TW200919035A - Phase difference film, laminated polarizing film, and liquid crystal display device - Google Patents

Abstract

This invention provides a phase difference film, which has been significantly improved in controllability of phase difference, can satisfactorily control the wavelength dependence of the phase difference, and can realize a highly widened view angle when adopted in a liquid crystal display device, a laminated polarizing film, which can realize a widened view angle using the phase difference film, and a liquid crystal display device having improved performance, particularly a widened view angle. The phase difference film uses a structure which simultaneously has both a structural birefringent index and a molecule oriented birefringent index.The structure is a repeated multilayered structure for developing the structural birefringent index is a structure comprising, as constituent units, a layer having negative optical anisotropy derived from a molecule oriented birefringent index having a different average refractive index and a layer having positive optical anisotropy.

Description

200919035 IX. The present invention relates to various optical devices, and more particularly to a retardation film suitable for use in a liquid crystal display device, a laminated polarizing film using the retardation film, and a liquid crystal display device. . [Prior Art] Conventionally, a film having optical anisotropy has been widely used as a retardation film, an optical compensation film, and a viewing angle-enhancing film, and has contributed significantly to an improvement in optical performance of a liquid crystal display device. In the present specification, a film for optically anisotropic films such as a retardation film, an optical compensation film, and a viewing angle-enhancing film is used as a "phase difference film" for all optical devices. For such a retardation film, various proposals have been made for the improvement of various performances expected. In particular, the technique for improving the viewing angle of a liquid crystal display device is very important for a phase difference film, and there have been many proposals. For example, in the first to fourth embodiments, the principal refractive index (nx, ny, nz' or less is referred to as a three-dimensional refractive index) in the three directions in which the retardation film is controlled to be in parallel or perpendicular to each other in the in-plane control. Specifically, in Patent Documents 1 to 4, it is described that the main refractive index (nz) in the thickness direction is larger than either of the two principal refractive indices (nx, ny) in the plane, and is smaller than the remaining one. As described above, by controlling the principal refractive indices (nx, ny, nz) in three directions, the viewing angle dependence of the phase difference of the retardation film can be controlled, and as a result, the viewing angle of the liquid crystal display device can be widened. -5-200919035 However, the methods described in Patent Documents 1 to 4 use the birefringence (hereinafter referred to as molecular alignment birefringence) due to the alignment of the polymer constituting the retardation film, so that the phase difference obtained is obtained. The properties of the film have its limitations. Further, in order to set the main refractive index (nz) in the thickness direction to the middle enthalpy of the two principal refractive indices (nx, ny) in the plane, a very complicated stretching method must be employed. Further, in order to obtain a retardation film having such a main refractive index, a complicated stretching method is required, so that it is difficult to finely control the phase difference ,, and the wavelength dependence of the phase difference is difficult to sufficiently control. Is the problem. As another method for realizing a wide viewing angle of a liquid crystal display device, there has been proposed an effect of bonding a plurality of retardation films with a binder or the like to achieve the object. For example, Patent Document 5 discloses that a uniaxial optical film having a positive optical axis in a lamination plane and a uniaxial optical film having an optical axis in the plane are used to improve the viewing angle dependence of the retardation film. Sexual technology. According to the method of Patent Document 5, the control of the phase difference can be performed without using a complicated extension method. However, the method described in Patent Document 5 is also a method of using only molecular orientation birefringence, and thus the performance of the phase difference film obtained is limited. Further, since the obtained optical characteristics are a result of mixing of two kinds of optical characteristics of the positive uniaxial optical film and the negative uniaxial optical film, it is difficult to freely control the optical characteristics (especially the wavelength dispersion of the phase difference). Another method for realizing a wide viewing angle of a liquid crystal display device is described in Patent Document 6 as an isotropic layer composed of two types of inorganic materials having different refractive indices in a single layer. The interactive formation -6-200919035 combines a method of forming a repeating multilayer structure, thereby imparting a birefringence (hereinafter referred to as structural birefringence) to a phase difference in the in-plane and thickness directions. The laminated retardation film described in Patent Document 6 is intended to utilize a structural birefringence, and a negative C plate (that is, two principal refractive indices (nx, ny) in the plane are equal to each other and to the normal direction of the surface) A plate having a main refractive index (nz) smaller than two principal refractive indices (nx, ny) in the plane is used in a liquid crystal display device. Patent Document 6 describes an example in which the film is used in a twisted nematic (tn) type liquid crystal display device to improve the viewing angle of the liquid crystal display device. However, the performance of the retardation film obtained by the method described in Patent Document 6 is only limited by the method of structural birefringence. Further, in the method described in Patent Document 6, only a negative uniaxial anisotropic multilayer structure can be obtained. The phase difference film used in the optical field is expected to have improved performance and better phase difference control, and this demand is endless. [Patent Document 1] 曰 特 特 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利Japanese Patent Laid-Open Publication No. Hei 07-230007 (Patent Document 5) Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. [Problem] The present invention has been made in view of the above-described conventional techniques, and one of the objects of the present invention 200919035 is to provide a freely controllable three-dimensional refractive index and to sufficiently control the wavelength dependence of the phase difference. When used in a liquid crystal display device, a phase difference film having a high level of viewing angle can be realized. Another object of the present invention is to provide a laminated polarizing film which can realize a wide viewing angle and a liquid crystal display device having a greatly enlarged viewing angle. [Means for Solving the Problems] In order to solve the above problems, the inventors of the present invention have found the following invention by repeating the results of the deliberate review. The retardation film of the present invention comprises a repeating multilayer structure in which at least two layers having different average refractive indices are constituent units, and the above-mentioned repeating multilayer structure may exhibit structural birefringence, and at least 1 of the at least two layers The seed layer has a negative optical anisotropy layer (A) due to molecular orientation birefringence, and at least one of the at least two other layers has positive optical anisotropy due to molecular orientation birefringence Sex layer (B). The laminated polarizing film of the present invention comprises a phase difference film of the present invention and a polarizing film. The liquid crystal display device of the present invention comprises the retardation film of the present invention. [Effects of the Invention] Since the retardation film of the present invention simultaneously uses both molecular compatibility and birefringence and structural birefringence, it has a controllability of a phase difference which is remarkably improved, that is, the retardation film of the present invention is A phase difference film having a novel configuration which is not required to be obtained in the past or which is difficult to obtain in the period of -8-200919035 and which is required to meet the wide-ranging requirements required for the retardation film is obtained. Therefore, according to the retardation film of the present invention, the main refractive index (nx) in the thickness direction can be set to the middle enthalpy of the two principal refractive indices (nx, ny) in the plane without performing complicated alignment treatment. Further, for example, according to the retardation film of the present invention, the wavelength dependence of the phase difference can be sufficiently controlled by simultaneously using molecular matching to both birefringence and structural birefringence, that is, the phase according to the present invention. The difference film can independently control the in-plane phase difference 値(R ( λ )値) and the thickness direction phase difference 値(Rth ( λ)値). Further, the retardation film of the present invention, as a layer constituting a repeating multilayer structure for exhibiting structural birefringence, is a layer having a negative optical anisotropy having an average refractive index and a layer having a positive optical anisotropy. Therefore, the wavelength dependence of the retardation (especially the in-plane retardation (R 値)) can be freely controlled, and as a result, the so-called inverse dispersion phase difference which increases the wavelength while increasing the absolute 値 is also obtained. film. The retardation film of the present invention can provide various optical characteristics. Therefore, as long as the retardation film of the present invention and the polarizing film are laminated, a laminated polarizing film having a high level of viewing angle expansion performance can be obtained. Further, by combining the retardation film of the present invention and a liquid crystal cell, a liquid crystal display device having remarkably improved display performance (especially, viewing angle characteristics) can be obtained. [Embodiment] -9-200919035 <Retardation film> The retardation film of the present invention uses both structural birefringence and molecular alignment birefringence. Specifically, the retardation film of the present invention comprises a repetitive multilayer structure in which at least two layers having different average refractive indices are used as constituent units, and the repetitive multilayer structure may exhibit structural birefringence and at least two layers At least one of the layers has a negative optical anisotropy layer (A) due to molecularly oriented birefringence, and at least one of the at least two other layers has positive optics due to molecularly oriented birefringence Anisotropic layer (B). Further, in order to effectively exhibit the structural birefringence, the film thickness of each layer must be sufficiently smaller than the wavelength of light, and as a result, the phase difference film of the present invention has a repeating multilayer structure and the internal reflection is substantially absent from the visible light region. Phase difference film. In the present invention, a film having optical anisotropy such as a retardation film, an optical compensation film, or an angle-enlarging film, which is used for various optical devices, is defined as a "phase difference film". [Comparison with a conventional retardation film] The thickness of each layer which is a constituent unit of the repeating multilayer structure contained in the retardation film of the present invention exhibits structural birefringence at the same time, and at the same time, the internal reflection due to the multilayer structure does not substantially exist. In the visible light region, it must be sufficiently smaller than the wavelength of visible light. Since the retardation film of the present invention has a very thin thickness as a constituent unit of the repeating multilayer structure, the retardation film of the present invention exhibits a function as a phase -10-200919035 poor film after forming a repeating multilayer structure. Further, in the conventional retardation film, although a plurality of retardation films are laminated and used, in this case, both the structural birefringence and the molecular alignment birefringence are not simultaneously used to control the high optical anisotropy. . Therefore, the retardation film of the present invention and the phase difference film of the prior art which are used by laminating only a plurality of retardation films are fundamentally different in design concept. [Molecular Alignment Birefringence and Structural Birefringence] The "molecular aligning birefringence" in the present invention means a difference in refractive index due to the direction of light transmission by the alignment or arrangement of molecules or atoms ( That is, birefringence) is an optical anisotropy which is exhibited by alignment of a polymer or a liquid crystal or the alignment of a crystalline substance. In the case of optical anisotropy due to molecularly oriented birefringence, at least one of the three refractive indices when the medium is approximated to the refractive index ellipsoid and expressed by the three-dimensional refractive index nx, ny, nz It is different from the other two refractive indices. In the retardation film, when nx and ny of the in-plane refractive index among the three refractive indexes are different, there is a state of molecular orientation birefringence in the plane. On the other hand, 'structural birefringence' means that it is different from the above-described molecular orientation birefringence, that is, it is not aligned by molecular or atomic gradation, and is formed by a medium having a different refractive index which is sufficiently smaller than the wavelength of light. The optical anisotropy exhibited by the structure. In the present invention, in order to exhibit structural birefringence, it is necessary to form a repeating multilayer structure of at least two layers having different average -11 - 200919035 luminosity. Further, in the repeated multilayer structure, the interface between the layers having different refractive indices is preferably substantially parallel to the surface of the film. [Principle of optical anisotropy presentation of retardation film] The following describes the principle of presentation of optical anisotropy of the retardation film of the present invention. Further, in the present invention, in the case of the uniaxial retardation film, the refractive index orientation of the extraordinary refractive index ellipsoid is defined as the "optical axis". On the other hand, in the case of a biaxial retardation film, the "optical axis" is not defined in the present invention. In addition, in either case, the maximum refractive index orientation in the plane of the medium is referred to as the "late phase axis". The retardation film of the present invention is used by highly combining a structural birefringence and a molecular orientation birefringence. Therefore, the retardation film of the present invention and other conventional retardation films (for example, even a portion having a structural birefringence and a portion having a molecularly-oriented birefringence exist simultaneously, which are optically independent, Other conventional retardation films which optically exhibit the action of a combination of two optically anisotropic media have a large difference in structure. In the retardation film of the present invention, the structural birefringence is highly fused with the molecular alignment birefringence system, and as a result, the obtained repetitive multilayer structure is an optically optically anisotropic medium. Moreover, this medium must be achieved using the repeated multilayer construction of the present invention. Since the retardation film of the present invention is an optical anisotropic medium, when the measurement wavelength is determined, optical anisotropy can be exhibited only by three three-dimensional refractive indices (nx, -12 - 200919035 ny, nz). Moreover, the three-dimensional refractive index can be freely controlled. Therefore, a phase difference film which has been difficult to obtain or which has not been obtained in the past can be obtained by control. Here, in order to explain in comparison with the present invention, the multilayer structure described in the above Patent Document 6 will be described. Fig. 2 is a schematic view showing a multilayer structure described in Patent Document 6. The multilayer structure of Patent Document 6 is a structure in which optical layers are optically isotropic. Here, in Fig. 2, 21 is a ruthenium layer (optical isotropic layer), 22 is an L layer (optical isotropic layer), 23 is a repeating multilayer structure composed only of an optically isotropic layer, and 24 is a multilayer structure. The refractive index ellipsoid of 23. The refractive index anisotropy of the optically anisotropic medium having the composition shown in Fig. 2 is represented by the following formulas (1 1 ) and (1 2 ). The basis of these two formulas is based on the "effective medium approximation theory". The theory is that the refractive index is averaged in a repeating multilayer structure that is sufficiently smaller than the wavelength of light. Forming a multilayer structure in which the film thickness of each layer is much smaller than the wavelength of light and the two layers having different refractive indices are repeated, and when the interface between the layers is parallel to the surface of the medium, the following formulas (11) and (12) are established. Know the person. [Math 1] %

+ dH+dL (11) (12)

dL dH + dLnH dH + dLnL2 Here, n. And ne are the normal light refractive index of the medium 23 of FIG. 2 and the abnormal light refractive index of -13-200919035, respectively.

The 24 in Fig. 2 indicates the refractive index ellipsoid of the medium 23, and the n shown in the refractive index ellipsoid 24. The direction of ne and the medium 23 are n. The direction of ne is the same. dH, dL, nH, and nL respectively indicate the film thickness 21 of the n layer, the film thickness 22 of the L layer, the refractive index of the germanium layer, and the refractive index of the L layer. It is mathematically clear from the equations (11) and (12), and the relationship of the following formula (1 3 ) is established under the condition that the refractive indices of the two layers are different. [Math 2] n〇 > ne (13) Equation (13) indicates that the medium 23 of Fig. 2 is negative uniaxial anisotropy. Next, a mode of the multilayer structure of the retardation film of the present invention is shown in Fig. 1. Here, in FIG. 1, 11 is a first layer, 12 is a second layer, and 13 is a repeating multilayer structure in the retardation film of the present invention, and two layers U and 12 having an average refractive index are alternately laminated. 14 is a refractive index ellipsoid in which the multilayer structure 13 is repeated, 15 is a refractive index ellipsoid of the first layer, and 16 is a refractive index ellipsoid of the second layer. In the repetitive multilayer structure of the present invention of Fig. 1, the optical anisotropy of any medium forming the layer may be more similar to the refractive index ellipsoid, and the three-dimensional refractive index of the multilayer structure may be repeated in the case of being applicable to an approximately effective medium. The following formulas (14) to (16) can be derived by extending the equations (11) and (12). -14- 200919035 [Math 3] bj + - 'T a ten b (14) = a αΛ-b ^ (15) 1 a 1 b 1 (1 6) a-tb where nx, ny, nz The three-dimensional refractive index of the repeating multilayer structure 13 of Fig. 1 is the three-dimensional refractive index X-axis direction of the orthogonal coordinates of the refractive index ellipsoid 14 in the X-axis, the y-axis, and the z-axis direction. In the case of optical anisotropy, the in-plane slow axis direction y-axis direction: an orientation perpendicular to the x-axis direction in the plane of the repeated multilayer structure 13 (ie, the plane formed by the X-axis and the y-axis) The plane parallel of the multilayer structure 13 is repeated. Z-axis direction: the normal direction nnx, nny, ηπ 对 of the face of the repeated multilayer structure 13: the refractive index ellipsoid of the layer 1 1 having negative optical anisotropy of FIG. The three-dimensional refractive index represented by 15 is the refractive index of the orthogonal coordinates in the X-axis, the y-axis, and the x-axis direction (in the case of optical anisotropy in the plane of the layer 11), the refractive index is the axis of the maximum orientation. The retardation axis is defined as parallel to either the X-axis or the y-axis), npy, npz: the refractive index of the layer ι2 having positive optical anisotropy in FIG. The three-dimensional refractive index represented by 丨6 is the refractive index of the orthogonal coordinates in the X-axis, y-axis, and z-axis directions (the case where optical anisotropy exists in the surface of layer 12), and the refractive index is the axis of maximum orientation. The retardation axis system -15-200919035 is defined as being parallel to either the X-axis or the y-axis) a, b: film thickness of the layer 11 having negative optical anisotropy and the layer 12 of positive optical anisotropy, respectively (nm) In the present invention, the definition of the three-dimensional refractive index of one repeating multilayer structure is as described above unless otherwise specified. That is, as shown by the above formulas (14) to (16), the retardation film of the present invention determines the optical anisotropy of the repeating multilayer structure by both the layer structure and the molecular orientation birefringence of each layer. Therefore, according to the present invention, by using the characteristics of both of them, it is possible to obtain a special optical anisotropy which has been difficult to achieve in the past. Furthermore, the above formulae (14) to (16) depend on the wavelength. Since the structural birefringence due to the layer structure and the molecular orientation birefringence of each layer generally have different wavelength dispersion characteristics, by controlling both of them, wavelength dispersion characteristics which have not been achieved in the past can be obtained. On the other hand, as described above, in the repetitive multilayer structure described in Patent Document 6 in which each layer is optically isotropic, only the anisotropy represented by the formula (13) can be obtained. Therefore, in the repetitive multi-layer structure described in Patent Document 6, it is understood that the controllability of the anisotropy is inferior to the repetitive multi-layer structure of the present invention. Further, an example of more specific optical anisotropy of the present invention will be described in detail in the design examples and examples described later. <Repeated multilayer structure> The retardation film of the present invention comprises a repeating multilayer structure in which two layers of at least -16 to 200919035 having different average refractive indices are used as constituent units. In the present invention, constructive birefringence can be exhibited by repeating a multilayer structure. [The number of the types of the layers constituting the repeating multilayer structure] The repeating multilayer structure included in the retardation film of the present invention may be at least two kinds of layers having different average refractive indices as constituent units, and may include three kinds of refractive indexes different from each other. The above layers are used as constituent units. However, in view of the ease of control of optical anisotropy (especially ease of fabrication), two types of layers having different average refractive indices of a repeating multilayer structure are preferred. Fig. 2 and the above formulas (14) to (16) show a case where two layers having different average refractive indices are used as a repeating multilayer structure of a constituent unit. In the case where the repeated multilayer structure includes only two layers A and B having different refractive indices, the arrangement of the layers A and B may be as follows: forming (AB ) ( AB ) (AB ) ···. ( AB ) The order of layer A and layer B is often the same, and the order of layer A and layer B in the form of (AB ) ( BA ) ( AB ) ···· ( BA ) is regularly or randomly different, and Any arrangement is possible in terms of obtaining the optical properties of the present invention. Here, although the minimum repeating unit is shown in (), it is preferable to consider the phase difference control property, and the order of the layer A and the layer B of the minimum repeating unit is kept constant in one repeated multilayer structure. Fig. 3 is a view showing a repeating multilayer structure in which three layers are used as constituent units. Here, in FIG. 3, 31 is the first layer, 32 is the second layer, 33 is the third layer, and 34 is the repeated multilayer structure of the retardation film of the present invention. 35 -17- 200919035 is a repeating multilayer structure 34 The refractive index ellipsoid, 36 is the refractive index ellipsoid of the kth layer (k = 1 to 3). The configuration of the repeating polyfluorene structure of three or more layers is, for example, when there are three layers A, B, and C having different refractive indices, '(A/B/C) / (A/B/) C ) / ( A/B/C ) /·· ( A/B/C ), (A/B/C) / ( B/C/A) / ( A/B/C) /... (C/B /A)etc. That is, as in the above, () indicates the minimum repeating unit, but the order of the layer A, the layer B, and the layer C in the minimum repeating unit is not limited. However, in terms of ease of manufacture or control of phase difference, the alignment of the minimum repeating unit is preferably the same in all of the repeated multilayer structures. Here, when the above formula (I4) to (Ιό) of a repeating multilayer structure of two types of layers having different average refractive indices is extended into a repeating multilayer structure of n kinds of layers having different average refractive indices, the following formula can be obtained. (17)~(19). [Math 4] Σ k=l

