JP2002322314A - Cellulose acylate film and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a cellulose acylate film having a good surface condition. SOLUTION: An ester-alcohol having a molecular structure in which 3-10 groups in total consisting of 1-5 alcoholic hydroxy groups and 1-5 acyloxy groups are bonded to a 3-20C backbone is added in an amount of 0.5-25 mass% of a cellulose acylate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cellulose acylate film which can be preferably used for a silver halide photographic material or a liquid crystal image display.

[0002]

2. Description of the Related Art Cellulose acylate films are used for silver halide photographic materials and liquid crystal image display devices. The cellulose acylate film can be produced from a solution in which cellulose acylate is dissolved in an organic solvent. As the organic solvent, a hydrocarbon containing chlorine such as methylene chloride is used. Methylene chloride (boiling point: 40 ° C.) has been conventionally used as a good solvent for cellulose acylate, and is preferably used because it has a low boiling point in the film-forming and drying steps of the production process, and is easily dried. Conversely, methylene chloride has a low boiling point and is easy to volatilize. Improvement is desired in this respect. Therefore, using methylene chloride, a study was made to reduce the amount of solvent used by preparing a cellulose acylate solution having a higher concentration.
The peeling from the metal support at the time of casting was insufficient, and its improvement has been desired. For this purpose, a search for a solvent for cellulose acylate other than methylene chloride has been made. Organic solvents exhibiting solubility in cellulose acylate, especially cellulose triester, include acetone (boiling point 56 ° C.), methyl acetate (boiling point 56 ° C.), tetrahydrofuran (boiling point 65 ° C.), 1,3-dioxolane (boiling point 75 ° C.) , 1,4-dioxane (boiling point: 101 ° C.) and the like are known. However, these organic solvents have not obtained sufficient solubility for practical use by conventional dissolution methods.

[0003] As a solution to this, J. J. M. G. FIG. Cowie
Et al., In the literature (Makromol.chem. 143, 105 (1971)), cellulose triacetate (acetylation degree: 60.1% to 61.3%) was cooled from -80 ° C to -70 ° C in acetone. Then, by heating, 0.5 to 5% by mass
Are reported to be obtained. Such a method of dissolving cellulose acylate at a low temperature is called a cooling dissolution method. Also, Kenji Ude et al., Journal of the Textile Machinery Society, 34
Vol., Pp. 57-61 (1981), "Spinning technology from cellulose triacetate in acetone" describes a spinning technique using a cooling dissolution method. Further, Japanese Unexamined Patent Publication No.
JP-A-95538, JP-A-9-95544 and JP-A-9-95557 disclose that cellulose acylate is dissolved by a cooling dissolution method using a non-chlorine-based organic solvent on the basis of the above technology. ing. The non-chlorine organic solvent used at that time is an organic solvent selected from ethers, ketones and esters, and a film is produced by dissolving cellulose acylate by a cooling dissolution method. It is described that acetone, 2-methoxyethyl acetate, cyclohexanone, ethyl formate, methyl acetate and the like are preferable as these specific organic solvents. Further, JP-A-11-6075
No. 2 proposes to improve by adding a fluoroalcohol to a cellulose acylate solution. However, there is a problem in that the addition of fluoroalcohol has a defect that the surface of cellulose acylate is poor due to its strong oil / water repellency.

On the other hand, cellulose acylate films are:
Generally, it is produced by a solvent casting method or a melt casting method. In the solvent casting method, a solution (dope) in which cellulose acylate is dissolved in a solvent is cast on a metal support, and the solvent is evaporated to form a film (another dissolving method, a melt casting method). In this method, a film obtained by melting cellulose acylate by heating is cast on a metal support and cooled to form a film). The solvent cast method can produce a good film having higher flatness than the melt cast method. For this reason, the solvent cast method is more commonly used in practical use. In the recent solvent casting method, it is possible to improve the productivity of the film forming process by shortening the time required from casting the dope on the metal support to peeling off the formed film on the metal support. It is an issue. In particular, when a cellulose acylate film is produced by a solvent casting method, when a cellulose acylate solution using a non-chlorine-based organic solvent is used, it is difficult to peel the cellulose acylate film from the metal support in a short time. The problem is that the productivity is poor.

[0005] In this method, cellulose acylate is cast on a band or a drum as a metal support, dried or cooled to form a strong gel film, and peeled from the metal support in a state containing an organic solvent. This is because the strength of the cellulose acylate film peeled off from the metal support when subsequently dried is insufficient. Methylene chloride, a chlorine-based organic solvent that has been conventionally used, can evaporate the solvent in a short time due to its low boiling point,
Since the film strength of the cellulose acylate film containing a solvent can be increased by significantly increasing the solid content concentration in the cellulose acylate film, there is no particular problem. However, when a non-chlorine solvent is used, it is not expected to volatilize the solvent in a short time because the solvent has a high boiling point and a high affinity for cellulose acylate. For this reason, after the cellulose acylate film containing the solvent is peeled off from the metal support, the flatness of the cellulose acylate film cannot be maintained during the handling at the time of drying, and the cellulose acylate film is held at the tenter holding portion or the central portion. There arises a problem that the flatness deteriorates remarkably due to elongation of the rate film. In particular, a step of casting a cellulose acylate solution on a cooled band-shaped or drum-shaped metal support, exfoliating the cellulose acylate film containing a large amount of the solvent from the metal support without drying, and then drying. This problem is serious when a casting / drying form having the following is taken.

[0006]

When a cellulose acylate solution is prepared using a non-chlorine organic solvent according to a room temperature dissolution method, a cooling dissolution method or a high-temperature high-pressure dissolution method, a metal is cast for drying after the solution is cast. There is a problem that it is difficult to peel off from the support. It is desired to solve this problem and produce an excellent planar cellulose acylate film.

An object of the present invention is to provide a cellulose acylate film whose surface condition can be easily improved.
Another object of the present invention is to prepare a cellulose acylate solution using an organic solvent (preferably a non-chlorine-based organic solvent) according to a room temperature dissolution method, a cooling dissolution method or a high-temperature high-pressure dissolution method to obtain a cellulose acylate having excellent surface properties. It is also about producing films. It is a further object of the present invention to provide a cellulose acylate solution that can easily peel the film from the support for drying after casting, and can obtain excellent productivity.

[0008]

Means for Solving the Problems The present invention provides the following (1) to
(30) A cellulose acylate film, a method for producing the same, and a cellulose acylate solution. (1) Cellulose acylate and ester alcohol in an amount of 0.5 to 25% by mass of the cellulose acylate, wherein the ester alcohol is linked to a linking group having 3 to 20 carbon atoms by 1 to 5 alcohols Hydroxyl group and 1
A cellulose acylate film having a molecular structure in which 3 to 10 acyloxy groups are bonded in total.

(2) The cellulose acylate film as described in (1), wherein the acyl substitution degree of the cellulose acylate is 2.60 to 3.00. (3) The acyl substitution degree of cellulose acylate is 2.80.
The cellulose acylate film according to (2), wherein (4) The cellulose acylate film according to (1), wherein the degree of substitution of the cellulose acylate with an acetyl group is from 2.00 to 3.00.

(5) The degree of substitution of cellulose acylate with an acyl group having 3 to 22 carbon atoms is 0.
The cellulose acylate film according to (1), which has a value of from 00 to 0.80. (6) The cellulose acylate is substituted with an acetyl group and an acyl group having 3 to 22 carbon atoms, and at least 30% of the acyl groups having 3 to 22 carbon atoms are substituted as a substituent of the 6-position hydroxyl group. The cellulose acylate film according to (1), which is present.

(7) The cellulose acylate film according to (1), wherein the degree of acyl substitution at the 6-position of the cellulose acylate is from 0.80 to 1.00. (8) The cellulose acylate film according to (1), wherein the degree of acyl substitution at the 6-position of the cellulose acylate is 0.85 to 1.00. (9) The cellulose acylate film according to (1), wherein the cellulose acylate has a viscosity average degree of polymerization of 250 to 550.

(10) The linking group is a glycerin residue, erythritol residue, arabitol residue, mannitol residue, trimethylolpropane residue, pentaerythritol residue, ditrimethylol residue, dipentaerythritol residue, sorbitol residue Group, sorbitan residue, butane-
1,2,3-triol residue and pentane-2,3
The cellulose acylate film according to (1), which is selected from the group consisting of 4-triol residues.

(11) The cellulose acylate film according to (1), which is for a protective layer of an optical material and has a thickness of 10 to 200 μm. (12) The cellulose acylate film according to (1), which is for a support of a silver halide photographic material and has a thickness of 30 to 250 μm.

(13) A method for producing a cellulose acylate film by applying a cellulose acylate solution obtained by dissolving cellulose acylate in an organic solvent, wherein the cellulose acylate solution contains 0.1% cellulose acylate and 0.1% cellulose acylate.
An ester alcohol in an amount of from 1 to 5% by weight, wherein the ester alcohol has 1 to 5 alcoholic hydroxyl groups and 1 to 5
A method for producing a cellulose acylate film, having a molecular structure in which 3 to 10 acyloxy groups are bonded in total.

(14) The production method according to (13), wherein the organic solvent comprises a substantially non-chlorine organic solvent. (15) The organic solvent is selected from the group consisting of ethers having 2 to 12 carbon atoms, ketones having 3 to 12 carbon atoms, and esters having 2 to 12 carbon atoms (1
The production method according to 4).

(16) The ether is diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-
(15) The production method according to (15), which is selected from the group consisting of dioxane, 1,3-dioxane, 1,3-dioxolan, tetrahydrofuran, anisole, and phenetole. (17) The ketone is selected from the group consisting of acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and methylcyclohexanone (15)
The production method described in 1.

(18) The ester is ethyl formate,
(15) The production method according to (15), which is selected from the group consisting of propyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, and pentyl acetate. (19) The organic solvent is a mixture of three or more different solvents, and the first solvent is selected from the group consisting of methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, dioxolan and dioxane; The second solvent is selected from the group consisting of ketones having 4 to 7 carbon atoms and acetoacetate, and the third solvent is
(14) The production method according to (14), which is selected from the group consisting of alcohols and hydrocarbons having 1 to 10 carbon atoms.

(20) The organic solvent contains 20 to 90% by mass of the first solvent, 5 to 60% by mass of the second solvent, and 5 to 30% by mass of the third solvent.
The production method according to 9). (21) The organic solvent is a mixture of three or more different solvents, wherein the first solvent and the second solvent are methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone,
Selected from the group consisting of dioxolane and dioxane,
And the third solvent is selected from the group consisting of alcohols and hydrocarbons having 1 to 10 carbon atoms (14)
The production method described in 1.

(22) The organic solvent contains the first solvent in an amount of 20 to 90% by mass, the second solvent in an amount of 5 to 60% by mass, and the third solvent in an amount of 5 to 30% by mass ( 21. The production method according to 21). (23) The organic solvent is methylene chloride (1
The production method according to 3). (24) Cellulose obtained by dissolving cellulose acylate in an organic solvent by swelling a mixture of cellulose acylate and an organic solvent at 10 to 40 ° C and heating the swollen mixture to 0 to 57 ° C. (13) The production method according to (13), wherein an acetate solution is used.

(25) a step of swelling a mixture of cellulose acylate and an organic solvent at -10 to 55 ° C, a step of cooling the swollen mixture to -100 to -10 ° C, and a step of cooling the cooled mixture to 0 to 57 ° C. (13) The production method according to (13), wherein a cellulose acetate solution obtained by dissolving cellulose acylate in an organic solvent is used in the step of heating to a temperature of ° C. (26) a step of swelling a mixture of cellulose acylate and an organic solvent at −10 to 55 ° C., a step of heating the swollen mixture to 60 to 240 ° C. at 0.2 to 30 MPa, and a step of swelling the heated mixture to 0 to 240 ° C. (13) The production method according to (13), wherein a cellulose acetate solution obtained by dissolving cellulose acylate in an organic solvent is used in the step of cooling to 57 ° C.

(27) As cellulose acylate, 9
Using cellulose acylate particles in which 0% by mass or more have a particle size of 0.1 to 5 mm, a process of filtering the cellulose acylate solution before coating is performed (13).
The production method described in 1. (28) The cellulose acylate solution contains 0.1 to 20% by mass of a plasticizer with respect to cellulose acylate, 0.001 to 5% by mass of an ultraviolet absorber with respect to cellulose acylate, and fine particles of cellulose acylate. 0.001 to 5% by mass with respect to cellulose acylate or 0.001 to 2% by mass with respect to cellulose acylate
(13) The production method according to (13). (29) The production method according to (13), wherein two or more cellulose acylate solutions are co-cast in the casting step.

(30) A cellulose acylate solution in which cellulose acylate is dissolved in an organic solvent, comprising cellulose acylate and an ester alcohol in an amount of 0.01 to 5% by mass, wherein the ester alcohol is in an amount of 3 to 5% by mass. A cellulose acylate having a molecular structure in which 1 to 5 alcoholic hydroxyl groups and 1 to 5 acyloxy groups are bonded to a linking group having 20 carbon atoms in a total of 3 to 10 groups. solution.

[0023]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Cellulose acylate is a cellulose derivative (cellulose ester) in which a hydrogen atom of a hydroxyl group of cellulose is substituted with an acyl group. The acyl group is generally an acetyl group (SA), but may be an acyl group (SB) having 3 or more (preferably 3 to 22) carbon atoms. The sum of the degrees of substitution of SA + SB is
Generally, it is 2.60 to 3.00, and the substitution degree of SB is 0.
00 to 0.80. Β- constituting cellulose
The 1,4-linked glucose unit has a free hydroxyl group at the 2-, 3- and 6-positions. Cellulose acylate is a polymer in which some or all of these hydroxyl groups are esterified with an acyl group. The degree of acyl substitution was determined for each of the 2-, 3- and 6-positions.
The ratio of cellulose esterification (100% esterification means substitution degree 1). The sum of the degrees of substitution of SA and SB in the hydroxyl group is preferably from 2.70 to 2.96, and more preferably from 2.80 to 2.95. Further, the substitution degree of SB is preferably from 0.00 to 0.80, and more preferably from 0.00 to 0.60.

In the cellulose acylate, it is particularly preferable that the degree of substitution of the cellulose with a hydroxyl group satisfies all of the following formulas (I) to (III). (I) 2.6 ≦ SA + SB ≦ 3.0 (II) 2.0 ≦ SA ≦ 3.0 (III) 0 ≦ SB ≦ 0.8 [wherein SA and SB are substituted by hydroxyl groups of cellulose. Is a substituent of an acyl group, SA is the degree of substitution of an acetyl group, and SB is the degree of substitution of an acyl group having 3 to 22 carbon atoms.]

The degree of substitution (SB) of an acyl group having 3 to 22 carbon atoms is preferably such that at least 28% is a substituent of a 6-position hydroxyl group and at least 30% is a substituent of a 6-position hydroxyl group. More preferably, 31% or more is more preferably a substituent of the 6-position hydroxyl group, and still more preferably 3% or more.
Most preferably, 2% or more is a substituent of the 6-position hydroxyl group. The sum of the degrees of substitution between the SA and SB at the 6-position of the cellulose acylate is preferably 0.80 or more.
It is more preferably at least 85, most preferably at least 0.90.

Acyl group having 3 to 22 carbon atoms (SB)
Is defined as -CO-R, wherein R is an aliphatic group, an aromatic group, or a heterocyclic group. R is preferably an aliphatic group or an aromatic group. The aliphatic group is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group or a substituted alkynyl group. The aromatic group is an aryl group or a substituted aryl group. 3 carbon atoms
Examples of the acyl group of -22 include propionyl, butyryl,
Valeryl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, isobutyryl, t-butyryl, cyclohexanoyl, oleoyl, benzoyl, naphthoyl and cinnamoyl. Propionyl, butyryl, dodecanoyl, octadecanoyl, t-butyryl, oleoyl, benzoyl, naphthoyl and cinnamoyl are preferred.

