compound may be used, or two or more kinds of cellulose compounds may be mixed and used. Moreover, polymer components other than a cellulose compound or various additives can also be mixed suitably. The component to be mixed is preferably a component having excellent compatibility with the cellulose compound, and is preferably added so that the transmittance of the formed film is 80% or more, more preferably 90% or more, even more preferably 92% or more. .

In the present invention, various additives (e.g., ultraviolet absorbers, plasticizers, deterioration inhibitors, microparticles and optical property modifiers) which can be generally added to cellulose acids can be added to the cellulose compound to prepare the composition. . At the time of addition of the additive to the cellulose compound represented by formula (I), the additive may be added at any time in the dope preparation step or at the end of the dope preparation process.

[Cellulose Compound Film]

The invention also relates to a cellulose compound film.

The cellulose compound film of this invention is a cellulose compound film formed from the cellulose composition of this invention.

In the cellulose compound film of the present invention, the cellulose compound of the present invention is preferably contained in an amount of at least 50% by weight, more preferably at least 80% by weight, most preferably at least 95% by weight.

Although the manufacturing method of the cellulose compound film of this invention is not specifically limited, It is preferable that a cellulose compound film is manufactured by the following melt film forming method or the solution film forming method.

<Solution film-forming>

Preferred embodiments for producing the cellulose compound film of the present invention by the solution film-forming method are described below.

In the present invention, the solvent of the cellulose compound is not particularly limited as long as the cellulose compound can be dissolved, cast and film-formed. Preferred solvents include chlorine-based organic solvents such as dichloromethane, chloroform, 1,2-dichloroethane and tetrachloroethylene, and chlorine-free organic solvents.

The non-chlorine organic solvent used in the present invention is preferably a solvent selected from esters, ketones and ethers each having 3 to 12 carbon atoms. Esters, ketones and ethers may have a cyclic structure. Compounds having two or more functional groups (ie, -O-, -CO- and -COO-) of esters, ketones and ethers can also be used as the main solvent, which compounds have other functional groups such as alcoholic hydroxyl groups. Can be. In the case of the main solvent which has two or more types of functional groups, this is enough as long as carbon number exists in the range prescribed | regulated about the compound which has any one functional group. Examples of esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate. Examples of ketones having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and methylcyclohexanone. Examples of ethers having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, anisole and phentol. Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol.

The chlorine-based organic solvent used in the present invention is not particularly limited as long as its object can be achieved and the cellulose compound can be dissolved, cast and film-formed. The chlorine organic solvent is preferably dichloromethane or chloroform, more preferably dichloromethane. Organic solvents other than chlorine-based organic solvents may also be mixed without any particular problem. In that case, it is required to use dichloromethane at a concentration of at least 50 mass%. Non-chlorine organic solvents used in combination in the present invention are described below. As the non-chlorine organic solvent, a solvent selected from esters having 3 to 12 carbon atoms, ketones, ethers, alcohols, hydrocarbons, and the like is preferable. Esters, ketone ethers and alcohols may each have a cyclic structure. Compounds having two or more functional groups (ie -0-, -CO- and -COO-) of esters, ketones and ethers can also be used as solvents, which compounds may simultaneously have other functional groups such as alcoholic hydroxyl groups. Can be. In the case of a solvent having two or more kinds of functional groups, this is sufficient as long as the carbon number is within the range specified for the compound having any one functional group. Examples of esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate. Examples of ketones having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and methylcyclohexanone. Examples of ethers having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, anisole and phentol. Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol.

Alcohols which are preferably used in combination with chlorine-based organic solvents may be linear, branched or cyclic. In particular, saturated aliphatic hydrocarbons are preferred. The hydroxyl group of the alcohol may be primary, secondary or tertiary. Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol and cyclohexanol. Fluorinated alcohol may also be used as the alcohol. Examples thereof include 2-fluoroethanol, 2,2,2-trifluoroethanol and 2,2,3,3-tetra-fluoro-1-propanol. The hydrocarbon may be linear, branched or cyclic, and either aromatic hydrocarbon or aliphatic hydrocarbon may be used. Aliphatic hydrocarbons may be saturated or unsaturated. Examples of hydrocarbons include cyclohexane, hexane, benzene, toluene and xylene.

The non-chlorine organic solvent used in combination with the chlorine organic solvent which is the main solvent for the cellulose compound is not particularly limited, but methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, dioxolane, dioxane, 4 to 4 carbon atoms Ketones, acetoacetic acid esters, alcohols having 1 to 10 carbon atoms and hydrocarbons. Non-chlorine organic solvents preferably used in combination include methyl acetate, acetone, methyl formate, ethyl formate, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl acetylacetate, methanol, ethanol, 1-propanol, 2- Propanol, 1-butanol, 2-butanol, cyclohexanol, cyclohexane and hexane.

In the present invention, the cellulose compound is preferably dissolved in an organic solvent at a concentration of 10 to 35 mass%, more preferably at 13 to 30 mass%, and the cellulose acylate in which the cellulose compound is dissolved at a concentration of 15 to 28 mass%. Even more preferred is the solution. In order to dissolve the cellulose compound at the above concentration, the cellulose compound can be dissolved at a predetermined concentration in its dissolution step, or a low concentration solution is prepared in advance (for example, 9 to 14 mass%), and then the concentration described later. In step a predetermined high concentration solution may be prepared. In addition, after producing cellulose at a high concentration in advance, a predetermined low concentration of the cellulose compound solution can be produced by adding various additives. In any of these methods, there is no particular problem if the cellulose compound solution is adjusted to the concentration of the present invention.

The method for dissolving the cellulose compound solution (dope) in the present invention is not particularly limited, and dissolution can be performed at room temperature or by a cooling dissolution method, a high temperature dissolution method, or a combination thereof. Regarding these methods, the manufacturing method of a cellulose acylate solution is JP-A-5-163301, JP-A-61-106628, JP-A-58-127737, JP-A-9-95544, JP-A, for example. -10-95854, JP-A-10-45950, JP-A-2000-53784, JP-A-11-322946, JP-A-11-322947, JP-A-2-276830, JP-A-2000 -273239, JP-A-11-71463, JP-A-04-259511, JP-A-2000-273184, JP-A-11-323017 and JP-A-11-302388. If the method of melt | dissolving a cellulose acylate in the organic solvent of these patent publications is in the range of this invention, it can apply suitably also in this invention. In particular, for non-chlorine solvent systems, see JIII Journal of Technical Disclosure , No. 2001-1745, pp. 22-25, Japan Institute of Invention and Innovation (March 15, 2001). Furthermore, the solution of cellulose compounds of the present invention is typically applied to concentration and filtration of the solution, which is similarly described in JIII Journal of Technical Disclosure , No. 2001-1745, page 25, Japan Institute of Invention and Innovation (March 15, 2001). When dissolving at a high temperature, the temperature is much higher than the boiling point of the organic solvent used, in which case the solvent is used under pressure.

In the present invention, the viscosity and the dynamic storage modulus of the cellulose compound solution are preferably within a certain range. The sample solution (1 mL) is measured with a galvanometer (CLS 500) using a Steel Cone (both manufactured by TA Instruments) having a diameter of 4 cm / 2 °. The measurement is carried out at varying temperatures at 2 ° C./min in the range of 40 ° C. to −10 ° C., under conditions of vibration step / temperature ramp, and static non-Newton viscosity at 40 ° C. The storage elastic ratio G '(Pa) at n * (Pa * s) and -5 degreeC is measured. Incidentally, the measurement is started after the sample solution is held at the measurement start temperature in advance until the liquid temperature becomes constant. In the present invention, the dope has a viscosity of 1 to 400 Pa · s at 40 ° C, a dynamic storage elastic modulus at 15 ° C of 500 Pa or more, a viscosity of 10 to 200 Pa · s at 40 ° C, and 15 ° C. More preferably, the dynamic storage elastic ratio is from 100 to 1,000,000. Furthermore, it is preferable that the dynamic storage elastic ratio at low temperature is larger, for example, when the casting support is -5 ° C, the dynamic storage elastic ratio at -5 ° C is preferably 10,000 to 1,000,000 Pa, and the support is When at -50 ° C, the dynamic storage elasticity ratio at -50 ° C is preferably 10,000 to 5,000,000 Pa.

