JP4186063B2 - Cellulose composition, cellulose film, and modifier for cellulose film - Google Patents

Description

  The present invention relates to a cellulose composition, a cellulose film, and a modifier for the cellulose film.

  Conventionally, a chlorine-containing hydrocarbon such as dichloromethane has been used as an organic solvent for a cellulose acylate solution used for producing a cellulose acylate used in a silver halide photographic light-sensitive material or a liquid crystal image display device. . Dichloromethane (boiling point of about 40 ° C.) has been conventionally used as a good solvent for cellulose acylate, and is preferably used due to the advantage that it is easy to dry because of its low boiling point in the film formation and drying steps of the production process. In recent years, chlorinated organic solvents, which have a low boiling point from the viewpoint of environmental conservation, have been able to significantly reduce leakage in the handling process in sealed facilities. For example, a thorough closed system was used to prevent leakage from the system, and in the unlikely event that a leak occurred, a gas absorption tower was installed before it was released to the outside air, and an organic solvent was adsorbed and treated. Furthermore, organic solvents are almost never exhausted by combustion with thermal power or decomposition of chlorinated organic solvents by electron beam before discharging, but further research is necessary before complete non-emission.

  On the other hand, a cellulose acylate solvent other than dichloromethane, which has been preferably used as a chlorinated organic solvent, has been searched. Cellulose acylates, particularly those known as organic solvents showing solubility in cellulose triester, include acetone (boiling point 56 ° C.), methyl acetate (boiling point 56 ° C.), tetrahydrofuran (boiling point 65 ° C.), 1,3- Examples include dioxolane (boiling point 75 ° C.) and 1,4-dioxane (boiling point 101 ° C.). However, these organic solvents do not have sufficient solubility for practical use by conventional dissolution methods.

  As a solution to this problem, J.A. M.M. G. Cowie et al. In Non-Patent Document 1 said that cellulose triacetate (degree of acetylation 60.1% to 61.3%) was cooled from −80 ° C. to −70 ° C. in acetone and then heated to 0.5 to 0.5%. It is reported that a 5% by weight dilute solution is obtained. Such a method for dissolving cellulose acylate at a low temperature is called a cooling dissolution method. In addition, Kenji Kamide et al. Described a spinning technique using a cooling dissolution method in “Non-Patent Document 2“ Dry spinning from cellulose triacetate in acetone ””. Patent Documents 1 to 3 disclose that cellulose acylate is dissolved by a cooling dissolution method using a non-chlorine organic solvent against the background of the above technique. The non-chlorine organic solvent used at that time is an organic solvent selected from ethers, ketones or esters, and in particular, a film is prepared by dissolving cellulose acylate by a cooling dissolution method. As these specific organic solvents, acetone, 2-methoxyethyl acetate, cyclohexanone, ethyl formate, methyl acetate and the like are preferable. However, even if these solvents are used, the conventional casting method is still insufficient to obtain a cellulose acylate film by high-speed casting.

  On the other hand, a cellulose acylate film is generally produced by a solvent cast method or a melt cast method. In the solvent cast method, a solution (dope) in which cellulose acylate is dissolved in a solvent is cast on a support, and the solvent is evaporated to form a film. In the melt casting method, a cellulose acylate melted by heating is cast on a support, and the support is cooled to form a film. The solvent cast method can produce a good film with higher flatness than the melt cast method. For this reason, the solvent cast method is generally adopted in practice. In the recent solvent casting method, it is a problem to improve the productivity of the film forming process by shortening the time required for casting the dope onto the support and then peeling the molded film on the support. It has become. In particular, when a cellulose acylate film is obtained by the solvent cast method, the cellulose acylate film is peeled from the support in the case of a cellulose acylate solution dissolved at room temperature, high temperature or cooling using the above-mentioned non-chlorine organic solvent. The problem is that it is difficult to do. Furthermore, it is demanded to increase productivity in response to the recent increase in demand for cellulose acylate films, and therefore high-speed casting is desired. Also from this viewpoint, the cellulose acylate film produced in a solution using a non-chlorine organic solvent is inferior in high-speed castability.