The basic principle of the method for synthesizing cellulose acylate is described in Migita et al., Wood Chemistry, pp. 180-190 (Kyoritsu Shuppan, 1968). A typical synthesis method is a liquid phase acetylation method using a carboxylic anhydride-acetic acid-sulfuric acid catalyst. Specifically, after a cellulose raw material such as cotton linter or wood pulp is pretreated with an appropriate amount of acetic acid, it is put into a carboxylation mixed solution that has been cooled in advance to be esterified, and complete cellulose acylate (second, third and sixth positions) is obtained. The total degree of acyl substitution at the position is approximately 3.00). The carboxylation mixture generally contains acetic acid as a solvent, carboxylic anhydride as an esterifying agent, and sulfuric acid as a catalyst. The carboxylic anhydride is usually used in a stoichiometric excess of the total amount of the cellulose reacting therewith and the water present in the system. After the completion of the acylation reaction, a neutralizing agent (for example, calcium, magnesium, iron, aluminum or zinc) is used for hydrolysis of excess carboxylic anhydride remaining in the system and neutralization of a part of the esterification catalyst. (Carbonate, acetate or oxide). Next, the obtained complete cellulose acylate is saponified and aged by keeping at 50 to 90 ° C. in the presence of a small amount of an acetylation reaction catalyst (generally, residual sulfuric acid),
The cellulose acylate having the desired degree of acyl substitution and degree of polymerization is changed. When the desired cellulose acylate is obtained, the catalyst remaining in the system may be completely neutralized using the neutralizing agent as described above, or may be neutralized with water or dilute sulfuric acid. Put the cellulose acylate solution (or into the cellulose acylate solution,
Water or diluted sulfuric acid is added) to separate the cellulose acylate, and the cellulose acylate is obtained by washing and stabilizing.

It is preferable that the polymer component of the cellulose acylate film is substantially composed of cellulose acylate having the above-mentioned definition. "Substantially" means 90% by weight or more (preferably 95% by weight or more, more preferably 98% by weight or more, and most preferably 99% by weight or more) of the polymer component. It is preferable to use cellulose acylate particles as a raw material for producing a film. 90% by mass of the particles used
The above preferably has a particle diameter of 0.5 to 5 mm. Further, 50% by mass or more of the particles used is 1 to 4%.
It preferably has a particle size of mm. It is preferable that the cellulose acylate particles have a shape as close to spherical as possible.

The polymerization degree of the cellulose acylate is preferably from 200 to 700 in terms of viscosity average degree of polymerization.
0 to 550, more preferably 250 to 400
Is more preferable, and most preferably 250 to 350. The average degree of polymerization was determined by the limiting viscosity method of Uda et al.
105-120, 1962). The viscosity average polymerization degree is also described in JP-A-9-95538. The viscosity average degree of polymerization is determined by the following equation from the intrinsic viscosity [η] of cellulose acetate measured by an Ostwald viscometer. (1) DP = [η] / Km where [η] is the intrinsic viscosity of cellulose acetate, and Km is a constant 6 × 10 −4. When the viscosity average degree of polymerization (DP) is 290 or more, the viscosity average degree of polymerization and the concentrated solution viscosity (η) according to the falling ball viscosity method are represented by the following formula (2).
Is preferably satisfied. (2) 2.814 × ln (DP) −11.753 ≦ ln
(Η) ≦ 6.29 × ln (DP) −31.469 In the formula, DP is a value of a viscosity average degree of polymerization of 290 or more,
η is the transit time (seconds) between the marked lines in the falling ball viscosity method. The above formula (2) is obtained by plotting the viscosity-average degree of polymerization and the viscosity of the concentrated solution and calculating from the results.

When the low molecular components are removed, the average molecular weight (degree of polymerization) increases, but the viscosity is lower than that of ordinary cellulose acylate, which is useful. Cellulose acylate having a small amount of low molecular components can be obtained by removing low molecular components from cellulose acylate synthesized by an ordinary method. The removal of low molecular components can be performed by washing the cellulose acylate with a suitable organic solvent. Examples of the organic solvent include ketones (eg, acetone), acetates (eg, methyl acetate), and cellosolves (eg, methyl cellosolve). In the present invention, it is preferable to use ketones, especially acetone. To increase the efficiency of removing low molecular components,
It is preferable to control the particle size by crushing or sieving the cellulose acylate particles before washing. In the case of producing cellulose silicate having a small amount of low molecular components, the amount of the sulfuric acid catalyst in the acetylation reaction is preferably adjusted to 5 to 25 parts by mass based on 100 parts by mass of cellulose. When the amount of the sulfuric acid catalyst is in the above range, cellulose acylate which is preferable in terms of molecular weight distribution (uniform molecular weight distribution) can be synthesized.

When the cellulose acylate is used for producing a film, the water content of the cellulose acylate is preferably 2% by mass or less, more preferably 1% by mass or less, and more preferably 0.7% by mass. It is most preferred that: Common (eg, commercially available) cellulose acylates have a moisture content of 2.5 to 5% by weight. Therefore, when a general cellulose acylate is used, it is preferable to reduce the water content to 2% by mass or less by drying. Drying can be performed by various known means. The cellulose acylate content in the cellulose acylate solution is 5
To 50% by mass, preferably 5 to 40% by mass, more preferably 7.5 to 30% by mass, most preferably 10 to 30% by mass.

In the present invention, an ester alcohol is further used. The ester alcohol used in the present invention has a molecular structure in which 1 to 5 alcoholic hydroxyl groups and 1 to 5 acyloxy groups are bonded in total to 3 to 10 linking groups having 3 to 20 carbon atoms. Is a compound having The ester alcohol is preferably a compound represented by the following formula (IV). (IV) (HO) m-A-(-O-CO-R) n wherein A is polyvalent (m + n valence) and has 3 to 20 carbon atoms.
R is an aliphatic group or an aromatic group; m is an integer from 1 to 5; n is an integer from 1 to 5; and m + n is an integer from 3 to 10 It is.

A is preferably a linking group having 3 to 18 carbon atoms. The linking group preferably has a molecular structure in which a hydrocarbon group (aliphatic group or aromatic group) or a hydrocarbon group is linked by an ether bond. The linking group is
It is preferably a polyhydric alcohol residue. Examples of the linking group include glycerin residue, erythritol residue, arabitol residue, mannitol residue, trimethylolpropane residue, pentaerythritol residue, ditrimethylol residue, dipentaerythritol residue, sorbitol residue,
Includes sorbitan residues, butane-1,2,3-triol residues and pentane-2,3,4-triol residues. Glycerin residues, trimethylolpropane residues and pentaerythritol residues are preferred.

R is an aliphatic group or an aromatic group. The aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group or a substituted alkynyl group. The alkyl group, alkenyl group and alkynyl group may have a cyclic structure or a branched structure. The alkyl, alkenyl and alkynyl moieties of the substituted alkyl, alkenyl and alkynyl groups are the same as the alkyl, alkenyl and alkynyl groups, respectively. Examples of the substituent of the substituted alkyl group, the substituted alkenyl group and the substituted alkynyl group include a halogen atom, hydroxyl, formyl, carboxyl, amino, carbamoyl, sulfamoyl, an aromatic group and a heterocyclic group. An aromatic group means an aryl group or a substituted aryl group. Preferably, the aryl group is phenyl or naphthyl. The aryl part of the substituted aryl group is the same as the aryl group. Examples of the substituent of the substituted aryl group include a halogen atom, hydroxyl, formyl, carboxyl, amino, carbamoyl, sulfamoyl, an aliphatic group, an aromatic group and a heterocyclic group. The heterocyclic group means an unsubstituted heterocyclic group or a substituted heterocyclic group. The heterocyclic ring of the heterocyclic group is a 5-membered ring, 6
It is preferably a membered ring or a fused ring thereof. Examples of the substituent of the substituted heterocyclic group are the same as the examples of the substituent of the substituted aryl group.

M is an integer of 1 to 5, preferably 1 or 2. n is an integer of 1 to 5, and preferably 2 to 5. m + n is an integer of 3 to 10, and preferably 3 to 8. Examples of the ester alcohol are shown below.

(1) glycerin monolaurate (2) glycerin monostearate (3) glycerin monooleate (4) glycerin dicalylate (5) glycerin monoacetyl monostearate (6) glycerin monoacetyl monooleate (7) tri Methylol propane monolaurate (8) Trimethylolpropane monopropionyl monolaurate (9) Trimethylolpropane monopalmitate (10) Trimethylolpropane monoacetyl monopalmitate (11) Trimethylolpropane monostearate (12) Trimethylol Propane monoacetyl monooleate (13) pentaerythritol distearate (14) pentaerythritol dioleate (15) pentaerythritol diacetyl monostearate (1) ) Pentaerythritol diacetyl mono-17
Hydroxystearate (17) Ditrimethylolpropane diacetyl monostearate (18) Ditrimethylolpropane diacetyl monostearate (19) Dipentaerythritol tetraacetyl monostearate (20) Dipentaerythritol tetraacetyl monostearate (21) Sorbitan acetyl monostearate rate

The ester alcohol represented by the formula (IV) is prepared by a usual ester synthesis method. That is,
The polyhydric alcohol and the carboxylic acid compound can be obtained by a dehydration reaction in the presence of an appropriate catalyst (for example, sulfuric acid or the like). , Tetrabutoxytitanium, etc.). The obtained ester alcohol is preferably purified by extracting with an appropriate organic solvent (eg, ethyl acetate, toluene, etc.), washing with water, and evaporating the solvent. The ester alcohol represented by the formula (IV) is characterized in that when added to a cellulose acylate solution, the solution is made to have a high viscosity or gel at a low temperature. Here, in the present invention, gelation is
By adding the ester alcohol represented by the formula (IV), the solution composed of the organic solvent of cellulose acylate is used for the interaction between the ester alcohols or the cellulose acylate, and the interaction with the organic solvent. Means that the solution does not flow or solidifies. That is, the ester alcohol represented by the formula (IV) is converted into hydrogen bond, electrostatic interaction, coordination bond, van der Waals force, π-
Self-association is performed using a secondary interaction that is not a covalent bond such as a π-electron interaction as a driving force to form a gel structure.

The content of the ester alcohol is 0.01 to 5% by mass in the cellulose acylate solution.
The content is preferably from 02 to 4% by mass, more preferably from 0.02 to 3% by mass. The method of adding the ester alcohol is not particularly limited, and may be mixed with cellulose acylate or another additive or an organic solvent described below in advance to form a solution, or the ester alcohol may be added in any step before the casting step. It may be added. Further, the ester alcohol represented by the formula (IV) is in a solid or liquid form, but may be added as it is, may be added as a solution by heating the solid, or may be a solution dissolved in an organic solvent. You may add in a state.

Various additives (for example, release agents, plasticizers, UV inhibitors, deterioration inhibitors, fine particles, optical property modifiers, etc.) depending on the use in each preparation step are added to the cellulose acylate solution. Can be. The doping may be added in any step of the dope preparation step, but may be performed by adding an additive to the dope preparation step in the last preparation step of the dope preparation step. First, the release agent will be described. In the present invention, in order to obtain a good planar cellulose acylate film, it is preferable to use an acid having an acid dissociation index (pKa, 25 ° C.) of 4.4 or less, a salt thereof, or an acid derivative thereof as a release agent. . The acid dissociation index pKa is preferably 1.9 to 4.4, more preferably 2.0 to 4.0,
It is particularly preferred that it is 2.0 to 3.9. Further, when these release agents are used, when the cellulose acylate solution is cast on a metal support and peeled off, it can be easily peeled off, which is preferable in view of production suitability. Examples of these acids include carboxylic acids, sulfates, sulfonic acids, phosphoric acids, and the like. Preferred materials include substituted or unsubstituted monoalkyl phosphates and salts thereof, dialkyl phosphates and salts thereof, monoalkylallyl phosphates and salts thereof, dialkylallyl phosphates and salts thereof, phosphoric acid Monoalkenyl esters and salts thereof, dialkenyl phosphates and salts thereof, alkyl sulfates and salts thereof, alkenyl sulfates and salts thereof, alkylsulfonic acids or salts thereof, alkenylsulfonic acids or salts thereof, alkylallylsulfonic acids and salts thereof Salts.

A preferred release agent is a carboxylic acid having a carboxylic acid or a salt thereof. In the case of a polycarboxylic acid, a derivative thereof may be used. Hydrocarbon polycarboxylic acid esters, hydrocarbon polycarboxylic acid amides, aromatic polycarboxylic acid esters, aromatic polycarboxylic acid amides, and heterocyclic polycarboxylic acid amides are also preferable. These are disclosed in JP-A-10-31670.
No. 1 publication. For the pKa of acids, see “Revised 3rd Edition Chemical Handbook, Basics II” (edited by The Chemical Society of Japan,
Maruzen Co., Ltd.). Hereinafter, the acid dissociation index pKa is shown in parentheses together with specific examples of the acid.

As the inorganic acid, for example, HClO ₂
(2.31), HOCN (3.48), molybdic acid (H ₂ MoO ₄ , 3.62), HNO ₂ (3.15),
Phosphoric acid (H ₃ PO, 2.15), tripolyphosphoric acid (H ₅ PO
P ₃ O ₁₀ , 2.0), vanadic acid (H ₃ VO ₄ , 3.7)
8) and the like.

Examples of the organic acid include formic acid (3.55) and oxaloacetic acid (2.2) as aliphatic monocarboxylic acids.
7), cyanoacetic acid (2.47), phenylacetic acid (4.1)
0), phenoxyacetic acid (2.99), fluoroacetic acid (2.59), chloroacetic acid (2.68), bromoacetic acid (2.72), iodoacetic acid (2.98), mercaptoacetic acid (3.43) , Acetic acid having a substituent such as vinyl acetic acid (4.12), and chloropropionic acid (2.71-3.9).
Halopropionic acid such as 2), 4-aminobutyric acid (4.0
3) and acrylic acid (4.26). Further, glycolic acid (3.63), lactic acid (3.66), and the like as oxycarboxylic acids are also included. Further, anilinesulfonic acid (3.74-3.3) which is an aromatic monocarboxylic acid such as glyoxylic acid (3.18), pyruvic acid (2.26), and levulinic acid (4.44) as aldehyde acid or ketone acid. 23), benzoic acid (4.
20), aminobenzoic acid (2.02-3.12), chlorobenzoic acid (2.92-3.99), cyanobenzoic acid (3.60-3.55), nitrobenzoic acid (2.17-
3.45), hydroxybenzoic acid (4.08-4.5).
8), anisic acid (4.09-4.48), fluorobenzoic acid (3.27-4.14), chlorobenzoic acid, bromobenzoic acid (2.85-4.00), iodobenzoic acid (2 Benzoic acid, salicylic acid (2.81), naphthoic acid (3.70-
4.16), cinnamic acid (3.88), mandelic acid (3.
19). Further, the organic acid may be an amino acid, for example, asparagine (2.14), aspartic acid (1.93), adenine (4.07), alanine (2.30), β-alanine (3. 53), arginine (2.05), isoleucine (2.32), glycine (2.36), glutamine (2.17), glutamic acid (2.18), serine (2.13), tyrosine (2.17) ), Tryptophan (2.35), threonine (2.21), norleucine (2.30), valine (2.26), phenylalanine (2.26), methionine (2.15), lysine (2.25).
04), leucine (2.35) and the like.

