KR101384875B1 - Retardation film, polarizing plate and liquid crystal display device - Google Patents

Abstract

(Problem) In the black display, the retardation film etc. which can improve the light leakage and a change of a color sense when seen from the diagonal direction are provided.

(Remedy) As a retardation film having a support and at least one optically anisotropic layer, the front retardation Re and the retardation Rth in the thickness direction of the support satisfy the following formula [1], and the wavelength of the support Dispersibility satisfy | fills following formula [2] -1, The said support body consists of a cellulose acylate film, The front retardation (Re) of the retardation film and the retardation (Rth) of thickness direction are following formula [3] And a wavelength dispersion of the retardation film satisfying the following formula [4].

[1] 0 ≤ Re (630) ≤ 10 and | Rth (630) | ≤ 25

[2] -1 | Re (400) -Re (700) | ≤ 10 and | Rth (400) -Rth (700) | ≤ 35

[3] 0 ≤ Re (550) ≤ 10 and 100 ≤ Rth (550) ≤ 300

[4] 1.04 ≤ Rth (450) / Rth (550) ≤ 1.30

[In formula, Re ((lambda)) is represented by Re ((lambda)) = (nx-ny) xd and shows the front retardation value (unit: nm) in wavelength (lambda) nm. Rth (λ) is represented by Rth (λ) = {(nx + ny) / 2-nz} × d and represents a retardation value (unit: nm) in the film thickness direction at a wavelength λnm. Nx is a refractive index in the slow axis direction in the film plane, ny is a refractive index in the fast axis direction in the film plane, nz is a refractive index in the thickness direction of the film, and d is the thickness (nm) of the film.]

Polarizer, retardation film, light leakage, retardation

Description

Retardation Film, Polarizer and Liquid Crystal Display {RETARDATION FILM, POLARIZING PLATE AND LIQUID CRYSTAL DISPLAY DEVICE}

1 is a schematic view showing an example of a liquid crystal display of the present invention.

2 is a schematic view showing an example of a polarizing plate usable in the present invention.

DESCRIPTION OF THE REFERENCE NUMERALS

1: upper polarizer

2: absorption axis direction of the upper polarizing plate

3: second retardation film

4: slow axis direction of the second retardation film

5: liquid crystal cell upper electrode substrate

6: upper substrate orientation control direction

7: liquid crystal molecules

8: liquid crystal cell lower electrode substrate

9: Lower substrate orientation control direction

10: first retardation film

14: lower polarizing plate

15: Absorption axis direction of the lower polarizing plate

101: polarizing plate protective film

102: slow axis direction of the polarizing plate protective film

103: polarizing plate polarizing film

104: absorption axis direction of the polarizing film

105: polarizing plate protective film

106: slow axis direction of the polarizing plate protective film

Patent Document 1: Japanese Patent Application Laid-Open No. 2-176625

Patent Document 2: Japanese Patent Application Laid-Open No. 11-95208

Patent Document 3: Japanese Patent Application Laid-Open No. 11-352328

Patent Document 4: Japanese Unexamined Patent Publication No. 2000-304931

Patent Document 5: Japanese Unexamined Patent Publication No. 2005-128050

TECHNICAL FIELD This invention relates to the technical fields of retardation film, a polarizing plate, and a liquid crystal display device, and it belongs especially to the technical fields, such as a vertically-aligned liquid crystal display device and the retardation film and polarizing plate used therefor.

The liquid crystal display device usually has a liquid crystal cell and a polarizing plate. The polarizing plate has a protective film and a polarizing film. And a polarizing plate is obtained by dyeing and extending | stretching the polarizing film which consists of polyvinyl alcohol films etc. with iodine, for example, and laminating | stacking a protective film on both surfaces. In a transmissive liquid crystal display device, this polarizing plate may be provided in both sides of a liquid crystal cell, and one or more optical compensation sheets may be arrange | positioned further. In a reflective liquid crystal display device, it arranges in order of a reflecting plate, a liquid crystal cell, one or more optical compensation sheets, and a polarizing plate. The liquid crystal cell is composed of liquid crystal molecules, two substrates for encapsulating it, and an electrode layer for applying voltage to the liquid crystal molecules. The liquid crystal cell performs ON and OFF display according to the difference in the alignment state of the liquid crystal molecules, and can be applied anywhere in the transmission and reflection type, TN (Twisted Nematic), IPS (In-Plane Switching), and OCB (0ptically Compensatory Bend). ), Display modes such as VA (Vertically Aligned) and ECB (Electrically Controlled Birefringence) have been proposed.

As for the applications requiring high display quality among such liquid crystal display devices, a 90-degree twisted nematic liquid crystal display device driven by a thin film transistor using nematic liquid crystal molecules having positive dielectric anisotropy (hereinafter, TN Mode is commonly used. However, the TN mode has excellent display characteristics when viewed from the front, but has a viewing angle characteristic that the display characteristics are deteriorated due to a decrease in contrast or a gray level inversion in which brightness is reversed in gray scale display. Therefore, there is a strong demand for improvement.

In recent years, as a method of a liquid crystal display device for improving this viewing angle characteristic, a nematic liquid crystal molecule having negative dielectric anisotropy is used, and the long axis of the liquid crystal molecules is substantially perpendicular to the substrate in the state where no voltage is applied. A vertically aligned nematic liquid crystal display device (hereinafter referred to as a VA mode) which is oriented in a vertical direction and driven by a thin film transistor is proposed (see Patent Document 1 above). This VA mode not only has excellent display characteristics as seen in the TN mode when viewed from the front, but also exhibits wide viewing angle characteristics by applying a retardation film for viewing angle compensation. In VA mode, wider viewing angle characteristics can be obtained by using two negative uniaxial retardation films having an optical axis in a direction perpendicular to the film plane, above and below the liquid crystal cell, and further in-plane retardation values are added to this liquid crystal display device. It is also known to realize a wider viewing angle characteristic by using the uniaxially oriented retardation film having positive refractive index anisotropy of 50 nm (SID 97 DIGEST, pages 845 to 848).

However, when the number of retardation films is increased, the production cost is increased, and since a large number of films are attached, the yield is likely to be lowered. And since a some film is used, thickness may become thick and it may become disadvantageous for thickness reduction of a display apparatus. Moreover, since an adhesion layer is used for lamination of a stretched film, the adhesion layer shrinks with the change of temperature-humidity, and defects, such as peeling and curvature between films, may arise.

As a method of improving these, the method of reducing the number of sheets of retardation film (refer patent document 2), and the method of using a cholesteric liquid crystal layer (refer patent document 2) are disclosed. However, these methods also had to adhere | attach at least some film, and were insufficient in the point of thinning of a liquid crystal display device and reducing production cost.

Moreover, in order to improve the said subject, the method of using a discotic liquid crystalline compound (refer patent document 3) is proposed. However, in the method of the said patent document 3, it is difficult to form an optically anisotropic layer continuously in a long support body, and productivity fell. And the method which solved this problem is disclosed by the said patent document 4. However, also in the method described in the publication, in order to obtain the necessary optical properties (particularly, the Rth value), the coating film thickness becomes thick, and thus problems such as coating unevenness have occurred.

In addition, Patent Document 5 discloses a method of improving coating unevenness by employing an optically anisotropic layer having an absolute value of refractive index anisotropy in a specific range.

However, the above method was not at a level capable of satisfying the display characteristics of the liquid crystal display.

An object of the present invention is to provide a retardation film and a liquid crystal display device which are used in a liquid crystal display device that can be used, that is, thinner, even if the liquid crystal cell is accurately optically compensated and the number of films to be attached is reduced.

In addition, the present invention contributes to the reduction of light leakage and color change when observed in the oblique direction at the time of black display of a liquid crystal display device, especially a liquid crystal display device having a VA mode, and is stable by a simple method. It is an object of the present invention to provide a retardation film and a polarizing plate which can be manufactured.

In addition, the present invention has good display characteristics in the case of observing from the front direction and good display characteristics in the case of observing in the oblique direction, specifically light in the case of observing in the oblique direction at the time of black display. An object of the present invention is to provide a liquid crystal display device, in particular, a VA mode liquid crystal display device, in which leakage and color change are reduced.

As a result of earnestly examining by the inventor in order to solve such a subject, in the conventional retardation film which combined the support body which consists of a polymer film, etc. and an optically anisotropic layer, most of them are researched and developed mainly paying attention to the characteristic of an optically anisotropic layer. However, in order to solve the said subject, it turned out that it is necessary to examine also about the optical characteristic of a support body. As a result of further studies, when a retardation film made of a predetermined material and having a support having Re, Rth and wavelength dispersion characteristics satisfying a predetermined relationship is used, the display characteristics of the liquid crystal display device are improved and various display characteristics are achieved. It was found that (as well as the front direction, display characteristics in the inclined direction, etc.) reached a satisfactory level.

Specifically, the means for solving the above problems are as follows.

(1) A retardation film having a support and at least one optically anisotropic layer,

The front retardation Re of the support body and the retardation Rth of the thickness direction satisfy the following formula [1],

The wavelength dispersion of the support satisfies the following formula [2] -1,

The support is made of a cellulose acylate film,

The front retardation Re and the retardation Rth of the thickness direction of the retardation film satisfy the following formula [3], and

Retardation film whose wavelength dispersion property of the said retardation film satisfy | fills following formula [4]:

[1] 0 ≤ Re (630) ≤ 10 and | Rth (630) | ≤ 25

[2] -1 | Re (400) -Re (700) | ≤ 10 and | Rth (400) -Rth (700) | ≤ 35

[3] 0 ≤ Re (550) ≤ 10 and 100 ≤ Rth (550) ≤ 300

[4] 1.04 ≤ Rth (450) / Rth (550) ≤ 1.30

In formula, Re ((lambda)) is represented by Re ((lambda)) = (nx-ny) xd and shows the front retardation value (unit: nm) in wavelength (lambda) nm; Rth (λ) is represented by Rth (λ) = {(nx + ny) / 2-nz} × d and represents a retardation value (unit: nm) in the film thickness direction at a wavelength λ nm; nx is the refractive index in the slow axis direction in the film plane, ny is the refractive index in the fast axis direction in the film plane, nz is the refractive index in the thickness direction of the film, and d is the thickness (nm) of the film.

(2) a retardation film having a support and at least one optically anisotropic layer,

The support is made of a cellulose acylate film containing at least one acrylic polymer,

The front retardation Re of the support body and the retardation Rth of the thickness direction satisfy the following formula [1],

The wavelength dispersion of the support satisfies the following formula [2] -2,

The front retardation Re and the retardation Rth of the thickness direction of the retardation film satisfy the following formula [3], and

Retardation film whose wavelength dispersion property of the said retardation film satisfy | fills following formula [4]:

[1] 0 ≤ Re (630) ≤ 10 and | Rth (630) | ≤ 25

[2] -2 | Re (400) -Re (700) | ≤ 10 and -35 ≤ Rth (400) -Rth (700) ≤ 60

[3] 0 ≤ Re (550) ≤ 10 and 100 ≤ Rth (550) ≤ 300

[4] 1.04 ≤ Rth (450) / Rth (550) ≤ 1.30

In formula, Re ((lambda)) is represented by Re ((lambda)) = (nx-ny) xd, and shows the front-face retardation value (unit: nm) in wavelength (lambda) nm, and Rth ((lambda)) is Rth ((lambda)). ) = {(nx + ny) / 2-nz} xd, and represents the retardation value (unit: nm) of the film thickness direction in wavelength (lambda), nx is the refractive index of the slow-axis direction in a film plane, ny Is the refractive index in the fast axis direction in the film plane, nz is the refractive index in the thickness direction of the film, and d is the thickness (nm) of the film.

(3) The retardation film of (1) or (2) in which the wavelength dispersion of the retardation film satisfies the following formula [5]:

[5] 1.06 ≤ Rth (450) / Rth (550) ≤ 1.30

(4) At least one layer of the optically anisotropic layer polymerizes the polymerizable liquid crystal composition containing at least one of the discotic liquid crystalline compounds in the state of the nematic liquid crystal phase by homeotropically aligning the molecules of the discotic liquid crystalline compound. The retardation film of (1) or (2) which is a layer formed by fixing by the.

(5) One or more layers of the said optically anisotropic layer superpose | polymerize the polymerizable liquid crystal composition containing 1 or more types of rod-like liquid crystalline compounds in the state of a cholesteric liquid crystal phase by molecule | numerator of the rod-like liquid crystalline compound. Retardation film of (1) or (2) which is a layer formed by fixing.

(6) The retardation film of (1) or (2), wherein at least one layer of the optically anisotropic layer is a polymer layer.

(7) The retardation film of (6) in which the polymer layer contains at least one polymer selected from the group consisting of polyamide, polyimide, polyester, polyether ketone, polyamideimide and polyesterimide.

(8) The retardation film of (1) or (2) in which at least one layer of the optically anisotropic layer contains a fluorine-containing compound.

(9) 0.01-30 mass of the said support body with respect to the said cellulose acylate 1 or more types of the compound which reduces Re ((lambda)) and / or Rth ((lambda)) to the cellulose acylate of acyl substitution degree 2.85-3.00. The retardation film of (1) obtained by adding in the ratio of%.

(10) The retardation film (1) whose film thickness of the said support body is 10-120 micrometers.

(11) The retardation film of (2) in which the wavelength dispersibility of the support satisfies the following formula [6]:

[6] Re (400) -Re (700) | ≦ 10 and 0 ≦ Rth (400) -Rth (700) ≦ 60.

(12) The retardation film of (2) in which the support is made of a cellulose acylate film containing cellulose acylate having an acyl substitution degree of 2.70 to 3.00.

(13) The retardation film of (2), wherein the weight average molecular weight of the acrylic polymer is 500 or more and less than 10,000.

(14) The retardation film of (2), wherein the acrylic polymer is an acrylic polymer having a hydroxyl group in a main chain and / or in a side chain.

(15) The retardation film of (2) in which the support is made of a cellulose acylate film containing a plasticizer.

(16) The phase difference film (2) whose film thickness of the said support body is 10-60 micrometers.

(17) The polarizing plate which has a polarizing film and the protective film formed on both surfaces of the said polarizing film, and at least one of the said protective films is retardation film of (1) or (2).

(18) It has a polarizing film, the retardation film of (1) or (2), and a 2nd retardation film, The front retardation of the said 2nd retardation film and the retardation of thickness direction satisfy | fill the following formula [7] Moreover, the polarizing plate in which the wavelength dispersion of a 2nd phase difference film satisfy | fills following formula [8]:

[7] 70 ≤ Re (550) ≤ 180 and 30 ≤ Rth (550) ≤ 140

[8] 0.7 ≤ Re (450) / Re (550) ≤ 1.0

(19) A liquid crystal display device comprising the retardation film of (1) or (2), or the polarizing plate of (17) or (18).

(20) Liquid crystal molecules having two polarizing plates having mutual absorption axes perpendicular to each other, and a liquid crystal cell disposed between the two polarizing plates, wherein the liquid crystal cell is sandwiched between a pair of substrates and the pair of substrates. In the non-driven state in which the liquid crystal layer is formed, and the external electric field is not applied, the liquid crystal molecules are aligned in a direction substantially perpendicular to the pair of substrates, and (1) or (2) The liquid crystal display device which further contains retardation film or whose said polarizing plate is the polarizing plate of (17) or (18).

(21) The liquid crystal display further has a second retardation film, wherein the second retardation film is made of a polymer stretched film, and the front retardation and the retardation in the thickness direction satisfy the following formula [7]. LCD display:

[7] 70 ≤ Re (550) ≤ 180 and 30 ≤ Rth (550) ≤ 140

(22) The liquid crystal display device of (19), wherein the liquid crystal display device further has a second retardation film, and the wavelength dispersion of the second retardation film satisfies the following formula [8].

[8] 0.7 ≤ Re (450) / Re (550) ≤ 1.0

(23) The liquid crystal display further has a second retardation film, wherein the second retardation film is a cellulose acylate film, norbornene-based film, polycarbonate-based film, polyallylate-based film, polyester-based film and poly The liquid crystal display device of (19) which consists of either of sulfone type films.

(24) The liquid crystal display device according to (19), wherein the liquid crystal display device further has a second retardation film, and the second retardation film is directly laminated on one side of the polarizing film in an arrangement in which the absorption axes of the polarizing film are orthogonal to each other.

Carrying out the invention  Best form for

EMBODIMENT OF THE INVENTION Below, the content of this invention is demonstrated in detail. In addition, it is used by the meaning which includes with "-" the numerical value described before and after that as a lower limit and an upper limit in this specification.

In this specification, "substantially" with respect to an angle means that the error with a rigid angle exists in the range less than +/- 5 degrees. Moreover, it is preferable that it is less than 4 degrees, and, as for the error with an exact angle, it is more preferable that it is less than 3 degrees. In addition, the measurement wavelength of a refractive index is a value in (lambda) = 550 nm of visible range unless there is particular notice. In addition, in this specification, "visible light" means the light whose wavelength is 400 nm-700 nm.

Re (λ) as used in the present invention is a front retardation value (unit: nm) at a wavelength λ nm, and is represented by the following formula.

Re (λ) = (nx-ny) × d

(Wherein nx is the refractive index in the slow axis direction in the film plane, ny is the refractive index in the fast axis direction in the film plane, nz is the refractive index in the thickness direction of the film, and d is the thickness (nm) of the film.)

In addition, Rth ((lambda)) said by this invention is a retardation value (unit: nm) of the film thickness direction in wavelength (lambda), It is represented by a following formula.

Rth (λ) = {(nx + ny) / 2-nz} × d

(Wherein nx is a refractive index in the slow axis direction in the film plane, ny is a refractive index in the fast axis direction in the film plane, nz is a refractive index in the thickness direction of the film, and d is the thickness (nm) of the film.)

In this specification, Re ((lambda)) is measured by making light of wavelength (lambda) nm into a film normal line direction in KOBRA 21ADH or WR (Oji Measurement Instruments Co., Ltd. product). Rth (λ) is the axis of rotation (referred to by KoBRA 21ADH or WR) as the in-plane slow axis (KOBRA 21ADH or WR). 6 points are measured by injecting light having a wavelength of λ nm from the inclined direction from the normal direction to 50 degrees to one side with respect to the film normal direction, and measuring six points in total, and the measured retardation value and average Based on the assumption of the refractive index and the input film thickness value, KOBRA 21ADH or WR is calculated. On the other hand, the slow axis is set as the inclination axis (rotation axis) (when there is no ground axis, any direction in the film plane is used as the rotation axis), and the retardation value is measured in two arbitrary directions, and the assumption of the value and the average refractive index is performed. Based on the value and the input film thickness value, Rth may be calculated by the following formula (1) and the above formula. Here, the assumption of the average refractive index may be a polymer handbook (JOHN WILEY & SONS, INC) and catalog values of various optical films. The thing which does not know the value of an average refractive index in advance can be measured with an Abbe refractometer. The value of the average refractive index of the main optical film is illustrated below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethylmethacrylate (1.49), polystyrene (1.59). By inputting the assumption values and film thicknesses of these average refractive indices, KOBRA 21ADH or WR calculates nx, ny, and nz.

Equation (1)

Note: The above Re (θ) represents the retardation value in the direction in which the angle θ is inclined from the normal direction.

In addition, the sign of Rth defines the case where the retardation measured by injecting light of wavelength 550nm from the direction inclined +20 degree with respect to the film normal line direction using the in-plane slow axis as an inclination axis (rotation axis) exceeds (Re). And Re is negative. However, in the sample whose | Rth / Re | is 9 or more, the polarizing plate is detected in a state inclined at + 40 ° with respect to the film normal direction using the polarization microscope provided with the rotational free base as the inclination axis (rotation axis). The case where the slow axis of the sample which can be determined by using is parallel to a film plane is made into positive, and the case where the slow axis is in the thickness direction of a film is made into negative.

In addition, "substituent", such as an alkyl group, in this specification may have a substituent further, and does not need to have it unless it mentions specially.

[Retardation film]

This invention relates to the retardation film which the absolute value of Re and Rth is small, combining the support body which consists of a cellulose acylate film, and an optically anisotropic layer.

[Retardation Film of First Aspect]

As for the 1st aspect of the retardation film of this invention, the front retardation of a support body and the retardation (Rth) of thickness direction satisfy | fill following formula [1], and the wavelength dispersion property of the said support body is following formula [2] -1 In addition, by combining with the optically anisotropic layer, the front retardation (Re) and the retardation (Rth) in the thickness direction of the retardation film as a whole satisfy the following formula [3], and the wavelength dispersion property is the following formula [ It is related with retardation film which satisfy | fills 4].

[1] 0 ≤ Re (630) ≤ 10 and | Rth (630) | ≤ 25

[2] -1 | Re (400) -Re (700) | ≤ 10 and | Rth (400) -Rth (700) | ≤ 35

[3] 0 ≤ Re (550) ≤ 10 and 100 ≤ Rth (550) ≤ 300

[4] 1.04 ≤ Rth (450) / Rth (550) ≤ 1.30

The front retardation (Re (550)) of the retardation film of the 1st aspect of this invention becomes like this. Preferably it is 8 nm or less, More preferably, it is 5 nm or less, More preferably, it is 3 nm or less. Moreover, retardation (Rth (550)) of the thickness direction of retardation film becomes like this. Preferably it is 120-280 nm, More preferably, it is 140-260 nm or less, More preferably, it is 160-240 nm or less. Moreover, the wavelength dispersibility of retardation film becomes like this. Preferably it is 1.06-1.30, More preferably, it is 1.08-1.28 or less, More preferably, it is 1.10-1.26 nm or less.

Hereinafter, the preferable optical characteristic of each of a support body and an optically anisotropic layer, and the material, method, etc. which are used for manufacturing them are demonstrated.

[Support]

A cellulose acylate film is used for the support body of the retardation film of 1st aspect of this invention. A cellulose acylate film is preferable from a viewpoint that there is no absorption in visible region, light transmittance is 80% or more, and the retardation based on birefringence is small. Moreover, it is preferable also to attach it directly to a polarizing film and to be integrated with a polarizing plate, and also from the durability viewpoint of a polarizing film.

Specifically, the cellulose acylate film having a small optical anisotropy (Re, Rth) used in the first aspect of the present invention is the front retardation (Re) of the cellulose acylate film (support) and the retardation (Rth) in the thickness direction. ) Satisfies the formula [1] and the wavelength dispersibility satisfies the formula [2] -1.

The formula [1] is preferably 0 ≦ Re (630) ≦ 5 and | Rth | ≦ 20nm, more preferably 0 ≦ Re (630) ≦ 2 and | Rth | ≦ 15nm.

Formula [2] -1 is preferably | Re (400) -Re (700) | ≤ 5 and | Rth (400) -Rth (700) | ≤ 25, more preferably | Re (400)- Re (700) | ≦ 3 and | Rth (400) -Rth (700) | ≦ 15.

An example of the support body used for the retardation film of the 1st aspect of this invention can be manufactured, for example by the following method.

[Cellulose Acylate Raw Material Cotton]

As cellulose of the cellulose acylate raw material used for manufacture of the retardation film of 1st aspect of this invention, there exist cotton linter and wood pulp (softwood pulp, coniferous pulp), etc., The cellulose acylate obtained from any raw material cellulose can be used, You may mix and use as needed. For detailed descriptions of these raw celluloses, for example, plastic material courses (17) fibrous resins (Maruzawa, Uda, Nikkan Kogyo Shimbun, issued in 1970); Cellulose described in the above) can be used, and any method can be preferably employed for the cellulose acylate film used in the retardation film of the first aspect of the present invention.

