TWI322042B - Method and apparatus for producing film from polymer solution, and optical polymer film - Google Patents

Description

1322042 IX. Description of the Invention: [Technical Field] The present invention relates to an optical polymer film, and a method and apparatus for manufacturing a film (and more particularly an optical polymer film having optical properties), and an optical polymerization process Method and apparatus for film (as a polarizing filter protective film for optical functional films and liquid crystal displays). [Prior Art] A liquid crystal display (hereinafter referred to as LC D) is composed of a liquid crystal tube, a polarizing element, and an optical compensation sheet (birefringent sheet). In the light-transmitting type LCD, two polarizing elements are provided on both sides of the liquid crystal tube, and one or two optical compensation sheets are disposed between the liquid crystal tube and the polarizing element. In the reflective LCD, the reflection sheet, the liquid crystal tube, the optical compensation sheet, and the polarizing element are overlapped in this order. The liquid crystal tube is composed of rod-shaped liquid crystal molecules, two substrates for accommodating the same, and an electrode layer for applying a voltage to the rod-shaped molecules. There are several types of display mode liquid crystal tubes which are used depending on the orientation of the liquid crystal molecules used. For example, as the light transmission type, there are TN (twisted nematic), IPS (switching in plane), FLC (ferroelectric liquid crystal), OCB (optical compensation bending), STN (super twisted nematic), VA (vertical alignment). Etc., and as a reflection type, there are TN (twisted nematic), HAN (mixed nematic), and the like. The polarizing element usually has a structure in which two transparent protective films are attached to both surfaces of the polarizing film. In addition, optical compensation sheets are used in many liquid crystal displays to reduce irregular discoloration of the displayed image or to magnify the viewing angle. In the optical compensation sheet, a birefringent film obtained by stretching or drawing is preferably used. In addition to an optical compensation sheet containing a birefringent film, it has been proposed in recent years to use an optical compensation sheet having optical anisotropy, which 1322042 provides liquid crystal molecules (especially disk type liquid crystal molecules) on a transparent substrate. The orientation of the liquid crystal molecules is fabricated and fixed in order to provide optical anisotropy. In this case, the liquid crystal molecules have a polymerizable group, and polymerization of liquid crystal molecules is carried out for fixation. This liquid crystal molecule has large birefringence and exhibits several orientations. With these characteristics, an optical compensation sheet having an optical property which cannot be obtained by using a prior art film can be provided. The optical properties of the optical compensation sheet are determined in accordance with the optical properties of the liquid crystal tube (specifically, the display mode described above). Therefore, when liquid crystal molecules (especially disk type liquid crystal molecules) are used, the optical compensation sheet manufactured can have several optical properties corresponding to the display mode of the liquid crystal cell. Several types of display mode optical compensation sheets are proposed in many patent applications in which disc type liquid crystal molecules are used. For example, U.S. Patent No. 5, 583, 679, No. 5, 646, 703, and German Patent Application Publication No. 391162 No. 1 teaches an optical compensation sheet for a ΤΝ mode liquid crystal cell. Japanese Patent Laid-Open Publication No. 1/54982 teaches an optical compensation sheet for an IPS mode or FLC mode liquid crystal tube. In addition, the optical compensation sheet for the OCB mode liquid crystal tube and the HAN mode liquid crystal tube is taught in the U.S. Patent No. 5,085,053, the entire disclosure of which is incorporated herein by reference. An optical compensation sheet for a STN mode liquid crystal tube, and an optical compensation sheet for a VA mode liquid crystal tube are taught by Japanese Patent No. 2863372. However, although there are many kinds of alignment modes of liquid crystal molecules, the above liquid crystal anisotropy sometimes fails to optically compensate the liquid crystal cell. U.S. Patent No. 5,646,703 sets optical crystal molecules and transparent substrates of optical compensation sheets to have optical anisotropy. This liquid crystal tube is thus optically compensated. 1322042 There are several advances in the performance of several of these products for many optical applications. In the progress of such optical use products (e.g., these LCDs), it is necessary to make the films constituting each layer of the product have a uniform thickness and uniformity of optical properties with high accuracy. For example, the thickness unevenness (or thickness build-up) of the polarizing filter protective film causes warpage when attached to the polarizing element, and a curl-shaped polarizing filter after adhesion. Further, the optical film is coated with a hard coat layer for surface protection and an antireflection layer for preventing reflection. Thickness non-uniformities often result in uneven coatings (or coating buildup). In particular, when unevenness (or build-up) occurs cyclically, the image quality of the LCD display becomes extremely poor. Japanese Patent Publication Nos. 2002-234042 and 2002-1745 each teach a solution casting method as a method of producing a film in which thickness uniformity is further improved. However, recently, although a thinner thickness and a larger amount of overlapping film and improvement in productivity have been gradually required, it is necessary to control the thickness of a film made of a polymer with high accuracy. Thus, the productivity is not sufficiently improved and the film produced cannot have a uniform thickness and uniform optical properties. In addition, when the optical properties (especially the retardation 値Re, Rth) of the birefringence are not uniform, the influence on the product is large. For example, lightening and inversion sometimes occur in an LCD, and when the optical compensation sheet is used in an LCD to enlarge a viewing angle, a change in viewing angle and a color inversion sometimes occur. SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a film in which the thickness of the optical film and the birefringence unevenness are lowered, and the optical properties are excellent. Another embodiment of the present invention provides a device for producing a film in which the thickness of the optical film and the birefringence unevenness are lowered, and the optical property 1322042 is excellent. Another object of the present invention is to provide an optical polymer film having optical properties suitable for optical applications. In order to achieve this and other objects, in the method of forming a film of the present invention, at least one polymer solution discharged from the mold is cast on the surface before the substrate is moved to form a film. The substrate is heated using a heater disposed along the back surface of the substrate. The solvent evaporating from the film is condensed by a condensing device disposed close to the surface of the film. An apparatus for producing a film from the polymer solution of the present invention comprises a movable substrate, a mold for casting a polymer solution on the surface of the moving substrate to form a film, and a heater provided facing the back surface of the substrate. The apparatus further includes a condensing unit disposed adjacent to the film on the ground. This condensing device recovers by condensing the solvent vapor generated by the film. In the present invention, the optical polymer film includes characteristics satisfying the following formula: MD 1 ^ 0.1 OxTA 1 ; sp1max^ O.lOxTAl wherein ΤΑ 1 is the number of measurement points arranged in the first direction on the polymer film The average 値 of a thickness 値, MD1 is the error average 値 of the plurality of first thickness 値, and SP1MAX is the maximum 値 of the frequency spectrum SP1, which is obtained by the fast Fourier transform of the first thickness 値. According to the method and apparatus for producing a film from the polymer solution of the present invention, the thickness and the birefringence unevenness are greatly reduced, and thus the optical polymer film produced can have excellent optical properties. Among them, the optical polymer film of the 1322042 optical filter, the protective film, the optical functional film', and the liquid crystal display are excellent in optical properties. [Embodiment] [Solution Casting Method] In the following explanation, the upper molding liquid represents a polymer solution containing a solution and a dispersion liquid in which a polymer or a plurality of additives are dissolved or dispersed. Further, in Fig. 1, the upper molding liquid 11 is prepared by preparing the upper molding liquid in the above molding liquid molding method, and the casting upper molding liquid 12 is prepared by changing the upper molding liquid 11 to have suitable casting. The characteristics come. The film manufacturing facility is composed of an upper molding liquid preparation device 15, a casting device 16, a drying device 17, and a winding device 18. The upper molding liquid preparation apparatus 15 is provided with a tank 21 in which the upper molding liquid 11 is prepared, a pump 22, first and second filtration devices 23, 24, a heating device 27, and a flash evaporation/generation device for performing rapid evaporation. 28 composition. The tank 21 has a thermostat 21a and a thermometer (not shown) to appropriately heat and cool the upper mold liquid. In the present invention, it is preferred to heat the prepared upper molding liquid 11 once and then to cool so that the solubility can be increased. In addition, * In the heating and cooling, consider the type of the molding liquid, especially the solvent composition of the upper molding liquid, and set the temperature. Specifically, when the mixture solvent is used as the solvent, it is preferred to heat and cool the preparation molding liquid 11 to a predetermined temperature in a plurality of stages. The upper molding liquid 11 is prepared by the pump 22 to be fed to the casting apparatus 16 at a predetermined flow rate. The first and second filtering means 23' 24 are disposed between the pump 22 and the mold 14 to remove residual solid material contained in the molding liquid 11 prepared. In addition to this 1322042, after the filtration by the first filtration unit 23, the preparation of the upper molding liquid 11 is heated by the heating means 27 supplied to the feed line, and the rapid evaporation is carried out in the flash evaporation unit 28. It should be noted that the heating device 27 can be disposed upstream of the first filter device 23. The flash evaporation unit 28 is used to change the characteristics of the preparation of the molding liquid 11 into a casting molding liquid 12 suitable for casting. In the flash evaporation unit 28, the high pressure preparation upper molding liquid 11 is flushed into atmospheric pressure air to carry out flash evaporation. The solvent vapor generated by evaporating the upper molding liquid 11 is usually condensed and removed using a condenser (not shown), and is discharged from the film manufacturing facility into a recovery solvent. After the flash evaporation, the preparation of the overmold 11 is sent from the flash evaporation unit 28, and preferably the residual solid material is removed by the second filtration unit 24 before being fed to the casting apparatus 16. It should be noted in the present invention that the means for removing a part of the solvent for preparing the upper mold liquid 11 is not limited to the above-described flash evaporation apparatus 28, and for example, a thin film evaporator known to have a rotary blade, a multi-function evaporator, or the like can be used. . Additionally, an on-line static mixer (not shown) may be provided between the second filter unit 24 and the casting apparatus 16. In this case, the characteristics of the above-mentioned molding liquid 11 can be appropriately changed. It should be noted in the present invention that filter paper is used as the filter of the first filter unit 23, and a sintered metal filter is used as the second filter unit 24. Further, the present invention does not attach to the above molding liquid preparation apparatus 15. The filtered upper molding liquid 1 1 is fed to a casting apparatus 16 as a casting upper molding liquid 12. The casting upper molding liquid 12 fed to the casting apparatus 16 is cast on the belt path 31 which is moved by the rotating means (not shown) as a substrate -10- 1322042 to form a jelly film 35 (see Fig. 2). The belt 31 is supported by at least the first and second cylinders 32, 33, and its rotation causes the belt 31 to continuously move in the circulation path. The solvent gradually evaporates from the gel film 35 on the tape 31, so that the gel film 35 has self-supporting properties. Then, the gel film 35 is peeled off from the belt 31 by the stripping roller 37 to become a film 36. A free roller or a driving roller can be used as the peeling roller 37. When the stripping roller 37 is a driving roller, it is preferable to adjust the pulling ratio, tension and slack of the film 36 to at least drive the stripping roller 37. It should be noted that in the above specific embodiment, the stripping roller 37 has two functions of stripping and guiding the film 36. However, in the present invention, a peeling roller for peeling off the film 36 and a guide roller for guiding the film 36 to the drying device 17 may be separately provided. The drying device 17 is composed of a tension device 41 and a roller drying device 42. In the tension device 41, the both sides of the film 36 are held by a clip (not shown) or the like to apply tension to the film 36 to dry the film 36. The film 36 is then further dried in a roll drying unit 42 comprising a plurality of rolls. After drying, the film 36 is cooled in a cooling device (not shown) provided downstream of the drying device 17, so that the temperature of the film 36 is lowered to room temperature. Preferably, the sides of the dried film 36 are cut by the cutter 46 so that the film can have the width of the product. The film 36 is then wound by a winding device 47. In the present invention, the roller 48 can be provided between the above apparatus and the apparatus, and the number of the rollers 48 is not limited. It should be noted that the present invention is independent of the drying apparatus 17, the structure of the winding apparatus 18, and the drying and winding methods. The film can be dried and wound by several known drying methods and winding methods. Referring to Fig. 2, there is explained a solution casting method as a method of producing a polymer film from the polymer solution of the present invention. The casting apparatus 16 includes a mold 14'-11- 1322042 first and second support rolls 3 2, 3 3, a belt 3 1 , a stripping roll 37, a heating plate 5 1 , a plurality of condensers 52, and a plurality of liquid receivers 53. Recovery tank 56, and feed line. However, the invention is not limited to the casting apparatus 16. It should be noted in this embodiment that three casting mold liquids 12 are prepared, and the casting processes are simultaneously performed to form a gel film 35 having a three-layer structure. Therefore, as shown in Fig. 3, the gel film 35 has the first layer 35a, the second layer 35b, and the third layer 35c sequentially from the side of the belt 31. The heating plate 51 and the condenser 52 are each connected to a temperature controller 5 1 a, 52a. The heating plate 51 is disposed close to the back surface of the belt 31 (on which the gel film 35 is not formed) as a heating member for heating the belt 31. Further, a plurality of condensers 52 are provided on the opposite side of the heating plate 51 to approach the colloidal film 35 on the belt pair 3 1 . The surface of the heating plate 51 is formed of metal, and its temperature is controlled by a temperature controller 51a. The heating plate 51 controls the heat to heat the gel film 35 on the belt 31 to evaporate the solvent. It should be noted that the material of the surface of the heating plate 51 is not limited in this specific embodiment, and may be, for example, ceramic. Parts of the heating plate can be independently controlled by a temperature controller. The temperature control range is predetermined to be the lowest room temperature and the highest heat resistant temperature of the polymer or the highest boiling point of the solvent used. In this case, the heating plate 51 is sufficiently effective. Further, the heating temperature is determined in accordance with the type of the casting mold liquid 12. This determination is suitably made by considering the boiling point of the solvent, the evaporation rate, the compatibility of the solvent with the solid material, and the heat resistance and thermal dependence of the polymer and other solid materials contained in the casting mold solution. The heating plate 51 heats the facing belt 31 almost uniformly, and supplies the heat energy almost uniformly to the entire gel film 35 on the belt 31. The uniform heating is accomplished by controlling the evaporation rate of the solvent at each portion of the gel film 35. Since -12-1322042, the shape of the heating plate 51 is not limited as long as the temperature is controlled as described above. Therefore, a heating plate 51 can be provided as shown in Fig. 2 or a plurality of heating plates can be provided and arranged in the same area facing the colloidal film 35, and the temperature thereof is individually controlled. Further, the heating plate 51 is disposed in a strip 3 1 which is almost parallel to the almost linear movement. Further preferably, the temperature of the belt 31 supported by the first and second support rollers 32, 33 is adjustable. The first and second support rollers 32, 33 preferably have a temperature controller (not shown) for heating the belt 31. Particularly preferably, a temperature controller is provided for the first support roller 32, which is disposed in the mold. In this case, the belt 31 is heated not only between the first and second support rollers 32, 33 but also on the first and second support rollers 32, 33. Therefore, the evaporation rate of the solvent in the gel film 35 can be appropriately controlled. Further, the condenser 52 is provided just downstream of the casting position PS and just upstream of the stripping roller 37. The condenser 52 is disposed on the front side of the belt 3 1 close to the adjacent side to form