JP2006348114A - Saturated norbornene film, method for producing the same, polarlizing plate, optical compensation film, reflection-preventing film and liquid crystal-displaying device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a saturated norbornene film capable of suppressing the generation of color unevenness on building it in a liquid crystal displaying device and placing it under a high temperature and high humidity. <P>SOLUTION: This saturated norbornene film has 0-0.2% both of wet heat dimensional change (δL(w)) and dry heat dimensional change (δL(d)), and 0-10% all of their wet heat change (δRe(w)) and dry heat change (δRe(d)) of a retardation within its plane (Re), and wet heat change (δRth(w)) and dry heat change (δRth(d)) of the retardation in thickness direction (Rth). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a saturated norbornene film that is stable even under high temperature and high humidity, and a method for producing the same. In particular, the present invention relates to a saturated norbornene film that suppresses color unevenness that occurs when it is incorporated in a liquid crystal display device and placed under high temperature and high humidity, and a method for producing the same. Furthermore, the present invention also relates to a polarizing plate, an optical compensation film, an antireflection film and a liquid crystal display device using the saturated norbornene film.

  Saturated norbornene films are conventionally used for liquid crystal display devices and the like. In use, the saturated norbornene film is stretched to develop in-plane retardation (Re) and thickness-direction retardation (Rth), so that the viewing angle of the liquid crystal display device can be increased as a retardation film, for example. I have to. As a method of stretching such a saturated norbornene film, a method of stretching in the longitudinal (longitudinal) direction (longitudinal stretching) and a method of stretching in the transverse (width) direction (transverse stretching), or a method of stretching in the longitudinal and lateral directions simultaneously. (Simultaneous stretching).

Of these, longitudinal stretching has been conventionally used because of its compact equipment. Usually, the longitudinal stretching is performed by heating the film to a glass transition temperature (Tg) or more between two or more pairs of nip rolls, and increasing the conveyance speed on the outlet side from the conveyance speed of the nip roll on the inlet side. Improvements have been attempted in the conditions of the longitudinal stretching method using this mechanism. For example, Patent Document 1 describes that the variation in Re is reduced by reducing the temperature unevenness during stretching.
JP 2001-42130 A

  However, when the stretched film obtained by the method described in this patent document is used as a retardation film of a liquid crystal display device, there is a problem that color unevenness occurs on a liquid crystal display screen after a lapse of time under high temperature and high humidity. . Such color unevenness significantly deteriorates the value of the liquid crystal display device, so that improvement has been desired.

  Accordingly, an object of the present invention is to provide a saturated norbornene film that can suppress the occurrence of color unevenness when it is incorporated in a liquid crystal display device and placed under high temperature and high humidity. Another object of the present invention is to provide a method for easily producing a saturated norbornene film having such properties. Furthermore, the present invention provides a polarizing plate, an optical compensation film, and an antireflection film that can suppress the occurrence of uneven color when incorporated in a liquid crystal display device and placed under high temperature and high humidity, and color when placed under high temperature and high humidity. An object of the present invention is to provide a liquid crystal display device in which the occurrence of unevenness is suppressed.

The present inventor has analyzed the cause of color unevenness that occurs when a retardation plate in which saturated norbornene is stretched is incorporated in a liquid crystal display device and then placed under high temperature and high humidity. ), Dry heat dimensional change (δL (d)), in-plane retardation (Re) wet heat change (δRe (w)), dry heat change (δRe (d)), and thickness direction retardation (Rth). ) Due to a wet heat change (δRth (w)) and a dry heat change (δRth (d)), the present invention described below has been provided.
[1] The wet heat dimensional change (δL (w)) and the dry heat dimensional change (δL (d)) are both 0% to 0.2%, and the wet heat change of the in-plane retardation (Re) (δRe ( w)) and dry heat change (δRe (d)) are both 0% to 10%, and the wet heat change (δRth (w)) and dry heat change (δRth (d) of retardation (Rth) in the thickness direction. )) Is a saturated norbornene film characterized in that all are from 0% to 10%.
[2] The saturated norbornene film according to [1], wherein the fine retardation unevenness is 0% to 10%.
[3] The saturated norbornene film according to [1] or [2], wherein Re is 0 nm to 300 nm and Rth is 30 nm to 500 nm.
[4] The saturated norbornene film according to any one of [1] to [3], which contains 1 mass ppm to 10,000 mass ppm of fine particles with respect to the saturated norbornene resin.
[5] The saturated norbornene film according to any one of [1] to [4], wherein the residual solvent amount is 0.01% by mass or less.

[6] The wet heat dimensional change (δL (w)) and the dry heat dimensional change (δL (d)) are both 0% to 0.2%, and the wet heat change of the in-plane retardation (Re) (δRe ( w)) and dry heat change (δRe (d)) are both 0% to 10%, and the wet heat change (δRth (w)) and dry heat change (δRth (d) of retardation (Rth) in the thickness direction. )) Is a method for producing a saturated norbornene film in which all are 0% to 10%,
After film formation of saturated norbornene, the length / width ratio (L / W), which is the ratio between the width (W) of the film before stretching and the stretching interval (L), exceeds 0.01 and is less than 0.3. A method for producing a saturated norbornene film, characterized by comprising a step of longitudinally stretching 1% to 300% and further relaxing 1% to 50% in the longitudinal direction.
[7] The method for producing a saturated norbornene film according to [6], wherein the longitudinal stretching is performed by passing a saturated norbornene film obliquely between two pairs of nip rolls.
[8] The method for producing a saturated norbornene film according to [6] or [7], wherein lateral stretching is performed after the longitudinal relaxation.
[9] The method for producing a saturated norbornene film according to [8], wherein the transverse stretching is performed at a stretch ratio of 1% to 250% using a tenter.
[10] The method for producing a saturated norbornene film according to [8] or [9], wherein after the transverse stretching, the relaxation is performed in the transverse direction by 1% to 50%.
[11] The method for producing a saturated norbornene film according to any one of [6] to [10], wherein the saturated norbornene film is formed by a melt film forming method.
[12] A saturated norbornene film produced by the production method according to any one of [6] to [11].

[13] A polarizing plate, wherein at least one layer of the saturated norbornene film according to any one of [1] to [5] and [12] is laminated on a polarizing film.
[14] An optical compensation film using the saturated norbornene film according to any one of [1] to [5] and [12] as a base material.
[15] An antireflection film using the saturated norbornene film according to any one of [1] to [5] and [12] as a base material.
[16] A liquid crystal display device using the saturated norbornene film according to any one of [1] to [5] and [12].

  The saturated norbornene film of the present invention can suppress the occurrence of color unevenness even when it is incorporated in a liquid crystal display device and placed under high temperature and high humidity. Moreover, according to the manufacturing method of this invention, the saturated norbornene film which has such a property can be manufactured efficiently. Furthermore, the polarizing plate, the optical compensation film, the antireflection film, and the liquid crystal display device of the present invention can exhibit excellent functions even under high temperature and high humidity.

Detailed Description of the Invention

  Hereinafter, the saturated norbornene film of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

<Saturated norbornene film>
"Characteristic"
The saturated norbornene film of the present invention has a wet heat dimensional change (δL (w)) and a dry heat dimensional change (δL (d)) both of 0% to 0.2%, and has an in-plane retardation (Re) of The wet heat change (δRe (w)) and the dry heat change (δRe (d)) are both 0% to 10%, and the wet heat change (δRth (w)) and dry heat of the retardation (Rth) in the thickness direction. Any change (δRth (d)) is 0% to 10%.

(ΔL (w) and δL (d))
ΔL (w) in the present invention is a dimensional change before and after 500 hours at 60 ° C. and 90% relative humidity, and δL (d) in the present invention is a dimension before and after 500 hours of dry at 80 ° C. It is a change. Preferred δL (w) and δL (d) are each independently 0% to 0.2%, more preferably 0% to 0.15%, and further preferably 0% to 0.1%. More desirably, both δL (w) and δL (d) are 0% to 0.2%, more preferably 0% to 0.15%, and still more preferably 0% to 0.1%. .

In the roll film, δL (w) is the larger value of the dimensional change in the width (TD) direction (δTD (w)) and the dimensional change in the longitudinal direction (MD) (δMD (w)) represented by the following formula. Point to.
δTD (w) (%) = 100 × | TD (F) −TD (t) | / TD (F)
δMD (w) (%) = 100 × | MD (F) −MD (t) | / MD (F)
(TD (F) and MD (F) are the dimensions before thermo treatment measured in the atmosphere after being left for 5 hours or more at 25 ° C. and 60% relative humidity. TD (t) and MD (t) are thermo treatment ( (Dimensions measured in the atmosphere after standing for 5 hours at 25 ° C and 60% RH)
In the roll film, δL (d) is the larger value of the dimensional change in the width (TD) direction (δTD (d)) and the dimensional change in the longitudinal direction (MD) (δMD (d)) represented by the following formula. Point to. Dry here refers to a state where the relative humidity is 10% or less.
δTD (d) (%) = 100 × | TD (F) −TD (T) | / TD (F)
δMD (d) (%) = 100 × | MD (F) −MD (T) | / MD (F)
(TD (F) and MD (F) are the dimensions before thermo-treatment measured in the atmosphere after being left for 5 hours or more at 25 ° C. and 60% relative humidity. TD (T) and MD (T) are thermo-treatment ( (Dimensions measured in the atmosphere after standing for 5 hours at 25 ° C and 60% relative humidity)

On the other hand, in a sheet film obtained by cutting from a roll or the like, δL (w) is a dimensional change (δFD (w)) and surface in a direction (FD) direction perpendicular to the in-plane slow axis represented by the following formula. The larger one of the dimensional changes (δSD (w)) in the slow axis (SD) direction.
δFD (w) (%) = 100 × | FD (F) −FD (t) | / FD (F)
δSD (w) (%) = 100 × | SD (F) −SD (t) | / SD (F)
(FD (F) and SD (F) are the dimensions before thermo treatment measured in the atmosphere after being left at 25 ° C. and 60% relative humidity for 5 hours or more, and FD (t) and SD (t) are thermo treatment ( (Dimensions measured in the atmosphere after standing for 5 hours at 25 ° C and 60% RH)
In the sheet film, δL (d) is a dimensional change (δFD (d)) in a direction (FD) orthogonal to the in-plane slow axis and the in-plane slow axis (SD) represented by the following formula. It indicates the larger value of the dimensional change (δSD (d)) in the direction. Dry means a state where the relative humidity is 10% or less.
δFD (d) (%) = 100 × | FD (F) −FD (T) | / FD (F)
δSD (d) (%) = 100 × | SD (F) −SD (T) | / SD (F)
(FD (F) and SD (F) are the dimensions before thermo-treatment measured in the atmosphere after standing at 25 ° C. and 60% relative humidity for 5 hours or longer. FD (T) and SD (T) are thermo-treatment ( (Dimensions measured in the atmosphere after standing for 5 hours at 25 ° C and 60% relative humidity)

(ΔRe (w), δRe (d), δRth (w) and δRth (d))
In the present invention, δRe (d) and δRth (d) are Re and Rth changes before and after 500 hours of dryness at 80 ° C., and are represented by the following equations. Dry means a state where the relative humidity is 10% or less.
δRe (d) (%) = 100 × | Re (F) −Re (T) | / Re (F)
δRth (d) (%) = 100 × | Rth (F) −Rth (T) | / Rth (F)
(Re (F) and Rth (F) refer to Re and Rth before aging for 500 hours after drying at 80 ° C., and Re (T) and Rth (T) refer to Re and Rth after aging for 500 hours after drying at 80 ° C. )
ΔRe (w) and δRth (w) in the present invention are Re and Rth changes before and after 500 hours at 60 ° C. and 90% relative humidity, and are represented by the following equations.
δRe (w) (%) = 100 × | Re (F) −Re (t) | / Re (F)
δRth (w) (%) = 100 × | Rth (F) −Rth (t) | / Rth (F)
(Re (F) and Rth (F) indicate Re and Rth before 60 hours at 60 ° C. and 90% relative humidity, and Re (t) and Rth (t) are 500 hours at 60 ° C. and 90% relative humidity. Re and Rth after time)

  δRe (w), δRe (d), δRth (w), and δRth (d) are each independently preferably 0% to 10%, more preferably 0% to 5%, and even more preferably 0. % To 2%. More desirably, δRe (w), δRe (d), δRth (w) and δRth (d) are all preferably 0% to 10%, more preferably 0% to 5%, Preferably, it is 0% to 2%.

(Fine retardation unevenness)
Further, in the present invention, the fine retardation unevenness is preferably 0% to 10%, more preferably 0% to 8%, still more preferably 0% to 5%, and thereby the color unevenness can be reduced. Such fine retardation unevenness has not been regarded as a problem in the past, but has become a problem as the resolution of liquid crystal display devices is increased.
The fine retardation unevenness referred to here refers to a change in retardation occurring in a minute region within 1 mm, and is measured by the following method. That is, in the case of a roll film, the length (TD) and the longitudinal direction (MD) each have a length of 1 mm, and the in-plane retardation (Re) is measured at a pitch of 0.1 mm between the maximum value. And the minimum value is divided by the average value and expressed as a percentage, and the larger of the MD percentage and the TD percentage is defined as fine retardation unevenness. In the case of a sheet film, the in-plane retardation (Re) is 10 points at a 0.1 mm pitch in the in-plane slow axis direction (SD) and in the direction perpendicular to the in-plane slow axis (FD). The difference between the maximum value and the minimum value is divided by the average value and expressed as a percentage, and the larger of the SD percentage and the FD percentage is defined as fine retardation unevenness.

  The in-plane retardation (Re) of the saturated norbornene film of the present invention is preferably 0 nm to 300 nm, more preferably 20 nm to 200 nm, still more preferably 40 nm to 150 nm. Further, the thickness direction retardation (Rth) is preferably 30 nm to 500 nm, more preferably 50 nm to 400 nm, and still more preferably 100 nm to 300 nm. Furthermore, those satisfying Re ≦ Rth are more preferable, and those satisfying Re × 2 ≦ Rth are more preferable.

  In the present invention, Re and Rth represent in-plane retardation and retardation in the thickness direction at a wavelength λ, respectively. Re is measured with KOBRA 21ADH (manufactured by Oji Scientific Instruments Co., Ltd.) by making light having a wavelength of λ nm incident in the normal direction of the film. Rth was measured by making light having a wavelength λ nm incident from a direction inclined + 40 ° with respect to the film normal direction with the Re, in-plane slow axis (determined by KOBRA 21ADH) as the tilt axis (rotation axis). Retardation value and retardation value measured by making light of wavelength λ nm incident from a direction inclined by −40 ° with respect to the film normal direction with the in-plane slow axis as the tilt axis (rotation axis) 3 in total KOBRA 21ADH is calculated based on retardation values measured in two or more directions. Here, as the assumed value of the average refractive index, the values in the polymer handbook (JOHN WILEY & SONS, INC) and catalogs of various optical films can be used. Those whose average refractive index is not known can be measured with an Abbe refractometer. The average refractive index values of main optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), Polystyrene (1.59).