(Specific method of solution film-forming)

The manufacturing method of the cellulose compound film of this invention is demonstrated below. As for the method and apparatus for producing the cellulose acylate film of the present invention, the solution casting film-forming method and the solution casting film-forming apparatus conventionally used for producing the cellulose acylate film are used. The dope (cellulose compound solution) produced in the dissolution apparatus (kettle) is once stored in a storage kettle and finished by removing the bubbles contained in the dope. The dope is fed from the dope outlet to the press die via a pressurized metering gear pump capable of supplying a certain amount of liquid with high precision, for example by rotational speed, and the mouth ring (slit) of the press die. slit) uniformly cast on the metal support in the casting part running indefinitely, and peeling off the dried dope film (often referred to as a web) from the metal support at the peel point after almost one round of the metal support. Let's do it. Both ends of the obtained web are sandwiched between clips and dried by conveying with a tenter while maintaining the width. Subsequently, the film is transferred to a roll group of drying apparatuses, and the drying is finished, followed by winding up to a predetermined length with a take-up machine. The combination of drying apparatus, including tenter and roll group, is variable depending on the purpose. In the solution casting film-forming method used for silver halide photosensitive materials or functional protective films for electronic displays, in addition to the solution casting film-forming apparatus, a subbing layer, an antistatic layer, an antihalation layer and In order to apply surface finish to a film such as a protective layer, a coating device is often added. These manufacturing steps are carried out in the categories of casting (co-casting, metal support, drying, separation, stretching, etc. JIII Journal of Technical Disclosure , No. 2001-1745, pp. 25-30, Japan Institute of Invention and Innovation (March 15, 2001).

<Process of Cellulose Compound Film>

(Extension)

The cellulose compound film of the present invention prepared by the molten film-forming method or the solution film-forming method in the above manner is preferably stretched for the purpose of reinforcing the surface state, expressing Re and Rth or improving the linear expansion rate.

The stretching can be carried out on-line in the film-forming step, or after the film formation is completed, the film can be stretched off-line after winding once. In other words, in the case of molten film-forming, the stretching may be carried out without cooling of the film forming being completed or after the end of cooling.

It is preferable to perform extending | stretching at the temperature of Tg-(Tg + 50 degreeC), More preferably, it is Tg-(Tg + 40 degreeC), More preferably, it is Tg-(Tg + 30 degreeC). Preferred elongation is from 0.1% to 500%, more preferably from 10 to 300%, even more preferably from 30 to 200%. Stretching can be carried out in one step or multiple steps. Elongation as used herein is determined according to the following formula:

Elongation (%) = 100 × {(length after stretching)-(length before stretching)} / length before stretching.

The stretching is carried out by longitudinal stretching, horizontal stretching or a combination thereof. In longitudinal stretching, for example, (1) stretching in a roll (where stretching is carried out in the longitudinal direction using two or more pairs of nip rolls with a faster peripheral speed at the exit side) and (2) fixed-edge stretching (Where the film is conveyed while grasping both edges of the film and gradually increasing the speed in the longitudinal direction to carry out stretching in the longitudinal direction). Further, horizontally, for example, tenter stretching may be used, in which both edges of the film are grasped with a chuck and the film is expanded in the horizontal direction (the direction perpendicular to the vertical direction) to perform stretching. Longitudinal stretching or lateral stretching can be performed independently (uniaxial stretching), or these can be performed in combination (biaxial stretching). In the case of biaxial stretching, longitudinal stretching and transverse stretching can be performed sequentially (sequential stretching) or simultaneously (simultaneous stretching).

In the longitudinal stretching and the horizontal stretching, the stretching speed is preferably 10 to 10,000% / min, more preferably 20 to 1,000% / min, even more preferably 30 to 800% / min. In the case of multistage stretching, the stretching speed means the average value of the stretching speeds in each stage.

Following such stretching, it may be desirable to also carry out 0-10% relaxation in the longitudinal or transverse direction. In addition, following stretching, it may be desirable to also perform heat fixation at a temperature of 150 to 250 ° C. for 1 second to 3 minutes.

10-300 micrometers is preferable, as for the film thickness after such extending | stretching, 20-200 micrometers is more preferable, 30-100 micrometers is still more preferable.

It is preferable that the angle θ at which the film-forming direction (vertical direction) forms with the slow axis of Re of the film is close to 0 °, + 90 ° or -90 °. That is, in the case of longitudinal stretching, the angle is preferably closer to 0 °, more preferably 0 ± 3 °, even more preferably 0 ± 2 °, and even more preferably 0 ± 1 °. In the case of lateral stretching, the angle is preferably 90 ± 3 ° or −90 ± 3 °, more preferably 90 ± 2 ° or −90 ± 2 °, even more preferably 90 ± 1 ° or −90 ± 1 °.

In order to suppress the light leakage which arises when making a polarizing plate look oblique, it is necessary to arrange | position the transmission axis of a polarizing film and the in-plane slow axis of a cellulose compound film in parallel. Since the transmission axis of the roll film-shaped polarizing film manufactured continuously is generally parallel with the width direction of a roll film, it continuously carries out the protective film containing the said roll film-shaped polarizing film and a roll film-shaped cellulose compound film. In order to laminate, it is required to make the in-plane slow axis of the roll film-shaped protective film parallel to the width direction of the film. Therefore, it is preferable to perform extending | stretching in the width direction at larger ratio. Stretching may be performed during the film-forming process, or may be carried out to stretch a manufactured and wound stock film. In the former case, the film can be stretched in a state containing a residual solvent, and preferably stretched when the amount of residual solvent is 2 to 30 mass%.

The thickness of the cellulose compound film obtained after drying, which is preferably used in the present invention, depends on the purpose of use, but is preferably 5 to 500 µm, more preferably 20 to 300 µm, and more preferably 30 to 150 µm. More preferred. When used for optics, especially VA liquid crystal display device, it is preferable that film thickness is 40-110 micrometers. The film thickness can be adjusted to the desired thickness, for example, by controlling the solid content concentration contained in the dope, the slit gap of the inlet ring of the die, the extrusion pressure from the die or the speed of the metal support.

The width of the cellulose compound film thus obtained is preferably 0.5 to 3 m, more preferably 0.6 to 2.5 m, even more preferably 0.8 to 2.2 m. Regarding the length, the film is preferably wound at 100 to 10,000 m per roll, more preferably 500 to 7,000 m, and still more preferably 1,000 to 6,000 m. When winding up the film, it is desirable to give a knurl to at least one corner. The width of the node is preferably 3 to 50 mm, more preferably 5 to 30 mm, and a height is preferably 0.5 to 500 m, more preferably 1 to 200 m. Nodes can be given by pressing on one side or pressing on both sides.

The unstretched or stretched cellulose compound films described above may be used alone or in combination with a polarizing plate, or thereon a liquid crystal layer, a layer having a controlled refractive index (low refractive layer), or a hardcoat ) May be used after providing the layer.

[Optical Properties of Cellulose Compound Film]

In the context of the present invention, Re (λ) and Rth (λ) each represent an in-plane delay and a delay in the thickness direction at a wavelength of λ. Re (λ) is measured by injecting light having a wavelength of λ nm in the film normal direction in KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments).