the gel film 35 with a space therebetween. Further, a liquid receiver 53 is provided below the interval between adjacent condensers 52. In this embodiment, each condenser 52 is in the shape of a plate. The surface of the condenser 52 is made of metal, and its temperature is controlled by a temperature controller 52a to cool and condense the solvent vapor generated from the gel film 35. Thus, the condenser 52 effectively condenses the solvent vapor as long as the temperature is controlled to the range of the lowest boiling point of the solvent used to the highest freezing point of the solvent used. The solvent solidifies on the surface of the condenser 52 when the cooling temperature is lower than the freezing point of the solvent. In this case, solvent recovery becomes difficult, or a dissolving member is required to be recovered. It should be noted that the material of the condenser 52 is preferably of high thermal conductivity and is not limited in this embodiment. -13- 1322042 The cooling temperature of the condenser 52 is determined according to the solvent cost and the boiling point of the solvent. The point 'condensation speed and the freezing point are appropriately determined. The solvent vapor condenses and liquefies the solvent to flow downward on the inclined surface formed from the inner side (the side of the colloidal film 35) to the outer side (the side opposite to the inner side). It is then recovered by receiving the solvent from the liquid receiver 53. In the present invention, for ease of recovery, the inclination between the inner side and the outer side may have a structure in which the liquid flows downward by gravity, and the inclination angle is not limited. The inner surface of each condenser 52 is in the width direction of the parallel belt 31' Therefore, the colloidal film 35 is almost parallel. It should be noted that in the jelly film 35, the surface on which the tape 31 is not contacted is referred to as a cast surface. At the point of approaching the casting surface, the movement of the belt 31 causes an unexpected flow of gas or air. Preferably, in the present invention, the unexpected air flow between the casting surface and the condenser 52 is as small as possible, and specifically at least 0.01 m/sec to 0.5 m/sec. The temperature of the gel film 35 is increased by the belt 3 1 heated by the heating plate 51, and there is a temperature gradient Q between the casting surface and the condenser 52. When Ts (°C) is the temperature formed on the belt 31, @(°(:) is the surface temperature of the condenser 52, and d (mm) is the distance between the casting surface and the condenser 52, the temperature gradient Q ® The definition is as follows: Q = (Ts - Tc) / d. The temperature gradient Q preferably satisfies the range: 5 < Q < 100. When the temperature gradient Q is in this range, the thickness variation of the gel film 35 is reduced, and the thickness is obtained. A film having excellent uniformity. It should be noted that the surface temperature Tc of the condenser 5 2 may be at least the temperature of the inner surface or the facing surface of the gel film 35. The solvent vapor concentration is higher near the casting surface and is lower when it is farther away. There is a gas that undergoes thermal diffusion in a system with a temperature gradient. Therefore, molecules with higher molecular weight of-14-1322042 move toward the low temperature side, and molecules with lower molecular weight move toward the high temperature side. The mixture gas is separated. When an organic solvent is used as the solvent, air molecules (including nitrogen molecules, oxygen molecules, carbon dioxide molecules, etc.) and molecules for evaporating organic solvents are present in the temperature gradient space between the casting surface and the condenser. Manufacturing The organic solvent molecules of the optical use film have a molecular weight greater than the molecular weight of the air. Therefore, thermal diffusion occurs so that the solvent molecules can be moved to the condenser. This prevents the solvent molecules from approaching the casting surface from being saturated, causing the solvent to evaporate from the gel film 35. The temperature gradient Q is At least 1 Torr, the difference between the heating temperature of the heating plate 51 and the cooling temperature of the condenser 52 is too large, and the condensed solvent droplets generated in the gas phase form a dew on the casting surface. Further, the temperature gradient is at most 5 The evaporation of the heating solvent and the condensation of the cooling solvent are performed at a lower speed, and the effect is insufficient. Further, in the uneven temperature ring region between the heating plate 51 and the condenser 52, the thermal energy is in this region. The moving molecules are transported. Therefore, when the heating plate 51 faces the belt 31 having a large facing area, the belt 31 is continuously and uniformly supplied with thermal energy to compensate the externally discharged thermal energy. Therefore, it is preferable that the temperature gradient Q · The maximum variation is 10% of the temperature gradient Q, and the temperature gradient Q is controlled by adjusting the temperature Ts (°C) of the gel film and the surface temperature Tc (°C) of the condenser 52. The change 値 exceeds 1% 温度% of the temperature gradient Q, so that the solvent cannot be uniformly evaporated from the polymer casting solution on the belt 31. In this case, the thickness of the film produced and the direction of the thickness and the surface direction (or surface) The mechanical properties or optical properties (blocking, etc.) of any of the directions are not good. In addition, the temperature ladder -15-1322042 degrees Q is preferably at most 8%, and especially at most 5%. Adjusting the surface temperature T c of the condenser 52 in the area facing the casting surface, so that the temperature change 値 is maximum; [〇 ° C. When the variation 値 exceeds 10 ° C, uniform solvent vapor condensation becomes difficult, thus allowing heat diffusion Not uniform. Thus, the evaporation rate of the solvent from the gel film 35 is not uniform. The change in surface temperature Tc is preferably at most 8 ° C, and especially at a maximum of 51. In the present invention, it is preferred that the change d of the distance d between the casting surface and the condenser 52 is at most 10% of the average 値dA of the distance d. In this case, the above temperature and distance can be maintained, and as a result, the thickness variation of the obtained film 36 becomes small. In order to control the distance between the casting surface and the condenser 52, the uniform nature or characteristics of the casting mold liquid 12, the uniform casting speed 'and the surface smoothness of the condenser 52 are necessary. In the solution casting method, the belt 31 is normally moved so that the casting mold liquid cast on the belt 31 can be transported upward or horizontally from the casting position PS above the first support roller 32. Thus, the initial state after casting (in which the solvent content is high) prevents the casting mold liquid from dripping from the gel film 35. However, it is particularly preferred in the present invention that the first and second support rollers 32, 33 are rotated to transport the casting mold liquid downward from the casting position PS above the first support roller 32. Thus, the casting position PS is disposed above the area where the support roller 32 passes the belt 31. It should be noted that the casting upper molding liquid 12 forms a curve from the mold to the belt, and it is preferable that the tangent line at the casting position PS on the curve is the same as the tangent line of the belt 31 at the casting position PS, or as much as possible. In the present invention, the heating plate 51 and the condenser 52 are provided as described above, and the casting position PS and the casting direction are determined. Therefore, even if the casting mold liquid 12 such as the jelly film 35, which is just after casting 1322042, is transported downward, the dropping of the casting mold liquid can be prevented, and the evaporation solvent which is generated immediately after the casting can be recovered at a high yield. The present invention does not depend on the thickness of the resulting film 36. However, the thickness T of the gel film 35 just after casting is preferably from 10 μm to 1000 μm because the present invention is effective in this case. The thickness T is particularly preferably from 20 μm to 500 μm, because the effect of the present invention is large. It should be noted that the gel film 35 just after casting the casting mold liquid represents the portion from the casting position PS to the gel film 35 of the first condenser 52. In this embodiment, the gel film 35 has a multilayer structure, and the thickness T is the total thickness of the layers simultaneously formed in one casting process. The moving speed of the belt 31 is preferably from 5 m/min to 200 m/min. It should be noted that the moving speed and the casting speed are the same. When the thickness T is less than 10 μm, the amount of the solvent in the polymer solution per unit area is small, so that the evaporation rate cannot be completely controlled. Further, when the thickness T is larger than 1000 μm, the solvent of the belt 31 will be approached in the jelly film 35 '. However, solvent evaporation is difficult to carry out because it is difficult for heat energy to penetrate to the side of the casting surface. Further, the solvent or solvent gas of the gel film 35 sometimes remains inside the film 36. Therefore, the surface condition is deteriorated. In addition, the drying speed is inversely proportional to the squareness of the thickness. Therefore, when the thickness is too large, the productivity of Sheng ® becomes low, which is not good. The present invention is also effective when the gel film 35 and the film 36 have a single layer structure. However, the present invention is particularly effective in the case where it has a multilayer structure. The casting method can be co-casting and sequential casting. The explanation of the casting procedure is carried out with reference to Fig. 4, and the same devices and members as those of Fig. 1·3 have the same reference numerals and their explanations are omitted. As shown in Fig. 4, the mirror 14 is a feed zone type. -17- 1322042 The mold 14 is composed of a mold zone 61 and a feed zone 62, and is generally referred to as a coater type. The feed zone 62 is disposed on the back of the mold zone 61 (or for discharging the opposite surface of the die lip 61a from which the molding liquid 12 is cast). The feed zone 62 has inlets 62a· 6 2c ' and the casting upper molding liquid κ includes casting mold liquids 12a-12c for forming the respective first to third adhesive films 35. The casting upper molding liquids 12a-12c are each supplied through the inlets 62a-62c in the feed zone 62, and the passages extending from the inlets 62a-62c are combined into one passage, so that the three casting upper molding liquids 12a-l 2c can constitute three layers. The structure can then be supplied to the mold area 61. The mold region 61 has a single passage 61b. The casting upper molding liquid 12 having a three-layer structure flows into the passage 61b and is discharged from the lip 61a. This casting is called co-casting. Further, in the present invention, each of the casting mold liquids 12a-12c may be subjected to a feed pressure ' to independently control the feed through the passage. Therefore, the thickness of each of the first to third layers 35 a - 35c is adjusted. In order to control the thickness of each of the first to third layers 35a-35c', the thickness of the path as the flow path of the three casting upper molding liquids 12a-12c is appropriately determined in the portion where the three passages are combined, or the respective applications are appropriately adjusted. The feed pressure to the casting mold liquids 12a-12c. As shown in Fig. 5, the mold 71 is of a multi-manifold type, and three layers can be simultaneously formed as the mold 14 of Fig. 4. The same devices and members as those in Figs. 1-4 have the same reference numerals and their explanations are omitted. The three casting upper molding liquids 12a-2b are supplied to the casting mold 71 via respective flow paths (not shown). » The inlets 72a-7 2c are formed on the back surface of the casting mold 71 to supply the casting upper molding liquids 12a-12c into the casting film 71. The casting mold liquids 12a-12c are temporarily stored in the respective pockets 75a, 76a, 77a formed on the passages 75-77. The casting mold liquids 12a-12c are then joined to the mold lip 71 to form a three-layer structure, and are simultaneously discharged in this condition. -18- 1322042 It should be noted in the mold 71 that the positions of the inlets 72a-72c of the casting upper molding liquid 12a-12C, the shape of the passages 75-77, the shape of the pockets 75a-77a, and the passages are close to the lip 7 1 a The structure of the combined portion is not limited, and the mold 71 can be a general mold for performing a co-cast multi-manifold type. In the present invention, a multi-manifold type mold which can simultaneously form an N layer (N is a natural number of at least 2) can be further used. In this case, the number of flow paths is N, and the substantial structure is the same as the above specific embodiment. In addition, 'in the present invention' can be combined with the feed zone type in FIG. 4 and the multi-manifold type in FIG. Co-casting In this case, a ring (see the 2nd to 4th figure) or a cylinder (see Figure 5) can be used as the substrate. In the present invention, as shown in Fig. 6, casting can be performed using a casting apparatus 81 so that sequential casting can be performed instead of co-casting. The same devices and members have the same numbers as in Figs. 1-4 and the explanation thereof is omitted. In the casting apparatus 81, three molds 82-84 are disposed above the belt 31, on which the upper mold is cast, and the liquids 12a-12c are sequentially cast from the molds 82-84 to form a gel having a three-layer structure. Membrane 3 5. It should be noted that the heating plate 51 and the condenser 52 are configured to have the same positional relationship with respect to the mold 84 (which is provided at the same position of the mold 丨 4 in Fig. 2). The liquid receiver is located at the same location as the recovery tank and is omitted from this figure. When it is designed to perform sequential casting, the number of molds used is not limited to three ' and may be equal to or less than the number of layers formed. For example, if it is designed to perform sequential casting NC times (NC is at least 2 natural numbers) to form an N layer, the following formula is satisfied: 2$NCSN (N is a natural number of at least 2). In the NC<N2-19-1322042 condition, co-casting is carried out at least once in the casting process. In the above method of the present invention, the thickness uniformity of the produced film becomes large, and an excellent optical polymer film can be obtained. The optical properties are often determined by variations in the thickness of the polymer film, and this tendency is particularly pronounced when the main component of the film is an aromatic polymer and the other polymer has a ring structure. The polymer film of the present invention produced by the above method and equipment can be excellent in thickness uniformity, birefringence, light transmittance and the like. Therefore, this polymer film is suitably used for a polarizing filter and a liquid crystal display. The polymer film is explained in detail below. In Fig. 7, the X-axis extends in the longitudinal direction of the film 36 and the Y-axis extends in the vertical direction in the width direction or the length direction. In order to adjust the thickness, the film 36 (hereinafter referred to as the thickness 値) is measured at a number on the line segment L1 between the selective two points pa' pb in the XY plane on the film 36. The length of the line segment li is relatively large. Further, since the surface condition change and the thickness variation in the film are generally cyclic, the length of the line segment L 1 is preferably at least one cycle change or variation. The thickness measurement of the film 36 is carried out using a meter that can measure the micron number. Specifically, in FIG. 8 'optionally from n positions of P(1) to p(n) between P 1 and P 2 (η is a selectivity and a natural number), and at n measurements The thicknesses were measured in terms of thickness at positions ρ(1), ρ(2), ρ(3), ..., ρ(η-2), ρ(η-1), ρ(η). The continuous advance measurement is thus performed to obtain thicknesses 値t(1), t(2), t(3)', ..., Un-2), t(n-1), t(n), and measurement position P ( l) Thickness data such as variations and changes between p(2), p(3), ..., P(n-2), p(nl), and p(n). Then calculate the first thickness average ΤΑ丨 as the average of these thicknesses (t(l), t(2)' t(3), ... 'Un-2), t(nl), t(n) -20- 1322042 値. In addition, 'calculate the thicknesses at the measurement positions p (1), p( 2 ), P(3 ), ... ' p(n-2) ' p(n-1), p(n) The error is obtained, and the average error of the thickness error is obtained as the first average error MD1. In the present invention, the first average error MD1 preferably satisfies the condition MD1 $ O.lxTAl, and particularly MD1 $ 0 · 0 8 X T A 1 . It should be noted in the present invention that the error indicates the standard deviation of the sample. In addition, the frequency spectrum data of the obtained thickness data is obtained by the FFT program in the operation in the thickness gauge. In the frequency spectrum data, the wavelength is converted from the forward distance in the continuous advance measurement of the thickness, and is a variable (or parameter). The Fourier transform system is defined as a conversion formula in which the Fourier component is used for time-to-frequency conversion. The Fourier transform system is applied to DFT (Discrete Fourier Transform) and in the FFT, the operation time is much shorter than the DFT. Data processing is usually performed in the thickness measurement, and the moving distance converted to the corresponding wavelength is also shown as the corresponding time. Several thickness gauges with this data processing function are on the market. It should be noted that the thickness tester KG601A (manufactured by Anritsu Corp.) is commercially available and used as a contact type thickness gauge in the present invention. In the present invention, the maximum frequency spectrum 値 is preferably 1% 平均% of the maximum first thickness average 値ΤΑ 1 . Further, in this case, when the frequency spectrum data is converted to obtain a spatial frequency, the wavelength range of the obtained specific frequency is preferably at most 20 cm.

