JP4667047B2 - Cellulosic composition, cellulose film, cellulose film modifier, polarizing plate protective film, liquid crystal display device, silver halide photographic light-sensitive material - Google Patents

Description

  The present invention relates to a cellulose body composition and a cellulose body film, and more specifically, a cellulose body film modifier that exhibits good moisture permeability and increases optical anisotropy, and contains the modifier. The present invention relates to a cellulose body composition and a cellulose body film. The present invention further relates to a polarizing plate protective film, a liquid crystal display device and a silver halide photographic light-sensitive material using the cellulose-based film.

  Conventionally, cellulose acylate films have been used for photographic supports and various optical materials because of their toughness and flame retardancy. In particular, in recent years, it has been widely used as an optical transparent film for liquid crystal display devices. Cellulose acylate film is excellent as an optical material for devices that handle polarized light, such as liquid crystal display devices, because of its high optical transparency and high optical isotropy. It has been used as a support for an optical compensation film that can improve the viewing angle (viewing angle compensation).

  In a polarizing plate which is one of members for a liquid crystal display device, a protective film for a polarizer is formed by bonding on at least one side of the polarizer. A general polarizer is obtained by dyeing a stretched polyvinyl alcohol (PVA) film with iodine or a dichroic dye. In many cases, a cellulose acylate film, particularly a triacetyl cellulose film, which can be directly bonded to PVA is used as a protective film for the polarizer. The optical characteristics of the protective film of the polarizer greatly affect the characteristics of the polarizing plate.

  On the other hand, a cellulose acylate film generally has a significantly deteriorated moisture permeability at high temperature and high humidity compared to other transparent supports such as polyethylene terephthalate film, and therefore a compound called a plasticizer is often added. . Known plasticizers added to cellulose acylate include phosphoric acid triesters such as triphenyl phosphate and biphenyl diphenyl phosphate, and phthalic acid esters (for example, Patent Document 1). However, in practice, the plasticizer is not compatible with the cellulose acylate film, causing the film to become cloudy, and the optical anisotropy of the film (for example, the retardation value Rth in the thickness direction) cannot be controlled. The choice is not easy.

When a cellulose acylate film is used as an optical material, it is preferable to increase the optical anisotropy of the film depending on the intended use. Among the compounds called plasticizers described above, those having an effect of increasing the optical anisotropy of cellulose acylate film are known. For example, aromatic phosphate triesters are known. The performance is not sufficient, and since such plasticizers have the adverse effect of deteriorating the moisture permeability under high temperature and high humidity, the optical anisotropy is large and the moisture permeability under high temperature and high humidity is low. The development of cellulose acylate films and their modifiers is eagerly desired.
JP-A-9-95557

The first object of the present invention is to provide a cellulosic film having a large optical anisotropy.
The second object of the present invention is to provide a cellulosic film having a large optical anisotropy and a low moisture permeability.
A third object of the present invention is to provide a polarizing plate protective film, a liquid crystal display device, and a support for silver halide photographic light-sensitive material prepared using a cellulose film having a large optical anisotropy and a low moisture permeability. It is in.

The object of the present invention has been achieved by the following means.
(1) A cellulose composition comprising at least one of a cellulose and a compound represented by the following general formula (1).

[Wherein, R ¹ represents an alkyl group or an aryl group, and R ² and R ³ each independently represents a hydrogen atom, an alkyl group or an aryl group. Moreover, the alkyl group and the aryl group may have a substituent. Two or more groups of R ¹ , R ² and R ³ may be bonded to each other to form a ring. ]

(2) A cellulosic film comprising at least one compound represented by the general formula (1).
(3) The cellulose film described in (2) above, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

[Wherein, R ⁴ and R ⁵ each represents an aryl group, and each may independently have a substituent. R ⁴ and R ⁵ may form a condensed ring. ]

(4) The cellulose body film as described in (2) or (3) above, wherein the cellulose body is cellulose acylate.
(5) Cellulose acylate, comprising at least one compound represented by the above general formula (1) and general formula (2) in an amount of 1 to 30% by mass of the cellulose acylate Film.

