TW200821642A - Retardation film - Google Patents

Abstract

Disclosed is a retardation film for use in a liquid crystal display device, particularly a retardation film which enables to improve the unevenness in a corner part of a big-screen VA-type liquid crystal panel. In the retardation film, the elastic modulus (E23) as measured in the film-stretching direction under the conditions of a temperature of 23 DEG C and a humidity of 55% RH is 3.4 to 4.4 Gpa, and the difference (E23-50) between the elastic modulus (E50) as measured in the film- stretching direction under the conditions of a temperature of 50 DEG C and a humidity of 55% RH and the above-mentioned elastic modulus (E23) satisfies the requierment shown by the formula (1). When the amount of an additive present on a surface of the retardation film to be bounded to a polarizer is defined as 100 by mass, the amount of the additive present on a surface of the retardation film to be adhered to a glass surface is 20 to 70 by mass. Formula (1): 0.30 ≤ E23-50 ≤ 0.80 [wherein, E23-50 = E23 - E50.]

Description

200821642 IX. INSTRUCTIONS OF THE INVENTION [Technical Field] The present invention relates to a phase difference film used in various display devices such as a liquid crystal display device (LCD) or an organic EL (electroluminescence) display, and more particularly to such display devices. The protective film for a polarizing plate and the retardation film having a birefringence used as a retardation film. [Prior Art] A basic configuration of a liquid crystal display device is a polarizer plate provided on both sides of a liquid crystal cell. The polarizing plate only passes the light of the deflecting surface in a certain direction, so in the liquid crystal display device, it is an important task to visualize the change of the liquid crystal alignment caused by the electric field, and the performance of the polarizing plate can greatly influence the liquid crystal display device. performance. In recent years, the demand for display quality of a liquid crystal display device with respect to a film has been improved, and there have been proposals for various liquid crystal display modes such as VA (vertical alignment mode), 〇CB, and IPS. In order to increase the viewing angle of the liquid crystal display device, a film for retardation correction is used in general. Further, the quality required for the retardation film is increasingly severe due to the large screen and high definition, and the uniformity of the broad side direction and the long side direction of the film phase difference is also required. A polarizing plate used in a liquid crystal panel of a VA type mode is a method in which a liquid crystal cell is attached to a liquid crystal cell to have a polarization axis in the longitudinal and lateral directions of the screen. The polarizing element 'in the elements of the polarizing plate used herein can be manufactured by substantially extending the PVA film, and the cellulose ester film or the paste for protecting the polarizing element is obtained as a result of shrinkage by temperature or humidity. Phase -4- 200821642 The film is subjected to shrinkage stress to decolorize the four corners when the screen is black-displayed, and there is a problem that the "substrate angle unevenness" becomes a problem. There are various proposals for the elastic ratio of the retardation film used in the liquid crystal display device, and the second patent document. Patent Document 1 discloses a non-cellulose ester film 'optical compensation sheet (phase difference plate) and an elliptically polarizing plate, and has a tensile modulus in the mechanical direction of the cellulose ester film, and a vertical direction in the mechanical direction. The modulus of elasticity and the ratio of the tensile modulus of elasticity in the machine direction to the tensile modulus of elasticity in the machine direction are adjusted, and the retardation (Rth) and the surface of the cellulose ester film in the thickness direction can be adjusted. The relationship between internal resistance and Re (Re). Patent Document 1: Japanese Laid-Open Patent Publication No. 2001-1 00039. SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION However, in the technique described in Patent Document 1, the "planar corner" is improved in the large-screen VA liquid crystal panel. There will be insufficient problems on the issue of unevenness. SUMMARY OF THE INVENTION An object of the present invention is to provide a phase difference film which can improve the unevenness of a substrate corner in a large-screen VA type liquid crystal panel, which solves the above-mentioned problems of the prior art. Means for Solving the Problem. The inventors of the present invention have repeatedly tried to solve the above-mentioned problems of the prior art, and have repeatedly found that the edge of the substrate is uneven in the large-screen VA type liquid crystal panel. In the improvement, it is preferable that the shrinkage force of the polarizing element is such that the protective film or the retardation film itself is deformed. In particular, it was first discovered that by the illumination of the panel backlight, the temperature of the retardation film can reach nearly 50 ° C, and the elastic modulus of the protective film or the retardation film monomer in this state is at 23 ° C. When the elastic modulus is as low as 0.3 to 0.8 GPa, the effect is remarkable, and thus the present invention has been completed. On the other hand, in the 23 t: normal temperature region, the low modulus of elasticity of the protective film or the retardation film monomer, especially in the polarizing plate for large-screen liquid crystal panels, cannot withstand the shrinkage of the polarizing element. Therefore, the protective film or the retardation film is liable to be deformed, so that the reduction in frontal contrast becomes a problem. The inventors of the present invention measured the modulus of elasticity (E23) at a temperature of 23 ° C and a humidity of 55% RH of 3.4 to 4.4 GPa, and a temperature of 50 ° C and a humidity of 5 5% in the measurement conditions and the modulus of elasticity ( The difference (E3·5()) of E5()) is a retardation film characterized by 0.30 to 0.80 GPa, and thus the present invention has been completed. Further, in the retardation film of the present invention, the amount of plasticity of the surface in contact with the polarizing element is smaller than that of the surface contacting the glass side, and the occurrence of unevenness of the substrate corners can be greatly suppressed. Although it is presumed that the surface of the retardation film on the side of the polarizing element is made to have a high plasticity amount, the bonding force between the retardation film and the PVA (polarizing element) can be improved. On the other hand, the glass side of the retardation film is considered to be the same. Since the surface has a small amount of plasticity, the stress caused by the contraction of PVA due to temperature change is transmitted to the phase difference film, so the force is relatively weak, so the disorder of the re-folding 200821642 is difficult to be caused. In order to achieve the above object, the invention of claim 1 is a retardation film which is provided in one part of the film forming step and which holds the end of the film and stretches in a direction orthogonal to the conveying direction. The retardation film produced in the manufacturing step of the method is characterized in that the elastic modulus (E23) of the film stretching direction measured under the measurement conditions of a temperature of 23 ° C and a humidity of 5 5 % RH is 3.4 to 4.4 GPa. And the difference between the elastic modulus (E5Q) and the elastic modulus (E23) in the tensile direction of the film measured in the measurement conditions of a temperature of 50 ° C and a humidity of 55% RH (ΔEn-so) can satisfy the following formula (1) And the amount of the additive present on the surface of the retardation film on the side of the polarizing element is 100% by mass, and the amount of the additive existing on the surface of the retardation film on the side of the glass surface is 20 to 70 by mass. . Formula (1) 0·30^ΛΕ23·50$0·80 However, ^^£23-50 =^23-^500 The invention of claim 2, such as the phase difference film of claim 1 of the patent scope, The film thickness of the film is '35~60 μηι. The invention system of the third application patent scope, such as the scope of patent application! The phase difference film of item 2 or 2, wherein the resin has an intrinsic viscosity (IV) of 1.3 to 1.7. The invention of claim 4, wherein the main component of the resin is a cellulose ester, and the cellulose ester contains a fiber selected from the group consisting of the fiber according to any one of the preceding claims. Acetate Ethyl ester: Fibrinogen-7-200821642 Acetate propionate, cellulose acetate butyrate in at least one of the group. The invention of claim 5 is the phase difference film of claim 4, wherein the cellulose ester has an ester group substitution of 2.42 to 2.60. Advantageous Effects of Invention The invention of the phase difference film of the first aspect of the invention is a manufacturing step of a means for holding the end portion of the film and stretching it in a direction orthogonal to the conveying direction, in one part of the film forming step. The retardation film produced by the method is characterized in that the elastic modulus (E23) of the film stretching direction measured under the measurement conditions of a temperature of 23 ° C and a humidity of 55% RH is 3.4 to 4.4 GPa, and the temperature is 5 〇 ° C. 'The difference between the elastic modulus (E5C) of the film stretching direction measured by the humidity of 55% RH and the above elastic modulus (E23) (E23-5G) can satisfy the following formula (1), and the polarizing element The amount of the additive present on the surface of the retardation film on the joint side is 20 to 70 in a mass ratio of the amount of the additive present on the surface of the retardation film to the surface of the glass surface at a mass ratio of 100 Å. Formula (1)0·30$ΔΕ 2 3·5〇^〇.80 However, ^£23-50=^23450° The measurement condition of the retardation film according to the present invention at a temperature of 23 ° C and a humidity of 55% RH The difference between the elastic modulus (E23) of the film in the tensile direction measured and the elastic modulus (E5G) of the film stretched by the measurement of the temperature of 5 〇t, the humidity of 55% RH (E23-5() The above formula (1) can be satisfied, that is, for example, by backlighting of a large-screen VA type liquid crystal panel, the phase difference film temperature can reach nearly 5 (TC until the phase difference film monomer in this state) When the elastic modulus (EM) is compared with the elastic modulus (Ευ) at a temperature of 23T: in the range of as low as 0.3 to 0.8 GPa, the protective film or the retardation film itself may be deformed in response to the contraction force of the polarizing element. In the large-screen VA type liquid crystal panel, the effect of improving the unevenness of the substrate corners is remarkable. In particular, according to the retardation film of the present invention, the contraction force of the polarizing element generated according to the environmental fluctuation does not deteriorate the retardation film. , which prevents the dimensional change of the polarizing film itself, and prevents the so-called polarizing film Curing, and the effect of the production of the liquid crystal panel can be achieved. The invention of the first aspect of the invention is in the phase difference film, the plasticized dose of the contact surface with the polarizing element is compared. The amount of plasticity of the surface contacting the glass side is smaller, and the effect of greatly suppressing the occurrence of unevenness of the corners of the substrate can be achieved. This is the case where the surface of the retardation film on the side of the polarizing element has a large plasticized dose, so that the retardation film and the PVA ( The bonding force of the polarizing element is improved. On the other hand, it is considered that the surface of the phase difference film glass side has a small amount of plasticity, and the stress generated by the contraction of the PVA due to the temperature change is transmitted to the phase difference film due to the force thereof. The invention is relatively weak, so that the disorder of the birefringence is difficult to be caused. The invention of claim 2 is the film of the film of the first aspect of the invention, wherein the thickness of the film contained in the film is 3 5~: -9- 200821642 6〇μηι 'In accordance with the present invention, a thin display in recent years, particularly a phase which can sufficiently satisfy the use of a thin display such as a large-sized TV The remarkable effect of the desired filming of the poor film. The invention of claim 3 is the inherent viscosity (IV) of the resin contained in the film of the phase difference film described in the first or second aspect of the patent application. According to the present invention, in the manufacturing stage of the retardation film, the film can be prevented from being broken, and at the same time, the effect of avoiding the risk of cracking in the film stretching step can be obtained. In the retardation film according to any one of the items 1 to 3, the main component of the resin contained in the film is a cellulose ester, and the cellulose ester is selected from cellulose acetate or fiber. According to the present invention, at least one of a cellulose acetate propionate and a cellulose acetate butyrate can be used as a resin constituting a film, and the above cellulose ester can be used to maintain not only the transparency of the film but also In the large-screen VA type liquid crystal panel, the effect of improving the retardation film of the substrate edge unevenness can be obtained. The invention of claim 5 is the phase difference film according to item 4 of the patent application, wherein the degree of substitution of the cellulose ester is 2.42 to 2.60, and according to the present invention, the degree of substitution with an ester group is used. The cellulose ester specified above can obtain the effect of a retardation film having good adhesion to the polarizing film while maintaining the transparency of the film. BEST MODE FOR CARRYING OUT THE INVENTION Next, an embodiment of the present invention will be described, but the present invention is not limited to -10. 200821642. The retardation film of the present invention has an elastic modulus (E23) of 3.4 to 4.4 GPa in the tensile direction of the film measured under the conditions of a temperature of 23 ° C and a humidity of 55% RH, and is at a temperature of 5 (TC, humidity 55). The difference between the elastic modulus (Ε5ϋ) in the tensile direction of the film and the elastic modulus (E23) measured under the measurement conditions of % RH (Ε23·50) can satisfy the following formula (1). 30$Ε23-5〇$〇·80 But 'E23-5G = E23-E5〇. In the present invention, the improvement of the unevenness of the substrate corners in the large-screen VA type liquid crystal panel' can be protected by the contraction force of the polarizing element. The deformation of the film or retardation film itself is important, especially, for example, a large-screen VA-type liquid crystal panel. The backlight is lit so that the temperature of the retardation film can reach nearly 50. In the state of the phase difference film monomer The elastic modulus (E50) is more effective than the elastic modulus (E23) at a temperature of 23 t, and is effective in the range of as low as 0.3 to 0.8 GPa. According to the present invention, the substrate can be improved in a large-screen VA liquid crystal panel. The corners are not uniform. Hereinafter, the above will be described in detail. The retardation film of the present invention can be exemplified to be manufactured. The film is excellent in adhesion to a polarizing film, optical transparency, etc., and a polymer film is preferred. The transparent means in the present invention means that the transmittance of visible light is 60% or more, preferably 80. % or more, particularly preferably 90% or more. • 11 - 200821642 The polymer film is not particularly limited as long as it has the above properties, and examples thereof include a cellulose diacetate film and a cellulose triacetate film. Cellulose acetate butyrate film, cellulose acetate film such as cellulose acetate propionate film, polyester film, polycarbonate film, polyarylate film, polyfluorene (also contains poly Ether") film, polyester film of polyethylene terephthalate, polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, polyvinyl chloride film, polyvinyl alcohol film, B. Ethyl alcohol film, syndiotactic polystyrene film, polycarbonate film, cycloolefin polymer film (Arton (JSR)), ZEONEX®, ZEONOR® (above, Japan Ze ο η company), polymethylpentene film, Polyetherketone film, polyether ketone imide film, polyamide thin: film, fluororesin film, nylon film, polymethyl methacrylate film, acrylic film or glass plate, etc. A film, a cycloolefin polymer film, a polycarbonate film, and a poly(polyether fluorene) film are preferred. In the present invention, a cellulose ester film, a cycloolefin polymer film 'polycarbonate system, particularly The film can be suitably used in terms of production, cost, transparency, adhesion, etc. The film can be a film produced by melt casting or a solution flow. A film made by casting a film. In addition, the retardation film of the present invention is described in Japanese Laid-Open Patent Publication No. 2000-1903, No. 2004-4474, and JP-A-2005-119. As the polymer layer, a polymer _ film of an optically anisotropic layer such as polyamine or polyimine is preferably used as the polymer layer. -12- 200821642 [Cellulose Ester Film] The cellulose ester of the present invention as a main component of the retardation film is preferably cellulose acetate, cellulose propionate, cellulose butyrate or cellulose acetate. The ester butyrate, cellulose acetate propionate is preferred, and cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate are preferred. In particular, the main component contained in the resin contained in the film is a cellulose ester containing a cellulose acetate, cellulose acetate propionate, cellulose acetate, and acid. At least one of the esters is preferred. As described above, in the present invention, by using the above-mentioned cellulose ester as the resin constituting the film, not only the transparency of the film can be maintained, but also the unevenness of the substrate corner can be improved in the large-screen V A type liquid crystal panel. Here, the degree of substitution of the ester of the cellulose ester is preferably 2.4 2 to 2.60. The degree of substitution of the ester group is such that the desired cellulose ester is used, and not only the transparency of the film but also the phase difference film having good adhesion to the polarizing film can be obtained. These cellulose esters can be synthesized by a known method. In the present invention, the intrinsic viscosity (IV) of the resin contained in the film is preferably 1.3 to 1.7. According to the present invention, in the manufacturing stage of the retardation film, not only the hanging of the film but also the avoidance of the film can be avoided. The risk of cracking in the film stretching step. Here, the measurement of the intrinsic viscosity (1 V) of the resin contained in the film can be carried out using a Ubbelohde type viscometer. Specifically, the solvent is prepared by dissolving the cellulose ester resin in a solvent using tetrahydrofuran' to prepare a sample concentration of 22 -13 - 200821642 g / d 1,0.6 g / d 1,1 · 0 g / d 1 Solution (temperature 20 ° C). The specific viscosity (hsp) is obtained in the respective concentrations (C) by Ubbelohde type viscometer, and the intrinsic viscosity is given by the formula [1].

