TW200927454A - Phase difference film manufacturing method, phase difference film, polarization plate and liquid crystal display device - Google Patents

Abstract

Provided is a method for manufacturing a phase difference film having at least two optical anisotropic layers different from each other. In the method, a base material layer composed of a positive birefringent polymer is drawn, a negative birefringent polymer solution is applied and dried on the base material layer to form a negative birefringent layer, then, a laminated body of the base material layer and the negative birefringent layer is drawn in a direction orthogonally intersecting with the drawing direction of the base material layer.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a poor film. ^ [Prior Art] In the past, in the liquid crystal, the retardation film has a critical phase difference in the phase difference of the stretching process, and in order to increase the in-plane, the thickness direction is made in the plane. And thickness field] Suitable for liquid crystal panels, etc. - optical compensation, retardation film, and phase plate and liquid using the same

Therefore, in order to take advantage of the difference of the complex phase difference film (for example, it is used for the phase difference plate provided with the deflection process and the viewing angle is increased by the adhesive layer, it is not suitable for use as a display device for optical compensation. A general method for producing a phase can be a method of stretching a polymer in a uniaxial or biaxial manner. However, depending on the optical characteristics of the polymer, it is not possible to obtain a sufficiently widened viewing angle effect phase difference 〇値(R〇値) and is extended. The phase difference 値(Rt値) of the pull also increases or decreases the phase of the desired phase difference 方向 in the direction to further enlarge the viewing angle effect, and the laminated retardation film is expressed, and Patent Document 1). The polarizing plate of the light-protecting film of Patent Document 1 is bonded to form a retardation film to realize a desired method. However, in this method, the retardation film of this portion is required to be controlled by the thin film of the liquid crystal display device which is thinned. For example, there are few treatments, and the technique of layer phase is different from the thickness of the layer. The thickness of the layer must be permeable to the thickness of the structure -4-200927454, and the adhesive layer also becomes the cause of uneven phase difference, especially for high The situation of the liquid crystal display device of image quality sometimes makes the problem significant. Further, since the misalignment between the films and the interface and the adhesive itself are disturbed at the time of bonding, the use of the liquid crystal display device causes a decrease in front contrast. Moreover, it is necessary to adjust the problem of attaching another retardation film, which leads to an increase in cost. [Problem to be Solved by the Invention] The inventors of the present invention have a positive birefringence polymerization having an increased refractive index characteristic in the stretching direction. a birefringent polymer (also known as a negative intrinsic complex refraction) having a negative refractive index in the direction of the tensile direction of the substrate (also a positive intrinsic birefringent polymer) The polymer is applied, dried, and the laminate is stretched, and a phase difference film which optimizes the phase difference 〇 is attempted. However, the expression of the phase difference in the above-described stretching treatment depends on the optical properties of various materials used for the substrate and the coating layer. Therefore, when a negative birefringent polymer layer is formed on a substrate made of a positive birefringent polymer and subjected to a stretching treatment, if the laminate has the necessary in-plane phase difference 厚度 and thickness direction When the phase difference 延 is stretched as a coating layer, the in-plane phase difference of the substrate layer is more than necessary in the stretching direction, and becomes a film which compensates for an uncomfortable phase difference 视野 in the viewing angle, and is difficult to manufacture. A phase difference film of phase difference 値. -5- 200927454 Further, in the case where a birefringent polymer layer is formed on a substrate made of a positively refractive polymer and a phase difference film is to be produced by one-time stretching treatment, it is apparent that a new phase difference does not occur. Problems such as uniformity and haze Therefore, it is an object of the present invention to provide suppression of unevenness in phase difference and degree of occurrence, and to have sufficient optical characteristics in an enlarged viewing angle, and to use a liquid crystal display device or the like to exhibit a high positive surface. A method of producing a phase film of contrast. 〇 (Means for Solving the Problem) The above object of the present invention is achieved by the following constitution. A method for producing a retardation film, which is a method for producing a retardation film having at least two layers of different optical anisotropic layers, characterized in that a substrate layer composed of a positive birefringent polymer is stretched, followed by After the negative birefringent polymer solution is coated on the substrate layer and dried to form a negative birefringent layer, © a laminate of the substrate layer and the negative birefringent layer, with respect to the stretching direction of the substrate (The first extension direction) is extended in the vertical direction (second extension). 2. The method for producing a retardation film according to the above 1, wherein the front substrate layer is a long-length film produced by a solution flow method or a melt flow method, and the base material layer is oriented in a broad axis direction of the long film. extend. 3. The method for producing a retardation film according to the above 1 or 2, wherein the glass transition temperature of the positive birefringent polymer is Tgl, and the glass transition temperature of the negative birefringent polymer is Tg2. , the full negative position of the fog and the difference between the cloth layer to the thin _, eight 刖 foot 200927454 The following formula (1), 0 ° C ^ Tgl -Tg2 ^ 40 ° C ... (1)" 4. A phase difference The method for producing a phase difference film according to any one of the above 1 to 3, wherein the retardation film of the phase difference film produced has a retardation 値R〇1 and a thickness 〇. The retardation 値Rt 1 in the degree direction, the retardation 値R〇2 in the plane of the negative birefringence layer, and the retardation 値Rt2 in the thickness direction have the following formulas (2) to (5) Optical phase difference film -20 ^ Rol ^ 40 ( 2 ) 80 ^ Rtl ^ 160 · ( 3 ) 50 ^ Ro2 ^ 200 (4 ) -180^ Rt2 ^ -80 (5)

However, the refractive index in the second stretching direction in the plane of the substrate layer is nxl, the refractive index perpendicular to the in-plane second stretching direction is nyl, the refractive index in the thickness direction is nzl, and the substrate layer The thickness is set to dl(nm)' The refractive index in the direction perpendicular to the second extension direction in the plane of the negative birefringence layer is nx2, the refractive index in the second extension direction is ny2, and the refractive index in the thickness direction When the thickness of the negative refractive layer of nz2 and negative is set to d2 (nm),

