JP2003226761A - Cellulose acylate film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cellulose acylate film having an excellent surface state by casting a solution in which a cellulose acylate is dissolved in a stable state in an organic solvent. <P>SOLUTION: The cellulose acylate film is prepared by a step comprising a casting step of casting a cellulose acylate solution containing a cellulose acylate whose degree of substitution on the hydroxyl groups of a cellulose meets all formulae (I) to (III): (I) 2.6≤SA+SB≤3.0, (II) 2.0≤SA≤3.0, and (III) 0≤SB≤0.8 (wherein SA is a degree of substitution of an acetyl group; and SB is a degree of substitution of a 3-22C acyl group), at least one calixarene derivative, and an organic solvent and having a total amount of the calixarene derivative of 0.05-10 wt.% and a concentration of the cellulose acylate of 5-40 wt.% based on the solution. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a cellulose acylate film useful for a silver halide photographic light-sensitive material or a liquid crystal image display device, a method for producing the cellulose acylate film, and an optical polarizing film using the cellulose acylate film. , Liquid crystal display devices, etc.

[0002]

2. Description of the Related Art Conventionally, an organic solvent of a cellulose acylate solution used for producing a cellulose acylate used for a silver halide photographic light-sensitive material or a liquid crystal image display device is a chlorine-containing carbonic acid such as methylene chloride. Hydrogen is used. Methylene chloride (boiling point 40 ° C)
Conventionally, it has been 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 manufacturing process and is easily dried. However, since methylene chloride has a low boiling point and is easily volatilized, it leaks a little in the handling process even in a closed facility and has a limit in recovery, and due to the problem that it cannot completely prevent its release into the atmosphere, its environmental safety. Improvement is desired in terms of. Therefore, in order to solve this problem, using methylene chloride as a solvent, it was investigated to prepare a cellulose acylate solution having a higher concentration and reduce the amount of the solvent used. And the improvement was desired. Therefore, a search for a solvent for cellulose acylate other than methylene chloride has been made. Known as organic solvents having solubility in cellulose acylate, particularly cellulose triester, are 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. However, these organic solvents have not been sufficiently soluble by the conventional dissolution method to be practically usable.

As a solution to this problem, J. M. G. Cowie
Et al., Makromol. chem. 143, page 105 (1971), cellulose triacetate (acetylation degree 60.1% to 61.3%) in acetone at -80 ° C.
To -70 ° C. and then warmed to 0.
It is reported that a dilute solution of 5 to 5% by weight can be obtained. The method of dissolving cellulose acylate at such a low temperature is referred to as a cooling dissolution method in the present invention. Kenji Uede et al., Journal of Textile Machinery, 34, 57-61 (19
81) "Dry-spinning of cellulose triacetate from acetone solution" describes the spinning technique using the cooling dissolution method. Further, in JP-A-9-95538, JP-A-9-95544 and JP-A-9-95557, cellulose acylate is dissolved by a cooling dissolution method using a chlorine-free organic solvent based on the above-mentioned technique. Is disclosed. The non-chlorine organic solvent used at that time is an organic solvent selected from ethers, ketones or esters, and cellulose acylate is dissolved by a cooling dissolution method to produce a film. Acetone, 2-methoxyethyl acetate, cyclohexanone, ethyl formate, methyl acetate, etc. are preferred as these specific organic solvents. further,
JP-A No. 11-60752 proposes to add a fluoroalcohol to a cellulose acylate solution for improvement. However, the addition of fluoroalcohol may cause a problem that the cellulose acylate has a poor surface condition due to its strong oil and water repellency.

On the other hand, the cellulose acylate film is
Generally, it is manufactured by a solvent cast method or a melt cast method. In the solvent cast 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. In the melt casting method, which is another 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 practice. In the recent solvent cast method, it is possible to improve the productivity of the film-forming process by shortening the time required for casting the dope on the metal support and peeling the molded film on the metal support. It is an issue. In particular, when obtaining a cellulose acylate film by the solvent cast method, in the case of a cellulose acylate solution dissolved by using the above-mentioned non-chlorine organic solvent, the cellulose acylate film is peeled from the metal support in a short time. Is difficult, and inferior productivity is a problem.

In this method, cellulose acylate is cast on a band or a drum which is a metal support, dried or cooled to give a gel film having high strength, which is 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 it is subsequently dried is insufficient. Methylene chloride, a chlorine-based organic solvent that has been conventionally used, can volatilize the solvent in a short time because of its low boiling point, and can significantly increase the solid content concentration in the cellulose acylate film, thereby containing the solvent. Since it is possible to increase the film strength of the cellulose acylate film, there was no particular problem. However, when the non-chlorine-based solvent preferably used in the present invention is used, it is not possible to expect volatilization of the solvent in a short time because it has a high boiling point and a strong affinity with cellulose acylate. Therefore, after peeling the solvent-containing cellulose acylate film from the metal support, the flatness of the cellulose acylate film cannot be maintained during the handling during drying, and the cellulose acylate film at the tenter holding part or the central part cannot be maintained. There is a problem that the rate film is elongated and the flatness is remarkably deteriorated. In particular, a step of casting the cellulose acylate solution on a cooled band-shaped or drum-shaped metal support, peeling off the cellulose acylate film containing a large amount of the solvent from the metal support without drying, and then drying. This problem is significant when it is in a cast and dry form with

[0006]

In the present invention, cellulose obtained by casting an organic solvent solution of cellulose acylate in an organic solvent, peeling the cellulose acylate film containing the organic solvent from the metal support, and drying. It is an object of the present invention to provide a cellulose acylate film having an excellent surface condition, which is an acylate film.

More specifically, the object of the present invention is to cast a cellulose acylate solution prepared by a room temperature dissolution method, a cooling dissolution method or a high temperature high pressure dissolution method using an organic solvent to obtain a cellulose cellulose film having an excellent surface condition. To provide. Furthermore, a further object of the present invention is that after casting, the film can be easily peeled from the support for drying, and the strength of the cellulose acylate film containing an organic solvent is excellent. It is to provide a method for producing a cellulose acylate film having excellent properties.

[0008]

The above-mentioned problems of the present invention have been solved by the solution means described in 1) below. Hereinafter, the preferred embodiments 2) and the following will be listed. 1) The degree of substitution of cellulose with hydroxyl groups is represented by the following formula (I):
A cellulose acylate solution containing all of (III), at least one calixarene derivative, and an organic solvent, wherein the total amount of the calixarene derivative is 0.05 to 10% by weight of the cellulose acylate. And a cellulose acylate film produced by a process including a casting process of casting a cellulose acylate solution having a concentration of cellulose acylate of 5 to 40% by weight of the solution. (I) 2.6 ≦ SA + SB ≦ 3.0 (II) 2.0 ≦ SA ≦ 3.0 (III) 0 ≦ SB ≦ 0.8 SA is the substitution degree of the acetyl group, and SB is the number of carbon atoms of 3 to 3.
22 represents the degree of substitution of the acyl group of 22. SA is an acetyl group, S
B also represents an acyl group of 3 to 22.

2) The cellulose acylate film according to 1), wherein the sum of the substitution degrees of SA and SB at the 6-position of the cellulose acylate is 0.8 or more. 3) In cellulose acylate substituted with an acetyl group and an acyl group having 3 to 22 carbon atoms, the sum of the substitution degrees of SA and SB is 2.80 to 2.95, and the substitution degree of SB is 0 to 0. 0.8 and 30% or more of SB is present as a substituent of the 6-position hydroxyl group, and the sum of the substitution degrees of SA and SB at the 6-position is 0.85 or more 1) or 2). Cellulose acylate film. 4) The acyl group having 3 to 22 carbon atoms is selected from the group consisting of a substituted or unsubstituted alkylcarbonyl group, alkenylcarbonyl group, aromatic carbonyl group, and aromatic alkylcarbonyl group 1) to 3 ) Any one
The cellulose acylate film described in 1. 5) an acyl group having 3 to 22 carbon atoms is propionyl,
Butanoyl, heptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl,
The cellulose acylate film according to 4) selected from the group consisting of iso-butanoyl, t-butanoyl, cyclohexanecarbonyl, oleoyl, benzoyl, naphthylcarbonyl, and cinnamoyl.

6) The organic solvent is a non-chlorine type organic solvent,
And, the non-chlorine organic solvent is at least one solvent selected from ethers having 3 to 12 carbon atoms, ketones having 3 to 12 carbon atoms, and esters having 3 to 12 carbon atoms. 1) The cellulose acylate film according to any one of 1) to 5). 7) Ethers having 3 to 12 carbon atoms are diisopropyl ether, dimethoxymethane, dimethoxyethane,
It is an organic solvent selected from the group consisting of 1,4-dioxane, 1,3-dioxane, 1,3-dioxolane, tetrahydrofuran, anisole and phenetole, and the ketones having 3 to 12 carbon atoms are acetone and methyl ethyl ketone. , An organic solvent selected from the group consisting of diethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and methylcyclohexanone, wherein the ester having 3 to 12 carbon atoms is ethyl formate, propyl formate. The cellulose acylate film according to any one of 1) to 6), which is an organic solvent selected from the group consisting of, pentyl formate, methyl acetate, ethyl acetate, propyl acetate and pentyl acetate. 8) The organic solvent is a mixed solvent of three or more kinds different from each other, and the first solvent is at least one selected from the group consisting of methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, dioxolane and dioxane, or A mixed solvent thereof, wherein the second solvent is selected from the group consisting of ketones or acetoacetic acid esters having 4 to 7 carbon atoms, and the third solvent is selected from alcohols or hydrocarbons having 1 to 10 carbon atoms. Selected, more preferably 1 carbon
The cellulose acylate film according to any one of 1) to 7), which is an alcohol of 8 to 8. In addition, when the first solvent is a solvent of two or more kinds, the second solvent may be omitted. 9) The first solvent is 20 to 90% by mass, and the second solvent is 5 to 5.
The cellulose acylate film according to any one of 1) to 8), which is a mixed solvent containing 60% by mass and a third solvent in a ratio of 5 to 30% by mass.