  This is because cellulose acylate is cast on a band or drum which is a metal support, dried or cooled to form a strong gel film, peeled off from the support in a state containing an organic solvent, and then sufficient This is because it is difficult to peel the cellulose acylate film from the support during the drying step. It was also observed in a chlorinated organic solvent of dichloromethane, and improvement was desired as described above. As one method for this improvement, in Patent Document 4, acid dissociation index pKa 1.93 to 4.50 [preferably 2.0 to 4.4, more preferably 2.2 to 4.3 (for example, 2.5 to 4.0), especially 2.6 to 4.3 (for example, about 2.6 to 4.0)] or a salt thereof is described as preferable as a release agent. However, this disadvantage is that the alkaline earth metal and fine salt contained in the cellulose acylate solution are produced in the cellulose acylate solution, causing the problem of adhering to the system in the long casting process. The improvement was expected. These stripping agents have been found to be significantly improved in some solutions, but not sufficient. In particular, in the production of a cellulose acylate film by a so-called drum method in which the substrate is peeled off and dried without being dried, there has been an expectation of improvement of the peelability at the time of peeling.

  In addition, the cellulose acylate film is generally difficult to control the retardation (Rth) in the film thickness direction with respect to the in-plane retardation (Re), and in particular, it is difficult to reduce Rth. Therefore, in the production of a film for optical use that requires a low Rth, a method of simply reducing the Rth by simply adding an additive to the cellulose acylate solution is desired.

Makromol. chem. 143, 105, 1971 Journal of the Textile Machinery Society, 34, 57-61, 1981 JP-A-9-95538 JP-A-9-95544 JP-A-9-95557 Japanese Patent Laid-Open No. 10-316701

  The objective of this invention is providing the modifier for cellulose acylates which has the effect | action which reduces the optical anisotropy of a cellulose acylate film. Another object of the present invention is to provide a cellulose acylate film having a small optical anisotropy by casting a cellulose acylate solution prepared by an ordinary temperature dissolution, a cooling dissolution method or a high temperature high pressure dissolution method using an organic solvent. It is in.

These purposes are
(1) Cellulose composition characterized by containing cellulose and ionic liquid,
(2) A cellulose composition comprising cellulose and a compound represented by the general formula (1),
General formula (1)

（式中、Ｒ^１〜Ｒ^５は水素原子、アルキル基、アリール基、複素環基またはアラルキル基を表し、各々同一でも異なっていてもよい。Ｘ⁻はＮ(ＣＦ_３ＳＯ_２)_２ ⁻、Ｃ(ＣＦ_３ＳＯ_２)_３ ⁻、ＣＦ_３ＳＯ_３ ⁻、Ｃ_２Ｆ_５ＳＯ_３ ⁻、Ｃ_３Ｆ_７ＳＯ_３ ⁻、Ｃ_４Ｆ_９ＳＯ_３ ⁻、ＢＦ_４ ⁻、ＰＦ_６ ⁻、Ａｌ_３Ｃｌ_８ ⁻、Ａｌ_２Ｃｌ_７ ⁻、ＡｌＣｌ_４ ⁻およびＣｌＯ_４ ⁻からなる群から選ばれるアニオン成分を表す。）
（３）セルロースと一般式（１）で表される化合物をセルロースに対し０．０１〜３０質量％含有することを特徴とする（２）に記載のセルロース組成物、
（４）セルロースと一般式（１）で表される化合物をセルロースに対し５〜３０質量％含有することを特徴とする（２）または（３）に記載のセルロース組成物、
（５）前記（１）〜（３）に記載のセルロース組成物からなるセルロースフィルム、
（６）膜厚方向のレターデーション値が１００ｎｍ以下であることを特徴とする、（５）に記載のセルロースフィルム、
（７）一般式（１）で表されるセルロースフィルム用改質剤、
によって達成された。

