JP2005247943A - Solution of cellulose compound and cellulose film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solution of a cellulose compound from which a film having excellent optical characteristics is produced. <P>SOLUTION: The solution of the cellulose compound comprises the cellulose compound, a naphthalene compound substituted with at least one of -COR<SP>1</SP>(R<SP>1</SP>is a hydrogen atom or a substituent) and an organic solvent. Preferably, the naphthalene compound is represented by the general formula (wherein, R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP>, R<SP>5</SP>, R<SP>6</SP>, R<SP>11</SP>and R<SP>12</SP>are each independently a hydrogen atom or a substituent). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a cellulose compound solution containing a naphthalene dicarbonyl compound (hereinafter also referred to as “cellulose compound composition” or “dope”) and a cellulose film produced using the cellulose compound solution.

Cellulose films, especially cellulose acetate films, are characterized by high optical isotropy (low retardation value) compared to other polymer films. Therefore, it is common to use a cellulose acetate film for an application requiring optical isotropy, for example, a polarizing plate.
On the other hand, optical anisotropy (high retardation value) is required for an optical compensation sheet (retardation film) such as a liquid crystal display device. Therefore, it has been common to use a synthetic polymer film having a high retardation value such as a polycarbonate film or a polysulfone film as the optical compensation sheet.

By the way, recently, a cellulose acetate film having a high retardation value has been required even for applications requiring optical anisotropy, and a technique corresponding to the cellulose acetate film has been proposed (for example, Patent Documents). 1). In the technique in Patent Document 1, in order to realize a high retardation value with a cellulose triacetate film, an aromatic compound having at least two aromatic rings, particularly a compound having a 1,3,5-triazine ring, is added and stretched. Technology to process.
In general, cellulose triacetate is a polymer material that is difficult to stretch, and it is known that it is difficult to increase the birefringence. However, in Patent Document 1, the aromatic compound added is simultaneously oriented by a stretching process. This increases the birefringence and achieves a high retardation value.

  Also, in recent years, TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal (FLC), Anti-Ferroelectric Liquid N Crystal (CV), OCB (Optically STP). Various display modes such as Vertically Aligned) and HAN (Hybrid Aligned Nematic) have been proposed, and an optical compensation film having optical anisotropy suitable for each mode has been demanded.

European Patent Application 0911656A2

  As a result of intensive studies on the method disclosed in Patent Document 1 using a known discotic compound having a 1,3,5-triazine ring, the present inventors have found that the Re retardation value and Rth letter It has been found that there is a problem that a film having a high (Re / Rth) value cannot be produced in any combination. Therefore, development of new optical performance control technology has become necessary.

  An object of the present invention is to provide a cellulose film having excellent optical properties. Another object is to provide a cellulose compound solution (dope) capable of producing a film excellent in such optical performance.

The object of the present invention has been achieved by the following means. That is, the present invention includes a cellulose compound, a naphthalene compound substituted by at least one -COR ¹ and (R ¹ represents a hydrogen atom or a substituent.), Cellulose compound, characterized in that it contains an organic solvent Solution. More specifically, the present invention is a cellulose compound solution comprising a cellulose compound, a naphthalene dicarbonyl compound represented by the following general formula (1), and an organic solvent.

General formula (1)

ここで、式中のＲ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^１１およびＲ^１２はそれぞれ独立に水素原子又は置換基を表す。なお、置換基については、後述する。

Here, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹¹ and R ¹² in the formula each independently represent a hydrogen atom or a substituent. The substituent will be described later.

  Further, the present invention includes a cellulose film obtained by casting the cellulose compound solution, that is, a cellulose compound and a naphthalenedicarbonyl compound represented by the general formula (1). It is the cellulose film characterized.

  Using the cellulose compound solution of the present invention, a film having a large (Re retardation value) / (Rth retardation value), that is, a high retardation value can be produced.

As described above, the cellulose compound solution of the present invention contains a cellulose compound, a naphthalene dicarbonyl compound of the general formula (1), and an organic solvent.
This will be described in more detail below.

[Cellulose compound solution (cellulose compound composition)]
In the naphthalene dicarbonyl compound of the general formula (1) used in the present invention, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹¹ and R ¹² are each independently a hydrogen atom or a substituent. As the substituent, a substituent T described later can be applied. If possible, these substituents may be further substituted.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are preferably a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, substituted or unsubstituted amino group, alkoxy group, aryloxy Group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, A ureido group, a hydroxy group, a halogen atom, a cyano group, a carboxyl group or a heterocyclic group,
More preferably, a hydrogen atom, an alkyl group, an aryl group, a substituted or unsubstituted amino group, an alkoxy group, an aryloxy group, a hydroxy group, a halogen atom,
More preferably, they are a hydrogen atom or a hydroxy group,
Particularly preferred is a hydrogen atom.

R ¹¹ and R ¹² are preferably a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, substituted or unsubstituted amino group, alkoxy group, aryloxy group, acyloxy group, alkoxycarbonylamino group, aryloxy A carbonylamino group, a sulfonylamino group, an alkylthio group, an arylthio group or a heterocyclic group, more preferably a substituted or unsubstituted amino group, an alkoxy group, an aryloxy group, an alkylthio group or an arylthio group.

Of the naphthalene dicarbonyl compounds represented by the general formula (1), the compounds represented by the general formula (1-A) are preferable.
Formula (1-A)

In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ have the same meanings as those in the general formula (1), and preferred ranges thereof are also the same. X ¹ and X ² are each independently —O— or NR— (R represents a hydrogen atom, an alkyl group or an aryl group), preferably —O— or NH—, more preferably — O-.

R ²¹ and R ²² each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and when possible, these are substituted with a substituent represented by the substituent T described later. May be.