Further, a polyvalent carboxylic acid or a derivative thereof as a release agent will be described. The hydrocarbon polycarboxylic acid may be substituted or unsubstituted. For example, oxalic acid (pKa: 1.27), malonic acid (2.6)
5), succinic acid (4.00), glutaric acid (4.1)
3), adipic acid (4.26), pimelic acid (4.3)
1), azelaic acid (4.39), fumaric acid (2.8)
5) and the like, and malic acid (3.24), tartaric acid (2.
82-2.99), citric acid (2.87), phthalic acid (2.75), which is an aromatic polycarboxylic acid, isophthalic acid (3.50), terephthalic acid (3.54), trimellitic acid And 2,6-pyridinedicarboxylic acid (2.09) as a heterocyclic polycarboxylic acid such as 4-methylphthalic acid. Further, amino acids may be used as the organic acid, and for example, aspartic acid (1.93), glutamic acid (2.18) and the like are used. Among these, malonic acid which is an aliphatic polycarboxylic acid, succinic acid,
Glutaric acid, fumaric acid, malic acid, tartaric acid, citric acid and the like are preferred.

Next, as the polyvalent carboxylic acid derivative as the release agent used in the present invention, those ester groups or amide groups are used as derivatives. First, the ester group is preferably a substituted or unsubstituted alkyl group, alkenyl group, or allyl group, and has a total carbon number of 1 to 200, more preferably 1 to 100, further preferably 1 to 50.
It is. As the substituent of the alkyl group, alkenyl group and allyl group, a (poly) oxyalkylene group is preferable, and a (poly) oxyalkylene group is particularly preferably a poly (oxyethylene) group, a (poly) oxypropylene group, a (poly) oxy It is preferably a butylene group or a (poly) oxyglycerin group. The amide derivative, which is a preferred embodiment of the polycarboxylic acid derivative, may be primary, substituted or unsubstituted secondary or tertiary, and is not particularly limited. As the substituent, an alkyl group, an alkenyl group, and an allyl group are preferable, and the total carbon number is 1 to 200, more preferably 1 to 100, and further preferably 1 to 50. As the substituent for the alkyl group, alkenyl group, and allyl group, a (poly) oxyalkylene group is preferable, and a (poly) oxyalkylene group is particularly preferably a poly (oxyethylene) group, a (poly) oxypropylene group, or a (poly) oxyalkylene group. Butylene group,
It is preferably a (poly) oxyglycerin group.

The above-mentioned acids may be used as free acids or as alkali metal salts, alkaline earth metal salts or heavy metals. Examples of the alkali metal include lithium, potassium, and sodium, and examples of the alkaline earth metal include calcium, magnesium, barium, and strontium. Heavy metals or transition metals include aluminum, zinc, tin, nickel, iron, lead,
Copper, silver and the like. Further, substituted or unsubstituted amines having 5 or less carbon atoms are also preferable, for example, ammonium, methylamine, ethylamine, propylamine, butylamine,
Dimethylamine, trimethylamine, triethylamine, hydroxyethylamine, di (hydroxyethyl)
Amine, tri (hydroxyethyl) amine and the like can be used. Preferred alkali metals include sodium, and preferred alkaline earth metals include calcium and magnesium. These alkali metals and alkaline earth metals can be used alone or in combination of two or more, and alkali metals and alkaline earth metals may be used in combination. The total content of the acid and its metal salt is in a range that does not impair the releasability, transparency, film forming property, etc., for example, 1 × 10 ^{−9 to} 3 × 10 per 1 g of cellulose acylate.
^-5 mol, preferably 1 × 10 ^-8 ~2 × 10 ^-5 mol ^{(e.g., 5 × 10 -7 ~1.5 × 10} -5 mol), more preferably 1 × 10 ^-7 ~1 × 10 ^{- 5} mol (for example, 5 × 10 ^-6
~ 8 × 10 ^-6 mol), usually 5
× 10 ^{-7 to} 5 × 10 ^-6 mol (for example, 6 × 10 ^{-7 to} 3 ×
10 ⁻⁶ mol). Particularly preferred specific compounds among the above-mentioned polyvalent carboxylic acid derivatives are described below, but are not limited thereto.

PK-1: C ₁₂ H ₂₅ OP (= O)-(OK) ₂ PK-2: C ₁₂ H ₂₅ OCH ₂ CH ₂ OP (= O)-(OK) ₂ PK-3: [C _{12 H 25 O (CH 2 CH 2} O) 5] 2 -P (= O) -OH PK- 4: [C 18 H 35 (OCH 2 CH 2) 8 O] 2 -P (= O) -ONH 4 PK −5: C ₁₂ H ₂₅ OSO ₃ Na PK− 6: iso-C ₈ H ₁₇ -C ₆ H ₄ -O- (CH ₂ CH ₂ O) _3- (CH ₂ ) ₂ SO ₃ Na PK− 7: Bird sodium isopropyl naphthalene sulfonate _{PK- 8: HOOC (CH 2)} k CO (OCH 2 CH 2) m OR, R = CH 3, k = 0, m =
6 PK-9: HOOC-CH ₂ CH (OH) -COOR, R = CH ₃ PK-10: HOOC-CH (OH) -CH (OH) -COOR, R = (CH ₂ CH ₂ O) ₃ -OC ₄ H
₉ PK-11: Citrate mono [ethoxy-tri (ethylene glycol)] ester PK-12: Citrate di [butoxy-hexa (ethylene glycol)] ester PK-13: Trimellitic acid di [butoxy-penta (ethylene glycol) )] Ester PK-14: N-acetyl-aspartic acid mono [butoxy-hepta (ethylene glycol)] ester PK-15: HOOC-CH ₂ -CONR1 / R2, R1 = H, R2 = (CH ₂ CH ₂ O)
₅ H PK-16: HOOC-CH (OH) -CH ₂ CONH (CH ₂ CH ₂ O) ₅ H PK-17: Monocitrate [N-octa (ethylene glycol)]
Amide _{PK-18: LiOOC-CH 2} CH (OH) -COOR, R = CH 2 CH (OH) CH 2 O) 5 H PK-19: citric acid di [butoxy - hexa (ethylene glycol)] Na salt of an ester

It is preferable that the cellulose acylate solution be peeled off from the metal support at 20 to 1000% by weight (% of the solution weight divided by the solid weight) after casting. If not, peeling is difficult unless the amount is 20 to 150% by mass, and there is a disadvantage that drying time is required. On the other hand, in the cellulose acylate solution containing the release agent preferred in the present invention, the release can be performed even when the residual solvent is 20 to 500% by mass, and the release load at the time of release can be significantly reduced. The surface condition was improved. Such a cellulose acylate film has high releasability from a metal support in the production of a film by a casting method, and can improve the film-forming speed and, consequently, the productivity of the cellulose acylate film. Further, the cellulose acylate film has excellent optical properties such as transparency, and its transparency is, for example, 60 to 100% (preferably 70 to 100%, more preferably 75 to 100%).
%), Usually about 70 to 98%, and the haze is 0.01 to 8%, preferably 0.02 to 5%.
Further, the Yellowness Index (YI), which is an index of the yellowness of cellulose acetate,
Is, for example, 0.05 to 10, preferably 0.08 to 7
It is.

The preferred plasticizer in the present invention has a boiling point of 200
Above, liquid at 25 ° C. or melting point of 25 to 25
Solid at 0 ° C. More preferably, the boiling point is 250 ° C.
Examples of the plasticizer which is liquid at 25 ° C or a solid having a melting point of 25 to 200 ° C are mentioned. Phosphoric acid esters or carboxylic acid esters are preferably used as the plasticizer. Examples of phosphate esters include triphenyl phosphate (TPP) and tricresyl phosphate (TPP).
CP), cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate. Representative carboxylic esters are phthalic esters and citric esters. Examples of phthalate esters include dimethyl phthalate (DM
P), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), diphenyl phthalate (DPP) and diethylhexyl phthalate (DEHP). Examples of citrate esters include O-acetyl triethyl citrate (OACT
E) and tributyl O-acetylcitrate (OACT
B), acetyl triethyl citrate, acetyl tributyl citrate, O-acetyl citrate tri (ethyloxycarbonylmethylene) ester. These plasticizers are liquid except for TPP (melting point about 50 ° C.) at 25 ° C., and have a boiling point of 250 ° C. or more.

Examples of other carboxylic esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic esters. Examples of glycolic acid esters include triacetin, tributyrin, butylphthalylbutyto, ethylphthalylethyl glycolate, methylphthalylethyl glycolate, butylphthalylbutyl glycolate, methylphthalylmethyl glycolate, propylphthalylpropyl glycolate And butyl phthalyl butyl glycolate and octyl phthalyl octyl glycolate. Among them, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, tributyl phosphate, dimethyl phthalate, diethyl phthalate,
Dibutyl phthalate, dioctyl phthalate, diethylhexyl phthalate, triacetin, and ethyl phthalyl ethyl glycolate are preferred. Particularly, triphenyl phosphate, diethyl phthalate, and ethyl phthalyl ethyl glycolate are preferred. These plasticizers may be used alone or in combination of two or more. The amount of the plasticizer added is 2 to 30% by mass, especially 5 to 20% by mass based on the cellulose acylate.
It is preferable that the content is mass%. In addition, in the present invention, as plasticizers for reducing the optical anisotropy, (di) pentaerythritol esters described in JP-A-11-124445 and glycerol esters described in JP-A-11-246704 are used. JP-A-2000-63
Diglycerol esters described in JP-A-560, citric acid esters described in JP-A-11-92574, and substituted phenyl phosphate esters described in JP-A-11-90946 are preferably used.

To the cellulose acylate film, a deterioration inhibitor (eg, an antioxidant, a peroxide decomposer, a radical inhibitor, a metal deactivator, an acid scavenger, an amine) and an ultraviolet inhibitor are added. Is also good. Regarding these deterioration inhibitors and ultraviolet inhibitors, JP-A-60-235852, JP-A-3-199201, JP-A-5-1907073, JP-A-5-194789, JP-A-5-271471,
JP-A-6-107854, JP-A-6-118233
JP-A-6-148430, JP-A-7-11056
JP-A-7-11055 and JP-A-7-11056
JP-A-8-29619, JP-A-8-239509
JP-A-7-11056, JP-A-2000-2041
No. 73, 5-1970073, JP-A-5-194789
JP-A-6-107854, JP-A-60-2358
No. 52, JP-A-12-193821, JP-A-8-29
No. 619, JP-A-6-118233 and JP-A-6-118233.
It is described in each publication of 148430. The amount of these additives is preferably 0.01 to 1% by mass of the solution (dope) to be prepared, and more preferably 0.01 to 0.08% by mass. When the addition amount is less than 0.01% by mass, the effect of the deterioration inhibitor is hardly recognized. If the amount exceeds 1% by mass, bleed-out (bleeding out) of the deterioration inhibitor on the film surface may be observed.

The preferred deterioration inhibitor of the present invention has a boiling point of 2
Liquid at 25 ° C. at a temperature of at least 00 or a melting point of 25 to
It is a solid at 250 ° C. More preferably, the boiling point is 25.
It is liquid at 25 ° C. of 0 ° C. or higher, or has a melting point of 25 to 200
Deterioration inhibitors which are solids at ℃. When the deterioration inhibitor is a liquid, its purification is usually carried out by distillation under reduced pressure, but the higher the vacuum, the more preferable it is. It is also particularly preferable to purify using a molecular distillation apparatus or the like. If the plasticizer is solid,
It is generally performed by recrystallization using a solvent, filtration, washing and drying. As a deterioration inhibitor,
Basic compounds having a pKa of 4 or more described in JP-A-5-194789 are exemplified. For example, first grade, 2
Preferred are primary and tertiary amines and aromatic base compounds.
Specifically, tributylamine, trihexylamine,
Trioctylamine, dodecyl-dibutylamine, octadecyl-dimethylamine, tribenzylamine, diethylaminobenzene and the like can be mentioned. -1 to A-73 and B-1 to B-67 can be used. A particularly preferred example of the deterioration inhibitor is butylated hydroxytoluene (BHT).

The ultraviolet absorber preferably used for the cellulose acylate film of the invention will be described. Specific examples of the ultraviolet absorber include, for example, an oxybenzophenone-based compound, a benzotriazole-based compound, a salicylate-based compound, a benzophenone-based compound, a cyanoacrylate-based compound, and a nickel complex salt-based compound. Specific examples of the benzotriazole-based ultraviolet absorber will be given, but the present invention is not limited thereto. 2
-(2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-
Di-tert-butylphenyl) benzotriazole, 2-
(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5
Chlorobenzotriazole, 2- (2'-hydroxy-
3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole, 2,2-methylenebis (4- (1,1,3,3
-Tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5
-Chlorobenzotriazole, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5
Sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenylmethane), (2,4-
Bis- (n-octylthio) -6- (4-hydroxy-
3,5-di-tert-butylanilino) -1,3,5-triazine, 2 (2′-hydroxy-3 ′, 5′-di-te
rt-butylphenyl) -5-chlorobenzotriazole, (2 (2′-hydroxy-3 ′, 5′-di-tert-
Amylphenyl) -5-chlorobenzotriazole,
2,6-di-tert-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- ( 3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6
-(4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxy) Phenyl) propionate], octadecyl-3
-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 1,3,5 -Trimethyl-2,4,6-
Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate and the like can be mentioned.

In particular, (2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, 2 (2'-hydroxy- 3 ', 5'-di-tert-butylphenyl)-
5-chlorobenzotriazole, (2 (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) -5-chlorobenzotriazole, 2,6-di-tert-butyl-
p-cresol, pentaerythrityl-tetrakis [3
-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] are preferred. Further, for example, a hydrazine-based metal deactivator such as N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine or tris (2,4-
A phosphorus-based processing stabilizer such as di-tert-butylphenyl) phosphite may be used in combination. The addition amount of these compounds is 0.01% by mass relative to cellulose acylate.
To 5% by mass, preferably 0.05 to 3% by mass.
Is more preferable.

A retardation increasing agent for controlling optical anisotropy is optionally added. In order to adjust the retardation of the cellulose acylate film, an aromatic compound having at least two aromatic rings is preferably used as a retardation increasing agent. Further, a colorant compound for preventing light piping may be added to the support for the light-sensitive material.
The content of the coloring agent is preferably from 10 to 1000 ppm by mass relative to cellulose acylate,
More preferably, it is 0 to 500 ppm. By including a coloring agent in this manner, the light piping of the cellulose acylate film can be reduced, and the yellow tint can be improved. These compounds may be added together with the cellulose acylate or the solvent when preparing the cellulose acylate solution, or may be added during or after the solution preparation.

Further, if necessary, various additives may be added to the cellulose acylate solution at any stage after the preparation of the solution or after the preparation. Examples of additives include inorganic fine particles, heat stabilizers such as alkaline earth metal salts,
Examples include an antistatic agent, a flame retardant, a lubricant, and an oil agent. In particular, the inorganic fine particles used have a role as an anti-smudge agent and have an antistatic property. In this case, the hardness of the metal or metal compound is not particularly limited, but Mohs hardness is preferably 1
-10, more preferably 2-10. At that time. The surface may be chemically modified, for example, using an alkyl group (for example, methyl, ethyl, butyl, hexyl, benzyl, etc.) by a silane coupling agent. Organic fine particles are also preferably used, for example, cross-linked polystyrene,
Crosslinked polymethyl methacrylate, crosslinked triazine resin and the like can be mentioned.

