KR20050076831A - Cellulose body composition, cellulose body film, modifier for cellulose body film, protective film of polarizing plate, liquid crystal display and silver halide photosensitive material - Google Patents

Abstract

By using a cellulose-based film having a large optical anisotropy and a small moisture permeability, a polarizing plate protective film, a liquid crystal display device, and a support for a silver halide photographic photosensitive material can be obtained.

Cellulosic composition or cellulosic film containing at least one of a cellulose body and a compound represented by the formula (1):

[Formula 1]

[Wherein, R ¹ represents an alkyl group or an aryl group, and R ² and R ³ each independently represent a hydrogen atom, an alkyl group or an aryl group. In addition, the alkyl group and the aryl group may have a substituent.].

Description

Cellulose composition, Cellulose body film, Modifier for cellulose body film, Polarizing plate protective film, Liquid crystal display device, Silver halide photosensitive material AND SILVER HALIDE PHOTOSENSITIVE MATERIAL}

TECHNICAL FIELD The present invention relates to a cellulose body composition and a cellulose body film. Specifically, the present invention relates to a cellulose body composition and a cellulose film, comprising a modifier for a cellulose body film having good moisture permeability and increasing optical anisotropy. The present invention also relates to a polarizing plate protective film, a liquid crystal display device and a silver halide photographic photosensitive material using the cellulose body film.

Conventionally, cellulose acylate film has been used as a photographic support or various optical materials because of its toughness and flame retardancy. In particular, recently, it is used a lot as an optical transparent film for liquid crystal display devices. The cellulose acylate film is excellent in optical transparency and optically isotropic in that it is excellent as an optical material for a device for handling polarization such as a liquid crystal display device, and the display of the polarizer protective film and the oblique direction so far is good. It has been used as a support for an optical compensation film capable of (viewing angle compensation).

In the polarizing plate, which is one of the members for the liquid crystal display device, a protective film of the polarizer is formed on at least one side of the polarizer by bonding. Common polarizers are obtained by dyeing stretched polyvinyl alcohol (PVA) based films with iodine or dichroic dyes.

In most cases, as a protective film of a polarizer, the cellulose acylate film which can be directly bonded to PVA, especially the triacetyl cellulose film, is used. The optical characteristics of this polarizer protective film greatly influence the characteristics of the polarizing plate.

On the other hand, since the moisture permeability under high temperature and high humidity generally deteriorates compared with other transparent support bodies, for example, a polyethylene terephthalate film, the compound called a plasticizer is often added. As a plasticizer added to cellulose acylate, phosphate triesters such as triphenyl phosphate and biphenyl diphenyl phosphate, phthalate esters and the like are known (for example, Patent Document 1). However, in practice, the plasticizer is not compatible with the cellulose acylate film, and there is a problem that the film is cloudy or the optical anisotropy (for example, the retardation value Rth in the thickness direction) of the film cannot be controlled. Not easy

When using a cellulose acylate film for an optical material, it is preferable to enlarge the optical anisotropy of a film depending on a use. It is known to have the effect of enlarging the optical anisotropy of a cellulose acylate film among the compounds called the plasticizer mentioned above. For example, although aromatic phosphate triester is known, the performance is not enough, and such a plasticizer is high temperature and high humidity. Since there is a disadvantage that the moisture permeability under the deterioration is deteriorated, development of a cellulose acylate film having high optical anisotropy and low moisture permeability under high temperature and high humidity and a modifier thereof is urgently desired.

[Patent Document 1] Japanese Patent Application Laid-Open No. 9-95557

The 1st objective of this invention is to provide the cellulose body film with large optical anisotropy.

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

A third object of the present invention is to provide a polarizing plate protective film, a liquid crystal display device, and a support for a silver halide photographic photosensitive material produced using a cellulosic film having a large optical anisotropy and a small moisture permeability.

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

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

[Wherein, R ¹ represents an alkyl group or an aryl group, and R ² and R ³ each independently represent a hydrogen atom, an alkyl group or an aryl group. In addition, the alkyl group and the aryl group may have a substituent. Two or more groups of R ¹ , R ² and R ^{3 may} combine with each other to form a ring.].