"Achievement means"
The method for producing a saturated norbornene film having the above features of the present invention is not particularly limited. For example, a saturated norbornene film having the above characteristics can be produced by appropriately selecting and combining the following (1) to (3). In particular, according to the production method of the present invention in which the following (1) and (2) are essential, a saturated norbornene film having the above characteristics can be produced easily.

(1) Aspect / Aspect Ratio In the production method of the present invention, the saturated norbornene film after film formation is subjected to an aspect ratio (ratio of stretch interval (L) used for stretching relative to the width (W) of the film before stretching: L / W) is stretched longitudinally under the condition of more than 0.01 and less than 0.3. The aspect ratio is more preferably 0.03 to 0.25, still more preferably 0.05 to 0.2. Longitudinal stretching is usually performed by giving a peripheral speed between two pairs of nip rolls, but such a small aspect ratio means that the length of the film to be stretched is short, and the film has a short time. Will be stretched rapidly. Since the film is stretched rapidly, the orientation can be strengthened, and the above-described δL (w), δL (d), δRe (w), δRe (d), δRth (w), δRth (d ) Can be reduced. Conventionally, it has been generally performed with a roll interval having an aspect ratio (L / W) of around 1 (0.7 to 1.5).
In order to perform such stretching with a small aspect ratio, as shown in FIG. 1, the cellulose acylate film is slanted between the first nip rolls 1a and 1b and the second nip rolls 2a and 2b. The film is preferably stretched through (in the figure, the film is conveyed in the direction of the arrow). Stretching is performed in the space between the time when the film leaves the first nip roll and contacts the second nip roll. For this reason, in order to reduce the distance between the contact points of the nip roll and the film (that is, the stretching interval L), it is preferable to pass the film diagonally between the nip rolls as shown in FIG. In this specification, “passing obliquely” means an angle (θ1) formed by the film entering the nip rolls 1a and 1b and the film between the nip rolls 1a and 1b and the nip rolls 2a and 2b, and between the nip rolls 1a and 1b and the nip rolls 2a and 2b. This means that at least one of the angles (θ2) formed by the film and the film exiting from the nip rolls 2a and 2b is not 0 °. A preferable angle of θ1 and θ2 is 1 ° to 85 °, more preferably 2 ° to 60 °, and further preferably 3 ° to 40 °. Normally, as shown in FIG. 2, since θ1 and θ2 are stretched at 0 ° between the first nip rolls 1a and 1b and the second nip rolls 2a and 2b, L can be made smaller than the diameter of the nip roll. Can not.

Further, in order to stretch rapidly as described above, the stretching speed is preferably high, and the preferable stretching speed is 10 m / min to 100 m / min, more preferably 20 m / min to 80 m / min, and further preferably 30 m / min. ~ 60 m / min. The stretching speed here refers to the speed at which the film before stretching is conveyed by the first nip roll in the stretching process.
Such longitudinal stretching is preferably carried out at the glass transition temperature (Tg) to (Tg + 50 ° C.) of the film, more preferably (Tg + 5 ° C.) to (Tg + 40 ° C.), and even more preferably (Tg + 8 ° C.) to (Tg + 30). ° C). A preferred longitudinal stretching ratio is 1% to 300%, more preferably 3% to 200%, and still more preferably 5% to 150%. In addition, the draw ratio here is the value calculated | required by the following formula | equation.
Stretch ratio (%) = 100 × (length after stretching−length before stretching) / (length before stretching)

  The Tg of the saturated norbornene film is preferably 80 ° C to 200 ° C, more preferably 100 ° C to 190 ° C, and further preferably 120 ° C to 180 ° C. The Tg of the saturated norbornene film here refers to the Tg of the film after all the additives and the like are added, not a saturated norbornene simple substance.

(2) Longitudinal relaxation In the production method of the present invention, after the longitudinal stretching, 1% to 50%, more preferably 1% to 30%, and further preferably 1% to 15% are relaxed in the longitudinal direction. This longitudinal relaxation is more preferably performed after the longitudinal stretching and before the lateral stretching, and more preferably immediately after the longitudinal stretching. Longitudinal relaxation can be carried out by slowing the speed of the transport roll after longitudinal stretching. For example, in the apparatus of FIG. 1, longitudinal relaxation can be performed by making the speed of the transport roll 3 slower than that of the second nip rolls 2a and 2b. In order to achieve the above-described relaxation rate, the speed of the transport roll 3 may be reduced as follows, for example. That is, when the draw ratio Z (%) and the relaxation rate Y (%) are V (m / min), the conveyance speed of the outlet nip rolls 2a and 2b is V × (100 + Z). ) / 100, and the speed of the transport roll 3 provided after the outlet nip roll may be V × {100+ (Z−Y)} / 100.
A preferable temperature for longitudinal relaxation is (Tg-20 ° C) to (Tg + 50 ° C), more preferably (Tg-15 ° C) to (Tg + 40 ° C), and further preferably (Tg-10 ° C) to (Tg + 30 ° C). . The “relaxation rate” here refers to a value obtained by dividing the length to be relaxed by the dimension before stretching. That is, when the film length before stretching is 100 cm, the film length becomes 130 cm if the film is longitudinally stretched by 30%, and if it is relaxed at a relaxation rate of 10%, the film length becomes 120 cm.
By performing such longitudinal relaxation, strain remaining in the film due to stretching can be efficiently released, and δL (w), δL (d), δRe (w), δRe (d), δRth (W) and δRth (d) can be reduced.

  By carrying out the rapid stretching of (1) and the longitudinal relaxation of (2) according to the production method of the present invention, the fine retardation unevenness of the obtained saturated norbornene film can be reduced. That is, when the aspect ratio is increased and the stretching length is increased, the film is stretched in order from the thin thickness and easily stretched, so that fine retardation unevenness is easily developed. If it is made small and stretched rapidly, fine retardation unevenness due to stretching unevenness can be reduced. Furthermore, if longitudinal relaxation is performed according to the present invention, unevenness in fine retardation can be reduced by releasing residual strain. That is, the more stretched portion is relaxed, and the fine retardation unevenness caused by the stretch unevenness can be reduced.

(3) Fine Particles In the production method of the present invention, it is preferable to produce a saturated norbornene film by containing fine particles in an amount of 1 mass ppm to 10,000 mass ppm with respect to the saturated norbornene resin. A more preferable content is 5 mass ppm to 7,000 mass ppm, and a more preferable content is 10 mass ppm to 5,000 mass ppm.
In the present invention, it is preferable to add fine particles as a lubricant. By adding fine particles as a slipping agent, it is possible to prevent the occurrence of sticking (adhesion) to the nip roll during longitudinal stretching, so that it is possible to prevent fine retardation unevenness due to sticking. In the longitudinal stretching, the film is pulled on the nip roll at a temperature that exceeds Tg and the film softens. However, if there is no easy-to-lubricant, local adhesion is likely to occur, and uneven stretching tends to occur there. If the lubricant is contained, it is possible to prevent the nip roll and the film from slipping and applying stress locally.
In the present invention, it is also preferable to add fine particles as a matting agent.
The fine particles used in the present invention include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and Mention may be made of calcium phosphate. In addition, fine particles made of a crosslinked polymer can also be used.

  These fine particles usually form secondary particles having an average particle size of 0.1 to 3.0 μm, and these fine particles exist in the film as aggregates of primary particles, and 0.1 to 3 on the film surface. An unevenness of 0.0 μm is formed. The secondary average particle size is preferably 0.2 to 1.5 μm, more preferably 0.4 to 1.2 μm, and most preferably 0.6 to 1.1 μm. For the primary and secondary particle sizes, the particles in the film were observed with a scanning electron microscope, and the diameter of a circle circumscribing the particles was defined as the particle size. In addition, 200 particles were observed at different locations, and the average value was taken as the average particle size.

The use of fine particles containing silicon is preferred because turbidity can be lowered, and silicon dioxide is particularly preferred. The fine particles of silicon dioxide preferably have a primary average particle size of 20 nm or less and an apparent specific gravity of 70 g / liter or more. A primary particle having an average diameter as small as 5 to 16 nm is more preferable because it can reduce the haze of the film. The apparent specific gravity is preferably 90 to 200 g / liter or more, and more preferably 100 to 200 g / liter or more. A larger apparent specific gravity is preferable because a high-concentration dispersion can be produced, and haze and aggregates are improved.
As fine particles of silicon dioxide, for example, commercially available products such as Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (above Nippon Aerosil Co., Ltd.) can be used. The fine particles of zirconium oxide are commercially available under the trade names of Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.), and can be used. Among these, Aerosil 200V and Aerosil R972V are fine particles of silicon dioxide having a primary average particle size of 20 nm or less and an apparent specific gravity of 70 g / liter or more. This is particularly preferable because it has a great effect of lowering.

<Manufacture of saturated norbornene film>
Below, the process of manufacturing the saturated norbornene film of this invention is demonstrated in detail along a procedure.

《Saturated norbornene resin》
Saturated norbornene resins-A and saturated norbornene resins-B described below can be given as preferred examples of the saturated norbornene resins used as the raw material for the saturated norbornene film of the present invention. Any of these saturated norbornene resins can be formed by a solution film forming method or a melt film forming method, which will be described later, but the saturated norbornene resin-A is more preferably formed by a melt film forming method. The resin-B is more preferably formed by a solution casting method. These films using saturated norbornene as a raw material have the property of expressing appropriate Re and Rth by stretching, and the Re and Rth are less likely to fluctuate even when placed in a high temperature and high humidity environment for a long time. It also has an excellent property that unevenness is hardly expressed.

(Saturated norbornene resin-A)
As the saturated norbornene resin-A, (1) a ring-opening (co) polymer of a norbornene monomer is subjected to polymer modification such as maleic acid addition or cyclopentadiene addition as necessary, and then further hydrogenated. Obtained resin, (2) resin obtained by addition polymerization of norbornene monomer, and (3) obtained by addition copolymerization of norbornene monomer and olefin monomer such as ethylene and α-olefin. Resins etc. can be mentioned. The polymerization method and the hydrogenation method can be performed by conventional methods.

  Examples of the norbornene-based monomer include norbornene and alkyl and / or alkylidene substituted products thereof (for example, 5-methyl-2-norbornene, 5-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl- 2-norbornene, 5-ethylidene-2-norbornene, etc.), polar substituents such as halogens thereof; dicyclopentadiene, 2,3-dihydrodicyclopentadiene, etc .; dimethanooctahydronaphthalene, its alkyl and / or alkylidene Substituents and polar group substituents such as halogen (for example, 6-methyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6- Ethyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octa Dronaphthalene, 6-ethylidene-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-chloro-1,4: 5,8-dimethano -1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-cyano-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a -Octahydronaphthalene, 6-pyridyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-methoxycarbonyl-1,4: 5 8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, etc.); adducts of cyclopentadiene and tetrahydroindene, etc .; 3-pentamers of cyclopentadiene (for example, 4, 9: 5,8-dimethano-3a, 4,4a, , 8,8a, 9,9a-octahydro-1H-benzoindene, 4,11: 5,10: 6,9-trimethano-3a, 4,4a, 5,5a, 6,9,9a, 10,10a, 11, 11a-dodecahydro-1H-cyclopentanthracene) and the like. These norbornene monomers may be used alone or in combination of two or more.

(Saturated norbornene resin-B)
Examples of the saturated norbornene resin-B include those represented by the following general formulas (1) to (4). Among these, those represented by the following general formula (1) are particularly preferable.

In general formulas (1) to (4), R ^{1 to} R ¹² each independently represent a hydrogen atom or a monovalent substituent (preferably an organic group), and at least one of them is a polar group. Is preferred. The mass average molecular weight of these saturated norbornene resins is usually preferably from 5,000 to 1,000,000, more preferably from 8,000 to 200,000.

  Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms such as a methyl group, an ethyl group, and iso- A propyl group, a tert-butyl group, an n-octyl group, an n-decyl group, an n-hexadecyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, etc.), an alkenyl group (having 1 to 20 carbon atoms, preferably 1 to 10 alkenyl groups such as vinyl group, allyl group, 2-butenyl group and 3-pentenyl group), alkynyl group (C1-C20, preferably 1-10 alkynyl group, For example, a propargyl group, a 3-pentynyl group, etc.), an aryl group (an aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, A phenyl group, a p-methylphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, etc.), an amino group (an amino group having 0 to 20 carbon atoms, preferably 0 to 10 carbon atoms, such as an amino group). , Methylamino group, dimethylamino group, diethylamino group, dibenzylamino group, etc.), alkoxy group (C1-C20, preferably 1-10 alkoxy group such as methoxy group, ethoxy group, butoxy group) Groups), aryloxy groups (C6-C20, preferably 6-15 aryloxy groups such as phenyloxy group and 2-naphthyloxy group), heterocyclic oxy groups (C1-C20, preferably C1-10 heterocyclic oxy group, for example, pyridyloxy group, pyrimidinyloxy group A pyridazinyloxy group, a benzimidazolyloxy group, etc.), a silyloxy group (a silyloxy group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, such as a trimethylsilyloxy group, a t-butyldimethylsilyloxy group, etc. ), Acyl groups (acyl groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as acetyl group, benzoyl group, formyl group, and pivaloyl group), alkoxycarbonyl groups (carbon number). An alkoxycarbonyl group having 2 to 20, preferably 2 to 10, such as a methoxycarbonyl group and an ethoxycarbonyl group), an aryloxycarbonyl group (C7-20, preferably 7-15 aryloxycarbonyl). Group, for example, a phenyloxycarbonyl group). An acyloxy group (acyloxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as an acetoxy group and a benzoyloxy group); ), An acylamino group (acylamino group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms such as acetylamino group and benzoylamino group), an alkoxycarbonylamino group (2 to 20 carbon atoms, preferably 2 carbon atoms). 10 to 10 alkoxycarbonylamino groups such as methoxycarbonylamino group), aryloxycarbonylamino groups (7 to 20 carbon atoms, preferably 7 to 15 aryloxycarbonylamino groups such as phenyloxycarbonyl Amino group, etc.), alkyl or arylsulfonylamino group (C1-C20, preferably 1-10 alkyl or arylsulfonylamino groups such as methanesulfonylamino group, benzenesulfonylamino group, etc.). .), Sul Amoyl group (sulfamoyl group having 0 to 20, preferably 0 to 10 carbon atoms, such as sulfamoyl group, N-methylsulfamoyl group, N, N-dimethylsulfamoyl group, N-phenylsulfamoyl group, etc.) ), A carbamoyl group (a carbamoyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as a carbamoyl group, an N-methylcarbamoyl group, an N, N-diethylcarbamoyl group, an N-phenylcarbamoyl group). ), Alkylthio groups (C1-C20, preferably C1-C10 alkylthio groups such as methylthio and ethylthio groups), arylthio groups (C6-C20, preferably C6-C15). An arylthio group such as a phenylthio group), a heterocyclic thio group (having 1 to 3 carbon atoms). 0, preferably 1 to 10 heterocyclic thio groups such as pyridinylthio group, pyrimidinylthio group, pyridazinylthio group, benzimidazolylthio group, thiadiazolylthio group, etc., alkyl or arylsulfonyl group (carbon number) 1-20, preferably 1-10 alkyl or arylsulfonyl groups, such as mesyl, tosyl, etc.), alkyl or arylsulfinyl groups (C1-C20, preferably 1-10 alkyl or Arylsulfonyl groups such as methanesulfinyl group, benzenesulfinyl group, etc.), hydroxy group, mercapto group, cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group , Heterocyclic groups (charcoal A heterocyclic group having a prime number of 1 to 20, preferably 1 to 10, for example, a nitrogen atom, an oxygen atom, a sulfur atom, specifically an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a thienyl group, a piperidyl group, a morpholino Group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, carbazolyl group, azepinyl group and the like. ), A silyl group (a silyl group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, such as a trimethylsilyl group or a triphenylsilyl group). The hydrogen atom of these substituents may be further substituted. Moreover, when there are two or more substituents in one molecule, these substituents may be the same or different. If possible, they may be linked together to form a ring. As the substituent, a halogen atom, an alkyl group, a silyl group, an aryl group, an alkoxy group and an aryloxy group are preferable, and a methyl group, a trimethylsilyl group, a phenyl group and a methoxy group are particularly preferable.