[Cellulose Acylate Substitution Degree]

Next, the cellulose acylate manufactured from the above-mentioned cellulose is described. The cellulose acylate preferably used in the first embodiment is one in which the hydroxyl group of the cellulose is acylated, and the substituent may be, for example, an acetyl group having 2 to 22 carbon atoms of the acyl group. In the cellulose acylate used in the first embodiment, the degree of substitution with respect to the hydroxyl group of cellulose is not particularly limited, but the degree of binding of acetic acid and / or fatty acids having 3 to 22 carbon atoms substituted with the hydroxyl group of cellulose is measured. The substitution degree can be obtained by calculation. The measurement can be carried out in accordance with ASTM D-817-91.

In the said cellulose acylate, although it does not specifically limit about the substitution degree with respect to the hydroxyl group of cellulose, It is preferable that the acyl substitution degree with respect to the hydroxyl group of cellulose is 2.85-3.00. And it is still more preferable that substitution degree is 2.87-3.00, and it is more preferable that it is 2.90-3.00.

The acyl group having 2 to 22 carbon atoms is not particularly limited among the acetic acid and / or fatty acids having 3 to 22 carbon atoms substituted with the hydroxyl group of cellulose, and may be an aliphatic group or an allyl group, or may be one kind or two kinds. The above mixture may be sufficient. Examples of such aliphatic groups include an alkylcarbonyl ester group, an alkenylcarbonyl ester group, an aromatic carbonyl ester group, an aromatic alkylcarbonyl ester group, and the like of cellulose. These groups may be further substituted by substituents.

Specifically, as the acyl group, an acetyl group, propionyl group, butanoyl group, heptanoyl group, hexanoyl group, octanoyl group, decanoyl group, dodecanoyl group, tridecanoyl group, tetradecanoyl group, hexadecanoyl group , An octadecanoyl group, an isobutanoyl group, a tert-butanoyl group, a cyclohexanecarbonyl group, an oleyl group, a benzoyl group, a naphthylcarbonyl group, a cinnamoyl group, and the like, and an acetyl group, propionyl group, butanoyl group and dodecanoyl The diary, octadecanoyl group, tert-butanoyl group, oleoyl group, benzoyl group, naphthylcarbonyl group and cinnamoyl group are more preferable, and an acetyl group, a propionyl group, butanoyl group is still more preferable.

In particular, in the case where the total substitution degree is 2.50-3.00 in the case where it consists of two or more of the acetyl group / propionyl group / butanoyl group among the acyl substituents substituted by the hydroxyl group of the cellulose mentioned above, a cellulose acylate film Can reduce the optical anisotropy more efficiently. It is preferable that it is 2.60-3.00, and, as for an acyl substitution degree, it is more preferable that it is 2.65-3.00.

[Structural Features of Compounds Reducing the Optical Anisotropy of Cellulose Acylate Films]

The cellulose acylate film used in the first aspect may contain a compound that reduces optical anisotropy. The optical anisotropy was fully reduced by using a compound which suppresses the cellulose acylate in the film from being oriented in the in-plane and film thickness directions, so that Re is zero and Rth is close to zero. For this purpose, a compound which lowers optical anisotropy is sufficiently compatible with cellulose acylate, and it is advantageous that the compound itself does not have a rod-like structure or a planar structure. Specifically, in the case where there are a plurality of planar functional groups such as aromatic groups, a structure having these functional groups on the non-planar surface rather than on the same plane is advantageous.

(LogP value)

In producing the cellulose acylate film of the first aspect, the octanol-water partition coefficient in the compound which inhibits the cellulose acylate in the film from being oriented in the in-plane and film thickness directions and lowers the optical anisotropy as described above. The compound whose (logP value) is 0-7 is preferable. Compounds having a logP value of greater than 7 lack compatibility with cellulose acylate, and are liable to cause cloudiness or blowing of the film. Moreover, since the compound whose logP value is smaller than 0 has high hydrophilicity, the water resistance of a cellulose acylate film may deteriorate. As a logP value, the more preferable range is 1-6, Especially preferable range is 1.5-5.

The octanol-water partition coefficient (logP value) can be measured by the flask shaking method described in JIS JP Z7260-107 (2000). In addition, the octanol-water partition coefficient (logP value) may be approximated by computational chemical or empirical methods instead of actual measurements. As a calculation method, Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)), Viswanadhan's fragmentation method (J. Chem. Inf. Comput. Sci., 29, 163 (1989) .), Broto's fragmentation method (Eur. J. Med. Chem.-Chim. Theor., 19, 71 (1984).) And the like are preferably used, Crippen's fragmentation method (J. Chem. Inf. Comput. Sci. , 27, 21 (1987).). When the value of logP of a compound differs depending on the measuring method or the calculation method, it is preferable to determine whether the compound is within the range by Crippen's fragmentation method.

[Physical Properties of Compounds Degrading Optical Anisotropy]

The compound which lowers optical anisotropy may or may not contain an aromatic group. Moreover, it is preferable that molecular weight is 150-3000, as for the compound which reduces optical anisotropy, it is more preferable that it is 170-2000, It is still more preferable that it is 200-1000. If it is such a molecular weight range, a specific monomer structure may be sufficient and the oligomer structure and polymer structure which the monomer unit couple | bonded two or more may be sufficient.

The compound that lowers the optical anisotropy is preferably a liquid at 25 ° C, a solid having a melting point of 25 to 250 ° C, more preferably a liquid at 25 ° C, or a solid having a melting point of 25 to 200 ° C. Moreover, the compound which does not volatilize at the time of dope casting and a drying process at the time of preparation of a cellulose acylate film is preferable for the compound which reduces optical anisotropy.

It is preferable that it is 0.01-30 mass% of cellulose acylate, as for the addition amount of the compound which reduces optical anisotropy, it is more preferable that it is 1-25 mass%, and it is especially preferable that it is 5-20 mass%.

Only 1 type may be used for the compound which lowers optical anisotropy, and you may use it, mixing 2 or more types of compounds by arbitrary ratios.

The timing of adding the compound which lowers the optical anisotropy may be added at any time during the dope production process or at the end of the dope production process.

As for the compound which reduces optical anisotropy, the average content rate of the compound in the part from at least one surface to 10% of the total film thickness is 80- of the average content rate of the compound in the center part of the cellulose acylate film. It is preferably 99%. The amount of the compound present can be determined by measuring the amount of the compound on the surface and the central portion, for example, by using the infrared absorption spectrum described in JP-A-8-57879.

Although the compound represented by either of the following general formula (13), (18), (19) is mentioned as a specific example of the compound which reduces the optical anisotropy of the cellulose acylate film used preferably in a 1st aspect below, It is not limited to these compounds.

[Chemical Formula 1]

[In General Formula (13), R ¹ represents an alkyl group or an aryl group, and R ² and R ³ each independently represent a hydrogen atom, an alkyl group, or an aryl group. Provided that the total number of carbon atoms in R ¹ , R ² and R ³ is 10 or more.]

(2)

[In General Formula (18), R ¹ represents an alkyl group or an aryl group, and R ² and R ³ each independently represent a hydrogen atom, an alkyl group or an aryl group.]

(3)

[In General formula (19), R <^4> , R <^5> and R <^6> respectively independently represents an alkyl group or an aryl group.]

The compound of General formula (13) is demonstrated.

In General Formula (13), R ¹ represents an alkyl group or an aryl group, and R ² and R ³ each independently represent a hydrogen atom, an alkyl group, or an aryl group. Moreover, it is especially preferable that the sum total of carbon number of R <^1> , R <^2> and R <^3> is 10 or more. R ¹ , R ² and R ³ may be substituted, and as a substituent, a fluorine atom, an alkyl group, an aryl group, an alkoxy group, a sulfone group and a sulfonamide group are preferable, and an alkyl group, an aryl group, an alkoxy group, a sulfone group and a sulfonamide Group is more preferable. Further, the alkyl group may be linear, branched or cyclic, preferably having 1 to 25 carbon atoms, more preferably 6 to 25, still more preferably 6 to 20 (eg, Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, cyclohexyl, heptyl, octyl, bicyclo Octyl, nonyl, adamantyl, decyl, tert-octyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadec Practical skills, didecyl). The aryl group preferably has 6 to 30 carbon atoms, and more preferably 6 to 24 (for example, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a binaphthyl group, and a triphenylphenyl group).

Although the preferable example of a compound represented by General formula (13) is shown below, it is not limited to these specific examples.

In the formula, Pr ⁱ represents an isopropyl group.

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

Although the preferable example of the compound represented by General formula (18) or General formula (19) below is shown below, it is not limited to these specific examples. Moreover, in the compound represented by General formula (18) or (19), the specific example of an alkyl group and an aryl group is the same as that of General formula (13).

[Formula 7]

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

As a preferable example of the compound which reduces another optical anisotropy, the compound represented by following General formula (1) is mentioned.

In general formula (1)

[Chemical Formula 17]

In the said General formula (1), R <^1> represents a hydrogen atom, a substituted or unsubstituted aliphatic acyl group, or a substituted or unsubstituted aromatic acyl group. It is more preferable that it is a hydrogen atom or an aliphatic acyl group. The aliphatic acyl group may be any of linear, branched or cyclic. It is preferable that carbon number of an aliphatic acyl group is 1-12, It is more preferable that it is 1-8, It is most preferable that it is 1-4. An aromatic acyl group may be an aromatic hydrocarbon acyl group or an aromatic heterocyclic acyl group, More preferably, it is an aromatic hydrocarbon acyl group. As aromatic hydrocarbon acyl group, it is preferable that carbon number is 6-24, and it is more preferable that it is 6-12. The substituent T mentioned later is mentioned as a substituent which the aliphatic acyl group and the aromatic acyl group may have.

R <^2> , R <^3> and R <^4> represent a hydrogen atom, a substituted or unsubstituted aliphatic group, or a substituted or unsubstituted aromatic group, respectively, and an aliphatic group is more preferable. The aliphatic group may be any of linear, branched or cyclic, but is preferably branched or cyclic, and particularly preferably cyclic. It is preferable that carbon number of an aliphatic group is 5-24, It is more preferable that it is 5-15, It is most preferable that it is 5-12. An aromatic hydrocarbon group or an aromatic heterocyclic group may be sufficient as an aromatic group, More preferably, it is an aromatic hydrocarbon group. As an aromatic hydrocarbon group, it is preferable that carbon number is 6-24, and it is more preferable that it is 6-12. The substituent T mentioned later is mentioned as a substituent which an aliphatic group and an aromatic group may have.

The substituted or unsubstituted aliphatic group described above is further described below. The aliphatic group may be linear, branched or cyclic, or preferably 1 to 25 carbon atoms, preferably 5 to 24, more preferably 5 to 15, and most preferably 5 to 12. Do. Specific examples of the aliphatic group include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, tert-butyl group, amyl group, isoamyl group, tert-amyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, bicyclooctyl group, adamantyl group, n-decyl group, tert-octyl group, dodecyl group, hexadecyl group, octadecyl group, didedec Practical skills are included.

The substituted or unsubstituted aromatic group described above is further described below. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, and more preferably an aromatic hydrocarbon group. As an aromatic hydrocarbon group, it is preferable that carbon number is 6-24, and it is more preferable that it is 6-12. Specific examples of the ring possessed by an aromatic hydrocarbon group include benzene, naphthalene, anthracene, biphenyl, terphenyl and the like. As the aromatic hydrocarbon group, benzene, naphthalene and biphenyl are particularly preferable. It is preferable that an aromatic heterocyclic group contains 1 or more of an oxygen atom, a nitrogen atom, or a sulfur atom. Specific examples of the heterocycle include, for example, furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazolin, thiadiazole, Oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, Benzimidazole, benzoxazole, benzthiazole, benzotriazole, tetrazaindene. As the aromatic heterocyclic group, pyridine, triazine and quinoline are particularly preferable.

In addition, the substituent T mentioned above is demonstrated below.

Substituent T:

Alkyl group (preferably C1-C20, More preferably, it is 1-12, Especially preferably, it is 1-8, For example, a methyl group, an ethyl group, isopropyl group, tert- butyl group, n-octyl group , n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, and the like), alkenyl group (preferably 2 to 20 carbon atoms, more preferably 2 to 12) Especially preferably, it is 2-8, For example, a vinyl group, an allyl group, 2-butenyl group, 3-pentenyl group, etc. are mentioned, The alkynyl group (preferably 2-20 carbon atoms, More preferable) Preferably it is 2-12, Especially preferably, it is 2-8, For example, a propargyl group, 3-pentynyl group, etc. are mentioned, An aryl group (preferably 6-30 carbon atoms, More preferably, 6-20, Especially preferably, it is 6-12, For example, a phenyl group, a biphenyl group, a naphthyl group, etc. are mentioned. Mino group (preferably 0-20 carbon atoms, More preferably, it is 0-10, Especially preferably, it is 0-6, For example, amino group, methylamino group, dimethylamino group, diethylamino group, dibenzylamino group, etc.) And an alkoxy group (preferably 1 to 20 carbon atoms, more preferably 1 to 12, particularly preferably 1 to 8, for example, a methoxy group, an ethoxy group, a butoxy group, etc. may be mentioned. Aryloxy group (preferably 6 to 20 carbon atoms, more preferably 6 to 16, particularly preferably 6 to 12, for example, a phenyloxy group, 2-naphthyloxy group, etc.) Acyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16, particularly preferably 1 to 12, for example, an acetyl group, a benzoyl group, a formyl group, or a pivaloyl group). Etc.), an alkoxycarbonyl group (preferably a carbon source) Embroidery 2-20, More preferably, it is 2-16, Especially preferably, it is 2-12, For example, a methoxycarbonyl group, an ethoxycarbonyl group, etc. are mentioned.), An aryloxycarbonyl group (preferably carbon number) 7-20, More preferably, it is 7-16, Especially preferably, it is 7-10, For example, a phenyloxycarbonyl group etc. are mentioned.), Acyloxy group (Preferably 2-20 carbon atoms, More Preferably it is 2-16, Especially preferably, it is 2-10, For example, an acetoxy group, a benzoyloxy group, etc. are mentioned.) An acylamino group (preferably C2-C20, More preferably, Is 2-16, Especially preferably, it is 2-10, For example, an acetylamino group, a benzoylamino group, etc. are mentioned.), The alkoxycarbonylamino group (preferably C2-C20, More preferably, 2 is To 16, particularly preferably 2 12, for example, a methoxycarbonylamino group, etc.), an aryloxycarbonylamino group (preferably 7 to 20 carbon atoms, more preferably 7 to 16, particularly preferably 7 to 12). And a phenyloxycarbonylamino group, for example.), A sulfonylamino group (preferably C1-C20, More preferably, it is 1-16, Especially preferably, it is 1-12, Example Examples thereof include a methanesulfonylamino group, a benzenesulfonylamino group, and the like.), A sulfamoyl group (preferably 0 to 20 carbon atoms, more preferably 0 to 16, particularly preferably 0 to 12, For example, sulfamoyl group, methyl sulfamoyl group, dimethyl sulfamoyl group, phenyl sulfamoyl group, etc. are mentioned.), Carbamoyl group (preferably 1-20 carbon atoms, More preferably, 1-16) , Especially preferably, it is 1-12, For example And a lebamoyl group, methylcarbamoyl group, diethylcarbamoyl group, phenylcarbamoyl group and the like.), Alkylthio group (preferably 1 to 20 carbon atoms, more preferably 1 to 16, in particular) Preferably it is 1-12, for example, a methylthio group, an ethylthio group, etc. are mentioned, an arylthio group (preferably 6-20 carbon atoms, More preferably, 6-16, Especially preferably, Is 6-12, For example, a phenylthio group etc. are mentioned, A sulfonyl group (preferably C1-C20, More preferably, it is 1-16, Especially preferably, it is 1-12, Example For example, a mesyl group, a tosyl group, etc.), a sulfinyl group (preferably C1-C20, More preferably, it is 1-16, Especially preferably, it is 1-12, For example, methanesulfinyl group , Benzenesulfinyl group and the like), ureido group (preferably 1 carbon atom) 20, More preferably, it is 1-16, Especially preferably, it is 1-12, For example, a ureido group, a methylureido group, a phenylureido group, etc. are mentioned, A phosphate amide group (preferably carbon atom number) 1-20, More preferably, it is 1-16, Especially preferably, it is 1-12, For example, diethyl phosphate amide, phenyl phosphate amide, etc. are mentioned, A hydroxyl group, a mercapto group, a halogen atom (Example For example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, a sulfino group, a hydrazino group, an imino group, a heterocyclic group (preferably a carbon atom) It is 1-30, More preferably, it is 1-12, As a hetero atom, For example, a nitrogen atom, an oxygen atom, a sulfur atom, For example, an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group , Piperidyl, morpholino group And a silyl group, a benzimidazolyl group, a benzthiazolyl group, and the like, and a silyl group (preferably 3 to 40 carbon atoms, more preferably 3 to 30, particularly preferably 3 to 24). For example, a trimethylsilyl group, a triphenyl silyl group, etc. are mentioned.

These substituents may be further substituted. In addition, when there are two or more substituents, they may be same or different. Moreover, when possible, you may connect and form a ring.

Although the preferable example of the compound represented by the said General formula (1) is shown below, this invention is not limited to these specific examples.

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Wavelength dispersion regulator]

You may add the compound (henceforth a "wavelength dispersion regulator") which reduces wavelength dispersion to a cellulose acylate film. In order to improve the wavelength dispersion of Rth of the cellulose acylate film used in a 1st aspect, the compound which reduces wavelength dispersion (DELTA) Rth = | Rth (400) -Rth (700) | of Rth represented by following formula (iv) It is preferable to contain 1 or more types in the range which satisfy | fills following formula (v) and (vi).

(iv) ΔRth = | Rth (400) -Rth (700) |

(v) (ΔRth (B) -ΔRth (0)) / B ≤ -2.0

(vi) 0.01 ≦ B ≦ 30

Formula (v), (vi) is

(v) (ΔRth (B) -ΔRth (0)) / B ≤ -3.0

(vi) 0.05 ≦ B ≦ 25

It is more preferable that it is

(v) (ΔRth (B) -ΔRth (0)) / B ≤ -4.0

(vi) 0.1 ≦ B ≦ 20

More preferably.

The said wavelength dispersion regulator normally has absorption in the ultraviolet region of 200-400 nm, and adjusts wavelength dispersion of Re and Rth of a cellulose acylate film by using 0.01-30 weight% with respect to a cellulose acylate solid content, for example. Can be.

In general, the values of Re and Rth of the cellulose acylate film used in the first embodiment tend to be a wavelength dispersion characteristic in which the long wavelength side is larger than the short wavelength side. Therefore, it is required to smooth the wavelength dispersion by increasing Re and Rth on the relatively small short wavelength side. On the other hand, the compound having absorption in the ultraviolet region of 200 to 400 nm has a wavelength dispersion characteristic in which the absorbance at the long wavelength side is larger than the short wavelength side. Therefore, if the compound having absorption in the ultraviolet region of 200 to 400 nm isotropically present inside the cellulose acylate film, the birefringence of the compound itself, and further, the wavelength dispersion of Re and Rth, is similar to the wavelength dispersion of absorbance. This tends to grow.

The wavelength dispersion of Re and Rth of a cellulose acylate film can be adjusted by using the compound which has absorption in the said ultraviolet-ray region of 200-400 nm, and whose wavelength dispersion of Re and Rth of the compound itself is assumed to be large in the short wavelength side. . For this purpose, the compound adjusting the wavelength dispersion must be compatible with cellulose acylate sufficiently uniformly. The absorption band range of the ultraviolet region of such a compound is preferably 200 to 400 nm, more preferably 220 to 395 nm, further preferably 240 to 390 nm.

In recent years, liquid crystal display devices such as televisions, notebook computers, and mobile portable terminals are required to have excellent transmittance of optical members used in liquid crystal display devices in order to increase luminance with less power. In such a point, the compound which has absorption in the ultraviolet region of 200-400 nm, and reduces | reduces | Re (400) -Re (700) | and | Rth (400) -Rth (700) | of a film is a cellulose acylate film When added to, it is required to have excellent spectral transmittance. In the cellulose acylate film used for a 1st aspect, it is preferable that the spectral transmittances in wavelength 380nm are 45%-95%, and the spectral transmittances in wavelength 350 nm are 10% or less.

As mentioned above, it is preferable that the wavelength dispersion regulator used preferably in 1st aspect is 250-1000 molecular weight from a volatilization viewpoint. More preferably, it is 260-800, More preferably, it is 270-800, Especially preferably, it is 300-800. The wavelength dispersion regulator may be any of a monomer and an oligomer or a polymer to which the monomer is linked.

It is preferable that the wavelength dispersion regulator which can be used in a 1st aspect does not volatilize in the dope casting | flow_spread and a drying process at the time of producing a cellulose acylate film.

(Addition amount of wavelength dispersion regulator)

It is preferable that it is 0.01-30 weight% of a cellulose acylate, It is more preferable that it is 0.1-20 weight%, It is still more preferable that it is 0.2-10 weight% of the addition amount of the wavelength-dispersion regulator which can be used in a 1st aspect.

(Addition method of wavelength dispersion regulator)

One type of wavelength dispersion regulator which can be used by a 1st aspect may be used, and 2 or more types may be mixed and used in arbitrary ratios.

Moreover, it is preferable to perform at the end of a dope manufacturing process in the dope manufacturing process for film forming the cellulose acylate film used by a 1st aspect at the time of adding a wavelength dispersion regulator.

As a specific example of the wavelength dispersion regulator used preferably for a 1st aspect, a benzotriazole type compound, a benzophenone type compound, the compound containing a cyano group, an oxybenzophenone type compound, a salicylic acid ester type compound, a nickel complex salt type compound, etc. Although these are mentioned, It is not limited only to these compounds.

As a benzotriazole type compound, what is represented by General formula (101) is used preferably.

General formula (101)

Q ¹ -Q ² -OH

(Wherein, Q ¹ represents a nitrogen-containing aromatic heterocycle, Q ² represents an aromatic ring.)

Q ¹ represents a nitrogen-containing aromatic heterocycle, preferably a nitrogen-containing aromatic heterocycle of 5 to 7 membered rings, more preferably a 5 to 6 membered ring nitrogen-containing aromatic heterocycle, for example, imida Sol ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, oxazole ring, selenazole ring, benzotriazole ring, benzothiazole ring, benzoxazole ring, benzo selenazole ring, thiadiazole ring, oxadiazole ring, naphthothiazole ring, naph A toxoazole ring, an azabenzimidazole ring, a purine ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazaindene ring, a tetrazaindene ring, etc. are mentioned, More preferably, a 5-membered ring A nitrogen-containing aromatic heterocyclic ring, specifically, an imidazole ring, a pyrazole ring, a triazole ring, a tetrazole ring, a thiazole ring, an oxazole ring, a benzotriazole ring, a benzothiazole ring, a benzoxazole ring, a thia The azole ring, may be made of oxadiazole jolhwan, particularly preferably benzotriazole jolhwan.

The nitrogen-containing aromatic heterocycle represented by Q ¹ may further have a substituent, and the substituent T described later may be applied as the substituent. In addition, when there are two or more substituents, each may be condensed and may form a ring again.

The aromatic ring represented by Q ² may be an aromatic hydrocarbon ring or an aromatic hetero ring. In addition, these may be mono-cyclic and may form another ring and a condensed ring again.

The aromatic hydrocarbon ring is preferably a monocyclic or bicyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms (benzene ring, naphthalene ring, etc.), more preferably an aromatic hydrocarbon ring having 6 to 20 carbon atoms, still more preferably. Preferably it is a C6-C12 aromatic hydrocarbon ring, Especially preferably, it is a benzene ring.

As an aromatic hetero ring, the aromatic hetero ring containing a nitrogen atom or a sulfur atom is preferable. Specific examples of the hetero ring include thiophene ring, imidazole ring, pyrazole ring, pyridine ring, pyrazine ring, pyridazine ring, triazole ring, triazine ring, indole ring, indazole ring, purine ring, thiazolin ring, thiazole ring, Thiadiazole ring, oxazoline ring, oxazole ring, oxadiazole ring, quinoline ring, isoquinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, pteridine ring, acridine ring, Phenanthroline ring, phenazine ring, tetrazole ring, benzimidazole ring, benzoxazole ring, benzthiazole ring, benzotriazole ring and tetrazaindene ring. As a specific example of an aromatic heterocyclic ring, a pyridine ring, a triazine ring, and a quinoline ring are mentioned.