(6) The cellulose acylate film according to the above (5), wherein the acyl substitution degree of the cellulose acylate is 2.60 to 3.00.
(7) The cellulose acylate film according to the above (5), wherein the acyl substitution degree of the cellulose acylate is 2.80 to 2.95.
(8) The cellulose acylate film according to the above (5), wherein the degree of substitution with the acetyl group of cellulose acylate is 2.60 to 3.00.

(9) The cellulose acylate film according to the above (5), wherein the substitution degree of the cellulose acylate substituted with an acyl group having 3 to 22 carbon atoms is 0.00 to 0.80.
(10) The cellulose acylate is substituted with an acetyl group and an acyl group having 3 to 22 carbon atoms, and 30% or more of the acyl groups having 3 to 22 carbon atoms are substituted for the hydroxyl group at the 6-position The cellulose acylate film as described in the above item (5).
(11) The cellulose acylate film according to the above (5), wherein the acyl substitution degree at the 6-position of the cellulose acylate is 0.80 to 1.00.
(12) The cellulose acylate film according to the above (5), wherein the acyl substitution degree at the 6-position of the cellulose acylate is 0.85 to 1.00.

(13) A cellulosic film modifier represented by the above general formula (1) and general formula (2).
(14) A polarizing plate protective film comprising at least one layer of the cellulose-based film according to any one of (2) to (12).

［式中、Ｒ^４およびＲ^５はそれぞれアリール基を表し、それぞれ独立に置換基を有していてもよい。その置換基はアルキル基、アリール基又はアシルアミノ基である。Ｒ^４およびＲ^５は、縮合環を形成してもよい。］
［２］ 上記［１］記載の一般式（２）で表される化合物を少なくとも１つを含有することを特徴とするセルロースアシレートフイルム。
［３］ 上記［１］記載の一般式（２）で表されるセルロースアシレートフイルム用改質剤。
［４］ 上記［２］に記載のセルロースアシレートフイルムを少なくとも１層含有することを特徴とする偏光板保護膜。
［５］ 上記［２］に記載のセルロースアシレートフイルムを少なくとも１層含有することを特徴とする液晶表示装置。
［６］ 上記［２］に記載のセルロースアシレートフイルムを支持体として使用することを特徴とするハロゲン化銀写真感光材料。
上記［１］〜［６］以外のその他の事項については参考のために記載するものである。 (15) A liquid crystal display device comprising at least one layer of the cellulose-based film according to any one of (2) to (12).
(16) A silver halide photographic light-sensitive material comprising the cellulose film according to any one of (2) to (12) as a support.
The present invention is described in the following [1] to [6].
[1] A cellulose acylate composition comprising cellulose acylate and at least one compound represented by the following general formula (2).

[Wherein, R ⁴ and R ⁵ each represent an aryl group, and may each independently have a substituent. The substituent is an alkyl group, an aryl group or an acylamino group. R ⁴ and R ⁵ may form a condensed ring. ]
[2] A cellulose acylate film comprising at least one compound represented by the general formula (2) according to the above [1].
[3] A cellulose acylate film modifier represented by the general formula (2) described in [1] above.
[4] A polarizing plate protective film comprising at least one layer of the cellulose acylate film according to [2].
[5] A liquid crystal display device comprising at least one layer of the cellulose acylate film according to [2].
[6] A silver halide photographic light-sensitive material using the cellulose acylate film as described in [2] above as a support.
Other matters other than the above [1] to [6] are described for reference.

  The cellulose body film to which the compounds represented by the general formula (1) and the general formula (2) are added has an excellent effect that the moisture permeability is small and the optical anisotropy is very large. Therefore, the cellulose film can be used for a polarizing plate protective film, a liquid crystal display device, and a silver halide photographic light-sensitive material.

  In this invention, the at least 1 compound represented by following General formula (1) is used as a modifier for cellulose bodies.

The compound represented by the general formula (1) of the present invention will be described in detail. In the general formula (1), R ¹ represents an alkyl group or an aryl group, and an aryl group is more preferable. R ² and R ³ each independently represent a hydrogen atom, an alkyl group or an aryl group, and more preferably each independently a hydrogen atom or an aryl group. Here, the alkyl group may be linear, branched or cyclic, and preferably has 1 to 25 carbon atoms, more preferably 6 to 25, and more preferably 6 to 20 Is most preferred. The aryl group preferably has 6 to 36 carbon atoms, and more preferably 10 to 36 carbon atoms. R ¹ , R ^2, and R ³ may each form a ring by combining two or more groups with each other.

