JP2005104148A - Cellulose acylate film and solution film forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To comprehensively improve defects in appearance accompanying the increase in the speed of a film forming process. <P>SOLUTION: A dope is prepared by dissolving in an organic solvent a cellulose acylate satiffying the following conditions: the degree of substitution of hydroxyl group in the cellulose conforms to 1.5≤A+B≤3.0, 2.0≤A≤3.0 and 0≤B≤1.0, wherein A and B represent acyl groups substituted for hydroxyl groups in the cellulose with A standing for the degree of substitution by the acetyl group and B standing for the degree of substitution by the acyl group having 3 to 22 carbon atoms. The dope is cast from a casting die 15 onto an endless belt 14 revolving within a casing 11, and dried to form a film 24. A wind pressure pulsation in the casing 11 is suppressed by installing a pulse absorption chamber 20 in the casing 11. A bead pulsation is suppressed; by arranging labyrinths 16, 17 and a seal at least in one side, front or rear, of a casting section A, and by depressurizing, from backside, a ribbon made of beads delivered from the casting die 15. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a cellulose acylate film suitably used in various apparatuses such as a silver halide photographic light-sensitive material and a functional film for electronic materials, and a method for producing the same.

Cellulose triacetate, which is representative of cellulose acylate, has been used for many years as a support for silver halide photographic light-sensitive materials because of its mechanical properties, transparency, and features of resolving curl due to development. In addition, the cellulose acetate film is from its optical isotropy,
Further, it is also used in liquid crystal display devices whose market is expanding in recent years. As a specific use in a liquid crystal display device, a protective film for a polarizing plate and a color filter are typical,
In recent years, there has been a significant increase in the development of electronic materials using the small optical anisotropy. For example, cellulose triacetate is rapidly used as a protective film for liquid crystal display devices for personal computers, which is the infrastructure, for the IT revolution that has recently brought about social changes all over the world. Furthermore, it is not just a protective film, but a WV film released by Fuji Photo Film Co., Ltd. (Wide View Film: a film that allows viewing angle expansion)
Some of them have been used with functions. WV has been introduced to the market rapidly, which greatly improves the visibility of liquid crystal display devices. Furthermore, instead of cathode ray tube type CRT,
Because it is energy-saving, lightweight, and does not take up space, it is also being applied to anti-reflection coatings for liquid crystal televisions (for example, CV films manufactured by Fuji Photo Film Co., Ltd.) that are currently being rapidly introduced into the market. . In recent years, it has been applied as a retardation film and an optical compensation film for VA-type and IPS-type liquid crystal display devices that also serve as a polarizing plate protective film by imparting appropriate optical characteristics to cellulose triacylate.

The cellulose acetate film is generally produced by a solution casting method or a melt casting method. In the solution casting method, a solution (dope) in which cellulose acetate is dissolved in a solvent is cast on a metal support, and the solvent is evaporated to form a film. In the melt film forming method, a cellulose acetate melted by heating is cast on a support and cooled to form a film. The solution casting method can produce a good film with higher planarity than the melt casting method. For this reason, the solution casting method is generally employed in practice. The solution casting method is described in many documents. In the recent solution casting method, it is a problem to improve the productivity of the casting process by shortening the time required to peel the molded film on the support after casting the dope onto the support. It has become. For example, Patent Document 1 proposes shortening the time until stripping after casting by casting a high-concentration dope on a cooling drum.

However, recent advances in high definition and large screens of liquid crystal display devices are remarkable, and the required quality for cellulose triacetate produced by the solution casting method is rapidly becoming severe.
As for appearance defects such as foreign matters that become bright spot defects, scratches during conveyance, and thickness variation, several levels of quality are required compared to several years ago. In particular, the thickness variation in the casting direction is the structure and arrangement of the casting die, the vacuum suction of beads discharged from the die lip, the physical properties such as the viscosity of the cellulose triacetate solution, the drying method on the support surface, the peeling method from the support, Individual improvements such as relaxation under stretching conditions have been proposed.
Japanese Patent Publication No. 5-17844

However, in order to respond to the rapid increase in demand for liquid crystal display devices in recent years, it has become essential to improve productivity by speeding up casting. As the speed increases, the amount of dope discharged from the die and the linear flow velocity increase, and the drying speed on the support surface requires an increase in the drying air supply.
The influence on the thickness fluctuation due to the vibration of the bead due to the wind pressure vibration and the accompanying air becomes large. In addition, the leveling effect on the support surface is also reduced, and complex factors such as worsening of step unevenness due to peeling resistance at the time of peeling and reduction of relaxation effect at the time of stretching are intricately entangled, and the required thickness for each measure There was a limit to achieving the change.

An object of the present invention is to establish a method for producing a stable cellulose acylate film that comprehensively improves appearance defects associated with higher speeds. In particular, the thickness variation in the casting direction is to be improved.

For this purpose, it was first necessary to suppress the vibration of the die bead part as much as possible in order to increase the speed. We found that this could not be achieved by a single strategy, but could be achieved by combining various strategies. That is, in order to increase the speed, a device for absorbing wind pressure vibrations is installed in the casing in order to suppress the fluctuation in the wind pressure of the dry supply air that increases to enhance drying on the support, and further the wind that goes around the die bead is suppressed. For this purpose, a labyrinth and a seal are provided around the bead, and the bead portion is depressurized later to hold down the bead in order to suppress the disturbance of the bead due to the air accompanying the rotation of the support. Furthermore, the length of the bead was shortened to increase the resistance to vibration. Furthermore, the vibration of the ear part could be suppressed by dropping a good solvent on the ear part of the bead which is most likely to vibrate. Even if the vibration of the bead is suppressed as much as possible, the drying speed on the support becomes faster and the leveling effect is reduced. Also, the resistance force at the time of peeling becomes stronger, and the unevenness due to the resistance at the time of peeling cannot be ignored. A stripping accelerator for reducing the resistance at the time of stripping was also employed, and it was found that the thickness variation could be improved by a combined effect.

  The object of the present invention has been achieved by the following embodiments.

(1) A solution in which a dope prepared by dissolving cellulose acylate in an organic solvent is cast from a casting die onto a support consisting of an endless belt or a drum rotating in a casing and dried to form a film. In the membrane method, at least one wind pressure vibration suppressing means for suppressing wind pressure vibration in the casing is provided in the casing, and at least in front of, behind, and behind the casting portion of the casting support on which the dope is cast from the die. However, a solution casting method characterized in that a labyrinth and a seal are provided on either side, and the ribbon formed by the beads discharged from the casting die is decompressed from the rear. The cellulose acylate has a degree of substitution with a hydroxyl group of cellulose.
(I) 2.5 ≦ A + B ≦ 3.0
(II) 0 ≦ A ≦ 3.0
(III) 0 ≦ B ≦ 2.9
Is more preferable,
(I) 2.5 ≦ A + B ≦ 2.95
(II) 0.1 ≦ A ≦ 2.95
(III) 0 ≦ B ≦ 2.5
And more preferably
(I) 2.5 ≦ A + B ≦ 2.95
(II) 2.0 ≦ A ≦ 2.95
(III) 0 ≦ B ≦ 1.2
It is. In the formula, A and B represent a substituent of an acyl group substituted with a hydroxyl group of cellulose, A represents a substitution degree of an acetyl group, and B represents a substitution degree of an acyl group having 3 to 22 carbon atoms.
(2) The wind pressure vibration suppressing means is formed using an elastic thin film, and is configured such that the thin film is elastically deformed in response to wind pressure vibration in the casing, and openings are provided at both ends of the seal. The solution casting method as described in (1) above, wherein
(3) The distance between the die and the support is set to 0.3 to 3.5 mm, the bead length is shortened, the bead vibration is set to 10 to 60 Hz, and the thickness variation of 1 to 100 mm period after film formation is suppressed. The solution casting method according to any one of (1) and (2) above,
(4) When depressurizing from the rear of the casting die using the decompression chamber, a buffer tank for absorbing pressure vibration is provided in the middle of the decompression chamber from the decompression pump, and the sectional area of the buffer tank / the sectional area of the duct piping 5 to 200 times, the buffer tank length is 1 m or more, and a buffer tank in which means for retaining the air flow is installed is used. The solution casting method as described in one.
(5) The solution casting method according to any one of (1) to (4) above, wherein a good solvent for the solute of the solution is dropped onto the ear portion of the bead portion cast from the die. .
(6) Any one of the above (1) to (5), characterized in that a peeling accelerator is added to the organic solvent-based dope or cellulose acylate to reduce the peeling resistance when the dope is peeled off from the support. One solution casting method.
(7) The stripping accelerator is a polybasic acid, partial ester, alkali metal salt, or alkaline earth metal salt having an acid dissociation constant pKa in an aqueous solution of 1.93 to less than 4.50, The solution casting method as described in (6) above.
(8) The cellulose acylate film has a multilayer structure of three or more layers, and the release accelerator is added to a layer in contact with the support at least. Solution casting method.
(9) The film after casting contains 3 to 20% by weight of a plasticizer, 0.001 to 5% by weight of an ultraviolet absorber, and 0.001% to 5% of fine particle powder with respect to cellulose acylate. A cellulose acylate film produced by the solution casting method according to any one of (1) to (8) above, wherein the cellulose acylate film is contained by weight%.
(10) comprising a retardation control agent for a lower fatty acid ester film of cellulose comprising a compound having a molecular structure that has at least two aromatic rings and does not sterically hinder the conformation of the two aromatic rings. A cellulose acylate film produced by the solution casting method according to any one of (1) to (8) above.
(11) Including 0.3 to 20 parts by weight of a compound having a molecular structure that has at least two aromatic rings and does not sterically hinder the conformation of the two aromatic rings with respect to 100 parts by weight of cellulose acylate The retardation value (Rth550) in the thickness direction at a wavelength of 550 nm is 70 to 4.
Characterized in that it comprises a lower fatty acid ester film of cellulose of 00 nm
(1) to (8) An optical compensation sheet produced by the solution casting method according to any one of the above.
(12) The optical compensation sheet as described in (11) above, wherein an optically anisotropic layer containing a discotic liquid crystalline molecule is provided on the aforementioned lower fatty acid ester film of cellulose.
(13) The composition comprises 0.01 to 20 parts by weight of a discotic compound with respect to 100 parts by weight of cellulose ester, and has a thickness direction retardation value (Rth550) measured at a wavelength of 550 nm of 60 to 1000 nm. A cellulose acylate film produced by the solution casting method according to any one of (1) to (8) above.
(14) The cellulose acylate film as described in (13) above, wherein the discotic compound is a compound having a 1,3,5-triazine ring.
(15) A compound having a triphenylene ring is added to 100 parts by weight of cellulose acylate.
. Including 01 to 20 parts by weight, retardation value in the thickness direction at a wavelength of 550 nm (Rt
A cellulose acylate film, wherein h550) is from 70 to 400 nm and is produced by the solution casting method according to any one of (1) to (8) above.
(16) Cellulose acylate containing 0.01 to 20 parts by weight of a compound having a triphenylene ring with respect to 100 parts by weight of cellulose acylate ester and having a retardation value (Rth550) in the thickness direction at a wavelength of 550 nm of 70 to 400 nm. An optical produced by the solution casting method according to any one of (1) to (8) above, wherein an optically anisotropic layer containing a discotic liquid crystalline molecule is provided on the film. Compensation sheet.
(17) The cellulose acylate film according to any one of (8) to (14) above, which is stretched from 101 to 130% in the casting direction and from 101 to 150% in the vertical direction of casting, and has a thickness of from 40 to 100 μm.
(18) A polarizing plate comprising the cellulose acylate described in (17) above.
(19) A liquid crystal display device equipped with the polarizing plate described in (18).
(20) The liquid crystal display panel according to (19) is a TN type, OCB type, VA type, IPS type, transflective type, reflective type, liquid crystal display device.

According to the present invention, the substitution degree of the hydroxyl group of cellulose is 2.5 ≦ A + B ≦ 3.0, 2.0 ≦.
A ≦ 3.0, 0 ≦ B ≦ 2.9 (A and B represent the degree of substitution of the acyl group substituted with the hydroxyl group of cellulose, A represents the degree of substitution of the acetyl group, and B represents 3 to 3 carbon atoms. In the solution film-forming method in which cellulose acylate satisfying the condition of 22) is dissolved in a solvent and cast, wind pressure fluctuation suppression means is installed in the casing of the support, A labyrinth seal that prevents the wind from flowing around is provided, the bead length is shortened as much as possible, the bead is fixed under reduced pressure, a solvent is dripped onto the ear, and an additive that reduces the peeling resistance when peeling off from the support is added. By adopting it, we were able to establish a manufacturing method that can improve the thickness fluctuation even if the casting speed is increased.
This was the same effect regardless of whether the solvent was a normal methylene chloride solvent or a non-chlorine solvent.

(Wind pressure vibration suppression means)
FIG. 1 is a schematic view showing an apparatus for suppressing wind pressure vibration. The solution casting apparatus 10 includes a casing 11, drums 12 and 13, a belt 14, a casting die 15, shielding plates 16, 17 and 18, a vibration absorption chamber 20, and a peeling roller 21. Two drums 12 and 13 are arranged in the casing 11, and an endless belt 14 serving as a support for the polymer solution is stretched between the two drums 12 and 13. Around one drum 12, there is a shielding plate 1
6, 17 and 18 are provided. The shield plates 16, 17 and 18 are provided with well-known labyrinths 16 a, 17 a and 18 a at portions facing the belt 14. These shielding plates 16
, 17 and 18, the inside of the casing 11 is divided into three regions A, B and C.

The area A is partitioned as a space covering the upper right half of the drum 12 by the shielding plates 16 and 17.
In the region A, a casting part for flowing the polymer solution on the belt 14 is arranged. A casting die 15 for flowing the polymer solution on the belt 14 is arranged on the upper right side of the drum 12, and the polymer solution is continuously flowed on the belt 14 from a die slit (not shown) to be cast into a film shape. . The shielding plates 16 and 17 prevent the drying air 22 from hitting the casting die 15 and the bead portion 15a. Further, a vibration absorbing chamber 20 described later is attached to the casing 11 in close contact with the opening 11 a provided in the casing 11 above the casting die 15.

The region B is partitioned as a space that covers most of the belt 14 by the shielding plates 16 and 18. Dry air 22 is sent to this region B. The drying air 22 is supplied from the air inlets 11 b and 1 of the casing 11.
1c is sent into the casing 11 and exhausted from the exhaust port 11d. The polymer solution cast on the belt 14 is dried by the drying air 22. Then, the dry air 22a containing the evaporated solvent is exhausted from the exhaust port 11d. The polymer solution cast on the belt 14 is dried by the drying air 22 while the belt 14 goes around between the drums 12 and 13 to form a film 24.

The region C is partitioned as a space that covers the lower right half of the drum 12 by the shielding plates 17 and 18.
In this region C, the stripping portion 25 is disposed. The stripping portion 25 is composed of a stripping roller 21. The stripping roller 21 strips the film 24 formed on the belt 14 and discharges it to the outside of the casing 11. The film 24 peeled off from the belt 14 is discharged from an opening 11e provided in the casing 11, passes through a drying device provided as necessary, and then provided outside the solution casting apparatus 10 (not shown). It is wound on a winding shaft.

In FIG. 2, the vibration absorption chamber 20 has a rectangular parallelepiped shape, and includes a lightweight frame 27 having elasticity and a thin film bag 28 formed of a thin film having elasticity. Around the vibration absorbing chamber 20, a protective frame 26 formed by a metal mesh or the like is provided. This protective frame 26 prevents the vibration absorbing chamber 20 from being damaged. The thin film bag 28 is made of polyethylene terephthalate (PET), and the opening thereof is disposed so as to cover the opening 11a of the casing 11, and is joined by an adhesive tape (not shown) or the like. The thin film bag 28 is attached to and held by the frame 27 with an adhesive or an adhesive tape. Each frame 2
7 and the protective frame 26 are arranged with coil springs 29a and 29b, respectively.
7 and the thin film bag 28 are held at predetermined positions with respect to the protective frame 26. The coil spring 29a is
It is provided so that the thin film bag 28 does not lose tension and lose its elasticity when the inside of the casing 11 is at a positive pressure due to static pressure. The coil spring 29b is provided to prevent the vibration absorbing chamber 20 from being crushed when the inside of the casing 11 is at a negative pressure due to static pressure. In addition, as for the film thickness of the thin film which forms the thin film bag 28, 20 micrometers-70 micrometers are preferable.

The vibration absorbing chamber 20 configured as described above has a thin film bag 28 so as to increase the volume of the vibration absorbing chamber 20 when the pressure of the atmosphere in the casing 11 increases due to wind pressure vibration accompanying the running of the drying air 22 and the belt 14. Is elastically deformed to absorb pressure fluctuations, and when the pressure of the atmosphere in the casing 11 is lowered, the thin film bag 2 is formed so as to reduce the volume of the vibration absorbing chamber 20.
8 is elastically deformed and similarly absorbs pressure fluctuations. In this way, the volume of the vibration absorbing chamber 20 is changed to absorb the pressure fluctuation of the atmosphere in the casing 11 to suppress the wind pressure vibration. Thereby, the film thickness nonuniformity of the film 24 which generate | occur | produces when the bead part 15a vibrates is reduced.

In the above-described embodiment, the vibration absorbing chamber 20 has a rectangular parallelepiped shape, but the present invention is not limited to this, and may have a box shape such as a columnar shape or a hemispherical shape. Moreover, you may make it close the opening 11a with one thin film, without making it into a box shape. Furthermore, although the thin film is a flat one, a bellows may be used.

FIG. 3 shows a second embodiment of the present invention, in which vibration absorbing chambers 31 and 32 are provided not only in the region A in the vicinity of the casting die 15 but also in the region B constituting the drying unit. These vibration absorption chambers 31 and 32 are configured in the same manner as the vibration absorption chamber 20 shown in FIG.
In FIG. 3, the same components as those in FIG. 1 are denoted by the same reference numerals, and redundant description is omitted. According to the present embodiment, the wind pressure vibration in the region B that directly causes the wind pressure vibration in the region A can also be suppressed by the vibration absorbing chambers 31 and 32, and the wind pressure vibration in the region A can be further suppressed. Thereby, the film thickness nonuniformity of the film 24 resulting from the vibration of the bead part 15a can be further reduced.

FIG. 4 shows a third embodiment of the present invention. In addition to the first vibration absorption chamber 20,
Sixth vibration absorbing chambers 41, 42, 43, 44, 45 are provided. As shown in FIG. 5, the second vibration absorption chamber 41 includes a thin film bag 46 having a bellows, and the thin film bag 46 expands and contracts to absorb pressure fluctuations. The third vibration absorption chamber 42 has the same configuration as that of the vibration absorption chamber 20 shown in FIG. The fourth vibration absorption chamber 43 and the fifth vibration absorption chamber 44 have substantially the same configuration as the vibration absorption chamber 20 shown in FIG.
As shown in FIG. 6, it is a positive pressure vibration absorbing chamber having only a coil spring 29a. The fifth vibration absorbing chamber 44 is held at a predetermined position with respect to a protective frame (not shown) by a holding coil spring 48. The sixth vibration absorption chamber 45 is configured substantially the same as the vibration absorption chamber 20 shown in FIG. 2, but as shown in FIG. 7, it is a negative pressure vibration absorption chamber having only a coil spring 29b. ing. 4, 6, and 7, the same components as those in FIGS. 1 and 2 are denoted by the same reference numerals, and redundant description is omitted.

According to the present embodiment, the vibration absorption chambers 43 and 44 for positive pressure are arranged in the positive pressure portion in the casing 11 in the vicinity of the air inlet 11b generated by the balance between the blowing of the dry air 22 and the exhaust gas, and the pressure fluctuations. The vibration absorbing chamber 45 for negative pressure is disposed in the negative pressure portion near the exhaust port 11d to absorb pressure fluctuation. Moreover, the vibration absorbing chamber 42 corresponding to both positive pressure and negative pressure
Thus, the pressure fluctuation in the vicinity of the shielding plate 16 is absorbed, and the pressure fluctuation in the vicinity of the casting die 15 is absorbed by the vibration absorbing chambers 20 and 41 corresponding to both the positive pressure and the negative pressure. As described above, the pressure fluctuation is absorbed by using the vibration absorption chamber corresponding to the positive pressure portion and the negative pressure portion in the casing 11 due to the balance between the blowing of the dry air 22 and the exhaust air, so that the wind pressure is more effectively achieved. Vibration can be suppressed. Thereby, the film thickness nonuniformity of the film 24 resulting from the vibration of the bead part 15a can be reduced more effectively. Note that the number and arrangement positions of the vibration absorbing chambers are not limited to those illustrated. A chamber for positive pressure or negative pressure may be provided at an appropriate position according to the wind pressure distribution of the drying air of each device.

FIG. 8 shows another embodiment in which wind pressure vibration is suppressed by using a pressure sensor 51, a low frequency amplifier 52, and a speaker 53 instead of the vibration absorption chamber 20. Pressure sensor 5
1 detects a pressure fluctuation in the region A. The output from the pressure sensor 51 is amplified by a low-frequency amplifier 52, and negative feedback is applied using a speaker 53 to absorb pressure fluctuations. Thereby, the film thickness nonuniformity of the film 24 resulting from the vibration of the bead part 15a can be reduced.

In the above embodiment, the coil spring is used to hold the frame. However, the present invention is not limited to this, and a band, a string, or the like may be used. Further, the frame itself may be composed of a band or a string. Further, the frame may be made of metal, wooden bar, plate or the like.

In each of the above-described embodiments, the solution casting apparatus using an endless belt stretched between two drums as a support has been described. However, this configuration is also applied to a solution casting apparatus that forms a support with only a drum. Needless to say, is applicable.

(Labyrinth and seal)
In FIG. 9, labyrinths 104 and 106 and seals 105 and 107 are provided on at least one of the front and rear sides of the casting die 103.
Is not particularly limited, and a fin having a large number of fins can be used. In the figure, reference numeral 101 denotes a casting band as a casting support, 102 denotes a driving drum, 10
3 is a casting die, 110 is a casing, 111 and 112 are drying air supply ducts, 115 and 11
Reference numeral 6 denotes a partition wall. The material used for the labyrinths 104 and 106 and the seals 105 and 107 is preferably a material having a low thermal conductivity. By using a material having a low thermal conductivity, condensation occurs on the labyrinths 104 and 106 and the seals 105 and 107. Can be prevented. The thermal conductivity is 15 × 10 ⁻⁴ cal / (sec · cm
² · ° C.) or less, more preferably 8 × 10 ⁻⁴ cal / (sec · cm ² · ° C.) or less, specifically, a fluororesin such as polytetrafluoroethylene is preferred.

The labyrinths 104 and 106 are preferably provided over substantially the entire width of the casing 110 so that both sides thereof are close to the casing 110. By providing the labyrinths 104 and 106 substantially in the full width, the drying air can be more completely blocked. The gap between the labyrinths 104 and 106 and the casing 110 is preferably in the range of 0 to 10 mm, and more preferably in the range of 0 to 3.0 mm. Moreover, if it exceeds 10 mm, the effect which suppresses inflow of a dry wind will become small.

The clearance between the lower surface of the labyrinths 104 and 106 and the surface of the casting band 101 is 0.7 to 10 m.
The range of m is preferable, and the range of 0.7 to 3.0 mm is more preferable. If the gap is less than 0.7 mm, there is a risk of contact with the base cast on the casting band 101, and 10 mm
If it exceeds, the effect of suppressing the inflow of dry air becomes small.

It is preferable that the seals 105 and 107 are made of shielding plates and are arranged so as to cover the dry air flowing from between the labyrinths 104 and 106 and the casting band 101. Also, openings are provided on both sides of the seals 105 and 107 so that the labyrinths 104 and 106 and the seal 10
It is preferable to prevent the drying air from reaching the casting portion by letting the drying air flowing through the lower portion 5,107 and flowing toward the casting portion to the side through the opening. Furthermore, the seals 105 and 107 are
It is preferable that the opening be formed between both ends of the seal and the casing so as to be not less than the width of the casting die 103 and not more than the width of the casing 110. The width of the opening (length in the width direction of the casting die) is preferably 5 to 300 mm on one side, more preferably 50 to 200 on one side.
mm, and double these on both sides. Moreover, the clearance gap between the lower surface of the front-end | tip part of the seals 105 and 107 and the surface of the casting band 101 has the preferable range of 0.7-10 mm, and is 0.7-3.0.
A range of mm is more preferable.

Further, the wind that leaks from the gap between the casting band 101 and the casing 110 provided around the casting band 101 is blocked by a wind shielding member, and the flow formed by the dope between the casting die 103 and the casting band 101 is blocked. It is preferable not to hit the rolled bead. The windshield member is disposed between the gap and the casting bead, and the gap between the windshield member and the casting support is 0.3 to 5
It is more preferable to use mm. Moreover, the said wind-shielding member is made into the casting band 1 in the said clearance gap.
01 or a labyrinth provided in either the casing 110 is preferable.

In the seal provided in front of the casting part, the tip is heated above the surface temperature of the base,
It is preferable to prevent the solvent from condensing on the seal tip due to the temperature of the gas around the seal tip being lowered due to the latent heat of vaporization of the base. The temperature at which the seal tip is heated is preferably 0 ° C. or more, more preferably 1 ° C. or more, higher than the surface temperature of the base. In addition, it is preferable that air supply means is provided in the casting part, and air is supplied by the air supply means so as not to hit the casting bead formed by the dope between the casting die and the casting support. In some cases, condensation of the solvent is prevented.

Although the labyrinths 104 and 106 and the seals 105 and 107 prevent the dry air from reaching the casting portion, the bead of the casting bead formed by the dope between the casting die 103 and the casting band 101 is suppressed. It is preferable that the wind speed of the wind striking from the drying zone is 20 m / sec or less, and the wind speed distribution in the casting width direction is within 20% of the average wind speed. More preferably, the wind speed at the seal outlet is 2 m / s or less, and more preferably 0.5 m / s or less. Also,
More preferably, the wind speed at the casting portion is 0.5 m / s or less, and still more preferably
1 m / s or less. By setting the wind speed of the casting part to 0.5 m / s or less, the ear part of the casting bead can be stabilized, the thickness unevenness at the base end part becomes small, and the casting after stripping is performed. It is possible to prevent the base from remaining on the support.

(Bead decompressor)
In FIG. 10, a back suction device 240 is provided behind the casting die 210, and the distance between the back suction device 240 and the casting band 230 is set to 0.3 to 3 mm. The pressure is set to −10 Pa to −1500 Pa, and the solution casting method back suction device is composed of two or more decompression chambers, and the widthwise end of the back suction chamber is The above solution casting method having a labyrinth structure is provided.

In the band type solution casting apparatus shown in FIG. 11, reference numeral 210 denotes a casting die.
A rotary drum 220 is provided opposite to the rotary drum 220, and the casting band 23 is provided on the rotary drum 220.
It is designed to run around 0. Further, a back suction device 240 is provided adjacent to the casting die 210, and the back suction device 240 is connected to the suction duct 25.
0 and the blower 270 via the buffer tank 260. Reference numeral 221 denotes a peeling roller.

FIG. 12 shows a partially enlarged view near the back suction device 240. Back suction device 2
Reference numeral 40 denotes a polymer solution sucked from the back of the ribbon-shaped polymer solution 201 cast from the casting die 210 to closely adhere to the support and prevent air entrainment.

The back suction device 240 has a box-like structure as a whole with a side surface corresponding to the casting die 210.

FIG. 12 is a plan view of a portion corresponding to FIG. 10, and FIG. 13 is a bottom view of the back suction device.
Shown in The back suction device 240 is closed on the top, front, rear, and both sides, and only the bottom is open. The back suction device 240 is provided for the entire width of the casting die discharge.

In the back suction device of FIG. 13, the decompression chambers 241 and 242 are divided into two chambers in the width direction, and the connection ports 243 of the suction duct are provided in the vicinity of both side ends of the upper surface of the decompression chamber 242 on the rear side. Yes. A partition 244 that partitions between the decompression chambers 241 and 242
Is a flat plate that partitions the chambers 241 and 242 from the upper end to the lower end. Accordingly, the front decompression chamber 241 is closed at the front, back, left, and right, and the top surface, and the decompression is performed by transmitting the decompression of the rear decompression chamber 242 through the gap between the bottom surface and the casting band 230 or the casting drum. Is called. The entire bottom surface of the rear decompression chamber 242 is open.
Thus, by partitioning the decompression chambers 241 and 242 into two chambers, the wind between the suction duct and the ribbon-like polymer solution is shielded to reduce the influence of the wind.

It is preferable that the end portion in the width direction of the back suction device 240 has a labyrinth structure. FIG.
In 0, the labyrinth 245 is provided at both ends of the front decompression chamber 241. Each labyrinth 245 is a flat plate that is partitioned from the upper end of the decompression chamber 241 to substantially the lower end. The labyrinth 245 suppresses the flow of wind at both ends and reduces the vortex.

The distance d between the bottom surface of the back suction device 240 and the surface of the casting band 230 is 0.3.
-3 mm, preferably 0.5-1.5 mm. If the width is smaller than 0.3 mm, the bottom surface of the back suction device 240 may rub against the surface of the support and may be damaged. If the width is larger than 3 mm, the amount of air flowing into the back suction device 240 due to the reduced pressure increases and casts. It causes the ribbon-like polymer solution to become unstable.

The static pressure of back suction is -10 to -1500 Pa, preferably -10 to -1000 Pa.
Is appropriate.

(Die height)
The distance h between the casting die and the support is usually set in the range of 0.3 mm to 3.5 mm, preferably in the range of 0.5 mm to 3 mm, but is not limited thereto. .

The polymer solution viscosity is usually set in the range of 10p to 1000p, and preferably in the range of 100p to 800p, but is not limited thereto.

The lip clearance cl is usually set in the range of 0.2 mm to 3 mm, preferably 0.
Although it is good to set in the range of 5 mm to 2 mm, it is not limited to this.

The casting speed v is usually set in the range of 3 m / min to 150 m / min, preferably 10 m / min.
Although it is good to set in the range from 100 to 100 m / min, it is not limited to this.

The thickness t of the film is preferably 20 to 500 μm, more preferably 30 to 300 μm,
Although 35-100 micrometers is the most preferable, it is not limited to this.

As the casting die, those shown in FIGS. 14 to 16 can be used.

FIG. 14 shows a casting die used for forming a single-layer film.
Two manifolds 251 are formed. FIG. 15 shows a multi-manifold type co-casting die. The co-casting die 260 is formed with three manifolds 261 and can form a film having a three-layer structure. FIG. 16 shows a feed block type co-casting die. The co-casting die 270 is provided with a manifold 271 and a feed block 272. The feed block 272 is joined to form a plurality of layers (FIG. 16). 3 layers)
The polymer solution obtained is cast.

In the above casting die, a coat hanger die is used, but the present invention is not limited to this, and a die having another shape such as a T die may be used.

In each of the above-described embodiments, the solution casting apparatus using an endless belt stretched between two drums as a support has been described. However, this configuration is also applied to a solution casting apparatus that forms a support with only a drum. Needless to say, is applicable.

(Ear part good solvent dropping method)
As shown in FIG. 17, the solution film forming apparatus 310 mainly includes a casting die 312, a casting band (corresponding to a support) 314, a decompression chamber 316, and a dropping device 318.
The casting band 314 is formed in an endless shape, and is wound around the casting drum 320 and a driving drum (not shown). The casting drum 320 runs around the driving drum and the casting drum 320 by rotating the driving drum. Casting band 3
The traveling speed of 14 is set according to the thickness of the film to be formed.

The casting die 312 is disposed to face the casting band 314 at the position of the casting drum 320. A dope containing a polymer material such as cellulose triacetate is extruded from the tip of the casting die 312 into a film shape. The extruded dope is temporarily attached to the surface of the running casting band 314 and cast. The dope on the casting band 314 is dried by evaporation of the solvent while the casting band 314 travels for one round, and a predetermined self-supporting property is obtained. Then, by stripping the cast film from the casting band 314 at a position below the casting die 312, for example, a belt-like film is obtained. A labyrinth seal 336 is provided before and after the casting die 312 with respect to the traveling direction of the casting band 314, so that the solvent gas concentration is kept constant before and after the casting portion 326. ing.

On the other hand, the decompression chamber 316 is provided on the upstream side of the casting die 312 with respect to the traveling direction of the casting band 314, and is connected to the blower 324 through the suction duct 322. By driving the blower 324, the inside of the decompression chamber 316 becomes negative pressure, and is temporarily attached to the casting band 314 in the dope casting portion 326 in the gap between the casting die 312 and the casting band 314. A suction force is applied to the surface on the side. Thereby, even if the casting band 314 is run at a high speed, the dope casting portion 326 can be stabilized. The suction duct 322 between the decompression chamber 316 and the blower 324 is provided with a buffer tank 328 having a capacity 10 to 100 times that of the decompression chamber 316, and vibrations are prevented from being transmitted to the decompression chamber 316. . The cross-sectional area of the buffer tank 316 is preferably 5 to 200 times the cross-sectional area of the suction duct 322, and more preferably 10 to 100. The length of the suction duct 322 is preferably 1 m or more. Further, it is more preferable to provide a means for retaining the air flow inside.

The dropping device 318 includes a tank 330, a pump 332, and a liquid feeding pipe 334.
By driving 32, the liquid stored in the tank 330 is fed to the liquid feeding pipe 334 and dropped from the tip of the liquid feeding pipe 334. As shown in FIG. 18, the tip of the liquid feeding pipe 334 is disposed at a position where the dropped liquid is absorbed by the ear portion 326 </ b> A of the casting portion 326.

Moreover, as a liquid dripped from the front-end | tip of the liquid feeding pipe 334, the liquid mixture which mixed the poor solvent with the good solvent with respect to the solute of dope or a good solvent is used. When the dope is a cellulose triacetate solution, dichloromethane is preferable as the good solvent, and methanol, ethanol, butanol, isobutanol, isopropanol, acetone, methyl acetate, toluene, or the like is preferable as the poor solvent. Moreover, when mixing a poor solvent with a good solvent, it is good to make the ratio of all the poor solvents to mix into less than 20 weight% with respect to the total solution of a dripping liquid, Preferably it is 13 weight% or less. The good solvent and the poor solvent are not limited to the above-described embodiments.

When the liquid whose composition is defined as described above is dropped onto the ear portion 326A of the casting portion 326, the ear portion 326 is dropped.
A becomes less susceptible to the influence of the inflow air into the decompression chamber 316. That is, when a liquid having a high proportion of the poor solvent is dropped on the ear portion 326A, gelation occurs and the ear portion 326A is likely to flutter, but when a liquid having a low proportion of the poor solvent is dropped on the ear portion 326A, the ear portion 326A is It becomes flexible and hardly shakes, and it is difficult for the ear portion 326 to flutter. Therefore, even when a high speed at which large fluctuations are likely to occur and a thin film of 20 to 100 μm (especially 35 to 80 μm) is manufactured, the generation of fluctuations can be suppressed and a good film without coating unevenness can be manufactured. can do.

Specifically, the flutter of the ear 326A has a frequency outside the range of 5 to 200 Hz and an amplitude of 1.3.
It is good to suppress to mm or less. When the flutter frequency is 5 Hz or less, the period is large and the thickness unevenness is not noticeable. When the frequency exceeds 200 Hz, the coating stripe disappears due to leveling (smoothing). Similarly, if the amplitude of the flutter is 1.3 mm or less, the coating streaks become thin, and the quality is not problematic. Therefore, the flutter of the ear portion 326A is reduced to a frequency of 5 to 200.
A film having no problem as a product can be produced by suppressing the amplitude to 1.3 mm or less outside the range of Hz.

As described above, according to the solution casting apparatus 310 of the present embodiment, a good solvent or a liquid obtained by mixing a poor solvent with a good solvent at less than 20% by weight (preferably 13% by weight or less) Ear 32
Since it dripped at 6A, the high-speed casting and thin film formation which are easy to generate | occur | produce fluttering are attained. That is, a thin film having a thickness of 20 to 100 μm (particularly 35 to 80 μm) can be manufactured, and the speed of the thin film can be increased.

(Cellulose acylate)
Details of cellulose acylate will be described. Cellulose acylate in which the substitution degree of hydroxyl group of cellulose satisfies all of the above formulas (I) to (III), and organic solvents for dissolving cellulose acylate include hydrocarbons (eg benzene, toluene), halogenated Hydrocarbons (eg methylene chloride, chlorobenzene), alcohols (eg methanol, ethanol,
Diethylene glycol), ketones (eg acetone), esters (eg methyl acetate, ethyl acetate, propyl acetate) and ethers (eg tetrahydrofuran, methyl cellosolve).

A halogenated hydrocarbon having 1 to 7 carbon atoms is preferably used, and methylene chloride is most preferably used. In addition to methylene chloride, the number of carbon atoms is 1 from the viewpoint of physical properties such as solubility of cellulose acylate, peelability from the support, mechanical strength of the film, and other optical properties.
It is preferable to mix one to several alcohols of ˜5. 2-25 mass% is preferable with respect to the whole solvent, and, as for content of alcohol, 5-20 mass% is more preferable. Specific examples of alcohol include methanol, ethanol, n-propanol, isopropanol,
Although n-butanol etc. are mention | raise | lifted, methanol, ethanol, n-butanol, or these mixtures are used preferably.

Recently, a solvent composition not using methylene chloride has been proposed in order to minimize the influence on the environment. For this purpose, ethers having 3 to 12 carbon atoms, ketones having 3 to 12 carbon atoms, and esters having 3 to 12 carbon atoms are preferable, and these are used by appropriately mixing them. These ethers, ketones and esters may have a cyclic structure. A compound having two or more functional groups of ether, ketone and ester (that is, —O—, —CO— and —COO—) can also be used as the organic solvent. Organic solvents are
It may have another functional group such as an alcoholic hydroxyl group. In the case of an organic solvent having two or more types of functional groups, the number of carbon atoms may be within the specified range of the compound having any functional group.

It is preferable that the raw material of the cellulose acylate is cotton linter and / or wood pulp. More preferably, the cotton linter and / or the wood pulp is a purified cellulose raw material. In this case, the mixing ratio of the cotton linter and the wood pulp is 0 /
It is preferable that it is 100-95 / 5. The cotton linter and / or wood pulp is α-
It is preferable to contain 80% or more of cellulose. Further, the cotton linter and / or the wood pulp is mannose / xylose = 0.35 / 1 to 3.0 / 1 (molar ratio),
It is preferable that the total content is 0.01 to 5 mol%.

The cellulose acylate is preferably cellulose alkylcarbonyl ester, alkenylcarbonyl ester, aromatic carbonyl ester, or aromatic alkylcarbonyl ester. The cellulose acylate is preferably cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate stearate, or cellulose acetate benzoate.

The cellulose acylate was produced by a combination of an activation step (pretreatment step), an acylation step (acetylation step in the case of acetyl), an aging step, a precipitation step, a purification step, a drying step, and a pulverization step. It is preferable.

The cellulose acylate preferably has a residual acetic acid amount or a C 3-22 fatty acid content of 0.5% by mass or less. Moreover, it is preferable that the cellulose acylate contains 1 ppb to 10000 ppm of at least one kind of alkali metal and / or alkaline earth metal. Further, the cellulose acylate may be aluminum, bismuth, silicon, heavy metal (chromium, manganese, iron, cobalt, nickel, copper, zinc, arsenic, silver, cadmium,
At least one of tin, antimony, gold, platinum, mercury, lead, etc.) from 1 ppb to 1000
It is preferable to contain ppm.

The amount of acetone extracted from the cellulose acylate at 25 ° C. is preferably 15% by mass or less. The substitution degree of the acyl group at the 6-position of the cellulose acylate is preferably 32% or more of the total acyl group. Further, the substitution degree of the acyl group at the 6-position of the cellulose acylate is preferably 0.88 or more. In addition, the cellulose acylate is
Cellulose acetate is preferred. Furthermore, the cellulose acylate is preferably cellulose triacetate.

The cellulose acylate preferably has a viscosity average polymerization degree of 200 to 700.
The ratio of the weight average molecular weight to the number average molecular weight of the cellulose acylate is 1.0 to 5.0.
Preferably, it is 1.0 to 4.0, more preferably 1.5 to 3.0.
Furthermore, the cellulose acylate preferably contains an acid having an acid dissociation index of 1.93 to 4.5, a partially esterified product, or a salt thereof.

The water content of the cellulose acylate is preferably 2% by mass or less. Moreover, it is preferable that the yellowness index of the said cellulose acylate is 0.1-10. Furthermore, it is preferable that the haze of the cellulose acylate is 0.05 to 5%.

The transparency of the cellulose acylate is preferably 85% or more. Moreover, it is preferable that Tg of the said cellulose acylate is 80-200 degreeC. Furthermore, it is preferable that the crystallization heat generation amount of the cellulose acylate is 2 to 20 J / g.

The organic compound having 3 to 12 carbon atoms is selected from diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxane, 1,3-dioxolane, tetrahydrofuran, anisole and phenetole. It may be a solvent.

The ketone having 3 to 12 carbon atoms may be an organic solvent selected from acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and methylcyclohexanone.

The ester having 3 to 12 carbon atoms is ethyl formate, propyl formate,
It may be an organic solvent selected from pentyl formate, methyl acetate, ethyl acetate, propyl acetate and pentyl acetate.

It is preferable that any one of the non-chlorine organic solvents is an ether, a ketone or an ester having a cyclic structure. The non-chlorine organic solvent is preferably a solvent having a solubility parameter of 19 to 21 MPa ^1/2 . Furthermore, the non-chlorine organic solvent may be an organic solvent having a dielectric constant of 2 to 35.

The non-chlorine organic solvent is preferably a solvent having an oxygen mass fraction of 0.6 to 0.15. The non-chlorine organic solvent is preferably a solvent having a dipole moment of 0.2 to 3.3. Furthermore, the non-chlorine organic solvent is preferably a solvent having a molecular weight of 150 or less. Furthermore, the non-chlorine organic solvent may be an organic solvent having an I / O value of 3 to 0.2.

The non-chlorine organic solvent is a mixed solvent of three or more different from each other, and the first solvent is at least one selected from methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, dioxolane, dioxane, or a combination thereof. The second solvent is selected from ketones having 4 to 7 carbon atoms or acetoacetate, and the third solvent has 1 carbon atom.
May be selected from 10 to 10 alcohols or hydrocarbons, and more preferably an alcohol having 1 to 8 carbon atoms. In this case, when the first solvent is a mixture of two or more solvents, the second solvent may not be present.

In the case where the non-chlorine organic solvent is a mixed solvent, the first solvent is methyl acetate,
Acetone, methyl formate, ethyl formate or a mixture thereof is preferable, and the second solvent is preferably methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl acetoacetate or a mixture thereof. The third solvent may be selected from methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, cyclohexanol, cyclohexane and hexane.

20 to 90% by mass of the first solvent, 5 to 60% by mass of the second solvent, and the third solvent.
A solvent mixed solution containing 5 to 30% by mass of the solvent may be used.

It is preferable that the composition of the mixed solvent is methyl acetate / acetone / methanol / ethanol. The composition of the mixed solvent may be methyl acetate / acetone / methanol / ethanol / butanol. The composition of the mixed solvent may be methyl acetate / methyl ethyl ketone / dioxolane / ethanol / butanol.

The plasticizer in the cellulose acylate solution is 2 to 2 with respect to the cellulose acylate solid content.
It is preferable to contain 30 mass%. It is preferable that the content of the plasticizer in the cellulose acylate film is 1-1000 mg / m ² . The plasticizer has a boiling point of 2
It is preferably a liquid of 00 to 400 ° C or a solid having a melting point of 10 to 250 ° C.

The plasticizer is preferably a phosphoric acid ester or a carboxylic acid ester. The plasticizer may be triphenyl phosphate (TPP), tricresyl phosphate (TC).
P), cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP)
), Dioctyl phthalate (DOP), diphenyl phthalate (DPP), diethyl hexyl phthalate (DEHP), triethyl O-acetylcitrate (OACTE), tributyl O-acetylcitrate (OACTB), acetyltriethyl citrate, acetyltributyl citrate , Butyl oleate, methyl acetyl ricinoleate, dibutyl sebacate, triacetin, tributyrin, butyl phthalyl butyl glycolate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate It is more preferable that Furthermore, the plasticizer is preferably (di) pentaerythritol esters, glycerol esters, diglycerol esters.

In the cellulose acylate solution, deterioration inhibitors (eg, antioxidants, peroxide decomposers,
A solution containing 0.01 to 1% by mass of a radical inhibitor, a metal deactivator, an acid scavenger, an amine) or an ultraviolet light inhibitor is preferred. It is preferable that the deterioration inhibitor is a liquid having a boiling point of 200 to 400 ° C, or a solid having a melting point of 10 to 250 ° C and 10 to 200 ° C.

The cellulose acylate film is preferably a film containing a fine particle matting agent. The Mohs hardness of the fine particle matting agent is preferably 2 to 10. Moreover, it is preferable that the average particle diameter of the said fine particle mat agent is 0.001-20 micrometers.

The cellulose acylate solution is preferably a solution containing a release agent. The release agent is preferably selected from phosphoric acid esters, sulfonic acids, and acids having an acid dissociation index pKa of 1.93 to 4.50 or salts thereof. Furthermore, the release agent is preferably selected from glycolic acid, lactic acid, malic acid, tartaric acid, citric acid, partially esterified products thereof, and salts thereof.

It is preferable that the cellulose acylate film is produced by casting the cellulose acylate solution containing any one of the above-described release agents and peeling off the metal support from 20 to 1000% by mass of the residual solvent.

The cellulose acylate film is 20% by mass of polyurethane or polyol.
It is preferable to contain the following. Moreover, it is preferable that the said cellulose acylate film is a cellulose acylate containing the antistatic agent.

In the cellulose acylate solution, the cellulose acylate preferably has a concentration of 5 to 40% by mass. Further, in the production of the cellulose acylate solution, -10 to
A method for preparing a cellulose acylate solution comprising a step of swelling at 55 ° C. and a step of heating the mixture to 0 to 97 ° C. to dissolve the cellulose acylate in a solvent is preferred.

When the cellulose acylate and the non-chlorine organic solvent are mixed, it is preferable that 90% by mass or more of the cellulose acylate use 0.1 to 4 mm particles.

The method for producing a cellulose acylate film of the present invention preferably includes a step of concentrating the cellulose acylate solution. Moreover, it is preferable that the temperature of a cellulose acylate solution is 0-200 degreeC including the process of filtering the said cellulose acylate solution.

In the step of filtering the solution, the filtration filter preferably has an average pore size of 100 μm or less. The filtration flow rate is preferably 50 liters / hr or more.

In the method for producing a cellulose acylate film of the present invention, a step of casting the cellulose acylate solution on a metal support, a step of stripping, and a drying step of evaporating the solvent to form a film are further produced. It is preferable to include a step of winding the rate film.

The cellulose acylate solution preferably has a viscosity at 40 ° C. of 10 to 3000 Pa · s.

In the step of casting the cellulose acylate solution, the solution temperature is −10 to 57 ° C.
It is preferable that Moreover, when casting the said cellulose acylate solution, it is preferable that the temperature of the process is kept at -10-57 degreeC. Furthermore, the metal support for casting the cellulose acylate solution is preferably a band-shaped or drum-shaped metal support having a surface temperature of -20 to 40 ° C.

In the method for producing a cellulose acylate film of the present invention, when the cellulose acylate solution is cast, two or more layers of the cellulose acylate solution are simultaneously laminated or co-cast, or sequentially laminated at separate positions. Co-casting is preferred. Moreover, in the cellulose acylate film obtained by co-lamination and casting from two or more cellulose acylate solutions at the same time, the thickness on the air surface side and / or the thickness on the metal support side is 0.5 to 30% of the whole.
It is preferable that Furthermore, when simultaneously laminating and co-casting two or more cellulose acylate solutions at the same time, it is preferable to wrap the high-viscosity solution with the low-viscosity solution when extruding from the die slit to the casting surface. In addition, when simultaneously laminating and co-casting two or more cellulose acylate solutions at the same time, it is preferable to wrap in an external solution containing more alcohol than the internal solution when extruding from the die slit to the casting surface. .

In the stripping step, the temperature of the drying air during stripping is preferably 20 to 250 ° C. Moreover, it is preferable that the undried cellulose acylate film at the time of drying is hold | maintained with a tenter.

The cellulose acylate film is at least 0.5 uniaxially or after casting.
It is preferable to be stretched by ~ 300%. The casting speed is preferably 10 to 200 m / min.

In the step of winding up the film, it is preferable that the wound form of the film is at least 100 m in the longitudinal direction and 60 cm or more in the width direction.

It is preferable that both ends of the cellulose acylate film are slit in any of the steps from the casting step to the step of winding the film. Moreover, it is preferable that the slit both ends are knurled. In this case, the unevenness of the knurled part is 1 to 200.
It is preferable that it is micrometer.

The degree of curl of the cellulose acylate film of the present invention at 23 ° C. and 60% RH is −1.
It is preferable that it is 0-10. The thickness of the cellulose acylate film is 5
It is preferable that it is -500 micrometers. Furthermore, the variation in thickness of the cellulose acylate film is preferably within ± 3%.

The cellulose acylate film preferably has a transparency of 80 to 99.5%. Moreover, it is preferable that the haze of the said cellulose acylate film is 0.005 to 5%. Furthermore, it is preferable that Re of the said cellulose acylate film is 0-500 nm.

The Rth of the cellulose acylate film is preferably 0 to 400 nm.
Further, it is preferable that variations in Re and Rth are within ± 3%.

The cellulose acylate film preferably has a molecular orientation axis of −5 to 5 °. Moreover, it is preferable that the transmittance | permeability in 380 nm of the said cellulose acylate film is 20% or less. Furthermore, the residual solvent amount of the cellulose acylate film is 1
It is preferable that it is below mass%.

The water content of the cellulose acylate film is preferably 4% by mass or less.
Moreover, it is preferable that the elastic modulus of the said cellulose acylate film is 100-600 kgf / mm < ² >. Furthermore, the elongation of the cellulose acylate film is 20 to 7
It is preferably 0%.

  It is preferable that the tensile strength of the cellulose acylate film is 5 to 500 MPa. Moreover, it is preferable that Tg of the said cellulose acylate film is 50-180 degreeC. Further, the heat shrinkage of the cellulose acylate film is preferably −2 to 2%.

It is preferable that the surface of the cellulose acylate film has a contact angle with water of 5 to 90 °. Also, the optical film disposed between two polarizing plates arranged in a crossed Nicol state with the bright point of the cellulose acylate film is observed from one polarizing plate side and observed from the other polarizing plate side. In this case, the number of bright spots having a diameter of 0.01 mm or more is preferably 200 / cm ² or less.

It is preferable that at least one surface of the cellulose acylate film is surface-treated. The surface treatment is preferably at least one of vacuum glow discharge treatment, atmospheric pressure plasma discharge treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid treatment or alkali treatment.

  At least one surface of the cellulose acylate film may be undercoated.

The cellulose acylate film of the present invention is preferably used as a functional material provided with another functional layer using the film as a support. The functional layer is preferably provided with at least one layer selected from an antistatic layer, a cured resin layer, an antireflection layer, an easy adhesion layer, an antiglare layer and an optical compensation layer.

The functional layer preferably contains 0.1 to 1000 mg / m ^{2 of} at least one surfactant. Further, the functional layer contains at least one kind of slip agent in a range of 0.1 to 1000 m.
It is preferable to contain g / m ² . Furthermore, it is preferable that the functional layer contains 0.1 to 1000 mg / m ^{2 of} at least one kind of matting agent. Furthermore, the functional layer preferably contains 1 to 1000 mg / m ^{2 of} at least one antistatic agent.

The functional material is preferably used for optical applications. The optical application is preferably used as a liquid crystal display device. A liquid crystal cell in which the liquid crystal display device carries a liquid crystal between two electrode substrates, two polarizing elements disposed on both sides thereof, and at least one sheet between the liquid crystal cell and the polarizing element The optical compensation sheet is preferably arranged.

The polarizing film of the polarizing element is preferably an iodine polarizing film, a dye polarizing film using a dichroic dye, or a polyene polarizing film. The polarizing film is preferably manufactured using a polyvinyl alcohol film.

The liquid crystal display device is TN, IPS, FLC, AFLC, OCB, STN, VA and H
An AN is preferred. Further, any of a transmissive type, a reflective type, and a transflective liquid crystal display device is preferable. In this case, it is preferable that the Re retardation value of the optical compensation sheet used in the VA liquid crystal display device is 0 to 150 nm and the Rth retardation value is 70 to 400 nm.

A polarizing protective film in which a polarizing plate is bonded to the cellulose acylate film is preferable.

In the cellulose acylate film of the present invention, it is preferable that the transmittance change rate after aging at 60 ° C. and 90% relative humidity for 500 hours is 10% or less in both parallel transmittance and orthogonal transmittance. Further, it is preferable that the transmittance change rate after aging at 80 ° C. for 500 hours is such that the parallel transmittance and the orthogonal transmittance are both 10% or less. Further, 60 ° C., relative humidity 90%
It is preferable that the change rate of the color tone when aged for 500 hours is 10% or less in both parallel and orthogonal directions. Furthermore, it is preferable that the color change rate after aging at 80 ° C. for 500 hours is 10% or less in both parallel and orthogonal directions.

Hereinafter, the present invention will be described in detail. In the evaluation of cellulose acylate, cellulose acylate solution or cellulose acylate film, and further an optical film,
The measurement was carried out by the following method.

(Thickness variation measurement)
Measured with an electronic micrometer manufactured by Anritsu Electric Co., Ltd. at a speed of 600 mm / min, recorded on chart paper at a scale of 1/20, and a chart speed of 30 mm / min. Round off.

(Haze)
A sample 40 mm × 80 mm was measured at 25 ° C. and 60% RH with a haze meter (HGM-2DP,
Measured in accordance with JIS K-6714 using a Suga tester.

(Transmittance)
The transmittance of visible light (615 nm) was measured on a 20 mm × 70 mm sample at 25 ° C. and 60% RH with a transparency measuring instrument (AKA phototube colorimeter, KOTAKI Corporation).

(Spectral characteristics)
A spectrophotometer (U-3210, Co., Ltd.) with a sample of 13 mm x 40 mm at 25 ° C and 60% RH
Hitachi, Ltd.) measured transmittance at a wavelength of 300 to 450 nm. Inclination width is 72%
The wavelength was obtained at a wavelength of 5%. The limit wavelength was expressed as a wavelength of (gradient width / 2) + 5%. The absorption edge is represented by a wavelength having a transmittance of 0.4%. Furthermore, the transmittance at 380 nm was evaluated.

(Retardation)
In this specification, Re (λ) and Rth (λ) respectively represent in-plane retardation and retardation in the thickness direction at a wavelength λ. Re (λ) is measured by making light having a wavelength of λ nm incident in the normal direction of the film in KOBRA 21ADH (manufactured by Oji Scientific Instruments). Rth (λ) is the light of wavelength λnm from the direction inclined by + 40 ° with respect to the normal direction of the film, with Re (λ) and the in-plane slow axis (determined by KOBRA 21ADH) as the tilt axis (rotary axis). The retardation value measured by injecting light, and the retardation measured by injecting light of wavelength λ nm from the direction inclined −40 ° with respect to the film normal with the in-plane slow axis as the tilt axis (rotation axis) KOBRA 21ADH is calculated based on the retardation values measured in a total of three directions. Here, as the assumed value of the average refractive index, 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. Examples of average refractive index values are: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), polystyrene (1.59). ). The KOBRA 21ADH calculates nx, ny, and nz by inputting the assumed value of the average refractive index and the film thickness. When the Nz factor is required, Nz = (nx−nz) / (nx−ny) is further calculated from the calculated nx, ny, and nz.

(Molecular orientation axis)
A sample 70 mm × 100 mm was conditioned at 25 ° C. and 65% RH for 2 hours, and an automatic birefringence meter (K
In OBRA21DH, Oji Scientific Co., Ltd., the molecular orientation axis was calculated from the phase difference when the incident angle at normal incidence was changed.

(Axis misalignment)
Moreover, the axis | shaft misalignment angle was measured with the automatic birefringence meter (KOBRA-21ADH, Oji Scientific Instruments). Twenty points were measured at equal intervals over the entire width in the width direction, and the average absolute value was determined. Moreover, the range of the slow axis angle (axis deviation) is measured at 20 points at equal intervals over the entire width direction,
The difference between the average of 4 points from the larger absolute value of the axis deviation and the average of 4 points from the smaller absolute value is taken.

(Tear strength)
Sample 50mm x 64mm is conditioned for 2 hours at 23 ° C and 65% RH, and the load required for tearing is measured in accordance with ISO 6383 / 2-1983 using a light load tear strength tester (Toyo Seiki Seisakusho). MD, TD direction Was averaged and evaluated.

(Folding strength)
Sample 120mm x 120mm was conditioned for 2 hours at 23 ° C, 65% RH, and ISO8776
The number of reciprocations until cutting by bending according to -1988 was measured.

(Tensile strength)
Sample 15 mm × 250 mm was conditioned at 23 ° C. and 65% RH for 2 hours using a Tensilon tensile tester (RTA-100, Orientec Co., Ltd.) according to ISO1184-1983.
The elastic modulus was calculated from the initial tensile stress and elongation at an initial sample length of 100 mm and a tensile speed of 200 ± 5 mm / min. Tensile strength, breaking stress, stretching force and breaking elongation were also evaluated at the same time.

(Rt difference between inside and outside of winding)
The sample 8 was wound up to a length of 100 m and allowed to stand at room temperature for 1 month as it was, and then the Rt of the surface film and the Rt of the inner film were determined by the method described above, and the difference was determined as the Rt difference.

(Kisimi)
Samples of 100 mm × 200 mm and 75 mm × 100 mm were measured at 23 ° C. and 65% R
H, humidity was adjusted for 2 hours, a large film was fixed on a table with a Tensilon tensile tester (RTA-100, Orientec Co., Ltd.), and a small film with a 200 g weight was placed thereon. Pull the weight in the horizontal direction and measure the force when it starts moving and the force when it moves. Then, the static friction coefficient and the dynamic friction coefficient were calculated according to the following equations, respectively.
F = μ × W (W: weight of weight (kgf))

(Dynamic friction (steel ball method))
Sample 35mm x 100mm was conditioned for 2 hours at 23 ° C, 65% RH, and with a dynamic friction coefficient measuring instrument (Toyo Baldwin), the sample was fixed on the table with the measurement surface facing up, and the steel ball was lowered onto the sample The table was sent and measured.

(Alkaline hydrolysis)
A 100 mm × 100 mm sample was saponified with a 2N aqueous sodium hydroxide solution at 60 ° C. for 2 minutes with an automatic alkali saponification treatment apparatus (Shinto Kagaku Co., Ltd.) and washed with water for 4 minutes. Neutralize with 30 ° C, 0.01N dilute nitric acid for 4 minutes, and wash with water for 4 minutes. The film was dried at 100 ° C. for 3 minutes and naturally dried for 1 hour, and evaluated by the following visual standard and haze values before and after the saponification treatment.
A: No whitening is observed B: Whitening is slightly observed C: Whitening is considerably recognized D: Whitening is remarkably recognized

(Curl value)
Sample 35mm x 3mm, curl humidity control tank (HEIDON (No. YG53-168),
Shinto Kagaku Co., Ltd.) is conditioned at 25%, 55% and 85% for 24 hours, and the radius of curvature is measured with a curl plate. In addition, the curl in wet is measured after standing in water at a water temperature of 25 ° C. for 30 minutes.

(Moisture and heat resistance)
Sample 35 mm x 25 mm was aged for 200, 500 and 1000 hours at 85 ° C and 90% RH, respectively, and the two samples were bonded with an adhesive using Platinum Rainbow (PR-1G, Tabai Espec). The sample was visually observed and the color change was measured and judged as follows.
A: No particular abnormality is observed.
B: Shape change due to decomposition odor or decomposition is recognized.

(Moisture content)
A 7 mm × 35 mm sample was measured by a Karl Fischer method using a moisture measuring device and a sample drying apparatus (CA-03, VA-05, both Mitsubishi Chemical Corporation). It was calculated by dividing the amount of water (g) by the sample weight (g).

(Residual solvent amount)
Sample 7mm x 35mm was gas chromatographed (GC-18A, Shimadzu Corporation)
The base residual solvent amount was measured.

(Heat shrinkage)
Sample 30 mm x 120 mm was aged at 90 ° C, 5% RH for 24, 120 hours, and automatic pin gauge (Shinto Kagaku Co., Ltd.) was used to drill 6mmφ holes at both ends at 100mm intervals, and the original size of the interval (L1) Was measured to a minimum scale of 1/1000 mm. Further, at 90 ° C. and 5% RH, 2
Measure the punch spacing (L2) by heat treatment for 4 hours and 120 hours. And heat shrinkage rate is {
It calculated | required by (L1-L2) / L1} * 100.

(High humidity dimensional evaluation)
Sample 30mm x 120mm was conditioned at 40 ° C, 95% RH, 60 ° C and 90% RH for 24 hours respectively, and automatic pin gauge (Shinto Kagaku Co., Ltd.) was used to make 6mmφ holes at both ends.
An interval of mm was opened, and an original size (L1) of the interval was measured to a minimum scale of 1/1000 mm. Then, heat treatment is performed at 90 ° C. and 5% RH for 24 hours and 120 hours, and the dimension of the punch interval (L3)
Was measured. The dimensional change rate was determined by {(L1-L2) / L1} × 100.

(Moisture permeability, moisture permeability coefficient)
A 70 mmφ sample was conditioned at 25 ° C., 90% RH, 40 ° C., and 90% RH for 24 hours, respectively, and in a moisture permeation test apparatus (KK-709007, Toyo Seiki Co., Ltd.) according to JIS Z-0208 The amount of water per unit was calculated (g / m ² ). And the water vapor transmission rate was calculated | required from the weight after humidity control-weight before humidity control. Furthermore, as a compulsory evaluation, it measured after 60-hour conditioning at 60 degreeC 95% RH, and was set as the moisture permeability coefficient.

(Flatness of base)
As a sample, the entire width × 1.5 m was examined by changing the angle with reflected light and transmitted light, and the flatness was evaluated. Regarding the surface shape, the film was inspected with a slide scope in a dark room, and evaluated with a base surface projector.

(Foreign substance inspection)
The sample was irradiated with reflected light over a total width of 1 m, and foreign matter in the film was visually detected. Then, the foreign matter (lint) was confirmed and evaluated with a deflection microscope.

(Dimensional stability)
Dimensional stability is expressed in terms of heat shrinkage. Three test pieces each having a width of 30 mm and a length of 120 mm are collected from the vertical and horizontal directions of the sample. Holes of 6 mmφ are punched at 100 mm intervals on both ends of the test piece. This is conditioned for at least 3 hours in a room at 23 ± 3 ° C. and a relative temperature of 65 ± 5%. Using an automatic pin gauge (manufactured by Shinto Kagaku Co., Ltd.), the original scale (L1) of the punch interval is the minimum scale / 1000
Measure to mm. Next, the test piece was suspended in a thermostat at 80 ° C. ± 1 ° C. and heat-treated for 3 hours, and 23 ±
After adjusting the humidity for 3 hours or more in a room at 3 ° C. and a relative humidity of 65 ± 5%, the dimension (L2) of the punch interval after the heat treatment is measured with an automatic pin gauge. And the thermal contraction rate is calculated by the following formula.
Thermal contraction rate = (L1-L2 / L1) × 100

(Heat shrinkage start temperature)
Cut to 35 mm length along the high draw ratio direction and 3 mm width along the low draw ratio direction.
The both ends are chucked at intervals of 25 mm in the longitudinal direction. This is a TMA measuring instrument (TA instr.
uments TMA2940 Thermo Mechanical Analyz
er) and measuring the dimensional change while increasing the temperature from 30 ° C. to 200 ° C. at 3 ° C./min while applying a force of 0.04 N. The 30 ° C. dimension is taken as the base length, and the temperature at which shrinkage by 2% is taken as the shrinkage start temperature.

(Elastic modulus)
Using Toyo Baldwin Universal Tensile Tester STM T50BP, 23 ° C, 70%
In the atmosphere, the stress at 0.5% elongation was measured at a pulling rate of 10% / min to obtain the elastic modulus.

(Measurement of bright spot foreign matter)
Two polarizing plates are arranged in an orthogonal state (crossed Nicols) to block transmitted light, and each sample is placed between the two polarizing plates. The polarizing plate used was a glass protective plate. Light was irradiated from one side, and the number of bright spots having a diameter of 0.01 mm or more per 1 cm ² was counted with an optical microscope (50 times) from the opposite side.

[Cellulose acylate]
The cellulose acylate used in the present invention is described below. Cellulose acylate raw material cellulose used in the present invention includes cotton linter and wood pulp (hardwood pulp, softwood pulp), etc., and any cellulose acylate obtained from any raw material cellulose can be used, optionally mixed. May be. Detailed descriptions of these raw material celluloses can be found in, for example, Plastic Material Course (17) Fibrous resin (manufactured by Marusawa and Uda, published by Nikkan Kogyo Shimbun, 1970).

According to it, the molecular weight of cellulose is wide, for example natural cellulose is 600,000-1
500,000 (the degree of polymerization is approximately 3500 to 10,000), and the purified linter is 10,000 to 500,000 (the degree of polymerization is approximately 2).
0 to 3000), and wood pulp is 10,000 to 1.34 million (rough polymerization degree 200 to 2100)
It is. Here, the molecular weight greatly affects the strength properties of cellulose or its derivatives,
As the molecular weight decreases, the mechanical strength suddenly decreases from a certain degree of polymerization.

In the present invention, cellulose acylate is produced by esterification from cellulose,
The particularly preferred cellulose described above is not necessarily usable as it is, and is used as refined linter and refined high-quality wood pulp by refining linter or pulp. Linter is a short fiber having a short fiber length among cotton fibers, has a high α-cellulose content (for example, 88 to 92% by mass), has a high purity, and has few impurities. This crude linter can be obtained by purifying litter, alkali cooking, bleaching, acid treatment, dehydration and drying. These details are in the plastic materials course (
17) It is described in pages 25 to 28 of a fiber-based resin (Marusawa, Uda, Nikkan Kogyo Shimbun, published in 1970), and its characteristics are described in Tables 2 and 3, and the preferred purified linter in the present invention. Is obtained.

Further, the refined pulp is also described on pages 28 to 32 of the same book, and the characteristics are also described in Tables 2 and 4, and the pulp refined by such a method is also preferable as the cellulose acylate raw material. Here, it is also preferable to use a mixture of purified cotton linter and wood pulp,
The ratio is not particularly limited, but is preferably 0/100 to 95/5. By mixing, the solubility can be improved, and the surface shape, mechanical properties and optical properties of the cellulose acylate film can be improved.

In JP-A-2002-371143, in order not to generate cutting powder during processing, and to prevent delamination and the like, at least 0.5 μm portion from one or both surfaces of the film,
The mass ratio of cotton linter to wood pulp (cotton linter / wood pulp) is 40 / 60-10
0/0, the content of the cotton linter is 5% by mass or more than the content of the cotton linter in the dope used for other parts, and the content of the alcohol and hydrocarbon having 1 to 10 carbon atoms in the solvent is 20% by mass. An invention using the following dope is described.

In addition, in JP-A-2002-371142, in order to suppress optical unevenness generated at the edge of the corner portion of the polarizing plate, a portion of at least 0.5 μm from one or both surfaces of the produced film, The mass ratio of cotton linter to wood pulp (cotton linter / wood pulp) is 5 / 95-0
/ 100, and the content of alcohol and hydrocarbon having 1 to 10 carbon atoms in the solvent is 15
An invention using a dope having a mass% or more is described.

The inventions relating to these cellulose acylates described above can also be applied to the present invention.

Here, the cellulose used also in the present invention has been variously analyzed.
STM standard Part 15, TAPPI Standard (Te
chemical association of the Pulp and Papé
r Industry) and JIS P 8101. Measurement items include ash, calcium oxide and magnesium oxide content, α-cellulose, β-cellulose, copper value, and the like.

Among these, the α-cellulose content that serves as an indicator of the purity of the pulp can be selected from a range of, for example, about 80 to 100% by mass, and is usually about 85 to 98% for wood pulp. In the present invention, low-purity pulp, for example, pulp having an α-cellulose content of about 80 to 96% (particularly 92 to 96%) can also be used. Of these pulps, wood pulp is usually used. Cellulose acylate made from hardwood pulp is poor in film peelability by casting, and softwood pulp is slightly deteriorated due to optical properties such as transparency. Can be used without problems for film applications.

Further, in the present invention, as described in JP-A-11-130301, the neutral constituent sugar component in pulp or cotton is mainly composed of glucose but may contain mannose and xylose. The ratio is not particularly limited, but mannose / xylose (molar ratio) = 0.35 / 1 to 3.0 / 1, preferably 0.35 / 1 to 2.5 / 1, more preferably 0.35 / 1. ~ 2/1. In the cellulose triacetate prepared in that case, the total content of mannose and xylose is 0.01-5 mol%, preferably 0
. 1 to 4 mol%. “Mannose” and “xylose” are the main constituent sugars of hemicellulose (xylan, glucomannan, etc.) contained in pulp. The constituent sugar components of these raw pulps and the obtained cellulose acylate (for cellulose triacetate) can be specifically analyzed by the method described in JP-A-11-130301.

On the other hand, X-ray analysis is also used as a means for evaluating the structure of cellulose. According to this document, it is described that the cellulose molecules are arranged in parallel to the fiber axis direction and attracted by hydrogen bonds to form one unit cell by the cellobiose unit of five cellulose molecules. Further, X-ray analysis shows that the crystallinity of natural cellulose is about 70%, and these celluloses can also be used for the production of cellulose acylate of the present invention.

Regarding the cellulose acylate described above, JP-A-10-45803 and JP-A-11
-269304, JP-A-8-231761, JP-A-10-60170, JP-A-9-407
92, JP-A-11-5851, JP-A-11-269304, JP-A-9-90101, JP-A57-182737, JP-A-4-277530, JP-A-11-292989, JP-A-1
It is also preferable to use cellulose acylate described in 2-131524, JP-A-12-137115, and the like. These materials are not particularly limited to the cellulose acylate film produced using a non-chlorine organic solvent.

[Preparation of cellulose acylate solution (dope) and production of film]
Next, the cellulose acylate of the present invention produced from the aforementioned cellulose as a raw material will be described. The cellulose acylate of the present invention has a substitution degree of cellulose with a hydroxyl group represented by the following formula (I):
Those satisfying all of (III) to (III) are preferred.
(I) 2.5 ≦ A + B ≦ 3
(II) 0 ≦ A ≦ 3.0
(III) 0 ≦ B ≦ 2.9
Here, A and B in the formula represent a substituent of an acyl group substituted with a hydroxyl group of cellulose,
A is the degree of substitution of the acetyl group, and B is the degree of substitution of the acyl group having 3 to 22 carbon atoms. Cellulose has three hydroxyl groups in one glucose unit, and the above number represents the degree of substitution with respect to the hydroxyl group 3.0, and the maximum degree of substitution is 3.0. Cellulose triacetate generally has a substitution degree of A of 2.5 to 3.0 (in this case, the maximum number of unsubstituted hydroxyl groups is 0.00.
5), the case of B = 0 is cellulose triacetate.

In addition, when all the acyl groups are acetyl groups, the substitution degree of the hydroxyl groups is usually represented by the acetylation degree. That is, the average degree of acetylation in cellulose acetate is
A range of about 58% to 62.5% (average acetyl group substitution degree of 2.64 to 3.0) is preferable depending on the application and characteristics. More preferably, it is about 59-62% (for example, 60-61%). Here, the degree of acetylation means the amount of bound acetic acid, refers to the weight percentage of bound acetic acid per unit weight of cellulose, and is a method for measuring the degree of acetylation according to ASTM: D-817-91 (testing method for cellulose acetate, etc.). It can be measured similarly. Specifically, 1.9 g of dried cellulose acetate was precisely weighed, and a mixed solvent of acetone and dimethyl sulfoxide (volume ratio 4: 1) 1
After dissolving in 50 ml, 30 ml of 1N aqueous sodium hydroxide solution is added and saponified at 25 ° C. for 2 hours. Phenolphthalein is added as an indicator, and 1N sulfuric acid (concentration factor:
Titrate excess sodium hydroxide in F). Moreover, it calculates | requires by performing a blank test by the method similar to the above, and calculating an acetylation degree according to a following formula.
Degree of acetylation (%) = [6.5 × (BA) × F] / W
(In the formula, A is a 1N sulfuric acid titration (ml) in the sample, B is a 1N sulfuric acid titration (ml) in the blank test, F is a concentration factor of 1N sulfuric acid, and W is the weight of the sample).

Glucose units having β-1,4 bonds constituting cellulose have free hydroxyl groups at the 2nd, 3rd and 6th positions. Cellulose acylate is a polymer obtained by esterifying some or all of these hydroxyl groups with an acyl group having 2 or more carbon atoms. The degree of acyl substitution means the ratio of the hydroxyl group of cellulose esterified at each of the 2-position, 3-position and 6-position (100% esterification has a substitution degree of 1).

The total acyl substitution degree, that is, DS2 + DS3 + DS6 is preferably 2.00 to 3.00,
More preferably, it is 2.22 to 2.90, and particularly preferably 2.40 to 2.88.
Further, DS6 / (DS2 + DS3 + DS6) is preferably 0.28 or more, more preferably 0.30 or more, and particularly preferably 0.31 to 0.34. Here, DS2 is the substitution degree of the hydroxyl group at the 2-position of the glucose unit with an acyl group (hereinafter, also referred to as “acyl substitution degree at the 2-position”).
DS3 is the substitution degree of the hydroxyl group at the 3-position with an acyl group (hereinafter referred to as “acyl substitution degree at the 3-position”).
DS6 is the substitution degree of the hydroxyl group at the 6-position with an acyl group (hereinafter also referred to as “acyl substitution degree at the 6-position”).

  Only one type of acyl group may be used in the cellulose acylate of the present invention, or two or more types of acyl groups may be used. When two or more kinds of acyl groups are used, it is preferable that one of them is an acetyl group. When the sum of the substitution degrees by the hydroxyl groups at the 2nd, 3rd and 6th positions is DSA, and the sum of the substitution degree by an acyl group other than the acetyl group at the 2nd, 3rd and 6th hydroxyl groups is DSB, the value of DSA + DSB is More preferably, it is 2.22 to 2.90, and particularly preferably 2.40 to 2.88. The DSB is 0.30 or more, particularly preferably 0.7 or more. Further, 20% or more of DSB is a substituent at the 6-position hydroxyl group, more preferably 25% or more is a substituent at the 6-position hydroxyl group, more preferably 30% or more, and particularly 33% or more is a 6-position hydroxyl group. It is preferable that it is a substituent. Furthermore, the cellulose acylate having a substitution degree of 6-position of cellulose acylate of 0.75 or more, further 0.80 or more, and particularly 0.85 or more can be mentioned. With these cellulose acylates, a solution having a preferable solubility (dope) can be produced. In particular, in a non-chlorine organic solvent, a good solution can be produced. Furthermore, it is possible to produce a solution having a low viscosity and good filterability.

  Cellulose, which is a raw material for cellulose acylate, may be obtained from either linter cotton or pulp cotton, but is preferably obtained from linter cotton.

  The acyl group having 2 or more carbon atoms of the cellulose acylate of the present invention may be an aliphatic group or an aryl group and is not particularly limited. These are, for example, cellulose alkylcarbonyl esters, alkenylcarbonyl esters, aromatic carbonyl esters, aromatic alkylcarbonyl esters, and the like, each of which may further have a substituted group. Preferred examples of these include propionyl, butanoyl, pentanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, iso-butanoyl, t-butanoyl, cyclohexanecarbonyl, oleoyl, benzoyl , Naphthylcarbonyl, cinnamoyl group and the like. Among these, propionyl, butanoyl, dodecanoyl, octadecanoyl, t-butanoyl, oleoyl, benzoyl, naphthylcarbonyl, cinnamoyl and the like are more preferable, and propionyl and butanoyl are particularly preferable.

Regarding the substitution degree of the 6-position hydroxyl group of cellulose acylate, JP-A-2003-105129 discloses a total acyl group for cellulose acylate in order to improve the planarity, moisture resistance (water content) and film strength. Cellulose acylate A having a substitution degree of 2.70 to 2.90, an acyl group having 3 to 22 carbon atoms having a substitution degree of 0.40 to 2.50, and an acyl substitution at the 6-position of less than 0.90, and a total acyl substitution degree of 2.75 to 2.90 In addition, there is a description of a cellulose acylate film containing cellulose acylate B having an acyl substitution degree of 3 to 22 carbon atoms and an acyl substitution degree of 0.00 to 0.40 and a 6-position acyl substitution degree of 0.90 or more, and the present invention can also be applied to the present invention.

The acyl group of the cellulose acylate of the present invention may be an aliphatic group or an allyl group and is not particularly limited. They are, for example, alkyl carbonyl esters, alkenyl carbonyl esters, aromatic carbonyl esters, aromatic alkyl carbonyl esters, etc. of cellulose, each of which may further have a substituted group, and an ester having a total carbon number of 22 or less. Groups are preferred. These preferred cellulose acylates include acyl groups having a total carbon number of 22 or less in the ester moiety (for example, acetyl, propionyl, butyroyl, barrel, heptanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, hexadecanoyl, octadecanoyl, etc. ), Arylcarbonyl groups (acrylic, methacrylic, etc.), allylcarbonylkis (benzoyl, naphthaloyl etc.) and cinnamoyl groups. Among these, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate stearate, cellulose acetate benzoate, etc. are not particularly limited in the case of mixed esters, but preferably acetate is the total ester. It is preferable that it is 30 mol% or more.

Among these, cellulose acylate is preferred, and photographic grades are particularly preferred, and commercially available photographic grades can be obtained with satisfactory quality such as viscosity average degree of polymerization and substitution degree. As manufacturers of photographic grade cellulose triacetate, Daicel Chemical Industries, Ltd. (for example, LT-20, 30, 40, 50, 70, 35, 55, 105, etc.), Eastman Kodak Company (for example, CAB-551) 0.01, CAB-551-
0.02, CAB-500-5, CAB-381-0.5, CAB-381-02, CA
B-381-20, CAB-321-0.2, CAP-504-0.2, CAP-482
-20, CA-398-3, etc.), Coatles, Hoechst, etc., any of which can use photographic grade cellulose acylate.

(Method for producing cellulose acylate)
The manufacturing method of the cellulose acylate used in the present invention will be described. Among the preferred cellulose acylates of the present invention, more preferred cellulose acetate will be described, but other esters can be produced in the same manner. In addition, the general description about the cellulose acetate which is a representative of the cellulose acylate is 54 to 54 of the aforementioned plastic material course (17) Fibrous resin (Marusawa, Uda, Nikkan Kogyo Shimbun, published in 1970).
107, and these cellulose acetates are also preferably used.

That is, although the manufacturing method of a cellulose acetate is not specifically limited, For example, it can manufacture by methods, such as a sulfuric acid catalyst method, an acetic acid method, a methylene chloride method. Cellulose acetate is prepared by treating cellulose raw material such as linter or pulp with acetic acid or the like (activation process), and then acetylating with acetic anhydride using sulfuric acid as an acid catalyst in the acetylation process to produce triacetate. Thereafter, it is produced as cellulose acetate by hydrolysis, aging, precipitation step, purification step and further drying step so as to have a predetermined degree of acetylation. The activation step can be performed by treating pulp (cellulose) by, for example, spraying acetic acid or hydrous acetic acid, or immersing in acetic acid or hydrous acetic acid. Acetic acid is used in an amount of 10 to 100 parts by weight, preferably 20 to 80 parts by weight, and more preferably 30 to 60 parts by weight with respect to 100 parts by weight of pulp (cellulose).
The amount of acetic anhydride in the acetylation step is 23 with respect to 100 parts by weight of pulp (cellulose).
0 to 300 parts by weight, preferably 240 to 290 parts by weight, more preferably 250 to 280
Parts by weight. In the acetylation step, acetic acid is usually used as a solvent,
For example, 200 to 700 parts by weight, preferably 3 to 100 parts by weight of pulp (cellulose)
It is about 00 to 600 parts by weight, more preferably about 350 to 500 parts by weight. As the acetylation or aging catalyst, sulfuric acid is preferably used, and the amount used is 1 to 15 parts by weight, preferably 5 to 15 parts by weight, particularly 5 to 10 parts by weight, based on 100 parts by weight of cellulose. .

In order to further improve the optical properties of cellulose acetate, it is useful to treat the produced cellulose acetate with an oxidizing agent at an appropriate stage in the cellulose acetate production process, for example, after completion of acetylation or saponification. . The treatment with an oxidizing agent is effective regardless of the amount of acetic acid in the acetylation step, but when applied to acetylated cellulose acetate with an increased amount of acetic acid solvent in the acetylation step, further optical The characteristic can be improved. Examples of the oxidizing agent include hydrogen peroxide; peracids such as performic acid, peracetic acid, perbenzoic acid, lauroyl peroxide, and benzoyl peroxide; and organic peroxides such as diacetyl peroxide. These oxidizing agents can be used alone or in combination of two or more. Preferred oxidizing agents include oxidizing agents that are easy to remove from cellulose acetate and have low persistence, such as hydrogen peroxide, performic acid,
Examples include peracetic acid, and hydrogen peroxide and peracetic acid are particularly preferable. The amount of the oxidizing agent used can be selected according to the level of optical properties desired, for example, 0.01 to 5 parts by weight, preferably 0.1 to 2.5 parts by weight, based on 100 parts by weight of cellulose acetate. Part, especially about 0.1 to 1 part by weight. The treatment with the oxidizing agent can be performed at, for example, 20 to 100 ° C., preferably 30 to 70 ° C., depending on the type of the oxidizing agent. The temperature of saponification / ripening is not particularly limited, but is 40 to 90 ° C, more preferably 50 to 80 ° C.

Next, the precipitation step can be generally achieved by adding a poor solvent of cellulose acylate to the reaction solution. The poor solvent used at this time is water, alcohol (methanol, ethanol, propanol, butanol, etc.), acetone or the like. The obtained precipitated cellulose acylate solid is preferably further washed with the aforementioned solvent, and a purification step is generally carried out.
Whether or not the cleaning is sufficient can be determined by measuring the pH of the cleaning liquid. That is, when the cleaning is insufficient, it can be judged that the cleaning liquid shows acidity. Further, in washing, it is preferable to subdivide and wash the precipitated cellulose acylate. For example, the lump of cellulose acylate is preferably 10 mm or less, and can be carried out with a crushing stirrer or the like.
In the case where the acyl group is a long-chain alkyl or the like, hexane or the like may be used.

According to JP-A-2001-26601, a cellulose acylate solution with good filterability can be obtained, which can be preferably implemented in the present invention. That is, after the acetylation reaction is completed, the neutralization treatment in the neutralization step reduces the insoluble components in the cellulose acetate solution and increases the filterability, so that the water concentration of the reaction system during the neutralization treatment is 0.1. It is adjusted to be not less than 18% by weight, preferably 0.4 to 12% by weight, more preferably 0.4 to 8% by weight, and still more preferably 0.4 to 5% by weight. For the same purpose, the water concentration is preferably 0.1% by weight or more and 1 after the unreacted acetic anhydride is decomposed after the neutralization treatment is started.
Less than 8% by weight, more preferably 0.4-12% by weight, still more preferably 0.4-8% by weight
It is particularly preferable to adjust the content to 0.4 to 5% by weight. Neutralization treatment
A method of adding a neutralizing agent as an aqueous solution or aqueous suspension, or first adding water to the reaction system,
A method of adding the neutralizing agent in the form of a powder, an aqueous solution or a water suspension can be applied, but an aqueous solution method is preferred from the viewpoint of workability. In the case of the aqueous solution method, the concentration of the neutralizing agent is preferably 10 to 45% by weight.
More preferably, it is 10 to 25% by weight. The neutralizing agent can be selected from alkali metal or alkaline earth metal hydroxides, alkali metals or alkaline earth metal salts, etc., but alkaline earth metal salts such as calcium and magnesium are preferred.

In addition, when adding a powdered neutralizing agent as a neutralization processing method, the time of adding aqueous solution or water suspension becomes the start of neutralization processing. The neutralization treatment is desirably performed at 35 to 80 ° C, preferably 45 to 75 ° C.

Next, the precipitation step can be generally achieved by adding a poor solvent of cellulose acylate to the reaction solution. The poor solvent used at this time is water, alcohol (methanol, ethanol, propanol, butanol, etc.), acetone or the like. The obtained precipitated cellulose acylate solid is preferably further washed with the aforementioned solvent, and a purification step is generally carried out.
Whether or not the cleaning is sufficient can be determined by measuring the pH of the cleaning liquid. That is, when the cleaning is insufficient, it can be judged that the cleaning liquid shows acidity. Further, in washing, it is preferable to subdivide and wash the precipitated cellulose acylate. For example, the lump of cellulose acylate is preferably 10 mm or less, and can be carried out with a crushing stirrer or the like.
When the acyl group is a long chain alkyl or the like, hexane or the like may be used.

Next, the drying step is essential for cellulose acylate. The drying is not particularly limited, and may be normal pressure or reduced pressure, and the drying temperature is arbitrarily selected from 30 to 250 ° C. here,
If the temperature of a cellulose acylate solid is 30-250 degreeC, the method may send a high temperature wind, and may heat a cellulose acylate by making the temperature of a conveyance roller high. Furthermore, it may be carried out by applying electron beam irradiation such as ultrasonic waves and dried. The drying time is preferably as short as possible in view of productivity, and is preferably 0.1 to 1000 hours. Furthermore, 1 to 100 hours are particularly preferable. Moreover, when drying under reduced pressure, 100-50,000 Pa is preferable, More preferably, 1000-30,000 Pa is preferable. A water pump may be used to achieve the reduced pressure, or the pressure may be reduced mechanically.

Furthermore, in order to improve the stability of cellulose acylate, the produced cellulose acylate contains a heat-resistant stabilizer such as an alkali metal salt (potassium or sodium salt) or an alkaline earth metal salt (calcium, magnesium, strontium, Barium etc.) may be added. The content is not particularly limited, as long as the metal of alkali metal or alkaline earth metal is in the range of 1 ppb to 10000 ppm relative to cellulose acylate,
Furthermore, it is 10 ppb to 1000 ppm, and 50 ppb to 500 ppm is particularly preferable. Further, the content of iron atoms present as an iron compound is preferably 1000 ppm, more preferably 100 ppm, further 20 ppm, and particularly preferably 1 ppm or less.
Other metals (for example, heavy metals such as zinc, tin, lead, nickel, and copper) are not particularly problematic as long as they do not interfere with the present invention, but are preferably 1000 ppm or less, and more preferably 100 ppm. It is as follows.

(Preferred characteristics of cellulose acylate)
The degree of polymerization of cellulose acylate preferably used in the present invention is a viscosity average degree of polymerization of 200.
-700, preferably 250-550, more preferably 200-400, still more preferably 250-400, particularly preferably a viscosity average degree of polymerization of 250-350. The average degree of polymerization was determined by the Uda et al. Intrinsic viscosity method (Kazuo Uda, Hideo Saito, Journal of Textile Science, Vol. 18, No. 1, 105
-120 pages, 1962). Further details are described in JP-A-9-95538. The viscosity average degree of polymerization is determined by the following formula from the intrinsic viscosity [η] of cellulose acetate measured with an Ostwald viscometer.
(A1) DP = [η] / Km
In the formula, [η] is the intrinsic viscosity of cellulose acetate, and Km is a constant 6 × 10 ⁻⁴ . When the viscosity average polymerization degree (DP) is 290 or more, it is preferable that the viscosity average polymerization degree and the concentrated solution viscosity (η) by the falling ball viscosity method satisfy the relationship of the following formula (a2).
(A2) 2.814 × ln (DP) −11.753 ≦ ln (η) ≦ 6.29 × ln (DP) −31.469
In the formula, DP is a value of a viscosity average polymerization degree of 290 or more, and η is a passage time (sec) between marked lines in the falling ball viscosity method. The above formula (a2) is obtained by plotting the viscosity average polymerization degree and the concentrated solution viscosity and calculating from the result. In cellulose acetate having a viscosity average degree of polymerization of 290 or more, the viscosity of the concentrated solution increases exponentially as the degree of polymerization generally increases. In contrast, in cellulose acetate satisfying the above formula, the increase in the viscosity of the concentrated solution with respect to the viscosity average degree of polymerization is linear.

In addition, the cellulose acylate used in the present invention preferably has a narrow molecular weight distribution of Mw / Mn (Mw is a weight average molecular weight, Mn is a number average molecular weight) by gel permeation chromatography. The specific value of Mw / Mn is 1.0 to 5.0, preferably 1.0 to 4.0, and more preferably 1.5 to 3.5.

Cellulose acylate with less low molecular components satisfies the uniformity because the relationship between the viscosity average polymerization degree (DP) and the concentrated solution viscosity (η), the molecular weight distribution of Mw / Mn, or the range of crystallization heat generation is reduced. Can do. When the low molecular component is removed, the average molecular weight (degree of polymerization) increases, but the viscosity becomes lower than that of normal cellulose acylate, which is useful. Cellulose acylate having a small amount of low molecular components can be obtained by removing low molecular components from cellulose acylate synthesized by a usual method.

The removal of the low molecular component can be carried out by washing the cellulose acylate with an appropriate organic solvent. Examples of the organic solvent include ketones (eg, acetone), acetates (eg, methyl acetate) and cellosolves (eg, methyl cellosolve). In the present invention, it is preferable to use ketones, particularly acetone. When cellulose acylate obtained by a usual method is washed once with an organic solvent, low molecular weight cellulose acetate of about 5 to 15% by mass with respect to the weight of the raw material is obtained. Here, the acetone extract of the final cellulose acylate is more preferably 5% by mass or less. In order to increase the efficiency of removing low molecular components, it is preferable to adjust the particle size by pulverizing or sieving the cellulose acetate particles before washing. Specifically, 70% of the particles passing through 20 mesh
It is preferable to adjust so that it may become the above. As a cleaning method, a solvent circulation method such as a Soxhlet extraction method can be employed. Moreover, it stirs with a solvent in a normal stirring tank,
Washing can also be carried out by separating from the solvent.

In addition, when manufacturing a cellulose acetate with few low molecular components, it is preferable to adjust the sulfuric acid catalyst amount in an acetylation reaction to 10 to 15 weight part with respect to 100 weight of cellulose. When the amount of the sulfuric acid catalyst is within the above range (relatively large amount), it is preferable in terms of molecular weight distribution (
Cellulose acylate having a uniform molecular weight distribution can be synthesized.

The cellulose acylate of the present invention has an acid dissociation index pKa in an aqueous solution of 1.93 to 4.5.
It may also contain at least one acid selected from 0, or at least one selected from partially esterified products, alkali metal salts of acids, and alkaline earth metal salts of the acids. In that case, the total content of alkali metal and alkaline earth metal in 1 g of cellulose acylate is 1 × 10 ^−8.
It is preferable that it is a cellulose acetate which is -5.5 * 10 < ^-6 > equivalent (ion equivalent conversion) or less. In this case, at least a part of the carboxyl groups integrated into cellulose acylate and / or hemicellulose acylate is present as cellulose acylate present in acid form.

The moisture content of the cellulose acylate of the present invention is preferably 2% by mass or less, more preferably 1% by mass or less, and particularly preferably a cellulose acylate having a moisture content of 0.7% by mass or less. In general, cellulose acylate contains water and is 2.5 to 5% by mass.
It has been known. In order to obtain the moisture content of the cellulose acylate in the present invention, it is necessary to dry, and the method is not particularly limited as long as the desired moisture content is obtained. For example, the temperature may be increased in a dryer, the air may be dried by sending high-temperature air, or the drying may be performed at a low temperature under reduced pressure. A preferable drying temperature is 50 to 150 ° C., and further 70 to 12 ° C.
0 ° C. When the reduced pressure state is carried out, it is 1 Pa to 0.05 MPa, and further 10 Pa.
It is -0.02MPa, Especially it is 50Pa-0.01MPa. Moreover, the moisture of a cellulose acylate may be reduced by making a desiccant absorb a water | moisture content using a desiccant, and the cellulose acylate which has the moisture content of this invention may be obtained. In addition, drying time is not specifically limited, It implements so that it may become the moisture content of the cellulose acylate of this invention. The water content of these cellulose acylates can be determined by collecting a certain amount of cellulose acylate and measuring it with Karl Fischer.

As for the moisture content, in JP2003-119296, in order to reduce the variation in retardation of the cellulose ester film used for the optical compensation film, the moisture content in the dope is 0.01 to 2% by mass, when drying after casting A cellulose ester film having a residual solvent amount of 0.1 to 480% by mass and a moisture content of the film of 5% by mass or less is described, and this invention is also applicable to the present invention.

In the cellulose acylate of the present invention, the yellowness index (YI) serving as an index of yellowness is, for example, 0.1 to 10 (preferably 0.1 to 7, and haze is 0.05 to 5). The transparency of the cellulose triacetate is, for example, 60 to 100%, preferably 8
It is 0 to 100%, more preferably 85 to 100%. In addition, the measuring method of YI, haze, and transparency is as follows.

(Yellowness index (YI) of cellulose acylate alone)
12.0 g of dried cellulose acylate is accurately weighed, and 88.0 g of a mixed solvent of methylene chloride / methanol = 9/1 (weight ratio) is added and completely dissolved (CTA12
(Mass% solution). Color difference meter (Nippon Denshoku Industries Co., Ltd., color difference Σ90) and glass cell (width 45mm)
, Height 45 mm, optical path length 10 mm), and YI is calculated by the following formula.
YI = YI2-YI1
(In the formula, YI1 is a mixed solvent Y of methylene chloride / methanol = 9/1 (weight ratio)).
I value and YI2 indicate the YI value of a CTA 12% by mass solution).

(Haze of cellulose acylate (single))
12.0 g of dried cellulose acylate is accurately weighed, and 88.0 g of a mixed solvent of methylene chloride / methanol = 9/1 (weight ratio) is added and completely dissolved (CTA12
(Mass% solution). Using a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd.), a glass cell (width 45 mm, height 45
mm, optical path length 10 mm), and measurement is performed as follows. A mixed solvent of methylene chloride / methanol = 9/1 (weight ratio) is put in a glass cell, set in a turbidimeter, and zero point alignment and standard alignment are performed. Next, a CTA 12% by mass solution is placed in a glass cell, set in a turbidimeter, and the numerical value is read.

(Transparency of cellulose acylate (single))
8.0 g of dried cellulose acylate is accurately weighed, and 125.3 g of a mixed solvent of methylene chloride / methanol = 9/1 (weight ratio) is added and completely dissolved (CTA6
(Mass% solution). Cesium phototube, filter no. 12 is used, a mixed solvent of methylene chloride / methanol = 9/1 (weight ratio) is put into a glass cell having an optical path length of 100 mm, and the transmittance is measured to obtain a blank. Next, a 6% by mass CTA solution is put into a glass cell having an optical path length of 100 mm, the transmittance is measured, and the transmittance of the sample solution when the blank is 100% is defined as the transparency of the sample.

(Thermal properties of cellulose acylate (alone))
The cellulose acylate of the present invention preferably has a glass transition temperature (Tg) of 70 to 200 ° C, more preferably 100 to 180 ° C. Generally, Tg of cellulose triacetate is about 150 to 170 ° C., and is slightly affected by the degree of acetylation and the degree of polymerization. If the Tg is too low, the mechanical durability is lost at a high temperature during handling. If the Tg is too high, the dissolution is poor or the produced cellulose acylate film is fragile and difficult to use.

The cellulose acylate of the present invention is not particularly limited in terms of crystallization heat generation. In general, cellulose acylate having a low degree of crystallinity is characterized by high solubility in a solvent and high moldability. On the other hand, however, the cellulose acylate in the present invention has a tendency that the film strength is inferior when it is made into a film, and the crystallization heat generation (ΔHcr) from the molten state is 2 to 20 J / g, preferably 3 to 18 J / g. g, more preferably 3.5 to 15 J / g cellulose acylate. Here, the crystallization calorific value of cellulose acylate was evaluated as follows. First, a 13% by mass solution of cellulose acylate in dichloromethane / ethanol = 9/1 (weight ratio) is prepared, and pressure filtered at 0.5 kgf / cm ² with a 10 μm cloth filter. The obtained dope was extruded onto a glass plate using a coater, dried at 35 ° C. for 20 minutes, peeled off from the glass plate, and vacuum dried at 100 ° C. for 0.5 hour. About 10 mg of the obtained sample is packed in a standard aluminum pan, placed on the sample stage of a heat-compensated differential scanning calorimeter (DSC), held at an appropriate melting temperature for a short time to melt the cellulose acylate, and then the temperature lowering rate It was cooled to room temperature at 4 ° C./min for crystallization. The crystallization exotherm (ΔHcr) was determined from the exothermic peak area of the obtained DSC curve. The DSC measurement is performed under a nitrogen atmosphere, the temperature calibration is performed by two-point calibration of In (melting point: 156.60 ° C.) Sn (melting point: 231.88 ° C.), and the calorific value calibration is performed by In ( The heat of fusion is 28.45 J / g). The analysis method for the crystallization temperature conforms to the provisions of JIS K 7121-1987, and the analysis method for the crystallization heat generation conforms to the provisions of JIS K 7122-1987.

The cellulose acylate of the present invention has high moisture resistance and dimensional stability, and has a crystallization exotherm as described above in spite of a high degree of acetylation. The solution viscosity is low and the molding processability at high speed is high. Since the cellulose acylate of the present invention is essentially low in crystallinity, a molded product can be obtained efficiently while maintaining high moldability without performing a special treatment during film molding or the like. Cellulose acylate
Although it may use for shaping | molding in the various forms (for example, powder shape, pellet shape, etc.) according to the kind of shaping | molding method, it is often used as a cellulose acylate solution (dope) normally.

In addition, the solvent about the cellulose acylate solution and film produced using a non-chlorine-type organic solvent is disclosed by the following patents including the melt | dissolution method, and is a preferable aspect. They are, for example, JP 2000-95876 A, JP 12-95877 A, JP
0-324774, JP-A-8-152514, JP-A-10-330538, JP-A-9-9
5538, JP-A-9-95557, JP-A-10-235664, JP-A-12-63534
JP-A-11-21379, JP-A-10-182853, JP-A-10-278056, JP-A-10-279702, JP-A-10-323853, JP-A-10-237186, JP-A-11-60807, JP-A-11-152342, Special Kaihei 11-292988, JP-A-1
1-60752, JP-A-11-60752, and the like. According to these descriptions, not only the preferred solvent for the cellulose acylate produced using the non-chlorine organic solvent of the present invention, but also the solution physical properties and coexisting substances to be coexisted are described. is there.

For example, Japanese Patent Application Laid-Open No. 2002-086467 discloses a cellulose acylate having a non-chlorine solvent having a dielectric constant in the range of 2.0 to 35.0 in order to improve liquid aging stability, mechanical properties and optical properties of the film. The production method of the rate film is described.

Furthermore, JP 2002-086468 discloses a mixture of a non-chlorine solvent main solvent and alcohol in order to improve the dope solution aging stability, the optical properties of the film after film formation, mechanical strength, dimensional stability, and the like. Disclosed is a method for producing a cellulose acylate film in which a main solvent is composed of carbon, hydrogen, and oxygen and an oxygen mass fraction is in the range of 0.60 to 0.10.

In addition, JP-A-2002-086469 discloses that the dipole moment of a non-chlorinated solvent is 0.2 to 0.2 in order to improve the stability over time of the liquid, improve the optical properties, mechanical strength, dimensional stability, etc. of the film after film formation. A process for producing a cellulose acylate film in the range of 3.3 is described.

Further, JP 2002-086470 discloses a non-chlorinated solvent and an alcohol mixed solvent in order to improve the liquid aging stability after dissolution and improve the optical properties, mechanical strength, dimensional stability, etc. of the film-forming film. Thus, a process for producing a cellulose acylate film in which the main solvent is a single / two or more mixed solvent and 5% by mass or more of a cyclic structure solvent is described.

JP-A-2002-088166 discloses ethers having a molecular weight of 150 or less, ketones, in order to improve liquid aging stability, optical properties of the film after film formation, mechanical strength, and dimensional stability. A process for producing a cellulose acylate film as one of esters is described.

Furthermore, JP-A-2002-122734 describes a protective film for a polarizing plate in which the water content in a solvent dope containing methylene chloride as a main component is 0.3 to 1% by weight in order to reduce variations in retardation. .

Further, JP-A-2003-055466 discloses a mixture of a chlorinated organic solvent and cellulose acylate to prevent white turbidity of the cellulose acylate solution and to improve the film surface state.
A method for producing a cellulose acylate solution that dissolves upon exposure to a temperature of 0 ° C. is described.

JP 2003-033931 discloses a cellulose acylate film formed by using at least one of ketones and esters as a main solvent in order to make it difficult to cause thermal shrinkage of the formed film. There is a description of a cellulose acylate film having a total residual solvent content of 0.1 to 0.6% by weight after drying.

The inventions relating to these cellulose acylates described above can also be applied to the present invention.

(Additive)
Various additives (for example, peeling accelerators, plasticizers, UV inhibitors, deterioration inhibitors, fine particles, optical property modifiers, etc.) according to applications are added to the cellulose acylate solution of the present invention in each preparation step. be able to. Further, the addition may be performed at any time in the dope preparation process, but may be performed by adding an additive to the final preparation process of the dope preparation process.

(Plasticizer)
The plasticizer preferred in the present invention is preferably a solid having a boiling point of 200 ° C. or higher and a liquid at 25 ° C., or a solid having a melting point of 25 to 250 ° C. More preferred are plasticizers having a boiling point of 250 ° C. or higher and a liquid at 25 ° C. or a solid having a melting point of 25 to 200 ° C. When the plasticizer is a liquid, purification is usually carried out by distillation under reduced pressure, but higher vacuum is preferred,
For example, 100 Pa or less is preferable. It is also particularly preferable to purify using a molecular distillation apparatus or the like. When the plasticizer is a solid, it is generally carried out by recrystallization using a solvent, filtering, washing and drying.

As these preferably added plasticizers, phosphate esters or carboxylic acid esters are used. Examples of phosphate esters include triphenyl phosphate (TPP) and tricresyl phosphate (TCP), cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate. Representative examples of the carboxylic acid ester include phthalic acid esters and citric acid esters. Examples of phthalic acid esters include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), diphenyl phthalate (DPP) and diethylhexyl phthalate (DEHP). Examples of citrate esters include triethyl O-acetyl citrate (OACTE) and tributyl O-acetyl citrate (OACTB), acetyl triethyl citrate, acetyl tributyl citrate. These preferred plasticizers are liquid except for TPP (melting point: about 50 ° C.) at 25 ° C. and have a boiling point of 250 ° C. or higher.

Examples of other carboxylic acid esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters. Examples of glycolic acid esters include triacetin, tributyrin, butylphthalyl butyl glycolate,
Ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, methyl phthalyl methyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, etc. is there. Among them, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, tributyl phosphate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diethyl hexyl phthalate,
Triacetin and ethylphthalyl ethyl glycolate are preferred. In particular, triphenyl phosphate, diethyl phthalate, and ethyl phthalyl ethyl glycolate are preferable. These plasticizers may be used alone or in combination of two or more. The addition amount of the plasticizer is preferably 2 to 30% by mass, particularly 5 to 20% by mass with respect to the cellulose acylate.

These are disclosed in JP-A-5-194788, JP-A-60-250053, JP-A-4-22.
7941, JP-A-6-16869, JP-A-5-271471, JP-A-7-2860.
68, JP-A-5-5047, JP-A-11-80381, JP-A-7-20317,
The plasticizers described in JP-A-8-57879, JP-A-10-152568 and JP-A-10-120824 are also preferred. According to these descriptions, there are many preferable descriptions regarding not only the plasticizer but also its utilization method or its characteristics, and it is also used in the present invention.

In the present invention, as a plasticizer for reducing the optical anisotropy, JP-A-11
(Di) pentaerythritol esters described in No. 124445, JP-A-11-24670
Glycerol esters described in No. 4, diglycerol esters described in JP-A No. 2000-63560, citric acid esters described in JP-A No. 11-92574, JP-A No. 11-909
Substituted phenyl phosphates described in No. 46 are preferably used.

JP 2003-012822 discloses that citrate ester compound as a plasticizer, 2 wt% to 20 wt%
In addition, it is described that by containing a UV agent, pinholes can be reduced, reflection light unevenness due to wrinkles and streaks of the coating film can be eliminated, and an optical film having a low average reflectance can be obtained.

Furthermore, as a plasticizer, in order to improve moisture permeability and dimensional stability, and further improve drying unevenness and wrinkles of adhesive polarizing plate bonding, in a cellulose ester film of a multilayer structure having at least a base layer and a surface layer, A cellulose ester film containing fine particles in at least one surface layer and a non-phosphate plasticizer and a UV agent in a base layer is described.

Further, in order to obtain a cellulose ester film excellent in moisture permeability and retention, Japanese Patent Application Laid-Open No. 2003-096
236 describes a cellulose resin composition in which a specific ester compound is blended as a plasticizer with a cellulose resin.

Further, in order to improve the transparency of the cellulose triacetate film, Japanese Patent No. 2001-122978, the ratio of the absorption of the ATR infrared 1490Cm ^-1 of measured surface by absorption spectrometry and 1370 cm ^-1 on average of both sides 0 An invention that is 20 or less is described.

The inventions relating to these cellulose acylates described above can also be applied to the present invention.

(Anti-degradation agent and UV protection agent)
Cellulose acylate films have degradation inhibitors (eg, antioxidants, peroxide decomposers,
Radical inhibitors, metal deactivators, acid scavengers, amines) and UV inhibitors may be added.

As for the deterioration preventing agent, JP-A-2002-286931 describes an optical film film having at least two layers laminated on a support in order to realize a PDP front filter having excellent durability.

Further, JP-A-2002-363420 discloses a resin containing a UV polymer containing a unit formed from a UV monomer in order to produce a film having excellent spectral absorption, little bleed-out, no coloring, and excellent transparency. The composition is described.

JP 2003-053882 also discloses that a highly functional thin film is formed directly on a cellulose ester film containing 1 to 30 wt% of an additive that is liquid at 20 ° C. in order to form a thin film with high productivity. It describes an optical film provided with a metal compound layer via a layer.

Further, in JP 2003-107201A, in order to prevent deterioration of the planarity of the cellulose ester film, a metal compound layer composed of at least one of oxygen atoms and nitrogen atoms and a metal atom includes at least the cellulose ester film. An optical film provided on one surface directly or via another layer is disclosed.

Japanese Patent Application Laid-Open No. 2003-113317 describes an optical film containing a UV agent in order to obtain an optical film excellent in ultraviolet absorption characteristics, transparency, durability (bleed-out failure) and light resistance.

Further, regarding UV agents, JP-A 2003-026668 describes a benzotriazole-based UV agent having a low melting point, low volatility, and excellent resin compatibility and hardly causes bleeding out.

  Degradation inhibitors (eg, antioxidants, peroxide decomposers, radical inhibitors, metal deactivators, acid scavengers, amines) and UV inhibitors may be added to the cellulose acylate film. With respect to these deterioration inhibitors and UV inhibitors, JP-A-60-235852, JP-A-3-199201, JP-A-5-190707, JP-A-5-194789, JP-A-5-271471, JP-A-5-271471, and JP-A-5-271471. JP-A-6-107854, JP-A-6-118233, JP-A-6-148430, JP-A-7-11056, JP-A-7-11055, JP-A-7-11056, JP-A-8-29619, JP-A-8 JP-A-239509, JP-A-2000-204173, JP-A-5-97073, JP-A-5-194789, JP-A-6-107854, JP-A-60-235852, JP-A-12-193821, JP-A-8 -29619, JP-A-6-118233, and JP-A-6-148430.

These addition amounts are preferably 0.01 to 1% by mass of the solution (dope) to be prepared, and more preferably 0.01 to 0.08% by mass. When the addition amount is less than 0.01% by mass, the effect of the deterioration preventing agent is hardly recognized. When the added amount exceeds 1% by mass,
Bleeding out (bleeding out) of the deterioration preventing agent to the film surface may be observed. The deterioration preventing agent preferable in the present invention is preferably a liquid having a boiling point of 200 ° C. or higher and a liquid at 25 ° C., or a solid having a melting point of 25 to 250 ° C. More preferably, a deterioration inhibitor having a boiling point of 250 ° C. or higher and a liquid at 25 ° C. or a solid having a melting point of 25 to 200 ° C. can be used.
When the deterioration inhibitor is a liquid, purification thereof is usually carried out by distillation under reduced pressure, but higher vacuum is preferable, for example, 100 Pa or less is preferable. It is also particularly preferable to purify using a molecular distillation apparatus or the like. When the plasticizer is a solid, it is generally carried out by recrystallization using a solvent, filtering, washing and drying.

As the deterioration preventing agent, for example, a basic compound having a pKa of 4 or more described in JP-A-5-194789 is preferably exemplified. For example, primary, secondary, tertiary amines and aromatic base compounds are preferred. Specific examples include tributylamine, trihexylamine, trioctylamine, dodecyl-dibutylamine, octadecyl-dimethylamine, tribenzylamine, diethylaminobenzene, and the like. And Compounds A-1 to A-73 and B-1 to B-67 described in (2) can be used. Also,
Preferable examples include compounds described in JP-A-5-197073. In particular,
General formulas (A-I), (A-II), (A-III), (BI), (C-I), (C-II),
Compounds (A-1) to (A-46), (B) classified as (C-III), (D-I) to (D-VII)
-I-1) to (DI-32), (C-1) to (C-10), (DI-1) to (DI)
-96), (D-1) to (D-12), (D-VII-1) to (D-VII-6), (D-VII
I-1) to (D-VIII-67) can be used.

Furthermore, preferred are compounds described in JP-A-6-107854. Specifically, basic compounds (D-1) to (D-69) represented by the general formula (I) of the publication, (AI) to (A-III), (B-I) ), (C-I) to (C-III) (D-1) to (D-69), compounds (A-1) to (A-46), (B-I-1) ~ (B
-I-32) and (CI) to (C-10) can also be preferably used. As a particularly preferred example of the deterioration preventing agent, butylated hydroxytoluene (BHT) can be mentioned.

The ultraviolet absorber preferably used for the cellulose acylate film of the present invention will be described. The cellulose acylate film of the present invention is used for a polarizing plate or a liquid crystal display member because of its high dimensional stability, but an ultraviolet absorber is preferably used from the viewpoint of preventing deterioration of the polarizing plate or the liquid crystal. As the ultraviolet absorber, those excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and having little absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties. Specific examples of the ultraviolet absorber preferably used in the present invention include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like.

Although the specific example as a benzotriazole type ultraviolet absorber is listed below, this invention is not limited to these. 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3) '-Tert-butyl-5'-methylphenyl)
Benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-(3 ", 4"
, 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole, 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6-
(2H-benzotriazol-2-yl) phenol), 2- (2'-hydroxy-3 '
-Tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2,4
-Dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4
-Hydroxy-5-benzoylphenylmethane), (2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, 2 (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5
Chlorbenzotriazole, (2 (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) -5-chlorobenzotriazole, 2,6-di-tert-butyl-p-cresol, pentaerythrityl- Tetrakis [3- (3,5-di-tert-butyl-4
-Hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-
tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-
Hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-
3,5-di-tert-butylanilino) -1,3,5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl -3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 1,3 , 5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris- (3
5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate and the like. In particular, (2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, 2 (2'-hydroxy-3 '
, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, (2 (2 ′
-Hydroxy-3 ', 5'-di-tert-amylphenyl) -5-chlorobenzotriazole, 2,6-di-tert-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate] and triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] are preferred. For example, N, N′-bis [3- (
3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine and other hydrazine-based metal deactivators and tris (2,4-di-tert-butylphenyl) phosphite and other phosphorus processing stabilizers May be used in combination. The addition amount of these compounds is preferably 1 ppm to 1.0% by mass with respect to cellulose acylate, and 10 to 1000 p.
More preferred is pm.

In addition, light stabilizers in the catalog of “Adeka Stub”, an outline of additives for Asahi Denka Plastics, can be used. Light stabilizers and UV absorbers from Ciba Special Chemicals' Tinuvin Product Guide can also be used. SESPRORB in the catalog of SHIPROKASEI KAISYA,
SEENOX, SEETEC, etc. can also be used. Jouhoku Chemical's UV absorbers and antioxidants can also be used. UV absorbers from Kyosho's VIOSORB and Yoshitomi Pharmaceutical can also be used.

Moreover, the ultraviolet absorber described in JP-A-6-148430 can also be preferably used. The ultraviolet absorber described above preferably used in the present invention has high transparency, is excellent in the effect of preventing the deterioration of the polarizing plate and the liquid crystal element, and is particularly preferably a benzotriazole-based ultraviolet absorber with less unnecessary coloring. The amount of the UV absorber used is not uniform depending on the type of compound and the use conditions, but usually 0.2 g to 5.0 g per 1 m ^{2 of the} cellulose acylate film.
g is preferable, 0.4 to 1.5 g is more preferable, and 0.6 to 1.0 g is particularly preferable.

As for spectral transmittance in the ultraviolet region, JP-A-2003-043259, 390 nm, which is necessary for obtaining an optical film, a polarizing plate and a display device excellent in color reproducibility and durability in ultraviolet irradiation.
Describes an optical film having a spectral transmittance of 50% to 95% at 350 nm and a spectral transmittance at 350 nm of 5% or less.

These inventions described above can also be applied to the present invention.

The ultraviolet absorber may be added in advance when a cellulose acylate mixed solution is prepared, or a cellulose acylate dope may be prepared in advance and added at any time until casting. Good. In the latter case, in-line addition of a dope solution in which cellulose acylate is dissolved in a solvent and a solution in which an ultraviolet absorber and a small amount of cellulose acylate are dissolved,
In order to perform mixing, for example, a static mixer (manufactured by Toray Engineering), SWJ
An inline mixer such as (Toray static type in-tube mixer Hi-Mixer) is preferably used. The UV absorber to be added later may be mixed with a matting agent at the same time, or may be mixed with additives such as a retardation control agent, a plasticizer, a deterioration preventing agent and a peeling accelerator. When using an in-line mixer, it is preferable to concentrate and dissolve under high pressure, and the type of the pressurized container is not particularly limited, as long as it can withstand a predetermined pressure and can be heated and stirred under pressure. In addition to the pressure vessel, other instruments such as a pressure gauge and a thermometer are appropriately disposed. The pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or by increasing the vapor pressure of the solvent by heating. Heating is preferably performed from the outside. For example, a jacket type is preferable because temperature control is easy. The heating temperature with the addition of the solvent is preferably not less than the boiling point of the solvent used and in a range where the solvent does not boil, and is preferably set to a range of 30 to 150 ° C, for example. The pressure is adjusted at a set temperature so that the solvent does not boil. After dissolution, it is taken out from the container while cooling, or extracted from the container with a pump or the like and cooled with a heat exchanger or the like, and used for film formation. The cooling temperature at this time may be cooled to room temperature, but 5 to 5 from the boiling point.
It is more preferable to cool to a temperature lower by 10 ° C. and perform casting at that temperature because the dope viscosity can be reduced.

For the cellulose acylate film, an ultraviolet absorber having a melting point of 30 ° C. or higher is preferable,
Furthermore, an ultraviolet absorber having a melting point of 50 ° C. to 200 ° C. is used. The cellulose acylate film of the present invention is preferably used for a liquid crystal display member because of its high dimensional stability and good ultraviolet cut performance. A liquid crystal display member is a member used in a liquid crystal display device. For example, a polarizing plate, a protective film for a polarizing plate, a retardation plate, a reflective plate, a viewing angle improving film, an anti-glare film, a non-reflective film, and charging Prevention films and the like. Among the above descriptions, the cellulose acylate film of the present invention is more preferably used for polarizing plates and protective films for polarizing plates that have strict requirements on dimensional stability. In particular, as a protective film for a polarizing plate of a recent notebook personal computer or the like, a cellulose acylate film having a thinner film than before has been demanded. Even when the film thickness is reduced, in order to sufficiently protect the ultraviolet rays, it is necessary to increase the amount of the ultraviolet absorber used per unit weight than before. Therefore, during the alkali saponification treatment as described above, the amount of the ultraviolet absorber is increased and the conventional polarizing plate protective film having a reduced thickness is likely to cause elution and precipitation of the ultraviolet absorber. In particular, the cellulose acylate film of the present invention containing an ultraviolet absorber having a melting point of 100 ° C. or higher is
Even if the amount of the ultraviolet absorber is increased and the film thickness is reduced, the elution of the ultraviolet absorber during the alkali saponification treatment is extremely small, and the merit in the production process is extremely high. Regarding these, JP-A-2
Although details are disclosed in Japanese Patent No. 000-351859, this technique has been generally used in the past.

JP-A-2002-031715 discloses a copolymer of an ultraviolet-absorbing monomer and an ethylenically unsaturated monomer having a molar extinction coefficient at 380 nm of 4000 or more in an optical film, The invention has been described in which an ultraviolet-absorbing copolymer having a weight average molecular weight of 2,000 to 20,000 is contained to obtain a film having no bleeding out and being transparent and having good long-term weather resistance. It can also be applied to.

(Optical anisotropy control agent)
A retardation control agent for controlling optical anisotropy is optionally added.

Examples thereof include compounds having a molecular structure that has at least two aromatic rings and does not sterically hinder the conformation of the two aromatic rings.

A compound having at least two aromatic rings has a π-bonding plane of 7 or more carbon atoms. Unless the steric hindrance of the conformation of the two aromatic rings, the two aromatic rings form the same plane. According to the study of the present inventors, in order to increase the retardation of the cellulose ester film, it is important to form the same plane by a plurality of aromatic rings. In the present specification, the “aromatic ring” includes an aromatic hetero ring in addition to an aromatic hydrocarbon ring.
The aromatic hydrocarbon ring is particularly preferably a 6-membered ring (that is, a benzene ring). The aromatic heterocycle is generally an unsaturated heterocycle. The aromatic heterocycle is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring. Aromatic heterocycles generally have the most double bonds. As the hetero atom, a nitrogen atom, an oxygen atom and a sulfur atom are preferable, and a nitrogen atom is particularly preferable. Examples of aromatic heterocycles include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring, pyridine ring , Pyridazine ring, pyrimidine ring, pyrazine ring and 1,3,5
-A triazine ring is included. Aromatic rings include benzene ring, furan ring, thiophene ring,
Pyrroyl ring, oxazole ring, thiazole ring, imidazole ring, triazole ring, pyridine ring, pyrimidine ring, pyrazine ring and 1,3,5-triazine ring are preferred.

The number of aromatic rings contained in the retardation control agent is preferably 2 to 20, and preferably 2
It is more preferably from 12 to 12, more preferably from 2 to 8, and most preferably from 2 to 6. In the case of having three or more aromatic rings, the conformation of at least two aromatic rings should not be sterically hindered. The bonding relationship between two aromatic rings can be classified into (a) when a condensed ring is formed, (b) when directly linked by a single bond, and (c) when linked via a linking group (for aromatic rings). , Spiro bonds cannot be formed). From the viewpoint of the retardation increasing function, any of (a) to (c) may be used. However, in the case of (b) or (c), it is necessary not to sterically hinder the conformation of the two aromatic rings.

Examples of the condensed ring (a) (condensed ring of two or more aromatic rings) include an indene ring, a naphthalene ring,
Azulene, fluorene, phenanthrene, anthracene, acenaphthylene, biphenylene, naphthacene, pyrene, indole, isoindole, benzofuran, benzothiophene, indolizine, benzoxazole, benzothiazole, Benzimidazole ring, benzotriazole ring, purine ring, indazole ring, chromene ring, quinoline ring, isoquinoline ring, quinolidine ring, quinazoline ring, cinnoline ring, quinoxaline ring, phthalazine ring, pteridine ring, carbazole ring, acridine ring, phenanthridine Ring, xanthene ring, phenazine ring, phenothiazine ring, phenoxathiin ring, phenoxazine ring and thianthrene ring are included. Naphthalene ring, azulene ring, indole ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzotriazole ring and quinoline ring are preferred.

The single bond (b) is preferably a bond between carbon atoms of two aromatic rings. Two aromatic rings may be bonded with two or more single bonds to form an aliphatic ring or a non-aromatic heterocyclic ring between the two aromatic rings.

The linking group in (c) is also preferably bonded to carbon atoms of two aromatic rings. The linking group is preferably an alkylene group, an alkenylene group, an alkynylene group, —CO—, —O—, —NH—, —S—, or a combination thereof. Examples of linking groups composed of combinations are shown below. In addition, the relationship between the left and right in the following examples of the linking group may be reversed.
c1: -CO-O-
c2: —CO—NH—
c3: -alkylene-O-
c4: —NH—CO—NH—
c5: —NH—CO—O—
c6: —O—CO—O—
c7: -O-alkylene-O-
c8: -CO-alkenylene-
c9: -CO-alkenylene-NH-
c10: -CO-alkenylene-O-
c11: -alkylene-CO-O-alkylene-O-CO-alkylene-
c12: -O-alkylene-CO-O-alkylene-O-CO-alkylene-O-
c13: -O-CO-alkylene-CO-O-
c14: -NH-CO-alkenylene-
c15: -O-CO-alkenylene-

The aromatic ring and the linking group may have a substituent. However, the substituent is required not to sterically hinder the conformation of the two aromatic rings. In steric hindrance, the type and position of substituents are problematic. As the type of the substituent, a sterically bulky substituent (for example, a tertiary alkyl group) tends to cause steric hindrance. As the position of the substituent, steric hindrance is likely to occur when a position adjacent to the bond of the aromatic ring (ortho position in the case of a benzene ring) is substituted. Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxyl, carboxyl, cyano,
Amino, nitro, sulfo, carbamoyl, sulfamoyl, ureido, alkyl group, alkenyl group, alkynyl group, aliphatic acyl group, aliphatic acyloxy group, alkoxy group, alkoxycarbonyl group, alkoxycarbonylamino group, alkylthio group, alkylsulfonyl group, An aliphatic amide group, an aliphatic sulfonamido group, an aliphatic substituted amino group, an aliphatic substituted carbamoyl group, an aliphatic substituted sulfamoyl group, an aliphatic substituted ureido group and a non-aromatic heterocyclic group are included.

