JP2005154550A - Cellulose film, optical film using the film, image display device and silver halide photographic sensitized material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cellulose film which has both hardness and resistance to brittleness at the same time and excels in film flexibility and durability and to obtain an optical film (such as a polarizing film and an optical compensating film) having excellent properties, an image display device, and a silver halide photographic sensitized material. <P>SOLUTION: The cellulose film contains an ester compound (E) having at least one polycyclic alicyclic hydrocarbon group and at least two ester bonds in the molecule and cellulose. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a cellulose film, an optical film using the cellulose film, an image display device, and a silver halide photographic light-sensitive material.
In particular, the present invention supports various functional optical films such as polarizing plate protective films, retardation films, field-of-view films, antireflection films used in liquid crystal display devices, and silver halide photographic materials. Relates to body film. Furthermore, this invention relates to the optical film which comprises the various functional films applied to an organic EL display etc.

  Cellulose film is transparent, has excellent physical and mechanical properties, and has little dimensional change with respect to temperature and humidity change. Conventionally, a support for silver halide photosensitive material film, drafting tracing film, electrical insulating material, etc. In recent years, it has been used as a protective film for polarizing plates in liquid crystal image display devices.

However, as it is, the tear strength and the bending strength are low, and there is a drawback that it becomes very brittle and easily tears especially under a low humidity condition. Therefore, in order to improve these, a solution casting film-forming method of cellulose acylate is used, and a plasticizer is used as an important (substantially essential) additive for the cellulose acylate solution. Representative plasticizers include phosphate ester plasticizers such as triphenyl phosphate (TPP) and aromatic carboxylic acid ester plasticizers such as dimethyl phthalate (DMP) (Non-patent Document 1).
In addition, citric acid ester (Patent Document 1), ester compound of alkane polyol and aliphatic monocarboxylic acid or aromatic monocarboxylic acid (Patent Document 2 etc.), lower fatty acid ester of glycerin (Patent Document 3 etc.), etc. Aliphatic ester compounds are also disclosed.
Furthermore, as an improvement in the moisture resistance of these aliphatic esters, a diaryl ester of 2-ethyl-2-butyl-1,3-propanediol (Patent Document 4), an aromatic ring or a cyclohexane ring is used as a molecule. Citric acid esters (Patent Document 5) containing 3 or more of them, and esters of alkane polyols with carboxylic acids containing aromatic rings or cyclohexane rings (Patent Document 6) have been proposed. However, even with these supports, film strength stability under long-term storage, film coloring, and the like were not sufficient.

  On the other hand, in recent years, liquid crystal image display devices have been increasingly refined, and have excellent light transmittance as a protective film for polarizing plates, optical non-orientation, good adhesion to polarizing elements, excellent flatness, There is a demand for improved performance such as ultraviolet absorption and antistatic properties and durability. Further, an optically anisotropic optical compensation film that can be used for a liquid crystal display device that has been attracting attention in place of a CRT is an oblique liquid crystal display device that uses an anisotropic liquid crystal material. There is a problem of viewing angle that the display performance deteriorates when viewed, and further performance improvement is desired.

As an optical compensation film, an anisotropic material obtained by fixing the alignment form of a liquid crystalline compound is the mainstream in recent years. However, the production method thereof has conventionally used a cellulose ester film as a support, and a liquid crystalline compound is formed thereon. Since the solvent is applied, the additives in the cellulose ester film are mixed into the liquid crystal compound due to the bleed phenomenon, and the orientation of the liquid crystal compound is disturbed or white turbid. It has been desired to reduce or eliminate the problem.
In particular, in recent years, the development of display devices has been rapidly progressing with the enlargement of the display unit and the widespread use of mobile display devices such as mobile phones. Further dimensional stability and durability are desired.
Marusawa et al., Plastic Materials Course 17 “Fiber-Based Resin”, p. 121, published by Nikkan Kogyo Shimbun (Showa 45) Japanese Patent Laid-Open No. 11-92574 JP 2001-247717 A JP 2000-63560 A JP 2003-96236 A JP 2003-12822 A JP 2003-12823 A

Accordingly, an object of the present invention is to provide a cellulose film that can achieve both hardness and brittleness resistance and is excellent in film flexibility and durability.
Another object of the present invention is to provide an optical film (polarizing film, optical compensation film, etc.), an image display device and a silver halide photographic light-sensitive material obtained by using the cellulose film having excellent properties.
Furthermore, another object of the present invention is to provide a cellulose film that is excellent in moisture resistance, tear strength, and bending strength even with a thin film having a thickness of 80 μm or less.

  According to the present invention, there are provided a cellulose film having the following constitution, a production method thereof, an optical film (such as an optical compensation film and a polarizing film), an image display device (such as a liquid crystal display device), and a silver halide photographic light-sensitive material. The object of the invention is achieved.

(1) A cellulose film comprising an ester compound (E) containing at least one polycyclic alicyclic hydrocarbon group and at least two ester bonds in the molecule, and cellulose.
(2) The cellulose film according to (1), wherein the polycyclic alicyclic hydrocarbon group is a hydrocarbon group having a polycyclic alicyclic hydrocarbon ring structure having 5 to 32 carbon atoms. .

(3) The above-mentioned ester compound (E) is an aliphatic polyol ester of an aliphatic polyol and one or more polycyclic alicyclic hydrocarbon-containing monocarboxylic acids, and an aliphatic polycarboxylic acid and one or more polycarboxylic acids. The cellulose film as described in (1) or (2) above, which is at least one ester compound selected from an aliphatic polycarboxylic acid ester with a cyclic alicyclic hydrocarbon-containing monool.
(4) The above ester compound (E) is a polycyclic alicyclic hydrocarbon compound containing at least two polar groups selected from a hydroxy group and a carboxy group and an aliphatic monool or an aliphatic monocarboxylic acid. The cellulose film as described in (1) or (2) above, which is an ester compound.

(5) The cellulose film according to any one of (1) to (4), further comprising fine particles.
(6) Any one of the above (1) to (4), wherein the cellulose is a cellulose acylate in which the degree of substitution with a hydroxyl group satisfies all of the following formulas (IIIa) to (IIIb): A cellulose acylate film according to any one of the above.
(IIIa) 2.6 ≦ SA ′ + SB ′ ≦ 3.0
(IIIb) 1.5 ≦ SA ′ ≦ 3.0
(IIIc) 0 ≦ SB ′ ≦ 0.8
SA ′ is the degree of substitution of the acetyl group, and SB ′ is the degree of substitution of the acyl group having 3 to 22 carbon atoms.

(7) A cellulose acylate film obtained by forming a cellulose composition containing cellulose acylate and the ester compound (E) by a solution casting method.
(8) A step in which the cellulose acylate film is prepared by dissolving cellulose acylate in a substantially non-chlorine solvent to prepare a cellulose acylate composition containing the ester compound (E), and cellulose acylate from the cellulose acylate solution. The cellulose acylate film as described in any one of (1) to (7) above, which is produced by a step of forming a rate film and a step of stretching the cellulose acylate film.

(9) An optical film using the cellulose film according to any one of (1) to (8) above.
(10) A display device using the optical film according to (9).
(11) A support for a silver halide photographic light-sensitive material using the cellulose film according to any one of the above (1) to (8) having a film thickness of 30 to 250 μm.
(12) A polarizing plate using the cellulose film according to any one of (1) to (8) above.

  Specifically, the ester compound (E) contained in the cellulose composition of the present invention as a plasticizer is preferably at least one ester compound of the following multi-ester compounds. As used herein, “multi-ester compound” means an ester compound having two or more ester bonds.

(E-1) A multi-ester compound of an aliphatic polyol and a monocarboxylic acid, wherein at least one of the monocarboxylic acids is a monocarboxylic acid containing a polycyclic alicyclic ring.
(E-2) A polyester compound of an aliphatic polycarboxylic acid and a monoalcohol, wherein at least one of the monoalcohols is a monool containing a polycyclic alicyclic ring.
(E-3) A polyester compound derived from a polycyclic alicyclic hydrocarbon compound containing at least two polar groups selected from a hydroxy group or a carboxy group, and an aliphatic monool or an aliphatic monocarboxylic acid.

  The polycyclic alicyclic ring structure is preferably a C6-C32 polycyclic alicyclic hydrocarbon ring structure.

  It has been found that the inclusion of at least one ester compound (E) of the present invention in the cellulose composition as a plasticizer improves the film brittleness resistance and the moisture resistance characteristics (moisture permeability and heat and humidity resistance) of the film. It was done. In addition, the ester compound (E) of the present invention can be used in an amount effective for improving film properties, and is effective in terms of film flexibility and durability.

  Hereinafter, the cellulose film of the present invention and the production method thereof will be described in more detail.

[Cellulose (and cellulose acylate)]
The cellulose used in the present invention is described below.
Cellulose raw material cellulose used in the present invention includes cotton linter, wood pulp (hardwood pulp, softwood pulp), kefna, etc., and any cellulose acylate obtained from any raw material cellulose can be used, optionally mixed. May be. In the present invention, it is preferable to produce cellulose acylate by esterification from cellulose. However, the particularly preferable cellulose is not always usable as it is, and these raw materials are purified and used.

[Preparation of cellulose acylate solution (dope) and production of film]
It describes about the cellulose acylate of this invention manufactured from the cellulose which is the above-mentioned raw material.
The cellulose acylate of the present invention preferably has a degree of substitution of cellulose with a hydroxyl group that satisfies all of the following formulas (IIIa) to (IIIc).

(IIIa): 2.6 ≦ SA ′ + SB ′ ≦ 3.0
(IIIb): 1.5 ≦ SA ′ ≦ 3.0
(IIIc): 0 ≦ SB ′ ≦ 0.8

  Here, SA ′ is the substitution degree of the acetyl group substituting the hydrogen atom of the hydroxyl group of cellulose, and SB ′ is the substitution degree of the acyl group having 3 to 22 carbon atoms substituting the hydrogen atom of the hydroxyl group of cellulose. Represents. SA represents an acetyl group substituting a hydrogen atom of a hydroxyl group of cellulose, and SB represents an acyl group having 3 to 22 carbon atoms substituting a hydrogen atom of a hydroxyl group of cellulose.

  Glucose units having β-1,4 bonds constituting cellulose have free hydroxyl groups at the 2nd, 3rd and 6th positions. Cellulose acylate is a polymer obtained by esterifying some or all of these hydroxyl groups with acyl groups. The degree of acyl substitution means the proportion of cellulose esterified at each of the 2-position, 3-position and 6-position (100% esterification at each position is substitution degree 1). In the present invention, the total sum of substitution degrees of SA and SB (SA ′ + SB ′) is more preferably 2.7 to 2.96, and particularly preferably 2.80 to 2.95. Further, the substitution degree (SB ′) of SB is 0 to 0.8, particularly 0 to 0.6. Further, 28% or more of SB is preferably a substituent at the 6-position hydroxyl group, more preferably 30% or more is a substituent at the 6-position hydroxyl group, more preferably 31% or more, and particularly 32% or more is 6%. It is also preferable that it is a substituent of a coordinate hydroxyl group. Furthermore, the cellulose acylate film in which the sum of the substitution degrees of SA and SB at the 6-position of cellulose acylate is 0.8 or more, more preferably 0.85 or more, and particularly preferably 0.90 or more. Can be mentioned. These cellulose acylate films can produce a solution having a preferable solubility, and in particular, a non-chlorine organic solvent can produce a good solution.

  The acyl group (SB) having 3 to 22 carbon atoms of 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, alkyl carbonyl esters, alkenyl carbonyl esters, aromatic carbonyl esters, aromatic alkyl carbonyl esters, and the like of cellulose, each of which may further have a substituted group. These specific acyl groups and a method for synthesizing cellulose acylate are described in detail on page 9 of the Japan Society of Invention and Innovation Technical Report (Technology No. 2001-1745, published on March 15, 2001). .