C—0 C is extrapolated at a concentration of zero to determine the intrinsic viscosity [η]. In the case of the phase difference film of the present invention, in the case of using a cellulose ester, the cellulose of the raw material of the cellulose ester is not particularly limited, and may be exemplified by a cotton aphid 'wood paper (from a coniferous tree, derived from a broad-leaved tree). , kenaf (kenaf) and so on. Further, the cellulose esters obtained from these can be used in combination at any ratio. In the case of the cellulose ester, when the thiolating agent is an acid anhydride (acetic anhydride, propionic anhydride 'butyric anhydride), an organic solvent such as an organic acid or dichloromethane is used as in the case of acetic acid, and a proton-like catalyst such as sulfuric acid is used. The cellulose raw material is obtained by reaction. In the case where the thiolating agent is cerium chloride (CH3C0C1, C2H5C0C1, C3H7C0C1), the catalyst is reacted using an amine-like basic compound. Specifically, it can be synthesized by referring to the method described in Japanese Patent Laid-Open No. Hei 10-45804. Further, the cellulose ester used in the present invention can be reacted with the above-mentioned thiolation amount in accordance with the degree of substitution, and the cellulose ester-based thiolating agent reacts with the hydroxyl group of the cellulose molecule. The cellulose molecule glucose unit is composed of a plurality of linkages, and has three hydroxyl groups in the glucose unit. Here, the number of the three hydroxyl groups derived from the thiol group is referred to as the degree of substitution (% by mole). Example -14- 200821642 For example, all three cellulose groups of the cellulose triacetate-based glucose unit are bonded to an acetyl group (actually 2.6 to 3.0). The cellulose ester used in the present invention is as described above, other than cellulose acetate propionate, cellulose acetate butyrate, or cellulose acetate propionate butyrate. It is particularly preferred to use a mixed fatty acid ester of cellulose having a propionate group or a butyrate group. Further, the cellulose acetate propionate containing a propionate group as a substituent is excellent in water resistance, and a film for a liquid crystal display device is useful. The method for determining the degree of substitution of the thiol group can be determined in accordance with the provisions of ASTM-D817-96. The number average molecular weight of the cellulose ester is from 40,000 to 200,000, and the mechanical strength in the case of molding is strong, and the moderate doping viscosity is preferably in the case of the solution casting method, and further preferably from 50,000 to 150,000. Further, the mass average molecular weight (Mw) / number average molecular weight (?η) is preferably in the range of from 1. 4 to 4·5. Here, since the average molecular weight of the cellulose ester is measured by gel permeation chromatography, the number average molecular weight (??) and the mass average molecular weight (Mw) can be calculated using this. The mass average molecular weight (Mw) and number average molecular weight (?n) of the cellulose ester were determined by gel permeation chromatography using the apparatus and materials shown below. The measurement conditions of the average molecular weight are as follows. Gel permeation chromatography solvent (dissolved solution): dichloromethane-15- 200821642 Column name: GPCk806-GPCk805-GPCk803 (3 pieces) manufactured by Showa Denko Co., Ltd. Sample concentration: 〇·! (% by mass) Flow rate: 1 · 0 ( Ιη1/min) Sample injection amount: 100 (μ1) Standard sample: Polystyrene (Mw: 5 million to 6.7 million)

Temperature: 2 5 °C Detection: RI (Enlightenance Refractometer) These cellulose esters are generally referred to as solution-casting film-forming cellulose ester solutions (doping), for example, in the endless transfer It is preferable that the metal strip or the metal drum of the rotating metal drum is formed by a method of forming a film by doping casting (casting) from a pressurizing mold. The organic solvent used for the preparation of the doping dissolves the cellulose ester, and is preferably a moderate boiling point, and examples thereof include dichloromethane, methyl acetate, ethyl acetate, amyl acetate, and ethyl acetate. Methyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2, 3,3-tetrafluoro-1-propanol, 1,3-difluoro-2.propanol, 15151,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1 ,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-p-propanol, nitroethane, 1,3-dimethyl-2-imidazolidinone (imidazolidinone), etc., may be an organic halogen compound such as dichloromethane, a dioxolane derivative, methyl acetate, ethyl acetate, acetone, methyl acetate or the like, preferably an organic solvent (ie, , good solvent). Further, as shown in the film forming step described below, in the solvent evaporation step, when the solvent is dried by the network (doped film) formed on the support for casting, it is -16-

200821642 From the viewpoint of preventing foaming in the web, the point used is preferably 30 to 80 ° C. For example, the above-mentioned dot can be dichloromethane (boiling point 4 0.4 ° C), 2 5 6 · 3 2 ° C), acetone (boiling point 5 6 · 3 ° C), ethyl acetate and the like. Among the above-described good solvents, it is preferred to use an excellent solubility or methyl acetate. In addition to the above organic solvent, it is preferred to contain an alcohol having 1 to 4 carbon atoms in an amount of 1% by weight. It is especially good for the above alcohols. These processes are carried out after the doping described above, and the solvent is evaporated. When the ratio of the alcohol is increased, the mesh is gelled to make the mesh firm, and it can be used as a gelling solvent which is easy to carry out for casting, or These ratios act to dissolve the cellulose ester of the chlorine-based organic solvent. Examples of the alcohol having 1 to 4 carbon atoms include methanol, isopropanol, n-butanol, secondary butanol, and tertiary hydride. The doping stability is good, and the boiling dryness is also good. Ethanol is preferred. Preferably, the phase mass % to 95% by mass is preferably 5% by mass of the ethanol-containing agent. It is also possible to use methyl acetate instead of dichloromethyl to modulate the doping by a cooling dissolution method. In the case of the plasticizer used in the present invention, an agent, a non-phosphate ester plasticizer is preferred. The phosphate ester-based plasticizer may, for example, be a boiling solvent of a good solvent of a triphenyl organic solvent: methyl ester (boiling point u boiling point 7 6 · 8 2 °c) different from dichloromethane, mass %~4 0 mass to 30% by mass of the cast support I-like material (doped film) is used to promote non-alcohol, ethanol, n-propanol, etc. when the support is peeled off. The point is also relatively low, since it is used for methylene chloride 70, ～30% by mass of lysine. At this time, it is plasticized with phosphate ester; phosphate, cresol • 17, 200821642 Phosphorous phenylenediyl chlorohydrin hydrochloride, p-phenylenediphenyl hydroxyphosphate, phosphorus phosphatidylphosphonate, phosphorus phenyl benzene, benzene, etc. Phosphate-based three plastics can be used as bismuth citrate to make it as a savory formula, can be acid, acid ester, non-methylenetetrazide, plastic, ester, acid, trimethylbenzene, sulphuric acid, plastic, acid, ester, acid, hydroxy 3/ plastic can be an acid acid price multi-agent plastic can be a plastic agent, πυ Qi plastic can be ester carboxylic acid V3 / valence multi-agent plastic can be a polyester agent can be acid fat, especially In order to obtain the effect of the present invention, it is preferred to use a polyvalent alcohol-based plasticizer, a polyester-based plasticizer, and a polyvalent carboxylic acid-based plasticizer. The polyvalent alcohol ester is composed of an ester of a divalent or higher aliphatic polyvalent alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule. The polyvalent alcohol used in the present invention is represented by the following formula (1). General formula (1) Ri-(〇H)n (however, 1 represents an η-valent organic group, and η represents a positive integer of 2 or more). As an example of a suitable polyvalent alcohol, for example, the following items can be exemplified, but the present invention is not limited thereto. Adenitol can be exemplified as 'arabitol, ethyl alcohol'-ethyl alcohol 'diethyl alcohol' tetraethylene alcohol, 1,2-propanediol, 1,3·propanediol, dipropylene glycol . 'Tripropylene glycol, 1,2-butyl alcohol,〗 3-butyl alcohol, l4. Ding diol 'dibutanol, 1,2,4 - Dingyuan triol' 1,5 · Pentylene glycol '1,6-hexadiol, hexatriol, galactitol 4&13(^丨1〇1), mannitol (1^111111〇1)'3-methylpentane -1,3,5·triol, tetramethyl glycol (Pinaco1), sorbitol 'trimethylolpropane, trimethylolethane, xylitol (xyntol), neopenta-4- 200821642 Alcohol, dipentaerythritol and the like. Among them, trimethylolpropane and neopentyltetramine are preferred. The monocarboxylic acid used in the polyvalent alcohol ester of the present invention is not particularly limited, and a known aliphatic monocarboxylic acid 'alicyclic monocarboxylic acid, aryl monocarboxylic acid or the like can be used. When an alicyclic monocarboxylic acid or an aromatic monocarboxylic acid is used, the moisture permeability is improved, and the retention is preferred. The following examples of the appropriate monocarboxylic acid are exemplified, but the present invention is not limited thereto. In the case of an aliphatic monocarboxylic acid, a linear or fatty acid having a carbon number of 1 to 32 can be suitably used. It is better to use a carbon number of 1 to 20, and it is particularly preferable to use 1 to 1 0. When acetic acid is used, the compatibility with the cellulose ester is preferably added, and acetic acid may be used in combination with other monocarboxylic acids. As the appropriate aliphatic monocarboxylic acid, acetic acid 'propionic acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, caprylic acid '2-ethyl-carboxylic acid, undecanoic acid, lauric acid, ten Triacid, myristic acid, pentadecanoic acid, heptadecanoic acid, stearic acid, nonadecanic acid, tauric acid 'tico acid, tetracosic acid, twenty-six acid, twenty-seven acid, two Saturated fatty acids such as octadecanoic acid, tridecanoic acid, tridecanoic acid, eleven carbonic acid, oleic acid, linoleic acid, linolenic acid, peanut-impregnated acid, etc. As an example of a suitable alicyclic monocarboxylic acid, a cyclopentane carboxylic acid, a cyclooctane carboxylic acid, or a derivative of the derivative When a benzene toluene ring such as benzoic acid or tolylmethyl amide is introduced into the alkyl group, the phenyl ring of the biphenyl carboxylic acid, the naphthalene carboxylic acid 'tetra M 彳匕 彳匕, etc. has two or more aromatic monocarboxylic acids' or It is better to use benzoic acid, especially benzoic acid. Alcohol is not limited to the fragrance of the family, the side chain carbon enthalpy can be increased, butane, brown, the second carbon, the fatty acid, the carboxylic acid of the aromatic acid. -19- 200821642 The molecular weight of the polyvalent alcohol ester is preferably in the range of 3 00 to 1 5 00, and is suitably in the range of 305 to 750. It is preferable that the molecular weight is large because it is difficult to volatilize. The preference for compatibility with moisture permeability and cellulose ester is preferably small. The carboxylic acid to be used for the polyvalent alcohol ester may be one type or a mixture of two or more types. Further, the OH group in the polyvalent alcohol may be all esterified, and a part may be left as an OH group. Specific compounds of the polyvalent alcohol ester are shown below. The content of the polyvalent alcohol ester of the present invention is preferably from 1 to 15% by mass, particularly preferably from 3 to 10% by mass, based on the cellulose ester film. •20-200821642 [Chemical 1 C4H9-C-〇-(CH2>2-〇-{CH2>2—〇-(CH2)2—oc-c4h9 one (ch2>2-o-,2> “o—“ Ch2)2-〇i-^^) 0~(CH2)2-0-(CH2)2~0~(CH2)2~0-C^ \ο ο χ==/ )γ^-〇4 〇τ Ο 4 ο of ch2-ch2—ο 6 c8h17-c~0-|ck2-ch2~0^c-c8h17 _ ο ο __ 7 (3~” and 2,2 - 0 ο as H2CH2CH2 a 0 ch2ch2ch2 - 〇 c - c4h9 o 10 C8H17— lean-〇-^CH2CH2CH2_〇^^-C8H17 _ 0 0 110~r〇如如~~ 0 0 ~ 12 〇-r0 as - O)r^-〇〇ch3 o 13 C4Hs~ C_0 such as HAH - 0^-g-C4H9 〇ch3 ° 14 C8Ht7-co-^ch2ch-o^-c — c8h1715〇°r ο C4H9 - - ο ten ch2ch2ch2- ο CH;十CH2CH—o ch3 -21 - 200821642 [Chemical 2] 16 ?H2 a 17 o ch2—〇一c-c4h9 ch3ch2_c-ch2-o 1-0 ch2.〇.c^0 ο ch3ch2—c-ch2—o- Good one c4h9I 0 ch2-oc-c4h〇II 0 18

ο II CH2-〇-C-C8Hn 19 ch2 one. Ch3ch2—c-ch2-o - c-c8h17 I 〇ch2-oc-c8h17 II ο ch3ch2_c-ch2· X〇! 20 21 CH2 an oc ch2-〇TcH3 o ch2-oc CH3CH2—9~CH2—oc-ch3 ο CH2 一〇_C-CH3 II ο 22 ?/-\ ch2-o~c-( > -〇i~0 ch3ch2-c-ch2-oc o 23 ch3ch2*-c-ch2-oc o

rO ch2-o-c-ch3 I! o ch2 I ch3ch2-c-ch2 ch2-oh

-22- 200821642

-23- 200821642

CH3-CH2-C-CH2-〇-C-^^/CH3-CH2-C-CH2-〇-|-^yox=/ 33 ^y~t〇>(cH2-CH2-CH2-〇^-. ―

〇 O 34

Cy^〇4cH2,-

O CH3 O

9 CUO (Polyester-based plasticizer) The polyester-based plasticizer is not particularly limited as long as it has no particular ring or a cycloalkyl ring. For example, a terminal terminal ester-based plasticizer is preferred. It is preferred to use an aromatic agent in the molecule. Appropriate polyester plasticizer to describe the aroma of general formula (2) 200821642

General formula (2) B-(GA)nGB (wherein B represents a benzene monocarboxylic acid residue, G represents an aryl diol residue having a carbon number of 2 to 12 or a carbon number of 6 to 12 or a carbon number of 4~ 1 diol residue, A represents an aryl dicarboxylic acid residue of a 12-to-1 2 alkylene dicarboxylic acid residue 12, and further: η shows a benzene monocarboxylic acid represented by 1 or more The residue may be reacted with an alkylene olefin diol residue or an aryl diol residue represented by G, or a aryl dicarboxylic acid residue represented by hydrazine, and may be reacted in the same manner as a normal agent. The benzene monocarboxylic acid of the polyester-based plasticizer used in the present invention is, for example, benzoic acid, p-tert-butylbenzoic acid, o-toluene toluene-methyl carboxylic acid, p-toluamyl carboxylic acid, dimethylbenzoic acid, Examples of the propyl benzoic acid, the amino benzoic acid, and the acetoxy group may be one or a mixture of two or more. The carbon number of the polyester plasticizer used in the present invention is 2, and the exemplified is B. Glycol '丨,2·propylene glycol, 1,2·butanediol, 1,3-butanediol, 1,2-propanediol propanediol, 1,4-butanediol, pentane II Alcohol, 2 propane diol (neopentyl glycol), 2,2-diethyl- 1,3-propoxymethylpentane), 2-n-butyl-2-ethyl-1,3 propanediylheptane, 3-methyl-1,5-pentanediol 1,6 - Hexanedifyl 1,3-pentanediol, 2-ethyl U3-hexanediol, 2-diol, 1,9-nonanediol, 1,1 〇-癸 diol, 1, 1 2 - an alkylene oxide residue having an alkylene group or a carbon number of 6 to 〇. The general formula (2) diol residue or oxyalkylene dicarboxylic acid residual polyester-based plastic acid component v, formazanic acid, m-formic acid, ethyl benzoic acid, etc., are used. ~1 2 alkylene di1,3-propanediol, 2-methyl 1,3 -,2-monomethyl-1,3-alkanediol (3,3·diol (3,3-dihydroxyl) Formazan, 2,2,4-trimethyl-methyl 1,8-octane, octadiol, etc., -25- 200821642 These diols may be used alone or in combination of two or more. In particular, carbon number 2 The alkylene glycol of ～12 is particularly suitable for compatibility with a cellulose ester, and is particularly suitable for the alkylene glycol component having a carbon number of 4 to 12 in the aromatic terminal ester used in the present invention. For example, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, etc., may be used as a mixture or a mixture of two or more. The aromatic terminal ester used in the present invention. Examples of the alkylene dicarboxylic acid component having 4 to 12 carbon atoms include, for example, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, sebacic acid, sebacic acid, and twelve An alkanedicarboxylic acid or the like, each of which may be used alone or in combination of two or more. The aryldicarboxylic acid component having a carbon number of 6 to 12 is phthalic acid, terephthalic acid, isophthalic acid. , 1,5 naphthalene dicarboxylic acid, 1 4. Naphthalene dicarboxylic acid, etc. The polyester-based plasticizer used in the present invention preferably has a number average molecular weight of _300 to 1,500, more preferably 400 to 1,000. Further, the acid value is 0.5 mgKOH/g or less. The hydroxyl value is 25 mgKOH/g or less, more preferably the acid value is mg3 mgKOH/g or less, and the hydroxyl value is 15 mgKOH/g or less. Hereinafter, the present invention represents an appropriate aromatic terminal ester-based plasticizer. Synthetic example. <Sample Νο·1 (aromatic terminal ester sample)> In a reaction vessel, 4 10 parts of citric acid, 6 〇 of benzoic acid, 7 3 parts of dipropylene glycol, and a catalyst were charged. 4 isopropyl titanate vinegar 0 · 4 〇-26 - 200821642 parts under a nitrogen stream with stirring, a reflux condenser is added to reflux excess monovalent alcohol, while the acid value is 2 or less, at 1 3 〇~2 5 0 °C, continuous heating, the generated water is continuously removed, and then the distillate is removed at a reduced pressure of 2 0 0 to 2 30 ° C 1 0 0 to finally 4 x 1 02 Pa or less, and thereafter Filtration to obtain an aromatic terminal ester plasticizer having the following properties: Viscosity (25 ° C, mPa · s); 43400 Acid value; 2 <Sample No. 2 (aromatic terminal ester sample)> In addition to use in the reaction vessel, 4 10 parts of citric acid, 610 parts of benzoic acid, 341 parts of ethylene glycol, and tetraisopropyl acrylate The other than 0.35 parts of the base titanate is exactly the same as the sample ο ο 1 to obtain the aromatic terminal ester with the second trait. Viscosity (25 ° C, mPa · s); 3 1000 acid value; 0.1 < sample No. 3 (aromatic terminal ester sample)> In addition to the use in the reaction vessel, 410 parts of citric acid, 610 parts of benzoic acid, 418 parts of 1,2-propanediol, and 0.35 parts of tetraisopropyl titanate of the catalyst The others were identical to the sample Ν 〇. 1 to obtain an aromatic terminal ester with a secondary trait. Viscosity (25 ° C, mPa * s); 3 8000 acid value; 0.0 5 -27- 200821642 <Sample No. 4 (aromatic terminal ester sample)> In addition to using 40 parts of citric acid in the reaction vessel, benzene The aromatic terminal ester having the next trait was obtained in the same manner as the sample No. 1 except that 610 parts of formic acid, 418 parts of 1,3-propanediol, and 0.35 parts of tetraisopropyl titanate of the catalyst were used. Viscosity (25 ° C, mPa · s); 37 00 0 acid value; 0 · 0 5 The following shows a specific compound of the aromatic terminal ester-based plasticizer used in the present invention, but the present invention is not limited thereto. ^—^louo£o£oo£o£oooul^l^l.ooot£o£oo£o£uooo £o£0 ^l^loooixo£ooool«^xowlouo»xo£oooo , ^loooi£o£o £oo£o£o£oooo\=r ^ y-*80L5x3£DO£u£ox88 - 08丨80"H3WH30NH3WHP003 £o£o 000ίχυ£ϋ1000! ! οοοχο£υοοο