The alkyl group preferably has 1 to 8 carbon atoms. A chain alkyl group is preferable to a cyclic alkyl group, and a linear alkyl group is particularly preferable. The alkyl group may further have a substituent (eg, hydroxy, carboxy, alkoxy group, alkyl-substituted amino group). Examples of alkyl groups (including substituted alkyl groups) include methyl, ethyl, n-butyl, n-hexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl and 2-diethylaminoethyl. The alkenyl group preferably has 2 to 8 carbon atoms. A chain alkenyl group is preferable to a cyclic alkenyl group, and a linear alkenyl group is particularly preferable. The alkenyl group may further have a substituent. Examples of alkenyl groups include vinyl, allyl and 1-hexenyl. The alkynyl group preferably has 2 to 8 carbon atoms. A chain alkynyl group is preferable to a cyclic alkynyl group, and a linear alkynyl group is particularly preferable. The alkynyl group may further have a substituent. Examples of alkynyl groups include ethynyl, 1-butynyl and 1-hexynyl.

The aliphatic acyl group preferably has 1 to 10 carbon atoms. Examples of the aliphatic acyl group include acetyl, propanoyl and butanoyl. The aliphatic acyloxy group preferably has 1 to 10 carbon atoms. Examples of the aliphatic acyloxy group include acetoxy. The number of carbon atoms of the alkoxy group is preferably 1 to 8. The alkoxy group may further have a substituent (eg, alkoxy group). Examples of alkoxy groups (including substituted alkoxy groups) include methoxy, ethoxy, butoxy and methoxyethoxy. The alkoxycarbonyl group preferably has 2 to 10 carbon atoms. Examples of the alkoxycarbonyl group include methoxycarbonyl and ethoxycarbonyl. The number of carbon atoms of the alkoxycarbonylamino group is preferably 2 to 10. Examples of the alkoxycarbonylamino group include methoxycarbonylamino and ethoxycarbonylamino.

The alkylthio group preferably has 1 to 12 carbon atoms. Examples of the alkylthio group include methylthio, ethylthio and octylthio. The alkylsulfonyl group preferably has 1 to 8 carbon atoms. Examples of the alkylsulfonyl group include methanesulfonyl and ethanesulfonyl. The aliphatic amide group preferably has 1 to 10 carbon atoms. Examples of the aliphatic amide group include acetamide. The aliphatic sulfonamide group preferably has 1 to 8 carbon atoms. Examples of the aliphatic sulfonamido group include methanesulfonamido, butanesulfonamido and n-octanesulfonamido. The number of carbon atoms of the aliphatic substituted amino group is preferably 1 to 10. Examples of the aliphatic substituted amino group include dimethylamino, diethylamino and 2-carboxyethylamino. The aliphatic substituted carbamoyl group has 2 to 10 carbon atoms.
It is preferable that Examples of the aliphatic substituted carbamoyl group include methylcarbamoyl and diethylcarbamoyl. The aliphatic substituted sulfamoyl group preferably has 1 to 8 carbon atoms. Examples of the aliphatic substituted sulfamoyl group include methylsulfamoyl and diethylsulfamoyl. The number of carbon atoms in the aliphatic substituted ureido group is preferably 2 to 10. Examples of the aliphatic substituted ureido group include methylureido. Examples of non-aromatic heterocyclic groups include piperidino and morpholino.

The molecular weight of the retardation control agent is preferably 300 to 800. The boiling point of the retardation control agent is preferably 260 ° C. or higher. The boiling point can be measured using a commercially available measuring device (for example, TG / DTA100, manufactured by Seiko Electronics Industry Co., Ltd.). Specific examples of the retardation control agent are shown below. In each specific example, the aromaticity of the aromatic ring is indicated by a circle.

A rod-shaped compound having at least two aromatic rings can also be used as a retardation control agent. The rod-like compound preferably has a linear molecular structure. The linear molecular structure means that the molecular structure of the rod-like compound is linear in the most thermodynamically stable structure. The most thermodynamically stable structure can be obtained by crystal structure analysis or molecular orbital calculation. For example, molecular orbital calculation software (for example, WinMOPAC2000 (
Molecular orbital calculation using (registered trademark), manufactured by Fujitsu Limited), and the molecular structure that minimizes the heat of formation of the compound can be obtained. The molecular structure being linear means that the angle of the molecular structure is 140 degrees or more in the thermodynamically most stable structure obtained by calculation as described above.

As the rod-shaped compound having at least two aromatic rings, a compound represented by the following general formula (I) is preferable.
Formula (I): Ar ¹ -L ¹ -Ar ²
In the general formula (I), Ar ¹ and Ar ² are each independently an aromatic group.
In the present specification, the aromatic group includes an aryl group (aromatic hydrocarbon group), a substituted aryl group, an aromatic heterocyclic group, and a substituted aromatic heterocyclic group. An aryl group and a substituted aryl group are more preferable than an aromatic heterocyclic group and a substituted aromatic heterocyclic group. The heterocycle of the aromatic heterocyclic group is generally unsaturated. Aromatic heterocycles are 5-membered, 6
A membered ring or a 7-membered ring is preferable, and a 5-membered ring or a 6-membered ring is more preferable. Aromatic heterocycles generally have the most double bonds. As a hetero atom, a nitrogen atom, an oxygen atom or a sulfur atom is preferable, and a nitrogen atom or a sulfur atom is more preferable. Examples of aromatic heterocycles include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring, pyridine Rings, pyridazine rings, pyrimidine rings, pyrazine rings, and 1,3,5-triazine rings are included. As the aromatic ring of the aromatic group, a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, a thiazole ring, an imidazole ring, a triazole ring, a pyridine ring, a pyrimidine ring and a pyrazine ring are preferable, and a benzene ring is particularly preferable. .

Examples of the substituent of the substituted aryl group and the substituted aromatic heterocyclic group include a halogen atom (F,
Cl, Br, I), hydroxyl, carboxyl, cyano, amino, alkylamino groups (
Eg, methylamino, ethylamino, butylamino, dimethylamino), nitro, sulfo,
Carbamoyl, alkylcarbamoyl groups (eg, N-methylcarbamoyl, N-ethylcarbamoyl, N, N-dimethylcarbamoyl), sulfamoyl, alkylsulfamoyl groups (eg, N-methylsulfamoyl, N-ethylsulfamoyl, N, N-dimethylsulfamoyl), ureido, alkylureido group (eg, N-methylureido, N, N-dimethylureido, N, N, N′-trimethylureido), alkyl group (eg, methyl, ethyl, Propyl, butyl, pentyl, heptyl, octyl, isopropyl, s-butyl, t-
Amyl, cyclohexyl, cyclopentyl), alkenyl groups (eg, vinyl, allyl, hexenyl), alkynyl groups (eg, ethynyl, butynyl), acyl groups (eg, formyl, acetyl, butyryl, hexanoyl, lauryl), acyloxy groups (eg, Acetoxy, butyryloxy, hexanoyloxy, lauryloxy), alkoxy groups (eg, methoxy, ethoxy, propoxy, butoxy, pentyloxy, heptyloxy, octyloxy), aryloxy groups (eg, phenoxy), alkoxycarbonyl groups (eg, Methoxycarbonyl,
Ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, heptyloxycarbonyl), aryloxycarbonyl groups (eg, phenoxycarbonyl), alkoxycarbonylamino groups (eg, butoxycarbonylamino, hexyloxycarbonylamino), alkylthio groups (eg, , Methylthio, ethylthio, propylthio, butylthio, pentylthio, heptylthio, octylthio), arylthio groups (e.g.,
Phenylthio), alkylsulfonyl groups (eg, methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, pentylsulfonyl, heptylsulfonyl, octylsulfonyl), amide groups (eg, acetamide, butylamide group, hexylamide, laurylamide) and non-aromatic Family heterocyclic groups (eg, morpholyl, pyrazinyl) are included.

Substituents of substituted aryl groups and substituted aromatic heterocyclic groups include halogen atoms, cyano, carboxyl, hydroxyl, amino, alkyl-substituted amino groups, acyl groups, acyloxy groups, amide groups, alkoxycarbonyl groups, alkoxy groups, alkylthios. And groups and alkyl groups are preferred. The alkyl part and alkyl group of the alkylamino group, alkoxycarbonyl group, alkoxy group and alkylthio group may further have a substituent. Examples of the alkyl moiety and the substituent of the alkyl group include halogen atom, hydroxyl, carboxyl, cyano, amino, alkylamino group, nitro, sulfo, carbamoyl, alkylcarbamoyl group, sulfamoyl, alkylsulfamoyl group, ureido, alkylureido Group, alkenyl group, alkynyl group, acyl group, acyloxy group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxycarbonylamino group, alkylthio group, arylthio group, alkylsulfonyl group, amide group and non-aromatic An aromatic heterocyclic group is included. As the substituent for the alkyl moiety and the alkyl group, a halogen atom, hydroxyl, amino, alkylamino group, acyl group, acyloxy group, acylamino group, alkoxycarbonyl group and alkoxy group are preferable.

In the general formula (I), L ¹ represents an alkylene group, an alkenylene group, an alkynylene group,-
A divalent linking group selected from the group consisting of O-, -CO-, and combinations thereof.
The alkylene group may have a cyclic structure. As the cyclic alkylene group, cyclohexylene is preferable, and 1,4-cyclohexylene is particularly preferable. As the chain alkylene group, a linear alkylene group is more preferable than a branched alkylene group. The alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 15, more preferably 1 to 10, still more preferably 1 to 8, and most preferably 1 to 6 carbon atoms. It is.

The alkenylene group and the alkynylene group preferably have a chain structure rather than a cyclic structure, and more preferably have a linear structure rather than a branched chain structure. The number of carbon atoms of the alkenylene group and the alkynylene group is preferably 2 to 10, more preferably 2 to 8, further preferably 2 to 6, further preferably 2 to 4, and most preferably 2. (Vinylene or ethynylene). The arylene group preferably has 6 to 20 carbon atoms, more preferably 6 to 16, and still more preferably 6 to 12.

The example of the bivalent coupling group which consists of a combination is shown.
L-1: —O—CO-alkylene group —CO—O—
L-2: -CO-O-alkylene group -O-CO-
L-3: —O—CO—alkenylene group —CO—O—
L-4: -CO-O-alkenylene group -O-CO-
L-5: -O-CO-alkynylene group -CO-O-
L-6: -CO-O-alkynylene group -O-CO-
L-7: -O-CO-arylene group -CO-O-
L-8: -CO-O-arylene group -O-CO-
L-9: -O-CO-arylene group -CO-O-
L-10: -CO-O-arylene group -O-CO-

In the molecular structure of the general formula (I), the angle formed by Ar ¹ and Ar ² across L ¹ is preferably 140 ° or more.
As the rod-like compound, a compound represented by the following formula (II) is more preferable.
Formula ^{(II): Ar 1 -L 2} -X-L 3 -Ar 2
In the general formula (II), Ar ¹ and Ar ² are each independently an aromatic group. The definition and examples of the aromatic group are the same as those of Ar ¹ and Ar ^{2 in} the general formula (I).

In the general formula (II), L ² and L ³ are each independently an alkylene group, —O—,
It is a divalent linking group selected from the group consisting of —CO— and combinations thereof.
The alkylene group preferably has a chain structure rather than a cyclic structure, and more preferably has a linear structure rather than a branched chain structure.
The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 8, more preferably 1 to 6, still more preferably 1 to 4, and 1 or 2 (methylene or Most preferred is ethylene).
L ² and L ³ are particularly preferably —O—CO— or —CO—O—.

In the general formula (II), X is 1,4-cyclohexylene, vinylene or ethynylene.
Specific examples of the compound represented by the general formula (I) are shown below.

Specific examples (1) to (34), (41), and (42) have two asymmetric carbon atoms at the 1-position and the 4-position of the cyclohexane ring. However, specific examples (1), (4) to (34), (41), (
No. 42) has a symmetrical meso type molecular structure, so there is no optical isomer (optical activity), and only a geometric isomer (trans type and cis type) exists. The trans type (1-trans) and cis type (1-cis) of specific example (1) are shown below.

As described above, the rod-like compound preferably has a linear molecular structure. for that reason,
The trans type is preferable to the cis type.
Specific examples (2) and (3) have optical isomers (a total of four isomers) in addition to geometric isomers. As for geometric isomers, the trans type is similarly preferable to the cis type. The optical isomer is not particularly superior or inferior, and may be D, L, or a racemate.
In specific examples (43) to (45), the central vinylene bond includes a trans type and a cis type.
For the same reason as above, the trans type is preferable to the cis type.

Two or more rod-shaped compounds having a maximum absorption wavelength (λmax) shorter than 250 nm in the ultraviolet absorption spectrum of the solution may be used in combination.
The rod-like compound can be synthesized with reference to methods described in literature. References include Mol. Cryst. Liq. Cryst., 53, 229 (1979), 89, 93 (1982), 145, 111 (1987), 170, 43 Page (1989), J. Am. Chem. Soc., 113, 1349 (1991), 118, 5346 (1996), 92, 1582 (1970), J. Org Chem., 40, 420 (1975), Tetrahedron, 48, 16, 3437 (1992). The addition amount of the retardation control agent is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, based on the amount of the polymer.

Moreover, the compound which has a triphenylene ring is mentioned as another retardation control agent. Examples of the compound having a triphenylene ring include compounds represented by the following general formula ().

In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, halogen atom, nitro, sulfo, aliphatic group, aromatic group, heterocyclic group, —O ^{-R 11, -S-R 12,} -
^{CO-R 13, -O-CO} -R 14, -CO-O-R 15, -O-CO-O-R 16, -NR 17 R
^{18, -CO-NR 19 R 20} , -NR 21 -CO-R 22, -O-CO-NR 23 R 24, -SiR 25
R ²⁶ R ²⁷ , —O—SiR ²⁸ R ²⁹ R ³⁰ , —S—CO—R ³¹ , —O—SO ₂ —R ³² , —SO—
R ³³ , —NR ³⁴ —CO—O—R ³⁵ , —SO ₂ —R ³⁶ or —NR ³⁷ —CO—NR ³⁸ R ³⁹ , wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² ,
^{R 23, R 24, R 25} , R 26, R 27, R 28, R 29, R 30, R 31, R 32, R 33, R 34, R 35, R
³⁶ , R ³⁷ , R ³⁸ and R ³⁹ are each independently a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group; and R ¹ and R ² , R ³ and R ⁴ or R ⁵ R ⁶ may be bonded to each other to form a ring. R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are —O—R ¹¹ , —S—R ^1.
2 , -O-CO-R ¹⁴ , -O-CO-O-R ¹⁶ , -NR ¹⁷ R ¹⁸ , -NR ²¹ -CO-R ²² or -O-CO-NR ²³ R ²⁴ —O—R ¹¹ , —S—R ¹² , —O—C
It is more preferably O—R ¹⁴ , —O—CO—O—R ¹⁶ or —O—CO—NR ²³ R ²⁴ , and more preferably —O—R ¹¹ or —O—CO—R ^14. , -O-CO-R ¹⁴
Most preferably. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ ,
^{R 20, R 21, R 22} , R 23, R 24, R 25, R 26, R 27, R 28, R 29, R 30, R 31, R 32, R
³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ are preferably a hydrogen atom, an aliphatic group or an aromatic group. R ¹⁴ of -O-CO-R ¹⁴ is most preferably an aromatic group.
In the formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are preferably the same group.

In this specification, an aliphatic group means an alkyl group, an alkenyl group, an alkynyl group, a substituted alkyl group, a substituted alkenyl group, and a substituted alkynyl group. The alkyl group may be cyclic (cycloalkyl group). Moreover, the alkyl group may have a branch. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and most preferably 1 to 10 carbon atoms. Examples of alkyl groups include methyl, ethyl, i-propyl, butyl, i-butyl, s-butyl, t-butyl, t-pentyl, hexyl, octyl, t-octyl, dodecyl and tetracosyl. The alkenyl group may be cyclic (cycloalkenyl group). The alkenyl group may have a branch. The alkenyl group may have two or more double bonds. The alkenyl group has preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and most preferably 2 to 10 carbon atoms. Examples of alkenyl groups include vinyl, allyl and 3-heptenyl. The alkynyl group may be cyclic (cycloalkynyl group). Moreover, the alkynyl group may have a branch. The alkynyl group may have two or more triple bonds. The alkynyl group has preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and most preferably 2 to 10 carbon atoms. Examples of the alkynyl group include ethynyl, 2-propynyl, 1-pentynyl and 2,4-octadiynyl.

Examples of the substituent of the substituted alkyl group, the substituted alkenyl group and the substituted alkynyl group include a halogen atom, nitro, sulfo, an aromatic group, a heterocyclic group, —O—R ⁴¹ , —S—R ⁴² , —CO—R. ⁴³
—O—CO—R ⁴⁴ , —CO—O—R ⁴⁵ , —O—CO—O—R ⁴⁶ , —NR ⁴⁷ R ⁴⁸ , —CO—
^{NR 49 R 50, -NR 51 -CO} -R 52, -O-CO-NR 53 R 54, -SiR 55 R 56 R 57 R 58
And —O—SiR ⁵⁹ R ⁶⁰ R ⁶¹ R ⁶² are included. R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ ,
R ⁴⁷ , R ⁴⁸ , R ⁴⁹ , R ⁵⁰ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁵⁸ , R ⁵⁹ , R
⁶⁰ , R ⁶¹ and R ⁶² are each independently a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. The alkyl part of the substituted alkyl group is the same as the above alkyl group. Examples of substituted alkyl groups include benzyl, phenethyl, 2-methoxyethyl, ethoxymethyl, 2- (2-
Methoxyethoxy) ethyl, 2-hydroxyethyl, hydroxymethyl, 2-carboxyethyl, carboxymethyl, ethoxycarbonylmethyl, 4-acryloyloxybutyl, trichloromethyl and perfluoropentyl. The alkenyl part of the substituted alkenyl group is the same as the above alkenyl group. Examples of substituted alkenyl groups include styryl and 4-methoxystyryl. The alkynyl part of the substituted alkynyl group is the same as the above alkynyl group. Examples of substituted alkynyl groups include 4-butoxyphenylethynyl, 4-
Propylphenylethynyl and trimethylsilylethynyl are included.

In the present specification, the aromatic group means an aryl group and a substituted aryl group. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and most preferably 6 to 10. Examples of the aryl group include phenyl, 1-naphthyl and 2-naphthyl. Examples of the substituent of the substituted aryl group include a halogen atom, nitro, sulfo, aliphatic group, aromatic group, heterocyclic group, —O—R ⁷¹ , —S—R ⁷² , —CO—.
R ⁷³ , —O—CO—R ⁷⁴ , —CO—O—R ⁷⁵ , —O—CO—O—R ⁷⁶ , —NR ⁷⁷ R ⁷⁸ , —
^{CO-NR 79 R 80, -NR} 81 -CO-R 82, -O-CO-NR 83 R 84, -SiR 85 R 86 R
⁸⁷ R ⁸⁸ and —O—SiR ⁸⁹ R ⁹⁰ R ⁹¹ R ⁹² are included. R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ ,
R ⁷⁶ , R ⁷⁷ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ , R ⁸⁸ , R
⁸⁹ , R ⁹⁰ , R ⁹¹ and R ⁹² are each independently a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

The aryl part of the substituted aryl group is the same as the above aryl group. Examples of substituted aryl groups include p-biphenylyl, 4-phenylethynylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 2- Propoxyphenyl, 3-propoxyphenyl, 4-propoxyphenyl, 2-butoxyphenyl, 3-butoxyphenyl, 4-butoxyphenyl, 2-hexyloxyphenyl, 3-hexyloxyphenyl, 4-hexyloxyphenyl, 2-octyloxy Phenyl, 3-octyloxyphenyl, 4-octyloxyphenyl, 2-dodecyloxyphenyl, 3-dodecyloxyphenyl, 4-dodecyloxyphenyl, 2-tetracosyloxyphenyl, 3-tetracosyloxyphenyl, 4
-Tetracosyloxyphenyl, 3,4-dimethoxyphenyl, 3,4-diethoxyphenyl, 3,4-dihexyloxyphenyl, 2,4-dimethoxyphenyl, 2,4-diethoxyphenyl, 2,4-dihexyl Oxyphenyl, 3,5-dimethoxyphenyl, 3
, 5-dimethoxyphenyl, 3,5-dihexyloxyphenyl, 3,4,5-trimethoxyphenyl, 3,4,5-triethoxyphenyl, 3,4,5-trihexyloxyphenyl, 2,4,6 -Trimethoxyphenyl, 2,4,6-triethoxyphenyl, 2,
4,6-trihexyloxyphenyl, 2-fluorophenyl, 3-fluorophenyl,
4-fluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 3,4-difluorophenyl, 3,4-dichlorophenyl, 3,4-dibromo Phenyl, 2,4-difluorophenyl, 2,4-dichlorophenyl, 2,4-dibromophenyl, 3,5-difluorophenyl, 3,5-dichlorophenyl, 3,5-dibromophenyl, 3,4,5-trifluoro Phenyl, 3,4,5-trichlorophenyl, 3,4,5-tribromophenyl,
2,4,6-trifluorophenyl, 2,4,6-trichlorophenyl, 2,4,6-tribromophenyl, pentafluorophenyl, pentachlorophenyl, pentabromophenyl, 2-iodophenyl, 3-iodophenyl, 4-iodophenyl, 2-formylphenyl, 3-formylphenyl, 4-formylphenyl, 2-benzoylphenyl, 3-
Benzoylphenyl, 4-benzoylphenyl, 2-carboxyphenyl, 3-carboxyphenyl, 4-carboxyphenyl, o-tolyl, m-tolyl, p-tolyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2- (2-methoxyethoxy)
Phenyl, 3- (2-methoxyethoxy) phenyl, 4- (2-methoxyethoxy) phenyl, 2-ethoxycarbonylphenyl, 3-ethoxycarbonylphenyl, 4-ethoxycarbonylphenyl, 2-benzoyloxyphenyl, 3-benzoyloxy Phenyl and 4-benzoyloxyphenyl are included.

In the present specification, the heterocyclic group may have a substituent. The heterocyclic ring of the heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic ring of the heterocyclic group may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring. Examples of heteroatoms of the heterocycle include B, N, O, S, Se and Te. Examples of heterocyclic groups include pyrrolidine ring, morpholine ring, 2-bora-1,3
-A dioxolane ring and a 1,3-thiazolidine ring are included. Examples of the unsaturated heterocyclic ring include imidazole ring, thiazole ring, benzothiazole ring, benzoxazole ring, benzotriazole ring, benzoselenazole ring, pyridine ring, pyrimidine ring and quinoline ring. Examples of the substituent of the heterocyclic group are the same as the examples of the substituent of the substituted aryl group.

The molecular weight of the compound having a triphenylene ring is preferably 300 to 2,000. The boiling point of the compound is preferably 260 ° C. or higher. The boiling point can be measured using a commercially available measuring device (for example, TG / DTA100, manufactured by Seiko Electronics Industry Co., Ltd.). Specific examples of the compound having a triphenylene ring are shown below. In addition, several R shown in each example means the same group. The definition of R is shown after the formula together with the specific example number.

(1) Fluoro (2) Chloro (3) Bromo (4) Formyl (5) Benzoyl (6) Carboxyl (7) Butylamino (8) Dibenzylamino (9) Trimethylsilyloxy (10) 1-pentynyl

(11) ethoxycarbonyl (12) 2-hydroxyethoxycarbonyl (13) phenoxycarbonyl (14) N-phenylcarbamoyl (15) N, N-diethylcarbamoyl (16) 4-methoxybenzoyloxy (17) N-phenylcarbamoyloxy (18) Hexyloxy (19) 4-hexyloxybenzoyloxy (20) ethoxy

(21) Benzoyloxy (22) m-dodecyloxyphenylthio (23) t-octylthio (24) p-fluorobenzoylthio (25) isobutyrylthio (26) p-methylbenzenesulfinyl (27) ethanesulfinyl (28) benzenesulfonyl (29) Methanesulfonyl (30) 2-methoxyethoxy

(31) propoxy,
(32) 2-hydroxyethoxy (33) 2-carboxyethoxy (34) 3-heptenyloxy (35) 2-phenylethoxy (36) trichloromethoxy (37) 2-propynyloxy (38) 2,4-octadiynyloxy (39) Perfluoropentyloxy (40) ethoxycarbonylmethoxy

(41) p-methoxyphenoxy (42) m-ethoxyphenoxy (43) o-chlorophenoxy (44) m-dodecyloxyphenoxy (45) 4-pyridyloxy (46) pentafluorobenzoyloxy (47) p-hexyloxy Benzoyloxy (48) 1-naphthoyloxy (49) 2-naphthoyloxy (50) 5-imidazolecarbonyloxy

(51) o-phenoxycarbonylbenzoyloxy (52) m- (2-methoxyethoxy) benzoyloxy (53) o-carboxybenzoyloxy (54) p-formylbenzoyloxy (55) m-ethoxycarbonylbenzoyloxy (56) p-Pivaloylbenzoyloxy (57) propionyloxy (58) phenylacetoxy (59) cinnamoyloxy (60) hydroxyacetoxy

(61) Ethoxycarbonylacetoxy (62) m-butoxyphenylpropioroyloxy (63) propioroyloxy (64) trimethylsilylpropioroyloxy (65) 4-octenoyloxy (66) 3-hydroxypropionyloxy (67) 2-methoxyethoxyacetoxy (68) perfluorobutyryloxy (69) methanesulfonyloxy (70) p-toluenesulfonyloxy

(71) Triethylsilyl (72) m-butoxyphenoxycarbonylamino (73) hexyl (74) phenyl (75) 4-pyridyl (76) benzyloxycarbonyloxy (77) m-chlorobenzamide (78) 4-methylanilino

(79) Nitro (80) sulfo (81) formyl (82) carboxyl (83) methoxycarbonyl (84) benzyloxycarbonyl (85) phenoxycarbonyl

(86) Butoxy (87) Hexyloxy (88) Dodecyloxy (89) Hexanoyloxy (90) Carboxymethoxy

You may use together the compound which has a 2 or more types of triphenylene ring as a retardation control agent.

Moreover, a disk-shaped compound is also mentioned as another retardation control agent. The discotic compound gave a sphere defined by van der Waals radii to the discoid nucleus of the molecule of the compound, and defined the shape as three edges a, b, c of the first rectangular parallelepiped in which the molecule can enter. When the shape of the mother nucleus is preferably a ≧ b> c and b ≧ 0.5a. The shape of the mother nucleus is further b ≧ 0.7
a is preferred. It is also preferable that 0.5b> c.

In this specification, the term “retardation control agent for cellulose ester film” means retardation of a cellulose ester film (specifically, at a wavelength of 550 nm when 3 parts by weight is added to 100 parts by weight of cellulose ester. A compound having a function of increasing the measured retardation value in the thickness direction = Rth ⁵⁵⁰ to 1.5 times or more (preferably 2 times or more, more preferably 2 to 10 times) of the case of no addition. Means. The discotic compound is used in the range of 0.01 to 20 parts by weight with respect to 100 parts by weight of the cellulose ester. Generally, a discotic compound tends to be included in a cellulose ester film in a direction in which the disc surface is perpendicular to the cellulose ester film surface. The discotic compound contained with the disc surface tilted from the cellulose ester film surface can control the orientation of the disc surface by stretching the cellulose ester film (as will be described later).

As the discotic compound, a compound having a 1,3,5-triazine ring or a compound having a porphyrin skeleton can be preferably used. The compound having a 1,3,5-triazine ring is preferably a compound represented by the following formula (I).

Wherein, X ¹ is a single bond, -NR ⁴ -, - a O- or -S-; X ² is a single bond, -NR ⁵ -, - a O- or -S-; X ³ is A single bond, —NR ⁶ —, —O— or —S—; R ¹ , R ² and R ³ are each independently an alkyl group, an alkenyl group, an aryl group or a heterocyclic group; and R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. The compound represented by formula (I) is particularly preferably a melamine compound. In the melamine compound, in formula (I), X ¹ , X ² and X ³ are —NR ⁴ —, —NR ⁵ — and —NR ⁶ —, respectively, or X ¹ , X ² and X ³ Is a single bond, and R ¹ , R ² and R ³ are heterocyclic groups having a free valence on the nitrogen atom. ^{-X 1 -R 1, -X 2 -R} 2 and -X ³ -R ³ are preferably the same substituents. R ¹ , R ² and R ³ are particularly preferably aryl groups. R ⁴ , R ⁵ and R ⁶ are particularly preferably a hydrogen atom.

The alkyl group is preferably a chain alkyl group rather than a cyclic alkyl group. A linear alkyl group is preferred to a branched alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 20, and more preferably 1 to 1.
0 is more preferable, 1 to 8 is still more preferable, and 1 to 6 is most preferable. The alkyl group may have a substituent. Examples of substituents include
Halogen atoms, alkoxy groups (eg, methoxy, ethoxy, epoxyethyloxy) and acyloxy groups (eg, acryloyloxy, methacryloyloxy) are included. The alkenyl group is preferably a chain alkenyl group rather than a cyclic alkenyl group. A linear alkenyl group is preferable to a branched chain alkenyl group. The number of carbon atoms in the alkenyl group is preferably 2 to 30, more preferably 2 to 20, still more preferably 2 to 10, still more preferably 2 to 8, and further preferably 2 to 6 is most preferred. The alkenyl group may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group (eg, methoxy, ethoxy, epoxyethyloxy) and an acyloxy group (eg, acryloyloxy, methacryloyloxy).

The aryl group is preferably phenyl or naphthyl, particularly preferably phenyl. The aryl group may have a substituent. Examples of the substituent include a halogen atom, hydroxyl, cyano, nitro, carboxyl, alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, acyloxy group, alkoxycarbonyl group, alkenyloxycarbonyl group, Aryloxycarbonyl group, sulfamoyl, alkyl-substituted sulfamoyl group, alkenyl-substituted sulfamoyl group, aryl-substituted sulfamoyl group, sulfonamido group, carbamoyl, alkyl-substituted carbamoyl group, alkenyl-substituted carbamoyl group, aryl-substituted carbamoyl group, amide group, alkylthio group, alkenyl A thio group, an arylthio group and an acyl group are included. The alkyl group has the same definition as the alkyl group described above. The alkyl part of the alkoxy group, the acyloxy group, the alkoxycarbonyl group, the alkyl-substituted sulfamoyl group, the sulfonamide group, the alkyl-substituted carbamoyl group, the amide group, the alkylthio group and the acyl group is the same as the alkyl group described above.

The alkenyl group has the same definition as the alkenyl group described above. An alkenyloxy group, an acyloxy group, an alkenyloxycarbonyl group, an alkenyl-substituted sulfamoyl group,
The alkenyl part of the sulfonamide group, alkenyl-substituted carbamoyl group, amide group, alkenylthio group and acyl group is the same as the alkenyl group described above. Examples of the aryl group include phenyl, α-naphthyl, β-naphthyl, 4-methoxyphenyl, 3,4-diethoxyphenyl, 4-octyloxyphenyl and 4-dodecyloxyphenyl. Examples of the aryloxy group, acyloxy group, aryloxycarbonyl group, aryl-substituted sulfamoyl group, sulfonamido group, aryl-substituted carbamoyl group, amide group, arylthio group, and acyl group are the same as the above examples of the aryl group.

When X ¹ , X ² or X ³ is —NR—, —O— or —S—, the heterocyclic group preferably has aromaticity. The heterocycle having aromaticity is generally an unsaturated heterocycle, preferably a heterocycle having the largest number of double bonds. The heterocyclic ring is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and most preferably a 6-membered ring. The hetero atom of the heterocyclic ring is preferably N, S or O, and particularly preferably N. As the heterocyclic ring having aromaticity, a pyridine ring (2-pyridyl or 4-pyridyl as the heterocyclic group) is particularly preferable. The heterocyclic group may have a substituent. Examples of the substituent of the heterocyclic group are the same as the examples of the substituent of the aryl moiety.
When X ¹ , X ² or X ³ is a single bond, the heterocyclic group is preferably a heterocyclic group having a free valence on the nitrogen atom. The heterocyclic group having a free valence on the nitrogen atom is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and a 5-membered ring. Is most preferred. The heterocyclic group may have a plurality of nitrogen atoms. In addition, the heterocyclic group may have a hetero atom other than the nitrogen atom (eg, O, S). The heterocyclic group may have a substituent. Examples of the substituent of the heterocyclic group are the same as the examples of the substituent of the aryl moiety. Examples of heterocyclic groups having free valences on nitrogen atoms are shown below.

The molecular weight of the compound having a 1,3,5-triazine ring is preferably 300 to 2,000. The boiling point of the compound is preferably 260 ° C. or higher. The boiling point can be measured using a commercially available measuring device (for example, TG / DTA100, manufactured by Seiko Electronics Industry Co., Ltd.). Specific examples of the compound having a 1,3,5-triazine ring are shown below. In addition, several R shown in each example means the same group. The definition of R is shown after the formula together with the specific example number.

(1) Butyl (2) 2-methoxy-2-ethoxyethyl (3) 5-undecenyl (4) phenyl (5) 4-ethoxycarbonylphenyl (6) 4-butoxyphenyl (7) p-biphenylyl (8) 4 -Pyridyl (9) 2-naphthyl (10) 2-methylphenyl (11)
3,4-dimethoxyphenyl (12) 2-furyl

(14) Phenyl (15) 3-ethoxycarbonylphenyl (16) 3-butoxyphenyl (17) m-biphenylyl (18) 3-phenylthiophenyl (19) 3-chlorophenyl (20) 3-benzoylphenyl (21) 3 Acetoxyphenyl (22) 3-benzoyloxyphenyl (23) 3-phenoxycarbonylphenyl (24) 3-methoxyphenyl (25) 3-anilinophenyl (26) 3-isobutyrylaminophenyl (27
) 3-phenoxycarbonylaminophenyl (28) 3- (3-ethylureido) phenyl (29) 3- (3,3-diethylureido) phenyl (30) 3-methylphenyl (3)
1) 3-phenoxyphenyl (32) 3-hydroxyphenyl

(33) 4-Ethoxycarbonylphenyl (34) 4-butoxyphenyl (35) p-biphenylyl (36) 4-phenylthiophenyl (37) 4-chlorophenyl (38) 4-
Benzoylphenyl (39) 4-acetoxyphenyl (40) 4-benzoyloxyphenyl (41) 4-phenoxycarbonylphenyl (42) 4-methoxyphenyl (43)
4-anilinophenyl (44) 4-isobutyrylaminophenyl (45) 4-phenoxycarbonylaminophenyl (46) 4- (3-ethylureido) phenyl (47) 4- (
3,3-diethylureido) phenyl (48) 4-methylphenyl (49) 4-phenoxyphenyl (50) 4-hydroxyphenyl

(51) 3,4-diethoxycarbonylphenyl (52) 3,4-dibutoxyphenyl (
53) 3,4-Diphenylphenyl (54) 3,4-diphenylthiophenyl (55) 3
, 4-dichlorophenyl (56) 3,4-dibenzoylphenyl (57) 3,4-diacetoxyphenyl (58) 3,4-dibenzoyloxyphenyl (59) 3,4-diphenoxycarbonylphenyl (60) 3 , 4-Dimethoxyphenyl (61) 3,4-dianilinophenyl (62) 3,4-dimethylphenyl (63) 3,4-diphenoxyphenyl (
64) 3,4-Dihydroxyphenyl (65) 2-naphthyl

(66) 3,4,5-triethoxycarbonylphenyl (67) 3,4,5-tributoxyphenyl (68) 3,4,5-triphenylphenyl (69) 3,4,5-triphenylthiophenyl (70) 3,4,5-trichlorophenyl (71) 3,4,5-tribenzoylphenyl (72) 3,4,5-triacetoxyphenyl (73) 3,4,5-tribenzoyloxyphenyl (74 ) 3,4,5-triphenoxycarbonylphenyl (7
5) 3,4,5-trimethoxyphenyl (76) 3,4,5-trianilinophenyl (7
7) 3,4,5-trimethylphenyl (78) 3,4,5-triphenoxyphenyl (7
9) 3,4,5-trihydroxyphenyl

(80) Phenyl (81) 3-ethoxycarbonylphenyl (82) 3-butoxyphenyl (83) m-biphenylyl (84) 3-phenylthiophenyl (85) 3-chlorophenyl (86) 3-benzoylphenyl (87) 3 -Acetoxyphenyl (88) 3-benzoyloxyphenyl (89) 3-phenoxycarbonylphenyl (90) 3-methoxyphenyl (91) 3-anilinophenyl (92) 3-isobutyrylaminophenyl (93
) 3-phenoxycarbonylaminophenyl (94) 3- (3-ethylureido) phenyl (95) 3- (3,3-diethylureido) phenyl (96) 3-methylphenyl (9)
7) 3-phenoxyphenyl (98) 3-hydroxyphenyl

(99) 4-Ethoxycarbonylphenyl (100) 4-butoxyphenyl (101) p
-Biphenylyl (102) 4-phenylthiophenyl (103) 4-chlorophenyl (1
04) 4-Benzoylphenyl (105) 4-acetoxyphenyl (106) 4-benzoyloxyphenyl (107) 4-phenoxycarbonylphenyl (108) 4-methoxyphenyl (109) 4-anilinophenyl (110) 4-iso Butyrylaminophenyl (111) 4-phenoxycarbonylaminophenyl (112) 4- (3-ethylureido) phenyl (113) 4- (3,3-diethylureido) phenyl (114) 4-methylphenyl (115) 4 -Phenoxyphenyl (116) 4-hydroxyphenyl

(117) 3,4-diethoxycarbonylphenyl (118) 3,4-dibutoxyphenyl (119) 3,4-diphenylphenyl (120) 3,4-diphenylthiophenyl (
121) 3,4-Dichlorophenyl (122) 3,4-dibenzoylphenyl (123)
3,4-diacetoxyphenyl (124) 3,4-dibenzoyloxyphenyl (125
) 3,4-diphenoxycarbonylphenyl (126) 3,4-dimethoxyphenyl (1
27) 3,4-dianilinophenyl (128) 3,4-dimethylphenyl (129) 3,
4-Diphenoxyphenyl (130) 3,4-dihydroxyphenyl (131) 2-naphthyl

(132) 3,4,5-triethoxycarbonylphenyl (133) 3,4,5-tributoxyphenyl (134) 3,4,5-triphenylphenyl (135) 3,4,5-triphenylthiophenyl (136) 3,4,5-Trichlorophenyl (137) 3,4,
5-Tribenzoylphenyl (138) 3,4,5-triacetoxyphenyl (139)
3,4,5-tribenzoyloxyphenyl (140) 3,4,5-triphenoxycarbonylphenyl (141) 3,4,5-trimethoxyphenyl (142) 3,4,5-trianilinophenyl (143 ) 3,4,5-trimethylphenyl (144) 3,4,5-
Triphenoxyphenyl (145) 3,4,5-trihydroxyphenyl

(146) phenyl (147) 4-ethoxycarbonylphenyl (148) 4-butoxyphenyl (149) p-biphenylyl (150) 4-phenylthiophenyl (151) 4
-Chlorophenyl (152) 4-benzoylphenyl (153) 4-acetoxyphenyl (154) 4-benzoyloxyphenyl (155) 4-phenoxycarbonylphenyl (156) 4-methoxyphenyl (157) 4-anilinophenyl (158) 4-isobutyrylaminophenyl (159) 4-phenoxycarbonylaminophenyl (160) 4
-(3-Ethylureido) phenyl (161) 4- (3,3-diethylureido) phenyl (162) 4-methylphenyl (163) 4-phenoxyphenyl (164) 4-hydroxyphenyl

(165) phenyl (166) 4-ethoxycarbonylphenyl (167) 4-butoxyphenyl (168) p-biphenylyl (169) 4-phenylthiophenyl (170) 4
-Chlorophenyl (171) 4-benzoylphenyl (172) 4-acetoxyphenyl (173) 4-benzoyloxyphenyl (174) 4-phenoxycarbonylphenyl (175) 4-methoxyphenyl (176) 4-anilinophenyl (177) 4-isobutyrylaminophenyl (178) 4-phenoxycarbonylaminophenyl (179) 4
-(3-Ethylureido) phenyl (180) 4- (3,3-diethylureido) phenyl (181) 4-methylphenyl (182) 4-phenoxyphenyl (183) 4-hydroxyphenyl

(184) phenyl (185) 4-ethoxycarbonylphenyl (186) 4-butoxyphenyl (187) p-biphenylyl (188) 4-phenylthiophenyl (189) 4
-Chlorophenyl (190) 4-benzoylphenyl (191) 4-acetoxyphenyl (192) 4-benzoyloxyphenyl (193) 4-phenoxycarbonylphenyl (194) 4-methoxyphenyl (195) 4-anilinophenyl (196) 4-Isobutyrylaminophenyl (197) 4-phenoxycarbonylaminophenyl (198) 4
-(3-Ethylureido) phenyl (199) 4- (3,3-diethylureido) phenyl (200) 4-methylphenyl (201) 4-phenoxyphenyl (202) 4-hydroxyphenyl

(203) phenyl (204) 4-ethoxycarbonylphenyl (205) 4-butoxyphenyl (206) p-biphenylyl (207) 4-phenylthiophenyl (208) 4
-Chlorophenyl (209) 4-benzoylphenyl (210) 4-acetoxyphenyl (211) 4-benzoyloxyphenyl (212) 4-phenoxycarbonylphenyl (213) 4-methoxyphenyl (214) 4-anilinophenyl (215) 4-isobutyrylaminophenyl (216) 4-phenoxycarbonylaminophenyl (217) 4
-(3-Ethylureido) phenyl (218) 4- (3,3-diethylureido) phenyl (219) 4-methylphenyl (220) 4-phenoxyphenyl (221) 4-hydroxyphenyl

(222) phenyl (223) 4-butylphenyl (224) 4- (2-methoxy-2-)
Ethoxyethyl) phenyl (225) 4- (5-nonenyl) phenyl (226) p-biphenylyl (227) 4-ethoxycarbonylphenyl (228) 4-butoxyphenyl (
229) 4-methylphenyl (230) 4-chlorophenyl (231) 4-phenylthiophenyl (232) 4-benzoylphenyl (233) 4-acetoxyphenyl (234)
) 4-Benzoyloxyphenyl (235) 4-phenoxycarbonylphenyl (236)
) 4-Methoxyphenyl (237) 4-anilinophenyl (238) 4-isobutyrylaminophenyl (239) 4-phenoxycarbonylaminophenyl (240) 4- (3-
Ethylureido) phenyl (241) 4- (3,3-diethylureido) phenyl (24
2) 4-phenoxyphenyl (243) 4-hydroxyphenyl

(244) 3-Butylphenyl (245) 3- (2-methoxy-2-ethoxyethyl) phenyl (246) 3- (5-nonenyl) phenyl (247) m-biphenylyl (248)
3-ethoxycarbonylphenyl (249) 3-butoxyphenyl (250) 3-methylphenyl (251) 3-chlorophenyl (252) 3-phenylthiophenyl (253)
3-benzoylphenyl (254) 3-acetoxyphenyl (255) 3-benzoyloxyphenyl (256) 3-phenoxycarbonylphenyl (257) 3-methoxyphenyl (258) 3-anilinophenyl (259) 3-isobutyryl Aminophenyl (26
0) 3-phenoxycarbonylaminophenyl (261) 3- (3-ethylureido) phenyl (262) 3- (3,3-diethylureido) phenyl (263) 3-phenoxyphenyl (264) 3-hydroxyphenyl

(265) 2-Butylphenyl (266) 2- (2-methoxy-2-ethoxyethyl) phenyl (267) 2- (5-nonenyl) phenyl (268) o-biphenylyl (269)
2-Ethoxycarbonylphenyl (270) 2-butoxyphenyl (271) 2-methylphenyl (272) 2-chlorophenyl (273) 2-phenylthiophenyl (274)
2-benzoylphenyl (275) 2-acetoxyphenyl (276) 2-benzoyloxyphenyl (277) 2-phenoxycarbonylphenyl (278) 2-methoxyphenyl (279) 2-anilinophenyl (280) 2-isobutyryl Aminophenyl (28
1) 2-phenoxycarbonylaminophenyl (282) 2- (3-ethylureido) phenyl (283) 2- (3,3-diethylureido) phenyl (284) 2-phenoxyphenyl (285) 2-hydroxyphenyl

(286) 3,4-dibutylphenyl (287) 3,4-di (2-methoxy-2-ethoxyethyl) phenyl (288) 3,4-diphenylphenyl (289) 3,4-diethoxycarbonylphenyl (290) ) 3,4-didodecyloxyphenyl (291) 3,4-
Dimethylphenyl (292) 3,4-dichlorophenyl (293) 3,4-dibenzoylphenyl (294) 3,4-diacetoxyphenyl (295) 3,4-dimethoxyphenyl (296) 3,4-di-N- Methylaminophenyl (297) 3,4-diisobutyrylaminophenyl (298) 3,4-diphenoxyphenyl (299) 3,4-dihydroxyphenyl

(300) 3,5-dibutylphenyl (301) 3,5-di (2-methoxy-2-ethoxyethyl) phenyl (302) 3,5-diphenylphenyl (303) 3,5-diethoxycarbonylphenyl (304 ) 3,5-didodecyloxyphenyl (305) 3,5-
Dimethylphenyl (306) 3,5-dichlorophenyl (307) 3,5-dibenzoylphenyl (308) 3,5-diacetoxyphenyl (309) 3,5-dimethoxyphenyl (310) 3,5-di-N- Methylaminophenyl (311) 3,5-diisobutyrylaminophenyl (312) 3,5-diphenoxyphenyl (313) 3,5-dihydroxyphenyl

(314) 2,4-dibutylphenyl (315) 2,4-di (2-methoxy-2-ethoxyethyl) phenyl (316) 2,4-diphenylphenyl (317) 2,4-diethoxycarbonylphenyl (318) ) 2,4-Didodecyloxyphenyl (319) 2,4-
Dimethylphenyl (320) 2,4-dichlorophenyl (321) 2,4-dibenzoylphenyl (322) 2,4-diacetoxyphenyl (323) 2,4-dimethoxyphenyl (324) 2,4-di-N- Methylaminophenyl (325) 2,4-diisobutyrylaminophenyl (326) 2,4-diphenoxyphenyl (327) 2,4-dihydroxyphenyl

(328) 2,3-dibutylphenyl (329) 2,3-di (2-methoxy-2-ethoxyethyl) phenyl (330) 2,3-diphenylphenyl (331) 2,3-diethoxycarbonylphenyl (332) ) 2,3-Didodecyloxyphenyl (333) 2,3-
Dimethylphenyl (334) 2,3-dichlorophenyl (335) 2,3-dibenzoylphenyl (336) 2,3-diacetoxyphenyl (337) 2,3-dimethoxyphenyl (338) 2,3-di-N- Methylaminophenyl (339) 2,3-diisobutyrylaminophenyl (340) 2,3-diphenoxyphenyl (341) 2,3-dihydroxyphenyl

(342) 2,6-dibutylphenyl (343) 2,6-di (2-methoxy-2-ethoxyethyl) phenyl (344) 2,6-diphenylphenyl (345) 2,6-diethoxycarbonylphenyl (346 ) 2,6-didodecyloxyphenyl (347) 2,6-
Dimethylphenyl (348) 2,6-dichlorophenyl (349) 2,6-dibenzoylphenyl (350) 2,6-diacetoxyphenyl (351) 2,6-dimethoxyphenyl (352) 2,6-di-N- Methylaminophenyl (353) 2,6-diisobutyrylaminophenyl (354) 2,6-diphenoxyphenyl (355) 2,6-dihydroxyphenyl

(356) 3,4,5-tributylphenyl (357) 3,4,5-tri (2-methoxy-2-ethoxyethyl) phenyl (358) 3,4,5-triphenylphenyl (359
) 3,4,5-triethoxycarbonylphenyl (360) 3,4,5-tridodecyloxyphenyl (361) 3,4,5-trimethylphenyl (362) 3,4,5-trichlorophenyl (363) 3 , 4,5-tribenzoylphenyl (364) 3,4,5-triacetoxyphenyl (365) 3,4,5-trimethoxyphenyl (366) 3,4
5-Tri-N-methylaminophenyl (367) 3,4,5-triisobutyrylaminophenyl (368) 3,4,5-triphenoxyphenyl (369) 3,4,5-trihydroxyphenyl

(370) 2,4,6-tributylphenyl (371) 2,4,6-tri (2-methoxy-2-ethoxyethyl) phenyl (372) 2,4,6-triphenylphenyl (373
) 2,4,6-triethoxycarbonylphenyl (374) 2,4,6-tridodecyloxyphenyl (375) 2,4,6-trimethylphenyl (376) 2,4,6-trichlorophenyl (377) 2 , 4,6-tribenzoylphenyl (378) 2,4,6-triacetoxyphenyl (379) 2,4,6-trimethoxyphenyl (380) 2,4
6-tri-N-methylaminophenyl (381) 2,4,6-triisobutyrylaminophenyl (382) 2,4,6-triphenoxyphenyl (383) 2,4,6-trihydroxyphenyl

(384) pentafluorophenyl (385) pentachlorophenyl (386) pentamethoxyphenyl (387) 6-N-methylsulfamoyl-8-methoxy-2-naphthyl (388) 5-N-methylsulfamoyl-2- Naphthyl (389) 6-N-phenylsulfamoyl-2-naphthyl (390) 5-ethoxy-7-N-methylsulfamoyl-
2-naphthyl (391) 3-methoxy-2-naphthyl (392) 1-ethoxy-2-naphthyl (393) 6-N-phenylsulfamoyl-8-methoxy-2-naphthyl (394
) 5-Methoxy-7-N-phenylsulfamoyl-2-naphthyl (395) 1- (4-
Methylphenyl) -2-naphthyl (396) 6,8-di-N-methylsulfamoyl-2
-Naphthyl (397) 6-N-2-acetoxyethylsulfamoyl-8-methoxy-2
-Naphtyl (398) 5-acetoxy-7-N-phenylsulfamoyl-2-naphthyl (399) 3-benzoyloxy-2-naphthyl

(400) 5-acetylamino-1-naphthyl (401) 2-methoxy-1-naphthyl (
402) 4-Phenoxy-1-naphthyl (403) 5-N-methylsulfamoyl-1-
Naphthyl (404) 3-N-methylcarbamoyl-4-hydroxy-1-naphthyl (40
5) 5-Methoxy-6-N-ethylsulfamoyl-1-naphthyl (406) 7-tetradecyloxy-1-naphthyl (407) 4- (4-methylphenoxy) -1-naphthyl (
408) 6-N-methylsulfamoyl-1-naphthyl (409) 3-N, N-dimethylcarbamoyl-4-methoxy-1-naphthyl (410) 5-methoxy-6-N-benzylsulfamoyl-1 -Naphthyl (411) 3,6-di-N-phenylsulfamoyl-1
-Naphthyl

(412) methyl (413) ethyl (414) butyl (415) octyl (416) dodecyl (417) 2-butoxy-2-ethoxyethyl (418) benzyl (419) 4-methoxybenzyl

(424) methyl (425) phenyl (426) butyl

(430) methyl (431) ethyl (432) butyl (433) octyl (434) dodecyl (435) 2-butoxy 2-ethoxyethyl (436) benzyl (437) 4-methoxybenzyl

A melamine polymer may be used as the compound having a 1,3,5-triazine ring. The melamine polymer is preferably synthesized by a polymerization reaction between a melamine compound represented by the following formula (II) and a carbonyl compound.

In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. The definitions and substituents of the alkyl group, alkenyl group, aryl group and heterocyclic group are the same as the definitions and substituents of each group described in the formula (I). The polymerization reaction between the melamine compound and the carbonyl compound is the same as the method for synthesizing a normal melamine resin (eg, melamine formaldehyde resin). A commercially available melamine polymer (melamine resin) may be used. The molecular weight of the melamine polymer is preferably 2,000 or more and 400,000 or less. The example of the repeating unit of a melamine polymer is shown below.

MP-1: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OH
MP-2: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OCH ₃
MP-3: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OiC ₄ H ₉
MP-4: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-5: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ NHCOCH═CH ₂
^{MP-6: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3

^{MP-7: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 OCH 3
MP-8: R ¹³ , R ¹⁴ , R ¹⁶ : CH ₂ OH; R ¹⁵ : CH ₂ OCH ₃
MP-9: R ¹³ , R ¹⁴ : CH ₂ OH; R ¹⁵ , R ¹⁶ : CH ₂ OCH ₃
MP-10: R ¹³ , R ¹⁶ : CH ₂ OH; R ¹⁴ , R ¹⁵ : CH ₂ OCH ₃
MP-11: R ¹³ : CH ₂ OH; R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OCH ₃
^{MP-12: R 13, R} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
MP-13: R ¹³ , R ¹⁶ : CH ₂ OCH ₃ ; R ¹⁴ , R ¹⁵ : CH ₂ OH

^{MP-14: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 OiC 4 H 9
^{MP-15: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 OiC 4 H 9
MP-16: R ¹³ , R ¹⁴ : CH ₂ OH; R ¹⁵ , R ¹⁶ : CH ₂ OiC ₄ H ₉
MP-17: R ¹³ , R ¹⁶ : CH ₂ OH; R ¹⁴ , R ¹⁵ : CH ₂ OiC ₄ H ₉
^{MP-18: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 OiC 4 H 9
^{MP-19: R 13, R} 14, R 16: CH 2 OiC 4 H 9; R 15: CH 2 OH
^{MP-20: R 13, R} 16: CH 2 OiC 4 H 9; R 14, R 15: CH 2 OH

MP-21: R ¹³ , R ¹⁴ , R ¹⁵ : CH ₂ OH; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-22: R ¹³ , R ¹⁴ , R ¹⁶ : CH ₂ OH; R ¹⁵ : CH ₂ OnC ₄ H ₉
MP-23: R ¹³ , R ¹⁴ : CH ₂ OH; R ¹⁵ , R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-24: R ¹³ , R ¹⁶ : CH ₂ OH; R ¹⁴ , R ¹⁵ : CH ₂ OnC ₄ H ₉
^{MP-25: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 OnC 4 H 9
MP-26: R ¹³ , R ¹⁴ , R ¹⁶ : CH ₂ OnC ₄ H ₉ ; R ¹⁵ : CH ₂ OH
MP-27: R ¹³ , R ¹⁶ : CH ₂ OnC ₄ H ₉ ; R ¹⁴ , R ¹⁵ : CH ₂ OH

MP-28: R ¹³ , R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ OCH ₃ ; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-29: R ¹³ , R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ OnC ₄ H ₉ ; R ¹⁶ : CH ₂ OCH ₃
MP-30: R ¹³ , R ¹⁶ : CH ₂ OH; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ OnC ₄ H ₉
MP-31: R ¹³ : CH ₂ OH; R ¹⁴ , R ¹⁵ : CH ₂ OCH ₃ ; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-32: R ¹³ : CH ₂ OH; R ¹⁴ , R ¹⁶ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ OnC ₄ H ₉
^{MP-33: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 OnC 4 H 9
MP-34: R ¹³ : CH ₂ OH; R ¹⁴ , R ¹⁵ : CH ₂ OnC ₄ H ₉ ; R ¹⁶ : CH ₂ OCH ₃
MP-35: R ¹³ , R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ OH; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-36: R ¹³ , R ¹⁶ : CH ₂ OCH ₃ ; R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ OnC ₄ H ₉
MP-37: R ¹³ : CH ₂ OCH ₃ ; R ¹⁴ , R ¹⁵ : CH ₂ OH; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-38: R ¹³ , R ¹⁶ : CH ₂ OnC ₄ H ₉ ; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ OH

MP-39: R ¹³ : CH ₂ OH; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ OnC ₄ H ₉ ; R ¹⁶ : CH ₂ NHCOCH = CH ₂
MP-40: R ¹³ : CH ₂ OH; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ NHCOCH = CH ₂ ; R ¹⁶ : CH ₂ OnC ₄ H ₉
^{MP-41: R 13: CH} 2 OH; R 14: CH 2 OnC 4 H 9; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
MP-42: R ¹³ : CH ₂ OCH ₃ ; R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ OnC ₄ H ₉ ; R ¹⁶ : CH ₂ NHCOCH = CH ₂
MP-43: R ¹³ : CH ₂ OCH ₃ ; R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ NHCOCH = CH ₂ ; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-44: R ¹³ : CH ₂ OnC ₄ H ₉ ; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ OH; R ¹⁶ : CH ₂ NHCOCH = CH ₂

MP-45: R ¹³ : CH ₂ OH; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ NHCO (CH ₂ ) ₇ CH═CH (CH ₂ ) ₇ CH ₃ ; R ¹⁶ : CH ₂ NHCOCH =
CH ₂
MP-46: R ¹³ : CH ₂ OH; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ NHCOCH═CH ₂ ; R ¹⁶ : CH ₂ NHCO (CH ₂ ) ₇ CH═CH (CH ₂ ) ₇
CH ₃
MP-47: R ¹³ : CH ₂ OH; R ¹⁴ : CH ₂ NHCO (CH ₂ ) ₇ CH═CH (CH ₂ ) ₇ CH ₃ ; R ¹⁵ : CH ₂ NHCOCH═CH ₂ ; R ¹⁶ : CH ₂ O
CH ₃
MP-48: R ¹³ : CH ₂ OCH ₃ ; R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ NHCO (CH ₂ ) ₇ CH═CH (CH ₂ ) ₇ CH ₃ ; R ¹⁶ : CH ₂ NHCOCH =
CH ₂
MP-49: R ¹³ : CH ₂ OCH ₃ ; R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ NHCOCH═CH ₂ ; R ¹⁶ : CH ₂ NHCO (CH ₂ ) ₇ CH═CH (CH ₂ ) ₇
CH ₃
^{MP-50: R 13: CH} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH =
CH ₂

^{MP-51: R 13, R} 14, R 15, R 16: CH 2 OH
MP-52: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OCH ₃
^{MP-53: R 13, R} 14, R 15, R 16: CH 2 OiC 4 H 9
MP-54: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-55: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ NHCOCH═CH ₂
^{MP-56: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3

^{MP-57: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 OCH 3
^{MP-58: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 OCH 3
MP-59: R ¹³ , R ¹⁴ : CH ₂ OH; R ¹⁵ , R ¹⁶ : CH ₂ OCH ₃
MP-60: R ¹³ , R ¹⁶ : CH ₂ OH; R ¹⁴ , R ¹⁵ : CH ₂ OCH ₃
MP-61: R ¹³ : CH ₂ OH; R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OCH ₃
^{MP-62: R 13, R} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
MP-63: R ¹³ , R ¹⁶ : CH ₂ OCH ₃ ; R ¹⁴ , R ¹⁵ : CH ₂ OH

^{MP-64: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 OiC 4 H 9
^{MP-65: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 OiC 4 H 9
MP-66: R ¹³ , R ¹⁴ : CH ₂ OH; R ¹⁵ , R ¹⁶ : CH ₂ OiC ₄ H ₉
MP-67: R ¹³ , R ¹⁶ : CH ₂ OH; R ¹⁴ , R ¹⁵ : CH ₂ OiC ₄ H ₉
^{MP-68: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 OiC 4 H 9
MP-69: R ¹³ , R ¹⁴ , R ¹⁶ : CH ₂ OiC ₄ H ₉ ; R ¹⁵ : CH ₂ OH
MP-70: R ¹³ , R ¹⁶ : CH ₂ OiC ₄ H ₉ ; R ¹⁴ , R ¹⁵ : CH ₂ OH

MP-71: R ¹³ , R ¹⁴ , R ¹⁵ : CH ₂ OH; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-72: R ¹³ , R ¹⁴ , R ¹⁶ : CH ₂ OH; R ¹⁵ : CH ₂ OnC ₄ H ₉
MP-73: R ¹³ , R ¹⁴ : CH ₂ OH; R ¹⁵ , R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-74: R ¹³ , R ¹⁶ : CH ₂ OH; R ¹⁴ , R ¹⁵ : CH ₂ OnC ₄ H ₉
MP-75: R ¹³ : CH ₂ OH; R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-76: R ¹³ , R ¹⁴ , R ¹⁶ : CH ₂ OnC ₄ H ₉ ; R ¹⁵ : CH ₂ OH
MP-77: R ¹³ , R ¹⁶ : CH ₂ OnC ₄ H ₉ ; R ¹⁴ , R ¹⁵ : CH ₂ OH

MP-78: R ¹³ , R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ OCH ₃ ; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-79: R ¹³ , R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ OnC ₄ H ₉ ; R ¹⁶ : CH ₂ OCH ₃
MP-80: R ¹³ , R ¹⁶ : CH ₂ OH; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ OnC ₄ H ₉
MP-81: R ¹³ : CH ₂ OH; R ¹⁴ , R ¹⁵ : CH ₂ OCH ₃ ; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-82: R ¹³ : CH ₂ OH; R ¹⁴ , R ¹⁶ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ OnC ₄ H ₉
MP-83: R ¹³ : CH ₂ OH; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ , R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-84: R ¹³ : CH ₂ OH; R ¹⁴ , R ¹⁵ : CH ₂ OnC ₄ H ₉ ; R ¹⁶ : CH ₂ OCH ₃
MP-85: R ¹³ , R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ OH; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-86: R ¹³ , R ¹⁶ : CH ₂ OCH ₃ ; R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ OnC ₄ H ₉
MP-87: R ¹³ : CH ₂ OCH ₃ ; R ¹⁴ , R ¹⁵ : CH ₂ OH; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-88: R ¹³ , R ¹⁶ : CH ₂ OnC ₄ H ₉ ; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ OH

MP-89: R ¹³ : CH ₂ OH; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ OnC ₄ H ₉ ; R ¹⁶ : CH ₂ NHCOCH = CH ₂
MP-90: R ¹³ : CH ₂ OH; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ NHCOCH = CH ₂ ; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-91: R ¹³ : CH ₂ OH; R ¹⁴ : CH ₂ OnC ₄ H ₉ ; R ¹⁵ : CH ₂ NHCOCH = CH ₂ ; R ¹⁶ : CH ₂ OCH ₃
MP-92: R ¹³ : CH ₂ OCH ₃ ; R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ OnC ₄ H ₉ ; R ¹⁶ : CH ₂ NHCOCH = CH ₂
MP-93: R ¹³ : CH ₂ OCH ₃ ; R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ NHCOCH = CH ₂ ; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-94: R ¹³ : CH ₂ OnC ₄ H ₉ ; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ OH; R ¹⁶ : CH ₂ NHCOCH = CH ₂

MP-95: R ¹³ : CH ₂ OH; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ NHCO (CH ₂ ) ₇ CH═CH (CH ₂ ) ₇ CH ₃ ; R ¹⁶ : CH ₂ NHCOCH =
CH ₂
^{MP-96: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7
CH ₃
MP-97: R ¹³ : CH ₂ OH; R ¹⁴ : CH ₂ NHCO (CH ₂ ) ₇ CH═CH (CH ₂ ) ₇ CH ₃ ; R ¹⁵ : CH ₂ NHCOCH═CH ₂ ; R ¹⁶ : CH ₂ O
CH ₃
MP-98: R ¹³ : CH ₂ OCH ₃ ; R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ NHCO (CH ₂ ) ₇ CH═CH (CH ₂ ) ₇ CH ₃ ; R ¹⁶ : CH ₂ NHCOCH =
CH ₂
MP-99: R ¹³ : CH ₂ OCH ₃ ; R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ NHCOCH═CH ₂ ; R ¹⁶ : CH ₂ NHCO (CH ₂ ) ₇ CH═CH (CH ₂ ) ₇
CH ₃
^{MP-100: R 13: CH} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOC
H = CH ₂

MP-101: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OH
MP-102: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OCH ₃
MP-103: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OiC ₄ H ₉
MP-104: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-105: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ NHCOCH = CH ₂
^{MP-106: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3

MP-107: R ¹³ , R ¹⁴ , R ¹⁵ : CH ₂ OH; R ¹⁶ : CH ₂ OCH ₃
^{MP-108: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 OCH 3
MP-109: R ¹³ , R ¹⁴ : CH ₂ OH; R ¹⁵ , R ¹⁶ : CH ₂ OCH ₃
MP-110: R ¹³ , R ¹⁶ : CH ₂ OH; R ¹⁴ , R ¹⁵ : CH ₂ OCH ₃
MP-111: R ¹³ : CH ₂ OH; R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OCH ₃
^{MP-112: R 13, R} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
^{MP-113: R 13, R} 16: CH 2 OCH 3; R 14, R 15: CH 2 OH

^{MP-114: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 OiC 4 H 9
MP-115: R ¹³ , R ¹⁴ , R ¹⁶ : CH ₂ OH; R ¹⁵ : CH ₂ OiC ₄ H ₉
MP-116: R ¹³ , R ¹⁴ : CH ₂ OH; R ¹⁵ , R ¹⁶ : CH ₂ OiC ₄ H ₉
MP-117: R ¹³ , R ¹⁶ : CH ₂ OH; R ¹⁴ , R ¹⁵ : CH ₂ OiC ₄ H ₉
^{MP-118: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 OiC 4 H 9
MP-119: R ¹³ , R ¹⁴ , R ¹⁶ : CH ₂ OiC ₄ H ₉ ; R ¹⁵ : CH ₂ OH
MP-120: R ¹³ , R ¹⁶ : CH ₂ OiC ₄ H ₉ ; R ¹⁴ , R ¹⁵ : CH ₂ OH

MP-121: R ¹³ , R ¹⁴ , R ¹⁵ : CH ₂ OH; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-122: R ¹³ , R ¹⁴ , R ¹⁶ : CH ₂ OH; R ¹⁵ : CH ₂ OnC ₄ H ₉
MP-123: R ¹³ , R ¹⁴ : CH ₂ OH; R ¹⁵ , R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-124: R ¹³ , R ¹⁶ : CH ₂ OH; R ¹⁴ , R ¹⁵ : CH ₂ OnC ₄ H ₉
^{MP-125: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 OnC 4 H 9
MP-126: R ¹³ , R ¹⁴ , R ¹⁶ : CH ₂ OnC ₄ H ₉ ; R ¹⁵ : CH ₂ OH
MP-127: R ¹³ , R ¹⁶ : CH ₂ OnC ₄ H ₉ ; R ¹⁴ , R ¹⁵ : CH ₂ OH

MP-128: R ¹³ , R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ OCH ₃ ; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-129: R ¹³ , R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ OnC ₄ H ₉ ; R ¹⁶ : CH ₂ OCH ₃
MP-130: R ¹³ , R ¹⁶ : CH ₂ OH; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ OnC ₄ H ₉
MP-131: R ¹³ : CH ₂ OH; R ¹⁴ , R ¹⁵ : CH ₂ OCH ₃ ; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-132: R ¹³ : CH ₂ OH; R ¹⁴ , R ¹⁶ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ OnC ₄ H ₉
^{MP-133: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 OnC 4 H 9
MP-134: R ¹³ : CH ₂ OH; R ¹⁴ , R ¹⁵ : CH ₂ OnC ₄ H ₉ ; R ¹⁶ : CH ₂ OCH ₃
MP-135: R ¹³ , R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ OH; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-136: R ¹³ , R ¹⁶ : CH ₂ OCH ₃ ; R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ OnC ₄ H ₉
MP-137: R ¹³ : CH ₂ OCH ₃ ; R ¹⁴ , R ¹⁵ : CH ₂ OH; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-138: R ¹³ , R ¹⁶ : CH ₂ OnC ₄ H ₉ ; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ OH

MP-139: R ¹³ : CH ₂ OH; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ OnC ₄ H ₉ ; R ¹⁶ : CH ₂ NHCOCH = CH ₂
MP-140: R ¹³ : CH ₂ OH; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ NHCOCH = CH ₂ ; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-141: R ¹³ : CH ₂ OH; R ¹⁴ : CH ₂ OnC ₄ H ₉ ; R ¹⁵ : CH ₂ NHCOCH = CH ₂ ; R ¹⁶ : CH ₂ OCH ₃
MP-142: R ¹³ : CH ₂ OCH ₃ ; R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ OnC ₄ H ₉ ; R ¹⁶ : CH ₂ NHCOCH = CH ₂
MP-143: R ¹³ : CH ₂ OCH ₃ ; R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ NHCOCH = CH ₂ ; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-144: R ¹³ : CH ₂ OnC ₄ H ₉ ; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ OH; R ¹⁶ : CH ₂ NHCOCH = CH ₂

MP-145: R ¹³ : CH ₂ OH; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ NHCO (CH ₂ ) ₇ CH═CH (CH ₂ ) ₇ CH ₃ ; R ¹⁶ : CH ₂ NHCOC
H = CH ₂
MP-146: R ¹³ : CH ₂ OH; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ NHCOCH═CH ₂ ; R ¹⁶ : CH ₂ NHCO (CH ₂ ) ₇ CH═CH (CH ₂
) ₇ CH ₃
MP-147: R ¹³ : CH ₂ OH; R ¹⁴ : CH ₂ NHCO (CH ₂ ) ₇ CH═CH (CH ₂ ) ₇ CH ₃ ; R ¹⁵ : CH ₂ NHCOCH═CH ₂ ; R ¹⁶ : CH
₂ OCH ₃
MP-148: R ¹³ : CH ₂ OCH ₃ ; R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ NHCO (CH ₂ ) ₇ CH═CH (CH ₂ ) ₇ CH ₃ ; R ¹⁶ : CH ₂ NHCOC
H = CH ₂
MP-149: R ¹³ : CH ₂ OCH ₃ ; R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ NHCOCH═CH ₂ ; R ¹⁶ : CH ₂ NHCO (CH ₂ ) ₇ CH═CH (CH ₂
) ₇ CH ₃
MP-150: R ¹³ : CH ₂ NHCO (CH ₂ ) ₇ CH═CH (CH ₂ ) ₇ CH ₃ ; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ OH; R ¹⁶ : CH ₂ NHCOC
H = CH ₂

MP-151: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OH
^{MP-152: R 13, R} 14, R 15, R 16: CH 2 OCH 3
MP-153: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OiC ₄ H ₉
MP-154: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-155: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ NHCOCH═CH ₂
^{MP-156: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3

^{MP-157: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 OCH 3
^{MP-158: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 OCH 3
MP-159: R ¹³ , R ¹⁴ : CH ₂ OH; R ¹⁵ , R ¹⁶ : CH ₂ OCH ₃
MP-160: R ¹³ , R ¹⁶ : CH ₂ OH; R ¹⁴ , R ¹⁵ : CH ₂ OCH ₃
MP-161: R ¹³ : CH ₂ OH; R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OCH ₃
^{MP-162: R 13, R} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
MP-163: R ¹³ , R ¹⁶ : CH ₂ OCH ₃ ; R ¹⁴ , R ¹⁵ : CH ₂ OH

MP-164: R ¹³ , R ¹⁴ , R ¹⁵ : CH ₂ OH; R ¹⁶ : CH ₂ OiC ₄ H ₉
MP-165: R ¹³ , R ¹⁴ , R ¹⁶ : CH ₂ OH; R ¹⁵ : CH ₂ OiC ₄ H ₉
MP-166: R ¹³ , R ¹⁴ : CH ₂ OH; R ¹⁵ , R ¹⁶ : CH ₂ OiC ₄ H ₉
MP-167: R ¹³ , R ¹⁶ : CH ₂ OH; R ¹⁴ , R ¹⁵ : CH ₂ OiC ₄ H ₉
^{MP-168: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 OiC 4 H 9
^{MP-169: R 13, R} 14, R 16: CH 2 OiC 4 H 9; R 15: CH 2 OH
^{MP-170: R 13, R} 16: CH 2 OiC 4 H 9; R 14, R 15: CH 2 OH

MP-171: R ¹³ , R ¹⁴ , R ¹⁵ : CH ₂ OH; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-172: R ¹³ , R ¹⁴ , R ¹⁶ : CH ₂ OH; R ¹⁵ : CH ₂ OnC ₄ H ₉
MP-173: R ¹³ , R ¹⁴ : CH ₂ OH; R ¹⁵ , R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-174: R ¹³ , R ¹⁶ : CH ₂ OH; R ¹⁴ , R ¹⁵ : CH ₂ OnC ₄ H ₉
MP-175: R ¹³ : CH ₂ OH; R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-176: R ¹³ , R ¹⁴ , R ¹⁶ : CH ₂ OnC ₄ H ₉ ; R ¹⁵ : CH ₂ OH
MP-177: R ¹³ , R ¹⁶ : CH ₂ OnC ₄ H ₉ ; R ¹⁴ , R ¹⁵ : CH ₂ OH

MP-178: R ¹³ , R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ OCH ₃ ; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-179: R ¹³ , R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ OnC ₄ H ₉ ; R ¹⁶ : CH ₂ OCH ₃
MP-180: R ¹³ , R ¹⁶ : CH ₂ OH; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ OnC ₄ H ₉
MP-181: R ¹³ : CH ₂ OH; R ¹⁴ , R ¹⁵ : CH ₂ OCH ₃ ; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-182: R ¹³ : CH ₂ OH; R ¹⁴ , R ¹⁶ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ OnC ₄ H ₉
^{MP-183: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 OnC 4 H 9
MP-184: R ¹³ : CH ₂ OH; R ¹⁴ , R ¹⁵ : CH ₂ OnC ₄ H ₉ ; R ¹⁶ : CH ₂ OCH ₃
MP-185: R ¹³ , R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ OH; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-186: R ¹³ , R ¹⁶ : CH ₂ OCH ₃ ; R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ OnC ₄ H ₉
MP-187: R ¹³ : CH ₂ OCH ₃ ; R ¹⁴ , R ¹⁵ : CH ₂ OH; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-188: R ¹³ , R ¹⁶ : CH ₂ OnC ₄ H ₉ ; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ OH

MP-189: R ¹³ : CH ₂ OH; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ OnC ₄ H ₉ ; R ¹⁶ : CH ₂ NHCOCH = CH ₂
MP-190: R ¹³ : CH ₂ OH; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ NHCOCH = CH ₂ ; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-191: R ¹³ : CH ₂ OH; R ¹⁴ : CH ₂ OnC ₄ H ₉ ; R ¹⁵ : CH ₂ NHCOCH = CH ₂ ; R ¹⁶ : CH ₂ OCH ₃
MP-192: R ¹³ : CH ₂ OCH ₃ ; R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ OnC ₄ H ₉ ; R ¹⁶ : CH ₂ NHCOCH = CH ₂
MP-193: R ¹³ : CH ₂ OCH ₃ ; R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ NHCOCH = CH ₂ ; R ¹⁶ : CH ₂ OnC ₄ H ₉
MP-194: R ¹³ : CH ₂ OnC ₄ H ₉ ; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ OH; R ¹⁶ : CH ₂ NHCOCH = CH ₂

MP-195: R ¹³ : CH ₂ OH; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ NHCO (CH ₂ ) ₇ CH═CH (CH ₂ ) ₇ CH ₃ ; R ¹⁶ : CH ₂ NHCOC
H = CH ₂
MP-196: R ¹³ : CH ₂ OH; R ¹⁴ : CH ₂ OCH ₃ ; R ¹⁵ : CH ₂ NHCOCH═CH ₂ ; R ¹⁶ : CH ₂ NHCO (CH ₂ ) ₇ CH═CH (CH ₂
) ₇ CH ₃
MP-197: R ¹³ : CH ₂ OH; R ¹⁴ : CH ₂ NHCO (CH ₂ ) ₇ CH═CH (CH ₂ ) ₇ CH ₃ ; R ¹⁵ : CH ₂ NHCOCH═CH ₂ ; R ¹⁶ : CH
₂ OCH ₃
MP-198: R ¹³ : CH ₂ OCH ₃ ; R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ NHCO (CH ₂ ) ₇ CH═CH (CH ₂ ) ₇ CH ₃ ; R ¹⁶ : CH ₂ NHCOC
H = CH ₂
MP-199: R ¹³ : CH ₂ OCH ₃ ; R ¹⁴ : CH ₂ OH; R ¹⁵ : CH ₂ NHCOCH═CH ₂ ; R ¹⁶ : CH ₂ NHCO (CH ₂ ) ₇ CH═CH (CH ₂
) ₇ CH ₃
^{MP-200: R 13: CH} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOC
H = CH ₂

A copolymer combining two or more kinds of repeating units may be used. Two or more homopolymers or copolymers may be used in combination. Two or more compounds having 1,3,5-triazine ring may be used in combination. Two or more kinds of discotic compounds (for example, a compound having a 1,3,5-triazine ring and a compound having a porphyrin skeleton) may be used in combination.

In the present invention, a dye for adjusting the hue may be added. The content of the dye is preferably 10 to 1000 ppm by mass with respect to cellulose acylate, and preferably 50 to 500 pp.
m is more preferable. By containing the dye in this way, light piping of the cellulose acylate film can be reduced and the yellowness can be improved. These compounds are
When preparing the cellulose acylate solution, it may be added together with cellulose acylate or a solvent, or may be added during or after the solution preparation. Moreover, you may add to the ultraviolet absorber liquid added in-line.

The dye used in the present invention is preferably a compound represented by the following general formula (I) or (II). Formula (I)

In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each a hydrogen atom, a hydroxyl group,
Aliphatic group, aromatic group, heterocyclic group, halogen atom, cyano group, nitro group, COR ₉ , COOR ₉ , NR ₉
R ₁₀ , NR ₁₀ COR ₁₁ , NR ₁₀ SO ₂ R ₁₁ , CONR ₉ R ₁₀ , SO ₂ NR ₉ R ₁₀ , COR ₁₁ , SO ₂ R ₁₁ , OCOR ₁₁ , NR ₉ CO
It represents _{NR 10 R 11, CONHSO 2 R} 11, SO 2 NHCOR 11, R 9, R 10 are each a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, R ₁₁ is an aliphatic group, an aromatic R ₉ and R ₁₀ may be linked to form a 5- or 6-membered ring, and R ₁ and R ₂ or R ₂ and R ₃ may be linked to form a ring. May be.

In the formula, R ₂₁ , R ₂₃ and R ₂₄ are a hydrogen atom, a hydroxyl group, a nitro group, a cyano group, an aliphatic group, an aromatic group, COR ₂₉ , COOR ₂₉ , NR ₂₉ R ₃₀ , NR ₃₀ COR ₃₁ , NR ₃₀ SO ₂ represents R ₃₁ and R _2
2 represents an aliphatic group or an aromatic group, R ₂₉ and R ₃₀ have the same meanings as R ₉ and R ₁₀ in formula (I), and R ₃₁ has the same meaning as R ₁₁ in formula (I). However, R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄
One or more of these are groups other than hydrogen.

Hereinafter, each group of the general formula (I) will be described in detail. The aliphatic group represented by R _{1 to} R ₁₁ is an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, n-butyl, isopropyl,
2-ethylhexyl, n-decyl, n-octadecyl), a cycloalkyl group having 1 to 20 carbon atoms (for example, cyclopentyl, cyclohexyl) or an allyl group, and a substituent [for example, a halogen atom (for example, F, Cl, Br) I), hydroxyl group, cyano group, nitro group, carboxylic acid group, aryl group having 6 to 10 carbon atoms (for example, phenyl, naphthyl), 0 to 2 carbon atoms
0 amino groups _{(e.g., NH 2, NHCH 3, N} (C 2 H 5) 2, N (C 4 H 9) 2, N (C 8 H 17) 2, anilino, 4-
Methoxyanilino), amide groups having 1 to 20 carbon atoms (for example, acetylamino, hexanoylamino, benzoylamino, octadecanoylamino), carbamoyl groups having 1 to 20 carbon atoms (for example, unsubstituted carbamoyl, methylcarbamoyl) , Ethylcarbamoyl, octylcarbamoyl, hexadecylcarbamoyl), ester groups having 2 to 20 carbon atoms (for example, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, n-butoxycarbonyl, dodecyloxycarbonyl), alkoxy groups having 1 to 20 carbon atoms Or aryloxy group (methoxy, ethoxy, butoxy, isopropoxy, benzyloxy, phenoxy,
Octadecyloxy), C1-C20 sulfonamide groups (for example, methanesulfonamide, ethanesulfonamide, butanesulfonamide, benzenesulfonamide, octanesulfonamide), C0-20 sulfamoyl groups (for example, unsubstituted) Sulfamoyl, methylsulfamoyl, butylsulfamoyl, decylsulfamoyl) of 5 or 6-membered heterocycle (eg pyridyl, pyrazolyl, morpholino, piperidino, pyrrolino, benzoxazolyl)) Also good.

The aromatic group represented by R _{1 to} R ₁₁ represents an aryl group having 6 to 10 carbon atoms (for example, phenyl or naphthyl), and is a substituent [for example, a substituent that the above-described aliphatic group may have. In addition to each group, it may have an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, butyl, t-butyl, octyl, etc.).

The heterocyclic group represented by R _{1 to} R ₁₁ represents a 5- or 6-membered heterocyclic ring (for example, pyridine, piperidine, morpholine, pyrrolidine, pyrazole, pyrazolidine, pyrazoline, pyrazolone, benzoxazole) and a substituent (for example, the above-mentioned Each group mentioned as a substituent which the aromatic group may have.

Examples of the 5- or 6-membered ring formed by connecting R ₉ and R ₁₀ include a morpholine ring, a piperidine ring, and a pyrrolidine ring. The ring formed by connecting R ₁ and R ₂ or R ₂ and R ₃ is preferably a 5- or 6-membered ring (for example, a benzene ring or a phthalimide ring).

Next, each group of general formula (II) is demonstrated. The aliphatic group represented by R _{21 to} R ₂₄ has the same meaning as the aliphatic group represented by R _{1 to} R ₁₁ in formula (I), and the aromatic group represented by R _{21 to} R ₂₄ represents the formula (I It is synonymous with the aromatic group which R < ₁ > -R < ₁₁ > in I) represents. Formula (I)
Specific examples of the compound represented by (II) are shown below, but the present invention is not limited thereto.

The compounds represented by the general formula (I) or (II) are described in JP-B Nos. 45-15187, 51-25335, 51-33724, 55-19933, and M.I. Matsuoka, M. Kisimomoto, tea. Kitao, Journal of the Society of Dyers and Colorists, 94, 435, 1978 (M. Matsuoka, M. Kishimoto, T. Kitao, J. Soc. Dyers and Colourists, 94, 435 (1978)) It can be synthesized by the method described in “Dye Chemistry”, pages 673 to 741, Gihodo (1957). The amount of the dye is preferably ^{0.001g / m 2 ~1g / m 2} , 0.005g / m 2 ~0.5g / m 2 is more preferable. These dyes may be used alone or in combination. The amount of dye used is preferably 0.005 to 0.5 in terms of the increase in transmission density, more preferably 0.01 to 0.3, and even more preferably 0.01 to 0.1. It is preferable to do this. In addition, as pigments to be used, carbon black, alkali metal, alkaline earth metal, oxides of Si, Al, Ti, Fe, sulfides, sulfates, sulfites, carbonates, hydroxides, halides , Nitrate, at least one pigment selected from at least one compound.
Carbon black, titanium dioxide, and the like are preferable. The amount of the pigment used is preferably 0.005 to 0.5 in terms of increase in transmission density, more preferably 0.01 to 0.3, and still more preferably 0.01 to 0.1. A pigment and a dye may be used in combination, but the total addition amount is preferably in the above range. Thus, light piping can be prevented by adding a dye and / or a pigment to the support.

In addition, various additives may be further added to the cellulose acylate solution of the present invention as needed at any stage from before preparation of the solution to after preparation. Additives include silicon dioxide,
Thermal stabilizers such as kaolin, talc, diatomaceous earth, quartz, calcium carbonate, barium sulfate, titanium oxide, and alumina, alkaline earth metal salts such as calcium and magnesium, antistatic agents, flame retardants, lubricants, oils Etc. In particular, the inorganic fine particles used have a role as an anti-smudge agent and an antistatic property. In that case, the hardness of the metal or metal compound is not particularly limited, but the Mohs hardness is preferably 1 to 10, more preferably 2 to 10. Organic fine particles are also preferably used, and examples thereof include crosslinked polystyrene, crosslinked polymethyl methacrylate, and crosslinked triazine resin.

(Fine particles)
In particular, in the present invention, when the produced cellulose acylate film is handled, it is generally performed to add fine particles in order to prevent damage and deterioration of transportability. They are called matting agents, anti-blocking agents or anti-scratching agents and have been used conventionally. They are not particularly limited as long as they are materials exhibiting the above-mentioned functions, but preferred specific examples of these matting agents include compounds containing silicon, silicon dioxide, titanium oxide, zinc oxide, aluminum oxide, oxidation as inorganic compounds. Barium, zirconium oxide, strongtium oxide, antimony oxide, tin oxide, tin / antimony oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate Etc., more preferably an inorganic compound containing silicon or zirconium oxide, but silicon dioxide is particularly preferably used because the turbidity of the cellulose acylate film can be reduced. Examples of the silicon dioxide fine particles include Aerosil R972, R974, R812, and 20
Commercial products having trade names such as 0, 300, R202, OX50, and TT600 (manufactured by Nippon Aerosil Co., Ltd.) can be used. As the fine particles of zirconium oxide, for example, those commercially available under trade names such as Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) can be used.

As the organic compound, for example, polymers such as silicone resin, fluorine resin and acrylic resin are preferable, and among them, silicone resin is preferably used. Of the silicone resins, those having a three-dimensional network structure are particularly preferable.
Commercial products having trade names such as 0 and Tospearl 240 (above Toshiba Silicone Co., Ltd.) can be used.

When these additives are added to the cellulose acylate solution, the method is not particularly limited, and any method can be used as long as a desired cellulose acylate solution can be obtained.
For example, an additive may be contained at the stage of mixing cellulose acylate and a solvent, or an additive may be added after preparing a mixed solution with cellulose acylate and a solvent. Further, it may be added and mixed immediately before casting the dope, which is a so-called immediately preceding addition method, and the mixing is used by installing screw-type kneading online. Specifically, a static mixer such as an in-line mixer is preferable, and as the in-line mixer, for example, a static mixer SWJ (Toray static type in-pipe mixer Hi-Mixer) (manufactured by Toray Engineering) is used. Is preferred.

Regarding in-line addition, in order to eliminate density unevenness, particle aggregation, etc.
In 53752, in the method for producing a cellulose ester film, the distance L between the tip of the addition nozzle for mixing additive liquids having different compositions into the main raw material dope and the starting end of the in-line mixer is 5 times or less the main raw material pipe inner diameter d. Thus, there is described an invention that eliminates concentration unevenness, aggregation of matte particles, and the like.

In a more preferred embodiment, the distance (L) between the tip opening of the additive liquid supply nozzle having a composition different from that of the main raw material dope and the starting end of the in-line mixer is the inner diameter (d
It is described that the in-line mixer is a static unstirred in-tube mixer or a dynamic agitated in-tube mixer. More specifically, the flow rate ratio of the cellulose ester film main raw material dope / in-line additive solution is 10/1 to 500/1, preferably 50.
/ 1 to 200/1.

In addition, additive is added to JP 2003-014933 of the invention which aims at a retardation film with little additive bleed-out, no delamination phenomenon, good slipperiness and excellent transparency As a method to do this, it may be added to the melting pot, or a solution in which additives or additives are dissolved or dispersed between the melting pot and the co-casting die may be added to the dope being fed. However, in the latter case, it is described that it is preferable to provide a mixing means such as a static mixer in order to improve the mixing property.

These inventions described above can also be applied to the present invention.

The additive may be added by itself, but it may be dissolved in advance using a solvent or binder (preferably cellulose acylate) or may be dispersed and stabilized as the case may be. Is also a preferred embodiment.

The primary average particle diameter of these fine particles is preferably 0.001 to 20 μm, more preferably 0.001 to 10 μm, and still more preferably 0.002 to 1 μm, from the viewpoint of keeping haze low. Especially preferably, it is 0.005-0.5 micrometer. The measurement of the primary average particle diameter of the fine particles is obtained by the average particle diameter of the particles with a transmission electron microscope. The apparent specific gravity of the fine particles is preferably 30 g / liter or more, more preferably
It is 40-200 g / liter, Most preferably, it is 50-200 g / liter.
For example, they are commercially available under the trade names of Aerosil 200V and Aerosil R972V (manufactured by Nippon Aerosil Co., Ltd.), and these can be used. Examples of the method for preparing a dispersion of fine particles according to the present invention include the following three types.

-After stirring and mixing the solvent and the fine particles, make a fine particle dispersion with a disperser, and stir in addition to the dope solution.
-After stirring and mixing the solvent and fine particles, make a fine particle dispersion with a disperser, and add a small amount of cellulose acylate to the solvent and dissolve with stirring. The fine particle dispersion obtained by adding the fine particle dispersion to this and stirring is sufficiently mixed with the dope solution using an in-line mixer.
-Add a small amount of cellulose acylate to the solvent and dissolve with stirring. Add fine particles to this and disperse with a disperser to obtain a fine particle addition solution. The fine particle additive solution is sufficiently mixed with the dope solution using an in-line mixer.

When the silicon dioxide fine particles are mixed with a solvent or the like and dispersed, the concentration of silicon dioxide is 5 to 3
0 mass% is preferable, 10 to 25 mass% is more preferable, and 15 to 20 mass% is most preferable.

Solvents used include lower alcohols, preferably methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol and the like. Although it does not specifically limit as solvents other than a lower alcohol, It is preferable to use the solvent used at the time of film formation of a cellulose acylate.

The amount of silicon dioxide fine particles added to cellulose acylate is cellulose acylate 1
The silicon dioxide fine particles are preferably 0.01 to 0.3 parts by mass with respect to 00 parts by mass, and 0.0
5 to 0.2 parts by mass is more preferable, and 0.08 to 0.12 parts by mass is most preferable.

As the dispersion, media dispersers include ball mills, sand mills, dyno mills, and the like, and medialess dispersers include ultrasonic types, centrifugal types, high pressure types, and the like. The high pressure dispersion device has a maximum pressure condition of 9.8 MP in a thin tube having a tube diameter of 1 to 2000 μm, for example.
It is preferable that it is a or more. More preferably, it is 19.6 MPa or more. At that time
Those having a maximum reaching speed of 100 m / sec or more and those having a heat transfer speed of 420 kJ / hr or more are preferred. Microfluidics Corp for high pressure disperser
There is a super high pressure homogenizer (trade name Microfluidizer) manufactured by ation Corporation or a nanomizer manufactured by Nanomizer Co., Ltd., in addition to a Manton Gorin type high pressure dispersion device such as a homogenizer manufactured by Izumi Food Machinery, UHN-01 manufactured by Sanwa Machinery Co., Ltd. Etc. In addition, it is preferable in terms of slipperiness to cast the layer containing fine particles according to the present invention so as to be in direct contact with the metal support. Details of the above fine particles are described in JP-A-7-11055, JP-A-10-45817, and JP-A-2000-356714.

Further, in JP-A-2003-014933, when the dispersion method is used, the higher the dispersion concentration, the lower the liquid turbidity with respect to the addition amount, which is preferable because haze and aggregates are improved. Is described. Dispersers are broadly divided into media dispersers and medialess dispersers. However, it is indicated that the use of a medialess disperser for dispersing silicon dioxide fine particles is preferable because film haze can be lowered. . Specifically, examples of the media disperser include a ball mill, a sand mill, and a dyno mill, and examples of the media-less disperser include an ultrasonic type, a centrifugal type, and a high pressure type, but a composition in which fine particles and a solvent are mixed, It is disclosed that a high-pressure dispersion apparatus that creates special conditions such as high shear and high-pressure conditions by passing through a narrow tube at high speed is preferable.

JP-A-2003-014933 discloses, for example, a pipe diameter of 1 to 200 when processing with a high-pressure dispersion apparatus.
It is preferable that the maximum pressure condition inside the apparatus in a 0 μm capillary is 10 MPa or more, more preferably 20 MPa or more. It is described that those reaching the above are preferable. Specifically, there is an ultrahigh pressure homogenizer (trade name: Microfluidizer) manufactured by Microfluidics Corporation or a nanomizer manufactured by Nanomizer, and also a Manton Gorin type high-pressure dispersion device such as a homogenizer manufactured by Izumi Food Machinery, Sanwa Machinery Co., Ltd. UHN-01 manufactured by the company is listed.

Furthermore, regarding the dispersion of fine particles, the dope without aggregates is prepared, and the film after film formation is
For the purpose of obtaining appropriate slipperiness, ease of winding, and excellent transparency, Japanese Patent Application Laid-Open No. 2002-128900
In the method for preparing a dope by mixing a fine particle dispersion obtained by mixing an organic solvent and a fine particle dispersion stock solution containing fine particles and an organic solvent, and a cellulose ester solution containing a cellulose ester and an organic solvent, An invention is described in which a fine particle dispersion is dispersed, prepared, stored, transferred and mixed with a cellulose ester solution without being substantially exposed to air.

Further, in JP-A-2002-128900, as a more preferable embodiment, a high pressure dispersion device is used without substantially contacting air with a mixture obtained by introducing an organic solvent into a container after degassing fine particles in the container.・ Use the fine particle dispersion stock solution obtained by dispersing the fine particles in the container, ・ Depressurize the inside of the container to 0.1 to 0.8 atm, ・ Organize the container with the saturated vapor pressure of the organic solvent. Use of a fine particle dispersion dispersed by introducing a fine particle dispersion stock solution together with an organic solvent into a container filled with an organic solvent vapor filled with a solvent vapor and having a saturated vapor pressure of the organic solvent. Use a fine particle dispersion prepared or stored in a container equipped with a device (liquid sealing device) that can shut off the outside and the interior with an organic solvent. ・ Select from a fine particle dispersion stock solution, a fine particle dispersion solution, and a dope. This A liquid containing fine particles and an organic solvent, after the dispersion, when transferring the containers to be transported through inlet port located near the bottom of the container filled with organic solvent vapor, etc. is disclosed.

Furthermore, in Japanese Patent Laid-Open No. 2002-128900, when a fine particle stock solution is preliminarily dispersed with a disperser such as a dissolver after a composition in which fine particles and an organic solvent are mixed, it is introduced at the moment of introduction. It is preferable to introduce a mixture of the fine particles and / or organic solvent while blocking the air and disperse it to a very fine level. It is described that the fine particle dispersion stock solution may be temporarily stored after preparation, but it is preferable to disperse it by directly putting it in a larger amount of organic solvent.

These inventions described above can also be applied to the present invention.

(paint remover)
Further, in the present invention, it is preferable to add a release agent in order to reduce the load at the time of peeling. For these, surfactants are effective, and phosphoric acid-based, sulfonic acid-based, carboxylic acid-based, nonionic-based, cationic-based and the like are not particularly limited. These are described, for example, in JP-A-61-243837 and JP-A-2000-99847.

As for the release agent, in Japanese Patent Application Laid-Open No. 2003-055501, in order to prevent white turbidity of the cellulose acylate solution and improve film production peelability and film surface shape, a cellulose acylate solution dissolved in a non-chlorine solvent, There is a description of a cellulose acylate solution containing an additive selected from a polybasic acid partial ester having an acid dissociation index pKA of 1.93 to 4.5, an alkali metal salt, and an alkaline earth metal salt.

Furthermore, in JP 2003-103545 A, a cellulose acylate having two or more layers of a co-casting method is provided to improve the peelability at the time of manufacture, improve the film surface shape, and provide a film having no problem in durability. Addition selected from a polybasic acid partial ester having an acid dissociation index of pKA 1.93 to 4.50, an alkali metal salt, or an alkaline earth metal salt dissolved in a non-chlorine solvent by a rate film production method. An amine compound containing peptidic acid A and not containing additive A in an amine compound having a pKA of 4.50 or more, or an amine having substantially no volatility and a molecular weight of 200 or less per basic group There is a description of a method for producing a cellulose acylate film containing additive B, which is a compound.

These inventions described above can also be applied to the present invention.

These release agents are specifically described below. That is, before casting the cellulose acylate solution, 0.005 to 2% by mass of the release agent represented by the general formula (HK1) or the general formula (HK2) is added.
Formula (HK1); (R1-B1-O) n1-P (= O)-(OM1) n2
Formula (HK2); R2-B2-X
Here, R1 and R2 represent a substituted or unsubstituted alkyl group, alkenyl group, aralkyl group, and allyl group having 4 to 40 carbon atoms, and M1 is an alkali metal, ammonia, or a lower alkylamine. B1 and B2 each represent a divalent linking group, and X represents a carboxylic acid (or a salt thereof), a sulfonic acid (or a salt thereof), or a sulfate ester (or a salt thereof). n1 is an integer of 1 or 2, and n2 represents an integer of (3-n1).

In the present invention, the cellulose acylate film contains at least one release agent represented by the general formula (HK1) or (HK2), and these release agents are described below.

  Preferred examples of R1 and R2 include substituted or unsubstituted alkyl groups having 4 to 40 carbon atoms (for example, butyl, hexyl, octyl, 2-ethylhexyl, nonyl, dodecyl, hexadecyl, octadecyl, eicosanyl, docosanyl, myricyl, etc. ), Substituted with 4 to 40 carbon atoms, unsubstituted alkenyl group (for example, 2-hexenyl, 9-decenyl, oleyl, etc.), substituted with 4 to 40 carbon atoms, unsubstituted aryl group (for example, phenyl, naphthyl, Methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, diisopropylphenyl, triisopropylphenyl, t-butylphenyl, di-t-butylphenyl, tri-t-butylphenyl, isopentylphenyl, octylphenyl, isooctyl Phenyl, isononi It represents phenyl, diisononyl phenyl, dodecylphenyl, and the like iso-pentadecyl phenyl, etc.).

  Among these, more preferred are alkyl as hexyl, octyl, 2-ethylhexyl, nonyl, dodecyl, hexadecyl, octadecyl, docosanyl, alkenyl as alkenyl, aryl as phenyl, naphthyl, trimethylphenyl, diisopropylphenyl, tripropyl. Isopropylphenyl, di-t-butylphenyl, tri-t-butylphenyl, isooctylphenyl, isononylphenyl, diisononylphenyl, dodecylisopentadecylphenyl.

Next, the divalent linking group of B1 and B2 will be described. C1-C10 alkylene, poly (polymerization degree 1-50) oxyethylene, poly (polymerization degree 1-50) oxypropylene, poly (polymerization degree 1-50) oxyglycerin, and these may be mixed. . Preferred linking groups among these are methylene, ethylene, propylene, butylene, poly (degree of polymerization 1-25).
) Oxyethylene, poly (degree of polymerization 1-25) oxypropylene, poly (degree of polymerization 1-15)
Oxyglycerin. X is then carboxylic acid (or salt), sulfonic acid (or salt),
Although it is a sulfate ester (or salt), sulfonic acid (or salt) and sulfate ester (or salt) are particularly preferable. Preferred salts are Na, K, ammonium, trimethylamine and triethanolamine.

Although the specific example of the preferable peeling agent of this invention is described below, it is not limited to these.
RZ-1 C ₈ H ₁₇ O—P (═O) — (OH) ₂
RZ-2 C ₁₂ H ₂₅ O—P (═O) — (OK) ₂
RZ-3 C ₁₂ H ₂₅ OCH ₂ CH ₂ O—P (═O) — (OK) ₂
RZ-4 C ₁₅ H ₃₁ (OCH ₂ CH ₂ ) ₅ O—P (═O) — (OK) _{2
RZ-5 {C 12 H 25} O (CH 2 CH 2 O) 5} 2 -P (= O) -OH
_{RZ-6 {C 18 H 35} (OCH 2 CH 2) 8 O} 2 -P (= O) -ONH 4
_{RZ-7 (t-C 4} H 9) 3 -C 6 H 2 -OCH 2 CH 2 O-P (= O) - (OK) 2
_{RZ-8 (iso-C 9} H 19 -C 6 H 4 -O- (CH 2 CH 2 O) 5 -P (= O) -
(OK) (OH)
RZ-9 C ₁₂ H ₂₅ SO ₃ Na
RZ-10 C ₁₂ H ₂₅ OSO ₃ Na
RZ-11 C ₁₇ H ₃₃ COOH
RZ-12 C ₁₇ H ₃₃ COOH · N (CH ₂ CH ₂ OH) _{3
RZ-13 iso-C 8 H} 17 -C 6 H 4 -O- (CH 2 CH 2 O) 3 - (CH 2) 2 SO 3 N
a
_{RZ-14 (iso-C 9} H 19) 2 -C 6 H 3 -O- (CH 2 CH 2 O) 3 - (CH 2) 4
SO ₃ Na
RZ-15 sodium triisopropyl naphthalene sulfonate RZ-16 sodium tri-t-butyl naphthalene sulfonate RZ-17 C ₁₇ H ₃₃ CON (CH ₃ ) CH ₂ CH ₂ SO ₃ Na
RZ-18 C ₁₂ H ₂₅ -C ₆ H ₄ SO ₃ .NH ₄

The amount of at least one of the general formula (1) or (2) used in the present invention is 0.002 to 2 of the solution.
Although it is mass%, More preferably, it is 0.005-1 mass%, More preferably, it is 0.05.
1 to 0.5% by mass. The addition method is not particularly limited, but it may be liquid or solid as it is and added together with other raw materials before dissolving, or may be added later to a cellulose acylate solution prepared in advance.

Furthermore, the acid dissociation index pKa 1.93-4 described in JP-A-10-316701 is disclosed.
. 50 [preferably 2.0 to 4.4, more preferably 2.2 to 4.3 (for example, 2.5
To 4.0), particularly 2.6 to 4.3 (for example, about 2.6 to 4.0)] or a salt thereof is preferable as the release agent. These may be either inorganic acids or organic acids. For the pKa of acids, “Revised 3rd edition, Chemical Handbook, Basics II” (Edited by The Chemical Society of Japan, published by Maruzen Co., Ltd.)
Can be referred to. The acid dissociation index pKa is shown below in parentheses together with specific examples of acids. Examples of the inorganic acids, for _{example, HC1O 2 (2.31), HOCN} (3.48), molybdic acid _{(H 2 MoO 4, 3.62)} , HNO 2 (3.15), phosphoric acid (H ₃ PO , 2.15)
, Tripolyphosphoric acid (H ₅ P ₃ O ₁₀ , 2.0), vanadic acid (H ₃ VO ₄ , 3.78), and the like.

Examples of the organic acid include formic acid (3.55), oxaloacetic acid (2.27), cyanoacetic acid (2.47), phenylacetic acid (4.10), and phenoxyacetic acid (2.99) as aliphatic monocarboxylic acids. ), Fluoroacetic acid (2.59), chloroacetic acid (2.68), bromoacetic acid (2.
72), iodoacetic acid (2.98), mercaptoacetic acid (3.43), vinylacetic acid (4.12).
), Halopropionic acid such as chloropropionic acid (2.71-3.92), 4-aminobutyric acid (4.03), acrylic acid (4.26) and the like. . Aliphatic polyvalent carboxylic acids include malonic acid (2.65) and succinic acid (4.0).
0), glutaric acid (4.13), adipic acid (4.26), pimelic acid (4.31), azelaic acid (4.39), fumaric acid (2.85) and the like as oxycarboxylic acid Glycolic acid (3.63), lactic acid (3.66), malic acid (3.24), tartaric acid (2.8)
2-2.99), citric acid (2.87) and the like. Further, glyoxylic acid (3.18), pyruvic acid (2.26), levulinic acid (4.
44) and the like, aniline sulfonic acid (3.74-3.23), which is an aromatic monocarboxylic acid,
Benzoic acid (4.20), aminobenzoic acid (2.02-3.12), chlorobenzoic acid (2.
92-3.99), cyanobenzoic acid (3.60-3.55), nitrobenzoic acid (2.17)
-3.45), hydroxybenzoic acid (4.08-4.58), anisic acid (4.09-4.
48), fluorobenzoic acid (3.27-4.14), chlorobenzoic acid, bromobenzoic acid (
2.85-4.00), benzoic acid having a substituent such as iodobenzoic acid (2.86-4.00), salicylic acid (2.81), naphthoic acid (3.70-4.16), silicic acid Cinnamic acid (3.
88), mandelic acid (3.19) and the like. Also, aromatic monocarboxylic acid nicotinic acid (2.05) such as phthalic acid (2.75), isophthalic acid (3.50), terephthalic acid (3.54), which are aromatic polycarboxylic acids. 2-furancarboxylic acid (2.97) and the like] and heterocyclic polycarboxylic acid [2,6-pyridinedicarboxylic acid (2.09) and the like are also included.

Further, as organic acids, amino acids are often used, for example, asparagine (2
. 14), aspartic acid (1.93), adenine (4.07), alanine (2.30)
, Β-alanine (3.53), arginine (2.05), isoleucine (2.32), glycine (2.36), glutamine (2.17), glutamic acid (2.18), serine (2
. 13), tyrosine (2.17), tryptophan (2.35), threonine (2.21)
), Norleucine (2.30), valine (2.26), phenylalanine (2.26),
Adenosine (3.50), adenosine triphosphate (4.06), adenosine phosphate (3.65) which are amino acid derivatives such as methionine (2.15), lysine (2.04) and leucine (2.35). -3.80), L-alanyl-L-alanine (3.20), L-alanyl glycine (3.10), β-alanyl glycine (3.18), L-alanyl glycyl glycine (3. 24), β-alanylglycylglycine (3.19), L-alanylglycylglycylglycine (3.18), glycyl-L-alanine (3.07), glycyl-β-alanine (3.91) Glycylglycyl-L-alanine (3.18), glycylglycylglycine (3.20), glycylglycylglycylglycine (3.18), glycylglycyl-L-histidine (2.7) ), Glycyl glycyl glycyl -L- histidine (2.
90), glycyl-DL-histidylglycine (3.26), glycyl-L-histidine (2.54), glycyl-L-leucine (3.09), γ-L-glutamyl-L-cysteinyl Glycine (2.03), N-methylglycine (sarcosine, 2.20), N, N-
Dimethylglycine (2.08), citrulline (2.43), 3,4-dihydroxyphenylalanine (2.31), L-histidylglycine (2.84), L-phenylalanylglycine (3.02) , L-prolylglycine (3.07), L-leucyl-L-tyrosine (3.15) and the like.

In the present invention, among the above acids, aliphatic polycarboxylic acids such as aliphatic monocarboxylic acids such as formic acid, haloacetic acids such as chloroacetic acid, saturated or unsaturated C1-3 monocarboxylic acids such as halopropionic acid and acrylic acid, etc. Acids such as saturated or unsaturated C2-4 dicarboxylic acids such as malonic acid, succinic acid, glutaric acid and fumaric acid, and further C1-6 such as glycolic acid, lactic acid, malic acid, tartaric acid and citric acid which are oxycarboxylic acids Oxycarboxylic acids are preferred. These acids may be water-insoluble or water-soluble.

The aforementioned acid may be used as a free acid, or may be used as a partially esterified product, alkali metal salt, alkaline earth metal salt, or heavy metal. Alkali metals include lithium, potassium,
Examples of the alkaline earth metal include calcium, magnesium, barium, and strontium. Heavy metals are zinc, tin, nickel, iron, etc.

Preferred alkali metals include sodium, and preferred alkaline earth metals include calcium and magnesium. These alkali metals and alkaline earth metals can be used alone or in combination of two or more thereof, and alkali metals and alkaline earth metals may be used in combination.

The total content of the acid and the metal salt thereof is within a range that does not impair the peelability, transparency, film forming property, etc., for example, 1 × 10 ^{−9 to} 3 × 10 ⁻⁵ mol per gram of cellulose acylate, preferably 1 × 10 ^{−8 to} 2 × 10 ⁻⁵ mol (for example, 5 × 10 ^{−7 to} 1.5 × 10 ⁻⁵ mol), more preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻⁵ mol (for example, 5 × × 10 ⁻⁶ to 8 × 10 ⁻⁶ mol), and can be selected from the range of about 5 × 10 ^{−7 to} 5 × 10 ⁻⁶ mol (for example, 6 × 10 ^{−7 to} 3 × 10 ⁻⁶ mol). It is.

In addition, content of the said acid and its metal salt in a cellulose acylate can be quantified with the following method.

(Ion chromatography analysis)
Weigh accurately 2.0 g of dried cellulose acetate in the form of fine powder, add 80 ml of hot water, stir and seal, let stand overnight, and then stir to sediment the sample. Using about 10 ml of the supernatant as a sample solution, the acid content is measured by ion chromatography.

In addition, these alkali metals and / or alkaline earth metals may be combined with an acidic group (such as a carboxyl group or a sulfonic acid group) of cellulose acetate when the content is small. The total content of alkali metals and alkaline earth metals in 1 g of cellulose acetate is
More than the effective amount that does not impair the heat resistance stability of cellulose acetate, and 5.5 × 10 ⁻⁶ equivalent or less (for example, 0.01 × 10 ^{−6 to} 5 × 10 ⁻⁶ equivalent) in terms of ion equivalent, preferably 3
. 5 × 10 ⁻⁶ equivalent or less (eg, 0.01 × 10 ^{−6 to} 3 × 10 ⁻⁶ equivalent), more preferably 2.5 × 10 ⁻⁶ equivalent or less (eg, 0.01 × 10 ⁻⁶ to 2). × 10 ⁻⁶ equivalent).
In particular, the total content of alkali metal and alkaline earth metal is 1 × 10 ⁻⁶ equivalent or less (for example,
0.1 × 10 ^{−6 to} 0.5 × 10 ⁻⁶ equivalent), particularly 0.3 × 10 ⁻⁶ equivalent or less (for example, 0.1
When cellulose acetate of about × 10 ^{−6 to} 0.3 × 10 ⁻⁶ equivalent) is used, when the dope is cast on a metal support by a casting method, and a semi-dried film is peeled from the metal support, Peel resistance can be greatly reduced. The content of alkali metal and alkaline earth metal in cellulose acetate can be quantified by atomic absorption analysis.

The cellulose acetate of the present invention can be prepared, for example, by mixing cellulose acetate and an acid having an acid dissociation index, or a partially esterified product or a metal salt thereof, and treating the cellulose acetate with the acid or the metal salt thereof. The mixing or treatment of the acid or the metal salt thereof is carried out after an optional step, for example, a cellulose acetate production step (for example, a heat stabilizer addition step after completion of the hydrolysis / ripening step) or the production of cellulose acetate. Can do. In addition, the treatment with an acid or a metal salt thereof may be performed by washing, dipping treatment, impregnation treatment or the like of powdered or flaky cellulose acetate. Further, the mixing and treatment may be performed by adding an acid or a metal salt thereof to a dope containing cellulose acetate. The mixing or treatment of the acid having the acid dissociation index pKa, the partially esterified product, or the metal salt thereof is performed at an appropriate temperature that does not impair workability, for example, 10 to 70 ° C. (preferably 15 to 50 ° C.
The mixing or processing time is in an appropriate range, for example, 1 minute to 12
You can select from a range of time. When such an acid of a specific pKa or a metal salt thereof is used,
At least a part of the carboxyl groups bonded to cellulose acetate and / or hemicellulose acetate can be present as an acid-type carboxyl group.

After the cellulose acylate solution is cast, the residual solvent is preferably peeled off from the metal support by 20% to 1000% by weight of the solution mass divided by the solid mass, and generally 20 to 20% when there is no release agent. If it is not 150% by mass, it is difficult to peel off and it takes a long time to dry. In contrast, in the cellulose acylate solution containing the release agent of the present invention,
Peeling is possible even when the residual solvent is 20 to 500% by mass, drying time can be shortened, and productivity can be greatly improved. Furthermore, by containing the release agent of the present invention, the peeling load at the time of peeling can be remarkably reduced, and thereby the surface shape is remarkably improved.

Such a cellulose acylate film is a film produced by the casting method.
The releasability from the metal support is high, and the film-forming speed and thus the productivity of the cellulose acylate film can be improved. The cellulose acylate film is excellent in optical properties such as transparency, and its transparency is, for example, about 60 to 100% (preferably 70 to 100%, more preferably 75 to 100%), and usually 70 to 98. %, Haze is 0.01-8%
, Preferably 0.02 to 5%. Furthermore, the yellowness index (Yellowness Index, YI) that is an index of the yellowness of cellulose acetate is, for example,
0.05-10, preferably 0.08-7.

As for the additive, Japanese Patent Application Laid-Open No. 2003-128838 discloses a cellulose acylate having a cross-linking agent having two or more groups that react with at least one kind of active hydrogen in order to improve the stripping property, surface shape, and film strength. There is a description of a cellulose acylate dope solution containing 0.1 to 10% by mass with respect to the rate.

Japanese Patent Application Laid-Open No. 2003-165868 proposes a film that has an additive, has good moisture permeability, and is excellent in dimensional stability.

[Manufacturing process of cellulose acylate film]
(Dissolution process)
The method for dissolving the cellulose acylate solution (dope) of the present invention is not particularly limited, and it may be performed at room temperature, further by a cooling dissolution method, a high temperature dissolution method, a supercritical dissolution method, or a combination thereof. Regarding these, for example, in the method described in JP-A-5-163301, the cellulose acylate solution is stirred at 35 ° C. for 60 minutes at normal pressure. The viscosity of the incompletely dissolved solution is 640 poise at 35 ° C., and it is heated and pressurized with a heat exchanger to be completely dissolved.

In addition, in JP 2001-129838 A, generation of dice lines is suppressed even in a thin film,
In order to enable film formation at high speed, the dope viscosity ρ (P) is within the range of the formula (1) with respect to the dry film thickness d (μm), and 15d / 4 + 170 <ρ <15d / 2 + 340 ( 1) and a manufacturing invention of a cellulose ester film having a dope solid content concentration y (%) within the range of the formula (2) is described, and this invention is also applicable to the present invention.

After that, it is disclosed that the temperature is lowered to 35 ° C. with a cooling heat exchanger, and the rate of decrease in the viscosity delivered from the exchanger is implemented in a range of 2 to 11% based on the incomplete liquid viscosity. JP 61-1066
In No. 28, cellulose acetate, a solvent and an additive are continuously supplied to a kneader and roughly mixed.
A method of preheating with a preheater, supplying continuously to a melting can (pressurized container), pressurizing to an equilibrium pressure due to the vapor pressure of the solvent, moving inside the container while stirring with scraping blades at both ends, and discharging from the outlet at the bottom It is disclosed that it dissolves in

JP-A-58-127737 discloses a method for producing a photosensitive material film in which cellulose acylate is immersed in a non-swelling solvent, and then cellulose acylate separated from the solvent is dissolved in an organic solvent to produce a film. It has been. Japanese Patent Application Laid-Open No. 2000-273239 discloses a method for preparing a cellulose acylate solution that is retained in a mixing container for 1 minute or longer, mixed and swollen, supplied to a second mixing container, and completely dissolved and homogenized. -71463 discloses that a cellulose acylate having an acetylation degree of 58 to 62.5% is a mixture of a solvent containing non-chlorinated carbonization of a main solvent such as acetone, in a preparation process by a cooling dissolution method or a pressure dissolution method. In addition, a method of ultrasonic irradiation is disclosed, and these inventions can be applied to the present invention.

(Room temperature dissolution)
In the case of dissolution at room temperature, cellulose acylate is mixed with a solvent or an additive at a temperature of 0 to 55 ° C., and dissolved by stirring and mixing in a dissolution vessel or the like. Regarding dissolution, it is important to sufficiently soak the cellulose acylate powder with a solvent, and it is essential not to generate so-called Mamako (a cellulose acylate powder part in which the solvent does not spread at all). For this reason, it may be preferable to add a solvent in the stirring vessel in advance, and then add the cellulose acylate under reduced pressure in the dissolution vessel. On the other hand, it may be preferable to add cellulose acylate in the stirring vessel in advance, and then add the solvent under reduced pressure in the dissolution vessel. It is also a preferable method for preparing a solution that cellulose acylate is previously moistened with a poor solvent such as alcohol and then the ether, ketone or ester solvent having 3 to 12 carbon atoms of the present invention is added. When a plurality of solvents are used, the order of addition is not particularly limited. For example, after cellulose acylate is added to the main solvent, another solvent (for example, a gelling solvent such as alcohol) may be added, or conversely after the gelling solvent is preliminarily moistened with cellulose acylate. The main solvent may be added, which is effective in preventing heterogeneous dissolution. In stirring, after cellulose acylate and a solvent are mixed, the cellulose acylate may be left still as it is to sufficiently swell the cellulose acylate with the solvent, and then stirred to obtain a uniform solvent. The amount of cellulose acylate is preferably adjusted so as to be contained in the mixture in an amount of 5 to 40% by mass. The amount of cellulose acylate is more preferably 10 to 30% by mass.

Regarding the dissolution, when preparing a polymer solution in JP-A-2001-113525, there is no pulsation of the additive solution even when the viscosity ratio is larger than a certain value, and it is always dispersed and mixed uniformly. In the method of preparing a polymer solution by continuously dispersing and mixing the liquid to be added and the liquid to be added, the average flow rate of the liquid additive discharged from the addition nozzle is 1 to 10 times the average flow rate of the liquid to be added. An invention has been described.

Furthermore, in JP-A-2001-340735, in order to improve the stirring of the gel-like material and efficiently and quickly dissolve without stagnation, the dissolution tank, the heating jacket heated from the outside, and the melt from the tank In the discharge port that continuously discharges and the continuous stirring and dissolving device that rotates in the tank,
An invention is described in which the stirrer has two or more rotating blades with different phases.

Japanese Patent Laid-Open No. 4-259511 discloses a low concentration TA in order to increase the productivity of the high concentration dope.
After preparing the C solution, this is guided between the cylinder and the outer peripheral locus of the rotating blade rotating in the circumferential direction, and a high-concentration TAC solution is produced while evaporating the solvent by giving a temperature difference with the solution. The invention obtained is described.

Furthermore, in JP-A-4-94704, in order to minimize the operation time and minimize the operation power, in the method of defoaming the high viscosity liquid in the tank, ultrasonic oscillation is generated on the circumferential wall surface of the tank so as to avoid the shaft of the agitator. An invention is described in which a child and a transducer are attached to each other, the amount and size of bubbles in the liquid are calculated from the amount of attenuation of ultrasonic waves, and the output of the decompression device and the defoamer is optimally controlled based on this amount. .

In order to efficiently prepare a uniform dope, Japanese Patent Application Laid-Open No. 2002-316331 describes an invention in which an organic solvent swelling solution is dissolved by irradiation with microwaves.

Furthermore, in JP-A-2002-71435, when liquid is sent to the storage tank, in order to eliminate the deterioration of accuracy due to fluctuations in the flow rate, an over from the liquid delivery stop signal to the actual stop is sent to follow the speed fluctuation. A weighing device is disclosed.

The above-described method for dissolving cellulose acylate in an organic solvent can be applied to the present invention as long as it is within the scope of the present invention.

(Cooling dissolution method)
The cellulose acylate solution (dope) preferably used in the present invention is prepared according to a cooling dissolution method, and the contents thereof will be described below. First, the temperature around room temperature (-10 to 5
The cellulose acylate is gradually added to the organic solvent with stirring at 5 ° C. When a plurality of solvents are used, the order of addition is not particularly limited. For example, after cellulose acylate is added to the main solvent, another solvent (for example, a gelling solvent such as alcohol) may be added, or conversely after the gelling solvent is preliminarily moistened with cellulose acylate. The main solvent may be added, which is effective in preventing heterogeneous dissolution. The amount of cellulose acylate is 5% in this mixture.
It is preferable to adjust so that it may contain ~ 40 mass%. The amount of cellulose acylate is 1
More preferably, it is 0-30 mass%. Furthermore, you may add the arbitrary additive mentioned later in a mixture.

The mixture is then cooled to -100 to -10 ° C (preferably -100 to -30 ° C, more preferably -100 to -50 ° C, most preferably -90 to -60 ° C). The cooling can be performed, for example, with a dry ice / methanol bath (−75 ° C.) or a mechanically cooled chlorofluorocarbon solution refrigerant. When cooled in this way, the mixture of cellulose acylate and organic solvent solidifies.
Although the cooling rate is not particularly limited, in the case of batch-type cooling, the viscosity of the cellulose acylate solution increases with cooling and the cooling efficiency is inferior. is required.

In addition, after the cellulose acylate solution of the present invention is swollen, it can be achieved by transferring a cooling device at a predetermined cooling temperature for a short time. The faster the cooling rate, the better, but 1000
0 ° C / sec is the theoretical upper limit, 1000 ° C / sec is the technical upper limit, and 100 ° C / sec is the practical upper limit. The cooling rate is a value obtained by dividing the difference between the temperature at the start of cooling and the final cooling temperature by the time from the start of cooling until the final cooling temperature is reached. Further, when this is heated to 0 to 200 ° C. (preferably 0 to 150 ° C., more preferably 0 to 120 ° C., most preferably 0 to 50 ° C.), a solution in which cellulose acylate flows in an organic solvent is obtained. . The temperature can be raised by simply leaving it at room temperature or in a warm bath. At this time, the pressure may be 0.3 to 30 MPa, but there is no particular problem. In that case, it is preferable to carry out in as short a time as possible, preferably within 0.5 to 60 minutes, and in particular, heating in a short time of 0.5 to 2 minutes is recommended.

If the dissolution is insufficient, the cooling and heating operations may be repeated. Whether or not the dissolution is sufficient can be determined by merely observing the appearance of the solution with the naked eye. In the cooling and melting method, it is desirable to use a sealed container in order to avoid moisture mixing due to condensation during cooling. In the cooling and heating operation, when the pressure is applied during cooling and the pressure is reduced during heating, the dissolution time can be shortened. In order to perform pressurization and decompression, it is desirable to use a pressure-resistant container. Regarding the above cooling and dissolving method, JP-A-9-95544 and JP-A-10-9.
This is described in detail in each publication of No. 5854.