When the film to be measured is a film represented by a uniaxial or biaxial refractive index ellipsoid, Rth (λ) is calculated by the following method.

Re (λ) described above is an inclined axis (rotation axis), which is a slow axis in the plane (as determined by KOBRA 21ADH or WR) (if there is no slow axis, any direction in the film plane is used as the rotation axis). 6 points were measured by injecting light of wavelength λnm from the direction inclined in 10 ° steps to 50 ° on one side from the normal direction with respect to the film normal direction. And based on the film thickness value input, Rth (λ) is calculated as KOBRA 21ADH or WR.

In the above, when the film has a direction in which the retardation value becomes zero at a specific inclination angle from the normal direction using the rotation axis which is the in-plane slow axis, the delay value at the inclination angle larger than the inclination angle is negative. Calculate with KOBRA 21ADH or WR after changing to negative sign.

Incidentally, by using the slow axis as the inclination axis (rotation axis) (if there is no slow axis, use any direction in the film plane as the rotation axis), by measuring the delay value from any two inclined directions, Rth is measured. Based on the obtained values, the assumption of the average refractive index, and the film thickness value input, it may be calculated according to the following formulas (1) and (2):

Formula (1):

[In formula, Re ((theta)) shows the delay value in the direction which inclined at angle (theta) from a normal line direction.).

In Equation (1), nx represents a refractive index in the slow axis direction in the plane, ny represents a refractive index in a direction perpendicular to nx at the plane, and nz represents a refractive index in a direction perpendicular to nx and ny D represents the thickness of the film.

Formula (2):

When the film to be measured is a film which cannot be represented by a single-axis or biaxial index ellipsoid, or a film not having a so-called optical axis, Rth (λ) is calculated by the following method.

Re (λ) is inclined in 10 ° steps from -50 ° to + 50 ° with respect to the film normal direction, using the tilt axis (rotation axis), which is the in-plane slow axis (judged by KOBRA 21ADH or WR). 11 points are measured by incidence of light having a wavelength of λ nm, and Rth (λ) is calculated as KOBRA 21ADH or WR based on the input of the measured delay value, the hypothesis of the average refractive index, and the film thickness value.

In the above measurement, as an assumption of the average refractive index, the values described in Polymer Handbook (John Wiley & Sons, Inc) and catalogs of various optical films can be used. The average refractive index for which the value of the average refractive index is unknown can be measured with an Abbe refractometer. For example, the values of the average refractive index of the main optical film are as follows: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49) and polystyrene ( 1.59). When inputting the film thickness and hypothesis of this average refractive index, KOBRA 21ADH or WR yields nx, ny and nz, and from these calculated nx, ny and nz, Nz = (nx-nz) / (nx-ny) Is further calculated.

In the cellulose compound film of the present invention, Re and Rth can be adjusted by total substitution degree, substitution degree distribution or elongation of 2-, 3-, and 6-positions of the substituent.

The variation in the Re (590) value in the film width direction is preferably ± 5 nm, more preferably ± 3 nm, and the variation in the Rth (590) value in the width direction is preferably ± 10 nm, more preferably Is ± 5 nm. The fluctuations in the Re value and the Rth value in the longitudinal direction are also preferably within each range of the fluctuation in the width direction.

Equilibrium Water Content

About the measurement method of moisture content, the cellulose acylate film sample (7 mm x 35 mm) of this invention was used for the moisture content meter or the sample drying apparatus (AQUACOUNTER AQ-200, LE-20S, both manufactured by Hiranuma Sangyo Co., Ltd.) Measured using Karl Fischer method. The water content (g) is divided by the mass (g) of the sample to calculate the equilibrium moisture content.

 The equilibrium moisture content of the cellulose acylate film of the present invention at 25 ° C. and 80% RH is preferably 0 to 3%, more preferably 0.1 to 2%, even more preferably 0.3 to 1.5%. When the equilibrium moisture content exceeds 3%, when used as a support for the optical compensation film, the film has a large dependency of retardation on humidity change, and the optical compensation performance is undesirably degraded.

In the case of using the cellulose compound film of the present invention in VA mode or OCB mode, two embodiments can be taken, i.e., one embodiment is arranged on each side of the cell by placing a total of two films on both sides. Use (two film forms), and one embodiment is the use of a film (one film form) only on one side of the cell above and below.

In the case of two film forms, Re (590) is preferably 20 to 100 nm, more preferably 30 to 70 nm, Rth (590) is preferably 70 to 300 nm, more preferably 100 to 200 nm. .

In the case of one film form, Re (590) is preferably 30 to 150 nm, more preferably 40 to 100 nm, Rth (590) is preferably 100 to 300 nm, more preferably 150 to 250 nm. Do.

[Haze]

For example, when measured using a haze meter (Model 1001DP, manufactured by Nippon Denshoku Industries Co., Ltd.), the haze value of the cellulose compound film of the present invention is preferably 0.1 to 0.8, more preferably 0.1 to 0.7. It is more preferable that it is 0.1-0.60. By controlling the haze to be in the above range, an image with high contrast is obtained when the film is inserted into the liquid crystal display device as an optical compensation film.

(Photoelastic coefficient)

It is preferable that the cellulose compound film of this invention is used as a polarizing plate protective film or a retardation plate. When used as a polarizing plate protective film or a retardation plate, birefringence (Re, Rth) sometimes changes by the stress caused by elongation or contraction by moisture absorption. The change in birefringence caused by stress, such as may be measured as the photoelastic coefficient, the photoelastic coefficient is preferably 5 × 10 ^-7 to ^{30 × 10 -7 (cm 2 /} kgf), and more preferably from 6 × 10 ^{- 7} a to ^{25 × 10 -7 (cm 2 /} kgf), still more preferably 7 × 10 ^-7 to ^{20 × 10 -7 (cm 2 /} kgf).

(Surface treatment)

The unstretched or stretched cellulose compound film is optionally surface treated, whereby the adhesion of the cellulose compound film with each functional layer (eg, an undercoat layer or a back layer) can be enhanced. Examples of surface treatments that can be used include glow discharge treatments, ultraviolet irradiation treatments, corona treatments, flame treatments and acid or alkali treatments. As used herein, the glow discharge treatment may be a low temperature plasma occurring under a low pressure gas of 10 ⁻³ to 20 Torr. Plasma treatment under atmospheric pressure is also preferred. Plasma excitating gas means a gas to which plasma is excited under such conditions, and examples thereof include chlorofluorocarbons such as argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, tetrafluoromethane and the like. Mixtures thereof. These are described in JIII Journal of Technical Disclosure , No. 2001-1745, pp. 30-32, Japan Institute of Invention and Innovation (March 15, 2001). Incidentally, in the atmospheric plasma treatment, which has recently attracted attention, for example, irradiation energy of 20 to 500 Kgy is used under 10 to 1,000 Kev, and irradiation energy of 20 to 300 Kgy is preferably used under 30 to 500 Kev. Among these treatments, alkali saponification treatment is preferred, which is very effective as a surface treatment of a cellulose compound film.

(Optical anisotropic layer)

Next, the liquid crystal molecules of the optically anisotropic layer are oriented on the alignment film. Thereafter, if necessary, the oriented film polymer and the polyfunctional monomer contained in the optically anisotropic layer are reacted, or a crosslinking agent is used to crosslink the oriented film polymer.

Liquid crystal molecules used in the optically anisotropic layer include rod-shaped liquid crystal molecules and disc-shaped liquid crystal molecules. Each of the rod-shaped liquid crystal molecules and the discotic liquid crystal molecules may be a polymer liquid crystal or a low molecular liquid crystal. Liquid crystal molecules also include low molecular liquid crystals that are crosslinked and no longer exhibit liquid crystallinity.