In particular, in the present invention, when the produced cellulose acylate film is handled, fine particles are generally added in order to prevent the film from being damaged or from being deteriorated in transportability. Preferred specific examples of these matting agents include, as inorganic compounds, compounds containing silicon, silicon dioxide, titanium oxide, zinc oxide, aluminum oxide, barium oxide, zirconium oxide, strongtium oxide, antimony oxide, tin oxide, and tin oxide.・ Antimony, calcium carbonate, talc, clay,
Examples thereof include calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, and calcium phosphate, and more preferred examples include inorganic compounds containing silicon and zirconium oxide. For example, Aerosil R972, R974, R8
12, 200, 300, R202, OX50, TT60
A commercially available product having a trade name such as 0 (all manufactured by Nippon Aerosil Co., Ltd.) can be used. As the fine particles of zirconium oxide, for example, those commercially available under trade names such as Aerosil R976 and R811 (both manufactured by Nippon Aerosil Co., Ltd.) can be used.

As the organic compound, for example, polymers such as silicone resin, fluorine resin and acrylic resin are preferable, and among them, silicone resin is preferably used. Among the silicone resins, those having a three-dimensional network structure are particularly preferable.
Commercial products having a trade name such as 0 (all manufactured by Toshiba Silicone Co., Ltd.) can be used. The primary average particle diameter of these fine particles is preferably 0.001 to 20 μm, more preferably 0.001 to 10 μm, and still more preferably 0.00, from the viewpoint of suppressing haze.
2-1 μm, particularly preferably 0.005-0.5 μm.
5 μm. The measurement of the primary average particle diameter of the fine particles is obtained by measuring the particles with an average particle diameter using a transmission electron microscope. The apparent specific gravity of the fine particles is preferably 70 g / L or more, more preferably 90 to 200 g / L, and particularly preferably 100 to 200 g / L. For example, Aerosil 200V, Aerosil R972V
(These are manufactured by Nippon Aerosil Co., Ltd.), and they can be used.

Next, an organic solvent used for preparing a solution of cellulose acylate will be described. In the present invention, cellulose acylate is dissolved and cast,
The organic solvent is not particularly limited as long as the film can be formed. These may be chlorinated organic solvents or non-chlorinated organic solvents. For example, examples of the chlorine-based organic solvent include methylene chloride and chloroform, and methylene chloride is particularly preferable. However, these chlorinated organic solvents have recently been concerned about their environmental safety, and the use of non-chlorinated organic solvents is preferred. The solvents particularly preferably used in the present invention are described in detail below. That is, it is preferable to produce a cellulose acylate film by a solvent casting method, and the film is produced using a solution (dope) in which cellulose acylate is dissolved in an organic solvent. The organic solvent preferably used as the main solvent has 3 to 1 carbon atoms.
It is preferable that the solvent is selected from the group consisting of esters, ketones and ethers. Esters, ketones, and ethers may have a cyclic structure. Compounds having two or more of ester, ketone and ether functional groups (i.e., -O-, -CO- and -COO-) can also be used as the main solvent. May be provided. In the case of a main solvent having two or more types of functional groups, the number of carbon atoms may be within the specified range of the compound having any one of the functional groups. Examples of the esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate. 3 or more carbon atoms
Examples of twelve ketones 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,
Examples include dimethoxyethane, 1,4-dioxane, 1,3-dioxolan, tetrahydrofuran, anisole and phenetole. Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate, 2-ethoxyethyl acetate,
Examples include methoxyethanol and 2-butoxyethanol.

These main solvents for cellulose acylate can exhibit a preferred range in the solubility parameter. That is, the solubility parameter of the cellulose acylate used in the present invention is represented by 17 to 22.
There are many books describing the solubility parameter. Brandrup, E .; H et al. (Po
lymer Handbook (fourth edition), VII / 671-VII / 714)
In more detail. The organic solvent which can be effectively used for the cellulose acylate used in the present invention is 19 to 21 M
It preferably has a solubility parameter of Pa ^1/2 . Examples of the organic solvent having a solubility parameter of 19 to 21 MPa ^1/2 include methyl ethyl ketone (19),
Cyclohexanone (20.3), cyclopentanone (2
0.9), methyl acetate (19.6), 2-butoxyethanol (19.4), methylene chloride (20.3), dioxane (19.6), 1,3-dioxolane (19.
8), acetone (20.3), ethyl formate (19.
2), methyl acetoacetate (about 20) and tetrahydrofuran (19.4). Among them, methyl acetate, acetone, methyl acetoacetate, cyclopentanone, cyclohexanone, methylene chloride and the like are most preferred. These are disclosed in JP-A-9-95538.
No., published in Japanese Unexamined Patent Publication No. Further, Japanese Unexamined Patent Application Publication No.
No. 0, N-methylpyrrolidone, JP-A-11-
60807, a fluoroalcohol described in JP-A-11-263534, and 1,3-dimethyl described in JP-A-11-263534.
2-imidazolidinone and the like are also used.

The above solvent is selected from the various viewpoints described above, but is preferably as follows. That is, the preferred solvent for the cellulose acylate used in the present invention is a mixed solvent of three or more different solvents, and the first solvent is selected from methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, dioxolan, and dioxane. At least one or a mixture thereof, wherein the second solvent is selected from ketones or acetoacetates having 4 to 7 carbon atoms, and the third solvent is alcohol or carbon having 1 to 10 carbon atoms. It is selected from hydrogen, more preferably an alcohol having 1 to 8 carbon atoms. When the first solvent is a mixture of two or more solvents, the second solvent may not be provided. The first solvent is
More preferably methyl acetate, acetone, methyl formate,
Ethyl formate or a mixture thereof, and the second solvent is preferably methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl acetylacetate, or a mixture thereof.

The alcohol as the third solvent is preferably linear, branched or cyclic, and among them, a saturated aliphatic hydrocarbon is preferred. 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. In addition, as the alcohol, a fluorinated alcohol is also used. For example, 2-fluoroethanol, 2,2,2-trifluoroethanol,
Also included are 2,2,3,3-tetrafluoro-1-propanol. Further, the hydrocarbon may be linear, branched or cyclic. Both aromatic hydrocarbons and aliphatic hydrocarbons can be used. Aliphatic hydrocarbons may be saturated or unsaturated.
Examples of the hydrocarbon include cyclohexane, hexane, benzene, toluene and xylene. These third
The alcohols and hydrocarbons as the solvents may be used alone or as a mixture of two or more, and are not particularly limited. Third
As the solvent, preferred specific compounds are methanol, ethanol, 1-propanol and alcohol.
2-propanol, 1-butanol, 2-butanol,
And cyclohexanol, cyclohexane and hexane. Particularly preferred are methanol, ethanol, 1-propanol, 2-propanol and 1-butanol.

The above three kinds of mixed solvents are such that the first solvent is contained in a ratio of 20 to 90% by mass, the second solvent is contained in a ratio of 5 to 60% by mass, and the third solvent is contained in a ratio of 5 to 30% by mass. Is preferable, and the first solvent is 30 to 86% by mass,
Preferably, the second solvent contains 10 to 50% by mass and the third alcohol 7 to 25% by mass. Particularly, the first solvent is 30 to 80% by mass, and the second solvent is 1% by mass.
0 to 50% by mass, the third solvent is alcohol
Preferably, the content is 20% by mass. When the first solvent is a mixed solution and the second solvent is not used, the first solvent is preferably contained in a ratio of 20 to 90% by mass, and the third solvent is preferably contained in a ratio of 5 to 30% by mass, Furthermore, the first solvent is 30 to
86% by mass, and the third solvent is 7 to 25% by mass.
Preferably, it is included. Specific examples of preferred combinations of these solvents in the present invention include the following.

Methyl acetate / acetone / methanol / ethanol / butanol (75/10/5/5/5, parts by mass), methyl acetate / acetone / methanol / ethanol / propanol (75/10/5/5/5, parts by mass) Department),
Methyl acetate / acetone / methanol / ethanol / cyclohexane (75/10/5/5/5, parts by mass), methyl acetate / methyl ethyl ketone / methanol / ethanol (80/10/5/5, parts by mass), methyl acetate / acetone / Methyl ethyl ketone / ethanol (75/10/1)
0/5, parts by mass), methyl acetate / cyclopentanone / methanol / ethanol (80/10/5/5, parts by mass), methyl acetate / cyclopentanone / methanol / ethanol (80/10/5/5, Parts by mass), methyl acetate / cyclopentanone / acetone / methanol / ethanol (60/15/15/5/5, parts by mass), methyl acetate / cyclohexanone / methanol / hexane (70/2)
0/5/5, parts by mass), methyl acetate / methyl ethyl ketone / acetone / methanol / ethanol (50/20 /
20/5/5, parts by mass), methyl acetate / 1,3 dioxolane / methanol / ethanol (70/20/5/5,
Parts by mass), methyl acetate / dioxane / acetone / methanol / ethanol (60/20/10/5/5, parts by mass), methyl acetate / acetone / cyclopentanone / ethanol / butanol / cyclohexane (65/10/1)
0/5/5/5, parts by mass), methyl formate / methyl ethyl ketone / acetone / methanol / ethanol (50/2
0/20/5/5, parts by mass), methyl formate / acetone /
Ethyl acetate / ethanol / butanol / hexane (65
/ 10/10/5/5/5/5, parts by mass), acetone / methyl acetoacetate / methanol / ethanol (65/20 /
10/5, parts by mass), acetone / cyclopentanone / ethanol / butanol (65/20/10/5, parts by mass), acetone / 1,3 dioxolan / ethanol / butanol (65/20/10/5, parts by mass) Parts) 1,3 dioxolane / cyclohexanone / methyl ethyl ketone /
Methanol / butanol (55/20/10/5/5/5 /
5, parts by mass), acetone / methylene chloride / methanol (85/5/5, parts by mass), methyl acetate / methylene chloride / methanol / ethanol (70/10/15/5, parts by mass), 1,3-dioxolane / Methylene chloride / methanol / butanol (70/15/10/5, parts by mass),
1,4-dioxane / methylene chloride / acetone / methanol / butanol (70/5/15/5/5, parts by mass), cyclohexanone / methylene chloride / acetone / methanol / ethanol / propanol (60/10/1)
5/5/5/5, parts by mass).
Among them, methyl acetate / acetone / methanol / ethanol (75/15/5/5, parts by mass), methyl acetate / acetone / methyl ethyl ketone / ethanol / butanol (75/10/5/5/5, parts by mass), Methyl acetate / cyclopentanone / methanol / ethanol (8
0/10/5/5, parts by mass), acetone / methyl acetoacetate / ethanol / isopropanol (65/15/1
(0/5/5, parts by mass) is a preferable combination.

The dissolution method of the cellulose acylate solution (dope) is not particularly limited, and may be room temperature, may be a cooling dissolution method or a high temperature dissolution method, or a combination thereof. For example, JP-A-5-163
No. 301, JP-A-61-106628 and JP-A-58-106
127737, JP-A-9-95544, JP-A-10-95544
-95854, JP-A-10-45950, JP-A-20
00-53784, JP-A-11-322946, JP-A-11-322947, JP-A-2-2768
30, JP-A-2000-273239, JP-A-11-
No. 71463, JP-A-04-259511, JP-A-20
00-273184, JP-A-11-332017,
And methods for preparing a cellulose acylate solution are described in JP-A-11-302388 and the like. The above-described methods for dissolving cellulose acylate in an organic solvent can also be applied to the present invention within the scope of the present invention as appropriate. The amount of cellulose acylate is adjusted so that the solution mixture contains 5 to 40% by mass. More preferably, the amount of cellulose acylate is from 10 to 30% by mass.
Hereinafter, dissolution of cellulose acylate in a non-chlorine organic solvent will be described in more detail.

In the case of dissolution at room temperature, cellulose acylate is mixed with a solvent or an additive at a temperature of 0 to 55 ° C., and the mixture is stirred and mixed in a dissolving pot or the like to dissolve. Regarding dissolution, it is important that the cellulose acylate powder is soaked sufficiently uniformly in the solvent, and it is essential not to generate so-called mamaco (cellulose acylate powder portion in which the solvent does not spread at all). Therefore, it may be preferable to add a solvent in advance to the stirring vessel and then reduce the pressure in the dissolution vessel to add the cellulose acylate. Conversely, in some cases, it is preferable to add cellulose acylate in advance to the stirring vessel, and then add the solvent while reducing the pressure in the dissolving vessel. It is also a preferable method of preparing a solution to wet cellulose acylate in advance with a poor solvent such as alcohol and then add an ether, ketone or ester solvent having 3 to 12 carbon atoms. When a plurality of solvents are used, the order of addition is not particularly limited. For example, after the cellulose acylate is added to the main solvent, another solvent (for example, a gelling solvent such as alcohol) may be added, or after the gelling solvent is wetted in advance by the cellulose acylate. May be added, which is effective in preventing heterogeneous dissolution. In addition, at the time of stirring, after mixing the cellulose acylate and the solvent, the mixture may be left as it is to allow the cellulose acylate to sufficiently swell with the solvent, and then may be stirred to obtain a uniform solvent.

Next, preparation of a cellulose acylate solution (dope) by a cooling dissolution method will be described. First, cellulose acylate is gradually added to an organic solvent at a temperature around room temperature (−10 to 55 ° C.) with stirring. When a plurality of solvents are used, the order of addition is not particularly limited. For example, after the cellulose acylate is added to the main solvent, another solvent (for example, a gelling solvent such as alcohol) may be added, or after the gelling solvent is wetted in advance by the cellulose acylate. May be added,
Effective for preventing heterogeneous dissolution. Further, an optional additive described below may be added to the mixture. next,
The mixture is -100 to -10C (preferably -100 to-
(30 ° C, more preferably -100 to -50 ° C, most preferably -90 to -60 ° C). The cooling can be performed, for example, in a dry ice / methanol bath (−75 ° C.) or a mechanically cooled fluorine-based solvent (CFC). When cooled in this way, the mixture of the cellulose acylate and the organic solvent solidifies. The cooling rate is not particularly limited,
In the case of batch-type cooling, the viscosity of the cellulose acylate solution increases with cooling and the cooling efficiency deteriorates, so it is necessary to provide an efficient melting vessel to reach a predetermined cooling temperature.

Further, after the cellulose acylate solution is swollen, it can be achieved by transferring the cooling device at a predetermined cooling temperature for a short time. The cooling rate is preferably as high as possible, but the theoretical upper limit is 10,000 ° C./sec.
00 ° C / sec is the technical upper limit and 100 ° C
/ Sec is a practical upper limit. Note that the cooling rate is a value obtained by dividing the difference between the temperature at which cooling is started and the final cooling temperature by the time from when cooling is started to when the temperature reaches the final cooling temperature. Furthermore, this is 0-200 degreeC
(Preferably from 0 to 150 ° C., more preferably from 0 to 12
Heating to 0 ° C, most preferably 0 to 50 ° C) results in a solution in which the cellulose acylate flows in the organic solvent.
The temperature may be raised only at room temperature or heated in a warm bath. At this time, the pressure may be 0.3 to 30 MPa, but there is no particular problem. In that case, the heating is preferably performed in a short time as much as possible, preferably within 0.5 to 60 minutes, and particularly, heating for a short time of 0.5 to 2 minutes is recommended. If the dissolution is insufficient, the operation of cooling and heating may be repeated. Whether the dissolution is sufficient
The determination can be made only by visually observing the appearance of the solution. In the cooling dissolution method, it is desirable to use a closed container in order to avoid water contamination due to condensation during cooling. Further, in the cooling and heating operation, if the pressure is increased during cooling and the pressure is reduced during heating, the dissolution time can be shortened. In order to perform pressurization and decompression, it is desirable to use a pressure-resistant container. The above cooling and melting methods are described in detail in JP-A-9-95544, JP-A-10-95854, and JP-A-10-95854.