Or b- xo I 0001 Ho£o— ooo I *{£0> 1000 \ 08 〇0〇£0|^1^- £οοοοι*50τουο£υ 1^1^1 ^—^loool£o£oo£ o£oooul^£OTOOO£ul^l^l£oooo £0000

9 τ- cni «〇 兮 in <〇 卜 〇〇 \ rj ν〇 -28- 200821642

I 10χ-ο — Ορο—xuwxololxo^xo £uχ-ο_ —OOY^HUTSOlH^s-oi^HUOS People》s&gt;” ^—^louo£o£uo£o£oo£o£uoout^ ^ ^—^有用 ο υ ^ ^ 有用 有用 有用 ^ 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用 有用Made of ester. Further, the aliphatic polyvalent carboxylic acid is preferably from 2 to 20, and in the case of an aromatic polyvalent carboxylic acid or an alicyclic polyvalent carboxylic acid, it is preferably from 3 to 20 valence. The polyvalent carboxylic acid used in the present invention is represented by the following general formula (3). General formula (3) R5(COOH)m(OH)n -29- 200821642 (wherein R5 represents an organic group of (m + n) valence, m represents an integer of 2 or more, and the COOH group represents a carboxyl group; , OH group is an alcoholic hydroxyl group). As an example of a suitable polyvalent carboxylic acid, for example, the present invention is exemplified, and the present invention is not limited thereto. Trimethic acid, trimesic acid, pyromellitic acid-like trivalent or higher aromatic carboxylic acid or its derivative, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid Diacids, tetrahydrofurfuric acid-like aliphatic carboxylic acids, tartaric acid, hydroxymalonic acid, malic acid, citric acid-like carboxylic acids and the like are preferred. Especially in the case of using a hydroxypolycarboxylic acid, the higher point is appropriate. The polyvalent carboxylic acid ester compound to be used in the invention is not particularly limited, and a well-known alcohol or phenol can be used. For example, an aliphatic saturated alcohol having a linear or side chain of 32 or an aliphatic unsaturated is preferably a carbon number of 1 to 20, and a carbon number of 1 to 1 is particularly preferred. An alicyclic alcohol such as an alcohol or a cyclohexanol or a derivative thereof, a benzyl alcohol, an aromatic alcohol or a derivative thereof, or the like is preferred. In the case of a polyvalent carboxylic acid, in the case of using a hydroxypolyvalent carboxylic acid, the following may be exemplified as an example in which an alcoholic or phenolic hydroxyl group of a polyvalent carboxylic acid is used as a suitable monocarboxylic acid, and the present invention is exemplified. herein. The aliphatic monocarboxylic acid is preferably a straight chain fatty acid having a carbon number of 1 to 32. It is further preferred that the carbon number is from 1 to 20, and the carbon number is Ξ integer, η or phenol is the same as the benzene tricarboxylic acid aromatic polyvalent diacid, and the grass aliphatic polyvalent hydroxyl group retains the alcohol and carbon. The number 1 ~ alcohol is preferred. Further, cyclopentanol or the like is esterified with a hydroxyl group. Not limited to or side chain 1~1 0 special -30- 200821642 Good. The suitable aliphatic monocarboxylic acid may, for example, be acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, n-decanoic acid, 2-ethyl-hexanecarboxylic acid, ^-- Acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nineteenth hospital acid, twenty acid, twenty-two acid, twenty-four acid, twenty Rare acid, octadecanoic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, peanut dicene, hexaic acid, twenty-seven acid, octadecanoic acid, tridecanoic acid An unsaturated fatty acid such as an acid. As an example of a suitable alicyclic monocarboxylic acid, a cyclopentanecarboxylic acid, a cyclohexanecarboxylic acid, a cyclooctanecarboxylic acid, or the like can be exemplified. Examples of a suitable aromatic monocarboxylic acid include a benzene ring of a benzoic acid such as benzoic acid or tolylmethyl carboxylic acid, which is introduced into an alkyl group, a biphenyl carboxylic acid, a naphthalene carboxylic acid, a tetrahydronaphthalene carboxylic acid or the like. An aromatic monocarboxylic acid having two or more benzene rings, or such derivatives. In particular, acetic acid, propionic acid, and benzoic acid are preferred. The molecular weight of the polyvalent carboxylic acid ester compound is not particularly limited, and is preferably in the range of molecular weight of 300 to 10 〇 ,, and further preferably in the range of 305 to 750. The point of improvement in retention is preferably larger, and it is preferably smaller in terms of compatibility with moisture permeability and cellulose ester. The polyvalent carboxylic acid ester used in the present invention may be used alone or in combination of two or more. The acid value of the polyvalent carboxylate compound used in the present invention is preferably 1 m g Κ Ο Η /g or less, and more preferably 0.2 mg KOH / g or less. Examples of particularly suitable polyvalent carboxylate compounds are as follows, but the present invention is not limited thereto. For example, triethyl citrate, tributyl citrate-31 - 200821642 citrate, ethyltriethyl citrate (ATEC), ethoxylated tributyl citrate (ATBC), benzoquinone III Butyl citrate, ethoxylated triphenyl citrate, acetyl benzyl tribenzyl citrate, dibutyl tartrate, dibutyl butyl tartrate, tributyl benzene tricarboxylate, homo benzene Tetrabutyl formate and the like. These plasticizers may be used alone or in combination of two or more. When the amount of the plasticizer is less than 1% by mass, the effect of reducing the Φ humidity of the film is not good, and when it exceeds 20% by mass, there is a plastic agent flow path from the film ( Bleed out), since the physical properties of the film are deteriorated, it is preferably 1 to 20% by mass. It is preferably 6 to 16% by mass, more preferably 8 to 13% by mass. 〇 In the retardation film of the present invention, it is preferred to use an ultraviolet absorber. In terms of the ultraviolet absorber, it is preferable that the absorption energy of ultraviolet light having a wavelength of 370 nm or less is excellent, and that the visible light absorption using a wavelength of 400 urn or more is preferable from the viewpoint of good liquid crystal display property. Specific examples of the ultraviolet absorber which is preferably a preferred embodiment of the present invention include a hydroxydiphenylketone compound, a benzotriazole compound, a water ester compound, a diphenyl ketone compound, and cyanide. An acrylate type compound, a nickel salt fault type compound, etc. are not limited to these. The benzotriazole-based ultraviolet absorber may be exemplified as a specific example of the ultraviolet absorber described below, but the present invention is not limited thereto. 1^-1: 2-(2, hydroxy-5,-methylphenyl)benzotriazole UV-2: 2-(2, hydroxy-3,5,2-di-tert-butylphenyl) Benzotriazole-32- 200821642 UV-3 : 2-(2,-hydroxy-3'-tertiary butyl-5,-methylphenyl)benzotriazole UV-4 : 2-(2'- Hydroxy·3',5'-di-tertiary butylphenyl)-5-chlorobenzotrienyl 1^-5:2-(2,-hydroxy-3, (3", 4", 5", 6"-tetrahydrophthalic acid imine methyl)-5,-methylphenyl)benzo-3-oxo UV-6: 2,2-methylenebis(4-(1,1,3) ,3·tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol) UV-7: 2-(2'-carbamic-3'-tertiary butyl-5'- Methylphenyl)-5-chlorobenzotriazole UV-8 ·· 2-(2H-benzotriazol-2-yl)-6-(linear and side chain dodecyl)-4-methyl Phenol (TINUVIN 171, manufactured by Ciba) UV-9: Octyl-3-[3-tert-butyl-4-hydroxy-5.(chloro-2H-benzotriazol-2-yl)phenyl]propionate Mixture with 2-ethylhexyl-3-[3-tert-butyl-4~hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate (TINUVIN1 09 , made by Ciba) In addition, the diphenyl ketone UV absorber can be used. Specific examples are shown below, but the present invention is not limited to such. UV-10: 2,4·dihydroxydiphenyl ketone UH1 : 2,2'-dihydroxy-4-methoxydiphenyl ketone UV-12: 2-hydroxy-4-methoxy-5-sulfonate Diphenyl ketone UV-13: bis(2-methoxy-4-hydroxy-5.phenylphenyl phenylmethane) is used in the use of the present invention as a preferred ultraviolet absorber, and the transparency is high to prevent the polarizing plate Or benzotriazole-based violet-33-200821642, which is excellent in the effect of liquid crystal deterioration, is preferably an external absorbent or a diphenylketone-based ultraviolet absorbent, and a benzotriazole-based ultraviolet absorbent having less coloring is not particularly required. good. Further, the ultraviolet absorber having a partition coefficient of 9.2 or more as described in JP-A No. 200 1 - 87825 is excellent in coatability while improving the surface quality of the elongated film. In particular, it is preferred to use a UV absorber above the partition coefficient of 1 〇. In addition, the general formula (1) ♦ or the general formula (2) described in Japanese Patent Laid-Open No. Hei 6- 1 843 0, and the general formula (3), (6), (7) of JP-A-2002-47357 are described. The ultraviolet absorbing polymer (or ultraviolet absorbing polymer) or the ultraviolet absorbing copolymer described in paragraphs [0027] to [0055] of JP-A-2002-69020 is preferred. The polymer ultraviolet absorber is commercially available as a PUVA-30M (manufactured by Otsuka Chemical Co., Ltd.). The retardation film of the present invention can use an antioxidant. When a liquid crystal display device or the like is placed in a state of high humidity and high temperature, there is a case where deterioration of the protective film of the polarizing plate occurs. The antioxidant can be delayed or prevented by the depolarizer of the polarizing plate protective film by, for example, protecting the amount of residual solvent in the film by a polarizing plate or a phosphoric acid of a phosphate-based plasticizer. The polarizing plate protective film is preferred. In the case of such an antioxidant, a hindered phenol-based compound may be preferably used, for example, 2,6-di-tris-butyl-p-cresol-neopentyl alcohol-four [3-(3,5-di) -Tris-butyl-4-hydroxyphenyl)propionate],.Triethylene glycol-bis[3 ·(3-tributyl)5-methyl-4-phenylphenyl)propionate ], 1,6-hexanediol-bis[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(n-octylsulfide) Generation)-6-(4-hydroxy-3,5-di-tertiary butylanilino)- -34- 200821642 1,3,5-triazine, 2,2·thio-divinyl bis[3- (3,5-di-tri-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate ,N,N'-hexylene bis(3,5-di-tertiary butyl-4-trans-hydrocinnamoguanamine)' 1,3,5-trimethyl-2,4,6-tri 3,5-di-tertiary butyl-4-hydroxybenzyl)benzene, three-(3,5-di-tri-butyl-4-hydroxybenzyl)-isocyanurate or the like. In particular, 2,6-di-tertiary butyl-p-cresol, pentaerythritol-four [3-(3s 5-di-tert-butyl-4-hydroxyphenyl)propionate ], triethylene glycol-bis[3-(3-tri-butyl-5-methyl-4-hydroxyphenyl)propionate] is preferred. Further, for example, a metal inert agent such as N,N,-bis[3-(3,5-di-tris-butyl-4-hydroxyphenyl)propanyl]anthracene or the like can be used. , a phosphorus-based processing stabilizer such as 4-di-tris-butylphenyl phosphite. The amount of the compound to be added is preferably 1 ppm to 1% by mass based on the mass ratio of the cellulose derivative, and is preferably 1 〇 to 1 〇〇〇 ppm. Further, in the retardation film of the present invention, it is preferred to use fine particles for imparting lubricity. The primary average particle diameter of the fine particles added to the retardation film of the present invention is preferably 20 nm or less, more preferably 5 to 16 nm, and particularly preferably 5 to 12 nm. The fine particles are preferably formed into a retardation film by forming secondary particles having a particle diameter of 0.1 to 5 μm, and an appropriate average particle diameter is 0.1 to 2 μΐΒ, more preferably 0.2 to 0.6 μη. Thereby, irregularities having a height of about 0.1 to 1.0 μηι are formed on the surface of the film, whereby appropriate lubricity can be imparted to the surface of the film. The measurement of the average particle diameter of the microparticles used in the present invention is carried out by observing the particles by a through-electron microscope (magnification of 500,000 to 2,000,000 times) through a -35-200821642, and observing the particle diameter by The average enthalpy is taken as the average particle diameter of one time. The aspect ratio of the fine particles is preferably 7 〇 g / liter or more, more preferably 90 to 200 g / liter, and particularly preferably 1 〇〇 to 200 g / liter. The larger the specific gravity of the appearance, the higher the concentration of the dispersion can be produced, and the haze and the agglomerate are preferably improved, and the present invention is particularly preferable when the doping having a high solid concentration is prepared. The primary particles having a primary diameter of 20 nm or less and an apparent specific gravity of 70 g/liter or more, for example, ruthenium tetrachloride and hydrogen to be vaporized: mixed at 1 000 to 1 200 ° C in the air Available under combustion. Further, for example, Aerosil 200V, Aerosil R972V (above, manufactured by Japan Aerosil Co., Ltd.) is commercially available as a commercial item, and such a product can be used. The apparent specific gravity described above is measured by using a certain amount of cerium oxide microparticles, and the weight is measured by the following formula. The specific gravity of the appearance (g/liter) = the mass of the cerium oxide (g) / the volume of the cerium oxide (liter). The method of preparing the dispersion of the fine particles used in the present invention may, for example, be as follows. <<Modulation Method A>> After the solvent and the fine particles were stirred and mixed, they were dispersed by a disperser. It is used as a fine particle dispersion. The fine particle dispersion was added to the dope to -36-200821642 to be stirred. <<Modulation Method B>> The solvent and the fine particles were stirred and mixed, and then dispersed by a disperser. This was used as a fine particle dispersion. Further, a small amount of cellulose triacetate was added to the solvent, and the mixture was stirred and dissolved. The fine particle dispersion was added thereto for stirring. It is used as a fine particle addition liquid. The microparticle addition solution is thoroughly mixed with the doping solution in an in-line mixer. <<Preparation Method C>> A small amount of cellulose triacetate is added to a solvent and stirred and dissolved. The microparticles were added to this dispersion in a disperser. Use it as a microparticle additive. The microparticle addition solution is thoroughly mixed with the doping solution in an in-line mixer. The week-by-side method A is excellent in the dispersibility of the fine particles of the oxidized sand, and the preparation method C is excellent in that the cerium oxide fine particles are hard to reaggregate. In the preparation method B described above, the dispersibility of the cerium oxide fine particles and the difficulty in re-aggregation of the cerium oxide fine particles are excellent modulation methods which are excellent in both. <<Dispersion Method>> The cerium oxide fine particles are mixed with a solvent or the like, and the concentration of cerium oxide at the time of dispersion is preferably 5% by mass to 3% by mass, and is preferably 1% by mass to 25% by mass. /〇 Further, it is most appropriate to use 1 5 to 20% by mass. The turbidity of the liquid having a higher dispersion relative to the added amount tends to be lower, and the haze is good, and the agglomerate can be improved -37-200821642. The solvent to be used is preferably a methyl alcohol, an ethyl alcohol, a propyl alcohol, an isopropyl alcohol or a butyl alcohol, in terms of a lower alcohol. The solvent other than the lower alcohol is not particularly limited, and a solvent used for film formation using a cellulose ester is preferred. The amount of the cerium oxide fine particles added to the cellulose ester is preferably 0.01 parts by mass to 5.0 parts by mass, based on 100 parts by mass of the cellulose ester, and is preferably 5 parts by mass to 1.0 part by mass. Good, it is appropriate to use 〇 mass parts ~ 〇 · 5 mass parts of violence. When the amount of addition is large, the coefficient of dynamic friction is excellent, and if the amount of addition is small, the amount of aggregates is small. The disperser can use a conventional disperser. Dispersers can be broadly divided into media dispersers and non-media dispersers. In the dispersion of the cerium oxide microparticles, it is appropriate to use a low haze of the non-dielectric disperser. The medium dispersing machine may, for example, be a ball mill, a sand mill, a Dino mill or the like. The non-media dispersing machine is of a supersonic type, a centrifugal type, a high pressure type, etc., and a high pressure dispersing device is preferable in the present invention. The high-pressure dispersing device is a device in which fine particles and a solvent are mixed, and is passed through a small tube at a high speed to produce a device having a special condition such as a high shear or a high pressure state. In the case of treatment with a high-pressure dispersing device, for example, in a capillary tube having a diameter of 1 to 2000 μm, the maximum pressure inside the device is preferably 9.807 MPa or more. Further preferably, it is 19.613 MPa or more. At this time, when the maximum arrival speed reaches 100 m/sec or more, the heat transfer rate is preferably 420 kJ/hr. In the above-mentioned high-pressure dispersing device, there is Microfluidics -38- 200821642