  The polar group refers to an organic group that is polarized by atoms having high electronegativity such as oxygen, sulfur, nitrogen, and halogen. Specifically, an amino group (an amino group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as an amino group, a methylamino group, a dimethylamino group, a diethylamino group, and a dibenzylamino group). Alkoxy groups (C1-C20, preferably 1-10 alkoxy groups such as methoxy, ethoxy and butoxy groups), aryloxy groups (C6-20, preferably 6-15). An aryloxy group such as a phenyloxy group and a 2-naphthyloxy group), a heterocyclic oxy group (a heterocyclic oxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms such as a pyridinyloxy group, Pyrimidinyloxy group, pyridazinyloxy group, benzimidazolyloxy group, etc.), silyloxy group (3 to 2 carbon atoms) A silyloxy group having 3 to 10 carbon atoms, such as a trimethylsilyloxy group and a t-butyldimethylsilyloxy group.), An acyl group (acyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, An acetyl group, a benzoyl group, a formyl group, a pivaloyl group, etc.), an alkoxycarbonyl group (a C2-C20, preferably a C2-C10 alkoxycarbonyl group, such as a methoxycarbonyl group, an ethoxycarbonyl group, etc.). An aryloxycarbonyl group (C6-C20, preferably a C6-C15 aryloxycarbonyl group such as a phenyloxycarbonyl group), an acyloxy group (C1-C20, preferably 1-10 acyloxy groups such as acetoxy group, benzoy An oxy group, etc.), an acylamino group (acylamino group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms such as an acetylamino group and a benzoylamino group), an alkoxycarbonylamino group (carbon number). An alkoxycarbonylamino group having 2 to 20, preferably 2 to 10, such as a methoxycarbonylamino group), an aryloxycarbonylamino group (having 6 to 20 carbon atoms, preferably 6 to 15 aryloxycarbonylamino groups) For example, a phenyloxycarbonylamino group), an alkyl or arylsulfonylamino group (an alkyl or arylsulfonylamino group having 1 to 20, preferably 1 to 10 carbon atoms, such as a methanesulfonylamino group, benzenesulfonyl Amino group And so on. ), A sulfamoyl group (a sulfamoyl group having 0 to 20, preferably 0 to 10 carbon atoms, such as a sulfamoyl group, an N-methylsulfamoyl group, an N, N-dimethylsulfamoyl group, an N-phenylsulfamoyl group). ), A carbamoyl group (a carbamoyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as a carbamoyl group, an N-methylcarbamoyl group, an N, N-diethylcarbamoyl group, an N-phenylcarbamoyl group, etc. Ureido group (C1-C20, preferably 1-10 ureido groups such as ureido group, methylureido group, phenylureido group, etc.), hydroxy group, halogen atom (for example, Fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, Toromoto, hydroxamic acid group, sulfino group, a hydrazino group, an imino group, a heterocyclic group. These substituents may be directly connected to the norbornene ring, may be connected by an alkylene group or the like, and may be further substituted. Moreover, when there are two or more substituents in one molecule, these substituents may be the same or different. If possible, they may be linked together to form a ring. Preferred as the polar group are amino group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, and aryl. An oxycarbonylamino group, more preferably an alkoxycarbonyl group, an acyloxy group, an acylamino group, and an alkoxycarbonylamino group, and particularly preferably an alkoxycarbonyl group.

Examples of saturated norbornene resins that can be used in the present invention include, for example, JP-A-60-168708, JP-A-62-252406, JP-A-62-2252407, JP-A-2-133413, Examples thereof include resins described in JP-A-63-145324, JP-A-63-264626, JP-A-1-240517, and JP-B-57-8815.
Among these resins, a hydrogenated polymer obtained by hydrogenating a ring-opening polymer of a norbornene monomer is particularly preferable.
The glass transition temperature (Tg) of these saturated norbornene resins is preferably 120 ° C. or higher, more preferably 140 ° C. or higher, and the saturated water absorption is preferably 1% by mass or lower, more preferably 0.8%. It is 8 mass% or less. The glass transition temperature (Tg) and saturated water absorption of the saturated norbornene resins represented by the general formulas (1) to (4) can be controlled by selecting the type of R ^{1 to} R ¹² .

  In the present invention, as the saturated norbornene resin, at least one tetracyclododecene derivative represented by the following general formula (5) is used alone, or the unsaturated compound capable of copolymerizing with the tetracyclododecene derivative. A hydrogenated polymer obtained by hydrogenating a polymer obtained by metathesis polymerization with a cyclic compound can also be used.

In General Formula (5), R ^{13 to} R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent (preferably an organic group), and at least one of these is preferably a polar group. Specific examples and preferred ranges of the substituents and polar groups herein are the same as those described for the general formulas (1) to (4).
In the tetracyclododecene derivative represented by the above general formula (5), when at least one of R ^{13 to} R ¹⁶ is a polar group, a polarizing film having excellent adhesion to other materials, heat resistance, etc. Obtainable. Further, the polar group is a group represented by — (CH ₂ ) _n COOR (where R is a hydrocarbon group having 1 to 20 carbon atoms, and n is an integer of 0 to 10). The resulting hydrogenated polymer (polarizing film substrate) is preferred because it has a high glass transition temperature. In particular, the polar substituent represented by — (CH ₂ ) _n COOR is preferably contained in one molecule of the tetracyclododecene derivative of the general formula (5) from the viewpoint of reducing the water absorption rate. In the above polar substituent, it is preferable in that the hygroscopicity of the obtained hydrogenated polymer decreases as the number of carbon atoms of the hydrocarbon group represented by R increases, but the balance with the glass transition temperature of the obtained hydrogenated polymer is good. From this point, the hydrocarbon group is preferably a chain alkyl group having 1 to 4 carbon atoms or a (poly) cyclic alkyl group having 5 or more carbon atoms, and particularly preferably a methyl group, an ethyl group, or a cyclohexyl group. preferable.

Furthermore, the tetracyclododecene derivative of the general formula (5) in which a hydrocarbon group having 1 to 10 carbon atoms is bonded as a substituent to a carbon atom to which a group represented by — (CH ₂ ) _n COOR is bonded, This is preferable because the resulting hydrogenated polymer has low hygroscopicity. In particular, the tetracyclododecene derivative of the general formula (5) in which the substituent is a methyl group or an ethyl group is preferable in terms of easy synthesis. Specifically, 8-methyl-8-methoxycarbonyltetracyclo [4,4,0,1 ^2.5, 1 ^7.10] dodeca-3-ene are preferred. These tetracyclododecene derivatives and mixtures of unsaturated cyclic compounds copolymerizable therewith are described, for example, in JP-A-4-77520, page 4, upper right column, line 12 to page 6, lower right column, line 6. Metathesis polymerization and hydrogenation can be carried out by the prepared method.
These norbornene resins preferably have an intrinsic viscosity (η _inh ) measured at 30 ° C. in chloroform of 0.1 to 1.5 dl / g, more preferably 0.4 to 1.2 dl / g. g. Further, the hydrogenation rate of the hydrogenated polymer is preferably 50% or more, more preferably 90% or more, and still more preferably 98% or more, as measured by 60 MHz and ¹ H-NMR. The higher the hydrogenation rate, the more the resulting saturated norbornene film has better stability to heat and light. The gel content contained in the hydrogenated polymer is preferably 5% by mass or less, more preferably 1% by mass or less.

(Other ring-opening polymerizable cycloolefins)
In the present invention, other cycloolefins capable of ring-opening polymerization can be used in combination as long as the object of the present invention is not impaired. Specific examples of such cycloolefins include compounds having one reactive double bond such as cyclopentene, cyclooctene, and 5,6-dihydrodicyclopentadiene. The content of these ring-opening polymerizable cycloolefins is preferably 0 mol% to 50 mol%, more preferably 0.1 mol% to 30 mol%, based on the norbornene-based monomer. And 0.3 mol% to 10 mol% is particularly preferable.

(Additive)
The saturated norbornene resin of the present invention includes known antioxidants such as 2,6-di-t-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-t-butyl-5. , 5'-dimethylphenylmethane, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 1,1,3-tris (2-methyl-4-hydroxy-) 5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, stearyl-β- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-dioxy-3,3'-di-t-butyl-5,5'-diethylphenylmethane, 3,9-bis [1,1 -Dimethyl-2- [β -(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl], 2,4,8,10-tetraoxpiro [5,5] undecane, tris (2,4-di-t -Butylphenyl) phosphite, cyclic neopentanetetraylbis (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,6-di-t-butyl-4-methyl) Phenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite; UV absorbers such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone and the like are added. Can be stabilized. Further, additives such as a lubricant can be added for the purpose of improving processability.
The addition amount of these antioxidants is 0.1-3 mass parts normally with respect to 100 mass parts of saturated norbornene-type resin, Preferably it is 0.2-2 mass parts.

  Furthermore, you may add various additives, such as anti-aging agents, such as a phenol type and a phosphorus type, an antistatic agent, a ultraviolet absorber, and the above-mentioned easy-to-slip agent, to a saturated norbornene-type resin. In particular, since the liquid crystal is usually deteriorated by ultraviolet rays, it is preferable to add an ultraviolet absorber when other protective measures such as laminating an ultraviolet protective filter are not taken. As the ultraviolet absorber, a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, an acrylonitrile ultraviolet absorber, or the like can be used. Among them, a benzophenone ultraviolet absorber is preferable, and the addition amount is saturated norbornene. It is 10-100,000 mass ppm normally with respect to resin, Preferably it is 100-10,000 mass ppm. Moreover, when producing a sheet | seat by the solution casting method, in order to make surface roughness small, it is preferable to add a leveling agent. As the leveling agent, for example, a coating leveling agent such as a fluorine-based nonionic surfactant, a special acrylic resin-based leveling agent, or a silicone-based leveling agent can be used, and among them, those having good compatibility with a solvent are preferable. The addition amount is usually 5 to 50,000 mass ppm, preferably 10 to 20,000 mass ppm, based on the saturated norbornene resin.

《Filming》
The saturated norbornene film can be formed by either a solution casting method or a melt casting method. These film forming methods will be described in detail below.

(Melting film formation)
(1) Melting The saturated norbornene resin and additive are preferably mixed and pelletized prior to melt film formation. By pelletizing, surging in the hopper of the melt extruder is suppressed and stable supply becomes possible. Preferably, the pellet size is such cross-sectional area is 1 mm ² to 300 mm ^2, a length 1Mm～30mm, and more preferably the cross-sectional area of 2 mm ² 100 mm ^2, length 1.5Mm～10mm.
The saturated norbornene resin pellets are put into a melt extruder, dehydrated at 100 ° C. to 200 ° C. for 1 minute to 10 hours, and then kneaded and extruded. Kneading can be performed using a single-screw or twin-screw extruder.

  The saturated norbornene resin is supplied into the cylinder through the supply port of the extruder. FIG. 3 shows a schematic diagram of a typical extruder 22 that can be used in the present invention. In the cylinder 32, in order from the supply port 40 side, a supply unit (region A) for quantitatively transporting the saturated norbornene resin supplied from the supply port, a compression unit (region B) for melt-kneading and compressing the saturated norbornene resin, and melt-kneading -It is comprised with the measurement part (area | region C) which measures the saturated saturated norbornene resin. In order to prevent the melted resin from being oxidized by the remaining oxygen, it is more preferable to carry out the inside of the extruder in an inert (nitrogen or the like) air flow or while evacuating it using a vented extruder. The screw compression ratio of the extruder is preferably set to 2.5 to 4.5, and L / D is set to 20 to 70. Here, the screw compression ratio is represented by the volume ratio between the supply unit A and the metering unit C, that is, the volume per unit length of the supply unit A ÷ the volume per unit length of the metering unit C. It is calculated using the outer diameter d1 of the shaft, the outer diameter d2 of the screw shaft of the measuring part C, the groove part diameter a1 of the supply part A, and the groove part diameter a2 of the measuring part C. L / D is the ratio of the cylinder length to the cylinder inner diameter. The extrusion temperature is preferably set to 240 to 320 ° C, more preferably 250 to 310 ° C, and still more preferably 260 ° C to 300 ° C.

As the type of the extruder, a single-screw extruder having a relatively low equipment cost is generally used, and there are screw types such as full flight, mudock, and dalmage, but the full flight type is preferable. In addition, although the equipment cost is effective, it is possible to use a twin-screw extruder that can be extruded while volatilizing unnecessary volatile components by providing a vent port in the middle by changing the screw segment. There are two types of shaft extruders, the same direction and the different direction, which can be used. However, the type of the same direction rotation with high self-cleaning performance is preferred because a stagnant portion is hardly generated. The twin-screw extruder is effective, but it is suitable for forming a saturated norbornene resin because it has high kneadability and high resin supply performance and can be extruded at a low temperature. By properly arranging the vent port, it is possible to use the saturated norbornene pellets and powder in an undried state as they are. Also, film smears produced during film formation can be reused as they are without drying.
In addition, although the diameter of a preferable screw changes with target extrusion rates per unit time, it is 10 mm-300 mm, More preferably, it is 20 mm-250 mm, More preferably, it is 30 mm-150 mm.

