KR101158461B1 - Transparent film for optical applications, and optical compensating film, polarizing plate and liquid crystal display device using the same - Google Patents

Abstract

(Problem) By providing a transparent film with little optical anisotropy, little difference in physical properties between the machine direction and the direction perpendicular to the machine direction, and small change in optical anisotropy due to the change in temperature and humidity, and the change in the longitudinal and horizontal dimensions. Providing an excellent liquid crystal display device that does not cause light leakage or color taste change even if the environment such as humidity changes.

(Measures) The tensile modulus in the machine direction is 2.4 × 10 ⁹ to 4.9 × 10 ⁹ N / m 2, and the tensile modulus in the direction perpendicular to the machine direction is 2.3 × 10 ⁹ to 4.7 × 10 ⁹ N / m 2, and the machine direction The elastic modulus ratio of the tensile modulus in the direction perpendicular to the tensile modulus / machine direction is 0.80 to 1.36, and the retardation value Re in the film plane is 20 or less, and the retardation value Rth in the film thickness direction is 25 or less. . Moreover, it is set as the optical compensation film, a polarizing plate, and a liquid crystal display device using the said transparent film.

Description

TRANSPARENT FILM FOR OPTICAL APPLICATIONS, AND OPTICAL COMPENSATING FILM, POLARIZING PLATE AND LIQUID CRYSTAL DISPLAY DEVICE USING THE SAME}

BRIEF DESCRIPTION OF THE DRAWINGS The liquid crystal display device of the IPS mode which arrange | positioned the transparent film 19 of this invention.

[Description of Drawings]

11a: upper polarizing film

11b: lower polarizing film

12a: transmission axis of upper polarizing film

12b: transmission axis of lower polarizing film

13: second optical compensation film

15: first optical compensation film

15a: slow axis of the first optical compensation film

16: substrate

17: liquid crystalline molecule

18: substrate

16, 17, 18: liquid crystal cell

19: transparent film of the present invention

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

A liquid crystal display (LCD) consists of a liquid crystal cell and a polarizing plate. The polarizing plate has a protective film and a polarizing film, and is obtained by, for example, dyeing and stretching a polarizing film made of a polyvinyl alcohol film with iodine and laminating both surfaces thereof with a protective film. In a transmissive liquid crystal display device, this polarizing plate may be attached to 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 consists of liquid crystal molecules, two substrates for encapsulating them, and an electrode layer for applying a voltage to the liquid crystal molecules. The liquid crystal cell is a difference in the alignment state of the liquid crystal molecules, and is ON, OFF display, TN (Twisted Nematic), IPS (In-Plane Switching), OCB (0ptically Compensatory) that can be applied to any of the transmission and reflection type Display modes such as Bend), VA (Vertically Aligned), and ECB (Electrically Contro1led Birefringence) have been proposed.

Among such LCDs, a neat liquid crystal molecule having positive dielectric anisotropy and a 90 degree twist nematic liquid crystal display device (hereinafter, referred to as a TN mode) using a nematic liquid crystal molecule having positive dielectric anisotropy are used. It 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 gray level inversion in which brightness is reversed in gray scale display. This improvement is strongly desired.

In order to solve this problem, the liquid crystal display device by the so-called inplane switching (IPS) mode which applies a lateral electric field to a liquid crystal, and the protrusion or slit electrode formed in the panel by vertically orienting the liquid crystal of dielectric anisotropy The vertical division (VA) mode which carried out the orientation division | segmentation is proposed and put into practical use. In recent years, these panels are not only used for monitors, but are being developed as TVs, and thus the brightness of screens is greatly improved. For this reason, some light leakage in the diagonal diagonal incidence direction at the time of black display which did not become a problem in these operation modes conventionally appeared as a cause of the fall 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, when a birefringent medium orthogonal to each other is arranged between the substrate and the polarizing plate having an optical axis having a function of compensating the increase or decrease of the retardation of the liquid crystal layer at the time of tilting, the white display or halftone display at the time of looking directly at the tilting direction. The thing which can improve coloring 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 of improving the viewing angle by negating the birefringence 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 angles when the orthogonal polarizing plate is inclined is sufficient. There is a problem that can not be solved. In addition, even in a manner known to compensate for the 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 one wavelength, it cannot be assumed that it can be compensated at another wavelength. For example, even if light leakage is compensated for by the green wavelength having the largest visibility, there is a problem that light leakage occurs in blue of a smaller wavelength or red of a larger wavelength. In order to solve this problem, Non-Patent Document 1 proposes to laminate two biaxial films. However, since two biaxial films were used for this method, there existed a problem that axial shift | offset | difference of a biaxial film is easy to generate | occur | produce, and screen nonuniformity is easy to generate | occur | produce. In light leakage at the time of black display, in-plane retardation Re is about 5 nm and retardation Rth of film thickness direction is about 50 nm in the triacetyl cellulose film conventionally used as a polarizing plate protective film between a liquid crystal cell and a polarizer. It also became the cause. Therefore, it is desired to develop a transparent film in which both in-plane retardation Re and retardation Rth of a film thickness direction are small, and to use it as a protective film of a polarizing plate.

In recent years, in liquid crystal displays, the temperature may be raised by the internal backlight or may be used under an environment of high temperature and high humidity. The triacetyl cellulose film as the polarizing plate protective film may change its Re and Rth due to temperature and humidity. There was a problem that the optical compensation performance changed, light leaked or unevenness occurred in the black display. In particular, in such a case, the phenomenon or color taste of light leakage during the original black display from the periphery of the display device is changed due to the fact that the length and width of the display device are different, and the member may have different physical properties from the original length and width. The trouble was a problem. Therefore, development of the film from which the liquid crystal display device with little change of the optical compensation function by such an environment is obtained is desired.

As one of the causes of the change of optical compensation ability due to the environment of high temperature, high humidity, etc., the physical properties of the transparent protective film are different in the machine conveying direction and the direction perpendicular to it at the time of film formation, If the film receives any force in the longitudinal and transverse directions when the environmental change occurs, the degree is different in the longitudinal and transverse directions. Therefore, as a physical characteristic of a transparent film, it is preferable that there is no difference in a machine direction and the direction perpendicular | vertical to it.

In recent years, liquid crystal displays have been developed not only for PC monitors but also for TVs, and thus, large screens have been developed. At the same time as the large screen, the thinning of the entire liquid crystal display device is also progressing, and warpage of the thin glass or resin substrate constituting the liquid crystal display device tends to occur, and the panel center portion is concave from the viewing side, and the edge portion is visually recognized. "War" bent to the side is a problem. When warping occurs, the edge portion or four corners of the panel may come into contact with the case body, which adversely affects the screen display performance.

The warp phenomenon causes expansion and contraction of various members laminated on the upper side (viewing side) and the lower side (rear side) with respect to a glass or resin liquid crystal cell substrate which does not cause warping inherently. Since a difference occurs in the lower side and the lower side, the balance between the forces of the outer and inner sides of the liquid crystal display device is broken and the entire screen is bent. In addition, in the normal liquid crystal display device, the surface on the viewing side is open, while the rear surface is incorporated in the case body and is in a semi-closed state. For this reason, a difference arises in heating, a moisture absorption, and a moisture absorption in the upper laminated body holding the board | substrate and the lower laminated body, and the difference also arises in expansion and contraction for this.

The liquid crystal display device arrange | positions the polarizing plate which makes polarization on both sides of the liquid crystal cell which enclosed the liquid crystal on the glass substrate, if necessary, laminates various optical elements, such as a phase difference plate, an antireflection film, and a brightness enhancement film, It is fixed by the fixing frame which consists of metal plates, such as stainless steel, called a "bezel", and it is set as a liquid crystal module, this liquid crystal module is assembled together with another structural member, and is accommodated and manufactured.

When the power supply of the liquid crystal display is turned on, a difference in temperature and humidity may occur between the viewer side and the backlight side due to a rise in temperature in the backlight. In this case, the conditions of the temperature and humidity which the laminated body on the viewing side including a polarizing plate and the laminated body on the backlight side expose to a liquid crystal cell are different, and it is thought that each laminated body is affected by this. When warping occurs, not only the edges or the four corners of the panel come into contact with the case body but also affect the adhesion to the backlight provided on the back side, which causes a problem in display performance. Furthermore, when a black display screen is used, there may be a "corner nonuniformity" phenomenon in which the four corners of the screen are lightly leaked into an uneven shape, which is a very big problem in display performance.

[Patent Document 1] Japanese Patent Application Laid-Open No. 9-80424

[Patent Document 2] Japanese Patent Application Laid-Open No. 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 1st subject of this invention reduces the in-plane retardation Re of the protective film of a polarizing plate, and the retardation Rth of a film thickness direction, makes it substantially zero, and changes Re and Rth by environmental changes, such as temperature and humidity. It is possible to provide a transparent film having a low physical property and having almost the same physical properties in the machine direction of the film and in a direction perpendicular to the film (in-plane longitudinal direction and transverse direction). The second object of the present invention is to provide an optical compensation film and a polarizing plate using the above-mentioned transparent film, so that even if the environment changes such as temperature and humidity, the physical properties of the longitudinal and horizontal properties of the film are almost the same, so that no light leakage or color taste changes. It is to provide an excellent liquid crystal display device.

Moreover, the 3rd subject of this invention is the outstanding liquid crystal display device in which the panel of the liquid crystal display device mentioned above prevents the warp generate | occur | produced by the curvature of a liquid crystal cell, and the fall of the display performance which arises by warp does not occur. To provide.

As a result of careful examination, the inventor of the present invention has a mechanical conveyance direction such that the physical properties of the transparent film, in particular, the tensile modulus, storage modulus, photoelastic coefficient, and dimensional stability are substantially the same in the direction perpendicular to the machine direction and the machine direction. The film was produced so as not to be extremely stretched. The transparent film having substantially the same physical properties in the machine direction and in the direction perpendicular to the machine direction has almost the same degree of orientation of the polymer in either direction. That is, retardation Re in film surface becomes small. In addition, the retardation (Rth) of the film thickness direction of a film is expressed by orienting a polymer in an in-plane and film thickness direction according to the situation of film forming irrespective of these mechanical properties. Therefore, as a result of earnest examination, the inventor of the present invention sufficiently reduces the optical anisotropy of the film by using a compound which suppresses the orientation of the transparent film in the in-plane and film thickness directions, and particularly reduces the retardation Rth in the film thickness direction. Succeeded. Moreover, the compound which reduces Rth made it possible to also reduce in-plane retardation value (Re).

Moreover, the inventor of this invention considered that the warp phenomenon generally tends to generate | occur | produce more largely in the screen long side direction, and thought to control the physical property of the laminated body which comprises a liquid crystal display device with respect to the screen long side direction. In addition, it was considered that the screen front side was normally opened and the screen back side was embedded in the closed case body, and it was considered to form a difference between the upper side (viewing side) of the substrate and the lower side of the substrate. As a result of earnestly examining the above, the value which multiplied the elastic modulus of each layer and its cross-sectional area with respect to the laminated body of the upper side (viewing side) and the lower side (back side) which sandwiched the board | substrate of a liquid crystal display device in the screen long side direction. It was found that when the total is larger than the upper side, the deterioration of the display performance due to warp and warp can be prevented.

The subject of this invention is a transparent film of following (1)-(7), the optical compensation film of following (8)-(12), the polarizing plate of following (13)-(14), and following (15)-(20) Was achieved by a liquid crystal display device.

(1) The tensile modulus in the machine direction is 2.4 × 10 ⁹ to 4.9 × 10 ⁹ N / m 2, and the tensile modulus in the direction perpendicular to the machine direction is 2.3 × 10 ⁹ to 4.7 × 10 ⁹ N / m 2, (machine direction Of the tensile modulus of elasticity) / (tensile modulus of elasticity in the direction perpendicular to the machine direction) is 0.80 to 1.36, and the retardation value Re (nm) in the film plane represented by the formula (i) and (ii) and the ritata in the film thickness direction Dation value Rth (nm) satisfy | fills Formula (iii) (iv), The transparent film characterized by the above-mentioned.

(i) Re = (nx-ny) × d

(ii) Rth = ((nx + ny) / 2-nz) × d

Re

20 (iii) 0

Re

20

25(iv) │Rth│

25

(2) The storage modulus in the machine direction and the storage modulus in the direction perpendicular to the machine direction are both 1.5 × 10 ⁹ to 7.8 × 10 ⁹ N / m 2, and the (storage modulus in the machine direction) / (direction perpendicular to the machine direction) The storage elastic modulus) is 0.80-1.20, The transparent film as described in (1) characterized by the above-mentioned.

(3) The photoelastic coefficient in the machine direction and the photoelastic coefficient in the direction perpendicular to the machine direction are both 5.0 × 10 ^-11 m 2 / N or less, (photoelastic coefficient in the machine direction) / (photoelastic coefficient in the direction perpendicular to the machine direction). The ratio of 0.80 to 1.20 is a transparent film in any one of (1)-(2) characterized by the above-mentioned.