  The above alkyl group and aryl group may have a substituent, such as a halogen atom (for example, chlorine, bromine, fluorine and iodine), an alkyl group, an aryl group, an alkoxy group, an aryloxy group, acyl Group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, sulfonylamino group, hydroxy group, cyano group, amino group and acylamino group, more preferably alkyl group, aryl group, alkoxy group, aryloxy group and halogen atom And particularly preferably an alkyl group and an aryl group.

  The general formula (1) is preferably a compound represented by the following general formula (2).

In the general formula (2), R ⁴ and R ⁵ each independently represents an aryl group. The aryl group preferably has 6 to 36 carbon atoms, and more preferably 10 to 36 carbon atoms. R ⁴ and R ⁵ may form a condensed ring.

  Each of the above aryl groups may have a substituent, such as a halogen atom (for example, chlorine, bromine, fluorine and iodine), an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, An alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a sulfonylamino group, a hydroxy group, a cyano group, an amino group, and an acylamino group are preferable, and an alkyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogen atom are more preferable. Particularly preferred are an alkyl group and an aryl group.

  The amount of the cellulose body modifier of the present invention added is preferably 2 to 30% by mass, more preferably 2 to 25% by mass, and more preferably 2 to 20% by mass with respect to the cellulose body. Most preferred.

  Next, although the preferable example of a compound represented by General formula (1) and General formula (2) is shown below, this invention is not limited to these specific examples.

Any of the compounds of the present invention can be prepared by known methods.
That is, the compounds of the general formula (1) and the general formula (2) are obtained by dehydration condensation reaction between carboxylic acids and amines using a condensing agent (for example, dicyclohexylcarbodiimide (DCC)), or carboxylic acid chloride derivatives and amine derivatives. It can be obtained by a substitution reaction with For example, A-8 can be obtained by a substitution reaction of 4-phenyl-benzoic acid chloride and aniline.
Moreover, a commercial item can also be utilized, for example, the commercial item of Tokyo Chemical Industry can be used about A-1.

  Next, the cellulose body used in the present invention will be described in detail. The cellulose body used in the present invention may be anything as long as it is a compound using cellulose as a raw material. Cellulose acylate is preferred. The cellulose acylate used in the present invention is not particularly limited as long as the effects of the present invention are exhibited, and two or more different cellulose acylates may be mixed and used. Preferred examples of the cellulose acylate include the following. That is, the cellulose acylate is a cellulose acylate in which the degree of substitution of the hydroxyl group of cellulose satisfies all of the following formulas (I) to (III).

(I) 2.6 ≦ SA + SB ≦ 3.0
(II) 2.0 ≦ SA ≦ 3.0
(III) 0 ≦ SB ≦ 0.8

  Here, SA and SB represent the substitution degree of the acyl group substituted with the hydroxyl group of cellulose, SA is the substitution degree of the acetyl group, and SB is the substitution degree of the acyl group having 3 to 22 carbon atoms. .

  Glucose units constituting cellulose with β-1,4 glycosidic bonds have free hydroxyl groups at the 2nd, 3rd and 6th positions. The cellulose acylate used in the present invention is a polymer obtained by esterifying some or all of these hydroxyl groups with acyl groups. In this specification, the degree of acyl substitution means the proportion of cellulose esterified at each of the 2-position, 3-position and 6-position, and the total acyl substitution degree represents the sum of these. Specifically, the degree of substitution is 1 when the hydroxyl groups at the 2-position, 3-position and 6-position of cellulose are each 100% esterified. Therefore, when all of the 2-position, 3-position and 6-position of cellulose are 100% esterified, the total degree of acyl substitution is 3, which is the maximum.

