JP5218416B2 - Retardation film, polarizing plate and liquid crystal display device - Google Patents

Description

  The present invention relates to a retardation film having an optically anisotropic layer made of liquid crystal, a polarizing plate using the retardation film, and a liquid crystal display device.

  As a liquid crystal display device, a liquid crystal display device using a so-called in-plane switching (IPS) mode in which a lateral electric field excellent in viewing angle characteristics is applied to the liquid crystal, or a liquid crystal having a negative dielectric anisotropy is vertically aligned. A vertical alignment (VA) mode in which alignment is divided by protrusions and slit electrodes formed in the panel has been proposed and put into practical use.

  In recent years, these panels have been developed not only for monitor applications but also for TV applications, and screen brightness has been greatly improved accordingly. For this reason, slight light leakage in the diagonally oblique incidence direction during black display, which has not been considered as a problem in these operation modes, has become apparent as a cause of deterioration in display quality.

  Many of the proposed methods for improving the viewing angle of the color tone and the black display are based on the birefringence anisotropy of the liquid crystal in the liquid crystal cell by using an optical compensation sheet such as a retardation film. Since this is an improved system, there is a problem in that light leakage based on the deviation from the orthogonal crossing angle of the polarization axes when the orthogonal polarizing plate is viewed obliquely cannot be sufficiently solved.

  Therefore, in Patent Document 1, a retardation layer formed by vertically aligning with an optical compensation sheet is provided on a support as an optically anisotropic layer, and by using an additive in the layer, not only a viewing angle but also a retardation is provided. Techniques have also been proposed for improving screen unevenness due to unevenness.

  In patent document 2, the technique which prescribed | regulated the characteristic of the cellulose acylate film used as the support body for providing an anisotropic layer is proposed.

However, these techniques are not sufficient to cope with the environmental variation of the support for providing the optically anisotropic layer, particularly the unevenness of the screen caused by the influence of the heat from the backlight, and the liquid crystal display device. The enlargement of the screen finally revealed uneven alignment of the liquid crystal layer, which is an optically anisotropic layer.
JP 2007-45993 A JP 2007-155972 A

  An object of the present invention is to provide a retardation film that is durable to environmental changes and has little alignment unevenness in a liquid crystal layer, a polarizing plate using the retardation film, and a liquid crystal display device.

  The object of the present invention has been achieved by the following.

1. An optically biaxial transparent film, an optically anisotropic layer in which rod-like liquid crystals are vertically aligned and fixed in alignment, and at least one intermediate layer between the biaxially transparent film and the optically anisotropic layer A retardation film having a layer, wherein the intermediate layer has a rod-like polarizability anisotropy represented by the following formula (1) of 200 × 10 ⁻²⁵ cm ³ or more and 2000 × 10 ⁻²⁵ cm ³ or less. Yes, a compound having a molecular end-to-end distance of 1.5 nm to 10 nm, or a plane polarizability anisotropy represented by the following formula (2): 150 × 10 ⁻²⁵ cm ³ or more and 1500 × 10 ⁻²⁵ cm ³ or less A retardation film comprising at least one compound selected from compounds having a molecular end-to-end distance of 1.5 nm to 10 nm.

Formula (1): Δα = αx− (αy + αz) / 2
Formula (2): Δα = (αx + αy) / 2−αz
(Where αx is the largest component of the eigenvalues obtained after diagonalizing the polarizability tensor; αy is the second largest component of the eigenvalues obtained after diagonalizing the polarizability tensor. Yes; αz is the smallest component of the eigenvalues obtained after diagonalizing the polarizability tensor.)
2. In the case where there are a plurality of the intermediate layers, the compound represented by the formula (1) or (2) included in the intermediate layer closest to the transparent film and the intermediate layer closest to the optically anisotropic layer. 2. The retardation film as described in 1 above, wherein the contents are different.

  3. In the polarizing plate comprising a polarizer and two polarizing plate protective films sandwiching the polarizer, at least one of the polarizing plate protective films is the retardation film according to 1 or 2, wherein the retardation film A polarizing plate, wherein an in-plane slow axis and an absorption axis of a polarizer are orthogonal to each other.

  4). 4. A liquid crystal display device comprising the first polarizing plate according to 3 above, a driving liquid crystal cell having a liquid crystal layer sandwiched between transparent substrates, and a second polarizing plate in this order, the first and second polarizing plates. The absorption axes of the plates are orthogonal, the optically anisotropic layer of the first polarizing plate is disposed on the driving liquid crystal cell side when viewed from the polarizer of the first polarizing plate, and the liquid crystal layer in the liquid crystal cell is 1. A liquid crystal display device, wherein the liquid crystal display device is oriented horizontally with respect to the substrate without applying voltage, and the orientation direction of the liquid crystal layer in the liquid crystal cell is perpendicular to the absorption axis of the first polarizing plate.

5. The second polarizing plate is a polarizing plate comprising a polarizer and two polarizing plate protective films sandwiching the polarizer, and at least one of the polarizing plate protective films is an optically isotropic film. , An optically negative uniaxial film and a film satisfying nx>ny> nz, and the selected polarizing plate protective film side as viewed from the polarizer is disposed in the driving liquid crystal cell. 5. The liquid crystal display device as described in 4 above, which is a polarizing plate.
(Nx represents the refractive index in the slow axis direction in the plane of the film, ny represents the refractive index in the direction perpendicular to the slow axis in the plane, and nz represents the refractive index in the thickness direction.)

  According to the present invention, it is possible to obtain a retardation film which is durable to environmental changes and has a small alignment unevenness of a liquid crystal layer, a polarizing plate and a liquid crystal display device using the retardation film.

It is one schematic of the embodiment which concerns on the liquid crystal display device of this invention.

Explanation of symbols

1, 9 TAC film 2, 8 Polarizers The absorption axes of the polarizers 2 and 8 are orthogonal to each other.

DESCRIPTION OF SYMBOLS 3 Optically biaxial transparent film 4 Intermediate layer 5 Optically anisotropic layer which fixed the orientation by aligning a rod-shaped liquid crystal perpendicularly 6 Driving liquid crystal cell 6-1 Viewing side glass substrate 6-2 Backlight side Glass substrate 6-3 Liquid crystal layer 7 Isotropic cellulose triacetate film 10 First polarizing plate (viewing side polarizing plate)
11 Retardation film of the present invention 12 Second polarizing plate (backlight side polarizing plate)
13 Backlight

<The retardation film of the present invention>
The present invention relates to a retardation film provided with an optically anisotropic layer in which a rod-like liquid crystal is vertically aligned and fixed in alignment on an optically biaxial transparent film, the biaxial transparent film and A transparent layer which is at least one intermediate layer is provided between the optically anisotropic layer and the transparent layer which is the intermediate layer has a rod-like polarizability anisotropy represented by the following formula (1) of 200 × 10 ⁻²⁵ cm ³ or more and 2000 × 10 ⁻²⁵ cm ³ or less, a compound having an end-to-end distance of 1.5 to 10 nm, or a plane polarizability anisotropy represented by the following formula (2) is 150 It is characterized by containing at least one compound selected from a compound having a molecular end-to-end distance of 1.5 nm to 10 nm, and a molecular weight of 10 × 10 ⁻²⁵ cm ^{3 to} 1500 × 10 ⁻²⁵ cm ^3. .

Formula (1): Δα = αx− (αy + αz) / 2
Formula (2): Δα = (αx + αy) / 2−αz
(Where αx is the largest component of the eigenvalues obtained after diagonalizing the polarizability tensor; αy is the second largest component of the eigenvalues obtained after diagonalizing the polarizability tensor. Yes; αz is the smallest component of the eigenvalues obtained after diagonalizing the polarizability tensor.)
The retardation film of the present invention has a thickness of 20 to 70 μm and the following characteristics.

40 nm ≦ Ro ≦ 330 nm
−100 nm ≦ Rt ≦ 50 nm
Ro and Rt are the total of Ro and Rt of the optically biaxial transparent film, the optically anisotropic layer in which the rod-like liquid crystal is vertically aligned and the alignment is fixed, and the intermediate layer.

  The retardation value was measured by adjusting the humidity to a wavelength of 590 nm and 23 ° C. and 55% RH using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments).

《Optically biaxial transparent film》
In the present invention, the optically biaxial transparent film means that the refractive index in the slow axis direction in the plane of the film is nx, the refractive index in the direction perpendicular to the slow axis in the plane is ny, and in the thickness direction. A transparent film having such a property that nx>ny> nz when the refractive index is nz.

  The transparent film of the present invention preferably has the following characteristics.

Transmittance: 80% or more Film thickness: 20-70 μm
40 nm ≦ Ro ≦ 330 nm
50 nm ≦ Rt ≦ 340 nm
1.1 ≦ Rt / Ro ≦ 10
The measurement wavelengths of Ro and Rt are 590 nm, Ro = (nx−ny) × d, and Rt = {(nx + ny) / 2−nz} × d, where d represents the film thickness (nm) of the transparent film.

  The transparent film is preferably selected from a cellulose ester film, a polycarbonate film, a polysulfone film, a polyether sulfone film and a polyacrylate film, and more preferably a cellulose ester film.

In order to adjust the biaxiality of the cellulose ester film of the present invention, the rod-like polarizability anisotropy represented by the formula (1) is 200 × 10 ⁻²⁵ cm ³ or more and 2000 × 10 ⁻²⁵ cm ³ or less. A compound having an end-to-end distance of 1.5 to 10 nm, a plane polarizability anisotropy represented by Formula (2) of 150 × 10 ⁻²⁵ cm ^{3 to} 1500 × 10 ⁻²⁵ cm ³ A compound having an end-to-end distance of 1.5 nm to 10 nm, an acrylic polymer, and at least one of at least one of a pyranose structure or a furanose structure and 12 or less of all OH groups of the structure are esterified It is preferable that the cellulose ester film contains at least one ester compound.

  The compound represented by the formula (1) or (2) of the present invention acts as a retardation increasing agent for increasing the so-called cellulose ester retardation.

  The end-to-end distance of the retardation increasing agent of the present invention is required to be 1.5 nm or more and 10 nm or less for the function expression.

  The end-to-end distance can be determined from the optimized molecular structure by calculation using the molecular orbital method or the density functional method.

  The retardation increasing agents used in the present invention are roughly classified into two types. The first is the type represented by the mathematical formula (1) having a large rod-like polarizability anisotropy of the molecule, and the second is the formula represented by the mathematical formula (2) having a large planar polarizability anisotropy of the molecule. It is.

  For these compounds, the compounds described in JP-A-2006-193724 can be referred to.

<Equation is a rod-like polarizability anisotropy represented by (1) is 200 × 10 ^-25 cm ³ or more 2000 × 10 ^-25 cm ³ or less, end-to-end distance is 1.5nm or more 10nm following compounds of molecular>
The polarizability of the molecule of the compound according to the formula (1) of the present invention can be determined by calculation using the molecular orbital method or the density functional method, and the rod-shaped polarizability anisotropy represented by the following formula (1) Is required to be 200 × 10 ⁻²⁵ cm ³ or more and 2000 × 10 ⁻²⁵ cm ³ or less.

The rod-shaped polarizability anisotropy is preferably 250 × 10 ⁻²⁵ cm ³ or more and 1500 × 10 ⁻²⁵ cm ³ or less for the function expression.

Formula (1): Δα = αx− (αy + αz) / 2
(Where αx is the largest component of the eigenvalues obtained after diagonalizing the polarizability tensor; αy is the second largest component of the eigenvalues obtained after diagonalizing the polarizability tensor. Yes; αz is the smallest component of the eigenvalues obtained after diagonalizing the polarizability tensor.)
Examples of the retardation increasing agent having a rod-like polarizability anisotropy of 200 × 10 ⁻²⁵ cm ³ or more and 2000 × 10 ⁻²⁵ cm ³ or less and a molecular end-to-end distance of 1.5 to 10 nm are as follows: The compound represented by the general formula (1) is particularly preferable.

Below, it demonstrates in detail regarding the compound represented by General formula (1).
General formula (1): Ar1-L1-X-L2-Ar2
{In the formula, Ar 1 and Ar 2 each independently represent an aryl group or an aromatic heterocycle. L1 and L2 each independently represent —C (═O) O— or —C (═O) NR— (R represents a hydrogen atom or an alkyl group). X represents the following general formula (2) or general formula (3). }

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom or a substituent.)

(In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represents a hydrogen atom or a substituent.)
In general formula (1), Ar1 and Ar2 each independently represent an aryl group or an aromatic heterocycle. The aryl group represented by Ar1 or Ar2 is preferably an aryl group having 6 to 30 carbon atoms, which may be a single ring or may form a condensed ring with another ring. Further, if possible, it may have a substituent, and the substituent T described later can be applied as such a substituent.
More preferably, the aryl group represented by Ar1 or Ar2 has 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, and naphthyl.

  In the general formula (1), the aromatic heterocycle represented by Ar1 or Ar2 may be anything as long as it is an aromatic heterocycle containing at least one of an oxygen atom, a nitrogen atom or a sulfur atom, preferably oxygen. It is a 5- to 6-membered aromatic heterocycle containing at least one of an atom, nitrogen atom or sulfur atom. Moreover, you may have a substituent further if possible. Substituent T described later can be applied as the substituent.

  In the general formula (1), L 1 and L 2 each independently represent —C (═O) O— or —C (═O) NR— (R represents a hydrogen atom or an alkyl group), Likewise preferred.

  The alkyl group represented by R is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. More preferably, R represents a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

In the general formula (2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a substituent, and the substituent will be described later. The substituent T can be applied.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are preferably a hydrogen atom, an alkyl group, an amino group, an alkoxy group, a hydroxy group or a halogen atom, more preferably A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, and a halogen atom, more preferably a hydrogen atom, a methyl group, a methoxy group, a hydroxy group, a chlorine atom, and a fluorine atom. And particularly preferably a hydrogen atom or a fluorine atom, and most preferably a hydrogen atom.

In the general formula (3), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or a substituent, and the substituent will be described later. The substituent T can be applied.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are preferably a hydrogen atom, an alkyl group, an amino group, an alkoxy group, a hydroxy group or a halogen atom, more preferably A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, and a halogen atom, more preferably a hydrogen atom, a methyl group, a methoxy group, a hydroxy group, a chlorine atom, and a fluorine atom. And particularly preferably a hydrogen atom or a fluorine atom, and most preferably a hydrogen atom.

  Examples of the substituent T include an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, a substituted or unsubstituted amino group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, and an 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, cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group, silyl group and the like. 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.

  Hereinafter, the compound represented by the general formula (1) will be described in detail with specific examples, but the present invention is not limited to the following specific examples.