In JP-A-10-45950, it is shown that in the cooling and dissolving method, the swelling mixture is heated to a temperature not lower than the boiling point of the solvent under a pressure adjusted so that the solvent does not boil in the heating step. Yes.

Japanese Patent Application Laid-Open No. 9-95544 discloses a cooling process in which a mixture of cellulose acetate in an acetone solvent and containing 10 to 40% by mass of cellulose acetate is -100 to -10 ° C, and heated to 0 to 50 ° C. The method of casting on a metal support and the method of producing in a solvent evaporation step are also disclosed in JP-A-10-95854, which is a cooling dissolution method, under a pressure adjusted so that the solvent does not boil in the heating step. In the method of heating the swelling mixture to a temperature equal to or higher than the boiling point of the solvent, JP-A-10-45950 discloses a cellulose acetate solution having an acetylation degree of 58 to 62.5%.
Non-chlorine organic solvent with an apparent viscosity of 100 to 2000 poise at 40 ° C. and 40 ° C.
A solution having an apparent viscosity of 100000 poise or more at a temperature of 0 ° C. or higher when cooled at a rate of 2 ° C./min. Is disclosed in Japanese Patent Application Laid-Open No. 2000-53784 by casting and drying a non-chlorine solution on a metal support. Cellulose acylate having a degree of acetyl substitution (A) and a degree of substitution of acyl groups having 3 and 4 carbon atoms (B) (1) to (3) described later, and containing 100 ppm of alkaline earth metal An acylate is disclosed. Where (1) 2.6 ≦ A + B ≦ 3, (2
) 1.4 ≦ A ≦ 2.5, (3) 0.5 ≦ B ≦ 1.2.

JP-A-11-322946 discloses cellulose acylate having an acetylation degree of 58 to 62.5%, an ester solvent having 3 to 12 carbon atoms, a ketone solvent having 4 to 12 carbon atoms, and 3 to 3 carbon atoms.
A mixture containing a solvent composed mainly of one of 12 ether solvents is added to 10 to 5000 kgf /
A process of cm ² and a method for preparing a cellulose acylate solution obtained by treating the treated mixture under a pressure of 0.1 to 10 kgf / cm ² are disclosed.

Further, JP-A-11-322947 discloses a mixture containing a cellulose acylate having 3 or more carbon atoms and containing an organic solvent containing a non-chlorine organic solvent as a main component.
A method for preparing a cellulose acylate solution through a treatment step under a pressure of / cm ² and a step of treating the mixture under a pressure of 0.1 to 10 kgf / cm ² is disclosed in JP-A-2-276830 as a TAC solution. Describes a method for producing a cellulose acylate in which a dye solution is added and mixed in-line, a color density is measured in a transport pipeline, and the amount of the prescribed dye solution added is controlled.

Furthermore, in JP-A No. 04-259511, after preparing a low-concentration TAC solution, this is guided between the cylinder and the outer peripheral locus of the rotating blade rotating in the circumferential direction, and a temperature difference is established between the solution and the solution. And a process for obtaining a high concentration TAC solution while evaporating the solvent is disclosed.

JP-A-2000-273184 discloses a method for adjusting a cellulose acylate dope, in which cellulose acylate and a poor solvent are mixed, and the solvent is mixed and dissolved in the mixture without separating the poor solvent. No. 10-10 in Japanese Patent Laid-Open No. 11-310640.
A mixture obtained by continuously adding 10 to 100 ppm of cellulosic acylate containing an alkaline earth metal to a non-chlorine solvent being transferred at 0 to −10 ° C. is swollen, and part of the solvent is separated and concentrated. A method of preparing a cellulose acylate solution by mixing a non-chlorinated solvent that is being transferred to the subsequent mixture at 0 to 120 ° C. is disclosed. JP-A-11-323017 discloses -100.
Particle size 0.05-2mm pulverized above 150 ° C in non-chlorine solvent being transferred at -10 ° C
Of cellulose acylate is continuously added to swell to form a mixture, and then a part of the solvent is separated and concentrated, and the solution of the same composition is mixed at 0 to 120 ° C. to form a solution. The law is disclosed. JP-A-11-302388 discloses-
The same composition being transferred at 0 to 120 ° C. After continuously adding cellulose substituted with an acyl group having 2 to 5 carbon atoms to the organic solvent being transferred at 100 to 10 ° C., the organic solvent was separated and concentrated after swelling. A method for preparing a cellulose acylate solution through dissolution / dilution steps of a mixture after concentration in a solvent is described.

Further, JP-A-11-071463 discloses that acetyl-substituted 58-62.5% TA is used to cope with environmental pollution.
C, a mixture of an acetone-based organic solvent is cooled at −100 to −10 ° C., heated and dissolved at 0 to 50 ° C., and if necessary, a TAC solution that is passed through an additive addition step is cast on a support And the invention of sonication in any of the steps of drying.

Further, in order to cool to a higher temperature to the limit at which the cooling dissolution method can be carried out, JP 2001-055403 A and JP 2001-059001 A include 10-40% of 58.25-62.5% cellulose acetate. An invention is described which is an organic solution, a cooled mixture in which cellulose acetate swells without dissolving in an organic solvent at a temperature (T) defined by a specific formula.

In addition, in order to carry out stable and efficient production, JP-A-2001-294667 describes a step of swelling cellulose acetate in a solvent in which 90% or more of 58-62.5% cellulose acetate particles are 0.1-4 mm, swelling The invention which melt | dissolves through the process which cools a sound article to -100--10, and the process which heats the swelling mixing part T to 0-120 degreeC is described.

Furthermore, Japanese Patent Application Laid-Open No. 11-302388 describes organic transporting at −100 to 10 ° C. in order to shorten the time of the TAC and solvent swelling process, cooling process, and heating process, and to reduce the use of methylochrome. In solvent, C2-5
An invention is described in which an acyl group-substituted cellulose swells a continuous additive, separates and concentrates an organic solvent, and dissolves and dilutes the mixture after concentration in the same composition solvent being transferred at 0 to 120 ° C.

Further, JP-A-2000-053784 discloses a TA prepared by extending a non-chlorine solution upstream and drying a non-chlorine solution for the purpose of obtaining a film having excellent optical characteristics and mechanical strength by adjusting the concentration with a non-halo solvent.
In C, the degree of acetyl substitution (A) and the degree of substitution of C3-4 acyl group (B) are (1)-(3), and C2-4 cellulose containing alkaline earth metal of 100 ppm or more ((1) 2.6 ≤ A + B ≤ 3 (2) 1.4 ≤ A ≤ 2.5 (3) 0.5 ≤ B ≤ 1.
2) The invention is described.

JP-A-9-157400 discloses a polymer that normally swells but does not dissolve,
After swelling (-10 to 55 degrees), cooling (-100 to -10 ° C) and then heating (0 to 55 ° C) to dissolve the dope, the cooling rate in cooling is 1 to 40 An invention is described in which the heating rate is 1 to 40 ° C./min.

Furthermore, in order to reduce the energy of cooling, conveying and heating with a simple device, Japanese Patent Laid-Open No. 10-114
No. 829 is a cooling / heating device that has a “cylindrical cooling container + rotatable spiral conveyance mechanism + cooling mechanism” and a plurality of divided by a cylindrical heating container + element (static mixer). ) + Warming mechanism ”is described.

Furthermore, in order to quickly penetrate the solvent into the powder and prevent the formation of aggregates, JP-A-11-005025
Describes the invention of cooling and dissolving after mixing the powder and solvent under reduced pressure.

In addition, for the purpose of a cellulose acetate film having excellent optical properties and physical properties, Japanese Patent Application Laid-Open No. 10-044327 discloses cellulose acetate obtained by cooling to −100 to 10 ° C. and heating to 0 to 120 ° C. An invention is described in which a coating layer of a coating solution containing fine particles having a polymer content of 1 μm or less is provided on a film and has a haze of 2.0% or less or an 80 μm thickness equivalent tear strength of 18 g or more and a coating layer surface friction coefficient of 0.4 or less ing.

Further, similarly, for the purpose of a cellulose acetate film having excellent optical properties and physical properties, Japanese Patent Application Laid-Open No. 10-095861 discloses that the solution is cooled to −100 to −10 ° C. and heated to 0 to 120 ° C. The obtained cellulose acetate film has an average degree of acetylation of 58 to 62.5%, a thickness converted haze of 80 μm, 0
. An invention is described in which the tear strength in terms of 4% or less or 80 μm thickness is 20 g or more.

In addition, for the purpose of a cellulose acetate film having excellent optical properties and physical properties, Japanese Patent Application Laid-Open No. 10-095862 discloses dissolving by cooling to −100 to −10 ° C. and heating to 0 to 120 ° C. 58 ~
An invention is described in which the haze is 62.5%, the haze of 80 μm equivalent in terms of thickness is 0.6% or less, or the thickness equivalent tear strength of 80 μm is 18 g or more, and the dynamic friction coefficient of the film surface is 0.4 or less, and this invention is also applicable to the present invention.

The above-described method for dissolving cellulose acylate in an organic solvent can also be applied in the present invention.

(High temperature dissolution method)
A high-temperature dissolution method that is preferably performed in the preparation of the cellulose acylate solution (dope) of the present invention will be described below. First, cellulose acylate is gradually added to an organic solvent at a temperature around room temperature (−10 to 55 ° C.) while stirring. When a plurality of solvents are used, the order of addition is not particularly limited. For example, after cellulose acylate is added to the main solvent, another solvent (for example, a gelling solvent such as alcohol) may be added, or conversely after the gelling solvent is preliminarily moistened with cellulose acylate. The main solvent may be added, which is effective in preventing heterogeneous dissolution. The cellulose acylate solution of the present invention is preferably swollen in advance by adding cellulose acylate to a mixed organic solvent containing various solvents. In that case, -10 to 55
The cellulose acylate may be gradually added with stirring to any solvent at ℃, and in some cases, it may be pre-swelled with a specific solvent and then mixed with another combined solvent to obtain a uniform swelling liquid. Further, the remaining solvent may be added after swelling with two or more solvents, and is not particularly limited.

Next, the organic solvent mixture is heated to 60 to 240 ° C. under a pressure of 0.2 MPa to 30 MPa (preferably 60 to 220 ° C., more preferably 70 to 200 ° C., most preferably 80
~ 190 ° C). The heating may be, for example, high-pressure steam or an electric heat source. A pressure vessel or a pressure line is required for high pressure, but any of iron, stainless steel, or other metal pressure vessel or line may be used, and is not particularly limited.

Furthermore, carbon dioxide may be enclosed in these high-temperature and high-pressure solutions to form a so-called supercritical solution.
In that case, the ratio of carbon dioxide to the solvent is preferably 5/95 to 70/30, more preferably 10 /
90-60 / 40 is preferable.

Next, since these heated solutions cannot be applied and cast as they are, it is necessary to cool them below the lowest boiling point of the solvent used. In that case, it is common to cool to -10-55 degreeC and to return to a normal pressure. For cooling, the high-pressure and high-temperature vessel or line containing the cellulose acylate solution may be left at room temperature, and more preferably, the apparatus may be cooled using a coolant such as cooling water. Note that heating and cooling operations may be repeated in order to accelerate dissolution. Whether or not the dissolution is sufficient can be determined by merely observing the appearance of the solution visually. In the high-pressure and high-temperature dissolution method, a closed container is used to avoid evaporation of the solvent. In addition, the dissolution time can be further shortened by increasing the pressure or reducing the pressure in the swelling step. In order to perform pressurization and decompression, a pressure-resistant container or line is essential.

Here, regarding high-temperature dissolution, Japanese Patent Application Laid-Open No. 61-129031 reduces the concentration of the dope and the gel,
In order to reduce the size of the equipment, an invention relating to a method for dissolving TAC is described in which a TAC solvent is sealed in a pressure vessel and heated under a pressure at a temperature not lower than the normal pressure boiling point and in a range where the solvent does not boil and stirred. Has been.

Furthermore, JP 2000-273184A discloses that cellulose acylate and a poor solvent are mixed to reduce filtration load and dissolution time without agglomeration of powder, and a good solvent is added to the mixture without separating the poor solvent. An invention in which a main solvent is mixed and dissolved is described.
Here, as a more preferable embodiment, 1.0 × 10 in the cellulose acylate dissolution step
Stirring to dissolve by applying a shearing force of ^{1 to} 1.0 × 10 ⁵ kgf / m / sec ² ;
A mixture of cellulose acylate and a solvent is pressurized and held at 3 to 4000 kgf / cm ² , and then an operation of releasing the pressure and holding it at normal pressure is performed. ・ Pressure speed is 1 kgf / cm ^2.
For example, operating at a reduced pressure rate of 1 kgf / cm ² / min or higher at a normal pressure. Furthermore, in the apparatus for preparing the cellulose acylate dope, when the storage tank and the heat exchanger, which are pressure-resistant containers equipped with a jacket tank and a stirrer that can be heated and cooled, are connected via a circulation path, the temperature condition is as follows. The relationship between the boiling point Bp (° C.) of the solvent having the lowest boiling point in the mixture in the storage tank and the temperature Ty (° C.) of the storage tank is expressed as Bp ≦ Ty ≦ B
p + 50, and the relationship between Ty and the temperature Tj (° C.) of the medium for heating the heat exchanger is Tj ≧ T
It has been shown that it is preferred to dissolve as y + 30.

Furthermore, in JP-A-2000-273184, cellulose acylate and a poor solvent thereof are mixed to form a mixture and to separate the poor solvent in order to improve work efficiency, reduce danger and improve productivity. Without mixing, the mixture is dissolved in a solvent mainly composed of a good solvent for cellulose acylate. At this time, it is described that the mixture in the storage tank is preferably dissolved such that the mixing ratio R of the cellulose acylate and the total amount of solvent is 16 to 40% by weight. In addition, an apparatus for mixing cellulose acylate and a poor solvent in advance can be used without limitation as long as it is a container with a general stirrer, but when the ratio of the poor solvent to cellulose acylate is small, a kneader or an extruder is used. A pressure-resistant container of such a closed system that is fed out while being kneaded is preferable, and as a stirring means for applying a shearing force, a shearing stress is generated by a stirrer such as a propeller type, a turbine type, a paddle type, a spiral type or an anchor type. It has been shown that it can. When mixing a mixture of cellulose acylate and a poor solvent and a solvent mainly composed of a good solvent, a solvent composed mainly of a good solvent may be added to the mixture and dissolved. It is also disclosed that it is easier to dissolve a mixture in a solvent mainly composed of a solvent, and the dissolution time can be further shortened.

Furthermore, in JP-A-2000-273184, as a suitable pressurizing method and pressurizing apparatus, the pressurizing apparatus used for dissolution on the high-pressure side is safe for a mixture of cellulose acylate and an organic solvent. In addition, since hydrostatic pressure can be applied uniformly from all directions, the hydrostatic pressure method used for ceramic molding is preferred. In this hydrostatic pressure method, the material of the container that encloses the mixture is easily made of rubber or pressure. A deformable metal, such as an aluminum container, may be used, and the mixture is sealed in an easily deformable sealed container such as rubber, and prepared intermittently by moving and transporting the sealed container while applying hydrostatic pressure. It is disclosed that it may be a device. In addition, the mixture can be put into a container having a lid that can be slid up and down, and a means for compressing the mixture by pushing the lid can be taken.Furthermore, using a pressure type extruder, for example, a kneader or an extruder, The mixture may be kneaded and extruded. During the dope preparation, the pressure treatment may be intermittently performed, and the solubility is increased by repeating the pressure treatment and the pressure reduction treatment (treatment for returning to normal pressure). It is described.

Further, in JP-A-2000-273184, the storage tank is preferably a pressure vessel equipped with a jacket inside or outside the tank and having a stirrer having a shearing force, in order to make the dope more uniform. In this case, as a preferable condition, the liquid temperature Ty of the pressure-resistant hermetic storage tank is Bp ≦
It is shown that when Ty ≦ (Bp + 50 ° C.) and further dissolved as Tj ≧ Ty + 30, the inside of the storage tank and the inside of the circulation path are in a pressurized state of about 3 to 5 kgf / cm ^2. Yes. Also, by passing the dope through the circulation path, the circulation path can give a shear force of 1.4 times or more than in the storage tank, and the high concentration dope can be shortened by the increased pressure and shear force. It is disclosed that it can be prepared as a completely homogeneous solution over time, and the solubility is increased by repeating the circulation 2 to 4 times. Furthermore, after circulation, it may be transferred to the next container and diluted with a solvent. In this case, the solvent may be a good solvent or a mixed solvent of a good solvent and a poor solvent. As a method of mixing the dope and the solvent, It is described that a solvent may be added to the dope, or a dope may be added to the solvent.

In addition, JP 2000-273239 A discloses that in order to suppress the generation of undissolved matter and gel even in high-speed casting,
In the continuous dissolution apparatus, an invention is described in which the mixture is retained in the mixing container A for 1 minute or longer, mixed and swollen, and supplied to the second mixing container B to be completely dissolved and homogenized. It is disclosed as a preferred condition. 1) The particle size d0 of the cellulose acylate supplied to the mixing vessel A is 5 × 10 ⁻¹ mm ≦ d0 ≦ 20 mm. 2) The final dissolution temperature (T2) in the second mixing vessel B and the mixing vessel B And the solvent temperature (T1) before mixing in the solvent is equal to or higher than the boiling point at normal pressure of the solvent having the lowest boiling point among the solvents in the mixture, and 3) a dissolution vessel having a stirrer for the mixture of cellulose acylate and solvent After stirring, the peripheral speed of the blade of the stirrer is stirred for 30 minutes or more at 0.5 m / sec or more to dissolve.

In JP-A-2000-273239, the mixing container A is compact and excellent in dispersibility, but the mixing container B is pressurized by setting the temperature to be equal to or higher than the boiling point of the solvent. Each of the pressure-resistant containers is shown to be necessary. Furthermore, when the mixture is introduced from the mixing vessel A to the mixing vessel B, it is necessary to introduce the mixture so as to overcome the pressure, but as a means for this, in order to suppress the generation of agglomerates and shorten the dissolution time, press-fitting is used. Specifically, it is disclosed that a pressure pump that can be introduced after mixing and dispersion, pressurization with nitrogen gas, particularly a method that can be supplied while mixing and dispersing such as a kneader or an extruder are preferred. The mixing container A itself may have a means such as an extruder, and the mixing container B can be used without limitation as long as it is a pressure-resistant sealed container, but the boiling point of the solvent having the lowest boiling point among the solvents used. From 40 to 50 ° C., the temperature in the container can be increased, and it is described that a material that can withstand the pressure is preferable. When introducing from the mixing vessel A to the mixing vessel B, it is important that the temperature of the solvent in the mixing vessel B is set to be equal to or higher than the boiling point of the solvent in advance, so that the introduced mixture is instantly dispersed and dissolved. It has been shown that by doing this, the generation of agglomerates can be suppressed and the dissolution time can be extremely shortened. As for the stirrer, it is necessary that the peripheral speed of the blade tip is 0.5 m / sec or more. Specifically, a propeller type, a turbine type, a paddle type, a helical type, an anchor type, a disperser It is disclosed that a stirrer such as a mold can be used.

Furthermore, in order to increase the stability and reduce the environmental load and capital investment, JP 2001-342257 A discloses a method for producing a cellulosic polymer powder in a method for producing a polymer easily soluble powder. An invention is described in which a raw material polymer is dissolved in an organic solvent under a pressure of less than 10 kgf / cm ² and then the solvent is removed.

Japanese Patent Laid-Open No. 2001-198935 discloses that a solvent at a temperature equal to or higher than the boiling point at 1 atm of the main solvent of cellulose ester is used to improve foreign matter failure caused by a low acetylation degree TAC and increase transparency and tear strength. Describes an invention in which a dope solution dissolved in is cast. Here, as a more preferable embodiment, the dope solution may be cast after being dissolved in a solvent at 60 ° C. or higher and 110 ° C. or lower, filtered at a temperature equal to or higher than the boiling point at 1 atm of the main solvent, It is disclosed that after filtration at a solid content concentration of 13% by mass or less as the solid content concentration of the ester, it is concentrated to 16% by mass or more as the solid content concentration of cellulose and then cast. More specifically, after the dope solution is filtered, the solvent of the dope solution may be evaporated. After dissolving the cellulose ester at a poor solvent concentration of 0 to 6% by mass of the cellulose ester, the poor solvent is added and the concentration is adjusted. 7-1
It describes that a dope solution of 6% by mass is cast.

Japanese Patent Application Laid-Open No. 2001-198935 discloses that cellulose ester is swollen with its swelling solvent, and then the good solvent may be added to dissolve the cellulose ester. May contain cellulose acetate propionate, the absolute filtration accuracy of the filter for filtering the dope solution may be 1 to 6 μm, the material of the filter may not contain cellulose, The material of the filter to be filtered may be mainly composed of metal or polypropylene, a dope solution having a turbidity of 20 ppm or less may be cast, and a preferable temperature range in the filtration step is 45 to 55 ° C. preferably, filtration pressure is smaller have been shown to be preferred in particular is ^{1.6 × 10 6 Pa1.0 × 10 6} Pa

Further, JP 2002-200629 discloses a dispersion of cellulose triacetate or a solution thereof.
A solution casting method is described in which the treatment is carried out at a temperature of ℃ or higher.

In addition, in Japanese Patent Laid-Open No. 2003-171471, in order to efficiently heat and dissolve the dope without boiling, the TAC dope is heated and heated to a temperature equal to or higher than the boiling point at normal pressure without being heated by boiling. In the TAC preparation method for cooling after promoting the heating, the heating heat source temperature of the jacket is controlled to be 40 ° C. or more higher than the heating target temperature of the dope in the static mixer when heating is performed in the static mixer with the jacket. With V = 32Q / πd3 (Q is the doping flow rate (m ³ / s)
, D is a method for preparing a TAC top, characterized in that the wall shear rate V of the static mixer determined by the inner diameter of the container (m) is controlled to 2 (1 / s) or more.

Furthermore, Japanese Patent Application Laid-Open No. 2002-241511 eliminates deformation over time even for a thin film of 20 to 60 μm, is optically isotropic, does not cause scratches, and eliminates bubbles and undissolved substances. For the purpose of dissolving the dope under specific dissolution conditions, and the amount of residual solvent at the time of winding is 0.05% by mass or less.

Here, as preferable dissolution conditions, the pressure-resistant dissolution container is sealed, and BP + 20 ° C. to BP
A method is described in which the temperature is continuously raised to + 50 ° C. to obtain a pressurized state, and the dope is dissolved by increasing the pressure according to the heating temperature. As more detailed conditions, as a more preferred embodiment, the rate of temperature increase is, for example, about 0.3 to 5 minutes / ° C., set as appropriate in the situation at that time, and the holding temperature in the sealed pressurized state is BP + 20 ° C. to BP + 50 ° C., preferably BP + 25
It has been disclosed that maintaining the temperature in a range from ℃ to BP + 45 ℃ and maintaining this state is about 10 to 180 minutes, but a shorter one is preferable.

Furthermore, in JP-A-2002-241511, after confirming the completion of dissolution, cooling is performed, and the cooling rate is, for example, about 0.05 to 10 minutes / ° C., and may be appropriately set depending on the situation at that time. It is described that it is preferably 0.5 to 5 minutes / ° C. The temperature of the cooled dope is not particularly limited as long as the boiling point of the solvent is BP, and it is preferably as high as possible from the standpoint of ease of filtration. From the relation of BP to BP-1
It is described that it is 5 degreeC, Preferably it is BP-0.5 degreeC-BP-10 degreeC.

In addition, regarding high temperature dissolution, JP-A-11-322946 and JP-A-11-322947 are disclosed.
Details are also described in each publication.

The above-described method for dissolving cellulose acylate in an organic solvent can be applied to the present invention as long as it is within the scope of the present invention.

As another dissolution method, for the purpose of not using a chlorinated solvent that is harmful to the environment, JP 2002-127166 A discloses a method for dissolving a cellulose polymer in a supercritical state in a method for producing a polymer film. The invention to be described is described.

Furthermore, for the purpose of excellent solubility, Japanese Patent Application Laid-Open No. 2000-256468 discloses that in a polymer solution preparation apparatus, at least one supercritical state selected from a supercritical temperature or higher and a supercritical pressure or higher of a substance that becomes a supercritical fluid. The invention has a means for forming a supercritical fluid of the substance and a means for dissolving the polymer using the substance in the state.

Japanese Patent Laid-Open No. 2002-317051 discloses a solution preparation method in which a mixture of a solvent and a polymer is irradiated with microwaves in order to efficiently prepare a uniform polymer solution.

A method for dissolving these cellulose acylates in an organic solvent is also applicable in the present invention.

(Solution concentration)
As described above, the concentration of the cellulose acylate solution of the present invention is characterized in that a high concentration dope can be obtained, and a cellulose acylate solution having a high concentration and excellent stability can be obtained without relying on a means of concentration. . Furthermore, in order to make it easy to melt | dissolve, you may melt | dissolve at a low density | concentration and may concentrate using a concentration means. The concentration method is not particularly limited, but for example,
A method of obtaining a high-concentration solution while evaporating the solvent by giving a temperature difference between the solution and the temperature of the low-concentration solution between the cylinder and the rotation trajectory of the outer periphery of the rotating blade rotating in the circumferential direction ( For example, Japanese Laid-Open Patent Publication No. 4-259511), a heated low concentration solution is blown into the container from the nozzle, the solvent is flash evaporated between the nozzle and the inner wall of the container, and the solvent vapor is extracted from the container. A method of extracting a high concentration solution from the bottom of the container (for example, US
P No. 2541012, USP No. 2858229, USP No. 4414341, USP
No. 4504355 described in each specification etc.).

These cellulose acylate dope concentration methods described above can also be applied to the present invention.

(Filtration and defoaming)
Prior to casting, it is preferable to filter off foreign matters such as undissolved matter, dust, and impurities using a suitable filter medium such as a wire mesh or flannel. For the filtration of the cellulose acylate solution, a filter having an absolute filtration accuracy of 0.1 to 100 μm is used, and further an absolute filtration accuracy of 0.5 to
It is preferable to use a filter having a thickness of 25 μm. In that case, the filtration pressure is 1
6 kgf / cm ² or less, more preferably 12 kgf / cm ² or less, more 10 kgf / c
It is preferable to filter at m ² or less, particularly preferably 2 kgf / cm ² or less. The filtration flow rate is preferably 5 liters / hr, more preferably 50 liters / hr.

Filtration of the cellulose acylate solution has a viscosity of 100% of the melt containing cellulose acylate.
It is preferably filtered at 00 P or less, more preferably 5000 P or less, and preferably 1
More preferably, it is 000 P or less, and more preferably 500 P or less. As the filter medium, conventionally known materials such as glass fibers, cellulose fibers, filter paper, fluororesins such as tetrafluoroethylene resin can be preferably used, and ceramics, metals and the like are particularly preferably used. The filter medium can be either a surface type or a depth type, but the depth type is preferably used because it is relatively less clogged.

Foreign matter with a size exceeding 50 μm recognized in the crossed Nicol state by this filtration has an area of 2
Virtually 0 pieces can be achieved per 50 mm ² , and a foreign matter of 5 to 50 μm has an area of 250 mm.
² per 200 or less can be achieved, the commercial value of the polarizing plate protective film can be a raised significantly.

At this time, the polarizing plate used for the evaluation is desirably composed of a protective film having no bright spot foreign matter, and a polarizing plate using a glass plate for protecting the polarizer is preferably used. The bright spot foreign matter is considered to be one of the causes due to unacetylated cellulose contained in cellulose acylate, and by using cellulose acylate with less bright spot foreign matter and removing dissolved cellulose acylate, Can be reduced. Further, the thinner the film thickness, the smaller the number of bright spot foreign matter per unit area, and the lower the content of cellulose acylate contained in the film, the less bright spot foreign matter tends to be.

Concerning bright spot foreign matter, Japanese Patent Application Laid-Open No. 2001-198935 casts a dope solution having an undissolved fiber number of 10 pieces / liter or less before filtration, has a bright spot foreign matter number of 200 pieces / cm ² or less ^{, and a} tear strength of 5 g. A method for obtaining the above film is described. In addition, the greater the diameter of the bright spot, the greater the actual damage.
If it is 50 μm or less, there is no practical problem, but 10 μm or less is preferable, 8 μm or less is more preferable, and 6 μm or less is particularly preferable, and this invention can also be applied to the present invention.

In addition, although the cause of a bright spot may be due to foreign matters in the dope, pinholes on the surface of the film generated due to bubbles at the time of casting due to bubbles in the dope can also be mentioned. Therefore, it is preferable to defoam the dope before casting.

Regarding defoaming, Japanese Patent Application Laid-Open No. 2003-200445 describes that a high-concentration cellulose acylate solution before casting on a casting support is saturated dissolved air at 1 atm to prevent failure due to casting bubbles. A solution casting method characterized by degassing to 90% or less of the amount is described.

Further, JP-A-2002-241511 discloses a method for reducing the number of bubbles of 0.3 μm or more in the dried film to zero, that is, a method for preventing bubbles. (1) Cellulose ester in a pressure-resistant dissolution vessel After mixing the organic solvent, etc., raise the temperature to around BP, (2) open the pressure-dissolving vessel to the atmosphere while standing at that temperature for 6 minutes or more, and (3) close the pressure-dissolving vessel from the atmosphere to the boiling point B
Assuming P, it is disclosed that the temperature is raised to BP + 20 ° C. to BP + 50 ° C. to be in a pressurized state, and (4) the dope is subsequently dissolved using the pressurized state.
Further, as a more preferable condition, after mixing cellulose ester flakes (large powder) and an organic solvent in a pressure-resistant dissolution vessel, the temperature is raised to the vicinity of the boiling point of the main organic solvent that dissolves the cellulose ester, It is described that when the temperature is reached, it is allowed to stand for 6 minutes or more, preferably 10 minutes or more. In the meantime, the cock at the top of the pressure-resistant dissolution vessel is opened and opened to the atmosphere, and the air in the upper space inside the vessel is replaced with organic solvent vapor. After standing for a predetermined time, the temperature is raised above BP. Complete dissolution of the cellulose ester, cool, filter,
It is disclosed that a cellulose ester film having zero bubbles can be obtained by forming a film by a solution casting film forming method described later. Here, the time to stand still in the atmosphere after the temperature rise may be increased immediately after 6 minutes to complete the dissolution, or may be left overnight or longer depending on the work procedure in the dissolution process. It is described that it may be.

Regarding additive-based defoaming, JP-A-2002-128900 preferably defoams before mixing when mixing a cellulose ester solution with a fine particle dispersion to form a dope. Has been described.

More specifically, when transferring or storing the fine particle dispersion stock solution after dispersion, the liquid containing the fine particles and the organic solvent is dissolved or dispersed and stored in order to prevent the dispersion from being exposed to air in either the transfer tube or the storage container. When transferring to a container for storage and raising the temperature in this container,
Alternatively, it is preferable to leave it for a long time and let the air contained in the solution be released as bubbles, and in particular, if the dope after mixing also has equipment or time allowance, such defoaming is recommended. It is described that it is good to do.

Here, as the vibration device, it is preferable to give as fine and strong vibration as possible, and ultrasonic waves are preferable, and in the case of pipes and filters, it is preferable to arrange the ultrasonic vibration elements directly inside them, especially It has also been shown to be a good way to attach to internal metal parts. Further, it is disclosed that the vibration frequency of a useful vibration device is preferably 100 Hz to 40 kHz, and particularly preferably 10 to 40 kHz as an ultrasonic vibration element.

These inventions described above can also be applied to the present invention.

The viscosity of the cellulose acylate solution immediately before film formation may be in a range that can be cast during film formation, and is usually adjusted to a range of 10 Pa · s to 2000 Pa · s, preferably 30 Pa.
-S-1000 Pa.s is more preferable, and 40 Pa-s-500 Pa.s is still more preferable. The temperature at this time is not particularly limited as long as it is the temperature at the time of casting, but preferably −5
It is -70 degreeC, More preferably, it is -5-55 degreeC.

Regarding filtration, for example, a method for producing a cellulose acylate film that reuses a cellulose acylate solution remaining in a filtration process described in JP-A-2000-273199 as a raw material, or a retained particle diameter according to JP-A-2000-256477. However, a production method of forming a film by filtering cellulose acylate with a filtration of 8 μm or less can also be used. In addition, the filtered cellulose acylate solution described in JP-A-11-254594 and the cellulose acylate solution filtered through a filter with high filtration accuracy are applied to the surface of a metal support by the simultaneous casting method, and dried and then peeled off. In addition, a method for producing a cellulose acylate film laminate having a high surface smoothness without a boundary surface inside the film may also be mentioned.

Japanese Patent Laid-Open No. 2002-137237 also discloses that the dope flow rate passing through the dope filter is kept constant by passing it at the maximum flow rate to prevent the outflow of foreign matters when the flow rate is changed, Is described in reverse.

Similarly, in order to prevent the outflow of foreign matter at the time of switching, Japanese Patent Application Laid-Open No. 2002-137238 describes an invention in which the dope filter to be switched is fed back upstream at a flow rate equal to or higher than the dope amount of casting. ing.

Regarding the filtration of the additive system, JP 2001-213974 describes an invention in which an additive solution added in-line to the main dope is added in-line after being filtered through a depth type filter. .

Further, as a preferred embodiment, the additive solution is filtered through two or more depth filters, the number of times of filtration is 3 to 10 times, and 8 kinds of 0 of the test powder 1 defined in JISZ8901 It is disclosed that the cartridge filter has a particle collection rate of 5 to 10 μm when a 0.5 ppm aqueous dispersion is filtered and is 20 to 60%. Furthermore, after being filtered with a thread-wound type filter in which long fibers are wound around a core made of polypropylene or stainless steel, a metal filter (Nippon Seiki) with an absolute filtration accuracy of 30-60 μm and a porosity ε = 60-80% There is a description that it is preferable to filter with fine pore NF series (NF-10, NF-12, NF-13, etc.) and then add in-line. Also,
-The additive solution added in-line to the main dope is fed by a reciprocating pump,
The additive solution is filtered at a flow rate of 10 ml / min / cm ² or less per unit area of the filter;
-The filtration flow rate just before in-line addition is 1 ml / min / cm ² or less,
-The differential pressure during filtration is 200 kPa or less,
-The temperature of the in-line additive solution during filtration is 30 to 110 ° C.
-The additive liquid may contain fine particles, the fine particles are silicon dioxide fine particles, the primary average particle diameter is 20 nm or less, the apparent specific gravity is 70 g / liter or more, and the like is described as a preferable embodiment.

Also, according to JP 2001-213974, surface type filters, when used for a long time, gel aggregates contact each other on the surface, grow into larger aggregates and pass through the filter due to increased pressure. It has been shown that aggregates cannot be removed and increase. Examples of the surface type include a filter paper pleated cartridge filter TC type manufactured by Advantech Toyo Co., Ltd. and a metal mesh used for a sieve. In addition, the depth type filter has a certain media thickness, and the possibility that the aggregates in the filter part will be in contact with each other is lower than that of the surface type, producing large gel aggregates. It is difficult to increase the pressure even when used for a long time.
It is disclosed to remove gel aggregates. Examples of the depth type include a wind cartridge filter TCW type manufactured by Advantech Toyo Co., Ltd., a depth cartridge filter TCPD type, and a fine pore NF series manufactured by Nippon Seisen Co., Ltd.

Furthermore, according to Japanese Patent Application Laid-Open No. 2001-213974, the agglomeration contained in the in-line additive solution is in the form of a secondary or tertiary agglomerate, so a membrane type (Advantech Toyo Co., Ltd. membrane cartridge filter TCF type, pleated cartridge filter TCPE) It is disclosed that agglomeration (product) is easy to come off in a filter medium of type etc., and that a thread wound type (wind cartridge filter TCW type manufactured by Advantech Toyo Co., Ltd.) is superior in capturing power of agglomeration (product). .

Moreover, in the pump which sends this to the metal filter provided just before mixing with an in-line mixer, a diaphragm pump, a plunger pump, etc. (Fuji Techno Kogyo Co., Ltd. plunger pump HYSA-16, JGC) It is preferable to increase the number of cylinders to 2 or 3 reciprocating pumps (Mill Flow Control Capacity Pump C23Y-1.5F-14D1D, etc.), which greatly reduces the load on the filter. It is disclosed that it can be done.

Furthermore, Japanese Patent Application Laid-Open No. 2000-273199 describes an invention in which a cellulose ester solution remaining in a filtration process is reused as a raw material in order to obtain good environmental suitability without optical defects. As a more preferred embodiment, the operation until the cellulose ester solution is added to the step of preparing the cellulose ester solution is carried out in a sealed environment, and the solid content concentration of the cellulose ester solution remaining and recovered in the filtration step is the cellulose ester solution. Lower than the solid concentration of the cellulose ester solution prepared in the step of preparing
It is disclosed that 0% is contained, more preferably 0.2 to 10%.

Japanese Patent Application Laid-Open No. 2000-256477 describes an invention for forming a film by filtering cellulose ester with a filter paper having a reserved particle diameter of 8 μm or less in order to obtain a film for a high-definition liquid crystal display element with little abnormal light emission. Yes. Further preferred conditions for the filter paper to be used are: • The drainage time is 20 sec or more; • The thickness is 0.75 mm or more; • The filter paper is made of cotton linter pulp and / or wood pulp. The flow rate of the dope composition to be filtered is 1
It is disclosed that it is 50 L / m ^{2 ·} hr or less. The number of foreign substances of 5 to 50 μm recognized in the polarization crossed Nicol state by these is 200 or less per 250 mm ² area.
There is a description that the number of foreign matters exceeding 50 μm is substantially zero.

Furthermore, JP 2003-014933 A, which is an invention aimed at a retardation film with little additive bleed-out, no delamination phenomenon between layers, good slipperiness and excellent transparency, Describes a case in which impurities such as non-acetylated substances are contained, and therefore, the cellulose ester is dissolved in an organic solvent, and then the dope is filtered with a filter medium. Furthermore, specifically, for example, using a filter press type filtration device, it can be carried out by passing the dope from a coarse filter to a fine filter, the filtration operation may be repeated by circulating the dope. Well, it is disclosed that the filtration flow rate is preferable because it slowly prevents the passage of gel or the like. Further, it is also described that the smaller the filtration pressure, the more preferable it is to prevent passage of gel and the like. Also, a metal fiber type leaf disk type filter can be preferably used, and the filtered dope is sent to a dope tank and allowed to stand and defoamed by a conventional method. For example, the dope is heated at a temperature from 30 ° C. to the boiling point of the solvent. It is shown that it can be degassed by standing for several hours.

Japanese Patent Application Laid-Open No. 2002-128900 describes a method of filtering while heating under pressure at a temperature that is equal to or higher than the boiling point of the solvent at normal pressure and does not boil during filtration. The increase in pressure (hereinafter sometimes referred to as filtration pressure) is preferably reduced, and the preferred temperature range is preferably 45 to 120 ° C (more preferably 45 to 55 ° C), and the filtration pressure is preferably smaller. Specifically, it is disclosed that the pressure is preferably 1.6 MPa or less (more preferably 1.0 MPa or less).

Japanese Patent Laid-Open No. 2002-128900 discloses a method in which fine particle dispersion is performed after degassing the filtration part of the filter or after filling with an organic solvent to be used before filtering the fine particle dispersion and / or the cellulose ester solution with a filter. It is disclosed that the liquid and / or the cellulose ester solution is passed, if necessary, both are mixed, and the fine particle dispersion is transferred while vibrating the fine particle dispersion liquid feeding tube and / or the filter. At this time, it may be mixed with the cellulose ester solution, the vibration applying device may be an ultrasonic vibrator, the fine particle dispersion may contain an ultraviolet absorber, and the cellulose ester solution is plasticized. It has also been shown that a cellulose ester solution may contain a UV absorber.

Furthermore, Japanese Patent Application Laid-Open No. 2002-137237 describes a part of the dope filtered between the continuous filtration device and the casting die so that a large number of foreign matters are not mixed in the film even if the casting die discharge amount changes due to the change of product type. By changing the reverse flow rate, the dope flow rate that passes through the continuous filtration device is always kept constant, and the discharge flow rate from the large casting is changed. A method for producing a cellulose ester film is described.

JP 2002-66220 discloses a filter switching method in which a plurality of filters are installed in parallel, and when switching to a specific filter, the new and old filter pressures are matched to prevent outflow of filter foreign matter. Yes.

The invention relating to filtration of these cellulose acylate dopes described above can also be applied to the present invention.

Moreover, it is preferable that the cellulose acylate solution of the present invention thus obtained has the following physical properties.

In Japanese Patent Laid-Open No. 2003-039458, in order to improve the productivity and improve the surface state, in the co-casting, a cellulose acylate having a static light scattering association molecular weight in solution of the outer layer smaller than that of the inner layer is smaller. The production method of the rate film is described.

Furthermore, in Japanese Patent Laid-Open No. 2003-055476, a cellulose acylate solution of 15 to 30% by mass with an organic solvent having the same composition is used in order to dissolve in a stable state and improve the peelability and surface. ~
Cellulose acylate aggregate molecular weight of diluted solution of 1% by mass is 4 million to 10 million (at 25 ° C)
There is a description of a cellulose acylate film prepared from a cellulose acylate solution.

In addition, JP 2003-094465 A discloses an optical compensation sheet having improved viewing angle characteristics, color spots, and a liquid crystal display device, in which cellulose acylate is reduced to 15 to 30% by mass with a non-chlorine organic solvent. A method for producing a cellulose acylate film is disclosed, which is dissolved and contains a cellulose acylate aggregate in a dope solution, and the weight fraction of the aggregate having an association number of 5 or more is 5 to 100%.

Further, JP-A-2003-094466 contains 15 to 30 mass units of cellulose acylate dissolved in a chlorinated organic solvent solution in order to dissolve in a stable state and improve the peelability and surface state. The weight fraction of cellulose acylate molecules or aggregates having a particle size of 100 nm or more in the solution is 5 to
A process for producing a 100% cellulose acylate film is described.

JP-A-2003-09620 discloses that a dope solution dissolves cellulose acylate in a non-chlorine organic solvent at 15 to 30% by mass in order to dissolve in a stable state and improve the peelability and surface condition. A method for producing a cellulose acylate film containing a cellulose acylate molecule or aggregate having a particle size of 100 nm or more and having a weight fraction of 5 to 100% is described.

Furthermore, in Japanese Patent Laid-Open No. 2003-103539, a cellulose acylate concentration of 15 to 30% by mass, a dope temperature to be cast in order to stably dissolve in a chlorinated organic solvent, easily peel off, and improve the surface shape Cellulose reed in a 25 ° C. solution having a viscosity of 1 to 200 Pa · s, a dynamic storage elastic modulus of −5 ° C. of 10,000 to 1 million Pa, and a dope diluted with the same organic solvent to a concentration of 0.1 to 5% by mass It describes a method for producing a cellulose acylate film having an associated molecular weight of 1 to 10 million.

JP 2003-103540 discloses that a solvent for an inner layer / outer layer is formed by a co-casting method in order to improve the peelability from a metal support and high-speed production suitability and the surface state with a chlorine solvent. 60% by mass of chlorinated solvent
Including the above, there is a description of a method for producing a cellulose acylate film that satisfies at least one of (I)-(IV). : (I) Solution concentration is lower for outer layer than for inner layer; (II) -5 ° C storage elastic modulus is lower for outer layer than for inner layer; (III) Alcohol content is lower for inner layer The outer layer is lower than the outer layer; (IV) The molecular weight of the cellulose acylate associated molecular weight in the solution is larger in the inner layer than in the outer layer.

Japanese Patent Laid-Open No. 2003-103541 discloses a cellulose acylate concentration of 15 in order to obtain a cellulose acylate film that dissolves in an organic solvent in a stable state, is easily peeled off, and has a good surface shape.
Up to 30% by mass, top viscosity at casting top temperature is 1 to 300 Pa · S, top storage dynamic modulus at −5 ° C. is 10,000 to 1 million Pa, casting space temperature is There is a description of a method for producing a cellulose acylate film having a temperature of −50 to 7 ° C. and a casting support temperature of −50 to 15 ° C.

The inventions relating to these cellulose acylates described above can also be applied to the present invention.

(Casting, drying, stretching process)
A method for producing a film using the cellulose acylate solution of the present invention will be described. For the method and equipment for producing the cellulose acylate film of the present invention, a solution casting film forming method and a solution casting film forming apparatus conventionally used for producing a cellulose triacetate film are used. The dope (cellulose acylate solution) prepared from the dissolving machine (kettle) is temporarily stored in a storage kettle, and the foam contained in the dope is defoamed for final preparation. The dope is sent from the dope discharge port to the pressure die through a pressure metering gear pump that can deliver a metered liquid with high accuracy by the number of rotations, for example.
The dope is cast uniformly from the die (slit) of the pressure die onto the metal support of the casting part running endlessly, and the dope film (web) is dry-dried at the peeling point where the metal support almost goes around. Is also peeled from the metal support. Both ends of the obtained web are sandwiched between clips, transported by a tenter while keeping the width, dried, then transported by a roll group of a drying device, dried, and wound up to a predetermined length by a winder. The combination of the tenter and the roll group dryer varies depending on the purpose. In the solution casting film forming method used for silver halide photographic light-sensitive materials and functional protective films for electronic displays, in addition to the solution casting film forming apparatus, an undercoat layer, an antistatic layer, an antihalation layer, a protective layer, etc. In many cases, a coating device is added to the surface processing of the film. Although each manufacturing process is described briefly below, it is not limited to these.

(Casting)
First, when the prepared cellulose acylate solution (dope) is produced by a solvent casting method, a dope is cast on a drum or a band, and the solvent is evaporated to form a film. It is preferable to adjust the concentration of the dope before casting so that the solid content is 5 to 40% by mass.

The temperature of the cellulose acylate solution used for casting is preferably −10 to 55 ° C., more preferably 25 to 50 ° C. In that case, all of the processes may be the same, or may be different at various points in the process. If they are different, the temperature may be a desired temperature just before casting.

Regarding casting, in Japanese Patent Application Laid-Open No. 2001-018241, in order to reduce thickness unevenness and coating unevenness, when casting a polymer solution dissolved in an organic solvent from a die onto a support, a ribbon (supported from a die discharge port) is used. An invention is described in which the length of the liquid film between the body landing and the body landing is 3 to 40 mm.

Furthermore, for the purpose of preventing unevenness in thickness in the casting direction and streak-like failure and improving the flatness, JP-A-2001-071338 discloses that a ribbon-like dope is cast from a casting die to a support. In the method of forming a film, an invention is described in which the tensile stress applied to the ribbon-like dope at the tip of the lip of the casting die is defined.

In addition, to prevent air entrainment by electrostatic application, to prevent fire and explosion in the solvent gas atmosphere,
In JP-A-2001-113544, in a film manufacturing method in which a casting ribbon is cast on a casting support from a casting die to form a film, at least the oxygen concentration in the casting process is less than 10 vol%, An invention is described in which electrostatic application is applied between a drawn ribbon and a cast support.

Further, JP-A-2002-103358 discloses a relationship in which the periodic thickness unevenness pitch and thickness unevenness in the longitudinal direction of the web are within a predetermined range so that coating unevenness does not occur even when various functional layers are applied to the film surface. The invention is described.

Japanese Patent Laid-Open No. 2002-337174 discloses a solution film-forming method in which the flutter of the dope ears discharged from the casting die is controlled to have an amplitude of 5 mm or less so that thickness unevenness does not occur even in a thin film of 65 μm or less. Is described.

Further, JP-A-2003-170447 discloses a cellulose acylate solution in which a cellulose acylate solution is substantially composed of a chlorinated solvent in order to obtain a film having an excellent surface shape. At least one solution of the cellulose acylate solution to be rolled contains at least an alcohol in addition to the chlorinated solvent, and the alcohol is added to the at least one cellulose acylate solution within 24 hours before casting. A method for producing a cellulose acylate film is described.

Further, in order to make it difficult to visually recognize a striped pattern due to uneven thickness in the longitudinal direction of the film, JP-A-20
No. 02-189127 describes an invention that is a solution film-forming film of 60 μm or less and has a maximum thickness variation ΔD of 1 mm in the longitudinal direction of 0.30 μm or less.

Furthermore, Japanese Patent Application Laid-Open No. 2002-028943 of the invention aiming at eliminating unevenness in horizontal steps shows the following as preferable various conditions at the time of casting. The angle formed by the center line of the die slit and the tangent of the endless metal support that moves infinitely is 40 to 90 °, the temperature of the casting film cast from the die is 10 to 50 ° C. The linear velocity of the casting membrane should be 10 to 200 m / min and the variation of the linear velocity should be within ± 15%. ・ The draft ratio of the linear velocity of the casting membrane to the linear velocity of the endless metal support 0.4 to 2.0, the gap between the tip of the die slit and the endless metal support surface that moves infinitely is 200 μm to 5 mm, and the ambient temperature around the die and the casting film is 10 to 40 The position where the casting film is in contact with the endless metal support where the casting film is infinitely transferred is the same position as the position where the casting back roll supporting the metal support from the back side is in contact with the metal support. And the like are disclosed. Further, the casting film discharged from the die slit is cast at a temperature of 10 to 50 (more preferably 20 to 30 ° C.), and the dope viscosity is 1 to 200 (more preferably 10 to 100) Pa.・
It is shown that sec is preferable, and that the linear flow velocity (linear velocity of the casting dope film) is 10 to 200 (more preferably 15 to 150) m / min, and the variation of the linear flow velocity is ± 15% or less. Has been.

In addition, in JP 2002-036266, which is an invention for obtaining a high-quality thin tack with a thickness of 20 to 85 μm, as a preferred embodiment, the angle formed between the surface of the support and the slit wall surface inside the die is as follows: 4
0 to 90 °, and the width of the slit that the dope in the die discharges is 150 to 150
A draft ratio β defined as a ratio value U ₁ / U ₂ between the linear flow velocity U ₁ (m / s) of the dope discharged from the slit and the traveling speed U ₂ (m / s) of the support is set to 0 μm. 0.4-2
. 0, and the wind is blown to the web from a plurality of slits provided to face the support, and the difference W between the maximum and minimum wind speeds along the die width direction of the wind
The ratio value W ₁ / W ₂ between ₁ (m / s) and the average wind speed W ₂ (m / s) along the wind die width direction is set to 0.3 or less. .

Japanese Patent Laid-Open No. 2003-071863 discloses a film forming apparatus having a belt and a cooling drum that conveys the belt to obtain a film that does not cause fogging. An invention is described in which the film is brought into contact with the drum at 0.5 ° C. for 0.5 to 20 seconds. In addition, as a more preferable embodiment, the dew point of the atmosphere when peeling the film from the belt is 7 ° C. or less, and the time until the belt where the film is peeled reaches the casting site of the dope composition is 0 .5-30 seconds ・ The surface temperature of the cooling drum is in particular 7 ° C. or more and 15 ° C. or less. ・ The time from when the film comes into contact with the cooling drum until it is peeled off is particularly 1.5 seconds or more. 12 seconds or less, the time until the belt where the film has been peeled (part) reaches the casting position of the dope composition is particularly 1 second or more and 10 seconds or less. It is described that it is desirable to peel the web from the belt within 30 to 900 seconds.

Japanese Patent Laid-Open No. 2000-246747, which is an invention for obtaining a film having a film thickness accuracy of less than 85 μm, has a linear flow rate of dope of 10 m / min to 200 m / min. The ratio v / u between the traveling speed v of the surface to be received and the linear flow velocity u of the dope flowing out from the die in the dope casting process is 0.4 or more and 2.0 or less. The residence time until contact with the surface of the support is 0.001 second or more and 0.2 second or less, and the temperature of the dope immediately after flowing out of the die is 10 ° C. or more and 48 ° C. or less. The process average atmosphere (US Federal Standard Federal Standard 209D) until the web is peeled off from the support is set to class 10 or more and class 10,000 or less, and after peeling from the support. It is disclosed that the process average atmosphere (Federal Standard 209D) is class 100 or higher and class 10000 or lower.

In order to reduce vertical and horizontal dimensional fluctuations during storage at high temperature and high humidity,
No. -248639 describes that the time from casting to peeling is generally preferably in the range of 0.5 to 5 minutes, although it varies depending on the film thickness and the solvent used. The reason for this is that when the time is less than 0.5 minutes, the drying of the film is not completed and the film cannot be peeled off. When the time exceeds 5 minutes, the process becomes longer and the film-forming efficiency is deteriorated. ing.

In order to obtain a film having a thin film thickness and excellent optical isotropy and flatness, Japanese Patent Application Laid-Open No. 2000-239403 discloses that the surface temperature of the casting support in all regions is 1 to 80 ° C. To do.
As a more preferable embodiment, the film is formed with the surface temperature of the casting support at the peeling point of the web being 50 ° C. or less, the web is formed with respect to the entire width of the web from the dope casting to the peeling point of the web The temperature of the casting support corresponding to the web portion having a width of 5 to 20% from the end portions on both sides of the film is made 5 ° C. lower than the temperature of the casting support at the inner portion, thereby forming a film. And the like are disclosed.

Further, JP-A-11-216732 describes that a TAC dope is cast from a die in order to obtain longitudinal streaks, die streaks, foaming, film formation, adhesion reduction, and peelability improvement in a dope film of die casting. When casting on a part of the support, the support temperature is 0.5 to 55 ° C. lower than the boiling point of the main solvent used for the dope, and the casting draw ratio is 1.0 or more and 3.0 or less. The invention has been described. As a more preferable embodiment, the temperature of the dope in the die lip is 3 to 20 ° C. lower than the boiling point of the main solvent used for the dope, and a roughening zone is provided at both ends of the support surface, and the dope is applied to the roughening zone The casting width is 5 to 30 mm, the average roughness of the roughened surface is 0.5 to 2 μm, and the angle between the support surface and the die slit is 30 °. It is disclosed that the angle is 90 ° or less and the gap between the support surface and the die lip is 200 μm or more and 10 μm. In addition, it is preferable to peel from a support body in the range of 50 to 200 weight% in this case, and it is also shown that the film forming speed | rate is 10-150 m / min.

The invention relating to the dope casting of cellulose acylate described above can also be applied to the present invention.

(Die)
One or two or more pressure dies used for producing the cellulose acylate film of the present invention may be installed above the metal support. Preferably 1 or 2 groups. When two or more units are installed, the amount of dope to be cast may be divided into various ratios for each die, or the dope may be fed to the dies from each of a plurality of precision quantitative gear pumps.

As for dies, in order to prevent streak defects, Japanese Patent Application Laid-Open No. 2002-254453 describes an invention that specifies a die lip surface hardness of Hv 400 or higher or a surface tension of 380 μN / cm and a lip tip shape. Yes.

Further, JP-A-2002-273746 discloses that the die lip surface roughness Ra is 0.1 μm and the lip clearance is 1.0 μm in order to make the rate of change in the width direction of the film 0.04% or less, which is an acceptable level of streak defects.
The invention of solution casting to be mm is described.

In order to prevent the clumping of the ears, Japanese Patent Application Laid-Open No. 2002-103361 describes an invention in which the slit end of the die is processed into a curve instead of a rectangle.

Further, in order to prevent instability of the process and deterioration of the surface quality even when dry air having a large air volume is used, Japanese Patent Application Laid-Open No. 2002-103360 describes that a casting die is cast in a casing. A casting support in which a dope is cast from a casting die in a method of casting a dope on a support and forming a film by blowing dry air onto a base made of the dope cast on the casting support. An invention is described in which a labyrinth and a seal are provided on at least one of the front and rear of the body casting part to suppress the influence of dry air on the casting part.

In order to obtain a film having a thickness of less than 85 μm and good film thickness accuracy, JP-A 2000-246747 describes an invention in which the die slit gap is 50 to 1500 μm.

Furthermore, in order to obtain a good surface quality with a uniform thickness with no unevenness and improved releasability, Japanese Patent Application Laid-Open No. 2002-292660 discloses a plurality of heat bolts 5 in the slit length direction. The invention is described that is arranged at a pitch satisfying the relationship of × 10 <pitch <slit gap × 130. As a more preferable embodiment, a gap adjusting member is a heat bolt, a thickness gauge is provided at a required position in the wake of the die, and the web thickness information detected thereby is fed back to the control device. Is compared with the set thickness information by the control device, and the power or ON rate of the heat bolt heating element is controlled by a correction control amount signal coming from the device. As a more detailed aspect, the heat bolt has a length of 20 to 40 cm and a diameter of 7 to 14 mm, and a plurality of, for example, several tens of heat bolts are arranged at a pitch of 20 to 40 mm. It is also disclosed that a gap adjusting member mainly composed of a bolt for adjusting the slit gap by manually moving back and forth in the axial direction can be provided. It is also shown that the slit gap adjusted by the gap adjusting member is usually 200 to 1000 μm, preferably 300 to 800 μm, more preferably 400 to 600 μm.

JP-A-2002-254450 discloses a die for casting a solution in order to obtain a film having excellent surface smoothness and thickness uniformity without generating streak defects in the casting direction due to die tip defects. It is disclosed that the hardness of the tip is Hv = 400 or more.

Furthermore, in Japanese Patent Laid-Open No. 2002-301731, an angle formed between the tip of the die lip and the support surface is predetermined in order to form a film having excellent surface smoothness and uniform thickness (particularly, periodic thickness unevenness in the longitudinal direction). The invention defined in the scope of is described.

In addition, JP 2003-200478 A discloses a die having a feed block and a single manifold (SM) in order to make the thickness distribution of each layer of the multilayer casting film more uniform using a feed block type casting die. Regarding the flow path from the junction to the SM, the width dimension Wf, the thickness dimension T,
When the width of the discharge port of the die is Wd, 2 <(Wf / T) <10, 10 ≦ (Wd / W
f) A process for producing a multilayer film characterized by ≦ 25 is described.

Furthermore, in Japanese Patent Laid-Open No. 2003-200444, in order to reduce the difference in distribution of the film thickness of the cast film, the die having a manifold is provided with an inclined surface in the manifold in which the flow path narrows in the dope flow direction. A method for producing a multilayer film, characterized in that the inclined surface is a smooth surface having a radius of curvature of 500 mm or more that is convex in the inlet direction of the die liquid in a range of 5 to 20 mm with respect to the center in the widening direction of the die. Has been described.

Japanese Patent Laid-Open No. 2003-181858 discloses a deckle that regulates the flow path width at both ends in the width direction in the manifold and in the slit in order to prevent the web from being interrupted and remaining on the support during peeling. Are dope casting dies that are provided so as to extend from the manifold to the dope discharge port, and are used in the solution casting film forming method, and the channel width regulated by the deckle is doped in the slit. There is a description of a dope casting die characterized by being gradually enlarged toward the discharge port.

The invention relating to the cellulose acylate dope for casting described above is applicable to the present invention as long as it is within the scope of the present invention.

(Decompression chamber)
Furthermore, a solution casting method in which the resin solution described in JP-A No. 2000-301555 is discharged in the form of a film from the tip of the casting die and cast on a metal support that moves below the tip of the die. A solution casting method for producing a film with improved thickness accuracy in the range of 0.5 to 9.0 m / min, and a metal support from the tip of a casting die described in JP-A-2000-301558 In the solution casting method in which the surface of the resin solution that has been extruded in the form of a film on the side that contacts the metal support is vacuum-suctioned by a vacuum chamber, the discharge speed is 5 to 50 m / min, and the vacuum chamber has a vacuum degree of A film forming method with improved thickness accuracy at −10 to −2000 Pa can also be used for casting in this report.

Further, in order to prevent wavy unevenness caused by the inflow air at the end, Japanese Patent Application Laid-Open No. 6-155494 describes that in the chamber located behind the casting die of the solution casting, from the both ends in the width direction of the reduced pressure material to the full width. On the other hand, it is described that the opening of the supply portion for pressure reduction is installed at a position in the range of 0 to 0.3 times to perform casting.

In order to improve the thickness by preventing pressure fluctuation in the chamber, Japanese Patent Application Laid-Open No. 2000-290388 describes an invention in which a buffer tank having a capacity of 10 times or more of the capacity of the decompression chamber is provided in the middle of the suction duct. ing.

Furthermore, in order to obtain a film with good plane quality, Japanese Patent Application Laid-Open No. 2002-103359 describes an invention that regulates the pressure balance in the decompression zone, the seal structure, and the seal dimensions.

Furthermore, a solution casting method in which the resin solution described in JP-A No. 2000-301555 is discharged in the form of a film from the tip of the casting die and cast on a metal support that moves below the tip of the die. A solution casting method for producing a film with improved thickness accuracy in the range of 0.5 to 9.0 m / min is disclosed.

JP-A-07-032391 circulates in hot water to maintain the temperature of the die body at a boiling point of -7 ° C to -1 ° C under the normal pressure of the dope, and the lip portion from the normal boiling point of the dope A to the boiling point to the boiling point + 30 ° C. A method in which a dope B maintained at a boiling point to + 30 ° C. under normal pressure of the dope is filled from the dope A and finally cast from the lip. JP-A 03-193316 discloses a polymer solution of an organic solvent from a die to a metal. The inner wall temperature of the vacuum chamber that is cast on the support and sucks the part from the back of the die under reduced pressure is kept above the condensation point of the sucked organic solvent, without condensing the solvent vapor in the vacuum chamber, A casting method has been implemented and can be applied in the present invention. Further, in Japanese Patent Laid-Open No. 05-086212, in casting film formation in which liquid is dropped at both ends to prevent skinning, the solvent is a poor solvent with respect to a solute and 30-9.
A casting method containing 0% by mass is described, and in Japanese Patent Application Laid-Open No. 62-037113, a dope having a solid content of 18 to 35% by mass and a non-methylene chloride solvent of 13 to 25% by mass, A method for producing a cellulose acylate cast on a metal support having a surface temperature of 10 ° C. or lower is also included, and the method can also be applied in the present invention.

Further, in order to maintain good flatness without generating melt fracture even when cast at high concentration at high speed, JP-A-7-32391 describes other parts excluding the dope temperature and the temperature of the casting die. An invention is described in which the temperature of the die body is 1-7 ° C. lower than the boiling point of the dope and the temperature of the lip is 0-30 ° C. higher than the boiling point of the dope.

Furthermore, in Japanese Patent Laid-Open No. 2003-181860, in order to suppress ear curl during peeling and improve transportability, the average thickness of the ear is thinner than the average thickness of the central portion excluding the ear. A film manufacturing method characterized by being cast as described above is described.

These inventions described above can also be applied to the present invention.

  Further, in Japanese Patent Application Laid-Open No. 02-276607, a unit near the side edge is a casting die having a shape in which the discharge amount per binder is smaller than the average discharge amount in the center, and the cellulose mesh in Japanese Patent Application Laid-Open No. 55-014201. A dope using 7-30% by mass of a non-solvent of rate and methylene chloride is cast on the surface of the band, heated to 30-42 ° C. within 3 minutes after casting, and at least 15 seconds at the temperature And a method of filling the exposed portion of the metal support with a gas having a dew point lower than the surface temperature of the metal support in Japanese Patent Application Laid-Open No. 02-111511. Japanese Patent Application Laid-Open No. 02-208650 discloses a manufacturing method in which a soluble solvent of cellulose triacetate flows down at both ends in the binder direction, and the die can also be applied to the present invention.

Furthermore, for the purpose of improving the production efficiency, in order to suppress the residue caused by insufficient drying at the edge peeling point and to prevent the occurrence of skinning, JP-A-2002-337173 discloses a casting die for solution casting. Describes that a solvent supply nozzle is provided at an interval of 0.5 to 3.0 mm outside the solution discharge end.

In addition, JP 2002-036266, which is an invention for obtaining a high-quality thin tack having a thickness of 20 to 85 μm, includes, as a preferred embodiment, a discharge from the lower end portion on the side surface of the die, a side surface side of the die Provide an enclosure near the lower end, or spray solvent vapor, make the solvent vapor concentration near the lower end on the side of the die, and dope-soluble on the support from the lower end on the side of the die. It describes that the solvent is allowed to flow down. Furthermore, preferable conditions for allowing the dopable solvent to flow down are such that the flow rate of the dope-soluble solvent is 0.1 to 1.0 (cm ³ / min), and the temperature of the dope-soluble solvent is below its boiling point. And the like are disclosed.

Furthermore, for the purpose of a manufacturing method and apparatus for reducing variation in in-plane retardation, Japanese Patent Application Laid-Open No. 2003-103547 defines the structure and conditions of a co-casting die, and by co-casting using this die, An invention that reduces the variation in in-plane retardation of the laminated cellulose ester film is described.
As a more preferred embodiment,
The ratio of the average flow rate of the core layer forming raw material resin dope to the average flow rate of the skin layer forming raw material resin dope immediately before the dope merge is 0.3 to 3,
-The average flow velocity ratio immediately before the joining of the raw material resin dopes forming two adjacent layers is 0.5-2,
-The joining angle when the raw material resin dopes forming two adjacent layers join is 30 degrees or less,
-It is disclosed that the distance from the portion where the raw material resin dopes merge in the co-casting die to the tip of the die discharge port is 50 mm or less.

Further, in order to detect the occurrence of film sag of the raw material resin in the vicinity of both ends of the die slit at an early stage, Japanese Patent Application Laid-Open No. 2002-361664 describes the width side edges of the dope film immediately after being discharged from the die slit. An image of a predetermined range including a predetermined width portion is taken, and the area of the film dripping of the raw material resin formed on the die in the vicinity of both ends of the slit is obtained, and whether or not harmful film dripping of the raw material resin has occurred on the die An invention for judging whether or not is described. As a detailed mode, an image determination range in which the edge of the doped film is centered is extracted from the obtained imaging range, and the area of the doped film within the image determination range is formed on the die in the vicinity of both ends of the slit. The area of the film-like sag of the raw material resin is added, and the area of the film-like sag formed on the die is obtained by subtracting one half of the image determination range from this total area. It is disclosed that when it is determined that a film-like sagging has occurred, a notification device notifies the user.

Further, JP-A-2002-361664 describes in time series the film sagging area of the raw resin formed in the vicinity of both ends of the slit in the die, thereby judging the film sagging state, When the meandering of the endless belt is detected, the amount of meandering is detected, and based on the detected amount of meandering, correction is made so that the edge of the dope film comes to the center of the image determination range. In addition, images of a predetermined range including a predetermined width portion on both side edges in the width direction of the doped film immediately after being discharged from the slits of the die are continuously displayed above the both side edges of the endless belt immediately downstream of the die. It describes that an imaging device for imaging is arranged. Furthermore, since the imaging device is used in a high-concentration solvent atmosphere, for example, a bendable light guide in which a bundle of glass optical fibers is covered with stainless steel, a light source and a CCD arranged at one end of the light guide It is disclosed that an image sensor is used, and that the other end of the light guide is arranged in the vicinity of the imaging range. Further, since the meandering amount detection device is also used in a high concentration solvent atmosphere, it discloses that, for example, a laser type sensor housed in a container having a glass wall surface that transmits light on the front surface is used.

Further, JP-A-2002-001745 discloses that a polymer solution of a die lip of a casting die is in contact with the casting die in order to produce a film having excellent surface smoothness and thickness uniformity with high productivity. A manufacturing method is described in which the surface roughness (Ra value) of the liquid portion is 0.1 μm or less.

Also, in order to prevent contact between the belt cast surface and the casting die / decompression chamber, and to prevent damage to the belt, Japanese Patent Application Laid-Open No. 2003-39459 discloses an endless belt made of a drive metal in a resin film manufacturing apparatus. A resin film manufacturing apparatus comprising a die cast in the form of a film on the upper surface (cast surface) of the upper transition portion, a decompression chamber and a peeling means, and a predetermined location behind the decompression chamber and a decompression chamber or casting die. The position of the cast surface of the belt upper transition portion, the amount of variation in the height direction of the cast surface, and the lower surface of the decompression chamber and the cast surface are at least one of the predetermined locations on the back side of the belt upper transition portion. An invention is described in which at least one distance detection device for detecting the distance between them is installed. Further, as a preferred embodiment, a control device is provided that records data on the amount of fluctuation in the height direction of the cast surface of the belt upper transition portion detected by the distance detection device and the distance between the lower surface of the decompression chamber and the cast surface. In the control device, a profile is created based on data recorded in the height direction of the cast surface at the upper transition part of the endless belt and the distance between the lower surface of the decompression chamber and the cast surface, and the endless belt is continuous. Compare the data sequentially detected by the distance detection device and the profile when operating, and calculate the amount of displacement in the height direction of the cast surface of the belt upper transition portion during operation, A belt support back roll raising / lowering means installed below the casting die and on the back side of the upper transition part of the endless belt is further provided for distance detection. When the amount of fluctuation in the height direction of the cast surface of the belt upper transition part exceeding the reference value or the distance between the lower surface of the decompression chamber and the cast surface is detected by the device, the back roll is moved against the belt by the operation of the lifting means The belt supporting back roll is moved 0.5 to 10 times the moving amount in the height direction of the cast surface of the endless belt upper transition portion by the operation of the lifting means. After the amount of movement in the height direction of the cast surface of the belt upper transition portion shows an appropriate value, the back roll returns to the specified position by the operation of the lifting / lowering means. A belt protection mechanism is provided, and the amount of fluctuation in the height direction of the cast surface of the belt upper transition portion detected by the distance detection device or the distance between the lower surface of the decompression chamber and the cast surface is an allowable value. The contact protection member is interposed between the casting die or the decompression chamber and the cast surface of the belt upper transition portion by the operation of the belt protection device, and the contact prevention member of the bell protection device. However, it is disclosed that the rotating roller presses the cast surface of the belt upper transition portion downward. In order to prevent contact between the belt cast surface and the casting die or the decompression chamber, the distance (a) between the belt cast surface and the decompression chamber lower surface is usually 1 to 5 mm, preferably 1 to 3 mm. It is described to set to. Specifically, the detection device is preferably an eddy current type non-contact distance detection sensor, and the eddy current type non-contact first distance detection sensor is 5 to 50 mm (preferably 10 to 30 mm) behind the decompression chamber. ) At a web wide edge at a distance. For an endless belt, it is also described that profiles of various data such as a passing time of a belt seam portion during operation, a seam width, and a seam height are recorded.

The above-described invention relating to the cellulose acylate dope casting die, chamber, casting conditions, and the like can also be applied to the present invention.

(Metal support)
The endlessly running metal support used for producing the cellulose acylate film of the present invention includes a drum whose surface is mirror-finished by chrome plating and a stainless steel belt whose surface is mirror-finished by surface polishing (referred to as a band). May be used). In order to obtain a support having a smooth surface, a material with few impurities is sufficiently polished in a clean environment from which foreign matters are excluded as much as possible to obtain a mirror surface. For example, as described in JP-A No. 2000-84960, by setting the center line average roughness Ra of the support surface to 1 to 3 nm, the film surface roughness and film haze (haze value) do not increase. I have to. The smoothness of the film formed by these solution casting film forming methods becomes better as the number of foreign matters and irregularities on the surface of the support is smaller. The casting and drying methods in the solvent casting method are described in US Pat. No. 2,336,310, US Pat. No. 2,367,603, US Pat. No. 2,429,078, US Pat. No. 2,429,297, US Pat. British Patent 640731, British Patent 736892, JP-B 45-4554, JP-B 49-5614, JP-A 60-176834, JP-A 60-203430, JP-A 62 No. -11,035, each publication. Dope is
Casting on a drum or band having a surface temperature of 30 ° C. or lower is preferably used, and a metal support temperature of −40 to 40 ° C. is particularly preferable.

With respect to the support, for the purpose of excellent dimensional stability, Japanese Patent Application Laid-Open No. 10-006351 discloses that the temperature of the support exceeds 10 ° C. after casting the dope on the support and until peeling. An invention is described that goes through a state of less than ° C. In a more preferred embodiment, the temperature of the support is adjusted in the first half of the period from the casting of the dope to the peeling, and the temperature of the support is set to 10
It is disclosed that it is preferable to pass through the second or more.

Furthermore, Japanese Patent Application Laid-Open No. 2002-234041 describes an invention that limits the size and number of pinholes on the welded part and other band surfaces for the purpose of obtaining a film having good appearance surface quality.

Furthermore, for the purpose of improving smoothness, transparency, and thickness accuracy, JP 2002-23404 A
In No. 2, the flow centerline roughness is less than 0.005μm and the thickness difference between the thickest part and the thinnest part is 0.06m.
An invention using a support that is less than or equal to m is described.

Japanese Patent Laid-Open No. 2002-001745 discloses a method for casting a die lip of a casting die in a method of casting on a metal support in order to prevent streak defects in the casting direction and to make the smoothness and thickness uniform. Describes an invention using a metal support having a surface roughness (Ra value) of 0.1 μm or less at a portion in contact with water.

Further, JP-A-11-216732 describes that a TAC dope is cast from a die in order to obtain longitudinal streaks, die streaks, foaming, film formation, adhesion reduction, and peelability improvement in a dope film of die casting. In which the support temperature is 0.5 to 55 ° C. lower than the boiling point of the main solvent used for the dope, and the casting draw ratio is 1.0 or more and 3.0 or less. Is described. As a more preferable embodiment, the temperature of the dope in the die lip is 3 to 20 ° C. lower than the boiling point of the main solvent used for the dope, and a roughening zone is provided at both ends of the support surface, and the dope is applied to the roughening zone. The casting width is 5 to 30 mm, the average roughness of the roughened surface is 0.5 to 2 μm, and the angle between the support surface and the die slit is 30 °. It is disclosed that the angle is 90 ° or less and the gap between the support surface and the die lip is 200 μm or more and 10 μm. In this case, it is preferable that the solvent content is peeled from the support in the range of 50 to 200% by weight, and the film forming speed is also shown to be 10 to 150 m / min.

Furthermore, JP-A-2002-264152 discloses that the surface of the support is continuously formed in order to suppress the accumulation of precipitates on the support surface while maintaining good peelability and to stably produce a smooth film for a long period of time. An invention in which a spiral groove is provided is described. As a more preferred embodiment, the maximum diameter of the spiral formed on the endless belt or drum support surface is 500 mm or less, and the interval in the support width direction (pitch) between adjacent grooves is 10 mm or less. It is disclosed that the grooves formed at positions shifted in the transport direction have a shared area with each other, the depth of the continuous spiral groove on the support surface is 1 to 5 nm, and the like. Furthermore, the polisher used for the surface processing (polishing) of the support is polished and used by rotating the polishing pad. By using the polishing pad and the polishing agent in a controlled manner, the polisher can be efficiently and moderately cycled. In other words, it is disclosed that a scratch having an appropriate depth can be provided and roughened, and a certain random continuous spiral (coil) -like groove can be provided to the support. In addition, as a preferable spiral shape capable of suppressing the accumulation of precipitates or the like for a long time while maintaining the peelability, the maximum diameter of the spiral loop is 500 mm, and more preferably 200 to 300 mm. In this range, the interval between adjacent spiral grooves (pitch (P)) is 10 mm or less, and the lower limit of the interval between adjacent spiral grooves (pitch) is about 0.2 mm, preferably 0.3 mm. As described above, the depth of the groove is in the range of 1 to 5 nm.

JP-A-2002-307460 was extended with a drive endless belt to suppress vibration of the endless belt during high-speed conveyance, enable stable film formation, and reduce surface quality and Re variation. Among a plurality of support rolls arranged between the pair of drums and supporting the upper transition part and the lower transition part of the endless belt from the back side, the distance between the support rolls adjacent to each other is greater than 0, The invention described in the range of 5 m or less is described. Further, as a preferred embodiment, the distance between the support rolls adjacent to each other is 2 m to a length that is −5% that is an integral multiple of the roll circumference, or a length that is + 5% that is an integral multiple of the roll circumference. The distance between the support rolls adjacent to each other among the support rolls that support the upper transition part of the endless belt from the back side is the support that supports the lower transition part of the endless belt from the back side. It is disclosed that the distance between support rolls adjacent to each other among the rolls is narrower, and the diameter of the support roll is 100 to 250 mm, preferably 100 to 200 mm. .

Further, in order to eliminate the minute movement of the belt and the film thickness fluctuation, Japanese Patent Laid-Open No. 2003-001654 describes an invention in which the amount of fluctuation in the vertical direction of the backup roll of the casting part is 100 μm, more preferably 60 μm or less. . Further, as a more preferable aspect, the surface roughness of the back roll is 0.2 to 1.2 μm (more preferably 0.2 to 1.0 μm) at the maximum height Rmax, The surface roughness is 3 to 100 μm (more preferably 5 to 80 μm) in terms of the average surface roughness Ra, and the amount of dirt deposited on the peripheral surface of the back roll is kept at 0.1 g / m ² or less. .. The reflectance when the light having a wavelength of 400 nm is projected onto the peripheral surface of the back roll that contacts the back surface of the endless belt and supports the endless belt at the dope casting portion, and the reflectance when the dirt is not attached. Keep it at 80% or more as 100%. ・ While sending the nonwoven fabric for cleaning backward in the rotation direction of the back roll, the back roll is brought into line contact with the back roll at a linear pressure of 1 kg / cm or more. Like for cleaning Le circumferential surface is described.

Further, in order to absorb or suppress the movement (lifting) of the endless belt when the temperature of the drying is increased, Japanese Patent Laid-Open No. 2003-025352 discloses that the drive endless belt is placed between a pair of drums. Among the plurality of rolls arranged and supporting the upper and lower transition portions of the endless belt from the back side, an invention is described in which at least the roll supporting the belt upper transition portion from the back side is constituted by a tendency drive roll. Yes.
In a more preferred embodiment, the diameter of the tendency driving roll body is 100 to 25.
0 mm (preferably 100 to 200 mm), the peripheral speed of the tendency drive roll is 10 to 200 m / min, and a small motor is individually provided at one end of the drive shaft of the tendency roll.・ The distance between the endency belts that support at least the belt upper transition part of the endless belt from the back side is the movement due to the thermal elongation of the endless belt when the web is heated to dry (lifting) In order to absorb or suppress odor, a range of 5 m or less (more preferably 2 to 4 m) is described. Japanese Patent Laid-Open No. 2003-025352 discloses that, when the tendency driving rolls are arranged at an interval of 1 m, the cost burden increases due to the increase in the number of rolls. Therefore, the distance between the tendency driving rolls is preferably 2 m or more. It is disclosed.

Furthermore, Japanese Patent Application Laid-Open No. 2002-028943 of the invention aimed at eliminating lateral unevenness describes that the angle for holding the endless metal support to which the casting back roll moves infinitely is 1 to 6 °. Has been. In addition, use of an inadvertently soiled metal support or accumulation of dirt due to web residue and fine debris accumulated while film formation continues, resulting in poor peeling and irregularities. Since it is easy to produce a horizontal stage, the cleaning method is disclosed in order to eliminate such a trouble. More specifically, the operation of wiping with a tool containing pure water and the operation of wiping with a tool containing an organic solvent can be solved, and the operation of wiping with pure water and the operation of wiping with an organic solvent are Any of these may be performed first, but preferably, after the operation of wiping with pure water, it is shown that the stain can be removed by wiping with an organic solvent while wet with water. In addition, as an organic solvent, what has a solubility with respect to a cellulose ester, what does not have a solubility may be used, and they may be mixed and used, the order is wiped with pure water, It is described that it may be wiped with any organic solvent, and after wiping with an organic solvent having solubility, it may be wiped with a solvent having no solubility, or vice versa. Furthermore, pure water is used so that impurities contained in water, such as scale, do not remain in the stainless steel belt, and the tool to be used is preferably a nonwoven fabric (especially cellulose) using long fibers. It is disclosed that it can be used without limitation as long as it is for cleaning used in precision machinery such as related equipment, and absorbs water and organic solvents sufficiently, does not dissolve in organic solvents, and does not desorb fibers. ing. As an example, such a commercial product includes the Bencott series manufactured by Asahi Kasei Corporation, and Bencot M-3 and M-1. Moreover, as an organic solvent which has a solubility with respect to a cellulose ester, a methylene chloride and methyl acetate are preferable. Moreover, as an organic solvent which does not have a solubility with respect to a cellulose ester, a lower aliphatic alcohol, for example, methanol, ethanol, propanol, butanol, etc. are preferable, More preferably, it is methanol or ethanol. In addition, it is disclosed that acetone, cyclohexane and the like can be used, and industrial grades of grade 1 or higher can be used.

In addition, JP 2002-273747, which is an invention for eliminating the meandering of the casting belt, stably running, and obtaining a high quality film, has a non-casting portion at both ends of the endless belt, The width of each non-casting part is 10 to 300 (mm), and the relationship between the wide non-casting part W _W (mm) and the narrow non-casting part W _N (mm) is W _W / W _N ≦ 2, and the temperature difference between the belt temperature of Hiryo distal portion _W W (T W) and the belt temperature of the non-casting unit W _N (T _N) is 10 ° C. or less, the endless belt width The relationship in which the tension difference ΔT (N) applied to both ends of the hand is expressed by ΔT ≦ 0.6 × L [ΔT is the tension difference (N) at both ends of the endless belt, and L is the circumference of the endless belt (mm)]. It is described.

In JP-A-2002-273747, in order to increase productivity, that is, to secure a drying time on a casting belt even at high speed, a belt 1 having a length of several tens of meters is used. Since a plurality of drying zones having different temperatures are provided between the circumferences, the belt that is running may swing in the width direction (displacement), but the belt may meander. In the case where the width fluctuation amplitude of the meandering of the belt exceeds 10 mm, it is shown that the possibility of causing a serious problem in production such as film breakage by the peeling roll is extremely high. Therefore, in general, when the position of the casting belt changes in the width direction of either the drum or the drum, the width position of the belt is detected in order to correct the position to the reference casting belt position. It is disclosed that a correction device comprising a combination of a sensor and a driving device that changes the shaft angle of the drum with respect to the running direction of the casting belt is provided. Further, as a method of changing the shaft angle of the drum, there are a method of driving both ends of the drum shaft and a method of driving one side of the drum shaft, but the latter is advantageous from the viewpoint of the device cost, It is described that a tension applying device for the casting belt is provided on either one of the drums together with the width position correcting device for the casting belt. This is a drum moving device that can change the distance between a pair of opposing drums. With this device, it is possible to always apply an appropriate tension to the casting belt, thereby stably running the casting belt. Is disclosed to be possible. Japanese Patent Laid-Open No. 2000-246747, which is an invention for obtaining a film with a film thickness accuracy of less than 85 μm, receives a dope on the support while the support is running with vertical vibration. It describes that the maximum value of the amplitude of the surface is 100 μm or less.

In addition, in order to obtain a film having a thin film thickness and excellent optical isotropy and flatness, JP-A-2000-239
No. 403 describes that a film is formed using a casting support having a surface roughness Ra of Ra ≦ 1 μm.

Furthermore, since JP 2002-086472 mentions the production of a continuous film for a long time, the cellulose acylate dissolved in a non-chlorinated solvent is cast on a drum having a radius of 0.75 m to 2.5 m to form a film. A method for producing an acylate film is described.

In addition, JP 2002-103357 A discloses that the width of the casting support is wide in order to prevent the dope from being foamed, the peelability of the dry film from the casting support is good, and the flatness is improved. A solution casting method that makes the distribution uniform is disclosed.

Furthermore, in Japanese Patent Laid-Open No. 2002-127169, even if an endless belt having a width of 1.6 m or more is used, in order to obtain a film having no problems such as drying unevenness, belt temperature unevenness, and belt flatness, In contrast, a solution casting method is described in which the casting width of the film from the die is ± 0.5% or less and the belt width is 70% or more and the belt width− (meandering amount × 4) or less.

Further, JP 2002-273747 A discloses an endless belt and a pair of drums in order to eliminate the meandering of the casting belt, stably run, and obtain a high quality film. Endless belt length change (ΔL1) between belt temperature of 20 ° C and casting film formation (ΔL1) of B1), and endlessness between belt temperature of 20 ° C and lower casting section (B2) An invention is described in which the relationship with the belt length change amount (ΔL2) is such that | ΔL ₁ −ΔL ₂ | ≦ 0.00025 × L.
As a more preferred embodiment, when a pair of drums for circulating and running the endless belt for casting is the drum 1 and the drum 2, respectively, the change in thermal expansion ΔL ₃ (mm) in the contact section between the drum 1 and the endless belt Alternatively, the thermal expansion change amount ΔL ₄ (mm) in the contact section between the drum 2 and the endless belt is ΔL _3, ΔL ₄ = ≦ 6.0 × 10 ⁻⁴ × L ₁₄ (mm
The thermal expansion change amount ΔL ₃ or ΔL ₄ per contact time t (seconds) ΔL _3t , ΔL _4t is ΔL _3t = ΔL ₃ /t≦0.2 (mm / sec), ΔL _4t = ΔL ₄ / t
It is disclosed that the relationship is represented by ≦ 0.2 (mm / sec).

The invention relating to the support for casting these cellulose acylate dopes described above,
The present invention can also be applied.

(Co-casting)
In the present invention, the obtained cellulose acylate solution may be cast as a single-layer liquid on a smooth band or drum as a metal support, or a plurality of cellulose acylate liquids of two or more layers may be cast. May be.
In the case of producing a multilayer casting film or a multilayer film by using the liquid casting method, a feed block type casting die is often used, and this feed block type casting die is disposed on the upstream side of the casting die. This is a casting apparatus in which a merging means for merging seeds or more dopes is joined. A typical structure of the feed block type casting die is provided with a channel for passing a dope serving as a core layer in the center, and a dope forming a front surface layer and a back surface layer on both sides thereof, and the latter The two solution streams are joined to both sides of the former solution stream. As an example of a method for producing a multilayer film using the above feed block type casting die, a relatively high viscosity dope is used for the resin layer as the core layer, and a relatively low viscosity dope is used for the front and back surface layers. Japanese Patent Publication No. 62-43846 discloses a method of performing dry peeling after forming a multilayer cast film. In addition, when casting a plurality of cellulose acylate solutions, the film is formed while casting and laminating a solution containing cellulose acylate from a plurality of casting openings provided at intervals in the traveling direction of the metal support. For example, methods described in JP-A-61-158414, JP-A-1-122419, and JP-A-11-198285 can be applied. Further, it may be formed into a film by casting a cellulose acylate solution from two casting ports. For example, JP-B-60-27562, JP-A-61-94724, JP-A-61-947245, It can be carried out by the methods described in JP-A Nos. 61-104813, 61-158413, and 6-134933. Further, a cellulose acylate film in which a flow of a high-viscosity cellulose acylate solution described in JP-A-56-162617 is wrapped with a low-viscosity cellulose acylate solution and the high- and low-viscosity cellulose acylate solutions are simultaneously extruded. A casting method may be used. Furthermore, it is also a preferred embodiment that the outer solution described in JP-A-61-94724 and JP-A-61-94725 contains a larger amount of an alcohol component which is a poor solvent than the inner solution.

  Alternatively, the film is formed by peeling the film formed on the metal support using the first casting port and performing the second casting on the side in contact with the metal support surface using the two casting ports. For example, it is a method described in Japanese Patent Publication No. 44-20235. The cellulose acylate solutions to be cast may be the same solution or different cellulose acylate solutions, and are not particularly limited. In order to give a function to a plurality of cellulose acylate layers, a cellulose acylate solution corresponding to the function may be extruded from each casting port. Furthermore, the cellulose acylate solution of the present invention can be cast simultaneously with other functional layers (for example, an adhesive layer, a dye layer, an antistatic layer, an antihalation layer, a UV absorbing layer, a polarizing layer).

In the conventional single-layer liquid, it is necessary to extrude a high-concentration and high-viscosity cellulose acylate solution in order to obtain the required film thickness. In many cases, this causes a problem such as a fault or flatness. As a solution to this, by casting a plurality of cellulose acylate solutions from the casting port, it is possible to extrude a highly viscous solution onto a metal support at the same time. In addition to being able to be produced, the use of a concentrated cellulose acylate solution could reduce the drying load and increase the production speed of the film.

In the case of co-casting, the inner and outer thicknesses are not particularly limited, but preferably the outer thickness is 1% of the total film thickness.
The thickness is preferably ˜50%, more preferably 2 to 30%. Here, in the case of co-casting with three or more layers, the total thickness of the layer in contact with the metal support and the layer in contact with the air side is defined as the outer thickness.

In the case of co-casting, a cellulose acylate film having a laminated structure can be produced by co-casting cellulose acylate solutions having different additive concentrations such as the plasticizer, ultraviolet absorber, and matting agent. For example, a cellulose acylate film having a structure of skin layer / core layer / skin layer can be produced. For example, the matting agent can be contained in the skin layer in a large amount or only in the skin layer. The plasticizer and the ultraviolet absorber can be contained in the core layer more than the skin layer, and may be contained only in the core layer. In addition, the type of plasticizer and ultraviolet absorber can be changed between the core layer and the skin layer. For example, the skin layer contains a low-volatile plasticizer and / or an ultraviolet absorber, and the core layer has excellent plasticity. It is also possible to add a plasticizer or an ultraviolet absorber excellent in ultraviolet absorption. Moreover, it is also a preferable aspect that a release agent is included only in the skin layer on the metal support side. Moreover, in order to cool a metal support body by a cooling drum method and to gelatinize a solution, it is also preferable to add more alcohol which is a poor solvent to a skin layer than a core layer. The Tg of the skin layer and the core layer may be different, and the Tg of the core layer is preferably lower than the Tg of the skin layer. Further, the viscosity of the solution containing cellulose acylate during casting may be different between the skin layer and the core layer, and the viscosity of the skin layer is preferably smaller than the viscosity of the core layer. It may be smaller than the viscosity.

The casting method according to the present invention will be described in more detail. A method for uniformly extruding the prepared dope from a pressure die onto a metal support, and a film thickness of the dope once cast on the metal support with a blade. There are a method using a doctor blade for adjustment, a method using a reverse roll coater for adjustment using a reverse rotating roll, and the like, but a method using a pressure die is preferred. The pressure die includes a coat hanger type and a T die type, and any of them can be preferably used.
In addition to the methods listed here, various methods for casting a cellulose triacetate solution known in the art (for example, JP-A-61-94724, JP-A-61-148013,
(Methods described in JP-A-4-85011, JP-A-4-286611, JP-A-5-185443, JP-A-5-185445, JP-A-6-278149, JP-A-8-207210, etc.) Can be preferably used, and the same effects as described in the respective publications can be obtained by setting each condition in consideration of the difference in the boiling point of the solvent used.

In addition, as an invention related to co-casting, in order to increase the casting speed, JP-A-53-134869
In the No., the cellulose acetate solution is cast from the first casting port to a thickness of 10-90% of the total thickness, and the first casting port is separated by 30-60% from the first casting port to the peeling. An invention is described in which the remainder is cast from two casting ports.

JP-A-61-018943 discloses that TAC is a dope composed of methichro and methanol and another poor solvent (A), and a dope having a higher ratio of the poor solvent than A in order to speed up the casting stably.
In B), the dope A is placed on the support surface so as to be 5 μm or more in an undried state.
An invention for co-casting and forming a film is described. Furthermore, it is also disclosed that it is desirable to join A and B in the middle of the slit with a composite slit die. This invention has the same effect even if the methylochrome is non-chlorine, and can be applied to the present invention.

Furthermore, for the purpose of obtaining a magnetic recording layer with good flatness, Japanese Patent Application Laid-Open No. 4-124645 discloses a stripe co-casting die in which the sectional name of the slit from one manifold to the joining portion is a comb-like shape. An invention using is described.

In addition, in order to reduce the solvent contained in the film immediately after production with excellent transparency, dimensional stability, heat and heat resistance, JP-A-8-207210 describes a core portion of cellulose acetate having a substitution degree <2.7, 0.5-15μ consisting of cellulose acetate with substitution degree> 2.8 on at least one side of the core part
An invention for providing a surface layer with a thickness of m is described.

Furthermore, in JP-A-10-058514, in order to prevent generation of a film residue with good smoothness, a surface layer dope is coated on a base layer dope (excluding both ends) and simultaneously extruded from a die. The invention to perform is described.

Japanese Patent Application Laid-Open No. 5-040321 describes an invention relating to a light-sensitive material in which magnetic dope and non-magnetic dope are co-cast.

In order to obtain a multilayer resin film with higher thickness accuracy, JP 2000-317960 A discloses a low-viscosity liquid and a high-viscosity liquid having a viscosity of 2 to 10 times from each flow path. An invention is described in which a multi-flow casting film is formed by discharging from a casting die lip for 5-25 seconds from the time of merging after joining and forming a liquid parallel flow contacting at the interface.

JP 2002-221620 discloses that, in a polarizing plate film, the slope of streaky unevenness having a pitch of 3 to 15 mm is set to less than 0.04 degrees by co-casting with a low concentration of the outer layer. Is described.

Furthermore, in Japanese Patent Application Laid-Open No. 2003-080541, in order to suppress generation of burrs, when casting a plurality of dopes from a die, a dope shear viscosity A and an intermediate layer are formed to form a front surface or a back surface layer. An invention is described in which the ratio A / B with the shear viscosity B of the dope is A / B <0.9.

Furthermore, JP 2003-014933 of the invention aimed at a retardation film with little additive bleed-out, no delamination phenomenon between layers and good slipperiness and excellent transparency includes resin and additive And an organic solvent, and a dope B containing a resin, an additive, and an organic solvent containing no additive or less additive than Dope A. Dope A is a core layer, Dope B Co-cast on the support so that the surface layer becomes a surface layer, evaporate the organic solvent until it can be peeled, and use the crushed product obtained by crushing the web peeled from the support as the resin material of the dope A again Is disclosed. In a more preferred embodiment, the resin is a cellulose ester satisfying the formula (I) 2.4 ≦ X + Y ≦ 3.00 (where X is the degree of substitution of acetyl group and Y is the degree of substitution of propionyl group and / or butyryl group) It is disclosed that the compounding amount of the additive in the dope A is 1 to 30% by mass (more preferably 6 to 20% by mass) with respect to the cellulose ester. Furthermore, it is described that the amount of the additive in the dope B is preferably 0 to 5% by mass with respect to the cellulose ester, and most preferably not containing the additive. Here, the dope A constitutes the core layer A and the dope B constitutes the surface layer B, but the film constitution may be the same dope formulation constituting both surfaces as B / A / B, for example, B / A It is disclosed that the dope formulations on both surfaces may be different as in / C. In this case, it is also shown that the amount of additive in the dope C is preferably smaller than the amount of additive in the dope A. Further, the cellulose ester concentration in the dope A is 15 to 35% by mass, and the alcohol having 1 to 4 carbon atoms is 4 to 20% by mass, preferably 6 to 12% by mass, based on the organic solvent in the dope A. The cellulose ester concentration in the solvent is 10 to 25% by mass, and the alcohol having 1 to 4 carbon atoms is preferably 6 to 30% by mass, and preferably 12 to 24% by mass with respect to the organic solvent in the dope B. Is also described.

Furthermore, in Japanese Patent Application Laid-Open No. 2003-014933, it is preferable to add fine particles to the surface layer in order to impart the slipperiness of the film, and it is not necessary to add fine particles to the core layer, but may be added. Is disclosed. However, since the transparency of the film deteriorates when the amount of fine particles added to the core layer is large, the amount added is preferably 1/10 or less of the amount added to the surface layer, more preferably substantially the core layer. It is shown that it does not contain fine particles. (Substantially not contained, the amount of fine particles added is 0 to 0.01% by mass per solid content) It is also disclosed that the effect of slipperiness can be obtained if blended on at least one side of both surface layers. 1 in particular of fine particles
The average particle size is preferably 20 nm or less from the viewpoint of keeping the haze low,
More preferably, it is 16-5 nm, It is disclosed that it is 12-5 nm especially preferably. The apparent specific gravity of the fine particles is preferably 70 g / liter or more, more preferably 90 to 200 g / liter, and particularly preferably 100 to 200 g / liter.
It is described that the higher the apparent specific gravity is, the higher the concentration can be made, and the better the haze and aggregates are. Here, the average diameter of the primary particles is 2
Silicon dioxide fine particles having an apparent specific gravity of 0 g or less and an apparent specific gravity of 70 g / liter or more can be obtained, for example, by burning vaporized silicon tetrachloride and hydrogen in air at 1000 to 1200 ° C. . For example, it is disclosed that it is marketed under the trade names of Aerosil 200V and Aerosil R972V (manufactured by Nippon Aerosil Co., Ltd.).

Furthermore, in order to improve the coating properties of the coating composition of the antistatic layer, heart coat layer, antiglare layer and antireflection layer, it is a cellulose ester laminated film with a film thickness of 20 to 80 μm, which is present within 10 μm from at least one film surface. Average substitution degree a of cellulose ester constituting the surface layer,
Proposing a cellulose ester laminated film in which the average substitution degree B of the cellulose ester exceeding 10 μm from the surface is 2.35 ≦ substitution degree a ≦ 2.85 and 2.75 ≦ substitution degree B ≦ 2.95, and the substitution degree a <substitution degree B Yes.

The invention relating to co-casting of these cellulose acylates described above can also be applied to the present invention.

(Drying on a metal support)
The drying of the dope on the metal support relating to the production of the cellulose acylate film of the present invention is generally performed by supplying hot air from the surface side of the metal support (drum or belt), that is, from the surface of the web on the metal support. Contact method, method of applying hot air from the back of the drum or belt, contact the temperature-controlled liquid from the back of the belt or drum opposite the dope casting surface, and heat the drum or belt by heat transfer to increase the surface temperature. Although there is a liquid heat transfer method to be controlled, the back surface liquid heat transfer method is preferable. The surface temperature of the metal support before casting may be any number as long as it is not higher than the boiling point of the solvent used for the dope. However, in order to promote drying and to lose fluidity on the metal support, the temperature should be set to 1 to 10 ° C. lower than the boiling point of the lowest boiling solvent used. Is preferred. This is not the case when the cast dope is cooled and peeled off without drying.

As an invention relating to drying on a support, Japanese Patent Application Laid-Open No. 61-100421 discloses that the TAC casting support temperature is higher than the gel temperature of the dope temperature in order to shorten the peeling time and drying time. However, an invention is described in which the temperature is 30 to the foaming temperature or lower and is peeled off at a peeling portion temperature of 20 ° C.
This invention has the same effect even if the methylochrome is made non-chlorine, and can be applied to the present invention.

Furthermore, for the purpose of improving stripping, Japanese Patent Application Laid-Open No. Sho 62-064514 states that the solid content is 18 to 35 wt%, non-methichro 13 to 25 wt% dope, the support temperature surface is 10 ° C. or less, and the surface is 2 seconds or more. The invention is described in which the film is selectively dried by applying a wind of the above and then peeled off. The present invention has the same effect even if the methylochrome is made non-chlorine, and can be applied to the present invention.

In order to make the film thickness in the width direction uniform, Japanese Patent Application Laid-Open No. 64-055214 gives drying air to the back surface, the drying start is within 15 seconds from the start of casting, and the direction of the drying air is the support. An invention is described in which the angle formed by the support surface is 40 to 80 degrees, the static pressure of the drying air is 5 mmHg or more, and the distance between the drying air outlet and the support surface is 5 to 50 mm, which is obliquely forward in the traveling direction.

Furthermore, in order to prevent the dope sticking and solve the problem of optical birefringence, Japanese Patent Laid-Open No. 4-201310 discloses that the support is heated by a radiant heat source from the back side of the support, and the residual solvent of the film-like material is removed. In the range up to 35% by weight or less, there is described an invention in which drying is performed only by a radiant heat source without using drying air.

Japanese Patent Laid-Open No. 11-058425 discloses a wind speed of about 0.1 to 2.0 m / s until the temperature of the film cast on the support reaches the gelation temperature in order to suppress drying unevenness and improve productivity. An invention is described in which the first stage drying is performed by applying the drying air, and the second drying is performed in order to dry the film faster after reaching the gelation completion temperature of the film.

Furthermore, Japanese Patent Application Laid-Open No. 2000-319412 discloses a casting support for transferring a dope from a casting die in order to obtain a cellulose ester film having a film thickness of 85 μm or less having excellent flatness for a liquid crystal image display device. An invention is described in which a web is formed by casting on the body, and the absolute value of the static pressure of the drying air applied to the surface of the web is 20 to 100 mmAq, and the lateral static pressure deviation within the longitudinal direction is ± 20% or less. Has been.

Japanese Patent Laid-Open No. 2001-315147 discloses an average heating temperature T (1) between the heating temperature T1 on the upper side of the endless metal support and the heating temperature T2 on the back side for the purpose of producing a thin TAC film at high speed. , 2) av and the difference between the average heating temperature T (3,4) av between the back side heating temperature T3 of the lower metal support and the front side heating temperature T4, 55> T (1,2) av−T ( 3,4) The invention of peeling after drying is described as av> 5. As a more preferable embodiment, when the drying area of the support is four, such as the upper side, the lower side, and the front and back sides of the respective metal supports (upper side B-1, the back side is B-2, the lower side The back side is referred to as B-3, and the lower front side is referred to as B-4). The heating method of B-1, B-3, and B-4 is performed by warm air or radiant heat (particularly warm air), B-2 Describes a heating method in which warm water is brought into contact with a support, and a heat supply method in which warm air is applied is used. As a more detailed temperature condition, the hot air temperature can be set without limitation as long as the temperature is such that the main organic solvent used for the dope is not rapidly foamed and foamed in the web during drying. However, T ₁ of B- ₁ and T _{2 of} B-2 are 20 to 90 ° C. (preferably 30 to 80 ° C.), and T ₃ of B- ₃ and T _{4 of} B- ₄ are 15 to 60 It is described that the temperature is good and the drying on the metal support is preferably high in the first half and low in the second half. The wind speed of the hot air for supplying heat is 10-20 m / sec for B-1, 10-30 m / sec for B-2, 20-30 m / sec for B-3, and 10-20 m / sec for B-4. It is shown that about a second is preferable, and the temperature and wind speed of each of B-1 to 4 may be changed to divide the warm air and add different temperatures and wind speeds.

Further, in order to eliminate lateral unevenness, Japanese Patent Application Laid-Open No. 2002-028943 describes that a dope is cast from a die on an endless metal support and the wind from the upstream and / or downstream side has a horizontal component of the maximum wind speed. An invention is described in which the deviation of the wind speed corresponding to the entire width of the casting film is within ± 20%, with the speed being 4 m / s or less.
Furthermore, it is described that it is most desirable to reduce the wind speed to zero and that it is necessary to apply heated air from the web surface side for drying after casting. Furthermore, even if the wind is not being applied to the casting film being cast, the irregular wind that circulates around the casting film may sway the casting film and promote the generation of horizontal stages. As a means to block the wind: ・ Balance the flow of the wind in the casting process from casting to casting ・ Provide a wind escape ・
It is disclosed that the maximum wind speed can be suppressed by providing a shielding plate in the vicinity of the casting film.

JP-A-2002-036263 discloses that the temperature of the gas blown onto the web in contact with the support with a web drying time of 0.3 to 20 minutes in order to obtain a 20 to 80 μm thin tack that is curled. In addition, it is described that the contact surface temperature of the support is 5 ° C. or more and 100 ° C. or less. Furthermore, when the section from dope casting to peeling is divided into six parts such as the upper and lower sides of the support, the front and back of each metal support, and the pair of drums between the upper and lower parts of the support ( In order from the casting side, the front side “first drying processing unit” on the upper side, the “second drying processing unit” on the back side, and the heating unit via the drum (anti-peeling side) are “third drying processing unit”. The lower front side is the “fourth drying processing section”, the lower back side is the “fifth drying processing section”, and the drum (peeling side) cooling section “cooling processing section”). The average drying temperature of the first drying processing unit is equal to or higher than the average drying temperature of the fourth drying processing unit, and / or the average heat transfer coefficient of the first drying processing unit is the fourth drying processing unit. The average heat transfer coefficient is higher than the average heat transfer coefficient. And / or the heat transfer coefficient of the first drying processing section is changed from the upstream side to the downstream side along the support traveling direction. The drying temperature of the fourth drying processing unit decreases from the upstream side to the downstream side along the support traveling direction, and / or The heat transfer coefficient of the drying processing unit is configured to decrease from the upstream side to the downstream side along the support traveling direction, and the average drying temperature of the second drying processing unit is The average drying temperature of the third drying processing unit and the average drying temperature of the third drying processing unit equal to or higher than the average drying temperature of the fifth drying processing unit, and the average of the second drying processing unit The heat transfer coefficient is equal to or higher than the average heat transfer coefficient of the fifth drying processing section; The average drying temperature of the first drying processing unit is set to be equal to or higher than the average drying temperature of the first drying processing unit, and the average heat transfer coefficient of the second drying processing unit is set to the average heat transfer coefficient of the first drying processing unit. The average drying temperature of the fifth drying processing unit is equal to or higher than the average drying temperature of the fourth drying processing unit, and / or the average heat transfer coefficient of the fifth drying processing unit is More than the average heat transfer coefficient of the fourth drying processing unit, the cooling temperature of the cooling processing unit may be lower than any drying temperature of the first to fifth drying processing unit, In the drying processing unit, the temperature of the support is increased by using warm water, so that the support is configured to heat the web. The cooling temperature of the cooling processing unit is 3 ° C. or higher and 20 ° C. or lower. And the like are disclosed.

In addition, in order to obtain a high quality thin tack with a thickness of 20 to 50 μm, Japanese Patent Laid-Open No. 2002-036266 describes a solvent vapor concentration near the lower end on the side of the die [= (volume of solvent vapor / volume of space including solvent). ) × 100] α
(%) And the ratio α / V (s / m) of the air wind speed V (m / s) near the lower end on the side surface of the die, 10
The manufacturing method described above is described. As a further preferred aspect, it is disclosed that the wind speed of the wind is 4 (m / s) or less when the wind is directed along the surface of the web toward the die from the downstream in the traveling direction. Yes.

Furthermore, in order to obtain excellent viewing angle expansion characteristics, Japanese Patent Application Laid-Open No. 2002-082225 manufactures an optical film having a thickness direction retardation value (Rt) of 50 to 300 nm under conditions of 23 ° C. and 55% RH. In doing so, an invention is described in which a dope is kept on a belt or drum kept at 30 ° C. or lower for 1 minute or more immediately after casting. Further, after passing through a drying zone in which the residual solvent amount of the optical film is 10% to 120% for 2 minutes to 90 minutes and then passing through the drying zone, the residual solvent amount is wound into a roll with a state of 7% or less. Taking is also disclosed.

Japanese Patent Laid-Open No. 2002-225054 discloses that a dope is cast on a metal support for the purpose of being thin and having a dry film thickness of 10 to 60 μm and being light and moisture-permeable and having small durability. An invention is described in which a web on a substrate is subsequently heated in a high temperature drying zone and then heated in a low temperature drying zone before peeling.

Japanese Patent Laid-Open No. 2003-071863, which is an invention for obtaining a film free from fogging, describes that when the film is peeled off from the band, the surface temperature of the cooling drum is 6 ° C., and the time for which the film is in contact with the drum is 0.5-20. The invention of the second is described. In JP 2003-071863 A, in order to adjust the amount of residual solvent at the time of peeling, the belt surface temperature after casting is controlled so that the organic solvent can be efficiently evaporated from the web. It is disclosed that the temperature at the upper peeling position is preferably set in the above range, and in order to control the belt temperature, it is disclosed that a method with good heat transfer efficiency such as a back surface heat transfer method using liquid is preferable. Furthermore, in the heat transfer method using radiant heat, hot air, etc., in the belt machine, the belt temperature can be adjusted with a gentle wind to control the temperature of the belt where the belt to be transferred has come to the lower side. It is described that it can be partially changed by dividing the heating means, and the casting position, the drying section, the peeling position, etc. of the casting belt can be set to different temperatures.

In order to improve the film flatness, Japanese Patent Application Laid-Open No. 2003-103544 describes that in the production of a cellulose ester film of 20 to 200 μm, the film has a surface residual solvent amount of 300 wt% or less in drying on the band. An invention is described that begins to blow dry air onto the surface. As further details of a preferred embodiment, a drying air blowing header is provided in a drying zone provided at the upper transition portion of the endless belt, and the drying air has a temperature of 20 to 60 ° C. and a static pressure in the header of 500 to 1500 Pa with respect to the web surface. Two drying zones are provided on the endless belt, and after passing through the first drying zone where the drying air is blown to the left, the second surface is further applied to the web surface in a state where the surface residual solvent amount is less than 100%. Spraying drying air at a temperature of 40 to 80 ° C. and static pressure in the header of 100 to 1200 Pa in the drying zone. ・ A nozzle having a slit-like opening is attached to the drying air blowing header of the drying zone provided on the endless belt. Spraying dry air on the surface of the web from a nozzle having a slit-like opening; Dry air blowing nozzles in the second drying zone in which the pitch of the drying air blowing nozzles in the first drying zone having a residual solvent amount of 300% or less and 100% or more is 50 to 300 mm and the surface residual solvent amount of the web is less than 100%. The gap between the nozzles having slit-like openings is 2 to 10 mm, and the gap between the tip of the nozzle having slit-like openings and the upper surface of the endless belt is 5 To be 100 mm, to the web on the endless belt, to set the blowing air blowing angle from the nozzle having the slit-shaped opening to 90 to 45 degrees, Divide it into at least three drying zones with different drying conditions and dry the belt from the back side of the belt. It is disclosed to divide into at least two drying zones, and to provide exhaust means at a location 10 to 200 mm away from the first drying zone where spraying of the drying air is started on the web. .

Further, Japanese Patent Application Laid-Open No. 2000-24674, which is an invention for obtaining a film having a thickness of less than 85 μm and good film thickness accuracy.
No. 7 describes that a dry air having a static pressure of 1 to 100 mmAq is blown against the dope cast on a support.

Furthermore, in Japanese Patent Application Laid-Open No. 2003-053750, in order to stably produce a good quality film with high productivity, the mass fraction of the solid content in the dope is set to 17% by mass or more and 30% by mass or less. The average drying speed from casting to stripping exceeds 300% by mass and 1000% by mass
The invention is described to be less than / min.

Furthermore, in Japanese Patent Laid-Open No. 2003-103543, in order to obtain a film having excellent flatness without drying unevenness, a film is produced by casting a dope on a casting support that runs or rotates from a casting die. In the solution casting method, a solution casting method is described in which a dryer for condensing and recovering the solvent in the casting film is disposed immediately after the casting to dry the casting film.

Japanese Patent Laid-Open No. 2001-098086 includes a step of casting a cellulose ester dope or melt on a support in a method for producing a cellulose ester film, and a step of solidifying the dope or melt while applying a magnetic field. The invention has been described and is applicable to the present invention.

Furthermore, Japanese Patent Application Laid-Open No. 2002-120246 discloses a method of reducing film thickness unevenness by providing means for suppressing fluctuations in the wind pressure of the atmosphere in the casing.

The invention relating to the drying conditions and the like of these cellulose acylates on the metal support described above can also be applied in a timely manner in the present invention.

(Peeling)
The rate at which the cellulose acylate film is produced varies depending on the length of the belt, the drying method, the composition of the dope solvent, etc., but the residual solvent when the film (containing an organic solvent, also referred to as web) is peeled from the belt. It is almost determined by the amount of. In other words, if the solvent concentration in the vicinity of the belt surface in the thickness direction of the dope film is too high, the dope remains on the belt when it is peeled off, which hinders the next casting. This is because the web strength is required to withstand the peeling force. The amount of residual solvent at the time of peeling differs depending on the drying method on the belt or drum, and the method of transferring heat from the belt or drum back is more effective than the method of drying by blowing air from the dope surface. Can be reduced.

For the purpose of achieving a uniform surface with good flatness, Japanese Patent Application Laid-Open No. 5-057739 discloses that the volatile content at the time of stripping is 10 to 30% by weight based on the dry weight, and the surface temperature of the support at the peeled portion. 20 ° C
Hereinafter, an invention for maintaining the temperature at 14 ° C. or higher is described.

JP-A-2000-239403 relates to a method for producing a cellulose acylate film having a residual solvent ratio X of 15 ≦ X ≦ 120 at the time of peeling, and after the web has been peeled off from a metal support and then formed into a dry film. This is a drying method for cellulose acylate which is optically isotropic and has good flatness.

In addition, in order to obtain a film having a thin film thickness and excellent optical properties and flatness, Japanese Patent Application Laid-Open No. 2000-239403 describes that the web is peeled off at the same position in the length direction of the support at the peeling point. It is disclosed that an external force is partially applied to the web in the width direction as much as possible to perform film formation. Further, as a more preferred embodiment, the drying air temperature of the web on the casting support is T1, the drying air temperature applied to the web for at least 10 seconds after peeling is T2, the boiling point of the main solvent is the boiling point Tbp, and in the peeling part When the temperature of the casting support is Ts, T1 is in the range of Tbp-20 ≦ T1 ≦ Tbp + 20, and T2 is in the range of Ts ≦ T2 ≦ Ts + 40. It describes that the film is formed at a width of 3 to 40 kg / m.

Furthermore, in order to prevent film scratches and suppress haze, Japanese Patent Application Laid-Open No. 2002-187146 describes an invention that defines stripping volatile content, stripping draw rate, and stripping roll wrap.

In order to prevent the roll adhesion of plasticizers and ultraviolet absorbers, JP-A-2002-292658 describes that a web obtained by casting a cellulose ester solution on a driving metal endless belt is peeled from the endless belt. The invention describes that the residual solvent of the web at the time of peeling is 20 to 150%, and the Vickers hardness of the peeling roll and the transfer roll from the peeling roll to the drying device is 500 to 800. Furthermore, as a more preferable aspect, at least the peeling roll is heated to 100 to 300 ° C. among the peeling roll and the transfer roll from the peeling roll to the drying device, and the Vickers hardness of the heated roll is set to 800 to 1000. The surface roughness Ry of at least the peeling roll of the roll and the transfer roll is 0.6 μm or less, and at least the surface layer of the peeling roll is formed of a Ni alloy among the peeling roll and the transfer roll, the peeling roll and the transfer Use at least a peeling roll having a surface energy of 70 to 100 mN / m at 20 ° C. among the rolls. For the peeling roll after peeling the web from the endless belt by the peeling roll and the transfer roll from the peeling roll to the drying device. When the residual solvent of the web in contact is 60 to 80%, And the surface temperature of the transfer roll is set to be equal to or higher than the melting point of the plasticizer added to the web, the Vickers hardness of the release roll and the transfer roll is set to 500 to 800, and the release roll and the transfer roll are set to 100 to 300 ° C. Heat and make the Vickers hardness of these rolls 800-1000 after heating, ・ Surface roughness Ry of the peeling roll and the transfer roll should be 0.6 μm or less, ・ The surface layer of the peeling roll and the transfer roll should be Ni alloy It is disclosed that the surface energy at 20 ° C. is 70 to 100 mN / m for the peeling roll and the transfer roll. Furthermore, it is described that a more preferable range of Vickers hardness is 550 to 800.

Furthermore, Japanese Patent Application Laid-Open No. 2002-028943 of the invention aimed at eliminating horizontal unevenness includes: noise other than peeling sound of 125 to 250 Hz component in the state without a shield at a distance of 100 to 150 cm from the peeling point. 125, which is emitted when the web is peeled off when measuring the volume after subtracting
The peeling sound of the 250 Hz component should be 90 dB or less. ・ After peeling with a peeling tension of 30 to 240 N / m width, the distance between the process point from the peeling point to the tension blocking means is the web length and the minimum 2
m, a maximum of 90 m is conveyed while maintaining the tension of the web between the process distances, and the change in the residual solvent amount of the web between the process distances is between 140% by mass and 10% by mass, etc. ing. There is also a description that the tension blocking means may be a drive roll.

Furthermore, Japanese Patent Application Laid-Open No. 2002-254451 discloses a method for preventing occurrence of failures such as haze-up caused by step unevenness, band streaks, bevel-like failure, flatness unevenness, fine surface roughness, etc., which occur during peeling. A solution that makes the film peeling angle in the range of 30 to 80 degrees when the tangential direction at the peeling point of the casting support is 0 degree and the normal direction is 90 degrees. A film forming method is described.

The above-described invention relating to conditions for peeling cellulose acylate from a metal support can be applied to the present invention.

(Drying process immediately after peeling)
In the drying process after peeling from the metal support, the film tends to shrink in the width direction by evaporation of the solvent. Shrinkage increases with drying at higher temperatures. In order to improve the flatness of the finished film, it is preferable to dry while suppressing the shrinkage as much as possible. From this point, for example, a method of drying the entire drying process or a part of the process as shown in Japanese Patent Application Laid-Open No. 62-46625 while holding the width at both ends of the web with a clip in the width direction (tenter method) ) Is preferred.

Further, when the cellulose acylate dope in JP-A-4-085011 is cast on a metal support cooled to 20 ° C. or less, cooled, solidified, peeled and dried, the solvent is 40% by mass.
In the above process, in the production method in which the surface material of the transport roller is 20 ° C. and the surface energy is 80 mN / m or less, and the film is formed by casting the dope of JP-A-11-090946 on a metal support. A step of peeling a film containing 60% by mass or less of the solvent from the metal support, and removing the peeled film at a temperature of 120 to 135 ° C.
A manufacturing method in which heat treatment is performed for more than a minute can also be applied to the present invention.

In addition, regarding the drying process after peeling from the metal support, JP-A-11-221833, in order to increase the productivity of cellulose ester film having good flatness and excellent optical properties,
In the rotary cooling drum method, an invention that conveys and dries using a moving tenter at a speed of 1.105 to 1.2 times the peripheral speed of the cooling drum in the direction perpendicular to the rotation axis while holding both ends in the width direction is described. Yes.

Japanese Patent Application Laid-Open No. 11-235728, which has good flatness and eliminates variations in the rotator and is stable to manufacture, describes the web width length as A at an arbitrary position in the drying process after web peeling. An invention for carrying dry transport with Sa ≦ 5 when the width B of the position where the residual solvent ratio is reduced by 10% from the position and the shrinkage ratio Sa between them is Sa = {(AB) / A} * 100 Is described. Further, as a preferred embodiment, the roll that the web first contacts after peeling the web from the support is a drive roll, and when the web is introduced into the tenter device, the elastic modulus in the width direction of the web is 1.5 kg. Introducing at / mm ^{2 to} 400 kg / mm ²・ Conveying the web in the direction of web conveyance as 10 to 50 kgf / m. ・ The roll in the drying conveyance process is on the outer side in the width direction of the roll. A structure in which tension is applied toward the width of the roll. When the friction coefficient of the surface in the width direction of the roll is the maximum value μ _max and the minimum value μ _min , the ratio Hμ between the maximum value and the minimum value is Hμ = μ _Conveying using a roll with _max / μ _min ≧ 1.2 ・ A coating solution containing a solvent having swelling property with respect to the web in the dry conveying step after peeling the web from the support Just before applying Distillate solvent ratio and Y _0, the width length of the position is C, the width length after final drying transporting process is D, also the shrinkage rate Sc in between Sc = {(C-D) / C} × When 100, Se = 0.15Y ₀ +0.57 and the like are described. Further, it is disclosed that the roll diameter is preferably 5 to 30 cm (especially 10 to 20 cm is preferable), the friction coefficient is 0.12 to 0.8, and the minimum value is preferably 0.1 to 0.5. Yes.

In order to obtain good flatness, Japanese Patent Application Laid-Open No. 2001-129839 describes that the surface potential of the web is −5 to +5 kV from the time when the web is peeled off from the casting support to the time when it is dried by the drying device. The invention to be described is described. Further, as a preferred embodiment, the static electricity removing device sprays a gas containing ions, the oxygen concentration in the gas containing ions is 10% by volume or less, a casting support and / or The ground leakage resistance of the roll in contact with the web is 10 ⁶ Ω or less, the surface temperature of the web when peeling from the casting support is a temperature at which the vapor pressure of the organic solvent is 6650 Pa or less, the web It is disclosed that an electrostatic removal device is provided in the vicinity of the peeling portion that peels off the casting support, a static elimination bar or static elimination yarn is used as the static elimination device, and a static elimination bar or static elimination yarn is provided immediately after the peeling roll. ing. Further, regarding the method of setting the web surface potential during film formation in the range of −5 to +5 kV, the roll material of the partner in contact with the web being conveyed is determined from the charged row, and the charged row is a cellulose ester web. The method of selecting the one with a small amount of charge relative to the surface, the method of reducing the contact area with the web by appropriately roughening the surface of the support for casting and the roll, or adding a matting agent to the web , A method of reducing the contact area with a casting support or roll by coating a composition containing a matting agent on the surface, and containing or applying a conductive substance in or on the web to increase the conductivity of the web A method of improving the relative humidity of the external atmosphere to reduce the surface leakage resistance of the web, a method of ionizing the gas and blowing ions onto the web to neutralize the charge on the web surface, How to reduce the surface potential of the probe or has been shown how to by point discharge by the needle-like or line-like metal grounded leaked charge of the web surface, such that a combination of these methods.

Furthermore, in JP-A-2001-129839, as the static eliminator, any device that can remove or reduce static electricity on the web may be used, and examples include a static eliminator bar, a static eliminator, or an ion blowing static eliminator. Among them, it is described that an ion blowing type static eliminator is preferable. Here, the ion blow type static eliminator is an apparatus with a structure in which gas is ionized by corona discharge, flame plasma, ultraviolet rays, a heated metal body, a radioisotope, etc. to generate ions, and the generated ions are blown onto the object. is there. The static eliminator using corona discharge is composed of an electrode unit with a built-in high-voltage transformer, a blowing unit, a gas supply unit, a controller, and the like. The electrode unit generates corona discharge, ionizes the gas, and blows out. The gas ionized by the unit is sprayed on the object. Furthermore, air is usually used as the gas to be supplied. However, by introducing an inert gas so that the oxygen concentration in the gas is 10% by volume or less, the effect of improving safety against dangerous substances can be obtained. It has been shown that Further, the kind of the inert gas may be a gas such as nitrogen, carbon dioxide, or argon. Nitrogen and carbon dioxide are preferable from the point of cost, and it describes that it implements by providing a flow meter in a gas supply part and supplying these gas. Further, it is described that the neutralizing yarn is usually a flexible yarn-like one, for example, 12/300 × 3 made by Naslon. In JP 2001-129839 A, the distance between the static eliminator and the web is preferably 10 to 100 mm, and the place where the static eliminator is installed is the position of the web after peeling after the peeling position of the web from the casting support. A length of 10 to 100 mm is preferable as the length, and the vicinity of the peeling roll is preferable, or may be between the casting support and the peeling roll, but after the peeling roll is preferable in view of cutting of the web and personal danger. It is shown. Further, the place where the static eliminator is installed is preferably a distance of 10 to 1000 m (more preferably 10 to 500 m) from the peeling roll after the web peeling position from the casting support, particularly in the vicinity of the peeling roll. It is described that the removal device can be installed on any surface of the web.