Roa= ( nxa-nya) xda 200927454

Rta=((nxa + nya) /2-nza) xda (wherein a is a one or two of the above), and a method for producing a retardation film according to any one of the above 1 to 4, The negative birefringent polymer is a polymerizable monomer unit having a bonded (heterocyclic) aromatic substituent and a polymerizable moiety and having a minimum number of atoms of 0 or more and 2 or less as a copolymerization component. A retardation film produced by the production method according to any one of the above-mentioned items 1 to 5. A polarizing plate </ RTI> characterized in that it has a retardation film as described above on at least one side. A liquid crystal display device comprising a polarizing plate according to the above 7 on at least one surface of the liquid crystal element. (Effects of the Invention) According to the present invention, it is possible to provide suppression of unevenness in phase difference and occurrence of haze. * It has sufficient optical characteristics in an enlarged viewing angle, and exhibits high front contrast in the case of a liquid crystal display device or the like. A method of producing a retardation film. [Embodiment] The best mode for carrying out the invention will be described in detail below, but the invention is not limited thereto. The method for producing a retardation film of the present invention is a method for producing a retardation film having at least two layers of different optical anisotropic layers, characterized in that the substrate layer composed of a positive birefringent polymer is -8 - 200927454 After stretching, the negative birefringent polymer solution is coated on the substrate layer and dried to form a negative birefringent layer, and then the laminate of the substrate layer and the negative birefringent layer is opposed to The stretching direction of the substrate layer is stretched in the vertical direction. The present inventors have directly applied a negative birefringent layer on a positive birefringence polymer substrate as described above, and subjected to a stretching treatment to attempt to form a retardation film, but it is not difficult to prepare. A retardation film having a desired phase difference , causes problems such as uneven phase difference, haze, and contrast reduction on the formed film. However, it was found that first, a base layer composed of a positive birefringent polymer was stretched, and after a negative birefringent layer was formed, a laminate of a base layer and a negative birefringent layer was formed with respect to the substrate. When the stretching direction of the layer (the first stretching direction) is stretched in the vertical direction (the second stretching direction), the phase difference unevenness and the haze are not generated, the front contrast is excellent, and the viewing angle is sufficient. A phase difference film of optical characteristics. © As in the present invention, after the substrate is stretched in advance, a coating layer of a negative birefringent polymer is disposed, and the film is stretched again in the vertical direction of the initial stretching direction, so that the phase difference is uneven and the haze is reduced. Although the cause is not certain, it is presumed that by performing a second degree of stretching treatment on the vertical direction of the substrate layer, the characteristics of the film and the stress applied to the film are uniformized, which is a factor. Hereinafter, the present invention will be described in detail. Whether or not the polymer resin exhibits positive birefringence in the direction of stretching can be judged according to the following test method. 200927454 (Testing method of birefringence of polymer resin) The polymer resin was dissolved in a solvent alone and cast into a film, and then dried and dried, and a film having a transmittance of 80% or more was evaluated for birefringence. The Abbe refractometer -4T (manufactured by Atago) uses a multi-wavelength light source to measure the refractive index, and when the film is stretched in the broad axis direction, the refractive index in the direction of stretching is Nx, and the in-plane is in the vertical plane. The refractive index of the direction is Ny. For the film of 5 90 nm each having a refractive index of (Nx - Ny ) &gt; ,, it was judged that the © polymer resin had positive birefringence for the stretching direction. Similarly, in the case of (Nx-Ny) &lt; 0, it is judged to have negative birefringence. (Positive birefringent polymer) The positively-oriented birefringent polymer of the present invention is not particularly limited as long as it has a property of increasing the refractive index in the stretching direction during stretching, and has high transparency. It is better to have thermoplasticity. However, if a positive phase difference is exhibited by a mixture type containing a plurality of materials, and the mass fraction, the volume fraction, and the most component are not necessarily positively birefringent. Specifically, for example, a cellulose resin such as triacetyl cellulose (TAC) or cellulose acetate propionate (CAP), a polybornene resin, a polycarbonate resin, a polyester resin, or a polyether may be mentioned. Anthracene resin, polyfluorene resin, polyamide resin, polyimide resin, polyolefin resin, polyarylate resin, polyvinyl alcohol resin, polyvinyl chloride resin, polyvinylidene chloride resin, and the like. In particular, a cellulose resin is preferred, and a cellulose ester is particularly preferred. (Production of Substrate Layer) -10-200927454 The base material layer in the present invention can be produced by a solution flow method or a melt flow method, and a negative birefringent layer and a stretching operation can be carried out, and a suitable cut can be produced. An anisotropic film. As a means for adjusting this birefringence anisotropy, a well-known means can be used. For example, the film thickness, the stretching temperature, the stretching ratio, etc. needless to say, in the solution flow method, the solution composition, the solution, the temperature, the time, the stripping temperature of the flowing belt-drum, the drying temperature thereafter, and the stretching time. The amount of solvent remaining, the subsequent drying temperature, the transport tension, and the like. Roots © According to these factors, the same applies to the melt flow method. (Negative birefringent polymer) The negative birefringent polymer is not particularly limited as long as it has a property of increasing the refractive index in the direction perpendicular to the stretching direction during stretching, and the result of containing a plurality of materials If it has a negative birefringence expression, it is the same as the above-mentioned positive birefringent polymer. It is preferred that the transparency is high and the thermoplasticity is high. More preferably, a polymer having a polymerizable monomer unit having a bonded (heterocyclic) aromatic radical and a polymerizable moiety having a minimum atomic number of 2 or more and 2 or less as a copolymerization component is preferred, and a (heterocyclic ring) is bonded. Aromatic. The polymerizable monomer unit having a minimum number of atoms of the group substituent and the polymerizable moiety of 0 or more and 2 or less is, for example, a structure represented by the following general formula (1). Here, the (hetero) aromatic means an aromatic compound composed only of a hydrocarbon and a monomer other than carbon in a ring structure, such as nitrogen, oxygen, sulfur, etc., in the cyclic unsaturated organic compound. A group of compounds in which a heteroaromatic compound is combined. -11 - 200927454 [化1] - hiding in the suburbs)

R =&lt;

Z

R = &lt; 〇 = (° 2 In the general formula (1), R is a halogen, a hydroxyl group, a carboxyl group, an amine group, a cyano group, a nitro group, a nitroso group, a thiol group representing hydrogen, F, Cl, Br or the like. And a saturated or unsaturated aliphatic hydrocarbon group having 1 to 12 carbon atoms. Further, Z represents a (heterocyclic) aromatic substituent. The (heterocyclic) aromatic substituent may, for example, be the following general formula (2)~ ( 6) The structure shown. [Chemical 2] - General (2)

-12- 200927454 [化3] - General (3)

-Remaining power ~^~Ra ~^ί r2 Ri % R2 ~^R, ft* 13⁄4

-13- 200927454 [Chem. 4]

14- 200927454 [Chem. 5]