Next, preparation of a cellulose acylate solution (dope) by a high-temperature dissolution method will be described. First, cellulose acylate is gradually added to an organic solvent at a temperature around room temperature (−10 to 55 ° C.) with stirring. When a plurality of solvents are used, the order of addition is not particularly limited. For example, after the cellulose acylate is added to the main solvent, another solvent (for example, a gelling solvent such as alcohol) may be added, or after the gelling solvent is wetted in advance by the cellulose acylate. May be added,
Effective for preventing heterogeneous dissolution. It is preferable that the cellulose acylate solution is swelled in advance by adding cellulose acylate to a mixed organic solvent containing various solvents.
In such a case, cellulose acylate may be gradually added to any of the solvents at −10 to 55 ° C. with stirring, or may be swollen in advance with a specific solvent and then added with another combined solvent. The mixture may be mixed to form a uniform swelling solution, and further the mixture may be swelled with two or more solvents, and then the remaining solvent may be added. Next, the mixed solution of cellulose acylate and the organic solvent is 0.2 MPa
It is heated to 60 to 240 ° C under a pressure of 30 to 30 MPa (preferably 80 to 220 ° C, more preferably 100 to 240 ° C).
200 ° C, most preferably 100-190 ° C). The heating may be, for example, high pressure steam or an electric heat source. A pressure vessel or pressure line is required for high pressure,
Any of iron or stainless steel or other metal pressure vessels or lines may be used, and there is no particular limitation. Further, carbon dioxide may be sealed in these high-temperature and high-pressure solutions to form a so-called supercritical solution. In that case, the ratio of carbon dioxide to solvent is
It is preferably 5/95 to 70/30, more preferably 1
It is preferably 0/90 to 60/40.

Next, since these heated solutions cannot be applied as they are, they need to be cooled to a temperature lower than the lowest boiling point of the solvent used. In that case, it is common to cool to −10 to 55 ° C. and return to normal pressure. For cooling, the high-pressure high-temperature container or line containing the cellulose acylate solution may be simply left at room temperature, and more preferably, the device may be cooled using a coolant such as cooling water. In addition,
The heating and cooling operations may be repeated to speed up the dissolution. Whether or not the dissolution is sufficient can be determined only by visually observing the appearance of the solution. In the high-pressure high-temperature dissolution method, a closed container is used to avoid evaporation of the solvent. Further, in the swelling step, the dissolution time can be further reduced by increasing the pressure or reducing the pressure. In order to perform pressurization and decompression, a pressure-resistant container or line is essential. These are described in JP-A-11-32.
No. 2,946, and JP-A-11-322947.

As described above, the concentration of the cellulose acylate solution is characterized in that a high-concentration dope can be obtained, and a cellulose acylate solution having a high concentration and excellent stability can be obtained without relying on concentration means. . After further dissolving at a low concentration to facilitate dissolution, the solution may be concentrated using a concentration means. The method of concentration is not particularly limited. A method of obtaining a high-concentration solution while evaporating the solvent by giving a difference (for example, Japanese Patent Application Laid-Open No.
No. 9511), a heated low-concentration solution is blown into a container from a nozzle, and the solvent is flash-evaporated until the solution hits the inner wall of the container from the nozzle. From U.S. Pat. No. 2,541,012, U.S. Pat.
SP 2,858,229, USP 4,414,3
No. 41, USP 4,504, 355, etc.).

Prior to casting, it is preferable that foreign substances such as undissolved matter, dust, and impurities are removed by filtration using a suitable filtering material such as a wire mesh or flannel. Absolute filtration accuracy is 0.1-100μ for filtration of cellulose acylate solution
m, preferably a filter having a size of 0.5 to 25 μm. The thickness of the filter is preferably from 0.1 to 10 mm, more preferably from 0.2 to 2 mm. In that case, filtration pressure is, 16 kgf / cm ² or less, more preferably 12 kgf / cm ² or less, more 1
0 kgf / cm ² or less, particularly preferably 2 kgf / cm 2
It is preferred to filter at ² or less. As the filter material, conventionally known materials such as glass fiber, cellulose fiber, filter paper, and fluororesin such as tetrafluoroethylene resin can be preferably used, and ceramics and metals are particularly preferably used. The viscosity of the cellulose acylate solution immediately before film formation may be within a range that can be cast during film formation.
It is preferably adjusted to a range of 0 Pa · s to 2000 Pa · s, more preferably 30 Pa · s to 1000 Pa · s, and still more preferably 40 Pa · s to 500 Pa · s. The temperature at this time is not particularly limited as long as it is the temperature at the time of casting, but is preferably -5 to 70C, more preferably -5 to 55C.

A method for producing a film using a cellulose acylate solution will be described. In the production of the cellulose acylate film of the present invention, a solution casting film forming method and a solution casting film forming apparatus conventionally used for producing a cellulose triacetate film are used. The dope (cellulose acylate solution) prepared from the dissolver (pot) is once stored in a storage pot, and the foam contained in the dope is defoamed for final preparation. The dope is fed from the dope discharge port to a pressurized die through a pressurized metering gear pump capable of, for example, high-precision quantitative liquid feeding by the number of rotations, and the dope of a casting part running endlessly from a die (slit) of the pressurized die. The freshly dried dope film (also referred to as a web) is peeled from the metal support at a peeling point where it is uniformly cast on the metal support and the metal support has made a round. The both ends of the obtained web are sandwiched by clips, transported by a tenter while maintaining the width, and dried,
Subsequently, the sheet is conveyed by a group of rolls of a drying device, dried, and wound up to a predetermined length by a winder. The combination of the tenter and the roll group drying device varies depending on the purpose. In a solution casting film forming method used for a silver halide photographic material or a functional protective film for an electronic display, in addition to a solution casting film forming apparatus, an undercoat layer, an antistatic layer, an antihalation layer, a protective layer, etc. In order to process the surface of the film, a coating device is often added. The following briefly describes each of the manufacturing steps, but is not limited thereto.

Using the prepared cellulose acylate solution (dope), a film is produced by a solvent casting method. The dope is cast on a metal support such as a drum or a band, and a film is formed by evaporating a solvent contained in the dope. The concentration of the dope before casting is preferably adjusted so that the solid content is 5 to 40% by mass. It is preferable that the surface of the drum or the band is finished in a mirror state. The dope has a surface temperature of 3
It is preferable to cast on a metal support such as a drum or band at 0 ° C. or lower. The surface temperature of the metal support is -1
It is particularly preferred that it is in the range of 0 to 20 ° C. Further, JP-A-2000-301555 and JP-A-2000-3015
No. 58, JP-A-07-032391, JP-A-03-1
No. 93316, Japanese Patent Application Laid-Open No. 05-086212, Japanese Patent Application Laid-Open
JP-A-2-037113, JP-A-02-276607, JP-A-55-014201, JP-A-02-111511
And the techniques described in JP-A-02-208650.

The cellulose acylate solution may be cast as a monolayer solution on a smooth band or drum,
It may be cast as two or more cellulose acylate solutions. When casting a plurality of cellulose acylate solutions, even if the film is produced while casting and laminating the cellulose acylate solution from a plurality of casting ports provided at intervals in the traveling direction of the metal support, respectively. For example, JP-A-61-158414, JP-A-1-122241
No. 9 and JP-A-11-198285 can be used. Alternatively, a film may be produced by casting a cellulose acylate solution from two casting ports.
562, JP-A-61-94724 and JP-A-61-9
No. 47245, Japanese Unexamined Patent Application Publication No.
The casting method described in each of JP-A-1-158413 and JP-A-6-134933 can be used. Further, a cellulose acylate solution described in JP-A-56-162617, in which a flow of a high-viscosity cellulose acylate solution is wrapped with a low-viscosity cellulose acylate solution, and the high- and low-viscosity cellulose acylate solutions are simultaneously extruded. A rate film casting method may be used. Further, Japanese Unexamined Patent Publication No.
As described in JP-A-1-94724 and JP-A-61-94725, it is also a preferable embodiment that the outer solution contains more alcohol component which is a poor solvent than the inner solution. Alternatively, by using two casting ports, the film formed on the metal support is peeled off by the first casting port, and the second casting is performed on the side in contact with the surface of the metal support to thereby remove the film. It may be produced, for example,
The method described in JP-A-4-220235 can be used. The cellulose acylate solutions to be cast may be the same solution or different cellulose acylate solutions, and are not particularly limited. In order to give a function to a plurality of cellulose acylate layers, a cellulose acylate solution corresponding to the function may be extruded from each casting port. Further, the cellulose acylate solution can be cast simultaneously with other functional layers (for example, an adhesive layer, a dye layer, an antistatic layer, an antihalation layer, a UV absorbing layer, a polarizing layer, etc.).

In the conventional method of casting a monolayer liquid, it is necessary to extrude a high-concentration and high-viscosity cellulose acylate solution to obtain a required film thickness. Instability was low and solids were generated, which often caused problems such as lumps and poor flatness. By casting a plurality of cellulose acylate solutions from the casting port, it is possible to simultaneously extrude a high-viscosity solution onto a metal support, thereby improving the flatness and producing an excellent planar film. Instead, by using a concentrated cellulose acylate solution, a reduction in drying load can be achieved, and the production speed of the film can be increased. In the case of co-casting, the thickness of the inner side and the outer side is not particularly limited, but preferably the outer side has a total thickness of 1 to 1.
The thickness is preferably 50%, more preferably 2 to 30%. Here, in the case of co-casting with three or more layers, the total thickness of the layer in contact with the metal support and the layer in contact with the air side is defined as the outer thickness. In the case of co-casting, the aforementioned plasticizers, ultraviolet absorbers, co-casting cellulose acylate solutions with different additive concentrations of matting agents,
A cellulose acylate film having a laminated structure can be produced. For example, a cellulose acylate film having a structure of skin layer / core layer / skin layer can be produced. For example, the matting agent can be contained in a large amount in the skin layer or only in the skin layer. The plasticizer and the ultraviolet absorber can be added to the core layer more than the skin layer, or may be added only to the core layer. The type of the plasticizer and the ultraviolet absorber can be changed between the core layer and the skin layer. For example, the skin layer contains a low-volatility plasticizer and / or an ultraviolet absorber, and the core layer has excellent plasticity. It is also possible to add a plasticizer or an ultraviolet absorber excellent in ultraviolet absorption.
In a preferred embodiment, the release agent is contained only in the skin layer on the metal support side. Further, in order to cool the metal support by the cooling drum method to gel the solution, it is also preferable to add more alcohol, which is a poor solvent, to the skin layer than to the core layer. Glass transition temperature of skin layer and core layer (T
g) may be different, and the Tg of the core layer is preferably lower than the Tg of the skin layer. The viscosity of the cellulose acylate solution at the time of casting may be different between the skin layer and the core layer, and the viscosity of the skin layer is preferably smaller than the viscosity of the core layer. It may be smaller than the viscosity.

The casting method useful in the present invention will be described in more detail. A method in which the prepared dope is uniformly extruded from a pressure die onto a metal support, and a method in which the dope once cast on the metal support is bladed. There is a method using a doctor blade for adjusting the film thickness by a method, a method using a reverse roll coater for adjusting with a roll rotating in the reverse direction, and the like, but a method using a pressure die is preferable. The pressure die includes a coat hanger type and a T-die type, and any of them can be preferably used. In addition, it can be carried out by various methods for casting and forming a cellulose triacetate solution conventionally known in addition to the methods mentioned here, and by setting each condition in consideration of a difference in the boiling point of the solvent used, etc. The same effects as those described in the above publication can be obtained. As a metal support running endlessly used for producing the cellulose acylate film of the present invention, a drum whose surface is mirror-finished by chrome plating or a stainless belt (surface called a band) which is mirror-finished by surface polishing is used. Is also used. One or more pressure dies may be provided above the metal support for the production of the cellulose acylate film of the invention. Preferably it is one or two. When two or more units are installed, the dope amount to be cast may be divided into various ratios for each die.
The dope may be sent to the die at a respective ratio from a plurality of precision metering gear pumps. The temperature of the cellulose acylate solution used for casting is preferably from -10 to 55C, more preferably from 25 to 50C.
In that case, all of the steps may be the same, or may be different at various points in the steps. If different, the temperature may be a desired temperature immediately before casting.

As a method for drying the dope cast on the metal support, generally, a hot air is applied from the surface side of the metal support (drum or belt), that is, from the surface of the web on the metal support. A method of applying hot air from the back side of a drum or belt, and a liquid whose temperature is controlled by bringing the liquid whose temperature is controlled into contact with the back side opposite to the dope casting surface of the belt or drum and heating the drum or belt by heat transfer. Heat transfer method, etc.,
It is preferable to use the backside liquid heat transfer system. The surface temperature of the metal support before casting may be any number of times as long as it is lower than the boiling point of the solvent used for the dope. However, in order to promote drying and to lose fluidity on the metal support, the surface of the metal support is brought to a temperature 1 to 10 ° C. lower than the boiling point of the solvent having the lowest boiling point among the solvents contained in the dope. It is preferable to set the temperature. This is not the case when the casting dope is cooled and peeled off without drying.

The obtained cellulose acylate film
May be stretched in the width direction. For the stretching process,
JP-A-62-115035, JP-A-4-152125
JP-A-4-284221, JP-A-4-29831
0 and JP-A-11-48271
Have been. By stretching the film, the cellulose
Increase the in-plane retardation value of the silicate film
can do. Stretching the film at room temperature or heating
It is carried out under the conditions. The heating temperature depends on the glass transition of the film.
It is preferable that the temperature is not higher than the temperature. The stretching of the film
Either axial stretching or biaxial stretching may be used. Stretching is 1 to 200
%, Preferably 1% to 100%.
It is more preferred that there be. Finish of the present invention (dry
The thickness of the cellulose acylate film after
Although it depends on the target, it is usually in the range of 5 to 500 μm.
More preferably in the range of 20 to 300 μm.
Most preferably in the range of 30-150 μm
No. The film thickness is adjusted so that the desired thickness is obtained.
Concentration of solids contained in dope, slit of die cap
Adjust the gap, extrusion pressure from the die, metal support speed, etc.
Just save.

The width of the cellulose acylate film is
0.5 to 3 m, preferably 0.6 to 2.5 m
Is more preferable, and more preferably 0.8 to 2.2 m. When the cellulose acylate film is wound into a roll, the length per roll is 1
It is preferably from 00 to 10,000 m, and from 500 to 7
000 m, more preferably 1000 to 600
More preferably, it is 0 m. When the film is wound into a roll, it is preferable to apply knurling to at least one end in the width direction of the film. The width of the knurling is preferably from 3 mm to 50 mm, and from 5 mm to
More preferably, it is 30 mm. The knurling height is preferably 0.5 to 500 μm,
More preferably, it is 200 μm. Knurling may be one-sided or two-sided. The knurling may be performed by continuously applying a surface treatment, an undercoat or a functional layer described later after casting. The film may be rolled up as it is, or may be slit and cut into a desired size for packaging.