The alkyl group represented by R ²¹ and R ²² may be linear or branched, preferably has 1 to 20 carbon atoms, more preferably has 1 to 12 carbon atoms, and still more preferably has carbon atoms. It is 1-8, Most preferably, it is C2-C8.
The alkenyl group represented by R ²¹ and R ²² may be linear or branched, preferably has 2 to 20 carbon atoms, more preferably has 2 to 12 carbon atoms, and still more preferably has carbon atoms. It is 2-8, Most preferably, it is C2-C6.
The alkynyl group represented by R ²¹ and R ²² may be linear or branched and preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 2 carbon atoms. 8 and particularly preferably 2 to 6 carbon atoms.

The aryl group represented by R ²¹ and R ²² preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, still more preferably 6 to 12 carbon atoms (for example, phenyl, p-methylphenyl, Naphthyl, etc.), particularly preferably a phenyl group.

The heterocyclic group represented by R ²¹ and R ²² is preferably a 5- or 6-membered heterocyclic ring containing at least one of an oxygen atom, a nitrogen atom and a sulfur atom, more preferably A 5- or 6-membered aromatic heterocyclic ring containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom, such as furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine , Indole, indazole, purine, thiazoline, thiazole, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole Benzoxazole, benzthiazole, benzotriazole, tetrazaindene. More preferred heterocyclic groups are pyridine and triazine.

R ²¹ and R ²² are preferably an alkyl group, an alkenyl group, and an aryl group.

The substituents in R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹¹ , R ¹² , R ²¹ and R ²² (and the substituent T in the substituents) will be described below. To do.
Examples of the substituent (substituent T) include an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as methyl, ethyl, iso- Propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms). Particularly preferably, it has 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, 3-pentenyl and the like, and an alkynyl group (preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms). , Particularly preferably having 2 to 8 carbon atoms, such as propargyl and 3-pentynyl).

An aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, naphthyl, etc.), substituted or not Substituted amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino, etc. An alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as methoxy, ethoxy, butoxy, etc.), aryloxy Group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, Oxy, 2-naphthyloxy, etc.), acyl groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl , Pivaloyl, etc.),

An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, etc.), an aryloxycarbonyl group ( Preferably it has 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms, and examples thereof include phenyloxycarbonyl, etc.), an acyloxy group (preferably 2 to 20 carbon atoms, More preferably, it has 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetoxy, benzoyloxy, etc.), an acylamino group (preferably 2 to 20 carbon atoms, more preferably 2 to 2 carbon atoms). 16, particularly preferably 2 to 10 carbon atoms, such as acetylamino, benzoylamino An alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino). An aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino);

A sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino, benzenesulfonylamino, etc.), a sulfamoyl group ( Preferably it is C0-20, More preferably, it is C0-16, Most preferably, it is C0-12, For example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl etc. are mentioned. ), A carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, and phenylcarbamoyl). An alkylthio group (preferably having 1 to 20 carbon atoms) Preferably it is C1-C16, Most preferably, it is C1-C12, for example, methylthio, ethylthio etc. are mentioned, for example, An arylthio group (Preferably C6-C20, More preferably C6-C16, Particularly preferably, it has 6 to 12 carbon atoms, and examples thereof include phenylthio, etc.), an alkylsulfonyl group or an arylsulfonyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably carbon numbers). 1 to 12, for example, mesyl, tosyl, etc.)

Alkylsulfonyl group or arylsulfinyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc.), ureido A group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as ureido, methylureido, phenylureido, etc.), phosphoric acid amide group ( Preferably it has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include diethyl phosphoric acid amide and phenyl phosphoric acid amide.), Hydroxy group, mercapto group , Halogen atoms (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, Pho group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms. An atom, an oxygen atom, a sulfur atom, specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, etc., a silyl group (preferably having 3 carbon atoms) To 40, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyl and triphenylsilyl). These substituents may be further substituted.

  Moreover, when there are two or more substituents, they may be the same or different. If possible, they may be linked together to form a ring.

  Specific examples of the compound represented by formula (1) or (1-A) will be described below in detail, but the present invention is not limited to the following specific examples.

  Although the synthesis | combination of compound (Re-13) of an example of the compound used by this invention is described concretely below, this invention is not limited at all by the following specific examples.

[Synthesis Example 1: Synthesis of Exemplified Compound Re-13]
After 162 g (0.75 mol) of 2,6-naphthalenedicarboxylic acid and 675 mL of N, N-dimethylformamide 189 g (2.25 mol) of sodium bicarbonate were heated to 80 ° C., 199.6 g (1.65) of allyl bromide was heated. Mol) was slowly added dropwise and heated at 95-98 ° C. for 4 hours after the addition. Thereafter, the reaction solution was cooled to room temperature and dropped into 3 L of water. The obtained crystals were dissolved in 1 L of ethyl acetate, magnesium sulfate was added to remove water, and then ethyl acetate was distilled off. The obtained crystals were dispersed in 1 L of hexane, and the crystals were filtered off to obtain 103 g (yield 46%) of the target compound as a white powder.

  It is preferable to add 0.1 to 20% by mass of the compound represented by the general formula (1) or (1-A) with respect to the cellulose compound, and more preferably 0.5 to 16%. It is 1 mass%, More preferably, it is 1-12 mass%, Most preferably, it is 2-8 mass%. Most preferably, it is 3-7 mass%.

The cellulose compound solution of the present invention is a cellulose compound or a compound having a cellulose skeleton obtained by introducing a functional group biologically or chemically using cellulose as a raw material, and the general formula (1) or (1-A). A composition comprising at least one of the compounds represented. The compound having a cellulose skeleton is preferably a cellulose ester, and more preferably cellulose acylate (including cellulose triacylate and cellulose acylate propionate). In the present invention, two or more different cellulose acylates may be mixed and used.
Hereinafter, the present invention will be described using a case where cellulose acylate is used as the cellulose compound as a representative example.