 (2) A cellulose-like film comprising at least one compound represented by the formula (1).

 (3) The cellulose-like film according to the above (2), wherein the compound represented by the formula (1) is a compound represented by the following formula (2):

[Wherein, R ⁴ and R ⁵ each represent an aryl group and may each independently have a substituent. R ⁴ and R ⁵ may form a condensed ring.].

 (4) Cellulose body is cellulose acylate, Cellulose body film as described in said (2) or (3) characterized by the above-mentioned.

 (5) A cellulose acylate film comprising cellulose acylate and at least one compound represented by the above formulas (1) and (2) in an amount of 1 to 30% by mass of cellulose acylate.

 (6) The cellulose acylate film as described in said (5) whose acyl substitution degree of cellulose acylate is 2.60-3.00.

 (7) The cellulose acylate film according to the above (5), wherein the acyl substitution degree of the cellulose acylate is 2.80 to 2.95.

 (8) The cellulose acylate film as described in said (5) whose substitution degree substituted by the acetyl group of a cellulose acylate is 2.60-3.00.

 (9) The cellulose acylate film as described in said (5) whose substitution degree is substituted with the C3-C22 acyl group of cellulose acylate 0.00-0.80.

 (10) The cellulose according to the above (5), wherein the cellulose acylate is substituted with an acetyl group and an acyl group having 3 to 22 carbon atoms, and 30% or more of the acyl group having 3 to 22 carbon atoms is present as a substituent for the 6th-position hydroxyl group. Acylate film.

 (11) The cellulose acylate film according to the above (5), wherein the acyl substitution degree at the 6th position of the cellulose acylate is 0.80 to 1.00.

 (12) The cellulose acylate film according to the above (5), wherein the acyl substitution degree at the 6th position of the cellulose acylate is 0.85 to 1.00.

 (13) A modifier for cellulose film, characterized by the above formula (1) and (2).

 (14) A polarizing plate protective film containing at least one layer of the cellulose-based film according to any one of the above (2) to (12).

 (15) A liquid crystal display device comprising at least one layer of the cellulose-based film according to any one of (2) to (12) above.

 (16) A silver halide photographic photosensitive material using the cellulose-based film according to any one of the above (2) to (12) as a support.

 (Optimal Mode of Implementation of the Invention)

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

[Formula 1]

The compound represented by General formula (1) of this invention is demonstrated in detail. In said Formula (1), R <^1> represents an alkyl group or an aryl group, and an aryl group is more preferable. R ² and R ³ each independently represent a hydrogen atom, an alkyl group or an aryl group, and more preferably each independently represents a hydrogen atom or an aryl group. Here, the alkyl group may be straight chain, branched chain and cyclic, preferably having 1 to 25 carbon atoms, more preferably 6 to 25, and most preferably 6 to 20 carbon atoms. The aryl group preferably has 6 to 36 carbon atoms, and more preferably 10 to 36 carbon atoms. In addition, two or more groups may combine with each other and R <^1> , R <^2> and R <^3> may form a ring.

The alkyl group and the aryl group may have a substituent, and examples of the substituent include a halogen atom (for example, chlorine, bromine, fluorine and iodine), an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, and an aryloxy group. Carbonyl group, acyloxy group, sulfonylamino group, hydroxy group, cyano group, amino group and acylamino group are preferred, more preferably alkyl group, aryl group, alkoxy group, aryloxy group and halogen atom, particularly preferably alkyl group and aryl Qi.

As Formula 1, a compound represented by Formula 2 is preferable:

[Formula 2]

.

In Formula 2, R ⁴ and R ⁵ each independently represent an aryl group. The aryl group preferably has 6 to 36 carbon atoms, and more preferably 10 to 36 carbon atoms. In addition, R ⁴ and R ⁵ may form a condensed ring.

The aryl groups may each have a substituent, and examples of the substituent include halogen atoms (for example, chlorine, bromine, fluorine and iodine), alkyl groups, aryl groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, Acyloxy group, sulfonylamino group, hydroxy group, cyano group, amino group and acylamino group are preferable, More preferably, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogen atom are mentioned, Especially preferably, an alkyl group and It is an aryl group.