A surface treatment can be applied to the cellulose acylate film. By the surface treatment, the adhesiveness between the cellulose acylate film and each functional layer (for example, the undercoat layer and the back layer) can be improved. As the surface treatment, for example, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment can be used. The glow discharge treatment here means 1
This is a so-called low-temperature plasma treatment that occurs under a low-pressure gas of 0 ^{-3 to} 20 Torr. Furthermore, plasma treatment under atmospheric pressure is also preferable. The plasma treatment used for the surface treatment of the cellulose acylate film of the invention will be described. Specifically, there are methods using vacuum glow discharge, atmospheric pressure glow discharge, and the like, and other methods include flame plasma processing. These are described, for example, in JP-A-6-123062 and JP-A-11-29301.
No. 1 and Nos. 11-5857. Above all, those based on atmospheric pressure glow discharge are preferably used. The plasma-excitable gas refers to a gas that is plasma-excited under the above conditions, and includes, for example, argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, fluorocarbons such as tetrafluoromethane, and mixtures thereof. it can. As these gases, those obtained by adding a reactive gas capable of imparting a polar functional group such as a carboxyl group, a hydroxyl group, or a carbonyl group to the surface of a plastic film to an inert gas such as argon or neon are used as an excitable gas. . As the reactive gas, in addition to hydrogen, oxygen, and nitrogen, in addition to gases such as steam and ammonia, low-boiling organic compounds such as lower hydrocarbons and ketones can be used as necessary. ,oxygen,
It is preferable to use a gas such as carbon dioxide, nitrogen, and water vapor. In the case of using steam, a gas obtained by bubbling another gas through water can be used. Alternatively, steam may be mixed.

The ultraviolet irradiation method is also preferably used in the present invention, and is disclosed in JP-B-43-2603 and JP-B-43-2604.
And the processing methods described in JP-B-45-3828. The mercury lamp is a high-pressure mercury lamp composed of a quartz tube, and has a wavelength of ultraviolet light of 180 to 38.
Those between 0 nm are preferred. With respect to the method of irradiating ultraviolet rays, a high-pressure mercury lamp having a main wavelength of 365 nm can be used as the light source if there is no problem in the performance of the support that the surface temperature of the cellulose acylate film rises to around 150 ° C. When low-temperature processing is required, a low-pressure mercury lamp having a main wavelength of 254 nm is preferable. It is also possible to use an ozoneless type high-pressure mercury lamp and a low-pressure mercury lamp. Regarding the amount of processing light, as the amount of processing light increases, the adhesive strength between the cellulose acylate film and the layer to be bonded improves, but the film becomes colored and becomes brittle as the amount of light increases. Therefore, in the case of a high-pressure mercury lamp for a 365nm main wavelength, it is preferable that irradiation light amount is ^{20~10000 (mJ / cm 2),} 50~2000 (mJ / cm 2)
Is more preferable. In the case of a low-pressure mercury lamp having a main wavelength of 254 nm, the irradiation light amount is 100 to 100.
00 (mJ / cm ² ), preferably from 300 to
More preferably, it is 1500 (mJ / cm ² ).

Corona discharge treatment is also preferably used as a surface treatment for the cellulose acylate film.
No. 12838, JP-A-47-19824, JP-A-Showa 4
It can be carried out by the processing methods described in JP-A-8-28067 and JP-A-52-42114.
Corona discharge treatment devices include Pillar's solid state corona treatment machine, LEPEL type surface treatment machine, VETA
A PHON type processor or the like can be used. The treatment can be performed at normal pressure in air. Describing the flame treatment, the gas used is natural gas, liquefied propane gas,
Any of city gas may be used, but the mixing ratio with air is important. This is because the effect of the surface treatment by the flame treatment is considered to be brought about by the plasma containing active oxygen. is there. These two factors are determined by the gas / oxygen ratio. When the reaction is performed without excess or deficiency, the energy density becomes highest and the plasma activity becomes high. Specifically, a preferable mixing ratio of natural gas / air is 1/6 to 1/1 in volume ratio.
0, preferably 1/7 to 1/9. In the case of liquefied propane gas / air, 1/14 to 1/22, preferably 1/16 to 1/19, and in the case of city gas / air, 1/2.
１ ／, preferably 1/3 to 1/7. Further, the flame treatment amount is preferably in the range of 1 to 50 Kcal / m ² , more preferably 3 to 20 Kcal / m ² .

Next, the alkali saponification treatment which is preferably used as a surface treatment for a cellulose acylate film will be specifically described. The alkali saponification treatment is preferably performed in a cycle in which the surface of the cellulose acylate film is immersed in an alkaline solution, neutralized with an acidic solution, washed with water, and dried. Examples of the alkaline solution include a potassium hydroxide solution and a sodium hydroxide solution. The specified concentration of hydroxide ion in the alkaline solution is 0.1
N to 3.0N, preferably 0.5N to 2.0N.
N is more preferred. The temperature of the alkaline solution is preferably in the range of room temperature to 90 ° C.
More preferably, it is in the range of from 70 ° C to 70 ° C. After the film is immersed in such an alkaline solution, it is generally washed with water, and then passed through an acidic aqueous solution and then washed with water to obtain a surface-treated cellulose acylate film. Examples of the acid used for the acidic aqueous solution include hydrochloric acid, nitric acid,
Sulfuric acid, acetic acid, formic acid, chloroacetic acid, and oxalic acid. The concentration of the acidic aqueous solution is 0.01 N to 3.0.
N, more preferably 0.05N to 2.0N. When a cellulose acylate film is used as a transparent protective film for a polarizing plate, it is particularly preferable to perform an acid treatment or an alkali treatment, that is, a saponification treatment on the cellulose acylate, from the viewpoint of adhesion to the polarizing film. These solutions may be water alone, or may be a mixture of water-soluble organic solvents (methanol, ethanol, isopropanol, acetone, etc.).

In order to achieve adhesion between the film and the emulsion layer, a surface activation treatment is carried out, and then a functional layer is applied directly on the cellulose acylate film to obtain an adhesive force. There is a method in which an undercoat layer (adhesive layer) is provided after treatment or without surface treatment, and a functional layer is applied thereon. Various contrivances have been made for the constitution of the undercoat layer, and a layer (hereinafter abbreviated as the first undercoat layer) which is well adjacent to the support is provided as a first layer, and a functional layer is formed as a second layer thereon. There is a so-called multi-layer method in which an undercoating second layer that adheres well is applied. In the single-layer method, good adhesion is often achieved by expanding the cellulose acylate film and mixing it with the undercoat material. Examples of the undercoat polymer used in the present invention include a water-soluble polymer, a cellulose acylate, a latex polymer, and a water-soluble polyester. As a polymer,
Gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, maleic anhydride copolymer, and the like. Examples of cellulose acylate include carboxymethyl cellulose and hydroxyethyl cellulose.

The cellulose acylate film of the invention can be preferably used for optical applications and photographic materials. In particular, it is preferable that the optical application is a liquid crystal display device, and the liquid crystal display device has a liquid crystal cell carrying liquid crystal between two electrode substrates, two polarizing elements disposed on both sides of the liquid crystal cell, and the liquid crystal. It is more preferable that at least one optical compensation sheet is disposed between the cell and the polarizing element. These liquid crystal display devices include TN, I
PS, FLC, AFLC, OCB, STN, VA, and HAN are preferable, and details will be described later. At that time, when the cellulose acylate film produced using the non-chlorine organic solvent of the present invention is used for the above-mentioned optical application, various functional layers are provided. They include, for example, an antistatic layer, a cured resin layer (a transparent hard coat layer),
Anti-reflection layer, easy adhesion layer, anti-glare layer, optical compensation layer, alignment layer,
For example, a liquid crystal layer. These functional layers and their materials include a surfactant, a slipping agent, a matting agent, an antistatic layer, a hard coat layer, and the like.

First, the surfactant is used depending on the purpose of use.
Although classified into a dispersant, a coating agent, a wetting agent, an antistatic agent, and the like, these objects can be achieved by appropriately using a surfactant described below. Surfactants are nonionic,
Any of ionic (anion, cation, betaine) can be used. Further, a fluorine-based surfactant is also preferably used as a coating agent in an organic solvent or as an antistatic agent. The layer used may be a cellulose acylate solution or any of the other functional layers. When used in optical applications, examples of functional layers include undercoat layers, intermediate layers,
Orientation control layer, refractive index control layer, protective layer, antifouling layer, adhesive layer,
A back undercoat layer, a back layer, and the like. The amount used is not particularly limited as long as it is an amount necessary to achieve the purpose, but is generally 0.0001 to the mass of the layer to be added.
-5% by mass, more preferably 0.0005% by mass.
It is preferably about 2% by mass. In that case, the coating amount is preferably 0.02 to 1000 mg per 1 m ² ,
0.05-200 mg is preferred. Preferred nonionic surfactants include surfactants having a nonionic hydrophilic group of polyoxyethylene, polyoxypropylene, polyoxybutylene, polyglycidyl or sorbitan, and specifically, polyoxyethylene alkyl ether, Polyoxyethylene alkyl phenyl ether,
Polyoxyethylene-polyoxypropylene glycol, polyhydric alcohol fatty acid partial ester, polyoxyethylene polyhydric alcohol fatty acid partial ester, polyoxyethylene fatty acid ester, polyglycerin fatty acid ester, fatty acid diethanolamide, triethanolamine fatty acid partial ester Can be.

Examples of the anionic surfactant include carboxylate, sulfate, sulfonate and phosphate salt. Representative examples thereof include fatty acid salt, alkylbenzene sulfonate, alkylnaphthalene sulfonate, Alkyl sulfonate, α-olefin sulfonate, dialkyl sulfosuccinate, α-sulfonated fatty acid salt, N-methyl-N-oleyltaurine, petroleum sulfonate, alkyl sulfate, sulfated oil, polyoxyethylene alkyl Examples include ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, polyoxyethylene styrenated phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, and naphthalene sulfonate formaldehyde condensates. Examples of the cationic surfactant include an amine salt, a quaternary ammonium salt, a pyridum salt and the like. , Alkylpyridium salts, alkylimidazolium salts, etc.).
Examples of amphoteric surfactants include carboxybetaine and sulfobetaine, and N-trialkyl-N-carboxymethylammonium betaine and N-trialkyl-
N-sulfoalkylene ammonium betaine and the like. These surfactants are described in Applications of Surfactants (Koshobo, Takao Karimei, published September 1, 1980). There are no particular restrictions on the amount of surfactant used, as long as the desired surfactant properties can be obtained. Specific examples of the surfactant are described below, but are not limited thereto (here, -C ₆ H _4- represents a phenylene group).

Further, any of the layers above the cellulose acylate film may contain a slipping agent, in which case the outermost layer is particularly preferred. As the slip agent used,
For example, polyorganosiloxanes disclosed in JP-B-53-292, U.S. Pat. No. 4,275,
No. 146, higher fatty acid amides as disclosed in JP-B-58-33541, UK Patent No. 92
No. 7,446, or JP-A-55-126238 and JP-A-58-90633, which are examples of a higher fatty acid ester (containing a fatty acid having 10 to 24 carbon atoms and an alcohol having 10 to 24 carbon atoms). Ester), and
Metal salts of higher fatty acids as disclosed in U.S. Pat. No. 3,933,516, and JP-A-58-505.
No. 34, an ester of a linear higher fatty acid and a linear higher alcohol, disclosed in WO 901081
Higher fatty acid-higher alcohol esters containing a branched alkyl group as disclosed in 15.8 are known. Among these, polyorganosiloxanes include polyalkylsiloxanes such as polydimethylsiloxane and polydiethylsiloxane, polyarylsiloxanes such as polydiphenylsiloxane and polymethylphenylsiloxane, and generally known polyorganosiloxanes. issue,
JP-B-55-49294, JP-A-60-140341
Nos. 4,019,086, 5,897,898, organopolysiloxanes having an alkyl group of C5 or more, alkylpolysiloxanes having a polyoxyalkylene group in a side chain, alkoxy in a side chain,
A modified polysiloxane such as an organopolysiloxane having a hydroxy, hydrogen, carboxyl, amino, or mercapto group can be used, and a block copolymer having a siloxane unit can also be used. Specific examples of such compounds are shown below, but are not limited thereto. Further, as higher fatty acids and derivatives thereof, higher alcohols and derivatives thereof,
Higher fatty acids, metal salts of higher fatty acids, higher fatty acid esters, higher fatty acid amides, polyhydric alcohol esters of higher fatty acids, etc .; higher fatty alcohols; Phyto, monoalkyl phosphate, dialkyl phosphate, trialkyl phosphate, higher aliphatic alkylsulfonic acid, an amide compound thereof, a salt thereof and the like can be used. Specific examples of such compounds are shown below, but the present invention is not limited thereto.

By using such a slipping agent, it is possible to obtain an excellent film having excellent scratching strength and free from repelling or the like on the undercoating surface. The amount of the slip agent used is not particularly limited, but the content is 0.0005 to 2 g /
m ² is preferred, and more preferably 0.001 to 1 g / m
² , particularly preferably 0.002 to 0.5 g / m ² . The layer to which the slip agent is added is not particularly limited, but is preferably contained in the outermost layer on the back surface. The surface layer containing the above-mentioned slipping agent can be formed by applying a coating solution obtained by dissolving the same in an appropriate organic solvent onto a support or a support having a back layer provided with another layer, and drying. Further, the slip agent can be added in the form of a dispersion in the coating solution. For the slip performance, the coefficient of static friction is preferably 0.30 or less, more preferably 0.25 or less, and particularly preferably 0.13 or less. Also,
It is preferable that the coefficient of static friction with the contacting partner material is small, which helps to prevent scratches and the like. At this time, the coefficient of static friction with the mating material is preferably 0.3 or less, and more preferably 0.3.
It is preferably 25 or less, particularly preferably 0.13 or less.
In many cases, it is preferable to reduce the coefficient of static friction between the front and back of the film or the optical film, and the coefficient of static friction between them is preferably 0.30 or less, more preferably 0.25 or less, particularly 0.13 or less. Preferably, there is. Further, the coefficient of kinetic friction is preferably 0.30 or less, more preferably 0.25 or less, and particularly preferably 0.15 or less. The coefficient of kinetic friction with the contacting material is preferably 0.3 or less, more preferably 0.25.
Below, it is particularly preferable that it is 0.15 or less. In many cases, it is preferable to reduce the coefficient of dynamic friction between the front and back of the film or the optical film, and the coefficient of dynamic friction between them is preferably 0.30 or less.
It is preferably 25 or less, particularly preferably 0.13 or less.

In the functional layer of the cellulose acylate film, it is preferable to use a matting agent in order to improve the slipperiness of the film and the adhesion resistance under high humidity. In that case, the average height of the protrusions on the surface is preferably 0.005 to 10 μm, and more preferably 0.01 to 5 μm. Also, the more the protrusions are on the surface, the better. As long as the preferred projection has the average height of the projection, the projection can be formed by, for example, a spherical or irregular matting agent, and its content is preferably 0.5 to 600 mg / m ^2. More preferably, it is 1 to 400 mg / m ² . At this time, as the matting agent to be used, fine particles added to the cellulose acylate film described above can be used, and the composition thereof is not particularly limited, and may be an inorganic or organic substance, or a mixture of two or more kinds. Inorganic compounds and organic compounds of the matting agent include, for example, barium sulfate, manganese colloid, titanium dioxide, strontium barium sulfate, silicon dioxide, aluminum oxide, tin oxide, zinc oxide, calcium carbonate, barium sulfate, talc, kaolin, calcium sulfate, etc. Inorganic fine powders such as silicon dioxide such as synthetic silica obtained by a wet method or gelling of silicic acid, and titanium dioxide (rutile type or anatase type) generated by titanium slag and sulfuric acid. It can also be obtained by pulverizing an inorganic substance having a relatively large particle size, for example, 20 μm or more, and then performing classification (vibration filtration, air classification, etc.). In addition, polytetrafluoroethylene, cellulose acetate, polystyrene, polymethyl methacrylate, polypropylene methacrylate, polymethyl acrylate, polyethylene carbonate, acrylic styrene resin, silicone resin, polycarbonate resin, benzoguanamine resin, melamine resin, polyolefin powder Also, pulverized and classified organic polymer compounds such as polyester-based resins, polyamide-based resins, polyimide-based resins, polyfluoroethylene-based resins, and starch can be used. Alternatively, a polymer compound synthesized by a suspension polymerization method, a polymer compound formed into a spherical shape by a spray drying method or a dispersion method, or an inorganic compound can be used.