(2) Filtration In order to filter foreign matters in the resin and avoid damage to the gear pump due to foreign matters, it is preferable to perform so-called breaker plate type filtration in which a filter medium is provided at the outlet of the extruder. In order to filter foreign matter with higher accuracy, it is preferable to provide a filtration device incorporating a so-called leaf type disk filter after passing through the gear pump. Filtration can be performed by providing one filtration section, or multistage filtration performed by providing a plurality of places. The filtration accuracy of the filter medium is preferably higher, but the filtration accuracy is preferably 15 μm to 3 μm, more preferably 10 μm to 3 μm, because of the pressure resistance of the filter medium and the increase in the filtration pressure due to clogging of the filter medium. In particular, when using a leaf-type disk filter device that finally filters foreign matter, it is preferable to use a filter medium with high filtration accuracy in terms of quality, and it is adjusted by the number of loaded sheets to ensure the suitability of pressure resistance and filter life. Is possible. The type of filter medium is preferably a steel material because it is used under high temperature and high pressure. Among steel materials, stainless steel, steel, etc. are particularly preferable, and stainless steel is particularly preferable in terms of corrosion. . As a configuration of the filter medium, for example, a sintered filter medium formed by sintering metal long fibers or metal powder can be used in addition to a knitted wire, and a sintered filter medium is preferable in terms of filtration accuracy and filter life.

(3) Gear pump To improve the thickness accuracy, it is important to reduce the fluctuation of the discharge amount. A gear pump is provided between the extruder and the die to supply a certain amount of saturated norbornene resin from the gear pump. It is effective to do. A gear pump is accommodated in a state where a pair of gears consisting of a drive gear and a driven gear are engaged with each other, and the drive gear is driven to engage and rotate the two gears so that a melted state is generated from the suction port formed in the housing. Resin is sucked into the cavity, and a certain amount of the resin is discharged from a discharge port formed in the housing. Even if there is a slight fluctuation in the resin pressure at the front end of the extruder, the fluctuation is absorbed by using a gear pump, the fluctuation in the resin pressure downstream of the film forming apparatus becomes very small, and the thickness fluctuation is improved. By using a gear pump, it is possible to keep the fluctuation range of the resin pressure in the die portion within ± 1%.
In order to improve the quantitative supply performance by the gear pump, a method of controlling the pressure before the gear pump to be constant by changing the number of rotations of the screw can also be used. In addition, a high-precision gear pump using three or more gears that eliminate the gear pump gear variation is also effective.

Other advantages of using a gear pump are that the pressure at the screw tip can be reduced to form a film, reducing energy consumption, preventing rise in resin temperature, improving transport efficiency, shortening the residence time in the extruder, L / D can be expected to be shortened. Also, when using a filter to remove foreign matter, if there is no gear pump, the amount of resin supplied from the screw may fluctuate as the filtration pressure rises. It can be resolved. On the other hand, the disadvantages of gear pumps are that the length of the equipment will be longer depending on the equipment selection method, the resin residence time will be longer, and the shearing stress of the gear pump may cause the molecular chain to break. is required.
The preferred residence time of the resin from the supply port through the extruder until it exits the die is 2 minutes to 60 minutes, more preferably 3 minutes to 40 minutes, and even more preferably 4 minutes to 30 minutes. is there.

  Since the flow of the polymer for bearing circulation of the gear pump is deteriorated, the sealing by the polymer in the drive part and the bearing part is deteriorated, and there is a problem that the fluctuation of the metering and liquid feeding extrusion pressure becomes large. A gear pump design (especially clearance) that matches the melt viscosity is required. Moreover, since the stay part of a gear pump causes deterioration of saturated norbornene resin, a structure with as little stay as possible is preferable. The polymer pipe and adapter that connect the extruder and gear pump or the gear pump and die also need to be designed with as little stagnation as possible. To stabilize the extrusion pressure, it is preferable to make the temperature fluctuation as small as possible. Generally, a band heater having a low equipment cost is often used for heating the polymer tube, but it is more preferable to use an aluminum cast heater with less temperature fluctuation.

(4) Die The saturated norbornene resin is melted by the extruder configured as described above, and the molten resin is continuously fed to the die via a filter and a gear pump as necessary. As long as the die is designed so that the molten resin stays in the die, any type of commonly used T die, fishtail die, and hanger coat die may be used. Moreover, there is no problem in placing a static mixer for improving the uniformity of the resin temperature immediately before the die. The clearance at the die outlet is generally 1.0 to 5.0 times the film thickness, preferably 1.2 to 3 times, more preferably 1.3 to 2 times. A lip clearance of 1.0 times or more of the film thickness is preferable because a sheet having a good surface shape can be easily obtained by film formation. Moreover, it is preferable if the lip clearance is 5.0 times or less of the film thickness because the thickness accuracy of the sheet can be easily increased. The die is a very important facility for determining the thickness accuracy of the film, and a die capable of strictly controlling the thickness adjustment is preferable. Normally, the thickness can be adjusted at intervals of 40 to 50 mm, but preferably a type capable of adjusting the film thickness at intervals of 35 mm or less, more preferably at intervals of 25 mm or less. In addition, it is important to have a design that minimizes the temperature unevenness of the die and the flow velocity unevenness in the width direction. An automatic thickness adjustment die that measures the downstream film thickness, calculates the thickness deviation, and feeds back the result to the die thickness adjustment is also effective in reducing the thickness fluctuation in long-term continuous production.
A single-layer film forming apparatus with a low equipment cost is generally used for manufacturing the film, but in some cases, a film having two or more types of structures can also be manufactured using a multilayer film forming apparatus in order to provide a functional layer on the outer layer. Is possible. In general, the functional layer is preferably thinly laminated on the surface layer, but the layer ratio is not particularly limited.

(5) Casting By the above method, the molten resin extruded from the die onto the sheet is cooled and solidified on a casting drum to obtain a film. At this time, it is preferable to use a method such as an electrostatic application method, an air knife method, an air chamber method, a vacuum nozzle method, or a touch roll method to increase the adhesion between the casting drum and the melt-extruded sheet. Such an adhesion improving method may be performed on the entire surface of the melt-extruded sheet or a part thereof. In particular, a method called edge pinning, in which only both ends of the film are brought into close contact with each other, is often used, but is not limited thereto.
More preferably, a plurality of casting drums are used for slow cooling. In particular, it is relatively common to use three cooling rolls, but this is not a limitation. The diameter of the roll is preferably 50 mm to 5000 mm, more preferably 100 mm to 2000 mm, and still more preferably 150 mm to 1000 mm. The interval between the plural rolls is preferably 0.3 mm to 300 mm, more preferably 1 mm to 100 mm, and still more preferably 3 mm to 30 mm.
The casting drum is preferably 60 ° C to 160 ° C, more preferably 70 ° C to 150 ° C, still more preferably 80 ° C to 140 ° C. Then, it peels off from a casting drum, winds up after passing through a nip roll. The winding speed is preferably 10 m / min to 100 m / min, more preferably 15 m / min to 80 m / min, still more preferably 20 m / min to 70 m / min.

The film forming width is preferably 0.7 m to 5 m, more preferably 1 m to 4 m, and still more preferably 1.3 m to 3 m. The thickness of the unstretched film thus obtained is preferably 30 μm to 400 μm, more preferably 40 μm to 300 μm, and still more preferably 50 μm to 200 μm.
The thickness unevenness of the formed saturated norbornene film is preferably 0% to 2% in both the longitudinal direction and the width direction, more preferably 0% to 1.5%, still more preferably 0% to 1%. The saturated norbornene film of the present invention can be obtained by stretching by this method.
When the so-called touch roll method is used, the surface of the touch roll may be a resin such as rubber or Teflon (registered trademark) or a metal roll. Further, it is possible to use a roll called a flexible roll because the roll surface is slightly dented by the pressure when touched by reducing the thickness of the metal roll, and the crimping area is widened.
The touch roll temperature is preferably 60 ° C to 160 ° C, more preferably 70 ° C to 150 ° C, and still more preferably 80 ° C to 140 ° C.

(6) Winding The sheet thus obtained is preferably trimmed at both ends and wound. The trimmed portion is recycled as a film raw material of the same type or as a film raw material of a different type after being pulverized or after being subjected to a granulation process or a depolymerization / repolymerization process as necessary. May be used. As the trimming cutter, any type of rotary cutter, shear blade, knife, or the like may be used. As for the material, either carbon steel or stainless steel may be used. In general, it is preferable to use a cemented carbide blade or a ceramic blade because the life of the blade is long and the generation of chips is suppressed.
Moreover, it is also preferable from a viewpoint of scratch prevention to attach a lami film to at least one surface before winding. A preferable winding tension is 1 kg / m width to 50 kg / width, more preferably 2 kg / m width to 40 kg / width, and further preferably 3 kg / m width to 20 kg / width. A winding tension of 1 kg / m width or more is preferable because the film can be easily wound up uniformly. If the take-up tension is 50 kg / width or less, the film will not be tightly wound, the winding appearance will be beautiful, and the film's bump will be extended by the creep phenomenon, causing the film to wavy. Residual birefringence due to elongation of the film does not occur. It is preferable that the winding tension is detected by tension control in the middle of the line and wound while being controlled so as to have a constant winding tension. If there is a difference in film temperature depending on the location of the film production line, the length of the film may be slightly different due to thermal expansion. It is necessary to prevent tension.
The winding tension can be wound at a constant tension by controlling the tension control. However, it is more preferable that the winding tension is tapered according to the wound diameter to obtain an appropriate winding tension. Generally, the tension is gradually reduced as the winding diameter increases, but in some cases, it may be preferable to increase the tension as the winding diameter increases.
Such a winding method can be similarly applied to the solution casting method described below.

(Solution casting)
When forming a saturated norbornene film by a solution casting method, first, a saturated norbornene resin is dissolved in a solvent. The concentration of the saturated norbornene resin when dissolved in the solvent is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 35% by mass. The viscosity of the resulting solution at room temperature is usually 1 to 1,000,000 (mPa · s), preferably 10 to 100,000 (mPa · s), more preferably 100 to 50,000 (mPa · s). Particularly preferably, it is 1,000 to 40,000 (mPa · s).
Solvents used include aromatic solvents such as benzene, toluene, xylene, cellosolve solvents such as methyl cellosolve, ethyl cellosolve, 1-methoxy-2-propanol, diacetone alcohol, acetone, cyclohexanone, methyl ethyl ketone, 4-methyl. -2-pentanone, cyclohexanone, ethylcyclohexanone, ketone solvents such as 1,2-dimethylcyclohexane, ester solvents such as methyl lactate and ethyl lactate, 2,2,3,3-tetrafluoro-1-propanol, methylene chloride And halogen-containing solvents such as chloroform, ether solvents such as tetrahydrofuran and dioxane, and alcohol solvents such as 1-pentanol and 1-butanol.

In addition to the above, the SP value (solubility parameter) is usually 10 to 30 (MPa ^1/2 ), preferably 10 to 25 (MPa ^1/2 ), more preferably 15 to 25 (MPa ^1/2 ), particularly It is preferable to use a solvent in the range of 15 to 20 (MPa ^1/2 ). The said solvent can be used individually or in combination of 2 or more types. When using 2 or more types of solvent together, it is preferable to make the range of SP value as a mixture into the said range. At this time, the value of the SP value as a mixture can be determined from the mass ratio. For example, in the case of two kinds of mixtures, the mass fraction of each solvent is W1, W2, and the SP value is SP1, SP2. Then, SP value of a mixed solvent can be calculated | required as a value calculated by the following formula.
SP value = W1 · SP1 + W2 · SP2
Further, a leveling agent may be added to improve the surface smoothness of the saturated norbornene film. Any general leveling agent can be used. For example, a fluorine-based nonionic surfactant, a special acrylic resin leveling agent, a silicone leveling agent, and the like can be used.

As a method for producing a saturated norbornene film by a solvent casting method, the above solution can be obtained by using a die or a coater to form a metal drum, a steel belt, a polyester film such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), polytetrafluoro In general, a method of coating on a base material such as an ethylene belt and then drying and removing the solvent to peel the film from the base material can be mentioned.
Alternatively, the resin solution can be applied to the substrate by means of spraying, brushing, roll spin coating, dipping, etc., and then the solvent is dried and removed to peel the film from the substrate. The thickness and surface smoothness may be controlled by repeating the coating.
Moreover, when using a polyester film as a base material, you may use the film by which surface treatment was carried out. As a surface treatment method, a hydrophilic treatment method generally performed, for example, a method of laminating an acrylic resin or a sulfonate group-containing resin by coating or lamination, or a hydrophilic property of the film surface by corona discharge treatment or the like. The method etc. which improve are mentioned.

The drying (solvent removal) step of the solvent casting method is not particularly limited and can be carried out by a generally used method, for example, a method of passing through a drying furnace through a large number of rollers. If bubbles are generated as a result of evaporation, the characteristics of the film are remarkably deteriorated. Therefore, in order to avoid this, it is preferable to control the temperature or air volume in each step by making the drying step into a plurality of steps of two or more steps.
Further, the residual solvent amount in the saturated norbornene film is usually 10% by mass or less, preferably 5% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less. By reducing the residual solvent in this way, it is preferable because the adhesion trace failure can be further reduced.
The thickness of the saturated norbornene film of the present invention is preferably 10 to 300 μm, more preferably 20 to 250 μm, still more preferably 30 to 200 μm, and the thickness distribution is preferably within ± 8% with respect to the average value. Preferably it is within ± 5%, more preferably within ± 3%. The variation in thickness per cm is usually 5% or less, preferably 3% or less, more preferably 1% or less, and particularly preferably 0.5% or less.

<Extension>
The saturated norbornene film formed as a solution or melt as described above is longitudinally stretched and laterally stretched by the method described above. These longitudinal stretching and lateral stretching may be carried out separately from solution casting or melt casting, or may be carried out continuously. In other words, after film formation, the one wound up may be sent out again and stretched, or may be continuously stretched as it is after film formation.
Such stretching is preferably carried out at a solvent amount of 0.5% by mass or less, more preferably 0.3% by mass or less, and still more preferably 0.1% by mass or less.

<Processing and use of saturated norbornene film>
The saturated norbornene film thus obtained may be used alone or in combination with a polarizing plate, and a liquid crystal layer or a layer with a controlled refractive index (low reflection layer) on these. Alternatively, a hard coat layer may be provided. These can be achieved by the following steps.