(4) The dimensional change rate after 24 hours at 60 ° C and 90% RH and the dimensional change rate after 24 hours at 90 ° C dry are both ± 0.5% or less in both the machine direction and the direction perpendicular to the machine direction. The ratio of dimensional change rate of () / (dimension change rate of the direction perpendicular to a machine direction) is 0.3-2.5, The transparent film in any one of (1)-(3) characterized by the above-mentioned.

(5) It is produced by the solvent cast method, The transparent film in any one of (1)-(4) characterized by the above-mentioned.

(6) It consists of cellulose acylate, The transparent film in any one of (1)-(5) characterized by the above-mentioned.

(7) At least 1 type of compound which reduces retardation Rth of a film film thickness direction in the range which satisfy | fills following formula (v) and (vi) is characterized by any one of (1)-(6) The transparent film of description.

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

-1.0

A

30(vi) 0.01

A

30

here,

Rth (A): Rth (nm) of the film containing A% of the compound which lowers Rth

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

A: Mass (%) of the compound when the mass of the film raw material polymer is 100

to be.

The optically anisotropic layer which satisfy | fills following formula (vii) was formed in the transparent film in any one of (8) (1)-(7), The optical compensation film characterized by the above-mentioned.

(vii) Re = 0 to 200 (nm) or Rth = 0 to 300 (nm)

(9) The optical compensation film according to any one of (8), wherein the optically anisotropic layer is formed using a discotic liquid crystalline compound.

(10) The optical compensation film as described in (8) or (9) characterized by the optically anisotropic layer being formed using the rod-shaped liquid crystal layer.

(11) The optical compensation film according to any one of (8) to (10), wherein the optically anisotropic layer consists of a polymer film having birefringence.

(12) The polymer film forming the optically anisotropic layer comprises at least one polymer material selected from the group consisting of polyamide, polyimide, polyester, polyether ketone, polyamideimide polyesterimide, and polyaryl ether ketone. It contains, The optical compensation film as described in (11) characterized by the above-mentioned.

(13) The polarizing plate which used the transparent film in any one of (1)-(7), or the optical compensation film in any one of (8)-(12) as a protective film of a polarizer.

(14) The polarizing plate according to (13), wherein one or more layers of a hard coat layer, an antiglare layer, and an antireflection layer are formed on the surface.

(15) Liquid crystal using any one of the transparent film in any one of (1)-(7), the optical compensation film in any one of (8)-(12), and the polarizing plate as described in (13) or (14). Display device.

(16) VA using any of the transparent film as described in any one of (1)-(7), the optical compensation film as described in any one of (8)-(12), and the polarizing plate as described in (13) or (14) Or IPS liquid crystal display.

(17) A panel having a liquid crystal cell in which a liquid crystal is sealed in a substrate made of glass or resin, a laminate formed on the front side of a liquid crystal cell including a polarizing plate, and a laminate formed on the back side of the liquid crystal cell including a polarizing plate. A liquid crystal display device having the front side as a visual side, comprising at least one of the laminate on the front side and the laminate on the back side, wherein the polarizing plate according to (13) or (14) is satisfied, and the following formula (viii) is satisfied. Liquid crystal display.

0.99(viii) ∑ _i (Ef _i × Sf _i ) / ∑ _j (Er _j × Sr _j )

0.99

[In the above formula, Ef _i represents the elastic modulus in the long side direction of the i-th layer constituting the laminate on the front side, and Sf _i represents the cross-sectional area with one side of the short side of the i-th layer constituting the laminate on the front side. , Er _j represents the elastic modulus in the long side direction of the j-th layer constituting the laminate on the substrate back side, and Sr _j represents the cross-sectional area of the short side of the j-th layer constituting the laminate on the substrate back side.

(18) The liquid crystal display device according to (17), wherein the surface of the front side of the liquid crystal display device is open, and this surface of the liquid crystal display device is closed by the case body.

(19) The liquid crystal display device according to (17) or (18), wherein the panel is rectangular or square and has a long side of 10 cm to 500 cm.

0.01 을 만족시키는 것을 특징으로 하는 (17)～(19) 중 어느 하나에 기재된 액정 표시 장치. (20) After 48 hours have elapsed at a temperature of 60 ° C. and a relative humidity of 90%, and under a temperature of 25 ° C. and a relative humidity of 60%, 20 minutes later, the warpage amount w (mm) of the panel is in the long side direction of the panel. W / L for length L (mm)

0.01 is satisfied, The liquid crystal display device in any one of (17)-(19) characterized by the above-mentioned.

Best Mode for Carrying Out the Invention

The transparent film of this invention can be used suitably as a transparent protective film of the polarizing plate which is a basic structural member of a liquid crystal display device. The transparent film of this invention is demonstrated in detail below.

[Production Method of Transparent Film]

The manufacturing method of the transparent film of this invention is demonstrated below.

[Film Production Method by Solvent Cast Method]

It is preferable that the transparent film of this invention produces a film by the solvent cast method. In the solvent cast method, the polymer of the film raw material is made into a solution (dope) dissolved in a suitable organic solvent, the dope is cast on a suitable support, preferably a metal support, and then the solvent is dried to dry the film from the support. It removes and manufactures by fully drying a solvent from a film again.

[Residual solvent amount when removing]

When the film is produced by the solvent cast method, the film is dried on a metal support and the solvent is removed at the time when the film is gelled. In order to remove 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 (ix). In addition, the residual volatile matter mass is the value which subtracted the film mass after heat processing from the film mass before heat processing, when heat-processing a film at 120 degreeC for 2 hours.

(ix) Residual solvent amount = remaining volatile mass / film mass after heating x 100 (%)

[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 of this invention, control is required so that a film may not be extended | stretched strongly in any direction of a machine direction and the direction perpendicular | vertical to it. Specifically, in the case of film conveyance 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 conveyance to 10 to 50 kgf / m. On the other hand, the strength of the tension applied in the machine direction and in the direction perpendicular to the machine direction is preferably the same strength. In this case, the tenter system using a tenter clip can also be preferably used to hold the film in the vertical direction and to adjust the tension. For example, a method (tenter method) of drying the entire process or a part of the processes shown in JP-A-62-46625 by drying the width both ends of the web with a clip in the width direction while maintaining the width can be preferably used. have.

[Physical Properties of Transparent Films]

Hereinafter, the physical properties of the transparent film of the present invention will be described.

[Elastic modulus of film]

The tensile modulus in the machine direction of the transparent film of the present invention is 2.4 × 10 ⁹ to 4.9 × 10 ⁹ N / m 2, and the tensile modulus in the direction perpendicular to the machine direction is 2.3 × 10 ⁹ to 4.7 × 10 ⁹ N / m 2, It is preferable that the ratio of (tensile modulus in the machine direction) / (tensile modulus in the direction perpendicular to the machine direction) is 0.80 to 1.36.

More preferably, the tensile modulus in the machine direction is 2.5 × 10 ⁹ to 4.7 × 10 ⁹ N / m 2, and the tensile modulus in the direction perpendicular to the machine direction is 2.4 × 10 ⁹ to 4.6 × 10 ⁹ N / m 2, ( The ratio of tensile modulus in the machine direction) / (tensile modulus in the direction perpendicular to the machine direction) is 0.85 to 1.30. More preferably, the tensile modulus in the machine direction is 2.6 × 10 ⁹ to 4.5 × 10 ⁹ N / m 2, and the tensile modulus in the direction perpendicular to the machine direction is 2.5 × 10 ⁹ to 4.4 × 10 ⁹ N / m 2, ( The ratio of tensile modulus in the machine direction) / (tensile modulus in the direction perpendicular to the machine direction) is 0.88 to 1.25. As a specific measuring method, the elasticity modulus was calculated | required by measuring the stress in 0.5% elongation at the tensile rate of 10% / min in 23 degreeC-70% atmosphere using the universal tensile tester STM T50BP by Toyoboldwin.

[Storage Modulus of Film]

In the transparent film of the present invention, the storage modulus in the machine direction and the storage modulus in the direction perpendicular to the machine direction are all 1.5 × 10 ⁹ to 7.8 × 10 ⁹ N / m 2, and the storage modulus in the machine direction is perpendicular to the machine direction. It is preferable that the ratio of storage modulus of is 0.80 to 1.20.

More preferably, the storage modulus is 1.8 × 10 ⁹ to 7.4 × 10 ⁹ N / m 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 is 2.0 × 10 ⁹ to 6.9 × 10 ⁹ N / m 2 in both the machine direction and the vertical direction, and the ratio of storage modulus in the direction perpendicular to the machine direction is 0.84 to 1.16. The specific measuring method calculated | required storage elastic modulus from the dynamic viscoelasticity measurement, changing temperature.

[Photoelastic coefficient of film]

In the transparent film of the present invention, both the photoelastic coefficient in the machine direction and the photoelastic coefficient in the direction perpendicular to the machine direction are 5.0 × 10 ⁻¹¹ m 2 / N or less, and the photoelastic coefficient in the direction perpendicular to the machine direction It is preferable that the ratio is 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 4.0 × 10 ⁻¹¹ m 2 / N or less, and the ratio of the photoelastic coefficient in the machine direction / photoelastic coefficient in the direction perpendicular to the machine direction 0.82-1.18.

More preferably, the photoelastic coefficient in the machine direction and the photoelastic coefficient in the direction perpendicular to the machine direction are all 3.0 × 10 ⁻¹¹ m 2 / N or less, and the ratio of the photoelastic coefficient in the machine direction / photoelastic coefficient in the direction perpendicular to the machine direction 0.84-1.16.

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

[Dimensional Change of Film]

The dimensional change rate at 60 ° C. 90% RH after 24 hours and the dimensional change rate at 90 ° C. after 24 hours of the transparent film of the present invention are both ± 0.5% or less in both the machine direction and the direction perpendicular to the machine direction. 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. and 90% RH after 24 hours and the dimensional change rate at 90 ° C. after 24 hours are both ± 0.4% or less in both the machine direction and the direction perpendicular to the machine direction. The ratio of the dimensional change rate in the machine direction) / (the dimensional change rate in the direction perpendicular to the machine direction) is 0.4 to 2.2.

As a specific measuring method, two 30 mm x 120 mm sample of the transparent film of this invention were prepared, it was humidified for 24 hours at 25 degreeC and 60% RH, and automatic pingauge (Shinto Science Co., Ltd.) was carried out to 6 at both ends. Holes of mmφ were drilled at intervals of 100 mm to obtain raw dimensions L0 of punch intervals. Punch spacing dimension (L1) after processing one sample at 60 ° C and 90% RH for 24 hours, and measuring the punch interval after treating another sample at 90 ° C and 5% RH for 24 hours (L2) Was measured. In the measurement of all the intervals, it measured to the minimum scale 1 / 1000mm. Dimensional rate of change at 60 ° C. and 90% RH = {(L0-L1) / L0} × 100 The rate of dimensional rate of change at 90 ° C. and 5% RH = {(L0-L2) / L0} × 100 was calculated. .

[Hygroscopic Expansion Coefficient of Film]

It is preferable that the moisture absorption expansion coefficient of the transparent film of this invention shall be 30x10 <^-5> /% RH or less. The hygroscopic expansion coefficient is preferably 15 × 10 ⁻⁵ /% RH or less, and more preferably 10 × 10 ⁻⁵ /% RH or less. Moreover, although the moisture absorption expansion coefficient is preferable, it is a value normally 1.0x10 <^-5> /% RH or more. In addition, it is preferable that the hygroscopic expansion coefficient be substantially equal in the machine direction and in the vertical direction. The moisture absorption expansion coefficient represents the amount of change in the length of the sample 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, the light leakage by frame rise, ie, a deformation | transformation can be prevented, maintaining the optical compensation function of an optical compensation film.

It is preferable that it is 20-200 micrometers, and, as for the thickness of the transparent film of this invention, it is more preferable that it is 40-180 micrometers.

[Evaluation Method of Transparent Film]

In the evaluation of the transparent film of this invention, it measured and performed by the following method.

(Inside retardation Re)

Re

20 인 것이 바람직하다. 보다 바람직하게는 0

Re

15 이고, 0

Re

10 인 것이 더욱 바람직하다.In the transparent film of this invention, the retardation value Re in the film plane represented by Re = (nx-ny) xd is 0.

Re

It is preferable that it is 20. More preferably 0

Re

15 and 0

Re

It is more preferable that it is ten.

The measurement was made to humidify a sample 70 mm x 100 mm at 25 degreeC and 60% RH for 2 hours, and it measured from the vertical direction at 589 nm with an automatic birefringence meter (KOBRA21DH, Oji measurement Co., Ltd.).