(Wherein R ^{1 to} R ⁵ represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or an aralkyl group, and each may be the same or different. X ⁻ represents N (CF ₃ SO ₂ ) ₂ ⁻ , _{C (CF 3 SO 2) 3} -, CF 3 SO 3 -, C 2 F 5 SO 3 -, C 3 F 7 SO 3 -, C 4 F 9 SO 3 -, BF 4 -, PF 6 -, Al 3 Represents an anionic component selected from the group consisting of Cl ₈ ⁻ , Al ₂ Cl ₇ ⁻ , AlCl ₄ ⁻ and ClO ₄ ⁻ .)
(3) The cellulose composition according to (2), which contains cellulose and a compound represented by the general formula (1) in an amount of 0.01 to 30% by mass based on cellulose.
(4) Cellulose composition according to (2) or (3), containing 5 to 30% by mass of cellulose and a compound represented by the general formula (1),
(5) A cellulose film comprising the cellulose composition according to the above (1) to (3),
(6) The cellulose film according to (5), wherein the retardation value in the film thickness direction is 100 nm or less,
(7) A cellulose film modifier represented by the general formula (1),
Achieved by.

  By using the modifier of the present invention, a cellulose film having a low Rth could be produced.

  The cellulose composition and cellulose film of the present invention are characterized by containing, as a modifier, an ionic liquid which is a salt having a melting point lower than room temperature and liquid at room temperature. In this invention, normal temperature means 25 degreeC. In the cellulose film, the modifier is preferably contained in an amount of 0.01 to 30% by mass, more preferably 2 to 30% by mass, and still more preferably 5 to 30% by mass with respect to cellulose.

The anionic component in the modifier of the present _{invention, N (CF 3 SO 2)} 2 -, C (CF 3 SO 2) 3 -, CF 3 SO 3 -, C 2 F 5 SO 3 -, C 3 F 7 SO ₃ ⁻ , C ₄ F ₉ SO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , Al ₃ Cl ₈ ⁻ , Al ₂ Cl ₇ ⁻ , AlCl ₄ ⁻ and ClO ₄ ⁻ can be mentioned.

Moreover, as a cation component in the modifier of this invention, an alkali metal ion and an imidazolium cation are mentioned, Preferably it is an imidazolium cation represented by General formula (1). However, in the general formula (1), the anion component which is a counter anion of the imidazolium cation is also represented as X ⁻ and the whole is represented in the form of an imidazolium salt.
General formula (1)

本発明においては、一般式（１）中、Ｒ^１〜Ｒ^５は水素原子、アルキル基、アリール基、複素環基またはアラルキル基を表し、各々同一でも異なっていてもよく、互いに環を形成していても良い。

In the present invention, in the general formula (1), R ^{1 to} R ⁵ each represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or an aralkyl group, which may be the same or different and each form a ring. May be.

In the general formula (1), as a combination of R ^{1 to} R ⁵ , it is preferable that R ¹ and R ³ are each independently an alkyl group, and R ² , R ⁴ and R ⁵ are hydrogen atoms.

  As said alkyl group, a C1-C10 linear or branched alkyl group is preferable, for example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl. And a straight chain or branched alkyl group such as a group, tert-butyl group, n-pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. Among these, a linear or branched alkyl group having 1 to 5 carbon atoms is more preferable, and a linear alkyl group having 1 to 5 carbon atoms is particularly preferable.

  Examples of the aryl group include a phenyl group, a naphthyl group, a toluyl group, and a xylyl group. The aryl group includes a halogen atom (F, Cl, Br, I), a hydroxyl group, a lower alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group), carboxyl group, acetyl group, propanoyl group, thiol group, alkylthio group. It may have some substituents such as (methylthio group, ethylthio group, propylthio group, butylthio group), amino group, lower alkylamino group, di-lower alkylamino group and the like.

  Examples of the heterocyclic group include pyridyl group, thienyl group, imidazolyl group, pyrazolyl group, oxazolyl group, isoxazolyl group, pyrrolidinyl group, piperazinyl group, morpholinyl group and the like.

  Examples of the aralkyl group include a benzyl group and a phenethyl group.