[6] - General {6}

-15- 200927454 In the general formulae (2) to (6), Ri, R2, Κ·3 and R4 represent a halogen, a hydroxyl group, a carboxyl group, an amine group, a cyano group, a nitro group, such as hydrogen, F, Cl or Br. a nitroso group, a thiol group, a saturated or unsaturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a fluorenyl group having 1 to 12 carbon atoms, and an oxygen having a carbon number of 1 to 12 Alkoxycarbonyl group having a carbon number of 1 to 12, a hydrocarbon having 1 to 4 carbon atoms having a hydroxyl group, a hydrocarbon group having 1 to 4 carbon atoms having an amine group, or a secondary or tertiary group having a hydrocarbon group having 1 to 4 carbon atoms. Amine group. Further, a polymerizable monomer unit which forms a compound having a (heterocyclic) aromatic substituent and a polymerizable moiety having a minimum atomic number of 0 or more and 2 or less is specifically exemplified by styrene and p-methylstyrene. , m-methylstyrene, o-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-di Alkyl-substituted styrene, 1,1-diphenylethylidene, N-vinyl, methylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, etc. Carbazole, 2-vinylcarbazole, 4-vinylphenol, 4-vinylbiphenyl, methylcarboxyphenylmethacrylamide, decylamine, (1-ethyloxazol-3-ylcarbonyloxy) Ethyl, stilbene, ethyl, 4-(1-hydroxy-1-methylpropyl)styrene, 2-hydroxymethylstyrene, .2-dimethylaminecarbonylstyrene, 2-aniline Carbonylstyrene, 3_(4-diphenyl)benzidine, 4-(4-diphenylene)benyl, 2,6-dichlorobenzene, perfluorostyrene, 2,4-di Isopropylstyrene, 2,5-diisopropylstyrene, 2,4,6-trimethylstyrene, α-A Styrene, 1-vinylnaphthalene, 2-vinyl naphthalene and the vinyl-substituted aromatic compound and the like. Further, in the negative birefringent polymer, the copolymerization component is a polymerizable monomer unit having a minimum atomic number of 0 to 16 to 200927454 in combination with the (heterocyclic) aromatic substituent and the polymerizable moiety. At the same time, it is also possible to have a polymerizable monomer which is copolymerizable other than the above, regardless of the number of kinds of the copolymerization component. The copolymerizable polymerizable monomer' is preferably a maleic imine, N-methyl maleimide, N-ethyl maleimide, or N-cyclohexylma, which is expected to impart heat resistance. An anhydride such as a quinone imine, an N-phenyl maleimide, an N-naphthyl maleate, an imide, a maleimide monomer, a cyanated vinyl group, a maleic anhydride, or the like The derivatives 'isopropenylbenzene (α-methylstyrene), isopropyl isopropenyltoluene, isopropenylethylbenzene, isopropenylpropylbenzene, isopropenylbutylbenzene, isopropenylpentylbenzene, Alkyl-substituted isopropenylbenzenes such as isopropenylhexylbenzene and isopropenyloctylbenzene, acrylamides such as propylene morpholine, hydrazine, hydrazine-dimethylaminopropyl acrylamide. Further, in order to adjust the solubility in a solvent, the coatability, the adhesion to a substrate, and the like, an acrylate, 2-hydroxyethyl acrylate, methyl acrylate, 2-hydroxyethyl methacrylate, or the like may be appropriately selected. Acrylates such as ethyl acrylate and butyl acrylate; methacrylates such as methyl methacrylate and ethyl methacrylate; vinyl carboxylic acids such as acrylic acid and methacrylic acid; Sexual monomer. Further, blending with a polymer which is compatible with the same can be suitably carried out. (Yura) About · Yanla 'If the direction of the extension (first extension) direction before the negative birefringence layer is given, and the direction of the post-tension (second extension) is perpendicular, then the infinite $ ° $ 'this In the invention, the direction of the extension is defined by the R state before the final extension, 'the extension in any direction, and the combination of the plurality of stages is extended -17-200927454. In particular, it is preferable to make the retardation axis direction (alignment angle) of the film uniform in a plurality of stages formed by different stretching ratios, speeds, and temperature conditions. For example, in the case of film formation of a long-length film, after the film formation of the base material layer, the film may be stretched in the conveyance direction, and then stretched by a tenter in a direction perpendicular to the conveyance direction. The extension of the same direction is not in the plural stage. However, it is necessary to make the stretch magnification in any direction large, and the retardation axis of the film is oriented in the transport direction or in the transport direction. In the case of the former 〇, the second extension is mainly for the horizontal extension, and the latter is mainly for the longitudinal extension. The extension operation of the second extension combination may also be the same as the first extension. The first extension direction and the second extension direction are appropriately selected in order to obtain a desired retardation film. The method of longitudinal drawing can be carried out by a so-called longitudinal drawing machine composed of a combined drum. Regarding the width contraction in the longitudinal drawing, it is appropriately selected according to the desired phase difference 値 and the film width, and the degree of shrinkage is adjusted by changing the film tension 'treatment temperature, film-to-roller width ratio. By shrinking by ❹, the absolute 値 of the phase difference 厚度 in the thickness direction is lowered, and the film width is narrowed. The transverse stretching can also be carried out using a known needle combing machine, a crepe type tenter _ machine or the like. Here, the first extension is carried out after the solution of the substrate layer is flowed, and is carried out in a state containing a solvent, and may be carried out after drying, and it is preferred that the second extension is carried out after the solvent of the coating layer is dried. Further, in any stretching, it is preferable that the film is inferior to the durability at a high temperature and the planarity is ensured at a high temperature, but since it is difficult to express the phase difference at a high temperature, the stretching temperature is arbitrary. The first layer is preferably close to Tg. -18- 200927454 However, in the case where the base material layer is particularly used in the case of using a cellulose ester, if it is extended beyond Tg (usually in the range of about Tg + 50 °C), there is a problem that the haze rises. When haze-rise is applied as a retardation film in a liquid crystal display device, there is a problem that contrast is impaired. Then, the inventors of the present invention have found that a negative birefringent layer is imparted to the base material layer. In the case of stretching, the Tg of the negative birefringent layer of the coating layer is made Tg or less of the base layer. In this case, it is possible to suppress the increase in the haze of the base material layer, and to establish the two phases of the planarity, the phase difference uniformity, and the phase difference. In other words, when the glass transition temperature of the positive birefringent polymer is Tgl and the glass transition temperature of the negative birefringent polymer is Tg2, the following formula (1) is preferable. 〇°C ^ Tgl-Tg2 ^ 40°c ·· (1 ) (Optical characteristics of retardation film) In the present invention, nxl, nyl, and nzl represent refractive indices in the second extension direction of the substrate layer, respectively. The refractive index in the direction perpendicular to the second extension direction in the plane, and the refractive index in the thickness direction. The substrate layer in the present invention satisfies nxl and nyl&gt; lk, and more preferably, the substrate layer has a retardation 値Rol, Rtl of -20gRol$40 and 80SRUS160 preferably satisfies -10SR〇1S20 and 100SRUS130. Further, in the present invention, nx2, ny2, and nz2 respectively indicate a refractive index perpendicular to the negative extension direction in the negative -19-200927454 refractive layer, and a refractive index and a thickness direction in the second extension direction. The refractive index, which satisfies nz2 2 nx2 &gt; ny2, is better, and the retardation of the birefringent layer is more preferably 50 ^ R 〇 2 ^ 200 and - 1 80 S Rt2 S - 80 . Better to meet. 80 ^ Ro2 ^ 180 and -150S Rt2S -100. © The optical characteristics of the retardation film laminated with the base layer and the negative birefringent layer formed by the manufacturing method disclosed in the present invention, the refractive index in the in-plane phase of the slow phase, the in-plane and the slow phase axis When the refractive index in the vertical direction and the refractive index in the thickness direction are regarded as nx3, ny3, and nz3, respectively, the retardation films Ro3 and Rt3 of the retardation film satisfy 50 S Ro3 S 200 and -70 $ Rt3 S 70, respectively. Each of the above retarding enthalpy is as defined below.