Further, as shown in Fig. 7, the thickness is also measured at a selected position of the line segment L2 between the points P3 and P4 in a manner similar to the thickness measurement of the line segment L1. A second average 値TA2 of the resulting thickness 値 is calculated. Then, the thickness error (thickness standard deviation) of the line segment L2 is calculated from the thickness 値, and the average error thereof is obtained as the second average error MD2. The second average error MD2 is preferably a condition that satisfies MD2S - 21 - 1322042 0 · 1 χΤΑ 2 and is particularly MD2 $0_08xTA2. Further, the frequency spectrum data was obtained from the thickness data as described above. In the present invention, the frequency spectrum maximum 値 is preferably 10% of the maximum second average 値TA 2 , and particularly at most 8%. Further, in this case, when the frequency spectrum data is converted to obtain a spatial frequency, the spatial frequency has a wavelength range of preferably 20 cm or more. In the following explanation, the vertical positional relationship of the two line segments indicates that the extension of the two line segments vertically intersects in one plane, even if the two line segments do not actually cross. The thickness 値 average error and frequency spectral intensity obtained by FFT analysis of the thickness data are in the above range in accordance with the thickness 测量 measured in one direction of the film 36. A polymer film having a thickness suitable for optical use is thus obtained. In addition, these flaws are obtained in both directions in the vertical direction, and are controlled in the above range. Therefore, the thickness of the polymer film is excellent. It should be noted that when the thickness is measured in the longitudinal direction of the film 36, it is preferable to obtain the thickness 値 in the middle portion in the width direction, and the thickness is measured in the width direction of the film 36. Positions are made. Incidentally, birefringence is induced when light passes through a material having a refractive index difference therein. In this material, the incident light is split into two light beams that are 90 degrees apart from each other and which differ in the speed of light passing through the material. The difference in speed causes a difference. Usually, when the speed of light passing through the vacuum is c and the speed of light passing through the material is v, the refractive index n is shown in the formula: n = c/v. As mentioned above, birefringence is a phenomenon caused by the difference in the two refractive indices of a material. The two axes in which light waves propagate are called the main axes. The light waves propagate in the plane of the 1322042 parallel spindle. This spindle includes a fast axis and a slow axis. The light wave propagating along the fast axis passes through the material faster than the other light wave propagating along the slow axis, that is, the penetration speed of the former wave is faster than the latter wave. The magnitude of the birefringence is detected and is shown as the relative ratio between the waves passing along the slow and fast axes. The absolute 双 of birefringence cannot be expressed in terms of the wavelength corresponding to the 3 6 〇 ° phase contrast. Therefore, the wavelength is used to normalize the relative ratio of detection to a unit of length (nano). The birefringence meter detects the major axis of the sample of the measured material and measures the relative ratio Δ nd. The relative ratio is defined as the following equation. When the sample thickness is d, the refractive index of the light wave propagating in the plane parallel to the incident angle is ne, and when the refractive index of the light wave propagating in the plane of the normal incident angle is no: Δη(1 = ί1(ne-no)° is thus relative or birefringent depending on the thickness of the material. In the present invention, since the thickness of the produced polymer film is uniform, the double refraction is excellent. There are two relatives in the birefringence. Specifically, it is known as the retardation Re of the plane 'the middle direction (or the selected direction in the surface) of the film 36, and the retardation Rth of the thickness of the film 36. In the present invention, it is arranged in the plane direction. At a number, or on the selected line segment in the XY plane of Fig. 7, the first block Re is obtained. Then the average error of the first block Re is calculated as the third mean error MD3. When the first block average 値RA1, the third average error MD3 satisfies the condition: MD3S O.lOxRAl. Furthermore, the frequency spectrum data of the first block Re is converted to obtain spatial frequency data. In this case, preferably The wavelength range for the spatial frequency is up to 20 cm And the frequency spectrum of the first block Re is the maximum 値 maximum of the first block average 値RA 1 of 1 0 ° / 〇. In addition, in the same way as the thickness data analysis, in the above selected line segment -23-1322042 vertical direction The frequency spectrum data of the second block Re is also obtained in the measurement of the same number. In the present invention, the average error of the second block Re measured in the vertical direction is calculated as the fourth mean error MD4. When the average value of Re is the block average 値RA2, the fourth average error MD4 satisfies the condition: MD4 S 0.10XRA2. In addition, the frequency spectrum data of the second block Re is converted to obtain a spatial frequency. In this case, preferably The wavelength range of the spatial frequency is at most 20 cm, and the frequency spectrum of the second block Re is at most 10% of the second block mean 値 RA2. As described above, in this embodiment, the direction is selected. The average error of the measured retardation Re and the intensity of the frequency spectrum obtained in the FFT analysis of the retarded Re are adjusted to the above range. The polymer film thus produced can have a thickness property suitable for optical use. The other retardation Re is measured in the vertical direction, and the frequency spectrum data obtained by the other retardation Re is also controlled in the above range. The polymer film thus produced can have a thickness property more suitable for optical use. Also, in the thickness direction The frequency spectrum data of the third block Rth is obtained in several places. In the present invention, the average error of the block Rth is calculated as the fifth average error. When the average value of the block Rth is the third block average 値RA3, the fifth The average error MD5 satisfies the condition: MD5S 0.10xRA3. In addition, the frequency spectrum of the third block Rth is converted to obtain a spatial frequency. In this case, it is preferable that the spatial frequency has a wavelength range of at most 20 cm, and the third resistance. The maximum frequency spectrum of the lag Rth is 10% of the third block average 値RA3. As for the thickness 値, the frequency spectrum data of the fourth retardation Rth is also obtained at the same number -24 - 1322042 arranged in the vertical direction of the thickness direction. In the present invention, the average error of the fourth retardation Rth is calculated as the sixth average error. When the average 値 of the fourth block Rth is the fourth block mean 値 RA4, the sixth mean error MD6 satisfies the condition: MD6 ‘0·1 0xRA4. In addition, the frequency spectrum of the fourth block Rth is converted to obtain a spatial frequency. In this case, it is preferable that the spatial frequency has a wavelength range of at most 20 cm, and the fourth block Rth has a frequency spectrum of at most 10% of the fourth block average 値 RA4. As described above, in the selected direction of the film 36, the average error of the Rth is retarded, and the intensity difference of the frequency spectrum obtained in the FFT analysis of the retarded Rth is in the above range. The polymer film thus produced has a thickness property suitable for optical use. In addition, the average error obtained in the vertical direction of the selection direction is distributed in the above range. The polymer film thus produced has a thickness variation suitable for optical use. It should be noted that it is preferable to measure the retardation Re in the plane direction and the retardation Rth in the thickness direction at the same position as the film thickness 値. It should be noted that the average 値 of the thickness 値 and the retardation Re and Rth are obtained according to two directions of rotation of one plane, that is, one selection direction and its vertical direction. In the present invention, when the polymer film is 80 μm thick, the transmittance of visible light through the polymer film is preferably at least 90%, and particularly at least 93%. Further, in the two selected positions on the XY plane in Fig. 7, that is, in the planar direction, the difference in transmittance in the thickness direction is preferably at most 5%, and particularly at most 2%. The film thus produced has birefringence and transparency which are effective for optical use. When the transmittance is less than 90%, the displayed image becomes dark and discoloration occurs. Therefore, in this case, the polymer film is not suitable for optical use and for use in displays and the like. Further, at a relative humidity of 1 〇%, the surface resistance of the polymer film is preferably in the range of 1 χ 1 〇 1 () Ω to ΐχΐ〇 13 Ω, and particularly in the range of 1 χ 101 β Ω to 1 χ 10 Μ Ω. The difference in surface resistance between the two selected points is preferably 20% of the average 値 of the surface resistance of the two points, and especially the maximum of 1%. In addition, the surface resistance of the polymer film is not preferable when it is larger than 1x1 013 Ω. In this case, when the polymer film is stacked on other films in a liquid crystal display or the like, the 'insulation 値 is too large to allow the charges of the other layers to flow through the film. In addition, it is not preferable to electrostatically adsorb dust near the polymer film. Alternatively, the surface resistance of the polymer film is less than ΙχΙΟ^Ω because the polymer film does not function as an insulating spring layer. In order to obtain the above optical properties and electrical properties, the polymer film of the present invention is produced in the above solution casting method. The present invention can be applied as long as the polymer or its prepolymer is dissolved in a solvent to prepare a molding liquid for use in the production of a film. As for the polymer or prepolymer, for example, 'with cellulose telluride, polycarbonate (PC), linalylamine resin, polyvinyl alcohol, : denatured polyvinyl alcohol, polyacrylate, polymethacrylate, poly For ethylene phthalate (PET), polybutylene terephthalate (PBT), chlorinated polyether, polyacetal, polyetheretherketone (PEEK), polyether mill (PES), polyimine ( PI), polyamine (PA) #, polyamidimide (PAI), polyepoxybenzene (PPO), polyphenylene sulfide, poly-rolling, polyallyl, polycarbonate (PC), poly Ethylene (PE), polypropylene (pp), polystyrene (PS), polyvinyl chloride (PVC), etc. One or a combination of them may be used. Particularly in the present invention, it is preferred that the polymer contains at least A cellulose halide, polycarbonate (PC), linaloamine resin, as shown in Chemical Formula 1-7, and a polystyrene. It should be noted that in Chemical Formula 1-7, nsm is 1 〇 to 1 The natural number of 000. -26- 1322042 Chemical Formula 1