(Retardation Rth in the film thickness direction)

25 인 것이 바람직하다. 보다 바람직하게는 │Rth│

23 이고, │Rth│

20 인 것이 더욱 바람직하다.In the transparent film of this invention, the retardation value Rth of the film film thickness direction represented by Rth = ((nx + ny) / 2-nz) xd is | Rth |

25 is preferred. More preferably │Rth│

23, │Rth│

It is more preferable that it is 20.

The measurement was made to humidify a sample 30 mm x 40 mm at 25 degreeC and 60% RH for 2 hours, and measured the value and film surface which were measured in the vertical direction at 632.8 nm with an ellipsometer (M150, Nippon Bunko Co., Ltd.). Retardation value and average refractive index measured in three directions of retardation value measured equally while tilting (direction inclined + 40 ° and -40 ° relative to film normal direction with in-plane slow axis as tilt axis (rotation axis)) An ellipsometer was calculated based on the hypothetical value (cellulose acylate: 1.48) and the input film thickness value.

[Evaluation Method of Transparent Film]

(Light leakage and color taste change on panel for humidity change, temperature change of polarizing plate)

The transparent film of this invention can be used suitably as the transparent protective film of the polarizer for liquid crystal display devices. In the case where it is mounted in a liquid crystal display and the temperature rises with the backlight inside the apparatus, or it is assumed to be used in an environment of high temperature and high humidity, especially when the whole screen should be displayed in black at the time of black display, It is preferable to reduce the trouble | wound malfunction which light leaks from the periphery of the edge, and the trouble that a color taste changes are changed from the protective film of the polarizing plate which has been used so far. More preferably, the above fault is zero.

[Material of transparent film]

As a material for forming the transparent film of the present invention, a polymer excellent in optical performance transparency, mechanical strength, thermal stability, water shielding property, isotropy, etc. is preferable, and Re and Rth described above are formulas (iii), ( Any material may be used as long as it satisfies iv). 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; Furthermore, polyolefins such as polyethylene and polypropylene, polyolefin polymers such as ethylene-propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamides, imide polymers, sulfone polymers, and polyether sulfone 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 of this invention can also be formed with the hardened layer of ultraviolet curing type, thermosetting resins, such as an acryl type, a urethane type, an acryl urethane type, an epoxy type, and a silicone type.

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

[Cellulose Acylate Raw Material Cotton]

Examples of the cellulose of the cellulose acylate raw material used in the transparent film of the present invention include cotton linter and wood pulp (softwood pulp, softwood pulp), and the like, and cellulose acylate obtained from any raw material cellulose can be used. May be used. For detailed descriptions of these raw celluloses, see, for example, Marsawa, Uda, `` Plastic Materials Course (17) Fibrin-Based Resin '' (Nigan Industrial Newspaper, 1970). Cellulose described in pages 7 to 8) can be used, and the cellulose acylate film is not particularly limited.

[Cellulose Acylate Substitution Degree]

Next, the cellulose acylate produced from the above-described cellulose as a raw material will be described. The cellulose acylate is obtained by acylating the hydroxyl group of the cellulose, and the substituent may be any one from an acetyl group having 2 carbon atoms of the acyl group to 22 carbon atoms. In the cellulose acylate, the degree of substitution of cellulose to a hydroxyl group 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, in the cellulose acylate, the degree of substitution of the cellulose to the hydroxyl group is not particularly limited, but the degree of acyl substitution to the hydroxyl group of the cellulose is preferably 2.50 to 3.00. Furthermore, it is preferable that substitution degree 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 or an allyl group, or is not particularly limited, and may be a single or a mixture of two or more kinds among the acetic acid and / or fatty acids 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 have a substituted group. Preferred acyl groups are acetyl, propionyl, butanoyl, heptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetra decanoyl, 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 earnestly examining by the inventor of this invention, when the acyl substituted group substituted by the hydroxyl group of the cellulose mentioned above is two or more types selected substantially 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 in viscosity average polymerization degree, 180-550 is more preferable, 180-400 are still more preferable, 180-350 are especially preferable in cellulose acetate. . 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 such as Uda et al. (Kazuo Uda, Hideo Saito, Textile Society, Vol. 18 No. 1, 105-120 pages, 1962). 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 optical film of the present invention can be further reduced.

In addition, the molecular weight distribution of the cellulose acylate preferably used in the present invention is evaluated by gel permeation chromatography, the polydispersity index Mw / Mn (Mw is the mass average molecular weight, Mn is the number average molecular weight), It is preferable that the molecular weight distribution is narrow. As a specific value of Mw / Mn, it is preferable that it is 2.0-4.0, It is more preferable that it is 2.0-3.5, It is most preferable that it is 2.3-3.3.

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 weight 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. When the amount of the sulfuric acid catalyst is in the above range, a cellulose acylate (uniform in molecular weight distribution) that is preferable also in terms of molecular weight distribution can be synthesized. 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, It is especially 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 this invention, in order to make it the moisture content of this cellulose acylate, it is necessary to dry, and the method will not be specifically limited if it becomes the target moisture content. These cellulose acylates of the present invention are described in detail on pages 7 to 12 in the Korean Journal of Invention Publication No. 2001-1745 (published on March 15, 2001, published by the 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, a polymerization degree, molecular weight distribution.

[Additives for Transparent Films]

The transparent film of this invention may heat-melt thermoplastic polymer resin, and may form into 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 the optical anisotropy, a wavelength dispersion regulator, a sunscreen, a plasticizer, a deterioration inhibitor, a fine particle, an optical property adjuster, etc.) can be added at the time of hot melting. . In addition, 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, UV light inhibitors, plasticizers, deterioration inhibitors, fine particles, optical property adjusting agents and the like) can be added, and these will be described below. Moreover, although the addition time may be added at any time at the time of a dope preparation process, you may perform the process of adding and preparing an additive to the last preparation 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 of this invention is demonstrated. As a result of careful examination, the inventors of the present invention have sufficiently reduced optical anisotropy by using a compound which suppresses the polymer in the film from being oriented in the in-plane and film thickness directions, so that Re is zero and Rth is close to zero. For this purpose, the compound which lowers optical anisotropy is fully compatible with a polymer, and it is advantageous that the compound itself does not have a rod-like structure or a planar structure. Specifically, in the case where there are a plurality of planar functional groups such as aromatic groups, a structure having these functional groups in the non-planar surface rather than the same plane is advantageous.

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

The compound which reduces the optical anisotropy of the cellulose acylate film of this invention, especially the retardation Rth of the film thickness direction represented by following formula (ii) is 1 type in the range which satisfy | fills following formula (v) and (vi). It is preferable to contain more than.

(ii) Rth = ((nx + ny) / 2-nz) × d

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

-1.0

A

30(vi) 0.01

A

30

Formula (v), (vi) is

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

-2.0

A

25 (vi) 0.05

A

25

It is more preferable that it is

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

-3.0

A

20 인 것이 더욱 바람직하다. 여기서,(vi) 0.1

A

It is more preferable that it is 20. here,

delete

Rth (A): Rth (nm) of the film containing A% of the compound which lowers Rth

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

A: Mass (%) of the compound when the mass of the film raw material polymer is 100

to be.

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.

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

General formula (1)

 General formula (2)

In the 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 more preferably 6 to 20 (eg, methyl, ethyl, propyl, iso). Propyl, butyl, isobutyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, cyclohexyl, heptyl, octyl, bicyclooctyl, nonyl, adamantyl, decyl, t-octyl, undecyl, dodecyl , Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, didecyl) are particularly preferred. As an aryl group, the thing of 6-30 carbon atoms is preferable, and the thing of 6-24 (for example, phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, triphenylphenyl) is especially preferable. Although the preferable example of a compound represented by General formula (1) or General formula (2) is shown below, this invention is not limited to these specific examples.

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 preferably a compound represented with the following general formula (4).

General formula (4)

In General Formula (4), R ^4d , R ^5d, and R ^6d each independently represent an alkyl group or an aryl group. The alkyl group may be linear, branched or cyclic, preferably having 1 to 20 carbon atoms, still 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 group. Carbonyl group, acyloxy group, sulfonylamino group, hydroxy group, cyano group, amino group and acylamino group are preferable, More preferably, they are a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a sulfonylamino group, and an 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.

Wavelength dispersion regulator

In the transparent film of the present invention, Re and Rth are small, and if further explained, it is preferable that the dependence of the Re and Rth wavelengths, that is, the wavelength dispersion is small. As a means of reducing this wavelength dispersion, in this invention, it is effective to add the compound which adjusts wavelength dispersion with respect to a transparent film (henceforth a wavelength dispersion regulator), and these compounds are demonstrated below. In order to make wavelength dispersion of Rth of the transparent film of this invention favorable, the compound which reduces the wavelength dispersion ₍ DELTA ₎ Rth = | Rth ₍₄₀₀₎ -Rth ₍₇₀₀₎ | of Rth represented by following formula (x) is made into the following formula ( It is preferable to contain 1 or more types in the range which satisfy | fills xi) and (xii).

(x) ΔRth = Rth ₍₄₀₀₎ -Rth ₍₇₀₀₎ │

-2.0 (xi) (ΔRth (B) -ΔRth (0)) / B

-2.0

B

30(xii) 0.01

B

30

Formula (xi), (xii) is

-3.0 (xi) (ΔRth (B) -ΔRth (0)) / B

-3.0

B

25 (xii) 0.05

B

25

It is more preferable that it is

-4.0 (xi) (ΔRth (B) -ΔRth (0)) / B

-4.0

B

20(xii) 0.1

B

20

More preferably.

The wavelength dispersion regulator is a compound having an absorption in an ultraviolet region of 200 to 400 nm and reducing the Re ₍₄₀₀₎ -Re ₍₇₀₀₎ and the Rth ₍₄₀₀₎ -Rth ₍₇₀₀₎ | of the _film. As mentioned above, the wavelength dispersion of Re and Rth of a transparent film was adjusted by containing 0.01-30 mass% with respect to a transparent film solid content. By adding 0.1-30 mass% as addition amount, the wavelength dispersion of Re and Rth of a transparent film was adjusted.

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 (O): ΔRth (nm) of film not containing a compound that lowers ΔRth

B: Mass (%) of the compound when the mass of the film raw material polymer is 100

to be.

The values of Re and Rth of the transparent film generally have 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 short wavelength side. Moreover, the compound which has absorption in the ultraviolet region of 200-400 nm has a wavelength dispersion characteristic with the light absorbency of the long wavelength side 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 in the short wavelength side, similarly to the wavelength dispersion of absorbance.

Therefore, the wavelength dispersion of Re and Rth of a transparent film is absorbed by using absorption in the ultraviolet region of 200-400 nm as mentioned above, and having wavelength dispersion of Re and Rth of the compound itself assumed large short wavelength side. Can be adjusted. For this purpose, the compound which modulates wavelength dispersion is required to be compatible with polymer solid content sufficiently uniformly. The absorption band range of the ultraviolet region of such a compound is preferably 200 to 400 nm, more preferably 220 to 395 nm and even more preferably 240 to 390 nm.

In recent years, in liquid crystal displays such as televisions, notebook computers, and mobile portable terminals, in order to increase the luminance with less power, it is required to have excellent transmittance of the optical member used in the liquid crystal display. In this regard, a compound having absorption in an ultraviolet region of 200 to 400 nm and having a lowering _of Re _{( 400)} -Re ₍₇₀₀₎ and Rth ₍₄₀₀₎ -Rth ₍₇₀₀₎ | of the film is added to the transparent film. In this case, excellent spectral transmittance is required. In the transparent film of the present invention, the spectral transmittance at a wavelength of 380 nm is 45% or more and 95% or less, and the spectral transmittance at a wavelength of 350 nm is preferably 10% or less.

As mentioned above, it is preferable that the wavelength-dispersion control agent used preferably by this invention is 250-1000 molecular weight from a volatility viewpoint. More preferably, it is 260-800, More preferably, it is 270-800, Especially preferably, it is 300-800. If it is the range of these molecular weights, 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 transparency, It is more preferable that it is 0.1-20 mass%, It is especially preferable that it is 0.2-10 mass%. .

(Compound addition method)

In addition, you may use these wavelength dispersion regulators individually, 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 any time in a dope preparation process, and you may carry out at the end of a dope preparation process.

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

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

Formula (101) Q ¹ -Q ² -OH

(In formula, Q <^1> represents a nitrogen-containing aromatic heterocycle and Q <^2> represents an aromatic ring.)

