TWI420159B - Optical compensation film and method of producing the same, polarizing plate and liquid crystal display - Google Patents

Description

Optical compensation film, preparation method thereof, polarizing plate and liquid crystal display device

The present invention relates to an optical compensation film, a method of manufacturing the same, a polarizing plate, and a liquid crystal display device.

The liquid crystal display device has a liquid crystal cell and a polarizing plate. The polarizing plate generally has a protective film composed of cellulose acetate and a polarizing film. For example, a polarizing film composed of a polyvinyl alcohol film is dyed with iodine and stretched, and then laminated with a protective film. Made on both sides.

In the transmissive liquid crystal display device, the polarizing plate is mounted on both sides of the liquid crystal cell, and there is also a case where one or more optical compensation films are further disposed.

In the reflective liquid crystal display device, generally, a reflector, a liquid crystal cell, one or more optical compensation films, and a polarizing plate are arranged in this order.

The liquid crystal cell is composed of a liquid crystal molecule, two substrates required for encapsulation, and an electrode layer for applying a voltage to liquid crystal molecules.

The liquid crystal cell system performs ON and OFF display by the difference in the alignment state of the liquid crystal molecules, and any of the transmission and reflection types are applicable, such as TN (Twisted Nematic), IPS (In-Plane Switching: Proposal for display modes such as In Plane Switching, OCB (Optically Compensatory Bend), VA (Vertically Aligned), and ECB (Electrically Controlled Birefringence).

In such liquid crystal display devices, for applications requiring high display quality, a nematic liquid crystal molecule having a positive dielectric anisotropy is used mainly, and 90° is driven by a thin film transistor. A twisted nematic liquid crystal display device (hereinafter referred to as "TN mode").

However, when viewed from the front, the TN mode has superior display characteristics, but when viewed from an oblique direction, it has a contrast reduction, resulting in a grayscale inverse as the brightness is reversed when displayed in grayscale. The viewing angle characteristics of deterioration of display characteristics caused by (grayscale inversion) and the like are desirably expected to be improved.

On the other hand, a wide viewing angle liquid crystal method such as an IPS mode, an OCB mode, and a VA mode has been expanding its market share in recent years as the demand for liquid crystal televisions has increased.

However, although each method has improved its display quality year by year, the problem of color shifting generated when viewed from an oblique direction has not been solved. (Japanese Laid-Open Patent Publication No. Hei 9-211444, Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. 2003-15134, Japanese Patent Application Laid-Open No. Hei 11-95208, Japanese Laid-Open Patent Publication No. 2002-221622, Japanese Patent Laid-Open No. Hei 9-80424, Japanese Invention Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Kaikai No. 11-305217, and Japanese Patent Application Laid-Open No. 10-307291

The reason for this color shift is known to be due to the wavelength dispersion of the optical compensation films Re and Rth. Especially in the case of Re, the Re value will increase monotonically with the "reverse dispersion" as the wavelength increases. In the case of Rth, if the wavelength increases, the Re value will monotonically decrease. When "positively dispersed", the hue is about to become neutral, and the effect of the angle of view change is less.

However, it is generally difficult to obtain an optical compensation film having the above-described characteristics in one piece, and therefore it has been conventional to use two optical compensation films to realize wavelength dispersion characteristics.

However, if two optical compensation films are used, the thickness of the polarizing plate to which the film is applied will increase. Further, since the cost is also increased, it has been desired to use an optical compensation film, that is, a method in which Re is "reversely dispersed" and Rth is "positively dispersed".

The present invention has been made to solve the above problems to date, and the object as described below is achieved for the purpose. That is, the object is to provide a liquid crystal display device which can reduce the color in the viewing angle direction, especially VA, IPS, and optical compensation, which is not only the front side but also the oblique direction optical compensation, by strictly implementing one optical compensation film. OCB mode liquid crystal display device.

The invention provides an optical compensation film which can correctly compensate the liquid crystal cell optically in one piece, and improves the color displacement depending on the viewing angle direction in high contrast and black display, especially VA, IPS and The optical compensation film for the OCB mode, the manufacturing method thereof, and the polarizing plate using the same are achieved by the inventors of the present invention and the like.

The method for solving the above problem is as follows. That is, the optical compensation film of the present invention is characterized in that it has a transparent support containing at least one Rth rising agent, and the transparent support is defined by the following formula (A) by X-ray diffraction measurement. The degree of alignment P" is 0.05 to 0.30: P = < 3 cos ² β-1 > 2 Formula (A). However, in the formula (A), <cos ² β>=∫(0,π)cos ² βI(β)sinβdβ/∫(0,π)I(β)sinβdβ.

Further, in the above formula, the angle formed by the incident surface of the X-ray incident on the β-ray and the direction in the plane of the transparent support is I 2 = 8° in the X-ray diffraction pattern measured by the angle β. The diffraction intensity of time.

A method of producing an optical compensation film according to the present invention, comprising: a casting step of casting a polymer solution of a raw material containing a transparent support of at least one Rth rising agent on a belt; and drying for the casting step a drying step of the obtained film; and an extending step of extending the film at a temperature higher than a glass transition temperature of the transparent support by +15 to +100 ° C after the film is peeled off from the tape.

The polarizing plate of the present invention is characterized in that the polarizing plate has a polarizing film and a pair of protective films for holding the polarizing film, at least one of the protective films having a transparent support body containing at least one Rth rising agent, and An optical compensation film having an orientation P defined by the above formula (A) calculated by an X-ray diffraction measurement of the transparent support of 0.05 to 0.30.

A liquid crystal display device of the present invention is characterized in that it has a liquid crystal cell and a polarizing plate, the polarizing plate has a polarizing film, and a pair of protective films for holding the polarizing film, at least one of the protective films having at least one Rth A transparent support of a rising agent, and an optical compensation film having an orientation P defined by the above formula (A) calculated by an X-ray diffraction measurement of the transparent support of 0.05 to 0.30.

[Detailed Description of the Best Mode for Carrying Out the Invention]

Hereinafter, the optical compensation film, the polarizing plate, and the liquid crystal display device of the present invention will be described in detail.

Further, in the description of the present embodiment, the term "45°", "parallel" or "orthogonal" means that it is within a range of less than a strict angle of ±5°. The error with the tight angle is preferably less than 4°, more preferably less than 3°. In addition, regarding the angle, "+" means clockwise, and "-" means counterclockwise. In addition, the "late phase axis" means that the refractive index will be the largest direction. In addition, the "visible light region" means 380 to 780 nm. Also, unless otherwise noted, the measurement wavelength of the refractive index is in the visible light region (λ = 550 nm).

In addition, in the description of the present embodiment, the "polarizing plate" is a polarizing plate including a long size and a polarizing plate of a size that can be assembled into a liquid crystal device unless otherwise specified. Meaning to use. In addition, the so-called "cropping" here should also include "punching" and "cutting out".

Further, in the description of the present embodiment, the "polarizing film" is distinguished from the "polarizing plate", but the "polarizing plate" means at least one side of the "polarizing film". A laminate having a transparent protective film for protecting the polarizing film.

Further, in the case of the "molecular symmetry axis" in the description of the present embodiment, when the molecule has a rotational symmetry axis, the symmetry axis is referred to, but the molecule is not required to have rotational symmetry in a strict sense.

In general, in a discotic liquid crystal compound, a molecular symmetry axis is aligned with a perpendicular axis to a disk surface passing through the center of the disk surface, and in a rod-like liquid crystal compound, The molecular symmetry axis is consistent with the long axis of the molecule.

Further, in the present specification, Re _(λ) and Rth _(λ) represent hysteresis in the plane of the wavelength λ and hysteresis in the thickness direction, respectively. Re _(λ) was measured by KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments, Ltd.), and light having a wavelength of λ nm was incident on the normal direction of the film.

When the film to be measured is represented by a uniaxial or biaxial refractive index ellipsoid, Rth _(λ) can be calculated by the method described below.

Rth _(λ) is the above-mentioned Re _(λ) with the in-plane retardation axis (which can be judged by KOBRA 21ADH or WR) as the tilt axis (rotation axis) (if there is no late phase axis, the film is In any direction of the plane as the rotation axis), light having a wavelength of λ nm is incident at a distance of 10° from the normal direction to a single side at 50°, and all of them are measured, and then all six are measured. KOBRA 21ADH or WR will be calculated based on the measured hysteresis value and the assumed value of the average refractive index and the input film thickness value.

As described above, when the retardation axis in the plane is the rotation axis from the normal direction and the hysteresis value at a certain inclination angle is a film in the direction of zero, the inclination is larger than the inclination angle. The hysteresis value at the angle is calculated by KOBRA 21ADH or WR after the sign is changed to negative.

In addition, the slow axis may be the tilt axis (rotation axis) (if there is no slow phase axis, the arbitrary direction in the film plane is set as the rotation axis), and the hysteresis value may be measured from the two directions of arbitrary inclination, and then, according to the value Rth is calculated by the following formula (B) and formula (C) from the assumed value of the average refractive index and the input film thickness value.

However, in the above formula, Re(θ) represents a hysteresis value in a direction inclined by the angle θ from the normal direction.

Further, in the formula (B), nx represents a refractive index in the in-plane axis direction, ny represents a refractive index in the plane orthogonal to nx, and nz represents orthogonal to nx and ny. The refractive index of the direction.

Rth=((nx+ny)/2-nz)×d Formula (C).

If the film to be measured cannot be represented by a uniaxial or biaxial refractive index ellipsoid, that is, a so-called film having no optical axis, Rth _(λ) is calculated by the following method.

Rth _(λ) is a Re _(λ) as described above, with the in-plane retardation axis (which can be judged by KOBRA 21ADH or WR) as the tilt axis (rotation axis), from -50° to the film normal direction until At +50°, light having a wavelength of λ nm is incident from the oblique direction at intervals of 10°, and 11 are measured. Then, KOBRA 21ADH or WR will be based on the measured hysteresis value and the assumed value of the average refractive index and input. The film thickness value is calculated.

Further, regarding the above-mentioned measurement, the assumed value of the average refractive index is a product catalogue of a polymer handbook (JOHN WILEY & SONS, INC) and various optical films. When the value of the average refractive index is not known, it can be measured by an Abbe refractometer. The values of the average refractive index of the main optical films are as follows: deuterated cellulose (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), polystyrene ( 1.59). By inputting the assumed value of the average refractive index and the film thickness, KOBRA 21ADH or WR can be calculated as nx, ny, nz. From this calculated nx, ny, nz, Nz = (nx - nz) / (nx - ny) can be calculated again.

In addition, in the present specification, the maximum absorption wavelength (λ _max ) is a value measured by UV-3150 (manufactured by Shimadzu Corp.).

(Composition of liquid crystal display device)

Fig. 1 is a view showing the configuration of a liquid crystal display device of the present invention.

As shown in FIG. 1, the OCB mode liquid crystal display device has a liquid crystal layer which is bent and aligned on the substrate surface when a voltage is applied, that is, in a black display, and a substrate 6 for sandwiching the liquid crystal layer. And a liquid crystal cell composed of the substrate 8.

The alignment treatment is performed on the surface of the substrate 6 and the substrate 8 on the liquid crystal layer side. Its alignment direction (friction direction) is indicated by an arrow mark RD. In addition, the back side is indicated by a dotted arrow mark. The polarizing films 1 and 101 are disposed so as to sandwich the liquid crystal cell, and are disposed such that the transmission axis 2 of the polarizing film 1 and the transmission axis 102 of the polarizing film 101 are orthogonal to each other, and the RD direction of the liquid crystal layer of the liquid crystal cell At an angle of 45°.

An optical compensation film 13A (113A) is disposed between the polarizing film 1 (101) and the liquid crystal cell, and the optical compensation film 13A (113A) is made of a cellulose film 13a (113a) and a molecular system of the disk compound. The oblique angle of the film plane is constituted by an optically anisotropic layer 5 (9) which is fixed in a hybrid alignment state in which thickness directions are different. The deuterated cellulose film 13a (113a) has its retardation axis 14a (114a) arranged in parallel with the direction of the transmission axis 2 (102) of the adjacent polarizing film 1 (101).

The liquid crystal cell in Fig. 1 is composed of an upper substrate 6 and a lower substrate 8, and a liquid crystal layer formed of liquid crystal molecules 7 sandwiched therebetween. An alignment film (not shown) is formed on the surface of the liquid crystal molecules 7 contacting the substrate 6 and the substrate 8 (hereinafter also referred to as "inner surface"), and liquid crystal molecules are not applied in a voltage state or in a low applied state. The alignment of 7 is controlled in a parallel direction with a pretilt angle.

Further, on the inner surfaces of the substrate 6 and the substrate 8, a transparent electrode (not shown) capable of applying a voltage to the liquid crystal layer composed of the liquid crystal molecules 7 is formed.

In the present invention, the product of the liquid crystal layer thickness d (μm) and the refractive index anisotropy Δn Δn. d, preferably set to 0.1 to 1.5 μm, more preferably set to 0.2 to 1.5 μm, and still more preferably set to 0.3 to 1.2 μm, particularly preferably set to 0.4 to 1.0 μm. If it is within these ranges, a bright high-contrast display device can be produced because of the high brightness of the white display when a white voltage is applied. The liquid crystal material to be used is not particularly limited. However, when a mode of applying an electric field between the upper and lower substrates 6 and the substrate 8 is used, the dielectric constants such as the liquid crystal molecules 7 are parallel to each other in the direction of the electric field. Positive liquid crystal material.

For example, when the liquid crystal cell is made into a liquid crystal cell of the OCB mode, a dielectric negligence is positive between the upper substrate 6 and the lower substrate 8, and a directional phase of Δn=0.16 and Δε=5 is used. Liquid crystal material, etc.

The thickness d of the liquid crystal layer is not particularly limited, but may be set to about 4 μm when a liquid crystal having the characteristics of the above range is used. Since the brightness in the white display is the product of the thickness d and the refractive index anisotropy Δn when the white voltage is applied, Δn. The size of d varies, so if sufficient brightness is to be obtained when a white voltage is applied, Δn of the liquid crystal layer in an unapplied state. d is preferably set in the range of 0.4 to 1.0 μm.

Further, in the OCB mode liquid crystal display device, a chiral agent which is generally used in a liquid crystal display device of the TN mode is used less because of deterioration of dynamic response characteristics, but also for reducing alignment. Bad additions.

Further, in the case of being made into a multi-domain structure, it is advantageous to adjust the alignment of the liquid crystal molecules in the boundary region between the domains.

The "multi-domain structure" refers to a structure in which one pixel of a liquid crystal display device is divided into a plurality of regions. For example, in the OCB mode, if a multi-domain structure is adopted, the viewing angle characteristics of luminance or hue will be improved, and thus it is preferable.

Specifically, by averaging two or more (preferably four or eight) regions in which the initial alignment states of the liquid crystal molecules are different from each other, the luminance or hue depending on the viewing angle can be reduced. Offset. Further, when each pixel is configured by two or more regions different from each other in which the alignment direction of the liquid crystal molecules continuously changes when a voltage is applied, the same effect can be obtained.

The transparent support 13a (113a) can also be used as a support for the optically anisotropic layer 5 (9), or as a protective film for the polarizing film 1 (101), or both. In other words, the polarizing film 1 (101), the transparent support 13a (113a), and the optically isotropic layer 5 (9) can be integrated into a liquid crystal display device as an integrated laminate, or can be separately used as separate Components are assembled.

In addition, a configuration may be adopted in which a protective film for a polarizing film is disposed between the transparent support 13a (113a) and the polarizing film 1 (101). However, it is preferable that the protective film is not disposed. The retardation axis 14a of the transparent support 13a and the retardation axis 114a of the transparent support 113a are preferably substantially parallel or orthogonal to each other. When the retardation axis 14a of the transparent support 13a and the retardation axis 114a of the transparent support 113a are orthogonal to each other, by mutually canceling the birefringence of each transparent support, vertical incidence on the liquid crystal display device can be reduced. The optical properties of light will degrade. Further, when the retardation axes 14a and 114a are parallel to each other, if there is a residual phase difference in the liquid crystal layer, the phase difference can be compensated by the birefringence of the protective film.

The transmission axis 2 (102) of the polarizing film 1 (101), the retardation axis direction 14a (114a) of the transparent support 13a (113a), and the alignment direction of the liquid crystal molecules 7 are used for the materials and displays of the respective members. The mode, the layered structure of the components, etc. are adjusted to the optimum range. That is, the transmission axis 2 of the polarizing film 1 and the transmission axis 102 of the polarizing film 101 are arranged to be substantially orthogonal to each other. However, the liquid crystal display device of the present invention is not limited to such a configuration.

The optically anisotropic layer 5 (9) is disposed between the transparent support 13a (113a) and the liquid crystal cell. The optically anisotropic layer 5 (9) is a layer formed of a liquid crystalline compound such as a composition containing a rod-like compound or a disk-like compound.

In the optically anisotropic layer 5 (9), the molecular system of the liquid crystalline compound is fixed in a specific alignment state.

The molecular symmetry axis of the liquid crystalline compound in the optically anisotropic layer 5 (9), at least in the alignment average direction 5a (9a) of the interface of the transparent support 13a (113a), and the transparent support 13a (113a) The in-plane retardation axis 14a (114a) intersects at approximately 45°. When configured in such a relationship, the optically anisotropic layer 5 (9) will cause hysteresis to incident light from the normal direction so as not to cause light leakage, and incident light from oblique direction The effects of the present invention are fully exerted. At the interface of the liquid crystal cell side, the alignment average direction of the molecular symmetry axis of the optically isotropic layer 5 (9) is preferably 45 for the retardation axis 14a (114a) in the plane of the transparent support 13a (113a). °.

Further, the alignment average direction 5a of the polarizing film side (optical anisotropic layer interface side) of the molecular symmetry axis of the liquid crystal compound of the optically anisotropic layer 5 is preferably substantially the same as the transmission axis 2 of the polarizing film 1 which is located closer. Configured to 45°. The alignment average direction 9a of the polarizing film side (optical anisotropic layer interface side) of the molecular symmetry axis of the liquid crystal compound of the optically anisotropic layer 9 is preferably substantially disposed on the transmission axis 102 of the polarizing film 101 which is closer. In 45°. When arranged in such a relationship, the optical switch can be performed in response to the hysteresis generated by the optical anisotropic layer 5 (9) and the hysteresis generated in the liquid crystal layer, and the incident light from the oblique direction can be sufficiently The effects of the present invention are exerted.

<Principles of Image Display>

Next, referring to Fig. 1, the principle of image display of the liquid crystal display device will be described below.

When a driving state corresponding to a driving voltage of black is applied to each of the transparent electrodes (not shown) of the substrate 6 and the substrate 8 of the liquid crystal cell, the liquid crystal molecules 7 in the liquid crystal layer are curved and aligned, and the in-plane retardation at that time is The in-plane hysteresis of the optically isotropic layer 5 (9) is offset, and as a result, the polarization state of the incident light hardly changes. Since the transmission axis 2 of the polarizing film 1 and the transmission axis 102 of the polarizing film 101 are orthogonal, the light incident from the lower side is polarized by the polarizing film 101, and is maintained in a polarized state, and is polarized by the liquid crystal cell. The film 1 is blocked.

That is, in the liquid crystal display device of Fig. 1, an ideal black display can be realized in the driving state. On the other hand, when a driving state corresponding to the driving voltage of white is applied to the transparent electrode (not shown), the liquid crystal molecules 7 in the liquid crystal layer will have a different bending alignment from the curved alignment corresponding to black, so that the front side is The in-plane hysteresis changes to the case of black. As a result, it is impossible to pass through the liquid crystal cell by the in-plane retardation of the optical anisotropic layer 5 (9), and the polarizing state is changed to pass through the polarizing film 1. That is, a white display can be obtained.

Conventionally, in the OCB mode, even if the contrast of the front side is high, the problem is reduced in the oblique direction. In the case of black display, high contrast can be obtained by compensation of the liquid crystal cell and the optical anisotropic layer on the front side, but when viewed from an oblique direction, birefringence and polarization of the polarization axis are generated in the liquid crystal molecule 7. .

Further, the intersection angle between the transmission axis 2 of the polarizing film 1 and the transmission axis 102 of the polarizing film 101 is orthogonal to 90° on the front side, but is shifted from 90° when viewed from the oblique direction. So far, there has been a problem that light leakage occurs in the oblique direction due to the two factors, resulting in a decrease in contrast.

In the liquid crystal display device of the present invention having the configuration shown in Fig. 1, by using the transparent support 13a (113a) in which the Re/Rth of each of R, G, and B is inconsistent and has optical characteristics conforming to specific conditions. Reduces light leakage during black display to improve contrast.

More specifically, the present invention achieves light of respective wavelengths of R, G, and B for oblique incidence by using a transparent support having optical characteristics as described above and an optically anisotropic layer, at different wavelengths. Optical compensation is implemented by the slow phase axis and hysteresis.

Further, the optically anisotropic layer 5 (9) in which the alignment of the liquid crystal compound is fixed is disposed such that the molecular symmetry axis of the liquid crystal compound is delayed in the alignment average direction of the transparent support side interface and the transparent support When the axes are crossed at 45°, a unique compensation method for OCB alignment can be achieved at all wavelengths.

As a result, the viewing angle contrast of the black display can be particularly improved, and the coloring in the viewing direction of the black display can be particularly reduced.

In particular, when the angle of view is changed in the left-right direction, for example, in the azimuth direction of 0° and the polar angle of 60° in the direction of 180°, although there is a difference in coloring and asymmetry in the left and right, it is also possible to obtain special Improve the land.