Preferably an aromatic ring represented by Q ² is an aromatic hydrocarbon ring, more preferably a naphthalene ring, a benzene ring, and more preferably a benzene ring. Q ² may further have a substituent, and substituent T described later is preferable.

As the substituent T, for example, an alkyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, for example, methyl, ethyl, iso Propyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc. can be mentioned), alkenyl group (preferably carbon 2-20 atoms, More preferably, it is 2-12 carbon atoms, Especially preferably, it is 2-8 carbon atoms, For example, a vinyl group, an allyl group, 2-butenyl group, 3-pentenyl group, etc. are mentioned. Alkynyl group (preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, for example, propargyl group and 3-penty). And an aryl group (preferably 6 to 30 carbon atoms), more preferably 6-20 small atoms, Especially preferably, it is 6-12 carbon atoms, For example, a phenyl group, p-methylphenyl group, a naphthyl group, etc. are mentioned, An amino group (preferably carbon number of 0-20, More preferably, they are 0-10 carbon atoms, Especially preferably, they are 0-6 carbon atoms, For example, an amino group, a methylamino group, a dimethylamino group, a diethylamino group, a dibenzylamino group, etc.), an alkoxy group (Preferably, it is C1-C20, More preferably, it is C1-C12, Especially preferably, it is C1-C8, For example, a methoxy group, an ethoxy group, butoxy group etc. are mentioned. ), An aryloxy group (preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, for example, a phenyloxy group or 2-naphthyl jade) Seasons, etc.) Preferably it is C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, an acetyl group, benzoyl group, formyl group, pivaloyl group etc. are mentioned. Alkoxycarbonyl group (preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, for example, a methoxycarbonyl group and ethoxy Carbonyl group, etc.), aryloxycarbonyl group (preferably 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms, for example, phenyl An oxycarbonyl group, etc.), an acyloxy group (preferably C2-C20, More preferably, it is C2-C16, Especially preferably, it is C2-C10, For example, ace Oxy group, benzoyloxy And acylamino groups (preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, for example, an acetylamino group, A benzoylamino group, etc.), an alkoxycarbonylamino group (preferably 2-20 carbon atoms, More preferably, it is 2-16 carbon atoms, Especially preferably, it is 2-12 carbon atoms, for example, A methoxycarbonylamino group etc. are mentioned, The aryloxycarbonylamino group (preferably C7-C20, More preferably, it is C7-C16, Especially preferably, it is C7-C12 For example, a phenyloxycarbonylamino group etc. are mentioned, sulfonylamino group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C1 One 2, for example, methanesulfonylamino group, benzenesulfonylamino group, etc.), sulfamoyl group (preferably 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, particularly preferably Is 0-12 carbon atoms, for example, a sulfamoyl group, methyl sulfamoyl group, dimethyl sulfamoyl group, phenyl sulfamoyl group, etc.), carbamoyl group (preferably 1-20 carbon atoms) More preferably, they are C1-C16, Especially preferably, it is C1-C12, For example, a carbamoyl group, a methyl carbamoyl group, a diethyl carbamoyl group, a phenylcarbamoyl group, etc. are mentioned. Alkylthio group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, methylthio group, ethyl tea Ogi etc.), an arylthio group (preferably Crab has 6-20 carbon atoms, More preferably, it has 6-16 carbon atoms, Especially preferably, it has 6-12 carbon atoms, For example, a phenylthio group etc. are mentioned, A sulfonyl group (preferably Is C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, a mesyl group, a tosyl group, etc. are mentioned, A sulfinyl group (preferably Preferably it is C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, methane sulfinyl group, a benzene sulfinyl group, etc. are mentioned), Pottery (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, a ureido group, a methyl ureido group, a phenyl ureido group, etc.) Phosphate amide group (preferably Small atoms of 1 to 20, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, diethyl phosphate amide, phenyl phosphate amide, etc.), a hydroxy group, Mercapto group, halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, Heterocyclic group (preferably C1-C30, More preferably, it is 1-12, As a hetero atom, For example, a nitrogen atom, an oxygen atom, a sulfur atom, For example, an imidazolyl group, a pyri Diyl group, quinolyl group, furyl group, piperidyl group, morpholino group, benzoxazolyl group, benzimidazolyl group, benzthiazolyl group, etc.), silyl group (preferably having 3 to 3 carbon atoms) 40, More preferably, it is 3-30 carbon atoms, Especially preferably, it is C3-C24, for example, a trimethylsilyl group, a triphenylsilyl group, etc. are mentioned. These substituents may be further substituted. In addition, when there are two or more substituents, they may be same or different. In addition, if possible, they may be connected to each other to form a ring.

As general formula (101), it is preferably a compound represented with the following general formula (101-A).

General formula (101-A)

[Chemical Formula 21]

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ each independently represent a hydrogen atom or a substituent)

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ each independently represent a hydrogen atom or a substituent, and the substituents may apply the above-mentioned substituent T. In addition, these substituents may be further substituted by other substituents, and the substituents may be condensed to form a ring structure.

R ¹ and R ³ are preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a hydroxy group, a halogen atom, and more preferably a hydrogen atom, an alkyl group, an aryl group, It is an alkoxy group, an aryloxy group, and a halogen atom, More preferably, it is a hydrogen atom and an alkyl group of 1 to 12 carbon atoms, Especially preferably, an alkyl group of 1 to 12 carbon atoms (preferably 4 to 12 carbon atoms) ) to be.

R ² and R ⁴ are preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a hydroxy group, a halogen atom, and more preferably a hydrogen atom, an alkyl group, an aryl group, It is an alkoxy group, an aryloxy group, a halogen atom, More preferably, it is a hydrogen atom and an alkyl group of 1-12 carbon atoms, Especially preferably, it is a hydrogen atom and a methyl group, Most preferably, it is a hydrogen atom.

R ⁵ and R ⁸ are preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a hydroxy group, a halogen atom, and more preferably a hydrogen atom, an alkyl group, an aryl group, It is an alkoxy group, an aryloxy group, a halogen atom, More preferably, it is a hydrogen atom and an alkyl group of 1-12 carbon atoms, Especially preferably, it is a hydrogen atom and a methyl group, Most preferably, it is a hydrogen atom.

R ⁶ and R ⁷ are preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a hydroxy group, a halogen atom, and more preferably a hydrogen atom, an alkyl group, an aryl group, It is an alkoxy group, an aryloxy group, and a halogen atom, More preferably, they are a hydrogen atom and a halogen atom, Especially preferably, they are a hydrogen atom and a chlorine atom.

As general formula (101), It is a compound represented by following General formula (101-B) more preferably.

General formula (101-B)

[Chemical Formula 22]

(In formula, R <^1> , R <^3> , R <^6> and R <^7> is synonymous with those in general formula (101-A), and its preferable range is also the same.)

Although the specific example of a compound represented by General formula (101) below is shown, it is not limited to the following specific example.

(23)

&Lt; EMI ID =

Among the benzotriazole-based compounds exemplified above, it was confirmed that the cellulose acylate film containing no one having a molecular weight of 320 or less was advantageous in terms of retention of the phase difference film obtained.

Moreover, as a benzophenone type compound which is one of the wavelength dispersion regulators which can be used by a 1st aspect, what is represented by General formula (102) is used preferably.

General formula (102)

(25)

(Wherein, Q ¹ and Q ² each represent an aromatic ring. X represents NR (R represents a hydrogen atom or a substituent), an oxygen atom or a sulfur atom.)

The aromatic ring represented by Q ¹ and Q ² may be an aromatic hydrocarbon ring or an aromatic hetero ring. In addition, these may be mono-cyclic and may form another ring and a condensed ring again.

The aromatic hydrocarbon ring represented by Q ¹ and Q ² is preferably a monocyclic or bicyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms (for example, a benzene ring and a naphthalene ring), and more preferably 6 carbon atoms. It is an aromatic hydrocarbon ring of -20, More preferably, it is an aromatic hydrocarbon ring of 6-12 carbon atoms. Especially preferably, it is a benzene ring.

As an aromatic heterocycle represented by Q <^1> and Q <^2> , Preferably, it is an aromatic heterocyclic ring containing any one or more of an oxygen atom, a nitrogen atom, or a sulfur atom. As a specific example of a hetero ring, For example, a furan ring, a pyrrole ring, a thiophene ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a triazole ring, a triazine ring, an indole ring, an indazole ring, Purine ring, thiazolin ring, thiazole ring, thiadiazole ring, oxazoline ring, oxazole ring, oxadiazole ring, quinoline ring, isoquinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline Ring, pteridine ring, acridine ring, phenanthroline ring, phenazine ring, tetrazole ring, benzimidazole ring, benzoxazole ring, benzthiazole ring, benzotriazole ring, tetrazaindene ring and the like. As an aromatic hetero ring, Preferably, they are a pyridine ring, a triazine ring, and a quinoline ring.

The aromatic ring represented by Q ¹ and Q ² is preferably an aromatic hydrocarbon ring, more preferably an aromatic hydrocarbon ring having 6 to 10 carbon atoms, still more preferably a benzene ring.

Q ¹ and Q ² may further have a substituent, and the aforementioned substituent T is preferable, but the substituent does not contain carboxylic acid, sulfonic acid or quaternary ammonium salt. If possible, substituents may be linked to each other to form a ring structure.

X represents NR (R represents a hydrogen atom or a substituent. The substituent T described above can be applied as a substituent), represents an oxygen atom or a sulfur atom, and NR (preferably R is an acyl group, sulfonyl group). These substituents may further be substituted) or an oxygen atom is preferable, and an oxygen atom is especially preferable.

As general formula (102), it is preferably a compound represented by the following general formula (102-A).

General formula (102-A)

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(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or a substituent.)

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ^8, and R ⁹ each independently represent a hydrogen atom or a substituent, and the substituent T described above may be applied as the substituent. In addition, these substituents may be further substituted by another substituent, and substituents may be condensed to form a ring structure.

R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ and R ⁹ are preferably hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, amino group, alkoxy group, aryloxy group, hydroxy group, halogen An atom, more preferably a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, still more preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, particularly preferably a hydrogen atom, It is a methyl group, Most preferably, it is a hydrogen atom.

R ² is preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a hydroxy group or a halogen atom, and more preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. , An amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, and a hydroxy group, more preferably an alkoxy group having 1 to 20 carbon atoms, particularly Preferably they are alkoxy groups of 1 to 12 carbon atoms.

R ⁷ is preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a hydroxy group or a halogen atom, and more preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. , An amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, and a hydroxy group, and more preferably a hydrogen atom and an alkyl group having 1 to 20 carbon atoms ( Preferably they are 1-12 carbon atoms, More preferably, they are 1-8 carbon atoms, More preferably, they are a methyl group, Especially preferably, they are a methyl group and a hydrogen atom.

As general formula (102), It is a compound represented by following General formula (102-B) more preferably.

General formula (102-B)

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In which R ¹⁰ Represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group.)

R <^10> represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, and an aryl group, The substituent T mentioned above is preferable as a substituent which these groups have.

R ¹⁰ is preferably an alkyl group, more preferably an alkyl group having 5 to 20 carbon atoms, still more preferably an alkyl group having 5 to 12 carbon atoms (eg, n-hexyl group, 2-ethylhexyl group, n). -Octyl group, n-decyl group, n-dodecyl group, benzyl group and the like), and particularly preferably an alkyl group having 6 to 12 carbon atoms (2-ethylhexyl group, n-octyl group, n-decyl group, n-dodecyl group, benzyl group).

The compound represented by General formula (102) can be synthesize | combined by the well-known method of Unexamined-Japanese-Patent No. 11-12219.

Although the specific example of a compound represented by General formula (102) below is given, it is not limited to the following specific example.

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[Chemical Formula 29]

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Moreover, as a compound containing the cyano group which is one of the wavelength dispersion regulators which can be used for a 1st aspect, what is represented by General formula (103) is used preferably.

General formula (103)

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(In formula, Q <^1> and Q <^2> represent an aromatic ring each independently. X <^1> and X <^2> represent a hydrogen atom or a substituent, and at least one represents a cyano group, a carbonyl group, a sulfonyl group, and an aromatic heterocycle.)

The aromatic ring represented by Q ¹ and Q ² may be an aromatic hydrocarbon ring or an aromatic hetero ring. In addition, these may be mono-cyclic and may form another ring and a condensed ring again.

As an aromatic hydrocarbon ring, Preferably it is a C6-C30 monocyclic or 2 ring aromatic hydrocarbon ring (for example, a benzene ring, a naphthalene ring, etc.), More preferably, an aromatic hydrocarbon ring of 6-20 carbon atoms, More preferably, it is a C6-C12 aromatic hydrocarbon ring, Especially preferably, it is a benzene ring.

As an aromatic hetero ring, Preferably, it is an aromatic hetero ring containing a nitrogen atom or a sulfur atom. As a specific example of a hetero ring, For example, a thiophene ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a triazole ring, a triazine ring, an indole ring, an indazole ring, a purine ring, a thiazolin ring , Thiazole ring, thiadiazole ring, oxazoline ring, oxazole ring, oxadiazole ring, quinoline ring, isoquinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, pteridine ring, Acridine ring, phenanthroline ring, phenazine ring, tetrazole ring, benzimidazole ring, benzoxazole ring, benzthiazole ring, benzotriazole ring, tetrazaindene ring, etc. are mentioned. As an aromatic hetero ring, Preferably, they are a pyridine ring, a triazine ring, and a quinoline ring.

As an aromatic ring represented by Q <^1> and Q <^2> , Preferably it is an aromatic hydrocarbon ring, More preferably, it is a benzene ring.

Q ¹ and Q ² may further have a substituent, and the aforementioned substituent T is preferable.

X ¹ and X ² represent a hydrogen atom or a substituent, and at least one of them represents a cyano group, a carbonyl group, a sulfonyl group or an aromatic heterocycle. The substituent represented by X <^1> and X <^2> can apply the above-mentioned substituent T. Moreover, the substituent represented by X <^1> and X <^2> may further be substituted by the other substituent, and X <^1> and X <^2> may be condensed, respectively, and may form ring structure.

X ¹ and X ² are preferably a hydrogen atom, an alkyl group, an aryl group, a cyano group, a nitro group, a carbonyl group, a sulfonyl group, an aromatic heterocycle, and more preferably a cyano group, a carbonyl group, a sulfonyl group, an aromatic heterocycle More preferably, it is a cyano group and a carbonyl group, Especially preferably, it is a cyano group, an alkoxycarbonyl group (-C (= O) OR (R: C1-C20 alkyl group, C6-C12 aryl group) And combinations thereof)).

As general formula (103), it is a compound preferably represented by the following general formula (103-A).

General formula (103-A)

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(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^9, and R ¹⁰ each independently represent a hydrogen atom or a substituent. X ¹ and X ² are It is synonymous with those in General formula (103), and its preferable range is also the same.)

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent, and as the substituents, the aforementioned substituent T may be applied. Can be. In addition, these substituents may be further substituted by another substituent, and substituents may be condensed and they may form a ring structure.

R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ are preferably hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, amino group, alkoxy group, aryloxy group, It is a hydroxyl group, a halogen atom, More preferably, it is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, More preferably, it is a hydrogen atom and an alkyl group of 1-12 carbon atoms, Especially preferably, It is a hydrogen atom and a methyl group, Most preferably, it is a hydrogen atom.

R ³ and R ⁸ are preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a hydroxy group or a halogen atom, and more preferably a hydrogen atom or 1 to 1 carbon atom. It is a 20 alkyl group, a C0-20 amino group, a C1-C12 alkoxy group, a C6-C12 aryloxy group, and a hydroxyl group, More preferably, it is a hydrogen atom and C1-C12 It is an alkyl group and a C1-C12 alkoxy group, Especially preferably, it is a hydrogen atom.

As general formula (103), It is a compound represented by following General formula (103-B) more preferably.

General formula (103-B)

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(In formula, R <^3> and R <^8> is synonymous with those in general formula (103-A), and its preferable range is also the same. X <^3> represents a hydrogen atom or a substituent.)

X <^3> represents a hydrogen atom or a substituent, The substituent T mentioned above can be applied as a substituent, and if possible, may be substituted further by another substituent. X ³ is preferably a hydrogen atom, an alkyl group, an aryl group, a cyano group, a nitro group, a carbonyl group, a sulfonyl group, an aromatic heterocyclic ring, more preferably a cyano group, a carbonyl group, a sulfonyl group, an aromatic heterocyclic ring, and more preferably Preferably it is a cyano group and a carbonyl group, Especially preferably, a cyano group, an alkoxycarbonyl group (-C (= O) OR (R is; C1-C20 alkyl group, C6-C12 aryl group, and combinations thereof) Is one)).

As general formula (103), it is more preferably a compound represented by general formula (103-C).

General formula (103-C)

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(In formula, R <^3> and R <^8> is synonymous with those in general formula (103-A), and its preferable range is also the same. R <^21> represents the C1-C20 alkyl group. "

As R <^21> , Preferably, when R <^3> and R <^8> are both hydrogen, it is a C2-C12 alkyl group, More preferably, it is a C4-C12 alkyl group, More preferably, a carbon atom It is a C6-C12 alkyl group, Especially preferably, it is n-octyl group, tert-octyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group, Most preferably, it is 2-ethylhexyl group .

As R <^21> , Preferably, when R <^3> and R <^8> is other than hydrogen, the molecular weight of the compound represented by General formula (103-C) will be 300 or more, and the alkyl group of 20 carbon atoms or less Is preferred.

The compound represented by General formula (103) can be synthesize | combined by the method as described in Journal of American Chemical Society, Vol. 63, Page 3452 (1941).

Although the specific example of a compound represented by General formula (103) below is given, it is not limited to the following specific example.

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[Formula 37]

In a 1st aspect, it is preferable that the thickness of the cellulose acylate film used as a support body is 10-120 micrometers.

[Retardation Film of Second Embodiment]

The retardation film of a 2nd aspect is related with the retardation film which the absolute value of Re and Rth is small, combining the support body which consists of a cellulose acylate film containing 1 or more types of acryl system polymers, and an optically anisotropic layer. Specifically, the front retardation of the support and the retardation Rth in the thickness direction satisfy the following formula [1], and the wavelength dispersion of the support satisfies the following formula [2] -2, and the optical thereon By combining with an anisotropic layer, as a whole retardation film, front retardation (Re) and retardation (Rth) of thickness direction satisfy | fill the following formula [3], and wavelength dispersion property satisfy | fills following formula [4] It is about a film.

[1] 0 ≤ Re (630) ≤ 10 and | Rth (630) | ≤ 25

[2] -2 | Re (400) -Re (700) | ≤ 10 and -35 ≤ Rth (400) -Rth (700) ≤ 60

[3] 0 ≤ Re (550) ≤ 10 and 100 ≤ Rth (550) ≤ 300

[4] 1.04 ≤ Rth (450) / Rth (550) ≤ 1.30

The front retardation (Re (550)) of the retardation film of a 2nd aspect becomes like this. Preferably it is 8 nm or less, More preferably, it is 5 nm or less, More preferably, it is 3 nm or less. Moreover, retardation (Rth (550)) of the thickness direction of retardation film becomes like this. Preferably it is 120-280 nm, More preferably, it is 140-260 nm, More preferably, it is 160-240 nm. Moreover, the wavelength dispersibility of retardation film becomes like this. Preferably it is 1.06-1.30, More preferably, it is 1.08-1.28, More preferably, it is 1.10-1.26.

The support body used for the retardation film of a 2nd aspect is a cellulose acylate film containing 1 or more types of acrylic polymer. As for the cellulose acylate film, the front retardation (Re) of the cellulose acylate film (support) and the retardation (Rth) in the thickness direction satisfy the above formula [1], and the wavelength dispersibility is in the above formula. [2] -2 is satisfied.

It is preferable that Re and Rth of the cellulose acylate film used as the said support body satisfy | fill following formula [1] ', and it is more preferable to satisfy following formula [1]' '.

[1] '0 ≤ Re (630) ≤ 5 and | Rth (630) | ≤ 20nm

[1] '' 0 ≤ Re (630) ≤ 2 and | Rth (630) | ≤ 15nm

In addition, the wavelength dispersion of the support preferably satisfies the following formula [2] '-2, and more preferably satisfies the following formula [2]' '-2.

[2] '-2 | Re (400) -Re (700) | ≤ 10 and 0 ≤ Rth (400) -Rth (700) ≤ 60

[2] ''-2 | Re (400) -Re (700) | ≤ 5 and 0 ≤ Rth (400) -Rth (700) ≤ 45

About the raw material of the said cellulose acylate, it is the same as that of the said 1st aspect.

The cellulose acylate used for the manufacture of the cellulose acylate film of the second example is that the hydroxyl group of the cellulose is acylated, for example, to use a cellulose acylate substituted with an acetyl group having 2 to 22 carbon atoms of the acyl group. desirable. The degree of substitution with respect to the hydroxyl group of cellulose is not particularly limited, but it is preferable that the degree of acyl substitution with respect to the hydroxyl group of cellulose is 2.70 to 3.00. Moreover, it is preferable that substitution degree is 2.80-3.00, and it is more preferable that it is 2.85-3.00.

In particular, in the acyl substituent substituted by the hydroxyl group of the above-mentioned cellulose, when it consists of two or more types of an acetyl group / propionyl group / butanoyl group, when the total substitution degree is 2.70-3.00, a cellulose acylate The optical anisotropy of a film can be reduced more effectively, and the cellulose acylate film which satisfy | fills said Formula [1] and [2] can be manufactured stably. It is preferable that it is 2.75-3.00, and, as for an acyl substitution degree, it is more preferable that it is 2.80-3.00.

About others, it is the same as the preferable example of the cellulose acylate used for manufacture of the cellulose acylate film of a 1st aspect.

[Acrylic polymer]

In the retardation film of a 2nd aspect, the cellulose acylate film used as a support body contains 1 or more types of acrylic polymer. In addition, in this specification, an "acrylic-type polymer" means the homopolymer and copolymer which make acrylic acid and its derivative (it contains not only acrylic acid ester but acrylic acid and acrylic acid ester which have substituents, such as a hydroxyl group), and a methacrylic acid, and It is a general term for the homopolymer and copolymer which make the derivative (it contains not only methacrylic acid ester but methacrylic acid and methacrylic acid ester which have substituents, such as a hydroxyl group) as a monomer.

The said acryl-type polymer reduces the optical anisotropy of the film by adding in a cellulose acylate film. In 2nd aspect, it is preferable to use the acryl-type polymer whose weight average molecular weights are 500 or more and less than 10,000 (more preferably, 500-5,000). When the weight average molecular weight is in the above range, compatibility with the cellulose ester is good, and evaporation and volatilization are less likely to occur during film formation. In particular, the (meth) acrylic acid or the (meth) acrylic acid ester type polymer, the acryl-type polymer which has an aromatic ring in a side chain, or the acryl-type polymer which has a cyclohexyl group in a side chain is the said molecular weight, In addition to the above, the cellulose acylate film obtained is It is excellent in transparency, and its water vapor transmission rate is also very low, and therefore shows the outstanding performance also as a protective film for polarizing plates.

Moreover, although represented by the acryl-type polymer, the acryl-type polymer whose weight average molecular weights are 500 or more and less than 10,000 exists between an oligomer and a low molecular weight polymer. In order to synthesize | combine such a polymer, it is preferable to use the method which can make molecular weight as uniform as possible by the method which does not control molecular weight hardly by normal polymerization and does not increase molecular weight very much. As such a polymerization method, a method of using a peroxide polymerization initiator such as cumene peroxide or t-butyl hydroperoxide, a method of using a polymerization initiator in a larger amount than normal polymerization, a mercapto compound, carbon tetrachloride, etc. in addition to the polymerization initiator A method of using a chain transfer agent, a method of using a polymerization terminator such as benzoquinone or dinitrobenzene in addition to a polymerization initiator, and a single thiol group and a second class in JP 2000-128911 or 2000-344823 A method of bulk polymerization using the compound which has a hydroxyl group of this, or the polymerization catalyst which used the compound and the organometallic compound together, etc. are mentioned, Although either method is preferably used for 2nd aspect, Especially The method described in the publication is preferred.