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 substitution degree of SB is 0 to 0.80, particularly 0 to 0.60. Further, 28% or more of SB is a 6-position hydroxyl group substituent, more preferably 30% or more is a 6-position hydroxyl group substituent, more preferably 31% or more, and particularly 32% or more is a 6-position hydroxyl group. It is also preferable that it is a substituent.
Furthermore, a cellulose acylate film in which the sum of the substitution degrees of 6-position SA and SB of the cellulose acylate is 0.8 or more, more preferably 0.85, and particularly preferably 0.90 can be mentioned.
With these cellulose acylate films, a solution having a preferable solubility can be prepared. In particular, in a non-chlorine organic solvent, a good solution can be prepared.

  The acyl group (SB) having 3 to 22 carbon atoms of cellulose acylate may be an aliphatic group or an aryl 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. Specific examples of these include propionyl, butanoyl, keptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, iso-butanoyl, t-butanoyl, cyclohexanecarbonyl, oleoyl, Examples include benzoyl, naphthylcarbonyl, cinnamoyl groups and the like. Among these, propionyl, butanoyl, dodecanoyl, octadecanoyl, t-butanoyl, oleoyl, benzoyl, naphthylcarbonyl, cinnamoyl and the like.

  The basic principle of the cellulose acylate synthesis method is described in Mita 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 cellulose acylate in which the polymer component constituting the film substantially has the above definition. “Substantially” means 55% by mass or more (preferably 70 to 100% by mass, more preferably 80 to 100% by mass) of the polymer component. Cellulose acylate particles are preferably used as raw materials 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 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 weight of celluloses. When the amount of the sulfuric acid catalyst is within 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 water content of the cellulose acylate in the present invention, it is necessary to dry it, and the method is not particularly limited as long as the desired water content is obtained.
These cellulose acylates of the present invention are described in detail on pages 7 to 12 of the raw material cotton and the synthesis method in 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.

The cellulosic film of the present invention has various additives (for example, plasticizers, UV inhibitors, deterioration inhibitors, optical anisotropy control agents, fine particles, release agents, infrared absorption) in each preparation step. Agents, etc.) can be added. They may be solid or oily. That is, the melting point and boiling point are not particularly limited. For example, mixing of an 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 in, for example, JP-A-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, but these are conventionally known techniques.
Furthermore, for these details, materials described in detail on pages 16 to 22 in the Japan Institute of Invention Disclosure Bulletin (Public Technical Number 2001-1745, published on March 15, 2001, Japan Institute of Invention) are preferably used.

Next, the organic solvent for dissolving the cellulose body used in the present invention will be described.
First, a non-chlorine organic solvent that is preferably used in preparing a cellulose solution will be described. In the present invention, the non-chlorine organic solvent to be used is not particularly limited as long as the object can be achieved within a range in which the cellulose body can be dissolved, cast and formed. The non-chlorine organic solvent used in the present invention is preferably a solvent selected from esters, ketones and ethers having 3 to 12 carbon atoms. The ester, ketone and ether may have a cyclic structure. 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 the ether 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 body is selected from the above-mentioned various viewpoints, but is preferably a mixed solvent of three or more different from each other.
The first solvent is at least one selected from methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, dioxolane, dioxane or a mixture thereof, preferably methyl acetate, acetone, methyl formate, ethyl formate or It is a mixture of these.
The second solvent is at least one selected from ketones having 4 to 7 carbon atoms or acetoacetate or a mixture thereof, preferably methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl acetylacetate, or these It is a mixed solution.
Note that when the first solvent is a mixed liquid of two or more kinds of solvents, the second solvent may be omitted.

The third solvent is selected from alcohols or hydrocarbons having 1 to 10 carbon atoms, preferably alcohols having 1 to 8 carbon atoms.
The portion other than the hydroxyl group of the alcohol serving as the third solvent may be linear, branched or cyclic, and is preferably a saturated aliphatic hydrocarbon. Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 2-methyl-2-butanol and cyclohexanol. 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.

  The hydrocarbon as the third solvent 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 that can be used in the present invention is more specifically described in the Invention Association's public technical bulletin (public technical number 2001-1745, published on March 15, 2001, Invention Association), pages 12 to 16. It is described in detail on the page. Although the combination of the preferable non-chlorine type organic solvent of this invention can be mentioned below, it is not limited to these.