An ultrahigh pressure homogenizer (trade name: Microfluidizer) manufactured by Corporation, or a Nanomizer manufactured by Nanomizer Co., Ltd., may be exemplified by a Manton Gaulin type pressure dispersion device such as 'Izumifood machinary homogenizer, UHN_01 manufactured by Sanwa Machinery Co., Ltd., and the like. Further, when the doping containing fine particles is directly contacted with the cast support, it is appropriate to obtain a film having high lubricity and low haze. Further, after being casted, it is peeled off and dried, and after being wound into a roll shape, a functional film such as a hard coat layer or an antireflection layer can be provided. In order to prevent, contaminate or electrostatically adhere to dust during self-processing or shipment, the product is usually packaged. The packaging material is not particularly limited in order to achieve the above object, and it is preferred that the solvent remaining from the film is not volatilized. Specifically, polyethylene, polyester, polypropylene, nylon, polystyrene, paper, various non-woven fabrics, and the like can be exemplified. The fiber is preferably used as a mesh cloth. The retardation film of the present invention preferably contains a retardation controlling agent to adjust the retardation. (Bar-shaped compound) The retardation film of the present invention preferably contains a rod-like compound having a wavelength shorter than 250 nm as a retardation controlling agent in such a manner that the maximum absorption wavelength (Omax) of the ultraviolet absorption spectrum of the solution is shorter. From the standpoint of the function of the retardation controlling agent, the rod-like compound is preferably one having at least one aromatic ring, and the one having at least two aromatic rings, and thus is -39-200821642. The rod-like compound is preferably one having a linear molecular structure. The linear molecular structure refers to the fact that the molecular structure of the rod-like compound in the most stable structure is thermodynamically constructed as a straight line. The thermodynamically most stable structure can be obtained by crystallographic structural analysis or molecular orbital calculation. For example, molecular orbital calculation software (Example 'WinMOPAC2000, manufactured by Fujitsu Co., Ltd.) is used for molecular orbital calculation to determine the molecular structure in which the heat of formation of the compound is the smallest. The molecular structure is a straight line finger, and the thermodynamically most stable structure obtained by the above calculation has a molecular structure angle of more than 140 degrees. The rod-like compound preferably exhibits liquid crystallinity. It is also preferable that the rod-like compound exhibits liquid crystallinity (having thermotropic liquid crystallinity) by heating. The liquid crystal phase is preferably a nematic phase or a smetic phase. In the case of a rod-like compound, a trans-1,4-cyclohexanedicarboxylate compound represented by the following general formula (4) is preferred. General formula (4) Arl-Ll-Ar2 In the general formula (4), Arl and Ar2 are each independently an aromatic group. In the present specification, the aromatic group contains an aryl group (aromatic hydrocarbon group), a substituted aryl group, an aromatic heterocyclic group and a substituted aromatic heterocyclic group. The aryl group and the substituted aryl group are more suitable than the aromatic heterocyclic group and the substituted aromatic heterocyclic group. The heterocyclic ring of the aromatic heterocyclic group is generally unsaturated. The aromatic heterocyclic ring is preferably a 5-membered ring, a 6-membered ring or a 7-membered ring, and is preferably a 5-member ring or a 6-member ring. Aromatic heterocycles generally have the most double bonds. The impurity -40-200821642 sub-aspect is preferably a nitrogen atom or an oxygen atom, and a nitrogen atom or a sulfur atom is further preferred. In the case of the aromatic heterocyclic ring, it may contain a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazine ring, an isothiazolidine ring, an imidazole ring, a pyrazole ring, and a furan (fUrazan). Ring, triterpene ring, nucleus ring, pyridine ring, anthracene ring, pyrimidine ring, pyrazine ring and 1,3,5-triantane ring. The aromatic ring of the aromatic group is a benzene ring, a furan ring, a _ ring, a p-ring ring, an oxazole ring, a thiazole ring, an imidazole ring, a triazole ring, a ruthenium ring, a methylene ring, and a pyridyl ring. The azine ring is preferred, and the benzene ring is particularly preferred. In the substitution of the substituted aryl group and the substituted aromatic heterocyclic group, g &amp; J, M may contain a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxyl group, a cyanide, an amine group, an alkylamine Base (eg, methylamino, ethylamino, butylamino, dimethylamino), nitro, sulfo, aminemethanyl, alkylamine methyl (eg, methylamine formazan) Base, N-ethylamine, mercapto, hydrazine, hydrazine-dimethylaminocarboxylic acid), amidoxime, alkylamine sulfonyl (eg, N-methylamine δ xanthyl, N-ethylamine) Sulfhydryl, N,N-dimethylaminesulfonyl), ureido, alkylureido (eg, N-methylureido, N,N-dimethylureido, N, N, N' -H methylureido), affiliation (eg, methyl, ethyl, propyl, butyl, pentyl, heptyl, octyl, isopropyl, butyl, tert-amyl, cyclohexyl) , cyclopentyl), alkenyl (eg, ethylene, propyl, hexenyl), alkynyl (eg, ethynyl, butyne), mercapto (eg, methyl, ethyl, butyl) , hexyl, lauryl), mercaptooxy (eg, ethoxylated, butyloxy, hexyloxy, lauryl) Oxygen), anthracene (eg, methoxy, ethoxy, propoxy, butoxy, pentyloxy, heptyloxy, octyloxy), aryloxy (eg, phenoxy), Alkoxycarbonyl (eg, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl-41 - 200821642 keto-butoxy-ylpentyloxycarbonyl, heptyloxycarbonyl), aryloxycarbonyl (example) 'Phenoxy group', alkoxycarbonylamino (eg, butoxycarbonylamino 'hexyloxylanido), alkylthio (example, methylthio, ethylthio'-propyl Thiothio-butylthio, pentylthio, heptylthio, octylthio) 'arylthio (eg, phenylthio), alkylsulfonyl (eg, methylsulfonate) 'Ethyl sulfonyl, propyl sulfonyl, butyl sulfonyl, pentyl sulfonyl 'heptyl fluorenyl 'octyl sulfonyl), guanamine (eg, acetamide, butyl) Sg stomach s 'hexyl decylamine, lauryl decylamine) and non-aromatic heterocyclic groups (eg, morpholinyl, pyrazine). In terms of the substituent of the substituted aryl group and the substituted aromatic heterocyclic group, the atomic 'amino' residue 'hydroxyl group, amine group, alkyl group substituted amine group, fluorenyl group, 醯s_ group 'nonylamino' alkoxy group The carbonyl group, the alkoxy group, the alkylthio group and the alkyl group of the alkyl group, the alkoxycarbonyl group, the alkoxy group and the alkyl group of the alkylthio group and the alkyl group may further have a substituent. Examples of the alkyl moiety and the alkyl group of the alkyl group may contain a halogen atom, a hydroxyl group, a carboxyl group, a cyanogen group, an amine group, an alkyl acetamyl group, a nitro group, a sulfo group, an amine group, an alkyl group. Sulfhydryl, sulfonyl 'alkylamine sulfonyl, ureido, alkyl ureido, alkenyl, alkynyl, fluorenyl 'fluorenyloxy, alkoxy, aryloxy, alkoxy Carbonyl, aryloxycarbonyl 'alkoxycarbonylamino, alkylthio, arylthio, alkylsulfonyl 'nonylamino and non-aromatic heterocyclic. The alkyl moiety and the substituent of the alkyl group are preferably a halogen atom, a hydroxyl group, an amine group, an alkylamino group, a fluorenyl group, a fluorenyl group, a ketone group, an alkoxy group and an alkoxy group. . In the general formula (4), L1 is selected from the group consisting of an alkylene group, an alkenylene group, a acetylene group, a divalent saturated heterocyclic group, -0-, -CO-, and the like -42-200821642 Groups of divalent linkages. The alkylene group may have a cyclic configuration. In terms of a cyclic alkylene group, cyclohexene is preferred, and 1,4-hexene is particularly preferred. In the case of a chain alkylene group, a linear alkylene group is more suitable than a branched alkyl group. The number of carbon atoms of the alkylene group is preferably from 1 to 20, more preferably from 1 to 15, more preferably from 1 to 10, even more preferably from 1 to 8, and most preferably from 1 to 6. The alkenylene group and the alkyne group are preferably a chain structure as compared with the ring structure, and are more suitable for a linear structure than a chain structure having a branch chain. The alkylene group and the alkynylene group have preferably 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and more preferably 2 to 4 carbon atoms. Ethylene or acetylene groups are most suitable. The divalent saturated heterocyclic group is preferably a heterocyclic ring having 3 to 9 members. The hetero atom of the hetero ring is preferably an oxygen atom, a nitrogen atom, a boron atom, a sulfur atom, a sand atom, a phosphorus atom or a ruthenium atom. In the case of a saturated heterocyclic ring, a piperidine ring may be contained, a hexahydropyridyl: anthracene ring, a morpholino ring, a deuterium D ring, an imida ζ ο 1 idine ring, a tetrahydrofuran ring, and a tetrahydroperazine. Ring, 1,3-dioxane ring, 1,4-dioxin ring, tetrahydrothiophene ring, 1,3- thiazolidine (thia ζ ο 1 idine ) ring, 1,3 -oxazolidine Ring, 1,3-dioxolane ring, 1,3-dithiolane ring and l,3,2-dioxabororane. Especially suitable divalent saturated heterocyclic hexahydropyrazine-1,4-diphenyl, 1,3-dioxane-2,5-diphenyl and 1,3,2 · di ο X ab 〇r 〇rane - 2,5 - di-subunit. An example of combining a divalent bond group. L-1 : ·0-(:0-alkylene-C0-0- レ2:-C0-0-alkylene-0-C0--43-200821642 L - 3 · -O-CO- Support group -CO-O- L-4: -CO-O-alkenylene-O-CO- L-5 : -O-CO -alkyne-CO-O- L-6: -CO-O -Alkynyl-O-CO- L-7: -O-CO-divalent saturated heterocyclic group-CO-O- L-8: -CO-O-divalent saturated heterocyclic group-O-CO- In the molecular structure of the formula (4), the angle formed by the bonding of the Arl and the Ar2 to the LI is preferably 140 or more. In terms of the rod-like compound, the compound represented by the following general formula (5) is further suitable. Ar 1 -L2-X-L3-Ar2 In the general formula (5), each of Arl and Ar2 is independently an aromatic group. The definition and examples of the aromatic group are the same as those of Arl and Ar2 of the general formula (4). In (5), each of L2 and L3 is independently a divalent linkage selected from the group consisting of an alkylene group, -0-, -C0-, and a combination thereof. The alkylene group is compared with the cyclic structure to have The chain structure is preferred, and it is more suitable to have a linear structure as compared with a chain structure having a branched chain. The number of carbon atoms of the alkylene group is preferably 1 to 1 Torr, and preferably 1 to 8, 1 to 6 is further preferred, preferably 1 to 4, and further preferably, 1 or 2 (methylene or ethylene) is most appropriate. L 2 and L 3 are -0 - C 0 - or -C Ο - 0 - especially. In general formula (5), X is 1,4· Cyclohexene, vinylene or ethynylene. The phase difference film of the present invention is prepared by dissolving a cellulose ester and an additive such as a plasticizer in a solvent to prepare a doping step, which is doped in a ribbon or -44- 200821642 The step of casting on a drum-shaped metal support, the step of casting the doped mesh by the process of casting, the step of peeling off from the metal support, the step of stretching, and the step of drying, the obtained The film is further subjected to a heat treatment step, followed by a step of cooling and winding. The retardation film of the present invention preferably contains 70 to 95% by mass of the cellulose ester in the solid content. The following describes the step of preparing the doping. The concentration of the cellulose ester in the heterogeneous group is preferably such that the dry load of the metal support after casting is reduced, and when the concentration of the cellulose ester is too high, the load during filtration is increased, and the filtration accuracy is deteriorated. It is preferable that the concentration of the coexistence is 10 to 35 mass%. Further, it is preferably 15 to 25% by mass. The solvent used for the doping of the present invention may be used singly or in combination of two or more. It is preferred that the cellulose solvent is mixed with a weak solvent at a production efficiency. The solvent solubility is appropriate for a good solvent. The appropriate range of the mixing ratio of the good solvent to the weak solvent is 70 to 98% by mass of the good solvent and 2 to 30% by mass of the weak solvent. A good solvent or a weak solvent is defined as a good solvent for the cellulose ester to be used alone, and a weak solvent for those who are inflated or insoluble. Therefore, due to the degree of substitution of the thiol group of the cellulose ester, the good solvent and the weak solvent are changed. For example, when acetone is used as a solvent, the acetate in the cellulose ester (the degree of substitution of acetyl group 2.4), cellulose acetate The ester propionate becomes a good solvent, and the acetate in cellulose (the degree of substitution of acetyl group 2.8) becomes a weak solvent. The good solvent to be used in the present invention is not particularly limited, and examples thereof include an organic halogen compound such as methylene chloride or a dioxolane, acetone, methyl acetate, and ethyl acetate. Particularly preferred is dichloromethane or ethyl acetate -45-200821642 ester. Further, the weak solvent used in the present invention is not particularly limited, and it is preferably used, for example, methanol, ethanol, n-butanol, cyclohexane or cyclohexanone. Further, it is preferable that the water is doped in an amount of 0 · 0 1 to 2% by mass. In the case of preparing the above-described doping, a general method can be used for the method of dissolving the cellulose ester. It can be heated to above the boiling point at normal pressure during combined heating and pressurization. At a temperature above the atmospheric pressure of the solvent and under pressure, the temperature at which the solvent does not boil can be stirred and dissolved while heating, so that it can be prevented from being called a gel or insoluble powder (anundiss ο 1 ved 1 ump 〇 ff 1) The blocky undissolved matter of our) occurs as appropriate. Further, it is preferred to mix and dissolve the cellulose ester with a weak solvent, and then to dissolve it by using a good solvent. The pressurization is preferably P a or less, and more preferably 1 · 〇 Μ P a or less. Here, the doping casting is explained. In the flow of the Iff (iff) process, the metal support is used to make the surface mirror-finished. The final processor is preferred. In terms of the metal support, it is preferable to use a stainless steel strip or a cast to make the surface of the drum finally processed by electroplating. The casting width can be 1 to 4 m. The surface temperature of the metal support in the casting step is set at _50 ° C ~ solvent boiling without foaming temperature. The temperature is higher because the drying speed of the mesh can be quickly performed, so that when the mesh is too high, the mesh may be foamed or the planarity may be deteriorated. The appropriate support temperature is suitably determined from 0 to 100 ° C, and is preferably 5 to 30 ° C. Alternatively, the mesh may be gelled by cooling so that the residual solvent contains -46-200821642. It is also an appropriate method to peel off the drum. The method of controlling the temperature of the metal support is not particularly limited, and it may be a method of blowing with warm air or cold air, or a method of bringing warm water into contact with the inner side of the metal support. In the case of using warm water, since heat conduction can be efficiently performed, the time until the temperature of the metal support is constant can be shortened to be appropriate. In the case of using warm air, the temperature of the mesh may be lowered in consideration of the latent heat of evaporation of the solvent, and the warm air above the boiling point of the solvent may be used, and the temperature may be higher than the intended temperature while preventing foaming. The situation of the wind. In particular, it is preferable to change the temperature of the support and the temperature of the dry air during the period from the time of casting to the peeling, so that drying can be performed efficiently. When the cellulose ester film exhibits good planarity, the amount of residual solvent in the case of peeling off the mesh is preferably from 10 to 150% by mass, more preferably from 20 to 40% by mass or 60 to 130% by mass, particularly preferably 20: -30% by mass or 7 0 to 120% by mass. Further, the metal support is peeled off, and the temperature is preferably -50 to 40 ° C in the position, preferably 10 to 40 ° C, and 15 to 30 ° C is most appropriate. In the present invention, the amount of residual solvent can be defined by the following formula. The amount of residual solvent (% by mass) = {(MN) / N}xl 00 In addition, the mass of the sample taken at any point in the manufacture of the mesh or film or after the manufacture, the tanning system is at 1 1 5 The mass after heating for 1 hour at °C. Further, in the drying step of the cellulose ester film, the web is peeled off from the metal support 47-200821642, dried, and dried to have a residual solvent amount of 0.5% by mass or less. The film drying step is generally carried out by means of roll drying (a method in which a plurality of rolls arranged up and down are alternately dried by means of a mesh) or by means of a stretcher while conveying the web. When the metal support is peeled off, the mesh is stretched in the longitudinal direction by the peeling tension and the subsequent transport tension. Therefore, in the present invention, when the mesh is peeled off from the cast support, the peeling can be performed. It is preferable to carry out the state in which the conveying tension is as low as possible. Specifically, for example, it is effective to be 50 to 1 70 N/m or less. At this time, it is preferable to blow a cold air of 20 ° C or less to make the mesh fast and fast. An example of the stretching step (referred to as a stretcher step) for forming a retardation film of the cellulose ester film of the present invention is as shown in Fig. 1 and Fig. 2 is a f. In Fig. 1 and Fig. 2, the steps of the A, B, and C stretching steps, and the arrow S indicate the direction in which the film is to proceed. The step A is a step of holding the mesh conveyed from the mesh transporting step DO not shown. In the next step B, in the drawing angle shown in Fig. 1, the web is stretched to the broad side direction (the direction orthogonal to the direction in which the web is made), and in step C, the stretching is completed. Carry the mesh as it is. In the method for producing a retardation film of the present invention, one of the steps of the film forming step is provided in the step of stretching the film at the end of the film and stretching in the direction orthogonal to the conveying