"surface treatment"
The saturated norbornene film can be improved in adhesion with each functional layer (for example, the undercoat layer and the back layer) by performing a surface treatment. For example, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment can be used. The glow discharge treatment here may be low-temperature plasma that occurs in a low-pressure gas of 10 ^{−3 to} 20 Torr, and plasma treatment under atmospheric pressure is also preferable. A plasma-excitable gas is a gas that is plasma-excited under the above-mentioned conditions, and examples thereof include chlorofluorocarbons such as argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, tetrafluoromethane, and mixtures thereof. It is done. Details of these are described in detail on pages 30 to 32 of the Japan Society of Invention Disclosure Technical Bulletin (Public Technical Number 2001-1745, published on March 15, 2001, Japan Society of Invention). In the plasma treatment at atmospheric pressure, which has been attracting attention in recent years, for example, irradiation energy of 20 to 500 kGy is used under 10 to 1000 keV, and more preferably irradiation energy of 20 to 300 kGy is used under 30 to 500 keV.
Of these, glow discharge treatment, corona treatment, and flame treatment are particularly preferred.
It is also preferable to provide an undercoat layer for adhesion to the functional layer. This layer may be applied after the above surface treatment or may be applied without the surface treatment. The details of the undercoat layer are described on page 32 of the Japan Society for Invention and Innovation (Public Technical Number 2001-1745, published on March 15, 2001, Japan Society of Invention). These surface treatment and undercoating processes can be incorporated at the end of the film forming process, can be performed alone, or can be performed in the functional layer application process described later.

《Granting functional layer》
The saturated norbornene film of the present invention is combined with the functional layer described in detail on pages 32 to 45 of the Japan Institute of Invention Disclosure Bulletin (Public Technical No. 2001-1745, published on March 15, 2001, Japan Society of Invention). Is preferred. Among these, application of a polarizing film (polarizing plate), application of an optical compensation layer (optical compensation sheet), and application of an antireflection layer (antireflection film) are preferable. Hereinafter, these preferred embodiments will be described in order.

(A) Application of polarizing film (preparation of polarizing plate)
(E1) Material used Currently, a commercially available polarizing film is produced by immersing a stretched polymer in a solution of iodine or dichroic dye in a bath, and allowing the iodine or dichroic dye to penetrate into the binder. It is common to be done. As the polarizing film, a coating type polarizing film represented by Optiva Inc. can also be used. The iodine and the dichroic dye in the polarizing film develop polarizing performance by being oriented in the binder. As the dichroic dye, an azo dye, stilbene dye, pyrazolone dye, triphenylmethane dye, quinoline dye, oxazine dye, thiazine dye or anthraquinone dye is used. The dichroic dye is preferably water-soluble. The dichroic dye preferably has a hydrophilic substituent (for example, a sulfo group, an amino group, or a hydroxyl group). For example, the compounds described in page 58 of the Japan Society of Invention Disclosure Technique (Public Technical No. 2001-1745, published on March 15, 2001, Japan Society of Invention).
As the binder for the polarizing film, either a polymer that can be crosslinked per se or a polymer that is crosslinked by a crosslinking agent can be used, and a plurality of combinations of these can be used. Examples of the binder include methacrylate copolymer, styrene copolymer, polyolefin, polyvinyl alcohol and modified polyvinyl alcohol, poly (N-methylolacrylamide), polyester described in paragraph No. [0022] of JP-A-8-338913. , Polyimide, vinyl acetate copolymer, carboxymethyl cellulose, polycarbonate and the like. Silane coupling agents can be used as the polymer. Water-soluble polymers (for example, poly (N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvinyl alcohol, and modified polyvinyl alcohol) are preferable, gelatin, polyvinyl alcohol, and modified polyvinyl alcohol are more preferable, and polyvinyl alcohol and modified polyvinyl alcohol are most preferable. . It is particularly preferable to use two types of polyvinyl alcohol or modified polyvinyl alcohol having different degrees of polymerization. The saponification degree of polyvinyl alcohol is preferably 70 to 100%, more preferably 80 to 100%. It is preferable that the polymerization degree of polyvinyl alcohol is 100-5000. The modified polyvinyl alcohol is described in JP-A-8-338913, JP-A-9-152509 and JP-A-9-316127. Two or more kinds of polyvinyl alcohol and modified polyvinyl alcohol may be used in combination.

The lower limit of the binder thickness is preferably 10 μm. The upper limit of the thickness is preferably as thin as possible from the viewpoint of light leakage of the liquid crystal display device. It is preferable that it is below the thickness (about 30 micrometers) of the commercially available polarizing plate now, it is preferable that it is 25 micrometers or less, and it is further more preferable that it is 20 micrometers or less.
The binder of the polarizing film may be cross-linked. A polymer or monomer having a crosslinkable functional group may be mixed in the binder, or a crosslinkable functional group may be imparted to the binder polymer itself. Crosslinking can be performed by light, heat, or pH change, and a binder having a crosslinked structure can be formed. The crosslinking agent is described in US Reissue Patent 23297. Boron compounds (for example, boric acid and borax) can also be used as a crosslinking agent. The addition amount of the crosslinking agent in the binder is preferably 0.1 to 20% by mass with respect to the binder. The orientation of the polarizing element and the moisture and heat resistance of the polarizing film are improved.
Even after the crosslinking reaction is completed, the amount of unreacted crosslinking agent is preferably 1.0% by mass or less, and more preferably 0.5% by mass or less. By doing in this way, a weather resistance improves.

(E2) Stretching of polarizing film The polarizing film is preferably dyed with iodine or a dichroic dye after the polarizing film is stretched (stretching method) or rubbed (rubbing method).
In the stretching method, the stretching ratio is preferably 2.5 to 30.0 times, and more preferably 3.0 to 10.0 times. Stretching can be performed by dry stretching in air. Moreover, you may implement wet extending | stretching in the state immersed in water. The stretch ratio of dry stretching is preferably 2.5 to 5.0 times, and the stretch ratio of wet stretching is preferably 3.0 to 10.0 times. The draw ratio here is (length after drawing / length before drawing). Stretching may be performed in parallel to the MD direction (parallel stretching) or may be performed in an oblique direction (oblique stretching). These stretching operations may be performed once or divided into several times. By dividing into several times, it can be stretched more uniformly even at high magnification.

a) Parallel stretch method Prior to stretching, the PVA film is swollen. The swelling degree is preferably 1.2 to 2.0 times (mass ratio before swelling and after swelling). Thereafter, the film is stretched at a bath temperature of preferably 15 to 50 ° C., more preferably 17 to 40 ° C. in an aqueous medium bath or a dye bath for dissolving a dichroic substance while being continuously conveyed through a guide roll or the like. . Stretching can be achieved by gripping with two pairs of nip rolls and increasing the conveyance speed of the subsequent nip roll to be higher than that of the previous nip roll. The draw ratio is based on the length ratio after stretching / initial state (hereinafter the same), but the draw ratio is preferably 1.2 to 3.5 times, more preferably 1.5 to 3. 0 times. Thereafter, the film is dried at 50 ° C. to 90 ° C. to obtain a polarizing film.

b) Diagonal Stretching Method For this purpose, a method of stretching using a tenter projecting in an obliquely inclined direction as described in JP-A-2002-86554 can be used. Since this stretching is performed in the air, it is necessary to make it easy to stretch by adding water in advance. The preferred water content is 5% to 100%, more preferably 10% to 100%.
The temperature during stretching is preferably 40 ° C to 90 ° C, more preferably 50 ° C to 80 ° C. The relative humidity is preferably 50% to 100%, more preferably 70% to 100%, and still more preferably 80% to 100%. The traveling speed in the longitudinal direction is preferably 1 m / min or more, more preferably 3 m / min or more.
After the completion of stretching, the film is preferably dried at 50 ° C to 100 ° C, more preferably 60 ° C to 90 ° C, and preferably 0.5 minutes to 10 minutes. The drying time is more preferably 1 minute to 5 minutes.
The absorption axis of the polarizing film thus obtained is preferably 10 to 80 degrees, more preferably 30 to 60 degrees, and still more preferably 45 degrees (40 to 50 degrees).

(E3) Bonding The saturated norbornene film after the surface treatment and the polarizing film prepared by stretching are bonded to prepare a polarizing plate. The laminating direction is preferably such that the casting axis direction of the saturated norbornene film and the stretching axis direction of the polarizing plate are 45 degrees.
The bonding adhesive is not particularly limited, and examples include PVA resins (including modified PVA such as acetoacetyl group, sulfonic acid group, carboxyl group, oxyalkylene group), boron compound aqueous solution, epoxy adhesive, and the like. Of these, PVA resins and epoxy adhesives are preferred. The thickness of the adhesive layer is preferably 0.01 to 10 μm after drying, and particularly preferably 0.05 to 5 μm.
The polarizing plate thus obtained preferably has a higher light transmittance, and preferably has a higher degree of polarization. The transmittance of the polarizing plate is preferably in the range of 30 to 50%, more preferably in the range of 35 to 50%, and most preferably in the range of 40 to 50% in light having a wavelength of 550 nm. . The degree of polarization is preferably in the range of 90 to 100%, more preferably in the range of 95 to 100%, and most preferably in the range of 99 to 100% in light having a wavelength of 550 nm.
Furthermore, the polarizing plate thus obtained can be laminated with a λ / 4 plate to produce circularly polarized light. In this case, lamination is performed so that the slow axis of λ / 4 and the absorption axis of the polarizing plate are 45 degrees. At this time, λ / 4 is not particularly limited, but more preferably has a wavelength dependency such that the lower the wavelength, the smaller the retardation. Furthermore, it is preferable to use a polarizing film having an absorption axis inclined by 20 to 70 degrees with respect to the longitudinal direction and a λ / 4 plate made of an optically anisotropic layer made of a liquid crystalline compound.

(B) Application of optical compensation layer (creation of optical compensation sheet)
The optically anisotropic layer is for compensating for the liquid crystal compound in the liquid crystal cell in the black display of the liquid crystal display device, forms an alignment film on the saturated norbornene film, and further provides an optically anisotropic layer. Is formed.

(Row 1) Alignment film An alignment film is provided on the surface-treated saturated norbornene film. This film has a function of defining the alignment direction of liquid crystalline molecules. However, if the alignment state is fixed after aligning the liquid crystalline compound, the alignment film plays the role, and thus is not necessarily an essential component of the present invention. That is, it is possible to produce the polarizing plate of the present invention by transferring only the optically anisotropic layer on the alignment film in which the alignment state is fixed onto the polarizer.
The alignment film is an organic compound (for example, ω-tricosanoic acid) formed by rubbing treatment of an organic compound (preferably polymer), oblique deposition of an inorganic compound, formation of a layer having a microgroove, or Langmuir-Blodgett method (LB film). , Dioctadecylmethylammonium chloride, methyl stearylate). Furthermore, an alignment film in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation is also known.
The alignment film is preferably formed by polymer rubbing treatment. In principle, the polymer used for the alignment film has a molecular structure having a function of aligning liquid crystal molecules.
In the present invention, in addition to the function of aligning liquid crystalline molecules, a crosslink having a function of aligning a side chain having a crosslinkable functional group (for example, a double bond) to the main chain or aligning liquid crystalline molecules. It is preferable to introduce a functional functional group into the side chain.

  As the polymer used in the alignment film, either a polymer that can be crosslinked by itself or a polymer that is crosslinked by a crosslinking agent can be used, and a plurality of combinations thereof can be used. Examples of the polymer include methacrylate copolymers, styrene copolymers, polyolefins, polyvinyl alcohols and modified polyvinyl alcohols, poly (N-methylol acrylamide) described in paragraph No. [0022] of JP-A-8-338913, for example. , Polyester, polyimide, vinyl acetate copolymer, carboxymethyl cellulose, polycarbonate and the like. Silane coupling agents can be used as the polymer. Water-soluble polymers (for example, poly (N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvinyl alcohol, and modified polyvinyl alcohol) are preferable, gelatin, polyvinyl alcohol, and modified polyvinyl alcohol are more preferable, and polyvinyl alcohol and modified polyvinyl alcohol are most preferable. . It is particularly preferable to use two types of polyvinyl alcohol or modified polyvinyl alcohol having different degrees of polymerization. The saponification degree of polyvinyl alcohol is preferably 70 to 100%, more preferably 80 to 100%. It is preferable that the polymerization degree of polyvinyl alcohol is 100-5000.

A side chain having a function of aligning liquid crystal molecules generally has a hydrophobic group as a functional group. The specific type of functional group is determined according to the type of liquid crystal molecule and the required alignment state. For example, the modifying group of the modified polyvinyl alcohol can be introduced by copolymerization modification, chain transfer modification or block polymerization modification. Examples of modifying groups include hydrophilic groups (carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, amino groups, ammonium groups, amide groups, thiol groups, etc.), hydrocarbon groups having 10 to 100 carbon atoms, fluorine atoms Examples include substituted hydrocarbon groups, thioether groups, polymerizable groups (unsaturated polymerizable groups, epoxy groups, azirinidyl groups, etc.), alkoxysilyl groups (trialkoxy, dialkoxy, monoalkoxy), and the like. Specific examples of these modified polyvinyl alcohol compounds include those described in, for example, paragraph numbers [0022] to [0145] of JP-A No. 2000-155216 and paragraph numbers [0018] to [0022] of JP-A No. 2002-62426. Etc.
When a side chain having a crosslinkable functional group is bonded to the main chain of the alignment film polymer, or a crosslinkable functional group is introduced into a side chain having a function of aligning liquid crystalline molecules, the alignment film polymer and the optically anisotropic film The polyfunctional monomer contained in the conductive layer can be copolymerized. As a result, not only between the polyfunctional monomer and the polyfunctional monomer, but also between the alignment film polymer and the alignment film polymer and between the polyfunctional monomer and the alignment film polymer is firmly bonded by a covalent bond. Therefore, the strength of the optical compensation sheet can be remarkably improved by introducing the crosslinkable functional group into the alignment film polymer.

The crosslinkable functional group of the alignment film polymer preferably contains a polymerizable group in the same manner as the polyfunctional monomer. Specific examples include those described in JP-A 2000-155216, paragraph numbers [0080] to [0100]. Apart from the crosslinkable functional group, the alignment film polymer can also be crosslinked using a crosslinking agent.
Examples of the crosslinking agent include aldehydes, N-methylol compounds, dioxane derivatives, compounds that act by activating carboxyl groups, active vinyl compounds, active halogen compounds, isoxazole, and dialdehyde starch. Two or more kinds of crosslinking agents may be used in combination. Specific examples include compounds described in paragraph numbers [0023] to [0024] of JP-A No. 2002-62426. Aldehydes having high reaction activity, particularly glutaraldehyde are preferred.

0.1-20 mass% is preferable with respect to a polymer, and, as for the addition amount of a crosslinking agent, 0.5-15 mass% is more preferable. The amount of the unreacted crosslinking agent remaining in the alignment film is preferably 1.0% by mass or less, and more preferably 0.5% by mass or less. By adjusting in this way, even if the alignment film is used for a long time in a liquid crystal display device or left in a high temperature and high humidity atmosphere for a long time, sufficient durability without reticulation can be obtained. May occur.
The alignment film can be basically formed by applying the polymer on the transparent support containing the alignment film forming material and the crosslinking agent, followed by drying by heating (crosslinking) and rubbing treatment. As described above, the crosslinking reaction may be carried out at any time after coating on the transparent support. When a water-soluble polymer such as polyvinyl alcohol is used as the alignment film forming material, the coating solution is preferably a mixed solvent of an organic solvent (for example, methanol) having a defoaming action and water. The ratio of water: methanol is preferably 0: 100 to 99: 1, and more preferably 0: 100 to 91: 9. Thereby, generation | occurrence | production of a bubble is suppressed and the defect of the layer surface of an alignment film and also an optically anisotropic layer reduces remarkably.