Moreover, it is preferable that the addition amount of the cellulose body modifier of this invention is 2-30 mass% with respect to a cellulose body, It is more preferable that it is 2-25 mass%, It is most preferable that it is 2-20 mass%.

Next, although the preferable example of the compound represented by General formula (1) and general formula (2) is shown below, this invention is not limited to these specific examples.

The compounds of the present invention can all be prepared by known methods.

That is, the compounds of the formulas (1) and (2) are reacted by dehydration condensation of carboxylic acids and amines using a condensing agent (for example, dicyclohexylcarbodiimide (DCC), etc.) or substitution reaction of carboxylic acid chloride derivatives and amine derivatives. Obtained. For example, about A-8, it can obtain by substitution reaction of 4-phenyl- benzoic acid chloride and aniline.

Moreover, a commercial item can also be used, For example, the commercial item of Tokyo Kasei can be used about A-1.

Next, the cellulose body used for this invention is demonstrated in detail. The cellulose body used in the present invention may be any compound which uses cellulose as a raw material. Preferably cellulose acylate. The cellulose acylate used in the present invention is not particularly limited as long as the effect of the present invention is expressed, and other two or more kinds of cellulose acylate may be mixed and used. The following are mentioned as a preferable cellulose acylate.

That is, a cellulose acylate is a cellulose acylate which the substitution degree with respect to the hydroxyl group of cellulose satisfy | fills all following formula (I)-(III).

 (I) 2.6 ≤ SA + SB ≤ 3.0

 (II) 2.0 ≤ SA ≤ 3.0

 (III) 0 ≤ SB ≤ 0.8

 (In this formula, SA and SB are the substitution degree of the acyl group substituted by the hydroxyl group of cellulose, SA is the substitution degree of an acetyl group, and SB is a substitution degree of the acyl group of C3-C22). .

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

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

Moreover, the cellulose acylate film of the sum total of substitution degree of SA and SB of the 6th position of a cellulose acylate is 0.8 or more, More preferably, it is 0.85 or more, Especially preferably, it is 0.90 or more.

These cellulose acylates make it possible to prepare a solution in which solubility is desirable, and in particular, to prepare a good solution in a non-chlorinated organic solvent.

The acyl group (SB) having 3 to 22 carbon atoms of the cellulose acylate may be an aliphatic group or an aryl group, and is not particularly limited. These are, for example, alkylcarbonyl esters, alkenylcarbonyl esters or aromatic carbonyl esters, aromatic alkylcarbonyl esters, and the like of cellulose, and each may further have a substituted group. Preferred embodiments thereof include propionyl, butanoyl, heptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, iso-butanoyl and t-butanoyl, cyclohexanecarbonyl, oleoyl, benzoyl, naphthylcarbonyl, cinnamoyl group and the like. Among these, propionyl, butanoyl, dodecanoyl, octadecanoyl, t-butanoyl, oleyl, benzoyl, naphthylcarbonyl, cinnamoyl and the like.

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

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

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

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

When used for production of the cellulose acylate of the present invention, the water content is preferably 2% by mass or less, more preferably 1% by mass or less, and particularly preferably cellulose acylate having a water content of 0.7% by mass or less. Generally cellulose acylate contains water and is known to be 2.5-5 mass%. In this invention, in order to make it the moisture content of this cellulose acylate, it is necessary to dry, and the method will not be specifically limited if the target moisture content can be obtained.

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

To the cellulosic film of the present invention, various additives (for example, a plasticizer, a sunscreen agent, a deterioration inhibitor, an optically anisotropic regulator, microparticles, a peeling agent, an infrared absorber, etc.) according to the use can be added to each cell in the production process. They may be solid and may be oily.

That is, the melting point or boiling point is not particularly limited. For example, it is mixing of the ultraviolet absorbing material of 20 degrees C or less and 20 degrees C or more, the mixing of a plasticizer similarly, etc., for example, are described in Unexamined-Japanese-Patent No. 2001-151901. Moreover, as an infrared absorption dye, it is described, for example in Unexamined-Japanese-Patent No. 2001-194522. In addition, the addition time may be added at any time in the dope preparation process, and you may further perform the process of adding and manufacturing an additive to the last manufacturing process of a dope preparation process. In addition, the addition amount of each raw material is not specifically limited as long as a function is expressed. In addition, when a cellulose acylate film is formed in multiple layers, the kind and addition amount of the additive of each layer may differ. For example, it is described in Unexamined-Japanese-Patent No. 2001-151902 etc. These are the techniques known conventionally.

