JP2007169523A - Cellulose derivative film, optical compensation film using the cellulose derivative film, polarizing plate and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a cellulose derivative film that has sufficiently low retardation (Rth) in the direction of film thickness in the case of use as a protection film for a polarizing plate, low equilibrium moisture content and improved durability at a high temperature and humidity. <P>SOLUTION: The cellulose derivative film comprises at least a cellulose derivative containing a substituent group with polarizability anisotropy of ≥2.5×10<SP>-24</SP>cm<SP>3</SP>and one or more kinds of retardation regulators satisfying a specific numerical expression. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a cellulose derivative film useful for a liquid crystal display device, an optical compensation film using the cellulose derivative film, an optical material such as a polarizing plate, and a liquid crystal display device.

  Conventionally, cellulose ester films represented by 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 ester 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 optical isotropy. Have been used as a support for optical protective films (hereinafter also referred to as protective films) and optical compensation films capable of improving the display viewed from an oblique direction (viewing angle compensation).

  In recent liquid crystal display devices, improvement in viewing angle characteristics has been strongly demanded, and the display mode of the liquid crystal display device is improved from the conventional TN system in view of improving response speed and viewing angle. In recent years, in addition to the STN method, various configurations of the optical compensation layer for improving the viewing angle characteristics are being studied in response to diversification such as the VA method, the IPS method, and the OCB method. Therefore, an optical compensation film having a negative retardation (Rth) in the film thickness direction, particularly a cellulose ester film that can be used as a protective film for a polarizing plate has been demanded as one of optical compensation means.

On the other hand, for example, Patent Document 1 proposes a technique for producing a cellulose acylate film having a negative Rth by selecting production conditions such as a substitution degree of cellulose acetate and a dissolution method. Patent Document 2 proposes a technique for reducing retardation with a compound having a specific structure.
JP 2005-120352 A JP 2005-99191 A

  In the technique of Patent Document 1, the equilibrium moisture content of the obtained film is high, and when a polarizing plate using these as a protective film is used under high temperature and high humidity, there is a problem that polarization performance deteriorates, and improvement is desired. It was.

  On the other hand, in the technique described in Patent Document 2, retardation of cellulose acylate film, that is, Re and Rth, is reduced by using a specific compound having an aromatic ring but low planarity with respect to cellulose acetate. A method has been proposed. However, even if the proposed method is used, there is a limit to the effect of reducing Rth, and Rth does not become a sufficiently negative value, or it is necessary to use a large amount of the compound described in the above-mentioned literature in combination. Crying out of the compound to the film surface and a decrease in handleability due to a decrease in elastic modulus have been problems.

An object of the present invention is to provide a cellulose derivative film having negative Rth that can be used as a member for optical compensation in various display modes. Furthermore, it is to provide a cellulose derivative film for producing a polarizing plate having excellent durability under high temperature and high humidity conditions.
Another object of the present invention is to provide an optical compensation film, a polarizing plate, and a liquid crystal display device using the polarizing plate, which are excellent in viewing angle characteristics and excellent in durability, using the cellulose derivative film.

As a result of intensive studies, the present inventors have efficiently used a cellulose derivative having a specific substituent and a compound that reduces the retardation Rth in the film thickness direction, thereby efficiently exhibiting a desired negative Rth. The present inventors have found that a film can be provided and have completed the present invention. Furthermore, it has been found that by using a substituent having high hydrophobicity as the specific substituent, the equilibrium moisture content of the film can be very low, and a polarizing plate having improved durability under high temperature and high humidity conditions can be provided.
That is, the present invention is as follows.

1. A cellulose derivative containing a substituent having a polarizability anisotropy represented by the following formula (1) of 2.5 × 10 ⁻²⁴ cm ³ or more, and 1 of a retardation regulator satisfying the following formula (11-1) A cellulose derivative film comprising at least one or more.
Formula (1): Δα = α _x − (α _y + α _z ) / 2
(Where α _x is the largest component of the eigenvalues obtained after diagonalizing the polarizability tensor;
α _y is the second largest component of the eigenvalues obtained after diagonalizing the polarizability tensor;
α _z is the smallest component of the eigenvalues obtained after diagonalizing the polarizability tensor. )
Formula (11-1): Rth (a) −Rth (0) /a≦−1.5
(However, 0.01 ≦ a ≦ 30)
Rth (a): Rth (nm) at a wavelength of 589 nm of a film having a film thickness of 80 μm comprising cellulose acylate having an acetyl substitution degree of 2.85 and 100 parts by mass of the cellulose acylate with a part by mass of the above retardation modifier.
Rth (0): Rth (nm) at a wavelength of 589 nm of a film having a film thickness of 80 μm made only of cellulose acylate having an acetyl substitution degree of 2.85 and not containing the above retardation regulator
a: parts by mass of the above retardation regulator with respect to 100 parts by mass of cellulose acylate; 2. The cellulose derivative film as described in 1 above, wherein the retardation regulator is any one of compounds represented by the following general formulas (1) to (21).

(In the general formula (1), the R ¹¹ to R ¹³ each independently represents an aliphatic group having 1 to 20 carbon atoms, the aliphatic groups may have a substituent group .R ¹¹ to R ¹³ may be linked together to form a ring.)

(In the general formulas (2) and (3), Z represents a carbon atom, an oxygen atom, a sulfur atom, or —NR ²⁵ —, and R ²⁵ represents a hydrogen atom or an alkyl group. 6-membered ring which may have a substituent .Y ^21, Y ²² each independently represent the carbon atoms 1 to 20, an ester group, an alkoxycarbonyl group, an amido group or a carbamoyl group, Y ^21, Y ²² may be linked to each other to form a ring, m represents an integer of 1 to 5, and n represents an integer of 1 to 6.)

(In General Formulas (4) to (12), Y ^{31 to} Y ⁷⁰ are each independently an ester group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. An amide group, a carbamoyl group having 1 to 20 carbon atoms or a hydroxy group, V ^{31 to} V ⁴³ each independently represents a hydrogen atom or an aliphatic group having 1 to 20 carbon atoms, and L ^{31 to} L ⁸⁰ each independently Represents a divalent saturated linking group having 0 to 40 atoms and 0 to 20 carbon atoms, wherein the number of atoms of L ^{31 to} L ⁸⁰ is 0 at both ends of the linking group. (This means that the group directly forms a single bond. V ^{31 to} V ⁴³ and L ^{31 to} L ⁸⁰ may further have a substituent.)

(In General Formula (13), R ¹ represents an alkyl group or an aryl group, and R ² and R ³ each independently represent a hydrogen atom, an alkyl group, or an aryl group. R ¹ , R ^2, and R ³ The total number of carbon atoms is 10 or more, and each of the alkyl group and aryl group may have a substituent.)

(In the general formula (14), R ⁴ and R ⁵ each independently represents an alkyl group or an aryl group. The total number of carbon atoms of R ⁴ and R ⁵ is 10 or more. The group may have a substituent.)

(In the general formula (15), R ¹ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, and R ² represents a hydrogen atom, a substituted or unsubstituted aliphatic group, or a substituted or unsubstituted group. L ¹ represents a divalent to hexavalent linking group, and n represents an integer of 2 to 6 according to the valence of L ¹ .

(In General Formula (16), R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group. X is formed from one or more groups selected from the following linking group group 1. Y represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group.
(Linking group group 1) A single bond, —O—, —CO—, —NR ⁴ —, an alkylene group or an arylene group is represented. R ⁴ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. )

(In the general formula (17), Q ¹ , Q ² and Q ³ each independently represent a 5- or 6-membered ring. X represents B, C—R (R represents a hydrogen atom or a substituent), N, P and P = O are represented.)

(In the general formula (19), 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. The alkyl group and the aryl group each represent a substituent. (You may have it.)

(In the general formula (21), R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. X ¹ , X ² , X ³ and X ⁴ are each independently a single bond, —CO— and —NR ⁵ — (R ⁵ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group) Represents a divalent linking group formed from one or more groups selected from the group consisting of: a, b, c and d are integers of 0 or more, a + b + c + d is 2 or more, Q ¹ is (a + b + c + d Represents a valent organic group.)

3. ^3. The cellulose derivative film as described in 1 or 2 above, wherein the substituent having a polarizability anisotropy of 2.5 × 10 ⁻²⁴ cm ³ or more is a substituent containing an aromatic.
4). 4. The cellulose derivative film as described in any one of 1 to ³ above, wherein the substituent having a polarizability anisotropy of 2.5 × 10 ⁻²⁴ cm ³ or more is an aromatic acyl group.
5. The cellulose derivative film as described in any one of 1 to 4 above, wherein the film has an equilibrium moisture content at 25 ° C. and 80% RH of 3.0% or less.
6). 6. The cellulose derivative film as described in 1 to 5, wherein Rth (λ) of the film satisfies the following mathematical formula (2).
Formula (2) −600 nm ≦ Rth (589) ≦ 0 nm
(Here Rth (λ) represents retardation in the film thickness direction of the film at a wavelength of λ nm.)
7). 7. An optical compensation film comprising an optically anisotropic layer on the cellulose derivative film according to any one of 1 to 6 above.
8). 8. A polarizing plate having a polarizing film and two transparent protective films disposed on both sides thereof, wherein at least one of the transparent protective films is the cellulose derivative film according to any one of 1 to 6 above or A polarizing plate, which is an optical compensation film.
9. A liquid crystal display device comprising a liquid crystal cell and two polarizing plates disposed on both sides thereof, wherein at least one polarizing plate is the polarizing plate described in 8 above.
10. 9. The liquid crystal display device as described in 9 above, wherein the display mode is a VA mode.
11. 9. The liquid crystal display device according to 9 above, wherein the display mode is an IPS mode.

  According to the present invention, a cellulose derivative film exhibiting negative Rth can be provided. Due to this performance, the cellulose derivative film of the present invention can be used as a retardation film suitable for, for example, an IPS mode liquid crystal display device, and can be used in combination with other optical films having various optical characteristics to reduce the freedom of optical design. The degree can be significantly improved. Furthermore, according to this invention, in addition to the said performance, the moisture content of a film is low and can provide the cellulose derivative film useful for manufacture of the polarizing plate excellent in durability in high temperature, high humidity conditions. Liquid crystal excellent in viewing angle characteristics and durability under high temperature and high humidity conditions when the cellulose derivative film of the present invention is used as a protective film for polarizing plates or a support for optical compensation films used in liquid crystal display devices. A display device can be provided.

  In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. The term “polymerization” as used in the present invention is intended to include copolymerization. Furthermore, the term “on the support” or “alignment film” as used in the present invention refers to a direct surface of the support or the like, and a surface provided with any layer (film) on the support or the like. This is intended to include both cases.

Details of the cellulose derivative film of the present invention will be described below.
The cellulose derivative film of the present invention includes at least a cellulose derivative containing a substituent having a specific polarizability anisotropy and at least one retardation adjusting agent satisfying a specific mathematical formula.

[Cellulose derivative]
First, the cellulose derivative used for the cellulose derivative film of the present invention will be described.
The cellulose derivative used in the cellulose derivative film of the present invention has a polarizability anisotropy described later as a substituent linked to at least one of the three hydroxyl groups on the β-glucose ring which is a constituent unit of the cellulose derivative. It is a cellulose derivative which has a substituent in the range of (the polarizability anisotropy is large). The cellulose derivative having a substituent having a large polarizability anisotropy is combined with a retardation regulator, which will be described later, but the detailed mechanism of action is unknown, but the polarizability anisotropy of the substituent is further increased in the film thickness direction. As a result, the Rth of the film can be further reduced.

The substituent having a specific large polarizability anisotropy in the present invention will be described in detail.
The polarizability of the substituent in the present invention can be determined by calculation using a molecular orbital method or a density functional method, and the cellulose derivative film of the present invention has the following formula ( It has a substituent whose polarizability anisotropy represented by 1) is 2.5 × 10 ⁻²⁴ cm ³ or more. In practice, the polarizability anisotropy of the substituent is preferably 300 × 10 ⁻²⁴ cm ³ or less. If the polarizability anisotropy is less than 2.5 × 10 ⁻²⁴ cm ³ , the Rth reduction effect due to the polarizability anisotropy of the substituent is not sufficient, and in order to obtain a film having a desired negative region of Rth The amount of the retardation regulator that satisfies the formula (11-1) is enormous, the Tg of the film is lowered, and the production suitability becomes a problem, and the cost is concerned. Moreover, if the polarizability anisotropy is 300 × 10 ⁻²⁴ cm ³ or less, the size of the substituent for achieving the polarizability anisotropy becomes excessive, and the solubility of the cellulose derivative is insufficient. This is preferable because the problem and the problem that the rigidity of the obtained film is insufficient and the handleability deteriorates do not occur. The polarizability anisotropy of the substituent is more preferably 4.0 × 10 ⁻²⁴ cm ³ or more and 300 × 10 ⁻²⁴ cm ³ or less, and 6.0 × 10 ⁻²⁴ cm ³ or more and 300 × 10 ^−. further preferably ²⁴ cm ³ or less, and most preferably 8.0 × 10 ^-24 cm ³ or more 300 × 10 ^-24 cm ³ or less.

Formula (1): Δα = α _x − (α _y + α _z ) / 2
(Where α _x is the largest component of the eigenvalues obtained after diagonalizing the polarizability tensor;
α _y is the second largest component of the eigenvalues obtained after diagonalizing the polarizability tensor;
α _z is the smallest component of the eigenvalues obtained after diagonalizing the polarizability tensor. )

(Polarity anisotropy of substituents)
The polarizability anisotropy of the substituent was calculated using Gaussian 03 (Revision B.03, US Gaussian software). Specifically, the polarizability anisotropy is calculated at the B3LYP / 6-311 + G ** level using a structure optimized at the B3LYP / 6-31G * level, and the obtained polarizability tensor is calculated. After diagonalization, it was calculated from the diagonal component. In the calculation of the polarizability anisotropy of the substituent in the present invention, the substituent linked to the hydroxyl group on the β-glucose ring, which is the structural unit of the cellulose derivative, is calculated by the partial structure containing the oxygen atom of the hydroxyl group. Asked.

  Moreover, it is preferable that the cellulose derivative used for the cellulose derivative film of this invention has a highly hydrophobic substituent. By using a cellulose derivative having a hydrophobic substituent, the equilibrium moisture content of the cellulose derivative film can be reduced, and the performance change at high temperature and high humidity when used for an optical member can be suppressed. As the hydrophobic substituent, the log P value in the structure of the —OH form obtained by hydrolyzing the substituent on the β-glucose ring that is a structural unit of cellulose is preferably 1.0 or more, and 1.5 or more. It is more preferable that it is 2.0 or more. By containing a substituent having a log P value of 1.0 or more, the effect of suppressing the performance change at high temperature and high humidity becomes remarkable, and the effect is larger as the log P value is larger. The logP value is preferably 10 or less.

The substituent having a high polarizability may be any substituent that can be linked to a hydroxyl group on β-glucose, and includes an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, and an alkyl phosphate oxy group. Arylphosphoric acid oxy group, alkyl boric acid oxy group, aryl boric acid oxy group, alkyl carbonic acid oxy group, aryl carbonic acid oxy group and the like. In addition, examples of the highly hydrophobic substituent include the substituents exemplified as the substituent having a high polarizability.
From the viewpoint of high polarizability anisotropy and high hydrophobicity, particularly preferable substituents in the present invention include aromatic-containing substituents, and aromatic acyl groups are more preferable.

  As the degree of substitution of the substituent having a high polarizability and the degree of substitution (SB) of the substituent having a high hydrophobicity, while maintaining the solubility in a solvent as a dope, the Rth of the film is reduced and the desired degree of substitution is obtained. It is 0.01 or more and 3.0 or less in order to improve the durability of the polarizing plate when it is used as a protective film for the polarizing plate by further reducing the parallel water content of the film and the purpose of being in the range. Is preferably 0.1 or more and 2.7 or less, and more preferably 0.3 or more and 2.5 or less.

In addition, the cellulose derivative of the present invention has β-glucose in order to make the film elasticity within the preferable range from the viewpoint of solubility in a solution when film-forming is performed and film handleability. The substituent linked to the above hydroxyl group preferably contains a substituent having a polarizability anisotropy smaller than 2.5 × 10 ⁻²⁴ cm ³ . Preferable examples of the substituent having a polarizability anisotropy smaller than 2.5 × 10 ⁻²⁴ cm ³ are any substituents that can be linked to a hydroxyl group on β-glucose, such as alkyloxy, aryloxy, alkylcarbonyl. Oxy, arylcarbonyloxy, alkyl phosphate oxy, aryl phosphate oxy, alkyl borate oxy, aryl borate oxy, alkyl carbonate oxy, aryl carbonate oxy, and the like. An aliphatic acyl group, specifically an acetyl group, a propionyl group, a butyryl group, and the like are preferable, and an acetyl group is more preferable. In addition, the total substitution degree SS of the substituent having a small polarizability anisotropy is preferably within a range satisfying the following formula (S1) with respect to the total substitution degree SB of the substituent having a high polarizability. More preferably, it is within the range satisfying (S2), and more preferably within the range satisfying (S3).
Formula (S1): 0 ≦ SS ≦ 3.0−SB
Formula (S2): 1.0 ≦ SS ≦ 3.0−SB
Formula (S3): 2.0 ≦ SS ≦ 3.0−SB

  As described above, particularly preferred substituents in the present invention from the viewpoint of high polarizability anisotropy and large hydrophobicity include substituents containing aromatic groups, and aromatic acyl groups and the like are more preferable.

As the cellulose derivative used in the present invention, a mixed acid ester having a fatty acid acyl group and a substituted or unsubstituted aromatic acyl group which is a substituent having a large polarizability anisotropy is preferably used. Examples of the substituted or unsubstituted aromatic acyl group include groups represented by the following general formula (A).
Formula (A)

In the general formula (A), X is a substituent. Examples of the substituent include a halogen atom, cyano, alkyl group, alkoxy group, aryl group, aryloxy group, acyl group, carbonamido group, sulfonamido group, ureido. Group, aralkyl group, nitro, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, carbamoyl group, sulfamoyl group, acyloxy group, alkenyl group, alkynyl group, alkylsulfonyl group, arylsulfonyl group, alkyloxysulfonyl group, aryl Oxysulfonyl group, alkylsulfonyloxy group, and aryloxysulfonyl group, —S—R, —NH—CO—OR, —PH—R, —P (—R) ₂ , —PH—O—R, —P (— R) (- O-R) , - P (-O-R) 2, -PH (= O) -R-P (= O) (- R) 2 -PH (= O) -O-R , -P (= O) (- R) (- O-R), - P (= O) (- O-R) 2, -O-PH (= O) —R, —O—P (═O) (— R) ₂ —O—PH (═O) —O—R, —O—P (═O) (— R) (— O—R), —O -P (= O) (-O-R) ₂ , -NH-PH (= O) -R, -NH-P (= O) (-R) (-O-R), -NH-P (= O) (- O-R) 2, -SiH 2 -R, -SiH (-R) 2, -Si (-R) 3, -O-SiH 2 -R, -O-SiH (-R) 2 and -O-Si (-R) ₃ is included. R is an aliphatic group, an aromatic group or a heterocyclic group. The number of substituents is preferably 0 or 1 to 5, more preferably 1 to 4, further preferably 1 to 3, and 1 or 2. Most preferred. As the substituent, a halogen atom, cyano, alkyl group, alkoxy group, aryl group, aryloxy group, acyl group, carbonamido group, sulfonamido group and ureido group are preferable, halogen atom, cyano, alkyl group, alkoxy group, An aryloxy group, an acyl group and a carbonamido group are more preferred, a halogen atom, cyano, an alkyl group, an alkoxy group and an aryloxy group are more preferred, and a halogen atom, an alkyl group and an alkoxy group are most preferred.

  The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The alkyl group may have a cyclic structure or a branch. The number of carbon atoms in the alkyl group is preferably 1-20, more preferably 1-12, still more preferably 1-6, and most preferably 1-4. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyl, cyclohexyl, octyl and 2-ethylhexyl. The alkoxy group may have a cyclic structure or a branch. The number of carbon atoms in the alkoxy group is preferably 1-20, more preferably 1-12, still more preferably 1-6, and most preferably 1-4. The alkoxy group may be further substituted with another alkoxy group. Examples of the alkoxy group include methoxy, ethoxy, 2-methoxyethoxy, 2-methoxy-2-ethoxyethoxy, butyloxy, hexyloxy and octyloxy.

  The number of carbon atoms of the aryl group is preferably 6-20, and more preferably 6-12. Examples of the aryl group include phenyl and naphthyl. The aryloxy group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. Examples of the aryloxy group include phenoxy and naphthoxy. The number of carbon atoms in the acyl group is preferably 1-20, and more preferably 1-12. Examples of acyl groups include formyl, acetyl and benzoyl. The number of carbon atoms of the carbonamide group is preferably 1-20, and more preferably 1-12. Examples of the carbonamido group include acetamide and benzamide. The number of carbon atoms in the sulfonamide group is preferably 1-20, and more preferably 1-12. Examples of the sulfonamide group include methanesulfonamide, benzenesulfonamide, and p-toluenesulfonamide. The number of carbon atoms in the ureido group is preferably 1-20, and more preferably 1-12. Examples of ureido groups include (unsubstituted) ureido.

The number of carbon atoms in the aralkyl group is preferably 7-20, and more preferably 7-12. Examples of aralkyl groups include benzyl, phenethyl and naphthylmethyl. The number of carbon atoms in the alkoxycarbonyl group is preferably 1-20, and more preferably 2-12. Examples of the alkoxycarbonyl group include methoxycarbonyl. The aryloxycarbonyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 12 carbon atoms. Examples of the aryloxycarbonyl group include phenoxycarbonyl. The number of carbon atoms in the aralkyloxycarbonyl group is preferably 8-20, and more preferably 8-12. Examples of the aralkyloxycarbonyl group include benzyloxycarbonyl. The number of carbon atoms of the carbamoyl group is preferably 1-20, and more preferably 1-12. Examples of the carbamoyl group include (unsubstituted) carbamoyl and N-methylcarbamoyl. The number of carbon atoms in the sulfamoyl group is preferably 20 or less, and more preferably 12 or less. Examples of sulfamoyl groups include (unsubstituted) sulfamoyl and N-methylsulfamoyl. The number of carbon atoms in the acyloxy group is preferably 1-20, and more preferably 2-12. Examples of the acyloxy group include acetoxy and benzoyloxy.

  The alkenyl group has preferably 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of alkenyl groups include vinyl, allyl and isopropenyl. The number of carbon atoms in the alkynyl group is preferably 2-20, and more preferably 2-12. Examples of alkynyl groups include thienyl. The number of carbon atoms in the alkylsulfonyl group is preferably 1-20, and more preferably 1-12. The number of carbon atoms of the arylsulfonyl group is preferably 6-20, and more preferably 6-12. The alkyloxysulfonyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms. The number of carbon atoms of the aryloxysulfonyl group is preferably 6-20, and more preferably 6-12. The number of carbon atoms in the alkylsulfonyloxy group is preferably 1-20, and more preferably 1-12. The number of carbon atoms of the aryloxysulfonyl group is preferably 6-20, and more preferably 6-12.

  Next, in the fatty acid ester residue in the cellulose mixed acid ester of the present invention, the aliphatic acyl group has 2 to 20 carbon atoms, specifically acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl, hexanoyl, octanoyl, Examples include lauroyl and stearoyl. Acetyl, propionyl and butyryl are preferred, and acetyl is particularly preferred. In the present invention, the aliphatic acyl group is meant to include those having a substituent, and examples of the substituent include those exemplified as X in the general formula (A).

  Further, when the number of substituents substituted on the aromatic ring is 2 or more, they may be the same or different from each other, but they may be linked together to form a condensed polycyclic compound (for example, naphthalene, indene, indane, phenanthrene, quinoline) , Isoquinoline, chromene, chroman, phthalazine, acridine, indole, indoline, etc.).

  Substitution of the aromatic acyl group to the hydroxyl group of cellulose generally includes a method using a symmetric acid anhydride and a mixed acid anhydride derived from an aromatic carboxylic acid claloid or an aromatic carboxylic acid. Particularly preferred is a method using an acid anhydride derived from an aromatic carboxylic acid (described in Journal of Applied Polymer Science, Vol. 29, 3981-3990 (1984)). As a method for producing the cellulose mixed acid ester compound of the present invention as the above-mentioned method, (1) once the cellulose fatty acid monoester or diester is produced, the remaining hydroxyl group is an aromatic acyl represented by the general formula (A) And (2) a method in which a mixed acid anhydride of an aliphatic carboxylic acid and an aromatic carboxylic acid is directly reacted with cellulose. In the first stage of (1), the method for producing cellulose fatty acid ester or diester is a well-known method, but the subsequent reaction for further introducing an aromatic acyl group varies depending on the type of the aromatic acyl group. The reaction temperature is preferably 0 to 100 ° C., more preferably 20 to 50 ° C., and the reaction time is preferably 30 minutes or more, more preferably 30 to 300 minutes. In the latter method using the mixed acid anhydride, the reaction conditions vary depending on the type of the mixed acid anhydride, but the reaction temperature is preferably 0 to 100 ° C., more preferably 20 to 50 ° C., and the reaction time is preferably 30 to 300. Minutes, more preferably 60 to 200 minutes. In any of the above reactions, the reaction may be performed in the absence of a solvent or in a solvent, but is preferably performed using a solvent. As the solvent, dichloromethane, chloroform, dioxane and the like can be used.

  In the case of cellulose fatty acid monoester, the substitution degree of the aromatic acyl group is preferably 0.01 or more and 2.0 or less, more preferably 0.1 or more and 2.0 or less, still more preferably 0.3 with respect to the remaining hydroxyl group. It is 2.0 or less. In the case of cellulose fatty acid diester (cellulose diacetate), it is preferably 0.01 or more and 1.0 or less, more preferably 0.1 or more and 1.0 or less, still more preferably 0.3 or more and 1 with respect to the remaining hydroxyl group. 0.0 or less. Specific examples of the aromatic acyl group represented by formula (A) are shown below, but the present invention is not limited thereto. Among these, No. 1 is preferable. 1, 3, 5, 6, 8, 13, 18, 28, more preferably 1, 3, 6, and 13.