The alignment film is preferably applied by spin coating, dip coating, curtain coating, extrusion coating, rod coating, or roll coating. The rod coating method is particularly preferable. The film thickness after drying is preferably 0.1 to 10 μm. Heating and drying can be performed at 20 ° C to 110 ° C. In order to form a sufficient crosslink, 60 ° C to 100 ° C is preferable, and 80 ° C to 100 ° C is particularly preferable. The drying time can be 1 minute to 36 hours, preferably 1 minute to 30 minutes. The pH is also preferably set to an optimum value for the crosslinking agent to be used. When glutaraldehyde is used, the pH is 4.5 to 5.5, and 5 is particularly preferable.
The alignment film is provided on the transparent support or the undercoat layer. The alignment film can be obtained by rubbing the surface after crosslinking the polymer layer as described above.
For the rubbing treatment, a treatment method widely adopted as a liquid crystal alignment treatment process of LCD can be applied. That is, a method of obtaining the orientation by rubbing the surface of the orientation film in a certain direction using paper, gauze, felt, rubber, nylon, polyester fiber or the like can be used. Generally, it is carried out by rubbing several times using a cloth or the like in which fibers having a uniform length and thickness are planted on average.

In industrial implementation, this is achieved by bringing the rotating rubbing roll into contact with the film with the polarizing film being transported. Is preferably 30 μm or less. The film wrap angle on the rubbing roll is preferably 0.1 to 90 °. However, as described in JP-A-8-160430, a stable rubbing treatment can be obtained by winding 360 ° or more. As for the conveyance speed of a film, 1-100 m / min is preferable. It is preferable to select an appropriate rubbing angle in the range of 0 to 60 °. When used in a liquid crystal display device, 40 to 50 ° is preferable, and 45 ° is particularly preferable.
The thickness of the alignment film thus obtained is preferably in the range of 0.1 to 10 μm.

Next, the liquid crystalline molecules of the optically anisotropic layer are aligned on the alignment film. Thereafter, as necessary, the alignment film polymer and the polyfunctional monomer contained in the optically anisotropic layer are reacted, or the alignment film polymer is crosslinked using a crosslinking agent.
The liquid crystalline molecules used in the optically anisotropic layer include rod-like liquid crystalline molecules and discotic liquid crystalline molecules. The rod-like liquid crystal molecules and the disk-like liquid crystal molecules may be high-molecular liquid crystals or low-molecular liquid crystals, and further include those in which low-molecular liquid crystals are cross-linked and no longer exhibit liquid crystallinity.

(Ro 2) Rod-like liquid crystalline molecules As rod-like liquid crystalline molecules, azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenyl Pyrimidines, alkoxy-substituted phenylpyrimidines, phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used.
The rod-like liquid crystalline molecule includes a metal complex. In addition, a liquid crystal polymer containing a rod-like liquid crystalline molecule in a repeating unit can also be used as the rod-like liquid crystalline molecule. In other words, the rod-like liquid crystal molecule may be bonded to a (liquid crystal) polymer.
For rod-like liquid crystalline molecules, see Chapter 4, Chapter 7 and Chapter 11 of the Chemical Chemistry of the Quarterly Chemical Review Vol. 22, Liquid Crystal Chemistry (1994), and the 142nd Committee of the Japan Society for the Promotion of Science. Described in Chapter 3.
The birefringence of the rod-like liquid crystal molecule is preferably in the range of 0.001 to 0.7.
The rod-like liquid crystalline molecule preferably has a polymerizable group in order to fix its alignment state. The polymerizable group is preferably a radical polymerizable unsaturated group or a cationic polymerizable group. Specifically, for example, the polymerizable group described in paragraphs [0064] to [0086] of JP-A No. 2002-62427 can be used. Liquid crystal compounds.

(Row 3) Discotic liquid crystalline molecules Discotic liquid crystalline molecules include C.I. Destrade et al., Mol. Cryst. 71, 111 (1981), benzene derivatives described in C.I. Destrade et al., Mol. Cryst. 122, 141 (1985), Physics lett, A, 78, 82 (1990); Kohne et al., Angew. Chem. 96, page 70 (1984) and the cyclohexane derivatives described in J. Am. M.M. Lehn et al. Chem. Commun. , 1794 (1985), J. Am. Zhang et al., J. Am. Chem. Soc. 116, 2655 (1994), azacrown type and phenylacetylene type macrocycles are included.

As a discotic liquid crystalline molecule, a compound having liquid crystallinity having a structure in which a linear alkyl group, an alkoxy group, and a substituted benzoyloxy group are radially substituted as a side chain of the mother nucleus with respect to the mother nucleus at the center of the molecule Is also included. The molecule or the assembly of molecules is preferably a compound that has rotational symmetry and can give a certain orientation. In the optically anisotropic layer formed from the discotic liquid crystalline molecules, the compound finally contained in the optically anisotropic layer does not need to be a discotic liquid crystalline molecule. Also included are compounds that have a group that reacts with heat or light, and that eventually polymerize or cross-link by reaction with heat or light to increase the molecular weight and lose liquid crystallinity. Preferred examples of the discotic liquid crystalline molecules are described in JP-A-8-50206. The polymerization of discotic liquid crystalline molecules is described in JP-A-8-27284.
In order to fix the discotic liquid crystalline molecules by polymerization, it is necessary to bond a polymerizable group as a substituent to the discotic core of the discotic liquid crystalline molecules. A compound in which the discotic core and the polymerizable group are bonded via a linking group is preferable, whereby the orientation state can be maintained even in the polymerization reaction. Examples thereof include compounds described in paragraph numbers [0151] to [0168] of JP-A No. 2000-155216.

It increases or decreases in the depth direction of the optically anisotropic layer and with increasing distance from the plane of the polarizing film. The angle preferably decreases with increasing distance. Further, the change in angle can be a continuous increase, a continuous decrease, an intermittent increase, an intermittent decrease, a change including a continuous increase and a continuous decrease, or an intermittent change including an increase and a decrease. The intermittent change includes a region where the inclination angle does not change in the middle of the thickness direction. Even if the angle includes a region where the angle does not change, the angle only needs to increase or decrease as a whole. Furthermore, it is preferable that the angle changes continuously.
The average direction of the major axis of the discotic liquid crystalline molecules on the polarizing film side can be generally adjusted by selecting a discotic liquid crystalline molecule or an alignment film material, or by selecting a rubbing treatment method. In addition, the major axis (disk surface) direction of the surface-side (air-side) discotic liquid crystalline molecules is generally adjusted by selecting the type of additive used together with the discotic liquid crystalline molecules or discotic liquid crystalline molecules. be able to. Examples of the additive used together with the discotic liquid crystalline molecule include a plasticizer, a surfactant, a polymerizable monomer and a polymer. The degree of change in the orientation direction of the major axis can also be adjusted by selecting liquid crystalline molecules and additives as described above.

(Raw 4) Other composition of optically anisotropic layer Along with the above liquid crystalline molecules, a plasticizer, a surfactant, a polymerizable monomer, etc. are used in combination to obtain coating film uniformity, film strength, and liquid crystal molecules. The orientation of the film can be improved. It is preferable that the compound has compatibility with the liquid crystal molecules and can change the tilt angle of the liquid crystal molecules or does not inhibit the alignment.
Examples of the polymerizable monomer include radically polymerizable or cationically polymerizable compounds. Preferably, it is a polyfunctional radically polymerizable monomer and is preferably copolymerizable with the above-described polymerizable group-containing liquid crystal compound. Examples thereof include those described in JP-A-2002-296423, paragraph numbers [0018] to [0020]. The amount of the compound added is generally in the range of 1 to 50% by mass and preferably in the range of 5 to 30% by mass with respect to the discotic liquid crystalline molecules.
Examples of the surfactant include conventionally known compounds, and fluorine compounds are particularly preferable. Specifically, for example, compounds described in JP-A-2001-330725, paragraph numbers [0028] to [0056] can be mentioned.

The polymer used together with the discotic liquid crystalline molecule is preferably capable of changing the tilt angle of the discotic liquid crystalline molecule.
A cellulose ester can be mentioned as an example of a polymer. Preferable examples of the cellulose ester include those described in paragraph No. [0178] of JP-A No. 2000-155216. The addition amount of the polymer is preferably in the range of 0.1 to 10% by mass, and preferably in the range of 0.1 to 8% by mass with respect to the liquid crystal molecule so as not to inhibit the alignment of the liquid crystal molecules. It is more preferable.
The discotic nematic liquid crystal phase-solid phase transition temperature of the discotic liquid crystalline molecules is preferably 70 to 300 ° C, more preferably 70 to 170 ° C.

(Raw 5) Formation of optically anisotropic layer The optically anisotropic layer is formed by applying a coating liquid containing liquid crystalline molecules and, if necessary, a polymerizable initiator and an optional component on the alignment film. Can be formed.
As a solvent used for preparing the coating solution, an organic solvent is preferably used. Examples of organic solvents include amides (eg N, N-dimethylformamide), sulfoxides (eg dimethyl sulfoxide), heterocyclic compounds (eg pyridine), hydrocarbons (eg benzene, hexane), alkyl halides (eg , Chloroform, dichloromethane, tetrachloroethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.
The coating liquid can be applied by a known method (for example, a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, or a die coating method).
The thickness of the optically anisotropic layer is preferably 0.1 to 20 μm, more preferably 0.5 to 15 μm, and most preferably 1 to 10 μm.

(Row 6) Fixation of alignment state of liquid crystalline molecules Aligned liquid crystalline molecules can be fixed while maintaining the alignment state. The immobilization is preferably performed by a polymerization reaction. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator. A photopolymerization reaction is preferred.
Examples of photopolymerization initiators include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ethers (US Pat. No. 2,448,828). No. description), α-hydrocarbon substituted aromatic acyloin compounds (U.S. Pat. No. 2,722,512), polynuclear quinone compounds (U.S. Pat. Nos. 3,046,127 and 2,951,758). ), Combinations of triarylimidazole dimers and p-aminophenyl ketones (described in US Pat. No. 3,549,367), acridine and phenazine compounds (Japanese Patent Laid-Open No. 60-105667), U.S. Pat. No. 4,239,850) and oxadiazole compounds (described in U.S. Pat. No. 4,212,970).

The amount of the photopolymerization initiator used is preferably in the range of 0.01 to 20% by mass, more preferably in the range of 0.5 to 5% by mass, based on the solid content of the coating solution.
It is preferable to use ultraviolet rays for light irradiation for polymerization of liquid crystalline molecules.
The irradiation energy is preferably in the range of ^{20mJ / cm 2 ~50J / cm 2} , more preferably in the range of 20~5000mJ / cm ^2, more preferably in the range of 100 to 800 mJ / cm ² . In order to accelerate the photopolymerization reaction, light irradiation may be performed under heating conditions.
A protective layer may be provided on the optically anisotropic layer.

It is also preferable to combine this optical compensation film and a polarizing film. Specifically, the optically anisotropic layer is formed by applying the coating liquid for the optically anisotropic layer as described above to the surface of the polarizing film. As a result, without using a polymer film between the polarizing film and the optically anisotropic layer, a thin polarizing plate having a small stress (strain × cross-sectional area × elastic modulus) associated with the dimensional change of the polarizing film is produced. . When the polarizing plate according to the present invention is attached to a large liquid crystal display device, an image with high display quality can be displayed without causing problems such as light leakage.
The tilt angle of the polarizing film and the optical compensation layer may be stretched so as to match the angle formed by the transmission axis of the two polarizing plates bonded to both sides of the liquid crystal cell constituting the LCD and the vertical or horizontal direction of the liquid crystal cell. preferable. A normal inclination angle is 45 °. Recently, however, devices that are not necessarily 45 ° have been developed in transmissive, reflective, and transflective LCDs, and it is preferable that the stretching direction can be arbitrarily adjusted according to the design of the LCD.

(Row 7) Liquid crystal display device Each liquid crystal mode in which such an optical compensation film is used will be described.

(TN mode liquid crystal display)
It is most frequently used as a color TFT liquid crystal display device and is described in many documents. The alignment state in the liquid crystal cell in the TN mode black display is an alignment state in which the rod-like liquid crystalline molecules rise at the center of the cell and the rod-like liquid crystalline molecules lie in the vicinity of the cell substrate.

(OCB mode liquid crystal display)
This is a bend alignment mode liquid crystal cell in which rod-like liquid crystal molecules are aligned in a substantially opposite direction (symmetrically) between the upper and lower portions of the liquid crystal cell. A liquid crystal display device using a bend alignment mode liquid crystal cell is disclosed in US Pat. Nos. 4,583,825 and 5,410,422. Since the rod-like liquid crystal molecules are symmetrically aligned at the upper and lower portions of the liquid crystal cell, the bend alignment mode liquid crystal cell has a self-optical compensation function. Therefore, this liquid crystal mode is also called an OCB (Optically Compensated Bend) liquid crystal mode.
Similarly to the TN mode, the liquid crystal cell in the OCB mode is in a black display, and the alignment state in the liquid crystal cell is such that the rod-like liquid crystal molecules rise in the center of the cell and the rod-like liquid crystal molecules lie in the vicinity of the cell substrate. .

(VA mode liquid crystal display device)
The feature is that the rod-like liquid crystalline molecules are oriented substantially vertically when no voltage is applied. In the VA mode liquid crystal cell, (1) the rod-like liquid crystalline molecules are oriented substantially vertically when no voltage is applied. In addition to a narrowly defined VA mode liquid crystal cell (described in JP-A-2-176625) that is aligned substantially horizontally when a voltage is applied, (2) the VA mode is multi-domained to expand the viewing angle ( Liquid crystal cell (in MVA mode) (SID97, Digest of tech. Papers 28 (1997) 845), (3) Rod-like liquid crystal molecules are substantially vertically aligned when no voltage is applied, and twisted A liquid crystal cell in a domain alignment mode (n-ASM mode) (described in the proceedings 58-59 (1998) of the Japanese Liquid Crystal Society) and (4) a SURVAVAL mode liquid crystal cell (LCD interface) Announced at National 98).

(IPS mode liquid crystal display)
The feature is that the rod-like liquid crystalline molecules are aligned substantially horizontally in the plane when no voltage is applied, and this is characterized by switching by changing the orientation direction of the liquid crystal with or without voltage application. Specifically, as described in JP-A No. 2004-365941, JP-A No. 2004-12731, JP-A No. 2004-215620, JP-A No. 2002-221726, JP-A No. 2002-55341, and JP-A No. 2003-195333. Things can be used.

(Other liquid crystal display devices)
The ECB mode and STN mode liquid crystal display devices can be optically compensated in the same way as described above.