Incidentally, the anion component X in the general formula (1) ^- _{The, N (CF 3 SO 2)} 2 -, C (CF 3 SO 2) 3 -, CF 3 SO 3 -, C 2 F 5 SO 3 -, C ₃ F ₇ SO ₃ ⁻ , C ₄ F ₉ SO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , Al ₃ Cl ₈ ⁻ , Al ₂ Cl ₇ ⁻ , AlCl ₄ ⁻ and ClO ₄ ⁻ are preferable, and N (CF ₃ SO _{3 2} ) ₂ , PF ₆ ⁻ , BF ₄ ^— and CF ₃ SO ₃ ^— are more preferable, and N (CF ₃ SO ₂ ) ₂ and PF ₆ ^— are particularly preferable.

  Specific examples of the compound represented by the general formula (1) are shown below.

  The manufacturing method of the compound represented by said A1-A10 is not specifically limited. For example, the compounds represented by the above A1 to A10 can be obtained by quaternizing the corresponding monosubstituted imidazole with an alkyl halide and then performing an anion exchange reaction using a salt having the target anion. .

  The compound represented by the general formula (1) of the present invention exhibits nonflammability, has extremely low scattering properties, and has an effect of lowering Rth of the obtained cellulose acylate film. , A cellulose acylate film having a low Rth can be obtained.

  Next, the cellulose preferably used in the present invention will be described in detail. The cellulose of the present invention is a cellulose compound and a compound having a cellulose skeleton obtained by introducing a functional group biologically or chemically using cellulose as a raw material. Among these, cellulose ester is preferable, and cellulose acylate is more preferable. Cellulose acylate is not particularly limited as long as it exhibits the effects of the present invention. In the present invention, two or more different cellulose acylates may be mixed and used. However, among them, preferable cellulose acylates include the following materials. That is, as a cellulose acylate, it is preferable that the substitution degree to the hydroxyl group of a cellulose satisfy | fills following formula (I), and the cellulose acylate which satisfies all of (I)-(III) is more preferable.

(I) 2.6 ≦ SA + SB ≦ 3.0
(II) 1.8 ≦ SA ≦ 3.0
(III) 0.0 ≦ 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, 28% or more of SB is 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%, and particularly 32% or more is a 6-position hydroxyl group. A substituent is also preferred. Furthermore, the cellulose acylate in which the sum of the substitution degrees of SA and SB at the 6-position of cellulose acylate is 0.8 or more, further 0.85, and particularly 0.90 can be mentioned. These cellulose acylates can produce a solution having a preferable solubility, and particularly a non-chlorine organic solvent can produce a good film.

  The acyl group (SB) having 3 to 22 carbon atoms of the cellulose acylate of the present invention 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 SBs include propionyl, butanoyl, keptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, iso-butanoyl, t-butanoyl, cyclohexanecarbonyl, oleoyl, benzoyl , Naphthylcarbonyl, cinnamoyl group, and the like. Among these, propionyl, butanoyl, dodecanoyl, octadecanoyl, t-butanoyl, 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.

  Further, in the present invention, 28% or more of SB is 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%, particularly 32% or more. It is also preferable that it is a 6-position hydroxyl group substituent. Furthermore, the cellulose acylate in which the sum of the substitution degrees of 6-position SA and SB of the cellulose acylate is 0.8 or more, further 0.85, and particularly 0.90 can be mentioned. The synthesis of these cellulose acylates having a high degree of substitution at the 6-position is described in JP-A Nos. 11-5851, 2002-212338 and 2002-338601.

  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. Cellulose acylate particles are preferably used as a raw material for film production. 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) increases, but the viscosity becomes lower than that of normal 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 silicate 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 weight 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 of the present invention, its moisture 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 rate. In general, cellulose acylate contains water and is known to be 2.5 to 5% by mass. In order to obtain the moisture content of the cellulose acylate in the present invention, it is necessary to dry, and the method is not particularly limited as long as the desired moisture content is obtained.

  The raw material cotton and synthesis method of these cellulose acylates used in the present invention 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 Society for Invention). Are listed.