  The cellulose derivative used in the present invention preferably has a mass average polymerization degree of 350 to 800, more preferably 370 to 600. The cellulose derivative used in the present invention preferably has a number average molecular weight of 70000 to 230,000, more preferably has a number average molecular weight of 75000 to 230,000, and most preferably has a number average molecular weight of 78000 to 120,000. .

  The cellulose derivative used in the present invention can be synthesized using an acid anhydride, an acid chloride, or a halide as an acylating agent, an alkylating agent, or an arylating agent. When an acid anhydride is used as an acylating agent, an organic acid (for example, acetic acid) or methylene chloride is used as a reaction solvent. As the catalyst, a protic catalyst such as sulfuric acid is used. When an acid chloride is used as the acylating agent, a basic compound is used as a catalyst. In the most general synthetic method in the industry, cellulose is an organic acid corresponding to acetyl group and other acyl groups (acetic acid, propionic acid, butyric acid) or their acid anhydrides (acetic anhydride, propionic anhydride, butyric anhydride). A cellulose ester is synthesized by esterification with a mixed organic acid component containing. In addition, as a general method for introducing an alkyl group or an aryl group as a substituent, cellulose is dissolved in an alkali solution and then etherified with an alkyl halide compound, an aryl halide compound, or the like. To do.

In this method, cellulose such as cotton linter and wood pulp is activated with an organic acid such as acetic acid, and then esterified using a mixture of organic acid components as described above in the presence of a sulfuric acid catalyst. There are many cases to do. The organic acid anhydride component is generally used in an excess amount relative to the amount of hydroxyl groups present in the cellulose. In this esterification treatment, in addition to the esterification reaction, a hydrolysis reaction (depolymerization reaction) of the cellulose main chain β1 → 4-glycoside bond) proceeds. When the hydrolysis reaction of the main chain proceeds, the degree of polymerization of the cellulose ester is lowered, and the physical properties of the cellulose ester film to be produced are lowered. Therefore, the reaction conditions such as the reaction temperature are preferably determined in consideration of the degree of polymerization and molecular weight of the resulting cellulose ester.

  In order to obtain a cellulose ester having a high degree of polymerization (high molecular weight), it is important to adjust the maximum temperature in the esterification reaction step to 50 ° C. or lower. The maximum temperature is preferably adjusted to 35 to 50 ° C, more preferably 37 to 47 ° C. A reaction temperature of 35 ° C. or higher is preferable because the esterification reaction proceeds smoothly. A reaction temperature of 50 ° C. or lower is preferable because there is no inconvenience such as a decrease in the degree of polymerization of the cellulose ester.

  After the esterification reaction, when the reaction is stopped while suppressing a temperature rise, a decrease in the degree of polymerization can be further suppressed, and a cellulose ester having a high degree of polymerization can be synthesized. That is, when a reaction terminator (for example, water or acetic acid) is added after completion of the reaction, the excess acid anhydride that did not participate in the esterification reaction is hydrolyzed to form a corresponding organic acid as a by-product. This hydrolysis reaction is accompanied by intense heat generation, and the temperature in the reactor rises. If the rate of addition of the reaction terminator is not too high, heat is rapidly generated exceeding the cooling capacity of the reactor, the hydrolysis reaction of the cellulose main chain proceeds significantly, and the degree of polymerization of the resulting cellulose ester decreases. Such a problem does not occur. In addition, a part of the catalyst is bonded to the cellulose during the esterification reaction, and most of the catalyst is dissociated from the cellulose during the addition of the reaction terminator. If the rate of addition of the reaction terminator is not too high at this time, a sufficient reaction time is secured for dissociating the catalyst, and problems such as part of the catalyst remaining in a state of being bound to cellulose are unlikely to occur. Cellulose esters to which a strong acid catalyst is partially bonded are very poor in stability, and are easily decomposed by heat during drying of the product to lower the degree of polymerization. For these reasons, after the esterification reaction, it is preferable to stop the reaction by adding a reaction terminator over a period of preferably 4 minutes or more, more preferably 4 to 30 minutes. In addition, it is preferable if the addition time of the reaction terminator is 30 minutes or less because problems such as a decrease in industrial productivity do not occur.

  As the reaction terminator, water or alcohol that decomposes an acid anhydride is generally used. However, in the present invention, a mixture of water and an organic acid is preferably used as a reaction terminator in order not to precipitate triesters having low solubility in various organic solvents. When the esterification reaction is carried out under the above conditions, a high molecular weight cellulose ester having a mass average polymerization degree of 350 or more and 800 or less can be easily synthesized.

[Retardation regulator]
The retardation regulator used as an essential component in the present invention is a compound that reduces retardation in the film thickness direction of the film, and is a compound that satisfies the following mathematical formula (11-1).
Formula (11-1): Rth (a) −Rth (0) /a≦−1.5
(However, 0.01 ≦ a ≦ 30)
Rth (a): Rth (nm) at a wavelength of 589 nm of a film having a thickness of 80 μm, comprising a cellulose acylate having an acetyl substitution degree of 2.85 and an a-part retardation modifier with respect to 100 parts by mass of cellulose acylate.
Rth (0): Rth (nm) at a wavelength of 589 nm of a film having a film thickness of 80 μm made only of cellulose acylate having a degree of acetyl substitution of 2.85 and containing no retardation regulator
a: part by mass of retardation regulator with respect to 100 parts by mass of cellulose acylate By using a compound satisfying the above formula (11-1) as a retardation regulator, sufficient Rth reduction can be obtained. A film showing the desired Rth can be produced without excessive use.
In the present invention, Rth can be further reduced by combining a cellulose derivative having a substituent having a large polarizability anisotropy (also referred to as “high polarizability anisotropy”) and a compound that reduces Rth. it can.
It is more preferable that the retardation adjusting agent satisfies Formula (11-2), and it is more preferable that Formula (11-3) is satisfied.
Formula (11-2): Rth (a) −Rth (0) /a≦−2.0
Formula (11-3): Rth (a) −Rth (0) /a≦−2.5
(However, 0.01 ≦ a ≦ 30)
Further, the retardation adjusting agent used in the present invention is preferably a compound in which Re at a wavelength of 589 nm satisfies the following formula (10) when added to a cellulose acylate film having an acetyl substitution degree of 2.86.
Formula (10): | Re (a) −Re (0) | /a≧1.0
Re (a): Re (nm) at a wavelength of 589 nm of a film having a film thickness of 80 μm comprising cellulose acylate having an acetyl substitution degree of 2.85 and a retardation modifier of a part by mass with respect to 100 parts by mass of cellulose acylate.
Re (0): Re (nm) at a wavelength of 589 nm of a film having a film thickness of 80 μm made only of cellulose acylate having a degree of acetyl substitution of 2.85 and containing no retardation modifier

  In the present invention, Rth can be further reduced by combining a cellulose derivative having a substituent having a large polarizability anisotropy (also referred to as “high polarizability anisotropy”) and a retardation modifier. Can do. Although the mechanism of action for further reducing Rth is not clarified, the above-mentioned retardation modifier having high compatibility with the substituent is used for the highly polarizable substituent on the cellulose derivative. It is estimated that the Rth of the film can be reduced as a result by increasing the degree of freedom of the orientation of the substituents and increasing the ratio of the substituents oriented in the film thickness direction.

  Examples of the retardation adjusting agent for cellulose derivative film that are preferably used in the present invention are shown below as general formulas (1) to (21), but the present invention is not limited to these compounds.

In the formula, R ^{11 to} R ¹³ each independently represents an aliphatic group having 1 to 20 carbon atoms. R ^{11 to} R ¹³ may be connected to each other to form a ring.

In the general formulas (2) and (3), Z represents a carbon atom, an oxygen atom, a sulfur atom or —NR ²⁵ —, and R ²⁵ represents a hydrogen atom or an alkyl group. The 5- or 6-membered ring configured to include Z may have a substituent. Y ²¹ and Y ²² each independently represent an ester group, alkoxycarbonyl group, amide group or carbamoyl group having 1 to 20 carbon atoms, and Y ²¹ and Y ²² may be linked to each other to form a ring. . m represents an integer of 1 to 5, and n represents an integer of 1 to 6.

In the general formulas (4) to (12), Y ^{31 to} Y ⁷⁰ are each independently an ester group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, and an amide having 1 to 20 carbon atoms. Group, a carbamoyl group having 1 to 20 carbon atoms or a hydroxy group, and V ^{31 to} V ⁴³ each independently represent a hydrogen atom or an aliphatic group having 1 to 20 carbon atoms. L ^{31 to} L ⁸⁰ are each independently
A divalent saturated linking group having 0 to 40 atoms and 0 to 20 carbon atoms is represented. Here, the fact that the number of atoms of L ^{31 to} L ⁸⁰ is 0 means that groups at both ends of the linking group directly form a single bond. V ^{31 to} V ⁴³ and L ^{31 to} L ⁸⁰ may further have a substituent.

In General Formula (13), R ¹ represents an alkyl group or an aryl group, and R ² and R ³ each independently represent a hydrogen atom, an alkyl group, or an aryl group. The total number of carbon atoms of R ¹ , R ² and R ³ is 10 or more, and each of the alkyl group and aryl group may have a substituent.

In general formula (14), R ⁴ and R ⁵ each independently represents an alkyl group or an aryl group. The total number of carbon atoms of R ⁴ and R ⁵ is 10 or more, and each of the alkyl group and aryl group may have a substituent.

In general formula (15), R ¹ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, and R ² represents a hydrogen atom, a substituted or unsubstituted aliphatic group, or a substituted or unsubstituted group. Represents an aromatic group. L ¹ represents a divalent to hexavalent linking group, and n represents an integer of 2 to 6 depending on the valence of L ¹ .

In general formula (16), R ¹ , R ² and R ³ each independently represents a hydrogen atom or an alkyl group. X represents a divalent linking group formed from one or more groups selected from the following linking group group 1. Y represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.

(Linking group 1)
It represents a single bond, —O—, —CO—, —NR ⁴ —, an alkylene group or an arylene group. R ⁴ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.

In the general formula (17), Q ¹ , Q ² and Q ³ each independently represents a 5- or 6-membered ring. X represents B, C—R (R represents a hydrogen atom or a substituent), N, P, P═O.

  The compound represented by the general formula (17) is preferably a compound represented by the following general formula (18).

In General Formula (18), X ² represents B, C—R (R represents a hydrogen atom or a substituent), or N. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are each independently a hydrogen atom. Or represents a substituent.

In General Formula (19), R ¹ represents an alkyl group or an aryl group, and R ² and R ³ each independently represent a hydrogen atom, an alkyl group, or an aryl group. Moreover, the alkyl group and the aryl group may have a substituent.

  The compound represented by the general formula (19) is preferably a compound represented by the following general formula (20).

In the general formula (20), R ⁴ , R ⁵ and R ⁶ each independently represents an alkyl group or an aryl group. Here, the alkyl group may be linear, branched or cyclic, and preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and 1 to 12 carbon atoms. Is most preferred. As the cyclic alkyl group, a cyclohexyl group is particularly preferable. The aryl group preferably has 6 to 36 carbon atoms, and more preferably 6 to 24 carbon atoms. Moreover, the alkyl group and the aryl group may have a substituent.

In general formula (21), R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. X ¹ , X ² , X ³ and X ⁴ are each a single bond, —CO— and —NR ⁵ — (R ⁵ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group) Represents a divalent linking group formed from one or more groups selected from the group consisting of: a, b, c and d are integers of 0 or more, and a + b + c + d is 2 or more. Q ¹ represents an (a + b + c + d) valent organic group.

  Specific examples of the compound that lowers the optical anisotropy of the cellulose derivative film that are preferably used in the present invention are shown below for the compounds represented by the above general formulas (1) to (21). It is not limited.

  The compound of the general formula (1) will be described.

In the general formula (1), R ^{11 to} R ¹³ each independently represents an aliphatic group having 1 to 20 carbon atoms, and the aliphatic group may have a substituent. R ^{11 to} R ¹³ may be connected to each other to form a ring.
R ^{11 to} R ¹³ will be described in detail. R ^{11 to} R ¹³ are preferably an aliphatic group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms. Here, the aliphatic group is preferably an aliphatic hydrocarbon group, more preferably an alkyl group (including chain, branched and cyclic alkyl groups), an alkenyl group or an alkynyl group. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, t-amyl, n-hexyl, n-octyl, decyl, Dodecyl, eicosyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, cycloheptyl, 2,6-dimethylcyclohexyl, 4-t-butylcyclohexyl, cyclopentyl, 1-adamantyl, 2-adamantyl, bicyclo [2.2.2] octane-3 Examples of the alkenyl group include vinyl, allyl, prenyl, geranyl, oleyl, 2-cyclopenten-1-yl, and 2-cyclohexen-1-yl. Examples of the alkynyl group include , Ethynyl, propargyl and the like.
The aliphatic group represented by R ^{11 to} R ¹³ may be substituted, and examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, or iodine atom), alkyl group (straight chain, Branched or cyclic alkyl group, including bicycloalkyl group and active methine group), alkenyl group, alkynyl group, aryl group, heterocyclic group (regardless of the position of substitution), acyl group, alkoxycarbonyl group, aryloxycarbonyl Group, heterocyclic oxycarbonyl group, carbamoyl group, N-acylcarbamoyl group, N-sulfonylcarbamoyl group, N-carbamoylcarbamoyl group, N-sulfamoylcarbamoyl group, carbazoyl group, carboxy group or a salt thereof, oxalyl group, oxamoyl Group, cyano group, carbonimidoyl group (Carbonimide group), Mill group, hydroxy group, alkoxy group (including groups containing ethyleneoxy group or propyleneoxy group unit repeatedly), aryloxy group, heterocyclic oxy group, acyloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group , Sulfonyloxy group, amino group, (alkyl, aryl or heterocyclic) amino group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group , A semicarbazide group, an ammonio group, an oxamoylamino group, an N- (alkyl or aryl) sulfonylureido group, an N-acylureido group, an N-acylsulfamoylamino group, a heterocyclic group containing a quaternized nitrogen atom ( For example, pyridinio group, imidazolio group, quinolinio group, isoquinolinio group), isocyano group, imino group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or a salt thereof, sulfamoyl group, N-acylsulfa Examples include a moyl group, an N-sulfonylsulfamoyl group or a salt thereof, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group.
These groups may be further combined to form a composite substituent, and examples of such a substituent include ethoxyethoxyethyl group, hydroxyethoxyethyl group, ethoxycarbonylethyl group and the like. R ^{11 to} R ¹³ can also contain a phosphate group as a substituent, and the compound of the general formula (1) can also have a plurality of phosphate groups in the same molecule.

  Although the example (C-1 to C-76) of a compound represented by General formula (1) is given below, this invention is not limited to these. In addition, the value of logP is obtained by the Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)).

(Wherein, R ¹ to R ³ has the same meaning as R ¹¹ to R ¹³ in the general formula (1), specific examples in C-1 through C-76 below.)

  The compounds of general formulas (2) and (3) will be described.

In the general formulas (2) and (3), Z represents a carbon atom, an oxygen atom, a sulfur atom, —NR ²⁵ —.
R ²⁵ represents a hydrogen atom or an alkyl group. The 5- or 6-membered ring configured to include Z may have a substituent, and a plurality of substituents may be bonded to each other to form a ring. Examples of 5- or 6-membered rings comprising Z include tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, thiane, pyrrolidine, piperidine, indoline, isoindoline, chroman, isochroman, tetrahydro-2-furanone, tetrahydro-2- Examples include pyrone, 4-butane lactam, and 6-hexanolactam.
Further, the 5- or 6-membered ring composed of Z includes a lactone structure or a lactam structure, that is, a cyclic ester or cyclic amide structure having an oxo group at the adjacent carbon of Z. Examples of such cyclic ester or cyclic amide structures include 2-pyrrolidone, 2-piperidone, 5-pentanolide, and 6-hexanolide.

R ²⁵ is a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms (chain, branched and cyclic alkyl). Group). Examples of the alkyl group represented by R ²⁵ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, t-amyl, n-hexyl, and n-octyl. , Decyl, dodecyl, eicosyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, cycloheptyl, 2,6-dimethylcyclohexyl, 4-t-butylcyclohexyl, cyclopentyl, 1-adamantyl, 2-adamantyl, bicyclo [2.2.2] There may be mentioned octan-3-yl. The alkyl group represented by R ²⁵ may further have a substituent, and examples of the substituent include groups that may be substituted with R ^{11 to} R ¹³ described above.

Y ²¹ and Y ²² each independently represents an ester group, an alkoxycarbonyl group, an amide group or a carbamoyl group. The ester group preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms. For example, acetoxy, ethylcarbonyloxy, propylcarbonyloxy, n -Butylcarbonyloxy, iso-butylcarbonyloxy, t-butylcarbonyloxy, sec-butylcarbonyloxy, n-pentylcarbonyloxy, t-amylcarbonyloxy, n-hexylcarbonyloxy, cyclohexylcarbonyloxy, 1-ethylpentylcarbonyl Oxy, n-heptylcarbonyloxy, n-nonylcarbonyloxy, n-undecylcarbonyloxy, benzylcarbonyloxy, 1-naphthalenecarbonyloxy, 2-naphthalenecarbonyloxy, 1-adamantanca Such as Boniruokishi can be exemplified. The alkoxycarbonyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms. For example, methoxycarbonyl, ethoxycarbonyl, n-propyloxy Carbonyl, isopropyloxycarbonyl, n-butoxycarbonyl, t-butoxycarbonyl, iso-butyloxycarbonyl, sec-butyloxycarbonyl, n-pentyloxycarbonyl, t-amyloxycarbonyl, n-hexyloxycarbonyl, cyclohexyloxycarbonyl, 2-ethylhexyloxycarbonyl, 1-ethylpropyloxycarbonyl, n-octyloxycarbonyl, 3,7-dimethyl-3-octyloxycarbonyl, 3,5,5-trimethylhexyloxycarbo 4-t-butylcyclohexyloxycarbonyl, 2,4-dimethylpentyl-3-oxycarbonyl, 1-adamantaneoxycarbonyl, 2-adamantaneoxycarbonyl, dicyclopentadienyloxycarbonyl, n-decyloxycarbonyl, n -Dodecyloxycarbonyl, n-tetradecyloxycarbonyl, n-hexadecyloxycarbonyl and the like can be exemplified. The amide group preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms. For example, acetamide, ethyl carboxamide, n-propyl carboxamide, isopropyl Carboxamide, n-butylcarboxamide, t-butylcarboxamide, iso-butylcarboxamide, sec-butylcarboxamide, n-pentylcarboxamide, t-amylcarboxamide, n-hexylcarboxamide, cyclohexylcarboxamide, 1-ethylpentylcarboxamide, 1-ethylpropyl Carboxamide, n-heptylcarboxamide, n-octylcarboxamide, 1-adamantancarboxamide, 2-adamantancarboxamide, n-nonylcarboxamide, n-dodecy Carboxamide, n- penta-carboxamide, such as n- hexadecyl carboxamide can be exemplified. The carbamoyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms. For example, methylcarbamoyl, dimethylcarbamoyl, ethylcarbamoyl, diethylcarbamoyl , N-propylcarbamoyl, isopropylcarbamoyl, n-butylcarbamoyl, t-butylcarbamoyl, iso-butylcarbamoyl, sec-butylcarbamoyl, n-pentylcarbamoyl, t-amylcarbamoyl, n-hexylcarbamoyl, cyclohexylcarbamoyl, 2-ethylhexyl Carbamoyl, 2-ethylbutylcarbamoyl, t-octylcarbamoyl, n-heptylcarbamoyl, n-octylcarbamoyl, 1-adamantancarbamoyl, 2-adamantanka Bamoiru, n- dodecylcarbamoyl, n--dodecylcarbamoyl, n- tetradecylcarbamoyl, n- hex dodecylcarbamoyl, and others. Y ²¹ and Y ²² may be connected to each other to form a ring. Y ²¹ and Y ²² may further have a substituent, and examples thereof include a group that may be substituted with R ^{11 to} R ¹³ described above.

  Although the example (C-201-C-231) of a compound represented by General formula (2) or (3) below is given, this invention is not limited to these. In addition, the value of logP described in parentheses is obtained by the Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)).

  The compounds of general formulas (4) to (12) will be described.

In General Formulas (4) to (12), Y ^{31 to} Y ⁷⁰ each independently represent an ester group, an alkoxycarbonyl group, an amide group, a carbamoyl group, or a hydroxy group. The ester group preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms. For example, acetoxy, ethylcarbonyloxy, propylcarbonyloxy, n -Butylcarbonyloxy, iso-butylcarbonyloxy, t-butylcarbonyloxy, sec-butylcarbonyloxy, n-pentylcarbonyloxy, t-amylcarbonyloxy, n-hexylcarbonyloxy, cyclohexylcarbonyloxy, 1-ethylpentylcarbonyl Oxy, n-heptylcarbonyloxy, n-nonylcarbonyloxy, n-undecylcarbonyloxy, benzylcarbonyloxy, 1-naphthalenecarbonyloxy, 2-naphthalenecarbonyloxy, 1-adamantanca Boniruokishi and the like. The alkoxycarbonyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms. For example, methoxycarbonyl, ethoxycarbonyl, n-propyloxy Carbonyl, isopropyloxycarbonyl, n-butoxycarbonyl, t-butoxycarbonyl, iso-butyloxycarbonyl, sec-butyloxycarbonyl, n-pentyloxycarbonyl, t-amyloxycarbonyl, n-hexyloxycarbonyl, cyclohexyloxycarbonyl, 2-ethylhexyloxycarbonyl, 1-ethylpropyloxycarbonyl, n-octyloxycarbonyl, 3,7-dimethyl-3-octyloxycarbonyl, 3,5,5-trimethylhexyloxycarbonyl Bonyl, 4-t-butylcyclohexyloxycarbonyl, 2,4-dimethylpentyl-3-oxycarbonyl, 1-adamantaneoxycarbonyl, 2-adamantaneoxycarbonyl, dicyclopentadienyloxycarbonyl, n-decyloxycarbonyl, n -Dodecyloxycarbonyl, n-tetradecyloxycarbonyl, n-hexadecyloxycarbonyl and the like. The amide group preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms. For example, acetamide, ethyl carboxamide, n-propyl carboxamide, isopropyl Carboxamide, n-butylcarboxamide, t-butylcarboxamide, iso-butylcarboxamide, sec-butylcarboxamide, n-pentylcarboxamide, t-amylcarboxamide, n-hexylcarboxamide, cyclohexylcarboxamide, 1-ethylpentylcarboxamide, 1-ethylpropyl Carboxamide, n-heptylcarboxamide, n-octylcarboxamide, 1-adamantancarboxamide, 2-adamantancarboxamide, n-nonylcarboxamide, n-dodecy Carboxamide, n- penta-carboxamide, such as n- hexadecyl carboxamide and the like. The carbamoyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms. For example, methylcarbamoyl, dimethylcarbamoyl, ethylcarbamoyl, diethylcarbamoyl , N-propylcarbamoyl, isopropylcarbamoyl, n-butylcarbamoyl, t-butylcarbamoyl, iso-butylcarbamoyl, sec-butylcarbamoyl, n-pentylcarbamoyl, t-amylcarbamoyl, n-hexylcarbamoyl, cyclohexylcarbamoyl, 2-ethylhexyl Carbamoyl, 2-ethylbutylcarbamoyl, t-octylcarbamoyl, n-heptylcarbamoyl, n-octylcarbamoyl, 1-adamantancarbamoyl, 2-adamantanka Bamoiru, n- dodecylcarbamoyl, n--dodecylcarbamoyl, n- tetradecylcarbamoyl, such as n- hex dodecylcarbamoyl the like. Y ^{31 to} Y ⁷⁰ may further have a substituent, and examples thereof include a group that may be substituted with R ^{11 to} R ¹³ described above.

V ^{31 to} V ⁴³ each independently represent a hydrogen atom or an aliphatic group having preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms. Here, the aliphatic group is preferably an aliphatic hydrocarbon group, more preferably an alkyl group (including chain, branched and cyclic alkyl groups), an alkenyl group or an alkynyl group. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, t-amyl, n-hexyl, n-octyl, decyl, dodecyl, and eicosyl. , 2-ethylhexyl, cyclopentyl, cyclohexyl, cycloheptyl, 2,6-dimethylcyclohexyl, 4-t-butylcyclohexyl, cyclopentyl, 1-adamantyl, 2-adamantyl, bicyclo [2.2.2] octan-3-yl, etc. Examples of the alkenyl group include vinyl, allyl, prenyl, geranyl, oleyl, 2-cyclopenten-1-yl, and 2-cyclohexen-1-yl. Examples of the alkynyl group include ethynyl, Propargyl can be mentioned. V ^{31 to} V ⁴³ may further have a substituent, and examples thereof include a group that may be substituted with R ^{11 to} R ¹³ described above.

L ^{31 to} L ⁸⁰ each independently represent a divalent saturated linking group having 0 to 40 atoms and 0 to 20 carbon atoms. Here, the fact that the number of atoms of L ^{31 to} L ⁸⁰ is 0 means that groups at both ends of the linking group directly form a single bond. Preferable examples of L ^{31 to} L ⁸⁰ include alkylene groups (eg, methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, methylethylene, ethylethylene), cyclic divalent groups (eg, Cis-1,4-cyclohexylene, trans-1,4-cyclohexylene, 1,3-cyclopentylidene, etc.), ether, thioether, ester, amide, sulfone, sulfoxide, sulfide, sulfonamide, ureylene, thioureylene, etc. Can be mentioned. These divalent groups may be bonded to each other to form a divalent composite group. Examples of the composite substituent include — (CH ₂ ) ₂ O (CH ₂ ) ₂ — and — (CH ₂ ). ₂ O (CH ₂ ) ₂ O (CH ₂ ) —, — (CH ₂ ) ₂ S (CH ₂ ) ₂ —, — (CH ₂ ) ₂ O ₂ C (CH ₂ ) ₂ — and the like can be mentioned. L ^{31 to} L ⁸⁰ may further have a substituent, and examples of the substituent include a group which may be substituted with R ^{11 to} R ¹³ described above.