Roa= ( nxa-nya) xda ❹ Rta= ( ( nxa + nya) /2-nza) xda (however, a is one of 1, 2, 3) &lt;Measurement of refractive index&gt; The refractometer-4T (manufactured by Atago) used a multi-wavelength light source and measured the average refractive index at a wavelength of 590 nm. In this case, the KOBRA21-ADH' manufactured by Oji Scientific Instruments Co., Ltd. was used to measure the third-order refractive index at a wavelength of 590 nm in an atmosphere of 23 ° C and 55% RH, and the refractive index in the direction of the slow axis was obtained. Nxa, folding in the direction of the phase axis -20- 200927454 The rate of incidence nya, the refractive index nza in the thickness direction. In the manufacturing method provided by the present invention, the base material layer is a single extension of only the base material layer, and a total of two extensions of the second extension is performed in the vertical direction with respect to the first extension after the formation of the laminate. . On the other hand, the negative birefringent layer is a second extension after only forming the laminate. In order to make the negative birefringent layer, the necessary phase difference is expressed, and the magnification of the second extension is determined. Therefore, when there is no first extension, the phase difference of the substrate is based on the phase difference of the negative birefringent layer. Decide. However, by applying the first stretching to the substrate in advance, only the phase difference of the substrate can be adjusted, so that the phase difference between the substrate and the negative birefringent layer can be independently controlled. Therefore, a laminate in which each layer has an arbitrary phase difference can be integrally formed. The retardation film formed by the production method disclosed in the present invention preferably has a haze of less than 1%, and is particularly preferably 0 to 0.5%. Therefore, the haze can be lowered in accordance with the processing temperature of the first film. In particular, in the two-stage extension of the aspect of the present invention, the second extension can suppress the increase of the haze through the temperature higher than the first extension temperature, and can further have the extension condition of the second extension. © Degree of freedom', it is possible to obtain a phase difference film in which both the desired phase difference and high transparency are established. Since the haze is suppressed, a display device exhibiting a high frontal contrast ratio can be obtained. The retardation film formed by the production method disclosed in the present invention preferably has a visible light transmittance of 90% or more, and more preferably 93% or more. In the present invention, the term "vertical direction" means that the angle is expressed by 〇 to 90 degrees, and the angle formed by the reference direction is from 8 7 to 90 degrees, preferably from 89 to 90 degrees, more preferably from 89.5 to 90 degrees. By. Further, the term "parallel direction" means that the angle formed with the reference direction is 3 to 〇, preferably dice, and -21 to 200927454 is more preferably 0.5 to 0. &lt;Measurement of Glass Transition Temperature (Tg)&gt; The glass transition temperature was measured by DSC6220) manufactured by Differential Scanning Co., Ltd. The ratio is raised from room temperature to 220 ° C, and the temperature is raised under the same conditions for the temporary sheet, and the second time is used for the treatment. Among the two-point bending points of the temperature-heating curve, they are regarded as points A and B, respectively, and the temperature ranges above the point A are respectively approximate straight lines, and the midpoints of the respective intersection points of the straight line 1 1 passing through the point 2 are regarded as Tg. In the case of the circumstance, it is possible to use 10 to 200 μm only by using a substantially straight (base layer) © the above-mentioned positive birefringent polymer. Especially with a good film. More preferably 20~60μιη. In the above-mentioned base material layer, it may be contained in the present invention as needed, and it is important to adjust the negative Tg difference. Moreover, not only has a plasticizing effect, but also a positive birefringence performance (phase I after stretching). In addition, the absolute ic calorimeter of the reduced photoelastic coefficient (Seiko Instruments film at 20 ° C / After the minute is reached to room temperature, the heat generated by the temperature is changed to the range of the high temperature side and the low temperature side, and the point of the B between the B and B, and the line 12 where the inflected point green is not read. Instead of 1 1 , the film thickness of the base material layer is not special, and 10 0 1 ΟΟ μ η is a special plasticizer. The plasticizer is particularly suitable for the compounding layer of the birefringent polymer:), the wavelength dispersion machine: the material is preferably The plasticizer-22-200927454 is not particularly limited, and is preferably a polyvalent carboxylate plasticizer, a glycolate plasticizer, a phthalate plasticizer, a fatty acid ester plasticizer, and a polyvalent alcohol. It is selected from ester-based plasticizers, polyester-based plasticizers, acrylic-based plasticizers, and phosphate-based plasticizers. In addition, in order to control the phase difference of the substrate layer, it may also contain materials exhibiting positive birefringence and adjustment. Wavelength-dispersed material'. Materials with a photoelastic coefficient close to zero, etc. A compound having a furanose structure or a pyranose structure is also preferred. More specifically, the substrate layer of the present invention is a compound (A) having a furanose structure or a pyranose structure, or a furanose structure. It is preferred that at least one of the pyranose structures is a compound in which all or a part of the OH groups in the compound (B) of two or more and 12 or less are esterified (hereinafter, these compounds are also referred to as sugar ester compounds). Preferred examples of the compound (A) and the compound (B) include the compounds shown below, but the present invention is not limited thereto. Examples of the compound (A) include glucose, galactose, mannose, rutose, and wood. Examples of the compound (B) include lactose, sucrose, and cellulose. Sugar, maltose, cellulose trisaccharide, maltotriose, raffinose, and cane trisaccharide. In the compound (A) and the compound (B), it is preferred to have both a furanose structure and a pyranose structure. Examples thereof include sucrose. All or a part of OH in the above compound (A) and compound (B) is synthesized. Esterification The monocarboxylic acid to be used in the case of the sugar ester compound is not particularly limited, and a known aliphatic monocarboxylic acid, an alicyclic mononic acid 'aromatic monocarboxylic acid, or the like can be used and esterified to synthesize the sugar used in the present invention. Ester-23-200927454 A compound may be used alone or in combination of two or more. Preferred aliphatic monocarboxylic acids include, for example, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, and hexanoic acid. Acid, heptanoic acid, octanoic acid, citric acid, citric acid, 2-ethyl hexane carboxylic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecane Acid, stearic acid, nonadecanic acid, peanuts, acid, behenic acid, tetracosanoic acid, hexadecanoic acid, heptacosanoic acid, montanic acid, tridecanoic acid, tridodecane Saturated fatty acids such as acid, eleven carbonic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, octenoic acid, and the like. Preferred examples of the alicyclic monocarboxylic acid include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, or a derivative thereof. Examples of preferred aromatic monocarboxylic acids include aromatic monocarboxylic acids, cinnamic acid, and benzylic acid in which a benzene ring of benzoic acid such as benzoic acid or toluic acid is introduced with a substituent such as 1 to 5 alkyl groups or an alkoxy group. An aromatic monocarboxylic acid having two or more benzene rings, such as a biphenylcarboxylic acid, a naphthalenecarboxylic acid or a tetrahydronaphthalenecarboxylic acid, or a derivative thereof, and particularly preferably benzoic acid. A detailed production method of such a compound is described in JP-A-8-245678. The ester compound of the above compound (A) and compound (B), together with the esterified compound of oligosaccharide, can be suitably used as a compound which binds 3 to 12 of the furanose structure or the pyranose structure of the present invention. The oligosaccharide is produced by the action of an enzyme such as an amylase such as starch or sucrose. Examples of the oligosaccharide which can be used in the present invention include maltose oligosaccharide, isomaltose oligosaccharide, fructose oligosaccharide, galactooligosaccharide, and xylose oligosaccharide. The oligosaccharide can also be acetylated by the same method as the above compound (A) and compound (B). Next, an example of a production example of a sugar ester compound will be described. Ethanol anhydride (200 ml) was added dropwise to a solution of glucose (29.8 g, 166 mmol) added to pyridine (liter), and reacted 24 thereafter, the solution was concentrated by an evaporator and placed in ice water, and placed at 1. The filter paper was filtered, the solid and water were separated, and the glass filter paper was dissolved in chloroform to cool the liquid until it was neutral. After drying, it was dried with anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the chloroform was removed by a hair dryer, and dried under reduced pressure to obtain 58-8 g of glucose vinegar, 150 mmol, and 90.9%. Alternatively, the above carboxylic acid may be used in place of the above acetic anhydride. The following is a specific example of the sugar ester compound, but it is not limited to 100 millihours. After the hour, the solid layer is separated by a dilute acid ester (described as a single cold. -25- 200927454 [Chem. 7]

〇 Rt= one c one CHS

Chemical inclusion 2

Thin

Ο II R3; one C

Ο I sleep -c-c2h5 -26 200927454 [Chemical 8] ib compound $

R5» II , C-CHa

Chemical inclusions?