1) Rod-shaped liquid crystal molecules

As the rod-shaped liquid crystal molecule, azomethine, azoxy, cyanobiphenyl, cyanophenyl ester, benzoic acid ester, cyclohexanecarboxylic acid phenyl ester, cyanophenylcyclohexane, cyano-substituted phenylpyrimidine, alkoxy-substituted Preference is given to using phenylpyrimidine, phenyldioxane, tolan and alkenylcyclohexylbenzonitrile.

Metal complexes are also included in the rod-like liquid crystal molecules. Furthermore, liquid crystal polymers containing rod-like liquid crystal molecules as repeating units can also be used as rod-shaped liquid crystal molecules. In other words, the rod-like liquid crystal molecules can be combined with the (liquid crystal) polymer.

Rod-shaped liquid crystal molecules are described in Kikan Kagaku - Sosetsu (General Chemistry Quarterly) , Vol. 22, edited by "Ekisho no Kagaku (Liquid Crystal Chemistry)", Chapters 4, 7 and 11, The Chemical Society of Japan (1994); And Ekisho Device Handbook (Liquid Crystal Device Handbook) ", Chapter 3, Japan Society for the Promotion of Science, edited the 142th Committee.

The birefringence of the rod-shaped liquid crystal molecules is preferably 0.001 to 0.7.

The rod-like liquid crystal molecules preferably have a polymerizable group in order to fix the alignment state of the molecules. The polymerizable group is preferably a radical polymerizable unsaturated group or a cationic polymerizable group, and specific examples thereof include polymerizable groups and polymerizable liquid crystal compounds described in JP-A-2002-62427, paragraphs [0064] to [0086]. .

2) disc-shaped liquid crystal molecules

Discoid (discotic) liquid crystal molecules include [C. Destrade, et al . , Mol . Cryst. , Vol. 71, page 111 (1981); benzene derivatives described in the study report; [C. Destrade, et al . , Mol Cryst. , Vol. 122, page 141 (1985) and Physics lett ., A , Vol. 78, page 82 (1990)] trucsen derivatives described in the research report; [B. Kohne, et al . , Angew . Chem . , Vol. 96, page 70 (1984)] cyclohexane derivatives; JM Lehn, et al . , J. Chem . Commun . , page 1794, (1985) and [J. Zhang, et al . , J. Am. Chem . Soc . , Vol. 116, page 2655 (1994)] include azacrown- or phenylacetylene-based macrocycles described in the research report.

Discotic liquid crystal molecules also include compounds having a structure in which a linear alkyl group, an alkoxy group or a substituted benzoyloxy group is radially substituted in the parent nucleus at the center of the molecule as a side chain of the mother nucleus and exhibits liquid crystallinity. Preferred are compounds in which the molecule or collection of molecules has rotational symmetry and can impart a constant orientation. In the case of forming the optically anisotropic layer from the discotic liquid crystal molecules, the compound finally included in the optically anisotropic layer need not be the discotic liquid crystal molecules, but polymerized or crosslinked through a reaction caused by the light effect to have a high molecular weight. As a result, compounds which lose liquid crystal are also included. Preferred examples of discotic liquid crystal molecules are described in JP-A-8-50206. Polymerization of discotic liquid crystal molecules is also described in JP-A-8-27284.

In order to fix the discotic liquid crystal molecules by polymerization, a polymerizable group must be bonded as a substituent to the discotic core of the discotic liquid crystal molecule. Compounds which bond polymerizable groups to the discotic core via the linking group are preferred, and by such a bond, the alignment can be maintained even in the polymerization reaction. Examples thereof include the compounds described in JP-A-2000-155216, paragraphs [0151] to [0168].

In the hybrid orientation, the angle between the long axis (disc side) of the discotic liquid crystal molecules and the side of the polarizing film increases or decreases as the distance from the side of the polarizing film in the depth direction of the optically anisotropic layer increases. The angle is preferably reduced as the distance increases. The change in angle may be a continuous increase, a continuous decrease, an intermittent increase, an intermittent decrease, a change including a continuous increase and a continuous decrease, or an intermittent change including an increase and a decrease. In the intermittent change, there is a region where the inclination angle does not change in the middle of the thickness direction. Even if there is an area with no angular change, this may be sufficient if the angle is increased or decreased as a whole. It is desirable for the angle to change continuously.

The average direction of the long axis of the discotic liquid crystal molecules on the polarizing film side can generally be adjusted by selecting the material for the discotic liquid crystal molecules or the oriented film, or by selecting the rubbing method. In addition, the long axis (disc face) direction of the discotic liquid crystal molecules on the surface side (air side) can generally be adjusted by selecting the type of additive used with discotic liquid crystal molecules or discotic liquid crystal molecules. Examples of additives used with discotic liquid crystal molecules include plasticizers, surfactants, polymerizable monomers and polymers. The degree of change in the orientation direction of the long axis can be adjusted by selecting liquid crystal molecules or additives similarly to the above.

(Formation of optically anisotropic layer)

The optically anisotropic layer can be formed by applying a coating solution containing liquid crystal molecules and a polymerization initiator and other optional components described below as necessary on the alignment film.

The solvent used for preparation of the coating solution is preferably an organic solvent. Examples of organic solvents include amides (eg N, N-dimethylformamide), sulfoxides (eg dimethylsulfoxide), heterocyclic compounds (eg pyridine), hydrocarbons (eg, Benzene, hexane), alkyl halides (eg chloroform, dichloromethane, tetra chloroethane), esters (eg methyl acetate, butyl acetate), ketones (eg acetone, methyl ethyl ketone) and ethers ( Tetrahydrofuran, 1,2-dimethoxyethane). Among these, alkyl halides and ketones are preferable. Two or more types of organic solvents can be used in combination.

The coating solution can be applied by known methods (eg wire bar coating, extrusion coating, direct gravure coating, reverse gravure coating, die coating). .

It is preferable that the thickness of an optically anisotropic layer is 0.1-20 micrometers, More preferably, it is 0.5-15 micrometers, Most preferably, it is 1-10 micrometers.

(Fixing the Orientation State of Liquid Crystal Molecules)

The oriented liquid crystal molecules can be fixed while maintaining the alignment state. It is preferable to perform fixation by a polymerization reaction. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator. Photopolymerization reaction is preferred.

Examples of photopolymerization initiators include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ethers (described in US Pat. No. 2,448,828), α-hydrocarbon-substituted aromatic acyls Combinations of phosphorus compounds (described in US Pat. No. 2,722,512), polynuclear quinone compounds (described in US Pat. Nos. 3,046,127 and 2,951,758), triarylimidazole dimers and p-aminophenyl ketones (US Pat. 3,549,367), acridine and phenazine compounds (described in JP-A-60-105667 and US Pat. No. 4,239,850), and oxadiazole compounds (described in US Pat. No. 4,212,970) do.

The usage-amount of a photoinitiator becomes like this. Preferably it is 0.01-20 mass%, More preferably, it is 0.5-5 mass% based on solid content of a coating solution.

It is preferable to perform light irradiation for superposition | polymerization of a liquid crystal molecule using an ultraviolet-ray.

The irradiation energy is preferably 20 mJ / cm ² to 50 J / cm ² , more preferably 20 to 5,000 mJ / cm ² , even more preferably 100 to 800 mJ / cm ² . In order to promote a photopolymerization reaction, light irradiation can be performed under heating conditions.

A protective layer may also be provided over the optically anisotropic layer.