Examples of the retardation increasing agent having a rod-like polarizability anisotropy of 200 × 10 ⁻²⁵ cm ³ or more and 2000 × 10 ⁻²⁵ cm ³ or less and a molecular end-to-end distance of 1.5 to 10 nm are as follows: A compound represented by the general formula (4) is also particularly preferable.

  Hereinafter, the compound of the general formula (4) will be described in detail.

(In the general formula (4), R ^2-1 , R ^4-1 and R ^5-1 each represent a hydrogen atom or a substituent, and R ^11-1 and R ^13-1 each represent a hydrogen atom or an alkyl group. , L ^1-1 and L ^2-1 each represent a single bond or a divalent linking group, Ar ^1-1 represents an arylene group or an aromatic heterocyclic ring, and Ar ^2-1 represents an aryl group or an aromatic group. Represents a terror ring, and n-1 represents an integer of 3 or more, and L ^2-1 and Ar ^1-1 present in n-1 types may be the same or different, provided that R ^11-1 , R ^13-1 is different from each other, and the alkyl group represented by R ^13-1 does not contain a hetero atom.)
In general formula (4), R ^{<2-1 >} , R ^{< 4-1>} , R ^<5-1> represents a hydrogen atom or a substituent, respectively, and the substituent T2 mentioned later can be applied to a substituent.

R ^2-1 is preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, or a hydroxyl group having 6 or less carbon atoms.

^R4-1 preferably has 6 or less carbon atoms and is a hydrogen atom or an electron donating group, and more preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, or a hydroxyl group.

R ^5-1 preferably has 6 or less carbon atoms and is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an amino group or a hydroxyl group, more preferably a hydrogen atom, an alkyl group or an alkoxy group. .

R ^11-1 and R ^13-1 each represent a hydrogen atom or an alkyl group, R ^11-1 and R ^13-1 are different from each other, and the alkyl group represented by R ^13-1 represents a ^hetero atom. Not included. Here, the heteroatom means an atom other than a hydrogen atom or a carbon atom, such as an oxygen atom, a nitrogen atom, a sulfur atom, phosphorus, silicon, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), boron, etc. Is mentioned.

The alkyl groups represented by R ^11-1 and R ^13-1 each represent a linear, branched, or cyclic alkyl group that is substituted or unsubstituted, preferably a substituted or unsubstituted carbon atom. An alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms (that is, a bicyclocarbon having 5 to 30 carbon atoms). A monovalent group in which one hydrogen atom is removed from an alkane.), And a tricyclo structure having many ring structures.

Ar ^1-1 represents an arylene group or an aromatic heterocyclic ring, and Ar ^1-1 in the repeating unit may all be the same or different. Ar ^2-1 represents an aryl group or an aromatic heterocyclic ring.

In the general formula (4), the arylene group represented by Ar ^1-1 is preferably an arylene group having 6 to 30 carbon atoms, which may be a single ring or further forms a condensed ring with another ring. May be. Further, if possible, it may have a substituent, and the substituent T2 described later can be applied as the substituent.

In general formula (4), the aryl group represented by Ar ^2-1 is preferably an aryl group having 6 to 30 carbon atoms, which may be a single ring or further forms a condensed ring with another ring. May be. Further, if possible, it may have a substituent, and the substituent T2 described later can be applied as the substituent.

The aryl group represented by Ar ^2-1 preferably has 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include a phenyl group, a p-methylphenyl group, and a naphthalene group.

In the general formula (4), the aromatic heterocycle represented by Ar ^1-1 or Ar ^2-1 is preferably an aromatic heterocycle containing at least one of an oxygen atom, a nitrogen atom or a sulfur atom, More preferably, it is an aromatic heterocycle containing at least one of a 5- to 6-membered oxygen atom, nitrogen atom or sulfur atom.

  Moreover, you may have a substituent further if possible. Substituent T2 described later can be applied as the substituent.

In General Formula (4), L ^1-1 and L ^2-1 each represent a single bond or a divalent linking group. L ^1-1 and L ^2-1 may be the same or different. Further, all L ^2-1 in the repeating unit may be the same or different.

Preferred as the divalent linking group is —O—, —NR ^1-1 — (R ^1-1 represents a hydrogen atom or an optionally substituted alkyl group or aryl group), —CO—, —SO ₂ —, —S—, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a group obtained by combining two or more of these divalent groups, more preferably among them. -O -, - NR -, - CO -, - SO 2 NR 1-1 -, - NR 1-1 SO 2 -, - CONR 1-1 -, - NR 1-1 CO -, - COO-, and -OCO-, an alkynylene group. R ^1-1 preferably represents a hydrogen atom.

In the compound represented by the general formula (4) in the present invention, Ar ^1-1 is bonded to L ^1-1 and L ^2-1 , but when Ar ^1-1 is a phenylene group, -L ^1-1 -Ar ^1-1 -L ^2-1 -, and -L ^2-1 -Ar ^1-1 -L ^2-1 - it is most preferable that a relation of mutually para position (1,4-position).

  In general formula (4), n-1 represents an integer greater than or equal to 3, Preferably it is 3-7, More preferably, it is 3-7, More preferably, it is 3-6.

  Examples of the substituent T2 include a halogen atom, an alkyl group, a cycloalkyl group, a bicycloalkyl group, an alkenyl group, a cycloalkenyl group, a bicycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, and a nitro group. , Carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonyl Amino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, Rufamoyl group, N, N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N-benzoylsulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl Group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group.

  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.

  Hereinafter, the compound represented by the general formula (4) will be described in detail with specific examples, but the present invention is not limited to the following specific examples.

Examples of the retardation increasing agent having a rod-like polarizability anisotropy of 200 × 10 ⁻²⁵ cm ³ or more and 2000 × 10 ⁻²⁵ cm ³ or less and a molecular end-to-end distance of 1.5 to 10 nm are as follows: A compound represented by the general formula (5) is also particularly preferable.

  Hereinafter, the compound of the formula (5) will be described in detail.

In General Formula (5), L ¹ and L ² each represent a single bond or a divalent linking group.

Specific examples of the divalent linking group include, for example, —NR ⁸ — (R ⁸ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, A hydrogen atom is preferred), —SO ₂ —, —CO—, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, an alkynylene group, a substituted or unsubstituted phenylene group, substituted or unsubstituted A substituted biphenylene group, a substituted or unsubstituted naphthalene group, —O—, —S—, —SO—, and a group obtained by combining two or more thereof.

More preferably, L ¹ and L ² are each a single bond, —NR ⁸ —, —O— or —S—, more preferably a single bond or —NR ⁸ —, and most preferably —NR. ⁸ −.

In General Formula (5), R ¹ and R ² are each a hydrogen atom or a substituent. As examples of the substituent, those of T and T2 can be applied.

  Among the above substituents, those having a hydrogen atom may be substituted with the above groups after removing this.

R ¹ and R ² preferably have 10 or less carbon atoms, and each is a chlorine atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, or an acyloxy group. An amino group, more preferably a chlorine atom, an alkyl group, an aryl group, a hydroxyl group, or an amino group.

In general formula (5), R ³ and R ⁴ each represent a substituent. Examples of the substituent include the examples given for R ¹ and R ² .

In general formula (5), n represents an integer of 0 to 4, and when n is 2 or more, a plurality of R ³ may be the same or different from each other, and if possible, bonded to each other to form a ring It may be formed. n is preferably an integer of 0 to 2, more preferably 0.

In general formula (5), m represents an integer of 0 to 4. When m is 2 or more, a plurality of R ⁴ may be the same or different from each other, and if possible, they may be bonded to each other to form a ring. m is preferably an integer of 0 to 3.

  In General Formula (5), X1 represents an integer of 1 to 5. When X1 is 2 or more, a plurality of (R4) m may be the same or different. X1 is preferably an integer of 1 to 3, more preferably 1 or 2.

In general formula (5), ^R41 represents a hydrogen atom or a substituent. Examples of the substituent include the examples given for R ¹ and R ² . Preferably, they are a halogen atom, an alkyl group, a cyano group, a hydroxyl group, an alkoxy group, an aryl group, an alkoxycarbonyl group, an acyloxy group, or an alkoxycarbonyloxy group.

  Hereinafter, the compound represented by the general formula (5) will be described in detail with specific examples, but the present invention is not limited to the following specific examples. Regarding the following compounds, unless otherwise specified, the number in parentheses () indicates the exemplified compound (X).

  Here, Ra, Rb, and Rc are groups represented by the following Table 1, respectively.

  Here, the groups R-1 to R-23 in Table 1 are as follows.

  It is necessary to add at least one of the retardation increasing agents having a large rod-shaped polarizability anisotropy of the molecule to the cellulose in an amount of 0.1 to 30% by mass, preferably 0.5 to 20% by mass. More preferably, it is 1-15 mass%, Most preferably, it is 1-10 mass%. When using 2 or more types, it is preferable that the total amount satisfy | fills said range.

  Other preferable rod-shaped polarizability anisotropy retardation increasing agents include the following compound D-1.

<Compound with a plane polarizability anisotropy represented by the formula (2) of 150 × 10 ⁻²⁵ cm ³ or more and 1500 × 10 ⁻²⁵ cm ³ or less and a distance between molecular ends of 1.5 nm or more and 10 nm or less>
The polarizability of the molecule can be obtained by calculation using the molecular orbital method or the density functional method, and the plane polarizability anisotropy represented by the formula (2) is 150 × 10 ⁻²⁵ cm ³ or more and 1500 × 10 ^−. It must be ²⁵ cm ³ or less.

In order to achieve the effect of the present invention, the plane polarizability anisotropy is preferably 350 × 10 ⁻²⁵ cm ³ or more and 1500 × 10 ⁻²⁵ cm ³ or less.

Formula (2): Δα = (αx + αy) / 2−αz
The retardation increasing agent of the present invention having a plane polarizability anisotropy of 150 × 10 ⁻²⁵ cm ³ or more and 1500 × 10 ⁻²⁵ cm ³ or less and a molecular end-to-end distance of 1.5 nm or more and 10 nm or less is generally used. A compound represented by formula (6) is particularly preferred.

(Wherein R ²¹ , R ²² and R ²³ are each independently an alkyl group, an alkenyl group, an aromatic ring group or a heterocyclic group.)
R ²¹ , R ²² and R ²³ each independently represents an alkyl group, an alkenyl group, an aromatic ring group or a heterocyclic group, and more preferably an aromatic ring or a heterocyclic ring.

The aromatic ring represented by each of R ²¹ , R ²² and R ²³ is preferably phenyl or naphthyl. R ²¹ , R ²² and R ²³ may have a substituent on the aromatic ring or heterocyclic ring.

  Examples of the substituent include 10 or less carbon atoms, halogen atom, hydroxyl group, cyano group, nitro group, carboxyl group, alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group , Acyloxy group, alkoxycarbonyl group, alkenyloxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, alkyl-substituted sulfamoyl group, alkenyl-substituted sulfamoyl group, aryl-substituted sulfamoyl group, sulfonamide group, carbamoyl group, alkyl-substituted carbamoyl group, alkenyl-substituted Examples thereof include a carbamoyl group, an aryl-substituted carbamoyl group, an amide group, an alkylthio group, an alkenylthio group, an arylthio group, and an acyl group.

When R ²¹ , R ²² and R ²³ represent a heterocyclic group, the heterocyclic ring preferably has aromaticity. The heterocycle having aromaticity is generally an unsaturated heterocycle, preferably a heterocycle having the largest number of double bonds.

  The heterocyclic ring is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and most preferably a 6-membered ring. The hetero atom of the heterocyclic ring is preferably a nitrogen atom, a sulfur atom or an oxygen atom, and particularly preferably a nitrogen atom. As the heterocyclic ring having aromaticity, a pyridine ring (2-pyridyl or 4-pyridyl as the heterocyclic group) is particularly preferable.

  The heterocyclic group may have a substituent. Examples of the substituent of the heterocyclic group are the same as the examples of the substituent described above. These substituents may be further substituted with the above substituents.

  Preferred examples of the compound represented by the general formula (6) of the present invention are shown below, but the present invention is not limited to these specific examples.

  It is necessary to add at least one of the retardation increasing agents having a large plane polarizability anisotropy of the molecule to the cellulose in an amount of 0.1 to 30% by mass, preferably 0.5 to 20% by mass. More preferably, it is 1-15 mass%, Most preferably, it is 1-10 mass%. When using 2 or more types, it is preferable that the total amount satisfy | fills said range.

  As other preferable retardation increasing agents for plane polarizability anisotropy, the following compound E-1 may be mentioned.

  In addition, the retardation increasing agent having a large rod-like polarizability anisotropy of the molecule of the present invention and a retardation increasing agent having a large planar polarizability anisotropy of the molecule can be used to suppress bleed out more effectively. And particularly preferred.

  When using together, it is preferable that the total amount satisfy | fills the same numerical range as said one type of case. The mixing ratio of these retardation increasing agents is 0.01 to 100 parts by mass of a retardation increasing agent having a large planar polarizability anisotropy with respect to 1 part by mass of the retardation increasing agent having a large rod-like polarizability anisotropy of the molecule. Is preferable, and 0.1-10 mass parts is further more preferable.

<Acrylic polymer>
In the present invention, an acrylic polymer is added to the cellulose ester film. Here, the acrylic polymer includes a methacrylic polymer.

  As an acrylic polymer used in the present invention, when it is contained in a cellulose ester film, it preferably exhibits negative birefringence as a function of the stretching direction, and the structure is not particularly limited. A polymer having a weight average molecular weight of 500 to 30,000 obtained by polymerizing an ethylenically unsaturated monomer is preferred.

(Test method for birefringence of acrylic polymer)
The acrylic polymer was dissolved in a solvent to form a cast film, and then dried by heating. The film having a transmittance of 80% or more was evaluated for birefringence.

  Refractive index measurement was performed using an Abbe refractometer-4T (manufactured by Atago Co., Ltd.) using a multi-wavelength light source. The refractive index ny in the stretching direction and the refractive index in the in-plane direction perpendicular to each other were defined as nx. For films with (ny−nx) <0 for each refractive index at 550 nm, the acrylic polymer is judged to be negatively birefringent with respect to the stretch direction.

  The acrylic polymer having a weight average molecular weight of 500 or more and 30000 or less used in the present invention may be an acrylic polymer having an aromatic ring in the side chain or an acrylic polymer having a cyclohexyl group in the side chain.

  When the weight average molecular weight of the polymer is 500 or more and 30000 or less and the composition of the polymer is controlled, for example, when the cellulose ester film is a particularly preferable cellulose ester film in the present invention, the cellulose ester and the polymer The compatibility with can be improved.

  As for the acrylic polymer having an aromatic ring in the side chain or the acrylic polymer having a cyclohexyl group in the side chain, if the weight average molecular weight is 500 or more and 10,000 or less, in addition to the above, cellulose after film formation The transparency of the ester film is excellent, the moisture permeability is extremely low, and it exhibits excellent performance as a protective film for polarizing plates.