Preferable examples of the compound formed by the combination of Y ^{31 to} Y ⁷⁰ , V ^{31 to} V ⁴³ and L ^{31 to} L ^{80 in} the general formulas (4) to (12) include citrate esters (for example, O-acetyl citrate). Acid triethyl, O-acetyl tributyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, O-acetyl citrate tri (ethyloxycarbonylmethylene) ester, etc.), oleic acid esters (eg ethyl oleate, butyl oleate, 2-ethylhexyl oleate, phenyl oleate, cyclohexyl oleate, octyl oleate, etc.), ricinoleic acid ester (eg, methylacetyl ricinoleate), sebacic acid ester (eg, dibutyl sebacate), carboxylic acid ester of glycerin (eg, , Triacetin, tributyrin, etc.), glycolic acid esters (eg, butyl phthalyl butyl glycolate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, methyl phthalyl methyl glycolate, propyl phthalyl) Propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, etc.), pentaerythritol carboxylate (eg, pentaerythritol tetraacetate, pentaerythritol tetrabutyrate, etc.), dipentaerythritol carboxylate ( For example, dipentaerythritol hexaacetate, dipentaerythritol hexabutyrate, dipentaerythritol tetraacetate), Carboxylic acid esters of roll propane (trimethylolpropane triacetate, trimethylolpropane diacetate monopropionate, trimethylolpropane tripropionate, trimethylolpropane tributyrate, trimethylolpropane tripivaloate, trimethylolpropane tri ( t-butyl acetate), trimethylolpropane di-2-ethylhexanate, trimethylolpropane tetra-2-ethylhexanate, trimethylolpropane diacetate monooctanoate, trimethylolpropane trioctanoate, trimethylolpropane tri (cyclohexanecarboxylate) )), Glycerol esters described in JP-A-11-246704, and diesters described in JP-A-2000-63560. Reserol esters, citric acid esters described in JP-A No. 11-92574, pyrrolidone carboxylic acid esters (methyl 2-pyrrolidone-5-carboxylate, ethyl 2-pyrrolidone-5-carboxylate, 2-pyrrolidone-5 -Butyl carboxylate, 2-pyrrolidone-5-carboxylic acid 2-ethylhexyl), cyclohexanedicarboxylic acid ester (dibutyl cis-1,2-cyclohexanedicarboxylate, dibutyl trans-1,2-cyclohexanedicarboxylate, cis-1,4 -Cyclohexanedicarboxylate dibutyl, trans-1,4-cyclohexanedicarboxylate dibutyl, etc.), xylitol carboxylate (xylitol pentaacetate, xylitol tetraacetate, xylitol pentapropionate, etc.) And so on.

  Although the example (C-401-C-448) of the compound represented by General formula (4)-(12) below is given, this invention is not limited to these. In addition, the value of logP described in parentheses is obtained by the Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)).

  The compounds of the general formulas (13) and (14) will be described.

In the general formula (13), R ¹ represents an alkyl group or an aryl group, and R ² and R ³ each independently represent a hydrogen atom, an alkyl group, or an aryl group. Further, the total number of carbon atoms of R ¹ , R ² and R ³ is 10 or more, and each of the alkyl group and aryl group may have a substituent. In the general formula (14), R ⁴ and R ⁵ each independently represents an alkyl group or an aryl group. The total number of carbon atoms of R ⁴ and R ⁵ is 10 or more, and each of the alkyl group and the aryl group may have a substituent.
As the substituent, a fluorine atom, an alkyl group, an aryl group, an alkoxy group, a sulfone group, and a sulfonamide group are preferable, and an alkyl group, an aryl group, an alkoxy group, a sulfone group, and a sulfonamide group are particularly preferable. Further, 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 (E.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, cyclohexyl, heptyl, octyl, bicyclooctyl, nonyl, adamantyl, decyl, t-octyl, undecyl, Dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, didecyl) are particularly preferred. As the aryl group, those having 6 to 30 carbon atoms are preferable, and those having 6 to 24 carbon atoms (for example, phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, triphenylphenyl) are particularly preferable.
Although the preferable example of a compound represented by General formula (13) or General formula (14) is shown below, this invention is not limited to these specific examples.

The compound represented by the general formula (15) will be described.
General formula (15)

In the general formula (15), R ¹ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, and R ² represents a hydrogen atom, a substituted or unsubstituted aliphatic group, or a substituted or unsubstituted group. Represents an aromatic group. Examples of the substituent include the substituent T described later (the same applies hereinafter unless otherwise specified). L ¹ represents a divalent to hexavalent linking group. The valence of L ¹ is preferably 2 to 4, more preferably 2 or 3. n represents an integer from 2 to 6 corresponding to the valency of L ^1, and more preferably 2 to 4, 2 or 3 is particularly preferred.
Two or more R ¹ and R ² contained in one compound may be the same or different. Preferably they are the same.

The general formula (15) is preferably a compound represented by the following general formula (15a).
General formula (15a)

In the general formula (15a), R ⁴ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. R ⁴ is preferably a substituted or unsubstituted aromatic group, and more preferably an unsubstituted aromatic group. R ⁵ represents a hydrogen atom, a substituted or unsubstituted aliphatic group, or a substituted or unsubstituted aromatic group. R ⁵ is preferably a hydrogen atom or a substituted or unsubstituted aliphatic group, more preferably a hydrogen atom. L ² represents —O—, —S—, —CO—, —NR ³ — (R ³ represents a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group), an alkylene group. And a divalent linking group formed from one or more groups selected from arylene groups. The combination of the linking groups is not particularly limited, but is preferably selected from —O—, —S—, —NR ³ —, and an alkylene group, and particularly preferably selected from —O—, —S—, and an alkylene group. The linking group is preferably a linking group comprising two or more selected from -O-, -S- and an alkylene group.

  The substituted or unsubstituted aliphatic group may be linear, branched or cyclic, preferably has 1 to 25 carbon atoms, more preferably has 6 to 25 carbon atoms, and 6 Those of ˜20 are particularly preferred. Specific examples of the aliphatic group include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, tert-butyl group, amyl group, isoamyl group, tert- Amyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, bicyclooctyl group, adamantyl group, n-decyl group, tert-octyl group, dodecyl group, hexadecyl group, octadecyl group, didecyl group, etc. Is mentioned.

  The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, and more preferably an aromatic hydrocarbon group. As the aromatic hydrocarbon group, those having 6 to 24 carbon atoms are preferable, and those having 6 to 12 carbon atoms are more preferable. Specific examples of the aromatic hydrocarbon group include benzene, naphthalene, anthracene, biphenyl, terphenyl, and the like. As the aromatic hydrocarbon group, benzene, naphthalene, and biphenyl are particularly preferable. As the aromatic heterocyclic group, those containing at least one of an oxygen atom, a nitrogen atom or a sulfur atom are preferable. Specific examples of the heterocyclic ring include, for example, furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazoline, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, Examples thereof include isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzthiazole, benzotriazole, tetrazaindene and the like. As the aromatic heterocyclic group, pyridine, triazine, and quinoline are particularly preferable.

  Moreover, the above-mentioned substituent T is synonymous with what is demonstrated by the following general formula (21).

Moreover, as a compound represented by the said General formula (15), the compound represented by the following general formula (15c) can be mentioned more preferably.
Formula (15c)

In the above general formula (15c), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represents a hydrogen atom or a substituent. Substituent T described later can be applied as the group. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are preferably alkyl groups, alkenyl groups, alkynyl groups, aryl groups, amino groups, alkoxy groups. Group, aryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group , Sulfonyl group, sulfinyl group, ureido group, phosphoric acid amide group, hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group , Hydroxamic acid group, sulfino group, hydrazide Group, imino group, heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably having 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom and a sulfur atom. Is an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a piperidyl group, a morpholino group, a benzoxazolyl group, a benzimidazolyl group, a benzthiazolyl group, etc.), and a silyl group, more preferably an alkyl group. Group, aryl group, aryloxycarbonylamino group, alkoxy group and aryloxy group, particularly preferably alkyl group, aryl group and aryloxycarbonylamino group. These substituents may be further substituted, and when there are two or more substituents, they may be the same or different. If possible, they may be linked together to form a ring. R ¹¹ and R ²¹ , R ¹² and R ²² , R ¹³ and R ²³ , R ¹⁴ and R ²⁴ and R ¹⁵ and R ²⁵ are preferably the same. Furthermore, it is more preferable that R ^{11 to} R ²⁵ are all hydrogen atoms.

L ³ is one or more selected from —O—, —S—, —CO—, —NR ³ — (R ³ represents a hydrogen atom, an aliphatic group or an aromatic group), an alkylene group, and an arylene group. Represents a divalent linking group formed from a group. The combination of the linking groups is not particularly limited, but is preferably selected from —O—, —S—, —NR ³ —, and an alkylene group, and particularly preferably selected from —O—, —S—, and an alkylene group. .
The linking group is more preferably a linking group consisting of two or more selected from -O-, -S- and an alkylene group.
Preferred examples of the compound represented by the general formula (15), particularly the general formula (15a), and the general formula (15c) are shown below, but the present invention is not limited to these specific examples.

  Any of the compounds used in the present invention can be produced from known compounds. The compounds represented by the general formula (15), particularly the general formulas (15a) and (15c) are generally obtained by a condensation reaction between a sulfonyl chloride and a polyfunctional amine.

The compound of the general formula (16) will be described.
General formula (16)

In the general formula (16), R ¹ , R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, butyl, amyl, Isoamyl), and at least one of R ¹ , R ² and R ³ is particularly preferably an alkyl group having 1 to 3 carbon atoms (eg, methyl, ethyl, propyl, isopropyl). X is a single bond, —O—, —CO—, an alkylene group (preferably having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms such as methylene, ethylene, propylene) or an arylene group (preferably carbon atoms). A number of 6 to 24, more preferably 6 to 12. For example, it is preferably a divalent linking group formed from one or more groups selected from phenylene, biphenylene, naphthylene), -O-, alkylene A divalent linking group formed from one or more groups selected from a group or an arylene group is particularly preferable. Y represents a hydrogen atom or an alkyl group (preferably having 2 to 25 carbon atoms, more preferably 2 to 20 carbon atoms. For example, ethyl, isopropyl, t-butyl, hexyl, 2-ethylhexyl, t-octyl, dodecyl, cyclohexyl , Dicyclohexyl, adamantyl), an aryl group (preferably having 6 to 24 carbon atoms, more preferably 6 to 18. For example, phenyl, biphenyl, terphenyl, naphthyl) or an aralkyl group (preferably having 7 to 30 carbon atoms). And more preferably 7 to 20. For example, benzyl, cresyl, t-butylphenyl, diphenylmethyl, triphenylmethyl) is preferable, and an alkyl group, an aryl group, or an aralkyl group is particularly preferable. As a combination of —X—Y, the total carbon number of —X—Y is preferably 0 to 40, more preferably 1 to 30, and most preferably 1 to 25.
Although the preferable example of a compound represented by these General formula (16) is shown below, this invention is not limited to these specific examples.

The compound of the general formula (17) will be described.
Formula (17)

In the general formula (17), Q ¹ , Q ² and Q ³ each independently represent a 5- or 6-membered ring, which may be a hydrocarbon ring or a hetero ring, and these may be a single ring. Further, a condensed ring may be formed with another ring. The hydrocarbon ring is preferably a substituted or unsubstituted cyclohexane ring, a substituted or unsubstituted cyclopentane ring, or an aromatic hydrocarbon ring, and more preferably an aromatic hydrocarbon ring. The hetero ring is preferably a ring containing at least one of a 5- or 6-membered ring oxygen atom, nitrogen atom or sulfur atom. More preferably, the heterocycle is an aromatic heterocycle containing at least one of an oxygen atom, a nitrogen atom or a sulfur atom.
Q ¹ , Q ² and Q ³ are preferably an aromatic hydrocarbon ring or an aromatic hetero ring. The aromatic hydrocarbon ring is preferably (preferably a monocyclic or bicyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms (for example, benzene ring, naphthalene ring etc.), more preferably 6 carbon atoms. -20 aromatic hydrocarbon ring, more preferably an aromatic hydrocarbon ring having 6 to 12 carbon atoms.) More preferred is a benzene ring.

The aromatic heterocycle is preferably an aromatic heterocycle containing an oxygen atom, a nitrogen atom or a sulfur atom. Specific examples of the heterocyclic ring include, for example, furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazoline, thiazole, thiadiazole, oxazoline, oxazole, oxadiazole, Examples include quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzothiazole, benzotriazole, and tetrazaindene. Preferred examples of the aromatic heterocycle include pyridine, triazine, and quinoline. Q ¹ , Q ² and Q ³ are more preferably an aromatic hydrocarbon ring, and more preferably a benzene ring. Q ¹ , Q ² and Q ³ may have a substituent, and examples of the substituent include the substituent T described later.

X represents B, C—R (R represents a hydrogen atom or a substituent), N, P, P═O, X is preferably B, C—R (R is preferably an aryl group, substituted or unsubstituted Substituted amino group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, hydroxy group, mercapto group , A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a carboxyl group, more preferably an aryl group, an alkoxy group, an aryloxy group, a hydroxy group, or a halogen atom, still more preferably an alkoxy group, A hydroxy group, particularly preferably a hydroxy group), N There, is more preferably X is C-R, N, particularly preferably C-R.
The compound represented by the general formula (17) is preferably a compound represented by the following general formula (18).
General formula (18)

(In the general formula (18), X ² represents B, C—R (R represents a hydrogen atom or a substituent), N, P, P═O. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ each independently represents a hydrogen atom or a substituent.)

X ² represents B, C—R (R represents a hydrogen atom or a substituent), N, P, P═O and X ² is preferably B, C—R (R is preferably an aryl group, substituted or Unsubstituted amino group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, hydroxy group, mercapto Group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), carboxyl group, more preferably aryl group, alkoxy group, aryloxy group, hydroxy group, halogen atom, more preferably alkoxy group. , A hydroxy group, particularly preferably a hydroxy group), N , P = O, more preferably C—R, N, and particularly preferably C—R.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are each independently a hydrogen atom. Alternatively, it represents a substituent, and the substituent T described below can be applied as the substituent. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are preferably alkyl groups, Alkenyl, alkynyl, aryl, substituted or unsubstituted amino, alkoxy, aryloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, acylamino, alkoxycarbonylamino, aryloxycarbonyl Amino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, ureido group, phosphoric acid amide group, hydroxy group, mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine) Atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group , Hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having a carbon number of 1-30, more preferably 1-12. Examples of the heteroatom include a nitrogen atom, an oxygen atom, a sulfur atom, Specific examples include imidazolyl, pyridyl, quinolyl, furyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, etc.), and a silyl group, more preferably an alkyl group, an aryl group, a substituted or non-substituted group. A substituted amino group, an alkoxy group and an aryloxy group are preferred, and an alkyl group, an aryl group and an alkoxy group are more preferred.
These substituents may be further substituted. Moreover, when there are two or more substituents, they may be the same or different. If possible, they may be linked together to form a ring.

  The aforementioned substituent T will be described below. Examples of the substituent T include an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms such as methyl, ethyl, iso-propyl, tert-butyl, and n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably carbon number). 2 to 8, for example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), an alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably carbon number). 2-8, for example, propargyl, 3-pentynyl, etc.), aryl groups (preferably having 6-30 carbon atoms) More preferably, it has 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, naphthyl and the like, and a substituted or unsubstituted amino group (preferably having 0 to 0 carbon atoms). 20, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino, etc.), an alkoxy group (preferably having a carbon number) 1 to 20, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as methoxy, ethoxy, butoxy, etc.), an aryloxy group (preferably 6 to 20 carbon atoms, more Preferably it has 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyloxy, 2-naphthyloxy and the like. An acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include acetyl, benzoyl, formyl, pivaloyl). An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, etc.), an aryloxycarbonyl group ( Preferably it has 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms, and examples include phenyloxycarbonyl, etc.), an acyloxy group (preferably 2 to 20 carbon atoms, More preferably, it has 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms. Nzoyloxy and the like. ), An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino), alkoxycarbonylamino group (Preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino), aryloxycarbonylamino group (preferably having carbon number) 7 to 20, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino, and the like, and sulfonylamino groups (preferably 1 to 20 carbon atoms, more preferably Has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms. And sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl and methylsulfamoyl). , Dimethylsulfamoyl, phenylsulfamoyl, etc.), a carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as carbamoyl). , Methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc.), an alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio, Ethylthio etc.), arylthio group (preferably Has 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, and a sulfonyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl, tosyl, etc.), sulfinyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably Has 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc.), ureido group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms). For example, ureido, methylureido, phenylureido, etc.), phosphoric acid amide group (preferably having 1 to 20 carbon atoms) More preferably, it is C1-C16, Most preferably, it is C1-C12, for example, diethyl phosphoric acid amide, phenylphosphoric acid amide etc. are mentioned. ), Hydroxy group, mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, Heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, piperidyl , Morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, etc.), silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms). For example, trimethylsilyl, triphenylsilyl, etc.) . These substituents may be further substituted. Moreover, when there are two or more substituents, they may be the same or different. If possible, they may be linked together to form a ring.

  Specific examples of the compound represented by formula (17) or (18) are shown below, but the present invention is not limited to the following specific examples.

The compound of the general formula (19) will be described.
General formula (19)

In General Formula (19), R ¹ represents an alkyl group or an aryl group, and R ² and R ³ each independently represent a hydrogen atom, an alkyl group, or an aryl group. Moreover, the alkyl group and the aryl group may have a substituent.

Preferred as the general formula (19) is a compound represented by the following general formula (20).
General formula (20)

In the general formula (20), R ⁴ , R ⁵ and R ⁶ each independently represents an alkyl group or an aryl group. Here, the alkyl group may be linear, branched or cyclic, and preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and 1 to 12 carbon atoms. Is most preferred. As the cyclic alkyl group, a cyclohexyl group is particularly preferable. The aryl group preferably has 6 to 36 carbon atoms, and more preferably 6 to 24 carbon atoms.

  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 halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group A sulfonylamino group and an acylamino group, particularly preferably an alkyl group, an aryl group, a sulfonylamino group and an acylamino group.

  Although the preferable example of a compound represented by General formula (19) or General formula (20) below is shown below, this invention is not limited to these specific examples.

Next, the compound represented by the following general formula (21) will be described.
Formula (21)

In general formula (21), R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. X ¹ , X ² , X ³ and X ⁴ are each a single bond, —CO— and —NR ⁵ — (R ⁵ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group) Represents a divalent linking group formed from one or more groups selected from the group consisting of: a, b, c and d are integers of 0 or more, and a + b + c + d is 2 or more. Q ¹ represents an (a + b + c + d) valent organic group.

The compound represented by (21) is preferably a compound represented by the following general formulas (21a) to (21d).
Formula (21a)

In the general formula (21a), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each represent a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. X ¹¹ , X ¹² , X ¹³ and X ¹⁴ are each a single bond, —CO— and —NR ⁵ — (R ⁵ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group) Represents a divalent linking group formed from one or more groups selected from the group consisting of: k, l, m and n are 0 or 1, and k + l + m + n is 2, 3 or 4. Q ² represents a divalent to tetravalent organic group.

  General formula (21b)

In the general formula (21b), R ²¹ and R ²² each represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. Y ¹ and Y ² each represent —CONR ²³ — or —NR ²⁴ CO— (R ²³ and R ²⁴ represent a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group). L ¹ represents —O—, —S—, —SO—, —SO ₂ —, —CO—, —NR ²⁵ — (R ²⁵ represents a hydrogen atom, a substituted or unsubstituted aliphatic group, or a substituted or unsubstituted group. Represents a divalent organic group formed from one or more groups selected from the group consisting of an alkylene group and an arylene group.

  Formula (21c)

In the general formula (21c), R ³¹ , R ³² , R ³³ and R ³⁴ each represent a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. L ² represents —O—, —S—, —SO—, —SO ₂ —, —CO—, —NR ³⁵ — (R ³⁵ represents a hydrogen atom, a substituted or unsubstituted aliphatic group, or a substituted or unsubstituted aroma. A divalent organic group formed from one or more groups selected from the group consisting of an alkylene group and an arylene group.

  Formula (21d)

In the general formula (21d), R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ each represent a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. L ⁴ represents —O—, —S—, —SO—, —SO ₂ —, —CO—, —NR ⁵⁵ — (R ⁵⁵ represents a hydrogen atom, a substituted or unsubstituted aliphatic group, or a substituted or unsubstituted aroma. A divalent organic group formed from one or more groups selected from the group consisting of an alkylene group and an arylene group.

Hereinafter, the compound represented by Formula (21) will be further described.
In the general formula (21), R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, and the aliphatic group is preferable. The aliphatic group may be linear, branched or cyclic, and more preferably cyclic. Examples of the substituent that the aliphatic group and the aromatic group may have include the substituent T described later, but an unsubstituted one is preferable. X ¹ , X ² , X ³ and X ⁴ are each a single bond, —CO—, —NR ⁵ — (R ⁵ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, An unsubstituted group and / or an aliphatic group is more preferable.) A divalent linking group formed from one or more groups selected from the group consisting of: The combination of X ¹ , X ² , X ³ and X ⁴ is not particularly limited, but is more preferably selected from —CO— and —NR ⁵ —. a, b, c and d are integers of 0 or more, and a + b + c + d is 2 or more. It is preferable that a + b + c + d is 2-8, More preferably, it is 2-6, More preferably, it is 2-4. Q ¹ represents an (a + b + c + d) -valent organic group (excluding a cyclic group). The valence of Q ¹ is preferably 2 to 8, more preferably 2 to 6, and most preferably 2 to 4.
An organic group refers to a group composed of an organic compound.

In the general formula (21a), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each represent a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, and the aliphatic group is preferable. The aliphatic group may be linear, branched or cyclic, and more preferably cyclic. Examples of the substituent that the aliphatic group and the aromatic group may have include the substituent T described later, but an unsubstituted one is preferable. X ¹¹ , X ¹² , X ¹³ and X ¹⁴ are each independently a single bond, —CO—, —NR ¹⁵ — (R ¹⁵ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group; An unsubstituted group and / or an aliphatic group is more preferable.) A divalent linking group formed from one or more groups selected from The combination of X ¹¹ , X ¹² , X ¹³ and X ¹⁴ is not particularly limited, but is more preferably selected from —CO— and —NR ¹⁵ —. k, l, m and n are 0 or 1, and k + 1 + m + n = 2, 3 or 4. Q ¹ represents a divalent to tetravalent organic group (excluding a cyclic group). The valence of Q ¹ is preferably 2 or 3.

In the general formula (21b), R ²¹ and R ²² each represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, and an aliphatic group is preferable. The aliphatic group may be linear, branched or cyclic, and more preferably cyclic. Examples of the substituent that the aliphatic group and the aromatic group may have include the substituent T described later, but an unsubstituted one is preferable. Y ¹ and Y ² each independently represent —CONR ²³ — or —NR ²⁴ CO—, wherein R ²³ and R ²⁴ represent a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, and More preferred are substituted and / or aliphatic groups. L ¹ is a divalent organic group formed from one or more groups selected from —O—, —S—, —SO—, —SO ₂ —, —CO—, —NR ²⁵ —, an alkylene group and an arylene group. Represents a group (excluding cyclic ones). The combination of L ¹ is not particularly limited, but is preferably selected from —O—, —S—, —NR ²⁵ —, and an alkylene group, and more preferably selected from —O—, —S—, and an alkylene group. Most preferably, it is selected from among —, —O—, —S— and an alkylene group.

In the general formula (21c), R ³¹ , R ³² , R ³³ and R ³⁴ each represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, and an aliphatic group is preferred. The aliphatic group may be linear, branched or cyclic, and more preferably cyclic. Examples of the substituent that the aliphatic group and the aromatic group may have include the substituent T described later, but an unsubstituted one is preferable. L ² represents —O—, —S—, —SO—, —SO ₂ —, —CO—, —NR ³⁵ — (R ³⁵ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. And a divalent linking group formed from one or more groups selected from an alkylene group and an arylene group. The combination of L ² is not particularly limited, but is preferably selected from —O—, —S—, —NR ³⁵ —, and an alkylene group, and more preferably selected from —O—, —S—, and an alkylene group. Most preferably, it is selected from among —, —O—, —S— and an alkylene group.

In the general formula (21d), R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ each represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, and an aliphatic group is preferable. The aliphatic group may be linear, branched or cyclic, and more preferably cyclic. Examples of the substituent that the aliphatic group and the aromatic group may have include the substituent T described later, but an unsubstituted one is preferable. L ⁴ represents —O—, —S—, —SO—, —SO ₂ —, —CO—, —NR ⁵⁵ — (R ⁵⁵ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. And a divalent linking group formed from one or more groups selected from an alkylene group and an arylene group. The combination of L ⁴ is not particularly limited, but is preferably selected from —O—, —S—, —NR ⁵⁵ —, and an alkylene group, and more preferably selected from —O—, —S—, and an alkylene group. Most preferably, it is selected from among —, —O—, —S— and an alkylene group.

  The substituted or unsubstituted aliphatic group described as a substituent of general formula (21) and general formula (21a)-(21d) is demonstrated below. The aliphatic 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 Particularly preferred. Specific examples of the aliphatic group include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, tert-butyl group, amyl group, isoamyl group, tert- Amyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group bicyclooctyl group, adamantyl group, n-decyl group, tert-octyl group, dodecyl group, hexadecyl group, octadecyl group, didecyl group, etc. Can be mentioned.

  The aromatic group described as a substituent of general formula (21) and general formula (21a)-(21d) below is demonstrated. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, and more preferably an aromatic hydrocarbon group. As the aromatic hydrocarbon group, those having 6 to 24 carbon atoms are preferable, and those having 6 to 12 carbon atoms are more preferable. Specific examples of the aromatic hydrocarbon group include ring groups such as benzene, naphthalene, anthracene, biphenyl, and terphenyl. As the aromatic hydrocarbon group, benzene, naphthalene, and biphenyl groups are particularly preferable. As the aromatic heterocyclic group, those containing at least one of an oxygen atom, a nitrogen atom or a sulfur atom are preferable. Specific examples of the heterocyclic ring include, for example, furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazoline, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, Examples of the ring include isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzthiazole, benzotriazole, and tetrazaindene. As the aromatic heterocyclic group, a pyridine ring, a triazine ring, and a quinoline ring are particularly preferable.