direction. The stretching condition is in the range of the following formula (2). -48- 200821642 Formula (2) 60^ΧχΥ^450 In the formula, X is the stretching speed [m/min], and Υ is the stretching ratio [%]. According to the present invention, in the stretching step of the film, the alignment of the film can be improved by controlling the stretching speed, and the crystallization of the cellulose ester resin can be suppressed or polymerized under the stretching ratio of the control film. The micro-phase separation of the substance and the additive can obtain a phase difference film which can maintain the transparency of the film and can improve the unevenness of the substrate corners in the large-screen VA type liquid crystal panel. Next, it is preferred to provide a slitting machine which can cut off the end portion in the width direction of the web after the web is peeled off from the casting support until the start of step B, and/or after step C. In particular, it is preferred to set the slitting machine at the end of the web to be cut before the start of step A. When the stretching is performed in the same direction as the broad side direction, especially before the start of step B, the former is more available when compared with the condition of cutting the end of the mesh and the condition of not cutting the end of the mesh. Improve the effect of the distribution of the optical slow axis (called the alignment angle distribution). In the past, the long-side direction from the peeling of the residual solvent amount to the wide-side stretching step of the step B is not the suppression effect of the stretching intended by us. In the stretching step, it is also appropriate to improve the alignment angle distribution even if it is made to have a different temperature division. Moreover, it is also appropriate to set a neutral zone so that there is no interference between the different divisions between different temperature divisions. -49 - 200821642 Further, the stretching operation can be carried out in multiple stages, and it is preferable to carry out the biaxial stretching in the direction of the casting and the wide side. Further, even in the case of biaxial stretching, biaxial stretching can be simultaneously performed, and it can be carried out in stages. In this case, the staged means that, for example, the stretching in different stretching directions may be sequentially performed, the stretching in the same direction may be divided into multiple stages, and the stretching in different directions may be added to any stage thereof. . The mesh which is peeled off from the metal support is conveyed while being dried, and the both ends of the mesh are stretched in a wide direction by a pin or a jig, and the effect of the present invention is obtained. Preferably, the phase difference can be given to the setting. In this case, it is possible to perform stretching only in the width direction and to perform 2-axis stretching at the same time. The appropriate stretching ratio is preferably 1.0 5 to 2 times, preferably 1. 5 to 1.5 times. When the 2-axis stretching is performed at the same time, the shrinkage in the longitudinal direction may be performed, and the shrinkage may be in the range of 0.8 to 0.99, preferably 0.9 to 0.99. Preferably, the area is from 1.12 times to 1.44 times, preferably from 1.15 times to 1.32 times, by stretching in the transverse direction and stretching or shrinking in the longitudinal direction. This is obtained by the draw ratio in the longitudinal direction of the draw ratio X in the transverse direction. Further, in the present invention, the "stretching direction" means that the direction in which the tensile stress is directly added in the case of performing the stretching operation is generally used, and the biaxial stretching is performed in multiple stages, and finally It is used in the sense that the stretching ratio is large (that is, the direction usually becomes the direction of the slow axis). In the case where the web is stretched in the widthwise direction, the distribution of the alignment angle in the width direction of the web is self-evident. When Rt and Ro are made to be -50-200821642, a certain ratio is made, and since the alignment angle distribution is wide-angled in a good state, the relative mesh temperature is present in steps A, B, and C. When the network temperatures at the end points of steps A, B, and C are each Ta ° C, Tb ° C, and Tc ° C, TaSTb-10 is preferred. Also, TcSTb is preferred. TaSTb-10 and Tc^Tb are further appropriate. The rate of temperature rise of the web in step B is preferably in the range of 0.5 to l 〇 ° c / sec in order to make the alignment angle distribution good. The stretching time in step B is preferably in a short time. However, from the viewpoint of the uniformity of the mesh, it is specified in the range of the minimum necessary stretching time. Specifically, the range of 1 to 10 seconds is preferable, and 4 to 10 seconds is more appropriate. Further, the temperature of the step B and the step C is such that the temperature of the film is in the range of the glass transition temperature of -30 to -1 ° C, preferably 100 to 160 ° C °. In the above stretching step, the heat transfer coefficient It can be fixed or changed. In terms of heat transfer coefficient, it is preferred to have a heat transfer coefficient in the range of 41.9 to 419 x 103 J/m2hr. Further preferably, it is in the range of 41.9 to 209.5 x 1 03 J/m 2 hr, and is most suitably in the range of 41.9 to 126 x 103 J/m 2 hr. The stretching speed in the width direction of the above step B may be constant or may be changed. The stretching speed is preferably 50 to 500%/min, more preferably 1 to 400%/min, and most preferably 200 to 30,000%/min. The control stress in the first 10 cm in the above step B is preferably to obtain the effect of the present invention, and it is preferable to control it in the range of 100 to 200 N/mm. -51 - 200821642 In the stretching step, the temperature distribution in the width direction of the atmosphere is small, and it is preferable from the viewpoint of improving the uniformity of the network, and the temperature distribution in the width direction of the stretching step is ±5 °. C is preferably inside, preferably within ±2 °C, and most preferably within db It. By reducing the above temperature distribution, it is expected that the temperature distribution on the wide side of the mesh tends to be small. In step C, it is preferred to moderate in the width direction. Specifically, it is preferred that the final web width after stretching in the previous step is adjusted to have a mesh width of 95 to 99.5%. Further, in the present invention, in order to improve the alignment accuracy of the polymer, the left and right holding means of the stretcher can be used to control the length of the web (the distance from the start of gripping to the completion of gripping). The ground controlled stretcher is appropriate. The length of the left and right ends of the mesh holding device by the stretcher stretching device is controlled to be left and right independent, and the means for making the mesh holding longer than the left and right are regarded as different means, specifically, for example, 3 shown in the figure. Fig. 3 is a view showing a polymer film used in the present invention, and a preferred example of a stretcher stretching device (l〇a) is shown in a schematic view. In the same figure, the holding position of the left and right holding means (clamp) (2a) (2b) of the stretcher stretching device (10 a) is changed to the left and right, that is, the clamp closer (3 a) (3 b) The setting position is changed to the left and right, and the left and right holding lengths of the film (F) can be changed by changing the holding start position to the left and right, whereby the resin film (F) can be twisted in the stretcher (10a) The force can be corrected by the positional deviation caused by the transfer other than the stretcher (10), and the transport distance from the peeling to the stretcher can be extended to effectively prevent the mesh snake-52-200821642 or The surface is rough and wrinkles occur. Further, the illustrated stretcher stretching device (10a) is described in a schematic diagram, usually in the form of a pair of left and right rotary drives (wheels) (la) (lb) In most of the jigs (2a) and (2b) of the one-row state, the clamps (2a) (2b) of the linearly-moving side of the chain-drawn side of the film (F) are stretched toward the film (F). The side of the chain (la) (lb) is provided in such a manner that the wide side direction is away, and the film (F) is stretched in the broad side direction. Further, in the present invention, it is preferable to use a device for preventing wrinkles, unevenness of the surface, deformation, and the like, and further improving the accuracy of the film, and it is preferable to use an edge position controller described in Japanese Patent Laid-Open No. Hei 6-8663. It is preferable to use an edge position controller (referred to as EPC) or a meandering correction device such as a central position controller (referred to as CPC). These devices use a pneumatic servo (air servo) sensor or a light sensor to detect the edge of the film, and control the transport direction according to the information, so that the center of the film or the center of the width direction is constant. The transfer position, as its actuator, specifically, 1 to 2 guide rolls or a flat expander roll with respect to the line direction, left and right (or up and down) Perform serpentine correction, or set a small two-piece 1 set of pinch rolls on the left and right sides of the film (set each on the surface of the film, on both sides of the film) 'Use this to hold the film and stretch Perform a meandering correction (guide guide device close guider mode). The serpentine correction principle of these devices is the method of making the roll tilt to the right of the film in the way of the film, for example, when the film is moved to the left, and the method of the latter is to make the right side i-53 - 200821642 The guide roller of the group is cut (nip) and stretched toward the right. It is preferable to provide at least one of the anti-snaking devices from the film peeling point to the stretcher stretching device. After the treatment in the stretching step, it is preferred to set the post-drying step (below, step D1). The tension of the mesh conveyed in step D1, the physical properties of the doping, the amount of residual solvent in the peeling and the step D0, are affected by the temperature of the step D1, etc., preferably 120 to 20 0 N/m, and 140~ 200 N/m is then appropriate. The most suitable is 140~160 N/m. It is preferable to provide a tension cutting roller for the purpose of preventing the extension of the mesh in the transport direction in the step D1. The means for drying the web is not particularly limited, and it can be generally carried out by hot air, infrared rays, heating rolls, microwaves, etc., and it is preferable to carry out hot air at a simple point. The drying temperature in the drying step of the mesh is preferably a glass transition temperature of the film of -5 ° C or less, and 100 ° C or more, and heat treatment for 10 minutes or more and 60 minutes or less is effective. The drying temperature is from 100 to 200 ° C, and further preferably from 110 to 160 ° C. Further, it is preferably at 105 to 155 ° C, and it is preferred to carry out the heat treatment at the same time as the atmosphere replacement rate of 12 times/time or more, preferably 12 to 45 times/time. In the retardation film of the present invention, in the relationship of the elastic modulus of the present invention, the free volume radius is preferably determined by the positron annihilation life method to be 0.250 to 0.350 nm, especially 〇·250~ 0.310 nm is preferred. -54· 200821642 The free volume here is intended to mean that the molecular chain of the cellulose resin does not occupy a void. This can be measured using the positron annihilation lifetime method. Specifically, the time when the positron is incident on the sample until it is destroyed is determined by a non-destructive observer from the annihilation lifetime of the atomic pore or the volume of the free volume, the number of concentrations, and the like. The retardation film of the present invention has an elastic modulus (E23) in a tensile direction of the film measured under the conditions of a temperature of 231: and a humidity of 55% RH of 3.4 to 4.4 GPa, and a temperature of 50 ° C and a humidity of 55% RH. The difference (E23_5G) between the elastic modulus (E5G) of the film in the tensile direction measured under the measurement conditions can satisfy the following formula (1). Formula (1) 0.30^ΔΕ23-5〇^〇.80 But » Ε23-5 0 = Ε23·Ε5〇° Here, the temperature difference film is measured under the measurement conditions of 23 ° C, humidity 5 5% RH When the stretch direction elastic modulus (E23) is less than 3.4 GPa, the contraction force of the polarizing element due to environmental changes is deteriorated, and the retardation film is deteriorated, which is not preferable because the size of the polarizing film itself largely changes. Especially in the case of large screens with large polarizing films, it is easy to be a problem. In addition, when the elastic modulus (E23) in the stretching direction of the retardation film measured under the measurement conditions of the temperature of 23 ° C and the humidity of 55% RH exceeds 4.4 GPa, the curl of the polarizing film becomes large, and the liquid crystal panel is manufactured. In the steps, it is not good because of the big obstacles. Next, in the present invention, the elastic modulus (E23) of the film stretching direction measured under the conditions of temperature 23, humidity 55% RH -55-200821642, and temperature 50 ° C 'humidity 55% RH The difference (E23.5G) of the elastic modulus (E5G) in the tensile direction of the film measured under the measurement condition can satisfy the above formula (1), that is, the temperature of the retardation film can be reached, for example, by lighting the panel backlight. Nearly 50 °C, the elastic modulus (E5G) of the phase difference film monomer in its state can be compared with the elastic modulus (E23) of the temperature of 23 °C in the range of as low as 0.3 to 0.8 GPa. The shrinkage force causes the protective film or the retardation film itself to be deformed, and the effect of improving the unevenness of the substrate corners in the large-screen VA liquid crystal panel is remarkable. [Cycloolefin polymer film] A cycloolefin polymer film which can be suitably used in the present invention will be described. The cycloolefin polymer used in the present invention is composed of a polymer resin having an alicyclic structure. A suitable cycloolefin polymer is a resin which polymerizes or copolymerizes a cyclic olefin. The cyclic olefin may, for example, be norbornene, dicyclopentadiene, tetracyclododecene, ethyltetracyclododecene, ethylene tetracyclododecene or tetracyclic [7.4.0.110]. , 13.02,7] 13-2,4,6,11-tetraene and other polycyclic structures of unsaturated hydrocarbons and their derivatives; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethyl Cyclopentene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methylene -1H-oxime, cycloheptene, cyclopentadiene, cyclohexadiene, etc., monocyclic structure of unsaturated hydrocarbons and derivatives thereof. The cyclic olefins may have a polar group as a substituent. The polar group may, for example, be a hydroxyl group, a carboxyl group, an alkoxy group, an epoxy group, a glycidyl group, a -56-200821642 hydroxycarbonyl group, a carbonyl group, an amine group, an ester group, a carboxylic acid anhydride group or the like, especially an ester group. A carboxyl group or a carboxylic acid anhydride group is appropriate. The appropriate cycloolefin polymer may be an addition copolymerization of a monomer other than the cyclic olefin. As the monomer which can be copolymerized, ethylene or an α-olefin such as ethylene, propylene, 1-butene or pentene can be exemplified; 1,4·hexadiene, 4-methyl-1,4-hexyl a diene such as a diene, 5-methyl-I,4-hexadiene or 1,7-octadiene. The cyclic olefin is obtained by an addition polymerization reaction or a metathesis ring-opening polymerization reaction. The polymerization is carried out in the presence of a catalyst. The catalyst for addition polymerization may, for example, be a polymerization catalyst such as a vanadium compound and an organoaluminum compound. As a catalyst for ring-opening polymerization, it is a catalyst of a metal such as ruthenium, rhodium, palladium, or ruthenium, or a metal halide such as platinum or a ruthenium acetonate compound, and a reducing agent; or titanium or vanadium. a metal halide such as chromium, tungsten or molybdenum or an ethyl acetonide compound, a polymerization catalyst formed with an organoaluminum compound, etc. The polymerization temperature, pressure, and the like are not particularly limited, and are usually -5 (TC to 100 ° C). Polymerization temperature, polymerization pressure polymerization of 〇~490N/cm2. The cycloolefin polymer used in the present invention is a polymerization reaction or copolymerization of a cyclic olefin, followed by hydrogenation reaction, and it is preferred to change the unsaturated bond in the molecule to a saturated bond. The hydrogenation reaction is carried out by blowing hydrogen in the presence of a known hydrogenation catalyst. The hydrogenation catalyst may, for example, be cobalt acetate/triethylaluminum, acetonitrile, acetonylacetone/triisobutylene. Aluminum, titanocene/n-butyllithium, zirconcene chloride/secondary butyllithium, tetrabutoxytitanate/dimethylmagnesium a combination of a transition metal compound/alkyl metal compound to form a homogeneous catalyst; -57- 200821642 Nickel 'palladium' platinum and other heterogeneous metal catalysts; nickel / cerium oxide, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / cerium oxide, palladium / diatomaceous earth, For example, the palladium/alumina supporting metal catalyst may be a heterogeneous solid supported catalyst or the like. Alternatively, the cycloolefin polymer may be exemplified by the following norbornene-based polymer. The polymer is preferably one having a norbornene skeleton as a repeating unit, and a specific example thereof can be exemplified by JP-A-61-2 _ 2 5 2 4 〇6. Japanese Patent Publication No. 252407, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei 6-3- 1 4 5 3 2 4, Japanese Patent Laid-Open No. 6 3 · 2 6 4 6 2 6 Special Kaiping} _ 2 4 〇5〗 No. 7 Bulletin, Special Public · „ 5 7 7 7 7 7 7 5 5 5 5 5 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Bulletin No. 28, Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei 9-24 1 484, etc., which is described in the above-mentioned Japanese Patent Application Laid-Open No. Hei 9-24 No. 484, etc., is not limited thereto. In the present invention, it is preferable that the reduction unit is a repeat unit represented by any one of the following structural formulas (1) to (IV). -58- 200821642 [ 7] (1)