  Since the polymer has a weight average molecular weight of 500 or more and 30000 or less, it is considered to be between the oligomer and the low molecular weight polymer. In order to synthesize such a polymer, it is difficult to control the molecular weight in normal polymerization, and it is desirable to use a method that can align the molecular weight as much as possible by a method that does not increase the molecular weight too much.

  In particular, the acrylic polymer used in the cellulose ester film of the present invention includes an ethylenically unsaturated monomer Xa having no aromatic ring and a hydroxyl group in the molecule, and an ethylene having a hydroxyl group and no aromatic ring in the molecule. Polymer X having a weight average molecular weight of 2,000 to 30,000 obtained by copolymerization of a polymerizable unsaturated monomer Xb and a copolymerizable ethylenically unsaturated monomer excluding Xa and Xb, or ethylene having no aromatic ring The polymer Y is preferably a polymer Y having a weight average molecular weight of 500 or more and 3000 or less, obtained by polymerizing the polymerizable unsaturated monomer Ya and an ethylenically unsaturated monomer copolymerizable with Ya.

[Polymer X, Polymer Y]
The method for adjusting Ro and Rt of the cellulose ester film according to the present invention includes ethylenically unsaturated monomer Xa having no aromatic ring and hydroxyl group in the molecule, and ethylene having a hydroxyl group and no aromatic ring in the molecule. High molecular weight polymer X having a weight average molecular weight of 2,000 to 30,000 obtained by copolymerization of the polymerizable unsaturated monomer Xb and a copolymerizable ethylenically unsaturated monomer excluding Xa and Xb, and more preferably, Contains a low molecular weight polymer Y having a weight average molecular weight of 500 to 3,000 obtained by polymerizing an ethylenically unsaturated monomer Ya having no aromatic ring and an ethylenically unsaturated monomer copolymerizable with Ya It is preferable.

  The polymer X used in the present invention includes an ethylenically unsaturated monomer Xa having no aromatic ring and a hydroxyl group in the molecule and an ethylenically unsaturated monomer Xb having no hydroxyl ring in the molecule and having a hydroxyl group, Xa and Xb. Is a polymer having a weight average molecular weight of 2000 or more and 30000 or less obtained by copolymerization with a copolymerizable ethylenically unsaturated monomer other than.

  Preferably, Xa is an acrylic or methacrylic monomer having no aromatic ring and hydroxyl group in the molecule, and Xb is an acrylic or methacrylic monomer having no aromatic ring and having a hydroxyl group in the molecule.

  The polymer X used in the present invention is represented by the following general formula (X).

Formula (X)
-[Xa] m- [Xb] n- [Xc] p-
In the general formula (X), Xa represents an ethylenically unsaturated monomer having no aromatic ring and hydroxyl group in the molecule, and Xb represents an ethylenically unsaturated monomer having no aromatic ring and having a hydroxyl group in the molecule. Xc represents a copolymerizable ethylenically unsaturated monomer excluding Xa and Xb. m, n, and p each represent a molar composition ratio. However, m ≠ 0 and m + n + p = 100.

  Furthermore, the polymer X is preferably a polymer represented by the following general formula (X-1).

Formula (X-1)
_{- [CH 2 -C (-R1)} (- CO 2 R2)] m- [CH 2 -C (-R3) (- CO 2 R4-OH) -] n- [Xc] p-
In the general formula (X-1), R1 and R3 each represent a hydrogen atom or a methyl group. R2 represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group. R4 is _{-CH 2 -, - C 2 H} 4 - or -C ₃ H ₆ - represents a. Xc _{is, [CH 2 -C (-R1)} (- CO 2 R2)] representing the a polymerizable monomer unit or _{[CH 2 -C (-R3) (} - - CO 2 R4-OH)]. m, n, and p represent a molar composition ratio. However, m ≠ 0 and m + n + p = 100.

  Although the monomer as a monomer unit which comprises the polymer X which concerns on this invention is mentioned below, it is not limited to this.

  In X, the hydroxyl group means not only a hydroxyl group but also a group having an ethylene oxide chain.

  Examples of the ethylenically unsaturated monomer Xa having no aromatic ring and hydroxyl group in the molecule include methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), and butyl acrylate (n-, i-, s). -, T-), pentyl acrylate (n-, i-, s-), hexyl acrylate (n-, i-), heptyl acrylate (n-, i-), octyl acrylate (n-, i -), Nonyl acrylate (n-, i-), myristyl acrylate (n-, i-), acrylic acid (2-ethylhexyl), acrylic acid (ε-caprolactone), etc. The thing changed into acid ester can be mentioned.

  Among these, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and propyl methacrylate (i-, n-) are preferable.

  The ethylenically unsaturated monomer Xb having no hydroxyl ring in the molecule and having a hydroxyl group is preferably acrylic acid or methacrylic acid ester as a monomer unit having a hydroxyl group, such as acrylic acid (2-hydroxyethyl), acrylic acid. (2-hydroxypropyl), acrylic acid (3-hydroxypropyl), acrylic acid (4-hydroxybutyl), acrylic acid (2-hydroxybutyl), or those obtained by replacing these acrylic acids with methacrylic acid. Preferred are acrylic acid (2-hydroxyethyl) and methacrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), and acrylic acid (3-hydroxypropyl).

  Xc is not particularly limited as long as it is a monomer other than Xa and Xb and is a copolymerizable ethylenically unsaturated monomer, but preferably has no aromatic ring.

  The molar composition ratio m: n of Xa and Xb is preferably in the range of 99: 1 to 65:35, more preferably in the range of 95: 5 to 75:25. P of Xc is 0-10. Xc may be a plurality of monomer units.

  When the molar composition ratio of Xa is large, the compatibility with the cellulose ester is improved, but the retardation value Rt in the film thickness direction is increased. When the molar composition ratio of Xb is large, the compatibility is deteriorated, but the effect of reducing Rt is high.

  Further, if the molar composition ratio of Xb exceeds the above range, haze tends to occur during film formation, and it is preferable to optimize these and determine the molar composition ratio of Xa and Xb.

  The molecular weight of the high molecular weight polymer X is more preferably 5,000 or more and 30,000 or less, and still more preferably 8,000 or more and 25,000 or less.

  By setting the weight average molecular weight to 5000 or more, advantages such as little dimensional change under high temperature and high humidity of the cellulose ester film can be obtained.

  When the weight average molecular weight is 30000 or less, compatibility with the cellulose ester is further improved, and bleeding out under high temperature and high humidity and further haze generation immediately after film formation are suppressed.

  The weight average molecular weight of the polymer X according to the present invention can be adjusted by a known molecular weight adjusting method. Examples of such a molecular weight adjusting method include a method of adding a chain transfer agent such as carbon tetrachloride, lauryl mercaptan, octyl thioglycolate, and the like.

  The polymerization temperature is usually from room temperature to 130 ° C., preferably from 50 ° C. to 100 ° C., and this temperature or the polymerization reaction time can be adjusted.

  In addition, a weight average molecular weight etc. can be calculated | required according to the above-mentioned method.

  The low molecular weight polymer Y used in the present invention is a polymer having a weight average molecular weight of 500 or more and 3000 or less obtained by polymerizing an ethylenically unsaturated monomer Ya having no aromatic ring. A weight average molecular weight of 500 or more is preferred because the residual monomer in the polymer is reduced.

  Moreover, it is preferable to set it as 3000 or less in order to maintain retardation value Rt fall performance. Ya is preferably an acrylic or methacrylic monomer having no aromatic ring.

  The polymer Y used in the present invention is represented by the following general formula (Y).

General formula (Y)
-[Ya] k- [Yb] q-
In the general formula (Y), Ya represents an ethylenically unsaturated monomer having no aromatic ring, and Yb represents an ethylenically unsaturated monomer copolymerizable with Ya. k and q each represent a molar composition ratio. However, k ≠ 0 and k + q = 100.

  The polymer Y according to the present invention is more preferably a polymer represented by the following general formula (Y-1).

General formula (Y-1)
_{- [CH 2 -C (-R5)} (- CO 2 R6)] k- [Yb] q-
In the general formula (Y-1), R5 represents a hydrogen atom or a methyl group, respectively. R6 represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group. Yb represents a monomer unit copolymerizable with [CH ₂ —C (—R 5) (— CO ₂ R 6)]. k and q each represent a molar composition ratio. However, k ≠ 0 and k + q = 100.

Yb is a _{Ya [CH 2 -C (-R5)} (- CO 2 R6)] and is not particularly limited as long as it is copolymerizable ethylenically unsaturated monomers. Yb may be plural. k + q = 100, q is preferably 0-30.

  The ethylenically unsaturated monomer Ya constituting the polymer Y obtained by polymerizing the ethylenically unsaturated monomer having no aromatic ring is, for example, methyl acrylate, ethyl acrylate, propyl acrylate ( i-, n-), butyl acrylate (n-, i-, s-, t-), pentyl acrylate (n-, i-, s-), hexyl acrylate (n-, i-), acrylic Acid heptyl (n-, i-), octyl acrylate (n-, i-), nonyl acrylate (n-, i-), myristyl acrylate (n-, i-), cyclohexyl acrylate, acrylic acid ( 2-ethylhexyl), acrylic acid (ε-caprolactone), acrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), acrylic acid (3-hydroxypropiyl) ), Acrylic acid (4-hydroxybutyl), acrylic acid (2-hydroxybutyl), methacrylic acid ester, the above acrylic acid ester changed to methacrylic acid ester; unsaturated acid, for example, acrylic acid, methacrylic acid And maleic anhydride, crotonic acid, itaconic acid and the like.

  Yb is not particularly limited as long as it is an ethylenically unsaturated monomer copolymerizable with Ya. Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl pivalate, and vinyl caproate. Vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, vinyl octylate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl cinnamate and the like are preferred. Yb may be plural.

  In order to synthesize the polymers X and Y, it is difficult to control the molecular weight in normal polymerization, and it is desirable to use a method that can make the molecular weights as uniform as possible without increasing the molecular weight.

  Such polymerization methods include a method using a peroxide polymerization initiator such as cumene peroxide and t-butyl hydroperoxide, a method using a polymerization initiator in a larger amount than normal polymerization, and a mercapto compound in addition to the polymerization initiator. And a method of using a chain transfer agent such as carbon tetrachloride, a method of using a polymerization terminator such as benzoquinone and dinitrobenzene in addition to the polymerization initiator, and further, Japanese Patent Application Laid-Open No. 2000-128911 or 2000-344823. Examples thereof include a compound having one thiol group and a secondary hydroxyl group, or a bulk polymerization method using a polymerization catalyst in which the compound and an organometallic compound are used in combination. Used.

  In particular, the polymer Y is preferably a polymerization method using a compound having a thiol group and a secondary hydroxyl group in the molecule as a chain transfer agent. In this case, the terminal of the polymer Y has a hydroxyl group and a thioether resulting from the polymerization catalyst and the chain transfer agent. The compatibility of Y and cellulose ester can be adjusted by this terminal residue.

  The hydroxyl values of the polymers X and Y are preferably 30 to 150 [mg KOH / g].

  The hydroxyl value is measured in accordance with JIS K 0070 (1992). This hydroxyl value is defined as the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated.

  Specifically, sample Xg (about 1 g) is precisely weighed in a flask, and 20 ml of an acetylating reagent (a solution obtained by adding pyridine to 20 ml of acetic anhydride to 400 ml) is accurately added thereto. An air cooling tube is attached to the mouth of the flask and heated in a glycerin bath at 95-100 ° C.

  After 1 hour and 30 minutes, the mixture is cooled, 1 ml of purified water is added from an air condenser, and acetic anhydride is decomposed into acetic acid.

  Next, titration is performed with a 0.5 mol / L potassium hydroxide ethanol solution using a potentiometric titrator, and the inflection point of the obtained titration curve is set as the end point.

  Further, as a blank test, titration is performed without a sample, and an inflection point of the titration curve is obtained. The hydroxyl value is calculated by the following formula.

Hydroxyl value = {(BC) × f × 28.05 / X} + D
In the formula, B is the amount (ml) of 0.5 mol / L potassium hydroxide ethanol solution used for the blank test, C is the amount (ml) of 0.5 mol / L potassium hydroxide ethanol solution used for titration, f is a factor of a 0.5 mol / L potassium hydroxide ethanol solution, D is an acid value, and 28.05 is 1/2 of 1 mol amount 56.11 of potassium hydroxide.

  The above-mentioned polymer X and polymer Y are both excellent in compatibility with cellulose ester, excellent in productivity without evaporation and volatilization, good retention as a protective film for polarizing plates, low moisture permeability, and dimension stability. Excellent in properties.

The content of the polymer X and the polymer Y in the cellulose ester film is preferably in a range satisfying the following formulas (i) and (ii). When the content of the polymer X is Xg (mass% = (mass of polymer X / mass of cellulose ester) × 100) and the content of the polymer Y is Yg (mass%),
Formula (i) 5 ≦ Xg + Yg ≦ 35 (mass%)
Formula (ii) 0.05 ≦ Yg / (Xg + Yg) ≦ 0.4
A preferable range of (Xg + Yg) in the formula (i) is 10 to 35% by mass. If the polymer X and the polymer Y are 5 mass% or more as a total amount with respect to the total mass of the cellulose ester, the polymer X and the polymer Y have a sufficient effect for adjusting the retardation value Rt.

  The polymer X and the polymer Y can be directly added and dissolved as a material constituting the dope solution described later, or can be added to the dope solution after being previously dissolved in an organic solvent for dissolving the cellulose ester.

<Ester compound in which at least one of pyranose structure or furanose structure is 1 or more and 12 or less and all or part of OH groups of the structure are esterified>
The cellulose ester film of the present invention is characterized by comprising an ester compound having at least one pyranose structure or at least one furanose structure and having all or part of OH groups in the structure esterified.

  The proportion of esterification is preferably 70% or more of the OH groups present in the pyranose structure or furanose structure.

  In the present invention, ester compounds are collectively referred to as sugar ester compounds.

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

  Glucose, galactose, mannose, fructose, xylose or arabinose, lactose, sucrose, nystose, 1F-fructosyl nystose, stachyose, maltitol, lactitol, lactulose, cellobiose, maltose, cellotriose, maltotriose, raffinose or kestose .

  In addition, gentiobiose, gentiotriose, gentiotetraose, xylotriose, galactosyl sucrose, and the like are also included.

  Among these compounds, compounds having both a pyranose structure and a furanose structure are particularly preferable.

  Examples include sucrose, kestose, nystose, 1F-fructosyl nystose, stachyose, and more preferably sucrose.