In order to obtain a good flatness, a high residual solvent web can be stably peeled under high-speed film formation.
In JP-A-2001-198933, the web is peeled from the metal support, and immediately after that, the surface of the web that is in close contact with the metal support is brought into contact with the first roll, and then the air side on the metal support. The invention is described in which the surface of the web in contact with the second roll is brought into contact with the second roll and then dried.
As a more preferred embodiment, the first contact roll becomes smaller as the roll diameter becomes the center, the second roll is a roll whose diameter becomes larger as the roll diameter becomes the center, and the web Is peeled off from the metal support, first passed through a nip roll and then dried. • The web is peeled off from the metal support, and immediately thereafter, the angle θ between the plane of the web and the roll axis and (180 ° − θ ′) and θ and θ ′ are θ> 0 ° and θ ′ <90 °
After two small rolls having the following relationship are applied to both ends of the web surface that is in close contact with the metal support, and then the first roll is brought into contact with the surface of the web that was on the air side on the metal support・ Drying ・ Drying after contacting the web to the first roll that changes its position according to the amount of residual solvent immediately after peeling or according to the surface temperature of the web at the time of peeling ・ Metal support A vertical slit wind of a wind speed of 20 m / second or more is applied to the web surface that is in close contact with the body side from a nozzle installed above the web, and then the first web surface that is on the air side on the metal support The roll is brought into contact and then dried. The distribution in the width direction of the web in the direction of the width of the vertical slit wind gradually increases from the center to both ends. The web is peeled off from the metal support and at the time of peeling. The amount of residual solvent in the web Changing the wrap angle at which the web contacts the first roll by changing the position of the second roll that the web is in contact with and then drying the web after contacting the second roll; The surface temperature of the first roll has a distribution that decreases from the center to both ends in the length direction of the roll, and after the web is peeled from the metal support, the surface temperature Tr of the roll that the web first contacts with The web is first brought into contact with a roll whose surface temperature Tb of the metal support at the time of peeling is (Tr−Tb) ≦ 50 ° C. and then dried, and the surface temperature Tr of the roll is that of the roll It has been disclosed that it has a distribution that decreases from the center to both ends in the length direction, and that the surface roughness Ra of the roll with which the peeled web first contacts is Ra ≦ 1.0 μm, etc. . Further, it is described that the drive roll may have a speed change of 1.001 to 1.100.

In order to improve flatness and prevent scratches and breakage at both ends, JP-A-2001-277267
There is described an invention having means for conveying the web in a non-contact manner to at least the air side surface of the web on the metal support immediately after the peeling roll to the tenter inlet.
As a further preferred embodiment, there is a means for conveying the web in a contactless manner with respect to the air-side surface on at least the metal support of the web, and the number of conveying rolls contacting the air-side surface is within three. -The web conveyance distance of the means for carrying out contactlessness is 10 to 60% of the web conveyance distance from immediately after the peeling roll to the tenter outlet.-The means for carrying out contactlessly blows air on both sides of the web. It is of the air floater type to be sprayed, and is at least one selected from the type of gripping both ends of the web and the type of suction roll in which only the surface on the metal support side of the web contacts the metal support. .. Passing the web having a residual solvent amount of 20 to 130% by mass through the means for carrying without contact, and the ambient temperature of the means for carrying without contact being 40 ° C.
In the following, passing the web through the apparatus is disclosed. In addition, it is disclosed that an apparatus having a means for conveying without contact can be an air floater type, a type capable of gripping both ends of a web with a clip or a nip roll, or a suction roll type. Furthermore, both ends of both sides of the web are gripped by a movable caterpillar belt and conveyed without contact, and both ends of both sides of the web are gripped by a plurality of narrow nip rolls and conveyed without contact. Etc. are described. Further, as a detailed mode of the nip roll type, the plurality of pairs of nip rolls are preferably easier to grip than those having a shape with unevenness, and have unevenness for embossing, and the upper and lower sides are male and female. Further, the shape is such that the shape, size, and height of the concave and convex portions can be firmly gripped, such as a sharp tip or groove shape, and a plurality of pairs of nip rolls 30. It is described that the pressure is 30 to 500 Pa (more preferably 50 to 200 Pa).

For the purpose of preventing the roll from becoming dirty, Japanese Patent Application Laid-Open No. 2002-086474 discloses a method for producing a cellulose ester film having a film thickness of 20 to 80 μm using a solution casting film forming apparatus. 10 to 150% by mass of a web having a surface roughness Ry of 0.6 μm or less and 2
An invention is described in which the material is conveyed while being brought into contact with a roll having a surface energy of 70 to 100 mN / m at 0 ° C.
As a further preferred embodiment, the first one of the rolls is a peeling roll, and the roll is only a roll that contacts the air side surface of the web on an endless metal support that moves infinitely. The roll is made of hard chrome plating, the diameter of the roll is 85 to 300 mm, and the solution casting film forming apparatus has a cleaning means for the roll and the roll surface, the cleaning means Has a means for adhering the organic solvent to the roll while moving in the roll axis direction and a means for wiping the roll surface adjacent to the roll. Supply solvent, or
Wiping with a non-woven fabric containing an organic solvent, ・ A good solvent in which the organic solvent is soluble in cellulose ester, or a good solvent in which the organic solvent is soluble in cellulose ester It is disclosed that it is a mixture of poor solvents that do not.

Furthermore, in order to prevent wrinkles from being generated on the film, JP 2003-094467 A relates to a process in which the amount of residual solvent is 40 wt% or less, and adsorbs and transports the film using a hollow drive roll that can be decompressed. The invention has been described. As a more preferred embodiment, a plurality of suction ports are formed over the entire circumference in at least a part of the peripheral wall of the drive roll,
Furthermore, the suction port is covered with a cover whose outer peripheral surface is made of a metal mesh (the mesh size of the metal mesh is 0.5 to 50 mm ² ). A mouth is formed, and the suction port is covered with a cover having an outer peripheral surface made of a porous plate (the size of the through hole of the porous plate is 0.5 to 50 mm ² ). The ratio of the length of the formed web or film in the width direction is 0.1 to 1 with respect to the entire width of the web or film. The suction port on the peripheral wall of the drive roll is circular or elliptical. Or it is made into the polygon more than a pentagon, and the magnitude | size shall be 1-100 mm < ² >, and the suction port in the surrounding wall of a drive roll is 30.
1 or more per mm × 30 mm range, the outer diameter of the drive roll is 65-4
It is disclosed that it is 50 mm. Furthermore, a drive shaft that is driven to rotate by a motor or the like is fixed to the lid that closes the opening at both ends of the peripheral wall of the drive roll, and the drive shaft fixed to one of the lids has an interior of the drive roll over its entire length. It is described that a suction path leading to is formed, and the inside of the drive roll is decompressed through the suction path by a vacuum pump. It is also described that the air sucked by the vacuum pump is sent to a solvent recovery device, where the solvent in the solvent dissolving the cellulose ester is recovered.

Furthermore, in Japanese Patent Application Laid-Open No. 10-006351, which is an invention aimed at excellent dimensional stability, the temperature for drying the film after being peeled off from the casting support is 3 in the range of 40 ° C. to 140 ° C. It is shown that it is preferable to increase the temperature stepwise by dividing the temperature into ˜4 steps.

Japanese Patent Laid-Open No. 2001-315147 of the invention for the purpose of producing a thin TAC film at high speed includes a roll group conveyance in which webs are arranged in a staggered manner when the transfer zones are arranged in a staggered manner. It is described that the web is conveyed so that the passage time is 10 to 70 seconds while the surface temperature of the web is 50 to 100 ° C. by means. As a more preferred embodiment,
The widest roll interval of the roll conveying means is set to the maximum web width at the time of peeling, the roll interval is set to 900 mm or less, and the residual solvent amount of the web at the time of peeling is 60
When the web is passed as a residual solvent amount of 30 to 120% by mass between the peeling roll and the tenter dryer introduction port, and is dried on an endless metal support that moves infinitely during that period. An organic solvent having solubility or swelling ability with respect to the cellulose ester is adhered to the air side surface of the web of the web, and the air side of the web when dried on an endless metal support that moves infinitely. It is disclosed that the surface is conveyed while being brought into contact with a conveying means selected from a drum and an arched roll.

Furthermore, in JP 2001-315147 A, between the peeling roll and the tenter drying device introduction port,
Between the peeling roll and the tenter drying device inlet, the residual solvent amount is 30 to 120% by mass.
It is preferable that the surface temperature of both ends of the web is 50 ° C. or higher, and the means for heating both ends of the web is selected from near infrared or far infrared irradiation and hot air blowing Is shown to do. Moreover, after heating both ends of the web, the same part may be cooled by a cooling roll, and the web is passed as a residual solvent amount of 30 to 120% by mass between the peeling roll and the tenter dryer introduction port, It is also described as a preferred embodiment that an organic solvent having solubility or swelling ability with respect to cellulose ester is attached to both ends of the air side surface of the web when it is dried on an endless metal support that moves indefinitely. Yes. Furthermore, it is also disclosed that both ends of the web may be cut with a width within 50 mm from the end in a region where the amount of residual solvent after peeling is 50% by mass or less.

In addition, JP 2003-071863, an invention for obtaining a film that does not cause fogging, has a problem in that, when peeling off at a time when the amount of residual solvent is larger, if the web is too soft, the flatness may be impaired at the time of peeling. Tension and vertical stripes are likely to occur due to the tension, and the peeling tension when peeling the belt and the film is usually 196 to 245 N / m.
Peeling is preferably performed at 0 N / m or less, and further, the minimum tension at which peeling is possible to 166.6 N /
It is preferred to peel at m, then at a minimum tension of ~ 137.2 N / m, but the most preferred is to peel at a minimum tension of ~ 100 N / m. In particular, the lower the release tension, the better the in-plane retardation Ro can be kept low.
It is described that o is preferably less than 20 nm, more preferably less than 10 nm, then less than 5 nm, and most preferably 0 to 1 nm.
Japanese Patent Application Laid-Open No. 2003-071863 further uses a drying device that alternately conveys the film through rolls arranged in a staggered manner and / or a tenter device that conveys the film while holding both ends of the film with clips or pins. It is disclosed that it is preferable to maintain the conveyance tension in the process of drying the film as low as possible while maintaining it, because Ro can be maintained low, specifically, it is preferably 190 N / m or less, more preferably Is 170 N / m or less, particularly 140 N / m or less, and most preferably 100 to 130 N / m. Also, it is effective to maintain the amount of residual solvent in the film below the conveying tension until at least 5% by mass or less. As a drying means, it is common to blow hot air on both sides of the film. However, a means of heating by applying a microwave instead of an air flow is shown.
However, since too rapid drying tends to impair the flatness of the film, drying at a high temperature is preferably performed from about 8% by mass or less of the residual solvent, and the drying is generally performed at 40 to 250 ° C. throughout. It is disclosed that it is preferable to dry at 40 to 160 ° C.

Japanese Patent Application Laid-Open No. 2002-241511 has been proposed in order to eliminate deformation with time even for a thin film of 20 to 60 μm, optically isotropic, no scratches, and to eliminate bubbles and undissolved materials. Is
The residual solvent amount at the time of winding is 0.05% by mass or less, and the tension is 10 to 100 N / m between the peeling of the web from the metal support and the tension breaking device (between peeling and tension breaking device). Is disclosed. As a further preferred embodiment, the distance between the peeling and the tension breaking device is 2 to 90 m as the length of the web, and the conveying means between the peeling and the tension breaking device is as follows:
It is described that it is a guide roll and / or an air float, and that a part or all of the guide roll is a tendency roll.

In JP-A-2003-094470, in order to control optical properties, dimensional stability, and flatness, -4 ≦ MD−TD ≦ 4% and -6 ≦ MD +
It is described that TD ≦ 6% (conveyance direction expansion ratio MD, width direction expansion ratio TD). As a more preferred embodiment, it is disclosed that TD1 ≧ −6% when the expansion ratio in the width direction of the film in the region from the peeling of the film from the support to the first stretching in the width direction is TD1. Yes.

Furthermore, JP-A-2003-175523 discloses that when the solvent content at the time of peeling is 60% by weight or less in order to prevent deformation such as curling and folding of both ears caused by the difference in drying speed between the front and back surfaces, the peeling point From the end of the film on the roll to the outside within 10 seconds and in the transition zone
An invention is disclosed in which the temperature at a location 2 cm away from the roll surface is set to the boiling point of the main solvent to the boiling point + 30 ° C.

In addition, in JP-A-2003-175521, in order to suppress the occurrence of planar defects due to the aggregation component of the solvent,
In the transition step, when the solvent content of the peeled film is 60% by weight or less, air is supplied to at least the film surface side that has been in contact with the endless support within 10 seconds after peeling. A solution casting method is described.

Japanese Patent Application Laid-Open No. 2001-315147 discloses a method of adhering an organic solvent to a web for curling suppression in a transition zone from a peeling roll to an entrance of a tenter device. As the adhering method, an organic solvent liquid is disclosed. The method of spraying, the method of spraying organic solvent gas, the method of spraying the organic solvent in the form of a mist, and the like are disclosed, and it is also disclosed that the amount of the organic solvent attached is adjusted depending on the size of the curl. Has been. In addition, as a method of applying the organic solvent, it is performed to such an extent that additives such as a plasticizer do not elute, and the entire surface of the guide roll (conveying roll) that is in contact with the support surface (drum surface) side (air surface) side is contacted with the organic solvent. It is described that a coating roll (which may be a peeling roll) for applying an organic solvent is provided by using a guide roll as a back roll. Furthermore, the organic solvent gas is sprayed on the entire air surface of the web, or the organic solvent is sprayed in the form of a mist, and the concentration of the organic solvent should be within the range where no explosion occurs. It is described that evaporation or excess gas is quickly discharged out of the system by suction. In addition, as an organic solvent, what has a solubility or swelling ability with respect to cellulose ester such as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, propyl acetate is used. Mixing with methanol, ethanol, propanol, hexane or the like that does not have solubility or swelling ability makes it easier to obtain better results when used alone, and the mixing ratio is preferably 20/80 to 90/10 as a mass ratio. It is shown that it is determined appropriately depending on the combination curl degree of each organic solvent. Moreover, in this case, it is effective by heating from the air surface side.

Furthermore, in JP-A-2001-315147, any curl correcting means can be used without limitation as long as it can heat both ends, but a means for correcting the ends with heated air on a roll, a pair of webs from the front and back sides. The means to correct by pinching with a heating roll, the means to correct by indirectly heating with near infrared rays or far infrared rays, etc., the heating air is blown from the nozzle, pipe cross section or pipe having a punch hole In addition, it is disclosed that the heated roll should be in contact with a roll such as a nip roll that is narrow and only at both ends. Moreover, the part to heat is less than 100 mm (more preferably 50 mm) from the both ends of a web, and it is shown that the temperature to heat is 50 degreeC (preferably 80-100 degreeC) or more.
Furthermore, in the case of a heating roll, the roll is preferably a metal roll, but a ceramic roll may be more preferred, and a method of heating the ceramic roll indirectly with infrared rays is also preferred. By the way, if left as it is after heating, the webs at both ends may be soft and curl may occur again. It is preferable to cool only the heated part as soon as it is heated. Although it can be used without limitation, it is disclosed that a method of applying cooling air or a method of contacting a cooling roll is preferable. As detailed conditions, it is disclosed that the cooling temperature is 10 ° C. or less lower than the heating temperature. In addition, after peeling, there is also described a method of correcting the curl by cutting off the curl generated at both ends in a region where the residual solvent amount of the web is 50% by mass or less from the both ends within a width of 50 mm or less. Shows that curling at both ends is likely to occur again and curl immediately after being cut, so that it is preferable to cut immediately before the inlet of the tenter drying device or just before the drive roll.

Japanese Patent Laid-Open No. 2002-292658, which is an invention for preventing the adhesion of plasticizers and UV absorbers to rolls, is also disclosed in Japanese Unexamined Patent Application Publication No. 2002-292658. When transported by a roll, the roll diameter is small, for example, less than 85 mm (thin roll)
However, the roll is easily deformed or stretched by the force of the web pressed against the roll surface, but not only that, but the additive that precipitates and evaporates from the web adheres to the roll, and is further transferred from the roll to the web. It is disclosed that this is soiled or is easily pressed by an additive to form a dent, and conversely, when the roll diameter is larger than, for example, 300 mm (thick roll), the roll rotates with a weak tension. Since it does not work well and scratches and the like are applied to the web, it is necessary to increase the tension in order to rotate the thick roll in synchronization with the web transfer, resulting in problems such as dirt and dents. It is described. Therefore, it is understood that the roll diameter is preferably 85 to 300 mm, and particularly preferably 100 to 200 mm. Further, as a preferred embodiment, when a plurality of plasticizers are used, it is described that the temperature is higher than the highest melting point.

The invention relating to the drying step immediately after peeling of the cellulose acylate from the metal support described above can also be applied to the present invention.

(Stretching)
Further, there is a method of positively stretching in the width direction. In the present invention, for example, JP-A-62-1
15035, JP-A-4-152125, JP-A-4-284111, JP-A-4-29
No. 8310 and JP-A-11-48271. In order to increase the in-plane retardation value of the cellulose acylate film, the produced film is stretched. The film is stretched at room temperature or under heating conditions. The heating temperature is preferably not higher than the glass transition temperature of the film. The film may be stretched uniaxially or biaxially. The film can be stretched by a treatment during drying, and is particularly effective when the solvent remains. For example, the film is stretched by adjusting the speed of the film transport roller so that the film winding speed is higher than the film peeling speed. The film can also be stretched by conveying the film while holding it with a tenter and gradually widening the width of the tenter. After the film is dried, it can be stretched using a stretching machine (preferably uniaxial stretching using a long stretching machine). The stretch ratio of the film (ratio of increase due to stretching relative to the original length) is preferably 0.5 to 300%, and more preferably 1
-200% stretching is preferred, especially 1-100% stretching. The cellulose acylate film produced in the present invention is particularly preferably applied to a retardation plate. The retardation plate is preferably manufactured by sequentially or continuously performing a film forming step by a solvent cast method and a step of stretching the formed film, and the stretching ratio is 1.2 times or more and 1.8.
It is preferable that it is less than 2 times. In addition, the stretching may be performed in one stage or in multiple stages.
When performing in multiple stages, the product of each draw ratio may be within this range.

The stretching speed is preferably 5% / min to 1000% / min, more preferably 10% / min to 50%.
It is preferably 0% / min. The stretching temperature is preferably 30 ° C to 160 ° C, more preferably 70 ° C to 150 ° C. 85-150 degreeC is especially preferable. The stretching is preferably performed by a heat roll or / and a radiant heat source (such as an IR heater) or warm air. Moreover, you may provide a thermostat in order to improve the uniformity of temperature. When performing uniaxial stretching by roll stretching, it is preferable that L / W which is ratio of the distance (L) between rolls and the film width (W) of this phase difference plate is 2.0-5.0.

It is preferable to provide a preheating step before stretching. You may heat-process after extending | stretching. The heat treatment temperature is preferably 20 ° C. to 10 ° C. higher than the glass transition temperature of the cellulose acetate film, and the heat treatment time is preferably 1 second to 3 minutes. Also,
The heating method may be zone heating or partial heating using an infrared heater. You may slit the both ends of a film in the middle or the end of a process. These slit scraps are preferably recovered and reused as raw materials. Further, regarding the tenter, JP-A-11-077
In No. 718, when drying the web while maintaining the width with a tenter, the drying gas blowing method, blowing angle, wind speed distribution, wind speed, air volume, temperature difference, air volume difference, up and down blowing air volume ratio, use of high specific heat drying gas, etc. By appropriately controlling this, it is possible to ensure the prevention of quality deterioration such as flatness when the speed by the solution casting method is increased or the web width is increased.

Japanese Patent Laid-Open No. 11-077822 describes an invention in which a stretched thermoplastic resin film is heat treated by providing a temperature gradient in the width direction of the film in the heat relaxation step after the stretching step in order to prevent unevenness. .

In order to reduce Re and reduce variations in the slow axis, Japanese Patent Laid-Open No. 2002-0
No. 79532 describes an invention in which the application of tension in the width direction is started at an arbitrary time when the solvent content of the cellulose ester film is 17 to 24% by weight and the widening ratio is 1 to 4%. .

Furthermore, in order to prevent the occurrence of unevenness, Japanese Patent Application Laid-Open No. 4-204503 describes an invention in which the film is stretched with a solvent content of 2 to 10% based on solid content.

Further, in order to suppress curling due to the regulation of the clip biting width, JP 2002-248680 discloses that the tenter clip biting width D ≦ (33 / (log stretching rate × log volatile content)). An invention that suppresses curling and facilitates film conveyance after the stretching process is described.

Further, in order to achieve both high-speed soft film conveyance and stretching, Japanese Patent Application Laid-Open No. 2002-337224 describes an invention in which tenter conveyance is switched between a first half pin and a second half clip.

Japanese Patent Laid-Open No. 2002-187960 discloses that a cellulose ester dope solution is cast on a casting support for the purpose of easily improving the viewing angle characteristics and improving the viewing angle, and then casting. The web (film) peeled off from the support for the web has a residual solvent amount of 100% by mass or less, in particular,
An optically biaxial invention obtained by stretching 1.0 to 4.0 times in at least one direction while in the range of 10 to 100% by mass is described. As a more preferable embodiment, it is described that the film is stretched 1.0 to 4.0 times in at least one direction while the residual solvent amount in the web is in the range of 100% by mass or less, particularly 10 to 100% by mass. . In addition, as another stretching method, a circumferential speed difference is applied to a plurality of rolls, and a longitudinal stretching is performed using the difference between the circumferential speeds of the rolls, and both ends of the web are fixed with clips or pins. Examples include a method of extending the interval in the traveling direction and stretching in the vertical direction, a method of expanding in the horizontal direction and extending in the horizontal direction, a method of expanding the vertical and horizontal directions simultaneously and stretching in both the vertical and horizontal directions, a method using a combination of these, and the like. It has been. Further, in the case of the so-called tenter method, it is shown that it is preferable to drive the clip portion by the linear drive method because smooth stretching can be performed and the risk of breakage or the like can be reduced.

In order to provide an elliptically polarizing plate having a dark field with no unevenness and excellent productivity,
In 96422, when the cellulose ester film was formed, the substitution degree of the acetyl substituent was X,
When the degree of substitution of the poropionyl group and / or butyryl group is 2.3 ≦ X + Y ≦ 2.85,
. A dope using cellulose ester that simultaneously satisfies 4 ≦ X ≦ 2.85 was cast on a metal support, and a web peeled from the metal support was subjected to a web transfer with an average residual solvent amount of 5 to 60% by mass. An invention is described in which the film is stretched by 1.15 to 2.0 times with respect to the width in which the web is sandwiched in the transverse (width) direction at a temperature of ˜170 ° C. Furthermore, as a preferred embodiment, the web peeled from the metal support is stretched in the transverse direction with the end portion at a temperature 1-30 ° C. higher than the center portion,
-Stretching the edge in the transverse direction with a residual solvent amount of 0.1 to 30% by mass greater than the central part-Performing transverse stretching of the web peeled from the metal support in two zones with different temperatures, Second
Performing horizontal stretching in the zone at a temperature 1 to 50 ° C. higher than the first zone, and performing the temperature of the web immediately before performing the horizontal stretching 1 to 100 ° C. lower than that during the horizontal stretching, etc. Is disclosed.

Further, for the purpose of a method for producing an optical film having a small Re and no variation, JP
No. 02-311245 includes a step of feeding a peeled web to a first tenter device, gripping both side edges of the web in the width direction, keeping the web width constant, or stretching the web in the width direction, A step of drying the film to obtain a film, and a step of secondly sending the film to a device to a tenter, holding both edges in the width direction of the film, and maintaining the film width constant or stretching the film in the width direction. An invention relating to a method for producing an optical film is described.
As a more preferred embodiment, a web is formed by drying until the residual solvent amount becomes 70 to 160% by mass, and the residual solvent amount of the web sent to the first tenter device is 10 to 50% by mass.
The amount of residual solvent in the web sent to the second tenter device is 5% by mass or less,
-The processing temperature in the second tenter device is within the range of ± 50 ° C of the glass transition temperature of the raw resin, and the stretch ratio is 0-3%.-In the plane of the web that has passed through the first tenter device Measure the retardation and control the stretch ratio in the first tenter device based on this measured value.-Dimensions in the conveyance direction and width direction of the web peeled from the support, before and after the first tenter device. The dimensions of the web in the transport direction and the width direction, and the dimensions in the transport direction and the width direction of the film before and after the second tenter device are measured. Based on the dimensions of the web peeled from the support, For example, it is disclosed that the dimensional ratios in the transport direction and the width direction before and after the second tenter device are set to 0.9 to 1.1, respectively.

Furthermore, for the purpose of a retardation film having little additive bleed-out, no delamination phenomenon between layers, good slipperiness and excellent transparency, Japanese Patent Application Laid-Open No. 2003-014933 discloses a resin, an additive and an organic layer. A dope A containing a solvent, and a dope B containing no additive or a resin containing an additive less than the dope A, an additive, and an organic solvent are prepared. After co-casting on the support so that B becomes a surface layer and evaporating the organic solvent until it becomes peelable, the web is peeled off from the support, and the residual solvent in the resin film during stretching is further removed. 3
An invention is described in which the film is stretched 1.1 to 1.3 times in at least one axial direction in the range of ˜50 mass%. Furthermore, as a preferred embodiment, the web is peeled from the support and the stretching temperature is 14
Stretching 1.1 to 3.0 times in the direction of at least one axis in the range of 0 ° C. to 200 ° C. Preparation of dope A containing resin and organic solvent and dope B containing resin, fine particles and organic solvent Then, after co-casting on the support so that the dope A becomes the core layer and the dope B as the surface layer, and evaporating the organic solvent until it becomes peelable, the web is peeled off from the support, and further stretched When the residual solvent amount in the resin film is in the range of 3% to 50% by mass, the film is stretched 1.1 to 3.0 times in at least one axial direction, and the stretching temperature is in the range of 140 ° C to 200 ° C. 1.1 to at least one axial direction
Stretching 3.0 times; Dope A containing resin, organic solvent, and additive; Dope B containing no additive or less additive than Dope A, additive, and organic solvent And a dope C containing a resin, fine particles and an organic solvent. The dope A is a core layer, the dope B is a surface layer, and the dope C is a surface layer opposite to the dope B. After casting and evaporating the organic solvent until it can be peeled, the web is peeled from the support, and the amount of residual solvent in the resin film at the time of stretching is at least 1 in the range of 3% to 50% by weight. 1.1-3 in the axial direction.
Stretching 0 times. 1. Stretching temperature in the range of 140 ° C to 200 ° C.
Stretching 1 to 3.0 times, The amount of additive in dope A is 1 to 30% by mass with respect to the resin, and the amount of additive in dope B is 0 to 5% by mass with respect to the resin. The agent is a plasticizer, an ultraviolet absorber, or a retardation control agent. The organic solvent in the dope A and the dope B contains methylene chloride or methyl acetate in an amount of 50% by mass or more based on the total organic solvent. It is disclosed.

Furthermore, in Japanese Patent Application Laid-Open No. 2003-014933, as a stretching method, there is a transverse stretching machine called a tenter that secures both ends of a web with clips and pins and widens the distance between the clips and pins in the lateral direction. It is described that it can be preferably used. It is also disclosed that stretching or shrinking in the longitudinal direction can be performed by widening or shrinking the interval in the transport direction of the clip or pin in the transport direction (longitudinal direction) using a simultaneous biaxial stretching machine. . Also,
When the clip portion is driven by the linear drive system, it is possible to perform the stretching smoothly and the risk of breakage or the like can be reduced. Moreover, as a method of extending | stretching to a vertical direction, the method of giving a circumferential speed difference to several rolls, and extending | stretching to a vertical direction using a roll circumferential speed difference among them can be used. In addition, it is described that these stretching methods can be used in combination, and the stretching process may be performed in two or more stages, such as longitudinal stretching, lateral stretching, longitudinal stretching or longitudinal stretching, longitudinal stretching. Has been.

Further, in order to have a positive wavelength dispersion characteristic and to reduce angular unevenness in the slow axis direction, Japanese Patent Laid-Open No. 2002-3
In No. 11240, a cellulose ester dope containing a cellulose ester and an organic solvent is cast on a support to evaporate the organic solvent until it can be peeled, and then the web is peeled from the support and further dried. It is described that the obtained cellulose ester film is stretched in the longitudinal direction while being conveyed in a direction opposite to the casting direction. As a more preferred embodiment, the cellulose ester film has a residual solvent amount of 2% by mass or less and is stretched by 1.05 to 2.0 times in the longitudinal direction, while being transported in the direction opposite to the casting direction and in the transverse direction.・ Draw the web from the support and then hold the width of the peeled web, or dry it while shrinking in the 0-10% width direction. It describes that it is transported while being wound around a plurality of rolls whose distance is 20 to 300% with respect to the width of the cast film, and that the cellulose ester film has a convex stretched line.

Furthermore, in order to prevent foaming of the tenter-dried web, improve detachability, and prevent dust generation, Japanese Patent Application Laid-Open No. 2003-004374 describes that in a drying apparatus, hot air from a dryer hits both edges of the web. There is described an invention in which the width of the dryer is made shorter than the width of the web.

In addition, in order to prevent foaming of the tenter-dried web, improve detachability, and prevent dust generation, JP 2003-019757 discloses that both end portions of the web should not be exposed to the tenter holding part. An invention in which a wind shield is provided on the inside is described.

Further, in order to stably carry and dry, Japanese Patent Application Laid-Open No. 2003-053749 describes that the thickness after drying of both ends of the film supported by the pin tenter is X μm, and the average thickness after drying of the product part of the film. When the thickness is T μm, when the relationship between X and T is expression (1) T ≦ 60, 40 ≦ X ≦ 200
(2) When 60 <T ≦ 120, 40+ (T−60) × 0.2 ≦ X ≦ 300 or Formula (3
) When 120 <T, the invention that satisfies the relationship of 52+ (T−120) × 0.2 ≦ X ≦ 400 is described.

In order to prevent wrinkles from occurring in the multistage tenter, Japanese Patent Application Laid-Open No. 2-186254 discloses a tenter device in which a heating chamber and a cooling chamber are provided in the dryer of the multistage tenter, and the left and right clip chains are separated. Describes an invention for cooling.

Further, in order to prevent web breakage, wrinkles, and conveyance failure, Japanese Patent Laid-Open No. 9-077315 describes an invention in which the pin density of the pin tenter is increased while the pin density on the outer side is decreased. .

Further, in order to prevent foaming of the web itself and adhesion of the web to the holding means in the tenter, Japanese Patent Application Laid-Open No. 9-085846 discloses a tenter dryer in which both-side edge holding pins of the web are blown out type coolers. In the invention, the pin is cooled to below the foaming temperature of the web and the pin immediately before the web is entrapped is cooled to a gelling temperature of the dope in the duct type cooler + 15 ° C. or lower.

Furthermore, in order to prevent pin tenter losing and improve foreign matter, JP 2003-103542 A discloses a surface temperature of a web that cools the insertion structure in the pin tenter and is in contact with the insertion structure. Describes an invention relating to a solution casting method in which the temperature does not exceed the gelling temperature of the web.

In order to prevent deterioration in quality such as flatness when the speed is increased by the solution casting method or the width of the web is widened by a tenter, JP-A-11-077718 discloses a web in the tenter. When drying, an invention in which the wind speed is 0.5 to 20 (40) m / s, the transverse temperature distribution is 10% or less, the web top and bottom air volume ratio is 0.2 to 1, and the dry gas ratio is 30 to 250 J / Kmol. Has been described. Furthermore, preferable drying conditions are disclosed depending on the amount of residual solvent in drying in the tenter. Specifically, after the web is peeled off from the support, the angle at which the blowout port blows out is 30 ° to 150 ° with respect to the film plane until the residual solvent amount in the web reaches 4% by weight. When the wind speed distribution on the surface of the film located within the range and in the extending direction of the drying gas is based on the upper limit of the wind speed, the difference between the upper limit and the lower limit is within 20% of the upper limit. The gas is blown to dry the web. When the amount of residual solvent in the web is 130% by weight or less and 70% by weight or more, the wind speed on the web surface of the dry gas blown from the blow type dryer is 0.5 m. When the residual solvent amount is less than 70% by weight and 4% by weight or more, the dry gas wind blown out at a wind speed of the dry gas of 0.5 m / sec to 40 m / sec. When the temperature distribution of the drying gas in the width direction of the web is based on the upper limit value of the gas temperature, the difference between the upper limit value and the lower limit value should be within 10% of the upper limit value. When the residual solvent amount is 4% by weight or more and 200% by weight or less, the air flow ratio q of the dry gas blown out from the blow-out port of the blow-type dryer located above and below the conveyed web should be 0.2 ≦ q ≦ 1. Is described. Further, as a preferred embodiment, at least one kind of gas is used for the drying gas, and its average specific heat is 31.0 J / K · mol or more and 250 J / K · mol or less, and it is included in the drying gas during drying. It is disclosed that the concentration of the organic compound which is liquid at room temperature is dried with a drying gas having a saturated vapor pressure of 50% or less.

Further, in order to prevent the flatness and coating from deteriorating due to the generation of contaminants, JP-A-11-077
No. 719 describes an invention in which a tenter clip incorporates a heating portion in a TAC manufacturing apparatus. As a further preferred embodiment, a device for removing foreign matter generated at the contact portion between the clip and the web is provided after the clip of the tenter releases the web until the web is carried again. And using a brush to remove foreign matter, and the residual amount when the clip or pin contacts the web is 12% to 50% by weight
It is disclosed that the surface temperature of the contact portion between the clip or the pin and the web is 60 ° or more and 200 ° or less (more preferably 80 ° or more and 120 ° or less).

To improve flatness, improve quality degradation due to tearing in the tenter, and increase productivity,
In Japanese Patent Laid-Open No. 11-090943, in a tenter clip, an arbitrary transport length Lt (
m) and the total length Ltt (m) in the conveyance direction of the portion where the clip of the tenter having the same length as Lt holds the web Lr = Ltt / Lt is 1.0 ≦ Lr ≦ 1 .99 is described. Furthermore, as a preferable aspect, it is disclosed that the portion holding the web is arranged without a gap when viewed from the web width direction.

Further, when introducing a web into a tenter, in order to improve the flatness deterioration due to web sagging and the instability of introduction, Japanese Patent Application Laid-Open No. 11-090944 discloses a plastic film manufacturing apparatus before the tenter entrance. An invention having a sag suppressing device in the web width direction is described. Further, as a more preferable aspect, the sagging suppression device is a rotating roller that rotates in the direction range of 2 to 60 ° in the width direction, has a suction device on the top of the web, under the web It has also been disclosed to have a blower that can blow air.

In order to prevent deterioration of quality and sagging that hinders productivity, Japanese Patent Application Laid-Open No. 11-090945 describes that in the TAC manufacturing method, the web peeled from the support has an angle with respect to the horizontal. The invention to be introduced into the tenter is described.

In order to produce a film having stable physical properties, Japanese Patent Application Laid-Open No. 2000-289903 discloses that in a transporting device that transports while tension is applied in the width direction of the web when the solvent content is 50 to 12 wt%. Width detection means, web holding means, and an invention that has two or more variable bending points, calculates the web width from the detection signal in web width detection, and changes the position of the bending point Yes.

Furthermore, in order to improve the clipping property, prevent web breakage for a long period of time, and obtain a film with excellent quality, JP 2003-033933 discloses on both the left and right sides of the portion near the entrance of the tenter.
A web contact resin in which a web side edge curl prevention guide plate is disposed at least below the upper and lower side edges of the web, and the web facing surface of the guide plate is arranged in the web conveyance direction. It is described that it is constituted by a part and a metal part for web contact. As a further preferred embodiment, the web contact resin part of the web facing surface of the guide plate is disposed on the upstream side in the web conveyance direction, and the web contact metal part is disposed on the downstream side, and the web contact resin of the guide plate The step (including the inclination) between the web contact metal part and the web contact metal part is within 500 μm. The distance in the width direction in contact with the web of the web contact resin part and the web contact metal part of the guide plate is as follows: The distance between the web contact resin portion of the guide plate and the web contact metal portion of the web contact direction in the web conveyance direction is 5 to 120 mm, respectively. The web contact resin of the guide plate. The part is provided on the metal guide substrate by surface resin processing or resin coating, and the web contact resin part of the guide plate is made of a single resin. The distance between the web-facing surfaces of the guide plates arranged above and below at the left and right side edges of the web is 3 to 30 mm, and the webs of the upper and lower guide plates at the left and right side edges of the web The distance between the surfaces is enlarged in the width direction of the web and inward at a rate of 2 mm or more per 100 mm width, and the upper and lower guide plates are 10 to 10 at the left and right side edges of the web, respectively. It has a length of 300 mm, and the upper and lower guide plates are arranged so as to be displaced back and forth along the web conveying direction, and the distance of deviation between the upper and lower guide plates is −200 to +200 mm. The web facing surface of the upper guide plate is made of resin or metal only. The web contact resin portion of the guide plate is Teflon (registered trademark). The metal part for web contact is made of stainless steel. The surface roughness of the web facing surface of the guide plate or the resin part for web contact and / or the metal part for web contact provided thereon is 3 μm. The following are disclosed. Further, it is also described that the installation position of the upper and lower guide plates for preventing web side edge curl generation is preferably between the peeling side end portion of the support and the tenter introduction portion, and more preferably installed near the tenter entrance. Has been.

Furthermore, in order to prevent the cutting and unevenness of the web that occurs during drying in the tenter, JP-A-11-0
In No. 48271, after peeling, when the web has a solvent content of 50 to 12 wt%, it is stretched and dried with a width stretcher, and when the web has a solvent content of 10 wt% or less, The invention which gives a pressure of 0.2 to 10 KPa is described. As a more preferred embodiment, when applying the tension using a nip roll as a method of terminating the application of tension when the solvent content is 4% by weight or more or applying pressure from both sides of the web (film), the number of nip roll pairs is from 1. It is also disclosed that about 8 sets are preferable, and the temperature when pressurizing is preferably 100 to 200 ° C.

In addition, JP 2002-036266, which is an invention for obtaining a high-quality thin tack having a thickness of 20 to 85 μm, has, as a preferred embodiment, a tension that acts on the web along the conveying direction before and after the tenter. The difference is 8 N / mm ² or less. After the peeling process, a preheating process for preheating the web, a stretching process for stretching the web using a tenter after the preheating process, and after the stretching process, And a relaxation step for relaxing the web by an amount smaller than the drawing amount in the drawing step, and the temperature T ₁ in the preheating step and the drawing step is set to (the glass transition temperature T of the film).
and _g -60) ° C. or higher, and the temperature T ₂ in the relaxation step, (T 1 _-10) ℃ be less, a web of stretch rate in-stretching step, immediately before entering the drawing step the web width It is disclosed that the stretch ratio of the web in the relaxation process is -10 to 10% in a ratio of 0 to 30%.

Further, JP 2002-225054 A, which aims to be a thin film having a dry film thickness of 10 to 60 μm and a light weight, moisture permeability and a small durability, has a residual solvent amount of 10% by mass after peeling. Until both ends of the web are gripped by clips to suppress drying shrinkage by holding the width, and / or
Alternatively, the film is stretched in the width direction to form a film having a plane orientation degree (S) represented by the formula S = {(Nx + Ny) / 2} -Nz of 0.0008 to 0.0020 (where Nx Is the refractive index in the direction of the highest refractive index in the plane of the film, Ny is the refractive index in the direction perpendicular to the plane of Nx, Nz is the refractive index in the film thickness direction), from casting to peeling It is disclosed that the time is 30 to 90 seconds, the web after peeling is stretched in the width direction and / or the longitudinal direction, and the like.

Japanese Patent Application Laid-Open No. 2002-341144 describes a solution film-forming method having a stretching process in which the weight concentration of the retardation control agent has a higher optical distribution toward the center of the film width direction in order to suppress optical unevenness. Has been.

Furthermore, in Japanese Patent Application Laid-Open No. 2003-071863, which is an invention for obtaining a film that does not cause fogging, the draw ratio in the width direction is preferably 0 to 100%. It is described that -20% is more preferable, and 8-15% is most preferable. On the other hand, when used as a retardation film, 10 to 40% is more preferable.
It is disclosed that 0 to 30% is most preferable, and that Ro can be controlled by the draw ratio, and that a higher draw ratio is preferable because the flatness of the finished film is excellent. Further, when the tenter is used, the residual solvent amount of the film is 20 to 20 at the start of the tenter.
It is preferably 100% by mass, and drying is preferably performed while applying a tenter until the residual solvent amount of the film is 10% by mass or less, and more preferably 5% by mass or less. . In addition, the drying temperature in the case of performing the tenter is preferably 30 to 150 ° C, more preferably 50 to 120 ° C, most preferably 70 to 100 ° C, and the lower the drying temperature, the less the transpiration of the ultraviolet absorber or the plasticizer. It is also disclosed that process contamination can be reduced, but that the higher the drying temperature, the better the flatness of the film.

In addition, JP 2002-248639, which is an invention that reduces vertical and horizontal dimensional fluctuations during storage under high temperature and high humidity conditions, continuously casts a cellulose ester solution on a support. In the method for producing a film to be peeled and dried, an invention is described in which the drying shrinkage rate satisfies the formula 0 ≦ dry shrinkage rate (%) ≦ 0.1 × residual solvent amount (%) when peeling. Yes. Furthermore, as a preferred embodiment, when the residual solvent amount of the cellulose ester film after peeling is in the range of 40 to 100% by mass, at least the residual solvent amount is 30 mass while holding both ends of the cellulose ester film by tenter conveyance. % Of the remaining solvent is 40 to 100% by mass at the entrance of the tenter transport of the cellulose ester film after peeling, and the residual solvent is 4 to 20% by mass at the exit of the cellulose ester film. Make the tension to convey the ester film increase from the entrance to the exit of the tenter conveyance, ・ The tension to convey the cellulose ester film in the tenter conveyance and the tension in the width direction of the cellulose ester film are almost equal, etc. Is disclosed.

Incidentally, in order to obtain a film having a thin film thickness and excellent optical isotropy and flatness, JP-A-2000-239
403 shows the relationship between the residual solvent ratio X at the time of peeling and the residual solvent ratio Y at the time of introduction into the tenter.
It is disclosed that film formation is performed in the range of 3X ≦ Y ≦ 0.9X.

JP-A-2002-286933 includes a method of stretching a film to be formed by casting, a method of stretching under heating conditions and a method of stretching under solvent-containing conditions, and when stretching under heating conditions For stretching, it is preferable to stretch the film at a temperature below the glass transition point of the resin. On the other hand, when the film formed by casting is stretched under solvent impregnation conditions, the dried film is brought into contact with the solvent again. It is disclosed that it can be impregnated with a solvent and stretched.

The invention relating to these cellulose acylate tenters described above can also be applied to the present invention.

(After drying and handling)
The drying temperature in the drying step after peeling from the support of the cellulose acylate film of the present invention or after the tenter is preferably 40 to 250 ° C, particularly preferably 70 to 180 ° C.
Further, in order to remove the residual solvent, it is preferably used that it is dried at 50 to 160 ° C., and in that case, the residual solvent is evaporated by drying with high-temperature air whose temperature is changed successively. The above method is described in Japanese Patent Publication No. 5-17844. The drying temperature, the amount of drying air, and the drying time vary depending on the solvent used, and may be appropriately selected according to the type and combination of the solvents used. The amount of residual solvent in the final finished film is preferably 2% by mass or less, and more preferably 0.4% by mass or less in order to obtain a film having good dimensional stability.

As for the residual solvent amount of the film after drying, JP 2002-241511 discloses that even a thin film having a thickness of 20 to 60 μm eliminates deformation over time, is optically isotropic, and causes scratches. In order to eliminate bubbles and undissolved materials, there is described an invention in which the amount of residual solvent during winding is 0.05% by mass or less. As a more preferred embodiment, the difference between the maximum value and the minimum value of the residual solvent amount in the width direction is 0.02% by mass or less. The residual solvent amount is preferably 0.04.
It is disclosed that it is not more than mass%, particularly preferably not more than 0.02 mass%, and that the drying temperature is 100 to 200 ° C. and the drying time is 5 to 30 minutes.

Moreover, in order to reduce stable conveyance, surface improvement, necessary optical properties, and heat shrinkage, JP 2003-053751 A
Describes the invention in which when the residual volatile content (dry basis) in the base at the time of drying is 3 to 7 mass%, the poor solvent ratio in the residual volatile content is 0.01 to 95 mass% .

In addition, in JP 2003-071863, which is an invention for obtaining a film that does not cause fogging, in the film drying step, the film peeled off from the belt is further dried to reduce the residual solvent amount to 0.
. It is described that the content is preferably 5% by mass or less, more preferably 0.1% by mass or less, and most preferably 0 to 0.01% by mass or less.

In addition, in Japanese Patent Application Laid-Open No. 5-278051, for the purpose of physical properties excellent in productivity and having little difference between the front and back of the solute,
The solute is selected such that the interaction parameter χ between the solute and the polymer is 0.9 or less, and drying until the weight ratio of the solvent in the cast film to the polymer is 23% or less is performed. An invention of a solution casting method performed while maintaining the weight ratio of the surface of the membrane at 12% or more is described.

These inventions described above can also be applied to the present invention.

These steps from casting to post-drying may be performed in an air atmosphere or an inert gas atmosphere such as nitrogen gas. For drying, far infrared rays, JP-A-8-134336, JP-A-8-2
As described in Japanese Patent Application Laid-Open No. 59706 and Japanese Patent Application Laid-Open No. 8-325388, drying can be performed using a microwave.

Japanese Patent Laid-Open No. 2002-283370 discloses that a film cleaning device is arranged before introduction into a drying device or heat straightening device and / or after removal to remove dust adhering to the web. Has been described. As the cleaning means, methods other than the vibration / high pressure air supply / suction method, flame treatment (corona treatment, plasma treatment), a method of installing an adhesive roll, and the like are disclosed. In addition, as a preferable mode for preventing further foreign matter from being mixed, a static eliminator is installed at a position to be wound in the winding source winding tangent. <A configuration in which a reverse potential is applied by a static eliminator or a forced charging device at the time of winding so as to be ± 2 KV. The forced charging potential is 1 to 150 Hz.
In other words, it is disclosed that a static eliminator that alternately converts positive and negative is used, and that an ionizer or a static eliminator that generates ion wind is used.

These inventions described above can also be applied to the present invention.

JP-A-07-108547 discloses a method for producing a TAC in which a dope having a solid content of 15 to 35 mass% is dried with the volatile content in the film being X and the film surface temperature (° C) being Y. When 20 ≦ X ≦ 60, Y> −0.5X + 70, 0 ≦ X ≦ 20
Y> -6X + 180 is described, and the production rate of cellulose acylate is increased,
It is also possible to improve mechanical strength such as tear strength and processability, as disclosed in JP-A-07-112446.
The publication discloses a method for producing a protective film for a polarizing plate in which the volatile content in cellulose acylate is X%, the film surface temperature is Y ° C., and X and Y are the following. When 0 <X <20, Y> −6X + 1802, 0
In the case of ≦ X ≦ 60, Y> −0.5X + 70, and it is described that the birefringence is extremely small and the polarization degree of the polarizing plate is improved.

In Japanese Patent Application Laid-Open No. 61-1000042, the cellulose acylate metal support temperature is set to a temperature equal to or higher than the gel temperature of the dope temperature, and the maximum temperature is set to 30 ° C.-the temperature below the foaming temperature. According to the acylate manufacturing method, and JP-A-08-118378, the gradient of the tear strength from −20 ° C. to + 23 ° C. with respect to the temperature is 0.3 or less, and the film thickness is from 115 to 135.
For a cellulose triacetate film of μm, a dope of 15 to 35% by mass with a drying wind temperature T, a tear strength W after drying, and To-15 <T <T with respect to an inflection point temperature To of W against T
o An invention for drying at a drying air temperature is disclosed, and a cellulose acylate film that hardly breaks at low temperatures can be obtained, and can be applied to the present invention.

In Japanese Patent Application Laid-Open No. 61-110520, a windshield plate having a U-shaped cross section is provided so as to cover only the band portion where the dope is cast, and the cellulose acetate dope is made to flow on a metal support composed of an endless band. Then, hot air is sent to the wind shielding plate to volatilize the solvent to form a film, which enables high-speed production without foaming. In Japanese Patent Laid-Open No. 02-131174, 50 to 150 ° C., wind speed 3
A drying method in which the solvent is dried by touching at ~ 30 m / s and the residual solvent is evaporated by a heating roller is disclosed in Japanese Patent Laid-Open No. 04-286611. In the final drying step, the residual solvent immediately before entering the final step is set to 10% by mass or less. A method for producing a cellulose acylate that maintains the surface temperature in the range of glass transition temperature + 40 ° C. and the surface temperature is 15 ° C. lower than the temperature before the final step is disclosed in
In No. 185443, when the cellulose acylate dope is cast on a metal support cooled to 20 ° C. or lower, cooled, solidified, peeled and dried, the solvent is 40% by mass or more, and 30 cm or more from the end of the film. A solution forming method of a cellulose triacetate film is disclosed in which the surface temperature up to the inside of the sheet is cooled to 20 ° C. or less, thereby reducing the number of cleaning operations of the foreign matter growth prevention roller on the conveyance roller. The cellulose acylate film produced in the present invention can also be applied.

In JP 2000-002809 A, alignment film formation is performed by maintaining the surface temperature in the drying process of the coating liquid layer at 30 to 60 ° C. by blowing hot air from the high temperature to the low temperature on the surface of the coating liquid layer. A method of manufacturing a long flexible sheet having a material layer is disclosed, and a flexible sheet having an alignment defect layer for a liquid crystal panel and an optical compensation sheet without alignment defects can be easily manufactured in a continuous process. No. 001009 discloses a cellulose acylate which has a surface temperature and a volatile content formula and has excellent tearing and folding resistance and good flatness.
No. 6 discloses surface improvement by a drying method of a cellulose acylate film which is transported while pulling side edges in the width direction with a force that does not stretch the film after peeling the cellulose acylate. In the first publication, in the first and second drying chambers and the final drying chamber, the residual solvent of the film is 10% or less, and the surface temperature of the film is lower by 15 ° C. or more than the final drying chamber. Streaks are prevented by a method in which the film is transported by being wound around a roll while maintaining the temperature in the range of Tg to Tg + 40 ° C. These contents can also be applied to the cellulose acylate film produced using the non-chlorine organic solvent according to the present invention.

  Japanese Patent Application Laid-Open No. 11-235728 discloses that the web width is A at an arbitrary position in the drying step after web peeling, the width B is a position where the residual solvent ratio is reduced by 10% from that position, and the shrinkage therebetween. When the rate Sa is Sa = {(A−B) / A} × 100, Sa ≦ 5 and the cellulose acylate manufacturing method for dry conveyance is a countermeasure against the rot variation against the large shrinkage in the width direction of the web by high-temperature treatment. Japanese Patent Application Laid-Open No. 11-090942 discloses a cellulose acylate manufacturing method in which curled portions generated at an end portion are suppressed and conveyed in a drying and conveying process between peeling and winding from a metal support. The folding is improved by curling. As a still more preferred embodiment, the film is peeled from the support defined by the drying shrinkage ratio = (1−size when dried to 1% of residual solvent (cm) / size immediately after peeling (cm)) × 100), It is described that the drying shrinkage rate in the transport direction and width direction of the cellulose ester film until it is dried and wound is 0.1 to 7.0%.

Furthermore, in order to increase the tear strength and strengthen the film against breaking and tearing, Japanese Examined Patent Publication No. 49-4554 has a shrinking rate of 20% in the length and width directions in the drying process. The invention described above is described.

Further, in order to suppress optical unevenness generated at the edge of the corner portion of the polarizing plate, JP-A-2002-243
In 939, the area expansion coefficient X% after immersion in water at 20 ° C for 30 minutes is 0 ≦ X ≦ 7.2 × Y with respect to the film thickness Yμm.
An invention of ^-0.5 is described.

In order to reduce vertical and horizontal dimensional fluctuations during storage at high temperature and high humidity,
In No.-248639, in a method for producing a film in which a cellulose ester solution is cast on a support and continuously peeled and dried, the dry shrinkage ratio is expressed by the formula: 0 ≦ dry shrinkage rate (%) ≦ 0.1 × An invention is described in which drying is performed so as to satisfy the residual solvent amount (%) at the time of peeling.

In JP 2003-094470 A, in order to control optical properties, dimensional stability, and flatness, -4 ≦ MD−TD ≦ 4% and -6 ≦ MD + TD ≦ 6%
(Conveyance direction expansion / contraction ratio MD, width direction expansion / contraction ratio TD) is described. As a more preferred embodiment, the relationship of TD ≧ −4% and MD ≦ −1% is satisfied, and the step of stretching the film in the width direction in the stage from peeling the film from the support to winding up It is disclosed that the stretching ratio in the width direction of the film in this stretching step is 5% or less.

These inventions described above can also be applied to the present invention.

In JP-A-11-048271, when the solvent is peeled off and the solvent content is 50 to 12% by mass,
It is also solved by stretching and drying with a width stretching device, and applying a pressure of 0.2 to 10 KPa from both sides of the web with a pressure device when the solvent content is 10% by mass or less. The width-stretching device prevents the film from being deteriorated in flatness due to rapid shrinkage cutting, unevenness, and tension. Further, in Japanese Patent Application Laid-Open No. 64-055214, drying air is given to the back surface, the drying start is within 15 seconds from the start of casting, the direction of the drying air is obliquely forward in the metal support traveling direction, and the surface of the metal support is The angle formed is 40 to 80 degrees, the static pressure of the drying wind is 5 mmHg or more,
A method for producing cellulose acylate having a distance between the drying air outlet and the metal support surface of 5 to 50 mm is disclosed.

These inventions described above can also be applied to the present invention.

In JP-A-11-216732, when casting a TAC dope from a die onto a metal support of a casting part, the temperature of the metal support is 0.5 to less than the boiling point of the main solvent used for the dope.
This is a method for producing a cellulose acylate film having a low temperature of 55 ° C. and a casting draw ratio of 1.0 or more and 3.0 or less. It is an invention intended to improve the property and peelability. In Japanese Patent Application Laid-Open No. 10-006351, a TAC by a solution casting method in which a support temperature passes through a state of 10 to 30 ° C. between casting and peeling.
This is an invention disclosure of cellulose acylate having excellent dimensional stability as a liquid crystal display member. It is applied to the cellulose acylate film produced in these inventions.

Furthermore, Japanese Patent Application Laid-Open No. 11-123732 discloses a dope having a solvent content of 300% by mass or more on the metal support of the cast part or in the dry region of the dry part after peeling. This is a method for producing cellulose acylate that is reduced at a rate of 300% by mass or less per minute, and prevents deterioration in flatness, applicability and mechanical properties during rapid drying in high-speed casting. JP-A-11
No. 138568 uses a casting apparatus having a plurality of cooling rolls, and after the web has passed the final temperature of the drying process immediately before the cooling process, the web is conveyed while winding the cooling roll. With respect to the method for producing a cellulose acylate to be cooled, a cellulose acylate excellent in flatness without vertical wrinkles or vertical slippage during high-temperature drying can be obtained. JP 2
No. 000-176950 discloses a cellulose acylate residual solvent of 20% by mass or less and a surface temperature of 80 in a drying process comprising two or more drive rollers and a large number of free rollers.
More than ℃, web draw ratio is 1-1.05, drive roller conveyance tension at the drying start is 10k
With respect to the conveyance of cellulose acylate having a total contact time of 10 seconds or more with a free roll of gf / m or more, an excellent sheet-like cellulose acylate that does not cause vertical wrinkles or horizontal wrinkles is disclosed. These inventions can also be applied to the cellulose acylate film produced using the present invention.

In addition, Japanese Patent Application Laid-Open No. 63-70248 discloses that, in order to increase the drying speed, a high wind speed is applied from nozzles arranged above and below the web when drying is carried out in a zone filled with an inert gas. An invention is described in which hot air of an inert gas is blown and dried, and this invention is also applicable to the present invention.

Further, JP-A-4-82212 discloses an invention that regulates the tension applied to the film and the drying temperature under conditions that are not more than the yield value of the film determined by the residual solvent and temperature in order to provide an appropriate phase difference in the film. Has been described.

Further, in order to prevent the inner wall of the vaporized material and the film from adhering, JP-A-2001-198934 describes the temperature of the portion in contact with the drying air in the drying casing in the method of drying the film by circulating the drying air. An invention is described in which the temperature is higher by 5 ° C. or more than the saturation temperature of the low molecular weight substance contained in the dry air.

Japanese Patent Application Laid-Open No. 2002-241511 has been proposed in order to eliminate deformation with time even for a thin film of 20 to 60 μm, optically isotropic, no scratches, and to eliminate bubbles and undissolved materials. Is
An invention is described in which the amount of residual solvent at the time of winding is 0.05% by mass or less, and as a more preferred embodiment, part or all of the guide roll is replaced with a tendency roll (which rotates following the web conveyance speed). Thus, it is disclosed that scratches and elongation can be completely suppressed, and in the case of a guide roll, a low inertia roll is used as much as possible.

Furthermore, Japanese Patent Laid-Open No. 2002-283370, which is an invention that winds a film without loosening, prevents deformation due to blocking, reduces static charge, reduces the amount of charge, and prevents foreign matter from being mixed, is included in the drying and / or heat correction process. It is described that a means for removing the plasticizer that evaporates is arranged to wind the web. Further, as a preferred embodiment, the means for removing the plasticizer is a means for lowering the vapor pressure of the plasticizer during the drying and / or thermal straightening process, and the means for removing the plasticizer is dry and / or heat. A means for adding 5% to 50% of fresh air during the straightening process, a means for removing the plasticizer is heating to the metal surface that the plasticizer contacts during the drying and / or heat straightening process The means for removing the plasticizer is a means for circulating the air supplied during the drying and / or thermal straightening process and removing the plasticizer evaporated in the circulation process, etc. It is disclosed.

Furthermore, in JP-A-2001-198934, in order to suppress the vaporization of low molecular weight substances in the dry casing from adhering to the inner wall surface, and as a result, to prevent low molecular weight substances from adhering to the film, A method for drying a cellulose acetate film is described in which the temperature of the portion in contact with the drying air in the drying casing is 5 ° C. or more higher than the saturation temperature of the low molecular weight substance contained in the drying air.

Japanese Patent Application Laid-Open No. 2003-145562 discloses a high-temperature drying zone having a drying air temperature of 115 ° C. or higher in order to produce a film that is excellent in processability and has low curl in water and is suitable for production of a polarizing plate. And spray from the support surface side, the air surface side opposite to the support surface, or from both the support surface side and the air surface side, and dry air of 115 ° C. or higher from the air surface side. There is a description of a film manufacturing method in which the wind speed of dry air on the air surface is 3 m / s or less when blowing.

Further, JP-A-2003-146505 has a fine flat part and a concave part on the peripheral surface of the roller body as an inexpensive roller that does not cause defects such as scratches, pulling wrinkles, and surface projections. The web guide roller is characterized in that the average depth is not less than 5 μm and not more than 50 μm, and the occupied area ratio of the flat portion is not less than 50% and not more than 70%.

JP-A-2003-175522 discloses a method for preventing scratches and wrinkles that occur during roll conveyance.
A solution casting method is described in which knurling due to unevenness is imparted to at least one side end of a film in a step of drying the film peeled from the endless support while being rolled.

The invention relating to the drying step of these cellulose acylates described above can also be applied to the present invention.

(Transport)
Moreover, the surface shape of the roller for conveyance used at each process can use what was described in the patent gazette of patent / 2683122-2683124 of smooth / satin / grooved.

Further, regarding the conveyance, Japanese Patent Application Laid-Open No. 11-090942 discloses a curled portion generated at an end portion in a dry conveyance process until peeling after winding from the support to improve folding due to curl at both ends of the web. An invention for conveying while suppressing the above is described. As a further preferable or another aspect, in the drying and transporting process after peeling from the support and before winding, the curled portion generated at the end is cut and transported. ・ Ultrasonic vibration is applied to the blade. In the case of using an ultrasonic cutter that is cut by feeding to the web, cutting from 5 mm to 15 mm from both ends of the web is described.

In addition, in order to obtain a film excellent in quality in which vertical wrinkles and horizontal wrinkles are not generated,
-176950 includes a web draw ratio between drive rolls in a drying process consisting of two drive rollers and a number of free rollers, with a TAC residual solvent of 20 wt% or less and a surface temperature of 80 ° C or more. Is 1.00 to 1.05, and the conveying tension of the drive roller at the drying start point is 10 kg.
An invention in which the total contact time with a free roll is 10 seconds or more is described. Further, as a more preferable aspect, it is disclosed that the free roll has a configuration in which a tension is applied to the web in the width outward direction from the center of the roll, and the free roll has a surface roughness smaller than 3.0 μm. Yes.

Further, in order to stably and efficiently produce a thin film having a thickness of less than 85 μm, Japanese Patent Application Laid-Open No. 2001-113546 discloses that the web is dried so that the elastic modulus of the web is maintained at 0.1 kgf / mm ² or more. The invention has been described. As a more preferable embodiment, the web is formed between at least one of the dope casting process and the peeling process, or between the peeling process and the drying process, or between the drying process and the winding process. The tension Tkgf / mm ² acting on the web in the conveying direction and the elastic modulus Ykgf / mm ^{2 of the} web are expressed by the following equation T ≦ 20Y.
(Provided that 0 ≦ Y ≦ 0.1) or T ≦ 0.01Y + 1.999 (provided that 0.1 ≦ Y) is satisfied. The web is configured to be pulled in the width direction by at least a part of the web, and the tension acting on the web along the web conveyance direction provided in the middle of the conveyance path The total mechanical loss caused by the rotational frictional resistance of the conveying roll existing between the conveying tension control means and the winding means for controlling the web is 5 kgf or less per 1 m of the web width per 200 m of the conveying path length of the web.・ The contact of the web in the drying process that is dried while being conveyed via a plurality of conveying rolls, excluding the driving rolls that generate the driving force among the conveying rolls. The pressure is set to 0.0001 to 0.5 kgf / cm ^{2. In} a drying process of drying while transporting through a plurality of transport rolls, 80% or more of all locations where the transport rolls exist In this case, when the web residual melt WS and the holding angle θ formed by two perpendicular lines drawn from the tangent to the transport roll in the web to the rotation center of the transport roll are WS> 30, 5 ° < When θ ≦ 180 °, and when 0 ≦ WS ≦ 30, the web is transported so as to satisfy 5 ° ≦ θ ≦ 270 °, and a drying means for drying while transporting through a plurality of transport rolls The tension control means for controlling the tension acting on the web is interposed between the peeling means and / or between the drying means and the winding means in the web conveyance direction. control The difference in tension acting on the web before and after the means is configured to be 1 kgf or more per 1 m of the web width. The tension control means includes a drive roll that also serves as a transport roll, and the drive roll One or more webs are provided per 500 m of the web conveyance path length, and the web is dried by passing through a drying area controlled to a predetermined drying temperature, and the temperature difference inside the drying area is low (or high) ) To be 10% or less of the drying zone temperature, the temperature range of the drying zone at the inlet portion for allowing the web to enter the drying zone and / or the outlet portion for discharging the web from within the drying zone It is disclosed that air having an internal temperature is supplied in the form of a curtain. The tension control means mainly includes a hollow roll provided with a partition inside and a vacuum pump connected to the internal space of the roll, and innumerable fine holes are formed on the peripheral surface. However, when the vacuum pump is operated, air is discharged and the space becomes negative pressure, so the contacting part is adsorbed on the surface of this roll. It is also described that the tension difference before and after the tension control means is controlled to be optimum.

Furthermore, in order to suppress fuzz during ear picking and reduce failures in the subsequent process, Japanese Patent Application Laid-Open No. 2002-370242 describes an invention that performs charge removal at the time of ear cutting and charge removal at the time of charge removal from the cut ear. .
As a more preferred embodiment, the amount of methylene chloride remaining in the film obtained by drying the web and before being wound is set to 0.2% by mass or less.
This film is subjected to charge removal treatment, and the charge amount of the film after charge removal treatment is set to −1 to 1 k.
Making it within the range of v is disclosed.

In order to prevent scratches, deformations, creases and wrinkles from the transfer roll and improve dimensional stability, Japanese Patent Application Laid-Open No. 2003-019726 describes all of the transfer rolls of at least one of the drying and winding means. In the web contact part of 70 to 100% of the number of transfer rolls, a strong part and a weak part are provided in the width direction and the conveyance direction in the web, and the area ratio of both is 1/2 to 1/50. The invention is described. As a more preferable aspect, the part where the regulation force is weak in the web width direction and the conveyance direction is a part having a mirror surface with a surface roughness of Rmax 0.8 μm or less, and the web width direction and the conveyance direction are restricted. The strong part has a large frictional force compared to the mirror surface, and the combination of the strong part and weak part of the regulation force is a matted surface with a grooved surface / surface roughness Rmax 0.8 μm (fine irregularities Surface), mirror surface with surface roughness Rmax greater than 0.8 μm / mirror surface with surface roughness Rmax 0.8 μm or less, grooved surface / mirror surface with surface roughness Rmax 0.8 μm or less, grooved surface is a roll Having at least one spiral groove surrounding the circumferential surface; the grooved surface has at least one groove in the circumferential direction of the roll, the groove width is 0.05 to 5 mm, and the groove depth Is 0.05-5mm, The radius of curvature (R) of the substantially arcuate corners of the cross section on both sides of the groove opening is 0.05 to 1, the groove pitch is 0.1 to 300 mm, and the web or film of each roll is restricted. The parts with strong force are at both ends in the width direction of the contact part of the web, and the parts with strong regulating force against the web provided at both ends in the width direction of the web contact part of each roll A grooved surface having at least one spiral groove surrounding the roll, and appearing as a parallel groove inclined so that the spiral grooves at both ends of the roll spread outward in the left and right directions in the web transfer direction as seen from the plane.・ The part with strong regulating force is a grooved surface having at least one spiral groove surrounding the circumferential surface of the roll, and the spiral grooves at both ends of the roll are oriented in the web transfer direction as seen from the plane. Or The parallel grooves inclined to narrow the web central portion is provided so as appearing Te, web transfer speed, it is in 2～200M / min, transfer the tension of the web is,
60 to 250 N / m. -The outer diameter of the peeling roll and the transfer roll is 60 to 400
It is disclosed that it is mm, and the atmospheric temperature of the drying means and the winding means is 5 to 200 ° C.

Furthermore, in order to quickly find the free roll causing the failure, Japanese Patent Laid-Open No. 2002-283371 describes that the web is sequentially applied to a plurality of free rolls in each of the peeling process, the drying process and the winding process. An invention is described that uses different roll diameters for each process when transporting. As a more preferable aspect, the roll diameter of the free roll is gradually increased from the upstream process toward the downstream process for each process. The roll diameter of the free roll in each process is increased from the upstream side to the downstream side. Gradually increase towards the roll diameter of all free rolls 60-60
0 mm, preferably in the range of 70-350 mm, the tension acting on the web is 60-2
50 N / m, preferably 80 to 200 N / m, and the like are disclosed.

In order to perform stable conveyance, Japanese Patent Application Laid-Open No. 54-72847 describes an invention that defines the waveform of a conveyance web in PAC conveyance (non-contact conveyance).

Furthermore, in order to obtain a high-quality optical film that can be used for optical applications, JP-A-2002-194107
Describes an invention that defines the surface temperature, suction pressure, and stress difference of the drive roll.

In order to accurately control the position of the web even when the width of the web changes or a web with high transmittance, Japanese Patent Application Laid-Open No. 4-298443 is provided with an infrared projector on the top of the web immediately before the transmission, and infrared rays are irradiated. The image of the web end is copied by an optical system that has a two-dimensional image sensor provided directly above the end, and the correct end position is obtained from the image, detected, and the roll moves left and right according to the size of the position. An invention is described in which the speed is switched between two stages of high and low.

Furthermore, in order to reduce the operating cost by stably transporting with a small amount of blown air, JP-A-63-27360 describes the static pressure support type air blow angle in PAC transfer (non-contact transfer). An invention is described in which the interval between the air outlets at both edges of the air blowing box is at least 20 cm and 30 to 80% of the width of the web at 15 to 45 degrees inward with respect to the surface perpendicular to the surface.

In order to reduce the loss by automating the manual work at the start, JP-A-8-244053 describes that in the casting start method, the rear end can be dissolved in the dope solvent from the support surface to the next process. An invention is described in which a guide base having components is set and then cast, and this invention is also applicable to the present invention.

In addition, in order to ensure sufficient flatness without unevenness in the form of chimmen, JP-A-2001-113545 includes
When drying on the support, the air supply and exhaust ports have a wind speed of 1 m / sec., And the air supply and exhaust ports are located within 50 cm above the endless support normal, and casting dope is applied to the endless support. It describes an invention provided at a position passing after t seconds of the formula t = 100−X / 4 (X: casting thickness (μm)).

Furthermore, in order to adjust the relationship between (Rth) and the in-plane retardation value (Re),
In 001-100039, the tensile modulus in the machine direction is 360 to 480 kgf / mm ² , the tensile modulus in the direction perpendicular to the machine direction is 260 to 440 kgf / mm ² , and the tensile elasticity in the machine direction rate/
An invention is described in which the ratio of the tensile modulus in the direction perpendicular to the machine direction is 0.8 to 1.35.

Furthermore, in order to be able to cope with emergencies in the film production line,
In No. 95496, in the web separation system, in the process of transporting and winding the web, the running state of the web is monitored by a monitor, and the signal obtained from the monitor is compared with a preset value. An invention is described in which when the set value is exceeded, the web is separated and wound in the middle of conveyance.

The invention relating to the cellulose acylate conveying step described above can also be applied to the present invention.

(Curl correction)
In recent years, as liquid crystal display devices (LCD) are used in various places, durability, particularly durability against changes in temperature and humidity is required, and accordingly, polarizing plates which are components of LCDs are also representative durability. The demand for dimensional stability has increased. In addition, a film excellent in curling properties is also desired from the viewpoint of handling ability in post-processing. In an industrial process, since continuous film formation is performed, tension is applied in conveyance such as casting, film formation, tenter, and drying, which generates internal stress of the film and leaves it as strain. Moreover, on the support, drying is performed from the side opposite to the support surface, so that either surface tends to shrink due to uneven distribution of a plasticizer or the like in the thickness direction. Therefore, the web after drying is easily curled, and such a protective film for a polarizing plate appears as a dimensional change of the film when incorporated in a liquid crystal display device or the like, and wrinkles are generated. , Causing peeling or dimensional change of the polarizing plate due to the dimensional change of the protective film, curling the film on either the front or back, making it difficult to handle in the polarizing plate making process such as the polarizing plate bonding process if the curl is strong This causes problems such as deterioration of yield and high cost. Therefore, it is more desirable to correct the curl by forming a film by casting and then performing a humidification treatment. As the humidifying means, any of dipping means, coating means, and air humidity adjusting means may be used.

Regarding curl correction, Japanese Patent Publication No. 39-29211 describes an invention for producing a film having good flatness by spraying a solvent vapor while applying tension to the undried film in the width direction.

Further, for the purpose of preventing curling, Japanese Patent Publication No. 54-26582 describes an invention that defines three conditions of humidity, temperature and spraying time of wet hot air sprayed on the film.

For the purpose of shortening the time easily by the water vapor method, Japanese Patent Application Laid-Open No. 4-281448 describes an invention in which a main component gas is blown onto the surface of a cellulose ester or PC film to be curled.

Furthermore, Japanese Patent Application Laid-Open No. 2002-179819 describes an invention in which a dimensional change is reduced by forming a film by casting and then performing a humidification treatment. Furthermore, as a preferred embodiment, the film is subjected to a process in which the moisture content of the film is at least 3% by mass by the humidification treatment, the humidification treatment is performed at a temperature higher than room temperature, and more preferably the room temperature. The high temperature is 50 ° C. or higher, the humidification process is performed in the process from film formation to winding, the humidification process is performed with a roll film, and the film is formed. Thereafter, it is disclosed that a humidification process is performed.

The above-described invention relating to curling correction of cellulose acylate can also be applied to the present invention.

(Flatness correction)
The solution casting method has a great difficulty in that the film forming speed is low, and increasing the drying speed in the drying process has been an important industrial issue. Therefore, it is preferable to peel off the cellulose triacetate film from the casting surface as soon as possible and dry it from both sides of the cellulose triacetate film at a high temperature, and only a film having poor flatness can be obtained. That is, when the cellulose triacetate film is transported in the drying process, continuous wrinkles (hereinafter referred to as streaks) occur in the transport direction, and the streaks tend to occur frequently as the temperature increases. For example, the pitch is 30 to 50 mm, and the height of the unevenness during conveyance is 5 to 6
mm (0.5 to 1.0 mm when there is no tension at rest) was generated.
Therefore, it is desirable to perform flatness correction as a method for solving such problems. Regarding flatness correction, Japanese Patent Application Laid-Open No. 11-255387 relates to a method for correcting flatness in a winding process with a winding tension and a winding diameter after drying, and is an invention that can maintain flatness even during storage after winding. is there.

As flatness correction means, Japanese Patent Application Laid-Open No. 2000-319412 describes that a heating roll and a cooling roll are provided. In addition, as a heating roll, a calender roll which can be heated and pressurized, or a dense roll having a small interval between the rolls is preferable, and a dense roll is particularly preferable because of good heat transfer. It is disclosed that a range of 180 ° C. is preferred. Furthermore, the cooling roll of the flatness correction means that follows the heating roll has the same structure as the heating roll, and the cooling temperature is preferably in the range of 20 to 80 ° C.

Furthermore, for the purpose of obtaining a film with good flatness and good transparency and no surface failure even in high-temperature drying and high-speed film formation, JP-A-9-225953 disclosed that the web was peeled off from the support and dried. When a coating film is applied continuously in the coating section upstream of the flatness improving section, which is later provided with a heating roller and a cooling roller, a cation is formed in the uppermost layer of the coating film applied to cellulose or in the vicinity of the uppermost layer. Or the invention which provides an anionic polymer is described.

Japanese Patent Laid-Open No. 11-138568 discloses that a web is cooled by using a casting apparatus having a plurality of cooling rolls in order to obtain a film having excellent flatness without vertical wrinkles or vertical warp during high temperature drying. An invention is described in which after passing through the final temperature of the drying process immediately before the process, the web is cooled while being conveyed while winding a cooling roll. In addition, as a more preferable aspect, the cooling of the web is started in the cooling process before the temperature of the web is not lower by 10 ° C. than the final temperature of the drying step, the temperature of the web is lowered by at least 10 ° C., the cooling The total time that the web is in contact with the roll is 2 seconds or more and 10 minutes or less, and the number of cooling rolls is 10 to
30 are preferable from the viewpoint of cooling efficiency, size of equipment, cost of equipment, etc. ・ The diameter of the cooling roll is preferably 5-30 cm, and it is 10-20 cm from the web contact curve, contact time on one side, production cost, etc. Is more preferable. Furthermore, it is preferable that the angle at which the web is held by the cooling roll is as large as possible because the cooling efficiency is good. The cooling distance is as short as possible until the web is separated from the cooling roll that is in contact with the web and comes into contact with the next roll. It is also disclosed that efficiency is high. Furthermore, the cooling method of the cooling roll may be to circulate a liquid at a predetermined temperature inside the cooling roll, or to maintain the temperature by a built-in heat source, or to blow a wind at a predetermined temperature from above the cooling roll. It has been shown. Here, the final solvent content is preferably 2.0% by weight or less, more preferably 1.0% by weight or less, and the drying time should be set so that the solvent content of the film falls within these ranges. It is disclosed.

In addition, JP 2002-036266, which is an invention for obtaining a high-quality thin tack having a thickness of 20 to 85 μm, includes a free span stay time t _F and a web conveyance roll contact time t _R as preferred embodiments.
It is described that after the dense roll process in which the ratio value t _F / t _R is 5 or less, a thermal correction process for performing a cooling process is further provided.

Japanese Patent Application Laid-Open No. 4-260576 describes an invention for a support for a light-sensitive material having a side cross-sectional shape in which the thickness of the tip of the support is sequentially reduced in order to improve folding marks, pressure fog, and wrinkles. ing.

The above-described invention relating to flatness correction of cellulose acylate can also be applied to the present invention.

The thickness (after drying) of the cellulose acylate film of the present invention varies depending on the purpose of use, but is usually in the range of 5 to 500 μm, more preferably in the range of 20 to 300 μm, and most preferably in the range of 30 to 150 μm. preferable. The thickness of the film may be adjusted by adjusting the solid content concentration contained in the dope, the slit gap of the die base, the extrusion pressure from the die, the metal support speed, and the like.

The width of the cellulose acylate film obtained as described above is preferably 0.5 to 3 m, more preferably 0.6 to 2.5 m, and still more preferably 0.8 to 2.2 m. The length is preferably 100 to 10,000 m per roll, more preferably 500
It is -7000m, More preferably, it is 1000-6000m. When winding, knurling is preferably applied to at least one end, the width is 3 mm to 50 mm, more preferably 5 m to 30 mm, and the height is 0.5 to 500 μm, more preferably 1 to 200 μm. This may be a single push or a double push.

As for knurling, in order to make it easy to thicken the web, JP-A-11-2
In No. 62950, the tooth shape of the knurling roller (embossing roller) is formed in a pyramid shape, and
An invention in which the tooth tip angle is formed at 90 to 130 ° is described.

Furthermore, even in the case of a thin film web, in order to process the web thickness at high speed,
No. 01813 describes an invention in which when a film is sandwiched between rollers with a knurled roller, the roller is pressed while rotating.

Further, JP 2002-283370 A, which is an invention that winds a film without loosening, prevents deformation due to blocking, further reduces static charge, reduces the amount of charge, and prevents foreign matter from being mixed. Range of 0.05 to 0.3 times thickness T, width W is 0.005 of film width L
It is described that it is set to a range of ~ 0.02 times. It also discloses that it is preferable that the pressing force of the touch roll against the embossing formed at both ends of the web can be adjusted independently at both ends.

Furthermore, Japanese Patent Laid-Open No. 2003-147092 discloses a film roll in which the thickness of the end face in the film width direction is 2 μm or more smaller than the thickness of the knurling portion in order to obtain a film roll free from a failure caused by winding, and a winding method thereof Is described.

Japanese Patent Laid-Open No. 2003-114108 discloses a method for measuring the thickness of a web thickening portion that is measured online by scanning in the web width direction in order to accurately control the thickness of the web thickening portion. A method for measuring the thickness of the processed part is described.

Furthermore, in JP2003-117997, in order to perform a thickening process so as not to damage the web, the edge of the web is thickened by pressing the knurled teeth formed with a large number of truncated pyramids. In the processing method, there is described a web thickening processing method characterized in that the number of the chevron is 10 to 300 / cm ² and the sum total of the summit areas of the chevron is 1 to ²⁰ mm ² / cm ² . ing.

Japanese Patent Laid-Open No. 2003-162028 discloses a web having convex portions formed on both sides of a web edge as a thickening process so as not to slip even when the web is conveyed at high speed. There is a description of a web that has been processed to be thickened, wherein the overlap of the formed convex portions is less than 70%.

Furthermore, in JP-A-2003-167314, in order to prevent the occurrence of uneven coating as much as possible, in the belt-like film provided with a knurling portion on the side end portion and coated on one surface, the knurling portion is A film characterized by being provided only on the side opposite to the surface to be coated is disclosed.

In order to identify the film side at the time of forming a cellulose acetate film,
Japanese Patent No. 2002-210822 describes an invention in which a knurling roll is marked with a mark for identifying a film forming side.

The invention relating to knurling formed on the cellulose acylate web described above can also be applied to the present invention.

(Winding)
If winding is not performed at an appropriate winding hardness, various problems occur. For example, if the winding hardness is too hard, a blackish failure caused by a difference in thickness, adhesion between films, and a nick-like appearance failure caused by them occur. Also, if the winding is loose, the film roll may be depressed or beveled when it is stored, or the width direction deviation (hereinafter referred to as end face deviation) may occur during film winding or film roll conveyance. Occur. Such a defect becomes a fatal problem particularly in the case of an optical use film that requires high optical characteristics and flatness.

Conventionally, various measures have been taken to solve these problems. For example, adjusting the winding tension, installing a contact roll, optimizing the winding condition, or
Optimization of film thickness pattern, provision of slipperiness, charge control, improvement of film flatness, etc. are performed. In recent years, knurling (which is minute irregularities, also referred to as embossing, knurling, etc.) is imparted to the end of the film in the width direction to prevent end face displacement and loose winding.

In addition, when the film is taken up or re-drawn, the film peeling charge becomes high, so that foreign matter or the like is easily attached, leading to foreign matter failure. Therefore, it is preferable to perform static elimination immediately before film formation or at the time of winding. Note that the amount of charge can be reduced by adding a matting agent and reducing the contact area between the film surfaces. These techniques can also be applied to the present invention in a timely manner.

In order to wind up the film without loosening, prevent deformation due to blocking, reduce static charge, reduce the amount of charge, and prevent foreign matter from entering, JP 2002-283370 A describes that at the start of initial winding, 280
An invention is described in which winding is performed so that N / m width> pressing force by winding a touch roll (N / m width) + initial winding tension (N / width)> 60 N / m width. In addition, as a preferred embodiment, as a touch roll, a flat roll that is substantially in contact with only the embossing formed on the web is used. The embossing formed on the web has a height of 0 of the web film thickness. 0.05 to 0.3, the width is set to 0.005 to 0.02 of the film width, and the pressing force of the touch roll against the embossing formed at both ends of the web is independent at both ends.・ It can be adjusted. ・ When the web peeled off from the casting support is dried and wound around the core after heat correction, if necessary, the diameter of the original roll after winding may be different at both ends. Well, the difference in radius between both ends of the original roll of the product should be within 5mm. ・ When the web peeled off from the casting support is dried and heat-corrected as necessary, the product after winding Winding so that the winding hardness is (Embossed portion hardness−Hardness at the midpoint between the film end and the center) <170, The tape thickness for adhering the web to the core is 50 μm or less, Adhere the tape over the entire width of the core width, or stick the adhesive tape only on one side of the embossed on both ends of the web and wind up the web. It is disclosed that the web may be wound so that the charging potential of the film when it is re-drawn from the roll is within ± 2 kV.

Furthermore, in JP-A-2002-283370, the tape for bonding the web to the core is not a double-sided adhesive tape, but the single-sided adhesive tape is used to bond the web and the core, and at one end of the core, A double-sided adhesive tape having a width of 5 to 50 mm and a length of 10 to 50 cm is attached to a position on one emboss, and only one of the film ends is connected. In this embodiment, the film end connected to the core is θ = Cutting obliquely in the range of 10 to 60 degrees is also shown. Moreover, regarding the air conditioning / atmosphere of a winding part, setting to temperature 20-45 degreeC and humidity 40-80% RH is disclosed. Furthermore, it is described that it is preferable that the pressure can be controlled independently from both sides, and the pressure on both sides is preferably measured by a pressure detector. Furthermore, as a preferred embodiment, the initial tension of winding is set to a low tension such as 60 to 180 N / m width, and the shape of the touch roll is a flat roll that contacts the entire width of the film at the beginning of winding.・ Essentially, it should be a roll that contacts only the embossed part by embossing. ・ In the case of a system that only contacts the embossed part, it is necessary to shift the touch roll position according to the embossed position when the film width changes. There is disclosure. Also, to control the tension, use methods such as taper tension setting, function control tension setting, etc. ・ The material of the touch roll should be metal or hard synthetic resin. It is preferable that the position is immediately after the tangent line in contact with the wire, and the direction in which the touch roll moves as it rolls up is more preferably the normal direction from the winding core. In addition, winding is performed by setting the edge point control (EPC) of the winding unit to be fixed automatically from 0 to 5 seconds before winding is completed and 0 to 5 seconds after winding is started. In particular, the present invention is applicable to the present invention.

Furthermore, in order to prevent winding folds and wrinkles around the winding core, JP 2002-187147 describes an invention that defines the film tip shape, matting agent, film width, thickness, degree of cotton acetylation, etc. ing.

In order to prevent failures such as black belts and depressions, Japanese Patent Application Laid-Open No. 2002-211803 describes that in a film roll, the thickness difference in the width direction of the film is 5 μm or less excluding the knurling portion, and the knurling thickness is 3 to 3. The invention of 15 μm is described.

Furthermore, in order to eliminate winding misalignment and the like, Japanese Patent Application Laid-Open No. 2002-220143 describes an invention in which a film is pressed and wound with a predetermined force by a leion roll according to the thickness of the polymer film.

In order to prevent failures such as black belts and depressions, JP 2002-255409 discloses an invention for controlling the thickness of the air layer of the winding roll using knurling, thickness difference in the width direction, In addition, the invention of the winding method and roll which prescribe | regulate an electrostatic voltage, an oscillating winding, and winding length is described.

Furthermore, in order to prevent winding deviation, bulk roll depression, and ear extension, Japanese Patent Application Laid-Open No. 2002-068538 describes an invention that defines a knurling thickness.

Japanese Patent Application Laid-Open No. 11-255387 discloses that when the winding tension after drying is 1 ≦ d ≦ 1.4 in order to maintain and correct the flatness during storage after winding, 50 ≧ T ≧ -10d + 181, 50 ≧ T when 4 ≦ d ≦ 2
≧ 42, when 0 ≦ d ≦ 5, −10−10d + 70 ≧ T ≧ 45, and when 0 ≦ d ≦ 9, −4d + 40 ≧ T
≧ 4 (d is the winding diameter ratio, film roll winding diameter / core diameter, T is winding tension kg / m), and the invention is described. As a more preferred embodiment, when the film is wound on a take-up roll, the free span length between the contact point of the dried film with the film roll and the transport roll with which the film finally comes into contact is within 2 m. The film after drying is cooled to 45 ° C. or lower and then wound on a take-up roll, and the wound original winding is stored at 45 ° C. or lower.
The winding roll can be used without limitation as long as it is made of a homogeneous material accurately processed into a perfect circle, but it is described that the winding roll itself is not deformed or biased. Specifically, the material of the winding roll is, for example, stainless steel, bakelite, glass wool-lined plastic or ceramic, and the diameter of the winding core can be about 5 to 60 cm. It is described that 10 to 40 cm is preferable from the viewpoint of processing accuracy or value. In JP-A-11-255387, the humidity during winding and storing the original winding is preferably 70% RH or less, preferably 60% RH or less. It is disclosed that it is preferable to store in a humidity-controlled room.

Japanese Patent Laid-Open No. 2002-3083 discloses a core that winds up an optical film raw material for the purpose of reducing winding of the core, making it difficult to cause wrinkles at the beginning of the winding, and preventing back trouble of the horse even if stored for a long time. The invention has been described in which the centerline peak height RP of the surface of this is 0.05 to 1.0 μm. In addition, as a preferred embodiment, the amount of residual good solvent in the optical film original is 1% or less, the dynamic friction coefficient between the core surface and the optical film original is 0.1 to 1.5, and the optical film Grooves or projections are formed on the inner side of the winding core for winding the original fabric, the surface resistivity of the winding core for winding the optical film original fabric is 10 ¹² Ω / cm ² or less, optical The material of the surface of the core that winds up the original film is a hard urethane resin and / or epoxy resin. The core that winds up the optical film is selected from graphite, carbon fiber, or carbon black. It is disclosed.

Japanese Patent Laid-Open No. 2002-3083 discloses that with respect to the centerline peak height Rp of the original optical film, the smaller the Rp, the less the core transfer, and the larger the Rp, the smaller the friction coefficient and the core. It is disclosed that Rp is 0.05 to 1.0 μm, preferably 0.1 to 0.8 μm, and more preferably 0.3 to 0.6 μm because wrinkles are less likely to occur when starting to roll the film. Has been. Further, the amount of residual good solvent in the original optical film is preferably 1% or less.
. It is further preferably 5% or less, and most preferably 0.2% or less. It is described that the dynamic friction coefficient between the surface of the core and the film is preferably 0.1 to 1.5, more preferably 0.3 to 1.0, and still more preferably 0.5 to 0.8. In addition, there are various methods for controlling the dynamic friction coefficient, and it is disclosed that there are a method of adding inorganic fine particles such as silica to the optical film and a method of providing fine grooves on the circumference of the core surface. And
Regarding the preferable shape of the fine grooves provided on the circumference of the surface of the core, the pitch is 0.1 to 3 m.
m is preferable, 0.3 to 1 mm is more preferable, and the width is preferably 0.1 to 1 mm, 0
. 1 to 0.8 mm is more preferable, 0.1 to 0.5 mm is most preferable. Depth is preferably 1 to 20 μm, more preferably 2 to 10 μm, and most preferably 3 to 6 μm.

In JP-A-2002-3083, when a fine groove is provided on the circumference of the core surface, a long pitch, a narrow width, and a shallow depth are preferable because the core transfer is less, and the pitch is short. It is shown that a wider and deeper depth is preferable because it has a large effect of lowering the friction coefficient, and the groove may be concentric or spiral, but the spiral is more suitable for making the core. It is described that it is preferable because it is excellent in workability. Japanese Patent Laid-Open No. 2002-3083 also describes that the film original is preferably stored in a state in which the film core is supported and the film is not in direct contact with it in order to prevent scratches and deformation. Furthermore, as a preferable aspect of the film storage conditions, the film raw material is wrapped with a sheet of polyethylene or the like to avoid adhesion of foreign matters, and the temperature environment for storing the film raw material is preferably 5 to 40 ° C. 15 to 25 ° C. is more preferable.
It is disclosed that the humidity environment for storing the original film is preferably 20 to 70% RH, and more preferably 40 to 60% RH. This is because the film shrinks or expands when the temperature and humidity change, so the film roll wound around the core may be deformed, so store it at a temperature and humidity close to the manufacturing conditions. It has been shown that this is preferred. In general, the temperature at this time for transportation by car or ship, in the preserved state of transporting the film raw material,
It is disclosed that the humidity is preferably controlled in the same range as the method for preserving the original film.

Furthermore, in Japanese Patent Laid-Open No. 2003-146498, a web that is fed at a high speed and a wide width is pulled, and there is no generation of wrinkles. The web is cut so that the angle is 45 ° to 80 °, and the sticking position or cutting is performed so that the adhesive tape piece is attached at a position 0 to 100 mm away from the web tip and 0 to 170 mm away from the web side edge. A web wrapping method characterized by adjusting the position is described.

Further, JP 2003-014933 of the invention aimed at a retardation film with little additive bleed-out, no delamination phenomenon between layers, good slipperiness and excellent transparency, It is described that embossing is preferably performed on both ends. As a more preferable embodiment, if the height of the emboss (the difference in thickness between the inner portion of the emboss and the embossed portion) is too low, the film surfaces may be brought into close contact with each other and the film may be deformed. Since deformation may occur, it is shown that 5 to 30 μm is preferable. As the embossing method, for example, a known method applied to a thermoplastic resin film such as a polyester film can be preferably used. In particular, embossing is performed only on one surface without deforming the back surface of the film. It is described that it is preferable. As such an embossing method, an embossing ring heated near the melting point of the resin constituting the film (in the case of an amorphous resin, near the softening temperature) is used as a back roll 19 having a surface of metal, rubber, ceramic or the like. It is disclosed that the processing method of pressing on the film surface is preferable.

Furthermore, in Japanese Patent Application Laid-Open No. 2003-014933, as a winding method, there are a constant torque method, a constant tension method, a taper tension method, a program tension control method with a constant internal stress, and the like. It is disclosed. In order to adjust the film thickness, the dope concentration, the pumping amount, the slit gap of the die cap, the die extrusion pressure, the speed of the casting support, etc. are controlled so as to obtain the desired thickness. As a means for making the film thickness uniform, there is shown a method of using a film thickness detection means to feed back and adjust the programmed feedback information to each of the above devices.

Furthermore, in Japanese Patent Application Laid-Open No. 2002-255409, when winding a plastic film having a static friction coefficient of 0.3 to 0.9 in order to suppress the occurrence of depressions and black belts generated by storing a film roll,
A winding method is described in which the thickness of the air layer per film is 2 to 6.5 μm. Japanese Patent Application Laid-Open No. 2003-165656 describes an invention of switching by suction without using a winding tape when rewinding.

Japanese Patent Application Laid-Open No. 2001-11354 which is an invention for stably and efficiently producing a thin film having a thickness of less than 85 μm
In No. 6, a step portion is formed along the rotation axis direction of the take-up core on the peripheral surface of the take-up core provided in the take-up means, and the height of the step surface in this step portion is determined by the thickness of the film. It is disclosed to be equal. Furthermore, as a preferred embodiment, as the take-up core provided in the take-up means, in the state where the film has been taken up, [(center portion deflection in the core longitudinal direction / core diameter) × 1
00] may be used, and the core deflection rate represented by [00] may be 5% or less. In the winding process, the thickness is represented by [thickness of wound film layer / (number of winding times × film thickness)]. The index R is 1.0
It is disclosed that the film is wound around the winding core so that ≦ R ≦ 1.3.

JP 2002-370242 describes an invention that performs static elimination during winding in order to suppress fuzz during ear picking and reduce failures in subsequent processes. As a more preferred embodiment, the amount of residual methylene chloride in the film obtained by drying the web and before being wound is set to 0.2% by mass or less. The amount of charge of the film after the treatment is set within the range of −1 to 1 kv, • The film is subjected to static elimination treatment immediately before and during winding, and • The static elimination treatment of the film immediately before winding. Is carried out from at least one side of the film by a static elimination bar or static elimination blower, and the static elimination treatment of the film at the time of winding is performed by blowing ion wind on both end faces and the peripheral surface of the roll film being wound by the static elimination blower.・ Ion wind is blown on the peripheral surface of the roll-shaped film being wound up by the static eliminator blower. In order to keep the distance between the peripheral surface of the roll-shaped film and the static elimination blower constant, the distance between the winding roll and the static elimination blower should be gradually increased, after the film has been wound on the winding roll Discharging the wound film mounted on the winding roll, subjecting the winding film removed from the winding roll, etc. to the discharging process are disclosed.

For the purpose of charge detection, Japanese Patent Application Laid-Open No. 2001-277412 describes a microcharged site in a laminated material having two or more application layers on a support having a surface specific resistance of 1 × 10 ¹³ Ω / cm ² or more. The invention has been described in which there are 10 or less per 0.02 m ^{2 of the} laminated material, and this invention is also applicable to the present invention.

In addition, JP 2002-283370, which is an invention that winds a film without loosening, prevents deformation due to blocking, reduces static charge, reduces the amount of charge, and prevents foreign matter from being mixed, is equipped with a static eliminating device or a forced charging device The charge potential of the film when the film is re-drawn from the original volume is ±
It describes that the web may be wound up so that it is within 2 kV.

Further, in JP-A-2002-187148, the difference in length from the shortest part of the longest part of the web width is within a predetermined dimension, so that it is wound around the core so as not to cause a knick and winding deviation. Is disclosed. The above-described invention relating to winding of cellulose acylate and the like can also be applied to the present invention.

(surface treatment)
The cellulose acylate film can achieve improved adhesion between the cellulose acylate film and each functional layer (for example, the undercoat layer and the back layer) by optionally 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 is 10 ⁻³ to
This is so-called low temperature plasma that occurs under a low pressure gas of 20 Torr. Furthermore, plasma treatment under atmospheric pressure is also preferable.

(Plasma treatment)
The plasma treatment used for the surface treatment of the cellulose acylate film of the present invention will be described. Specifically, there are methods using vacuum glow discharge, atmospheric pressure glow discharge, etc., and other methods include methods such as flame plasma treatment. These are disclosed in, for example,
The methods described in Japanese Patent Nos. 123062, 11-293011 and 11-5857 can be used.

According to these plasma treatments, the surface of the cellulose acylate film in the plasma can be treated to give it a strong hydrophilic property, and in the plasma generator by glow discharge, between the opposing electrodes. These films to be imparted with hydrophilicity are placed, a plasma-exciting gas is introduced into the apparatus, and a high-frequency voltage is applied between the electrodes, so that the gases are plasma-excited and glow discharge is performed between the electrodes. Surface treatment can be performed. Among these, those using atmospheric pressure glow discharge are preferably used. A plasma-excitable gas is a gas that is plasma-excited under the above conditions, and includes chlorofluorocarbons such as argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, tetrafluoromethane, and mixtures thereof. It is done.

As these gases, an inert gas such as argon or neon and a reactive gas capable of imparting a polar functional group such as a carboxyl group, a hydroxyl group, or a carbonyl group to the surface of the plastic film is used as an exciting gas. . As reactive gas, in addition to hydrogen, oxygen, nitrogen,
In addition to gases such as water vapor and ammonia, organic compounds with low boiling points such as lower hydrocarbons and ketones can be used as necessary, but for handling, gases such as hydrogen, oxygen, carbon dioxide, nitrogen and water vapor are used. preferable. In the case of using water vapor, a gas obtained by bubbling other gas through water can be used. Alternatively, water vapor may be mixed.

The frequency of the high-frequency voltage to be applied is preferably 1 kHz or more and 100 kHz or less, more preferably 1 kHz or more and 10 kHz or less. There are a method of performing this under vacuum and a method of performing this under atmospheric pressure in plasma processing by glow discharge. In the vacuum plasma discharge process using glow discharge, it is necessary to introduce the reactive gas so as to keep the atmosphere in the range of 0.005 to 20 torr in order to cause discharge effectively. In order to increase the processing speed, it is preferable to adopt a high output condition on the high pressure side as much as possible. However, if the electric field strength is increased too much, the cellulose acylate film may be damaged. In the case of atmospheric pressure glow discharge in which plasma discharge is performed in the vicinity of atmospheric pressure, an inert gas such as helium or argon is necessary to cause stable discharge.
Stable discharge will not occur unless more than% is inert gas. However, if the inert gas is too much and the proportion of the reactive gas is small, the processing speed decreases. If the electric field strength is increased too much, the substrate may still be damaged. Even when plasma treatment is performed in the vicinity of atmospheric pressure, when generating plasma by pulsed electrolysis, the inert gas is not necessarily required, and the reaction gas concentration can be increased and the reaction rate can be increased. Can do

In order to form a uniform thin film on the surface of a long base material by discharge plasma treatment, JP 2002-33907 A
In No. 5, the long base material is arranged between the electrodes facing each other, and the atmospheric pressure or the atmospheric pressure from the gas inlet arranged in the slit shape along the width direction of the long base material provided between the electrodes. The invention describes that a thin film is formed on the surface of a substrate by applying a high-frequency voltage between electrodes while discharging a reaction gas under a pressure in the vicinity to discharge.

Furthermore, in order to increase transparency, decrease water vapor permeability, particularly increase the lifetime, increase contrast, or reduce color misregistration in a display method using birefringence, Japanese Patent Application Laid-Open No. 2002-292
No. 659 describes an invention in which a solution containing an organic polymer and a reactive metal compound is cast on a support, dried and peeled, and then dried by at least one transport method selected from roll transport and tenter transport. ing.

Furthermore, in order to obtain excellent adhesiveness, Japanese Patent Application Laid-Open No. 2000-356714 describes an invention in which the contact angle with the pure water on the surface in contact with the polarizer in the protective film for polarizing plate is less than 55 degrees. In more detail, as an embodiment, the plasma treatment may be hydrophilized, the plasma treatment may be selected from vacuum glow discharge, atmospheric pressure glow discharge and flame plasma treatment. The surface to be bonded to the polarizer may be plasma-treated before bonding, or the surface to be bonded to the polarizer of the polarizing plate protective film may be bonded to the polarizer through the water washing step after the plasma treatment. It is described that it is good.

In order to obtain a film that does not peel off from the photosensitive layer even by cutting,
In No. 01-255625, in the hydrophobizing surface treatment method for a support, one surface of the support is treated with argon in a gas discharge plasma treatment at atmospheric pressure or near pressure and 50% by pressure or more of the introduced inert gas. An invention is described in which a reactive gas such as a hydrocarbon gas and / or a fluorinated hydrocarbon gas is contained as a gas and is continuously conveyed and processed.

Furthermore, in order to reduce the dimensional change without deteriorating even at high temperature and high humidity, JP 2003-066202 discloses an optical film and a method for producing the same directly on the cellulose ester film with little dimensional change or other An invention is described in which a metal compound layer is formed by discharge plasma through a layer.

In addition, it improves the adhesion of the support surface even during ultra-high speed conveyance, and increases the polar functional group application efficiency.
For the purpose of uniformly performing the surface treatment, JP 2000-246091 discloses an arbitrary substrate,
In the surface treatment method for performing surface treatment with plasma, an invention using plasma generated in a pulsed electric field at atmospheric pressure or in the vicinity thereof is described.

In addition, JP 2000-248091 discloses a surface treatment of a support for the purpose of improving the adhesion of the surface of the support even during ultra-high speed conveyance, increasing the efficiency of imparting polar functional groups, and performing the surface treatment uniformly. In the method, there is described an invention in which a continuous support that is continuously conveyed is subjected to a plasma treatment under atmospheric pressure or a pressure in the vicinity thereof, and is processed in air using a pulsed electric field. Yes.

Furthermore, in order to provide a metal compound thin film and provide an optical film that is stable and excellent over time at high temperature and high humidity, Japanese Patent Application Laid-Open No. 2003-114333 describes a dope for a base layer having a different composition in a method for producing an optical film. On one surface layer of the co-cast / sequential cast cellulose ester film with the surface layer dope, plasma discharge treatment with a reactive gas at atmospheric pressure / near is performed to form a metal compound thin film having a carbon content of 0.1 to 5 wt% The invention has been described.

Further, in order to form a multilayer thin film uniformly at a low cost, continuous processing, JP 2002-322558 A,
In the thin film forming method, an invention in which plasma discharge treatment is performed while supplying a reactive gas to an electrode gap under atmospheric pressure or a pressure near atmospheric pressure on the surface of a base film having a dynamic friction coefficient of 0.9 or less on the back surface. Has been described.

Further, for the purpose of preventing curling, JP-A-9-218302 describes an invention in which at least one surface of a transparent resin film is treated with a solvent in a protective film for polarizing plate.

Further, in order to lower the color and improve the adhesion, hydrophilicity and dyeability, Japanese Patent Application Laid-Open No. 55-018469 discloses an invention in which a polymer surface is heated and discharged in a method of vacuum glow discharge treatment of the polymer surface. Is described.

Furthermore, JP 2003-098303 A has a counter electrode, high-frequency voltage applying means, and means for supplying a rare gas and a reactive gas between the electrodes. This is a device that performs plasma discharge treatment of the base material, supplies the reaction gas for forming the antifouling layer between the counter electrodes, applies a high frequency voltage, and performs plasma discharge treatment at atmospheric pressure / near the base material transferred between the counter electrodes. An optical film having an antifouling function and an antireflection effect has been proposed in which an antifouling layer is formed on a thin film.

Further, regarding other plasma processing, JP 2003-161807, JP 2003-166063, JP 2003-171770, JP 2003-183836, JP 2003-201568, JP 2003-201570, etc. Are disclosed in each of the following publications.

These inventions described above can also be applied to the present invention.

The surface energy of the solid obtained by these methods is obtained by the contact angle method, the wet heat method, and the adsorption method as described in “Basics and Application of Wetting” (issued by Realize 1989.12.10). It is preferable to use the contact angle method, and the contact angle of water is 5 to 90 °
Furthermore, 5-70 degrees is preferable.

Other glow discharge treatments are described in US Pat. No. 3,462,335, US Pat. No. 3,761,299, US Pat. No. 4,072,769 and British Patent No. 891469.
A method described in JP-A-59-556430 in which the discharge atmosphere gas composition is changed to only the gas species generated in the container by subjecting the polyester support itself to a discharge treatment after the start of discharge is also used. In addition, the method described in Japanese Examined Patent Publication No. 60-16614, in which the surface treatment of the cellulose acylate film is performed at 80 ° C. or more and 180 ° C. or less when the vacuum glow discharge treatment is performed, can also be applied. The vacuum degree during the glow discharge treatment is preferably 0.5 to 3000 Pa, more preferably 2 to 300 Pa. The voltage is preferably between 500 and 5000V, more preferably between 500 and 3000V. The discharge frequency to be used is from direct current to several thousand MHz, more preferably 50 Hz to 20 MHz, and further preferably 1 KHz to 1 MHz. The discharge treatment intensity is preferably 0.01 KV · A · min / m ^{2 to 5} KV · A · min / m ² , more preferably 0.15 KV · A · min / m ^{2 to 1} KV · A · min / m ² . is there.

The ultraviolet irradiation method is also preferably used in the present invention, and is preferably carried out by the treatment methods described in JP-B 43-2603, JP-B 43-2604 and JP-B 45-3828. The mercury lamp is a high-pressure mercury lamp made of quartz tube, and the wavelength of ultraviolet rays is 180-380.
Those between nm are preferred. As for the method of ultraviolet irradiation, a high pressure mercury lamp with a dominant wavelength of 365 nm can be used as long as the surface temperature of the cellulose acylate film rises to around 150 ° C. in terms of the performance of the support. When low-temperature treatment is required, a low-pressure mercury lamp having a dominant wavelength of 254 nm is preferable. It is also possible to use an ozone-less high-pressure mercury lamp and a low-pressure mercury lamp. With respect to the amount of processed light, the greater the amount of processed light, the better the adhesion between the cellulose acylate film and the adherend layer, but the problem arises that the film becomes colored and becomes brittle as the amount of light increases. Therefore, 365
A high-pressure mercury lamp having a main wavelength of nm has a good irradiation light quantity of 20 to 10,000 (mJ / cm ² ), more preferably 50 to 2000 (mJ / cm ² ). In the case of low-pressure mercury lamp for a 254nm main wavelength, the irradiation light amount 100~10000 (mJ / cm ²⁾ C., more preferably 300~1500 (mJ / cm ^2).

Next, corona discharge treatment is also preferably used as the surface treatment of the cellulose acylate film, and each of JP-B-39-12838, JP-A-47-19824, JP-A-48-28067, and JP-A-52-42114. It can be performed by a processing method described in the publication. As the corona discharge treatment apparatus, a solid state corona treatment machine manufactured by Pillar, a LEPEL type surface treatment machine, a VETAPHON type treatment machine, or the like can be used. The treatment can be performed at normal pressure in air. The discharge frequency during processing is 5 to 40 KV, more preferably 10 to 30.
KV and the waveform is preferably an alternating sine wave. The gap transparent lance between the electrode and the dielectric roll is 0.1 to 10 mm, more preferably 1.0 to 2.0 mm. The discharge is processed above a dielectric support roller provided in the discharge zone, and the treatment amount is 0.3 to 0.4 KV · A · min /
m ² , more preferably 0.34 to 0.38 KV · A · min / m ² .

Next, the flame treatment will be described. The gas used may be natural gas, liquefied propane gas, or city gas, but the mixing ratio with air is important. This is because the effect of surface treatment by flame treatment is thought to be brought about by plasma containing active oxygen, and the point is how much plasma activity (temperature) and oxygen are important properties of flame. is there. These two factors are determined by the gas / oxygen ratio. When the reaction is performed without excess or deficiency, the energy density is the highest and the plasma activity is increased. Specifically, the preferable mixing ratio of natural gas / air is 1/6 to 1/10, preferably 1/7 to 1/9 in volume ratio. In the case of liquefied propane gas / air, 1/14 to 1/22, preferably 1/16 to 1/1.
9. In the case of city gas / air, it is 1/2 to 1/8, preferably 1/3 to 1/7. Also,
The flame treatment amount may be 1 to 50 Kcal / m ² , more preferably 3 to 20 Kcal / m ² . The distance between the tip of the burner inner flame and the film is 3 to 7 cm, more preferably 4 to 6 cm. The burner nozzle shapes are: Flynburner (USA) ribbon type, Wise (USA) multi-hole type, Aerogen (UK) ribbon type, Kasuga Electric (Japan) staggered multi-hole type, Koike Oxygen ( Japan) is preferred. The backup roll that supports the film for flame treatment is a hollow roll, which is cooled with water through cooling water and is always 20-50 ° C.
It is better to process at a constant temperature.

[Alkaline saponification]
The saponification treatment is performed by immersing, spraying or coating a saponification solution on a transparent support. Preferably, a saponification treatment is preferably performed by coating, and examples of the coating method include a dip coating method, a curtain coating method, an extrusion coating method, a bar coating method, and an E-type coating method.

[Alkaline solution]
The alkaline solution of the present invention is preferably an alkaline solution having a pH of 11 or more. More preferably pH 1
2-14. Examples of the alkali agent include inorganic alkali agents such as sodium hydroxide, potassium, lithium and ammonium, diethanolamine, triethanolamine, DBU (1,8-diazabicyclo [5,4,0] -7- Undesen), DBN (1
, 5-diazabicyclo [4,3,0] -5-nonene), tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, triethylbutylammonium hydroxide, etc. Is also used. These alkali agents can be used alone or in combination of two or more, and a part of them may be added in the form of a salt, for example, halogenated. Among these alkali agents, sodium hydroxide or potassium hydroxide is preferable because the pH can be adjusted in a wide pH range by adjusting these amounts. The concentration of the alkaline solution is determined according to the type of alkaline agent used, the reaction temperature and the reaction time. The content of the alkaline agent is preferably 0.1 to 5 mol / Kg in the alkaline solution, 0
. 5-3 moL / Kg is more preferable.

The solvent of the alkaline solution of the present invention is preferably composed of a mixed solution of water and a water-soluble organic solvent. As the organic solvent, any organic solvent miscible with water can be used, but those having a boiling point of 120 ° C. or lower, more preferably 100 ° C. or lower are preferable. Among them, a preferable organic solvent has an inorganic / organic value (I / O value) of 0.5 or more and a solubility parameter of 1.
The thing of the range of 6-40 [mJ / m < ³ >] < ^1/2 > is preferable. More preferably, the I / O value is 0
. 6-10, and a solubility parameter is 18-31 [mJ / m < ³ >] ^1/2 . I / O
If the value is more inorganic than this range or the solubility parameter is low, the alkali saponification rate decreases and the overall uniformity of the saponification degree becomes unsatisfactory. On the other hand, when the I / O value is on the organic side of the above range, or the solubility parameter is highly soluble, the saponification rate is fast,
Haze is likely to occur, and therefore it is similarly unsatisfactory in terms of overall uniformity. In addition, when an organic solvent, particularly an organic solvent in each of the above-mentioned organic and soluble ranges, is used in combination with a surfactant, a compatibilizing agent, etc. described later, a high saponification rate is maintained and the saponification degree is uniform over the entire surface. Improves.

Examples of the organic solvent having preferable characteristic values include those described in “Synthetic Organic Chemistry Association”, “New Edition Solvent Pocket Book” (Ohm Co., Ltd., published in 1994) and the like. (Also,
Regarding the inorganic / organic values (I / O values) of organic solvents, for example, Yoshio Tanaka's organic conceptual diagram)
Sankyo Publishing Co., Ltd. published in 1983, pages 1-31).

Specifically, monohydric aliphatic alcohols (eg, methanol, ethanol, propanol,
Butanol, pentanol, hexanol, etc.), alicyclic alkanols (eg, cyclohexanol, methylcyclohexanol, methoxycyclohexanol, cyclohexyl methanol, cyclohexyl ethanol, cyclohexyl propanol, etc.), phenyl alkanols (eg, benzyl alcohol, phenyl ethanol) , Phenylpropanol, phenoxyethanol, methoxybenzyl alcohol, benzyloxyethanol, etc.), heterocyclic alkanols (furfuryl alcohol, tetrahydrofurfuryl alcohol, etc.), monoethers of glycol compounds (methyl cellosolve, ethyl cellosolve, propyl cell) Solve, methoxymethoxyethanol, butyl cell solve, hexyl cell solve, methyl carbitol, ethyl carb , Propyl carbitol, butyl carbitol, methoxy triglycol, ethoxy triglycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, etc.) ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) ),
Amides (eg, N, N-dimethylformamide, dimethylformamide, N-methyl-2-pyrrolidone, 1,3 dimethylimidazolidinone), sulfoxides (eg, dimethylsulfoxide) and ethers (eg, tetrahydrofuran, pyran) , Dioxane, trioxane, dimethylcellosolve, diethylcellosolve, dipropylcellosolve, methylethylcellosolve, dimethylcarbitol, dimethylcarbitol, methylethylcarbitol and the like. The organic solvent to be used may be used alone or in combination of two or more.

When the organic solvent is used alone or in combination of two or more, at least one organic solvent is preferably one having high solubility in water. The solubility of water in the organic solvent is preferably 50% by mass or more, and more preferably freely mixed with water. An alkaline solution having sufficient solubility in an alkali agent, a salt of a fatty acid by-produced by a saponification treatment, a carbonate salt generated by absorbing carbon dioxide in the air, and the like can be prepared. The use ratio of the organic solvent in the solvent is determined according to the type of the solvent, the miscibility (solubility) with water, the reaction temperature and the reaction time. The mixing ratio of water and organic solvent is preferably 3/97 to 85/15 mass ratio. The ratio is more preferably 5/95 to 60/40, and still more preferably 15 /
It is 85-40 / 60 mass ratio. Within this range, the entire film surface can be easily saponified uniformly without impairing the optical properties of the acylate film.

As the organic solvent contained in the alkaline solution used in the present invention, an organic solvent (for example, a fluorinated alcohol) different from the organic solvent having the above preferable I / O value is used as a surfactant described later.
You may use together as a solubilizing agent of a compatibilizer. The content is 0.1 with respect to the total weight of the working solution.
~ 5% is preferred. The alkaline solution used in the present invention preferably contains a surfactant. By adding a surfactant, the surface tension can be lowered to facilitate coating, and the uniformity of the coating film can be increased to prevent cissing failure, and haze that tends to occur in the presence of an organic solvent is suppressed. Progress evenly. The effect becomes particularly remarkable by the coexistence of a compatibilizer described later. There is no restriction | limiting in particular in surfactant used, Any of anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, a fluorochemical surfactant, etc. may be sufficient.

Specifically, for example, Tokiyuki Yoshida “Surfactant Handbook (new edition)” (Engineering Books, published in 1987), “Functional Creation / Material Development / Applied Technology of Surfactant”, Volume 1 (Technical Education Publishing) , Published in 2000) and the like. Among these surfactants, quaternary ammonium salts as cationic surfactants, various polyalkylene glycol derivatives as nonionic surfactants, polyethylene oxide derivatives such as various polyethylene oxide adducts, Betaine-type compounds as amphoteric surfactants are preferred. In the alkaline solution, it is also preferable to use a nonionic activator and an anionic activator or a nonionic activator and a cationic activator together in order to enhance the effect of the present invention. The amount of these surfactants added to the alkaline solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass.

The alkaline solution used in the present invention preferably contains a compatibilizing agent. In the present invention, the “compatibilizer” refers to a hydrophilic compound having a water solubility of 50 g or more with respect to 100 g of the compatibilizer at a temperature of 25 ° C. The solubility of the water of the compatibilizing agent is preferably 80 g or more, more preferably 100 g or more with respect to 100 g of the compatibilizing agent. When the compatibilizer is a liquid compound, the boiling point is preferably 100 ° C. or higher, and more preferably 120 ° C. or higher.

The compatibilizing agent has an action of preventing drying of the alkaline solution attached to a wall surface such as a bath for storing the alkaline solution, suppressing fixation, and stably holding the alkaline solution. Also, after applying the alkali solution to the surface of the polymer film and holding it for a certain period of time, until the saponification treatment is stopped, the applied alkali solution thin film is dried, resulting in precipitation of solids, This has the effect of preventing the solid from being difficult to be washed out. Furthermore, phase separation between water as a solvent and the organic solvent is prevented. In particular, due to the coexistence of the surfactant, the organic solvent and the compatibilizer described above, the treated polymer film has less haze and is stable and uniform even in the case of long continuous saponification treatment. This is the degree of saponification.

The compatibilizing agent is not particularly limited as long as it is a material satisfying the above conditions. For example, a water-soluble polymer containing a repeating unit having a hydroxy group and / or an amide group such as a polyol compound and a saccharide is preferably exemplified. . As the polyol compound, any of a low molecular compound, an oligomer compound, and a high molecular compound can be used. Examples of aliphatic polyols include alkanediols having 2 to 8 carbon atoms (for example, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, glycerol monomethyl ether, glycerol monoethyl ether, cyclohexanediol, cyclohexanedimethanol). , Diethylene glycol, dipropylene glycol, etc.), C3-C18 alkanes containing 3 or more hydroxy groups (for example, glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, hexanetriol, pentaerythritol, diglycerin) , Dipentaerythritol, inositol, etc.).
As the polyalkyleneoxy polyols, the same alkylene diols as described above may be bonded to each other, or different alkylene diols may be bonded to each other, but a polyalkylene polyol in which the same alkylene diols are bonded to each other is more preferable. . In any case, the number of bonds is preferably 3 to 100, more preferably 3 to 50. Specific examples include polyethylene glycol, polypropylene glycol, and poly (oxyethylene-oxypropylene).

Examples of saccharides include, for example, Chapter 2 of “Natural Polymers” edited by the Society of Polymer Science, Japan
Kyoritsu Publishing Co., Ltd., published in 1984), Ryohei Oda, “Modern Industrial Chemistry 22, Natural Products Industrial Chemistry I”
I ”(Asakura Shoten Co., Ltd., published in 1967) and the like.
Among them, saccharides that do not have a free aldehyde group and a ketone group and do not exhibit reducibility are preferable.
Sugars are generally classified into glucose, sucrose, trehalose-type oligosaccharides in which reducing groups are bonded, glycosides in which reducing groups of saccharides and non-saccharides are bonded, and sugar alcohols reduced by hydrogenation of saccharides. Both are suitably used in the present invention. For example, sucrose, trehalose, alkyl glycoside, phenol glycoside, mustard oil glycoside, D, L-arabit,
Rebit, Xyrit, D, L-Sorbit, D, L-Mannit, D, L-Exit,
D, L-Tallit, Zulsicit, Allozulcit, and reduced water candy are mentioned. These saccharides can be used alone or in combination of two or more.

Examples of the water-soluble polymer having a repeating unit having a hydroxy group and / or an amide group include natural gums (for example, gum arabic, guar gum, tragand gum, etc.),
Examples include polyvinylpyrrolidone, dihydroxypropyl acrylate polymer, addition reactants of celluloses or chitosans and epoxy compounds (ethylene oxide or propylene oxide). Of these, polyol compounds such as alkylene polyols, polyalkyleneoxy polyols and sugar alcohols are preferred.

The content of the compatibilizer is preferably 0.5 to 25% by mass and more preferably 1 to 20% by mass with respect to the alkaline solution.

Both the alkaline solution and the replenisher used in the present invention can contain other additives. Other additives include, for example, antifoaming agents, alkaline solution stabilizers, pH
Buffering agents, preservatives, antibacterial agents, etc.

[Alkaline saponification method]
The surface treatment method of the cellulose acylate film using the above alkaline solution may be any conventionally known method, but in particular, when only one surface of the film is uniformly saponified without unevenness, the coating method is preferable. As a coating method, a conventionally known coating method [for example, die coater (extrusion coater, slide coater), roll coater (forward roll coater, reverse roll coater, gravure coater), rod coater, blade coater, etc.] is preferable. Available. The saponification treatment is preferably carried out at a treatment temperature in a range not exceeding 120 ° C. at which deformation of the film to be treated and alteration of the treatment liquid do not occur. Further temperature 1
A range of 0 ° C. or higher and 100 ° C. or lower is preferable. In particular, a temperature of 20 to 80 degrees is preferable. The saponification time is determined by appropriately adjusting the alkali solution and the processing temperature, but it is preferably performed in the range of 1 second to 60 seconds. Further, the step of saponifying the cellulose acylate film with an alkali solution at a surface temperature of at least 10 ° C., the step of maintaining the temperature of the cellulose acylate film at least at 10 ° C., and the alkali solution to the cellulose acylate film It is preferable to carry out an alkali saponification treatment by a step of rinsing off. For the saponification treatment of the cellulose acylate film with an alkaline solution at a predetermined temperature, a step of adjusting the temperature to a predetermined temperature before coating, a step of adjusting the alkaline liquid to a predetermined temperature in advance, or The combined process etc. are mentioned. It is preferable to combine with a step of adjusting to a predetermined temperature before coating. After the saponification reaction, it is preferable to wash and remove the alkaline solution and the saponification treatment reaction product from the film surface by washing with water, neutralizing and washing with water. Specifically, for example, the contents described in WO02 / 46809 and the like can be mentioned.

(Solvent recovery)
In solution casting, a polymer solution is cast from a casting die onto a band or drum support, and after the cast film is dried, it is peeled off from the support with self-supporting properties, dried and wound up. In the processes up to this point, a gas containing a solvent (generally air or nitrogen) is generated. for that reason,
It is necessary to purify the gas by removing the organic solvent from such a gas.