Further, the above-described substituent T according to each general formula will be described in detail below.
Examples of the substituent T include an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, and tert-butyl. Group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl, cyclohexyl group, etc.), alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms). In particular, it is 2 to 8, and examples thereof include a vinyl group, an allyl group, a 2-butenyl group, and a 3-pentenyl group.), An alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12, particularly preferably 2 to 8, for example, propargyl group, 3-pentynyl group, etc.), aryl group (preferably carbon The number of children is 6 to 30, more preferably 6 to 20, particularly preferably 6 to 12, and examples thereof include a phenyl group, a biphenyl group, and a naphthyl group.), An amino group (preferably having 0 to 20 carbon atoms, More preferably, it is 0-10, Most preferably, it is 0-6, for example, an amino group, a methylamino group, a dimethylamino group, a diethylamino group, a dibenzylamino group etc. are mentioned.

An alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms such as methoxy group, ethoxy group and butoxy group), aryloxy group (preferably The number of carbon atoms is 6 to 20, more preferably 6 to 16, particularly preferably 6 to 12, and examples thereof include a phenyloxy group and a 2-naphthyloxy group.), An acyl group (preferably 1 to 1 carbon atom). 20, More preferably, it is 1-16, Most preferably, it is 1-12, for example, an acetyl group, a benzoyl group, a formyl group, a pivaloyl group etc.), an alkoxycarbonyl group (preferably 2-20 carbon atoms, More preferably, it is 2 to 16, particularly preferably 2 to 12, and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group. ), An aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms such as a phenyloxycarbonyl group), an acyloxy group (preferably Has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include an acetoxy group and a benzoyloxy group.

An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms such as acetylamino group and benzoylamino group), alkoxycarbonylamino group (preferably The number of carbon atoms is 2 to 20, more preferably 2 to 16, particularly preferably 2 to 12, and examples thereof include a methoxycarbonylamino group.), An aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, More preferably, it is 7-16, Most preferably, it is 7-12, for example, a phenyloxycarbonylamino group etc. are mentioned, A sulfonylamino group (preferably 1-20 carbon atoms, More preferably, it is 1-16, Especially Preferably it is 1-12, for example, methanesulfonylamino group, benzenesulfonyla A sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as a sulfamoyl group, a methylsulfamoyl group, and dimethylsulfa). And a carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms such as a carbamoyl group and a methylcarbamoyl group). , Diethylcarbamoyl group, phenylcarbamoyl group, etc.).

An alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms such as a methylthio group and an ethylthio group), an arylthio group (preferably having 6 carbon atoms). -20, more preferably 6-16, particularly preferably 6-12, for example, phenylthio group, etc.), sulfonyl group (preferably 1-20 carbon atoms, more preferably 1-16, particularly preferably 1-12, for example, mesyl group, tosyl group, etc.), sulfinyl group (preferably 1-20 carbon atoms, more preferably 1-16, particularly preferably 1-12, for example methane Sulfinyl group, benzenesulfinyl group, etc.), ureido group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, particularly preferably 1 to 12, and examples thereof include a ureido group, a methylureido group, and a phenylureido group.), A phosphoric acid amide group (preferably having 1 to 20 carbon atoms, more preferably 1 to 1). 16, particularly preferably 1 to 12, and examples thereof include diethyl phosphoric acid amide and phenyl phosphoric acid amide), hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom) , Cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, As, for example, a nitrogen atom, an oxygen atom, a sulfur atom, specifically, for example, an imidazolyl group, a pyridyl group, a quinolyl group A furyl group, a piperidyl group, a morpholino group, a benzoxazolyl group, a benzimidazolyl group, a benzthiazolyl group, etc.), a silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably Is 3 to 24, and examples thereof include a trimethylsilyl group and a triphenylsilyl group).
These substituents may be further substituted. Moreover, when there are two or more substituents, they may be the same or different. If possible, they may be linked together to form a ring.

  Preferred examples of the compound represented by the general formula (21) are shown below, but the present invention is not limited to these specific examples.

  Any of the compounds used in the present invention can be produced from known compounds. The compound represented by the general formula (21) or any one of (21a) to (21d) is obtained, for example, by a condensation reaction of carbonyl chloride and an amine.

(Log P value)
In producing the cellulose derivative film of the present invention, as described above, the substituent on the cellulose derivative in the film becomes a film by increasing the compatibility between the substituent having high polarizability anisotropy and the retardation modifier. In order to further increase the ratio of orientation in the thickness direction, it is preferable to use a compound having an octanol-water partition coefficient (log P value) of 0 to 10 as a retardation regulator. When the log P value is 10 or less, the compatibility with the substituents on the cellulose derivative is good, and there is an effect of sufficiently reducing Rth, and there is no problem of causing cloudiness or powder blowing of the film. ,preferable. Moreover, when the log P value is 0 or more, the hydrophilicity does not become too high, and the problem of deteriorating the water resistance of the cellulose derivative film does not occur, which is preferable. A more preferable range for the logP value is 1 to 6, and a particularly preferable range is 1.5 to 5.
The octanol-water partition coefficient (log P value) can be measured by a flask immersion method described in JIS Japanese Industrial Standard Z7260-107 (2000). Further, the octanol-water partition coefficient (log P value) can be estimated by a computational chemical method or an empirical method instead of the actual measurement. As a calculation method, Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)), Viswanadhan's fragmentation method (J. Chem. Inf. Comput. Sci., 29, 163). (1989)), Broto's fragmentation method (Eur. J. Med. Chem.-Chim. Theor., 19, 71 (1984)) and the like are preferably used, but the Crippen's fragmentation method (J. Chem. Inf .Comput.Sci., 27, 21 (1987)) is more preferable. When the log P value of a certain compound varies depending on the measurement method or calculation method, it is preferable to determine whether or not the compound is within the scope of the present invention by the Crippen's fragmentation method.

[Physical properties of retardation regulator]
As described above, the retardation modifier may or may not contain an aromatic group. The retardation regulator preferably has a molecular weight of 3000 or less, more preferably a molecular weight of 150 or more and 3000 or less, further preferably 170 or more and 2000 or less, and particularly preferably 200 or more and 1000 or less. preferable. A specific monomer structure may be used as long as these molecular weights are within the range, and an oligomer structure or a polymer structure in which a plurality of the monomer units are bonded may be used.
The retardation regulator is preferably liquid at 25 ° C. or a solid having a melting point of 25 to 250 ° C., more preferably liquid at 25 ° C. or a solid having a melting point of 25 to 200 ° C. . Moreover, it is preferable that a retardation regulator does not volatilize in the process of dope casting and drying for producing a cellulose derivative film.
The addition amount of the retardation modifier is preferably 0.01 to 30% by mass of the cellulose derivative, more preferably 1 to 25% by mass, and particularly preferably 3 to 20% by mass.
The retardation adjusting agent may be used alone, or two or more compounds may be mixed and used in an arbitrary ratio.
The retardation adjusting agent may be added at any time during the dope preparation process or at the end of the dope preparation process.

[Other retardation regulators]
Optical anisotropy can also be reduced by adding a polyhydric alcohol ester compound, a carboxylic acid ester compound, a polycyclic carboxylic acid compound, or a bisphenol derivative to the cellulose derivative. That is, these compounds are also compounds that reduce the optical anisotropy of the cellulose derivative film. In the present invention, these compounds can also be used as the retardation regulator. These compounds preferably have an octanol-water partition coefficient (Log P value) of 0 to 10 as in the compounds represented by the general formulas (1) to (21).

  Specific examples of polyhydric alcohol ester compounds, carboxylic acid ester compounds, polycyclic carboxylic acid compounds, and bisphenol derivatives having an octanol-water partition coefficient (Log P value) of 0 to 10 are shown below.

(Polyhydric alcohol ester compound)
The polyhydric alcohol ester suitably used in the present invention is an ester of a dihydric or higher polyhydric alcohol and one or more monocarboxylic acids. Examples of the polyhydric alcohol ester compound include the following, but the present invention is not limited thereto.

(Polyhydric alcohol)
Examples of preferable polyhydric alcohol include, for example, adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1 , 2-butanediol, 1,3-butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, Examples thereof include galactitol, mannitol, 3-methylpentane-1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, xylitol and the like. In particular, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferable.

(Monocarboxylic acid)
The preferred monocarboxylic acid is not particularly limited, and known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid and the like can be used. It is preferable to use alicyclic monocarboxylic acid or aromatic monocarboxylic acid in terms of improving the moisture permeability, moisture content, and retention of the cellulose derivative film.

  Examples of preferred monocarboxylic acids include the following, but the present invention is not limited thereto.

  As the aliphatic monocarboxylic acid, a fatty acid having a straight chain or side chain having 1 to 32 carbon atoms can be preferably used. The number of carbon atoms is more preferably 1-20, and particularly preferably 1-10. When acetic acid is contained, compatibility with the cellulose ester is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid.

  Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid, tridecylic acid , Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, laccelic acid, undecylenic acid, Examples thereof include unsaturated fatty acids such as oleic acid, sorbic acid, linoleic acid, linolenic acid and arachidonic acid. These may further have a substituent.

  Examples of preferred alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, or derivatives thereof.

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

  The carboxylic acid in the polyhydric alcohol ester of the present invention may be one kind or a mixture of two or more kinds. Moreover, all the OH groups in the polyhydric alcohol may be esterified, or a part of the OH groups may be left as they are. Preferably, it has 3 or more aromatic rings or cycloalkyl rings in the molecule.

  Examples of the polyhydric alcohol ester compound include the following compounds, but the present invention is not limited thereto.

(Carboxylic acid ester compound)
Examples of the carboxylic acid ester compound include the following compounds, but the present invention is not limited thereto. Specifically, phthalic acid esters such as phthalic acid esters and citric acid esters, phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dicyclohexyl phthalate, dioctyl phthalate and diethyl hexyl phthalate, etc. Mention may be made of acetyltributyl acid. Other examples include butyl oleate, methyl acetyl ricinoleate, dibutyl sebacate, triacetin, trimethylolpropane tribenzoate and the like. Alkyl phthalyl alkyl glycolates are also preferably used for this purpose. The alkyl in the alkylphthalylalkyl glycolate is an alkyl group having 1 to 8 carbon atoms. Examples of alkyl phthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, methyl phthalyl ethyl glycolate, Ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, propyl phthalyl ethyl glycolate, methyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, butyl Phthalyl ethyl glycolate, propyl phthalyl butyl glycolate, butyl phthalyl propyl glycolate, methyl phthalyl octyl glycolate, ethyl phthalyl octyl Collate, octyl phthalyl methyl glycolate, octyl phthalyl ethyl glycolate and the like can be mentioned, methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, Octyl phthalyl octyl glycolate is preferable, and ethyl phthalyl ethyl glycolate is particularly preferably used. Two or more of these alkylphthalylalkyl glycolates may be used in combination.

  Examples of the carboxylic acid ester compound include the following compounds, but the present invention is not limited thereto.

(Polycyclic carboxylic acid compound)
The polycyclic carboxylic acid compound used in the present invention is preferably a compound having a molecular weight of 3000 or less, and particularly preferably a compound having a molecular weight of 250 to 2000. Regarding the cyclic structure, the size of the ring is not particularly limited, but it is preferably composed of 3 to 8 atoms, particularly preferably a 6-membered ring and / or a 5-membered ring. These may contain carbon, oxygen, nitrogen, silicon or other atoms, and a part of the ring bond may be an unsaturated bond. For example, the 6-membered ring may be a benzene ring or a cyclohexane ring. The compound of the present invention contains a plurality of such cyclic structures. For example, the compound of the present invention has both a benzene ring and a cyclohexane ring in the molecule, has two cyclohexane rings, It may be a naphthalene derivative or an anthracene derivative. More preferably, it is a compound containing three or more such cyclic structures in the molecule. Moreover, it is preferable that at least one bond of the cyclic structure does not contain an unsaturated bond. Specifically, abietic acid derivatives such as abietic acid, dehydroabietic acid, and parastrinic acid are typical, and chemical formulas of these compounds are shown below, but are not particularly limited thereto.

  In K-5, R represents a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, and an aliphatic group is preferable. The aliphatic group may be linear, branched or cyclic, and more preferably cyclic. Moreover, n should just be an integer greater than or equal to 1, It is preferable that it is 1 <= n <= 20, and it is more preferable that it is 1 <= n <= 10.

(Bisphenol derivative)
The bisphenol derivative used in the present invention preferably has a molecular weight of 10,000 or less, and may be a monomer, an oligomer, or a polymer within this range. Moreover, the copolymer with another polymer may be sufficient and the reactive substituent may be modified by the terminal. The chemical formulas of these compounds are shown below, but are not particularly limited thereto.

In the above specific examples of the bisphenol derivative, R1 to R4 represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. l, m, and n represent a repeating unit and are not particularly limited, but an integer of 1 to 100 is preferable, and an integer of 1 to 20 is more preferable.
The blending amount of the polyhydric alcohol ester compound, the carboxylic acid ester compound, the polycyclic carboxylic acid compound, and the bisphenol derivative having the LogP value of 0 to 10 is 0.1 to 30 parts by mass with respect to 100 parts by mass of the cellulose derivative. It is preferable to use 1 to 20 parts by mass.

[Other additives]
In the cellulose derivative film of the present invention, various additives according to the use in each preparation step (for example, wavelength dispersion adjusting agent, ultraviolet ray preventing agent, plasticizer, deterioration preventing agent, matting agent fine particles, optical property adjusting agent, etc.) These are described below. Further, the addition may be performed at any time in the dope preparation process, but may be performed by adding an additive to the final preparation process of the dope preparation process.

(Wavelength dispersion modifier)
In the cellulose derivative film of the present invention, a compound having a spectral absorption maximum at 250 nm to 400 nm can be used as a wavelength dispersion modifier.
The λmax of the chromatic dispersion regulator is more preferably 270 nm or more and 360 nm.
Further, the absorbance at 400 nm is preferably 0.20 or less, and more preferably 0.10 or less.
By using the wavelength dispersion modifier having the above absorption characteristics, a film having high optical isotropy over the entire visible range and no coloring can be obtained.
The wavelength dispersing agent may also function as an ultraviolet absorber.
As the wavelength dispersion regulator, it is particularly preferable to use compounds represented by the following general formulas (III) to (VII).
Formula (III)

In the formula, Q ¹ and Q ² each independently represents an aromatic ring. X represents a substituent, and Y represents an oxygen atom, a sulfur atom or a nitrogen atom. XY may be a hydrogen atom.
Formula (IV)

In the formula, R ¹ , R ² , R ³ , R ^4, and R ⁵ are each independently a monovalent organic group, and at least one of R ¹ , R ^2, and R ³ is an allyl group having 10 to 20 carbon atoms. A substituted branched or straight chain alkyl group.
General formula (V)

In the formula, R ¹ , R ² , R ⁴ and R ⁵ are each independently a monovalent organic group, and R ⁶ is a branched alkyl group.

Further, as described in JP-A No. 2003-315549, a compound represented by the general formula (VI) can also be preferably used.
Formula (VI)

In the formula, R ⁰ and R ¹ are each independently a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, an unsubstituted or substituted phenyl group having 1 to 4 carbon atoms, A substituted or unsubstituted oxycarbonyl group or a substituted or unsubstituted aminocarbonyl group is represented. R ^{2 to} R ⁵ and R ^{19 to} R ²³ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 2 to 20 carbon atoms.

  Furthermore, for example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, cyanoacrylate compounds, nickel complex compounds, and the like can also be used as the wavelength dispersion regulator.

  Examples of the compound represented by the general formula (III) include benzophenone compounds.

Specific examples of the benzotriazole-based compounds are listed below, but the benzotriazole-based compounds that can be used in the present invention are not limited to these.
2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3) '-Tert-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy -3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl) benzotriazole, 2,2-methylenebis (4- (1,1,3, 3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazol 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenylmethane) , (2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, 2 (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, (2 (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) -5-chlorobenzotriazole, 2,6-di -Tert-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) pro Pionate], triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, 2, 2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 1,3,5-tri Methyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, etc. Is mentioned. In particular, (2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, 2 (2′-hydroxy-3 ′, 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, (2 (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) -5-chlorobenzotriazole, 2,6-di -Tert-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-tert-butyl -5-methyl-4-hydroxyphenyl) propionate], for example, N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxy). A hydrazine-based metal deactivator such as (cyphenyl) propionyl] hydrazine or a phosphorus-based processing stabilizer such as tris (2,4-di-tert-butylphenyl) phosphite may be used in combination. Is preferably 1 ppm to 1.0%, more preferably 10 to 1000 ppm, by weight with respect to the cellulose derivative.

Formula (VII) Q ¹ -Q ² -OH

In the formula, Q ¹ represents a 1,3,5-triazine ring, and Q ² represents an aromatic ring.

A more preferred example of the wavelength dispersion regulator represented by the general formula (VII) is a compound represented by the following general formula (VII-A).
Formula (VII-A)

In the formula (VII-A), more preferably R ¹ Is an alkyl group having 1 to 18 carbon atoms; a cycloalkyl group having 5 to 12 carbon atoms; an alkenyl group having 3 to 18 carbon atoms; a phenyl group; a phenyl group, OH, an alkoxy group having 1 to 18 carbon atoms; C 5-12 cycloalkoxy group, C 3-18 alkenyloxy group, halogen atom, —COOH, —COOR ⁴ , -O-CO-R ⁵ , —O—CO—O—R ₆ , —CO—NH ₂ , —CO—NHR ⁷ , —CO—N (R ⁷ ) (R ⁸ ), CN, NH ₂ , NHR ⁷ , —N (R ⁷ ) (R ⁸ ), —NH—CO—R ₅ , phenoxy group, phenoxy group substituted with an alkyl group having 1 to 18 carbon atoms, phenyl-alkoxy group having 1 to 4 carbon atoms, bicycloalkoxy having 6 to 15 carbon atoms Group, a bicycloalkylalkoxy group having 6 to 15 carbon atoms, a bicycloalkenylalkoxy group having 6 to 15 carbon atoms, or an alkyl group having 1 to 18 carbon atoms substituted with a tricycloalkoxy group having 6 to 15 carbon atoms A group: OH, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a cycloalkyl group having 5 to 12 carbon atoms substituted with —O—CO—R ⁵ ; a glycidyl group; CO-R ⁹ Or represents a -SO ₂ -R ^10; or R ¹ Represents an alkyl group having 3 to 50 carbon atoms interrupted with one or more oxygen atoms and / or substituted with OH, a phenoxy group or an alkylphenoxy group having 7 to 18 carbon atoms; or R ¹ is- _{A; -CH 2 -CH (XA)} -CH 2 -O-R 12; -CR 13 R '13 - (CH 2) m -X-A; -CH 2 -CH (OA) -R 14; -CH _{2 -CH (OH) -CH 2 -XA} ;

^{-CR 15 R '15 -C (=} CH 2) -R "15; -CR 13 R' 13 - (CH 2) m -CO-X-A; -CR 13 R '13 - (CH 2) m - CO—O—CR ¹⁵ R ′ ¹⁵ —C (═CH ₂ ) —R ″ ¹⁵ or —CO—O—CR ¹⁵ R ′ ¹⁵ —C (═CH ₂ ) —R ” ¹⁵ (wherein A is —CO —CR ¹⁶ ═CH—R ¹⁷ ); one of the definitions represented by; and the groups R ² , independently of one another, are alkyl groups having 6 to 18 carbon atoms; Phenyl group; phenylalkyl group having 7 to 11 carbon atoms; COOR ₄ ; CN; —NH—CO—R ⁵ ; halogen atom; trifluoromethyl group; —O—R ³ ; R ³ represents R represents the definitions given for ^1; R ⁴ is an alkyl group having 1 to 18 carbon atoms; an alkenyl group having 3 to 18 carbon atoms; a phenyl group; Fe C7-11 A cycloalkyl group having 5 to 12 carbon atoms; or R ⁴ is interrupted by one or more —O—, —NH—, —NR ⁷ —, —S— and OH, phenoxy group or Represents an alkyl group having 3 to 50 carbon atoms which may be substituted with an alkylphenoxy group having 7 to 18 carbon atoms; R ⁵ represents H; an alkyl group having 1 to 18 carbon atoms; 18 alkenyl groups; cycloalkyl groups having 5 to 12 carbon atoms; phenyl groups; phenylalkyl groups having 7 to 11 carbon atoms; bicycloalkyl groups having 6 to 15 carbon atoms; bicycloalkenyl groups having 6 to 15 carbon atoms group; represents a tricycloalkyl group having a carbon number of 6 to 15; R ⁶ is H; phenyl; C7-11 alkenyl group having 3 to 18 carbon atoms, alkyl group having 1 to 18 carbon atoms Phenylalkyl group; a cycloalkyl group having a carbon number of 5 to 12; R ⁷ and R ⁸ independently of one another are an alkyl group having 1 to 12 carbon atoms; carbon atoms; an alkoxyalkyl group having 3 to 12 carbon atoms A dialkylaminoalkyl group having 4 to 16 carbon atoms; or a cycloalkyl group having 5 to 12 carbon atoms; or R ⁷ and R ^{8 taken} together are an alkylene group having 3 to 9 carbon atoms, a carbon atom An oxaalkylene group having 3 to 9 carbon atoms or an azaalkylene group having 3 to ⁹ carbon atoms; R ⁹ is an alkyl group having 1 to 18 carbon atoms; an alkenyl group having 2 to 18 carbon atoms; a phenyl group; A cycloalkyl group having 5 to 12 carbon atoms; a phenylalkyl group having 7 to 11 carbon atoms; a bicycloalkyl group having 6 to 15 carbon atoms; a bicycloalkyl group having 6 to 15 carbon atoms; Represents tricycloalkyl group or having 6 to 15 carbon atoms; group, bicycloalkenyl group having 6 to 15 carbon atoms R ¹⁰ represents an alkyl group having 1 to 12 carbon atoms; a phenyl group; a naphthyl group; or carbon Represents an alkylphenyl group having 7 to 14 atoms; the groups R ¹¹ are independently of each other H; an alkyl group having 1 to 18 carbon atoms; an alkenyl group having 3 to 6 carbon atoms; a phenyl group; 11 phenylalkyl group; a halogen atom; an alkoxy group having 1 to 18 carbon atoms; R ¹² is an alkyl group having 1 to 18 carbon atoms; an alkenyl group having 3 to 18 carbon atoms; a phenyl group; A phenyl group substituted 1 to 3 times with an alkyl group of 1 to 8, an alkoxy group of 1 to 8 carbon atoms, an alkenoxy group of 3 to 8 carbon atoms, a halogen atom or a trifluoromethyl group; Or a phenylalkyl group having 7 to 11 carbon atoms; a cycloalkyl group having 5 to 12 carbon atoms; a tricycloalkyl group having 6 to 15 carbon atoms; a bicycloalkyl group having 6 to 15 carbon atoms; a carbon atom number 6-15 bicycloalkyl group of; represents -CO-R ^5;; bicycloalkenyl group having 6 to 15 carbon atoms or R ¹² is one or more -O -, - NH -, - NR 7 -, interrupted by -S- been and OH, optionally substituted phenoxy group or an alkylphenoxy group having a carbon number of 7 to 18, an alkyl group having a carbon number of 3 to 50; R ¹³ and R ^'13 are Independently of each other; H; an alkyl group having 1 to 18 carbon atoms; a phenyl group; R ¹⁴ is an alkyl group having 1 to 18 carbon atoms; an alkoxyalkyl group having 3 to 12 carbon atoms; a phenyl group; Phenyl represents an alkyl group having 1 to 4 carbon atoms; R ¹⁵ , R ′ ¹⁵ and R ″ ¹⁵ each independently represent H or CH ₃ ; R ¹⁶ represents H; —CH ₂ —COO—R ⁴ ; An alkyl group having 1 to 4 carbon atoms; or CN; R ¹⁷ represents H; —COOR ⁴ ; an alkyl group having 1 to 17 carbon atoms; or a phenyl group; X represents —NH—; —NR ⁷ —. ; -O -; - NH- (CH 2) p -NH-; an n is the number 1-8; or -O- (CH _{2) q} -NH- and represents; and index m is a number 0-19 P represents the number 0 to 4; q represents the number 2 to 4; provided that in general formula (VII-A), at least one of R ¹ , R ² and R ¹¹ contains two or more carbon atoms. .

Furthermore, the compound represented by general formula (VII-A) is demonstrated.
The groups R ^{1 to} R ¹⁰ , R ^{12 to} R ¹⁴ , R ¹⁶ and R ¹⁷ as alkyl groups are branched or branched alkyl groups, such as methyl, ethyl, propyl, isopropyl, n- Butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2-ethylbutyl group, n-pentyl group, isopentyl group, 1-methylpentyl group, 1,3-dimethylbutyl group, n-hexyl group, 1- Methylhexyl group, n-heptyl group, isoheptyl group, 1,1,3,3-tetramethylbutyl group, 1-methylheptyl group, 3-methylheptyl group, n-octyl group, 2-ethylhexyl group, 1,1 , 3-trimethylhexyl group, 1,1,3,3-tetramethylpentyl group, nonyl group, decyl group, undecyl group, 1-methylundecyl group, dodecyl group, 1,1, A 3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.

R ₁ , R _{3 to} R ₉ and R ₁₂ as a cycloalkyl group having 5 to 12 carbon atoms are, for example, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, Cyclododecyl group. Preference is given to a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and a cyclododecyl group.

R ⁶ , R ⁹ , R ¹¹ and R ¹² as alkenyl groups are in particular allyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-diethyl, 3- Methyl-but-2-enyl group, n-oct-2-enyl group, n-dodec-2-enyl group, iso-dodecenyl group, n-dodec-2-enyl group and n-octadec-4-enyl group Is included.