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

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

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

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

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

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

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

In addition, when a 1st solvent is a liquid mixture of 2 or more types of solvent, there may be no 2nd solvent.

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

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

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

The alcohols and hydrocarbons which are these third solvents may be single or a mixture of two or more kinds, and are not particularly limited. As the third solvent, preferred specific compounds include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol and cyclohexanol, cyclohexane, hexane as alcohols, and in particular methanol, ethanol, 1-propanol, 2-propanol, 1-butanol.

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

In addition, when a 1st solvent does not use a 2nd solvent in a liquid mixture, it is preferable to contain 20-90 mass% of a 1st solvent, and 5-30 mass% of a 3rd solvent, and also a 1st solvent It is preferable that it is 30-86 mass%, and 7-25 mass% of 3rd solvents are contained.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Etc. can be mentioned.

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

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

Moreover, when manufacturing the solution of the cellulose acylate of this invention, a chlorine organic solvent is also used as a main solvent in some cases. In the present invention, the chlorine organic solvent is not particularly limited as long as the object can be achieved within the range in which the cellulose acylate is dissolved and can be cast and formed into a film. These chlorine organic solvents are preferably dichloromethane and chloroform. Dichloromethane is particularly preferred. In addition, there is no problem in particular in mixing organic solvents other than a chlorine organic solvent. In that case, dichloromethane should be used at least 50 mass%.

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

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

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

Although it does not specifically limit about the non-chlorine organic solvent used together with the chlorine organic solvent which is a main solvent used for the above-mentioned cellulose acylate, Methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, dioxolane, dioxane, and carbon number 4 It is selected from ketones or acetoacetic acid esters of -7, alcohols or hydrocarbons of 1 to 10 carbon atoms. Further preferred non-chlorine organic solvents used together are methyl acetate, acetone, methyl formate, ethyl formate, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl acetyl acetate, methanol, ethanol, 1-propanol, 2-propanol, 1 -Butanol, 2-butanol and cyclohexanol, cyclohexane and hexane. Although the following is mentioned as a combination with the chlorine type organic solvent which is a preferable main solvent of this invention, It is not limited to these.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Etc. can be mentioned.

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

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

First, cellulose acylate was dissolved in a solvent used for dope to prepare a solution of 0.1% by mass, 0.2% by mass, 0.3% by mass, and 0.4% by mass. In addition, the weighing was performed at 25 degreeC and 10% RH using what dried the cellulose acylate for 2 hours at 120 degreeC, in order to prevent moisture absorption. The dissolution method was carried out according to the method (normal temperature dissolution method, cooling dissolution method, high temperature dissolution method) employed at the time of dope dissolution. Subsequently, these solutions and solvents were filtered with a filter made of 0.2 μm Teflon. And static light scattering of the filtered solution was measured at 10 degreeC from 30 degreeC to 140 degreeC at 25 degreeC using the light-scattering measuring apparatus (Otsuka Electronics Co., Ltd. product DLS-700, brand name). The obtained data were interpreted by the BERRY plot method. In addition, the refractive index required for this analysis uses the value of the solvent calculated | required with the Abbe refractometer, the concentration gradient (dn / dc) of refractive index uses the differential refractometer (DRM-1021, brand name from Otsuka Electronics Co., Ltd.), and measures light scattering It measured using the solvent and solution which were used for.

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

It is preferable that the cellulose acylate solution of this invention is a range with the viscosity and the dynamic storage elastic modulus of this solution. The viscosity and dynamic storage modulus of the solution can be measured by the following method. 1 ml of a sample solution is measured on a rheometer (made by TA Instruments, brand name: CLS 500) using the Steel Cone (made by TA Instrumennts) of diameter 4cm / 2 degrees. The measurement conditions are Oscillation Step / a range of 40 ℃ ~-10 ℃ in Temperature Ramp 2 ℃ / min and by varying the measurement, a static non-Newton viscosity n ^* 40 ℃ (Pa and s) and the storage modulus G 'of -5 ℃ Find (Pa). In addition, the sample solution starts the measurement after keeping the liquid temperature at a predetermined starting temperature until the liquid temperature becomes constant.

