KR101139264B1 - Long polarizing plate and method for producing the same, and liquid crystal display - Google Patents

Abstract

(Problem) It is possible to provide a polarizing plate having a small deviation in the axial angle and improving polarizer performance (particularly, the axial shift angle and light leakage), and which does not cause light leakage or color change even when an environment change such as temperature or humidity occurs. To provide an excellent liquid crystal display device.

(Solution means) A long polarizer having an absorption axis parallel to the longitudinal direction, and a slow axis orthogonal or parallel to the longitudinal direction, the retardation value Re in the film plane and the retardation value Rth in the film film thickness direction. It is set as the polarizing plate in which the long transparent film which satisfy | fills this Formula (i) (ii) is laminated | stacked. At this time, the orthogonal or parallel axis shift angle of an absorption axis and a slow axis should just be 10 degrees or less. Moreover, it is set as the liquid crystal display device using these polarizing plates.

Re₍₆₃₀₎

20 (Ⅰ) 0

Re ₍₆₃₀₎

20

25 (Ii) | Rth ₍₆₃₀₎ |

25

Long polarizer, liquid crystal cell, liquid crystal display device

Description

Long polarizing plate, its manufacturing method, and liquid crystal display device {LONG POLARIZING PLATE AND METHOD FOR PRODUCING THE SAME, AND LIQUID CRYSTAL DISPLAY}

(Patent Document 1) Japanese Patent Application Laid-Open No. 9-80424

(Patent Document 2) Japanese Unexamined Patent Publication No. Hei 10-54982

(Patent Document 3) Japanese Patent Application Laid-Open No. 11-202323

(Patent Document 4) Japanese Patent Application Laid-Open No. 9-292522

(Non-Patent Document 1) Jpn. J. Appl. Phys. 41. (2002) 4553

The present invention relates to a polarizing plate produced by laminating a long polarizer and a long transparent film having a small optical anisotropy, a manufacturing method thereof, and a liquid crystal display device using the polarizing plate.

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

Among such LCDs, 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 used for applications requiring high display quality. Is mainly 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. There is a strong demand for improvement.

In order to solve this problem, the liquid crystal display device by the so-called inplane switching (IPS) mode which applies a transverse electric field with respect to a liquid crystal, or the protrusion or slit formed in the panel by vertically aligning the liquid crystal whose dielectric anisotropy is negative The vertical orientation (VA) mode which carried out the orientation division by the electrode is proposed, and it is utilized. In recent years, these panels are being developed for TV use without remaining in monitor use, and the brightness of screen is greatly improved accordingly. For this reason, microscopic light leakage in the diagonal diagonal incidence direction at the time of black display, which has not conventionally been a problem in these operating modes, has been shown as a cause of deterioration of display quality.

As one of the means of improving the viewing angle of this color tone or black display, disposing an optical compensation material having birefringence property between the liquid crystal layer and the polarizing plate is also examined in the IPS mode. For example, by disposing a birefringent medium having a function of compensating increase or decrease in retardation of the liquid crystal layer at an inclination between the substrate and the polarizing plate, coloration when white display or halftone display is viewed directly in the inclined direction What can be improved is disclosed (refer patent document 1). Moreover, the method (refer patent document 2, 3, 4) using the optical compensation film which consists of a styrene polymer and a discotic liquid crystalline compound which have negative intrinsic birefringence is proposed. However, since most of the proposed methods are methods for improving the viewing angle by eliminating the birefringent anisotropy of the liquid crystal in the liquid crystal cell, the light leakage based on the deviation from the orthogonality of the polarization axis crossing angle when the orthogonal polarizer is viewed in the oblique direction is sufficiently solved. There is a problem that can not be. In addition, even in a system capable of compensating for this light leakage, it is very difficult to completely optically compensate the liquid crystal cell without problems. This is because even if light leakage can be completely compensated for at any wavelength, it is not necessarily compensable at other wavelengths. For example, even if light leakage is compensated for at the green wavelength having the largest visibility, there is a problem that light leakage occurs in the blue of the smaller wavelength or the red of the larger wavelength. In order to solve this problem, Non-Patent Document 1 proposes to laminate two biaxial films. However, in this method, since two biaxial films were used, there existed a problem that axial shift | offset | difference of a biaxial film is easy to generate | occur | produce, and a screen nonuniformity tends to occur. In addition, the light leakage at the time of black display is the triacetyl cellulose film conventionally used as a polarizing plate protective film between a liquid crystal cell and a polarizer, and in-plane retardation (Re) is about 5 nm, retardation (Rth) of a film thickness direction This was about 50 nm. Therefore, it is expected to develop a transparent film with small in-plane retardation Re and the retardation Rth of a film thickness direction, and to use it as a protective film of a polarizing plate. Moreover, the polarizing plate with a polarizer is anticipated also in the state which has a small axis shift of this transparent film.

In recent years, in liquid crystal displays, the temperature may increase due to the internal backlight or may be used in an environment of high temperature and high humidity. The triacetyl cellulose film as the polarizing plate protective film changes its Re and Rth depending on temperature and humidity. There was a problem that the optical compensating ability was changed and light leaked or unevenness occurred in the black display. In particular, in such a case, light leaks from the periphery of the frame of the display device due to a difference in the length and width of the display device, or the member may have different physical properties in the original width and width. The trouble that color and color change was a problem. Therefore, development of the film which can obtain the liquid crystal display device with little change of the optical compensation function by such an environment is calculated | required.

The 1st subject of this invention reduces in-plane retardation (Re) of the protective film of a long polarizing plate, retardation (Rth) of a film thickness direction, makes it substantially zero, and also the polarizing plate performance at the time of polarizing plate processing is favorable. It is to provide a polarizing plate. In addition, a shape with a long length here will not be specifically limited if the length of a longitudinal direction is 5 m or more. Preferably it is 100 m or more, More preferably, it is 1000 m or more and 10000 m or less, It is preferable at the manufacturing process.

A second object of the present invention is to provide an excellent liquid crystal display device which does not cause light leakage or color change even when a change in environment such as temperature or humidity occurs.

(1) a long polarizer having an absorption axis parallel to the longitudinal direction, and a slow axis perpendicular to or parallel to the longitudinal direction, and having a retardation value Re in the film plane and a retarder in the film thickness direction; The long polarizing plate in which the long transparent film in which a decimation value (Rth) satisfy | fills Formula (i) (ii) is laminated | stacked.

Re₍₆₃₀₎

20 (Ⅰ) 0

Re ₍₆₃₀₎

20

25 (Ii) | Rth ₍₆₃₀₎ |

25

[In formula, Re ((lambda)) is an in-plane retardation value (unit: nm) in wavelength (lambda) nm, and Rth ((lambda)) is a retardation value (unit: nm) of the film thickness direction in wavelength (lambda) nm.]

(2) The perpendicular | vertical or parallel axial shift angle of the absorption axis of the said polarizer and the slow axis of the said transparent film is less than 10 degrees, The long polarizing plate as described in (1) characterized by the above-mentioned.

(3) The length of the polarizing plate as described in (1) or (2) containing cellulose acylate as a polymer raw material which forms the said transparent film.

(4) Single plate transmittance (TT), parallel transmittance (PT), orthogonal transmittance (CT), and polarization degree (P) of 400 to 700 nm at 25 ° C. and 60% RH are 1 in the following formulas (a) to (d): The long polarizing plate of any one of (1)-(3) characterized by the above-mentioned.

TT

45.0(a) 40.0

TT

45.0

PT

40.0(b) 30.0

PT

40.0

2.0(c) CT

2.0

P(d) 95.0

P

(5) When orthogonal transmittance in wavelength ((lambda)) is made into T ((lambda)), T ₍₃₈₀₎ , T ₍₄₁₀₎ , and T ₍₇₀₀₎ are one or more of following formulas (e)-(g). It is satisfied, The long polarizing plate of any one of (1)-(4) characterized by the above-mentioned.

2.0(e) T ₍₃₈₀₎

2.0

1.0(i) T ₄₁₀

1.0

0.5(g) T ₍₇₀₀₎

0.5

(6) The change amount (ΔCT) and polarization change amount (ΔP) of 400 to 700 nm orthogonal transmittance at 500 ° C. under conditions of 95 ° C. and 95% RH for at least one of the following formulas (h) and (i) The long polarizing plate of any one of (1)-(5) characterized by the above-mentioned.

ΔCT

6.0(h) -6.0

ΔCT

6.0

ΔP

0.0(i) -10.0

ΔP

0.0

(However, the change amount represents the value obtained by subtracting the pre-test measurement from the post-test measurement)

(7) The change amount (ΔCT) and the change in polarization degree (ΔP) of 400 to 700 nm orthogonal transmittance at 500 ° C. under conditions of 90 ° C. at 90% RH for at least one of the following formulas (j) and (k) The long polarizing plate of any one of (1)-(6) characterized by the above-mentioned.

ΔCT

3.0(j) -3.0

ΔCT

3.0

ΔP

0.0(k) -5.0

ΔP

0.0

(8) The amount of change (ΔCT) and the degree of polarization change (ΔP) of 400 to 700 nm orthogonal transmittance when left to stand for 500 hours under the condition of 80 ° C satisfies at least one of the following formulas (l) and (m): The long polarizing plate of any one of (1)-(7) characterized by the above-mentioned.

ΔCT

3.0(l) -3.0

ΔCT

3.0

ΔP

0.0(m) -2.0

ΔP

0.0

(9) The optically anisotropic layer which satisfy | fills following formula (iii) was formed in the transparent film of the polarizing plate in any one of (1)-(8), and it was set as the optical compensation film integral type, The long polarizing plate characterized by the above-mentioned .

(Iii) Re ₍₆₃₀₎ = 0 to 200 (nm) and Rth ₍₆₃₀₎ = 0 to 400 (nm)

(10) The long polarizing plate according to (9), wherein the optically anisotropic layer is formed using a discotic liquid crystalline compound.

(11) The long polarizing plate according to (9) or (10), wherein the optically anisotropic layer is formed using a rod-like liquid crystal compound.

(12) The long polarizing plate according to any one of (9) to (11), wherein the optically anisotropic layer is made of a polymer film having birefringence.

(13) at least one polymer selected from the group consisting of polyamide, polyimide, polyester, polyetherketone, polyamideimide polyesterimide, and polyaryletherketone, wherein the polymer film forming the optically anisotropic layer is A long polarizing plate as described in (12) characterized by containing a material.

(14) The long polarizing plate in any one of (1)-(13) which provided one or more layers of a hard-coat layer, an anti-glare layer, and an antireflection layer on the surface.

(15) The polarizing plate cut out from the long polarizing plate of any one of (1)-(14).

The liquid crystal display device using the polarizing plate of (16) (15).

(17) The liquid crystal display device according to (16), wherein the liquid crystal display device is a VA or an IPS type.

(18) Roll-to-roll of a long polarizer and a long transparent film in which the retardation value (Re) in the film plane and the retardation value (Rth) in the film film thickness direction satisfy the formula (i) (ii). A method for producing a long polarizing plate, which is attached by (Roll to Roll).

Re₍₆₃₀₎

20 (i) 0

Re ₍₆₃₀₎

20

25 (Ii) | Rth ₍₆₃₀₎ |

25

[In formula, Re ((lambda)) is an in-plane retardation value (unit: nm) in wavelength (lambda) nm, and Rth ((lambda)) is a retardation value (unit: nm) of the film thickness direction in wavelength (lambda) nm.]

Carrying out the invention  Best form for

A polarizing plate consists of a polarizer and the transparent film which protects both surfaces.

Below, the detail of the transparent film (henceforth "the transparent film concerning this invention") used for the polarizing plate of this invention is demonstrated.

[Production Method of Transparent Film]

Hereinafter, the manufacturing method of the transparent film which concerns on this invention is demonstrated.

[Film Production Method by Solvent Cast Method]

It is preferable that the transparent film which concerns on this invention produces a film with a long length continuously by the solvent cast method. In the solvent cast method, the dope is cast on a suitable support, preferably a metal support, using a solution (dope) in which the raw material polymer of the film is dissolved in a suitable organic solvent, and then the solvent is dried to release the film from the support. Then, the solvent is sufficiently dried from the film to prepare.

[Residual Solvent Amount at Peeling]

When producing a film by the solvent cast method, a film is dried on a metal support body, and it peels at the time a film gelatinized. In order to peel a film, it is preferable that the amount of residual solvent in a film is 60 to 150%. The residual solvent amount is represented by the following formula. In addition, the residual volatile matter weight is the value which subtracted the film weight after heat processing from the film weight before heat processing, when heat-processing a film at 120 degreeC for 2 hours.