CH20 \ H 〇H2 CH2OH6' / " OH Chemical Formula 2

Chemical formula 3

-NH

^-NHOC-

-27- 1322042 Chemical Formula 4

- one NH

Chemical formula 5

-28- 1322042 Chemical Formula 7

Further, the cellulose halide content in the polymer is at least 50% by weight. In the cellulose oxime, in a repeating unit, when the thiol substitution degree of the sixth position is X and the thiol substitution degree of the other position is Y, it is preferable to satisfy the following conditions: X > 〇.85 and 2.70<;Χ + Υ<2·99, and especially Χ>0.90 and 2·80<Χ + Υ<2·99. The present invention is also effective when the direction of transport of the gel film is horizontal or from the casting position PS upward. This embodiment is described as casting apparatus 91 of Figures 9 and 1 . In these figures, the same devices and members as those in Fig. 2 have the same reference numerals, and the explanation thereof is omitted. In the casting apparatus 91, a heating plate 92 and a condenser 93 are provided to the casting apparatus 16 of Fig. 2. It should be noted that the liquid receiver 53 and the recovery tank 56, and the feed path of the connection are not described in these figures. The temperatures of the heating plate 92 and the condenser 93 are controlled by the temperature controllers 92a, 93a. The first and second support rollers 32, 33 are rotated opposite to the direction of rotation of the second figure. The casting mold liquid 14 cast on the belt 31 by the mold 14 above the first support roller 32 forms a gel-like film which is transported almost horizontally from the casting position P S . The heating plate 92 is provided below the upper portion of the belt 3 1 between the first and second support rollers 32, 33 (hereinafter referred to as the upper belt), and the condenser 93 is provided above the gel film 35 on the upper belt. Thus, the solvent of the gel film 35 on the moving belt 31 is evaporated and condensed by the condenser 93. -29- 1322042 In Fig. 10, each condenser 93 is shaped differently from the condenser 52. In the width direction of each condenser 93, the middle portion of the lower surface is horizontal, and the edge portion has a small inclination to make the thickness large. The condensed solvent flows on the inclined edge portions of the respective condensers to reach the side ends, and then falls into the liquid receiver. The condensed solvent is then recovered in the recovery tank. It should be noted that the distance d between the condenser film 35 and the condenser 93 is preferably in the range of from 1 mm to 15 mm, and not in the range of from 2 mm to 10 mm. The gel film 35 is further transported to the second support roller 33, which has a heat device (not shown). Then, the gel film 35 on the lower portion of the transfer belt 31 between the first and second support rollers 32, 33 (hereinafter referred to as the lower belt) is transported to the stripping roller, which strips the gel film 35 into a film. 36. When the gel film 35 is transported on the lower belt and on the first support roller 32, the solvent is evaporated and condensed by the heating plate 52 and the condenser 52. Thus, in this embodiment, regardless of the direction of transport of the gel-like film, the solvent is uniformly evaporated and condensed from the casting position, and the solvent is recovered in a high yield. Further, the present invention is also effective when a cylinder is used as the substrate. In the figure, the casting apparatus 101 has a cylinder 1〇2 as a substrate. In the drawings, the same devices and members have the same reference numerals as in Fig. 2, and the explanation thereof is omitted. The casting mold liquid 12 discharged from the mold 14 forms a gel film on the cylinder 102. The casting position PS is slightly lower than the top of the cylinder 1 〇 2, and the gel film is first transported downward from the casting position P S . Also in this case, it is preferred to determine the casting PS so that the tangent to the cylinder 102 at the casting position PS can almost coincide with the tangent of the curve formed by the casting mold from the mold, and almost -30-1322042 The cylinder l'〇2 is connected to a temperature controller to heat the surface of the cylinder 102 and evaporate the solvent. Therefore, the cylinder 1〇2 also has the effect of the heating plate as shown in Fig. 2. A plurality of condensers 105' are disposed on the outer side of the gel film 35, and the condensed solvent flows on the slope of the condenser 〇5, and falls into the liquid receiver 53, and the condensed solvent is recovered by the recovery tank 56 to be a recovery solvent. By stripping 37, the gel film 35 on the rotating cylinder 102 is peeled off into a film 36' and a transport drying device 17 (see Fig. 1) for the next progress. Thus, the mold liquid is prevented from dripping from the gel film, the gel film 35 is uniformly dried, and the solvent is recovered at a high rate. It should be noted that when the direction of rotation of the cylinder is in the opposite direction of this embodiment, the gel film 35 is first transported upward from the casting position. Also in this case, the gel film 35 is uniformly dried and the thickness uniformity of the film is changed. It should be noted that the temperature of the condenser 105 is controlled by the temperature controller 105a. Furthermore, the invention is also applied to the tensioning device 41 in the drying apparatus 17 to dry the film 36 therein. As shown in Fig. 12, each of the clip type tension machines 1 has a main body 111a and a clip member 111b. In the tension device 41, the side portions of the film are sandwiched by the clip tensioner 1 1 1 , that is, sandwiched between the main body 1 1 1 a and the member 111b, and the film is transported by moving the clamp tension machine ill. And pulling. The tensioning device 41 further includes a heating plate 1 12 for evaporating the agent in the film 36, and a condenser i for condensing the solvent vapor. Such a film has a uniform thickness suitable for optical use, and solvent recovery is also accomplished in the drying unit 17. Therefore, the present invention should be effective for the tension device 41. Further, the heating member is not limited to the heating plate 1 12 . The microwave guide 122 is used as the heating member for heating the film 36 as shown in Fig. 13. Micro-31- 1322042 The guide member 1 2 2 irradiates the microwave to the film 36, so that the energy of the solvent molecules contained in the film 36 becomes high, thus evaporating the solvent. The solvent vapor is condensed by the condenser 1 2 3 . The present invention is also effective when applied to a plurality of other tension devices that replace the tension device 41 of the clip type tension machine 111 in Fig. 12. As shown in Fig. 13, the tension device 121 includes a needle tensioner 125. Each of the needle tensioners 125 has a plurality of needles 125a for fixing the film 36 to the needle tensioner 125. It should be noted that the microwave guide member is used not only for the tension device but also for the casting device as long as the power of the generated energy is sufficient. The film obtained in the above method can be used as a polarizing filter protective film. The polymer which is the main content of the polarizing film of the polarizing filter is particularly preferably a polyvinyl alcohol type polymer. As for the polyvinyl alcohol type polymer, there are not only a polyethylene glycol but also an alkyl modified polyvinyl alcohol. Further, a polyvinyl alcohol type polymer is usually produced by saponifying polyvinyl acetate in which vinyl acetate is polymerized. However, the polyvinyl alcohol type polymer may be in a polyvinyl alcohol type polymer with a small amount of an unsaturated carboxylic acid, a derivative thereof (for example, a salt 'ester, a guanamine, a nitrile, etc.), a cannon, a vinyl ether 'unsaturated sulfonic acid. Manufactured in the polymerization of salt. The alkyl-denatured polyvinyl alcohol has an alkyl group at the molecular end and a degree of saponification of at least 80%, and a degree of polymerization of at least 200. Other polymers than the polyvinyl alcohol type polymer can be used in the polarizing film of the present invention, for example, a 'polycarbonate type polymer', a cellulose type polymer or the like. When the polyethyl alcohol model is used as the main content of the polarizing film 12, the polarizing film can be dyed by a vapor phase adsorption method or a liquid phase adsorption method. In this embodiment, the polarizing film is dyed by liquid phase adsorption. However, the present invention does not rely on these -32-1322042 methods. Iodine is used in the liquid phase adsorption staining of this embodiment. However, the invention is not limited thereto. The polyvinyl alcohol film is immersed in an aqueous solution of iodine/potassium iodide (KI) for at least 30 seconds and at most 50 seconds. Preferably, the iodine concentration in the solution is from 1 g/L to 20 g/L, and the potassium iodide is from 1 g/L to Ig/L. It should be noted that the temperature of the solution for impregnating the polyvinyl alcohol is preferably 5. (: to 50. 0. In the liquid phase adsorption method, in addition to the above method of impregnating a polyvinyl alcohol film, a solution of iodine or other dye may be applied or sprayed on the polyethylene film in a known manner. The polyvinyl alcohol can be colored before and after stretching. However, after the dyeing, the polyvinyl alcohol film is appropriately expanded, and the film is opened after dyeing. Therefore, it is preferred to dye the polyvinyl alcohol film before stretching. Dichroic dyes (including pigments) can be used. Dichromatic dyes are azo dyes, stilbene dyes, pyrazol dyes, triphenylmethane dyes, porphyrin dyes, anthraquinone dyes, triterpenoid dyes, anthraquinone dyes. Preferably, the dye material is soluble in water. Preferably, the dichroic dye has a hydrophilic substituent such as a sulfonic acid group, an amine group, a hydroxyl group, etc. Lu is a dichromatic dye having Cl Direct Yellow 12. CI Direct 〇range 39, Cl Direct Orange 72, Cl Direct Red 39, ci Direct Red 79, Cl Direct Red 81 'Cl Direct Red 83, qi Direct Red 89,