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

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

In this invention, when using for a polarizing plate, as a film thickness of a cellulose body film, 10-120 micrometers is preferable, 20-100 micrometers is more preferable, 30-90 micrometers is the most preferable. Moreover, when using as a support body of a photosensitive material, 80-300 micrometers is preferable, 90-250 micrometers is more preferable, 100-200 micrometers is the most preferable.

Here, although the space temperature of a flexible part is not specifically limited in this invention, It is preferable that it is -50-50 degreeC. Moreover, it is preferable that it is -30-40 degreeC, and it is especially preferable that it is -20-30 degreeC. In particular, the cellulose acylate solution softened by the space temperature at low temperature can be instantaneously cooled on the support to increase the gel strength to maintain a film containing the organic solvent. Thereby, it becomes possible to peel off from a support body in a short time, without evaporating an organic solvent from a cellulose acylate, and high speed casting can be achieved. In addition, the means for cooling the space may be ordinary air, nitrogen, argon, helium and the like, and is not particularly limited. In addition, the humidity in that case is preferably 0 to 70% RH, and more preferably 0 to 50% RH. Moreover, in this invention, the support body temperature of the flexible part which casts a cellulose acylate solution is -50-+130 degreeC, Preferably it is -30-+25 degreeC, More preferably, it is -20-+15 degreeC. In order to maintain a flexible part at the temperature of this invention, you may achieve by introducing the gas cooled to the flexible part, or you may arrange | position a cooling apparatus to the flexible part, and cool the space. At this time, it is important to be careful not to get water, and can be carried out by a method such as using a dried gas.

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

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

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

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

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

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

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

An alkali saponification process is performed by apply | coating a saponification liquid. As a coating method, the dip coating method, the curtain coating method, the extrusion coating method, the bar coating method, and the E-type coating method are mentioned. The solvent of the alkali saponification treatment coating liquid is preferably selected from a solvent having good wettability in order to be applied to the transparent support of the saponification liquid and keeping the cotton in a good state without forming irregularities on the surface of the transparent support by the saponification liquid solvent. .

Specifically, an alcohol solvent is preferable and isopropyl alcohol is particularly preferable. Moreover, the aqueous solution of surfactant can also be used as a solvent. Alkali which melt | dissolves in the said solvent as alkali of the alkali saponification coating liquid is preferable, and KOH and NaOH are more preferable. 10 or more are preferable and, as for pH of saponification coating liquid, 12 or more are more preferable. 1 second or more and 5 minutes or less are preferable at room temperature, as for reaction conditions at the time of alkali saponification, 5 seconds or more and 5 minutes or less are more preferable, 20 seconds or more and 3 minutes or less are especially preferable. After the alkali saponification reaction, it is preferable to wash the saponified solution coated surface with water or acid, followed by water washing.

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

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

As a water vapor transmission rate of the cellulose acylate of this invention, it is preferable that it is 200-2000g / (m <2> * day), It is more preferable that it is 400-2000g / (m <2> * day), 400-1800g / (m <2> *) Is most preferred.

In the present invention, the moisture permeability is the mass change before and after leaving the cup containing calcium chloride sealed for 24 hours under the condition of 60 ° C. and 95% RH using each film sample (g / (m 2 · day)). From the moisture permeability of the cellulose triacetate film based on the hygroscopicity of calcium chloride.

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

In-plane retardation (Re) and retardation (henceforth Rth) which are optical performances of the cellulose acylate film of this invention are measured using the ellipsometer (AEP-100, Shimadzu Corporation make).

Specifically, Re is a value obtained by multiplying the film thickness by the difference in in-plane transverse refractive index measured at a wavelength of 632.8 nm, which can be obtained according to the following equation:

Re = (nx-ny) × d

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

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

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

Rth = {(nx + ny) / 2-nz} × d

[Wherein nx is the refractive index in the slow axis direction (the direction in which the refractive index becomes the largest); ny is the refractive index in the direction orthogonal to the slow axis; nz is the refractive index in the thickness direction; and d is the thickness of the film (unit : Nm).]