In the present specification, the wavelengths of R, G, and B are R at 630 nm, G at 550 nm, and B at 450 nm. Although the wavelengths of R, G, and B are not necessarily represented by the wavelength, they are suitable wavelengths for specifying optical characteristics capable of exerting the effects of the present invention.

Particularly in the present invention, particular attention is paid to the ratio of Re to Rth of the transparent support Re/Rth. This is because the value of Re/Rth is used to determine the two intrinsic polarization axes in the light propagation of the biaxial birefringent medium in an oblique direction. The two natural polarization axes in the light propagation of the biaxial birefringence medium in the oblique direction correspond to the major axis and the minor axis of the profile formed when the refractive index ellipsoid is cut in the normal direction of the light proceeding direction. direction. Fig. 2 shows the direction of one of the two natural polarizations when the incident oblique light is applied to the transparent support of the present invention, that is, in this case, the angle of the retardation axis is calculated and Re An example of the result of the /Rth relationship.

In addition, Fig. 2 assumes that the direction of light propagation is azimuth = 45° and polar angle = 34°. As shown in Fig. 2, the angle of the slow phase axis is independent of the wavelength of the incident light and depends only on Re/Rth. The change in the polarization state of the incident light due to the transparent support depends mainly on the azimuth axis orientation of the transparent support and the hysteresis of the transparent support, but the prior art does not relate to R, G. The values of Re/Rth are the same for each wavelength of B, that is, the angles of the slow phase axes are also substantially the same.

On the other hand, in the present invention, the relationship between Re/Rth is defined for each of the wavelengths of R, G, and B, so that both the slow phase axis and the hysteresis of the factor that mainly determines the change in the polarization state are G and B are optimized for each wavelength.

Further, when the oblique light passing through the transparent support passes through the optically anisotropic layer which is fixed by the alignment of the liquid crystalline compound and passes through the liquid crystal layer which is aligned, the Re/Rth of the transparent support can be obtained. The value is adjusted in response to the wavelength to compensate for both wavelengths, such as hysteresis and the fact that the transmission axis on the surface of the upper and lower polarizing films is offset from the front side.

Specifically, by increasing the Re/Rth of the transparent support by increasing the wavelength, the difference between the polarization states of the R, G, and B due to wavelength dispersion of the optical anisotropic layer and the liquid crystal cell layer can be eliminated. .

As a result, complete compensation can be achieved to reduce contrast reduction. That is, if the parameters of the film are determined by R, G, and B representing all areas of visible light, substantially complete compensation can be achieved in all areas of visible light.

Here, the polar angle and the azimuth angle are defined as follows. "Polar angle" is the normal direction of the optical compensation film surface, that is, the inclination angle from the z-axis in Fig. 1, for example, the normal direction of the optical compensation film surface is 0° The direction.

"Azimuth" means an azimuth that rotates counterclockwise based on the positive direction of the x-axis. For example, the positive direction of the x-axis is azimuth angle = 0°, and the positive direction of the y-axis is azimuth = 90° direction.

The black light leakage will be the most problematic oblique direction. Since the polarizing axis of the polarizing layer is ±45°, it mainly means that the polar angle is not 0°, and the azimuth angle is 0°, 90°. 180°, 270°.

To explain the effects of the present invention in more detail, the polarized state of light incident on the liquid crystal display device is shown on the Poincare sphere in FIG. In addition, in Fig. 3, the S2 axis is a shaft that runs vertically downward from the paper surface, and Fig. 3 is a view of the Puancarre ball viewed from the positive direction of the S2 axis. In addition, since the third figure is shown in a plane manner, the displacement before the change of the polarization state and the point after the change is indicated by the arrow mark of the straight line in the figure, but actually the polarization state caused by the liquid crystal layer or the transparent support The change is represented on the Puancarre ball by rotating a specific angle around a specific axis determined by the respective optical characteristics. Hereinafter, the same applies to the fifth and sixth figures.

Fig. 3A is a view showing a change in the polarization state of the G light incident from the left 60° in the liquid crystal display device of Fig. 1, and Fig. 3B is a view showing a change in the polarization state of the G light incident from the right 60°. Further, the optical characteristics of the transparent support 13a (113a) and the optical characteristics of the optically anisotropic layer 5 (9) are assumed to be calculated under the same conditions as the Puankare ball of Fig. 6 which will be described later. The G light incident from the left 60° is as shown by the point on the 3A map of the Pu'an Carre sphere, and the polarization state changes.

Specifically, the polarization state of light polarizing film 101 G I _1, 113a through the transparent support ₂ become the polarization state I, with anisotropic optical layer 9 become the polarization state I _3, the time of black display by The liquid crystal layer of the liquid crystal cell is in a polarized state of I ₄ , is in a polarized state of I ₅ by the optically isotropic layer 5, and is in a polarized state of I ₆ by the transparent support 13a, and is displayed by being shielded by the polarizing film 1. Ideal black. In contrast, the G light incident from the right 60° changes its polarization state as I ₁ '→I ₂ '→I ₃ '→I ₄ '→I ₅ '→I ₆ '.

When the form of the polarization state change is reviewed, the polarization state caused by the optically isotropic layer 5 (9) and the liquid crystal layer 7 is changed, and the incident light from the left 60° and the right 60° is mirror-finished. The symmetry changes, but the change in the polarization state caused by the transparent support 13a (113a) relatively is uniform with the incident light from the left 60° and the right 60°. In order to reduce the left and right black light leakage and the left and right color shifts, it is necessary to satisfy the compensation condition simultaneously for any wavelength. That is, not only the G light, but also the incident light of each of R (red) and B (blue) in the visible light region, it is necessary to make the positions of I6 and I6' coincide, and the position thereof is to be covered by the polarizing film 1. The position of the broken polarized state. The change as described above is represented by a straight line on the graph, but the Puankare sphere is not limited to this linear change.

Fig. 4 is a view showing the configuration of a conventional liquid crystal display device of the OCB mode disclosed in Japanese Laid-Open Patent Publication No. H11-316378. As shown in Fig. 4, this configuration is not provided with an optical compensation film in which Re/Rth exhibits wavelength dependence as described above, and the transparent support 3a (103a) is disposed. The transparent support 3a (103a) is used for the purpose of supporting the optically anisotropic layer 5 (9), and is composed of a general polymer film.

Therefore, there is no wavelength dependence on the Re/Rth exhibited by the transparent support 13a (113a), and the same Re and Rth appear at any of R, G, and B.

As a result, the conventional OCB mode liquid crystal display device, when a voltage is applied, that is, in the black display, will cause the front side to be retarded against the front side of the liquid crystal cell and the optical anisotropic layer to obtain black, but In the oblique direction, the problem of light leakage of the black display cannot be completely suppressed. In addition, sufficient viewing angle contrast cannot be obtained, and since all wavelengths cannot be compensated for, there is a problem of coloring.

For a more detailed explanation, the polarization states of the R, G, and B lights of the OCB mode liquid crystal display device of the conventional configuration shown in Fig. 4 are calculated, and the results are shown on the Puankare ball of Fig. 5. Fig. 5A is a diagram showing changes in the polarization state of light incident from the left 60° to each of R, G, and B, and Fig. 5B is a change in the polarization state of light incident from the right 60° to each of R, G, and The picture shown by B. In the figure, the polarization state of R incident light is represented by I _R , the polarization state of G incident light is represented by I _G , and the polarization state of B incident light is represented by I _B . In addition, in the conventional OCB mode liquid crystal display device, it is assumed that the transparent support 3a (103a) in FIG. 4 is Re=45 nm and Rth=160 nm for any wavelength of R, G, and B, and The optically isotropic layer 5 (9) was calculated by Re = 30 nm.

First, in Fig. 5A, I _R1 , I _G1 and I _B1 are equal in the polarized state after passing through the polarizing film 101. When looking at the change of the polarization state of the B light, it can be understood that the B light incident from the left 60°, the polarization state I _B2 after passing through the transparent support 103a, is displaced and the transition due to the optically different directional layer 9 The direction of the B light incident from the right 60° in the same direction is the polarization state I _B2 ' after passing through the transparent support 103a, and is displaced in a direction opposite to the direction in which the optically isotropic layer 9 is displaced. That is, the light incident from the left and the light incident from the right have different effects on the polarization state of the transparent support 103a. As a result, not only the positions of the final transition states I _R6 , I _{G6 ,} and I _B6 of the incident light from R, G, and B of the left 60°, but also the incident lights of R, G, and B from the right 60° are caused. The positions of the final transition states I _R6 ', I _G6 ' and I _B6 ' are inconsistent, and are completely different in terms of the left 60° and the right 60°. Therefore, the light leakage of the left and right sides and the displacement of the left and right colors are caused, but it has been difficult to improve them at the same time.

In the present invention, a transparent support having a specific optical characteristic is disposed to simultaneously improve the black light leakage and the left and right color shift of the OCB mode liquid crystal display device. To explain in more detail, the results of the calculation of the polarization states of the R, G, and B lights of the OCB mode liquid crystal display device constructed by the present invention shown in Fig. 1 are shown on the Puancarre ball of Fig. 6.

Fig. 6A is a diagram showing changes in the polarization state of light incident from the left 60° for each of R, G, and B, and Fig. 6B is a diagram showing changes in the polarization state of light incident from the right 60° to R, G, and B. The picture shown.

In FIGS. 6A and 6B, the polarization state of the R incident light is represented by I _R , the polarization state of the G incident light is represented by I _G , and the polarization state of the B incident light is represented by I _B . In addition, it is assumed that the transparent support 13 (113) has a Re/Rth (Re ₍₄₅₀₎ / Rth ₍₄₅₀₎ ) of 0.17 at a wavelength of ₄₅₀ nm, and Re/Rth (Re ₍₅₅₀₎ / Rth ₍₅₅₀ at a wavelength of 550 nm _{). )} ) is 0.28, and the Re/Rth ((Re ₍₆₃₀₎ / Rth ₍₆₃₀₎ ))) at a wavelength of 650 nm is 0.39, and the Rth (Rth ₍₅₅₀₎ ) at a wavelength of 550 nm is 160 nm. Regarding the Re of the optically isotropic layer 5 (9), it is assumed to be the same value as the Pampere ball shown in Fig. 5.

As shown in FIGS. 6A and 6B, the R light, the G light, and the B light incident from the left and right pass through the transparent support 113a, that is, change to a position near S1=0, and reflect the transparent support 113a. The polarization state of the position displaced by the Re/Rth wavelength dependence. This displacement is used to cancel the polarization state displacement of the R light, the G light, and the B light due to the wavelength dispersion of the optically isotropic layer 9 (5) and the liquid crystal layer 7. As a result, the light incident from either of the left and right directions may be at the same position without depending on the wavelength. As a result, it is possible to simultaneously improve the light leakage of the left and right black and the color shift of the left and right.

The present invention is a transparent support body as described above by using a wavelength dispersion having hysteresis because the incident light is a normal direction and an optical characteristic which is oblique to the oblique direction, for example, a 60° polar angle direction. a cellulose film) and an optically anisotropic layer, and actively using such optical characteristics of the transparent support and the optically anisotropic layer for optical compensation to simultaneously improve left and right black light leakage, left and right color shifts . Therefore, as long as the principle is utilized, the scope of the present invention is not limited to the display mode of the liquid crystal layer, and the liquid crystal display device having the liquid crystal layer of any display mode such as the VA mode, the IPS mode, or the ECB mode and the TN mode be usable.

Further, the liquid crystal display device of the present invention is not limited to the configuration shown in Fig. 1, and may include other members. For example, a color filter may be disposed between the liquid crystal cell and the polarizing film. Further, when used in a transmissive type, a backlight using a cold cathode or a hot cathode fluorescent tube, or a light emitting diode, a field emission element, or an electroluminescence element as a light source may be disposed on the back surface.

Further, the "liquid crystal display device" of the present invention includes an image direct view type, an image projection type, or a light modulation type. The present invention is particularly effective for a method of using an active matrix type liquid crystal display device using, for example, a TFT (Thin Film Transistor) or a MIM (Metal Insulator Metal) three-terminal or two-terminal semiconductor element. Of course, it can also be effectively applied to a passive matrix type liquid crystal display device typified by an STN (Super Torsional Nematic) type called time division driving.

(optical compensation film)

The optical compensation film of the present invention has at least a transparent support. Further, an optically anisotropic layer may be formed on the transparent support as needed. Hereinafter, each member constituting the optical compensation film of the present invention will be described in detail.

<Transparent support>

The transparent support for constituting the optical compensation film of the present invention is not particularly limited as long as it is a transparent film, and may be appropriately selected depending on the purpose, but may be an extended polymer film or may be an extended polymer film. The coating type polymer layer is used in combination with a polymer film. The material of the polymer film is generally a synthetic polymer. The "synthetic polymer" includes, for example, polycarbonate, polyfluorene, polyether oxime, polyacrylate, polymethacrylate, norbornene resin, cellulose ester, and the like.

In the method of controlling Re of the transparent support, assuming that the glass transition temperature of the transparent support is (Tg), it is preferred to use a method of extending the transparent support at a temperature of (Tg + 15) to (Tg + 100) °C. In the extending step of extending the transparent support, a shrinking step of shrinking may also be included.

In the present invention, the reverse wavelength dispersion characteristic of Re and the forward wavelength dispersion characteristic of Rth, which are difficult to achieve by one film, are achieved by division and adjustment as described below. That is, the reverse wavelength dispersion property of Re is mainly performed by changing the film extension conditions, and the forward wavelength dispersion property of Rth is mainly carried out by adding an additive (Rth riser).

At this time, the results of the known extension can be expressed in the orientation degree P (the alignment order parameter; the Peifeng Pavilion, the liquid crystal dictionary page 175, and the 1989 12/5 preliminary edition) described in the present invention.

Fig. 7A shows the wavelength dispersion in the case where the additive was not extended and only the additive was added, and Fig. 7B shows the wavelength dispersion when the case was extended without adding the additive.

As shown in Figures 7A and 7B, neither of them can achieve the reverse dispersion characteristics of Re and the forward dispersion characteristics of Rth.

In contrast to the above, Figure 7C shows the wavelength dispersion of the case where the extension was carried out and the additive was added.

As shown in Fig. 7C, if a reverse wavelength dispersion characteristic of Re and a forward wavelength dispersion characteristic of Rth are to be achieved in a single film, it is apparent that these two conditions (extension and addition of an Rth rising agent) are simultaneously required.

<Orientation P>

The transparent support for constituting the optical compensation film of the present invention preferably has a desired value of Re at each wavelength by stretching in a high temperature region. The mechanism is as follows, taking the best example of deuterated cellulose as an example.

The deuterated cellulose is formed by a main chain composed of a glucopyranose ring and a side chain composed of a mercapto group. When a film made of deuterated cellulose is stretched, Re is observed in the direction in which the polymer main chain extends.

As a result of intensive research, the inventors of the present invention found that when extended at a very high temperature such as 175 ° C or higher (Tg of deuterated cellulose used is 148 ° C), Re has a decrease at 450 nm, The phenomenon that Re at 650 nm will rise.

This is caused by a significant increase in the alignment of the deuterated cellulose due to the elongation in the high temperature region under the conditions described above. The parameter representing the alignment of deuterated cellulose is the degree of orientation P calculated by X-ray diffraction measurement. The X-ray diffraction measurement uses RAPID R-AXIS manufactured by Rigaku Corp., and the X-ray source uses a CuKα line and generates X-rays at 40 kV-36 mA. Collimation tube is 0.8 mm The deuterated cellulose film as a sample was fixed by a transmission sample stage. The measurement was carried out under the conditions of 22 ° C and 60% RH. The degree of alignment P of the deuterated cellulose defined by the following formula (A) from the detected X-ray pattern is preferably from 0.05 to 0.30, more preferably from 0.06 to 0.30, particularly preferably from 0.08 to 0.30. Further, the upper limit of the degree of orientation P is 1.0.

P=<3 cos ² β-1>/2 (A)

However, <cos ² β>=∫(0,π)cos ² βI(β)sinβdβ/∫(0,π)I(β)sinβdβ.

Further, in the above formula, the angle formed by the incident surface of the X-ray incident on the β-ray and the direction in the plane of the transparent support (deuterated cellulose film) is the X-ray diffraction pattern measured at the angle β. The diffraction intensity of 2θ=8°. Further, since the cellulose-deposited film which has been extended at a high temperature exhibits a peak of X-ray diffraction which may be derived from crystallization, the crystallization of the cellulose-deposited film is effective for exhibiting the desired Re.

If it is desired to improve the color shift of the liquid crystal display device, it is also important to control Rth. In the present invention, it is preferred to use an Rth rising agent for selectively controlling Rth. The Rth rising agent is preferably a compound which selectively exhibits Rth to Re in a transparent support. Specifically, when the transparent support is uniaxially stretched at 160 ° C and 115% of the fixed end, it is preferable that the difference between the Rth values before and after the addition and the difference between the Re before and after the addition is 5 or more, and more preferably 8 or more. Further preferably, it is 10 or more.

In the optical compensation film of the present invention, when a transparent support is produced, Rth can be controlled by an added Rth rising agent and an extending step.

If you want to achieve the desired Rth value, you need to control the cohesive state of the additives in the transparent support.

The measure for controlling the aggregation state of the additive in the transparent support body is effective to control the drying speed in the drying step after casting the polymer solution of the raw material of the transparent support on the belt.

In the drying step, the average drying speed of the transparent support in the range of 10 to 100% by mass in the drying step is preferably at least 1.2% by mass/minute, more preferably 1.4% by mass or more. . The Rth rising agent in the transparent support body dried by using this condition has a small aggregation size, and the desired Rth can be achieved while maintaining the transparency of the transparent support.

The Re ₍₅₅₀₎ for the transparent support for constituting the optical compensation film of the present invention preferably ranges from 10 to 100 nm, more preferably from 10 to 90 nm, and still more preferably from 20 to 80 nm.

Further, the Rth ₍₅₅₀₎ for the transparent support constituting the optical compensation film of the present invention preferably ranges from 100 to 200 nm, more preferably from 110 to 200 nm, and still more preferably from 120 to 200 nm.

The range of the following formula (3) for constituting the transparent support of the optical compensation film of the present invention is preferably from 0.40 to 0.95, more preferably from 0.55 to 0.8, and still more preferably from 0.55 to 0.75.

Further, the range of the following formula (4) for constituting the transparent support of the optical compensation film of the present invention is preferably from 1.02 to 1.50, more preferably from 1.10 to 1.45, and still more preferably from 1.10 to 1.42.

0.5<Re ₍₄₅₀₎ /Re ₍₅₅₀₎ <1.0 Equation (3) 1.0<Re ₍₆₃₀₎ /Re ₍₅₅₀₎ <1.5 Equation (4)

In the formula, the absolute value of Re is preferably controlled in a preferred range depending on the manner of each liquid crystal layer. For example, in the case of the OCB and VA modes, it is preferably 20 to 110 nm, more preferably 20 to 100 nm, and still more preferably 35 to 90 nm.

Further, the range of the following formula (5) for constituting the transparent support of the optical compensation film of the present invention is preferably from 1.01 to 1.50, more preferably from 1.02 to 1.40, and still more preferably from 1.05 to 1.30.

Further, the range of the following formula (6) for forming the transparent support of the optical compensation film of the present invention is preferably from 0.60 to 1.00, more preferably from 0.65 to 0.99, and still more preferably from 0.75 to 0.97.

1.0<Rth ₍₄₅₀₎ /Rth ₍₅₅₀₎ <1.5 Equation (5) 0.5<Rth ₍₆₃₀₎ /Rth ₍₅₅₀₎ <1.0 Equation (6)

Further, the hysteresis (Rth) in the thickness direction of the entire transparent support has a function of canceling the hysteresis of the liquid crystal layer in the thickness direction at the time of black display, and the preferable range differs depending on the mode of each liquid crystal layer.

For example, in optical compensation of a liquid crystal cell used in an OCB mode (for example, an OCB mode liquid crystal cell having a liquid crystal layer having a product of thickness d (μm) and a refractive index anisotropy Δn of Δn.d of 0.2 to 1.5 μm) It is preferably from 70 to 400 nm, more preferably from 100 to 400 nm, and still more preferably from 130 to 200 nm.

<醯化纤维素〉>

A raw material for use as a transparent support of the support material of the present invention (hereinafter also referred to as "deuterated cellulose (film)") can be used as a conventional raw material (see, for example, the Invention Association Open Technical Report 2001). -1745).

In addition, the synthesis of deuterated cellulose can also be carried out by a known method (see, for example, Uchida and others, "Wood Chemistry", pp. 180-190 (Kyoritsu Publishing, 1968)).

The average degree of polymerization of the deuterated cellulose is preferably from 200 to 700, more preferably from 250 to 500, and still more preferably from 250 to 350.

Further, the cellulose ester used in the present invention preferably has a narrow distribution of molecular weight distribution of Mw/Mn (Mw-based mass average molecular weight, Mn coefficient amount average molecular weight) measured by gel permeation chromatography.

The specific value of Mw/Mn is preferably from 1.5 to 5.0, more preferably from 2.0 to 4.5, and still more preferably from 3.0 to 4.0.

The mercapto group of the cellulose-degraded cellulose film of the present invention is not particularly limited, but is preferably an ethyl fluorenyl group, a propyl fluorenyl group, and particularly preferably an ethyl fluorenyl group. Further, the degree of substitution of the all-fluorenyl group is preferably from 2.7 to 3.0, more preferably from 2.8 to 2.95. Further, the degree of substitution of the thiol group in the present embodiment is a value calculated according to ASTM (AMERICAN SOCIETY FOR TESTING AND MATERIALS) D817.