10) The cellulose acylate film according to any one of 1) to 9), which is prepared from a cellulose acylate solution obtained by at least one of the following preparation methods (1) to (3). (1) a step of swelling cellulose acylate with an organic solvent at -20 to 40 ° C, and a step of heating a mixture of cellulose acylate and an organic solvent to 0 to 57 ° C to dissolve cellulose acetate in the organic solvent. A method for preparing a cellulose acetate solution containing the same. (2) The step of swelling the cellulose acylate with an organic solvent at -20 to 55 ° C, the step of cooling the mixture of cellulose acylate and the organic solvent to -100 to -10 ° C, and the cooled mixture to 0 to 57 ° C. A method for preparing a cellulose acetate solution, which comprises the step of heating and dissolving cellulose acetate in an organic solvent. (3) Step of swelling cellulose acylate with an organic solvent at -20 to 55 ° C, 60 to 2 at 0.2 to 30 MPa
Heating the mixture of cellulose acylate and organic solvent under high pressure and high temperature of 40 ° C., and heating the mixture to 0
A method for preparing a cellulose acylate solution, which comprises the steps of cooling to ~ 57 ° C and dissolving the cellulose acylate in an organic solvent. 11) When the cellulose acylate and the organic solvent are mixed, 90% by mass or more of the cellulose acylate is 0.1 to 0.1% by mass.
Using a particle having a particle size of 5 mm, including a step of filtering the obtained cellulose acylate solution, a step of casting the cellulose acylate solution on a support, a step of stripping off, and a film by evaporating the solvent. The cellulose acylate film according to any one of 1) to 10), which is produced by a drying step of forming a film and a step of winding the produced cellulose acylate film.

12) At least one of the following (1) to (4)
The cellulose acylate film according to any one of 1) to 11), which is a cellulose acylate solution satisfying the following requirements. (1) The cellulose acylate solution contains at least one plasticizer in an amount of 0.1 to 20% by weight based on the cellulose acylate. (2) The cellulose acylate solution contains at least one kind of ultraviolet absorber in an amount of 0.001 with respect to the cellulose acylate.
~ 5% by weight. (3) The cellulose acylate solution contains at least one kind of fine particle powder in an amount of 0.001-
Contains 5% by weight. (4) The cellulose acylate solution contains at least one fluorosurfactant in an amount of 0.
001 to 2% by weight. 13) Prepared from a cellulose acylate solution having a viscosity of 1 to 300 Pa · sec at 40 ° C. and a dynamic storage elastic modulus at −5 ° C. of 10 to 15 million Pa of the cellulose acylate solution 1 ) To 12) The cellulose acylate film as described in any one of the above. 14) The molecular weight of aggregates of cellulose acylate in the diluted solution prepared by adding 0.1 to 1% by mass of the cellulose acylate solution in the organic solvent system having the same composition is 1 to 10,000,000 (25
C.) A cellulose acylate film according to any one of 1) to 13) prepared from a cellulose acylate solution.

15) The cellulose acylate film according to any one of 1) to 14), which is a production step in which two or more kinds of cellulose acylate solutions are co-cast in the casting step. 16) The cellulose acylate film used as an optical protective layer, wherein the film thickness is 10 to 200 μm, and the cellulose acylate film according to any one of 1) to 15). 17) An optical polarizing film using the cellulose acylate film described in 16). 18) A liquid crystal display material using the cellulose acylate film according to 16). 19) The produced cellulose acylate film is a support for a silver halide photographic light-sensitive material and has a film thickness of 3
The cellulose acylate film according to any one of 1) to 15), which has a thickness of 0 to 250 μm. 20) The cellulose acylate film according to any one of 1) to 5), wherein the organic solvent is methylene chloride.

First, the cellulose acylate preferably used in the present invention will be described in detail. The cellulose acylate of the present invention is not particularly limited as long as it exhibits the effects of the present invention. In the present invention, two or more different types of cellulose acylate may be mixed. However, among them, preferred cellulose acylates include the following materials. That is, the cellulose acylate is a cellulose acylate in which the substitution degree of the hydroxyl group of cellulose 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 In the formula, SA and SB are acyl groups substituted with a hydroxyl group of cellulose. , SA is the substitution degree of the acetyl group, and SB is the substitution degree of the acyl group having 3 to 22 carbon atoms.

The β-1,4-bonded glucose unit constituting the cellulose has a free hydroxyl group at the 2-position, 3-position and 6-position. Cellulose acylate is a polymer obtained by esterifying some or all of these hydroxyl groups with an acyl group. The degree of acyl substitution is 2
For each of the 3rd, 6th, and 6th positions, the ratio of esterification of cellulose (100% esterification means a substitution degree of 1) is meant. In the present invention, the sum of the substitution degrees of SA and SB of the hydroxyl group is more preferably 2.7 to 2.96, and particularly preferably 2.80 to 2.95. Also,
The substitution degree of SB is 0 to 0.8, and particularly 0 to 0.6. Further, 28% or more of SB is a substituent of the 6-position hydroxyl group, more preferably 30% or more is a substituent of the 6-position hydroxyl group, further preferably 31%, particularly preferably 32%.
It is also preferable that the above is a substituent of the 6-position hydroxyl group. Further, a cellulose acylate film having a total substitution degree of SA and SB at the 6-position of cellulose acylate of 0.8 or more, further 0.85, and particularly 0.90 can be mentioned. With these cellulose acylate films, a solution having a favorable solubility can be prepared, and particularly in a non-chlorine organic solvent, a good solution can be prepared.

The acyl group (SB) having 3 to 22 carbon atoms in the cellulose acylate used in the present invention may be an aliphatic group or an aryl group and is not particularly limited. They are, for example, alkylcarbonyl esters of cellulose,
Alkenyl carbonyl ester, aromatic carbonyl ester, aromatic alkyl carbonyl ester, etc., each of which may further have a substituted group. These preferred SBs include propionyl, butanoyl, keptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl,
Examples thereof include iso-butanoyl, t-butanoyl, cyclohexanecarbonyl, oleoyl, benzoyl, naphthylcarbonyl and cinnamoyl groups. Among these, preferable SB is propionyl, butanoyl, dodecanoyl, octadecanoyl, t-butanoyl, oleoyl, benzoyl, naphthylcarbonyl, cinnamoyl and the like.

The basic principle of the method for synthesizing cellulose acylate is described in Ueda et al., Wood Chemistry, pages 180-190 (Kyoritsu Shuppan, 1968). A typical synthesis method is a liquid phase acetylation method using a carboxylic acid anhydride-acetic acid-sulfuric acid catalyst. Specifically, after pre-treating a cellulose raw material such as cotton linter or wood pulp with an appropriate amount of acetic acid, the mixture is put into a pre-cooled carboxylic oxidation mixed solution to be esterified to obtain a complete cellulose acylate (2nd, 3rd and 6th). The total degree of acyl substitution at positions is about 3.00). The above-mentioned carboxylic oxidation mixed liquid generally contains acetic acid as a solvent, carboxylic acid anhydride as an esterifying agent, and sulfuric acid as a catalyst. Carboxylic anhydride is usually used in a stoichiometric excess over the total of the cellulose that reacts with it and the water present in the system. After the completion of the acylation reaction, in order to hydrolyze the excess carboxylic anhydride remaining in the system and to partially neutralize the esterification catalyst, a neutralizing agent (for example, calcium, magnesium,
An aqueous solution of iron, aluminum or zinc carbonate, acetate or oxide) is added. Next, the obtained complete cellulose acylate is saponified and aged by keeping it at 50 to 90 ° C. in the presence of a small amount of an acetylation reaction catalyst (generally, residual sulfuric acid), to obtain a desired degree of acyl substitution and polymerization. The cellulose acylate having a certain degree is changed. When the desired cellulose acylate is obtained, the catalyst remaining in the system is completely neutralized using the above-mentioned neutralizing agent, or
Alternatively, without neutralization, the cellulose acylate solution is added to water or diluted sulfuric acid (or water or diluted sulfuric acid is added to the cellulose acylate solution) to separate the cellulose acylate, which is then washed and stabilized by a treatment. Obtain cellulose acylate.

In the cellulose acylate film of the invention, it is preferable that the polymer component constituting the film is substantially composed of cellulose acylate having the above definition. “Substantially” means 55% by mass of all polymer components
Or more (preferably 70% by mass or more, more preferably 8
0 mass% or more). Cellulose acylate particles are preferably used as a raw material for film production. 90% by mass or more of the particles used are 0.1-5 mm
It is preferable to have a particle size of. Further, it is preferable that 50% by mass or more of the particles used have a particle diameter of 0.2 to 4 mm. The cellulose acylate particles preferably have a flat or spherical shape as much as possible.

The degree of polymerization of cellulose acylate preferably used in the present invention is a viscosity average degree of polymerization of 200 to 700,
Preferably 230-550, more preferably 230-3
50, and particularly preferably the viscosity average degree of polymerization 240 to 3
Twenty. The average degree of polymerization is determined by the limiting viscosity method of Uda et al. (Kazuo Uda, Hideo Saito, Journal of the Fiber Society, Vol. 18, No. 1, 105
~ 120, 1962). Further, it is described in detail in JP-A-9-95538.

When the low molecular weight component is removed, the average molecular weight (average degree of polymerization) increases, but the viscosity becomes 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 a usual method. The removal of low molecular components can be carried out by washing the cellulose acylate with a suitable organic solvent. When producing a cellulose citrate containing a small amount of low-molecular components, it is preferable to adjust the amount of the sulfuric acid catalyst in the acetylation reaction to 0.5 to 25 parts by mass with respect to 100 parts by weight of cellulose. When the amount of the sulfuric acid catalyst is in the above range, it is possible to synthesize a cellulose acylate which is preferable in terms of molecular weight distribution (uniform molecular weight distribution). When the cellulose acylate of the invention is used during film production, its water content is preferably 2% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.7% by mass or less. It is a cellulose acylate having a water content. Generally, cellulose acylate contains water and is known to be 2.5 to 5 mass%. In the present invention, in order to obtain the water content of the cellulose acylate, it is necessary to dry it, and the method is not particularly limited as long as the desired water content can be obtained.
For these cellulose acylates of the present invention, the raw material cotton and the synthesis method are described in JIII Journal of Technical Disclosure (Publication No. 2001-2001).
1745, published by Mar. 15, 2001, Institute of Invention) on pages 7-12.

Next, the calixarene derivative of the present invention will be described. The calixarene derivative is a cyclic oligomer formed by a condensation reaction between phenol and formaldehyde. In the present invention, any calixarene derivative applicable to this definition can be used without particular limitation. The number of carbon atoms constituting this ring is 12 to 3
It is 0, preferably 16 to 24.

Next, the calixarene derivative of the present invention will be described in detail. Here, the gelation in the present invention means that by adding a calixarene derivative to a cellulose acylate solution, the calixarene derivatives are interacted with each other or with the cellulose acylate, and further due to the interaction with an organic solvent or the like. The fluidity of the solution is lowered or the solution is solidified to form a so-called gelled state. That is, the calixarene derivative of the present invention is a secondary non-covalent bond such as hydrogen bond, electrostatic interaction, coordination bond, van der Waals force, and π-π electron interaction in an organic solvent of cellulose acylate. It forms a gel structure by self-association with a dynamic interaction as a driving force.