  In the cellulose acylate film of the present 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 or more (preferably 70% by mass or more, more preferably 80% by mass or more) of the total polymer components.

The degree of polymerization of the cellulose acylate preferably used in the present invention is a viscosity average degree of polymerization of 200 to 700, preferably 230 to 550, more preferably 230 to 350, and particularly preferably a viscosity average degree of polymerization of 240 to 320. The average degree of polymerization can be measured by Uda et al.'S intrinsic viscosity method (Kazuo Uda, Hideo Saito, Journal of Textile Society, Vol. 18, No. 1, pages 105-120, 1962). Further details are described in JP-A-9-95538.
These cellulose acylates are described in detail on pages 7 to 12 of the above-mentioned public technical number 2001-1745 in terms of raw material cotton and synthesis method.

[Ester Compound (E) of the Present Invention]
The ester compound (E) used in the present invention is a polyester compound containing at least one polycyclic alicyclic hydrocarbon group and at least two ester bonds in the molecule. Here, the “polycyclic alicyclic hydrocarbon group” means an alicyclic aliphatic group having a non-aromatic condensed polycyclic, cross-linking sensitive, or spiro alicyclic cyclic structure. The polycyclic alicyclic hydrocarbon group is preferably a group selected from polycyclic alicyclic hydrocarbon ring structures having 5 to 32 carbon atoms.
Specific examples include groups having a bicyclo, tricyclo, tetracyclo, or pentacyclo structure having 5 or more carbon atoms. In particular, 6 to 25 carbon atoms are preferable.
Examples of the structure of the polycyclic alicyclic ring are given below. In addition, in the following structural example, you may contain a double bond in the position which is not conjugated.

  Moreover, these alicyclic hydrocarbon rings may have at least one substituent. As the substituent of the alicyclic hydrocarbon ring, an alkyl group, a substituted alkyl group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, alkoxy group, amide group, acyl group, alkoxycarbonyl group Etc.

As these substituents, monovalent nonmetallic atomic groups excluding hydrogen are used. Specific examples of the nonmetallic atom group include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a cyano group, a nitro group, a hydrocarbon ^{group, -OR 11, -SR 11, -COR} 11, —COOR ¹¹ , —OCOR ¹¹ , —SO ₂ R ¹¹ , —NHCONHR ¹¹ , —N (R ¹² ) COR ¹¹ , —N (R ¹² ) SO ₂ R ¹¹ , —N (R ¹³ ) (R ¹⁴ ), — CON (R ¹³ ) (R ¹⁴ ), —SO ₂ N (R ¹³ ) (R ¹⁴ ), —P (═O) (R ¹⁵ ) (R ¹⁶ ), —OP (═O) (R ¹⁵ ) (R ¹⁶ ), -Si (R ¹⁷ ) (R ¹⁸ ) (R ¹⁹ ) and the like.

  Examples of the hydrocarbon group include aliphatic groups, aryl groups, and heterocyclic groups. As the aliphatic group, a linear or branched alkyl group having 1 to 22 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nanodecyl group, eicosanyl group, heneicosanyl group, docosanyl group, etc.), straight chain having 2 to 22 carbon atoms Or a branched alkenyl group (e.g., vinyl group, propenyl group butenyl group, pentenyl group, hexenyl group, octenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, eicosenyl group, dococenyl group, butadienyl group, Pentadienyl group, hexadienyl group, A C2-C22 linear or branched alkynyl group (eg, ethynyl group, propynyl group, butynyl group, hexynyl group, octanyl group, decanyl group, dodecanyl group, etc.), C5-C22 22 alicyclic hydrocarbon groups (the alicyclic hydrocarbon groups include monocyclic, polycyclic, and bridged cyclic aliphatic hydrocarbon groups, and specific examples thereof include cyclopentane and cyclopentene. , Cyclopentadiene, cyclohexane, cyclohexene, cyclohexadiene, cycloheptane, cycloheptene, cycloheptadiene, cyclooctane, cyclooctene, cyclooctadiene, cyclooctatriene, cyclosonane, cyclosonene, cyclodecane, cyclodecene, cyclodecanediene, cyclodecanetriene, Cycloundecane, cyclododeca And the above-mentioned polycyclic alicyclic hydrocarbon groups and the like. These aliphatic groups may further have a substituent, and the substituent that can be introduced is the same as the substituent that can be introduced into the polycyclic alicyclic hydrocarbon group.

Examples of the aryl group include aryl groups having 6 to 18 carbon atoms (the aryl ring includes benzene, naphthalene, dihydronaphthalene, indene, fluorene, acenaphthylene, acenaphthene, biphenylene, and the like).
As the heterocyclic group, a heterocyclic group having a monocyclic or polycyclic ring structure containing at least one of an oxygen atom, a sulfur atom and a nitrogen atom (for example, a furanyl group, Tetrahydrofuranyl group, pyranyl group, pyroyl group, chromenyl group, phenoxathiinyl group, indazoyl group, pyrazoyl group, pyridiyl group, pyrazinyl group, pyrimidinyl group, indoyl group, isoindoyl group, quinoniyl group, pyrrolidinyl group, pyrrolinyl group, imidazolinyl Group, pyrazolidinyl group, piperidinyl group, piperazinyl group, morpholinyl group, thienyl group, benzothienyl group and the like. These aryl group and heterocyclic group may further have a substituent, and the substituent is the same as those exemplified as the group that can be introduced into the polycyclic alicyclic hydrocarbon group. Is mentioned.
Among these, a straight chain having 1 to 8 carbon atoms, a branched chain having 3 to 8 carbon atoms, and a cyclic aliphatic group having 5 to 16 carbon atoms, an aralkyl group having 7 to 9 carbon atoms, and a phenyl group Is more preferable.

R ¹¹ represents an aliphatic group, an aryl group, or a heterocyclic group. Specifically, those having the same contents as exemplified as the substituent of the above-mentioned polycyclic alicyclic hydrocarbon group can be mentioned. R ¹² represents the same as the hydrogen atom or the R ¹¹ group.

R ¹³ and R ¹⁴ each independently represents a hydrogen atom or the same as R ^11, and R ¹³ and R ¹⁴ are bonded to each other to form a 5-membered or 6-membered ring containing an N atom. May be formed.

R ¹⁵ and R ¹⁶ each independently represent —OH, an aliphatic group having 1 to 22 carbon atoms, an aryl group having 6 to 14 carbon atoms, or —OR ¹¹ . The aliphatic group for R ¹⁵ and R ¹⁶ has the same meaning as the aliphatic group represented by R ¹¹ . Examples of the aryl group in R ¹⁵ and R ¹⁶ include the same aryl groups as those exemplified as the substituent that can be introduced into the polycyclic alicyclic hydrocarbon group. Such an aryl group may further have a substituent, and examples of the substituent include the same groups as those exemplified as the substituent that can be introduced into the polycyclic alicyclic hydrocarbon group. However, in such polar substituents, both R ¹⁵ and R ¹⁶ are not represented by —OH.
R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent a hydrocarbon group having 1 to 22 carbon atoms or —OR ^20, and at least one of these substituents represents a hydrocarbon group. The hydrocarbon group is the same as the aliphatic group represented by R ¹¹ and the aryl group that can be introduced into the alicyclic hydrocarbon group, and —OR ²⁰ represents the same contents as —OR ¹¹ .

The multi-ester compound of the present invention can be produced by a conventionally known esterification reaction.
For example, dehydration condensation reaction between an alcohol compound and a carboxylic acid compound (reaction using dicyclohexylcarbodiimide as a dehydrating agent, reaction using p-toluenesulfonic acid, tetrabutyltin or the like as a catalyst), ester compound of a lower alcohol of an alcohol compound and a carboxylic acid (Transesterification reaction with methyl ester, ethyl ester, etc.) (tetrabutoxy titanate as a catalyst), substitution reaction of alcohol compound with corresponding carboxylic acid halide, equivalent carboxylate and aliphatic hydrocarbon halogenated compound Substitution reaction (potassium iodide as a catalyst) etc. are mentioned.
Specifically, for example, S.M. Patai, “The Chemistry of Carboxylic Acids and Esters” (INTERSCIENCE-PUBLISHERS, published in 1969), “New Experimental Chemistry Course Volume 14, Organic Compound Synthesis and Reaction (II)” pp1000, Maruzen Co., Ltd. (1977) Another object of the present invention is to use the chemical reaction described in the above.

The following (E1)-(E3) are mentioned as a preferable aspect of the multiester compound (E) of this invention.
(E-1) A polyester compound of an aliphatic polyol and a monocarboxylic acid, wherein at least one monocarboxylic acid is a monocarboxylic acid containing a polycyclic alicyclic ring. (E-2) A polyester compound of an aliphatic polycarboxylic acid and a monoalcohol, wherein at least one of the monoalcohols is a monool containing a polycyclic alicyclic ring. -3) A polyester compound derived from a polycyclic alicyclic hydrocarbon compound containing at least two polar groups selected from a hydroxy group and a carboxy group, and an aliphatic monool and / or an aliphatic monocarboxylic acid

  The polyester compound (E) preferably contains two or more polycyclic alicyclic hydrocarbon rings in the molecule. More preferably, it contains 3 to 10 polycyclic alicyclic hydrocarbon rings, and preferably 3 to 20 ester bonds. Here, the other substituent that forms the ester bond in the molecule may not be a polycyclic alicyclic hydrocarbon ring group.

The multi-ester compound (E-1) will be described.
The multiester compound (E-1) is a multiesterified product of an aliphatic polyol and a monocarboxylic acid containing a polycyclic alicyclic ring.
As the aliphatic polyols, those having a valence of 2 to 20 are preferable. More preferably, 2-10 are mentioned.

  Specific examples of aliphatic polyols include alkanediols having 2 to 8 carbon atoms (for example, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanediol, cyclohexanedimethanol, diethylene glycol, dipropylene glycol, etc.) C3-C18 alkanes containing 3 or more hydroxy groups (for example, glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, hexanetriol, pentaerythritol, diglycerin, triglycerin, dipentaerythritol, Cyclohexanetriol, cyclohexanetrimethanol, inositol, etc.), polyalkyleneoxypolyols, and sugar alcohols. As polyalkyleneoxy polyols, the same alkylene diols as described above may be bonded to each other or different alkylene diols may be bonded to each other, but polyalkylene polyols having the same alkylene diols bonded to each other are more preferable. In any case, the number of bonds is preferably from 3 to 10. More preferably, it is 3-5. Specific examples include diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and di (oxyethylene-oxypropylene).

  Examples of sugar alcohols include “Natural Polymers” Chapter 2 (Kyoritsu Shuppan Co., Ltd., published in 1984) edited by the Society of Polymer Science and Engineering, Editorial Committee of Polymer Science, “Modern Industrial Chemistry 22, Natural Products Industry” Polyhydric alcohol compounds described in “Chemical II” (Asakura Shoten Co., Ltd., 1967) and the like. Saccharides that do not have a free aldehyde group or ketone group and do not exhibit reducibility are preferred. Glucose, sucrose, trehalose-type oligosaccharides in which reducing groups are bonded, glycosides in which reducing groups of saccharides and non-saccharides are combined, and sugar alcohols reduced by hydrogenation of saccharides are all suitable for the present invention. Used. Trehalose type oligosaccharides include saccharose and trehalose. Examples of glycosides include alkyl glycosides, phenol glycosides, mustard oil glycosides, and the like. Examples of sugar alcohols include D, L-arabit, rebit, xylit, D, L-sorbit, D, L-mannit, D, L-exit, D, L galactite, D, L-talit, zulsicit and allozulcit. Can be mentioned. Furthermore, maltitol obtained by hydrogenation of a disaccharide and a reduced form (reduced water candy) obtained by hydrogenation of an oligosaccharide are also preferably used.

  As monocarboxylic acid containing a polycyclic alicyclic ring, what is represented by the following general formula (I) is preferable.