Although the monomer as a monomer unit which comprises the said acrylic polymer is illustrated below, it is not limited to this.

Examples of the monomer unit constituting the polymer include: methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), butyl acrylate (n-, i-, s-, t-) and pentyl acrylate (n- , i-, s-), hexyl acrylate (n-, i-), heptyl acrylate (n-, i-), octyl acrylate (n-, i-), nonyl acrylate (n-, i-), acrylate Steel (n-, i-), cyclohexyl acrylate, acrylic acid (2-ethylhexyl), benzyl acrylate, phenethyl acrylate, acrylic acid (ε-caprolactone), acrylic acid (2-hydroxyethyl), acrylic acid (2-hydric Hydroxypropyl), acrylic acid (3-hydroxypropyl), acrylic acid (4-hydroxybutyl), acrylic acid (2-hydroxybutyl), acrylic acid (2-methoxyethyl), acrylic acid (2-ethoxyethyl), acrylic acid Phenyl, acrylic acid (2 or 4-chlorophenyl), acrylic acid (2 or 3 or 4-ethoxycarbonylphenyl), acrylic acid (o or m or p-tolyl), benzyl acrylate, phenethyl acrylate, acrylic acid (2-naph Teal), acrylic acid Chlorohexyl, acrylic acid (4-methylcyclohexyl), acrylic acid (4-ethylchlorohexyl), acrylic acid -p-hydroxymethylphenyl, acrylic acid -p- (2-hydroxyethyl) phenyl; As methacrylic acid ester, what changed the said acrylic acid ester into methacrylic acid ester; Examples of the unsaturated acid include acrylic acid, methacrylic acid, maleic anhydride, crotonic acid, itaconic acid, and the like. The polymer composed of the monomer may be a copolymer or a homopolymer.

When the said acryl-type polymer has a hydroxyl group in a principal chain and / or a side chain, since compatibility with a cellulose acylate and transparency of the film obtained are improved significantly, it is preferable. The acrylic polymer which has a hydroxyl group in a side chain can be manufactured by using the (meth) acrylic acid derivative which has a hydroxyl group (for example, the compound which has a hydroxyl group in the ester part of (meth) acrylic acid ester) as a monomer. Specific examples of the (meth) acrylic acid derivative having a hydroxyl group include acrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), acrylic acid (3-hydroxypropyl), acrylic acid (4-hydroxybutyl), and acrylic acid. (2-hydroxybutyl), acrylic acid-p-hydroxymethylphenyl, acrylic acid-p- (2-hydroxyethyl) phenyl and the like; The thing which replaced the said acrylic acid ester with methacrylic acid ester is included.

As an acrylic polymer which has a hydroxyl group in a side chain, the copolymer of the compound which has a hydroxyl group in the ester part of an acrylic acid ester, and the methacrylic acid ester (compound which does not have a hydroxyl group in an ester part) are especially preferable.

Moreover, as above-mentioned, the acryl-type polymer which has a hydroxyl group in a principal chain, especially a hydroxyl group in at least one terminal of a polymer main chain is also preferable. In order to manufacture the polymer which has a hydroxyl group in a principal chain terminal, For example, the method of using the radical polymerization initiator which has a hydroxyl group, such as azobis (2-hydroxyethyl butyrate); A method of using a chain transfer agent having a hydroxyl group such as 2-mercaptoethanol; A method of using a polymerization terminator having a hydroxyl group; A method of having a hydroxyl group at a terminal by living ion polymerization; A method of bulk polymerization using a compound having one thiol group and a secondary hydroxyl group in JP-A-2000-128911 or 2000-344823, or a polymerization catalyst using the compound and an organometallic compound in combination; And the like, and the method described in the above publication is particularly preferable. The polymer produced by the method according to this publication is commercially available as an ACTFLOW series manufactured by Soken Chemical Co., Ltd., and can be preferably used.

In addition, you may add the compound and wavelength dispersion regulator which reduce optical anisotropy to the cellulose acylate film used as a support body of the retardation film of a 2nd aspect. The specific example, addition method, etc. are the same as that of the said 1st aspect.

In a 2nd aspect, it is preferable that the thickness of the cellulose acylate film used as a support body is 10-60 micrometers.

[Plasticizer]

It is preferable to add a plasticizer to the cellulose acylate film which can be used as a support body in this invention, especially the cellulose acylate film used as a support body in 2nd aspect in the point which improves brittleness of a film. Specifically, generation of cracks and the like during film cutting can be prevented. As a compound which has a plasticizing effect, the compound which has functional groups, such as a phosphate ester, a carboxylic acid ester, an amide, an ether, and a urethane, is preferable. Although the following are mentioned as an example of such a preferable compound, It is not limited to these.

Examples of the phosphate esters include triphenyl phosphate, biphenyl diphenyl phosphate, tricredil phosphate, credil diphenyl phosphate, octyl diphenyl phosphate, trioctyl phosphate, tributyl phosphate, resorcinol bis diphenyl phosphate and 1,3-phenyl. Lenbisdic silenyl phosphate, bisphenol A bis diphenyl phosphate, etc. are mentioned.

As carboxylic acid ester, polyhydric alcohols, such as trimethylol propane tribenzoate, trimethylol propane tricyclohexyl carboxylate, pentaerythritol tetrabutylate, glycerin tributylate, triacetin, tributyrin, and tripropionine Carboxylic acid ester of; Dibutyl succinate, diphenyl adipic acid, dibutyl phthalate, diaryl phthalate, dimethyl phthalate, diethyl phthalate, di-2-methoxyethyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate phthalate, trimethyl trimellitate Saturated, unsaturated polyhydric carboxylic acid esters such as tetraethyl pyromellitate acid; Oligomers of methyl methacrylate and ethyl acrylate; And the like.

As esters of oxyacids, glycols such as triethyl citrate, acetyl triethyl citrate, dibutyl tartrate, dibutyl diacetyl tartrate, butyl phthalyl butyl glycolate, ethyl phthalyl ethyl glycolate and methyl phthalyl ethyl glycolate Esters of oxyacids such as acid, salicylic acid, citric acid, malic acid and tartaric acid.

Examples of the amides include carboxylic acid amides and sulfonic acid amides such as N-phenyl-benzenecarboxyamide, N-phenyl-p-toluenesulfonamide and N-ethyltoluenesulfonamide.

In addition, sulfonic acid esters, such as p-toluenesulfonic acid o-credyl, urethane by reaction of toluene diisocyanate, and alcohol, such as ethanol and hexyl alcohol, etc. are mentioned.

Ether oligomers, such as glycidyl ether of bisphenol A, and low molecular weight oligomers, such as urethane oligomer by reaction of toluene diisocyanate, dihydric alcohol, and monohydric alcohol mixture, are also mentioned as a preferable example.

In addition, trityl alcohol etc. are mentioned as a preferable example.

5-30 mass parts is preferable with respect to 100 mass parts of cellulose acylate, and, as for the addition amount of the compound which shows such a plasticizing effect, 10-25 mass parts is more preferable.

In addition to the cellulose acylate films used in the first and second aspects, matte fine particles, deterioration inhibitors, release agents and the like may be added as additives that have conventionally been used in cellulose acylate films. Specifically, the compound described in [0212] to [0219] of JP 2006-30937 A and its usage are used.

It is preferable to manufacture the cellulose acylate film used as a support body in a 1st and 2nd aspect by the solvent cast method, Specifically, to the method of Unexamined-Japanese-Patent No. 2006-30937-[0225] It is preferable to manufacture by.

[Optical anisotropic layer]

The retardation film of the present invention (hereinafter, referred to as "the retardation film of the present invention" means a meaning including both of the first and second retardation films) has one or more optically anisotropic layers on the support. . Basically, as long as it becomes the retardation film of this invention which satisfy | fills the said optical characteristic by laminating | stacking with the said support body which has predetermined optical characteristic, it does not restrict | limit especially about the material and a form. For example, a polymer film (preferably a retardation film composed of a birefringent polymer film) may be used, or a film obtained by forming a layer containing a polymer compound on a support and then heating and stretching the film, and the liquid crystal composition may be a predetermined film. After making it into a liquid crystal phase, the layer formed by fixing in that state may be sufficient. Moreover, you may laminate | stack each.

[Optical Anisotropic Layer Formed from Polymerizable Liquid Crystal Composition]

It is preferable that the said optically anisotropic layer is a layer which fixed and formed the orientation state by superposition | polymerization, after making a polymeric liquid crystalline composition into a predetermined liquid crystal phase.

As the 1 aspect, the layer formed by making the polymerizable liquid crystal composition containing 1 or more types of a discotic liquid crystalline compound homeotropically orientate the molecule | numerator of the discotic liquid crystalline compound, and fixing it by superposition | polymerization in the state of a nematic liquid crystal phase is mentioned. Can be. Moreover, as another aspect, the layer which formed the polymeric liquid crystal composition containing 1 or more types of rod-shaped liquid crystalline compounds by fixing the molecule | numerator of the rod-shaped liquid crystalline compound in the state of a cholesteric liquid crystal phase is mentioned.

Discoid Liquid Crystal Compound

As a disk-like liquid crystalline compound which can be used for formation of the optically anisotropic layer, various literatures (C. Destrade et al., Mol. Crysr. Liq. Cryst., Vol. 71, page 111 (1981); Quarterly Chemistry, No. 22, Chemistry of Liquid Crystals, Chapter 5, Chapter 10, Section 2 (1994), B. Kohne et al., Angew. Chem. Soc. Chem. Comm., Page 1794 (1985); J. Zhang et al., J. Am. Chem. Soc., Vol. 116, page 2655 (1994)) can be employed in various ways.

About polymerization of a discotic liquid crystalline compound, the method of Unexamined-Japanese-Patent No. 8-27284 can be employ | adopted, for example.

It is preferable that a disk type liquid crystalline compound has a polymeric group so that it may be fixed by superposition | polymerization. For example, there exists a structure which couple | bonded the polymeric group as a substituent to the disk-shaped core of a disk-shaped liquid crystalline compound. Moreover, the structure which has a coupling group between a disk-shaped core and a polymeric group is more preferable. When the structure which has a coupling group is employ | adopted, it becomes easier to maintain an orientation state in a polymerization reaction. As for the disk type liquid crystalline compound which has a polymeric group, the compound represented by the following general formula (VI) is preferable.

General formula (VI)

D (-LP) _n

(In General Formula (VI), D is a disc shaped core, L is a divalent linking group, P is a polymerizable group, and n is an integer of 4 to 12.)

The disk-shaped core (D), the divalent linking group (L) and the polymerizable group (P) in the formula (VI) are, for example, (D1) to (D15) and (L1) described in JP 2001-4837 A. (L25), (P1)-(P18) can be used, respectively. Specifically, TE-8 shown below is mentioned.

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A disk-shaped liquid crystalline compound can be oriented substantially horizontally with respect to the cellulose acylate film surface which is a support body by using together 1 or more types of the fluorine-containing compound mentioned later. Here, substantially horizontal means that the average angle (average inclination angle) of the disk surface of a disk-shaped liquid crystalline compound and the surface of an optically anisotropic layer exists in the range of 0 degrees-10 degrees. Moreover, also when using the discotic liquid crystalline compound which has a polymeric group, the molecule of a discotic liquid crystalline compound is substantially horizontally oriented similarly to the above-mentioned. As a specific example of a disk-shaped liquid crystalline compound in this case, what is described in page 58 line 6-page 65 line 8 of the international publication WO01 / 88574 A1 pamphlet can be employ | adopted preferably.

[Fluorine-containing compound]

At the time of forming the optically anisotropic layer, in order to orient the liquid crystalline compound (particularly, the discotic liquid crystalline compound), or to make the optical properties uniform in the plane, to include at least one fluorine-containing compound in the composition for forming a layer. desirable. It is preferable that a fluorine-containing compound is a fluorine-containing surfactant. A low molecular weight compound or a high molecular compound may be sufficient as a fluorine-containing compound, For example, the compound illustrated in Unexamined-Japanese-Patent No. 2005-128050 is preferable about a low molecular weight compound.

As a fluorine-containing compound of a polymer, the fluoro aliphatic containing polymer containing the repeating unit represented by following General formula (1) is preferable.

In general formula (1)

[Chemical Formula 39]

In general formula (1), R <^1> , R <^2> and R <^3> are respectively independently a hydrogen atom, an alkyl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), or it mentions later It is group represented by -LQ, Preferably it is a hydrogen atom, a C1-C6 alkyl group, a chlorine atom, the group represented by -LQ, More preferably, it is a hydrogen atom and a C1-C4 alkyl group, Especially preferable It is a hydrogen atom and a C1-C2 alkyl group. As a specific example of the said alkyl group, a methyl group, an ethyl group, n-propyl group, n-butyl group, sec-butyl group, etc. are mentioned. The alkyl group may have a suitable substituent. Examples of the substituent include a halogen atom, an aryl group, a heterocyclic group, an alkoxyl group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, a hydroxyl group, an acyloxy group, an amino group, an alkoxycarbonyl group, an acylamino group, and an oxycarbonyl group. , Carbamoyl group, sulfonyl group, sulfamoyl group, sulfonamide group, sulforyl group, carboxyl group and the like.

In addition, the carbon number of an alkyl group does not contain the carbon atom of a substituent. Hereinafter, the same also applies to the carbon number of another group.

L is a single bond, -O-, -CO-, -NR ^4- , -S-, -SO _2- , -PO (OR ⁵ )-, an alkylene group, an arylene group or a divalent linking group formed by combining them Indicates. R <^4> represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group here. R ⁵ Represents an alkyl group, an aryl group, or an aralkyl group.

As L, it is preferable to include a single bond, -O-, -CO-, -NR ^4- , -S-, -SO _2- , an alkylene group or an arylene group, and -CO-, -O-, -NR Particularly preferred is a ^4- , alkylene group or arylene group.

When L contains an alkylene group, carbon number of an alkylene group becomes like this. Preferably it is 1-10, More preferably, it is 1-8, Especially preferably, it is 1-6. As an example of especially preferable alkylene group, methylene, ethylene, trimethylene, tetrabutylene, hexamethylene group, etc. are mentioned.

When L contains an arylene group, carbon number of an arylene group becomes like this. Preferably it is 6-24, More preferably, it is 6-18, Especially preferably, it is 6-12. As a specific example of an especially preferable arylene group, a phenylene, a naphthalene group, etc. are mentioned.

When L contains the bivalent coupling group (that is, aralkylene group) obtained by combining an alkylene group and an arylene group, carbon number of an aralkylene group becomes like this. Preferably it is 7-34, More preferably, it is 7-26, Especially preferable Preferably it is 7-16. As a specific example of an especially preferable aralkylene group, a phenylene methylene group, a phenylene ethylene group, a methylene phenylene group, etc. are mentioned.

The group illustrated as L may have a suitable substituent. Such substituents are preceded by R ¹ The same thing as the substituent illustrated as a substituent in R <^3> is mentioned.

Although the specific structure of L is illustrated below, this invention is not limited to these specific examples.

(40)

(41)

Q is not particularly limited as long as it is a polar group having hydrogen bonding. Preferably salts of hydroxyl groups, carboxyl groups, carboxyl groups (e.g. lithium salts, sodium salts, potassium salts, ammonium salts (e.g. ammonium, tetramethylammonium, trimethyl-2-hydroxyethylammonium, tetrabutylammonium, trimethylbenzylammonium) , Dimethylphenylammonium, etc.), pyridinium salts, etc.), the amide group of the carboxylic acid (N unsubstituted, N-mono lower alkyl substituent or N-di lower alkyl substituent, for example -CONH ₂ , -CONHCH ₃ ,- CON (CH ₃ ) _2, etc.), sulfo groups, salts of sulfo groups (examples of cations forming salts) are the same as those described above for carboxyl groups, sulfonamide groups (N unsubstituted, N-mono lower alkyl substituents or N- Di lower alkyl substituents such as -SO ₂ NH ₂ , -SO ₂ NHCH ₃ , -SO ₂ N (CH ₃ ) _2, etc.), phospho groups, salts of phospho groups (examples of cations forming salts are carboxyl groups Same as described in phosphonamide (N unsubstituted, N-mono lower alkyl substitution) , For example, _{-OP (= O) (NH 2} ) 2, -OP (= O) (NHCH 3) 2 and the like), a ureido group (-NHCONH _2), N position is non-substituted or mono-substituted amino group (- NH ₂ , -NHCH ₃ ), and the lower alkyl group represents a methyl group or an ethyl group. More preferably, they are a hydroxyl group, a carboxyl group, a sulfo group, and a phospho group, and a hydroxyl group or a carboxyl group is especially preferable.

1 type may be sufficient as the said repeating unit contained in a polymer, and 2 or more types of repeating units may exist simultaneously. Particularly preferred are repeating units having a carboxylic acid or repeating units having an acrylamide group.

Moreover, the said fluoro aliphatic containing polymer may have 1 type, or 2 or more types of repeating units guide | induced from a fluoro aliphatic group containing monomer. It is preferable to contain the fluoro aliphatic group containing monomer described in general formula (I) or general formula (II) of Unexamined-Japanese-Patent No. 2006-126768 preferably. Specifically, 1 type of repeating units guide | induced from the monomer chosen from the group of monomers of Unexamined-Japanese-Patent No. 2006-126768 may be contained, and 2 or more types may be contained.

In addition, the said fluoro aliphatic containing polymer may contain the other repeating unit of that excepting the above. The other repeating unit is not particularly limited, and a repeating unit derived from a monomer capable of a normal radical polymerization reaction can be given as a preferred example. The said fluoro aliphatic containing polymer may contain 1 type of repeating units derived from the monomer chosen from the monomer group of Unexamined-Japanese-Patent No. 2004-46038, and may contain 2 or more types. do.

Moreover, the said fluoro aliphatic containing polymer may contain the repeating unit derived from the monomer represented by general formula [2] described in Unexamined-Japanese-Patent No. 2004-333852.

And the said fluoro aliphatic containing polymer may have a polymeric group as a substituent in order to fix the orientation state of a liquid crystalline compound.

In the said fluoroaliphatic containing polymer used for this invention, it is preferable that the polymer unit of the monomer which has a fluoro aliphatic group is 25-99 mass% based on all the polymer units which comprise this fluoropolymer. A more preferable ratio differs according to the structure of a fluoro aliphatic group, and the polymerization unit of the monomer represented by general formula (I) of Unexamined-Japanese-Patent No. 2006-126768 is 50 based on the total polymerization unit which comprises this fluoropolymer. It is preferable that it is -99 mass%, It is more preferable that it is 60-97 mass%, It is still more preferable that it is 70-95 mass%. It is preferable that the polymer unit of the monomer represented by General formula (II) of Unexamined-Japanese-Patent No. 2006-126768 is 25-80 mass% based on all the polymerization units which comprise this fluoropolymer, and is 30-70 mass% It is more preferable, and it is still more preferable that it is 35-65 mass%. Moreover, two or more types of fluoro aliphatic group containing monomers may be contained in one polymer, and the monomer represented by general formula (I) and the monomer represented by general formula (II) may respectively contain 1 or more types simultaneously. .

The mass average molecular weight of the fluoroaliphatic containing polymer used in the present invention is preferably 2,000 to 100,000, more preferably 3000 to 80,000, still more preferably 4,000 to 60,000. Here, a mass mean molecular weight and molecular weight are molecular weight shown by solvent THF and polystyrene conversion by differential refractometer detection by the GPC analyzer which used TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all are brand names of Tosoh Corporation) columns. .

The said fluoro aliphatic containing polymer used for this invention can be manufactured by a well-known method. For example, it can manufacture by adding and polymerizing a general purpose radical polymerization initiator in the organic solvent containing a fluorine-type monomer, the monomer which has a hydrogen bond group, etc. In addition, it can be manufactured by the same method as the above by adding another addition polymeric unsaturated compound as needed. Depending on the polymerizability of each monomer, the dropping polymerization method for polymerization while dropping a monomer and an initiator into the reaction vessel is also effective in order to obtain a polymer having a uniform composition. More specifically, it is preferable to use the method described in [0035] to [0041] of JP-A-2004-46038.

[Bar type liquid crystalline compound]

As described above, the optically anisotropic layer is formed by fixing a polymerizable liquid crystal composition containing at least one of the rod-like liquid crystalline compounds in the state of the cholesteric liquid crystal phase. It is also preferable that it is one layer. As said rod-like liquid crystalline compound, the liquid crystal monomer molecule (polymerizable liquid crystal molecule) used for the twisted oriented polymeric chiral nematic (cholesteric) liquid crystal layer whose reflection wavelength which can be three-dimensional bridge | crosslinking is in an ultraviolet region is mentioned. Can be. Moreover, as said polymeric liquid crystal composition, there exists a mixture of the liquid crystalline monomer and chiral compound disclosed by Unexamined-Japanese-Patent No. 7-258638 and Unexamined-Japanese-Patent No. 10-508882, for example. The following compounds A-K are contained in the specific example of the polymeric rod liquid crystal compound which can be used for the said polymeric liquid crystal composition. These compounds may be mixed and, for example, two or more types selected from the compounds of the following compounds A to J and the compounds included in the range of the following compounds K may be used in combination. Moreover, in the following compound K, although X represents an integer, it is preferable that X is an integer of 2-5.

Moreover, the chiral agent represented by the following compound L-compound N is contained in the specific example of the said chiral agent. Moreover, in the compound L or the compound M, although X shows an integer in a formula, X is an integer of 2-12, It is preferable. Moreover, also in compound N, X shows an integer in a formula, X is an integer of 2-5. It is preferable.

Compound A

(42)

Compound B

(43)

Compound C

(44)

Compound D

[Chemical Formula 45]

Compound E

(46)

Compound F

(47)

Compound G

(48)

Compound H

(49)

Compound I

(50)

Compound J

(51)

Compound K

(52)

Compound L

(53)

Compound M

[Formula 54]

Compound N

(55)

[Fixation of alignment state of liquid crystal compound]

When forming the said optically anisotropic layer with the liquid crystal composition containing a liquid crystalline compound, it is preferable to fix the molecule | numerator of the oriented liquid crystalline compound, maintaining the orientation state. It is preferable to perform fixation by the polymerization reaction of the polymeric group introduce | transduced into the molecule | numerator of a liquid crystalline compound. Although the polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator, a photopolymerization reaction is more preferable. As a photoinitiator, For example, the (alpha) -carbonyl compound (as described in each specification of US Pat. No. 23,684,1, 2367670), an acyloinether (as described in the specification of US Pat. No. 2448828), and (alpha) -hydrocarbon substitution, for example. Aromatic acyloin compounds (described in the specifications of US Pat. No. 2722512), polynuclear quinone compounds (described in the specifications of US Pat. No. 3046127, 2951758), triarylimidazole dimers and p-aminophenylketones Combinations (as described in US Pat. No. 3549367), acridine and phenazine compounds (as described in JP-A-60-105667, US Pat. No. 4239850) and oxadiazole compounds (US Pat. 4212970) can be employed.

It is preferable that it is 0.01-20 mass% of the composition for optically anisotropic layer formation (solid content in the case of coating liquid), and, as for the usage-amount of a photoinitiator, it is more preferable that it is 0.5-5 mass%. It is preferable to use ultraviolet-ray for the light irradiation for superposition | polymerization of a liquid crystalline compound. The irradiation energy is preferably 20 mJ / cm 2 to 50 J / cm 2, more preferably 100 to 800 mJ / cm 2. In order to accelerate the photopolymerization reaction, light may be irradiated under heating conditions.