Σ d k=l * k (19) ® 3 Repeated multilayer construction 34 with refraction axis, y-axis,

Where, the rate ellipsoid: X-axis direction: '18- 200919035, is the in-plane slow axis direction y-axis direction: the orientation perpendicular to the x-axis direction in the plane of the repeated multilayer structure (ie, by the X-axis And the plane formed by the y-axis is parallel to the surface of the repeated multilayer structure 34.) Z-axis direction: the normal direction iUx'nky'nkZ__ of the face of the repeated multilayer structure 34 (for example, in the figure) 31, 32 or 3 3) The three-dimensional refractive index represented by the refractive index ellipsoid 36 is the refractive index of the orthogonal coordinates in the X-axis, the y-axis, and the Z-axis direction (the optical difference exists in the surface of the k-th layer) In the case of directionality, the late phase axis is defined as being parallel to either the X-axis or the y-axis.) dk: film thickness (nm) of the k-th layer [inter-layer blending region] between the layers of the repeated multilayer structure, There may also be blending regions in which the materials forming the layers are mixed. In particular, in the case of repeating a multilayer structure by multi-layer melt extrusion, such a region may exist depending on the extrusion conditions or materials used. However, the film thickness of the blended regions must be much smaller than the wavelength of the light. When the film thickness is not much smaller than the wavelength of light, internal reflection or haze may occur. The thickness of the blended region can be confirmed by observing the cross section of the multilayer structure by an electron microscope such as a scanning electron microscope or an electron microscope. For example, the thickness of each layer and the thickness of the blended region can be confirmed by the line profile of the number of transmitted electrons observed in the thickness direction observed by a transmission electron microscope. -19- 200919035 I believe that the blending ratio of the two materials in the blending zone is approximately linear with respect to the thickness direction. Therefore, since the optical anisotropy of the blending region can be expressed by the constituent fraction of the linear change, in the case where the blending region exists, the equations (11) and (12) are respectively expressed by the following formula (11,). And (12') indicates. [Math 5]

Η02 =Ηη/ + ΒΓη2 -dn + Ln^ = HnH2 + ^-(n„2 +nHnL+nL )+ LnL

Tiff a Tit ^ (11,)

1 H r» 1 dn , 2 H ^ B

nH2 _ nHnL nL

[Math 6] H =——^—— n ds 5 =-^-

Dji + dL

In L--dL, the film thickness of the blending region is similarly the same as in the case of equations (14) to (16), and can be transformed into the following formula (14,)~ (16' ). -20- 200919035 [Math 7] 2 = HnJ Β( +—{«』 3 v J «2 + ««V +v2)+i?v2 (14,) 2 ny = Hnn; B{ +—1« 3V, nrrynpy + npy2) + Lnj^ (15,) 1 Η BL (1 6') 2 -2-1 '{ in^pz [Math 8] d + d ^ + h : dB a-\-dB+ Bb a-\-dB-\-b where dB is the film thickness of the blending zone. This way of thinking can also be applied to the case where there are blending zones between the layers in the repeated multilayer structure of n layers, and the above formula (17) ) (19) can be changed to form the following formula (1 7 ') to (1 9 '), respectively. [Math 9] y «ΐ/ +Σ{-γ-«(*-!)/ +Tf(«fe2 + /Σ(^* +t,)r) (17,) ny

(18,) -21 - 200919035

Wherein dk : film thickness (nm) of the kth layer bk: film thickness of the blending region between the kth layer and the k-1th layer (nm) film thickness of the blending region, for example, using a plurality of layers The case where the multilayer structure is formed by the melt extrusion method can be adjusted by the residence time until the extrusion from the die, the laminar flow, and the like. Further, the film thickness of the blended region can be adjusted by the compatibility of the materials forming the respective layers. By the presence of the blending region, it is possible to have an effect of improving the adhesion, or the optical characteristics of the entire phase difference film with respect to the variation of the thickness of each layer are not easily changed. However, as can be seen from the above formulas (14,) to (16,) and (17,) to (1 9 '), since the blending region increases, the structural birefringence becomes smaller. It is preferred to adjust the thickness of the blended region within a range that satisfies the refractive index of the material forming the respective layers or the optical properties for the purpose. In addition, as a result of the increased blending area, the individual material layers disappear and become a continuum in which only the blended region 'repeated multilayer structure can be a refractive index gradient. At this time, the equations (1, 1) and (I2,) refract the highest part of the blending ratio of the low refractive index material by setting the refractive index of the highest portion of the blending ratio of the high refractive index material in the blending region to nH. The rate is set to nL and can be handled in the same manner. The equations (14,) to (16,) and (17,) to (19,) can also be handled in the same manner. -22-200919035 [Layer thickness as a constituent unit of the repeating multilayer structure] The layer thickness of the constituent unit of the repeating multilayer structure included in the retardation film of the present invention is considered as the phase difference control property, regardless of the number of layers. It is preferable that the film thickness of each layer in one repeated multilayer structure is made substantially the same according to the type of the layer. Further, regarding the same type of layer, the average thickness of the film of the same type is preferably within a range of ± 50% or less. The deviation from the average enthalpy is preferably ±40% or less, more preferably 30% or less, and most preferably less than 1%. Further, the thickness of each layer can be confirmed by observing the cross section of the multilayer structure by an electron microscope such as a scanning electron microscope or an electron microscope. Further, as can be seen from the above formulas (14') to (16'), and (1 7 ') to (19'), the three-dimensional refraction of the multilayer structure of the multilayer structure is repeated for different types of layer thicknesses of the multilayer structure. The rate is very important. [Optical anisotropy of a layer which is a constituent unit of a repeating multilayer structure] The optical anisotropy of the layer constituting the repeating multilayer structure included in the retardation film of the present invention is determined by the phase difference control property. It is better to keep the type as constant as possible. Regarding the optical anisotropy of each layer, since each film thickness is much smaller than the wavelength of light, it is generally difficult to directly observe it. However, as described above, the film thickness of each layer can be determined by an electron microscope to determine the average enthalpy. Therefore, the refractive index wavelength dispersion of the intrinsic physical properties of the material forming each layer, the birefringence wavelength dispersion, the thickness of each layer of the multilayer structure, the number of layers, and the phase difference 面(R値(nm )) in the surface -23-200919035 a wavelength dispersion data of a thickness direction phase difference 値 (Rth 値 (nm)), in the case where the above formula (μ) to (16) or the above formulas (17) to (19) or a blending layer are present, by using the above The average optical anisotropy of each layer can be obtained by the formulas (14,) to (16,) or the above formulas (17,) to (19,). Further, the in-plane phase difference 値 (R 値 (nm )) is defined by the following formula (40 ′). R = (nx - ny) d (40,) Further, the thickness direction phase difference 値 (Rth 値 (nm )) is defined by the following formula (40). [Math. 1 0] ~2^ (4 0) In addition, according to the above-mentioned "analysis of effective medium approximation theory", for a repetitive multi-layer structure, the equation (14) ~ (16) or (17) ~ ( 1 9 ) indicates that, in the case where the blending layer is present, the wavelength is specified by the above formula (14,) to (16,) or the above formulas (17,) to (19,) The optical anisotropy can be expressed by a set of three-dimensional refractive indices. Therefore, in the present invention, the parameters of the three-dimensional refractive index such as the in-plane phase difference 値(R値), the thickness direction phase difference 値(Rth値), and the thickness direction alignment index (NZ値) of the repeated multilayer structure are used as long as there is no special -24- 200919035 Other regulations' are set to relate to a number of repeated multilayer structures. [Repeat the thickness of the multilayer structure] The film thickness of one repeating multilayer structure is preferably from 1 to 300 μm, preferably from 5 to 200 μm, and more preferably from 1 to 150 μm, and the optimum is from 20 to 100 μm. When the film thickness of the structure is too thin, "there may be a case where sufficient optical anisotropy is not obtained. On the other hand, if it is too thick", there is a problem that the ruthenium film cannot be wound. [Number of Repeated Multilayer Structures] The number of the repeated multilayer structures in the retardation film of the present invention may be only one, and may include a plurality of laminates having a repeating multilayer structure having different materials, different thickness ratios of layers, and the like. . In the case of a complex multilayer structure including a plurality of plural layers, the structure of a repeating multilayer structure in which a plurality of layers are composed of the same two kinds of layers and the thickness ratio of the repeating structure is different or the thickness ratio is different from the number of layers is laminated as Better. Fig. 4 shows a retardation film 43 made of a repeating multilayer structure 42 having a thickness ratio of α and a repeating multilayer structure 42 having a thickness ratio of β, using only two materials of ruthenium and iridium as a layer. In Fig. 4, the multilayer structure is repeated as two, but in the present invention, it is also possible to include two or more repeated multilayer structures, as long as they are most suitable for use. However, as the number of multilayer structures increases, the thickness of the retardation film also increases. Therefore, the number of repeating multilayer structures is preferably 5 or less, preferably 3 or less, and most preferably 2 or less. -25- 200919035 Further, even a phase film having a plurality of repeating multilayer film structures can be formed at one time by, for example, using a well-known splitting block (multi-layer melt extrusion method of feed) to control film thickness. Internal reflection of the multilayer structure] The reflection of the retardation film of the present invention can be roughly classified into "external and "internal reflection". Here, "external reflection" means that between the two surfaces of the phase film and other media having different refractive indices A phenomenon which is also generated in an anti-general phase difference film produced. On the other hand, "reflection" means a reflection other than external reflection, that is, reflection of a film sheet. Therefore, in the phase of the present invention including a repeating multilayer structure In the film, "internal reflection" means interference generated at a plurality of interfaces thereof. The repetitive multilayer structure of the retardation film of the present invention must be substantially absent from the visible light region. Specifically, the internal rate Preferably, it is 2% or less, preferably 1% or less, more preferably lower, and more preferably 0.1% or less. Further, the "internal reflectance" of the present invention means the wavelength of measurement. For example, it is determined by subtracting the external reflection caused by the surface according to the reflectance and the transmission result of the spectrophotometer. Further, the phase difference film of the present invention is preferably absorbed in the visible light region. The absorption system depends on the wavelength dependence of the absorption of the material used, so it is selected from materials that the visible light does not absorb: and the 'phase difference film of the present invention is used to reflect the light in the visible light region. The difference between the internal surface and the thin surface reflection or partial reflection is 0. 5 %. The measurement coefficient is not good at the 550 nm rate. It does not produce -26-200919035. The scattering is better. The polarization characteristics of the retardation film are deteriorated, and generally appear to be a structure having a size close to the wavelength of light. In the present invention, the interface at the repeated multilayer structure is not parallel to the surface of the retardation film (that is, the multilayer structure is repeated). In the case where the interface is disordered, there is a case where scattering occurs. Therefore, in the present invention, it is preferable that each interface forming the repeating multilayer structure is limited to be parallel to the surface of the retardation film. The method for observing the scattering is measured by haze, and the haze is preferably 2% or less, preferably 1.5% or less, more preferably 1% or less, and most preferably 〇·8 % or less. [Optical thickness (nd (nm )) of the layer as a constituent unit of the repeated multilayer structure] In order to prevent the internal reflection of the retardation film of the present invention, it is necessary to make the thickness of each layer which is a constituent unit of the repeated multilayer structure much smaller than that of light. At the same time, the thickness of the above-mentioned minimum repeating unit is also much smaller than the wavelength of light. Here, since the interference effect depends on the product nd (optical thickness) of the refractive index η of the layer and the thickness d, it is a repetitive multilayer structure. The optical thickness nd (nm) of each layer of the constituent unit is preferably λ/5 or less. Preferably, it is λ/15 or less, more preferably λ/20 or less. The most preferable one is λ/25 or less, and the most preferable one is λ/30 or less. Here, λ means 400 to 800 nm of the range of visible light, and it is preferable to design it at 550 nm having the highest visual sensitivity. -27- 200919035 [Layer (A) having negative optical anisotropy due to molecularly oriented birefringence] The repeating multilayer structure contained in the retardation film of the present invention will constitute at least two layers of a multilayer structure. At least one layer is set to have a layer (A) ° having a negative optical anisotropy due to molecular orientation birefringence, and as shown in the multilayer structure described in the above Patent Document 6 as a constituent unit of the repeated multilayer structure In the case where the faces of the respective layers are isotropic, as can be seen from the above formulas (14) to (16) or (17) to (19), only the normal direction of the obtained multilayer structure can be made. A uniaxial structure having a negative optical axis. Here, "having a negative optical anisotropy" in the present invention is defined as a three-dimensional refractive index satisfying the following formula (20) or (2 1 ). Nz > nx = ny (2 0) nz ^ nx > ny (2 1) In the formulas (20) and (21), nx and ny are refractive indices parallel to the in-plane of the layer and perpendicular to each other. , nx is defined as the largest in-plane refractive index (refractive index of the azimuth axis direction). Further, nz is defined as the refractive index in the normal direction of the plane of the layer. Further, since a more complicated optical anisotropy is obtained in the preferred embodiment of the present invention, the state of optical anisotropy in the plane of the layer can satisfy the formula (2 1 ). As shown in the above formula (13), a structure having a repeating multilayer structure in which only a layer of optical isotropic is used as a constituent unit has a refractive index in the normal direction of the surface which is smaller than the in-plane direction of the structure. Refractive index. That is, only -28-200919035, by constructing the birefringence by repeating the multilayer structure, cannot make the refractive index in the normal direction larger than the refractive index in the in-plane direction. On the other hand, in the present invention, the layer (A) having a negative optical anisotropy of the formula (20) or (2!) (preferably (2 1 )) is introduced as a constituent unit of the repeated multilayer structure. 'The refractive index difference between the normal direction and the in-plane direction can be freely controlled. [Layer (B) of positive optical anisotropy due to molecularly-oriented birefringence] In the repetitive multilayer structure contained in the retardation film of the present invention, at least one of at least two layers constituting the multilayer structure is used. The layer is set to a layer (B) having positive optical anisotropy due to molecularly oriented birefringence. Here, the term "having positive optical anisotropy" in the present invention is defined as a three-dimensional refractive index satisfying the following formula (22) or (23). Nx > ny = nz (22) nx ^ ny > nz (23) The definitions of the three-dimensional refractive indices in the equations (22) and (23) are the same as those defined in the above formulas (20) and (21). Further, since more complicated optical anisotropy can be obtained by the present invention, the state of optical anisotropy in the plane of the layer can satisfy the formula (23). In the present invention, 'the layer (b) having the positive optical anisotropy of the formula (22) or (23) (preferably, the formula (2 3 )) can be more freely introduced as a constituent unit of the repeated multilayer structure. The phase difference in the ground control plane, and the wavelength dependence of the phase difference in the plane can be freely controlled -29 - 200919035. [Combination of layer (A) having negative optical anisotropy and layer (B) having positive optical anisotropy] In the repetitive multilayer structure contained in the retardation film of the present invention, at least two kinds of multilayer structures are formed. At least one of the layers is set to a layer (A) having a negative optical anisotropy due to molecularly oriented birefringence, and at least one of the at least two layers is set to have a molecularly oriented birefringence A layer of positive optical anisotropy (B). In the repetitive multilayer structure included in the retardation film of the present invention, the layer (A) having negative optical anisotropy and the layer (B) having positive optical anisotropy are not necessarily included as constituent units. Here, the retardation absolute enthalpy of one of the retardation films composed of a general polymer tends to decrease as the wavelength increases. However, as a constituent unit of the repetitive multilayer structure included in the retardation film of the present invention, since both the negative optical anisotropy layer (A) and the positive optical anisotropic layer (B) exist, it is freely The retardation (especially the wavelength dependence of the retardation in the plane) is controlled, and as a result, a so-called reverse dispersion retardation film in which the absolute 値 is also increased while increasing the wavelength is obtained. In the repetitive multilayer structure of the present invention, a layer having positive optical anisotropy due to molecularly oriented birefringence and a layer having negative optical anisotropy due to molecular orthogonal birefringence are combined. According to this configuration, for example, the case where the slow axis of each layer is perpendicularly intersected, that is, for example, a case where a layer having positive optical anisotropy and a layer having negative optical anisotropy are laminated is extended, since each layer has Since the difference between R 与 and R 値 of the whole is substantially the same, -30-200919035 can greatly change the dispersion of R 。 . That is, the wavelength dispersion of R値 is combined by a layer having positive optical anisotropy due to molecularly oriented birefringence and a layer having negative optical anisotropy due to molecularly oriented birefringence, and Compared with the combination of isotropic and isotropic, negative and negative, negative and isotropic, positive and isotropic optical anisotropy, it can be controlled in a wider range. Here, the R 値 is defined by the front incident light, specifically, as shown by the formula (40 '), the three-dimensional refraction of the three-dimensional refractive index of the front incident light in the X-axis direction and the y-axis direction is used. The rate (ηx and ny) is defined. As shown by the formulas (14) and (15), the three-dimensional refractive index (ηX and ny) in the X-axis direction and the y-axis direction of the three-dimensional refractive index of the front incident light is equally affected by the structural birefringence. Therefore, the wavelength dispersion of R値 can be freely controlled between self-reverse dispersion and general dispersion without substantially considering the influence of structural birefringence. On the other hand, the Rth lanthanum is defined by obliquely incident light, and specifically, three three-dimensional refractive indices in the X-axis direction, the y-axis direction, and the z-axis direction are used as shown in the formula (40). (nx, ny, nz) is defined. The three-dimensional refractive index (, ny ) in the X-axis direction and the y-axis direction of the three-dimensional refractive index in the plane direction and the three-dimensional refractive index in the z-axis direction of the three-dimensional refractive index in the thickness direction are expressed by the formulas (14) to (16). (nz) is influenced by structural birefringence in a different pattern from each other. Therefore, the wavelength dispersion of 'Rth値 is different from the wavelength dispersion of R値, that is, 'not only the influence of molecular alignment birefringence, but also the influence of structural birefringence, which can be freely controlled. Reverse dispersion to the general dispersion. As described above, by controlling the wavelength dispersion of R 値 -related wavelength dispersion and Rth 値 phase -31 - 200919035 in different patterns, for example, R 値 has inverse dispersion and R 値 値 has the opposite Dispersed phase difference film. The R 値 of the retardation film having such characteristics can be suitably used for a display device such as a transflective vertical alignment liquid crystal mode. Specifically, for example, a design example in which R値 has a reverse dispersion and Rth値 has a generally dispersed retardation film is described in Design Examples 1 and 3 and Examples 3, 4 and 5 which will be described later. That is, as long as R ( λ ) and Rth (λ) can achieve the above object, the wavelength dependence is determined in the formulas (14) to (16), the respective parameters are determined, and the material whose parameters can be realized is selected. And the process can be. (Arrangement of the retardation axis) In the repetitive multilayer structure included in the retardation film of the present invention, the phase difference controllability or the phase difference is ensured, and the layer having negative optical anisotropy and positive optics are considered. The in-plane retardation axes of the respective anisotropic layers (β) are preferably arranged to intersect each other substantially perpendicularly. Further, in the case of repeating the multilayer structure, in the case of a layer other than the layer having negative optical anisotropy and the layer having positive optical anisotropy (作为), the in-plane phase is delayed. Preferably, the shafting is disposed substantially parallel or substantially perpendicular to the slow axis in the plane of the layer (A) or layer (Β). The angle formed by the retardation axes in the in-plane of the layer (A) having negative optical anisotropy and the layer (B) having positive optical anisotropy is at 90 ± 3. The range is preferably 'the better is 90 ± 2. The range is better than 90 ± 1. The range of -32- 200919035, the best is 90 ± 0 · 5 ° range. (Difference in refractive index in the plane) The three-dimensional refractive index of the layer (A) having negative optical anisotropy satisfies the above formula (21), or the three-dimensional refraction of the layer (B) having positive optical anisotropy When the rate satisfies the above formula (2 3 ), that is, in the case where optical anisotropy exists in the surface, the relationship between nx and ny of the refractive index in the plane satisfies the following formula (1). In the case where I nx - ny I is 0.000 1 or less, sufficient in-plane anisotropy cannot be obtained in the repeated multilayer structure, and in the case of 〇·1 or more, there is a case where the phase difference control property is deteriorated. good. 0.000 1 < I nx — ny | <0.1 (1) In the formula, a three-dimensional refraction of the layer (A) having a negative optical anisotropy or the layer (B) having a positive optical anisotropy in the X-axis direction Rate ny: three-dimensional refractive index X-axis in the y-axis direction of the layer (A) having negative optical anisotropy or the layer (B) having positive optical anisotropy: the late phase of the repeated multilayer structure in the plane of the repeated multilayer structure Axis y-axis: an axis perpendicular to the X-axis in the plane of the repeated multilayer structure). The 値 of nx - ny | is preferably in the range satisfying the following formula (26), and more preferably in the range satisfying the following formula (27), and the most preferable one is located in the following formula (2 8) Range: -33- 200919035 0.0003 < 1 ηχ - ny | < 0.05 (26) 0.0005 < 1 nx — 1 < 0.01 (27) 0.0007 < 1 nx - ny 1 < 0.007 (28) [ The number of layers forming the repeating multilayer structure] The number of layers forming one repeating multilayer structure is preferably 100 or more and 30,000 or less. If the number of layers is less than 100 layers, if there is a considerable refractive index difference between the layers, sufficient structural birefringence may not be obtained. On the other hand, in consideration of the purpose of achieving the preset purpose, An optical design with more than 30,000 layers is required. Preferably, it is 500 layers or more and 20,000 layers or less, more preferably 1 layer or more and 15,000 layers or less, and most preferably 2000 layers or more and 10000 layers or less. The retardation film of the present invention may comprise a plurality of repeating multilayer structures, and all the layers at this time are preferably 200 layers or more and 1,000 or less layers, and more than 1,000 layers and 50,000 layers for the same reason. The following is preferable, and it is more preferably 3,000 or more and 30,000 or less, and more preferably 4,000 or more and 20,000 or less. [Difference in average refractive index between layers of a repeating multilayer structure] Average refractive index difference of each layer of a repeating multilayer structure (average refractive index of layer (A) having negative optical anisotropy and layer having positive optical anisotropy ( The difference in average refractive index of B) is preferably in the following formula (2). The repeated multilayer structure is composed of two layers of a layer (A) having negative optical anisotropy and a layer (B) having positive optical anisotropy of -34 to 200919035; ^ 0.001 < I δη I < 0.5 (2) When the average refractive index difference is 0.001 or less, in order to achieve birefringence, it is necessary to make the number of layers higher than the above. On the other hand, it is difficult to make the average refractive index difference into a combination of 0.5 molecular materials. It is impractical to combine the necessary machine materials. Further, the structure mainly depends on the ratio of the interlayer film thickness to the refractive index difference, and when 値 5 or more, the influence of the structural birefringence affects the directional birefringence, so that it is difficult to repeat the multilayer structure control. Here, the relationship of the average refractive index here can be expressed by the following formula (29). [Equation 1 1] | 値 η | 値 is preferably in the range satisfying the following formula, and is in the range of the range (3 2 ) satisfying the following formula (3 1 ). 0.0 1 < | δη I < 0-3 0.02 < | δη I <0.2 The case is particularly good. A sufficient structure is obtained for more cases' above, especially for the range of η and three-dimensional refractive index (3 0 ) which are high in the size of the inorganic material and the characteristic birefringence but the average refractive index difference is excessively larger than the three-dimensional refractive index of the molecule. , the best is under the satisfaction of (30) (31) -35- 200919035 0.03 < | δ η < 0.18 (31,) 0.03 < 1 δ η 1 < 0.15 (32) 0.05 < 1 δ η 1 < 0.12 (32,) 0.07 < 1 δ η 1 < 0.1 (3 2,,) Further, the 'average refractive index can be set to the optically isotropic film state of the material forming each layer' by Abbe refracting Determined by an ellipsometer or an ellipsometer. In the state of optical anisotropy, the three-dimensional refractive index can be measured by the same method, and the average refractive index can be obtained from the above formula (29). [Alignment index in the thickness direction of the multilayer structure (^^2値)) As described above, in the present invention, the film which satisfies the formula (20) or (21) is defined as a film which has a negative optical anisotropy. The film "haves a positive optical anisotropy" as defined by the formula (22) or (23). As described above, in the above-described technical field, the general refractive index (nz) of the retardation film in the thickness direction is set as shown in the following formula (3'). It is greater than one of the two principal refractive indices (nx, ny) in the plane of the retardation film and is smaller than the remaining one. Nx >>