In General Formula (I), U ¹ represents a direct bond or a divalent linking group, J ¹ represents an atomic group for forming a polycyclic alicyclic ring, and is the same as the above polycyclic alicyclic ring. The contents are listed.

Examples of the divalent linking group represented by U ¹ include the following groups and divalent alicyclic groups (the hydrocarbon ring having an alicyclic structure includes, for example, a cycloheptane ring, a cyclohexane ring, a cyclooctane ring, and a bicyclopentane. A ring, a tricyclohexane ring, a bicyclooctane ring, a bicyclononane ring, a tricyclodecane ring, etc.), a divalent aryl ring group (such as a benzene ring, a naphthalene ring, etc.), or a group consisting of a combination of these groups. Can be mentioned.

In the above, j ¹ and j ² may be the same or different, and may be a hydrogen atom, a halogen atom (fluorine atom, halogen atom, bromine atom, iodine atom) or an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, trifluoromethyl group, a methoxyethyl group, a cyanoethyl group chloroethyl group, etc.), j ³ is substituted C 1-12 hydrogen or C Hydrocarbon group (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, cyclohexylmethyl group, benzyl group, phenethyl group, phenyl group, chlorophenyl group, methoxyphenyl group, acetylphenyl group) , Trifluorophenyl group, etc.). j ⁴ and j ⁵ are hydrocarbon groups having 1 to 12 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, cyclohexylmethyl group, benzyl group, phenethyl group) , Phenyl group, chlorophenyl group, methoxyphenyl group, acetylphenyl group, trifluorophenyl group, etc.). J ⁴ and j ⁵ may be the same or different.

  The polyester compound (E-1) is preferably an esterified product of 2 to 20 polyhydric alcohols as described above, and the carboxylic acid bonded to the polyhydric alcohol ester may be one kind or two or more kinds. It may be mixed. In addition, the OH group in the polyhydric alcohol may be partially left as it is, but preferably all OH groups are esterified. In the case of a polyesterified product from a trihydric or higher polyhydric alcohol, an ester bond of a non-polycyclic alicyclic group may be contained together with an ester bond of a polycyclic alicyclic ring-containing group. Preferred monocarboxylic acids for forming these include aliphatic monocarboxylic acids, aromatic carboxylic acids, alicyclic monocarboxylic acids, and the like.

  As the aliphatic monocarboxylic acid, a fatty acid having a straight chain or side chain having 1 to 32 carbon atoms can be preferably used. The number of carbon atoms is more preferably 1-20, and particularly preferably 1-10. When acetic acid is contained, compatibility with the cellulose ester is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid. Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid, tridecylic acid , Myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, laccelic acid, phenylacetic acid, phenylpropionic acid, Examples thereof include saturated fatty acids such as cyclohexylacetic acid, unsaturated fatty acids such as butenoic acid, pentenoic acid, hexenoic acid, octenoic acid, undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid. These may further have a substituent.

Preferred alicyclic carboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, or derivatives thereof.
Examples of preferred aromatic monocarboxylic acids include those in which an alkyl group is introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, and two or more benzene rings such as biphenylcarboxylic acid, naphthalenecarboxylic acid, and tetralincarboxylic acid. The aromatic monocarboxylic acid which has, or those derivatives can be mentioned.

Next, the multiester compound (E-2) will be described.
The polyester compound (E-2) is a polyester compound of an aliphatic polycarboxylic acid and a monoalcohol, wherein at least one monoalcohol is a monool containing a polycyclic alicyclic ring. Is a multi-ester compound.

As for aliphatic polycarboxylic acid, 2-15 polyvalent carboxylic acid is mentioned, More preferably, it is 2-10 polyvalent carboxylic acid.
Specifically, for example, at least one of polycarboxylic acid, oxyacid, and polyol containing at least two carboxyl groups in oxalic acid, linear or branched aliphatic hydrocarbon having 1 to 22 carbon atoms, or the like. Examples thereof include compounds obtained by esterifying a hydroxyl group with a cyclic carboxylic acid anhydride, oxypolycarboxylic acids, and the like.

Examples of the aliphatic hydrocarbon of a polycarboxylic acid containing at least two or more carboxy groups in a linear or branched aliphatic hydrocarbon having 1 to 22 carbon atoms include alkanes having 1 to 22 carbon atoms and 2 carbon atoms. -22 alkene, C2-C22 alkyne, C5-C12 cycloalkane, C6-C12 cycloalkene, etc. are mentioned. In the case of an acyclic hydrocarbon, 2 to 4 carboxy groups may be mentioned. The cyclic hydrocarbon includes 2 to 6 carboxy groups. For example, “Dai Organic Chemistry”, Vol. 4-III, pp 403-415 (Asakura Shoten, published 1959), supervised by Fujio Kotake, Beilstein, “Organish Chemie”
Examples thereof include compounds described in BandIX and the like.

  Examples of the oxyacid include glycolic acid, lactic acid, glyceric acid, α-oxyalkanoic acid (alkane having 3 to 18 carbon atoms), and the like. The polyol in the esterified compound has the same content as the above aliphatic polyol, and examples include alkanediol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, cyclohexanediol, etc. Examples of the cyclic carboxylic acid anhydride obtained by esterifying one hydroxyl group include anhydrides such as succinic acid, maleic acid, glutaric acid, adipic acid, and cyclohexanedicarboxylic acid. Examples of the oxypolycarboxylic acid include tartronic acid, malic acid, tartaric acid, citric acid, oxyglutamic acid (β-form, γ-form) and the like.

  Examples of the monoalcohol containing a polycyclic alicyclic ring include compounds represented by the following formula (II).

In formula (II), J ² and U ² each represent the same contents as J ¹ and U ^{1 in} formula (I).

  Examples of the monoalcohol corresponding to the hydrocarbon group of the non-polycyclic alicyclic group of another ester substituent include those represented by the formula (III).

  General formula (III) R-OH

  In formula (III), R represents an aliphatic group or a heterocyclic group. Specific contents of these substituents include those having the same contents as the aliphatic group and heterocyclic group that are substituted on the above polycyclic alicyclic ring. Preferably, a C1-C8 alkyl group, a C3-C8 alkenyl group, a C5-C10 cycloalkyl group, and a C7-C10 aralkyl group are mentioned. These groups may be substituted, and specific examples thereof include the same substituents as those substituted on the polycyclic alicyclic ring.

  The polyester compound (E-3) is derived from a polycyclic alicyclic hydrocarbon compound containing at least two polar groups selected from a hydroxy group or a carboxy group and an aliphatic monool or an aliphatic monocarboxylic acid. It is a multi-ester compound.

  Examples of the polycyclic alicyclic hydrocarbon compound containing at least two polar groups selected from a hydroxy group or a carboxy group include compounds represented by the following formula (IV).

In formula (IV), n and m each represent an integer of 1 to 10.

  The ester compound (E) of the present invention is preferably contained in the range of 1 to 35% by mass with respect to the cellulose acylate. More preferably, it is 5-30 mass%, More preferably, it is 5-25 mass%. In this range, the molecules are uniformly dispersed without depositing as foreign matter in the film, and the film properties of the film can be improved.

[Fine particles]
In the present invention, it is preferable to add fine particles to the cellulose acylate composition in order to maintain good scratch resistance and film transportability.
They are conventionally used as a matting agent, an antiblocking agent or an anti-scratch agent. They are not particularly limited as long as they are materials exhibiting the functions described above. Preferred examples of these fine particles include inorganic compounds such as silicon-containing compounds, silicon dioxide, titanium oxide, zinc oxide, aluminum oxide, barium oxide, zirconium oxide, strontium oxide, antimony oxide, tin oxide, tin oxide / antimony oxide. , Calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate are preferred, more preferably inorganic compounds containing silicon and zirconium oxide, cellulose Silicon dioxide is particularly preferred because the turbidity of the acylate film can be reduced.
Surface-treated inorganic fine particles are also preferable because of good dispersibility in cellulose acylate. Examples of the treatment method include the method described in JP-A No. 54-57562. Examples of the particles include those described in JP-A No. 2001-151936.

  As the organic compound, for example, polymers such as cross-linked polystyrene, silicone resin, fluororesin and acrylic resin are preferable, and among them, silicone resin is preferably used. Among silicone resins, those having a three-dimensional network structure are particularly preferable.

  When these fine particles are added to the cellulose acylate solution, the method is not particularly limited, and any method can be used as long as a desired cellulose acylate solution can be obtained. For example, an additive may be contained at the stage of mixing cellulose acylate and a solvent, or an additive may be added after preparing a mixed solution with cellulose acylate and a solvent. Furthermore, it may be added and mixed immediately before casting the dope, and it is a so-called immediately preceding addition method, and screw type kneading is installed online and used for the mixing. For the mixing of the fine particles, the mixture itself may be added, but it is also preferable to use it as a solvent which has been dissolved in advance using a solvent or a binder (preferably cellulose acylate) or dispersed and stabilized in some cases. It is an aspect.

The primary average particle diameter of these fine particles is preferably 3 to 200 nm from the viewpoint of keeping haze low. More preferably, it is 5-100 nm, More preferably, it is 5-80 nm.
The amount of fine particles added to cellulose acylate is preferably 0.01 to 0.3 parts by mass, more preferably 0.05 to 0.2 parts by mass with respect to 100 parts by mass of cellulose acylate.

  In the preparation of the cellulose acylate composition of the present invention, in each preparation step, various additives (for example, UV inhibitors, deterioration inhibitors, optically anisotropic) depending on the application are used in the same manner as the ester compound (E) of the present invention. Property control agents, release agents, infrared absorbers, other plasticizers other than the compounds of the present invention, and the like. The addition time may be added at any time in the dope preparation step, but may be added by adding an additive to the final preparation step of the dope preparation step. Furthermore, the amount of each material added is not particularly limited as long as the function is manifested. Moreover, when a cellulose acylate film is formed from a multilayer, the kind and addition amount of the additive of each layer may differ. For example, it describes in Unexamined-Japanese-Patent No. 2001-151902 etc., These are techniques conventionally known. Further, for these details, the materials described in detail on pages 16 to 22 of the above-mentioned public technical number 2001-1745 are preferably used. The amount of these additives used is preferably used in the range of 0.001 to 20% by mass in the entire cellulose acylate composition.

Next, the organic solvent that dissolves the cellulose acylate of the present invention will be described.
Examples of the organic solvent to be used include conventionally known organic solvents. For example, those having a solubility parameter in the range of 17 to 22 are preferable. Lower aliphatic hydrocarbon chloride, lower aliphatic alcohol, ketone having 3 to 12 carbon atoms, ester having 3 to 12 carbon atoms, ether having 3 to 12 carbon atoms, fat having 5 to 8 carbon atoms Group hydrocarbons, aromatic hydrocarbons having 6 to 12 carbon atoms, fluoroalcohols (for example, paragraph numbers [0020] in JP-A-8-143709, and JP-A-11-60807) Compounds described in paragraph [0037] and the like.

  The ether, ketone and ester may have a cyclic structure. A compound having two or more functional groups of ether, ketone and ester (that is, —O—, —CO— and —COO—) can also be used as the organic solvent. The organic solvent may have another functional group such as an alcoholic hydroxyl group. In the case of an organic solvent having two or more types of functional groups, the number of carbon atoms may be within the specified range of the compound having any functional group. Specifically, for example, detailed compounds can be mentioned on pages 12 to 16 of the aforementioned public technical number 2001-1745.

In particular, in the present invention, the solvent is preferably used by mixing two or more kinds of organic solvents, and particularly preferred organic solvents are three or more kinds of mixed solvents different from each other, and the first solvent has the number of carbon atoms. A ketone having 3 to 4 carbon atoms and an ester having 3 to 4 carbon atoms, or a mixture thereof, and the second solvent is selected from ketones having 5 to 7 carbon atoms or acetoacetic acid ester; It is preferably selected from alcohol having a boiling point of 30 to 170 ° C or hydrocarbon having a boiling point of 30 to 170 ° C.
In particular, it is preferable from the viewpoint of solubility of cellulose acylate to use 20 to 90% by mass of acetate, 5 to 60% by mass of ketone, and 5 to 30% by mass of alcohol.