The mercapto group is preferably an ethyl ketone group. When a cellulose acetate having a mercapto group is an ethyl group, the degree of acetylation is preferably from 57.0 to 62.5%, more preferably from 58.0 to 62.0%. If the degree of acetylation is within this range, the Re will be larger than the desired value due to the transport tension of the flow delay, and the in-plane unevenness is small, due to the change in the hysteresis value of the temperature and humidity. There are also few.

In particular, a thiol group having 2 or more carbon atoms is substituted for the hydroxyl group of the glucose unit for constituting cellulose, and it is assumed that the degree of substitution of the hydroxyl group at the 2-position of the glucose unit is DS2. When the degree of substitution of the hydroxy group at the 3-position hydroxyl group is DS3, and the degree of substitution at the 6-position hydroxyl group with the thiol group is DS6, if the formula (I) and formula (II) shown below are satisfied, the temperature and humidity are satisfied. The resulting change in Re value will be smaller, so it is better: 2.0≦DS2+DS3+DS6≦3.0 (I); DS6/(DS2+DS3+DS6)≧0.315 (II).

<Extension method>

The cellulose-deposited film of the present invention exhibits its function by being extended as described above.

Hereinafter, an extension method suitable for the present invention will be specifically described.

The deuterated cellulose film of the present invention is preferably applied to a polarizing plate and is preferably extended in the width direction. The Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. Hei 4-298310, Japanese Laid-Open Patent Publication No. H11-48271, and the like.

Further, the extension of the cellulose-deposited film of the present invention is carried out under the conditions of 155 to 250 ° C of +5 to +100 ° C of Tg (150 ° C) of the film as described above.

The extension of the cellulose-deposited film of the present invention may also be uniaxially extended or biaxially extended.

Further, the cellulose-degraded film of the present invention can be extended in the treatment in drying, and is particularly effective when the solvent remains. For example, if the conveying roller speed of the cellulose-desulfurized film is adjusted so that the winding speed of the cellulose-deposited film is faster than the peeling speed of the cellulose-deposited film, the cellulose-deposited film can be extended.

Further, the cellulose-deposited cellulose film can be extended by maintaining the width of the cellulose-deposited film on one side and feeding it while slowly expanding the width of the tenter.

Further, after the deuterated cellulose film is dried, it is extended using an extension machine (preferably, a uniaxial extension using a long stretcher).

The stretching ratio of the cellulose-deposited film of the present invention (ratio of the portion after the extension of the original length) is preferably from 0.5 to 300%, more preferably from 1 to 200%, and still more preferably from 1 to 100% extension.

The cellulose-deposited film of the present invention is preferably produced by a film forming step of performing a solution casting method stepwise or continuously, and an extending step of stretching the film by the film, and the stretching ratio is preferably 1.2 times or more. , 1.8 times or less.

In addition, the extension step may be carried out in one step or in multiple stages. When it is carried out in a multi-stage manner, the product of the respective stretching ratios may be within the range (1.2 times or more and 1.8 times or less) as described above.

Further, the stretching speed is preferably from 5 to 1,000%/min, more preferably from 10 to 500%/min.

Further, the extending step preferably uses a heat roller and/or a radiant heat source (IR heater or the like) and warm air. In addition, a thermostatic bath can also be provided to increase temperature uniformity. When the uniaxial stretching is performed by the roll extension, the ratio L/W of the ratio of the distance between the rolls (L) to the width (W) of the protective film is preferably from 2.0 to 5.0.

It is preferred to further set up a preheating step before the stretching step, and a heat treatment may also be applied after the stretching step. The heat treatment temperature is preferably carried out at a temperature between a temperature lower than a glass transition temperature (Tg) of the cellulose acetate film by a temperature of 20 ° C up to a temperature 10 ° C higher than the glass transition temperature (Tg), and heat treatment. The time is preferably from 1 to 3 minutes.

Alternatively, the heating method may be regional heating, or localized heating using an infrared heater, or both ends of the cellulose acetate film may be cut during or at the end of the heating step. Further, the cutting chips generated at this time are preferably recovered and reused as a raw material.

In the Japanese Patent Application Laid-Open No. H11-077718, it is disclosed that the drying method is performed by appropriately controlling the drying gas when the substrate is dried while maintaining the width by a tenter. Angle, wind speed distribution, wind speed, air volume, temperature difference, air volume difference, up and down air volume ratio, and use of high specific heat drying gas to ensure the speed of the solution casting method or to prevent flatness when expanding the width of the substrate. Such techniques of reduced quality can also be employed in the present invention.

Further, in Japanese Laid-Open Patent Publication No. H11-077822, it is disclosed that, in order to prevent unevenness, the stretched thermoplastic resin film is set in the heat relaxation step after the stretching step, and the width direction of the film is set in the heat relaxation step. A technique of heat treatment for temperature gradient, which can also be applied to the heat treatment step as described above.

In Japanese Laid-Open Patent Publication No. 4-204503, a technique for setting a solvent content of a film to prevent the occurrence of unevenness and extending it by 2 to 10% on a solid content basis is disclosed. Techniques can also be employed in the present invention.

In Japanese Laid-Open Patent Publication No. 2002-248680, a curl is specified to suppress the width of the film nip, and the width D ≦ is clamped in the tenter film (33/(log extension). The technique of performing extension to suppress curling and allowing film transport after the stretching step to proceed easily can also be employed in the present invention.

In Japanese Laid-Open Patent Publication No. 2002-337224, it is disclosed that in order to coexist both the high-speed flexible film transport and the extension, the tenter transfer is converted into the first half and the second half is the diaphragm type. Techniques, this technique can also be employed in the present invention.

In Japanese Laid-Open Patent Publication No. 2002-187960, a cellulose ester coating liquid is cast on a casting support for the purpose of easily improving the viewing angle characteristics and improving the viewing angle, and then casting is carried out. The base material (film) peeled off on the support is prepared by allowing the amount of residual solvent in the substrate to be 100% by mass or less, particularly at least 1.0 to 4.0 times in one direction during the range of 10 to 100% by mass. The invention has optical biaxiality.

Further, this technique also discloses a more preferred embodiment in which the amount of the residual solvent in the substrate is 100% by mass or less, particularly in the range of 10 to 100% by mass, at least 1.0 to 4.0 times in one direction.

In addition, the other extension method of the technology also exemplifies a method of imparting a circumferential speed difference to a plurality of rollers and longitudinally extending the circumferential speed difference therebetween; fixing the both ends of the substrate with a film crucible or a pin and proceeding a method of expanding the spacing of the film or the pin to extend in the longitudinal direction; similarly, expanding in the lateral direction to extend in the lateral direction; or expanding in the longitudinal and lateral directions to extend in both the longitudinal and transverse directions; and combining the methods for use Wait.

Further, it is disclosed that, in the case of the so-called tenter method, when the film portion is driven by the linear driving method, a smooth extension can be applied, and the risk of breakage or the like can be reduced, and therefore, the techniques are also preferable. It is used in the present invention.

In Japanese Laid-Open Patent Publication No. 2003-014933, an optical compensation film which exhibits less bleed-out of an additive and which has no peeling phenomenon between layers, and which has good slidability and excellent transparency, is disclosed. The coating liquid A containing the resin, the additive and the organic solvent is prepared, and the coating liquid B containing the resin, the additive and the organic solvent containing no additive or additive content less than the coating liquid A, and the coating liquid A as the core layer is coated. The liquid B is coextensive on the support in the state of the surface layer, and after evaporating the organic solvent until peeling off, the substrate is peeled off by the transparent support, and the residual solvent in the resin film at the time of extension is 3 to 50 A technique that extends at least 1.1 to 1.3 times in a single axial direction over a range of mass %.

Furthermore, this technique also reveals a more preferred embodiment, preferably by utilizing various measures as follows: the substrate is peeled off from the support and extends at least in a uniaxial direction at an extension temperature of 140 to 200 °C. Up to 3.0 times; preparing a coating liquid A containing a resin and an organic solvent, and a coating liquid B containing a resin, a fine particle, and an organic solvent, and coextruding with a coating liquid A as a core layer and a coating liquid B as a surface layer. On the transparent support, and after evaporating the organic solvent until peeling off, the substrate is peeled off from the transparent support, and the residual solvent in the resin film at the time of stretching is in the range of 3 to 50% by mass, at least in a uniaxial direction. 1.1 to 1.3 times; further extending at least 1.1 to 3.0 times in a uniaxial direction at an extension temperature of 140 to 200 ° C; preparing a coating liquid A containing a resin, an organic solvent and an additive, and containing no additives or additives a coating liquid B containing a resin, an additive, and an organic solvent having a lower content than the coating liquid A, and a coating liquid C containing a resin, fine particles, and an organic solvent, and a coating liquid A as a core layer and a coating liquid B as a surface layer. The coating liquid C is a table located on the opposite side to the coating liquid B. The surface layer is continuously cast on the support, and after the organic solvent is evaporated until peeling off, the substrate is peeled off from the support, and the residual solvent in the resin film at the time of stretching is in the range of 3 to 50% by mass. , extending at least 1.1 to 1.3 times in a single axial direction; extending at a temperature of 140 to 200 ° C, at least 1.1 to 3.0 times in a uniaxial direction; and the amount of the additive in the coating liquid A is 1 to 30 by mass relative to the resin %, the amount of the additive in the coating liquid B is 0 to 5% by mass based on the resin, and the additive is a plasticizer, an ultraviolet absorber or a hysteresis controlling agent; and the organic solvent in the coating liquid A and the coating liquid B are contained. Methylene chloride or methyl acetate is 50% by mass or more based on the entire organic solvent. These techniques can also be employed in the present invention.

In Japanese Laid-Open Patent Publication No. 2003-014933, it is disclosed that the stretching method is suitable for fixing the both ends of the substrate with a film or a pin, and expanding the film or the gap of the pin in the lateral direction to extend in the lateral direction. A tenter called a lateral stretcher.

Further, in the publication, it is also disclosed that when it is intended to extend in the longitudinal direction or to contract it, the distance between the transport direction of the film bundle or the pin may be increased in the transport direction (longitudinal direction) by using a simultaneous biaxial stretching machine, or Shorten it to implement.

Further, in this publication, it is also disclosed that when the film portion is driven by the linear driving method, the stretching can be smoothly performed, and the risk of breakage or the like can be reduced, so that it is preferable to use a method of longitudinal stretching. A method of imparting a peripheral speed difference to a plurality of rolls while extending in the longitudinal direction by a roll peripheral speed difference therebetween.

Further, in this publication, it is also disclosed that the extension methods can also be used in combination, for example, (longitudinal extension, lateral extension, longitudinal extension), or (longitudinal extension, longitudinal extension), etc., the extension step can be divided into two or more stages. Implementations, such techniques can also be employed with the present invention.

In Japanese Laid-Open Patent Publication No. 2003-004374, it is disclosed that in order to prevent foaming of a tenter-dried substrate, to improve detachment, and to prevent dust flying, in a drying apparatus, the design is such that the width of the dryer is formed as a ratio. The technique is also applicable to the technique in which the width of the substrate is short so that the hot air of the dryer does not blow to both edges of the substrate.

In Japanese Laid-Open Patent Publication No. 2003-019757, it is disclosed that a windshield is provided on the inner side of both ends of the substrate in order to prevent foaming of the tenter-dried substrate, improve detachability, and prevent dust from flying. This technique can also be employed in the present invention so that the dry wind does not blow to the tenter holder.

In Japanese Laid-Open Patent Publication No. 2003-053749, it is disclosed that the conveying and drying are performed stably, and the thickness of both ends of the film to be held by the pin tenter is X (μm) after drying. When the average thickness of the film product part after drying is T (μm), it can meet the condition of 40≦X≦200 at T≦60, and 40+(T-60) when 60<T≦120. The condition of × 0.2 ≦ X ≦ 300; when 120 < T, the technique of satisfying the condition of 52 + (T - 120) × 0.2 ≦ X ≦ 400 can also be employed in the present invention.

In Japanese Laid-Open Patent Publication No. 2-182654, it is disclosed that in the multi-stage tenter, wrinkles are not generated, and in the tenter apparatus, a heating chamber is provided in the dryer of the multi-stage tenter. And the cooling chamber to separately cool the left and right membrane 铗-bond strips, this technique can also be employed in the present invention.

In Japanese Laid-Open Patent Publication No. Hei 9-077315, it is disclosed that in order to prevent breakage, wrinkles, and poor conveyance of the substrate, the needle of the needle-clamp tenter increases the density of the inner needle and the outer side. A technique in which the density of the needles is reduced, and the technique can also be applied to the present invention.

In Japanese Laid-Open Patent Publication No. 9-085846, a tenter drying device is disclosed in a tenter to prevent foaming of a substrate itself or adhesion of a substrate to a holding device. The cooler keeps the needle edges of both sides of the substrate cool to below the foaming temperature of the substrate, while cooling the needles before clamping the substrate to the gelation temperature of the coating liquid in the trough cooler +15 This technique can also be applied to the present invention at a temperature below °C.

In Japanese Laid-Open Patent Publication No. 2003-103542, it is disclosed that in order to prevent the pincer tenter from falling off and to optimize foreign matter, in the pin tenter, the insert structure is cooled and brought into contact with the inserted structure. The technique of the solution film forming method in which the surface temperature of the substrate does not exceed the gelation temperature of the substrate can also be employed in the present invention.

In Japanese Laid-Open Patent Publication No. H11-077718, it is disclosed that in order to increase the speed by the solution casting method or to prevent deterioration in the planarity when the tenter expands the width of the substrate, the quality is lowered in the tenter. When the substrate is dried, a technique is set in which the wind speed is 0.5 to 20 (40) m/s, the lateral temperature distribution is 10% or less, the substrate up-and-down air ratio is 0.2 to 1, and the dry gas ratio is 30 to 250 J/Kmol. . Further, regarding the drying in the tenter, preferred drying conditions according to the amount of residual solvent are disclosed.

Specifically, it is disclosed that the amount of residual solvent in the substrate reaches 4% by mass after the substrate is peeled off via the support, and the blowing angle from the outlet is set to be in the range of 30 to 150° with respect to the film plane. And the wind speed distribution on the surface of the film in the direction in which the drying gas is blown out is set to be within 20% of the upper limit value when the upper limit value of the wind speed is used as a reference, and the supply is blown out. When drying the gas to dry the substrate; when the amount of the residual solvent in the substrate is 70% by mass or more and 130% by mass or less, the drying gas blown by the blow dryer is set to have a wind speed of 0.5 m/sec or more on the surface of the substrate. When the amount of the residual solvent is less than 70% by mass and 4% by mass or more, the dry gas of the drying gas is blown at a wind speed of 0.5 m/sec or more and 40 m/sec or less. Drying, and the dry gas temperature distribution in the width direction of the substrate, if the upper limit of the gas temperature is used as a reference, the difference between the upper limit and the lower limit is set to be within 10% of the upper limit; and in the substrate The amount of residual solvent is 4% by mass or more and 200% by mass. In the case of the lower portion, the air volume ratio q of the dry gas blown out from the air outlet of the blow-drying machine located above the substrate to be conveyed is set to 0.2 ≦q ≦1. Moreover, a preferred example reveals that the dry gas uses at least one gas and has an average specific heat of 31.0 J/K. Above mol, 250 J/K. The concentration of the organic compound which is liquid at normal temperature in the dry gas which is dried is dried by a drying gas having a saturated vapor pressure of 50% or less, and the like can also be employed in the present invention.

In Japanese Laid-Open Patent Publication No. H11-077719, a tenter is disclosed in a TAC (cellulose triacetate) film manufacturing apparatus for preventing flatness or coating deterioration due to generation of a contaminant. The membrane of the machine is built with the technology of heating part.

Moreover, the technique also discloses a more preferred embodiment for removing the contact portion generated between the film and the substrate during the release of the film from the tenter of the tenter until the substrate is held again. Foreign matter device; using a gas or liquid and a brush to remove foreign matter; the residual amount of the film or the contact of the pin with the substrate is 12% by mass or more and 50% by mass or less; and the film or the pin and the substrate The surface temperature of the contact portion is 60. Above, 200. Hereinafter, the technique (more preferably 80. or more, 120 or less) or the like can be employed in the present invention.

In Japanese Laid-Open Patent Publication No. Hei 11-090943, it is disclosed that in order to optimize planarity and improve the quality reduction caused by the breakage in the tenter, the productivity is improved, and regarding the tenter film, the setting is pulled. The arbitrary transport length Lt(m) of the web, and the ratio of the total length Ltt=Lt/Lt of the transport direction length of the substrate of the tenter of the tenter having the same length as Lt is L≦=Ltt/Lt is 1.0≦ The invention of Lr≦1.99. Further, a preferred embodiment discloses a technique for maintaining a portion of the substrate to be configured to have no gap from the width direction of the substrate, and the technique can also be applied to the present invention.

Japanese Laid-Open Patent Publication No. Hei 11-090944 discloses a manufacturing apparatus for a plastic film for optimizing planarity deterioration and introduction instability caused by bending of a substrate when introducing a substrate to a tenter. Then, there is a technique of a substrate width direction bending suppressing device before the tenter entrance.

Moreover, this technique also discloses a more preferred embodiment in which the bending suppression device is a rotating roller that rotates in a direction of 2 to 60° in an angle that expands in the width direction; has a suction device on the upper portion of the substrate; A blower or the like that can be blown from below the substrate can also be used in the present invention.

In Japanese Laid-Open Patent Publication No. Hei 11-090945, the disclosure of the present invention discloses a substrate which is not peeled off and inhibits productivity. In the TAC manufacturing method, the substrate which is peeled off via the support is in the opposite direction. The technique of introducing into a tenter at a horizontal angle is also applicable to the present invention.

In Japanese Laid-Open Patent Publication No. 2000-289903, a film having a stable physical property is disclosed, and when peeled off and the solvent content is 50 to 12% by mass, tension is applied to the width direction of the substrate. The conveying device for conveying one side has a substrate width detecting device and a substrate holding device, and two or more variable bending points, and detecting the width of the substrate by the detection signal by detecting the width of the substrate to change the position of the bending point. Techniques, this technique can also be employed in the present invention.

In Japanese Laid-Open Patent Publication No. 2003-033933, it is disclosed that, in order to improve the nip property and prevent breakage of the substrate for a long period of time, to obtain a film excellent in quality, the left and right sides of the tenter adjacent to the entrance portion are On the side, at least in the upper and lower sides of the left and right edge portions of the substrate, a guide plate for preventing curling of the side edge portion of the substrate is disposed at least below, and the opposite surface of the substrate of the guide plate is disposed at the base of the substrate transport direction. The material contact resin portion and the substrate contact metal portion are formed.

Further, this technique also discloses a preferred embodiment in which the substrate contact resin portion on the substrate facing surface of the guide plate is disposed on the upstream side in the substrate transport direction, and the substrate contact metal portion is disposed on the downstream side. The step (including the inclination) between the resin-contacting resin portion of the guide plate and the substrate-contacting metal portion is within 500 μm; and the substrate-contacting resin portion of the guide plate is in contact with the substrate-contacting metal portion. The distance in the width direction of the substrate is 2 to 150 mm, respectively; the distance between the substrate contact resin portion of the guide plate and the substrate contact metal portion in the substrate transport direction of the substrate is 5 to 120 mm, respectively. The base material for contacting the substrate of the guide plate is provided on the metal guide substrate by surface resin processing or resin coating; the resin portion for contacting the substrate of the guide plate is made of a resin monomer; and the left and right edges of the substrate are The distance between the opposite faces of the substrate disposed on the upper and lower guide plates is 3 to 30 mm; the distance between the opposite faces of the substrate of the lower and lower guide plates on the left and right edges of the substrate is toward each other The width direction of the substrate and the inner side Each 100 mm width is expanded by a ratio of 2 mm or more; the lower two guide plates are respectively 10 to 300 mm in length on the left and right side edges of the substrate, and the upper and lower guide plates are oriented along the substrate conveying direction In the staggered configuration, the upper and lower guide plates are offset from each other by -200 to +200 mm; the opposite surface of the upper guide plate is composed only of resin or metal; and the substrate for contacting the substrate is Teflon (Teflon) (registered trademark), and the metal part for substrate contact is made of stainless steel; and the surface of the base material of the guide plate or the surface of the base material for contacting the substrate and/or the metal part for contacting the substrate The roughness is 3 μm or less.

Further, it is also disclosed that a preferred example is to prevent the occurrence of the position of the upper and lower guide plates for curling the side edge portion of the substrate, preferably from the peeling side end portion of the support body to the tenter introduction portion, particularly preferably These techniques can also be employed in the present invention, disposed adjacent to the entrance of the tenter.

In Japanese Laid-Open Patent Publication No. 11-048271, a solvent content ratio in a substrate after peeling is disclosed in order to prevent cutting or unevenness of a substrate which is generated during drying in a tenter. When it is 50 to 12% by mass, it is extended and dried by a width extending device; and when the solvent content of the substrate is 10% by mass or less, a technique of applying a pressure of 0.2 to 10 KPa from both sides of the substrate by a pressurizing device is employed.

Further, this technique also discloses a more preferred embodiment, that is, when the solvent content is 4% by mass or more, the tension is applied, or when the pressure is applied from both sides of the substrate (film), the nip roll is used. When pressure is applied, the number of sets of the nip rolls is preferably from about 1 to 8 sets, and the temperature at the time of pressurization is preferably from 100 to 200 ° C. This technique can also be employed in the present invention.