The compounds which are these calixarene derivatives are described, for example, in J. Chem. Soc. Japan, Ind. C.
hem.Soc., 46,779 (1943), J. Am. Chem.Soc., 111,5542
(1989), J. Chem. Soc., Chem. Commun., 1993,390, Ang
ew. Chem. Int. Ed. Engl., 35, 1949 (1996), Chem. Let
t., 1996, 885, J. Chem. Soc., Chem. Commun., 1997,
You can refer to 545. In addition, the collection of polymer papers,
VOL.55, No.10, 585-589 (Oct., 1998), Surface, VOL.3
6, No. 6, 291-303 (1998), Textile and Industry, VOL. 56, No.
11, 329-332 (2000), JP-A-7-247473, JP-A-7-24
7474, JP-A-7-247475, JP-A-7-300578, JP-A-10-
265761, JP-A-7-208446, JP-A-2000-3003, JP-A-5-
The materials described in 230435 and JP-A-5-320617 can be applied.

The preferred specific compounds of the calixarene derivative are described below, but the invention is not limited thereto.

[Chemical 1] In the formula, l, m and n are each an integer of 0 to 7, l + m + n = 3 to 7, and X ¹ and X ² are
It is an atomic group represented by -R or -OR which is the same or different from each other (wherein R represents a linear or branched alkyl group having 6 to 22 carbon atoms, an alkenyl group, an alkynyl group, or a hydroxyalkyl group). Shown), Y ¹ and Y ² are
The same or different atomic groups, -CH = N-,
_{-CH 2 -NH -, - CH =} CH -, - N = N -, - C
Selected from O—O— and —NO═N—, Z ¹ , Z ² and Z ³ are the same or different atomic groups from each other,
OH or its substituent is shown.

That is, Z¹, Z^TwoAnd Z^ThreeIs Cali
Xarene phenolic OH groups or
Depending on the intended function of Cuslane, the OH group is
Various functional groups that have been substituted or introduced are shown. did
Thus, examples of such substituents include -OR¹, -O
CH_TwoCOOR^Two, OCH_TwoCOR^Three, Or -OCH
_TwoCON (R^Four)_Two(However,
R¹, R^Two, R^ThreeAnd R ^FourIs a linear or branched
Kill, alkenyl, alkynyl or hydroxy
An alkyl group having 1 to 18 carbon atoms,
It is generally from 1 to 10. Z¹, Z^TwoAnd Z^ThreePreferred
A good example is -OCH_Three, -OC_ThreeH₇, -OC₆H_Thirteen
And so on.

The calixarene derivative represented by the general formula (Formula 1) is excellent in solubility and has a significantly lowered melting point and good solubility in many solvents. The Caaryx arene derivative of the present invention is specifically described in JP-A-5-271175 and JP-A-6-321883. A preferred specific example is the following structure.
[Chemical Formula 9] and [Chemical Formula 11] to [Chemical Formula 45] described in JP-A No. 175 and [Chemical Formula 2] to [Chemical Formula 1] described in JP-A-6-321883.
2]. Among these, specific examples of structural formulas are given below.

[0027]

[Chemical 2] Compound KA-1

[0028]

[Chemical 3] Compound KA-2

[0029]

[Chemical 4] Compound KA-3

[0030]

[Chemical 5] Compound KA-4

The calixarene derivative of the present invention is added to a cellulose acylate solution and exhibits a function as a gelling agent. Hereinafter, such an application will be described, but the application of the present invention is not limited to the following.

The calixarene derivative of the present invention is a
Containing 0.05 to 10% by mass relative to lulose acylate
However, more preferably 0.1 to 5 quality
%, More preferably 0.2 to 3% by mass
It is to let. Of the calixarene derivative of the present invention
In addition, the addition method is not particularly limited.
It may be added to the cellulose acylate solution as it is,
It may be dissolved in a desired organic solvent in advance and added. This and
The organic solvent used is the cellulose acylate of the present invention.
The solvent may be the same as or different from that of the solvent. Change
In addition, the cellulose acylate solution of the present invention is
Sylates, organic solvents and calixarene derivatives of the present invention
The conductors may be added to the melt tank separately and continuously
There is no problem even if all or all of them are added continuously at the same time.
Yes. Furthermore, after swelling in the first tank and then the second
Transfer to melting tank and heat or cool during transfer to melt
It may be understood or it may be dissolved in the second tank. this
Regarding JP-A-61-29031, JP-A-2000.
No. -273239.

The cellulose acylate solution of the present invention contains
Various additives (for example, plasticizers, UV inhibitors, deterioration inhibitors, optical anisotropy control agents, fine particles, release agents, infrared absorbers, etc.) can be added in each preparation step depending on the application. , They may be solid or oily. That is, the melting point and the boiling point are not particularly limited. For example, mixing of UV absorbing materials at 20 ° C. or lower and 20 ° C. or higher, mixing of plasticizers, and the like are also described, for example, in JP-A No. 2001-151901. Furthermore, the infrared absorbing dye is described in, for example, JP-A No. 2001-194522. Further, the addition may be carried out at any time in the dope preparation step, but may be carried out by adding a step of adding an additive to the final preparation step of the dope preparation step. Furthermore,
The addition amount of each material is not particularly limited as long as the function is exhibited. Further, when the cellulose acylate film is formed from multiple layers, the type and amount of the additive in each layer may be different. For example, it is described in Japanese Patent Application Laid-Open No. 2001-151902, but these are known techniques. Further details of these can be found in JIII Journal of Technical Disclosure (Kogi No. 2001-1745, March 1, 2001).
Materials described in detail on pages 16 to 22 by the Institute of Invention and Innovation, 5th day are preferably used.

Next, the organic solvent capable of dissolving the cellulose acylate of the present invention will be described. First, a non-chlorine organic solvent (organic solvent containing no chlorine) which is preferably used when preparing the cellulose acylate solution of the present invention will be described. In the present invention, the non-chlorine organic solvent is not particularly limited as long as the purpose can be achieved within the range in which the cellulose acylate can be dissolved, cast and film-formed. The non-chlorine organic solvent used in the present invention is preferably a solvent selected from esters, ketones, and ethers having 3 to 12 carbon atoms. The ester, ketone and ether may have a cyclic structure. Functional groups of esters, ketones and ethers (ie -CO
A compound having two or more of any one of O-, -CO- and -O-) can also be used as a main solvent and may have another functional group such as an alcoholic hydroxyl group. In the case of a main solvent having two or more kinds of functional groups, the number of carbon atoms may be within the specified range of the compound having any functional group. Examples of the esters having 3 to 12 carbon atoms include ethyl formate, propyl formate,
Mention may be made of pentyl formate, methyl acetate, ethyl acetate and pentyl acetate. Examples of ketones having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and methylcyclohexanone. Examples of ethers having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,
Included are 3-dioxolane, tetrahydrofuran, anisole and phenetole. Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol.

The non-chlorine type organic solvent used for the above cellulose acylate is selected from the various viewpoints described above, but is preferably as follows. That is, the preferred solvent of the cellulose acylate of the present invention is a mixed solvent of three or more kinds (first solvent,
A second solvent, and a third solvent), wherein the first solvent is at least one selected from methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, dioxolane, dioxane or a mixed solution thereof, The second solvent is selected from ketones or acetoacetic acid esters having 4 to 7 carbon atoms, and the third solvent is selected from alcohols or hydrocarbons having 1 to 10 carbon atoms, more preferably 1 to 1 carbon atoms. 8 alcohol. When the first solvent is a mixed solution of two or more kinds of solvents, the second solvent may be omitted. The first solvent is more preferably methyl acetate,
Acetone, methyl formate, ethyl formate, or a mixture thereof, and the second solvent is preferably methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl acetylacetate, or a mixture thereof.

The alcohol as the third solvent may be straight-chain, branched or cyclic, and is preferably saturated aliphatic hydrocarbon. The hydroxyl group of the alcohol may be any of primary to tertiary. Examples of alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-
Includes butanol, 2-butanol, t-butanol, 1-pentanol, 2-methyl-2-butanol and cyclohexanol. Fluorine-based alcohol is also used as the alcohol. For example, 2-fluoroethanol, 2,2,2-trifluoroethanol,
2,2,3,3-tetrafluoro-1-propanol etc. are also mentioned. Further, the hydrocarbon may be linear, branched or cyclic. Both aromatic hydrocarbons and aliphatic hydrocarbons can be used. The aliphatic hydrocarbon may be saturated or unsaturated.
Examples of hydrocarbons include cyclohexane, hexane, benzene, toluene and xylene. These third
The alcohol and the hydrocarbon as the solvent may be used alone or as a mixture of two or more kinds, and are not particularly limited. Third
As a solvent of, preferred specific compounds are alcohols such as methanol, ethanol, 1-propanol,
2-propanol, 1-butanol, 2-butanol,
And cyclohexanol, cyclohexane, hexane, especially methanol, ethanol,
They are 1-propanol, 2-propanol and 1-butanol.

The above-mentioned three kinds of mixed solvents must contain the first solvent in an amount of 20 to 95% by mass, the second solvent in an amount of 2 to 60% by mass, and the third solvent in an amount of 2 to 30% by mass. Is preferred, and further the first solvent is 30 to 90 mass%,
It is preferable that the second solvent is contained in an amount of 3 to 50% by mass and the third alcohol is contained in an amount of 3 to 25% by mass. Moreover, especially the 1st solvent is 30-90 mass%, and the 2nd solvent is 3-.
It is preferable that the content of the third solvent is 30% by mass, and the third solvent is alcohol, and the content is 3 to 15% by mass. Note that when the first solvent is a mixed liquid and the second solvent is not used, the first solvent is 20 to
90% by mass, the third solvent is preferably contained in a ratio of 5 to 30% by mass, further, the first solvent is 30 to 86% by mass, and the third solvent is further contained in 7 to 25% by mass. It is preferable. The above-mentioned non-chlorine organic solvent used in the present invention is described in more detail in Japan Institute of Invention and Innovation Technical Report (publication number 2001-1745, published on Mar. 15, 2001,
Inventive Society), pages 12-16. Examples of preferable combinations of non-chlorine-based organic solvents of the present invention include, but are not limited to, 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) , Mass part), methyl acetate / acetone / methanol / butanol / cyclohexane (75/10/5/5/5, mass part), methyl acetate / methyl ethyl ketone / methanol / butanol (80/10/5/5, mass) Part), Methyl acetate / acetone / methyl ethyl ketone / ethanol /
Isopropanol (75/10/10/5/7, parts by mass), methyl acetate / cyclopentanone / methanol /
Isopropanol (80/10/5/8, parts by mass),
Methyl acetate / acetone / butanol (85/5/5, parts by mass), methyl acetate / cyclopentanone / acetone /
Methanol / butanol (60/15/15/5/6,
Parts by mass), methyl acetate / cyclohexanone / methanol / hexane (70/20/5/5, parts by mass), methyl acetate / methyl ethyl ketone / acetone / methanol /
Ethanol (50/20/20/5/5, parts by mass),
Methyl acetate / 1,3 dioxolane / methanol / ethanol (70/20/5/5, parts by mass), methyl acetate /
Dioxane / acetone / methanol / ethanol (60
/ 20/20/5/5, parts by mass), methyl acetate / acetone / cyclopentanone / ethanol / isobutanol / cyclohexane (65/10/10/5/5/5, parts by mass),

Methyl formate / methyl ethyl ketone / acetone / methanol / ethanol (50/20/20/5
/ 5, parts by mass), methyl formate / acetone / ethyl acetate / ethanol / butanol / hexane (65/10/1
0/5/5/5, parts by mass), acetone / methyl acetoacetate / methanol / ethanol (65/20/10 /
5, acetone / cyclopentanone / ethanol / butanol (65/20/10/5, parts by mass),
Acetone / 1,3 dioxolane / ethanol / butanol (65/20/10/5, parts by mass), 1,3 dioxolane / cyclohexanone / methyl ethyl ketone / methanol / butanol (55/20/10/5/5 /
5, parts by mass) and the like. The dope used in the present invention, in addition to the non-chlorine organic solvent of the present invention,
Dichloromethane may be contained in an amount of 10% by mass or less based on the total amount of the organic solvent of the present technology.