  Further, non-halogen organic solvent systems that do not contain halogenated hydrocarbons are particularly preferred. Technically, halogenated hydrocarbons such as methylene chloride can be used without problems, but from the viewpoint of the global environment and working environment, it is preferable that the organic solvent is substantially free of halogenated hydrocarbons. “Substantially free” means that the proportion of halogenated hydrocarbon in the organic solvent is less than 5% by mass (preferably less than 2% by mass). Moreover, it is preferable that halogenated hydrocarbons such as methylene chloride are not detected at all from the produced cellulose acylate film.

  Specific examples of the organic solvent used in the present invention include paragraph numbers [0021] to [0025] in JP-A No. 2002-146043 and paragraph numbers [0016] to [0021] in JP-A No. 2002-146045. ] Examples of the solvent system described in the above.

  The cellulose acylate of the present invention is preferably a solution in which 10 to 30% by mass is dissolved in an organic solvent, more preferably 13 to 27% by mass, and particularly 15 to 25% by mass. A cellulose acylate solution is preferred. The method for preparing cellulose acylate at these concentrations may be prepared so as to be a predetermined concentration at the stage of dissolution, or it is prepared in advance as a low concentration solution (for example, 9 to 14% by mass) and then concentrated later. You may adjust to a predetermined high concentration solution by a process. In addition, a cellulose acylate solution having a high concentration may be added to the cellulose acylate solution at a predetermined low concentration by adding various additives, and the cellulose acylate solution concentration of the present invention may be obtained by any method. There is no particular problem if it is implemented.

  In 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. Regarding these, for example, JP-A-5-163301, JP-A-61-106628, JP-A-58-127737, JP-A-9-95544, JP-A-10-95854, JP-A-10-45950, JP 2000-53784, JP 11-322946, JP 11-322947, JP 2-276830, JP 2000-273239, JP 11-71463, JP 04-259511, JP JP-A Nos. 2000-273184, 11-323017, and 11-302388 describe methods for preparing cellulose acylate solutions. These techniques for dissolving cellulose acylate in an organic solvent can be applied to these techniques as appropriate in the present invention. These details are carried out by the method described in detail on pages 22 to 25 of the aforementioned technical number 2001-1745, particularly for non-chlorinated solvent systems. Furthermore, the cellulose acylate dope solution of the present invention is usually subjected to solution concentration and filtration, and is also described in detail on page 25 of the aforementioned technical number 2001-1745. In addition, when it melt | dissolves at high temperature, it is the case where it is more than the boiling point of the organic solvent to be used, and in that case, it uses in a pressurized state.

The cellulose acylate solution of the present invention preferably has a viscosity and dynamic storage modulus within the range. 1 mL of the sample solution was measured with a rheometer (CLS 500) using Steel Cone (both manufactured by TA Instruments) with a diameter of 4 cm / 2 °. Measurement conditions were measured at Oscillation Step / Temperature Ramp by changing the range from 40 ° C to -10 ° C at 2 ° C / min, static non-Newtonian viscosity n ^* (Pa · sec) at 40 ° C and storage at -5 ° C The elastic modulus G ′ (Pa) was determined. The measurement was started after the sample solution was kept warm at the measurement start temperature until the liquid temperature became constant. 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 200 Pa · sec, and the dynamic storage elastic modulus at −5 ° C. is 30,000 to 500,000 Pa.

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 conventionally known solution casting film forming method and solution casting film forming apparatus called a drum method or a band method used for producing a cellulose triacetate film are used. .

  Hereinafter, the film forming process will be described using the band method as an example. The dope (cellulose acylate solution) prepared from the dissolving machine (kettle) is temporarily stored in a storage kettle, and the foam contained in the dope is defoamed for final preparation. The dope is sent from the dope discharge port to the pressure die through a pressure metering gear pump capable of delivering a constant amount of liquid with high accuracy, for example, by the number of rotations, and the dope is run endlessly from the die (slit) of the pressure die. The dry-dried dope film (also referred to as web) is peeled off from the metal support at a peeling point that is uniformly cast on the metal support and substantially rounds the metal support. Both ends of the obtained web are sandwiched between clips, transported by a tenter while keeping the width, dried, then transported by a roll group of a drying device, dried, and wound up to a predetermined length by a winder. The combination of the tenter and the roll group dryer varies depending on the purpose. In the solution casting film forming method used for silver halide photographic light-sensitive materials and functional protective films for electronic displays, in addition to the solution casting film forming apparatus, an undercoat layer, an antistatic layer, an antihalation layer, a protective layer, etc. In many cases, a coating device is added to the surface processing of the film. Each of these manufacturing processes is described in detail on pages 25 to 30 of the above-mentioned public technical number 2001-1745, and is classified into casting (including co-casting), metal support, drying, peeling, stretching, etc. Is done.

  Here, although the space temperature of a casting part is not specifically limited in this invention, It is preferable that it is -50-50 degreeC. Furthermore, it is preferable that it is -30-40 degreeC. In particular, the cellulose acylate solution cast at a low space temperature can be cooled on the support instantly to increase the gel strength, thereby holding the film containing the organic solvent. Thereby, without evaporating the organic solvent from the cellulose acylate, it can be peeled off from the support in a short time, and high-speed casting can be achieved. The means for cooling the space may be normal air, nitrogen, argon, helium or the like, and is not particularly limited. The humidity in that case is preferably 0 to 70% RH, and more preferably 0 to 50% RH. Moreover, in this invention, the temperature of the support body of the casting part which casts a cellulose acylate solution is -50-130 degreeC, Preferably it is -30-25 degreeC. In order to keep the casting part at the temperature of the present invention, it may be achieved by introducing a cooled gas into the casting part, or a cooling device may be arranged in the casting part to cool the space. At this time, it is important to take care not to attach water, and it can be carried out by a method such as using dry gas.

  In the casting step, one kind of cellulose acylate solution may be cast as a single layer, or two or more kinds of cellulose acylate solutions may be cast simultaneously and / or sequentially.

  As a method of co-casting a plurality of cellulose acylate solutions of two or more layers as described above, for example, a solution containing cellulose acylate from a plurality of casting openings provided at intervals in the traveling direction of the support. A method of casting and laminating each (for example, a method described in JP-A-11-198285) A method of casting a cellulose acylate solution from two casting ports (a method described in JP-A-6-134933) A method of wrapping a flow of a high-viscosity cellulose acylate solution with a low-viscosity cellulose acylate solution and simultaneously extruding the high- and low-viscosity cellulose acylate solution (method described in JP-A-56-162617), etc. Can be mentioned. The present invention is not limited to these.

The obtained film is peeled off from the support (band) and further dried. The drying temperature in the drying step is preferably 40 to 250 ° C, particularly preferably 70 to 180 ° C.
Further, in order to remove the residual solvent, it is preferably dried at 50 to 160 ° C., and in that case, the residual solvent is preferably evaporated by drying with high-temperature air whose temperature is changed successively. The above method is described in Japanese Patent Publication No. 5-17844. According to this method, the time from casting to stripping can be shortened. The drying temperature, the amount of drying air, and the drying time vary depending on the solvent used, and can be appropriately selected according to the type and combination of the solvents used. The amount of residual solvent in the final finished film is preferably 2% by mass or less, and more preferably 0.4% by mass or less in order to obtain a film having good dimensional stability. The specific method of these drying processes may use, for example, any of the conventionally known methods and apparatuses described in the above-mentioned Technical Report of the Invention Association, and is not particularly limited.

  The thickness of the film produced according to the present invention is preferably 5 to 500 μm, more preferably 15 to 300 μm, and most preferably 20 to 200 μm. In the case of an optical film, 20 to 120 [mu] m, and further 30 to 80 [mu] m are also preferable embodiments.

[Characteristics of polymer film]
[Film surface properties]
The coefficient of dynamic friction of the transparent support used in the present invention is preferably 0.4 or less, and particularly preferably 0.3 or less. If the coefficient of dynamic friction is large, the substrate will be rubbed strongly between the rolls, resulting in dust generation from the support, increasing the amount of foreign matter adhering to the film, and the frequency of point defects and coating streaks as optical films will exceed the allowable value. End up. The dynamic friction coefficient can be measured by a steel ball method using a 5 mmφ steel ball.

The surface resistivity of the transparent support used in the present invention is preferably 1.2 × 10 ¹² Ω / □ or less, more preferably 1.0 × 10 ¹² Ω / □ or less, and It is particularly preferably 8 × 10 ¹² Ω / □ or less. By setting the surface resistivity within the range of the present invention, adhesion of foreign matter to the transparent support or the optical film can be suppressed.

[Mechanical properties of film]
The curl value in the width direction of the transparent support used in the present invention is preferably −10 / m to + 10 / m. When the transparent support of the present invention is subjected to the surface treatment, rubbing treatment, orientation layer, and optical anisotropic layer, which will be described later, on a long and wide transparent support, the width direction of the transparent support is described below. If the curl value is outside the above range, film handling may be hindered and the film may be cut. In addition, the film is strongly in contact with the transport roll at the edge and center of the film, so it is easy to generate dust, and foreign matter adheres to the film more frequently. It became clear that the value was exceeded. In addition, curling within the scope of the present invention is preferable because it can reduce color spot failures that are likely to occur when an optically anisotropic layer is installed, and can prevent bubbles from entering when the polarizing film is bonded.
The curl value can be measured according to a measurement method (ANSI / ASCPH1.29-1985) defined by the American National Standards Institute.

  In the present invention, the amount of residual solvent of the transparent support (cellulose film) is preferably 1.5% or less from the viewpoint of curling, and more preferably 1.0% or less. This is presumably because free deposition is reduced by reducing the amount of residual solvent during film formation by the above-described solvent casting method.

The tear strength of the cellulose film is preferably 3 to 50 g at 30 ° C. and 85% RH. The scratch strength is preferably 3 g or more, more preferably 5 g or more, and particularly preferably 10 g or more. Within these ranges, the scratch resistance and handling properties of the film surface can be maintained without problems.
The scratch strength can be evaluated with a load (g) by which the surface of the support is scratched with a sapphire needle having a cone apex angle of 90 degrees and a tip radius of 0.25 m, and the scratch mark can be visually confirmed.

[Hygroscopic expansion coefficient of film]
The hygroscopic expansion coefficient of the cellulose acylate film of the present invention is preferably 30 × 10 ⁻⁵ /% RH or less. The hygroscopic expansion coefficient is preferably 15 × 10 ⁻⁵ /% RH or less, and more preferably 10 × 10 ⁻⁵ /% RH or less. The hygroscopic expansion coefficient is preferably small, but usually it is 1.0 × 10 ⁻⁵ /% RH or more. The hygroscopic expansion coefficient indicates the amount of change in the length of the sample when the relative humidity is changed at a constant temperature.
By adjusting the hygroscopic expansion coefficient, the durability of the polarizing plate protective film is improved, or while maintaining the optical compensation function when used for the support film of the optical compensation sheet, the frame-shaped transmittance increases, that is, Light leakage due to distortion can be prevented.

  The method for measuring the hygroscopic expansion coefficient is shown below. A sample having a width of 5 mm and a length of 20 mm was cut out from the produced cellulose acylate film, and one end was fixed and suspended in an atmosphere of 25 ° C. and 20% RH (R0). A weight of 0.5 g was hung from the other end and left for 10 minutes to measure the length (L0). Next, the length (L1) was measured while maintaining the temperature at 25 ° C. and the humidity at 80% RH (R1). The hygroscopic expansion coefficient was calculated by the following equation. The measurement was performed 10 samples for the same sample, and the average value was adopted.