Cl Direct Violet 48 'Cl Direct Blue 67 > ci Direct Blue 90, CI Direct Green 59, CI Acid Red 37, etc. In addition, there are other dyes described in Japanese Patent Publication No. i_1 6 1202 ' 1 -1 72906 ' 1 - 1 72907 ' 1 - 1 836 〇 2 > 1 - 248 1 05 ' 1 - 265205 - 33 - 1322042 , 7 -26 1 024 and so on. These dichroic dyes are used as free acid, alkali metal salt 'ammonium salt, and amine salt. When a plurality of dichroic dyes are mixed, the polarizer (or polarizing film) may have several hue or hue. Preferably, the polarizing filter (or polarizing element) has a compound that causes the two polarizing passes (or polarizing elements) to display black at a crossed Nicol position. When it is designed to open the polyvinyl alcohol type film after coloring, a compound (or a crosslinking agent) for crosslinking polyvinyl alcohol is used. Specifically, the polyvinyl alcohol type film is immersed in the crosslinking agent solution, or the crosslinking agent is coated or sprayed onto the polyvinyl alcohol type film. The polyvinyl alcohol type film is thus hardened to have an appropriate orientation. It should be noted that the crosslinking agent of the polyvinyl alcohol type film is described in U.S. Patent Application Serial No. 232,897, or may be other known. It is especially good for citric acid. In order to adhere the obtained film to the polarizing film, there is a method of applying an adhesive, or a surface chemical treatment to supply an adhesive property to at least one surface of the polarizing film and the obtained film. When a cellulose halide is used as the polymer in the protective film, for example, a particularly preferred surface treatment method is an acid treatment, an alkali treatment, a corona discharge treatment, a glow discharge treatment, and exposure to UV rays. In this embodiment, the film is adhered to the polarizing film with an adhesive after the surface treatment. The surface treatment is alkali saponification. Specifically, the film formed of the cellulose halide is immersed in an alkali solution, then neutralized in an acid solution, then rinsed with water, and dried. As the alkali solution, for example, sodium hydroxide and potassium hydroxide are used, and the concentration thereof is preferably from 0.1 N to 3.0 N. Alternatively, the temperature of the alkali solution is preferably from room temperature to 90 °C. -34- 1322042 The film is adhered to the polarizing film with an adhesive, and the adhesive can be known. More preferably, it is a solution of a boron compound or a polyvinyl alcohol containing a denatured polyvinyl alcohol having an ethyl acetonitrile group, a sulfonic acid group 'carboxyl' epoxyalkyl group or the like. Preferably, the adhesive has a thickness of from 0.01 to 10 microns, and particularly preferably from 005 to 5 microns, after drying. Further, the resulting film is used for an optical compensation film in which the film is coated with an antireflection layer and for an optical functional film such as an antireflection film, wherein an antiglare layer is formed on the resulting film. These products can be used as parts of liquid crystal displays. In order to increase the effect of the present invention, the following specific embodiments are carried out. It should be noted that the present invention is not to be construed as the following specific embodiments. [Preparation of Preparation Molding Solution] A method of preparing the above molding liquid is usually to dissolve the polymer at room temperature. In order to improve the uniformity of dissolution, the cold solution method and the hot solution method are suitably applied to the present invention. In a cold solution method, a polymer (fiber: vitamin, etc.), an additive (particles, etc.) are gradually stirred and added at a temperature close to -10 ° C to 4 ° C. Material addition can be done simultaneously or sequentially. It should be noted that a solution or dispersion of each material may be prepared, and then the solution or dispersion may be mixed. The dispersion is prepared by a method using a stirring tank, for example, a continuous mixing method using a continuous jet mixer (product name: flow jet mixer, manufactured by Funken Powtechs, Inc.) or the like. However, when the dispersion of the upper molding liquid is sufficient for the solution casting method of the present invention, the method of preparing the dispersion is not limited thereto. For example, cooling is carried out in a dry ice/methanol bath (-7 5 ° C) or a diethylene glycol solution (-30 ° C to -20 ° C). The mixture of the solvent and the solid material in the polymer solution is thus cured. The mixture is then heated to have a temperature of about 〇 ° C to 200 ° C to obtain a solution in which the material exhibits -35 - 1322042 fluidity in a solvent. In order to make the temperature higher, the mixture can be allowed to stand at room temperature or heated in a warm bath. In the hot-melt method, the polymer (cellulose hydrazine, etc.), additives (particles, etc.) are gradually stirred into the solvent at -10 ° C to 4 (TC near room temperature. The material addition can be carried out simultaneously or sequentially. Then The solvent is heated under a pressurization of about 22 MPa to 30 MPa to have a temperature of about 7 〇t: to 240 ° C. The preferred heating temperature is from 80 ° C to 220 ° C. The heated solution or dispersion is then cooled. Having a temperature lower than the lowest boiling point of the solvent component used. The solution or dispersion is usually cooled to -10 ° C to 50 ° C to reduce the pressure to atmospheric pressure. Preferably, cooling water is used as the cooling medium. Cooling by means of a cooling device. It should be noted that additives may be added if necessary. It is preferred to filter the above-prepared molding liquid obtained in the above method so that the insoluble particles or the gel-like material can be removed. The filter medium includes filter paper, filter cloth, metal mesh, metal fiber, non-woven fabric, etc. In addition, when the upper molding liquid is strict against the residual foreign particles or insoluble particles, a plurality of filtering devices are arranged in series, and The grounding or the individual is off-line, so that the uniformity of the upper molding liquid can be improved by multiple filtrations. Further, in the system in which the particles are added to the molding liquid, it is preferred to filter the molding liquid containing the particles. Some of the particles are glued to affect the particle itself or to the compatibility of the molding solution. Therefore, the cemented particles have a larger diameter, which is usually preferably removed. This particle has cerium oxide added as a matting agent (si〇2). [Solvent] The solvent used in the present invention is a halogenated hydrocarbon 'ester, ketone, ether, alcohol, etc. However, -36-1322042' is not limited thereto. A single solvent (i 〇〇 weight %) can be used as the upper The solvent of the molding liquid' may be mixed with several solvents in a predetermined mixing ratio. As the solvent to be used, there may be a halogenated hydrocarbon (for example, dichloromethane, chloroform, etc.) 'vinegar (methyl acetate' methyl formate, ethyl acetate, Amyl acetate 'butyl acetate, etc.), ketone (eg 'acetone, methyl ethyl ketone' cyclopentanone' cyclohexanone, etc.), ether (eg 'di-hospital, dioxaline' tetrahydrofuran' diethyl ether, methyl second Butyl ether, etc.) 'alcohol (eg, methanol) Ethanol 'isopropyl alcohol, n-propanol, n-butanol, cyclohexanol, cyclopentanol, etc.) 'aromatic hydrocarbons (for example, benzene, toluene' xylene, hexane, etc.), etc. Using methyl acetate as a single solvent Or the main content of the solvent of the mixture is effective in the present invention. When the solvent of the mixture is used, the characteristics of the upper molding liquid (such as gel strength and shear viscosity, etc.) can be easily adjusted. The solvent of the substance is not only a ketone but also an alcohol (methanol, n-butanol, etc.) Further, the solvent of the mixture can be prepared by mixing methyl acetate with at least two solvents. It should be noted that the main content of the solvent of the mixture A solvent having a maximum content ratio of a mixture solvent, and a secondary content means a solvent having no maximum content ratio of the solvent of the mixture. Further, the secondary content is not limited to one solvent. When preparing the upper molding liquid using cellulose triacetate (TAC) as a polymer and using methyl acetate as a main content of the solvent, in terms of solubility of TAC, it is preferred that the methyl acetate content in the mixture solvent The percentage is from 50% by weight to 93% by weight, and the ketone is from 2% by weight to 20% by weight (for example, acetone, methyl ethyl ketone, cyclopentanone 'cyclohexanone, etc., and one or a plurality of them may be used), and an alcohol It is 5 wt% to 30 wt% (for example, methanol, ethanol-37-1322042, isopropanol, n-propanol, n-butanol, cyclohexanol, cyclopentanol, etc., and one of them may be used or a plurality of kinds may be used) . Further, at least 93% by weight of ethyl formate may be mixed with a ketone and an alcohol to obtain a mixture solvent. 'When it is designed to use cellulose triacetate (TAC) as a polymer, dichloromethane can be used as the main content of a single solvent or a mixture solvent. The preparation of the polymer solution is easy because TAC is easily soluble in dichloromethane. Further, when methylene chloride is used as the main content of the solvent of the mixture, the methyl ketone is used together with the methyl acetate to adjust the characteristics of the polymer solution. Preferably, the ratio of the methylene chloride content in the solvent of the mixture is from 50% by weight to 95% by weight, and the ketone is from 8% by weight to 20% by weight (for example, acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc. One of them may be used or a plurality of) may be used, and the alcohol may be 5% by weight to 30% by weight (for example, methanol, ethanol, isopropanol, n-propanol, n-butanol, cyclohexanol, cyclopentanol, etc.) One of them can be used or a plurality of can be used. Further, a ketone may be mixed with at least 95% by weight of methylene chloride to obtain a mixture solvent. [Additive] The additive used in the present invention is not particularly limited. As for the additive, there are a plasticizer, a UV stabilizer, a "matting agent" mold lubricant, a fluoride type surfactant, a mold release agent, a degradation inhibitor, a retardation modifier, a gelling agent, and the like. The additive may be used to mix the polymer at any step of preparing the upper mold solution, or the casting mold liquid may be added just before the completion of casting. For example, the additive may be added during expansion of the polymer, or may be added to the casting mold liquid by a static mixer and mixed during or just prior to casting the casting solution from the mold on the substrate. -38- 1322042 [Plastic agent] · As for the plasticizer used in the present invention, there is a phosphate type (for example, triphenyl phosphate (TPP), tricresyl phosphate, tolyldiphenyl phosphate phthalate diphenyl phosphate Ester, biphenyldiphenyl phosphate (BDP), trioctyl phosphate, tributyl phosphate, etc.), phthalate type (for example, diethyl phthalate, dimethoxymethyl phthalate phthalate) Methyl ester, dioctyl phthalate, etc., glycolic acid ester type (for example, triacetin, tributyrin, butyl butyl hydroxyacetate, ethyl decyl ethyl hydroxyacetate, glycolic acid Methyl decyl ethyl ester, butyl butyl hydroxy butyl acetate, etc., and other plasticizers. It is desirable to use only one type of plastic agent, or to mix a variety of plastic agents. The plasticizer is preferably from 1 to 20% by weight of the polymer in the upper mold solution. Further, other plastic agents described in Japanese Laid-Open Patent Publication No. 11-80381 '11-124445, No. 11-248940 may be used. _ [U V absorbent]: In the present invention, it is preferred that the solution contains one or more UV absorbers. In terms of protection against degradation of the liquid crystal compound, the U V absorbent is preferably superior to UV rays having an absorption wavelength of 37 Å or less. Further, in terms of the display force of the liquid crystal*, the UV absorber preferably does not absorb visible light having a wavelength of 400 nm or more. As the UV absorber, for example, an oxydiphenyl ketone type compound, a benzotriazole type compound, a salicylate type compound, a diphenyl ketone type compound, a cyanoacrylate type compound, a nickel complex salt type compound . Particularly preferred are benzotriazole type compounds and diphenyl ketone type compounds. It is particularly preferred to be a diphenylketone type compound because it is unexpectedly caused to cause discoloration of the cellulose ester. Further, it is a UV absorber of a benzotriazole type compound disclosed in Japanese Laid-Open Patent Publication No. H08-296119, and a UV absorber disclosed in Japanese Laid-Open Patent Publication No. H08-239509. In addition, other known UV absorbers may be added. The UV absorber is preferably contained in an amount of from 0.1 to 10% by weight based on the polymer. As a preferred UV absorber, there are 2,6-di-t-butyl-p-cresol, pentaerythritol-indole [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate. ]' Triethylene glycol-贰[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-贰[3- (3,5 -di-t-butyl-4-hydroxyphenyl)propionate], 2,4·贰(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)- H5-three tillage, 2,2-sulfan-diethylethyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2-(2,-hydroxy-3) ',5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3,5'-di-t-butylpentylphenyl)-5-chloro Benzotriazole, octadecyl-3-(3,5-di-t-butyl-4-yl-hydroxyphenyl)propionate '^^,1'>1'-extended hexyl wear (3,5 -di-tert-butyl-4-yl group 117 <11'〇〇)〇1611 decylamine), 1,3,5-trimethyl-2,4,6-para (3,5-di 3rd Benzyl-4-hydroxydiphenylethylenedione) benzene, ginseng-di-tert-butyl-dehydroxy hydroxydiphenylethylenedione). ..."!^^^, etc. Particularly preferred is 2,6-di-t-butyl-p-cresol, pentaerythritol-indole [3-(3,5-di-t-butyl-4-hydroxyphenyl) Propionate]' triethylene glycol-indole [3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate]. In addition, hydrazine compounds (such as N, N'-贰[3 - (3,5-di-t-butyl-4-hydroxyphenyl)propanyl]anthracene) and phosphate ester stabilizers (such as ginseng (2,4-di-t-butyl) Metal deactivator of phenyl) phosphate, etc. [Matting agent] The upper mold solution preferably contains a matting agent (particulate powder) to improve the adhesion durability and sliding properties of the film at a high -40 to 1322042 humidity. The average convex height on the surface is preferably 0.005 U0 μm, particularly 0.01-5 μm. The number of convex shapes is preferably large. However, when it is larger than necessary, the convex shape causes haze. In addition, the main particles The diameter is preferably from 1 nm to 500 nm. However, the invention is not limited to the description. The matting agent may be an inorganic or organic compound. As for the inorganic compound, there are inorganic particles such as barium sulfate, manganese colloid, titanium dioxide, sulfuric acid saw, Yttrium oxide Type (cerium oxide, etc.), alumina, zinc oxide 'tin oxide, carbonic acid fishing 'barium sulfate, talc, kaolin, sulfuric acid. In addition, there are silica sand (for example 'in wet processing or by phthalic acid glue Synthetic vermiculite obtained by the invention and titanium dioxide (rutile type 'anatase type) 〇 inorganic matting agent made of titanium slag and sulfuric acid can also be obtained by honing an inorganic compound having a diameter of more than 20 μm. 'After honing, for example, classification of inorganic compounds by vibration filtration and wind classification. As for organic compounds, there are organic polymer compounds that have been honed and classified, such as 'polytetrafluoroethylene, cellulose acetate, poly Styrene, polymethyl methacrylate, polypropyl methacrylate, polymethyl acrylate, polyethylene carbonate 'nonyl styrene type resin, polyfluorene type resin, polycarbonate type resin, benzopyrene Amine type resin, melamine type resin, polyolefin type powder, polyester type resin, polyamid type resin, polyimine type resin, polyvinyl fluoride type resin, and starch. Others are mixed in suspension polymerization The polymer is a spherical polymer obtained by a spray drying method or a dispersion method, and an inorganic compound. However, when the amount of the particulate powder in the upper mold solution is too large, the elasticity of the film becomes low. It is a granule powder of 0.01 to 5% by weight of the polymer. -41 - 1322042 [Mold lubricant] The mold lubricant is often added to the upper molding liquid to make molding easier. It has a high boiling point in the mold lubricant. a wax, a high-carbon fatty acid and a salt thereof, an ester, a polyoxygenated oil, a polyvinyl alcohol, a low molecular weight polyethylene, a vegetable protein derivative, etc. However, the present invention is not limited thereto. It is preferred to adjust the addition of a mold lubricant. The amount of the mold lubricant to the polymer in the upper molding liquid may range from 0.001% by weight to 1% by weight because the mold lubricant has an influence on the brightness and smoothness of the film. [Fluorosurfactant] In the upper molding solution, a fluorosurfactant may also be added. The fluorosurfactant has a hydrophobic group of a fluorocarbon chain, and thus acts as a coating agent in an organic solvent or an antistatic agent to lower the surface tension. As the fluorosurfactant, for example, there are C8F17CH2CH20-(CH2CH20)1()-0S03Na 'C8F17S02N(C3H7)(CH2CH20)16-H, C8F17S02N(C3H7)CH2C00K 'C7F15COONH4 'C8F17S02N(C3H7)(CH2CH20)4- : ( CH2)4-S03Na, C8F17S02N(C3H7)(CH2)rN+(CH3)3-r, C8F17S02N(C3H7)CH2CH2CH2N+(CH3)2-CH2CO〇-, C8F17CH2CH20(CH2CH20)16-H, C8F17CH2CH20(CH2)3-N+ (CH3)3.I· 'H(CF2)8- ® CH2CH20C0CH2CH(S03)C00CH2CH2CH2CH2-(CF2)8-H 'h(cf2)6ch2ch2o(ch2ch2o)16-h,h(cf2)8ch2ch2o(ch2)3- n+(ch3)3.i·, h(cf2)8ch2ch2ococh2ch(so3)cooch2ch2ch2ch2c8f丨7,c9fI7-c6h4-so2n(c3h7)(ch2ch2o)16-h,c9f17-c6h4-cso2n(c3h7)-(ch2)3- n+(ch3)3 Γ. The amount of the fluorosurfactant in the upper mold solution is preferably 0.00% by weight of the polymer. [Release agent] -42- 1322042 The release agent can be added to the upper molding solution to reduce the stripping force. As for the release agent, the surfactant is particularly excellent. The release agent is a phosphoric acid type or a carboxylic acid type 'nonionic type' cationic type. However, the release agent is not limited to this. These release agents are described in Japanese Patent Laid-Open Publication No. 61-243837. In addition, Japanese Patent Laid-Open Publication No. 57-5 00 83 3 teaches polyethoxylated phosphate as a release agent. In the Japanese Patent Publication No. 61-69845, the stripping is smoothly carried out by adding a cellulose ester mono/diphosphate alkyl ester in which the unesterified hydroxyl group has a free acid form. Further, in Japanese Patent Laid-Open Publication No. Hei No. 1-299847, the peeling force is lowered by the addition of inorganic particles and a phosphate compound having an unesterified hydroxyl group and a propylene oxide chain. These materials can be used as release agents. The amount of the releasing agent is 0.01 to 1% by weight of the polymer. [Degradation inhibitor] Further, a degradation inhibitor (an antioxidant, a peroxide decomposing agent, a radical-based inhibitor, a metal deactivator, an acid-reducing agent, an amine, etc.) and a UV stabilizer can be added to the upper molding solution. This degradation inhibitor and UV stabilizer are disclosed in Japanese Patent Laid-Open Publication Nos. 60-235852, 3-199201, 5-1907073, 5-194789, 5-271471' 6-107854' 6-118233' 6-148430' 7-11056 ' 7-11055, 7-11056 > 8-29619, 8-239509, and 2000-204173. A particularly preferred degradation inhibitor is butylated hydroxytoluene (B HT). Further, it is preferred to prepare a polymer solution of a degradation inhibitor containing 1% by weight to 5% by weight of the polymer. (Blocking Adjusting Agent) In the present invention, the unevenness of the retardation is lowered. Further, a retardation adjusting agent may be added to the upper molding liquid to control optical anisotropy. The retarder adjuster increases the average enthalpy of the film produced by the -43-1322042 film. It is preferred to use an aromatic compound having at least two aromatic groups as a retardation modifier. In addition, at least two aromatic compounds can be used simultaneously. Among the aromatic groups of the aromatic compound, there are not only an aromatic hydrocarbon group but also a heterocyclic group having an aromatic hydrocarbon property. It should be noted that it is preferred to prepare a polymer solution containing 0.01% by weight to 10% by weight of the retarder of the polymer. The aromatic hydrocarbon group is preferably a 6-membered ring (benzene ring). The heterocyclic group having an aromatic hydrocarbon group property is preferably a 5-membered ring, a 6-membered ring or a 7-membered ring, and particularly preferably a 5-membered ring or a 6-membered ring. The double bond in the heterocyclic group usually having an aromatic hydrocarbon property is formed in the maximum amount (or the maximum amount). As the hetero atom used in the present invention, a nitrogen atom, an oxygen atom and a sulfur atom are preferred, and a nitrogen atom is particularly preferred. As the heterocyclic group having an aromatic hydrocarbon property, there are a furan ring, a thiophene ring, a pyrrole ring 'carbazole ring, an azole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, a furazan ring, a triazole ring, and a pyran. Ring, tftD ring, tower ring, 1^ dense ring, Talk ring _, and 1,3,5-three ring and so on. Specifically, a oxydiphenyl ketone or a 2,4- oxydiphenyl ketone or the like can be used as a retardation adjuster. Preferred aromatic rings are benzene ring 'furan ring, thiophene ring, pyridyl ring, anthracene ring, salivary ring, taste π ring, two ring, steep ring, chew steep ring, 哄 ring, thick 1 , 3, 5 - three tillage rings, etc. The benzene ring is especially good with 1,3,5-three tillage rings. Preferably, the aromatic compound has at least 1,3,5-three tillage rings. The number of aromatic rings in the aromatic compound is preferably from 2 to 20, particularly from 2 to 12, and particularly from 2 to 8. The combination of the two aromatic rings is accomplished in one of the following combinations: (a) forming a condensed ring, and (b) forming a single bond '(c) which is uprightly combined with two groups. (When two aromatic groups are combined, 'the spiral bond cannot be formed.) The specific group in each combination relationship is shown in the following -44- 1322042. As for the condensed ring in (a), there are an anthracene ring, a naphthalene ring, and a ring. , anthracene ring, phenanthrene ring, anthracene ring, anthracene ring, anthracene ring, isoindole ring, benzofuran ring 'benzothiophene ring, porphyrin ring 'benzoxazole ring, benzothiazole ring, benzo Imidazole ring, benzotriazole ring 'anthracene ring' carbazole ring 'kalkenyl ring, quinoline ring, isoquinoline ring, quinacrid ring 'quinazoline ring, octyl ring, quinoxaline ring, anthracene ring' Acridine ring 'carbazole ring 'DY pyridine ring, pyridine ring, dibenzopyran ring, morphine ring, morphine ring, oxazepine ring, morphe ring, and thioindole ring. Preferred are a naphthalene ring, a molybdenum ring, an anthracene ring, a benzoxazole ring, a benzimidazole ring, and a fluorene ring. It is preferred to form a single bond in (b) to combine the carbon atoms of the two aromatic groups. In order to combine two aromatic rings, two or more single bonds may be formed such that an aliphatic ring on the non-aromatic heterocyclic ring may be formed between the two aromatic rings. Preferably, the bonding group in (c) is combined with each of the carbon atoms of two or more aromatic rings. The linkage is alkyl, alkenyl, alkynyl, _C 〇 _, - 〇 _, -NH-, -S-, and combinations thereof. Examples of the combination of the bond groups are shown as follows (cd) to (c-15). It should be noted that the positions of the right and left sides of each bonding group can be reversed. (c-1): -C0-0- (c-2): -CO-NH- (c-3): -alkyl-O-(c-4): -NH-CO-NH- (c - 5 ): -NH-C0-0- (c-6): -0-C0-0- (c-7): -〇-alkyl--0-(c-δ): -CO-exene -45- 1322042 (c-9): -CO-alkenyl-NH-(c-10): -CO-alkenyl-O-(C-1 1):-alkyl-CO- O-Alkyl-anthracene-c O-Alkyl-(c-12): -〇-Extension-based-CO-O-Alkyl-O-CO-Extension-Based----c-13 ): -O-CO-alkylene-CO-O- (c-14): -NH-CO-alkenyl-(c-15): -O-CO-alkenyl-aromatic ring and bond The linking group may have a substituent. As the substituent, there are a halogen atom (F, Cl, Br, I) 'hydroxy' carboxyl group, a cyano group, an amine group, a nitro group, a thio group, an amine carbaryl group, an amine sulfonyl group, a ureido group, an alkyl group, an alkene group. Alkyl, alkynyl, aliphatic fluorenyl, aliphatic methoxy, alkoxy, alkoxycarbonyl, alkoxycarbonylamino 'alkylthio'alkylsulfonyl, aliphatic guanylamino a sulfonamide group, an aliphatic substituted amine group, an aliphatic substituted amine carbenyl group, an aliphatic substituted amine sulfonyl group, an aliphatic substituted ureido group, and a non-aromatic bond ring. The number of carbon atoms is preferably from 1 to 8. Alkyl groups, especially linear alkyl groups, are preferred over cyclic alkyl groups. Further, the alkyl group may have a substituent (for example, a hydroxyl group, a carboxyl 'alkoxy group, an alkyl-substituted amine group). As for alkyl (including substituted alkyl), there are methyl, ethyl, n-butyl, n-hexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl, and 2-diethyl Aminoethyl. The number of carbon atoms in the alkenyl group is preferably from 2 to 8. Alkenyl groups, especially linear alkenyl groups, are preferred over cyclic alkenyl groups. The alkenyl group may have a substituent. As the alkenyl group, there are a vinyl group, an allyl group and a 1-hexenyl group. The number of carbon atoms in the alkynyl group is preferably from 2 to 8. An alkynyl group, especially a linear alkynyl group, is preferred over a cyclic alkynyl group. The alkynyl group may have a substituent. As the alkynyl group, there are an ethynyl group, a 1-butynyl group and a 1-hexynyl group. -46- 1322042 The number of carbon atoms in the aliphatic sulfhydryl group is preferably from 1 to 10. As for the aliphatic thiol group, there are an ethyl group, a propyl group and a butyl group. The number of carbon atoms in the aliphatic methoxy group is preferably from 1 to 10. As for the aliphatic methoxy group, there is an ethoxy group. The number of carbon atoms in the alkoxy group is preferably from 1 to 8. The alkoxy group may have a substituent (e.g., an alkoxy group). As for the alkoxy group (including the substituted alkoxy group), there are a methoxy group, an ethoxy 'butoxy group' and a methoxyethoxy group. The number of carbon atoms in the alkoxycarbonyl group is preferably from 2 to 10. As the alkoxycarbonyl group, there are a methoxycarbonyl group and an ethoxycarbonyl group. The number of carbon atoms in the alkoxycarbonylamino group is preferably from 2 to 10. As the alkoxycarbonylamino group, there are a methoxycarbonylamino group and an ethoxycarbonylamino group. The number of carbon atoms in the alkylthio group is preferably from 1 to 12. As for the alkylthio group, there are a methylthio group, an ethylthio group and an octylthio group. The number of carbon atoms in the alkylsulfonyl group is preferably from 1 to 8. As for the alkylsulfonyl group, there are a fluorenyl group and a fluorene group. The number of carbon atoms in the aliphatic guanamine group is preferably from 1 to 10. As for the aliphatic guanamine group, there is acetaminophen. The number of carbon atoms in the aliphatic sulfonamide group is preferably from 1 to 8. As the aliphatic sulfonamide group, there are methotrexate, butazone and n-octylsulfonamide. The number of carbon atoms in the aliphatic substituted amine group is preferably from 1 to 10 carbon atoms. As the aliphatic substituted amino group, there are a dimethylamino group, a diethylamino group and a 2-carboxyethylamino group. The number of carbon atoms in the aliphatic substituted amine indenyl group is preferably from 2 to 10. As for the aliphatic substituted amine carbenyl group, there are methylamine methyl sulfonyl group and diethylamine methyl fluorenyl group. The number of carbon atoms in the aliphatic substituted amine sulfonyl group is preferably from 1 to 8. As the aliphatic substituted sulfonyl group, there are methylamine sulfonyl group and diethylamine sulfonyl group. The number of carbon atoms in the aliphatic substituted urea group is preferably from 2 to 10. As for the aliphatic substituted urea group, there is a methylurea group. As the non-aromatic heterocyclic group, there are -47- 1322042 piperidyl group and morpholinyl group. The molecular weight of the retardation modifier is preferably from 300 to 800. Specifically, the retardation adjusting agent is disclosed in Japanese Patent Laid-Open Publication No. 2000_U1914, No. 200-27 5434, and International Patent Application No. WOOO/653 No. 84 (Measurement Method of Solid Material Concentration in Upper Mould Liquid) for Measurement The concentration of the solid material in the molding liquid is obtained by taking a predetermined volume of the molding liquid from the film production line as a sample, and measuring the sample. The sample was then heated at 1200 °C for 2 hours and the weight of the residual material was measured. The weight ratio of residual material to sample is then obtained. It should be noted in the present invention that the solid material is a mixture of an additive and a polymer as a raw material of the film. The pure material of each film is not always a solid material at room temperature. Furthermore, the present invention is independent of the method of measuring the concentration of solid materials. [Experiment] The experiment of the present invention was carried out as follows. However, the invention is not limited by this experiment. Three kinds of upper molding liquids A, B, and C were prepared from the following components. It should be noted that the cellulose triacetate raw material for the upper molding liquids A and B is wood pulp, and the upper molding liquid c is cotton wool. Further, each of the UV absorbers I, II, and III is 2-( 2'-hydroxy-5,-methylphenyl)benzotriazole ' 2,2'-dihydroxy-4-methoxydiphenyl ketone And 2-(2'-hydroxy-3,5'-di-t-butylpentylphenyl)-5-chlorobenzotriazole. These UV absorbers I, II, and III also have the effect of retarding the modifier. (Preparation of the upper molding liquid A) The contents of the upper molding liquid A were prepared as follows. First, the mixed solvent of dichloromethane, methanol, ethanol, and n-butanol is cooled to 0 ° C, and the solid material is stirred -48- 1322042