Residual Solvent Amount = Residual Volatile Weight / Film Weight x 100 (%) after Heat Treatment

[Tension on Film Transfer]

In the drying step after peeling from the metal support, the film generally tries to shrink in the width direction (direction perpendicular to the machine direction) by evaporation of the solvent. In preparation of the transparent film which concerns on this invention, it is necessary to control so that a film may not be extended | stretched strongly in any of the direction of a machine and a direction perpendicular | vertical to it. Specifically, at the time of conveyance of the film in the machine direction, it is preferable to set the strength of the tension applied to the machine direction of the film from the roll for film transport to 10 to 50 kgf / m. On the other hand, it is preferable to make the strength of the tension applied to the direction perpendicular to the machine direction the same. In this case, a tenter system using a tenter clip for supporting the film in the vertical direction and adjusting the tension can also be preferably used. For example, it is preferable to dry the whole process or part of the processes disclosed in Japanese Patent Application Laid-open No. 62-46625 by picking both ends of the web by a clip in the width direction while maintaining the width (tenter method). Can be used.

[Physical Properties of Transparent Films]

The physical properties of the transparent film according to the present invention will be described below.

[Elastic modulus of film]

The tensile modulus in the machine direction of the transparent film according to the present invention is 240 to 500 kgf / mm 2, the tensile modulus in the direction perpendicular to the machine direction is 230 to 480 kgf / mm 2, and the tensile modulus in the machine direction is perpendicular to the machine direction. It is preferable that ratio of tensile modulus of elasticity of a direction is 0.80-1.36.

More preferably, the tensile modulus in the machine direction is 250 to 480 kgf / mm 2, the tensile modulus in the direction perpendicular to the machine direction is 240 to 470 kgf / mm 2, and the tensile modulus in the machine direction / perpendicular to the machine direction. The ratio of tensile modulus is 0.85-1.30. More preferably, the tensile modulus in the machine direction is 260 to 460 kgf / mm 2, the tensile modulus in the direction perpendicular to the machine direction is 250 to 450 kgf / mm 2, and the tensile modulus in the machine direction / perpendicular to the machine direction. The tensile modulus ratio is 0.88 to 1.25. As a specific measuring method, using a universal tensile tester STM T50BP manufactured by Toyobold Co., Ltd., the stress at 0.5% elongation was measured at a tensile rate of 10% / min in a 23 ° C. 70% atmosphere to obtain an elastic modulus.

[Storage Modulus of Film]

In the transparent film according to the present invention, the storage modulus in the machine direction and the storage modulus in the direction perpendicular to the machine direction are all 15000 to 80000 kgf / cm 2, and the storage modulus in the direction perpendicular to the machine direction. It is preferable that ratio is 0.80-1.20.

More preferably, the storage modulus is 18000 to 7500 kgf / cm 2 in both the machine direction and the vertical direction, and the ratio of the storage modulus in the direction perpendicular to the machine direction is 0.82 to 1.18. More preferably, the storage modulus in the machine direction and the vertical direction is 20000 to 70,000 kgf / cm 2, and the ratio of the storage modulus in the machine direction / storage modulus in the direction perpendicular to the machine direction is 0.84 to 1.16.

The specific measuring method measured dynamic viscoelasticity while changing temperature, and calculated | required storage elastic modulus from it.

[Photoelastic coefficient of film]

In the transparent film according to the present invention, both the photoelastic coefficient in the machine direction and the photoelastic coefficient in the direction perpendicular to the machine direction are 50 × 10 ⁻¹³ cm 2 / dyne or less, and the photoelastic coefficient in the machine direction / direction perpendicular to the machine direction. The ratio of photoelastic coefficient of is preferably 0.80 to 1.20.

More preferably, both the photoelastic coefficient in the machine direction and the photoelastic coefficient in the direction perpendicular to the machine direction are 40 × 10 ⁻¹³ cm 2 / dyne or less, and the photoelastic coefficient in the machine direction / photoelastic coefficient in the direction perpendicular to the machine direction. The ratio of is from 0.82 to 1.18.

More preferably, both the photoelastic coefficient in the machine direction and the photoelastic coefficient in the direction perpendicular to the machine direction are 30 × 10 ⁻¹³ cm 2 / dyne or less, and the photoelastic coefficient in the machine direction / photoelastic coefficient in the direction perpendicular to the machine direction. The ratio of is 0.84 to 1.16.

As a specific measuring method, tensile stress is applied to the major axis direction of the transparent film sample 12 mm x 120 mm which concerns on this invention, and the retardation at that time is measured with the ellipsometer (M150, Nippon Spectroscopy), The photoelastic coefficient was calculated from the amount of change in retardation with respect to the stress.

[Change of Dimension of Film]

The dimensional change rate after 60 hours at 90 ° C and 90% RH and the dimensional change rate after 90 hours at dry temperature of 24 ° C. of the transparent film according to the present invention are ± 0.5% or less in both the machine direction and the direction perpendicular to the machine direction. In all cases, the ratio of (dimension change rate in the machine direction) / (dimension change rate in the direction perpendicular to the machine direction) is preferably 0.3 to 2.5.

More preferably, both the dimensional change rate at 60 ° C. 90% RH after 24 hours and the dimensional change rate at 90 ° C. dry 24 hours are ± 0.4% or less in both the machine direction and the direction perpendicular to the machine direction. In this case, the ratio of (the rate of change of dimensions in the machine direction) / (the rate of change of dimensions in the direction perpendicular to the machine direction) is 0.4 to 2.2.

As a specific measuring method, two transparent film samples 30 mm x 120 mm which concerns on this invention were prepared, and after adjusting humidity for 24 hours at 25 degreeC and 60% RH, it was made to automatic pingauge (Shinto Scientific Co., Ltd.). Thereby, holes of 6 mmφ were formed at intervals of 100 mm at both ends to obtain raw dimensions L0 of punch intervals. Punch spacing dimension (L1) after processing one sample at 60 degreeC and 90% RH for 24 hours, and measuring the punch spacing after processing another sample at 90 degreeC and 5% RH for 24 hours ( L2) was measured. In the measurement of all the intervals, it measured to the minimum division 1 / 1000mm. Dimensional change rate of 60 degreeC and 90% RH = {(L0-L1) / L0} * 100 The dimension change rate of 90% and 5% RH of dimensional change = {(L0-L2) / L0} x100 was calculated | required.

[Hygroscopic Expansion Coefficient of Film]

It is preferable that the moisture absorption expansion coefficient of the transparent film which concerns on this invention shall be 30x10 <^-5> /% RH or less. The hygroscopic expansion coefficient is preferably 15 × 10 ⁻⁵ /% RH or less, more preferably 10 × 10 ⁻⁵ /% RH or less. The smaller the moisture absorption expansion coefficient is, the more preferably 1.0 × 10 ⁻⁵ /% RH or more. In addition, it is preferable that the moisture absorption expansion coefficients become substantially equal in the machine direction and the vertical direction. The moisture absorption expansion coefficient represents the amount of change in the sample length when the relative humidity is changed under a constant temperature. By adjusting this hygroscopic expansion coefficient, when using a transparent film as an optical compensation film support body, it can prevent the light leakage by frame-type transmittance rise, ie distortion ,, maintaining the optical compensation function of an optical compensation film.

Since the thickness of the transparent film which concerns on this invention improves the protective property with respect to a polarizer in the one where the film thickness is thick, it is preferable, but when too thick, problems, such as a fall of the optical characteristic of a polarizing plate, curling, handleability, etc., arise, It is preferable that it is 20-200 micrometers, It is more preferable that it is 40-180 micrometers, It is especially preferable that it is 40-100 micrometers.

[Film moisture permeability]

The water vapor transmission rate of the transparent film which concerns on this invention is measured on the conditions of the temperature of 60 degreeC, and the humidity of 95% RH based on JIS standard JIS Z-0208, and it is 400-2000 g / m <2> * 24h in conversion of 80 micrometers in film thickness. desirable. It is more preferable that it is 500-1800g / m <2> * 24h, and it is especially preferable that it is 600-1600g / m <2> * 24h. When it exceeds 2000 g / m <2> * 24h, the tendency which the absolute value of the humidity dependence of Re value of a film and Rth value exceeds 0.5 nm /% RH becomes strong. Moreover, even when the optically anisotropic layer is laminated | stacked on the cellulose acylate film which concerns on this invention, and it is set as an optical compensation film, the tendency which the absolute value of humidity dependence of Re value and Rth value exceeds 0.5 nm /% RH becomes unpreferable. Can not do it. When this optical compensation sheet or polarizing plate is affixed on a liquid crystal display device, a change of a color sense and a fall of a viewing angle are caused. In addition, when the moisture permeability of the cellulose acylate film is less than 400 g / m 2 · 24h, drying of the adhesive is hindered by the cellulose acylate film in the case of attaching to both surfaces of the polarizer and the like to produce a polarizing plate, resulting in poor adhesion.

As a method for measuring the moisture permeability, the method described in pages 285 to 294: Measurement of Vapor Permeation (Mass Method, Thermometer Method, Vapor Pressure Method, and Adsorption Method) of Polymer Properties II (Polymer Experiment Lecture 4 Gyoritsu Publication) can be applied. And humidity control of the cellulose acylate film sample 70 mmφ according to the present invention at 25 ° C., 90% RH, and 60 ° C. and 95% RH for 24 hours, respectively, and then a moisture permeation test apparatus (KK-709007, Toyosei Co., Ltd.). )), The moisture content per unit area was calculated (g / m 2) according to JIS Z-0208, and the water vapor permeability was determined as the weight after moisture-pre-humidification.

[Evaluation of Optical Properties of Transparent Film]

In this specification, Re ((lambda)) and Rth ((lambda)) represent the in-plane retardation in wavelength (lambda), and the retardation of the thickness direction, respectively. Re (λ) is measured by injecting light having a wavelength of λnm in the film normal direction in KOBRA 21ADH (manufactured by Oji Measurement Instruments Co., Ltd.). Rth (λ) is the Re (λ) and the in-plane slow axis (determined by KOBRA 21ADH) as the inclination axis (rotation axis) to inject light having a wavelength of λnm in a direction inclined at + 40 ° to the film normal direction. The measured retardation value and the in-plane slow axis as the inclination axis (rotation axis) were measured in three directions of the total retardation value measured by injecting light having a wavelength of λ nm in a direction inclined at -40 ° to the film normal direction. The KOBRA 21ADH is calculated based on the retardation value. Here, the assumption of the average refractive index may be a value of a catalog of polymer handbooks (John Wiley & Sons, Inc.) and 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 the film thicknesses of these average refractive indices, KOBRA 21ADH calculates nx, ny, and nz. From this calculated nx, ny and nz, Nz = (nx-nz) / (nx-ny) is further calculated.

(In-plane retardation (Re))

Re₍₆₃₀₎

20 인 것이 바람직하다. 보다 바람직하게는 0

Re₍₆₃₀₎

15 이고, 0

Re₍₆₃₀₎

10 인 것이 더욱 바람직하다. In the transparent film which concerns on this invention, in-plane retardation is 0.

Re ₍₆₃₀₎

It is preferable that it is 20. More preferably 0

Re ₍₆₃₀₎

15 and 0

Re ₍₆₃₀₎

It is more preferable that it is ten.

(Retardation in the film thickness direction (Rth))

25 인 것이 바람직하다. 보다 바람직하게는 ｜Rth₍₆₃₀₎｜

23 이고, ｜Rth₍₆₃₀₎｜

20 인 것이 더욱 바람직하다. In the transparent film which concerns on this invention, the retardation of a film thickness direction is | Rth ₍₆₃₀₎ |

25 is preferred. More preferably | Rth ₍₆₃₀₎ |

23 and | Rth ₍₆₃₀₎ |

It is more preferable that it is 20.

(Humidity change of polarizing plate, light leakage on panel with temperature change, color change)

The transparent film which concerns on this invention can be used suitably as a transparent protective film of the polarizer for liquid crystal display devices. In the case where this is mounted in a liquid crystal display device and the temperature rises due to the backlight inside the device, or when it is used in an environment of high temperature and high humidity, the screen of the display device should be displayed in black, if it is inherently black at the time of black display. It is preferable to reduce the trouble which the light leaks from the surroundings, and the trouble which the nonuniformity changes, and the fault which a color change changes rather than the protective film of the polarizing plate used until now. More preferably, the failure as described above is zero.

[Material of transparent film]

As a material which forms the transparent film which concerns on this invention, the polymer excellent in optical performance transparency, mechanical strength, thermal stability, moisture shielding property, isotropy, etc. is preferable, and Re and Rth mentioned above are represented by Formula (i) ( Any material can be used as long as it satisfies ii). For example, polycarbonate-based polymers, polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate, acrylic polymers such as polymethyl methacrylate, and styrene-based polymers such as polystyrene and acrylonitrile-styrene copolymer (AS resin) Polymers; Polyolefins such as polyethylene and polypropylene, polyolefin-based polymers such as ethylene-propylene copolymers, vinyl chloride-based polymers, amide-based polymers such as nylon and aromatic polyamides, imide-based polymers, sulfone-based polymers, and polyether sulfone-based polymers , Polyether ether ketone polymer, polyphenylene sulfide polymer, vinylidene chloride polymer, vinyl alcohol polymer, vinyl butyral polymer, allylate polymer, polyoxymethylene polymer, epoxy polymer, or the polymer Mixed polymers are also exemplified. Moreover, the transparent film which concerns on this invention can also be formed as a cured layer of ultraviolet curable type and thermosetting resins, such as an acryl type, a urethane type, an acryl urethane type, an epoxy type, and a silicone type.