[Anti-reflective film]

The invention also relates to an antireflective film comprising a cellulose acylate film and an antireflective layer. The antireflective film can be manufactured according to a conventional manufacturing method, for example, can be manufactured with reference to JP-A-2006-241433.

[Polarizing Plate]

The present invention also relates to a polarizing plate comprising a polarizing film and two protective films sandwiching the polarizing film, wherein at least one of these two protective films is a cellulose acylate film of the present invention. The cellulose acylate film may be laminated to the polarizing film as part of an optical compensation film having an optically anisotropic layer or as part of an antireflective film having an antireflective layer. When having another layer, it is preferable that the surface of the cellulose acylate film of this invention is laminated | stacked on the surface of a polarizing film. A polarizing plate can be manufactured with reference to JP-A-2006-241433, for example.

(Image display device)

The present invention relates to an image display apparatus including at least one of a cellulose compound film or a retardation film, a polarizing plate, an optical compensation film, and an antireflection film.

<Liquid crystal display device>

The cellulose compound film of this invention and the polarizing plate, retardation film, or optical film which respectively use this cellulose compound film can be preferably incorporated in a liquid crystal display device. Liquid crystal display devices include TN type, IPS type, FLC type, AFLC type, OCB type, STN type, ECB type, VA type and HAN type. In addition, the cellulose compound film can be preferably used in any of a transmissive, reflective and transflective liquid crystal display device. Each liquid crystal mode is described below.

(TN type liquid crystal display device)

The cellulose compound film of this invention can be used as a support body of an optical compensation sheet in the TN-type liquid crystal display device which has the liquid crystal cell of TN mode. TN-mode liquid crystal cells and TN-type liquid crystal display devices are commonly well known. Optical compensatory sheets used in TN-type liquid crystal display devices may be manufactured according to the specifications of JP-A-3-9325, JP-A-6-148429, JP-A-8-50206 and JP-A-9-26572. Or prepared according to Mori et al . ( Jpn . J. Appl . Phys. , Vol. 36, page 143 (1997), Jpn . J. Appl . Phys. , Vol. 36, page 1068 (1997)). Can be.

(STN-type liquid crystal display device)

The cellulose compound film of the present invention can be used as a support for an optical compensation sheet in an STN-type liquid crystal display device having a liquid crystal cell of STN mode. In the STN-type liquid crystal display device, the bar liquid crystal molecules in the liquid crystal cell are generally twisted in the range of 90 to 360 °, and the product of the refractive index anisotropy (Δn) and the cell spacing (d) of the bar liquid crystal molecules (Δn) D) is 300-1,500 nm. The optical compensatory sheet used for STN-type liquid crystal display device can be manufactured according to description of JP-A-2000-105316.

(VA-type liquid crystal display device)

The cellulose compound film of this invention is used advantageously as a support body of the optical compensation sheet in VA-type liquid crystal display device which especially has a liquid crystal cell of VA-mode. The optical compensatory sheet used for the VA-type liquid crystal display device preferably has a Re value of 0 to 150 nm and an Rth value of 70 to 400 nm. When using two optically anisotropic polymer films for VA-type liquid crystal display devices, it is preferable that the Rth value of a film is 70-250 nm. When using one optically anisotropic polymer film for VA-type liquid crystal display devices, it is preferable that the Rth value of a film is 150-400 nm. The VA-type liquid crystal display device can use, for example, the orientation divided mode described in JP-A-10-123576.

(IPS-type liquid crystal display device and ECB-type liquid crystal display device)

The cellulose compound film of this invention is used suitably as an optical compensation sheet or a polarizing plate protective film in an IPS-type liquid crystal display device which has an IPS-mode liquid crystal cell, and an ECB-type liquid crystal display device which has an ECB-mode liquid crystal cell. These modes allow the liquid crystal material to be oriented almost parallel to the black display timing, wherein the liquid crystal molecules are oriented parallel to the substrate in the absence of voltage to provide a black display. In such a mode, the polarizing plate using the cellulose compound film of this invention contributes to the improvement of color tone, expansion of viewing angle, and contrast improvement. In these modes, the polarizing plate using the cellulose compound film of this invention for the protective film (protective film of a cell side) arrange | positioned between a polarizing plate among the protective films of a liquid crystal cell and the polarizing plate above and below a liquid crystal cell is at least one of a liquid crystal cell. It is preferred to be used on the side. It is more preferable that an optically anisotropic layer is arrange | positioned between a polarizing plate protective film and a liquid crystal cell, and the retardation value of the optically anisotropic layer arrange | positioned is set to 2 times or less of the (triangle | delta) n * d value of a liquid crystal layer.

 (OCB-type liquid crystal display device and HAN-type liquid crystal display device)

The cellulose compound film of the present invention is also advantageously used as a support for an optical compensation sheet in an OCB-type liquid crystal display device having a liquid crystal cell of OCB-mode and an HAN-type liquid crystal display device having a liquid crystal cell of HAN-mode. In the optical compensation sheet used for the OCB-type liquid crystal display device or the HAN-type liquid crystal display device, it is preferable that neither the normal direction nor the direction in which the absolute value of the delay is minimum exists in the plane of the optical compensation sheet. The optical properties of the optical compensation sheet used in the OCB-type liquid crystal display device or the HAN-type liquid crystal display device are also determined by the optical properties of the optically anisotropic layer, the optical properties of the support and the arrangement of the optically anisotropic layer and the support. Optical compensation sheets used in OCB-type liquid crystal display devices or HAN-type liquid crystal display devices are described in JP-A-9-197397, or by Mori et al. ( Jpn . J. Appl. Phys. , Vol. 38, page 2837 ( 1999).

(Reflective liquid crystal display device)

The cellulose compound film of the present invention is also advantageously used as an optical compensation sheet in a TN-type, STN-type, HAN-type or guest-host (GH) type reflective liquid crystal display device. These display modes have long been well known. The TN-type reflective liquid crystal display device can be manufactured according to JP-A-10-123478, International Publication WO9848320 pamphlet, and Japanese Patent No. 3022477, and the optical compensation sheet used for the reflective liquid crystal display device is international publication. It can be prepared according to the description of WO00-65384.

(Other liquid crystal display device)

The cellulose compound film of the present invention is also advantageously used as a support for an optical compensation sheet in an ASM-type liquid crystal display device having a liquid crystal cell in an axially symmetric aligned microcell (ASM) mode. A liquid crystal cell of the ASM-mode is characterized in that the thickness of the cell is maintained by a position-adjustable resin spacer. The other properties are the same as those of the liquid crystal cell of the TN-mode. Liquid crystal cells and ASM-type liquid crystal display devices in ASM mode can be manufactured according to the description of Kume et al. (Kume et al., SID 98 Digest , 1089 (1998)).

EXAMPLE

The present invention will be described in more detail below with reference to Examples, but the present invention is not limited thereto.

Synthesis Example 1 Synthesis of Intermediate Compound T-1

In a 5-liter three-necked flask equipped with a mechanical stirrer, thermometer, cooling tube, and dropping funnel, 200 g of cellulose acetate, 115 mL of pyridine and 2,000 mL of acetone with a degree of substitution of 2.15 were weighed and stirred at room temperature. did. To this, 160 mL of benzoyl chloride (manufactured by Aldrich) was slowly added dropwise and added, and then the mixture was further stirred at 50 ° C. for 2 hours. After the reaction, the reaction solution is allowed to cool to room temperature and then poured into 20 L of methanol with vigorous stirring, resulting in the deposition of a white solid material. The white solid material is separated by suction filtration and washed three times with a large amount of methanol. The white solid material obtained is dried overnight at 60 ° C. and then vacuum dried at 90 ° C. for 6 hours to give 215 g of the desired intermediate compound T-1 as a white powder. The average degree of polymerization is 254.