Q ¹ represents a nitrogen-containing aromatic aromatic heterocycle, preferably a 5-7 membered nitrogen-containing aromatic heterocycle, more preferably a 5-6 membered nitrogen-containing aromatic heterocycle, for example, imidazole, pyra Sol, triazole, tetrazole, thiazole, oxazole, serenazol, benzotriazole, benzothiazole, benzoxazole, benzocerenazol, thiadiazole, oxadiazole, naphthothiazole, naphthooxazole, aza Benzimidazole, purine, pyridine, pyrazine, pyrimidine, pyridazine, triazine, triazadene, tetrazaindene, etc. are mentioned, More preferably, it is a 5-membered nitrogen-containing aromatic heterocycle, Specifically, , Imidazole, pyrazole, triazole, tetrazole, thiazole, oxazole, benzotriazole, benzothiazole, benzoxazole, thiadiazole and oxadiazole are preferred, particularly preferably benzotriazole.

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

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

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.

The aromatic hetero ring is preferably an aromatic hetero ring containing a nitrogen atom or a sulfur atom. As a specific example of a heterocyclic ring, 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 aromatic heterocycle, Preferably they are pyridine, triazine, quinoline.

The aromatic ring represented by Q ² is preferably an aromatic hydrocarbon ring, more preferably a naphthalene ring or 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.), 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, C2-C) -12, Especially preferably, it is C2-C8, For example, a propargyl, 3-pentynyl, etc. are mentioned.), An aryl group (preferably C6-C30, More preferably, C6-C20) Especially preferably, they are 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, a part Oxy), and an aryloxy group (preferably C6-C20, More preferably, it is C6-C16, Especially preferably, it is C6-C12, For example, phenyloxy, 2-naphthyl Oxy, etc.), acyl group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, acetyl, benzoyl, formyl, p Baloyl, etc.) and an alkoxycarbonyl group (preferably Is 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 Preferably it is C7-20, More preferably, it is C7-16, Especially preferably, it is C7-10, For example, a phenyloxycarbonyl etc. are mentioned.), Acyloxy group (Preferably C2 -20, More preferably, it is C2-C16, Especially preferably, it is C2-C10, For example, acetoxy, benzoyloxy, etc. are mentioned.), Acylamino group (Preferably C2-C20, More Preferably it is C2-C16, Especially preferably, it is C2-C10, For example, acetylamino, benzoylamino, etc. are mentioned, The alkoxycarbonylamino group (Preferably C2-C20, More preferably Is 2 to 16 carbon atoms, in particular Preferably it is C2-C12, and a methoxycarbonylamino etc. are mentioned, for example.) An aryloxycarbonylamino group (preferably C7-C20, More preferably, C6-C16 is especially preferable. Preferably it is C7-C12, and a phenyloxycarbonylamino etc. are mentioned, for example, A sulfonylamino group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, carbon number 1-12, for example, methanesulfonylamino, benzenesulfonylamino, etc.), sulfamoyl group (preferably carbon 0-20, more preferably 0-16, especially preferably It has 0-12 carbons, For example, sulfamoyl, methyl sulfamoyl, dimethyl sulfamoyl, phenyl sulfamoyl, etc.), carbamoyl group (preferably C1-C20, More preferably, C1-C20) 16, particularly preferably carbon 1-12, for example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc.), alkylthio group (preferably C1-C20, more preferably Is C1-C16, Especially preferably, it is C1-C12, For example, methylthio, ethylthio, etc. are mentioned.), An arylthio group (preferably C6-C20, More preferably, C6-C6) -16, Especially preferably, it is C6-C12, For example, a phenylthio etc. are mentioned.), A sulfonyl group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, C1-C12, mesyl, tosyl, etc. are mentioned, for example, sulfinyl group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, methanesulfinyl, benzenesulfinyl, etc.), ureido group (bar More preferably, it is C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, ureido, methylureido, phenylureido, etc. are mentioned), Phosphate amide Group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, diethyl phosphate amide, phenyl phosphate amide, etc. are mentioned), A hydroxyl group, Mercapto group, halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, Heterocyclic groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms), and heteroatoms include, for example, nitrogen, oxygen, and sulfur atoms, specifically, imidazolyl, pyridyl, quinolyl, Furyl, piperidyl, morpholino, benzoocta Zolyl, benzimidazolyl, benzthiazolyl, etc.), silyl group (preferably, C3-C40, More preferably, it is C3-C30, Especially preferably, it is C3-C24, Example Trimethylsilyl, triphenylsilyl, and the like). These substituents may be substituted again. In addition, when there are two or more substituents, they may be same or different. In addition, when possible, you may connect with each other and form a ring.

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

General formula (101-A)

(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 , R ⁸ and R ⁹ each independently represent a hydrogen atom or a substituent, and the above-mentioned substituent T can be applied as the substituent. . In addition, these substituents may be substituted by another substituent, and substituents may be condensed and may form 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 alkyloxy 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 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, An alkyl group, an aryl group, an alkyloxy group, an aryloxy group, a halogen atom, More preferably, they are a hydrogen atom, a C1-C12 alkyl group, Especially preferably, they are a hydrogen atom and a methyl group, Most preferably, they are 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 alkyloxy group, an aryloxy group, and a halogen atom, More preferably, they are a hydrogen atom and a C1-C12 alkyl group, Especially preferably, they are a hydrogen atom and a methyl group, Most preferably, they are 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 alkyloxy 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 more preferably a compound represented by the following general formula (101-B).

General formula (101-B)

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

Although the specific example of a compound represented by General formula (101) below is given, this invention is not limited to the following specific example at all.

Among the benzotriazole compounds cited above, when the transparent film film of the present invention was produced without containing 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)

(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 bicyclic aromatic hydrocarbon ring (For example, a benzene ring, a naphthalene ring, etc. are mentioned.), More preferably, it is carbon number It is a 6-20 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 one or more of any one of an oxygen atom, a nitrogen atom or a sulfur atom. Specific examples of heterocycles include, for example, furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazolin, thiazole, thia Diazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetra Sol, benzimidazole, benzoxazole, benzthiazole, benzotriazole, tetrazaindene and the like. As aromatic heterocycle, 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 the substituent T described later is preferable, but the carboxylic acid, sulfonic acid, and quaternary ammonium salt are not contained in the substituent. In addition, when possible, substituents may connect and form a ring structure.

X represents NR (R represents a hydrogen atom or a substituent. The substituent T mentioned later can be applied as a substituent), an oxygen atom or a sulfur atom, and preferably represents X as NR (preferably an acyl group , A sulfonyl group, and these substituents may be substituted again.) Or 0, and particularly preferably 0.

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, C2-C) -12, Especially preferably, it is C2-C8, For example, a propargyl, 3-pentynyl, etc. are mentioned.), An aryl group (preferably C6-C30, More preferably, C6-C20) Especially preferably, they are 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, a part Oxy), and an aryloxy group (preferably C6-C20, More preferably, it is C6-C16, Especially preferably, it is C6-C12, For example, phenyloxy, 2-naphthyl Oxy, etc.), acyl group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, acetyl, benzoyl, formyl, p Baloyl, etc.) and an alkoxycarbonyl group (preferably Is 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 Preferably it is C7-20, More preferably, it is C7-16, Especially preferably, it is C7-10, For example, a phenyloxycarbonyl etc. are mentioned.), Acyloxy group (Preferably C2 -20, More preferably, it is C2-C16, Especially preferably, it is C2-C10, For example, acetoxy, benzoyloxy, etc. are mentioned.), Acylamino group (Preferably C2-C20, More Preferably it is C2-C16, Especially preferably, it is C2-C10, For example, acetylamino, benzoylamino, etc. are mentioned, The alkoxycarbonylamino group (Preferably C2-C20, More preferably Is 2 to 16 carbon atoms, in particular Preferably it is C2-C12, and a methoxycarbonylamino etc. are mentioned, for example.) An aryloxycarbonylamino group (preferably C7-C20, More preferably, C6-C16 is especially preferable. Preferably it is C7-C12, and a phenyloxycarbonylamino etc. are mentioned, for example, A sulfonylamino group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, carbon number 1-12, for example, methanesulfonylamino, benzenesulfonylamino, etc.), sulfamoyl group (preferably carbon 0-20, more preferably 0-16, especially preferably It has 0-12 carbons, For example, sulfamoyl, methyl sulfamoyl, dimethyl sulfamoyl, phenyl sulfamoyl, etc.), carbamoyl group (preferably C1-C20, More preferably, C1-C20) 16, particularly preferably carbon atoms 1-12, for example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc.), alkylthio group (preferably C1-C20, more preferably Is C1-C16, Especially preferably, it is C1-C12, For example, methylthio, ethylthio, etc. are mentioned.), An arylthio group (preferably C6-C20, More preferably, C6-C6) -16, Especially preferably, it is C6-C12, For example, a phenylthio etc. are mentioned.), A sulfonyl group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, C1-C12, mesyl, tosyl, etc. are mentioned, for example, sulfinyl group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, Examples include methanesulfinyl, benzenesulfinyl, and the like. More preferably, it is C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, ureido, methylureido, phenylureido, etc. are mentioned), Phosphate amide Group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, diethyl phosphate amide, phenyl phosphate amide, etc. are mentioned), A hydroxyl group, Mercapto group, halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, Heterocyclic group (preferably C1-C30, More preferably, it is 1-12, As a hetero atom, For example, a nitrogen atom, an oxygen atom, a sulfur atom, For example, imidazolyl, pyridyl, quinolyl , Furyl, piperidyl, morpholino, benzooxy Sazolyl, benzimidazolyl, benzthiazolyl, and the like.), Silyl group (preferably, 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms). For example, trimethylsilyl, triphenylsilyl, etc. can be mentioned), etc. are mentioned. These substituents may be substituted again. In addition, when there are two or more substituents, they may be same or different. In addition, when possible, you may connect with each other and form a ring.

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

General formula (102-A)

(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 above-mentioned substituent T can be applied as the substituent. . In addition, these substituents may be substituted by another substituent, and substituents may be condensed and may form 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 alkyloxy 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 hydroxyl group, a halogen atom, more preferably a hydrogen atom, 1 to 20 carbon atoms. It is an alkyl group, a C0-20 amino group, a C1-C12 alkoxy group, a C6-C12 aryloxy group, and a hydroxyl group, More preferably, it is a C1-C20 alkoxy group, Especially preferably, it is C1-C20 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)

(Wherein 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 can be applied as a substituent. have.

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). And a practical group, 2-ethylhexyl group, n-octyl group, n-decyl group, n-dodecyl group, benzyl group, etc.), and particularly preferably a substituted or unsubstituted alkyl group having 6 to 12 carbon atoms ( 2-ethylhexyl group, n-octyl group, n-decyl group, n-dodecyl group, benzyl group).

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

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

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)

(In formula, Q <^1> and Q < ² > represent an aromatic ring each independently. X <^1> and X <^2> represent a hydrogen atom or a substituent, and any one or more represents a cyano group, a carbonyl group, a sulfonyl group, and an aromatic heterocycle.) The aromatic ring represented by Q ¹ and Q ² may be an aromatic hydrocarbon ring or an aromatic hetero ring. In addition, these may be mono-cyclic and may form another ring and a condensed ring.

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.

The aromatic hetero ring is preferably an aromatic hetero ring containing a nitrogen atom or a sulfur atom. Specific examples of heterocycles include, for example, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazolin, thiazole, thiadiazole, oxa Sleepy, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimi Dazole, benzoxazole, benzthiazole, benzotriazole, tetrazaindene, etc. are mentioned. As aromatic heterocycle, Preferably they are pyridine, triazine, quinoline.