Moreover, thermoplastic norbornene-type resin can be used as a material which forms the transparent film which concerns on this invention. Examples of the thermoplastic norbornene-based resins include Nippon Zeon Co., Ltd. manufactured Zeonex, Zeonoa, JSR Co., Ltd. manufactured aton, and the like.

Moreover, as a material which forms the transparent film which concerns on this invention, the cellulose polymer represented by the triacetyl cellulose conventionally used as the transparent protective film of a polarizing plate (henceforth cellulose acylate) can be used preferably. . A cellulose acylate is demonstrated in detail below.

[Cellulose Acylate Raw Material Cotton]

As cellulose of the cellulose acylate raw material used for the transparent film which concerns on 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, and it may be used in some cases. You may mix and use. For a detailed description of these raw celluloses, see, for example, `` Plastic Material Lecture 17 Fiber Fiber Resin '' (Maruzawa, Utaze, Nikkan Kogyo Shimbun, 1970). The cellulose described in an issue (pages 7 to 8) can be used, and the cellulose acylate film is not particularly limited.

[Cellulose Acylate Substitution Degree]

Next, the cellulose acylate manufactured from the above-mentioned cellulose is described. The cellulose acylate is obtained by acylating the hydroxyl group of cellulose, and the substituent may be any of acetyl group having 2 carbon atoms of acyl group and 22 carbon atoms. In the cellulose acylate, 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 hydroxyl groups of cellulose is measured, and the degree of substitution is calculated by calculation. Can be obtained. As a measuring method, it can carry out according to ASTM D-817-91.

As mentioned above, although it does not specifically limit about the substitution degree with respect to the hydroxyl group of a cellulose in a cellulose acylate, It is preferable that the acyl substitution degree with respect to the hydroxyl group of a cellulose is 2.50-3.00. It is further more preferable that it is 2.75-3.00, and it is more preferable that it is 2.85-3.00.

The acyl group having 2 to 22 carbon atoms may be an aliphatic group, an allyl group, or is not particularly limited, and may be a single type or a mixture of two or more kinds of acetic acid and / or fatty acid having 3 to 22 carbon atoms substituted with a hydroxyl group of cellulose. These are, for example, alkylcarbonyl esters, alkenylcarbonyl esters or aromatic carbonyl esters of cellulose, aromatic alkylcarbonyl esters, and the like, and may each further have a substituted group. These preferred acyl groups include acetyl, propionyl, butanoyl, heptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, iso-butanoyl and t-butanoyl, cyclohexanecarbonyl, oleoyl, benzoyl, naphthylcarbonyl, cinnamoyl group and the like. Among these, acetyl, propionyl, butanoyl, dodecanoyl, octadecanoyl, t-butanoyl, oleoyl, benzoyl, naphthylcarbonyl, cinnamoyl and the like are preferred, and acetyl, propionyl and butanoyl are more preferred. desirable.

As a result of earnest examination by the inventor of this invention, when the acyl substituent substituted by the hydroxyl group of the cellulose mentioned above is two or more types substantially selected from an acetyl group, a propionyl group, and butanoyl group, the whole substitution degree is 2.50. In the case of -3.00, it turned out that the optical anisotropy of a cellulose acylate film can be reduced. More preferable acyl substitution degree is 2.60-3.00, More preferably, it is 2.65-3.00.

[Polymerization degree of cellulose acylate]

The polymerization degree of the cellulose acylate used preferably by this invention is 180-700 with a viscosity average polymerization degree, 180-550 is more preferable, 180-400 is still more preferable, 180-350 is especially preferable in cellulose acylate Do. When the degree of polymerization is too high, the viscosity of the dope solution of cellulose acylate becomes high, and film production becomes difficult by casting. If the degree of polymerization is too low, the strength of the produced film is lowered. The average degree of polymerization can be measured by the intrinsic viscosity method other than Uda (Kazao Uda, Hideo Hideo, Textile Society Journal, Vol. 18 No. 1, 105-120 pages, 1962). Moreover, it is described in detail in Unexamined-Japanese-Patent No. 9-95538.

In particular, when an acyl substituent consists only of an acetyl group and the cellulose acylate whose average degree of polymerization is 180-550 is used, the transparent film which concerns on this invention can be manufactured, and optical anisotropy can be reduced more.

In addition, the molecular weight distribution of the cellulose acylate preferably used in the present invention is evaluated by gel permeation chromatography, and the polydispersity index (Mw / Mn: Mw is mass average molecular weight, Mn is number average molecular weight) is small, It is preferable that the distribution is narrow. As a specific value of Mw / Mn, it is preferable that it is 1.0-3.0, It is more preferable that it is 1.0-2.0, It is most preferable that it is 1.0-1.6.

When the low molecular weight component is removed, the average molecular weight (polymerization degree) increases, but the viscosity is lower than that of the usual cellulose acylate, which is useful. The cellulose acylate with few low molecular weight components can be obtained by removing the low molecular weight component from the cellulose acylate synthesized by a conventional method. Removal of the low molecular weight component can be performed by washing a cellulose acylate with a suitable organic solvent. Moreover, when manufacturing the cellulose acylate with few low molecular components, it is preferable to adjust the amount of sulfuric acid catalysts in an acetylation reaction to 0.5-25 mass parts with respect to 100 mass parts of cellulose acylates. When the amount of the sulfuric acid catalyst is in the above range, cellulose acylate (which has a uniform molecular weight distribution) can also be synthesized in terms of molecular weight distribution. When used at the time of manufacture of a cellulose acylate, it is preferable that the water content is 2 mass% or less, More preferably, it is 1 mass% or less, Especially preferably, it is the cellulose acylate which has a water content of 0.7 mass% or less. Generally, cellulose acylate contains water and 2.5-5 mass% is known. In order to set it as the moisture content of this cellulose acylate, it should be dried, and the method will not be specifically limited if it can be set as the target moisture content. These cellulose acylates are described in detail in pages 7 to 12 of the raw material surface and the synthesis method of Korean Patent Publication No. 2001-1745 (published on March 15, 2001, Invention Association).

A cellulose acylate can mix and use single or another 2 or more types of cellulose acylate as long as it is the range mentioned above, such as a substituent, substitution degree, polymerization degree, molecular weight distribution.

[Additives for Transparent Films]

The transparent film which concerns on this invention may heat-melt thermoplastic polymer resin, and may produce a film | membrane, and may form a film by the solution film forming (solvent cast method) from the solution which melt | dissolved the polymer uniformly. In the case of a hot melt film forming, various additives (for example, a compound which lowers optical anisotropy, a wavelength dispersion regulator, an ultraviolet inhibitor, a plasticizer, a deterioration inhibitor, a fine particle, an optical property regulator, etc.) can be added at the time of thermal melting. On the other hand, when adjusting a transparent film from a solution, in a polymer solution (henceforth dope), various additives according to a use in each preparation process (for example, the compound which reduces optical anisotropy, a wavelength dispersion regulator, and an ultraviolet-ray) Inhibitors, plasticizers, deterioration inhibitors, fine particles, optical property regulators and the like) can be added, and these will be described below. Moreover, the addition time may be added at any time in a dope preparation process, and you may add and implement the process of adding and manufacturing an additive to the last manufacturing process of a dope preparation process.

[Structural Features of Compounds Reducing the Optical Anisotropy of Transparent Films]

First, the compound which reduces the optical anisotropy of the transparent film which concerns on this invention is demonstrated. As a result of earnest examination, the inventors of the present invention sufficiently reduced the optical anisotropy by using a compound which suppresses the orientation of the polymer in the film in the in-plane and film thickness directions, so that Re is zero and Rth is close to zero. For this purpose, it is advantageous that the compound which lowers the optical anisotropy becomes sufficiently compatible with a polymer, and 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-plane rather than the same plane is advantageous.

[Added Amount of Compound Degrading Optical Anisotropy of Transparent Film]

It is preferable to contain the compound which reduces the optical anisotropy of the cellulose acylate film which concerns on this invention, especially the retardation (Rth) of a film film thickness direction in the range which satisfy | fills following formula (iv) and (v) at least. Do.

-1.0(iv) (Rth (A) -Rth (0)) / A

-1.0

A

30(v) 0.01

A

30

Formulas (ii) and (iii)

-2.0(iv) (Rth (A) -Rth (0)) / A

-2.0

A

25 인 것이 보다 바람직하고. (v) 0.05

A

More preferably 25.

-3.0(iv) (Rth (A) -Rth (0)) / A

-3.0

A

20 인 것이 더욱 바람직하다. (v) 0.1

A

It is more preferable that it is 20.

Although the following general formula (1)-(4) is shown as a specific example of the compound which lowers optically anisotropy, ie, Re and Rth of the transparent film used preferably by this invention below, this invention is not limited to these compounds. . These will be described in detail below.

First, the compound of General formula (1) and (2) is demonstrated.

[Formula 1]

General formula (1)

[Formula 2]

General formula (2)

In General Formula (1), R ^1a represents an alkyl group or an aryl group, and R ^2a and R ^3a each independently represent a hydrogen atom, an alkyl group, or an aryl group. Moreover, it is especially preferable that the sum total of carbon atoms of R <^1a> , R <^2a> and R < ^3a > is 10 or more. In General Formula (2), R ^4a and R ^5a each independently represent an alkyl group or an aryl group. The total number of carbon atoms of R ^4a and R ^5a is 10 or more, and the alkyl group and the aryl group may each have a substituent. As the substituent, a fluorine atom, an alkyl group, an aryl group, an alkoxy group, a sulfone group and a sulfonamide group are preferable, and an alkyl group, an aryl group, an alkoxy group, a sulfone group and a sulfonamide group are particularly preferable. The alkyl group may be linear, branched or cyclic, preferably having 1 to 25 carbon atoms, more preferably 6 to 25, and having 6 to 20 (eg, methyl, ethyl, propyl, Isopropyl, butyl, isobutyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, cyclohexyl, heptyl, octyl, bicyclooctyl, nonyl, adamantyl, decyl, t-octyl, undecyl, dodec Particularly preferred are yarn, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, didecyl). The aryl group preferably has 6 to 30 carbon atoms, and particularly preferably 6 to 24 carbon atoms (eg, phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, triphenylphenyl). Although the preferable example of a compound represented by General formula (1) is shown below, this invention is not limited to these specific examples.

(3)

Next, the compound of General formula (3) and (4) is demonstrated.

[Formula 4]

General formula (3)

In the formula, R ^1d represents an alkyl group or an aryl group, and R ^2d and R ^3d each independently represent a hydrogen atom, an alkyl group or an aryl group. In addition, the alkyl group and the aryl group may have a substituent.

As general formula (3), it is a compound preferably represented by the following general formula (4).

[Chemical Formula 5]

General formula (4)

In General Formula (4), R ^4d , R ^5d, and R ^6d each independently represent an alkyl group or an aryl group. Here, the alkyl group may be linear, branched, or cyclic, preferably having 1 to 20 carbon atoms, more preferably 1 to 15, and most preferably 1 to 12. As a cyclic alkyl group, a cyclohexyl group is especially preferable. The aryl group preferably has 6 to 36 carbon atoms, and more preferably 6 to 24 carbon atoms.

The alkyl group and the aryl group may have a substituent, and examples of the substituent include a halogen atom (for example, chlorine, bromine, fluorine and iodine), an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group and an aryloxy. Carbonyl group, acyloxy group, sulfonylamino group, hydroxy group, cyano group, amino group and acylamino group are preferred, more preferably halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, sulfonylamino group and acylamino group, Especially preferably, they are an alkyl group, an aryl group, a sulfonylamino group, and an acylamino group.

Although the preferable example of a compound represented by General formula (3) or General formula (4) below is shown below, this invention is not limited to these specific examples.

[Formula 6]

[Formula 7]

[Formula 8]

[Wavelength dispersion regulator]

In the transparent film according to the present invention, Re and Rth are small, and more specifically, it is preferable that the dependence of the Re and Rth wavelengths, that is, the wavelength dispersion is small. In this invention, it is effective to add the compound (henceforth a wavelength dispersion regulator) which adjusts wavelength dispersion with respect to a transparent film as a means to reduce this wavelength dispersion, and these compounds are demonstrated below. In order to improve the wavelength dispersion of Rth of the transparent film which concerns on this invention, the compound which reduces the wavelength dispersion ₍ DELTA ₎ Rth = | Rth ₍₄₀₀₎ -Rth ₍₇₀₀₎ | of Rth represented by following formula (vi) is a following formula (vii It is preferable to contain 1 or more types in the range which satisfy | fills) and (viii).

(vi) ΔRth = | Rth ₍₄₀₀₎ -Rth ₍₇₀₀₎ |

-2.0(vii) (ΔRth (B) -ΔRth (0)) / B

-2.0

B

30(viii) 0.01

B

30

here,

Rth ₍₄₀₀₎ : Rth (nm) at 400 nm

Rth ₍₇₀₀₎ : Rth (nm) at ₇₀₀ nm

ΔRth (B): ΔRth (nm) of a film containing B% of a compound that lowers ΔRth

ΔRth (0): ΔRth (nm) of the film which does not contain a compound that lowers ΔRth

B: Weight (%) of the compound when the weight of the film raw material polymer is 100

to be.