Synthesis Example 2: Synthesis of Compound A-4

In a 3 L-volume three-necked flask equipped with a mechanical stirrer, thermometer, cooling tube and dropping funnel, 40 g of intermediate compound T-1 and 400 ml of pyridine obtained by the above reaction are weighed and stirred at room temperature. To this, 40 mL of n-hexanoyl chloride (manufactured by Aldrich) was slowly added dropwise and added, and then the mixture was further stirred at 50 ° C. for 5 hours. After the reaction, the reaction solution is allowed to cool to room temperature and then poured into 10 L of methanol with vigorous stirring to deposit a white solid material as a result. The white solid material is separated by suction filtration and washed three times with a large amount of methanol. The white solid material obtained is dried overnight at 60 ° C. and then vacuum dried at 90 ° C. for 6 hours to give 44 g of compound A-4 as a white powder. The average degree of polymerization is 254.

Synthesis Example 3: Synthesis of Compound A-7

Compound A desired as a white solid in the same manner as in the preparation of compound A-4, except that 40 mL of n-hexanoyl chloride (manufactured by Aldrich) was changed to 60 mL of 2-ethylhexanoyl chloride (manufactured by Aldrich). -7 (45 g) is obtained. The average degree of polymerization is 255.

Synthesis Example 4: Synthesis of Intermediate Compound T-2

In the preparation of intermediate compound T-1 except for changing 160 mL of benzoyl chloride (manufactured by Aldrich) to 300 mL of 2-ethylhexanoyl chloride (manufactured by Aldrich) and changing the amount of pyridine from 230 mL to 150 mL In the same manner the desired intermediate compound T-2 (223 g) is obtained as a white solid. The average degree of polymerization is 255.

Synthesis Example 5: Synthesis of Compound A-10

In the same manner as in the preparation of compound A-4 except that the intermediate compound T-1 is replaced with T-2 and 40 mL of n-hexanoyl chloride (manufactured by Aldrich) is replaced with 60 mL benzoyl chloride (manufactured by Aldrich) This affords the desired compound A-10 (45 g) as a white powder. The average degree of polymerization is 255.

Synthesis Example 6 Synthesis of Intermediate Compound T-3

In the same manner as in the preparation of intermediate compound T-1, except that 160 mL of benzoyl chloride (manufactured by Aldrich) was converted to 280 mL of octanoyl chloride (manufactured by Aldrich) and the amount of pyridine was changed from 230 mL to 130 mL. The desired intermediate compound T-3 (235 g) is obtained as a white powder. The average degree of polymerization is 255.

Synthesis Example 7: Synthesis of Compound A-13

The desired compound A-13 (41 g) is obtained as a white powder in the same manner as in the preparation of compound A-10, except that the intermediate compound T-2 is changed to T-3. The average degree of polymerization is 255.

Synthesis Example 8: Synthesis of Intermediate Compound T-4

In the same manner as in the preparation of intermediate compound T-1, except that 160 mL of benzoyl chloride (manufactured by Aldrich) was converted to 400 mL lauroyl chloride (manufactured by Aldrich) and the amount of pyridine was changed from 230 mL to 180 mL To give the desired intermediate compound T-4 (235 g) as a white powder. The average degree of polymerization is 253.

Synthesis Example 9: Synthesis of Compound A-18

The desired compound A-18 (42 g) is obtained as a white powder in the same manner as in the preparation of compound A-10, except that the intermediate compound T-2 is changed to T-4. The average degree of polymerization is 253.

Synthesis Example 10 Synthesis of Intermediate Compound T-5

The desired intermediate in the same manner as in the preparation of the intermediate compound T-1, except that 160 mL of benzoyl chloride was changed to 500 mL of octadecanoyl chloride (manufactured by Aldrich) and the amount of pyridine was changed from 230 mL to 200 mL. Compound T-5 (235 g) is obtained as a white powder. The average degree of polymerization is 253.

Synthesis Example 11: Synthesis of Compound A-35

The desired compound A-35 (46 g) is obtained as a white powder in the same manner as in the preparation of compound A-10, except that the intermediate compound T-2 is changed to T-5. The average degree of polymerization is 253.

Synthesis Example 12 Synthesis of Intermediate Compound T-6

The desired intermediate compound T-6 (210 g) in the same manner as in the preparation of intermediate compound T-1, except that the amount of benzoyl chloride was changed from 160 mL to 200 mL and the amount of pyridine was changed from 230 mL to 260 mL. Is obtained as a white powder. The average degree of polymerization is 257.

Synthesis Example 13: Synthesis of Compound A-9

The desired compound A-9 (45 g) is obtained as a white powder in the same manner as in the preparation of compound A-7, except that the intermediate compound T-1 is changed to T-6. The average degree of polymerization is 255.

Synthesis Example 14 Synthesis of Compound A-20

Except for changing intermediate compound T-1 to T-6 and replacing 40 mL of n-hexanoyl chloride (manufactured by Aldrich) with 75 mL of dodecanoyl chloride, the desired procedure was carried out in the same manner as in the preparation of compound A-4. Compound A-20 (45 g) is obtained as a white powder. The average degree of polymerization is 255.

Synthesis Example 15 Synthesis of Compound A-37

Except for changing intermediate compound T-1 to T-6 and replacing 40 mL of n-hexanoyl chloride (manufactured by Aldrich) with 100 mL of octadecanoyl chloride, the desired procedure was carried out in the same manner as in the preparation of compound A-4. Compound A-37 (45 g) is obtained as a white powder. The average degree of polymerization is 255.

Synthesis Example 16: Synthesis of Comparative Compound B-5

The desired comparative compound B-5 (225 g) in the same manner as in the preparation of the intermediate compound T-1, except that 160 mL of benzoyl chloride (manufactured by Aldrich) was changed to 240 g 4-phenylbenzoyl chloride (manufactured by Aldrich). ) Is obtained as a white powder. The average degree of polymerization is 254.

Synthesis Example 17 Synthesis of Compound A-8

The desired compound A-8 (46 g) is obtained as a white powder in the same manner as in the preparation of compound A-10, except that Intermediate Compound T-2 is replaced with Comparative Compound B-5. The average degree of polymerization is 253.

Synthesis Example 18 Synthesis of Asaronil Chloride

In a 3 L-volume three-necked flask equipped with a mechanical stirrer, thermometer, cooling tube, and dropping funnel, 200 g of asaronic acid (manufactured by Aldrich) and 300 mL of toluene are weighed and stirred at room temperature. To this, 560 g of thionyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 10 mL of dimethylformamide were slowly added dropwise and added, and then the mixture was further stirred at 80 ° C. for 1 hour. After the reaction, toluene and unreacted thionyl chloride are removed by distillation under reduced pressure and 500 mL of hexane is poured into the residue with vigorous stirring to deposit a white solid material as a result. The white solid material is separated by suction filtration and washed three times with a large amount of hexane. The white solid material obtained is dried to give 195 g of the desired asaronyl chloride.

Synthesis Example 19 Synthesis of Compound A-32

In the same manner as in the preparation of compound A-4, except for changing the intermediate compound T-1 to T-4 and replacing 40 mL of n-hexanoyl chloride (manufactured by Aldrich) with 192 g of asaronyl chloride Compound A-32 (43 g) was obtained as a white powder. The average degree of polymerization is 255.

Synthesis Example 20 Synthesis of Compound A-33

In the same manner as in the preparation of Compound A-4, except that Intermediate Compound T-1 was changed to T-4 and 40 mL of n-hexanoyl chloride (manufactured by Aldrich) was replaced with 200 mL of 4-heptylbenzoyl chloride The desired compound A-33 (47 g) is obtained as a white powder. The average degree of polymerization is 255.