The aromatic ring represented by Q ¹ and Q ² is preferably an aromatic hydrocarbon ring, and more preferably 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.), 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, C2-C) -12, Especially preferably, it is C2-C8, For example, a propargyl, 3-pentynyl, etc. are mentioned.), An aryl group (preferably C6-C30, More preferably, C6-C20) Especially preferably, they are 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, a part Oxy), and an aryloxy group (preferably C6-C20, More preferably, it is C6-C16, Especially preferably, it is C6-C12, For example, phenyloxy, 2-naphthyl Oxy, etc.), acyl group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, acetyl, benzoyl, formyl, p Baloyl, etc.) and an alkoxycarbonyl group (preferably Is C2-C20, More preferably, it is C2-C16, Especially preferably, it is C2-C12, For example, methoxycarbonyl, ethoxycarbonyl, etc. are mentioned.), Aryloxycarbonyl group ( Preferably it is C7-20, More preferably, it is C7-16, Especially preferably, it is C7-10, For example, Phenyloxycarbonyl etc. are mentioned.), Acyloxy group (Preferably carbon number 2-20, 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 C2-C16, Especially preferably, it is C2-C10, For example, acetylamino, benzoylamino etc. are mentioned.), The alkoxycarbonylamino group (Preferably C2-C20, More preferably Preferably with 2 to 16 carbon atoms, especially Preferably it is C2-C12, and a methoxycarbonylamino etc. are mentioned, for example.) An aryloxycarbonylamino group (preferably C7-C20, More preferably, C6-C16 is especially preferable. Preferably it is C7-C12, and a phenyloxycarbonylamino etc. are mentioned, for example, A sulfonylamino group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, carbon number 1-12, for example, methanesulfonylamino, benzenesulfonylamino, etc.), sulfamoyl group (preferably carbon 0-20, more preferably 0-16, especially preferably It has 0-12 carbons, For example, sulfamoyl, methyl sulfamoyl, dimethyl sulfamoyl, phenyl sulfamoyl, etc.), carbamoyl group (preferably C1-C20, More preferably, C1-C20) 16, particularly preferably carbon atoms 1-12, for example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc.), alkylthio group (preferably C1-C20, more preferably Is 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methylthio, ethylthio, and the like.), An arylthio group (preferably 6 to 20 carbon atoms, more preferably carbon number); 6-16, Especially preferably, it is C6-C12, For example, a phenylthio etc. are mentioned.), A sulfonyl group (Preferably C1-C20, More preferably, C1-C16, Especially preferably, Is C1-C12, and mesyl, tosyl, etc. are mentioned, for example, sulfinyl group (preferably C1-C20, More preferably, C1-C16, Especially preferably, it is C1-C12 , For example methanesulfinyl, benzenesulfinyl, etc.), ureido group (wind More preferably, it is C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, ureido, methylureido, phenylureido, etc. are mentioned), Phosphate amide Group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, diethyl phosphate amide, phenyl phosphate amide, etc. are mentioned), A hydroxyl group, Mercapto group, halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, Heterocyclic group (preferably C1-C30, More preferably, it is 1-12, As a hetero atom, For example, a nitrogen atom, an oxygen atom, a sulfur atom, For example, imidazolyl, pyridyl, quinolyl , Furyl, piperidyl, morpholino, benzooxy Sazolyl, benzimidazolyl, benzthiazolyl, and the like.), Silyl group (preferably, 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms). For example, trimethylsilyl, triphenylsilyl, etc. can be mentioned), etc. are mentioned. These substituents may be substituted again. In addition, when there are two or more substituents, they may be same or different. In addition, when possible, you may connect with each other and form a ring.

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

X ¹ and X ² are preferably a hydrogen atom, an alkyl group, an aryl group, a cyano group, a nitro group, a carbonyl group, a sulfonyl group, an aromatic heterocyclic ring, 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 and an alkoxycarbonyl group (-C (= O) OR (R is a C1-C20 alkyl group, a C6-C12 aryl group, and those combined) ) to be.

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

General formula (103-A)

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

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

R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ are preferably hydrogen 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 alkyloxy group, an aryloxy group, a halogen atom, still more preferably a hydrogen atom or a carbon 1-12 alkyl group, in particular 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 C0-20 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, 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)

(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, you may substitute by another substituent. X ³ is preferably a hydrogen atom, an alkyl group, an aryl group, a cyano group, a nitro group, a carbonyl group, a sulfonyl group, an aromatic heterocyclic ring, more preferably a cyano group, a carbonyl group, a sulfonyl group, an aromatic heterocyclic ring, and more preferably Is a cyano group and a carbonyl group, and particularly preferably a cyano group and an alkoxycarbonyl group (-C (= O) OR (R is a C1-20 alkyl group, a C6-12 aryl group and a combination thereof).

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

General formula (103-C)

(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, it is 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 the following specific example at all.

[Surface treatment]

The transparent film of this invention can implement improvement of the adhesion of a transparent film and each functional layer (for example, an undercoat layer and a back layer) by performing surface treatment 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 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 above conditions, and examples thereof include argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, prolons such as tetrafluoromethane, and mixtures thereof. . About these, the details are described in detail in pages 30 to 32 of the Invention Association Publication No. 2001-1745 (published on March 15, 2001, Invention Association), and are preferably used in the present invention. Can be.

[Contact Angle of Film Surface by Alkali Saponification]

Alkali saponification treatment is mentioned as one of the effective means of surface treatment at the time of using the transparent film of this invention as the transparent protective film of a polarizing plate. In this case, it is preferable that the contact angle 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 for the evaluation of hydrophilicity by the conventional method which drops the water droplet of diameter 3mm to the film surface after alkali soaping treatment, and calculates the angle which a film surface and water droplet make.

[Functional layer]

The transparent film of this invention is applied to an optical use and a photosensitive material as the use. It is particularly preferable that the optical use is a liquid crystal display device, the liquid crystal cell in which the liquid crystal display device carries a liquid crystal between two electrode substrates, two polarizing elements arranged on both sides thereof, and between the liquid crystal cell and the polarizing element It is more preferable that it is the structure which has arrange | positioned 1 or more optical compensation sheets in the inside. 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 optical uses mentioned above, 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 easily adhesive 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 a transparent film can be used include surfactants, lubricants, matting agents, antistatic layers, hard coat layers, and the like, and the Invention Association Publication No. 2001-1745 (March 2001). It is described in detail on pages 32-45 of the 15th issue, invention association), and can be used conveniently in this invention.

[Application (Polarizing Plate)]

The use of the transparent film of this invention is demonstrated.

The transparent film of this invention is especially useful as a polarizing plate protective film. When using it as a polarizing plate protective film, the manufacturing method of a polarizing plate is not specifically limited, It can manufacture by a general method. Alkali treatment of the obtained transparent film and the polyvinyl alcohol film are immersed and stretched in the iodine solution, and there exists a method of bonding together using the fully saponified polyvinyl alcohol aqueous solution on both sides of the polarizer produced. Instead of alkali treatment, easy adhesion processing as described in JP-A-6-94915 and JP-A-6-118232 may be performed.

As an adhesive agent used for bonding 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, Moreover, a protective film is bonded to one surface of this polarizing plate, and it is comprised by bonding 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 bonded for the purpose of protecting the surface of a polarizing plate, and is used for the opposite surface side of the surface which bonds a polarizing plate to a liquid crystal plate. In addition, a separator film is used for the purpose of covering the contact bonding layer bonded to a liquid crystal plate, and is used for the surface side which bonds a polarizing plate to a liquid crystal 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 which part the polarizing plate protective film which applied the optical film of 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 transparent film of this invention can be used for various uses, and when used as an optical compensation film of a liquid crystal display device, it is especially effective. In addition, the optical compensation film generally refers to an optical material used in a liquid crystal display device to compensate for a phase difference, and has the same meaning as a phase difference plate, an optical compensation sheet, and the like. 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.

Therefore, when the transparent film of the present invention is used as an optical compensation film of a liquid crystal display device, any optically anisotropic layer required as an optical compensation film is not limited to the optical performance or driving method of the liquid crystal cell of the liquid crystal display device used. It can be used together. As an optically anisotropic layer used 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 that can be used in the present invention include C. Destrade et al., Mol. Crysr. Liq. Cryst., Vol. 71, page 111 (1981); REVIEW, No. 22, Chemistry of Liquid Crystals, Chapter 5, Chapter 10 Section 2 (1994); B. Kohne et al., Angew.Chem.Soc.Chem.Comm., Page 1794 (1985); J Zhang et al., J. Am. Chem. Soc., 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 to a discotic core of a discotic liquid crystalline compound as a substituent may be considered. However, if the polymerizable group is directly connected to the discotic core, it is difficult to maintain the alignment state in the polymerization reaction. Become. Therefore, a structure having a linking group between the discotic 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 disk-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 above formula are (D1) to (D15) and (L1) described in JP 2001-4837 A, respectively. (L25), (P1)-(P18), The content of the said publication can be used preferably.

(Bar-shaped liquid crystalline compound)

In the present invention, examples of rod-like liquid crystalline compounds that can be used include azomethines, azoxy compounds, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, and cyanophenylcyclohexane. And cyano substituted phenylpyrimidines, alkoxy substituted phenylpyrimidines, phenyldioxanes, tolans and alkenylcyclohexylbenzonitriles. Not only the low molecular liquid crystalline compounds 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 alignment 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. Patent 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- The compounds described in each publication, such as 80081 and Unexamined-Japanese-Patent No. 2001-328973, are included.

(Optical anisotropic layer made of polymer film)

As described above, the optically anisotropic layer may be formed of a polymer film. The polymer film is formed of a polymer capable of expressing optical anisotropy. Examples of such polymers include polyolefins (e.g. polyethylene, polypropylene, norbornene-based polymers), polycarbonates, polyallylates, polysulfones, polyvinyl alcohols, polymethacrylic acid esters, polyacrylic acid esters and cellulose esters ( Examples include cellulose triacetate and 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 circumferential speed difference of two or more rolls, or tenter stretching in which both sides of the polymer film are stretched in the width direction, and biaxial stretching in combination thereof are preferable. Moreover, using 2 or more sheets of polymer films, the optical properties of the whole 2 or more sheets may satisfy | fill said condition. The polymer film is preferably produced by the solvent cast method in order to reduce birefringence staining. 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, at least one polymer material selected from the group consisting of polyamide, polyimide, polyester, polyether ketone, polyamideimide polyesterimide and polyaryl ether ketone as a polymer film forming the optically anisotropic layer, The method of apply | coating the solution melt | dissolved in the solvent to a base material, drying a solvent, and forming into a film can also be used preferably. 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, The transparent film of 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 bond with the transparent film of this invention, and to use together as an optically anisotropic layer. The thickness of a polymer film can be made thin by this method, It is preferable that it is 50 micrometers or less, and it is more preferable that it is 1-20 micrometers.

(Composition of General Liquid Crystal Display)

When using the transparent film of this invention as an optical compensation film, you may arrange | position the slow axis of the optical compensation film which consists of a transmission axis of a polarizing element and a transparent film at any angle.

In a liquid crystal display device, polarizing plates are arranged on both sides of a liquid crystal cell formed by supporting liquid crystals between two electrode substrates, and various optical elements such as a retardation film, an antireflection film, and a brightness enhancement film are laminated as necessary.

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 usually formed on a substrate. The substrate of the liquid crystal cell generally has a thickness of 50 µm to 2 mm.

Generally, a liquid crystal display device is manufactured by fixing the outer circumferential portion of the liquid crystal panel with a fixing frame made of a metal plate such as stainless steel such as a "bezel" to form a liquid crystal module. . In the present invention, the same configuration is used.

(Board)

The board | substrate of the liquid crystal cell which comprises the liquid crystal display device of this invention consists of glass or resin (plastic). The said glass or resin may contain the additive, and the board | substrate may have components other than glass or resin. And liquid crystal can be enclosed between the cell substrates which consist of glass or resin.

From the viewpoint of thinning the liquid crystal display device, the substrate is preferably 1 mm or less in thickness, preferably 0.7 mm or less, and most preferably 0.5 mm or less.

Here, as a resin substrate, if it has transparency and mechanical strength, it will not specifically limit, Any conventionally well-known thing can be used. Examples of the resin for forming the resin substrate include thermoplastic resins such as polycarbonate, polyallylate, polyether sulfone, polyester, polysulfone, polymethyl methacrylate, polyetherimide and polyamide, and epoxy resins. And thermosetting resins such as unsaturated polyester, polydiallyl phthalate and polyisobornyl methacrylate. Such resin can be used 1 type, or 2 or more types, and can also be used as a copolymer and mixture with another component.

(Polarizer)

Next, the polarizing plate which comprises a laminated body in a liquid crystal display device is demonstrated.

In the present invention, the kind of polarizing plate is not particularly limited as long as it can satisfy the conditions of the present invention. For example, a polyvinyl alcohol (PVA) film is dyed with iodine or dichroic dye having dichroism and stretched. After orientation, the absorption type polarizing plate manufactured by bonding crosslinked and dried polarizer and a protective film can be used preferably. It is preferable that a polarizer is excellent in light transmittance and polarization degree. The light transmittance is preferably 30% to 50%, more preferably 35% to 50%, and most preferably 40% to 50%. The degree of polarization is preferably 90% or more, more preferably 95% or more, and most preferably 99% or more. In the case of the transmittance | permeability of 30% or less, or the polarization degree of 90% or less, the brightness | luminance and contrast of a liquid crystal display device are low, and display quality falls. 1-50 micrometers is preferable, as for the thickness of a polarizer, 1-30 micrometers is more preferable, It is most preferable that it is 8-25 micrometers.

Although the adhesive treatment of a polarizer and a protective film in this invention is not specifically limited, For example, it is a water-soluble crosslinking agent of vinyl alcohol type polymers, such as adhesive agent which consists of vinyl alcohol type polymers, or boric acid, borax, glutaraldehyde, melamine, and oxalic acid. It can carry out through the adhesive agent etc. which are formed. It is preferable to use a polyvinyl alcohol-type adhesive agent from the point that adhesiveness with a polyvinyl alcohol-type film is the most favorable. Such an adhesive layer can be formed as a coating and drying layer of an aqueous solution, and when preparing the aqueous solution, other additives, a catalyst such as an acid, and the like can also be blended if necessary.