(C) Application of an antireflection layer (antireflection film)
The antireflection film generally comprises a low refractive index layer which is also an antifouling layer, and at least one layer having a higher refractive index than that of the low refractive index layer (ie, a high refractive index layer and a medium refractive index layer). It is provided above.
Colloidal metal by multilayer deposition of transparent thin films of inorganic compounds (metal oxides, etc.) with different refractive indexes by chemical vapor deposition (CVD) method, physical vapor deposition (PVD) method, sol-gel method of metal compounds such as metal alkoxides Examples include a method of forming a thin film by post-processing (ultraviolet irradiation: JP-A-9-157855, plasma processing: JP-A-2002-327310) after forming an oxide particle film.
On the other hand, various antireflection films formed by laminating and applying a thin film in which inorganic particles are dispersed in a matrix have been proposed as an antireflection film having high productivity.
The antireflection film which consists of the antireflection layer which provided the anti-glare property which the antireflection film by application | coating as mentioned above provided the surface of the uppermost layer with the shape of a fine unevenness | corrugation is also mentioned.
The saturated norbornene film of the present invention can be applied to any of the above systems, but the system by coating (coating type) is particularly preferable.

(Her 1) Layer structure of coating type antireflection film An antireflection film comprising at least a middle refractive index layer, a high refractive index layer, and a low refractive index layer (outermost layer) in order on the substrate has the following relationship: Designed to have a satisfactory refractive index.
The refractive index of the high refractive index layer> The refractive index of the medium refractive index layer> The refractive index of the transparent support> The refractive index of the low refractive index layer. Also good. Furthermore, it may consist of a medium refractive index hard coat layer, a high refractive index layer and a low refractive index layer.
Examples thereof include JP-A Nos. 8-122504, 8-110401, 10-300902, JP-A 2002-243906, JP-A 2000-11706, and the like.
Other functions may be imparted to each layer, for example, an antifouling low refractive index layer or an antistatic high refractive index layer (for example, JP-A-10-206603, JP-A-2002). -243906 publication etc.) etc. are mentioned.
The haze of the antireflection film is preferably 5% or less, more preferably 3% or less. The strength of the film is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test according to JIS K5400.

(Her 2) High Refractive Index Layer and Medium Refractive Index Layer The antireflective coating layer having a high refractive index is formed from a curable film containing at least an inorganic compound ultrafine particle having a high refractive index with an average particle size of 100 nm or less and a matrix binder. Become.
Examples of the high refractive index inorganic compound fine particles include inorganic compounds having a refractive index of 1.65 or more, preferably those having a refractive index of 1.9 or more. Examples thereof include oxides such as Ti, Zn, Sb, Sn, Zr, Ce, Ta, La, and In, and composite oxides containing these metal atoms.
In order to obtain such ultrafine particles, the surface of the particles is treated with a surface treating agent (for example, silane coupling agents, etc .: JP-A Nos. 1-295503, 11-153703, 2000-9908). , Anionic compounds or organometallic coupling agents: Japanese Patent Application Laid-Open No. 2001-310432), a core-shell structure with high refractive index particles as a core (Japanese Patent Application Laid-Open No. 2001-166104, etc.), a specific dispersant Combined use (for example, Unexamined-Japanese-Patent No. 11-153703, US Patent 6,210,858B1, Unexamined-Japanese-Patent No. 2002-27776069 etc.) etc. are mentioned.
Examples of the material forming the matrix include conventionally known thermoplastic resins and curable resin films.

Further, the composition is selected from a polyfunctional compound-containing composition containing at least two radically polymerizable and / or cationically polymerizable groups, an organometallic compound containing a hydrolyzable group, and a partial condensate composition thereof. At least one composition is preferred. Examples thereof include compounds described in JP-A Nos. 2000-47004, 2001-315242, 2001-31871, and 2001-296401.
A curable film obtained from a colloidal metal oxide obtained from a hydrolyzed condensate of metal alkoxide and a metal alkoxide composition is also preferred. For example, it describes in Unexamined-Japanese-Patent No. 2001-293818.
The refractive index of the high refractive index layer is generally 1.70 to 2.20. The thickness of the high refractive index layer is preferably 5 nm to 10 μm, and more preferably 10 nm to 1 μm.
The refractive index of the middle refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.50 to 1.70.

(Her 3) Low Refractive Index Layer The low refractive index layer is formed by sequentially laminating on the high refractive index layer. The refractive index of the low refractive index layer is 1.20 to 1.55. Preferably it is 1.30-1.50.
It is preferable to construct as the outermost layer having scratch resistance and antifouling property. As means for greatly improving the scratch resistance, it is effective to impart slipperiness to the surface, and conventionally known thin film layer means such as introduction of silicone or introduction of fluorine can be applied.
The refractive index of the fluorine-containing compound is preferably 1.35 to 1.50. More preferably, it is 1.36-1.47. The fluorine-containing compound is preferably a compound containing a crosslinkable or polymerizable functional group containing fluorine atoms in the range of 35 to 80% by mass.
For example, paragraph numbers [0018] to [0026] in JP-A-9-222503, paragraph numbers [0019] to [0030] in JP-A-11-38202, and paragraph number [0027] in JP-A-2001-40284. To [0028], paragraph numbers [0012] to [0077] of JP 2000-284102 A, JP 2003-26732 A, paragraph numbers [0030] to [0047] of JP 2004-45462 A, and the like. And the compounds described.

The silicone compound is a compound having a polysiloxane structure, preferably containing a curable functional group or a polymerizable functional group in the polymer chain and having a crosslinked structure in the film. For example, reactive silicone (for example, Silaplane (manufactured by Chisso Corporation), silanol group-containing polysiloxane (Japanese Patent Laid-Open No. 11-258403, etc.) and the like can be mentioned.
The crosslinking or polymerization reaction of the fluorine-containing and / or siloxane polymer having a crosslinking or polymerizable group is performed simultaneously with or after the coating composition for forming the outermost layer containing a polymerization initiator, a sensitizer and the like is applied. It is preferable to carry out by light irradiation or heating.
Also preferred is a sol-gel cured film in which an organometallic compound such as a silane coupling agent and a specific fluorine-containing hydrocarbon group-containing silane coupling agent are cured by a condensation reaction in the presence of a catalyst.
For example, a polyfluoroalkyl group-containing silane compound or a partially hydrolyzed condensate thereof (Japanese Patent Laid-Open Nos. 58-142958, 58-147483, 58-147484, Japanese Patent Laid-Open No. 9-157582, Compounds described in JP-A-11-106704, etc.), silyl compounds containing a poly "perfluoroalkyl ether" group which is a fluorine-containing long chain group (JP 2000-117902 A, JP 2001-48590 A, Compounds described in JP 2002-53804 A) and the like.

The low refractive index layer has an average primary particle diameter of 1 to 150 nm such as a filler (for example, silicon dioxide (silica), fluorine-containing particles (magnesium fluoride, calcium fluoride, barium fluoride)) as an additive other than the above. A low refractive index inorganic compound, organic fine particles described in paragraphs [0020] to [0038] of JP-A-11-3820), silane coupling agents, slip agents, surfactants, and the like.
When the low refractive index layer is located below the outermost layer, the low refractive index layer may be formed by a vapor phase method (vacuum deposition method, sputtering method, ion plating method, plasma CVD method, etc.). The coating method is preferable because it can be manufactured at a low cost.
The film thickness of the low refractive index layer is preferably 30 to 200 nm, more preferably 50 to 150 nm, and most preferably 60 to 120 nm.

(Her 4) Hard coat layer The hard coat layer is provided on the surface of the transparent support in order to impart physical strength to the antireflection film. In particular, it is preferably provided between the transparent support and the high refractive index layer.
The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of a light and / or heat curable compound. The curable functional group is preferably a photopolymerizable functional group, and the hydrolyzable functional group-containing organometallic compound is preferably an organic alkoxysilyl compound.
Specific examples of these compounds are the same as those exemplified for the high refractive index layer.
Specific examples of the constituent composition of the hard coat layer include those described in JP-A Nos. 2002-144913, 2000-9908, and WO 00/46617.

The high refractive index layer can also serve as a hard coat layer. In such a case, it is preferable to form fine particles dispersed in the hard coat layer using the method described for the high refractive index layer.
The hard coat layer can also serve as an antiglare layer (described later) provided with particles having an average particle size of 0.2 to 10 μm to provide an antiglare function (antiglare function).
The film thickness of the hard coat layer can be appropriately designed depending on the application. The film thickness of the hard coat layer is preferably 0.2 to 10 μm, more preferably 0.5 to 7 μm.
The strength of the hard coat layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test according to JIS K5400. Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

(Her 5) Forward scattering layer The forward scattering layer is provided in order to give a viewing angle improvement effect when the viewing angle is inclined in the vertical and horizontal directions when applied to a liquid crystal display device. By dispersing fine particles having different refractive indexes in the hard coat layer, it can also serve as a hard coat function.
For example, Japanese Patent Application Laid-Open No. 11-38208 specifying a forward scattering coefficient, Japanese Patent Application Laid-Open No. 2000-199809 having a relative refractive index of a transparent resin and fine particles in a specific range, and Japanese Patent Application Laid-Open No. 2002 specifying a haze value of 40% or more. -107512 gazette etc. are mentioned.

(He 6) Other layers In addition to the above layers, a primer layer, an antistatic layer, an undercoat layer, a protective layer, and the like may be provided.

(He 7) Coating method Each layer of the anti-reflection film is formed by the dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating, micro gravure method and extrusion coating method (US Patent No. 1). 2, 681, 294 specification).

(He 8) Anti-glare function The antireflection film may have an anti-glare function that scatters external light. The antiglare function is obtained by forming irregularities on the surface of the antireflection film. When the antireflection film has an antiglare function, the haze of the antireflection film is preferably 3 to 30%, more preferably 5 to 20%, and most preferably 7 to 20%.
As a method for forming irregularities on the surface of the antireflection film, any method can be applied as long as these surface shapes can be sufficiently maintained. For example, a method of forming irregularities on the film surface using fine particles in the low refractive index layer (for example, JP 2000-271878 A), a lower refractive index layer (high refractive index layer, medium refractive index layer) Alternatively, a small amount (0.1 to 50% by mass) of relatively large particles (particle size 0.05 to 2 μm) is added to the hard coat layer to form a surface uneven film, and these shapes are maintained thereon. A method of providing a low refractive index layer (for example, JP 2000-281410 A, JP 2000-95893 A, JP 2001-100004 A, 2001-281407, etc.), an uppermost layer (antifouling layer) And a method of physically transferring the uneven shape onto the surface after coating (for example, as an embossing method, Japanese Patent Laid-Open Nos. 63-278839, 11-183710, 2000-275401) Include equal forth) and the like.

<Measurement method>
The measurement method used in the present invention is described below.
(1) Wet heat dimensional change (δL (w))
A roll-shaped sample film was cut out in the MD and TD directions, conditioned for 5 hours or more at 25 ° C. and 60% relative humidity, and then measured using a 20 cm base length pin gauge (MD (F) and TD (F), respectively). To do). This was left to stand for 500 hours in a constant temperature and humidity chamber of 60 ° C. and a relative humidity of 90% (thermo treatment). After taking out from the thermostatic chamber, the humidity was adjusted for 5 hours or more at 25 ° C. and 60% relative humidity, and then the length was measured using a 20 cm base length pin gauge (MD (t) and TD (t), respectively). The wet heat dimensional change (δMD (w), δTD (w)) in the MD and TD directions was determined by the following formula, and the larger value was defined as the wet heat dimensional change (δL (w)).
δTD (w) (%) = 100 × | TD (F) −TD (t) | / TD (F)
δMD (w) (%) = 100 × | MD (F) −MD (t) | / MD (F)

(2) Dimensional change in dry heat (δL (d))
The thermo-treatment of the above wet heat dimensional change was obtained in the same manner except that it was changed to 500 hours at 80 ° C. dry.

(3) Re, Rth
After the sample film was conditioned for 24 hours at 25 ° C. and 60% relative humidity, the film surface was measured at 25 ° C. and 60% relative humidity using an automatic birefringence meter (KOBRA-21ADH: manufactured by Oji Scientific Instruments). In contrast, the retardation value at the wavelength of 590 nm was measured from the direction inclined in increments of 10 ° from + 50 ° to −50 ° from the normal to the film plane with the vertical direction and the slow axis as the rotation axis. Re) and the retardation value (Rth) in the film thickness direction were calculated.

(4) Moist heat change of Re and Rth After adjusting the humidity of the sample film at 25 ° C. and a relative humidity of 60% for 5 hours or more, Re and Rth were measured by the above method (referred to as Re (F) and Rth (F)). . This was left to stand for 500 hours in a constant temperature and humidity chamber of 60 ° C. and a relative humidity of 90% (thermo treatment). After taking out from the constant temperature and humidity chamber, the humidity was adjusted for 5 hours or more at 25 ° C. and 60% relative humidity, and then Re and Rth were measured by the above-described method (referred to as Re (t) and Rth (t)). Changes in wet heat of Re and Rth were determined by the following formula.
Change in wet heat of Re (%) = 100 × (Re (F) −Re (t)) / Re (F)
Change in wet heat of Rth (%) = 100 × (Rth (F) −Rth (t)) / Rth (F)

(5) Changes in dry heat of Re and Rth All of the above were obtained in the same manner except that the thermotreatment of the change in wet heat of Re and Rth was changed to 500 hours at 80 ° C. dry.

(6) Fine retardation unevenness After adjusting the sample film to 25 ° C. and 60% relative humidity for 5 hours or more, 0.1 mm using an ellipsometer (manufactured by UNIOPT Co., Ltd., automatic birefringence measuring apparatus ABR-10A-10AT) Ten points of Re were measured while shifting in the MD direction. A value (MD fine retardation unevenness) obtained by dividing the difference between the maximum value and the minimum value by the average value of 10 points was obtained. Similarly, the measurement was performed while shifting in the TD direction by 0.1 mm (uneven TD fine retardation). The larger one of MD fine retardation unevenness and TD fine retardation unevenness was defined as fine retardation unevenness.

(7) Longitudinal / Horizontal ratio Calculate the value (L / W) obtained by dividing the distance between the nip rolls used for stretching (L: the distance between the cores of two pairs of nip rolls) by the width (W) of the saturated norbornene film before stretching. Asked. When there were three or more pairs of nip rolls, the largest L / W value was taken as the aspect ratio.

(8) Relaxation rate It calculated | required by dividing the length to ease by the dimension before extending | stretching, and showing by a percentage.

(9) Tg
20 mg of a sample was placed in a DSC measurement pan, and this was heated from 30 ° C. to 250 ° C. at 10 ° C./min in a nitrogen stream, and then cooled to 30 ° C. at −10 ° C./min. Thereafter, the temperature was raised again from 30 ° C. to 250 ° C., and the temperature at which the baseline started to deviate from the low temperature side was defined as the glass transition temperature (Tg).