The polarizing plate used as the optical film or the polarizing plate protective film of the present invention can be subjected to antistatic processing, transparent hard coat processing, antiglare processing, antireflection processing, easy adhesion processing and the like. Alternatively, an optical compensation function can be provided by forming an alignment film and providing a liquid crystal layer. These details can be applied to the technology described in JP-A-2000-352620, and are described below. What is antistatic processing?
When the resin film is handled, the resin film is provided with a function of preventing the resin film from being charged. Specifically, this is performed by providing a layer containing an ion conductive substance or conductive fine particles. Here, the ionic conductive substance refers to a substance that exhibits electric conductivity and contains ions that are carriers that carry electricity, and examples thereof include ionic polymer compounds. Of these, preferred are those in which the conductive substance is in the form of fine particles, which are finely dispersed and added in the resin, and preferred conductive substances used in these include metal oxides and these. It is desirable to contain conductive fine particles composed of a composite oxide and ionicene conductive polymers or quaternary ammonium cation conductive polymer particles having an intermolecular crosslink as described in JP-A-9-203810. The preferred particle size is in the range of 5 nm to 10 μm, and the more preferred range depends on the type of fine particles used.

Examples of metal oxides that are conductive fine particles include ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂
O ₃ , SiO ₂ , MgO, BaO, MoO ₂ , V ₂ O ₅
And the like, or a composite oxide of these is preferable.
O, TiO ₂ and SnO ₂ are preferred. Examples of containing heteroatoms include, for example, addition of Al and In to ZnO, addition of Nb and Ta to TiO ₂ , and addition of SnO.
_{For 2} , the addition of Sb, Nb, a halogen element or the like is effective. The addition amount of these different atoms is 0.01 to 2
It is preferably in the range of 5 mol%, and 0.1 to 15
It is particularly preferred that it is in the range of mol%. Furthermore,
Organic electronically conductive organic compounds can also be used. For example, polythiophene, polypyrrole, polyaniline, polyacetylene, polyphosphazene, and the like. These are preferably used in a complex with polystyrene sulfonic acid, perchloric acid or the like as an acid donor.

The optical film of the present invention can be provided with a transparent hard coat layer. Active ray curable resin or thermosetting resin is preferably used as the transparent hard coat layer. The actinic ray-curable resin layer refers to a layer mainly composed of a resin which cures through a crosslinking reaction or the like by irradiation with actinic rays such as ultraviolet rays or electron beams. Typical examples of the actinic ray-curable resin include an ultraviolet ray curable resin and an electron beam curable resin. Examples of the ultraviolet-curable resin include an ultraviolet-curable acrylic urethane-based resin, an ultraviolet-curable polyester acrylate-based resin, an ultraviolet-curable epoxy acrylate-based resin, an ultraviolet-curable polyol acrylate-based resin, and an ultraviolet-curable epoxy resin. be able to. UV-curable acrylic urethane-based resins are generally obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer, and further adding 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter acrylate includes methacrylate). Can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate, etc., and described in, for example, JP-A-59-151110.

The optical film of the present invention may be provided with an antireflection layer. Various types of antireflection layers are known, such as a single layer and a multilayer. However, a multilayer having a structure in which high-refractive-index layers and low-refractive-index layers are alternately laminated is generally used. Examples of the configuration include a layer composed of two layers of a high refractive index layer / a low refractive index layer in order from the transparent substrate side, or a layer having a different refractive index, and a medium refractive index layer (a transparent substrate or a hard substrate). A layer having a higher refractive index than the coating layer and a lower refractive index than the high refractive index layer) / a layer having a high refractive index / a layer having a low refractive index; Some suggestions have been made. Above all, from the viewpoint of durability, optical properties, cost, productivity, and the like, it is preferable to apply a high-refractive-index layer / a medium-refractive-index layer / a low-refractive-index layer on a substrate having a hard coat layer in this order. On the substrate surface, a high-refractive-index layer (which may be provided with a middle-refractive-index layer) and a low-refractive-index layer in the order of air are laminated in order. It is particularly preferable that the optical interference layer is formed by setting it to a certain value to form an anti-reflection layered product as the anti-reflection layer. The refractive index and the film thickness can be calculated by measuring the spectral reflectance. The optical film of the present invention may be subjected to a curl prevention process. What is anti-curl processing?
This function gives the function of rounding with the surface on which it is applied to the inside, but by performing this processing, one surface of the transparent resin film is subjected to some kind of surface treatment, and both surfaces have different degrees and types of surface When processing is performed, it functions to prevent curling with the surface inside. The anti-curl layer is provided on the side opposite to the side having the anti-glare layer or the anti-reflection layer of the substrate, or for example, an easy-adhesion layer may be applied on one side of a transparent resin film, Is applied.

The physical properties of the cellulose acylate film produced by the above method will be described in more detail. When the optical film of the present invention is a polarizing plate protective film, the thickness of the protective film is preferably in the range of 5 to 500 μm, more preferably in the range of 20 to 300 μm, and more preferably in the range of 30 to 150 μm. Most preferably. The retardation Re in the in-plane direction of the cellulose acylate film is 500 n
m, preferably less than 300 nm, more preferably less than 200 nm, even more preferably 100 nm or less, and 50 n
m or less, more preferably 30 nm or less. It is particularly preferably 10 nm or less, and more preferably 5 nm. The Rth of the cellulose acylate film is 100 μm
0 nm to 600 nm, and more preferably 0 nm to 600 nm
Used at 400 nm. In particular, it is preferable to use it at 0 nm to 250 nm. The angle θ (here, θ1) between the film forming direction (corresponding to the longitudinal direction) of the optical film of the present invention and the slow axis of the film is 0 °, + 90 °, or −9.
The closer to 0 °, the better. Here, θ1 is a narrow angle formed between the film forming direction and the slow axis, and is in a range of + 90 ° to −90 °. Particularly when used as a protective film for a polarizing plate, it contributes to an improvement in the degree of polarization of the obtained polarizing plate. Here, the slow axis is the direction in which the refractive index in the film plane is highest.

In the present invention, the cellulose acylate film formed as described above preferably has a vertical and horizontal dimensional shrinkage of ± 0.1% or less at 105 ° C. for 5 hours. . Further, the haze of the cellulose acylate film in terms of 80 μm is preferably 0.6% or less, more preferably 0.5% or less, and further preferably 0.1% or less. The lower limit of the haze value is not particularly limited. The tear strength of the optical film of the present invention is preferably 10 g or more, more preferably 12 g or more, and more preferably 1 g or more.
The weight is more preferably 5 g or more, more preferably 18 g or more, further preferably 20 g or more, and even more preferably 22 g or more. Moreover, the tensile strength of the cellulose acylate film is 50 N / mm.
It is preferably at least ² , and the elastic modulus is 3 kN / mm
It is preferably at least ² . The dynamic friction coefficient of the cellulose acylate film is preferably 0.40 or less, more preferably 0.35 or less. The optical film of the present invention has excellent dimensional stability, a temperature of 80 ° C.,
The dimensional shrinkage when left for 12 hours in an environment with a relative humidity of 90% RH is less than ± 0.5%, more preferably less than 0.3%, and still more preferably less than 0.1%; It is more preferably less than 0.08%, more preferably less than 0.06%, and still more preferably 0.02%.
Less than 4%.

First, the use of the cellulose acylate of the present invention will be briefly described, and the details will be described later. The optical film of the present invention is particularly useful for a polarizing plate protective film. When used as a protective film for a polarizing plate, the method for manufacturing the polarizing plate is not particularly limited, and the polarizing plate can be manufactured by a general method. There is a method in which the obtained cellulose acylate film is alkali-treated, and the polyvinyl alcohol film is immersed and stretched in an iodine solution, and bonded to both surfaces of the polarizer using a completely saponified polyvinyl alcohol aqueous solution. JP-A-6-94915 instead of the alkali treatment
And an easy bonding process as described in JP-A-6-118232. Examples of the adhesive used for bonding the protective film-treated surface and the polarizer include a polyvinyl alcohol-based adhesive such as polyvinyl alcohol and polyvinyl butyral, and a vinyl-based latex such as butyl acrylate.
The polarizing plate includes a polarizer and a protective film for protecting both surfaces of the polarizer, and further includes a protect film on one surface of the polarizer and a separate film on the other surface. The protect film and the separate film are used for protecting the polarizing plate at the time of shipping the polarizing plate, at the time of product inspection, and the like. In this case, the protective film is bonded for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the surface where the polarizing plate is bonded to the liquid crystal plate. The separate film is used for the purpose of covering the adhesive layer to be bonded to the liquid crystal plate, and is used on the side where the polarizing plate is bonded to the liquid crystal plate. In a liquid crystal display device, a substrate containing a liquid crystal is usually disposed between two polarizing plates, but a polarizing plate protective film to which the optical film of the present invention is applied can obtain excellent display properties regardless of the position. . In particular, since a transparent hard coat layer, an antiglare layer, an antireflection layer, and the like are provided on the polarizing plate protective film on the outermost surface on the display side of the liquid crystal display device, it is particularly preferable to use the polarizing plate protective film in this portion.

The cellulose acylate film of the invention can be used for various applications, and is particularly effective when used as an optical compensation sheet for a liquid crystal display. When a cellulose acylate film is used as the optical compensation sheet, the transmission axis of the polarizing element (described later) and the slow axis of the optical compensation sheet made of the cellulose acylate film may be arranged at any angle. A liquid crystal display device has a liquid crystal cell holding liquid crystal between two electrode substrates, two polarizing elements disposed on both sides thereof, and at least one sheet between the liquid crystal cell and the polarizing element. It has a configuration in which an optical compensation sheet is arranged. The liquid crystal layer of a liquid crystal cell is usually formed by enclosing liquid crystal in a space formed by sandwiching a spacer between two substrates. The transparent electrode layer is formed on a substrate as a transparent film containing a conductive substance. The liquid crystal cell may further be provided with a gas barrier layer, a hard coat layer or an undercoat layer (used for bonding the transparent electrode layer). These layers are usually provided on a substrate. The substrate of the liquid crystal cell is generally 50 μm to 2 m.
m. The optical compensation sheet has birefringence,
It is used for the purpose of removing coloring of the display screen of the liquid crystal display device and improving the viewing angle characteristics. The cellulose acylate film of the present invention itself can be used as an optical compensation sheet. Further, a function may be provided as an antireflection layer, an antiglare layer, a λ / 4 layer, or a biaxially stretched cellulose acylate film. Further, in order to improve the viewing angle of the liquid crystal display device, the cellulose acylate film of the present invention and a film exhibiting the opposite birefringence (positive / negative relationship) may be used as an optical compensation sheet. . The thickness range of the optical compensation sheet is the same as the preferred thickness of the film of the present invention described above.

The cellulose acylate film of the invention can be used for liquid crystal cells of various display modes. TN (Twisted Nematic), IPS (In-Plane Swit)
ching), FLC (Ferroelectric Liquid Crystal),
AFLC (Anti-ferroelectric Liquid Crystal), O
CB (Optically Compensatory Bend), STN (Suppe
Various display modes such as r Twisted Nematic), VA (Vertically Aligned) and HAN (Hybrid Aligned Nematic) have been proposed. In addition, a display mode in which the above-mentioned display mode is orientation-divided has been proposed. The cellulose acylate film is effective in a liquid crystal display device of any display mode. Further, the present invention is effective in any of the transmissive, reflective, and transflective liquid crystal display devices.
The cellulose acylate film of the invention may be used as a support for an optical compensation sheet of a TN type liquid crystal display device having a TN mode liquid crystal cell. The TN mode liquid crystal cell and the TN type liquid crystal display device have been well known for a long time. Optical compensatory sheets used for TN type liquid crystal display devices are disclosed in JP-A-3-9325 and JP-A-6-1484.
No. 29, JP-A-8-50206 and JP-A-9-2
There is a description in each publication of No. 6572. Also, Mori
i) Other papers (Jpn. J. Appl. Phys. Vol. 36 (1997) p. 14)
3, Jpn. J. Appl. Phys. Vol. 36 (1997) p. 1068). The cellulose acylate film of the present invention was
It may be used as a support for an optical compensation sheet of an STN liquid crystal display device having a TN mode liquid crystal cell. Generally, in an STN-type liquid crystal display device, rod-like liquid crystal molecules in a liquid crystal cell are twisted in a range of 90 to 360 degrees, and the refractive index anisotropy (△ n) of the rod-like liquid crystal molecules and the cell gap (d) ) Is in the range of 300 to 1500 nm.
The optical compensation sheet used for the STN liquid crystal display device is described in JP-A-2000-105316.

The cellulose acylate film of the present invention is particularly advantageously used as a support for an optical compensation sheet of a VA type liquid crystal display device having a VA mode liquid crystal cell. Re of optical compensation sheet used for VA liquid crystal display device
It is preferable that the retardation value be 0 to 150 nm and the Rth retardation value be 70 to 400 nm. The Re retardation value is more preferably from 20 to 70 nm. When two optically anisotropic polymer films are used in a VA liquid crystal display device, the Rth retardation value of the film is preferably from 70 to 250 nm. When one optically anisotropic polymer film is used in a VA liquid crystal display device, the R
The th retardation value is preferably from 150 to 400 nm. VA liquid crystal display devices are disclosed in, for example,
An orientation-divided system as described in Japanese Patent Application Laid-Open No. 0-123576 may be used. The cellulose acylate film of the invention is advantageously used as a support for an optical compensation sheet of an OCB type liquid crystal display device having an OCB mode liquid crystal cell or a HAN type liquid crystal display device having a HAN mode liquid crystal cell. In the optical compensatory sheet used for the OCB type liquid crystal display device or the HAN type liquid crystal display device, it is preferable that the direction in which the absolute value of the retardation becomes minimum does not exist in the plane of the optical compensatory sheet nor in the normal direction. The optical properties of the optical compensatory sheet used in the OCB type liquid crystal display device or the HAN type liquid crystal display device also include the optical properties of the optically anisotropic layer, the optical properties of the support, and the optically anisotropic layer and the support. Is determined by the arrangement. OC
An optical compensatory sheet used for a B-type liquid crystal display device or a HAN type liquid crystal display device is disclosed in JP-A-9-197497.
There is a description in the publication. Also described in a paper by Mori et al. (Jpn. J. Appl. Phys. Vol. 38 (1999) p. 2837).

The cellulose acylate film of the present invention can be made of TN type, STN type, HAN type, GH (Guest-Host).
It is also used advantageously as an optical compensation sheet of a reflection type liquid crystal display device. These display modes have been well known since ancient times. The TN type reflection type liquid crystal display device is described in JP-A-10-123478, WO98848320, and Japanese Patent No. 30222477. Regarding the optical compensation sheet used for the reflection type liquid crystal display device, WO00
-65384. The cellulose acylate film of the present invention is manufactured by ASM (Axially Symmetric Aligne).
d Microcell) It is also advantageously used as a support for an optical compensation sheet of an ASM type liquid crystal display device having a liquid crystal cell of a mode. The ASM mode liquid crystal cell is characterized in that the thickness of the cell is maintained by a resin spacer whose position can be adjusted. Other properties are the same as those of the TN mode liquid crystal cell. As for the ASM mode liquid crystal cell and the ASM type liquid crystal display device, a paper by Kume et al.
al., SID98 Digest 1089 (1998)).

[0102]

EXAMPLES In each of the examples, cellulose acylate,
The chemical and physical properties of solutions and films are
It was measured and calculated as follows.