  The number of substituents in the substituted alkyl group, cycloalkyl group or phenyl group is 1 or 2 or more, and may have a substituent at the carbon atom to which it is bonded (in the α-position) or at another carbon atom. Yes; when the substituent is bonded via a heteroatom (for example, an alkoxy group), the bonding position of the substituent is preferably other than the α-position, and the number of carbon atoms of the substituted alkyl group is preferably 2 or more. Preferably it is 3 or more. Two or more substituents are preferably bonded to different carbon atoms.

Alkyl groups interrupted by —O—, —NH—, —NR ⁷ —, —S— may be interrupted by one or more of these groups, each generally having one group in one bond. Inserted and does not result in hetero-hetero bonds, such as OO, SS, NH-NH, etc .; when the interrupted alkyl group is further substituted, the substituent is generally to the heteroatom Not in alpha position. When two or more —O—, —NH—, —NR ⁷ —, —S— type interrupting groups occur within a group, they are generally the same.

  The aryl group is generally an aromatic hydrocarbon group, such as a phenyl group, a biphenylyl group or a naphthyl group, preferably a phenyl group and a biphenylyl group. Aralkyl is generally an alkyl group substituted by an aryl group, especially a phenyl group; therefore, an aralkyl having 7 to 20 carbon atoms is, for example, a benzyl group, an α-methylbenzyl group, a phenylethyl group, a phenylpropyl group, a phenyl group. Including a butyl group, a phenylpentyl group and a phenylhexyl group; the phenylalkyl group having 7 to 11 carbon atoms is preferably a benzyl group, an α-methylbenzyl group and an α, α-dimethylbenzyl group.

  The alkylphenyl group and the alkylphenoxy group are a phenyl group or a phenoxy group each substituted with an alkyl group.

  The halogen atom serving as the halogen substituent is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom or a chlorine atom, and particularly preferably a chlorine atom.

  Examples of the alkylene group having 1 to 20 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group. Here the alkyl chain can also be branched, for example an isopropylene group.

  Examples of the cycloalkenyl group having 4 to 12 carbon atoms include 2-cyclobuten-2-yl group, 2-cyclopenten-1-yl group, 2,4-cyclopentadien-1-yl group, and 2-cyclohexe- 1-yl group, 2-cyclohepten-1-yl group, or 2-cycloocten-1-yl group.

Examples of the bicycloalkyl group having 6 to 15 carbon atoms include a bornyl group, a norbornyl group,
[2.2.2] Bicyclooctyl group. A bornyl group and a norbornyl group, particularly a bornyl group and a norborn-2-yl group are preferred.

  The bicycloalkoxy group having 6 to 15 carbon atoms is, for example, a bornyloxy group or a norborn-2-yloxy group.

  A bicycloalkyl-alkyl group or alkoxy group having 6 to 15 carbon atoms is an alkyl group or alkoxy group substituted with a bicycloalkyl group, and the total number of carbon atoms is 6 to 15; specific examples are norbornane A 2-methyl group and a norbornyl-2-methoxy group.

  The bicycloalkenyl group having 6 to 15 carbon atoms is, for example, a norbornenyl group or a norbornadienyl group. Preference is given to norbornenyl groups, especially norborn-5-ene groups.

  A bicycloalkenylalkoxy group having 6 to 15 carbon atoms is an alkoxy group substituted with a bicycloalkenyl group and having a total number of carbon atoms of 6 to 15; for example, a norbornene-5-ene-2-methoxy group is there.

  The tricycloalkyl group having 6 to 15 carbon atoms is, for example, a 1-adamantyl group or a 2-adamantyl group. Preferred is a 1-adamantyl group.

  The tricycloalkoxy group having 6 to 15 carbon atoms is, for example, an adamantyloxy group. The heteroaryl group having 3 to 12 carbon atoms is preferably a pyridinyl group, a pyrimidinyl group, a triazinyl group, a pyrrolyl group, a furanyl group, a thiophenyl group or a quinolinyl group.

The compound represented by the formula (VII-A) is more preferably R ¹ is an alkyl group having 1 to 18 carbon atoms; a cycloalkyl group having 5 to 12 carbon atoms; an alkenyl group having 3 to 12 carbon atoms; Phenyl group; phenyl group, OH, alkoxy group having 1 to 18 carbon atoms, cycloalkoxy group having 5 to 12 carbon atoms, alkenyloxy group having 3 to 18 carbon atoms, halogen atom, —COOH, —COOR ⁴ , —O—CO—R ⁵ , —O—CO—O—R ⁶ , —CO—NH ₂ , —CO—NHR ⁷ , —CO—N (R ⁷ ) (R ⁸ ), CN, NH ₂ , NHR ⁷ , —N (R ⁷ ) (R ⁸ ), —NH—CO—R ⁵ , a phenoxy group, a phenoxy group substituted with an alkyl group having 1 to 18 carbon atoms, and a phenyl-alkoxy group having 1 to 4 carbon atoms. , Bornyloxy group, norbornyl-2-yloxy , A norbornyl-2-methoxy group, a norbornene-5-ene-2-methoxy group, an adamantyloxy group substituted with an alkyl group having 1 to 18 carbon atoms; OH, an alkyl group having 1 to 4 carbon atoms, a carbon atom Represents a cycloalkyl group having 5 to 12 carbon atoms substituted with an alkenyl group having 2 to 6 and / or —O—CO—R ⁵ ; a glycidyl group; —CO—R ⁹ or —SO ₂ —R ¹⁰ Or R ¹ represents an alkyl group having 3 to 50 carbon atoms interrupted by one or more oxygen atoms and / or substituted with OH, a phenoxy group or an alkylphenoxy group having 7 to 18 carbon atoms; or R ¹ is —A; —CH ₂ —CH (XA) —CH ₂ —O—R ¹² ; —CR ¹³ R ′ ¹³ — (CH ₂ ) _m —XA; —CH ₂ —CH (OA) —R _{^{14; -CH 2 -CH (OH)}} -C ₂ -XA;

^{-CR 15 R '15 -C (=} CH 2) -R "15; -CR 13 R' 13 - (CH 2) m -CO-X-A; -CR 13 R '13 - (CH 2) m - CO—O—CR ₁₅ R ′ ¹⁵ —C (═CH ₂ ) —R ″ ¹⁵ or —CO—O—CR ¹⁵ R ′ ¹⁵ —C (═CH ₂ ) —R ” ¹⁵ (wherein A is —CO -CR ¹⁶ = CH-R ¹⁷ )); the group R ² is an alkyl group having 6 to 18 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; a phenyl group; Represents —O—R ³ or —NH—CO—R ⁵ ; and the group R ₃ independently of one another represents the definition given for R ¹ ; R ⁴ is an alkyl group of 1 to 18 carbon atoms; or a cycloalkyl group of 5 to 12 carbon atoms; a phenyl group; a phenyl alkyl group of C7-11 alkenyl group having 3 to 18 carbon atoms or R ⁴ one or more O -, - NH -, - NR 7 -, - interrupted by S- and OH, optionally substituted phenoxy group or an alkylphenoxy group having a carbon number of 7 to 18, alkyl of carbon atoms 3 to 50 R ⁵ is H; an alkyl group having 1 to 18 carbon atoms; an alkenyl group having 2 to 18 carbon atoms; a cycloalkyl group having 5 to 12 carbon atoms; a phenyl group; A phenylalkyl group; a norborn-2-yl group; a norborn-5-en-2-yl group; an adamantyl group; R ⁶ is H; an alkyl group having 1 to 18 carbon atoms; A phenyl group; a phenylalkyl group having 7 to 11 carbon atoms; a cycloalkyl group having 5 to 12 carbon atoms; and R ⁷ and R ⁸ independently of each other, an alkyl group having 1 to 12 carbon atoms; Number of atoms 12 alkoxyalkyl group; or represents dialkylaminoalkyl group having a carbon number of 4 to 16; or a cycloalkyl group having 5 to 12 carbon atoms; or R ⁷ and R ⁸ carbon atoms together An alkylene group having 3 to 9 carbon atoms; an oxaalkylene group having 3 to 9 carbon atoms or an azaalkylene group having 3 to ⁹ carbon atoms; R ⁹ is an alkyl group having 1 to 18 carbon atoms; A phenyl group; a cycloalkyl group having 5 to 12 carbon atoms; a phenylalkyl group having 7 to 11 carbon atoms; a norborn-2-yl group; a norborn-5-en-2-yl group; and an adamantyl group. It represents; R ¹⁰ is an alkyl group having 1 to 12 carbon atoms; represents an alkyl phenyl group having a carbon number of 7 to 14; phenyl; naphthyl radical R ¹¹ independently of one another are ; Represents or phenylalkyl group having a carbon number of 7 to 11; alkyl group having 1 to 18 carbon atoms R ¹² represents an alkyl group having 1 to 18 carbon atoms; a phenyl group; an alkenyl group having 3 to 18 carbon atoms A phenyl group substituted 1 to 3 times with an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenoxy group having 3 to 8 carbon atoms, a halogen atom or a trifluoromethyl group; carded; or phenylalkyl group having a carbon number of 7-11; a cycloalkyl group having a carbon number of 5 to 12; 1-adamantyl; 2-adamantyl group; norbornyl group; norbornane-2-methyl -; - CO-R ⁵ the expressed; or R ¹² is one or more -O -, - NH -, - NR 7 -, - interrupted by S- and OH, phenoxy or alkyl phenol having a carbon number of 7 to 18 Shi may be substituted with a group, an alkyl group having a carbon number of 3 to 50; R ¹³ and R ^'13 is H independently of each other; a phenyl group; an alkyl group having 1 to 18 carbon atoms; R ¹⁴ represents an alkyl group having 1 to 18 carbon atoms; an alkoxyalkyl group having 3 to 12 carbon atoms; a phenyl group; a phenyl-alkyl group having 1 to 4 carbon atoms; R ¹⁵ , R ′ ¹⁵ and R ″ ¹⁵ represents independently of each other H or CH ₃ ; R ¹⁶ represents H; —CH ₂ —COO—R ⁴ ; an alkyl group having 1 to 4 carbon atoms; or CN; R ¹⁷ represents H; —COOR ⁴ An alkyl group having 1 to 17 carbon atoms; or a phenyl group; X represents —NH—; —NR ₇ —; —O—; —NH— (CH ₂ ) _p —NH—; or —O— (CH _{2) q} -NH- and represents; and index m is a number 0-19; n is a number 1-8 p is a number 0-4; q is a number 2-4, it is.

  The compounds of the general formulas (VII) and (VII-A) can be obtained by conventional methods, for example published by EP 434608 or H. Brunetti and CELuthi, Helv. Chim. Acta 55, 1566 (1972). It can be obtained analogously to known compounds by Friedel-Crafts addition of halotriazines to the corresponding phenols according to or analogously to the methods indicated in the product.

  Next, preferable examples of the compounds represented by the general formulas (VII) and (VII-A) are shown below, but the compounds that can be used in the present invention are not limited to these specific examples.

  In addition, the light stabilizers listed in the catalog of Asahi Denka, Plastic Additives, “Adeka Stub” can be used, and the light stabilizers and UV absorbers listed in the Chibin Special product guide of Ciba Special Chemicals can also be used. SESORB, SEENOX, SEETEC (all trade names), etc. in the catalog of SHIPROKASEI KAISYA can also be used. Jouhoku Chemical's UV absorbers and antioxidants can also be used. Kyosho's VIOSORB (trade name) and Yoshitomi's UV absorbers can also be used.

Furthermore, as described in JP-A No. 2001-187825, the use of a UV-absorbing compound having a melting point of 20 ° C. or less and a UV-absorbing compound having an ester group in the molecule is possible. It is also preferable to use a UV absorbing compound having a partition coefficient of 9.2 or more in a benzotriazole type in combination with a UV absorbing compound having a melting point of higher than 20 ° C. and a UV absorbing compound having a melting point higher than 20 ° C.
In particular, it is preferable to use an ultraviolet absorbing compound having a melting point of 20 ° C. or lower or an ultraviolet absorbent having a distribution coefficient of 9.2 or higher because the effect of reducing the wavelength dispersion of the Rth value is increased. The distribution coefficient is more preferably 9.3 or more.

  In the present invention, the wavelength dispersion adjusting agent has a transmittance of 50 when a spectral absorption spectrum is measured by comparing a sample of only the solvent in a 1 cm square cell with a concentration of 0.1 g / liter. % Having a function as an ultraviolet absorber having a spectral absorption spectrum in the range of 392 to 420 nm and a function as an ultraviolet absorber having a spectral absorption spectrum in the range of 360 to 390 nm. It is also preferable to use what has.

  In the cellulose derivative film of the present invention, it is preferable to adjust the amount of the wavelength dispersion modifier used according to the target wavelength dispersion of the optical performance. Although it depends on the wavelength dispersion of the optical performance to be obtained, the amount of the wavelength dispersion adjusting agent used is preferably 0.1 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the cellulose derivative. It is more preferable that the amount is not less than 25 parts by weight and not more than 25 parts by weight.

  The wavelength dispersion modifier may be added in advance when preparing a mixed solution of cellulose derivatives, but it may be added in advance at any time until the dope of the cellulose derivative is prepared and cast. Good. In the latter case, for example, a static mixer (Toray Industries, Inc.) can be used for in-line addition and mixing of a dope solution in which a cellulose derivative is dissolved in a solvent and a solution in which the above-described wavelength dispersion modifier and a small amount of cellulose derivative are dissolved. An in-line mixer such as SWJ (Toray Static In-Pipe Mixer Hi-Mixer) is preferably used. A matting agent may be mixed at the same time with the wavelength dispersion adjusting agent to be added later, or additives such as a retardation control agent, a plasticizer, a deterioration preventing agent, and a peeling accelerator may be mixed. When using an in-line mixer, it is preferable to concentrate and dissolve under high pressure, and the type of the pressurized container is not particularly limited, as long as it can withstand a predetermined pressure and can be heated and stirred under pressure. In addition to the pressure vessel, other instruments such as a pressure gauge and a thermometer are appropriately disposed. The pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or by increasing the vapor pressure of the solvent by heating. Heating is preferably performed from the outside. For example, a jacket type is preferable because temperature control is easy. The heating temperature with the addition of the solvent is preferably not less than the boiling point of the solvent used and in a range where the solvent does not boil, and is preferably set to a range of 30 to 150 ° C, for example. The pressure is adjusted at a set temperature so that the solvent does not boil. After dissolution, it is taken out from the container while cooling, or extracted from the container with a pump or the like and cooled with a heat exchanger or the like, and used for film formation. Although the cooling temperature at this time may be cooled to room temperature, it is more preferable to cool to a temperature 5 to 10 ° C. lower than the boiling point and perform casting at that temperature because the dope viscosity can be reduced.

[Matting agent fine particles]
It is preferable to add fine particles as a matting agent to the cellulose derivative film of the present invention. The fine particles used in the present invention include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, silica Mention may be made of magnesium and calcium phosphates. Fine particles containing silicon are preferable from the viewpoint of low turbidity, and silicon dioxide is particularly preferable. The fine particles of silicon dioxide preferably have a primary average particle diameter of 20 nm or less and an apparent specific gravity of 70 g / liter or more. Those having an average primary particle size as small as 5 to 16 nm are more preferred because they can reduce the haze of the film. The apparent specific gravity is preferably 90 to 200 g / liter or more, and more preferably 100 to 200 g / liter or more. A larger apparent specific gravity is preferable because a high-concentration dispersion can be produced, and haze and aggregates are improved.

  These fine particles usually form secondary particles having an average particle diameter of 0.1 to 3.0 μm, and these fine particles are present as aggregates of primary particles in the film, and 0.1 to 0.1 μm on the film surface. An unevenness of 3.0 μm is formed. The secondary average particle size is preferably from 0.2 μm to 1.5 μm, more preferably from 0.4 μm to 1.2 μm, and most preferably from 0.6 μm to 1.1 μm. The primary and secondary particle sizes were determined by observing the particles in the film with a scanning electron microscope and determining the diameter of a circle circumscribing the particles as the particle size. In addition, 200 particles were observed at different locations, and the average value was taken as the average particle size.

  As the fine particles of silicon dioxide, for example, commercially available products such as Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (above Nippon Aerosil Co., Ltd.) can be used. Zirconium oxide fine particles are commercially available, for example, under the trade names Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used.

  Among these, Aerosil 200V and Aerosil R972V are fine particles of silicon dioxide having a primary average particle diameter of 20 nm or less and an apparent specific gravity of 70 g / liter or more, and the coefficient of friction is maintained while keeping the turbidity of the optical film low. It is particularly preferable because it has a great effect of reducing the effect.

In order to obtain a cellulose derivative film having particles having a small secondary average particle diameter in the present invention, several methods are conceivable when preparing a dispersion of fine particles. For example, a fine particle dispersion prepared by stirring and mixing a solvent and fine particles is prepared in advance, and this fine particle dispersion is added to a small amount of a separately prepared cellulose derivative solution, stirred and dissolved, and further mixed with the main cellulose derivative solution (dope solution). There is a way. This method is a preferable preparation method in that the dispersibility of the silicon dioxide fine particles is good and the silicon dioxide fine particles are more difficult to reaggregate. In addition, a small amount of cellulose ester is added to the solvent, stirred and dissolved, and then the fine particles are added and dispersed with a disperser to make this fine particle additive solution. There is also a way to do it. The present invention is not limited to these methods, but the concentration of silicon dioxide when the silicon dioxide fine particles are mixed and dispersed with a solvent or the like is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, and 15 to 20%. Mass% is most preferred. A higher dispersion concentration is preferable because the liquid turbidity with respect to the added amount is lowered, and haze and aggregates are improved. The addition amount of the matting agent fine particles in the final dope solution of cellulose derivative is preferably 0.01 to 1.0 g, more preferably 0.03 to 0.3 g, and 0.08 to 0.16 g per 1 m ^3. Most preferred. Further, the blending amount of the matting agent fine particles is preferably 0.01 to 2.0 parts by mass, and more preferably 0.01 to 1.0 part by mass with respect to 100 parts by mass of the cellulose derivative.

  The solvent used is preferably lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol and the like. Although it does not specifically limit as solvents other than a lower alcohol, It is preferable to use the solvent used at the time of film forming of a cellulose ester.

[Plasticizer, degradation inhibitor, release agent]
In addition to the wavelength dispersion adjusting agent, various additives (for example, a plasticizer, a deterioration inhibitor, a release agent, an infrared absorber, etc.) can be added to the cellulose derivative film of the present invention. , They may be solid or oily. That is, the melting point and boiling point are not particularly limited. For example, it is a mixture of plasticizers of 20 ° C. or lower and 20 ° C. or higher, and is described in, for example, JP-A No. 2001-151901. Furthermore, as an infrared absorber, it describes in Unexamined-Japanese-Patent No. 2001-194522, for example. In addition, the addition time may be any time in the dope production process, but it is preferable to add an additive at the end of the dope production process. Furthermore, the amount of each additive added is not particularly limited as long as the function is exhibited. Moreover, when a cellulose derivative 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. For these details, materials described in detail on pages 16 to 22 in the Japan Institute of Invention Disclosure Technical Bulletin (Public Technical No. 2001-1745, published on March 15, 2001, Japan Institute of Invention) are preferably used.

[Organic solvent for cellulose derivative solution]
In this invention, it is preferable to manufacture a cellulose derivative film by the solvent cast method, and a film is manufactured using the solution (dope) which melt | dissolved the cellulose derivative in the organic solvent.
In the present invention, the gelation of an undried dope film formed by casting a cellulose derivative solution on a metal support in the casting step described later is promoted, and the peelability is improved. For the purpose of increasing the elastic modulus of the film, it is preferable to contain at least two alcohol solvents as the organic solvent (solvent) for dissolving the cellulose derivative. As the alcohol solvent, any alcohol may be used as long as it has 1 to 8 carbon atoms. Moreover, it is preferable that at least 1 type is a C3-C8 alcohol, and it is more preferable that it is C4-C6. Further, the alcohol content in the solvent composition may be 0.1 to 40%, more preferably 1.0 to 30%, still more preferably 2.0 to 20%.
The organic solvent preferably used as the main solvent of the present invention is preferably a solvent selected from esters, ketones, ethers having 3 to 12 carbon atoms, and halogenated hydrocarbons having 1 to 7 carbon atoms. Esters, ketones and ethers may have a cyclic structure. A compound having two or more functional groups of esters, ketones and ethers (that is, —O—, —CO— and —COO—) can also be used as a main solvent. 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. The main solvent is preferably a chlorinated solvent or an acetate ester, more preferably methylene chloride or methyl acetate.

As described above, chlorine-based halogenated hydrocarbons may be used as the main solvent for the cellulose derivative film of the present invention, and as described in JIII Journal of Technical Disclosure 2001-1745 (pages 12-16), A chlorinated solvent may be used as the main solvent.

  In addition, the solvent for the cellulose derivative solution and film of the present invention is disclosed in the following published patent gazette including the dissolution method, and is a preferred embodiment. They are, for example, JP 2000-95876, JP 12-95877, JP 10-324774, JP 8-152514, JP 10-330538, JP 9-95538, JP 9-95557, JP 10-10. -235664, JP-A-12-63534, JP-A-11-21379, JP-A-10-182853, JP-A-10-278056, JP-A-10-279702, JP-A-10-323853, JP-A-10-237186, JP-A-11-60807. JP-A-11-152342, JP-A-11-292898, JP-A-11-60752, JP-A-11-60752, and the like. According to these publications, not only the preferred solvent for the cellulose derivative of the present invention, but also the physical properties of the solution and coexisting substances to be coexisted are described, which is also a preferred embodiment in the present invention.

[Manufacturing process of cellulose derivative film]
[Dissolution process]
Preparation of the cellulose derivative solution (dope) of the present invention is not particularly limited in its dissolution method, and may be performed at room temperature or further by a cooling dissolution method or a high temperature dissolution method, or a combination thereof. Regarding the preparation of the cellulose derivative solution in the present invention, as well as the solution concentration and filtration steps accompanying the dissolution step, the Technical Report of the Invention Association (Public Technical Number 2001-1745, published on March 15, 2001, Invention Association) The manufacturing processes described in detail on pages 22 to 25 are preferably used.

(Transparency of dope solution)
The dope transparency of the cellulose derivative solution of the present invention is preferably 85% or more. More preferably, it is 88% or more, and more preferably 90% or more. In the present invention, it was confirmed that various additives were sufficiently dissolved in the cellulose derivative dope solution. As a specific method for calculating the dope transparency, the dope solution was poured into a 1 cm square glass cell, and the absorbance at 550 nm was measured with a spectrophotometer (UV-3150, Shimadzu Corporation). Only the solvent was measured in advance as a blank, and the transparency of the cellulose derivative solution was calculated from the ratio to the absorbance of the blank.

[Casting, drying, winding process]
Next, a method for producing a film using the cellulose derivative solution of the present invention will be described. As the method and equipment for producing the cellulose derivative film of the present invention, a solution casting film forming method and a solution casting film forming apparatus used for producing a conventional cellulose triacetate film are used. The dope (cellulose derivative 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. The both ends of the obtained web are sandwiched between clips, transported by a tenter while holding the width and dried, and then the obtained film is mechanically transported by a roll group of a drying device, dried, and then rolled by a winder Wind up to a predetermined length. The combination of the tenter and the roll group dryer varies depending on the purpose. In the solution casting film forming method used for the functional protective film that is an optical member for electronic displays, which is the main use of the cellulose derivative film of the present invention, in addition to the solution casting film forming apparatus, an undercoat layer, In many cases, a coating apparatus is added for surface processing of a film such as an antistatic layer, an antihalation layer, or a protective layer. These are described in detail on pages 25 to 30 in the Japan Society for Invention and Innovation Technical Report (Public Technical Number 2001-1745, published on March 15, 2001, Japan Society of Inventions). Including), metal support, drying, peeling and the like, and can be preferably used in the present invention.
As the metal support, a method using an endless belt stretched between two drums as a support, or a method using the drum itself as an endless support is generally used, but productivity is improved. From the viewpoint, use a method in which the drum itself is used as an endless support, use a cellulose derivative solution containing a solvent containing two or more alcohol solvents as the dope solution, and further adjust the temperature of the drum to an appropriate temperature. Thus, the gelation of the web is promoted, the peelability of the web from the support can be improved, and as a result, the productivity can be improved.
Moreover, 10-200 micrometers is preferable, as for the thickness of the cellulose derivative film produced, 20-150 micrometers is more preferable, and 30-100 micrometers is further more preferable.

[Change in optical performance of film after high humidity treatment]
Regarding the change in the optical performance due to the environmental change of the cellulose derivative film of the present invention, Re (400), Re (700), Rth (400) and Rth of the film conditioned for 240 hours in an environment of 90% RH at 60 ° C. The amount of change in (700) is preferably 0 nm or more and 15 nm or less. More preferably, it is 0 nm or more and 12 nm or less, and more preferably 0 nm or more and 10 nm or less.
[Change in optical performance of film after high temperature treatment]
Further, it is preferable that the amount of change in Re (400), Re (700), Rth (400) and Rth (700) of the film conditioned at 80 ° C. for 240 hours is from 0 nm to 15 nm. More preferably, it is 0 nm or more and 12 nm or less, and further preferably 0 nm or more and 10 nm or less.
[Compound volatilization after film heat treatment]
The compound having the maximum value of the spectral absorption spectrum in the range of 250 nm to 400 nm, which can be preferably used in the cellulose derivative film of the present invention, has a volatilization amount of the compound from the film conditioned at 80 ° C. for 240 hours. % Or more and 30% or less is preferable. More preferably, it is 0% or more and 25% or less, and more preferably 0% or more and 20% or less.
The amount of volatilization from the film was determined by dissolving the film conditioned at 80 ° C. for 240 hours and the film not conditioned in a solvent, detecting the compound by high performance liquid chromatography, and determining the peak area of the compound in the film. The remaining compound amount is calculated by the following formula.
Volatilization amount (%) = {(remaining compound amount in untreated product) − (remaining compound amount in treated product)} / (remaining compound amount in untreated product) × 100

[Glass Transition Temperature Tg of Film]
The glass transition temperature Tg of the cellulose derivative film of the present invention is preferably 80 to 165 ° C. From the viewpoint of heat resistance, Tg is more preferably 100 to 160 ° C, and particularly preferably 110 to 150 ° C. The glass transition temperature Tg is measured with a differential scanning calorimeter (for example, DSC2910, manufactured by TA Instruments) using a cellulose derivative film sample of the present invention 10 mg at a temperature rising / falling rate of 5 ° C./min. Measurement is performed to calculate the glass transition temperature Tg.