Formula (vii), (viii) is

-3.0(vii) (ΔRth (B) -ΔRth (0)) / B

-3.0

B

25 (viii) 0.05

B

25

It is more preferable that it is.

-4.0(vii) (ΔRth (B) -ΔRth (0)) / B

-4.0

B

20 (viii) 0.1

B

20

More preferably.

The said wavelength dispersion regulator has 1 type of compounds which have absorption in the ultraviolet region of 200-400 nm, and reduce | reduce | Re ₍₄₀₀₎ -Re ₍₇₀₀₎ | and | Rth ₍₄₀₀₎ -Rth ₍₇₀₀₎ | of a _film. As mentioned above, the wavelength dispersion of Re and Rth of a transparent film was adjusted by containing 0.01-30 weight% with respect to a transparent film solid content.

Generally, the value of Re and Rth of a transparent film becomes 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. If the compound itself is isotropically present inside the transparent film, the birefringence of the compound itself, and further, the wavelength dispersion of Re and Rth, is assumed to be large on the short wavelength side as in the wavelength dispersion of absorbance.

Therefore, the wavelength dispersion of Re and Rth of a transparent film is made by using absorption which has absorption in the ultraviolet region of 200-400 nm as mentioned above, and the wavelength dispersion of Re and Rth of a compound itself is assumed to be large. I can prepare it. This requires that the compound adjusting the wavelength dispersion be compatible with the polymer solids sufficiently uniformly.

Also, in recent years, liquid crystal displays such as televisions, notebook computers, and mobile portable terminals require high transmittance of optical members used in liquid crystal displays in order to increase luminance with less power. In that respect, 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 added to a transparent film. In this case, it is required to have excellent spectral transmittance. In the transparent film which concerns on this invention, it is preferable that the spectral transmittances in wavelength 380nm are 45% or more and 95% or less, and the spectral transmittances in wavelength 350nm are 10% or less.

As described above, the wavelength dispersion regulator preferably used in the present invention preferably has a molecular weight of 250 to 1000 from the viewpoint of volatilization. More preferably, it is 260-800, More preferably, it is 270-800, Especially preferably, it is 300-800. 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.

It is preferable that a wavelength dispersion regulator does not volatilize in the process of dope casting of a transparent film preparation, and drying.

(Compound addition amount)

It is preferable that the addition amount of the wavelength-dispersion regulator used preferably in this invention mentioned above is 0.01-30 mass% of a transparent film, It is more preferable that it is 0.1-20 mass%, It is especially preferable that it is 0.2-10 mass% Do.

(Compound addition method)

In addition, these wavelength dispersion regulators may be used independently, or may mix and use 2 or more types of compounds by arbitrary ratios.

In addition, the time of adding these wavelength dispersion regulators may be added at any time during the dope preparation process, and may be added at the end of a dope preparation process.

As a specific example of the wavelength-dispersion regulator used preferably for this invention, a benzotriazole type compound, a benzophenone type compound, the compound containing a cyano group, an oxy benzophenone type compound, a salicylic acid ester type compound, a nickel complex salt type system, for example Although a compound etc. are mentioned, this invention is not limited by these compounds.

As a benzotriazole type compound, what is represented by General formula (101) is used suitably as a wavelength-dispersion regulator in this invention.

Formula (101) Q ¹ -Q ² -OH

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

Q ¹ represents a nitrogen-containing aromatic heterocycle, preferably a 5- to 7-membered nitrogen-containing aromatic heterocycle, more preferably a 5- to 6-membered nitrogen-containing aromatic heterocycle, for example, imidazole, pyra Sol, triazole, tetrazole, thiazole, oxazole, selenazole, benzotriazole, benzothiazole, benzoxazole, benzoselenazole, thiadiazole, oxadiazole, naphthothiazole, naphthoox Azoles, azabenzimidazoles, purines, pyridine, pyrazine, pyrimidines, pyridazines, triazines, triazadenenes, tetrazaindenes, and the like. More preferably, they are 5-membered nitrogen-containing aromatic heterocycles. As imidazole, pyrazole, triazole, tetrazole, thiazole, oxazole, benzotriazole, benzothiazole, benzoxazole, thiadiazole, oxadiazole, it is especially preferable that it is benzotriazole. .

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 a plurality of substituents, each may be condensed to form a ring.

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 or may form a condensed ring with another 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. are mentioned), More preferably, a C6-C20 aromatic hydrocarbon ring, More preferably, they are a C6-C12 aromatic hydrocarbon ring. More 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. Specific examples of the heterocycle include, for example, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazolin, thiazole, thiadiazole , Oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole , Benzimidazole, benzoxazole, benzthiazole, benzotriazole, tetrazaindene and the like. As an aromatic heterocyclic ring, Preferably, they are pyridine, triazine, quinoline.

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

The substituent T is, for example, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms), for example methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably C2-C20, more preferably C2-C12, especially preferable) Preferably it is C2-C8, for example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc., an alkynyl group (preferably C2-C20, More preferably, it is C2-C12) Especially preferably, it is C2-C8, For example, propargyl, 3-pentenyl, etc. are mentioned, An aryl group (preferably C6-C30, More preferably, C6-C20, Especially Preferably it is C6-C12, For example, phenyl, p-methylphenyl, naphthyl, etc. are mentioned), Ring or unsubstituted amino group (preferably 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, for example amino, methylamino, dimethylamino, diethylamino, di Benzylamino, etc.), an alkoxy group (preferably C1-C20, More preferably, it is C1-C12, Especially preferably, it is C1-C8, For example, methoxy, ethoxy, butoxy And an aryloxy group (preferably C6-C20, More preferably, it is C6-C16, Especially preferably, it is C6-C12, For example, phenyloxy, 2-naphthyloxy, etc. And the acyl group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, acetyl, benzoyl, formyl, pivaloyl, etc.) And alkoxycarbonyl groups (preferably C2-C20, More preferably, it is C2-C16, Especially preferably, it is C2-C12, For example, methoxycarbonyl, ethoxycarbonyl, etc. are mentioned, An aryloxycarbonyl group (preferably C7-20, More preferably, it is C7-16, Especially preferably, it is C7-10, For example, Phenyloxycarbonyl etc. are mentioned, Acyloxy group (Preferably C2-20, More preferably, it is C2-C16, Especially preferably, it is C2-C10, For example, an acetoxy, benzoyloxy, etc. are mentioned, Acylamino group (Preferably C2-C20, More preferably, it is C1-C10) 2-16, Especially preferably, it is C2-C10, For example, acetylamino, benzoylamino, etc. are mentioned, The alkoxycarbonylamino group (Preferably C2-C20, More preferably, C2-C16 , Especially preferred Crab has 2 to 12 carbon atoms, and examples thereof include methoxycarbonylamino and the like, and an aryloxycarbonylamino group (preferably 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms), and particularly preferably C7-C12 is high, for example, phenyloxycarbonylamino etc. are mentioned, sulfonylamino group (preferably C1-C20, More preferably, C1-C16, Especially preferably, C1-C12 12, methanesulfonylamino, benzenesulfonylamino, etc.), sulfamoyl group (preferably carbon number 0-20, More preferably, carbon number 0-16, Especially preferably, carbon number 0- 12, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, and the like, carbamoyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms), particularly preferred. Preferably 1 to 12 carbon atoms And, for example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like, an alkylthio group (preferably C1-20, more preferably C1-20) 16, Especially preferably, it is C1-C12, For example, methylthio, ethylthio, etc. are mentioned, An arylthio group (preferably C6-C20, More preferably, C6-C16, Especially preferable Preferably it is C6-C12, a phenylthio etc. are mentioned, for example, a sulfonyl group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, mesyl, tosyl, etc.), sulfinyl group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, methanesulfinyl, Benzene sulfinyl, etc.), ureido group (preferably burnt) A minority 1-20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, ureido, methylureido, phenylureido etc. are mentioned, The phosphate amide group (preferably Is C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, diethyl phosphate amide, a phenyl phosphate amide, etc.), A hydroxy group, a 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 Preferably it is C1-C30, More preferably, it is 1-12, A hetero atom is a nitrogen atom, an oxygen atom, a sulfur atom, for example, imidazolyl, pyridyl, quinolyl, furyl, piperi Dill, morpholino, benzoxazolyl, benzi Dazolyl, benzthiazolyl, etc.), silyl group (preferably C3-C40, more preferably C3-C30, especially preferably C3-C24, for example, trimethylsilyl, tri Phenylsilyl etc.) etc. are mentioned. These substituents may be further substituted. Moreover, 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)

[Formula 9]

(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 be the substituent T described above. In addition, these substituents may be further substituted by another substituent, and 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, a substituted or unsubstituted amino group, an alkoxy group, an aryloxy group, a hydroxy group, a halogen atom, more preferably a hydrogen atom, It is an alkyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogen atom, More preferably, it is a hydrogen atom and a C1-C12 alkyl group, Especially preferably, a C1-C12 alkyl group (preferably C4-C12) to be.

R ² and R ⁴ are preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted or unsubstituted amino group, an alkoxy group, an aryloxy group, a hydroxy group, a halogen atom, more preferably a hydrogen atom, It is an alkyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogen atom, More preferably, it is a hydrogen atom and a C1-C12 alkyl group, 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, a substituted or unsubstituted amino group, an alkoxy group, an aryloxy group, a hydroxy group, a halogen atom, more preferably a hydrogen atom, It is an alkyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogen atom, More preferably, it is a hydrogen atom and a C1-C12 alkyl group, 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, a substituted or unsubstituted amino group, an alkoxy group, an aryloxy group, a hydroxy group, a halogen atom, more preferably a hydrogen atom, It is an alkyl group, an aryl group, 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)

[Formula 10]

(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.)

[Formula 11]

Among the benzotriazole-based compounds exemplified above, when the transparent film according to the present invention was produced without containing one having a molecular weight of 320 or less, it was confirmed that it was advantageous in terms of retention.

Moreover, as a benzophenone type compound which is one of the wavelength dispersion regulators used for this invention, what is represented by General formula (102) is used preferably.

General formula (102)

[Chemical Formula 12]

(Wherein Q ¹ and Q ² each independently 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.

As an aromatic hydrocarbon ring represented by Q <^1> and Q <^2> , Preferably, they are a C6-C30 monocyclic or 2 ring aromatic hydrocarbon ring (For example, a benzene ring, a naphthalene ring, etc. are mentioned), More preferably, it is C6 It is a C20 aromatic hydrocarbon ring, More preferably, it is a C6-C12 aromatic hydrocarbon ring. More preferably, it is a benzene ring.

The aromatic heterocycle represented by Q ¹ and Q ² is preferably an aromatic heterocycle containing at least one 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, thiazole, Thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine And tetrazole, benzimidazole, benzoxazole, benzthiazole, benzotriazole, tetrazaindene and the like. As an aromatic heterocyclic ring, Preferably, they are pyridine, triazine, quinoline.

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 substituted or unsubstituted benzene ring.

Q ¹ and Q ² may further have a substituent, and substituent T described later 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. Substituent T to be described later may be applied), an oxygen atom or a sulfur atom, and preferably represents X, preferably NR (preferably an acyl group, It is a sulfonyl group, These substituents may further substitute), or O, Especially preferably, it is O.