  The monocarboxylic acid used for esterifying all or part of the OH groups in the pyranose structure or furanose structure of the present invention is not particularly limited, and known aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, An aromatic monocarboxylic acid or the like can be used. The carboxylic acid used may be one type or a mixture of two or more types.

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

  Examples of preferable alicyclic monocarboxylic acids include acetic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and derivatives thereof.

  Examples of preferred aromatic monocarboxylic acids include aromatic monocarboxylic acids having an alkyl group or alkoxy group introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, cinnamic acid, benzylic acid, biphenylcarboxylic acid, and naphthalene. Examples thereof include aromatic monocarboxylic acids having two or more benzene rings such as carboxylic acid and tetralin carboxylic acid, or derivatives thereof. More specifically, xylyl acid, hemelic acid, mesitylene acid, prenylic acid, γ-isoduric acid, jurylic acid, mesitic acid, α-isoduric acid, cumic acid, α-toluic acid, hydroatropic acid, atropic acid, hydrocinnamic acid, salicylic acid, o-anisic acid, m-anisic acid, p-anisic acid , Creosote acid, o-homosalicylic acid, m-homosalicylic acid, p-homosalicylic acid, o-pyroca Succinic acid, β-resorcylic acid, vanillic acid, isovanillic acid, veratrumic acid, o-veratrumic acid, gallic acid, asaronic acid, mandelic acid, homoanisic acid, homovanillic acid, homoveratrumic acid, o-homoveratrumic acid, phthalonic acid, p- Although coumaric acid can be mentioned, benzoic acid is particularly preferable.

  The oligosaccharide ester compound can be applied as a compound having 1 to 12 at least one of the pyranose structure or furanose structure according to the present invention.

  Oligosaccharides are produced by allowing an enzyme such as amylase to act on starch, sucrose, etc. Examples of oligosaccharides that can be applied to the present invention include maltooligosaccharides, isomaltoligosaccharides, fructooligosaccharides, galactooligosaccharides, xylooligos. Sugar.

Moreover, the said ester compound is a compound which condensed 1 or more and 12 or less of at least 1 sort (s) of the pyranose structure or furanose structure represented with the following general formula (A). However, R < ₁₁ > -R < ₁₅ >, R < ₂₁ > -R < ₂₅ > represents a C2-C22 acyl group or a hydrogen atom, m and n represent the integer of 0-12 respectively, and m + n represents the integer of 1-12.

R _{11 to} R ₁₅ and R _{21 to} R ₂₅ are preferably a benzoyl group or a hydrogen atom. The benzoyl group may further have a substituent R ₂₆ (p is 0 to 5), and examples thereof include an alkyl group, an alkenyl group, an alkoxyl group, and a phenyl group, and further, these alkyl groups, alkenyl groups, and phenyl groups. May have a substituent. Oligosaccharides can also be produced by the same method as the ester compound of the present invention.

  Although the specific example of the ester compound which concerns on this invention is given to the following, this invention is not limited to this.

  The cellulose ester film of the present invention preferably contains the ester compound of the present invention in an amount of 1 to 30% by mass of the cellulose ester film in order to suppress the fluctuation of the retardation value and stabilize the display quality. 5 to 30% by mass is preferable.

<Cellulose ester>
The cellulose ester of the present invention is not particularly limited, but the cellulose ester is a carboxylic acid ester having about 2 to 22 carbon atoms, and may be an aromatic carboxylic acid ester, particularly a lower fatty acid ester having 6 or less carbon atoms. It is preferable.

  The acyl group bonded to the hydroxyl group may be linear or branched or may form a ring. Furthermore, another substituent may be substituted. When the degree of substitution is the same, birefringence decreases when the number of carbon atoms is large, and therefore, the number of carbon atoms is preferably selected from acyl groups having 2 to 6 carbon atoms. The cellulose ester preferably has 2 to 4 carbon atoms, more preferably 2 to 3 carbon atoms.

  Specifically, the cellulose ester includes cellulose acetate propionate, cellulose acetate butyrate, or a mixed fatty acid ester of cellulose to which a propionate group or a butyrate group is bonded in addition to an acetyl group such as cellulose acetate propionate butyrate. Can be used.

  The butyryl group forming butyrate may be linear or branched. As the cellulose ester preferably used in the present invention, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, and cellulose acetate phthalate are particularly preferably used.

  Preferred cellulose esters other than cellulose acetate phthalate for the present invention preferably satisfy the following formulas (1) and (2).

Formula (1) 2.0 <= X + Y <= 3.0
Formula (2) 0 ≦ Y ≦ 1.5
In the formula, X is the degree of substitution of the acetyl group, and Y is the degree of substitution of the propionyl group or butyryl group, or a mixture thereof.

  Further, in order to obtain optical characteristics that meet the purpose, resins having different degrees of substitution may be mixed and used. The mixing ratio is preferably 100: 0 to 50:50 (mass ratio).

  Of these, cellulose acetate propionate is particularly preferably used. In cellulose acetate propionate, 1.0 ≦ X ≦ 2.5, preferably 0.1 ≦ Y ≦ 1.5, and 2.0 ≦ X + Y ≦ 3.0. The measuring method of the substitution degree of an acyl group can be measured according to ASTM-D817-96.

  The number average molecular weight of the cellulose ester used in the present invention is preferably in the range of 60,000 to 300,000 because the mechanical strength of the resulting film is strong. Furthermore, the thing of 70000-200000 is used preferably.

  The weight average molecular weight Mw and number average molecular weight Mn of the cellulose ester were measured using gel permeation chromatography (GPC).

  The measurement conditions are as follows.

Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three Showa Denko Co., Ltd.)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (manufactured by GL Sciences)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) Mw = 100000 to 500 calibration curves with 13 samples were used. Thirteen samples are used at approximately equal intervals.

  The cellulose used as a raw material of the cellulose ester used in the present invention is not particularly limited, and examples thereof include cotton linter, wood pulp, and kenaf.

  Moreover, the cellulose ester obtained from them can be mixed and used in arbitrary ratios, respectively.

  The cellulose ester of the present invention can be produced by a known method. Specifically, it can be synthesized with reference to the method described in JP-A-10-45804.

<Other additives>
(Plasticizer)
The cellulose ester film of the present invention can contain a plasticizer as necessary to obtain the effects of the present invention.

  The plasticizer is not particularly limited, but is preferably a polycarboxylic acid ester plasticizer, a glycolate plasticizer, a phthalate ester plasticizer, a fatty acid ester plasticizer, a polyhydric alcohol ester plasticizer, or a polyester plasticizer. Agent, acrylic plasticizer and the like.

  Of these, when two or more plasticizers are used, at least one plasticizer is preferably a polyhydric alcohol ester plasticizer.

  The polyhydric alcohol ester plasticizer is a plasticizer comprising an ester of a dihydric or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule. Preferably it is a 2-20 valent aliphatic polyhydric alcohol ester.

  The polyhydric alcohol preferably used in the present invention is represented by the following general formula (a).

Formula (a) R1- (OH) n
However, R1 represents an n-valent organic group, n represents a positive integer of 2 or more, and the OH group represents an alcoholic and / or phenolic hydroxyl group.

  Examples of preferred polyhydric alcohols include the following, but the present invention is not limited to these.

  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, galactitol, mannitol, 3-methylpentane- Examples include 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.

  There is no restriction | limiting in particular as monocarboxylic acid used for polyhydric alcohol ester, Well-known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid, etc. can be used. Use of an alicyclic monocarboxylic acid or aromatic monocarboxylic acid is preferred in terms of improving moisture permeability and retention.

  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, the 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-hexanoic 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, olein Examples thereof include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid.

  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 1 to 3 alkoxy groups such as alkyl group, methoxy group or ethoxy group are introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, biphenylcarboxylic acid, Examples thereof include aromatic monocarboxylic acids having two or more benzene rings such as naphthalenecarboxylic acid and tetralincarboxylic acid, or derivatives thereof. Benzoic acid is particularly preferable.

  The molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably 300 to 1500, and more preferably 350 to 750. A higher molecular weight is preferred because it is less likely to volatilize, and a smaller one is preferred in terms of moisture permeability and compatibility with cellulose ester.

  The carboxylic acid used for the polyhydric alcohol ester 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.

  Below, the specific compound of a polyhydric alcohol ester is illustrated.

  The glycolate plasticizer is not particularly limited, but alkylphthalylalkyl glycolates can be preferably used.

  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, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, butyl phthalyl ethyl glycolate, propyl phthalyl butyl glycol Butyl phthalyl propyl glycolate, methyl phthalyl octyl glycolate, ethyl phthalyl octyl glycolate, octyl phthalyl methyl glycolate, octyl phthalate Ethyl glycolate, and the like.

  Examples of the phthalate ester plasticizer include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, and dicyclohexyl terephthalate.

  Examples of the citrate plasticizer include acetyl trimethyl citrate, acetyl triethyl citrate, and acetyl tributyl citrate.

  Examples of fatty acid ester plasticizers include butyl oleate, methylacetyl ricinoleate, and dibutyl sebacate.

  Examples of the phosphate ester plasticizer include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate and the like.

  The polyvalent carboxylic acid ester compound is composed of an ester of divalent or higher, preferably divalent to 20 valent polyvalent carboxylic acid and alcohol. The aliphatic polyvalent carboxylic acid is preferably 2 to 20 valent, and in the case of an aromatic polyvalent carboxylic acid or an alicyclic polyvalent carboxylic acid, it is preferably 3 to 20 valent.

  The polyvalent carboxylic acid is represented by the following general formula (b).

Formula (b) R2 (COOH) m (OH) n
(Wherein R2 is an (m + n) -valent organic group, m is a positive integer of 2 or more, n is an integer of 0 or more, a COOH group is a carboxyl group, and an OH group is an alcoholic or phenolic hydroxyl group)
Examples of preferred polyvalent carboxylic acids include the following, but the present invention is not limited to these.

  Trivalent or higher aromatic polyvalent carboxylic acids such as trimellitic acid, trimesic acid, pyromellitic acid or derivatives thereof, succinic acid, adipic acid, azelaic acid, sebacic acid, oxalic acid, fumaric acid, maleic acid, tetrahydrophthal An aliphatic polyvalent carboxylic acid such as an acid, an oxypolyvalent carboxylic acid such as tartaric acid, tartronic acid, malic acid and citric acid can be preferably used. In particular, it is preferable to use an oxypolycarboxylic acid from the viewpoint of improving retention.

  There is no restriction | limiting in particular as alcohol used for the polyhydric carboxylic acid ester compound which can be used for this invention, Well-known alcohol and phenols can be used.

  For example, an aliphatic saturated alcohol or aliphatic unsaturated alcohol having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. It is more preferable that it is C1-C20, and it is especially preferable that it is C1-C10.

  In addition, alicyclic alcohols such as cyclopentanol and cyclohexanol or derivatives thereof, aromatic alcohols such as benzyl alcohol and cinnamyl alcohol, or derivatives thereof can also be preferably used.

  When an oxypolycarboxylic acid is used as the polycarboxylic acid, the alcoholic or phenolic hydroxyl group of the oxypolycarboxylic acid may be esterified with a monocarboxylic acid. 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 a side chain having 1 to 32 carbon atoms can be preferably used. It is more preferable that it is C1-C20, and it is especially preferable that it is C1-C10.

  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, and laccelic acid, undecylenic acid, olein Examples thereof include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid.

  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 biphenyl carboxylic acid, naphthalene carboxylic acid, and tetralin carboxylic acid. And aromatic monocarboxylic acids possessed by them, or derivatives thereof. Particularly preferred are acetic acid, propionic acid, and benzoic acid.

  The molecular weight of the polyvalent carboxylic acid ester compound is not particularly limited, but is preferably in the range of 300 to 1000, and more preferably in the range of 350 to 750. The larger one is preferable in terms of improvement in retention, and the smaller one is preferable in terms of moisture permeability and compatibility with cellulose ester.

  The alcohol used for the polyvalent carboxylic acid ester that can be used in the present invention may be one kind or a mixture of two or more kinds.

  The acid value of the polyvalent carboxylic acid ester compound that can be used in the present invention is preferably 1 mgKOH / g or less, and more preferably 0.2 mgKOH / g or less. Setting the acid value in the above range is preferable because the environmental fluctuation of retardation is also suppressed.

  In addition, an acid value means the milligram number of potassium hydroxide required in order to neutralize the acid (carboxyl group which exists in a sample) contained in 1g of samples. The acid value is measured according to JIS K0070.

  Examples of particularly preferred polyvalent carboxylic acid ester compounds are shown below, but the present invention is not limited thereto.

  For example, triethyl citrate, tributyl citrate, acetyl triethyl citrate (ATEC), acetyl tributyl citrate (ATBC), benzoyl tributyl citrate, acetyl triphenyl citrate, acetyl tribenzyl citrate, dibutyl tartrate, diacetyl dibutyl tartrate, Examples include tributyl trimellitic acid and tetrabutyl pyromellitic acid.

  The polyester plasticizer is not particularly limited, and a polyester plasticizer having an aromatic ring or a cycloalkyl ring in the molecule can be used. Although it does not specifically limit as a polyester plasticizer, For example, the aromatic terminal ester plasticizer represented by the following general formula (c) can be used.

General formula (c) B- (GA) n-GB
(In the formula, B is a benzene monocarboxylic acid residue, G is an alkylene glycol residue having 2 to 12 carbon atoms, an aryl glycol residue having 6 to 12 carbon atoms, or an oxyalkylene glycol residue having 4 to 12 carbon atoms, A represents an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms or an aryl dicarboxylic acid residue having 6 to 12 carbon atoms, and n represents an integer of 1 or more.)
In the general formula (c), a benzene monocarboxylic acid residue represented by B and an alkylene glycol residue, oxyalkylene glycol residue or aryl glycol residue represented by G, an alkylene dicarboxylic acid residue or aryl dicarboxylic group represented by A It is composed of an acid residue and can be obtained by a reaction similar to that of a normal polyester plasticizer.

  Examples of the benzene monocarboxylic acid component of the polyester plasticizer used in the present invention include benzoic acid, para-tert-butylbenzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, dimethylbenzoic acid, ethylbenzoic acid, and normalpropyl. There exist benzoic acid, aminobenzoic acid, acetoxybenzoic acid, etc., and these can be used as 1 type, or 2 or more types of mixtures, respectively.

  Examples of the alkylene glycol component having 2 to 12 carbon atoms of the polyester plasticizer that can be used in the present invention include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1, 3-butanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neo Pentyl glycol), 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3propanediol (3,3-dimethylolheptane) 3-methyl-1,5-pentanediol 1,6-hexanediol, 2,2,4-trimethyl 1,3-penta Diol, 2-ethyl 1,3-hexanediol, 2-methyl 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, and the like. It is used as one kind or a mixture of two or more kinds.