C and D are independent of each other.

In the structural formulas (1) to (IV), A, B

Represents a hydrogen atom or a monovalent organic group. Further, among the norbornene-based polymers, at least one of the following compounds of the following structural formula (¥) or (乂〇) is used, and a polymer obtained by metathesis-polymerizing an unsaturated cyclic compound copolymerizable therewith is subjected to a metathesis polymerization. The hydrogenated polymer obtained by hydrogenation is also suitable.

B C D -59 - (V) 200821642

(VI) In the structural formula, A, B, C and D are each independently represented by a hydrogen atom or a monovalent organic group. Here, the above A ' B, C and D are not particularly limited, and are preferably a hydrogen atom, a halogen atom, a monovalent organic group, or an organic group may be bonded through at least a divalent linking group, and these may be the same or phase. different. Also, A or B and C or D may form a monocyclic or polycyclic structure. Here, the at least divalent linking group means a hetero atom which may be represented by an oxygen atom, a sulfur atom or a nitrogen atom, and may, for example, be an ether, an ester, a carbonyl group or a urethane ethyl amide amine amine thioether. Etc., and not limited to such. Further, the organic group can be further substituted by the above-mentioned bonding group. Further, in terms of other monomers copolymerizable with the norbornene-based monomer, for example, ethylene, propylene, butene, pentene, 1 · hexene, 1-octene, 1-decene, - dodecene, 1-tetradecene, 1-hexadecene '1-octadecene, 1-eicene and the like, an a-olefin having a carbon number of 2 to 20' and such derivatives; cyclobutene, a cyclic olefin such as cyclopentene, cyclohexene, cyclooctene, 3a, 5, 6, 7a-tetrahydro-4,7-methyl-1H-indole, and the like; and 4-hexyl Occasionally, 4-methyl-1,4-hexadiene, 5-methyl-I,4·hexadiene', non-conjugated diene such as 7-octadiene; Among these, α-olefins, especially ethylene, are preferred. In addition, the other monomers copolymerizable with the norbornene-based monomer may be used alone or in combination of two or more. The addition of the sinter-sintering monomer to the other copolymerizable monomers in the case of addition copolymerization in the addition copolymer -60-200821642 The structural unit of the self-reducing decene monomer can be copolymerized from other The ratio of the structural unit of the monomer is usually in the range of 3 0: 7 0 to 9 9 : 1, preferably 50: 5 0 to 97: 3, more preferably 7 Q: 30 to 95: 5 Suitable for ^bb choice. When the unsaturated bond remaining in the polymer chain of the synthesized polymer is saturated by the hydrogenation reaction, the hydrogenation rate is 90% or more, preferably 95, from the viewpoints of light resistance deterioration, weather resistance deterioration, and the like. More than %, especially better than 99%. In addition, the cycloolefin polymer to be used in the present invention may be described in paragraphs [〇〇14] to [0019] of JP-A-5-2108. Thermoplastic saturated decene-based resin, JP-A-20001 - 2 7 7 4 3 0&gt; The thermoplastic norbornene-based polymer described in paragraphs [0015] to [0031], JP-A-2003- The thermoplastic, norbornene-based resin described in paragraphs [0008] to [0045], which is described in paragraphs [0014P to [0 0 2 8] of JP-A No. 203-139950; jfg olefinic resin The composition of the composition of the present invention is described in the paragraph [〇〇29]~[0〇37], which is described in the paragraph [〇〇29]~[0〇37], and the paragraph [0027] ~ [0036] The decene-based resin, Japanese Patent Laid-Open No. 2〇〇3-21, No. 5, 89, paragraph [〇〇〇9] ~ [0 0 2 3 ] alicyclic structure-containing polymer resin, Japan The norbornene-based polymer resin or the vinyl alicyclic hydrocarbon polymer resin described in paragraphs [0008] to [0 0 24] of JP-A-2003-2115. Specifically, it is preferable to use ZE ONEX®, ZEONOR® manufactured by Japan Zeon Co., Ltd., Arton manufactured by JSR Corporation, and appel (APL8008T, APL6509T, APL6013T, APL5014DP, -61 - 200821642 APL6015T) manufactured by Mitsui Chemicals Co., Ltd., and the like. The molecular weight of the cycloolefin polymer used in the present invention can be appropriately selected depending on the purpose of use, but the polyisodazole determined by gel permeation chromatography of a cyclohexane solution (the toluene solution in the case where the polymer resin is not dissolved) The mass average molecular weight of pentadiene or converted polystyrene is usually 5,000 to 500,000, preferably 8,000 to 200,000, more preferably 1 to 10,000 to 1,400, and the mechanical strength and formability of the molded body are It is appropriate for a high degree of balance. The cycloolefin polymer film may be contained in the plastic film as a generally compatible additive as needed. As such an additive, a heat stabilizer, a light stabilizer, a UV absorber, an antistatic agent, a slip agent, a plasticizer, a chelating agent, etc. may be exemplified, and the content thereof may be selected without damaging the object of the present invention. By. The method for forming the cycloolefin polymer film is not particularly limited, and any one of the layer heating and melt molding methods and the solution casting method can be used. The heat-melting forming method can be further classified into an extrusion molding method, a press molding method, an inflation molding method, an injection molding method, a blow molding method, a stretch forming method, etc., and the like. Among the methods, in order to obtain a film excellent in mechanical strength and surface precision, an extrusion molding method, an inflation molding method, and a press molding method are preferred, and an extrusion molding method is most suitable. The molding conditions can be appropriately selected depending on the purpose of use or the molding method. In the case of the heat fusion molding method, the cylinder temperature is usually 150 to 400 ° C, preferably 200 to 3 50 ° C, more preferably It is suitable to set in the range of 23 0 to 3 30 °C. When the resin temperature is excessively low, the fluidity is deteriorated, and the film is foamed (inverted - 62 - 200821642 blister) or strain. When the resin temperature is too high, voids or silver streak due to thermal decomposition of the resin may occur. There is a flaw in the formation of defects such as yellowing of the film. The thickness of the film is usually 5 to 3 μm, preferably 10 to 200 μm, more preferably 20 to 100 μm. In the case where the thickness is too thin, handling becomes difficult when laminating, and in the case of too thick, the drying time after lamination becomes long, which deteriorates productivity. The cycloolefin polymer film preferably has a wetting tension on the surface of 40 mN/m or more, more preferably 50 mN/m or more, and still more preferably 55 mN/m or more. When the wetting tension of the surface is in the above range, the adhesion strength between the film and the polarizing film can be improved. To adjust the wetting tension of the surface, for example, faint discharge treatment, ozone spraying, ultraviolet irradiation, flame treatment, chemical treatment, and other well-known surface treatments can be carried out. The thickness of the sheet before stretching is about 50~500 μm, and the thickness is not less than ±8%, preferably less than 8%, preferably less than 4%. . The cycloolefin polymer film can be obtained as the phase difference film of the present invention in the same manner as the above-mentioned cellulose ester film. Further, it is obtained by stretching the sheet in at least one axial direction. Further, the stretching can be carried out in a substantially one-axis direction, for example, after stretching in a range not affecting the molecular alignment, and may be a biaxial stretching in which one direction of the molecular alignment is to be stretched. It is preferable to stretch to use the stretcher device or the like. The stretching ratio may be 1.1 to 1 〇, preferably 1 · 3 to 8 times, and it is preferable if the range is desired to be delayed. When the draw ratio is too low, the delay of the delay is not improved, and it cannot be set. If it is too high, there will be a break. -63- 200821642 Shape. The stretching is usually carried out at a temperature at which the glass transition temperature (Tg) of the resin constituting the sheet is from Tg + 50 ° C, preferably from Tg to Tg + 40 °C. When the stretching temperature is too low, the film is broken. When the film is too high, the molecules are not aligned, so that the desired retardation film cannot be obtained. In this way, the obtained film can be aligned by the stretching, and can have a delayed retardation of a desired size. In the present invention, the in-plane phase difference 値Ro in the range of 5 8 9 nm is 30 to 10 0 nm, and more preferably 40 to 70 nm. Further, the phase difference 値Rt in the thickness direction is 70 to 300 nm, and it is more appropriate to be 1 0 0 to 2 5 0 nm. The retardation can be controlled by the retardation and stretching ratio of the sheet before stretching, the stretching temperature, and the thickness of the stretched alignment film. The film having a certain thickness before stretching has a tendency that the film having a larger stretching ratio tends to have a larger absolute retardation, so that a stretched alignment film which is delayed by a stretching ratio can be obtained. The measurement deviation of the retardation is preferably as small as possible. The retardation of the cycloolefin polymer film of the present invention is usually within ±50 nm, preferably less than 30 nm, more preferably less than 2 nm. Below 0 nm. The deviation or thickness unevenness in the retarded surface can be made smaller by applying an equal stress to the sheet in addition to the use of the sheets before the stretching. Therefore, under a uniform temperature distribution, it is preferably within the range of 5 Å, and more preferably within, particularly preferably: t 〇 5t: stretching in an environment with controllable temperature is desirable. -64-200821642 [Polycarbonate-based film] In the various ways of producing a polycarbonate-based resin for polycarbonate film, aromatic polycarbon is preferable in terms of chemical properties and physical properties, especially double Phenol A-based polycarbonate is preferred. Further preferably, bisphenol A is introduced into a phenol A derivative such as a benzene ring, a cyclohexane ring or an aliphatic hydrocarbon group, and particularly a derivative which is asymmetric with respect to the central carbon. It is preferred that the polycarbonate obtained is a structure having a reduced intramolecular specificity. For example, in the case where the two methyl groups in the center of bisphenol A are substituted with a benzene ring, it is preferred that the methyl group or the phenyl group of one of the benzene rings of bisphenol A is asymmetrically substituted with respect to the central carbon. Specifically, a compound obtained by a phosgene method or a transesterification method from 4,4'-dihydroxydiphenylalkane or the halogen may, for example, be 4J hydroxydiphenylmethane, 4,4'. - Dihydroxydiphenylethane, 4,4'-dihydroxyphenylbutane, and the like. The retardation film used in the polycarbonate resin of the present invention is mixed with a transparent resin such as a polystyrene resin, a methyl methacrylate resin or a cellulose ester resin, and is also used in a cellulose acetate film. It is also possible to laminate the polycarbonate resin on at least one side. The method for producing the polycarbonate-based film which can be used in the present invention is not limited. Any one of a film obtained by extrusion, a film by a solvent casting method, a film by calendering (c a 1 e n d e r), or the like may be used. The present invention uses either one of 1-axis stretching or 2-axis stretching, and the same manufacturing method as the cellulose ester, the temperature of the present invention is 23 ° C, and the acid ester is a double-introduction carbon. The hydrogen is replaced by carbonic acid by S. One by one and the acetate type is not particularly thin. The film is wettable. -65-200821642 55% The elastic modulus (E23) of the film tensile direction measured under the measurement conditions of RH, and the temperature 5CTC , humidity 55% RH measured under the conditions of the film tensile direction elastic modulus (E5Q) difference (E23-5G) can satisfy the relationship of the formula (1), and can obtain the phase in the in-plane and thickness direction Polycarbonate film in the range of the range. The polycarbonate-based film which can be used in the present invention can be used having a glass transition temperature (Tg) of 110 ° C or higher and a water absorption ratio (measured in 23 ° C water and 24 hours) of 0.3% or less. . More preferably, it is a material having a Tg of 120 ° C or more and a water absorption ratio of 0.2% or less. Here, in order to increase the ratio of the front surface of the liquid crystal display device of the present invention, it is important that the deformation of the polymer constituting the film disposed between the polarizing film and the liquid crystal cell is minimized. As described above, in the stretched film, the polymer constituting the film is quickly aligned, and it is necessary to remove the light leakage as much as possible, and for the same reason, the film thickness of the film is also It is important that the retardation film of the present invention has a film thickness of 100 μm or less. When the film thickness of the film is thicker, the element for causing the light leakage to occur is not only an increase in the film thickness portion, but particularly when the film thickness of the film exceeds 1 μm, a tendency to easily leak light is observed by an increase in film thickness. The film thickness of the appropriate film is 80 μm or less, and the film thickness of the appropriate film is 35 to 60 μm. When the film thickness of the retardation film of the present invention is in the range of 35 to 60 μm, the film of the phase difference film which is used for a thin display such as a large-sized TV in recent years can be sufficiently matched. . -66- 200821642 (Polarizing Plate) The polarizing plate can be produced by a general method. The inner surface side of the retardation film of the present invention is subjected to alkali saponification treatment, and is immersed and stretched in at least one surface of the produced polarizing film in an iodine solution, and is preferably laminated using a completely saponified polyvinyl alcohol aqueous solution. On the other hand, even if the film is used, other polarizing plates can be used to protect the film. Commercially available cellulose ester films (eg, Konika Minolta Tac KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, • KC8UY, KC4UY, KC12UR, KC8UCR-3, KC8UCR-4, - KC8UCR-5, KC8UY-HA, KC8UX-RHA KC8UX-RHA-N, manufactured by Konica Minoltaopt Co., Ltd., Fuji Tac TD 8 OUF ? T 8 0 U Ά, T40UZ, anti-reflective film (Fuji Film CV clear view UA), Fuji Photo Film Co., Ltd.). The optically isotropic polarizer protective film having an in-plane retardation Ro of 0 to 20 nm and a Rt of -5 0 to 50 nm is preferable for the retardation film of the present invention. . Further, it is preferable that the polarizing plate protective film has a hard coating layer or an antiglare layer having a thickness of 8 to 20 μm, for example, Japanese Patent Publication No. 2 003 - 礞 1 1 43 33, Japanese Patent Laid-Open A polarizing plate protective film having a hard coat layer or an antiglare layer described in, for example, Japanese Patent Publication No. 2004-203009, and the like. Further, in the hard coat layer or the antiglare layer, an antireflection layer, an antifouling layer or the like is preferably laminated. Alternatively, it is preferable to use a polarizing plate protective film having an optically complementary film and having an optically anisotropic layer formed by alignment of a liquid crystal compound such as a discotic liquid crystal, a rod-like liquid crystal or a cholesteric liquid crystal. For example, an optically anisotropic layer can be formed by the method described in Japanese Patent Laid-Open Publication No. 2003-9-8348. By using in combination with the polarizing plate of the invention of the present invention, it is possible to obtain a liquid crystal display device having excellent planarity and stable viewing angle expansion effect. The polarizing film which is a main component of a polarizing plate means the element which only passes the light of the polarizing surface in a certain direction, and the typical polarizing film currently known is a polyvinyl alcohol type polarizing film, and this is a polyvinyl alcohol type film. The iodine dyed person is dyed with a dichroic dye. The polarizing film is formed by forming a film of a polyvinyl alcohol aqueous solution, stretching it by one axis, or dyeing it, and after performing one-axis stretching of Φ after dyeing, it is preferred to use a material treated with a boron compound for durability treatment. On one surface of the polarizing film, a single side of the optical film of the present invention is bonded to form a polarizing plate. Preferably, it is bonded by a water-based soap adhesive which is completely saponified with polyvinyl alcohol or the like as a main component. Further, ethylene-modified polyvinyl alcohol can be suitably used as a polarizing film. The film thickness of the polarizing film is preferably 5 to 30 μm, particularly preferably 10 to 25 μm. (Display device) # A liquid crystal display device comprising a polarizing plate using the retardation film of the present invention exhibits high display quality as compared with a normal polarizing film. In particular, a multi-domain type liquid crystal display device is more preferably used in a multi-domain type liquid crystal display device in a birefringence mode to further exert the effects of the present invention. Multi-domainization is also suitable for the improvement of the symmetry of the screen display, and reports of various methods have been published in "Maeda, Yamauchi: LCD, 6(3), 303 (2 0 0 2)". The liquid crystal display cell is also described in "Yamada, Yamahara: Liquid Crystal, 7 (2), 1 84 (2003)", but is not limited thereto. -68- 200821642 The polarizing plate of the present invention is a MVA (Multi-do mein Vertical Alig nment) mode represented by the vertical alignment mode, especially in the MVA mode of 4 divisions, and is known as multi-domain by electrode arrangement. The PVA (Patterned Vertical Alignment) mode allows the electrode configuration and the CPA (Continuous Pinwheel Alignment) mode to be integrated with the chiral. In addition, the OCB (Optical Compensated Bend) mode has a proposal to disclose a film with optical biaxiality - "T. Miyashita, T. Uchida: J, SID, 3(1), 2 9 (1995), the inferiority of the present invention can also be exhibited by the display quality of the polarizing plate of the present invention. According to the use of the polarizing plate of the present invention, if the effect of the present invention is exhibited, the liquid crystal mode and the arrangement of the polarizing plate are not limited. The phase difference film of the present invention is preferably used in a vertical alignment mode liquid crystal display device, and particularly preferably a liquid crystal display device used in an MVA (Multi-Domein Vertical Alignment) mode. ® shows the display quality of the unit cell, which is preferably symmetrical in the human eye. Therefore, the case where the unit cell is a liquid crystal display unit cell is displayed, and the domain (d 〇 m a i η ) can be multi-domainized by giving priority to the symmetry of the observation side. The division of the domain 舎! J ' can be determined by a well-known method, and can be determined by considering the properties of a well-known liquid crystal mode by a two-division method, more preferably a four-division method. The liquid crystal display device is being applied as a device for colorization and animation display. In the present invention, the display quality can be improved by contrast or the resistance of the polarizing plate is improved, and the display of the faithful animated surface which can prevent the eyes from being fatigued is feasible. In the liquid crystal display device of the present invention, the polarizing plate using the retardation film of the present invention is disposed only on one surface of the liquid crystal cell or on both sides. In this case, the retardation film of the present invention contained in the polarizing plate is used as a liquid crystal cell side, which contributes to an improvement in display quality. [Embodiment] Hereinafter, examples and comparative examples of the present invention will be described, but the present invention is not limited to the examples. Example 1 (Preparation of main doping) Cellulose acetate propionate 1 〇〇 parts by mass (total degree of substitution 2.50, number average molecular weight 70,000, mass average molecular weight 1 80 000, intrinsic viscosity (IV) 1·4 : It is called cellulose ester A) aromatic terminal ester type plasticizer (an example of compound (1)) 6 parts by mass of 2-(2'-hydroxy-3',5'-di-tertiary butylphenyl)benzotriene Azole (ultraviolet absorber) 1 part by mass of ethyl phenenyl ethyl hydroxyacetate 4 parts by mass of dichloromethane 450 parts by mass of ethyl alcohol 5 parts by mass to prepare a main dope of the above composition. First, methylene chloride and ethyl alcohol were added to the pressure dissolution tank. The cellulose ester oxime was stirred while being charged in a pressure-dissolving tank filled with a solvent. It is heated, stirred, and completely dissolved. Adding a plasticizer and a UV absorber to dissolve in -70-200821642. For this purpose, the filter paper N 〇 · 24 4 manufactured by Anchip Filter Co., Ltd. was used for filtration to modulate the main dope. &lt;Preparation of fine particle dispersion&gt; Microparticles (Aerosil R972V (manufactured by Nippon Aerosil Co., Ltd.) 11 parts by mass (average diameter of primary particles: 16 nm, apparent specific gravity: 90 g/liter) Ethyl alcohol, 8 parts by mass, using the above material as a dissolver After stirring and mixing for 50 minutes, dispersion was carried out by Manton-Gaulin to prepare a fine particle dispersion. 9 9 parts by mass of 4 parts by mass of 1 part by mass &lt;modulation of fine particle addition liquid&gt; dichloromethane cellulose ester A microparticle dispersion The cellulose ester A was added to a dissolution tank of methylene chloride, and the cellulose ester A was added thereto, and the mixture was heated to completely dissolve the mixture. Then, the filter paper No. 244 manufactured by Angki Paper Co., Ltd. was used for filtration. The fine particle dispersion was gradually added thereto while being stirred, and the dispersion was carried out using an attritor to set the particle size of the secondary particles to a predetermined size. (fine pore) NF filtration to prepare a fine particle addition liquid. Next, add 100 parts by mass of the main doping liquid and 5 parts by mass of the fine particle addition liquid to the on-line mixer (Toray still In-line mixer ‘Hi- - 71 - 200821642