(Laminated body on the front side including the polarizing plate)

The laminate on the front side of the liquid crystal display device may include a polarizing plate, and may also include an optical member adhered to the viewing side and the liquid crystal cell side of the polarizing plate.

On the visual side of the polarizing plate, a hard coat film, an antireflection film, an antiglare film, or the like may be appropriately formed by bonding or surface treatment. The hard coat film or the hard coat treatment is carried out for the purpose of preventing scratches on the surface of the polarizing plate, and the like, for example, a cured film excellent in hardness, slipperiness, etc., by a suitable ultraviolet curable resin such as silicone, etc., on the surface of the transparent protective film. It can be formed by a method such as added to. The antireflection film or antireflection treatment (anti reflection) is carried out for the purpose of antireflection of external light on the surface of the polarizing plate, and the antiglare film or antiglare treatment (antiglare) is reflected from the panel with external light reflected from the surface of the panel (screen). It is carried out for the purpose of preventing impairing the visibility of the transmitted light of the light, for example, a roughening method by a sandblasting method, an embossing method or the like, or a suitable method such as coating a coating liquid containing transparent fine particles. It can form by providing a fine uneven structure to the protective film surface.

An optical compensation film may be used on the liquid crystal cell side of a polarizing plate as needed. The optical compensation film generally refers to an optical material for compensating a viewing angle in an oblique direction of a liquid crystal display device, and has the same meaning as a retardation plate, an optical compensation sheet, and the like. The optical compensation film may be an integral type that gave optical performance to the protective film itself of the polarizing plate, for example, a triacetyl cellulose acylate film to give optical compensation performance to be a protective film of the polarizer, for example, to a triacetyl cellulose film. The form which apply | coats a discotic liquid crystal and integrates with a polarizing plate after that may be sufficient. Moreover, you may bond using a plurality of optical compensation films. As an optical compensation film to bond, a polymer film is mainly used preferably. For example, a bidirectional stretched film such as a polymer film having birefringence stretched biaxially in the plane direction, or a diagonally oriented polymer film stretched on one axis in the plane direction and stretched in the thickness direction to control the refractive index. This is used. Inclined orientation films are also used. For example, the thing which carried out the extending | stretching process of the polymer film, and / or the shrinkage | contraction process, the diagonal orientation of the liquid crystal polymer, etc. are mentioned under the effect of the heat shrinkable film adhere | attached to a polymer film and the shrinkage force by heating.

It is common for each member which comprises each layer of these viewing side and the liquid crystal cell side to adhere | attach using an adhesive. The adhesion layer at this time is also contained in each laminated body.

The pressure-sensitive adhesive layer can be formed of a conventional pressure-sensitive adhesive such as acrylic. It is preferable that it is the adhesion layer which is low in moisture absorption and excellent in heat resistance from the point of prevention of foaming phenomenon and peeling phenomenon by moisture absorption, and the fall of the optical characteristic by thermal expansion difference. What is necessary is just to form an adhesion layer as needed, and in this invention, it can form as needed, for example, adhesion of an optical compensation film and a protective film, adhesion of a liquid crystal cell, and a protective film.

(Layer of the back side containing a polarizing plate)

In this invention, the laminated body of the back side containing a polarizing plate contains a polarizing plate, and may also contain the optical member adhere | attached to the liquid crystal cell side and a backlight side of a polarizing plate.

An optical compensation film may be used on the liquid crystal cell side of the polarizing plate, and a diffusion sheet, a brightness enhancement film, or the like may be used on the backlight side as necessary. Each of these members may be adhered using an adhesive, and the adhesive at this time is also included in the laminate on the back side. However, even if a diffusion sheet, a brightness improving film, etc. are arrange | positioned at the backlight side, in the present invention, it is not included in the laminated body of this side, unless it is directly adhere | attached with the polarizing plate of this side.

(Condition of formula (viii))

In the liquid crystal display device of the present invention, the total of values obtained by multiplying the cross-sectional area of the elastic modulus of each layer with respect to the layers constituting the laminate on the front side (viewing side) of the substrate and the laminate on the substrate back side is larger than the surface side of the substrate. By enlarging the back side of the substrate, it is possible to prevent display deterioration (occuring corner unevenness in the liquid crystal display device) due to warpage and warpage. Specifically, by satisfying the following formula (viii), display deterioration due to warpage and warpage can be effectively prevented. Since the corner unevenness by curvature of a panel can be seen especially by the IPS system liquid crystal display device, it is especially effective when a panel design is made to satisfy following formula (viii) in an IPS type liquid crystal display device.

0.99(viii) ∑ _i (Ef _i × Sf _i ) / ∑ _j (Er _j × Sr _j )

0.99

[In the above formula, Ef _i represents the tensile modulus in the long side direction of the i-th layer constituting the laminate on the front side, and Sf _i represents the cross-sectional area of one side of the i-th layer constituting the laminate on the front side. Where Er _j represents the tensile modulus in the long side direction of the j-th layer constituting the laminate on the substrate back side, and Sr _j represents the cross-sectional area of the short side of the j-th layer constituting the laminate on the substrate back side.

Although the upper limit of formula (viii) is 0.99, 0.95 is more preferable, 0.90 is still more preferable, and 0.85 is especially preferable. Moreover, it is preferable that the value of Formula (viii) is 0.7 or more. If it is 0.7 or more, since the balance of the force which the whole laminated body opposes to drag does not bias either the front side or the back side, it is hard to produce the case where the surface bends convexly to the visual side. Light leakage or color taste by using the transparent film of this invention as a member (polarizer protective film, support body of an optical compensation film, etc.) to at least one of a front side laminated body or a back side laminated body, and also designing a panel to satisfy said formula. The liquid crystal display device with little change and also suppressing corner unevenness can be provided.

In Formula (viii), Ef _i x Sf _i is the product of the elastic modulus Ef _{i in} the long side direction of the i-th layer constituting the laminate on the front side of the substrate (liquid crystal cell) and the cross-sectional area Sf _i on one side. When a layer is square, the short side here is made into one side. The larger the modulus of elasticity Ef _i , the more difficult the i-th layer is to stretch / reduce in the long side direction. Since the elastic modulus E _{f i} is a value per unit area, the cross-sectional area S f _i (= thickness × short side) can be expressed to indicate the magnitude of the force resisting the stretching / reduction applied to the layer i. Therefore, ∑ (Ef _i × Sf _i ) is the stretch / contraction of the long side of the panel with respect to each layer constituting the laminate on the front side of the substrate (for example, the protective film, polarizer, adhesive, optical compensation film, etc. constituting the polarizing plate). Represents the sum of the forces resisting. Similarly, (Er _j × Sr _j ) represents the total of the forces applied to the long side direction of the panel with respect to each layer constituting the laminate on the substrate back side. From the above, equation (viii) means that the sum of the forces on the back side of the substrate is larger than the sum of the forces on the front side of the substrate, and by satisfying this equation, the warp to the front side of the substrate and the decrease in display performance due to the warp can be prevented. Can be.

In the present invention, the method of adjusting Σ (Ef _i × Sf _i ) of the front side laminate and Σ (Er _j × Sr _j ) of the back side laminate is not particularly limited so as to satisfy the formula (viii). An appropriate method can be selected in consideration of the layer structure of the front and back laminates, the characteristics of the liquid crystal display device to be manufactured, the use environment, and the like. For example, in the liquid crystal display device, a method of enlarging the physical properties of the backside laminate to the front side laminate by incorporating an optical compensation film only in the front side laminate or by integrating a brightness enhancement film into the back side laminate. You can think of The present invention can also be achieved by using a material having a high elastic modulus for the back laminate and a material having a small modulus for the front laminate. Moreover, it is also effective in this invention to adjust the thickness of each layer in the range which does not impair the function of each layer.

(Section area)

In this invention, since the thickness of each layer of a front side and a back side is related to the cross-sectional area in said Formula (viii), it is preferable to adjust suitably. If the thickness is large, the cross-sectional area of each layer can be increased. It is preferable to adjust suitably according to a polarizer, a protective film, an optical member, an adhesion layer, and each raw material.

The size of each layer used for the liquid crystal display of the present invention is the same as that of the panel (screen). In this invention, since the physical property of the long side direction of a panel is considered by Formula (viii), the width represented by a cross-sectional area (= thickness x width) is the same as the length of a short side direction. Although it changes with the panel size of a liquid crystal display device, it is preferable that the length of a long side is 10-500 cm from a practical size or a manufacturing viewpoint. More preferably, it is 20-500 cm, More preferably, it is 30-500 cm, Especially preferably, it is 50-500 cm. Although there is no restriction | limiting in particular about a magnitude | size, It is easy to produce curvature of a liquid crystal panel when an area is large, It is effective to satisfy said formula (viii) especially in a big screen liquid crystal display device.

(Panel bending)

0.01 을 만족시키는 것이 바람직하다. w/L

0.01 이면 패널의 휨에 의한 코너 불균일의 표시 성능의 저하를 억제할 수 있다. 보다 바람직하게는 w/L

0.005 이고, w/L

0.03 을 만족시키는 것이 더욱 바람직하다.The liquid crystal display device of the present invention transfers the panel under an environment of a temperature of 25 ° C. and a relative humidity of 60% after 48 hours at a temperature of 60 ° C. and a relative humidity of 90%. Mm) is w / L with respect to length L (mm) of the long side direction of a panel.

It is preferable to satisfy 0.01. w / L

If it is 0.01, the fall of the display performance of a corner nonuniformity by the curvature of a panel can be suppressed. More preferably w / L

0.005, w / L

It is more preferable to satisfy 0.03.

0.05 를 만족시키는 것이 바람직하다. 보다 바람직하게는 w/L

0.02 이고, w/L

0.01 을 만족시키는 것이 더욱 바람직하다.Further, after 4 hours at 50 ° C and 50% RH, the panel warpage amount w (mm) is equal to the length L of the long side of the panel even after 20 minutes. Mm), w / L

It is preferable to satisfy 0.05. More preferably w / L

0.02, w / L

It is more preferable to satisfy 0.01.

(Humidity and humidity at the time of environmental change)

The liquid crystal display device of the present invention is transferred to an environment of a temperature of 25 ° C and a relative humidity of 60% after 48 hours at a temperature of 60 ° C and a relative humidity of 90%, and at a point of time after 20 minutes, the surface of the front (viewing side) and the interior of the case body. In the case where the environment of temperature and humidity may be different, it is preferable to satisfy the following formulas (xiii) and (xiv) at a time point 20 minutes after changing the environmental conditions.

(xiii) Hf≥Hr

Tr(xiv) Tf

Tr

In the above formula, Hf is the relative humidity (%) of the outermost layer surface of the laminate on the front side, Hr is the relative humidity (%) of the outermost layer surface of the laminate on the substrate back side, and Tf is the outermost layer surface of the laminate on the front side. The temperature (° C) and Tr represent the temperature (° C) of the outermost layer surface of the laminate on the substrate back side.

(Type of liquid crystal display device)

The transparent film of 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 of 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 of 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 the TN mode and the TN type liquid crystal display have been well known for a long time. 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. In addition, it is described in Mori et al. (Jpn. J. Appl. Phys. Vol. 36 (1997) p. 143 or Jpn. J. Appl. Phys. Vol. 36 (1997) p. 1068). .

(STN type liquid crystal display device)

You may use the transparent film of 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 crystal molecules in the liquid crystal cell are twisted in the range of 90 to 360 degrees, and the product (Δnd) of the refractive index anisotropy (Δn) and the cell gap (d) of the rod-shaped liquid crystal molecules is 300. It exists in the range of -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 of 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 make Re-retardation value of the optical compensation sheet used for VA type liquid crystal display device into 0-150 nm, and to set Rth retardation value to 70-400 nm. As for Re retardation value, it is more preferable that it is 20-70 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 an orientation-divided system 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 of 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 substantially in parallel when displaying black, and the liquid crystal molecules are arranged in parallel with respect to the substrate surface in a state where no voltage is applied, thereby displaying black. In these aspects, the polarizing plate using the transparent film of this invention contributes to viewing angle enlargement and contrast improvement. In this aspect, it is preferable to set the value of the retardation of the optically anisotropic layer arrange | positioned between the protective film, protective film, and liquid crystal cell of the said polarizing plate to 2 times or less of the value of (DELTA) n * d of a liquid crystal layer. In addition, since it is preferable to set 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 of this invention is used advantageously.

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

The transparent film of 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 in which the absolute value of retardation becomes minimum does not exist also in the surface of an optical compensation sheet in 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. The optical compensation sheet used for an OCB type liquid crystal display device or an HAN type liquid crystal display device is described in Japanese Patent Laid-Open No. 9-197397. It is also described in a paper by Mori et al. (Jpn. J. Appl. Phys. Vol. 38 (1999) p. 2837).