  In particular, an alkylene glycol having 2 to 12 carbon atoms is particularly preferable because of excellent compatibility with a cellulose ester.

  In addition, examples of the oxyalkylene glycol component having 4 to 12 carbon atoms of the aromatic terminal ester include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol. It can be used as a seed or a mixture of two or more.

  Examples of the alkylene dicarboxylic acid component having 4 to 12 carbon atoms of the aromatic terminal ester include succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid. These are used as one kind or a mixture of two or more kinds. Examples of the arylene dicarboxylic acid component having 6 to 12 carbon atoms include phthalic acid, terephthalic acid, isophthalic acid, 1,5 naphthalene dicarboxylic acid, and 1,4 naphthalene dicarboxylic acid.

  The polyester plasticizer used in the present invention has a number average molecular weight of preferably 300 to 1500, more preferably 400 to 1000. The acid value is 0.5 mgKOH / g or less, the hydroxyl value is 25 mgKOH / g or less, more preferably the acid value is 0.3 mgKOH / g or less, and the hydroxyl value is 15 mgKOH / g or less.

  Although the specific compound of the aromatic terminal ester plasticizer which can be used for this invention below is shown, this invention is not limited to this.

(UV absorber)
The cellulose ester film B according to the present invention can also contain an ultraviolet absorber. The ultraviolet absorber is intended to improve durability by absorbing ultraviolet rays of 400 nm or less, and in particular, the transmittance at a wavelength of 370 nm is preferably 10% or less, more preferably 5% or less, and further Preferably it is 2% or less.

  Although the ultraviolet absorber used in the present invention is not particularly limited, for example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, inorganic powders Examples include the body.

  For example, 5-chloro-2- (3,5-di-sec-butyl-2-hydroxylphenyl) -2H-benzotriazole, (2-2H-benzotriazol-2-yl) -6- (linear and side Chain dodecyl) -4-methylphenol, 2-hydroxy-4-benzyloxybenzophenone, 2,4-benzyloxybenzophenone, etc., and tinuvin 109, tinuvin 171, tinuvin 234, tinuvin 326, tinuvin 327, tinuvin 328, etc. These are commercially available products manufactured by Ciba Specialty Chemicals and can be preferably used.

  The UV absorbers preferably used in the present invention are benzotriazole UV absorbers, benzophenone UV absorbers, and triazine UV absorbers, particularly preferably benzotriazole UV absorbers and benzophenone UV absorbers. .

  In addition, a discotic compound such as a compound having a 1,3,5 triazine ring is also preferably used as the ultraviolet absorber.

  It is preferable that the polarizing plate protective film concerning this invention contains 2 or more types of ultraviolet absorbers.

  As the UV absorber, a polymer UV absorber can also be preferably used, and in particular, a polymer type UV absorber described in JP-A-6-148430 is preferably used.

  The method for adding the UV absorber is to add the UV absorber to the dope after dissolving the UV absorber in an alcohol such as methanol, ethanol or butanol, an organic solvent such as methylene chloride, methyl acetate, acetone or dioxolane, or a mixed solvent thereof. Or you may add directly in dope composition.

  For an inorganic powder that does not dissolve in an organic solvent, a dissolver or a sand mill is used in the organic solvent and cellulose ester to disperse and then added to the dope.

  The amount of the UV absorber used is not uniform depending on the type of UV absorber, the operating conditions, etc., but when the dry film thickness of the polarizing plate protective film is 30 to 200 μm, it is 0.5 with respect to the polarizing plate protective film. -10 mass% is preferable, and 0.6-4 mass% is still more preferable.

(Antioxidant)
Antioxidants are also referred to as deterioration inhibitors. When a liquid crystal image display device or the like is placed in a high humidity and high temperature state, the cellulose ester film may be deteriorated.

  The antioxidant has a role of delaying or preventing the cellulose ester film from being decomposed by, for example, a residual solvent amount of halogen in the cellulose ester film or phosphoric acid of a phosphoric acid plasticizer. It is preferable to make it contain in a film.

  As such an antioxidant, a hindered phenol compound is preferably used. For example, 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di- -T-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino)- 1,3,5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octa Sil-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide) 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-t-butyl-4-hydroxy Benzyl) -isocyanurate and the like.

  In particular, 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3 -(3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] is preferred. Further, for example, hydrazine-based metal deactivators such as N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine and tris (2,4-di- A phosphorus processing stabilizer such as t-butylphenyl) phosphite may be used in combination.

  The addition amount of these compounds is preferably 1 ppm to 1.0%, more preferably 10 to 1000 ppm in terms of mass ratio with respect to the cellulose derivative.

(Fine particles)
The cellulose ester film according to the present invention preferably contains fine particles.

  As fine particles used in the present invention, examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, and hydrated silicic acid. Mention may be made of calcium, aluminum silicate, magnesium silicate and calcium phosphate.

  Fine particles containing silicon are preferable in terms of low turbidity, and silicon dioxide is particularly preferable.

  The average primary particle diameter of the fine particles is preferably 5 to 400 nm, and more preferably 10 to 300 nm.

  These may be mainly contained as secondary aggregates having a particle size of 0.05 to 0.3 μm, and may be contained as primary particles without being aggregated if the particles have an average particle size of 100 to 400 nm. preferable.

  The content of these fine particles in the polarizing plate protective film is preferably 0.01 to 1% by mass, particularly preferably 0.05 to 0.5% by mass. In the case of a polarizing plate protective film having a multilayer structure by the co-casting method, it is preferable to contain fine particles of this addition amount on the surface.

  Silicon dioxide fine particles are commercially available, for example, under the trade names Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (above Nippon Aerosil Co., Ltd.). it can.

  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.

  Examples of the polymer include silicone resin, fluororesin, and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.) It is marketed by name and can be used.

  Among these, Aerosil 200V and Aerosil R972V are particularly preferably used because they have a large effect of reducing the friction coefficient while keeping the turbidity of the polarizing plate protective film low. In the polarizing plate protective film used in the present invention, the dynamic friction coefficient of at least one surface is preferably 0.2 to 1.0.

  Various additives may be batch-added to a dope that is a cellulose ester-containing solution before film formation, or an additive solution may be separately prepared and added in-line. In particular, it is preferable to add a part or all of the fine particles in-line in order to reduce the load on the filter medium.

  When the additive solution is added in-line, it is preferable to dissolve a small amount of cellulose ester in order to improve mixing with the dope. The amount of the cellulose ester is preferably 1 to 10 parts by mass, more preferably 3 to 5 parts by mass with respect to 100 parts by mass of the solvent.

  In order to perform in-line addition and mixing in the present invention, for example, an in-line mixer such as a static mixer (manufactured by Toray Engineering), SWJ (Toray static type in-tube mixer Hi-Mixer) or the like is preferably used.

<Method for producing biaxial transparent film made of cellulose ester film>
Next, the manufacturing method of the cellulose-ester film of this invention is demonstrated.

  The cellulose ester film according to the present invention can be preferably used regardless of whether it is a film produced by a solution casting method or a film produced by a melt casting method.

  The cellulose ester film of the present invention is prepared by dissolving a cellulose ester and an additive in a solvent to prepare a dope, casting a dope onto an endless metal support, and casting the dope. It is carried out by a step of drying as a web, a step of peeling from a metal support, a step of stretching or maintaining the width, a step of further drying, and a step of winding up the finished film.

  The process for preparing the dope will be described. The concentration of cellulose ester in the dope is preferably higher because the drying load after casting on the metal support can be reduced. However, if the concentration of cellulose ester is too high, the load during filtration increases and the filtration accuracy is poor. Become. As a density | concentration which makes these compatible, 10-35 mass% is preferable, More preferably, it is 15-25 mass%.

  The solvent used in the dope may be used alone or in combination of two or more, but it is preferable to use a mixture of a good solvent and a poor solvent of cellulose ester in terms of production efficiency, and there are many good solvents. This is preferable from the viewpoint of the solubility of the cellulose ester.

  The preferable range of the mixing ratio of the good solvent and the poor solvent is 70 to 98% by mass for the good solvent and 2 to 30% by mass for the poor solvent. With a good solvent and a poor solvent, what dissolve | melts the cellulose ester to be used independently is defined as a good solvent, and what poorly swells or does not melt | dissolve is defined as a poor solvent.

  Therefore, depending on the average acetylation degree (acetyl group substitution degree) of the cellulose ester, the good solvent and the poor solvent change. For example, when acetone is used as the solvent, the cellulose ester acetate ester (acetyl group substitution degree 2.4), cellulose Acetate propionate is a good solvent, and cellulose acetate (acetyl group substitution degree 2.8) is a poor solvent.

  Although the good solvent used for this invention is not specifically limited, Organic halogen compounds, such as a methylene chloride, dioxolanes, acetone, methyl acetate, methyl acetoacetate, etc. are mentioned. Particularly preferred is methylene chloride or methyl acetate.

  Moreover, although the poor solvent used for this invention is not specifically limited, For example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone, etc. are used preferably. Moreover, it is preferable that 0.01-2 mass% of water contains in dope.

  Moreover, the solvent used for melt | dissolution of a cellulose ester collect | recovers the solvent removed from the film by drying at the film-forming process, and uses this again.

  The recovery solvent may contain trace amounts of additives added to the cellulose ester, such as plasticizers, UV absorbers, polymers, monomer components, etc., but even if these are included, they are preferably reused. Can be purified and reused if necessary.

  A general method can be used as a dissolution method of the cellulose ester when preparing the dope described above. When heating and pressurization are combined, it is possible to heat above the boiling point at normal pressure.

  It is preferable to stir and dissolve while heating at a temperature that is equal to or higher than the boiling point of the solvent at normal pressure and that the solvent does not boil under pressure, in order to prevent the generation of massive undissolved materials called gels and mamaco.

  Moreover, after mixing a cellulose ester with a poor solvent and making it wet or swell, the method of adding a good solvent and melt | dissolving is also used preferably.

  The pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or a method of 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 a solvent is preferably higher from the viewpoint of the solubility of the cellulose ester, but if the heating temperature is too high, the required pressure increases and the productivity deteriorates.

  A preferable heating temperature is 45 to 120 ° C, more preferably 60 to 110 ° C, and still more preferably 70 ° C to 105 ° C. The pressure is adjusted so that the solvent does not boil at the set temperature.

  Alternatively, a cooling dissolution method is also preferably used, whereby the cellulose ester can be dissolved in a solvent such as methyl acetate.

  Next, this cellulose ester solution is filtered using a suitable filter medium such as filter paper. As the filter medium, it is preferable that the absolute filtration accuracy is small in order to remove insoluble matters and the like, but there is a problem that the filter medium is likely to be clogged if the absolute filtration accuracy is too small.

  For this reason, a filter medium with an absolute filtration accuracy of 0.008 mm or less is preferable, a filter medium with 0.001 to 0.008 mm is more preferable, and a filter medium with 0.003 to 0.006 mm is still more preferable.

  There are no particular restrictions on the material of the filter medium, and ordinary filter media can be used. However, plastic filter media such as polypropylene and Teflon (registered trademark), and metal filter media such as stainless steel do not drop off fibers. preferable.

  It is preferable to remove and reduce impurities, particularly bright spot foreign matter, contained in the raw material cellulose ester by filtration.

Bright spot foreign matter means that when two polarizing plates are placed in a crossed Nicol state, an optical film or the like is placed between them, light is applied from one polarizing plate side, and observation is performed from the other polarizing plate side. It is a point (foreign matter) where light from the opposite side appears to leak, and the number of bright spots having a diameter of 0.01 mm or more is preferably 200 / cm ² or less.

More preferably, it is 100 pieces / cm < ² > or less, More preferably, it is 50 pieces / m < ² > or less, More preferably, it is 0-10 pieces / cm < ² > or less. Further, it is preferable that the number of bright spots of 0.01 mm or less is small.

  The dope can be filtered by a normal method, but the method of filtering while heating at a temperature not lower than the boiling point of the solvent at normal pressure and in a range where the solvent does not boil under pressure is the filtration pressure before and after filtration. The increase in the difference (referred to as differential pressure) is small and preferable.

  A preferred temperature is 45 to 120 ° C, more preferably 45 to 70 ° C, and still more preferably 45 to 55 ° C.

  A smaller filtration pressure is preferred. The filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and further preferably 1.0 MPa or less.

  Here, the dope casting will be described.

  The metal support in the casting (casting) step preferably has a mirror-finished surface. As the metal support, a stainless steel belt or a drum whose surface is plated with a casting is preferably used.

  The cast width can be 1 to 4 m. The surface temperature of the metal support in the casting step is −50 ° C. to a temperature lower than the boiling point of the solvent, and a higher temperature is preferable because the web can be dried faster. May deteriorate.

  A preferable support body temperature is 0-40 degreeC, and 5-30 degreeC is still more preferable. Alternatively, it is also a preferable method that the web is gelled by cooling and peeled from the drum in a state containing a large amount of residual solvent.

  The method for controlling the temperature of the metal support is not particularly limited, and there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short. When warm air is used, wind at a temperature higher than the target temperature may be used.

  In order for the cellulose ester film to exhibit good flatness, the residual solvent amount when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or 60 to 130% by mass. Especially preferably, it is 20-30 mass% or 70-120 mass%.

  In the present invention, the amount of residual solvent is defined by the following formula.

Residual solvent amount (% by mass) = {(MN) / N} × 100
M is the mass of a sample collected during or after the production of the web or film, and N is the mass after heating M at 115 ° C. for 1 hour.

  Further, in the drying step of the cellulose ester film, the web is peeled off from the metal support, and further dried, and the residual solvent amount is preferably 1% by mass or less, more preferably 0.1% by mass or less, Especially preferably, it is 0-0.01 mass% or less.

  In the film drying step, generally, a roll drying method (a method in which webs are alternately passed through a plurality of rolls arranged above and below) and a method in which the web is dried while being conveyed by a tenter method are employed.

  In order to produce the cellulose ester film of the present invention, it is particularly preferable to perform stretching in the width direction (lateral direction) by a tenter method in which both ends of the web are held with clips or the like. Peeling is preferably performed at a peeling tension of 300 N / m or less.

  The means for drying the web is not particularly limited, and can be generally performed with hot air, infrared rays, a heating roll, microwave, or the like, but it is preferably performed with hot air in terms of simplicity.

  The drying temperature in the web drying step is preferably increased stepwise from 40 to 200 ° C.

  In order to obtain the target retardation values Ro and Rt in the present invention, it is preferable that the cellulose ester film has the configuration of the present invention and further the refractive index is controlled by a stretching operation.