It is preferable that it is 0.1-10 micrometers, and, as for the thickness of an optically anisotropic layer, it is more preferable that it is 0.5-5 micrometers.

The optically anisotropic layer is prepared as a coating liquid by using a liquid crystal compound and, if desired, a polymerizable liquid crystal composition containing the polymerization initiator and other additives, and applying the coating liquid to the surface of the support (orientation film, if necessary), It is preferable to form by drying and superposing | polymerizing. As a solvent used for preparation of an optically anisotropic layer coating liquid, an organic solvent is used preferably. As the organic solvent, for example, amide (e.g., N, N-dimethylformamide), sulfoxide (e.g., dimethyl sulfoxide), heterocyclic compound (e.g., pyridine), hydrocarbon (e.g., benzene, hexane), Alkyl halides (eg chloroform, dichloromethane), esters (eg methyl acetate, butyl acetate), ketones (eg acetone, methyl ethyl ketone), ethers (eg tetrahydrofuran, 1,2-dimethoxyethane) It can be adopted. Among these, alkyl halides and ketones are preferable. Two or more kinds of organic solvents may be used in combination. The application of the coating liquid can employ a wide variety of known methods (eg, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method).

[Alignment film]

When forming the said optically anisotropic layer, in order to orient the molecule | numerator of a liquid crystalline compound, it is preferable to use an oriented film. Moreover, the orientation film which an orientation function produces by provision of an electric field, provision of a magnetic field, or light irradiation is also known. The kind of polymer used for an oriented film can be determined according to the orientation pattern (for example, average inclination angle) of liquid crystalline compound molecule | numerator. For example, in order to orientate a liquid crystalline compound horizontally, the polymer (normally polymer for orientation) which does not reduce the surface energy of an oriented film is used. About the kind of specific polymer, the matter described in the well-known document regarding a liquid crystal cell or an optical compensation sheet can be employ | adopted widely. In particular, when the molecules of the liquid crystalline compound are oriented in a direction orthogonal to the direction of the rubbing treatment, for example, modified polyvinyl alcohol described in JP-A-2002-62427, JP-A-2002-98836 The acrylic acid copolymer described in the above, the polyimide described in JP-A-2002-268068, and the polyamic acid can be preferably used. Also in any orientation film, in order to improve the adhesiveness of an optically anisotropic layer and an orientation film (resultingly, an optically anisotropic layer and a support body), it is preferable to contain the polymer which has a polymeric group in an orientation film. A polymerizable group can introduce | transduce the repeating unit which has a polymeric group in a side chain, or can introduce | transduce as a substituent of a cyclic group. It is more preferable to use the alignment film which forms a chemical bond with a liquid crystalline compound at an interface, and what is described in Unexamined-Japanese-Patent No. 9-152509 can be employ | adopted as such an alignment film, for example.

The thickness of the alignment layer is preferably 0.01 to 5 mu m, more preferably 0.05 to 2 mu m. Moreover, after orienting the molecule | numerator of a liquid crystalline compound using an oriented film, you may fix an liquid crystalline compound as it is in the orientation state, and form an optically anisotropic layer, and only this optically anisotropic layer may be transferred on a support body.

[Optical Anisotropic Layer Made of Polymer Layer]

The optically anisotropic layer may be a polymer layer made of a stretched or unstretched polymer film, or a polymer layer formed by applying a polymer composition to a surface of a support. And after forming a polymer layer on the said support body, you may perform an extending | stretching process as a whole and express the optical characteristic which satisfy | fills the conditions required as a support body and retardation film. Although it does not restrict | limit especially about the polymer material used for formation of the said polymer layer, Various polymer materials in which the refractive index of the in-plane direction with respect to the normal line direction of a film surface becomes large after film-forming are preferable. Moreover, superposition | polymerization advances in the process of forming a polymer layer, In this case, it is preferable to use the polymerizable low molecular weight compound etc. which can provide this polymer. Specifically, the material disclosed in Unexamined-Japanese-Patent No. 2000-190385 and Unexamined-Japanese-Patent No. 2004-226945 can be used. For example, various polymers such as polyamide, polyimide, polyamic acid, polyester, polyether ketone, polyaryl ether ketone, polyamideimide, polyesterimide or polyesteramide having one or more aromatic rings, or such The polymerizable low molecular compound which can provide a polymer is mentioned. These may be used alone or in combination.

Moreover, you may employ | adopt the film which further extended the film after film-forming the said polymer film etc. and added the process which enlarges in-plane optical anisotropy. In the stretching treatment, one or two or more kinds of suitable methods, such as a biaxial stretching method such as a sequential method or a simultaneous method, a uniaxial stretching method such as a free end method or a fixed end method, can be used. The biaxial stretching method is preferable from the viewpoint of effectively expressing Rth.

As said polyamide, the polymer containing the polymerization unit represented by following formula (1) is mentioned, for example.

(56)

In formula, X and R <^1> are arbitrary residues, and at least one is a group containing an aromatic ring.

It is preferable that said X is represented by either of the following. Here, Me is a methyl group.

(57)

R ¹ is preferably represented by any of the following.

(58)

[Chemical Formula 59]

However, in said formula, r shows the number of 2-12, s shows the number of 1-500, t shows the number of 0-500.

In addition, as said polyamideimide, the polyamideimide of Unexamined-Japanese-Patent No. 61-162512 is mentioned, for example.

As said polyimide, the polymer represented by following formula (2), for example:

(60)

(Wherein m is the average degree of polymerization. Y is

(61)

And groups such as R ² ,

(62)

And so on.

As said polyimide, the in-plane orientation is high, for example, and the polyimide soluble in an organic solvent is preferable. Specifically, it contains the condensation polymerization product of 9,9-bis (aminoaryl) fluorene and aromatic tetracarboxylic dianhydride disclosed by Unexamined-Japanese-Patent No. 2000-511296, and is represented by following formula (3). The polymer containing one or more repeating units shown can be used.

(63)

In said formula (3), R <^3> -R <^6> is independently chosen from the group which consists of a hydrogen, a halogen, a phenyl group, the phenyl group substituted by 1-4 halogen atoms, or a C1-10 alkyl group, and a C1-10 alkyl group, respectively. It is one or more types of substituents. Preferably, R ³ to R ⁶ are one or more types of substituents each independently selected from the group consisting of a halogen, a phenyl group, a phenyl group substituted with 1 to 4 halogen atoms or a C1-10 alkyl group, and a C1-10 alkyl group.

In said formula (3), Z is a C6-20 tetravalent aromatic group, For example, a pyromellitic group, a polycyclic aromatic group, the derivative of a polycyclic aromatic group, or following formula (4) Is represented by.

&Lt; EMI ID =

In the formula (4), Z 'is, for example, a covalent bond, a C (R ⁷ ) ₂ group, a CO group, an O atom, an S atom, an SO ₂ group, a Si (C ₂ H ₅ ) ₂ group, or NR ⁸ groups, and in a plurality of cases, the same or different. In addition, w represents the integer of 1-10. R ^{7 's} are each independently hydrogen or C (R ⁹ ) ₃ . R ⁸ is hydrogen, an alkyl group having 1 to about 20 carbon atoms, or a C 6-20 aryl group, and in a plurality of cases, the same or different. R ^{9 's} are each independently hydrogen, fluorine, or chlorine.

As said polycyclic aromatic group, the tetravalent group derived from naphthalene, fluorene, benzofluorene, or anthracene is mentioned, for example. Moreover, as a substituted derivative of the said polycyclic aromatic group, the said polycyclic aromatic substituted by the at least 1 group chosen from the group which consists of a C1-10 alkyl group, its fluorinated derivative, and halogen, such as F and Cl, for example The group can be mentioned.

In addition, the homopolymer in which the repeating unit described in Unexamined-Japanese-Patent No. 8-511812 is represented by following General formula (5) or (6), and a repeating unit are represented by following General formula (7), for example Polyimide, and the like. Moreover, the polyimide of following formula (7) is a preferable form of the homopolymer of following formula (5).

(65)

In General Formulas (5) to (7), G and G 'are, for example, a covalent bond, a CH ₂ group, a C (CH ₃ ) ₂ group, a C (CF ₃ ) ₂ group, and a C (CX ₃ ) Each independently selected from the group consisting of ₂ groups (where X is halogen), CO group, O atom, S atom, SO ₂ group, Si (CH ₂ CH ₃ ) ₂ group, and N (CH ₃ ) group The groups may be represented and may be the same or different from each other.

In said Formula (5) and Formula (7), L is a substituent, d and e represent the number of substitutions. L is, for example, a halogen, a C1-3 alkyl group, a C1-3 halogenated alkyl group, a phenyl group, or a substituted phenyl group, and in the case of a plurality, each is the same or different. As said substituted phenyl group, the substituted phenyl group which has 1 or more types of substituents chosen from the group which consists of a halogen, a C1-3 alkyl group, and a C1-3 halogenated alkyl group is mentioned, for example. Moreover, as said halogen, fluorine, chlorine, bromine, or iodine is mentioned, for example. d is an integer of 0-2 and e is an integer of 0-3.

In said formula (5)-(7), Q is a substituent and f shows the number of substitutions. Q is, for example, an atom selected from the group consisting of hydrogen, a halogen, an alkyl group, a substituted alkyl group, a nitro group, a cyano group, a thioalkyl group, an alkoxy group, an aryl group, a substituted aryl group, an alkylester group, and a substituted alkylester group, or Group, and when there are a plurality of Q's, they are the same or different. As said halogen, a fluorine, chlorine, bromine, and iodine are mentioned, for example. As said substituted alkyl group, a halogenated alkyl group is mentioned, for example. Moreover, a halogenated aryl group is mentioned as said substituted aryl group, for example. f is an integer of 0-4, g and h are the integers of 0-3 and 1-3, respectively. In addition, g and h are preferably larger than one.

In said formula (6), R <^10> and R <^11> is group selected independently from the group which consists of hydrogen, a halogen, a phenyl group, a substituted phenyl group, an alkyl group, and a substituted alkyl group, respectively. Especially, it is preferable that R <^10> and R <^11> is a halogenated alkyl group each independently.

In said formula (7), M <^1> and M <^2> are the same or different, For example, they are a halogen, a C1-3 alkyl group, a C1-3 halogenated alkyl group, a phenyl group, or a substituted phenyl group. As said halogen, fluorine, chlorine, bromine, and iodine are mentioned, for example. Moreover, as said substituted phenyl group, the substituted phenyl group which has one or more types of substituents chosen from the group which consists of a halogen, a C1-3 alkyl group, and a C1-3 halogenated alkyl group is mentioned, for example.

As a specific example of the polyimide shown by said formula (5), what is represented by following formula (8), etc. are mentioned, for example.

(66)

And as said polyimide, the copolymer which suitably copolymerized acid dianhydride and diamine other than the skeleton (repeated unit) mentioned above is mentioned, for example.

As said acid dianhydride, aromatic tetracarboxylic dianhydride is mentioned, for example. As said aromatic tetracarboxylic dianhydride, For example, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, a heterocyclic aromatic tetracarboxylic dianhydride, 2, 2'-substituted biphenyl tetracarboxylic dianhydride etc. are mentioned.

As said pyromellitic dianhydride, For example, pyromellitic dianhydride, 3, 6- diphenyl pyromellitic dianhydride, 3, 6-bis (trifluoromethyl) pyromellitic dianhydride, 3, 6-dibromo pyromellitic dianhydride, 3, 6- dichloro pyromellitic dianhydride, etc. are mentioned. As said benzophenone tetracarboxylic dianhydride, it is 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, 2,3,3', 4'- benzophenone tetracarboxylic, for example. Acid dianhydride, 2,2 ', 3,3'- benzophenone tetracarboxylic dianhydride, etc. are mentioned. As said naphthalene tetracarboxylic dianhydride, For example, 2,3,6,7-naphthalene- tetracarboxylic dianhydride, 1,2,5,6-naphthalene- tetracarboxylic dianhydride, 2 And 6-dichloro-naphthalene-1,4,5,8-tetracarboxylic dianhydride and the like. Examples of the heterocyclic aromatic tetracarboxylic dianhydride include thiophene-2,3,4,5-tetracarboxylic dianhydride and pyrazine-2,3,5,6-tetracarboxylic dianhydride. Water, pyridine-2,3,5,6-tetracarboxylic dianhydride, and the like. As said 2,2'-substituted biphenyl tetracarboxylic dianhydride, For example, 2,2'- dibromo-4,4 ', 5,5'- biphenyl tetracarboxylic dianhydride, 2,2'-dichloro-4,4 ', 5,5'-biphenyltetracarboxylic dianhydride, 2,2'-bis (trifluoromethyl) -4,4', 5,5'-ratio Phenyl tetracarboxylic dianhydride etc. are mentioned.

Other examples of the aromatic tetracarboxylic dianhydride include 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride and bis ( 2,5,6-trifluoro-3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexa Fluoropropane dianhydride, 4,4'-bis (3,4-dicarboxyphenyl) -2,2-diphenylpropane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 4,4 ' -Oxydiphthalic dianhydride, bis (3,4-dicarboxyphenyl) sulfonic dianhydride, 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride, 4,4'-[4,4 '-Isopropylidene-di (p-phenyleneoxy)] bis (phthalic anhydride), N, N- (3,4-dicarboxyphenyl) -N-methylamine dianhydride, bis (3,4-dicarboxy Phenyl) diethylsilane dianhydride etc. are mentioned.

Among these, as said aromatic tetracarboxylic dianhydride, 2,2'-substituted biphenyl tetracarboxylic dianhydride is preferable, More preferably, 2,2'-bis (trihalomethyl) -4 , 4 ', 5,5'-biphenyltetracarboxylic dianhydride, more preferably 2,2'-bis (trifluoromethyl) -4,4', 5,5'-biphenyltetracar Acid dianhydrides.

As said diamine, aromatic diamine is mentioned, for example, A benzenediamine, a diamino benzophenone, a naphthalenediamine, a heterocyclic aromatic diamine, and other aromatic diamine are mentioned as a specific example.

As said benzenediamine, o-, m- and p-phenylenediamine, 2, 4- diamino toluene, 1, 4- diamino-2- methoxybenzene, 1, 4- diamino- And diamines selected from the group consisting of benzenediamines such as 2-phenylbenzene and 1,3-diamino-4-chlorobenzene. 2,2'- diamino benzophenone, 3,3'- diamino benzophenone, etc. are mentioned as an example of the said diamino benzophenone. As said naphthalenediamine, 1, 8- diamino naphthalene, 1, 5- diamino naphthalene, etc. are mentioned, for example. Examples of the heterocyclic aromatic diamine include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-S-triazine and the like.

Examples of the aromatic diamine include 4,4'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 4,4 '-(9-fluorenylidene) -dianiline, 2, 2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,2'-dichloro-4,4 ' -Diaminobiphenyl, 2,2 ', 5,5'-tetrachlorobenzidine, 2,2-bis (4-aminophenoxyphenyl) propane, 2,2-bis (4-aminophenyl) propane, 2 , 2-bis (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4 -Aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4 -(4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4'-diaminodiphenylthioether, 4,4'-di Amino diphenyl sulfone etc. are mentioned.

As said polyamic acid, the polymer represented by following formula (10)-(12) is mentioned, for example.

(67)

(In formula, n shows the number of 2-400.)

Moreover, when using the said polyamic acid, it is preferable to imidize by heat processing, after apply | coating a solution and drying.

As said polyether ketone, the polyaryl ether ketone represented by following General formula (13) described in Unexamined-Japanese-Patent No. 2001-49110 is mentioned, for example.

(68)

In said formula (13), X represents a substituent and q represents the number of substitution. X is a halogen atom, a lower alkyl group, a halogenated alkyl group, a lower alkoxy group, or a halogenated alkoxy group, for example, and when X is multiple, each is the same or different.

As said halogen atom, a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom are mentioned, for example, A fluorine atom is preferable among these. As said lower alkyl group, the lower alkyl group which has a C1-6 linear or branched chain is preferable, for example, More preferably, it is a C1-4 linear or branched alkyl group. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, and tert-butyl group are preferable, and methyl group and ethyl group are particularly preferable. As said halogenated alkyl group, the halide of the said lower alkyl groups, such as a trifluoromethyl group, is mentioned, for example. As said lower alkoxy group, C1-6 linear or branched alkoxy group is preferable, for example, More preferably, it is C1-4 linear or branched alkoxy group. Specifically, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, and tert-butoxy group are more preferable, and particularly preferably methoxy group and ethoxy group to be. As said halogenated alkoxy group, the halide of the said lower alkoxy group, such as a trifluoro methoxy group, is mentioned, for example.

In said formula (13), q is an integer of 0-4. In said Formula (13), it is preferable that q = 0 and the oxygen atom of the carbonyl group and ether couple | bonded at the both ends of a benzene ring exists in a para position mutually. In addition, in said Formula (13), R <^1> is group represented by following formula (14), and m is an integer of 0 or 1.

(69)

In said formula (14), X 'represents a substituent and is the same as X in the said Formula (13), for example. In the formula (14), when there are a plurality of X's, they are the same or different. q 'represents the number of substitution of said X', is an integer of 0-4, and q '= 0 is preferable. In addition, p is an integer of 0 or 1.

In said formula (14), R <^2> represents a bivalent aromatic group. As this bivalent aromatic group, it is o-, m- or p-phenylene group, or naphthalene, biphenyl, anthracene, o-, m- or p-terphenyl, phenanthrene, dibenzofuran, a ratio, for example. Or a divalent group derived from phenyl ether or biphenyl sulfone. In these bivalent aromatic groups, hydrogen directly bonded to the aromatic group may be substituted with a halogen atom, a lower alkyl group or a lower alkoxy group. Among these, as said R <^2> , the aromatic group chosen from the group which consists of following formula (15)-(21) is preferable.

(70)

In said Formula (13), as said R <^1> , group represented by following formula (22) is preferable, and in following formula (22), R <^2> and p are synonymous with said Formula (14).

(71)

In addition, in said formula (13), n shows a polymerization degree, it is the range of 2-5000, for example, Preferably it is the range of 5-500. Moreover, the superposition | polymerization may consist of repeating units of the same structure, and may consist of repeating units of another structure. In the latter case, block polymerization may be sufficient as the superposition | polymerization form of a repeating unit, and random polymerization may be sufficient as it.

And it is preferable that the terminal of the polyaryl ether ketone represented by said Formula (13) is a fluorine on the p- tetrafluoro benzoylene group side, and an oxyalkylene group side is a hydrogen atom, and such a polyaryl ether ketone is an example. For example, it can represent with following General formula (23). In addition, in the following formula, n represents the same polymerization degree as said Formula (13).

(72)

As a specific example of the polyaryl ether ketone represented by said Formula (13), what is represented by following formula (24)-(27) is mentioned, In each following formula, n is said Formula (13), The same degree of polymerization is shown.

(73)

In addition to these, as said polyamide or polyester, the polyamide and polyester of Unexamined-Japanese-Patent No. 10-508048 are mentioned, for example, These repeating units are the following general, for example, It can be represented by Formula (28).

&Lt; EMI ID =

In said formula (28), Y is O or NH. Further, E is, for example, a covalent bond, a C2 alkylene group, a halogenated C2 alkylene group, a CH ₂ group, a C (CX ₃ ) ₂ group (where X is halogen or hydrogen), a CO group, an O atom, S At least one group selected from the group consisting of atoms, SO ₂ groups, Si (R) ₂ groups, and N (R) groups, may be the same or different. In said E, R is one or more types of C1-3 alkyl groups and C1-3 halogenated alkyl groups, and is in meta position or para position with respect to a carbonyl functional group or Y group.

In addition, in said (28), A and A 'are substituents, t and z represent each substitution number. In addition, p is an integer of 0-3, q is an integer of 1-3, r is an integer of 0-3.

A is, for example, a substituted aryl group by hydrogen, halogen, C1-3 alkyl group, C1-3 halogenated alkyl group, alkoxy group represented by OR (where R is defined above), aryl group, halogenation, etc., C1-9 alkoxycarbonyl group, C1-9 alkylcarbonyloxy group, C1-12 aryloxycarbonyl group, C1-12 arylcarbonyloxy group and its substituted derivatives, C1-12 arylcarbamoyl group, and C1-12 arylcarbons It is selected from the group which consists of a carbonylamino group and its substituted derivatives, and when it is multiple, they are the same or different, respectively. A 'is selected from the group consisting of a halogen, a C1-3 alkyl group, a C1-3 halogenated alkyl group, a phenyl group, and a substituted phenyl group, and in the case of a plurality, each is the same or different. As a substituent on the phenyl ring of the said substituted phenyl group, a halogen, a C1-3 alkyl group, a C1-3 halogenated alkyl group, and a combination thereof are mentioned, for example. T is an integer of 0-4, and z is an integer of 0-3.

It is preferable to represent with the following general formula (29) also in the repeating unit of the polyamide or polyester represented by said Formula (28).

(75)

In said Formula (29), A, A ', and Y are what was defined in the said Formula (28), v is an integer of 0-3, Preferably it is an integer of 0-2. x and y are each 0 or 1, but are not 0 together.

[Polarizer]

In addition, the present invention relates to a polarizing plate having a linear polarizing film (hereinafter referred to as "linear polarizing film" in the present specification, simply referred to as "linear polarizing film") and a phase difference film of the present invention as a protective film of the polarizing film. Do too. Since the retardation film of this invention has a predetermined cellulose acylate film as a support body, the back surface (side surface in which an optically anisotropic layer is not formed) of this cellulose acylate film can be directly attached to the surface of a polarizing film. For example, a long cellulose acylate film is continuously supplied, a polymerizable liquid crystal composition, a composition for forming a polymer layer, or the like is applied to the surface of the film to form an optically anisotropic layer, thereby producing a long retardation film. By attaching on the long polarizing film on it, a polarizing plate can be manufactured stably continuously.

[Polarizing Film]

The polarizing film employed in the present invention is not particularly limited, and known ones can be widely adopted. For example, a dichroism, such as iodine and / or azo, anthraquinone, tetrazine, or the like, is formed on a film made of a hydrophilic polymer such as polyvinyl alcohol, partially formalized polyvinyl alcohol, or ethylene / vinyl acetate copolymer partial saponified product. The thing which adsorbed the dichroic substance which consists of dyes, etc., and extended | stretched orientated can be used. In this invention, it is preferable to use the extending | stretching method of Unexamined-Japanese-Patent No. 2002-131548, It is especially preferable to use the width direction uniaxial stretching tenter drawing machine whose absorption axis of a polarizing film is substantially orthogonal to a longitudinal direction. desirable.

The polarizing film is used as a polarizing plate whose both surfaces were protected by the protective film. The retardation film of this invention is used suitably as a protective film of a polarizing film as mentioned later.

When using protective films other than the retardation film of this invention as a protective film, the kind of protective film is not specifically limited, Cellulose esters, such as cellulose acetate, cellulose acetate butylate, and cellulose propionate, polycarbonate, polyolefin , Polystyrene, polyester and the like can be used. It is preferable that a protective film is normally supplied in roll form, and is made to stick continuously so that a longitudinal direction may correspond with an elongate polarizing film. Here, although the orientation axis (ground axis) of a protective film may be in any direction, it is preferable that the orientation axis of a protective film is parallel to a longitudinal direction from an operation simplicity point. Moreover, the angle of the slow axis (orientation axis) of a protective film and the absorption axis (stretch axis) of a polarizing film is not specifically limited, either, According to the objective of a polarizing plate, it can set suitably.