  Hygroscopic expansion coefficient [/% RH] = {(L1-L0) / L0} / (R1-R0)

  By adding the plasticizer of the present invention, the dimensional change due to moisture absorption of the produced cellulose acylate film can be reduced. Furthermore, the dimensional change can be further reduced by adding fine particles or the like. This seems to be because a plasticizer having a polycyclic alicyclic structure having a bulky and hydrophobic property in the molecule works effectively. It is also preferable from the viewpoint of reducing dimensional change to reduce the free volume by decreasing the amount of residual solvent in the cellulose acylate film. Specifically, it is preferable to dry under the condition that the residual solvent amount with respect to the cellulose acylate film is in the range of 0.001 to 1.5% by mass. More preferably, it is 0.01-1.0 mass%.

[Moisture permeability and moisture content of film]
The moisture permeability of the cellulose acylate film of the present invention is ^{2 to} 150 g / m ² · 24 h in JIS standard JISZ0208, condition B (temperature 40 ° C., humidity 90% RH). More preferably 10~120g / m ² · 24h, and particularly preferably 10~100g / m ² · 24h. At 150 g / m ² · 24 h or less, the absolute value of the humidity dependency of the Re value and Rth value of the film can be 0.5 nm /% RH or less, which is preferable. Further, when the optical compensation sheet is formed by laminating an optically anisotropic layer on a cellulose acylate film, the absolute value of the humidity dependence of the Re value and the Rth value can be 0.3 nm /% RH or less, preferable. When this optical compensation sheet or polarizing plate is incorporated in a liquid crystal display device, it is preferable because it does not cause a change in color and a decrease in viewing angle.

In addition, when the moisture permeability of the cellulose acylate film is 2 g / m ² · 24 h or more, when the polarizing plate is produced by sticking to both surfaces of the polarizing film, drying of the adhesive is not hindered by the cellulose acylate film. Good adhesion is obtained, which is preferable. The measurement method of moisture permeability is “Polymer Physical Properties II” (Polymer Experiment Course 4, Kyoritsu Shuppan), pages 285-294: Measurement of vapor permeation amount (mass method, thermometer method, vapor pressure method, adsorption amount method) The method described in can be applied.

The water content of the cellulose acylate film constituted as the polarizing plate protective film or the optical compensation sheet of the present invention is not affected by the film thickness so as not to impair the adhesiveness with a water-soluble polymer such as polyvinyl alcohol. It is preferable that it is 0.3-12 g / m < ² > under 30 degreeC85% RH, and it is more preferable that it is 0.5-5 g / m < ² >. At 12 g / m ² or less, the dependency of retardation due to humidity change can be satisfactorily suppressed, which is preferable.

[Method of imparting adhesion to transparent support]
The cellulose acylate film is a method for obtaining adhesion by directly applying a functional layer on a cellulose acylate film after surface activation treatment in order to achieve adhesion with the functional layer provided thereon, There is a method in which an undercoat layer (adhesive layer) is provided after a certain surface treatment or without a surface treatment, and a functional layer is applied thereon. Details of these subbing layers are described on page 32 of the aforementioned technical number 2001-1745. Further, various functional layers of the functional layer of the cellulose acylate film of the present invention are described in detail on pages 32 to 45 of the aforementioned technical number 2001-1745.

  By performing surface treatment depending on the case, it is possible to achieve improved 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. Details of these are described in detail on pages 30 to 32 of the aforementioned public technical number 2001-1745. Among these, an alkali saponification treatment is particularly preferable, and it is extremely effective as a surface treatment of a cellulose acylate film.

  The alkali saponification treatment is also preferably performed 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 coating solution has good wettability because it is applied to the transparent support of the saponification solution, and the surface state remains good without forming irregularities on the surface of the transparent support by the saponification solution solvent. It is preferred to select a solvent to keep. Specifically, description of the content is mentioned, for example in Unexamined-Japanese-Patent No. 2002-82226 and WO02 / 46809.

The contact angle of the transparent support after the surface treatment with water is preferably 20 to 55 degrees. More preferably, it is 25 to 45 degrees. The surface energy is preferably 55 mN / m or more, more preferably 55 to 75 mN / m.
The surface energy of the transparent support can be determined by a contact angle method, a wet heat method, and an adsorption method as described in “Basics and Applications of Wetting” (Realize, 1989.12.10). The contact angle method is preferably used.
Specifically, two kinds of solutions having known surface energies are dropped on a transparent support, and at the intersection between the surface of the liquid droplet and the surface of the support, the angle formed by the tangent line drawn on the liquid drop and the surface of the support The angle containing the droplet is defined as the contact angle, and the surface energy of the support is calculated by calculation.

[Optical film]
The use of the cellulose acylate film produced in the present invention will be briefly described first.
The optical film comprising the cellulose acylate film of the present invention is particularly useful for a polarizing plate protective film. When using as a polarizing plate protective film, the manufacturing method of a polarizing plate is not specifically limited, It can manufacture by a general method. There is a method in which the obtained cellulose acylate film is treated with an alkali and bonded to both sides of a polarizer prepared by immersing and stretching a polyvinyl alcohol film in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. Instead of alkali treatment, easy adhesion processing as described in JP-A-6-94915 and JP-A-6-118232 may be performed. Examples of the adhesive used to bond the protective film treated surface and the polarizer include polyvinyl alcohol adhesives such as polyvinyl alcohol and polyvinyl butyral, vinyl latexes such as butyl acrylate, and the like. The polarizing plate is composed of a polarizer and a protective film that protects both surfaces of the polarizer, and further includes a protective film bonded to one surface of the polarizing plate and a separate film bonded to the other surface. The protective film and the separate film are used for the purpose of protecting the polarizing plate at the time of shipping the polarizing plate and at the time of product inspection. In this case, the protect film is bonded for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the surface where the polarizing plate is bonded to the liquid crystal plate. Moreover, a separate film is used in order to cover the adhesive layer bonded to a liquid crystal plate, and is used for the surface side which bonds a polarizing plate to a liquid crystal plate. In a liquid crystal display device, a substrate containing liquid crystal is usually disposed between two polarizing plates. However, a polarizing plate protective film to which the optical film of the present invention is applied can provide excellent display properties regardless of the location. . In particular, since the polarizing plate protective film on the outermost surface of the display side of the liquid crystal display device is provided with a transparent hard coat layer, an antiglare layer, an antireflection layer, and the like, the polarizing plate protective film is particularly preferably used in this portion.

  The cellulose acylate film of the present invention can be used in various applications, and is effective when used as an optical compensation sheet for an image display device, particularly a liquid crystal display device. The cellulose acylate film of the present invention can be used for liquid crystal cells in various display modes. TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), AFLC (Anti-Ferroly Liquid Liquid Crystal), OCB (Optically Charged TNS). Various display modes such as HAN (Hybrid Aligned Nematic) have been proposed. There has also been proposed a display mode in which the display mode is orientation-divided. The cellulose acylate film is effective in any display mode liquid crystal display device. Further, it is effective in any of a transmissive, reflective, and transflective liquid crystal display device. The cellulose acylate film of the present invention may be used as a support for an optical compensation sheet of a TN type liquid crystal display device having a TN mode liquid crystal cell. The cellulose acylate film of the present invention may be used as a support for an optical compensation sheet of an STN type liquid crystal display device having an STN mode liquid crystal cell. In general, in a STN type liquid crystal display device, rod-like liquid crystalline molecules in a liquid crystal cell are twisted in the range of 90 to 360 degrees, and the refractive index anisotropy (Δn) and cell gap (d) of the rod-like liquid crystalline molecules. Product (Δnd) is in the range of 300 to 1500 nm. The optical compensation sheet used in the STN type liquid crystal display device is described in JP-A-2000-105316. The cellulose acylate film of the present invention is particularly advantageously used as a support for an optical compensation sheet of a VA liquid crystal display device having a VA mode liquid crystal cell. The cellulose acylate film of the present invention is also advantageously used as a support for an optical compensation sheet of an OCB type liquid crystal display device having an OCB mode liquid crystal cell or a HAN type liquid crystal display device having a HAN mode liquid crystal cell.

  The cellulose acylate film of the present invention is also advantageously used as an optical compensation sheet for TN-type, STN-type, HAN-type, and GH (Guest-Host) type reflective liquid crystal display devices. These display modes have been well known since ancient times. The TN type reflection type liquid crystal display device is described in JP-A-10-123478, WO98848320, and Japanese Patent No. 3022477. The optical compensation sheet used for the reflection type liquid crystal display device is described in WO00-65384. The cellulose acylate film of the present invention is also advantageously used as a support for an optical compensation sheet of an ASM type liquid crystal display device having an ASM (Axially Symmetric Aligned Microcell) mode liquid crystal cell. The ASM mode liquid crystal cell is characterized in that the thickness of the cell is maintained by a resin spacer whose position can be adjusted. Other properties are the same as those of the TN mode liquid crystal cell. The ASM mode liquid crystal cell and the ASM type liquid crystal display device are described in a paper by Kume et al. (Kume et al., SID 98 Digest 1089 (1998)). The use of these detailed cellulose acylate films described above is described in detail on pages 45 to 59 of the aforementioned technical number 2001-1745.

  The cellulose acylate film of the present invention is also useful as a support for silver halide photographic light-sensitive materials. The cellulose acylate film of the present invention can be used as a support for any silver halide photographic light-sensitive material for printing plate making, medical use, general photography and the like. The film thickness is more preferably 30 to 250 μm. Such silver halide photographic light-sensitive materials are described in T. H. James et. Al. The Theory of the Photographic Process 4th edition (Macmillan Publishing Co., Inc. 1977).

  Although the specific Example about the cellulose film of this invention is described below, this invention is not limited to these.

<Synthesis example>
Synthesis Example 1 of Polyester Compound: Synthesis of Plasticizer (A-1) The following alcohol compound and a carboxylic acid having the following structure were made into a 30% by mass solution of tetrahydrofuran, and dicyclohexylcarbodiimide (abbreviation: DCC) (carbon An acid and an equimolar amount) and a 50% by mass solution of N, N-dimethylaminopyridine (1 part by mass of DCC) were dropped at a temperature of 25 ° C. and reacted for 5 hours to carry out a dehydration reaction. The reaction mixture was poured into 5 times the amount of water as the reaction mixture, and the reaction mixture was extracted with ethyl acetate and washed thoroughly with water. The ethyl acetate solution was dehydrated with magnesium sulfate, and the product obtained by concentrating the solvent was purified.

Synthesis Example 2 of Polyester Compound: Synthesis of Plasticizer (A-11) A mixture of the following dicarboxylic acid dimethyl ester compound, the following alcohol compound and tetrabutoxy titanate (1 part by mass of the alcohol compound) was reduced to a degree of vacuum of 1 The mixture was heated to 120 to 130 ° C. under 2 mmHg and reacted for 6 hours with stirring. The reaction mixture was dissolved in ethyl acetate, taken out, washed thoroughly with water, the ethyl acetate solution was dehydrated with magnesium sulfate, and the solvent was concentrated to purify the product.

Synthesis Example 3 of Polyester Compound: Synthesis of Plasticizer (A-18) A 30% by mass acetone solution of the following carboxylic acid chloride was cooled to 0 ° C. with stirring. To this solution, a 30% by mass acetone solution of triethylamine (equal molar amount with acid chloride) and a 30% by mass acetone solution of the following alcohol compound (o.95 molar amount of acid chloride) were simultaneously added dropwise at a temperature of 0 ° C. , Reacted for 6 hours. The reaction mixture was poured into 5 times the amount of water, and the reaction product was extracted with ethyl acetate and washed thoroughly with water. The ethyl acetate solution was dehydrated with magnesium sulfate, and the product obtained by concentrating the solvent was purified.