The substituent T is, for example, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms), for example methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), alkenyl group (preferably C2-C20, more preferably C2-C12, especially Preferably it is C2-C8, for example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc., an alkynyl group (preferably C2-C20, More preferably, it is C2-C8) 12, Especially preferably, it is C2-C8, For example, a propargyl, 3-pentenyl, etc. are mentioned, An aryl group (preferably C6-C30, More preferably, C6-C20, Especially preferably, it is C6-C12, For example, phenyl, p-methylphenyl, naphthyl, etc. are mentioned), Ring or unsubstituted amino group (preferably 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, for example amino, methylamino, dimethylamino, diethylamino, di Benzylamino, etc.), an alkoxy group (preferably C1-C20, More preferably, it is C1-C12, Especially preferably, it is C1-C8, For example, methoxy, ethoxy, butoxy And an aryloxy group (preferably C6-C20, More preferably, it is C6-C16, Especially preferably, it is C6-C12, For example, phenyloxy, 2-naphthyloxy, etc. And the acyl group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, acetyl, benzoyl, formyl, pivaloyl, etc.) And alkoxycarbonyl groups (preferably C2-C20, More preferably, it is C2-C16, Especially preferably, it is C2-C12, For example, methoxycarbonyl, ethoxycarbonyl, etc. are mentioned, An aryloxycarbonyl group (preferably C7-20, More preferably, it is C7-16, Especially preferably, it is C7-10, For example, Phenyloxycarbonyl etc. are mentioned, Acyloxy group (Preferably C2-20, More preferably, it is C2-C16, Especially preferably, it is C2-C10, For example, an acetoxy, benzoyloxy, etc. are mentioned, Acylamino group (Preferably C2-C20, More preferably, it is C1-C10) 2-16, Especially preferably, it is C2-C10, For example, acetylamino, benzoylamino, etc. are mentioned, The alkoxycarbonylamino group (Preferably C2-C20, More preferably, C2-C16 , Especially preferred Preferably it is C2-C12, For example, a methoxycarbonylamino etc. are mentioned, An aryloxycarbonylamino group (preferably C7-20, More preferably, it is C7-16, Especially preferably, C7-C12, a phenyloxycarbonylamino etc. are mentioned, for example, sulfonylamino group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12 Methanesulfonylamino, benzenesulfonylamino, etc.), sulfamoyl group (preferably carbon 0-20, more preferably 0-16 carbon, especially preferably 0-12 carbon) For example, sulfamoyl, methyl sulfamoyl, dimethyl sulfamoyl, phenyl sulfamoyl, etc.), carbamoyl group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, Has 1 to 12 carbon atoms And, for example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like, an alkylthio group (preferably C1-20, more preferably C1-20) 16, Especially preferably, it is C1-C12, For example, methylthio, ethylthio, etc. are mentioned, An arylthio group (preferably C6-C20, More preferably, C6-C16, Especially preferable Preferably it is C6-C12, a phenylthio etc. are mentioned, for example, a sulfonyl group (preferably C1-C20, More preferably, C1-C16, Especially preferably, it is C1-C12) For example, mesyl, tosyl, etc.), sulfinyl group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, methanesulfinyl , Benzenesulfinyl, etc.), ureido group (preferably A minority 1-20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, ureido, methylureido, phenylureido etc. are mentioned, The phosphate amide group (preferably Is C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, diethyl phosphate amide, a phenyl phosphate amide, etc.), A hydroxyl group, a mercapto group, Halogen Atoms (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 Is a C1-C30, More preferably, it is 1-12, A hetero atom is a nitrogen atom, an oxygen atom, a sulfur atom, specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, piperidyl , Morpholino, benzoxazolyl, benz Dazolyl, benzthiazolyl, etc.), silyl group (preferably C3-C40, more preferably C3-C30, especially preferably C3-C24, for example, trimethylsilyl, tri Phenylsilyl etc.) etc. are mentioned. These substituents may be further substituted. Moreover, 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 (102), it is preferably a compound represented by the following general formula (102-A).

General formula (102-A)

[Formula 13]

(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 substituents may apply the above-mentioned substituent T. 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, substituted or unsubstituted amino group, alkoxy group, aryl jade It is a time period, a hydroxy 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 a C1-C12 alkyl group, Especially preferably, It is a hydrogen atom and 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, a substituted or unsubstituted amino group, an alkoxy group, an aryloxy group, a hydroxy group or a halogen atom, and more preferably a hydrogen atom or C1-C It is an alkyl group of 20, a C0-20 amino group, a C1-C12 alkoxy group, a C6-C12 aryloxy group, and a hydroxy group, More preferably, it is a C1-C20 alkoxy group, Especially preferably, it is C1 It is an alkoxy group of -12.

R ⁷ is preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted or unsubstituted amino group, an alkoxy group, an aryloxy group, a hydroxy group, a halogen atom, more preferably a hydrogen atom, C 1-20 An alkyl 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 having 1 to 20 carbon atoms). 12, More preferably, they are C1-C8, 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)

[Formula 14]

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

R ¹⁰ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, and the substituent T described above may be applied. .

R ¹⁰ is preferably a substituted or unsubstituted alkyl group, more preferably a substituted or unsubstituted alkyl group having 5 to 20 carbon atoms, still more preferably a substituted or unsubstituted alkyl group having 5 to 12 carbon atoms (n-hex). The actual group, 2-ethylhexyl group, n-octyl group, n-decyl group, n-dodecyl group, benzyl group etc. are mentioned, Especially preferably, a C6-C12 substituted or unsubstituted alkyl group ( 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, this invention is not limited to a following specific example at all.

[Formula 15]

[Formula 16]

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

General formula (103)

[Formula 17]

(Wherein, Q ¹ and Q ² each independently represent an aromatic ring. X ¹ and X ^{2 each} represent a hydrogen atom or a substituent, and at least one represents a cyano group, a carbonyl group, a sulfonyl group, or an aromatic heterocycle.) Q ¹ And 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.

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. are mentioned), More preferably, a C6-C20 aromatic hydrocarbon ring, More preferably, they are a C6-C12 aromatic hydrocarbon ring. More 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. Specific examples of the heterocycle include, for example, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazolin, thiazole, thiadiazole, Oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, Benzimidazole, benzoxazole, benzthiazole, benzotriazole, tetrazaindene, etc. are mentioned. As an aromatic heterocyclic ring, Preferably, they are pyridine, triazine, quinoline.

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 substituent T described later is preferable. The substituent T is, for example, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms), for example methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably C2-C20, more preferably C2-C12, especially preferable) Preferably it is C2-C8, for example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc., an alkynyl group (preferably C2-C20, More preferably, it is C2-C12) Especially preferably, it is C2-C8, For example, propargyl, 3-pentenyl, etc. are mentioned, An aryl group (preferably C6-C30, More preferably, C6-C20, Especially Preferably it is C6-C12, For example, phenyl, p-methylphenyl, naphthyl, etc. are mentioned), Ring or unsubstituted amino group (preferably 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, for example amino, methylamino, dimethylamino, diethylamino, di Benzylamino, etc.), an alkoxy group (preferably C1-C20, More preferably, it is C1-C12, Especially preferably, it is C1-C8, For example, methoxy, ethoxy, butoxy And an aryloxy group (preferably C6-C20, More preferably, it is C6-C16, Especially preferably, it is C6-C12, For example, phenyloxy, 2-naphthyloxy, etc. And the acyl group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, acetyl, benzoyl, formyl, pivaloyl, etc.) And alkoxycarbonyl groups (preferably C2-C20, More preferably, it is C2-C16, Especially preferably, it is C2-C12, For example, methoxycarbonyl, ethoxycarbonyl, etc. are mentioned, An aryloxycarbonyl group (preferably C7-20, More preferably, it is C7-16, Especially preferably, it is C7-10, For example, Phenyloxycarbonyl etc. are mentioned, Acyloxy group (Preferably C2-20, More preferably, it is C2-C16, Especially preferably, it is C2-C10, For example, an acetoxy, benzoyloxy, etc. are mentioned, Acylamino group (Preferably C2-C20, More preferably, it is C1-C10) 2-16, Especially preferably, it is C2-C10, For example, acetylamino, benzoylamino, etc. are mentioned, The alkoxycarbonylamino group (Preferably C2-C20, More preferably, C2-C16 , Especially preferred Crab has 2 to 12 carbon atoms, and examples thereof include methoxycarbonylamino and the like, and an aryloxycarbonylamino group (preferably 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms), and particularly preferably C7-C12, a phenyloxycarbonylamino etc. are mentioned, for example, sulfonylamino group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12 Methanesulfonylamino, benzenesulfonylamino, etc.), sulfamoyl group (preferably carbon 0-20, more preferably 0-16 carbon, especially preferably 0-12 carbon) For example, sulfamoyl, methyl sulfamoyl, dimethyl sulfamoyl, phenyl sulfamoyl, etc.), carbamoyl group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, Has 1 to 12 carbon atoms Examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, and the like, alkylthio groups (preferably C1-20, more preferably C1-20). 16, Especially preferably, it is C1-C12, For example, methylthio, ethylthio, etc. are mentioned, An arylthio group (preferably C6-C20, More preferably, C6-C16, Especially preferable Preferably it is C6-C12, a phenylthio etc. are mentioned, for example, a sulfonyl group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, mesyl, tosyl, etc.), sulfinyl group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, methanesulfinyl, Benzene sulfinyl, etc.), ureido group (preferably burnt) C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, ureido, methylureido, phenylureido, etc. are mentioned, The phosphate amide group (preferably Is C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, diethyl phosphate amide, a phenyl phosphate amide, etc.), A hydroxyl group, a mercapto group, Halogen Atoms (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 Is a C1-C30, More preferably, it is 1-12, A hetero atom is a nitrogen atom, an oxygen atom, a sulfur atom, specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, piperidyl , Morpholino, benzoxazolyl, benzimi Dazolyl, benzthiazolyl, etc.), silyl group (preferably C3-C40, more preferably C3-C30, especially preferably C3-C24, for example, trimethylsilyl, tri Phenylsilyl etc.) etc. are mentioned. These substituents may be further substituted. Moreover, 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.

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, an aromatic heterocycle. The substituent represented by X <^1> and X <^2> can apply the above-mentioned substituent T. Further, X ^1, and the substituent represented by X ² may additionally be substituted by another substituent, X ¹ and X ² may form a ring structure, each chukhwan.

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 heterocyclic ring. More preferably, it is a cyano group and a carbonyl group, Especially preferably, a cyano group, an alkoxycarbonyl group (-C (= O) OR (R is a C1-C20 alkyl group, a C6-C12 aryl group, and these combinations) will be.

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

General formula (103-A)

[Formula 18]

(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 The same meaning as those in the general formula (20), and the preferred 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 other substituents, and the substituents may be condensed to form a ring structure.

R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ are preferably hydrogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, substituted or unsubstituted amino groups, alkoxy groups , An aryloxy group, a hydroxy group, a halogen 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 or an alkyl group having 1 to 12 carbon atoms. Preferably they are a hydrogen atom and a methyl group, Most preferably, they are a hydrogen atom.

R ³ and R ⁸ are preferably hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, substituted or unsubstituted amino group, alkoxy group, aryloxy group, hydroxyl group, halogen atom, more preferably hydrogen atom, carbon number It is a 1-20 alkyl group, a C0-C20 amino group, a C1-C12 alkoxy group, a C6-C12 aryloxy group, and a hydroxyl group, More preferably, it is a hydrogen atom, a C1-C12 alkyl group, C1-C12 It is an alkoxy group of 12, 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)

[Formula 19]

(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 heterocycle, and more preferably a cyano group, a carbonyl group, a sulfonyl group, an aromatic heterocycle, and more preferably. Preferably it is a cyano group and a carbonyl group, Especially preferably, it is a cyano group and an alkoxycarbonyl group (-C (= O) OR (R is: a C1-C20 alkyl group, a C6-C12 aryl group, and these combined) .

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

General formula (103-C)

[Formula 20]

(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 a 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 C6-C12 alkyl group Especially preferably, they are n-octyl group, tert-octyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group, Most preferably, they are 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 a C20 or less alkyl group is preferable.

The compound represented by the general formula (103) of the present invention can be synthesized by the method described in Jounal of American Chemical Society, Vol. 63, Page 3452 (1941).

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

[Formula 21]

(remover)

Moreover, in this invention, in order to make the load at the time of peeling small, it is preferable to add a peeling agent.

These surfactants are effective in phosphoric acid, sulfonic acid, carboxylic acid, nonionic, cationic and the like. These are described in Unexamined-Japanese-Patent No. 61-243837, Unexamined-Japanese-Patent No. 2000-99847, etc., for example. As for addition amount, 0.1 mass% or less is preferable with respect to cellulose acylate.

Moreover, regarding a releasing agent, Unexamined-Japanese-Patent No. 2003-055501 is a cellulose acylate solution which melt | dissolved in the non-chlorine-type solvent in order to prevent the cloudiness of a cellulose acylate solution, and to improve film manufacture peelability and film surface shape, the acid dissociation index (pK _a) have been described with respect to the cellulose acylate solution containing an additive selected from the group consisting of 1.93 ~ 4.5 parts of a polybasic acid ester material, alkali metal salts, alkaline earth metal salts.

As for the additive, Japanese Laid-Open Patent Publication No. 2003-128838 discloses a crosslinking agent having two or more groups reactive with at least one active hydrogen to cellulose acylate in order to improve peelability, surface shape, and film strength. It describes about the cellulose acylate dope solution containing -10 mass%.

In addition, Japanese Laid-Open Patent Publication No. 2003-165868 proposes a film to which an additive is added, has good moisture permeability, and is excellent in dimensional stability.

[Surface treatment]

The transparent film which concerns on this invention can achieve the adhesive improvement of a transparent film and each functional layer (for example, an undercoat layer and a white layer) by surface-treating in some cases. For example, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment can be used. The glow discharge treatment herein may be a low temperature plasma generated under a low pressure gas of 10 ⁻³ to 20 Torr, and also preferably a plasma treatment under atmospheric pressure. The plasma excited gas refers to a gas that is plasma excited under the conditions described above, and examples thereof include argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, and freons such as tetrafluoromethane, and mixtures thereof. . About these, the detail is described in detail in pages 30-32 of Unexamined-Japanese-Patent Publication No. 2001-1745 (published on March 15, 2001, Invention Association), and can be used conveniently by this invention.