-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, part 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 non-chlorine organic solvent of the present technology, the dope used in the present technology may contain dichloromethane in an amount of 10% by mass or less based on the total amount of the organic solvent of the present technology.

  In preparing the cellulose acylate solution of the present invention, a chlorinated organic solvent is sometimes used as a main solvent. 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 cellulose acylate can be dissolved and cast and formed. 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 necessary to use at least 50% by mass of dichloromethane.

  The non-chlorine organic solvent used in combination is preferably a solvent selected from esters, ketones, ethers, alcohols, hydrocarbons, etc. having 3 to 12 carbon atoms. 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 the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 2-methyl-2-butanol and cyclohexanol. 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, 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 of the present invention is preferably a solution in which 10 to 30% by mass is dissolved in an organic solvent, more preferably 13 to 27% by mass, and particularly 15 to 25% by mass. It is a cellulose acylate solution. 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 to 5 mass% with the organic solvent of the same composition is 150,000 to 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 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 Teflon 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. 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, with respect to the preparation of the cellulose acylate solution (dope) of the present invention, the dissolution method is not particularly limited, and may be room temperature, further a cooling dissolution method or a high temperature dissolution method, or a combination thereof. With respect to 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-10-95854 -45950, JP-A-2000-53784, JP-A-11-322946, JP-A-11-322947, JP-A-2-276830, JP-A-2000-273239, JP-A-11-71463. No. 4, JP-A No. 04-259511, JP-A No. 2000-273184, JP-A No. 11-323017, JP-A No. 11-302388, and the like describe preparation methods of cellulose acylate solutions. 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. These details are described in detail on pages 22 to 25 in the Japan Society for Invention and Technology (Publication No. 2001-1745, published on March 15, 2001, Japan Society for Inventions), especially for non-chlorine solvent systems. Be implemented in a way that Further, the cellulose acylate dope solution of the present invention is usually subjected to solution concentration and filtration. Similarly, the dope solution of the invention is published in the technical report of the Invention Association (public technical number 2001-1745, published on March 15, 2001, Invention Association). It is described in detail on the page. In addition, when it melt | dissolves at high temperature, it is the case where it is more than the boiling point of the organic solvent to be used, and in that case, it uses in a pressurized state.

  The cellulose acylate solution of the present invention preferably has a viscosity and dynamic storage modulus within the range. The viscosity and dynamic storage modulus of the solution can be measured by the following method. 1 mL of the sample solution is measured using a Steel Cone (manufactured by TA Instruments) having a diameter of 4 cm / 2 ° on a rheometer (manufactured by TA Instruments, trade name: CLS 500). Measurement conditions were measured at Oscillation Step / Temperature Ramp with a range of 40 ° C. to −10 ° C. being changed at 2 ° C./min, and static non-Newtonian viscosity at 40 ° C. n * (Pa · s) and storage at −5 ° C. Obtain the elastic modulus G '(Pa). The sample solution is preliminarily kept at the measurement start temperature until the liquid temperature becomes constant, and then the measurement is started.

  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 a cellulose body solution will be described. As a method and equipment for producing the cellulose body 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 apparatus is added to the surface processing of the film. Each of these manufacturing processes is described in detail on pages 25 to 30 in the Japan Institute of Invention Disclosure Technical Report (public technical number 2001-1745, issued on March 15, 2001, Japan Institute of Invention). (Including rolling), metal support, drying, peeling, stretching and the like.
In this invention, as a film thickness of a cellulose body film, when using for a polarizing plate, 10-120 micrometers is preferable, 20-100 micrometers is more preferable, 30-90 micrometers is the most preferable. Moreover, when using as a support body of a photosensitive material, 80-300 micrometers is preferable, 90-250 micrometers is more preferable, 100-200 micrometers is the most preferable.

  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. The co-casting can be performed, for example, in the manner described in JP-A-56-162617 and JP-A-2002-316387. The number of layers in the case of producing the cellulose acylate film of the present invention by co-casting is preferably 2 to 5 layers, more preferably 2 to 4 layers, and particularly preferably 2 to 3 layers.