Example 1 and Comparative Example 1
<Manufacture of cellulose acylate film>
[Preparation of fine particle dispersion (RL-1)]
A mixture having the following composition and zirconia beads having a bead diameter of 0.2 mm were charged by a dynomill disperser and wet-dispersed to achieve a volume average particle diameter of 55 nm. From the obtained dispersion, beads were separated with a 200-mesh nylon cloth to prepare a fine particle dispersion (RL-1).
The dispersed particle size of the obtained dispersion was measured with a scanning electron microscope. Moreover, as a result of measuring the particle size distribution of the dispersion (Laser analysis / scattered particle size distribution measuring apparatus LA-920, manufactured by Horiba, Ltd.), the particle size of 300 nm or more was 0%.

(Fine particle dispersion composition)
-Hydrophobic silica {AEROSIL 972 (methyl group modified, primary particle size 16 nm), manufactured by Nippon Aerosil Co., Ltd.} 2.20 parts by mass-Cellulose having an acetylation degree of 59.9% (6-position substitution degree: 0.90) Triacetate
2.00 parts by mass-dispersion aid (B) having the following structure 0.22 parts by mass-methyl acetate 71.0 parts by mass-methanol 6.2 parts by mass-acetone 6.1 parts by mass-ethanol 6.1 parts by mass- 1-butanol 6.1 parts by mass

(Preparation of cellulose acylate solution)
The following components were put into a mixing tank and heated and stirred to prepare a cellulose acylate solution.

(Cellulose acylate solution composition)
・ Cellulose triacetate with acetylation degree of 59.9% (6-position substitution degree: 19.3%)
100 parts by mass
-Plasticizer A (each compound described in Table-A) 12 parts by mass-1.0 part by mass of UV agent (UV-1) having the following structure-1.0 part by mass of UV agent (UV-2) having the following structure-Acetic acid Methyl 290 parts by mass, methanol 25 parts by mass, acetone 25 parts by mass, ethanol 25 parts by mass, 1-butanol 25 parts by mass

10.5 parts by mass of the fine particle dispersion was added to 464 parts by mass of the cellulose acylate solution, and the mixture was sufficiently stirred and allowed to stand at room temperature (25 ° C.) for 3 hours. After cooling for 6 hours at 50 ° C., the dope in which cellulose acylate was completely dissolved was obtained by heating and stirring to 50 ° C. Next, the obtained dope was filtered with a filter paper having an absolute filtration accuracy of 0.01 mm (manufactured by Toyo Filter Paper Co., Ltd., # 63) at 50 ° C., and further a filter paper having an absolute filtration accuracy of 0.0025 mm (FH025, manufactured by Pole Corporation). The dope was prepared by performing filter filtration and defoaming.
Next, the obtained dope was filtered with a filter paper having an absolute filtration accuracy of 0.01 mm (manufactured by Toyo Filter Paper Co., Ltd., # 63) at 50 ° C., and further a filter paper having an absolute filtration accuracy of 0.0025 mm (FH025, manufactured by Pole Corporation). The dope was prepared by performing filter filtration and defoaming. The obtained dope was cast using a band casting machine.

As the casting band, a band made of stainless steel and having a width of 2 m and a length of 56 m (area 112 m ² ) was used. The casting band had a center line average roughness (Ra) of 0.006 μm, a maximum height (Ry) of 0.06 μm, and a ten-point average roughness (Rz) of 0.009 μm. Centerline average roughness (Ra), maximum height (Ry), and ten-point average roughness (Rz) were measured according to JIS B 0601.

The cast dope was dried at a wind speed of 0.5 m / s or less for 1 second immediately after casting, and thereafter dried at a wind speed of 15 m / s. The temperature of the drying air was 50 ° C.
After the film surface temperature on the band reached 40 ° C, after drying for 1 minute and peeling off, the temperature of the drying air was 120 ° C, and the temperature distribution in the width direction of the film at this time was 5 ° C or less. Yes, the average wind speed of drying was 5 m / s, the average value of the heat transfer coefficient was 25 kcal / m ² · Hr · ° C., and the distribution in the width direction of the film was within 5%. Also, the pin tenter supporting portion in the drying zone was prevented from being directly exposed to the hot dry air by a wind shield. In the state of a film having a residual solvent amount of 15% by mass, the film was stretched transversely at a stretch ratio of 25% using a tenter under the condition of 130 ° C., held at 50 ° C. for 30 seconds with the stretched width, and then the clip was removed. And wound up. It was 97% of the total amount of solvent evaporated between stripping and winding. The dried film is further dried with a drying air of 145 ° C. in a drying process in which the film is dried while being conveyed by a roller. Then, the humidity and temperature are adjusted, and the residual solvent amount at the time of winding is 0.35% by mass, the moisture amount is 0. The cellulose acylate films (CA-101), (CA-102), (CAR-101) and (CAR-102) each having a thickness of 65 μm were wound up at 8% by mass.

<Production of polarizer>
The PVA film was immersed in an aqueous solution of 2.0 g / L of iodine and 4.0 g / L of potassium iodide at 25 ° C. for 240 seconds, and further immersed in an aqueous solution of boric acid 10 g / L at 25 ° C. for 60 seconds, followed by tenter stretching. The film was introduced into a machine, stretched 5.3 times, and thereafter, the width was kept constant and dried in an atmosphere at 80 ° C. while shrinking, and then separated from the tenter and wound up. The moisture content of the PVA film before starting stretching was 31%, and the moisture content after drying was 1.5%.
The difference in transport speed between the left and right tenter clips was less than 0.05%. Wrinkles and film deformation at the tenter exit were not observed. The obtained polarizer had a transmittance of 43.7% at 550 nm and a degree of polarization of 99.97%.

<Preparation of polarizing plate>
Each cellulose acylate film formed above is passed through a dielectric heating roll at a temperature of 60 ° C. and heated to a film surface temperature of 40 ° C., and then an alkali solution (S-1) having the composition shown below is applied to a rod coater. Was applied for 15 seconds under a steam far infrared heater manufactured by Noritake Co., Ltd., which was heated to 110 ° C. and applied at a coating amount of 15 cc / m ² , and then pure water using a rod coater. Was applied at 3 cc / m ² . The film temperature at this time was 40 ° C. Next, washing with a fountain coater and draining with an air knife were repeated three times, and then the film was retained in a drying zone at 70 ° C. for 5 seconds and dried.

{Alkaline solution (S-1) composition}
-Potassium hydroxide 8.55 mass%
・ Water 23.235 mass%
・ Isopropanol 54.20% by mass
Surfactant _{(K-1: C 14 H} 29 O (CH 2 CH 2 O) 20 H) 1.0 wt%
Propylene glycol 13.0% by mass
-Antifoaming agent Surfynol DF110D (Nissin Chemical Industry Co., Ltd.) 0.015% by mass

  After drying, a polyvinyl alcohol-based pressure-sensitive adhesive was applied to each cellulose acylate film on the side subjected to alkali saponification treatment to a thickness of about 30 μm, bonded to both sides of the polarizer, and further dried at 80 ° C. to prepare a polarizing plate. .

<Result>
The results of the performance of the obtained cellulose acylate film and polarizing plate are shown in Table B. In addition, the evaluation method of the evaluation item of Table-B was performed as follows.

1) Peelability of film During the film-forming experiment of the cellulose acylate film, the peelability of the film-forming film from the casting band was visually observed.
○: Can be released from the casting band without any problem.
X: An adhesion phenomenon occurs on the casting band, and the mold is not released.

2) Haze The haze of the cellulose triacetate film was measured by using a 1001DP type manufactured by Nippon Denshoku Industries Co., Ltd., stored at a high temperature and high humidity of 90 ° C./80% for 500 hours, and then examined.

3) Tear strength As for the tear strength of the cellulose triacetate film, the excess weight required for tearing was evaluated according to ISO 6383 / 2-1983 using a light heavy tear strength tester manufactured by Toyo Seiki Seisakusho. The sample was stored at 90 ° C./80% under high temperature and high humidity for 500 hours and then examined. The sample size was 50 mm × 64 mm, adjusted at 25 ° C. and 60% RH for 2 hours. The evaluation was performed according to the following criteria.
◎ Overload 600g / mm or more, ○ Overload 400g / mm or more △ Overload 200g / mm or more, × Overload 150g / mm or less

4) Bendability According to ISO8776, it measured using the Toyo Seiki folding tester. The measurement was performed 10 times for each level in the longitudinal direction and the width direction of the sample, and the average value was obtained. This was converted from the thickness of the sample to a value of 100 μm thickness using the following formula.
Folding strength in terms of 100μm (times) = Actual bending strength (times) × (Thickness (μm) / 100)
Evaluation was according to the following criteria.
400 times or more, ○ 200 times or more, △ 100 times or more, × 80 times or less

5) Durability of the film (foreign matter / dirt)
The sample film was examined after being exposed to (50 ° C./80% RH) conditions for 100 hours. The film was cut to a length of 1 m in the longitudinal direction with the full width, and the presence or absence and size of foreign matters and dirt were observed with a magnifying glass while allowing light to pass through the sample on the Schacus Ten, and evaluated according to the following grades.
A: There were no foreign matter and dirt having a size of 50 μm or more, and less than 10 particles of less than 50 μm were observed.
◯: There were no foreign matters and dirt having a size of 50 μm or more, and 10 to 30 particles having a size of less than 50 μm were observed.
(Triangle | delta): The foreign material of a magnitude | size of 50 micrometers or more and dirt were observed less than 1-10 pieces, and 31-50 pieces of 50 micrometers or less were observed.
×: 10 or more foreign matters having a size of 50 μm or more and 51 or more stains of 50 μm or less were observed.

6) Alkali treatment durability (surface after treatment)
The sample film was left in a 1N sodium hydroxide solution at 40 ° C. for 2 minutes. Then, it washed with water and dried for 10 minutes at 70 degreeC. The state of the film surface was visually evaluated in the following three stages.
○: No change is observed Δ: The entire surface is slightly white but is transparent ×: The entire surface is white and opaque

7) Preservability of polarizing plate First, the parallel transmittance and the direct transmittance were measured for the polarizing plate, and the degree of polarization was calculated according to the following formula. Thereafter, each polarizing plate was forcedly deteriorated at 60 ° C. and 90% for 500 hours, and then the parallel transmittance and the direct transmittance were measured again, and the degree of polarization was calculated according to the following formula. The amount of change in polarization degree was determined by the following formula.

Polarization degree P = ((H ₀ −H ₉₀ ) / (H ₀ + H ₉₀ )) 1/2 × 100
Polarization degree change amount = P ₀ −P ₅₀₀
H ₀ : Parallel transmittance, H ₉₀ : Direct transmittance,
P ₀ : Polarization degree before forced deterioration, P ₅₀₀ : Polarization degree after 500 hours of forced deterioration ○: Polarization degree change rate of less than 10% Δ: Polarization degree change rate of 10% or more and less than 25% ×: Polarization degree change rate of 25% that's all.

8) Durability of polarizing plate Two samples having a size of 150 mm × 150 mm are cut out from the polarizing plate, exposed to the condition of (50 ° C./80% RH) for 120 hours, and white generated at the edge of the polarizing plate by crossed Nicols. The area of the void was observed as an area ratio with respect to the entire area, and evaluated according to the following grade.
A: There were no white spots at all.
○: White spots are less than 2% of the entire area.
○ to Δ: The white areas are 2% or more and less than 6% with respect to the entire area.
(Triangle | delta): A blank part is 5% or more and less than 10% with respect to the whole area.
X: The white spot part was 10% or more with respect to the whole area.