(3,) -36- 200919035 When the relationship (Nz値) in the thickness direction defined by the following formula (4) is used, the relationship shown by the formula (3') can be expressed by the formula (3). . [Expression 12] where nx is the three-dimensional refractive index ny in the X-axis direction of the repeated multilayer structure: the three-dimensional refractive index nz in the y-axis direction of the repeated multilayer structure: the three-dimensional refractive index in the z-axis direction of the repeated multilayer structure X-axis: The slow-phase axis y-axis of the repeating multilayer structure in the plane of the repeated multilayer structure: the axis z perpendicular to the X-axis in the plane of the repeated multilayer structure: the axis of the normal orientation of the face of the repeated multilayer structure} 1 > Nz > 0 (3) Here, when the orientation index (Nz値) in the thickness direction is used, and the film means “having negative optical anisotropy” (2〇) and (2 1 ), the next step is obtained. Said (25).

Nz ^ 0 (25) In addition, when the orientation index (Nz値) in the thickness direction is used, it can be obtained by the formulas (22) and (23) of the film "positive optical anisotropy" of the film meaning -37-200919035. Said (24).

Nz ^ 1 (24) Therefore, the orientation index (Nz値) in the thickness direction of the range specified by the above formula (3) cannot be obtained in the extension of a general polymer film. Therefore, in order to obtain the retardation film of the above formula (3) in order to obtain the alignment index (Nz値) in the thickness direction, it is necessary to carry out a special stretching method for applying stress to the normal direction of the film surface. Therefore, the retardation film satisfying the above formula (3) is difficult to extend in the current state, and the control of the phase difference is extremely difficult. Therefore, it is a film which is extremely difficult in production and has a very poor wavelength dispersion control. However, a retardation film which satisfies the characteristics of the above formula (3) is known to have a great effect on the angle of view expansion in various types of liquid crystal display devices. Therefore, proposals in the industry that can easily perform phase difference control are highly anticipated. In the present invention, as a constituent unit of the repeating multilayer structure, a layer (A) having a negative optical anisotropy satisfying the above formula (20) or (21) (preferably satisfying the formula (21)), and The layer (B) satisfying the positive optical anisotropy of the above formula (22) or (23) (preferably satisfying the formula (23)) can obtain good controllability of the phase difference 'and has the above formula (3) An optically anisotropic retardation film. -38- 200919035 [Preferred parameters for satisfying the repeated multilayer structure of the above formula (3)] Deliberately reviewing the optical anisotropy of a repetitive multilayer structure contained in the retardation film of the present invention, In the case where the repeating multilayer structure is composed of two layers of a layer (A) having negative optical anisotropy and a layer (B) having positive optical anisotropy, in order to satisfy the above formula (3), the following formula is satisfied. (5) ~ (7) is better. This formula (5) is obtained by combining the above formula (3) with the formulas (14) to (16) relating to the structural birefringence. Further, the measurement wavelength here is set to 5 5 Onm ° of the wavelength at which the human visual sensitivity is the highest [Math. 13] ^jan„ +bnfX > __ -1' , -a (5) η ηχ ηζ (6) η (7) where a: film thickness (nm) of one layer of layer (A) having negative optical anisotropy b: film thickness (nm) of one layer of layer (B) having positive optical anisotropy nnx : three-dimensional refractive index nny in the X-axis direction of layer (A) having negative optical anisotropy: three-dimensional in the y-axis direction of layer (A) having negative optical anisotropy - 39 - 200919035 refractive index nnz : having negative optics Three-dimensional refractive index npx in the z-axis direction of the anisotropic layer (A): three-dimensional refractive index npy in the x-axis direction of the layer (B) having positive optical anisotropy: layer having positive optical anisotropy (B) Three-dimensional refractive index npz in the y-axis direction: three-dimensional refractive index in the z-axis direction of the layer (B) having positive optical anisotropy X-axis: the slow-phase axis y-axis of the repeating multilayer structure in the plane of the repeated multilayer structure: Repeating the axis of the X-axis perpendicularly intersecting the axis of the multi-layered structure: the axis of the normal orientation of the face of the repeating multilayer structure, as described above, in a repetitive multilayer construction, Since each parameter of each layer may have a certain degree of variation, the above formulas (5) to (7) may be satisfied by the average film thickness and optical anisotropy of each layer. The average film thickness may be, for example, transmitted electrons. The observation of the cross section of the microscope is performed by averaging 100 points of each layer. Further, the average optical anisotropy of each layer is as described above, and the above formula (14) can be used from the data such as the obtained average film thickness. (16). [Parameters for obtaining a phase difference film of reverse dispersion] As described above, since the phase difference film of the present invention contains a layer (A) having a negative optical anisotropy and having a positive optical difference Since the directional layer (B) has a repeating multilayer structure as a constituent unit, it is possible to freely control the wavelength dependence of the delay - especially the in-plane retardation, as a result of the directional layer (B). A so-called reverse dispersion retardation film in which the absolute enthalpy is also increased at the same time. [Dispersion in wavelength with respect to in-plane retardation] With respect to the present invention, the retardation film may have an inverse dispersion in terms of in-plane retardation. By the following (8') to represent Ι1(λ)/Ι1(λ')< 1 (8,) λ, λ': measurement wavelength (400ηηι^λ<λ'^7〇〇ηηι' is preferably λ= 450ηηι and λ7 = 5 5 Onm ) Therefore, when a reverse-dispersion retardation film is to be obtained, 'the repeated multilayer structure is composed of a layer (A) having negative optical anisotropy and a layer (B) having IE % twinning. The case of the seed layer is preferably such that the following formula (8) is satisfied. This formula (8) is obtained by combining the above formula (8) with the formulas (14) to (16) associated with the structural birefringence. [Math 14] (Λ) - ^α»^(Λ)+ bn% [λ) ^ ^Ι〇?ιΙχ(Λ,)+ΒηΙχ(Λ,) - ^ where, a: has negative optical anisotropy Film thickness of one layer of layer (A) -41 - 200919035 b: film thickness (nm) of layer (B) having positive optical anisotropy nnx : layer having negative optical anisotropy (A) Two-dimensional refractive index nny in the X-axis direction: two-dimensional refractive index npx in the y-axis direction of the layer (Α) having negative optical anisotropy: three-dimensionality in the X-axis direction of the layer (B) having positive optical anisotropy Refractive index npy: two-dimensional refractive index in the y-axis direction of the layer (B) having positive optical anisotropy. X-axis: the slow-phase axis of the repeated multilayer structure in the plane of the repeated multilayer structure: the surface of the repeated multilayer structure The x-axis perpendicularly intersects by λ(ηιη): the measured wavelength of the refractive index, and 4〇〇$λ<λ'$7〇ί), preferably 1=45011111 and λ'=550ηηι. In the case where an inversely dispersed retardation film is to be obtained, it is preferable that the repeating multilayer structure is composed of two layers of a layer having negative optical anisotropy and a layer having positive optical anisotropy (Β). The layer (8) having the negative optical anisotropy and the layer having the positive optical anisotropy have a molecularly-oriented birefringence in the plane and having a negative The retardation axes in the plane of the optically anisotropic layer (A) and the layer (Β) having positive optical anisotropy are arranged to substantially perpendicularly intersect each other. The sharp vertical intersection at this time means that the angle formed by the slow phase axis is at 90 ± 3. The range is preferably 'the preferred range is 90 ± 2 °, and more preferably 90 ± 1. The range, the best is 90 ± 0.5. The scope. -42- 200919035 [Repeating the in-plane phase difference 多层 of the multilayer structure (R · The weight contained in the retardation film of the present invention: R 値 (nm)) is suitable for the consideration of the phase, to satisfy The following formula (1 〇) 10 nm < R < lOOOnm R 値 preferably satisfies the following formula (3 3 formula (34 ), and the best one satisfies the following formula (3 20 nm < R < 800 nm 30 nm < R < 600 nm 40 nm < R < 400 nm [Wavelength dispersion relating to retardation in the thickness direction With respect to the present invention, the phase difference film having reverse dispersion in thickness f can be expressed by the following formula.

Rth(X)/Rth(X?)< 1 { λ, λ ' : measurement wavelength (4 0 0 nm $ λ < λ ' = 450 nm and λ, = 550 nm) } 値(η m ))] The in-plane phase difference film of the structure is preferably mounted on the liquid crystal display. (1〇) ), and the better ones satisfy the following 5) ° (33) (34) (35) properties] S700nm in the direction of retardation, preferably λ -43- 200919035 [with in-plane and thickness Wavelength Dispersion Related to Delay in Direction] As described above, the retardation film according to the present invention can individually control the in-plane phase difference 値(R ( λ )値) and the thickness direction phase difference 値 (Rth ( λ ) )value). [Wavelength Dispersibility Related to Delay in In-Plane and Thickness Direction-Independent Control 1] In this regard, for example, the retardation film in accordance with the present invention, the in-plane phase difference 値(R ( λ )値) is related to wavelength dispersion { R ( λ ) / R ( λ ')} The difference in wavelength dependence (Rth ( λ ) 値) with respect to the thickness direction 値 (Rth ( λ ) 値) can be such that it satisfies the following formula: . {Rth(X)/Rth(X5)} - {R(X)/R(X,)} I ^0.1 {λ,λ': measurement wavelength (400ηιη$λ<λ'$700ηιη, preferably λ = 450 nm and λ, = 550 nm) }. Further, for example, according to the retardation film of the present invention, the wavelength dependence of the in-plane phase difference 値 correlation {R(X) / ΙΙ(λ')} is related to the wavelength dependence of the thickness direction phase difference { { Rth ( λ ) / The difference of Rth (λ')} can be set to 0.15 or more, 0.2 or more, or 0.25 or more. In this connection, the optical anisotropy of a repeating multilayer structure contained in the retardation film of the present invention was deliberately reviewed, and it was found that the repeating multilayer structure was composed of a layer (A) having negative optical anisotropy and having positive optics. The two layers of the anisotropic layer (B) are formed, and have measurement wavelengths λ(ηηι) and λ'(ηιη) (400ηιη$λ <λ'$700ηηι) -44 - satisfying the following formula (200). 200919035 is better. This formula (200) is obtained by combining the above formulas with the formulas (10 0 to ( 1 2 ) related to the structural birefringence. Further, the 値 on the right side is, for example, 0.15 or more, 0.2 or more, or 〇·25 or more. [Math 15] ν^(Α)+^)+ν<(Λ)+^(Λ)-