As retardation (Rth) of the thickness direction of a cellulose ester film, it is preferable that it is 100 nm-300 nm, It is more preferable that it is 120 nm-300 nm, It is most preferable that it is 150 nm-300 nm.

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

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

The cellulose body film of this invention can be advantageously used also as an optical compensation sheet of a TN type, STN type, HAN type, and GH (Guest-Host) reflection type liquid crystal display device. These display modes are well known from the example. TN type reflective liquid crystal display devices are described in Japanese Patent Application Laid-open No. Hei 10-123478, International Publication No. WO98 / 48320, and Japanese Patent No. 3024277. The optical compensatory sheet used for a reflective liquid crystal display device is described in pamphlet of international publication WO00 / 65384.

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

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

The cellulosic film of the present invention can also be applied as a support for a silver halide photographic photosensitive material, and is described in "Basics of Photographic Engineering," Japanese Society of Photography, Korona Co., pp. 276-291 and 291. Various materials, prescriptions, and treatment methods described in the above can be applied. About these techniques, the color negative is described in detail in Unexamined-Japanese-Patent No. 2000-105445, The cellulose body film of this invention is used preferably. In addition, application of the color inversion silver halide photographic photosensitive material as a support is also preferable, and various materials, prescriptions, and treatment methods described in JP-A-11-282119 can be applied.

 (Example)

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

Example 1 Modifiers for Cellulose Films and Cellulose Films

 (1-1) Preparation of Cellulose Acylate Solution

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

Cellulose triacetate A (SA + SB is 2.78, SA is 2.78, SB is 0, cellulose acylate flake having a viscosity-average degree of polymerization of 303 and a water content of 1% by mass or less. Sample 1 in Table 1 using (15 parts by mass), methyl acetate (87.0 parts by mass), acetone (8.0 parts by mass), ethanol (5.0 parts by mass), and TPP / BDP (8.O parts by mass). Was produced. Next, Sample 2 having the same composition as Sample 1 was prepared except that TPP / BDP of Sample 1 was 12.0 parts by mass. And instead of TPP / BDP of sample 1, the samples 3-15 which added the modifier of Table 1 by the addition amount of Table 1 were produced.

 (1-2) Cellulose Triacetate Film Solution

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

 (1-3) Preparation of Cellulose Triacetate Film

The filtered cellulose triacetate solution at 50 ° C. was cast on a mirror stainless steel support through a casting dye. The temperature of the support was 5 ° C, the casting speed was 3 m / min, and the coating width thereof was 30 cm. It left to stand at room temperature for 1 minute, and after that, the drying air of 55 degreeC was blown for drying. 5 minutes later, it removed from the mirror stainless steel support body, and after that, it dried for 27 minutes at 133 degreeC, and obtained the 60-micrometer-thick cellulose triacetate film.

 (1-4) Water vapor permeability measurement of cellulose acetate film

The moisture permeability of the obtained cellulose triacetate film was measured using the respective film samples as a lid, and the weight change before and after leaving the cup filled with calcium chloride for 24 hours at 60 ° C. and 95% RH (g / (m 2 · day) The moisture permeability of the cellulose triacetate film based on the hygroscopicity of calcium chloride was calculated from)).

 (1-5) Rth measurement of cellulose acetate film

It was calculated | required according to the following formula as a value which multiplied the film film thickness by the in-plane longitudinal transverse refractive index difference measured at wavelength 632.8 nm using the ellipsomter (AEP-100, the Shimadzu Corporation make).