[Haze of film]
The haze of the cellulose derivative film of the present invention is preferably 0.0% to 2.0%. More preferably, it is 0.0% to 1.5%, and more preferably 0.0% to 1.0%. As an optical film, the transparency of the film is important. The haze is measured by measuring a cellulose derivative film sample 40 mm × 80 mm of the present invention at 25 ° C. and 60% RH with a haze meter (HGM-2DP, Suga Test Instruments) according to JIS K-6714.

[Retardation]
In the present specification, the Re retardation value and the Rth retardation value of the cellulose derivative film (transparent support) are calculated based on the following. Re ₍ λ ₎ and Rth ₍ λ ₎ respectively represent in-plane retardation and retardation in the thickness direction at the wavelength λ. Re ₍ λ ₎ is measured by making light with a wavelength of λ nm incident in the normal direction of the film in KOBRA 21ADH (manufactured by Oji Scientific Instruments).

Rth ₍ λ ₎ is incident on light having a wavelength of λ nm from the direction inclined by + 40 ° with respect to the normal direction of the film, with Re ₍ λ ₎ and the slow axis (determined by KOBRA 21ADH) as the tilt axis (rotation axis). The retardation value measured in this manner and the retardation value measured by making light of wavelength λ nm incident from a direction inclined by −40 ° with respect to the film normal direction with the slow axis as the tilt axis (rotation axis). KOBRA 21ADH calculates based on the retardation value measured in the direction, the assumed value of the average refractive index, and the input film thickness value. Furthermore, KOBRA 21ADH calculates nx, ny, nz, and Rth by inputting an assumed value of average refractive index of 1.48 and a film thickness. In addition, the retardation of wavelengths that cannot be directly measured was obtained by curve fitting from the retardation values of peripheral wavelengths using the Cauchy equation.
In the present invention, Rth ₍₅₈₉₎ of the cellulose derivative film preferably satisfies the following mathematical formula (2). More preferably, it is satisfy | filling the following numerical formula (2-1), Most preferably, it is satisfying the following numerical formula (2-2).
Formula (2); −600 nm ≦ Rth ₍₅₈₉₎ ≦ 0 nm
Formula (2-1): −500 nm ≦ Rth ₍₅₈₉₎ ≦ −20 nm
Formula (2-2); −400 nm ≦ Rth ₍₅₈₉₎ ≦ −40 nm
Here, Rth ₍ λ ₎ is retardation in the film thickness direction of the film at the wavelength λnm.
Further, as a result of intensive studies, the inventors of the present invention did not color the film by using a compound having absorption in the ultraviolet region having a wavelength of 250 to 400 nm, and the Re ₍ λ ₎ and Rth ₍ λ ₎ of the film. The chromatic dispersion can be controlled. As a result, the difference between Re and Rth at wavelengths of 400 nm and 700 nm, the values of (Re ₍₄₀₀₎ −Re ₍₇₀₀₎ ) and (Rth ₍₄₀₀₎ −Rth ₍₇₀₀₎ ) The present inventors have found that it can be reduced and have completed the present invention.

[Humidity dependency of Re and Rth of film]
It is preferable that both Re and Rth of the cellulose derivative film of the present invention have a small change due to humidity. Specifically, it is preferable that the front retardation Re ₍ λ ₎ of the film and the retardation Rth ₍ λ _{) in the} film thickness direction (λ represents a wavelength (nm)) satisfy the following formula (4).
Formula (4)
(Rth _A ) − (Rth _B ) ≦ 30 nm and (Re _A ) − (Re _B ) ≦ 10 nm,
(Here, (Rth _A ) represents Rth ₍₅₈₉₎ under the conditions of 25 ° C. and 10% RH, and (Rth _B ) represents Rth ₍₅₈₉₎ under the conditions of 25 ° C. and 80% RH. (Re _A ) represents Re ₍₅₈₉₎ under conditions of 25 ° C. and 10% RH, and (Re _B ) represents Re ₍₅₈₉₎ under conditions of 25 ° C. and 80% RH.)
For Rth, (Rth _A )-(Rth _B ) is preferably 0 to 25 nm, more preferably 0 to 20 nm, and Re is more preferably (Re _A )-(Re _B ). Is 0 to 8 nm, more preferably 0 to 5 nm.

[Equilibrium moisture content of film]
The equilibrium moisture content of the cellulose derivative film of the present invention is such that when used as a protective film for a polarizing plate, the adhesiveness with a water-soluble polymer such as polyvinyl alcohol is not impaired, and the durability of the polarizing plate at high temperature and high humidity is sufficiently good. Therefore, the equilibrium moisture content at 25 ° C. and 80% RH is preferably 3.0% or less, and more preferably 0.1 to 3.0% regardless of the film thickness. It is more preferably 0.1 to 2.5%, and particularly preferably 0.1 to 2.0%. By controlling the equilibrium moisture content within the above range, changes in the polarization performance of the polarizing plate under high temperature and high humidity can be reduced.
Equilibrium moisture content was determined by allowing a cellulose derivative film sample 7 mm × 35 mm of the present invention to stand at 25 ° C. and 80% RH for 6 hours or longer, adjusting the humidity, and then measuring the moisture, measuring device, sample drying device (CA-03, VA- 05, both measured by the Karl Fischer method (Mitsubishi Chemical Corporation), by dividing the amount of water (g) by the sample mass (g).

[Method for evaluating cellulose derivative film of the present invention]
The cellulose derivative film of the present invention was evaluated by the following method.

(Transmittance)
The transmittance of visible light (615 nm) is measured on a 20 mm × 70 mm sample at 25 ° C. and 60% RH with a transparency measuring instrument (AKA phototube colorimeter, KOTAKI Corporation).

(Surface energy)
The surface energy of the cellulose derivative film of the present invention can be measured by the following method. That is, the sample is placed horizontally on a horizontal table, and a contact angle of water and methylene iodide on the sample surface after a fixed time has elapsed after placing a certain amount of water and methylene iodide on the sample surface. From the measured contact angle, the surface energy is obtained by the method of Owens.

[In-plane variation of retardation of cellulose derivative film]
The cellulose derivative film of the present invention preferably satisfies the following formula.
| Re _(MAX) −Re _(MIN) | ≦ 3 and | Rth _(MAX) −Rth _(MIN) | ≦ 5
[In the formula, Re _(MAX) and Rth _(MAX) are the maximum retardation values of 1 m square film cut out arbitrarily, and Re _(MIN) and Rth _(MIN) are the minimum values. ]

[Retention of film]
In the cellulose derivative film of the present invention, retention of various compounds added to the film is required. Specifically, it is preferable that the mass change of the film when the cellulose derivative film of the present invention is allowed to stand at 80 ° C. and 90% RH for 48 hours is 0 to 5%. More preferably, it is 0 to 3%, and still more preferably 0 to 2%.
<Reservation evaluation method>
The sample was cut into a size of 10 cm × 10 cm, and after adjusting the mass after conditioning for 24 hours in an atmosphere of 23 ° C. and 55% RH, the sample was allowed to stand for 48 hours at 80 ± 5 ° C. and 90 ± 10% RH. did. Lightly wipe the surface of the sample after conditioning, measure the mass after conditioning for 1 day at 23 ° C. and 55% RH, and calculate retention by the following method.
Retention property (mass%) = {(mass before leaving-mass after leaving) / mass before leaving} × 100

[Functional layer]
The cellulose derivative film of the present invention is applied to optical uses and photographic light-sensitive materials as its uses. In particular, the optical application is preferably a liquid crystal display device, the liquid crystal display device is a liquid crystal cell that carries a liquid crystal between two electrode substrates, two polarizing plates arranged on both sides thereof, Further, it is preferable that at least one optical compensation film (hereinafter also referred to as an optical compensation sheet) is disposed between the liquid crystal cell and the polarizing plate. As these liquid crystal display devices, TN, IPS, FLC, AFLC, OCB, STN, ECB, VA and HAN are preferable. IPS and VA are particularly preferable.
In that case, when using the cellulose derivative film of this invention for the above-mentioned optical use, providing various functional layers is implemented. These are, for example, an antistatic layer, a cured resin layer (transparent hard coat layer), an antireflection layer, an easy adhesion layer, an antiglare layer, an optical compensation layer, an alignment layer, a liquid crystal layer, and the like. These functional layers and materials for which the cellulose derivative film of the present invention can be used include surfactants, slip agents, matting agents, antistatic layers, hard coat layers, and the like. No. 2001-1745 (issued on March 15, 2001, Invention Association), which is described in detail on pages 32 to 45, and can be preferably used in the present invention.

[Application (Polarizing plate)]
As a use of the cellulose derivative film of the present invention, a protective film for a polarizing plate is particularly mentioned.
That is, the polarizing plate of the present invention is a polarizing plate having a polarizing film and two transparent protective films (protective films) disposed on both sides thereof, and at least one of the transparent protective films is the cellulose derivative film of the present invention described above. Or it is the optical compensation film which provided the optically anisotropic layer on the cellulose acylate derivative film, It is characterized by the above-mentioned.
The polarizing plate is composed of a polarizing film and a protective film for protecting both surfaces of the polarizing film, and further comprises 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 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 cell. Moreover, a separate film is used in order to cover the contact bonding layer bonded to a liquid crystal cell, and is used for the surface side which bonds a polarizing plate to a liquid crystal cell. As the protective film, the cellulose derivative film of the present invention may be used.

The polarizing film is preferably a coating type polarizing film typified by Optiva, or a polarizing film composed of a binder and iodine or a dichroic dye.
Iodine and dichroic dye in the polarizing film exhibit deflection performance by being oriented in the binder. It is preferable that the iodine and the dichroic dye are aligned along the binder molecule, or the dichroic dye is aligned in one direction by self-assembly such as liquid crystal.
Currently, a general-purpose polarizing film is produced by immersing a stretched polymer in a solution of iodine or dichroic dye in a bath and allowing the iodine or dichroic dye to penetrate into the binder. Is common. In general-purpose polarizing films, iodine or dichroic dye is distributed about 4 μm (about 8 μm on both sides) from the polymer surface, and a thickness of at least 10 μm is necessary to obtain sufficient polarization performance. The penetrability can be controlled by the solution concentration of iodine or dichroic dye, the temperature of the bath, and the immersion time.

The binder of the polarizing film may be cross-linked. As the crosslinked binder, a polymer that can be crosslinked per se can be used. A polarizing film can be formed by reacting a polymer having a functional group or a binder obtained by introducing a functional group into a polymer between the binders by light, heat, or pH change.
Moreover, you may introduce | transduce a crosslinked structure into a polymer with a crosslinking agent. It can be formed by cross-linking between binders by introducing a bonding group derived from the cross-linking agent between binders using a cross-linking agent which is a compound having high reaction activity.
Crosslinking is generally carried out by applying a coating solution containing a polymer or a mixture of a polymer and a crosslinking agent on a transparent support and then heating. Since it is sufficient if durability can be secured at the final product stage, the crosslinking treatment may be performed at any stage until the final polarizing plate is obtained.

As the binder of the polarizing film, either a polymer that can be crosslinked per se or a polymer that is crosslinked by a crosslinking agent can be used. Examples of polymers include polymethyl methacrylate, polyacrylic acid, polymethacrylic acid, polystyrene, gelatin, polyvinyl alcohol, modified polyvinyl alcohol, poly (N-methylolacrylamide), polyvinyltoluene, chlorosulfonated polyethylene, nitrocellulose, chlorinated Polyolefin (eg, polyvinyl chloride), polyester, polyimide, polyvinyl acetate, polyethylene, carboxymethylcellulose, polypropylene, polycarbonate and copolymers thereof (eg, acrylic acid / methacrylic acid copolymer, styrene / maleimide copolymer, styrene) / Vinyl toluene copolymer, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer). Water-soluble polymers (eg, poly (N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvinyl alcohol and modified polyvinyl alcohol) are preferred, gelatin, polyvinyl alcohol and modified polyvinyl alcohol are more preferred, and polyvinyl alcohol and modified polyvinyl alcohol are most preferred. .

The saponification degree of polyvinyl alcohol and modified polyvinyl alcohol is preferably 70 to 100%, more preferably 80 to 100%, and most preferably 95 to 100%. As for the polymerization degree of polyvinyl alcohol, 100-5000 are preferable.
The modified polyvinyl alcohol is obtained by introducing a modifying group into polyvinyl alcohol by copolymerization modification, chain transfer modification or block polymerization modification. In the copolymerization modification, COONa, Si (OH) ₃ , N (CH ₃ ) ₃ .Cl, C ₉ H ₁₉ COO, SO ₃ Na, C ₁₂ H ₂₅ can be introduced as modifying groups. In chain transfer modification, COONa, SH, or SC ₁₂ H ₂₅ can be introduced as a modifying group. The degree of polymerization of the modified polyvinyl alcohol is preferably 100 to 3000. The modified polyvinyl alcohol is described in JP-A-8-338913, JP-A-9-152509 and JP-A-9-316127.
Unmodified polyvinyl alcohol and alkylthio-modified polyvinyl alcohol having a saponification degree of 85 to 95% are particularly preferable.
Two or more kinds of polyvinyl alcohol and modified polyvinyl alcohol may be used in combination.

When a large amount of the crosslinking agent for the binder is added, the heat and humidity resistance of the polarizing film can be improved. However, when 50 mass% or more of a crosslinking agent is added to the binder, the orientation of iodine or the dichroic dye is lowered. 0.1-20 mass% is preferable with respect to a binder, and, as for the addition amount of a crosslinking agent, 0.5-15 mass% is more preferable.
The binder contains some crosslinking agent that has not reacted even after the crosslinking reaction has been completed. However, the amount of the remaining crosslinking agent is preferably 1.0% by mass or less in the binder, and more preferably 0.5% by mass or less. When the crosslinking agent is contained in the binder layer in an amount exceeding 1.0% by mass, there may be a problem in durability. That is, when a polarizing film having a large amount of residual crosslinking agent is incorporated in a liquid crystal display device and used for a long time or left in a high-temperature and high-humidity atmosphere for a long time, the degree of polarization may decrease. The crosslinking agent is described in US Reissue Patent 23297. Boron compounds (eg, boric acid, borax) can also be used as a crosslinking agent.

  As the dichroic dye, an azo dye, stilbene dye, pyrazolone dye, triphenylmethane dye, quinoline dye, oxazine dye, thiazine dye or anthraquinone dye is used. The dichroic dye is preferably water-soluble. The dichroic dye preferably has a hydrophilic substituent (eg, sulfo, amino, hydroxyl). Examples of dichroic dyes include C.I. I. Direct Yellow 12, C.I. I. Direct Orange 39, C.I. I. Direct Orange 72, C.I. I. Direct Red 39, C.I. I. Direct Red 79, C.I. I. Direct Red 81, C.I. I. Direct Red 83, C.I. I. Direct Red 89, C.I. I. Direct Violet 48, C.I. I. Direct Blue 67, C.I. I. Direct Blue 90, C.I. I. Direct Green 59, C.I. I. Acid Red 37 is included. As for the dichroic dyes, those described in JP-A-1-161202, 1-172906, 1-172907, 1-183602, 1-248105, 1-265205, 7-261024 are used. There are descriptions in each publication. The dichroic dye is used as a free acid or an alkali metal salt, ammonium salt or amine salt. By blending two or more kinds of dichroic dyes, polarizing films having various hues can be produced. A polarizing film using a compound (pigment) that exhibits a black color when the polarization axes are orthogonal to each other, or a polarizing film or a polarizing plate in which various dichroic molecules are blended so as to exhibit a black color, have both a single-plate transmittance and a polarizability. It is excellent and preferable.

In the present invention, the single plate transmittance, parallel transmittance, and orthogonal transmittance of the polarizing plate were measured using UV3100PC (manufactured by Shimadzu Corporation). In the measurement, the measurement was performed in the range of 380 nm to 780 nm under the condition of 25 ° C. and 60% RH, and the average value of 10 measurements was used for each of the single plate, parallel and orthogonal transmittances. The polarizing plate durability test was performed as follows in two types of forms: (1) only the polarizing plate and (2) a polarizing plate attached to glass via an adhesive. The measurement of only the polarizing plate was performed by preparing two identical ones that were combined and orthogonalized so that an optical compensation film was sandwiched between two polarizers. Two samples (about 5 cm × 5 cm) are prepared by attaching a polarizing plate on glass so that the optical compensation film is on the glass side. In the single-plate transmittance measurement, the film side of this sample was set facing the light source. Each of the two samples was measured, and the average value was taken as the transmittance of the single plate. The preferable range of the polarization performance is 40.0 ≦ TT ≦ 45.0, 30.0 ≦ PT ≦ 40 in the order of single plate transmittance (TT), parallel transmittance (PT), and orthogonal transmittance (CT), respectively. 0.0, CT ≦ 2.0, and more preferable ranges are 40.2 ≦ TT ≦ 44.8, 32.2 ≦ PT ≦ 39.5, and CT ≦ 1.6, and a more preferable range is 41. 0.0 ≦ TT ≦ 44.6, 34 ≦ PT ≦ 39.1, and CT ≦ 1.3.
The degree of polarization P is calculated from these transmittances, and the greater the degree of polarization P is, the less light leaks when arranged in a cross, indicating that the performance of the polarizing plate is higher. The degree of polarization P is preferably 95.0% or more, more preferably 96.0% or more, and further preferably 97.0% or more.

In the polarizing plate of the present invention, T ₍₃₈₀₎ , T ₍₄₁₀₎ , and T ₍₇₀₀₎ are at least one of the following formulas (e) to (g), where T ₍ λ ₎ is the orthogonal transmittance at wavelength λ. It is preferable to satisfy one or more.
(E) T ₍₃₈₀₎ ≦ 2.0
(F) T ₍₄₁₀₎ ≦ 1.0
(G) T ₍₇₀₀₎ ≦ 0.5
More preferably, T ₍₃₈₀₎ ≤1.95, T ₍₄₁₀₎ ≤0.9, T ₍₇₀₀₎ ≤0.49, and even more preferably T ₍₃₈₀₎ ≤1.90, T ( ₍₄₁₀₎ ). ≦ 0.8 and T ₍₇₀₀₎ ≦ 0.48.
The polarizing plate of the present invention has an orthogonal single plate transmittance change ΔCT and a polarization degree change ΔP of at least the following formulas (h) and (i) when left at 60 ° C. and 95% RH for 650 hours. It is preferable to satisfy one or more.
(H) −0.6 ≦ ΔCT ≦ 0.6
(I) −0.3 ≦ ΔP ≦ 0.0
In the polarizing plate of the present invention, the amount of change ΔCT and the degree of polarization change ΔP of the orthogonal single plate when the state is adjusted for 650 hours at 80 ° C. are at least one of the following formulas (l) and (m). It is preferable to satisfy.
(H) −0.6 ≦ ΔCT ≦ 0.6
(I) −0.3 ≦ ΔP ≦ 0.0
In the polarizing plate durability test, the amount of change is preferably smaller.

(Configuration of liquid crystal display device)
In a liquid crystal display device, a liquid crystal cell is usually disposed between two polarizing plates, but the cellulose derivative film of the present invention can provide excellent display properties regardless of where it is disposed. In particular, since the protective film of the polarizing plate on the outermost surface of the liquid crystal display device is provided with a transparent hard coat layer, an antiglare layer, an antireflection layer, etc., the cellulose derivative film of the present invention is used for this part. Is particularly preferred.

  In producing the polarizing plate of the present invention, in order to use the cellulose derivative film of the present invention as a protective film for the polarizing film (protective film for polarizing plate), the surface of the side to be bonded to the polarizing film and polyvinyl alcohol are the main components. It is necessary to improve the adhesiveness with the polarizing film. If the adhesiveness is insufficient, the workability for use in a panel such as a liquid crystal display device after manufacturing a polarizing plate is poor, or the durability is insufficient and the film is peeled off after long-term use. Is a problem. For adhesion, a pressure-sensitive adhesive can be used, and examples of the component of the pressure-sensitive adhesive include polyvinyl alcohol pressure-sensitive adhesives such as polyvinyl alcohol and polyvinyl butyral, vinyl latex such as butyl acrylate, and the like. In consideration of adhesiveness, the surface energy should be considered as an index, and the surface energy of the pressure-sensitive adhesive layer made of polyvinyl alcohol, which is the main component of the polarizing film, or a pressure-sensitive adhesive mainly composed of polyvinyl alcohol or vinyl latex If the surface energy of the protective film to be bonded is closer, the bondability and the workability and durability of the bonded polarizing plate are further improved. For these reasons, the surface energy on the side to be bonded to the polarizing film or the pressure-sensitive adhesive is brought into the desired range by a surface treatment such as a hydrophilization treatment, thereby sufficiently adhering to the polarizing film containing polyvinyl alcohol as a main component. Can be granted.

  Since the cellulose derivative film of the present invention usually contains an additive such as a compound that reduces optical anisotropy and a wavelength dispersion adjusting agent, the surface of the film is more hydrophobic. Therefore, it is more necessary to improve the bonding property by the hydrophilization treatment described later in order to impart the workability and durability of the polarizing plate.

  The surface energy of the film after film formation before performing surface treatment such as hydrophilization treatment is hydrophobized because of the use of the additive, and the humidity dependence of the optical properties and mechanical properties of the film, From the viewpoint of ease of processing for improving the bonding property, 30 mN / m or more and 50 mN / m or less is preferable, and 40 mN / m or more and 48 mN / m or less is more preferable. When the surface energy before the treatment is less than 30 mN / m, a large amount of energy is required to improve the bonding property by the hydrophilization treatment described later, and as a result, the film characteristics are deteriorated or the productivity is compatible. It becomes difficult. On the other hand, when the surface energy before the treatment exceeds 50 mN / m, the hydrophilicity of the film itself is too large, and the optical performance and mechanical properties of the film are too dependent on humidity, which causes a problem.

  Further, the surface energy of the polyvinyl alcohol surface is in the range of 60 mN / m or more and 80 mN / m or less although it depends on the additive used in combination, the degree of drying and the pressure-sensitive adhesive used. The surface energy of the surface of the film of the present invention to be bonded to the polarizing film is preferably from 50 mN / m to 80 mN / m, more preferably from 60 mN / m to 75 mN / m, and more preferably from 65 mN / m to 75 mN. / M or less is more preferable.

[Surface treatment such as hydrophilization]
The hydrophilic treatment of the film surface of the present invention can be performed by a known method. Examples thereof include a method of modifying the film surface by corona discharge treatment, glow discharge treatment, ultraviolet irradiation treatment, flame treatment, ozone treatment, acid treatment, alkali treatment, and the like. The glow discharge treatment here may be low-temperature plasma that occurs under a low pressure gas of 10 ^{−3 to} 20 Torr (0.133 to 2660 Pa), and plasma treatment under atmospheric pressure is also preferable. Examples of the plasma-excitable gas that is plasma-excited under the above conditions include chlorofluorocarbons such as argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, and tetrafluoromethane, and mixtures thereof. Details of these are described in detail in pages 30 to 32 of the Invention Association Public Technical Bulletin No. 2001-1745 (issued on March 15, 2001, Invention Association), and preferably used in the present invention. be able to.

[Alkaline saponification]
Among these, alkali saponification treatment is particularly preferable, and it is extremely effective as the surface treatment of the cellulose derivative film. The following method is mentioned as a processing method.

(1) Immersion method This is a technique in which a film is immersed in an alkaline solution under appropriate conditions to saponify all surfaces having reactivity with alkali on the entire surface of the film, and no special equipment is required. It is preferable from the viewpoint of cost. The alkaline liquid is preferably a sodium hydroxide aqueous solution. A preferred concentration is 0.5 to 3 mol / l, particularly preferably 1 to 2 mol / l. The liquid temperature of a preferable alkali liquid is 25-70 degreeC, Most preferably, it is 30-60 degreeC.
After being immersed in the alkaline solution, it is preferable to sufficiently wash with water or neutralize the alkaline component by immersing in a dilute acid so that the alkaline component does not remain in the film.

By saponification treatment, both sides of the film are made hydrophilic. The protective film for polarizing plate is used by adhering a hydrophilic surface to a polarizing film.
The hydrophilized surface is effective for improving the adhesion with a polarizing film containing polyvinyl alcohol as a main component.

  On the other hand, in the dipping method, when the protective film has an antireflection layer laminated thereon, the main surface is damaged by alkali, so that it is important to set the minimum reaction conditions. When the contact angle to the water of the support on the opposite main surface is used as an index of damage received by the antireflection layer due to alkali, particularly when the support is a cellulose derivative, it is preferably 20 to 50 degrees, more preferably Is 30 to 50 degrees, more preferably 40 to 50 degrees. Within this range, the damage received by the antireflection film is not actually harmful, and the adhesiveness with the polarizing film can be maintained.

(2) Alkaline liquid coating method As a means for avoiding damage to the antireflection film in the above-described dipping method, the alkaline liquid is applied only to the main surface opposite to the main surface having the antireflection film under appropriate conditions, and heated. An alkaline solution coating method of washing with water and drying is preferably used. Examples of the alkaline solution and treatment include the contents described in JP-A No. 2002-82226 and WO 02/46809 pamphlet. However, since an equipment and a process for applying an alkaline solution are required separately, it is inferior to the immersion method (1) from the viewpoint of cost.

[Plasma treatment]
Examples of the plasma treatment used in the present invention include vacuum glow discharge, atmospheric pressure glow discharge, and the like, and other methods include flame plasma treatment and the like. For example, methods described in JP-A-6-123062, JP-A-11-293011, JP-A-11-5857 and the like can be used.