Synthesis Example 21 Synthesis of Comparative Compound B-7

Replacing cellulose acetate having a degree of substitution of 2.15 with cellulose acetate having a degree of substitution of 2.44, replacing 160 mL of benzoyl chloride with 200 mL of octadecanoyl chloride (made by Aldrich), and changing the amount of pyridine from 230 mL to 80 mL Except for the preparation of the intermediate compound T-1, the desired comparative compound B-7 (235 g) is obtained as a white powder. The average degree of polymerization is 253.

Synthesis Example 22 Synthesis of Compound A-34

The desired compound A-34 (46 g) is obtained as a white powder in the same manner as in the preparation of compound A-10, except that the intermediate compound T-2 is changed to B-7. The average degree of polymerization is 253.

Synthesis Example 23 Synthesis of Comparative Compound B-9

Desired comparison in the same manner as in the preparation of intermediate compound T-1, except 160 mL of benzoyl chloride was changed to 150 mL of cyclohexanoyl chloride (manufactured by Aldrich) and the amount of pyridine was changed from 230 mL to 93 mL Compound B-9 (202 g) is obtained as a white powder. The average degree of polymerization is 256.

Synthesis Example 24 Synthesis of Compound A-38

The desired compound A-38 (46 g) is obtained as a white powder in the same manner as in the preparation of compound A-10, except that the intermediate compound T-2 is changed to B-9. The average degree of polymerization is 256.

Synthesis Example 25 Synthesis of Comparative Compound B-12

The desired comparative compound B-12 (212 g) in the same manner as in the preparation of intermediate compound T-1, except that the amount of benzoyl chloride was changed from 160 mL to 180 mL and the amount of pyridine was changed from 230 mL to 250 mL. ) Is obtained as a white powder. The average degree of polymerization is 257.

Synthesis Example 26 Synthesis of Compound A-21

Except for changing intermediate compound T-1 to T-6 and 40 mL of n-hexanoyl chloride (manufactured by Aldrich) to 85 mL of dodecanoyl chloride, the desired procedure was carried out in the same manner as in the preparation of compound A-4. Compound A-21 (50 g) is obtained as a white powder. The average degree of polymerization is 257.

Synthesis Example 27 Synthesis of Intermediate Compound T-7

The desired intermediate compound T-7 (201 g) in the same manner as in the preparation of intermediate compound T-1, except the amount of benzoyl chloride was changed from 160 mL to 130 mL and the amount of pyridine was changed from 230 mL to 180 mL. Is obtained as a white powder. The average degree of polymerization is 258.

Synthesis Example 28 Synthesis of Compound A-22

Except for changing intermediate compound T-1 to T-7 and 40 mL of n-hexanoyl chloride (manufactured by Aldrich) to 65 mL of dodecanoyl chloride, the desired procedure was carried out in the same manner as in the preparation of compound A-4. Compound A-22 (45 g) is obtained as a white powder. The average degree of polymerization is 258.

Synthesis Example 29 Synthesis of Compound A-23

Except for changing intermediate compound T-1 to T-7 and 40 mL of n-hexanoyl chloride (manufactured by Aldrich) to 50 mL of dodecanoyl chloride, the desired procedure was carried out in the same manner as in the preparation of compound A-4. Compound A-23 (43 g) is obtained as a white powder. The average degree of polymerization is 258.

Synthesis Example 29 Synthesis of Compound A-24

The desired procedure was carried out in the same manner as in the preparation of compound A-4, except that intermediate compound T-1 was changed to T-7 and 40 mL of n-hexanoyl chloride (manufactured by Aldrich) was replaced with 30 mL of dodecanoyl chloride. Compound A-24 (39 g) is obtained as a white powder. The average degree of polymerization is 258.

Synthesis Example 30 Synthesis of Comparative Compound B-1

In the same manner as in the preparation of compound A-4, except that the intermediate compound T-1 was changed to diacetyl cellulose having a substitution degree of 2.15 and the amount of n-hexanoyl chloride (manufactured by Aldrich) was changed from 40 mL to 30 mL. Desired Comparative Compound B-1 (43 g) is obtained as a white powder. The average degree of polymerization is 258.

Synthesis Example 31 Synthesis of Comparative Compound B-2

Compound A, except replacing intermediate compound T-1 with diacetyl cellulose having a degree of substitution of 2.15 and replacing 40 mL of n-hexanoyl chloride (manufactured by Aldrich) with 35 mL of 2-ethylhexanoyl chloride (manufactured by Aldrich) In the same manner as in the preparation of -4, the desired comparative compound B-2 (43 g) is obtained as a white powder. The average degree of polymerization is 258.

Synthesis Example 32 Synthesis of Comparative Compound B-3

Same as in the preparation of compound A-4 except that intermediate compound T-1 is replaced with diacetyl cellulose having a degree of substitution of 2.15 and 40 mL of n-hexanoyl chloride (manufactured by Aldrich) is replaced with 23 mL of benzoyl chloride. In the manner to give the desired comparative compound B-3 (44 g) as a white powder. The average degree of polymerization is 257.

Synthesis Example 33 Synthesis of Comparative Compound B-4

Intermediate compound T-1 was replaced with diacetyl cellulose having a degree of substitution of 2.15 and 120 mL of n-hexanoyl chloride (manufactured by Aldrich) to 69 mL benzoyl chloride (manufactured by Aldrich) except that In the same manner as in the preparation, the desired comparative compound B-4 (46 g) is obtained as a white powder. The average degree of polymerization is 258.

Synthesis Example 34 Synthesis of Intermediate Compound T-8

Diacetyl cellulose (acetyl substitution degree: 2.15) (200 g) was dissolved in 1,500 mL of tetrahydrofuran, and 316 mL of pyridine and 927 g of triphenylmethyl chloride were added thereto, followed by 11 hours at 70 ° C. Stir. After adding 300 mL of methanol and confirming that the exotherm ceased, the resulting solution was mixed with 7,000 mL of methanol to precipitate the polymer. The polymer is subsequently washed with methanol at 40-50 ° C. and purified to yield 236 g of intermediate compound T-8.

Synthesis Example 35 Synthesis of Intermediate Compound T-9

400 mL of pyridine to 800 mL of pyridine, 40 g of intermediate compound T-1 to 80 g of T-8, and 40 mL of n-hexanoyl chloride (manufactured by Aldrich) to 240 mL of benzoyl chloride (Aldrich). Production) Intermediate compound T-9 (82 g) is obtained as a white powder in the same manner as in the preparation of compound A-4.

Synthesis Example 37 Synthesis of Comparative Compound B-6

Intermediate compound T-9 (82 g) is dissolved in 500 parts by mass of dichloromethane, and 31 parts by mass of a 25% hydrobromide acetic acid solution is added thereto. After 5 minutes of stirring at room temperature, 10 parts by mass of triethylamine dissolved in 70 parts by mass of methanol are added, and the solution is stirred for a further 20 minutes, and then mixed with methanol to precipitate the polymer. The polymer is washed successively with methanol at 40-50 ° C., then filtered and further vacuum dried to yield 45 g of comparative compound B-6. The average degree of polymerization is 255.

Synthesis Example 38 Synthesis of Intermediate Compound T-10

Diacetyl cellulose with an acetyl substitution degree of 2.15 was converted to diacetyl cellulose with an acetyl substitution degree of 2.44, except that the amount of pyridine was changed from 316 mL to 250 mL, and the amount of triphenylmethyl chloride was changed from 741 g to 560 g. Then intermediate compound T-10 (205 g) is obtained as a white powder in the same manner as in the preparation of intermediate T-8.