Rth = {(nx + ny) / 2-nz} × d

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

ny: Refractive index of direction orthogonal to ground axis

nz: refractive index in the thickness direction

d ： film thickness (unit: nm)

sample Contents Modifier Added amount (mass%) Rth (nm) Moisture permeability (g / ㎡ ・ day) Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 Comparative Comparison Comparison Comparison Comparison -TPP / BDPTPP / BDPC-1C-2C-3 -812121212 76767712010090 290022002200210022002200 Sample 7 Sample 8 Sample 9 Sample 10 Sample 11 Sample 12 Sample 13 Sample 14 Sample 15 Inventive Invention Invention Invention Invention Invention Invention Invention Invention Invention Invention A-1A-1A-8A-8A-10A-13A-21A-31A-34 81281288121212 140175210190180180174230202 175017001750170017001700173017401750

Comparative Compound

From Table 1, a cellulose acetate film having a lower water vapor transmission rate and a larger optical anisotropy (larger Rth) than TPP / BDP or C-1, C-2 and C-3 having a similar skeleton widely used by adding the compound of the present invention. It can be seen that can be produced. In particular, by adding the modifier of the present invention, the optical anisotropy can be greatly increased with respect to TPP / BDP.

<Example 2>

A cellulose acylate film was produced in the same manner as in Example 1 using the following composition. Also in this case, the favorable result was obtained like Example 1.

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

Methylene chloride (300 parts by mass)

Methanol (45 parts by mass)

Examples 1 to 15 (11.7 parts by mass) described

Example 3 Polarizing Plate Protective Film

About Samples 1-15 of Example 1, samples 201-205 were produced and evaluated by the method of Example 1 of Unexamined-Japanese-Patent No. 11-316378. The optical characteristic of the elliptical polarizing plate obtained by the cellulose-based film of the present invention was excellent. In addition, durability over time was also no problem compared to Comparative Sample 2.

Example 4 Liquid Crystal Display

The sample 1-15 of Example 1 contains the liquid crystal display device of Example 1 of Unexamined-Japanese-Patent No. 10-48420, and the discotic liquid crystal molecule of Example 1 of Unexamined-Japanese-Patent No. 9-26572. Optically anisotropic layer, alignment film coated with polyvinyl alcohol, VA type liquid crystal display device shown in FIGS. 2-9 of JP 2000-154261, OCB type liquid crystal display shown in FIGS. 10-15 of JP 2000-154261 When the device was evaluated, good performance was obtained in any case.

Example 5 Silver Halide Photosensitive Material

About samples 1-15 of Example 1, except having set the film thickness to 120 nm, it carried out similarly to Example 1, and produced samples 401-405. On one side of the obtained film, the 1st layer and 2nd layer of Example 1 of Unexamined-Japanese-Patent No. 4-73736 were formed, and the white layer which made a cationic polymer an electroconductive layer was produced. And the sample 105 of Example 1 of Unexamined-Japanese-Patent No. 11-38568 was apply | coated to the opposite surface of the film base in which the obtained white layer was formed, and the silver halide photosensitive material was produced. The obtained silver halide photographic photosensitive material was obtained with an excellent image and there was no problem also in the handleability.

The cellulose body film to which the compound represented by the said Formula (1) and Formula (2) was added has the outstanding effect that moisture permeability is small and optical anisotropy is very large. Therefore, this cellulose film can be used also for a polarizing plate protective film, a liquid crystal display device, and a silver halide photographic photosensitive material.

Claims (8)

A cellulose body composition comprising at least one of a cellulose body and a compound represented by the following formula (1): [Formula 1] [Wherein, R ¹ represents an alkyl group or an aryl group, and R ² and R ³ each independently represent a hydrogen atom, an alkyl group or an aryl group. In addition, the alkyl group and the aryl group may have a substituent. Two or more groups of R ¹ , R ² and R ^{3 may} combine with each other to form a ring.]. A cellulosic film comprising at least one compound represented by the formula (1) according to claim 1. The cellulose-based film of claim 2, wherein the compound represented by the formula (1) is a compound represented by the following formula (2): [Formula 2] [Wherein, R ⁴ and R ⁵ each represent an aryl group and may each independently have a substituent. R ⁴ and R ⁵ may form a condensed ring.]. The cellulose body film according to claim 2 or 3, wherein the cellulose body is cellulose acylate. The modifier for cellulosic films represented by Formula 1 of Claim 1. It contains 1 or more layers of the cellulose body film of Claim 2, The polarizing plate protective film characterized by the above-mentioned. A liquid crystal display device comprising at least one layer of the cellulose-based film according to claim 2. The cellulose body film of Claim 2 is used as a support body, The silver halide photographic photosensitive material characterized by the above-mentioned.