In the Japanese Patent Laid-Open Publication No. 2002-036266, a preferred embodiment of a technique for producing a high-quality thin pleat having a thickness of 20 to 85 μm is disclosed, which is to be applied to the substrate along the front and rear of the tenter. The difference in the tension acting in the conveying direction is set to 8 N/mm ² or less; after the peeling step, a "preheating step" for preheating the substrate is provided; for using the tenter after the preheating step Extending the "extension step" of the substrate; for relaxing the "tempering step" of the substrate only after the stretching step is less than the amount of extension of the stretching step; and in the preheating step and the stretching step as described above The temperature T _{1 is} set at (glass transition temperature Tg-60 of the film) ° C or more, and the temperature T ₂ in the relaxation step is set to be (T ₁ -10) ° C or less; and the elongation of the substrate in the stretching step is relatively The ratio of the width of the substrate immediately before the extension step is set to 0 to 30%, and the elongation of the substrate in the relaxation step is set to -10 to 10%, etc., and the technique can also be applied to the present invention. .

In the Japanese Patent Laid-Open Publication No. 2002-225054, it is disclosed that the thickness of the dried film is 10 to 60 μm, the thickness is reduced, the weight is reduced, and the moisture permeability and durability are excellent. When the amount of the residual solvent of the material is 10% by mass, the both ends of the substrate are grasped by the film, and the drying shrinkage by the holding width is suppressed and/or extended in the width direction to form the following formula (III). The film having a surface alignment S of 0.0008 to 0.0020 (in the following formula (III), Nx means a refractive index in a direction in which the refractive index in the film plane is the largest, and Ny means a refractive index in a direction orthogonal to Nx in the plane. , Nz means the refractive index in the film thickness direction of the film; the time from casting until peeling is set to 30 to 90 seconds; and the substrate after peeling is extended in the width direction and/or the length direction, etc. It can also be employed in the present invention.

S={(Nx+Ny)/2}-Nz (III)

Further, in Japanese Laid-Open Patent Publication No. 2002-341144, in order to suppress optical unevenness, it is revealed that a mass concentration including a retardation enhancer has a higher optical density as it is closer to the center in the film width direction. A solution film forming method for the extension step of the distribution, which can also be employed in the present invention.

In Japanese Laid-Open Patent Publication No. 2003-071863, it is disclosed that, in order to produce a film which does not cause turbidity, the stretching ratio in the width direction is preferably from 0 to 100%, and when used as a protective film for a polarizing plate, it is more preferable. It is 5 to 20%, and most preferably 8 to 15%.

On the other hand, this publication discloses that when used as a retardation film (optical compensation film), it is more preferably 10 to 40%, and most preferably 20 to 30%, and Ro can be controlled at a stretching ratio, if a high elongation is employed At the time of magnification, the obtained film system has superior planarity, and therefore is preferable.

Further, it is disclosed that the amount of residual solvent of the film when the tenter is applied is preferably from 20 to 100% by mass at the start of tentering, and it is preferred that the residual solvent amount of the film is up to 10% by mass or less, and is dried while being stretched. More preferably, it is 5% by mass or less.

Further, it is also disclosed that the drying temperature at the time of applying the tenter is preferably from 30 to 150 ° C, more preferably from 50 to 120 ° C, and most preferably from 70 to 100 ° C, and if a low drying temperature is employed, the ultraviolet absorber or the plasticizer If the volatilization is small, the process contamination can be reduced, but if a high drying temperature is used, the film has superior planarity of the film, and the technique can also be applied to the present invention.

Further, in Japanese Laid-Open Patent Publication No. 2002-248639, a cellulose ester solution is cast on a support to reduce longitudinal and lateral dimensional changes during storage under high temperature and high humidity conditions, and In the method for producing a film which is continuously peeled off and dried, the drying is carried out so that the drying shrinkage ratio satisfies the conditions of the following formula (IV).

0≦dry shrinkage ratio (%)≦0.1×residual solvent amount at the time of peeling (%) Formula (IV)

Moreover, this technique also reveals a more preferred embodiment in which the amount of residual solvent of the cellulose ester film after peeling is in the range of 40 to 100% by mass, and the cellulose ester film is grasped by a tenter. At least the amount of residual solvent is reduced by 30% by mass or more at both end portions and one side; the residual solvent amount at the tenter transfer inlet of the cellulose ester film after peeling is 40 to 100% by mass, and the residual solvent amount at the outlet is 4 to 20 % by mass; the tension of the cellulose ester film conveyed by the tenter is set to be increased by the tenter conveying inlet toward the outlet; and the conveying tension of the cellulose ester film by the tenter is in the width direction The tension of the cellulose ester film is approximately the same, and the like can also be employed in the present invention.

In addition, Japanese Laid-Open Patent Publication No. 2000-239403 discloses that a film having a thin film thickness and excellent optical equivalence and planarity is used, and the residual solvent ratio X at the time of peeling is introduced. The relationship between the residual solvent ratio Y at the tenter and the range of 0.3 X ≦ Y ≦ 0.9 X is carried out to form a film, and this technique can also be applied to the present invention.

Japanese Laid-Open Patent Publication No. 2002-286933 discloses a method for extending a film for casting a film, which comprises a method of stretching under heating conditions, and a method of stretching under a solvent-containing condition, If the stretching is carried out under heating, it is preferred to carry out the stretching at a temperature lower than the glass transition temperature of the resin, and when the film is formed by casting the film under the impregnation solvent, the dried film will be once dried. It is further extended by contact with a solvent to impregnate the solvent. This technique can also be applied to the present invention.

<hysteresis riser> [Controlling the retardation riser of Rth]

The transparent support for constituting the optical compensation film of the present invention contains a hysteresis riser (Rth riser) for selectively controlling Rth.

The Rth ascending agent of the present invention is a general hysteresis-increasing agent which can increase the Re and Rth of the transparent support by being added to the transparent support, and can be selectively added to the transparent support by adding it to the transparent support. A compound that exhibits Rth. For example, when the Re value and the Rth value of the transparent support obtained by adding the transparent support are subtracted from the Re value and the Rth value of the transparent support (the transparent support without the Rth rising agent added), the added compound ( The Rth which appears in the Rth ascending agent) is a compound which exhibits a specific value or more with respect to Re.

Preferably, the Rth rising agent has at least one absorption maximum at 250 nm or more, more preferably at least one absorption maximum at 250 or more and 360 nm or less, and further preferably at least one absorption maximum at 300 or more and 355 nm or less. .

With this configuration, the difference in Rth values at respective wavelengths of 630 nm, 550 nm, and 450 nm is increased, so that the hue change can be suppressed.

Further, the Rth rising agent contained in the transparent support for constituting the optical compensation film of the present invention is preferably a compound having at least a diaromatic ring.

Further, the Rth rising agent contained in the transparent support for constituting the optical compensation film of the present invention is preferably selected from the compounds represented by the general formulae (II) to (V) shown below.

In the formula (II), R ¹² each independently represents an aromatic ring or a heterocyclic ring having a substituent in at least one of an ortho, meta and para, and each of the X ¹¹ systems Independently represents a single bond or NR ¹³ -. Wherein R ¹³ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group or a heterocyclic group.

The aromatic ring represented by R ¹² is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aromatic ring represented by R ¹² may have at least one substituent at any of the substitution positions. Examples of the "substituent" include: a halogen atom, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group, a decyloxy group, an alkoxy group. Alkylcarbonyl, alkenyloxycarbonyl, aryloxycarbonyl, aminesulfonyl, alkyl-substituted amine sulfonyl, alkenyl-substituted amine sulfonyl, aryl substituted sulfonamide, sulfonium sulfonate Amino group, amine mercapto group, alkyl substituted amine carbenyl group, alkenyl substituted amine carbenyl group, aryl group substituted amine carbenyl group, decylamino group, alkylthio group, alkylthio group, Arylthio, and sulfhydryl.

The heterocyclic group represented by R ¹² is preferably aromatic. The aromatic heterocyclic ring is generally an unsaturated heterocyclic ring, preferably a heterocyclic ring having the most double bonds. The heterocyclic ring is preferably a 5-membered ring, a 6-membered ring or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and most preferably a 6-membered ring. The hetero atom of the hetero ring is preferably a nitrogen atom, a sulfur atom or an oxygen atom, and particularly preferably a nitrogen atom. The aromatic heterocyclic ring is particularly preferably a pyridine ring (heterocyclic group is 2-pyridyl or 4-pyridyl). The heterocyclic group may have a substituent. Examples of the substituent of the heterocyclic group are the same as the examples of the substituent of the aryl moiety as described above.

X ¹¹ is a heterocyclic group in the case of a single bond, and preferably a heterocyclic group having a free valence in a nitrogen atom. The heterocyclic group having a free valence in the nitrogen atom is preferably a 5-membered ring, a 6-membered ring or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and most preferably a 5-membered ring. The heterocyclic group may also have a plurality of nitrogen atoms. Further, the heterocyclic group may have a hetero atom other than a nitrogen atom (for example, O, S). Hereinafter, an example of a heterocyclic group having a free valence of a nitrogen atom is exemplified.

In the formula (II), X ¹¹ is a single bond or NR ¹³ -, and R ¹³ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group or a heterocyclic group.

The alkyl group represented by R ¹³ may be a cyclic alkyl group or a chain alkyl group, but a preferred chain alkyl group is more preferably a linear chain than a branched chain alkyl group. alkyl. The number of carbon atoms of the alkyl group is preferably from 1 to 30, more preferably from 1 to 20, still more preferably from 1 to 10, still more preferably from 1 to 8, and most preferably from 1 to 6. The alkyl group may also have a substituent. Examples of the substituent include a halogen atom, an alkoxy group (e.g., methoxy group, ethoxy group), and a decyloxy group (e.g., acryloxy group, methacryloxy group).

The alkenyl group represented by R ¹³ , although it may be a cyclic alkenyl group or a chain alkenyl group, preferably represents a chain alkenyl group, and is more preferably a straight one than a branched chain alkenyl group having a branch. Chain alkenyl. The number of carbon atoms of the alkenyl group is preferably from 2 to 30, more preferably from 2 to 20, still more preferably from 2 to 10, still more preferably from 2 to 8, and most preferably from 2 to 6. The alkenyl group may also have a substituent. Examples of the substituent are the same as the substituent of the alkyl group as described above.

The aromatic ring group and the heterocyclic group represented by R ¹³ are the same as the aromatic ring and the hetero ring represented by R ¹² , and the preferred range is also the same. The aromatic ring group and the heterocyclic group may have a substituent, and the substituent examples are the same as those of the aromatic ring and the hetero ring of R ¹² .

Hereinafter, specific examples of the Rth rising agent represented by the general formula (II) used in the present invention are shown. The plurality of Rs shown in the same structural formula in each of the exemplified compounds means the same group. The definition of R is represented at the same time as the specific instance number.

II-(1)Phenyl II-(2)3-ethoxycarbonylphenyl II-(3)3-butoxyphenyl II-(4) m-biphenyl II-(5)3-benzene Phenylthio-II-(6)3-chlorophenyl-II-(7)3-benzylidenephenyl II-(8)3-ethyloxyphenyl-II-(9)3-benzamide Oxyphenyl phenyl-(10)3-phenoxycarbonylphenyl II-(11)3-methoxyphenyl II-(12)3-anilinophenyl II-(13)3-isobutyldecylamine Phenylphenyl-(14)3-phenoxycarbonylaminophenyl II-(15)3-(3-ethylureido)phenyl II-(16)3-(3,3-diethyl Ureido)phenyl II-(17)3-methylphenyl II-(18)3-phenoxyphenyl II-(19)3-hydroxyphenyl II-(20)4-ethoxycarbonylbenzene Group II-(21)4-butoxyphenyl II-(22) p-biphenylyl-(23)4-phenylphenylthio-II-(24)4-chlorophenyl-II-(25) 4-Benzylmercaptophenyl II-(26)4-ethenyloxyphenyl II-(27)4-benzylideneoxyphenyl II-(28)4-phenoxycarbonylphenyl II- (29) 4-Methoxyphenyl II-(30)4-anilinophenyl II-(31)4-isobutyldecylaminophenyl II-(32)4-phenoxycarbonylaminophenyl II -(33)4-(3-ethylureido)phenyl II -(34)4-(3,3-diethylureido)phenylII-(35)4-methylphenylII-(36)4-phenoxyphenylII-(37)4-hydroxyl Phenyl II-(38) 3,4-diethoxycarbonylphenyl II-(39) 3,4-dibutoxyphenyl II-(40) 3,4-diphenylphenyl II-( 41) 3,4-Diphenylphenylthio II-(42)3,4-dichlorophenyl II-(43)3,4-diphenylmethylphenylphenyl II-(44)3,4- Diethoxymethoxyphenyl II-(45) 3,4-dibenzoyloxyphenyl II-(46) 3,4-diphenoxycarbonylphenyl II-(47)3,4-di Methoxyphenyl II-(48) 3,4-diphenylaminophenyl II-(49)3,4-dimethylphenyl II-(50)3,4-diphenoxyphenyl II- (51) 3,4-Dihydroxyphenyl II-(52)2-naphthyl II-(53)3,4,5-triethoxycarbonylphenyl II-(54)3,4,5-tri Butoxyphenyl II-(55)3,4,5-triphenylphenyl II-(56)3,4,5-triphenylphenylthio-II-(57)3,4,5-tri Chlorophenyl II-(58)3,4,5-tritylmercaptophenyl II-(59)3,4,5-triethoxymethoxyphenyl II-(60)3,4,5- Trityl methoxyphenyl II-(61) 3,4,5-triphenyloxycarbonylphenyl II-(62)3,4,5-trimethoxyphenyl II-(63)3,4 5-triphenylamine Phenyl II- (64) 3,4,5- trimethylphenyl II- (65) 3,4,5- triphenyl-phenyl II- (66) 3,4,5- trihydroxyphenyl

II-(67)phenyl II-(68)3-ethoxycarbonylphenyl II-(69)3-butoxyphenyl II-(70) m-biphenyl II-(71)3-benzene Phenylthio-II-(72)3-chlorophenyl-II-(73)3-benzylidenephenyl II-(74)3-acetoxyphenyl-II-(75)3-benzamide Oxyphenyl phenyl II-(76) 3-phenoxycarbonylphenyl II-(77) 3-methoxyphenyl II-(78)3-anilinophenyl II-(79)3-isobutyldecylamine Phenylphenyl-(80)3-phenoxycarbonylaminophenyl II-(81)3-(3-ethylureido)phenyl II-(82)3-(3,3-diethyl Ureido)phenyl II-(83)3-methylphenyl II-(84)3-phenoxyphenyl II-(85)3-hydroxyphenyl II-(86)4-ethoxycarbonylbenzene Base II-(87)4-butoxyphenyl II-(88) p-biphenylyl-(89)4-phenylphenylthio-II-(90)4-chlorophenyl-II-(91) 4-Benzylmercaptophenyl II-(92)4-ethenyloxyphenyl II-(93)4-benzylideneoxyphenyl II-(94)4-phenoxycarbonylphenyl II- (95) 4-Methoxyphenyl II-(96)4-anilinophenyl II-(97) 4-isobutylguanidinophenyl II-(98) 4-phenoxycarbonylaminophenyl II -(99)4-(3-ethylureido group Phenyl II-(100)4-(3,3-diethylureido)phenyl II-(101)4-methylphenyl II-(102)4-phenoxyphenyl II-(103 4-hydroxyphenyl II-(104) 3,4-diethoxycarbonylphenyl II-(105) 3,4-dibutoxyphenyl II-(106) 3,4-diphenylbenzene Group II-(107) 3,4-diphenylphenylthio II-(108)3,4-dichlorophenyl II-(109)3,4-diphenylmethylphenylphenyl-II(110) 3,4-Diethoxymethoxyphenyl II-(111)3,4-dibenzoyloxyphenyl II-(112)3,4-diphenoxycarbonylphenyl II-(113)3 , 4-dimethoxyphenyl II-(114) 3,4-diphenylaminophenyl II-(115)3,4-dimethylphenyl II-(116)3,4-diphenoxy Phenyl II-(117)3,4-dihydroxyphenyl II-(118)2-naphthyl II-(119)3,4,5-triethoxycarbonylphenyl II-(120)3,4 ,5-tributyloxyphenyl II-(121)3,4,5-triphenylphenyl II-(122)3,4,5-triphenylphenylthio-II-(123)3,4 , 5-trichlorophenyl II-(124)3,4,5-tritylphenylphenyl II-(125)3,4,5-triethoxymethoxyphenyl II-(126)3, 4,5-trityloxyphenyl-II-(127)3,4,5-triphenyloxycarbonylphenyl II-(128)3,4,5-trimethyl Phenylphenyl-II(129)3,4,5-triphenylaminophenyl II-(130)3,4,5-trimethylphenyl II-(131)3,4,5-triphenyloxy Phenyl II-(132)3,4,5-trihydroxyphenyl