  In the case of having a casting process consisting of two or more layers, the composition of the chlorinated solvent in each layer is either the same or different in the cellulose acylate solution and the cellulose acylate film to be produced. 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, the solution in each layer The temperature of each layer is either the same or different, the coating amount of each layer is either the same or different, and the viscosity of each layer is the same Or different viscosities, each layer has the same or different thickness after drying, and the materials present in each layer are in the same or different state Or a distribution, a physical property of each layer being the same or a different physical property, and a physical property of each layer being either a uniform physical property or a different physical property distribution An acylate solution and a cellulose acylate film prepared 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 Society of Inventions). 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, Thermophysical Properties (Tg) of Cellulose Acylate described in detail on page 11 in the Japan Society of Invention Disclosure Technical Report (Public Technical No. 2001-1745, issued on March 15, 2001, Invention Association) , Heat of crystallization).
The cellulose acylate film of the present invention may be stretched in any direction at the time of casting and after drying for the purpose of adjusting optical performance.

The cellulose acylate film can achieve an 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 is so-called low temperature plasma that occurs under a low pressure gas of 10 ^{−3 to} 20 Torr (0.1 Pa to 2.7 kPa). Furthermore, plasma treatment under atmospheric pressure is also preferable.

  A plasma-excitable gas is a gas that is plasma-excited under the above conditions, and examples thereof include 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 in the technical report of the Invention Association (Public Technical Number 2001-1745, published on March 15, 2001, Invention Association). 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 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 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 onto 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 Society of Inventions). In addition, various functional layers of the cellulose acylate film of the present invention are also disclosed on pages 32 to 45 in the Japan Institute of Technology (Technology No. 2001-1745, published on March 15, 2001, Invention Association). Are described in detail.

The moisture permeability of the cellulose acylate film of the present invention is preferably 200~2000g / (m ² · day), more preferably from 400~2000g / (m ² · day), 400～1800G / Most preferred is (m ² · day).
The moisture permeability in the present invention is a change in weight before and after leaving a cup containing calcium chloride covered and sealed with each film sample at 60 ° C. and 95% RH for 24 hours. (G / (m ² · day)) is a value obtained by evaluating the moisture permeability of the cellulose triacetate film based on the hygroscopicity of calcium chloride.

The optical performance of the cellulose acylate film will be described below.
In-plane retardation (Re) and retardation (hereinafter referred to as Rth), which are optical performances of the cellulose acylate film of the present invention, are measured using an ellipsometer (AEP-100, manufactured by Shimadzu Corporation). is there.

Specifically, Re can be obtained according to the following formula as a value obtained by multiplying the longitudinal and lateral refractive index difference measured at a wavelength of 632.8 nm by the film thickness.
Re = (nx−ny) × d
[Where nx is the refractive index in the slow axis direction (direction in which the refractive index is maximum); ny is the refractive index in the direction perpendicular to the slow axis; and d is the thickness of the film (Unit: nm). ]
The in-plane retardation (Re) of the cellulose ester film is preferably 50 nm or less, more preferably 40 nm or less, further preferably 30 nm or less, and most preferably 20 nm or less.

Specifically, the retardation (Rth) in the thickness direction of the film can be determined according to the following formula as a value obtained by multiplying the birefringence index in the thickness direction measured at a wavelength of 632.8 nm by the film thickness.
Rth = {(nx + ny) / 2−nz} × d
[Wherein nx is the refractive index in the slow axis direction (direction in which the refractive index is maximum); ny is the refractive index in the direction perpendicular to the slow axis; nz is the refractive index in the thickness direction] And d is the thickness of the film (unit: nm). ]

  The thickness direction retardation (Rth) of the cellulose ester film is preferably 100 nm to 300 nm, more preferably 120 nm to 300 nm, and most preferably 150 nm to 300 nm.

First, the use of the cellulosic film produced in the present invention will be briefly described. 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 production method of a polarizing plate is not specifically limited, It can produce 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 for bonding 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 sides of the polarizer, and is further constructed by laminating a protective film on one surface of the polarizing plate and a separate film on 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 protective film is bonded for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the surface where the polarizing plate is bonded to the liquid crystal plate. The separate film is used for the purpose of covering the adhesive layer to be bonded to the liquid crystal plate, and is used on the side of the surface for bonding the polarizing plate to the 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 an excellent display property regardless of the position. . In particular, the polarizing plate protective film on the outermost surface on the display side of the liquid crystal display device is provided with a transparent hard coat layer, an antiglare layer, an antireflective layer, and the like.