  According to the plasma treatment, a strong hydrophilicity can be imparted to the surface of the plastic film in the plasma. For example, in the above-described plasma generator using glow discharge, a film to be imparted with hydrophilicity is placed between opposing electrodes, a plasma-exciting gas is introduced into the apparatus, and a high-frequency voltage is applied between the electrodes. When applied, the gas can be plasma-excited and glow discharge can be performed between the electrodes to perform surface treatment. Among these, those using atmospheric pressure glow discharge are preferably used.

[Corona discharge treatment]
Among the surface treatments, corona discharge treatment is the most well-known method, and any conventionally known method such as Japanese Patent Publication Nos. 48-5043, 47-51905, and Japanese Patent Publication No. 47-28067. This can be achieved by the methods disclosed in Japanese Patent Publication Nos. 49-83767, 51-41770, 51-131576, and the like. As a corona treatment machine used for corona treatment, various commercially available corona treatment machines currently used as means for surface modification of plastic films and the like can be applied. Among them, a multi-knife electrode manufactured by SOFTAL is used. The corona treatment machine has a number of electrodes and has a structure that sends air between the electrodes. It can prevent the heating of the film and remove low molecules that appear on the film surface. Since it is very high and high corona treatment is possible, it is a corona treatment machine particularly useful for the present invention.

  In order to use the cellulose derivative film of the present invention for the purpose of a protective film for a polarizing plate, it is necessary to make the surface energy of at least one side of the cellulose derivative film within an appropriate range. I do. On the other hand, the surface treatment of the cellulose derivative film of the present invention may cause volatilization / elution / decomposition of additives contained in the cellulose derivative film, and the optical performance, film performance and durability of the cellulose derivative film may occur. There is a concern that the quality will deteriorate. Further, when volatilization or elution occurs, the processing system is further contaminated and the processability is lowered, so that the processing cannot be performed continuously. Therefore, it is necessary to suppress a decrease in the amount of the additive, and the amount of change in the amount of the additive due to the surface treatment is preferably 0.2% or less of the total amount of the additive before the treatment. It is more preferably 1% or less, and still more preferably 0.01% or less.

[Application (Optical compensation film)]
The cellulose derivative film of the present invention can be used in various applications, and is particularly effective when used as an optical compensation film for a liquid crystal display device.
The optical compensation film is generally used for a liquid crystal display device and refers to an optical material that compensates for a retardation, and is synonymous with a retardation plate, an optical compensation sheet, and the like. The optical compensation film has birefringence and is used for the purpose of removing the color of the display screen of the liquid crystal display device or improving the viewing angle characteristics. The cellulose derivative film of the present invention exhibits negative Rth, preferably Rth (589) is in the range of −600 ≦ Rth ≦ 0 nm, and is preferably used in combination with other optically anisotropic layers having birefringence. By doing so, an optical compensation film having desired optical performance can be obtained.

Therefore, when the cellulose derivative film of the present invention is used as an optical compensation film for a liquid crystal display device, Re (589) and Rth (589) of the optically anisotropic layer used together are Re (589) = 0 to 200 nm and | Rth (589 ) | = 0 to 400 nm is preferable, and any optically anisotropic layer may be used within this range. The optical performance and driving method of the liquid crystal cell of the liquid crystal display device in which the cellulose derivative film of the present invention is used are not limited, and any optical anisotropic layer required as an optical compensation film can be used in combination. The optically anisotropic layer used in combination may be formed from a composition containing a liquid crystalline compound or may be formed from a polymer film having birefringence.
The liquid crystal compound is preferably a discotic liquid crystal compound or a rod-like liquid crystal compound.

(Discotic liquid crystalline compounds)
Examples of discotic liquid crystalline compounds that can be used in the present invention include various documents (C. Destrade et al., Mol. Crysr. Liq. Cryst., 71, 111 (1981); Quarterly Chemical Review, No. 22, Chemistry of Liquid Crystals, Chapter 5, Chapter 10 Section 2 (1994); B. Kohne et al., Angew. Chem. Soc. Chem. Comm., Page 1794 (1985); J. Zhang et al., J. Am.Chem.Soc., 116, 2655 (1994)).

  In the optically anisotropic layer, the discotic liquid crystalline molecules are preferably fixed in an aligned state, and most preferably fixed by a polymerization reaction. The polymerization of discotic liquid crystalline molecules is described in JP-A-8-27284. In order to fix the discotic liquid crystalline molecules by polymerization, it is necessary to bond a polymerizable group as a substituent to the discotic core of the discotic liquid crystalline molecules. However, when the polymerizable group is directly connected to the disc-shaped core, it becomes difficult to maintain the orientation state in the polymerization reaction. Therefore, a linking group is introduced between the discotic core and the polymerizable group. JP-A-2001-4387 discloses a discotic liquid crystalline molecule having a polymerizable group.

(Bar-shaped liquid crystalline compound)
Examples of rod-like liquid crystalline compounds that can be used in the present invention include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, and cyano-substituted compounds. Phenyl pyrimidines, alkoxy substituted phenyl pyrimidines, phenyl dioxanes, tolanes and alkenyl cyclohexyl benzonitriles are included. Not only the above low-molecular liquid crystalline compounds but also high-molecular liquid crystalline compounds can be used.

  In the optically anisotropic layer, the rod-like liquid crystalline molecules are preferably fixed in an aligned state, and most preferably fixed by a polymerization reaction. Examples of polymerizable rod-like liquid crystalline compounds that can be used in the present invention include Makromol. Chem. 190, 2255 (1989), Advanced Materials 5, 107 (1993), US Pat. Nos. 4,683,327, 5,622,648, and 5,770,107, International Publication No. 95/22586. Pamphlet, pamphlet of 95/24455, pamphlet of 97/00600, pamphlet of 98/23580, pamphlet of 98/52905, JP-A-1-272551, JP-A-6-16616, 7-110469 And the compounds described in JP-A-11-80081, JP-A-2001-328773, and the like.

(Optically anisotropic layer made of polymer film)
The optically anisotropic layer may be formed from a polymer film. The polymer film is formed from a polymer that can exhibit optical anisotropy. Examples of such polymers include polyolefins (eg, polyethylene, polypropylene, norbornene-based polymers), polycarbonates, polyarylate, polysulfone, polyvinyl alcohol, polymethacrylates, polyacrylates and cellulose esters (eg, cellulose triacetate, Cellulose diacetate). Further, a copolymer or a polymer mixture of these polymers may be used.

  The optical anisotropy of the polymer film is preferably obtained by stretching treatment such as stretching. The stretching is preferably uniaxial stretching or biaxial stretching. Specifically, longitudinal uniaxial stretching using a difference in peripheral speed between two or more rolls, tenter stretching for grasping both sides of the polymer film and stretching in the width direction, or biaxial stretching in combination of these is preferable. In addition, tenter stretching or biaxial stretching is more preferable from the viewpoint of productivity of an optical compensation film and a polarizing plate described later. In addition, using two or more polymer films, the optical properties of the entire two or more films may satisfy the above conditions. The polymer film is preferably produced by a solvent cast method in order to reduce unevenness in birefringence. The thickness of the polymer film is preferably 20 to 500 μm, and most preferably 40 to 100 μm.

[Formation of optically anisotropic layer by application of polymer]
The formation of the optically anisotropic layer by the application of the polymer in the present invention is carried out by spreading the polymer liquefied by dissolving in a solvent on the cellulose derivative film of the present invention and drying the resulting laminate to the in-plane The treatment can be performed by orienting molecules. Thereby, an optical compensation film having desired optical characteristics can be obtained. Examples of the molecular orientation treatment include stretching treatment, shrinking treatment, or both, but stretching treatment is preferred from the viewpoint of productivity and ease of control.

The polymer is not particularly limited, and one or two or more appropriate light-transmitting materials can be used. Among them, a polymer capable of forming a film having a light transmittance of 75% or more, particularly 85% or more and excellent in light transmittance is preferable. From the viewpoint of stable mass productivity of the film, a solid polymer exhibiting positive birefringence that increases the retardation in the stretching direction can be preferably used.
Incidentally, examples of the above-described solid polymer include polyamide, polyester (for example, JP-T-10-5008048), polyimide (for example, JP-T 2000-511296), polyether ketone, and particularly polyaryl ether ketone (for example, JP-A-JP-A-10-50896). 2001-49110), polyamideimide (for example, Japanese Patent Laid-Open No. 61-162512), polyesterimide (for example, Japanese Patent Laid-Open No. 64-38472), and the like. For the formation of the birefringent film, one of the solid polymers or a mixture of two or more thereof can be used. Although there is no limitation in particular about the molecular weight of a solid polymer, generally it is 2000-1 million, Preferably it is 1500-750,000, More preferably, it is 1000-500,000 based on points, such as the workability to a film.

In forming the polymer film, various additives including stabilizers, plasticizers, metals, and the like can be blended as necessary. For liquefaction of the solid polymer, an appropriate method such as a method in which a thermoplastic solid polymer is heated and melted or a method in which a solid polymer is dissolved in a solvent to form a solution can be employed.
Solidification of the polymer (developing layer) developed on the cellulose derivative film is performed by cooling the developing layer in the former melt and removing the solvent from the developing layer and drying in the latter solution. be able to. For the drying, one or more of appropriate methods such as a natural drying (air drying) method, a heat drying method, particularly a heat drying method at 40 to 200 ° C., and a vacuum drying method can be employed. From the viewpoint of suppressing production efficiency and generation of optical anisotropy, a method of applying a polymer solution is preferable.

As said solvent, 1 type, or 2 or more types of suitable things, such as a methylene chloride, cyclohexanone, a trichloroethylene, tetrachloroethane, N-methylpyrrolidone, tetrahydrofuran, can be used, for example. From the viewpoint of the viscosity suitable for film formation, the solution is preferably a solution in which 2 to 100 parts by mass, preferably 5 to 50 parts by mass, particularly 10 to 40 parts by mass of the polymer are dissolved with respect to 100 parts by mass of the solvent.
For the development of the liquefied polymer, for example, spin coating method, roll coating method, flow coating method, printing method, dip coating method, casting film forming method, casting method such as bar coating method and gravure printing method, extrusion method, etc. The appropriate film forming method can be adopted. Among them, a solution film forming method such as a casting method can be preferably applied from the viewpoint of mass productivity of a film with little thickness unevenness and alignment strain unevenness. In particular, it is preferable to form a film by laminating a polymer liquefied by dissolving in a solvent on a cellulose derivative film by a co-casting method. In this case, as the polyimide, a solvent-soluble one prepared from an aromatic dianhydride and a polyaromatic diamine (see JP-A-8-511812) can be preferably used.

In the production method of the present invention in which the polymer is liquefied and spread on a cellulose derivative film and stretched or shrunk, the Rth is controlled in the formation process of the spread layer on the cellulose derivative film, and the laminate is stretched or shrunk. Thus, the molecules are oriented to control Re. Such a role-sharing method can achieve the purpose with a smaller stretching ratio than the conventional method of simultaneously controlling Rth and Re, such as a biaxial stretching method, and can achieve the characteristics of Rth and Re and the accuracy of the optical axis. There is an advantage in design and manufacturing that an excellent biaxial optical compensation film is easily obtained.

The molecular orientation treatment can be performed as a film stretching process or / and a shrinking process, and the stretching process can be performed, for example, as a stretching process. For the stretching treatment, one or two or more suitable methods such as a biaxial stretching method such as a sequential method or a simultaneous method, a uniaxial stretching method such as a free end method or a fixed end method can be applied. From the viewpoint of suppressing the bowing phenomenon, the uniaxial stretching method is preferable.
In this case, the stretching treatment temperature can be the same as that of the conventional one, for example, generally in the vicinity of the glass transition temperature of the solid polymer and above the glass transition temperature. For the purpose of further reducing the retardation of the stretched cellulose derivative film of the present invention, the stretching temperature is preferably in the vicinity of the glass transition temperature Tg of the cellulose derivative film, and the stretching may be performed at Tg−20 ° C. or higher. Preferably, stretching at Tg-10 ° C or higher is more preferable, and stretching at Tg or higher is more preferable.
Moreover, as a range of a preferable draw ratio, 1.03 times or more and 2.50 times or less are preferable, more preferably 1.04 times or more and 2 times or less, as a ratio of the film length after stretching to the film length before stretching. 20 times or less, more preferably 1.05 times or more and 1.80 times or less. When the draw ratio is 1.05 times or less, the draw ratio is insufficient for the purpose of forming the optically anisotropic layer described above. When the draw ratio is 2.50 times or more, the film durability test is performed. Later changes in curl and optical characteristics will increase.

On the other hand, the shrinkage treatment can be performed by, for example, a method in which a polymer film is applied and formed on a substrate, and a shrinkage force is applied by utilizing a dimensional change accompanying a temperature change of the substrate. In that case, it is also possible to use a base material imparted with a shrinking ability such as a heat-shrinkable film. At that time, it is desirable to control the shrinkage rate using a stretching machine or the like.
The birefringent film produced by the above method is suitably used as an optical compensation film that improves the viewing angle characteristics of a liquid crystal display device, and further improves productivity by making the liquid crystal display device thinner and reducing the number of production steps. Therefore, it is preferable to use it as a protective film for the polarizing plate in a form directly bonded to a polarizer (polarizing film). At this time, it is required that a polarizing plate using the optical compensation film can be provided at a lower cost and with a higher productivity, and it is desired to reduce the manufacturing process up to the polarizing plate with a higher productivity and a lower cost. Here, the optical compensation film of the present invention is used in the form of being bonded to a polarizer so that the in-plane Re expression direction of the optically anisotropic layer is perpendicular to the absorption axis of the polarizing plate. . Moreover, the polarizer of the general structure which consists of an iodine and PVA is produced by longitudinal uniaxial stretching, and the absorption axis of a polarizer becomes a longitudinal direction. Furthermore, in order to provide a polarizing plate using an optical compensation film having the above birefringent film with high productivity and low cost, it is first required to perform the above production process consistently by roll-to-roll. Due to these factors, in particular, from the viewpoint of productivity, as a method for producing an optical compensation film comprising the above birefringent film, the development layer comprising the above polymer is laminated on the cellulose derivative film of the present invention, and then the development layer is formed. It is preferable to perform the stretching treatment or the shrinking treatment so that the polymer is oriented in the width direction and Re is developed in the width direction. By using the roll-shaped optical compensation film thus produced as a protective film for a polarizer, it is possible to produce a polarizing plate having an effective optical compensation function using a roll-to-roll as it is.
Here, the roll-shaped film in the present invention refers to a film having a length of 1 m or more in the longitudinal direction and further wound three or more times in the longitudinal direction. In addition, roll-to-roll refers to any process that can be performed on a roll-shaped film, such as film formation or lamination / bonding with other roll-shaped films, surface treatment, heating / cooling treatment, stretching treatment / shrinking treatment, etc. Is to maintain a roll shape before and after applying, especially from the viewpoint of productivity, cost, handling,
It is preferable to perform the processing in a roll-to-roll manner.

The size of Rth and Re in the obtained birefringent film is determined depending on the type of solid polymer, the development method of the development layer such as the coating method of the liquefied material, the solidification method of the development layer such as the drying conditions, and the solid to be formed. It can be controlled by the thickness of the optical compensation layer made of a polymer. The general thickness of the solid polymer layer used as the optical compensation layer is 0.5 to 100 μm, preferably 1 to 50 μm, particularly 2 to 20 μm.
The birefringent film produced by this method may be used as it is, or may be bonded to another film with an adhesive or the like.

(Configuration of liquid crystal display device)
As described above, in the [functional layer], the liquid crystal display device includes a liquid crystal cell in which liquid crystal is supported between two electrode substrates, two polarizing plates disposed on both sides thereof, and the liquid crystal. It is preferable that at least one optical compensation film is disposed between the cell and the polarizing plate. When the cellulose acylate film is used as an optical compensation film, the transmission axis of the polarizing plate and the slow axis of the optical compensation film made of the cellulose acylate film may be arranged at any angle. The liquid crystal display device of the present invention is a liquid crystal display device having a liquid crystal cell and two polarizing plates arranged on both sides thereof, and at least one polarizing plate is the polarizing plate of the present invention. It is characterized by.
The liquid crystal layer of the liquid crystal cell is usually formed by sealing liquid crystal in a space formed by sandwiching a spacer between two substrates. The transparent electrode layer is formed on the substrate as a transparent film containing a conductive substance. The liquid crystal cell may further be provided with a gas barrier layer, a hard coat layer, or an undercoat layer (undercoat layer) (used for adhesion of the transparent electrode layer). These layers are usually provided on the substrate. The substrate of the liquid crystal cell generally has a thickness of 50 μm to 2 mm.

(Types of liquid crystal display devices)
The cellulose derivative film of the present invention can be used for liquid crystal cells in various display modes. TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), AFLC (Anti-Ferroly Liquid Liquid Crystal), OCB (Optically Charged STP). Various display modes such as ECB (Electrically Controlled Birefringence) and 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 derivative 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.
In the liquid crystal display device of the present invention, the display mode is preferably VA mode or IPS mode.

(TN type liquid crystal display device)
The cellulose derivative film of the present invention may be used as a support for an optical compensation film of a TN type liquid crystal display device having a TN mode liquid crystal cell or as a protective film for a polarizing plate. TN mode liquid crystal cells and TN type liquid crystal display devices have been well known for a long time. The optical compensation film used in the TN liquid crystal display device is described in JP-A-3-9325, JP-A-6-148429, JP-A-8-50206, and JP-A-9-26572. Moreover, it is described in Mori et al. (Jpn. J. Appl. Phys. 36 (1997) 143, Jpn. J. Appl. Phys. 36 (1997) 1068).

(STN type liquid crystal display)
You may use the cellulose derivative film of this invention as a support body of the optical compensation film of a STN type liquid crystal display device which has a liquid crystal cell of STN mode, or a protective film of a polarizing plate. In general, in a STN type liquid crystal display device, rod-like liquid crystalline molecules in a liquid crystal cell are twisted in the range of 90 to 360 degrees, and the refractive index anisotropy (Δn) and cell gap (d) of the rod-like liquid crystalline molecules. Product (Δnd) is in the range of 300 to 1500 nm. The optical compensation sheet used for the STN type liquid crystal display device is described in JP-A-2000-105316.

(VA type liquid crystal display device)
The cellulose derivative film of the present invention is particularly advantageously used as a support for an optical compensation film of a VA liquid crystal display device having a VA mode liquid crystal cell. Moreover, you may use as a protective film of a polarizing plate. It is preferable that Re (589) of the optical compensation film used for the VA liquid crystal display device is 0 to 150 nm and Rth (589) is 70 to 400 nm. Re (589) is more preferably 20 to 70 nm. When two optically anisotropic polymer films are used in the VA liquid crystal display device, the Rth (589) of the film is preferably 70 to 250 nm. When one optically anisotropic polymer film is used for the VA liquid crystal display device, the Rth (589) of the film is preferably 150 to 400 nm. The VA-type liquid crystal display device may be an alignment-divided system as described in, for example, JP-A-10-123576.

(IPS liquid crystal display device and ECB liquid crystal display device)
The cellulose derivative film of the present invention is particularly advantageously used as a support for an optical compensation film of an IPS liquid crystal display device having an IPS mode and an ECB mode liquid crystal cell and an ECB liquid crystal display device, or as a protective film for a polarizing plate. . In these modes, the liquid crystal material is aligned substantially in parallel during black display, and black is displayed by aligning liquid crystal molecules parallel to the substrate surface in the absence of voltage. In these embodiments, the polarizing plate using the cellulose derivative film of the present invention contributes to widening the viewing angle and improving the contrast. In this embodiment, the retardation value of the optically anisotropic layer disposed between the protective film of the polarizing plate and the protective film and the liquid crystal cell is set to be not more than twice the value of Δn · d of the liquid crystal layer. Is preferred. The absolute value | Rth (589) | of the Rth (589) value is preferably set to 25 nm or less, more preferably 20 nm or less, and even more preferably 15 nm or less, and therefore the cellulose derivative film of the present invention is advantageously used. .

(OCB type liquid crystal display device and HAN type liquid crystal display device)
The cellulose derivative film of the present invention is also advantageous as a support for an optical compensation film or a protective film for a polarizing plate 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. Used. In the optical compensation film used for the OCB type liquid crystal display device or the HAN type liquid crystal display device, it is preferable that the direction in which the absolute value of retardation is minimum does not exist in the plane of the optical compensation film or in the normal direction. The optical properties of the optical compensation film used in the OCB type liquid crystal display device or the HAN type liquid crystal display device are also the optical properties of the optical anisotropic layer, the optical properties of the support, and the optical anisotropic layer and the support. Is determined by the arrangement of An optical compensation film used for an OCB type liquid crystal display device or a HAN type liquid crystal display device is described in JP-A-9-197397. Moreover, it is described in a paper by Mori et al. (Jpn. J. Appl. Phys. Vol. 38 (1999) p. 2837).

(Reflective liquid crystal display)
The cellulose derivative film of the present invention is also advantageously used as an optical compensation film or a protective film of a polarizing plate in a TN type, STN type, HAN type, GH (Guest-Host) type reflective liquid crystal display device. 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, International Publication No. 98/48320, and Japanese Patent No. 3022477. The optical compensation sheet used in the reflective liquid crystal display device is described in International Publication No. 00/65384 pamphlet.

(Other liquid crystal display devices)
The cellulose derivative film of the present invention is made of ASM (Axially Symmetric.
It is also advantageously used as a support for an optical compensation film or a protective film for a polarizing plate of an ASM type liquid crystal display device having an aligned microcell (liquid crystal cell) 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, page 1089 (1998)).

(Self-luminous display device)
An optical compensation film, a polarizing plate and the like using the cellulose derivative film according to the present invention can be provided in a self-luminous display device to improve display quality. There is no particular limitation on the self-luminous display device. Incidentally, organic EL, PDP, FED, etc. are mentioned as the example. By applying a birefringent film having a Re wavelength of ¼ wavelength to a self-luminous flat panel display, linearly polarized light can be converted to circularly polarized light to form an antireflection filter.
In the above, the components for forming a display device such as a liquid crystal display device may be laminated and integrated, or may be in a separated state. In forming the display device, for example, appropriate optical elements such as a prism array sheet, a lens array sheet, a light diffusing plate, and a protective plate can be appropriately disposed. Such an element can also be used for forming a display device in the form of the above-described optical member formed by laminating with an optical compensation film.

(Hard coat film, antiglare film, antireflection film)
The cellulose derivative film of the present invention can be preferably applied to a hard coat film, an antiglare film and an antireflection film. For the purpose of improving the visibility of flat panel displays such as LCD, PDP, CRT, EL, etc., any or all of a hard coat layer, an antiglare layer and an antireflection layer are provided on one or both sides of the cellulose derivative film of the present invention. can do. Preferred embodiments of such an antiglare film and antireflection film are described in detail in pages 54 to 57 of the Japan Society for Invention and Innovation Technical Report No. 2001-1745 (issued March 15, 2001, Japan Society of Invention and Innovation). The cellulose derivative film of the present invention can be preferably used.

(Photo film support)
Furthermore, the cellulose derivative film of the present invention can be applied as a support for silver halide photographic light-sensitive materials. Regarding these techniques, Japanese Patent Application Laid-Open No. 2000-105445 discloses details regarding color negatives, and the cellulose derivative 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.

(Transparent substrate)
Since the cellulose derivative film of the present invention has excellent transparency, it can be used as an alternative to the liquid crystal cell glass substrate of a liquid crystal display device, that is, as a transparent substrate for encapsulating driving liquid crystal.
Since the transparent substrate enclosing the liquid crystal needs to be excellent in gas barrier properties, a gas barrier layer may be provided on the surface of the cellulose derivative film of the present invention as necessary. Although the form and material of the gas barrier layer are not particularly limited, SiO ₂ or the like is vapor-deposited on at least one surface of the cellulose derivative film of the present invention, or a relatively high gas barrier property such as vinylidene chloride polymer or vinyl alcohol polymer. A method of providing a polymer coat layer can be considered, and these can be used as appropriate.
In order to use as a transparent substrate for enclosing liquid crystal, a transparent electrode for driving the liquid crystal by applying a voltage may be provided. Although it does not specifically limit as a transparent electrode, A transparent electrode can be provided by laminating | stacking a metal film, a metal oxide film, etc. on the at least single side | surface of the cellulose derivative film of this invention. Among these, a metal oxide film is preferable from the viewpoint of transparency, conductivity, and mechanical characteristics, and in particular, a thin film of indium oxide mainly containing tin oxide and 2 to 15% of zinc oxide can be preferably used. Details of these techniques are disclosed in, for example, Japanese Patent Application Laid-Open Nos. 2001-125079 and 2000-227603.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to the following example.

[Example 1]
<Preparation of cellulose derivative solution>
The composition shown in Table 7 was put into a pressure-resistant mixing tank and stirred for 6 hours to dissolve each component to prepare cellulose derivative solutions (hereinafter also referred to as dopes) T-1 to T-30. In addition, () in the column of the degree of substitution in Table 7 indicates the group name of the substituted acyl group, and the polarization of each group calculated by the method described in the text in () following each group name. The rate anisotropy was shown.

TPP: Triphenyl phosphate BDP: Biphenyl diphenyl phosphate UVB-3: 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole UVB-7: 2- ( 2'-hydroxy-3 ', 5'-di-tert-pentylphenyl) -benzotriazole asalonyl: substituent of the following structure

<Preparation of Cellulose Derivative Film Sample 001>
The adjusted cellulose derivative solution T-1 was cast on a metal support with a band casting machine and then dried, and the dope casting film having a self-supporting property was peeled from the band. The peeled dope film is dried while being held with a tenter so that the film width is maintained, and then wound on a roll to produce a cellulose derivative film sample 001 having a thickness of 80 μm so that the width direction is 1.3 m. did.

<Preparation of Cellulose Derivative Film Samples 002-030>
In the production method of the cellulose derivative film sample 001, a cellulose derivative film sample 002 having a thickness of 80 μm was obtained in the same manner except that the cellulose derivative solution used for the dope preparation and the additive solution were changed to those shown in Table 8. 030 was produced so that the width direction had a length described in Table 8.