R6: -I- GHa &lt;匕合铷7

〇 R7= —G-CH3 compound β

CH2OR8 RBO

ORS Ο R8= —e-CHs -27 200927454 [Chemical 9] Compound 9

H OR9 H OR9 H OR9

Ο R9= —C-CH3 Compound 10 CH2OR10

ο R10= —C-CH3

-28- 200927454 [Chemical 10] Compound ΐΐ

CHiORli &gt;p—〇, CH2OR11 Jp°\ 1 0 riio\〇R11 y ^CHiORU R11 = —C I I H OR11 1 1 OR11 H OGH,

〇GH3 och3 Ο compound 12 CH^pRIl

R120V?r12 Η H〆 Nf R12C&gt; V OR12 1 OR12 1 H CH20R12 R12= 〇ch3 Compound 13 CH2〇R13 CH2〇R13 O' R13〇\?r13

dH2〇R13 R13* ❿化含物

R14» OCH3

OCHs OCH3 29- 200927454 [Chem. 11] Chemicals 15 Ο

R15=—C—^ Compound 16

ο R16= —C—CH2 chemical inclusion bamboo

ο ιι R17= 一 O-CHj ORIT 200927454 [化 12]

CHjpSl#

OR18 OR18 Compound 19

-31 - 200927454 [Chemical Formula 13] Compound 20 R20O, R20〇\OR2°

R20O

R20O

R20O&gt; OR20

R20O

R20O&gt; OR20 R20O, R20= —C-CH3

R20〇v OR20 〇,

R20O

R20O&gt; 〇, OR20 CH2 OR20 -32- 200927454 [Chem. 14]

Compound 21

Η · OR21 compound 22 CHzOR22

0阳 OR22 OR22 CH2 R22= —C-CHa OR22 OR22 0R22 n=1-

OR22 〇1^22 Ok22 Further, fine particles may be added to these base material layers as needed. Examples of the inorganic particles of the fine particles include cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium citrate, calcium citrate hydrate, aluminum citrate, magnesium citrate, and phosphoric acid. calcium. The primary particles of the microparticles preferably have an average particle diameter of 5 to 400 nm, and more preferably 10 to 300 nm. These are mainly contained in the second-stage coagulation -33-200927454 collective type having a particle diameter of 0.05 to 0.3 μm, and the particles having an average particle diameter of from 10 〇〇 to 400 nm are not aggregated and are preferably contained in the primary particle type. In the polarizing plate protective film, the content of these fine particles is preferably 0.01 to 1% by mass, particularly preferably 0.05 to 0.5% by mass. The fine particles of cerium oxide are commercially available, for example, under the trade names of Aerosil R972, R972V, .R974, R812, 200, 200V, 300, R202, 0X50, TT600 (based on Japan Aerosil Co., Ltd.).微粒 The zirconia fine particles are commercially available, for example, under the trade names of Aerosil R976 and R81 1 (manufactured by Japan Aerosil Co., Ltd.). Further, polymer type microparticles may be added. Examples of the polymer include a polyoxyl resin, a fluororesin, and an acrylic resin. Polyoxymethylene resin is preferred, especially those having a three-dimensional network structure, for example, Tospearl 103, the same 105, the same 108, the same 120, the same 145, the same 3120 and the same 240 (above Toshiba Silicon) The product name is commercially available and can be used. In any of the inorganic or organic fine particles, the refractive index of the fine particles ® of the present invention is also preferably close to the average refractive index of the substrate layer. Furthermore, it may contain an ultraviolet absorber. The ultraviolet absorber is preferably one having an optical film suitability such as excellent color and transparency. For example, a hydroxybenzophenone-based compound, a benzotriazole-based compound, a salicylic acid ester-based compound, a benzophenone-based compound, a cyanoacrylate-based compound, a nickel-salted salt-based compound, and the like can be listed. Further, a polymer ultraviolet absorber described in JP-A-2002-169020, JP-A-2006-113175, and the like is preferably used. Other ingredients may also contain antioxidants such as antistatic agents, slip materials, mold release materials, colorants, anti-colorants, and flame retardants. In particular, in the case of producing a film according to the melt flow-34-200927454, it is preferable to introduce an antioxidant, particularly to increase the transparency of the film to the maximum, and it is preferable to use a sliding material or a release material instead of the foregoing. Microparticles. Further, an antistatic layer, a slip layer, and an easy adhesion layer may be provided on either side of the substrate. _ (negative birefringent layer) The thickness of the negative birefringent layer composed of the negative birefringent polymer is not particularly limited, and 2 to 50 μm can be used. In particular, it is particularly preferable that the film thickness is 3 to 40 μm. More preferably 5~30μιη. When it is desired to further improve the adhesion between the substrate layer and the negative birefringent layer, an easy adhesion layer may be provided between the two layers. The material of the adhesive layer is not particularly limited, and a known material can be suitably used. The film thickness of the easy-adhesive layer is preferably Ιμπι or less, and more preferably 0.5 μm or less. © (Application of Negative Birefringent Layer) The coating method is not particularly limited, and specific examples thereof include a gravure coating, a comma coating, a bar coating, a die coating, and a lip coating. , roll coating, flow coating, printing coating, dip coating, rogue film formation, spin coating. These methods are suitably selected by solution viscosity and film thickness. As the solvent, a generally known organic solvent can be used. For example, an alcohol such as methanol, ethanol, propanol or butanol, a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone or a benzene can be used. An aromatic hydrocarbon such as toluene or xylene, a glycol such as ethylene glycol, propylene glycol or hexanediol, ethyl solubilized fiber-35-200927454 agent, butyl cellosolve, ethyl carbitol, butyl group a glycol ester such as carbitol, diethyl cellosolve or diethyl carbitol, an ester of methyl acetate or ethyl acetate, N-methylpyrrolidone, dimethylformamide, An organic solvent such as dichlorocarbamate, chloroform or tetrahydrofuran, or water. They may be used alone or in combination of two or more. In order to ensure the physical properties of the coating film, it may be subjected to heat treatment or active energy ray irradiation treatment such as ultraviolet light before or after stretching, and it is also effective to contain a crosslinkable material in advance in the coating solution. The Tg of the film can be controlled. (Retardation film) The phase difference film produced by the production method disclosed in the present invention is suitably used for a polarizing plate in an expanded viewing angle film type as a liquid crystal display device. In this case, it is possible to directly bond on at least one side of the polarizer, and it is also possible to function as a protective film for the polarizing plate. At this time, it is preferable to bond the substrate layer side and the polarizer. © Polarizer can be made in the usual way. The phase difference film substrate layer side of the present invention is subjected to alkaline alkalization treatment. The polyvinyl alcohol film is immersed in at least one side of the polarizer produced by the iodine solution. The phase difference film which is alkalized is preferably laminated using a fully alkalized polyvinyl alcohol aqueous solution. A retardation film can also be used on the other side and an additional polarizer protective film can also be used. When the negative birefringent layer side is bonded to the polarizer, a known adhesive can be used, but a water-based adhesive is preferred. For the polarizer protective film used on the inside side, any suitable material can be used. Such a material may, for example, be an excellent plastic film such as 'transparency, mechanical strength, thermal stability-36-200927454, moisture barrier property, isotropic property, and the like. Specific examples of the resin constituting the plastic film include a deuterated resin such as triacetin cellulose (TAC), a polyester resin, a polyether maple resin, a poly maple resin, a polycarbonate resin, a polyamide resin, and a polyphthalamide. Amine resin, polyolefin resin, acrylic resin, polybornene resin, cellulose resin, polyarylate resin, polyphenyl-ethylene resin, polyvinyl alcohol resin, polyacrylic resin, and mixtures thereof. Further, a thermosetting resin such as an acrylic type, an urethane type, an acrylamide group, an epoxy type or a polyoxymethylene type, or an ultraviolet hardening type resin may be used. From the viewpoint of polarizing characteristics and durability, a TAC film whose surface is alkalized by alkali or the like is preferred. Further, commercially available cellulose oximation films are KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC12UR, KC4UE, KC8UE, KC8UY-HA, KC8UX-RHA, KC8UXW-RHA-C, KC8UXW-RHA -NC, KC4UXW-RHA-NC (above, Konica-Minolta Opt, etc.) and the like are preferably used. The polarizer protective film of the present invention is industrially produced into a thin film and is bonded to a polarizer which is also formed into a film of a long scale. The state of the sheet is most useful. Further, the polarizing plate is further bonded to each other, and the simple retardation film type which is not a function of the polarizer protective film can be used. The polarizer of the main constituent elements of the polarizing plate is an element that passes only the deflected surface light in a certain direction. A representative polarizer is a polyvinyl alcohol-based polarizing film which has a polyvinyl alcohol-based film dyed with iodine. And those who dye with dichroic dyes, but are not limited thereto. The polarizer -37-200927454 can be formed by using a polyvinyl alcohol aqueous solution, allowing it to be uniaxially stretched and dyed, or uniaxially stretching after dyeing, preferably after treatment with a boron compound. It is preferred to use a polarizer of 5 to 3 Ομιη for the film thickness of the polarizer.