Synthesis Example 39 Synthesis of Intermediate Compound T-11

Intermediate compound T-11 (in the same manner as in the preparation of intermediate compound T-9, except that the intermediate compound T-8 was changed to T-10 and the amount of benzoyl chloride (manufactured by Aldrich) was changed from 240 mL to 120 mL). 215 g) is obtained as a white powder.

Synthesis Example 40 Synthesis of Comparative Compound B-8

Comparative Compound B-8 (41 g) is obtained as a white powder in the same manner as in the preparation of Comparative Compound B-6, except that Intermediate Compound T-9 is changed to T-11. The average degree of polymerization is 255.

Synthesis Example 41 Synthesis of Intermediate Compound T-12

Intermediate compound T-12 (225 g) is obtained as a white powder in the same manner as in the preparation of the intermediate compound T-9, except that the amount of benzoyl chloride (manufactured by Aldrich) is changed from 120 mL to 130 mL mL.

Synthesis Example 42 Synthesis of Comparative Compound B-10

Comparative Compound B-10 (41 g) is obtained as a white powder in the same manner as in the preparation of Comparative Compound B-6, except that Intermediate Compound T-9 is replaced with T-12. The average degree of polymerization is 255.

Synthesis Example 43 Synthesis of Comparative Compound B-11

Comparative Compound B-11 (200 g) was white in the same manner as in the preparation of Intermediate Compound T-1, except that 160 mL of benzoyl chloride (manufactured by Aldrich) was converted to 100 mL of lauroyl chloride (manufactured by Aldrich). Obtained as a powder. The average degree of polymerization is 258.

Synthesis Example 44 Synthesis of Comparative Compound B-12

The desired comparative compound B-12 (210 g) is obtained as a white powder in the same manner as in the preparation of the intermediate compound T-1, except that the amount of benzoyl chloride (manufactured by Aldrich) is changed from 160 mL to 200 mL. The average degree of polymerization is 256.

Synthesis Example 45 Synthesis of Compound A-41

The desired compound A-41 (48 g) was prepared in the same manner as in the preparation of Compound A-4, except that 40 mL of n-hexanoyl chloride (manufactured by Aldrich) was changed to 120 mL benzoyl chloride (manufactured by Aldrich). Obtained as a white powder. The average degree of polymerization is 254.

(Example 2)

<Production of Cellulose Compound Solution>

The raw material shown below is charged into a mixing tank and stirred under heating to dissolve the raw material, thereby preparing a solution with a cellulose compound solution. In addition, the cellulose compound solution of the present invention cellulose compounds A-4, 7, 8, 10, 13, 14, 18, 20 to 24, 32 to 35, 37, 38, and B-1 to 12 the degree of substitution of 2.15 It is prepared in the same manner as above by using instead of phosphorus cellulose acetate.

<Cellulose Compound Solution>

100 parts by mass of cellulose acetate having a degree of substitution of 2.15

Methylene chloride (first solvent) 402 parts by mass

60 parts by mass of methanol (second solvent)

<Production of Cellulose Compound Film Samples S-1 to S-32>

A 562 parts by mass solution having a cellulose compound solution composition was cast using a band casting machine, and a film having 15% by mass of residual solvent was uniaxially stretched under a condition of 160 ° C using a tenter as necessary. Film sample 001 (comparative example, thickness: 80 micrometers) is produced. In the following, unless otherwise stated, the thickness of all the films produced is 80 μm. Subsequently, film samples S-1 to S-31 are produced in the same manner. The results are shown in Table 2.

In the evaluation of the film sample, a part (120 mm x 120 mm) of each film sample obtained above was cut out, and the retardation value was 25 degreeC and 60% RH conditions by "KOBRA 21ADH" (made by Oji Scientific Instruments). Re and Rth for the light of wavelength 590 nm are measured under. Furthermore, each ΔRe (10), which is the difference between Re or Rth for light at wavelength 590 nm under conditions of 25 ° C. and 10% RH, and Re or Rth for light with wavelength 590 nm under conditions of 25 ° C. and 80% RH. % -80%) and ΔRth (10% -80%). The obtained results are shown in Table 2.

As can be seen from the results in Table 2, in the film sample obtained from the conventional cellulose acylate or the comparative example, the humidity dependence is large or the expression of delay is small, whereas in the film of the present invention, the absolute value of the delay is Large, both the manifestation of delay and the reduction in humidity dependence can be satisfied.

Example 3 Polarizing Plate Protective Film

Elliptical polarizing plate samples 001 to 007 were prepared and evaluated by the method described in Example 1 of JP-A-11-316378 using the sample of Example 2. The optical properties of the elliptical polarizing plate obtained from the cellulose compound film of the present invention are excellent.

Example 4 Liquid Crystal Display Device

Discrete liquid crystal molecule-containing optical and alignment film obtained by coating the liquid crystal display device described in Example 1 of JP-A-10-48420, the polyvinyl alcohol described in Example 1 of JP-A-9-26572 An anisotropic layer, a VA-type liquid crystal display device shown in FIGS. 2 to 9 of JP-A-2000-154261, and an OCB-type liquid crystal display device shown in FIGS. 10 to 15 of JP-A-2000-154261, It manufactures and evaluates using the samples 001-007. The device obtained with the cellulose compound film of the present invention obtains good performance in all cases.

The entire disclosure of each and every foreign patent application for which the benefit of a foreign priority is claimed in this application is hereby incorporated by reference as if fully stated.

Claims (14)

Cellulose compound composition comprising: The cellulose compound containing the acyl group (B) containing a C5-C30 aliphatic acyl group (A) and an aromatic group. The cellulose compound composition according to claim 1, wherein the cellulose compound further comprises an aliphatic acyl group (C) having 2 to 4 carbon atoms. The cellulose compound composition of claim 2, wherein the cellulose compound satisfies the following formula (I): Formula I 2.4 ≤ DSA + DSB + DSC ≤3.0 [Wherein, DSA, DSB and DSC each represent a degree of substitution of the acyl group (A), the acyl group (B) and the acyl group (C).]. The cellulose compound composition of claim 1, wherein the cellulose compound satisfies the following formula (II): Formula II 0.1 <DSA <0.8 [In formula, DSA shows the substitution degree of the said acyl group (A).]. The cellulose compound composition of claim 1, wherein the cellulose compound satisfies the following formula (III): Formula III 0.1 <DSB <0.8 [In formula, DSB shows substitution degree of the said acyl group (B).]. The cellulose compound composition of claim 1, wherein the cellulose compound satisfies the following formula (IV) or (IV-I): Formula IV 0.7DSB ≤ DSB ₆ Formula IV-I DSB ₆ ≤ 0.3DSB [In the meal, DSB represents the substitution degree of the said acyl group (B), DSB ₆ represents the substitution degree at the 6-position of the acyl group (B)]. The cellulose compound composition according to claim 1, wherein the acyl group (A) is selected from the group consisting of hexanoyl group, octanoyl group, 2-ethylhexanoyl group, dodecanoyl group, octadecanoyl group, and cyclohexanoyl group. The cellulose compound composition according to claim 1, wherein the acyl group (B) is selected from the group consisting of benzoyl group, phenylbenzoyl group and 4-heptylbenzoyl group. A cellulose compound film formed from the cellulose compound composition according to claim 1. A retardation film comprising the cellulose compound film of claim 9. A cellulose compound film according to claim 9; And Optically anisotropic layer formed by orienting the liquid crystal compound Optical compensation film comprising a. A cellulose compound film according to claim 9; And Antireflective layer Antireflection film comprising a. Polarizing film; And 2 protective films sandwiching the polarizing film A polarizing plate comprising a polarizing plate, wherein at least one of the two protective films comprises the cellulose compound film of claim 9. An image display apparatus comprising the cellulose compound film of claim 9.