V«»^)+^W-VaniW+in»W ^0.1 (2 0 0) (wherein, a: film thickness (nm) of one layer of layer (A) having negative optical anisotropy b: positive Film thickness (nm) of one layer of the optically anisotropic layer (B) nnx : three-dimensional refractive index nny of the layer (A) having negative optical anisotropy in the X-axis direction • layer having negative optical anisotropy ( A) three-dimensional refractive index nnz in the y-axis direction: three-dimensional refractive index npx in the z-axis direction of the layer (A) having negative optical anisotropy: three-dimensional X-axis direction of the layer (B) having positive optical anisotropy Refractive index npy : three-dimensional refractive index in the y-axis direction of the layer (B ) having positive optical anisotropy - 45 - 200919035 npz : three-dimensional refractive index X-axis in the z-axis direction of the layer (B ) having positive optical anisotropy • The y-axis of the retardation axis of the repeated multilayer structure in the plane of the multilayer structure: the axis z perpendicular to the X-axis in the plane of the repeated multilayer structure: the axis of the normal orientation of the surface on which the multilayer structure is repeated). [Wavelength Dispersibility-Independent Control Related to Delay in In-Plane and Thickness Directions 2] Further, according to the retardation film of the present invention, R (λ) / R (λ') and Rth (λ) / Rth ( Any of λ,) is 値 greater than 1, and the other is 値 less than 1, that is, one of the retardation in the plane direction and the retardation in the thickness direction may exhibit general wavelength dispersion, and One shows a female with a reverse wavelength division. Here, the measurement wavelengths λ, λ ' are 4 0 0 n m S λ < λ' € 700 ηηι' are preferably λ = 450ηπι and λ, = 550ηηι. In this connection, the optical anisotropy of a repeating multilayer structure contained in the retardation film of the present invention is deliberately reviewed, and it is found that the repeating multilayer structure is preferably a layer having negative optical anisotropy. It is composed of two layers of a layer (Β) having positive optical anisotropy, and one of the following formulas (100) and (100') is less than 1, and the other is a measurement wavelength exceeding one. λ(ηιη) and λ'(ηηι) (400ηηι^λ < λ'€700ηιη). The equations (100) and (100) are obtained by combining the above formulas with the equations (14) to (16) relating to the structural birefringence. -46 - 200919035 [Math 16] ^nl(A')+bnlXA,)-^an2ny{A,)^bn2py(X,) Π〇〇) 2(a+b) ν°«» 2{a+ b) yian^+bn^iT) ylanl(X)-i-b>^x(A) + ^αη^{λ)+ΒηΙ(λ) - _ (Λ'Χ(Λ')+Χ(;Γ ) + ί>η^(Λ')- (1〇〇,) (wherein, a: film thickness (nm) of the layer having negative optical anisotropy (b) b: having positive optical anisotropy Film layer thickness (nm) of the layer (B) nnx: three-dimensional refractive index nny of the layer (A) having negative optical anisotropy in the x-axis direction: layer (A) having negative optical anisotropy Three-dimensional refractive index nnz in the y-axis direction: three-dimensional refractive index npx in the z-axis direction of the layer (A) having negative optical anisotropy: three-dimensional refractive index npy in the X-axis direction of the layer (B) having positive optical anisotropy : Three-dimensional refractive index npz in the y-axis direction of the layer (B) having positive optical anisotropy: Three-dimensional z-axis direction of the layer (B) having positive optical anisotropy - 47 - 200919035 Refractive index X-axis: Repeated multilayer The y-axis of the retardation axis of the repeating multilayer structure in the plane of the structure: the axis perpendicular to the x-axis in the plane of the repeated multilayer structure: the Z-axis: the normal orientation of the face of the repeated multilayer structure <Material of retardation film> As a material constituting the retardation film of the present invention, a layer having negative optical anisotropy due to molecular orientation birefringence which can form a structural unit of a repeating multilayer structure is used. (A) The material of the layer (B) having positive optical anisotropy is not particularly limited. A layer having negative optical anisotropy due to molecular orientation birefringence of a structural unit of a repeating multilayer structure ( A) and the layer (B) having a positive optical anisotropy, it is preferable to use a polymer in consideration of moldability. As the polymer, any of crystallinity, liquid crystallinity, and amorphousness may be used. However, in consideration of the phase difference control property, it is preferable to use an amorphous group molecule, and it is preferable to use a thermoplastic polymer in consideration of formability. Further, a layer (A) having negative optical anisotropy and having The molecularly-oriented birefringence of the positive optical anisotropic layer (B) is considered to improve the manufacturing efficiency of the retardation film, and is preferably exhibited by molecular alignment of the polymer. It is used for having negative optical anisotropy. Layer (A) and The glass transition point temperature of the polymer having the positive optical anisotropy layer (B) is preferably 120 ° C or more, preferably 1 2 5 ° C or more, in consideration of the long-term retention of the alignment. The best is 1 3 〇 °C or more, and the best is 1 3 5 °C or more. In addition, in terms of formability, the upper limit of the glass transition point temperature is preferably -80 to 200919035. Preferably, it is 170 ° C or less, more preferably 160 ° C or less, and most 15 (TC or less). Here, the term "glass transition point temperature" as used herein means an apparent glass transition point temperature at which a polymer also contains an additive or the like. The shift temperature can be measured by a differential scanning calorimeter (D S C ). Further, the material having a transition point as a constituent unit of the repeated multilayer structure is preferably substantially the same. In particular, the difference between the temperature of the sub-glass transition point of the material having the negative optical property (A) and the layer (B) having positive optical anisotropy is preferably 20 ° C or less, preferably lower, and more preferably The temperature is below 1 〇 ° C, and the best is below 5 ° C. In the retardation film of the present invention, a plasticizer such as a known oxidation preventive agent or a slip ester ester such as IRGANOX 1010 (manufactured by Ciba-Geigy Co., Ltd.) or the like may be added to the material forming the layer without impairing the effect thereof. An additive such as an activator, a phenyl salicylate, a 2-hydroxyketone or a triphenyl phosphate such as a UV absorber, a charge inhibitor, or a blue agent. Further, in order to adjust the temperature or rate of the glass transition point, an additive having excellent compatibility may be added. [Layer of negative optical anisotropy due to molecularly oriented birefringence <Material] Layer (A) having negative optical anisotropy, in consideration of control of phase difference, to contain molecular polarizability anisotropy Polymer having a negative property: Here, the term "molecular polarizability anisotropy is negative" is defined as a range in which the glass transition point temperature of the polymer is Tg ( ° C ) Tg ± 10 ° C. In the longitudinal uniaxial extension, the best in-plane film is 'not only the glass-to-glass transfer anisotropy high score of 15 °c to the inside, 1076, diphenylmethyl dye ink birefringence: A) It is preferred that the maximum orientation of the refractive index -49-200919035 is a polymer having a property perpendicular to the extending direction. Examples of the polymer having a negative molecular polarizability and anisotropy include polymethyl methacrylate, polypropylene ruthenium, propylene, polyester, polycarbonate, and polystyrene. , syndiotactic polystyrene, hydrogenated polystyrene, organic acid-substituted cellulose, phenyl-containing copolyolefin maleimide, polycarbonate having an anthracene skeleton, A polymer such as a styrene-anhydrous maleic acid copolymer, a blend of polyphenylene ether and polystyrene, a blend of such a composition, and the like. a polymer having a negative molecular anisotropy, a copolymer of styrene and anhydrous maleic acid having a copolymerization molar ratio of 70/30 to 86/14 of styrene and anhydrous maleic acid, especially light. A copolymer having a modulus of elasticity of 8 X 1 Ο -1 2P a_1 or less. Such copolymers have improved heat-resistant phase difference stability, a small photoelastic coefficient and a negative optical anisotropy. For example, when the copolymerization molar ratio of styrene/anhydrous maleic acid is 85/15, the glass transition temperature can be set to 133 ° C and the photoelastic coefficient can be SJxlO^Pa·1, when the ratio is 78/22. , the glass transition temperature can be set to 150 ° C and the photoelastic coefficient becomes 4.3 xl (Γ1 2Pa" ' and when the ratio is 74/26, the glass transition temperature can be set to 150 ° C and the photoelastic coefficient is made 2.8 X 1 0 ·12 P a·1 [Material of layer (B) having positive optical anisotropy due to molecularly oriented birefringence] Layer (B) having positive optical anisotropy, in phase The control of the difference is -50, 200919035. It is preferable to use a polymer containing a positive molecular anisotropy. Here, "a polymer having a positive molecular anisotropy is positive" It is defined as: when the glass transition point temperature of the polymer is Tg ( τ ) ' and the longitudinal uniaxial stretching is performed in the range of Tg ± 1 〇 °c, the maximum orientation of the refractive index in the plane of the film is substantially parallel to the extending direction. The polymer which is positive in molecular polarizability and anisotropy is, for example, polyvinyl alcohol-based, denatured. a vinyl alcohol type, an organic stanol type, a propylene type, an anthraquinone type, a polyester type, a polyurethane type, a polyether type, a rubber type, a polycarbonate type, an amorphous terpene polyolefin, a polymer having a norbornene skeleton, a cyclic olefin polymer having a norbornene skeleton, an organic acid-substituted cellulose system, a polyether oxime system, a polyarylate type, an olefin butylene iminoimide system, a copolyolefin pentylene group having a phenyl group a quinone imine, a polyamidene, a polyamine, a polyether ketone, a polyaryl ether ketone, a polyamidamine-imide, a polyester, an anthracene, a polyfluorene a carbonate-based polymer, a polyphenylene ether-based polymer, an alloy of polyphenylene ether and polystyrene, a blend of the above, etc. [Other layers] The retardation film of the present invention may have a repeating multilayer structure. a layer having a negative optical anisotropy (A) and a layer other than the layer (B) having positive optical anisotropy due to molecular birefringence of the constituent unit, that is, in addition to repeating the multilayer structure, Other layers, or, in repeated multilayer constructions, except for negative optical anisotropy The layer (A) and the layer (B) having positive optical anisotropy may have other layers. -51 - 200919035 As the material of the other layer, there is no particular limitation as long as it does not impair the effect. It is suitably selected from known materials. For example, in order to improve the mechanical strength of the retardation film itself, a two-sided laminated protective film (X) of a multilayer structure can be formed. Here, the film (X) can also be broken by strength. L〇~5〇Mpa, break 3 00~1 5 00 %, surface impact damage energy 5) (1〇-4; 4111 or more, and the dynamic storage elastic modulus and dynamic loss elasticity in the frequency of 1 Hz _ 105~ 2xl08Pa of a thermoplastic resin composition is produced, and the light can be substantially isotropic. The various measurement systems related to this 'protective film' are as follows. (1) Breaking strength The breaking strength is a sample film having a width of 1 mm in accordance with the method specified in Π SC 2 1 5 1 - 1 9 9 0, with a stretching speed of 1 〇〇 mm between the lengths of the samples 2 0 0 The tensile test was carried out under the conditions of mm/min, and the stress was determined by the stress of the film breaking. (2) Breaking elongation and elongation The tensile strength of the sample film having a width of 10 mm was carried out in accordance with the method specified in JIS C2151-1990, and the tensile test was carried out under the conditions of a test length of 100 mm and a tensile force of 200 mm/min. The (elongation) at which the film breaks is determined. And in the heavy protection extension 40 ° CS 1X theoretical test 2 3 〇 C, pull crack 2 3 〇 C speed shape -52- 200919035 (3) surface impact damage energy (50% crushing damage energy) The impact-breaking energy system is provided with a pin (size < t > 4.0 mm) in the center of the sample fixed around, and a weight (weight 0.5 kg) is dropped from above. A data processing method using JIS Km 1 - 1 (Ladder method) 'By calculating the breaking energy of each film thickness. (4) Dynamic storage elastic modulus and dynamic loss elastic modulus The enthalpy measured at a measurement temperature of _ 40 ° C and a frequency of 1 Hz in a tensile mode using RS Α - II manufactured by Rheometrics Co., Ltd. As can be understood from the above-mentioned breaking strength, elongation at break, surface impact destruction energy, dynamic storage modulus, and dynamic loss modulus, the thermoplastic resin composition (P) for the protective film (X) has a large Mechanical strength and elasticity. By using such a protective film, the crack resistance of the phase difference film of the present invention at the time of handling or impact test can be improved. The thermoplastic resin composition (P) preferably has a breaking strength of 1 〇 MPa or more and 20 MPa or more. When the breaking strength is less than 10 MPa, when the laminated retardation film having the protective film for retardation film formed by the thermoplastic resin composition (P) is stretched, there is a fear that cracking occurs in the film, and The protective film for a retardation film obtained by the thermoplastic resin composition (P) does not sufficiently function as a protective film for a retardation film. The thermoplastic resin composition (P) preferably has a elongation at break of 300% or more and 500% or more. When the elongation at break is less than 300%, the laminated retardation film of the protective film for retardation film-53-200919035 which is made of the thermoplastic resin composition (P) is stretched, and cracks may occur in the film. In addition, the protective film for a retardation film obtained from the thermoplastic resin composition (p) does not sufficiently function as a protective film for a retardation film. In the thermoplastic resin composition (p), the surface impact energy is 5 χ 1 (Γ4 / / μηη or more, especially 8 χ 1 (Γ4·Τ / μιη or more. In the case where the surface impact damage energy is small, the thermoplastic resin is used. The protective film for a retardation film obtained by the composition (Ρ) does not sufficiently function as a protective film for a retardation film. The dynamic storage elastic modulus of the thermoplastic resin composition (Ρ) at _40t, frequency 1HZ, and The dynamic loss elastic modulus is preferably 1×1 〇5~2 X 108Pa, 5xl05~5xl07Pa, respectively. If the two 値 are lower than lxl〇5Pa, the adhesiveness when winding the film may become larger. The protective film for a retardation film formed of the thermoplastic resin composition (P) is present on both sides of the laminated retardation film of the present invention, so that it is important to suppress the adhesion of the protective film for the dislocation film. When the two enthalpies exceed 2 x 1 08 Pa, the laminated retardation film having the protective film for retardation film made of the thermoplastic resin composition (P) may be broken during the heat cycle test. The photoelastic coefficient of the plastic resin composition (P) when it is not extended is preferably 10 χ1 (Γ12 ～+10×10 −12/Pa, preferably 7×l (T12 ～ 7×l 〇 -12/Pa, especially one) 5χ10·12~+ 5xl〇-12/Pa. By making the photoelastic coefficient in the unextended range within this range, it can be applied to optical applications such as a polarizing plate protective film and a retardation film. -54- 200919035 Thermoplastic resin The composition (p) may be any thermoplastic resin composition satisfying the above conditions, and as the example, a vinyl copolymer resin (B-1) having a polymer composed of styrene may be suitably mentioned. a copolymer of a block and a polymer block composed of a butadiene or a polymer block composed of isoprene or a hydride polymer (B-2) containing the polymer. ) is optically substantially isotropic 'means satisfying, for example, the following formula: | R(x) | S20nm (10nm is particularly good, 5nm is particularly good)

Re ( X ): In-plane retardation of the protective film (X) measured by light having a wavelength of 400 to 700 nm (in the case where the protective film for the retardation film is present in plural, it is in the surface of the protective film for all retardation films) The sum of the delays)). <Method for Producing Phase Difference Film> When the optical anisotropy due to molecular orientation birefringence of the retardation film of the present invention is exhibited, the control of optical anisotropy is easily considered, and the elongation treatment is employed. good. The extension treatment may be either uniaxial extension or biaxial extension, and may be either a sequential biaxial extension or a simultaneous biaxial extension in the case of biaxial extension. Further, the method of stretching is not particularly limited, and for example, -55-200919035 can be used for longitudinal uniaxial stretching extending between rolls, transverse uniaxial stretching using a tenter, or a combination of the above modes. A well-known method such as shaft extension, sequential biaxial extension, and the like. The elongation temperature is preferably in the vicinity of the glass transition point of the polymer to be used. For example, in the case of using a thermoplastic polymer, it is set at (Tg - 20 ° C) with respect to the glass transition point temperature (Tg). The range of ~(Tg + 3〇 °C) is preferably, and more preferably (Tg - 10 ° C) ~ (Tg + 20 ° C). Further, since the retardation film of the present invention contains a multilayer repeating structure composed of a plurality of constituent units, it is preferable to appropriately set the layer having the highest Tg as the elongation temperature. In addition, the formation of the multilayer structure before the stretching is not particularly limited as long as it can form a multilayer structure, and examples thereof include a multilayer spin coating method, a multilayer solution casting method, and a multilayer melt extrusion method. . A preferred method of forming the retardation film of the present invention is a method of forming a multilayer film by using a material composed of a polymer and forming a plurality of layers by a multilayer melt extrusion method, followed by stretching the multilayer film. According to this method, even if it is a complicated multilayer structure, it can be treated as a film after melt extrusion, and as a result, complicated optical anisotropy can be easily obtained. Further, according to the method, each layer constituting the repeating multilayer structure can exhibit molecularly-oriented birefringence in the plane by molecular alignment of the polymer, and can easily produce a layer having negative optical anisotropy and having a positive optical difference A repeating multilayer structure in which the retardation axes of the directional layers intersect each other substantially perpendicularly. The multilayer melt extrusion method is not particularly limited, and a known method described in, for example, Japanese Patent No. 3,649,585 can be employed. The multi-layer melt extrusion-56-200919035 method may, for example, be a multi-manifold method or a split block method, and in the present invention, a split block method is preferred. In the case of performing multilayer melt extrusion, it is preferred that the melt viscosity of the polymer to be used is substantially the same. When the melt viscosity is significantly different, it may be difficult to form a multilayer structure. In the present invention, the melt viscosity measured at a temperature of 250 ° C and a shear rate UOsec·1 is preferably 100 to 6000 Pa, s, preferably 200 to 4000 Pa*s, more preferably 300 to 2000 Pa. «s, the best is the range of 4〇0~1 800 Pa*s. If the melt viscosity deviates from the above range, the film formation in which the multilayer structure is repeated may be unstable. Further, in the multilayer melt extrusion step, when the difference in melt viscosity between the materials forming the multilayer structure is large, it may be difficult to form a layer structure. The difference in melt viscosity is preferably the smaller one. For example, the difference in melt viscosity measured at a temperature of 250 ° C and a shear rate of HOsec T1 is preferably 500 kPa or less, preferably 3,000 Pa_s or less. The number is below 2000Pa*s, and the best is below 1 000Pa«s. If the melt viscosity deviates from the above range, the film formation of the repeated multilayer structure may be unstable. However, in the case of using a material having a poor viscosity, there is also a case where the cutting speed is changed depending on the shape of the flow path, so that a stable repeating multilayer structure can be formed. In the multilayer melt extrusion method, a method in which a resin is extruded using a T-die and then transferred to a cooling roll is preferred. The resin temperature at the time of extrusion can be appropriately set by calculating the fluidity, thermal stability, and the like of the resin. Further, in order to prevent the peeling of the interface of the multilayer structure, it is preferable that the polymer used for the multilayer melt extrusion is excellent in adhesion to each other. -57-200919035 <Design Example of Phase Difference Film> Hereinafter, a design example will be described, and the best mode for carrying out the invention will be described in more detail. In each design example, an actual polymer was used as a material, and the parameters of the polymer were used for design. [Design Example 1] (A layer) Material: Copolymerized polycarbonate Since the copolymerized polycarbonate has a negative molecular polarizability anisotropy, it exhibits negative optical anisotropy by stretching. The three-dimensional refractive indices used for the three wavelengths calculated (450, 550, 65 Onm) are shown in Table 1. [Table 1] Table 1 In (_) η χ Π η, 4 5 0 1. 63516 1 . 6 3 8 3 7 1 . 6 3 8 3 7 5 5 0 1 . 6 14 4 0 1. 61740 1. 61740 6 5 0 1. 60438 1. 60726 1. 60726 (layer B) Material: Ethylene-norbornene copolymer Since ethylene-norbornene copolymer has positive molecular polarizability anisotropy, it is extended by Positive optical anisotropy. The three-dimensional refractive index used for the three wavelengths calculated (45 0, 55 〇, 65 0 nm) is shown in Table 2 〇-58- 200919035