The retardation film produced by the production method disclosed in the present invention can be used for liquid crystal display devices of various driving methods such as STN, TN, OCB, HAN, VA (MVA, PVA) &gt; IPS, FFS, OCB. Preferably, it is an IPS, FFS, VA (MVA PVA) type liquid crystal display device. In the case of the S TN, Ο C B, and TN type liquid crystal display devices, it is not necessary to make the absorption axis direction of the polarizer be parallel or perpendicular to each of the extension axes, and any form is preferably used. By using such a liquid crystal display device, it is possible to obtain a liquid crystal display device having a wide viewing angle and a high front contrast with excellent visibility. A description will be given of a configuration example in which a phase difference film formed by the production method disclosed in the present invention is used in an IPS or FFS type liquid crystal display device. In the case of black display, the retardation axis direction of the liquid crystal has an absorption axis in the vertical direction. The phase difference film is disposed between the polarizer disposed as usual and the glass substrate. In the case where a negative complex refraction layer is disposed on the polarizer side, the negative complex axis of the negative birefringent layer is parallel to the absorption axis of the polarizer, and a negative birefringent layer is disposed on the side of the glass substrate to make a negative When the retardation axis of the birefringent layer is arranged perpendicular to the absorption axis of the polarizer, an excellent viewing angle can be obtained. In this case, it is preferred to use a retardation film of the present invention in which the substrate layer has a retardation 〇R 〇 = 〇 nm, or a retardation 基材 of the substrate layer is R 〇 〇 , nm, and it is preferred to use a substrate layer. The retardation film of the present invention is perpendicular to the retardation axis of the negative complex refraction layer. At this time, the parallel direction of the liquid crystal slow axis direction in the case of black display -38 - 200927454 is directed to a polarizer having an absorption axis, that is, a polarizer that sandwiches the liquid crystal element and is located on the opposite side, and is disposed between the glass substrate. For the retardation film, it is preferable that the face-inside retardation 値R〇 is about zero. More preferably, the retardation 値Rt in the thickness direction is 丨Rt丨s 45 nm, and further preferably I Rt丨S 5 nm. This retardation film also serves as a polarizing plate protective film. The retardation film of the present invention is also preferably used as a wavelength plate. For example, _ is also preferably used as a reflection type, a transflective liquid crystal display device, and a Λ/4 wavelength plate used for an electric field illumination type display device. According to the manufacturing method of the present invention, the laminated structure of the positive birefringent substrate layer and the negative birefringent layer is further adjusted according to the second degree of stretching operation conditions. After that. In such display devices, it is generally preferable that the phase difference of λ /4 is also omnidirectional in the front direction and the oblique direction. In the constitution of the present invention, the R 〇 2 of the negative complex refractive index layer is close to λ /4. Further, it is preferable that Rt2 is close to Rtl, and there is no such limitation in a system for expanding the viewing angle effect particularly in a liquid crystal display device.实施 EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited thereto. &lt;&lt;Preparation of retardation film&gt;&gt;&lt;Production and extension of base material layer A1 having positive birefringence&gt; Cellulose acetate propionate (acetamyl substitution degree 1.9, propylene Base substitution degree 0.7, number average molecular weight 80000, weight average molecular weight 220000 -39- 200927454) 100 parts by mass of triphenyl phosphate 8 parts by mass - ethyl decyl ethyl benzoate 4 parts by mass of cerium oxide microparticles (Aerosil R972V Japan Manufactured by Aerosil (manufactured by Co., Ltd.) 0.2 parts by mass. 330 parts by mass of methylene chloride. 60 parts by mass of ethanol ❹ The above is put into a sealed container, heated, and completely dissolved while stirring, and filtered using a filter paper No. 24 made of a filter paper (stock). , the blending solution A was prepared. The blend A was filtered by Fine Mat NF manufactured by Nippon Seisaku Co., Ltd. The cerium oxide fine particles are dispersed and added by using a part of ethanol added in advance. Next, a belt type rogue device was used to uniformly flow on a 2 m wide stainless steel belt support (surface temperature of 25 ° C). The solvent was evaporated until the residual solvent dose was 100% and peeled off from the stainless steel belt support. The stripped cellulose ester film web was evaporated at 55 ° C, and then clamped by a stenter and stretched 1.3 times at 125 ° C in the TD direction (direction perpendicular to the film transport direction) (30) %). Thereafter, the film was conveyed at 120 °C while being dried by a roll, slit at a width of 1500 mm, and embossed at a width of 15 mm and an average height of 12 μm at both ends of the film to obtain a base material layer A1. The cellulose ester film had an average film thickness of 50 μm, a film thickness variation in the width direction, and a long axis direction of ±1 μm, and a roll length of 2000 m. The substrate layer Α1 had a Tg of 142 °C. In addition, the amount of residual solvent is represented by the following formula. -40- 200927454 Residual solvent amount (% by mass) = { ( MN ) / N} xl 〇〇 where Μ is the mass of the mesh at any time, Ν is the mass Μ substance dried at 1 l 〇 ° C for 3 hours the quality of. The obtained film was measured by Abbe's refractometer - 4T (manufactured by At). ^ The refractive index was measured using a multi-wavelength light source, and the refractive index in the extension direction was set.