II-(133)phenyl II-(134)4-butylphenyl II-(135)4-(2-methoxy-2-ethoxyethyl)phenyl II-(136)4-( 5-nonenyl)phenyl II-(137) p-biphenylyl-(138)4-ethoxycarbonylphenyl II-(139)4-butoxyphenyl II-(140)4- Methylphenyl II-(141)4-chlorophenyl II-(142)4-phenylphenylthio-II-(143)4-benzylidinylphenyl II-(144)4-ethenyloxy Phenyl II-(145)4-benzylideneoxyphenyl II-(146)4-phenoxycarbonylphenyl II-(147)4-methoxyphenyl II-(148)4-anilinyl Phenyl II-(149)4-isobutyldecylaminophenyl II-(150)4-phenoxycarbonylaminophenyl II-(151)4-(3-ethylureido)phenyl II-( 152) 4-(3,3-Diethylureido)phenyl II-(153)4-phenoxyphenyl II-(154)4-hydroxyphenyl II-(155)3-butylphenyl II-(156)3-(2-Methoxy-2-ethoxyethyl)phenyl II-(157)3-(5-nonenyl)phenyl II-(158) m-biphenyl II-(159)3-ethoxycarbonylphenyl II-(160)3-butoxyphenyl II-(161)3-methylphenyl II-(162)3-chlorophenyl II-(163 ) 3-phenylphenylthio II-(1) 64) 3-Benzylmercaptophenyl II-(165)3-acetoxyphenyl II-(166)3-benzylideneoxyphenyl II-(167)3-phenoxycarbonylphenyl II-(168)3-methoxyphenyl II-(169)3-anilinophenyl II-(170)3-isobutyldecylaminophenyl II-(171)3-phenoxycarbonylaminobenzene Group II-(172)3-(3-ethylureido)phenyl II-(173)3-(3,3-diethylureido)phenyl II-(174)3-phenoxyphenyl II-(175)3-hydroxyphenyl II-(176)2-butylphenyl II-(177)2-(2-methoxy-2-ethoxyethyl)phenyl II-(178) 2-(5-decenyl)phenyl II-(179)o-biphenylyl-(180)2-ethoxycarbonylphenyl II-(181)2-butoxyphenyl-II-(182 2-methylphenyl II-(183)2-chlorophenyl II-(184)2-phenylphenylthio-II-(185)2-benzimidylphenyl II-(186)2-B Nonyloxyphenyl II-(187)2-benzylideneoxyphenyl II-(188)2-phenoxycarbonylphenyl II-(189)2-methoxyphenyl II-(190)2 -anilinophenyl II-(191)2-isobutyldecylaminophenyl II-(192)2-phenoxycarbonylaminophenyl II-(193)2-(3-ethylureido)phenyl II-( 194) 2-(3,3-Diethylureido)phenyl II-(195)2-phenoxyphenyl II-(196)2-hydroxyphenyl II-(197)3,4-dibutyl Phenylphenyl-(198)3,4-bis(2-methoxy-2-ethoxyethyl)phenyl II-(199)3,4-diphenylphenyl II-(200)3 ,4-diethoxycarbonylphenyl II-(201) 3,4-dodedodecyloxyphenyl II-(202)3,4-dimethylphenyl II-(203)3,4- Dichlorophenyl II-(204) 3,4-dibenzofurfurylphenyl II-(205) 3,4-diethoxymethoxyphenyl II-(206) 3,4-dimethoxybenzene Group II-(207)3,4-di-N-methylaminophenyl II-(208) 3,4-diisobutylaminophenyl phenyl II-(209) 3,4-diphenoxybenzene Group II-(210) 3,4-dihydroxyphenyl II-(211)3,5-dibutylphenyl II-(212)3,5-bis(2-methoxy-2-ethoxyl) Ethyl)phenyl II-(213)3,5-diphenylphenyl II-(214)3,5-diethoxycarbonylphenyl II-(215)3,5-didodecyloxy Phenyl II-(216)3,5-dimethylphenyl II-(217)3,5-dichlorophenyl II-(218)3,5-diphenylmercaptophenyl II-(219) 3,5-diethoxymethoxyphenyl II-(220)3,5-dimethoxyphenyl II-(221)3,5 Di-N-methylaminophenyl II-(222)3,5-diisobutylguanidinoaminophenyl II-(223)3,5-diphenoxyphenyl II-(224)3,5- Dihydroxyphenyl II-(225) 2,4-dibutylphenyl II-(226) 2,4-bis(2-methoxy-2-ethoxyethyl)phenyl II-(227) 2,4-diphenylphenyl II-(228) 2,4-diethoxycarbonylphenyl II-(229) 2,4-bisdodecyloxyphenyl II-(230) 2,4 -Dimethylphenyl II-(231) 2,4-dichlorophenyl II-(232) 2,4-diphenylmercaptophenyl II-(233) 2,4-diethoxy benzene Group II-(234) 2,4-dimethoxyphenyl II-(235) 2,4-di-N-methylaminophenyl II-(236) 2,4-diisobutylguanidinoaminobenzene Group II-(237) 2,4-diphenoxyphenyl II-(238) 2,4-dihydroxyphenyl II-(239) 2,3-dibutylphenyl II-(240) 2, 3-bis(2-methoxy-2-ethoxyethyl)phenyl II-(241) 2,3-diphenylphenyl II-(242) 2,3-diethoxycarbonylphenyl II-(243)2,3-bisdodecyloxyphenyl II-(244)2,3-dimethylphenyl II-(245)2,3-dichlorophenyl II-(246)2 ,3-diphenylmercaptophenyl II-(247) 2,3-diethyloxyphenyl II -(248)2,3-dimethoxyphenyl II-(249) 2,3-di-N-methylaminophenyl II-(250) 2,3-diisobutylaminophenyl phenyl -(251) 2,3-diphenoxyphenyl II-(252) 2,3-dihydroxyphenyl II-(253) 2,6-dibutylphenyl II-(254) 2,6- Bis(2-methoxy-2-ethoxyethyl)phenyl II-(255) 2,6-diphenylphenyl II-(256) 2,6-diethoxycarbonylphenyl II- (257) 2,6-Dia-dodecyloxyphenyl II-(258) 2,6-dimethylphenyl II-(259) 2,6-dichlorophenyl II-(260) 2,6 -Benzylmercaptophenyl II-(261) 2,6-diethoxymethoxyphenyl II-(262) 2,6-dimethoxyphenyl II-(263) 2,6-di- N-methylaminophenyl II-(264) 2,6-diisobutylaminophenyl phenyl II-(265) 2,6-diphenoxyphenyl II-(266) 2,6-dihydroxy Phenyl II-(267) 3,4,5-tributylphenyl II-(268)3,4,5-tris(2-methoxy-2-ethoxyethyl)phenyl II-( 269) 3,4,5-Triphenylphenyl II-(270) 3,4,5-triethoxycarbonylphenyl II-(271) 3,4,5-nondodecyloxyphenyl II-(272)3,4,5-trimethylphenyl II-(273)3,4,5-trichlorophenyl II-(274)3,4,5 Tritylmercaptophenyl II-(275)3,4,5-triethoxymethoxyphenyl II-(276)3,4,5-trimethoxyphenyl II-(277)3,4, 5-tri-N-methylaminophenyl II-(278) 3,4,5-triisobutylamylaminophenyl II-(279)3,4,5-triphenyloxyphenyl II-( 280) 3,4,5-trihydroxyphenyl II-(281) 2,4,6-tributylphenyl II-(282)2,4,6-tris(2-methoxy-2-ethyl Oxyethyl)phenyl II-(283) 2,4,6-triphenylphenyl II-(284) 2,4,6-triethoxycarbonylphenyl II-(285) 2,4, 6-Dodecyloxyphenyl II-(286) 2,4,6-trimethylphenyl II-(287) 2,4,6-trichlorophenyl II-(288) 2,4, 6-tritylmercaptophenyl II-(289) 2,4,6-triethoxymethoxyphenyl II-(290) 2,4,6-trimethoxyphenyl II-(291) 2, 4,6-tri-N-methylaminophenyl II-(292) 2,4,6-triisobutylamylaminophenyl II-(293) 2,4,6-triphenyloxyphenyl II -(294) 2,4,6-trihydroxyphenyl II-(295) pentafluorophenyl II-(296) pentachlorophenyl II-(297)pentamethoxyphenyl II-(298)6- N-methylamine sulfonyl-8-methoxy-2-naphthyl II-(299)5-N-methylamine sulfonyl-2-naphthyl II- (300) 6-N-Phenylaminesulfonyl-2-naphthyl II-(301)5-ethoxy-7-N-methylaminesulfonyl-2-naphthyl II-(302)3 -Methoxy-2-naphthyl II-(303)1-ethoxy-2-naphthalenyl-(304)6-N-phenylaminesulfonyl-8-methoxy-2-naphthyl II-(305)5-Methoxy-7-N-phenylaminesulfonyl-2-naphthyl II-(306)1-(4-methylphenyl)-2-naphthyl II-(307 6,8-Di-N-methylamine sulfonyl-2-naphthyl II-(308)6-N-2-ethenyloxyethylamine sulfonyl-8-methoxy-2- Naphthyl II-(309)5-acetoxy-7-N-phenylamine sulfonyl-2-naphthyl II-(310)3-benzylideneoxy-2-naphthyl II-(311 5-Ethylamino-1-naphthyl II-(312)2-methoxy-1-naphthalenyl-(313)4-phenoxy-1-naphthalenyl-II-(314)5- N-Methylamine sulfonyl-1-naphthyl II-(315)3-N-methylamine-methylmethyl-4-hydroxy-1-naphthalenyl-(316)5-methoxy-6- N-ethylaminesulfonyl-1-naphthyl II-(317)7-tetradecyloxy-1-naphthalenyl-(318)4-(4-methylphenoxy)-1-naphthalene Base II-(319)6-N Methylamine sulfonyl-1-naphthyl II-(320)3-N,N-dimethylamine-methylmethyl-4-methoxy-1-naphthyl II-(321)5-methoxy -6-N-benzylaminesulfonyl-1-naphthyl II-(322)3,6-di-N-phenylamine sulfonyl-1-naphthyl II-(323)methyl II- (324) Ethyl II-(325)butyl II-(326)octyl II-(327) dodecyl II-(328)2-butoxy-2-ethoxyethyl II-(329 Phenylmethyl-(330)4-methoxybenzyl

II-(331)methyl II-(332)phenyl II-(333) butyl

The compounds represented by the formula (III) are explained below.

In the above formula (III), R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or a substituent.

The substituent represented by each of R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ includes an alkyl group (preferably having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms). Particularly preferred is an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, and ring. a propyl group, a cyclopentyl group, a cyclohexyl group or the like; an alkenyl group (preferably having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, particularly preferably an alkenyl group having 2 to 20 carbon atoms) , for example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.; alkynyl (preferably having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms) An alkynyl group having 2 to 20 carbon atoms, such as propargyl group, 3-pentynyl group or the like; an aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms). Particularly preferred are aryl groups having 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, naphthyl, etc.; substituted or unsubstituted amine groups (preferably having 0 to 40 carbon atoms) More preferably, the number of carbon atoms is from 0 to 30, particularly preferably an amine group having from 0 to 20 carbon atoms, such as an unsubstituted amine. Base, methylamino group, dimethylamino group, diethylamino group, anilino group, etc.).

An alkoxy group (preferably having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, particularly preferably an alkoxy group having 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group, Butoxy or the like; an aryloxy group (preferably having 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, particularly preferably an aryloxy group having 6 to 20 carbon atoms, such as phenoxyl) Base, 2-naphthyloxy group, etc.; fluorenyl group (preferably having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, particularly preferably a fluorenyl group having 1 to 20 carbon atoms, for example Ethylene, benzylidene, methionyl, trimethylethenyl, etc.; alkoxycarbonyl (preferably having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms) An alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group or an ethoxycarbonyl group; and an aryloxycarbonyl group (preferably having 7 to 40 carbon atoms, more preferably a carbon number) It is preferably from 7 to 30, particularly preferably an aryloxycarbonyl group having 7 to 20 carbon atoms, such as a phenoxycarbonyl group; and a decyloxy group (preferably having 2 to 40 carbon atoms, more preferably a carbon atom). The number is 2 to 30, particularly preferably a fluorenyl group having 2 to 20 carbon atoms, such as an ethoxy group, benzene. Acyl group, etc.).

Amidino group (preferably having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, particularly preferably a fluorenylamino group having 2 to 20 carbon atoms, such as an ethylamino group or a benzyl group) An alkoxycarbonylamino group (preferably having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, particularly preferably an alkoxycarbonyl group having 2 to 20 carbon atoms) An amine group such as a methoxycarbonylamino group or the like; an aryloxycarbonylamino group (preferably having 7 to 40 carbon atoms, more preferably 7 to 30 carbon atoms, particularly preferably 7 carbon atoms). An aryloxycarbonylamino group to 20, such as a phenoxycarbonylamino group; a sulfonylamino group (preferably having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms), particularly preferably a sulfonylamino group having 1 to 20 carbon atoms, such as a methylsulfonylamino group, a benzenesulfonylamino group or the like; an aminesulfonyl group (preferably having a carbon number of 0 to 40, more preferably carbon) The number of atoms is from 0 to 30, particularly preferably a sulfonyl group having from 0 to 20 carbon atoms, such as an amine sulfonyl group, a methylamine sulfonyl group, a dimethylamine sulfonyl group, or a phenylamine sulfonyl group. Et.); an amine carbenyl group (preferably having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms) Particularly preferred is an amine carbenyl group having 1 to 20 carbon atoms, such as an unsubstituted amine methyl sulfonyl group, and a methylamine methyl fluorenyl group, a diethylamine methyl fluorenyl group, a phenylamine methyl fluorenyl group, etc.) .

An alkylthio group (preferably having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, particularly preferably 1 to 20 carbon atoms, such as a phenylthio group, etc.); a sulfonyl group (preferably) a carbon atom number of 1 to 40, more preferably 1 to 30 carbon atoms, particularly preferably a sulfonyl group having 1 to 20 carbon atoms, such as a methylsulfonyl group, a toluenesulfonyl group, etc.; Sulfhydryl (preferably having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, particularly preferably a sulfinyl group having 1 to 20 carbon atoms, such as sulfinyl group, phenylene Sulfhydryl group, etc.; ureido group (preferably having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, particularly preferably a ureido group having 1 to 20 carbon atoms, such as unsubstituted Urea group, methylurea group, phenylureido group, etc.; guanidinium phosphate group (preferably having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, particularly preferably 1 carbon atom) a guanamine group to 20, such as diethylphosphonium phosphinate, phenylphosphonium amide, etc.; a hydroxyl group, a thiol group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); Base, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfinic acid group, a (hetero group), an imido group; a heterocyclic group (preferably a heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12), for example, a hetero atom having a nitrogen atom, an oxygen atom, a sulfur atom or the like Heterocyclic group, such as imidazolyl, pyridyl, quinolyl, furyl, piperidinyl, morpholinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, 1,3,5-tri nitrogen a fluorenyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably a decyl group having 3 to 24 carbon atoms, such as trimethyldecyl group, Triphenyldecylalkyl, etc.). These substituents may be substituted for such substituents. Further, when the substituent has two or more, the same or different may be used. Also, if possible, they may be bonded to each other to form a ring.

a substituent represented by each of R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , preferably an alkyl group, an aryl group, a substituted or unsubstituted amino group, an alkoxy group, an alkylthio group Or a halogen atom.

Specific examples of the compound represented by the formula (III) are listed below, but are not limited thereto.

The compound represented by the formula (IV) will be described below.

In the above formula (IV), Q ⁷¹ represents a nitrogen-containing aromatic heterocyclic ring, and Q ⁷² represents an aromatic ring.

Further, in the formula (IV), Q ⁷¹ represents a nitrogen-containing aromatic heterocyclic ring, and preferably a nitrogen-containing aromatic heterocyclic ring of 5 to 7 members, more preferably a nitrogen-containing aromatic heterocyclic group of 5 to 6 members. Heterocyclic.

The nitrogen-containing aromatic heterocyclic ring is preferably, for example, an imidazole, a pyrazole, a triazole, a tetrazole, a thiazole, an oxazole, a selenazole, a benzotriazole, a benzothiazole, a benzoxazole, a benzoseazole, or a thiazide. Oxazole, oxadiazole, naphthylthiazole, naphthoxazole, phthalimidazole, hydrazine, pyridine, pyridyl Pyrimidine Trinitrogen Each of the rings of Sancha, Siqi, etc., more preferably trinitrogen And a nitrogen-containing aromatic heterocyclic ring of 5 members; specifically, preferably 1,3,5-trinitrogen , imidazole, pyrazole, triazole, tetrazole, thiazole, oxazole, benzotriazole, benzothiazole, benzoxazole, thiadiazole, oxadiazole, etc., especially preferably 1,3, 5-trinitrogen Ring and benzotriazole ring.

The nitrogen-containing aromatic heterocyclic ring represented by Q ⁷¹ may have a substituent which is applicable to the substituent T as described later. Further, when the substituent has a plurality of substituents, each of the substituents may be condensed to form a ring.

The Q ⁷² series represents an aromatic ring. The aromatic ring system represented by Q ⁷² may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Also, these may be monocyclic or form a condensed ring with other rings. The aromatic hydrocarbon ring is preferably a monocyclic or bicyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms (e.g., a benzene ring, a naphthalene ring, etc.), more preferably an aromatic hydrocarbon ring having 6 to 20 carbon atoms. Further, it is more preferably an aromatic hydrocarbon ring having 6 to 12 carbon atoms, particularly preferably a benzene ring.

The aromatic heterocyclic ring is preferably an aromatic heterocyclic ring containing a nitrogen atom or a sulfur atom. Specific examples of the heterocyclic ring include, for example, thiophene, imidazole, pyrazole, pyridine, pyridyl ,despair Triazole, trinitrogen , hydrazine, carbazole, hydrazine, thiazoline, thiazole, thiadiazole, oxazolyl, oxazole, oxadiazole, quinoline, isoquinoline, hydrazine , naphthyridine, quinoxaline, quinazoline, Cinnoline, acridine, acridine, morphine, brown , tetrazole, benzimidazole, benzoxazole, benzothiazole, benzotriazole, tetraterpene and the like. The aromatic heterocyclic ring is preferably pyridine or trinitrogen ,quinoline.

The aromatic ring represented by Q ⁷² is preferably an aromatic hydrocarbon ring, more preferably a naphthalene ring or a benzene ring, and particularly preferably a benzene ring. The Q ⁷² group may further have a substituent, which is preferably a substituent T as described below.

The "substituent T" includes, for example, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as methyl group, ethyl group, isopropyl group, or tertiary group). -butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.); alkenyl (preferably having 2 to 20 carbon atoms, more preferably It is 2 to 12, particularly preferably 2 to 8, such as a vinyl group, an allyl group, a 2-butenyl group, a 3-pentenyl group or the like; an alkynyl group (preferably having 2 to 20 carbon atoms, more preferably It is 2 to 12, particularly preferably 2 to 8, such as propargyl, 3-pentynyl, etc.; aryl (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6) Up to 12, for example, phenyl, biphenylyl, naphthyl, etc.; an amine group (preferably having a carbon number of 0 to 20, more preferably 0 to 10, particularly preferably 0 to 6, such as an amine group or a methyl group) Amino group, dimethylamino group, diethylamino group, benzhydrylamino group, etc.; alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1) Up to 8, for example, a methoxy group, an ethoxy group, a butoxy group or the like; an aryloxy group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, for example, An oxy group, a 2-naphthyloxy group, or the like; a fluorenyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, particularly preferably 1 to 12, such as an ethyl fluorenyl group, a benzamidine group, or a group) Anthracenyl, trimethylethenyl, etc.; alkoxycarbonyl (preferably having 2 to 20 carbon atoms, more preferably 2 to 16, particularly preferably 2 to 12, such as methoxycarbonyl, ethoxy) An aryloxycarbonyl group (preferably having a carbon number of 7 to 20, more preferably 7 to 16, particularly preferably 7 to 10, such as a phenoxycarbonyl group, etc.); a decyloxy group (preferably The number of carbon atoms is from 2 to 20, more preferably from 2 to 16, particularly preferably from 2 to 10, such as acetoxy, benzhydryloxy, and the like.

Further, as the substituent T as described above, the other includes: an amidino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as an ethyl fluorenylamino group or a benzene group). Alkylaminocarbonyl, etc.; alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16, particularly preferably 2 to 12, such as methoxycarbonylamino group, etc.); An oxycarbonylamino group (preferably having a carbon number of 7 to 20, more preferably 7 to 16, particularly preferably 7 to 12, such as a phenoxycarbonylamino group, etc.); a sulfonylamino group (preferably carbon) The number of atoms is from 1 to 20, more preferably from 1 to 16, particularly preferably from 1 to 12, such as a methylsulfonylamino group, a benzenesulfonylamino group, etc.; an aminesulfonyl group (preferably having a carbon number of 0 to 20, more preferably 0 to 16, particularly preferably 0 to 12, such as amidoxime, methylamine sulfonyl, dimethylamine sulfonyl, phenylamine sulfonyl, etc.; Sulfhydryl (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, particularly preferably 1 to 12), such as an amine methyl sulfhydryl group, a methyl amine methyl fluorenyl group, a diethyl amine fluorenyl group, and a benzene group. Alkylthio group, etc.; alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, particularly preferably 1 to 12, such as methyl sulfide) , ethylthio group, etc.; arylthio group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16, particularly preferably 6 to 12, such as phenylthio group, etc.); sulfonyl group (preferably The number of carbon atoms is from 1 to 20, more preferably from 1 to 16, particularly preferably from 1 to 12, such as methylsulfonyl, toluenesulfonyl, etc.); sulfinyl group (preferably having 1 to 1 carbon atom) 20, more preferably 1 to 16, particularly preferably 1 to 12, such as sulfinyl, phenylsulfinyl, etc.; urea group (preferably having 1 to 20 carbon atoms, more preferably 1 to 2) 16, particularly preferably from 1 to 12, such as ureido, methylureido, phenylureido, etc.; guanidinium phosphate (preferably having from 1 to 20 carbon atoms, more preferably from 1 to 16, particularly preferred) It is 1 to 12, for example, diethylphosphonium amide, phenylphosphonium amide, etc.).

Further, as the substituent T as described above, the others include: a hydroxyl group, a hydrogenthio group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.); a cyano group, a sulfo group, a carboxyl group, a nitro group, and an oxygen group. a decanoic acid group, a sulfinic acid group, a hydrazino group (fluorenyl group), an imido group; a heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and a hetero atom such as a nitrogen atom) The oxygen atom or the sulfur atom, specifically, includes, for example, an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a piperidinyl group, a morpholinyl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group. And decyl) (preferably, the number of carbon atoms is from 3 to 40, more preferably from 3 to 30, particularly preferably from 3 to 24, such as trimethyldecyl, triphenyldecyl, etc.).

These substituents can be substituted. Further, when there are two or more substituent groups, they may be the same or different. Also, if possible, they may be bonded to each other to form a ring.

Specific examples of the compound represented by the general formula (IV) are listed below, but the present invention is not limited to the specific examples shown below.

The compounds represented by the general formula (V) are explained below.

However, in the general formula (V), Q ⁸¹ and Q ⁸² each independently represent an aromatic ring, and X ⁸¹ represents NR ⁸¹ (the R ⁸¹ represents a hydrogen atom or a substituent), and represents an oxygen atom or a sulfur atom.

The aromatic hydrocarbon ring represented by Q ⁸¹ and Q ⁸² is preferably a monocyclic or bicyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms (e.g., a benzene ring, a naphthalene ring, etc.), preferably a carbon atom. The number of aromatic hydrocarbon rings of 6 to 20 is more preferably an aromatic hydrocarbon ring having 6 to 12 carbon atoms, particularly preferably a benzene ring.

The aromatic heterocyclic ring represented by Q ⁸¹ and Q ⁸² preferably contains at least one of an oxygen atom, a nitrogen atom or a sulfur atom. Specific examples of the aromatic heterocyclic ring include, for example, furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyridyl ,despair Triazole, trinitrogen , hydrazine, carbazole, hydrazine, thiazoline, thiazole, thiadiazole, oxazolyl, oxazole, oxadiazole, quinoline, isoquinoline, hydrazine , naphthyridine, quinoxaline, quinazoline, Porphyrin, acridine, acridine, morphine, brown Each of the rings of tetrazole, benzimidazole, benzoxazole, benzothiazole, benzotriazole, tetraterpene, and the like. The aromatic heterocyclic ring is preferably a pyridine ring or a trinitrogen Ring, quinoline ring.

The aromatic group represented by Q ⁸¹ and Q ⁸² is preferably an aromatic hydrocarbon ring, more preferably an aromatic hydrocarbon ring having 6 to 10 carbon atoms, a substituted or unsubstituted benzene ring.

The Q ⁸¹ and Q ⁸² groups may have a substituent, and although the substituent is preferably the substituent T as described above, the substituent does not contain a carboxylic acid or a sulfonic acid or a quaternary ammonium salt. Further, if possible, the substituents may be bonded to each other to form a ring structure.

X ⁸¹ represents NR ⁸¹ (R ⁸¹ represents a hydrogen atom or a substituent, and the substituent may be a substituent T as described above), an oxygen atom or a sulfur atom. X ^{81 is} preferably NR ⁸¹ (R ^{81 is} preferably a fluorenyl group, a sulfonyl group, and the substituents may be substituted) or an oxygen atom, more preferably an oxygen atom.

Specific examples of the compound represented by the general formula (V) are listed below, but the present invention is not limited to the specific examples shown below.

The Rth rising agent used in the present invention is preferably a compound represented by the general formulae (II) and (III). Further, it is also suitable to use a compound represented by the formula (IV) in a mixture of the compounds represented by the general formulae (II) and (III).

The amount of the Rth-increasing agent (the compound represented by the general formulae (II) to (IV)) used in the present invention is preferably 2.0 to 30% by mass, more preferably 2.0% by mass to the base polymer of the film. 2.5 to 20% by mass, and further more preferably 2.5 to 10% by mass. When two or more types are used, the total amount thereof is preferably a condition that satisfies the range of the added amount.

The Rth rising agent used in the present invention preferably exhibits liquid crystallinity. More preferably, liquid crystallinity (having thermotropic liquid crystallinity) is exhibited by heating, and liquid crystallinity is preferably exhibited in a temperature range of 100 to 300 °C. The liquid crystal phase is preferably a columnar phase, a nematic phase, or a smectic phase, more preferably a columnar phase.