The cellulose acylate preferably used in the cellulose compound includes the following materials. That is, the cellulose acylate is a cellulose acylate in which the degree of substitution of the cellulose with a hydroxyl group satisfies all of the following formulas (I) to (III).
(I) 2.3 ≦ SA + SB ≦ 3.0
(II) 1.5 ≦ SA ≦ 3.0
(III) 0 ≦ SB ≦ 0.8

  Here, SA and SB in the formula represent a substituent of an acyl group substituted with a hydroxyl group of cellulose, SA is a substitution degree of an acetyl group, and SB is a substitution degree of an acyl group having 3 to 22 carbon atoms. . 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 has a degree of substitution of 1). In the present invention, the total sum of the substitution degree of the hydroxyl group SA and SB is more preferably 2.7 to 2.96, and particularly preferably 2.80 to 2.95. Further, the degree of substitution of SB is 0 to 0.8, particularly 0 to 0.6. Further, SB is preferably 28% or more of the substituent group of the 6-position hydroxyl group, more preferably 30% or more is the substituent of the 6-position hydroxyl group, more preferably 35% or more, and particularly preferably 40% or more. It is also preferable that the substituent is a 6-position hydroxyl group. Furthermore, the cellulose acylate in which the total substitution degree of SA and SB at the 6-position of the cellulose acylate is 0.8 or more, further 0.85 or more, and particularly 0.90 or more can be mentioned. .

  In the present invention, the acyl group having 3 to 22 carbon atoms representing the above-mentioned SB of cellulose acylate may be an aliphatic acyl group or an aromatic acyl group, and is not particularly limited. These are, for example, cellulose alkylcarbonyl esters, alkenylcarbonyl esters, aromatic carbonyl esters, aromatic alkylcarbonyl esters, and the like, each of which may further have a substituted group. These preferred substituents representing SB include propionyl, butanoyl, heptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, iso-butanoyl, pivaloyl, cyclohexanecarbonyl, oleyl, Examples include benzoyl, naphthylcarbonyl, cinnamoyl groups and the like. Among these, propionyl, butanoyl, dodecanoyl, octadecanoyl, pivaloyl, oleoyl, benzoyl, naphthylcarbonyl, cinnamoyl and the like are more preferable.

  The basic principle of the cellulose acylate synthesis method is described in Nobuhiko Umeda et al., Wood Chemistry pages 180-190 (Kyoritsu Shuppan, 1968). A typical synthesis method is a liquid phase acetylation method using a carboxylic acid anhydride-acetic acid-sulfuric acid catalyst. Specifically, cellulose raw materials such as cotton linter and wood pulp are pretreated with an appropriate amount of acetic acid, and then put into a pre-cooled carboxylic acid mixture to be esterified to complete cellulose acylate (2nd, 3rd and 6th). The total degree of acyl substitution at the position is approximately 3.00). The carboxylated mixed solution generally contains acetic acid as a solvent, carboxylic anhydride as an esterifying agent, and sulfuric acid as a catalyst.

  The carboxylic anhydride is usually used in a stoichiometric excess over the sum of the cellulose that reacts with it and the water present in the system. After completion of the acylation reaction, a neutralizing agent (for example, calcium, magnesium, iron, aluminum or zinc) is used for hydrolysis of excess carboxylic anhydride remaining in the system and neutralization of a part of the esterification catalyst. Of carbonate, acetate or oxide). Next, the obtained complete cellulose acylate is saponified and aged by maintaining it at 50 to 90 ° C. in the presence of a small amount of an acetylation reaction catalyst (generally, remaining sulfuric acid) to obtain the desired degree of acyl substitution and polymerization. The cellulose acylate having a degree is changed. When the desired cellulose acylate is obtained, the catalyst remaining in the system is completely neutralized with a neutralizing agent as described above, or in water or dilute sulfuric acid without neutralization. The cellulose acylate solution is added (or water or dilute sulfuric acid is added into the cellulose acylate solution) to separate the cellulose acylate, and the cellulose acylate is obtained by washing and stabilizing treatment.

  The cellulose acylate film of the present invention is preferably composed of a cellulose acylate in which the polymer component constituting the film substantially has 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 polymer component. The balance is a naphthalene dicarbonyl compound of the general formula (1), a plasticizer, an ultraviolet absorber and the like. When preparing a cellulose composition which is a raw material for film production, it is preferable to use cellulose acylate particles. 90% by mass or more of the particles to be used preferably have a particle diameter of 0.5 to 5 mm. Moreover, it is preferable that 50 mass% or more of the particle | grains to be used have a particle diameter of 1-4 mm. The cellulose acylate particles preferably have a shape as close to a sphere as possible.

  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 250 to 550, more preferably 250 to 400, and particularly preferably a viscosity average degree of polymerization of 250 to 350. 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.

  When the low molecular component is removed, the average molecular weight (degree of polymerization) is increased, but the viscosity is lower than that of ordinary cellulose acylate, which is useful. Cellulose acylate having a small amount of low molecular components can be obtained by removing low molecular components from cellulose acylate synthesized by a usual method. The removal of the low molecular component can be carried out by washing the cellulose acylate with an appropriate organic solvent.

  In addition, when manufacturing a cellulose acylate with few low molecular components, it is preferable to adjust the sulfuric acid catalyst amount in an acetylation reaction to 0.5-25 mass parts with respect to 100 mass parts of cellulose. When the amount of the sulfuric acid catalyst is in the above range, cellulose acylate that is preferable in terms of molecular weight distribution (uniform molecular weight distribution) can be synthesized. When used in the production of the cellulose acylate used in the present invention, the water content is preferably 2% by mass or less, more preferably 1% by mass or less, and particularly 0.7% by mass or less. It is a cellulose acylate having a water content. In general, cellulose acylate contains water and is known to be 2.5 to 5% by mass. In order to reduce the moisture content of the cellulose acylate, drying is necessary, and the method is not particularly limited as long as the desired moisture content (for example, 2% by mass or less) can be achieved.