In any of the examples and comparative examples, the peelability in the cellulose acylate film forming process was good. The films of Example 1-1 and Example 1-2 were good in haze, tear strength, and surface condition (whether foreign matter, dirt, etc. were generated) even in the samples after storage under high temperature and high humidity. In addition, the film was excellent in bendability and exhibited excellent brittleness resistance. Furthermore, the surface state of the film surface after the alkali saponification treatment in the polarizing plate preparation step was good, and the sample after storage of the prepared polarizing plate under high temperature and high humidity showed good performance that was the same as before aging.
On the other hand, in Comparative Example 1-1 and Comparative Example 1-2, each characteristic after storage under high temperature and high humidity was deteriorated. In addition, the polarizing plate also deteriorated in quality such as change in polarization and occurrence of white spots over time.

Example 1-3 to Example 1-16
In Example 1-1, a film thickness of 65 μm was obtained in the same manner as in Example 1-1 except that each compound shown in Table-C was used instead of the plasticizer (A-1) in the cellulose acylate composition. A film was formed. As a result of evaluating the performance of the film and the polarizing plate in the same manner as in Example 1-1, good results equivalent to those in Example 1-1 were obtained.

Example 2
(Preparation of fine particle dispersion)
A solution having the following composition was prepared and dispersed with an attritor so that the volume average particle diameter was 80 nm. The particle size distribution of the obtained dispersion was 0% for particles having a particle size of 500 nm or more.

(Fine particle dispersion composition)
-Hydrophobic silica {AEROSIL R812 (methyl group modified, primary particle size 7 nm), manufactured by Nippon Aerosil Co., Ltd.} 2.00 parts by mass-Acetylation degree 60.7% (6-position substitution degree 18.5%) Cellulose triacetate
2.00 parts by mass, methylene chloride 78.70 parts by mass, methanol 14.20 parts by mass, 1-butanol 2.80 parts by mass

(Preparation of cellulose acylate solution)
A composition having the following contents was dissolved by stirring to prepare a cellulose acylate solution.

(Composition)
-Cellulose triacetate with acetylation degree of 60.7% (6-position substitution degree of 0.90)
100 parts by mass-Plasticizer with the following structure (A-17) 7.5 parts by mass-Plasticizer with the following structure (A-18) 5 parts by mass-300 parts by mass of methylene chloride-54 parts by mass of methanol-11 parts by mass of 1-butanol Part

  The following components were heated and stirred to prepare a retardation adjusting agent solution.

(Retardation adjuster solution composition)
-2-hydroxy-4-benzyloxybenzophenone 12 parts by mass-2,4-benzyloxybenzophenone 4 parts by mass-Methylene chloride 82.2 parts by mass-Methanol 14.8 parts by mass-1-butanol 3.0 parts by mass

  After adding 15.3 parts by mass of the fine particle dispersion to 474 parts by mass of the cellulose acylate solution and sufficiently stirring, 22 parts by mass of the retardation adjusting agent solution is added and sufficiently stirred to further room temperature (25 ° C.). The resulting non-uniform gel-like solution was cooled at −70 ° C. for 6 hours, and then heated to 50 ° C. and stirred to obtain a completely dissolved dope.

  Next, the obtained dope was filtered with a filter paper having an absolute filtration accuracy of 0.01 mm (manufactured by Toyo Filter Paper Co., Ltd., # 63) at 50 ° C., and further a filter paper having an absolute filtration accuracy of 0.0025 mm (FH025, manufactured by Pole Corporation). The dope was prepared by performing filter filtration and defoaming. The drum is hard chrome plated and the surface has a center line average roughness (Ra) of 0.010 μm, a maximum height (Ry) of 0.60 μm, and a ten-point average roughness (Rz) of 0.016 μm. The one with a diameter of 200 mm and a width of 2500 mm was used.

  The casting method was performed under the same conditions as the band casting described in Example 1. After the film surface temperature on the drum surface reaches 40 ° C., the film is dried for 1 minute, and after peeling off the film having a residual solvent amount of 50% by mass, the residual solvent amount is 40% by mass with 140 ° C. drying air. The film was stretched 17% in the width direction using a tenter, and held at 130 ° C. for 30 seconds with the width after stretching. Thereafter, the cellulose acylate film (CA-2) having a residual solvent amount of 0.25% by mass is dried with a drying air at 130 ° C. for 20 minutes, and a winding roll having a thickness of 60 μm, a length of 1000 m, and a width of 1.34 m. Manufactured in the form.

The cellulose acylate film (CA-2) obtained had a retardation value (Re) at a wavelength of 550 nm of 8 nm and a retardation value (Rth) at a wavelength of 590 nm of 75 nm.
The retardation value was measured by using an ellipsometer (M-150, manufactured by JASCO Corporation), the Re retardation value (Re550) and the Rth retardation value (Rth550) at a wavelength of 550 nm.

Comparative Example 2
In Example 2, instead of the plasticizer (A-17) in the cellulose acylate composition, a cellulose acylate film (in the same manner as in Example 2 except that the following comparative compound (AR-3) was used) CAR-2) was produced.

(Characteristics of cellulose acylate film)
Each performance of the obtained films was evaluated in the same manner as in Example 1. The results are shown in Table-D.

  Subsequently, an alkali saponification treatment, formation of an alignment film, and formation of an optically anisotropic layer were performed as follows to prepare an optical compensation sheet, and the following evaluations were performed.

[Alkaline saponification]
The following alkali saponification treatment was performed on one side of each film sample shown in Table-D.
On the film, hot air of 100 ° C. was collided and heated to 45 ° C., and then an alkali solution (S-2) having the following contents kept at 25 ° C. was applied using a rod coater at 14 cc / m ² for 13 seconds. After the lapse of time, 5 cc / m ^{2 of} pure water was applied again using a rod coater. The film temperature at this time was 45 ° C. Next, 1000 cc / m ² of pure water was applied using an extrusion type coater and washed with water. After 5 seconds, 100 m / s of wind was made to collide with the water application surface from an air knife. Washing with an extrusion coater and draining with an air knife were repeated twice, and then, the film was retained in a drying zone at 80 ° C. for 10 seconds and dried. The contact angle of the treated surface with water was 32 degrees.

{Alkaline solution (S-2) composition}
・ Sodium hydroxide 4.0% by mass
・ Water 62.0 mass%
・ N-propanol 33.0% by mass
-Surfactant (K-2: ethylenediamine ethylene oxide adduct) 1.0% by mass
・ Antifoamer Surfynol 104 (Nissin Chemical Industry Co., Ltd.) 0.01% by mass

[Film properties after alkali saponification]
(Surface shape: foreign matter, cloudiness)
A saponified film was cut out to a length of 1 m in the longitudinal direction with the full width, and the sample was observed visually and with a loupe for light and foreign matter and turbidity while allowing light to pass through the shaucus ten, and evaluated using the following criteria.
◯: No foreign matter or turbidity is found (level evaluated by 10 people and unrecognizable by one person)
Δ: Foreign matter and turbidity are weakly generated (level evaluated by 10 people and recognized by 2 to 5 people)
X: Foreign matter and turbidity are strongly generated (level evaluated by 10 people and recognized by 6 or more people)

Each film subjected to hydrophilization surface treatment was evaluated for the above contents, and the results are shown in Table-E. In Example 2 (CA-2) of the present invention, the contact angle with water was 34 degrees within the surface of 1 square meter, and it was a uniform treatment with no in-plane variation. Generation of foreign matter and turbidity was not observed on the entire surface of the film. In Comparative Example 2 (CAR-2), the variation in the contact angle with water in a 1 square meter plane was large, which was 33 to 39 degrees. Further, the surface condition deteriorated, and in particular, many foreign matters were observed.
As described above, it was revealed that Example 2 of the present invention can make the in-plane hydrophilic uniformly.

<Formation of alignment film>
On each hydrophilized surface-treated film, an alignment film coating solution having the following composition was coated with a rod coater at a coating amount of 28 ml / m ² . Drying was performed with warm air of 60 ° C. for 60 seconds, and further with warm air of 90 ° C. for 150 seconds.
When the pH of the coated surface after drying was measured, the value was 4.0. Further, the pH values at the center and the positions at the left and right ends in the coating width direction were in the range of 3.95 to 4.10.
Next, a rubbing treatment was performed in the longitudinal direction of each hydrophilically treated surface-treated film.

(Alignment film coating solution)
-20% by mass of the following modified polyvinyl alcohol
・ Citric acid 0.06% by mass
・ Glutaraldehyde 0.5% by mass
・ 360% by mass of water
・ Methanol 120% by mass

[Evaluation method of alignment film adhesion]
In accordance with the cross-cut tape method of JIS K-5400 on the surface of the alignment layer, 100 cross hatches (1 mm × 1 mm) using a specified cutter knife and cutter guide are placed at a temperature of 25 ° C. and a relative humidity of 60. After being left for 2 hours under the condition of%, the specified cellophane adhesive tape is applied and rubbed with an eraser to adhere to the coating film. The evaluation was made by measuring the number of squares from which the alignment film was peeled off from the transparent support when the tape was peeled off in a direction perpendicular to the coating surface 2 minutes after the tape was attached.
A: No peeling at 100 mm was observed. ○: No peeling was observed at 100 mm within 2 mm. Δ: 10-100 mm was observed at 100 mm. Thing that has been peeled off at 100 mm exceeds 10 mm

<Formation of optically anisotropic layer>
A discotic liquid crystal coating solution (DA-1) having the following composition is applied with a # 4 wire bar coater, heated in a high-temperature bath at 125 ° C. for 3 minutes to align the discotic liquid crystal, and then a high-pressure mercury lamp is used. Then, UV was irradiated at 500 mJ / cm ² and allowed to cool to room temperature to prepare optical compensation sheets (KS-1) and (KSR-1) described in Table-E. The thickness of the optically anisotropic layer of each film was 1.6 μm.

(Discotic liquid crystal coating solution (DA-1))
-9.1 parts by mass of the following discotic liquid crystal (DLC-A)-0.9 parts by mass of ethylene oxide-modified trimethylolpropane acrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.)-Cellulose acetate butyrate (CAB551- 0.2, manufactured by Eastman Chemical) 0.2 parts by mass, cellulose acetate butyrate (CAB531-1, manufactured by Eastman Chemical) 0.05 parts by mass, fluorine-containing compound having the following structure 1.3 parts by mass, Irgacure 907 (manufactured by Ciba Geigy) 3.0 parts by mass, Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) 0.1 parts by mass, 29.6 parts by mass of methyl ethyl ketone

[Performance evaluation method of optical compensation sheet]
(Adhesion)
The optical compensation sheets (KS1-1) and (KSR-1) shown in Table-E were attached to a glass plate using an acrylic adhesive and stored at 90 ° C. for 20 hours. The acrylic adhesive is the same as that used for assembling the liquid crystal display device, and the glass plate is the same as that used for the liquid crystal cell. The adhesiveness was evaluated by peeling the optical compensation sheet from the glass plate in the vertical direction and examining the part where the peeling residue occurred.
◎: Not generated at all (level that 10 people can evaluate and no one can recognize)
○: Slightly occurring (level evaluated by 10 people and recognized by 1 to 3 people)
Δ: Weak occurrence (level evaluated by 10 people and recognized by 3 to 5 people)
X: Strongly generated (level evaluated by 10 people and recognized by 6 or more people)

(Uneven transmission light)
Each optical compensation sheet was sandwiched between two polarizing plates arranged in crossed Nichols, and the unevenness of transmitted light was visually observed for sensory evaluation.
○: Not generated at all (a level at which 10 people evaluate and one cannot recognize)
Δ: Weak occurrence (level evaluated by 10 people and recognized by 1 to 5 people)
X: Strongly generated (level evaluated by 10 people and recognized by 6 or more people)

  These results are listed in Table E. The optical compensation sheet (KS-1) of the present invention had a sufficiently good adhesion and was very good with no unevenness in transmitted light.

<Creation of liquid crystal display device>
A pair of polarizing plates provided in a liquid crystal display device (6E-A3, manufactured by Sharp Corporation) using a TN type liquid crystal cell is peeled off, and each polarizing plate prepared above is replaced with the optical compensation prepared above. The sheets were attached to the observer side and the backlight side one by one through an adhesive so that the sheet was on the liquid crystal cell side. The transmission axis of the polarizing plate on the observer side and the transmission axis of the polarizing plate on the backlight side were arranged so as to be in the O mode.