Mixer, SW)) was thoroughly mixed, and then uniformly cast using a belt casting device with a 2 m wide stainless steel band support. The stainless steel strip support was peeled off under the conditions of a peeling tension of 130 N/m and a residual solvent amount of 1 〇〇% by mass. The temperature of the stainless steel belt is divided into two equal parts from the distance from the casting to the stripping, and the average temperature is maintained at 32t before the halving, and the average temperature in the second half is maintained at 28 °C to control the supply to the belt. The temperature of the surface and the inner surface φ wind temperature. - Next, the both ends in the widthwise direction of the mesh (film) are held by a stretcher at a temperature of 140 ° C, a draw ratio of 1.25 times, and a draw speed of 40 mm / sec. After stretching, heat treatment was carried out at 130 ° C for 20 minutes while maintaining the width thereof, and the width was kept relaxed after the tension in the broad direction was relaxed, and further, the third drying zone set at 1 25 ° C was carried out. The film was dried for 0 minutes to produce a phase difference film having a width of 1 · 4 η η and a thickness of 1 cm and a height of 6 μm knurled with a film thickness of 45 μm. * Example 2 The main doping and fine particle addition liquid system were the same as in Example 1, and the temperature of the stainless steel band and the stretching conditions by the stretcher were changed as follows to form a film. The average temperature of the first half of the stainless steel strip was 35 °C, and the average temperature of the second half was 25T: The stretch condition of the stretcher was made at a temperature of 130 艽, a draw ratio of 1.23 times, and a draw speed of 40 mm/sec to prepare a retardation film. . Except for the above conditions, the same procedure as in the first embodiment was carried out. -72-200821642 Example 3 The main doping and fine particle addition liquid system was the same as in Example 1. The temperature of the stainless steel strip was changed, and the stretching conditions by the stretcher were changed as follows. The average temperature of the first half of the stainless steel strip was 30 ° C, the average temperature of the second half was 33 ° C, and the stretching conditions of the stretcher were made at a temperature of 135 ° C, a draw ratio of 1.3 times, and a tensile speed of 34 mm / sec. Phase difference film. The above conditions were carried out in the same manner as in Example 1 except for the above conditions. Example 4 The adjustment of the main doping was carried out under the second conditions. The type of the raw material used was the same as in Example 1, and the doping was carried out by changing the ratio of dichloromethane to ethyl alcohol. Cellulose acetate vinegar vinegar 1 0 0 parts (total degree of substitution 2.50, number average molecular weight 70,000, mass average molecular weight 1 80000' intrinsic viscosity (ΐν) ι·4: called cellulose ester a) aromatic terminal ester a plasticizer (an example of a compound ()) 6 parts by mass of 2-(2'-hydroxy-3',5'-di-tertiary butylphenyl)benzotriazole (ultraviolet absorber) 1 part by mass ethyl 4 parts by mass of o-phenyl-mercaptoethyl group acetate, monochloromethane; U 4 0 parts by mass of ethyl alcohol 10 parts by mass - 73-200821642 Hereinafter, film formation was carried out by the same method as in Example 1. membrane. At this time, the temperature of the warm air supplied to the surface of the belt and the inner surface was controlled so that the temperature of the first half of the stainless steel strip and the temperature of the second half were maintained at 28 °C. Further, the stretcher stretching conditions were carried out under the conditions of a temperature of 145 ° C, a draw ratio of 1.35 times, and a draw speed of 30 mm / sec to prepare a retardation film. Film formation was carried out in the same manner as in Example 1 except for the other parts which were not described. - Example 5 (Adjustment of main doping) The type of the raw material used was the same as in Example 1, and the doping concentration was adjusted to the following manner. 100 parts by mass of cellulose acetate propionate (total degree of substitution 2 · 50, number average molecular weight 7 0 0 0 0, mass average molecular weight 1 80000, intrinsic viscosity (IV) 1 · 4 : called cellulose ester A Aromatic terminal ester type plasticizer (an example of compound (1)) 6 parts by mass of 2-(2'-hydroxy-3',5'-di-tertiary butylphenyl)benzotriazole (ultraviolet absorber) 1 part by mass of ethyl phthalyl ethyl hydroxyacetate, 4 parts by mass of dichloromethane, 60 parts by mass of ethyl alcohol, 40 parts by mass or less, and film formation was carried out in the same manner as in Example 。. At this time, the temperature of the first half of the stainless steel strip and the temperature of the second half are maintained at 25. (: The method to control the temperature of the warm air supplied to the surface of the belt and the inner surface. • 74- 200821642 In addition, the stretching conditions of the stretcher are at a temperature of 130 ° C, a draw ratio of L35 times, and a tensile speed of 50 mm / sec. A retardation film was produced under the conditions. The other portions were not formed, and film formation was carried out in the same manner as in Example 1. Examples 6 and 7 (Adjustment of main doping)

The type of the raw material used was the same as in Example 1, and the doping concentration and the solvent mixing ratio were adjusted in the following manner. Cellulose acetate propionate 100 mass stealing (total degree of substitution 2.50, number average molecular weight 70,000, mass average molecular weight 1 8 0000, intrinsic viscosity (1 ¥) 1.4: called cellulose ester VIII) aromatic terminal ester system plastic Agent (Compound-Example (1)) 6 parts by mass of 2-(2'-hydroxy-3',5'-di-tertiary butylphenyl)benzotriazole (ultraviolet absorber) 1 part by mass of ethyl ortho The film formation of the film was carried out in the same manner as in Example 1 except that the amount of the benzodiazetoethyl glycolate was 4 mass parts: methylene chloride, 320 parts by mass of ethyl alcohol, 80 parts by mass or less. In Example 6, the temperature of the warm air supplied to the surface of the belt and the inner surface was controlled so that the temperature of the first half of the stainless steel belt was maintained at 3 8 Torr and the temperature of the second half was maintained at 40 Torr. Further, the condition of the stretcher was to produce a retardation film at a temperature of 1 5 5 ° C, a draw ratio of 1.35 times, and a draw speed of 30 mm / sec. In Example 7, the temperature of the warm air supplied to the surface of the belt and the inner surface was controlled by maintaining the temperature of the first half of the stainless steel strip at 35 and then -75-200821642 while maintaining the half temperature at 33 °C. Further, the stretcher was subjected to stretching conditions at a temperature of 15 (TC, a draw ratio of 1 · 35 5 times, and a draw speed of 15 mm / sec.) A retardation film was produced. Example 1 was carried out in the same manner as in Example 1. • Example 8: Using the same main doping as in Example 5, the supply of the stainless steel strip was maintained at 22 ° C and the latter half temperature was maintained at 33 ° C to control the supply. The temperature of the warm air with the surface and the inner surface. Further, the stretching condition is to produce a retardation film at a temperature of 1600, a draw ratio of 145 times, and a tensile speed of 2 5 mm/sec. The other parts which were not described were film-formed in the same manner as in Example 1. Example 9 'In the case of main doping adjustment, the following cellulose ester was used instead of cellulose ester A, and a stretching temperature of 135 ° was produced. C, a draw ratio of 1.29 times, and a film thickness of 45 μm. The temperature of the stainless steel strip is controlled to be supplied to the belt surface by maintaining the first half temperature at 3 (TC and the latter half temperature is maintained at 35 ° C). And the temperature of the warm air inside. The above is the same as the case of the first embodiment. -76- 200821642 (Modulation of main doping) Cellulose acetate butyrate 100 Stomach i parts (total degree of substitution 2.42, number average molecular weight no 〇〇〇, weight average molecular weight 230,000 intrinsic viscosity (IV) 1, 4) Aromatic terminal ester type plasticizer (an example of compound (1)) 6 parts by mass of 2_(2'-hydroxy-3',5'-di-tertiary butylphenyl)benzotriazole (ultraviolet absorber) 1 mass The ethylidene phthalate ethyl hydroxyacetate 4 parts by mass of the dichlorocarbyl 225 parts by mass of the ethyl alcohol 25 parts by mass to prepare the main doping liquid of the above composition. Hereinafter, the conditions until the casting are Example 1 was carried out in the same manner. The temperature of the stainless steel was set so that the average temperature of the first half was maintained at 20. (:, after • ί. The average temperature of the half was kept at 30 ° C to control the supply to the surface of the belt and the inner surface. The temperature of the warm air. The stretching condition of the stretcher is to produce a retardation film at a temperature of 158 ° C, a draw ratio of 1.34 times, and a draw speed of 15 mm / sec. Example 1 〇 at the time of main doping modulation , using the following cellulose ester instead of cellulose ester A, at the time of main doping adjustment, use the following fiber The ester of the stainless steel strip was prepared by replacing the cellulose ester A with a stretching temperature of 1 4 5 ° C, a draw ratio of 1.66 times, and a tensile speed of 45 mm/sec. 77 - 200821642 The temperature of the warm air of the belt surface and the inner surface was controlled so that the temperature of the first half was maintained at 40 ° C and the temperature of the second half was maintained at 35 ° C. The above was carried out in the same manner as in the first embodiment. Cellulose acetate butyrate: total substitution 2.42, number average molecular weight 11 000, mass average molecular weight 230,000, intrinsic viscosity (IV) 14. Example 1 1 At the time of main doping adjustment, the following cellulose ester was used in place of cellulose ester A, and at a stretching temperature of 175 ° C, a stretching ratio of 155 times, and a stretching speed of 1 A retardation film was produced at 5 mm/sec. At this time, the temperature of the stainless steel strip can be controlled at a temperature of 20 ° C together with the temperature of the first half and the second half to control the temperature of the warm air supplied to the surface of the belt and the inner surface. Except for the above, it was carried out in the same manner as in the case of Example 1. Cellulose acetate butyrate: total substitution 2.7 9, number average molecular weight: 1 5 0000 'mass average molecular weight 3 00000, intrinsic viscosity (IV) 2.2. Example 1 2 Preparation of a cycloolefin-based polymer film by melt-flow casting film method Under a nitrogen atmosphere, 500 parts of dehydrated cyclohexane, 1-hexene 1-2.2 parts, dibutyl ether 0.15 Parts, triisobutylaluminum hydrazine. 30 parts were placed in the reactor at room temperature and mixed, while maintaining at 45 Τ: while tricyclic [4·3·0·12,5]癸-3,7- 20 parts of a diene (dicyclopentadiene, hereinafter abbreviated as DCP), 140 parts of 1,4-methylene-l,4,4a,9a-tetrahydroanthracene (hereinafter, MTF for short), and 8-methyl- Tetracycline [4·4·0·12,5·17,10]-dodec-3-ene (hereinafter, abbreviated as -78 - 200821642 MTD) 40 parts of a terpene-based monomer mixture, and hexachlorinated 40 parts of tungsten (0.7% toluene solution) was polymerized by continuous addition over 2 hours. In the polymerization solution, 6 parts of butyl glycidyl ether 1·〇 and 0.52 parts of isopropyl alcohol were added to inertize the polymerization catalyst and the polymerization reaction was stopped. Then, 270 parts of cyclohexane was added to 100 parts of the reaction solution containing the obtained ring-opening polymer, and further 5 parts of a nickel-alumina catalyst (manufactured by Nippon Chemical Co., Ltd.) was added to the hydrogenation catalyst to hydrogen addition. The pressure was changed to 5 MPa, and the mixture was heated to a temperature of 200 ° C while stirring, and then reacted for 4 hours to obtain a reaction solution containing 20% of a DCP/MTF/MTD ring-opening polymer hydrogenated polymer. After the hydrogenation catalyst was removed by filtration, a soft polymer (manufactured by Kuraray Co., Ltd.; septon 2002) and an antioxidant (manufactured by Chiba Special Chemicals Co., Ltd.; Irganoxs 1 0 10 0) were each added to the obtained solution and dissolved. (all 0.1 parts per 1 part of the polymer). Then, the cyclohexane and other volatile components from the solution were removed using a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.), and the hydrogenated polymer was extruded into a strand shape from the extruder in a molten state. After cooling, it is granulated and recovered. The copolymerization ratio of each of the decene-based monomers in the polymer is calculated as DCP/MTF/MTDM 0/7 0/2 when the composition of the remaining 71 olefins in the solution is reduced (caused by gas chromatography). 0 is approximately equal to the load composition. The ring-opened polymer hydride had a mass average molecular weight (Mw) of 31,000, a molecular weight distribution (Mw/Mn) of 2.5, a hydrogenation rate of 99.9%, and a Tg of 134 〇C. -79- 200821642 The obtained particles of the ring-opening polymer hydride are removed by using a hot air dryer which circulates air at 7 (TC is dried for 2 hours to remove moisture. Next, the pellet is used to have a mouthpiece (Π p) A single-axis extruder with a width of 1.5 m and a T-die of a hanger type (manufactured by Mitsubishi Heavy Industries Co., Ltd.: a spiral diameter of 90 mm, a T-die member with a tungsten carbide, and a peeling strength of molten resin of 44 N), which is melt-extruded. A film of a cyclic olefin resin having a length of 2,500 m and a thickness of 60 μm is produced. The extrusion molding is carried out in a clean φ room of a grade of 1 0000 or less, at a temperature of 24 〇t at a molten resin: and a molding temperature of 240 ° C at a mold temperature. In the same manner as the retardation film of Example 1, the film was peeled off at a peeling tension of 85 N/m, a residual solvent amount of 5 mass%, and a cold air temperature of 23 ° C, and the both ends of the mesh were held by a stretcher. As shown in Fig. 2, the stress from the start of the step B to the position of 10 cm is 135 N/mm, the temperature is 160 ° C, and the stretching ratio is 1.3 times, and the obtained cyclic olefin resin film is coated on both sides. Open a slit, add The width is 1.4 m, and the retardation film 17 having a film thickness of 80 μm is obtained. Further, the protective film is wound around the polyester film at the time of winding, thereby producing the ultraviolet ray in the thickness direction of the film. The distribution of the agent was measured in accordance with the method for measuring the amount of the additive described later, and the results are shown in Table 1. Example 13 Production of a polycarbonate-based film by a solution casting method Film formation &lt;Doping composition&gt; Resin-80- 200821642 (viscosity average molecular weight 40,000 'bisphenol A type) 100 parts by mass of Lu 2-(2'-hydroxy-3',55-di-tertiary butylphenyl)benzotriazole (UV absorption) (Agent) 0 parts by mass of dichloromethane 430 parts by mass of methanol 90 parts by mass The above-mentioned composition was placed in a sealed container, and the mixture was kept at 80 ° C under pressure while stirring, and completely dissolved to obtain a doping composition.

Next, the doping composition was filtered, cooled and kept at 33 ° C, uniformly cast on a stainless steel belt support, and dried at 33 ° C for 5 minutes. Then, when the web (film) was peeled off from the support, the peeling tension was 1 20 N/m, the residual solvent amount was 45% by mass, and the cold air temperature was 23 ° C, similarly to the retardation film of Example 1 described above. The conditions are peeled off, and the ends of the mesh are held by the stretcher, and the stress from the start of the step B to the position of 10 cm as shown in Fig. 2 is 140 N/mm, the temperature is 125 ° C, and the stretching ratio is increased. The film was stretched under conditions of 1.21 times, and subjected to a stretching treatment to obtain a phase difference film having a stomach width of 1.4 m and a film thickness of 65 μm. The distribution of the ultraviolet absorber in the thickness direction of the film thus produced is measured in accordance with the method of measuring the additive * described later, and is shown in Table 1. Comparative Example 1 (Preparation of main doping) Cellulose acetate propionate 100 mass parts (total degree of substitution 2.50, number average molecular weight 70,000, weight average molecular weight 1 80 000, intrinsic viscosity (IV) 1.4 : called fiber Ester ester Α) -81 - 200821642 Aromatic terminal ester plasticizer (an example of compound (1)) 2-(2, hydroxy-3', 5, di-tert-butylphenyl) 6 parts by mass of benzotriazole (Ultraviolet absorber) 1 part by mass of ethyl phenenyl ethyl hydroxyacetate 4 parts by mass of dichloromethane 470 parts by mass of ethyl alcohol 3 parts by mass to prepare a main dope of the above composition. First, dichloromethane and ethyl alcohol were added to the pressure dissolution tank. The cellulose ester A was stirred while being charged in a pressure-dissolving tank filled with a solvent. This is heated, stirred while being completely dissolved, and then a plasticizer and an ultraviolet absorber are added and dissolved. In this case, the main mixed solution was prepared by filtering using the filter paper No. 244 manufactured by Anchip Paper Co., Ltd. The adjustment of the fine particle dispersion and the adjustment of the fine particle addition liquid were carried out in the same manner as in the description of Example 1. Next, 1 part by mass of the main doping solution was added, and 5 parts by mass of the microparticle-added liquid was thoroughly mixed with an in-line mixer (Toray static in-line mixer, Hi-Mixer, SWJ), followed by strip casting. The device was uniformly cast in a stainless steel belt support having a width of 2 m. On the stainless steel belt support, peeling was carried out under the conditions of a peeling tension of 130 N/m and a residual solvent amount of 100% by mass. The temperature of the stainless steel belt was such that the average temperature of the first half was maintained at 30 ° C, and the average temperature of the latter half was maintained at 25 ° C to control the temperature of the warm air supplied to the surface of the belt and the inside. The stretching condition of the stretcher was to produce a retardation film under the conditions of a temperature of 12 (TC, a draw ratio of 1.2 times, and a draw speed of 40 mm/sec. -82- 200821642 Comparative Example 2 (modulation of main doping) Cellulose B 100 parts by mass of ester propionate (total degree of substitution 2 · 50, number average molecular weight 7 0 0 0 0, weight average molecular weight 1 80000, intrinsic viscosity (IV) 1 · 4 : called cellulose ester a) aromatic Terminal ester plasticizer (an example of compound (1)) 6 parts by mass