When using protective films other than the retardation film of this invention as a protective film, Re value of a protective film has preferable 10 nm or less, for example at 632.8 nm, and 5 nm or less is more preferable. In view of such low retardation, the polymer used as the protective film is preferably a polyolefin such as cellulose triacetate, zeonex, zeonoa (all manufactured by Nippon Xeon Co., Ltd.), ARTON (manufactured by JSR Co., Ltd.). do. In addition, the non-birefringent optical resin material described in Unexamined-Japanese-Patent No. 8-110402 or 11-293116 is mentioned, for example. Moreover, when using cellulose acetate for a protective film, it is preferable that Re and Rth are less than 10 nm, and also it is 2 nm or less for the purpose of suppressing the retardation change by temperature-humidity of environment small.

In this invention, one of the protective films of a polarizing film may serve as the support body of an optically anisotropic layer for the purpose of thinning etc., and the optically anisotropic layer itself may be sufficient as it. It is preferable that the optically anisotropic layer and the polarizing film are adhered to each other from the viewpoint of preventing misalignment of the optical axis and preventing intrusion of foreign matter such as dust. Appropriate methods, such as the adhesion method through a transparent adhesive layer, can be applied to the fixing lamination, for example. It does not specifically limit about the kind of the adhesive agent, It is preferable not to require a high temperature process at the time of hardening at the time of adhesion | attachment or drying from a viewpoint of the prevention of the change of the optical characteristic of a structural member, etc. It is preferable not to require drying time. In view of this, a hydrophilic polymer adhesive or an adhesive layer is preferably used.

For formation of the pressure-sensitive adhesive layer, a transparent pressure-sensitive adhesive made of an appropriate polymer such as an acrylic polymer, a silicone polymer, polyester or polyurethane, polyether or synthetic rubber can be used. Among these, an acrylic adhesive is preferable from a viewpoint of optical transparency, adhesive characteristics, weather resistance, etc. Moreover, an adhesion layer can also be formed in the single side | surface or both surfaces of a polarizing plate as needed for the purpose of adhesion | attachment to adherends, such as a liquid crystal cell. In that case, when the adhesive layer is exposed to the surface, it is preferable to temporarily attach a separator or the like to prevent contamination of the surface of the adhesive layer until it is actually used.

Even if one side or both sides of a polarizing film use the polarizing plate which provided the protective film of various objectives, such as water resistance based on the above-mentioned protective film, and the appropriate functional layer, such as an anti-reflective layer for the purpose of prevention of surface reflection, and / or an anti-glare treatment layer. do. The antireflection layer can be appropriately formed, for example, as a coating layer of a fluorine-based polymer or an optical interference film such as a multilayer metal deposition film. The anti-glare layer may also be formed in a suitable manner in which the surface reflection light is diffused by imparting a fine concavo-convex structure to the surface by a suitable method such as, for example, a resin coating layer containing fine particles, embossing, sandblasting, or etching. have.

Examples of the fine particles include inorganic fine particles having a conductivity such as silica, calcium oxide, alumina or titania, zirconia or tin oxide, indium oxide, cadmium oxide, and antimony oxide or polymethyl having an average particle size of 0.5 to 20 µm. One kind or two or more kinds of suitable ones such as crosslinked or uncrosslinked organic fine particles composed of a suitable polymer such as methacrylate or polyurethane can be used. Moreover, said adhesive layer-adhesion layer may contain such microparticles | fine-particles, and may show light diffusivity.

[Optical Performance of Polarizing Plate]

The polarizing plate of this invention contains a polarizing film and a protective film (at least one phase difference film of this invention). It is preferable that the optical property and durability (short-term, long-term storage property) of the polarizing plate of this invention have the performance equivalent to or more than the commercially available super high contrast product (for example, HLC2-5618 by Sanlitz Corporation). Specifically, visible light transmittance is 42.5% or more, polarization degree ({(Tp-Tc) / (Tp + Tc)} ^1/2 ≥ 0.9995 (where Tp is parallel transmittance and Tc is orthogonal transmittance), and the temperature is 60 deg. The rate of change of light transmittance before and after 500 hours in a humidity of 90% RH atmosphere and 500 hours in a dry atmosphere is 3% or less based on absolute value, further 1% or less, and the rate of change of polarization degree is It is preferable that it is 1% or less based on absolute value and also 0.1% or less.

The polarizing plate of this invention may have another retardation film (2nd retardation film) with the retardation film (1st retardation film) of this invention. Preferable optical characteristics of a 2nd phase difference film change with the mode of the liquid crystal display device in which the polarizing plate of this invention is used. For example, when using for vertical alignment type liquid crystal display devices, such as VA mode, it is preferable that a 2nd retardation film is A plate, More specifically, it is a retardation film which satisfy | fills following formula [7] desirable. Moreover, it is more preferable that the wavelength dispersibility satisfy | fills following formula [8].

[7] 70 ≤ Re (550) ≤ 180 and 30 ≤ Rth (550) ≤ 140

[8] 0.7 ≤ Re (450) / Re (550) ≤ 1.0

Moreover, it is preferable to laminate | stack a 2nd phase difference film in the arrangement which the in-plane slow axis orthogonally crosses with the absorption axis of a polarizing film.

The detail of a 2nd phase difference film is demonstrated in the following [liquid crystal display device] columns.

[Liquid crystal display device]

This invention relates also to the liquid crystal display device which has the retardation film or polarizing plate of this invention. The liquid crystal display of the present invention is a vertical alignment type in which the liquid crystal molecules in the liquid crystal cell are vertically oriented with respect to the substrate in a non-driven state in which no driving voltage is applied or a voltage less than the applied voltage is applied. For example, it is preferable that liquid crystal cells, such as VA mode, MVA mode, PVA mode, CPA mode, SURVIVAL mode, are included. Hereinafter, one aspect of the liquid crystal display device of the present invention will be described with reference to FIGS. 1 and 2. FIG. 1: shows the schematic diagram of an example of the structure of the polarizing plate which can be used by this invention of the liquid crystal display device of this invention. In FIG. 1, it is an example in which active driving was performed using the nematic liquid crystal which has negative dielectric anisotropy as a field effect type liquid crystal element.

In FIG. 1, a liquid crystal display device has a liquid crystal cell and a pair of polarizing plate (upper polarizing plate 1 and lower polarizing plate 14) arrange | positioned at both sides of a liquid crystal cell. The second retardation film 3 is disposed between the upper polarizing plate 1 and the liquid crystal cell, and the first retardation film 10 is disposed between the lower polarizing plate 14 and the liquid crystal cell. The liquid crystal cell is composed of the upper electrode substrate 5 and the lower electrode substrate 8 and the liquid crystal molecules 7 sandwiched therebetween. The liquid crystal molecule 7 is a non-driven state in which an external electric field is not applied by the orientation control directions (upper substrate alignment control direction 6 and lower substrate alignment control direction 9) performed on the opposite surface of the electrode substrate. In the direction substantially perpendicular to the substrate. In addition, the upper polarizing plate 1 and the lower polarizing plate 14 are laminated so that the absorption axis and the absorption axis are orthogonal to each other. Here, in FIG. 1, 2 represents the direction of an upper polarizing plate absorption axis, and 15 represents the direction of a lower polarizing plate absorption axis, respectively. And in the 2nd phase difference film, the direction 4 of the slow axis is orthogonally arrange | positioned with respect to the absorption axis direction 2 of an upper polarizing plate.

As shown in FIG. 2, the polarizing plate consists of the polarizing film 103 clamped between the protective films 101 and 105. FIG. The polarizing plate can be produced by, for example, dyeing a polarizing film made of a polyvinyl alcohol film with iodine and stretching to obtain a polarizing film, and laminating protective films 101 and 105 on both surfaces thereof. At the time of lamination, in terms of productivity, it is preferable to attach a pair of protective films and a total of three films of a polarizing film with a roll to roll. In addition, in lamination | stacking of a roll to roll, as shown in FIG. 2, it can laminate | stack easily so that the directions 102 and 106 of the slow axis of a protective film, and the absorption axis direction 104 of a polarizing film may become parallel, and of a polarizing plate It is preferable because a change in dimensionality and curling do not occur easily, and a polarizing plate having high mechanical stability is obtained. Moreover, the same effect is acquired when two or more axes which consist of three films, for example, the slow axis of one protective film, the polarizing film absorption axis, or the slow axis of two protective films, etc. are substantially parallel.

In FIG. 1, the 1st retardation film 10 is a retardation film (retardation film of a 1st aspect or a 2nd aspect) of this invention, As for the detail, it is as above-mentioned. When arrange | positioning the retardation film of this invention as a 1st retardation film, it is preferable to arrange | position so that the support body which is a predetermined cellulose acylate film may be a polarizing plate side, and an optically anisotropic layer may be a liquid crystal cell side. Moreover, the same effect is acquired even if arrange | positioning the polarizing plate of this invention as a polarizing plate 1 instead of disposing a 1st retardation film. Moreover, when attaching the polarizing plate of this invention to a liquid crystal display device, it arrange | positions so that the retardation film of this invention assembled as a protective film in a polarizing plate may become a liquid crystal cell side.

In FIG. 1, the 2nd phase difference film 3 is comprised by the optically anisotropic layer of 1 or 2 axes optically, and there is no restriction | limiting in particular, A cellulose acylate, norbornene type polymer, a polycarbonate polymer, polyallyl The rate type polymer, the polyester type polymer, or polysulfone, or the polymer which mixed 2 or 3 or more types of these polymers, etc. are mentioned. Among them, it is preferable that excellent controllability, transparency and heat resistance of the birefringence characteristics are obtained. In addition, although the 2nd retardation film 3 changes also with the combination with the 1st retardation film 10, it is the uniaxial property of what is called reverse wavelength dispersibility which the absolute value of Re becomes large according to a wavelength in terms of display characteristics. More preferred. On the other hand, the first retardation film 10 is so-called forward wavelength dispersion in which optically negative refractive index anisotropy is obtained and the absolute value of Rth decreases with the wavelength, and Re is preferably -10 to 10 nm. These 2nd phase difference film 3 and the 1st phase difference film 10 eliminate image coloring of a liquid crystal cell, and contribute to expansion of a viewing angle.

In FIG. 1, when the upper side is the observer's side, in FIG. 1, the second retardation film 3 is formed between the upper polarizing plate 1 on the observer's side and the liquid crystal cell upper electrode substrate 5 that is the observer's side liquid crystal cell substrate. Although the retardation film 10 showed the structure arrange | positioned between the lower polarizing plate 14 of the back side, and the liquid crystal cell lower electrode substrate 8 which is a board | substrate for back side liquid crystal cells, the 2nd phase difference film 3 and the 1st phase difference The structure which the film 10 reversed may be sufficient, and both the 2nd retardation film 3 and the 1st retardation film 10 are arrange | positioned between the upper polarizing plate 1 and the liquid crystal cell upper electrode substrate 5, May be present, or may be disposed between the lower polarizing plate 14 and the liquid crystal cell lower electrode substrate 8. In such an aspect, the first retardation film 10 may also serve as the support for the second retardation film 3.

The retardation film may be integrated with the polarizing plate, and for example, in FIG. 1, the second retardation film 3 may be integrated with the upper polarizing plate 1. In this case, it can mount in a liquid crystal display device in the state integrated with the upper polarizing plate 1. For example, the support body of a 2nd phase difference film may function as a protective film of one side of a polarizing film, and it is preferable to set it as the integral polarizing plate laminated | stacked in order of a protective film, a polarizing film, and a 2nd phase difference film. When attaching the said integral polarizing plate in a liquid crystal display device, it is preferable to mount so that it may become the order of a protective film, a polarizing film, and the 2nd phase difference film 3 from the outer side (side from a liquid crystal cell) of an apparatus.

In addition, the polarizing plate of the present invention may be used as the upper polarizing plate 1, and as described above, the second retardation film 3 may also be integrated with the polarizing plate of the present invention and attached to the liquid crystal display device. In such an aspect, it is set as the integral polarizing plate laminated | stacked in order of a protective film, a polarizing film, a 1st retardation film (the order of a support body and an optically anisotropic layer), and a 2nd retardation film, and the integral polarizing plate is made into the outer side (away from a liquid crystal cell). Side), it is preferable to mount in a liquid crystal display device so that a protective film, a polarizing film, a 1st retardation film, and a 2nd retardation film may be in order.

The second retardation film will be described in more detail.

Second Retardation Film

It is preferable to use a 2nd phase difference film with the 1st phase difference film which is the retardation film of this invention for the liquid crystal display device of this invention, especially the liquid crystal display device of a vertical alignment type. Here, it is preferable that the front retardation of a 2nd phase difference film and the retardation of the thickness direction satisfy | fill following formula [7], and / or wavelength dispersion of a 2nd phase difference film satisfy | fills following formula [8].

[7] 70 ≤ Re (550) ≤ 180 and 30 ≤ Rth (550) ≤ 140

[8] 0.7 ≤ Re (450) / Re (550) ≤ 1.0

The 2nd phase difference film which can be used by this invention may be optically monoaxial or biaxial. Moreover, a polymer film may be sufficient as the 2nd retardation film which can be used by this invention, and the layer formed from the polymerizable liquid crystal composition may be sufficient, and there will be no restriction | limiting in particular as long as various desired characteristics are obtained. The polymer to be employed is not particularly limited as long as it can achieve a uniform biaxial orientation, but for example, norbornene polymer, polycarbonate polymer, polyallylate polymer, polyester polymer, polysulfone What can form into a film by the solution casting | flow_spreading method, the extrusion molding system, etc., such as aromatic polymers, such as triacetyl cellulose, are mentioned. The biaxial optically anisotropic layer is stretched by a film produced by a suitable method such as an extrusion molding method or a flexible film forming method by a longitudinal stretching method with a roll, a transverse stretching method with a tenter, a biaxial stretching method, or the like. It can form by doing.

Re value of the 2nd phase difference film which can be used by this invention becomes like this. Preferably it is 80-170 nm, More preferably, it is 90-160 nm. Moreover, Rth value becomes like this. Preferably it is 40-120 nm, More preferably, it is 50-100 nm.

The wavelength dispersion represented by Re (450) / Re (550) is preferably 0.73 to 0.95, and more preferably 0.75 to 0.90.

In the longitudinal stretching method using the above rolls, a heating method such as a method of using a heating roll, a method of heating an atmosphere, a method of using them in combination, or the like can be adopted. Moreover, in the biaxial stretching method by a tenter, methods, such as the simultaneous biaxial stretching method by the whole tenter system, the sequential biaxial stretching method by the roll tenter method, etc. can be employ | adopted. Moreover, it is preferable that there are few orientation nonuniformity and retardation nonuniformity. Although the thickness can be suitably determined according to retardation etc., generally 1-300 micrometers is preferable from a thinning viewpoint, 10-200 micrometers is more preferable, 20-150 micrometers is more preferable.

Examples of norbornene-based polymers that can be used in the preparation of the second retardation film include norbornene and its derivatives, tetracyclododecene and its derivatives, dicyclopentadiene and its derivatives, metanotetrahydrofluorene and derivatives thereof, and the like. The polymer of the monomer which has a norbornene-type monomer of as a main component is mentioned. For example, a ring-opening polymer of a norbornene-based monomer, a ring-opening copolymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization with this, an addition polymer of a norbornene-based monomer, another norm that can be copolymerized with a norbornene-based monomer Addition copolymer with a monomer, These hydrogenated products, etc. are mentioned. Among these, the ring-opening polymer hydride of a norbornene-type monomer is the most preferable from a viewpoint of heat resistance, mechanical strength, etc. The molecular weight of a norbornene-type polymer, a monocyclic cyclic olefin polymer, or a cyclic conjugated diene polymer is suitably selected according to a use purpose. For example, the weight average molecular weight in terms of polyisoprene or polystyrene measured by gel permeation chromatography of a cyclohexane solution (toluene solution when the polymer resin is not dissolved) is preferably 5,000 to 500,000, more preferably. 8,000-200,000, More preferably, it is the range of 10,000-100,000. When it is such an average molecular weight, it is preferable because the mechanical strength and moldability of the film of the optically anisotropic layer obtained are highly balanced.

As a polycarbonate polymer which can be used for manufacture of a said 2nd retardation film, the mixture with a polycarbonate and another polymer is mentioned.

As a polyallylate type polymer which can be used for manufacture of a said 2nd phase difference film, a mixture with polyoxy benzoate etc. and other polymers is mentioned.

As polyester polymer which can be used for manufacture of said 2nd phase difference film, polyethylene terephthalate, polyethylene isophthalate, polyphenylene isophthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, etc., and other polymers And mixtures thereof.

As aromatic polymers, such as polysulfone which can be used for manufacture of a said 2nd phase difference film, a mixture with polysulfone, a polyether sulfone, polyaryl sulfone, etc., and another polymer is mentioned.

The glass transition temperature (Tg) of the polymer which can be used for manufacture of the said 2nd retardation film is suitably determined according to a use purpose. The glass transition temperature of the said resin becomes like this. Preferably it is 70 degreeC or more, More preferably, it is 80 degreeC-250 degreeC, More preferably, it is the range of 90 degreeC-200 degreeC. It is preferable to employ a resin in this range because heat resistance and molding processability are highly balanced.

The most preferable examples of the second retardation film include Japanese Unexamined Patent Publication No. 2000-137116, Japanese Unexamined Patent Publication No. 2002-14234, Japanese Unexamined Patent Publication No. 2002-48919, International Publication WO00 / 26705 pamphlet, and Japanese Unexamined Patent Publication. The retardation disclosed in JP-A 2-120804 or the like may use a stretched polymer film or a composite stretched film having reverse wavelength dispersion characteristics. Typically, a polycarbonate film having a fluorene skeleton prepared by film formation and stretching by containing liquid crystals, a cellulose acetate film produced by filming and stretching, an aromatic polyester polymer having a constant wavelength dispersion characteristic and a reverse wavelength dispersion characteristic A film prepared by filming and stretching a mixture with an aromatic polyester polymer, a film prepared by filming and stretching a polymer comprising a copolymer comprising monomer units forming polymers having different wavelength dispersion characteristics, and a wavelength dispersion characteristic The composite film etc. which laminated | stacked two different stretched films are mentioned.

The method of shape | molding resin in a sheet | seat or a film form can use either the hot melt molding method or the solution casting method, for example. In more detail, the hot melt molding method may be classified into an extrusion molding method, a press molding method, an inflation molding method, an injection molding method, a blow molding method, a stretch molding method, and the like. Among these methods, in order to obtain a film having excellent mechanical strength, surface precision, etc., Extrusion molding, inflation molding, and press molding are preferred, and extrusion molding is most preferred. Molding conditions are appropriately selected depending on the purpose of use and the molding method, but in the case of the hot melt molding method, the cylinder temperature is preferably set in the range of preferably 100 to 400 ° C, more preferably 150 to 350 ° C. The thickness of the sheet or film is preferably 0 to 300 µm, more preferably 30 to 200 µm.

Stretching of the sheet or film, when the glass transition temperature of the polymer employed in the optically anisotropic layer is Tg, preferably a temperature range of (Tg-30) ° C to (Tg + 60) ° C, more preferably (Tg At a temperature of −10) ° C. to (Tg + 50) ° C., at least one direction is preferably performed at a draw ratio of 1.01 to 2 times. In the case where the stretching direction is obtained by extrusion molding, the stretching direction is preferably the mechanical flow direction (extrusion direction) of the resin. The stretching method is preferably a free shrink uniaxial stretching method, a width fixed uniaxial stretching method, a biaxial stretching method, or the like.

Here, an example of the specific method of extending | stretching is given.

(1) The sheet is passed through a roll (heating roll) heated to a constant temperature to adjust to a desired temperature.

(2) Next, the sheet which adjusted temperature is extended | stretched by passing from the 1st roll with a relatively slow rotational speed in order of the 2nd roll with a higher rotational speed. By controlling the speed ratio between the rotational speed of the first roll and the rotational speed of the second roll, the draw ratio can be adjusted to a range of 1 to 4 times. Moreover, it is preferable to install an infrared heater etc. between a heating roll, a 1st roll, and a 2nd roll, and to keep the temperature of a sheet constant.

(3) The stretched film is passed through a cooling roll to cool.

(4) The cooled stretched film is wound up by a winding roll and collected. In order to prevent the blocking of films by winding, a masking film of the same width as the stretched film may be overlapped and wound together, or a tape having a narrow width of weak adhesive force on at least one end, preferably both ends, of the stretched film. You may wind it together while attaching.

In the step (1) of the said method, the sheet | seat which passes a heating roll may be a state whose temperature is higher than a heating roll, ie, the state immediately after shape | molding by an extruder etc. Moreover, the thing of temperature lower than a heating roll and room temperature (for example, 25-30 degreeC) may be sufficient from the point which can be made into high draw ratio. Preferably at room temperature. Thus low temperature sheet can be obtained by shape | molding a sheet | seat, and then cooling once and winding | stacking and collect | recovering on a roll. In addition, the stretching speed is preferably 5 to 1000 mm / sec, more preferably 10 to 750 mm / sec. When the stretching speed is in the above range, the stretching control becomes easy, and the surface accuracy and the in-plane variation in retardation can be made smaller.

The liquid crystal display device of the present invention is not limited to the above configuration and may include other members. For example, you may arrange | position a color filter between a liquid crystal cell and a polarizing film. Moreover, in the aspect of a transmissive liquid crystal display device, the backlight which uses a cold or hot cathode fluorescent tube, a light emitting diode, and an electroluminescent element as a light source can be arrange | positioned at the back surface. On the other hand, in the aspect of a reflection type liquid crystal display device, only one polarizing plate may be arrange | positioned at an observation side, and a reflection film is provided in the back surface of a liquid crystal cell or the inner surface of the lower substrate of a liquid crystal cell. Of course, it is also possible to provide a front light using the light source on the observation side of the liquid crystal cell. The transflective type in which the transmissive portion and the reflecting portion are provided in one pixel of the display device is also possible.

It does not specifically limit about the kind of liquid crystal display device of this invention, All liquid crystal display devices, such as an image direct view type, an image projection type, and a light modulation type, are included. An active matrix liquid crystal display device using a three-terminal or two-terminal semiconductor element such as a TFT or a MIM is particularly effective in the present invention. Of course, it is also effective in the passive matrix liquid crystal display device represented by Super-Twisted Nematic type (STN type) called time division driving.

[VA mode liquid crystal cell]

In the present invention, the liquid crystal cell is preferably in the Vertically Aligned mode (VA mode). In the VA mode liquid crystal cell, in a non-driven state where no external electric field is applied, the liquid crystal molecules are aligned in a direction substantially perpendicular to the substrate of the liquid crystal cell. Such a liquid crystal cell is formed by enclosing, for example, liquid crystal molecules having negative dielectric anisotropy between upper and lower electrode substrates on which opposing surfaces are subjected to rubbing treatment.

More specifically, using liquid crystal molecules of Δn = 0.0813 and Δε = −4.6, a director indicating the alignment direction of the liquid crystal molecules and a so-called tilt angle of about 89 ° can be manufactured. At this time, the thickness (d) (nm) of a liquid crystal layer can be about 3.5 micrometers, for example. The brightness at the time of white display changes with the magnitude | size of the product ((DELTA) n * d) of the thickness (d) of a liquid crystal layer and refractive index anisotropy ((DELTA) n). In order to obtain maximum brightness, the thickness d of the liquid crystal layer is preferably in the range of 2 to 5 µm (2000 to 5000 nm), and Δn is preferably in the range of 0.060 to 0.085. Here, refractive index anisotropy (Δn) is represented by Δn = Rth / film thickness (nm).

When the liquid crystal display device shown in FIG. 1 has a liquid crystal cell in VA mode, transparent electrodes (not shown) are formed inside the liquid crystal cell upper electrode substrate 5 and the liquid crystal cell lower electrode substrate 8, In the non-driven state where no drive voltage is applied, the liquid crystal molecules 7 in the liquid crystal layer are oriented substantially perpendicular to the substrate surface, and as a result, the polarization state of the light passing through the liquid crystal panel hardly changes. As described above, since the direction 2 of the upper polarizing plate absorption axis of the liquid crystal cell and the direction 15 of the lower polarizing plate absorption axis are approximately orthogonal, the light does not pass through the polarizing plate. That is, the liquid crystal display of FIG. 1 realizes ideal black display in a non-driven state. In contrast, in the driving state, the liquid crystal molecules are inclined in a direction parallel to the substrate surface, and the light passing through the liquid crystal panel changes the polarization state by the inclined liquid crystal molecules and passes through the polarizing plate.