[Contact angle of film surface by alkali saponification treatment]

When processing the polarizing plate of the transparent film which concerns on this invention, an alkali saponification process is mentioned as one of the effective means of surface treatment. In this case, it is preferable that the contact angle of the water of the film surface after alkali saponification process is 55 degrees or less. More preferably, it is 50 degrees or less, and it is still more preferable that it is 45 degrees or less. The evaluation method of a contact angle can be used as evaluation of hydrophilicity by the conventional method of dropping the water droplet of diameter 3mm on the film surface after alkali saponification process, and obtaining the angle which the film surface and water droplet form.

[Functional layer]

The transparent film which concerns on this invention is applied to an optical use as the use. It is preferable that especially an optical use is a liquid crystal display device, The liquid crystal cell in which a liquid crystal display device carries a liquid crystal between two electrode substrates, two polarizing elements arrange | positioned at both sides, and between this liquid crystal cell and this polarizing element It is more preferable that it is the structure which arrange | positioned one or more optical compensation sheets. As these liquid crystal display devices, TN, IPS, FLC, AFLC, OCB, STN, ECB, VA and HAN are preferable.

At this time, when using a transparent film for the above-mentioned optical use, providing various functional layers is performed. These are, for example, an antistatic layer, a cured resin layer (transparent hard coat layer), an antireflection layer, an adhesive easy layer, an antiglare layer, an optical compensation layer, an alignment layer, a liquid crystal layer, and the like. These functional layers and materials for which the transparent film can be used include surfactants, lubricants, matting agents, antistatic layers, hard coat layers, and the like, and the Korean Institute of Patent Publication No. 2001-1745 (March 2001). 15th issue, Invention Association) page 32 to page 45, and can be preferably used in the present invention.

[Polarizing Plate]

The manufacturing method of the polarizing plate of this invention will not be specifically limited if it can manufacture especially in long shape, It can manufacture by a general method. There exists a method of alkali-processing the obtained transparent film and attaching a polyvinyl alcohol film to both surfaces of the polarizer produced by immersing and extending | stretching in iodine solution using the fully saponified polyvinyl alcohol aqueous solution. Instead of alkali treatment, you may perform the easily bonding process described in Unexamined-Japanese-Patent No. 6-94915 and Unexamined-Japanese-Patent No. 6-118232.

As an adhesive agent used for attaching a protective film process surface and a polarizer, polyvinyl alcohol adhesives, such as polyvinyl alcohol and polyvinyl butyral, vinyl latexes, such as butylacrylate, etc. are mentioned, for example.

A polarizing plate is comprised from the polarizer and the protective film which protects both surfaces, and is further comprised by attaching a protective film to one surface of this polarizing plate, and attaching a separate film to the opposite surface. A protective film and a separate film are used for the purpose of protecting a polarizing plate at the time of a polarizing plate shipment, a product inspection, etc. In this case, a protective film is affixed in order to protect the surface of a polarizing plate, and is used for the opposite surface side of the surface which affixes a polarizing plate with respect to a liquid crystal plate. Moreover, a separator film is used for the purpose of covering the adhesive layer adhering to a liquid crystal plate, and is used in the surface side which attaches a polarizing plate to a liquid crystal plate.

As for the method of attaching the transparent film according to the present invention with respect to the polarizer, the method of attaching a long film by roll to roll has high productivity, and variations in polarizing plate characteristics (particularly, axial angle and light leakage) Is very small and is preferred. Moreover, in a long polarizer, an absorption axis is parallel to a longitudinal direction, and in a long transparent film, a slow axis is orthogonal or parallel to a longitudinal direction.

Moreover, when the axial shift angle of the slow axis of the transparent film which concerns on this invention, the absorption axis of a polarizer, or the transmission axis | shaft of a transparent film which concerns on this invention is larger than 10 degree | times, the polarization degree performance under polarizing plate cross nicol will fall, and light When coloring occurs and a sufficient black level and contrast are not obtained when it combines with a liquid crystal cell, the axis shift angle of the direction of the slow axis of the transparent film which concerns on this invention, and the absorption axis or transmission axis of a polarizing plate is 10 degrees. It is preferred to be within degrees, preferably within 5 degrees, more preferably within 1 degree.

In the measurement of an axial shift angle, the produced polarizing plate was peeled off with a transparent film and a polarizer, and it measured as follows.

Measurement of the axial angle of the polarizer:

Using the polarizer A which already knows the axis, the position where the superimposed transmitted light of the polarizer B and the polarizer A to be measured becomes the minimum is determined, and the direction coinciding with the absorption axis of the polarizer A is determined. The transmission axis of (B) and the orthogonal direction were made into the absorption axis.

Measurement of slow axis of transparent film:

As for the axial angle of the transparent film, the slow-axis angle with respect to the longitudinal direction was measured using KOBRA 21DH (made by Oji Measurement Instruments Co., Ltd.).

As for the polarizing plate of this invention, the single plate transmittance (TT), parallel transmittance (PT), orthogonal transmittance (CT), and polarization degree (P) of 400-700 nm in 25 degreeC 60% RH are following formula (a)-(d It is preferable to satisfy | fill one or more of (). (In addition, "400-700 nm" means the average value which scanned the range of 400-700 nm. Hereinafter, it is the same.)

Transmittance and parallel transmittance of one polarizing plate are the transmittance | permeability measured in the state which made the two polarizing plates parallel to the transmission axis, and the orthogonal transmittance are the transmittance measured in the state which orthogonally crossed the transmission axis of two polarizing plates.

TT

45.0(a) 40.0

TT

45.0

PT

40.0(b) 30.0

PT

40.0

2.0(c) CT

2.0

P(d) 95.0

P

TT

45.0, 32.0

PT

40.0, CT

1.5 이고, 더욱 바람직 하게는 41.0

TT

45.0, 34.0

PT

40.0, CT

1.3 이다. 편광도 (P) 는 95.0% 이상인 것이 바람직하고, 보다 바람직하게는 96.0% 이상, 더욱 바람직하게는 97.0% 이상이다. Single plate transmittance (TT), parallel transmittance (PT) and orthogonal transmittance (CT) are each in this order, more preferably, 40.5

TT

45.0, 32.0

PT

40.0, CT

1.5, more preferably 41.0

TT

45.0, 34.0

PT

40.0, CT

1.3. It is preferable that polarization degree P is 95.0% or more, More preferably, it is 96.0% or more, More preferably, it is 97.0% or more.

In the polarizing plate of the present invention, T ₍₃₈₀₎ , T ₍₄₁₀₎ , and T ₍₇₀₀₎ are 1 in the following formulas (e) to (g) when the orthogonal transmittance in the wavelength λ is T (λ). It is desirable to satisfy more than two.

2.0(e) T ₍₃₈₀₎

2.0

1.0(i) T ₄₁₀

1.0

0.5(g) T ₍₇₀₀₎

0.5

1.95, T₍₄₁₀₎

0.9, T₍₇₀₀₎

0.49 이고, 더욱 바람직하게는 T₍₃₈₀₎

1.90, T₍₄₁₀₎

0.8, T₍₇₀₀₎

0.48 이다. More preferably T ₃₈₀

1.95, T ₍₄₁₀₎

0.9, T ₍₇₀₀₎

0.49, more preferably T ₍₃₈₀₎

1.90, T ₄₁₀

0.8, T ₍₇₀₀₎

0.48.

In the polarizing plate of the present invention, the amount of change (ΔCT) and the degree of polarization change (ΔP) of 400-700 nm orthogonal transmittance at 500 ° C. under 500 ° C. under conditions of 95% RH are represented by the following formulas (h) and (i): It is preferable to satisfy one or more.

ΔCT

6.0(h) -6.0

ΔCT

6.0

ΔP

0.0(i) -10.0

ΔP

0.0

(However, the change amount represents the value obtained by subtracting the pre-test measurement from the post-test measurement)

ΔCT

5.8, -9.5

ΔP

0.0, 더욱 바람직하게는, -5.6

ΔCT

5.6, -9.0

ΔP

0.0 이다. More preferably -5.8

ΔCT

5.8, -9.5

ΔP

0.0, more preferably, -5.6

ΔCT

5.6, -9.0

ΔP

0.0.

In the polarizing plate of the present invention, the amount of change (ΔCT) and the degree of polarization change (ΔP) of 400-700 nm orthogonal transmittance at 500 ° C. under 500 ° C. under conditions of 90% RH are represented by the following formulas (j) and (k). It is preferable to satisfy one or more.

ΔCT

3.0(j) -3.0

ΔCT

3.0

ΔP

0.0(k) -5.0

ΔP

0.0

(However, the change amount represents the value obtained by subtracting the pre-test measurement from the post-test measurement)

ΔCT

2.0, -0.5

ΔP

0.0, 더욱 바람직하게는, -0.2

ΔCT

0.2, -0.2

ΔP

0.0 이다. More preferably -2.0

ΔCT

2.0, -0.5

ΔP

0.0, more preferably, -0.2

ΔCT

0.2, -0.2

ΔP

0.0.

In the polarizing plate of the present invention, the amount of change (ΔCT) and the degree of polarization change (ΔP) of 400 to 700 nm orthogonal transmittance when left to stand for 500 hours at 80 ° C. is one or more of the following formulas (l) and (m): It is desirable to satisfy.

ΔCT

3.0(l) -3.0

ΔCT

3.0

ΔP

0.0(m) -2.0

ΔP

0.0

(However, the change amount represents the value obtained by subtracting the pre-test measurement from the post-test measurement)

ΔCT

2.0, -0.5

ΔP

0.0, 더욱 바람직하게는, -0.2

ΔCT

0.2, -0.2

ΔP

0.0 이다. More preferably -2.0

ΔCT

2.0, -0.5

ΔP

0.0, more preferably, -0.2

ΔCT

0.2, -0.2

ΔP

0.0.

Single plate transmittance (TT), parallel transmittance (PT), and orthogonal transmittance (CT) of the polarizing plate were measured in the range of 380 nm to 780 nm using UV3100PC (manufactured by Shimadzu Corporation), and TT, PT, and CT were measured 10 times. The average value (average value in 400 nm-700 nm) of is used. The polarizing plate durability test is carried out in two forms: (1) polarizing plate only and (2) attaching polarizing plate to glass through pressure sensitive adhesive as follows. The measurement of only a polarizing plate combines so that the transparent film which concerns on this invention interposes between two polarizers, and prepares and measures two identical things. The polarizing plate of the state which stuck to glass produces two samples (about 5 cm x 5 cm) which affixed the polarizing plate on glass so that the transparent film which concerns on this invention may come to a glass side. In single plate transmittance measurement, the film side of this sample is set toward a light source and measured. Two samples are respectively measured and the average value is made into the transmittance | permeability of a single plate.

Although the board | substrate containing a liquid crystal is normally arrange | positioned between two polarizing plates in a liquid crystal display device, the outstanding display property is acquired even if it arrange | positions in what site the polarizing plate protective film which applied the optical film which concerns on this invention. In particular, since a transparent hard coat layer, an antiglare layer, an antireflection layer, etc. are formed in the polarizing plate protective film of the display side outermost surface of a liquid crystal display device, it is especially preferable to use this polarizing plate protective film for this part.

[Applications (Optical Compensation Film)]

The polarizing plate of this invention can be used for various uses, and when used together with the optical compensation film of a liquid crystal display device, it is especially effective. Moreover, an optical compensation film generally refers to the optical material used for a liquid crystal display device, and compensates for a phase difference, and has the same meaning as a retardation plate, an optical compensation sheet, etc. An optical compensation film has birefringence and is used for the purpose of removing coloring of the display screen of a liquid crystal display device, or improving viewing angle characteristic.

When using the polarizing plate of this invention as a polarizing plate integrated optical compensation film of a liquid crystal display device, Re and Rth of the optically anisotropic layer to add are Re ₍₆₃₀₎ = 0-200nm and | Rth ₍₆₃₀₎ | = 0-400nm Is preferable, and any optically anisotropic layer may be sufficient as it is this range. Any optically anisotropic layer required as an optical compensation film can be added together without being limited to the optical performance of the liquid crystal cell of the liquid crystal display device in which the polarizing plate of this invention is used, and a drive system. As an optically anisotropic layer added together, you may form with the composition containing a liquid crystalline compound, and you may form with the polymer film which has birefringence.

As said liquid crystalline compound, a discotic liquid crystalline compound or a rod-shaped liquid crystalline compound is preferable.

(Discotic liquid crystalline compound)

Examples of discotic liquid crystalline compounds usable in the present invention include various documents (C. Destrade et al., Mol. Crysr. Liq. Cryst., Vol. 71, page 111 (1981); 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)).

It is preferable that a discotic liquid crystalline compound has a polymeric group so that fixation is possible by superposition | polymerization. For example, a structure in which a polymerizable group is bonded as a substituent to a disk-shaped core of a discotic liquid crystal compound is conceivable. However, when the polymerizable group is directly linked to the disk-shaped core, it becomes difficult to maintain the alignment state in the polymerization reaction. Therefore, a structure having a linking group between the disk-shaped core and the polymerizable group is preferable. That is, it is preferable that the discotic liquid crystalline compound which has a polymeric group is a compound represented by a following formula.