  For example, biaxial stretching or uniaxial stretching can be performed sequentially or simultaneously with respect to the longitudinal direction (film forming direction) of the film and the direction orthogonal to the longitudinal direction of the film, that is, the width direction.

  The draw ratios in the biaxial directions perpendicular to each other are preferably in the range of 0.8 to 1.5 times in the casting direction and 1.1 to 2.5 times in the width direction, respectively. It is preferable to carry out in the range of 0.8 to 1.0 times in the direction and 1.2 to 2.0 times in the width direction.

  The stretching temperature is preferably 120 ° C. to 200 ° C., more preferably 160 ° C. to 200 ° C., and more preferably over 170 ° C. and 200 ° C. or less.

  The residual solvent in the film is preferably 20 to 0%, more preferably 15 to 0%.

  Specifically, the residual solvent is preferably stretched at 11% at 175 ° C., or the residual solvent is stretched at 2% at 175 ° C. Alternatively, it is preferred that the residual solvent is stretched at 11% at 185 ° C., or it is preferred that the residual solvent is stretched at less than 1% at 185 ° C.

  There is no particular limitation on the method of stretching the web. For example, a method in which a difference in peripheral speed is applied to a plurality of rolls, and the roll peripheral speed difference is used to stretch in the longitudinal direction between the rolls. And a method of stretching in the vertical direction, a method of stretching in the horizontal direction and stretching in the horizontal direction, a method of stretching in the vertical and horizontal directions and stretching in both the vertical and horizontal directions, and the like. Of course, these methods may be used in combination.

  In the case of the so-called tenter method, driving the clip portion by the linear drive method is preferable because smooth stretching can be performed and the risk of breakage and the like can be reduced.

  It is preferable to perform the width maintenance or the transverse stretching in the film forming process by a tenter, and it may be a pin tenter or a clip tenter.

  The slow axis or the fast axis of the cellulose ester film of the present invention is present in the film plane, and θ1 is preferably −1 ° or more and + 1 ° or less, assuming that the angle formed with the film forming direction is θ1. More preferably, it is 5 ° or more and + 0.5 ° or less.

  This θ1 can be defined as an orientation angle, and θ1 can be measured using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments). Each of θ1 satisfying the above relationship can contribute to obtaining high luminance in a display image, suppressing or preventing light leakage, and contributing to obtaining faithful color reproduction in a color liquid crystal display device.

<< Optically anisotropic layer with fixed orientation by vertically aligning rod-like liquid crystal >>
The optically anisotropic layer of the present invention preferably has the following characteristics.

0 ≦ Ro ≦ 10
−500 ≦ Rt ≦ −100
The optically anisotropic layer of the present invention is obtained by applying a liquid crystal material or a liquid crystal solution on an intermediate layer provided on a cellulose ester film, drying and heat-treating (also referred to as alignment treatment), and curing the liquid crystal by ultraviolet curing or thermal polymerization. It is characterized by having a retardation layer made of rod-like liquid crystals that are fixed in alignment and aligned in the vertical direction.

  Here, “orienting in the vertical direction” means that the rod-like liquid crystal is in the range of 70 to 90 ° (the vertical direction is 90 °) with respect to the film surface serving as the support.

  The rod-like liquid crystal may be oriented obliquely or the orientation angle may be gradually changed. Preferably it is the range of 80-90 degrees.

  The retardation layer of the present invention is a retardation layer made of rod-like liquid crystal aligned in the vertical direction in which Ro is in the range of 0 to 10 nm and Rt is in the range of −500 to −100 nm. Further, Ro is more preferably in the range of 0 to 5 nm. The phase difference of the phase difference of the layer on which the liquid crystal alignment on the support is fixed can be measured using an AxoScan manufactured by Opto Science Co., Ltd.

  When forming a retardation layer by aligning rod-shaped liquid crystals, an alignment film coated with a vertical alignment agent that aligns the so-called liquid crystal material in the vertical direction is used, and the liquid crystal material is vertically aligned and then fixed. be able to.

  When the liquid crystal material itself is aligned in the vertical direction at the air interface, the alignment regulating force extends to the interface opposite to the air interface, and the alignment film is not particularly necessary, and this is also preferable from the viewpoint of simplifying the configuration. preferable.

  As a specific method for vertically aligning the liquid crystal material, an alignment film composed of a cross-linked product of a block polymer composition containing a (meth) acrylic block polymer described in JP-A-2005-148473 and the like is used. Known methods such as a method of using, a method of using a vertical alignment film described in JP 2005-265889 A, and a method of using an air interface vertical alignment agent can be used.

  In order to make the retardation layer in the above range, it is preferable to control the orientation of the rod-like liquid crystal layer, the film thickness control, the temperature during UV curing, the tilt angle control, and the control of the pretilt angle at the support / air interface.

  The liquid crystal layer is formed by curing a liquid crystal material capable of forming a liquid crystal phase at a predetermined temperature with a predetermined liquid crystal regularity. The upper limit of the temperature showing the liquid crystal phase is not particularly limited as long as the cellulose ester film of the base material is not damaged.

  Specifically, a temperature of 120 ° C. or lower is preferable from the viewpoint of easy control of process temperature and maintenance of dimensional accuracy, and a liquid crystal material that becomes a liquid crystal phase at a temperature of 100 ° C. or lower is preferably used. On the other hand, the lower limit of the temperature showing the liquid crystal phase can be said to be a temperature at which the liquid crystal material can maintain the alignment state when used as a polarizing plate.

  As the liquid crystal material used for the retardation layer of the present invention, a polymerizable liquid crystal material is preferably used. The polymerizable liquid crystal material can be used by being polymerized by irradiating with predetermined actinic radiation. In the polymerized state, the vertical alignment state is fixed.

  As the polymerizable liquid crystal material, any of a polymerizable liquid crystal monomer, a polymerizable liquid crystal oligomer, and a polymerizable liquid crystal polymer can be used, and they can also be mixed with each other.

  Of the above, a polymerizable liquid crystal monomer is preferably used as the polymerizable liquid crystal material because of its high sensitivity during alignment and easy vertical alignment.

  Specific examples of the polymerizable liquid crystal monomer include a rod-like liquid crystal compound (I) represented by the following general formula (1) and a rod-like liquid crystal compound (II) represented by the following general formula (2). be able to. As the compound (I), two or more compounds included in the general formula (1) can be mixed and used. Similarly, the compound (II) is included in the general formula (2). Two or more kinds of compounds may be mixed and used. In addition, one or more compounds (I) and one or more compounds (II) may be mixed and used.

In the general formula (1) representing the compound (I), R ¹ and R ² each represent hydrogen or a methyl group, but R ¹ and R ² are both hydrogen due to the wide temperature range showing the liquid crystal phase. preferable.

  X may be hydrogen, chlorine, bromine, iodine, an alkyl group having 1 to 4 carbon atoms, a methoxy group, a cyano group, or a nitro group, but is preferably chlorine or a methyl group.

  Moreover, a and b which show the chain length of the alkylene group which is a spacer with the (meth) acryloyloxy group of both ends of the molecular chain of a compound (I), and an aromatic ring are respectively arbitrary integers in the range of 2-12. Although it can take, it is preferable that it is the range of 4-10, and it is more preferable that it is the range of 6-9.

  In addition to the above, in the present invention, conventionally known materials can be appropriately selected and used as the polymerizable liquid crystal oligomer and the polymerizable liquid crystal polymer.

  For example, as a polymerizable rod-like liquid crystalline compound, Makromol. Chem. 190, 2255 (1989), Advanced Materials 5, 107 (1993), US Pat. No. 4,683,327, US Pat. No. 5,622,648, US Pat. No. 5,770,107, International Publication WO95 / 22586. No. 95/24455, No. 97/00600, No. 98/23580, No. 98/52905, JP-A-1-272551, No. 6-16616, and No. 7-110469. 11-80081, JP 2001-328773, JP 2004-240188, JP 2005-99236, JP 2005-99237, JP 2005-121827, JP It is possible to use the compounds described in 2002-30042 Yes.

    As commercially available compounds, UCL-018 (Dainippon Ink Chemical Co., Ltd.), Palio Color LC242 (BASF Co., Ltd.), etc. can be used.

  In the present invention, a photopolymerization initiator is used as required in addition to the polymerizable liquid crystal material. When polymerizing a polymerizable liquid crystal material by electron beam irradiation, a photopolymerization initiator may not be necessary. However, in the case of curing by, for example, ultraviolet (UV) irradiation, which is generally used, photopolymerization is usually performed. An initiator is used to promote polymerization.

  Photopolymerization initiators include benzyl (also called bibenzoyl), benzoin isobutyl ether, benzoin isopropyl ether, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-benzoyl-4'-methyldiphenyl sulfide, benzyl methyl ketal, dimethylamino Methylbenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 3,3′-dimethyl-4-methoxybenzophenone, methylobenzoylformate, 2-methyl-1- (4 -(Methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 1- (4-dodecylphenyl) -2- Droxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2- Examples include methylpropan-1-one, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, or 1-chloro-4-propoxythioxanthone. it can.

  In general, the addition amount of the photopolymerization initiator is preferably 0.01% to 20%, more preferably 0.1% to 10%, and still more preferably 0.5% to 5%. Can be added to the polymerizable liquid crystal material of the present invention.

  In addition to the photopolymerization initiator, a sensitizer can be added as long as the object of the present invention is not impaired.

  The film thickness of the liquid crystal layer in the present invention is preferably in the range of 0.1 μm to 10 μm, and more preferably in the range of 0.2 to 5 μm.

  A polymerizable liquid crystal material is prepared by using a composition for forming a liquid crystal layer by blending a photopolymerization initiator, a sensitizer, etc., if necessary, and coating on a substrate to form a liquid crystal layer forming layer. To do.

  As a method of forming a layer in which the alignment of liquid crystal is fixed, for example, a dry film or the like is formed in advance and a layer in which the alignment of liquid crystal is fixed is laminated on a substrate, or a liquid crystal composition is dissolved. Alternatively, it is possible to use a method of melting and coating on a substrate, but in the present invention, a liquid crystal composition is added with a solvent and a coating composition in which other components are dissolved is used. It is preferable to form a layer in which the orientation of the liquid crystal is fixed by coating on the substrate and removing the solvent. This is simple in terms of process as compared with other methods.

  The solvent is not particularly limited as long as it is a solvent capable of dissolving the above-described polymerizable liquid crystal material and the like and does not deteriorate the properties of the transparent resin film. Specifically, benzene, Hydrocarbons such as toluene, xylene, n-butylbenzene, diethylbenzene, tetralin; ethers such as methoxybenzene, 1,2-dimethoxybenzene, diethylene glycol dimethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, or 2,4- Ketones such as pentanedione; ethyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, or γ-butyrolactone Amides solvents such as 2-pyrrolidone, N-methyl-2-pyrrolidone, dimethylformamide or dimethylacetamide; chloroform, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloroethane, tritrichloroethylene, tetrachloroethylene, chlorobenzene, or orthodichlorobenzene Halogen solvents such as t-butyl alcohol, diacetone alcohol, glycerin, monoacetin, ethylene glycol, triethylene glycol, hexylene glycol, ethylene glycol monomethyl ether, ethyl cellosolve, or butyl cellosolve; phenols, One or more of phenols such as parachlorophenol can be used.

  If only a single type of solvent is used, the solubility of the polymerizable liquid crystal material or the like may be insufficient, or the substrate may be eroded as described above. However, this inconvenience can be avoided by using a mixture of two or more solvents.

  Of the above-mentioned solvents, preferred as a single solvent are a hydrocarbon solvent and a glycol monoether acetate solvent, and a preferred mixed solvent is a mixed system of ethers or ketones and glycols. It is.

  The concentration of the solution depends on the solubility of the polymerizable liquid crystal material or the like and the film thickness of the liquid crystal layer to be produced, but cannot be defined unconditionally, but is usually preferably 1% to 60%, more preferably 3% to It is adjusted within the range of 40%.

  Compounds other than those described above can be added to the composition for forming a liquid crystal layer used in the present invention within a range not impairing the object of the present invention.

  Examples of compounds that can be added include polyester (meth) acrylate obtained by reacting (meth) acrylic acid with a polyester prepolymer obtained by condensing polyhydric alcohol and monobasic acid or polybasic acid; A polyurethane (meth) acrylate obtained by reacting a compound having two isocyanate groups with each other and then reacting the reaction product with (meth) acrylic acid; bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak Type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ether, aliphatic or cycloaliphatic epoxy resin, amine epoxy resin, triphenolmethane type epoxy resin, dihydroxybenzene type epoxy resin and the like (meth) Ak A photopolymerizable compound such as epoxy (meth) acrylate obtained by reacting phosphoric acid, a photopolymerizable liquid crystal compound having an acrylic group or a methacryl group, an onium salt described in JP-A-2007-45993, and a fluorine compound. Acrylate polymers and the like.

  The amount of these compounds added to the composition for forming a liquid crystal layer of the present invention is selected within a range that does not impair the purpose of the present invention, and is generally 40% or less of the composition for forming a liquid crystal layer of the present invention. Preferably, it is 20% or less.

  Addition of these compounds improves the curability of the liquid crystal material in the present invention, increases the mechanical strength of the resulting liquid crystal layer, and improves its stability.

  In addition, a surfactant or the like can be added to the composition for forming a liquid crystal layer containing a solvent in order to facilitate coating.

  Examples of surfactants that can be added include cationic surfactants such as imidazoline, quaternary ammonium salts, alkylamine oxides and polyamine derivatives; polyoxyethylene-polyoxypropylene condensates, primary or secondary Alcohol ethoxylates, alkylphenol ethoxylates, polyethylene glycol and esters thereof, sodium lauryl sulfate, ammonium lauryl sulfate, lauryl sulfate amines, alkyl-substituted aromatic sulfonates, alkyl phosphates, aliphatic or aromatic sulfonic acid formalin condensates, etc. Anionic surfactants; amphoteric surfactants such as laurylamidopropylbetaine and laurylaminoacetic acid betaine; nonionics such as polyethylene glycol fatty acid esters and polyoxyethylene alkylamine Surfactant: Perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl trimethyl ammonium salt, perfluoroalkyl group / hydrophilic group-containing oligomer, perfluoroalkyl / lipophilic group Fluorosurfactants such as containing oligomer perfluoroalkyl group-containing urethanes.

  The amount of surfactant added depends on the type of surfactant, the type of liquid crystal material, the type of solvent, and the type of alignment film on which the solution is applied. 10 ppm to 10% is preferable, more preferably 100 ppm to 5%, and still more preferably 0.1 to 1%.

  As a method for coating the composition for forming a liquid crystal layer, a spin coating method, a roll coating method, a printing method, a dip pulling method, a die coating method, a casting method, a bar coating method, a blade coating method, a spray coating method, a gravure coating method , Reverse coating method or extrusion coating method.