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

1. Saturated norbornene resin (1-1) Saturated norborn resin-A
6-methyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 10 parts by mass of a 15% cyclohexane solution of triethylaluminum as a polymerization catalyst, triethylamine 5 parts by mass and 10 parts by mass of a 20% cyclohexane solution of titanium tetrachloride were added to perform ring-opening polymerization in cyclohexane, and the resulting ring-opening polymer was hydrogenated with a nickel catalyst to obtain a polymer solution. This polymer solution was coagulated in isopropyl alcohol and dried to obtain a powdery resin. The number average molecular weight of this resin was 40,000, the hydrogenation rate was 99.8% or more, and the Tg was 139 ° C.

(1-2) Saturated norvol resin-B
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2.5, 1 ^7.10] -3- dodecene (specific monomer B) and 100 parts by mass, 5- (4-biphenyl carbonyl oxy) bicyclo [ 2.2.1] Charged 150 parts by mass of hept-2-ene (specific monomer A), 18 parts by mass of 1-hexene (molecular weight regulator), and 750 parts by mass of toluene into a nitrogen-substituted reaction vessel, This solution was heated to 60 ° C. Subsequently, 0.62 parts by mass of a toluene solution of triethylaluminum (1.5 mol / l) as a polymerization catalyst and tungsten hexachloride modified with t-butanol and methanol (t-butanol: methanol: By adding 3.7 parts by mass of a toluene solution (concentration 0.05 mol / l) of tungsten = 0.35 mol: 0.3 mol: 1 mol), the system is heated and stirred at 80 ° C. for 3 hours. A ring-opening polymer solution was obtained by a ring-opening polymerization reaction. The polymerization conversion rate in this polymerization reaction was 97%, and the resulting ring-opened polymer had an intrinsic viscosity (ηinh) measured in chloroform at 30 ° C. of 0.65 dl / g.
The autoclave was charged with 4,000 parts by mass of the ring-opening polymer solution thus obtained, and 0.48 part by mass of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution. And a hydrogenation reaction was performed by heating and stirring for 3 hours under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C. After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover a coagulated product, which was dried to obtain a hydrogenated polymer (specific cyclic polyolefin resin). The hydrogenated polymer thus obtained was measured for hydrogenation rate of olefinically unsaturated bonds using 400 MHz, ¹ H-NMR, and found to be 99.9%. The Tg was 110 ° C., and when the number average molecular weight (Mn) and the mass average molecular weight (Mw) in terms of polystyrene were measured by the GPC method (solvent: tetrahydrofuran), the number average molecular weight (Mn) was 39,000 and the mass average The molecular weight (Mw) was 126,000, and the molecular weight distribution (Mw / Mn) was 3.23.

2. Film Formation (2-1) Melt Film Formation Fine particles composed of silicon dioxide listed in Table 1 were added to the saturated norbornene resin-A, and formed into cylindrical pellets having a diameter of 3 mm and a length of 5 mm. This was dried with a vacuum dryer at 110 ° C., the water content was adjusted to 0.1% or less, and then charged into a hopper adjusted to (Tg−10 ° C.). Similar results were obtained when titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, talc, clay or the like was used instead of silicon dioxide.
After adjusting the melting temperature so that the melt viscosity becomes 5000 Pa · s and melting using a single-screw kneader at this temperature for 5 minutes, from a T-die set higher by 10 ° C. than the melting temperature (Tg-5 ° C. The film was cast on a casting drum set to) and solidified to form a film. At this time, each level electrostatic application method (a 10 kV wire was placed 10 cm from the point where the melt was attached to the casting drum) was used. The solidified melt was peeled off and wound up. In addition, after trimming both ends (each 3% of the total width) just before winding, the both ends were subjected to thicknessing (knurling) with a width of 10 mm and a height of 50 μm. In each level, the width was 1.5 m, and 3000 m was wound at 30 m / min.
In addition, a commercially available saturated norbornene film (melted film), ZEONOR (ZF-14 manufactured by Nippon Zeon Co., Ltd .: described as Z in Table 1) was also used. The Tg of this film was 136 ° C.

(2-2) Solution Film Formation Fine particles comprising the above saturated norbornene resin-B and silicon dioxide described in Table 1 were added to toluene with stirring so as to have a concentration of 30%. Similar results were obtained when titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, talc, clay or the like was used instead of silicon dioxide.
When the addition was completed, stirring was stopped and the slurry was swelled at 25 ° C. for 3 hours to prepare a slurry. This was stirred again and dissolved completely (this solution is called a dope). The viscosity of this solution at room temperature was 30,000 mPa · s). This was filtered with a filter paper having an absolute filtration accuracy of 0.01 mm (manufactured by Toyo Filter Paper Co., Ltd., # 63), and further filtered with a filter paper having an absolute filtration accuracy of 2.5 μm (manufactured by Pall, FH025).
The above-mentioned dope was heated to 35 ° C. and cast on a mirror surface stainless steel support having a band length of 60 m set at 25 ° C. The Gieseer used was similar to that described in Japanese Patent Application Laid-Open No. 11-314233. The casting speed was 60 m / min and the casting width was 250 cm.
The residual solvent was peeled off at 100% by mass, dried at 130 ° C., and then wound up when the residual solvent amount became 0.3% by mass or less to obtain a saturated norbornene film. The obtained film was trimmed at both ends by 3 cm, and then a knurling having a height of 100 μm was imparted to a portion 2 to 10 mm from both ends, and wound into a 3000 m roll.

3. Stretching (3-1) Longitudinal (MD) Stretching The saturated norbornene film obtained by the above melt film formation and solution film formation was used in two pairs of nip rolls, and the aspect ratio / method shown in Table 1 (diagonal, parallel) The film was stretched at a stretching speed of (Tg + 15 ° C.) at the magnification described in Table 1. After longitudinal stretching, longitudinal relaxation was performed in Tg at the relaxation rate and position described in Table 1 (after longitudinal stretching and after lateral stretching (described as “longitudinal after” and “after lateral” in Table 1)). The longitudinal relaxation after the longitudinal stretching was carried out by slowing the speed of the transport roll arranged immediately after the longitudinal stretching nip roll. On the other hand, relaxation after transverse stretching was carried out by providing a heat treatment zone immediately after the tenter and transporting it at a low tension at Tg.

(3-2) Transverse (TD) Stretching After longitudinal stretching and longitudinal relaxation, stretching was performed in the transverse direction at a magnification described in Table 1 using a tenter (Tg + 10 ° C.). After this, Tg was relaxed in the lateral direction as described in Table 1.

4). Evaluation of stretched film Wet heat dimensional change (δL (w)), dry heat dimensional change (δL (d)), wet heat, Re, Rth before dry heat treatment (fresh), and fine retardation Unevenness, wet heat changes of Re and Rth (δRe (w), δRth (w)), and dry heat changes of Re and Rth (δRe (d), δRth (d)) were measured by the above methods and listed in Table 1. did. Those implementing the present invention showed good performance. On the other hand, those outside the scope of the present invention have deteriorated optical characteristics. In particular, the reduction according to Example 1 of JP 2001-42130 A (Comparative Example 7 in Table 1) was particularly remarkable. On the other hand, Example 30 which implemented this invention on the conditions close | similar to the comparative example 7 showed favorable performance.

5. Preparation of polarizing plate (5-1) Surface treatment In any level, the film surface was subjected to corona treatment so that the contact angle with water was 45 degrees.

(5-2) Preparation of Polarizing Film According to Example 1 of JP-A-2001-141926, a polarizing film having a thickness of 20 μm was prepared by giving a circumferential speed difference between two pairs of nip rolls and extending in the longitudinal direction. In addition, although the polarizing film extended | stretched so that an extending | stretching axis | shaft might become 45 degrees diagonally like Example 1 of Unexamined-Japanese-Patent No. 2002-86554 was produced similarly, subsequent evaluation results are the same results as the above-mentioned thing. Obtained.

(5-3) Bonding The polarizing film obtained in (5-2) and a stretched saturated norbornene film (retardation plate) surface-treated in (5-1) and a saponified polarizing plate protective film (trade name: Fujitac) ). At this time, the retardation plate and the polarizing film were bonded using an epoxy adhesive. Moreover, between Fujitac and a polarizing film, it bonded together using 3% aqueous solution (PVA-117H by Kuraray Co., Ltd.) as an adhesive agent. The laminating direction was such that the longitudinal direction of the polarization axis and the retardation plate was 45 degrees.
The fresh polarizing plate thus obtained, the polarizing plate after wet thermo treatment (60 ° C., relative humidity 90% for 500 hours) and dry thermo treatment (drying at 80 ° C. for 500 hours), and saturated norbornene film as liquid crystal The 20-inch VA liquid crystal display device described in FIGS. 2 to 9 of JP-A-2000-154261 was attached to the liquid crystal display device. This was compared with a product using a fresh polarizing plate and a product using a dry thermo-treated or wet thermo-treated polarizing plate, and visually evaluated to show the ratio of the color unevenness generation area to the total area. It was described in. Good performance was obtained with the present invention.

6). Preparation of optical compensation film (6-1) Preparation of optical compensation film The stretched saturated norbornene film of the present invention was used in place of the cellulose acetate film coated with the liquid crystal layer of Example 1 of JP-A-11-316378. . At this time, an optical compensation film prepared using a stretched saturated norbornene film (fresh product) immediately after film formation / stretching, and wet thermo treatment (60 ° C., relative humidity 90% for 500 hours) or dry thermo treatment (80 ° C. dry Optical compensation films prepared using stretched saturated norbornene films after 500 hours) were compared. The region where the color unevenness occurred was visually evaluated, but no color unevenness was observed in any of the optical compensation films using the stretched saturated norbornene film of the present invention, and good optical performance was obtained.

(6-2) Preparation of optical compensation filter film An optical compensation filter using the stretched norbornene film of the present invention described above instead of the cellulose acetate film coated with the liquid crystal layer of Example 1 of JP-A-7-333433. A film was prepared. When a comparative test was conducted in the same manner as in (6-1) above, good optical performance was obtained in all cases.

7). Preparation of Low Reflective Film According to Example 47 of the Japan Society of Invention Public Technical Report (Public Technical Number 2001-1745, Issued on March 15, 2001, Invention Association) As a result, good optical performance was obtained.

8). Preparation of liquid crystal display element The polarizing plate of the present invention is applied to the liquid crystal display device described in Example 1 of JP-A-10-48420 and the discotic liquid crystal molecule described in Example 1 of JP-A-9-26572. Including an optically anisotropic layer, an alignment film coated with polyvinyl alcohol, a 20-inch VA liquid crystal display device described in FIGS. 2 to 9 of JP-A-2000-154261, and FIGS. 10 to 10 of JP-A-2000-154261. The 20-inch OCB type liquid crystal display device described in No. 15 and the IPS type liquid crystal display device shown in FIG. 11 of JP-A-2004-12731 were used. Furthermore, the low reflection film of the present invention was applied to the outermost layer of these liquid crystal display devices for evaluation. A good liquid crystal display element in which color unevenness did not occur even when placed in a high temperature and high humidity environment for a long time was obtained.

  The saturated norbornene film of the present invention can suppress the occurrence of color unevenness even when it is incorporated in a liquid crystal display device and placed under high temperature and high humidity. Moreover, according to the manufacturing method of this invention, the saturated norbornene film which has such a property can be manufactured efficiently. Furthermore, the polarizing plate, the optical compensation film, the antireflection film, and the liquid crystal display device of the present invention can exhibit excellent functions even under high temperature and high humidity. Therefore, the present invention has high industrial applicability.

It is the schematic which shows the apparatus for performing longitudinal stretch through the film diagonally, and also carrying out longitudinal relaxation. It is the schematic which shows the conventional regular longitudinal stretch apparatus. It is the schematic which shows the structure of an extruder.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1a, 1b 1st nip roll 2a, 2b 2nd nip roll 3 Conveyance roll L Stretching interval 22 Extruder 32 Cylinder 40 Supply port A Supply part B Compression part C Measurement part

Claims (16)

  Both wet heat dimensional change (δL (w)) and dry heat dimensional change (δL (d)) are 0% to 0.2%, and in-plane retardation (Re) wet heat change (δRe (w)) And the change in dry heat (δRe (d)) is 0% to 10%, and the wet heat change (δRth (w)) and the dry heat change (δRth (d)) of the retardation (Rth) in the thickness direction. A saturated norbornene film characterized in that all are 0% to 10%.   The saturated norbornene film according to claim 1, wherein the fine retardation unevenness is 0% to 10%.   The saturated norbornene film according to claim 1, wherein Re is 0 nm to 300 nm and Rth is 30 nm to 500 nm.   The saturated norbornene film according to any one of claims 1 to 3, further comprising 1 mass ppm to 10,000 mass ppm of fine particles with respect to the saturated norbornene resin.   The saturated norbornene film according to any one of claims 1 to 4, wherein the amount of residual solvent is 0.01 mass% or less. Both wet heat dimensional change (δL (w)) and dry heat dimensional change (δL (d)) are 0% to 0.2%, and in-plane retardation (Re) wet heat change (δRe (w)) The change in dry heat (δRe (d)) is 0% to 10%, and the wet heat change (δRth (w)) and dry heat change (δRth (d)) of the retardation (Rth) in the thickness direction. Both are methods for producing a saturated norbornene film that is 0% to 10%,
After film formation of saturated norbornene, the length / width ratio (L / W), which is the ratio between the width (W) of the film before stretching and the stretching interval (L), exceeds 0.01 and is less than 0.3. A method for producing a saturated norbornene film, characterized by comprising a step of longitudinally stretching 1% to 300% and further relaxing 1% to 50% in the longitudinal direction.   The method for producing a saturated norbornene film according to claim 6, wherein the longitudinal stretching is performed by passing the saturated norbornene film diagonally between two pairs of nip rolls.   The method for producing a saturated norbornene film according to claim 6 or 7, wherein transverse stretching is performed after relaxation in the longitudinal direction.   The method for producing a saturated norbornene film according to claim 8, wherein the transverse stretching is performed at a stretch ratio of 1% to 250% using a tenter.   10. The method for producing a saturated norbornene film according to claim 8, wherein after the transverse stretching, relaxation is performed in the transverse direction by 1% to 50%.   The method for producing a saturated norbornene film according to any one of claims 6 to 10, wherein the film formation of the saturated norbornene is performed by a melt film forming method.   The saturated norbornene film manufactured by the manufacturing method as described in any one of Claims 6-11.   A polarizing plate comprising at least one layer of the saturated norbornene film according to any one of claims 1 to 5 and 12 laminated on a polarizing film.   The optical compensation film which used the saturated norbornene film as described in any one of Claims 1-5 and 12 for the base material.   The antireflection film which used the saturated norbornene film as described in any one of Claims 1-5 and 12 for the base material.   The liquid crystal display device using the saturated norbornene film as described in any one of Claims 1-5 and 12.

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