(Multilayered body) The interactive multilayer film (a/b/a/b/... A/B) composed of the A layer and the B layer was calculated according to the condition of the effective medium approximation by the condition of nS in Table 3. The calculation results are shown in Tables 3 and 4. Here, a and b in Table 4 are the film thicknesses of the A layer and the B layer, respectively. Further, the azimuth axis orientation in the plane of the layer A is set to be substantially perpendicular to the longitudinal axis orientation in the plane of the layer B, and the slow phase axis orientation of the layer B and the slow phase axis orientation in the plane of the repeated multilayer structure Set to be consistent. -59- 200919035 [Table 3] Table 3 Full film thickness (nml A layer total B layer total A layer film thickness (nml B layer film thickness (nm) 100000 2000 2000 20 30 λ (nra) R (nm) Rth (nm ) ny nz Hz 450 101 472 1. 56952 1. 56851 1. 56430 5.16 550 109 367 1. 55854 1, 55745 1. 55433 3.85 650 112 344 1. 55092 1. 54980 1. 54692 3. 56 R (450) R (650) Rth (450) Rth (650) /R (550) /R (550) /Rth (550) /Rth (550) 0. 93 1.03 I. 29 0. 94 [Table 4] Table 4 λ (nm a + b Vaw« +bnpx yla»m'2+bn^2 V(10)X 4 5 0 1 1 . 09 82 1 1. 0 6 12 11. 0910 5 5 0 1 1. 0206 1 0. 9 908 1 1 . 0 128 6 5 0 1 0. 9 6 6 7 1 0. 9 384 1 0. 9587

Failed / R /Rth )/R It is known from Tables 3 and 4 that Nz値 satisfies the above formula (3) at all calculated wavelengths. Further, if attention is paid to the wavelength dispersion indicating the retardation, R ( 4 5 0 ) (550 ) > R ( 650 ) / R ( 550 ) , Rth ( 450 ) ( 5 5 0 ) , Rth ( 65 0 ) / Rth ( 550), R (450 -60- 200919035 (5 50 ) and Rth ( 45 0 ) /Rth ( 5 5 0 ), and R ( 650 (5 5 0 ) and Rth ( 65 0 ) /Rth ( 5 5 0 It is shown that different Nz値 also show different 値 in three wavelengths. The phase difference film composed of a single layer (especially in the liquid crystal display) is widely used by the polymer extension method. In the phase film), R ( 45 0 ) /R ( 5 5 0 ) and Rth ( 45 0 ) (5 5 0 ), and R ( 65 0 ) /R ( 5 50 ) and Rth ( 65 0 ) (55 0) Generally, the same enthalpy is imparted. Further, in the retardation film composed of a single layer, Nz 値 does not depend on the wavelength, and is generally determined. R 値 indicates the optical anisotropy of the film when incident light is incident on the front side. On the other hand, Rth値 and Nz値 are information indicating the optical anisotropy at oblique incidence. Therefore, the retardation film of Design Example 1 shows optical anisotropy at the time of frontal incidence and oblique incidence. Wavelength dispersion It is shown that the optical wavelength dispersion at the time of frontal incidence and oblique incidence can be independently controlled, which is not possible in the conventional retardation film. This is because the retardation film system of the present invention uses the structural birefringence alignment. It is possible to realize both of the characteristics of the conventional birefringence, and it is one of the characteristics that has not existed in the past. For example, in the liquid crystal display device using a vertical liquid crystal or the like, the viewing angle performance can be improved. According to the approximation theory of the effective medium of the design example, the Jones calculation of 4x4 is performed for the multilayer body which is completely the same as the above. As a comparison method, the refractive index ellipsoid which is formed by the multi-layered structure like the effective medium shown in Table 1 is used. And A layer and B layer respectively) /R 値. Displaying the position difference /Rth /Rth constitutes a constant film of the film, which is a non-independent achievement and a special combination of the special orientation type -61 - 200919035 A multilayer structure of 2000 layers (a total of 4,000 layers) is a method in which various polarized lights are incident and the emitted polarized light is compared. As a result, it can be confirmed that the two are approximately the same, and the device can be confirmed. The approximate effective medium is effective in the example. [Design Example 2] (A layer) Material: Polystyrene copolymer Since the polystyrene copolymer has a negative molecular polarizability anisotropy, it is negative by the retardation. Optical anisotropy. The three-dimensional refractive indices used for the three wavelengths calculated (450, 550, 650 nm) are shown in Table 5. [Table 5] Table 5 Λ (nm) ηηκ ηη > Gate 12 4 5 0 1.5 7 3 5 5 Ί. 56927 1 . 5 7 4 0 8 5 5 0 1 - 5 6 0 3 7 1 . 5 5 6 3 7 1 . 5 6 0 8 7 6 5 0 1 . 5 5 2 6 2 1 . 5 4 8 7 8 1. 55310 (B layer) Ethylene-norbornene copolymer of the same material as Design Example 1 will be used for calculation The three-dimensional refractive index of the three wavelengths (45 〇, 550, 65 〇 nm) is not shown in Table 6. [Table 6] Table 6 Λ (nm) π Μ Gate ρζ 4 5 0 1 · 5 2 14 2 1. 52192 1.52116 5 5 0 1 - 5 17 4 2 1. 51792 1.51717 6 5 0 1.51152 1 . 5 1201 1. 51127 -62 - 200919035 (Multilayer) According to the conditions described in Table 7, the interactive multilayer film composed of layer A and layer B is calculated according to the effective medium approximation theory (a/b/A/B/.... A/B) ). The calculation results are shown in Tables 7 and 8. Here, a and b in Table 8 are the film thicknesses of the a layer and the b layer, respectively. Further, the azimuth axis direction in the plane of the layer a and the slow axis direction in the plane of the layer B are set to be substantially perpendicularly intersected, and the azimuth direction of the layer B and the slow phase axis orientation in the plane of the repeated multilayer structure are set. Set to be consistent. [Table 7] Table 7 Full film thickness (ηιη) Total number of bismuth layers Total number of B layers A film thickness (run) B layer film thickness (nml 90000 3000 3000 20 10 λ (nml R (mn) Rth (nm) Πχ n2 Nz 450 245 -75 1. 55636 1. 55365 1. 55583 a 2〇550 227 -87 1. 54618 1-54366 1. 54588 0.12 650 218 -85 1. 53904 1-53662 1. 53877 0.11 R (450) R ( 650) Rth (450) Rth (650) /R (550) /R (550) /Rth (550) /Rth (550) 1.08 0.96 0. 86 0. 98 -63- 200919035 [Table 8] Table 8 Nm) 1 2-7 a + b +bn]J Van>«2+bnpi2 vart« 4 5 0 8. 5 2 4 6 8.5217 8. 5 0 9 7 5 5 0 8. 4 6 8 8 8. 4 6 7 2 8. 4 55 0 6 50 8. 4 2 9 7 8. 4 2 S 2 8. 4 16 4 From the calculation results in Table 7 and Table 8, it is known that Nz値 satisfies the above formula at all calculated wavelengths. (3) and also satisfy the above formulas (5) to (7). Also, if attention is paid to the wavelength dispersion of the phase difference, R ( 4 5 0 ) / R (550 ) , R ( 650 ) / R ( 550 ) ' Rth ( 450 ) /Rth (5 5 0 ) , Rth ( 6 5 0 ) /Rth ( 5 5 0 ), R (450 ) /R ( 55 0 ) and Rth ( 450 ) / Rth ( 5 50 ), And R ( 65 0 ) /R (5 5 0 ) and Rth ( 65 0 ) /Rth ( 5 50 ) are respectively displayed. Nz値 also shows different enthalpies in three wavelengths. [Design Example 3] (A layer) Material: The copolymerized polycarbonate of the same material as Design Example 1 will be used for the calculation of the three wavelengths ( The three-dimensional refractive indices of 45 Å, 55 0, and 65 nm are shown in Table 9. -64 - 200919035 [Table 9] Table 9 λ (ηιη) Gate ηχ n ny Gate μ 4 5 0 1 - 6 3 5 5 9 1 63816 1 . 6 3 8 1 6 5 5 0 1 61480 1. 61720 1.61720 6 5 0 1 . 6 0 4 ^ 1. 6070 7 λ. 60 7 0 7 (B layer) Material: Same as Design Example 1 The three-dimensional refractive index of the dilute-norbornene dilute copolymer used for the calculation of the three wavelengths (450, 550, 650 ηηι) is shown in Table 1 0 ° [Table 1〇] Table 10 λ fnm) ^ ρχ Gate ρζ 1.5 2 0 1 5 4 5 0 1. 52419 1.5 2 0 1 5 5 5 0 1. 52017 1 · 5 16 17 1 . 5 16 17 6 50 1. 51424 1 · 5 10 2 8 1. 51028 (multi-layer body) According to the conditions of Table 11, the interactive multilayer film (a/b/a/B/...·A/B) composed of the A layer and the B layer was calculated according to the effective medium approximation theory. The calculation results are shown in Table 11 and Table 12. Here, a and b in Table 12 are the film thicknesses of the A layer and the B layer, respectively. Further, the azimuth axis direction in the plane of the layer a is set to be substantially perpendicular to the direction of the slow axis in the plane of the layer B, and the azimuth direction of the B layer and the direction of the slow phase axis in the plane of the repeated multilayer structure Set to be consistent. -65- 200919035 [Table η] Table 1 1 Full film thickness (run) Total A layer total B layer total A layer film thickness (nm) B layer film thickness (nm) 70000 1750 1750 20 20 λ (nm) R (nm) Rth(nm) Πχ 门 y nz Nz 450 43 330 L 58087 1. 58026 1.57585 8.16 550 49 252 1. 56820 1. 56750 1. 56424 5. 65 650 51 236 1. 56016 1. 55943 1. 55642 5.09 R (450 R (650) Rth (450) Rth (650) /R (550) /R (550) /Rth (550} /Rth (550) 0. 88 1.05 1.31 0.93 [Table 12] Table 12 Λ (nm) ^ Jan^+bn^1 a + b Va/,«-2 ”anX 4 5 0 9. 9 9 8 3 9. 9 6 6 6 9. 9 9 4 4 5 5 0 9. 9 18 2 9. 8 9 3 1 9. 9 13 7 6 5 0 9. 8 6 7 3 9, 84 3 7 9. 8 6 2 7 From the calculation results in Table 1 1 and Table 1 2, NZ値 is not found in all calculated wavelengths. Can satisfy the above formula (3).

Further, if attention is paid to the wavelength dispersion of the phase difference, R ( 4 5 0 ) / R (550 ) , R ( 650 ) / R ( 550 ) , Rth ( 450 ) / Rth (5 5 0 ) , Rth ( 65 0 ) /Rth ( 5 50 ), R ( 450 ) /R -66 - 200919035

( 5 50 ) and Rth ( 45 0 ) / Rth ( 5 5 0 ), and R ( 650 ) /R (55 0 ) and Rth ( 650 ) /Rth ( 5 50 ) are different 値. Nz値 also shows different enthalpies in three wavelengths. Furthermore, if R(450) / R( 550) and Rth (450) / Rth ( 550 ) are compared in detail, the latter is greater than 1 'is the dispersion of the so-called general delay 'the former is less than 1 ' and Rth increases with wavelength It becomes smaller and is called reverse dispersion. This means that the wavelength dispersion of optical anisotropy at the time of frontal incidence and oblique incidence can be independently controlled. [Design Example 4] (A layer) material: a polystyrene copolymer of the same material as in Design Example 2, and a three-dimensional refractive index used at two wavelengths of 50 volts (450, 550, 650 nm) is shown in Table 13. . [Table 13] Table 13 Λ (nm) n„ M , n ny 4 5 0 1. 57319 ^ΓΓΤΤοΤΓ" Ti丨丨--- 1 . 5 7 3 1 9 5 5 0 1 . 5 6 00 3 1· 55753 1.5 6 00 3 6 5 0 1. 55230 1· 54990 1 . 5 5 2 3 0 (layer B) Material: The ethylene-norbornene copolymer of the same material as in Design Example 1 will be used for the calculation of the three wavelengths ( The three-dimensional refractive index of 450, 550, 650 nm) is shown in Table 14. 4.67- 200919035 [Table 14] Table 14

(Multilayered body) The interactive multilayer film (A/B/A/B/... A/B) composed of the A layer and the B layer was calculated according to the condition of the effective medium based on the conditions of Table i5. The calculation results are shown in Table 15 and Table μ. Here, a and b in Table 16 are the film thicknesses of the A layer and the B layer, respectively. Further, the azimuth axis direction in the plane of the layer a and the slow axis direction in the plane of the layer B are set to substantially perpendicularly intersect, and the azimuth direction of the layer A is delayed and the azimuth direction of the plane in the plane of the repeated multilayer structure Set to be consistent. -68 - 200919035 [Table 15] Table 15 Full film thickness (nm) Total A layer total B layer total A layer film thickness (nm) B layer film thickness (nm) 1QOOOO 2500 2500 20 20 A (nm) R (nm) Rth (nm) n, nz Nz 450 111 31 1-54748 1. 54637 1. 54661 0.78 550 102 8 1. 53883 1. 53781 1. 53824 0.58 650 97 6 1.53200 1.53103 1. 53146 0.56 R (450} R (650) Rth (450) Rth (6501 /R (550) /R (550) /Rth (550) /Rth (550} 1.09 0. 95 3. 80 0.72 [Table 16] Table 1 6 λ (nm) a + b yjanK -2 4-6/1^-2 4 5 0 9. 7 8 7 1 9. 7 8 16 9. 7 8 0 1 5 5 0 9. 7 3 2 4 9.7 2 8 7 9. 7 2 6 0 6 5 0 9. 6 8 9 2 9. 6 8 5 8 9. 6 8 3 1 From the calculation results of Table 1 5 and Table 16 , it is known that Nz値 satisfies the above formula (3) at all calculated wavelengths. It also satisfies the above formulas (5) to (7).

Further, if attention is paid to the wavelength dispersion of the phase difference, R ( 4 5 0 ) / R (550 ) , R ( 650 ) / R ( 550 ) , Rth ( 450 ) / Rth