The compound of the formula (I) and the Rth rising agent as described above may be added simultaneously to dissolve the substrate polymer of the film, or may be added to the coating liquid after dissolution. In particular, it is preferable to use a static mixer or the like and to add the ultraviolet absorber solution to the coating liquid immediately before casting, since the spectral absorption characteristics can be easily adjusted.

[Controlling the retardation riser of Re]

When it is desired to control the absolute value of Re of the protective film (optical compensation film) of the present invention, it is preferred that the compound having a maximum absorption wavelength (λ _max ) in the ultraviolet absorption spectrum of the solution is shorter than 250 nm as a hysteresis rise. Agent.

By using a compound as described above, the absolute value can be controlled without substantial changes in the Re wavelength dependence of the visible domain.

Further, from the viewpoint of the function of the hysteresis-increasing agent, it is preferably a rod-like compound, and preferably has at least one aromatic ring, and more preferably has at least two aromatic rings.

The rod-like compound preferably has a linear molecular structure. The so-called "linear molecular structure" means the most thermodynamically stable structure, and the molecular structure of the rod-like compound is linear.

In addition, the thermodynamically most stable structure can be obtained by crystal structure analysis or molecular orbital calculation.

For example, using a molecular orbital calculation software (for example, WinMOPAC2000: manufactured by Fujitsu (FUJITSU) Co., Ltd.) for molecular orbital calculation, it is calculated that the heat of formation of a compound becomes the smallest molecular structure.

Here, the molecular structure is linear, which means that the thermodynamically most stable structure obtained by the calculation as described above has an angle of 140° or more.

Further, the amount of the retardation-increasing agent added is preferably from 0.1 to 30% by mass, more preferably from 0.5 to 20% by mass, based on the total solid content of the polymer.

[Humidity Dependence Improver]

In the transparent support of the present invention, it is preferable to use a humidity dependency improver for the additive for reducing the variation of Re and Rth caused by the change in the environmental humidity.

The humidity-dependent improver is preferably a compound having at least a plurality of hydrogen-bonding groups in one molecule, and more preferably the hydrogen-bonding group is selected from a hydroxyl group, an amine group, a thiol group, and a carboxylic acid group. Particularly preferred is a group selected from a hydroxyl group and a carboxylic acid group.

Further, it is preferred to have a plurality of different functional groups in one molecule.

The humidity dependency improver as described above preferably has one or two aromatic rings, and preferably the number of the functional groups contained in one molecule, divided by the molecular weight of the additive. The value obtained is 0.01 or more.

These features are presumed to be bonded (hydrogen bonding) to the hydrogen bonding site of the deuterated cellulose resin by the humidity dependency modifier as described above to offset the alignment of water molecules in the deuterated cellulose resin. And the hysteresis change of the charge distribution change of the deuterated cellulose due to the desorption of water molecules acts.

Specific examples of the humidity dependency improver may be the compounds (A-1) to (A-17) shown below, but are not limited thereto.

Further, the molecular weight modifier has a molecular weight of preferably 130 or more and 500 or less. When the molecular weight is less than 130, the volatility is insufficient, and when it is 500 or more, the solubility in a solvent and the compatibility with the deuterated cellulose resin are deteriorated.

Specific examples of the humidity-dependent improver which can satisfy the conditions as described above include compounds (A-18) to (A-42) shown below, but are not limited thereto.

<Application to optical compensation film>

Next, the optical compensation film for realizing optical compensation will be specifically described below.

The optical compensation film of the present invention contributes to the expansion of the liquid crystal display device, particularly the viewing angle contrast of the OCB mode, the VA mode liquid crystal display device, and the reduction of the color shift depending on the viewing angle.

The optical compensation film of the present invention may be disposed between the polarizing plate on the observer side and the liquid crystal cell, between the polarizing plate on the back side and the liquid crystal cell, or both.

For example, it may be incorporated as a separate member in the liquid crystal display device, or an optical property may be imparted to the protective film for protecting the polarizing film so that it can also function as a transparent film, and one of the polarizing plates can be used. The member is assembled inside the liquid crystal display device.

Further, the optical compensation film of the present invention may have at least two layers of a transparent support and an optically anisotropic layer having other optical characteristics.

[optical anisotropic layer (mixed alignment anisotropic layer)]

The optical compensation film of the present invention has at least one optically anisotropic layer formed of a liquid crystal compound depending on the liquid crystal method of the object. The optically anisotropic layer may be formed directly on the surface of the optical compensation film or form an alignment film on the optical compensation film and then formed on the alignment film.

Further, the liquid crystalline compound layer formed on another substrate may be transferred onto an optical compensation film by using an adhesive or an adhesive to produce an optical compensation film having an optically anisotropic layer.

The liquid crystalline compound for forming the optically anisotropic layer as described above includes a rod-like liquid crystal compound and a discotic liquid crystalline compound (hereinafter, a discotic liquid crystalline compound is also referred to as a "disc liquid crystal compound"). The situation). The rod-like liquid crystal compound and the discotic liquid crystal compound may be a polymer liquid crystal or a low molecular liquid crystal. Further, finally, the compound contained in the optically anisotropic layer does not need to exhibit liquid crystallinity. For example, when the optically anisotropic layer is produced by using a low molecular liquid crystalline compound, it may be optically different. In the course of the directional layer, the compound is subjected to crosslinking and no longer exhibits a pattern of liquid crystallinity.

[rod liquid crystalline compound]

The "rod-like liquid crystalline compound" which can be used in the optically anisotropic layer of the present invention is suitably used: azomethine, azobenzene, cyanide, cyanophenyl ester Classes, benzoates, phenylcyclohexanecarboxylates, cyanophenylcyclohexanes, cyano substituted phenylpyrimidines, alkoxy substituted phenylpyrimidines, phenyldioxane Classes, toluenes and alkenylcyclohexylbenzonitriles.

Further, the rod-like liquid crystalline compound also includes a metal complex. Further, a liquid crystal polymer containing a rod-like liquid crystal compound in the repeating unit can also be used. In other words, the rod-like liquid crystalline compound may be bonded to the (liquid crystal) polymer.

The rod-like liquid crystal compound is disclosed in Chapter 4, Chapter 7, and Chapter 11 of the "Liquid Crystal Chemistry" (edited by the Chemical Society of Japan, 1994), and the Handbook of Liquid Crystal Devices (Japanese Academic Revitalization) Chapter 3 of the 142th Committee.

The birefringence of the rod-like liquid crystal compound used in the present invention is preferably in the range of 0.001 to 0.7.

The rod-like liquid crystalline compound as described above preferably has a polymerizable group in order to fix its alignment state. The polymerizable group is preferably an unsaturated polymerizable group or an epoxy group, more preferably an unsaturated polymerizable group, and still more preferably an ethylenically unsaturated polymerizable group.

[Disc liquid crystal compound]

Discotic liquid crystal compounds include: benzene derivatives disclosed in C. Destrade et al., Mol. Cryst., Vol. 71, p. 111 (1981); disclosed in C. Destrade et al. Research Report, Mol. Cryst., Vol. 122, p. 141 (1985), Physics Lett, A, Vol. 78, p. 82 (1990) Toluxene derivatives; disclosed in B. Kohn et al. Research Report, Angew. Chem., Vol. 96, p. 70 (1984), Cyclohexane Derivatives; and J. Chem. Commun., 1794 (1985) J. Zhang et al., J. Am. Chem. Soc., Vol. 116, p. 2655 (1994) Nitrogen crown ethers and phenylacetylene macrocycles.

The discotic liquid crystalline compound as described above also includes a linear structure in which a linear alkyl group, an alkoxy group or a substituted benzamidine group is used as a side chain of a mother nucleus for a core of a molecular center, and is substituted with a radial structure. And a compound which exhibits liquid crystallinity. The aggregate of molecules or molecules is preferably a compound having rotational symmetry and capable of imparting a certain alignment.

As described above, when the optically anisotropic layer is formed of a liquid crystal compound, the compound contained in the optically anisotropic layer does not need to exhibit liquid crystallinity, for example, a low molecular disk-like liquid crystalline compound. A compound which is contained in an optically anisotropic layer when the reaction is carried out by heat or light, and the reaction is carried out by heat or light, and the optically anisotropic layer or the like is formed by polymerization or crosslinking. It is also possible to lose liquid crystallinity. A preferred example of the dish-like liquid crystal compound is disclosed in Japanese Laid-Open Patent Publication No. 8-50206. Further, the polymerization of the discotic liquid crystal compound is disclosed in Japanese Laid-Open Patent Publication No. Hei 8-27284.

When it is desired to fix a discotic liquid crystalline compound by polymerization, it is necessary to bond a polymerizable group as a substituent to a disc-shaped core of a discotic liquid crystalline compound. However, when the polymerizable group is directly bonded to the disk-shaped core, it is difficult to maintain the alignment state during the polymerization reaction. Therefore, it is preferred to introduce a linking group between the disc-shaped core and the polymerizable group.

In the optically anisotropic layer as described above in the present invention, the rod-like compound or the molecular system of the discotic compound is fixed in an aligned state. The angle of intersection of the molecular symmetry axis of the liquid crystal compound at the optical compensation film side interface and the retardation axis of the optical compensation film in the plane of the optical compensation film is approximately 45°. Further, "substantially 45°" as used herein means an angle in the range of 45 ± 5°, and preferably 42 to 48°, more preferably 43 to 47°.

The molecular symmetry axis of the liquid crystal compound is aligned in the average direction, and can be generally adjusted by selecting a liquid crystal compound or an alignment film material or selecting a rubbing treatment method.

In the present invention, for example, in the case of manufacturing an optical compensation film for an OCB mode, an alignment film for forming an optical anisotropic layer is formed by a rubbing treatment, and a 45° phase is formed for the retardation axis of the optical compensation film. In the direction in which the rubbing treatment is applied, the molecular symmetry axis of the liquid crystal compound can be formed at least at an orientation average direction of the interface of the bismuth cellulose film, which is an optically anisotropic layer of 45° with respect to the retardation axis of the cellulose fluorite film.

For example, when the optical compensation film of the present invention has a long-length optical compensation film of the present invention having a longitudinal axis orthogonal to the longitudinal direction, it can be produced in a continuous manner.

The plasticizer, the surfactant, and the polymerizable monomer which are used together with the liquid crystal compound are preferably compatible with the discotic liquid crystalline compound, and can impart a change in the tilt angle of the liquid crystal compound or prevent the alignment. A polymerizable monomer (for example, a compound having a vinyl group, a vinyloxy group, an acryloyl group, and a methacryl group) is preferred. The amount of the compound to be added is generally in the range of 1 to 50% by mass, preferably 5 to 30% by mass based on the liquid crystalline compound. In addition, when a monomer having a polymerizable reactive functional group of 4 or more is used, the adhesion between the alignment film and the optically anisotropic layer can be improved.

When a liquid crystalline compound is used as the liquid crystalline compound, it is preferred to use a polymer having a certain degree of compatibility with the liquid crystalline compound and capable of imparting a change in the tilt angle to the liquid crystalline compound.

Examples of the polymer include cellulose esters. The amount of the polymer added is preferably in the range of 0.1 to 10% by mass, more preferably in the range of 0.1 to 8% by mass, and still more preferably 0.1 to 5% by mass based on the discotic liquid crystalline compound. The range is such that it does not hinder the alignment of the discotic liquid crystalline compound.

The dish-like liquid crystal phase-solid phase transfer temperature of the discotic liquid crystalline compound is preferably from 70 to 300 ° C, more preferably from 70 to 170 ° C.

In the present invention, the "other" optically anisotropic layer as described above has at least in-plane optical anisotropy. The in-plane retardation Re of the optically anisotropic layer is preferably from 3 to 300 nm, more preferably from 5 to 200 nm, and still more preferably from 10 to 100 nm. The retardation Rth in the thickness direction of the optically anisotropic layer is preferably from 20 to 400 nm, more preferably from 50 to 200 nm. Further, the thickness of the optically anisotropic layer is preferably from 0.1 to 20 μm, more preferably from 0.5 to 15 μm, and still more preferably from 1 to 10 μm.

[alignment film]

The optical compensation film of the present invention may have an alignment film between the support and the optically anisotropic layer. Alternatively, the alignment film may be used only in the production of the optically anisotropic layer, and then the optically anisotropic layer may be transferred to the optical compensation film (support) of the present invention after the optically anisotropic layer is formed on the alignment film. )on.

In the present invention, the alignment film is preferably a layer composed of a crosslinked polymer. The polymer used for the alignment film may be either a crosslinkable polymer itself or a polymer which can be crosslinked by using a crosslinking agent. The alignment film can be formed by reacting a polymer having a functional group or a functional group into a polymer to cause a reaction between the polymers by light, heat, or pH change; or using a high reaction. A method in which a crosslinking agent of an active compound is introduced between a polymer and a binder derived from a crosslinking agent to form a crosslink between the polymers.

The alignment film composed of the crosslinked polymer is usually formed by applying a coating liquid containing a polymer as described above or a mixture of a polymer and a crosslinking agent to a support, followed by heating or the like.

In the rubbing step described below, it is preferred to increase the degree of crosslinking in advance to suppress dust flying of the alignment film. When the amount (Mb) of the crosslinking agent added to the coating liquid relative to the amount of the crosslinking agent (Mb) added to the coating liquid is subtracted from the value (Ma/Mb) (1-(Ma/Mb) When the degree of crosslinking is defined as the degree of crosslinking, the degree of crosslinking is preferably from 50 to 100%, more preferably from 65 to 100%, and still more preferably from 75 to 100%.

(polarizer)

The polarizing plate of the present invention comprises a polarizing film and a protective film for polarizing plates for sandwiching one of the polarizing films. When it has such a structure, it is preferable from a viewpoint of a polarizing energy and a transmittance. The optical compensation film as described above includes a protective film for a polarizing plate on at least one side of the pair of protective films for a polarizing plate. In the method for producing the polarizing plate, for example, the optical compensation film may be bonded to the polarizing film after being cut into a desired shape such as a rectangular shape, or may be bonded to the long-length polarizing film. Cut into the desired shape.

The polarizing plate of the present invention not only has a polarizing function but also has an excellent optical compensation function, and can be easily matched with a liquid crystal display device. Further, the embodiment in which the optical compensation film is used as a protective film for a polarizing film contributes to a reduction in thickness of the liquid crystal display device.

<cover layer>

The protective film for a polarizing plate of the present invention is particularly preferably used as a protective film disposed on the side of the polarizing film, and a coating layer (barrier layer) is preferably formed on the transparent substrate film. The thickness of the coating layer differs depending on the type of the coating layer. When the coating layer is set to have the most appropriate thickness, it is preferable because it has excellent low moisture permeability and does not cause the occurrence of curling or the like. If the curl is too large, the polarizing plate step is followed, for example, in the subsequent step with the polarizing film, an obstacle is about to occur in the processing. In addition, not only the manufacturing process, but also if the polarizing plate itself has curl remaining, display unevenness or the like is caused to the LCD, which is not preferable. Therefore, it is preferable to control the film thickness of the coating layer to be within an optimum range if it is desired to cause curling or to suppress it to an extent that is practically not problematic. As for the lower limit of the film thickness, the preferred range is determined in accordance with the moisture permeability. The coating layer is composed of at least one layer, but a pattern of two or more layers is also possible. A mode in which two or more different coating layers are used simultaneously in the coating layer is particularly preferable from the viewpoint of reducing moisture permeability.

<Hylet permeability>

Next, the moisture permeability is described in detail below.

The method for measuring the moisture permeability can be applied to the "Physical Properties of Polymers II" (Polymer Experiment Lecture 4, Co-published), pages 285 to 294: Determination of vapor permeation (mass method, thermometer method, vapor pressure method) According to the method of JS Z-0208, the 70 mm enamel sample of the present invention is conditioned for 24 hours under the conditions of 60 ° C and 95% RH, and the quality difference before and after the humidity control is calculated according to JIS Z-0208. The amount of water per unit area (g/m ² ) is obtained. At this time, the operation of taking out and weighing the cup placed in the constant temperature and humidity apparatus at appropriate intervals is repeated, and the mass increase per unit time is calculated by two consecutive weighings, and the continuous operation is continued. Until it is within 5% and becomes certain. Further, in order to eliminate the influence of moisture absorption of the sample or the like, an empty cup to which the moisture absorbent has not been placed is measured to correct the value of the moisture permeability.

In addition, when the value of the moisture permeability used in the present invention is measured as a protective film having a coating layer in which a layered inorganic compound is dispersed in a polyvinyl alcohol, an ethylene-vinyl alcohol copolymer, and the resin layer, Then, the value of the moisture permeability from the side of the substrate layer is used. The moisture permeability of the commercially available cellulose acetate film measured by this measurement is generally 80 μm thick, and the moisture permeability under the conditions as described above is 1,400 to 1,500 g/m ² . Day. The upper limit of the moisture permeability of the polarizing plate protective film of the present invention is preferably 300 g/m ² . Below day, more preferably 200 g/m ² . Below day. If the moisture permeability is higher than the upper limit value, the effect of reducing display image unevenness is low when used for a long period of time. The display image unevenness is a change in the size of the polarizing film due to a change in temperature or humidity. Although the lower limit is not particularly limited, it is preferably 20 g/m ² from the viewpoint of productivity in processing of the polarizing plate. Above day, more preferably 30 g/m ² . More than day. If it is within this range, it can suppress the polarizing film caused by the change of temperature or humidity during long-term use without deteriorating the performance (polarization, single-plate transmittance) of the polarizing plate. Display image non-uniformity caused by dimensional changes.

Further, the constitution of the present invention can significantly reduce the display performance (angle of view contrast/hue viewing angle dependence) of the liquid crystal display device depending on the use environment by using the protective film as described above. Although it has been mentioned above that the deuterated cellulose film is made to contain water, a hysteresis change in the charge distribution change of the deuterated cellulose due to the alignment in the deuterated cellulose resin and the desorption of water molecules will occur. . As a result, the liquid crystal display device generates a contrast and a hue which are particularly oblique in accordance with the environmental humidity. It can be retarded by using a protective film to which a barrier layer is applied as a protective film for a polarizer. Since the water molecules are prevented from intruding into the deuterated cellulose disposed on the opposite side through the polarizing plate, the change in optical characteristics of the deuterated cellulose corresponding to the humidity can be suppressed, and as a result, the humidity dependence of the display characteristics of the liquid crystal display device can be obtained. cut back.

The hardened coating layer may be composed of a single layer or a plurality of layers, but is preferably a simple single layer in the production steps. In this case, the single layer refers to a coating layer formed of the same composition, and if the composition after coating and drying is the same composition, it may be formed by coating several times. As for the so-called number layer, it is formed by several compositions having different compositions.

<Adhesive>

The adhesive agent for the polarizing film and the protective film is not particularly limited, but includes a PVA resin (modified PVA containing an ethyl acetonitrile group, a sulfonic acid group, a carboxyl group, a hydroxyl alkyl group, etc.) or an aqueous solution of a boron compound. Among them, a PVA resin is preferred. The thickness of the subsequent layer is preferably from 0.01 to 10 μm, particularly preferably from 0.05 to 5 μm after drying.

<Consistent Manufacturing Steps of Polarizing Film and Transparent Protective Film>

The polarizing plate to be used in the present invention may have a drying step of shrinking to reduce the volatile content after stretching the film for a polarizing film, but it is preferred to apply a transparent protective film at least on one side after drying or drying. After that, there is a post heating step.

In the mode in which the transparent protective film also serves as an optically anisotropic layer support having a function of a transparent film, it is preferable to apply a transparent protective film on one surface and a transparent support having an optical anisotropic layer on the other surface. After the body, a post-heating step is performed.

<Performance of polarizing plate>

The optical properties and durability (storage in the short-term and long-term) of the polarizing plate composed of the transparent protective film, the polarizer (polarizing film), and the transparent support relating to the present invention are preferably commercially available. Ultra-high contrast products (for example, HLC2-5618 manufactured by SANRITZ Co., Ltd.) are equal to the above performance.

Specifically, the visible light transmittance is 42.5% or more, and the degree of polarization is {(Tp-Tc) / (Tp + Tc)} ^1/2 ≧ 0.9995 (however, Tp is parallel transmittance, Tc is orthogonal transmittance), When the temperature is 60 ° C and the humidity is 90% RH for 500 hours, and at 80 ° C for 500 hours in a dry environment, the rate of change of the light transmittance before and after the film is preferably 3% based on the absolute value. Hereinafter, it is more preferably 1% or less. Further, the rate of change in the degree of polarization is preferably 1% or less, and more preferably 0.1% or less, based on the absolute value.

(liquid crystal display device)

The polarizing plate obtained by bonding the optical compensation film as described above or the optical compensation film and the polarizing film can be advantageously used for a liquid crystal display device, particularly a transmissive liquid crystal display device. The transmissive liquid crystal display device is composed of a liquid crystal cell and two polarizing plates disposed on both sides thereof.

Further, the polarizing plate is composed of a polarizing film and at least two transparent protective films disposed on both sides of the polarizing film. Further, the liquid crystal cell system as described above sandwiches the liquid crystal between the two electrode substrates.

In the optical compensation film of the present invention, one piece is disposed between the liquid crystal cell and one side of the polarizing plate, or two pieces are disposed between the liquid crystal cell and the polarizing plate.

The polarizing plate of the present invention is used as at least one of two polarizing plates disposed on both sides of a liquid crystal cell. In this case, the polarizing plate of the present invention should be configured such that its optical compensation film is located on the liquid crystal cell side.

The liquid crystal cell is preferably a VA mode, an OCB mode, an IPS mode, or a TN mode.