(Reflective liquid crystal display)

The transparent film of this invention is advantageously used also as an optical compensation sheet of the reflection type liquid crystal display device of TN type, STN type, HAN type, and GH (Guest-Host) type | mold. These display modes are well known for a long time. A TN type reflective liquid crystal display device is described in Japanese Patent Laid-Open No. Hei 10-123478, International Publication No. 98/48320, and Japanese Patent No. 3024277. The optical compensation sheet used for the reflective liquid crystal display device is described in International Publication No. 00/65384.

(Other liquid crystal display)

The transparent film of 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 the ASM mode is characterized in that the thickness of the cell is maintained by the adjustable resin spacer. Other properties are the same as those of the liquid crystal cell of the TN mode. A liquid crystal cell of 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, anti-glare film, antireflection film)

The transparent film of 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 of the present invention. . Such preferred 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 March 15, 2001, Invention Association). The transparent film of the invention can be preferably used.

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)

The cellulose acylate was used as a raw material of the transparent film of this invention.

(Preparation of cellulose acylate solution)

The following composition was put into the mixing tank, it stirred, each component was melt | dissolved, and the cellulose acylate solution was prepared. In addition, three kinds (Ac: OH = 2.86: 0.14), (Ac: OH = 2.92: 0.08), and (Ac: Pro: OH = 1.9.0.8:0.3) having different acylation levels were used as cellulose acylate (parentheses). Ac represents an acetyl substituent, Pro represents a propionyl substituent, OH represents an unsubstituted hydroxyl group, and the ratio is the ratio of the degree of acylation).

(Cellulose acylate solution composition)

100.0 parts by mass of cellulose acetate

Methylene chloride (first solvent) 402.0 parts by mass

60.0 parts by mass of methanol (second solvent)

(Preparation of Matte Solution)

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

(Mat agent solution composition)

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

Methylene chloride (first solvent) 76.3 parts by mass

3.4 parts by mass of methanol (second solvent)

10.3 parts by mass of cellulose acylate solution

(Preparation of additive solution)

The following composition was put into the mixing tank, it stirred while heating, each component was melt | dissolved, and the additive solution was prepared. About the compound and wavelength-dispersion regulator which reduce optical anisotropy (Re, Rth), what was shown in following Table 1 was used.

(Additive solution composition)

49.3 parts by mass of compound which lowers optical anisotropy

7.6 parts by weight of wavelength dispersion regulator

Methylene chloride (first solvent) 58.4 parts by mass

8.7 parts by mass of methanol (second solvent)

12.8 parts by mass of cellulose acylate solution

(Production of Cellulose Acylate Samples 101-105)

94.6 parts by mass of the cellulose acylate solution, 1.3 parts by mass of the mat agent solution, and 4.1 parts by mass of the additive solution were mixed with each other after filtration and cast using a band softener. The mass ratio with respect to the cellulose acylate of the compound and wavelength-dispersion modifier which reduce optical anisotropy by the said composition was 12% and 1.2%, respectively. The film was peeled off from the band with a residual solvent amount of 30% and dried at 140 ° C. for 40 minutes to prepare a cellulose acylate film. The residual solvent amount of the completed cellulose acylate film was 0.2%, and the film thickness was 80 µm.

(Comparative Example)

The comparative sample 001 was produced like Example 1 except not using the compound which reduces the optical anisotropy used in the said Example 1, and a wavelength dispersion regulator.

Similarly, the comparative sample 002 was produced like Example except having used TPP (triphenyl phosphate) which is a plasticizer used for a cellulose acylate instead of the compound which reduces optical anisotropy.

Moreover, although the prescription of film preparation is the same, the comparative sample 003 which produced only the tension applied to the machine direction at the time of conveying a film strongly was produced.

The evaluation results of the sample of the present invention and the comparative sample produced in Example 1 are shown in Tables 1-3. From this, the transparent film of the present invention has a small Re, Rth (Table 1), tensile modulus, storage modulus, photoelastic coefficient (Table 2), and dimensional change rate (Table 3) at high humidity or high temperature. It turned out that the aspect ratio of the phosphorus direction is almost 1.

Example 2 (Evaluation of Polarizer Performance)

The transparent film of this invention obtained in Example 1 was polarized plate-processed, and the same polarizing plate as what was mounted in the panel of the liquid crystal display device was evaluated as follows.

(Production of polarizing plate)

The transparent film sample 101 of the present invention was immersed in a 1.5 N sodium hydroxide aqueous solution at 55 ° C. 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 again 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 polarizing film having a thickness of 20 µm. Using a polyvinyl alcohol (PVA-117H manufactured by Kuraray) 3% aqueous solution as an adhesive, two saponified transparent film samples 101 were prepared and bonded to each other with a polarizing film interposed therebetween, so that both surfaces of the polarizing plate protected by the transparent film 101 were prepared. Got it. At this time, the slow axis of both transparent film samples 101 was adhere | attached so that it might become parallel to the transmission axis of a polarizing film, and the polarizing plate 101 was produced. Similarly, a polarizing plate is produced also about transparent film samples 102-105 and comparative samples 001-003, and these polarizing plates are called polarizing plates 102-105, 001-003 below. All polarizing plates 101-105 had sufficient polarization degree.

(Durability Test of Polarizing Plate)

The polarizing plate samples 001-003 which consist of the polarizing plate samples 101-105 and the comparative sample which were produced above were cut into 20 cm x 30 cm, this was fixed to the glass plate through the adhesive, and it was made to stand under the high humidity of 60 degreeC 90% RH for 500 hours. After returning this to normal-temperature-humidity conditions, light leakage with respect to the frame (place 1 cm from the edge of a sample) of the polarizing plate sample was detected as cross nicol with another polarizing plate. The results are shown in Table 4. The polarizing plates 101-105 which consist of the transparent film of this invention were less than the polarizing plates 001-003 which consist of a comparative sample, and were excellent in not seeing a color taste change.

Example 3 (Mounting Evaluation of Transparent Film for IPS Mode Liquid Crystal Display)

The liquid crystal display device of the IPS mode of the structure shown in FIG. 1 was produced. Specifically, the liquid crystal cell prepared by encapsulating the liquid crystal molecules 17 between the pair of substrates 16 and 18 was disposed between the pair of polarizing films 11a and 11b. The transparent film 19 of this invention is arrange | positioned between a liquid crystal cell and the lower polarizing film 11b, and the 1st optical compensation film 15 and the 2nd optical compensation film between a liquid crystal cell and the upper polarizing film 11a. (13) was disposed. In addition, the relationship between the transmission axis 12a, 12b of a polarizing film, and the slow axis 15a of a 1st optical compensation film is described in description of each Example. In addition, in FIG. 1, each member is depicted as an independent member for convenience, and after each member is integrated with another member, for example, after the transparent film 19 is integrated with the polarizing film 11b as a protective film, It may be attached in the apparatus.

Hereinafter, the manufacturing method of each member is demonstrated in detail.

(Production of IPS Mode Liquid Crystal Cell)

On one glass substrate, electrodes were arranged so that the distance between adjacent electrodes became 20 micrometers, the polyimide film was formed as an orientation film on it, and the rubbing process was performed. A polyimide film was formed on one surface of one glass substrate separately prepared, followed by a rubbing treatment to obtain an alignment film. The two glass substrates are arranged so that the alignment films face each other, the substrate gap (gap) d is 3.9 µm, and the two glass substrates are laminated so that the rubbing directions of the two glass substrates become parallel, and then the refractive index anisotropy (Δn) is 0.0769 and A nematic liquid crystal composition having a dielectric constant anisotropy (Δε) of 4.5 was enclosed. The value of d? Δn of the liquid crystal layer was 300 nm.

(Production of Lower Polarizer Plate)

In the present Example, the transparent film 19 and the lower polarizing film 11b shall be integrated. That is, the lower polarizing plate used the polarizing plates 101-105 produced by the transparent film samples 101-105 of Example 1, and the polarizing plates 001-002 produced by the comparative example samples 001-002.

(Production of Second Optical Compensation Film 13)

The optical compensation film 13 was produced by extending | stretching 15% longitudinal uniaxially at 150 degreeC with Fuji Tak TD80UF (Fuji Photography Film Co., Ltd. product). The optical properties of this film were Re = 5 nm and Rth = 70 nm.

(Production of First Optical Compensation Film 15)

After saponifying the surface of the 2nd optical compensation film produced above, 20 ml / m <2> was apply | coated on this film with the orientation film application liquid of the following composition. A film was formed by drying 60 seconds with a warm air of 60 degrees and 120 seconds with a warm air of 100 degrees. Next, the formed film was subjected to a rubbing treatment in the direction parallel to the slow axis direction of the film to form an alignment film.

(Composition of Alignment Film Coating Liquid)

10 parts by mass of the following modified polyvinyl alcohol

371 parts by mass of water

119 parts by mass of methanol

Glutalaldehyde 0.5 parts by mass

0.3 parts by mass of tetramethylammonium fluoride

 Modified polyvinyl alcohol

Next, 1.8 g of the following discotic liquid crystalline compounds, ethylene oxide-modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.), 0.2 g of photopolymerization initiator (Irgacure 907, Chiba) A solution obtained by dissolving 0.06 g of Gaigi Co., Ltd., 0.02 g of sensitizer (Kayacure DETX, Nippon Chemical Co., Ltd.) and 0.01 g of the following fluorine-based polymer (air machine side vertical alignment agent) in 3.9 g of methyl ethyl ketone # 5 wire bars were applied. This was adhere | attached to the metal mold | die, it heated for 3 minutes in 125 degreeC thermostat, and orientated the discotic liquid crystal compound. Subsequently, UV irradiation was performed for 30 seconds using a 120 W / cm high-pressure mercury lamp at 100 degrees to crosslink the discotic liquid crystal compound. Thereafter, the mixture was allowed to cool to room temperature. In this way, the retardation film 2 in which the 1st optical compensation film was formed on the 2nd optical compensation film was produced.

Discotic Liquid Crystal Compound

delete

delete

The optical characteristic of only the discotic liquid crystal retardation layer (first optical compensation film) is calculated by measuring the light incidence angle dependency of Re of the produced retardation film 2 and subtracting the contribution of the second optical compensation film measured in advance. As a result, it was confirmed that Re was 110 nm, Rth was -55 nm, and the average inclination angle of the liquid crystal was 89.9 degrees, and the discotic liquid crystal was vertically aligned with respect to the film plane. The direction of the slow axis was parallel to the rubbing direction of the alignment film.

(Production of Upper Polarizing Plate)

Next, iodine was adsorbed to the stretched polyvinyl alcohol film to prepare an upper polarizing film 11a. A cellulose acetate film (Fujitak TD80UF, manufactured by Fuji Photo Film Co., Ltd.) was adhered to one surface of this polarizing film by using a polyvinyl alcohol adhesive. Thereafter, the phase difference film 2 is bonded to the other surface of the polarizing film 11a so that the second optical compensation film 13 is on the polarizing film 11a side, and an upper polarizing plate integrated with the optical compensation layer is produced. It was.

(Production of liquid crystal display device)

Moreover, the said produced IPS mode cell was bonded to the upper polarizing plate so that the 1st optical compensation film side might be a liquid crystal cell side. Here, the rubbing direction of the slow axis 15a of the 1st optical compensation film 15 and the alignment film of an IPS mode liquid crystal cell was made parallel to the transmission axis 12a of the upper polarizing film 11a. Next, the lower polarizing plate produced above was bonded together so that the transmission axis 12b of the polarizing film 11b might be orthogonal to the transmission axis 12a of the upper polarizing film 11a, and the liquid crystal display device was produced.

(Measurement of leaked light of manufactured liquid crystal display device)

In the liquid crystal display device thus produced, the leakage light when observed from the left tilt direction 60 ° was measured. The results are shown in Table 4. When the transparent film of this invention is used, it is understood that all have less leakage light with respect to a comparative example, and the transparent film of this invention is excellent in the contrast (little light leakage) of the liquid crystal display device, and the viewing angle characteristic of color taste display.

Example 4 Optical Compensation Film Performance: Mount for VA Type Liquid Crystal Display

Using the transparent film sample of 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 sample 103 of the present invention prepared in Example 1 was prepared a solution prepared by preparing a mass 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. Thickness of 80 µm). Then, the optical compensation film 103 by which the polyimide film with a thickness of 6 micrometers was apply | coated to the transparent film of this invention was obtained by heat-processing at 100 degreeC for 10 minutes, and 15% longitudinal uniaxial stretching at 160 degreeC. The optical characteristic of this optical compensation film 103 was Re = 72 nm, Rth = 220 nm, and the shift | offset | difference angle of an orientation axis was within ± 0.3 degree | times, and it was an optical compensation film which has a birefringence layer of nx> ny> nz.