When Nx and the refractive index in the vertical in-plane direction are Ny (Nx-Ny) &gt; 0, 具 has positive birefringence. &lt;Preparation and Stretching of Base Material Layer A2 with Positive Birefringence&gt; The base material layer A2 was treated with the base material layer A1 except that the stretching temperature and film thickness described in Table 1 were changed. The base material layer A2 had a Tg of 142 ° C, and also had positive birefringence as measured by the above refractive index. &lt;Preparation and elongation of base material layer B1 having positive birefringence&gt; G cellulose triacetate (acetamyl substitution degree 2.85, number average molecular weight 1 20000, weight average molecular weight 2 80000) 1 Tannin _ parts by weight of triphenyl phosphate, 8 parts by mass of diphenyl diphenyl phosphate, 4 parts by mass of silica sand microparticles (Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.) Q. 2 parts by mass of dichloromethane, 300 parts by mass, 54 parts by mass of methanol -41 - 200927454 The above-mentioned 11 parts by mass of 1-butanol was put into a sealed container, and it was overheated, and completely dissolved while stirring. The mixture was filtered using Angstrom filter paper No. 24, manufactured by Azumi filter paper, to prepare a blend B. The mixture was filtered by Fine Mat NF manufactured by Nippon Seisaku Co., Ltd. The cerium oxide fine particles are dispersed and added by using a part of ethanol added in advance. 〇 Next, use a belt type rogue device to evenly flow on a 2 m wide stainless steel belt support (surface temperature 25 °C). The solvent was evaporated until the residual solvent amount was 100%, and it was peeled off from the stainless steel belt support. The stripped cellulose ester film web was evaporated at 55 ° C, and then clamped by a stenter and stretched 1.25 times (at 25%) at 120 ° C in the TD direction (direction perpendicular to the film transport direction). ). Thereafter, the mixture was conveyed by a dropping cylinder at 120 ° C, and the drying was completed, and slitting was performed at a width of 1,500 mm, and embossing was performed at both ends of the film by a width of 15 mm and an average height of 12 μm to obtain a base material layer B1. ❹ The cellulose ester film has an average film thickness of 90 μm and a film thickness variation of ±1 μm in both the broad axis direction and the long axis direction, and the roll length is 2000 m. The Tg of the substrate layer Β 1 _ was 1461, and the refractive index was also positively refractive as measured by the above refractive index. &lt;Preparation of base material layer A3 having positive birefringence&gt; The base material layer A3 was produced by the same treatment as the base material layer A1 except that the stretching was not carried out. The base material layer A3 had a Tg of 142 ° C and had positive birefringence as measured by the above refractive index. -42-200927454 &lt;Preparation and elongation of base material layer B2 having positive birefringence&gt; The base material layer B2 was produced by the same treatment as the base material layer B1 except that the stretching temperature and the magnification described in Table 1 were changed. The base material layer B2 had a Tg of 146 ° C, and also had positive birefringence as measured by the above refractive index. &lt;Preparation of base material layer B3 having positive birefringence&gt; The base material layer B B2 was produced by the same treatment as the base material layer B1 except that the stretching was not performed. The base material layer B2 had a Tg of 146 ° C and had positive birefringence as measured by the above refractive index. &lt;Negative birefringent layer is imparted&gt; (negative birefringent resin (N 1 )) contains styrene unit of 56%, N-phenylmaleimide unit of 24%, methyl methacrylate The copolymer was 20%, and the glass transition temperature was 122 ° C according to DSC. ❹ (negative birefringent resin (N2)) A copolymer containing 46% styrene unit and 54% methyl methacrylate unit. The glass transition temperature is 10 °C °C according to DSC (negative birefringence) Resin (N3)) Copolymer containing 30% N-vinylcarbazole unit, N-propenylmorpholine unit 40% methyl methacrylate unit, 30%, according to DSC, 'glass transition temperature is 154° C. -43-200927454 (Preparation of coating solution) Negative birefringence resin N 1 20 parts by mass Toluene ^ 80 parts by mass The above mixture was mixed and stirred to prepare a coating solution. (Coating, drying) © The substrate layer A1 was coated with a comma applicator to form a coating layer having a dry film thickness of 19 μm, and dried at 80 ° C to evaporate the solvent to obtain a laminate 1. &lt;Post-stretching&gt; The obtained laminate 1 was stretched by 28% in a transport direction by a drawing machine while heating at 140 ° C to obtain a retardation film 1 . The retardation of the obtained retardation film 1 was measured by KOBRA 21-ADH manufactured by Oji Scientific Instruments Co., Ltd., and the in-plane retardation Ro3 was 130 nm. The phase difference in the film thickness direction 〇 Rt3 is 20 nm, and the film of the film which is stretched by the substrate layer A1 in place of the laminate 1 is of Onm and Rtl is llOnm. Therefore, the negative refractive index of the negative _ of the retardation film 1 is estimated to be R 〇 2 of 130 and Rt 2 of -90 nm. In the same manner, the base layer A1, A2, B1, B2, and the negative birefringent resins N1, N2, and N3 were used, and the negative birefringent layer was applied and the post-stretching was performed under the conditions described in Table 1. The laminates 2 to 6 and the retardation films 2 to 6 were obtained. &lt;Preparation of retardation film of comparative example&gt; -44 - 200927454 (Retardation film 7) A retardation film 7 was produced by using the substrate layer B3 which was not stretched and having the structure shown in Table 1. - (Retardation film 8) _ The retardation film 8 was produced by using the substrate layer A3 which was not stretched and in the configuration of Table 1. 〇 (Retardation film 9) A retardation film 9 was produced by using the base material layer A1 and not stretching the laminate in the configuration of Table 1. (Retardation film 1 〇) A negative co-refractive resin (N1) was used to form a film, and a negative complex refractive layer N4 (dried film thickness: 19 μm) was obtained. This was bonded to the base layer Α1 which was alkali-alkali treated using an acrylic adhesive, and then stretched under the conditions described in Table 1, to prepare a retardation film 1 〇. (Retardation film 11) A negative co-refractive resin (?1) was used to form a film, and a negative refractive layer Ν5 (dry film thickness: 24 μm) was obtained. This was bonded to the base layer Β1 of the alkaline alkalization treatment using an acrylic adhesive, and then stretched under the conditions described in Table 1, to prepare a retardation film 11. -45- 200927454

1 丨 丨 丨 丨 丨 丨 丨 丨 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较% 23% 1 28% 1 23% § 5 § ο 〇§ 5 •-H 5 ••Η / 5 5 «—I Coating layer (negative birefringent layer) Coating film thickness (before stretching) 19//IB 19 24 μη 31/in 19//m [16//m 1 27 &quot;m 27//m 19μπι 19^m 24 μ m ί?Ρ &gt;_^ CM ca CM CsJ rH ο ο in rH CS3 CS] »H Cv3 〇α CQ iH csj CSJ CS3 CNJ rH Type «-Η iH 21 r-1 2! 03 2 CM CO rH 1 2: iH I? inch in 闼1 塑一•m Ur 幽!1 After film thickness, 50// m 53 &quot;m 90//m 90μκ 50 μ m 50 um 90卩ra 怃Extension) 50/im (no extension) 50 μ id 50 μ id 90 μ m magnification 1 30% 1 | 30% 1 | 25% | 1 20% 1 1 30% 1 I 303⁄4 I / / | 30% | 30% 25% mm οα CO «-Η ΙΛ inch rH in CNJ rH 1ft CN3 rH / / in eg in o CO substrate layer ifp CN5 CO (Ο CQ 呀 CNJ inch CVJ 呀 CQ ττ CSI co 呀rH type r-t &lt; CO &lt; ▼H CO 03 CQ τΗ &lt; rH &lt; CO CQ CO &lt; t-1 &lt;&lt; fH m phase Dispersion film No. tH (M CO inch ΙΟ CO 00 〇o • Ή -46- 200927454 &lt;Evaluation of retardation film&gt;&gt; (Measurement of Roa and Rta) Used in Sub-Measurement Machinery Co., Ltd. KOBRA2 1-ADH, and R〇 and Rth were measured at a relative humidity of 55% at 23 °C, and were regarded as Roa and Rta, respectively (however, a is any one of 1, 2, and 3) (evaluation of unevenness) φ Two retardation films were produced, and two of the retardation axes were vertically overlapped between two polarizing plates that overlap in the crossed Nicols state, and the slow phase axis (or the phase axis) and the polarizing plate were used. The penetrating axis (or absorption axis) is placed in parallel (or perpendicular) to 'evaluate the unevenness of the light leakage. A... no unevenness. B...Unevenness C... quite uneven. φ (Evaluation of Haze) For each of the produced film samples, one of the film samples was measured in accordance with JIS K-6714 using a haze meter (Model 1001DP, manufactured by Nippon Denshoku Industries Co., Ltd.). -47- 200927454