  In the cellulose acylate solution of the present invention, various additives (for example, a modifier, an ultraviolet inhibitor, an optical anisotropy control agent, fine particles, a release agent, an infrared absorber, etc.) according to the use in each preparation step. ), Which may be solid or oily. That is, the melting point and boiling point are not particularly limited. For example, a mixture of ultraviolet absorbing materials having a melting point of 20 ° C. or lower and a melting point of 20 ° C. or higher, and a mixture of modifiers are also described, for example, in 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, they are described in JP-A 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.

  Next, the organic solvent that dissolves the cellulose acylate of the present invention will be described.

  First, the non-chlorine organic solvent that is preferably used in preparing the cellulose acylate solution of the present invention will be described. In the present invention, the non-chlorine organic solvent is not particularly limited as long as the object can be achieved as long as the cellulose acylate can be dissolved and cast and formed into 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. The ester, ketone and ether 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, a preferred solvent for the cellulose acylate of 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. At least one kind or a mixture thereof, wherein the second solvent is selected from ketones having 4 to 7 carbon atoms or acetoacetate, and the third solvent is an alcohol or hydrocarbon having 1 to 10 carbon atoms. More preferably, it is 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 may be 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 non-chlorine organic solvent combinations of 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 / 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, the following cellulose acylate solution can also be used.
-Cellulose acylate solution is prepared with methyl acetate / acetone / ethanol / butanol (81/8/7/4, parts by mass), filtered and concentrated, and 2 parts by weight of butanol is added after addition.-Methyl acetate / acetone / ethanol / butanol (84/10/4/2, parts by mass) A cellulose acylate solution was prepared and after filtration and concentration, 4 parts by weight of butanol was added additionally. In methyl acetate / acetone / ethanol (84/10/6, parts by mass) Add 5 parts by weight of butanol after preparing a cellulose acylate solution and filtering and concentrating. In addition to the non-chlorine organic solvent, the dope used in the present invention contains 10% by mass or less of the total organic solvent amount. May be.

  In preparing the cellulose acylate solution of the present invention, a chlorinated organic solvent may be used as a main solvent in some cases. In the present invention, the chlorinated organic solvent is not particularly limited as long as 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 chlorine-free organic solvent used in combination with the chlorine-based organic solvent that is the main solvent used in the cellulose acylate is not particularly limited, but methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, dioxolane, dioxane , A ketone having 4 to 7 carbon atoms or an acetoacetate ester, an alcohol or hydrocarbon 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 of 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, parts 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 of the present invention is characterized in that it is a solution dissolved in an organic solvent in an amount of 10 to 30% by mass, more preferably 13 to 27% by mass, particularly 15 to 25% by mass. The 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.

Next, 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 that 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 in accordance with the method (room temperature dissolution method, cooling dissolution method, high temperature dissolution method) employed during dope dissolution. Subsequently, these solutions and the solvent were filtered through a 0.2 μm polytetrafluoroethylene filter. Then, static light scattering of the filtered solution was measured at intervals of 10 degrees from 30 degrees to 140 degrees at 25 ° C. using a light scattering measuring apparatus (DLS-700 manufactured by Otsuka Electronics Co., Ltd.). The obtained data was analyzed by the BERRY plot method. The refractive index necessary for this analysis is the value of the solvent obtained with an Abbe refractometer, and the refractive index concentration gradient (dn / dc) is a differential refractometer (DRM-1021 manufactured by Otsuka Electronics Co., Ltd.). The measurement was performed using the solvent and the solution used for the light scattering measurement.

  Next, in the present invention, for the preparation of the cellulose acylate solution (dope), the dissolution method is not particularly limited, and may be room temperature, or 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-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.

  In the present invention, the cellulose acylate solution 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 with Oscillation Step / Temperature Ramp by changing the range from 40 ° C to -10 ° C at 2 ° C / min, and static non-Newtonian viscosity at 40 ° C n * (Pa · s) 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.

  Next, a method for producing a film using the cellulose acylate solution of the present invention will be described. 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 modifier with respect to cellulose acylate at 25 ° C. and / or It is a cellulose acylate solution containing 0.001 to 5% by mass of at least one liquid or solid UV absorber with respect to cellulose acylate, and / or the average particle size of at least one solid is 5 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 to cellulose acylate And / or a cellulose acylate solution containing 0.001 to 2% by mass. 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).