  These cellulose acylates used in the present invention, the raw material cotton and the synthesis method are described in detail on pages 7 to 12 of the Japan Society for Invention and Technology (public technical number 2001-1745, published on March 15, 2001, Japan Institute of Invention). It is described in.

  In the cellulose acylate film of the present invention, various additives (for example, plasticizers, ultraviolet inhibitors, deterioration inhibitors, optical anisotropy control agents, fine particles, release agents, infrared rays) according to the use in each preparation step. Absorbents, etc.) can be added and they can be solid or oily. That is, the melting point and boiling point are not particularly limited. For example, mixing of ultraviolet absorbing material at 20 ° C. or lower and 20 ° C. or higher, and similarly mixing of a plasticizer is described in, for example, JP-A-2001-151901. Furthermore, infrared absorbing dyes are described, for example, in JP-A No. 2001-194522. Moreover, 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 is described in Japanese Patent Application Laid-Open No. 2001-151902, and these are conventionally known techniques.

  Furthermore, for these details, materials described in detail on pages 16 to 22 of the Japan Society for Invention and Innovation Technical Report (Public Technical Number 2001-1745, published on March 15, 2001, Japan Society for Invention) are preferably used.

The organic solvent for dissolving the cellulose acylate used in the present invention will be described.
First, the non-chlorine organic solvent that is preferably used in preparing the cellulose acylate solution used in the present invention will be described. In the present invention, the non-chlorine organic solvent is not particularly limited as long as the object can be achieved as long as the cellulose acylate can be dissolved and cast to form a film. The non-chlorine organic solvent used in the present invention is preferably a solvent selected from esters, ketones and ethers having 3 to 12 carbon atoms.

  Esters, ketones and ethers may have a cyclic structure. A compound having two or more functional groups of esters, ketones and ethers (that is, —O—, —CO— and —COO—) can also be used as a main solvent, such as an alcoholic hydroxyl group. It may have a functional group of In the case of the main solvent having two or more kinds of functional groups, the number of carbon atoms may be within the specified range of the compound having any functional group.

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

  The non-chlorine organic solvent used in the above cellulose acylate is selected from the various viewpoints described above, and is preferably as follows. That is, the preferred solvent for cellulose acylate used in the present invention is a mixed solvent of three or more different from each other, and the first solvent is selected from methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, dioxolane, and dioxane. The second solvent is selected from ketones having 4 to 7 carbon atoms or acetoacetate, and the third solvent is an alcohol or carbonized carbon having 1 to 10 carbon atoms. It is selected from hydrogen, and more preferably an alcohol having 1 to 8 carbon atoms.

  Note that when the first solvent is a mixed liquid of two or more kinds of solvents, the second solvent may be omitted. The first solvent is more preferably methyl acetate, acetone, methyl formate, ethyl formate, or a mixture thereof, and the second solvent is preferably methyl ethyl ketone, cyclopentanone, cyclohexanone, or methyl acetyl acetate. It may be.

  The alcohol as the third solvent is preferably linear, branched or cyclic, and is preferably a saturated aliphatic hydrocarbon. The hydroxyl group of the alcohol may be any of primary to tertiary. Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-methyl-2-butanol and cyclohexanol. included. As the alcohol, fluorine-based alcohol is also used. Examples thereof include 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol and the like.

  Furthermore, the hydrocarbon may be linear, branched or cyclic. Either aromatic hydrocarbons or aliphatic hydrocarbons can be used. The aliphatic hydrocarbon may be saturated or unsaturated. Examples of hydrocarbons include cyclohexane, hexane, benzene, toluene and xylene. These alcohols and hydrocarbons as the third solvent may be used alone or in combination of two or more, and are not particularly limited. As the third solvent, preferred specific compounds include alcohol, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and cyclohexanol, cyclohexane, hexane, Are methanol, ethanol, 1-propanol, 2-propanol, 1-butanol.

  The above three types of mixed solvents preferably contain a first solvent in a proportion of 20 to 95% by mass, a second solvent in a proportion of 2 to 60% by mass, and a third solvent in a proportion of 2 to 30% by mass, Furthermore, it is preferable that a 1st solvent is 30-90 mass%, a 2nd solvent is 3-50 mass%, and also 3-25 mass% of 3rd alcohol is contained. In particular, it is preferable that the first solvent is 30 to 90% by mass, the second solvent is 3 to 30% by mass, and the third solvent is alcohol and 3 to 15% by mass.

  In addition, when the first solvent is a mixed solution and the second solvent is not used, the first solvent is preferably contained in a ratio of 20 to 90% by mass and the third solvent in a ratio of 5 to 30% by mass, Furthermore, it is preferable that a 1st solvent is 30-86 mass%, and also a 3rd solvent is contained 7-25 mass%. The non-chlorine organic solvent used in the present invention is described in more detail in pages 12 to 16 of the Japan Society for Invention and Technology (Public Technical Number 2001-1745, published on March 15, 2001, Japan Society for Invention). It is described in. Preferred combinations of non-chlorine organic solvents used in the present invention can be listed below, but are not limited thereto.

-Methyl acetate / acetone / methanol / ethanol / butanol (75/10/5/5/5, parts by mass),
-Methyl acetate / acetone / methanol / ethanol / propanol (75/10/5/5/5, parts by mass),
Methyl acetate / acetone / methanol / butanol / cyclohexane (75/10/5/5/5, parts by mass),
・ Methyl acetate / acetone / ethanol / butanol (81/8/7/4, parts by mass)
・ Methyl acetate / acetone / ethanol / butanol (82/10/4/4, parts by mass)
・ Methyl acetate / acetone / ethanol / butanol (80/10/4/6, part by mass)
Methyl acetate / methyl ethyl ketone / methanol / butanol (80/10/5/5, parts by mass),
-Methyl acetate / acetone / methyl ethyl ketone / ethanol / isopropanol (75/10/10/5/7, parts by mass)
Methyl acetate / cyclopentanone / methanol / isopropanol (80/10/5/8, parts by mass),
・ Methyl acetate / acetone / butanol (85/5/5, part by mass),
Methyl acetate / cyclopentanone / acetone / methanol / butanol (60/15/15/5/6, parts by mass),
-Methyl acetate / cyclohexanone / methanol / hexane (70/20/5/5, parts by mass)
・ Methyl acetate / methyl ethyl ketone / acetone / methanol / ethanol (50/20/20/5/5, part by mass),
Methyl acetate / 1,3-dioxolane / methanol / ethanol (70/20/5/5, parts by mass),
-Methyl acetate / dioxane / acetone / methanol / ethanol (60/20/10/5/5, parts by mass),
Methyl acetate / acetone / cyclopentanone / ethanol / isobutanol / cyclohexane (65/10/10/5/5/5, parts by mass),