When preparing the cellulose acylate solution of the present invention, a chlorine-based organic solvent may be used as a main solvent in some cases. Details will be described below. In the present invention, the chlorine-based organic solvent is not particularly limited as long as the cellulose acylate can be dissolved, cast and film-formed. These chlorine-based organic solvents are preferably dichloromethane and chloroform. Dichloromethane is particularly preferable. There is no particular problem in mixing an organic solvent other than the chlorine-based organic solvent. In that case, it is preferable to use at least 50 mass% of dichloromethane. The non-chlorine organic solvent used together in the present invention is described below. That is, as a preferable non-chlorine-based organic solvent, an ester or ketone having 3 to 12 carbon atoms,
A solvent selected from ether, alcohol, hydrocarbon and the like is preferable. The ester, ketone, ether and alcohol may have a cyclic structure. Functional groups of esters, ketones and ethers (ie -COO-,-
A compound having two or more of any one of CO- and -O-) can also be used as a solvent, and may have other functional groups such as alcoholic hydroxyl groups at the same time. In the case of a solvent having two or more kinds of functional groups, the number of carbon atoms may be within the specified range of the compound having any functional group. Examples of esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate. 3 carbon atoms
Examples of ketones of to 12 include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and methylcyclohexanone. Examples of ethers having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-
Included are dioxolane, tetrahydrofuran, anisole and phenetole. Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate,
2-Methoxyethanol and 2-butoxyethanol are mentioned.

The alcohol used in combination with the chlorine-based organic solvent may preferably be linear, branched or cyclic, and among them, saturated aliphatic hydrocarbon is preferable. preferable. 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-
Includes butanol, 1-pentanol, 2-methyl-2-butanol and cyclohexanol. Fluorine-based alcohol is also used as the alcohol. For example, 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1
-Propanol and the like can also be mentioned. Further hydrocarbons
It may be linear, branched or cyclic. Both aromatic hydrocarbons and aliphatic hydrocarbons can be used. The aliphatic hydrocarbon may be saturated or unsaturated. Examples of hydrocarbons include cyclohexane, hexane, benzene, toluene and xylene.

The non-chlorine organic solvent used in combination with the chlorine-based organic solvent which is the main solvent used for dissolving the above-mentioned cellulose acylate is not particularly limited, but methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone,
It is selected from dioxolane, dioxane, ketones or acetoacetic acid esters having 4 to 7 carbon atoms, alcohols or hydrocarbons having 1 to 10 carbon atoms. Further preferred non-chlorine organic solvents used in combination are methyl acetate, acetone,
Methyl formate, ethyl formate, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl acetyl acetate,
Mention may be made of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and cyclohexanol, cyclohexane, hexane. Examples of combinations of chlorine-based organic solvents that are preferred main solvents of the present invention include the following,
It is not limited to these.

Dichloromethane / methanol / ethanol / butanol (75/10/5/5/5, parts by mass),
-Dichloromethane / acetone / methanol / propanol (80/10/5/5, parts by mass) -Dichloromethane / methanol / butanol / cyclohexane (75/1
0/5/5/5, parts by mass), dichloromethane / methyl ethyl ketone / methanol / butanol (80/10 /
5/5, parts by mass), dichloromethane / acetone / methyl ethyl ketone / ethanol / isopropanol (75
/ 10/10/5/7, parts by mass), dichloromethane /
Cyclopentanone / methanol / isopropanol (8
0/10/5/8, parts by mass), dichloromethane / methyl acetate / butanol (80/10/10, parts by mass),
Dichloromethane / cyclohexanone / methanol / hexane (70/20/5/5, parts by mass), dichloromethane / methyl ethyl ketone / acetone / methanol / ethanol (50/20/20/5/5, parts by mass), dichloromethane / 1, 3 dioxolane / methanol / ethanol (70/20/5/5, mass part), dichloromethane / dioxane / acetone / methanol / ethanol (60/20/10/5/5, mass part), dichloromethane / acetone / cyclo Pentanone / Ethanol / Isobutanol / Cyclohexane (65/10/10/5
/ 5/5, parts by mass), dichloromethane / methyl ethyl ketone / acetone / methanol / ethanol (70/1
0/10/5/5, mass part), dichloromethane / acetone / ethyl acetate / ethanol / butanol / hexane (65/10/10/5/5/5, mass part), dichloromethane / methyl acetoacetate / methanol / Ethanol (65/20/10/5, parts by mass), dichloromethane / cyclopentanone / ethanol / butanol (65 /
20/10/5, parts by mass), and the like.

The cellulose acylate of the present invention is characterized by being a solution dissolved in an organic solvent in an amount of 10 to 30% by mass, more preferably 13 to 27% by mass,
In particular, a cellulose acylate solution having 15 to 25% by mass dissolved therein is preferable. The method of carrying out the cellulose acylate at these concentrations may be carried out so that the solution has a predetermined concentration at the stage of dissolution, or may be prepared as a low-concentration solution (for example, 9 to 14% by mass) in advance and then concentrated as described below. You may adjust to a predetermined high concentration solution in a process. Furthermore, after a high-concentration cellulose acylate solution is prepared in advance, various additives may be added to give a predetermined low-concentration cellulose acylate solution, and the cellulose acylate solution concentration of the present invention may be adjusted by any method. There is no particular problem if it is carried out.

Next, in the present invention, the molecular weight of the aggregate of the cellulose acylate is 10,000 to 1 in a diluted solution prepared by making the cellulose acylate solution 0.1 to 5 mass% with the organic solvent of the same composition.
It is preferably 5 million. More preferably, the associated molecular weight is 1 to 10 million. This associated molecular weight can be determined by the static light scattering method. At this time, it is preferable that the radius of gyration, which is simultaneously obtained, be 40 to 200 nm. A more preferable radius of inertia square is 70 to 200 nm. Furthermore, it is preferable that the second virial coefficient is dissolved so as to be −2 × 10 ⁻⁴ to 4 × 10 ^−4, and more preferably the second virial coefficient is −2 × 10 ⁻⁴ to 2 × 10 ^−4. Is. Here, the definition of the associated molecular weight, the radius of inertia square and the second virial coefficient in the present invention will be described. These were measured using the static light scattering method according to the following method. The measurement was carried out in a dilute region for the convenience of the device, but these measured values reflect the behavior of the dope in the high concentration region of the present invention. First, cellulose acylate is dissolved in a solvent used for dope, and 0.1% by mass, 0.2% by mass, 0.3% by mass,
A 0.4% by weight solution was prepared. In order to prevent moisture absorption, cellulose acylate was dried at 120 ° C. for 2 hours, and the weighing was performed at 25 ° C. and 10% RH. The melting method was carried out according to the method adopted at the time of melting the dope (normal temperature melting method, cooling melting method, high temperature melting method). Subsequently, these solutions and the solvent were mixed with 0.2 μm Teflon (registered trademark).
It filtered with the filter made. Then, the filtered solution was subjected to static light scattering using a light scattering measuring device (DLS-manufactured by Otsuka Electronics Co., Ltd.).
700) at 25 ° C. from 30 ° to 140 ° at 10 ° intervals. Obtained data is BERRY
It was analyzed by the plotting method. For the refractive index required for this analysis, the value of the solvent obtained by the Abbe refraction system was used, and the concentration gradient (dn / dc) of the refractive index was measured by a differential refractometer (Otsuka Electronics Co.
DRM-1021) manufactured by Mitsui Chemicals, Inc. was used to measure the solvent and solution used for the light scattering measurement.

Regarding the preparation of the cellulose acylate solution (dope) of the present invention, the dissolution method is not particularly limited, and may be a room temperature dissolution method, a cooling dissolution method or a high temperature dissolution method, or a combination thereof. Be implemented. Regarding these, for example, JP-A-5-16330
1, JP-A-61-106628, JP-A-58-1277
37, JP-A-9-95544, and JP-A-10-9585.
4, JP-A-10-45950, JP-A-2000-5378.
4, JP-A-11-322946, and further JP-A-11-3
22947, JP-A-2-276830, and JP-A-2000-
273239, JP-A-11-71463, JP-A-04-
259511, JP 2000-273184, JP 1
1-323017, JP-A No. 11-302388 and the like describe methods for preparing a cellulose acylate solution.
The above-described methods for dissolving these cellulose acylates in an organic solvent can also be applied to these techniques within the scope of the present invention. For details of these, especially regarding non-chlorine-based solvent systems, JIII Journal of Technical Disclosure (Kogi No. 2001-1745, March 1, 2001).
(Published on 5th, Japan Institute of Invention) by the method described in detail on pages 22 to 25. Further, the dope solution of the cellulose acylate of the present invention is usually subjected to solution concentration and filtration.
-1745, published by Mar. 15, 2001, Institute of Invention), page 25. When it is dissolved at a high temperature, it is almost equal to or higher than the boiling point of the organic solvent used, and in that case, it is used under pressure.