  The cellulose-based 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 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-based film is effective in the liquid crystal display device in any display mode. Further, it is effective in any of a transmissive type, a reflective type, and a transflective liquid crystal display device. The cellulose 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 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 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 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-based film of the present invention is also advantageously used as an optical compensation sheet for a reflective liquid crystal display device of TN type, STN type, HAN type, and GH (Guest-Host) type. 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, International Publication WO98 / 48320, and Japanese Patent No. 3022477. The optical compensation sheet used in the reflective liquid crystal display device is described in the pamphlet of International Publication WO00 / 65384.

The cellulosic 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 of 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 Kume et al. (Kume et al., SID 98 Digest 1089 (1998)).
The uses of these detailed cellulose-based films described above are described in detail on pages 45-59 in the Japan Society for Invention and Technology (Publication No. 2001-1745, published on March 15, 2001, Japan Society for Invention). ing.
Furthermore, the cellulose acylate film of the present invention can also be used as a support for silver halide photographic light-sensitive materials, and is a reference document described on pages 276 to 291 of the foundation of photographic engineering (edited by Japan Photographic Society, Corona). Various materials, prescriptions, and processing methods described in the above can be applied. Regarding these techniques, JP-A-2000-105445 describes in detail the color negative, and the cellulose acylate film of the present invention is preferably used. Further, application as a support for a color reversal silver halide photographic light-sensitive material is also preferable, and various materials, formulations and processing methods described in JP-A No. 11-282119 can be applied.

  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> Cellulose body film and cellulose body film modifier (1-1) Preparation of cellulose acylate solution In a 5 L glass container having a stirring blade, while stirring and dispersing well in the following solvent mixed solution, The cellulose triacetate powder A (flakes) described below was gradually added, and the whole was charged to 2 kg. In addition, all the methyl acetate, acetone, and ethanol which are solvents used the thing whose water content is 0.2 mass% or less. First, the powder of cellulose triacetate was dispersed in a dispersion tank for 30 minutes with nitrogen gas sealed and having a dissolver type eccentric stirring shaft and an anchor blade on the central shaft. The starting temperature of dispersion was 30 ° C. 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 (SA + SB is 2.78, SA is 2.78, SB is 0, viscosity-average polymerization degree is 303, and moisture content is 1% by mass or less. Cellulose acylate flakes are substituted at the 6-position of cellulose acylate. A degree of 0.90 was used.) (15 parts by mass), methyl acetate (87.0 parts by mass), acetone (8.0 parts by mass), ethanol (5.0 parts by mass), TPP / BDP ( 8.0 parts by mass) was used to prepare Sample 1 in Table 1. Next, Sample 2 having the same composition as Sample 1 was prepared, except that TPP / BDP of Sample 1 was changed to 12.0 parts by mass. Furthermore, instead of TPP / BDP of Sample 1, Samples 3 to 15 were prepared by adding the modifiers shown in Table 1 to the addition amounts shown in Table 1.

(1-2) Cellulose triacetate film solution The obtained non-uniform gel solution was fed with a screw pump and allowed to pass through the cooling part at -70 ° C for 3 minutes. Cooling was performed using a -80 ° C refrigerant cooled by a refrigerator. The solution obtained by cooling is transferred to a stainless steel container, stirred at 50 ° C. for 2 hours to obtain a uniform solution, and then filtered with a filter paper with absolute filtration accuracy of 0.01 mm (manufactured by Toyo Filter Paper Co., Ltd., # 63). The solution was filtered, and further filtered through a filter paper having an absolute filtration accuracy of 2.5 μm (manufactured by Pall, FH025).

(1-3) Production of Cellulose Triacetate Film A filtered cellulose triacetate solution at 50 ° C. was cast on a mirror surface stainless steel support through a casting Giuser. The temperature of the support was 5 ° C., the casting speed was 3 m / min, and the coating width was 30 cm. The mixture was left at room temperature for 1 minute, and then a drying air of 55 ° C. was blown for drying. After 5 minutes, the film was peeled off from the mirror surface stainless steel support, and then dried at 133 ° C. for 27 minutes to obtain a cellulose triacetate film having a film thickness of 60 μm.