・ Methyl formate / methyl ethyl ketone / acetone / methanol / ethanol (50/20/20/5/5, part by mass),
-Methyl formate / acetone / ethyl acetate / ethanol / butanol / hexane (65/10/10/5/5/5, parts by mass),
Acetone / methyl acetoacetate / methanol / ethanol (65/20/10/5, parts by mass),
Acetone / cyclopentanone / ethanol / butanol (65/20/10/5, parts by mass),
Acetone / 1,3-dioxolane / ethanol / butanol (65/20/10/5, parts by mass),
・ 1,3-Dioxolane / cyclohexanone / methyl ethyl ketone / methanol / butanol (55/20/10/5/5/5, parts by mass)
Etc.

Furthermore, a cellulose acylate solution can also be used by the following method.
In addition to the above non-chlorine organic solvent, the dope in the present invention may contain dichloromethane in an amount of 10% by mass or less of the total organic solvent amount.

  In preparing the cellulose acylate solution in the present invention, a chlorinated organic solvent is sometimes used as a main solvent, and is described below. In the present invention, the chlorinated organic solvent is not particularly limited as long as the object can be achieved within a range in which the cellulose acylate is dissolved and can be cast and formed into a film. These chlorinated organic solvents are preferably dichloromethane and chloroform. Particularly preferred is dichloromethane.

  In addition, there is no particular problem in mixing an organic solvent other than the chlorinated organic solvent. In that case, it is preferable to use at least 50% by mass of dichloromethane. The non-chlorine organic solvent used in the present invention is described below. That is, as a preferable non-chlorine organic solvent, a solvent selected from esters, ketones, ethers, alcohols, hydrocarbons and the like having 3 to 12 carbon atoms is preferable. Esters, ketones, ethers and alcohols may have a cyclic structure. A compound having two or more functional groups of esters, ketones and ethers (that is, —O—, —CO— and —COO—) can also be used as a solvent. For example, other functional groups such as alcoholic hydroxyl groups can be used. You may have group simultaneously. In the case of a 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. Examples of esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate.

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

  The alcohol used in combination with the chlorinated organic solvent may be linear, branched or cyclic, and among them, saturated aliphatic hydrocarbon is preferable. The hydroxyl group of the alcohol may be any of primary to tertiary. Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-methyl-2-butanol and cyclohexanol. included. As the alcohol, fluorine-based alcohol is also used. Examples thereof include 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol and the like.

  Furthermore, the hydrocarbon may be linear, branched or cyclic. Either aromatic hydrocarbons or aliphatic hydrocarbons can be used. The aliphatic hydrocarbon may be saturated or unsaturated. Examples of hydrocarbons include cyclohexane, hexane, benzene, toluene and xylene.

  The non-chlorine organic solvent used in combination with the chlorine-based organic solvent that is the main solvent used for the cellulose acylate is not particularly limited, but methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, dioxolane , Dioxane, ketones having 4 to 7 carbon atoms or acetoacetic acid esters, alcohols or hydrocarbons having 1 to 10 carbon atoms. Preferred non-chlorine organic solvents used in combination are methyl acetate, acetone, methyl formate, ethyl formate, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl acetyl acetate, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol. , 2-butanol, and cyclohexanol, cyclohexane, and hexane. Although the following can be mentioned as a combination of the chlorinated organic solvent which is a preferable main solvent used by this invention, It is not limited to these.

Dichloromethane / methanol / ethanol / butanol (75/10/5/5/5, parts by mass),
Dichloromethane / acetone / methanol / propanol (80/10/5/5, parts by mass),
Dichloromethane / methanol / butanol / cyclohexane (75/10/5/5/5, parts by mass),
Dichloromethane / methyl ethyl ketone / methanol / butanol (80/10/5/5, parts by mass),
Dichloromethane / acetone / methyl ethyl ketone / ethanol / isopropanol (75/10/10/5/7, parts by mass),
Dichloromethane / cyclopentanone / methanol / isopropanol (80/10/5/8, parts by mass)
Dichloromethane / methyl acetate / butanol (80/10/10, parts by mass),
Dichloromethane / cyclohexanone / methanol / hexane (70/20/5/5, parts by mass)
Dichloromethane / methyl ethyl ketone / acetone / methanol / ethanol (50/20/20/5/5, parts by mass),
・ Dichloromethane / 1, 3 dioxolane / methanol / ethanol (70/20/5/5, part by mass),
Dichloromethane / dioxane / acetone / methanol / ethanol (60/20/10/5/5, parts by mass),
Dichloromethane / acetone / cyclopentanone / ethanol / isobutanol / cyclohexane (65/10/10/5/5/5, parts by mass),
・ Dichloromethane / methyl ethyl ketone / acetone / methanol / ethanol (70/10/10/5/5, parts by mass),
Dichloromethane / acetone / ethyl acetate / ethanol / butanol / hexane (65/10/10/5/5/5, parts by mass),
Dichloromethane / methyl acetoacetate / methanol / ethanol (65/20/10/5, parts by mass),
Dichloromethane / cyclopentanone / ethanol / butanol (65/20/10/5, parts by mass),
Etc.