(550), Rth ( 650 ) /Rth ( 550 ), R ( 450 ) /R -69- 200919035

(5 5 0 ) and Rth ( 450 ) / Rth ( 5 5 0 ), and R ( 65 0 ) /R (5 5 0 ) and Rth ( 65 0 ) /Rth ( 5 5 0 ) respectively show different 値. Nz値 also shows different enthalpies in three wavelengths. [Design Example 5] (A layer) material: a polystyrene copolymer of the same material as in Design Example 2, and a three-dimensional refractive index used for the calculation of three wavelengths (45 0, 5 50, 65 0 nm) is shown in Table 1. 7. m 17] Table 17 λ (run) ηΠχ nny 4 5 0 1 . 5 7 3 5 5 1 . 5 6 9 8 0 1 . 5 7 3 5 5 5 5 0 1.5 6 0 3 7 1 . 5 5 6 8 7 1 . 5 6 0 3 7 6 5 0 1 . 5 5 2 6 2 1 . 5 4 9 2 6 1 . 5 5 2 6 2 (B layer) Material: Ethylene-norbornene of the same material as Design Example 1. The three-dimensional refractive index of the copolymer used for the three wavelengths calculated (45 0, 550, 65 Onm) is shown in Table 18. [Table 18] Table 18 λ (nm) Gate ρ χ π M Gate ρ ζ 4 5 0 1.52049 1.5 2 3 5 2 1 . 5 2 0 4 9 5 5 0 1 . 5 16 5 0 1.51950 1 . 5 16 5 0 6 5 0 1, 51061 1 . 5 13 5 8 1 . 5 10 6 1 -70- 200919035 (Multilayer) According to the conditions described in Table 19, the Α layer and the β layer are calculated according to the city % _ effective medium approximation theory. A 迕 multilayer film (A/B/A/B/..·. A/B). The calculation results are shown in Table U and Table 2〇. Here, a b in Table 2A is a film thickness of the A layer and the B layer. Further, the azimuth axis direction in the plane of the layer a and the slow axis direction in the plane of the layer B are set to substantially perpendicularly intersect, and the azimuth direction of the layer A is delayed and the azimuth direction of the plane in the plane of the repeated multilayer structure Set to be consistent. [Table 19] Table 19 Total film thickness (nm) Total A layer total B layer total A layer film thickness (nn) B layer film thickness (mn) 20 120000 3000 3000 20 Λ (nm) R (nm) Rth (nm) Πχ Ny Πχ Nz 450 49 84 1. 54725 1. 54683 1. 54634 2.21 550 35 57 1. 53859 1. 53830 1. 53796 2.14 650 28 55 1. 53176 1.53152 1.53118 2.45 R(450) R (650) Rth(450) Rth (650) /R (550) /R (550) /Rth (550) /Rth (550) 1.41 0.80 1.47 0.96 -71 - 200919035 [Table 20] Table 20 λ (nm) I ~ 2 2 a+b ^ Ann~2 +bnpi~t 4 5 0 9. 7 8 5 6 9. 7 7 9 9 9. 7 8 3 0 5 5 0 9. 7 3 0 9 9. 7 2 6 9 9.7 2 9 0 6 5 0 9. 6 8 7 7 9. 6 8 4 1 9, 6 8 6 2 From the calculation results of Table 1 9 and Table 2 0, N z値 does not satisfy the above formula (3) at all calculated wavelengths. 'If you look at the wavelength dispersion of the phase difference, R ( 45 0 ) / R (550 ) , R ( 650 ) / R ( 550 ) , Rth ( 450 ) / Rth ( 5 5 0 ) , Rth ( 65 0 ) /Rth ( 5 5 0 ), R ( 4 5 0 ) /R ( 5 5 0 ) and Rth ( 45 0 ) / Rth ( 5 5 0 ), and R ( 650 ) /R (5 5 0 ) and Rth ( 6 5 0 ) /Rth ( 5 50 ) shows different 値. Nz値 also shows different enthalpies in three wavelengths. <Application of retardation film> [Laminated retardation film] The retardation film of the present invention can sufficiently exhibit the function as a retardation film even when used alone, but may be different from other phases as needed. The film is used in combination. [Laminated polarizing film] The retardation film of the present invention may be laminated with a polarizing film to form a laminated polarizing film. Fig. 5 shows an example of a laminated polarizing film. Here, in the figure 5-72-200919035, 51 is a polarizing film, 52 is a retardation film of the present invention, 53 is an optical arrangement of the laminated polarizing film of the present invention, 54 is an absorption axis, and 55 is a phase difference film surface. The inner retardation axis, 56 is the laminated polarizing film of the present invention. Further, in the case where a laminated polarizing film is used for the purpose of expanding the viewing angle of the liquid crystal display device, it is preferable that the polarizing axis of the polarizing film and the in-plane retardation axis of the phase difference film of the present invention are arranged to be parallel or perpendicular. When the polarization axis of the polarizing film is parallel to the in-plane slow axis of the retardation film of the present invention, the angle difference between the two is preferably within ±2 °, preferably 0. ±1°, more preferably 〇±〇.5°, and the best is 0±0.3°. The angle between the polarization axis of the polarizing film and the in-plane retardation axis of the retardation film of the present invention is perpendicular to the angle of 90 ± 2. The range is preferably 90 ± 1 °, more preferably 90 ± 0.5 〇, and the best is 90 ± 0.3 〇. Further, in order to increase the viewing angle of the liquid crystal display device to a higher degree, the polarization axis of the polarizing plate and the retardation axis of the retardation film of the present invention are arranged to be parallel or perpendicular to each other, and satisfy the following formula (36) and The above formula (3) is preferred. Further, the retardation film used herein is preferably composed of only one repeating multilayer structure. (36) 100 nm < R < 350 nm Especially in the case where a high degree of viewing angle expansion is required 'The polarization axis of the polarizing plate and the retardation axis of the retardation film of the present invention are arranged to be parallel or perpendicular -73 to 200919035, and satisfy The following formulas (37) and (38) are preferably 150 nm < R < 300 nm (37) 0.2 < Nz < 0.8 (38) The polarizing film is not particularly limited, and a suitable light capable of obtaining a specific polarized state can be selected. The film is used. It is preferable to use a light that can obtain a linearly polarized state. In the case where the polarizing film has a protective film for a polarizing film, the optical anisotropy of the protective film for a polarizing film is preferably as small as possible. Specifically, the in-plane retardation is 1 Onm or less, preferably 7 nm or less. The best is below 5nm. Further, the 'Rth (λ) is preferably 70 nm or less, more preferably 50 nm or less, still more preferably 30 nm or less, and most preferably 20 nm or less. Further, it is preferable that the retardation axis in the film surface of the protective film for a polarizing film is perpendicularly intersected or parallel with the absorption axis of the polarizing film, and it is preferable to carry out the continuous production of the polarizing film. In the laminated polarizing film of the present invention, the retardation film of the present invention may also have a protective film for a polarizing film. According to this configuration, the use of the protective film for a polarizing film can be omitted, and the influence of the optical anisotropy of the protective film for a polarizing film can be eliminated, and the optical performance can be further improved. When the polarizing film and the retardation film are laminated, they may be fixed by a binder or the like as needed. Further, it is preferable to prevent the shift of the axial relationship and the like. The polarizing film and the retardation film are preferably bonded and fixed. When bonding, -74- 200919035 A transparent adhesive can be used, and the type thereof is not particularly limited. In view of the viewpoint of preventing changes in optical characteristics, a process which does not require high temperature at the time of hardening or drying is preferable, and it is preferable that a hardening treatment or a drying treatment is not required for a long period of time. Further, under heating or humidification conditions, it is preferred that no peeling occurs. Further, each of the layers such as the polarizing film, the retardation film, the protective film for a polarizing film, and the adhesive layer may be, for example, a salicylate-based compound, a diphenol-based compound, a benzotriazole-based compound, or a cyanoacrylate. The ultraviolet absorber such as an ester compound or a nickel complex salt compound is treated to have an ultraviolet absorbing function. [Liquid crystal display device] Further, by using the retardation film or the laminated polarizing film of the present invention in a liquid crystal display device, a liquid crystal display device having significantly improved viewing angle characteristics and the like can be obtained. The liquid crystal display device that can be used is not particularly limited, and can be applied to various methods such as IPS, VA, TN, and OCB modes. Fig. 6 is a view showing an arrangement of a preferred optical film in the case of an IP S mode liquid crystal display device as an example of the liquid crystal display device of the present invention. As the retardation film, R 构成 composed of one repetitive multilayer structure of the present invention is λ/2 (ηηι) and Nz 値 0.5. Here, in FIG. 6, 61 is a polarizing film, 62 is an IPS liquid crystal cell, 63 is a retardation film of the present invention, 64 is a polarizing film, 65 is an absorption axis, and 6 6 is a slow phase axis of the liquid crystal layer. 6 7 is a slow phase axis of the retardation film of the present invention, and 6 8 is an absorption axis. -75-200919035 [Photoelastic coefficient of retardation film] The photoelastic coefficient of the retardation film of the present invention is measured by using a known ellipsometer or the like. If the absolute 値 of the photoelastic coefficient is large, in the case of assembly in a liquid crystal display device, there may be a case where a phase difference 値 is caused, a contrast is lowered, or a dim light is leaked on the screen in a dark state of the liquid crystal display device to generate a spot. . It is preferable to use the light having a wavelength of 550 nm to make the absolute value of the photoelastic coefficient below. Preferably, it is 1 〇 xltTUpa·1 or less, and more preferably SxlO^Pa·1 or less. The sign of the photoelastic coefficient of the material forming the layer (A) and the layer (B) used in the repeated multilayer structure is preferably different from each other. This is because the photoelastic coefficients of each other are offset by the sign of the photoelastic coefficient of each other, and the absolute enthalpy of the photoelastic coefficient is made small. EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples but the present invention is not limited thereto. <Measurement and Evaluation Method> In the examples, the following items were used to perform measurement and evaluation by the following methods. (1) In-plane phase difference 値(R ( λ )値(nm )), thickness direction phase difference 値(Rth ( λ )値(nm )), and thickness direction alignment index (Νζ(λ)値) in-plane The phase difference 値(R ( λ )値), the thickness direction phase difference 値-76- 200919035 (Rth ( λ )値), and the thickness direction alignment index (Nz値) are obtained by using a spectroscopic ellipsometer (Japan Spectroscopic) (Stock) system, the product name: Μ 1 5 0) is determined by the measurement. The R 测定 is measured in a state where the incident light intersects the surface of the film perpendicularly. In addition, in order to obtain Rth値 and Nz 値, the angle formed by the incident light and the surface of the film is changed, and the phase difference 各 of each angle is measured, and the curve is matched by using the formula of the well-known refractive index ellipsoid (curve Fitting), and performing the numerical calculation of the nx, ny, and nz of the three-dimensional refractive index. Further, at this time, as another parameter, the average refractive index η is necessary, and this is by using an Abbe refractometer (AT AGO Co., Ltd., trade name: Abbe refractometer 2 - T ) or 稜鏡The coupler method (manufactured by Prism Coupler Metricon, trade name: prism Coupler MODEL 2010) was measured. Nz 値 and R 値 分别 are obtained by substituting the obtained three-dimensional refractive index into the following formulas (4) and (40), respectively. Further, in the present embodiment, the measurement wavelength is set to 5 5 0 n m unless otherwise specified. [Math. 17] -n„ (4) A-' } Solitary = (4 0) (2) Glass transition point temperature (Tg) The glass transition point temperature (Tg) is measured by a differential scanning calorimeter (τα Instruments -77-200919035 (3) The thickness of the film is measured by an electronic microfilm thickness meter (manufactured by Anritsu Co., Ltd.). (4) The total light transmittance and haze of the film are used. The turbidity meter (made by Nippon Denshoku Industries Co., Ltd., model: NDH-2000 type) was measured. (5) Microtome (manufactured by Leica Microsystems Co., Ltd.), product name ULTRACUT, for measuring the film thickness of each layer. S) A film slice (thickness of about 60 ηιη) of the cross section of the retardation film was formed. Then, the slice was observed and photographed at an acceleration voltage of 120 kV using a transmission electron microscope (manufactured by FEI, trade name TECNAI - G2). The thickness of each layer was measured from the photograph, and the thickness of the blended region was measured from the spectral line profile of the number of transmitted electrons in the thickness direction of the film. (6) Verification of the relationship between the above formulas (1), (5), and (8) Method (6 - i ) forms a single layer of each layer of a repeating multilayer structure The physical properties of the resin were measured by a melt extrusion method or a solution molding method using an Abbe refractometer (made by ATAGO Co., Ltd., trade name: Abbe's design 2 - T) or a 稜鏡 coupler method (Prism Coupler M etric ο η company, trade name: Prism Coupler MODEL 2010) to measure the dispersion of the average refractive index of the a-layer and the tantalum layer separately (η(450), η(550) > η -78- 200919035 (650): ( The internal system indicates the measurement wavelength (nm).) The film is longitudinally uniaxially stretched at a respective glass transition temperature of + 10 °C, and is subjected to a spectroscopic ellipsometer (Japan Spectrophotometer) Trade name: M150) to determine the birefringence dispersion 値 (Δη ( 45 0 ) / Δη (5 5 0 ), Δη ( 65 0 ) / Δη ( 5 5 0 ): () is the measurement wavelength (nm) (6_ii) The dispersion measurement of R and Rth of the retardation film composed of the multilayer structure is measured by a spectroscopic ellipsometer (product name: M150 manufactured by JASCO Corporation). The measurement wavelength is set to 450. 550, 65 〇 nm. (6 - iii) Determination of the film thickness of each layer of the repeated multilayer structure The above (5) is measured in the same manner, and the average thickness of the A, B layer and the blended layer is determined. (ό一iv) The determination of the dispersion of the one-dimensional refractive index wavelength of each layer in the repeated multilayer structure is observed by an electron microscope. It is not possible to observe the presence of a blended layer in a repeating multilayer structure' using equations (14) to (16) or formulas (17) to (19), and on the other hand 'in the presence of a blended layer, Use equations (14,) to (16,) or equations (17') to (19'). The three-dimensional refractive index wavelength dispersion of each layer in the repeated multilayer structure was determined using these relationships and the data obtained in the above (ό i i ) ~ (6 - 111). -79- 200919035 (6 - v ) Verification of the relational expressions of equations (1), (5), and (8) used in the verification of the above-mentioned (6 - i ) to (6 - iv ) The relationship between (1), (5), and (8). (7) Measurement of melt viscosity The measurement of the melt viscosity was carried out using the trade name Kepirogula 1B manufactured by Toyo Kogyo Co., Ltd. The experimental temperature was 250 C and the breaking speed was 180 sec-1. <Example 1 > [Optical design of repeating multilayer structure] As in the above-described design example, 'as shown in Tables 2 to 24', a layer (A) having a negative optical anisotropy is provided The optically anisotropic layer (B) has a repeating multilayer structure as a constituent unit, and is formed into a repeating multilayer structure in accordance with the design. Here, a and b in Table 24 are the film thicknesses of the A layer and the B layer, respectively. Further, the azimuth axis direction in the plane of the layer A is set to be substantially perpendicular to the direction of the slow phase axis in the plane of the layer B, and the azimuth direction of the layer A is delayed and the direction of the slow phase in the plane of the repeated multilayer structure Set to be consistent. (1) Preparation of a material for forming a layer (A) having negative optical anisotropy Using a monomer represented by the following chemical formula (I) (manufactured by Xingren Co., Ltd., trade name: ACMO), starting agent (Ciba) Specialty C hemica 1 s company, trade name: Iruka Qiuya 1 8 4) Mixing monomer-80-200919035 to ο·1 mass%, and putting the obtained mixture into argon flask , to be sealed. Subsequently, a mercury lamp was used as a light source, and polymerization was carried out for 2 minutes to obtain ultraviolet light having a polymerization light intensity of 30 mW/cm2. The resulting polymer had a glass transition point temperature of 14%. Water was added to the obtained polymer to form a 1% by mass aqueous solution, and this aqueous solution was used as the solution A for spin coating. [Chemical Formula 1]

In a mold made of Teflon (registered trademark) resin (designed to form a film-like mold), pour the monomer with the same mixing ratio as described above into the nitrogen atmosphere, and use it in a nitrogen atmosphere. A film having a thickness of 150 μm was formed by the UV polymerization method under the same conditions as above. The obtained film was uniaxially stretched by a longitudinal uniaxial stretching machine at a width of 30 mm, a chuck pitch of 50 m, an extension temperature of 140 ° C, and a stretching ratio of 2 times to obtain a stretched film. The obtained stretched film had a film thickness of 〇〇μηι, R 値 = 40 nm, and had a negative optical anisotropy of Νζ値=〇. That is, the obtained polymer has a negative molecular polarizability anisotropy. The three-dimensional refractive index wavelength dispersion data of the obtained stretched film is shown in Table 21. -81 - 200919035 [Table 21] Table 21 Λ (nm) n„x door ny____ 1. 50945 〇ηι 4 5 0 1. 51373 1 . 5 13 7 3 5 5 0 1.4 9 5 5 3 1. 49153 1 . 9 5 5 3 6 5 0 1 . 4 8 0 8 8 1. 47704 1. 4 80 8 8 (1 2) Modulation of a material forming a layer (B) having positive optical anisotropy as positive optical anisotropy The material is a copolymerized polycarbonate having an anthracene skeleton. The polymerization of the polycarbonate uses an interfacial polycondensation method using a well-known phosgene. Specifically, a reaction tank equipped with a stirrer, a thermometer, and a circulation cooler. Medium in which an aqueous sodium hydroxide solution and ion-exchanged water are placed, and a monomer having a structure represented by the following chemical formulas (H) and (m) is dissolved therein at a molar ratio of 50 to 5 Torr, respectively, and then, a small amount is added. Bisulfite. [Chemical Formula 2]

Then '82- 1 2 will be - the chlorine plant is added to it, at 20. (: phosgene was blown in at a time of about 60 minutes 200919035. Then, after p-tert-butylphenol was added to emulsify it, triethylamine was added and stirred at 3 (TC for about 3 hours to complete the reaction. The reaction was completed. Thereafter, the organic phase was separated, and dichloromethane was evaporated to obtain a polycarbonate copolymer. The composition ratio of the obtained copolymer was approximately the same as the addition ratio, and the glass transition point temperature was 250 ° C. The glass transition point temperature of the polymers forming the multilayer structure is a phosphate compound having a structure of the following chemical formula (IV) as a main component (manufactured by Daiha Chemical Industry Co., Ltd., trade name: PX200) and obtained therefrom. The ratio of the polycarbonate copolymer was 30% by mass to 70% by mass, and both of them were dissolved in dichloromethane to prepare a doping solution having a concentration of 20% by mass.