<VA mode>

In the VA mode liquid crystal cell, when no voltage is applied, the rod-like liquid crystal molecules are substantially aligned vertically.

The liquid crystal cell system of the VA mode includes: in addition to (1) a liquid crystal cell of a VA mode in which a rod-like liquid crystal molecule is substantially vertically aligned when no voltage is applied, and a substantially horizontal alignment is applied when a voltage is applied (disclosed in Japan) In addition to (2) a liquid crystal cell (MVA mode) for multi-domain VA mode for expanding the viewing angle (disclosed in SID 97, Digest of Tech. Papers ( (Preface) 28 (1997), p. 845); (3) The rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied, and the mode of twisting the multi-domain alignment when voltage is applied (n- ASM mode) liquid crystal cells (disclosed in the Japanese Liquid Crystal Symposium, Proceedings 58 to 59 (1998)); and (4) SURVAIVAL mode liquid crystal cells (published in LCD INTERNATIONAL 98).

<OCB mode>

The liquid crystal cell of the OCB mode is a liquid crystal cell in which the rod-like liquid crystal molecules are aligned in the opposite direction (symmetry) of the liquid crystal cell in the opposite direction (symmetry).

A liquid crystal display device using a curved alignment mode liquid crystal cell is disclosed in each specification of U.S. Patent No. 4,583,825 and U.S. Patent No. 5,410,422. Since the rod-like liquid crystal molecule system symmetrically aligns the upper portion and the lower portion of the liquid crystal cell, the liquid crystal cell in the curved alignment mode has a self-optical compensation function.

Therefore, this liquid crystal mode is also referred to as an OCB (Optically Compensatory Bend) liquid crystal mode. The liquid crystal display device in the curved alignment mode has the advantage of a fast response speed.

<IPS mode>

In the liquid crystal cell of the IPS mode, the rod-like liquid crystal molecules are substantially aligned parallel to the substrate, and the liquid crystal molecules are to respond in a planar manner by applying an electric field parallel to the substrate surface. The IPS mode is black when no electric field is applied, and the transmission axes of the upper and lower polarizing plates are orthogonal. A method of using an optical compensation film to reduce light leakage in an oblique black display to improve a viewing angle, which is disclosed in Japanese Laid-Open Patent Publication No. Hei 10-54982, Japanese Patent Application Laid-Open No. Hei No. 11-202323, Japanese Laid-Open Patent Publication No. Hei 9-292522, Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei.

<TN mode>

In the liquid crystal cell of the TN mode, the rod-like liquid crystalline molecules are substantially horizontally aligned when no voltage is applied, and are twist-aligned at 60 to 120°.

The liquid crystal cell of the TN mode is most utilized as a color TFT liquid crystal display device, and has been disclosed in many documents.

According to the present invention, it is possible to provide an optical compensation film which can reduce coloring in the viewing angle direction by an optical compensation film which is not only front side but also strictly in the oblique direction, in particular, VA, IPS and OCB modes. An optical compensation film for use, and a polarizing plate using the same.

In addition, according to the present invention, it is possible to provide a liquid crystal display device capable of reducing coloring in the viewing angle direction by performing optical compensation in an oblique direction not only on the front side but also in the VA, IPS, and OCB modes. Device.

"Embodiment"

Hereinafter, the embodiments of the present invention will be described, but the present invention is not limited to the embodiments.

[Example 1] <Manufacture of Optical Compensation Film> <Manufacturing of Transparent Support>

The composition shown below was placed in a mixing tank, and while stirring, the components were dissolved while heating to prepare a cellulose triacetate (triethylenesulfonyl cellulose: TAC) solution.

Further, the maximum absorption wavelength λ _max measured for the compound of the structural formula (A) shown below is shown in Table 3.

(material. solvent composition)

The prepared solution (coating liquid) was cast using a casting machine having a belt having a width of 2 m and a length of 65 m. After the film surface temperature of the belt was 40 ° C, it was dried for 1 minute, and then peeled off, and then dried at 140 ° C for 30 minutes in a dry air to produce a film. At this time, the average drying speed at a solvent volatile content of 20% in the film was 1.5% by mass/min. Thereafter, the film was subjected to a uniaxial extension of 140% at a temperature of 190 ° C to obtain a transparent support. Further, the Tg cellulose film used had a Tg of 148 °C. The thickness of the transparent support produced was 90 μm.

<Measurement of Re and Rth>

The optical properties of the transparent support obtained after conditioning for 2 hours in an environment of 25 ° C and 55% RH were measured by KOBRA 21ADH (manufactured by Oji Scientific Instruments Co., Ltd.) according to the method described above. Re and Rth of the support at wavelengths of 450 nm, 550 nm, and 630 nm. The measurement results are shown in Table 2.

<Measurement of Humidity Dependence of Re and Rth (△Re, △Rth)

The optical support obtained after adjusting the transparent support at 25 ° C, 10% RH, and 25 ° C, 80% RH for 2 hours, according to the method described above, with KOBRA 21ADH (Prince Measurement) (manufactured by Co., Ltd.) measures Re and Rth of the support at a wavelength of 550 nm. Then, based on the measured results, ΔRe=Re (25° C., 10% RH)-Re (25° C., 80% RH), and ΔRth=Rth (25° C., 10% RH)-Rth (25° C.) are set. The values calculated by 80% RH) are shown in Table 3.

<Measurement of the degree of orientation P>

The degree of alignment of the obtained transparent support was measured. Specifically, a single crystal X-ray diffraction device (RAPID R-AXIS, manufactured by Rigaku Corporation) was used, and the X-ray source used a CuKα line to generate X-rays at 40 kV to 36 mA. Collimation tube is 0.8 mm The support system is fixed using a transmission sample stage. In addition, the exposure time was set to 600 seconds. The alignment measured by using the single crystal X-ray diffraction apparatus is shown in Table 3.

<Saponification treatment>

10 mL/m ² of 1.0 N potassium hydroxide solution (solvent: water / isopropanol / propylene glycol = 69.2 parts by mass / 15 parts by mass / 15.8 parts by mass) was applied to the tape side of the obtained transparent support. After holding for about 30 seconds at about 40 ° C, the lye was scraped off, washed with pure water, and then water droplets were blown off with an air knife. Thereafter, it was dried at 100 ° C for 15 seconds. The contact angle of the support treated surface with respect to pure water was determined to be 42°.

<Manufacture of alignment film>

On the support, an alignment film coating liquid having the composition shown below was applied at 28 mL/m ² using a #16 wire bar coater. It was dried at 60 ° C for 60 seconds, and then dried at 90 ° C for 150 seconds to obtain an alignment film.

(composition film coating liquid composition)

It was dried at 25 ° C for 60 seconds, dried at 60 ° C for 60 seconds, and further dried at 90 ° C for 150 seconds. The thickness of the alignment film after drying was 1.1 μm. In addition, the surface roughness of the alignment film was 1.147 nm as measured by an atomic force microscope (AFM: Atomic Force Microscope, SPI3800N, manufactured by Seiko Instrument Co., Ltd.).

<Formation of Optical Anisotropic Layer>

40 parts by mass of methyl ethyl ketone was dissolved in 100 parts by mass of the discotic liquid crystal compound represented by the following structural formula (C), and 0.4 parts by mass of the air interface alignment represented by the structural formula (D) shown below Control agent, 3 parts by mass of a photopolymerization initiator (Irgacure 907, manufactured by Ciba-Geigy Co., Ltd.), and 1 part by mass of a sensitizer (Kayacure DETX, Nippon Kayaku Co., Ltd.) , Ltd.) manufactured by the company to prepare a coating liquid.

The coating liquid was applied onto the alignment film as described above using a #2.0 wire rod. It was attached to a metal frame and heated in a 120 ° C thermostat bath for 90 seconds to align the discotic liquid crystal compound.

Next, ultraviolet rays were irradiated for 1 minute at 120 ° C using a 120 W/cm high-pressure mercury lamp to polymerize the discotic liquid crystal compound. Thereafter, it is naturally cooled to room temperature. Thereby, an optically anisotropic layer was formed on the support as described above via the alignment film to obtain an optical compensation film.

<Measurement of Optical Properties of Optically Irregular Layers>

An alignment film was produced on the glass in the same manner as above, and an optically anisotropic layer was formed on the alignment film, and then Re _{(550) was} measured using a KOBRA 21ADH at a wavelength of 550 nm, and as a result, it was 30 nm.

In addition, the hysteresis ratio was measured using KOBRA 2lADH at 450 nm and 650 nm, and the result was Re ₍₄₅₀₎ / Re _{(650) of} 1.15. Further, the thickness of the optically anisotropic layer was measured and found to be 0.8 μm.

The discotic liquid crystal compound represented by the structural formula (C) shown above was injected while allowing the director of the discotic liquid crystal compound to be aligned in parallel in the in-plane 2 μm glass cell, and left for 2 minutes.

The hysteresis value Re_m _{(550) was} measured with a light of 550 nm using a KOBRA 21ADH, and the result was 235 nm. Since the interstitial space is 2 μm, the value of Re_m ₍₅₅₀₎ /d is 0.118.

[Example 2] <Manufacture of Optical Compensation Film> <Manufacturing of Transparent Support>

The composition shown below was placed in a mixing tank, stirred while heating, and the components were dissolved to prepare a cellulose triacetate (triethylenesulfonyl cellulose: TAC) solution.

(material. solvent composition)

The prepared coating liquid was cast using a casting machine having a belt having a width of 2 m and a length of 65 m. After the film surface temperature of the belt was 40 ° C, it was dried for 1 minute, and then peeled off, and then dried at 140 ° C for 30 minutes in a dry air to produce a film. At this time, the average drying speed at a solvent volatile content of 20% in the film was 1.5% by mass/min. Thereafter, the film was subjected to a uniaxial extension of 150% at a temperature of 185 ° C to obtain a transparent support. Further, the Tg of the cellulose film used was 149 °C. The thickness of the transparent support produced was 85 μm.

The Re and Rth, the humidity dependency, and the orientation P were measured for the obtained transparent support. The results are shown in Tables 2 and 3.

<Formation of optical anisotropic layer>

In the same manner as in Example 1, after the saponification treatment was applied to the support, an alignment film was formed, and an optically anisotropic layer was formed on the alignment film to obtain an optical compensation film.

[Example 3] <Manufacture of Optical Compensation Film> <Manufacturing of Transparent Support>

The composition shown below was placed in a mixing tank, stirred while heating, and the components were dissolved to prepare a cellulose triacetate (triethylenesulfonyl cellulose: TAC) solution.

(material. solvent composition)

The prepared coating liquid was cast using a casting machine having a belt having a width of 2 m and a length of 65 m. After the film surface temperature of the belt was 40 ° C, it was dried for 1 minute, and then peeled off, and then dried at 140 ° C for 30 minutes in a dry air to produce a film. At this time, the average drying speed at a solvent volatile content of 20% in the film was 1.5% by mass/min. Thereafter, the film was subjected to uniaxial stretching at a temperature of 200 ° C at 140% to produce a transparent support, which was used as an optical compensation film. Further, the Tg of the cellulose film used was 149 °C. The thickness of the obtained transparent support (optical compensation film) was 95 μm.

The Re and Rth, the humidity dependency, and the orientation P were measured for the obtained transparent support. The results are shown in Tables 2 and 3.

[Example 4] <Manufacture of Optical Compensation Film> <Manufacturing of Transparent Support>

The coating liquid prepared in the same composition as in Example 1 was cast using a casting machine having a belt having a width of 2 m and a length of 65 m. After the film surface temperature of the belt was 40 ° C, it was dried for 1 minute, and then peeled off, and then dried at 140 ° C for 30 minutes in a dry air to produce a film. At this time, the average drying rate at a solvent volatile content of 20% in the film was 1.5% by mass/min. Thereafter, the film was subjected to a uniaxial extension of 110% at a temperature of 180 ° C to obtain a transparent support. Further, the Tg cellulose film used had a Tg of 148 °C. Further, the thickness of the transparent support produced was 90 μm.

The Re and Rth, the humidity dependency, and the orientation P were measured for the obtained transparent support. The results are shown in Tables 2 and 3.

<Formation of optical anisotropic layer>

In the same manner as in Example 1, after the saponification treatment was applied to the support, an alignment film was formed, and an optically anisotropic layer was formed on the alignment film to obtain an optical compensation film.

[Example 5] <Manufacture of Optical Compensation Film> <Manufacturing of Transparent Support>

The coating liquid prepared in the same composition as in Example 1 was cast using a casting machine having a belt having a width of 2 m and a length of 65 m. After the film surface temperature of the belt was 40 ° C, it was dried for 1 minute, and then peeled off, and then dried at 140 ° C for 30 minutes in a dry air to produce a film. At this time, the average drying rate at a solvent volatile content of 20% in the film was 1.5% by mass/min. Thereafter, the film was subjected to a uniaxial extension of 160% at a temperature of 190 ° C to obtain a transparent support. Further, the Tg cellulose film used had a Tg of 148 °C. Further, the thickness of the transparent support produced was 95 μm.

The Re and Rth, the humidity dependency, and the orientation P were measured for the obtained transparent support. The results are shown in Tables 2 and 3.

<Formation of optical anisotropic layer>

In the same manner as in Example 1, after the saponification treatment was applied to the support, an alignment film was formed, and an optically anisotropic layer was formed on the alignment film to obtain an optical compensation film.

[Example 6] <Manufacture of Optical Compensation Film> <Manufacture of Supports>

The composition shown below was placed in a mixing tank, stirred while heating, and the components were dissolved to prepare a cellulose triacetate (triethylenesulfonyl cellulose: TAC) solution.

(material. solvent composition)

The prepared coating liquid was cast using a casting machine having a belt having a width of 2 m and a length of 65 m. After the film surface temperature of the belt was 40 ° C, it was dried for 1 minute, and after peeling, it was dried by drying air at 100 ° C for 10 minutes, and dried by drying at 140 ° C for 20 minutes to obtain a film. The average drying speed at which the solvent volatile content in the film was 20% at this time was 1.1% by mass/minute. Thereafter, the film was subjected to a uniaxial extension of 140% at a temperature of 190 ° C to obtain a transparent support. Further, the Tg cellulose film used had a Tg of 148 °C. Further, the thickness of the transparent support produced was 90 μm.

The Re and Rth, the humidity dependency, and the orientation P were measured for the obtained transparent support. The results are shown in Tables 2 and 3.

<Formation of optical anisotropic layer>

In the same manner as in Example 1, after the saponification treatment was applied to the support, an alignment film was formed, and an optically anisotropic layer was formed on the alignment film to obtain an optical compensation film.

[Example 7] <Manufacture of Optical Compensation Film> <Manufacture of Supports>

The composition shown below was placed in a mixing tank, stirred while heating, and the components were dissolved to prepare a CAP (cellulose acetate-propionate) solution.

(material. solvent composition)

The prepared coating liquid was cast on a glass plate, dried at room temperature for 1 minute, and then dried at 70 ° C for 6 minutes. The obtained cellulose propionate film was peeled off from a glass plate and dried at 140 ° C for 30 minutes. The dried film was subjected to a uniaxial extension of 130% of the free end at a temperature of 130 ° C to prepare a support. The film thickness of the obtained film was 80 μm.

The Re and Rth, the humidity dependency, and the orientation P were measured for the obtained transparent support. The results are shown in Tables 2 and 3.

<Formation of optical anisotropic layer>

In the same manner as in Example 1, after the saponification treatment was applied to the support, an alignment film was formed, and an optically anisotropic layer was formed on the alignment film to obtain an optical compensation film.

[Example 8] <Manufacture of Optical Compensation Film> <Manufacture of Supports>

The composition shown below was placed in a mixing tank, stirred while heating, and the components were dissolved to prepare a cellulose triacetate (triethylenesulfonyl cellulose: TAC) solution.

(material. solvent composition)

The prepared solution (coating liquid) was cast using a casting machine having a belt having a width of 2 m and a length of 65 m. After the film surface temperature of the belt was 40 ° C, it was dried for 1 minute, and then peeled off, and then dried at 140 ° C for 30 minutes in a dry air to produce a film. At this time, the average drying speed at a solvent volatile content of 20% in the film was 1.5% by mass/min. Thereafter, the film was subjected to a uniaxial extension of 140% at a temperature of 190 ° C to obtain a transparent support. Further, the Tg of the cellulose film used was 146 °C. The thickness of the transparent support produced was 80 μm.

The Re and Rth, the humidity dependency, and the orientation P were measured for the obtained transparent support. The results are shown in Tables 2 and 3.

<Formation of optical anisotropic layer>

In the same manner as in Example 1, after the saponification treatment was applied to the support, an alignment film was formed, and an optically anisotropic layer was formed on the alignment film to obtain an optical compensation film.

[Example 9] <Manufacture of Optical Compensation Film>

An optical compensation film was produced in the same manner as in Example 1.

The Re and Rth, the humidity dependency, and the orientation P were measured for the obtained transparent support. The results are shown in Tables 2 and 3.

<Formation of optical anisotropic layer>

In the same manner as in Example 1, after the saponification treatment was applied to the support, an alignment film was formed, and an optically anisotropic layer was formed on the alignment film to obtain an optical compensation film.

[Example 10] <Manufacture of Optical Compensation Film>

The obtained solution (coating liquid) was produced under the same conditions as in Example 8 and cast using a casting machine having a belt having a width of 2 m and a length of 65 m. After the film surface temperature of the belt was 40 ° C, it was dried for 1 minute, and then peeled off, and then dried at 140 ° C for 30 minutes in a dry air to produce a film. At this time, the average drying speed at a solvent volatile content of 20% in the film was 1.5% by mass/min. Thereafter, the film was subjected to a uniaxial extension of 140% at a temperature of 200 ° C to obtain a transparent support. Further, the Tg of the cellulose film used was 146 °C. The thickness of the transparent support produced was 80 μm.

The Re and Rth, the humidity dependency, and the orientation P were measured for the obtained transparent support. The results are shown in Tables 2 and 3.

<Formation of optical anisotropic layer>

In the same manner as in Example 1, after the saponification treatment was applied to the support, an alignment film was formed, and an optically anisotropic layer was formed on the alignment film to obtain an optical compensation film.

[Example 11] <Manufacture of Optical Compensation Film>

An optical compensation film was produced in the same manner as in Example 10.

The Re and Rth, the humidity dependency, and the orientation P were measured for the obtained transparent support. The results are shown in Tables 2 and 3.

<Formation of optical anisotropic layer>

In the same manner as in Example 1, after the saponification treatment was applied to the support, an alignment film was formed, and an optically anisotropic layer was formed on the alignment film to obtain an optical compensation film.

[Example 12] <Manufacture of Optical Compensation Film>

An optical compensation film was produced in the same manner as in Example 4.

The Re and Rth, the humidity dependency, and the orientation P were measured for the obtained transparent support. The results are shown in Tables 2 and 3.

<Formation of optical anisotropic layer>

In the same manner as in Example 1, after the saponification treatment was applied to the support, an alignment film was formed, and an optically anisotropic layer was formed on the alignment film to obtain an optical compensation film.

[Comparative Example 1] <Manufacture of Optical Compensation Film> <Manufacturing of Transparent Support>

The composition shown below was placed in a mixing tank, stirred while heating, and the components were dissolved to prepare a cellulose triacetate (triethylenesulfonyl cellulose: TAC) solution.

(material. solvent composition)

The prepared coating liquid was cast using a casting machine having a belt having a width of 2 m and a length of 65 m. After the film surface temperature of the belt was 40 ° C, it was dried for 1 minute, and then peeled off, and then dried at 140 ° C for 30 minutes in a dry air to produce a film. At this time, the average drying speed at a solvent volatile content of 20% in the film was 1.5% by mass/min. Thereafter, the film was subjected to a uniaxial extension of 140% at a temperature of 190 ° C to obtain a transparent support. Further, the Tg cellulose film used had a Tg of 148 °C. Work The thickness of the transparent support was 90 μm.

The Re and Rth, the humidity dependency, and the orientation P were measured for the obtained transparent support. The results are shown in Tables 2 and 3.

<Formation of optical anisotropic layer>

In the same manner as in Example 1, after the saponification treatment was applied to the support, an alignment film was formed, and an optically anisotropic layer was formed on the alignment film to obtain an optical compensation film.

[Comparative Example 2] <Manufacture of Optical Compensation Film> <Manufacturing of Transparent Support>

The composition shown below was placed in a mixing tank, stirred while heating, and the components were dissolved to prepare a cellulose triacetate (triethylenesulfonyl cellulose: TAC) solution.

(material. solvent composition)

The prepared coating liquid was cast using a casting machine having a belt having a width of 2 m and a length of 65 m. After the film surface temperature of the belt was 40 ° C, it was dried for 1 minute, and then peeled off, and then dried at 140 ° C for 30 minutes in a dry air to produce a film. At this time, the average drying speed at a solvent volatile content of 20% in the film was 1.5% by mass/min. Thereafter, the film was subjected to a uniaxial extension of 120% at a temperature of 150 ° C to obtain a transparent support. Further, the Tg cellulose film used had a Tg of 148 °C. The thickness of the transparent support produced was 90 μm.

The Re and Rth, the humidity dependency, and the orientation P were measured for the obtained transparent support. The results are shown in Tables 2 and 3.

<Formation of optical anisotropic layer>

In the same manner as in Example 1, after the saponification treatment was applied to the support, an alignment film was formed, and an optically anisotropic layer was formed on the alignment film to obtain an optical compensation film.