The cellulose acylate solution of the present invention preferably has a viscosity and a dynamic storage elastic modulus within a range. Add 1 mL of sample solution to the rheometer (CLS 5
00) using a Steel Cone (both manufactured by TA Instruments) having a diameter of 4 cm / 2 °. Measurement conditions are Oscillation Step / T
40 ° C to -10 ° C with the temperature ramp
Was measured while varying the range at 2 ° C./min, and the static non-Newtonian viscosity n ^* (Pa · sec) at 40 ° C. and the storage elastic modulus G ′ (Pa) at −5 ° C. were obtained. The sample solution was kept warm at the measurement starting temperature until the liquid temperature became constant, and then the measurement was started. In the present invention, the viscosity at 40 ° C. is 1 to 300 Pa.
-Sec and the dynamic storage elastic modulus at -5 ° C is 10,000 to 1,000,000 Pa. More preferably, the viscosity at 40 ° C. is 1 to 2000 Pa · sec, and the dynamic storage elastic modulus at −5 ° C. is 30,000 to 500,000 Pa, and particularly preferably, the viscosity at 40 ° C. is 10 to 10. 150 Pa · sec and a dynamic storage elastic modulus at −5 ° C. of 50,000 to 500,000 Pa
Is.

Next, a method for producing a film using the cellulose acylate solution of the present invention will be described. As the method and equipment for producing the cellulose acylate film of the present invention, a solution casting film forming method and a solution casting film forming apparatus conventionally used for producing a cellulose triacetate film are used. The dope (cellulose acylate solution) prepared from the dissolver (pot) is temporarily stored in a storage pot, and the bubbles contained in the dope are removed to make the final preparation. The dope is sent from the dope outlet to the pressurizing die through a pressurizing constant quantity gear pump that can deliver the dope with high accuracy by the number of rotations, and the dope of the casting part running endlessly from the die (slit) of the pressurizing die. The dope film (also referred to as a web), which is dry and dried, is peeled from the metal support at a peeling point which is evenly cast on the metal support and the metal support makes one round. Both ends of the obtained web are sandwiched by clips and conveyed by a tenter while keeping the width and dried, and then conveyed by rolls of a drying device to complete the drying and wound by a winder to a predetermined length. The combination of the tenter and the roll group drying device varies depending on the purpose. In the solution casting film forming method used for the silver halide photographic light-sensitive material and the functional protective film for electronic displays, in addition to the solution casting film forming device, an undercoat layer, an antistatic layer, an antihalation layer, a protective layer, etc. A coating device is often added for surface treatment of the film.
Each of these manufacturing steps is described in detail in pages 25 to 30 of the Institute of Invention and Innovation public technical report (Kogi No. 2001-1745, issued March 15, 2001, Society of Invention).
It is classified into casting (including co-casting), metal support, drying, peeling and stretching.

In the present invention, the space temperature of the casting portion is not particularly limited, but it is preferably -50 to 50 ° C. Further, it is preferably −30 to 40 ° C., particularly preferably −20 to 30 ° C. In particular, the cellulose acylate solution cast by the space temperature at a low temperature is instantaneously cooled on the support to increase the gel strength, so that the film containing the organic solvent can be retained. As a result, the cellulose acylate can be stripped from the support in a short time without evaporating the organic solvent, and high-speed casting can be achieved. The means for cooling the space may be ordinary air, nitrogen, argon, helium or the like, and is not particularly limited. In that case, the humidity is preferably 0 to 70% RH, more preferably 0 to 50% RH. Further, in the present invention, the temperature of the support at the casting portion for casting the cellulose acylate solution is -50 to 130 ° C, preferably -3.
It is 0 to 25 ° C, and further -20 to 15 ° C. In order to maintain the temperature of the casting portion at the temperature of the present invention, cooling gas may be introduced into the casting portion, or a cooling device may be arranged in the casting portion to cool the space. At this time, it is important to take care not to attach water, and it can be carried out by using a dry gas.

In the present invention, one or a plurality of solutions can be used as the cellulose acylate solution. Regarding the content and casting of each solution, it is particularly preferable to adopt one or more of the following constitutions. That is, (1) the cellulose acylate solution is a cellulose acylate solution containing at least one liquid or solid plasticizer in an amount of 0.1 to 20 mass% with respect to the cellulose acylate at 25 ° C., ( 2) A cellulose acylate solution containing at least one liquid or solid ultraviolet absorber in an amount of 0.001 to 5 mass% with respect to the cellulose acylate.
(3) At least one kind of solid having an average particle size of 5 to 30
A cellulose acylate solution containing 0.001 to 5 mass% of fine particle powder having a size of 00 nm with respect to the cellulose acylate, (4) at least one fluorine-based surfactant with respect to the cellulose acylate 0.00
It is a cellulose acylate solution containing 1 to 2% by mass, and (5) a cellulose acylate solution containing 0.0001 to 2% by mass of at least one release agent with respect to the cellulose acylate. (6) A cellulose acylate solution containing 0.0001 to 2% by mass of at least one deterioration inhibitor based on cellulose acylate, and (7) at least one optical anisotropy control agent being cellulose. 0 for Acylate.
1 to 15% by mass, (8) at least one kind of infrared absorber with respect to cellulose acylate 0.1
A cellulose acylate solution containing 5% by mass to 5% by mass. Further, the cellulose acylate film produced from the above-mentioned preferable cellulose acylate solution has preferable characteristics.

In the casting step, one type of cellulose acylate solution may be cast in a single layer, or two or more types of cellulose acylate solution may be cast simultaneously or successively. When there is a casting step consisting of two or more layers, in the cellulose acylate solution and the cellulose acylate film to be produced, the composition of the chlorine-based solvent in each layer is the same or different, and each layer is The additive is one kind or a mixture of two or more kinds, the addition position of the additive to each layer is the same layer or different layers, The concentration in the solution is either the same or different in each layer, the molecular weight of the aggregates in each layer is the same or different, and the concentration of the solution in each layer is different. The temperature is the same or different, the coating amount of each layer is the same or different, the viscosity of each layer is the same Either one of the different viscosities, the film thickness after drying of each layer is the same or one of different thicknesses, and the materials present in each layer are in the same state or distribution or different state or Cellulose reed characterized by a distribution, physical properties of each layer being the same or different, and physical properties of each layer being uniform or having a distribution of different physical properties. A rate solution and a cellulose acylate film produced from the rate solution are also preferable. Here, the physical properties mean the Institute of Invention and Innovation public technical report (Kogi No. 2001-1745, issued on March 15, 2001,
Inventive Society), pages 6 to 7, including physical properties, such as haze, transmittance, spectral characteristics, retardation Re, Rth, molecular orientation axis, axis deviation,
Tear strength, folding endurance, tensile strength, Rt difference between inside and outside, crease, dynamic friction, alkali hydrolysis, curl value, water content, residual solvent amount, heat shrinkage rate, high humidity dimension evaluation, moisture permeability, flatness of base , Dimensional stability, thermal shrinkage initiation temperature, elastic modulus, measurement of bright spot foreign matter, and the like, and also includes impedance and surface condition used for evaluation of the base. In addition, the Technical Report of the Invention Association (Official Number 2001-174)
5, Yellow Issue, Transparency, Thermophysical properties (Tg, heat of crystallization), etc. of cellulose acylate, which are described in detail on page 11 by the Institute of Invention and Innovation (March 15, 2001).

The cellulose acylate film can be subjected to a surface treatment as the case may be to improve the adhesion between the cellulose acylate film and each functional layer (for example, the undercoat layer and the back layer). For example, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment can be used. The glow discharge treatment here may be low-temperature plasma that occurs under a low pressure gas of 10 ^{−3 to} 20 Torr, and plasma treatment under atmospheric pressure is also preferable. The plasma-excitable gas is a gas that is plasma-excited under the above conditions, and includes argon, helium, neon, krypton,
Examples include xenon, nitrogen, carbon dioxide, CFCs such as tetrafluoromethane, and mixtures thereof. Details of these are disclosed in the Technical Bulletin for Invention
2001-1745, published by Mar. 15, 2001, Institute of Invention), pages 30 to 32. In the plasma treatment at atmospheric pressure, which has been attracting attention in recent years, for example, irradiation energy of 20 to 500 Kgy is used under 10 to 1000 Kev, and more preferably 30 to 500.
Irradiation energy of 20-300 Kgy under Kev is used. Of these, the alkali saponification treatment is particularly preferable and is extremely effective as the surface treatment of the cellulose acylate film.

The alkali saponification treatment is also preferably carried out by applying a saponification solution. Examples of the coating method include a dip coating method, a curtain coating method, an extrusion coating method, a bar coating method and an E-type coating method. The solvent of the alkali saponification treatment coating liquid has good wettability because it is applied to the transparent support of the saponification liquid, and the saponification liquid solvent does not form irregularities on the surface of the transparent support, and the surface state remains good. It is preferable to select a solvent to keep. Specifically, alcohol solvents are preferable, and isopropyl alcohol is particularly preferable.
Also, an aqueous solution of a surfactant can be used as a solvent. The alkali of the coating solution for alkali saponification is preferably an alkali soluble in the above solvent, more preferably KOH or NaOH. The pH of the saponification coating solution is preferably 10 or more,
12 or more is more preferable. The reaction conditions during alkali saponification are preferably 1 second or more and 5 minutes or less at room temperature, more preferably 2 seconds or more and 1 minute or less, and particularly preferably 3 seconds or more and 30 seconds or less. After the alkali saponification reaction, the surface coated with the saponification solution is preferably washed with water or an acid and then with water. In addition, the coating-type saponification treatment and the later-described coating of the alignment film can be continuously performed, and the number of steps can be reduced. Further, the cellulose acylate film obtained in the present invention may be subjected to alkali treatment by a dipping method. That is, surface treatment can be carried out by arranging an alkaline treatment bath, a water washing bath, an acid treatment bath, a water washing bath, and optionally a rinse bath continuously or intermittently. In this case, each solution has the same composition as the corresponding solution used in the coating method.

In order to achieve the adhesion between the film and the emulsion layer, a method of applying a functional layer directly on the cellulose acylate film to obtain an adhesive force after surface activation treatment, There is a method in which an undercoat layer (adhesive layer) is provided after the treatment or without the surface treatment and a functional layer is applied thereon. For details of these undercoat layers, refer to the Japan Institute of Invention and Innovation Technical Report (Kogi No. 2001-174).
5, Issued March 15, 2001, Institute of Invention), page 32. Also, regarding the functional layer of the cellulose acylate film of the present invention, various functional layers have various technical layers disclosed by the Institute of Invention and Innovation.
Issued by the Institute of Invention and Innovation, 15th March), pages 32 to 45.