Regarding solvent recovery, Japanese Patent Application Laid-Open No. 4-59015 discloses a gas treatment method in which primary treatment is performed with a rotary continuous adsorption / desorption device in order to reduce the amount of the regenerating gas and reduce the size of the secondary device. In the solvent gas adsorption treatment device that sends the solvent to the secondary device and treats the solvent, 30 to 90% of the rich solvent gas-containing gas obtained from the regeneration zone outlet of the primary device is circulated and recycled to the regeneration zone inlet side. The invention to be sent to is described.

In order to fully utilize the adsorption capacity of the adsorbent, Japanese Patent Laid-Open No. 4-59019 describes the use of a dilute concentration and a rich concentration in adsorbing two or more solvent gases by a solvent recovery method having two solvent adsorption devices. An invention is described that defines the order in which a concentration of gas is fed into two adsorbers.

Furthermore, for the purpose of solvent circulation regeneration, JP 2002-079533 discloses a solution casting method,
An invention is described in which 80 to 98% of the solvent released from the cast film to be dried is condensed and recovered, and the remainder is adsorbed on an adsorbent and recovered.

Japanese Patent Laid-Open No. 2002-178347 discloses a volatile solvent volatilized from a cellulose acylate solution and a volatile solvent adsorbed by an adsorbent in order to prevent decomposition and modification of the solvent that is adsorbed and recovered in the solution casting method. A solution casting method is described in which desorption is performed using a non-condensable gas having a relative humidity of 80% or less in the desorption process.

Further, Japanese Patent Laid-Open No. 2003-165129 discloses a first method for recovering a solvent that volatilizes when forming a film in order to recover and reuse the solvent to form a film having a good optical property value Rth. And the process of
A second step of removing water contained in the recovered solvent to 5.0% by weight or less, a third step of adjusting components to use the solvent from which water has been removed as a solvent for dissolving the polymer,
A solution casting method is described.

Japanese Patent Laid-Open No. 2003-165866 also discloses a method for removing a volatile additive contained in a recovered gas by reducing the gas temperature in order to remove the additive by a simple method and suppress the blockage of the gas recovery line. A first step and a second step of removing the volatilized additive by lowering the gas temperature than the first step.
The temperature T on the outlet side of the apparatus for lowering the gas temperature in the first step is M, where the melting point of the substance with the highest solid content of the volatilized additive contained in the gas is M. (M-20) ≦ T ≦ M
A method for removing additives in the range of is described.

The above-described invention relating to the solvent recovery of cellulose acylate can also be applied to the present invention.

(Film recovery)
Cellulose esters are plastics obtained by chemically treating pulp from natural resources such as linter and wood. With the recent increase in environmental awareness, from the standpoint of forest protection, further depletion of petroleum resources and carbon dioxide. Also from the viewpoint of reducing carbon emissions, it is preferable that the waste plastics be recycled without film reclamation or incineration. Cellulose plastics are made from various cellulose derivatives obtained by chemically treating cellulose, which is a natural polymer. Cellulose plastics are mainly used in the support of photographic films because of their optical properties and strength, and cellulose plastics are widely used as protective films for polarizing plates.

Regarding film recovery, in order to increase the transmittance and eliminate insoluble matter,
Describes the invention of pretreatment with an organic solvent solution containing at least one organic solvent capable of dissolving or swelling the cellulose triacetate film, or a solution containing an inorganic acid.

Furthermore, Japanese Patent Application Laid-Open No. 3-54557 describes an invention in which a photographic film is pretreated with a surfactant and the undercoat layer is removed by a process: proteolytic enzyme, and this invention is also applicable to the present invention.

In order to reduce impurities, Japanese Patent Application Laid-Open No. 5-271461 describes an TAC recovery method in which TAC is immersed in an alkaline aqueous solution or an acidic aqueous solution, and then treated with cellulase. The present invention can also be applied.

In addition, in order to enable collection processing in a short time, Japanese Patent Application Laid-Open No. 5-281686 discloses a TAC recovery method in which a molded product in which a surface layer is provided on a TAC is a peroxide or a participating halogen compound. And a treatment with a water-soluble organic solvent or an aqueous solution thereof.

Furthermore, JP-A-2000-273199 describes that the cellulose ester solution remaining in the step of filtering the solution is reused as a raw material.

Furthermore, for the purpose of cost reduction, Japanese Patent Application Laid-Open No. 2002-079534 describes an invention in which the remainder of the product film is used as a part of the raw material, and this invention can also be applied to the present invention.

In order to treat colored foreign matters and insoluble matter in a short time, JP 2001-019793 A discloses a cellulose plastic containing impurities based on a lower fatty acid ester of cellulose in a cellulose plastic impurity removing method. An invention is described for treatment with an aqueous solution containing a peroxide and a transition metal compound.

Furthermore, JP-A-2001-181440 describes an invention in which a polarizing plate is treated in an aqueous liquid in a method for recovering cellulose ester.

In addition, for the purpose of TAC high-purity recovery and reuse, JP-A-2001-300939 discloses a cellulose ester recovery method in which a film laminate for polarizing plates is crushed or cut, and then the cellulose ester film is separated by an electrostatic separator. It describes an invention that separates from other films, and may be further treated with an aqueous solution and dried, or may be purified by dissolving in an organic solvent capable of dissolving cellulose ester. It is described that the separating device may be by triboelectric charging.

Furthermore, in order to provide a regenerated cellulose ester, Japanese Patent Application Laid-Open No. 2001-213995 discloses a method for recovering a cellulose ester, for a liquid crystal image display device having a cellulose ester film having an acyl group substitution degree of 2.5 to 3.0. An invention is described in which the waste of the polarizing sheet is treated with an organic solvent having a solubility in cellulose ester.

Further, in order to regenerate cellulose acetate from a polarizing plate at a low cost, JP-A-2002-17983
In No. 5, cellulose acetate film containing acetone-soluble cellulose acetate was not dissolved in cellulose acetate film containing acetone-soluble cellulose acetate at 23 ° C and acetone or required cellulose acetate was dissolved in the cellulose acetate film regeneration method. And the invention of treating with an organic solvent is described.

Furthermore, in order to accurately prepare a dope having a constant composition by adding a part of the return material, Japanese Patent Laid-Open No. 2002-16114
In No. 3, in the preparation method of the cellulose ester dope, the content of the additive is changed to the content of the return material, the step of combining and transferring the additive solution transferring step, the step of mixing both solutions, and before each step. An invention is described that uses a dope preparation step having means (a) for calibrating and means for feeding back the calibrated additive content to the containing solution transfer step.

JP-A-2002-348403 discloses either a calcium compound or a polyol after crushing or cutting a polarizing plate containing a cellulose ester in a method for recovering cellulose ester in order to recover and reuse the polarizing plate. An invention of immersing in an aqueous solution containing benzene is described.

Furthermore, in order to regenerate from a polarizing plate at a low cost, Japanese Patent Application Laid-Open No. 2002-179835 discloses a cellulose acetate film containing acetone-soluble cellulose acetate in a cellulose acetate film regeneration method, cellulose triacetate having an acetylation degree of 60%. Is treated with an organic solvent that does not dissolve at 23 ° C. and dissolves acetone-soluble cellulose acetate.

The above-described invention relating to film recovery of cellulose acylate can also be applied to the present invention.

(Undercoat / Back material)
In order to achieve adhesion between the film and the emulsion layer, after surface activation treatment, a functional layer was directly applied on the cellulose acylate film to obtain adhesive force, and some surface treatment was performed once. There is a method in which an undercoat layer (adhesive layer) is provided or a functional layer is applied thereon after or without surface treatment. Various contrivances have also been made for the constitution of the undercoat layer, and a layer that is often adjacent to the support (hereinafter abbreviated as the undercoat first layer) is provided as the first layer, and a functional layer is provided as the second layer thereon. There is a so-called multi-layer method in which an undercoat second layer that adheres well is applied.

In the single layer method, the cellulose acylate film is often expanded to achieve good adhesion by interfacial mixing with the undercoat layer material. Examples of the primer polymer used in the present invention include water-soluble polymers, cellulose acylates, latex polymers, water-soluble polyesters and the like. Examples of water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, maleic anhydride copolymers, and cellulose acylates include carboxymethyl cellulose, hydroxy For example, ethyl cellulose. Examples of the latex polymer include a vinyl chloride-containing copolymer, a vinylidene chloride-containing copolymer, an acrylate ester-containing copolymer, a vinyl acetate-containing copolymer, and a butadiene-containing copolymer.

In the first subbing layer in the multi-layer method, for example, a copolymer starting from a monomer selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride and the like is used. As oligomers or polymers of polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, etc. (for these, see EH Immergut, Polymer Handbook IV187-2).
31, Interscience Pub. New York 1966)
.

Moreover, as a preferable aspect, the cellulose acylate film according to the present invention is provided with a hydrophilic binder layer for adhering to a polarizer. For example, a -COOM group-containing vinyl acetate-maleic acid copolymer compound, a hydrophilic cellulose derivative (for example, methyl cellulose, carboxymethyl cellulose, hydroxyalkyl cellulose, etc.), a polyvinyl alcohol derivative (for example, vinyl acetate-vinyl alcohol copolymer, polyvinyl Acetal, polyvinyl formal, polyvinyl benzal, etc.) natural polymer compounds (for example, gelatin, casein gum arabic, etc.) and hydrophilic group-containing polyester derivatives (for example, sulfone group-containing polyester copolymers).

The undercoat layer optionally applied to the cellulose acylate film according to the present invention can contain inorganic or organic fine particles as a matting agent to such an extent that the transparency of the functional layer is not substantially impaired. Silicon dioxide (SiO ₂ ), titanium dioxide (TiO ₂ ), calcium carbonate, magnesium carbonate, or the like can be used as the inorganic fine particle matting agent. Examples of organic fine-particle matting agents include polymethyl methacrylate, cellulose acetate propionate, polystyrene, a treatment solution-soluble one described in US Pat. No. 4,142,894, and US Pat. No. 4,396,706. A polymer or the like can be used. These fine particle matting agents preferably have an average particle size of 0.01 to 10 μm. More preferably, it is 0.05-5 micrometers. Further, the content thereof is preferably 0.5~600mg / m ^2, and more preferably from 1 to 400 mg / m ^2.

The undercoating liquid is generally a well-known coating method such as a dip coating method, an air knife coating.
Coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, slide coating method, or as described in US Pat. No. 2,681,294. The coating can be performed by an extrusion coating method using a hopper.

In order to realize a process that is easy to adhere to the PVA film and is safe and has no adverse environmental impact, JP-A-6-18183
In No. 2, in a protective film bonded adjacent to a polarizer composed of dyed and uniaxially stretched PVA, at least the surface to be bonded is coated with a hydrophilic polymer compound in a solvent having an affinity for the protective film. It describes a protective film for polarizing plate that has been dissolved and layered, and this invention is applicable to the present invention.

When using the produced cellulose acylate film, various functional layers are provided. These are, for example, an antistatic layer, a cured resin layer (transparent hard coat layer), an antireflection layer, an easy adhesion layer, an antiglare layer, an optical compensation layer, an alignment layer, a liquid crystal layer, and the like. Examples of these functional layers and materials thereof according to the present invention include surfactants, slip agents, matting agents, antistatic layers, and hard coat layers.

In JP-A-9-201912, when an actinic radiation curable resin layer is provided, an actinic radiation curable resin layer is provided on one side of the transparent resin film and a curl is provided on the opposite side in order to improve winding properties. There is a description of a protective film for a polarizing plate provided with a layer having a prevention function.

Furthermore, in JP-A-9-203810, a protective film for polarizing plate is provided on one side of a transparent plastic film in order to achieve both scratch resistance and antistatic properties, with low loss and good yield and low cost. A protective film for a polarizing plate having an antistatic layer containing an ionene conductive polymer and a hydrophobic binder, and further having a cured film layer formed by irradiating and curing an ultraviolet ray on a layer containing an ultraviolet curable resin composition Is described. These inventions described above can also be applied to the present invention.

(Surfactant)
First, the surfactant is classified into a dispersant, a coating agent, a wetting agent, an antistatic agent, and the like according to the purpose of use. However, the purpose can be achieved by appropriately using the surfactant described below. As the surfactant used in the present invention, either nonionic or ionic (anion, cation, betaine) can be used. Further, a fluorosurfactant is also preferably used as a coating agent in an organic solvent or an antistatic agent. The layer used may be a cellulose acylate solution or any other functional layer. When used in optical applications, examples of the functional layer include an undercoat layer, an intermediate layer, an orientation control layer, a refractive index control layer, a protective layer, an antifouling layer, an adhesive layer, a back undercoat layer, and a back layer. Although the amount used is not particularly limited as long as it is an amount necessary to achieve the purpose, it is generally preferably 0.0001 to 5% by mass, more preferably 0.0005 to the mass of the layer to be added. 2% by mass is preferred. The coating amount in that case is 1m
0.02-1000 mg per ² is preferable, and 0.05-200 mg is preferable.

Preferred nonionic surfactants include surfactants having nonionic hydrophilic groups such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyglycidyl and sorbitan, specifically, polyoxyethylene alkyl ether, polyoxyethylene Oxyethylene alkyl phenyl ether, polyoxyethylene-polyoxypropylene glycol, polyhydric alcohol fatty acid partial ester, polyoxyethylene polyhydric alcohol fatty acid partial ester, polyoxyethylene fatty acid ester, polyglycerin fatty acid ester, fatty acid diethanolamide, triethanolamine Mention may be made of fatty acid partial esters.

Examples of the anionic surfactant include carboxylate, sulfate, sulfonate, and phosphate ester salt. Representative examples include fatty acid salt, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfonate, α-olefin sulfonate, dialkylsulfosuccinate, α-sulfonated fatty acid salt, N-methyl-N oleyl taurine, petroleum sulfonate, alkyl sulfate, sulfated oil, polyoxyethylene alkyl ether sulfate, Examples thereof include polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene styrenated phenyl ether sulfate, alkyl phosphate, polyoxyethylene alkyl ether phosphate, and naphthalene sulfonate formaldehyde condensate.

Examples of cationic surfactants include amine salts, quaternary ammonium salts, pyridinium salts, etc., and primary to tertiary fatty amine salts, quaternary ammonium salts (tetraalkyl ammonium salts, trialkylbenzyl ammonium salts, Alkyl pyridium salt, alkyl imidazolium salt, etc.). Examples of amphoteric surfactants include carboxybetaine and sulfobetaine, such as N-trialkyl-N-carboxymethylammonium betaine and N-trialkyl-N-sulfoalkyleneammonium betaine.

These surfactants are described in Application of Surfactants (written by Koshobo, Takao Karie, published on September 1, 1980). In the present invention, the preferred surfactant is not particularly limited in the amount used, and may be any amount that provides the desired surface active characteristics. Specific examples of the surfactant are described below, but are not limited thereto (wherein —C ₆ H ₄ — represents a phenylene group).
WA-1: C ₁₂ H ₂₅ (OCH ₂ CH ₂ ) ₁₀ OH
_{WA-2: C 9 H 19} -C 6 H 4 - (OCH 2
CH ₂ ) ₁₂ OH
WA-3: Poly (polymerization degree 20) oxyethylene sorbitan monolaurate ester WA-4: Sodium dodecylbenzenesulfonate WA-5: Tri (isopropyl) sodium naphthalenesulfonate WA-6: Sodium dodecyl sulfate WA-7: α- Surufakohaku di (2-ethylhexyl) ester sodium salt WA-8: cetyltrimethylammonium chloride _{WA-9: C 11 H 23} CONHCH 2
CH ₂ N ⁺ (CH ₃ ) ₂ —CH ₂ COO ⁻
_{WA-10: C 8 F 17} SO 2 N (C 3 H 7) (CH 2 CH 2 O) 16 H
WA-11: C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ COOK
WA-12: C ₇ F ₁₅ COONH ₄
WA-13: C ₈ F ₁₇ SO ₃ K
_{WA-14: C 8 F 17} SO 2 N (C 3 H 7) (CH 2 CH 2
O) ₄ (CH2) ₄ SO ₃ N
a
_{WA-15: C 8 F 17} SO 2 N (C 3 H 7) - (CH 2) 3 -N + (CH 3) 3 · I -
_{WA-16: C 8 F 17} SO 2 N (C 3 H 7) CH 2 CH 2 CH 2 N + (CH 3) 2 -CH 2 C
OO ^-
_{WA-17: C 8 F 17} CH 2 CH 2 O (CH 2
CH ₂ O) ₁₆ H
_{WA-18: C 8 F 17} CH 2 CH 2 O (CH 2
) ₃ −N ⁺ (CH ₃ ) ₃ · I ⁻
_{WA-19: H (CF 2} ) 8 CH 2 CH 2
OCOCH ₂ CH (SO ₃ Na) COOCH ₂
CH ₂ CH ₂ CH ₂ (CF ₂ ) ₈ H
_{WA-20: H (CF 2} ) 6 CH 2 CH 2 O (CH 2 CH 2 O) 16 H
WA-21: H (CF ₂ ) ₈ CH ₂ CH ₂ O (CH ₂ ) ₃ —N ⁺ (CH ₃ ) ₃ · I ⁻
_{WA-22: H (CF 2} ) 8 CH 2 CH 2 OCOCH 2 CH (SO 3 K) COOCH 2 C
H ₂ CH ₂ CH ₂ C ₈
F ₁₇
WA-23: C _{9
F 17 -C 6 H 4 -SO 2} N (C 3 H 7) (CH 2 CH 2 O) 16 H
WA-24: C _{9
F 17 -C 6 H 4 -CSO 2} N (C 3 H 7) - (CH 2) 3 -N + (CH 3
) ₃ · I ^-

(Slip agent)
Further, a slipping agent may be contained in any layer on the cellulose acylate film, and in that case, the outermost layer is particularly preferable. As the slip agent used, for example, JP-B 53-
No. 292, US Pat. No. 4,275,514
Higher fatty acid amides as disclosed in No. 6 specification, Japanese Examined Patent Publication No. 58-33541,
British Patent No. 927446 or JP-A-55-126238 and JP-A-58-9
Higher fatty acid esters as disclosed in US Pat. No. 0633 (esters of fatty acids having 10 to 24 carbon atoms and alcohols having 10 to 24 carbon atoms) and higher fatty acids as disclosed in US Pat. No. 3,933,516 Fatty acid metal salts, and esters of linear higher fatty acids and linear higher alcohols as disclosed in JP-A-58-50534, International Publication 90
Higher fatty acid-higher alcohol esters containing branched alkyl groups as disclosed in No. 108115 are known.

Among these, as polyorganosiloxane, in addition to polyalkylsiloxanes such as polydimethylsiloxane polydiethylsiloxane and polyarylsiloxanes such as polydiphenylsiloxane and polymethylphenylsiloxane, which are generally known, JP-B 53-2
No. 92, Japanese Patent Publication No. 55-49294, Japanese Patent Application Laid-Open No. 60-140341, etc., an organopolysiloxane having an alkyl group of C5 or more, an alkylpolysiloxane having a polyoxyalkylene group in the side chain A modified polysiloxane such as an organopolysiloxane having an alkoxy, hydroxy, hydrogen, carboxyl, amino or mercapto group in the side chain can be used, and a block copolymer having a siloxane unit can also be used. Specific examples of such compounds are shown below, but are not limited thereto.
_{(S-1) (CH 3} ) 3 SiO- (Si (CH 3) 2
O) _a -Si (CH ₃ ) ₃
a = 5 to 1000
_{(S-2) (C 6} H 5) 3 SiO- (Si (CH 3) 2 O) a -Si (CH 3) 3

a = 5 to 1000
_{(S-3) (CH 3} ) 3 SiO- (Si (C 5 H 11) (CH 3) -O) a -Si (CH 3) 3
a = 10
_{(S-4) (CH 3} ) 3 SiO- (Si (C 12 H 25) (CH 3) -O) 10 - (Si (CH 3
) ₂ O) ₁₈ -Si (CH ₃ ) _{3
(S-5) (CH 3} ) 3 SiO- (Si (CH 3) 2 O) x - (Si (CH 3) ((CH 2) 3
_{-O (CH 2 CH 2 O)} 10 H) -O) y - (Si (CH 3) 2 O) z -Si (CH 3) 3 x
+ Y + z = 30
_{(S-6) (CH 3} ) 3 SiO- (Si (CH 3) 2 O) x - (Si (CH 3) {(CH 2) 3
_{-O (CH 2 CH (CH 3} ) -O) 10 (CH 2 CH 2 O) 10 C 3 H 7} O) y - (Si (CH 3
_{) 2 O) z -Si (CH} 3) 3 x + y + z = 35

In addition, higher fatty acids and derivatives thereof, higher alcohols and derivatives thereof include higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, higher fatty acid amides, higher fatty acid polyhydric alcohol esters, and the like. Use of monoalkyl phosphites, dialkyl phosphites, trialkyl phosphites, monoalkyl phosphates, dialkyl phosphates, trialkyl phosphates, higher aliphatic alkyl sulfonic acids, amide compounds or salts thereof of aliphatic alcohols Can do.
Specific examples of such compounds are shown below, but the present invention is not limited thereto.
(S-7) n-C 15 H 31 COOC 30 H 61 -n
(S-8) n-C 17 H 35 COOC 30 H 61 -n
(S-9) n-C 15 H 31 COOC 50 H 101 -n
(S-10) n-C 21 H 43 COO- (CH 2) 7
_{CH (CH 3) -C 9 H} 19
(S-11) n-C 21 H 43 COOC 24 H 49 -iso
(S-12) n-C 18 H 37 OCO (CH 2) 4
COOC ₄₀ H ₈₁ -n
(S-13) n-C 50 H 101 O (CH 2 CH 2 O) 15 H
(S-14) n-C 40 H 81 OCOCH 2 CH 2 COO (CH 2 CH 2 O) 16 H
(S-15) n-C ₂₁ H ₄₁ CONH ₂
(S-14) Liquid paraffin H
(S-16) Carnauba wax

By using such a slipping agent, it is possible to obtain an excellent film that has excellent scratch strength and does not cause repelling or the like on the undercoat surface. The amount of slip agent to be used is not particularly limited, but the content is preferably 0.0005 to 2 g / m ² , more preferably 0.001 to 1 g / m ^2.
m ² , particularly preferably 0.002 to 0.5 g / m ² . Although it does not specifically limit as an additive layer of the slip agent of this invention, It is preferable to make it contain in the outermost layer of a back surface. The surface layer containing the above-mentioned slipping agent can be formed by applying a coating solution obtained by dissolving this in a suitable organic solvent on a support or a support provided with another layer on the back layer, and drying. The slipping agent can also be added in the form of a dispersion in the coating solution. Solvents used include water, alcohols (such as methanol, ethanol, isopropanol), ketones (such as acetone, methyl ethyl ketone, cyclohexanone), esters (methyl such as acetic acid, formic acid, oxalic acid, maleic acid, succinic acid, Ethyl, propyl, butyl ester, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.) and amides (dimethylformamide, dimethylacetamide, n-methylpyrrolidone, etc.) are preferred.

In coating the slip agent, it can be used together with a binder having a film forming ability. As such a polymer, known thermoplastic resins, thermosetting resins, radiation curable resins, reactive resins, mixtures thereof, and hydrophilic binders such as gelatin can be used.

The sliding performance preferably has a static friction coefficient of 0.30 or less, more preferably 0.25 or less, and particularly 0.13.
The following is preferred. Further, it is preferable that the coefficient of static friction with the mating material to be contacted is small, which also helps prevent scratches. In this case, the coefficient of static friction with the mating material is preferably 0.3 or less, more preferably 0.25 or less, particularly preferably 0.13 or less. In many cases, it is preferable to reduce the static friction coefficient between the front and back surfaces of the film or optical film. The static friction coefficient between them is preferably 0.30 or less, more preferably 0.25 or less, and particularly preferably 0.13 or less. The coefficient of dynamic friction is preferably 0.30 or less, more preferably 0.25 or less, and particularly preferably 0.15 or less. The coefficient of dynamic friction with the mating material to be contacted is preferably 0.3 or less, more preferably 0.25 or less, and particularly preferably 0.15 or less. In many cases, it is preferable to reduce the dynamic friction coefficient of the front and back surfaces of the film or optical film. The dynamic friction coefficient between them is preferably 0.30 or less, more preferably 0.25 or less, and particularly preferably 0.13 or less.

Furthermore, in Japanese Patent Laid-Open No. 2003-096208, the coefficient of friction between film contact surfaces at a temperature of 23 ° C. and a humidity of 55% is set so that wrinkles and breakage do not occur even in a thin film having a thickness of 60 μm or less. When the same coefficient at a temperature of 23 ° C. and humidity of 80% is b and the same coefficient at a temperature of 23 ° C. and humidity of 85% is C, 1.0 ≦ b
There is a description of a cellulose ester film in which a relationship of /a≦1.5 and 1.0 ≦ C / a ≦ 5.0 is established.

For the purpose of excellent optical properties, Japanese Patent Application Laid-Open No. 2001-002807 has an average degree of acetylation of 58 to 62.5% provided with a coating layer containing a polymer and fine particles having an average particle size of 1.0 μm or less.
The cellulose acetate film has a haze of 2.0% converted to a thickness of 80 μm.
An invention is described in which the dynamic friction coefficient of the surface provided with the coating layer is 0.40 or less.

(Matting agent)
In the functional layer of the cellulose acylate film according to the present invention, it is preferable to use a matting agent for improving the slipperiness of the film and the resistance to adhesion under high humidity. In that case, the average height of the protrusions on the surface is preferably 0.005 to 10 μm, more preferably 0.01 to 5 μm.
m. Further, it is better that there are a large number of protrusions on the surface. A preferable protrusion is in a range having an average height of the protrusion, for example, when the protrusion is formed with a spherical or irregular matting agent, the content is 0.5 to 600 mg / m ² , and more preferable. Is 1 to 400 mg / m ² . At this time, as the matting agent used, the fine particles added to the cellulose acylate film described above can be used, and the composition thereof is not particularly limited, and may be an inorganic material, an organic material, or a mixture of two or more.

  Inorganic and organic compounds of matting agents include, for example, barium sulfate, manganese colloid, titanium dioxide, strontium barium sulfate, silicon dioxide, aluminum oxide, tin oxide, zinc oxide, calcium carbonate, barium sulfate, talc, kaolin, calcium sulfate, etc. Examples of the inorganic fine powder include silicon dioxide such as synthetic silica obtained by a wet method or gelation of silicic acid, and titanium dioxide (rutile type or anatase type) produced by titanium slug and sulfuric acid. It can also be obtained by pulverizing from an inorganic substance having a relatively large particle diameter, for example, 20 μm or more, followed by classification (vibration filtration, wind classification, etc.). In addition, polytetrafluoroethylene, cellulose acetate, polystyrene, polymethyl methacrylate, polypropyl methacrylate, polymethyl acrylate, polyethylene carbonate, acrylic styrene resin, silicone resin, polycarbonate resin, benzoguanamine resin, melamine resin, polyolefin powder Further, examples thereof include pulverized and classified products of organic polymer compounds such as polyester resins, polyamide resins, polyimide resins, polyfluorinated ethylene resins, and starch. Alternatively, a polymer compound synthesized by a suspension polymerization method, a polymer compound made spherical by a spray dry method or a dispersion method, or an inorganic compound can be used. Moreover, it is also possible to form an antiglare layer by adding 0.1 to 10 [mu] m particles having the same material and larger particle diameter and / or the aforementioned fine particles. It is preferable to add 0.5 to 20% by mass of fine particles. These fine particles are preferably silicon dioxide such as silica, for example, Silicia manufactured by Fuji Silysia Chemical Co., Ltd. and Nippon Sil E manufactured by Nippon Silica Co., Ltd.

For these fine particles according to the present invention, it is also preferable to use fine particles having an alkyl group or aryl group having 2 to 20 carbon atoms on the surface. The alkyl group preferably has 4 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms. The smaller the number of carbons, the better the dispersibility, and the larger the number of carbons, the less reaggregation when mixed with the dope. The surface used in the present invention has 2 to 2 carbon atoms.
Examples of inorganic compounds among the materials of fine particles having 20 alkyl groups and fine particles having aryl groups include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, and calcined. Calcium silicate,
Mention may be made of hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. Silicon dioxide, titanium dioxide and zirconium oxide are preferred,
Of these, compounds containing silicon atoms, particularly silicon dioxide, are preferred. Silicon dioxide fine particles are commercially available under trade names such as Aerosil 130, Aerosil 200, Aerosil 300 (manufactured by Nippon Aerosil Co., Ltd.). Further, silicon dioxide fine particles whose surfaces are modified with silicone oil and spherical monodispersed silicon dioxide fine particles are also preferably used.

Fine particles of an inorganic compound having an alkyl group having 2 to 20 carbon atoms on the surface can be obtained, for example, by treating the fine particles of silicon dioxide with octylsilane. Moreover, it is marketed by the brand name of Aerosil R805 (made by Nippon Aerosil Co., Ltd.) which has an octyl group on the surface, and can be used.

Fine particles of an inorganic compound having a phenyl group on the surface can be obtained, for example, by treating the fine particles of silicon dioxide with trichlorophenylsilane.

Among the materials of fine particles having an alkyl group having 2 to 20 carbon atoms and fine particles having a phenyl group on the surface, examples of the polymer include silicone resins, fluorine resins, and acrylic resins, and polymethyl methacrylate is particularly preferable. . As described above, a compound containing silicon is preferable, but silicon dioxide or a silicone resin having a three-dimensional network structure is particularly preferable, and silicon dioxide is most preferable.

JP-A-2001-183528 contains fine particles having a water content of 5 wt% or less having at least a resin and a solvent in order to improve optical characteristics, surface quality, antistatic performance, scratch resistance, adhesion, and the like. There is a description of an optical film in which a coating composition is applied on a film substrate and a resin layer is provided.

In order to prevent the adhesion of the roll film, Japanese Patent Application Laid-Open No. 2001-151936 discloses that in a cellulose triacetate film, at least the surface layer has an average particle size of 0.5 μm or more and 1.0 μm.
An invention containing 0.10% by mass to 0.15% by mass of silicon dioxide fine particles which is less than 10% is described.

Japanese Patent Laid-Open No. 2002-317059 discloses that the matting agent content is set to 0.03 to 0.15% by weight and the static friction coefficient is set to 0.4 in order to suppress a scratch failure during film winding without reducing the transmittance. ~ 0.7
The cellulose acylate film is described.

Furthermore, in JP-A-2003-119297, in order to prevent particle size control of secondary particle aggregates, spot-like defects, film sticking and deformation, uneven bonding with a polarizer, and coating unevenness, A cellulose ester film containing fine particles and a UV agent, where the average particle size of fine particles immediately after dispersion in a solvent is a μm, and the average particle size of fine particles in the dry film is B μm, a / B = 0.5
A cellulose ester film in the range of -1.0 is disclosed. These inventions described above can also be applied to the present invention.

These fine particles are preferably used in an amount of 0.005 to 0.3% by weight, more preferably 0.01 to 0.1% by weight, based on cellulose acylate. Thus, by using the fine particles according to the present invention, it is possible to obtain a cellulose acylate film having a very excellent fine particle dispersibility and containing 10 / m ² or less aggregated particles having a particle diameter of 10 μm or more.
These are described in JP-A-2001-2788.

(Antistatic agent)
The polarizing plate used as the optical film or polarizing plate protective film of the present invention can be subjected to antistatic processing, transparent hard coat processing, antiglare processing, antireflection processing, easy adhesion processing and the like. Alternatively, an alignment film can be formed and a liquid crystal layer can be provided to provide an optical compensation function. Details of these can be applied to the invention described in Japanese Patent Application Laid-Open No. 2000-352620, and will be described below.

Antistatic processing is a function to prevent the resin film from being charged when the resin film is handled. Specifically, a layer containing an ion conductive substance or conductive fine particles is provided. By doing. Here, the ion conductive substance is a substance that shows electric conductivity and contains ions that are carriers for carrying electricity, and examples include ionic polymer compounds.

Examples of the ionic polymer compound include Japanese Patent Publication No. 49-23828 and Japanese Patent Publication No. 49-23828.
And anionic polymer compounds as described in JP-B-47-28937; JP-B-55-734, JP-A-50-54672, JP-B-59-14735, JP-B-57
Ionene type polymers having a dissociating group in the main chain as seen in JP-B Nos. 18175, 57-18176, 57-56059, etc .;
, JP-B 57-15376, JP-B 53-45231, JP-B 55-145783
No. 55, 65950, No. 55-67746, No. 57-11342, No. 57-19735, No. 58-56858, No. Sho 61-27853,
Examples thereof include a cationic pendant type polymer having a cationic dissociation group in the side chain as seen in JP-B-62-2346.

Among these, the conductive material is preferably in the form of fine particles, and these are finely dispersed and added in the resin. As the preferable conductive material used for these, metal oxides and these It is desirable to contain conductive fine particles made of a complex oxide and ionene conductive polymer or quaternary ammonium cation conductive polymer particles having intermolecular crosslinking as described in JP-A-9-203810. The preferred particle size is in the range of 5 nm to 10 μm, and the more preferred range depends on the type of fine particles used.

Examples of metal oxides that are conductive fine particles include ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₂ , V ₂ O _5.
Or composite oxides thereof are preferable, and ZnO, TiO ₂ and SnO ₂ are particularly preferable. Examples of containing different atoms include, for example, addition of Al, In, etc. to ZnO, addition of Nb, Ta, etc. to TiO ₂ , and addition of Sb, Nb, halogen elements, etc. to SnO ₂ . Addition is effective. The amount of these different atoms added is preferably in the range of 0.01 to 25 mol%, particularly preferably in the range of 0.1 to 15 mol%.

These metal oxide powders having electrical conductivity have a volume resistivity of 10 ⁷ Ωcm or less, particularly 10 ⁵ Ωcm or less, and a primary particle diameter of 100 μm or more and 0.2 μm or less. It is preferable that the conductive layer contains a powder having a specific structure having a major axis of 30 nm to 6 μm in a volume fraction of 0.01% to 20%.

In addition, the characteristics of the cross-linked cationic conductive polymer as a dispersible granular polymer are that it has a high concentration and high density of the cation component in the particles, so that it has not only excellent conductivity. However, even when the relative humidity is low, the conductivity is not deteriorated, and the particles are well dispersed in the dispersed state. In addition, other substances such as a support have excellent adhesiveness and excellent chemical resistance.

These cross-linked cationic conductive polymers used in the antistatic layer are generally in the particle size range of about 10 nm to 1000 nm, preferably 0 nm to
A particle size in the range of 300 nm is used. The dispersible granular polymer used here is
A polymer that appears as a clear or slightly turbid solution by visual observation but appears as a granular dispersion under an electron microscope. By using a coating composition that does not substantially contain dust (foreign matter) larger than the particle diameter corresponding to the film thickness of the upper layer in the lower layer coating composition, failure of the upper layer foreign matter can be prevented.

The ratio between the fine particles and the resin is preferably 0.5 to 4 parts by mass of the resin with respect to 1 part by mass of the fine particles. It is preferable that it is -2 mass parts. Furthermore, organic electronically conductive organic compounds can also be used. For example,
Polythiophene, polypyrrole, polyaniline, polyacetylene, polyphosphazene and the like. These are preferably used in a complex with polystyrene sulfonic acid, perchloric acid or the like as an acid donor.

The resin used here is, for example, cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate phthalate, or cellulose nitrate, polyvinyl acetate, polystyrene, polycarbonate, polybutylene terephthalate, or copolybutylene / terephthalate. / Polyesters such as isophthalate, polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, polyvinyl butyral, polyvinyl alcohol derivatives such as polyvinyl benzal, norbornene-based polymers containing norbornene compounds, polymethyl methacrylate, polyethyl methacrylate, polypropylyl methacrylate, Acrylics such as polybutyl methacrylate and polymethyl acrylate It can be used a copolymer of fat or acrylic resin and other resins but not particularly limited thereto. Among these, a cellulose derivative or an acrylic resin is preferable, and an acrylic resin is most preferably used.

As the resin used for the resin layer such as the antistatic layer, the above-mentioned thermoplastic resin having a weight average molecular weight exceeding 400,000 and a glass transition point of 80 to 110 ° C. is in terms of optical characteristics and surface quality of the coating layer. preferable.

The glass transition point can be determined by the method described in JIS K7121. The resin used here is 60% by mass or more of the total resin used in the lower layer, more preferably 80% by mass.
The above is preferable, and an actinic radiation curable resin or a thermosetting resin can be added as necessary. These resins are coated as a binder in a state dissolved in the above-mentioned appropriate solvent.

In the coating composition for coating the antistatic layer, the following solvents are preferably used. As the solvent, hydrocarbons, alcohols, ketones, esters, glycol ethers, and other solvents can be used by appropriately mixing them, but are not particularly limited thereto.

Of these solvents, solvents with low boiling points tend to condense moisture in the air by evaporation,
It is easy to incorporate moisture into the coating composition in the preparation step and the coating step. In particular, it is easily affected by an increase in external humidity during rainfall, and the effect becomes prominent in an environment where the humidity is 65% RH or higher. Especially when the dissolution time of the resin is long in the liquid preparation process, the time that the coating composition is exposed to air in the coating process is long, or the contact area between the coating composition and air is large. Will grow.

Examples of the hydrocarbons include benzene, toluene, xylene, hexane, cyclohexane and the like, and examples of alcohols include methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butanol, 2-butanol, tert- Butanol, pentanol, 2-methyl-2-butanol, cyclohexanol, etc.
Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of esters include methyl formate, ethyl formate, methyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, ethyl lactate, and methyl lactate. As glycol ethers (C1 to C4), methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, As propylene glycol monobutyl ether or propylene glycol mono (C1-C4) alkyl ether esters, propylene glycol monomethyl ether acetate , Propylene glycol monoethyl ether acetate,
Examples of other solvents include N-methylpyrrolidone. Although not particularly limited to these, a solvent in which these are appropriately mixed is also preferably used.

The method of applying the coating composition in the present invention includes a doctor coat, an extrusion coat, a slide coat, a roll coat, a gravure coat, a wire bar coat, a reverse coat, a curtain coat, an extrusion coat, or a hopper described in US Pat. No. 2,681,294. It can apply | coat so that it may become a dry film thickness of 0.1-10 micrometers by the extrusion coating method etc. which use this. Preferably, it is applied so as to have a dry film thickness of usually 0.1 to 1 μm.

(Hard coat layer)
The film of the present invention can be provided with a transparent hard coat layer. An actinic ray curable resin or a thermosetting resin is preferably used as the transparent hard coat layer. The actinic radiation curable resin layer refers to a layer mainly composed of a resin that is cured through a crosslinking reaction or the like by irradiation with actinic rays such as ultraviolet rays or electron beams. Typical examples of the actinic radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, but a resin that is cured by irradiation with actinic rays other than ultraviolet rays and electron beams may be used. Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. I can do it. JP-A-2003-039014 discloses an invention having high flatness by winding a coated film or holding it in the width direction and drying it, and curing the coating solution containing an actinic radiation curing substance. The present invention is also applicable to the present invention.

UV curable acrylic urethane resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate) in products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. (Only acrylate is indicated), and can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate, and is described in, for example, JP-A-59-151110.

UV curable polyester acrylate resins can be easily obtained by reacting polyester polyols with 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers, and are described, for example, in JP-A-59-151112. ing.

Specific examples of the ultraviolet curable epoxy acrylate resin include those obtained by reacting epoxy acrylate with an oligomer, a reactive diluent and a photoreaction initiator added thereto. In the official gazette. As the photoinitiator, one or more kinds selected from benzoin derivatives, oxime ketone derivatives, benzophenone derivatives, thioxanthone derivatives and the like can be selected and used.

Specific examples of ultraviolet curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate. Etc. can be mentioned. These resins are usually used together with known photosensitizers.

Moreover, the said photoinitiator can also be used as a photosensitizer. Specific examples include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. When using an epoxy acrylate photoreactive agent, n-butylamine, triethylamine, tri-
A sensitizer such as n-butylphosphine can be used.

The photoreaction initiator or photosensitizer contained in the ultraviolet curable resin composition excluding the solvent component that volatilizes after coating and drying is particularly preferably 2.5 to 6% by mass of the composition. If it is less than 2.5%, the plasticizer and / or UV absorber eluted from the resin film will inhibit the curing, resulting in a decrease in scratch resistance. Therefore, on the contrary, the surface quality of the coating film may be deteriorated because the scratch resistance is lowered and the coating property is deteriorated.

Examples of the resin monomer may include common monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, vinyl acetate, benzyl acrylate, cyclohexyl acrylate, and styrene as monomers having one unsaturated double bond. In addition, monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above-mentioned trimethylolpropane. A triacrylate, a pentaerythritol tetraacryl ester, etc. can be mentioned.

The solid concentration of the coating composition for the actinic radiation curable resin layer is preferably 10 to 95% by mass, and an appropriate concentration is selected depending on the coating method. As the light source for forming the cured film layer of the actinic radiation curable resin by photocuring reaction, any light source that generates ultraviolet rays can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. The irradiation conditions vary depending on individual lamps, but the amount of light irradiated may be any 20~10000mJ / cm ^2, preferably 50~2000mJ / cm ^2. From the near ultraviolet region to the visible light region, it can be used by using a sensitizer having an absorption maximum in that region. The ultraviolet irradiation may be performed once or twice or more.

  As a solvent for coating the actinic radiation curable resin layer, a solvent for coating the above resin layer, for example, hydrocarbons, alcohols, ketones, esters, glycol ethers, and other solvents as appropriate. Can be selected or mixed for use. Preferably, a solvent containing 5% by mass or more, more preferably 5 to 80% by mass or more of propylene glycol mono (C1 to C4) alkyl ether or propylene glycol mono (C1 to C4) alkyl ether ester is used.

As a coating apparatus for the ultraviolet curable resin composition coating liquid, known apparatuses such as a gravure coater, a spinner coater, a wire bar coater, a roll coater, a reverse coater, an extrusion coater, and an air doctor coater can be used. The coating amount is 0.1 by wet film thickness.
-200 micrometers is suitable, Preferably, it is 0.5-100 micrometers. The coating speed is preferably 5 to 200 m / min. When the film thickness is thick, it may be divided and applied twice or more to form a transparent hard coat layer. The UV curable resin composition is applied and dried, and then irradiated with UV light from a light source. The irradiation time is preferably 0.5 seconds to 5 minutes, and 3 seconds to 2 from the curing efficiency and work efficiency of the UV curable resin. Minutes are more preferred. The resulting hard coat layer has a thickness of 0.
2-100 micrometers is preferable, More preferably, it is 1-50 micrometers, Especially, it is 2-45 micrometers.

In order to impart slipperiness to such a coating layer, the aforementioned inorganic or organic fine particles may be added. These can use the matting agent described above. Further, as described above, these actinic radiation curable resin layers can be provided on a resin layer such as an antistatic layer. The antistatic layer or the transparent hard coat layer can be provided alone or in layers. Specifically, JP-A-6-123806, JP-A-9-11728, and JP-A-9-203810.
Can be provided directly or via an undercoat layer on any surface of an optical film with antistatic, a polarizing plate protective film, a cellulose acylate film, etc.

(Antireflection layer)
The film of the present invention can be provided with an antireflection layer. Various configurations such as a single layer and a multilayer are known as the structure of the antireflection layer, but a multilayer structure generally has a structure in which high refractive index layers and low refractive index layers are alternately laminated.

Examples of the configuration include those composed of two layers of a high refractive index layer / low refractive index layer from the transparent substrate side, or three layers having different refractive indexes, a medium refractive index layer (transparent substrate or hard Layers with higher refractive index than coat layer and lower refractive index than high refractive index layer) / high refractive index layer / low refractive index layer, etc. Something to do is also proposed. Above all,
In view of durability, optical characteristics, cost, productivity, and the like, it is preferable to apply a high refractive index layer / medium refractive index layer / low refractive index layer in this order on a substrate having a hard coat layer.

A high refractive index layer (which may be provided with a middle refractive layer) on the substrate surface, and a low refractive index layer are laminated in order toward the air, and the optical film thickness of the high refractive index layer and the low refractive index layer with respect to the wavelength of light. An optical interference layer is made by setting a certain value, and an antireflection laminate is particularly preferable as the antireflection layer,
The refractive index and the film thickness can be calculated and calculated by measuring the spectral reflectance. The refractive index level is largely determined by the metal or compound contained therein, for example, Ti is high, Si is low, F-containing compounds are even lower, and the refractive index is set by such a combination.

In order to produce an antireflection layer by sequentially laminating a plurality of antireflection layers on a transparent substrate, at least one of the antireflection layers is used, and as a high refractive index layer, a metal alkoxide such as titanium or zirconium and its hydrolyzed layer. A high refractive index layer formed by applying a composition containing a compound selected from decomposition products, an active energy ray-reactive compound and an organic solvent and irradiating active energy rays (with a middle refractive layer provided) In some cases, after applying a low refractive index layer composition containing a low refractive material and an organic solvent to form a low refractive index coating film, an active energy is applied to form a low refractive index layer to form an antireflection layer. To do.

A preferred high refractive index layer in the present invention is at least one of multilayer antireflection layers on a transparent substrate, at least one selected from a metal alkoxide having no active energy ray reactive group and a hydrolyzate thereof, An active energy ray reactive metal alkoxide compound,
Preferably, it contains an active energy ray-reactive compound. After coating a high refractive index composition on the transparent substrate, the coating film is irradiated with active energy rays to form a high refractive index layer having an arbitrary refractive index. To do.

At least one compound selected from metal alkoxides and partial hydrolysates thereof used in the high refractive index layer and any of the active energy ray-reactive metal alkoxide compounds of the general formula (II) described later are the same. There are metals such as Al, Si, Ti, V, Ni,
Cu, Zn, Y, Ga, Ge, Zr, In, Sn, Sb, Sr, La, Ta, Tl, W,
Ce and Nd can be mentioned. Any metal compound of the active energy ray-reactive metal alkoxide compound is useful for changing the refractive index of the layer containing them, particularly by ultraviolet irradiation. Preferred metals include Al, Si, Ti, V, Zn, Y, Zr, In, S
n, Sr, Ta, Tl, a W and Ce, Ti as easily preferred metal is particularly change the refractive index, Zr, Tl, (as In-Sn complex) an In, with Sr (as Sr-TiO ₂ complex) is there. In the case of Ti, it is known to react to light, but it is not known to change the refractive index of a layer containing a Ti compound by light.

As a metal alkoxide which does not have an active energy ray reactive group, it is C1-C10.
It is preferable that it has 1 to 4 carbon atoms. The hydrolyzate of the metal alkoxide reacts like -metal atom-oxygen atom-metal atom when the alkoxide group is hydrolyzed to form a crosslinked structure and form a hardened layer.

Examples of metal alkoxides having no active energy ray reactive groups; Al alkoxides include Al (O—CH ₃ ) ₃ , Al (OC ₂ H ₅ ) ₃ , Al (Oi—C ₃ H ₇ ). _{3, Al (O-n-} C 4 H 9) 3;
Examples of Si include Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (Oi—C ₃ H ₇ ) ₄ , Si (Ot—C ₄ H ₉ ) ₄ ;
Examples of Ti include Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On—C ₃ H ₇ ) ₄ , Ti (Oi—C ₃ H ₇ ) ₄ , Ti ( On-C ₄ H ₉ ) ₄ , 2-10 mer of Ti (On-C ₃ H ₇ ) ₄ , 2-10 mer of Ti (Oi-C ₃ H ₇ ) ₄ , Ti 2-10 mer _{(O-n-C 4 H} 9) 4;
Examples of V include VO (OC ₂ H ₅ ) ₃ ;
Examples of Zn include Zn (OC ₂ H ₅ ) ₂ ;
Examples of Y include Y (OC ₄ H ₉ ) ₃ ;
Examples of Zr include Zr (OCH ₃ ) ₄ , Zr (OC ₂ H ₅ ) ₄ , Zr (On-C ₃ H ₇ ) ₄ , Zr (Oi-C ₃ H ₇ ) ₄ , Zr ( Oi-C ₄ H ₉ ) ₄ , Zr (On-C ₄ H ₉ ) ₄ di- to 10-mer;
Examples of In, In (O-n-C 4 H 9) 3;
Examples of Sn is, Sn (O-n-C 4 H 9) 4,;
Examples of Ta is _{Ta (OCH 3) 5, Ta} (O-n-C 3 H 7) 5, Ta (O-i-C 3 H 7) 5, Ta (O-n-C 4 H 9) 5 ;
Examples of W include W (OC ₂ H ₅ ) ₆ ;
Examples of Ce include Ce (OC ₃ H ₇ ) ₃ . These can be used alone or in combination of two or more. Among them, Ti (O-n-C 3 H 7) 4, Ti (O-i-C 3 H 7) 4, Ti (O-n-C 4 H 9) 4, Ti (O-n-C 3 H _{7) 4} 2-10 mer, Ti (O-n-C 4 H 9) 4 2-10 mer; Zr (O-i-C 3 H 7) 4, Zr (O-n-C 4 _{H 9) 4; Si (OC} 2 H 5) 4, Si (O-i-C 3 H 7) 4 are particularly preferred.

The metal alkoxide may be used after being hydrolyzed (partially or completely hydrolyzed), and can be obtained, for example, by hydrolyzing the metal alkoxide in an organic solvent in the presence of an acidic catalyst or a basic catalyst. Examples of the acidic catalyst include mineral acids such as nitric acid and hydrochloric acid, and organic acids such as oxalic acid and acetic acid, and examples of the basic catalyst include ammonia.

The layer containing the metal alkoxide compound is a layer in which the metal alkoxide itself is self-condensed to be crosslinked and network-bonded. In order to accelerate the reaction, a catalyst or a curing agent can be used. These include metal chelate compounds, organometallic compounds such as organic carboxylates, organosilicon compounds having amino groups, photoacid generators, and the like. is there. Among these catalysts or curing agents, an aluminum chelate compound and a light acid generator (photo acid generator) are particularly preferable. Examples of the aluminum chelate compound include ethyl acetoacetate aluminum diisopropylate and aluminum trisethyl. Acetoacetate, alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bisethylacetoacetate, aluminum trisacetylacetonate, etc. Examples of other photoacid generators include benzyltriphenylphosphonium hexafluorophosphate and other Examples thereof include phosphonium salts and salts of triphenylphosphonium hexafluorophosphate.

To the coating composition containing a metal alkoxide having no active energy ray reactive group and / or a hydrolyzate thereof to be used, a chelate compound is added after reacting with a β-diketone for the storage stability of the coating solution. Thus, a stable coating composition can be obtained.

The active energy ray reactive compound preferably used for the high refractive index layer has two or more polymerizable groups such as a polymerizable vinyl group, allyl group, acryloyl group, methacryloyl group, isopropenyl group, and epoxy group. Those that form a crosslinked structure or a network structure by irradiation with active energy rays are preferred. Among these active groups, an acryloyl group, a methacryloyl group or an epoxy group is preferable from the viewpoint of polymerization rate and reactivity. For example, they are described in JP-A-59-151110 and JP-A-59-151112. Yes. In addition, these compounds
A polyfunctional monomer or oligomer is more preferred.

An active energy ray reactive epoxy resin is also preferably used. As the active energy ray-reactive epoxy resin, an aromatic epoxy compound (polyglycidyl ether of polyhydric phenol) is preferable. As the active energy ray-reactive compound epoxy resin, in addition to those having two or more epoxy groups in the molecule, monoepoxide can also be used depending on the desired performance. The active energy ray-reactive compound epoxy resin forms a polymerized, crosslinked structure or network structure not by radical polymerization but by cationic polymerization. Unlike radical polymerization, it is not affected by oxygen in the reaction system, and is therefore a preferred active energy ray reactive resin.

Aromatic halonium salts described in JP-A-50-151996, JP-A-50-158680, etc., JP-A-50-151997, JP-A 52-30899, JP-A 59-
No. 55420, JP-A 55-125105, VIA group aromatic onium salts, JP-A 56-8428, JP-A 56-149402, JP-A 57-192429
Preferred are oxosulfonium salts described in each of the gazettes, aromatic diazonium salts described in JP-B-49-17040, thiopyrylium salts described in US Pat. No. 4,139,655, and the like. Moreover, an aluminum complex, a photodegradable silicon compound polymerization initiator, etc. can be mentioned. The cationic polymerization initiator, benzophenone, benzoin isopropyl ether,
A photosensitizer such as thioxanthone can be used in combination.

Specific examples of the active energy ray-reactive metal alkoxide include vinyl trimethoxy titanium, vinyl tri (β-methoxy-ethoxy) titanium, divinyloxydimethoxy titanium, glycidyloxyethyl triethoxy titanium, and γ-acryloyloxypropyl tri-n. −
Propyl titanium, γ-methacryloyloxy-n-propyl tri-n-propyl titanium,
Di (γ-acryloyloxy-n-propyl) di-n-propyltitanium, acryloyloxydimethoxyethyltitanium, vinyltrimethoxyzircon, divinyloxydimethoxyzircon, acryloyloxyethyltriethoxyzircon, γ-acryloyloxy-n-
Propyl tri-n-propyl zircon, γ-methacryloyloxy-n-propyl tri-
n-propyl zircon, di (γ-acryloyloxy-n-propyl) di-n-propyl zircon, acryloyloxydimethoxyethyl zircon, vinyl dimethoxythallium,
Vinyldi (β-methoxy-ethoxy) thallium, divinyloxymethoxythallium, acryloyloxyethyldiethoxythallium, γ-acryloyloxy-n-propyldi-n
-Propylthallium, γ-methacryloyloxy-n-propyldi-n-propylthallium, di (γ-acryloyloxy-n-propyl) -n-propylthallium, acryloyloxymethoxyethylthallium, vinyltrimethoxysilane, vinyltri (β- Methoxy-ethoxy) silane, divinyloxymethoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrialkoxysilane, acryloyloxyethyltriethoxysilane, glycidyloxyethyltriethoxysilane, γ-acryloyloxy-n-propyl Tri-n-propylsilane, γ-methacryloyloxy-n-propyltri-n-propylsilane, di (γ-acryloyloxy-n-propyl) di-n-propylsilane, acryloyloxydimethoxyethyl It can be mentioned the run, and the like.

The behavior of photopolymerization by active energy rays with respect to the active energy ray reactive group used in the high refractive index layer and the reactive group of the active energy ray reactive compound preferably used is almost the same, and the light of the aforementioned active energy ray compound is not changed. Similar sensitizers and photoinitiators are used.

The active energy ray can be used without limitation as long as it is an energy source that activates the compound by ultraviolet rays, electron rays, γ rays, etc., but ultraviolet rays and electron rays are preferable, and handling is particularly simple and high energy can be easily obtained. In this respect, ultraviolet rays are preferable. As the ultraviolet light source for photopolymerizing the ultraviolet reactive compound, any light source that generates ultraviolet light can be used. For example,
A low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. ArF excimer laser, KrF
An excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used. Irradiation conditions vary depending on each lamp, but the amount of irradiation light is 50 mJ / m ² or more, preferably 100 mJ / cm ² or more, and more preferably 400 mJ / cm ² or more. The ultraviolet rays may be irradiated to the multilayer antireflection layer one by one or after lamination. From the viewpoint of productivity, it is preferable to irradiate ultraviolet rays after laminating multiple layers. In this case, it is efficient to carry out under the condition that the oxygen concentration is 0.5% or less, which is preferable from the viewpoint of curing speed.

Moreover, an electron beam can be used similarly. As the electron beam, 50 to 1000 keV emitted from various electron beam accelerators such as cockroft Walton type, bandegraph type, resonance transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type, preferably 100 to 100 An electron beam having an energy of 300 keV can be given.

The low refractive index layer as the outermost layer contains the following low refractive index material containing fluorine atoms or silicon atoms in order to lower the refractive index of the layer. Examples of the low refractive index substance include at least one compound selected from a fluorine-containing resin, a compound formed from a silicate oligomer, and a compound formed from a SiO ₂ sol and a reactive organosilicon compound. The compounds described in 126552, JP-A-7-188582, JP-A-8-48935, JP-A-8-100136, JP-A-9-220791, JP-A-9-272169, etc. are preferably used. It is done.

Examples of the fluorine-containing resin that can be preferably used in the present invention include a polymer mainly containing a fluorine-containing unsaturated ethylenic monomer component and a fluorine-containing epoxy compound. Examples of the fluorine-containing unsaturated ethylenic monomer include fluorine-containing alkenes, fluorine-containing acrylic esters, fluorine-containing methacrylate esters, fluorine-containing vinyl esters, and fluorine-containing vinyl ethers. For example, tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, trifluoropropylene, heptafluoropropylene, hexafluoropropylene, 3,3,4,4,5,5,6,6,6-nonafluoro- 1-hexene, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octene, 4-ethoxy-1,1,1-trifluoro -3-buten-2-one, pentadecafluorooctyl acrylate, tetrafluoro-3- (pentafluoroethoxy) propyl acrylate, tetrafluoro-3-trifluoromethoxypropyl acrylate, undecafluorohexyl acrylate, nonafluoropentyl acrylate, Octafluoropentyl acrylate, pentafluoropi Pill acrylate, 2
Heptafluorobutoxyethyl acrylate, 2,2,3,4,4,4-hexafluorobutoxy acrylate, trifluoroethyl acrylate, 2- (1,1,2,2-tetrafluoroethoxy) ethyl acrylate, trifluoroisopropyl methacrylate ,
(2,2,2-trifluoro-1-methyl) ethyl methacrylate, 3-trifluoromethyl-4,4,4-trifluorobutyl acrylate, 1-methyl-2,2,3,3,3
-Pentafluoropropyl acrylate, 1-methyl-2,2,3,3,4,4,4-heptaurobutyl acrylate, 2,2,2-trifluoroethyl acrylate, pentafluoropropyl acrylate, 1,1, 1,3,3,3-hexafluoroisopropyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,2-
Trifluoroethyl methacrylate, 2,2,3,3,4,4,4-heptafluorobutyl acrylate, nonafluoropentyl acrylate, undecafluorohexyl acrylate, tridecafluoroheptyl acrylate, pentadecafluorooctyl acrylate, tridecafluoro Octyl acrylate, nonadecafluorodecyl acrylate,
Heptadecafluorodecyl acrylate, hexafluoroisopropyl acrylate, tetrafluoropropyl acrylate, hexafluorobutyl acrylate (the above acrylate may be methacrylate or α-fluoro acrylate), vinyl trifluoroacetate, vinyl-2,2,2 -Trifluoropropionate, vinyl-3,
3,3,2,2-heptabtylate, 2,2,2-trifluoroethyl vinyl ether,
1- (trifluoromethyl) ethenyl acetate, allyl trifluoroacetate, allyl-1,1,2,2-tetrafluoroethyl ether, allyl-1,2,3,3,3-hexafluoropropyl ether, ethyl- 4,4,4-trifluorocrotonate, isopropyl-2,2,2-trifluoroethyl fumarate, isopropyl-pentafluoropropyl fumarate, isopropyl-2,2,3,3,4,4,4-hepta Fluorobutyl fumarate, isopropyl-2,2,3,3,4,4,5,5,5-nonapropylpentyl fumarate, isopropyl-2,2,3,3,4,4,5,5,6 , 6,6-undecafluorohexyl fumarate, isopropyl-tridecafluoroheptyl fumarate,
Isopropyl-pentadecafluorooctyl fumarate, isopropyl-tridecafluorooctyl fumarate, isopropyl-nonadecafluorodecyl fumarate, isopropyl-heptadecafluorodecyl fumarate, isopropyl-2-trifluoromethyl-3
, 3,3-trifluoropropyl fumarate, isopropyl-3-trifluoromethyl-
4,4,4-trifluorobutyl fumarate, isopropyl-1-methyl-2,2,3
3,3-pentafluoropropyl fumarate, isopropyl-1-methyl-heptafluorooctyl fumarate, tert-butyl-pentylfluoropropyl fumarate, te
Fluorine-containing unsaturated ethylenic monomers such as rt-butyl-heptafluorobutyl fumarate can be mentioned, but are not limited thereto. The copolymerization partner monomer may or may not contain fluorine.

Monomers that can be copolymerized with the fluorine-containing monomer include, for example, ethylene, propylene, butene, vinyl acetate, vinyl ethyl ether, vinyl ethyl ketone, methyl acrylate, methyl methacrylate, ethyl acrylate, propyl acrylate, and butyl acrylate. , Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl-α-fluoroacrylate, ethyl-α-fluoroacrylate, propyl-α-fluoroacrylate, butyl-α-fluoroacrylate, cyclohexyl-α-fluoroacrylate, hexyl- α-fluoroacrylate, benzyl-α-fluoroacrylate, acrylic acid, methacrylic acid, α-fluoroacrylic acid,
Styrene, styrene sulfonic acid or the like may be copolymerized, but is not limited thereto.

The refractive index of a single resin of the fluorine-containing ethylenically unsaturated monomer is approximately 1.33-1.
The refractive index of a monomer-free resin remer of a monomer containing no fluorine that is in the range of 42 and can be copolymerized is 1.44 or more, and these are copolymerized at an arbitrary ratio to contain fluorine having a desired refractive index. It can be used as a resin, and the fluorine-containing resin of the present invention and a resin not containing fluorine may be mixed at an arbitrary ratio and used as a target refractive index. The fluorine content of the substance is preferably 50% by mass or more, and varies depending on the substance, but is particularly preferably 60 to 90% by mass. In the case of a fluorine-containing polymer, if the fluorine content is in such a range, not only is it easy to process by having good solubility in an organic solvent, but also excellent adhesion to the underlying substrate and layer, A layer with high transparency and low refractive index can be obtained.

As the polymerization initiator for polymerizing the fluorine-containing alkene, acrylate, vinyl ester or vinyl ether to be used, a normal radical polymerization initiator can be used. Specific examples of the polymerization initiator include azo radical polymerization initiators such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobisvaleronitrile, benzoyl peroxide, t
-Organic peroxide radical polymerization initiators such as butyl hydroperoxide, cumene peroxide, diacyl peroxide, inorganic radical polymerization initiators such as ammonium persulfate and potassium persulfate, hydrogen peroxide-ferrous ammonium sulfate, Examples include various radical polymerization initiators such as redox polymerization initiators such as ammonium persulfate-sodium metasulfite.

Using these, known radical polymerization such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization or radiation polymerization can be performed. At this time, the reaction temperature is 10 to 100 ° C., and the reaction time is 1-1.
It is preferably 00 hours. The number average molecular weight of the fluorine-containing resin thus obtained is desirably 1000 to 300,000. The fluorine-containing epoxy resin as the fluorine-containing resin can be obtained, for example, by reacting the following epoxy compound by a conventional method.

As the fluorine-containing epoxy compound, mono-, di-, tri- and oligoglycidyl ethers of fluorine-based alcohols are preferable. Among them, examples of the fluorine-containing alkane-terminated diol glycidyl ether include 2,2,3,3-tetrafluoro-1,4-butanediol diglycidyl ether, 2,2,3,3,4,4,5,5-octa Although fluoro-1, 6-hexanediol diglycidyl ether etc. can be mentioned, it is not limited to these. In addition to these, a small amount of an epoxy compound containing no fluorine may be used so that the refractive index does not increase so much. Although there is no restriction | limiting in the structure of the fluorine-containing epoxy compound used here, It is better that there are few use of the epoxy compound which has a benzene nucleus which raises a refractive index, and an alicyclic epoxy compound.

Another preferred low refractive index material is a compound formed from a silicate oligomer. Examples of silicate oligomers used for compounds formed from silicate oligomers include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, and tetra-2,2,2-trifluoroethoxysilane. Tetra-2-fluoroethoxysilane, tetra-2,2,3,3-tetrafluoro-1-propoxysilane, tetra-1,1,1,3,3,3-hexafluoro-2
-Propoxysilane, tetra-2,2,3,3,3-pentafluoro-1-propoxysilane, tetra-1,3-difluoro-2-propoxysilane, tetra-2,2,3
, 3,4,4,4-heptafluoro-1-butoxysilane, tetra-2,2,3,4,4
, 4-hexafluoro-1-butoxysilane, tetracyclohexyloxysilane, tetraphenoxysilane, and the like, and a silicate oligomer can be obtained by hydrolyzing them.

As described above, a hydrolyzate cured by a method such as adding a solvent to a hydrolyzate obtained by adding a catalyst and water to tetraalkoxysilane and then adding a curing catalyst and water is obtained.
As such a solvent, it is preferable to use one or two kinds of methanol and ethanol because it is inexpensive and the properties of the resulting film are excellent and the hardness is good. Although isopropanol, n-butanol, isobutanol, octanol, and the like can be used, the hardness of the obtained film tends to be low. The amount of solvent is 50 with respect to 100 parts by mass of the partial hydrolyzate.
-400 mass parts, Preferably it is 100-250 mass parts. Examples of the curing catalyst include acids, alkalis, organic metals, metal alkoxides, and the like, and acids such as acetic acid, maleic acid, oxalic acid, and fumaric acid are preferably used. The SiO ₂ content in the silicate oligomer is desired to be 1 to 100%, preferably 10 to 99%. Such SiO
_{2 If the} content is less than 1%, the durability is not improved, and the effects of the present invention are not exhibited.

The method for forming a silicon layer from these silicate oligomers is not particularly limited, but for example, a solvent that does not inhibit the optical performance of the optical film of the silicate oligomer, such as alcohol (methanol, ethanol, isopropanol, etc.), ethyl acetate, butyl acetate, acetic acid Cellosolve, methyl glycol acetate, methoxybutyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylene chloride, toluene, xylene, mineram spirit, cresol, xylenol, furfural, etc. What is necessary is just to apply | coat to a base material and to heat-process with a well-known apparatus, such as a coater, a gravure coater, a reverse coater, a lip coater.

Further preferred low refractive index material, a compound formed from the reactive organic silicon compound SiO ₂ sol, using a sol solution containing a reactive organic silicon compound SiO ₂ sol, S
A low refractive index layer is formed as an iO ₂ gel film. The SiO ₂ sol is prepared by dissolving silicon alkoxide in an organic solvent suitable for coating and adding a certain amount of water to perform hydrolysis. Preferred silicon alkoxides used to form the SiO ₂ sol are, for example, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra -T-butoxysilane, tetrapentaethoxysilane, tetrapentaisopropoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-t-butoxysilane, methyltrimethoxysilane , Methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, dimethyldimethylmethoxysilane, dimethyldiethoxysilane, dimethylmethoxysilane, dimethyleth Shishiran, dimethylpropylidene silane, dimethyl-butoxy silane, methyl dimethoxy silane, methyl diethoxy silane, hexyl trimethoxy silane and the like.

A SiO ₂ sol can be obtained by dissolving the alkyl silicon alkoxide or silicon alkoxide in a suitable solvent. Examples of the solvent used include methyl ethyl ketone, isopropyl alcohol, methanol, ethanol, methyl isobutyl ketone,
Alcohols such as ethyl acetate and butyl acetate, ketones, esters, halogenated hydrocarbons,
Aromatic hydrocarbons such as toluene and xylene, or a mixture thereof can be mentioned. Alkyl silicon alkoxide or silicon alkoxide is converted into SiO ₂ produced as a result of 100% hydrolysis and condensation in the solvent so that the concentration is 0.1% by mass or more, preferably 0.1 to 10% by mass. Dissolve. If the concentration of the SiO ₂ sol is less than 0.1% by mass, the formed sol film cannot sufficiently exhibit the desired characteristics, while if it exceeds 10% by mass, it becomes difficult to form a transparent homogeneous film. Moreover, in this invention, if it is less than the above solid content, it is also possible to use an organic substance and an inorganic binder together.

To this solution, more water than necessary for hydrolysis is added, 15 to 35 ° C., preferably 22 to 28.
Stirring is carried out at a temperature of 0 ° C. for 0.5 to 10 hours, preferably 2 to 5 hours. In the hydrolysis, it is preferable to use a catalyst. As these catalysts, acids such as hydrochloric acid, nitric acid, sulfuric acid or acetic acid are preferable. These acids are added in an amount of about 0.001 to 40.0 mol / l, preferably 0.0
It can be added as an aqueous solution of about 05 to 10.0 mol / l, and the water in the aqueous solution can be used as water for hydrolysis.

Although the gel film finally obtained is used as a low refractive index layer of an antireflection film, it may be necessary to adjust the refractive index. For example, a fluorine-based organic silicon compound can be added to lower the refractive index, an organic silicon compound can be added to increase the refractive index, and a boron-based organic compound can be added to further increase the refractive index. Specifically, tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, tetrabutoxysilane, alkyltrialkoxysilane, Colcoat 40 (manufactured by Colcoat), MS51 (manufactured by Mitsubishi Chemical Corporation), Snowtex (manufactured by Nissan Chemical Industries, Ltd.) ), Etc., Zaflon FC-110, 220, 250 (manufactured by Toa Gosei Chemical Co., Ltd.), sexual coat A-402B (manufactured by Central Glass Co., Ltd.), heptadecafluorodecyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, Examples thereof include fluorine compounds such as trifluorooctyltrimethoxysilane and trifluoropropyltrimethoxysilane, and boric acid compounds such as triethyl borate, trimethyl borate, tripropyl borate, and tributyl borate.

These additives may be added during the preparation of the sol, or may be added after the formation of the sol. By using these additives, during the hydrolysis of the alkyl silicon alkoxide or silicon alkoxide, or after that, it reacts with the silanol group, and more uniformly reacts to obtain and form a more uniform and transparent sol solution. The refractive index of the gel film can be changed within a certain range.

Next, the fluorine-containing resin, a compound formed from a silicate oligomer, and SiO
_{2 The} low refractive index layer (provided on the high refractive index layer) containing at least one low refractive index substance selected from compounds formed from a sol and a reactive organosilicon compound has the high refractive index The active energy ray reactive compound mentioned at the layer may be added. Of these, epoxy-based active energy ray-reactive compounds are preferably used. The epoxy-based active energy ray-reactive compound is a compound having two or more epoxy groups in the molecule and capable of releasing cationic polymerization as an initiator by irradiation with active energy rays as described above. Examples of the epoxy-based active energy ray-reactive compounds include (a) glycidyl ether of bisphenol A (this compound is obtained by reaction of epichlorohydrin and bisphenol A, and is obtained as a mixture having different degrees of polymerization); (b) bisphenol A, etc. A compound having a glycidyl ether group at the terminal by reacting epichlorohydrin, ethylene oxide and / or propylene oxide with a compound having two phenolic OHs. The photopolymerization initiator or photosensitizer for cationically polymerizing an epoxy-based active energy ray-reactive compound is a compound capable of releasing a cationic polymerization initiator by irradiation with active energy rays, and particularly preferably a cation by irradiation. It is a group of double salts of onium salts that release Lewis acids capable of initiating polymerization. Since these are the same as those in the general formula (I), they are omitted here. These active energy ray-reactive compounds are cured by the application of ultraviolet rays, active energy rays such as electron beams, plasma treatment, or thermal energy similar to those described in the high refractive index layer. Is the same.

The antireflection layer is formed as described above. The optical film of the present invention can also be provided with an antiglare layer. The antiglare layer has a structure containing fine particles in the layer in order to have an antiglare function by scattering the light on the surface of the antiglare layer or inside the antiglare layer by providing a structure having irregularities on the surface. Yes. Preferred configurations for these layers are as shown below. This is a layer having a film thickness of 0.5 to 5.0 μm and containing one or more kinds of fine particles having an average particle diameter of 0.25 to 10 μm, and the average particle diameter is 1.1 to 2 times the film thickness A layer containing silicon dioxide particles and silicon dioxide fine particles having an average particle size of 0.005 to 0.1 μm in a binder such as diacetylcellulose, for example, and can exhibit an antiglare function.
Examples of the “particles” include inorganic particles and organic particles.

Examples of the inorganic particles that can be used in the present invention include silicon dioxide, titanium oxide, aluminum oxide, zinc oxide, tin oxide, calcium carbonate, barium sulfate, talc, kaolin, and calcium sulfate. Organic particles include poly (meth) acrylate resins, silicone resins, polystyrene resins, polycarbonate resins, acrylic styrene resins, benzoguanamine resins, melamine resins, polyolefin resins, polyester resins, polyamide resins. Polyimide resin, polyfluorinated ethylene resin, etc. can be used.

Among these, silicon dioxide such as silica is particularly preferably used to achieve the antiglare property applied in the present invention. As the silicon dioxide particles preferably used here, ultrafine hydrated silicic acid produced by a wet method among synthetic amorphous silicas is preferable because of its great effect of reducing the glossiness. The wet method is a method in which sodium silicate is reacted with mineral acid and salts in an aqueous solution, and examples thereof include silicia manufactured by Fuji Silysia Chemical Co., Ltd. and Nippon Sil E manufactured by Nippon Silica Co., Ltd.

In JP-A-2003-121620, an anti-glare layer having a fine unevenness on the surface is provided on one surface of the support as a film with high visibility, good adhesion and scratch resistance, and uneven coating. The antiglare layer contains at least one kind of particles having an average particle diameter of 0.01 μm to 4 μm, and a high refractive index layer having a refractive index of 1.55 to 2.5 and a low refractive index of 1.3 to 1.5 on the antiglare layer. Anti-glare property, comprising an anti-reflection layer containing at least one rate layer, and the center line average roughness (Ra) of the anti-reflection layer defined by JISB 0601 being 0.08 μm to 0.5 μm A low reflection film is disclosed and the invention is also applicable to the present invention.

The antiglare layer also preferably uses an actinic radiation curable resin as a binder, and the actinic radiation curable resin layer containing silicon dioxide particles or silicon dioxide fine particles is formed by irradiation with actinic radiation after coating. In view of increasing the mechanical strength of the polarizing plate surface, an antiglare layer using an actinic radiation curable resin as a binder is more preferable.

The actinic radiation curable resin that can be used here refers to a resin that is cured through a crosslinking reaction or the like by irradiation with actinic radiation such as ultraviolet rays or electron beams. Typical examples of the actinic radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, but a resin that is cured by irradiation with an actinic ray other than ultraviolet rays or an electron beam may be used. Examples of UV curable resins include UV curable polyester acrylate resins, UV curable acrylic urethane resins, UV curable acrylate resins, UV curable methacrylate resins, UV curable polyester acrylate resins and Examples thereof include ultraviolet curable polyol acrylate resins.

Examples of ultraviolet curable polyol acrylate resins that can be used in the present invention include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate,
Photopolymerizable monomer oligomers such as pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and alkyl-modified dipentaerythritol pentaerythritol. These polyol acrylate resins are characterized by high crosslinkability, high curability, high hardness, low cure shrinkage, low odor, low toxicity and relatively high safety.

The ultraviolet curable polyol acrylate resin may contain other ultraviolet curable resins, for example, an ultraviolet curable epoxy resin as long as the effect is not impaired.
Cured coatings with thick acrylate resin coatings are curled due to cure shrinkage,
It may interfere with handling work. Epoxy resins generally have less cure shrinkage and less curling of cured coatings than acrylate resins. The ultraviolet curable epoxy resin referred to here is a compound containing two or more epoxy groups in the molecule, is a epoxy resin containing a cationic polymerization initiator, and undergoes a crosslinking reaction when irradiated with ultraviolet rays.

Examples of the electron beam curable resin that can be used are preferably those having an acrylate functional group, such as a polyester resin, polyether resin, acrylic resin, epoxy resin, urethane resin, alkyd having a relatively low molecular weight. Examples include resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, and the like.

Among these, it is preferable to use an ultraviolet curable resin. The actinic radiation curable resin can be cured by irradiation with actinic rays such as an electron beam or ultraviolet rays. For example, in the case of electron beam curing, 50 to 1000 emitted from various electron beam accelerators such as a Cockloft Walton type, a bandegraph type, a resonant transformation type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type.
An electron beam or the like having an energy of keV, preferably 100 to 300 keV is used. In the case of ultraviolet curing, ultraviolet rays emitted from rays such as ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, carbon arc, xenon arc, metal halide lamp, etc. Available. The film thickness is 0.5
It is preferable that it is -5.0 micrometers. Of these, the case of 2.0 to 4.0 μm is particularly preferable.

Instead of the active radiation used for curing each component layer of the optical film having the antireflection layer or the antiglare layer and the easy-adhesion layer on the opposite side of the base material, plasma treatment, Such a method is also preferable. As a plasma treatment, Japanese Patent Application No. 11-14320
The method described in Japanese Patent No. 6 can be preferably used. Further, as the heat treatment for imparting active energy, it is also effective to perform heat treatment after coating and drying of the antireflection layer or the antiglare layer. 70
It is preferable to heat at 30 [deg.] C. for 30 seconds to 10 minutes, more preferably 30 seconds to 5 minutes. By providing these antiglare layers, it is desirable that the visible light transmittance does not decrease, and the haze value is preferably 3% or more. Further, the transmittance at that time is preferably 90% or more in terms of transmittance at 550 nm. The surface layer of the antiglare layer has a critical surface tension of 20 × 10 ⁻⁶ N /
It is preferable that it is cm or less. When the critical surface tension is larger than 20 × 10 ⁻⁶ N / cm, it becomes difficult to remove the dirt attached to the surface layer. A fluorine-containing fluorine material is preferable in terms of preventing contamination.

Fluorine-containing materials include vinylidene fluoride copolymers, fluoroolefin / hydrocarbon olefin copolymers, fluorine-containing epoxy resins, fluorine-containing epoxy acrylates, fluorine-containing silicones that are soluble in organic solvents and easy to handle. , Fluorine-containing alkoxysilane, TEFRON (registered trademark) AF1600 (manufactured by DuPont, n = 1.30), C
YTOP (Asahi Glass Co., Ltd., n = 1.34), 17FM (Mitsubishi Rayon Co., Ltd., refractive index n = 1.35), LR201 (Nissan Chemical Industries, Ltd., n = 1. 38). These can be used alone or in combination.

Also, 2- (perfluorodecyl) ethyl methacrylate, 2- (perfluoro-7-methyloctyl) ethyl methacrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl methacrylate, 2- (perfluoro-9-methyldecyl) ) Fluorinated methacrylates such as ethyl methacrylate, 3- (perfluoro-8-methyldecyl) 2-hydroxypropyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2- (perfluorodecyl) ethyl acrylate, 2- (per Fluoro-9-
Fluorine-containing acrylates such as methyl decyl) ethyl acrylate, radiation curing type epoxides such as 3-perfluorodecyl 1,2-epoxypropane, 3- (perfluoro-9-methyldecyl) -1,2-epoxypropane, and epoxy acrylate Fluorine-containing monomers, oligomers, prepolymers and the like can be mentioned. These can be used alone or in combination.

The optical film of the present invention can be subjected to anti-curl processing. Anti-curl processing gives the function of trying to curl with the surface to which it is applied inside, but by applying this processing, some surface processing is performed on one side of the transparent resin film, It works to prevent curling with the surface facing inward when different degrees and types of surface treatment are applied.

A mode in which the anti-curl layer is provided on the side opposite to the side having the anti-glare layer or anti-reflection layer of the substrate, or
For example, an easy-adhesion layer may be coated on one side of the transparent resin film, and an anti-curling process may be coated on the opposite side.

Specific examples of the anti-curl processing include solvent coating, and a method in which a solvent and a transparent resin layer such as cellulose triacetate, cellulose diacetate, and cellulose acetate propionate are coated. The method using a solvent is specifically performed by applying a composition containing a solvent for dissolving or swelling a cellulose acylate film used as a protective film for a polarizing plate. Accordingly, the coating solution for the layer having the function of preventing curling preferably contains a ketone-based or ester-based organic solvent. Examples of preferred ketone-based organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl lactate, acetyl acetone, diacetone alcohol, isophorone, ethyl-n-butyl ketone, diisopropyl ketone, diethyl ketone, di-n-propyl ketone, Examples thereof include methylcyclohexanone, methyl-n-butyl ketone, methyl-n-propyl ketone, methyl-n-hexyl ketone, methyl-n-heptyl ketone, etc. Examples of preferable ester organic solvents include methyl acetate, ethyl acetate, acetic acid Examples include butyl, methyl lactate, and ethyl lactate. However, the solvent used is a solvent to be dissolved and / or
Alternatively, in addition to a mixture of solvents to be swelled, a solvent that does not dissolve may be further contained, and this is performed using a composition and a coating amount in which these are mixed at an appropriate ratio depending on the curl degree of the transparent resin film and the type of resin. In addition, the anti-curl function is exhibited even if transparent hard processing or antistatic processing is applied.

In the optical film of the present invention, it is preferable to provide a layer having a function of preventing curling on the side opposite to the side having the antiglare layer or antireflection layer of the substrate. The optical film thus produced preferably has a curl degree of −10 to +10 at 23 ° C. and 60% RH.

The curl degree is measured by the following method. The film sample is left for 48 hours in an environment of 80 ° C. and 90% RH, and then the film is cut into a width direction of 50 mm and a longitudinal direction of 2 mm. Further, the film piece is conditioned for 24 hours in an environment of 23 ° C. ± 2 ° C. and 55% RH, and the curl value of the film is measured using a curvature scale.

The curl value is represented by 1 / R, where R is a radius of curvature and the unit is m. For curl values,
A film with less deformation is preferable, and the deformation direction may be the + direction or the-direction.
That is, it is sufficient that the absolute value of the curl value is small. Specifically, when the absolute value of the curl value of the film is greater than 10, when a polarizing plate or the like is produced using the film, , Leaving at 80 ° C. and 90% RH for 48 hours), the deformation such as warpage becomes large and it cannot be used. If the curl value of the film is 10 or less, when a polarizing plate or the like is produced using the film, deformation such as warping is caused even under high temperature and high humidity (for example, left at 80 ° C. and 90% RH for 48 hours). Can be used small.

Despite the coating of these anti-curl layers and other layers, the optical film of the present invention preferably has a haze value of 3% or more and a transmittance at 550 nm of 90% or more. In addition, these outermost surface layers have a certain degree of hydrophilicity because they are used by bonding an easy-adhesion layer to a polarizer or by attaching an antireflection layer surface to a protective layer film surface. In particular, the contact angle of water at 23 ° C. and 60% RH of the easily adhesive layer is preferably 50 degrees or less.

(Easily adhesive layer)
In the optical film of the present invention, an easy-adhesion layer can be applied. The easy-adhesion layer refers to a layer that imparts a function of facilitating adhesion between the protective film for polarizing plate and its adjacent layer, typically a polarizing film.

Examples of the easy-adhesion layer preferably used in the present invention include a layer containing a polymer compound having a -COOM (M represents a hydrogen atom or a cation) group, and a more preferable embodiment is a film substrate. A layer containing a polymer compound having a —COOM group is provided on the side, and a layer containing a hydrophilic polymer compound as a main component is provided on the polarizing film side adjacent to the layer. Examples of the polymer compound having -COOM group herein include a styrene-maleic acid copolymer having -COOM group and a vinyl acetate-maleic acid copolymer having -COOM group,
Examples thereof include vinyl acetate-maleic acid-maleic anhydride copolymer, and it is particularly preferable to use a vinyl acetate-maleic acid copolymer having a —COOM group. These polymer compounds are used alone or in combination of two or more, and the preferred weight average molecular weight is 500 to 500,000.
It is good that it is about. Particularly preferred examples of the polymer compound having a —COOM group include those described in JP-A-6-094915 and JP-A-7-333436.

The hydrophilic polymer compound is preferably a hydrophilic cellulose derivative (eg, methylcellulose, carboxymethylcellulose, hydroxycellulose, etc.), a polyvinyl alcohol derivative (eg, polyvinyl alcohol, vinyl acetate-vinyl alcohol copolymer, polyvinyl acetal, polyvinyl formal, Polyvinyl benzal, etc.), natural polymer compounds (eg, gelatin, casein, gum arabic, etc.), hydrophilic polyester derivatives (eg, partially sulfonated polyethylene terephthalate), hydrophilic polyvinyl derivatives (eg, poly- N-vinylpyrrolidone, polyacrylamide, polyvinylindazole, polyvinylpyrazole and the like), and may be used alone or in combination of two or more.

[Cellulose acylate film properties]
The physical properties of the cellulose acylate film produced by the above method will be described in more detail. When the optical film of the present invention is used as a polarizing plate protective film, the thickness of the protective film is preferably 5 to 500 μm. Furthermore, the range of 20 to 300 μm is preferable, especially 30.
A range of ˜150 μm is most preferred. Incidentally, in Japanese Patent Application Laid-Open No. 2003-011143, in order to make it difficult to see the drying process slip and to improve the quality on the appearance, among the film thickness fluctuations of the film, the fluctuation period corresponds to 20 to 100 mm. There is a description of a method for producing a cellulose ester film in which the thickness variation is within 0.5 μm, and the present invention can also be applied to the present invention.

In the present invention, the retardation Re in the in-plane direction of the cellulose acylate film formed as described above is particularly preferably less than 500 nm,
It is preferably less than m, more preferably less than 200 nm, still more preferably 100 nm or less, still more preferably 50 nm or less, and even more preferably 30 nm or less. The thickness is particularly preferably 10 nm or less, and more preferably 5 nm. The Rth of the cellulose acylate film of the present invention is 100 μm.
The hit is 0 nm to 600 nm, and further, 0 nm to 400 nm. Especially 0
It is preferable to use at nm to 250 nm.

The angle θ (here, θ1) formed by the film-forming direction (corresponding to the longitudinal direction) of the optical film of the present invention and the slow axis of the film is preferably closer to 0 °, + 90 °, or −90 °. However, θ1 is a narrow angle formed by the film forming direction and the slow axis, and is in the range of + 90 ° to −90 °. When using as a polarizing plate protective film especially, it contributes to the polarization degree improvement of the polarizing plate obtained. Here, the slow axis is the direction in which the in-plane refractive index is highest.

In the present invention, the cellulose acylate film formed as described above is 105
It is preferable that the vertical and horizontal dimensional shrinkage under the condition of 5 ° C. at 5 ° C. is ± 0.1% or less. Further, the haze in terms of 80 μm of the cellulose acylate film is preferably 0.6% or less, particularly preferably that having a haze value of 0.5% or less, more preferably 0.8.
1% or less. The lower limit of the haze value is not particularly limited.

In JP-A-2002-214432, in order to improve the light transmittance of the polarizing plate, the light transmittance measured with one film and the four films are stacked so as to be in the same direction, and a polarizing plate is produced. There is a description about a polarizing plate protective film made of a film having a difference of 1.0% or less from the light transmittance measured with a laminate bonded with the adhesive used in the process.

Furthermore, Japanese Patent Laid-Open No. 2002-221620 discloses that the inclination of streaky unevenness having a horizontal pitch of 3 to 15 mm is 0.04 so that the screen quality of the liquid crystal display device is improved without visible streaky unevenness. There is a description about a film for polarizing plates that is less than 1 degree.

Japanese Patent Application Laid-Open No. 2003-055477 discloses at least one of the vertical direction (mD) and the horizontal direction (TD) in order to improve frame-shaped light leakage and optical density unevenness generated on the display screen of a liquid crystal display device. A cellulose acetate film is described in which variations in thermal expansion coefficient, in-plane Re, and thickness direction Rth in one direction are defined.

Further, in JP 2003-14556, the ratio of the plasticizer content to the other when divided into two in the thickness direction is 1.2 to 2.0, and the curl radius in water at 25 ° C. is 25 mm or more. There is a description of a cellulose acylate film suitable for producing a polarizing plate having a small size and excellent workability. These inventions described above can also be applied to the present invention.

The tear strength of the optical film of the present invention is preferably 10 g or more, more preferably 12 g or more, further preferably 15 g or more, further preferably 18 g or more, and further preferably 20 g or more. Preferably, it is more preferably 22 g or more. The tensile strength of the cellulose acylate film is preferably 50 N / mm ² or more, and the elastic modulus is preferably 3 kN / mm ² or more. Further, the coefficient of dynamic friction of the cellulose acylate film is preferably 0.40 or less, more preferably 0.8.
35 or less.

The optical film of the present invention is excellent in dimensional stability, and the dimensional shrinkage when left for 12 hours at 80 ° C. and 90% RH is less than ± 0.5%, more preferably less than 0.3%. More preferably, it is less than 0.1%, More preferably, it is less than 0.08%, More preferably, it is less than 0.06%, More preferably, it is less than 0.04%.

In addition, in JP 2003-098345, even if the thickness of the polarizing plate protective film is as thin as 20 to 60 μm, there is no wrinkle, bending, distortion, and a polarizing plate having excellent dimensional stability is obtained. A polarizing plate to which a cellulose ester protective film is bonded. When the dimensional change rate of the polarizing film is a and the dimensional change rate of the protective film is b, b / a ≦ 0.20 and the cellulose ester film thickness is 20 to 60 μm.
Thus, a polarizing plate protective film that has a cellulose ester film elastic modulus ≧ 3000 mPa is proposed.

In addition, JP 2000-009931 A relates to a protective film, the surface shape is good, there is no moiré failure, and the cylinder on the surface of the resin film and the profile after tilt correction are 7.5 mm × in order to prevent scratches due to conveyance slip. Within a 0.5mm field of view, the pitch is 1 to 4mm and the height is 0.1 to 0.3μ
There is at least one swell of m, and the center line average roughness of the three-dimensional profile is Ra1,
If the maximum roughness is Rt1, the centerline average roughness of the 3D profile after tilt correction in the 75mmX55.6mm field of view is Ra2, and the maximum roughness is Rt2, (Ra1 / Ra2) X (Rt1 / Rt2) is 20 ~ There is a description of a protective film for polarizing plate to be 70.

Further, JP 2001-343528 A describes that at least one surface of a polarizing plate protective film polarizing element is used in order to improve the productivity without degrading the polarizing performance, good adhesion to the polarizing plate protective film with the polarizing element, and improving productivity. In the polarizing plate protective film to be adhered, a polarizing plate protective film having a moisture permeability of 3 to 10 g / m ² · 24 Hr is described.

Japanese Patent Application Laid-Open No. 2002-122735 discloses a polarizing plate having a shrinkage rate of 0.2% or less after heat treatment at 80 ° C. for 24 hours in order to provide a protective film for a polarizing plate in which a liquid crystal display device does not leak light for a long period of time. There is a description about the film.

Japanese Patent Laid-Open No. 2002-194107 discloses that the maximum scratch size per 5 m ² of at least one side of the film is 1 in order to provide an optical film that can be used stably for high-quality optical applications such as LCD. An optical film is described in which a single flaw formed by combining single flaws or a plurality of flaws has a length of 50 μm or less, a width of 15 μm or less, and a depth of 0.1 μm or less. These inventions described above can also be applied to the present invention.

[Usage]
The use of the cellulose acylate produced in the present invention will be briefly outlined first, and details will be described later. The optical film of the present invention is particularly useful for a polarizing plate protective film. When using as a polarizing plate protective film, the manufacturing method of a polarizing plate is not specifically limited, It can manufacture by a general method. There is a method in which the obtained cellulose acylate film is treated with an alkali and bonded to both sides of a polarizer prepared by immersing and stretching a polyvinyl alcohol film in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. Instead of alkali treatment, easy adhesion processing as described in JP-A-6-94915 and JP-A-6-118232 may be performed.

As an adhesive used to bond the protective film treated surface and the polarizer, for example,
Examples thereof include polyvinyl alcohol adhesives such as polyvinyl alcohol and polyvinyl butyral, and vinyl latexes such as butyl acrylate. The polarizing plate is composed of a polarizer and a protective film that protects both surfaces of the polarizer. Further, a protective film is laminated on one surface of the polarizing plate, and a separate film is laminated on the opposite surface. The protective film and the separate film are used for the purpose of protecting the polarizing plate at the time of shipping the polarizing plate and at the time of product inspection. In this case, the protect film is bonded for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the surface where the polarizing plate is bonded to the liquid crystal plate. Moreover, a separate film is used in order to cover the adhesive layer bonded to a liquid crystal plate, and is used for the surface side which bonds a polarizing plate to a liquid crystal plate.
In a liquid crystal display device, a substrate containing liquid crystal is usually disposed between two polarizing plates. However, a polarizing plate protective film to which the optical film of the present invention is applied can provide excellent display properties regardless of the location. . Especially for the polarizing plate protective film on the outermost surface of the liquid crystal display device, a transparent hard coat layer
Since a glare-proof layer, an antireflection layer, etc. are provided, it is preferable to use this polarizing plate protective film for this part.

These include, for example, an area shrinkage ratio of less than 10% at 85 ° C., 90%, and 500 hours described in JP-A-09-096722, and an equilibrium moisture content of the film at 25 ° C. and 65% of 2.5 mass. It is a lower fatty acid cellulose acylate polarizing plate protective film that is less than%,
This is intended to improve wet heat resistance and workability of the polarizing plate protective film. Japanese Laid-Open Patent Publication No. 07-2187
No. 24 is a polarizing plate using a film made of cellulose acylate having a Re value of 590 nm in the range of 30 nm to 70 nm as a protective film of the polarizing plate.
The cellulose acylate of the present invention is also preferably used for polarizing plates that can significantly improve the coloring and contrast of reflective STN-LCDs and elliptically polarizing plates.

In addition, in order to obtain a polarizing plate protective film with excellent optical isotropy, flatness, and a small orientation angle distribution, in-plane retardation RO and orientation angle θ are 10-2√2XsiN2θXπ / 180-RO ≧ 0RO
There is a description that a film satisfying (film thickness (nm)) is used as a polarizing plate protective film, and the present invention can also be applied to the present invention.

Japanese Patent Laid-Open No. 2000-154261 discloses a cellulose acetate film having an acetylation degree of 55 to 58% and a retardation (Rth) in the thickness direction at a wavelength of 550 nm of 200 to 40.
There is a description of a cellulose acetate film having a thickness of 0 nm.
No. 52328 is an optical compensatory sheet having discotic liquid crystalline molecules, and the discotic liquid crystalline molecules are oriented in a state where the average inclination angle between the disc surface and the base surface is less than 5 °,
This is a patent disclosure in which discotic liquid crystal molecules are fixed in the alignment state, and can be developed into an optical compensation sheet suitable for a liquid crystal device of a VA liquid crystal mode or an OCB liquid crystal mode. Japanese Laid-Open Patent Publication No. 1
No. 1-316378 relates to a laminated body of an anisotropic layer including a disk-like material, an anisotropic base, and a polarizing film, and an orthogonal projection direction of the outer elliptical polarizing plate, a disk surface normal base, and an in-plane of the base An optically anisotropic layer having an angle of 45 ° to the slow axis and the in-plane slow axis of the base and the in-plane transmission axis of the polarizing film being parallel or perpendicular, and an elliptically polarizing plate of the base and the polarizing film, The object is to further improve the viewing angle characteristics of the liquid crystal device of the bend alignment liquid crystal mode and horizontal alignment liquid crystal mode without causing coloring of the display image. Regarding these contents, the cellulose acylate film of the present invention can be preferably used.

Japanese Patent Application Laid-Open No. 08-050206 discloses an optical compensation sheet in which an optical anisotropic layer is formed of a discotic compound, a disc surface is inclined with respect to a base, and changes in the depth direction of the optical anisotropic layer, and the sheet The present invention relates to a liquid crystal device and a color liquid crystal device, and is used for an optical compensation sheet or a liquid crystal device and a color liquid crystal device that can be easily manufactured and has a wide viewing angle. JP-A 09-216955 discloses that the surface orientation in the vicinity of the surface on at least one side of the cellulose acylate film is weaker than the surface orientation inside the film, and has excellent scratch resistance and dimensional stability. It is said that a cellulose acylate film can be obtained. Furthermore, in Japanese Patent Laid-Open No. 10-043427, -100 to 10 is used.
The cellulose acetate film produced by cooling to 0 ° C and heating to 0 to 120 ° C is provided with a coating layer of a coating solution containing a polymer and fine particles of 1 µm or less, and the haze is 2.0% or less or converted to 80 µm thickness Has a tear strength of 18 g or more and a coating layer dynamic friction coefficient of 0
. No. 4 or less cellulose acetate film is disclosed, and relates to a cellulose acetate film having excellent optical properties and physical properties.

In Japanese Patent Laid-Open No. 10-095861, it is cooled to -100 to -10 ° C and dissolved at 0 to 120 ° C.
The cellulose acetate film obtained by heating to 80% with an average degree of acetylation of 58-62.5%
The haze in terms of thickness of μm is 0.4% or less, or the tear strength in terms of thickness of 80 μm is 20 g
The present invention relates to a cellulose acetate film as described above, and a cellulose acetate film having excellent optical properties or physical properties is disclosed. Further, JP-A-10-09
No. 5862 discloses a degree of acetylation of 5 obtained by cooling at −100 to −10 ° C. and heating to 0 to 120 ° C.
8 to 62.5% cellulose acylate, 80 μm thickness haze is 0.6% or less, or 80 μm thickness conversion tear strength is 18 g or more, and dynamic friction coefficient of film surface is 0 .4 or less cellulose acetate film, and a cellulose acetate film having excellent optical properties is disclosed. Furthermore, JP-A 09-113727 relates to a film having a longitudinal shrinkage rate of less than 0.05% and a Re value of less than 10 nm after standing at 80 ° C. for 3 hours as a polarizing plate protective film. What improved the dimensional stability and optical characteristic of the polarizing plate protective film is disclosed. The cellulose acylate of the present invention is preferably used for the engineering applications disclosed in the above publications.

Japanese Patent Laid-Open No. 2000-284124 discloses an elliptically polarizing plate in which a transparent protective film, a polarizing film, and an optically anisotropic protective film are laminated in this order, and the optically anisotropic protective film is 0.7 to 1 .3
An elliptically polarizing plate having a refractive index anisotropy wavelength dispersion value is disclosed and has excellent optical characteristics. In JP 2000-284123 A, a transparent protective film, a polarizing film,
The transparent support, the optically anisotropic protective film of liquid crystalline molecules are laminated elliptical polarizing plates in order, and the optically anisotropic protective film has an elliptical refractive index anisotropy wavelength dispersion value of 0.7 to 1.3 It is described that a polarizing plate is excellent in optical characteristics. Further, in JP-A-11-254466, when two polarizing plates are arranged on both sides of a cellulose acylate film so as to block transmitted light, the number of bright spot diameters of 0.05 mm is 0 / cm ^2. The number of bright spots having a diameter of 0.01 to 0.05 mm is 500 / c.
A cellulose acylate film of m ² is disclosed, and it is disclosed to provide a cellulose acylate film exhibiting particularly excellent visibility for optical applications such as a polarizing plate protective film of a liquid crystal device. These inventions can also be applied to the cellulose acylate film of the present invention,
This is a preferred embodiment.

Further, Japanese Patent Application Laid-Open No. 2000-131523 is a protective film for a polarizing plate of a vertical alignment type liquid crystal display device, and the retardation value of the film is 5 to 25.
The present invention relates to a polarizing plate protective film having a thickness of nm, and the viewing angle is improved. Japanese Patent Application Laid-Open No. 06-130226 discloses that the amount of change in transmittance of 400 nm or more after 1000 hours at 80 ° C., 90% RH is 2% or less, and 10 degrees field of view XYZ system three-dimensional in accordance with JISZ8720 standard light. Stimulus value a value, b value change amount is 0.1
0.3 is a cellulose acylate film containing a specific benzotriazole UV absorber, and the UV absorption performance is not deteriorated or colored even when exposed to high temperature and high humidity for a long time. It is disclosed. Japanese Patent Laid-Open No. 06-235819 discloses that the amount of change in transmittance at a wavelength of 400 nm or more after 1000 hours at 80 ° C. and 90% RH is 2% or less, and a JISZ8729 standard light of JISZ8720 defines a 10 degree visual field XYZ system tristimulus. The cellulose acylate having a value of change of a and b of 0.1 to 0.3 is characterized by containing a benzotriazole-based UV agent and a metal oxide having a particle size of 0.1 μm. It has been shown that the cellulose acylate does not deteriorate in UV absorption performance or color even when exposed to high humidity for a long time. Japanese Patent Laid-Open No. 2000-2122
No. 98 discloses a cellulose acylate film used for a liquid crystal display member having a film thickness of 20 to 60 μm and a film thickness variation within ± 3.0% of a reference film thickness. It is disclosed that it suppresses wrinkles, increases the yield, and has good transparency and Rth. Further, in Japanese Patent Laid-Open No. 2000-204173, the number of foreign matters having a size of 5 to 50 μm recognized in the crossed Nicol state is 200 or less per 250 mm ² , and the size recognized in the crossed Nicol state exceeds 50 μm. The foreign matter relates to a film characterized in that the number is substantially 0 per 250 mm ² , and a cellulose acylate film suitable for a high-definition liquid crystal display element without irregular light emission is disclosed.

Furthermore, in JP2003-073485, in order to obtain an optical compensation film having a high viewing angle widening effect, the in-plane retardation (R0) and the thickness direction retardation (Rt) are represented by the formula (1) 0.8 <
Rt / R0 <2.5, formula (2)
41nm <R0 <300nm
And a cellulose ester film containing two or more types of cellulose esters having different degrees of substitution of acyl groups or different substituents, satisfying Nx>Ny> NZ. In any of the above inventions, the cellulose acylate film of the present invention can be applied.

(General liquid crystal display configuration)
The cellulose acylate film of the present invention can be used in various applications, and is particularly effective when used as an optical compensation sheet for liquid crystal display devices. When a cellulose acylate film is used as an optical compensation sheet, the transmission axis of a polarizing element (described later) and the slow axis of an optical compensation sheet made of a cellulose acylate film may be arranged at any angle.
The liquid crystal display device includes a liquid crystal cell having a liquid crystal supported between two electrode substrates, two polarizing elements disposed on both sides thereof, and at least one sheet between the liquid crystal cell and the polarizing element. An optical compensation sheet is arranged.

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

The optical compensation sheet has birefringence and is used for the purpose of removing the color of the display screen of the liquid crystal display device or improving the viewing angle characteristics. The cellulose acylate film itself of the present invention can be used as an optical compensation sheet. Furthermore, antireflection layer, antiglare layer, λ
A function may be imparted as a / 4 layer or biaxially stretched cellulose acylate film. In addition, in order to improve the viewing angle of the liquid crystal display device, the cellulose acylate film of the present invention and a film showing birefringence (positive / negative relationship) opposite thereto may be used as an optical compensation sheet. . The thickness range of the optical compensation sheet is the same as the preferable thickness of the film of the present invention described above.

Examples of the polarizing film of the polarizing element include an iodine polarizing film, a dye polarizing film using a dichroic dye, and a polyene polarizing film. Any polarizing film is generally manufactured using a polyvinyl alcohol film. The protective film of the polarizing plate preferably has a thickness of 25 to 350 μm,
More preferably, it has a thickness of ˜200 μm. The liquid crystal display device may be provided with a surface treatment film. The functions of the surface treatment film include hard coat, anti-fogging treatment, anti-glare treatment and antireflection treatment.

As described above, there has also been proposed an optical compensation sheet in which an optically anisotropic layer containing a liquid crystal compound (particularly a discotic liquid crystal molecule) is provided on a support (Japanese Patent Application Laid-Open Nos. 3-9325 and Hei. 6-148429, JP-A-8-50206, JP-A-9-26572). The cellulose acylate film of the present invention can also be used as a support for such an optical compensation sheet.

Japanese Patent Application Laid-Open No. 2002-243942 discloses a polarizing plate a, an optically anisotropic layer formed by aligning and fixing a liquid crystal compound in a specific direction, and an optical biaxial, in order to improve viewing angle characteristics. In the viewing angle compensation elliptically polarizing plate having the transparent support C having the property, (1) the optically anisotropic layer is formed directly on the polarizing plate a or via another transparent support, and then (2 A viewing angle compensated elliptically polarizing plate manufactured through the step of providing the transparent support C having the optical biaxiality directly or via another layer on the optically anisotropic layer is described.

Furthermore, Japanese Patent Application Laid-Open No. 2003-021718 describes an optical compensation sheet for a biaxial support for improving contrast reduction, coloring, and color reversal in an oblique direction in the vertical and horizontal directions.

JP 2002-286933 discloses a stretched film composition having birefringence that stretches in a direction perpendicular to the transport direction in order to improve the viewing angle characteristics of a TN type LCD. A stretched film composition is described in which a stretched second film stretched under the same conditions as the first film is laminated so that the angle formed by the transport direction is 180 degrees.

Furthermore, Japanese Patent Laid-Open No. 2001-249223 describes an acetylation degree of 59 to 61.5% in order to optically compensate the liquid crystal cell.
An optical compensatory sheet using only cellulose acetate film of TAC and two or more aromatic ring compounds of 0.01 to 20%, Re20 to 70 nm, and Rth 70 to 400 nm is disclosed.

Japanese Patent Application Laid-Open No. 2002-090541 has at least two aromatic rings and cellulose acetate having an acetylation degree of 59 to 61.5% in order to produce a liquid crystal display device free from light leakage due to thermal distortion and excellent in display quality. An optical compensation sheet comprising an optically anisotropic layer formed from a liquid crystalline compound on a cellulose acetate film containing 0.01 to 20 parts by mass of an aromatic compound, and has a hygroscopic expansion coefficient of 30 × 10 ⁻⁵ /% An optical compensation sheet that is RH or less is described.

Furthermore, Japanese Patent Application Laid-Open No. 2002-131549 optically compensates for liquid crystal cells and causes plasticizer precipitation (bleed out).
) Degree of acetylation 59.0-61.5% cellulose acetate film contains 5-30% by weight plasticizer, surface partial plasticizer amount of film is less than the overall average, Re20-70nm, Rth70-400nm
The optical compensation sheet is described.

Furthermore, Japanese Patent Application Laid-Open No. 2002-139621 discloses a liquid crystal display device with a high display quality of 59-6.
Re is 20-70 nm comprising a single cellulose acetate film having a degree of acetylation of 0.01 to 20 parts by mass of an aromatic compound having at least two aromatic rings and a thickness of 10 to 70 μm. There is a description of an optical compensation sheet of Rth 70 to 400 nm.

Further, JP-A-2002-156527 discloses that a cellulose acetate film having an acetylation degree of 59 to 61.5% is used to provide a liquid crystal display device having a high display quality using an optical compensation film made of a positive uniaxial liquid crystalline compound. In addition, an optically anisotropic layer formed from a liquid crystalline compound exhibiting optically positive uniaxiality and fixing a nematic hybrid alignment structure in a liquid crystalline compound liquid crystal state is provided. An optical compensation film having a thickness of 0 to 20 nm and Rth of 30 to 70 nm is described. JP-A-2002-169023 discloses a cellulose acetate having an acetylation degree of 59.0 to 61.5% in order to provide a liquid crystal display device excellent in display quality without light leakage due to thermal distortion.
An optical compensation sheet comprising an optically anisotropic layer formed of a liquid crystalline compound on a cellulose acetate film containing 0.01 to 20 parts by mass of at least two aromatic ring aromatic compounds. ~ 20nm, Rth70 ~ 400nm and thickness 10 ~ 70μm
The optical compensation sheet is described.

Furthermore, Japanese Patent Laid-Open No. 2002-196137 discloses a uniaxial / biaxial optical compensation sheet along the film surface of Re (550) in order to uniformly optically compensate the liquid crystal cell surface of the liquid crystal display device. The fluctuation in any direction is in the range of ± 5 nm with respect to the average value of Re in each direction, and the fluctuation in any direction along the Rth film surface is in any direction. In addition, an optical compensation sheet that is ± 10 nm with respect to the average value of Rth in each direction is described.

Japanese Patent Laid-Open No. 2002-196138 discloses a uniaxial / biaxial optical compensation sheet that has been subjected to stretching treatment in order to extend optically the liquid crystal cell in order to reduce frame failure and bright spot failure. Describes an optical compensation sheet having an elongation at break of 10 to 30%.

Furthermore, in JP-A-2002-196146, in order to provide a liquid crystal display device having excellent display quality, the optically anisotropic layer is a layer made of a discotic structural unit compound, and the disc surface of the discotic structural unit is transparently supported. An optical compensation sheet that is inclined with respect to the body surface and the angle between the disc surface of the discotic structural unit and the transparent support surface has local fluctuations and changes in the depth direction of the optical anisotropic layer. Has been described.

Japanese Patent Application Laid-Open No. 2002-267840 describes an optical compensation sheet having a polymer film having a thermal shrinkage start temperature of 130 ° C. or more and 190 ° C. or less in order to provide an optical compensation sheet in which display unevenness hardly occurs. .

Furthermore, in JP2003-066230, in order to provide an optical compensation sheet with improved viewing angle characteristics and color spots, Re20 to 70 nm, Rth 70 to 400 nm, the axis of the misalignment angle between the slow axis angle and the stretching direction. Range
An optical compensation sheet composed of a polymer film of 5 ° or less is described.

In order to provide an optical compensation sheet having excellent adhesion durability in JP-A-2003-043250,
It is composed of a polymer film containing C, H, O in the polymer skeleton and a polymer film containing 0.5 to 15% by mass of two or more aromatic ring-containing compounds.
(X) There is a description of an optical compensation sheet in which Δm (X) or Δm (O) defined as B is 5% or less. These inventions described above can also be applied to the present invention.

[Optically anisotropic layer containing discotic liquid crystalline molecules]
The optical anisotropy including the discotic liquid crystalline molecules may be in a hybrid orientation in which the angle between the disc surface and the support surface changes in the depth direction of the optical anisotropic layer, and the disc surface supports it. Homeotropic orientation parallel to the surface of the body, homogeneous orientation where the disc surface is perpendicular to the support surface, twist orientation where the disc surface is twisted in the depth direction of the optically anisotropic layer, or the disc surface is uniformly inclined and negative You may take the orientation which shows uniaxiality. Moreover, the orientation in which these orientations are mixed (for example, hybrid orientation + twist orientation) may be used. Among these, the hybrid orientation is preferable. Further, the optical axis does not exist in the layer in which the discotic liquid crystalline molecules are hybrid-aligned.

The angle of the surface of the discotic structural unit (average inclination angle) has fluctuations at a certain local depth, but generally the depth of the optical anisotropic layer when viewed as the entire optical anisotropic layer. Increase or decrease with increasing direction and distance from the bottom of the optically anisotropic layer. The average inclination angle preferably increases with increasing distance while having this fluctuation. Furthermore, examples of changes in the average inclination angle include continuous increase, continuous decrease, intermittent increase, intermittent decrease, change including continuous increase and continuous decrease, and intermittent change including increase and decrease. Can do. It is preferable that the intermittent change includes an area where the average inclination angle does not change in the middle of the thickness direction, but the average inclination angle increases or decreases as a whole even if the average inclination angle includes an area which does not change. Furthermore, the average tilt angle generally increases as a whole of the optically anisotropic layer, and it is particularly preferable that the average tilt angle changes continuously.

The average inclination angle (angle) is preferably changed in the range of 5 to 85 degrees (particularly in the range of 10 to 80 degrees). The minimum value of the average average inclination angle is preferably in the range of 0 to 85 degrees (particularly 5 to 40 degrees), and the maximum value is preferably in the range of 5 to 90 degrees (particularly 30 to 85 degrees). The average tilt angle (eg, θa) of the discotic structural unit on the support side corresponds to a substantially minimum value, and the average tilt angle (eg, θc) of the discotic structural unit corresponds to a substantially maximum value. . Furthermore, the difference between the minimum value and the maximum value of the average average inclination angle is in the range of 5 to 70 degrees (
In particular, it is preferably 10 to 60 degrees.

(Liquid crystal display device)
The cellulose acylate film of the present invention can be used for liquid crystal cells in various display modes. TN (Twisted Nematic), IPS (In-Plane Sw
itching), FLC (Ferroelectric Liquid Crysta)
l), AFLC (Anti-ferroelectric Liquid Crysta)
l), OCB (Optically Compensatory Bend), STN (
Super Twisted Nematic), VA (Vertically Al
Various display modes have been proposed, such as “igned” and HAN (Hybrid Aligned Nematic). In addition, a display mode in which the above display mode is oriented and divided has been proposed. The cellulose acylate film of the present invention is effective in any display mode liquid crystal display device. Further, it is effective in any of a transmissive, reflective, and transflective liquid crystal display device.

(TN type liquid crystal display device)
The cellulose acylate film of the present invention may be used as a support for an optical compensation sheet of a TN type liquid crystal display device having a TN mode liquid crystal cell. TN mode liquid crystal cells and TN type liquid crystal display devices have been well known for a long time. As for the optical compensation sheet used in the TN type liquid crystal display device, JP-A-3-9325, JP-A-6-148429, JP-A-8-
No. 50206 and JP-A-9-26572. Also, Mori
Other papers (Jpn. J. Appl. Phys. Vol. 36 (1997) p. 1
43, Jpn. J. et al. Appl. Phys. Vol. 36 (1997) p. 10
68).

(TN mode liquid crystal display)
Hereinafter, constituent members of one embodiment of the TN mode liquid crystal display device of the present invention will be sequentially described. FIG. 19 is a schematic view of an embodiment of the liquid crystal display device of the present invention. The liquid crystal display device shown in FIG. 19 includes an upper polarizing plate TN1 and a lower polarizing plate TN12 that are disposed with a liquid crystal cell interposed therebetween. The polarizing plates TN1 and TN12 are sandwiched between a polarizing film and a pair of transparent protective films, but are shown as integrated polarizing plates TN1 and TN12 in FIG. The liquid crystal cell includes a liquid crystal layer formed of an upper substrate TN5 and a lower substrate TN8 and liquid crystal molecules TN7 sandwiched between them. An alignment film (not shown) is formed on the surfaces of the substrates TN5 and TN8 that are in contact with the liquid crystal molecules TN7 (hereinafter also referred to as “inner surface”). The alignment of the liquid crystal molecules TN7 in a state where no voltage is applied or a state where a voltage is not applied is controlled. Further, on the inner surfaces of the substrates TN5 and TN8, a transparent electrode (not shown) capable of applying a voltage to the liquid crystal layer made of the liquid crystal molecules TN7 is formed.

19 has a positive dielectric anisotropy, a refractive index anisotropy, Δn = 0.0854 (589 nm, 20 ° C.), and a liquid crystal having Δε = + 8.5 (for example, MLC manufactured by Merck & Co., Inc.). -9100). The alignment control of the liquid crystal layer is controlled by the alignment film and rubbing. A director indicating the alignment direction of the liquid crystal molecules, that is, a so-called tilt angle is created with rubbing of about 3 °. The rubbing direction is provided in a direction perpendicular to the upper and lower substrates, and the tilt angle can be controlled by the strength and the number of rubbing times. The alignment film is formed by applying and baking a polyimide film. The twist angle (twist angle) of the liquid crystal layer is determined by the crossing angle of the rubbing direction between the upper and lower substrates and the chiral material added to the liquid crystal material. Here, a chiral material having a pitch of about 60 μm is added so that the twist angle is 90 °. The twist angle is about 90 ° (85 to 95 °) in the case of a liquid crystal display device for notebook computers, personal computer monitors, and televisions, and 0 to 70 ° in the case of use as a reflective display device such as a mobile phone. Set. The thickness d1 of the liquid crystal layer is set to 5 μm. Here, the brightness at the time of white display changes depending on the size of the product Δn · d1 of the thickness d1 and the refractive index anisotropy Δn. Therefore, in order to obtain the maximum brightness, the thickness d1 is set to be in the range of 0.2 to 0.5 μm.

The liquid crystal material is not particularly limited as long as it is a nematic liquid crystal. The larger the value of the dielectric anisotropy Δε, the lower the driving voltage, and the smaller the refractive index anisotropy Δn, the thicker the liquid crystal layer (gap), the shorter the liquid crystal sealing time, and the gap. Variation can be reduced. The upper polarizing plate TN1 and the lower polarizing plate TN12 are stacked so that the absorption axis TN2 of the upper polarizing plate TN1 and the absorption axis TN13 of the lower polarizing plate TN12 are substantially orthogonal to each other. Further, lamination is performed so that the absorption axis TN2 and the rubbing direction TN6 of the upper substrate TN5 are substantially parallel. Further, the absorption axis TN13 and the rubbing direction TN9 of the lower substrate TN8 are laminated so as to be substantially parallel. Transparent electrodes (not shown) are formed inside the alignment films of the upper substrate TN5 and the lower substrate TN8. In a non-driving state in which no driving voltage is applied to the electrodes, the liquid crystal molecules TN7 in the liquid crystal cell As a result, the polarization state of light passing through the liquid crystal panel is propagated along the twisted structure of the liquid crystal molecules, and the polarization plane is rotated by 90 ° and emitted. That is, the liquid crystal display device realizes white display in the non-driven state. In contrast,
In the driving state, the liquid crystal molecules are aligned substantially perpendicular to the substrate surface, so that the light passing through the liquid crystal panel passes through without changing the polarization state. In other words, an ideal black display can be obtained in the driving state in the liquid crystal display device.

The liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 19 and may include other members. For example, a color filter may be disposed between the liquid crystal cell and the polarizing film. Further, as will be described later, optical compensation sheets TN3 and TN10 can be separately disposed between the liquid crystal cell and the polarizing plate.

In JP-A-6-214116, an optical compensation sheet for a TN mode liquid crystal cell performs optical compensation of an orientation state in which liquid crystal molecules are tilted to a substrate surface while eliminating a twisted structure by applying a voltage, and displays black. Improving the viewing angle characteristic of contrast by preventing light leakage in the oblique direction.

In the case of use as a transmission type, a cold cathode or a hot cathode fluorescent tube, or a backlight using a light emitting diode, a field emission element, or an electroluminescent element as a light source can be disposed on the back surface. In addition, the liquid crystal display device of the present invention may be of a reflective type. In such a case, only one polarizing plate may be disposed on the observation side, and reflected on the back surface of the liquid crystal cell or the inner surface of the lower substrate of the liquid crystal cell. Install the membrane. Of course, it is also possible to provide a front light using the light source on the liquid crystal cell observation side.

(STN type liquid crystal display device)
The cellulose acylate film of the present invention may be used as a support for an optical compensation sheet of an STN type liquid crystal display device having an STN mode liquid crystal cell. In general, in a STN type liquid crystal display device, rod-like liquid crystalline molecules in a liquid crystal cell are twisted in the range of 90 to 360 degrees, and the refractive index anisotropy (Δn) and cell gap (d ) Product (Δnd) is 300-1
It is in the range of 500 nm. The optical compensation sheet used for the STN type liquid crystal display device is described in JP-A-2000-105316.

(VA type liquid crystal display device)
The cellulose acylate film of the present invention is particularly advantageously used as a support for an optical compensation sheet of a VA liquid crystal display device having a VA mode liquid crystal cell. It is preferable that the Re retardation value of the optical compensation sheet used in the VA liquid crystal display device is 0 to 150 nm and the Rth retardation value is 70 to 400 nm. Re retardation value is 2
More preferably, it is 0 to 70 nm. When two optically anisotropic polymer films are used in a VA liquid crystal display device, the Rth retardation value of the film is 70 to 250 n.
m is preferable. When a single optically anisotropic polymer film is used for the VA liquid crystal display device, the Rth retardation value of the film is preferably 150 to 400 nm. The VA-type liquid crystal display device may be an alignment-divided system as described in, for example, JP-A-10-123576.

Next, constituent members of one embodiment of the VA mode liquid crystal display device of the present invention will be sequentially described.
FIG. 20 is a schematic view of an embodiment of the liquid crystal display device of the present invention. The liquid crystal display device shown in FIG. 20 includes an upper polarizing plate VA1 and a lower polarizing plate VA14 that are disposed with a liquid crystal cell interposed therebetween. In the VA mode, the dielectric anisotropy is negative between the upper and lower substrates, and Δn = 0.0813, Δε = −4.6.
A liquid crystal (for example, MLC-6608 manufactured by Merck & Co., Inc.) is formed by rubbing alignment so that a director indicating the alignment direction of liquid crystal molecules, that is, a tilt angle with respect to a substrate surface is about 89 °.
The thickness d2 of the liquid crystal layer VA7 is set to 3.5 μm. Where the thickness d2 and the refractive index anisotropy Δ
The brightness at the time of white display changes depending on the magnitude of the product of n, Δn · d2. Therefore, in order to obtain maximum brightness, the thickness d2 is in the range of 0.2 to 0.5 μm, preferably 0.25 to 0.3 μm.
It sets so that it may become the range of 5 micrometers.

The polarizing plates VA1 and VA14 are stacked so that the absorption axis VA2 of the upper polarizing plate VA1 of the liquid crystal cell and the absorption axis VA15 of the lower polarizing plate VA14 are substantially orthogonal to each other. Transparent electrodes (not shown) are formed inside the alignment films (not shown) of the upper substrate VA5 and the lower substrate VA8, but in a non-driving state where no driving voltage is applied to the electrodes, the liquid crystal layer VA7 The liquid crystal molecules therein are aligned substantially perpendicular to the substrate surface like the liquid crystal molecules VA16. As a result, the polarization state of the light passing through the liquid crystal panel hardly changes. That is, this liquid crystal display device realizes an ideal black display in the non-driven state. On the other hand, in the driving state, the liquid crystal molecules are inclined substantially parallel to the substrate surface, and the light passing through the liquid crystal panel changes the polarization state by the inclined liquid crystal molecules.
In other words, in the liquid crystal display device, white display is obtained in the driving state.

Here, since an electric field is applied between the upper and lower substrates VA5 and VA8, a liquid crystal material having a negative dielectric anisotropy is used so that the liquid crystal molecule VA16 responds perpendicularly to the electric field direction. When an electrode is arranged on one substrate and an electric field is applied in a lateral direction parallel to the substrate surface, a liquid crystal material having a positive dielectric anisotropy is used. In addition, in a VA mode liquid crystal display device, the addition of a chiral material generally used in a TN mode liquid crystal display device is rarely used to degrade dynamic response characteristics, but in order to reduce alignment defects. Sometimes added.