[Comparative Example 3] <Manufacture of Optical Compensation Film> <Manufacturing of Transparent Support>

The composition shown below was placed in a mixing tank, stirred while heating, and the components were dissolved to prepare a cellulose triacetate (triethylenesulfonyl cellulose: TAC) solution.

Further, the maximum absorption wavelength λ _max measured for the compound of the structural formula (E) shown below is shown in Table 3.

(material. solvent composition)

The prepared coating liquid was cast using a casting machine having a belt having a width of 2 m and a length of 65 m. After the film surface temperature of the belt was 40 ° C, it was dried for 1 minute, and then peeled off, and then dried at 140 ° C for 30 minutes in a dry air to produce a film. At this time, the average drying speed at a solvent volatile content of 20% in the film was 1.5% by mass/min. Thereafter, the film was subjected to a uniaxial extension of 120% at a temperature of 185 ° C to obtain a transparent support. Further, the Tg cellulose film used had a Tg of 148 °C. The thickness of the transparent support produced was 80 μm.

The Re and Rth, the humidity dependency, and the orientation P were measured for the obtained transparent support. The results are shown in Tables 2 and 3.

<Formation of optical anisotropic layer>

In the same manner as in Example 1, after the saponification treatment was applied to the support, an alignment film was formed, and an optically anisotropic layer was formed on the alignment film to obtain an optical compensation film.

[Comparative Example 4] <Manufacture of Optical Compensation Film> <Manufacturing of Transparent Support>

The coating liquid prepared in the same composition as in Example 1 was cast using a casting machine having a belt having a width of 2 m and a length of 65 m. After the film surface temperature of the belt was 40 ° C, it was dried for 1 minute, and then peeled off, and then dried at 140 ° C for 30 minutes in a dry air to produce a film. At this time, the average drying rate at a solvent volatile content of 20% in the film was 1.5% by mass/min. Thereafter, although a uniaxial extension of 200% was applied to the film at a temperature of 190 ° C, the film was broken. The degree of alignment of the ruptured transparent support was measured in the same manner as in Example 1 and found to be 0.31. Therefore, a transparent support having an orientation P of more than 0.30 cannot be obtained.

[Comparative Example 5] <Manufacture of Optical Compensation Film> <Manufacturing of Transparent Support>

A transparent support was obtained in the same manner as Comparative Example 1 as described above, and was used as an optical compensation film.

The Re and Rth, the humidity dependency, and the orientation P were measured for the obtained transparent support. The results are shown in Tables 2 and 3.

<Formation of optical anisotropic layer>

In the same manner as in Example 1, after the saponification treatment was applied to the support, an alignment film was formed, and an optically anisotropic layer was formed on the alignment film to obtain an optical compensation film.

(Manufacture of polarizing plate)

First, iodine is adsorbed on the stretched polyvinyl alcohol film to obtain a polarizing film.

Thereafter, each of the optical compensation films of Examples 1 to 8, 11 and Comparative Examples 1 to 3 and Comparative Example 5 was attached to the polarizing film using a polyvinyl alcohol-based adhesive, and the other side of the polarizing film was attached. Then, a commercially available cellulose triacetate film (Fujitac TD80UF, manufactured by Fuji Photo Film Co., Ltd.) to which saponification treatment was applied was attached using a polyvinyl alcohol-based adhesive. Further, when an optical compensation film is attached to one surface of the polarizing film, the transmission axis of the polarizing film and the slow axis of the optical compensation film are arranged in parallel. Ten kinds of polarizing plates according to Examples 1 to 8, 11 and Comparative Examples 1 to 3 and Comparative Example 5 were obtained in the above manner.

<Manufacture of protective film for polarizing plate with coating layer> <Modulation of coating liquid for coating layer>

As shown in the following composition, the layered inorganic compound is mixed with water in such a manner as to have a desired concentration. Thereafter, a high-pressure dispersing treatment was applied three times at 30 Mpa using a high-pressure disperser to disperse it in water.

[Composition of coating liquid for coating layer]

(coating of the coating)

For triethylenesulfonyl cellulose (TAC-TD80U, manufactured by Fujifilm Co., Ltd.), it was applied to one side of the coating layer to apply saponification at 50 ° C in a 1 mol/L alkaline solution. deal with.

Thereafter, the coating liquid for a coating layer as described above was applied to a saponified surface of a triethylenesulfonated cellulose film to a coating thickness of 20 μm after being dried.

Thereafter, it was applied under the conditions of a conveying speed of 30 m/min, dried at 130 ° C for 5 minutes, and then taken up.

(Measurement of moisture permeability)

The measurement method of the moisture permeability can be applied to the measurement of the vapor permeation amount (mass method, thermometer method, vapor pressure method, etc.), which is disclosed in "Physical Properties of Polymers II" (Multimedia Experiment Lecture 4). Method of adsorption amount), that is, 70 mm to be used in the present invention The film samples were conditioned at 60 ° C and 95% RH for 24 hours, respectively, and the amount of water per unit area (g/m ² ) was calculated in accordance with JIS Z-0208 with moisture permeability = mass after conditioning - quality before conditioning. At this time, at an appropriate time interval, the cup placed in the constant temperature and humidity device is repeatedly taken out and weighed, and the mass increase per unit time is determined by two consecutive weighings until it can be 5 The evaluation continues until within %. Further, in order to avoid the influence of the sample moisture absorption or the like, an empty cup in which the moisture absorbent is not placed is measured to correct the value of the moisture permeability.

The moisture permeability of the triethylsulfonated cellulose coated with the coating layer as described above was 230 g/m ² , and the moisture permeability of the triethylsulfonated cellulose which was not coated with the coating layer was 1,400 g/m ^{2 .} Significantly reduced.

(Manufacture of polarizing plate with coating)

Iodine is adsorbed on the stretched polyvinyl alcohol film to prepare a polarizing film.

Thereafter, each of the optical compensation films of Examples 9, 10, and 12 was attached to the polarizing film using a polyvinyl alcohol-based adhesive, and a polyvinyl alcohol-based adhesive was used on the other surface of the polarizing film. The triethylenesulfonyl cellulose to which the saponification treatment was applied and which was coated as described above was applied. Further, when an optical compensation film is attached to one surface of the polarizing film, the transmission axis of the polarizing film and the slow axis of the optical compensation film are arranged in parallel. In this way, the polarizing plates of Examples 9, 10 and 12 were obtained.

<Installation evaluation of liquid crystal display device> <Manufacture of curved alignment liquid crystal cells>

On the glass substrate with the ITO electrode, a polyimide film was provided as an alignment film, and a rubbing treatment was applied to the alignment film. The two glass substrates thus obtained were placed in a state in which the rubbing directions were arranged in parallel, and the cell gap was set to 4.7 μm. A liquid crystal compound (ZLI 1132, manufactured by Merck & Co.) having a Δn of 0.1396 was injected into the interstitial space to prepare a curved alignment liquid crystal cell.

The upper side and lower side polarizing plates of the liquid crystal display device using the curved alignment type liquid crystal cell, which were obtained by using the optical compensation films obtained in Examples 1 to 2, 4 to 6, and Comparative Examples 1 to 3, were used. The polarizing plate is attached to each of the viewer side and the backlight side via an adhesive so that the optical compensation film is positioned on the liquid crystal cell side. Further, the optically anisotropic layer of the polarizing plate is disposed opposite to the cell substrate, and the rubbing direction of the liquid crystal cell is antiparallel to the rubbing direction of the optically anisotropic layer of the surface. Further, the crossed Nichol is disposed so that the transmission axis of the observer-side polarizing plate can be vertically moved and the transmission axis of the backlight-side polarizing plate is oriented in the left-right direction.

After the obtained liquid crystal panel was left in an environment of 25 ° C and 60% RH for 7 days, the evaluation of the display characteristics was evaluated based on the evaluation criteria as described below. The results are shown in Table 5.

[Evaluation Criteria] Viewing angle (contrast ratio is 10 or more and there is no polar angle range of gray scale inversion on the black side) ○: Up and down and left and right are 75° polar angle or more; ○ △: 3 directions of up, down, left and right are 75° polar angle or more; △: 2 directions in the upper, lower, left and right are 75° or more; X: 3 in the upper, lower, left and right directions is less than 75°.

A rectangular wave voltage of 55 Hz was applied to the liquid crystal cells. A normal white mode with a white display of 2 V and a black display of 5 V is adopted. The voltage applied to the front side, which is the minimum voltage, that is, the black voltage, and the black display transmittance (%) at the 0° azimuth angle, the 60° polar angle view, and the 0° azimuth angle, The color displacement Δx of the 60° polar angle and the 180° azimuth angle and the 60° polar angle. The results are shown in Table 3.

In addition, in Table 3 shown below, the so-called "color shift" is ΔCu'v' at azimuth angle of 0°: u'v' (60° polar angle)-u'v' (0° pole Angle) is the sum of ΔCu'v':u'v' (60° polar angle)-u'v' (0° polar angle) at 180° azimuth. (u’v’: color coordinates in CIELAB space)

In addition, the ratio of transmittance (white display/black display) was set to a contrast ratio, and a measuring machine (EZ-Contrast 160D, manufactured by ELDIM) was used, and the display from black (L1) to white was used. The 8-stage measurement angle of view up to (L8) is displayed. The results are shown in Table 4.

In addition, in Table 4 shown below, the "viewing angle" means a range in which the contrast coefficient is 10 or more and there is no "black-level gray-scale inversion (reversal between L1 and L2)".

<Manufacture of VA Alignment Liquid Crystal Cell>

The liquid crystal cell has a cell gap of 3.6 μm between the substrates, and a liquid crystal material having a negative dielectric anisotropy ("MLC6608", manufactured by Merck & Co.) is dropped and injected between the substrates. And sealed to form a liquid crystal layer between the substrates. The hysteresis of the liquid crystal layer (that is, the product of the thickness d (μm) of the liquid crystal layer and the refractive index anisotropy Δn Δn.d) is set to 300 nm. In addition, the liquid crystal material is aligned to be vertically aligned.

In the upper side and lower side polarizing plates of the liquid crystal display device using the vertically aligned type liquid crystal cells as described above, the polarizing plates of the optical compensation films obtained in Examples 3, 12 and Comparative Example 5 were used to enable The optical compensation film side of the polarizing plate is opposed to the liquid crystal cell side, and one piece is attached to each of the observer side and the backlight side via an adhesive. Further, the crossed Nicols are arranged such that the transmission axis of the observer-side polarizing plate is in the vertical direction, and the transmission axis of the backlight-side polarizing plate is in the left-right direction.

After the obtained liquid crystal panel was allowed to stand in an environment of 25 ° C and 60% RH for 7 days, the evaluation of the display characteristics was evaluated based on the above [Evaluation Criteria]. The results are shown in Table 5.

A rectangular wave voltage of 55 Hz was applied to the liquid crystal cells. Set to normal black mode with white display 5V and black display 0V. The black display transmittance (%) at the 0° azimuth angle of the black display and the 60° polar angle view, and the color displacement of the 0° azimuth angle, the 60° polar angle and the 180° azimuth angle, and the 60° polar angle are determined. x. The results are shown in Table 3.

In addition, the ratio of transmittance (white display/black display) is set to a contrast ratio, and a measuring machine (EZ-Contrast 160D, manufactured by ELDIM Co., Ltd.) is used, and eight stages from black display (L1) to white display (L8) are used. The viewing angle is measured. The results are shown in Table 4.

<Measurement of Humidity Dependence of Display Characteristics>

After the liquid crystal panel obtained as described above was allowed to stand in an environment of 25 ° C 10% RH and 25 ° C 80% RH for 7 days, the evaluation of the display characteristics was evaluated based on the above [Evaluation Criteria]. The results are shown in Table 5.

It can be understood from the results shown in Tables 2 to 5 that the alignment P is in compliance with the conditions of 0.05 ≦ P ≦ 0.30, and the optical characteristics are in accordance with 10 < Re ₍₅₅₀₎ < 100, 100 < Rth ₍₅₅₀₎ < 200, 0.5. _{<Re (450) / Re (} 550) <1.0,1.0 <Re (630) / Re (550) <1.5,1.0 <Rth (450) / Rth (550) <1.5, and 0.5 <Rth ₍₆₃₀₎ / Rth ₍₅₅₀₎ <1.0 Conditions The liquid crystal display devices of the optical compensation films of Examples 1 to 12 are compared with the liquid crystal display devices having the optical compensation films of Comparative Examples 1 to 5 at a black display of a polar angle of 60°. The transmittance is low and the color shift with the front side is also small, resulting in a significant improvement in contrast.

The optical compensation film of the present invention, and the polarizing plate, particularly for the VA mode, the IPS mode, or the OCB mode, can improve high contrast, and the color shift depending on the viewing direction in the black display, and the viewing angle contrast is remarkably improved, so that it is suitable Used in liquid crystal display devices.

The liquid crystal display device of the invention can optically compensate the liquid crystal cell, improve the contrast, and reduce the color displacement depending on the viewing angle direction, and is therefore suitable for use in a portable telephone, a personal computer monitor, a television, a liquid crystal projector, etc. .

1, 101. . . Polarizing film

2, 102. . . Transmission axis

4a, 14a, 104a, 114a. . . Delay phase axis

5, 9. . . Optical anisotropy

5a, 9a. . . Orientation

6, 8. . . Substrate

7. . . Liquid crystal molecule

13a, 103a, 113a. . . Transparent support

13A, 113A. . . Optical compensation film

I ₁ -I ₆ . . . Polarized state of G light incident from 60° left

I ₁ '-I ₆ '. . . Polarized state of G light incident from the right 60°

I _B1 -I _B6 . . . Polarized state of B light incident from 60° left

I _B1 '~I _B6 '. . . Polarized state of B light incident from 60° right

I _R1 ~I _R6 . . . Polarized state of R light incident from 60° left

I _R1 '~I _R6 '. . . Polarized state of R light incident from the right 60°

RD. . . Arrow mark

Re. . . In-plane hysteresis

Rth. . . Thickness direction lag

Fig. 1 is a schematic view showing a configuration example of a liquid crystal display device of the present invention.

Fig. 2 is a graph showing optical characteristics relating to an example of the optical compensation film used in the present invention.

Fig. 3A is a schematic view for explaining a Puancarre ball used for the change in the polarization state of incident light of the liquid crystal display device of the present invention.

Fig. 3B is a schematic view for explaining a Puancarre ball used for the change in the polarization state of the incident light of the liquid crystal display device of the present invention.

Fig. 4 is a schematic view showing an example of a configuration of a conventional OCB mode liquid crystal display device.

Fig. 5A is a schematic view showing a Puancarre ball used for explaining a change in the polarization state of incident light of an example of a conventional liquid crystal display device.

Fig. 5B is a schematic view showing a Puancarre ball used for explaining a change in the polarization state of incident light in an example of a conventional liquid crystal display device.

Fig. 6A is a schematic view for explaining a Puancarre ball used for the change in the polarization state of incident light of the liquid crystal display device of the present invention.

Fig. 6B is a view for explaining a Puancarre ball used for the change in the polarization state of the incident light of the liquid crystal display device of the present invention.

Figure 7A is a graph showing the wavelength dispersion of a film obtained by adding an Rth rising agent but not extending.

Figure 7B shows a wavelength dispersion map of the film obtained by stretching only Rth without adding a rising agent.

Figure 7C shows a wavelength dispersion map of the film obtained by adding an Rth rising agent and extending the film.

Claims (14)

An optical compensation film characterized by having a transparent support containing at least one Rth rising agent, and the alignment P defined by the following formula (A) calculated from the X-ray diffraction measurement of the transparent support is 0.05 to 0.30, but exclude the range of 0.17 or more: P=<3 cos ² β-1>/2 Formula (A) However, in the formula (A), <cos ² β>=ʃ(0,π)cos ² βI( β) sinβdβ/ʃ(0,π)I(β)sinβdβ, and the angle formed by the incident surface of the X-ray incident on the β-system in a certain direction in the plane of the transparent support in the formula (A), I is the diffraction intensity at 2θ = 8° in the X-ray diffraction pattern measured at angle β. The optical compensation film of claim 1, wherein the optical property of one of the transparent supports satisfies the relationship of the following formulas (1) to (6): 10 nm < Re ₍₅₅₀₎ < 100 nm (1) 100 nm <Rth ₍₅₅₀₎ <200nm Equation (2) 0.5<Re ₍₄₅₀₎ /Re ₍₅₅₀₎ <1.0 Equation (3) 1.0<Re ₍₆₃₀₎ /Re ₍₅₅₀₎ <1.5 Equation (4) 1.0<Rth _{(450 )} /Rth ₍₅₅₀₎ <1.5 Equation (5) 0.5<Rth ₍₆₃₀₎ /Rth ₍₅₅₀₎ <1.0 Equation (6) However, in the equations (1) to (6), Re _(λ) is for wavelength The hysteresis value in the plane of the transparent support of _λ nm light, Rth _(λ) is the hysteresis value of the thickness direction of the transparent support for light having a wavelength of _λ nm. The optical compensation film according to claim 1, wherein the Rth rising agent is a compound represented by any one of the following formulas (II) to (IV): however, the formula is as follows In (II), R ¹² each independently represents an aromatic ring or a heterocyclic ring having a substituent in at least one of an ortho, meta and para, and the X ¹¹ each independently represents a single bond or NR ¹³ - wherein R ¹³ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and further, in the formula (III), R as shown below ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or a substituent, and in the following formula (IV), Q ⁷¹ represents a nitrogen-containing aromatic heterocyclic ring. Q ⁷² series represents an aromatic ring, Q ⁷¹ -Q ⁷² -OH Formula (IV). The optical compensation film according to claim 1, wherein the Rth ascending agent has two or more aromatic rings. The optical compensation film according to claim 1, wherein the solution absorption spectrum of the Rth rising agent comprises a compound having a maximum absorption wavelength (λ _max ) of at least 250 nm. The optical compensation film according to claim 1, which comprises a humidity dependency improver having a hydrogen bonding group in at least one molecule. The optical compensation film according to claim 6, wherein the humidity dependency improver has an aromatic ring and satisfies the following formula (7): a hydrogen bonding group/humidity dependency improver in one molecule Molecular weight >0.01 Formula (7). The optical compensation film according to claim 1, wherein the transparent support system satisfies the following formulas (8) to (9): 2.0 ≦ SA + SB ≦ 3.0 (8) 0 < SB (9) However, In the formulae (8) to (9), the degree of substitution of the sulfhydryl group of the hydrogen atom of the hydroxyl group in the cellulose substituted by the cellulose, and the substitution of the sulfhydryl group of the hydrogen atom of the hydroxyl group of the hydroxy group in the cellulose of 3 to 22 in the SB-substituted cellulose. degree. A method for producing an optical compensation film, characterized in that the optical compensation film has a transparent support containing at least one Rth rising agent, and the transparent support is defined by the following formula (A) by X-ray diffraction measurement The degree of alignment P is 0.05 to 0.30, but excludes the range of 0.17 or more, and includes a casting step of casting a polymer solution of a raw material containing a transparent support of at least one Rth rising agent on the belt; a drying step of the film obtained by the casting step; and an extending step of extending the film at a temperature higher than a glass transition temperature of the transparent support by +15 to +100 ° C after the film is peeled off by the tape: P =<3cos ² β-1>/2 Equation (A) However, in the formula (A), <cos ² β>=ʃ(0,π)cos ² βI(β)sinβdβ/ʃ(0,π)I (β) sinβdβ, in the formula, the angle formed by the incident surface of the X-ray incident on the β-ray in a certain direction in the plane of the transparent support, and the X-ray diffraction pattern measured at the angle β Diffraction intensity at 2θ = 8°. Method for producing optical compensation film according to claim 9 Wherein the drying step is set to an average drying speed in the region of the film having a volatile matter ratio of 10 to 100% by mass, which is at least 1.2% by mass/minute. A polarizing plate characterized in that the polarizing plate has a polarizing film and a pair of protective films for holding the polarizing film, at least one of the protective films having a transparent support body containing at least one Rth rising agent, and The transparent support is calculated from the X-ray diffraction measurement to have an orientation P defined by the following formula (A) of 0.05 to 0.30, but excludes an optical compensation film in the range of 0.17 or more: P=<3 cos ² β-1> /2 Formula (A) However, in the above formula (A), <cos ² β>=ʃ(0,π)cos ² βI(β)sinβdβ/ʃ(0,π)I(β)sinβdβ, and this formula The angle between the incident surface of the X-ray incident on the β-ray and the direction in the plane of the transparent support, I is the diffraction at 2θ=8° in the X-ray diffraction pattern measured by the angle β. strength. The polarizing plate of claim 11, wherein the coating layer has a low moisture permeability coating on at least one side of the protective film, and the coating layer has a moisture permeability of 300 g/m ² at 60 ° C and 95% relative humidity. . Below day. A liquid crystal display device characterized by having a liquid crystal cell and a polarizing plate, the polarizing plate having a polarizing film and a pair of protective films for holding the polarizing film, at least one of the protective films having at least one Rth rising agent a transparent support, and the alignment P defined by the following formula (A) calculated by X-ray diffraction measurement of the transparent support is 0.05 to 0.30, but the optical compensation film in the range of 0.17 or more is excluded, P=< 3 cos ² β-1>/2 Formula (A) However, in the formula (A), <cos ² β>=ʃ(0,π)cos ² βI(β)sinβdβ/ʃ(0,π)I( β) sinβdβ, in the equation, the angle formed by the incident surface of the X-ray incident on the β-ray in a certain direction in the plane of the transparent support, I is in the X-ray diffraction pattern measured by the angle β Diffraction intensity at 2θ = 8°. The liquid crystal display device of claim 13, wherein the liquid crystal cell is in a VA mode, an OCB mode, or an IPS mode.