In FIG. 1, since the electric field is applied between the upper and lower substrates, an example in which the dielectric anisotropy, the negative liquid crystal material, in which the liquid crystal molecules respond perpendicular to the electric field direction, is used is shown. Moreover, when an electrode is arrange | positioned on one board | substrate and an electric field is applied in the horizontal direction parallel to a board | substrate surface, the liquid crystal material can use what has positive dielectric constant anisotropy. In the liquid crystal display of the VA mode, the addition of the chiral agent generally used in the liquid crystal display of the Twisted Nematic mode (TN mode) deteriorates the dynamic response characteristics. It may be added in order to.

The VA mode features high speed response and high contrast. However, although contrast is high in the front, there exists a subject that it falls in the inclination direction. In black display, the liquid crystal molecules are oriented perpendicular to the substrate surface. When observed from the front side, since there is almost no birefringence of the liquid crystal molecules, the transmittance is low and a high contrast is obtained. However, when observed in the oblique direction, birefringence occurs in the liquid crystal molecules. Moreover, although the crossing angle of the up-and-down polarizing plate absorption axis is orthogonal 90 degrees from the front, it becomes larger than 90 degrees when it sees from a diagonal direction. Due to these two factors, leakage light is generated in the inclined direction, and the contrast tends to be lowered. In this invention, in order to solve this, the retardation film of this invention is arrange | positioned 1 or more. It is preferable to arrange | position the retardation film and 2nd retardation film of this invention one by one or more layers.

In the VA mode, the liquid crystal molecules are inclined at the time of white display, but the birefringence of the liquid crystal molecules observed in the oblique direction is different in the oblique direction and in the opposite direction, resulting in a difference in luminance and color tone. In order to solve this, it is preferable to make a liquid crystal cell into a multi-domain. The multi-domain refers to a structure in which a plurality of regions having different alignment states are formed in one pixel. For example, in the liquid crystal cell of the VA mode of the multi-domain system, a plurality of regions exist in one pixel in which the inclination angles of the liquid crystal molecules at the time of electric field application are different from each other. In the VA mode liquid crystal cell of the multi-domain system, the inclination angles of the liquid crystal molecules due to electric field application can be averaged for each pixel, thereby visualizing the visual characteristics. In order to divide the orientation within one pixel, slits or protrusions are formed on the electrodes to change the direction of the electric field or to give variation to the electric field density. In order to obtain a uniform viewing angle in all directions, the number of divisions may be increased.

Moreover, the liquid crystal molecules hardly respond at the region boundary of the orientation division. For this reason, in the normally black display, since black display is maintained, brightness deterioration becomes a problem. Adding chiral agent to the liquid crystal material contributes to making the boundary area small.

Example

Hereinafter, the present invention will be described in more detail with reference to examples. Materials, reagents, amounts of substances, proportions thereof, operations, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

[Example 1-1]

&Lt; Production of liquid crystal cell &

(Manufacture of vertically oriented liquid crystal cell)

To the 3 wt% aqueous solution of polyvinyl alcohol, 1 wt% of octadecyldimethylammonium chloride (coupling agent) was added. This was spin-coated on the glass substrate in which the ITO electrode was formed, and after heat-processing at 160 degreeC, the rubbing process was performed and the vertical alignment film was formed. The rubbing treatment was carried out so as to be opposite to each other in the two glass substrates. Two glass substrates were faced so that cell gap (d) might be set to about 5.0 micrometers. The liquid crystal compound ((DELTA) n: 0.06) which has an ester system and an ethane system as a main component was injected into the cell gap, and the vertically aligned liquid crystal cell was produced. The product of Δn and d was 300 nm.

<Production of Support 1-1>

The following composition was thrown into the mixing tank, it stirred, each component was dissolved, and the cellulose acetate solution A was prepared.

Composition of Cellulose Acetate Solution A

100.0 parts by mass of cellulose acetate having an acetyl substitution degree of 2.94

Methylene chloride (first solvent) 402.0 parts by mass

60.0 parts by mass of methanol (second solvent)

(Preparation of Mat Solution)

20 mass parts and 80 mass parts of methanol of the average particle size 16 nm silica particle (AEROSIL R972, Nippon Aerosol Co., Ltd. product) were stirred and mixed well for 30 minutes, and it was set as the silica particle dispersion liquid. This dispersion was added to the disperser together with the following composition, and stirred for 30 minutes or more to dissolve each component to prepare a mat solution.

Matte Solution Composition

10.0 parts by mass of silica particle dispersion having an average particle size of 16 nm

Methylene chloride (first solvent) 76.3 parts by mass

3.4 parts by mass of methanol (second solvent)

10.3 parts by mass of cellulose acetate solution A

(Preparation of additive solution)

The following composition was put into the mixing tank, it stirred while heating, and each component was dissolved and the additive solution was prepared.

Additive solution composition

49.3 parts by mass of the following retardation lowering agent

4.9 parts by mass of the following wavelength dispersion regulator

Methylene chloride (first solvent) 58.4 parts by mass

8.7 parts by mass of methanol (second solvent)

Cellulose acetate solution A 12.8 parts by mass

[Formula 76]

Retardation lowering agents

[Formula 77]

Wavelength dispersion adjusting agent

(Preparation of cellulose acetate film)

94.6 parts by mass of the cellulose acetate solution A, 1.3 parts by mass of the mat solution and 4.1 parts by mass of the additive solution were respectively filtered and mixed, and the mixture was cast using a band softener. In this composition, the mass ratio of the retardation lowering agent and the wavelength dispersion adjusting agent to cellulose acetate was 12% and 1.2%, respectively. After peeling a film from the band with 30% of the residual solvent quantity, it dried for 40 minutes at 140 degreeC, and produced the elongate cellulose acetate film of 80 micrometers in length. In-plane retardation (Re) of the obtained film was 1 nm, and retardation (Rth) of the thickness direction was 3 nm.

Re (400) -Re (700) was 4 nm, and Rth (400) -Rth (700) was 12 nm.

<Production of Support 1-2>

By the same method as the support body 1-1, the flexible film thickness was adjusted and the long cellulose acetate film of 35 micrometers in thickness was produced. In-plane retardation (Re) of the obtained film was 0 nm, and retardation (Rth) of the thickness direction was 0 nm.

Re (400) -Re (700) was 2 nm, and Rth (400) -Rth (700) was 6 nm.

<Production of Supports 1-3>

Supports 1-3 were prepared by the method described below.

(Preparation of Polymer 1-1)

The following composition was added to a four-necked flask (equipped with an inlet, a thermometer, a reflux condenser, a nitrogen inlet, and a stirrer), and gradually heated up to 80 ° C, polymerized for 5 hours with stirring, and after completion of the polymerization, a large amount of methanol was added to the polymer solution. Was poured into the precipitate, washed with methanol, purified and dried to obtain Polymer 1-1 having a weight average molecular weight of 3,000 (measured by GPC).

10 parts by mass of methyl acrylate

1 part by mass of 2-hydroxyethyl acrylate

1 part by mass of azobisisobutyronitrile (AIBN)

Toluene 30 parts by mass

(Film forming of support 1-3)

The following dope composition was put into a pressurized airtight container, it heated to 70 degreeC, the pressure in a container was made into 1 atmosphere or more, and the cellulose ester was melt | dissolved completely, stirring. The dope temperature was lowered to 35 degreeC, and it left still overnight, and after filtering this dope using Azumi filter paper No. 244 by Azumi Paper Co., Ltd., it was left to stand overnight and defoamed again. Filtration pressure 1.0 using Nippon Seonsen Co., Ltd. FineMet NM (absolute filtration accuracy 100 micrometers), Finepoa NF (absolute filtration precision 50 micrometers, 15 micrometers, and 5 micrometers in order) filtered through a × 10 ⁶ Pa, which was used for the film formation. The film thickness was 40 micrometers.

In-plane retardation (Re) of the obtained film was 0.6 nm, and retardation (Rth) of the thickness direction was -2.9 nm.

Re (400) -Re (700) was 3 nm, and Rth (400) -Rth (700) was 15 nm.

<Dope composition>

100 parts by mass of cellulose triacetate (degree of substitution 2.83)

15 parts by mass of polymer 1-1 of the above synthesis

0.8 parts by mass of the following UV agent (1)

0.2 parts by mass of the following UV agent (2)

475 parts by mass of methylene chloride

50 parts by mass of ethanol

UV agent (1)

(78)

UV agent (2)

(79)

<Production of Support 1-4>

Support 1-4 was manufactured like support 1-1 except having replaced the retardation reducing agent of support 1 with the compound A-1 mentioned above.

In-plane retardation (Re) of the obtained film was 0 nm, and retardation (Rth) of the thickness direction was 2 nm.

Re (400) -Re (700) was 3 nm, and Rth (400) -Rth (700) was 10 nm.

<Production of First Retardation Film 1-1>

After saponifying the surface of the support body 1-1, 20 ml / m <2> was apply | coated on this film with the coating film of the orientation film of the following composition. It dried for 60 second by the warm air of 60 degreeC, and 120 second by the warm air of 100 degreeC, and formed the film | membrane. Next, the formed film was subjected to a rubbing treatment in a direction parallel to the slow axis direction of the film to form an alignment film.

Composition of alignment film coating liquid

10 parts by mass of the following denatured polyvinyl alcohol

371 parts by mass of water

119 parts by mass of methanol

Glutaraldehyde 0.5 parts by mass

0.2 parts by mass of compound B

(80)

[Formula 81]

Modified polyvinyl alcohol

Next, the optically anisotropic layer coating liquid of the following composition was apply | coated so that Rth of the thickness direction after hardening might be 200 nm with a wire bar.

1.8 g of the discotic liquid crystalline compound shown below

Ethylene oxide-modified trimethylolpropane triacrylate

0.2 g (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.)

Photoinitiator (Igure Cure 907, Chiba Co., Ltd. product) 0.06 g

Sensitizer (Kayacure DETX, Nippon Gunpowder Co., Ltd.) 0.02g

0.01 g of fluorine-containing polymer (compound A)

Methyl ethyl ketone 3.9 g

This was attached to a metal mold and heated for 3 minutes in a 125 degreeC thermostat, and the disk-shaped liquid crystalline compound was orientated. Next, UV irradiation was carried out for 30 seconds using a 120 W / cm high-pressure mercury lamp to crosslink the discotic liquid crystalline compound. The temperature at the time of UV hardening was 80 degreeC, and the retardation film was obtained. The thickness of the optically anisotropic layer was 2.8 mu m. Thereafter, the mixture was allowed to cool to room temperature. Thus, retardation film 1-1 was manufactured. The optical characteristic of the retardation film 1-1 is shown to Table 1-1.

Discotic liquid crystalline compound

(82)

Compound A

(83)

<Production of First Retardation Film 1-2 to 1-5>

Next, except having changed the application amount of the optically anisotropic layer coating liquid, the 1st phase difference films 1-2-1-5 were manufactured by the method similar to the 1st phase difference film 1-1. The thickness of the optically anisotropic layer of the obtained 1st phase difference film was 3.5 micrometers, 2.1 micrometers, 0.7 micrometer, and 4.9 micrometer in order. The optical characteristic of the manufactured retardation film is shown in Table 1-1.

<Production of First Retardation Film 1-6>

Next, except having used the support body 1-2, the 1st phase difference film 1-6 was manufactured by the method similar to the 1st phase difference film 1-1. The optical characteristic of the manufactured retardation film is shown in Table 1-1.

<Production of First Retardation Film 1-7>

Next, except that the support body 1-3 was used, the 1st retardation film 1-7 was manufactured by the method similar to the 1st retardation film 1-1. The optical characteristic of the manufactured retardation film is shown in Table 1-1.

<Production of First Retardation Film 1-8>

Next, the first retardation film 1-7 was manufactured in the same manner as the first retardation film 1-3 except that a commercially available cellulose acetate film (Fujitak TD80UF, manufactured by Fuji Photo Film Co., Ltd.) was used as the support.

As for the optical characteristic of the support body used here, in-plane retardation (Re) was 3 nm and retardation (Rth) of the thickness direction was 45 nm.

Re (400) -Re (700) was 5 nm, and Rth (400) -Rth (700) was 13 nm. The optical characteristic of the manufactured retardation film is shown in Table 1-1.

<Production of First Retardation Film 1-9>

Next, except that the optically anisotropic layer coating liquid of the following composition was used, the 1st phase difference film 1-9 was manufactured by the method similar to the 1st phase difference film 1-1. The optical characteristic of the manufactured retardation film is shown in Table 1-1.

1.8 g of the discotic liquid crystalline compound shown below

Ethylene oxide-modified trimethylolpropane triacrylate

0.2 g (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.)

0.04 g of photoinitiator (following compound B)

0.01 g of fluorine-containing polymer (Compound A)

Methyl ethyl ketone 3.9 g

Discotic liquid crystalline compound

(84)

Compound B

(85)

<Production of First Retardation Film 1-10>

Next, the 1st phase difference film 1-10 was manufactured by the method similar to the 1st retardation film 1-9 except having changed the application amount of the coating liquid. The optical characteristic of the manufactured retardation film is shown in Table 1-1.

<Production of First Retardation Film 1-11>

75 parts by weight of a rod-like liquid crystalline compound having a spacer between the mesogen in the center and the acrylate, and 1 part by weight of a photopolymerization initiator (manufactured by Chiba Specialty Chemicals, Ilgacure Irg184). And 25 parts by weight of methyl ethyl ketone as a solvent were mixed, and as the chiral agent, 10 parts by weight of a chiral agent having a polymerizable acrylate group was added to prepare an optically anisotropic layer coating liquid.

Rod-like liquid crystalline compound

&Lt; EMI ID =

Chiralze

[Chemical Formula 87]

Where x is four.

The prepared optically anisotropic layer coating liquid is applied, dried, and UV-cured to an alignment film surface subjected to saponification treatment, an alignment film coating and a rubbing treatment to the support 1-1 in the same manner as the first retardation film, and is subjected to chiral nematic (cholesteric). A liquid crystal layer (optical anisotropic layer) was obtained. The thickness of the obtained optically anisotropic layer was 4.2 micrometers. The spiral pitch of the liquid crystal layer was 180 nm and the reflection wavelength was 280 nm. The optical characteristic of the manufactured retardation film is shown in Table 1-1.

<Production of First Retardation Film 1-12>

Next, except that the support body 1-3 was used, the 1st retardation film 1-12 was manufactured by the method similar to the 1st retardation film 1-11. Optical properties of the prepared retardation film are shown in Table 1-1.

<Production of First Retardation Film 1-13>

Next, the 1st retardation film 1-13 was manufactured by the method similar to the 1st retardation film 1-11 except having used the cellulose acetate film (Fuji-Tak TD80UF, Fuji Fujifilm Co., Ltd. product) commercially available as a support body. The optical characteristic of the manufactured retardation film is shown in Table 1-1.

<Production of First Retardation Film 1-14>

Next, using the support body 1-1, the laminated film which attached the cellulose acetate film (Fujitak TD80UF, Fuji Photo Film Co., Ltd. product) commercially available as an optically anisotropic layer with 3 sheets of adhesives was produced, and laminated | stacked with a support body The film was affixed with an adhesive, and 1st phase difference film 1-14 was manufactured. The optical characteristic of the manufactured retardation film is shown in Table 1-1.

<Production of First Retardation Film 1-15>

Next, except that the support body 1-4 was used, the 1st retardation film 1-15 was manufactured by the method similar to the 1st retardation film 1-1. The optical characteristic of the manufactured retardation film is shown in Table 1-1.

&Lt; Preparation of lower polarizer plate >

The first retardation films 1-1 to 1-15 and Fuji Tak TD80UF were attached to both surfaces of the polarizing film with a roll-to-roll using a polyvinyl alcohol-based adhesive to prepare an integrated polarizing plate. When the lamination angle of each film is based on the left and right directions when the display device is viewed from above (0 °), as shown in Fig. 2, the axial angle of the polarizing film absorption axis 104 (15 in Fig. 1) is 90 °. , The angles of the protective film slow axes 102 and 106 were set to 90 °. The manufactured lower polarizing plate was attached to the liquid crystal display so that the optically anisotropic layer (10 in FIG. 1) might contact the upper liquid crystal cell substrate (8 in FIG. 1).

<Production of Upper Polarizing Plate>

As a protective film (105 in FIG. 2), a commercially available cellulose acetate film (Fujitak TD80UF, manufactured by Fuji Photo Film Co., Ltd., Re value of 3 nm, Rth value of 50 nm) was used. In addition, between the upper polarizing plate (1 in FIG. 1) and the upper liquid crystal cell substrate (5 in FIG. 1), a polycarbonate film (trade name: Pure Ace WR (Teijin Co., Ltd.)) is used as a uniaxial retardation film made of a stretched film. At this time, it arrange | positioned so that the in-plane slow axis of retardation film might correspond with the transmission axis of an upper polarizing plate.

As for the optical characteristic of the polycarbonate film, Re was 155 nm, Rth was 78 nm, and Re (450) / Re (550) = 0.8.

<Evaluation of Display Characteristics of Liquid Crystal Display Device>

In the liquid crystal display device manufactured by the above method, the light leakage at the time of black display in the azimuth direction 45 degree from the front of an apparatus, and the color change from the front in the polar angle 60 degree were evaluated with the following criteria visually. .

(Judgment standard of light leakage)

A: No light leakage

B: Weak light leakage

C: Weak light leakage

D: Strong light leakage

(Judgment standard of color change)

A: No coloring

B: Slightly colored

C: weakly colored

D: Strongly Colored

In Table 1-1, the optical characteristic of each retardation film, and a display characteristic evaluation result are shown.

[Table 1-1]

From the evaluation result of Table 1-1, the retardation of a support body is made small and the leakage of the diagonal direction in the black display of VA liquid crystal display device is made by making the optical characteristic of retardation film into a desired value by combining with an optically anisotropic layer. It was possible to attain a high level of light and color change.

Moreover, not only the display quality but also the viewing angle of the liquid crystal display device of this invention was remarkably improved.

[Example 2-1]

&Lt; Production of liquid crystal cell &

(Manufacture of vertically oriented liquid crystal cell)

To the 3 wt% aqueous solution of polyvinyl alcohol, 1 wt% of octadecyldimethylammonium chloride (coupling agent) was added. This was spin-coated on the glass substrate in which the ITO electrode was formed, and after heat-processing at 160 degreeC, the rubbing process was performed and the vertical alignment film was formed. The rubbing treatment was carried out so as to be opposite to each other in the two glass substrates. Two glass substrates were faced so that cell gap (d) might be set to about 5.0 micrometers. The liquid crystal compound ((DELTA) n: 0.06) which has an ester system and an ethane system as a main component was injected into the cell gap, and the vertically aligned liquid crystal cell was produced. The product of Δn and d was 300 nm.

<Production of Support 2-1>

Support 2-1 was prepared by the method described below.

(Preparation of Polymer 2-1)

The following composition was added to a four-necked flask (equipped with an inlet, a thermometer, a reflux condenser, a nitrogen inlet, and a stirrer), and gradually heated up to 80 ° C, polymerized for 5 hours with stirring, and after completion of the polymerization, a large amount of methanol was added to the polymer solution. It injected | threw-in and precipitated, and wash | cleaned again with methanol, refine | purified and dried, and obtained the polymer 2-1 (acrylate type polymer) of the weight average molecular weight 3,000 (measured by GPC).

10 parts by mass of methyl acrylate

1 part by mass of 2-hydroxyethyl acrylate

Azobisisobutyronitrile (AIBN) 1.5 parts by mass

Toluene 30 parts by mass

(Film forming of support 2-1)

The following dope composition was put into a pressurized airtight container, it heated to 70 degreeC, the pressure in a container was made into 1 atmosphere or more, and the cellulose ester was melt | dissolved completely, stirring. The dope temperature was lowered to 35 degreeC, and it was left to stand overnight, and this dope was azumi filter paper No. of Azumi Filtration Co., Ltd. product. After filtration using 244, it was left to stand overnight and defoamed again. Filtration pressure 1.0 using Nippon Seonsen Co., Ltd. FineMet NM (absolute filtration accuracy 100 micrometers), Finepoa NF (absolute filtration precision 50 micrometers, 15 micrometers, and 5 micrometers in order) filtered through a × 10 ⁶ Pa, which was used for the film formation.

<Dope composition>

100 parts by mass of cellulose triacetate (degree of substitution 2.83)

15 parts by mass of polymer 2-1 of the above synthesis

0.8 parts by mass of the following UV agent (1)

0.2 parts by mass of the following UV agent (2)

475 parts by mass of methylene chloride

50 parts by mass of ethanol

[Formula 88]

UV agent (1)

(89)

UV agent (2)

The film thickness of the produced support body 2-1 was 80 micrometers.

Moreover, the in-plane retardation (Re (630)) of the obtained film is 2 nm, the retardation (Rth (630)) of thickness direction is -7 nm, and | Re (400) -Re (700) | is 3 nm, In addition, Rth (400) -Rth (700) was -25 nm.

<Production of Support 2-2>

Support 2-2 was prepared by the method described below.

(Preparation of Polymer 2-2)

Using the following composition, Polymer 2-2 (acrylate-based polymer) was synthesized in the same manner as Polymer 2-1. The weight average molecular weight of polymer 2-2 was 2,000.

6 parts by mass of methyl methacrylate

5 parts by mass of ethyl methacrylate

1 part by mass of 2-hydroxyethyl acrylate

2 parts by mass of azobisisobutyronitrile (AIBN)

Toluene 30 parts by mass

(Film forming of support 2-2)

A support 2-2 was prepared in the same manner as the support 2-1 except that Polymer 2-1 of the dope composition was replaced with Polymer 2-2.

The film thickness of the produced support body 2-2 was 80 micrometers.

Moreover, in-plane retardation (Re (630)) of the obtained film is 2 nm, retardation (Rth (630)) of thickness direction is -5 nm, | Re (400) -Re (700) | is 2 nm, In addition, Rth (400) -Rth (700) was -20 nm.

<Production of Support 2-3>

A support 2-3 was prepared in the same manner as the support 2-2 except that the support film thickness was changed to 40 µm.

Moreover, in-plane retardation (Re (630)) of the obtained film is 2 nm, retardation (Rth (630)) of thickness direction is -5 nm, | Re (400) -Re (700) | is 2 nm, In addition, Rth (400) -Rth (700) was -20 nm.

<Production of Support 2-4>

Support 2-4 was prepared by the method described below.

(Film forming of support 2-4)

A support 2-4 was prepared in the same manner as the support 2-1 except that the following dope composition was changed to the following composition.

(Dope composition)

100 parts by mass of cellulose triacetate (degree of substitution 2.90)

10 parts by mass of the polymer 2-1 of the above synthesis

Triphenyl phosphate 4 parts by mass

2 parts by mass of biphenyldiphenylphosphate

0.8 parts by mass of the UV agent (1)

0.2 parts by mass of the UV agent (2)

475 parts by mass of methylene chloride

50 parts by mass of ethanol

The film thickness of the prepared support body 2-4 was 80 micrometers.

Moreover, in-plane retardation (Re (630)) of the obtained film is 3 nm, retardation (Rth (630)) of thickness direction is -5 nm, | Re (400) -Re (700) | is 2 nm, In addition, Rth (400) -Rth (700) was -13 nm.

<Production of Support 2-5>

Support 2-5 was prepared by the method described below.

(Film forming of support 2-5)

A support 2-5 was prepared in the same manner as the support 2-1 except that the following dope composition was changed to the following composition.