  The cellulose acylate used in the present invention is preferably dissolved in an organic solvent at a concentration of 10 to 30% by mass, more preferably a concentration of 13 to 27% by mass, and particularly a concentration of 15 to 25% by mass. A cellulose acylate solution is preferred. The method for carrying out the cellulose acylate at these concentrations may be carried out so as to obtain a predetermined concentration at the stage of dissolution, or it is prepared as a low-concentration solution (for example, 9 to 14% by mass) and then concentrated as described 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 this invention, it is preferable that the aggregate molecular weight of the cellulose acylate of the diluted solution which made the cellulose acylate solution 0.1-5 mass% with the organic solvent of the same composition is 150,000-15 million. More preferably, the associated molecular weight is 180,000 to 9 million. This associated molecular weight can be determined by a static light scattering method. In this case, it is preferable to dissolve so that the inertial square radius required at the same time is 10 to 200 nm. A more preferable inertial square radius is 20 to 200 nm. Furthermore, it is preferable to dissolve so that the second virial coefficient is −2 × 10 ⁻⁴ to 4 × 10 ^−4, and more preferably, the second virial coefficient is −2 × 10 ⁻⁴ to 2 × 10 ^−4. It is. Here, the definition of the associated molecular weight, the inertial square radius and the second virial coefficient in the present invention will be described.

  These were measured using the static light scattering method according to the following method. Although the measurement was performed in a dilute region for the convenience of the apparatus, these measured values reflect the behavior of the dope in the high concentration region of the present invention. First, cellulose acylate was dissolved in a solvent used for the dope to prepare 0.1 mass%, 0.2 mass%, 0.3 mass%, and 0.4 mass% solutions. In order to prevent moisture absorption, the cellulose acylate was dried at 120 ° C. for 2 hours and measured at 25 ° C. and 10% RH. The dissolution method was carried out according to the method employed at the time of dope dissolution (room temperature dissolution method, cooling dissolution method, high temperature dissolution method).

  Subsequently, these solutions and the solvent were filtered through a 0.2 μm polytetrafluoroethylene filter. The filtered solution was measured for static light scattering at intervals of 10 degrees from 30 degrees to 140 degrees at 25 ° C. using a light scattering measuring device (DLS-700 manufactured by Otsuka Electronics Co., Ltd.). The obtained data was analyzed by the BERRY plot method. In addition, the refractive index required for this analysis uses the value of the solvent calculated | required with the Abbe refractive system, and the refractive index gradient (dn / dc) uses the differential refractometer (Otsuka Electronics Co., Ltd. product DRM-1021). The measurement was performed using the solvent and the solution used for the light scattering measurement.

  Next, regarding the preparation of the cellulose acylate solution (dope) in the present invention, the dissolution method is not particularly limited, and it may be room temperature, further a cooling dissolution method or a high temperature dissolution method, and further 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-A-2000-53784, Kaihei 11-322946, JP-A-11-322947, JP-A-2-276830, JP-A-2000-273239, JP-A-11-71463, JP-A-04-259511, JP-A-2000-273184, JP-A-11-323017, JP-A-11-323017 11-302388 describes a method for preparing a cellulose acylate solution. The above-described method for dissolving cellulose acylate in an organic solvent is applicable to the present invention as long as it is within the scope of the present invention.

  The details of these are described in detail on pages 22 to 25 of the Japan Society for Invention and Technology (Publication No. 2001-1745, published on March 15, 2001, Japan Society of Invention and Innovation) for non-chlorine solvent systems. Implemented in the method. Further, the cellulose acylate dope solution of the present invention is usually subjected to solution concentration and filtration, and similarly, page 25 of the Japan Society for Invention and Technology (Publication No. 2001-1745, published on March 15, 2001, Japan Society of Inventions). Are described in detail. 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 in the present invention preferably has a viscosity and a 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) having a diameter of 4 cm / 2 °. Measurement conditions were measured by varying the range from 40 ° C. to −10 ° C. at 2 ° C./min using an Oscillation Step / Temperature Ramp, static non-Newtonian viscosity n ^* (Pa · s) 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 400 Pa · s, the dynamic storage elastic modulus at 15 ° C. is preferably 500 Pa or more, more preferably the viscosity at 40 ° C. is 10 to 200 Pa · s, The dynamic storage elastic modulus at 15 ° C. is preferably 1 to 1,000,000. Furthermore, it is preferable that the dynamic storage elastic modulus at a low temperature is large. For example, when the casting support is −5 ° C., the dynamic storage elastic modulus is preferably 10,000 to 1,000,000 Pa at −5 ° C. When the body is at −50 ° C., the dynamic storage elastic modulus at −50 ° C. is preferably 10,000 to 5 million Pa.

[Film (cellulose film)]
Next, the film (cellulose film) containing at least one compound of the general formula (1) or (1-A) of the present invention will be described. First, the production method will be described by taking as an example a film using a cellulose acylate solution as the film of the present invention (cellulose film).

  For the method and equipment for producing the cellulose acylate film of the present invention, a solution casting film forming method and a solution casting film forming apparatus conventionally used for producing a cellulose triacetate film are used. The dope (cellulose acylate solution) prepared from the 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 Japan Society of Invention Disclosure Technical Report (Public Technical Number 2001-1745, published on March 15, 2001, Japan Society of Invention). ), Metal support, drying, peeling, stretching and the like.