The features of the VA mode are high-speed response and high contrast. However,
The contrast is high in the front, but there is a problem that it deteriorates in the oblique direction. During black display, the liquid crystal molecules are aligned perpendicular to the substrate surface. When viewed from the front, the liquid crystal molecules have little birefringence, so the transmittance is low and high contrast is obtained. However, when observed obliquely, birefringence occurs in the liquid crystal molecules. Furthermore, the crossing angle between the upper and lower polarizing plate absorption axes is 90 ° perpendicular to the front, but is greater than 90 ° when viewed from an oblique direction. Because of these two factors, leakage light occurs in the oblique direction, and the contrast is lowered. To solve this, the optical compensation sheets VA3, V
A10 and VA12 are arranged. The liquid crystal molecules are tilted during white display, but the birefringence of the liquid crystal molecules when viewed from an oblique direction differs between the tilt direction and the opposite direction, resulting in differences in brightness and color tone. In order to solve this problem, a structure called a multi-domain in which one pixel of a liquid crystal display device is divided into a plurality of regions is adopted.

(OCB type liquid crystal display device and HAN type liquid crystal display device)
The cellulose acylate film of the present invention is also advantageously used as a support for an optical compensation sheet of an OCB type liquid crystal display device having an OCB mode liquid crystal cell or a HAN type liquid crystal display device having a HAN mode liquid crystal cell. In the optical compensation sheet used for the OCB type liquid crystal display device or the HAN type liquid crystal display device, it is preferable that the direction in which the absolute value of retardation is minimum does not exist in the plane of the optical compensation sheet or in the normal direction. The optical properties of the optical compensation sheet used in the OCB type liquid crystal display device or the HAN type liquid crystal display device are also the optical properties of the optically anisotropic layer, the optical properties of the support, and the optically anisotropic layer and the support. Is determined by the arrangement of An optical compensation sheet used for an OCB type liquid crystal display device or a HAN type liquid crystal display device is described in JP-A-9-197397. Also, Mori et al. (Jpn. J. Appl. Phys. Vol. 38 (1999) p. 2837).
There is a description.

(Bent mode liquid crystal display)
Next, components of one embodiment of the bend mode liquid crystal display device of the present invention will be sequentially described. FIG. 21 is a schematic view of an embodiment of the liquid crystal display device of the present invention. The liquid crystal display device shown in FIG. 21 includes an upper polarizing plate OCB1 and a lower polarizing plate OC that are arranged with a bend-aligned liquid crystal cell interposed therebetween.
B12, a pair of optically anisotropic layers OCB3 and OCB10 disposed on both sides of the liquid crystal cell, and a backlight (not shown).

The rubbing direction OCB6 of the upper substrate OCB5 of the liquid crystal cell and the rubbing direction OCB9 of the lower substrate OCB8 are the same direction (parallel). The rubbing directions OCB4 and OCB11 for aligning the optically anisotropic layers OCB3 and OCB10 are respectively the substrates OCB5 and OCB facing each other.
8 rubbing directions OCB6 and OCB9 are in antiparallel relation. Polarizing plate OCB1, OCB
The absorption axes OCB2 and OCB13 of 12 are in the rubbing directions OCB4 and OCB1 of the optically anisotropic layer.
In the same plane as 1, the angle is substantially 45 °. And two polarizing plates OCB1, OCB
12, in-plane absorption axes OCB2 and OCB13 are arranged so as to be orthogonal to each other (crossed Nicols).

In the bend alignment liquid crystal cell, a liquid crystal layer OCB14 having a positive dielectric anisotropy between ΔB = 0.0813 and Δε = 4.6 between the upper substrate OCB5 and the lower substrate OCB8 is rubbed to align the liquid crystal molecules OCB14. A director indicating the orientation direction of the film, that is, a so-called tilt angle is created at about 8 °.
Here, the rubbing directions OCB6 and OCB9 are substantially parallel and the same direction. As a result, the alignment of the liquid crystal molecules OCB14 in the liquid crystal layer OCB7 becomes spray alignment in the cell cross-sectional direction. Here, when a chiral agent is added to the liquid crystal layer OCB7 to impart a twisting component, the alignment is stabilized. At this time, when no electric field is applied, the twist angle is 180 degrees. Alternatively, the rubbing directions may be orthogonal and the twist angle may be set to 90 or near 270 degrees.

The thickness d3 of the liquid crystal layer OCB7 is set to 7 μm. Where the thickness d3 and the refractive index anisotropy Δn
The brightness at the time of white display changes depending on the magnitude of the product Δn · d3. Therefore, in order to obtain the maximum brightness, the thickness d3 is set to be in the range of 0.6 to 0.9 μm. The upper substrate OCB5 and the lower substrate OCB8 of the liquid crystal cell each have an alignment film (not shown) and an electrode layer (not shown). The alignment film has a function of aligning the liquid crystal molecules OCB14. The electrode layer has a function of applying a voltage to the liquid crystal molecules OCB14.

When the applied voltage of the bend alignment liquid crystal cell is low, the liquid crystal molecules on the upper substrate OCB5 side and the liquid crystal molecules on the lower substrate OCB8 side of the liquid crystal cell are aligned in substantially opposite directions (vertically symmetrical). Further, the liquid crystal molecules in the vicinity of the substrates OCB5 and OCB8 are aligned in a substantially horizontal direction, and the rod-like liquid crystal molecules in the center of the liquid crystal cell are aligned in a substantially vertical direction. When the applied voltage is high, the substrate OCB5, O
The liquid crystal molecules in the vicinity of CB8 remain substantially horizontally aligned. In addition, the rod-like liquid crystal molecules at the center of the liquid crystal cell remain substantially vertically aligned. The liquid crystal molecules positioned in the middle between the substrate and the central portion of the liquid crystal cell change in alignment with the increase in voltage, and these are aligned perpendicular to the off state. However, the liquid crystal molecules on the upper substrate OCB5 side and the liquid crystal molecules on the lower substrate OCB8 side of the liquid crystal cell are aligned in substantially opposite directions (vertically symmetrical) as in the off state.

The concept of optical compensation in a bend alignment mode liquid crystal display device is that a bend alignment liquid crystal cell includes optically anisotropic layers OCB3 and OCB10 formed from discotic liquid crystalline molecules and a transparent support having optical anisotropy (not shown). ) And optically compensate. Optically anisotropic layer OCB
3, directions OCB4, OCB1 for aligning the discotic liquid crystalline molecules of OCB10
1 is set in an antiparallel relationship with the rubbing directions OCB6 and OCB9 of the liquid crystal cell, the liquid crystal molecules OCB14 of the bend alignment liquid crystal cell correspond to the discotic liquid crystal molecules of the optically anisotropic layers OCB3 and OCB10, Compensate optically. And it is designed so that the optical anisotropy of the transparent support corresponds to the liquid crystal molecules aligned substantially vertically in the center of the bend alignment liquid crystal cell.

(Reflective liquid crystal display)
The cellulose acylate film of the present invention has TN type, STN type, HAN type, GH (Gu
It is also advantageously used as an optical compensation sheet for an est-host type reflective liquid crystal display device. These display modes have been well known since ancient times. The TN type reflection type liquid crystal display device is described in JP-A-10-123478, WO98848320, and Japanese Patent No. 3022477. Regarding the optical compensation sheet used in the reflection type liquid crystal display device, WO00-
There is description in 65384 gazette.

(Other liquid crystal display devices)
The cellulose acylate film of the present invention is an ASM (Axial Symmetr).
It is also advantageously used as a support for an optical compensation sheet of an ASM type liquid crystal display device having a liquid crystal cell of ic Aligned Microcell) mode. The ASM mode liquid crystal cell is characterized in that the thickness of the cell is maintained by a resin spacer whose position can be adjusted.
Other properties are the same as those of the TN mode liquid crystal cell. ASM mode liquid crystal cell and ASM
As for the liquid crystal display device, Kume et al. (Kume et al., S)
ID 98 Digest 1089 (1998)).

  Next, constituent members of one embodiment of the transflective mode liquid crystal display device of the present invention will be sequentially described. FIG. 22 is a schematic view of an embodiment of the liquid crystal display device of the present invention. The liquid crystal display device shown in FIG. 22 includes an upper polarizing plate ECB1 and a lower polarizing plate ECB18 which are disposed with a transflective parallel alignment liquid crystal cell interposed therebetween, and optically anisotropic layers ECB3 and ECB4 which are disposed on both sides of the liquid crystal cell. , ECB14, ECB16 and a backlight (not shown). Since a liquid crystal display device does not emit light by itself unlike a CRT (CRT), it has been used as a transmissive display device in which a backlight composed of a cold cathode fluorescent lamp or the like is installed on the back surface of a panel for illumination. Recently, however, liquid crystal display devices have become smaller and thinner, and have come to be used for mobile applications that are used outdoors or always. At this time, particularly when used outdoors, there was a problem that the influence of outside light was strong, the backlight did not function effectively, and the display quality was greatly degraded. Therefore, a reflection mode has been proposed in which a metallic reflection film having an uneven structure is provided on the inner surface of the liquid crystal cell. Further, in order to achieve both transmission and reflection modes, a transflective mode in which a reflection portion and a transmission portion are provided in one pixel of a display device has been proposed.

FIG. 22 is a schematic diagram of a liquid crystal cell of one pixel. The rubbing direction ECB8 of the upper substrate ECB7 of the liquid crystal cell and the rubbing direction ECB12 of the lower substrate ECB13 are set in parallel, and the liquid crystal layer ECB9 has a parallel alignment without a twist structure. The upper substrate ECB7 and the lower substrate ECB13 in both the transmission part and the reflection part are respectively an alignment film (not shown) and an electrode layer (not shown).
(Not shown). The alignment film has a function of aligning the liquid crystal molecules ECB20. The electrode layer has a function of applying a voltage to the liquid crystal molecules ECB20. The electrode layer is usually made of transparent indium tin oxide (ITO), but in the reflective part, an opaque interlayer insulating layer ECB is formed on the transparent electrode.
11 is formed, and a reflective electrode ECB10 made of metal aluminum or the like is formed thereon, and is electrically connected to the lower transparent electrode layer through a contact through hole (not shown).

In the parallel mode, the dielectric anisotropy is positive between the upper and lower substrates, the refractive index anisotropy, Δn = 0.0854 (5
89 nm, 20 ° C.), Δε = + 8.5 liquid crystal (for example, MLC-910 manufactured by Merck)
0) is used. The thickness d4 of the liquid crystal layer in the transmission part is set to 3.5 μm. Here, the brightness at the time of white display changes depending on the magnitude of the product Δn · d4 of the thickness d4 and the refractive index anisotropy Δn. Therefore, in order to obtain the maximum brightness, the thickness d4 is set to be in the range of 0.2 to 0.4 μm. Further, since the reflective portion is apparently doubled in thickness by the reflective electrode, the thickness may ideally be half that of the transmissive portion, 1.75 μm. However, there are factors such as interlayer insulation process restrictions, and it is not always necessary to set this relationship.

The concept of optical compensation in the transflective mode liquid crystal display device can be explained by the polarization state of the liquid crystal cell and the optically anisotropic layers ECB3, ECB5, ECB14, and ECB16. In the reflection part of FIG. 22, the liquid crystal molecules ECB20 are aligned in parallel to the substrates ECB7 and ECB13 when no voltage is applied. The product of the thickness d4 of the liquid crystal layer and the refractive index anisotropy Δn sets the retardation to ¼ of the wavelength of light, for example, near 138 nm for visible light λ = 550 nm. This value is a value called a λ / 4 plate and has the property of converting linearly polarized light into circularly polarized light. On the other hand, the retardation values of the optical anisotropic layers ECB3 and ECB5 are similarly set to ¼ of the wavelength of light.

When no voltage is applied to the liquid crystal cell, the linearly polarized light that has passed through the polarizing plate is circularly polarized because the retardation values of the optically anisotropic layers ECB3 and ECB5 correspond to λ / 4 plates. Next, when passing through the liquid crystal cell, the rubbing direction ECB8 of the upper substrate ECB7 of the liquid crystal cell and the slow axis of the optically anisotropic layer ECB5 so that the retardation is also a λ / 4 plate and the direction of circularly polarized light is reversed. When ECB6 is adjusted, it returns to linearly polarized light again. Further, the polarized light is returned by the reflecting plate, passes through the upper polarizing plate ECB1 without changing the polarization state by linearly polarized light by performing the same polarization conversion, and a substantially bright white display is obtained.

  On the other hand, in the voltage application state, the liquid crystal cell retardation is close to 0 because the liquid crystal molecules ECB20 are aligned perpendicular to the substrate surface. The light that has passed through the polarizing plate becomes circularly polarized light by passing through the optically anisotropic layer, but the direction of circularly polarized light is reversed by being reflected by the reflective film. When the light passes again through the optically anisotropic layer, the polarization plane is changed by 90 [deg.] And cannot pass through the polarizing plate. As a result, a dark black display is obtained when a voltage is applied.

Here, when setting the retardation value of the optically anisotropic layer to λ / 4, it is necessary to set at all wavelengths in the visible light region in order to obtain high display quality. Therefore, two layers of optically anisotropic layers ECB3 and ECB5 are used, the crossing angle between slow axis ECB4 and ECB6, the retardation value of each optically anisotropic layer, and the crossing with absorption axis ECB2 of upper polarizing plate ECB1. By setting the angle, it is designed to be approximately λ / 4 in the visible light wavelength region. In this configuration, the retardation value of the optically anisotropic layer ECB3 is set to a λ / 2 plate, and the retardation value of the optically anisotropic layer ECB5 is set to a λ / 4 plate, and the slow axis ECB4 and ECB6 are The crossing angle is 60 °, the crossing angle between the absorption axis ECB2 of the upper polarizing plate ECB1 and the slow axis ECB4 of the optically anisotropic layer ECB3 is 15 °, the absorption axis ECB2 of the upper polarizing plate ECB1 and the upper substrate of the liquid crystal cell. The crossing angle of the ECB 7 with the rubbing direction ECB 8 is set to 45 °. In addition, the optically anisotropic layers ECB14 and ECB16 having the same retardation value as that of the reflecting portion may be ideally disposed in the transmitting portion, and the angle formed by the angles of the optical axes may be symmetrically disposed. Of course, the individual values may be adjusted according to the thickness of the liquid crystal layer in the transmission portion.

The optical compensation sheet for LCD will be described in detail below for the cellulose acylate film used in the optical application of the present invention.

(Optical compensation sheet for LCD)
A liquid crystal display device using an optical compensation sheet in which an optically anisotropic layer made of a discotic compound is coated on a transparent support of a cellulose acylate film produced using the present invention is directly used as a protective film for a polarizing plate. Although the application example of the cellulose acylate film of this invention is described about this, it is not limited to this.

  Discotic compounds used in these are described in detail in JP-A-7-267902, JP-A-7-281028, and JP-A-7-306317. According to them, the optically anisotropic layer is a layer formed from a compound having a discotic structural unit. That is, the optically anisotropic layer is a polymer layer obtained by polymerization (curing) of a low molecular weight liquid crystal discotic compound layer such as a monomer or a polymerizable liquid crystal discotic compound. Examples of these discotic compounds are 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, page 2655 (1994), and azacrown-based and phenylacetylene-based macrocycles. The above-mentioned discotic (discotic) compound generally has a structure in which these are used as a mother nucleus at the center of a molecule, and a linear alkyl group, an alkoxy group, a substituted benzoyloxy group, etc. are radially substituted as the linear chain. , Which shows liquid crystallinity and is generally called a discotic liquid crystal. However, the molecular assembly is not limited to the above description as long as it has a negative uniaxial property and can give a certain orientation. Further, in the above publication, the term “formed from a discotic compound” does not require the final product to be the above compound. For example, the low molecular discotic liquid crystal has a group that reacts with heat, light, or the like. As a result, it may be polymerized or cross-linked by reaction with heat, light or the like, resulting in high molecular weight and loss of liquid crystallinity. Furthermore, it is preferable to use a compound containing at least one discotic compound capable of forming a discotic nematic phase or a uniaxial columnar phase and having optical anisotropy. The discotic compound is preferably a triphenylene derivative. Here, the triphenylene derivative is preferably a compound represented by (Chemical Formula 2) described in JP-A-7-306317.

In addition, the cellulose acylate film produced in the present invention is preferably used as a support for the alignment film. As those, those described in detail in JP-A-9-152509 can be applied. That is, the alignment film is provided on the cellulose acylate film prepared in the present invention or on an undercoat layer coated on the cellulose acylate film. The alignment film functions so as to define the alignment direction of the liquid crystalline discotic compound provided thereon. Here, the orientation film may be any layer as long as it can impart orientation to the optically anisotropic layer.

Preferred examples of the alignment film include a layer subjected to a rubbing treatment of an organic compound (preferably a polymer), an oblique deposition layer of an inorganic compound, and a layer having a microgroove, and ω-tricosanoic acid, dioctadecylmethylammonium chloride and stearyl. Examples thereof include a cumulative film formed by Langmuir-Blodgett method (LB film) such as methyl acid, or a layer in which a dielectric is oriented by applying an electric field or a magnetic field.

Examples of organic compounds for alignment films include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleimide copolymer, polyvinyl alcohol, poly (N
-Methylol acrylamide), styrene / vinyl toluene copolymer, chlorosulfonated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, Mention may be made of polymers such as carboxymethylcellulose, polyethylene, polypropylene and polycarbonate, and compounds such as silane coupling agents. Examples of preferable polymers include polyimide, polystyrene, polymers of styrene derivatives, gelatin, polyvinyl alcohol, and alkyl-modified polyvinyl alcohol having an alkyl group (preferably having 6 or more carbon atoms).

Among them, alkyl-modified polyvinyl alcohol is particularly preferable, and has an excellent ability to uniformly align a liquid crystal discotic compound. This is presumably because of the strong interaction between the alkyl chain on the alignment film surface and the alkyl side chain of the discotic liquid crystal. In addition, the alkyl group preferably has 6 to 14 carbon atoms, and further, polyvinyl alcohol through —S—, — (CH ₃ ) C (CN) — or — (C ₂ H ₅ ) N—CS—S—. It is preferable that it is couple | bonded with. The alkyl-modified polyvinyl alcohol has an alkyl group at the end, and preferably has a saponification degree of 80% or more and a polymerization degree of 200 or more. As the polyvinyl alcohol having an alkyl group in the side chain, commercially available products such as MP103, MP203, and R1130 manufactured by Kuraray Co., Ltd. can be used.

A polyimide film (preferably fluorine atom-containing polyimide) widely used as an alignment film for LCD is also preferable as the organic alignment film. This is a polyamic acid (for example, LQ / LX series manufactured by Hitachi Chemical Co., Ltd., SE series manufactured by Nissan Chemical Co., Ltd., etc.) applied to the support surface and baked at 100 to 300 ° C. for 0.5 to 1 hour. Thereafter, it is obtained by rubbing.

  Furthermore, the alignment film applied to the cellulose acylate film of the present invention can be obtained by introducing a reactive group into the polymer or using the polymer together with a crosslinking agent such as an isocyanate compound and an epoxy compound. A cured film obtained by curing is preferred.

It is preferable that the polymer used for the alignment film and the liquid crystalline compound of the optically anisotropic layer are chemically bonded via the interface between these layers. The polymer of the alignment film is preferably formed from polyvinyl alcohol in which at least one hydroxyl group is substituted with a group having a vinyl part, an oxiranyl part or an aziridinyl part. A group having a vinyl moiety, an oxiranyl moiety or an aziridinyl moiety is preferably bonded to the polymer chain of the polyvinyl alcohol derivative via an ether bond, a urethane bond, an acetal bond or an ester bond. It is preferred that the group having a vinyl moiety, an oxiranyl moiety or an aziridinyl moiety does not have an aromatic ring. The polyvinyl alcohol is disclosed in JP-A-9-1.
(Chemical Formula 22) described in Japanese Patent No. 52509 is preferable.

Moreover, the rubbing process can utilize a processing method widely adopted as a liquid crystal alignment process of LCD. That is, a method of obtaining alignment by rubbing the surface of the alignment film in a certain direction using paper, gauze, felt, rubber, nylon, polyester fiber or the like can be used. In general, it is carried out by rubbing several times using a cloth in which fibers having a uniform length and thickness are flocked on average.

Further, as a vapor deposition material for the inorganic oblique vapor deposition film, SiO is representative, and metal oxides such as TiO ₂ and ZnO ₂ , fluorides such as MgF ₂ , and metals such as Au and Al can be cited. The metal oxide can be used as an oblique deposition material if it has a high dielectric constant,
It is not limited to the above. The inorganic oblique deposition film can be formed using a deposition apparatus. An inorganic oblique vapor deposition film can be formed by fixing the film (support) and performing vapor deposition, or moving the long film and performing continuous vapor deposition. Examples of a method for aligning an optical anisotropic layer without using an alignment film include a method of applying an electric field or a magnetic field while heating the optical anisotropic layer on the support to a temperature at which a discotic liquid crystal layer can be formed. Can do.

Further, the cellulose acylate film of the present invention is disclosed in JP-A-8-5837 and JP-A-7-
No. 191217, JP-A-8-50206, and JP-A-7-281028 can be used for an optical compensation sheet having the following basic structure. The non-chlorine cellulose acylate film of the present invention and an optical compensation sheet comprising an optical anisotropic layer provided thereon are application examples, and the optical anisotropic layer is formed of a compound having a discotic structural unit. It is. As an application example to the LCD, the optical compensation sheet is bonded to one side of the polarizing plate through an adhesive, or the optical compensation sheet is bonded to the polarizing element as a protective film through an adhesive. Is preferred. The optical anisotropic element preferably has at least a discotic structural unit (preferably a discotic liquid crystal).

The disc surface of the discotic structural unit (hereinafter also simply referred to as “plane”) is inclined with respect to the cellulose acylate film surface of the present invention, and the disc surface of the discotic structural unit and the cellulose acylate film Is preferably changed in the depth direction of the optically anisotropic layer.

Preferred embodiments of the optical compensation sheet used together with the cellulose acylate film of the present invention are as follows.
(B1) The average value of the angles increases as the distance from the bottom surface of the optical anisotropic layer increases in the depth direction of the optical anisotropic layer.
(B2) The angle changes in the range of 5 to 85 °.
(B3) The minimum value of the angle is in the range of 0 to 85 ° (preferably 0 to 40 °), and the maximum value is in the range of 5 to 90 ° (preferably 50 to 85 °).
(B4) The difference between the minimum value and the maximum value of the angle is in the range of 5 to 70 degrees (preferably 10 to 60 °.
)It is in.
(B5) The angle continuously changes (preferably increases) in the depth direction of the optical anisotropic layer and as the distance from the bottom surface of the optical anisotropic layer increases.
(B6) The optically anisotropic layer further contains cellulose acylate.
(B7) The optically anisotropic layer further contains cellulose acetate butyrate.
(B8) An alignment film (preferably a polymer cured film) is formed between the optically anisotropic layer and the transparent support.
(B9) An undercoat layer is formed between the optically anisotropic layer and the alignment film.
(B10) The optically anisotropic layer has a minimum absolute value of retardation other than 0 in a direction inclined from the normal direction of the optical compensation sheet.
(B11) The optical compensation sheet according to (b8), wherein the alignment film is a rubbed polymer layer.
It is preferable to include an organic compound that can be added to the optical anisotropic layer to change the orientation temperature of the optical anisotropic layer. The organic compound is preferably a monomer having a polymerizable group.

For the production method of the optical compensation sheet of the notation to which the cellulose acylate film produced in the present invention is applied, for example, JP-A-9-73081, JP-A-8-160431, and JP-A-9-73016. Although described in detail, it is not limited to these.

An example of a method for producing this optical compensation sheet is shown below.
(C1) A transparent resin layer is formed by applying and drying a coating liquid containing a resin for forming an alignment film on the surface of a cellulose acylate film produced with the long non-chlorinated organic solvent of the present invention sent out. The
(C2) A rubbing process is performed on the surface of the transparent resin layer using a rubbing roller to form an alignment film on the transparent resin layer. By placing a rubbing roll between two conveying rolls in the continuous conveying step of the film substrate and conveying the film substrate while wrapping the film substrate on the rotating rubbing roll, the film substrate is continuously provided. It is preferable to perform a rubbing treatment on the alignment film surface on the substrate. It is also possible to dispose the rubbing roll with the rotation axis inclined with respect to the transport direction of the film substrate. The roundness, cylindricity, and runout of the rubbing roll itself are preferably 30 μm or less. In the apparatus using the rubbing method described above, it is preferable that one or more spare rubbing rolls are provided in the apparatus.
(C3) A coating liquid containing a liquid crystalline discotic compound is applied onto the alignment film. It is preferable that the surface of the transparent resin layer is rubbed while dusting the rubbing roller, and the surface of the rubbed resin layer is removed. A liquid crystal discotic compound having a crosslinkable functional group can be used as the liquid crystal discotic compound. The surface of the formed coating layer is sealed with a gas layer, the solvent is evaporated while being suppressed, and the coating layer in which most of the solvent is evaporated is heated to form a liquid crystal layer in a discotic nematic phase. It is preferable. For sealing the gas layer on the surface of the coating layer, it is preferable to move the gas along the surface of the coating layer so as to have a relative speed of −0.1 to 0.1 m / sec with respect to the moving speed of the coating layer. . In order to evaporate the solvent under suppression, it is preferable to carry out the evaporation within a period in which the decrease rate of the solvent content in the coating layer is proportional to the time.
(C4) After drying the applied layer, it is preferable to form a liquid crystal layer having a discotic nematic phase by heating, and to continuously irradiate the liquid crystal layer with light to cure the discotic liquid crystal. The coating layer is preferably heated by applying hot air or far infrared rays to the side of the transparent resin film that does not have a liquid crystal layer, or by bringing a heating roller into contact therewith. Moreover, it is preferable to perform the heating after drying of this coating layer by providing a hot air or a far infrared ray to both surfaces of this transparent resin film.
(C5) It is preferable to wind up the cellulose acylate film produced with the non-chlorine organic solvent of the present invention in which the alignment film and the liquid crystal layer are formed.

Next, the example which applies the cellulose acylate film produced by this invention to a panel is shown.
They are disclosed in JP-A-8-95034, JP-A-9-197397, JP-A-11-3163.
It is described in detail in each publication of No. 78. The optical compensation sheets described in the above publications are advantageously used for liquid crystal display devices, particularly transmissive liquid crystal display devices. The transmissive liquid crystal display device
It consists of a liquid crystal cell and two polarizing plates arranged on both sides thereof. The liquid crystal cell carries a liquid crystal between two electrode substrates. One optical compensation sheet is disposed between the liquid crystal cell and one polarizing plate, or two optical compensation sheets are disposed between the liquid crystal cell and both polarizing plates. The mode of the liquid crystal cell is preferably a VA mode, a TN mode, or an OCB mode.

In a VA mode liquid crystal cell, rod-like liquid crystal molecules are aligned substantially vertically when no voltage is applied. In VA mode liquid crystal cell,
(D1) In addition to a narrowly-defined VA mode liquid crystal cell (described in JP-A-2-176625) in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when voltage is applied. And
(D2) Liquid crystal cell (SID97, Digest of tech. Papers (Preliminary Proceeds) 28 (1
997) 845)),
(D3) Liquid crystal cell in a mode (n-ASM mode) in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied (Procedures 58-59 (1998) ) Description) and (d4) SURVAVAL mode liquid crystal cell (announced at LCD International 98)
Is included.

In a TN mode liquid crystal cell, rod-like liquid crystalline molecules are substantially horizontally aligned when no voltage is applied,
Further, it is twisted at 60 to 120 °. TN mode liquid crystal cell is color TFT
It is most frequently used as a liquid crystal display device and is described in many documents. Preferred embodiments are shown below.
(E1) The pretilt angle of the liquid crystal of the liquid crystal cell is 5 ° or less.
(E2) The product Δnd of the refractive index anisotropy Δn of the liquid crystal cell and the thickness d of the liquid crystal layer in the liquid crystal cell
Is in the range of 0.3 μm to 1.0 μm.
(E3) One substrate of the liquid crystal cell has a pixel electrode having a nonlinear active element, and the other substrate has a counter electrode.
(E4) A pixel electrode having a TFT or MIM element as a nonlinear active element and a counter electrode are included.
(E5) The absorption axes of the two polarizing plates are almost orthogonal and are used in a normally white mode.
(E6) The absorption axes of the two polarizing plates are substantially parallel and are used in a normally black mode.

The OCB mode liquid crystal cell is a liquid crystal display device using 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 part and the lower part of the liquid crystal cell. It is disclosed in Japanese Patent No. 458825 and US Pat. No. 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 OCB (O
(Ptally Compensatory Bend) This is also called a liquid crystal mode.
The bend alignment mode liquid crystal display device has an advantage of high response speed.

  An application example of the optical compensation sheet of the present invention to an OCB mode liquid crystal cell will be described. (E7) Disposed between the liquid crystal cell and at least one polarizing plate. (E8) It is comprised from the optically anisotropic layer which consists of a transparent support body and the compound which has a discotic structural unit provided on it. (E9) The transparent support satisfies the conditions of Re 0 to 200 nm and Rth of 20 to 400 nm. (E10) There is a minimum direction of refractive index in a direction inclined from the normal direction of the optical compensation sheet, and an absolute value Re1 of retardation represented by the following of the optical compensation sheet (when a plurality of optical compensation sheets are arranged) Is the sum of the absolute values of the retardation of each optical compensation sheet) and the absolute value Re2 of the retardation of the liquid crystal layer, which satisfies the following relationship. 0.2 × Re2 ≦ Re1 ≦ 2.0 × Re2. (E11) A liquid crystal display device comprising a bend alignment mode liquid crystal cell and a pair of polarizing elements disposed on both sides of the liquid crystal cell, wherein at least one of the polarizing elements includes a discotic compound, An elliptically polarizing plate consisting of a laminate of a transparent support having anisotropy and a polarizing film, the polarizing film being arranged on the outermost side, and orthogonal projection of the normal of the disc surface of the discotic compound onto the transparent support surface The angle between the average direction of the transparent support and the in-plane slow axis of the transparent support is substantially 45 °, and the in-plane slow axis of the transparent support and the in-plane transmission axis of the polarizing film are substantially parallel or The optically anisotropic layer, the transparent support and the polarizing film are preferably disposed so as to be substantially vertical. (E12) The cellulose acylate film described in (e5) may be composed of a plurality of sheets.

(Detailed explanation of retardation plate)
The cellulose acylate film of the present invention can be used for a retardation plate composed of a single polymer film. Although the content is described below, it is not necessarily limited to this. First, optical characteristics of the retardation plate will be described. Preferred optical properties of the retardation plate in which the cellulose acylate film of the present invention is used are as follows. 450n wavelength
The retardation value (Re (450)) measured in m is 10 to 150 nm, the retardation value (Re (590)) measured at a wavelength of 590 nm is 10 to 100 nm, and | Re (590) −Re (450 ) | ≦ 40 nm is preferably satisfied.
The retardation value (Re (450)) measured at a wavelength of 450 nm is 20 to 150 nm.
The retardation value (Re (550)) measured at a wavelength of 550 nm is 20 to 15.
The retardation value measured at a wavelength of 590 nm (Re (590)) of 20 nm is 20 nm.
More preferably, the thickness is from 160 nm to 160 nm, and | Re (590) −Re (550) | ≦ 30 nm.

In JP 2003-057443, as an optically anisotropic film that has a favorable viewing angle and is less likely to cause surface failure (stain failure), the formula (1) 0.60 <Re (450) / Re (550) < 0.97 and formula (2) 1.01 <Re (650) / Re
There is a description of an optically anisotropic film having a retardation value satisfying (550) <1.35 and a crying index of 0.6% or less.

Japanese Patent Application Laid-Open No. 2003-057444 also describes an optical anisotropy that has a good viewing angle and is less likely to cause planar failure (color spot failure). Re (550) <0.97 and formula (2) 1.01 <Re
Retension value satisfying (650) / Re (550) <1.35, Re (550) in the width direction, Re (550) in the longitudinal direction, thickness distribution in the width direction, and thickness distribution in the longitudinal direction However, there is a description of an optically anisotropic stretched film that is 10% or less.

In order to improve the viewing angle characteristics of a TN type LCD, Japanese Patent Application Laid-Open No. 2002-286933 discloses a first film after stretching in a stretched film composition having birefringence that stretches in a direction perpendicular to the transport direction. And an invention in which the stretched second film stretched under the same conditions as the first film are laminated so that the angle formed by the transport direction is 180 degrees. These inventions described above can also be applied to the present invention.

Variation coefficients CRe450 and CRe590 for variation in the retardation value are C
It is preferable that Re450 ≦ 0.1 and CRe590 ≦ 0.1. The CRe value is a value obtained by dividing an absolute value of a difference between measured values at adjacent measurement points by an average value (expressed as a percentage).
The maximum value among the values divided by cm) is defined.
Moreover, it is preferable that the relationship of 1 ≦ (nx−nz) / (nx−ny) ≦ 2 is satisfied.
(Where, nx: refractive index in the slow axis direction in the plane of the retardation plate, ny: refractive index in the direction perpendicular to the slow axis in the plane, nz: refractive index in the thickness direction)
A value obtained by standardizing wavelength dispersion (DRα (λ)) measured in a wavelength range of 380 nm to 780 nm from a direction that makes an angle α with the normal direction of the film surface and a retardation measured from the normal direction of the film surface. Absolute value of difference between normalized values (DR0 (λ)) | DRα (λ) −
It is preferable that DR0 (λ) | falls within the range and is 0.02 or less in the entire wavelength range.
[However, DR0 (λ) = Re (λ) / Re (550), DRα (λ) = Reα (λ) /
Reα (550)]
The average direction of the slow axis in the film plane is preferably within ± 5 ° from the stretching direction, and its standard deviation is preferably within 2.0. α is preferably 40 ° or less, and most preferably within a measurable range. The haze of the retardation plate is preferably 2.0% or less.

Japanese Patent Application Laid-Open No. 2002-131538 discloses that in order to provide a reflective liquid crystal display element having excellent display quality, birefringence at a wavelength of 400 to 700 nm is larger as a longer wavelength, Re (450) 80 to 125 nm, Re (590 120 ~
Coefficient of variation of Re value CRe450, CRe590 with one 160nm polymer film retardation plate
However, there is a description of each of CRe450 ≦ 0.1 and CRe590 ≦ 0.1 dial retardation plate.

In JP-A-2002-267844, when a polarizing plate produced from a roll-like retardation film is used in a liquid crystal display device, 0.5 ≦
A long retardation film of (Nx−Nz) / (Nx−Ny) ≦ 2 is wound in a roll shape with a protective film laminated on at least one surface without damaging the surface of the film. There is a description of the retardation film roll taken.

Japanese Patent Laid-Open No. 2003-035821 discloses a film of Re (550)) 100 to 130 nm in order to improve the color and contrast of a reflective liquid crystal display device. 450) and Re (550) satisfy the relationship 0.800 ≦ Re (450) / Re (550) ≦ 0.920, and R
A retardation plate is described in which e (700)) and Re (550) satisfy a relationship of 1.065 ≦ Re (700) / Re (550) ≦ 1.300. These inventions described above can also be applied to the present invention.

In the retardation plate of the present invention, a retardation control agent is added to the cellulose acylate film in order to adjust the retardation value at each wavelength. In that case, preferred examples of the retardation control agent are as follows. They may be used alone or in combination of two or more.

They have a maximum absorption wavelength (λmax) in the wavelength region of 30 nm to 360 nm and a retardation control agent (RA-1) having substantially no absorption in the visible region and 750 nm.
It is a retardation control agent (RA-2) having a maximum absorption wavelength in a wavelength region of 1100 nm and having substantially no absorption in the visible region.

Further preferred as RA-1 is as follows. It is preferable to use a compound having at least two aromatic rings in the molecule. “Aromatic ring” includes aromatic heterocycles in addition to aromatic hydrocarbon rings. The aromatic hydrocarbon ring is particularly preferably a 6-membered ring (that is, a benzene ring). The aromatic heterocycle is generally an unsaturated heterocycle. The aromatic heterocycle is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring. Aromatic heterocycles generally have the most double bonds. As the hetero atom, a nitrogen atom, an oxygen atom and a sulfur atom are preferable, and a nitrogen atom is particularly preferable. Examples of aromatic heterocycles include furan ring, thiophene ring, pyrrole ring, oxazole ring,
Isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring, pyridine ring, pyridazine ring, pyrimidine ring,
A pyrazine ring and a 1,3,5-triazine ring are included. Here, as the aromatic ring, benzene ring, furan ring, thiophene ring, pyrrole ring, oxazole ring, thiazole ring, imidazole ring, triazole ring, pyridine ring, pyrimidine ring, pyrazine ring and 1,3,5
-A triazine ring is preferred. The number of aromatic rings is preferably 2 to 20.
The connection relationship between two aromatic rings can be classified into a case where a condensed ring is formed, a case where they are directly connected by a single bond, and a case where they are connected via a linking group, and any of them may be used. The aromatic ring and the linking group may have a substituent. Examples of the substituent include a halogen atom (F, Cl, Br, I
), Hydroxyl, carboxyl, cyano, amino, nitro, sulfo, carbamoyl, sulfamoyl, ureido, alkyl group, alkenyl group, alkynyl group, aliphatic acyl group,
Aliphatic acyloxy group, alkoxy group, alkoxycarbonyl group, alkoxycarbonylamino group, alkylthio group, alkylsulfonyl group, aliphatic amide group, aliphatic sulfonamido group, aliphatic substituted amino group, aliphatic substituted carbamoyl group, aliphatic substitution A sulfamoyl group, an aliphatic substituted ureido group and a non-aromatic heterocyclic group are included.

Further preferred as RA-2 is as follows. As RA-2, an infrared absorbing dye or an infrared absorbing pigment is preferably used. Either an organic compound or an inorganic compound may be used. For infrared absorbing dyes, see Coloring Materials, 61 [4] 215-226 (1988).
), And Chemical Industry, 43-53 (1986, May). In particular, materials developed in the technical field of silver halide photographic light-sensitive materials can be preferably used. RA-1 and RA
-2 retardation adjustment is adjusted by its content, preferably polymer 1
RA-1 is in the range of 0.05 to 20 parts by weight, and RA-2 is 0.01.
It is preferable to use in the range of 5 parts by weight. The molecular weight of the retardation control agent is 3
It is preferably 00 to 800.

Next, the development of the retardation plate of the present invention for optical applications will be described below. First, application to polarizing plates and panels will be described. The retardation plate of the present invention is advantageously used for a circularly polarizing plate, a touch panel and a liquid crystal display device, particularly a reflective liquid crystal display device. λ / 4 plate and polarizing film are
A circularly polarizing plate is obtained by laminating so that the angle between the slow axis in the plane of the / 4 plate and the polarization axis of the polarizing film is substantially 45 °. The retardation plate of the present invention can be preferably used as a λ / 4 plate. Here, substantially 45 ° means 40 ° to 50 °.

Examples of the polarizing film include an iodine polarizing film, a dye polarizing film using a dichroic dye, and a polyene polarizing film. The iodine polarizing film and the dye polarizing film are generally produced using a polyvinyl alcohol film. The polarization axis of the polarizing film corresponds to a direction perpendicular to the stretching direction of the film. A transparent protective film is preferably provided on the surface of the polarizing film opposite to the λ / 4 plate. Further, it is preferable to provide an antireflection layer as the outermost layer. The touch panel has a fixed substrate close to the display element,
It consists of an opposing movable substrate. Transparent electrodes are provided on opposing surfaces of the fixed substrate and the movable substrate, respectively. The fixed substrate and the movable substrate are preferably made of a transparent optical material. The retardation plate of the present invention can be used for either a fixed substrate, a movable substrate, or both, but is more preferably used as a movable substrate. Examples of the material of the substrate that is not the retardation plate of the present invention include polymer films such as glass, amorphous film, polyethersulfone, polycarbonate, polyarylate, and polyethylene terephthalate. A polarizing plate can be provided outside the touch panel.

A gap is formed between the two transparent electrodes. An air layer is usually present between the gaps, but a liquid having a refractive index close to that of the transparent electrode can be filled for optical matching. Moreover, an undercoat layer can be provided on the substrate side of the transparent electrode film, or an overcoat layer can be provided on the opposite side of the substrate to reduce light reflection. Eliminate sticking,
In order to improve the keying life, the transparent electrode film surface may be roughened. Spacers can be provided between the gaps. As the spacer, a dot-shaped spacer, a bonding material provided in the peripheral portion of the fixed substrate and the movable substrate, or the like is used.

  The touch panel is used as both a digital type and an analog type. The reflective liquid crystal display device has a basic structure in which a reflector, a liquid crystal cell, and a polarizing film are laminated in this order. An example of the basic configuration of a reflective liquid crystal display device is shown in European Patent WO 00/65384. In order from the bottom, the lower substrate (1), the reflective electrode (2), the lower alignment film (3), the liquid crystal layer (4), the upper alignment film (5), the transparent electrode (6), the upper substrate (7), λ / It consists of four plates (8) and a polarizing film (9). The lower substrate (1) and the reflective electrode (2) constitute a reflective plate. The lower alignment film (3) to the upper alignment film (5) constitute a liquid crystal cell.

The retardation plate of the present invention can be used as a λ / 4 plate. The λ / 4 plate (8) can be disposed at an arbitrary position between the reflecting plate and the polarizing film (9). In the case of color display, a color filter layer is further provided. The color filter layer comprises a reflective electrode (2) and a lower alignment film (3
) Or between the upper alignment film (5) and the transparent electrode (6). Instead of the reflective electrode (2), a transparent electrode may be used and a separate reflector may be attached. As the reflecting plate used in combination with the transparent electrode, a metal plate is preferable. Uneven structure on the surface of the reflector (Patent 2
It is preferable to introduce (described in Japanese Patent No. 75620). When the surface of the reflector is flat (instead of introducing an uneven structure on the surface), a light diffusion film may be attached to one side (cell side or outside) of the polarizing film.

Furthermore, regarding the display mode of the liquid crystal cell, TN (Twisted Nematic), S
TN (Super Twisted Nematic), HAN (Hybrid Al)
signed Nematic), ECB (Electrically control)
ed birefringence), HPDLC (Holographic Poly)
Various display modes such as “mer Dispersed Liquid Crystal” have been proposed. In particular, the TN type, STN type, or HAN type is preferable.

The twist angle of the TN liquid crystal cell is preferably 40 ° to 100 °. The product (Δnd) of the refractive index anisotropy (Δn) of the liquid crystal layer and the thickness (d) of the liquid crystal layer has a value of 0.1 to 0.00.
It is preferable that it is 5 micrometers.

The twist angle of the STN type liquid crystal cell is preferably 180 ° to 360 °, and Δnd is preferably 0.3 to 1.2 μm.

In the HAN type liquid crystal cell, it is preferable that the liquid crystal is aligned substantially vertically on one substrate and the pretilt angle on the other substrate is 0 to 45 °. Δnd is 0.1 to 1.0 μm
It is preferable that

The λ / 4 plate according to the present invention can be used as a λ / 4 plate of a guest-host reflective liquid crystal display element. Regarding a guest-host reflection type liquid crystal display element provided with a λ / 4 plate, JP-A-6-2223 is disclosed.
No. 50, JP-A-8-36174, JP-A-10-268300, JP-A-10-2921
75, JP-A-10-293301, JP-A-10-311976, JP-A-10-31
9442, JP-A-10-325953, JP-A-10-333138, JP-A-11-
There are descriptions in each publication of No. 38410. The λ / 4 plate according to the present invention can also be used for the guest-host reflective liquid crystal display element described in the above publications.

In addition, with a single polymer film, λ / 4 or λ / 2 is achieved over the entire visible light range,
And in order to prevent plasticizer precipitation (bleed out), JP-A-2002-090544 includes 5-30.
Comprising a cellulose ester film containing a weight percent plasticizer, the amount of plasticizer on the surface of the film is less than the overall average, and Re (450) 100-125 nm, Re (590) 120-160 nm, Re590-Re450 ≧ 2 nm There is a description about the board.

Further, JP 2002-131537 discloses Re (450) 100 to 125 nm in order to provide a retardation plate that achieves λ / 4 or λ / 2 in the entire visible light region and has improved adhesion. Re (590) 120-160nm, Re (590)
There is a description of a retardation plate comprising a polymer film of ~ Re (450) ≧ 2 nm and having a surface treatment on one side / both sides of the polymer film.

Further, JP-A-2002-131542 discloses that a polymer film having a scratch strength of ≧ 1 g is used to provide a retardation plate that achieves λ / 4 or λ / 2 in the entire visible light range and generates less dust. (45
0) is 100 to 125 nm, Re (590) 120 to 160 nm, Re590−Re450 ≧ 2 nm, the refractive index Nx in the slow axis direction in the plane of the polymer film, and the direction perpendicular to the slow axis in the plane There is a description of a retardation plate in which the refractive index Ny and the refractive index Nz in the thickness direction have a relationship of 1 ≦ (Nx−Nz) / (Nx−Ny) ≦ 2.

Japanese Patent Laid-Open No. 2002-202411 also discloses birefringence at a wavelength of 400 to 700 nm in order to provide a retardation plate that achieves λ / 4 over the entire visible light region with a single film and has improved flatness. Is described for a retardation plate of a film made of a single cellulose acylate film of Re (450) 80-125 nm and Re (590) 120-160 nm, and formed by a co-casting method. ing.

Further, JP 2002-267847 discloses a wavelength (λmax) that provides a UV absorption maximum of a solution in order to provide a retardation plate that has excellent durability and achieves λ / 4 or λ / 2 in a wide wavelength region. ) Contains a rod-like compound with a wavelength shorter than 250 nm, Re (450) is 60-135 nm, Re (590) is 100-170 nm, Re (590) -Re (450) ≧ 2 nm There is a description about. These inventions described above can also be applied to the present invention.

(Biaxial cellulose acylate film)
Next, details of the biaxial cellulose acetate film in which the cellulose acylate film of the present invention is preferably used will be described. The cellulose acetate film of the present invention is
It can be used as an optical film for optically compensating a liquid crystal cell. In other words, European patent 0
The cellulose acetate film disclosed in 91611656A2 is improved,
The liquid crystal cell can be optically compensated only by the film. Thereby, an optical compensation function can be added to the polarizing plate without increasing the number of components of the polarizing plate. Such a cellulose acylate film preferably has the following characteristics. This can also be used as a polarizing plate protective film.

The average value in the plane of the angle between the slow axis angle and the drawing direction (axial misalignment) is within 3 °, the range of axial misalignment is 5 ° or less, the Re retardation value is 20 to 70 nm, and Rth retardation. Optical compensation sheet with a value of 70 to 400 nm, Re, Rth range is 0% or more 1
The optical compensation sheet being not more than 0%, 30% or less elongation at break 10% or more, the breaking strength is characterized in that it is 11 kgf / mm ² or more 20 kgf / mm ² or less, thermal shrinkage start temperature An optical compensation sheet characterized in that it is 130 ° C. or more and 190 ° C. or less, an optical compensation sheet comprising a single cellulose acylate film, and stretched in the width direction at a stretch ratio of 3 to 50% An optical compensation sheet characterized in that it is a cellulose acylate film, particularly composed of cellulose acetate. An optical compensation sheet characterized in that the cellulose acetate film has an aromatic compound having at least two aromatic rings in an amount of 0.01.
The optical compensation sheet, wherein the aromatic compound includes at least one 1,3,5-triazine ring. Further, the polarizing film and a polarizing plate comprising two transparent protective films disposed on both sides thereof, one of the transparent protective films is an optical compensation sheet, and further the average direction of the slow axis of the optical compensation sheet and A polarizing plate characterized by being arranged so that the absolute value of the angle formed by the transmission axis of the polarizing film is 3 ° or less is also preferable.

Furthermore, the liquid crystal cell comprises a liquid crystal cell and two polarizing plates disposed on both sides thereof, and the polarizing plate comprises a polarizing film and two transparent protective films disposed on both sides of the liquid crystal cell. One of the two transparent protective films arranged between the film is the optical compensation sheet described above, and the absolute value of the angle formed by the average direction of the slow axis of the optical compensation sheet and the transmission axis of the polarizing film is A liquid crystal display device characterized by being arranged to be 3 ° or less is also preferable.

In addition, the liquid crystal cell includes a liquid crystal display device in which a VA mode, a TN mode, or an n-ASM mode liquid crystal cell, a liquid crystal cell and two polarizing plates arranged on both sides thereof, and the polarizing plate is provided on the polarizing film and both sides thereof. A liquid crystal display device comprising two transparent protective films arranged, each of the two transparent protective films arranged between the liquid crystal cell and the polarizing film is an optical compensation sheet,
Furthermore, a liquid crystal display device is also provided in which the sum of the absolute values of the angles formed by the average direction of the slow axes of the optical compensation sheet and the transmission axis of the polarizing film adjacent to the optical compensation sheet is 3 ° or less. It is done.

An optical compensation sheet characterized in that an optically anisotropic layer containing a discotic compound is further provided on the above optical compensation sheet, and is preferably composed of a polarizing film and three or more transparent protective films disposed on both sides thereof. An elliptically polarizing plate, which is a polarizing plate, in which one of the transparent protective films is an optical compensation sheet and at least one is the above-described optical compensation sheet, is also preferable. The present invention can also be applied to a liquid crystal display device, which is a liquid crystal cell in a bend alignment mode and a pair of elliptically polarizing plates disposed on both sides of the liquid crystal cell, wherein the elliptically polarizing plate is an elliptically polarizing plate.

The biaxial cellulose acylate film in which the cellulose acylate film produced using the present invention is used will be described in further detail.

(Slow axis angle of film)
The slow axis angle (axis misalignment) in the cellulose acylate film plane is defined as the angle between the slow axis and the reference line with the stretching direction as the reference line (0 °). Here, when the roll-shaped film is stretched in the width direction, the width direction is taken as a reference line, and when it is stretched in the longitudinal direction, the longitudinal direction is taken as a reference line. The average value of the slow axis angle (axis deviation) is preferably 3 ° or less, more preferably 2 ° or less, and most preferably 1 ° or less. The direction of the average value of the slow axis angle is defined as the average direction of the slow axis. Further, the range of the slow axis angle (axis deviation) is preferably 5 ° or less, more preferably 3 ° or less, and most preferably 2 ° or less. The range is obtained by measuring 20 points at equal intervals over the entire width direction, and taking the difference between the average of the four points from the larger absolute value of the axis deviation and the average of the four points from the smaller absolute value.

(Stretching process of biaxial cellulose acylate film)
Regarding stretching of the cellulose acylate film, first, heat treatment before stretching (pre-heat treatment) is performed. Stretching is performed in the above-described stretching step. And the obtained stretched cellulose acylate film is cooled to room temperature after stretching, and during this time, it is 5 to 100 with respect to the original length in the stretching direction.
%, More preferably 5 to 70%, more preferably 1 to 50%, still more preferably% or more 8
It is preferable to shrink and relax by% or less. The cooling rate is preferably 10 to 300 ° C./min, more preferably 30 to 250 ° C./min, and still more preferably 50 to 200 ° C./min.
When the film is stretched, the residual solvent amount of the film is preferably 0 to 100% by mass, particularly preferably 5 to 70% by mass. Also, the atmosphere during stretching is not particularly limited relative humidity,
0 to 98% is preferable, and 0 to 90% is more preferable. Further, the above-described organic solvent or a solvent may be applied for stretching. The solvent used at this time is more preferably a solvent used for dissolution.

In JP 2003-170492 A, in order to supply a physically and engineeringly uniform TAC film, polarizing plate, etc., the residual solvent amount of the film at the start of stretching is 90 to 5% by mass, and in-plane retardation is achieved. A method for producing a cellulose ester film in which Rt / R0 of R0 (nm) and retardation Rt (nm) in the thickness direction is 0.8 to 3.5 is described.

JP-A-2002-286933 discloses a web (film) in which a cellulose ester-dissolved dope solution is cast on a casting support and then peeled off from the casting support in the production of a stretched cellulose ester film according to an optical compensation film. The residual solvent amount in the web is 10 to 100% by mass (particularly 2
It is disclosed that it is preferable to stretch 1.01 to 3.0 times (preferably range is 1.01 to 2.5 times) in the width direction while it is in the range of 0 to 40% by mass. Yes. further,
If the amount of residual solvent in the web is too large, it will be difficult to obtain the effect of stretching, and if it is too small, stretching may be extremely difficult, and the web may break.
It has been shown that if the draw ratio is too small, a sufficient phase difference cannot be obtained, and if it is too large, stretching becomes difficult and white turbidity or breakage may occur. In addition, the film thickness may decrease with stretching, but if the film thickness variation of the cellulose ester film support is too large, the retardation will become uneven, causing problems such as coloring when used as an optical compensation film. It is described that the film thickness distribution of the ester film support is preferably ± 3%, and more preferably ± 1%. Furthermore, in order to obtain such a prescribed condition, a method of stretching in the biaxial directions orthogonal to each other is effective, and the stretching ratio in the biaxial directions orthogonal to each other is 0.8.
It is preferable to be in the range of -4.0 times and 0.4-1.2 times. These inventions described above can also be applied to the present invention.

(Mechanical and thermophysical properties of film-forming film)
The biaxial cellulose acylate film thus obtained preferably has the following physical properties. Mechanical properties include elongation at break and strength at break. The breaking elongation is preferably 10% or more and 30% or less, more preferably 15% or more and 29% or less, and still more preferably 20%.
% To 28%. Breaking strength is preferably 11 kgf / mm ² or more 20 kgf / mm ² or less, more preferably 12 kgf / mm ² or more 19 kgf / mm ² or less, further preferably 13 kgf / mm ² or more 18 kgf / mm ² or less.

The optical compensation sheet is cut and pasted to the liquid crystal cell, but the cutting waste and burrs generated here adhere to it, and when this displays the liquid crystal in black, the bright spot becomes a bright spot in the night sky. However, in the present invention, this failure is greatly reduced by creating an optical compensation sheet in the above range.

Next, the thermal shrinkage start temperature, which is a thermophysical property, will be described. Thermal shrinkage starting temperature is 80 ° C or higher 19
0 ° C. or lower is preferable, more preferably 100 ° C. or higher and 180 ° C. or lower, and further preferably 10 ° C. or lower.
It is 0 degreeC or more and 170 degrees C or less. The heat shrinkage starting temperature is TMA (Thermal Mechanical).
It is measured using a (Nical Analyzer). That is, when measuring the dimension of the sample in the stretching direction while raising the temperature, it indicates the temperature contracted by 2% with respect to the original length.

In a transmissive liquid crystal display device using an optical compensation sheet, “display unevenness” may occur in the periphery of the screen when time passes after energization. This unevenness is due to an increase in the transmittance at the periphery of the screen, and is particularly noticeable during black display. This “display unevenness” failure is caused by uneven tension that is subtly present when the optical compensation sheet is attached to the liquid crystal cell. This failure can be resolved by setting the heat shrinkage start temperature. That is, the heat from the backlight of the transmissive liquid crystal display device is used to shrink the optical compensation sheet with heat, and the tension is applied to the entire surface by the generated shrinkage stress, thereby eliminating the uneven tension and eliminating the “display unevenness”. is there.

(Anti-glare film, anti-reflection film)
The cellulose acylate film produced in the present invention can be preferably applied to an antiglare film and an antireflection film. For the purpose of improving the visibility of flat panel displays such as LCD, PDP, CRT, EL, etc., either or both of an antiglare layer and an antireflection layer on one side or both sides of a cellulose acylate film produced using the present invention Can be granted. A film imparted with such a function is called an antiglare film or an antireflection film, and a film provided with both an antiglare layer and an antireflection layer is called an antiglare antireflection film. Generally, an antiglare film is composed of a transparent support and an antiglare layer, and an antireflection film is provided with an antireflection layer consisting of a single layer to a plurality of light interference layers on the outermost surface on the transparent support, If necessary, a hard coat layer and an antiglare layer are provided between the support and the light interference layer.

As the transparent support, the cellulose acylate film produced in the present invention is preferably used for LCD applications, more preferably cellulose acylate, and particularly preferably cellulose acetate. When the antiglare and antireflection film of the present invention is used in an LCD, it is disposed on the outermost surface of the display or the interface with the air inside the display by providing an adhesive layer on one side. Since cellulose triacetate is used as a protective film for protecting the polarizer of the polarizing plate, it is preferable to use the antiglare and antireflection film of the present invention as it is for the protective film from the viewpoint of cost and thinning of the display.

Hereinafter, preferred embodiments of the antiglare film and the antireflection film will be described first.
(Aspect A1) In an antiglare antireflection film comprising a cellulose acylate film produced in the present invention and a low refractive index layer comprising a fluororesin having at least one refractive index of 1.38 to 1.49, The refractive index is 1.57 between the cellulose acylate film and the low refractive index layer.
An antiglare antireflection film comprising an antiglare layer containing a binder of from 2.00 to 2.00.
(Aspect A2) The antiglare antireflection film according to aspect A1, which has at least one hard coat between the cellulose acylate film prepared in the present invention and the antiglare layer.
(Aspect A3) The antiglare antireflection film according to aspect A1 or A2, wherein the low refractive index layer made of the fluororesin has heat or ionizing radiation curability.
(Aspect A4) The antiglare antireflection film according to aspect A3, wherein the antiglare layer is composed of a binder containing mat fine particles and an ionizing radiation curable resin.
(Aspect A5) The antiglare antireflection film according to aspect A4, wherein the antiglare layer has a refractive index difference of less than 0.05 between the matt fine particles and the binder containing the ionizing radiation curable resin.
(Aspect A6) The antiglare antireflection film according to aspect A4, wherein in the antiglare layer, the average particle size of the mat fine particles is 1 μm to 10 μm.
(Aspect A7) In the antiglare layer, the binder having a refractive index of 1.57 to 2.00 is a heat or ionizing radiation cured product of a mixture of a high refractive index monomer and a tri- or higher functional (meth) acrylate monomer. The antiglare antireflection film according to aspect A4, wherein the antiglare antireflection film is present.
(Aspect A8) In the antiglare layer, the binder having a refractive index of 1.57 to 2.00 is a metal oxide ultrafine particle selected from Al, Zr, Zn, Ti, In, and Sn and has a trifunctional or higher functionality. The antiglare antireflection film according to aspect A4, which is a heat or ionizing radiation cured product of a mixture with a (meth) acrylate monomer.
(Aspect A9) The low refractive index layer made of the fluorine-containing resin has a dynamic friction coefficient of 0.03 to 0.15.
Aspects A4 to A are characterized in that the contact angle with water is 90 to 120 °.
The antiglare antireflection film according to any one of 8.
(Aspect A10) A polarizing plate characterized in that the antiglare antireflection film described in any one of aspects A1 to A9 is used for at least one of the two protective films of the polarizing layer in the polarizing plate. .
(Aspect A11) The anti-glare antireflection film according to any one of aspects A1 to A9 or the antireflection layer of the antiglare antireflection polarizing plate according to aspect A10 is used as the outermost layer of the display. A liquid crystal display device.
(Aspect A12) A high refractive index layer having a refractive index of 1.65 to 2.40, and a refractive index of 1.2.
An anionic antireflection film having a low refractive index layer of 0 to 1.55, wherein the high refractive index layer is cross-linked with 5 to 65% by volume of inorganic fine particles having an average particle diameter of 1 to 200 nm 2. The antireflection film according to aspect 1, comprising 35 to 95% by volume of a polymer having a functional group.
(Aspect A13) The antireflection film according to aspect A12, wherein the polymer having an anionic group of the high refractive index layer has a phosphate group or a sulfonic acid group as an anionic group.
(Aspect A14) The antireflection film according to Aspect A12, wherein the polymer having an anionic group in the high refractive index layer further has an amino group or an ammonium group.
(Aspect A15) The antireflection film according to aspect A12, wherein the inorganic fine particles of the high refractive index layer have a refractive index of 1.80 to 2.80.
(Aspect A16) The antireflection according to aspect A12, wherein the high refractive index layer is a layer formed by coating, and the polymer having an anionic group is a polymer formed by a polymerization reaction simultaneously with or after coating of the layer. film.
(Aspect A17) The antireflective film according to aspect A12, wherein the low refractive index layer is made of a fluorine-containing resin and has heat or ionizing radiation curability.
(Aspect A18) The low refractive index layer contains 50 to 95% by mass of inorganic fine particles having an average particle diameter of 0.5 to 200 nm and 5 to 50% by mass of a polymer, and the inorganic fine particles are stacked at least two or more. The antireflection film according to aspect A12, which is a layer in which microvoids are formed between the fine particles.
(Aspect A19) The surface of the antireflection film according to any one of Aspects A12 to A18 has an uneven shape, and the film thicknesses of the low refractive index layer and the high refractive index layer are substantially uniform. Antiglare antireflection film.
(Aspect A20) In the antiglare antireflection film of Aspect A19, a step of providing at least one layer having a refractive index lower than that of the support on the transparent support, and a surface on at least one surface of the transparent support by an external pressure A method for producing an antiglare antireflection film by carrying out the steps of forming irregularities in this order.
(Aspect A21) A polarizing plate comprising the antireflection film according to any one of aspects A12 to A20 on one or both sides of a polarizing plate as a protective film for a polarizer or as a film to be bonded to the surface of a protective film .
(Aspect A22) An image display device, wherein the polarizing plate according to aspect A21 is disposed so that a low refractive index layer disposed on at least one outermost surface is on the viewing side.

If necessary, the antiglare and antireflection film of the present invention can be provided with a hard coat layer. Although the hard coat layer, which has been described above, further includes the structure, the compound used is preferably a polymer having a saturated hydrocarbon or polyether as the main chain, and preferably has a crosslinked structure. In order to obtain a polymer having a crosslinked structure,
It is preferred to crosslink monomers having two or more ethylenically unsaturated groups with ionizing radiation or heat.

Examples of monomers having two or more ethylenically unsaturated groups include polyhydric alcohols and (meth)
Esters with acrylic acid (eg, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, pentaerythritol tetra (meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate , Trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate , Polyester polyacrylate), vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-
2-acryloyl ethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylene bisacrylamide) and methacrylamide are included.

The polymer having a polyether as the main chain is preferably synthesized by a ring-opening polymerization reaction of a polyfunctional epoxy compound. These monomers having an ethylenically unsaturated group need to be cured by a polymerization reaction by ionizing radiation or heat after coating.

Instead of or in addition to the monomer having two or more ethylenically unsaturated groups, a crosslinked structure may be introduced into the binder polymer by the reaction of a crosslinkable group. Examples of the crosslinkable functional group include isocyanate group, epoxy group, aziridine group, oxazoline group, aldehyde group, carbonyl group, hydrazine group, carboxyl group, methylol group and active methylene group. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. In the present invention, the cross-linking group is not limited to the above compound, and may be one showing reactivity as a result of decomposition of the functional group. These compounds having a crosslinking group need to be crosslinked by heat after application.

As a means for imparting antiglare properties to the film, a method of forming an antiglare layer having surface irregularities by dispersing matte particles having a particle size that scatters visible light in a binder, a support by embossing or sandblasting, etc. Various methods, such as a method for imparting irregularities to the surface, a method for imparting irregularities to the surface by the phase separation structure of the coating composition, have been disclosed in public patent gazettes. It is put into practical use by dispersing in the inside. In the present invention, a method using mat particles and a method of imparting surface irregularities by embossing are preferably used.

For the formation of the antiglare layer, fine particles (mat agent) made of a resin or an inorganic compound are used in addition to a binder made of a resin compound for the purpose of imparting antiglare properties by forming surface irregularities. The average particle size is preferably 1.0 to 10.0 μm, more preferably 1.5 to 5.0 μm. Further, it is preferable that fine particles having a particle size smaller than the binder film thickness of the antiglare layer is less than 50% of the total fine particles. The particle size distribution can be measured by the Coulter counter method, but the distribution is considered in terms of the particle number distribution. The thickness of the antiglare layer is preferably 0.5 to 10 μm, more preferably 1 to 5 μm.

For the resin binder used for forming the antiglare layer, a material used for forming the hard coat layer is preferably used from the viewpoint of film strength and transparency. When combined with an antireflection layer, in addition to the hard coat material, the refractive index of the layer is increased from 1.58 to 2.00 by using a high refractive index monomer or high refractive index inorganic fine particles in combination. In some cases, the antireflection performance can be improved. Examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, and the like. Examples of the high refractive index inorganic fine particles include a particle size of at least one oxide selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony.
It is preferable to contain fine particles of nm or less, preferably 50 nm or less. Examples of the fine particles include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO
Etc. The amount of inorganic fine particles added is 10 to 90% by mass of the total weight of the hard coat layer.
Preferably, the content is 20 to 80% by mass.

When unevenness is imparted to the surface of the support by embossing, it is preferable to form the unevenness on the surface after forming all of the optical interference layers. If a plurality of optical interference layers are formed by wet coating after the surface irregularities are formed, it is not preferable because the antireflection performance is remarkably deteriorated due to the unevenness of the thickness of each layer caused by the accumulation of the coating liquid in the recesses. By embossing after forming the entire optical interference layer, the thickness of the optical interference layer becomes substantially uniform. Here, “substantially uniform” means that the central film thickness is within ± 3%.

The antireflection film has a film thickness, refractive index, and single layer of low refractive index layer or low refractive index layer and high refractive index layer so as to have a film thickness, refractive index, and layer structure designed based on the principle of optical interference by an optical thin film. An antireflection layer composed of a plurality of layers is provided. Here, the low refractive index layer and the high refractive index layer refer to a layer having a refractive index lower than the refractive index of the support and a layer having a refractive index higher than the refractive index of the support, respectively. It has a film thickness equal to or less than the wavelength order of the target light. Such a layer having a very thin film thickness is called an optical thin film, and has been put into practical use for various purposes as an optical functional layer based on the principle of optical interference, such as an antireflection film or a reflection film.

As the antireflection layer, it is preferable that the low refractive index layer and the high refractive index layer satisfy the following formulas (f1) and (f2), respectively.
Formula (f1) mλ / 4 × 0.7 <n1d1 <mλ / 4 × 1.3
Formula (f2) nλ / 4 × 0.7 <n2d2 <nλ / 4 × 1.3
In the formula, m is a positive odd number (generally 1), n is a positive integer, n1 and n2 are the refractive indices of the low refractive index layer and the high refractive index layer, respectively, and d1 and d2 are low refractive indices, respectively. It is the film thickness of a refractive index layer and a high refractive index layer.

A low refractive index layer having a refractive index of 1.38 to 1.49 can be selected as a material having a balance between film strength and refractive index. Specifically, a low refractive index having air gaps between fine particles having such a small particle size that does not cause light scattering as disclosed in JP-A-11-38202 and JP-A-11-326601. A layer or a fluorine-containing compound that is crosslinked by heat or ionizing radiation is preferably used. Examples of the crosslinkable fluoropolymer compound include a perfluoroalkyl group-containing silane compound (for example, (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane), etc. And a fluorine-containing copolymer having a monomer as a constituent unit.

Specific examples of the fluorine-containing monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole, etc. ), (Meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (manufactured by Osaka Organic Chemicals) and M-2020 (manufactured by Daikin)), fully or partially fluorinated vinyl ethers, and the like.

As a monomer for imparting a crosslinkable group, in addition to a (meth) acrylate monomer having a crosslinkable functional group in the molecule in advance such as glycidyl methacrylate, it has a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group, etc. ) Acrylate monomers (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, etc.). It is described in JP-A-10-25388 and JP-A-10-147739 that the latter can introduce a crosslinked structure after copolymerization.

Moreover, you may use the copolymer with the monomer which does not contain a fluorine atom other than the polymer which uses the said fluorine-containing monomer as a structural unit. The monomer unit that can be used in combination is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid 2) -Ethylhexyl), methacrylates (methyl methacrylate,
Ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.),
Styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers (methyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamides (N-tertbutyl) Acrylamide, N-cyclohexylacrylamide, etc.), methacrylamides, acrylonitrile derivatives and the like.

For the high refractive index layer, a material preferably used for increasing the refractive index of the antiglare layer is used in the same manner. A preferable refractive index range is 1.60 to 2.20, and a preferable film thickness range is 5 to 5.
The thickness is 300 nm, and the refractive index and film thickness are designed according to the above formula (f2).

Each of the hard coat layer, the antiglare layer and the antireflection layer is formed by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a micro gravure method or an extrusion coating method ( U.S. Pat. No. 2,681,294) can be formed by coating. Two or more layers may be applied simultaneously. The method of simultaneous application is described in US Pat. No. 2,761,789, US Pat. No. 2,941,898, US Pat. No. 3,508,947, US Pat. No. 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, Asakura Shoten (1973). .

In JP-A-2003-149413, a degree of acetylation of 59.0 to 61.5 is provided in order to provide a liquid crystal display device with excellent display quality, in which contrast reduction, gradation or black-and-white reversal, hue change, etc. hardly occur due to angular change. % Light-diffusing film having a light-diffusing layer containing light-transmitting fine particles in a light-transmitting resin on a cellulose acetate film, the thickness of the cellulose acetate film being 20 to 70 μm, and cut-off per 100 mm length The average surface roughness Ra with a value of 0.8mm is 0.2μm
There is a description of the following light diffusion film, and the present invention can also be applied to the present invention.

The antiglare film and antireflection film of the present invention are polarized light used for various applications including LCDs by saponifying the back surface of the support by any means before or after the formation of the antiglare layer and antireflection layer. In the production of the plate, the polarizer can be directly bonded to one or both sides as a protective film for the polarizer.

In particular, in the case where a retardation film is disposed between a polarizing plate and a cell in which liquid crystal is encapsulated in order to increase the viewing angle of the LCD, polarized light used on the viewing side among polarizing plates disposed on both sides of the cell. An antiglare film or an antireflection film is used as a protective film on the air interface side of the plate, and a retardation film is bonded to both sides of the polarizer as a protective layer on the opposite surface between the cell and the polarizer. be able to. A polarizing plate having such a structure can provide functions such as a wide viewing angle and low reflection while having a thickness equivalent to that of a conventional polarizing plate.
Very preferred for use.

Colloidal metal as a multilayer film with transparent thin films of inorganic compounds (metal oxides, etc.) with different refractive indexes formed by chemical vapor deposition (CVD) method, physical vapor deposition (PVD) method, or metal compound sol-gel method such as metal alkoxide Post-treatment after forming the oxide particle film (UV irradiation: JP-A-9-157)
No. 855, plasma treatment: Japanese Patent Laid-Open No. 2002-327310), and a method of forming a thin film. On the other hand, various antireflective films formed by laminating and applying a thin film in which inorganic particles are dispersed in a matrix have been proposed as an antireflective film having high productivity.
The antireflection film which consists of the antireflection layer which provided the anti-glare property in which the surface of the uppermost layer has the shape of a fine unevenness to the antireflection film by application | coating as mentioned above is also mentioned.

[Layer structure of coating type antireflection film]
An antireflection film having a layer structure of at least a medium refractive index layer, a high refractive index layer, and a low refractive index layer (outermost layer) on the substrate is designed to have a refractive index satisfying the following relationship. Refractive index of high refractive index layer> refractive index of medium refractive index layer> refractive index of transparent support> refractive index of low refractive index layer Alternatively, a hard coat layer is provided between the transparent support and the intermediate refractive index layer. Also good. Further, it may comprise a medium refractive index hard coat layer, a high refractive index layer and a low refractive index layer. For example, JP-A-8-122504, JP-A-8-110401, JP-A-10-300902, JP-A-2002-243
No. 906, JP-A No. 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 (eg, 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. Further, the strength of the film is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test according to JIS K5400.

[Transparent support for antireflection film]
The light transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more. The haze of the transparent support is preferably 2.0% or less, and more preferably 1.0% or less. The refractive index of the transparent support is preferably 1.4 to 1.7. Moreover, it is preferable to use a plastic film. Examples of plastic film materials include cellulose ester, polyamide, polycarbonate, polyester (eg, polyethylene terephthalate, polyethylene naphthalate, etc.), polystyrene, polyolefin, polysulfone, polyethersulfone, polyarylate, polyetherimide, polymethyl methacrylate. And polyether ketone.

[High refractive index layer and medium refractive index layer]
The layer having a high refractive index of the antireflection film is composed of a curable film containing at least an inorganic compound ultrafine particle having a high refractive index having an average particle diameter of 100 nm or less and a matrix binder. 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. For example, Ti, Zn, Sb, Sn, Zr, Ce,
Examples thereof include oxides such as 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 treatment agent (for example, silane coupling agents and the like: JP-A Nos. 1-295503, 11-153703, and 2).
No. 000-9908, anionic compound or organometallic coupling agent:
-310432), a core-shell structure with high refractive index particles as a core (: JP-A No. 2001-166104, etc.), specific dispersant combination (eg, JP-A No. 11-153703, Patent No. US6110858B1) And JP-A-2002-27776069). Examples of the material forming the matrix include conventionally known thermoplastic resins and curable resin films. Further, it is selected from a polyfunctional compound-containing composition containing at least two radical polymerizable and / or cationic polymerizable groups, an organometallic compound containing a hydrolyzable group, and a partial condensate composition thereof. At least one composition is preferred. For example, JP 2000-47004 A, 2001-315242, 2001-318.
71, 2001-296401, and the like. 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.

[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 1.20-1
. 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] and 11-38 of JP-A-9-222503.
No. 202, paragraph numbers [0019] to [0030], Japanese Patent Laid-Open No. 2001-40284.
And compounds described in paragraphs [0027] to [0028] of JP-A No. 2000-284102 and the like. 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 (e.g. silaplane (
Manufactured by Chisso Corporation), polysiloxanes containing silanol groups at both ends (JP-A-11-258)
No. 403) and the like. 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 application of the coating composition for forming the outermost layer containing a polymerization initiator, a sensitizer and the like. It is preferable to carry out by light irradiation or heating. A sol-gel cured film is also preferred 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, 58-147).
484, JP-A-9-157582, JP-A-11-106704, etc.), silyl compounds containing a poly (perfluoroalkyl ether) group which is a fluorine-containing long chain group (JP-A 2000- 117902, 2001-48590,
And the like described in JP-A-2002-53804).

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. Low refractive index inorganic compound, paragraph number [002 of JP-A-11-3820
0] to [0038], 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 is a vapor phase method (vacuum deposition method, sputtering method, ion plating method, plasma CVD method, etc.)
May be formed. 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.

[Other layers of antireflection film]
Further, a hard coat layer, a forward scattering layer, a primer layer, an antistatic layer, an undercoat layer, a protective layer, and the like may be provided.

[Hard coat layer]
The hard coat layer is provided on 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 hydrous 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 composition of the hard coat layer include those described in JP-A Nos. 2002-144913, 2000-9908, and WO 0/46617.
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 contains particles having an average particle size of 0.2 to 10 μm to prevent glare (
It can also serve as an antiglare layer (described later) provided with an 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 0.2 to 10
It is preferable that it is micrometer, More preferably, it is 0.5-7 micrometer. 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. Also, JISK54
In the Taber test according to 00, the smaller the wear amount of the test piece before and after the test, the better.

[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 Laid-Open No. 11-38208 specifying a forward scattering coefficient, Japanese Patent Laid-Open No. 2000-199809 having a relative refractive index of a transparent resin and fine particles in a specific range, and Japanese Patent Laid-Open No. 2002 specifying a haze value of 40% or more. -1
No. 07512 and the like.

Each layer of the antireflection film is formed by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating, a micro gravure method or an extrusion coating method (US Pat. No. 2,681,294). It can be formed by coating.

[Anti-glare function]
The antireflection film may have an antiglare 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%, and 5-2
0% is more preferable, and 7 to 20% is most preferable. 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 relatively large particle (particle size 0.05 to 2 μm) is added to a hard coat layer in a small amount (0.1 to 50% by mass) to form a surface uneven film, and these shapes are maintained on the surface uneven film. A method of providing a low refractive index layer (for example, JP 2000-281410 A, 2000-9
5893, 2001-100004, 2001-281407, etc.), a method of physically transferring the uneven shape to the surface after coating the uppermost layer (antifouling layer) (for example, embossing method) JP-A-63-278839, JP-A-11-183710, JP-A-2000-275401, etc.) and the like.

(Polarizer)
Next, the application example is described about the polarizing plate which can apply the cellulose acylate film manufactured by this invention preferably. The cellulose acylate film produced in the present invention can be preferably used as a protective film for a polarizing plate. In general, a polarizing plate is produced by adhering a protective film on at least one surface of a polarizing film prepared by adsorbing and orienting a dichroic substance on a base film. Examples of the polymer used for the base film include polyvinyl alcohol (hereinafter referred to as P
VA) based polymers are common. As the dichroic substance, iodine or a dichroic dye is used alone or in combination. The protective film is required to have physical properties such as low birefringence, transparency, appropriate moisture permeability, and dimensional stability.

Here, the PVA used for the polarizing film is usually saponified polyvinyl acetate. For example, a component copolymerizable with vinyl acetate such as unsaturated carboxylic acid, unsaturated sulfonic acid, olefins, and vinyl ethers is used. You may contain. In addition, modified PVA containing an acetoacetyl group, a sulfonic acid group, a carboxyl group, an oxyalkylene group, or the like can also be used. The degree of saponification of PVA is not particularly limited, but is preferably 80 to 100 mol%, particularly preferably 90 to 100 mol% from the viewpoints of solubility, polarization, heat resistance, moisture resistance, and the like. The degree of polymerization of PVA is not particularly limited, but it is 1000 to 1000 due to film strength, heat resistance, moisture resistance, stretchability, and the like.
10,000 is preferable, and 1500 to 5000 is particularly preferable. Moreover, it does not specifically limit about the syndiotacticity of PVA, It can also take arbitrary values according to the objective.

In order to obtain a polarizing film by dyeing and stretching PVA, a PVA film as a raw fabric is stretched dry or wet, and then immersed in a solution of iodine or dichroic dye. There are a method in which a PVA film is stretched and oriented in a solution, a method in which a PVA film is immersed in iodine or a dichroic dye, and then stretched and oriented in a wet or dry manner. Moreover, when forming a PVA raw fabric by a solution casting method, a method of previously containing a dichroic substance in the PVA solution can be used.

A manufacturing method by wet stretching of a typical polarizing plate will be described below. First, the raw fabric PVA film is pre-swelled with an aqueous solution. Subsequently, it is immersed in the solution of a dichroic substance, and a dichroic substance is adsorbed. Further, it is uniaxially stretched in the traveling direction in an aqueous solution of a boron compound such as boric acid. If necessary, a color adjustment bath, a curing bath or the like may be provided after this. After drying to some extent, a protective film is bonded using an adhesive such as PVA. Furthermore, it dries and a polarizing plate is obtained. Various organic solvents, inorganic salts, plasticizers, boric acids and the like may be added to the pre-swelled solution in the aqueous solution.

As an example of the case where iodine is used as the dichroic substance, an iodine-potassium iodide aqueous solution is used as the staining liquid. Iodine is 0.1-20 g / liter, potassium iodide is 1-100 g
/ Liter, and the weight ratio of iodine and potassium iodide is preferably 1 to 100. Dyeing time is 30
˜5000 seconds are preferable, and the liquid temperature is preferably 5 to 50 ° C. Boron compounds, etc. P in the staining solution
It is also preferable to contain a compound that crosslinks VA. The boron compound in the stretching bath is particularly preferably boric acid. The boric acid concentration is preferably 1 to 200 g / liter, more preferably 10 to 120 g / liter. In addition to the boron compound, the stretching bath can contain an inorganic salt such as potassium iodide, various organic solvents, or a dichroic dye. Color adjustment bath,
In addition to the dichroic dye, the curing bath contains an inorganic salt such as potassium iodide, a boron compound, or the like as necessary.

The stretching process of PVA is generally a method in which tension is applied in the traveling direction of the continuous film, and the film is stretched and oriented in the traveling direction as exemplified above. A method of applying tension in the width direction and orienting in the width direction is also applicable. The stretching is preferably performed 3 times or more in a uniaxial direction, and more preferably 4.5 times or more. Biaxial stretching may be performed depending on the purpose of use of the polarizing film. The film thickness after stretching is not particularly limited, but is preferably 5 to 100 μm, preferably 10 to 40 μm from the viewpoints of handleability, durability and economy.
Is more preferable. The temperature during stretching varies depending on the stretching conditions, but is usually 10 to 250 ° C. When dry stretching at a temperature of 100 ° C. or higher, it is preferably performed in an inert gas atmosphere such as nitrogen. Moreover, it is preferable to perform a crystallization treatment at a temperature of 100 ° C. or higher before dyeing a previously stretched film.

As the dyeing method, not only the immersion method exemplified above but also any means such as application or spraying of iodine or a dye solution is possible. In addition to the liquid layer adsorption described above, adsorption by donation can be performed as necessary. It is also preferable to dye with a dichroic dye. Specific examples of dichroic dyes include, for example, dye compounds such as azo dyes, stilbene dyes, pyrazolone dyes, triphenylmethane dyes, quinoline dyes, oxazine dyes, thiazine dyes and anthraquinone dyes. I can give you. A water-soluble one is preferred, but not limited thereto. Further, it is preferable that a hydrophilic substituent such as a sulfonic acid group, an amino group or a hydroxyl group is introduced into these dichroic molecules.

Typical examples of dichroic molecules include C.I. Ai. direct. Yellow 12,
Sea. Ai. direct. Orange 39, sea. Ai. direct. Orange 72, sea. Ai. direct. Red 28, Sea. Ai. direct. Red 39, Sea. Ai.
direct. Red 79, Sea. Ai. direct. Red 81, Sea. Eye. direct. Red 83, Sea. Ai. direct. Red 89, Sea. Eye. direct. Violet 48, C.I. Ai. direct. Blue 67, Sea. Ai. direct. Blue 90, Sea. Ai. direct. Green 59, Sea. Ai. Acid. Red 37 and the like, and further, JP-A-1-161202, JP-A-1-172906, JP-A-1-1-1.
72907, JP-A-1-183602, JP-A-200048105, JP-A-20006
Examples thereof include dyes described in JP-A-5205 and JP-A-7-261024.
In particular, Sea. Ai. direct. Red 28 (Congo Red) has long been known as preferred for this application. These dichroic molecules are used as free acids or alkali metal salts, ammonium salts, and salts of amines.

By blending two or more of these dichroic molecules, it is possible to produce polarizers having various hues. As a polarizing element or polarizing plate, a compound (pigment) that exhibits black when the polarization axes are orthogonal to each other and a compound in which various dichroic molecules are blended so as to exhibit black are excellent in terms of both single-plate transmittance and polarization rate.

From the viewpoint of increasing the heat resistance and moisture resistance of the polarizing film, it is preferable to include an additive that crosslinks PVA in the manufacturing process of the polarizing film. As the crosslinking agent, those described in US Reissue Patent No. 232897 can be used, but boric acid and borax are preferably used practically. In addition, it is known that the polarizing film contains a metal salt such as zinc, cobalt, zirconium, iron, nickel, manganese and the like because it is known to improve durability. These crosslinking agents and metal salts may be contained in any of the above-described pre-swelling bath, dichroic substance dyeing bath, stretching bath, curing bath, color adjusting bath, etc., and the order of the steps is particularly limited. Not. The adhesive that bonds the protective film and the polarizing film is not particularly limited, and any known adhesive such as PVA-based, modified PVA-based, urethane-based, or acrylic-based can be used. The thickness of the adhesive layer is preferably 0.01 to 20 μm.
1-10 micrometers is further more preferable.

Furthermore, the cellulose acylate film produced in the present invention can be applied as a support for a silver halide photographic light-sensitive material, and various materials, formulations and processing methods described in the patent can be applied. Regarding these inventions, JP-A-2000-105445 describes in detail the color negative, and a cellulose acylate film produced using the non-chlorine organic solvent of the present invention is preferably used. Further, application as a support for a color reversal silver halide photographic light-sensitive material is also preferable, and various materials, formulations, and processing methods described in JP-A No. 11-282119 can be applied.

Moreover, in the polarizing plate, in order to improve the adhesiveness between the change prevention and the polarizing plate protective film and improve the productivity without deteriorating the changing performance, JP-A-2001-343528 has a moisture permeability. 3-10g / m ²・
A polarizing plate protective film having an equilibrium water content of 0.01 to 1.5% at 24 hr and 25 ° K 0% RH is described.

Furthermore, in order not to deteriorate the durability of the polarizing plate even when the polarizing plate protective film is thinned to 20 μm to 65 μm, Japanese Patent Application Laid-Open No. 2001-122980 discloses a cellulose ester film with 2
An invention is described in which the water absorption when immersed in water at 3 ° C. for 24 hours is 1.0% to 4.5%.

Japanese Patent Laid-Open No. 2003-029036 describes a low reflection polarizing plate excellent in display characteristics such as visibility and viewing angle.

Furthermore, Japanese Patent Application Laid-Open No. 2003-098348 discloses that on the surface opposite to the polarizing layer of one support in order to have excellent productivity and durability, and to prevent deterioration of external light reflection display quality and to expand the viewing angle. Is formed with an optical compensation layer comprising an optically anisotropic layer, an antireflection layer is formed on the surface of the other transparent support opposite to the polarizing layer, and the transparent support has a total substitution degree of 2.55 to 2.80. It describes a polarizing plate made of cellulose ester.

Japanese Patent Application Laid-Open No. 2002-139622 discloses that one transparent support is not provided in order to prevent display quality deterioration due to reflection of external light and to expand the viewing angle of a TN mode liquid crystal display device and a color liquid crystal display device. A polarizing plate having an optical compensation layer comprising an optical anisotropic layer on the surface opposite to the polarizing layer, and an antireflection layer on the surface opposite to the polarizing layer of the other transparent support. The optically anisotropic layer is a layer formed from a discotic structural unit compound, the disc surface of the discotic structural unit is inclined with respect to the transparent support surface, and the disc surface of the discotic structural unit and the transparent support surface There is a description of a polarizing plate in which the angle formed by is changed in the depth direction of the optically anisotropic layer.

Furthermore, Japanese Patent Application Laid-Open No. 2002-189126 discloses a method for improving the durability and the like of a polarizing plate particularly at high temperatures by defining the sound wave propagation velocity in the longitudinal direction of the film within a predetermined range. The invention relating to cellulose acylate described in these publications described above can also be applied to the present invention.

In addition, the cellulose film described in this invention can be used for the apparatus and optical film which are described in the open patent publication of the following paragraph.

JP-A-5-19216, JP-A-5-162261, JP-A-5-1882518, JP-A-5-19115, JP-A-5-96819, JP-A-5-26411, JP-A-5-214411, Kaihei 5-218417, JP-A-5-281537, JP-A-5-288921, JP-A-5-288923, JP-A-5-311119, JP-A-5-339395, JP-A-5-40204, JP-A-5-40204 JP 5-45512, JP 6-109922, JP 6-123805, JP 6-160626, JP 6-214107, JP 6-214108, JP 6-214109, JP 6-214109, JP JP-A-222209, JP-A-6-222353, JP-A-6-234175, JP-A-6-235810, JP-A-64-241397, JP-A-6-2558520, JP-A-6-2463030, JP-A-6-6 305270, JP-A-6-331826, JP-A-6-347641, JP-A-6-75110, JP-A-6-75111, JP-A-6-82779, JP-A-6-93133, JP-A-7-104126 JP, JP 7-134212, JP 7-181322, JP 7-188383, JP 7-230086, JP 7-290652, JP 7-294903, JP 7-294904, etc. JP-A-7-294905 JP-A-7-325219, JP-A-7-56014, JP-A-7-56017, JP-A-7-92321, JP-A-8-12525, JP-A-8-14220, JP-A-8110016, JP-A-8-188661, JP-A-8-21999, JP-A-8-240712, JP-A-8-25575, JP-A-8-286179, JP-A-8-292322, JP-A-8-297211, Special Kaihei 8-304624, JP-A-8-313881, JP-A-8-43812, JP-A-8-62419, JP-A-8-62422, JP-A-8-76112, JP-A-8-94834, JP-A-8-94834 No. 9-137143, JP-A-9-197127, JP-A-9-251110, JP-A-9-258023, JP-A-9-269413, JP-A-9-269414, JP-A-9-281483, JP-A-9 -288212, JP-A-9-288213, JP-A-9-292525, JP-A-9-292526, JP-A-9-294959, JP-A-9-318817, JP-A-9-80233, JP-A-9-233 99515, JP 10-10320, JP 10-104428, JP 10-111403, JP 10-111507, JP 10-123302, JP 10-123322, JP 10-123323 No. 10 176118, JP 10-186133, JP 10-264322, JP 10-268133, JP 10-268134, JP 10-319408, JP 10-332933, JP 10-39137 JP, 10-39140, JP 10-68821, JP 10-68824, JP 10-90517, JP 11-116903, JP 11-181131, JP 11-211901 JP-A-11-211914, JP-A-11-242119, JP-A-11-246693, JP-A-11-246694, JP-A-11-256117, JP-A-11-258425, JP-A-11-263861, JP-A-11-287902, JP-A-11-295525, JP-A-11-295527, JP-A-11-302423, JP-A-11-309830, JP-A-11-323552, JP-A-11-335641, Special Kaihei 11-344700, JP 11-349947, JP 11-95011, JP 11-95030, JP 11-95208, JP 2000-109780, JP 2000-110070, JP JP 2000-119657, JP 2000-141556, JP 2000-147208, JP 2000-17099, JP 2000-171603, JP 2000-171618, JP 2000-180615 JP 2000-187102, JP 2000-187106, JP 2000-191819, JP 2000-191821, JP 2000-193804, JP 2000-204189, JP 2000-206306, JP 2000-214323, JP 2000-214329, JP 2000-230159, JP 2000-235107, JP 2000-241626, JP 2000-250038, JP 2000-267095, JP JP 2000-284122, JP 2000-292780, JP 2000-292781, JP 2000-304927, JP 2000-304928, JP 2000-304929, JP 2000-309195, JP 2000 JP-A-309196, JP-A-2000-309198, JP-A-2000-309642, JP-A-2000-310704, JP-A-2000-310708, JP-A-2000-310709, JP-A-2000-310710, JP-A-2000- 310711, JP 2000-310712, JP 2000-310713, JP 2000-310714, JP 2000-310715, JP 2000-310716, JP 2000-310717, JP 2000-321560 JP, 2000-321567, JP 2000-329936, JP 2000-329941, JP 2000-338309, JP 2000-338329, JP 2000-344905, JP 2000-347016 , JP200 0-347017, JP 2000-347026, JP 2000-347027, JP 2000-347029, JP 2000-347030, JP 2000-347031, JP 2000-347032, JP 2000 -347033, JP 2000-347034, JP 2000-347035, JP 2000-347037, JP 2000-347038, JP 2000-86989, JP 2000-98392, JP 2001- JP 100012, JP 2001-108805, JP 2001-108806, JP 2001-133627, JP 2001-133628, JP 2001-142062, JP 2001-142072, JP 2001-174630 JP, 2001-174634, JP 2001-174637, JP 2001-179902, JP 2001-183526, JP 2001-183653, JP 2001-188103, JP 2001-188124 , JP 2001-188125, JP 2001-188225, JP 2001-188231, JP 2001-194505, JP 2001-228311, JP 2001-228333, JP 2001-242461, JP 2001-242546, JP 2001-247834, JP 2001-26061, JP 2001-264517, JP 2001-272535, JP 2001-278924, JP 2001-2797, Special Open 2001-287308, JP 2001-305345, JP 2001-311823, JP 2001-311827, JP 2001-350005, JP 2001-356207, JP 2001-356213, JP 2001-42122, JP 2001-42323, JP 2001-42325, JP 2001-4819, JP 2001-4829, JP 2001-4830, JP 2001-4831, JP 2001-4832, JP 2001 -4834, JP-A-2001-4835, JP-A-2001-4836, JP-A-2001-4838, JP-A-2001-4839, JP-A-2001-51118, JP-A-2001-51119, JP-A-2001- 51120, JP 2001-51273, JP 2001-51274, JP 2001-55573, JP 2001-66431, JP 2001-66597, JP 2001-74920, JP 2001-81469 JP, 2001-83329, JP 2001-83515, JP 2001-91719, JP 2002-162628, JP 2002-169024, JP 2002-189421, JP 2002-201367 JP, 2002-20410, JP 2002-258046, JP 2002-275391, JP 2002-294174, JP 2002-311214, JP 2002-311246, JP 2002-328233, JP2002-338703, JP2002-363266, Special JP 2002-365164, JP 2002-370303, JP 2002-40209, JP 2002-48917, JP 2002-6109, JP 2002-71950, JP 2002-82222, JP 2002 -90528, JP2003-105540, JP2003-114331, JP2003-131036, JP2003-139952, JP2003-153353, JP2003-172819, JP2003- JP-A-35819, JP-A-2003-43252, JP-A-2003-50318, JP-A-2003-96066.

In addition, it is preferable that the manufacturing process conditions of the width direction and longitudinal direction (conveyance direction) of the film of this invention do not have dispersion | variation in each direction except when changing conditions to a width direction and a longitudinal direction intentionally. . Thereby, the obtained film has a substantially uniform desired physical property in each direction of the casting width direction and the longitudinal direction.

Examples are given below, but the present invention is not limited thereto. The parts by mass of the compound used are shown below.
Cellulose triacetate A (degree of substitution 2.84, viscosity average polymerization degree 306, water content 0.2% by weight, viscosity of 6% by weight in dichloromethane solution 315 mPa · s, average particle size 1.5 mm
100 parts by weight methylene chloride (first solvent) 320 parts by weight methanol (second solvent) 83 parts by weight 1-butanol (third solvent) 3 parts by weight plasticizer A (powder having a standard deviation of 0.5 mm) Triphenyl phosphate) 7.6 parts by mass plasticizer B (biphenyl, diphenyl phosphate) 3.8 parts by mass UV agent a: 2 (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzo Triazole 0.7 parts by mass UV agent b: 2 (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) -5
Chlorbenzotriazole 0.3 parts by mass Citric acid ester mixture (citric acid, monoethyl ester, diethyl ester, triethyl ester mixture) 0.006 parts by mass fine particles (silicon dioxide (particle size 15 nm), Mohs hardness about 7) 0.05 Parts by mass Dye (Dyestuff Example 115 (I-4)) 0.0005 parts by mass

The cellulose triacetate A used here has a residual acetic acid content of 0.1% by mass or less, a Ca content of 58 ppm, an Mg content of 42 ppm, and an Fe content of 0.5 ppm.
And 40 ppm free acetic acid and 15 ppm sulfate ions. Also 6
The degree of substitution of the coordinate acetyl group was 0.91, 32.5% of the total acetyl. The acetone extract was 8% by mass, and the weight average molecular weight / number average molecular weight ratio was 2.5. The yellow index is 1.7, haze is 0.08, transparency is 93.5%, Tg
(Glass transition temperature; measured by DSC) was 160 ° C., and the crystallization exotherm was 6.4 J / g. This cellulose triacetate A was synthesized using cellulose collected from cotton as a raw material. In the following description, this is called cotton raw material TAC.

(1-1) Preparation of cellulose triacetate solution (hereinafter referred to as dope) Cellulose triacetate powder while mixing and mixing well with a plurality of solvents in a 4000 L stainless steel dissolution tank having stirring blades Body (flakes) was gradually added to prepare a total of 2000 kg. In addition, all the solvents used that the water content is 0.5 mass% or less. First, powder of cellulose triacetate is charged into a dispersion tank, and the stirring shear rate is initially 5 m / sec (shear stress 5 × 10 ⁴ k).
gf / m / sec ² ) Dissolver type eccentric stirring shaft that stirs at a peripheral speed and an anchor blade on the central axis, and a peripheral speed of 1 m / sec (shear stress 1 × 10 ⁴ kgf / m / sec ² ) The mixture was dispersed for 30 minutes under the stirring conditions of The dispersion start temperature is 25 ° C. and the final temperature reached 4 ° C.
It became 8 ° C. After completion of the dispersion, the high-speed stirring was stopped, and the peripheral speed of the anchor blade was set at 0.5 m / sec and further stirred for 100 minutes to swell the cellulose triacetate flakes. Until the end of swelling, the inside of the tank was pressurized to 0.12 MPa with nitrogen gas. At this time, the oxygen concentration in the tank was less than 2 vol%, and the state of no problem was maintained in terms of explosion protection. The water content in the dope was confirmed to be 0.5% by mass or less, and 0.3% by mass in this experiment.

(1-2) Dissolution / Filtering Step The swollen solution was heated from the tank to 50 ° C. with a jacketed pipe, and further heated to 90 ° C. with a pressure of 2 MPa to completely dissolve. The heating time was 15 minutes.
Next, the temperature was lowered to 36 ° C., and a dope was obtained by passing through a filter medium having a nominal pore diameter of 8 μm. At this time, the primary pressure of filtration was 1.5 MPa, and the secondary pressure was 1.2 MPa. Filters exposed to high temperatures,
The housing and piping used were made of Hastelloy (registered trademark) and had excellent corrosion resistance and had a jacket for circulating a heat medium for heat insulation and heating.

(1-3) Concentration / filtration The pre-concentration dope thus obtained is flushed at 80 ° C. in a normal pressure tank,
The evaporated solvent was recovered and separated by a condenser. The solid content concentration of the dope after the flash is 21.8
It became mass%. The condensed solvent was sent to a recovery process to be reused as a solvent in the preparation process (recovery is carried out by a distillation process, a dehydration process, etc.). The flash tank had an anchor blade on the central axis, and deaerated by stirring at a peripheral speed of 0.5 m / sec. The temperature of the dope in the tank was 25 ° C., and the average residence time in the tank was 50 minutes. The shear viscosity measured at 25 ° C. after collecting this dope was 450 (Pa · s) at a shear rate of 10 (sec ⁻¹ ).
-S).

Next, the dope was defoamed by applying weak ultrasonic waves. Then 1.5M
In a state of being pressurized to Pa, first, a sintered fiber metal filter having a nominal pore diameter of 10 μm was passed, and then a sintered fiber filter having a same pore diameter of 10 μm was passed. Each primary pressure is 1.5,
The pressure was 1.2 MPa, and the secondary pressure was 1.0 and 0.8 MPa. The dope temperature after filtration is
The temperature was adjusted to 36 ° C. and stored in a 2000 L stainless steel stock tank. The stock tank had an anchor blade on the center axis and was constantly stirred at a peripheral speed of 0.3 m / sec. In the following description, this dope is referred to as sample 001. In addition, when the dope was prepared from the dope before concentration, no problem such as corrosion occurred at all in the wetted part of the dope.

Cellulose triacetate A of sample 001 was mixed with 50 parts by mass of cotton raw material TAC and chip TAC5
The dope was prepared under the same conditions except that the mixture was changed to 0 parts by mass. In the following description, this dope is referred to as sample 002. The chip TAC is obtained by pulverizing the ears of a film sample 101-1, which will be described later.

A dope was prepared under the same components and under the same conditions as sample 001 except that UV agents a and b, ethyl citrate as a peeling accelerator and silicon dioxide as a matting agent were not used, and a solid content was 2
A 1.8% by mass dope was obtained. In the following description, this dope is referred to as sample 003.
Further, a dope having a solid content of 21.8% by mass was obtained by preparing a dope under the same components and under the same conditions as in the sample 002 except that the peeling accelerator and the matting agent were not used. Hereinafter, it is referred to as sample 004.

Further, 86.5 parts by mass of methylene chloride, 13 parts by mass of acetone, and 0.
5 parts by mass of a mixed solvent was prepared. In the following description, this mixed solvent is referred to as Sample 070.

(1-4) Casting step Subsequently, the dope in the stock tank was fed by a feedback control using an inverter motor so that the primary pressure of the high precision gear pump became 0.8 MPa with a gear pump for primary pressure increase. The high-precision gear pump had a volume efficiency of 99.2% and a discharge rate variation of 0.5% or less. The discharge pressure was 1.5 MPa.

The casting die has a width of 1.8m and is equipped with a feed block adjusted for co-casting. In addition to the mainstream, a device that can be laminated on both sides to form a three-layer film is used. It was. In the following description, a layer formed from the mainstream is referred to as an intermediate layer, a support surface side layer is referred to as a support surface, and an opposite surface is referred to as an air surface. The dope liquid flow path is for the intermediate layer,
Three flow paths for the support surface and the air surface were used.

Samples 070 (mixed solvent) and material 003 dope were mixed with UV agents a and b to form a solution. This solution was mixed in-line with the sample 003 being fed via a static mixer to obtain an intermediate layer dope. The mixing amount was adjusted so that the total solid concentration was 21.8% by mass and the retardation control agent B was 1.0% by mass in the form of a film. In the following description, this dope is referred to as Sample 010A.

A matting agent (silicon dioxide), a peeling accelerator (citric acid ethyl ester), and sample 003 were dissolved or dispersed in sample 070 to obtain a dispersion. This dispersion was mixed in-line with a sample 003 being fed via a static mixer to produce a support surface dope. The amount added is
The total solid concentration is 20.5% by mass, the matting agent concentration is 0.05% by mass, and the release accelerator concentration is 0. 0%.
It carried out so that it might become 03 mass%. In the following description, this dope is referred to as sample 011.

A matting agent (silicon dioxide) was dispersed in Sample 070 to obtain a dispersion. This dispersion was mixed in-line with the sample 003 being fed via a static mixer to produce an air surface dope. The amount added was such that the total solid content concentration was 20.5% by mass and the matting agent concentration was 0.1% by mass. In the following description, this dope is referred to as sample 012. These samples 01
What consists of 0A, 011 and 012 is referred to as a dope sample 101-1 in the following description.

And the film thickness of the completed cellulose triacetate film sample 101-1 (air surface,
The intermediate layer and the support surface are 4 μm, 73 μm, and 3 μm, respectively, and the casting width is 1700 mm so that the product thickness is 80 μm, and the flow rate of cellulose triacetate dope at each die protrusion is adjusted. It was. In order to adjust the temperature of each dope (samples 012, 010A, 011) to 36 ° C., a jacket was provided on the casting die, and the inlet temperature of the heat transfer medium supplied into the jacket was set to 36 ° C.

The die, feed block, and piping were all kept at 36 ° C. during the work process. The die was a coat hanger type die, with thickness adjusting bolts provided at a pitch of 20 mm, and having an automatic thickness adjusting mechanism using a heat bolt. This heat bolt can also set a profile according to the liquid feed amount of the high precision gear pump by a preset program, and feedback control can also be performed by an adjustment program based on the profile of the infrared thickness gauge installed in the film forming process It has performance. Casting edge 20m
The thickness difference between any two points 50 mm apart in the film excluding m was within 1 μm, and the smallest difference in thickness in the width direction was adjusted to be 3 μm / m or less. The average thickness accuracy of each layer was controlled to ± 2% or less for both outer layers and ± 1% or less for the mainstream, and the overall thickness was adjusted to ± 1.5% or less.

In addition, a chamber for decompressing was installed on the primary side of the die. The degree of decompression of the decompression chamber can apply a pressure difference of 1 Pa to 5000 Pa before and after the casting bead, and can be adjusted according to the casting speed. At that time, the bead length is 2mm ~
The pressure difference was set to 50 mm. Further, the chamber temperature was provided with a mechanism that can be set higher than the condensation temperature of the gas around the casting portion. Labyrinth was provided at the front and rear of the bead. Openings were provided at both ends. Furthermore, from there, the one to which an edge suction device was attached was used in order to adjust the turbulence of the flow at both edges of the beads. Moreover, the apparatus which can set the temperature of a chamber higher than the condensation temperature of the gas around a casting part was attached.

(1-5) Casting die Here, the material of the die is a duplex stainless steel having a mixed composition of an austenite phase and a ferrite phase, and the coefficient of thermal expansion is 2 × 10 ⁻⁵ (° C. ⁻¹ ) or less. A material having a corrosion resistance substantially equivalent to that of SUS316 was used in a forced corrosion test with an aqueous electrolyte solution. In addition, a material having corrosion resistance that does not cause pitting (opening) at the gas-liquid interface even when immersed in a mixed solution of dichloromethane, methanol, and water for 3 months was used. Furthermore, the material that had been aged for more than one month after casting was ground to keep the surface state of the cellulose triacetate solution constant. The finishing accuracy of the wetted surface of the casting die and the feed block is 1 μm or less in surface roughness, the straightness is 1 μm / m or less in any direction, and the clearance of the slit is 0.5 mm to 3.5 mm by automatic adjustment. It was adjustable until. In this example, the measurement was performed at 1.5 mm. About the corner | angular part of the liquid-contact part of die-die tip, it processed so that R might be set to 50 micrometers or less over the slit full width. The shear rate inside the die was in the range of 1 (1 / sec) to 5000 (1 / sec).

The casting die has a width of 1.7 m. In addition, the temperature was kept at 36 ° C. during the work process. The casting die was a coat hanger type die, in which thickness adjusting bolts were provided at a pitch of 20 mm and equipped with an automatic thickness adjusting mechanism using a heat bolt. This heat bolt can also set a profile according to the liquid feeding amount of the high precision gear pump by a preset program. The thing which has the performance which can also be feedback-controlled by the adjustment program based on the profile of the infrared thickness meter installed in the film forming process was used. The thickness difference between two arbitrary points separated by 50 mm in the film excluding the casting edge portion of 20 mm was within 1 μm, and the largest difference in the width direction thickness was adjusted to be 3 μm or less. The thickness accuracy was adjusted to ± 1.5 μm or less.

Further, a casting die provided with a cured film was used at the lip tip. Examples of means for providing a hard film include ceramic coating, hard chrome plating, and nitriding. When ceramics are used as the cured film, those that can be ground, have low porosity, are not brittle, have good corrosion resistance, have good adhesion to the die, and do not have adhesion to the dope are preferable. Specifically, tungsten carbide (WC), Al ₂ O ₃ , TiN, Cr ₂ O _{3 and the} like are preferable, and WC is particularly preferable. In the present invention, a WC coating formed by spraying is used.

Furthermore, in order to prevent the dope flowing out at the slit end of the die from locally drying and solidifying, a mixed solvent (sample 070), which is a solvent for solubilizing the dope, is applied to the gas-liquid interface between the bead end and the slit. It was supplied at 0.5 cc / min on one side. The pulsation rate of the pump supplying this liquid is 5%
It was the following. In addition, the pressure on the back surface of the bead was reduced by 150 Pa by the decompression chamber. A jacket was attached to keep the temperature of the vacuum chamber constant. A heat transfer medium adjusted to 35 ° C. was supplied into the jacket. Edge suction air volume is 1L / min to 100L
In the present example, adjustment was appropriately made in the range of 30 L / min to 40 L / min.

(1-6) Metal support A stainless steel endless band having a width of 2.1 m and a length of 70 m was used as the support. The band was 1.5 mm thick and polished so that the surface roughness was 0.05 μm or less. The material was made of SUS316 and had sufficient corrosion resistance and strength. The thickness unevenness of the entire band was 0.5% or less. The band uses a type driven by two drums, and the tension of the band at that time is adjusted to 1.5 × 10 ⁴ kg / m, and the relative speed difference between the band and the drum becomes 0.01 m / min or less. It was a thing. Also,
Band drive speed fluctuation was 0.5% or less. Moreover, the meandering in the width direction of one rotation is 1.5 mm
Both ends of the band were detected and controlled so as to limit to the following. Further, the positional fluctuation in the vertical direction accompanying the drum rotation on the support surface just below the casting die was set to 200 μm or less. The support is installed in a casing having wind pressure vibration suppression means. 3 from the die on this support
The layer dope was co-cast.

As the casting drum, a drum having equipment for circulating a heat transfer medium (refrigerant) therein was used so as to cool the support. Moreover, since the other drum supplies heat for drying, the heat transfer medium can pass water. The temperature of each heat transfer medium was 5 ° C. (casting die side) and 40 ° C. The surface temperature of the central part of the support just before casting was 15 ° C. The temperature difference between both ends was 6 ° C. or less.

The drum can be directly used as a casting support. In this case, the drum is rotated with an accuracy of 0.2 mm or less. The average surface roughness of the drum is also 0.01 μm.
The following are sufficient hardness and durability by chrome plating treatment.

There should be no surface defects in either the drum or the band.
The above pinholes are completely absent, and the number of pinholes of 10 to 30 μm is 1 / m ² or less, 1
A support having 2 pinholes / m ² or less was used.

(1-7) Casting drying The temperature of the casting chamber provided with the casting die and the support was kept at 35 ° C. The dope cast on the band was first dried by sending parallel-flow drying air. The overall heat transfer coefficient from the drying air to the dope during drying was 24 kcal / m ² · hr · ° C. The temperature of the drying air was 135 ° C on the upstream side of the upper part of the band, and 140 ° C on the downstream side. The lower part of the band
The temperature was 65 ° C. The saturation temperature of each gas was around -8 ° C. The oxygen concentration in the dry atmosphere on the support was kept at 5 vol%. Note that the air was replaced with nitrogen gas in order to maintain the oxygen concentration at 5 vol%. In order to condense and recover the solvent in the casting chamber,
A condenser (condenser) was provided, and the outlet temperature was set to -10 ° C.

For 5 seconds after casting, the static pressure fluctuation in the immediate vicinity of the casting die was suppressed to ± 1 Pa or less so that the dry wind did not directly hit the dope with a wind shield. When the solvent ratio in the dope reached 50% by mass on a dry basis, the film was peeled off from the casting support. The peeling tension at this time is 10k
gf / m, and the peeling speed (peeling roll draw) is 100.1 with respect to the support speed.
It set so that it could peel off appropriately in the range of% -110%. The surface temperature of the peeled film was 15 ° C. The drying rate on the support was an average of 60% by weight dry weight reference solvent / min. The solvent gas generated upon drying was led to a condenser, liquefied at −10 ° C., recovered, and reused as a charging solvent. The drying air from which the solvent was removed was heated again and reused as drying air. At that time, the water content in the solvent was adjusted to 0.5% or less and reused.

The peeled film was conveyed by the transfer part provided with many rollers. In the transition part,
Three rollers were provided, and the temperature at the crossover was kept at 40 ° C. During conveyance with the roller at the crossing portion, a tension of 16N to 160N was applied to the film.

(1-8) Tenter Transport / Drying Process Conditions The peeled film was transported in the drying zone of the tenter while being fixed at both ends with a tenter having a clip, and dried with drying air. The clip was cooled by supplying a heat transfer medium at 20 ° C. The tenter is driven by a chain, and the speed fluctuation of the sprocket is zero.
. It was 5% or less. Further, the interior of the tenter was divided into three zones, and the drying air temperature in each zone was set to 90 ° C., 100 ° C., and 110 ° C. from the upstream side. The gas composition of the drying air was set to a saturated gas concentration of −10 ° C. The average drying rate in the tenter was 120% by mass (dry weight reference solvent) / min. At the outlet of the tenter, the amount of residual solvent in the film was adjusted to 10% by mass or less, and in this experiment, the conditions of the drying zone were adjusted to 7% by mass. In the tenter, the film was stretched in the width direction while being conveyed. The amount of widening when the width when conveyed to the tenter was 100% was 103%. Stretching rate from stripping roller to tenter entrance (tenter-driven draw)
Was 102%. As for the stretching ratio in the tenter, the difference in the substantial stretching ratio at a portion 10 mm or more away from the tenter biting portion was 10% or less, and the difference in the stretching ratio at any two points 20 mm apart was 5% or less. The ratio of the length of the base end fixed with a tenter is 9
0%. Further, the tenter clip was transported while being cooled so as not to exceed 50 ° C. The solvent evaporated in the tenter part was condensed and liquefied at a temperature of −10 ° C. and recovered. A condenser (condenser) was provided for condensation recovery, and the outlet temperature was set to -8 ° C. The water content contained in the solvent was adjusted to 0.5% by mass or less and reused.

Then, the ears were cut at both ends within 30 seconds from the tenter exit. Ears 50 mm on both sides were cut with an NT-type cutter, and the cut ears were blown by a cutter blower to a crusher and crushed into chips of about 80 mm ² on average. This chip is the chip TAC described above. This chip was again used as a raw material in the preparation process together with cellulose triacetate flakes as a raw material for preparation. The oxygen concentration in the dry atmosphere of the tenter part was kept at 5 vol%. Note that the air was replaced with nitrogen gas in order to maintain the oxygen concentration at 5 vol%. The film was preheated in a predrying zone supplied with 100 ° C. drying air before being dried at a high temperature in a roller conveyance zone described later.

(1-9) Post-drying process conditions The trimmed cellulose triacetate film obtained by the method described above was dried at high temperature in the roller transport zone. The roller transport zone is divided into 4 sections, and 120 ° C, 13 ° C from the upstream side.
Dry air of 0 ° C, 130 ° C, and 130 ° C was supplied. At this time, the roller conveying tension of the film was set to 100 N / width, and the film was dried for about 10 minutes until the residual solvent amount finally reached 0.3% by mass. The wrap angle of the roller was 90 degrees and 180 degrees. The roller was made of aluminum or carbon steel, and a hard chrome plating was applied to the surface. As the surface shape of the roller, a flat one and a mat formed by blasting were used. All the shakes due to the rotation of the roller were 50 μm or less. The roller deflection at a tension of 100 N / width was selected to be 0.5 mm or less.

A forced charge removal device (charge removal bar) was installed during the process so that the film voltage during conveyance was always in the range of -3 kV to 3 kV. In the winding part, not only the charge removal bar but also ion wind charge removal was installed so that the charge would be -1.5 kv to 1.5 kv.

The solvent gas contained in the drying air was adsorbed and recovered using an adsorbent. The adsorbent was activated carbon, and desorption was performed using dry nitrogen. The recovered solvent was adjusted to a water content of 0.3% by mass or less and reused as a charged solvent. In addition to solvent gas, the drying air contains plasticizers, UV absorbers, and other high-boiling substances, so they were removed by a cooler and pre-adsorber to be removed by cooling and recycled. And adsorption / desorption conditions were set so that VOC in outdoor exhaust gas would be 10 ppm or less finally. The amount of solvent recovered by the condensation method of all evaporated solvents is 90% by mass.
Most of the rest was recovered by adsorption recovery.

The dried film was conveyed to the 1st humidity control chamber. Dry air at 110 ° C. was supplied to the transition portion between the roller conveyance zone and the first humidity control chamber. The first humidity chamber has a temperature of 50 ° C and a dew point of 20 ° C.
The air was supplied. Further, the film was conveyed to a second humidity control chamber that suppresses the curling of the film. In the second humidity control chamber, air of 90 ° C. and humidity 70% was directly applied to the film.

(1-10) Post-treatment and winding conditions The dried cellulose triacetate film was cooled to 30 ° C. or lower, and both ends were trimmed and further knurled on both ends of the film. The knurling is applied by embossing from one side, the knurling width is 10 mm, and the maximum height is 1 on average than the average thickness.
The pressing pressure was set to be 2 μm higher.

And the film was conveyed to the winding chamber. The winding chamber was kept at a room temperature of 28 ° C. and a humidity of 70%. Cellulose triacetate film thus obtained (thickness 80 μm)
The product width was 1475 mm. The diameter of the core is 169mm and the tension is 36
The tension pattern was 0 N / width and the end of winding was 250 N / width. The total winding length was 3940 m. The oscillating period during winding was 400 m, and the oscillating width was ± 5 mm. Moreover, the press roll was set to the winding roll and the pressure was set to 50 N / width. The temperature of the film during winding is 25 ° C., the water content is 1.4% by mass, and the residual solvent amount is 0
. It was 3 mass%. The average drying rate was 20% by mass (dry weight reference solvent) / min throughout the entire process. Moreover, there was no winding looseness and wrinkles, and no winding slip occurred in the impact test at 10G. The roll appearance was also good. Through the above steps, a cellulose triacetate film sample 101-1 was formed.

This film sample 101-1 roll was stored in a storage rack at 25 ° C. and 55% RH for 1 month, and further examined in the same manner as described above. As a result, no significant change was observed. Further, no adhesion was observed in the roll. Moreover, after film sample 101-1 was formed, no peeling residue of the cast film formed from the dope was found on the endless belt as the metal support.

(1-11) Evaluation and Results Evaluation methods for the samples obtained in the examples are shown below.

(1) Stability of solution The dope after filtration and concentration obtained in (1-3) is collected and observed while standing still at 30 ° C., and evaluated in the following four stages of A, B, C, and D did.
A: Transparency and liquid uniformity are exhibited even over 20 days.
B: Transparency and liquid uniformity are maintained until lapse of 10 days, but a little white turbidity is observed in 20 days.
C: The liquid is transparent and uniform at the end of the liquid preparation, but after one day, it gels and becomes a non-uniform liquid.
D: The liquid is in an opaque and non-uniform solution state with no swelling / dissolution.

(2) Film surface condition The film was observed visually, and the surface condition was evaluated as follows.
A: The film surface is smooth.
B: Although the film surface is smooth, a little foreign material is seen.
C: Weak irregularities are seen on the film surface, and the presence of foreign matter is clearly observed.
D: Unevenness is seen on the film, and many foreign matters are seen.

(3) Moisture and heat resistance of film 1 g of sample is folded and placed in a 15 ml capacity glass bottle, temperature is 90 ° C. and relative humidity is 100%.
After conditioning the humidity under the conditions, it was sealed. This was taken out after 90 days at 90 ° C. The state of the film was visually confirmed and the following judgment was made.
A: No particular abnormality is observed B: A slight decomposition odor is observed C: A considerable decomposition odor is recognized D: A change in shape due to decomposition odor and decomposition is observed

The obtained cellulose triacetate film sample 101-1 has a solution stability of A, a film surface shape of A, a film tear test of 16 g, and a film folding test of 71.
The heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0.
Less than 01% by mass, containing less than 0.05% by mass of Ca and less than 0.01% by mass of Mg,
The thickness of the cellulose triacetate film was 80 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less. In addition, the longitudinal and transverse average heat shrinkage (80 ° C., 90% RH 48 hours) of the film was −0.1%, and a film that hardly caused heat shrinkage was obtained. The residual solvent amount at the tenter outlet was 7% by mass, and the ear silo LEL at that time was good at less than 25%.

The film sample 101-1 has a haze of 0.3%, a transparency (transparency) of 92.4%,
The tilt width is 19.6 nm, the limit wavelength is 392.7 nm, the absorption edge is 374.1 nm, 380 n
The absorption of m is 2.0%, Re is 1.2 nm, Rth is 48 nm, and the molecular orientation axis is 1
. The elastic modulus is 3.54 GPa in the longitudinal direction and 3.45 GPa in the width direction, the tensile strength is 142 MPa in the longitudinal direction, 141 MPa in the width direction, and the elongation is 43% in the longitudinal direction and 49% in the width direction.
Kisimi value (static friction coefficient) is 0.65, Kisimi value (dynamic friction coefficient) is 0.51, Alkaline hydrolyzability is A, curl value is -0.4 at 25% RH, 1 at wet .7. The moisture content was 1.4% by mass, the residual solvent amount was 0.3% by mass, and the thermal shrinkage was −0.09% in the longitudinal direction and −0.08% in the width direction. . The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.02 mm to 0.05 mm, less than 10/3 m, 0
. 05-0.1 mm was less than 5/3 m, and there was no more than 0.1 mm. These had excellent properties for optical applications. Moreover, adhesion after application was not observed (◯), and the moisture permeability was good (◯).

Next, a cellulose triacetate film sample 101-2 was prepared. Sample 003
Sample 010 which is each dope of dope sample 101-1, except that sample 004 was used instead of
Samples 013A, 014, and 015 were prepared under the same conditions as A, 011 and 012. These samples 013A, 014, and 015 are collectively referred to as a dope sample 101-2. Sample 013A
, 014, 015 were used to form a film sample 101-2 under the same conditions as the sample 101-1, and the same evaluation as the film sample 101-1.

The obtained cellulose triacetate film sample 101-2 has a solution stability of A, a film surface shape of A, a film tear test of 15 g, and a film folding resistance test of 73.
The heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0.
Less than 01% by mass, containing less than 0.05% by mass of Ca and less than 0.01% by mass of Mg,
The thickness of the cellulose triacetate film was 80 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 101-2 has a haze of 0.3% and a transparency (transparency) of 92.4%.
The slope width is 19.5 nm, the limit wavelength is 392.5 nm, the absorption edge is 374.2 nm, 380
Absorption of nm is 1.9%, Re is 1.2 nm, Rth is 49 nm, molecular orientation axis is 1.5 °, elastic modulus is 3.58 GPa in the longitudinal direction, 3.4 GPa in the width direction, tensile strength Is 140MPa in the longitudinal direction and 141MPa in the width direction. The elongation is 42% in the longitudinal direction and 48% in the width direction.
Kisimi value (static friction coefficient) is 0.64, Kisimi value (dynamic friction coefficient) is 0.52, Alkaline hydrolyzability is A, curl value is -0.6 at 25% RH, 1 at wet .8. Further, the water content was 1.4% by mass, the residual solvent amount was 0.31% by mass, and the thermal shrinkage was -0.10% in the longitudinal direction and -0.09% in the width direction. . Foreign matter is lint 5
It was less than pieces / m. The bright spot is 0.02 mm to 0.05 mm, less than 10/3 m,
0.05 to 0.1 mm was less than 5/3 m, and there was no more than 0.1 mm. These had excellent properties for optical applications. Also, no adhesion after application (○),
The moisture permeability was also good (◯).

Next, a cellulose triacetate film sample 102-1 having a thickness of 40 μm was formed. In addition, the location which is not demonstrated in particular was performed on the same conditions as the film forming method of the film sample 101-1.
For the dope, samples 010A, 011 and 012 constituting the dope sample 101-1 were used. Hereinafter, these samples are collectively referred to as a dope sample 102-1. And it cast so that the film thickness of the completed cellulose triacetate film sample 102-1 might be 4 micrometers, 33 micrometers, and 3 micrometers, respectively, and a product thickness might be 40 micrometers. In addition, the bead back pressure of the casting die is -1.
The pressure was 500 Pa. The temperature of the drying air in the casting chamber is 50 ° C at the top of the band and 7 ° at the bottom of the band.
The temperature was 0 ° C. After peeling off the film from the band, the transfer part was conveyed and sent to the tenter. In addition, the tension | tensile_strength of 10N-100N was provided to the film, when conveying with the roller of a transfer part. While drying with a tenter, the desired widening was also performed. The amount of widening when the width when transported to the tenter is 100% was 102%, and the stretch ratio from the peeling roller to the tenter inlet (tenter drive draw) was 101%. After the preliminary drying zone was conveyed, it was dried at a high temperature in the roller conveyance zone. Moreover, during the process, a forced charge removal device (charge removal bar) was installed, and the pressure was set to -3 kV to 3 kV. After the transfer section was transported, it was transported to the humidity control chamber, after which knurling was applied and then transported to the winding chamber. In winding, the charge is -1.5KV ~ 1.5
The charge was removed to KV.