(1) Viscosity of Cellulose Acylate Solution The obtained cellulose acylate solution was heated to 50 ° C.
The solution viscosity at that temperature was measured.

(2) Elongation of Cellulose Acylate Film at Peeling The obtained cellulose acylate solution was heated to 50 ° C.
A cellulose acylate solution having a width of 20 cm was cast on a smooth and uneven SUS metal plate which had been previously heated to 5 ° C. so as to have a dry film thickness of 100 μm. Note that a 100 μm-thick cellulose triacetate film was provided at the end of the SUS plate. One minute after the casting, the cellulose triacetate film at the end was held, and the cellulose acylate film was peeled off at right angles. At this time, the peeling speed was 60 cm / min, the length of the cellulose acylate film peeled per 20 cm length on the SUS plate was measured, and the elongation percentage per 20 cm was expressed in%.

(3) Unevenness of the film (abbreviated as unevenness) The obtained film was visually observed, and the unevenness of coating on the surface was evaluated as follows. A: No coating unevenness was observed on the film surface. B: Coating unevenness was slightly observed on the film surface. C: considerable coating unevenness was observed on the film surface. D: Irregularities were observed on the film surface, and many coating irregularities were observed.

(4) Film spots (abbreviated as spots) The obtained film was visually observed, and spots on the surface were evaluated as follows. A: No bumps were found on the film surface. B: Slight bumps were observed on the film surface. C: Significant bumps were observed on the film surface. D: Irregularities were observed on the film surface, and a lot of bumps were observed.

(5) The haze of the film was measured using a haze meter (Model 1001DP, manufactured by Nippon Denshoku Industries Co., Ltd.).

Example 1 (1-1) Preparation of Cellulose Acylate Solution In a 5 L glass container having stirring blades, the cellulose acylate shown in Table 1 was thoroughly stirred and dispersed in the following solvent mixed solution. Rate powder (flakes) was gradually added, and the whole was charged to 2 kg. The solvents methyl acetate, butanol, acetone, methanol, and ethanol all used had a water content of 0.2% by mass or less. First, a powder of cellulose triacetate was charged into a dispersion tank, charged with nitrogen gas, and dispersed for 30 minutes by a dissolver type eccentric stirring shaft and a stirrer having an anchor blade at the center axis. Dispersion start temperature is 30
° C. After the dispersion, the high-speed stirring was stopped, and the peripheral speed of the anchor blade was set to 0.5 m / sec, and the mixture was further stirred for 100 minutes to swell the cellulose triacetate flakes. 0.12MP in the tank with nitrogen gas until swelling ends
a. At this time, the oxygen concentration in the tank was less than 2 vol%, and a state in which there was no problem in explosion protection was maintained. It was also confirmed that the water content in the dope was 0.2% by mass or less. The composition of the cellulose acylate solution is as follows.

Cellulose triacetate (substitution degree 2.8)
2, viscosity average degree of polymerization 305, water content 0.3 mass%, viscosity of 6 mass% in methylene chloride solution 296 mPa ·
s, average particle diameter 1.4 mm, standard deviation 0.4 mm
(20 parts by mass), methyl acetate (58 parts by mass), acetone (5 parts by mass), methyl ethyl ketone (5 parts by mass)
Parts by mass), ethanol (5 parts by mass), butanol (5 parts by mass), plasticizer A (ditrimethylolpropanetetraacetate) (1.2 parts by mass), plasticizer B (triphenyl phosphate) (1.2 parts by mass) Parts), UV agent a (2, 4
-Bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-
Triazine (0.2 parts by mass), UV agent b (2 (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl)-
5-chlorobenzotriazole) (0.2 parts by mass), U
V agent c (2 (2′-hydroxy-3 ′, 5′-di-tert
-Amylphenyl) -5-chlorobenzotriazole)
(0.2 parts by mass), fine particles (silicon dioxide (particle size: 20 n)
m), Mohs hardness about 7) (0.05 parts by mass), formula (I
The material of the ester alcohol (described in Table 1) represented by V) was used. The main solvent used herein, methyl acetate, has a solubility parameter of 19.6, and acetone used in combination has a solubility parameter of 20.3. Furthermore, the cellulose triacetate used here has a residual acetic acid content of 0.1% by mass or less and a Ca content of 0.1% by mass.
05% by mass, Mg is 0.007% by mass, and F
e was 5 ppm. The acetyl group at the 6-position is 0.95
And was 32.2% of the total acetyl. The acetone extractables were 11% by mass, the ratio of the weight average molecular weight to the number average molecular weight was 0.5, and the distribution was uniform. The haze is 0.08, the transparency is 93.5%, and the Tg
Was 160 ° C., and the heat of crystallization was 6.2 J / g.

(1-2) Cellulose Triacetate Film Solution The resulting non-uniform gel solution was fed by a screw pump and passed through a cooling part at -70 ° C. for 3 minutes. Cooling was carried out using a −80 ° C. refrigerant cooled by a refrigerator. Then, the solution obtained by cooling is transferred to a stainless steel container, heated to 50 ° C., and stirred for 2 hours.
# 63), and further through a filter paper (FH025, manufactured by Pall Corporation) having an absolute filtration accuracy of 2.5 μm.

(1-3) Preparation of Cellulose Triacetate Film A filtered cellulose triacetate solution at 50 ° C.
It was cast on a mirror-finished stainless steel support through a casting gieser. The temperature of the support was 5 ° C., the casting speed was 3 m / min, and the coating width was 30 cm. It was left at room temperature for 1 minute, and then a drying air at 55 ° C. was blown for drying. After 5 minutes, the film was peeled off from the mirror-finished stainless steel support (the solid content immediately after the peeling was about 30 to 60% by mass), and then 110 ° C, 10 minutes, and 150 ° C for 3 minutes.
After drying for 0 minutes (film temperature is about 140 ° C.), a cellulose triacetate film (film thickness: 80 μm) was obtained.

(1-4) Results Table 1 shows the solution viscosity, film elongation, film surface condition (unevenness, spots) and haze obtained when the ester alcohol represented by the formula (IV) was used. The evaluation results are described. The control sample 1-1 not using the ester alcohol represented by the formula (IV) has a large peeling elongation,
Unevenness, spots and haze were also inferior. On the other hand, Samples 1-2 to 1-14 of the present invention did not have a large increase in solution viscosity, and had a small peeling elongation,
The obtained film had good surface conditions (unevenness and bumps), small haze, and was excellent. On the other hand, comparative compound A,
Comparative samples 1-22 to 1-25 using B, C, D and E
Has a large peeling elongation and does not satisfy all of unevenness, spots and haze.

[0113]

[Table 1]

Example 2 Samples 1-4 of the present invention
(1-2) Sample 2 was prepared in exactly the same manner as in Example 1 except that the cellulose triacetate film solution was changed as follows.
-4 was obtained.

(1-2) Cellulose triacetate film solution of the obtained non-uniform gel-like solution was fed by a screw pump, and passed through a heated portion heated and pressurized to 180 ° C. and 1 Mpa for 3 minutes. , 110 ° C., 1 Mpa, heated and pressurized, and filtered through a filter paper having an absolute filtration accuracy of 0.01 mm (manufactured by Toyo Roshi Kaisha, Ltd., # 63). Further, a filter paper having an absolute filtration accuracy of 0.0025 mm (manufactured by Pall Corporation, FH025) ).

(2-1) Result The obtained sample 2-4 of the present invention showed no increase in solution viscosity and a small elongation after peeling, and the surface state (unevenness, bumps) of the obtained film And the haze was as small as 0.4 and excellent. From this, it was confirmed that in the present invention, a cellulose acetate solution and a cellulose acetate film excellent in high-temperature and high-pressure dissolution can be produced.

Example 3 Sample 3-8 of the present invention was prepared in exactly the same manner as in Example 1 except that both plasticizers A and B were removed as 0 parts by mass. Produced. The obtained sample 3-8 has no increase in solution viscosity, a small peeling elongation, a good surface condition (unevenness and bumps) of the obtained film, and a small haze of 0.4, which is excellent. Met. On the other hand, when the bending test was conducted, Sample 1-8 was 103 times, whereas Sample 3-8 which was within the scope of the present invention but did not have a plasticizer had a cut resistance test of 91 times, which was a practical problem. None but slightly inferior.
Therefore, it is clear that in the present invention, it is a more preferable embodiment that the cellulose acylate film contains a plasticizer. Here, the evaluation of the bending strength was performed for a sample of 120 m.
The mx 120 mm was humidified at 23 ° C and 65% RH for 2 hours, and the number of reciprocations until cutting by bending according to ISO 8776-1988 was measured and evaluated.

Example 4 Sample 4-6 of the present invention was prepared in exactly the same manner as in Example 1 except that UV agents a, b, and c were all removed as 0 parts by mass in Sample 1-6 of Example 1. No. 6 was produced. The obtained sample 4-6 was excellent in that the solution viscosity was not increased, the peeling elongation was small, the surface condition (unevenness and bumps) of the obtained film was good, and the haze was as small as 0.3. Met. On the other hand, when the light-fading test was performed on a xenon lamp at 30,000 lux for one month, the sample 1
Although -6 is 0.7%, the haze is within the range of the present invention, but the haze of sample 4-6 is slightly increased to 1.1. Therefore, it is clear that in the present invention, it is a more preferable embodiment that the cellulose acylate film contains a UV agent.

Example 5 A sample 5-6 of the present invention was prepared in exactly the same manner as in Example 1 except that the fine particles of silica were removed from the sample 1-6 of Example 1 as 0 parts by mass. The obtained sample 5-6 had no increase in solution viscosity, had a small peeling elongation, had a good surface condition (unevenness and bumps), and had a small haze of 0.3, which was excellent. there were. On the other hand, when the two films were piled up and examined for slipperiness, Sample 1-6 could be moved smoothly, whereas Sample 5-6 was within the scope of the present invention. The movement was a little bad. Therefore, it is clear that in the present invention, it is a more preferable embodiment that the cellulose acylate film contains fine particles.

Example 6 Sample 1 of the present invention of Example 1
10, a cellulose triacetate film of Sample 6-10 of the present invention was prepared in exactly the same manner as in Example 1 except that the preparation of (1-2) cellulose triacetate film of Example 1 was changed as follows. That is, (1
A part of the cellulose triacetate solution obtained in -1) was sampled, and a cellulose triacetate solution (solution A) was prepared by diluting with 10% by mass of methyl acetate. According to the co-casting method described in JP-A-06-134993, the obtained solution was layered and co-cast with the cellulose triacetate solution of sample 1-3 and on both sides thereof. Thus, a co-cast cellulose triacetate film was obtained. The film thickness is 3 μm on both sides and 34 μm on the inside, and the total thickness is 4 μm.
The thickness was set to 0 μm. The surface state of the obtained sample 6-10 was smoother than that of the sample 1-3, and was more excellent without irregularities. Therefore, it is clear that co-casting is a more excellent aspect in the present invention.

[Example 7] In Example 1 described in JP-A-11-316378, the first transparent support was replaced with the cellulose triacetate film (second Film) thickness 100
Example 1 described in JP-A-11-316378 was carried out in exactly the same manner, except that the thickness was changed to μm, thereby producing a sample 7-6. The obtained elliptically polarizing plate had excellent optical characteristics. Therefore, it is clear that the use of a specific washing solution in the production process of the present invention is a preferable embodiment without any problem even if the cellulose acylate film produced thereafter is applied to an optical polarizing plate.

Example 8 Sample 1 of the present invention of Example 1
No. 8 to the cellulose triester film of JP-A-7-3
No. 33433, cellulose triacetate manufactured by Fuji Photo Film Co., Ltd. of Example 1 was used as the sample 1 of the present invention.
Example 1 described in JP-A-7-333433, except that the cellulose triacetate film of No. -8 was changed to
An optical compensation filter film sample was prepared in exactly the same manner as described above. The obtained filter film had excellent viewing angles in the right, left, up and down directions. Therefore, it is understood that the cellulose triacetate film of the present invention is excellent for optical use.

[Example 9] In the present invention, samples 1 to 12 which are used for various kinds of optical applications and are representative of the present invention were prepared as follows.
For example, a liquid crystal display device described in Example 1 of JP-A-10-48420, an optically anisotropic layer containing discotic liquid crystal molecules described in Example 1 of JP-A-9-26572, and polyvinyl alcohol are applied. Alignment film, JP-A-2
Good performance was obtained when used in the VA liquid crystal display device described in FIGS. 2 to 9 of 000-154261 and the OCB liquid crystal display device described in FIGS. 10 to 15 of JP-A-2000-154261. .

Example 10 Sample 1 of the present invention of Example 1
-9, except that the film thickness was changed to 120 μm, a sample 10-9 of the present invention as the film was produced in the same manner as in Example 1. One of the obtained films was provided with the first layer and the second layer (back layer composition) of Example 1 described in JP-A-4-73736, and a back layer having a cationic polymer as a conductive layer was provided. Produced. Further, the sample 105 of Example 1 described in JP-A-11-38568 was applied to the opposite side of the film base provided with the obtained back layer, to prepare a silver halide color photographic light-sensitive material. The obtained color film was excellent in image quality and had no problem in handling.

[0125]

According to the present invention, it is possible to provide a solution which has a good surface condition when the film is peeled off after the film is cast on a support of a cellulose acylate solution in the production process. it can. Further, the cellulose acylate film solution of the present invention can provide a cellulose acylate film free from unevenness and unevenness. Further, a cellulose triester film having excellent optical anisotropy and excellent film strength can be provided. Further, a cellulose triacetate film excellent as a support for a light-sensitive material can be produced.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02B 5/30 G03C 1/795 4J002 G03C 1/795 B29K 1:00 // B29K 1:00 B29L 7:00 B29L 7:00 G02B 1/10 A F-term (reference) 2H023 FA01 2H049 BA02 BA04 BA06 BA27 BA42 BB03 BB18 BB33 BB49 BB65 BC03 BC22 2K009 AA03 BB28 CC01 4F071 AA09 AA86 AA87 AF30 AH12 GC02 GE01 GC02 4J002 AB021 EH056 FD336 GA01 GP03

Claims (5)

[Claims] 1. A cellulose acylate comprising an ester alcohol in an amount of 0.5 to 25% by mass of the cellulose acylate, wherein the ester alcohol has 1 to 5 carbon atoms in a linking group having 3 to 20 carbon atoms. A total of 3 to 10 alcoholic hydroxyl groups and 1 to 5 acyloxy groups
A cellulose acylate film having a molecular structure in which it is bonded individually. 2. The linking group is a glycerin residue, an erythritol residue, an arabitol residue, a mannitol residue, a trimethylolpropane residue, a pentaerythritol residue,
Ditrimethylol residue, dipentaerythritol residue,
Sorbitol residue, sorbitan residue, butane-1,2,2
The cellulose acylate film according to claim 1, which is selected from the group consisting of a 3-triol residue and a pentane-2,3,4-triol residue. 3. A method for producing a cellulose acylate film by applying a cellulose acylate solution obtained by dissolving a cellulose acylate in an organic solvent, wherein the cellulose acylate solution contains 0.01 to 5% by mass of the cellulose acylate. % Of the ester alcohol, wherein the ester alcohol has 3 to 20 alcoholic hydroxyl groups and 1 to 5 acyloxy groups bonded to the linking group having 3 to 20 carbon atoms in total. A method for producing a cellulose acylate film, characterized by having a molecular structure as described above. 4. The method according to claim 3, wherein the organic solvent comprises a substantially non-chlorinated organic solvent. 5. The organic solvent according to claim 3, wherein the organic solvent is selected from the group consisting of ethers having 2 to 12 carbon atoms, ketones having 3 to 12 carbon atoms and esters having 2 to 12 carbon atoms. Production method.