  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, and it is especially preferable that it is -20-30 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, Furthermore, it is -20-15 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 present invention, the following configurations are particularly preferred for the contents and casting of each layer. That is, the cellulose acylate solution is a cellulose acylate solution containing 0.1 to 20% by mass of at least one liquid or solid plasticizer with respect to cellulose acylate at 25 ° C. and / or at least It is a cellulose acylate solution containing 0.001 to 5% by mass of one kind of liquid or solid UV absorber with respect to cellulose acylate, and / or an average particle size of 5 to 5 of at least one kind of solid. It is a cellulose acylate solution containing 0.001 to 5% by mass of fine particle powder of 3000 nm with respect to cellulose acylate, and / or at least one fluorosurfactant with respect to cellulose acylate A cellulose acylate solution containing 0.001 to 2% by mass and / or a small amount Both are cellulose acylate solutions containing 0.0001 to 2% by mass of one type of release agent with respect to cellulose acylate, and / or at least one type of deterioration inhibitor is 0.0001 with respect to cellulose acylate. A cellulose acylate solution containing ˜2 mass%, and / or containing 0.1-15 mass% of at least one optical anisotropy control agent with respect to cellulose acylate, and / or Or a cellulose acylate solution containing 0.1 to 5% by mass of at least one infrared absorber with respect to the cellulose acylate, and a cellulose acylate produced therefrom. A film is preferred.

  In the casting step, one type of cellulose acylate solution may be cast as a single layer, or two or more types of cellulose acylate solutions may be cast simultaneously and / or sequentially. In the case of having a casting process consisting of two or more layers, the composition of the chlorine-based solvent in each layer is either the same or different in each of the produced cellulose acylate solution and cellulose acylate film, and each layer The additive is one kind or a mixture of two or more kinds, the addition position of the additive to each layer is either the same layer or a different layer, The concentration in the solution is either the same or different in each layer, the aggregate molecular weight of each layer is either the same or a different aggregate molecular weight, Either the temperature is the same or a different temperature, the coating amount of each layer is the same or different, and the viscosity of each layer is the same Either one of the different viscosities, the film thickness after drying of each layer is the same or different, and the material present in each layer is the same or distribution or different or A cellulose acylate that is characterized by the distribution, the physical properties of each layer being the same or different, and the physical properties of each layer being either uniform or different. A rate solution and a cellulose acylate film produced from the solution are also preferred.

Here, the physical properties include physical properties described in detail on pages 6 to 7 of the Japan Society for Invention and Innovation Technical Report (Public Technical Number 2001-1745, issued on March 15, 2001, Japan Institute of Invention). For example, haze, transmittance, spectral characteristics, retardation Re, Rth, molecular orientation axis, axial misalignment, tear strength, folding strength, tensile strength, roll-in / out Rt difference, creaking, dynamic friction, alkaline hydrolysis, curl value, water content Rate, residual solvent amount, heat shrinkage rate, high humidity dimensional evaluation, moisture permeability, base flatness, dimensional stability, heat shrinkage starting temperature, elastic modulus, and measurement of bright spot foreign matter, etc. Impedance and surface shape used for evaluation are also included.
In addition, the Yellow Index, Transparency, and Thermophysical Properties (Tg, Cellulose Acylate) described in detail on page 11 of the Japan Society for Invention and Innovation (Public Technical Number 2001-1745, published on March 15, 2001, Invention Association) (Crystallization heat).

The cellulose acylate film can achieve improved adhesion between the cellulose acylate film and each functional layer (for example, the undercoat layer and the back layer) by optionally performing a surface treatment. For example, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment can be used. The glow discharge treatment here may be low-temperature plasma that occurs in a low pressure gas of 10 ^{−3 to} 20 Torr, and plasma treatment under atmospheric pressure is also preferable.

  A plasma-excitable gas is a gas that is plasma-excited under the above conditions, and includes chlorofluorocarbons such as argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, tetrafluoromethane, and mixtures thereof. It is done. Details of these are described in detail on pages 30 to 32 of the Japan Society for Invention and Innovation Technical Report (Public Technical Number 2001-1745, published on March 15, 2001, Japan Society for Invention). Note that, in the plasma treatment at atmospheric pressure which has been attracting attention in recent years, for example, irradiation energy of 20 to 500 Kgy is used under 10 to 1000 Kev, and more preferably irradiation energy of 20 to 300 Kgy is used under 30 to 500 Kev. 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 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, an alcohol solvent is preferable, and isopropyl alcohol is particularly preferable.

An aqueous solution of a surfactant can also be used as a solvent. The alkali of the alkali saponification coating solution is preferably an alkali that dissolves in the above solvent, and more preferably KOH or NaOH. The pH of the saponification coating solution is preferably 10 or more, more preferably 12 or more. The reaction conditions during alkali saponification are preferably 1 second to 5 minutes at room temperature, more preferably 5 seconds to 5 minutes, and particularly preferably 20 seconds to 3 minutes. After the alkali saponification reaction, it is preferable to wash the surface on which the saponification solution is applied with water or with an acid and then with water.
Further, the coating-type saponification treatment and the alignment film uncoating described later can be performed continuously, and the number of steps can be reduced.

  In order to achieve adhesion between the film and the emulsion layer, after surface activation treatment, a functional layer was directly applied on the cellulose acylate film to obtain adhesive force, and some surface treatment was performed once. There is a method in which an undercoat layer (adhesive layer) is provided or a functional layer is applied thereon after or without surface treatment. Details of these subbing layers are described on page 32 of the Japan Society for Invention and Innovation (Public Technical Number 2001-1745, published on March 15, 2001, Japan Institute of Invention). Various functional layers of the cellulose acylate film of the present invention are also disclosed in pages 32 to 45 of the Japan Society for Invention and Technology (public technical number 2001-1745, published on March 15, 2001, Japan Institute of Invention). It is described in detail.

The use of the cellulose acylate film produced in the present invention will be briefly described first. The film of the present invention is particularly useful as a polarizing plate protective film, an optical compensation sheet for a liquid crystal display device, an optical compensation sheet for a reflective liquid crystal display device, and a support for a silver halide photographic light-sensitive material.
Accordingly, the thickness of the film of the present invention is determined by these uses and is not particularly limited, but is preferably 30 μm or more, more preferably 30 to 200 μm.