D (-LP) _n

In formula, D is a disc shaped core, L is a bivalent coupling group, P is a polymeric group, n is an integer of 4-12. Preferable specific examples of the disk-shaped core (D), the divalent linking group (L) and the polymerizable group (P) in the formulas include (D1) to (D15) and (L1) to JP 2001-4837A. (L25), (P1)-(P18), and the content of the said publication can be used preferably.

[Bar type liquid crystalline compound]

Examples of the rod-shaped liquid crystalline compounds usable in the present invention include azomethines, azoxy compounds, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, Cyano substituted phenylpyrimidines, alkoxy substituted phenylpyrimidines, phenyldioxanes, tolans and alkenylcyclohexylbenzonitriles. Not only the low molecular liquid crystalline molecules mentioned above but a high molecular liquid crystalline compound can also be used.

In the optically anisotropic layer, the rod-like liquid crystalline molecules are preferably fixed in an aligned state, and most preferably fixed by a polymerization reaction. Examples of the polymerizable rod-like liquid crystalline compound usable in the present invention include Makromol. Chem., 190, 2255 (1989), Advanced Materials 5, 107 (1993), U.S. Pat. No. 4683327, U.S. Patent 5622648, U.S. Patent No. 5770107, International Publication No. 95/22586, U.S. 95/24455, 97/00600, 98/23580, 98/52905, pamphlets, Japanese Patent Laid-Open Nos. 1-272551, 6-16616, 7-110469, 11- 80081 and the compounds of Unexamined-Japanese-Patent No. 2001-328973, etc. are contained.

(Optical anisotropic layer made of polymer film)

The optically anisotropic layer may be formed of a polymer film. A polymer film is formed from the polymer which can express optical anisotropy. Examples of such polymers include polyamides, polyimides, polyesters, polyetherketones, polyamideimidepolyesterimides, and polyaryletherketones, polyolefins (e.g., polyethylene, polypropylene, norbornene-based polymers), poly Carbonates, polyallylates, polysulfones, polyvinyl alcohols, polymethacrylic acid esters, polyacrylic acid esters and cellulose esters (eg cellulose triacetate, cellulose diacetate). Moreover, you may use the copolymer or polymer mixture of these polymers.

It is preferable to obtain the optical anisotropy of a polymer film by extending | stretching. It is preferable that extending | stretching is uniaxial stretching or biaxial stretching. Specifically, longitudinal uniaxial stretching using the rotational speed difference of two or more rolls, or tenter stretching holding both sides of the polymer film and stretching in the width direction, and biaxial stretching combining these are preferable. Moreover, the optical property of the 2 or more sheets whole film may satisfy | fill the above conditions using 2 or more sheets of polymer films. It is preferable to manufacture a polymer film by the solvent cast method in order to reduce the birefringence deviation. It is preferable that it is 20-500 micrometers, and, as for the thickness of a polymer film, it is most preferable that it is 40-100 micrometers.

In addition, in the formation of the optically anisotropic layer, a method in which a solution obtained by dissolving a polymer material in a solvent is applied to a substrate, and the solvent is dried to form a film. At this time, the method of extending | stretching the said polymer film and a base material, expressing optical anisotropy, and using it as an optically anisotropic layer can also be used preferably, and the transparent film which concerns on this invention can be used suitably as said base material. Moreover, it is also preferable to produce the said polymer film on another base material, to peel a polymer film from a base material, and to adhere with the transparent film which concerns on this invention, and to use it together as an optically anisotropic layer. In this method, the thickness of the polymer film can be made thin, preferably 50 µm or less, more preferably 0.5-20 µm, and more preferably 0.5-10 µm.

(Composition of General Liquid Crystal Display)

 The liquid crystal display device has a structure in which a liquid crystal cell formed by supporting a liquid crystal between two electrode substrates, two polarizing elements arranged on both sides thereof, and a configuration in which at least one optical compensation film is disposed between the liquid crystal cell and the polarizing element. Have

The liquid crystal layer of the liquid crystal cell is usually formed by sealing a liquid crystal in a space formed by sandwiching a spacer between two substrates. The transparent electrode layer is formed on the substrate as a transparent film containing a conductive material. In the liquid crystal cell, a gas barrier layer, a hard coat layer or an undercoat layer (undercoat layer) (used for bonding the transparent electrode layer) may be further formed. These layers are normally formed on a board | substrate. The substrate of the liquid crystal cell generally has a thickness of 50 µm to 2 mm.

(Type of liquid crystal display device)

The transparent film which concerns on this invention can be used for the liquid crystal cell of various display modes. TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), AFLC (Anti-ferroelectric Liquid Crystal), OCB (0ptically Compensatory Bend), STN (Supper Twisted Nematic), VA (Vertically Aligned), Various display modes have been proposed, such as Electrically Controlled Birefringence (ECB) and Hybrid Aligned Nematic (HAN). Moreover, the display mode which orientation-divided the said display mode is also proposed. The transparent film which concerns on this invention is effective also in the liquid crystal display device of any display mode. Moreover, it is effective also in any liquid crystal display device of transmissive type, reflective type, and transflective type.

(TN type liquid crystal display device)

You may use the transparent film which concerns on this invention as a support body of the optical compensation sheet of the TN type liquid crystal display device which has a liquid crystal cell of TN mode. The liquid crystal cell of TN mode and a TN type liquid crystal display device are known well conventionally. As for the optical compensation sheet used for a TN type liquid crystal display device, Japanese Patent Laid-Open Nos. H3-9325, Japanese Patent Laid-Open No. 6-148429, Japanese Patent Laid-Open No. 8-50206, and Japanese Patent Laid-Open No. Each publication of 9-26572 is described. See also, Mori et al. (Jpn. J. Appl. Phys. Vol. 36 (1997) p. 143 or Jpn. J. Appl. Phys. Vol. 36 (1997) p. 1068). have.

(STN type liquid crystal display device)

You may use the transparent film which concerns on this invention as a support body of the optical compensation sheet of STN type liquid crystal display device which has a liquid crystal cell of STN mode. Generally in STN type liquid crystal display devices, the rod-like liquid crystalline molecules in the liquid crystal cell are twisted in the range of 90 to 360 degrees, and the product of the refractive index anisotropy (Δn) and the cell gap (d) of the rod-shaped liquid crystal molecules (Δnd) It exists in the range of 300-1500 nm. About the optical compensation sheet used for STN type liquid crystal display device, it describes in Unexamined-Japanese-Patent No. 2000-105316.

(VA type liquid crystal display device)

The transparent film which concerns on this invention is used especially advantageously as a support body of the optical compensation sheet of VA type liquid crystal display device which has a liquid crystal cell of VA mode. It is preferable to set Re-retardation value of the optical compensation sheet used for VA type liquid crystal display device to 0-150 nm, and to set Rth retardation value to 70-400 nm. The Re retardation value is more preferably 20 to 70 nm. When using two optically anisotropic polymer films for VA type liquid crystal display devices, it is preferable that the Rth retardation value of a film is 70-250 nm. When using one optically anisotropic polymer film for VA type liquid crystal display devices, it is preferable that the Rth retardation value of a film is 150-400 nm. The VA type liquid crystal display device may be a method of orientation division as described, for example, in JP-A-10-123576.

(IPS type liquid crystal display device and ECB type liquid crystal display device)

The transparent film which concerns on this invention is especially advantageous also used as a support film of the optical compensation sheet of an IPS type liquid crystal display device and an ECB type liquid crystal display device which have a liquid crystal cell of an IPS mode and an ECB mode, or a polarizing plate. These modes are embodiments in which the liquid crystal material is oriented almost in parallel during black display. In the state where no voltage is applied, liquid crystal molecules are aligned in parallel with the substrate surface and displayed in black. In these aspects, the polarizing plate using the transparent film which concerns on this invention contributes to viewing angle expansion and an improvement of contrast. In this aspect, it is preferable to set the value of the retardation of the protective film of the said polarizing plate, and the optically anisotropic layer arrange | positioned between a protective film and a liquid crystal cell to 2 times or less of the (DELTA) n * d value of a liquid crystal layer. Moreover, since it is preferable to set the absolute value | Rth | of the Rth value to 25 nm or less, More preferably, it is 20 nm or less, More preferably, it is 15 nm or less, The transparent film concerning this invention is used advantageously.

(OCB type liquid crystal display device and HAN type liquid crystal display device)

The transparent film which concerns on this invention is advantageously used also as a support body of the optical compensation sheet of the OCB type liquid crystal display device which has a liquid crystal cell of OCB mode, or the HAN type liquid crystal display device which has a liquid crystal cell of HAN mode. In the optical compensation sheet used for an OCB type liquid crystal display device or an HAN type liquid crystal display device, it is preferable that the direction which the absolute value of retardation becomes minimum does not exist in the surface of a optical compensation sheet nor a normal direction. The optical properties of the optical compensation sheet used for the OCB type liquid crystal display device or the HAN type liquid crystal display device are also determined by the optical properties of the optically anisotropic layer, the optical properties of the support, and the arrangement of the optically anisotropic layer and the support. About the optical compensation sheet used for an OCB type liquid crystal display device or an HAN type liquid crystal display device, it describes in Unexamined-Japanese-Patent No. 9-197397. See also, Mori et al. (Jpn. J. Appl. Phys. Vol. 38 (1999) p. 2837).

(Reflective liquid crystal display)

The transparent film which concerns on this invention is advantageously used also as the optical compensation sheet of the reflection type liquid crystal display device of TN type, STN type, HAN type, and GH (Guest-Host) type. These display modes are conventionally well known. TN type reflective liquid crystal display devices are described in Japanese Patent Application Laid-Open No. Hei 10-123478, International Publication No. 98/48320, and Japanese Patent No. 3024277. About the optical compensation sheet used for a reflective liquid crystal display device, it is described in the international publication 00/65384 pamphlet.

(Other liquid crystal display)

The transparent film which concerns on this invention is advantageously used also as a support body of the optical compensation sheet of an ASM type liquid crystal display device which has a liquid crystal cell of ASM (Axially Symmetric Aligned Microcell) mode. The liquid crystal cell of ASM mode has the characteristic that the thickness of the cell is hold | maintained by the resin spacer which can be adjusted. The other property is the same as that of the liquid crystal cell of TN mode. A liquid crystal cell of the ASM mode and an ASM type liquid crystal display device are described in Kume et al. (Kume et al., SID 98 Digest 1089 (1998)).

(Hard coat film, antiglare film, antireflection film)

The transparent film according to the present invention can further preferably be applied to a hard coat film, an antiglare film, and an antireflection film. For the purpose of improving the visibility of flat panel displays such as LCD, PDP, CRT, EL, etc., one or both of a hard coat layer, an antiglare layer, and an antireflection layer can be provided on one or both surfaces of the transparent film according to the present invention. have. Preferred embodiments of such anti-glare films and anti-reflection films are described in detail on pages 54 to 57 of the Invention Association Publication No. 2001-1745 (published on March 15, 2001, Invention Association), and the present invention. The transparent film which concerns on can be used preferably.

Example

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, reagents, ratios, 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 specific example shown below.

Example 1

(Production of the transparent film)

A cellulose acylate was used as a raw material of the transparent film which concerns on this invention.

(Production of Cellulose Acylate Sample 101)

As the cellulose acylate, two kinds of Ceyl (Ac: OH = 2.94: 0.06) and Ce-2 (Ac: Pro: OH = 1.7: 1.0: 0.3) having different acylation degrees were used. Here, Ac in parentheses represents an acetyl substituent, Pro represents a propionyl substituent, and OH represents an unsubstituted hydroxyl group, and the ratio is the ratio of the degree of acylation.

(Cellulose acylate solution composition)

Cellulose Acylate (Ce) 100.0 parts by mass

Methylene chloride (first solvent) 480.0 parts by mass

71.7 parts by mass of methanol (second solvent)

0.15 parts by mass of silica particle dispersion having an average particle diameter of 16 nm

11.7 parts by mass of a compound (KI) which lowers optical anisotropy

1.2 mass parts of wavelength dispersion regulators (HB)

Citric acid ester mixture (citric acid,

Monoethyl ester, diethyl ester,

0.01 parts by mass of triethyl ester mixture)

The used cellulose acylate (Ce), the compound (KI) which reduces optical anisotropy, and the wavelength-dispersion regulator (HB) were shown in Table 1.

The cellulose acylate solution was cast using a band softener. The film was peeled from the band at 30% of the residual solvent amount, and dried at 130 ° C. for 40 minutes to prepare a cellulose acylate film. The residual solvent amount of the completed cellulose acylate film was 0.1%, and the film thickness was 80 µm.

(Production of Cellulose Acylate Samples 102-104)

It produced by the same method as the sample 101 except having changed used cellulose acylate (Ce), the compound (KI) which reduces optical anisotropy, a wavelength dispersion regulator (HB), and addition amount as shown in Table 1. In addition, the created sample was measured by the method mentioned above at the measurement wavelength of 630 nm.

Table 1 shows measurement results such as fabrication conditions, optical properties, and the like of the sample of the present invention produced in the above examples.