The winding chamber was kept at a room temperature of 35 ° C. and a humidity of 80%, the tension at the start of winding was 250 N / width, and the tension pattern was such that the end of winding was 170 N / width, and oscillating was also performed. The cellulose triacetate film of the present invention produced through the above steps was used as Sample 102-1. The roll of this film sample 102-1 was stored in a storage rack at 25 ° C. and 55% RH for one month and further examined in the same manner as described above. As a result, no significant change was observed. Further, no adhesion was observed in the roll.

The obtained cellulose triacetate film sample 102-1 has a solution stability of A, a film surface shape of A, a film tear test of 10 g, and a film folding test of 12
Nine times, the heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0
. The content of the cellulose triacetate film was less than 01% by mass, less than 0.05% by mass of Ca and less than 0.01% by mass of Mg, and the thickness of the cellulose triacetate film was 40 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 102-1 has a haze of 0.3%, a transparency (transparency) of 92.5%,
Inclination width is 19.5 nm, critical wavelength is 392.6 nm, absorption edge is 374.1 nm, 380 n
The absorption of m is 2.40%, Re is 0.9 nm, Rth is 51 nm, the molecular orientation axis is 1.6 °, the elastic modulus is 3.54 GPa in the longitudinal direction, 3.45 GPa in the width direction, tensile strength Is 139 MPa in the longitudinal direction and 141 MPa in the width direction, and the elongation is 43% in the longitudinal direction and 49 in the width direction.
%, The kishimi value (static friction coefficient) is 0.63, the kishimi value (dynamic friction coefficient) is 0.51,
Alkaline hydrolyzability is A, curl value is -0.4 at 25% RH, 2.9 for wet.
Met. The water content is 1.20% by mass, the residual solvent amount is 0.19% by mass,
The thermal shrinkage rate was −0.07% in the longitudinal direction and −0.08% in the width direction. The foreign matter had a lint of less than 5 pieces / m. The bright spots were 0.02 mm to 0.05 mm less than 10/3 m, 0.05 to 0.1 mm less than 5/3 m, and 0.1 mm or more. These had excellent properties for optical applications. Also, no adhesion after application (○)
The water vapor transmission rate was slightly high but at a level (Δ) with no practical problems.

Next, a cellulose triacetate film sample 102-2 was prepared. Sample 010
Instead of A, 011 and 012, Samples 013A, 014 and 015 were used. Hereinafter, these samples are collectively referred to as a dope sample 102-2. Other than that, the cellulose triacetate film sample 102-2 was formed on the same conditions as film formation of the film sample 102-1, and the same evaluation as the film sample 101-1 was performed.

The obtained cellulose triacetate film sample 102-2 has a solution stability of A, a film surface shape of A, a film tear test of 11 g, and a film folding test of 13
It was 0 times, and the heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0
. The content of the cellulose triacetate film was less than 01% by mass, less than 0.05% by mass of Ca and less than 0.01% by mass of Mg, and the thickness of the cellulose triacetate film was 40 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 102-2 has a haze of 0.3%, a transparency (transparency) of 92.5%,
The tilt width is 19.6 nm, the limit wavelength is 392.7 nm, the absorption edge is 374.2 nm, 380 n
The absorption of m is 2.20%, Re is 0.8 nm, Rth is 50 nm, the molecular orientation axis is 1.4 °, the elastic modulus is 3.53 GPa in the longitudinal direction, 3.41 GPa in the width direction, tensile strength Is 138 MPa in the longitudinal direction and 141 MPa in the width direction, and the elongation is 43% in the longitudinal direction and 49 in the width direction.
%, The Kisimi value (static friction coefficient) is 0.65, the Kisimi value (dynamic friction coefficient) is 0.5, the alkali hydrolyzability is A, the curl value is -0.3 at 25% RH, 3.1. Further, the water content was 1.21% by mass, the residual solvent amount was 0.18% by mass, and the thermal shrinkage was −0.08% in the longitudinal direction and −0.08% in the width direction. . The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.02 mm to 0.05 mm, less than 10/3 m
0.05-0.1 mm was less than 5/3 m, and there was no more than 0.1 mm. These had excellent properties for optical applications. Also, no adhesion after application (○),
Although the water vapor transmission rate was slightly higher, it was a level (Δ) with no practical problem.

Next, a cellulose triacetate film sample 103-1 having a thickness of 60 μm and preferably used for a WV film was formed. In addition, the part which is not demonstrated in particular was performed on the same conditions as the film forming method of the sample 101-1. Retardation control agent N, N, N ′, N ″ -tri-m-toluyl-1,3,5-triazine-2,4,6-triamine is added to samples 010A, 011 and 012 010B, 011B, and 012B were adjusted. Adjustment conditions are 010
A, 011 and 012 were performed under the same conditions. The concentration of the retardation control agent is 1
. The UV absorber d was adjusted to 0% by mass and 0.5% by mass. Sample 010B,
The dope composed of 011B and 012B is referred to as a dope sample 103-1 in the following description.
Called.

The finished cellulose triacetate film sample 103-1 was cast at a casting speed (line speed) of 50 m / min so that the film thicknesses were 6 μm, 50 μm, and 4 μm, respectively, and the product thickness was 60 μm. The bead back pressure was adjusted to be −150 Pa. The temperature of the casting chamber was maintained at 35 ° C, and the temperature of the drying air was 30 ° C on the upstream side of the upper part of the band and 125 ° C on the downstream side. The lower part of the band was set to 80 ° C. After peeling off the film from the support, the film was transported at the crossover and sent to the tenter. During conveyance with the roller at the crossover, a tension of 15N to 150N was applied to the film. Divide the inside of the tenter into 3 zones, and set the drying air temperature in each zone to 100 ° C, 110 ° C, 120 ° C from the upstream side, and the widening amount when the width when transported to the tenter is 100% is 102% The stretch ratio from the peeling roller to the tenter entrance (tenter driven draw) was 105%. High temperature drying was performed in the preliminary drying zone and the roller conveyance zone. A forced static eliminator (static neutralization bar) was installed during the process, and was set to −5 kV to 5 kV. The air supply temperature of the air in the second humidity control chamber was 50 ° C. The cellulose triacetate film after drying was cut off at both ends and knurled at both ends of the film. And the film was conveyed to the winding chamber. A tension pattern having a winding start tension of 300 N and a winding end of 210 N using a core having a diameter of 300 mm was used. The total winding length was 2840 m. The roll of this film sample 103-1 was stored in a storage rack at 25 ° C. and 55% RH for one month and further examined in the same manner as described above. As a result, no significant change was observed. Further, no adhesion was observed in the roll. In addition, 1.0 mass% retardation control agent N and 0.5 mass% UV agents a and b are contained in this film sample 103-1.

The obtained cellulose triacetate film sample 103-1 has a solution stability of A, a film surface shape of A, and a film tear test of 11 g.
The heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0.
Less than 01% by mass, containing less than 0.05% by mass of Ca and less than 0.01% by mass of Mg,
The thickness of the cellulose triacetate film was 60 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 103-1 has a haze of 0.3% and a transparency (transparency) of 92.4%.
Met. Re is 10.2 nm, Rth is 81 nm, molecular orientation axis is 1.4 °, elastic modulus is 3.59 GPa in the longitudinal direction, 3.43 GPa in the width direction, and tensile strength is 139 MP in the longitudinal direction.
a, 141 MPa in the width direction, 43% in the longitudinal direction, 49% in the width direction, 0.65 for the kishimi value (static friction coefficient), 0.5 for the kishimi value (dynamic friction coefficient), alkaline hydrolysis The curability was -0.3 at 25% RH and 2.2 when wet. The moisture content was 1.34% by mass, the residual solvent amount was 0.24% by mass, and the thermal shrinkage was −0.09% in the longitudinal direction and −0.09% in the width direction. . The foreign matter had a lint of less than 5 pieces / m. The bright spots are 0.02 mm to 0.05 mm, less than 10/3 m, 0.05 to 0.00 mm.
1 mm was less than 5/3 m, and no more than 0.1 mm. These had excellent properties for optical applications. Further, no adhesion after coating was observed (◯), and the water vapor transmission rate was slightly high, but at a level (Δ) with no practical problem.

Next, a cellulose triacetate film sample 103-2 was prepared. Sample 010
Samples 013B, 014B, and 015B were used in place of B, 011B, and 012B. Hereinafter, these samples are collectively referred to as a dope sample 103-2. Otherwise, film sample 103
The cellulose triacetate film sample 103-2 was formed under the same conditions as -1, and the same evaluation as the film sample 101-1.

The obtained cellulose triacetate film sample 103-2 has a solution stability of A, a film surface shape of A, a film tear test of 12 g, and a film folding resistance test of 74.
The heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0.
Less than 01% by mass, containing less than 0.05% by mass of Ca and less than 0.01% by mass of Mg,
The thickness of the cellulose triacetate film was 60 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 103-2 has a haze of 0.3% and a transparency (transparency) of 92.4%.
Met. Re is 10.5 nm, Rth is 79 nm, molecular orientation axis is 1.3 °, elastic modulus is 3.50 GPa in the longitudinal direction, 3.42 GPa in the width direction, and tensile strength is 140 MP in the longitudinal direction.
a, 142 MPa in the width direction, 43% in the longitudinal direction, 49% in the width direction, 0.63 for the kishimi value (static friction coefficient), 0.52 for the kishimi value (dynamic friction coefficient), alkaline hydrolysis The property was A, the curl value was -0.5 at 25% RH, and 2.3 when wet. Also,
The water content was 1.35% by mass, the residual solvent amount was 0.25% by mass, and the heat shrinkage was −0.09% in the longitudinal direction and −0.08% in the width direction. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.02 mm to 0.05 mm, less than 10/3 m, 0.05 to 0.
. 1 mm was less than 5/3 m, and no more than 0.1 mm. These had excellent properties for optical applications. Further, no adhesion after coating was observed (◯), and the water vapor transmission rate was slightly high, but at a level (Δ) with no practical problem.

Next, a cellulose triacetate film sample 104-1 having a thickness of 80 μm and preferably used for an OCB film was formed. Parts not specifically described are film samples 1
It was performed under the same conditions as the film forming method of 01-1. Retardation control agent N, N, N ', N'
Samples 010C, 011C, and 012C were prepared by adding '-tri-m-toluyl-1,3,5-triazine-2,4,6-triamine to all layers. In addition, the retardation control agent N was prepared so that it might become 4 mass% with a film form. The preparation conditions were as follows: Sample 010A,
011, 012 and TO were performed under the same conditions. What consists of samples 010C, 011C, and 012C will be referred to as a doped sample 104-1 in the following description.

The film thickness of the finished cellulose triacetate film sample 104-1 is 10 μm.
, 60μm, 10μm, casting speed (line speed) so that the product thickness is 80μm
Was 50 m / min. The temperature of the casting chamber was maintained at 35 ° C, and the temperature of the drying air was 30 ° C on the upstream side of the upper part of the band and 100 ° C on the downstream side. The lower part of the band was set to 80 ° C. The film was peeled off from the support, and the transition part was conveyed and sent to the tenter. While being conveyed by the roller at the crossover, a tension of 13N to 130N was applied to the film. The desired widening was performed while drying was progressing with a tenter. The inside of the tenter is divided into three zones, and the drying temperature of each zone is 120 ° C, 130 ° C, 140 ° C from the upstream side, and the widening amount when the width when transported to the tenter is 100% is 130%. . The stretching ratio from the peeling roller to the tenter inlet (tenter-driven draw) was 102%. Then cut the ears at both ends,
The film was preheated in the predrying zone and dried at a high temperature in the roller conveyance zone. Also,
A forced static eliminator (static neutralization bar) was installed during the process, and was set to -3 kV to 3 kV. Dry air of 95 ° C. was supplied to the transition part from the roller conveyance zone to the first humidity control chamber. The dried film was conveyed to a humidity control chamber. In the second humidity control chamber, the air supply temperature was 95 ° C. And the film was conveyed to the winding chamber. The winding chamber was kept at a room temperature of 35 ° C. and a humidity of 80%. The tension pattern was such that the winding start tension was 190N and the winding end was 130N. The total winding length was 2840 m. The cellulose triacetate film of the present invention was used as Sample 104-1. The roll of Sample 104-1 was stored in a storage rack at 25 ° C. and 55% RH for 1 month and further examined in the same manner as described above. As a result, no significant change was observed. Further, no adhesion was observed in the roll. The film sample 104-1 contains 4% by mass of a retardation control agent.

The obtained cellulose triacetate film sample 104-1 has a solution stability of A, a film surface shape of A, a film tear test of 15 g, and a film folding resistance test of 72.
The heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0.
Less than 01% by mass, containing less than 0.05% by mass of Ca and less than 0.01% by mass of Mg,
The thickness of the cellulose triacetate film was 80 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 104-1 has a haze of 0.3% and a transparency (transparency) of 92.4%.
Met. Re is 42 nm, Rth is 175 nm, molecular orientation axis is 1.9 °, elastic modulus is 3.54 GPa in the longitudinal direction, 3.4 GPa in the width direction, tensile strength is 145 MPa in the longitudinal direction,
The width direction is 139 MPa, the elongation is 43% in the longitudinal direction, and 49% in the width direction.
The static friction coefficient was 0.63, the kishimi value (dynamic friction coefficient) was 0.51, the alkali hydrolyzability was A, the curl value was -0.5 at 25% RH, and 1.6 when wet. The moisture content was 1.45% by mass, the residual solvent amount was 0.35% by mass, and the thermal shrinkage was -0.09% in the longitudinal direction and -0.10% in the width direction. . The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.02 mm to 0.05 mm, less than 10/3 m, 0.05 to 0.1
There was no mm less than 5/3 m and 0.1 mm or more. These had excellent properties for optical applications. Also, no adhesion after application (○) and good moisture permeability (○
)Met.

Next, a cellulose triacetate film sample 104-2 was prepared. Sample 010
Samples 013C, 014C, and 015C were used instead of C, 011C, and 012C. In the following description, these samples are collectively referred to as a dope sample 104-2. Otherwise, the cellulose triacetate film sample 104- under the same conditions as the film sample 104-1.
2 was formed and evaluated in the same manner as the film sample 101-1.

The obtained cellulose triacetate film sample 104-2 has a solution stability of A, a film surface shape of A, a film tear test of 16 g, and a film folding test of 71.
The heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0.
Less than 01% by mass, containing less than 0.05% by mass of Ca and less than 0.01% by mass of Mg,
The thickness of the cellulose triacetate film was 80 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 104-2 has a haze of 0.3% and a transparency (transparency) of 92.4%.
Met. Re is 40 nm, Rth is 172 nm, molecular orientation axis is 1.7 °, elastic modulus is 3.53 GPa in the longitudinal direction, 3.41 GPa in the width direction, and tensile strength is 140 MPa in the longitudinal direction.
, The width direction is 143 MPa, the elongation is 43% in the longitudinal direction and 49% in the width direction, the kishimi value (static friction coefficient) is 0.65, the kishimi value (dynamic friction coefficient) is 0.52, and the alkali hydrolyzability Was A, and the curl value was -0.7 at 25% RH and 1.8 at wet. The moisture content was 1.44% by mass, the residual solvent amount was 0.34% by mass, and the thermal shrinkage was -0.09% in the longitudinal direction and -0.10% in the width direction. . The foreign matter had a lint of less than 5 pieces / m. The bright spots are 0.02 mm to 0.05 mm, less than 10/3 m, 0.05 to 0.00 mm.
1 mm was less than 5/3 m, and no more than 0.1 mm. These had excellent properties for optical applications. Also, no adhesion after application (○) and good moisture permeability (
○).

Next, an embodiment using a single layer die will be described. Here, the material of the die is a two-phase stainless steel having a mixed composition of an austenite phase and a ferrite phase, a material having a coefficient of thermal expansion of 2 × 10 ⁻⁵ (° C. ⁻¹ ) or less, and forced in an electrolyte aqueous solution. A material having corrosion resistance substantially equivalent to that of SUS316 was used in the corrosion test. In addition, a corrosion-resistant material that does not cause pitting at the gas-liquid interface even when immersed in a mixed solution of dichloromethane, methanol, and water for 3 months was used. Furthermore, the surface of the cellulose triacetate solution was kept constant by grinding the one that was aged for one month or more after casting. The finishing accuracy of the wetted surface of the casting die is 1 μm or less in terms of surface roughness, the straightness is 1 μm / m or less in any direction, and the clearance of the slit can be adjusted from 0.5 mm to 3.5 mm by automatic adjustment. Met. About the corner | angular part of the liquid-contact part of die-tip tip, it processed so that R might be 50 micrometers or less over the slit full width. The shear rate inside the die was in the range of 1 (1 / sec) to 5000 (1 / sec).

Furthermore, in order to prevent the dope flowing out from the slit end of the die from locally drying and solidifying, a mixed solvent (sample 080), which is a solvent for solubilizing the dope, is added to the gas-liquid interface between the bead end and the slit. Was supplied at 0.5 cc / min on one side. The pulsation rate of the pump supplying this mixed liquid was 5% or less. In addition, the pressure on the back of the bead was reduced by 50 Pa using a vacuum chamber attached to the die. The edge suction air volume was appropriately adjusted in the range of 30 L / min to 40 L / min.

Using the above-described single layer casting die, the dope sample 001 was used to form a film under the same conditions as the cellulose triacetate film sample 101-1, thereby obtaining a cellulose triacetate film sample 101-3. This cellulose triacetate film sample 101-3 was evaluated in the same manner as the film sample 101-1.

The obtained cellulose triacetate film sample 101-3 has a solution stability of A, a film surface shape of A, a film tear test of 15 g, and a film folding resistance test of 70.
The heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0.
Less than 01% by mass, containing less than 0.05% by mass of Ca and less than 0.01% by mass of Mg,
The thickness of the cellulose triacetate film was 80 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 101-3 has a haze of 0.3%, a transparency (transparency) of 92.2%,
Tilt width is 19.7 nm, critical wavelength is 392.5 nm, absorption edge is 374.0 nm, 380 n
The absorption of m is 2.1%, Re is 1.1 nm, Rth is 49 nm, and the molecular orientation axis is 1
. The elastic modulus is 3.52 GPa in the longitudinal direction, 3.45 GPa in the width direction, the tensile strength is 140 MPa in the longitudinal direction, 141 MPa in the width direction, and the elongation is 41% in the longitudinal direction and 48% in the width direction.
Kisimi value (static friction coefficient) is 0.64, Kisimi value (dynamic friction coefficient) is 0.51, Alkaline hydrolyzability is A, curl value is -0.4 at 25% RH, 1 at wet .6. Further, the moisture content was 1.4% by mass, the residual solvent amount was 0.3% by mass, and the thermal shrinkage was −0.10% in the longitudinal direction and −0.09% in the width direction. . The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.02 mm to 0.05 mm, less than 10/3 m, 0
. 05-0.1 mm was less than 5/3 m, and there was no more than 0.1 mm. These had excellent properties for optical applications. Further, some adhesion after application was observed, but it was at a level that was not problematic for practical use (Δ), and the moisture permeability was good (◯).

Using dope sample 002, cellulose acetate sample 101 using a single layer casting die
Film formation was carried out under the same conditions as -2, and a cellulose acetate sample 101-4 was obtained. This 101-
4 was evaluated in the same manner as 101-2.

The obtained cellulose triacetate film sample 101-4 has a solution stability of A, a film surface shape of A, a film tear test of 16 g, and a film folding resistance test of 73.
The heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0.
Less than 01% by mass, containing less than 0.05% by mass of Ca and less than 0.01% by mass of Mg,
The thickness of the cellulose triacetate film was 80 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 101-4 has a haze of 0.3%, a transparency (transparency) of 92.1%,
Inclination width is 19.5 nm, critical wavelength is 392.4 nm, absorption edge is 374.2 nm, 380 n
The absorption of m is 2.0%, Re is 1.0 nm, Rth is 49 nm, and the molecular orientation axis is 1
. The elastic modulus is 3.58 GPa in the longitudinal direction, 3.41 GPa in the width direction, the tensile strength is 140 MPa in the longitudinal direction, 139 MPa in the width direction, and the elongation is 42% in the longitudinal direction and 49% in the width direction.
Kisimi value (static friction coefficient) is 0.64, Kisimi value (dynamic friction coefficient) is 0.52, Alkaline hydrolyzability is A, curl value is -0.5 at 25% RH, 1 in wet condition .8. The moisture content was 1.4% by mass, the residual solvent amount was 0.3% by mass, and the thermal shrinkage was −0.09% in the longitudinal direction and −0.09% in the width direction. . The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.02 mm to 0.05 mm, less than 10/3 m, 0
. 05-0.1 mm was less than 5/3 m, and there was no more than 0.1 mm. These had excellent properties for optical applications. Further, some adhesion after application was observed, but it was at a level that was not problematic for practical use (Δ), and the moisture permeability was good (◯).

Next, a cellulose triacetate film sample 102-3 was produced. Using a single-layer casting die, the thickness of the product film was 40 μm, a film was formed under the same conditions as the cellulose triacetate film sample 102-2, and evaluation was performed under the same conditions as the film sample 101-1.

The obtained cellulose triacetate film sample 102-3 has a solution stability of A, a film surface shape of A, and a film tear test of 11 g.
Nine times, the heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0
. The content of the cellulose triacetate film was less than 01% by mass, less than 0.05% by mass of Ca and less than 0.01% by mass of Mg, and the thickness of the cellulose triacetate film was 40 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

  The film sample 102-3 has a haze of 0.3%, a transparency (transparency) of 92.3%, a slope width of 19.6 nm, a limit wavelength of 392.5 nm, an absorption edge of absorption of 374.0 nm and 380 nm. 2.3%, Re 0.9 nm, Rth 50 nm, molecular orientation axis 1.5 °, elastic modulus 3.54 GPa in the longitudinal direction, 3.44 GPa in the width direction, tensile strength in the longitudinal direction Is 138 MPa, width direction is 141 MPa, elongation rate is 43% in the longitudinal direction and 49% in the width direction, the kishimi value (static friction coefficient) is 0.63, the kishimi value (dynamic friction coefficient) is 0.51, Decomposability was A, curl value was -0.3 at 25% RH, and 2.8 when wet. The water content was 1.20% by mass, the residual solvent amount was 0.19% by mass, and the thermal shrinkage was -0.08% in the longitudinal direction and -0.08% in the width direction. . The foreign matter had a lint of less than 5 pieces / m. Further, the bright spot was 0.02 mm to 0.05 mm less than 10 pieces / 3 m, 0.05 to 0.1 mm was less than 5 pieces / 3 m, and there was no 0.1 mm or more. These had excellent properties for optical applications. Further, some adhesion after application was observed, but it was at a level (Δ) with no problem in practical use, and the water vapor transmission rate was slightly high (Δ) with no problem in practical use.

Next, a cellulose triacetate film sample 102-4 was prepared. Using a single-layer casting die, a product film having a thickness of 40 μm was formed under the same conditions as the cellulose triacetate film sample 102-2, and the same evaluation as the film sample 101-1 was performed.

The obtained cellulose triacetate film sample 102-4 has a solution stability of A, a film surface shape of A, a film tear test of 11 g, and a film folding test of 13
Once, the heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0
. The content of the cellulose triacetate film was less than 01% by mass, less than 0.05% by mass of Ca and less than 0.01% by mass of Mg, and the thickness of the cellulose triacetate film was 40 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 102-4 has a haze of 0.3%, a transparency (transparency) of 92.4%,
Inclination width is 19.5 nm, critical wavelength is 392.8 nm, absorption edge is 374.2 nm, 380 n
The absorption of m is 2.4%, Re is 0.9 nm, Rth is 50 nm, and the molecular orientation axis is 1.
. 4 °, elastic modulus is 3.53 GPa in the longitudinal direction, 3.42 GPa in the width direction, tensile strength is 138 MPa in the longitudinal direction, 140 MPa in the width direction, and elongation is 43% in the longitudinal direction and 49% in the width direction.
Kisimi value (static friction coefficient) is 0.65, Kisimi value (dynamic friction coefficient) is 0.5, alkali hydrolyzability is A, curl value is -0.4 at 25% RH, 3 at wet .1. Further, the water content was 1.21% by mass, the residual solvent amount was 0.19% by mass, and the thermal shrinkage was −0.08% in the longitudinal direction and −0.09% in the width direction. . Foreign matter is lint 5
It was less than pieces / m. The bright spot is 0.02 mm to 0.05 mm, less than 10/3 m,
0.05 to 0.1 mm was less than 5/3 m, and there was no more than 0.1 mm. These had excellent properties for optical applications. Also, some adhesion after application was seen,
The practically no problem level (Δ) and the water vapor transmission rate were slightly higher, but the practically no problem level (Δ).

Retardation control agent N was mixed with dope sample 001 in sample 070 (mixed solvent) to give a solution. This solution was mixed in-line with the sample 001 being fed via a static mixer. This dope below is referred to as a dope sample 001B. The retardation control agent N was adjusted to 1.0 mass% in the film form, and the ultraviolet absorber d was adjusted to 0.5 mass%. Using sample 001B using a single layer casting die, film formation was performed under the same conditions as cellulose triacetate film sample 103-1, and cellulose triacetate film sample 103-
3 was obtained. Moreover, this cellulose triacetate film sample 103-3 performed the same evaluation as the film sample 101-1.

The obtained cellulose triacetate film sample 103-3 has a solution stability of A, a film surface shape of A, and a film tear test of 11 g.
The heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0.
Less than 01% by mass, containing less than 0.05% by mass of Ca and less than 0.01% by mass of Mg,
The thickness of the cellulose triacetate film was 60 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 103-3 had a haze of 0.3% and a transparency (transparency) of 92.4%. Re is 10.2 nm, Rth is 80 nm, molecular orientation axis is 1.4 °, elastic modulus is 3.57 GPa in the longitudinal direction, 3.41 GPa in the width direction, and tensile strength is 141 MPa in the longitudinal direction.
, 140 MPa in the width direction, 44% in the longitudinal direction and 48% in the width direction, 0.63 for the kishimi value (static friction coefficient), 0.52 for the kishimi value (dynamic friction coefficient), alkaline hydrolyzability Was A, and the curl value was -0.4 at 25% RH and 2.2 at wet. Further, the moisture content was 1.37% by mass, the residual solvent amount was 0.24% by mass, and the thermal shrinkage was -0.10% in the longitudinal direction and -0.09% in the width direction. . The foreign matter had a lint of less than 5 pieces / m. The bright spots are 0.02 mm to 0.05 mm, less than 10/3 m, 0.05 to 0.00 mm.
1 mm was less than 5/3 m, and no more than 0.1 mm. These had excellent properties for optical applications. Moreover, although adhesion after application was slightly observed, it was a level (Δ) having no practical problem, and the water vapor transmission rate was slightly high (Δ) with no practical problem.

Next, a cellulose triacetate film sample 103-4 was prepared. Retardation control agent N, sample 070 (mixed solvent), and dope sample 001 were mixed to form a solution.
This solution was mixed inline with the sample 002 being fed via a static mixer. Hereinafter, this dope is referred to as a dope sample 002B. Dope sample 002B using a single layer casting die
Was used under the same conditions as the cellulose triacetate film sample 103-2, and the same evaluation as the film sample 101-1 was performed.

The obtained cellulose triacetate film sample 103-4 has a solution stability of A, a film surface shape of A, a film tear test of 12 g, and a film folding resistance test of 74.
The heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0.
Less than 01% by mass, containing less than 0.05% by mass of Ca and less than 0.01% by mass of Mg,
The thickness of the cellulose triacetate film was 60 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 103-4 had a haze of 0.3% and a transparency (transparency) of 92.4%. Re is 10.5 nm, Rth is 80 nm, molecular orientation axis is 1.4 °, elastic modulus is 3.51 GPa in the longitudinal direction, 3.41 GPa in the width direction, and tensile strength is 141 MPa in the longitudinal direction.
, 141 MPa in the width direction, 44% in the longitudinal direction and 48% in the width direction, 0.65 for the kishimi value (static friction coefficient), 0.53 for the kishimi value (dynamic friction coefficient), and alkali hydrolyzability Was A, and the curl value was −0.5 at 25% RH and 2.4 when wet. The moisture content was 1.36% by mass, the residual solvent amount was 0.25% by mass, and the thermal shrinkage was -0.10% in the longitudinal direction and -0.10% in the width direction. . The foreign matter had a lint of less than 5 pieces / m. The bright spots are 0.02 mm to 0.05 mm, less than 10/3 m, 0.05 to 0.00 mm.
1 mm was less than 5/3 m, and no more than 0.1 mm. These had excellent properties for optical applications. Moreover, although adhesion after application was slightly observed, it was a level (Δ) having no practical problem, and the water vapor transmission rate was slightly high (Δ) with no practical problem.

Retardation control agent N was mixed with sample 070 (mixed solvent) and dope sample 001 to obtain a solution. This solution was mixed in-line with the sample 001 being fed via a static mixer. Hereinafter, this dope is referred to as a dope sample 001C. The retardation control agent is
It adjusted so that it might become 4.0 mass% with a film form, and was mixed. A sample 001C was used using a single layer casting die, and a film was formed under the same conditions as the film sample 104-1 with a thickness of the product film of 80 μm. In the following description, this film is referred to as cellulose triacetate film sample 104-3. Cellulose triacetate film sample 104-3 is
The same evaluation as film sample 101-1 was performed.

The obtained cellulose triacetate film sample 104-3 has a solution stability of A, a film surface shape of A, a film tear test of 15 g, and a film folding test of 71.
The heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0.
Less than 01% by mass, containing less than 0.05% by mass of Ca and less than 0.01% by mass of Mg,
The thickness of the cellulose triacetate film was 80 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 104-3 has a haze of 0.3% and a transparency (transparency) of 92.4%.
Met. Re is 41 nm, Rth is 174 nm, the molecular orientation axis is 1.8 °, the elastic modulus is 3.53 GPa in the longitudinal direction, 3.44 GPa in the width direction, and the tensile strength is 146 MPa in the longitudinal direction.
The width direction is 141 MPa, the elongation is 43% in the longitudinal direction and 49% in the width direction, the kishimi value (static friction coefficient) is 0.61, the kishimi value (dynamic friction coefficient) is 0.52, and the alkali hydrolyzability Was A, and the curl value was −0.4 at 25% RH and 1.5 when wet. The water content was 1.44% by mass, the residual solvent amount was 0.33% by mass, and the thermal shrinkage was -0.08% in the longitudinal direction and -0.10% in the width direction. . The foreign matter had a lint of less than 5 pieces / m. The bright spots are 0.02 mm to 0.05 mm, less than 10/3 m, 0.05 to 0.00 mm.
1 mm was less than 5/3 m, and no more than 0.1 mm. These had excellent properties for optical applications. Further, some adhesion after application was observed, but it was at a level that was not problematic for practical use (Δ), and the moisture permeability was good (◯).

Next, a cellulose triacetate film sample 104-4 was prepared. Retardation control agent N was mixed with sample 070 (mixed solvent) to obtain a solution. This solution was mixed inline with the sample 002 being fed via a static mixer. Hereinafter, this dope is referred to as a dope sample 002C. In addition, it adjusted so that the density | concentration of the retardation control agent N might be 4.0 mass% with a film form. A sample 002C was used using a single layer casting die, the product film thickness was 80 μm, a film was formed under the same conditions as the cellulose triacetate film sample 104-2, and the same evaluation as the film sample 101-1 was performed.

The obtained cellulose triacetate film sample 104-4 has a solution stability of A, a film surface shape of A, a film tear test of 15 g, and a film folding resistance test of 71.
The heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0.
Less than 01% by mass, containing less than 0.05% by mass of Ca and less than 0.01% by mass of Mg,
The thickness of the cellulose triacetate film was 80 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

Film sample 104-4 had a haze of 0.3% and a transparency (transparency) of 92.4%. Re is 40 nm, Rth is 173 nm, molecular orientation axis is 1.8 °, elastic modulus is 3.51 GPa in the longitudinal direction, 3.42 GPa in the width direction, tensile strength is 141 MPa in the longitudinal direction,
The width direction is 142 MPa, the elongation is 43% in the longitudinal direction and 48% in the width direction.
The static friction coefficient was 0.65, the kishimi value (dynamic friction coefficient) was 0.53, the alkali hydrolyzability was A, the curl value was −0.7 at 25% RH, and 1.9 when wet. The moisture content was 1.43% by mass, the residual solvent amount was 0.34% by mass, and the heat shrinkage was −0.09% in the longitudinal direction and −0.09% in the width direction. . The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.02 mm to 0.05 mm, less than 10/3 m, 0.05 to 0.1
There was no mm less than 5/3 m and 0.1 mm or more. These had excellent properties for optical applications. Further, some adhesion after application was observed, but it was at a level that was not problematic for practical use (Δ), and the moisture permeability was good (◯).

The parts by mass of the compound used are shown below.
Cellulose triacetate A-2 (substitution degree 2.80, viscosity average polymerization degree 306, water content 0.8.
2% by mass, viscosity of 6% by mass in dichloromethane solution 315 mPa · s, average particle size 1.5
14.5 parts by weight Methyl acetate 67.69 parts by weight Acetone 6.69 parts by weight Ethanol 5.85 parts by weight n-butanol 3.34 parts by weight Plasticizer A: (Trimethylolpropane triacetate) 0.29 parts by mass plasticizer B: (triphenyl phosphate) 0.91 parts by mass plasticizer C: (biphenyldiphenyl phosphate) 0.54 parts by mass plasticizer D: (ethyl phthalyl glycol) Ethyl ester) 0.091 parts by mass UV agent a: (2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine
0.05 parts by mass of UV agent b: 2 (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5
Chlorbenzotriazole 0.05 parts by mass UV agent c: (2 (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) -benzotriazole 0.1 part by mass Release agent: citric acid ethyl ester (citrate Acid: ethyl alcohol = 1: 1 (molar ratio) reaction mixture) 0.031 parts by mass Matting agent: (silicon dioxide (particle size 20 nm), Mohs hardness about 7 0.005 parts by mass

The cellulose triacetate A-2 used here has a residual acetic acid content of 0.1% by mass.
The Ca content is 58 ppm, the Mg content is 42 ppm, and the Fe content is 0.5 p.
pm, 40 ppm free acetic acid and 15 ppm sulfate ion. The degree of substitution of the 6-position acetyl group was 0.91, 32.5% of the total acetyl. Also,
The acetone extract was 8% by mass, and the weight average molecular weight / number average molecular weight ratio was 2.5. Also,
Yellow index is 1.7, haze is 0.08, transparency is 93.5%,
Tg (glass transition temperature; measured by DSC) was 160 ° C., and the crystallization exotherm was 6.4 J / g. This cellulose triacetate A was synthesized using cellulose collected from cotton as a raw material. In the following description, this is called cotton raw material TAC-2.

The main solvent methyl acetate has a solubility parameter of 19.6, a dielectric constant of 6.68,
Oxygen fraction 0.43, dipole moment 1.61D, molecular weight 74, boiling point 57 ° C,
The I / O value is 2.13, a solvent within the preferred solvent range of the present invention. Further, acetone used in combination has a solubility parameter of 20.3, a dielectric constant of 20.7, an oxygen fraction of 0.28, a dipole moment of 2.69 D, a molecular weight of 58, a boiling point of 56 ° C., and an I / O value. Is 1.08, which is the preferred solvent range of the present invention.

(2-1) Preparation of cellulose triacetate solution (hereinafter referred to as dope) Cellulose triacetate powder while mixing and mixing well with a plurality of solvents in a 4000 L stainless steel dissolution tank having stirring blades Body (flakes) was gradually added to prepare a total of 2000 kg. In addition, methyl acetate as a solvent,
As n-butanol, acetone, and ethanol, those having a water content of 0.5% by mass or less were used. First, powder of cellulose triacetate is charged into a dispersion tank.
A dissolver-type eccentric agitation shaft that initially stirs the stirring shear rate at a peripheral speed of 15 m / sec (shear stress 5 × 10 ⁴ kgf / m / sec ² ) and an anchor blade on the central axis, and a peripheral speed of 1 m The mixture was dispersed for 30 minutes under the condition of stirring at / sec (shear stress 1 × 10 ⁴ kgf / m / sec ² ). The starting temperature of dispersion was 25 ° C., and the final temperature reached 48 ° C. After completion of the dispersion, the high-speed stirring was stopped, and the peripheral speed of the anchor blade was set at 0.5 m / sec and further stirred for 100 minutes to swell the cellulose triacetate flakes. Until the end of swelling, the inside of the tank was pressurized to 0.12 MPa with nitrogen gas. At this time, the oxygen concentration in the tank was less than 2 vol%, and the state of no problem was maintained in terms of explosion protection. The water content in the dope was confirmed to be 0.5% by mass or less, and 0.3% by mass in this experiment.

(2-2) Dissolution / filtration step The swollen solution was fed from a tank to a screw extruder using a gear pump. The screw primary pressure at this time was 0.55 MPa. The screw has a jacket that circulates the refrigerant, and the refrigerant is −80 ° C. using 3M Fluorinert FC-77 (registered trademark).
The liquid was sent. The refrigerant was cooled by a direct expansion refrigerator. Average velocity in jacket is 2m / se
c, and the average residence time of the solution inside the screw was 35 seconds. And 3 weight% of addition liquid was added with respect to dope. The additive liquid used was adjusted to n-butanol: sample 080 = 50: 50 (weight ratio). After the additive solution was added to the dope, it was prepared by allowing it to stay in a static mixer for 30 minutes. Then, the hydrogen ion index (pH) of the obtained dope (hereinafter, this dope is referred to as pre-concentration dope) was adjusted to 5. Moreover, after adjusting this dope, the film-forming process was performed in the atmosphere whose oxygen concentration is 5 vol%. In addition, generation | occurrence | production of the microgel was not seen at all in the dope before concentration after adding the addition liquid and retaining. Thereafter, the dope before concentration was heated to 50 ° C. through a jacketed pipe into which a static mixer was inserted, and passed through a sintered metal fiber filter having a nominal pore diameter of 10 μm to obtain a dope. At this time, the primary pressure of filtration was 1.5 MPa, and the secondary pressure was 1.2 MPa.

(2-3) Concentration and Filtration The pre-concentration dope thus obtained was flushed in a tank at 120 ° C. and normal pressure, and the evaporated solvent was recovered and separated by a condenser. The solid content concentration of the dope after flashing is 21.
It became 8 mass%. The condensed solvent was sent to a recovery process to be reused as a solvent in the preparation process (recovery is carried out by a distillation process, a dehydration process, etc.). The flash tank had an anchor blade on the central axis, and deaerated by stirring at a peripheral speed of 0.5 m / sec.
The temperature of the dope in the tank was 25 ° C., and the average residence time in the tank was 50 minutes. The shear viscosity measured at 25 ° C. after collecting the dope was 450 (P at a shear rate of 10 (sec ⁻¹ ).
a)).

Next, the dope was defoamed by applying weak ultrasonic waves. The defoamed dope temperature was adjusted to 25 ° C. and stored in a 2000 L stainless steel stock tank. The stock tank had an anchor blade on the center axis and was constantly stirred at a peripheral speed of 0.3 m / sec. In the following description, this dope is referred to as Sample 001-2. In addition, when the dope was prepared from the dope before concentration, no problem such as corrosion occurred at all in the wetted part of the dope.

Sample 001 cellulose triacetate A-2 was mixed with 50 parts by weight of cotton TAC and chip TA.
A dope was produced under the same conditions except that the mixture was changed to a mixture of 50 parts by mass of C. In the following description, this dope is referred to as sample 002-2. In addition, chip | tip TAC grind | pulverizes the ear | edge part of the film sample 101-12 mentioned later.

The dope was prepared under the same components and under the same conditions as sample 001-2 except that citric acid ethyl ester as a peeling accelerator and silicon dioxide as a matting agent were not used, and a dope having a solid content of 21.8% by mass was obtained. It was. In the following description, this dope is referred to as Sample 003-2. Also,
A dope having a solid content of 21.8% by mass was obtained by preparing a dope under the same components and under the same conditions as in Sample 002-2 except that the peeling accelerator and the matting agent were not used. Hereinafter, it is referred to as Sample 004-2.

Moreover, the mixed solvent which consists of 81 mass parts of methyl acetate, 8 mass parts of acetone, 7 mass parts of ethanol, and 4 mass parts of n-butanol was produced. In the following description, this mixed solvent is referred to as Sample 080.

(2-4) Casting step Subsequently, the dope in the stock tank was fed by performing feedback control with an inverter motor so that the primary pressure of the high precision gear pump became 0.8 MPa with a gear pump for primary pressure increase. The high-precision gear pump had a volume efficiency of 99.2% and a discharge rate variation of 0.5% or less. The discharge pressure was 1.5 MPa.

The casting die has a width of 1.8m and is equipped with a feed block adjusted for co-casting. In addition to the mainstream, a device that can be laminated on both sides to form a three-layer film is used. It was. In the following description, a layer formed from the mainstream is referred to as an intermediate layer, a support surface side layer is referred to as a support surface, and an opposite surface is referred to as an air surface. The dope liquid flow path is for the intermediate layer,
Three flow paths for the support surface and the air surface were used.

Retardation control agent A trimethylolpropane triacetate sample 080
A solution was prepared by dissolving in (mixed solvent). Sample 003-2 while sending this solution in-line
Were mixed through a static mixer to obtain an intermediate layer dope. The mixing amount was adjusted so that the total solid content concentration was 21.8% by mass and the retardation control agent A was 4.0% by mass in the form of a film. In the following description, this dope is referred to as Sample 010A-2.

A matting agent (silicon dioxide) and a peeling accelerator (citric acid ethyl ester) were dissolved or dispersed in Sample 080 to obtain a dispersion. Sample 003-2 while sending this dispersion liquid in-line
Were mixed through a static mixer to prepare a support surface dope. The addition amount was such that the total solid content concentration was 20.5% by mass, the matting agent concentration was 0.05% by mass, and the release accelerator concentration was 0.03% by mass. In the following description, this dope is referred to as Sample 01-2.

A matting agent (silicon dioxide) was dispersed in Sample 080 to obtain a dispersion. This dispersion was mixed with sample 003-2 being fed in-line via a static mixer to produce an air surface dope. The amount added was such that the total solid content concentration was 20.5% by mass and the matting agent concentration was 0.1% by mass. In the following description, this dope is referred to as Sample 012-2. A sample consisting of these samples 010A-2, 011-2, and 012-2 is referred to as a dope sample 101-12 in the following description.

The finished cellulose triacetate film sample 101-12 has a film thickness (air surface, intermediate layer, support surface) of 4 μm, 73 μm, and 3 μm, respectively, and a casting speed (line speed) so that the product thickness is 80 μm. Was set to 100 m / min, the casting width was set to 1700 mm, and the flow rate of the cellulose triacetate dope at each die protrusion was adjusted to perform casting. In order to adjust the temperature of each dope (samples 012-2, 010A-2, 011-2) to 25 ° C., the inlet temperature of the heat transfer medium supplied to the jacket by providing the casting die with a jacket is set to 2
The temperature was 5 ° C.

The die, feed block, and piping were all kept at 25 ° C. during the work process. The die was a coat hanger type die, with thickness adjusting bolts provided at a pitch of 20 mm, and having an automatic thickness adjusting mechanism using a heat bolt. This heat bolt can also set a profile according to the liquid feed amount of the high precision gear pump by a preset program, and feedback control can also be performed by an adjustment program based on the profile of the infrared thickness gauge installed in the film forming process It has performance. Casting edge 20m
The thickness difference between any two points 50 mm apart in the film excluding m was within 1 μm, and the smallest difference in thickness in the width direction was adjusted to be 3 μm / m or less. The average thickness accuracy of each layer was controlled to ± 2% or less for both outer layers and ± 1% or less for the mainstream, and the overall thickness was adjusted to ± 1.5% or less.

In addition, a chamber for decompressing was installed on the primary side of the die. The degree of decompression of the decompression chamber is such that a pressure difference of 1 Pa to 5000 Pa can be applied before and after the casting bead, and can be adjusted according to the casting speed. At that time, the bead length is 5 mm to 5 mm.
The pressure difference was set to 0 mm. Further, the chamber temperature was provided with a mechanism that can be set higher than the condensation temperature of the gas around the casting portion. Furthermore, in order to adjust the turbulence of the flow at both edges of the bead, an apparatus equipped with an edge suction device was used.

(2-5) Casting die Here, the material of the die is a duplex stainless steel having a mixed composition of an austenite phase and a ferrite phase, and the thermal expansion coefficient is 2 × 10 ⁻⁵ (° C. ⁻¹ ) or less. A material having a corrosion resistance substantially equivalent to that of SUS316 was used in a forced corrosion test with an aqueous electrolyte solution. In addition, a material having corrosion resistance that does not cause pitting (opening) at the gas-liquid interface even when immersed in a mixed solution of dichloromethane, methanol, and water for 3 months was used. Furthermore, the material that had been aged for more than one month after casting was ground to keep the surface state of the cellulose triacetate solution constant. The finishing accuracy of the wetted surface of the casting die and the feed block is 1 μm or less in surface roughness, the straightness is 1 μm / m or less in any direction, and the clearance of the slit is 0.5 mm to 3.5 mm by automatic adjustment. It was adjustable until. About the corner | angular part of the liquid-contact part of die-die tip, it processed so that R might be set to 50 micrometers or less over the slit full width. The shear rate inside the die was in the range of 1 (1 / sec) to 5000 (1 / sec).

Further, a casting die provided with a cured film was used at the lip tip. Examples of means for providing a hard film include ceramic coating, hard chrome plating, and nitriding. When ceramics are used as the cured film, those that can be ground, have low porosity, are not brittle, have good corrosion resistance, and have good adhesion to the die and no adhesion to the dope are preferable. Specifically, tungsten carbide (WC), Al ₂ O ₃ , TiN, Cr ₂ O _{3 and the} like are preferable, and WC is particularly preferable. In the present invention, a WC coating formed by spraying is used.

Furthermore, in order to prevent the dope flowing out at the slit end of the die from locally drying and solidifying, a mixed solvent (sample 080) which is a solvent for solubilizing the dope is applied to the gas-liquid interface between the bead end and the slit. One side was supplied at 0.5 cc / min. The pulsation rate of the pump supplying this liquid is 5%
It was the following. In addition, the pressure on the back surface of the bead was reduced by 150 Pa by the decompression chamber. A jacket was attached to keep the temperature of the vacuum chamber constant. A heat transfer medium adjusted to 35 ° C. was supplied into the jacket. Edge suction air volume is 1L / min to 100L
In the present example, adjustment was appropriately made in the range of 30 L / min to 40 L / min.

(2-6) Metal support A stainless steel endless band having a width of 2.1 m and a length of 70 m was used as the support. The band was 1.5 mm thick and polished so that the surface roughness was 0.05 μm or less. The material was made of SUS316 and had sufficient corrosion resistance and strength. The thickness unevenness of the entire band was 0.5% or less. The band uses a type driven by two drums, and the tension of the band at that time is adjusted to 1.5 × 10 ⁴ kg / m, and the relative speed difference between the band and the drum becomes 0.01 m / min or less. It was a thing. Also,
Band drive speed fluctuation was 0.5% or less. Moreover, the meandering in the width direction of one rotation is 1.5 mm
Both ends of the band were detected and controlled so as to limit to the following. Further, the positional fluctuation in the vertical direction accompanying the drum rotation on the support surface just below the casting die was set to 200 μm or less. Three layers of dope were co-cast from this die on this support.

As the casting drum, a drum having equipment for circulating a heat transfer medium (refrigerant) therein was used so as to cool the support. Moreover, since the other drum supplies heat for drying, the heat transfer medium can pass water. The temperature of each heat transfer medium was 5 ° C. (casting die side) and 40 ° C. The surface temperature of the central part of the support just before casting was 15 ° C. The temperature difference between both ends was 6 ° C. or less.

The drum can be directly used as a casting support. In this case, the drum is rotated with an accuracy of 0.2 mm or less. The average surface roughness of the drum is also 0.01 μm.
The following are sufficient hardness and durability by chrome plating treatment.

There should be no surface defects in either the drum or the band.
The above pinholes are completely absent, and the number of pinholes of 10 to 30 μm is 1 / m ² or less, 1
A support having 2 pinholes / m ² or less was used.

(2-7) Casting drying The temperature of the casting chamber provided with the casting die and the support was kept at 35 ° C. The dope cast on the band was first dried by sending parallel-flow drying air. The overall heat transfer coefficient from the drying air to the dope during drying was 24 kcal / m ² · hr · ° C. The temperature of the drying air was 135 ° C on the upstream side of the upper part of the band, and 140 ° C on the downstream side. The lower part of the band
The temperature was 65 ° C. The saturation temperature of each gas was around -8 ° C. The oxygen concentration in the dry atmosphere on the support was kept at 5 vol%. Note that the air was replaced with nitrogen gas in order to maintain the oxygen concentration at 5 vol%. In order to condense and recover the solvent in the casting chamber,
A condenser (condenser) was provided, and the outlet temperature was set to -10 ° C.

For 5 seconds after casting, the static pressure fluctuation in the immediate vicinity of the casting die was suppressed to ± 1 Pa or less so that the dry wind did not directly hit the dope with a wind shield. The solvent ratio in the dope is 150% by mass on a dry basis.
When it became, it peeled as a film from the casting support body. The peeling tension at this time is 10
kgf / m, and the peeling speed (peeling roll draw) with respect to the support speed is 100.
It set so that it could peel off appropriately in the range of 1% to 105%. The surface temperature of the peeled film was 15 ° C. The drying rate on the support was an average of 180% by weight of dry weight standard solvent / minute. The solvent gas generated upon drying was led to a condenser, liquefied at −10 ° C., recovered, and reused as a charging solvent. The drying air from which the solvent was removed was heated again and reused as drying air. At that time, the water content in the solvent was adjusted to 0.5% or less and reused.

The peeled film was conveyed by the transfer part provided with many rollers. In the transition part,
Three rollers were provided, and the temperature at the crossover was kept at 40 ° C. During conveyance with the roller at the crossing portion, a tension of 16N to 160N was applied to the film.

(2-8) Tenter Transport / Drying Process Conditions The peeled film was transported in the drying zone of the tenter while being fixed at both ends with a tenter having a clip, and dried with drying air. The clip was cooled by supplying a heat transfer medium at 20 ° C. The tenter is driven by a chain, and the speed fluctuation of the sprocket is zero.
. It was 5% or less. Further, the interior of the tenter was divided into three zones, and the drying air temperature in each zone was set to 90 ° C., 100 ° C., and 110 ° C. from the upstream side. The gas composition of the drying air was set to a saturated gas concentration of −10 ° C. The average drying rate in the tenter was 120% by mass (dry weight reference solvent) / min. At the outlet of the tenter, the amount of residual solvent in the film was adjusted to 10% by mass or less, and in this experiment, the conditions of the drying zone were adjusted to 7% by mass. In the tenter, the film was stretched in the width direction while being conveyed. The amount of widening when the width when conveyed to the tenter was 100% was 103%. Stretching rate from stripping roller to tenter entrance (tenter-driven draw)
Was 102%. As for the stretching ratio in the tenter, the difference in the substantial stretching ratio at a portion 10 mm or more away from the tenter biting portion was 10% or less, and the difference in the stretching ratio at any two points 20 mm apart was 5% or less. The ratio of the length of the base end fixed with a tenter is 9
0%. Further, the tenter clip was transported while being cooled so as not to exceed 50 ° C. The solvent evaporated in the tenter part was condensed and liquefied at a temperature of −10 ° C. and recovered. A condenser (condenser) was provided for condensation recovery, and the outlet temperature was set to -8 ° C. The water content contained in the solvent was adjusted to 0.5% by mass or less and reused.

Then, the ears were cut at both ends within 30 seconds from the tenter exit. Ears 50 mm on both sides were cut with an NT-type cutter, and the cut ears were blown by a cutter blower to a crusher and crushed into chips of about 80 mm ² on average. This chip is the chip TAC described above. This chip was again used as a raw material in the preparation process together with cellulose triacetate flakes as a raw material for preparation. The oxygen concentration in the dry atmosphere of the tenter part was kept at 5 vol%. Note that the air was replaced with nitrogen gas in order to maintain the oxygen concentration at 5 vol%. The film was preheated in a predrying zone supplied with 100 ° C. drying air before being dried at a high temperature in a roller conveyance zone described later.

(2-9) Post-drying process conditions The cellulose triacetate film after the edge cutting obtained by the method described above was dried at high temperature in the roller transport zone. The roller transport zone is divided into 4 sections, and 120 ° C, 13 ° C from the upstream side.
Dry air of 0 ° C, 130 ° C, and 130 ° C was supplied. At this time, the roller conveying tension of the film was set to 100 N / width, and the film was dried for about 10 minutes until the residual solvent amount finally reached 0.3% by mass. The wrap angle of the roller was 90 degrees and 180 degrees. The roller was made of aluminum or carbon steel, and a hard chrome plating was applied to the surface. As the surface shape of the roller, a flat one and a mat formed by blasting were used. All the shakes due to the rotation of the roller were 50 μm or less. The roller deflection at a tension of 100 N / width was selected to be 0.5 mm or less.

A forced charge removal device (charge removal bar) was installed during the process so that the film voltage during conveyance was always in the range of -3 kV to 3 kV. The take-up portion was neutralized so as to be −1.5 KV to 1.5 KV.

The solvent gas contained in the drying air was adsorbed and recovered using an adsorbent. The adsorbent was activated carbon, and desorption was performed using dry nitrogen. The recovered solvent was adjusted to a water content of 0.3% by mass or less and reused as a charged solvent. In addition to solvent gas, the drying air contains plasticizers, UV absorbers, and other high-boiling substances, so they were removed by a cooler and pre-adsorber to be removed by cooling and recycled. And adsorption / desorption conditions were set so that VOC in outdoor exhaust gas would be 10 ppm or less finally. The amount of solvent recovered by the condensation method of all evaporated solvents is 90% by mass.
Most of the rest was recovered by adsorption recovery.

The dried film was conveyed to the 1st humidity control chamber. Dry air at 110 ° C. was supplied to the transition portion between the roller conveyance zone and the first humidity control chamber. The first humidity chamber has a temperature of 50 ° C and a dew point of 20 ° C.
The air was supplied. Further, the film was conveyed to a second humidity control chamber that suppresses the curling of the film. In the second humidity control chamber, air of 90 ° C. and humidity 70% was directly applied to the film.

(2-10) Post-treatment and winding conditions The dried cellulose triacetate film was cooled to 30 ° C. or lower, and both ends were trimmed, and further, both ends of the film were knurled. The knurling is applied by embossing from one side, the knurling width is 10 mm, and the maximum height is 1 on average than the average thickness.
The pressing pressure was set to be 2 μm higher.

And the film was conveyed to the winding chamber. The winding chamber was kept at a room temperature of 28 ° C. and a humidity of 70%. Cellulose triacetate film thus obtained (thickness 80 μm)
The product width was 1475 mm. The diameter of the core is 169mm and the tension is 36
The tension pattern was 0 N / width and the end of winding was 250 N / width. The total winding length was 3940 m. The oscillating period during winding was 400 m, and the oscillating width was ± 5 mm. Moreover, the press roll was set to the winding roll and the pressure was set to 50 N / width. The temperature of the film during winding is 25 ° C., the water content is 1.4% by mass, and the residual solvent amount is 0
. It was 3 mass%. The average drying rate was 20% by mass (dry weight reference solvent) / min throughout the entire process. Moreover, there was no winding looseness and wrinkles, and no winding slip occurred in the impact test at 10G. The roll appearance was also good. Through the above steps, the cellulose triacetate film sample 101-12 was formed.

The roll of this film sample 101-12 was stored in a storage rack at 25 ° C. and 55% RH for 1 month and further examined in the same manner as described above. As a result, no significant change was observed.
Further, no adhesion was observed in the roll. In addition, this film sample 101-1
The film No. 2 contains 4% by mass of retardation control agent A (trimethylolpropane triacetate). Moreover, after film sample 101-1 was formed, no peeling residue of the cast film formed from the dope was found on the endless belt as the metal support.

(2-11) Evaluation and results The evaluation methods of the samples obtained in the examples are shown below.

(1) Stability of solution The dope after filtration and concentration obtained in (1-3) is collected and observed while standing still at 30 ° C., and evaluated in the following four stages of A, B, C, and D did.
A: Transparency and liquid uniformity are exhibited even over 20 days.
B: Transparency and liquid uniformity are maintained until lapse of 10 days, but a little white turbidity is observed in 20 days.
C: The liquid is transparent and uniform at the end of the liquid preparation, but after one day, it gels and becomes a non-uniform liquid.
D: The liquid is in an opaque and non-uniform solution state with no swelling / dissolution.

(2) Film surface condition The film was observed visually, and the surface condition was evaluated as follows.
A: The film surface is smooth.
B: Although the film surface is smooth, a little foreign material is seen.
C: Weak irregularities are seen on the film surface, and the presence of foreign matter is clearly observed.
D: Unevenness is seen on the film, and many foreign matters are seen.

(3) Moisture and heat resistance of film 1 g of sample is folded and placed in a 15 ml capacity glass bottle, temperature is 90 ° C. and relative humidity is 100%.
After conditioning the humidity under the conditions, it was sealed. This was taken out after 90 days at 90 ° C. The state of the film was visually confirmed and the following judgment was made.
A: No particular abnormality is observed B: A slight decomposition odor is observed C: A considerable decomposition odor is recognized D: A change in shape due to decomposition odor and decomposition is observed

The obtained cellulose triacetate film sample 101-12 had a solution stability of A, a film surface shape of A, a film tear test of 16 g, and a film folding test of 7
Once, the heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0
. The content of Ca was less than 0.05% by mass, Ca was less than 0.05% by mass, and Mg was less than 0.01% by mass. The thickness of the cellulose triacetate film was 80 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less. In addition, the longitudinal and transverse average heat shrinkage (80 ° C., 90%, 48 hours) of the film was −0.10%, and a film that hardly caused heat shrinkage was obtained. The residual solvent amount at the tenter outlet was 7% by mass, and the ear silo LEL at that time was good at less than 25%.

Next, a cellulose triacetate film sample 101-22 was prepared. Sample 00
Samples 013A-2, 014- under the same conditions as Samples 010A-2, 011-2, 012-2, which are the respective dopes of Dope Sample 101-12, except that Sample 004-2 was used instead of 3-2
2,015-2 was prepared. These samples 013A-2, 041-2, and 015-2 are collectively referred to as a dope sample 101-22. A film sample 101-22 was formed under the same conditions as the sample 101-12 using the samples 013A-2, 014-2, and 015-2, and the same evaluation as the film sample 101-12 was performed.

The obtained cellulose triacetate film sample 101-22 has a solution stability of A, a film surface shape of A, a film tear test of 15 g, and a film folding test of 7
It was 3 times, and the heat and humidity resistance was A, all of which were excellent. The amount of residual acetic acid is 0
. The content of Ca was less than 0.05% by mass, Ca was less than 0.05% by mass, and Mg was less than 0.01% by mass. The thickness of the cellulose triacetate film was 80 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 101-22 has a haze of 0.3% and a transparency (transparency) of 92.4%.
The slope width is 19.5 nm, the limit wavelength is 392.5 nm, the absorption edge is 374.2 nm, 380
Absorption of nm is 1.9%, Re is 1.2 nm, Rth is 49 nm, molecular orientation axis is 1.5 °, elastic modulus is 3.58 GPa in the longitudinal direction, 3.4 GPa in the width direction, tensile strength Is 140MPa in the longitudinal direction and 141MPa in the width direction. The elongation is 42% in the longitudinal direction and 48% in the width direction.
Kisimi value (static friction coefficient) is 0.64, Kisimi value (dynamic friction coefficient) is 0.52, Alkaline hydrolyzability is A, curl value is -0.6 at 25% RH, 1 at wet .8. The moisture content is 1.4% by mass, the residual solvent amount is 0.31% by mass, the moisture permeability coefficient is 1538 g / (m ² · day), and the thermal shrinkage is −0.10% in the longitudinal direction. And the width direction was -0.09%. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.0.
2 mm to 0.05 mm is less than 10/3 m, 0.05 to 0.1 mm is less than 5/3 m, 0.
There was no more than 1 mm. These had excellent properties for optical applications. Moreover, adhesion after application was not observed (◯), and the moisture permeability was good (◯).

Next, a cellulose triacetate film sample 101-32 was produced. Sample 00
A dope prepared under the same conditions as Sample 003-2 except that 1% by mass of a hydrophobizing agent (benzenesulfonanilide) is added to TAC of 3-2 in an external ratio is referred to as Sample 005. In addition, a dope prepared under the same conditions as Sample 004-2 was added to Sample 006 except that 1% by mass of a hydrophobizing agent (benzenesulfonanilide) was added in an external ratio to the TAC of Sample 004-2.
It is called -2. In addition, the hydrophobizing agent was contained so that it might become 0.5 mass% in a film form.

Sample 01 except that the dope being fed was changed from sample 003-2 to sample 005-2
A dope produced under the same conditions as 0A-2 is referred to as Sample 020A-2. Further, the dope being transferred is changed from sample 003-2 to sample 005-2, and other than that, sample 01-1-2
Dopes manufactured under the same conditions as 012-2 are referred to as Samples 021-2 and 022-2. These samples 020A-2, 021-2, and 022-2 are collectively referred to as a dope sample 101-32. A cellulose triacetate film sample 101-32 was formed using the dope sample 101-32 under the same conditions as the film sample 101-12, and the same evaluation as the film sample 101-12 was performed.

The obtained cellulose triacetate film sample 101-32 has a solution stability of A, a film surface shape of A, a film tear test of 16 g, and a film folding test of 7
It was twice, and the heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0
. The content of Ca was less than 0.05% by mass, Ca was less than 0.05% by mass, and Mg was less than 0.01% by mass. The thickness of the cellulose triacetate film was 80 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 101-32 has a haze of 0.3% and a transparency (transparency) of 92.5%.
, Slope width is 19.6 nm, limit wavelength is 392.7 nm, absorption edge is 374.2 nm, 380
Absorption of nm is 2.0%, Re is 1.1 nm, Rth is 50 nm, molecular orientation axis is 1.4 °, elastic modulus is 3.51 GPa in the longitudinal direction, 3.41 GPa in the width direction, tensile strength The longitudinal direction is 140 MPa, the width direction is 143 MPa, the elongation is 44% in the longitudinal direction, and the width direction is 49%.
%, The kishimi value (static friction coefficient) is 0.65, the kishimi value (dynamic friction coefficient) is 0.53,
Alkaline hydrolyzability is A, curl value is -0.5 at 25% RH, 1.5 at wet.
Met. The water content is 1.25% by mass, the residual solvent amount is 0.30% by mass,
The moisture permeability coefficient was 1115 g / (m ² · day), and the thermal shrinkage rate was −0.09% in the longitudinal direction and −0.09% in the width direction. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.
02mm ~ 0.05mm is less than 10 / 3m, 0.05-0.1mm is less than 5 / 3m, 0
. There was no more than 1 mm. These had excellent properties for optical applications. Further, no adhesion was observed after application (◯), and the moisture permeability was very good (良好).

Sample 01 except that the dope being fed was changed from Sample 004-2 to Sample 006-2
A dope manufactured under the same conditions as 3A-2 is referred to as Sample 023A-2. In addition, instead of the sample 004-2 to the sample 006-2, the liquid dope being transferred is changed to the sample 014-2.
Dopes produced under the same conditions as in 015-2 are referred to as Samples 04-2 and 025-2. These samples 023A-2, 04-2, and 05-2 are collectively referred to as a dope sample 101-42. Using these samples 023A-2, 0242-2, and 05-2, film samples 101-12
Cellulose triacetate film sample 101-42 was formed under the same conditions as in Example 1, and the same evaluation as film sample 101-12 was performed.

The obtained cellulose triacetate film sample 101-42 has a solution stability of A, a film surface shape of A, a film tear test of 15 g, and a film folding test of 7
It was 0 times, and the heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0
. The content of Ca was less than 0.05% by mass, Ca was less than 0.05% by mass, and Mg was less than 0.01% by mass. The thickness of the cellulose triacetate film was 80 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 101-42 has a haze of 0.3% and a transparency (transparency) of 92.5%.
The slope width is 19.4 nm, the limit wavelength is 392.6 nm, the absorption edge is 374.1 nm, 380
Absorption at nm is 1.80%, Re is 1.0 nm, Rth is 48 nm, molecular orientation axis is 1.5 °, elastic modulus is 3.59 GPa in the longitudinal direction, 3.4 GPa in the width direction, tensile strength The longitudinal direction is 138 MPa, the width direction is 141 MPa, the elongation is 43% in the longitudinal direction, and the width direction is 48
%, The kishimi value (static friction coefficient) is 0.65, the kishimi value (dynamic friction coefficient) is 0.51,
Alkaline hydrolyzability is A, curl value is -0.3 at 25% RH, 1.7 when wet.
Met. The water content is 1.24% by mass, the residual solvent amount is 0.30% by mass,
The moisture permeability coefficient was 1121 g / (m ² · day), and the heat shrinkage rate was −0.09% in the longitudinal direction and −0.07% in the width direction. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.
02mm ~ 0.05mm is less than 10 / 3m, 0.05-0.1mm is less than 5 / 3m, 0
. There was no more than 1 mm. These had excellent properties for optical applications. Further, no adhesion was observed after application (◯), and the moisture permeability was very good (良好).

Next, a cellulose triacetate film sample 102-12 having a thickness of 40 μm was formed. In addition, the location which is not demonstrated in particular was performed on the same conditions as the film forming method of the film sample 101-12. The dope is sample 010A-2, 011-2, 01 constituting the dope sample 101-12.
2-2 was used. The content of retardation control agent A (trimethylolpropane triacetate) contained in Sample 010A-2 was adjusted to be 3.0% by mass in the form of a film. Hereinafter, these samples are collectively referred to as a dope sample 102-12. The film thickness of the finished cellulose triacetate film sample 102-12 was 4 μm.
m, 33μm, 3μm, casting speed (line speed) so that the product thickness is 40μm
Was cast at 100 m / min. Note that the pressure at the back of the casting die bead is -150
a. The temperature of the drying air in the casting chamber was 50 ° C. at the upper part of the band and 70 ° C. at the lower part of the band. After peeling off the film from the band, the transfer part was conveyed and sent to the tenter. In addition, the tension | tensile_strength of 10N-100N was provided to the film, when conveying with the roller of a transfer part. While drying with a tenter, the desired widening was also performed. The amount of widening when the width when transported to the tenter is 100% was 102%, and the stretch ratio from the peeling roller to the tenter inlet (tenter drive draw) was 101%. After the preliminary drying zone was conveyed, it was dried at a high temperature in the roller conveyance zone. During the process, a forced static eliminator (static neutralization bar) is installed and -3
kV to 3 kV. After the transfer section was transported, it was transported to the humidity control chamber, after which knurling was applied and then transported to the winding chamber.

The winding chamber was kept at a room temperature of 35 ° C. and a humidity of 80%, the tension at the start of winding was 250 N / width, and the tension pattern was such that the end of winding was 170 N / width, and oscillating was also performed. The cellulose triacetate film of the present invention produced by the above steps was used as Sample 102-12. The roll of this film sample 102-12 was placed at 25 ° C. and 55% RH.
As a result of storing in a storage rack for 1 month and further testing in the same manner as described above, no significant change was observed. Further, no adhesion was observed in the roll. In addition, 3 mass% retardation control agent A is contained in this film sample 102-12.

The obtained cellulose triacetate film sample 102-12 has a solution stability of A, a film surface shape of A, and a film tear test of 10 g.
It was 29 times, the heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is
The content of Ca was less than 0.01% by mass, Ca was less than 0.05% by mass and Mg was less than 0.01% by mass. The thickness of the cellulose triacetate film was 40 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 102-12 has a haze of 0.3% and a transparency (transparency) of 92.5.
%, The slope width is 19.5 nm, the critical wavelength is 392.6 nm, the absorption edge is 374.1 nm, 38
Absorption at 0 nm is 2.40%, Re is 0.9 nm, Rth is 51 nm, molecular orientation axis is 1.6 °, elastic modulus is 3.54 GPa in the longitudinal direction, 3.45 GPa in the width direction, tensile strength The longitudinal direction is 139 MPa, the width direction is 141 MPa, the elongation rate is 43% in the longitudinal direction, and the width direction is 49%.
1. Alkaline hydrolyzability is A, curl value is -0.4 at 25% RH, 2 at wet.
. It was 9. The moisture content is 1.20% by mass, the residual solvent amount is 0.19% by mass, the moisture permeability coefficient is 2510 g / (m ² · day), and the heat shrinkage is −0.07% in the longitudinal direction. And the width direction was -0.08%. The foreign matter had a lint of less than 5 pieces / m. The bright spot is
0.02 mm to 0.05 mm was less than 10 pieces / 3 m, 0.05 to 0.1 mm was less than 5 pieces / 3 m, and there was no more than 0.1 mm. These had excellent properties for optical applications. Further, no adhesion after coating was observed (◯), and the water vapor transmission rate was slightly high, but at a level (Δ) with no practical problem.

Next, a cellulose triacetate film sample 102-22 was prepared. Sample 01
Samples 013A-2, 014-2, and 015-2 instead of 0A-2, 011-2, and 012-2
Was used. The amount of retardation control agent A in Sample 013A-2 was adjusted to 0.3% by mass in the form of a film. Hereinafter, the dope sample 102 is combined with these samples.
Called -22. Other than that, the cellulose triacetate film sample 102-22 was formed on the same conditions as film formation of the film sample 102-12, and the same evaluation as the film sample 101-12 was performed.

The obtained cellulose triacetate film sample 102-22 has a solution stability of A, a film surface shape of A, and a film tear test of 11 g.
It was 30 times, the heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is
The content of Ca was less than 0.01% by mass, Ca was less than 0.05% by mass and Mg was less than 0.01% by mass. The thickness of the cellulose triacetate film was 40 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 102-22 has a haze of 0.3% and a transparency (transparency) of 92.5.
%, Slope width is 19.6 nm, limit wavelength is 392.7 nm, absorption edge is 374.2 nm, 38%
Absorption at 0 nm is 2.20%, Re is 0.8 nm, Rth is 50 nm, molecular orientation axis is 1.4 °, elastic modulus is 3.53 GPa in the longitudinal direction, 3.41 GPa in the width direction, tensile strength The longitudinal direction is 138 MPa, the width direction is 141 MPa, the elongation rate is 43% in the longitudinal direction, and the width direction is 49%.
Alkaline hydrolyzability is A, curl value is -0.3 at 25% RH, 3.
1 The moisture content is 1.21% by mass, the residual solvent amount is 0.18% by mass, the moisture permeability coefficient is 2518 g / (m ² · day), and the thermal shrinkage is −0.08% in the longitudinal direction. And the width direction was -0.08%. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0
. 02 mm to 0.05 mm is less than 10/3 m, 0.05 to 0.1 mm is less than 5/3 m,
There was no more than 0.1 mm. These had excellent properties for optical applications. Further, no adhesion after coating was observed (◯), and the water vapor transmission rate was slightly high, but at a level (Δ) with no practical problem.

Next, a cellulose triacetate film sample 102-32 was produced. Sample 01
Samples 020A-2, 021-2, and 022-2 instead of 0A-2, 011-2, and 012-2
Was used. In addition, the retardation controlling agent A in Sample 020A-2 is 3 in film form.
. It prepared so that it might become 0 mass%. Moreover, the hydrophobizing agent was contained so that it might become 0.5 mass% with a film form. Hereinafter, these samples are collectively referred to as a dope sample 102-32.
Other than that, the cellulose triacetate film sample 102-32 was formed on the same conditions as the film sample 102-12, and the same evaluation as the film sample 101-12 was performed.

The obtained cellulose triacetate film sample 102-32 has a solution stability of A, a film surface shape of A, and a film tear test of 11 g.
It was 25 times, the heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is
The content of Ca was less than 0.01% by mass, Ca was less than 0.05% by mass and Mg was less than 0.01% by mass. The thickness of the cellulose triacetate film was 40 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 102-32 has a haze of 0.3% and a transparency (transparency) of 92.5.
%, Slope width is 19.6 nm, limit wavelength is 392.6 nm, absorption edge is 374.2 nm, 38%
Absorption at 0 nm is 2.30%, Re is 0.6 nm, Rth is 49 nm, molecular orientation axis is 1.5 °, elastic modulus is 3.52 GPa in the longitudinal direction, 3.4 GPa in the width direction, tensile strength Is 140 MPa in the longitudinal direction and 142 MPa in the width direction, and the elongation is 43% in the longitudinal direction and 4 in the width direction.
9%, the Kishimi value (static friction coefficient) is 0.62, and the Kishimi value (dynamic friction coefficient) is 0.51.
Alkaline hydrolyzability is A, curl value is -0.2 at 25% RH, 3.
2. The moisture content is 1.11% by mass, the residual solvent amount is 0.20% by mass, the moisture permeability coefficient is 1231 g / (m ² · day), and the thermal shrinkage is −0.07% in the longitudinal direction. And the width direction was -0.08%. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0
. 02 mm to 0.05 mm is less than 10/3 m, 0.05 to 0.1 mm is less than 5/3 m,
There was no more than 0.1 mm. These had excellent properties for optical applications. Further, no adhesion was observed after application (◯), and the moisture permeability was very good (良好).

Next, a cellulose triacetate film sample 102-42 was produced. Sample 01
Samples 023A-2, 0242-2, and 05-2-2 instead of 3A-2, 014-2, and 015-2
Was used. In addition, the retardation controlling agent A in Sample 023A-2 is 3 in film form.
. It prepared so that it might become 0 mass%. Moreover, the hydrophobizing agent was contained so that it might become 0.5 mass% with a film form. Hereinafter, these samples are collectively referred to as a dope sample 102-42.
Other than that, the cellulose triacetate film sample 102-42 was formed on the same conditions as the film sample 102-22, and the same evaluation as the film sample 101-12 was performed.

The obtained cellulose triacetate film sample 102-42 has a solution stability of A, a film surface shape of A, and a film tear test of 10 g.
It was 35 times, the heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is
The content of Ca was less than 0.01% by mass, Ca was less than 0.05% by mass and Mg was less than 0.01% by mass. The thickness of the cellulose triacetate film was 40 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 102-42 has a haze of 0.3% and a transparency (transparency) of 92.5.
%, Slope width is 19.6 nm, limit wavelength is 392.7 nm, absorption edge is 374.1 nm, 38%
Absorption at 0 nm is 2.30%, Re is 0.7 nm, Rth is 52 nm, molecular orientation axis is 1.4 °, elastic modulus is 3.54 GPa in the longitudinal direction, 3.41 GPa in the width direction, tensile strength The longitudinal direction is 143 MPa, the width direction is 141 MPa, the elongation is 43% in the longitudinal direction, and the width direction is 49%. The kishimi value (static friction coefficient) is 0.65, and the kishimi value (dynamic friction coefficient) is 0.5.
1. Alkaline hydrolyzability is A, curl value is -0.5 at 25% RH, 3 at wet.
. 4. The moisture content is 1.09% by mass, the residual solvent amount is 0.20% by mass, the moisture permeability coefficient is 1228 g / (m ² · day), and the thermal shrinkage is −0.09% in the longitudinal direction. And the width direction was -0.09%. The foreign matter had a lint of less than 5 pieces / m. The bright spot is
0.02 mm to 0.05 mm was less than 10 pieces / 3 m, 0.05 to 0.1 mm was less than 5 pieces / 3 m, and there was no more than 0.1 mm. These had excellent properties for optical applications. Further, no adhesion was observed after application (◯), and the moisture permeability was very good (良好).

Next, a cellulose triacetate film sample 103-12 having a thickness of 60 μm and preferably used for a WV film was formed. In addition, the part which is not demonstrated in particular is the sample 101-1.
It carried out on the same conditions as the film forming method of 2. Samples 010A-2, 013A-2, 020A-2, 0
TPP (triphenyl phosphate) + BDP as retardation control agent B instead of trimethylolpropane triacetate as retardation control agent A in 23A-2
(Biphenyldiphenyl phosphate) (TPP / BDP = 2/1; weight ratio) and UV absorber d (2-hydroxy-4-benzyloxybenzophenone / 2,4-bis (benzyloxy) benzophenone = 3/1; weight ratio ) And 010B-2, 013B-
2,020B-2,023B-2 was prepared. Preparation conditions were as follows: Sample 010A-2, 013A
The test was carried out under the same conditions as those for -2, 020A-2 and 023A-2. The concentration of the retardation control agent B was adjusted to 1.0% by mass in the film form, and the ultraviolet absorber d was adjusted to 0.5% by mass. The dope composed of the samples 010B-2, 011-2, and 012-2 is referred to as a dope sample 103-12 in the following description.

The finished cellulose triacetate film sample 103-12 was cast at a casting speed (line speed) of 100 m / min so that the film thickness was 6 μm, 50 μm, and 4 μm, respectively, and the product thickness was 60 μm. The bead back pressure was adjusted to be −150 Pa. The temperature of the casting chamber was maintained at 35 ° C, and the temperature of the drying air was 30 ° C on the upstream side of the upper part of the band and 125 ° C on the downstream side. The lower part of the band was set to 80 ° C. After peeling off the film from the support, the film was transported at the crossover and sent to the tenter. During conveyance with the roller at the crossover, a tension of 15N to 150N was applied to the film. Divide the inside of the tenter into 3 zones, and set the drying air temperature in each zone to 100 ° C, 110 ° C, 120 ° C from the upstream side, and the widening amount when the width when transported to the tenter is 100% is 102% The stretch ratio from the peeling roller to the tenter entrance (tenter driven draw) was 105%. High temperature drying was performed in the preliminary drying zone and the roller conveyance zone. A forced static eliminator (static neutralization bar) was installed during the process, and was set to −5 kV to 5 kV. The air supply temperature of the air in the second humidity control chamber was 50 ° C. The cellulose triacetate film after drying was cut off at both ends and knurled at both ends of the film. And the film was conveyed to the winding chamber. A tension pattern having a winding start tension of 300 N and a winding end of 210 N using a core having a diameter of 300 mm was used. The total winding length was 2840 m. The roll of this film sample 103-12 was stored in a storage rack at 25 ° C. and 55% RH for 1 month and further examined in the same manner as described above. As a result, no significant change was observed. Further, no adhesion was observed in the roll. In addition, 1.0 mass% retardation control agent B and 0.5 mass% UV agent d are contained in this film sample 103-12.

The obtained cellulose triacetate film sample 103-12 had a solution stability of A, a film surface shape of A, a film tear test of 11 g, and a film folding test of 7
It was 5 times, and the heat and humidity resistance was A, all of which were excellent. The amount of residual acetic acid is 0
. The content of the cellulose triacetate film was 60 μm ± 1.5 μm over the entire area. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 103-12 has a haze of 0.3% and a transparency (transparency) of 92.4.
%Met. Re is 10.2 nm, Rth is 81 nm, molecular orientation axis is 1.4 °, elastic modulus is 3.59 GPa in the longitudinal direction, 3.43 GPa in the width direction, and tensile strength is 139 M in the longitudinal direction.
Pa, 141 MPa in the width direction, 43% in the longitudinal direction, 49% in the width direction, 0.65 for the kishimi value (static friction coefficient), 0.5 for the kishimi value (dynamic friction coefficient), alkaline hydrolysis The curability was -0.3 at 25% RH and 2.2 when wet. Also,
The water content is 1.34% by mass, the residual solvent amount is 0.24% by mass, and the moisture permeability coefficient is 181.
1 g / (m ² · day), thermal shrinkage is −0.09% in the longitudinal direction and −0.09% in the width direction
Met. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.02 mm to 0.0.
5 mm was less than 10/3 m, 0.05 to 0.1 mm was less than 5/3 m, and there was no more than 0.1 mm. These had excellent properties for optical applications. Further, no adhesion after coating was observed (◯), and the water vapor transmission rate was slightly high, but at a level (Δ) with no practical problem.

Next, a cellulose triacetate film sample 103-22 was prepared. Sample 01
Samples 013B-2, 014-2, and 015-2 instead of 0B-2, 011-2, and 012-2
Was used. Hereinafter, these samples are collectively referred to as a dope sample 103-22. Other than that, the cellulose triacetate sample 103-22 was formed on the same conditions as the film sample 103-12, and the same evaluation as the film sample 101-12 was performed.

The obtained cellulose triacetate film sample 103-22 has a solution stability of A, a film surface shape of A, a film tear test of 12 g, and a film folding test of 7
It was 4 times, and the heat and humidity resistance was A, all of which were excellent. The amount of residual acetic acid is 0
. The content of the cellulose triacetate film was 60 μm ± 1.5 μm over the entire area. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 103-22 has a haze of 0.3% and a transparency (transparency) of 92.4.
%Met. Re is 10.5 nm, Rth is 79 nm, molecular orientation axis is 1.3 °, elastic modulus is 3.50 GPa in the longitudinal direction, 3.42 GPa in the width direction, and tensile strength is 140 M in the longitudinal direction.
Pa, 142 MPa in the width direction, 43% in the longitudinal direction, 49% in the width direction, 0.63 for the kishimi value (static friction coefficient), 0.52 for the kishimi value (dynamic friction coefficient), alkaline hydrolysis The property was A, the curl value was -0.5 at 25% RH, and 2.3 when wet. The moisture content is 1.35% by mass, the residual solvent amount is 0.25% by mass, and the moisture permeability coefficient is 18%.
09 g / (m ² · day), thermal shrinkage rate is −0.09% in the longitudinal direction and −0.08 in the width direction
%Met. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.02 mm to 0.00.
05 mm was less than 10/3 m, 0.05-0.1 mm was less than 5/3 m, and there was no more than 0.1 mm. These had excellent properties for optical applications. In addition, adhesion after application was not observed (◯), and the water vapor transmission rate was slightly higher, but there was no practical problem (△).
Met.

Next, a cellulose triacetate film sample 103-32 was prepared. Sample 01
Samples 020B-2, 021-2, 022-2 instead of 0B-2, 011-2, 012-2
Was used. In addition, the hydrophobizing agent was contained so that it might become 0.5 mass% in a film form. Hereinafter, these samples are collectively referred to as a dope sample 103-32. Other than that, the cellulose triacetate film sample 103-32 was formed on the same conditions as the film sample 103-1, and the same evaluation as the film sample 101-12 was performed.

The obtained cellulose triacetate film sample 103-32 has a solution stability of A, a film surface shape of A, and a film tear test of 11 g.
It was 3 times, and the heat and humidity resistance was A, all of which were excellent. The amount of residual acetic acid is 0
. The content of the cellulose triacetate film was 60 μm ± 1.5 μm over the entire area. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 103-32 has a haze of 0.3% and a transparency (transparency) of 92.5.
%Met. Re is 9.8 nm, Rth is 81 nm, molecular orientation axis is 1.2 °, elastic modulus is 3.54 GPa in the longitudinal direction, 3.4 GPa in the width direction, and tensile strength is 144 MPa in the longitudinal direction.
, 141 MPa in the width direction, 43% in the longitudinal direction, 49% in the width direction, 0.65 for the kishimi value (static friction coefficient), 0.51 for the kishimi value (dynamic friction coefficient) Was A, and the curl value was −0.4 at 25% RH and 2.4 when wet. The moisture content is 1.30% by mass, the residual solvent amount is 0.24% by mass, and the moisture permeability coefficient is 1173.
g / (m ² · day), the heat shrinkage rate was −0.08% in the longitudinal direction and −0.08% in the width direction. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.02 mm to 0.05.
No mm was less than 10/3 m, 0.05-0.1 mm was less than 5/3 m, and no more than 0.1 mm. These had excellent properties for optical applications. Further, no adhesion was observed after application (◯), and the moisture permeability was very good (良好).

Next, a cellulose triacetate film sample 103-42 was prepared. Sample 01
Instead of 3B-2, 014-2, and 015-2, Samples 023B-2, 0242-2, and 05-2
Was used. In addition, the hydrophobizing agent was contained so that it might become 0.5 mass% in a film form. Hereinafter, these samples are collectively referred to as a dope sample 103-42. Other than that, the cellulose triacetate film sample 103-42 was formed on the same conditions as the film sample 103-22, and the same evaluation as the film sample 101-12 was performed.

The obtained cellulose triacetate film sample 103-42 has a solution stability of A, a film surface shape of A, and a film tear test of 11 g.
It was 4 times, and the heat and humidity resistance was A, all of which were excellent. The amount of residual acetic acid is 0
. The content of the cellulose triacetate film was 60 μm ± 1.5 μm over the entire area. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 103-42 has a haze of 0.3% and a transparency (transparency) of 92.5.
%Met. Re is 9.9 nm, Rth is 78 nm, the molecular orientation axis is 1.3 °, the elastic modulus is 3.54 GPa in the longitudinal direction, 3.42 GPa in the width direction, and the tensile strength is 140 MP in the longitudinal direction.
a, 141 MPa in the width direction, 43% in the longitudinal direction, 49% in the width direction, 0.63 for the kishimi value (static friction coefficient), 0.51 for the kishimi value (dynamic friction coefficient), alkaline hydrolysis The curability value was -0.2 at 25% RH and 2.1 when wet. Also,
The water content is 1.29% by mass, the residual solvent amount is 0.25% by mass, and the moisture permeability coefficient is 118.
2 g / (m ² · day), thermal shrinkage is −0.09% in the longitudinal direction and −0.08% in the width direction
Met. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.02 mm to 0.0.
5 mm was less than 10/3 m, 0.05 to 0.1 mm was less than 5/3 m, and there was no more than 0.1 mm. These had excellent properties for optical applications. Further, no adhesion was observed after application (◯), and the moisture permeability was very good (良好).

Next, a cellulose triacetate film sample 104-12 having a thickness of 80 μm and preferably used for an OCB film was formed. In addition, the location which is not demonstrated in particular was performed on the same conditions as the film forming method of the film sample 101-12. Sample 010A-2, 013A-2, 020
N, N ′, N ″ -tri-m-toluyl-1,3,5 which is retardation control agent N instead of trimethylolpropane triacetate which is retardation control agent A in A-2,023A-2 -Sample 010C-2, 013 using triazine-2,4,6-triamine
C-2,020C-2,023-2C was prepared. The retardation controlling agent N is
It prepared so that it might become 3 mass% in a film form. The preparation conditions were as follows: Sample 010A-2
, 013A-2, 020A-2 and 023A-2. Sample 010C-2
In the following description, the one composed of 011-2 and 012-2 is referred to as a dope sample 104-12.

  The finished cellulose triacetate film sample 104-12 had a casting speed (line speed) of 100 m / min so that the film thickness was 10 μm, 60 μm, and 10 μm, respectively, and the product thickness was 80 μm. The temperature of the casting chamber was maintained at 35 ° C, and the temperature of the drying air was 30 ° C on the upstream side of the upper part of the band and 100 ° C on the downstream side. The lower part of the band was set to 80 ° C. The film was peeled off from the support, and the transition part was conveyed and sent to the tenter. While being conveyed by the roller at the crossover, a tension of 13N to 130N was applied to the film. The desired widening was performed while drying was progressing with a tenter. The inside of the tenter is divided into three zones, and the drying temperature of each zone is 120 ° C, 130 ° C, 140 ° C from the upstream side, and the widening amount when the width when transported to the tenter is 100% is 130%. . The stretching ratio from the peeling roller to the tenter inlet (tenter-driven draw) was 102%. Then, both ends were cut off, the film was preheated in the preliminary drying zone, and dried at a high temperature in the roller conveyance zone. Moreover, the forced static elimination apparatus (static elimination bar) was installed in the process, and it was set to -3kV-3kV. Dry air of 95 ° C. was supplied to the transition part from the roller conveyance zone to the first humidity control chamber. The dried film was conveyed to a humidity control chamber. In the second humidity control chamber, the air supply temperature was 95 ° C. And the film was conveyed to the winding chamber. The winding chamber was kept at a room temperature of 35 ° C. and a humidity of 80%. The tension pattern was such that the winding start tension was 190N and the winding end was 130N. The total winding length was 2840 m. The cellulose triacetate film of the present invention was designated as Sample 104-12. The roll of Sample 104-12 was stored in a storage rack at 25 ° C. and 55% RH for 1 month and further examined in the same manner as described above. As a result, no significant change was observed. Further, no adhesion was observed in the roll. The film sample 104-12 contains 3% by mass of the retardation control agent N.

The obtained cellulose triacetate film sample 104-12 has a solution stability of A, a film surface shape of A, a film tear test of 15 g, and a film folding test of 7
It was twice, and the heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0
. The content of Ca was less than 0.05% by mass, Ca was less than 0.05% by mass, and Mg was less than 0.01% by mass. The thickness of the cellulose triacetate film was 80 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 104-12 has a haze of 0.3% and a transparency (transparency) of 92.4.
%Met. Re is 42 nm, Rth is 175 nm, molecular orientation axis is 1.9 °, elastic modulus is 3.54 GPa in the longitudinal direction, 3.4 GPa in the width direction, and tensile strength is 145 MPa in the longitudinal direction.
The width direction is 139 MPa, the elongation is 43% in the longitudinal direction and the width direction is 49%, the kishimi value (static friction coefficient) is 0.63, the kishimi value (dynamic friction coefficient) is 0.51, and the alkali hydrolyzability Was A, and the curl value was −0.5 at 25% RH and 1.6 when wet. The moisture content is 1.45% by mass, the residual solvent amount is 0.35% by mass, and the moisture permeability coefficient is 1528.
g / (m ² · day), the heat shrinkage rate was −0.09% in the longitudinal direction and −0.10% in the width direction. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.02 mm to 0.05.
No mm was less than 10/3 m, 0.05-0.1 mm was less than 5/3 m, and no more than 0.1 mm. These had excellent properties for optical applications. Moreover, adhesion after application was not observed (◯), and the moisture permeability was good (◯).

Next, a cellulose triacetate film sample 104-22 was prepared. Sample 01
Samples 013C-2, 014-2, and 015-2 instead of 0C-2, 011-2, and 012-2
Was used. In the following description, these samples are combined together to form a dope sample 104-22.
Called. Other than that, the cellulose triacetate film sample 104-22 was formed on the same conditions as the film sample 104-12, and the same evaluation as the film sample 101-12 was performed.

The obtained cellulose triacetate film sample 104-22 has a solution stability of A, a film surface shape of A, a film tear test of 16 g, and a film folding test of 7
Once, the heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0
. The content of Ca was less than 0.05% by mass, Ca was less than 0.05% by mass, and Mg was less than 0.01% by mass. The thickness of the cellulose triacetate film was 80 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 104-22 has a haze of 0.3% and a transparency (transparency) of 92.4.
%Met. Re is 40 nm, Rth is 172 nm, molecular orientation axis is 1.7 °, elastic modulus is 3.53 GPa in the longitudinal direction, 3.41 GPa in the width direction, and tensile strength is 140 MP in the longitudinal direction.
a, 143 MPa in the width direction, 43% in the longitudinal direction, 49% in the width direction, 0.65 for the kishimi (static friction coefficient), 0.52 for the kishimi (dynamic friction coefficient), alkaline hydrolysis The property was A, and the curl value was −0.7 at 25% RH and 1.8 at wet. Also,
The water content is 1.44% by mass, the residual solvent amount is 0.34% by mass, and the moisture permeability coefficient is 152.
4 g / (m ² · day), heat shrinkage rate is −0.09% in the longitudinal direction and −0.10% in the width direction
Met. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.02 mm to 0.0.
5 mm was less than 10/3 m, 0.05 to 0.1 mm was less than 5/3 m, and there was no more than 0.1 mm. These had excellent properties for optical applications. Moreover, adhesion after application was not observed (◯), and the moisture permeability was good (◯).

Next, a cellulose triacetate film sample 104-32 was prepared. Sample 01
Sample 020C-2, 021-2, 022-2 instead of 0C-2, 011-2, 012-2
Was used. In addition, the hydrophobizing agent was contained so that it might become 0.5 mass% in a film form. In the following description, these samples are collectively referred to as a dope sample 104-32. Otherwise, the cellulose triacetate film sample 104 under the same conditions as the film sample 104-12
-32 was formed and evaluated in the same manner as the film sample 101-12.

The obtained cellulose triacetate film sample 104-32 has a solution stability of A, a film surface shape of A, and a film tear test of 17 g.
Once, the heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0
. The content of Ca was less than 0.05% by mass, Ca was less than 0.05% by mass, and Mg was less than 0.01% by mass. The thickness of the cellulose triacetate film was 80 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 104-32 has a haze of 0.3% and a transparency (transparency) of 92.4.
%Met. Re is 41 nm, Rth is 174 nm, the molecular orientation axis is 1.8 °, the elastic modulus is 3.52 GPa in the longitudinal direction, 3.4 GPa in the width direction, and the tensile strength is 142 MPa in the longitudinal direction.
, 141 MPa in the width direction, 43% in the longitudinal direction and 49% in the width direction, 0.63 for the kishimi value (static friction coefficient), 0.5 for the kishimi value (dynamic friction coefficient), and alkali hydrolyzability Was A, and the curl value was −0.5 at 25% RH and 1.6 when wet. The water content is 1.39% by mass, the residual solvent amount is 0.33% by mass, and the moisture permeability coefficient is 1112 g.
/ (M ² · day), the thermal shrinkage was −0.10% in the longitudinal direction and −0.11% in the width direction. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.02 mm to 0.05 m.
m was less than 10/3 m, 0.05-0.1 mm was less than 5/3 m, and there was no more than 0.1 mm. These had excellent properties for optical applications. Further, no adhesion was observed after application (◯), and the moisture permeability was very good (良好).

Next, a cellulose triacetate film sample 104-42 was prepared. Sample 01
Instead of 3C-2, 014-2, and 015-2, Samples 023C-2, 0242-2, and 05-2
Was used. In addition, the hydrophobizing agent was contained so that it might become 0.5 mass% in a film form. In the following description, these samples are collectively referred to as a dope sample 104-42. Otherwise, the cellulose triacetate film sample 104 under the same conditions as the film sample 104-12
-42 was formed and evaluated in the same manner as the film sample 101-12.

The obtained cellulose triacetate film sample 104-42 has a solution stability of A, a film surface shape of A, a film tear test of 16 g, and a film folding test of 7
It was 3 times, and the heat and humidity resistance was A, all of which were excellent. The amount of residual acetic acid is 0
. The content of Ca was less than 0.05% by mass, Ca was less than 0.05% by mass, and Mg was less than 0.01% by mass. The thickness of the cellulose triacetate film was 80 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 104-42 has a haze of 0.3% and a transparency (transparency) of 92.5.
%Met. Re is 42 nm, Rth is 172 nm, molecular orientation axis is 1.7 °, elastic modulus is 3.54 GPa in the longitudinal direction, 3.45 GPa in the width direction, and tensile strength is 140 MP in the longitudinal direction.
a, the width direction is 143 MPa, the elongation is 43% in the longitudinal direction, and the width direction is 49%, the kishimi value (static friction coefficient) is 0.62, the kishimi value (dynamic friction coefficient) is 0.51, and alkaline hydrolysis The curability was -0.5 at 25% RH and 1.7 when wet. Also,
The water content is 1.38% by mass, the residual solvent amount is 0.33% by mass, and the moisture permeability coefficient is 110.
9 g / (m ² · day), thermal shrinkage is −0.10% in the longitudinal direction and −0.09% in the width direction
Met. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.02 mm to 0.0.
5 mm was less than 10/3 m, 0.05 to 0.1 mm was less than 5/3 m, and there was no more than 0.1 mm. These had excellent properties for optical applications. Further, no adhesion was observed after application (◯), and the moisture permeability was very good (良好).

Retardation control agent A (trimethylolpropane triacetate) was added to sample 080 (
It was dissolved in a mixed solvent) to obtain a solution. This solution was mixed with sample 001-2 being fed in-line via a static mixer. This dope below is referred to as a dope sample 001A-2. In addition, the retardation control agent A was adjusted so that it might be 4.0 mass% with a film form.

The single-layer casting die has a width of 1.7 m. Moreover, it kept at 25 degreeC during the work process. The casting die was a coat hanger type die, in which thickness adjusting bolts were provided at a pitch of 20 mm and equipped with an automatic thickness adjusting mechanism using a heat bolt. This heat bolt can also set a profile according to the liquid feeding amount of the high precision gear pump by a preset program. The thing which has the performance which can also be feedback-controlled by the adjustment program based on the profile of the infrared thickness meter installed in the film forming process was used.
The thickness difference between two arbitrary points separated by 50 mm in the film excluding the casting edge portion of 20 mm was within 1 μm, and the largest difference in the width direction thickness was adjusted to be 3 μm or less. The thickness accuracy was adjusted to ± 1.5 μm or less.

Moreover, the chamber for decompressing was installed in the primary side of the casting die. The pressure reduction degree of this decompression chamber can apply a pressure difference of 1 Pa to 5000 Pa before and after the casting bead, and can be adjusted according to the casting speed. At that time, the pressure difference was set such that the bead length was 5 mm to 50 mm. Moreover, the apparatus which can set the temperature of a chamber higher than the condensation temperature of the gas around a casting part was attached.

Here, the material of the die is a two-phase stainless steel having a mixed composition of an austenite phase and a ferrite phase, a material having a coefficient of thermal expansion of 2 × 10 ⁻⁵ (° C. ⁻¹ ) or less, and forced in an electrolyte aqueous solution. A material having corrosion resistance substantially equivalent to that of SUS316 was used in the corrosion test. In addition, a corrosion-resistant material that does not cause pitting at the gas-liquid interface even when immersed in a mixed solution of dichloromethane, methanol, and water for 3 months was used. Furthermore, the surface of the cellulose triacetate solution was kept constant by grinding the one that was aged for one month or more after casting. The finishing accuracy of the wetted surface of the casting die is 1 μm or less in terms of surface roughness, the straightness is 1 μm / m or less in any direction, and the clearance of the slit can be adjusted from 0.5 mm to 3.5 mm by automatic adjustment. Met. About the corner | angular part of the liquid-contact part of die-tip tip, it processed so that R might be 50 micrometers or less over the slit full width. The shear rate inside the die was in the range of 1 (1 / sec) to 5000 (1 / sec).

Furthermore, in order to prevent the dope flowing out from the slit end of the die from locally drying and solidifying, a mixed solvent (sample 080), which is a solvent for solubilizing the dope, is applied to the gas-liquid interface between the bead end and the slit. It was supplied at 0.5 cc / min on one side. The pulsation rate of the pump supplying this mixed liquid was 5% or less. In addition, the pressure on the back of the bead was reduced by 50 Pa using a vacuum chamber attached to the die. The edge suction air volume was appropriately adjusted in the range of 30 L / min to 40 L / min.

Cellulose triacetate film sample, except that the dope sample 001A-2 was used using the single layer casting die described above and the casting speed was 100 m / min in order to suppress the occurrence of irregularities in the film surface. Film formation was performed under the same conditions as 101-12 to obtain cellulose triacetate film samples 101-52. This cellulose triacetate film sample 10
1-52 performed the same evaluation as the film sample 101-12. The cellulose triacetate film sample 101-52 contained 4.0% by mass of retardation control agent A (trimethylolpropane triacetate).

The obtained cellulose triacetate film sample 101-52 has a solution stability of A, a film surface shape of A, a film tear test of 15 g, and a film folding test of 7
It was 0 times, and the heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0
. The content of Ca was less than 0.05% by mass, Ca was less than 0.05% by mass, and Mg was less than 0.01% by mass. The thickness of the cellulose triacetate film was 80 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 101-52 has a haze of 0.3% and a transparency (transparency) of 92.2.
%, Slope width is 19.7 nm, limit wavelength is 392.5 nm, absorption edge is 374.0 nm, 38
Absorption at 0 nm is 2.1%, Re is 1.1 nm, Rth is 49 nm, molecular orientation axis is 1.4 °, elastic modulus is 3.52 GPa in the longitudinal direction, 3.45 GPa in the width direction, tensile strength Is 140 MPa in the longitudinal direction and 141 MPa in the width direction, and the elongation is 41% in the longitudinal direction and 4 in the width direction.
8%, the Kishimi value (static friction coefficient) is 0.64, and the Kishimi value (dynamic friction coefficient) is 0.51.
Alkaline hydrolyzability is A, curl value is -0.4 at 25% RH, 1.
6. The moisture content is 1.4% by mass, the residual solvent amount is 0.3% by mass, the moisture permeability coefficient is 1525 g / (m ² · day), and the thermal shrinkage is −0.10% in the longitudinal direction. And the width direction was -0.09%. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.0.
2 mm to 0.05 mm is less than 10/3 m, 0.05 to 0.1 mm is less than 5/3 m, 0.
There was no more than 1 mm. These had excellent properties for optical applications. Further, some adhesion after application was observed, but it was at a level that was not problematic for practical use (Δ), and the moisture permeability was good (◯).

Next, a cellulose triacetate film sample 101-62 was produced. Retardation control agent A was dissolved in Sample 080 (mixed solvent) to obtain a solution. This solution was mixed with sample 002-2 being fed in-line via a static mixer. Hereinafter, this dope is referred to as a dope sample 002A-2. The retardation control agent A (trimethylolpropane triacetate) was adjusted to 4.0% by mass in the form of a film. Except having used dope sample 002A-2 using the casting die for single layers, it formed into the film on the same conditions as the cellulose triacetate film sample 101-22, and performed the same evaluation as the film sample 101-12.

  The obtained cellulose triacetate film sample 101-62 has a solution stability of A, a film surface shape of A, a film tear test of 16 g, a film folding resistance test of 73 times, and a moisture heat resistance of A And all were excellent. The amount of residual acetic acid is less than 0.01% by mass, Ca is less than 0.05% by mass, Mg is less than 0.01% by mass, and the thickness of the cellulose triacetate film is 80 μm ± It was 1.5 μm. At this time, for each of the top, middle portion, and last in the length direction, further evaluation of both end portions and the center portion in the width direction was performed, and the data confirmed that the error was 0.2% or less.

The film sample 101-62 has a haze of 0.3% and a transparency (transparency) of 92.1.
%, The slope width is 19.5 nm, the critical wavelength is 392.4 nm, the absorption edge is 374.2 nm, 38
Absorption at 0 nm is 2.0%, Re is 1.0 nm, Rth is 49 nm, molecular orientation axis is 1.4 °, elastic modulus is 3.58 GPa in the longitudinal direction, 3.41 GPa in the width direction, tensile strength Is 140 MPa in the longitudinal direction and 139 MPa in the width direction, and the elongation is 42% in the longitudinal direction and 4 in the width direction.
9%, the Kishimi value (static friction coefficient) is 0.64, and the Kishimi value (dynamic friction coefficient) is 0.52.
Alkaline hydrolyzability is A, curl value is -0.5 at 25% RH, 1.
It was 8. The moisture content is 1.4% by mass, the residual solvent amount is 0.3% by mass, the moisture permeability coefficient is 1531 g / (m ² · day), and the thermal shrinkage is −0.09% in the longitudinal direction. And the width direction was -0.09%. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.0.
2 mm to 0.05 mm is less than 10/3 m, 0.05 to 0.1 mm is less than 5/3 m, 0.
There was no more than 1 mm. These had excellent properties for optical applications. Further, some adhesion after application was observed, but it was at a level that was not problematic for practical use (Δ), and the moisture permeability was good (◯).

Next, a cellulose triacetate film sample 101-72 was prepared. Retardation control agent A and hydrophobizing agent (benzenesulfonanilide) sample 080 (mixed solvent)
To give a solution. This solution was mixed with sample 001-2 being fed in-line via a static mixer. Hereinafter, this dope is referred to as a dope sample 030A-2. The retardation control agent A (trimethylolpropane triacetate) was adjusted to 4.0% by mass in the film form and the hydrophobizing agent to 1% by mass. Except having used dope sample 030A-2 using the casting die for single layers, it formed into the film on the same conditions as the cellulose triacetate film sample 101-32, and performed the same evaluation as the film sample 101-12.

The obtained cellulose triacetate film sample 101-72 has a solution stability of A, a film surface shape of A, a film tear test of 15 g, and a film folding test of 7
It was twice, and the heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0
. The content of Ca was less than 0.05% by mass, Ca was less than 0.05% by mass, and Mg was less than 0.01% by mass. The thickness of the cellulose triacetate film was 80 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 101-72 has a haze of 0.3% and a transparency (transparency) of 92.0.
%, Slope width is 19.5 nm, limit wavelength is 392.7 nm, absorption edge is 374.2 nm, 38%
Absorption at 0 nm is 2.0%, Re is 1.2 nm, Rth is 51 nm, molecular orientation axis is 1.4 °, elastic modulus is 3.51 GPa in the longitudinal direction, 3.40 GPa in the width direction, tensile strength Is 140 MPa in the longitudinal direction and 141 MPa in the width direction, and the elongation is 43% in the longitudinal direction and 4 in the width direction.
9%, the Kishimi value (static friction coefficient) is 0.65, and the Kishimi value (dynamic friction coefficient) is 0.53
Alkaline hydrolyzability is A, curl value is -0.5 at 25% RH, 1.
6. The water content is 1.25% by mass, the residual solvent amount is 0.3% by mass,
The moisture permeability coefficient was 1110 g / (m ² · day), and the thermal shrinkage rate was −0.09% in the longitudinal direction and −0.08% in the width direction. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.
02mm ~ 0.05mm is less than 10 / 3m, 0.05-0.1mm is less than 5 / 3m, 0
. There was no more than 1 mm. These had excellent properties for optical applications. Although some adhesion after application was observed, it was at a level (Δ) that had no practical problem, and the moisture permeability was very good (良好).

Next, a cellulose triacetate film sample 101-82 was produced. Retardation control agent A and the hydrophobizing agent described above were dissolved in sample 080 (mixed solvent) to obtain a solution. This solution was mixed with sample 002-2 being fed in-line via a static mixer. Hereinafter, this dope is referred to as a dope sample 031A-2. The retardation control agent A (trimethylolpropane triacetate) was adjusted to 4.0% by mass in the form of a film and the hydrophobizing agent to 1% by mass. Dope sample 031A using a single layer casting die
Except having used 2, it formed into the film on the same conditions as the cellulose triacetate film sample 101-42, and performed the same evaluation as the film sample 101-12.

The obtained cellulose triacetate film sample 101-82 has a solution stability of A, a film surface shape of A, a film tear test of 15 g, and a film folding test of 7
Once, the heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0
. The content of Ca was less than 0.05% by mass, Ca was less than 0.05% by mass, and Mg was less than 0.01% by mass. The thickness of the cellulose triacetate film was 80 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 101-82 has a haze of 0.3% and a transparency (transparency) of 92.0.
%, Slope width is 19.4 nm, limit wavelength is 392.4 nm, absorption edge is 374.1 nm, 38%
Absorption at 0 nm is 1.9%, Re is 0.8 nm, Rth is 48 nm, molecular orientation axis is 1.5 °, elastic modulus is 3.58 GPa in the longitudinal direction, 3.4 GPa in the width direction, tensile strength The longitudinal direction is 137 MPa, the width direction is 141 MPa, the elongation is 43% in the longitudinal direction, and the width direction is 49%.
%, The kishimi value (static friction coefficient) is 0.65, the kishimi value (dynamic friction coefficient) is 0.52,
Alkaline hydrolyzability is A, curl value is -0.4 at 25% RH, 1.7 when wet.
Met. The moisture content is 1.23% by mass, the residual solvent amount is 0.3% by mass, the moisture permeability coefficient is 1118 g / (m ² · day), and the thermal shrinkage is −0.09% in the longitudinal direction. And the width direction was -0.08%. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.0.
2 mm to 0.05 mm is less than 10/3 m, 0.05 to 0.1 mm is less than 5/3 m, 0.
There was no more than 1 mm. These had excellent properties for optical applications. Although some adhesion after application was observed, it was at a level (Δ) that had no practical problem, and the moisture permeability was very good (良好).

Next, a cellulose triacetate film sample 102-52 was produced. Using a single layer casting die, the thickness of the product film is set to 40 μm, the casting speed is set to 100 m / min in order to suppress the occurrence of irregularities in the surface of the film, and the retardation control agent A (trimethylolpropane) is used. Triacetate) concentration of 3.0% by mass in the form of film 00
Except using 1A-2, it formed into the film on the same conditions as the cellulose triacetate film sample 102-22, and evaluated on the same conditions as the film sample 101-12.

The obtained cellulose triacetate film sample 102-52 has a solution stability of A, a film surface shape of A, and a film tear test of 11 g.
It was 29 times, the heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is
The content of Ca was less than 0.01% by mass, Ca was less than 0.05% by mass and Mg was less than 0.01% by mass. The thickness of the cellulose triacetate film was 40 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 102-52 has a haze of 0.3% and a transparency (transparency) of 92.3.
%, The slope width is 19.6 nm, the limit wavelength is 392.5 nm, the absorption edge is 374.0 nm, 38
Absorption at 0 nm is 2.3%, Re is 0.9 nm, Rth is 50 nm, molecular orientation axis is 1.5 °, elastic modulus is 3.54 GPa in the longitudinal direction, 3.44 GPa in the width direction, tensile strength The longitudinal direction is 138 MPa, the width direction is 141 MPa, the elongation is 43% in the longitudinal direction, and the width direction is 4%.
9%, the Kishimi value (static friction coefficient) is 0.63, and the Kishimi value (dynamic friction coefficient) is 0.51.
Alkaline hydrolyzability is A, curl value is -0.3 at 25% RH, 2.
It was 8. The moisture content is 1.20% by mass, the residual solvent amount is 0.19% by mass, the moisture permeability coefficient is 2524 g / (m ² · day), and the thermal shrinkage is −0.08% in the longitudinal direction. And the width direction was -0.08%. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0
. 02 mm to 0.05 mm is less than 10/3 m, 0.05 to 0.1 mm is less than 5/3 m,
There was no more than 0.1 mm. These had excellent properties for optical applications. Moreover, although adhesion after application was slightly observed, it was a level (Δ) having no practical problem, and the water vapor transmission rate was slightly high (Δ) with no practical problem.

Next, a cellulose triacetate film sample 102-62 was prepared. The thickness of the product film is 40 μm using a single layer casting die, the casting speed is 100 m / min in order to suppress unevenness in the surface of the film, and the retardation control agent A (trimethylolpropane) is used. Triacetate) concentration of 3.0% by weight in the form of film 0
Except using 02A-2, it formed into the film on the same conditions as the cellulose triacetate film sample 102-22, and performed the same evaluation as the film sample 101-12.

The obtained cellulose triacetate film sample 102-62 has a solution stability of A, a film surface shape of A, and a film tear test of 11 g.
It was 31 times, the heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is
The content of Ca was less than 0.01% by mass, Ca was less than 0.05% by mass and Mg was less than 0.01% by mass. The thickness of the cellulose triacetate film was 40 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 102-62 has a haze of 0.3% and a transparency (transparency) of 92.4.
%, Slope width is 19.5 nm, limit wavelength is 392.8 nm, absorption edge is 374.2 nm, 38%
Absorption at 0 nm is 2.4%, Re is 0.9 nm, Rth is 50 nm, molecular orientation axis is 1.4 °, elastic modulus is 3.53 GPa in the longitudinal direction, 3.42 GPa in the width direction, tensile strength The longitudinal direction is 138 MPa, the width direction is 140 MPa, the elongation is 43% in the longitudinal direction, and the width direction is 4
9%, the Kishimi value (static friction coefficient) is 0.65, the Kishimi value (dynamic friction coefficient) is 0.5,
Alkaline hydrolyzability is A, curl value is -0.4 at 25% RH, 3.1 when wet
Met. The water content is 1.21% by mass, the residual solvent amount is 0.19% by mass,
The moisture permeability coefficient was 2531 g / (m ² · day), and the thermal shrinkage rate was −0.08% in the longitudinal direction and −0.09% in the width direction. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.
02mm ~ 0.05mm is less than 10 / 3m, 0.05-0.1mm is less than 5 / 3m, 0
. There was no more than 1 mm. These had excellent properties for optical applications. Moreover, although adhesion after application was slightly observed, it was a level (Δ) having no practical problem, and the water vapor transmission rate was slightly high (Δ) with no practical problem.

Next, a cellulose triacetate film sample 102-72 was prepared. Using a single-layer casting die, the thickness of the product film is 40 μm, the casting speed is 100 m / min, and the concentration of retardation control agent A (trimethylolpropane triacetate) is 3.0% by mass in the form of a film. The hydrophobizing agent (benzenesulfonanilide) was formed under the same conditions as the cellulose triacetate film sample 102-32 except that 1% by weight of the dope sample 030A-2 was used, and the same evaluation as the film sample 101-12 was performed. It was.

The obtained cellulose triacetate film sample 102-72 has a solution stability of A, a film surface shape of A, and a film tear test of 11 g.
It was 28 times, the heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is
The content of Ca was less than 0.01% by mass, Ca was less than 0.05% by mass and Mg was less than 0.01% by mass. The thickness of the cellulose triacetate film was 40 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 102-72 has a haze of 0.3% and a transparency (transparency) of 92.3.
%, Slope width is 19.6 nm, limit wavelength is 392.7 nm, absorption edge is 374.2 nm, 38%
Absorption at 0 nm is 2.2%, Re is 0.8 nm, Rth is 48 nm, molecular orientation axis is 1.4 °, elastic modulus is 3.53 GPa in the longitudinal direction, 3.4 GPa in the width direction, tensile strength Is 141 MPa in the longitudinal direction and 142 MPa in the width direction, and the elongation is 43% in the longitudinal direction and 49 in the width direction.
%, The kishimi value (static friction coefficient) is 0.62, the kishimi value (dynamic friction coefficient) is 0.51,
Alkaline hydrolyzability is A, curl value is -0.2 at 25% RH, 3.2 when wet
Met. The water content is 1.11% by mass, the residual solvent amount is 0.19% by mass,
The moisture permeability coefficient was 1245 g / (m ² · day), and the thermal shrinkage rate was −0.07% in the longitudinal direction and −0.09% in the width direction. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.
02mm ~ 0.05mm is less than 10 / 3m, 0.05-0.1mm is less than 5 / 3m, 0
. There was no more than 1 mm. These had excellent properties for optical applications. Further, although some adhesion after application was observed, it was at a level (Δ) that had no problem in practical use, and the moisture permeability was very low (Excellent).

Next, a cellulose triacetate film sample 102-82 was produced. Using a single-layer casting die, the thickness of the product film is 40 μm, the casting speed is 100 m / min, and the concentration of retardation control agent A (trimethylolpropane triacetate) is 3.0% by mass in film form. A film was formed under the same conditions as the cellulose triacetate film sample 102-42 except that a dope sample 031A-2 having a hydrophobizing agent (benzenesulfonanilide) of 1% by mass was used, and the same evaluation as the film sample 101-12 was performed. .

The obtained cellulose triacetate film sample 102-82 has a solution stability of A, a film surface shape of A, and a film tear test of 11 g.
It was 34 times, the heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is
The content of Ca was less than 0.01% by mass, Ca was less than 0.05% by mass and Mg was less than 0.01% by mass. The thickness of the cellulose triacetate film was 40 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 102-82 has a haze of 0.3% and a transparency (transparency) of 92.3.
%, Slope width is 19.6 nm, limit wavelength is 392.7 nm, absorption edge is 374.2 nm, 38%
Absorption at 0 nm is 2.2%, Re is 0.6 nm, Rth is 52 nm, molecular orientation axis is 1.4 °, elastic modulus is 3.53 GPa in the longitudinal direction, 3.41 GPa in the width direction, tensile strength Is 142 MPa in the longitudinal direction and 141 MPa in the width direction. The elongation is 43% in the longitudinal direction and 4 in the width direction.
9%, the Kishimi value (static friction coefficient) is 0.65, and the Kishimi value (dynamic friction coefficient) is 0.51.
Alkaline hydrolyzability is A, curl value is −0.4 at 25% RH, 3.
4. The moisture content is 1.09% by mass, the residual solvent amount is 0.20% by mass, the moisture permeability coefficient is 234 g / (m ² · day), and the thermal shrinkage is −0.08% in the longitudinal direction. And the width direction was -0.09%. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.
02mm ~ 0.05mm is less than 10 / 3m, 0.05-0.1mm is less than 5 / 3m, 0
. There was no more than 1 mm. These had excellent properties for optical applications. Further, although some adhesion after application was observed, it was at a level (Δ) that had no problem in practical use, and the moisture permeability was very low (Excellent).

Retardation control agent B (TPP (triphenyl phosphate) + BDP (biphenyl diphenyl phosphate) (TPP / BDP = 2/1)) and ultraviolet absorber d (2-hydroxy-4-benzyloxybenzophenone / 2,4-bis ( (Benzyloxy) benzophenone = 3/1) was dissolved in sample 080 (mixed solvent) to give a solution. This solution was mixed with sample 001-2 being fed in-line via a static mixer. This dope below is referred to as a dope sample 001B-2. The concentration of the retardation control agent B was adjusted to 1.0 mass% in the film form, and the ultraviolet absorber d was adjusted to 0.5 mass%. Cellulose triacetate film sample 103-12, except that sample 001B-2 was used using a single layer casting die and the casting speed was 100 m / min in order to suppress the occurrence of irregularities on the film surface. Film formation under the same conditions as in cellulose triacetate film sample 1
03-52 was obtained. In addition, this cellulose triacetate film sample 103-52 is
The same evaluation as film sample 101-12 was performed.

The obtained cellulose triacetate film sample 103-52 has a solution stability of A, a film surface shape of A, a film tear test of 11 g, and a film folding test of 7
It was 5 times, and the heat and humidity resistance was A, all of which were excellent. The amount of residual acetic acid is 0
. The content of the cellulose triacetate film was 60 μm ± 1.5 μm over the entire area. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 103-52 has a haze of 0.3% and a transparency (transparency) of 92.4.
%Met. Re is 10.2 nm, Rth is 80 nm, molecular orientation axis is 1.4 °, elastic modulus is 3.57 GPa in the longitudinal direction, 3.41 GPa in the width direction, and tensile strength is 141 M in the longitudinal direction.
Pa, 140 MPa in the width direction, 44% in the longitudinal direction and 48% in the width direction, 0.63 for the kishimi (static friction coefficient), 0.52 for the kishimi (dynamic friction coefficient), alkaline hydrolysis The curability value was -0.4 at 25% RH and 2.2 when wet. The moisture content is 1.37% by mass, the residual solvent amount is 0.24% by mass, and the moisture permeability coefficient is 18%.
22 g / (m ² · day), heat shrinkage rate is −0.10% in the longitudinal direction and −0.09 in the width direction
%Met. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.02 mm to 0.00.
05 mm was less than 10/3 m, 0.05-0.1 mm was less than 5/3 m, and there was no more than 0.1 mm. These had excellent properties for optical applications. Moreover, although adhesion after application was slightly observed, it was a level (Δ) having no practical problem, and the water vapor transmission rate was slightly high (Δ) with no practical problem.

Next, a cellulose triacetate film sample 103-6 was prepared. Retardation control agent B (TPP (triphenyl phosphate) + BDP (biphenyl diphenyl phosphate) (TPP / BDP = 2/1)) and UV absorber d (2-hydroxy-4-
Benzyloxybenzophenone / 2,4-bis (benzyloxy) benzophenone = 3 /
1) was dissolved in Sample 080 (mixed solvent) to prepare a solution. This solution was mixed with sample 002-2 being fed in-line via a static mixer. Hereinafter, this dope is added as a dope sample 0.
This is referred to as 02B-2. In addition, the density | concentration of the retardation control agent B is 1.0 in a film form.
It adjusted so that it might become mass%, and the ultraviolet absorber d was adjusted to 0.5 mass%. Except having used dope sample 002B-2 using the casting die for single layers, it formed into the film on the same conditions as cellulose triacetate film sample 103-22, and performed the same evaluation as film sample 101-12.

The obtained cellulose triacetate film sample 103-62 has a solution stability of A, a film surface shape of A, and a film tear test of 12 g.
It was 4 times, and the heat and humidity resistance was A, all of which were excellent. The amount of residual acetic acid is 0
. The content of the cellulose triacetate film was 60 μm ± 1.5 μm over the entire area. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 103-62 has a haze of 0.3% and a transparency (transparency) of 92.4.
%Met. Re is 10.5 nm, Rth is 80 nm, molecular orientation axis is 1.4 °, elastic modulus is 3.51 GPa in the longitudinal direction, 3.41 GPa in the width direction, and tensile strength is 141 M in the longitudinal direction.
Pa, 141 MPa in the width direction, 44% in the longitudinal direction, 48% in the width direction, 0.65 for the kishimi (static friction coefficient), 0.53 for the kishimi (dynamic friction coefficient), alkaline hydrolysis The curability was -0.5 at 25% RH and 2.4 when wet. The moisture content is 1.36% by mass, the residual solvent amount is 0.25% by mass, and the moisture permeability coefficient is 18%.
05 g / (m ² · day), heat shrinkage rate is −0.10% in the longitudinal direction and −0.10 in the width direction
%Met. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.02 mm to 0.00.
05 mm was less than 10/3 m, 0.05-0.1 mm was less than 5/3 m, and there was no more than 0.1 mm. These had excellent properties for optical applications. Moreover, although adhesion after application was slightly observed, it was a level (Δ) having no practical problem, and the water vapor transmission rate was slightly high (Δ) with no practical problem.