The optical compensation films 101, 102, 104, 105 were similarly obtained also about the transparent film samples 101, 102, 104, 105 of this invention produced in Example 1.

(Comparative Example)

Instead of the transparent film sample 103, a polyimide film having a thickness of 6 μm was applied to the transparent film of the comparative film sample 001 by the same operation except that the film was applied to the comparative film sample (001; thickness of 80 μm). Obtained optical compensation film (001). The optical properties of this optical compensation film (001) were Re = 75 nm and Rth = 280 nm.

The same was true about the other comparative film samples (002, 003), and the optical compensation films (002, 003) were obtained.

(Mounting evaluation for VA type liquid crystal display device)

The polarizer and the poly | silicone which adsorbed iodine to the polyvinyl alcohol which carried out the alkaline soaping treatment of the side which did not apply the polyimide film of the optical compensation films (101-105, 001-003) obtained by the said Example 4 and a comparative example It was directly bonded by bonding using a vinyl alcohol adhesive. At this time, it bonded together so that the nx direction of an optical compensation film and the absorption axis of a polarizing plate may orthogonally cross. It bonded to the lower side of 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 marketed so that the absorption axes of a polarizing plate may orthogonally cross on the opposite side (upper side) of a liquid crystal cell was bonded to VA liquid crystal panel through an adhesive. In the liquid crystal display device obtained as mentioned above, the leakage light when it observed from the inclination direction was measured. When the viewing angle characteristic of contrast (low light leakage) was measured, the thing using the optical compensation films 101-105 obtained from the transparent film samples 101-105 of this invention obtained in Example 1 is a comparative sample (001-003). (○: excellent contrast between left and right and up and down, △: slightly light leakage, slightly less contrast, ×: light leakage) Contrast drops). Therefore, it turned out that it is excellent also when using the transparent film of this invention as retardation film for VA. The results are shown in Table 4.

Example 5 (Production of Liquid Crystal Display)

The said transparent film samples (001-003, 101-105) were immersed in 1.5 mol / L sodium hydroxide aqueous solution at 55 degreeC for 2 minutes. It wash | cleaned in the water bath of room temperature, and it neutralized at 30 degreeC using 0.1 mol / L sulfuric acid. Again, it wash | cleaned in the water washing bath of room temperature, and further dried by the warm air of 100 degreeC. In this way, the surface of the transparent film was surface-treated.

The polarizer with a thickness of 25 µm was obtained by stretching and drying a roll-shaped polyvinyl alcohol film having a thickness of 80 µm successively 5 times in an iodine aqueous solution. The tensile modulus in the stretching direction of the polarizer having a thickness of 25 μm was 12.7 × 10 ⁹ N / m 2, and the tensile modulus in the stretching direction and the vertical direction was 6.1 × 10 ⁹ N / m 2.

The surface-treated transparent film samples (001 to 003, 101 to 105) were used as a protective film on both surfaces of a polarizer having a thickness of 25 µm, and the polyvinyl alcohol-based adhesives were bonded to each other in the configuration shown in Table 5 to form an iodine system. The polarizing plate (polarizing plate of front side, the polarizing plate of back side) was produced.

Bonding the polarizing plate and the substrate to the front and back sides of an IPS-type liquid crystal cell of 26 inches (58 cm long and 35 cm long) using a glass substrate having a thickness of 0.5 mm with the structure shown in Table 5 through an acrylic adhesive. The liquid crystal panel was produced, this liquid crystal panel was built in the case body, and the liquid crystal display device was produced (Invention Examples 1-6, Comparative Example 1). It was confirmed in advance that the tensile modulus of the adhesive and the adhesive used at this time had almost no difference in the long side direction and the short side direction, and the value of the tensile modulus was negligible for the other members.

In Examples 1 to 4 and 6 of the present invention, the polarizer absorption axis of the polarizing plate constituting the laminate on the front side, the machine conveyance direction of the protective film constituting the laminate on the front side, and the short side direction of the panel are parallel, and the lamination on the back side. The polarizer absorption axis of the polarizing plate constituting the body and the machine conveyance direction of the protective film constituting the laminate on the back side are parallel, and the absorption axis of the polarizing plate constituting the laminate on the side and the absorption axis of the polarizing plate constituting the laminate on the front side Each member was placed to be orthogonal. In Table 5, this arrangement is referred to as the "reverse" arrangement.

Moreover, in the liquid crystal display of Example 5 of this invention and a comparative example, the polarizer absorption axis of the polarizing plate which comprises the laminated body of a front side, the mechanical conveyance direction of the protective film which comprises the laminated body of a front side, and the long side direction of a panel are parallel, and The polarizer absorption axis of the polarizing plate which comprises a laminated body and the mechanical conveyance direction of the protective film which comprises the laminated body of this side are parallel, and the absorption axis of the polarizing plate which comprises the absorption axis of the polarizing plate which comprises the laminated body of a front side, and the laminated body of this side. Each member was arrange | positioned so that it may orthogonally cross. In Table 5, this arrangement is referred to as a "net" arrangement.

(3) Evaluation by the moist heat treatment of the liquid crystal display device

The produced liquid crystal display device was left to stand for 48 hours in the environment of the temperature of 60 degreeC, and 90% of a relative humidity. After the treatment, the mixture was transferred to an environment having a temperature of 25 ° C. and a relative humidity of 60%. The power was turned on and the black display state was visually observed. Next, only the panel was taken out of the liquid crystal display device, and the amount of warpage at the time point 20 minutes passed after the transfer was carried out under an environment of a temperature of 25 ° C. and a relative humidity of 60% was measured. The curvature amount w was described in Table 5 as a value w / L (mm / mm) with respect to the length L of the long side direction.

From Table 5, in the liquid crystal display device (Invention Examples 1-5) in which the total of the physical property value expressed by the product of the tensile elasticity modulus of each layer and the cross-sectional area is larger than a front side laminated body, the warpage of the panel resulting from a wet heat process is shown. It can be seen that it can be suppressed. In all of these liquid crystal display devices, the warpage amount was small, and no deterioration of the display due to the "corner nonuniformity" phenomenon in which the four corners of the screen were lightly leaked in a non-uniform shape in the black display state was not seen. In the present invention example 2 in which the transparent film of the present invention is used only in one side laminate, warping of the panel can be suppressed, but compared with the present inventions 1 and 3 to 6 in which the transparent film of the present invention is used in the laminate on both front and back sides. As a result, slight inclined light leakage was observed.

Moreover, in the liquid crystal display device in which the total of the physical-property value expressed by the product of the tensile elasticity modulus of each layer and the cross-sectional area is larger than a back side laminated body, in Example 6 which used the transparent film of this invention for the laminated body of both front and back, Also in the same manner as in Comparative Example 1 in which the transparent film of the comparative example was used for the laminates on both sides of the front and back, the warpage amount w / L was larger than 0.01, and the corner unevenness caused by the slight warpage occurred, so that some light leakage occurred at the four corners. Occurred. In addition, in the comparative example 1, since the transparent film of the comparative example is used for the laminated body of both front and back, in addition to a corner unevenness, the light leakage of the diagonal direction was observed clearly.

By studying the present inventors, the liquid crystal display device is adjusted by adjusting the physical properties of the optical transparent film, in particular, the tensile modulus, storage modulus, photoelastic coefficient, and dimensional stability to be substantially the same in the direction perpendicular to the machine direction and the machine direction. It has been found that light leakage and color taste change that occur when used under severe temperature or humidity conditions can be reduced. In particular, when the in-plane retardation Re of the transparent film and the retardation Rth in the film thickness direction were made small, it was found that the rate of change of Re and Rth due to the environment was small, which was more effective in reducing light leakage and color taste change.

In addition, a transparent film having substantially the same tensile modulus, storage modulus, photoelastic modulus, and dimensional stability of the present invention in the direction perpendicular to the machine direction and the machine direction is used as a protective film for the polarizing plate, and in the long side direction of the screen, With respect to the laminate on the upper side (viewing side) and the laminate on the lower side (side), the total of the values obtained by multiplying the elastic modulus of each layer and its cross-sectional area is made larger than the upper side so that light leakage due to the above environment In addition to the reduction of color taste change, it turned out that the corner unevenness by the warp and warp of a liquid crystal display device can be prevented.

Claims (12)

Tensile modulus in the machine direction is 2.4 × 10 ⁹ to 4.9 × 10 ⁹ N / m 2, tensile modulus in the direction perpendicular to the machine direction is 2.3 × 10 ⁹ to 4.7 × 10 ⁹ N / m 2, and (machine direction Tensile modulus of elasticity) / (tensile modulus of elasticity in the direction perpendicular to the machine direction) is 0.80 to 1.36, The retardation value Re (nm) in the film surface represented by Formula (i) and Formula (ii) and the retardation value Rth (nm) of the film film thickness direction satisfy | fill Formula (iii) and Formula (iv), It is characterized by the above-mentioned. Transparent film made with. (i) Re = (nx-ny) × d (ii) Rth = ((nx + ny) / 2-nz) × d (iii) 0

Re

20 (iv) │Rth│

25 The method of claim 1, The storage modulus in the machine direction and the storage modulus in the direction perpendicular to the machine direction are both 1.5 × 10 ⁹ to 7.8 × 10 ⁹ N / m 2, and (storage modulus in the machine direction) / (direction perpendicular to the machine direction) The storage elastic modulus of the ratio of 0.80 to 1.20. 3. The method according to claim 1 or 2, Both the photoelastic coefficient in the machine direction and the photoelastic coefficient in the direction perpendicular to the machine direction are 5.0 × 10 ⁻¹¹ m 2 / N or less, and also the (photoelastic coefficient in the machine direction) / (photoelastic coefficient in the direction perpendicular to the machine direction). ) Is a ratio of 0.80 to 1.20 transparent film. 3. The method according to claim 1 or 2, The dimensional change rate after 60 ° C 90% RH 24 hours and the dimensional change rate after 90 ° C dry 24 hours are both ± 0.5% or less in both the machine direction and the direction perpendicular to the machine direction, and in any case (the dimensional change rate in the machine direction ) / (Ratio of dimensional change in the direction perpendicular to the machine direction) is a ratio of 0.3 to 2.5. 3. The method according to claim 1 or 2, A cellulose acylate is contained, The transparent film characterized by the above-mentioned. 3. The method according to claim 1 or 2, The transparent film characterized by containing at least 1 sort (s) of the compound which reduces the retardation Rth of the said film film thickness direction in the range which satisfy | fills following formula (v) and formula (vi). (v) (Rth (A) -Rth (O)) / A

-1.0 (vi) 0.01

A

30 [here, Rth (A) is Rth (nm) of the film containing A% of the compound which lowers Rth, Rth (O) is Rth (nm) of the film which does not contain the compound which lowers Rth, A is the mass (%) of the compound when the mass of the film raw material polymer is 100.] The optically anisotropic layer which satisfy | fills following formula (vii) was formed in the transparent film of Claim 1, The optical compensation film characterized by the above-mentioned. (vii) Re = 0 to 200 (nm) or Rth = 0 to 300 (nm) The polarizing plate which used the transparent film of Claim 1 or the optical compensation film of Claim 7 at least 1, and made it the protective film of a polarizer. The liquid crystal display device using either the transparent film of Claim 1 or the optical compensation film of Claim 7. VA or IPS liquid crystal display device using either the transparent film of Claim 1, or the optical compensation film of Claim 7. Liquid crystal cell which enclosed liquid crystal with the board | substrate which consists of glass or resin, the laminated body formed in the front side of the said liquid crystal cell containing a polarizing plate, and the laminated body formed in the back side of the said liquid crystal cell containing the said polarizing plate. A liquid crystal display device comprising a panel having a side surface and having the front side as a viewer side, The polarizing plate of Claim 8 is included in at least one of the said laminated body of the front side, and the said laminated body of this side, and satisfy | fills following formula (viii), The liquid crystal display device characterized by the above-mentioned. (viii) ∑ _i (Ef _i × Sf _i ) / ∑ _j (Er _j × Sr _j )

0.99 [Equation (viii), Ef _i represents the tensile modulus in the long side direction of the i-th layer constituting the laminate on the front side, and Sf _i represents the short side of the i-th layer constituting the laminate on the front side. Er _j represents the tensile modulus in the long side direction of the j-th layer constituting the laminate on the back side of the substrate, and Sr _j denotes the short side of the j-th layer constituting the laminate on the back side of the substrate. It shows the cross-sectional area of one side.] The method of claim 11, wherein After 48 hours have elapsed at a temperature of 60 ° C. and a relative humidity of 90%, and under a temperature of 25 ° C. and a relative humidity of 60%, at a time point of 20 minutes, the warpage amount w (mm) of the panel is equal to the length L of the long side direction of the panel. Mm / w

The liquid crystal display device which satisfy | fills 0.01.

Images