The application of the cellulose acylate prepared in the present invention will be briefly described first. The optical film of the present invention is particularly useful as a polarizing plate protective film. When used as a polarizing plate protective film, the method for producing the polarizing plate is not particularly limited, and it can be produced by a general method. There is a method in which the obtained cellulose acylate film is treated with an alkali, and a polyvinyl alcohol film is dipped and stretched in an iodine solution and laminated on both surfaces of the polarizer using a completely saponified polyvinyl alcohol aqueous solution. Instead of alkali treatment, JP-A-6-94915,
You may perform easy adhesion processing as described in Unexamined-Japanese-Patent No. 6-118232. As the adhesive used to bond the protective film-treated surface and the polarizer, for example,
Examples thereof include polyvinyl alcohol-based adhesives such as polyvinyl alcohol and polyvinyl butyral, and vinyl-based latex such as butyl acrylate. The polarizing plate is composed of a polarizer and a protective film that protects both sides of the polarizer,
Further, a protective film is attached to one surface of the polarizing plate, and a separate film is attached to the other surface. Protect film and separate film are
Used to protect the polarizing plate during product inspection. In this case, the protect film is attached for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the side where the polarizing plate is attached to the liquid crystal plate. Further, the separate film is used for the purpose of covering the adhesive layer that is stuck to the liquid crystal plate, and is used on the surface side where the polarizing plate is stuck to the liquid crystal plate. In a liquid crystal display device, a substrate containing a liquid crystal is usually arranged between two polarizing plates, but a polarizing plate protective film to which the optical film of the present invention is applied can obtain excellent displayability at any position. . In particular, since a transparent hard coat layer, an antiglare layer, an antireflection layer, etc. 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 present invention can be used in various applications and is particularly effective when used as an optical compensation sheet for liquid crystal display devices. The cellulose acylate film of the invention can be used in liquid crystal cells of various display modes. TN (Twisted
Nematic), IPS (In-Plane Sw)
etching), FLC (Ferroelectric)
c Liquid Crystal), AFLC (An
ti-ferroelectric Liquid C
physical), OCB (optically com)
Penstory Bend), STN (Suppe
r Twisted Nematic), VA (Ver
Tally Aligned) and HAN (Hy
Various display modes such as bridge aligned nematic) have been proposed. In addition, a display mode in which the above display mode is orientation-divided is also proposed. The cellulose acylate film is effective in liquid crystal display devices of any display mode. It is also effective in any of the transmissive, reflective, and semi-transmissive liquid crystal display devices. The cellulose acylate film of the present invention is
It may be used as a support of an optical compensation sheet of a TN type liquid crystal display device having a mode liquid crystal cell. The cellulose acylate film of the invention may be used as a support of an optical compensation sheet of an STN type liquid crystal display device having an STN mode liquid crystal cell. Generally, in an STN type liquid crystal display device, rod-shaped liquid crystalline molecules in a liquid crystal cell are twisted within a range of 90 to 360 degrees, and the refractive index anisotropy (Δn) and cell gap (d) of the rod-shaped liquid crystalline molecules are twisted. ) And product (△ nd) is 30
It is in the range of 0 to 1500 nm. Regarding the optical compensation sheet used in the STN type liquid crystal display device, see JP-A 2000-1
It is described in Japanese Patent No. 05316. The cellulose acylate film of the present invention is a V having a VA mode liquid crystal cell.
It is particularly advantageously used as a support for an optical compensation sheet of an A type liquid crystal display device. The cellulose acylate film of the present invention is an OCB type liquid crystal display device having an OCB mode liquid crystal cell or an HA having a HAN mode liquid crystal cell.
It is also advantageously used as a support for an optical compensation sheet of an N-type liquid crystal display device.

The cellulose acylate film of the present invention is TN type, STN type, HAN type, GH (Guest-type).
It is also advantageously used as an optical compensation sheet for a (Host) type reflective liquid crystal display device. These display modes have long been well known. Regarding the TN reflective liquid crystal display device, JP-A-10-123478 and WO984832
No. 0 and Japanese Patent No. 3022477 have descriptions.
The optical compensation sheet used for the reflective liquid crystal display device is described in WO00-65384. The cellulose acylate film of the present invention has an ASM (Axial)
y Symmetric Aligned Micro
It is also advantageously used as a support for an optical compensation sheet of an ASM type liquid crystal display device having a cell) mode liquid crystal cell. The ASM mode liquid crystal cell is characterized in that the cell thickness is maintained by a resin spacer whose position can be adjusted. Other properties are similar to those of the TN mode liquid crystal cell. Regarding the ASM mode liquid crystal cell and the ASM type liquid crystal display device, a paper by Kume et al.
et al. , SID 98 Digest 108
9 (1998)). The applications of these detailed cellulose acylate films described above are disclosed in JIII Journal of Technical Disclosure (Jpn. Pat. No. 2001-1745, 200).
Invention Society, published March 15, 1), pages 45-59. Specific embodiments of the cellulose acylate of the invention are described below, but the invention is not limited thereto.

[0058]

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

(1) Unpeeled film residue The surface of the support when the obtained film was peeled from the support was visually observed, and the unpeeled film residue of the cellulose acylate film was evaluated as follows. A: No peeling residue is observed on the support. B: A slight peeling residue was observed on the support. C: A large amount of peeling residue was observed on the support. D: A large amount of peeling residue was observed on the support.

(2) Horizontal unevenness of film (abbreviated as unevenness) The obtained film was visually observed, and defects of the horizontal unevenness were evaluated as follows. A: No horizontal unevenness is observed on the film. B: Horizontal unevenness was slightly observed on the film. C: Lateral unevenness was considerably observed on the film. D: A large amount of horizontal unevenness was observed on the film.

(3) Buds of Film (abbreviated as "butsu") The obtained film was visually observed, and the bumps on the surface were evaluated as follows. A: No spots were found on the film surface. B: A few spots were observed on the film surface. C: Significant spots were recognized on the film surface. D: Unevenness was observed on the film surface, and many spots were recognized.

(4) Haze of film Measured using a haze meter (1001DP type, manufactured by Nippon Denshoku Industries Co., Ltd.).

(5) Viscosity of solution and dynamic viscoelastic sample solution (1 mL) was measured with a rheometer (CLS 500) using a steel cone having a diameter of 4 cm / 2 ° (both manufactured by TA Instruments). Measurement conditions are Oscillation Step / temper
The temperature range of 40 ° C to -10 ° C was varied at 2 ° C / min and the static non-Newtonian viscosity n ^* (Pa
-Sec) and storage elastic modulus G '(Pa) at -5 ° C were determined. The sample solution was kept warm at the measurement starting temperature until the liquid temperature became constant, and then the measurement was started.

Examples will be given below, but the present invention is not limited thereto. Example 1 (1-1) Preparation of Cellulose Triacetate Solution In a 200 L stainless steel dissolution tank having a stirring blade in which cooling water circulates around the outer periphery, while well stirring and dispersing in the solvent mixed solution described below, Cellulose triacetate powder (flakes) was gradually added, and the whole was charged to 100 kg. In addition, as the solvent, methyl acetate, butanol, acetone, methanol, and ethanol were used, all having a water content of 0.2 mass% or less.
First, as the powder of cellulose triacetate, the powder was put into a dispersion tank, the pressure in the tank was reduced to 1300 Pa, and the stirring shear rate was initially 15 m / sec (shear stress 5 × 10 5).
Dissolver type eccentric stirring shaft that stirs at a peripheral speed of ⁴ kgf / m / sec ² ) and an anchor blade on the central axis has a peripheral speed of 1 m / sec (shear stress 1 × 10 ⁴ kgf / m).
/ Sec ² ; 9.8 × 10 ⁴ N / m / sec ² ) for 60 minutes under the condition of stirring. Start temperature of dispersion is 0 ℃
Therefore, the final temperature reached was 25 ° C. by running the cooling water composed of ethylene glycol and water. After the dispersion was completed, the high-speed stirring was stopped and the peripheral speed of the anchor blade was 0.5 m / s.
The mixture was further stirred for 100 minutes as ec to swell the cellulose triacetate flakes. Until the end of swelling, the inside of the tank was pressurized with nitrogen gas to 0.12 MPa.
At this time, the oxygen concentration in the tank was less than 2 vol%, and there was no problem in explosion protection. It was also confirmed that the water content in the dope was 0.2% by mass or less. The composition of the cellulose triacetate solution is as follows.

(Components of Cellulose Triacetate Solution)
Cellulose triacetate (substitution degree 2.83, viscosity average degree of polymerization 270, water content 0.2 mass%, viscosity of 6 mass% in dichloromethane solution 280 mPa · sec, average particle diameter 1.5 mm, standard deviation 0.5 mm) A certain powder)
(20 parts by mass), calixarene derivative according to the present invention (described in Table 1), methyl acetate (58 parts by mass), acetone (5 parts by mass), methanol (6 parts by mass), butanol (5 parts by mass), plasticizer A (glycerin monododecanoyl diacetate) (1 part by mass), plasticizer B (triphenyl phosphate) (1 part by mass), plasticizer C (biphenyl diphenyl phosphate) (0.2 parts by mass), plasticizer D (ethyl phthalyl glycol ethyl ester)
(0.2 parts by mass), UV agent a (2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t)
ert-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), UV 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), and citric acid monoethyl ester (0.04 parts by mass). Furthermore, the cellulose triacetate used here has a residual acetic acid content of 0.1% by mass or less and a Ca ion content of 0.0
6% by mass, Mg ions were 0.007% by mass, and Fe ions were 5 ppm. The 6-position acetyl group was 0.937, which was 33.1% of all acetyl groups. The acetone-extracted content was 8% by mass, and the ratio of the weight average molecular weight to the number average molecular weight was 0.5, showing a uniform distribution. The haze is 0.07% and the transparency is 93.3.
%, Tg is 160 ° C., crystallization heat value is 6.0 J /
It was g.

(1-2) Dissolution and Filtration of Cellulose Triacetate Film Solution The obtained non-uniform gel-like solution is fed by a screw pump whose center portion is heated to 30 ° C. and cooled from the outer peripheral portion of the screw. Then, it was passed through the cooling part at −75 ° C. for 5 minutes. Cooling was carried out using a -85 ° C refrigerant cooled in a refrigerator. Then, the solution obtained by cooling was heated to 35 ° C. while being fed by a screw pump and transferred to a stainless steel container. After stirring at 50 ° C. for 2 hours to form a uniform solution, the solution was filtered with a filter paper having an absolute filtration accuracy of 0.01 mm (# 63 manufactured by Toyo Roshi Kaisha, Ltd.), and further a filter paper having an absolute filtration accuracy of 2.5 μm (manufactured by Pall Ltd., It was filtered through FH025). The obtained cellulose triacetate solution had a viscosity (35 ° C.) of Pa · sec and a dynamic storage elastic modulus (−
5 ° C.) is shown in Table 1 in Pa. It was confirmed that the sample of the present invention had an aggregate size of 2 to 10 million, and had a solution property within the preferred range of the present invention.