Using the obtained doping solution, film formation was carried out on the glass by solution casting. After placing in a constant temperature dryer at 40 ° C for 10 minutes, the film was peeled off from the glass. Then, the film was sandwiched between rectangular metal frames, and then placed in a constant temperature drier at 80 ° C for 10 minutes for 10 minutes to dry. The film obtained was measured to have a glass transition point temperature of 120 C and a film thickness of 148 μm. -83- 200919035 The obtained film was uniaxially stretched by a longitudinal uniaxial stretching machine at a width of 30 m, a distance between the jigs of 50 m, an extension temperature of 140 ° C, and a stretching ratio of 2 times. The obtained stretched film had a film thickness of i 00 μm, R 値 = 90 nm, and Ν ζ値 = 1. The three-dimensional refractive index wavelength dispersion data of the obtained stretched film is shown in Table 22. [Table 22] Table 22 λ (ηη) Threshold η„ Gate PZ 450 1 . 6 2 3 0 9 1 . 6 2 4 0 2 1 . 6 2 3 0 9 550 1 . 6 14 9 0 1 . 6 15 8 0 1 . 6 14 9 0 6 5 0 1 . 6 0 8 8 1 1 . 6 0 9 6 9 1.6 088 1 The obtained polycarbonate copolymer and the above phosphate compound (Da Ba Chemical Industry Co., Ltd.) The ratio of the product name: PX2 00) was 70% by mass and 30% by mass, respectively, and dissolved in toluene to prepare a toluene solution having a solid concentration of 0.15 mass%, and the solution was used as a toluene solution. Rotary coating solution B. (3) Preparation of a retardation film composed of one repeating multilayer structure is described in Table 23, and a layer having negative optical anisotropy is formed by a spin coating method (A) And a layer (B) having a positive optical anisotropy as a constituent unit of the interactive multilayer film. Specifically, the spin coating solutions A and B obtained in the above manner are alternately laminated by spin coating. After honing the surface of the glass substrate (diameter: 15 cm). Before the coating of each layer, as a surface treatment, the first step was -5 〇 -84- 200919035 UV ozone treatment. When UV ozone treatment is used, it is made by Eye Graphics, trade name: Eye UV ozone cleaning device 〇c — 250615 — D+A, and trade name: Eye ozonolysis device 〇ca — 1 5 0 L - D. The coating amount of the spin coating is 3 m 1 for the spin coating solution A, 7 m 1 ' for the solution B, and 4,000 rotations for the rotation condition. The time is set to 20 seconds. The obtained repeating multilayer film is peeled off from the glass by a longitudinal uniaxial stretching machine with a width of 30 mm, a distance between the jigs of 5 mm, and an extension temperature of 140%. (3. Extension ratio 2 times uniaxial stretching was performed to thereby obtain a retardation film. [Table 23] Table 23 Total film thickness (nm) Total number of A layers Total number of B layers A film thickness (nm) B layer film thickness (nm) 9000D 3000 3000 25 5 λ (nm) R Inm) Rth (nm) nx n, n2 Nz 450 302 35 1. 53250 1.52914 1. 53043 0.62 550 281 83 1. 51608 1.51295 1.51360 0.79 650 270 123 1. 50296 1.49996 1. 50009 0.96 R ( 450) R(650) Rth (450) Rth (650) /R (550) /R (550) /Rth (550) /Rth (550) 1.07 0.96 0.43 1.49 -85 - 200919035 Table 24 [Table 24] λ frim) a+b +bnpx Vfln«"2 4 5 0 8. 3 9 3 8 8. 3 8 2 5 8. 3 7 5 4 5 5 0 8. 3 0 3 9 8 2 9 0 3 8. 2 8 6 8 6 5 0 8. 2 3 2 0 8. 2 16 3 8. 2 15 6 (4) The phase difference film obtained by the evaluation of the phase difference thin is R値=273 nm, A biaxial retardation film having a film thickness of 92 μm and Ν 0.8 = 0.8. In addition, the total light transmittance was 9 1 %, and the haze was 0.5%. The transmittance and reflectance were measured using a spectrophotometer (manufactured by Hitachi, Ltd., trade name: U4000) at a measurement wavelength of 550 nm. The internal reflectivity is approximately 0%. Next, the cross-section of the retardation film was observed by a transmission electron microscope, and it was confirmed that the thickness was substantially the same as that of the design. Here, the layers formed by the spin coating solution A and the solution B are each referred to as an A layer or a B layer, and the average optical anisotropy of each layer is obtained by using the above formulas (14) to (16). The optical anisotropy of each layer in the multilayer structure of the retardation film is not easily measured directly. However, as described above, the refractive index wavelength dispersion of the inherent physical properties of the material forming the A layer and the B layer, and the birefringence wavelength dispersion and repetition are repeated. The film thickness and the number of layers of each layer of the multilayer structure, and the wavelength dispersion data of R値 and Rth値 can be obtained by using the above formulas (14) to (16), and the average optical anisotropy of each layer can be obtained. As a result, it was confirmed that it was substantially in accordance with the design and satisfied the above formulas (5) to (7). -86-200919035 <Example 2 > [Optical design of repeating multilayer structure] As shown in Tables 25 to 28, as shown in Tables 25 to 28, a layer (A) having a negative optical anisotropy and having a positive The optically anisotropic layer (B) has a repeating multilayer structure as a constituent unit, and is formed into a repeating multilayer structure in accordance with the design. Here, a and b in Table 28 are the film thicknesses of the A layer and the B layer, respectively. Further, the azimuth axis orientation in the plane of the tantalum layer is set to be substantially perpendicular to the longitudinal axis orientation in the plane of the tantalum layer, and the slow phase axis orientation of the B layer and the slow phase axis orientation in the plane of the repeated multilayer structure Set to be consistent. (1) Preparation of material for forming layer (A) having negative optical anisotropy A polymerized polymer was obtained in the same manner as in Example 1, and then a solution A for spin coating was produced. Further, in the same manner as in Example 1, a film having a thickness of 150 μm was formed. The obtained film was subjected to uniaxial stretching by a longitudinal uniaxial stretching machine at a width of 3 Omm, a distance between the inter-clamps of 50 mm, an extension temperature of 146 t, and a stretching ratio of 2 times to obtain a stretched film. The obtained stretched film had a film thickness of 99 μm, R 値 = 90 nm, and had a negative optical anisotropy of Nz 値 0. That is, the obtained polymer has a negative molecular polarizability anisotropy. The three-dimensional refractive index wavelength dispersion data of the obtained stretched film is shown in Table 25. -87- 200919035 [Table 25] Table 25 λ Μ Gate (Ιϊ 4 50 1 . 5 T 1 6 6 1 . 5 12 6 2 1 . 5 12 6 2 5 5 0 1. 49360 ΓΓ^ΤΤΓο~ 1.49 4 5 0 6 5 0 1. 4 7 9 0 2 4 79—8—9~ 1.4 7 9 8 9 (2) Modification of the material forming the layer (B) having positive optical anisotropy in the same manner as in the first embodiment' A copolymerized polycarbonate having a glass transition point temperature of 205 ° C is obtained. Next, in order to make the glass transition point temperature of the polymers satisfying the formation of the multilayered structure, the phosphate ester system having the structure of the following chemical formula (IV) as a main component The ratio of the compound (manufactured by Daihachi Chemical Co., Ltd., trade name: PX200) to the obtained polycarbonate copolymer was 20% by mass and 80% by mass, respectively, so that both of them were dissolved in dichloromethane to prepare a concentration. 20% by mass of the doping solution. Using the obtained doping solution, a film was formed on the glass by a solution casting method, and placed in a constant temperature dryer at 40 ° C for 1 minute, and then the film was peeled off from the glass. Then 'clip the film in a rectangular metal frame' and then, at 80 ° C, 1 〇 minutes At 140 ° C for 1 hour, it was placed in a constant temperature dryer to be dried. The glass transition point temperature of the obtained film was measured to be 140 ° C, and the film thickness was 149 μηη. Uniaxial stretching machine, uniaxially extending with a width of 30 mm, a distance between clamps of 50 mm, an extension temperature of 146 °C, and a stretching ratio of 2 times. The obtained stretched film has a film thickness of 100 μm. , R値=2 3 0 nm, N z値=1. The three-dimensional folding-88-200919035 radiance wavelength dispersion data of the obtained stretched film is not shown in Table 26. [Table 26] Table 2 6 λ (run) Πρχ η Ρ» n pz 4 5 0 1. 62498 1 . 6 2 2 6 1 1 . 6 2 2 6 1 5 5 0 1. 61673 1 . 6 14 4 3 1. 61443 6 5 0 1 . 6 10 6 0 1.6083 5 1 . 6 0 8 3 5 Next, the ratio of the obtained polycarbonate copolymer to the above phosphate compound (manufactured by Daisaku Chemical Co., Ltd., trade name: PX200) was made 80% by mass. /〇, 20% by mass, dissolved in toluene, and a toluene solution having a solid concentration of 0.35% by mass was prepared, and this solution was used as a solution B for spin coating. Under the conditions of 7, a layer (A) having negative optical anisotropy and a layer (b) having positive optical anisotropy were used as a constituent multilayer interfacial film by a spin coating method. Specifically, the spin coating solutions A and B obtained in the above manner were alternately laminated on a glass substrate (diameter: 15 c m ) subjected to surface honing by a spin coating method. Further, before the application of each layer, as a surface treatment, a UV treatment of 15 seconds was performed first. For UV ozone treatment, use Eye Graphics, trade name: Eye UV ozone cleaning device 〇c — 250615 — D+A, and trade name: Eye ozonolysis unit 〇CA 1-5 0 L - D. The coating amount of the spin coating was set to 3 ml for the spin coating solution a and 7 ml for the solution B, and the rotation number was set to 4000 rotation/min., and the time was set to 20 seconds. -89- 200919035 The obtained multilayer film was peeled off from the glass, and uniaxially stretched by a longitudinal uniaxial stretching machine at a width of 30 mm, a distance between the jigs of 50 mm, an elongation temperature of 14 6 ° C, and a stretching ratio of 2 times. Extend the film. [Table 27] Table 27 Total film thickness (nm) Total A layer total B layer total A layer film thickness (nm) B layer film thickness (nm) 70000 1750 1750 25 15 λ (nm) R (nm) Rth (nm) nx Nz 450 24 263 1. 5551 1. 5548 1.5512 11.47 550 25 313 1. 5409 1, 5406 1. 5363 12. 96 650 26 360 1. 5297 1. 5293 1. 5244 14.50 R (450) R (650) Rth ( 450] Rth(650) /R (550) /R(550) /Rth(550) /Rth (550) 0. 95 1.02 0.84 1.15 [Table 28] Table 28 α + ό ^anv'2 + bn λ W vaw * XJ yjann/ +bnj 4 5 0 9. 8 3 5 5 9. 8 10 6 9. 8 3 3 3 5 5 0 9. 7 4 5 7 9. 7 16 3 9. 7 4 3 4 6 5 0 9 6 7 4 6 9. 6 4 10 9. 6 7 2 3 (4) Evaluation of phase difference thinness -90- 200919035 The phase difference film obtained is R値=25 nm, film thickness=72 Pm, Νζ値=13, A biaxial retardation film of Rth 値 = 308. Further, the total light transmittance was 91%, and the haze was 〇·5 %. Further, a spectrophotometer (manufactured by Hitachi, Ltd., trade name: U4000) was used for measurement. The transmittance and the reflectance were about 〇% at a measurement wavelength of 550 nm. Next, the phase difference film profile was observed using a transmission electron microscope to confirm the thickness. Here, the layer formed by the spin coating solution A and the solution B is used as the A layer and the B layer, respectively, and the average optical of each layer is obtained by using the above formulas (14) to (16). As a result, it was confirmed that it was substantially in accordance with the design. <Example 3 > In the repeated multilayer structure, the polymer used as the layer (B) having positive optical anisotropy was used. The olefin copolymer (B3) of the bornene copolymer skeleton is trade name: TOPAS 6013 (manufactured by Topas Advanced Polymers Co., Ltd.), and on the other hand, as a material for forming the layer (A) having negative optical anisotropy, styrene is used. - The trade name of the anhydrous maleic acid copolymer (A3): dYLARK D3 3 2 (manufactured by NOVA Chemicalse Co., Ltd.) These polymer materials are separately dried and then supplied to a press machine. The melt viscosities of the polymer materials (A3) and (B3) were 500 Pa.s and 7 () () Pa.s, respectively. Each of the molecular materials (A3) and (B3) is made into a molten state of 260 C by an extruder, and after passing through a gear pump and a filter, a shunt block of 2〇1 -91 - 200919035 layer is fed. Block) merges, and then, by means of four static mixers, a structure of 3 2 〇 1 layers having the same thickness is formed. The mold was introduced into the mold while maintaining the lamination, and the mold was cast on a casting cylinder to prepare a total of 320 1 layers of the unstretched multilayer film in which the polymer materials (A3) and (B3) were alternately laminated. At this time, the amount of extrusion of the polymer materials (A3) and (B3) was adjusted to 58:42. Further, the residence time from the splitting block to the extrusion from the die is about 8 seconds. The unstretched multilayer film obtained in this manner was subjected to uniaxial 2.5-fold extension under 14 〇 to obtain a retardation film having a repeating multilayer structure. The thickness of the retardation film is 1 20 μm, the film thickness of the layer having positive optical anisotropy is 41 nm on average, and the film thickness of the layer (a) having negative optical heterogeneity is 30 nm on average, and the mismatched region is 3 nm. Almost no observations have been made below. The characteristics of the obtained multilayer retardation film are shown in Table 29. When it is incident on the front side, the wavelength characteristic of the retardation R is an inverse dispersion characteristic. On the other hand, the wavelength of Rth is dispersed, and the wavelength dispersion of the shorter wavelength becomes larger, which shows that the dispersion of R and Rth can be independently controlled. It is extremely difficult to achieve in the conventional phase difference film. -92- 200919035 [Table 29] Table 29 Full Film Thickness A Layer Average Film Thickness B Layer Average Film Thickness (nm) (nm) (nm) 120000 41 30 λ (nm) R (nm) Rth (nm) Kz 450 80 179 2.7 550 99 156 2.1 650 109 145 1.8 R (450) R (650) Rth (450) Rth (650) /R (550} /R (550) /Rth (550) /Rth (550) 0. 80 1.10 1,15 0.93 In addition, the individual resin optical properties of the respective layers forming the repeating multilayer structure which were carried out by the method of the above (6) (i) are shown in Table 30. Further, 'repeated by the method of the above (6) The average in-plane refractive index difference |nx-ny| of the layer (A) having negative optical anisotropy and the layer (B) having positive optical anisotropy is determined for each layer parameter of the multilayer structure, and is recorded in the table. 31. Further, the late-phase axis in the plane of the layer (A) having negative optical anisotropy intersects the direction of the extension substantially perpendicularly, and the late-phase axis in the plane of the layer (B) having positive optical anisotropy The extending direction is substantially parallel. Further, the retardation axis orientation in the entire plane of the retardation film is substantially parallel to the extending direction. -93- 200919035 [Table 30] Table 30 The resin constituting each layer - Optical property A3 (negative) Β 3 GH) η (4 5 0) 1 . 6 0 14 1 . 5 4 3 3^ η (5 5 0) 1.5 8 5 3 1.5 3 5"〇^ η (6 5 0) 1 . 5 7 6 4 1.53 OT^- Δη (4 5 0) / Δ η (5 5 0) 1.07 1.01 ^ 厶η (6 5 0) /厶η (5 5 0) 0.9 7 0.9 9, [Table 31] Table 31 λ = 5 5 0 nm Α layer B layer 1 η ny 1 0. 006 0.006 It is known that the left side of the above formula (8) is 0.8 1 6 ' is less than 〖, satisfies the formula <Example 4 > (1) forms a negative optical difference Modification of the material of the directional layer (A) 950 parts by weight of a styrene polymer (Haima s τ - 95 manufactured by Sanyo Chemical Industries Co., Ltd.) was dissolved in 3250 parts by weight of the ring, and the polymer solution was set. Into a stainless steel autoclave, followed by adding 650 parts by weight of methyl t-butyl ether, nickel/cerium oxide/alumina catalyst (Ni holding amount of Aldrich, 65% by weight) 80 parts by mass, hydrogen pressure 9.8 1 Μ P a, 1 0 0 ° C was subjected to a hydrogenation reaction for 3 hours to obtain a hydrogen-added polystyrene (A4) having a hydrogenation ratio of 99.9 mol% and Tg = 148 °C. The melt viscosity is 700 Pa.s. -94- 200919035 (2) Modulation of a material forming layer (B) having positive optical anisotropy In the modulation of (2) of Example 1, 'except that the monomer addition ratio is set to (11): (111) = 3 0 : 7 0, the same method is used to get