In the present invention, retardation means humidity adjustment of a cellulose acylate film at 25 ° C. and 60% RH for 24 hours, and then an ellipsometer (M-150: manufactured by JASCO Corporation) is used, and a He—Ne laser is used. Measured value. The retardation value (Rth) and the in-plane retardation value (Re) in the thickness direction can be calculated according to the following formulas (1) and (2), respectively.
Formula (1)
Re = (nx−ny) × d
Formula (2)
Rth = {(nx + ny) / 2−nz} × d
In the formula, nx is the refractive index in the x direction in the film plane, ny is the refractive index in the y direction in the film plane, nz is the refractive index in the direction perpendicular to the film surface, and d is the thickness of the film. (Nm).
The Rth of the cellulose acylate film of the present invention is preferably 100 nm or less, more preferably 80 nm or less, and still more preferably 60 nm or less.

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 (Public Technical Number 2001-1745, published on March 15, 2001, Japan Institute of 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 or immersing in 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 the 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 produced in the present invention will be briefly described first. The optical 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, it can be used particularly advantageously as a plastic film disposed between a polarizer and a liquid crystal layer in a liquid crystal display device.

  The cellulose acylate film of the present invention can be used for 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 type, a reflective type, and a 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 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 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 uses of these detailed cellulose acylate films described above are described in detail on pages 45 to 59 of the Japan Society for Invention and Technology (Publication No. 2001-1745, published on March 15, 2001, Japan Institute of Invention). ing.

Although the specific embodiment about the cellulose acylate of this invention is described below, it is not limited to these.
Example 1
(1) Preparation of Cellulose Acylate Solution Cellulose triacetate powder as described below while stirring and dispersing well in the following solvent mixture solution in a 400 L stainless steel dissolution tank having stirring blades and circulating cooling water around the outer periphery A (flakes) was gradually added, and the whole was charged to 200 kg. The solvents methyl acetate, butanol, acetone, methanol, ethanol, and dichloromethane were all used with a water content of 0.2% by mass or less.
First, the powder of cellulose triacetate is charged into a dispersion tank, the pressure in the tank is reduced to 1300 Pa, and the stirring shear rate is initially stirred at a peripheral speed of 15 m / sec (shear stress 5 × 104 kgf / m / sec ² ). The dispersion was carried out for 30 minutes under the condition of having a dissolver type eccentric stirring shaft and an anchor blade on the central shaft and stirring at a peripheral speed of 1 m / sec (shear stress 1 × 104 kgf / m / sec ² ). The starting temperature of the dispersion was 25 ° C., and the final temperature reached 35 ° C. by flowing cooling water. After completion of the dispersion, the high-speed stirring was stopped, and the peripheral speed of the anchor blade was set to 0.5 m / sec and further stirred for 100 minutes to swell the cellulose triacetate flakes. Until the end of swelling, the inside of the tank was pressurized to 0.12 MPa with nitrogen gas. At this time, the oxygen concentration in the tank was less than 2 vol%, and the state of no problem was maintained in terms of explosion protection. Further, it was confirmed that the water content in the dope was 0.2% by mass or less. The composition of the cellulose acylate solution is as follows.

  Cellulose triacetate A (substitution degree 2.80, viscosity average polymerization degree 300, 6-position acetyl group substitution degree 0.90, acetone extract is 7% by mass, weight average molecular weight / number average molecular weight ratio 2.3, Tg 160 ° C., water content 0.2 mass%, 6 mass% viscosity in dichloromethane solution of 305 mPa · s, residual acetic acid content of 0.1 mass% or less, Ca content 65 ppm, Mg 26 ppm, iron 0.8 ppm, sulfate ion 18 ppm, yellow index 9, 47 ppm free acetic acid, powder having an average particle diameter of 1.5 mm and a standard deviation of 0.5 mm) (20 parts by mass), methyl acetate (70.3 parts by mass), acetone (6.5 parts by mass), Ethanol (4.0 parts by mass), the exemplary compound A1 (2.4 parts by mass), UV agent A (2,4-bis- (n-octylthio) -6- (4-hydroxy-3, -Di-tert-butylanilino) -1,3,5-triazine (0.2 parts by mass), UV agent B (2 (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5 Chlorobenzotriazole) (0.2 parts by mass), UV agent C (2 (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) -5-chlorobenzotriazole (0.2 parts by mass), Fine particles (silicon dioxide (particle size: 20 nm), Mohs hardness of about 7) (0.05 parts by mass) and citric acid ethyl ester (monoester and diester mixed 1: 1, 0.04 parts by mass) were used.