Next, a cellulose triacetate film sample 103-72 was prepared. Retardation control agent B (TPP (triphenyl phosphate) + BDP (biphenyl diphenyl phosphate) (TPP / BDP = 2/1)), hydrophobizing agent (benzenesulfonanilide), and UV absorber d (2-hydroxy-4-benzyl) Oxybenzophenone / 2,4-bis (benzyloxy) benzophenone = 3/1) was dissolved in sample 080 (mixed solvent) to prepare a solution. This solution was mixed with sample 001-2 being fed in-line via a static mixer. Hereinafter, this dope is referred to as a dope sample 030B-2. Retardation control agent B is 1.0% by mass in film form, hydrophobizing agent is 1% by mass, and ultraviolet absorber d is 0%.
. It adjusted so that it might become 5 mass%. Dope sample 030 using a single layer casting die
Except using B-2, it formed into the film on the same conditions as the cellulose triacetate film sample 103-32, and performed the same evaluation as the film sample 101-12.

The obtained cellulose triacetate film sample 103-72 has a solution stability of A, a film surface shape of A, a film tear test of 11 g, and a film folding test of 7
It was 3 times, and the heat and humidity resistance was A, all of which were excellent. The amount of residual acetic acid is 0
. The content of the cellulose triacetate film was 60 μm ± 1.5 μm over the entire area. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 103-72 has a haze of 0.3% and a transparency (transparency) of 92.5.
%Met. Re is 9.7 nm, Rth is 79 nm, molecular orientation axis is 1.3 °, elastic modulus is 3.53 GPa in the longitudinal direction, 3.40 GPa in the width direction, and tensile strength is 143 MP in the longitudinal direction.
a, 140 MPa in the width direction, 43% in the longitudinal direction and 48% in the width direction, 0.64 for the kishimi value (static friction coefficient), 0.52 for the kishimi value (dynamic friction coefficient), alkaline hydrolysis The curability was -0.4 at 25% RH and 2.4 when wet. Also,
The water content is 1.32% by mass, the residual solvent amount is 0.25% by mass, and the moisture permeability coefficient is 117.
4 g / (m ² · day), thermal shrinkage is −0.11% in the longitudinal direction and −0.08% in the width direction
Met. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.02 mm to 0.0.
5 mm was less than 10/3 m, 0.05 to 0.1 mm was less than 5/3 m, and there was no more than 0.1 mm. These had excellent properties for optical applications. Further, although some adhesion after application was observed, it was at a level (Δ) that had no problem in practical use, and the moisture permeability was very low (Excellent).

Next, a cellulose triacetate film sample 103-82 was produced. Retardation control agent B (TPP (triphenyl phosphate) + BDP (biphenyl diphenyl phosphate) (TPP / BDP = 2/1)), the above-described hydrophobizing agent, and the above-described ultraviolet absorber d in sample 080 (mixed solvent) Dissolved to make a solution. This solution was mixed with sample 002-2 being fed in-line via a static mixer. Hereinafter, this dope is referred to as a dope sample 031B-2. The retardation control agent B was adjusted to 1.0% by mass in the film form, 1% by mass of the hydrophobizing agent, and 0.5% by mass of the ultraviolet absorber d. Except having used sample 031B using the casting die for single layers, it formed into the film on the same conditions as the cellulose triacetate film sample 103-42, and performed the same evaluation as the film sample 101-12.

The obtained cellulose triacetate film sample 103-82 has a solution stability of A, a film surface shape of A, a film tear test of 11 g, and a film folding test of 7
It was 4 times, and the heat and humidity resistance was A, all of which were excellent. The amount of residual acetic acid is 0
. The content of the cellulose triacetate film was 60 μm ± 1.5 μm over the entire area. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 103-82 has a haze of 0.3% and a transparency (transparency) of 92.5.
%Met. Re is 9.8 nm, Rth is 80 nm, molecular orientation axis is 1.4 °, elastic modulus is 3.51 GPa in the longitudinal direction, 3.43 GPa in the width direction, and tensile strength is 141 MP in the longitudinal direction.
a, 142 MPa in the width direction, 43% in the longitudinal direction, 49% in the width direction, 0.63 for the kishimi (static friction coefficient), 0.52 for the kishimi (dynamic friction coefficient), alkaline hydrolysis The curability was -0.4 at 25% RH and 2.2 when wet. Also,
The water content is 1.29% by mass, the residual solvent amount is 0.25% by mass, and the moisture permeability coefficient is 116.
8g / (m ² · day), thermal shrinkage is −0.09% in the longitudinal direction and −0.08% in the width direction
Met. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.02 mm to 0.0.
5 mm was less than 10/3 m, 0.05 to 0.1 mm was less than 5/3 m, and there was no more than 0.1 mm. These had excellent properties for optical applications. Further, although some adhesion after application was observed, it was at a level (Δ) that had no problem in practical use, and the moisture permeability was very low (Excellent).

Retardation control agent N (N, N ′, N ″ -tri-m-toluyl-1,3,5-triazine-2,4,6-triamine) was dissolved in sample 080 (mixed solvent) did. This solution was mixed with sample 001-2 being fed in-line via a static mixer. Hereinafter, this dope is referred to as a dope sample 001C-2. In addition, the retardation control agent N was adjusted and mixed so that it might become 3.0 mass% in a film form. Sample 001C-2 was used using a single-layer casting die, the thickness of the product film was 80 μm, and the casting speed was 100 m / min in order to suppress the occurrence of irregularities in the film surface, Film formation was performed under the same conditions as for cellulose triacetate film sample 104-12. In the following description, this film is referred to as cellulose triacetate film sample 104-5. Cellulose triacetate film sample 104-52 was evaluated the same as film sample 101-12.

The obtained cellulose triacetate film sample 104-52 has a solution stability of A, a film surface shape of A, and a film tear test of 15 g.
Once, the heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0
. The content of Ca was less than 0.05% by mass, Ca was less than 0.05% by mass, and Mg was less than 0.01% by mass. The thickness of the cellulose triacetate film was 80 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 104-52 has a haze of 0.3% and a transparency (transparency) of 92.4.
%Met. Re is 41 nm, Rth is 174 nm, the molecular orientation axis is 1.8 °, the elastic modulus is 3.53 GPa in the longitudinal direction, 3.44 GPa in the width direction, and the tensile strength is 146 MP in the longitudinal direction.
a, 141 MPa in the width direction, 43% in the longitudinal direction and 49% in the width direction, 0.61 for the kishimi (static friction coefficient), 0.52 for the kishimi (dynamic friction coefficient), alkaline hydrolysis The curability was -0.4 at 25% RH and 1.5 when wet. Also,
The water content is 1.44% by mass, the residual solvent amount is 0.33% by mass, and the moisture permeability coefficient is 152.
0 g / (m ² · day), thermal shrinkage is −0.08% in the longitudinal direction and −0.10% in the width direction
Met. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.02 mm to 0.0.
5 mm was less than 10/3 m, 0.05 to 0.1 mm was less than 5/3 m, and there was no more than 0.1 mm. These had excellent properties for optical applications. Further, some adhesion after application was observed, but it was at a level that was not problematic for practical use (Δ), and the moisture permeability was good (◯).

Next, a cellulose triacetate film sample 104-62 was prepared. Retardation control agent N (N, N ′, N ″ -tri-m-toluyl-1,3,5-triazine-2,
4,6-triamine) was dissolved in Sample 080 (mixed solvent) to prepare a solution. This solution was mixed with sample 002-2 being fed in-line via a static mixer. Hereinafter, this dope is referred to as a dope sample 002C-2. In addition, it adjusted so that the density | concentration of the retardation control agent N might be 3.0 mass% with a film form. Cellulose triacetate except that sample 002C was used using a single layer casting die, the product film thickness was 80 μm, and the casting speed was 100 m / min in order to suppress the occurrence of irregularities on the film surface. Film formation was performed under the same conditions as the film sample 104-22, and the same evaluation as the film sample 101-12 was performed.

The obtained cellulose triacetate film sample 104-62 has a solution stability of A, a film surface shape of A, a film tear test of 15 g, and a film folding test of 7
Once, the heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0
. The content of Ca was less than 0.05% by mass, Ca was less than 0.05% by mass, and Mg was less than 0.01% by mass. The thickness of the cellulose triacetate film was 80 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 104-62 has a haze of 0.3% and a transparency (transparency) of 92.4.
%Met. Re is 40 nm, Rth is 173 nm, molecular orientation axis is 1.8 °, elastic modulus is 3.51 GPa in the longitudinal direction, 3.42 GPa in the width direction, and tensile strength is 141 MP in the longitudinal direction.
a, 142 MPa in the width direction, 43% in the longitudinal direction, 48% in the width direction, 0.65 for the kishimi value (static friction coefficient), 0.53 for the kishimi value (dynamic friction coefficient), alkaline hydrolysis The property was A, and the curl value was −0.7 at 25% RH, and 1.9 when wet. Also,
The water content is 1.43 mass%, the residual solvent amount is 0.34 mass%, and the moisture permeability coefficient is 151.
9 g / (m ² · day), heat shrinkage rate is −0.09% in the longitudinal direction and −0.09% in the width direction
Met. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.02 mm to 0.0.
5 mm was less than 10/3 m, 0.05 to 0.1 mm was less than 5/3 m, and there was no more than 0.1 mm. These had excellent properties for optical applications. Further, some adhesion after application was observed, but it was at a level that was not problematic for practical use (Δ), and the moisture permeability was good (◯).

Next, a cellulose triacetate film sample 104-72 was prepared. Retardation control agent N (N, N ′, N ″ -tri-m-toluyl-1,3,5-triazine-2,
4,6-triamine) and a hydrophobizing agent (benzenesulfonanilide) were dissolved in Sample 080 (mixed solvent) to prepare a solution. This solution was mixed with sample 001-2 being fed in-line via a static mixer. Hereinafter, this dope is referred to as a dope sample 030C-2. In addition,
Retardation control agent N was adjusted to be 3.0% by mass in the film form and 1% by mass of the hydrophobizing agent. Sample 030C-2 was used using a single layer casting die, the thickness of the product film was 80 μm, and the casting speed was 100 m / min to suppress the occurrence of irregularities on the film surface, Film formation was performed under the same conditions as the cellulose triacetate film sample 104-32, and the same evaluation as the film sample 101-12 was performed.

The obtained cellulose triacetate film sample 104-72 has a solution stability of A, a film surface shape of A, and a film tear test of 15 g.
Once, the heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0
. The content of Ca was less than 0.05% by mass, Ca was less than 0.05% by mass, and Mg was less than 0.01% by mass. The thickness of the cellulose triacetate film was 80 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 104-72 has a haze of 0.3% and a transparency (transparency) of 92.4.
%Met. Re is 42 nm, Rth is 174 nm, the molecular orientation axis is 1.8 °, the elastic modulus is 3.53 GPa in the longitudinal direction, 3.48 GPa in the width direction, and the tensile strength is 144 MP in the longitudinal direction.
a, 142 MPa in the width direction, 42% in the longitudinal direction, 49% in the width direction, 0.63 for the kishimi (static friction coefficient), 0.51 for the kishimi (dynamic friction coefficient), alkaline hydrolysis The curability value was -0.6 at 25% RH and 1.6 when wet. Also,
The water content is 1.40% by mass, the residual solvent amount is 0.33% by mass, and the moisture permeability coefficient is 110.
8g / (m ² · day), thermal shrinkage is −0.09% in the longitudinal direction and −0.11% in the width direction
Met. The foreign matter had a lint of less than 5 pieces / m. The bright spot is 0.02 mm to 0.0.
5 mm was less than 10/3 m, 0.05 to 0.1 mm was less than 5/3 m, and there was no more than 0.1 mm. These had excellent properties for optical applications. Further, although some adhesion after application was observed, it was at a level (Δ) that had no problem in practical use, and the moisture permeability was very low (Excellent).

Next, a cellulose triacetate film sample 104-82 was produced. Retardation control agent N (N, N ′, N ″ -tri-m-toluyl-1,3,5-triazine-2,
4,6-triamine) and the hydrophobizing agent described above were dissolved in Sample 080 (mixed solvent) to form a solution. This solution was mixed with sample 002-2 being fed in-line via a static mixer. Hereinafter, this dope is referred to as a dope sample 031C-2. The retardation control agent N was adjusted to 3.0% by mass in the film form and the hydrophobizing agent to 1% by mass. Sample 031C-2 was used using a single layer casting die, except that the thickness of the product film was 80 μm, and the casting speed was 100 m / min in order to suppress the occurrence of irregularities on the film surface. Film formation was performed under the same conditions as the cellulose triacetate film sample 104-42, and the same evaluation as the film sample 101-12 was performed.

The obtained cellulose triacetate film sample 104-82 has a solution stability of A, a film surface shape of A, a film tear test of 16 g, and a film folding test of 7
It was twice, and the heat and humidity resistance was A, and all were excellent. The amount of residual acetic acid is 0
. The content of Ca was less than 0.05% by mass, Ca was less than 0.05% by mass, and Mg was less than 0.01% by mass. The thickness of the cellulose triacetate film was 80 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.2% or less.

The film sample 104-82 has a haze of 0.3% and a transparency (transparency) of 92.5.
%Met. Re is 41 nm, Rth is 173 nm, molecular orientation axis is 1.8 °, elastic modulus is 3.53 GPa in the longitudinal direction, 3.44 GPa in the width direction, and tensile strength is 141 MP in the longitudinal direction.
a, the width direction is 142 MPa, the elongation is 43% in the longitudinal direction, and the width direction is 48%, the kishimi value (static friction coefficient) is 0.62, the kishimi value (dynamic friction coefficient) is 0.51, and alkaline hydrolysis The property was A, and the curl value was −0.4 at 25% RH and 1.7 when wet. Also,
The water content is 1.38% by mass, the residual solvent amount is 0.33% by mass, and the moisture permeability coefficient is 110.
7 g / (m ² · day), thermal shrinkage is −0.10% in the longitudinal direction and −0.11% in the width direction
It was <according to Excel data>. The foreign matter had a lint of less than 5 pieces / m. The bright spots were 0.02 mm to 0.05 mm less than 10/3 m, 0.05 to 0.1 mm less than 5/3 m, and 0.1 mm or more. These had excellent properties for optical applications. Further, although some adhesion after application was observed, it was at a level (Δ) with no practical problem, and the moisture permeability was very good (（).

  For comparison, Example 3 shown below was performed. In (1-1) of sample 101-1 of Example 1, cellulose triacetate was substituted at a degree of substitution of 2.45, a viscosity average polymerization degree of 290, a water content of 0.5% by mass, and a viscosity of 6% by mass in a methylene chloride solution. A comparative cellulose triacetate film sample 301 was prepared in exactly the same manner as in Example 1 except that the powder was changed to powder having an average particle diameter of 1.3 mm and a standard deviation of 0.4 mm.

  When the sample 301 was evaluated according to the evaluation method of Example 1, it was as follows. Sample 301 had a solution stability of A, the film surface shape was B, the film tear test was 285 g, the film folding test was 86, the heat and humidity resistance was C, and Re was 16 nm and haze were 0.9%, which was inferior. The residual acetic acid amount is 0.04% by mass, Ca is 0.06% by mass, Mg is 0.02% by mass, the residual solvent is 0.04% by mass, and the water content is 2.6. It was the mass% (25 degreeC, 60% RH). The thickness of the cellulose triacetate film was 80 μm ± 1.5 μm over the entire region. At this time, for each of the top, middle portion and last in the length direction, both end portions and the center portion in the width direction were further evaluated, and the data confirmed that the error was 0.5% or less.

From the above, in the present invention, when the substitution degree of the hydroxyl group of cellulose acylate is small, the liquid stability is inferior, and it is clear that the film has a folding resistance test of 86, and the moist heat resistance is inferior to C. It is clear that cellulose acylate is useful.

In (1-1) of sample 101-1 of Example 1, cellulose triacetate was changed to the cellulose acylate of the present invention described below, and cellulose triacylate film samples 401 to 401 of the present invention were completely used in the same manner as in Example 1. 409 was produced.

When samples 401 to 409 were evaluated according to the evaluation method of Example 1, the solution stability, film surface, film tear test, film folding test, moisture heat resistance, Re, and A cellulose acylate solution and a film having haze could be obtained.

(Sample 401)
Cellulose triacetate (degree of substitution 2.60, viscosity average degree of polymerization 380, water content 0.4% by weight, viscosity 6% by weight in methylene chloride solution 360 mPa · s, average particle size 1.4
mm, with a standard deviation of 0.4 mm, residual acetic acid content of 0.01% by mass or less, and Ca is 0
. 01 mass%, Mg is 0.006 mass%, Fe is 0.05 ppm, and the 6-position acetyl group is 0.00.
89, 34% of the total acetyl, 14% by mass of acetone extracted, the ratio of the weight average molecular weight to the number average molecular weight is 1.4, the yellowness index is 0.4, the haze is 0.9, and the transparency is 92. 7%, Tg was 152 ° C., and the crystallization exotherm was 3.1 J / g).

(Sample 402)
Cellulose triacetate (substitution degree 2.83, viscosity average polymerization degree 350, water content 0.3% by mass, viscosity of 6% by mass in methylene chloride solution 350 mPa · s, average particle size 1.0
mm, standard deviation 0.3 mm, residual acetic acid content 0.01% by mass or less, Ca is 0
. 008 mass%, Mg is 0.004 mass%, Fe is 0.8 ppm, and the 6-position acetyl group is 0.00.
85, 30% of the total acetyl, 9% by mass of acetone extracted, the ratio of the weight average molecular weight to the number average molecular weight is 0.8, the yellowness index is 0.6, the haze is 0.06, and the transparency is 94. 2%, Tg of 155 ° C., and crystallization exotherm of 4.9 J / g) were used.

(Sample 403)
Cellulose triacetate (substitution degree 2.86, viscosity average polymerization degree 280, water content 0.4% by mass, viscosity of 6% by mass in methylene chloride solution 315 mPa · s, average particle size 1.2
mm, with a standard deviation of 0.4 mm, residual acetic acid content of 0.01% by mass or less, and Ca is 0
. 01 mass%, Mg 0.05 mass%, Fe 2 ppm, 6-position acetyl group is 0.94, 33% in total acetyl, acetone extract 6 mass%, ratio of weight average molecular weight to number average molecular weight Is 0.7, yellowness index is 1.0, haze is 0.4, transparency is 94.2%
, Tg was 162 ° C., and the crystallization exotherm was 5.8 J / g).

(Sample 404)
Cellulose acetate propionate (acetyl substitution degree 2.45, propionate substitution degree 0.25, total substitution degree 2.70, viscosity average polymerization degree 320, moisture content 0.3 mass%, 6 mass% in methylene chloride solution A powder having a viscosity of 275 mPa · s, an average particle diameter of 1.3 mm and a standard deviation of 0.4 mm, and the amount of residual acetic acid and the amount of propionic acid are both 0.05% by mass.
Hereinafter, Ca is 0.012 mass%, Mg is 0.07 mass%, Fe is 5 ppm, 6-position acetyl group and propionyl group are 0.70 and 0.17, respectively, 33% of all substituents, acetone extractables Is 7% by mass, the ratio of the weight average molecular weight to the number average molecular weight is 0.9, the yellowness index is 1.3, the haze is 0.2, the transparency is 93.6%, the Tg is 157 ° C., and the crystallization calorific value is 4.3 J / g) was used.

(Sample 405)
Cellulose acetate butyrate (acetyl substitution degree 2.39, butyrate substitution degree 0.4
5 with a total degree of substitution of 2.84, a viscosity average degree of polymerization of 340, a water content of 0.4% by weight, a viscosity of 6% by weight in a methylene chloride solution of 295 mPa · s, an average particle size of 1.3 mm and a standard deviation of 0.8. 4 mm powder, residual acetic acid amount and butanoic acid amount are both 0.03 mass% or less, Ca is 0.005 mass%, Mg is 0.004 mass%, Fe is 5 ppm, 6-position acetyl group and propionyl group The sum is 0.72 and 0.20, respectively, 32% of the total substituents, acetone extract is 14% by mass, the ratio of weight average molecular weight to number average molecular weight is 1.3, yellowness index is 0.9, haze Is 0.5, the transparency is 92.9%, the Tg is 153 ° C., and the crystallization exotherm is 3
. 9 J / g) was used.

(Sample 406)
Cellulose acetate propionate butyrate (acetyl substitution degree 2.46, propionate substitution degree 0.20, butyrate substitution degree 0.09, total substitution degree 2.75, viscosity average polymerization degree 390, water content 0.3 Viscosity 3% by weight, 6% by weight in methylene chloride solution 3
20 mPa · s, powder having an average particle diameter of 1.6 mm and a standard deviation of 0.5 mm, the amount of residual acetic acid and the amount of propionic acid and butanoic acid are both 0.03 mass% or less, Ca is 0.006 mass%, Mg is 0.005% by mass, Fe is 4 ppm, 6-position acetyl group, propionyl group and butyroyl group are 0.73, 0.7 and 0.7, respectively, 32% of all substituents, acetone extract is 6 % By weight, ratio of weight average molecular weight to number average molecular weight is 1.2, yellowness index is 0.7, haze is 0.4, transparency is 95.3%, Tg is 150 ° C., crystallization heating value is 3
. 7 J / g) was used.

(Sample 407)
Cellulose acetate propionate laurate (acetyl substitution degree 2.42, propionate substitution degree 0.18, laurate substitution degree 0.08, total substitution degree 2.68, viscosity average polymerization degree 320, water content 0.4 mass% , A viscosity of 6% by weight in methylene chloride solution 290
MPa · s, powder having an average particle diameter of 1.2 mm and a standard deviation of 0.4 mm, the amount of residual acetic acid, propionic acid and lauric acid are both 0.03% by mass or less, and Ca is 0.005% by mass.
, Mg is 0.003% by mass, Fe is 5 ppm, 6-position acetyl group, propionyl group and lauroyl group are 0.77, 0.08 and 0.04, respectively, 33% of all substituents, acetone extract is 7% % By weight, ratio of weight average molecular weight to number average molecular weight is 1.1, yellowness index is 0.9, haze is 0.6, transparency is 92.6%, Tg is 149 ° C., crystallization heating value is 4
. 4 J / g) was used.

(Sample 408)
Cellulose acetate valeroyl (acetyl substitution degree 2.58 and valeroyl substitution degree 0
. 20 with a total degree of substitution of 2.78, a viscosity average polymerization degree of 330, a water content of 0.3% by weight, a viscosity of 6% by weight in methylene chloride solution of 305 mPa · s, an average particle size of 1.3 mm and a standard deviation of 0.8. 4 mm powder, the amount of residual acetic acid and valeric acid are both 0.02% by mass or less, Ca is 0.006% by mass, Mg is 0.004% by mass, Fe is 3 ppm, 6-position acetyl group and valeroyl group are respectively 0.84 and 0.08, 33% of all substituents, 8% by mass of acetone extract, ratio of weight average molecular weight to number average molecular weight is 1.0, yellowness index is 0.7,
(Haze is 0.4, transparency is 93.8%, Tg is 150 ° C., crystallization heat generation is 4.6 J / g)
Was used.

(Sample 409)
Cellulose acetate benzoate (acetyl substitution degree 2.55, benzoyl substitution degree 0.10, total substitution degree 2.65, viscosity average polymerization degree 290, moisture content 0.4 mass%, viscosity of 6 mass% in methylene chloride solution) Powder having 320 mPa · s, average particle size of 1.5 mm and standard deviation of 0.4 mm, the amount of residual acetic acid and benzoic acid are both 0.03% by mass or less, Ca is 0.005% by mass, and Mg is 0.00%. 003 mass%, Fe 4 ppm, 6-position acetyl group and benzoic acid group are 0.82 and 0.06, respectively, 33% of all substituents, acetone extract 9 mass%
The ratio of the weight average molecular weight to the number average molecular weight is 1.3, the yellowness index is 0.5, the haze is 0.6, the transparency is 93.4%, the Tg is 153 ° C., and the crystallization calorific value is 5.2 J / g) was used.

(Sample 410)
Cellulose acetate propionate (acetyl substitution degree 1.9, propionate substitution degree 0.8, total substitution degree 2.70, viscosity average polymerization degree 260, water content 0.2 mass%, 6 mass% in methylene chloride solution The powder having a viscosity of 180 mPa · s, an average particle diameter of 1.2 mm and a standard deviation of 0.4 mm, the amount of residual acetic acid and propionic acid are both 0.05% by mass or less,
Ca is 0.015% by mass, Mg is 0.08% by mass, Fe is 0.5ppm, and the sum of the 6-position acetyl group and propionyl group is 0.3 and 0.57 groups, respectively, and the total substitution degree is 33%. The ratio of the weight average molecular weight to the number average molecular weight is 2.4, the yellowness index is 1.2, the haze is 0.2, and the transparency is 93.2%.

(Sample 411)
Cellulose acetate butyrate (acetyl substitution degree 1.0 and butyrate substitution degree 1.
The total substitution degree is 2.65, the water content is 0.3% by mass, the average particle size is 1.3 mm, and the standard deviation is 0.4 mm. The residual acetic acid amount and butanoic acid are both 0.3% by mass. Hereinafter, Ca is 0.0.
05 mass%, Mg is 0.004 mass%, Fe is 1.5 ppm, the sum of 6-position acetyl group and butyl group is 0.22 and 0.70 groups, respectively, the total substitution degree is 32%, and the weight average molecular weight The number average molecular weight ratio is 2.0, the yellowness index is 0.8, the haze is 0.4, and the transparency is 93.0%.

(Sample 412)
Cellulose acetate propionate (acetyl substitution degree 0.18, propionate substitution degree 2.47, total substitution degree 2.65, water content 0.3 mass%, average particle diameter 1.3 mm with standard deviation 0.8. 3 mm powder, the amount of residual acetic acid and propionic acid are both 0.2% by mass or less, Ca is 0.06% by mass, Mg is 0.04% by mass, Fe is 3 ppm, the total of 6-position acetyl group and propionyl group Are 0.08 and 0.84 groups, respectively, with a total substitution degree of 33%, a yellowness index of 0.6, a haze of 0.4, and a transparency of 93.1%.

The cellulose triacetate film sample 501 of the present invention was exactly the same as Example 2 except that methyl acetate, acetone, methanol, ethanol, and butanol were changed to the following in (2-1) of Sample 101-12 of Example 2. -521 were produced. In addition, the implementation scale was implemented with the scale from which a casting winding film length will be 1000 m.

When Samples 501 to 521 were evaluated according to the evaluation method of Example 1, Sample 101-12
As well as excellent solution stability, film surface, film tear test, film folding test,
It was a cellulose triacetate film having heat-and-moisture resistance, Re, and haze.

The ratio of the solvent used for each sample preparation is shown below in parts by mass.
Sample 501: methyl acetate / acetone / methanol / ethanol / propanol / butanol = 55/10/5/5/3/2.
Sample 502: methyl acetate / acetone / methanol / ethanol / propanol / butanol = 45/20/5/5/3/2.
Sample 503: methyl acetate / acetone / methanol / ethanol / propanol / butanol = 35/30/5/5/3/2.
Sample 504: methyl acetate / acetone / ethanol / cyclohexane / butanol = 50
/ 20/5/3/2.
Sample 505: methyl acetate / acetone / ethanol / butanol = 55/15/5/5.
Sample 506: methyl acetate / acetone / ethanol = 60/15/5.
Sample 507: methyl acetate / cyclopentanone / methanol / ethanol = 60/10 /
5/5.
Sample 508: methyl acetate / cyclopentanone / methanol / ethanol / butanol =
60/10/3/2/5.
Sample 509: methyl acetate / cyclohexanone / methanol / ethanol = 60/10 /
5/5.
Sample 510: methyl acetate / methyl ethyl ketone / acetone / methanol / ethanol =
50/10/10/5/5.
Sample 511: methyl acetate / 1, 3 dioxolane / methanol / ethanol = 50/20
/ 5/5.
Sample 512: methyl acetate / dioxane / acetone / methanol / ethanol = 50/1
0/10/5/5.
Sample 513: methyl acetate / acetone / cyclopentanone / ethanol / butanol / cyclohexane = 50/10/10/5/2/3.
Sample 514: methyl formate / methyl ethyl ketone / acetone / methanol / ethanol =
50/10/10/5/5.
Sample 515: methyl formate / acetone / ethyl acetate / ethanol / butanol / hexane = 50/10/5/5/5/5.
Sample 516: acetone / methyl acetoacetate / methanol / ethanol = 55/10/1
0/5.
Sample 517: acetone / cyclopentanone / ethanol / butanol = 45/20/1
0/5.
Sample 518: acetone / 1,3 dioxolane / ethanol / butanol = 45/20 /
10/5.
Sample 519: 1,3 dioxolane / cyclohexanone / acetone / methanol / butanol = 35/20/10/5/5/5.
Sample 520: 1,3 dioxolane / methyl acetoacetate / butanol = 55/20/5.
Sample 521: 1,3 dioxolane / acetone / ethanol / water = 53/20/5/2

Example (2) of Sample 101-12 of Example 2 except that cellulose triacetate is changed to the following cellulose acylate and methyl acetate, acetone, methanol, ethanol, and butanol are changed to the following. In the same manner as in No. 2, cellulose acylate film samples 601 to 606 of the present invention were produced. In addition, the implementation scale was implemented with the scale from which a casting winding film length will be 1000 m.

When Samples 601 to 606 were evaluated according to the evaluation method of Example 2, Sample 101-12 was obtained.
As well as excellent solution stability, film surface, film tear test, film folding test,
It was a cellulose acylate film having heat-and-moisture resistance, Re, and haze.

The physical properties of the compounds used for the preparation of each sample are summarized below. In addition, the number described in a solvent represents a mass part.

(Sample 601)
Cellulose acetate propionate has an acetyl substitution degree of 2.45, a propionate substitution degree of 0.25, a total substitution degree of 2.70, a viscosity average polymerization degree of 320, a water content of 0.3% by mass, and 6% in methylene chloride solution. % Of powder having an average particle size of 1.3 mm and a standard deviation of 0.4 mm, the amount of residual acetic acid and the amount of propionic acid are both 0.05% by mass or less, Ca is 0.012% by mass, Mg is 0.07 mass%, Fe is 5 ppm, 6-position acetyl group and propionyl group are 0.70 and 0.17, respectively, 33% of all substituents, acetone extract is 7 mass%, weight average molecular weight and number The average molecular weight ratio was 0.9, the yellowness index was 1.3, the haze was 0.2, the transparency was 93.6%, the Tg was 157 ° C., and the crystallization exotherm was 4.3 J / g. As the solvent, methyl acetate / acetone / methanol / ethanol / propanol / butanol = 55/10/5/5/3/2 was used.

(Sample 602)
Cellulose acetate butyrate has an acetyl substitution degree of 2.39 and a butyrate substitution degree of 0.
. 45 with a total degree of substitution of 2.84, a viscosity average degree of polymerization of 340, a water content of 0.4% by weight, a viscosity of 6% by weight in a methylene chloride solution of 295 mPa · s, an average particle size of 1.3 mm and a standard deviation of 0.8. 4 mm powder, residual acetic acid amount and butanoic acid amount are both 0.03% by mass or less, C
a is 0.005 mass%, Mg is 0.004 mass%, Fe is 5 ppm, 6-position acetyl group and butyroyl group are 0.72 and 0.20, respectively, 32% of all substituents, and acetone extract is 14 % By weight, ratio of weight average molecular weight to number average molecular weight is 1.3, yellowness index is 0.9, haze is 0.5, transparency is 92.9%, Tg is 153 ° C., crystallization heat generation is 3. 9
J / g was used. As the solvent, methyl acetate / acetone / methanol / ethanol / propanol / butanol = 55/10/5/5/3/2 was used.

(Sample 603)
Cellulose acetate propionate has an acetyl substitution degree of 2.45, a propionate substitution degree of 0.25, a total substitution degree of 2.70, a viscosity average polymerization degree of 320, a water content of 0.3% by mass, and 6% in methylene chloride solution. % Of powder having an average particle size of 1.3 mm and a standard deviation of 0.4 mm, the amount of residual acetic acid and the amount of propionic acid are both 0.05% by mass or less, Ca is 0.012% by mass, Mg is 0.07 mass%, Fe is 5 ppm, 6-position acetyl group and propionyl group are 0.70 and 0.17, respectively, 33% of all substituents, acetone extract is 7 mass%, weight average molecular weight and number The average molecular weight ratio was 0.9, the yellowness index was 1.3, the haze was 0.2, the transparency was 93.6%, the Tg was 157 ° C., and the crystallization exotherm was 4.3 J / g. The solvent used was methyl acetate / cyclopentanone / methanol / ethanol / butanol = 60/10/3/2/5.

(Sample 604)
Cellulose acetate butyrate has an acetyl substitution degree of 2.33 and a butyrate substitution degree of 0.
. 45, the total substitution degree is 2.78, the viscosity average polymerization degree is 340, the water content is 0.4% by mass, the viscosity of 6% by mass in the methylene chloride solution is 295 mPa · s, the average particle size is 1.3 mm, and the standard deviation is 0.8. 4 mm powder, residual acetic acid amount and butanoic acid amount are both 0.03% by mass or less, C
a is 0.005 mass%, Mg is 0.004 mass%, Fe is 5 ppm, 6-position acetyl group and propionyl group are 0.75 and 0.16, respectively, 33% of all substituents, and acetone extract is 14 % By weight, ratio of weight average molecular weight to number average molecular weight is 1.3, yellowness index is 0.9, haze is 0.5, transparency is 92.9%, Tg is 153 ° C., crystallization heat generation is 3.
9 J / g was used. The solvent used was methyl acetate / cyclopentanone / methanol / ethanol / butanol = 60/10/3/2/5.

(Sample 605)
Cellulose acetate propionate butyrate has an acetyl substitution degree of 2.46, a propionate substitution degree of 0.20, a butyrate substitution degree of 0.09, and a total substitution degree of 2.75.
Viscosity average degree of polymerization 390, water content 0.3% by mass, viscosity of 6% by mass in methylene chloride solution 320 mPa · s, average particle size 1.6 mm, standard deviation 0.5 mm, residual acetic acid amount Both propionic acid and butanoic acid content is 0.03% by mass or less, and Ca is 0.006%.
Mass%, Mg 0.005 mass%, Fe 4 ppm, 6-position acetyl group, propionyl group and butyroyl group are 0.76, 0.07 and 0.04 respectively, 32% of all substituents, acetone extractables Is 6% by mass, the ratio of the weight average molecular weight to the number average molecular weight is 1.2, the yellowness index is 0.7, the haze is 0.4, the transparency is 95.3%, the Tg is 150 ° C., and the crystallization calorific value is 3.7 J / g was used. As the solvent, methyl acetate / acetone / methanol / ethanol / propanol / butanol = 55/10/5/5/3/2 was used.

(Sample 606)
Cellulose acetate propionate laurate has an acetyl substitution degree of 2.42, a propionate substitution degree of 0.18, a laurate substitution degree of 0.08, and a total substitution degree of 2.68.
Viscosity average degree of polymerization 320, moisture content 0.4% by mass, 6% by mass viscosity 290 mPa · s in methylene chloride solution, average particle size 1.2 mm, standard deviation 0.4 mm, residual acetic acid amount Both propionic acid and lauric acid amounts are 0.03% by mass or less, and Ca is 0.00%.
5% by mass, Mg 0.003% by mass, Fe 5ppm, 6-position acetyl group, propionyl group and lauroyl group are 0.80, 0.06 and 0.03 respectively, 33% of all substituents, acetone extraction 7% by weight, ratio of weight average molecular weight to number average molecular weight is 1.1, yellowness index is 0.9, haze is 0.6, transparency is 92.6%, Tg is 149 ° C., crystallization heat generation Used 4.4 J / g. The solvent used was methyl acetate / cyclopentanone / methanol / ethanol / butanol = 60/10/3/2/5.

(Sample 607)
Cellulose acetate valeroyl has a degree of acetyl substitution of 2.58, a degree of substitution of valeroyl of 0.20, a total degree of substitution of 2.78, a viscosity average polymerization degree of 330, a water content of 0.3% by mass, 6 in methylene chloride solution. A powder having a viscosity of 305 mPa · s, an average particle diameter of 1.3 mm, and a standard deviation of 0.4 mm, the amount of residual acetic acid and valeric acid are both 0.02% by mass or less, Ca is 0.006% by mass, Mg is 0.004 mass%, Fe is 3 ppm, 6-position acetyl group and valeroyl group are 0.08 and 0.12, respectively, 33% of all substituents, acetone extract is 8 mass%, weight average molecular weight and number The average molecular weight ratio is 1.0, the yellowness index is 0.7, the haze is 0.4, the transparency is 93.8%, the Tg is 150 ° C., and the crystallization exotherm is 4.6.
J / g was used. The solvent includes 1,3 dioxolane / cyclohexanone / acetone /
Methanol / butanol = 35/20/10/5/5/5 was used.

(Sample 608)
Cellulose acetate benzoate has an acetyl substitution degree of 2.55, a benzoyl substitution degree of 0.10, a total substitution degree of 2.65, a viscosity average polymerization degree of 290, a water content of 0.4% by mass, and 6% by mass in a methylene chloride solution. Viscosity of 320 mPa · s, average particle diameter of 1.5 mm, standard deviation of 0.4 mm, residual acetic acid amount and benzoic acid are both 0.03% by mass or less, C
a is 0.005 mass%, Mg is 0.003 mass%, Fe is 4 ppm, 6-position acetyl group and benzoic acid group are 0.83 and 0.05, respectively, 33% of all substituents, acetone extract is 9% by mass, the ratio of weight average molecular weight to number average molecular weight is 1.3, yellowness index is 0.5
The haze is 0.6, the transparency is 93.4%, the Tg is 153 ° C., and the crystallization heat generation is 5.2 J / g.
Was used. As the solvent, 1,3 dioxolane / cyclohexanone / acetone / methanol / butanol = 35/20/10/5/5/5 was used.

In (1-1) of Sample 101-1 of Example 1, the same procedure as in Example 1 was performed except that plasticizer A and plasticizer B were changed to the following plasticizers (type and amount of plasticizer are described). Thus, cellulose acylate film samples 701 to 712 of the present invention were produced. In addition, the implementation scale was implemented with the scale from which a casting winding film length will be 150 m.

When samples 701 to 712 were evaluated according to the evaluation method of Example 1, the solution stability, film surface shape, film tear test, film folding test, moisture and heat resistance, Re and It was a cellulose acylate film having haze.

The physical properties of the compounds used for the preparation of each sample are summarized below. In addition, the number of description represents a mass part.
Sample 701: triphenyl phosphate / diphenyl biphenyl phosphate = 0
. 8 / 1.6.
Sample 702: tris (triisopropylphenyl) phosphate / dioctyl phthalate = 1.2 / 1.2.
Sample 703: Tributyl phosphate = 2.4.
Sample 704: tributyl o-acetylcitrate = 2.4.
Sample 705: ethylphthalyl ethyl glycolate / triphenyl phosphate = 1.
6 / 0.8.
Sample 706: di (2-ethylhexyl) phthalate = 2.4.
Sample 707: dipentaerythritol hexaacetate = 2.4.
Sample 708: dipentaerythritol tetraacetate dibutyrate = 2.4.
Sample 709: glycidol hexaacetate = 2.4.
Sample 710: Diglycerol tetraacetate = 2.4.
Sample 711: sorbitan triacetate = 2.4.
Sample 712: triphenyl phosphate / diphenyl biphenyl phosphate / ditrimethylolpropane tetraacetate = 0.4 / 0.4 / 1.6.

In (1-1) of sample 101-1 of Example 1, UV agents a and UVb were changed to the following UV agents (
Cellulose acylate film samples 801 to 805 of the present invention were produced in exactly the same manner as in Example 1 except that the UV agent type and amount were described. In addition, the implementation scale was implemented with the scale from which a casting winding film length will be 1000 m.

When samples 801 to 805 were evaluated according to the evaluation method of Example 1, the solution stability, film surface, film tear test, film folding test, moisture heat resistance, Re and It was a cellulose acylate film having haze.

The physical properties of the compounds used for the preparation of each sample are summarized below. In addition, the number of description represents a mass part.
(Sample 801)
UV agent: 4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-te
rt-butylanilino) -1,3,5-triazine / 2 (2′-hydroxy-3 ′,
5′-di-tert-butylphenyl) -5-chlorobenzotriazole, (2 (2′-
Hydroxy-3 ', 5'-di-tert-amylphenyl) -5-chlorobenzotriazole / 2,6-di-tert-butyl-p-cresol = 0.15 / 0.15 / 0.
1.
(Sample 802)
UV agent: 6-di-tert-butyl-p-cresol / pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] / triethylene glycol-bis [3- (3-tert-butyl-5-methyl-
4-hydroxyphenyl) propionate] = 0.1 / 0.1 / 0.1.
(Sample 803)
UV agent: 2,6-di-tert-butyl-p-cresol / pentaerythrityl-
Tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] / triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] = 0.15 / 0.15 / 0.15.
(Sample 804)
UV agent: 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4
-Hydroxyphenyl) propionate] / 2,4-bis- (n-octylthio)-
6- (4-Hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine / 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-
Hydroxyphenyl) propionate] = 0.2 / 0.1 / 0.1.
(Sample 805)
UV agent: N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine / tris (2,4-di-tert-butylphenyl) phosphite = 0. 2 / 0.2.

In (1-1) of Sample 101-1 of Example 1, C ₁₂ H ₂₅ OCH ₂ CH ₂ O—P (=
The cellulose acylate of the present invention was exactly the same as in Example 1 except that O)-(OK) ₂ and the citrate ester (release agent) were changed to the following release agents (describe the release agent type and amount). Film samples 901 to 907 were prepared. In addition, the implementation scale was implemented with the scale from which a casting winding film length will be 1000 m.

When samples 901 to 907 were evaluated according to the evaluation method of Example 1, the solution stability, film surface shape, film tear test, film folding test, moisture and heat resistance, Re and It was a cellulose acylate film having haze.

The physical properties of the compounds used for the preparation of each sample are summarized below. In addition, the number of description represents a mass part.
(Sample 901)
Release _{agent: {C 12 H 25 O (} CH 2 CH 2 O) 5} 2 -P (= O) -OH / tartaric = 0.0
1 / 0.02.
(Sample 902)
Release agent: C ₁₂ H ₂₅ OSO ₃ Na / oxalic acid = 0.02 / 0.02.
(Sample 903)
Release agent: sodium triisopropyl naphthalene sulfonate / citric acid = 0.02 /
0.005.
(Sample 904)
Release agent: Chloroacetic acid / chlorobenzoic acid = 0.02 / 0.005.
(Sample 905)
Stripping agent: 4-methylphthalic acid / tartaric acid = 0.025 / 0.005.
(Sample 906)
Release agent: Aspartic acid / glutamine = 0.02 / 0.01.
(Sample 907)
Release agent: ammonium aspartate / glutamine = 0.02 / 0.01.

The (2-2) dissolution / filtration step of the sample 101-12 of Example 2 is performed by the following step (10-2).
A cellulose acylate film sample 1001 of the present invention was produced in exactly the same manner as in Example 2 except that the above was changed. In addition, the implementation scale was implemented with the scale from which a casting winding film length will be 150 m.

When the sample 1001 was evaluated according to the evaluation method of Example 2, the solution stability, film surface state, film tear test, film folding test, moisture and heat resistance, Re, and haze were excellent as in the sample 101-12. It was a cellulose acylate film.

(10-2) Dissolution / filtration step The swollen solution was fed from a tank to a screw extruder using a gear pump. The screw primary pressure at this time was 0.55 MPa. The screw was provided with a jacket through which silicone oil was distributed, and was heated at 200 ° C. by a heater. The average flow velocity in the jacket was 1 m / sec, and the average solution residence time in the screw was 120 seconds. The dope exiting the screw was heated to 50 ° C. by a jacketed pipe into which a static mixer was inserted, and further heated to 130 ° C. under a pressure of 2 MPa. The heating time was 15 minutes. Further, the temperature was lowered to 120 ° C., and the mixture was passed through a sintered metal fiber filter having a nominal pore diameter of 10 μm. At this time, the primary pressure of filtration was 1.5 MPa, and the secondary pressure was 1.2 MPa. The filters, housings and pipes exposed to high temperatures were made of Hastelloy alloy and had excellent corrosion resistance, and those having a jacket for circulating a heat medium for heat insulation and heating were used.

The cellulose acylate film of the present invention is exactly the same as Example 1 except that the (2-4) casting process of Sample 101-12 of Example 2 is changed to the following casting process (11-4). A sample 1101 was produced. In addition, the implementation scale was implemented with the scale from which a casting winding film length will be 1000 m.

When the sample 1101 was evaluated according to the evaluation method of Example 2, the solution stability, the film surface state, the film tear test, the film folding test, the heat and humidity resistance, Re, and haze, which were excellent as in the sample 101-12, were evaluated. It was a cellulose acylate film.

(11-4) Casting Subsequently, the dope in the stock tank is a gear pump for primary pressure increase and is one of high precision gear pumps.
Feedback control was performed by an inverter motor so that the secondary pressure was 0.8 MPa. The high-precision gear pump had a volume efficiency of 99.2% and a discharge rate variation of 0.5% or less. The discharge pressure was 1.5 MPa. As the casting die, an apparatus equipped with a feed block having a width of 1.8 m was used. And the flow volume of the cellulose triacetate dope of a die | dye protrusion opening was adjusted so that the film thickness of the completed cellulose triacetate might be set to 80 micrometers. The additive (fine particles (silicon dioxide (particle size 20
nm) 0.1 parts by mass and a mixture of 1 part by mass of methyl acetate) were mixed and supplied to the feed block using a primary pressure-increasing gear pump and a high-precision gear pump so as to obtain a predetermined flow rate. Further UV agent c (2 (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl)-
5-chlorobenzotriazole 0.2 parts by mass) was added.

The die, feed block, and piping were all kept at 50 ° C. The die was a coat hanger type die, with thickness adjusting bolts provided at a pitch of 20 mm, and having an automatic thickness adjusting mechanism using a heat bolt. This heat bolt can also set a profile according to the liquid feed amount of the high precision gear pump by a preset program,
It has a performance capable of feedback control by an adjustment program based on the profile of an infrared thickness meter installed in the film forming process. The thickness difference between two arbitrary points 50 mm apart in the film excluding the casting edge portion 20 mm was within 1 μm, and the difference between the maximum and minimum values in the width direction thickness was adjusted to 3 μm / m or less. The average thickness accuracy of each layer is ± 2 for both outer layers.
%, The mainstream was controlled to ± 1% or less, and the overall thickness was adjusted to ± 1.5% or less.

A chamber for depressurization was installed on the primary side of the die. The decompression degree of the decompression chamber can apply a pressure difference of 1 to 1000 mPa before and after the casting bead, and can be adjusted according to the casting die speed. At that time, the bead length is 5 to 40 mm.
The pressure difference was set to be Further, the chamber temperature was provided with a mechanism that can be set higher than the condensation temperature of the gas around the casting portion.

(1-6) Casting support of sample 101-1 of Example 1, (1-7) Casting drying step and (
1-8) Except for changing to tenter transport / drying process conditions, (12-6) casting support, (12-7) cast drying process, and (12-8) tenter transport / drying process conditions described below. In the same manner as in Example 1, a cellulose acylate film sample 1201 of the present invention was produced. In addition,
The implementation scale was a scale at which the length of the wound winding film was 3000 m. Further, samples 1202 and 120 are similarly formed so that the film thicknesses are 40 μm, 100 μm, and 120 μm.
3, 1204 were produced.

When Samples 1201-1204 were evaluated according to the evaluation method of Example 1, Sample 101-
1 was a cellulose acylate film having excellent solution stability, film surface shape, film tear test, film folding test, wet heat resistance, Re, and haze.

(12-6) Casting Support The dope for three-layer co-casting projected from the die was cast using a steel drum having a diameter of 3 m and a width of 2.1 m as a support. The surface was nickel cast and hard chrome plated. Use a surface that has been polished so that the surface roughness of the drum is 0.01 μm or less, and 50 μm.
The above pinholes are completely absent, and 10-50 μm pinholes are 1 / m ² or less, 10 μm
A support having ² or less m ² pinholes / m ² was used. At this time, the number of revolutions of the drum was set so that the peripheral speed of the drum was 100 m / min. Further, the rotation flare was 200 μm or less, and the rotation unevenness was 2% or less.

(12-7) Casting drying Subsequently, the cellulose triacetate dope which was cooled and gelled by rotating by 320 ° on a drum was peeled off as the gelled film. The surface temperature of the peeled film was 0 ° C. The peeling tension at this time was 10 kgf / m, and the peeling speed was set to 1.15 times the support speed.

(12-8) Tenter Transport / Drying Process Conditions The peeled film was transported through the drying zone while being fixed at both ends with a tenter having a pin clip, and dried with drying air. The tenter was driven by a chain, and the speed fluctuation of the sprocket was 0.5% or less. The drying rate on the support was an average of 200% by weight dry weight standard solvent / minute. The drying air temperature was 140 ° C., and the overall heat transfer coefficient from the drying air was 70 Kcal / m ² · hr · ° C. The gas composition of the drying air was set to a saturated gas concentration of −30 ° C. The average drying speed in the tenter was 120% by mass of dry weight reference solvent / min. At the exit of the tenter, the amount of residual solvent in the film was 15% by mass or less. In the tenter, the film was stretched in the width direction while being conveyed. The stretching ratio from the tenter entrance to the exit was 5%. As for the stretching ratio in the tenter, the difference in the substantial stretching ratio at a portion 10 mm or more away from the tenter biting portion was 10% or less, and the difference in the stretching ratio at two points 20 mm apart was 5% or less. The ratio of the length of the base end fixed by the tenter was 70%. Further, the tenter clip was transported while being cooled so as not to exceed 50 ° C. The solvent evaporated in the tenter portion was condensed and liquefied at a temperature of −30 ° C. and recovered. The water content in the solvent was adjusted to 0.15% by mass or less and reused. The ears were cut at both ends within 30 seconds from the tenter exit. Ears of 50 mm on both sides were cut with a rotary cutter, and the cut ears were blown to a crusher by a cutter blower and crushed into chips of about 80 mm ² on average. This chip was used as a raw material in the preparation process together with cellulose triacetate flakes as a charged raw material.

(13-1) Production of Cellulose Triacetate A production example of a bend alignment liquid crystal cell will be described using the sample 104-3 of Example 1.

(13-2) Formation of Optically Anisotropic Layer The cellulose triacetate film sample 104-3 of Example 1 was immersed in a 1.5N potassium hydroxide solution (40 ° C.) for 5 minutes, and then with 0.5N sulfuric acid. Neutralize at 30 ° C for 30 seconds, 3
It was washed with pure water at 0 ° C. for 5 minutes and dried at 100 ° C. for 2 minutes. The surface energy of this cellulose triacetate film was determined by a contact angle method and found to be 68 mN / m.

Next, 24 ml / m ² of a coating solution having the following composition was applied onto the alkali-treated cellulose triacetate film with a # 14 wire bar coater. 60 seconds with warm air of 60 ℃,
Furthermore, it was dried for 150 seconds with warm air of 90 ° C. Subsequently, the film formed was rubbed in the direction of 45 ° with the slow axis (measured at a wavelength of 632.8 nm) of the cellulose acetate film.

The composition of the alignment film coating solution is summarized below.
Polymer No. of polyvinyl alcohol (Chemical Formula 22) described in JP-A-9-152509. 1 20 parts by mass Water 360 parts by mass Methanol 120 parts by mass Glutaraldehyde (crosslinking agent) 1.0 part by mass

  On the alignment film, 41.01 g of a discotic (liquid crystalline) compound (Chemical Formula 2) described in JP-A-7-306317, ethylene oxide-modified trimethylolpropane triacrylate (V # 360, Osaka Organic Chemical Co., Ltd.) )) 4.06 g, cellulose acetate butyrate (CAB551-0.2, manufactured by Eastman Chemical) 0.90 g, cellulose acetate butyrate (CAB531-1, manufactured by Eastman Chemical) 0.23 g, photopolymerization started A coating solution prepared by dissolving 1.35 g of an agent (Irgacure 907, manufactured by Ciba Geigy Co., Ltd.) and 0.45 g of a sensitizer (Kaya Cure DETX, manufactured by Nippon Kayaku Co., Ltd.) in 102 g of methyl ethyl ketone is applied with a wire bar # 3 Applied. This was affixed to a metal frame and heated in a thermostatic chamber at 130 ° C. for 2 minutes to orient the discotic compound. Next, using a 120 W / cm high-pressure mercury lamp at 130 ° C., UV irradiation was performed for 1 minute to polymerize the discotic compound. Then, it stood to cool to room temperature. In this manner, a cellulose triacetate film sample 1302 having an optically anisotropic layer was produced. The retardation value measured from the normal direction of the optically anisotropic layer measured at a wavelength of 550 nm was 38 nm. The angle (tilt angle) between the disc surface and the cellulose acetate film surface was 40 ° on average.

(13-3) Preparation of Polarizing Plate Sample A polarizing film was prepared by adsorbing iodine to a stretched polyvinyl alcohol film, and using a polyvinyl alcohol adhesive, a commercially available cellulose triacetate film (Fujitac TD80U, Fuji Photo Film Co., Ltd.) )) And affixed to one side of the polarizing film using a polyvinyl alcohol-based adhesive.

Further, the optical compensation sheet sample 1302 prepared in (13-2) was bonded to the opposite side of the cellulosic acetate film of the polarizing plate via an adhesive so that the slow axes thereof were parallel to each other. In this way, a polarizing plate sample 1303 was manufactured.

(13-4) Preparation of Bend Alignment Liquid Crystal Cell A polyimide film was provided as an alignment film on a glass substrate with an ITO (indium oxide) electrode, and the alignment film was rubbed. The obtained two glass substrates were faced to each other so that the rubbing directions were parallel to each other, and the cell gap was set to 6 μm. Δn is 0.1 in the cell gap
A 396 liquid crystal compound (ZLI1132, manufactured by Merck & Co., Inc.) was injected to prepare a bend alignment liquid crystal cell.

Two polarizing plate samples 1303 prepared in (13-3) were attached so as to sandwich the manufactured bend alignment cell, and a liquid crystal display device 1304 was manufactured. The optically anisotropic layer of the polarizing plate faced the cell substrate, and the rubbing direction of the liquid crystal cell and the rubbing direction of the optically anisotropic layer facing it were antiparallel.

A rectangular wave voltage of 55 Hz was applied to the liquid crystal cell. A normally white mode of 2V white display and 5V black display was set. Using the ratio of transmittance (white display / black display) as the contrast ratio,
Using EZ-Contrast 160D (manufactured by ELDIM), the viewing angle was measured in 8 stages from black display (L1) to white display (L8). The results are shown in Table 1. It was confirmed that a display device having excellent vertical and horizontal viewing angles can be obtained.

(14-1) Production of Cellulose Triacetate A production example of a TN type liquid crystal cell is described using the sample 103-1 of Example 1.

Optical characteristics of the produced cellulose triacetate film sample 103-1 were measured. Here, the optical properties are Re retardation value and Rth at a wavelength of 550 nm.
The retardation value was measured. Re was 8 nm and Rth was 80 nm. Subsequently, the produced cellulose acetate film sample 1401 was immersed in a 2.0 N potassium hydroxide solution (25 ° C. water / isopropanol: 8/2 mass ratio) for 3 minutes, neutralized with sulfuric acid, washed with pure water, Dried. The surface energy of this cellulose acetate film was determined by a contact angle method and found to be 40 mN / m. On this cellulose acetate film, an alignment film coating solution having the following composition was coated at 24 ml / m ² with a # 14 wire bar coater. 6
The film was dried with warm air of 0 ° C. for 60 seconds and further with warm air of 90 ° C. for 150 seconds.

Next, the formed film was rubbed in a direction parallel to the longitudinal direction of the cellulose acetate film. Here, the composition of the alignment film coating solution was polymer No. 22 described in JP-A-9-152509. 1 (20 parts by mass), water (360 parts by mass), methanol (120 parts by mass), and glutaraldehyde (crosslinking agent) (1.0 part by mass).

(14-2) Formation of optically anisotropic layer On the above-mentioned alignment film, 41.01 g of a discotic (liquid crystalline) compound (Chemical Formula 2) described in JP-A-7-306317, ethylene oxide-modified trimethylolpropane 4.06 g of triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.), 0.90 g of cellulose acetate butyrate (CAB551-0.2, manufactured by Eastman Chemical Co.), cellulose acetate butyrate (CAB531-1, yeast) Mang Chemical Co., Ltd.) 0.23 g, Photopolymerization initiator (Irgacure 907, Ciba Geigy Co., Ltd.) 1.35 g, Sensitizer (Kayacure DETX, Nippon Kayaku Co., Ltd.) 0.45 g was added to 102 g of methyl ethyl ketone. The dissolved coating solution was applied with a # 3.6 wire bar. This was heated in a constant temperature zone of 130 ° C. for 2 minutes to orient the discotic compound. Next, UV irradiation was performed for 1 minute using a 120 W / cm high pressure mercury lamp in an atmosphere of 60 ° C. to polymerize the discotic compound. Then, it stood to cool to room temperature. Thus, an optically anisotropic layer was formed, and an optical compensation sheet sample 1402 was produced. The retardation value measured from the normal direction of the optically anisotropic layer measured at a wavelength of 550 nm was 43 nm. The angle (tilt angle) between the disk surface and the cellulose acetate film surface was 42 ° on average.

(14-3) Preparation of polarizing plate sample A polarizing film is prepared by adsorbing iodine to a stretched polyvinyl alcohol film, and the sample 1402 prepared in (14-2) is used as an optical compensation layer using a polyvinyl alcohol-based adhesive. Is attached to one side of the polarizing film so that is on the opposite side of the polarizing film. Saponification treatment was performed on a commercially available cellulose triacetate film (Fujitac TD80U, manufactured by Fuji Photo Film Co., Ltd.)
Using a polyvinyl alcohol-based adhesive, it was attached to the opposite side of the polarizing film. The transmission axis of the polarizing film and the slow axis of the sample 1402 were arranged in parallel. Thus, polarizing plate sample 1
403 was produced.

(14-4) Production of liquid crystal display device A pair of polarizing plates provided in a liquid crystal display device (LC-20SD1, manufactured by Sharp Corporation) using a TN type liquid crystal cell is peeled off, and instead (14-3) The liquid crystal display device 1404 was manufactured by attaching the polarizing plate 1403 manufactured in step 1 to the viewer side and the backlight side one by one through an adhesive so that the sample 1402 is on the liquid crystal cell side. The transmission axis of the polarizing plate on the viewer side,
The transmission axis of the polarizing plate on the backlight side was arranged to be in the O mode. The liquid crystal display device thus manufactured was measured using a measuring instrument (EZ-Contrast 160D, ELDIM
The viewing angle was measured in 8 steps from black display (L1) to white display (L8).
The results are shown in Table 2 including comparison. From Table 2, the cellulose triacetate film using the non-chlorine organic solvent of the present invention was excellent with superior vertical and horizontal viewing angle characteristics and no light leakage.

(14-5) Comparative Example A pair of polarizing plates provided on a liquid crystal display device (LC-20SD1, manufactured by Sharp Corporation) using a TN type liquid crystal cell is peeled off, and a commercially available polarizing plate (HLC2-5618HCS) is used instead.
(Manufactured by Sanlitz Co., Ltd.) was attached to the observer side and the backlight side one by one via an adhesive to produce a liquid crystal display device 1405 for comparison. The transmission axis of the polarizing plate on the observer side and the transmission axis of the polarizing plate on the backlight side were arranged so as to be in the O mode. About the produced liquid crystal display device 1405, the viewing angle was measured in eight steps from black display (L1) to white display (L8) using a measuring machine (EZ-Contrast 160D, manufactured by ELDIM). Table 2 summarizes the results of the liquid crystal display device of the present invention.

In addition, about the light leakage at the time of backlight lighting, after lighting a backlight continuously for 5 hours at normal temperature and normal humidity, the black display state of the whole surface was evaluated visually in a dark room.

Although Example 15 using a preferable retardation plate is described below, the present invention is not limited to this range.

(15-1) Production of Retardation Plate In (2-1) of Example 2, casting is performed so that the film thickness after stretching for changing the solvent mixture composition to 101 μm is as follows. 9) A cellulose triacetate film (sample 1501) of the present invention was produced in the same manner as in Example 2, except that the residual solvent was dried to 2% by mass in the post-drying step.
Cellulose triacetate (substitution degree 2.76, 6-position acetyl group 0.92, viscosity average polymerization degree 320, water content 0.4 mass%, viscosity 6 mass% in methylene chloride solution 305 mPa · sec, average particle diameter 1.5 mm Powder with a standard deviation of 0.5 mm)
20 parts by weight methyl acetate 60 parts by weight acetone 5 parts by weight methanol 5 parts by weight ethanol 5 parts by weight butanol 5 parts by weight Plasticizer A (ditrimethylolpropane tetraacetate) 0.4 parts by weight plasticizer B (triphenyl phosphate) 0 parts by mass plasticizer C (diphenylbiphenyl phosphate) 1.0 part by mass UV agent a: (2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tertbutylanilino) -1,3,5-triazine
0.2 parts by mass of UV agent b: 2 (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole
0.2 part by mass tribenzylamine 0.40 part by mass retardation control agent N 0.7 part by mass C ₁₂ H ₂₅ OCH ₂ CH ₂ O—P (═O) — (OK) ₂ (release agent)
0.02 parts by mass Citric acid ester mixture (release agent) 0.02 parts by mass Fine particles (silicon dioxide (particle size 20 nm), Mohs hardness about 7) 0.05 parts by mass

Next, a cellulose triacetate sample (sample 1501) having a residual solvent amount of 2.0% by mass produced with a non-chlorine organic solvent was subjected to longitudinal uniaxial stretching using a roll stretching machine. The roll of the roll drawing machine was an induction heating jacket roll having a mirror-finished surface, and the temperature of each roll could be adjusted individually. The stretching zone was covered with a casing at 130 ° C. The roll before the stretching part was set so that it could be gradually heated to 130 ° C. The distance between the stretches was adjusted so that the L / W ratio was 2.5. The stress at the time of stretching is 7.2 kgf / m
m ² . After stretching, the film was cooled and wound up. When the draw ratio was measured, it was 1.45 times. The film thickness was 101 μm.

The optical characteristics of the produced retardation plate sample (sample 1502) were measured. Re is 115
. 7 nm (450 nm), 136.5 nm (550 nm), 142.3 nm (590 nm)
), (Nx−nz) / (nx−ny) = 1.53, the deviation of the slow axis was ± 1.2, the standard deviation was 0.3, and the haze was 0.8. . Re at each angle is-
0.84 nm (450 nm) and 1.20 nm (750 nm) at 40 °, and 0. 0 at 0 °.
85 nm (450 nm), 1.19 nm (750 nm), and 0.85 nm at 20 ° (
450 nm), 1.19 nm (750 nm), and 0.84 nm (450 nm at 40 °)
), 1.20 nm (750 nm). As a result, it was confirmed that Re was almost the same for each angle.

(15-2) Preparation of Circular Polarizing Plate A protective film (cellulose triacetate sample 1501 obtained in Example 15), a polarizing film, and a retardation plate sample (sample 1502) prepared in (15-1) are laminated in this order. Thus, a circularly polarizing plate was obtained. The angle between the slow axis of the retardation plate and the polarization axis of the polarizing film was adjusted to 45 °. As a result of examining the optical properties of the obtained circularly polarizing plate, almost complete circularly polarized light was achieved in a wide wavelength region (450 to 590 nm). A circularly polarizing plate was mounted on a reflective liquid crystal panel, and viewing angle characteristics were measured using a measuring instrument (EZ Contrast 160D, manufactured by ELDIM). The results are shown in Table 3. It is confirmed that a wide viewing angle can be obtained when the produced circularly polarizing plate is used.

Here, as a comparative example in the table, a retardation plate made of the following polycarbonate was prepared. That is, a polycarbonate having a weight average molecular weight of 100,000 was dissolved in methylene chloride to obtain a 17% by mass solution. This solution was cast on a glass plate so as to have a dry film thickness of 80 μm, dried at room temperature for 30 minutes, and then dried at 70 ° C. for 30 minutes. The polycarbonate film was peeled from the glass plate and stretched 4% at 158 ° C. to obtain a stretched birefringent film of polycarbonate. About the obtained polycarbonate film (retardation plate), Re, (nx-nz) / (nx-ny)
) Was measured. Re is 147.8 nm (450 nm), 137.5 nm (550 nm)
134.9 nm (590 nm) and (nx−nz) / (nx−ny) = 1.12.

Using this polycarbonate phase difference plate, a transparent protective film, a polarizing film and the polycarbonate phase difference plate produced in the comparative example were laminated in this order to obtain a circularly polarizing plate. The angle between the slow axis of the retardation plate and the polarization axis of the polarizing film was adjusted to 45 °. Viewing angle characteristics of the obtained circularly polarizing plate were evaluated in the same manner as in the Examples. It is clear that the viewing angle is extremely inferior both vertically and horizontally.

A glass substrate provided with an ITO transparent electrode and a glass substrate provided with an aluminum reflective electrode formed with fine irregularities were prepared. A polyimide alignment film (SE-7992, manufactured by Nissan Chemical Industries, Ltd.) was formed on each of the electrode sides of the two glass substrates, and a rubbing treatment was performed. 2.5μ
The two substrates were stacked with the alignment film facing each other through a spacer of m. The orientation of the substrate was adjusted so that the rubbing directions of the two alignment films intersected at an angle of 117 °. Liquid crystal (MLC-6252, manufactured by Merck) was injected into the gap between the substrates to form a liquid crystal layer. In this manner, a TN liquid crystal cell having a twist angle of 63 ° and a Δnd value of 198 nm was produced.

On the side of the glass substrate provided with the ITO transparent electrode, the produced retardation plate (sample 1502 of the present invention).
) Was pasted through an adhesive. On top of that, a polarizing plate (a polarizing film in which a protective film whose surface was subjected to AR treatment was laminated) was attached.

A rectangular wave voltage of 1 kHz was applied to the manufactured reflective liquid crystal display device. White display 1.5V,
As a result of visual evaluation with a black display of 4.5 V, it was confirmed that neutral gray was displayed with no color in both white display and black display. Next, the measuring machine (
When the contrast ratio of reflected luminance was measured using EZcontrast 160D (manufactured by Eldim), the contrast ratio from the front was 23, and the viewing angle at which the contrast ratio was 3 was 120 ° or higher and 120 ° or more left and right. It was.

On a glass substrate provided with an ITO transparent electrode, a vertical alignment film-forming polymer (LQ-18)
00, manufactured by Hitachi Chemical DuPont Microsystems Co., Ltd.) was applied, dried, and then rubbed.

A sample 150 of the present invention produced on a glass substrate on which aluminum was deposited as a reflector.
2 retardation plates were attached with an adhesive. Furthermore, a SiO layer by sputtering was provided on the retardation plate of the sample 1502 of the present invention, and an ITO transparent electrode was provided thereon. On the transparent electrode, a solution of vertical alignment film forming polymer (LQ-1800, manufactured by Hitachi Chemical DuPont Microsystems) was applied, dried, and then 45 ° from the slow axis direction of the retardation plate of Sample 1502 of the present invention. The rubbing process was performed in the direction of. Two glass substrates through a 7.6 μm spacer,
The alignment films were stacked so as to face each other. The orientation of the substrate was adjusted so that the rubbing direction of the alignment film was antiparallel. Dichroic dye (NKX-1366, manufactured by Nippon Photosensitive Dye) 2 in the gap between the substrates
. A mixture of 0% by mass and liquid crystal (ZLI-2806, Merck) 98.0% by mass was injected by a vacuum injection method to form a liquid crystal layer.

A rectangular wave voltage of 1 kHz was applied between ITO electrodes of the produced guest-host reflective liquid crystal display element. The transmittances at white display 1V and black display 10V were 65% and 6%, respectively. The transmittance ratio (contrast ratio) between white display and black display was 11: 1. Further, when the viewing angle at which a contrast ratio of 2: 1 was obtained in the vertical and horizontal directions was measured, it was 120 ° or more in both the vertical and horizontal directions. The transmittance was measured while increasing and decreasing the voltage, but no hysteresis was observed in the transmittance-voltage curve.

(18-1) Production of Retardation Plate In production of the retardation plate of Example 15, the film thickness of the three-layer co-casting is 12 μm, 96 μm, 12
It produced so that it might become micrometer. At this time, the outer layer dope having a thickness of 12 μm was prepared by diluting the dope of (2-1) of Example 15 with methyl acetate / acetone / methanol / ethanol / butanol by 10%. At this time, the ratio of the diluted solvent was set to be exactly the same as the ratio of the solution of (2-1) in Example 2.

In Example 2 (2-1), the film thickness after stretching to change the solvent mixture composition to 10 is as follows.
Exactly in the same manner as in Example 2, except that casting was performed to 1 μm and drying was performed so that the residual solvent was 1% by mass in the post-drying step of Example 2 (2-9). An inventive cellulose triacetate film (sample 1801) was prepared.

The obtained film was stretched in the same manner as in Example 15 (2-1). When the draw ratio was measured, it was 1.45 times. The film thickness was 101 μm.

The optical characteristics of the obtained retardation plate (sample 1801) and the variation of the variation were measured. Re
Are 116.2 nm (450 nm), 136.7 nm (550 nm), 142.2 nm (
590 nm), (nx−nz) / (nx−ny) = 1.50, Re at 450 nm
The standard deviation of 0.023 was 0.023 and the standard deviation of Re at 590 nm was 0.020.

Examples of optical applications using biaxial cellulose acylate films are described in detail below.

(19-1) Production of Biaxial Cellulose Acylate Film In the cellulose acetate film sample 104-3 of Example 1, the transverse draw ratio of 13
Cellulose acetate film TAC under the same conditions, 0% reduced to 120%
1 was cast. The physical properties were measured by the above methods and are shown in Table 4.

In the cellulose acetate film sample 104-3 of Example 1, the addition amount of the letter control agent N was increased to 6%, and the cellulose acetate film TAC-2 was cast under the same conditions for all others. The physical properties were measured by the above methods and are shown in Table 4.

In the cellulose acetate film sample 104-3 of Example 1, the transverse draw ratio was 12
The cellulose acetate film TAC-3 was cast under the same conditions, with the amount lowered to 0%, the retardation control agent reduced to 1%, and all other conditions. The physical properties were measured by the above methods and are shown in Table 4.

In the cellulose acetate film sample 104-4 of Example 1, the transverse draw ratio is 1
The cellulose acetate film TAC-4 was cast under the same conditions, with the amount lowered to 20%, the retardation control agent reduced to 1%, and everything else. The physical properties were measured by the above methods and are shown in Table 4.

A sample 2301 was produced in exactly the same manner as 104-3, with the transverse stretch ratio increased to 170% in 104-3 of Example 1. The physical properties were measured by the above methods and are shown in Table 4. Further, Example 23 was performed under the same conditions as in Example 23 except that the transverse draw ratio was 160% and the film thickness was 60 μm.
-1. The retardation control agent includes N, N, N-tri-m-toluyl-
1,3,5-triazine-2,4,6-triamine was used. The physical properties were measured by the above methods and are shown in Table 4. Further, the retardation control agent is N, N, N-tri-m-toluyl-1,3.
, 5-triazine-2,4,6-triamine was changed to N, N-di-m-toluyl-Nm-methoxyphenyl-1,3,5-triazine-2,4,6-triamine. Example 23-2 was conducted under the same conditions as Example 23-1. The results are shown in Table 4.

In 104-3 of Example 1, cellulose triacetate (substitution degree 2.76, 6-position acetyl substitution degree 0.92, viscosity average polymerization degree 320, water content 0.4 mass%, viscosity of 6 mass% in methylene chloride solution) A powder having an average particle diameter of 305 mPa · sec and an average particle diameter of 1.5 mm and a standard deviation of 0.5 mm is referred to as cellulose acetate propionate (CAP).
Acetyl substitution degree 2.45, propionate substitution degree 0.25, total substitution degree 2.70, 6-position acetyl substitution degree 0.80, 6-position propionate substitution degree 0.10, viscosity average polymerization degree 320, water content 0. 3% by mass, viscosity of 6% by mass in a methylene chloride solution 275 mPa · sec,
Powder having an average particle size of 1.3 mm and a standard deviation of 0.4 mm, the amount of residual acetic acid and the amount of propionic acid are both 0.05% by mass or less, Ca is 0.012% by mass, and Mg is 0.07% by mass. ,
Fe is 5 ppm, the sum of 6-position acetyl group and propionyl group is 0.87, 33% of all substituents, acetone extract is 7% by mass, the ratio of weight average molecular weight to number average molecular weight is 0.9, yellowness Index: 1.3, Haze: 0.2, Transparency: 93.6%, Tg: 157 ° C
A sample 2401 was prepared in exactly the same manner as 104-3 in Example 1 except that the crystallization heat generation amount was changed to 4.3 J / g). The physical properties were measured by the above methods and are shown in Table 4.

From Table 4 above, the cellulose triacetate film stretched 20 to 30% in the transverse direction was excellent in breaking strength and breaking progress, small in axial deviation, Re, and Rth, and in small range. Also, the heat shrinkage starting temperature is stable at a high temperature.

A polarizing film was prepared by adsorbing iodine to a stretched polyvinyl alcohol film. The cellulose triacetate film TAC-1 produced in Example 19 was saponified and attached to one side of the polarizing film using a polyvinyl alcohol-based adhesive. Here, the saponification treatment of the cellulose acetate film was immersed in a 2.0N potassium hydroxide solution (25 ° C.) for 2 minutes, neutralized with sulfuric acid, washed with pure water and dried. The surface energy of this cellulose acetate film was determined by a contact angle method and found to be 59 mN / m. In addition, since it stuck so that the longitudinal direction of TAC-1 and a polarizing film might become parallel, the angle which the average direction of the slow axis of TAC-1 and the transmission axis of a polarizing film make was 0.5 degree. A commercially available cellulose triacetate film (Fujitac TD80UF, manufactured by Fuji Photo Film Co., Ltd.) was similarly saponified and attached to the opposite side of the polarizing film using a polyvinyl alcohol adhesive. In this way, a polarizing plate was produced.

Example 25 except that the cellulose triacetate film prepared in Example 20 was used.
A polarizing plate was produced in the same manner as described above. The angle formed by the average direction of the slow axes of TAC-2 and the transmission axis of the polarizing film was 0.3 °.

Example 25 except that the cellulose triacetate film prepared in Example 21 was used.
A polarizing plate was produced in the same manner as described above. The angle formed by the average direction of the slow axes of TAC-3 and the transmission axis of the polarizing film was 1.0 °.

Example 25 except that the cellulose triacetate film prepared in Example 22 was used.
A polarizing plate was produced in the same manner as described above. The angle formed by the average direction of the slow axes of TAC-4 and the transmission axis of the polarizing film was 0.4 °.

A polarizing film was prepared by adsorbing iodine to a stretched polyvinyl alcohol film. The sample 2301 produced in Example 23 was attached to one side of the polarizing film using an acrylic adhesive. The sample 2301 and the polarizing film were pasted so that their longitudinal directions were parallel, and the angle formed by the average direction of the slow axis of the sample 2301 and the transmission axis of the polarizing film was 0.4 °.

A commercially available cellulose triacetate film (Fujitac TD80UF, manufactured by Fuji Photo Film Co., Ltd.) was saponified by the above-described method and attached to the opposite side of the polarizing film using a polyvinyl alcohol adhesive. In this way, a polarizing plate sample 2901 was produced.

A polarizing film was prepared by adsorbing iodine to a stretched polyvinyl alcohol film. The sample 2401 produced in Example 24 was attached to one side of the polarizing film using an acrylic adhesive. The sample 2401 and the polarizing film were pasted so that their longitudinal directions were parallel to each other, and the angle formed by the average direction of the slow axis of the sample 2401 and the transmission axis of the polarizing film was 0.3 °.

A commercially available cellulose triacetate film (Fujitac TD80UF, manufactured by Fuji Photo Film Co., Ltd.) was saponified and attached to the opposite side of the polarizing film using a polyvinyl alcohol adhesive. In this way, a polarizing plate sample 3001 was produced.

A pair of polarizing plates and a pair of optical compensation sheets provided in a liquid crystal display device (VL-1530S, manufactured by Fujitsu Limited) using a vertical alignment type liquid crystal cell were peeled off. Instead, Example 25
The polarizing plates prepared in (1) were attached to the observer side and the backlight side one by one through an adhesive so that the cellulose acetate film prepared in Example 19 was on the liquid crystal cell side. The crossed Nicols were arranged so that the transmission axis of the polarizing plate on the viewer side was in the vertical direction and the transmission axis of the polarizing plate on the backlight side was in the horizontal direction. These polarizing plates and cellulose acetate film were measured for both the combination (center) and the combination (end) of the ends of the original stretched film.

About the produced liquid crystal display device, a measuring machine (EZ-Contrast160D, ELDI
The minimum viewing angle at which a contrast ratio of 10: 1 can be obtained in the vertical and horizontal directions using M) is shown, and the results are shown in Table 5. In addition, the number of bright spots that shine like stars in the darkroom was counted as a full black display. At the same time, display unevenness (a region brightly cloudy and cloudy) was determined (a transparent film with 1 cm square grids placed on the liquid crystal and the number of bright regions was counted and displayed as a percentage).

A liquid crystal display device was produced in the same manner as in Example 31 except that the polarizing plate produced in Example 26 was used. The viewing angle, the number of bright spots, and display unevenness were determined in the same manner as in Example 31, and the results are shown in Table 5.

A pair of polarizing plates and a pair of optical compensation sheets provided in a liquid crystal display device (VL-1530S, manufactured by Fujitsu Limited) using a vertical alignment type liquid crystal cell were peeled off. Instead, Example 27
The polarizing plate prepared in (1) was attached to the viewer side through an adhesive so that the cellulose acetate film prepared in Example 21 was on the liquid crystal cell side. In addition, on the backlight side,
A sheet of commercially available polarizing plate (HLC2-5618HCS, manufactured by Sanritz Co., Ltd.) was attached. The crossed Nicols were arranged so that the transmission axis of the polarizing plate on the viewer side was in the vertical direction and the transmission axis of the polarizing plate on the backlight side was in the horizontal direction. The viewing angle, the number of bright spots, and display unevenness were determined in the same manner as in Example 31, and the results are shown in Table 5.

A liquid crystal display device was produced in the same manner as in Example 31 except that the polarizing plate produced in Example 28 was used. The viewing angle, the number of bright spots, and display unevenness were determined in the same manner as in Example 31, and the results are shown in Table 5.

A liquid crystal display device was produced in the same manner as in Example 31 except that the polarizing plate produced in Example 29 was used. The viewing angle, the number of bright spots, and display unevenness were determined in the same manner as in Example 31, and the results are shown in Table 5.

A liquid crystal display device was produced in the same manner as in Example 31 except that the polarizing plate produced in Example 30 was used. The viewing angle, the number of bright spots, and display unevenness were determined in the same manner as in Example 31, and the results are shown in Table 5.

From Table 5, the cellulose triacetate film produced in the present invention was excellent in all of viewing angle, bright spot failure and display unevenness.

A pair of polarizing plates provided in a liquid crystal display device (6E-A3, manufactured by Sharp Corporation) using a TN type liquid crystal cell was peeled off, and a polarizing plate produced in Example 25 was produced in Example 19 instead. The obtained cellulose acetate film was attached to the viewer side and the backlight side one by one through an adhesive so that the cellulose acetate film was on the liquid crystal cell side. The transmission axis of the polarizing plate on the observer side and the transmission axis of the polarizing plate on the backlight side are orthogonal to each other and are arranged in the O mode. The viewing angle, the number of bright spots, and display unevenness were determined in the same manner as in Example 33, and the results are shown in Table 6.

A liquid crystal display device was produced in the same manner as in Example 37 except that the polarizing plate produced in Example 26 was used. The viewing angle, the number of bright spots, and display unevenness were determined in the same manner as in Example 33, and the results are shown in Table 6.

From Table 6, the cellulose triacetate film produced in the present invention was excellent in all of viewing angle, bright spot failure and display unevenness.

The amount of the retardation control agent in Example 21 was changed to 6.0 parts by mass, and 45% by mass of redissolved cellulose triacetate (cellulose triacetate used in Example 21) in the total cellulose triacetate was used. The characteristics are shown in Table 7.

The amount of the retardation control agent in Example 21 was changed to 8.0 parts by mass. In addition, 60 mass% of redissolved cellulose triacetate (cellulose triacetate used in Example 19) in the total cellulose triacetate was used. The characteristics are shown in Table 7.

(Saponification treatment of cellulose acetate film)
The cellulose acetate film TAC-9 produced in Example 39 was immersed in an aqueous 1.5N sodium hydroxide solution (55 ° C.) for 2 minutes, and then washed in a water bath at room temperature to give 0.1N
The mixture was neutralized with sulfuric acid (30 ° C.), washed again in a room temperature water bath, and further dried with warm air at 100 ° C. Thus, the surface of the cellulose acetate film TAC-9 was saponified.

(Formation of alignment layer)
On a saponified cellulose acetate film TAC-9, a coating solution having the following composition was #
24 ml / m ^{2 was} applied with a 14 wire bar coater. Drying was performed with warm air of 60 ° C. for 60 seconds, and further with warm air of 90 ° C. for 150 seconds. Next, the formed film was rubbed in the direction of 45 ° with the stretching direction of the cellulose acetate film TAC-9 (almost coincident with the slow axis).

The composition of the alignment film coating solution is summarized below.
Modified polyvinyl alcohol (Polymer No. 1 of (Chemical Formula 22) described in JP-A-9-152509) 20 parts by weight Water 360 parts by weight Methanol 120 parts by weight Glutaraldehyde (crosslinking agent) 0.5 parts by weight

(Formation of optically anisotropic layer)
The cellulose acetate film TAC-9 on which the above-mentioned alignment film layer was formed was used as a support for forming the optically anisotropic layer. On the alignment film, 41.01 parts by mass of a discotic (liquid crystalline) compound described in JP-A-7-306317 (chemical formula 2), ethylene oxide-modified trimethylolpropane triacrylate (V # 360, Osaka Organic Chemistry ( 4.06 parts by mass, cellulose acetate butyrate (CAB551-0.2, manufactured by Eastman Chemical Co.) 0
. 90 parts by mass, 0.23 parts by mass of cellulose acetate butyrate (CAB531-1, Eastman Chemical), photopolymerization initiator (Irgacure 907, Ciba Geigy)
A coating solution in which 1.35 parts by mass and 0.45 parts by mass of a sensitizer (Kaya Cure DETX, manufactured by Nippon Kayaku Co., Ltd.) were dissolved in 102 parts by mass of methyl ethyl ketone was applied with a # 3 wire bar. This was heated in a thermostatic bath at 130 ° C. for 2 minutes to orient the discotic compound. Next, 1
Using a 120 W / cm high pressure mercury lamp at 30 ° C., 250 mJ / cm ² of UV light was irradiated to polymerize the discotic compound. Then, it stood to cool to room temperature. Thus, an optically anisotropic layer was formed, and an optical compensation sheet RF-1 was produced. The optical properties of the produced optical compensation sheet were measured. The results are shown in Table 8.

The cellulose acetate film TAC-10 produced in Example 40 was used as a 1.5 N KO.
H-isopropyl alcohol solution was applied at 25 ml / m ^{2 and} dried at 25 ° C. for 5 seconds.
The film was washed with running water for 10 seconds, and the film surface was dried by blowing air at 25 ° C. Thus, the surface of the cellulose acetate film TAC-10 was saponified. On the saponified cellulose acetate film TAC-10, an alignment film was formed in the same manner as in Example 41, and after rubbing, an optically anisotropic layer was formed, and an optical compensation sheet RF
-2 was produced. The optical properties of the produced optical compensation sheet were measured. The results are shown in Table 8.

First, iodine was adsorbed on a stretched polyvinyl alcohol film to prepare a polarizing film. The optical compensation sheet RF-1 produced in Example 41 was attached to one side of the polarizing film using a polyvinyl alcohol-based adhesive. Since the optical compensation sheet RF-1 and the polarizing film are pasted so that the longitudinal directions thereof are parallel to each other, the average direction of the slow axis of TAC-9 which is the support of the optical compensation sheet RF-1 and the transmission axis of the polarizing film The angle formed was 0.3 °. The cellulose triacetate film produced in Example 21 of the present invention was saponified by the method of Example 41 and attached to the opposite side of the polarizing film using a polyvinyl alcohol-based adhesive. Thus, an elliptically polarizing plate was produced.

A polarizing film was prepared by adsorbing iodine to a stretched polyvinyl alcohol film. The saponified surface of the cellulose acetate film TAC-10 saponified in Example 42 was placed on the polarizing film side and attached to one side of the polarizing film using a polyvinyl alcohol-based adhesive. The cellulose triacetate film produced in Example 21 of the present invention was saponified by the method of Example 41 and attached to the opposite side of the polarizing film using a polyvinyl alcohol-based adhesive. Further, the optical compensation sheet RF-2 produced in Example 42 was attached using an acrylic adhesive so that the cellulose acetate film TAC-10 attached to the polarizing film as described above was in contact with the cellulose acetate film side. It was. Cellulose acetate film T
Since TAC-10, which is a support for AC-10 and optical compensation sheet RF-2, was attached so that the longitudinal direction of the polarizing film was parallel, the average direction of the slow axis of TAC-10 and the transmission axis of the polarizing film Was an angle of 0.4 °. Thus, an elliptically polarizing plate was produced.

(Preparation of bend alignment liquid crystal cell)
A polyimide film was provided as an alignment film on a glass substrate with an ITO electrode, and the alignment film was rubbed. The obtained two glass substrates were faced to each other so that the rubbing directions were parallel to each other, and the cell gap was set to 6 μm. A bend-aligned liquid crystal cell was prepared by injecting a liquid crystal compound (ZLI1132, manufactured by Merck & Co., Inc.) having a Δn of 0.1396 into the cell gap.

(Production of liquid crystal display device)
Two elliptical polarizing plates prepared in Example 25 were attached so as to sandwich the manufactured bend alignment cell. The optically anisotropic layer of the elliptically polarizing plate was arranged so as to face the cell substrate, and the rubbing direction of the liquid crystal cell and the rubbing direction of the optically anisotropic layer facing it were antiparallel.

With respect to the manufactured liquid crystal display device, the minimum viewing angle at which a white display voltage of 2 V and a black display voltage of 6 V are applied and a contrast ratio of 10: 1 can be obtained in the vertical and horizontal directions using a measuring instrument (EZ-Contrast 160D, manufactured by ELDIM). The results are shown in Table 9. In addition, the number of bright spots shining like a star in a dark room and display unevenness were measured as a full black display. The results are shown in Table 9.

A liquid crystal display device was produced in the same manner as in Example 45 except that the elliptically polarizing plate produced in Example 44 was used. Evaluation was conducted in the same manner as in Example 45, and the results are shown in Table 9.

Examples 45 and 46 made from the biaxially stretched cellulose acylate film of the present invention using the present invention had minimum viewing angles, bright spot failures and display irregularities superior to those in Table 9.

In Example 47, an experiment was conducted on the production of an antiglare antireflection film of the present invention, the production of a polarizing plate, and application to an LCD.

(Preparation of coating solution for hard coat layer)
250 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) was dissolved in 439 g of a mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50 mass%. A solution obtained by dissolving 7.5 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and 5.0 g of a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) in 49 g of methyl ethyl ketone was added to the obtained solution. added. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.51. Further, this solution was filtered through a polypropylene filter having a pore diameter of 30 μm to prepare a coating solution for a hard coat layer.

(Preparation of coating solution for antiglare layer)
A hard coat coating solution containing zirconium dioxide ultrafine particle dispersion (KZ) in a mixed solvent of 104.1 g of cyclohexanone and 61.3 g of methyl ethyl ketone while stirring with an air disperser.
-7886A, manufactured by JSR Corporation) 217.0 g. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.61. Further, 5 g of crosslinked polystyrene particles having an average particle diameter of 2 μm (trade name: SX-200H, manufactured by Soken Chemical Co., Ltd.) were added to this solution, and the mixture was stirred and dispersed at 5000 rpm for 1 hour with a high speed dispaper. It filtered with the filter made from a polypropylene, and prepared the coating liquid for glare-proof layers.

(Preparation of coating solution A for low refractive index layer)
Thermally crosslinkable fluorine-containing polymer having a refractive index of 1.46 (JN-7221, manufactured by JSR Corporation) 20
200 g of methyl isobutyl ketone was added to 0 g, and after stirring, the mixture was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for a low refractive index layer.

(Preparation of coating solution B for low refractive index layer)
205 g of heat-crosslinkable fluorine-containing polymer (JN-7228, manufactured by JSR Corporation), 18 g of silica sol (MEK-ST, manufactured by Nissan Chemical Co., Ltd.), 165 g of methyl isobutyl ketone and 12 g of cyclohexanone were added, and the pore size was stirred. The mixture was filtered through a 1 μm polypropylene filter to prepare a coating solution for a low refractive index layer having a solid refractive index of 1.42.

[Example 47-1]
Cellulose triacetate film sample 101-1 obtained in Example 1 (80 μm thick)
In addition, the above-mentioned coating liquid for hard coat layer was applied using a bar coater, dried at 120 ° C. and then 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.),
The coating layer was cured by irradiating with ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ² to form a hard coat layer having a thickness of 4 μm. Further, the anti-glare layer coating solution A is applied with a bar coater, dried under the same conditions as the hard coat layer, and then subjected to nitrogen purge in an atmosphere having an oxygen concentration of 0.01%. UV-cured under the same conditions as above, and a thickness of about 1.
A 5 μm antiglare layer was formed. On top of that, the low refractive index layer coating solution is applied using a bar coater, dried at 80 ° C., and further heated at 120 ° C. for 10 minutes to promote the thermal crosslinking reaction, resulting in a thickness of 0. A low refractive index layer of 096 μm was formed.

The surface of the cellulose triacetate film on the back side of the film was prepared by immersing the antiglare antireflection film thus prepared in 55 ° C, 1.5N NaOH aqueous solution for 2 minutes, neutralizing with 1N nitric acid aqueous solution, and washing with water. Only a saponified film was obtained. Next, the conventional P
The cellulose acylate film sample 101-1 produced by the present invention was immersed in a 1.5N KOH aqueous solution for 2 minutes at 55 ° C. on one side of a polarizer made of VA / iodine, neutralized with a 1N nitric acid aqueous solution, A polarizing plate was prepared by laminating the saponified film by washing with a protective film. Thereafter, the above-mentioned antiglare antireflection film subjected to saponification treatment is converted to L.
Placed as a polarizing plate on the viewing side of the C cell, and a polarizer made of PVA / iodine with the above cellulose triacetate bonded to the saponified cellulose triacetate surface improves visibility by providing an antireflection function. An LCD panel was created.

The obtained LCD panel exhibited excellent antireflection properties, and almost no reflection of the fluorescent lamp was observed even under a fluorescent lamp, indicating excellent LCD display performance.

[Example 47-2]
In Example 47-1, anti-glare was applied in the same manner as in Example 47-1, except that the coating liquid B for low refractive index layer was used instead of the coating liquid A for low refractive index layer and the film thickness was changed to 0.098 μm. An antireflection film and a polarizing plate were prepared, and an LCD panel with an excellent antireflection function was also prepared.

[Example 47-3]
In Example 47-2, WV FILM wide view A WV A03B (manufactured by Fuji Photo Film Co., Ltd.) having an optical compensation layer for improving the LCD viewing angle instead of a saponification-treated product of uncoated cellulose triacetate film A polarizing plate is prepared by using saponification treatment, and is disposed on the viewing side surface of the LC cell. The LC cell has the WV film on one side on the backlight side and an uncoated cellulose triacetate film on the opposite side. The saponification product was placed with the WV film side facing the cell, and an LCD panel with significantly improved visibility by providing a viewing angle widening function and an antireflection function was produced.

An experiment for producing a multilayer antireflection film of the present invention, producing a polarizing plate and applying it to an LCD was conducted as Example 48.

(Preparation of titanium dioxide dispersion)
Titanium dioxide (primary particle weight average particle size: 0.050 μm, refractive index: 2.70) 30 parts by weight, anionic monomer (DMAEA, manufactured by Kojin Co., Ltd.) 1 part by weight, cationic monomer (
KAYAMER PM-21, Nippon Kayaku Co., Ltd.) 6 parts by weight and cyclohexanone 63
Part by weight was dispersed with a sand grinder to prepare a titanium dioxide dispersion.

(Preparation of coating solution for medium refractive index layer)
To 172 g of cyclohexanone and 43 g of methyl ethyl ketone, 0.18 g of photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and photosensitizer (Kayacure DETX,
0.059 g of Nippon Kayaku Co., Ltd. was dissolved. Further, 15.8 g of titanium dioxide dispersion and 3.1 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) were added and stirred at room temperature for 30 minutes. The solution was filtered through a mesh filter to prepare a medium refractive index layer coating solution.

(Preparation of coating solution for high refractive index layer)
To 183 g of cyclohexanone and 46 g of methyl ethyl ketone, 0.085 g of photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and photosensitizer (Kayacure DETX)
0.028 g of Nippon Kayaku Co., Ltd.) was dissolved. In addition, 17.9 g of titanium dioxide dispersion
And 1.0 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), stirred at room temperature for 30 minutes, filtered through a 1 μm mesh filter, A coating solution for the refractive index layer was prepared.

[Example 48-1]
A film in which a hard coat layer was formed in the same manner as in Example 47-1 on a cellulose triacetate film obtained by saponifying Sample 101-1 of Example 1 was prepared, and a coating solution for a medium refractive index layer was placed on the film. After coating using a coater and drying at 120 ° C. for 5 minutes, the coating layer is cured by irradiating with an ultraviolet ray having an illuminance of 500 mW / cm ² and an irradiation amount of 600 mJ / cm ² in an atmosphere with an oxygen concentration of 4% by nitrogen purge. Medium refractive index layer (refractive index: 1.68, film thickness: 0.081
μm).

On the middle refractive index layer, a coating solution for a high refractive index layer is applied using a bar coater, and the coating layer is dried and cured under the same conditions as the above middle refractive index layer to obtain a high refractive index layer (refractive index: 1.92, film thickness: 0.0
53 μm). On the high refractive index layer, the low refractive index layer coating solution used in Example 47-2 was applied using a bar coater, dried at 80 ° C., and further heated at 120 ° C. for 10 minutes to heat. Promotes cross-linking reaction, low refractive index layer (refractive index: 1.42, film thickness: 0.098 μm)
Was provided. Thus, an antireflection film having an antireflection layer composed of three optical thin films was prepared. Further, a polarizing plate was prepared and applied to an LC cell in the same manner as in Example 47-1, and it had an extremely low reflectance (average reflectance in the wavelength region of 450 nm to 650 nm: 0.001).
3%), an LCD panel having a high contrast enough to withstand outdoor use could be produced.

[Example 48-2]
An embossing roll having surface irregularities with a maximum surface roughness of 10 μm is set on a single-sided embossing calender (manufactured by Yuri Roll Co., Ltd.) on the antireflection film prepared in Example 48-1, press pressure 600 kgf / cm, preheating Surface roughness was imparted by embossing under conditions of a roll temperature of 120 ° C., an embossing roll temperature of 120 ° C., and a processing speed of 2 m / min, to produce an antiglare antireflection film. Further, in the same manner as in Example 48-1, an LCD panel having a high contrast enough to withstand outdoor use and having no background reflection could be produced.

In Example 48-1, an LCD panel was produced in the same manner as in Example 48-1, except that instead of the sample 101-1 of Example 1, the sample 101-12 was used. The LCD panel had a high contrast enough to withstand outdoor use and no background reflection.

A PVA film (75 μm) was immersed in an aqueous solution of iodine 1.0 g / L and potassium iodide 60.0 g / L at 25 ° C. for 60 seconds, and further boric acid 80 g / liter, potassium iodide 30
g / L, ferrous chloride 10 g / L, stretched 5.0 times in an aqueous solution at 50 ° C.,
Dry at 60 ° C. for 5 minutes. Thereafter, both surfaces of the cellulose acylate film sample 101-1 produced in the present invention of Example 1 were saponified using a 4% aqueous solution of PVA (PVA-117H manufactured by Kuraray Co., Ltd.) as an adhesive. Bonding and further drying at 80 ° C. gave a polarizing plate. Here, the saponification treatment of the cellulose acylate film sample 101-1 was 1.5.
Soaked in N sodium hydroxide aqueous solution (55 ° C) for 2 minutes, washed with running water at 30 ° C for 15 seconds, further soaked in 0.1N sulfuric acid aqueous solution (30 ° C) for 30 seconds, followed by running water at 30 ° C 15
It was washed with water for 2 seconds and then dried at 120 ° C. for 1 minute.

The transmittance of this polarizing plate was 43.14%, and the degree of polarization was 99.95%. This polarizing plate is 6
Transmittance after standing at 0 ° C. and 90% RH for 24 hours, 43.12%, polarization degree is 99.96
%Met. Here, the characteristics of the polarizing plate were measured as follows.

(Transparency of polarizing plate)
The transmittance was measured with a Shimadzu spectrophotometer UV-3100PC, and calculated according to the following formula from the spectral transmittance τ (λ) obtained every 10 nm. In the equation, P (λ) is a spectral distribution of the standard light C light source, and y (λ) is a color matching function based on the two-degree field of view X, Y, Z system.
Transmittance T = {∫ (780-380) P (λ) y (λ) τ (λ) dλ} / {∫ (
780-380) P (λ) · y (λ) dλ}

(Polarization degree of polarizing plate)
The degree of polarization is calculated by the following formula.
Polarization degree P = ((Tp−Tc) / (Tp + Tc) ^1/2
However, Tp is the transmittance (%) when the absorption axes of the two polarizing plates are superposed in parallel in the sample of two polarizing plates, and Tc is perpendicular to the absorption axis of the two polarizing plates. It is the transmittance (%) when superimposed.

In Examples 1 to 23 described in JP 2000-301588 A, except that the resin solution (dope) is changed to the dope sample 001 of Example 1 of the present invention, JP 2000-301 A is disclosed.
Samples 5101 to 5123 were produced in exactly the same manner as in Examples 1 to 23 described in Japanese Patent No. 588. All of the obtained samples had a thickness unevenness of AA or BB, and the produced cellulose acylate film was excellent in flatness.

Here, the evaluation of the thickness unevenness of the film is based on the above-mentioned publication, and minute irregularities on the surface were evaluated using an optical interferometer. The thickness unevenness occurrence state is evaluated by AA to CC.
AA: No unevenness in thickness occurred. BB: The thickness unevenness was weak, but there was no practical problem. CC: Unevenness in thickness occurred strongly and was not suitable for practical use.

In Examples 1 to 9 described in JP-A No. 2000-301555, the resin solution (dope) is changed to the dope sample 001 in Example 1 of the present invention.
Samples 5201 to 5209 were produced in exactly the same manner as in Examples 1 to 9 described in Japanese Patent No. 55. All of the obtained samples had a thickness unevenness of AA or BB, the non-chlorine organic solvent of the present invention was an excellent solution, and the produced cellulose acylate film was also excellent in flatness. Here, the evaluation of the film thickness unevenness was in accordance with Example 51.

In Example 1 described in JP-A No. 11-262950, except that cellulose triacetate having a thickness of 80 μm is changed to Sample 101-52 which is a cellulose acylate film produced using the non-chlorine organic solvent of the present invention. Produced a sample 5301 in exactly the same manner as in Example 1 described in JP-A-11-262950. The obtained knurled film had an excellent shape.

In Examples 1 to 4 described in JP-A No. 11-248940, except that triacetyl cellulose is changed to Sample 101-52 which is a cellulose acylate film prepared using the non-chlorine organic solvent of the present invention. Samples 5401 to 5404 were prepared in exactly the same manner as in Example 1 described in JP-A-11-248940. The obtained triacetyl cellulose provided with a gelatin layer had excellent adhesiveness.

In Example 1 described in JP-A-4-85011, except that the solute and the solvent are changed to the dope sample 001 of Example 1 of the present invention, Example 1 described in JP-A-4-85011 Sample 5501 was produced in exactly the same manner. The adhesion of the dope to the roller as the casting support was not generated and was an excellent cellulose triacetate solution.

In the examples described in JP-A-5-86212, the cellulose triacetate and the solvent composition are changed to the cellulose triacetate solution of (2-1) in Example 2 of the present invention, in JP-A-5-86212. Examples described in JP-A-5-86212 except that the dropping solvent of Example 2 described is changed to methyl acetate / acetone / methanol / ethanol / butanol = 60/5/5/5/5 parts by mass. Casting was performed in exactly the same manner as in 1. As a result, the occurrence of skinning was at a level with no problem, and it was confirmed that the cellulose acylate solution produced using a non-chlorine organic solvent had favorable productivity.

In Example 1 described in JP-A-5-185445, the dope used is changed to the cellulose triacetate solution of (2-1) of Example 2 of the present invention, JP-A-5-1854.
The dropping composition of Example 1 described in Japanese Patent No. 45 was changed to methyl acetate / acetone / methanol / ethanol / butanol = 60/5/5 / which is a dropping solvent system composed of the non-chlorine organic solvent of the present invention.
Except for changing to 5/5 parts by mass, casting was performed in the same manner as in Example 1 described in JP-A-5-86212. As a result, the occurrence of skinning was at a level with no problem, and it was confirmed that the cellulose acylate solution produced using a non-chlorine organic solvent had favorable productivity.

In Example 12, (12-1) cellulose triacetate solution was added to
A sample 5801 was produced in the same manner as in Example 12 except that 0.5 part by mass of Compound A-45 (tribenzylamine) described in No. 7073 was additionally added (thickness was 80 μm). The obtained sample 5801 had almost the same characteristics as the sample 1201 of Example 12. On the other hand, when the mixture was aged at 60 ° C. and 90% for 4 months, no change in appearance was observed and there was no problem. On the other hand, sample 1201 showed no change in appearance, but when it smelled near the nose, a slight acetic acid odor was observed. Therefore, in the present invention, it is apparent that the present invention is also a preferred embodiment for the invention described in JP-A-5-107073.

In Example 12, (12-1) cellulose triacetate solution was added to Japanese Patent Application Laid-Open No. 6-10.
Sample 5901 and Sample 5902 were prepared in exactly the same manner as in Example 12 except that 0.5 parts by mass of Compound D-8 or Compound BI-12 described in No. 7854 was added (thickness was 80 μm). The obtained samples 5901 and 5902 had almost the same characteristics as the sample 1201 of Example 12. Furthermore, when it was aged for 4 months at 60 ° C. and 90%, no change in appearance was observed, and there was no problem, and it was preferable to carry out the present invention for the invention described in JP-A-6-107854. It is clear that there is.

In Examples 1 to 4 described in JP-A-8-50206, a sample 540 which is a cellulose acylate film prepared by using triacetyl cellulose using a non-chlorine organic solvent.
An optical compensation sheet of Sample 6001 was prepared in exactly the same manner as Example 1 described in JP-A-8-50206, except for changing to 1. The characteristics of the obtained sample have optical anisotropy and indicate that a cellulose acylate film produced using a non-chlorine organic solvent is useful.

In Examples 1 to 5 described in JP-A-8-94838, Sample 1 which is a cellulose acylate film prepared by using cellulose triacetate film A using a non-chlorine organic solvent
Except for changing to 01-12, elliptical polarizing plates for optical use of samples 6101 to 6105 were prepared in exactly the same manner as in Examples 1 to 5 described in JP-A-8-94838. The properties of the obtained sample were confirmed to have the same properties as those described in JP-A-8-94838, and a cellulose acylate film produced using a non-chlorine organic solvent was obtained. This shows that the present invention can be applied to saponification in JP-A-8-94838 and is useful.

In Example 1 described in JP-A-8-95030, triacetylcellulose is used.
Sample 101-, which is a cellulose acylate film prepared using a non-chlorine organic solvent
Except for changing to 12, an optical compensation sheet of the sample 6201 and its liquid crystal display device were produced in exactly the same manner as in Example 1 described in JP-A-8-95030. The characteristics of the obtained sample are recognized to have the same characteristics as those described in JP-A-8-94838, and a cellulose acylate film produced using a non-chlorine organic solvent is particularly characteristic. Kaihei 8-
The invention described in Japanese Patent No. 95030 also shows that it can be applied without problems and is useful.

In the production of the sample 110 of Example 1 described in Japanese Patent Laid-Open No. 2000-105445, P
Except for changing the EN film to a cellulose triacetate support obtained by adding the following undercoat layer and back layer to Sample 101-52 (thickness: 125 μm), which is a cellulose acylate film prepared using a non-chlorine organic solvent. Produced a silver halide photographic light-sensitive material (color negative light-sensitive material) of Sample 6301 in exactly the same manner as in Example 1 described in JP-A-2000-105445. The characteristics of the resulting light-sensitive material were confirmed to have the same characteristics as Example 1 described in JP-A-2000-105445, and were prepared using a non-chlorine organic solvent. This shows that the film can be applied without any problem even in the invention described in JP-A-2000-105445.

  For the support used in this example, an undercoat layer and a back layer were prepared by the following method.

(Coating the undercoat layer)
The cellulose acylate film sample 101-12 prepared using the non-chlorine organic solvent of the present invention as a support was subjected to corona discharge treatment, UV irradiation treatment, and glow discharge treatment, and then gelatin 0 on one surface. .1g / m ^2, Sodium α- Suruhoji-2-ethylhexyl succinate 0.01 g / m ^2, salicylic acid 0.04g / m ^2, p- chlorophenol _{^{0.2g / m 2, (CH 2}} = CHSO 2 CH 2 CH ₂ NHCO) ₂ CH ₂ 0.01
A primer solution of ² g / m ² , polyamide-epichlorohydrin polycondensate 0.02 g / m ² was applied (10 mL / m ² , using a bar coater) to provide a primer layer. Drying was carried out at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.).

(Coating back layer)
An antistatic layer having the following composition and a slipping layer were coated as a back layer on the other surface of the support after the undercoating.

(Coating of antistatic layer)
The specific resistance of the tin oxide-antimony oxide composite having an average particle size of 0.005 μm is 0.2 g / m ^{2 of} a dispersion of fine powder (secondary aggregated particle size of about 0.08 μm) of 5 Ω · cm, 0.05 g of gelatin. / M ² , (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.02 g
/ M ² , polyoxyethylene-p-nonylphenol (degree of polymerization 10) 0.005 g / m
² and resorcin 0.22 g / m ² .
(Preparation of sliding layer)
Diacetylcellulose (25 mg / m ² ), C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H
_A mixture of ₈₁ (6 mg / m ² ) / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (9 mg / m ² ) was applied. This mixture is made of xylene / propylene glycol monomethyl ether (
1/1) melted at 105 ° C., and propylene glycol monomethyl ether (1
It was prepared by pouring and dispersing in (0 times the amount), and then adding the dispersion in acetone (average particle size 0.01 μm). Silicon dioxide particles (0.3 μm) were added as a matting agent so as to be 15 mg / m ² . Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were 115 ° C.). The sliding layer has a dynamic friction coefficient of 0.06 (5 mmφ stainless hard ball, load 100 g, speed 6 cm / min), static friction coefficient 0.07 (clip method), and the dynamic friction coefficient of the emulsion surface and the sliding layer is also excellent at 0.12. It was a characteristic.

In Example 1 (production of sample 132) described in JP-A-11-282119,
Sample 101-52, which is a cellulose acylate film prepared using a non-chlorine organic solvent, from a cellulose triacetate film having a thickness of 127 μm to which an undercoat has been applied.
except that the cellulose triacetate support provided with (undercoat layer), (antistatic layer) and a slipping layer as in Example 63 is completely changed from Example 1 described in JP-A No. 11-282119. Similarly, a silver halide photographic light-sensitive material (color reversal light-sensitive material) of Sample 6401 was produced. The characteristics of the obtained light-sensitive material were recognized as having the same characteristics as Example 1 described in JP-A No. 11-282119, and were produced using the non-chlorine organic solvent of the present invention. This indicates that the cellulose acylate film can be applied without any problem even in the invention described in JP-A-11-282119.

In the preparation of the coated sample of the example described in JP-A-4-163542, the coated sample 1
The silver halide photographic light-sensitive material of Samples 6510 to 6514 was exactly the same as the example described in JP-A-4-163542 except that 0 to 14 triacetylcellulose was changed to Sample 101-52 of the present invention. (Monochrome sensitive material) was produced. The characteristics of the resulting light-sensitive material are described in JP-A-4-
No. 163542 is recognized to have the same characteristics as the examples described in the above, and a cellulose acylate film produced using a non-chlorine organic solvent is disclosed in JP-A-4-163.
This indicates that the invention described in Japanese Patent No. 542 is applicable without problems and is useful.

A cellulose acetate film, an optical compensation sheet, and a polarizing plate were produced in exactly the same manner as in Example 13 except that the cellulose acetates of Examples 1 to 3 described in JP-A No. 11-5851 were used. The obtained performance was almost the same as in Example 13, and there was no problem at all.

In Example 1, the dope was obtained by the cooling dissolution method in the same manner as in Example 2. It was able to dissolve without problems. Further, when this was cast and evaluated in the same manner as the cellulose acylate film sample 101-1, it was almost the same as the sample 101-1.

The following experiment was performed for comparison with Example 1.
The decompression of the decompression chamber of (1-4) in Example 1 was stopped, and the rabin rinse was also removed. Moreover, the partition plate was provided in the wind pressure vibration suppression means of the casting support of Example 1 (1-6), and the experiment was performed with the suppression effect removed. Except for this, a cellulose acylate film sample 6701 was prepared in exactly the same manner as 101-1 of Example 1. In addition, the implementation scale was implemented with the scale from which a casting winding film length will be 150 m.
When the thickness variation of the sample 6901 was measured, it was an unacceptable use of 80 μm ± 3 μ in a length of 1 m.

Under the conditions of Example 67, the solvent supply at the bead end of Example 1 (1-5) was further stopped.
Except for this, a material 7001 similar to that in Example 67 was prepared. The implementation scale was a scale with a casting winding length of 150 m. Similarly, when measuring the thickness variation,
It was further deteriorated to 80 μm ± 5 μ.

Under the conditions of Example 68, the die height of (1-5) of Example 1 was set to 3.5 mm. Other than this, a material 6901 similar to that in Example 68 was prepared. The implementation scale is 15 in the winding length.
The scale was 0 m. Similarly, when measuring the thickness variation,
It further deteriorated to 80 μm ± 8 μ.

Further, in Example, a material 7001 similar to that in Example 69 was prepared except that the citrate ester mixture was removed from the composition in Example 1. The actual scale is 150 in terms of the winding length.
The scale was m. Similarly, when the thickness variation was measured, it was further deteriorated to 80 μm ± 12 μm.

`` Fujitac '', `` FUJITAC '', ``
Fuji TAC, Fuji TAC, Fuji Tac, TD80, TD80U, TD80UF, T80
, "T80U", "T80UZ", "T80UF", "FTUV", "FTUV80", "FTUV50", "UVD", "U
It is useful to use the cellulose film described in the present invention in place of each cellulose film such as “VD50”, “UVE”, “UVE50” and the like.

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294959, JP-A-9-318817, JP-A-9-80233, JP-A-10-10320, JP-A-10-104428, JP-A-10-111403, JP-A-10-111507, JP-A-10-123302 , JP 10-123322, JP 10-123323, JP 10-176118, JP 10-186133, JP 10-264322, JP
JP-A-10-268133, JP-A-10-268134, JP-A-10-319408, JP-A-10-332933, JP-A-10-3
No. 9137, JP-A-10-39140, JP-A-10-68821, JP-A-10-68824, JP-A-10-90517,
JP-A-11-116903, JP-A-11-181131, JP-A-11-211901, JP-A-11-211914, JP-A-11-242119, JP-A-11-246693, JP-A-11-246694, Special Kaihei 11-256117, JP-A-11
-258425, JP-A-11-263861, JP-A-11-287902, JP-A-11-295525, JP-A-11-295
No. 527, JP-A-11-302423, JP-A-11-309830, JP-A-11-323552, JP-A-11-335641
JP, 11-344700, JP 11-349947, JP 11-95011, JP 11-95030, JP 11-95208, JP 2000-109780, JP 2000-110070. , JP2000-119657, JP200
0-141556, JP 2000-147208, JP 2000-17099, JP 2000-171603, JP 2000-171
618, JP 2000-180615, JP 2000-187102, JP 2000-187106, JP 2000-191819
JP, 2000-191821, JP 2000-193804, JP 2000-204189, JP 2000-206306,
JP 2000-214323, JP 2000-214329, JP 2000-230159, JP 2000-235107, JP
2000-241626, JP 2000-250038, JP 2000-267095, JP 2000-284122, JP 2000
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196, JP 2000-309198, JP 2000-309642, JP 2000-310704, JP 2000-310708
JP, 2000-310709, JP 2000-310710, JP 2000-310711, JP 2000-310712,
JP 2000-310713, JP 2000-310714, JP 2000-310715, JP 2000-310716, JP
JP 2000-310717, JP 2000-321560, JP 2000-321567, JP 2000-338309, JP 2000
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026, JP 2000-347027, JP 2000-347029, JP 2000-347030, JP 2000-347031
JP, 2000-347032, JP 2000-347033, JP 2000-347034, JP 2000-347035,
JP 2000-347037, JP 2000-347038, JP 2000-86989, JP 2000-98392, JP 20
01-100012, JP 2001-108805, JP 2001-108806, JP 2001-133627, JP 2001-1
33628, JP 2001-142062, JP 2001-142072, JP 2001-174630, JP 2001-17463
4, JP 2001-174637, JP 2001-179902, JP 2001-183526, JP 2001-188103, JP 2001-188124, JP 2001-188125, JP 2001-188225 JP, 2001-188231, JP 2001-194505, JP 2001-228311, JP 2001-228333, JP 2001-242461, JP 20
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JP 2001-51119, JP 2001-51120, JP 2001-51273, JP 2001-51274, JP 2001
JP-A-55573, JP-A-2001-66431, JP-A-2001-66597, JP-A-2001-74920, JP-A-2001-81469, JP-A-2001-83329, JP-A-2001-83515, JP-A-2002- 162628, JP 2002-169024, JP
2002-189421, JP 2002-201367, JP 2002-20410, JP 2002-258046, JP 2002-
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JP 3-105540, JP 2003-114331, JP 2003-131036, JP 2003-139952, JP 2003-17
Publication Nos. 2819, 2003-35819, 2003-43252, 2003-50318, and 2003-96066.

It is the schematic which shows the structure of the solution casting apparatus of this invention. It is a perspective view which shows the structure of a vibrational absorption chamber. It is the schematic which shows the structure of the solution casting apparatus of another embodiment. It is the schematic which shows the structure of the solution casting apparatus of another embodiment. It is a perspective view which shows the structure of a bellows type vibration absorption chamber. It is a perspective view which shows the structure of the vibrational absorption chamber for positive pressures. It is a perspective view which shows the structure of the vibrational absorption chamber for negative pressures. It is the schematic which shows the structure of the solution casting apparatus of another embodiment. It is the schematic of the side surface of the casting die vicinity of the solution casting apparatus which enforces the solution casting method by this invention. It is a schematic diagram of the casting die part of a solution casting apparatus. It is a schematic diagram of the solution casting apparatus which enforces the solution casting method of this invention. It is a top view of a casting die part. It is a bottom view of a back suction device. It is a schematic cross section of the casting die used in the present invention. It is a schematic cross section of the casting die used in the present invention. It is a schematic cross section of the casting die used in the present invention. It is a side view which shows schematic structure of the solution casting apparatus used by this invention. It is a top view which shows a casting part. It is a schematic diagram which decomposes | disassembles and shows one Embodiment of the liquid crystal display device of this invention. It is a schematic diagram which decomposes | disassembles and shows one Embodiment of the liquid crystal display device of this invention. It is a schematic diagram which decomposes | disassembles and shows one Embodiment of the liquid crystal display device of this invention. It is a schematic diagram which decomposes | disassembles and shows one Embodiment of the liquid crystal display device of this invention.

Explanation of symbols

10, 30, 40, 50 Solution casting apparatus 11 Casing 12, 13 Drum 14 Belt 15 Casting dies 16, 17, 18 Shield plates 20, 31, 32, 41, 42, 43, 44, 45 Vibration absorption chamber 22 Drying Wind 102 Driving drum 103 Casting dies 104, 106 Labyrinth 105, 107 Seal 108 Opening 109 Heat insulation jacket 110, 121 Casing 111, 112 Drying air supply duct 201 Ribbon polymer solution 202 Support 203 Decompression chamber 204 Ribbon 210 Casting die 211 Manifold 212 Manifold 213 Manifold 214 Feed block 220 Rotating drum 221 Stripping roller 230 Casting band (support)
240 Back Suction Device 241 Decompression Chamber 242 Decompression Chamber 243 Suction Duct Connection Port 244 Partition 245 Labyrinth 250 Suction Duct 260 Buffer Tank 270 Blower 280 Casting Drum 310 Solution Casting Device 312 Casting Die 314 Casting Band 316 Depressurization Chamber 318 Dropping Device 320 Casting drum 322 Suction duct 324 Blower 326 Casting part 326A Ear part 328 Buffer tank 330 Tank 332 Pump 334 Feed pipe 336 Labyrinth seal

Claims (20)

In a solution casting method in which a dope in which cellulose acylate is dissolved in an organic solvent is cast from a casting die onto a support consisting of an endless belt or a drum rotating in a casing and dried to form a film. ,
Wind pressure vibration suppressing means for suppressing wind pressure vibration in the casing is provided in at least one casing, and either at the front or rear of the casting portion of the casting support on which the dope is cast from the die. A solution casting method characterized in that a labyrinth and a seal are provided, and a ribbon formed by a bead discharged from a casting die is decompressed from the rear. The wind pressure vibration suppressing means is formed using an elastic thin film, is configured such that the thin film elastically deforms in response to wind pressure vibration in the casing, and has openings at both ends of the seal. The solution casting method according to claim 1. The distance between the die and the support is set to 0.3 to 3.5 mm, the bead length is shortened, the bead vibration is set to 10 to 60 Hz, and the thickness variation of 1 to 100 mm period after film formation is suppressed. The solution casting method according to claim 1 or 2. When depressurizing from the rear of the casting die using the decompression chamber, a buffer tank that absorbs pressure vibration is provided in the middle of the decompression chamber from the decompression pump, and the sectional area of the buffer tank / the sectional area of the duct piping is 5 ~ 200 times, buffer tank length is 1m or more,
4. The solution casting method according to any one of claims 1 to 3, wherein a buffer tank in which means for retaining an air flow is installed is used. The solution casting method according to any one of claims 1 to 4, wherein a good solvent for the solute of the solution is dropped onto an ear portion of a bead portion cast from the die. A solution accelerator according to any one of claims 1 to 5, wherein a peeling accelerator is added to the organic solvent-based dope or cellulose acylate to reduce the peeling resistance when the dope is peeled off from the support. Membrane method. The peeling accelerator is a polybasic acid having an acid dissociation constant pKa in an aqueous solution of less than 1.93 to 4.50,
7. The solution casting method according to claim 6, which is a partial ester, an alkali metal salt, or an alkaline earth metal salt. The cellulose acylate film has a multilayer structure of three or more layers, and the release accelerator is
7. The solution casting method according to claim 6, wherein at least the layer is added to a layer in contact with the support. The film after casting contains 3 to 20% by weight of a plasticizer with respect to cellulose acylate,
The ultraviolet ray absorber is contained by 0.001 to 5% by weight, and the fine particle powder is contained by 0.001% to 5% by weight. Cellulose acylate film. A retardation control agent for a lower fatty acid ester film of cellulose comprising a compound having a molecular structure having at least two aromatic rings and having a steric hindrance to the conformation of the two aromatic rings. A cellulose acylate film produced by the solution casting method according to any one of 1 to 8. It contains 0.3 to 20 parts by weight of a compound having a molecular structure that has at least two aromatic rings and does not sterically hinder the conformation of the two aromatic rings with respect to 100 parts by weight of cellulose acylate, and has a wavelength of 550 nm The retardation value in the thickness direction (Rth550) at 70 to 400
It consists of a lower fatty acid ester film of cellulose which is nm.
An optical compensation sheet produced by the solution casting method according to any one of 8 to 8. 12. The optical compensation sheet according to claim 11, wherein an optically anisotropic layer containing a discotic liquid crystalline molecule is provided on the cellulose lower fatty acid ester film. The retardation value (Rth550) in the thickness direction measured at a wavelength of 550 nm is 60 to 10 with 0.01 to 20 parts by weight of a discotic compound per 100 parts by weight of cellulose ester.
The cellulose acylate film produced by the solution casting method according to claim 1, wherein the film is 00 nm. 14. The cellulose acylate film according to claim 13, wherein the discotic compound is a compound having a 1,3,5-triazine ring. 0.0100% of a compound having a triphenylene ring is added to 100 parts by weight of cellulose acylate.
Including 1 to 20 parts by weight, retardation value in the thickness direction at a wavelength of 550 nm (Rth55
The cellulose acylate film produced by the solution casting method according to any one of claims 1 to 8, wherein 0) is 70 to 400 nm. On a cellulose acylate film containing 0.01 to 20 parts by weight of a compound having a triphenylene ring with respect to 100 parts by weight of cellulose acylate ester and having a retardation value (Rth550) in the thickness direction at a wavelength of 550 nm of 70 to 400 nm. 9. An optical compensation sheet produced by the solution casting method according to claim 1, further comprising an optically anisotropic layer containing discotic liquid crystalline molecules. The cellulose acylate film according to any one of claims 8 to 14, wherein the cellulose acylate film is stretched by 101 to 130% in the casting direction and 101 to 150% in the vertical direction of the casting and has a thickness of 40 µm to 100 µm. A polarizing plate comprising the cellulose acylate according to claim 17. A liquid crystal display device comprising the polarizing plate according to claim 18. 20. The liquid crystal display device according to claim 19, wherein the liquid crystal display panel is a TN type, OCB type, VA type, IPS type, transflective type, or reflective type.

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