[Evaluation of unevenness in drawn images]
With respect to the liquid crystal display device thus fabricated, the drawing unevenness during black display (L1) was visually observed using a measuring instrument (EZ-Contrast 160D, manufactured by ELDIM). The results are shown in Table-E.
○: Not generated at all (a level at which 10 people evaluate and one cannot recognize)
Δ: Weak occurrence (level evaluated by 10 people and recognized by 1 to 5 people)
X: Strongly generated (level evaluated by 10 people and recognized by 6 or more people)

(Drawing image contrast and viewing angle)
A white display voltage of 2 V and a black display voltage of 6 V were applied to the liquid crystal cell of the liquid crystal display device, and the front contrast ratio was measured using a measuring instrument (EZ-Contrast 160D, manufactured by ELDIM). Further, the viewing angle (angle range where the contrast ratio is 10 or more) in the left-right direction (the direction orthogonal to the cell rubbing direction) was examined. The results are shown in Table-E.

As a result, the cellulose acylate film (CA-2) according to the above-described method of the present invention installed so as to be a protective film is a clear and high-brightness image with no fog on the entire screen surface, and contrast and A drawn image with an excellent viewing angle was obtained. On the other hand, the comparative film (CAR-1) has a problem in that it has unevenness over the entire screen and is put to practical use.
From the above visual observation results, it was shown that the film using the cellulose acylate film of the present invention has good optical characteristics, and the liquid crystal image device provided with the film has excellent drawing properties.

Example 3
<Preparation of cellulose acylate film>
[Preparation of cellulose acetate solution]
A cellulose acetate stock solution (original dope solution) having the composition shown in Table F below was prepared. In the dissolution, raw materials were put into a mixing tank and stirred while heating to dissolve each component.

[Preparation of Retardation Adjuster Solution]
The following structural retardation adjusting agent, 16 parts by mass, methyl acetate part, methanol part, acetone part and n-butanol part are put into another mixing tank and stirred while heating to obtain a retardation adjusting solution. Prepared.

[Preparation of cellulose acetate dope solution for inner layer and outer layer]
As shown in Table-G, the composition was added to the mixing tank under stirring in the order of the original dope solution, the retardation agent solution, and then the fine particle dispersion (RL-2), stirred, and mixed, for the inner layer and the outer layer. A cellulose acetate dope solution was prepared. The amount of each of the retardation adjusting agent and fine particle dispersion added to 100 parts by mass of cellulose acetate is shown in Table-G.
The obtained dope was filtered at 50 ° C. with a filter having an absolute filtration accuracy of 0.01 mm (manufactured by Toyo Roshi Kaisha, Ltd., # 63) and a filter having an absolute filtration accuracy of 0.0025 mm (manufactured by Pall, FH025).

  Using a three-layer co-casting die, the filtered dope was placed so that the inner layer dope was on the inside and the outer layer dope was on both sides, and the layers were cast using a band casting machine. The same band casting machine as in Example 1 was used. The dope discharge amount was adjusted so that the inner layer thickness was 48 μm and both outer layer thicknesses were 6 μm, the casting and drying conditions were the same as in Example 1, and the stretching ratio was 16% using a tenter and stretched. The cellulose acylate film (CA-3) in the form of a wound roll having a length of 3000 m and a width of 1.2 m was produced by maintaining the subsequent width at 130 ° C. for 30 seconds. Re was 23 nm and Rth was 78 nm.

[Characteristics of cellulose acylate film]
Each characteristic of the obtained transparent support was evaluated, and the results are shown in Table-H.

(Saponification treatment of cellulose acylate film)
On the inner surface of the cellulose acylate film (CA-3), a 1.0 mol / liter potassium hydroxide solution (solvent: isopropyl alcohol / propylene glycol / water = 75/13/12% by mass) is # After applying at 6 bar and heating at 40 ° C for 10 seconds, apply water to the wet application surface with # 1.6 bar and immediately spray 500 cc / m ² of washing water at 25 ° C from the nozzle. The film surface was washed with water three times in succession and dried with hot air at 100 ° C. to prepare a cellulose acylate film (FS-3) having a saponified surface.

<Formation of alignment film>
An alignment film coating solution of the following formulation is applied to one side of a saponified cellulose acylate film with a # 14 wire bar coater and dried for 60 seconds with hot air at 60 ° C. and for 160 seconds with hot air at 90 ° C. Thus, a long roll-like cellulose acylate film provided with an alignment film was produced. Next, rubbing treatment was performed in a direction in which the angle formed with the slow axis direction of the long roll-like cellulose acylate film provided with the alignment film was 45 °.

(Orientation film coating solution formulation)
-19 parts by weight of the following modified polyvinyl alcohol-0.06 parts by weight of the acid compound (A) having the following structure-360 parts by weight of water-120 parts by weight of methanol-1 part by weight of glutaraldehyde

<Preparation of optical compensation sheet>
An optically anisotropic layer having the optically anisotropic layer formed by coating the coating solution for the optically anisotropic layer used in Example 2 on the alignment film of the above-described long roll-like cellulose acetate film in the same manner as in Example 2. A compensation sheet was prepared.
When the performance of the obtained sheet was examined in the same manner as in Example 2, good performance equivalent to that of the optical compensation sheet of Example 2 was obtained.

<Preparation of polarizing plate protective film>
[Preparation of antireflection film]
The light transmissive resin constituting the light diffusing layer is 50 parts of UV curable resin (Nippon Kayaku PETA, refractive index 1.51) and 2 parts by weight of curing initiator (Ciba Geigy, Irgacure 184). As the first translucent fine particles, acrylic-styrene beads (manufactured by Soken Chemical Co., Ltd., particle size 3.5 μm, refractive index 1.55) are 5 parts by weight, and as the second translucent fine particles, styrene beads are used. 5.2 parts by weight (manufactured by Soken Chemical Co., Ltd., particle size 3.5 μm, refractive index 1.60), 10 parts by mass of silane coupling agent KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.), fluorine-based polymer ( f1) was mixed with 0.03 part by mass, and these were mixed with 50 parts by weight of toluene to prepare a coating solution. On the one side of the same polarizing plate produced in Example 1, a dry film thickness of 6.0 μm After coating and solvent drying, 1 Using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 60 W / cm, the coating layer was cured by irradiating ultraviolet rays with an illuminance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ² .

  On the light diffusion layer, a low refractive index layer coating solution having the following formulation is stirred and prepared, filtered through a polypropylene filter having a pore size of 1 μm, coated with a bar coater, dried at 80 ° C. for 5 minutes, and then at 120 ° C. The polymer was crosslinked by heating for 10 minutes to form a low refractive index layer having a thickness of 0.1 μm, and a polarizing plate protective film (a polarizing plate with an antireflection film) was produced.

(Refractive index layer coating formulation)
・ Heat-crosslinkable fluorine-containing polymer (JN-7228, solid content concentration 6%, manufactured by JSR Corporation) 210 parts by mass ・ Silica sol (MEK-ST, average particle size 10-20 nm, solid content concentration 30 wt%, Nissan Chemical ( Co., Ltd.) 18 parts by mass / methyl ethyl ketone 200 parts by mass

<Preparation of polarizing plate>
This polarizing plate protective film and the optical compensation sheet having the optically anisotropic layer prepared as described above are immersed in a 1.5 mol / liter aqueous sodium hydroxide solution having a liquid temperature of 55 ° C. for 1 minute to obtain cellulose acylate. After the surface of the rate film was saponified, it was thoroughly washed with dilute sulfuric acid and water, dried and then coated with a polyvinyl alcohol pressure-sensitive adhesive on the surface side of each cellulose acylate film to a thickness of about 15 μm. A polarizing plate was produced by drying at 0 ° C.

<Production of bend alignment liquid crystal cell>
A polyimide film was provided as an alignment film on a glass substrate with an ITO electrode, and the alignment film was rubbed. The obtained two glass substrates were faced to each other so that the rubbing directions were parallel to each other, and the cell gap was set to 6 μm. A liquid crystal compound having a Δn (wavelength of 550 nm) of 0.1396 (ZLI1132, manufactured by Merck & Co., Inc.) was injected into the cell gap to produce a bend alignment liquid crystal cell.

<Production of bend alignment mode transmission type liquid crystal display device>
Acrylic adhesive is applied on the optically anisotropic layer of the produced polarizing plate so that the produced bend alignment cell is sandwiched so that the rubbing direction of the liquid crystal cell and the rubbing direction of the optical compensation sheet are antiparallel. A transmissive liquid crystal display device in a bonded and bend alignment mode was produced.
A white display voltage of 2 V and a black display voltage of 6 V were applied to the liquid crystal cell of this liquid crystal display device, and the front contrast ratio was measured using a measuring instrument (EZ-Contrast 160D, manufactured by ELDIM). Further, the viewing angle (angle range where the contrast ratio is 10 or more) in the left-right direction (the direction orthogonal to the cell rubbing direction) was examined.
The liquid crystal display device using the film of the present invention has a front contrast ratio of 200 and a viewing angle of 160 °, and has a good contrast and a wide viewing angle. In addition, it was confirmed that the liquid crystal display device had excellent display quality with no fogging or foreign matter on the surface.

Claims (12)

  A cellulose film comprising an ester compound (E) containing at least one polycyclic alicyclic hydrocarbon group and at least two ester bonds in the molecule, and cellulose.   The cellulose film according to claim 1, wherein the polycyclic alicyclic hydrocarbon group is a hydrocarbon group having a polycyclic alicyclic hydrocarbon ring structure having 5 to 32 carbon atoms.   The ester compound (E) is an aliphatic polyol ester of an aliphatic polyol and one or more polycyclic alicyclic hydrocarbon-containing monocarboxylic acids, and an aliphatic polycarboxylic acid and one or more polycyclic alicyclic rings. The cellulose film according to claim 1, wherein the cellulose film is at least one ester compound selected from aliphatic polycarboxylic acid esters with monools containing a hydrocarbon.   The ester compound (E) is an ester compound of a polycyclic alicyclic hydrocarbon compound containing at least two polar groups selected from a hydroxy group and a carboxy group and an aliphatic monool or an aliphatic monocarboxylic acid. The cellulose film according to claim 1, wherein the cellulose film is present.   Furthermore, microparticles | fine-particles are contained, The cellulose film in any one of Claims 1-4 characterized by the above-mentioned. The cellulose film according to any one of claims 1 to 4, wherein the cellulose is a cellulose acylate satisfying all of the following formulas (IIIa) to (IIIb) in terms of substitution degree with hydroxyl groups. .
(IIIa) 2.6 ≦ SA ′ + SB ′ ≦ 3.0
(IIIb) 1.5 ≦ SA ′ ≦ 3.0
(IIIc) 0 ≦ SB ′ ≦ 0.8
SA ′ is the degree of substitution of the acetyl group, and SB ′ is the degree of substitution of the acyl group having 3 to 22 carbon atoms.   A cellulose acylate film obtained by forming a cellulose acylate composition containing the cellulose acylate and the ester compound (E) according to claim 1 by a solution casting method.   A cellulose acylate film is a step of preparing a cellulose acylate composition containing an ester compound (E) by dissolving cellulose acylate in a substantially non-chlorine solvent, a cellulose acylate film from a cellulose acylate solution The cellulose acylate film according to any one of claims 1 to 7, wherein the cellulose acylate film is produced by a step of forming a film and a step of stretching the cellulose acylate film.   An optical film using the cellulose acylate film according to claim 1.   A display device using the optical film according to claim 9.   A support for a silver halide photographic light-sensitive material using the cellulose acylate film according to any one of claims 1 to 8, which has a thickness of 30 to 250 µm.   A polarizing plate using the cellulose acylate film according to claim 1.