The mixture solvent is added to mix to uniformly disperse the solid material. The dispersion pressure was then increased to 20 kg/cm 2 in a line (including a static mixer) while the dispersion was heated to two preset temperatures. The solid material is dissolved in this way to obtain a molding liquid. The preset temperature is first 70 °C and then 3 8 °C. Further, the upper molding liquid was sequentially cooled to two preset temperatures, and then filtered using a filter paper having an absolute pore size of 10 μm. The preset temperature for cooling is first 7 then 3 8 t. The filtered solution was heated to effect flash evaporation. The solvent was evaporated in this way and the concentration of the solid content was 23%. Then, it was filtered using a sintered metal filter having an absolute pore diameter of 5 μm to obtain an upper molding liquid A. 1 8 · 90 0% by weight 1 .0 0% by weight 0.6 0% by weight 〇. 5 0% by weight 〇·1 0% by weight 0.2 0% by weight 0 · 3 0 Weight °/〇〇. 0 5重量% 〇. 〇 2% by weight 〇 _ 3 0% by weight ό 0.9 0% by weight

Cellulose triacetate (degree of acetylation 6 0.7%, degree of polymerization 315, degree of substitution of thiol group at the sixth position 〇·94, average particle size 0.5 mm) Triphenyl phosphate (TPP) Phosphate Phenyldiphenyl ester (BDP) Diethyl citrate UV absorber I UV absorber II UV absorber III cerium oxide particles (particle size 15 nm, Mo type hardness about 7) Partial ester form of citric acid B Triacetamide chloroformate-49- 1322042 Methanol 1 5.6 0 wt% Ethanol 1.20 wt% n-butanol 0.40 wt% (Preparation of the upper molding liquid B) The contents of the upper molding liquid B were prepared as follows. First, a mixed solvent of dichloromethane, methanol, ethanol 'n-butanol, and acetone was cooled to _ 2 Ot, and a solid material and a diatomaceous earth as a filter aid were stirred into a mixed solvent in a continuous kneader. It should be noted that the diatomaceous earth particles have an average diameter of 60 μm, and the content of the diatomaceous earth to the sum of the solid material and the diatomaceous earth is 0.2%. Then, the mixture ffi was dispersed and dispersed by a screw extruder having a cooling jacket to _ 9 〇 ° C ' to become a gel-like material. The gelatinous material is heated to two preset temperatures, first 7 ° C and then 135 ° C. The mixture was then filtered using a pre-coated Tefi〇n (trade name) non-woven fabric to remove diatomaceous earth particles having a diameter of 60 μm. It should be noted that in the nonwoven fabric, the absolute pore diameter is 2 Å. The solution was then filtered using a sintered metal crucible having an absolute pore size of 2.5 microns. The filtered solution is cooled to two preset temperatures, first 701 and then 3 (rc, and the upper molding liquid is obtained. Note that the cellulose acetate propionate (as a polymer) having the following content is obtained from wood pulp. Triacetate 18.90% by weight (total degree of acetylation 2.83, degree of polymerization 270, degree of substitution of thiol group at the sixth position of 0.86, average particle size 〇·5 mm) Cellulose tripropionate 5.90% by weight (total The degree of deuteration is 2.89, the degree of total acetylation is 2.59 1322042, the degree of polymerization is 270, the degree of substitution of acetyl group in the sixth position is 〇. 94, the average particle diameter is 0 · 5 mm) diisopentaerythritol hexaacetate 1.00 weight % Triphenyl phosphate (TPP) 1.00% by weight Biphenyldiphenyl phosphate (BDP) 0.10% by weight Diethyl citrate 0.10% by weight UV absorber I 0.1 0% by weight UV absorber II 0.2 0% by weight UV Absorbent III 0.30% by weight of cerium oxide particles 0.05% by weight (particle size 15 nm, Mohs hardness of about 7) Partial ester form of citric acid 0.0 2% by weight Noon amine 0.30% by weight Acetic acid Methyl ester 6 2.1 0% by weight methanol 4.0 0% by weight ethanol 5.0 0 weight N-butanol 3.00% by weight Acetone 5.00% by weight (Preparation of the upper molding liquid C) The contents of the upper molding liquid C were prepared as follows. It should be noted that the upper molding liquid C was prepared in the same manner as the above molding liquid A. Acetate 19.00% by weight (total degree of deuteration 2.5, degree of polymerization 25 0, degree of substitution of thiol group in the sixth position 0.86, average particle -51 - 1322042 diameter 〇 5 mm) cerium oxide particles 0 · 0 5 % by weight (particle size 15 nm 'Mo type hardness about 7) Partial ester form of citric acid 0-02 Weight Tribenzylamine 0 · 30% by weight Dichloromethane 6 0.9 0% by weight Methanol 1 5 · 60% by weight Ethanol 1.20% by weight n-butanol 0-40% by weight (Preparation of the upper molding liquid D) The upper molding liquid A was diluted with a static mixer so that the concentration of the solid material was changed to 19.5%. Thus, the upper molding liquid D is obtained. The solvent used for the dilution is the same as the solvent mixture of the upper molding liquid A. (Preparation of the upper molding liquid E). The upper molding liquid B is diluted on the line using a static mixer to make the concentration of the solid material. It becomes 1 9 · 5 %. The upper molding liquid E is obtained in this way. The amount is the same as the solvent mixture of the upper molding liquid B. _ [Example 1] (Film manufacturing method) The casting is carried out by the coating mold of Fig. 4, which has a feeding zone in which co-casting is performed to form three layers. The cylinder described in Fig. 11 is 〇2, and hard chromium is plated on the surface of the cylinder 1〇2. The mirror finish was polished so that the centerline average roughness was 0. 〇 3 μm. It should be noted that in the cylinder 1〇2, the surface temperature was maintained at 51, the diameter was 1800 mm', and the width was 1 mm. -52- 1322042 is designed such that the film 36 can have first to third layers 35a-35c each formed by the molding liquid A of the upper molding liquid C' and the upper molding liquid C, so that after drying, first and third The layers 35a, 35c have a thickness of 1 - 5 microns and the second layer 5b has a thickness of 57 microns. The upper molding liquid A and the upper molding liquid C were fed to the feed zone 62, and cast on the cylinder 102 to have a width of 1,580 mm. Thus, the relative speed of the cylinder 102 to the lip of the mold 14 was adjusted to 30 m/min. In addition, the plates are provided such that air flow that occurs as a result of moving the cylinder 102 does not escape from the edges of the casting surface. The solvent was evaporated from the gel-like film 35, and the solvent vapor was condensed by a condenser 105, which was placed at a temperature of 5.0 mm from the gel film 35 and cooled to -25 °C. The condensed solvent is received by the liquid receiver 53. Therefore, the temperature gradient Q is 35 and the difference in the width direction is 5%, and the temperature Tc of the condenser 95 is 5 °C in the width direction. The winding speed between the jelly film 35 and the condenser 105 is at most 0.5 m/sec. The casting equipment 1 〇 1 series is supplied in a gastight shell through which a small amount of nitrogen flows. Thus maintain the oxygen concentration at up to 6% by volume in the atmosphere and keep the dew point at the most -3 °C. The gel film 35 containing 250% by weight of the solvent was peeled off from the cylinder 1 〇 2 to a film 36 at a peeling force of 60 Newtons. Each of the pin tensioners 125 is then nailed to the side edge portion of the film 36. The film 36 was then heated to dry in two steps, i.e., first 80 ° C and then 12 ° C. The film 36 is then transported to a roll drying unit 42 where a tension of 110 Newtons is applied for thermal drying and cooling. The thermal drying in the roll drying unit 42 is carried out in two steps, i.e., 120 ° C first, then 135 ° C. The cooling system was carried out at 25 °C. The cooled film 36 is wound by a winding device 47. -53- 1322042 [Example 2] (Film manufacturing method) The casting was carried out by the casting apparatus of Fig. 2. Belt 3 1 is made of stainless steel. The mirror finish was polished such that the centerline average roughness was 0.03 microns. It should be noted that the surface temperature of the heating plate 25 was maintained at 25 using a radiant heater. (: The belt 31 is 10 meters long and 800 mm wide. It is designed such that the film 36 may have first to third layers 35a-35c each formed by the upper molding liquid C, the upper molding liquid B and the upper molding liquid C, After drying, the first and third layers 35a, 35c have a thickness of 1.5 μm, and the second layer 35b is 3 μm. The upper molding liquid B and the upper molding liquid C are fed to the feed zone 62, and The belt 31 is cast to a width of 650 mm. Thus, the relative speed of the belt 31 to the lip of the mold 14 is adjusted to 6 m/min. Further, a plate for shielding the unexpected flow is provided so that the air flow due to the moving belt 31 does not flow. The solvent is evaporated from the gel film 35 from the side edge of the casting surface, and the solvent vapor is condensed by the condenser 52, which is disposed at a temperature of 5.0 mm from the gel film 35 and cooled to a temperature of -5 ° C. The liquid receiver 53 receives the condensed solvent. Thus, the temperature gradient Q is 30 and its difference in the width direction is 5%. The temperature Tc of the condenser 52 is 5 ° C in the width direction. The gel film 35 and the condenser 52 The speed of the roll is up to 0.5 m/s. The casting equipment 1 is supplied in a gas-tight shell through which a small amount of nitrogen flows. The oxygen concentration was maintained at a maximum of 6% by volume, and the dew point was maintained at a maximum of -15 ° C. The gel film 35 containing 150% by weight of the solvent was stripped from the cylinder 102 by a stripping force of 40 Newtons to form a film 36. Other conditions Same as example 1 - 54 - 1322042