(1-4) Measurement of moisture permeability of cellulose acetate film The moisture permeability of the obtained cellulose triacetate film was obtained by sealing a cup containing calcium chloride with each film sample and sealing it. The moisture permeability of the cellulose triacetate film based on the hygroscopicity of calcium chloride was calculated from the weight change (g / (m ² · day)) before and after standing for 24 hours under the conditions of ° C and 95% RH.

(1-5) Measurement of Rth of Cellulose Acetate Film Using an ellipsometer (AEP-100, manufactured by Shimadzu Corporation), the film thickness is determined by the in-plane vertical and horizontal refractive index difference measured at a wavelength of 632.8 nm. As a multiplied value, it was obtained according to the following formula.

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 perpendicular to the slow axis nz: refractive index in the thickness direction d: film thickness (unit: nm) )

  From Table 1, the moisture permeability is smaller and optically anisotropic than C-1, C-2, and C-3 having TPP / BDP and similar skeletons that are widely used by adding the compound of the present invention. It can be seen that a cellulose acetate film having high properties (large Rth) can be produced. In particular, the optical anisotropy can be drastically increased with respect to TPP / BDP by adding the modifier of the present invention.

<Example 2>
A cellulose acylate film was produced using the following composition in the same manner as in Example 1. In this case as well, good results were obtained as in Example 1.

Cellulose triacetate (acetylation degree 60.9%) (100 parts by mass)
Methylene chloride (300 parts by mass)
Methanol (45 parts by mass)
Samples 1 to 15 described in Example 1 (11.7 parts by mass)

<Example 3> Polarizing plate protective film For Samples 1 to 15 of Example 1, Samples 201 to 205 were prepared and evaluated by the method described in Example 1 of JP-A-11-316378. The optical properties of the elliptically polarizing plate obtained with the cellulose film of the present invention were excellent. Further, the durability over time was not particularly problematic as compared with Comparative Sample 2.

<Example 4> Liquid crystal display device Regarding samples 1 to 15 of Example 1, the liquid crystal display device described in Example 1 of Japanese Patent Laid-Open No. 10-48420 and the first example of Japanese Patent Application Laid-Open No. 9-26572 are described. An optically anisotropic layer containing discotic liquid crystal molecules, an alignment film coated with polyvinyl alcohol, a VA liquid crystal display device described in FIGS. 2 to 9 of JP-A-2000-154261, and a diagram of JP-A-2000-154261 When the OCB type liquid crystal display device described in 10 to 15 was evaluated, good performance was obtained in any case.

<Example 5> Silver halide photographic light-sensitive material Samples 401 to 405 were prepared in the same manner as in Example 1 except that the film thickness of Samples 1 to 15 of Example 1 was changed to 120 nm. One of the obtained films was provided with the first layer and the second layer described in Example 1 of JP-A-4-73736 to form a back layer having a cationic polymer as a conductive layer. Further, the sample 105 described in Example 1 of JP-A No. 11-38568 was applied to the opposite side of the obtained film base provided with the back layer to produce a silver halide photographic light-sensitive material. The obtained silver halide photographic light-sensitive material was excellent in image quality and had no problem in handling.

Claims (6)

A cellulose acylate composition comprising cellulose acylate and at least one compound represented by the following general formula (2).

[Wherein, R ⁴ and R ⁵ each represent an aryl group, and may each independently have a substituent. The substituent is an alkyl group, an aryl group or an acylamino group. R ⁴ and R ⁵ may form a condensed ring. ] A cellulose acylate film comprising at least one compound represented by formula (2) according to claim 1. The modifier for cellulose acylate films represented by the general formula (2) according to claim 1. A polarizing plate protective film comprising at least one layer of the cellulose acylate film according to claim 2. A liquid crystal display device comprising at least one layer of the cellulose acylate film according to claim 2. A silver halide photographic light-sensitive material, wherein the cellulose acylate film according to claim 2 is used as a support.