(Production of Polarizing Plates (H101-105))

The long transparent film sample of this invention was made to continuously pass through 1.5 N sodium hydroxide aqueous solution, and it was immersed at 55 degreeC for 2 minutes. It wash | cleaned in the water washing bath of room temperature, and it neutralized using 0.1 sulfuric acid at 30 degreeC. Again, it wash | cleaned in the water washing bath of room temperature, and dried by the warm air of 100 degreeC. In this way, the surface of the transparent film was saponified.

Subsequently, a roll-shaped polyvinyl alcohol film having a thickness of 80 µm was continuously stretched 5 times in an aqueous solution of iodine and dried to obtain a polarizer having a thickness of 20 µm. Said saponified transparent film sample and a commercially available cellulose acetate film (Fuji Tak TD80UF, Fujifilm Co., Ltd. make, film thickness of 80 micrometers) using polyvinyl alcohol (PVA-117H by Kuraray) 3% aqueous solution as an adhesive agent The Re value is 3 nm and the Rth value is 50 nm), which is attached by roll-to-roll with a polarizer in between. The film length is 500 m, the absorption axis is in the longitudinal direction, and the slow axis is in the longitudinal direction orthogonal to the film. The polarizing plate protected by was obtained.

(Production of Polarizing Plates H106 and H107)

H106 and H107 produced a polarizing plate in a batch type. The production cuts out the above-mentioned transparent film and a commercially available cellulose acetate film (Fujitak TD80UF, manufactured by Fuji Photo Film Co., Ltd., film thickness of 80 µm, Re value of 3 nm, Rth value of 50 nm) to A4 size, and A4 size. A stretched polarizer of size was sandwiched between. Saponification conditions and the adhesive used the same thing as the polarizing plate H101 manufacture.

Polarizer performance is shown in Tables 2 and 3 below. If it is a roll-to-roll, it turns out that there exists little axial shift | offset | difference, and that a characteristic is favorable and a polarizing plate characteristic is favorable in the polarizing plate of a present Example. However, when the film thickness of a sample is thin, it turns out that durability is bad.

(Mount evaluation on panel)

The polarizing plate of this invention was mounted and evaluated on the panel of a liquid crystal display device.

[IPS Mode]

<Polarizer for IPS Liquid Crystal Cell>

A ton film (manufactured by JSR Corporation) was stretched to produce an optical compensation film of Re = 270 nm and Rth = 0 nm, and the slow axis of the optical compensation film and the polarizing plate on the transparent film side of the present invention of the polarizing plate of the present invention. It adhere | attached so that an absorption axis might correspond and the polarizing plate integrated optical compensation film was produced.

<Production of IPS Mode Liquid Crystal Cell>

On one glass substrate, the electrode was arrange | positioned so that the distance between adjacent electrodes might be set to 20 micrometers, the polyimide film was formed as an orientation film on it, and the rubbing process was carried out. A polyimide film was formed on one surface of one glass substrate prepared separately, and the rubbing process was carried out to set it as an orientation film. The two glass substrates face each other, and the gaps (gaps; d) of the substrates are overlapped and bonded so that the rubbing directions of the two glass substrates are parallel to each other, and then the refractive index anisotropy (Δn) is 0.0769 and the dielectric constant. The nematic liquid crystal composition whose anisotropy (Δε) is positive 4.5 was sealed. The value of d · Δn of the liquid crystal layer was 300 nm.

Attached to the light source side of this liquid crystal cell with an adhesive so that the slow axis of a liquid crystal cell and the absorption axis of a polarizing plate may correspond so that the film of this invention of the polarizing plate of this invention may be a cell side, and the polarizing plate and absorption axis which oppose the opposite side of a liquid crystal cell The IPS type liquid crystal display device was produced by making the optical compensation film side of the said polarizing plate integrated optical compensation film into the liquid crystal cell side so that it may orthogonally cross, and affixing with an adhesive.

[VA mode]

(Optical Compensation Film for VA)

Using the transparent film sample which concerns on this invention, the optical compensation film sample was produced according to the method of Example 1 of Unexamined-Japanese-Patent No. 2003-315541. 2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (TFMB Transparent film samples 101 to 104 prepared in Example or Comparative Example using a solution prepared by preparing a weight average molecular weight (Mw) of 70,000 and a polyimide having a Δn of about 0.04 in a solvent at 25 wt% using cyclohexanone. , 001 to 004 were applied. Then, after heat-processing for 10 minutes at 100 degreeC, the optical compensation film by which the polyimide film with a thickness of 6 micrometers was apply | coated to the transparent film which concerns on this invention was obtained by uniaxially stretching 15% at 160 degreeC. The optical characteristic of this optical compensation film was Re = 72 nm, Rth = 220 nm, and the shift | offset | difference angle of an orientation axis is within ± 0.3 degree | times, and it was an optical compensation film which has a birefringence layer of nx> ny> nz.

(Mounting evaluation for VA type liquid crystal display device)

The side where the polyimide film was not coated on the optical compensation film obtained in the above example was subjected to alkali saponification and adhered to the polarizer directly by adhering to the polarizer with a polyvinyl alcohol-based adhesive. At this time, it adhere | attached so that the nx direction of an optical compensation film and the absorption axis of a polarizing plate may orthogonally cross. It adhere | attached on VA liquid crystal panel with an adhesive so that these optical compensation films might become a liquid crystal cell side. Moreover, only the polarizing plate was affixed to VA liquid crystal panel through an adhesive so that the absorption axis of a polarizing plate might orthogonally cross on the opposite side of a liquid crystal cell.

[Panel evaluation]

<Evaluation of phase difference film and measurement of leakage light of the produced liquid crystal display device>

The viewing angle dependence of the transmittance | permeability of the produced liquid crystal display device was measured. The azimuth was measured from the front side to 80 ° every 10 ° in the oblique direction, and the azimuth angle was measured up to 360 ° every 10 ° based on the horizontal right direction (0 °). It was found that the luminance at the time of black display increased as light intensity increased in the front direction, and the light transmittance also increased, and had a maximum value near 70 degree angle. It was also found that the contrast deteriorated as the black display transmittance increased. Therefore, the viewing angle characteristic was evaluated based on the maximum value of the black display transmittance of the front side and the leakage light transmittance of 60 degrees of depression.

In addition, in the durability test, unevenness of display such as contrast and color after 500 hours of treatment at 60 ° C. 90%, 60 ° C. 95%, and 80 ° C. was observed. The obtained results are shown in Table 4.

Since H101-105 which is a polarizing plate of this invention is small in axial shift | offset | difference and high in durability, it turns out that not only not only a viewing angle characteristic but a generation | occurrence | production of a nonuniformity is few and favorable.

Evaluation of display characteristics

(Viewing angle characteristic)

(Double-circle): It is favorable because the difference of viewing angle characteristic is very minute.

○: small difference in viewing angle characteristics

×: large difference in viewing angle characteristics

(Uneven)

(Double-circle): Unevenness is very fine and is favorable

○: less uneven

△: slightly non-uniformity

×: non-uniformity is large

The 1st effect of this invention reduces in-plane retardation (Re) of the protective film of a polarizing plate, retardation (Rth) of a film thickness direction, makes it substantially zero, and attaches a long roll with a roll to roll, By setting it as a polarizing plate, the polarizing plate which the dispersion | variation of an axial angle is small and improved polarizing plate performance (especially axial angle and light leakage) can be provided. The second effect of the present invention is to provide an optical compensation film and a polarizing plate using the transparent film, and can provide an excellent liquid crystal display device that does not cause light leakage or color change even if an environment change such as temperature or humidity occurs. have.

Claims (18)

A long polarizer having an absorption axis parallel to the longitudinal direction, and It has a slow axis orthogonal or parallel to the longitudinal direction, and the retardation value Re in the film plane and the retardation value Rth in the film film thickness direction satisfy the formulas (i) and (ii). Long transparent film is laminated, (Ⅰ) 0

Re ₍₆₃₀₎

20 (Ii) | Rth ₍₆₃₀₎ |

25 In the above formula, Re (λ) is an in-plane retardation value (unit: nm) at wavelength λ nm, Rth (λ) is a retardation value (unit: nm) in the film thickness direction at wavelength λ nm, Single plate transmittance (TT), parallel transmittance (PT), orthogonal transmittance (CT), and polarization degree (P) of 400 to 700 nm at 25 ° C. and 60% RH are represented by the following formulas (a) to (d), (a) 40.0

TT

45.0 (b) 30.0

PT

40.0 (c) CT

2.0 (d) 95.0

P It satisfies at least 1 or more of them, The long polarizing plate characterized by the above-mentioned. The method of claim 1, An orthogonal or parallel axis shift angle between the absorption axis of the polarizer and the slow axis of the transparent film is within 10 degrees. The method of claim 1, Cellulose acylate is contained as a polymer raw material which forms the said transparent film, The long polarizing plate characterized by the above-mentioned. delete The method of claim 1, When the orthogonal transmittance in the wavelength λ is T (λ), T ₍₃₈₀₎ , T ₍₄₁₀₎ , and T ₍₇₀₀₎ are represented by the following formulas (e) to (g), (e) T ₍₃₈₀₎

2.0 (i) T ₄₁₀

1.0 (g) T ₍₇₀₀₎

0.5 It satisfies at least 1 or more of them, The long polarizing plate characterized by the above-mentioned. The method of claim 1, The change amount (ΔCT) and the change in polarization degree (ΔP) of the 400 to 700 nm orthogonal transmittance at 500 ° C. under the condition of 60 ° C. 95% RH for the following 500 hours are represented by the following formulas (h) and (i), (h) -6.0

ΔCT

6.0 (i) -10.0

ΔP

0.0 Satisfy at least one of In the above formula, the change amount represents a value obtained by subtracting the pre-test measurement from the post-test measurement. The method of claim 1, The change amount (ΔCT) of the orthogonal transmittance (ΔCT) and the change in polarization degree (ΔP) of 400 to 700 nm when allowed to stand for 500 hours under the condition of 60 ° C. and 90% RH are represented by the following formulas (j) and (k), (j) -3.0

ΔCT

3.0 (k) -5.0

ΔP

0.0 It satisfies at least 1 or more of them, The long polarizing plate characterized by the above-mentioned. The method of claim 1, The change amount (ΔCT) of the orthogonal transmittance (ΔCT) and the change in polarization degree (ΔP) of 400 to 700 nm when allowed to stand for 500 hours under the conditions of 80 ° C. are represented by the following formulas (l) and (m), (l) -3.0 ΔCT

3.0 (m) -2.0

ΔP

0.0 It satisfies at least 1 or more of them, The long polarizing plate characterized by the above-mentioned. In the transparent film of the long polarizing plate of Claim 1, following formula (VII), (Iii) Re ₍₆₃₀₎ = 0 to 200 (nm) and Rth ₍₆₃₀₎ = 0 to 400 (nm) The optically anisotropic layer which satisfy | fills is formed, and it is set as an optical compensation film integral type, The long polarizing plate characterized by the above-mentioned. The method of claim 9, The optically anisotropic layer is formed using a discotic liquid crystal compound, characterized in that the long polarizing plate. The method of claim 9, The optically anisotropic layer is formed using a rod-like liquid crystal compound, characterized in that the long polarizing plate. The method of claim 9, The optically anisotropic layer contains a polymer film having birefringence, wherein the length of the polarizing plate. 13. The method of claim 12, The polymer film forming the optically anisotropic layer contains at least one polymer material selected from the group consisting of polyamide, polyimide, polyester, polyether ketone, polyamideimide polyesterimide, and polyaryl ether ketone. Long polarizing plate characterized by the above-mentioned. The method according to any one of claims 1 to 3 and 5 to 13, A long polarizing plate, wherein at least one of a hard coat layer, an antiglare layer, and an antireflection layer is formed on a surface thereof. It cut out from the long polarizing plate of any one of Claims 1-3 and 5-13, The polarizing plate characterized by the above-mentioned. The polarizing plate of Claim 15 was used, The liquid crystal display device characterized by the above-mentioned. The method of claim 16, The liquid crystal display device is characterized in that the VA or IPS type. A long polarizer, and A roll-to-roll is used to attach a long transparent film whose retardation value (Re) in the film plane and the retardation value (Rth) in the film thickness direction satisfy the following formulas (i) and (ii), (i) 0

Re ₍₆₃₀₎

20 (Ii) | Rth ₍₆₃₀₎ |

25 In the above formula, Re (λ) is an in-plane retardation value (unit: nm) at wavelength λ nm, Rth (λ) is a retardation value (unit: nm) in the film thickness direction at wavelength λ nm, Single plate transmittance (TT), parallel transmittance (PT), orthogonal transmittance (CT), and polarization degree (P) of 400 to 700 nm at 25 ° C. and 60% RH are represented by the following formulas (a) to (d), (a) 40.0

TT

45.0 (b) 30.0

PT

40.0 (c) CT

2.0 (d) 95.0

P At least 1 or more is satisfied, The manufacturing method of the long polarizing plate characterized by the above-mentioned.