2-(2'-hydroxy-3',5'-di-tertiary butylphenyl) benzotriazole (ultraviolet absorber) 1 part by mass of ethylphthalic acid ethyl glycolate 4 mass A main dope of the above composition was prepared by dissolving 630 parts by mass of methylene chloride (70 parts by mass) of ethyl alcohol. Hereinafter, the conditions up to the casting are carried out in the same manner as in the first embodiment. The temperature of the stainless steel strip was such that the average temperature of the first half was maintained at 15 ° C, and the average temperature of the latter half was maintained at 20 ° C to control the temperature of the warm air supplied to the surface of the belt and the inside. The stretcher stretching conditions were made at a temperature of 11 or more, a draw ratio of 1.15 times, and a draw speed of 20 mm/sec to prepare a retardation film. Comparative Example 3 The adjustment of the main doping was carried out in the same manner as in Example 1, and the temperature of the warm wind supplied to the surface of the belt and the inner surface was controlled so that the temperature of the stainless steel strip was kept at an average temperature of 55 ° C in the first half and the second half. . The stretcher stretching conditions were carried out under the conditions of a temperature of -83 to 200821642 140 ° C, a draw ratio of 1.30 times, and a draw speed of 70 mm / sec to prepare a retardation film. Comparative Example 4 The adjustment of the main doping was the same as in Example 1, and the temperature of the stainless steel strip was maintained. The average temperature of the first half was maintained at 25 ° C, and the average temperature of the latter half was maintained at 15 ° C to control the supply to the belt surface. The temperature of the inner wind. Stretcher The stretch condition was made at a temperature of 1 〇 〇 ° C, a draw ratio of 1.1 times, and a draw speed of 2 〇 mm / sec. Comparative Example 5 The adjustment of the main doping was the same as in Example 1, and the temperature of the stainless steel strip was maintained, the first half average temperature was maintained at 35 ° C, and the latter half average temperature was maintained at 20 ° C to control the temperature supplied to the belt surface and the inner surface. The temperature of the wind. The stretcher was subjected to a retardation film at a temperature of 105 ° C, a draw ratio of 1.17 times, and a draw speed of 40 mm / sec. Comparative Example 6 The adjustment of the main doping was carried out in the same manner as in Example 1, and the temperature of the stainless steel was maintained so that the average temperature of the first half was maintained at 15 ° C, and the average temperature of the latter half was maintained at 30 ° C to control the supply to the surface of the belt. The temperature of the warm wind. The stretching condition of the stretcher was to produce a retardation film at a temperature of 1 75 ° C, a draw ratio of 1.43 times, and a draw speed of 30 mm / sec. -84- 200821642 Comparative Example 7 (Preparation of main doping) Cellulose acetate propionate (total degree of substitution 2.60, number average molecular weight 80000, weight 1 90000, intrinsic viscosity (IV) 1.7) Aromatic terminal ester type plastic Agent (compound example (1)) 2-(2'-hydroxy-3',5'-di-tertiary butylphenyl) benzotriazole (ultraviolet absorber) ethyl phthalic acid ethyl hydroxy Acetate dichloromethane ethyl alcohol modulates the main dope of the above composition. Hereinafter, the conditions for the casting are the same as in the first embodiment, the temperature of the stainless steel strip is the same, and the temperature of the warm air supplied to the surface of the belt and the inner surface is controlled by the average temperature in the first half and the second half at a temperature of 100 ° C. The retardation film was produced under the condition of 1.30 times magnification and pulling seconds. Comparative Example 8 (Preparation of main doping) Cellulose acetate butyrate (total degree of substitution 2.42, number average molecular weight 1 1 〇〇〇〇, amount 230,000, intrinsic viscosity (IV) 1.4) Aromatic terminal ester type plastic Agent (Example (1) of compound) 100 parts by mass of an average molecular weight of 6 parts by mass of 1 part by mass of 4 parts by mass of 4 parts by mass of 1 part by mass of I. t is the square of 15 °c. Stretcher stretching speed l〇mm/100 parts by weight weight average molecule 6 parts by mass -85- 200821642 1 part by mass 4 parts by mass 350 parts by mass 1 50 parts by mass 2-(2'-hydroxyl3' , 5, di-tertiary butylphenyl) benzotriazole (ultraviolet absorber) Ethyl phthalate ethyl hydroxyacetate dichloromethane ethyl alcohol The main doping solution of the above composition was prepared. Hereinafter, the conditions up to the casting were carried out in the same manner as in Example 1.

The temperature of the stainless steel strip was maintained at a temperature of 35 ° C in the first half and the average temperature in the latter half was maintained at 25 ° C to control the temperature of the warm air supplied to the surface of the belt and the inner surface. The stretcher stretching conditions were such that a retardation film was produced under the conditions of a temperature of 1 3 5 ° C, a draw ratio of 1.28 times, and a draw speed of 35 mm/sec. Comparative Example 9 (Preparation of main doping) 100 parts by mass of cellulose acetate butyrate (total degree of substitution 2.42, number average molecular weight lioooo, weight average molecular weight 23 0000, intrinsic viscosity (IV) 1.4) Aromatic terminal ester system Plasticizer (an example of compound (1)) 6 parts by mass of 2-(2,-hydroxy-3,5'-di-tertiary butylphenyl) benzotriazole (ultraviolet absorber) 1 part by mass of ethyl ortho To the benzene dimercaptoethyl glycol acetate 4 parts by mass of dichloromethane 225 parts by mass of ethyl alcohol 25 parts by mass, the main dope of the above composition was prepared. -86-200821642 Hereinafter, the conditions up to the casting were carried out in the same manner as in Example 1. The temperature of the stainless steel strip is maintained at a temperature of 2 (TC, and the average temperature of the latter half is maintained at 30 ° C to control the temperature of the warm air supplied to the surface of the belt and the inner surface. The tension condition of the stretcher is 1 A retardation film was produced under the conditions of a stretching ratio of 1.34 times and a stretching speed of 15 mm/sec at 58 ° C. Evaluation test • The phase difference-film obtained in the above Examples 1 to 13 and Comparative Examples 1 to 9, The elastic modulus (E23) of the film stretching direction under the measurement conditions of a temperature of 23 ° C and a humidity of 55% RH, and the tensile direction of the film measured under the measurement conditions of a temperature of 50 ° C and a humidity of 55% RH were measured. The elastic modulus (E5〇), and the difference between the elastic modulus (E23) and the elastic modulus (E5G) (Ε23·5〇), and the results obtained are shown in Table 1 below. [Measurement of the modulus of elasticity] • The above implementation The samples of the retardation films obtained in Examples 1 to 13 and Comparative Examples 1 to 9 were placed in an environment of a temperature of 23 ° 2 and a humidity of 55 ± 5 % RH for 14 hours, and the TD direction of each sample was made long. In the way of the side, cut into a thin rectangular shape with a width of lOmmx and a length of 200 mm. Then, using Minebea The TG-2KN tensile tester made by the company has a chucking pressure of 0.25 MPa and a distance between the marking lines of 100 ztlOmm. The thin rectangular sample is set and stretched at a tensile speed of 100 ± 10 mm/min. The tensile test is carried out in the same environment as in the cutting. 妾 , 以 以 以 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸 拉伸The wiring drawn between them is extrapolated'. The elastic modulus (E23) in the MD direction and the TD direction is obtained for each sample. Further, the setting of the film setting portion and the chuck @份' of the tensile testing machine can be arbitrarily selected. The unit for heating and humidifying keeps the inside of the chamber at a temperature of 50 ± 2 ° C 'humidity 55 ± 5% RH. After each sample is sterilized in the above-mentioned library for 2 hours, the same method as described above is carried out. In the tensile test, the elastic modulus (E 5 〇) was obtained for each sample. Further, the in-plane retardation 値R 〇 was measured in the retardation film obtained in the above Examples 1 to 13 and Comparative Examples 1 to 9, and the thickness direction was The results obtained by the phase difference 値Rt ' are shown in Table 1 below. [Surface plastic dose The amount of the additive on the surface of the film is about 10 μm from the surface of the film using a cutter. After the mass is measured, it is dissolved in acetone. The amount of the additive contained therein is gas tomography (using HP). Gas Chromatography Model 5 890 SERISII) Method for Quantitative Analysis [Phase Difference 値R〇, Rt Measurement] The above Examples 1 to 13 and Comparative Example 1 were measured using an ABB refractometer (1 T) and a spectroscopic light source. The average refractive index of each sample of the retardation film obtained in ～9. Further, the thicknesses of the respective samples of the retardation films obtained in the above Examples 1 to 13 and Comparative Examples 1 to 9 were measured using a commercially available micrometer. Using an automatic complex refractometer KOBRA-21ADH (manufactured by Oji Scientific Instruments Co., Ltd.), it was allowed to stand for 24 hours in an environment of a temperature of 23 ° C and a humidity of 55% RH - 88 - 200821642 The above Examples 1 to 13 and Comparative Examples 1 to 9 The obtained phase samples were subjected to delayed measurement of each sample at a wavelength of 5 89 nm under the same environment. The average refractive index and the film thickness are input to the following equations, the position difference 値R〇, and the phase difference 値Rt in the thickness direction. Also, the direction of the axis. The phase difference film of the dislocation film is used to determine the phase in phase.

Ro=(nx-ny)xd Rt={(nx + ny)/2-nz}xd where nx shows the refractive index of the phase in the axial direction of the film in the plane of the film, and the refractive index in the direction of the in-phase axis of the film surface, nz shows The film thickness ratio, d is the thickness (nm) of the film. Next, using the samples of the above-described Examples 1 to 13 and the comparative retardation film, the evaluation of the polarized light was carried out in the following manner. The inch rate, ny shows the plate obtained by the refraction of the thinness direction 1 1 to 9, and the following "production of a polarizing plate" is carried out. The polyvinyl alcohol film having a thickness of 120 μm is subjected to 1 l 〇 ° C, and the stretching ratio is 5 times. ). This was immersed in an aqueous solution of iodine.075S '100 g for 60 seconds, followed by immersion in an acid solution of 7.5 g of acid and 100 g of water to make a solution at 68 °C. Make a polarizing film. Then, according to the following steps 1 to 5 ', the polarizing® is axially stretched (temperature 5 g of potassium telluride, potassium iodide 6 g, boron; washed with water, dried and obtained, and the above-mentioned implementation -89-200821642 examples 1 to 1 3 and The surface side film of each sample of the retardation film obtained in Comparative Examples 1 to 9 was bonded to a Konica MinoltaTac KC8UX-RHA film (manufactured by Konica Minolta opt Co., Ltd.) of the cellulose ester film on the inner surface side to prepare a polarizing plate. Step 1: Each sample of the retardation film obtained in the above Examples 1 to 13 and Comparative Examples 1 to 9 was immersed in a sodium hydroxide solution at a temperature of 5 Torr: 1 mol/L for 60 seconds, followed by dipping. The mixture was washed with water and dried to obtain a cellulose ester film which was saponified on the side where the polarizing film was bonded. Further, each of the samples of the retardation films obtained in Examples 1 2 and 13 and Comparative Examples 6 and 7 was subjected to plasma treatment. In place of the saponification treatment step and hydrophilization. Step 2: The polarizing film is immersed in a polyvinyl alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds. Step 3; Attached to the polarizing film in Step 2. Excess adhesive is gently wiped off to place it The antireflection layer is laminated on each of the samples of the retardation film treated in the step 1, and the antireflection layer is laminated on the outer side. Step 4: The retardation film and the polarizing film and the cellulose which are laminated in the step 3 are laminated. The ester film sample was bonded at a pressure of 20 to 30 N/cm 2 and a conveying speed of about 2 m/min. Step 5: The above Examples 1 to 13 and Comparative Examples 1 to 9 which were produced in the step 4 in an 80-charge dryer were used. Each of the obtained phase difference film samples was dried with a polarizing film and a cellulose ester film to form a polarizing film for 2 minutes. "Production of Liquid Crystal Display Device" -90-200821642 Commercially available liquid crystal TV The polarizing plate of the aquos 32AD5 manufactured by Sharp Corporation was peeled off, and the polarizing film produced by using the retardation films obtained in the above Examples 1 to 13 and Comparative Examples 1 to 9 was bonded to the glass surface of the liquid crystal cell. The bonding direction of the polarizing plate is such that the surface of each of the retardation films is on the liquid crystal cell side, and the liquid crystal display device is produced by moving toward the absorption axis in the same direction as the polarizing plate to be bonded in advance. "Inconsistent corners of the substrate Evaluation" The polarizing film produced by using the retardation film obtained in the above Examples 1 to 13 and Comparative Examples 1 to 9 was used, and each liquid crystal display device using the polarizing film was at a temperature of 45 ° C ± 2 ° C. Store in a humidity of 95% 3% RH for 24 hours. Immediately thereafter, move to a room with a temperature of 23 °C and a humidity of 55% RH. The panel backlight will be lit. After lighting for 24 hours, the measurement is in black. In the fourth corner of the corner, the average 値 is calculated. In addition, the term "four corners" as used herein means that the distance from the corner is 50 mm on the diagonal of the effective display screen. In each liquid crystal display device, the occurrence of unevenness of the substrate corners is evaluated by the following five stages by the ratio of the front luminance average 値 of the four corners to the front luminance of the center portion of the screen. The rating is as follows. Further, the front luminance of the center portion of the screen of the liquid crystal display device is set to 1. The results obtained are shown in Table 1 below. Evaluation Level • 91 - 200821642 A : No unevenness of the substrate corners (average brightness of the four corners; 1.00 to 1.05) B: Unevenness of the substrate is not recognized by the naked eye (average brightness of the four corners; 1.06 to 1.10) C : It can be seen that the edge of the substrate is uneven, and it is not accessible when used (four-corner front brightness average; 1.11~1.20) D: There is a problem in display quality (four corner front brightness average; 1.21~1·30) Ε: display There are major problems in quality (four corners of the front brightness average; more than 1.31) -92- 200821642

[Is substrate edge unevenness level &lt;&lt;&lt;&lt;&lt;&lt;&lt; PQ PQ PQ PQ uuu QQQQQQQWW /-NS 1 in mr-t rs| r-H o 宕o &lt;N CN 〇o τ- H o tH O o O omo (N tn ON § m tH v—i jrj 1—H o rH o (N m ▼-H oo 占1 Nw/ Ο jr&gt; m VO jo tn m 〇»n Os 〇rH o (N 4/Ί m in ^T) |〇沄to V〇o 褂§ i® ill ψ li7 &lt;π An sniper • sea g O vn m SO V〇m 〇〇o ON ▼—i 〇〇 \ oo ON OO oo ft ? 鲣3 jrj 〇mov〇VO 沄»r&gt; § VO- s jrj cn o S v〇mm difference 0^23-50) (GPa) Ο 〇 (N m O o (N m O sogo r- o vn o 〇CN 〇JO 2 so 〇(N mo § oom 〇oo VO 〇r—H o Elasticity (e50) (GPa) cn rn S VO Ό rn g rn OO r4 (M rn mv〇 (N (M rn in 1 -i cn mm rn § (N s rn 00 (N rn o rn rn v〇rn rH! (N &lt; N JO rsi rn Elasticity (e23) (GPa) Ο γ- Γπ 〇 inch P; inch * 〇 inch ' 1—Hi rn et cn s inch · 〇rn p- cn cn s inch · »n rn rn 0\ r〇〇rn ▼-H inch rn or -4 inch o inch · S t-H another · ΓΟ 冢Oi 1 1 Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Example 9 Example 10 Example 11 Example 12 Example 13 Comparison Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 -93-200821642 From the results of Table 1, the polarizing film produced by using the retardation film of Examples 1 to 13 of the present invention was observed. In the liquid crystal panel using the polarizing film, the evaluation results of the unevenness of the substrate corners are grades A to C, and the occurrence of unevenness of the substrate corners of the liquid crystal panel can be improved. Further, according to the retardation film of Examples 1 to 13 of the present invention, in the retardation film, the plasticity of the surface in contact with the polarizing element is less than the plastic amount of the surface contacting the glass side, and the substrate can be greatly suppressed. The unevenness of the corner Φ occurs. - I believe that this system can increase the bonding force between the retardation film and the PVA (polarizing element) while making the surface of the retardation film on the side of the polarizing element low, and on the other hand, the glass of the phase difference film. The surface of the side has a large amount of plasticity, and the stress generated by the contraction of PV A due to the temperature change is relatively weak when the stress is transmitted to the phase difference film, so that the disorder of the birefringence is hard to be caused. On the other hand, in the liquid crystal panel using the polarizing film produced by using the phase difference-thin film obtained in Comparative Examples 1 to 9, the average 値 of the square brightness of the four corners of the liquid crystal panel was 1.21 to 1.30, and the substrate side was used. The evaluation result 1 of the angular unevenness is the grade D. There is a problem that the substrate corners are uneven at the level D, and there is a problem in the display quality of the liquid crystal panel. Further, in the liquid crystal panel using the polarizing film produced by using the retardation film obtained in Comparative Examples 8 and 9, the average 値 of the front luminance of the four corners of the liquid crystal panel was 1.31 or more, and the evaluation result of the unevenness of the substrate corner was grade E. . Significant substrate edge unevenness occurs at level E, and there is a major problem in the display quality of the liquid crystal panel. -94- 200821642 [Simple description of the drawings] [Fig. 1] is an explanatory view showing the stretching angle in the film stretching step. Fig. 2 is a schematic plan view showing an example of a stretching step used in the method of the present invention. [Fig. 3] An example of a stretcher stretching device used in the method of the present invention is a plan view schematically shown in the mode. [Main component symbol description] 1 a : Left wheel chain (rotary drive unit) 1 b : Right wheel chain (rotary drive unit) · 2 a : Left side clamp 2b : Right side clamp 3a: Left side clamp closer (Clip closer 3b; right clamp closer 4a: left grip opener 4b: right clamp opener 10a: stretcher stretching device - 95-

Claims (1)

200821642 X. Patent Application No. 1. A retardation film which is provided in a manufacturing step of a means for holding an end portion of a film and stretching it in a direction orthogonal to a conveying direction, in one part of a film forming step The phase-difference film is characterized in that the elastic modulus (E23) of the film in the tensile direction measured under the conditions of a temperature of 2 3 ° C and a humidity of 55% RH is 3.4 to 4.4 GPa, and at a temperature of 50 ° C, The difference between the measurement conditions of the humidity of 55% RH and the elastic modulus (E5〇) (ΔEu.m) satisfies the following formula (1), and the amount of the additive present on the surface of the retardation film on the side of the bonding element with the polarizing element is mass. When the ratio is 100.0, the amount of the additive existing on the surface of the retardation film on the glass surface side is 20 to 70 by mass ratio, and the formula (1) 0·30'ΔΕ23·50'0·80 △ Ε 2 3 - 5 0 = Ε 2 3 - Ε 5 〇, t η The additive here means that the material constituting the retardation film is intended to be a material other than the main resin and solvent. 2. For the phase difference film of claim 1, wherein the film thickness is 35 to 60 μm. 3. For the phase difference film of claim 1 or 2, the inherent viscosity (IV) of the resin is 1.3 to 1.7. 4. The retardation film according to any one of claims 1 to 3, wherein the main component of the resin is a cellulose ester, and the cellulose ester is selected from the group consisting of cellulose acetate and cellulose acetate. At least one of a group of ester propionate and cellulose acetate butyrate. -96-200821642 5. A retardation film according to item 4 of the patent application, wherein the cellulose ester has a degree of ester substitution of 2.42 to 2.60.