(2) Cellulose triacetate film solution The obtained non-uniform gel-like solution is fed with a screw pump whose center is heated to 30 ° C., cooled from the outer periphery of the screw, and at −75 ° C. for 3 minutes. The cooling part was allowed to pass. Cooling was performed using a -80 ° C refrigerant cooled by a refrigerator. And the solution obtained by cooling was heated at 35 degreeC during liquid sending with the screw pump, and was transferred to the stainless steel container. After stirring at 50 ° C. for 2 hours to obtain a homogeneous solution, the solution is filtered with a filter paper having absolute filtration accuracy of 0.01 mm (manufactured by Toyo Filter Paper Co., Ltd., # 63), and further filtered with absolute filter accuracy of 2.5 μm (manufactured by Pole Corporation FH025). The obtained cellulose triacetate solution is heated to 110 ° C. and 1 MPa at the heating part pressure part of the liquid feeding pipe, and is discharged to normal pressure (about 0.1 MPa) to volatilize the organic solvent and cool. A solution having a cellulose triacetate concentration of 24.0% at a temperature of 40 ° C. was obtained. The viscosity (40 ° C.) of this solution is 120 Pa · s, the dynamic storage elastic modulus (15 ° C.) is 3800 Pa, the dynamic storage elastic modulus (−5 ° C.) is 35,000 Pa, The storage elastic modulus (−50 ° C.) was 240,000 Pa. In addition, the aggregate polymerization degree had a solution characteristic of 2.8 to 3.2 million.

(3) Preparation of Cellulose Triacetate Film The filtered cellulose triacetate solution at 50 ° C. was cast on a mirror surface stainless steel support, which is a drum having a diameter of 3 m, through a casting Giuser (the temperature of the support was −5 ° C.). Set). The Gieser used was similar to that described in JP-A-11-314233. The casting speed was 75 m / min and the coating width was 200 cm. The temperature of the entire space of the casting part was set to 15 ° C. Then, the cellulose acylate film cast and rotated 50 cm before the cast part was peeled off from the drum, and both ends were clipped with a pin tenter. Thereafter, the cellulose acylate film held by the pin tenter was conveyed to the drying zone. First, the drying was performed by blowing a 45 ° C. drying air. The film was further dried at 110 ° C. for 5 minutes and further at 145 ° C. for 10 minutes (film temperature was about 140 ° C.) to obtain a cellulose triacetate film (film thickness 80 μm). The obtained sample was cut at 3 cm at both ends, and further knurled at a height of 2 to 10 mm from the end and wound up in a roll shape.

(4) Measurement of Rth After conditioning the cellulose acylate film at 25 ° C. and 60% RH for 24 hours, using an ellipsometer (AEP-100, manufactured by Shimadzu Corporation), a He—Ne laser (wavelength 632.8 nm). ). The retardation value (Rth) in the thickness direction and the in-plane retardation value (Re) were calculated according to the following formulas (1) and (2), respectively.
(Formula 1)
Re = (nx−ny) × d
(Formula 2)
Rth = {(nx + ny) / 2−nz} × d
(Where nx is the refractive index in the fast axis direction in the film plane, ny is the refractive index in the slow axis direction in the film plane, and nz is the refractive index in the direction perpendicular to the film surface, d is the thickness (nm) of the film.

Example 2
The same procedure was performed as in Example 1 except that the exemplified compound A1 in Example 1 was changed to the exemplified compound A2.

Example 3
The same procedure was performed as in Example 1 except that the exemplary compound A1 in Example 1 was changed to the exemplary compound A3.