<Preparation of Cellulose Derivative Film Sample 031>
(Preparation of cellulose derivative solution)
In a stainless steel dissolution tank having stirring blades and circulating cooling water around the outer periphery, 80.0 parts by mass of dichloromethane (main solvent), 10.0 parts by mass of methanol (second solvent), 5.0 parts of butanol (third solvent) Parts by mass, 2.4 parts by mass of trimethylolpropane triacetate (plasticizer), UVB-3 (0.2 parts by mass), UVB-7 (0.2 parts by mass), 2- (2'-hydroxy-3 ', 0.2 part by mass of 5′-di-t-amylphenyl) -5-chlorobenzotriazole (UV absorber C) was added.

While stirring and dispersing each component, 20 parts by mass of cellulose acetate powder (flakes) having an acetyl substitution degree of 2.92 was gradually added. After the cellulose acetate powder was put into the dispersion tank, the pressure inside the tank was reduced to 1300 Pa. Stirring has a dissolver-type eccentric stirring shaft that stirs at a peripheral speed of 15 m / sec (shear stress 5 × 104 kgf / m / sec ² ) and an anchor blade on the central axis, and a peripheral speed of 1 m / sec (shear stress 1 It was carried out for 30 minutes using a stirring shaft that was stirred at × 104 kgf / m / sec ² ). The starting temperature of stirring was 25 ° C., stirring was performed while flowing cooling water, and the final temperature reached 35 ° C. Thereafter, the high-speed stirring shaft was stopped, the peripheral speed of the stirring shaft having anchor blades was set to 0.5 m / sec, and stirring was further performed for 100 minutes to swell the cellulose acetate powder (flakes).

  The obtained non-uniform gel-like substance is fed with a screw pump whose center is heated to 30 ° C., cooled from the outer periphery of the screw, and the cooling portion is set at −75 ° C. for 3 minutes. I let it pass. Cooling was performed using a -80 ° C refrigerant cooled by a refrigerator. The solution obtained by cooling was heated to 35 ° C. during liquid feeding by a screw pump and transferred to a stainless steel container. After stirring at 50 ° C. for 2 hours to obtain a homogeneous solution, the solution was filtered with a filter paper (FH025, manufactured by Pall) having an absolute filtration accuracy of 2.5 μm. The obtained cellulose derivative solution is heated and pressurized to 110 ° C. and 1 MPa at the heating and pressurizing part of the liquid feeding pipe, and is released to normal pressure (about 0.1 Mpa), thereby volatilizing the organic solvent and cooling. A dope solution was obtained.

(Preparation of cellulose derivative film)
By using the filtered cellulose derivative solution at 50 ° C. and casting by the same method as in Example 1, a cellulose derivative film having a film thickness of 80 μm was prepared so that the width direction becomes the length shown in Table 8 to obtain cellulose. A derivative film 031 was obtained.

<Surface treatment>
Next, the following surface treatment was performed on the produced film sample 001.
The produced film sample 001 was immersed in an aqueous 1.5 mol / L sodium hydroxide solution at 55 ° C. for 2 minutes. It wash | cleaned in the room temperature water-washing bath, and neutralized using 0.05 mol / L sulfuric acid at 30 degreeC. Again, it was washed in a water bath at room temperature and further dried with hot air at 100 ° C. In this way, a sample in which the surface of the cellulose derivative film was alkali saponified was produced.
Moreover, the sample which surface-treated similarly about the other produced film samples 002-031 was created.

<Evaluation of optical performance>
For each of the prepared samples, the optical performance of Re (589) and Rth (589) was evaluated by the method described in this specification. The results are shown in Table 8.

<Measurement of equilibrium moisture content of film>
About each produced sample film, the equilibrium moisture content of the film in 25 degreeC80% RH was measured by the method as described in this specification. The results are shown in Table 8.

<Preparation of polarizing plate>
The following polarizing plate preparation was performed using said surface-treated film samples 001 to 031. That is, a roll-shaped polyvinyl alcohol film having a thickness of 80 μm was continuously stretched 5 times in an iodine aqueous solution and dried to obtain a polarizing film. Prepare two surface-treated film samples and use a polyvinyl alcohol-based adhesive so that one side (surface-treated side) of each surface is the polarizing film side and the polarizing film is sandwiched from both sides. The polarizing plate which bonded and the both surfaces were protected by the cellulose derivative film 001 was obtained. At this time, the cellulose derivative film samples 001 on both sides were pasted so that the slow axis was parallel to the transmission axis of the polarizing film. Polarizers were also produced for surface-treated film samples 002 to 031 produced in the same manner.

<Evaluation of polarizing plate sample>
About the produced polarizing plate sample, durability evaluation was performed with the following method.
<Evaluation of polarizing plate durability>
About each produced polarizing plate sample, polarizing plate durability is calculated | required by calculating | requiring the difference before and after leaving still for 1300 hours on the conditions of 60 degreeC and 95% RH about the average value of 400 nm-700 nm of the transmittance | permeability in crossed Nicols. Evaluated.

  Table 8 shows the obtained results.

  From the above results, the film samples 16 to 23 and 26 to 30 in which the cellulose derivative having a substituent having high polarizability anisotropy and the retardation modifier satisfying the mathematical expression (11-1) are combined have a reduced Rth. It has been found that the effect becomes larger and the retardation (Rth) in the film thickness direction can be sufficiently lowered. In addition, the equilibrium moisture content can be further reduced, and a decrease in the degree of deflection after a durability test under high temperature and high humidity conditions when used as a protective film for a polarizing plate can be suppressed. It was found that durability could be improved.

[Example 2]
<Preparation of polarizing plate integrated optical compensation film sample 001>
The surface of the cellulose derivative film sample 001 produced in Example 1 was saponified by the same method as in Example 1, and then an alignment film coating solution having the following composition was applied onto this film with a wire bar coater at 20 ml / m ^2. did. The film was formed by drying with warm air of 60 ° C. for 60 seconds and further with warm air of 100 ° C. for 120 seconds. Next, the formed film was rubbed in a direction parallel to the slow axis direction of the film to form an alignment film.
(Composition of alignment film coating solution)
The following modified polyvinyl alcohol 10 parts by weight Water 371 parts by weight Methanol 119 parts by weight Glutaraldehyde 0.5 parts by weight Tetramethylammonium fluoride 0.3 parts by weight

Next, 1.8 g of the following discotic liquid crystalline compound, 0.2 g of ethylene oxide-modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.), a photopolymerization initiator (IRGA) Cure 907, manufactured by Ciba Geigy Co., Ltd.) 0.06 g, sensitizer (Kaya Cure DETX, manufactured by Nippon Kayaku Co., Ltd.) 0.02 g, 0.01 g of the following air interface side vertical alignment agent (Exemplary Compound P-6) 3 A solution dissolved in 9.9 g of methyl ethyl ketone was applied with a # 5.4 wire bar. This was attached to a metal frame and heated in a thermostatic bath at 125 ° C. for 3 minutes to align the discotic liquid crystal compound. Next, using a 120 W / cm high-pressure mercury lamp at 90 ° C., UV irradiation was performed for 30 seconds to crosslink the discotic liquid crystal compound, and then the mixture was allowed to cool to room temperature to form a discotic liquid crystal retardation layer. The thus-prepared film made of the cellulose derivative film sample 001 and the discotic liquid crystal retardation layer was used as the cellulose derivative film sample 001 with an optically anisotropic layer.
Discotic liquid crystalline compounds

  Air interface side vertical alignment agent P-6

  Using an automatic birefringence meter (KOBRA-21ADH, manufactured by Oji Scientific Instruments Co., Ltd.), the dependence of Re on the light incident angle of the cellulose derivative film 001 with an optically anisotropic layer of the present invention is measured in advance. The optical properties of the discotic liquid crystal retardation layer alone were calculated by subtracting the contribution of the cellulose derivative film sample 001. Re was 195 nm, Rth was −97 nm, and the average tilt angle of the liquid crystal was 89.9 °. It was confirmed that the discotic liquid crystal was aligned perpendicular to the film surface. The slow axis direction was parallel to the rubbing direction of the alignment film. The discotic liquid crystal retardation layer produced as described above was a retardation layer having negative refractive index anisotropy and an optical axis substantially parallel to the layer surface. This discotic liquid crystal retardation layer was designated as an optical compensation layer 1.

  In the same manner as in Example 1, iodine was adsorbed on a stretched polyvinyl alcohol film to produce a polarizing film. Using a polyvinyl alcohol-based adhesive, the surface of the cellulose derivative film sample 001 with an optically anisotropic layer is saponified by the same method as in Example 1 so that the cellulose derivative film is on the polarizing film side. Affixed to one side. The transmission axis of the polarizing film and the slow axis of the cellulose derivative film sample 001 with an optically anisotropic layer (the slow axis of the optical compensation layer 1 also coincides with this) were arranged so as to be orthogonal to each other. Further, a commercially available cellulose acetate film (Fujitac TD80UF, manufactured by Fuji Photo Film Co., Ltd.) is saponified and attached to the opposite side of the polarizing film using a polyvinyl alcohol adhesive, and a polarizing plate integrated optical compensation film Made 001.

<Preparation of polarizing plate integrated optical compensation film samples 002 to 031>
A polarizing plate integrated optical compensation film 002 is manufactured in the same manner as the polarizing plate integrated optical compensation film sample 001 except that the cellulose derivative film samples 002 to 031 prepared in Example 1 are used instead of the cellulose derivative film sample 001. ˜031 were produced.

<Production of IPS mode liquid crystal cell>
As shown in FIG. 1, electrodes (2 and 3 in FIG. 1) are arranged on one glass substrate so that the distance between adjacent electrodes is 20 μm, and a polyimide film is used as an alignment film on it. A rubbing process was performed. The rubbing process was performed in the direction 4 shown in FIG. A polyimide film was provided on one surface of a separately prepared glass substrate, and a rubbing treatment was performed to obtain an alignment film. The two glass substrates are stacked and bonded so that the alignment films face each other, the distance between the substrates (gap; d) is 3.9 μm, and the rubbing directions of the two glass substrates are parallel. A nematic liquid crystal composition having a refractive index anisotropy (Δn) of 0.0769 and a dielectric anisotropy (Δε) of 4.5 was enclosed. The value of d · Δn of the liquid crystal layer was 300 nm.

<Evaluation of light leakage in IPS mode liquid crystal display>
Next, a liquid crystal display device was manufactured using the polarizing plate-integrated optical compensation film prepared above, and light leakage was evaluated. In addition, the polarizing plate integrated optical compensation film produced in a long shape was cut into a predetermined size and then incorporated into a liquid crystal display device.
Using an adhesive, the polarizing plate integrated optical compensation film 001 is placed on one of the produced IPS mode liquid crystal cells, and the slow axis of the cellulose derivative film sample 001 with an optically anisotropic layer is perpendicular to the rubbing direction of the liquid crystal cell. (That is, the slow axis of the optical compensation layer 1 is orthogonal to the slow axis of the liquid crystal molecules of the liquid crystal cell during black display), and the discotic liquid crystal retardation layer side is the liquid crystal cell side. Pasted like so. Subsequently, a commercially available polarizing plate (HLC2-5618, manufactured by Sanritz Co., Ltd.) was attached to the other side of the IPS mode liquid crystal cell 1 in a crossed Nicol arrangement to produce a liquid crystal display device 001.
With respect to the polarizing plate integrated optical compensation films 002 to 031, liquid crystal display devices 002 to 031 incorporated in the IPS mode liquid crystal display device were produced in the same manner.

<Evaluation test>
[Panel evaluation]
<Evaluation of viewing angle dependency of liquid crystal display device>
The viewing angle dependence of the transmittance of the prepared liquid crystal display device was measured. The suppression angle was measured from the front to the diagonal direction up to 80 ° every 10 °, and the azimuth angle was measured up to 360 ° every 10 ° on the basis of the horizontal right direction (0 °). It has been found that the luminance during black display increases due to leaked light as the angle of suppression increases from the front direction, and takes a maximum value near the angle of suppression of 70 °. It was also found that the contrast deteriorates as the luminance during black display increases. Therefore, the luminance LA measured from a direction rotated by 45 ° to the left from the rubbing direction of the liquid crystal cell during black display, and the luminance LA measured from the direction rotated 45 ° to the left from the rubbing direction of the liquid crystal cell and the rubbing of the liquid crystal cell during white display. The luminance LB measured from a direction rotated 45 ° from the direction to the left was measured, and the contrast was evaluated by obtaining the leaked light (%) as a ratio of LA to LB. The results are shown in Table 8.
(Leakage light) = LA / LB

<Durability evaluation of the manufactured liquid crystal display device>
Measure the front black luminance and the black luminance after the durability test at the center of the image of the created liquid crystal display device, and determine the ratio (%) of the difference in black luminance before and after the black luminance relative to the white luminance before the aging. The durability of the liquid crystal display device was evaluated as the black luminance increase rate before and after. Table 8 shows the evaluation results. (Durability evaluation) = ((Black luminance after aging) − (Black luminance before aging)) / (White luminance before aging)
As a result, a liquid crystal display device using a polarizing plate using the film samples of the present invention (film samples 015 to 023 and 025 to 030) as a protective film for a polarizing plate has excellent viewing angle characteristics and durability at high temperature and high humidity. It was found that a liquid crystal display device excellent in durability can be obtained by suppressing an increase in black luminance after the property test.

Example 3
<Preparation of polarizing plate integrated optical compensation film sample 001A>
In the same manner as in Example 1, iodine was adsorbed on a stretched polyvinyl alcohol film to produce a polarizing film. The surface of the cellulose derivative film sample 001 of the present invention was saponified by the same method as in Example 1, and then attached to one side of the polarizing film using a polyvinyl alcohol-based adhesive. The transmission axis of the polarizing film and the slow axis of the cellulose derivative film sample 001 were arranged in parallel. Furthermore, a commercially available cellulose acetate film (Fujitac TD80UF, manufactured by Fuji Photo Film Co., Ltd.) is saponified and attached to the opposite side of the polarizing film using a polyvinyl alcohol adhesive, and a polarizing plate integrated optical compensation film 001A was manufactured.

<Preparation of polarizing plate integrated optical compensation film samples 002A to 031A>
A polarizing plate integrated optical compensation film 002A is produced in the same manner as the polarizing plate integrated optical compensation film sample 001A except that the cellulose derivative film samples 002 to 031 prepared in Example 1 are used instead of the cellulose derivative film sample 001. ˜031A was produced.

<Preparation of polarizing plate integrated optical compensation film sample 003B>
The surface of the cellulose derivative film sample 003 produced in Example 1 was saponified by the same method as in Example 1, and then an alignment film coating solution having the following composition was applied onto this film with a wire bar coater at 20 ml / m ^2. did. The film was formed by drying with warm air of 60 ° C. for 60 seconds and further with warm air of 100 ° C. for 120 seconds. Next, the formed film was rubbed in a direction parallel to the slow axis direction of the film to form an alignment film.

(Composition of alignment film coating solution)
The following modified polyvinyl alcohol 10 parts by weight Water 371 parts by weight Methanol 119 parts by weight Glutaraldehyde 0.5 parts by weight Tetramethylammonium fluoride 0.3 parts by weight

  Modified polyvinyl alcohol

Next, 1.8 g of the following discotic liquid crystalline compound, 0.2 g of ethylene oxide-modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.), a photopolymerization initiator (IRGA) Cure 907, manufactured by Ciba Geigy Co., Ltd.) 0.06 g, sensitizer (Kaya Cure DETX, manufactured by Nippon Kayaku Co., Ltd.) 0.02 g, 0.01 g of the following air interface side vertical alignment agent (Exemplary Compound P-6) 3 A solution dissolved in 9.9 g of methyl ethyl ketone was applied with a # 5.4 wire bar. This was attached to a metal frame and heated in a thermostatic bath at 125 ° C. for 3 minutes to align the discotic liquid crystal compound. Next, using a 120 W / cm high-pressure mercury lamp at 90 ° C., UV irradiation was performed for 30 seconds to crosslink the discotic liquid crystal compound, and then the mixture was allowed to cool to room temperature to form a discotic liquid crystal retardation layer. The thus-prepared film made of the cellulose derivative film sample 003 and the discotic liquid crystal retardation layer was used as a cellulose derivative film sample 003B with an optically anisotropic layer.
Discotic liquid crystalline compounds

  Air interface side vertical alignment agent P-6

  Using an automatic birefringence meter (KOBRA-21ADH, manufactured by Oji Scientific Instruments Co., Ltd.), the dependency of Re on the light incident angle of the cellulose derivative film 003B with an optically anisotropic layer of the present invention is measured and measured in advance. The optical properties of the discotic liquid crystal retardation layer alone were calculated by subtracting the contribution of the cellulose derivative film sample 003B. As a result, Re was 191 nm, Rth was −105 nm, and the average tilt angle of the liquid crystal was 89.3 °. It was confirmed that the discotic liquid crystal was aligned perpendicular to the film surface. The slow axis direction was parallel to the rubbing direction of the alignment film. The discotic liquid crystal retardation layer produced as described above was a retardation layer having negative refractive index anisotropy and an optical axis substantially parallel to the layer surface. This discotic liquid crystal retardation layer was designated as an optical compensation layer 3B.

  In the same manner as in Example 1, iodine was adsorbed on a stretched polyvinyl alcohol film to produce a polarizing film. Using a polyvinyl alcohol-based adhesive, the surface of the cellulose derivative film sample 003B with an optically anisotropic layer is saponified by the same method as in Example 1 so that the cellulose derivative film is on the polarizing film side. Affixed to one side. The transmission axis of the polarizing film and the slow axis of the cellulose derivative film sample 003B with an optically anisotropic layer (the slow axis of the optical compensation layer 3B coincides with this) were arranged in parallel. Further, a commercially available cellulose acetate film (Fujitac TD80UF, manufactured by Fuji Photo Film Co., Ltd.) is saponified and attached to the opposite side of the polarizing film using a polyvinyl alcohol adhesive, and a polarizing plate integrated optical compensation film 003B was produced.

<Evaluation of light leakage in IPS mode liquid crystal display>
Next, a liquid crystal display device was manufactured using the polarizing plate-integrated optical compensation film prepared above, and light leakage was evaluated. In addition, the polarizing plate integrated optical compensation film produced in a long shape was cut into a predetermined size and then incorporated into a liquid crystal display device.
Using an adhesive, polarizing plate-integrated optical compensation film 003B was rubbed on one side of the IPS mode liquid crystal cell produced in Example 2 with the slow axis of the cellulose derivative film sample 003 with an optically anisotropic layer as the liquid crystal cell. So that the slow axis of the optical compensation layer 1 is perpendicular to the slow axis of the liquid crystal molecules of the liquid crystal cell during black display, and the discotic liquid crystal retardation layer side is the liquid crystal Affixed to the cell side. Subsequently, a polarizing plate-integrated optical compensation film 001A was attached to the other side of the IPS mode liquid crystal cell in a crossed Nicols arrangement to produce a liquid crystal display device 001C.
With respect to the polarizing plate-integrated optical compensation films 002 to 031, liquid crystal display devices 002C to 031C incorporated in the IPS mode liquid crystal display device were produced in the same manner.

<Evaluation test>
[Panel evaluation]
<Evaluation of viewing angle dependency of liquid crystal display device>
The contrast was evaluated by obtaining leakage light (%) by the same method as in Example 2. The results are shown in Table 8.
(Leakage light) = LA / LB
<Durability evaluation of the manufactured liquid crystal display device>
The durability of the liquid crystal display device was evaluated by obtaining the black luminance increase rate in the same manner as in Example 2. Table 8 shows the evaluation results.
As a result, a liquid crystal display device using a polarizing plate using the film samples of the present invention (film samples 015 to 023 and 025 to 030) as a protective film for a polarizing plate has excellent viewing angle characteristics and durability at high temperature and high humidity. It was found that a liquid crystal display device excellent in durability can be obtained by suppressing an increase in black luminance after the property test.

It is explanatory drawing of an IPS mode liquid crystal cell.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Liquid crystal element pixel area 2 Pixel electrode 3 Display electrode 4 Rubbing direction 5a, 5b Liquid crystal compound director at the time of black display 6a, 6b Liquid crystal compound director at the time of white display

Claims (11)

A cellulose derivative containing a substituent having a polarizability anisotropy represented by the following formula (1) of 2.5 × 10 ⁻²⁴ cm ³ or more, and 1 of a retardation regulator satisfying the following formula (11-1) A cellulose derivative film comprising at least one or more.
Formula (1): Δα = α _x − (α _y + α _z ) / 2
(Where α _x is the largest component of the eigenvalues obtained after diagonalizing the polarizability tensor;
α _y is the second largest component of the eigenvalues obtained after diagonalizing the polarizability tensor;
α _z is the smallest component of the eigenvalues obtained after diagonalizing the polarizability tensor. )
Formula (11-1): Rth (a) −Rth (0) /a≦−1.5
(However, 0.01 ≦ a ≦ 30)
Rth (a): Rth (nm) at a wavelength of 589 nm of a film having a film thickness of 80 μm comprising cellulose acylate having an acetyl substitution degree of 2.85 and 100 parts by mass of the cellulose acylate with a part by mass of the above retardation modifier.
Rth (0): Rth (nm) at a wavelength of 589 nm of a film having a film thickness of 80 μm made only of cellulose acylate having an acetyl substitution degree of 2.85 and not containing the above retardation regulator
a: parts by mass of the above retardation regulator with respect to 100 parts by mass of cellulose acylate The cellulose derivative film according to claim 1, wherein the retardation regulator is any one of compounds represented by the following general formulas (1) to (21).

(In the general formula (1), the R ¹¹ to R ¹³ each independently represents an aliphatic group having 1 to 20 carbon atoms, the aliphatic groups may have a substituent group .R ¹¹ to R ¹³ may be linked together to form a ring.)

(In the general formulas (2) and (3), Z represents a carbon atom, an oxygen atom, a sulfur atom, or —NR ²⁵ —, and R ²⁵ represents a hydrogen atom or an alkyl group. 6-membered ring which may have a substituent .Y ^21, Y ²² each independently represent the carbon atoms 1 to 20, an ester group, an alkoxycarbonyl group, an amido group or a carbamoyl group, Y ^21, Y ²² may be linked to each other to form a ring, m represents an integer of 1 to 5, and n represents an integer of 1 to 6.)

(In General Formulas (4) to (12), Y ^{31 to} Y ⁷⁰ are each independently an ester group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. An amide group, a carbamoyl group having 1 to 20 carbon atoms or a hydroxy group, V ^{31 to} V ⁴³ each independently represents a hydrogen atom or an aliphatic group having 1 to 20 carbon atoms, and L ^{31 to} L ⁸⁰ each independently Represents a divalent saturated linking group having 0 to 40 atoms and 0 to 20 carbon atoms, wherein the number of atoms of L ^{31 to} L ⁸⁰ is 0 at both ends of the linking group. (This means that the group directly forms a single bond. V ^{31 to} V ⁴³ and L ^{31 to} L ⁸⁰ may further have a substituent.)

(In General Formula (13), R ¹ represents an alkyl group or an aryl group, and R ² and R ³ each independently represent a hydrogen atom, an alkyl group, or an aryl group. R ¹ , R ^2, and R ³ The total number of carbon atoms is 10 or more, and each of the alkyl group and aryl group may have a substituent.)

(In the general formula (14), R ⁴ and R ⁵ each independently represents an alkyl group or an aryl group. The total number of carbon atoms of R ⁴ and R ⁵ is 10 or more. The group may have a substituent.)

(In the general formula (15), R ¹ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, and R ² represents a hydrogen atom, a substituted or unsubstituted aliphatic group, or a substituted or unsubstituted group. L ¹ represents a divalent to hexavalent linking group, and n represents an integer of 2 to 6 according to the valence of L ¹ .

(In General Formula (16), R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group. X is formed from one or more groups selected from the following linking group group 1. Y represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group.
(Linking group group 1) A single bond, —O—, —CO—, —NR ⁴ —, an alkylene group or an arylene group is represented. R ⁴ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. )

(In the general formula (17), Q ¹ , Q ² and Q ³ each independently represent a 5- or 6-membered ring. X represents B, C—R (R represents a hydrogen atom or a substituent), N, P and P = O are represented.)

(In the general formula (19), 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. The alkyl group and the aryl group each represent a substituent. (You may have it.)

(In the general formula (21), R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. X ¹ , X ² , X ³ and X ⁴ are each independently a single bond, —CO— and —NR ⁵ — (R ⁵ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group) Represents a divalent linking group formed from one or more groups selected from the group consisting of: a, b, c and d are integers of 0 or more, a + b + c + d is 2 or more, Q ¹ is (a + b + c + d Represents a valent organic group.) The cellulose derivative film according to claim 1, wherein the substituent having a polarizability anisotropy of 2.5 × 10 ⁻²⁴ cm ³ or more is a substituent containing an aromatic. The cellulose derivative film according to claim 1, wherein the substituent having a polarizability anisotropy of 2.5 × 10 ⁻²⁴ cm ³ or more is an aromatic acyl group.   The cellulose derivative film according to claim 1, wherein the film has an equilibrium moisture content at 25 ° C. and 80% RH of 3.0% or less. Rth ((lambda)) of a film satisfy | fills following Numerical formula (2), The cellulose derivative film of Claims 1-5 characterized by the above-mentioned.
Formula (2) −600 nm ≦ Rth (589) ≦ 0 nm
(Here Rth (λ) represents retardation in the film thickness direction of the film at a wavelength of λ nm.)   An optical compensation film comprising an optically anisotropic layer provided on the cellulose derivative film according to claim 1.   The polarizing film and the polarizing plate which has two transparent protection arrange | positioned at the both sides, Comprising: At least one of a transparent protective film is a cellulose derivative film in any one of Claims 1-6, or Claim 7. A polarizing plate characterized by being an optical compensation film.   A liquid crystal display device having a liquid crystal cell and two polarizing plates disposed on both sides thereof, wherein at least one polarizing plate is the polarizing plate according to claim 8.   The liquid crystal display device according to claim 9, wherein the display mode is a VA mode.   The liquid crystal display device according to claim 9, wherein the display mode is an IPS mode.

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