  The method for removing the solvent after coating the composition for forming a liquid crystal layer is performed, for example, by air drying, heat removal, or removal under reduced pressure, or a combination thereof. By removing the solvent, a layer in which the alignment of the liquid crystal is fixed is formed.

  In the step of curing the polymerizable liquid crystal material, energy for curing the polymerizable liquid crystal material is given, and thermal energy may be used, but it is usually performed by irradiation with ionizing radiation capable of causing polymerization.

  If necessary, a polymerization initiator may be contained in the polymerizable liquid crystal material. The ionizing radiation is not particularly limited as long as it is a radiation capable of polymerizing the polymerizable liquid crystal material, but usually ultraviolet light or visible light is used from the viewpoint of the ease of the apparatus, and the wavelength. Is preferably from 150 to 500 nm, more preferably from 250 to 450 nm, and even more preferably from 300 to 400 nm.

  In the present invention, a method of performing radical polymerization by irradiating ultraviolet rays (UV) as actinic radiation and generating radicals from the polymerization initiator with ultraviolet rays is preferable. Since the method using UV as the actinic radiation is an already established technique, it can be easily applied to the present invention including the polymerization initiator to be used.

  As a light source for irradiating ultraviolet rays, a low-pressure mercury lamp (sterilization lamp, fluorescent chemical lamp, black light), a high-pressure discharge lamp (high-pressure mercury lamp, metal halide lamp), or a short arc discharge lamp (ultra-high-pressure mercury lamp, xenon) Lamp, mercury xenon lamp) and the like.

  In particular, the use of metal halide lamps, xenon lamps, high-pressure mercury lamps, etc. is recommended. The irradiation intensity may be appropriately adjusted depending on the composition of the polymerizable liquid crystal material used for forming the layer in which the alignment of the liquid crystal is fixed and the amount of the photopolymerization initiator.

  The alignment fixing step by irradiation with actinic radiation may be performed at the processing temperature in the step of forming the liquid crystal layer forming layer described above, that is, the temperature condition in which the polymerizable liquid crystal material becomes a liquid crystal phase, It may be performed at a lower temperature.

《Middle layer》
The intermediate layer of the present invention is provided between an optically biaxial transparent film and an optically anisotropic layer in which the alignment is fixed by vertically aligning rod-like liquid crystals. Painted.

  The intermediate layer of the present invention is made of a transparent resin. The transparent resin is preferably a binder polymer having a saturated hydrocarbon chain or a polyether chain as a main chain, and more preferably a binder polymer having a saturated hydrocarbon chain as a main chain.

  Particularly preferred is a resin that is cured through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays or electron beams, or a mixed composition of a crosslinking agent and a resin having a reactive site.

  Examples of the curable resin include UV curable urethane acrylate resins, UV curable polyester acrylate resins, UV curable epoxy acrylate resins, UV curable polyol acrylate resins, and UV curable epoxy resins. A type acrylate resin is preferably used.

  The UV curable urethane acrylate resin generally includes a product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer, and further includes 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter, acrylate includes methacrylate). It can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate.

  For example, those described in JP 59-151110 A can be used. For example, a mixture of purple light UV-7510B (manufactured by Nippon Synthetic Chemical Co., Ltd.), Unidic 17-806 (manufactured by Dainippon Ink Co., Ltd.) and 1 part of Coronate L (manufactured by Nippon Polyurethane Co., Ltd.) Preferably used.

  Examples of UV curable polyester acrylate resins include those which are easily formed when 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers are generally reacted with polyester polyols. JP-A-59-151112 Those described in the publication can be used.

  Specific examples of the ultraviolet curable epoxy acrylate resin include an epoxy acrylate as an oligomer, a reactive diluent and a photopolymerization initiator added thereto, and reacted to form an oligomer. Those described in Japanese Patent No. 105738 can be used.

  Specific examples of UV curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, etc. Can be mentioned.

  Specific examples of photopolymerization initiators for these curable resins include benzoin and its derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer.

  In addition, when using an epoxy acrylate photopolymerization initiator, a sensitizer such as n-butylamine, triethylamine, tri-n-butylphosphine can be used.

  The photopolymerization initiator or photosensitizer used in the curable resin composition is 0.1 to 25 parts by mass, preferably 1 to 15 parts by mass with respect to 100 parts by mass of the composition.

  As acrylate resins, methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyl dimethyl adiacrylate , Trimethylolpropane triacrylate, pentaerythritol tetraacrylic ester and the like.

  As these commercial products, Adekaoptomer KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (manufactured by Asahi Denka Co., Ltd.); -101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT-102Q8, MAG -1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Co., Ltd.); Seika Beam PHC2210 (S), PHCX-9 (K-3), PHC2213, DP-10, DP-20, DP- 30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (manufactured by Dainichi Seika Kogyo Co., Ltd.); KRM7033, KRM7039 KRM 7130, KRM 7131, UVECRYL 29201, UVECRYL 29202 (manufactured by Daicel UCB); RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by Dainippon Ink & Chemicals, Inc.); 340 clear (manufactured by China Paint Co., Ltd.); Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (manufactured by Sanyo Chemical Industries); SP -1509, SP-1507 (manufactured by Showa Polymer Co., Ltd.); RCC-15C (manufactured by Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.), NK hard B-420, NK ester A-DOG, NK ester A-IBD-2E (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like can be appropriately selected and used.

  Other examples include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dioxane glycol acrylate, ethoxylated acrylate, alkyl-modified dipentaerythritol pentaacrylate, etc. Can be mentioned.

  Examples of the mixed composition of the crosslinking agent and the resin having a reactive site according to the present invention include polyvinyl alcohol and glyoxal, gelatin and glyoxal.

  Further, the intermediate layer may contain a fluorine-acrylic copolymer resin. The fluorine-acrylic copolymer resin is a copolymer resin composed of a fluorine monomer and an acrylic monomer, and a block copolymer composed of a fluorine monomer segment and an acrylic monomer segment is particularly preferable.

The intermediate layer of the present invention has a rod-like polarizability anisotropy represented by the formula (1) described in detail above in a range from 300 × 10 ⁻²⁵ cm ^{3 to} 2000 × 10 ⁻²⁵ cm ³ , A compound having an inter-distance of 1.5 nm or more and 10 nm or less, or a plane polarizability anisotropy represented by the following formula (2) of 150 × 10 ⁻²⁵ cm ³ or more and 1500 × 10 ⁻²⁵ cm ³ or less; It contains at least one compound selected from compounds having an end-to-end distance of 1.5 nm to 10 nm.

Formula (1): Δα = αx− (αy + αz) / 2
Formula (2): Δα = (αx + αy) / 2−αz
(Where αx is the largest component of the eigenvalues obtained after diagonalizing the polarizability tensor; αy is the second largest component of the eigenvalues obtained after diagonalizing the polarizability tensor. Yes; αz is the smallest component of the eigenvalues obtained after diagonalizing the polarizability tensor.)
Content is 0.0001-10 mass% with respect to resin which comprises an intermediate | middle layer, Preferably it is 0.0005-5 mass%.

  The intermediate layer of the present invention may be two or more layers. In the case of two or more layers, the content of the compound that is the retardation increasing agent of the present invention can be adjusted for each layer, and the intermediate layer located closest to the biaxial transparent film is an anisotropic layer. Preferably more compounds are present than the nearest intermediate layer.

  The amount of the compound present in the intermediate layer closest to the anisotropic layer is 70 to 99% by mass of the amount of the compound present in the intermediate layer closest to the biaxial transparent film. It is preferable.

<Method for producing intermediate layer>
For the intermediate layer, a coating composition for forming the intermediate layer containing the retardation increasing agent of the present invention is applied using a known method such as a gravure coater, dip coater, reverse coater, wire bar coater, die coater, and ink jet method. It is preferable that after coating on a support, it is dried by heating and UV-cured.

  The coating amount is suitably 0.1 to 40 μm, preferably 0.5 to 30 μm, as the wet film thickness.

  Moreover, as a dry film thickness, it is an average film thickness of 0.01-1 micrometer, Preferably it is 0.02-0.7 micrometer.

  As the light source for the UV curing treatment, any light source that generates ultraviolet rays can be used without limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.

Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually 5 to 500 mJ / cm ² , preferably 5 to 150 mJ / cm ² .

  Moreover, when irradiating actinic radiation, it is preferable to carry out while applying tension | tensile_strength in the conveyance direction of a film, More preferably, it is performing applying tension | tensile_strength also in the width direction. The tension to be applied is preferably 30 to 300 N / m.

  The method for applying tension is not particularly limited, and tension may be applied in the transport direction on the back roll, or tension may be applied in the width direction or biaxial direction by a tenter. This makes it possible to obtain a film having further excellent flatness.

  The coating composition for forming the intermediate layer may contain a solvent. Examples of the organic solvent contained in the coating composition include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone), These may be appropriately selected from esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, and other organic solvents, or may be used by mixing them.

As the organic solvent, propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate (1 to 4 carbon atoms of the alkyl group) is preferable. Moreover, as content of an organic solvent, 5-80 mass% is preferable in a coating composition.
<Polarizing plate using retardation film of the present invention as polarizing plate protective film>
In the polarizing plate comprising the polarizer and two polarizing plate protective films sandwiching the polarizer, the retardation film of the present invention can be at least one of the polarizing plate protective films.

  The polarizing plate of the present invention is characterized in that it is a polarizing plate bonded to at least one surface of a polarizer using the retardation film of the present invention as a polarizing plate protective film.

  The polarizing plate of the present invention can be produced by a general method. The cellulose ester film which is the retardation film of the present invention is subjected to alkali saponification treatment on the polarizer side, and is attached to at least one surface of a polarizer prepared by immersion and stretching in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. It is preferable to match.

  Even if the retardation film is used on the other surface, it is preferable to paste another polarizing plate protective film.

  For example, a commercially available cellulose ester film (for example, Konica Minoltak KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC12UR, KC4UE, KC8UE, KC8UY-HA, KC8UY-HA, KC8UY-C8 -RHA-NC, KC4UXW-RHA-NC, manufactured by Konica Minolta Opto Co., Ltd.) are also preferably used.

  The polarizing plate protective film used on the surface side of the display device preferably has an antireflection layer, an antistatic layer, an antifouling layer, and a backcoat layer in addition to the intermediate layer or the clear hard coat layer.

  A polarizer, which is a main component of a polarizing plate, is an element that allows only light of a plane of polarization in a certain direction to pass. A typical polarizer currently known is a polyvinyl alcohol-based polarizing film, which is polyvinyl alcohol. There are one in which iodine is dyed on a system film and one in which dichroic dye is dyed.

  For the polarizer, a polyvinyl alcohol aqueous solution is formed into a film and dyed by uniaxial stretching or dyed or uniaxially stretched and then preferably subjected to a durability treatment with a boron compound. The film thickness of the polarizer is preferably 5 to 30 μm, particularly preferably 10 to 20 μm.

  Further, the ethylene unit content described in JP-A-2003-248123, JP-A-2003-342322, etc. is 1 to 4 mol%, the degree of polymerization is 2000 to 4000, and the degree of saponification is 99.0 to 99.99 mol%. Ethylene-modified polyvinyl alcohol is also preferably used.

  Among them, an ethylene-modified polyvinyl alcohol film having a hot water cutting temperature of 66 to 73 ° C. is preferably used.

  The difference in hot water cutting temperature between two points 5 cm away in the TD direction of the film is more preferably 1 ° C. or less in order to reduce color spots, and two points separated 1 cm in the TD direction of the film. In order to reduce color spots, it is more preferable that the difference in the hot water cutting temperature is 0.5 ° C. or less.

  A polarizer using this ethylene-modified polyvinyl alcohol film is excellent in polarization performance and durability, and has few color spots, and is particularly preferably used for a large-sized liquid crystal display device.

  The polarizer obtained as described above is used as a polarizing plate by bonding a polarizing plate protective film, which is the retardation film of the present invention, on both sides or one side thereof.

  Examples of the adhesive used for pasting include a PVA-based adhesive and a urethane-based adhesive. Among them, a PVA-based adhesive is preferably used.

  The in-plane slow axis of the retardation film of the present invention and the absorption axis of the polarizer are preferably bonded to each other at right angles.

In the present invention, the terms “parallel” and “orthogonal” in an optical film such as a retardation film mean within a range of ± 15 ° relative to strict parallel and orthogonal.
<Liquid crystal display device using the polarizing plate of the present invention>
By using the polarizing plate of the present invention for a liquid crystal display device, the liquid crystal display device of the present invention with improved alignment unevenness can be produced.

  The liquid crystal display device of the present invention has a first polarizing plate using the retardation film of the present invention, a driving liquid crystal cell having a liquid crystal layer sandwiched between transparent substrates, and a second polarizing plate in this order. It is a liquid crystal display device.

  The absorption axes of the first and second polarizing plates are arranged in crossed Nicols and are orthogonal to each other as in a normal liquid crystal display device.

  Further, the optically anisotropic layer of the first polarizing plate of the present invention is disposed on the driving liquid crystal cell side when viewed from the polarizer of the first polarizing plate, and the liquid crystal layer in the liquid crystal cell does not apply voltage. The liquid crystal layer is aligned horizontally with respect to the substrate, and the alignment direction of the liquid crystal layer in the liquid crystal cell is arranged parallel to the transmission axis of the first polarizing plate.

《Second polarizing plate》
The second polarizing plate of the present invention is a polarizing plate comprising a polarizer and two polarizing plate protective films sandwiching the polarizer, and at least one of the polarizing plate protective films is optically isotropic. Film, an optically negative uniaxial film, and a film satisfying nx>ny> nz, and the selected polarizing plate protective film side as viewed from the polarizer is disposed in the driving liquid crystal cell. It is characterized by being a polarizing plate.

  In addition, nx represents the refractive index in the slow axis direction in the plane of the film, ny represents the refractive index in the direction perpendicular to the slow axis in the plane, and nz represents the refractive index in the thickness direction.

  The film thickness of the selected polarizing plate protective film is 20 to 70 μm.

  An optically isotropic film refers to a film that is substantially nx = ny = nz, and means that 0 ≦ Ro ≦ 10 nm and −10 ≦ Rt ≦ 10 nm.

  An optically negative uniaxial film means a film substantially satisfying nx <ny = nz, and means that 0 ≦ Ro ≦ 10 nm and 120 ≦ Rt ≦ 500 nm.

  The film in which nx> ny> nz is 30 ≦ Ro ≦ 95 nm, 70 ≦ Rt ≦ 400 nm, and 1.1 ≦ Rt / Ro ≦ 11.

  By selecting the second polarizing plate in this way, it is possible to cope with various types of liquid crystal display devices such as VA type and IPS type.