[Example 3 J (film manufacturing method) The first and third layers 35a, 35c were formed of an upper molding liquid, which was prepared from the contents of the molding liquid C without the UV absorber and the plastic agent. The upper molding liquid was cast so that the first and third layers 35a, 35c were 0.5 μm and 1.5 μm thick after drying. The second layer 35b is formed of the upper molding liquid A and is 28 μm thick after drying. Other conditions are the same as in Example 1. [Example 4] (Film manufacturing method) The first layer 35a was formed of an upper molding liquid, which was prepared from the contents of the molding liquid C without the UV absorber and the plasticizer. The upper molding liquid was cast so that the first layer 35a was 1.5 μm thick after drying. The second layer 35b is formed of the upper molding liquid A and is 57 μm thick after drying. The third layer 35c is formed of the upper molding liquid E and is 0.2 μm thick after drying. Co-casting to form first to third layers 3 5a-3 5c » Other conditions are the same as in Example 1. [Example 5] (Film manufacturing method) The first and third layers 35a, 35c are formed of an upper molding liquid, which is prepared from a content of a mold liquid D without a UV absorber and a plasticizer. The casting is such that the first and third layers 35a, 35c are 1.0 micron and 2 microns thick after drying. The second layer 3 5b was formed from the upper molding liquid B and was 77 μm thick after drying. Co-casting is performed to form first to third layers 35a-35c. The other conditions are the same as in Example 1. -55- 1322042 [Comparative 1] (Film manufacturing method) In the casting apparatus 91, the condenser 95 is not used, and dry air is blown to the casting surface to be dried. Dry air has a blowing speed and temperature of 15 m/s and 40 °C. The dry air is used cyclically, and the solvent vapor in the exhaust gas is condensed at a temperature of up to -30 ° C in a cooling device (not shown) to recover the solvent. Other conditions are the same as in Example 1. [Comparative 2] (Film manufacturing method) In the casting apparatus 16, the condenser 52 was not used, and dry air was blown to the casting surface to be dried. Dry air blowing speed and temperature of 10 m / s and 80 ° C » The dry air is used cyclically, and the solvent vapor in the exhaust gas is condensed at a temperature of up to -5 ° C in a cooling device (not shown) Recover solvent. Other conditions are the same as in Example 1. [Comparative 3] (Film manufacturing method) The solvent vapor was condensed by a condenser 95, which was disposed at a distance of 20 mm from the gel film 35 and cooled to _5 (temperature: the casting surface of the gel film 35 and The percentage of the difference between the condensers 95 is .11%. The temperature gradient Q is 3, and the temperature Tc of the condenser 95 is 12 °C in the width direction. [Comparative 4] (Film manufacturing method) First And the third layer 35a, 35c is formed by the upper molding liquid, which is prepared from the content of the mold liquid C without the UV absorber and the plastic agent. The upper mold liquid casting - 56-1322042 makes the first and third layers 35a, 35c are 0.5 micrometers and 1.5 micrometers thick after drying. The second layer 3bb is formed by the upper molding liquid A and is 28 micrometers thick after drying. Further, in the casting apparatus 91, the condenser 95 is not used. Dry air is blown onto the casting surface to dry. The air blowing speed and temperature of the dry air are 15 m/s and 4 ° C. The dry air is used cyclically, and the exhaust gas is used in a cooling device (not shown). The solvent vapor is condensed at a temperature of up to -3 ° C to recover the solvent. Other conditions are the same as in Example 1. Measurement and Judgment of Thickness] In Example 1-5 and Comparative 1-4, the thickness of the film was measured, and the frequency spectrum was obtained from the measurement results. The thickness measurement was first measured by continuous advancement in the longitudinal direction of the middle portion between the side edges of the film. Next, the measurement was carried out continuously in the width direction. The judgment of the appearance of the film was carried out with the naked eye, and the results thereof are shown in Table 1. In Table 1, "A" indicates that the film was good in appearance, and "N" indicates that unevenness was observed. In Table 1, R1 and R2 are calculated from the thickness 値 obtained in the first embodiment. R1値 is the ratio of the average error MD1 of the thickness 对 to the thickness average 値ΤΑ 1 of the thickness 。. The frequency spectrum of this experiment is obtained by FFT analysis of a measured thickness 。. In Table 1, R2値 is the ratio of the maximum frequency spectrum 値SPl^ to the thickness average 値TA1. In addition, R3 and R4 are based on the second specific The thickness 値 obtained in the example is calculated. R3 値 is the ratio of the average error MD1 of the thickness 对 to the thickness average 値TA1. In addition, the FFT analysis of the thickness 値 of the second measurement is performed to obtain the frequency spectrum of the experiment. In 1 , R4値 is the ratio of the maximum frequency spectrum to the thickness average 値TA1. -57- 1322042 [Table 1] R1 (%) R2 (%) R3 (%) R4 (%) FA PSA _ Example 1 6.2 1.3 8.5 3.6 AA Example 2 7.4 3.2 9.2 5.3 AA Example 3 8.2 3.9 9.5 4.6 AA Example 4 6.3 2.3 8.2 3.6 AA Example 5 4.1 2.8 6.7 2.9 AA Comparison 1 8.9 4.5 13.5 7.2 NN Comparison 2 9.7 5.3 14.5 8.6 NN Comparison 3 17.8 10.8 19.5 10.2 NN comparison 4 18.6 11.0 18.3 10.0 NN — FA : Film appearance PSA: Polarized filter appearance [Measurement of retardation ]] In the following method of measuring birefringence, we get in Example 1-5 and compare! The retardation of each film made in _4. Blocking 値Re and Rth are measured throughout the thickness measurement. The measurement results are shown in Tables 2 & The retardation 値Re is measured at the position where they are arranged in the length direction. In Table 2, R5 値 is the ratio of the average error MD3 of the block 値Re to the block mean 値RA1 of the thickness 値. R6値 is the ratio of the frequency spectrum of the block 値Re to the maximum 阻SP2MAX versus the mean 値. In addition, the retardation 値 Re is measured at the positions arranged in the length direction. In Table 2, R7値 is the ratio of the average error of the block 値Re to the block mean 値. R8値 is the ratio of the maximum frequency spectrum of the block 値Re to the block average 値. In addition, the retardation 値Rth is measured in the length direction. In Table 3, R9値 is the ratio of the average error MD5 of the block 値Rth to the block mean 値RA3 of the thickness 値. R1 0値 is the ratio of the maximum frequency spectrum of the block 値Rth to the block average 値. Further, the retardation 値 Rth is measured in continuous measurement in the width direction. In Table 3, R 1 1値 is the ratio of the average error of the block 値Rth to the block average of -58 to 1322042 。. R1 2値 is the ratio of the maximum frequency spectrum of the block 値Rth to the average 値 block. (Measurement of Block 値Re) The block 値Re is calculated by the difference of the measured block 测量 measured by the light in the direction perpendicular to the surface of the film by irradiation with 63 2.8 nm. Therefore, this measurement was carried out by an automatic birefringence meter (K0BRA21DII manufactured by Oji Scientific Instrument). The frequency spectrum is obtained by performing FFT analysis of the block 値Re. (Measurement of block 値Rth) Lu will illuminate the film by illuminating the film with 2.8 nm light, and then block the 照射Re, and then gradually tilt the surface of the film to the illuminating film to obtain resistance. The 値Re » block 値Rth system The measurement of the block 値Re is calculated. Therefore, this measurement was carried out by an automatic birefringence meter (Ellipsometer Ml 50 manufactured by Jusco Corporation). The frequency spectrum is obtained by performing FFT analysis of the block 値Rth. [Table 2] R5 (%) R6 (%) R7 (%) R8 (%) Example 1 7.2 4.2 8.8 4.6 Example 2 7.5 3.5 9.3 5.7 Example 3 8.5 4.2 9.8 6.5 Example 4 6.5 2.7 8.6 4.2 Example 5 4.5 2.2 7.2 3.2 Comparison 1 10.2 6.0 10.2 6.2 Comparison 2 11.5 6.6 11.2 7.6 Comparison 3 13.9 10.5 16.3 10.9 Comparison 4 14.0 11.5 16.2 10.5 -59- 1322042 [Table 3] R9 (%) R10 (%) R11 (%) R12 (%) Example 1 6.1 2.6 3.2 Instance 2 7.3 3.3 9.5 4.0 Example 3 8.4 4.5 9.4 6.0 Example 4 6.4 2.9 7.9 3.0 Example 5 4.2 2.5 6.5 2.7 Comparison 1 10.8 6.8 10.5 7.2 Comparison 2 11.8 7.2 12.2 8.3 Comparison 3 13.2 10.6 15.9 13.8 Comparison 4 14.0 11.1 15.5 12.6 [Manufacture of polarizing filter] A polarizing film was produced by adsorbing iodine to a oriented polyvinyl alcohol film. Then, the films of Examples 1-5 and Comparative 1-4 were adhered to both sides of the polarizing film by a polyvinyl alcohol type adhesive so that the slow axis of the film and the transmission axis of the polarizing film were parallel. The polarizing filter sample was fixed in an atmosphere of 80 ° C and 90% RH humidity for 500 hours. The appearance of the sample was judged by the naked eye, and the results thereof are shown in Table 1. It should be noted that "A" indicates that no change in color intensity of the crossed Nicols position was observed, and "N" indicates that a change in color intensity was clearly observed. [Evaluation of the degree of polarization] The parallel transparency Υρ φ and the direct transparency Yc of the polarization in the visible light region are measured by a spectrophotometer. Then, based on the parallel transparency Υρ and the direct transparency Yc, the degree of polarization is calculated from the following formula: P = [(Yp-Yc) / (Yp + Yc)], /2x100 (%) In which the film of each of Examples 1-4 is used In the polarizing filter, the degree of polarization is over 99.6%. The polarizing filter has sufficient durability. However, in the polarizing filter in which the films of Comparative 1-3 were used, the degree of polarization was over 9 9.4 % - 9 9 · 6 %. [Production of Optical Compensation Film] -60 - 1322042 A polarizing film was produced by adsorbing iodine to a drawn polyvinyl alcohol film. Then, the film produced in Example 1 was adhered to the surface of the polarizing film with a polyvinyl alcohol type adhesive so that the slow axis of the film and the transmission axis of the polarizing film were parallel. Further, another film obtained in Example 1 was produced, and then the saponified film was adhered to the other side of the polarizing film with a polyvinyl alcohol type adhesive. Further, an optical compensation sheet (WV film manufactured by Fuji Photo Film Co. Ltd.) was adhered to the former film (or unsaponified film) so that the slow axis of the film and the optical compensation sheet were parallel. The optical compensation film was thus obtained. Further, an optical compensation film was produced using the films produced in each of Examples 2-4 and Comparative 1-3. φ A pair of optical compensation films obtained from the films of Examples 1-4 and 1-3 were used for a TFT (Thin Film Transistor) type liquid crystal display. When using the films of Examples 1-4, the viewing angle and contrast were appropriate. When using a film of Comparative 1-3, the contrast is lowered. [Production of antireflection film]: In the following procedure, an antireflection film having an antiglare layer was produced using the films of Example 1 and Comparative Example 1. (Preparation of coating solution F for anti-glare layer) * To prepare a coating solution F for an anti-glare layer, a mixture (manufactured by DPHA' NIPPON KAYAKU CO., LTD.) in which diisopentaerythritol pentaacrylate and diisoprene are mixed is used. Tetraol hexaacrylate. 125 g of the mixture and 125 g of ruthenium (4-propenylmercaptothiophene) sulfide (manufactured by MPSMA' SUMITOMO SEIKA CHEMICALS CO., LTD.) were dissolved in 439 g of a mixed solvent containing 50% by weight of methyl ethyl ketone and 50% by weight. Cyclohexanone). The first solution was thus obtained. Further, a second solution was prepared. In a second solution of -61 - 1322042, 5.0 g of a photoinitiator for radical polymerization (IRGACURE 907 'Chiba Gaigy Japan Limited) and 3.0 g of a sensitizer (manufactured by KAYACURE DTEX, NIPPON KAYAKU CO., LTD.) were dissolved. 49 grams of methyl ethyl ketone. The second solution is added to the first solution to obtain an addition solution. This addition solution was applied and then cured by ultraviolet light to have a coating having a reflectance of 1.60. Further, 1 gram of crosslinked polystyrene particles (product name: SX-200H' Soken Chemical & Engineering Co., Ltd.) having an average particle diameter of 2 μm was added to the addition solution, and this mixture was stirred at a high speed mixer. The mixture was stirred for 1 hour to disperse the crosslinked polystyrene particles. The stirring speed is 5000 rpm. The dispersion solution was then filtered through a polypropylene filter having a pore size of 30 μm each. Then, a coating solution F for an antiglare layer was obtained. (Preparation of coating solution G for anti-glare layer) A mixture of 104.1 g of a mixture solvent containing cyclohexanone and 61.3 g of methyl ethyl ketone was stirred with an air stirrer. Then, 217.0 g of a zirconia-containing hard coating coating solution (DeSolite KZ-78 86A, manufactured by JSR Corporation) was added to the mixture solvent to obtain an addition solution. The addition solution was cast and then cured by ultraviolet light to obtain a coating having a refractive index of 1.6. Further, 5 g of crosslinked polystyrene particles (product name: SX-200H, manufactured by Soken Chemical & Engineering Co., Ltd.) having an average particle diameter of 2 μm were added to the addition solution, and this was taken up by a high-speed stirrer. The mixture was stirred for 1 hour to disperse the crosslinked polystyrene particles. The stirring speed is 5000 rpm. The dispersion solution was then filtered through a polypropylene filter having a pore size of 30 μm each. Then, a coating solution G for an antiglare layer was obtained. -62- 1322042 (Preparation of coating solution for antiglare layer) To prepare a coating solution H for an antiglare layer, methyl ethyl ketone and cyclohexanone were mixed at a ratio of 54% by weight to 46% by weight as a solvent. Further, a mixture (DPHA, manufactured by NIPPON KAYAKU CO., LTD) was used in which diisopentaerythritol pentaacrylate and diisopentaerythritol hexaacrylate were mixed. A mixture of 91 g of a solvent of 52 g of a solvent, 199 g of a hard coating solution containing cerium oxide (DeSolite KZ-7115, manufactured by JSR Corporation), and 19 g of a hard coating solution containing a chromium oxide dispersion (DeSolite KZ-7161, manufactured by JSR Corporation) ). The mixture was dissolved in this way to obtain a mixed solution. Then, 10 g of the radical polymerizable composition was dissolved in the mixed solution with a photoinitiator (IRGACURE 907, manufactured by Chiba Gaigy Japan Limited) to obtain a solution. This addition solution was applied and then cured by ultraviolet light to obtain a coating having a refractive index of 1.61. Further, 20 g of crosslinked polystyrene particles (product name: SX-200H, manufactured by Soken Chemical & Engineering Co., Ltd.) having an average particle diameter of 2 μm were added to 80 g of a mixture solvent in which 54% by weight of methyl ethyl ketone was mixed. With 46% by weight of cyclohexanone. This mixture was stirred for 1 hour at a high speed stirrer of 5000 rpm to disperse the crosslinked polystyrene particles, and an addition solution was added to obtain a dispersion solution. The dispersion solution was then filtered through a polypropylene filter having a pore size of 30 μm each. Then, a coating solution for an anti-glare layer was obtained. (Preparation of coating solution I for hard coat layer) In order to prepare a coating solution I for a hard coat layer, 62 g of methyl ethyl ketone was mixed with 88 g of cyclohexanone as a solvent. Then, 25 0 g of a UV radiation hardenable hard coating composition (DeSolite® 76 8 9, 72% by weight, manufactured by JSR Corporation - 63-1322042) was dissolved in the solvent. Coating this addition solution and then hardening it with ultraviolet light

I coating with a refractive index of 1.53. Further, the solution was filtered with a polypropylene filter having a pore size of 30 μm each. Then, a coating solution I for a hard coat layer was obtained. (Preparation of coating solution J for low reflectivity layer) 8 g of MEK-ST (average particle diameter of 10 nm to 20 nm, SiO 2 sol dispersion of methyl ethyl ketone, solid content of 30% by weight, Nissan Chemical Industries Co., Ltd., and 100 g of methyl ethyl ketone were added to 20093 g of a fluoride-containing heated crosslinked polymer (TN-049, manufactured by JSR Corporation) having a refractive index of 1.42. The mixture was stirred and the solution was filtered through a polypropylene filter having a pore size of 1 μm. Thus, a coating solution J for a low refractive index layer was obtained. The surfaces of the films of Examples 1-5 and Comparative 1-4 were coated with a coating solution I using a bar coater, followed by drying at 120 °C. UV light was then applied to the coating on the film at a 160 watt/cm air-cooled metal toothed lamp (manufactured by Eyegraphics Co., Ltd.). The illumination is 400 mW/cm 2 and the illumination density is 300 mJ/cm 2 . The coating of the upper molding liquid was thus hardened to form a hard coat layer having a thickness of 2.5 μm on the film. Further, the coating solution F was applied to the hard coat layer on the film by a bar coater. The coating solution F is dried and hardened under the same conditions as the formation of the hard coat layer. The 1.5 micron antiglare layer A was thus formed. Further, the anti-glare layer A was coated with the coating solution j for the low refractive index layer, and then the coating solution J was dried at 80 ° C. Then, the film was crosslinked at 120 ° C for 10 minutes to form a low refractive index layer, and the thickness thereof was formed. Is the coating solution G replaced with a coating solution of 0.096 μm? Coating the film. Other conditions are the same as those for forming an antireflection film. In this case, the anti-glare layer B is formed. Further, -64 - 1322042 was used to coat the coating solution F with a coating solution 。. Other conditions are the same as those for forming an anti-reflection film. In this case, the anti-glare layer C is formed. (Evaluation of Antireflection Film) The following experiment was conducted for the estimation of each antireflection film having antiglare layers A, B, and C. The test results are shown in Table 2. (1) Spectral reflectance and color lightening Spectrophotometer V-550 (manufactured by JASCO Corporation) has a joint A RV-474 to measure at a 5° incident angle at an incident angle of 380 to 780 nm. The spectral reflectance at the location. The average spectral reflectance of the reflections from 450 nm to 65 nm is then calculated to evaluate the antireflective properties. 反射 The reflectance spectra are obtained from the observations. Then, the L* number, the a* number and the b* number of the CIE 1 976 L*a*b* space are calculated from the reflection spectrum, which represents the color change of the regular reflection of the light generated by the CIE standard light source D65 at an incident angle of 5°. light. The color fade is calculated based on the L* number, the a* number, and the b* number. (2) Overall reflectance The spectrophotometer V-550 (manufactured by JASCO Corporation) has a connector ILV-471 to measure the overall reflectance at an incident angle of 5° in accordance with incident light between wavelengths of 380 to 780 nm. The average overall reflectance of the reflection between wavelengths from 450 nm to 650 nm is then calculated to evaluate the anti-reflective properties. (3) Haze The haze of the antireflection film was measured using a fog meter 1001 DP type (manufactured by Nippon Denshoku Industries Co., Ltd.). (4) Pencil hardness -65- 1322042 The pencil hardness was evaluated as described in JIS Κ 5400, and its data was used as a basis for scratch resistance. The antireflection film was fixed in an atmosphere at a temperature of 25 ° C and a humidity of 60% RH for 2 hours, and the surface of the antireflection film was scratched with a 3H test pencil and measured by Π S S 6 0 0 6 . Therefore, a force of 1 kg is applied to the test lead pen. The pencil hardness was evaluated as "Α" when no scratches were left on the surface in the evaluation of n = 5 (η is the number of tests for the scratching performance). When one or two scratches were left on the surface in the evaluation of η = 5, it was evaluated as "Β". When more than three scratches were left on the surface in the evaluation of η = 5, it was evaluated as "Ν". (5) Contact angle # After the anti-reflection film was fixed in an atmosphere of humidity of 25 ° C and 60% RH for 2 hours, the water contact angle on the anti-reflection film was measured, and the data was used as a reference for stain resistance, particularly It is resistant to fingerprint contamination. (6) Dynamic friction coefficient: The anti-reflection film is fixed at a temperature of 25 ° C and a humidity of 60% RH: After 2 hours in the gas, the dynamic friction coefficient is measured by a mechanical HEIDON-14 measuring the dynamic friction coefficient, wherein Stainless steel ball with a diameter of 5 mm. The speed was set to 60 cm/min, and a force of 1.00 x 10 3 Newtons was applied to the antireflection film. * (7) Anti-glare properties One-time and two-time stimulation of anti-glare properties of 27 kinds of anti-reflective films obtained. The louver-free fluorescent lamp (800 cd/m2) emits light to each anti-reflection film and reflects light. Observe the image of the fluorescent lamp formed by the reflection. This completes an estimate. The anti-glare property is estimated to be "E" (excellent) when no contour of the illuminator is observed. When the outline is slightly recognized, it is estimated to be "G" (good). When the contour is not clear but identifiable, it is estimated to be "P" (pass). When the contour is almost 淸 -66- 1322042, it is estimated to be "R" (cull). In addition, the grade of anti-glare properties is estimated by observation of macroscopic inhomogeneity. Therefore, a second estimate is made. [Table 4]