  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 particularly effective when used as an optical compensation sheet for liquid crystal display devices. 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 Crystals), AFLC (Anti-Ferroelectric Liquid Crystals), OCB (Optically Charged TNS). Various display modes such as HAN (Hybrid Aligned Nematic) have been proposed. In addition, a display mode in which the above display mode is oriented and divided has been proposed.

  The cellulose acylate film of the present invention 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 ) 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 reflective liquid crystal display device is described in JP-A-10-123478, WO98 / 48320, 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 a liquid crystal cell in ASM (Axial Symmetrical Microcell) mode. The ASM mode liquid crystal cell is characterized in that the thickness of the cell is maintained by a resin spacer whose position can be adjusted.

  Other properties are the same as those of the TN mode liquid crystal cell. 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 the cellulose acylate film described above is described in detail on pages 45 to 59 of the Japan Society for Invention and Innovation (Public Technical Number 2001-1745, published on March 15, 2001, Japan Society of Invention).

EXAMPLES Next, although this invention is demonstrated further in detail based on an Example, this invention is not limited at all by the following Example.
[Example 1]
Each component of the following cellulose acetate solution composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acetate solution.

(Cellulose acetate solution composition)
Cellulose acetate having an acetylation degree of 60.9% 100 parts by weight Triphenyl phosphate (plasticizer) 7.8 parts by weight Biphenyl diphenyl phosphate (plasticizer) 3.9 parts by weight Methylene chloride (first solvent) 318 parts by weight Methanol (No. 1) 2 solvents) 47 parts by mass

Into another mixing tank, 16 parts by mass of the naphthalene dicarbonyl compound or the comparative compound used in the present invention, 87 parts by mass of methylene chloride and 13 parts by mass of methanol are added and stirred while heating to prepare a retardation control agent solution. did.
A dope was prepared by mixing 36 parts by mass of the retardation control (raising) agent solution with 474 parts by mass of the cellulose acetate solution and stirring sufficiently. The addition amount of the retardation adjusting agent was the amount (part by mass) shown in Table 1 with respect to 100 parts by mass of cellulose acetate.

  The obtained dope was cast using a band casting machine. A film having a residual solvent amount of 15% by mass was laterally stretched at a stretch ratio of 26% using a tenter under the conditions of 130 ° C. to produce a cellulose acetate film (thickness: 80 μm). About the produced cellulose acetate film (optical compensation sheet), the Re retardation value and Rth retardation value at a wavelength of 633 nm were measured using an ellipsometer (M-150, manufactured by JASCO Corporation). The results are shown in Table 1.

<Measurement of Rth and Re>
Using an ellipsometer (AEP-100, manufactured by Shimadzu Corporation), the value obtained by multiplying the longitudinal and lateral refractive index difference measured at a wavelength of 632.8 nm by the film thickness was determined according to the following formula.
Re = (nx−ny) × d
Rth = {(nx + ny) / 2−nz} × d
nx: refractive index in the slow axis direction (direction in which the refractive index is maximum) ny: refractive index in the direction orthogonal to the slow axis nz: refractive index in the thickness direction d: film thickness (unit: nm)

比較化合物１

Comparative compound 1

As can be seen from the results in Table 1, it can be seen that Comparative Compound 1 satisfies Re = Rth × 0.52-55.1 (Formula 1) by changing the addition amount.
Since the film containing the comparative compound 1 exhibits Re by stretching and Rth is not changed so much, the comparative compound is a film satisfying the optical characteristics in the region of Re ≦ Rth × 0.52-55.1 (Formula 2). Can be made.
However, the film to which the naphthalene dicarbonyl compound is added has a higher Re expression than the film to which Comparative Compound 1 is added (that is, a novel cellulose having a large Re / Rth ratio outside the range of (Formula 2)). It can be seen that a film can be produced.

[Example 2]
Further, even when Re-7 and Re-14 are used instead of Re-13 at the same addition amount as Table 1 No. 5 in Example 1, it has a greater Re expression property that could not be realized with Comparative Compound 1 (that is, (Formula 2 ) And a new cellulose compound film (having a large Re / Rth ratio) can be produced, and similar effects can be obtained.
In addition, a cellulose film having an arbitrary Re / Rth ratio can be produced by the combined use of the naphthalene dicarbonyl compound and the comparative compound 1 in the present invention.

Claims (7)

A cellulose compound;
A naphthalene compound substituted with at least one -COR ¹ (R ¹ represents a hydrogen atom or a substituent);
A cellulose compound solution comprising an organic solvent. A cellulose compound;
A naphthalene dicarbonyl compound represented by the following general formula (1):
A cellulose compound solution comprising an organic solvent.
General formula (1)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹¹ and R ¹² each independently represents a hydrogen atom or a substituent.) The cellulose compound solution according to claim 2, wherein the naphthalene dicarbonyl compound is a compound represented by the general formula (1-A).
Formula (1-A)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a substituent. R ²¹ and R ²² each independently represent an alkyl group, an alkenyl group, or an alkynyl group. A group, an aryl group, or a heterocyclic group, X ¹ and X ² each independently represent —O— or —NR— (R represents a hydrogen atom, an alkyl group, or an aryl group);   The cellulose compound solution according to claim 2 or 3, wherein the cellulose compound is cellulose acylate. A cellulose compound;
A cellulose film comprising a naphthalene dicarbonyl compound represented by the following general formula (1).
General formula (1)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹¹ and R ¹² each independently represents a hydrogen atom or a substituent.) The cellulose film of Claim 5 whose naphthalene dicarbonyl compound is a compound represented by general formula (1-A).
Formula (1-A)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a substituent. R ²¹ and R ²² each independently represent an alkyl group, an alkenyl group, or an alkynyl group. A group, an aryl group, or a heterocyclic group, X ¹ and X ² each independently represent —O— or —NR— (R represents a hydrogen atom, an alkyl group, or an aryl group);   The cellulose film according to claim 5 or 6, wherein the cellulose compound is cellulose acylate.