Example 4
The same operation as in Example 1 was performed except that the exemplary compound A1 in Example 1 was changed to the exemplary compound A4.

Example 5
The same procedure was performed as in Example 2 except that the exemplified compound A2 in Example 2 was changed to the exemplified compound A5.

Example 6
The same procedure was performed as in Example 3 except that the exemplary compound A3 in Example 3 was changed to the exemplary compound A6.

Example 7
The same operation as in Example 1 was carried out except that the solvent in Example 1 was changed to dichloromethane (80.0 parts by mass), methanol (10.0 parts by mass), and butanol (5.0 parts by mass).

Example 8
The same operation as in Example 4 was carried out except that the solvent in Example 4 was changed to dichloromethane (80.0 parts by mass), methanol (10.0 parts by mass), and butanol (5.0 parts by mass).

<< Comparative Example 1 >>
Example 1 except that Example Compound A1 in Example 1 was changed to plasticizer A (triphenyl phosphate) (1.6 parts by mass) and plasticizer B (biphenyl diphenyl phosphate) (0.8 parts by mass). It carried out similarly.

  The evaluation results of Examples 1 to 8 and Comparative Example 1 are shown in Table 1.

  As is apparent from Table 1, according to the present invention, a cellulose acylate film having a low Rth can be obtained, and the optical characteristics of a film having a film thickness of 80 μm are not to mention, and good results are obtained even with films having different film thicknesses. Got. Further, all the films had a good surface shape, low chargeability, and other physical properties.

Claims (6)

Cellulose acylate , a salt having a melting point lower than 25 ° C. and liquid at 25 ° C., and N (CF ₃ SO ₂ ) ₂ ⁻ , C (CF ₃ SO ₂ ) ₃ ⁻ , CF ₃ SO ₃ ⁻ , C ₂ F ^{_{5 SO 3 -, C 3 F}} 7 SO 3 -, C 4 F 9 SO 3 -, BF 4 -, PF 6 -, Al 3 Cl 8 -, Al 2 Cl 7 -, AlCl 4 - and ClO ₄ ^- consisting of contains an ionic liquid having an anion component selected from the group,
A cellulose acylate composition comprising 0.01 to 30 % by mass of the ionic liquid based on cellulose acylate . Contains a compound represented by the cellulose acylate and the general formula (1),
A cellulose acylate composition comprising 0.01 to 30 % by mass of the compound represented by the general formula (1) with respect to cellulose acylate .
General formula (1)

(Wherein R ^{1 to} R ⁵ represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or an aralkyl group, and may be the same or different. X ⁻ is N (CF ₃ SO ₂ ) ₂ ⁻ , C (CF ₃ SO ₂ ) ₃ ⁻ , CF ₃ SO ₃ ⁻ , C ₂ F ₅ SO ₃ ⁻ , C ₃ F ₇ SO ₃ ⁻ , C ₄ F ₉ SO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , Al ₃ Represents an anionic component selected from the group consisting of Cl ₈ ⁻ , Al ₂ Cl ₇ ⁻ , AlCl ₄ ⁻ and ClO ₄ ⁻ .) Cellulose acylate film comprising a cellulose acylate composition according to claim 1 or 2. The cellulose acylate film according to claim 3 , wherein a retardation value in a film thickness direction is 100 nm or less. A cellulose acylate film modifier represented by the general formula (1).
General formula (1)

(Wherein R ^{1 to} R ⁵ represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or an aralkyl group, and may be the same or different. X ⁻ is N (CF ₃ SO ₂ ) ₂ ⁻ , C (CF ₃ SO ₂ ) ₃ ⁻ , CF ₃ SO ₃ ⁻ , C ₂ F ₅ SO ₃ ⁻ , C ₃ F ₇ SO ₃ ⁻ , C ₄ F ₉ SO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , Al ₃ Represents an anionic component selected from the group consisting of Cl ₈ ⁻ , Al ₂ Cl ₇ ⁻ , AlCl ₄ ⁻ and ClO ₄ ⁻ .) The modifier for a cellulose acylate film according to claim 5, which is for a cellulose acylate optical film.