(1-3) Preparation of Cellulose Triacetate Film The above-mentioned filtered cellulose triacetate solution at 50 ° C. was cast onto a mirror-like stainless steel support which is a drum having a diameter of 3 m through a casting Giser (temperature of the support). Is -5
℃ was set). The Giesser used is JP-A-11-3.
A form similar to that described in 14233 was used. The casting speed was 45 m / min and the coating width was 80 cm. The temperature of the entire space of the casting part was set to 15 ° C. Then, the cellulose triacetate film that had been cast and rotated 50 cm before the casting portion was peeled off from the drum, and both ends were clipped with pin tenters. Thereafter, the cellulose triacetate film held by the pin tenter was conveyed to the drying zone. For the first drying, 45 ° C. drying air was blown. Further drying at 110 ° C for 5 minutes, then at 145 ° C for 10 minutes (film temperature is about 140 ° C)
Then, the cellulose triacetate film (film thickness 40μ
m) was obtained. Both ends of the obtained sample were cut into 3 cm, and knurling having a height of 100 μm was performed on a portion 2 to 10 mm from the end, and the sample was wound into a roll of 500 m in length.

(1-4) Results Table 1 shows the evaluation results of the obtained samples. Comparative sample 1 without addition of the calixarene derivative in the present invention
1 and Comparative Sample 1-10 with a small amount of addition had large peeling residue and had poor film characteristics. Further, in Comparative Sample 1-11 in which the addition amount was outside the range of the present invention, unevenness, spots and haze were remarkably inferior. In addition, Comparative Compounds A and B similar to the calixarene of the present invention, and Comparative Samples 1-12 to 15 using the comparative compound known as a gelling agent have high peeling residue, unevenness, spots and haze, It was unacceptable as a film.
On the other hand, Samples 1-2 to 1-9 of the present invention had a small amount of peeling residue, no unevenness, no spots, and a small haze, and were excellent in surface condition. It was also preferable in terms of viscosity and dynamic viscoelasticity.

[0069]

[Table 1]

Example 2 Sample 2-7 was obtained in the same manner as in Example 1 except that (1-2) Cellulose triacetate film solution was changed to the following for Sample 1-4 of Example 1.

The heterogeneous gel-like solution obtained in the preparation of the cellulose triacetate film solution of (1-1) was sent by a screw pump and passed through a heating part heated and pressurized at 140 ° C. and 1 MPa for 3 minutes. After that, 110 ℃, 1M
It is heated and pressurized to pa, filtered with a filter paper having an absolute filtration accuracy of 0.01 mm (# 63 manufactured by Toyo Roshi Kaisha, Ltd.), and further, a filter paper having an absolute filtration accuracy of 0.0025 mm (manufactured by Pall, FH02).
It was filtered in 5). The obtained solution has a viscosity (35 ° C.) of 65 Pa · sec and a dynamic storage elastic modulus of 143,000 P.
The molecular weight of the aggregate was 4.8 million, which was within the preferred range of the present invention.

(2-1) The sample 2-4 of the present invention obtained as a result was excellent in filterability, and the unpeeled residue, unevenness, and spots were A, and the haze was 0.4%, which was excellent. From this, it was confirmed that in the present invention, a cellulose triacetate solution and a cellulose triacetate film which are excellent in high temperature and high pressure dissolution can be produced.

Example 3 Sample 3-4 of the present invention was prepared in exactly the same manner as in Example 1 except that the plasticizers A and B were both removed as 0 parts by weight in Sample 1-4 of Example 1. The viscosity (35 ° C.) of the obtained solution was 65 Pa · sec, the dynamic storage elastic modulus was 132,000 Pa, and the molecular weight of the associated product was 4.5 million, which was within the preferred range of the present invention. Sample 3 obtained
In No. 4, no unevenness was left, and both unevenness and spots were A, and haze was 0.3, which was excellent. On the other hand, when the folding endurance test was carried out, Samples 1-4 showed 129 times,
Sample 3-4, which is within the scope of the present invention but does not contain a plasticizer, had a cutting resistance test of 98 times, which was not a problem in practical use, but was slightly inferior. Therefore, in the present invention, it is apparent that the cellulose triacetate film containing a plasticizer is a more preferable embodiment. Here, the folding endurance was evaluated by subjecting a sample 120 mm × 120 mm to humidity control at 23 ° C., 65% RH for 2 hours, and measuring the number of reciprocations until cutting by bending according to ISO8776-1988.

Example 4 Sample 4-4 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 weight in Sample 1-4 of Example 1. . The obtained solution had a viscosity (35 ° C.) of 62 Pa · sec, a dynamic storage elastic modulus of 1390,000 Pa, and an aggregate molecular weight of 3,300,000, which were in the preferred range of the present invention. Obtained Sample 4-4
No peeling remained, unevenness and spots were evaluated as A, and haze was 0.3, which was excellent. On the other hand, when the photo-fading test was carried out for 1 month for a xenon lamp of 20,000 lux, the haze of Sample 1-4 was 0.6%, whereas the haze of Sample 4-4 was within the scope of the present invention. Is 0.9%
And a little up. Therefore, in the present invention, it is clear that the cellulose triacetate film containing a UV agent is a more preferable embodiment.

Example 5 A sample 5-4 of the present invention was prepared in exactly the same manner as in Example 1 except that the fine particles of silica were removed as 0 parts by weight in Sample 1-4 of Example 1. The resulting solution has a viscosity (3
5 ° C) is 69 Pa · sec and the dynamic storage elastic modulus is 1
It was 43,000 Pa and the molecular weight of the aggregate was 3,820,000, which was within the preferred range of the present invention. The obtained sample 5-4 had no peeling residue, unevenness and spots were evaluated as A, and haze was 0.7, which was excellent. Meanwhile, the film 2
When the slipperiness was examined by stacking the sheets, Sample 1-4 was able to move two sheets smoothly, whereas Sample 5-4, which is within the scope of the present invention, had a slightly bad movement between the films. Therefore, in the present invention, it is apparent that the cellulose triacetate film containing fine particles is a more preferable embodiment.

Example 6 A sample 1-4 of the present invention of Example 1 was prepared in the same manner as in Example 1 except that the production of the (1-3) cellulose triacetate film of Example 1 was changed as follows. A cellulose triacetate film of Sample 6-4 of the invention was prepared. That is, a part of the cellulose triacetate solution obtained in (1-1) was sampled, and a cellulose triacetate solution (solution A) was prepared by adding 10% by mass of methyl acetate to dilute the cellulose triacetate solution. The obtained solution A had a viscosity (35 ° C.) of 63 Pa · sec and a dynamic storage elastic modulus of 135,000 Pa, which was within the preferred range of the present invention.
The resulting solution was co-cast by stacking the cellulose triacetate solution of Sample 1-4 inside and on both sides thereof with the cellulose triacetate solution (solution A) by co-casting according to the co-casting method described in JP-A 06-134993. A rolled cellulose triacetate film was obtained. The film thickness was set to 3 μm on both sides and 34 μm inside so that the total thickness was 40 μm. The surface condition of the obtained sample 6-4 is as shown in sample 1-4.
The surface was smoother and had no irregularities, which was even better than that. Therefore, it is apparent that co-casting is an even more excellent mode in the present invention.

Example 7 In (Example 1) of JP-A-11-316378,
Except that the first transparent support was changed to the one having the thickness of the cellulose triacetate film (second film) obtained in Sample 1-6 of Example 1 of the present invention as 100 μm, the procedure was carried out in the same manner as in JP-A No. 11-1999. (Example 1) of No. -316378 was implemented and sample 7-6 was produced. 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 mode in which a cellulose triacetate film produced thereafter can be applied to an optical polarizing plate without any problem.

Example 8 Except that the cellulose triacetate manufactured by Fuji Photo Film Co., Ltd. of Example 1 of JP-A-7-333433 was changed to the cellulose triester film of Sample 1-9 of the invention of Example 1 of the invention, An optical compensation filter film sample was prepared in exactly the same manner as in Example 1 of JP-A-7-333433. The obtained filter film had an excellent viewing angle on the left, right, top and bottom. Therefore, it can be seen that the cellulose triacetate film of the present invention is excellent for optical use.

Example 9 The present invention is further used in various optical applications, and as a representative of the present invention, Sample 1-9 is used, for example, JP-A-10-4842.
0 Liquid crystal display device described in Example 1, JP-A-9-2657.
2 Optically anisotropic layer containing discotic liquid crystal molecules described in Example 1, alignment film coated with polyvinyl alcohol, V described in FIGS. 2 to 9 of JP-A-2000-154261.
A type liquid crystal display device, FIG. 1 of JP-A-2000-154261.
When used in the OCB type liquid crystal display devices described in 0 to 15, good performance was obtained.

Example 10 A sample 10-3 of the present invention, which is a film thereof, was prepared in the same manner as in Example 1 except that the film thickness of the sample 1-3 of the present invention of Example 1 was 120 μm. It was made. On one side of the obtained film, JP-A-4-73736
(Back layer composition) of Example 1 of No. 1 was applied to prepare a back layer having a cationic polymer as a conductive layer. Further, sample 105 of Example 1 of JP-A No. 11-38568 was coated on the opposite surface of the obtained film base provided with a back layer to prepare a silver halide color photographic light-sensitive material. The color film obtained had excellent images and was easy to handle.

Example 11 A film which is the same as Example 1 except that the butanol was changed to isopropanol and the amount thereof was changed to 8 parts by mass in Sample 1-3 of the present invention of Example 1. Inventive Sample 11-3 was made. The obtained solution had a viscosity (35 ° C.) of 73 Pa · sec and a dynamic storage elastic modulus of 203,000 Pa, which was within the preferred range of the present invention. The resulting dilute solution had an aggregate molecular weight of 5,600,000, unpeeled residue A, unevenness A and spot A, and a haze of 0.4, which was excellent in all respects.