  These polarizing plate protective films can be produced by a known method.

  As the protective film on the side opposite to the selected polarizing plate protective film, the selected polarizing plate protective film may be used, or another polarizing plate protective film may be bonded.

  For example, a commercially available cellulose ester film (for example, Konica Minoltak KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC12UR, KC4UE, KC8UE, KC8UY-HA, KC8UY-HA, KC8UY-C8 -RHA-NC, KC4UXW-RHA-NC, manufactured by Konica Minolta Opto Co., Ltd.) are also preferably used, but those having a film thickness of 20 to 70 μm are preferable.

<Liquid crystal display device>
In the liquid crystal display device of the present invention, either the first polarizing plate or the second polarizing plate can be arranged on the backlight side, but the arrangement of the first polarizing plate on the backlight side is against heat. This is preferable because the influence can be improved.

  The retardation film of the present invention can be used for liquid crystal display devices of various drive systems such as STN, TN, OCB, HAN, VA (MVA, PVA), IPS, OCB.

  In particular, even a large-screen liquid crystal display device with a 30-inch or larger screen can provide a liquid crystal display device with excellent visibility such as uneven coloring and front contrast with little environmental fluctuation and reduced light leakage.

  The driving liquid crystal cell has a structure in which a driving circuit is provided on two transparent supports, such as a glass plate and a transparent resin film, which are used in a normal liquid crystal display device, and liquid crystal is enclosed. Can be used in the usual way.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
Example 1
<Preparation of retardation film 101>
(Synthesis of acrylic polymer X1)
Bulk polymerization was performed by the polymerization method described in JP-A No. 2000-344823. That is, the contents were heated to 70 ° C. while introducing the following methyl acrylate and ruthenocene into a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, an inlet, and a reflux condenser.

  Next, half of the following β-mercaptopropionic acid which had been sufficiently purged with nitrogen gas was added to the flask under stirring. After the addition of β-mercaptopropionic acid, the contents in the stirring flask were maintained at 70 ° C. and polymerization was carried out for 2 hours.

  Further, after adding the other half of β-mercaptopropionic acid substituted with nitrogen gas, the temperature of the content being stirred was maintained at 70 ° C., and polymerization was carried out for 4 hours. The temperature of the reaction product was returned to room temperature, and 20 parts by mass of a 5% by mass benzoquinone tetrahydrofuran solution was added to the reaction product to stop the polymerization.

  While gradually heating the polymer to 80 ° C. under reduced pressure with an evaporator, the tetrahydrofuran, residual monomer and residual thiol compound were removed to obtain an acrylic polymer X1. The weight average molecular weight Mw was 1000.

Methyl acrylate 100 parts by mass Ruthenocene (metal catalyst) 0.05 parts by mass β-mercaptopropionic acid 12 parts by mass (additive solution A)
Aerosil 200V (manufactured by Nippon Aerosil Co., Ltd.) 2 parts by mass (average diameter of primary particles 12 nm, apparent specific gravity 100 g / liter)
18 parts by mass or more of ethanol was stirred and mixed with a dissolver for 30 minutes, and then dispersed with Manton Gorin. The liquid turbidity after dispersion was 100 ppm. To this silicon dioxide dispersion, 18 parts by mass of methylene chloride was added while stirring, and the mixture was stirred and mixed for 30 minutes with a dissolver to prepare additive liquid A.

(Dope solution for cellulose ester)
Cellulose ester (total substitution degree 2.48, propionyl substitution degree 0.82)
100 parts by mass Compound of formula (1) or (2) Table 1 Acrylic polymer X1 2.5 parts by mass Sugar ester compound 3 10 parts by mass Methylene chloride 400 parts by mass Ethanol 62 parts by mass Additive liquid A 2 parts by mass The solution was put into a closed container, heated, stirred and completely dissolved, and Azumi filter paper No. 1 manufactured by Azumi Filter Paper Co., Ltd. 24, and the dope liquid A was prepared. The dope solution was filtered with Finemet NF manufactured by Nippon Seisen Co., Ltd. in the film production line.

  The dope liquid whose temperature was adjusted to 33 ° C. was fed to a die and uniformly cast from a die slit onto a stainless steel belt. The cast part of the stainless steel belt was heated from the back with hot water of 37 ° C. After casting, the dope film (referred to as a web after casting on a stainless steel belt) on a metal support was dried by applying hot air of 44 ° C., and peeling was performed at a residual solvent amount of 120% by mass.

The film was stretched so as to have a stretching ratio of 1.1 times in the casting direction by applying tension at the time of peeling.
The film thickness is adjusted by adjusting the flow rate of the dope, and the residual dissolution is 120% by mass by controlling the air flow on the stainless steel belt.

  After the dope flow rate adjustment and the film prepared and peeled in the same manner as described above, the film was preheated at 155 ° C. for 2 seconds and then subjected to a stretching process of 1.41 times at 163 ° C. The tension in the width direction was relaxed to release the width retention, and the film was dried at 120 ° C.

  The optically biaxial transparent film 101 which is a support for the retardation film having a thickness of 60 μm and a width of 1.5 m produced as described above was wound up.

(Interlayer coating solution)
25 parts by mass of urethane acrylate oligomer (UV-7510B Nippon Synthetic Chemical Co., Ltd.)
Propylene glycol monomethyl ether 290 parts by mass Isopropyl alcohol 685 parts by mass Compound of formula (1) or (2) Table 1 Photopolymerization initiator 0.05 part by mass (manufactured by Lucillin TPO Basf)
This coating solution was applied to the transparent film 100 with a wire bar # 3, dried at 80 ° C. for 30 seconds, and then cured by irradiating ultraviolet rays at 120 mJ / mm for 10 seconds. The film thickness of the intermediate layer after drying was 0.5 μm.

On this intermediate layer, a commercially available vertical alignment film (JALS-204R, manufactured by Nippon Synthetic Rubber Co., Ltd.) as a second intermediate layer was diluted 1: 1 with methyl ethyl ketone, and then 2.4 ml / m ² with a wire bar coater. Applied. Immediately, it was dried with warm air of 120 ° C. for 120 seconds.

(Anisotropic layer coating solution)
UV-polymerizable liquid crystal material 20 parts by mass (UCL-018 manufactured by Dainippon Ink & Chemicals, Inc.)
Propylene glycol monomethyl ether 80 parts by mass Photopolymerization initiator 0.04 parts by mass (Lucirin TPO (manufactured by BASF Corp.))
Hindered amine 0.02 parts by mass LS-765 (manufactured by Sankyo Lifetech Co., Ltd.)
0.10 parts by mass of sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.)
Air interface side vertical alignment agent 1 0.01 part by mass This anisotropic layer coating solution was applied on the straight alignment film with a thickness of 12 μm by a die coater. Then, it heated for 2 minutes in a 100 degreeC thermostat, and the rod-shaped liquid crystal compound was orientated.

  Next, the coated film was irradiated with ultraviolet rays of 250 mJ / mm for 10 seconds at an oxygen concentration of 0.2% and a temperature of 28 ° C. to cure the polymerizable liquid crystal composition, whereby a retardation film 101 was obtained. The thickness of the anisotropic layer was 1.8 μm.

  The overall retardation film had Ro of 64.5 nm and Rt of -20 nm. All retardation films were adjusted so that the total retardation Ro was 63 ± 3 nm and Rt was −30 ± 25 nm, and the results are shown in Table 2.

The retardation film thus obtained was evaluated as follows.
(Evaluation method for uneven orientation)
<Phase difference unevenness>
A retardation film sample was subjected to retardation Ro measurement at a measurement spot of 0.5 mm and a pitch of 0.5 mm using a birefringence phase difference measuring device AD-175SI manufactured by Saitoh Co., Ltd. The measurement was performed by inclining 40 ° with the in-plane slow axis of the film as the tilt axis.

  Before applying the liquid crystal layer, the retardation unevenness of the biaxial transparent film support was measured, and it was confirmed that there was no unevenness at an interval of 0.1 mm and less than 0.1 nm.

  The following was used as a reference for phase difference unevenness.

Interval Retardation difference Evaluation 0.1 mm Less than 0.100 nm ◎
0.1mm 0.100 or more and less than 0.150nm ○
0.1 mm 0.150 nm or more ×
<Heat unevenness>
Remove the polarizing plate of the Matsushita Electric 26-inch LCD TV, VIERA 26LX60 liquid crystal panel, and place the polarizing plate using the retardation film of the present invention instead on the viewing side of the liquid crystal panel and the liquid crystal layer on the liquid crystal cell side. Pasted together.

  On the backlight side, a polarizing plate using an isotropic cellulose triacetate (TAC) film whose phase difference was adjusted to Ro = 0.8 nm and Rt = 1.1 nm was bonded.

  These configurations are shown in FIG. In the figure, what is described as a TAC film was Konica Minolta Tack KC4UY (manufactured by Konica Minolta Opto).

  The viewing-side polarizing plate was produced as follows. A saponified KC4UY was bonded to one surface of a polarizer obtained by adsorbing iodine to a stretched polyvinyl alcohol film using a polyvinyl alcohol-based adhesive. On the other surface, the retardation film of the present invention was bonded using a polyurethane-based adhesive to produce a viewing side polarizing plate.

  The backlight side polarizing plate saponified the cellulose ester film as usual, and bonded using the polyvinyl alcohol-type adhesive agent, and produced the polarizing plate.

  The liquid crystal panel produced as described above was stored at 60 ° C. and 90% RH for 24 hours, the backlight was turned on to display black, and the intensity of unevenness was visually observed after 2 hours.

Situation Evaluation Strong unevenness at the four corners and cloudy unevenness on the entire surface XX
Strong unevenness occurs at the four corners ×
Weak cloudy unevenness occurs △
No unevenness ○

Example 2
<Preparation of retardation film 201>
(Additive solution B)
Aerosil R972V (manufactured by Nippon Aerosil Co., Ltd.) 2 parts by mass (average primary particle diameter 16 nm, apparent specific gravity 90 g / liter)
18 parts by mass or more of ethanol was stirred and mixed with a dissolver for 30 minutes, and then dispersed with Manton Gorin. The liquid turbidity after dispersion was 100 ppm. To this silicon dioxide dispersion, 18 parts by mass of methylene chloride was added while stirring, and the mixture was stirred and mixed for 30 minutes with a dissolver to prepare additive liquid B.

(Dope solution for cellulose ester)
Cellulose triacetate (degree of substitution 2.86) 100 parts by weight Triphenyl phosphate (plasticizer) 7.8 parts by weight Biphenyl diphenyl phosphate (plasticizer) 3.9 parts by weight Methylene chloride (first solvent) 300 parts by weight Methanol (second Solvent) 54 parts by mass 1-butanol 11 parts by mass Additive liquid B 0.5 parts by mass The same as in Example 1 using the above dope solution, which is a support for a retardation film having a thickness of 80 μm and a width of 1.5 m, The optically biaxial transparent film 201 was wound up.

The transparent film 201 was saponified, and an intermediate layer coating solution having the following composition was applied onto the film with a wire bar coater at 20 ml / m ² . The intermediate layer was provided by drying with warm air of 60 ° C. for 60 seconds and further with warm air of 100 ° C. for 120 seconds.

(Interlayer coating solution)
The following modified polyvinyl alcohol 10 parts by weight Water 371 parts by weight Methanol 119 parts by weight Compound of formula (1) or (2) 0.2 part by weight Glutaraldehyde 0.5 part by weight

  On the intermediate layer, the same anisotropic layer as in Example 1 was provided to obtain a retardation film 201.

  The overall retardation film had Ro of 64.5 nm and Rt of -20 nm. All retardation film samples were adjusted so that the total retardation Ro was 63 ± 3 nm and Rt was −30 ± 25 nm.

  Evaluation similar to Example 1 was performed about this sample. The results are shown in Table 4.

Claims (5)

An optically biaxial transparent film, an optically anisotropic layer in which rod-like liquid crystals are vertically aligned and fixed in alignment, and at least one intermediate layer between the biaxially transparent film and the optically anisotropic layer A retardation film having a layer, wherein the intermediate layer has a rod-like polarizability anisotropy represented by the following formula (1) of 200 × 10 ⁻²⁵ cm ³ or more and 2000 × 10 ⁻²⁵ cm ³ or less. Yes, a compound having a molecular end-to-end distance of 1.5 nm to 10 nm, or a plane polarizability anisotropy represented by the following formula (2): 150 × 10 ⁻²⁵ cm ³ or more and 1500 × 10 ⁻²⁵ cm ³ or less A retardation film comprising at least one compound selected from compounds having a molecular end-to-end distance of 1.5 nm to 10 nm.
Formula (1): Δα = αx− (αy + αz) / 2
Formula (2): Δα = (αx + αy) / 2−αz
(Where αx is the largest component of the eigenvalues obtained after diagonalizing the polarizability tensor; αy is the second largest component of the eigenvalues obtained after diagonalizing the polarizability tensor. Yes; αz is the smallest component of the eigenvalues obtained after diagonalizing the polarizability tensor.)   In the case where there are a plurality of the intermediate layers, the compound represented by the formula (1) or (2) included in the intermediate layer closest to the transparent film and the intermediate layer closest to the optically anisotropic layer. The retardation film according to claim 1, wherein the content is different.   In the polarizing plate comprising a polarizer and two polarizing plate protective films sandwiching the polarizer, at least one of the polarizing plate protective films is the retardation film according to claim 1 or 2. A polarizing plate, wherein an in-plane slow axis of the retardation film and an absorption axis of a polarizer are orthogonal to each other.   A liquid crystal display device comprising the first polarizing plate according to claim 3, a driving liquid crystal cell having a liquid crystal layer sandwiched between transparent substrates, and a second polarizing plate in this order, The absorption axis of the second polarizing plate is orthogonal, and the optically anisotropic layer of the first polarizing plate is disposed on the driving liquid crystal cell side when viewed from the polarizer of the first polarizing plate. The liquid crystal layer is aligned horizontally with respect to the substrate without applying a voltage, and the alignment direction of the liquid crystal layer in the liquid crystal cell is perpendicular to the absorption axis of the first polarizing plate. apparatus. The second polarizing plate is a polarizing plate comprising a polarizer and two polarizing plate protective films sandwiching the polarizer, and at least one of the polarizing plate protective films is an optically isotropic film. , An optically negative uniaxial film and a film satisfying nx>ny> nz, and the selected polarizing plate protective film side as viewed from the polarizer is disposed in the driving liquid crystal cell. 5. The liquid crystal display device according to claim 4, wherein the liquid crystal display device is a polarizing plate.
(Nx represents the refractive index in the slow axis direction in the plane of the film, ny represents the refractive index in the direction perpendicular to the slow axis in the plane, and nz represents the refractive index in the thickness direction.)