(Dope composition)

100 parts by mass of cellulose triacetate (degree of substitution 2.92)

20 parts by mass of UMM-1001 (acrylic polymer)

1.4 parts by mass of the following UV agent (3)

475 parts by mass of methylene chloride

50 parts by mass of ethanol

UMM-1001: Act Flow of Toa Synthetic Co., Ltd.

(90)

UV agent (3)

The film thickness of the prepared support body 2-5 was 80 micrometers.

The in-plane retardation (Re (630)) of the obtained film is 2 nm, the retardation (Rth (630)) of the thickness direction is 5 nm, | Re (400) -Re (700) | is 1 nm, and Rth ( 400) -Rth (700) was 20 nm.

<Production of First Retardation Film 2-1>

After saponifying the surface of the support body 2-1, 20 ml / m <2> was apply | coated on this film with the coating film of the orientation film of the following composition. It dried for 60 second by the warm air of 60 degreeC, and 120 second by the warm air of 100 degreeC again, and formed the film | membrane. Next, the formed film was subjected to a rubbing treatment in a direction parallel to the slow axis direction of the film to form an alignment film.

(Composition of alignment film coating liquid)

10 parts by mass of the following denatured polyvinyl alcohol

371 parts by mass of water

119 parts by mass of methanol

Glutalaldehyde 0.5 parts by mass

0.2 parts by mass of compound B

[Formula 91]

&Lt; EMI ID =

Modified polyvinyl alcohol

Next, the optically anisotropic layer coating liquid of the following composition was apply | coated so that Rth of the thickness direction after hardening might be 200 nm with a wire bar.

(Optical anisotropic layer coating liquid)

1.8 g of the discotic liquid crystalline compound shown below

Ethylene oxide-modified trimethylolpropane triacrylate

0.2 g (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.)

Photoinitiator (Igure Cure 907, Chiba Co., Ltd. product) 0.06 g

Sensitizer (Kayacure DETX, Nippon Gunpowder Co., Ltd.) 0.02g

0.01 g of fluorine-containing polymer (compound A)

Methyl ethyl ketone 3.9 g

Discotic liquid crystalline compound

&Lt; EMI ID =

Compound A

(94)

This was attached to a metal mold and heated for 3 minutes in a 125 degreeC thermostat, and the disk-shaped liquid crystalline compound was orientated. Next, UV irradiation was carried out for 30 seconds using a 120 W / cm high-pressure mercury lamp to crosslink the discotic liquid crystalline compound. The temperature at the time of UV hardening was 80 degreeC, and the retardation film was obtained. The thickness of the optically anisotropic layer was 2.9 micrometers. Thereafter, the mixture was allowed to cool to room temperature. Thus, retardation film 2-1 was produced. The optical characteristics of the retardation film 2-1 are shown in Table 2-1.

<Manufacture of 1st phase difference film 2-2-film 2-5>

Next, except for changing the application amount of the optically anisotropic layer coating liquid, the first retardation film 2-2 to film 2-5 were manufactured by the same method as the 1st retardation film 2-1. The thickness of the optically anisotropic layer of the obtained 1st phase difference film was 3.6 micrometers, 2.2 micrometers, 0.8 micrometer, and 5.0 micrometers in order. Optical characteristics of the produced retardation film are shown in Table 2-1.

<Production of First Retardation Film 2-6>

Next, a cellulose acetate film (Fujitak TD80UF, manufactured by Fuji Photo Film Co., Ltd., Re (630) = 3 nm, Rth (630) = 45 nm, Re (400) -Re (700) = −) Using the 5 nm and Rth (400) -Rth (700) = -13 nm), the 1st phase difference film 2-6 was manufactured by the method similar to the 1st retardation film 2-1 except having adjusted the coating film thickness. .

Optical characteristics of the produced retardation film are shown in Table 2-1.

<Production of First Retardation Film 2-7>

75 parts by weight of a rod-like liquid crystalline compound having a spacer between the mesogen in the center and the acrylate and a photopolymerization initiator (manufactured by Chiba Specialty Chemicals, Ilgacure Irg184), having a polymerizable acrylate group at both ends. 25 mass parts of methyl ethyl ketone as a solvent were mixed, and also 10 mass parts of chiral agents which have an acrylate group which can superpose | polymerize as both chiral agents were added, and the optically anisotropic layer coating liquid was prepared.

Rod-like liquid crystalline compound

&Lt; EMI ID =

Chiralze

&Lt; EMI ID =

Where x is 4.

The prepared optically anisotropic layer coating liquid is applied, dried, and UV-cured to an alignment film surface subjected to saponification treatment, application of an alignment film, and rubbing to the support 2-1 in the same manner as the first retardation film, and subjected to chiral nematic (cholesteric). A liquid crystal layer (optical anisotropic layer) was obtained. The thickness of the obtained optically anisotropic layer was 4.2 micrometers. The spiral pitch of the liquid crystal layer was 180 nm and the reflection wavelength was 280 nm. Optical characteristics of the produced retardation film are shown in Table 2-1.

<Production of First Retardation Film 2-8>

Next, except having used the support body 2-2, the 1st retardation film 2-8 was manufactured by the method similar to the 1st retardation film 2-7. Optical characteristics of the produced retardation film are shown in Table 2-1.

<Production of First Retardation Film 2-9>

Next, except having used the support body 2-3, the 1st retardation film 2-9 was manufactured by the same method as the 1st retardation film 2-7. Optical characteristics of the produced retardation film are shown in Table 2-1.

<Production of First Retardation Film 2-10>

Next, except having used the support body 2-4, the 1st retardation film 2-10 was manufactured by the method similar to the 1st retardation film 2-7. Optical characteristics of the produced retardation film are shown in Table 2-1.

<Production of First Retardation Film 2-11>

Next, except having used the support body 2-5, the 1st retardation film 2-11 was manufactured by the method similar to the 1st retardation film 2-7. Optical characteristics of the produced retardation film are shown in Table 2-1.

<Production of First Retardation Film 2-12>

Next, a 1st retardation film was carried out by the method similar to 1st retardation film 2-7 except having used the cellulose acetate film (Fujitak TD80UF, Fuji Photographic Film Co., Ltd. product) marketed as a support body, and adjusting the coating film thickness. 2-12 were prepared.

<Production of First Retardation Film 2-13>

Weight average molecular weight synthesized from 2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane and 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl ( Mw) 120,000 polyimides were dissolved in cyclohexanone to prepare a 15 wt% polyimide solution. And the said polyimide solution was apply | coated on the support body 2-4. And as a result of drying this coating film at 100 degreeC for 10 minutes, the polyimide film of thickness 5micrometer was formed. Thus, retardation film 2-13 was produced. The optical characteristics of the retardation film are shown in Table 2-1.

<Production of First Retardation Film 2-14>

Weight average molecular weight synthesized from 4,4'-bis (3,4-dicarboxyphenyl) -2,2-diphenylpropane dianhydride and 2,2'-dichloro-4,4'-diaminobiphenyl ( Mw) 30,000 polyimide was dissolved in cyclopentanone to prepare a 20% by weight polyimide solution. And the said polyimide solution was apply | coated on the support body 2-4. And when this coating film was heat-processed at 130 degreeC for 5 minutes, the transparent and smooth polyimide film of thickness 8micrometer was formed. Thus, retardation film 2-14 was produced. The optical characteristics of the retardation film are shown in Table 2-1.

<Production of First Retardation Film 2-15>

The polyimide used for retardation film 2-13 was apply | coated on the support body 2-4. This coating film was dried for 10 minutes at 100 ° C. Subsequently, the laminate of the polyimide coating film and the support was subjected to biaxial stretching of 10% at 160 ° C with respect to the length of the laminate before stretching, to form a polyimide biaxially stretched film having a thickness of 4 μm on the support. It became. Thus, retardation film 2-15 was manufactured. The optical characteristics of the retardation film are shown in Table 2-1.

<Production of First Retardation Film 2-16>

Next, using a cellulose acetate film (Fujitak TD80UF, manufactured by Fuji Photo Film Co., Ltd.) commercially available as a support, and adjusting the coating film thickness, the first retardation film in the same manner as in the first retardation film 2-13 2-16 were prepared.

&Lt; Preparation of lower polarizer plate >

Said 1st retardation film 2-1-film 2-12 and Fuji Tak TD80UF were affixed by the roll-to-roll on both surfaces of a polarizing film using the polyvinyl alcohol-type adhesive agent, and the integral polarizing plate was produced. When the lamination angle of each film is based on the left and right directions when the display device is viewed from above (0 °), as shown in Fig. 2, the axial angle of the polarizing film absorption axis 104 (15 in Fig. 1) is 90 °, The angles of the protective film slow axes 102 and 106 were set to 90 degrees. The manufactured lower polarizing plate was attached to the liquid crystal display so that the optically anisotropic layer (10 in FIG. 1) might contact the upper liquid crystal cell substrate (8 in FIG. 1).

<Production of Upper Polarizing Plate>

As a protective film (105 in FIG. 2), a commercially available cellulose acetate film (Fujitak TD80UF, manufactured by Fuji Photo Film Co., Ltd., Re value of 3 nm, Rth value of 50 nm) was used. In addition, between the upper polarizing plate (1 in FIG. 1) and the upper liquid crystal cell substrate (5 in FIG. 1), a polycarbonate film (trade name: Pure Ace WR (Teijin Co., Ltd.)) is used as a uniaxial retardation film made of a stretched film. At this time, it arrange | positioned so that the in-plane slow axis of retardation film might correspond with the transmission axis of an upper polarizing plate.

As for the optical characteristic of the polycarbonate film, Re was 155 nm, Rth was 78 nm, and Re (450) / Re (550) = 0.8. That is, the optical characteristic requested | required of the 2nd phase difference film was satisfied.

<Evaluation of Display Characteristics of Liquid Crystal Display Device>

In the liquid crystal display device manufactured by the above method, the light leakage at the time of black display in the azimuth direction 45 degree from the front of an apparatus, and the color change from the front in the polar angle 60 degree were evaluated with the following criteria visually. .

(Judgment standard of light leakage)

A: No light leakage

B: Weak light leakage

C: Weak light leakage

D: Strong light leakage

(Judgment standard of color change)

A: No coloring

B: Slightly colored

C: weakly colored

D: Strongly Colored

In Table 2-1, the optical characteristic and display characteristic evaluation result of each retardation film are shown.

<Fragility Evaluation of Retardation Film>

Five film samples were piled up and punched on the 18 cm x 16 cm rubber mat of the Thompson punching machine, and the length of the crack formed longest from the four corners inward was measured, and brittleness was evaluated by punching aptitude. (Circle) and 2 to 3 mm or less, (triangle | delta) and the thing exceeding 3 mm are represented by x as 2 mm or less.

TABLE 2-1

From the evaluation result of Table 2-1, the polarizing plate which has the retardation film of this invention, ie, the liquid crystal display device of VA mode using the polarizing plate of this invention, light leakage and color change at the time of black display at the time of observing from the inclination direction are all Was hardly observed.

On the other hand, since film 2-4-film 2-6 do not satisfy | fill said formula [3] and / or said formula [4], in the comparative example using this as a 1st phase difference film, it is the time of black display in a diagonal direction. Light leakage and color change were observed. In addition, since film 2-12 also did not satisfy said formula [4], in the comparative example using this as a 1st phase difference film, the light leakage at the time of black display and color change in the inclination direction were observed.

By using the retardation film and polarizing plate of this invention, it is possible to optically compensate a liquid crystal cell (especially liquid crystal cell of VA mode) with the structure similar to the conventional liquid crystal display device.

In particular, in the black display of a liquid crystal display device (especially, liquid crystal display device of VA mode), the retardation film and polarizing plate of this invention contribute to reduction of both light leakage of a tilt direction and color change, and not only a front direction but a tilt direction. Contributes to the improvement of display characteristics.

Moreover, in the conventional liquid crystal display device, in order to optically compensate a liquid crystal cell accurately, the process of laminating | stacking the some retardation film while adjusting the angle of those in-plane slow axis and the absorption axis of a polarizing plate strictly was needed. However, although the retardation film of this invention does not need to go through this process, it is possible, for example, to form and manufacture an optically anisotropic layer continuously in a long support body, and also when manufacturing the polarizing plate of this invention, It is possible to manufacture by laminating a long polarizing film continuously. Furthermore, when forming an optically anisotropic layer by application | coating, it is not necessary to thicken a layer thickness in order to ensure an optical characteristic, and it is possible to manufacture stably without the problem of nonuniformity etc. at the time of application | coating.

In addition, according to the present invention, the display characteristics in the case of observing from the front direction are good, and the display characteristics in the case of observing from the oblique direction are also good, specifically, in the case of observing in the oblique direction at the time of black display. A liquid crystal display device, in particular, a VA mode liquid crystal display device, in which light leakage and color change are reduced can be provided.

Claims (41)

A retardation film having a support and at least one optically anisotropic layer, The front retardation Re of the support body and the retardation Rth of the thickness direction satisfy the following formula [1], The wavelength dispersion of the support satisfies the following formula [2] -1, The support is made of a cellulose acylate film, The front retardation Re and the retardation Rth of the thickness direction of the retardation film satisfy the following formula [3], and The wavelength dispersion of the retardation film satisfies the following formula [4]: [1] 0 ≤ Re (630) ≤ 10 and | Rth (630) | ≤ 25 [2] -1 | Re (400) -Re (700) | ≤ 10 and | Rth (400) -Rth (700) | ≤ 35 [3] 0 ≤ Re (550) ≤ 10 and 100 ≤ Rth (550) ≤ 300 [4] 1.04 ≤ Rth (450) / Rth (550) ≤ 1.30 In formula, Re ((lambda)) is represented by Re ((lambda)) = (nx-ny) xd and shows the front retardation value (unit: nm) in wavelength (lambda) nm; Rth (λ) is represented by Rth (λ) = {(nx + ny) / 2-nz} × d and represents a retardation value (unit: nm) in the film thickness direction at a wavelength λ nm; nx is the refractive index of the slow-axis direction in a film plane, ny is the refractive index of the fast axis direction in a film plane, nz is the refractive index of the thickness direction of a film, and d is the thickness (nm) of a film. A retardation film having a support and at least one optically anisotropic layer, The support is made of a cellulose acylate film containing at least one acrylic polymer, The front retardation Re of the support body and the retardation Rth of the thickness direction satisfy the following formula [1], The wavelength dispersion of the support satisfies the following formula [2] -2, The front retardation Re and the retardation Rth of the thickness direction of the retardation film satisfy the following formula [3], and The wavelength dispersion of the retardation film satisfies the following formula [4]: [1] 0 ≤ Re (630) ≤ 10 and | Rth (630) | ≤ 25 [2] -2 | Re (400) -Re (700) | ≤ 10 and -35 ≤ Rth (400) -Rth (700) ≤ 60 [3] 0 ≤ Re (550) ≤ 10 and 100 ≤ Rth (550) ≤ 300 [4] 1.04 ≤ Rth (450) / Rth (550) ≤ 1.30 In formula, Re ((lambda)) is represented by Re ((lambda)) = (nx-ny) xd, and shows the front-face retardation value (unit: nm) in wavelength (lambda) nm, and Rth ((lambda)) is Rth ((lambda)). ) = {(nx + ny) / 2-nz} xd, and represents the retardation value (unit: nm) of the film thickness direction in wavelength (lambda), nx is the refractive index of the slow-axis direction in a film plane, ny Is a refractive index in the fast axis direction in the film plane, nz is a refractive index in the thickness direction of the film, and d is a thickness (nm) of the film. 3. The method according to claim 1 or 2, The wavelength dispersion property of the said retardation film is a following formula [5], [5] A retardation film, satisfying 1.06 ≦ Rth (450) / Rth (550) ≦ 1.30. 3. The method according to claim 1 or 2, At least one layer of the optically anisotropic layer fixes the polymerizable liquid crystal composition containing at least one of the discotic liquid crystalline compounds by homeotropic alignment of the molecules of the discotic liquid crystalline compound, and polymerization by polymerization in a state of the nematic liquid crystal phase. The retardation film which is a layer formed by making it. 3. The method according to claim 1 or 2, At least one layer of the optically anisotropic layer is formed by fixing the polymerizable liquid crystal composition containing at least one of the rod-like liquid crystalline compounds by polymerizing the molecules of the rod-like liquid crystalline compound in a cholesteric liquid crystal phase. Retardation film, which is a layer. 3. The method according to claim 1 or 2, A retardation film, wherein at least one layer of the optically anisotropic layer is a polymer layer. The method according to claim 6, Retardation film in which the said polymer layer contains 1 or more types of polymers chosen from the group which consists of a polyamide, a polyimide, polyester, a polyether ketone, a polyamideimide, and a polyester imide. 3. The method according to claim 1 or 2, Retardation film in which 1 or more layers of the said optically anisotropic layer contain a fluorine-containing compound. The method of claim 1, 0.01 to 30% by mass of one or more of compounds in which the support lowers at least one of Re (λ) and Rth (λ) to cellulose acylate having an acyl substitution degree of 2.85 to 3.00, based on the cellulose acylate. The retardation film obtained by adding. The method of claim 1, The retardation film whose film thickness of the said support body is 10-120 micrometers. 3. The method of claim 2, The wavelength dispersion of the support is represented by the following formula [6], [6] Re (400) -Re (700) | Retardation film which satisfies ≤ 10 and 0 ≤ Rth (400)-Rth (700) ≤ 60. 3. The method of claim 2, The retardation film in which the said support body consists of the cellulose acylate film containing the cellulose acylate of acyl substitution degree 2.70-3.00. 3. The method of claim 2, The phase difference film whose weight average molecular weights of the said acrylic polymer are 500 or more and less than 10,000. 3. The method of claim 2, A retardation film, wherein the acrylic polymer is an acrylic polymer having a hydroxyl group in at least one of a main chain and a side chain. 3. The method of claim 2, The retardation film in which the said support body consists of a cellulose acylate film containing a plasticizer. 3. The method of claim 2, The retardation film whose film thickness of the said support body is 10-60 micrometers. It has a polarizing film and the protective film formed in both surfaces of the said polarizing film, At least one of the said protective film is a retardation film of Claim 1 or 2, The polarizing plate. It has a polarizing film, the retardation film of Claim 1 or 2, and a 2nd retardation film, The front retardation of the said 2nd phase difference film and the retardation of thickness direction are following formula [7], [7] 70 ≤ Re (550) ≤ 180 and 30 ≤ Rth (550) ≤ 140, and The wavelength dispersion of the second retardation film is the following formula [8], [8] A polarizing plate satisfying 0.7 ≦ Re (450) / Re (550) ≦ 1.0. The retardation film according to claim 1 or 2, or The polarizing plate which has a polarizing film and the protective film formed on both surfaces of the said polarizing film, and at least one of the said protective films is the retardation film of Claim 1 or 2, or It has a polarizing film, the retardation film of Claim 1 or 2, and a 2nd retardation film, The front retardation of the said 2nd retardation film and the retardation of thickness direction are following formula [7], [7] 70 ≤ Re (550) ≤ 180 and 30 ≤ Rth (550) ≤ 140, and The wavelength dispersion of the second retardation film is the following formula [8], [8] A liquid crystal display device comprising a polarizing plate satisfying 0.7 ≦ Re (450) / Re (550) ≦ 1.0. It has two polarizing plates which mutual absorption axes mutually orthogonally cross, and the liquid crystal cell arrange | positioned between the said two polarizing plates, The liquid crystal cell has a liquid crystal layer composed of liquid crystal molecules sandwiched between a pair of substrates and the pair of substrates, and in a non-driven state in which no external electric field is applied, the liquid crystal molecules with respect to the pair of substrates Oriented in a vertical direction, further comprising the retardation film of claim 1 or 2, The polarizer The polarizing plate which has a polarizing film and the protective film formed on both surfaces of the said polarizing film, and at least one of the said protective films is the retardation film of Claim 1 or 2, or It has a polarizing film, the retardation film of Claim 1 or 2, and a 2nd retardation film, The front retardation of the said 2nd retardation film and the retardation of thickness direction are following formula [7], [7] 70 ≤ Re (550) ≤ 180 and 30 ≤ Rth (550) ≤ 140, and The wavelength dispersion of the second retardation film is the following formula [8], [8] A liquid crystal display device, wherein the polarizing plate satisfies 0.7 ≦ Re (450) / Re (550) ≦ 1.0. 20. The method of claim 19, The liquid crystal display further has a second retardation film, the second retardation film is made of a polymer stretched film, the front retardation and retardation in the thickness direction is represented by the following formula [7], [7] A liquid crystal display device satisfying 70 ≦ Re (550) ≦ 180 and 30 ≦ Rth (550) ≦ 140. 20. The method of claim 19, The liquid crystal display further has a second retardation film, the wavelength dispersion of the second retardation film is the following formula [8], [8] A liquid crystal display device satisfying 0.7 ≦ Re (450) / Re (550) ≦ 1.0. 20. The method of claim 19, The liquid crystal display further has a second retardation film, wherein the second retardation film is a cellulose acylate film, a norbornene-based film, a polycarbonate-based film, a polyallylate-based film, a polyester-based film, and a polysulfone-based film. The liquid crystal display device which consists of either. 20. The method of claim 19, The liquid crystal display device further has a second retardation film, and the second retardation film is directly laminated on one side of the polarizing film in an arrangement in which absorption axes of the polarizing film are perpendicular to each other. 3. The method according to claim 1 or 2, Retardation film whose said front retardation (Re (550)) is 8 nm or less. 3. The method according to claim 1 or 2, Retardation film whose said front retardation (Re (550)) is 5 nm or less. 3. The method according to claim 1 or 2, Retardation film whose said front retardation (Re (550)) is 3 nm or less. 3. The method according to claim 1 or 2, Retardation (Rth (550)) of the said thickness direction is 120-280 nm, retardation film. 3. The method according to claim 1 or 2, Retardation (Rth (550)) of the said thickness direction is 140-260 nm, retardation film. 3. The method according to claim 1 or 2, Retardation (Rth (550)) of the said thickness direction is 160-240 nm, retardation film. 3. The method according to claim 1 or 2, The retardation film whose wavelength dispersion property of the said retardation film is 1.06 <= Rth (450) / Rth (550) <= 1.30. 3. The method according to claim 1 or 2, The retardation film whose wavelength dispersion property of the said retardation film is 1.08 <= Rth (450) / Rth (550) <= 1.28. 3. The method according to claim 1 or 2, The retardation film whose wavelength dispersion property of the said retardation film is 1.10 <= Rth (450) / Rth (550) <= 1.26. The method of claim 1, The retardation film in which said Formula [1] satisfies 0 <Re (630) <= 5 and | Rth (630) | ≤20. The method of claim 1, The retardation film in which the formula [1] satisfies 0 ≦ Re (630) ≦ 2 and | Rth (630) | ≦ 15. The method of claim 1, The retardation film in which said formula [2] -1 satisfies | Re (400) -Re (700) | <5 and 0 <Rth (400) -Rth (700) <= 25. The method of claim 1, The retardation film in which said formula [2] -1 satisfies | Re (400) -Re (700) | <3 and 0 <Rth (400) -Rth (700) <= 15. 3. The method of claim 2, Retardation film in which said formula [1] satisfy | fills following formula [1] '. [1] '0 ≤ Re (630) ≤ 5 and | Rth (630) | ≤ 20 nm The method of claim 2, Retardation film in which said formula [1] satisfy | fills following formula [1] ". [1] "0 ≤ Re (630) ≤ 2 and | Rth (630) | ≤ 15 nm 3. The method of claim 2, The phase difference film in which said formula [2] -2 satisfy | fills following formula [2] '-2. [2] '-2 | Re (400) -Re (700) | ≤ 10 and 0 ≤ Rth (400) -Rth (700) ≤ 60 3. The method of claim 2, The phase difference film in which said formula [2] -2 satisfy | fills following formula [2] "-2. [2] "-2 | Re (400) -Re (700) | ≤ 5 and 0 ≤ Rth (400) -Rth (700) ≤ 45

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