Example 12 In the sample 1-5 of the present invention of Example 1, the cellulose triacetate (15 parts by mass) and cellulose acetate propionate (acetyl substitution degree 2.45, propionate substitution degree 0.25) were used. The total degree of substitution is 2.70, the viscosity average degree of polymerization is 320, and the water content is 0.3.
Mass%, viscosity of dichloromethane solution 6% by mass 275 m
Pa · sec, powder having an average particle diameter of 1.3 mm and standard deviation of 0.4 mm, residual acetic acid amount and propionic acid amount are both 0.05% by mass or less, Ca is 0.012% by mass, and Mg is 0. 0.07% by mass, Fe at 5 ppm, 6-position acetyl group and propionyl group at 0.70 and 0.1, respectively.
7 and 33% of all substituents, 7% by mass of acetone extracted, the ratio of the weight average molecular weight to the number average molecular weight is 0.9, the yellowness index is 1.3, the haze is 0.2, and the transparency is 93. 6%, Tg 157 ° C., crystallization heat value 4.
3 J / g) (5 parts by mass), and cellulose acetate butyrate (acetyl substitution degree 2.39, butyrate substitution degree 0.45, total substitution degree 2.84, viscosity average degree of polymerization 34).
0, water content 0.4% by mass, viscosity of dichloromethane solution 6% by mass 295 mPa · sec, average particle size 1.3 mm
And the standard deviation is 0.4 mm, the residual acetic acid content and the butanoic acid content are both 0.03% by mass or less, and the Ca content is 0.
005 mass%, Mg 0.004 mass%, Fe 5 pp
m, 6-position acetyl group and butyroyl group are each 0.7
2 and 0.20, 32% of all substituents, 14% by mass of acetone extracted, the ratio of the weight average molecular weight to the number average molecular weight is 1.3, the yellowness index is 0.9, the haze is 0.5, A sample of the present invention, which is a film thereof, in exactly the same manner as in Example 1 except that the transparency is changed to 92.9%, the Tg is 153 ° C., and the crystallization heat value is 3.9 J / g) (5 parts by mass). 11-5 was produced. The resulting solution has a viscosity (3
5 ° C.) was 135 Pa · sec, and the dynamic storage elastic modulus was 36,000 Pa, which was within the range of the present invention. The obtained dilute solution had an aggregate molecular weight of 43 million, peeling residue A, unevenness A and spot A, and a haze of 0.5, which was excellent in all respects. Therefore, in the present invention, an excellent cellulose acylate film can be obtained even if two or more kinds of cellulose acylate are mixed and used.

Example 13 (13-1) Preparation of cellulose triacetate solution It has a stirring blade of 200L with cooling water circulating around the circumference.
In a non-soluble dissolution tank, mix well with the following solvent mixture solution
・ While dispersing, the following cellulose triacetate powder
(Flake) is gradually added, and the total amount becomes 100 kg.
I prepared it. In addition, the solvent dichloromethane,
Tanol, acetone, methanol and ethanol
All of those having a water content of 0.2 mass% or less were used.
First, the cellulose triacetate powder is placed in a dispersion tank.
The powder is thrown into the tank and the pressure inside the tank is reduced to 1300 Pa.
The stirring shear speed is initially 15 m / sec (shear stress 5 × 10
^Fourkgf / m / sec^Two4.9 × 10⁵N / m / se
c^Two) Dissolver type eccentric stirring that stirs at the peripheral speed
Shaft and central axis with anchor blades, peripheral speed 1m / se
c (shear stress 1 × 10^Fourkgf / m / sec^Two9.8
× 10^FourN / m / sec^Two) For 30 minutes under stirring conditions
Dispersed. The starting temperature of dispersion is 5 ° C, and cooling water is flowed.
The final temperature reached was 25 ° C by pouring water. End of distribution
After that, the high speed stirring is stopped and the peripheral speed of the anchor blade is 0.5m.
/ Sec and stir for another 100 minutes to
The reacetate flakes were swollen. Until the end of swelling
Pressurize the inside of the tank with elementary gas to 0.12 MPa
It was Oxygen concentration in the tank at this time is less than 1.5 vol%
So, I kept it in good condition for explosion protection. Also during the dope
It was confirmed that the water content was 0.2 mass% or less. SE
The composition of the lulose triacetate solution is as follows.
It

Cellulose triacetate (degree of substitution 2.8
2. Viscosity average degree of polymerization 320, water content 0.2 mass%, viscosity in dichloromethane solution 6 mass% 305 mPa · se
c, average particle size 1.5 mm, standard deviation 0.5 mm
Powder (20 parts by mass), compound KA-1 of the present invention
(2 mass% of cellulose triacetate solid content), dichloromethane (58 mass parts), acetone (5 mass parts), methanol (6 mass parts), butanol (5 mass parts), plasticizer A (ditrimethylolpropane tetraacetate)
(1 part by mass), plasticizer B (triphenyl phosphate) (1 part by mass), plasticizer C (biphenyl diphenyl phosphate (0.2 parts by mass), plasticizer D (ethyl phthalyl glycol ethyl ester) ( 0.2 parts by mass), U
V 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-t
ert-Butylphenyl) -5-chlorobenzotriazole) (0.2 parts by mass), UV agent c (2 (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl)-
5-chlorobenzotriazole) (0.2 parts by mass), fine particles (silicon dioxide (particle size 20 nm), Mohs hardness of about 7) (0.05 parts by mass), citric acid monoethyl ester (0.04 parts by mass) Using. Further, the cellulose triacetate used here has a residual acetic acid content of 0.1% by mass or less, Ca of 0.05% by mass, and Mg of 0.00% by mass.
It was 7 mass%, and Fe was 5 ppm. The acetyl group at the 6-position is 0.95, which is 32.
It was 2%. The acetone extracted content was 11% by mass, and the ratio of the weight average molecular weight to the number average molecular weight was 0.5, showing a uniform distribution. The haze was 0.08%, the transparency was 93.5%, the Tg was 160 ° C., and the crystallization heat value was 6.2 J / g.

(13-2) Cellulose triacetate film solution The obtained non-uniform gel-like solution is fed by a screw pump whose axial center is heated to 30 ° C. and cooled from the outer peripheral portion of the screw to -75. The cooling part was passed through for 3 minutes at 0 ° C. Cooling was performed using a refrigerant of -80 ° C cooled in a refrigerator. Then, the solution obtained by cooling was heated to 35 ° C. while being fed by a screw pump and transferred to a stainless steel container. After stirring at 35 ° C. for 2 hours to form a uniform solution, the solution was filtered with a filter paper having an absolute filtration precision of 0.01 mm (# 63 manufactured by Toyo Roshi Kaisha, Ltd.), and further a filter paper having an absolute filtration precision of 2.5 μm (manufactured by Pall Ltd., It was filtered through FH025). The obtained cellulose triacetate solution had a viscosity (35 ° C.) of 49 Pa · sec and a dynamic storage elastic modulus (−5 ° C.) of 317,000 Pa. In addition, the degree of association polymerization was 6.2 million, and it was confirmed that the polymer had a solution property within the range of the present invention.

(13-3) Preparation of Cellulose Triacetate Film The above-mentioned filtered cellulose triacetate solution at 35 ° C. was cast onto a mirror-like stainless steel support, which is a drum having a diameter of 3 m, through a casting Giesser (temperature of the support). Is -5
℃ was set). The Giesser used is JP-A-11-3.
A form similar to that described in 14233 was used. The casting speed is 75 m / min and the coating width is 200 cm.
And The temperature of the entire space of the casting part was set to 10 ° C. Then, the cellulose triacetate film that had been cast and rotated 50 cm before the casting portion was peeled off from the drum, and both ends were clipped with pin tenters. Thereafter, the cellulose triacetate film held by the pin tenter was conveyed to the drying zone. For the first drying, a 35 ° C. drying air was blown. After further drying at 70 ° C for 5 minutes and then at 145 ° C for 10 minutes (film temperature is about 140 ° C), a cellulose triacetate film (film thickness 60μ
m) was obtained. Both ends of the obtained sample were cut into 3 cm, and knurling having a height of 100 μm was performed on a portion 2 to 10 mm from the ends, and the sample was wound into a roll having a length of 300 m.

(13-4) As a result, the sample 13-1 of the present invention was excellent in surface state because all the unpeeled parts, unevenness and spots were A, and the haze was 0.3. Furthermore, the foreign matter size is 50 μm in diameter
The above (within 20 μm in the depth direction) is 1 in 10 m ² .
The number of foreign matters having a size of 20 to 50 μm was 5 or less within 10 m ² . Further, the number of foreign matter having a size of 20 μm or less was within 5 within ² m ² . From the above, it is clear that an excellent cellulose triacetate film can be produced in the present invention.

[0088]

According to the present invention, there is provided a solution having good strippability even at high speed when the cellulose acylate film is stripped off after being cast on the support of the cellulose acylate solution in the production process. be able to. Furthermore, the cellulose acylate film solution of the present invention can provide a cellulose acylate film free from unevenness and spots. Furthermore, a cellulose triester film having excellent optical anisotropy and excellent film strength can be provided. Furthermore, a cellulose triacetate film excellent as a support for a light-sensitive material can be produced.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 1:10 C08L 1:10 F term (reference) 2H049 BA02 BA06 BA42 BB18 BB33 BC01 BC22 4F071 AA09 AC11A AE22 AF30Y AF35Y AH12 BA02 BB02 BC01 BC13 4F205 AA01 AB19 AC05 AG01 AH73 AR06 AR20 GA07 GB02 GC06 GE21 GE24 GF24 GN13 GN18 GN19 GN22 GN29

Claims (3)

[Claims] 1. A cellulose acylate solution containing a cellulose acylate in which the degree of substitution of cellulose with hydroxyl groups satisfies all of the following formulas (I) to (III), at least one calixarene derivative, and an organic solvent. And a casting step of casting a cellulose acylate solution in which the total amount of the calixarene derivative is 0.05 to 10% by weight of the cellulose acylate and the concentration of the cellulose acylate is 5 to 40% by weight of the solution. A cellulose acylate film produced by a process. (I) 2.6 ≦ SA + SB ≦ 3.0 (II) 2.0 ≦ SA ≦ 3.0 (III) 0 ≦ SB ≦ 0.8 SA is the substitution degree of the acetyl group, and SB is the number of carbon atoms of 3 to 3.
22 is the degree of substitution with the acyl group of 22. 2. The cellulose acylate film according to claim 1, which is produced by using a cellulose acylate solution obtained by at least one of the following preparation methods (1) to (3). (1) A step of swelling a cellulose acylate with an organic solvent at −20 to 40 ° C., and a step of heating a mixture of the cellulose acylate and the organic solvent to 0 to 57 ° C. to dissolve the cellulose acylate in the organic solvent. And (2) a step of swelling the cellulose acylate with an organic solvent at -20 to 55 ° C, a step of cooling the mixture of the cellulose acylate and the organic solvent to -100 to -10 ° C, And a method for preparing a cellulose acylate solution, which comprises the step of heating the cooled mixture to 0 to 57 ° C to dissolve the cellulose acylate in the organic solvent, (3) adding the cellulose acylate to the organic solvent at -20 to 55 ° C. Swelling step, 60-2 at 0.2-30 MPa
Heating the mixture of cellulose acylate and organic solvent under high pressure and high temperature of 40 ° C., and heating the mixture to 0
A method for preparing a cellulose acylate solution, which comprises the steps of cooling to ~ 57 ° C and dissolving the cellulose acylate in an organic solvent. 3. When the cellulose acylate and the organic solvent are mixed, 90% by mass or more of the cellulose acylate has particles having a particle diameter of 0.1 to 5 mm, and the obtained cellulose acylate solution is prepared. Including a step of filtering, a step of casting a cellulose acylate solution on a support, a step of peeling off, and a drying step of forming a film by evaporating a solvent, and a step of winding the cellulose acylate film prepared further. The produced cellulose acylate film according to claim 1 or 2.