SA SR (%) IR (%) Color fades L^/a^/b H (%) PH (3H) CA DF 1AP/ 2AP Example 1 A 1.1 2.0 10/1.9/1.3 8 A 103° 0.08 E/GB 1.1 2.0 9/2.0/-4.0 8 A 103° 0.08 E/GC 1.1 2.0 9/1.7/0.2 12 A 103° 0.07 E/G Example 2 A 1.1 2.0 10/1.8/1.3 8 A 103° 0.08 E/GB 1.1 2.0 9/2.0/-4.0 8 A 103° 0.08 E/GC 1.1 2.0 9/1.9/0.2 12 A 102° 0.07 E/G Example 3 A 1.1 2.0 10/1.8/1.2 8 A 103° 0.08 E/GB 1.1 2.0 9/2.0/-4.0 9 A 102° 0.08 E/GC 1.1 2.0 9/1.7/0.3 11 A 103° 0.07 E/G Example 4 A 1.1 2.0 10/1.7/1.3 8 A 103° 0.08 E/GB 1.1 2.0 9 /2.0/-4.0 9 A 102° 0.08 E/GC 1.1 2.0 9/1.7/0.3 12 A 102° 0.07 E/G Example 5 A 1.1 2.0 10/1.8/1.3 9 A 102° 0.08 E/GB 1.1 2.0 9/ 2.0/-3.9 8 A 102° 0.08 E/GC 1.1 2,0 9/1.6/0.2 12 A 102° 0.07 E/G Comparison 1 A 1.1 2.0 10/1.9/1.3 8 A 103° 0.08 E/RB 1.1 2.0 9 /2.0/-0,4 8 A 103° 0.08 E/RC 1.1 2.0 9/1.7/0.2 11 A 103° 0.08 E/R Comparison 2 A 1.1 2.0 10/1.8/1.3 8 A 103° 0.08 E/RB 1.1 2.0 9/2.0/-4.0 9 A 102° 0.07 E/RC 1.1 2.0 9/1.8/0.2 12 A 102° 0.08 E/R Comparison 3 A 1.1 2 .0 10/1.7/1.2 8 A 103° 0.08 E/RB 1.1 2.0 9/2.0/-4.0 9 A 103° 0.08 E/RC 1.1 2.0 9/1.7/0.2 12 A 102° 0.07 E/R Comparison 4 A 1.1 2.0 10/1.7/1.3 8 A 103° 0.08 E/RB 1.1 2.0 9/2.1/-4.0 8 A 103° 0.08 E/RC 1.1 2.0 9/1.8/0.2 12 A 102° 0.08 E/RSA : Anti-glare layer Solution type SR : Spectral reflectance IR : Overall reflectance H : Haze PH : Pencil hardness CA : Contact angle DF : Dynamic rub coefficient 67 - 1322042 1 API - Sub-estimated anti-glare property 2AP : Anti-glare property of secondary estimation Table 4 teaches that the films produced in Examples I-5 and 1-4 are excellent in anti-glare properties. In addition, the color becomes lighter and the pencil hardness is 'contact angle or anti-fingerprint contamination, and the dynamic friction coefficient is excellent. The antireflection properties of the antireflection films of Examples 1 - 5 were excellent. However, aggregation (including thickness unevenness) and uneven coating were observed in the anti-reflection film manufactured in Comparative 1-4. Various changes and modifications are possible in the present invention, and it should be understood that they are within the scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS The above objects and advantages of the present invention will be readily understood by those skilled in the art from this disclosure. 1 is a schematic view showing a method of manufacturing a film in which a solution casting method is employed as a method of producing a film from the polymer solution of the present invention; FIG. 2 is a schematic view showing a first embodiment of the casting apparatus of the present invention; Figure 3 is a cross-sectional view taken along line III-III of Figure 2; Figure 4 is a cross-sectional view of the mold of the present invention; Figure 5 is a schematic view of another embodiment of the mold of the present invention. Figure 6 is a plan view showing a second embodiment of the casting apparatus; Figure 7 is a plan view showing the measurement position of the film thickness and the measurement position of the birefringence; and Figure 8 is a view showing the measurement position of the film thickness and the measurement position of the birefringence -68- 1322042 cutaway view; Fig. 9 is a partial plan view of a third embodiment of the casting apparatus of the present invention; Fig. 10 is a cross-sectional view taken along line IX-IX of Fig. 9; Partial plan view of a third embodiment of the inventive casting apparatus; Fig. 12 is a plan view and a partial cutaway view of the first embodiment of the tensioning device; Fig. 13 is a plan view of the second embodiment of the tensioning device Partial cut _ face map. [Main component symbol description] 11...Preparation of the upper molding liquid 12... casting upper molding liquid 12a-12c". Praying upper molding liquid 14...molding mold 1 5...Upper molding liquid preparation equipment 16...Casting equipment·1 7...Drying equipment 1 8...winding device 2 1...slot 2 1a·.·thermostat 2 2...chest 23...first filter device 24...second filter device 27...heating device 69- 1322042 28...flash evaporation device 3·· 3 2...first support Yukun 33...second support roller 35...colloidal film 3 5 a...first layer 35b...second layer 35c···third layer 36...film 37...stripping roller 41...tension device 42...roll drying device 4 6...cutter 4 7...winding device 4 8...聿, 51, 92, 11 2...heating plates 51a, 52a, 92a-93a, 105a ...temperature controller 5 2, 9 3, 1 0 5, 1 1 3,123 ...condenser 5 3, 94···liquid receiver 5 6...recovery tank 6 1...module 6 1 a...mould lip 61b, 75-77...passage 6 2...feeding zone 6 2 a - 6 2 c , 72a-72c···Inlet-70- 1322042 7 1,82-84... Mold 75a-77a··· Bag 91, 101...Foundry equipment 1 02...Cylinder 1 1 1...clip Tension machine 1 1 la... body 1 1 lb... clip member 121... sheet Force device 122...microwave guide 1 2 5...needle tension machine 12 5a···needle

-71 -

Claims (1)

1322042 No. I 曰修(吏)王Replacement page No. 93 121244 "Method and apparatus for manufacturing film from polymer solution, and optical polymer film" Patent (Revised on December 17, 2009) X. Patent application scope A method of casting a film formed of at least one polymer solution discharged from a mold before moving a substrate, the method comprising the steps of heating the substrate using a heater disposed along a back surface of the substrate; A condensing device that is closely disposed on the substrate facing the film condenses the solvent evaporated from the film for recovery. 2. The method of claim 1, wherein the film speed near the surface of the film is from 0.01 m/sec to 0.5 m/sec. 3. The method of claim 2, wherein the substrate moves downward at a casting location where the flowing polymer solution contacts the substrate. 4- The method of claim 1, wherein Tw (°C) is the surface temperature of the condensing device facing the film, Ts (°C) is the temperature of the film, and d (mm) is the condensing device The distance to the film, the temperature gradient Q satisfies the following formulas (1) and (2): Q = (Ts-Tw) / d (1) 5 < Q < 1 00 ... (2). 5. The method of claim 4, wherein the temperature gradient Q has a variation range of at most 10% of the temperature gradient Q. 6. The method of claim 5, wherein the temperature of the facing surface of the condensing device ranges from a maximum of 10 °C. 1322042 — I r··^* II ·__··1 f The annual P month % repair (tg 膂 page 7), as in the method of claim 6, wherein the distance d varies in the width direction of the substrate The maximum range is 10% of the average d of the distance d. 8. The method of claim 1, wherein the co-casting of the plurality of polymer solutions is carried out. 9. The method of claim 1, wherein the method The method of claim 1, wherein the film is formed on the substrate, the film has a thickness of from 10 micrometers to 1000 micrometers, and the substrate is opposite to the mold. The speed is from 5 m/min to 200 m/min. The method of claim 10, wherein the polymer contained in the polymer solution is cellulose oxime, polycarbonate, and lanthanum. The method of claim 11, wherein the polymer solution contains at least 50% by weight of the cellulose component of the polymer component, and X is in the cellulose: The sixth place in the repeat unit of the telluride Wherein the thiol substitution ratio, and γ is the thiol substitution ratio at other positions, the following conditions are satisfied in the polymer solution: I Χ>0·85 and 2.70<(X + Y)<2.99 » 13 The method of claim 1, wherein the film is an optical film. 14. The method of claim 13, wherein the optical film is used in a polarizing filter. The method of the present invention, wherein the optical film is used as a polarizing filter protective film. 16. The method of claim 13, wherein the optical film is used for light -2- 1322042 — _____ The history of the invention is as follows: 1. The method of claim 13, wherein the optical film is used for a display device. 18. A method for producing a film from a polymer solution. a device comprising: a movable substrate; a mold for casting a polymer solution on a surface of the substrate before the moving substrate to form a film; a heater provided facing the back surface of the substrate; the heater passes the film through the substrate Heating: configured to be close to ground Facing the condensing device of the film, the condensing device condenses the solvent evaporated from the film to recover. 19. The device of claim 18, wherein Tw (°C) is the surface of the condensing device facing the film Temperature, Ts (°C) is the temperature of the film, and d (mm) is the distance from the condensing device to the film. The temperature gradient Q satisfies the following formulas (1) and (2): Q = (Ts-Tw)/ d ......(1) 5<Q<1 00...(2). 20. The device of claim 19, wherein the temperature gradient Q has a range of variation of at most 10% of the temperature gradient Q. 21. The device of claim 20, wherein the temperature of the surface of the condensing device varies by a maximum of 10 °C. 2. The device of claim 21, wherein the distance d from the condensing device to the film varies in the width direction of the substrate by a maximum of 10% of the average d of the distance d. Ι333Θ43-~·___ λ? Year of the month repair (-........... 23 · The device of claim 22, wherein the substrate is a belt. 2 4. If the scope of patent application is 22 The device wherein the substrate is a cylinder. 25. An optical polymer film comprising a property satisfying the following formula: MD1 ^ O.lOxTAl ; SPImax^ O.lOxTAl wherein TA1: on the polymer film The average thickness 値MD1 of the first thickness 测量 measured by the plurality of measurement points arranged in one direction: the error average 値 of the plurality of first thickness 値, · SP1MAX: the maximum 値 of the frequency spectrum SP1, which is the first thickness 26. The optical polymer film of claim 25, wherein the maximum 値 SP1MAX of the frequency spectrum SP1 is at least the first thickness in a range corresponding to: a wavelength converted into a spatial frequency domain 10% of the average 値TA1: 〇27. The optical polymer film of claim 25 or 26, which includes the characteristics of the following formula: ® MD2 ^ 0.1 0xTA2 · where TA2: perpendicular to the two selected directions The average thickness 测量MD2 of the measured second thickness :: The error of the second thickness 値 is 値, wherein the frequency spectrum SP2 is obtained by the fast Fourier transform of the second thickness ,, and in the range corresponding to the wavelength converted into the spatial frequency domain, the frequency M M/yi repair ( The maximum 値 SP2MAX of the U-density spectrum SP2 is at most 10% of the average 値TA 2 of the first thickness 2. 2 8. The optical polymer film of claim 27, which includes the following formula Characteristics: MD3 ^ 0. 1 OxRA 1 > SP3max^ O.lOxRAl where MD3: the average error of the first block 値Re in the plane direction, the first block 値Re is measured in a selected direction, Φ RA 1 : The average 値 of the first block 値Re in the plane direction, SP3MAX: the maximum 频率 of the frequency spectrum SP3, which is obtained by the fast Fourier transform of the first block 値Re. 2 9. Apply for a patent The optical polymer film of item 28, wherein the frequency spectrum SP3 is in a range corresponding to a wavelength converted into a spatial frequency domain: the maximum 値 SP3MAX is at most 10% of the average 値 RA1 of the first thickness 。 30. , such as the optical polymer of claim 28 The film, which includes the characteristics of the following formula: 'MD4 S 0· 1 0xRA2, where MD4: the error average 値 of the second block 値Re measured perpendicular to the two selected directions, RA2: measured in two vertical directions The average value of the second block 値Re, I322042 The frequency spectrum SP4 is obtained by fast Fourier transform of the second block 値Re measured by two vertical selection directions, and the maximum 値SP4MAX of the frequency spectrum SP2 is the range corresponding to the wavelength converted into the spatial frequency domain. 10% of the average 値RA2 of the second block 测量 measured for two vertical selection directions. 31. The optical polymer film of claim 30, which comprises the property of: MD5^0.1 0xRA3 > SP5max = 0.10xRA3 wherein MD 5: the average error of the third block 値Rth in the direction of the thick face The third block 値Rth is measured in a selected direction, RA3: the average of the third block 値Rth, SP5MAX: the maximum 频率 of the frequency spectrum SP3, which is the fast Fourier of the third block 値Rth Converted. 32. The optical polymer film of claim 31, wherein the maximum 値SP 5 MAX of the frequency spectrum SP5 is the third block of the thickness direction in a range corresponding to a wavelength converted into a spatial frequency domain. The average of Rth is 10% of RA3. 33. The optical polymer film according to claim 31, which comprises the characteristic z MD6 ^ 0.1 0xRA4 satisfying the following formula, wherein MD6: the third block 値Rth measured by two vertical selection directions is 1322042_______ /邛, 换 1 ' , , kiss 》 You -- error average 値, RA4 : the fourth block 値 Rth average 値 where the frequency spectrum SP6 is obtained by the fast Fourier transform of the fourth block 値 Rth, And in the range corresponding to the wavelength converted into the spatial frequency domain, the maximum 値SP6MAX of the frequency spectrum SP6 is at most 10% of the average 値RA4 of the fourth block 値Rth. 3. The optical polymer film according to claim 33, wherein the surface resistance is 10 χ 1 〇 1 (1 Ω to 1 χ 1013 Ω) at a relative humidity of 10%, and the difference between the surface resistance and the selected two is at most The average of the surface resistances of the two places is 20%. 1322042 Generation but in January - 玥曰 repair (嵬) coveted for sale XI, Figure 1 - two Li I狨 1322042 ____ • Year (Month 4th repair (more) is replacing page 1322042 Figure 3 35b 1322042 v IJ /' ' ' Γ _ - - Ί*·-·ΐΓΤ--π r .-.-n J.r-L --iw-i*-- -h years! Month repair leather)··.. 82 31 51 1322042 Air f 1322042 代年丨月4曰修(ί. +Ί换I 1322042 '??年丨月呐日修ν史vniw第10图 93a 91 1322042 Seto Shot: if Figure 11 105a 10 Temperature controller 56 12 105a PS ) 101 1322042 , rf year (month #修第12图 41 Figure 13 -10-