[SI

Remark l l The present invention I | The present invention | m 恃鹬恃 l The present invention 1 丨 The present invention 1 Comparative example Lfc Comparative Example L Comparative example 镒du Comparative example Front contrast 1757 1757 1711 1527 1701 1541 1452 1358 1315 i 1349 1333 —0.24” | 0.22 | | 0.22 | 1 0.22 1 0.23 1 1 0.25 1 in o —0—,_79” | 0.25 | CO CO rH Uneven&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&gt; CQ &lt; 〇o CQ 〇o 举I Rt3 I | 20nm | 20nm| | 20nm 1 20nm| 1 15nm | 20nm| | A 39nm| 1 30nm| | dOnm| | 20nm| 20nm 酗| Ro3 i 130nm 1130nmj 130nm 1130nm| 1152nm 135nmj 1130nm| 130nm| Onin 130nta | 130nm 0&lt 1Rtl 1 |ll0nm IllOnmJ IllOnn | |llOnm | |llOnm ] |llOnm | | 63nm | |l20nm | 120nm llOnm | IllOnm U Slightly 1 R〇i 1 | Onm Onm | Onm | 〇〇| 17nm | | 50nm | 55nra | 〇Onn m 某&amp; goose S job 1 Rt2 i | — 90nm | —90nm | —90am | — 90nm 丨95nm —90nm | a 102nm| —90ara —30nm —90nm —90nm | Ro2 1 | 130nm | 130nm | 130nn | | 130nm | | 152nm ] | 135nm | | 147nm | '130nm 1_ s 130nm 130nm 1 Phase Difference Thin _〇· tH 03 CO l〇CD 00 O -48- 200927454 From Table 2, it is apparent that the retardation films 1 to 5 of the present invention have a desired enthalpy, and have excellent smear and haze. &lt;&lt;Application of polarizing plate and liquid crystal display device&gt;&gt; The retardation film 1 to 6 produced by the production method of the present invention, and the cellulose ester side of the retardation film 7 to 1 1 of the comparative example ( The base material layer side was subjected to alkaline alkalization treatment to prepare a polarizing plate protective film described below. Next, a polyvinyl alcohol film having a thickness of ❹120 μm was immersed in 100 kg of an aqueous solution containing 1 kg of iodine and 4 kg of boric acid, and was stretched 6 times at 5 (TC) to prepare a polarizer, and the single photon was obtained. In the surface, the phase difference film is made of a fully alkalized polyvinyl alcohol 5% aqueous solution as an adhesive, and the second stretching direction is matched with the stretching direction of the polarizer, and the substrate layer side is a polarizer side, respectively On the other hand, Konica Minolta Film KC8UX (Konica Minolta Opt Co., Ltd.) is also alkali-alkalined and bonded to make a polarizing plate. © The LCD TV VIERALX60 (26吋) made by Matsushita Electric Industrial Co., Ltd. The polarizing plate is removed by the polarizing plate, and the polarizing plate CS962 1 made by Nitto Denko Co., Ltd. is bonded to the original polarizing sub-axis.

Konica Minolta Film KC4UE (manufactured by Konica Minolta Opt Co., Ltd.) is used as a polarizing plate for a polarizing plate protective film, and when the viewing angle and front contrast are confirmed, the liquid crystal television using the retardation film 1 to 6 of the present invention has a good viewing angle, and As shown in Table 2, the front contrast measured by EZcontrastl 60D manufactured by ELDIM was also good. In addition, the front side -49-200927454 ratio is the brightness of the normal direction of the component for the white display of the liquid crystal element and the black display, and is calculated by the ratio. In addition, an aqueous emulsion of a polyester ionomer type urethane resin (Hydolan AP-20, manufactured by Dainippon Ink Chemical Industry Co., Ltd.), a solid component concentration of 30% was produced in the same manner. , viscosity 30mPa. . sec) In 100 parts, a polyisocyanate compound (trade name "Hydolan Asister Cl" manufactured by Dainippon Ink Chemicals Co., Ltd.) was added as a binder, and a phase difference film 1 was added. ～6. The first stretching direction of the retardation film 7 to 11 of the comparative example and the stretching direction of the polarizer, and the side of the negative birefringence layer is bonded to the polarizer side, and the other side of the polarizer is Konica Minolta. Film KC8UX (manufactured by Konica Minolta Opt Co., Ltd.) was subjected to alkaline alkalization treatment to prepare a polarizing plate. For these polarizing plates, the polarizing plate in the liquid crystal TV VIERALX60 (26 吋) manufactured by Matsushita Electric Industrial Co., Ltd. is also stripped, instead of the absorption axis of the polarizer with the polarizer, the same as the absorption axis of the original polarizer. The treatment is carried out by bonding Nitto Denko® (sold) adhesive CS962 1 as a polarizing plate on the backlight side, which is a polarizing film used as a polarizing plate protective film by Konica Minolta Film KC4UE (Konica Minolta Opt, manufactured by Konica Minolta Opt) In the case of confirming the viewing angle and the front contrast, the liquid crystal television using the retardation films 1 to 6 of the present invention has a good viewing angle and a good front contrast. -50-

Claims (1)

200927454 X. Patent Application Range: · A method for producing a retardation film, which is a method for producing a retardation film having at least two layers of different optical anisotropic layers, which is characterized by being composed of a positive birefringent polymer The substrate layer is stretched, and then the negative birefringent polymer solution is coated on the substrate layer. After drying to form a negative birefringent layer, the substrate layer and the negative birefringent layer are The laminate is stretched in the vertical direction (second stretching direction) with respect to the stretching direction of the substrate layer (first stretching direction). 2. The method for producing a retardation film according to the first aspect of the invention, wherein the substrate layer is a long-length film produced by a solution flow method or a melt flow method, and the base material layer is made of the long-length film. Extends in the direction of the wide axis. 3. The method for producing a retardation film according to claim 1 or 2, wherein the glass transition temperature of the positive birefringent polymer is Tgl, and the glass transition of the negative birefringent polymer When the temperature is set to ® Tg2, the following formula (1) is satisfied, 〇 °C ^ Tgl-Tg2 ^ 40 ° C (1). A method for producing a retardation film, which is a method for producing a retardation film according to any one of the preceding claims, wherein the J is characterized by a substrate of the phase difference film produced. The retention 値Rol in the layer, the retention 値Rtl in the thickness direction, and the retention 値Ro2 in the plane of the negative birefringence layer and the retention 値Rt2 in the thickness direction have the following formulas (2) to (5) Phase difference film of optical characteristics, -51 - 200927454 -20 g Ro 1 g 40 -· ( 2 ) 80^ Rtl ^ 160 ··· ( 3 ) 50^ Ro2 ^ 200 · ( 4 ) -180^ Rt2 ^- 80 (5) However, the refractive index in the second stretching direction in the plane of the base material layer is nX 鬌〇, and the refractive index perpendicular to the in-plane second stretching direction is nyl, and the refractive index in the thickness direction It is assumed that the thickness of the base layer is dl (nm) ' and the second direction of the diverging direction in the plane of the negative birefringent layer is perpendicular to the direction @ refractive index is set to nx2, and the refractive index of the second extension direction is set. When ny2, the refractive index in the thickness direction is nz2, and the thickness of the negative birefringent layer is set to d2 (nm), Roa=(nxa-nya) xda R Ta= ( ( nxa + nya) /2 -nza ) xda ® (where a is one of 1 and 2). 5. The phase difference of any one of the first to fourth aspects of the patent application. The method for producing a film wherein the negative birefringent polymer has a bonded (heterocyclic) aromatic substituent and polymerizability The polymerizable monomer unit having a minimum atomic number of 0 or more and 2 or less is used as a copolymerization component. A phase difference film is produced according to the manufacturing method of any one of the first to fifth aspects of the patent application. A polarizing plate characterized by having a retardation film as in item 6 of the patent application on at least one side. A liquid crystal display device characterized by having a polarizing plate according to item 7 of the patent application of at least one side of the liquid crystal element. 〇 -53- 200927454 VII. Designated representative map (1) The designated representative figure of this case is: None (2), the representative symbol of the representative figure is a simple description: none 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none -3 -