Tg = l 30 ° C thermoplastic tree (B4). The melt viscosity is 900 Pa·s. (3) Creation of multilayer structure The thermoplastic resins (A4) and (B4) were dried and supplied to an extruder. Each of the thermoplastic resins was melted at a temperature of 280 ° C by an extruder, and after passing through a gear pump and a filter, it was joined by a split block of 210 layers, and then passed through four The static mixer is a structure of 320 layers of equal thickness of each layer. The mold was introduced into the mold while maintaining the lamination, and the mold was cast on a casting cylinder to form a total of 3 20 1 layers of the unstretched multilayer film in which the thermoplastic resin (A4) and the thermoplastic resin (B4) were alternately laminated. At this time, the amount of extrusion of the thermoplastic resin (B4) and the thermoplastic resin (A4) was adjusted to 32:68. Further, the residence time from the splitting block to the extrusion from the die was about 40 seconds. The unstretched multilayer film obtained in this manner was subjected to uniaxial 2 _ 3 times extension at 150 ° C to obtain a retardation film composed of a repeating multilayer structure. The retardation film had a thickness of about 1 20 μm, the thermoplastic resin B 4 layer had an average of 9 nm. The thermoplastic resin crucible 4 had an average of 36 nm, and the blended region had an average of 15 nm. The characteristics of the obtained multilayer retardation film are shown in Table 32. When it is incident on the front side, the wavelength characteristic of the retardation r is inverse-95-200919035. On the other hand, the wavelength dispersion of Rth becomes the general wavelength dispersion of the shorter wavelength dispersion, showing that R and Rth can be independently controlled. This is extremely difficult to achieve in the conventional phase difference film. [Table 32] Table 32 Full film thickness (nm) A layer average film thickness (nm) B layer average film thickness (nm) 120000 36 9 λ (nm) R (nm) Rth (nm) Nz 450 25 238 9. 9 550 42 217 5. 6 650 52 199 4 3 R (450) R (650) Rth (450) Rth (650) /R (550) /R(550) /Rth (550) /Rth (550) 0.60 1.22 1.10 0.92 Further, the individual resin optical properties of the respective layers forming the multilayer structure which were carried out by the method of (6) (i) above are shown in Table 33. According to the method of the above (6), the layer parameters of the repeated multilayer structure are obtained, and the layer (A) having negative optical anisotropy and the average in-plane refractive index difference with positive optical anisotropy (B) |nx - ny| In the surface of the layer (A) having a negative optical anisotropy, the direction of the late-phase axis is substantially perpendicularly intersected, and the late-phase axis in the layer (B) having positive optical anisotropy It is roughly parallel to the direction of extension. Further, the phase difference is divided by the fraction of the layer 34 obtained. The direction of the azimuth axis in the plane of the body of the film is approximately perpendicular to the direction of extension. [Table 33] Table 33 Optical properties of the resin constituting each layer Α 4 (negative) Β 4 (positive) η (4 5 0) 1.5166 1 . 6 2 3 4 η (5 5 0) 1 . 5 113 1 . 6 15 2 η (6 5 0) 1 . 5 0 8 2 1. 6091 Δη (4 5 0) / Δη (5 5 0) 0.9 4 1.03 Δη (6 5 0) / Δ η (5 5 0) 1.03 0.9 8 [Table 34 Table 34 Λ = 5 5 0 nm Α layer 1 layer 1 η xn y1 0. 0 0 2 5 0. 004 It is found that the left side of the above formula (8) is 0.8 7 1, the system is small 1, and the formula is satisfied. 5 > In the same manner as in the third embodiment, the polymer material (A3) was prepared into two types of thermoplastic resins. These thermoplastic trees are dried and then supplied to the extruder. Each of the thermoplastic resins is brought into a state by an extruder, and after passing through a gear pump and a filter, it is merged by 2 0 1 , and then passed through a double 4 division (to | Further arranged in the thickness direction), thereby forming a name and (B 3 ) as a shunting layer for the molten layer of 260 ° C, respectively: splitting in the direction direction - thickness of the layer is 80-1 of the phase -97 - 200919035, etc. The structure of the layer. The mold was introduced into the mold while maintaining the lamination, and the mold was cast on the casting drum to form a total of 801 unstretched multilayer films in which the thermoplastic resin (A3) and the thermoplastic resin (Β 3 ) were alternately laminated. At this time, the amount of extrusion of the thermoplastic resin (Β3) and the thermoplastic resin (A3) was adjusted to be 6 2 : 3 8 . Further, the residence time from the splitting block to the extrusion from the die was about 30 seconds. The unstretched multilayer film obtained in this manner was subjected to uniaxial 2.5-fold stretching at 40 ° C to obtain a multilayer retardation film. The thickness of the multilayer retardation film was about 40 μm, the layer of the thermoplastic resin B3 was 42 nm on average, the layer of the thermoplastic resin A3 was an average of 18 nm, and the blending region was about 20 nm. The characteristics of the obtained retardation film are shown in Table 35. When it is incident on the front side, the wavelength characteristic of the retardation R is an inverse dispersion characteristic. On the other hand, the wavelength of Rth is dispersed, and the shorter the wavelength, the larger the dispersion of the wavelength is, and the dispersion of R and Rth can be independently controlled. It is extremely difficult to achieve in the conventional phase difference film. -98- 200919035 [Table 35] Table 35 Full film thickness (nm) Average thickness of layer A (nm) Average thickness of layer B (nm) 40000 18 42 λ (nm) R (nm) Rth (nm) Nz 450 50 58 1.7 550 55 53 1.5 650 58 51 1.4 R (4501 R(650) Rth (450) Rth (650) /R (550) /R (550} /Rth (550) /Rth (550) 0. 90 1. 05 1.10 0.96 According to the method of the above (6), the parameters of the layers of the repeated multilayer structure are obtained, and the average in-plane of the layer (A) having negative optical anisotropy and the layer (B) having positive optical anisotropy is obtained. The refractive index difference |nx - ny | is shown in Table 36. Further, the late-phase axis in the plane of the layer (A) having negative optical anisotropy intersects the direction of the direction substantially perpendicularly, and has positive optical anisotropy. The retardation axis in the plane of the layer (B) is substantially parallel to the extending direction. Further, the orientation of the slow phase axis in the plane of the retardation film as a whole is substantially parallel to the extending direction. -99- 200919035 [Table 36] 3 6 Λ — 5 5 0 nm A layer B calendar I nx-nv I 0. 0 0 6 0.006 It is known that the left side of the above formula (8) is ο·”?, which is less than 1, and satisfies the formula <Example 6 &gt In addition to the extrusion amount of resin (Β3) and (Α3) In the same manner as in Example 3, the unstretched multilayer film was formed in the same manner as in Example 3, in which 44: 5 6 'the retention time from the completion of the flow of the split block to about 30 seconds was obtained. The multilayer film is stretched at 140° (by: transversely uniaxial 2·0 times extension to obtain a retardation film composed of a repeating multilayer structure. The thickness of the retardation film is about 120 μm, thermoplasticity The layer of the resin (B3) was an average of 18 nm, the layer of the thermoplastic resin (A3) was an average of 27 nm, and the mismatched area was I5 nm. The characteristics of the obtained multilayer retardation film are shown in Table 37. Νζ = 0.5 was obtained. Phase difference film. -100- 200919035 [Table 37] Table 37 Full film thickness (nn) A layer average film thickness (nm) B layer average film thickness (nm) 120000 27 18 Λ (nm) R (nm) Rth (nm ) Wz 0.5 450 121 0 550 94 "1 0.5 650 81 0 0.5 R (450) /R (550) R(650) /R (550} Rth (450) /Rth(55〇) Rth (650) /Rth (550} 1. 28 0.86 ' 明丨0.33 0.48 According to the method of the above (6), the parameters of each layer of the repeated multilayer structure are determined, and the layer having negative optical anisotropy is further obtained (A) Average in-plane refractive index difference has a positive optical anisotropy in the layer (B) of | Πχ a ny Shu, which is shown in Table 38. Further, it is known from Table 39 that the formula (5) can be satisfied. Further, the slow phase axis in the plane of the layer (A) having the optical anisotropy of the chamber intersects the extending direction substantially perpendicularly, and the retardation axis and the extending direction in the plane of the layer (B) having positive optical anisotropy Roughly parallel. Further, the retardation axis orientation in the plane of the entire retardation film is substantially perpendicular to the extending direction. -101 - 200919035 [Table 38] Table 38 λ —5 5 0 nm A layer B layer i nx~n yI 0. 006 0. 0 0 6 [Table 39] Table 39 λ {m) Ql· b +Aiifc-2 — ^anj +bntt1 4 5 0 1 0. 58 98 1 0. 5 8 5 9 1 0.5 796— 5 5 0 1 0. 5023 1 0. 4 9 9 6 1 0- 4 9 3 7 6 5 0 1 0 45 31 1 0. 4509 1 0. 4 4 5 3 <Example 7 > In the same manner as in Example 3 except that other resin layers were changed to change the mechanical properties on both sides of the multilayer structure. A phase difference film is formed by extrusion. A resin which forms the other resin layer (a vinyl-based copolymer resin (product name of Sumitomo Chemical Co., Ltd.) is used. The mechanical properties of the resin are shown in Table 40. Two kinds of thermoplastic resins constituting a repeating multilayer structure (A3 (B3) is melted at 260 ° C by an extruder, and after passing through the pump and the filter, it is merged by a 201-layer split block, and then passed through 4 static mixers. A structure in which layers of equal thickness are formed. The structure is introduced into the mold while maintaining the lamination state. Then, the resin (C6) is joined to the two outermost layers of the laminated structure, and then cast in a casting cylinder to form a resin (C 6 A film laminated on both sides of a total of 3 2 0 1 layers. At this time, 'the thermoplastic resin B3 and the heat are provided with a plurality of layers C6): A) and by the teeth, by 320 1 , the upper multi-plastic mold -102 - 200919035 The resin (A3) was adjusted in a way that the extrusion amount was 58:42. Further, the residence time from the joining of the splitter block to the extrusion from the die was about 8 seconds. The unstretched multilayer film obtained in this manner was subjected to uniaxial 2.5-fold stretching at 1, 40 ° C to obtain a multilayer retardation film. The thickness of the multilayer retardation film was 140 μm, and the thickness of the two outermost layers composed of the resin (C6) was 1 Ομηι, and the optical characteristics and the average thickness of each layer of the repeated multilayer structure were substantially the same as those of Example 3. The mechanical properties of the retardation film composed of the repeating multilayer structure prepared in this example are shown in Table 40. [Table 40] Table 40 Repeated multilayer structure Breaking strength (MPa) 79.8 Breaking elongation (%) 5.0 Surface impact failure energy (J/μπι) 7x10'5 Breaking strength (MPa) 22.4 Breaking elongation (%) 1120 Resin (C6 ) Surface impact damage energy (J/μιη) 1.6xl0'3 Dynamic storage modulus (Pa) 9·1χ107 Dynamic loss modulus (Pa) 8.2χ105 [Industrial use possibility] Since the phase difference film of the present invention is used Both the molecularly oriented birefringence and the structural birefringence caused by the repeated multilayer structure can realize optical anisotropy and wavelength dispersion characteristics which are difficult to achieve by conventional methods. Therefore, the phase difference film of the present invention is used alone in a liquid crystal display device, or the -103-200919035 is combined with a polarizing plate or other retardation film, and is used in a liquid crystal display device to improve the performance of the display device. (especially a wide viewing angle) has a great contribution. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic diagram showing a repeating multilayer structure and a refractive index ellipsoid of a retardation film of the present invention. Fig. 2 is a schematic diagram showing a repeating multilayer structure and a refractive index ellipsoid of a conventional technique in which each layer is optically isotropic. Fig. 3 is a schematic diagram showing the repeated multilayer structure of the present invention and the refractive index ellipsoid in which three layers are used as constituent units. Fig. 4 is a schematic view showing a repeating multilayer structure of the present invention in which two kinds of layers having different thickness ratios are used as constituent units. Fig. 5 is a schematic view showing the constitution of the laminated polarizing film of the present invention. Fig. 6 is a schematic view showing the configuration of a liquid crystal display device of the present invention. [Description of main component symbols] 1 1 : First layer 12 : Second layer 13 : Repeated multilayer structure 1 4 : Refractive index ellipsoid 1 5 : Refractive index ellipsoid of the first layer 1 6 : Refractive index ellipse of the second layer Body a, b, dH, dL ' dl, d2, d3 : film thickness -104- 200919035 21: Η layer (optical isotropic layer) 22: L layer (optical isotropic layer) 23 : optically isotropic Repeated multilayer structure 24 composed of layers: refractive index ellipsoid 3 1 of multilayer structure 23: first layer 32: second layer 33: third layer 3 4: repeated multilayer structure of retardation film of the present invention 35: repeated multilayer Refractive index ellipsoid 36 of structure 34: refractive index ellipsoid 4 of kth layer (k=l~3): repeated multilayer structure 42 having a thickness ratio of α: repeated multilayer structure of thickness ratio β: retardation film 5 1 : polarizing film 5 2 : phase difference film 53 of the invention: optical arrangement of the laminated polarizing film of the invention 5 4 : absorption axis 5 5 = phase difference film in the plane of the retardation film 56: lamination of the invention Polarizing film 6 1 : polarizing film 62 : IPS liquid crystal cell 63 : retardation film 64 of the present invention : polarizing film 6 5 : absorption axis -105 - 200919035 6 6 : liquid crystal layer Axis 67: the slow axis 68: absorption axis of -106

Claims (1)

200919035 X. Patent Application Area 1. A retardation film comprising a repeating multilayer structure comprising at least two layers having different average refractive indices as constituent units, wherein: the repeated multilayer structure exhibits structural birefringence, at least At least one of the two layers has a negative optical anisotropy layer (A) due to molecularly oriented birefringence, and at least one of the at least two layers has molecular alignment birefringence The positive optical anisotropy layer (B). 2. The retardation film of claim 1, wherein the repeating multilayer structure satisfies the following formula (2): 0.001 < |δη| < 0.5 (2) (wherein δη represents negative The difference between the average refractive index of the optically anisotropic layer (A) and the average refractive index of the layer (B) having positive optical anisotropy). 3. A phase difference film of claim 1 or 2, which has one of { R ( λ ) /R ( λ5 ) } and {Rth(X) /Rth(X,) } is less than 1, The other is a measurement wavelength λ (nm) and λ' (nm) (400ηιη^λ < λ, ^700ηπι) exceeding one. 4. The retardation film according to any one of claims 1 to 3, which has a measurement wavelength λ (nm) and λ' (nm) satisfying the following formula (8'): 400 ηηι$λ < λ' $700ηηι): ίΙ(λ)/ΙΙ(λ,)< 1 (8,). The phase difference film according to any one of claims 1 to 4, which has a measurement wavelength λ (nm) and λ' (nm) (4〇〇ηηι$λ) satisfying the following relationship: λ'$700ηηι) · I {Rth(X)/RthQ,)}— {Ι1(λ)/Ι1(λ,)} I gO.l ° 6. As in any of items 1 to 5 of the patent application scope a phase difference film in which the layer having negative optical anisotropy and the layer having positive optical anisotropy have optical anisotropy due to molecular orientation birefringence in the plane, The retardation axes of the layer having negative optical anisotropy and the layer having positive optical anisotropy (Β) are arranged to substantially perpendicularly intersect each other. 7. The retardation film according to any one of claims 1 to 6, wherein the alignment index (Νζ 値 (λ)) of the repeating multilayer structure in the thickness direction satisfies the following formula (3): (3) 0 < Ν ζ < {wherein, [Math 1] nx - (4) (nx: three-dimensional refractive index in the X-axis direction of the repeated multilayer structure ny: three-dimensional refractive index in the y-axis direction of the repeated multilayer structure nz: repetition Three-dimensional refractive index in the x-axis direction of the multilayer structure -108- 200919035 X-axis: the slow-phase axis y-axis of the repeated multilayer structure in the plane of the repeated multilayer structure · the axis perpendicular to the x-axis in the plane of the repeated multilayer structure Axis: the axis of the normal orientation of the face of the repeating multilayer structure). 8. The retardation film of any one of claims 1 to 7 wherein 'the above-mentioned layer (A) having negative optical anisotropy and/or layer (B) having positive optical anisotropy is satisfied. The following formula (1): (wherein, ηχ: layer having negative optical anisotropy or layer having positive optical anisotropy (Β) has a three-dimensional refractive index ny: negative optical difference Three-dimensional refractive index X-axis of the directional layer (a) or the layer (B) having positive optical anisotropy in the y-axis direction: the slow-phase axis y-axis of the repeated multilayer structure in the plane of the repeated multilayer structure: The axis of the perpendicular intersection of the χ axes in the plane of the structure). The retardation film 'where' as the constituent unit of the above-mentioned repeated multilayer structure is the χ/5 or less of the retardation film of any one of the above-mentioned patents. The retardation film of any one of the above-mentioned items of the first to ninth aspect, wherein the number of layers forming the above-mentioned repeating multilayer structure is 100 or more and 30,000 or less 〇1 1 . The phase difference thin film of any one of the items -109-200919035, wherein the layer having the negative optical anisotropy (A) and the above-mentioned molecular anisotropic birefringence of the layer (B) having positive optical anisotropy It is represented by the molecular alignment of the polymers constituting the layer (A) and the layer (B), respectively. The phase difference film according to any one of claims 1 to 11, wherein the layer (A) having a negative optical anisotropy contains a smell molecule having a negative molecular anisotropy. The phase difference film according to any one of claims 1 to 2, wherein the layer (B) having positive optical anisotropy contains a polymer having a positive molecular anisotropy. The retardation film according to any one of claims 1 to 3, wherein the in-plane phase difference 値(R値(nm)) of the above-mentioned repeated multilayer structure satisfies the following formula (1 0 ) : 10nm<R< lOOOnm (10). The phase difference film according to any one of claims 1 to 4, wherein the molecular alignment birefringence is represented by extension. The phase difference film 'in any one of the first to fifth aspects of the invention is formed by multilayer melt-extruding of a polymer to form a multilayer film, and then the multilayer film is stretched. 1 7 · The phase difference film of any one of the first to sixth aspects of the patent application, wherein the absolute enthalpy of the photoelastic coefficient is 15xl (less than ri2Pa_i. 1 8. In the scope of claims 1 to 17) Any one of the retardation films is laminated on both sides of the retardation film, and has a breaking strength of 10 〇 50 MPa, an elongation at break of 3 〇〇 15 〇〇 %, and a surface impact destruction energy “ ίο·4 J/μηι The dynamic storage elastic modulus at the frequency of 1 Hz and 4 〇 °C and the dynamic loss elastic modulus of the dynamic -110-200919035 state loss elastic modulus 1 x 1 05~2 x 1 08 P a are made by the thermoplastic resin composition (P). And a retardation film (X) which is optically substantially isotropic. The retardation film according to any one of claims 1 to 18, wherein the negative optics due to molecularly oriented birefringence The anisotropic layer (A) is made of a styrene resin containing a copolymer of styrene and anhydrous maleic acid, and the copolymerized molar ratio of styrene/anhydrous maleic acid is 70/30 to 86/14. And the photoelastic coefficient is SxlO — Upa·1 or less. 20. The phase difference thin film according to any one of claims 1 to 19. The above-mentioned repeating multilayer structure is composed of two layers of a layer (A) having negative optical anisotropy and a layer (B) having positive optical anisotropy, and having the following formulas (100) and (100) One of the ') is less than 1, and the other is the measurement wavelength λ (nm) and λ'(nm) (400ηιη^λ< λ' S 700nm ) exceeding 1: [Math 2] ^anlW+bnl ^Xj-^an^+bnliX) such as ί(又Χ(Λ')- 卿十Η(8)十卿+H(7)-灰Π Ο Ο' Ί (where, a: layer with negative optical anisotropy (Α) Film thickness of one layer -111 - 200919035 b: film thickness (nm) of layer (B) having positive optical anisotropy ηηχ: three-dimensional X-axis direction of layer (A) having negative optical anisotropy Refractive index nny: three-dimensional refractive index nnz in the y-axis direction of the layer (A) having negative optical anisotropy: three-dimensional refractive index npx in the z-axis direction of the layer (A) having negative optical anisotropy: having positive optical difference Three-dimensional refractive index npy in the x-axis direction of the directional layer (B): three-dimensional refractive index npz in the seven-axis direction of the layer (B) having positive optical anisotropy: layer (B) having positive optical anisotropy Three in the z-axis direction Refractive index X-axis: the slow-phase axis of the repeating multilayer structure in the plane of the repeated multilayer structure: the axis z perpendicular to the x-axis perpendicular to the plane of the repeated multilayer structure: the normal orientation of the face of the repeated multilayer structure The retardation film according to any one of claims 1 to 20, wherein the above-mentioned repeating multilayer structure is composed of a layer (A) having a negative optical anisotropy and having a positive optical anisotropy. The two layers of the layer (B) constitute 'and have a measurement wavelength λ (nm) and λ' (nm) satisfying the following formula (200): (400ηιη$λ < λ'$700ηηι): -112- 200919035 [Math 3] v^{a)+6<(a)+V«4W+6<W--t-^^577T r-jT-τ~~r-τ^· ^0.1 _ Ά (丨)+ such as "(又)__广1(乂)+&4(4)-,.such as 4(义)+&nM again) /屺(咖拥+>/<(加"网-·^ For the second job? 4 (must disaster,) - MM + Ming (200) (wherein, a: film thickness (nm) of one layer of layer (A) with negative optical anisotropy b: with positive optical anisotropy Film thickness (nm) of one layer of the layer (B) ηηχ: three-dimensional refractive index nny of the layer (A) having negative optical anisotropy in the X-axis direction: Three-dimensional refractive index nnz in the y-axis direction of the negative optical anisotropy layer (A): three-dimensional refractive index ηρχ in the z-axis direction of the layer (A) having negative optical anisotropy: a layer having positive optical anisotropy (三维) three-dimensional refractive index npy in the X-axis direction: three-dimensional refractive index npz in the y-axis direction of a layer having positive optical anisotropy: three-dimensional z-axis direction of layer (B) having positive optical anisotropy Refractive index X-axis: the slow-phase axis of the repeating multilayer structure in the plane of the repeated multilayer structure: the axis z perpendicular to the X-axis perpendicular to the plane of the repeated multilayer structure: the normal orientation of the face of the repeated multilayer structure axis). The retardation film according to any one of claims 1 to 21, wherein the above-mentioned repeating multilayer structure is composed of a layer (A) having a negative optical anisotropy and having a positive optical anisotropy. The two layers of the layer (B) are formed, and have measurement wavelengths λ (nm) and λ'(nm) satisfying the following formula (8): (400ηιη^λ < λ, ^700ηιη): [Math 4 (wherein, a: film thickness (nm) of one layer of the layer (A) having negative optical anisotropy b: film thickness (nm) of one layer of the layer (B) having positive optical anisotropy nnx : having Three-dimensional refractive index nny of the negative optical anisotropy layer (A) in the X-axis direction: three-dimensional refractive index npx of the layer (A) having a negative optical anisotropy in the y-axis direction: a layer having positive optical anisotropy ( B) three-dimensional refractive index npy in the X-axis direction: three-dimensional refractive index in the y-axis direction of the layer (B) having positive optical anisotropy. X-axis: the slow-phase axis y-axis of the repeating multilayer structure in the plane of the repeated multilayer structure : -114- 200919035 axis perpendicular to the X-axis in the plane of the repeated multilayer structure). The retardation film according to any one of claims 1 to 22, wherein the above-mentioned repeating multilayer structure is composed of a layer (A) having negative optical anisotropy and a layer having positive optical anisotropy ( B) is composed of two layers and satisfies the following formulas (5) to (7), [Math. 5] > D. a > +bnry (5) yj ga ta η (6) nx nz n ( 7) PX P2 (wherein, a: film thickness (nm) of one layer of layer (A) having negative optical anisotropy b: film thickness (nm) of one layer of layer (B) having positive optical anisotropy Nnx : three-dimensional refractive index nny in the X-axis direction of the layer (A) having negative optical anisotropy: three-dimensional refractive index nnz in the y-axis direction of the layer (A) having negative optical anisotropy: having negative optical anisotropy Three-dimensional refractive index npx of the layer (A) in the z-axis direction: three-dimensional refractive index of the layer (B) having positive optical anisotropy in the X-axis direction -115 - 200919035 npy : layer having positive optical anisotropy (B) The three-dimensional refractive index npz in the y-axis direction: the three-dimensional refractive index in the Z-axis direction of the layer (B) having positive optical anisotropy. The X-axis: the retardation axis y of the repeating multilayer structure in the plane of the repeated multilayer structure : The axis perpendicular to the X-axis intersects the inner surface of the multilayer structure of repeating Z-axis: the axis of the multilayer structure is repeated orientation of the surface normal). 2 - A laminated polarizing film characterized by laminating a phase difference film and a polarizing film according to any one of claims 1 to 23. A liquid crystal display device comprising: a phase difference film according to any one of claims 1 to 23. -116-